Scandium complexes with the tetraphenylethylene and anthracene dianions

research papers

Scandium complexes with the tetraphenylethylene

and anthracene dianions

ISSN 2053-2296

a

b

b,c

d

John E. Ellis, Mikhail E. Minyaev, * Ilya E. Nifant’ev and Andrei V. Churakov

a

b

Chemistry Department, University of Minnesota, 207 Pleasant Str. SE, Minneapolis, MN 55455, USA, A.V. Topchiev

Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky prospect, Moscow 119991, Russian

c

Federation, Chemistry Department, M.V. Lomonosov Moscow State University, 1 Leninskie Gory Str., Building 3,

Received 20 April 2018

Accepted 15 May 2018

d

Moscow 119991, Russian Federation, and N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian

Academy of Sciences, 31 Leninsky Prospect, Moscow 119991, Russian Federation. *Correspondence e-mail:

mminyaev@mail.ru

Edited by I. D. Williams, Hong Kong University

of Science and Technology, Hong Kong

The structural study of Sc complexes containing dianions of anthracene and

tetraphenylethylene should shed some light on the nature of rare-earth metal–

carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-

Keywords: scandium; rare-earth complex;

dianion; tetraphenylethylene; anthracene; di-

phenylcyclopentadiene; NMR; crystal structure.

6

ꢀ

O)sodium bis(ꢁ -1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran

disolvate, [Na(C H O) (C H O )][Sc(C H ) ]ꢀ2C H O or [Na(18-crown-6)-

4

8

2

12 24

6

26 20 2

5

4

8

CCDC references: 1843318; 1843317;

6

(

THF) ][Sc(ꢁ -C Ph ) ]ꢀ2(THF), (1b), (ꢁ -1,3-diphenylcyclopentadienyl)(tetra-

2

4 2

1843316; 1843315

6

hydrofuran-ꢀO)(ꢁ -1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemi-

5

6

solvate, [Sc(C H )(C H )(C H O)]ꢀ0.5C H or [(ꢁ -1,3-Ph C H )Sc(ꢁ -C Ph )-

Supporting information: this article has

17 13

26 20

4

8

7

3

8

2

5

3

6

2

4

3

supporting information at journals.iucr.org/c

(THF)]ꢀ0.5(toluene), (5b), poly[[(ꢂ

-ꢁ :ꢁ -anthracenediyl)bis(ꢁ -anthracenedi-

2

yl)bis(ꢁ -1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassium-

discandium(III)] tetrahydrofuran monosolvate], {[K Sc (C H ) (C H ) -

5

2

14 10 3 17 13 2

(

1

C H O) ]ꢀC H O} or [K(THF) ] [(1,3-Ph C H ) Sc (C H ) ]ꢀTHF, (6), and

4

8

4

8

n

2 2

2

5

3 2

2

14 10 3

,4-diphenylcyclopenta-1,3-diene, C H , (3a), have been established. The

17 14

6

ꢁ

[Sc(ꢁ -C Ph ) ] complex anion in (1b) contains the tetraphenylethylene

2 4 2

3

dianion in a symmetrical bis-ꢁ -allyl coordination mode. The complex

6

ꢁ

homoleptic [Sc(ꢁ -C Ph ) ] anion retains its structure in THF solution,

2

4 2

1

displaying hindered rotation of the coordinated phenyl rings. The 1D H and

13

1

13

1

C{ H}, and 2D COSY H– H and C– H NMR data are presented for

M[Sc(Ph C ) ]ꢀxTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in

4

2 2

3

THF-d media. Complex (5b) exhibits an unsymmetrical bis-ꢁ -allyl coordina-

tion mode of the dianion, but this changes to a ꢁ coordination mode for (1,3-

Ph C H )Sc(Ph C )(THF) , (5a), in THF-d solution. A Sc NMR study of (2a)

8

4

45

2

5

3

4

2

and UV–Vis studies of (1a), (2a) and (5a) indicate a signiﬁcant covalent

contribution to the Sc—Ph C bond character. The unique Sc ate complex, (6),

4

2

6

contains three anthracenide dianions demonstrating both a ꢁ -coordination

3

mode for two bent ligands and a ꢂ -ꢁ :ꢁ -bridging mode of a ﬂat ligand. Each

[

2

ꢁ

(1,3-Ph C H ) Sc (C H ) ] dianionic unit is connected to four neighbouring

2 5 3 2 2 14 10 3

+

units via short contacts with [K(THF) ] cations, forming a two-dimensional

2

coordination polymer framework parallel to (001).

1

. Introduction

Rare-earth complexes with dianions of aromatic hydrocarbons

are currently of mainly fundamental interest. Generally, the

Ln—C bond is considered to be ionic in character in many

organometallic compounds (Raymond & Eigenbrot, 1980).

However, a substantial covalent component is sometimes

present in Ln—C bonding in rare-earth complexes with some

dianionic ligands, which has been demonstrated, for example,

for anthracenide complexes (Roitershtein et al., 1993). The

purpose of this work is the structural study of Sc complexes

containing dianions of anthracene and tetraphenylethylene in

order to shed some light on the nature of the rare-earth metal–

carbon bonding.

#

2018 International Union of Crystallography

Acta Cryst. (2018). C74, 769–781

https://doi.org/10.1107/S2053229618007295 769

research papers

Tetraphenylethylene (for its crystal structure, see, for

example, Hua et al., 2007; Jin et al., 2016) is easily reduced to

the dianion by alkali metals in ꢃ-donating solvent media

2007; Minyaev et al., 2007; see Results and discussion (x3)

below], in some part due to their extremely high reactivity to

traces of moisture and oxygen.

(

Et O, THF, diglyme, etc.) (Matsui et al., 1994; Szwarc, 1968).

2

Anthracene ꢄ-complexes of d-metals have been explored

extensively in recent decades [57 crystal structures according

to the Cambridge Structural Database (CSD; Version 5.39,

with latest updates to February 2018; Groom et al., 2016)], but

rare-earth anthracenide complexes have been poorly explored

to date, including their crystal structures (see The CSD survey,

x3.6.3) and possible practical applications.

Although detailed preparation and reactivity studies of the

disodium tetraphenylethylene salt were reported 90 years ago

We report herein the synthesis and structures of two Sc–

tetraphenylethenide complexes, namely [Na(18-crown-6)-

6

5

(

THF) ][Sc(ꢁ -C Ph ) ]ꢀ2(THF), (1b), and [(ꢁ -1,3-Ph C H )-

2

4 2

2

5

3

6

Sc(ꢁ -C Ph )(THF)]ꢀ0.5(toluene), (5b), and the Sc–anthrace-

2 4

6

nide complex [K(THF) ] [(1,3-Ph C H ) Sc (ꢁ -C H ) (ꢂ -

2

5

3 2

2

14 10 2

2

3

ꢁ

:ꢁ -C H )]ꢀTHF, (6) (Scheme 1).

14

10

Complexes Na[Sc(C Ph ) ]ꢀ4THF, (1a), and K[Sc(C Ph ) ]ꢀ-

2 4 2

2

4 2

3.5THF, (2a), were obtained in reactions between M [C Ph ]

and ScCl (THF) (or anhydrous ScI ) in a 2:1 molar ratio in

2 2 4

3

THF (Fig. 1). Numerous attempts to obtain suitable single

crystals of the THF solvates (1a) and (2a) for X-ray diffraction

studies were unsuccessful, presumably due to the easy loss of

THF at low temperature and upon vacuum drying. This

problem was noted earlier for the analogous complexes

M[Lu(C Ph ) ]ꢀ5THF (M = Na and K; Roitershtein et al.,

2

4 2

2

004). Slow diffusion of Et O into a THF solution of (1a),

2

containing 18-crown-6, allowed us to isolate single crystals of

(

1b) (Fig. 1).

Metallation of a mixture of isomeric 1,4- and 1,3-di-

phenylcyclopentadienes, (3a)/(3b), with KCH Ph led to in situ-

2

generated K(1,3-Ph C H ), which was then reacted with

2

5

3

ScCl (THF) , leading to Sc(1,3-Ph C H )Cl (THF) , (4)

2

3

2

5

3

(Fig. 2). We were not able to obtain single crystals of (4)

suitable for X-ray studies. One attempt to crystallize (4) from

a THF/pentane mixture resulted in the formation of 1,4-di-

phenylcyclopenta-1,3-diene, (3a), likely due to unintended

partial hydrolysis of (4). The reaction of in situ-generated (4)

with disodium tetraphenylethylene provided microcrystals of

5

6

[

Sc(ꢁ -1,3-Ph C H )(ꢁ -C Ph )(THF)]ꢀTHF, (5a) (Fig. 2).

2

5

3

2

4

Recrystallization of the latter from a toluene/hexane mixture

resulted in the formation of (5b), the structure of which was

established by X-ray diffraction analysis.

Poorly soluble complex (6) was ﬁrst synthesized by the

reaction of in situ-generated (4) and 2 equiv. of potassium

+

ꢂ

ꢁ

(Fig. 3, upper synthesis), targeting

10

anthracenide, K ꢀC H

14

an unknown (1,3-Ph C H )Sc(C H ) complex. A higher

2

5

3

14 10

yield of (6) was then obtained by reaction of ScCl (THF) with

3

+

equiv. of K C H

ꢂ

ꢁ

1

generated K(1,3-Ph C H ) (Fig. 3, middle synthesis). Analo-

, and then with 1 equiv. of in situ-

14

10

2

5

3

(Schlenk & Bergmann, 1928), the crystal structures of alkali-

metal adducts with the tetraphenylethylene dianion were

established much later (Bock et al., 1989, 1996; Minyaev et al.,

2007; Minyaev & Ellis, 2014). These alkali-metal salts of

gous reactions to prepare Y and Lu derivatives failed, leading

to mixtures of solids containing considerable amounts of

paramagnetic impurities. Crystallization of (6) was performed

from a THF/hexane mixture in both cases. An attempt to

synthesize (6) from potassium–graphite, anthracene and in

situ-generated (4) failed (Fig. 3, lower synthesis), providing a

black solid, which was presumably an unknown Sc anthrace-

tetraphenylethylene are synthetic precursors to rare-earth

tetraphenylethenide complexes, of which the number with

II

established crystal structures is limited [Ln = Y, Yb and Lu;

Roitershtein et al., 1998, 2004; Roitershtein, Minyaev et al.,

1

nide compound, and K(1,3-Ph C H ) ( H NMR data).

2

5

3

ꢂ

7

70 Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide

Acta Cryst. (2018). C74, 769–781

research papers

Figure 1

Synthesis of (1a) and (2a), and crystallization of (1b).

2

. Experimental

.1. Synthesis and crystallization

.1.1. General experimental remarks. The studied dianionic

distilled from Na prior to the preparation of the specimens for

X-ray diffraction studies. Benzyl potassium was prepared

according to the published procedure of Schlosser & Hart-

2

mann (1973). ScCl

literature procedure of Herrmann (1997). The scandium

content in ScCl (THF) and in all the studied Sc complexes

3 3

(THF) was synthesized according to the

Sc complexes are extremely sensitive to oxygen and moisture.

All described synthetic manipulations were performed under

an argon atmosphere or under vacuum, using an argon-ﬁlled

glove-box, standard Schlenk glassware or evacuated sealed

Schlenk-type vessels equipped with Teﬂon stopcocks, vacuum-

line techniques and absolute solvents. Tetrahydrofuran (THF)

and diethyl ether were predried over NaOH and distilled from

sodium/benzophenone ketyl. Pentane, hexane and THF-d₈

were distilled from Na/K alloy. Toluene was distilled from

sodium/benzophenone ketyl. 18-Crown-6 was distilled from

sodium. Tetraphenylethylene was puriﬁed by recrystallization

from anhydrous toluene and dried under vacuum. Anthracene

was vacuum sublimed. Aliphatic hydrocarbon oil was vacuum

3

was determined by direct complexometric titration with the

disodium salt of EDTA (ethylenediaminetetraacetic acid),

using xylenol orange indicator. Due to the highly pyrophoric

nature of the dianionic complexes, their elemental C/H

analyses were not performed. Diphenylcyclopenta-1,3-diene

was obtained according to the literature as a mixture of 1,3-

and 1,4-isomers (Roitershtein, Minyaev et al., 2007), and was

puriﬁed by vacuum sublimation.

Electronic absorption spectra were recorded on a Varian

Cary 300 Bio instrument (software Version 3.0, double beam

method, baseline correction, 200–800 nm range). The C/H

Figure 2

Synthesis of (4) and (5a), and crystallization of (3a) and (5b).

ꢂ

Acta Cryst. (2018). C74, 769–781

Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide 771

research papers

Figure 3

The synthesis of (6).

elemental analysis of (4) was performed with a PerkinElmer

1

product was extracted from one ampoule to another by

multiple operations of decanting the solution from the preci-

pitate, condensing THF back at low temperatures and stirring

for 15 min. The shiny dark-red crystals were washed with THF

(3 ꢃ 5 ml) and dried under vacuum for 3 h to a constant mass.

The yield of obtained microcrystalline powder was 1.805 g

(1.77 mmol, 79%). Analysis found (calculated for C H -

13

1

2

400 Series II elemental analyzer. H and C{ H} NMR

spectra were registered with Varian VI-300, Bruker AM-300

1

300 MHz for H and 75.5 MHz for C) and Bruker AV-600

13

(

1

13

600 MHz for H and 150.9 MHz for C) spectrometers in

(

THF-d for the Sc complexes and in CDCl for (3a).

8

3

2.1.2. Synthesis of (1a) (see Fig. 1). A solution of

6

8

72

Na [C Ph ] was prepared from a sodium mirror (0.615 g,

4

NaO Sc): Sc 4.35% (4.40%).

4

2

1

26.7 mmol) and tetraphenylethylene (1.509 g, 4.54 mmol) in

THF (95 ml) over a period of 2 d. The Na [C Ph ] solution was

H NMR (243 K, 300 MHz, 128 scans, THF-d ): ꢅ 4.65 (dd,

8

4H, H ), 6.29 (t, 4H, H ), 6.58 (t, 4H, H_p_a_r_a), 6.87 (br t, 12H,

5

2

4

3

added to a suspension of ScCl (THF) (0.825 g, 2.24 mmol) in

3

H + H ), 7.07 (t, 4H, H ), 7.14 (d, 8H, H_o_r_t_h_o), 7.65 (dd, 4H,

2 meta 4

3

13

1

THF (50 ml). The reaction mixture was stirred for 2 d. The

H₁). C{ H} NMR (253 K, 150.9 MHz, THF-d ): ꢅ 86.1

8

Figure 4

1

13

4 2 2

H NMR spectrum of K[Sc(Ph C ) ], (2a), at 253 K and the atom-numbering scheme for the H and C signals.

ꢂ

7

72 Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide

Acta Cryst. (2018). C74, 769–781

research papers

Table 1

Experimental details.

Experiments were carried out with Mo Kꢇ radiation.

(1b)

(3a)

(5b)

(6)

Crystal data

Chemical formula

[Na(C

Sc(C26

1285.51

Triclinic, P1

173

4

H

8

O)

H

20

2

(C12

H

24

O

6

)]-

C

17

H

14

[Sc(C17

H

13)(C26

H

20)-

[K

(C

1497.84

Orthorhombic, Ibam

150

18.1056 (12), 19.9164 (13),

21.8633 (14)

90, 90, 90

2

Sc

2

(C14

H

10

)

3

(C17

H O

4 8

H

13

)

2

-

[

)

2

]ꢀ2C

4

8

H O

(C

4

H

8

O)]ꢀ0.5C

7

H

8

4

H

8

O)

4

]ꢀC

M

r

218.28

Monoclinic, P2

123

7.3278 (5), 5.9440 (4),

26.6551 (18)

90, 94.352 (1), 90

712.82

Monoclinic, C2/c

173

36.060 (5), 9.5557 (14),

23.662 (3)

90, 113.840 (2), 90

Crystal system, space group

Temperature (K)

˚

a, b, c (A)

1

/n

12.6071 (18), 14.764 (2),

8.585 (3)

84.507 (2), 88.508 (2),

4.033 (2)

1

ꢄ

ꢇ, ꢈ, ꢉ ( )

8

˚

3

V (A )

Z

3424.2 (9)

2

0.17

0.40 ꢃ 0.25 ꢃ 0.25

1157.65 (14)

4

0.07

0.60 ꢃ 0.20 ꢃ 0.20

7457.9 (19)

8

0.24

0.50 ꢃ 0.40 ꢃ 0.25

7883.9 (9)

4

0.33

0.25 ꢃ 0.08 ꢃ 0.07

ꢁ

1

ꢂ (mm

)

Crystal size (mm)

Data collection

Diffractometer

Bruker SMART Platform

CCD area detector

Multi-scan (SADABS; Bruker, Multi-scan (SADABS; Bruker, Multi-scan (SADABS; Bruker, Multi-scan SADABS (Bruker,

Bruker SMART Platform

CCD area detector

Bruker SMART Platform

CCD area detector

Bruker APEXII CCD area

detector

Absorption correction

2

003)

2003)

0.829, 0.985

13442, 2788, 2406

2003)

0.869, 0.967

42147, 8560, 6319

2008)

0.922, 0.977

28915, 3990, 2831

Tmin, Tmax

0.869, 0.967

No. of measured, independent 32161, 11986, 6407

and observed [I > 2ꢃ(I)]

reﬂections

R

int

0.073

0.595

0.083

0.667

0.044

0.650

0.072

0.617

˚

ꢁ1

)

(sin ꢊ/ꢆ)max (A

Reﬁnement

2

R[F > 2ꢃ(F )], wR(F ), S

No. of reﬂections

0.074, 0.183, 1.03

0.044, 0.128, 1.03

0.058, 0.159, 1.04

0.055, 0.150, 1.03

3990

307

11986

860

46

2788

210

0

8560

467

0

No. of parameters

No. of restraints

H-atom treatment

128

H atoms treated by a mixture All H-atom parameters

H atoms treated by a mixture H-atom parameters

of independent and

constrained reﬁnement

0.40, ꢁ0.48

reﬁned

of independent and

constrained reﬁnement

1.17, ꢁ0.45

constrained

˚

ꢁ3

)

Áꢋmax, Áꢋmin (e A

0.32, ꢁ0.25

0.77, ꢁ0.47

Computer programs: SMART (Bruker, 2003), APEX2 (Bruker, 2008), SAINT (Bruker, 2003), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SIR2002 (Burla et al., 2003),

SHELXL2017 (Sheldrick, 2015) and SHELXTL (Sheldrick, 2008).

