Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-opening polymerization of ?-caprolactone with initiators of different natures

research papers

Phenoxide and alkoxide complexes of Mg, Al and

Zn, and their use for the ring-opening polymerization

of "-caprolactone with initiators of different natures

ISSN 2053-2296

Mikhail E. Minyaev,^a* Ilya E. Nifant’ev,^a,bAndrey V. Shlyakhtin,^a,bPavel V.

Ivchenko^a,band Konstantin A. Lyssenko^c

Received 14 February 2018

Accepted 29 March 2018

^aA.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky prospect, Moscow

119991, Russian Federation, ^bChemistry Department, M.V. Lomonosov Moscow State University, 1 Leninskie Gory Str.,

Building 3, Moscow 119991, Russian Federation, and ^cA.N. Nesmeyanov Institute of Organoelement Compounds,

Russian Academy of Sciences, 28 Vavilova Str., Moscow 119991, Russian Federation. *Correspondence e-mail:

mminyaev@mail.ru

Edited by V. Langer, Chalmers University of

Technology, Sweden

Keywords: magnesium; aluminium; zinc;

butylated hydroxytoluene; coordination

compounds; packing polymorphism; ring-

opening polymerization; "-caprolactone; crystal

structure; NMR.

A new packing polymorph of bis(2,6-di-tert-butyl-4-methylphenolato-ꢀO)bis-

(tetrahydrofuran-ꢀO)magnesium, [Mg(C₁₅H₂₃O)₂(C₄H₈O)₂] or Mg(BHT)₂(THF)₂,

(BHT is the 2,6-di-tert-butyl-4-methylphenoxide anion and THF is tetrahydro-

furan), (1), has the same space group (P2₁) as the previously reported

modiﬁcation [Nifant’ev et al. (2017d). Dalton Trans. 46, 12132–12146], but

contains three crystallographically independent molecules instead of one. The

structure of (1) exhibits rotational disorder of the tert-butyl groups and

positional disorder of a THF ligand. The complex of bis(2,6-di-tert-butyl-4-

methylphenolato-ꢀO)bis(ꢁ₂-ethyl glycolato-ꢀ²O,O⁰:ꢀO)dimethyldialuminium,

[Al₂(CH₃)₂(C₄H₇O₃)₂(C₁₅H₂₃O)₂] or [(BHT)AlMe(OCH₂COOEt)]₂, (2), is a

dimer located on an inversion centre and has an Al₂O₂rhomboid core. The

2-ethoxy-2-oxoethanolate ligand (OCH₂COOEt) displays a ꢁ₂-ꢀ²O,O⁰:ꢀO semi-

bridging coordination mode, forming a ﬁve-membered heteronuclear Al–O–C–

C–O ring. The same ligand exhibits positional disorder of the terminal methyl

group. The redetermined structure of the heptanuclear complex octakis(ꢁ₃-

benzyloxo-ꢀO:ꢀO:ꢀO)hexaethylheptazinc, [Zn₇(C₂H₅)₆(C₇H₇O)₈] or [Zn₇-

(OCH₂Ph)₈Et₆], (3), possesses a bicubic Zn₇O₈core located at an inversion

centre and demonstrates positional disorder of one crystallographically

independent phenyl group. Cambridge Structural Database surveys are given

for complexes structurally analogous to (2) and (3). Complexes (2) and (3), as

well as derivatives of (1), are of interest as catalysts for the ring-opening

polymerization of "-caprolactone, and polymerization results are reported.

CCDC references: 1833490; 1833489;

1833488

Supporting information: this article has

supporting information at journals.iucr.org/c

1. Introduction

Aryloxide complexes of nontoxic metals are among prospec-

tive catalysts in the ring-opening polymerization (ROP) of

cyclic esters (Dubois et al., 2009; Devaine-Pressing et al., 2015;

Klitzke et al., 2014; Li, Chen et al., 2012; Sarazin & Carpentier,

2015; Sun et al., 2014; Wheaton et al., 2009; Zhang et al., 2014)

for obtaining various polymers and polymeric materials,

including biodegradable ones. Therefore, the number of

aryloxide complexes of main group and transition metals has

increased dramatically in recent years. ortho-Disubstituted

bulky phenols, including 2,6-di-tert-butyl-4-methylphenol

(butylated hydroxytoluene or BHT-H), have been used

successfully to synthesize highly active catalysts for the ROP

of rac-lactide, "-caprolactone and !-pentadecalactone (see

Chen et al., 2012; Fang et al., 2012; Ivchenko et al., 2017;

Nifant’ev et al., 2016, 2017a,b,d; Wilson et al., 2014, 2015, and

references therein) or cyclic phosphoesters (Nifant’ev et al.,

2017c, 2018). We report herein the synthesis and structures of

# 2018 International Union of Crystallography

548 https://doi.org/10.1107/S2053229618005090

Acta Cryst. (2018). C74, 548–557

research papers

Mg, Al and Zn complexes (Scheme 1) and present results on

the ROP of "-caprolactone ("-CL) associated with these

complexes.

OCH₂COOEt, O(CH₂)₃CON(CH₃)₂and O-C₆H₄-4-^tBu; see

Nifant’ev et al., 2016, 2017d]. While using any of these

complexes as a catalyst, polymerization of "-caprolactone

("-CL) leads to the formation of poly-"-caprolactone (PCL)

with a terminal OR group. However, analogous reactions

involving either Mg(BHT)₂(THF)₂or Mg(BHT)(n-Bu)-

(THF)₂and other alcohols, including secondary, tertiary or

sterically crowded ones, usually provides insoluble or poorly

THF-soluble suspensions in equilibrium with soluble species

and not precipitating from solution after days or weeks.

Obtained by centrifugation, the precipitates contained less of

the BHT ligand than expected. It should be noted that isolated

samples of complexes ‘Mg_x(BHT)_y(OR)_2x–y(THF)_z’ (OR =

t

ⁱPrO, BuO or BuCH₂O) underwent slow metathesis in

toluene, providing, upon crystallization from toluene/hexane

1

mixtures, Mg(BHT)₂(THF)₂(based on H NMR data), for

which the unit-cell dimensions were analogous to those found

previously for Mg(BHT)₂(THF)₂(Nifant’ev et al., 2017d).

Nevertheless, polymerization of "-CL with Mg(BHT)₂(THF)₂

t

activated by 1 molar equivalent of alcohol (ⁱPrOH, BuOH,

^tBuCH₂OH and cholesterol) in THF leads to PCL containing a

corresponding OR terminal group [see Fig. 1 (bottom) and the

¹H NMR spectra in Figs. S2–S5 in the supporting information].

The latter allowed us to think that we were dealing with

polynuclear alkoxide complexes containing terminal BHT

groups as a result of aggregation (Nifant’ev et al., 2017d).

Indeed, the tetranuclear complex [Mg₄(BHT)₂(OCH₂CH₂-

NH₂)₆], which was obtained from the reactions of

Mg(BHT)₂(THF)₂with HOCH₂CH₂NH₂in 4:6 and even 1:1

molar ratios (Minyaev et al., 2017), can be regarded as such an

example.

Mg(BHT)₂(THF)₂itself (THF is tetrahydrofuran) is cata-

lytically inactive but displays high catalytic activity in the

polymerization of cyclic esters when activated by alcohols (e.g.

Chen et al., 2012), whereas the [Mg(BHT)(OR)(THF)_n]₂

complexes (n = 0 or 1) do not require an initiator for the ROP

process to occur (Nifant’ev et al., 2016, 2017d). The reaction of

either Mg(BHT)₂(THF)₂or Mg(BHT)(n-Bu)(THF)₂with 1

molar equivalent of a primary alcohol allowed us to prepare

dimeric complexes possessing deﬁnite compositions and

established crystal structures [Fig. 1, top; OR = OEt, OCH₂Ph,

However, some Mg–BHT complexes bearing secondary

alkoxide anions and being soluble in THF can presumably be

synthesized. A cyclohexyl-protected furanose form of glucose

was used to produce its soluble Mg–BHT derivative (Fig. 2,

1

middle; the structure of the intermediate is based on its H

NMR spectrum). Due to its high solubility in THF or toluene,

we were not able to obtain pure crystalline samples of the

complex. An attempt to crystallize it from a toluene/hexane

mixture resulted in a slow metathesis reaction providing

crystals of another polymorphic modiﬁcation of Mg(BHT)₂-

Figure 1

The synthesis of various Mg–BHT complexes containing alkoxide anions and the catalytic polymerization of "-caprolactone.

ꢀ

Acta Cryst. (2018). C74, 548–557

Minyaev et al.

Ring-opening polymerization of "-caprolactone 549

research papers

Figure 2

The synthesis of an Mg–BHT derivative of a cyclohexyl-protected furanose and polymerization of "-caprolactone.

(THF)₂, (1) (based on ¹H NMR and X-ray studies), for which

the unit-cell dimensions differed from those reported

previously for Mg(BHT)₂(THF)₂(Nifant’ev et al., 2017d).

Another proof for the BHT–Mg–(protected glucose) forma-

tion is polymerization of "-CL by the complex, leading to

PCL with a corresponding terminal group (Fig. 2, right; see

absence of the BHT ligand. It should be noted that complex

(3) was obtained previously from ZnEt₂and benzyl alcohol (in

a 1:1 ratio) in THF (Fig. 3, bottom right) and has been studied

crystallographically by Li, Nie et al. (2012).