1

3

1

(

1

(

Ph CCPh or C ), 100.5 (br, C ), 112.0 (C ), 118.6 (br, C ),

1

C{ H} NMR (253 K, 150.9 MHz, THF-d ): ꢅ 86.2 (C ), 100.5

8 =

2

=

5

3

1

19.4 (C_p_a_r_a), 125.5 (C_m_e_t_a), 128.1 (C_o_r_t_h_o), 129.7 (br, C ), 137.4

2

(br, C , J = 147.3 Hz), 112.1 (C , J = 160.6 Hz), 118.6

5 CH 3 CH

1

br, C ), 137.8 (C ), 144.3 (C ). Please refer to Fig. 4 for the

4

(br, C , J = 154.6 Hz), 119.5 (C_p_a_r_a, J = 156.5 Hz), 125.5

1 CH CH

6

ipso

1

NMR numbering scheme. Low-temperature H NMR spectra

are presented in the supporting information in Fig. S6 (the

temperature range is from 203 to 283 K, with a step of 20 K).

UV–Vis (THF) ꢆ_m_a_x: 312, 392, 555 (sh) nm.

(C_m_e_t_a, J = 154.2 Hz), 128.1 (C_o_r_t_h_o, J = 156.1 Hz), 129.8

CH CH

1

(br, C , J = 154.2 Hz), 137.4 (br, C , J = 148.6 Hz), 144.3

1

2

CH

4

CH

(C_i_p_s_o), 137.8 (C ). Please refer to Fig. 4 for the NMR

6

45

numbering scheme. Sc NMR (295 K, 72.94 MHz, THF-d ): ꢅ

8

2

.1.3. Crystallization of (1b). Na[Sc(Ph C ) ]ꢀ4.5(THF)

64.0 [reference: 203.3 ppm for ScCl (THF) ; see Figs. S10 and

3

4

2 2

3

(

170 mg, 0.17 mmol) and 18-crown-6 (70 mg, 0.26 mmol) were

S11 in the supporting information]. UV–Vis (THF) ꢆ_m_a_x: 312,

391, 520 (sh) nm.

dissolved in THF (15 ml). Diethyl ether (35 ml) was layered

on top of the formed solution. Crystals of (1b) formed over a

period of three weeks.

2.1.5. Synthesis of (4) (see Fig. 2). A cold (203 K) solution

of KCH Ph (2.103 g, 16.2 mmol) in THF (55 ml) was added

2

.1.4. Synthesis of (2a). The product (2a) was obtained in an

analogous manner to (1a), starting from potassium (1.191 g,

0.5 mmol), tetraphenylethylene (2.001 g, 6.02 mmol) and

ScCl (THF) (1.092 g, 2.97 mmol). The yield of a dark-red

dropwise to a stirred cold (203 K) solution of diphenylcyclo-

penta-1,3-diene [a mixture of (3a) and (3b); 3.420 g,

15.7 mmol] in THF (100 ml). The mixture was stirred for

30 min, heated to 303 K and stirred for another 30 min. The

resulting solution was added dropwise to a stirred suspension

of ScCl (THF) (5.650 g, 15.4 mmol) in THF (10 ml) at 203 K.

3

microcrystalline powder was 1.904 g (1.90 mmol, 64%).

Analysis found (calculated for C H KO Sc): Sc 4.47%

66

68

3.5

3

(

4.49%).

1

The mixture was stirred for 30 min at 203 K and then for 1 h at

303 K. Almost all the THF was evaporated under reduced

pressure. The complex was extracted from the residue with

portions of toluene (270 ml total) at room temperature. The

H NMR (253 K, 600 MHz, THF-d ): ꢅ 4.70 (dd, 4H, H ),

8

5

6

7

.32 (t, 4H, H ), 6.60 (t, 4H, H ), 6.90 (br t, 12H, H + H_m_e_t_a),

3 para 2

.10 (br t, 4H, H ), 7.18 (d, 8H, H_o_r_t_h_o), 7.68 (dd, 4H, H₁).

4

ꢂ

Acta Cryst. (2018). C74, 769–781

Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide 773

research papers

resulting solution was ﬁltered through a ﬁne frit. Almost all

the toluene was evaporated. The resulting product was

dissolved in THF (160 ml) and the mixture was ﬁltered. All

but ca 60 ml of solvent was then evaporated from the solution.

Pentane (150 ml) was layered on top. The next day the two-

layer mixture was stirred and left for 5 h without stirring. The

precipitated product was ﬁltered off and dried under vacuum.

The yield of pale-yellow microcrystals of (4) was 3.749 g

for 15 h until all the potassium pieces were dissolved. The

resulting blue solution of KC H was added to a stirred

suspension of ScCl (THF)₃(368 mg, 1.00 mmol) in THF

14

10

3

(10 ml). The colour of the reaction mixture turned deep violet.

The mixture was stirred for 2 h. A solution of K(1,3-Ph C H ),

prepared from KCH Ph (135 mg, 1.04 mmol) and (3a)/(3b)

2

5

3

2

(224 mg, 1.03 mmol) in THF (20 ml), was dropwise added to

the reaction mixture, which was then stirred for 2 h. The

mixture was centrifuged. All but the THF (ca 25 ml) was

evaporated from the resulting solution under reduced pres-

sure. Hexane (60 ml) was layered on top of the THF solution.

After two weeks, the solution was decanted from the resulting

black needle-shaped crystals. Some of these were taken for

X-ray studies. The remaining crystals were washed with

hexane (2 ꢃ 5 ml) and dried brieﬂy under vacuum. The yield

of crystals was 535 mg (0.36 mmol, 71%). Analysis found

(calculated for C H K O Sc ): Sc 6.12% (6.00%). The

(6.82 mmol, 44%). Analysis found (calculated for

C H Cl O Sc): C 63.28 (63.39), H 6.61 (6.79), Sc 8.23%

2

9

37

2

3

1

(

8.18%). H NMR (300 MHz, THF-d ): ꢅ 6.01 (br s, 1H), 6.46

8

(

br s, 1H), 6.96–7.00 (m, 1H), 7.11–7.19 (m, 2H), 7.25–7.37 (m,

4H), 7.58–7.64 (m, 4H).

2.1.6. Crystallization of (3a). Pentane (40 ml) was layered

on top of a solution of (4) (160 mg) in THF (18 ml). Crystals

had not formed within two weeks after the layers were mixed

at room temperature. A Schlenk vessel containing this solu-

96

2

5

2

tion was placed in a freezer (ca 250 K). A few crystals of (3a)

1

complex is poorly soluble in THF.

formed within a week. H NMR (295 K, 300 MHz, CDCl ): ꢅ

3

.77 (s, 2H, CPh—CH —CPh ), 6.93 (s, 2H, –CPh CH—

2

.2. Refinement

CH CPh–), 7.19 (t, 2H, H_p_a_r_a), 7.33 (t, 4H, H_m_e_t_a), 7.54 (d, 4H,

H_o_r_t_h_o).

Crystal data, data collection and structure reﬁnement

2

.1.7. Synthesis of (5a) (see Fig. 2). A solution of K(1,3-

details are summarized in Table 1. Non-H atoms were reﬁned

with individual anisotropic displacement parameters, with the

exception of a toluene molecule in (5b) and a noncoordinating

THF molecule in (6), which were reﬁned with individual

[toluene C atoms in (5b)] or equal [C and O atoms of the THF

molecule in (6)] isotropic displacement parameters. The

positions of the H atoms in all the Sc complexes [with the

exception of the disordered molecules and fragments in (1b),

(5b) and (6)] were found from difference maps. The positions

of two H atoms per tetraphenylethylene dianion [atoms H4,

H16, H30 and H42 in (1b), and atoms H4 and H16 in (5b)],

Ph C H ), which was obtained by adding a solution of

2

5

3

KCH Ph (425 mg, 3.26 mmol) in THF (40 ml) to a stirred

2

solution of (3a)/(3b) (693 mg, 3.18 mmol) in THF (40 ml),

followed by stirring the resulting mixture for 1 h at room

temperature, was added dropwise to a stirred suspension of

ScCl (THF) (1.132 g, 3.08 mmol) in THF (30 ml). The formed

reaction mixture was stirred overnight at room temperature. A

solution of Na [C Ph ], prepared from C Ph (1.035 g,

3

2

4

2

4

3

2

.11 mmol) in THF (70 ml) over a potassium mirror (975 mg,

5 mmol) for a period of 2 d, was added dropwise to the

3+

stirred reaction mixture over a period of 30 min at room

temperature. The resulting mixture was then stirred for 2 d.

All the THF was evaporated under vacuum. The product was

extracted from the residue with toluene (3 ꢃ 50 ml). The

resulting black–green solution was decanted from the preci-

pitate. All the toluene was evaporated under vacuum. The

residue was extracted with THF (3 ꢃ 30 ml). Almost all the

THF was evaporated (to ca 3 ml) and the THF was then

decanted. The resulting green microcrystals were washed with

THF (3 ꢃ 1 ml), hexane (2 ꢃ 10 ml) and dried under vacuum.

interacting with the Sc cation, were reﬁned since they

deviated from geometrically calculated positions, but the other

H atoms in (1b) and (5b), and all the H atoms in (6) were

˚

positioned geometrically [C—H = 0.95 A for aromatic, 0.98 A

˚

for methyl, 0.99 A for methylene and 1.00 A for Cp (cyclo-

pentadienyl) H atoms] and reﬁned as riding atoms with rela-

tive isotropic displacement parameters [U (H) = 1.5U (C)

iso

eq

for methyl H atoms and 1.2U (C) otherwise]. A rotating-

eq

group model was applied for the methyl groups. The positions

and isotropic displacement parameters of all the H atoms in

(3a) were reﬁned due to the sufﬁciently good collected data.

Only a major twinning component (over 95% according to

CELL_NOW; Sheldrick, 2003) of (3a) was used in the

reﬁnement. For (6), reﬂection 110 was affected by the beam

stop and was therefore omitted from the reﬁnement.

The yield was 933 mg (1.26 mmol, 41%).

1

H NMR (243 K, 300 MHz, THF-d ): ꢅ 4.54 (br s, 1H), 5.57

8

(

7

t, 1H), 5.72 (br s, 1H), 5.99 (t, 1H), 6.20 (dd, 1H), 6.69–6.93 (m,

H), 6.98 (t, 2H), 7.02–7.23 (m, 9H), 7.27 (t, 2H), 7.37 (dt, 1H),

.45–7.51 (m, 4H), 7.59–7.64 (m, 2H), 8.03 (dd, 1H). UV–Vis

(THF) ꢆ_m_a_x: 210, 313, 382, 570 (br sh) nm. Analysis found

The crystal structure of (1b) has a disordered CH —CH

2

(

calculated for C H O Sc): Sc 5.89% (6.08%).

49

fragment in a coordinated THF molecule with a disorder ratio

of 0.639 (12):0.361 (12) for the C71A/C72A and C71B/C72B

atoms. Displacement ellipsoids for some non-H atoms in the

disordered fragment and in two noncoordinating THF mol-

ecules were restrained to approximately simulate isotropic

behaviour. The toluene molecule in (5b) lies on a twofold

rotation axis, and its C atoms are disordered equally over two

overlapping sets of positions (see Fig. S1 in the supporting

5

1

2

2.1.8. Crystallization of (5b). Hexane (27 ml) was layered

on top of a solution of (5a) (82 mg) in toluene (23 ml). Crystals

of (5b) suitable for X-ray diffraction analysis had formed in

5

d.

2.1.9. Synthesis and crystallization of (6) (see Fig. 3, middle

reaction). Potassium (120 mg, 3.06 mmol) and a solution of

anthracene (556 mg, 3.12 mmol) in THF (100 ml) were reacted

ꢂ

7

74 Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide

Acta Cryst. (2018). C74, 769–781

research papers

Table 2

Selected bond lengths (A) for (3a).

Table 3

Selected bond lengths (A) for (1b).

˚

C1—C2

C2—C3

C3—C4

C4—C5

1.3615 (15)

1.4548 (16)

1.3598 (15)

1.5077 (14)

C1—C5

C1—C6

C4—C12

1.5051 (14)

1.4641 (14)

1.4651 (14)

Sc1—C1

Sc1—C2

Sc1—C3

Sc1—C4

Sc1—C15

Sc1—C16

Sc1—C27

Sc1—C28

Sc1—C29

Sc1—C30

Sc1—C41

Sc1—C42

C1—C3

C3—C4

C4—C5

C5—C6

C6—C7

C7—C8

C3—C8

C1—C9

C1—C2

2.351 (4)

2.357 (4)

2.577 (4)

2.518 (4)

2.559 (4)

2.536 (4)

2.354 (4)

2.380 (4)

2.590 (4)

2.563 (4)

2.562 (4)

2.560 (4)

1.434 (5)

1.418 (6)

1.393 (5)

1.370 (6)

1.387 (6)

1.369 (6)

1.432 (5)

1.482 (6)

1.501 (5)

1.442 (5)

1.425 (6)

C16—C17

C17—C18

C18—C19

C19—C20

C15—C20

C2—C21

1.385 (6)

1.357 (6)

1.397 (6)

1.353 (5)

1.431 (5)

1.486 (5)

1.451 (5)

1.426 (5)

1.391 (6)

1.362 (6)

1.393 (6)

1.370 (6)

1.424 (5)

1.488 (5)

1.503 (5)

1.444 (5)

1.434 (5)

1.388 (5)

1.365 (6)

1.400 (6)

1.360 (5)

1.428 (5)

1.487 (5)

C27—C29

C29—C30

C30—C31

C31—C32

C32—C33

C33—C34

C29—C34

C27—C35

C27—C28

C28—C41

C41—C42

C42—C43

C43—C44

C44—C45

C45—C46

C41—C46

C28—C47

information). The noncoordinating THF molecule in (6) is

disordered over three twofold rotation axes (25% site occu-

pancies; see Fig. S3 in the supporting information). Atoms

C22–C25 of the coordinated THF molecule in (6) are disor-

dered over two positions (C22A–C25A and C22B–C25B), with

a corresponding disorder ratio of 0.728 (10):0.272 (10). Similar

C—O and C—C bond distances were restrained to be equal

within 0.01 A in this molecule. The disordered C atoms

(C22A–C25A and C22B–C25B) still exhibited rather high

atomic displacement parameters, but further reﬁnement

intended to resolve this problem only complicated the crys-

tallographic model. Four atoms of the phenyl group in (6) are

disordered equally [0.501 (5):0.499 (5)] over two positions

˚

C2—C15

C15—C16

(C5A–C8A/C5B–C8B). Similarity constraints were applied to

the anisotropic displacement parameters of these atoms. In

order to further improve the model, constraints were applied

to the anisotropic displacement parameters of nine C atoms

exhibiting high atomic displacement parameters to approxi-

mately simulate isotropic behaviour. This did not improve the

crystallographic model signiﬁcantly, but considerably changed

the parameter/restraint ratio from 307/128 to 307/188. There-

fore, the latter modelling was not used in the ﬁnal model of

rationalized by localization of the negative charge predomi-

nantly at two atoms of the former double bond (C ) and also

=

at all eight C_o_r_t_h_oatoms [see Minyaev & Ellis (2014) for

details]. However, the situation changes upon coordination of

the easily polarizable dianionic ligand with the strongly

3+

polarizing Sc cation.

6

The ate complex (1b) contains the homoleptic [Sc(ꢁ -

ꢁ

C Ph ) ] complex anion (Fig. 6a), the [Na(18-crown-6)-

2

4 2

(

6).