1

2. Experimental

Fig. S6 in the supporting information for the H NMR spec-

trum).

All synthetic manipulations were performed under a puriﬁed

argon atmosphere using Schlenk glassware, dry-box techni-

ques and absolute solvents. "-Caprolactone was distilled from

CaH₂under reduced pressure in argon. Tetrahydrofuran was

predried over NaOH and distilled from potassium/benzo-

phenone ketyl. Hexane was distilled from Na/K alloy in the

presence of 18-crown-6 and benzophenone ketyl. Toluene was

distilled from sodium/benzophenone ketyl. Toluene-d₈and

We were able to crystallize two other complexes that might

exhibit ROP catalytic activity, which were then studied in the

polymerization of "-CL. The reaction of (BHT)₂AlMe with

ethyl glycolate (ethyl 2-hydroxyacetate) in toluene upon loss

of BHT-H leads to the formation of the binuclear complex

[(BHT)AlMe(OCH₂COOEt)]₂, (2), which was crystallized

from a toluene/hexane mixture (Fig. 3, top). An analogous

reaction of [(BHT)Zn(ꢁ₂-Et)]₂with benzyl alcohol produced

the heptanuclear complex [Zn₇(OCH₂Ph)₈Et₆], (3) (Fig. 3,

bottom left). We undertook an X-ray diffraction study of (3) in

order to conﬁrm its structure, since the ¹H NMR spectrum of

its toluene-d₈solution sample prepared from a single crystal

suggested the existence of two forms in solution and the

1

benzene-d₆were distilled from Na/K alloy. H NMR spectra

were recorded with Bruker AVANCE 400 and Bruker AM-

300 spectrometers in toluene-d₈, benzene-d₆(for the com-

plexes) and in CDCl₃(for the polymers). C/H elemental

analysis was performed with a PerkinElmer 2400 Series II

elemental analyzer. Gel-permeation chromatography (GPC)

Figure 3

Syntheses of [(BHT)AlMe(OCH₂COOEt)]₂, (2) (top), and of [Zn₇(OCH₂Ph)₈Et₆], (3) (bottom).

ꢀ

550 Minyaev et al.

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Acta Cryst. (2018). C74, 548–557

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Table 1

Experimental details.

All experiments were carried out at 120 K with Mo Kꢃ radiation using a Bruker SMART APEXII diffractometer. Absorption was corrected for by multi-scan

methods (SADABS; Bruker, 2008). H-atom parameters were constrained.

(1)

(2)

(3)

Crystal data

Chemical formula

M_r

Crystal system, space group

[Mg(C₁₅H₂₃O)₂(C₄H₈O)₂]

607.18

Monoclinic, P2₁

[Al₂(CH₃)₂(C₄H₇O₃)₂(C₁₅H₂₃O)₂]

728.88

Monoclinic, C2/c

27.7603 (18), 9.0454 (6),

18.4921 (13)

[Zn₇(C₂H₅)₆(C₇H₇O)₈]

1488.95

Orthorhombic, Pbca

13.9163 (5), 20.4248 (7),

23.0316 (8)

˚

a, b, c (A)

16.847 (3), 15.6786 (18), 21.787 (2)

ꢃ, ꢄ, ꢅ (^ꢃ)

90, 106.954 (4), 90

5504.9 (12)

90, 118.401 (2), 90

4084.5 (5)

90, 90, 90

6546.4 (4)

3

˚

V (A )

Z

6

0.08

4

0.12

4

2.57

ꢁ (mm^ꢁ1

Crystal size (mm)

)

0.48 ꢂ 0.40 ꢂ 0.37

0.45 ꢂ 0.33 ꢂ 0.23

0.41 ꢂ 0.35 ꢂ 0.29

Data collection

T_min, T_max

0.951, 0.975

69149, 29225, 20602

0.952, 0.979

17279, 5888, 4280

0.438, 0.542

75283, 9558, 8071

No. of measured, independent and

observed [I > 2ꢆ(I)] reﬂections

R_int

0.036

0.682

0.044

0.703

0.034

0.703

ꢁ1

˚

(sin ꢇ/ꢈ)_max(A

)

Reﬁnement

R[F²> 2ꢆ(F²)], wR(F²), S

No. of reﬂections

0.047, 0.122, 0.98

29225

0.043, 0.109, 1.01

5888

0.024, 0.055, 1.02

9558

No. of parameters

No. of restraints

Áꢉ_max, Áꢉ_min(e A

Absolute structure

Absolute structure parameter

1238

17

241

2

395

0

ꢁ3

˚

)

0.27, ꢁ0.21

0.38, ꢁ0.26

0.39, ꢁ0.33

Reﬁned as an inversion twin

0.07 (15)

–

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXT (Sheldrick, 2015a), SHELXL2017 (Sheldrick, 2015b) and SHELXTL (Sheldrick, 2008).

2.1.2. Synthesis of (BHT)₂AlMe. A solution of AlMe₃

(740 mg, 10 mmol, 97% purity) in hexane (4 ml) was added

dropwise to a stirred solution of 2,6-di-tert-butyl-4-methyl-

phenol (4.408 g, 20 mmol) in hexane (7 ml). The reaction

mixture was stirred for 10 min until the product started to

precipitate. The reaction mixture was heated under reﬂux for

40 min and then cooled to room temperature. After 3 h, the

mother liquor was decanted. The crystalline precipitate was

recrystallized from boiling hexane (5 ml) and dried under

vacuum. The yield of colourless crystals was 3.992 g

measurements were recorded on an Agilent PL-GPC 220

chromatograph equipped with a PLgel Olexis column (eluent:

THF, 1 ml min^ꢁ1, 313 K), using universal calibration with

polystyrene (PS) standard. Mg(BHT)₂(THF)₂was prepared as

described previously (Nifant’ev et al., 2017d).

2.1. Synthesis and crystallization

2.1.1. Crystallization of Mg(BHT)₂(THF)₂, (1). A solution of

(3a⁰R,5⁰S,6⁰S,6a⁰R)-5⁰-(1,4-dioxaspiro[4.5]decan-2-yl)tetrahydro-

spiro[cyclohexane-1,2⁰-furo[2,3-d][1,3]dioxol]-6⁰-ol (C₁₈H₂₈O₆;

340 mg, 0.4 mmol) in THF (2 ml) was added dropwise to a

solution of Mg(BHT)₂(THF)₂(243 mg, 0.4 mmol) in THF

(2 ml). The reaction mixture was stirred for 30 min. The

solvent was almost completely evaporated from the solution

under reduced pressure. The residue was then washed with

hexane (3 ꢂ 1.5 ml) and dried under vacuum, providing an

amorphous powder. The ¹H NMR spectrum showed the

presence of coordinated glucose and BHT (in a 1:1 ratio), and

the absence of free BHT-H. The solid was dissolved in toluene

(1.5 ml) and hexane (9 ml) was layered on top. Crystals of (1)

formed after two weeks. Some of these were taken for X-ray

diffraction analysis. The remaining crystals were washed with

hexane (3 ꢂ 1 ml) and dried under vacuum. The yield was

1

(8.30 mmol, 83%). H NMR (C₆D₆, 302 K, 300 MHz): ꢂ 7.14

(4H, s, H_meta), 2.32 (6H, s, CH₃, BHT), 1.59 (36H, s, ^tBu, BHT),

0.24 (3H, s, Al–CH₃).

2.1.3. Synthesis of [(BHT)AlMe(OCH₂COOEt)]₂, (2). A

solution of ethyl 2-hydroxyacetate (HOCH₂COOEt; 104 mg,

1.0 mmol) in toluene (1 ml) was added dropwise to a stirred

solution of (BHT)₂AlMe (481 mg, 1.0 mmol) in toluene (3 ml)

containing 4 drops of THF. The resulting solution was stirred

for 3 min. Hexane (16 ml) was layered on top of the solution.

Colourless crystals formed after 10 d. Some crystals were

taken for X-ray studies. The mother liquor was decanted. The

remaining crystals were washed with hexane (2 ꢂ 2 ml) and

dried under vacuum. The yield of (2) was 288 mg (0.40 mmol,

79%). Analysis found (calculated for C₄₀H₆₆Al₂O₈) (%): C

65.54 (65.91), H 9.52 (9.13). m/z: 728.44 (100.0%), 729.44

(43.6%), 730.45 (9.6%), 731.45 (2.1%), 730.44 (1.6%). ¹H

NMR (C₆D₅CD₃, 300 K, 400 MHz): ꢂ ꢁ0.20 (3H, s, Al–CH₃),

0.57 (3H, t, CH₂–CH₃, ³J_HH= 7.07 Hz), 1.62 [18H, s, C(CH₃)₃],

1

140 mg. H NMR (C₆D₅CD₃, 299 K, 300 MHz): ꢂ 1.27–1.37

(4H, m, O–CH₂–CH₂, THF), 1.60 [18H, s, Ar–C(CH₃)₃], 2.41

(3H, s, Ar–CH₃), 3.66–3.76 (4H, m, O–CH₂, THF), 7.21 (2H, s,

H_meta).