+

THF)₂] cation (Fig. 6b) and two noncoordinating THF

(

molecules (not shown), which are well separated in the crystal

˚

structure. The Na—O(18-crown-6) bonds [2.663 (3) A for

˚

Na1—O4 to 2.860 (3) A for Na1—O2] are longer than the

3

. Results and discussion

˚

corresponding Na—O(THF) bonds [2.394 (3) A for Na1—O7

3

.1. 1,4-Diphenylcyclopenta-1,3-diene, (3a)

6

˚

and 2.355 (3) A for Na1—O8] in the complex cation. In [Sc(ꢁ -

Partial hydrolysis of (4) at low temperature resulted in the

formation of a few crystals of thermodynamically favourable

ꢁ

6

3+

Ph C ) ] , the Sc cation is nearly symmetrically coordinated

4

2 2

2ꢁ

by two ꢁ -Ph C

dianions, each of them exhibiting six short

Sc—C contacts, i.e. to two atoms of the former double bond

(C is C1 C2 and C27 C28), two Cipso atoms of two phenyl

4

2

hydrocarbon 1,4-Ph C H , (3a) (Figs. 2 and 5). The C—C bond

2

5

4

lengths were as expected (Table 2). The ﬁve-membered C1–C5

˚

ring is ﬂat, with a maximum deviation of 0.0156 (6) A for atom

=

˚

C5. The C_i_p_s_o(Ph) atoms are out of the plane by 0.1063 (18) A

rings (C3/C15 and C29/C41) and two Cortho atoms (C4/C16 and

C30/C42) (Fig. 6a and Table 3). The determined positions of

the H atoms at coordinated Cortho atoms deviate noticeably

from the corresponding phenyl-ring planes. Therefore, the

geometrical positions of these H atoms (H4, H16, H30 and

H42) were reﬁned (see x2.2). Due to the reduction to the

˚

for atom C6 and 0.1126 (18) A for C12. The Cp–Ph (cyclo-

ꢄ

pentadienyl–phenyl) dihedral angle is 10.50 (5) for the C6–

ꢄ

C11 phenyl ring and 11.66 (5) for the C12–C17 phenyl ring.

These data may be considered as reference parameters for 1,3-

diphenylcyclopentadienyl complexes.

dianion, the length of a former double bond (C —C

=

C1 C2 and C27 C28) is elongated to a single C—C bond

3

.2. Tetraphenylethenide complexes with the homoleptic

ꢁ

[Sc(C Ph ) ] complex anion

2

4 2

The reference points for the crystal structures of tetra-

phenylethenide rare-earth complexes are structures of alkali-

+

metal adducts with tetraphenylethylene, viz. [Na(Et O) ] -

2 2

2

ꢁ

[

C Ph ]

2

(CSD refcode VEDXOR; Bock et al., 1989),

2ꢁ

4

+

2

Na(diglyme) ] [C Ph ] (FOGFUE; Minyaev & Ellis, 2014),

2

+

2

2ꢁ

K(DME) ] [C Ph ] (XIDHIC; Minyaev et al., 2007) and

4

2

Figure 5

The molecular structure of 1,4-Ph C H . Displacement ellipsoids are

drawn at the 50% probability level.

+

2

2ꢁ

Cs(diglyme)] [C Ph ] (ZUXXIZ; Bock et al., 1996). The

2

4

2

5

4

C—C bond-length redistribution inside the dianion could be

ꢂ

Acta Cryst. (2018). C74, 769–781

Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide 775

research papers

(Table 3). The Sc—C bond lengths are considerably shorter

than the Sc—C_i_p_s_oand Sc—C_o_r_t_h_obond lengths. The C —C

distances for the noncoordinated phenyl groups are slightly

longer than those for the coordinated phenyl groups. The C—

C bond-distance redistribution within the coordinated phenyl

S6 in the supporting information). We have estimated

previously the rotation barrier for coordinated phenyl groups

=

ipso

ꢁ 2ꢁ

to be ca 70 kJ mol for C Ph₄in [(1,3-Ph C H )Lu(C Ph )-

2 2 5 3 2 4

1

ꢁ

1

(THF)] (Roitershtein, Minyaev et al., 2007) and ca 67 kJ mol

for the coordinated azobenzene dianion in a related complex

rings and the C —C

=

and Sc—C bond lengths (Table 3)

3

{[(C H )Lu(THF)] (ꢂ -N Ph ) }(THF) (NIXMOW; Roiter-

ipso

5

2

2 2

2

indicate that the tetraphenylethenide ligand displays a bis-ꢁ -

allylic coordination mode. The Sc coordination number

shtein et al., 1997; Petrov et al., 2002). Qualitatively, the rota-

6

ꢁ

tion barrier in the [Sc(ꢁ -Ph C ) ] anion is noticeably lower.

4 2 2

(

CN ) is therefore 8, since each allyl fragment occupies two

Sc

3

coordination sites. The bis-ꢁ -allylic coordination type is

consistent with the major resonance forms with predominant

localization of an excessive negative charge at the C and

=

coordinated C_o_r_t_h_oatoms (Scheme 2), unlike in alkali-metal

3

+

M [C Ph ] salts (see above). This relatively strong Sc –

2

4

2

C Ph₄interaction is also reﬂected in a considerable short

ꢁ

2

wavelength shift of a LMCT (ligand-to-metal charge transfer)

absorbance band as compared to M [C Ph ] (M = Na and K)

adducts (see below).

2

4

The structures of similar homoleptic anions were deter-

+

6

ꢁ

mined previously for [Na(THF) ] [Y(ꢁ -C Ph ) ] ꢀ2(THF)

6

2

4 2

+

6

(

FIGQER; Roitershtein et al., 1998), [Na(diglyme) ] [Lu(ꢁ -

2

ꢁ

C Ph ) ] ꢀ0.5(THF) (KAMZII; Roitershtein et al., 2004) and

2

4 2

+

6

2ꢁ

4 2

[

Na(THF) ] [Na(THF) ] [Yb(ꢁ -C Ph ) ] (XIDHEY; Min-

3 4 2

6

2ꢁ

yaev et al., 2007). Unlike the labile [Yb(ꢁ -C Ph ) ] complex

2

4 2

II

6

ꢁ

dianion of Yb , the rather rigid [Ln(ꢁ -Ph C ) ] anions (Ln =

4

2 2

3

Y and Lu) demonstrated retention of the bis-ꢁ -allylic ligand

coordination mode in a THF-d solution. They also displayed

8

a temperature-dependent hindered rotation of the coordi-

nated phenyl groups along the C —C

bonds, whereas the

ipso

=

1

H NMR spectrum for Na [C Ph ] displayed a free rotation

4

2

for all the phenyl groups at room temperature (Roitershtein et

1

al., 1998). H NMR studies of (1a) and (2a) demonstrated a

6

ꢁ

similar behaviour of the [Sc(ꢁ -C Ph ) ] anion in a THF-d

8

2

4 2

1

solution to the Lu and Y analogs. The H NMR spectrum of

2a) and the NMR numbering scheme are shown in Fig. 4. The

signals of atoms H , H , H and H are very broad at room

(

Figure 6

The structures of (a) the [Sc(ꢁ -C

crown-6)(THF) ] cation in (1b). The minor component of the THF

disorder is shown with solid open lines. Displacement ellipsoids are drawn

at the 50% probability level and all but the H atoms interacting with Sc

atoms have been omitted for clarity.

6

ꢁ

anion and (b) the [Na(18-

2

4

Ph )

2

]

1

2

4

5

+

2

temperature due to a noticeable rotation of the coordinated

phenyl groups in relation the NMR time scale. The structures

of these signals become resolved at ca 263 K and below (Fig.

ꢂ

7

76 Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide

Acta Cryst. (2018). C74, 769–781

research papers

Table 4

The C NMR signals for the [Ln(C

Table 5

Selected bond lengths (A) for (5b).

13

ꢁ

2 4 2

Ph ) ] anions (Ln = Y, Lu and Sc) in

˚

THF-d at room temperature.

8

Sc1—C1

Sc1—C2

Sc1—C3

Sc1—C4

Sc1—C15

Sc1—C16

Sc1—C27

Sc1—C28

Sc1—C29

Sc1—C30

Sc1—C31

Sc1—O1

Sc1—Cpcentroid

2.312 (2)

2.392 (2)

2.522 (2)

2.547 (2)

2.589 (2)

2.465 (2)

2.565 (2)

2.553 (2)

2.546 (2)

2.489 (2)

2.490 (2)

2.2024 (17)

2.224 (1)

1.415 (6)

1.434 (3)

1.439 (3)

1.409 (3)

C5—C6

C6—C7

C7—C8

C3—C8

C1—C9

C2—C15

C15—C16

C16—C17

C17—C18

C18—C19

C19—C20

C15—C20

C2—C21

C27—C32

C29—C38

C1—C2

1.366 (4)

1.404 (4)

1.366 (3)

1.432 (3)

1.498 (3)

1.433 (3)

1.434 (3)

1.406 (4)

1.366 (4)

1.400 (4)

1.367 (4)

1.431 (3)

1.481 (3)

1.482 (3)

1.480 (3)

1.506 (3)

Data for K[Y(C Ph ] and K[Lu(C

2

4

)

2

Ph42] are taken from the literature and

any supporting information ﬁles (Roitershtein et al., 1998, 2004).

C atoms

K[Y(C Ph

2

4 2

) ]

K[Lu(C

2 4

Ph )

2

]

(1a)

(2a)

C

=

88.3

120.1

131.2

111.5

138.9

99.6

139.0

129.2

127.7

120.9

145.9

86.8

120.6

133.2

112.6

141.5

98.1

141.1

130.4

128.5

122.1

146.6

86.1

118.6

129.7

112.0

137.4

100.5

137.8

128.1

125.5

119.4

144.3

86.2

118.6

129.8

112.1

137.4

100.5

137.8

128.1

125.5

119.5

144.3

C-1

C-2

C-3

C-4

C-5

C-6

C

ortho

C

Cpꢀ ꢀ ꢀCCp (ave)

meta

C1—C3

C3—C4

C4—C5

para

ipso(Ph)

The proton signal assignments in (1a) and (2a) were based

ꢁ

compounds are consistent with the localization of excessive

negative charge at these atoms and the bis-allylic coordination

type of the dianionic ligand.

on those for [Ln(C Ph ) ] (Ln = Lu and Y) and on the COSY

2

4 2

1

correlation spectroscopy) H– H spectrum (Fig. S7 in the

(

supporting information). The most upﬁeld shifted signal, i.e.

For a better understanding of the charge redistribution in

45

ate complexes, a Sc NMR spectrum of (2a) (Fig. S10 in the

H (4.7 ppm; Fig. 4), corresponds to H atoms interacting with

5

3

Sc (H4, H16, H30 and H42; Fig. 6a).

+

supporting information) was recorded using ScCl (THF)

3

1

3

1

The C{ H} spectra of (1a) and (2a), recordered at room

temperature, display broad signals of the C , C , C and C

5

(Fig. S11 in the supporting information) as a reference

1

2

4

(203 ppm in THF-d ; Mason, 1987). A strong upﬁeld shift of

the scandium signal [64 ppm in (2a)] compared to that of

8

1

13

atoms. The 2D H– C HSQC (heteronuclear single quantum

coherence; Fig. S8 in the supporting information) and HMBC

ScCl (THF) suggests that an essential part of the electron

3

(heteronuclear multiple-bond correlation; Fig. S9 in the

supporting information) spectra of (1a) allowed us to make

3+

density is shifted from the dianionic ligand to the Sc cation,

which supports the idea of a signiﬁcant covalent contribution

1

3

the C signal assignments presented in Table 4, along with the

data for the related Y and Lu complexes. The highest upﬁeld

chemical shifts for the C₌and C atoms in all the title

3+

to the Sc –C Ph

tral data below).

2ꢁ

ionic interaction (see also UV–Vis spec-

2

4

5

3.3. Heteroleptic tetraphenylethenide complex [(1,3-

Ph C H )Sc(C Ph )(THF)]

2

5

3

2

4

5

The crystal structure of (5b) contains the complex [(ꢁ -1,3-

6

Ph C H )Sc(ꢁ -C Ph )(THF)] (Fig. 7) and a toluene molecule

2

5

3

2

4

(

Fig. S1 in the supporting information). The tetraphenyl-

3

ethylene dianion exhibits the unsymmetrical bis-ꢁ -allylic

coordination type (compare the Sc—C and C—C bond lengths

within the two allylic fragments; Table 5). The 1,3-Ph C H

3

2

5

ligand is ꢁ -coordinated. The Sc atom is additionally coordi-

nated by a THF molecule (CN_S_c= 8). The C —C distances

Cp

˚

vary from 1.405 (3) (C30—C31) to 1.423 (3) A (C28—C29),

˚

with an average value of 1.415 (6) A. The Cp–Ph dihedral

ꢄ

angle is 10.49 (18) for the C32–C37 phenyl ring and 4.08 (18)

for the C38–C43 phenyl ring, and the C_i_p_s_o(Ph) atom deviation

˚

from the Cp plane is 0.150 (4) A for C32 and 0.073 (4) A for

C38, being somewhat different compared to corresponding

data for (3a). However, the overall molecular structure of the

5

complex in (5b) is very similar to that of [(ꢁ -1,3-Ph C H )-

2

5

3

6

Lu(ꢁ -C Ph )(THF)] (CN = 8; IFUHIB; Roitershtein,

Lu

2

4

5

6

2

0

Minyaev et al., 2007) and [(ꢁ -C H )Lu(ꢁ -C Ph )(ꢀ O,O -

5

2

4

DME)](DME) (DME is dimethoxyethane; CN_L_u= 9;

KAMZOO; Roitershtein et al., 2004).

Figure 7

5

6

2 5 3 2 4

The molecular structure of [(ꢁ -1,3-Ph C H )Sc(ꢁ -C Ph )(THF)] in (5b).

Displacement ellipsoids are drawn at the 30% probability level and all

but two H atoms have been omitted for clarity.

1

According to comparisons of the H NMR spectra of (1), (4)

and (5a), recordered in THF-d , (5a) exhibits temperature-

8

ꢂ

Acta Cryst. (2018). C74, 769–781

Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide 777

research papers

dependent hindered rotation of only one phenyl group of the

dianionic ligand [unlike complexes (1a) and (2a)] and the

phenyl groups of the Cp ligand. Therefore, the coordination

Table 6

LMCT absorbance bands for tetraphenylethylenide complexes in THF.

Áꢆmax is a short wavelength shift of a LMCT band with respect to that of

M [C Ph ] (M = Na and K).

6

4

2

4

type of the dianion changes in solution from ꢁ to ꢁ (Scheme

). This has been observed previously for analogous Lu

3

1

2

3

4

5

6

7

8

9

1

Na [C

2

Na [Yb(C Ph ) ]

2

Ph ] and K

4

2

[C Ph

2

4

]

485

–

Roberts & Szwarc (1965)

5

0

6

0

365, 475 –* Minyaev et al. (2007)

370, 495 –* Minyaev et al. (2007)

2

4 2

complexes [(ꢁ -Cp )Lu(ꢁ -C Ph )(THF) ] (Cp = C H or 1,3-

2

4

2

5

2

K [Yb(C

2 4 2

Ph ) ]

Ph C H ; Roitershtein et al., 2004; Roitershtein, Minyaev et al.,

2

5

3

Na[Y(C Ph ) ]

4 2

Na[Lu(C

405

395

397

392

391

421

410

390

80 Roitershtein et al. (1998)

90 Roitershtein et al. (2004)

88 Roitershtein et al. (2004)

93 This work

2

2007).

2

Ph

4 2

) ]

K[Lu(C

Na[Sc(C

K[Sc(C Ph

(1,3-TMS

0 (C

2

4

2

) ]

2

4

)

2

], (1a)

2

4

2

) ], (2a)

94 This work

C

2 5

3

H )Lu(C

2

Ph

4

)

64 Unpublished results

75 Roitershtein et al. (2004)

95 Roitershtein, Minyaev et al.

(2007)

103 This work

5

H )Lu(C

2

4

Ph )

1 (1,3-Ph

2

C

5

H

3

)Lu(C

)Sc(C

2

4

)

12 (1,3-Ph

C

2 5

H

3

2

4

), (5a) 382

Note: (*) the

superposition of ꢆmax for M

equilibrium in solution (Minyaev et al., 2007): M

[C Ph ].

ꢆ

max values of labile complexes

M

2

[Yb(C Ph ] are likely due to

2

4

2

[Yb(C Ph ] and M [(C

2

4

)

2

Ph )] because of existing dynamic

[Yb(C Ph ] = [Yb(C Ph )(THF) ] +

4

2

4

)

2

4

M

2

4

signiﬁcant short wavelength shift of the LMCT band, indi-

cating the tight and efﬁcient ligand coordination to the metal

3

.4. UV–Vis data of tetraphenylethenide complexes

ꢁ

An efﬁcient interaction between an organic anionic ligand

cation in THF solution. The [Ln(C

2

Ph

4

)

] anions have closely

2

with a metal cation is generally reﬂected in a strong short

wavelength shift of a ligand-to-metal charge transfer (LMCT)

absorbance band as compared to alkali-metal salts of the

anion (Szwarc, 1972). The LMCTabsorbance bands of various

similar Áꢆmax values (80–94 nm). An interesting trend is seen

for the Cp derivative, namely that the smallest Áꢆmax value is

observed for the complex bearing electron-donating substi-

tuents (1,3-TMS

observed for (5a), in which the 1,3-Ph

more pronounced electron-withdrawing property. This is

C H

2 5 3

), whereas the highest ꢆmax shift is

tetraphenylethylenide complexes are summarized in Table 6.