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Acta Cryst. (2018). C74, 548–557

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Ring-opening polymerization of "-caprolactone 551

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2.33 (3H, s, C_ipso–CH₃), 3.37–3.47 (1H, m, CH₂–CH₃), 3.52–

3.62 (1H, m, CH₂–CH₃), 4.23–4.35 (2H, m, O–CH₂–CO), 7.19

(2H, s, H_meta). See Fig. S1 in the supporting information for the

¹H NMR spectrum.

obtained using catalyst (3) is given in Fig. S7 of the supporting

information.

2.2. Refinement

2.1.4. Synthesis of [(BHT)ZnEt]₂. A solution of ZnEt₂in

hexane (20 ml, 1.0 M, 20 mmol) was added dropwise to a

stirred solution of 2,6-di-tert-butyl-4-methylphenol (4.407 g,

20 mmol) in toluene (6 ml). The reaction mixture was stirred

for 30 min. The next day the mother liquor was decanted from

the precipitated crystals, which were then washed with hexane

(2 ꢂ 10 ml) and dried under dynamic vacuum. The yield of

Crystal data, data collection and structure reﬁnement

details are summarized in Table 1. The H atoms were posi-

˚

tioned geometrically (C—H = 0.95 A for aromatic, 0.98 A for

˚

methyl and 0.99 A for methylene H atoms) and reﬁned as

riding atoms, with relative isotropic displacement parameters

U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C)

otherwise. A rotating group model was applied for methyl

groups.

1

colourless crystals was 5.589 g (8.89 mmol, 89%). H NMR

(C₆D₆, 293 K, 400 MHz): ꢂ 7.20 (2H, s, H_meta), 2.27 (3H, s, CH₃,

Reﬂections 101 and 100 in (1) were affected by the beam

stop and were therefore omitted from the reﬁnement.

Reﬂections 606 and 508 in (1) were also omitted from the

reﬁnement since their (I_obsꢁ I_calcd)/ꢆ(W) values were over 10.

Complex (1) was reﬁned as an inversion twin with a domain

ratio of 0.93 (15):0.07 (15), where the rather high s.u. value

might be explained by low anomalous scattering, as well as by

pseudosymmetry. Two of the three independent molecules in

(1) exhibit rotational disorder of the tert-butyl groups, with

ratios of 0.741 (3):0.259 (3) and 0.900 (3):0.100 (3) for the

C28A–C30A/C28B–C30B and C23C–C25C/C23D–C25D

atoms, respectively (Figs. 4a and 4b). The third molecule

contains a conformationally disordered THF molecule [atoms

C32E/C32F; the disorder ratio is 0.809 (6):0.191 (6); Fig. 4c].

The terminal methyl group in the OCH₂COOCH₂CH₃ligand

in (2) is almost equally disordered over two positions, with a

ratio of 0.507 (11):0.493 (11) for the C19A/C19B atoms (Fig. 5).

One of four non-equivalent phenyl groups is disordered over

two positions; the ratio is 0.622 (6):0.378 (6) for atoms C30A–

C34A/C30B–C34B (Fig. 6a). All the disorder was reﬁned in a

regular manner, including the same anisotropic displacement

parameters for similar atoms. All six C—CH₃bond lengths in

each of the two disordered tert-butyl groups and the four

CH₂—CH₂bond lengths in the disordered THF fragment in

(1), together with two CH₂—CH₃bond lengths in (2), were

BHT), 1.63 (18H, s, ^tBu, BHT), 1.13 (3H, t, –CH₂CH₃, ³J_HH

3

8.08 Hz), 0.60 (3H, q, –CH₂CH₃, J_HH= 8.08 Hz).

=

2.1.5. Synthesis of [Zn₇(OCH₂Ph)₈Et₆], (3). A solution of

benzyl alcohol (110 mg, 1.02 mmol) in toluene (2 ml) was

added to crystals of [(BHT)ZnEt]₂(325 mg, 0.52 mmol). The

mixture was stirred for 2 min to give a colourless solution.

After 30 min, hexane (8 ml) was layered on top of the solu-

tion. Colourless crystals of [Zn₇(OCH₂Ph)₈Et₆], (3), formed

over a period of 10 d (yield: 183 mg, 0.12 mmol, 84%). Half

of the crystals were taken for X-ray studies. The other half

were washed with hexane (2 ꢂ 0.5 ml) and dried under

1

vacuum. H NMR (C₆D₅CD₃, 300 K, 400 MHz): ꢂ ꢁ0.07 to

+0.26 (6H, m, Zn–CH₂–CH₃), 0.95–1.03 (9H, m, Zn–CH₂–

CH₃), 4.67–5.24 (8H, m, Zn–CH₂–Ph), 7.07–7.55 (20H, m, Zn–

CH₂–C₆H₅).

2.1.6. Polymerization of "-caprolactone. In a typical poly-

merization experiment, 1 ml of a 0.1 M solution of ROH in

THF (0.1 mmol) was added dropwise to a solution of Mg-

(BHT)₂(THF)₂(61 mg, 0.1 mmol) in THF (1 ml). The reaction

mixture was stirred for 20 min. A solution of "-CL (1.141 g,

10.0 mmol) in THF (up to 3 ml of the solution) was added at

i

once to the resulting stirred suspension (for ROH = PrOH,

^tBuOH and ^tBuCH₂OH). The "-CL/ROH/Mg molar ratio was

100:1:1. After a certain amount of time (see reaction time in

Table 5), a sample of the reaction mixture was dissolved in

CDCl₃containing a small amount of acetic acid to neutralize

the catalyst. The "-CL conversion into PCL was calculated

from a recordered ¹H NMR spectrum, based on integral

intensities of the CH₂OC O proton resonance signals being

4.14 ppm for "-CL and 3.98 ppm for PCL. The vial was then

taken out of the dry-box. The resulting viscous solution was

poured into a large excess of methanol (up to 100 ml)

containing a few drops (a ﬁvefold excess with respect to Mg)

of acetic acid. The resulting precipitate was ﬁltered off and

reprecipitated from a THF/methanol mixture (ca 1:10 v/v),

ﬁltered off and dried under dynamic vacuum until a constant

mass was noted. For cholesterol and cyclohexyl-protected

furanose, the "-CL/ROH/Mg molar ratios were 60:1:1 and

˚

restrained to be equal within 0.002 A for each group of

distances using free variables.

3. Results and discussion

3.1. Mg(BHT)₂(THF)₂, (1)

The asymmetric unit of (1) contains three independent

Mg(BHT)₂(THF)₂molecules (Fig. 4), which exhibit disorder

either of the tert-butyl groups (Figs. 4a and 4b) or a coordi-

nated THF molecule (Fig. 4c). The Mg atom adopts a distorted

tetrahedral environment. The O—Mg—O angles lie in the

following ranges for all three molecules: 89.26 (7)–89.59 (7)^ꢃ

for O_THF–Mg–O_THF, 97.82 (7)–125.24 (8)^ꢃfor O_THF–Mg–O_BHT

and 122.30 (8)–125.31 (8)^ꢃfor O_BHT–Mg–O_BHT, which is in

1

75:1:1, respectively. The H NMR spectra of PCL with term-

inal RO groups can be found in the supporting information

(Figs. S2–S6).

agreement with steric hindrance of the ligands. The Mg—

˚

O

_BHTbond lengths are shorter by 0.18–0.21 A than the Mg—

Complexes (2) and (3) were generated in situ. "-CL poly-

merization experiments with (2) and (3) were performed

1

under similar conditions. The H NMR spectrum of PCL

O_THFbond lengths (Table 2), presumably due to the presence

of a negative charge at the phenoxide BHT^ꢁanion regardless

of its bulkiness.

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552 Minyaev et al.

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Table 2

Selected bond lengths (A) for (1).

˚

Mg1—O1A

Mg1—O2A

Mg1—O3A

Mg1—O4A

Mg2—O1C

Mg2—O2C

1.8575 (17)

1.8653 (16)

2.0438 (18)

2.0595 (18)

1.8557 (17)

1.8639 (17)

Mg2—O3C

Mg2—O4C

Mg3—O2E

Mg3—O1E

Mg3—O4E

Mg3—O3E

2.0502 (18)

2.0699 (18)

1.8554 (17)

1.8660 (17)

2.0444 (18)

2.0653 (18)

The crystal structure of another packing polymorph modi-

ﬁcation of Mg(BHT)₂(THF)₂has been established previously

by our group (Nifant’ev et al., 2017d). It belongs to the same

space group (P2₁), but contains one crystallographically

independent molecule and has quite different unit-cell

dimensions. The Mg—O bond lengths and O—Mg—O angles

are nearly identical in both polymorphs of Mg(BHT)₂(THF)₂.

Very similar Mg—O bond lengths and O—Mg—O angles have

also been found in Mg(BHT)₂(DMSO)₂(DMSO is dimethyl

sulfoxide; Nifant’ev et al., 2017d).

The crystal structures of Mg–BHT derivatives are currently

being studied, mainly due to their application in the ROP of

cyclic esters, but until recently they were poorly explored. A

short survey of the Cambridge Structural Database (CSD,

Version 5.38, with updates to May 2017; Groom et al., 2016) for

crystal structures of Mg–OAr complexes, including Mg–BHT

compounds, has been presented recently (Minyaev et al.,

2017), which, however, does not cover the latest dimeric Mg–

BHT structures published by Nifant’ev et al. (2017d).