III

C H

2 5 3

ligand displays a

All tetraphenylethenide Ln

complexes demonstrate a

Figure 8

6

3

2 2 2 5 3 2 2 10 2 2

The structure of the [K(THF) ] [(1,3-Ph C H ) Sc (ꢁ -C14H ) (ꢂ -ꢁ :ꢁ -C14H10)] unit in (6). H atoms have been omitted and disorder is not shown.

Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, y, ꢁz + 1; (ii) ꢁx + 1, ꢁy, ꢁz + 1; (iii) ꢁx + 1, ꢁy, z.]

ꢂ

7

78 Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide

Acta Cryst. (2018). C74, 769–781

research papers

4

Table 7

Selected bond lengths (A) for (6).

ꢁ for an unsymmetrical bonding type for rare-earth anthra-

˚

3+

cenide compounds. The Sc cation in (6) is bound to C atoms

i

at the 9- and 10-positions (atoms C13 and C13 ; Fig. 8) of the

bent anthracene dianion and has four additional short contacts

Sc1—C1

Sc1—C2

Sc1—C3

2.522 (4)

2.512 (3)

2.470 (3)

2.616 (3)

2.348 (3)

2.874 (3)

2.524 (3)

2.582 (3)

2.605 (3)

3.079 (4)

3.106 (3)

3.138 (3)

3.431 (3)

3.020 (3)

3.404 (3)

1.411 (3)

C2—C3

C2—C4

C3—C3

1.418 (4)

1.478 (4)

1.400 (6)

1.362 (10)

1.385 (6)

1.415 (5)

1.428 (7)

1.450 (5)

1.474 (4)

1.397 (4)

1.418 (6)

1.383 (5)

1.380 (8)

1.281 (5)

1.393 (5)

1.438 (4)

1.390 (11)

1.371 (7)

1.411 (3)

1.466 (7)

2.190 (2)

i

with C atoms (C12, C12 , C14 and C14 ). The ligand folding

i

C10—C10

C10—C11

C11—C12

C12—C12

C12—C13

C13—C14

C14—C15

C14—C14

C15—C16

C16—C16

C19—C18

C19—C19

C19—C20

C17—C17

C17—C18

C20—C21

C21—C21

i

angle between planes deﬁned by the C10–C13/C10 –C13 and

Sc1—C12

Sc1—C13

Sc1—C14

Sc1—C20

Sc1—C21

K1—O1

i

C13–C16/C13 –C16 atoms is 33.74 (12) . The other anthrace-

i

ꢄ

i

3

nide ligand is planar and exhibits the ꢂ -ꢁ :ꢁ bridging bis-

2

allylic coordination mode. This coordination type is also

common for rare-earth anthracenide complexes. However, (6)

is the only example displaying both coordination modes for

the anthracene dianion, according to the CSD (Groom et al.,

i

2016). The Sc—C and C—C bond distances in the anthrace-

iii

ii

nide ligands are consistent with the anticipated major reso-

nance forms (Scheme 4).

K1—C1

ii

K1—C2

ii

K1—C3

3+

Besides coordination with two dianions, the Sc cation is

K1—C11

K1—C12

K1—C14

C1—C2

5

iv

also ꢁ -coordinated by a 1,3-diphenylcyclopentadienyl ligand

˚

with a Cp(centroid)—Sc distance of 2.190 (2) A. The Cp–Ph

Sc1—Cpcentroid

ꢄ

dihedral angles in the 1,3-Ph C H ligand are 19.0 (2) (for the

2

5

3

1

2

1

2

ꢄ

Symmetry codes: (i) x; y; ꢁz þ 1; (ii) x ꢁ ; ꢁy þ ; z; (iii) ꢁx þ 1; ꢁy; z; (iv)

C4/C5A–C8A/C9 phenyl ring) and 27.4 (2) (for the C4/C5B–

C8B/C9 phenyl ring), indicating noticeable steric hindrance

ꢁ

x þ 1; ꢁy; ꢁz þ 1.

[

are 0.065 (4) A (atoms C4 and C4 ), directed outward from

see data for (3a)]. The C_i_p_s_o(Ph) deviations from the Cp plane

i

˚

consistent with partial electron-density transfer from the

3+

+

3+

Sc . The K cation is bound to two THF molecules and

displays six short contacts with the bent dianion [atoms C11,

dianionic ligand via the Ln cation to the antibonding orbital

0

of the Cp ligand in Cp Ln(C Ph ) complexes (Roitershtein,

4

2

i

C12, C14, C11 , C12 and C14 ; symmetry code: (i) x, y, ꢁz + 1;

Minyaev et al., 2007).

+

Table 7]. The K cation also has contacts to the 1,3-Ph C H

2

5

3

2ꢁ

ligand of another [(1,3-Ph C H ) Sc (C H ) ] dianionic

2

5

3 2

2

14 10 3

3.5. Crystal structure of (6)

iv

1

2

unit [atoms C1 , C2 and C3 ; symmetry code: (iv) x ꢁ ,

1

2

To the best of our knowledge, the crystal structure of (6) is

ꢁy + , z; Table 7] with a Cp

—K distance of

(centroid)

˚

2.873 (2) A. Thus, complex (6) itself represents an example of

entirely unique. The crystal data for (6) (crystals were

obtained as shown in Fig. 3, upper synthesis) were initially

collected on a Bruker SMART CCD Platform. Due to rather

high R_i_n_tvalue (16.4%) and the presence of many disordered

atoms after reﬁnement, its synthesis was repeated under

different conditions (Fig. 3, middle synthesis); and better

crystal data were recollected on an Bruker APEXII CCD

instrument. The second reﬁnement demonstrated that the

presence of many disordered atoms is an intrinsic property of

the structure.

a 2D (two-dimensional) coordination polymer {[K(THF) ] -

2

Sc (1,3-Ph C H ) (C H ) } , where coordination between

2

5

3 2 14 10 3 1

2

neighboring [Sc (1,3-Ph C H ) (C H ) ] dianionic units

ꢁ

2

5

3 2 14 10 3

+

occurs via short Kꢀ ꢀ ꢀC contacts with [K(THF) ] units: one

2

+

unit has interactions with four [K(THF) ] cations, and each

2

cation connects two units (see Fig. 8 and Fig. S5 in the

supporting information). The 2D layers of {[K(THF) ] Sc -

(1,3-Ph C H ) (C H ) } are parallel to (001) (Fig. S5).

2

5

3 2 14 10 3 1

Upon formation, crystals of (6) are poorly soluble in THF,

probably due to its coordination polymer structure.

The crystal structure of (6) is highly symmetrical. A quarter

of the compound (6) (Fig. 8) is crystallographically unique (see

0

Fig. S2 in the supporting information; Z = 0.25). Atoms Sc1,

K1, C1, H1 and C21 lie in the same mirror plane. The

remaining atoms are generated by this mirror plane (the

symmetry operation is x, y, ꢁz + 1) and by a twofold rotation

axis (the symmetry operation is ꢁx + 1, ꢁy, ꢁz + 1). One

anthracenide ligand (atoms C17–C21 and their symmetrical

equivalents; Fig. 8) lies on both the mirror plane and the

twofold rotation axis (see Fig. S4 in the supporting informa-

tion for disorder details); therefore, the occupancies for atoms

Sc1, K1, C1, H1, C17, H17, C18, H18 and H19 are 50%.

Selected bond distances in (6) are presented in Table 7.

Perhaps, the most striking feature of (6) is the presence of

two different coordination modes of the anthracene dianion.

3

.6. The CSD survey

All known crystal structures with the tetaphenylethylene

dianion have been discussed above. No crystal structures of

any other rare-earth, alkaline-earth and d-metals are known

where the tetraphenylethylene ligand bears a negative charge.

Moreover, only three structures of Ag ꢄ-complexes with an

uncharged C Ph ligand have been reported to date (Ino et al.,

+

2

4

6

Two anthracenide ligands display the ꢁ -coordination mode.

2000). Therefore, this ligand remains unique within the

organometallic chemistry of d- and rare-earth metals.

2

Sometimes in the literature, it is also referred to as ꢁ or even

ꢂ

Acta Cryst. (2018). C74, 769–781

Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide 779

research papers

3

The crystal structures or rare-earth metals bearing poly-

phenyl-substituted cyclopentadienyl ligands are still poorly

explored (Roitershtein et al., 2012; Minyaev et al., 2016). This

especially concerns complexes with 1,3-diphenyl- and 1,2,4-

triphenylcyclopentadienyl ligands. Here, we bring attention to

known crystal structures containing the 1,3-diphenylcyclo-

pentadienyl ligand and the anthracene dianion.

ligand binding modes. The ꢂ -ꢁ :ꢁ bis-allylic coordination

2

3

+

mode can be found in structures where two Ln cations are

coordinated by a ﬂat anthracene ligand via the C atoms at the

8, 8a and 9, and 4, 4a and 10 ligand positions. This ligand type

3

was found in {(ꢂ -ꢁ :ꢁ -C H )[La(C Me ) ] } (NAGSOD;

2

14 10

5

5 2 2

3

Thiele et al., 1996) and {(ꢂ -ꢁ :ꢁ -C H )[Sm(C Me ) ] }ꢀ-

2

14 10

5

5 2 2

(toluene) (WEVNAM; Evans et al., 1994). The bis-allylic

coordination type is also observed in the related tetracene

3.6.1. Crystal structures substituted with 1,4-diphenyl-

3

cyclopenta-1,3-dienes. The crystal structures of 1,3- or 1,4-

diphenylcyclopenta-1,3-dienes have not been determined to

date, likely due to the facile 1,2-prototropic shift induced even

by slightly elevated temperatures (Prinzhuch & Thyes, 1971)

during puriﬁcation, and leading to a thermodynamic mixture

complex {(ꢂ -ꢁ :ꢁ -C H )[Sm(C Me ) ] }ꢀ(benzene) (WEV-

2

18 12

5

5 2 2

NOA; Evans et al., 1994). Another coordination type of a bent

anthracene dianion involves positions 9 and 10 (short contacts

via positions 4a, 8a, 9a and 10a may also be present). This

coordination type is displayed by heavier lanthanide

complexes and Y, i.e. [(C H )Lu(C H CH CH PPh )-

1

of 1,3- and 1,4-isomers ( H NMR data), whereas three struc-

14

10

5

4

2

tures of analogous perﬂuorinated 1,4-diphenylcyclopenta-1,3-

dienes are known, namely 1,4-bis(pentaﬂuorophenyl)cyclo-

penta-1,3-diene (ACEDAN/ACEDAN01; Thornberry et al.,

(DME)] (QOFFIB; Roitershtein, Romanenkov et al., 2007),

[(C H )Lu(C H )(THF) ] (VUJDAF; Roitershtein et al.,

14

10

5

2

+

ꢁ

1992), [Na(diglyme) ] [(C H )Lu(C H ) ]

(YAXSUL;

Roitershtein et al., 1993), [(C H )TmI(DME) ] (UCOXEP;

2

14 10

5

5 2

0

2000), dimethyl 4,4 -cyclopenta-3,5-diene-1,3-diylbis(tetra-

14

10

2

+

ﬂuorobenzoate) (POCTIM; Enk et al., 2009) and 1,4-bis(per-

ﬂuoro-4-tolyl)cyclopentadiene (YEJCAS; Deck et al., 2006).

Moreover, the crystal structures of 1,2,4-triphenyl-, 1,2,3,4-

tetraphenyl- and 1,2,3,4,5-pentaphenylcyclopenta-1,3-dienes

and their substituted derivatives are known (22 structures in

the CSD, Version 5.39, latest update of February 2018; Groom

et al., 2016).

Fedushkin et al., 2001), and [K(18-crown-6] [(C H )Y-

14 10

t

2

ꢁ

(C H NSiMe Bu) Fe] ꢀEt O (YEMYEW; Huang et al.,

5

4

2

2013).

Bulky dianionic ligands, such as in the latter case

3+

(YEMYEW), do not allow two Ln cations to be coordinated

3

by the anthracene dianion via the allylic positions (ꢂ -ꢁ :ꢁ

coordination type), even in the case of small Sc . Instead, one

cation is coordinated via the 9- and 10-positions of the bent

dianion, whereas the second cation is ꢁ - or ꢁ -bound to a

nearly ﬂat terminal ring of the anthracenide ligand (the third

3

2

3+

3

.6.2. Crystal structures with the 1,3-diphenylcyclopenta-

dienyl ligand. Rare-earth complexes with the 1,3-Ph C H

3

4

6

2

5

ligand are not numerous, viz. the two isostructural complexes

1,3-Ph C H )LnCl (THF) [Ln = Lu (IFUHEX; Roitersh-

t

2

(

coordination type): {(C H )[Ln(C H NSiMe Bu) Fe(THF)] }

2

5

3

2

3

14 10

5

4

2

tein, Minyaev et al., 2007) and Yb (OFUHEE; Roitershtein et

al., 2012)] and complex (1,3-Ph C H )Lu(C Ph )(THF)

[Ln = Y (SIRRAO; Huang et al., 2014) and Sc (UXUMIK;

Huang et al., 2011)] and [(C H ){Y[PhP(CH SiMe NSi-

2

5

3

2

4

14 10

2

(IFUHIB; Roitershtein, Minyaev et al., 2007). The crystal

structures of other metal complexes are represented by (1,3-

Me CH ) PPh] }] (WIYLIZ; Fryzuk et al., 2000). In these

2 2 2 2

3+

complexes with two Ln cations, the folding angle of the

anthracene dianion is noticeably smaller than in the cases of

Ph C H )(C H )ZrCl (EYUSIA; Thornberry et al., 2004),

5

2

5

3

5

2

3+

(

1,3-Ph C H ) TiCl (PCYPTC; van Soest et al., 1973), [(1,3-

2

complexes with one coordinated Ln cation. {(C H )[Sc-

14 10

2

5

3 2

t

2

Ph C H )Ru(CO)(ꢂ -CO)] ꢀ(toluene) (VUZYOE; Schumann

(C H NSiMe Bu) Fe(THF)] } is the only Sc–anthracenide

4

2

5

3

2

5

2

et al., 2002), [(1,3-Ph C H )Ru C(CO) (ꢂ -CO)(ꢂ -CPh)]

complex known to date.

2

5

3

6

12

2

3

(YUZPEO; Haggitt et al., 1995), (1,3-Ph C H ) Fe

2 5 3 2

(

ꢁ

YOCWOC; Schumann et al., 1995), [(ꢂ -1,3-Ph C H ) Tl -

2 2 5 3 2 2

4

. Concluding remarks

ꢂ -THF) ] (YOCWIW; Schumann et al., 1995) and {(ꢂ₂-

2 2 1

5

6

:ꢁ -1,3-Ph C H )[Mn(CO) ][Cr(CO) ]} (NOYCUZ; Kang et

The tetraphenylethenide ligand in (1b) demonstrates a

3

symmetrical bis-ꢁ -allyl coordination mode, which was

reported previously for analogous homoleptic anions [Ln(ꢁ -

C Ph ) ] (Ln = Y, Lu, n = 1; Ln = Yb, n = 2; Roitershtein et

2

5

3

al., 1997). There are six related d-metal complexes bearing

various substituents in the phenyl rings of the 1,3-diaryl-

cyclopentadienyl ligand, including ansa complexes and

heterobimetallic derivatives, i.e. ACEFAP (Thornberry et al.,

6

nꢁ

4 2

3

al., 1998, 2004; Minyaev et al., 2007). The bis-ꢁ -allyl coordi-

nation mode is retained in THF solutions of (1a) and (2a).

Complex (5b) exhibits an unsymmetrical bis-ꢁ -allyl coordi-

nation mode of the dianion in the crystal structure, but this

2

000), NEYDEB and NEYDIF (Muraoka et al., 2007),

3

NOYTIG (Sasamori et al., 2014), QONVUL (Tanaka &

Kinbara, 2008) and UHIWOX (Muraoka et al., 2003).

Therefore, according to the CSD, the crystal structures of f-

and even d-metal complexes with this ligand are still poorly

explored. One possible reason for this is that the corre-

sponding precursor, namely diphenylcyclopentadiene, is less

synthetically available than other polyphenyl-substituted

cyclopentadienes.