3.2. [(BHT)AlMe(OCH₂COOEt)]₂, (2)

The molecule of [(BHT)AlMe(OCH₂COOEt)]₂, (2), is

located on an inversion centre, forming a dimeric structure

(Fig. 5) and having an Al₂O₂rhomboid core (Fig. 3, top,

coloured atoms). The terminal BHT ligand is ꢀO-coordinated

to the Al atom, whereas the OCH₂COOEt ligand displays a

ꢁ₂-ꢀ²O,O⁰:ꢀO semi-bridging coordination mode, forming a

ﬁve-membered heteronuclear Al–O–C–C–O ring. The

shortest Al—O bond is Al1—O1(BHT) involving the steri-

cally more crowded BHT ligand (Table 3). Atoms Al1, O1, O2

and C20 lie in one plane, with the greatest deviation of

˚

0.0037 (6) A being for atom Al1. The Al coordination number

(CN_Al) is 5. The closest polyhedron for the Al environment is

a trigonal bipyramid, with atoms O2ⁱand O3 in axial, and

atoms O1, O2 and C20 in equatorial positions (see the selected

bond lengths and angles in Table 3) [symmetry code: (i) ꢁx + 1,

ꢁy + 1, ꢁz + 1]. The fragment containing 14 atoms (Al1, Al1ⁱ,

O2, O2ⁱ, O3, O3ⁱ, C16, C16ⁱ, C17, C17ⁱ, O4, O4ⁱ, C18 and C18ⁱ)

Table 3

Selected geometric parameters (A, ) for (2).

ꢃ

˚

Al1—O1

Al1—O2

Al1—O2ⁱ

1.7390 (10)

1.8665 (10)

1.9080 (10)

Al1—C20

Al1—O3

1.9562 (14)

2.1219 (10)

Figure 4

Al1—O2—Al1ⁱ

O2—Al1—O2ⁱ

O2—Al1—O3

107.13 (5)

72.87 (5)

77.98 (4)

O2ⁱ—Al1—O3

O1—Al1—C20

150.25 (4)

119.07 (6)

The structures of the three crystallographically independent molecules of

Mg(BHT)₂(THF)₂, (1). Displacement ellipsoids were set at the 50%

probability level and H atoms have been omitted. The minor components

of disorder are shown with open solid lines.

Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.

ꢀ

Acta Cryst. (2018). C74, 548–557

Minyaev et al.

Ring-opening polymerization of "-caprolactone 553

research papers

Figure 5

The crystal structure of [(BHT)AlMe(OCH₂COOEt)]₂, (2). Displace-

ment ellipsoids were set at the 50% probability level and H atoms have

been omitted. The second components of the C19A/C19B disorder are

shown with open solid lines. [Symmetry code: (i) ꢁx + 1, ꢁy + 1, ꢁz + 1.]

is nearly planar, with the greatest deviations from the plane

i

being of 0.0828 (7) A for atoms Al1/Al1 , 0.0764 (8) A for O3/

˚

i

˚

O3 and 0.0378 (10) A for O4/O4 . The terminal CH₃group of

the OCH₂COOEt ligand is nearly equally disordered over two

positions [see x2.2 (Reﬁnement) and Fig. 5].

Some negligible nonvalence interactions are present in the

crystal structure, including a rather long C18—Hꢄ ꢄ ꢄO3ⁱⁱⁱ

interaction [the C18ꢄ ꢄ ꢄO3ⁱⁱⁱdistance is 3.5142 (18) A; sym-

˚

3

2

metry code: (iii) ꢁx + 1, y, ꢁz + ].