4

changes to ꢁ in THF-d solution, analogous to what is

observed for complexes [(C H )Lu(C Ph )(THF) ] and [(1,3-

5

8

5

2

4

2

Ph C H )Lu(C Ph )(THF)] (Roitershtein et al., 2004;

2

5

3

2

4

Roitershtein, Minyaev et al., 2007). Based on X-ray diffraction,

NMR and UV–Vis studies, we have demonstrated the

presence of a signiﬁcantly covalent contribution to the ionic

2ꢁ

Sc —C Ph bonding. The unique ate complex (6) contains

4

3+

3.6.3. Crystal structures of rare-earth metals with the

2

2ꢁ

anthracene dianion. Previously described crystal structures of

rare-earth anthracenide complexes exhibit three types of

a complex [Sc (1,3-Ph C H ) (C H ) ]

2

dianionic unit,

2

6

5

3 2 14 10 3

3

which displays both the ꢁ and ꢂ -ꢁ :ꢁ coordination modes of

2

ꢂ

7

80 Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide

Acta Cryst. (2018). C74, 769–781

research papers

+

the anthracene ligands. The dianionic unit and [K(THF)₂]

cations form a 2D coordination polymer structure.

Mason, J. (1987). Multinuclear NMR , ch. 19, Early Transition Metals,

Lanthanides and Actinides , by D. Rehder. New York: Plenum Press.

Matsui, H., Yoshino, A. & Takahashi, K. (1994). Bull. Chem. Soc. Jpn ,

67 , 363–367.

Acknowledgements

Minyaev, M. E. & Ellis, J. E. (2014). Acta Cryst. E 70 , m249–m250.

Minyaev, M. E., Lyssenko, K. A., Belyakov, P. A., Antipin, M. Yu. &

Roitershtein, D. M. (2007). Mendeleev Commun. 17 , 102–104.

Minyaev, M. E., Vinogradov, A. A., Roitershtein, D. M., Borisov, R. S.,

Ananyev, I. V., Churakov, A. V. & Nifant’ev, I. E. (2016). J.

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Muraoka, T., Kinbara, K., Wakamiya, A., Yamaguchi, S. & Aida, T.

The authors are grateful to P. A. Belyakov (deceased) for

recording the HMBC and HSQC NMR spectra of (1a), to

45

Letitia Yao for help in recording the Sc NMR spectrum of

2a), and to D. M. Roitershtein for inspiration for studying

(

tetraphenylethenide rare-earth complexes. The ﬁnal X-ray

diffraction study of compound (6) was carried out within the

State Assignment on Fundamental Research to the Kurnakov

Institute of General and Inorganic Chemistry.

(2007). Chem. Eur. J. 13 , 1724–1730.

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Funding information

Funding for this research was provided by: US National

Science Foundation program (grant No. CHE–0841014); The

State Program of TIPS RAS supported by FASO Russia.

1

18–120.

Roitershtein, D. M., Lyssenko, K. A., Belyakov, P. A., Antipin, M. Yu.

Petrov, E. S. (1997). Russ. Chem. Bull. Int. Ed. 46 , 1590–1594.

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(

ꢂ

Acta Cryst. (2018). C74, 769–781

Ellis et al.

Scandium complexes with tetraphenylethylenide and anthracenide 781

supporting information

Acta Cryst. (2018). C74, 769-781 [https://doi.org/10.1107/S2053229618007295]

Scandium complexes with the tetraphenylethylene and anthracene dianions

John E. Ellis, Mikhail E. Minyaev, Ilya E. Nifant'ev and Andrei V. Churakov

Computing details

Data collection: SMART (Bruker, 2003) for (1b), (3a), (5b); APEX2 (Bruker, 2008) for (6). Cell refinement: SAINT

(

Bruker, 2003) for (1b), (3a), (5b); SAINT (Bruker, 2008) for (6). Data reduction: SAINT (Bruker, 2003) for (1b), (3a),

5b); SAINT (Bruker, 2008) for (6). Program(s) used to solve structure: SHELXS (Sheldrick, 2008) for (1b), (5b), (6);

SIR2002 (Burla et al., 2003) for (3a). For all structures, program(s) used to refine structure: SHELXL2017 (Sheldrick,

015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL

Sheldrick, 2008).

2

(

6

(

18-Crown-6)bis(tetrahydrofuran-κO)sodium bis(η -1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran

disolvate (1b)

Crystal data

[

M

Na(C

= 1285.51

Triclinic, P1

4

H

8

O)

2

24 6 20 2

(C12H O )][Sc(C26H ) ]·2C

H

4 8

O

Z = 2

F(000) = 1376

D = 1.247 Mg m

x

r

−3

a = 12.6071 (18) Å

b = 14.764 (2) Å

c = 18.585 (3) Å

α = 84.507 (2)°

β = 88.508 (2)°

γ = 84.033 (2)°

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 4092 reflections

θ = 2.2–27.8°

µ = 0.17 mm

T = 173 K

−1

Needle, red

0.40 × 0.25 × 0.25 mm

3

V = 3424.2 (9) Å

Data collection

SMART Platform CCD area detector

diffractometer

Radiation source: normal-focus sealed tube

Graphite monochromator

32161 measured reflections

11986 independent reflections

6407 reflections with I > 2σ(I)

R

int = 0.073

φ and ω scans

θmax = 25.0°, θmin = 1.1°

Absorption correction: multi-scan

h = −14→14

k = −17→17

l = −22→22

(

SADABS; Bruker, 2003)

T

min = 0.869, Tmax = 0.967

Refinement

2

Refinement on F

860 parameters

Least-squares matrix: full

46 restraints

Primary atom site location: structure-invariant

direct methods

2

R[F > 2σ(F )] = 0.074

2

wR(F ) = 0.183

S = 1.02

Secondary atom site location: difference Fourier

map

11986 reflections

Acta Cryst. (2018). C74, 769-781

sup-1

supporting information

2

Hydrogen site location: mixed

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ (F

o

) + (0.0778P) + 1.9339P]

2

where P = (F

(Δ/σ)max < 0.001

Δρmax = 0.40 e Å

o

+ 2F )/3

c

−3

Δρmin = −0.48 e Å

Special details

Experimental. moisture and air sensitive

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;

correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate

(

isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

2

Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,

conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > 2sigma(F ) is

used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based

2

on F are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )

x

y

z

Uiso*/Ueq

Occ. (<1)

Sc1

C1

C2

C3

C4

H4

C5

H5

C6

H6

C7

H7

C8

H8

C9

C10

H10

C11

H11

C12

H12

C13

H13

C14

H14

C15

C16

H16

C17

0.79311 (6)

0.8864 (3)

0.9393 (3)

0.7843 (3)

0.7245 (3)

0.755 (3)

0.6214 (3)

0.583860

0.5732 (3)

0.502078

0.6312 (3)

0.599837

0.7321 (3)

0.768566

0.9536 (3)

0.9163 (4)

0.843051

0.9838 (4)

0.956080

1.0901 (4)

1.136157

1.1289 (4)

1.201940

1.0635 (3)

1.093372

0.9946 (3)

0.9779 (3)

0.949 (3)

1.0235 (3)

0.73855 (5)

0.8495 (3)

0.7566 (3)

0.8736 (3)

0.8055 (3)

0.746 (3)

0.8255 (3)

0.777447

0.9133 (3)

0.926623

0.9824 (3)

1.043934

0.9647 (3)

1.014204

0.9178 (3)

0.9895 (3)

0.996628

1.0503 (3)

1.098111

1.0419 (3)

1.083214

0.9731 (3)

0.967962

0.9110 (3)

0.862346

0.7058 (3)

0.7327 (3)

0.789 (3)

0.6815 (3)

0.22090 (4)

0.1545 (2)

0.1411 (2)

0.1218 (2)

0.0991 (2)

0.096 (2)

0.0729 (2)

0.059214

0.0666 (2)

0.050116

0.0849 (2)

0.078738

0.1117 (2)

0.123904

0.1775 (2)

0.2191 (2)

0.232911

0.2408 (3)

0.268884

0.2219 (3)

0.237006

0.1809 (3)

0.166478

0.1603 (2)

0.133722

0.2015 (2)

0.2729 (2)

0.280 (2)

0.3327 (2)

0.0275 (2)

0.0311 (10)

0.0324 (10)

0.0309 (10)

0.0306 (10)

0.037*

0.0363 (10)

0.044*

0.0409 (11)

0.049*

0.0407 (11)

0.049*

0.0373 (10)

0.045*

0.0346 (10)

0.0432 (11)

0.052*

0.0519 (13)

0.062*

0.0574 (14)

0.069*

0.0557 (14)

0.067*

0.0470 (12)

0.056*

0.0304 (10)

0.0324 (10)

0.039*

0.0396 (11)

Acta Cryst. (2018). C74, 769-781

sup-2

supporting information

H17

C18

H18

C19

H19

C20

H20

C21

C22

H22

C23

H23

C24

H24

C25

H25

C26

H26

C27

C28

C29

C30

H30

C31

H31

C32

H32

C33

H33

C34

H34

C35

C36

H36

C37

H37

C38

H38

C39

H39

C40

H40

C41

C42

H42

C43

H43

C44

1.010442

1.0863 (3)

1.114697

1.1082 (3)

1.154394

1.0649 (3)

1.081931

0.9624 (3)

0.9685 (3)

0.955456

0.9933 (3)

0.997370

1.0121 (3)

1.032169

1.0014 (3)

1.011378

0.9761 (3)

0.967787

0.7084 (3)

0.6372 (3)

0.7125 (3)

0.6767 (3)

0.637 (3)

0.6847 (3)

0.659789

0.7273 (4)

0.733697

0.7612 (3)

0.789503

0.7546 (3)

0.779037

0.7355 (3)

0.8236 (3)

0.870475

0.8440 (3)

0.903875

0.7794 (4)

0.793232

0.6931 (4)

0.647778

0.6724 (3)

0.613326

0.6759 (3)

0.7841 (3)

0.829 (3)

0.8241 (3)

0.896566

0.7625 (3)

0.702341

0.6022 (3)

0.566147

0.5749 (3)

0.520864

0.6238 (3)

0.602763

0.7374 (3)

0.6504 (3)

0.599280

0.6370 (4)

0.577090

0.7096 (4)

0.699634

0.7964 (4)

0.847185

0.8103 (3)

0.870994

0.6782 (3)

0.6713 (3)

0.7703 (3)

0.8468 (3)

0.838 (3)

0.9363 (3)

0.985192

0.9557 (3)

1.017022

0.8829 (3)

0.895256

0.7940 (3)

0.746424

0.5949 (3)

0.5817 (3)

0.628204

0.5036 (3)

0.497824

0.4336 (3)

0.380137

0.4439 (3)

0.396303

0.5220 (3)

0.526418

0.6084 (3)

0.5674 (3)

0.574 (3)

0.5133 (3)

0.488126

0.4951 (3)

0.379273

0.3262 (2)

0.367734

0.2570 (2)

0.251457

0.1977 (2)

0.151591

0.0649 (2)

0.0400 (2)

0.072888

−0.0318 (2)

−0.046942

−0.0814 (2)

−0.129902

−0.0597 (2)

−0.093714

0.0120 (2)

0.025730

0.3265 (2)

0.26412 (19)

0.3467 (2)

0.2975 (2)

0.255 (2)

0.3123 (2)

0.277957

0.3750 (2)

0.384267

0.4252 (2)

0.469715

0.4120 (2)

0.447578

0.37686 (19)

0.4230 (2)

0.422239

0.4694 (2)

0.500098

0.4722 (2)

0.504559

0.4259 (2)

0.426318

0.3794 (2)

0.348145

0.2121 (2)

0.2129 (2)

0.252 (2)

0.048*

0.0452 (12)

0.054*

0.0439 (12)

0.053*

0.0384 (11)

0.046*

0.0338 (10)

0.0425 (11)

0.051*

0.0520 (13)

0.062*

0.0549 (14)

0.066*

0.0524 (13)

0.063*

0.0452 (12)

0.054*

0.0286 (9)

0.0265 (9)

0.0285 (9)

0.0315 (10)

0.038*

0.0369 (10)

0.044*

0.0444 (12)

0.053*

0.0423 (11)

0.051*

0.0350 (10)

0.042*

0.0282 (9)

0.0366 (10)

0.044*

0.0414 (11)

0.050*

0.0486 (12)

0.058*

0.0427 (11)

0.051*

0.0337 (10)

0.040*

0.0287 (9)

0.0328 (10)

0.039*

0.1593 (2)

0.161064

0.1041 (2)

0.0385 (11)

0.046*

0.0457 (12)

Acta Cryst. (2018). C74, 769-781

sup-3

supporting information

H44

C45

H45

C46

H46

C47

C48

H48A

C49

H49A

C50

H50A

C51

H51A

C52

H52A

Na1

O1

O2

O3

O4

0.791310

0.6557 (3)

0.611433

0.6138 (3)

0.540514

0.5225 (3)

0.4585 (3)

0.489123

0.3511 (3)

0.309601

0.3036 (3)

0.229768

0.3661 (3)

0.335092

0.4744 (3)

0.516297

0.37921 (13)

0.4239 (2)

0.4224 (2)

0.3400 (2)

0.3337 (2)

0.3433 (2)

0.4299 (2)

0.1962 (2)

0.5614 (2)

0.4701 (4)

0.546282

0.465302

0.4114 (4)

0.335076

0.441328

0.3665 (4)

0.392516

0.289479

0.3835 (4)

0.347860

0.460668

0.3510 (4)

0.427261

0.323228

0.2906 (4)

0.214250

0.296182

0.2810 (4)

0.275575

0.207994

0.3429 (4)

0.310103

0.458439

0.5322 (3)

0.519908

0.5853 (3)

0.607965

0.7051 (3)

0.7437 (3)

0.750997

0.7718 (3)

0.796881

0.7641 (3)

0.782410

0.7290 (3)

0.723847

0.7011 (3)

0.678926

0.25410 (12)

0.19929 (19)

0.38248 (19)

0.43418 (19)

0.3067 (2)

0.1224 (2)

0.07066 (19)

0.2560 (2)

0.2612 (2)

0.2602 (3)

0.262147

0.238997

0.3534 (3)

0.351478

0.396738

0.4693 (3)

0.514507

0.466699

0.4977 (3)

0.560033

0.498522

0.4584 (3)

0.451027

0.523179

0.3985 (3)

0.405629

0.415984

0.2441 (3)

0.264961

0.240489

0.1532 (3)

0.109376

0.067595

0.1029 (2)

0.065066

0.1546 (2)

0.152372

0.2713 (2)

0.2139 (2)

0.166683

0.2242 (3)

0.183765

0.2913 (3)

0.297646

0.3496 (2)

0.396775

0.3398 (2)

0.380728

0.27731 (9)

0.42279 (14)

0.37589 (14)

0.23880 (14)

0.13954 (15)

0.18819 (15)

0.32220 (15)

0.31551 (17)

0.24862 (18)

0.4642 (2)

0.450593

0.516266

0.4502 (2)

0.463488

0.479770

0.3583 (2)

0.387960

0.055*

0.0410 (11)

0.049*

0.0331 (10)

0.040*

0.0288 (9)

0.0359 (10)

0.043*

0.0435 (11)

0.052*

0.0442 (12)

0.053*

0.0435 (12)

0.052*

0.0354 (10)

0.043*

0.0483 (5)

0.0400 (7)

0.0388 (7)

0.0394 (7)

0.0453 (8)

0.0433 (8)

0.0417 (7)

0.0585 (9)

0.0551 (9)

0.0448 (12)

0.054*

0.0460 (12)

0.055*

0.0445 (12)

0.053*

O5

O6

O7

O8

C53

H53A

H53B

C54

H54A

H54B

C55

H55A

H55B

C56

H56A

H56B

C57

H57A

H57B

C58

H58A

H58B

C59

H59A

H59B

C60

0.368842

0.2804 (2)

0.268092

0.269519

0.1635 (2)

0.148971

0.151741

0.1234 (2)

0.137938

0.070785

0.1034 (2)

0.051319

0.053*

0.0435 (11)

0.052*

0.0502 (12)

0.060*

0.0523 (13)

0.063*

0.0505 (13)

0.061*

0.123694

0.1133 (2)

0.085728

0.061*

0.0513 (13)

0.062*

H60A

Acta Cryst. (2018). C74, 769-781

sup-4

supporting information

H60B

C61

H61A

H61B

C62

H62A

H62B

C63

H63A

H63B

C64

H64A

H64B

C65

H65A

H65B

C66

H66A

H66B

C67

H67A

H67B

C68

0.416864

0.4060 (4)

0.482110

0.383213

0.3919 (4)

0.315570

0.432491

0.4157 (5)

0.445926

0.338745

0.4707 (4)

0.464550

0.547343

0.1082 (4)

0.080143

0.130110

0.0240 (4)

−0.001074

−0.037779

0.0776 (5)

0.027559

0.111697

0.1589 (4)

0.217873

0.126180

0.6222 (4)

0.599596

0.612072

0.7360 (4)

0.784719

0.755033

0.769194

0.777192

0.7365 (7)

0.789115

0.755502

0.6272 (8)

0.602463

0.626401

0.7305 (13)

0.725105

0.791468

0.6296 (14)

0.646660

0.593368

0.3893 (4)

0.4175 (5)

0.397005

0.157339

0.0373 (3)

0.044654

−0.008139

0.0054 (3)

−0.000438

−0.055234

0.0465 (3)

−0.017498

0.051406

0.1093 (3)

0.090930

0.105395

0.3010 (4)

0.258884

0.354570

0.3312 (5)

0.396778

0.294934

0.3146 (5)

0.297417

0.368811

0.2366 (4)

0.232294

0.178156

0.3359 (4)

0.366787

0.381018

0.2977 (5)

0.343289

0.274563

0.293284

0.335904

0.2231 (7)

0.171475

0.244575

0.1936 (7)

0.186939

0.134091

0.2064 (8)

0.208369

0.162456

0.1867 (15)

0.153380

0.145748

0.7876 (3)

0.6889 (4)

0.666681

0.095091

0.2027 (2)

0.191774

0.171990

0.2802 (2)

0.291462

0.291280

0.3969 (3)

0.409471

0.409644

0.4382 (3)

0.490670

0.424568

0.2762 (3)

0.244704

0.245442

0.3301 (4)

0.319629

0.329708

0.3997 (3)

0.439355

0.411203

0.3863 (3)

0.420961

0.391196

0.2549 (4)

0.298594

0.212065

0.2602 (4)

0.241559

0.310458

0.211644

0.287787

0.2133 (8)

0.230310

0.162961

0.2168 (8)

0.167664

0.246171

0.2988 (11)

0.351857

0.286388

0.2676 (14)

0.224373

0.303356

−0.0311 (3)

−0.0294 (4)

−0.075196

0.062*

0.0469 (12)

0.056*

0.0464 (12)

0.056*

0.0643 (15)

0.077*

0.0602 (15)

0.072*

0.0731 (16)

0.088*

0.094 (2)

0.113*

0.088 (2)

0.105*

0.0783 (18)

0.094*

0.0805 (18)

0.097*

0.090 (2)

0.108*

0.109 (5)

0.131*

0.076 (4)

0.091*

0.087 (7)

0.104*

0.088 (7)

0.105*

H68A

H68B

C69

H69A

H69B

C70

H70A

H70B

H70C

H70D

C71A

H71A

H71B

C72A

H72A

H72B

C71B

H71C

H71D

C72B

H72C

H72D

O9

0.639 (12)

0.361 (12)

0.639 (12)

0.361 (12)

0.1246 (18)

0.089 (2)

0.106*

C73

H73A

Acta Cryst. (2018). C74, 769-781

sup-5

supporting information

H73B

C74

H74A

H74B

C75

H75A

H75B

C76

H76A

H76B

O10

0.495396

0.3612 (4)

0.403872

0.343897

0.2627 (5)

0.238927

0.204388

0.2940 (5)

0.236902

0.305428

0.0414 (7)

0.1301 (8)

0.160710

0.110320

0.2055 (6)

0.257303

0.245068

0.1375 (7)

0.117257

0.176044

0.0422 (6)

−0.023166

0.048045

0.674202

0.6457 (4)

0.639506

0.584413

0.7087 (4)

0.708262

0.691288

0.8011 (5)

0.834682

0.837329

0.8450 (6)

0.8443 (7)

0.780949

0.875877

0.8941 (7)

0.850963

0.932398

0.9521 (7)

1.013508

0.959342

0.9039 (6)

0.947367

0.869296

−0.023630

0.0306 (3)

0.075134

0.020311

0.0382 (3)

0.089407

0.009326

0.0101 (4)

−0.020452

0.050852

0.4779 (4)

0.5225 (5)

0.537321

0.566342

0.4760 (5)

0.452221

0.504575

0.4214 (5)

0.437868

0.374458

0.4145 (4)

0.411209

0.371283

0.106*

0.0615 (14)

0.074*

0.0778 (18)

0.093*

0.097 (2)

0.117*

0.227 (4)

0.178 (4)

0.213*

0.125 (3)

0.150*

0.163 (4)

0.196*

0.122 (3)

0.147*

C77

H77A

H77B

C78

H78A

H78B

C79

H79A

H79B

C80

H80A

H80B

0.147*

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

Sc1

C1

C2

C3

C4

C5

C6

C7

C8

0.0240 (4)

0.027 (2)

0.029 (2)

0.028 (2)

0.027 (2)

0.037 (3)

0.029 (2)

0.031 (3)

0.038 (3)

0.028 (2)

0.036 (3)

0.047 (3)

0.039 (3)

0.027 (3)

0.030 (3)

0.022 (2)

0.025 (2)

0.031 (2)

0.040 (3)

0.032 (3)

0.028 (2)

0.0292 (5)

0.037 (3)

0.032 (2)

0.036 (3)

0.035 (3)

0.047 (3)

0.053 (3)

0.038 (3)

0.032 (3)

0.038 (3)

0.042 (3)

0.046 (3)

0.048 (3)

0.050 (3)

0.047 (3)

0.032 (2)

0.031 (3)

0.051 (3)

0.049 (3)

0.042 (3)

0.043 (3)

0.0282 (4)

0.028 (2)

0.035 (2)

0.028 (2)

0.027 (2)

0.024 (2)

0.038 (3)

0.047 (3)

0.040 (3)

0.036 (2)

0.053 (3)

0.064 (3)

0.085 (4)

0.088 (4)

0.062 (3)

0.037 (2)

0.040 (3)

0.037 (3)

0.041 (3)

0.052 (3)

0.042 (3)

0.0010 (3)

0.0009 (3)

−0.0004 (18)

0.0020 (19)

0.0058 (18)

0.0022 (18)

0.0008 (19)

0.000 (2)

−0.001 (2)

0.005 (2)

−0.0027 (19)

0.000 (2)

−0.006 (3)

−0.023 (3)

−0.003 (3)

0.003 (2)

−0.0011 (18)

0.0007 (19)

0.000 (2)

−0.006 (2)

0.000 (2)

0.002 (2)

−0.0016 (3)

0.0013 (19)

0.0003 (19)

0.0008 (19)

0.000 (2)

0.006 (2)

0.008 (2)

0.002 (2)

0.005 (2)

−0.007 (2)

−0.008 (3)

0.009 (3)

0.005 (3)

0.002 (2)

0.0030 (19)

0.001 (2)

0.015 (2)

0.008 (2)

0.002 (2)

−0.0026 (19)

0.0009 (19)

−0.0022 (19)

0.002 (2)

−0.004 (2)

0.000 (2)

0.009 (2)

0.000 (2)

C9

−0.001 (2)

−0.007 (2)

−0.008 (2)

−0.010 (2)

0.001 (2)

−0.0071 (18)

−0.0013 (19)

−0.010 (2)

0.001 (2)

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

0.010 (2)

0.003 (2)

Acta Cryst. (2018). C74, 769-781

sup-6

supporting information

C21

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

C39

C40

C41

C42

C43

C44

C45

C46

C47

C48

C49

C50

C51

C52

Na1

O1

O2

O3

O4

O5

O6

O7

O8

C53

C54

C55

C56

C57

C58

C59

0.018 (2)

0.032 (2)

0.038 (3)

0.037 (3)

0.025 (2)

0.028 (2)

0.025 (2)

0.027 (2)

0.032 (2)

0.053 (3)

0.042 (3)

0.041 (3)

0.029 (2)

0.028 (2)

0.034 (3)

0.056 (3)

0.051 (3)

0.038 (3)

0.032 (2)

0.034 (3)

0.035 (3)

0.043 (3)

0.048 (3)

0.032 (2)

0.029 (2)

0.034 (3)

0.032 (3)

0.026 (2)

0.040 (3)

0.031 (2)

0.0311 (9)

0.0446 (18)

0.0401 (17)

0.0408 (17)

0.0411 (18)

0.0420 (18)

0.0457 (18)

0.043 (2)

0.0341 (18)

0.050 (3)

0.057 (3)

0.047 (3)

0.043 (3)

0.062 (3)

0.056 (3)

0.045 (3)

0.052 (3)

0.074 (4)

0.093 (4)

0.076 (4)

0.050 (3)

0.032 (2)

0.029 (2)

0.034 (2)

0.033 (3)

0.032 (3)

0.033 (3)

0.055 (3)

0.034 (3)

0.032 (2)

0.046 (3)

0.050 (3)

0.043 (3)

0.032 (3)

0.033 (3)

0.025 (2)

0.033 (3)

0.036 (3)

0.048 (3)

0.046 (3)

0.035 (2)

0.023 (2)

0.037 (3)

0.040 (3)

0.041 (3)

0.038 (3)

0.0619 (12)

0.0394 (18)

0.0414 (18)

0.0394 (18)

0.056 (2)

0.054 (2)

0.0386 (18)

0.086 (3)

0.050 (2)

0.048 (3)

0.047 (3)

0.040 (3)

0.035 (3)

0.048 (3)

0.058 (3)

0.071 (4)

0.036 (2)

0.042 (3)

0.044 (3)

0.030 (3)

0.036 (3)

0.045 (3)

0.029 (2)

0.023 (2)

0.028 (2)

0.034 (2)

0.044 (3)

0.050 (3)

0.034 (3)

0.030 (2)

0.023 (2)

0.035 (2)

0.036 (3)

0.041 (3)

0.045 (3)

0.030 (2)

0.032 (2)

0.044 (3)

0.048 (3)

0.032 (3)

0.034 (2)

0.036 (2)

0.037 (3)

0.057 (3)

0.065 (3)

0.049 (3)

0.037 (3)

0.0506 (11)

0.0361 (17)

0.0323 (17)

0.0369 (17)

0.0389 (18)

0.0352 (18)

0.0424 (19)

0.043 (2)

0.083 (2)

0.038 (3)

0.034 (3)

0.045 (3)

0.052 (3)

0.040 (3)

0.037 (3)

0.0041 (19)

0.003 (2)

0.009 (3)

0.004 (3)

0.0003 (18)

0.002 (2)

0.001 (2)

0.004 (2)

−0.001 (2)

−0.007 (2)

−0.019 (3)

−0.007 (3)

0.013 (3)

0.008 (2)

0.000 (2)

0.004 (2)

0.0001 (18)

−0.0043 (18)

−0.0030 (18)

−0.0008 (19)

0.002 (2)

−0.013 (2)

−0.015 (2)

−0.007 (2)

−0.0017 (19)

−0.006 (2)

0.002 (2)

0.0023 (17)

0.0000 (17)

0.0036 (17)

0.0022 (19)

0.002 (2)

−0.0033 (19)

−0.0033 (18)

−0.0073 (19)

−0.006 (2)

−0.002 (2)

−0.014 (2)

−0.002 (2)

−0.0064 (18)

0.000 (2)

0.008 (2)

0.003 (2)

−0.0014 (19)

0.0061 (18)

0.008 (2)

−0.002 (2)

0.005 (2)

0.009 (2)

0.011 (2)

0.002 (2)

0.005 (3)

−0.011 (2)

−0.004 (2)

−0.0061 (18)

−0.007 (2)

0.004 (2)

−0.003 (2)

−0.014 (2)

−0.0084 (19)

−0.0052 (18)

−0.006 (2)

0.003 (2)

−0.0016 (19)

0.0046 (18)

0.0013 (19)

0.004 (2)

0.010 (2)

0.000 (2)

0.0041 (19)

0.0028 (19)

0.000 (2)

−0.007 (2)

0.003 (2)

−0.003 (2)

−0.0021 (18)

−0.003 (2)

−0.007 (2)

−0.019 (2)

−0.010 (2)

−0.008 (2)

−0.0098 (18)

−0.003 (2)

−0.007 (2)

−0.010 (2)

−0.009 (2)

−0.010 (2)

−0.0021 (9)

−0.0038 (14)

−0.0013 (14)

0.0031 (14)

−0.0060 (16)

−0.0109 (15)

−0.0049 (15)

0.0025 (18)

−0.0187 (19)

−0.007 (2)

−0.009 (2)

−0.003 (2)

0.003 (2)

0.002 (2)

−0.003 (2)

−0.002 (2)

−0.0024 (8)

−0.0033 (15)

0.0046 (14)

−0.0058 (14)

−0.0041 (16)

−0.0070 (16)

−0.0086 (14)

0.0010 (18)

−0.0024 (17)

−0.007 (2)

−0.003 (2)

0.002 (2)

0.017 (2)

−0.001 (2)

0.0044 (8)

−0.0065 (14)

0.0044 (13)

0.0004 (14)

−0.0055 (14)

0.0031 (14)

−0.0067 (14)

0.0036 (16)

0.0015 (17)

−0.010 (2)

0.009 (2)

0.000 (2)

−0.005 (2)

−0.011 (3)

−0.003 (3)

−0.002 (2)

−0.001 (2)

−0.004 (2)

0.007 (2)

0.005 (2)

−0.012 (3)

Acta Cryst. (2018). C74, 769-781

sup-7

supporting information

C60

C61

C62

C63

C64

C65

C66

C67

C68

C69

C70

C71A

C72A

C71B

C72B

O9

C73

C74

C75

C76

O10

C77

C78

C79

C80

0.056 (3)

0.039 (3)

0.046 (3)

0.100 (4)

0.090 (4)

0.068 (4)

0.048 (4)

0.075 (4)

0.056 (4)

0.055 (4)

0.041 (3)

0.042 (6)

0.067 (7)

0.063 (10)

0.077 (12)

0.119 (4)

0.072 (4)

0.065 (4)

0.069 (4)

0.274 (8)

0.187 (9)

0.103 (6)

0.118 (7)

0.140 (7)

0.072 (4)

0.046 (3)

0.039 (3)

0.046 (3)

0.047 (3)

0.089 (4)

0.115 (6)

0.108 (5)

0.111 (5)

0.069 (4)

0.119 (6)

0.081 (7)

0.042 (6)

0.075 (12)

0.060 (11)

0.087 (4)

0.081 (5)

0.066 (4)

0.095 (5)

0.107 (6)

0.255 (8)

0.175 (9)

0.162 (8)

0.218 (10)

0.122 (7)

0.030 (3)

0.058 (3)

0.057 (3)

0.045 (3)

0.041 (3)

0.060 (4)

0.108 (5)

0.083 (5)

0.062 (4)

0.121 (5)

0.116 (5)

0.206 (13)

0.123 (11)

0.116 (14)

0.118 (15)

0.160 (5)

0.118 (6)

0.053 (3)

0.078 (4)

0.107 (5)

0.164 (6)

0.171 (9)

0.118 (7)

0.157 (8)

0.107 (6)

−0.013 (3)

−0.006 (2)

−0.010 (2)

−0.007 (3)

0.009 (3)

0.002 (2)

0.001 (2)

−0.004 (2)

−0.012 (3)

−0.027 (3)

−0.007 (3)

−0.003 (4)

0.015 (4)

−0.004 (3)

0.021 (3)

−0.002 (3)

0.026 (7)

0.033 (7)

−0.015 (10)

0.027 (12)

0.057 (3)

0.020 (4)

−0.009 (3)

0.007 (3)

0.031 (4)

−0.102 (6)

−0.069 (8)

0.004 (6)

0.006 (6)

−0.017 (5)

−0.018 (2)

−0.019 (2)

−0.009 (2)

0.003 (3)

0.001 (2)

0.004 (3)

0.019 (4)

−0.033 (4)

0.013 (3)

−0.029 (4)

−0.035 (5)

−0.046 (8)

−0.029 (7)

0.026 (10)

0.020 (12)

0.004 (3)

−0.033 (4)

0.010 (3)

−0.010 (4)

0.010 (4)

0.081 (6)

0.049 (7)

−0.057 (6)

0.021 (8)

0.009 (5)

−0.005 (3)

0.017 (4)

−0.007 (4)

−0.002 (3)

−0.014 (3)

−0.016 (4)

0.010 (5)

−0.019 (5)

−0.004 (9)

−0.005 (9)

0.001 (3)

−0.016 (4)

−0.014 (3)

−0.034 (4)

0.006 (4)

−0.155 (7)

−0.060 (8)

−0.010 (6)

−0.074 (7)

−0.038 (6)

Geometric parameters (Å, º)

Sc1—C1

Sc1—C2

Sc1—C3

Sc1—C4

Sc1—C15

Sc1—C16

Sc1—C27

Sc1—C28

Sc1—C29

Sc1—C30

Sc1—C41

Sc1—C42

Sc1—H4

C1—C3

C3—C4

C4—C5

C5—C6

C6—C7

C7—C8

C3—C8

2.351 (4)

Na1—O8

2.355 (3)

2.357 (4)

2.577 (4)

2.518 (4)

2.559 (4)

2.536 (4)

2.354 (4)

2.380 (4)

2.590 (4)

2.563 (4)

2.562 (4)

2.560 (4)

2.38 (4)

1.434 (5)

1.418 (6)

1.393 (5)

1.370 (6)

1.387 (6)

1.369 (6)

1.432 (5)

Na1—O7

Na1—O4

Na1—O3

Na1—O5

Na1—O6

Na1—O1

Na1—O2

O1—C64

O1—C53

O2—C55

O2—C54

O3—C57

O3—C56

O4—C58

O4—C59

O5—C61

O5—C60

O6—C63

O6—C62

2.394 (3)

2.663 (3)

2.685 (3)

2.751 (3)

2.770 (3)

2.801 (3)

2.860 (3)

1.404 (5)

1.416 (5)

1.411 (5)

1.415 (5)

1.418 (5)

1.431 (5)

1.414 (5)

1.420 (5)

1.423 (5)

1.412 (5)

1.424 (5)

Acta Cryst. (2018). C74, 769-781

sup-8

supporting information

C1—C9

C1—C2

1.482 (6)

1.501 (5)

1.442 (5)

1.425 (6)

1.385 (6)

1.357 (6)

1.397 (6)

1.353 (5)

1.431 (5)

1.486 (5)

1.451 (5)

1.426 (5)

1.391 (6)

1.362 (6)

1.393 (6)

1.370 (6)

1.424 (5)

1.488 (5)

1.503 (5)

1.444 (5)

1.434 (5)

1.388 (5)

1.365 (6)

1.400 (6)

1.360 (5)

1.428 (5)

1.487 (5)

0.93 (4)

0.9500

O7—C68

O7—C65

O8—C72B

O8—C72A

O8—C69

1.399 (6)

1.415 (6)

1.35 (2)

1.397 (10)

1.422 (6)

1.496 (6)

0.9900

1.485 (6)

0.9900

1.487 (6)

0.9900

1.479 (6)

0.9900

1.484 (6)

0.9900

1.491 (6)

0.9900

1.504 (7)

0.9900

1.462 (8)

0.9900

1.494 (8)

0.9900

C2—C15

C15—C16

C16—C17

C17—C18

C18—C19

C19—C20

C15—C20

C2—C21

C27—C29

C29—C30

C30—C31

C31—C32

C32—C33

C33—C34

C29—C34

C27—C35

C27—C28

C28—C41

C41—C42

C42—C43

C43—C44

C44—C45

C45—C46

C41—C46

C28—C47

C4—H4

C53—C54

C53—H53A

C53—H53B

C54—H54A

C54—H54B

C55—C56

C55—H55A

C55—H55B

C56—H56A

C56—H56B

C57—C58

C57—H57A

C57—H57B

C58—H58A

C58—H58B

C59—C60

C59—H59A

C59—H59B

C60—H60A

C60—H60B

C61—C62

C61—H61A

C61—H61B

C62—H62A

C62—H62B

C63—C64

C63—H63A

C63—H63B

C64—H64A

C64—H64B

C65—C66

C65—H65A

C65—H65B

C66—C67

C66—H66A

C66—H66B

C67—C68

C5—H5

C6—H6

C7—H7

C8—H8

0.9500

C9—C10

C9—C14

C10—C11

C10—H10

C11—C12

C11—H11

C12—C13

C12—H12

C13—C14

C13—H13

C14—H14

C16—H16

C17—H17

C18—H18

C19—H19

C20—H20

1.406 (6)

1.409 (5)

1.393 (6)

0.9500

1.372 (6)

0.9500

1.370 (7)

0.9500

1.382 (6)

0.9500

0.89 (4)

0.9500

C67—H67A

C67—H67B

C68—H68A

C68—H68B

C69—C70

0.9900

1.488 (7)

0.9900

0.9500

C69—H69A

Acta Cryst. (2018). C74, 769-781

sup-9

supporting information

C21—C22

C21—C26

C22—C23

C22—H22

C23—C24

C23—H23

C24—C25

C24—H24

C25—C26

C25—H25

C26—H26

C30—H30

C31—H31

C32—H32

C33—H33

C34—H34

C35—C40

C35—C36

C36—C37

C36—H36

C37—C38

C37—H37

C38—C39

C38—H38

C39—C40

C39—H39

C40—H40

C42—H42

C43—H43

C44—H44

C45—H45

C46—H46

C47—C52

C47—C48

C48—C49

C48—H48A

C49—C50

C49—H49A

C50—C51

C50—H50A

C51—C52

C51—H51A

C52—H52A

1.401 (6)

1.407 (6)

1.389 (6)

0.9500

1.382 (7)

0.9500

1.372 (7)

0.9500

1.391 (6)

0.9500

0.97 (4)

0.9500

C69—H69B

C70—C71A

C70—C71B

C70—H70A

C70—H70B

C70—H70C

C70—H70D

C71A—C72A

C71A—H71A

C71A—H71B

C72A—H72A

C72A—H72B

C71B—C72B

C71B—H71C

C71B—H71D

C72B—H72C

C72B—H72D

O9—C76

0.9900

1.469 (11)

1.473 (3)

0.9900

1.485 (12)

0.9900

1.478 (3)

0.9900

0.9500

1.401 (5)

1.407 (5)

1.379 (6)

0.9500

1.377 (6)

0.9500

1.390 (6)

0.9500

1.379 (5)

0.9500

0.95 (4)

0.9500

0.9900

1.414 (7)

1.461 (7)

1.440 (7)

0.9900

1.484 (7)

0.9900

1.501 (8)

0.9900

O9—C73

C73—C74

C73—H73A

C73—H73B

C74—C75

C74—H74A

C74—H74B

C75—C76

C75—H75A

C75—H75B

C76—H76A

C76—H76B

O10—C80

0.9900

1.397 (8)

1.408 (10)

1.475 (3)

0.9900

1.491 (10)

0.9900

1.473 (3)

0.9900

0.9500

O10—C77

C77—C78

1.395 (5)

1.388 (5)

0.9500

1.369 (6)

0.9500

1.385 (6)

0.9500

1.397 (5)

0.9500

C77—H77A

C77—H77B

C78—C79

C78—H78A

C78—H78B

C79—C80

C79—H79A

C79—H79B

C80—H80A

C80—H80B

0.9500

0.9900

C1—Sc1—C27

C1—Sc1—C2

C27—Sc1—C2

C1—Sc1—C28

152.76 (14)

37.20 (13)

154.47 (13)

154.60 (13)

C49—C48—H48A

C47—C48—H48A

C50—C49—C48

C50—C49—H49A

119.3

121.5 (4)

119.2

Acta Cryst. (2018). C74, 769-781

sup-10

supporting information

C27—Sc1—C28

C2—Sc1—C28

C1—Sc1—C4

C27—Sc1—C4

C2—Sc1—C4

37.02 (12)

154.15 (14)

61.16 (13)

132.87 (13)

71.13 (13)

97.91 (13)

71.33 (13)

96.97 (13)

61.19 (13)

132.00 (13)

129.81 (13)

60.94 (13)

120.87 (13)

33.81 (12)

143.51 (13)

104.60 (13)

32.49 (12)

133.49 (13)

71.57 (13)

97.59 (13)

60.86 (13)

101.65 (14)

99.28 (14)

86.41 (13)

144.86 (13)

61.27 (13)

120.73 (13)

33.73 (12)

87.68 (13)

129.24 (13)

118.44 (12)

32.50 (12)

97.59 (13)

60.60 (13)

133.92 (14)

69.38 (13)

97.36 (14)

104.20 (14)

133.68 (13)

128.47 (13)

102.50 (13)

33.44 (12)

143.97 (13)

60.15 (13)

121.63 (13)

32.30 (13)

104.56 (13)

91.35 (12)

C48—C49—H49A

C49—C50—C51

C49—C50—H50A

C51—C50—H50A

C50—C51—C52

C50—C51—H51A

C52—C51—H51A

C47—C52—C51

C47—C52—H52A

C51—C52—H52A

O8—Na1—O7

O8—Na1—O4

O7—Na1—O4

O8—Na1—O3

O7—Na1—O3

O4—Na1—O3

O8—Na1—O5

O7—Na1—O5

O4—Na1—O5

O3—Na1—O5

O8—Na1—O6

O7—Na1—O6

O4—Na1—O6

O3—Na1—O6

O5—Na1—O6

O8—Na1—O1

O7—Na1—O1

O4—Na1—O1

O3—Na1—O1

O5—Na1—O1

O6—Na1—O1

O8—Na1—O2

O7—Na1—O2

O4—Na1—O2

O3—Na1—O2

O5—Na1—O2

O6—Na1—O2

O1—Na1—O2

C64—O1—C53

C64—O1—Na1

C53—O1—Na1

C55—O2—C54

C55—O2—Na1

C54—O2—Na1

C57—O3—C56

C57—O3—Na1

C56—O3—Na1

C58—O4—C59

119.2

118.3 (4)

120.9

120.6 (4)

119.7

121.6 (4)

119.2

C28—Sc1—C4

C1—Sc1—C16

C27—Sc1—C16

C2—Sc1—C16

C28—Sc1—C16

C4—Sc1—C16

C1—Sc1—C15

C27—Sc1—C15

C2—Sc1—C15

C28—Sc1—C15

C4—Sc1—C15

C16—Sc1—C15

C1—Sc1—C42

C27—Sc1—C42

C2—Sc1—C42

C28—Sc1—C42

C4—Sc1—C42

C16—Sc1—C42

C15—Sc1—C42

C1—Sc1—C41

C27—Sc1—C41

C2—Sc1—C41

C28—Sc1—C41

C4—Sc1—C41

C16—Sc1—C41

C15—Sc1—C41

C42—Sc1—C41

C1—Sc1—C30

C27—Sc1—C30

C2—Sc1—C30

C28—Sc1—C30

C4—Sc1—C30

C16—Sc1—C30

C15—Sc1—C30

C42—Sc1—C30

C41—Sc1—C30

C1—Sc1—C3

119.2

174.52 (14)

89.11 (12)

94.23 (11)

90.22 (11)

87.50 (11)

62.31 (10)

97.47 (11)

87.95 (11)

61.66 (10)

123.20 (11)

87.50 (11)

94.54 (12)

120.31 (11)

176.47 (11)

59.83 (9)

91.72 (11)

84.92 (10)

179.14 (11)

117.47 (10)

118.41 (10)

59.95 (9)

81.84 (11)

92.70 (11)

121.62 (11)

60.20 (9)

176.57 (11)

116.75 (10)

58.33 (9)

111.0 (3)

116.2 (2)

118.8 (2)

111.5 (3)

112.0 (2)

116.1 (2)

111.8 (3)

113.8 (2)

119.4 (2)

112.8 (3)

C27—Sc1—C3

C2—Sc1—C3

C28—Sc1—C3

C4—Sc1—C3

C16—Sc1—C3

C15—Sc1—C3

Acta Cryst. (2018). C74, 769-781

sup-11

supporting information

C42—Sc1—C3

C41—Sc1—C3

C30—Sc1—C3

C1—Sc1—C29

C27—Sc1—C29

C2—Sc1—C29

C28—Sc1—C29

C4—Sc1—C29

C16—Sc1—C29

C15—Sc1—C29

C42—Sc1—C29

C41—Sc1—C29

C30—Sc1—C29

C3—Sc1—C29

C1—Sc1—H4

C27—Sc1—H4

C2—Sc1—H4

C28—Sc1—H4

C4—Sc1—H4

C16—Sc1—H4

C15—Sc1—H4

C42—Sc1—H4

C41—Sc1—H4

C30—Sc1—H4

C3—Sc1—H4

C29—Sc1—H4

C3—C1—C9

130.93 (13)

119.69 (13)

86.00 (13)

119.66 (13)

33.70 (12)

145.17 (13)

59.91 (12)

127.51 (13)

88.99 (13)

121.22 (12)

105.15 (13)

91.50 (12)

32.12 (12)

117.37 (13)

69.3 (9)

133.5 (9)

64.4 (9)

96.7 (9)

21.6 (9)

125.3 (9)

94.2 (9)

82.2 (9)

75.9 (9)

117.3 (10)

49.0 (9)

143.9 (9)

123.3 (4)

115.3 (3)

118.2 (3)

82.0 (2)

131.8 (3)

71.6 (2)

122.9 (3)

115.9 (3)

117.8 (3)

80.8 (2)

134.2 (3)

71.2 (2)

114.5 (4)

120.8 (4)

124.6 (4)

71.6 (2)

137.2 (3)

64.6 (2)

122.4 (4)

131.7 (3)

76.1 (2)

C58—O4—Na1

C59—O4—Na1

C61—O5—C60

C61—O5—Na1

C60—O5—Na1

C63—O6—C62

C63—O6—Na1

C62—O6—Na1

C68—O7—C65

C68—O7—Na1

C65—O7—Na1

C72B—O8—C69

C72A—O8—C69

C72B—O8—Na1

C72A—O8—Na1

C69—O8—Na1

116.7 (2)

115.3 (3)

112.1 (3)

115.0 (2)

114.3 (3)

111.5 (3)

115.2 (3)

117.6 (2)

106.2 (4)

126.1 (3)

125.4 (3)

104.0 (8)

107.6 (5)

117.9 (8)

125.0 (4)

127.3 (3)

108.8 (3)

109.9

108.3

108.4 (3)

110.0

108.4

109.3 (3)

109.8

108.3

108.7 (3)

109.9

108.3

109.3 (4)

109.8

108.3

O1—C53—C54

O1—C53—H53A

C54—C53—H53A

O1—C53—H53B

C54—C53—H53B

H53A—C53—H53B

O2—C54—C53

O2—C54—H54A

C53—C54—H54A

O2—C54—H54B

C53—C54—H54B

H54A—C54—H54B

O2—C55—C56

O2—C55—H55A

C56—C55—H55A

O2—C55—H55B

C56—C55—H55B

H55A—C55—H55B

O3—C56—C55

O3—C56—H56A

C55—C56—H56A

O3—C56—H56B

C55—C56—H56B

H56A—C56—H56B

O3—C57—C58

C3—C1—C2

C9—C1—C2

C3—C1—Sc1

C9—C1—Sc1

C2—C1—Sc1

C15—C2—C21

C15—C2—C1

C21—C2—C1

C15—C2—Sc1

C21—C2—Sc1

C1—C2—Sc1

C4—C3—C8

C4—C3—C1

C8—C3—C1

C4—C3—Sc1

C8—C3—Sc1

C1—C3—Sc1

C5—C4—C3

C5—C4—Sc1

C3—C4—Sc1

C5—C4—H4

O3—C57—H57A

C58—C57—H57A

O3—C57—H57B

C58—C57—H57B

H57A—C57—H57B

O4—C58—C57

108.7 (4)

110.0

115 (2)

O4—C58—H58A

Acta Cryst. (2018). C74, 769-781

sup-12

supporting information

C3—C4—H4

Sc1—C4—H4

C6—C5—C4

C6—C5—H5

C4—C5—H5

C5—C6—C7

C5—C6—H6

C7—C6—H6

C8—C7—C6

C8—C7—H7

C6—C7—H7

C7—C8—C3

C7—C8—H8

122 (2)

71 (2)

121.1 (4)

119.5

118.1 (4)

120.9

122.1 (4)

118.9

121.7 (4)

119.1

C57—C58—H58A

O4—C58—H58B

C57—C58—H58B

H58A—C58—H58B

O4—C59—C60

O4—C59—H59A

C60—C59—H59A

O4—C59—H59B

C60—C59—H59B

H59A—C59—H59B

O5—C60—C59

O5—C60—H60A

C59—C60—H60A

O5—C60—H60B

C59—C60—H60B

H60A—C60—H60B

O5—C61—C62

O5—C61—H61A

C62—C61—H61A

O5—C61—H61B

C62—C61—H61B

H61A—C61—H61B

O6—C62—C61

O6—C62—H62A

C61—C62—H62A

O6—C62—H62B

C61—C62—H62B

H62A—C62—H62B

O6—C63—C64

O6—C63—H63A

C64—C63—H63A

O6—C63—H63B

C64—C63—H63B

H63A—C63—H63B

O1—C64—C63

O1—C64—H64A

C63—C64—H64A

O1—C64—H64B

C63—C64—H64B

H64A—C64—H64B

O7—C65—C66

O7—C65—H65A

C66—C65—H65A

O7—C65—H65B

C66—C65—H65B

H65A—C65—H65B

C67—C66—C65

C67—C66—H66A

110.0

108.3

108.7 (4)

110.0

108.3

108.6 (4)

110.0

C3—C8—H8

119.1

C10—C9—C14

C10—C9—C1

C14—C9—C1

C11—C10—C9

C11—C10—H10

C9—C10—H10

C12—C11—C10

C12—C11—H11

C10—C11—H11

C13—C12—C11

C13—C12—H12

C11—C12—H12

C12—C13—C14

C12—C13—H13

C14—C13—H13

C13—C14—C9

C13—C14—H14

C9—C14—H14

C16—C15—C20

C16—C15—C2

C20—C15—C2

C16—C15—Sc1

C20—C15—Sc1

C2—C15—Sc1

C17—C16—C15

C17—C16—Sc1

C15—C16—Sc1

C17—C16—H16

C15—C16—H16

Sc1—C16—H16

C18—C17—C16

C18—C17—H17

C16—C17—H17

C17—C18—C19

115.6 (4)

124.3 (4)

120.0 (4)

121.8 (4)

119.1

120.6 (5)

119.7

119.1 (5)

120.5

121.1 (4)

119.5

110.0

108.3

108.4 (4)

110.0

108.4

108.1 (4)

110.1

108.4

109.1 (4)

109.9

108.3

109.5 (4)

109.8

108.2

107.5 (4)

110.2

119.5

121.8 (4)

119.1

113.8 (4)

120.9 (4)

125.1 (4)

72.9 (2)

133.7 (3)

65.4 (2)

122.3 (4)

130.7 (3)

74.6 (2)

116 (3)

121 (3)

77 (3)

110.2

108.5

104.2 (5)

110.9

121.3 (4)

119.3

118.4 (4)

Acta Cryst. (2018). C74, 769-781

sup-13

supporting information

C17—C18—H18

C19—C18—H18

C20—C19—C18

C20—C19—H19

C18—C19—H19

C19—C20—C15

C19—C20—H20

C15—C20—H20

C22—C21—C26

C22—C21—C2

C26—C21—C2

C23—C22—C21

C23—C22—H22

C21—C22—H22

C24—C23—C22

C24—C23—H23

C22—C23—H23

C25—C24—C23

C25—C24—H24

C23—C24—H24

C24—C25—C26

C24—C25—H25

C26—C25—H25

C25—C26—C21

C25—C26—H26

C21—C26—H26

C29—C27—C35

C29—C27—C28

C35—C27—C28

C29—C27—Sc1

C35—C27—Sc1

C28—C27—Sc1

C41—C28—C47

C41—C28—C27

C47—C28—C27

C41—C28—Sc1

C47—C28—Sc1

C27—C28—Sc1

C34—C29—C30

C34—C29—C27

C30—C29—C27

C34—C29—Sc1

C30—C29—Sc1

C27—C29—Sc1

C31—C30—C29

C31—C30—Sc1

C29—C30—Sc1

C31—C30—H30

120.8

121.4 (4)

119.3

122.6 (4)

118.7

115.9 (4)

124.6 (4)

119.5 (4)

121.5 (4)

119.2

121.0 (5)

119.5

119.0 (4)

120.5

120.3 (5)

119.9

122.2 (4)

118.9

C65—C66—H66A

C67—C66—H66B

C65—C66—H66B

H66A—C66—H66B

C66—C67—C68

C66—C67—H67A

C68—C67—H67A

C66—C67—H67B

C68—C67—H67B

H67A—C67—H67B

O7—C68—C67

O7—C68—H68A

C67—C68—H68A

O7—C68—H68B

C67—C68—H68B

H68A—C68—H68B

O8—C69—C70

O8—C69—H69A

C70—C69—H69A

O8—C69—H69B

C70—C69—H69B

H69A—C69—H69B

C71A—C70—C69

C71B—C70—C69

C71A—C70—H70A

C69—C70—H70A

C71A—C70—H70B

C69—C70—H70B

H70A—C70—H70B

C71B—C70—H70C

C69—C70—H70C

C71B—C70—H70D

C69—C70—H70D

H70C—C70—H70D

C70—C71A—C72A

C70—C71A—H71A

C72A—C71A—H71A

C70—C71A—H71B

C72A—C71A—H71B

H71A—C71A—H71B

O8—C72A—C71A

O8—C72A—H72A

C71A—C72A—H72A

O8—C72A—H72B

C71A—C72A—H72B

H72A—C72A—H72B

C70—C71B—C72B

C70—C71B—H71C

110.9

108.9

101.6 (5)

111.5

109.3

105.4 (5)

110.7

108.8

107.0 (5)

110.3

108.6

100.1 (5)

103.4 (8)

111.8

109.5

111.1

118.9

123.1 (3)

114.8 (3)

118.2 (3)

82.1 (2)

132.2 (2)

72.4 (2)

122.4 (3)

116.9 (3)

117.9 (3)

80.1 (2)

134.7 (3)

70.5 (2)

114.3 (4)

125.9 (4)

119.7 (3)

134.5 (3)

72.9 (2)

64.2 (2)

122.1 (4)

132.1 (3)

75.0 (2)

117 (2)

111.1

109.0

106.8 (7)

110.4

108.6

106.9 (7)

110.3

108.6

97.3 (11)

112.3

Acta Cryst. (2018). C74, 769-781

sup-14

supporting information

C29—C30—H30

Sc1—C30—H30

C32—C31—C30

C32—C31—H31

C30—C31—H31

C31—C32—C33

C31—C32—H32

C33—C32—H32

C34—C33—C32

C34—C33—H33

C32—C33—H33

C33—C34—C29

C33—C34—H34

C29—C34—H34

C40—C35—C36

C40—C35—C27

C36—C35—C27

C37—C36—C35

C37—C36—H36

C35—C36—H36

C38—C37—C36

C38—C37—H37

C36—C37—H37

C37—C38—C39

C37—C38—H38

C39—C38—H38

C40—C39—C38

C40—C39—H39

C38—C39—H39

C39—C40—C35

C39—C40—H40

C35—C40—H40

C46—C41—C42

C46—C41—C28

C42—C41—C28

C46—C41—Sc1

C42—C41—Sc1

C28—C41—Sc1

C43—C42—C41

C43—C42—Sc1

C41—C42—Sc1

C43—C42—H42

C41—C42—H42

Sc1—C42—H42

C44—C43—C42

C44—C43—H43

C42—C43—H43

C43—C44—C45

120 (2)

71 (2)

121.6 (4)

119.2

118.1 (4)

120.9

121.6 (4)

119.2

122.3 (4)

118.8

C72B—C71B—H71C

C70—C71B—H71D

112.3

109.9

114.7 (15)

108.6

107.6

107.0 (5)

107.9 (5)

110.1

108.4

103.8 (5)

111.0

109.0

104.5 (4)

110.9

108.9

107.9 (5)

110.1

C72B—C71B—H71D

H71C—C71B—H71D

O8—C72B—C71B

O8—C72B—H72C

C71B—C72B—H72C

O8—C72B—H72D

C71B—C72B—H72D

H72C—C72B—H72D

C76—O9—C73

C74—C73—O9

C74—C73—H73A

O9—C73—H73A

C74—C73—H73B

O9—C73—H73B

H73A—C73—H73B

C73—C74—C75

C73—C74—H74A

C75—C74—H74A

C73—C74—H74B

C75—C74—H74B

H74A—C74—H74B

C74—C75—C76

C74—C75—H75A

C76—C75—H75A

C74—C75—H75B

C76—C75—H75B

H75A—C75—H75B

O9—C76—C75

O9—C76—H76A

C75—C76—H76A

O9—C76—H76B

C75—C76—H76B

H76A—C76—H76B

C80—O10—C77

118.8

115.4 (4)

120.0 (3)

124.6 (4)

122.1 (4)

118.9

121.4 (4)

119.3

117.8 (4)

121.1

121.1 (4)

119.5

122.2 (4)

118.9

114.6 (3)

124.2 (3)

121.2 (4)

131.8 (3)

73.7 (2)

66.2 (2)

121.3 (4)

129.1 (3)

73.8 (2)

119 (2)

120 (2)

72 (2)

108.4

115.2 (6)

103.3 (7)

111.1

109.1

104.8 (7)

110.8

O10—C77—C78

O10—C77—H77A

C78—C77—H77A

O10—C77—H77B

C78—C77—H77B

H77A—C77—H77B

C77—C78—C79

C77—C78—H78A

C79—C78—H78A

C77—C78—H78B

C79—C78—H78B

H78A—C78—H78B

122.0 (4)

119.0

110.8

108.9

118.1 (4)

Acta Cryst. (2018). C74, 769-781

sup-15

supporting information

C43—C44—H44

C45—C44—H44

C46—C45—C44

C46—C45—H45

C44—C45—H45

C45—C46—C41

C45—C46—H46

C41—C46—H46

C52—C47—C48

C52—C47—C28

C48—C47—C28

C49—C48—C47

121.0

121.4 (4)

119.3

122.5 (4)

118.7

116.5 (4)

119.0 (3)

124.5 (3)

121.5 (4)

C80—C79—C78

105.8 (7)

110.6

108.7

103.6 (7)

111.0

C80—C79—H79A

C78—C79—H79A

C80—C79—H79B

C78—C79—H79B

H79A—C79—H79B

O10—C80—C79

O10—C80—H80A

C79—C80—H80A

O10—C80—H80B

C79—C80—H80B

H80A—C80—H80B

111.0

109.0

C3—C1—C2—C15

C9—C1—C2—C15

Sc1—C1—C2—C15

C3—C1—C2—C21

C9—C1—C2—C21

Sc1—C1—C2—C21

C3—C1—C2—Sc1

C9—C1—C2—Sc1

C9—C1—C3—C4

C2—C1—C3—C4

Sc1—C1—C3—C4

C9—C1—C3—C8

C2—C1—C3—C8

Sc1—C1—C3—C8

C9—C1—C3—Sc1

C2—C1—C3—Sc1

C8—C3—C4—C5

C1—C3—C4—C5

Sc1—C3—C4—C5

C8—C3—C4—Sc1

C1—C3—C4—Sc1

C3—C4—C5—C6

Sc1—C4—C5—C6

C4—C5—C6—C7

C5—C6—C7—C8

C6—C7—C8—C3

C4—C3—C8—C7

C1—C3—C8—C7

Sc1—C3—C8—C7

C3—C1—C9—C10

C2—C1—C9—C10

Sc1—C1—C9—C10

C3—C1—C9—C14

C2—C1—C9—C14

Sc1—C1—C9—C14

−140.6 (4)

58.9 (5)

−69.3 (3)

59.3 (5)

C28—C27—C35—C40

Sc1—C27—C35—C40

C29—C27—C35—C36

C28—C27—C35—C36

Sc1—C27—C35—C36

C40—C35—C36—C37

C27—C35—C36—C37

C35—C36—C37—C38

C36—C37—C38—C39

C37—C38—C39—C40

C38—C39—C40—C35

C36—C35—C40—C39

C27—C35—C40—C39

C47—C28—C41—C46

C27—C28—C41—C46

Sc1—C28—C41—C46

C47—C28—C41—C42

C27—C28—C41—C42

Sc1—C28—C41—C42

C47—C28—C41—Sc1

C27—C28—C41—Sc1

C46—C41—C42—C43

C28—C41—C42—C43

Sc1—C41—C42—C43

C46—C41—C42—Sc1

C28—C41—C42—Sc1

C41—C42—C43—C44

Sc1—C42—C43—C44

C42—C43—C44—C45

C43—C44—C45—C46

C44—C45—C46—C41

C42—C41—C46—C45

C28—C41—C46—C45

Sc1—C41—C46—C45

C41—C28—C47—C52

−19.1 (5)

−110.5 (4)

−43.5 (5)

159.7 (4)

68.3 (5)

−2.2 (6)

179.0 (4)

0.8 (6)

−101.1 (4)

130.7 (3)

−71.4 (3)

128.2 (3)

178.3 (4)

19.0 (5)

−46.2 (3)

−4.2 (6)

−163.5 (4)

131.2 (4)

−135.4 (4)

65.3 (3)

−3.3 (5)

174.4 (4)

130.9 (4)

−134.3 (3)

43.4 (3)

0.7 (6)

−0.7 (6)

−0.8 (6)

2.1 (6)

−179.0 (4)

11.7 (6)

172.3 (3)

−125.6 (4)

−171.5 (4)

−10.9 (5)

51.2 (3)

137.3 (4)

−62.1 (3)

2.8 (6)

−174.3 (4)

−126.3 (4)

129.1 (3)

−48.0 (3)

−1.1 (6)

−95.4 (5)

−0.6 (7)

0.5 (7)

1.2 (6)

101.9 (5)

1.9 (6)

−2.8 (6)

0.5 (6)

2.5 (6)

−175.1 (4)

−86.4 (5)

48.5 (6)

−152.8 (4)

−62.8 (5)

−134.3 (4)

24.5 (5)

1.4 (6)

−2.9 (6)

174.0 (4)

86.7 (5)

130.7 (4)

114.5 (4)

Acta Cryst. (2018). C74, 769-781

sup-16

supporting information

C14—C9—C10—C11

C1—C9—C10—C11

C9—C10—C11—C12

C10—C11—C12—C13

C11—C12—C13—C14

C12—C13—C14—C9

C10—C9—C14—C13

C1—C9—C14—C13

C21—C2—C15—C16

C1—C2—C15—C16

Sc1—C2—C15—C16

C21—C2—C15—C20

C1—C2—C15—C20

Sc1—C2—C15—C20

C21—C2—C15—Sc1

C1—C2—C15—Sc1

C20—C15—C16—C17

C2—C15—C16—C17

Sc1—C15—C16—C17

C20—C15—C16—Sc1

C2—C15—C16—Sc1

C15—C16—C17—C18

Sc1—C16—C17—C18

C16—C17—C18—C19

C17—C18—C19—C20

C18—C19—C20—C15

C16—C15—C20—C19

C2—C15—C20—C19

Sc1—C15—C20—C19

C15—C2—C21—C22

C1—C2—C21—C22

Sc1—C2—C21—C22

C15—C2—C21—C26

C1—C2—C21—C26

Sc1—C2—C21—C26

C26—C21—C22—C23

C2—C21—C22—C23

C21—C22—C23—C24

C22—C23—C24—C25

C23—C24—C25—C26

C24—C25—C26—C21

C22—C21—C26—C25

C2—C21—C26—C25

C29—C27—C28—C41

C35—C27—C28—C41

Sc1—C27—C28—C41

C29—C27—C28—C47

C35—C27—C28—C47

0.9 (6)

C27—C28—C47—C52

−29.7 (5)

−119.4 (4)

−51.3 (6)

148.3 (4)

58.6 (5)

−3.6 (6)

178.3 (4)

1.1 (6)

1.2 (6)

−0.8 (6)

4.0 (6)

−177.8 (4)

−1.9 (6)

−175.4 (4)

45.9 (4)

178.5 (4)

48.6 (4)

−61.2 (5)

178.2 (4)

−49.8 (4)

178.5 (3)

−45.0 (4)

62.7 (4)

−171.6 (4)

49.4 (4)

−179.9 (4)

43.2 (4)

−61.1 (5)

170.2 (4)

−52.3 (4)

−176.9 (4)

−43.8 (4)

63.4 (5)

−173.5 (3)

53.7 (4)

178.0 (4)

41.8 (4)

−62.1 (4)

171.9 (4)

−50.8 (5)

176.7 (4)

−43.5 (5)

62.4 (5)

15.3 (6)

−148.6 (4)

9.5 (7)

−28.6 (7)

−34.1 (6)

178.3 (4)

−0.1 (7)

0.5 (7)

−1.8 (7)

2.8 (7)

Sc1—C28—C47—C52

C41—C28—C47—C48

C27—C28—C47—C48

Sc1—C28—C47—C48

C52—C47—C48—C49

C28—C47—C48—C49

C47—C48—C49—C50

C48—C49—C50—C51

C49—C50—C51—C52

C48—C47—C52—C51

C28—C47—C52—C51

C50—C51—C52—C47

C64—O1—C53—C54

Na1—O1—C53—C54

C55—O2—C54—C53

Na1—O2—C54—C53

O1—C53—C54—O2

C54—O2—C55—C56

Na1—O2—C55—C56

C57—O3—C56—C55

Na1—O3—C56—C55

O2—C55—C56—O3

C56—O3—C57—C58

Na1—O3—C57—C58

C59—O4—C58—C57

Na1—O4—C58—C57

O3—C57—C58—O4

C58—O4—C59—C60

Na1—O4—C59—C60

C61—O5—C60—C59

Na1—O5—C60—C59

O4—C59—C60—O5

C60—O5—C61—C62

Na1—O5—C61—C62

C63—O6—C62—C61

Na1—O6—C62—C61

O5—C61—C62—O6

C62—O6—C63—C64

Na1—O6—C63—C64

C53—O1—C64—C63

Na1—O1—C64—C63

O6—C63—C64—O1

C68—O7—C65—C66

Na1—O7—C65—C66

O7—C65—C66—C67

C65—C66—C67—C68

C65—O7—C68—C67

−2.3 (6)

−179.8 (4)

173.3 (4)

14.4 (5)

−49.3 (3)

−10.0 (6)

−168.9 (4)

127.4 (4)

−137.4 (4)

63.7 (3)

−2.1 (6)

175.0 (4)

128.8 (4)

−130.9 (3)

46.2 (3)

−0.4 (6)

97.1 (5)

2.8 (6)

−2.6 (7)

0.0 (7)

2.3 (6)

−174.7 (4)

−86.4 (5)

49.3 (6)

−152.1 (4)

−61.9 (5)

−132.9 (4)

25.6 (5)

115.9 (4)

3.9 (6)

−178.2 (4)

−0.5 (7)

−2.8 (7)

2.5 (7)

1.2 (7)

−4.3 (6)

177.8 (4)

139.7 (3)

−61.6 (5)

67.4 (3)

−58.8 (5)

99.9 (4)

Acta Cryst. (2018). C74, 769-781

sup-17

Article Doi

Scandium complexes with the tetraphenylethylene and anthracene dianions

DOI: 10.1107/S2053229618007295

Source and publish data:

Authors:

Article abstract of DOI:10.1107/S2053229618007295

Full text of DOI:10.1107/S2053229618007295

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