According to the CSD, there are numerous structures of Al

derivatives possessing the Al₂O₂rhomboid core. However, the

number of closely related Al compounds containing (RO)Al-

(Alkyl/Aryl)(OAryl) fragments with CN_Al= 5 is limited to seven

structures. These are the ﬁve dinuclear complexes [AlMe(O-2,6-

R₂C₆H₃)(ꢁ₂-OCH₂THF-ꢀ²O,O⁰:ꢀO)]₂[where OCH₂THF is

tetrahydrofuran-2-ylmethoxide; R = Me (CSD refcode FIL-

LOC) or ^tBu (FILMAP); Boyle et al., 2005), [AlEt(THF)(ꢁ₂-

mbpcp-ꢀ²O,O⁰:ꢀO]₂[mbpcp is 2,2⁰-methylenebis(4-chloro-

phenoxide); HIBKAF; Zevaco et al., 2007], [AlR(THF)(ꢁ₂-

OC₆H₄OC₆H₄O-ꢀ³O,O⁰,O⁰⁰:ꢀO)] [OC₆H₄OC₆H₄O is the 2,2⁰-

oxobis(phenoxide) dianion; R = ^tBu (PAKLEU) and Ph

(PAKLIY); Ziemkowska et al., 2011], [AlMe(THF)(ꢁ₂-BINOL-

ꢀ²O,O⁰:ꢀO)]₂[BINOL is the binaphthoxide dianion; PERKAY

(Arai et al., 1998) and PERKAY01 (Graves et al., 2007)], and the

two tetranuclear complexes [R⁰₂(AlR⁰⁰)₄(ꢁ₂-OAryl)₂] [where R⁰=

OPh, R⁰⁰= Et and OAryl = OPh (IWEBIW; Karpiniec et al.,

2011); R⁰= Me, R⁰⁰= Me and OAryl = O-3,5-(CF₃)₂C₆H₃

Figure 6

(a) The asymmetric unit and (b) the molecule in the crystal structure of

[Zn₇(OCH₂Ph)₈Et₆], (3). Displacement ellipsoids were set at the 50%

probability level and

H atoms have been omitted. The second

components of the phenyl-ring disorder (atoms C30–C34) are shown

with open solid lines (left). For the entire molecule (right), all but the

C_ipsoatoms of the phenyl groups have been omitted. C_ipsoatoms are

labelled as ‘Ph’ and the disorder is not shown. [Symmetry code: (ii) ꢁx + 1,

ꢁy + 1, ꢁz + 1.]

(WODXET; Martinez et al., 2008)]. None of these compounds

contains a glycolate O–CR₂–COO–R fragment.

On the other hand, there are ﬁve mononuclear Al structures

bearing the ^ꢁO–CR₂–COO–R anionic ligand, viz. [Al(L-ꢀ⁴O,O⁰,-

N,N⁰)(OCHMeCOOMe-ꢀ²O,O⁰)]ꢄtoluene (NIFPAU; Nomura et

al., 2007), [Al(L-ꢀ⁴O,O⁰,N,N⁰)(OCHMeCOOMe-ꢀO)] (ODA-

ꢀ

554 Minyaev et al.

Ring-opening polymerization of "-caprolactone

Acta Cryst. (2018). C74, 548–557

research papers

Table 4

Selected geometric parameters (A, ) for (3).

3.3. [Zn₇(OCH₂Ph)₈Et₆], (3)

ꢃ

˚

The structure of [Zn₇(OCH₂Ph)₈Et₆] is located on an

inversion centre. The asymmetric unit is shown in Fig. 6(a).

The phenylmethanolate ligand displays a ꢁ₃-ꢀO:ꢀO:ꢀO coor-

dination mode. The site occupancy for atom Zn1 is 50%. The

heptanuclear complex (Fig. 6b) has a distorted bicubic Zn₇O₈

core (Fig. 3, bottom, coloured atoms; see also selected Zn—O

bond lengths and O—Zn—O angles in Table 4), in which the

central Zn1 atom has CN_Zn= 6, whereas CN_Zn= 4 for the

other Zn atoms. All Znꢄ ꢄ ꢄZn distances are in the range from

Zn1—O1

Zn1—O2

Zn1—O3

Zn2—O1

Zn2—O2

Zn2—O4

Zn3—O2

Zn3—O3

2.1148 (9)

2.1062 (10)

2.1332 (9)

2.0596 (10)

2.0922 (10)

2.1203 (10)

2.0631 (10)

2.0524 (10)

Zn3—O4

Zn4—O1

Zn4—O3

Zn4—O4

Zn2—C1

Zn3—C3

Zn4—C5

2.0553 (10)

2.1228 (10)

2.0858 (10)

2.0511 (10)

1.9637 (15)

1.9655 (16)

1.9695 (15)

O2—Zn1—O1

O2—Zn1—O1ⁱ

O1—Zn1—O3

O1—Zn1—O3ⁱ

O2—Zn1—O3

O2—Zn1—O3ⁱ

O1—Zn2—O2

O1—Zn2—O4

81.39 (4)

98.61 (4)

81.72 (4)

98.28 (4)

82.72 (4)

97.28 (4)

83.04 (4)

82.80 (4)

O2—Zn2—O4

O3—Zn3—O2

O4—Zn3—O2

O3—Zn3—O4

O3—Zn4—O1

O4—Zn4—O1

O4—Zn4—O3

82.36 (4)

85.79 (4)

84.67 (4)

83.54 (4)

82.65 (4)

82.94 (4)

82.82 (4)

˚

3.0771 (2) (for Zn3ꢄ ꢄ ꢄZn4) to 3.1443 (2) A (for Zn1ꢄ ꢄ ꢄZn2).

The crystal structure of the complex [Zn₇(OCH₂Ph)₈Et₆] has

been established previously (CSD refcode BANRUF; Li, Nie

et al., 2012). However, sufﬁciently good single-crystal quality

has allowed us to obtain a better crystallographic model

presented herein.

Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.

The cubic Zn₄O₄core is rather robust and common – there

are 61 crystal structures upon exclusion of duplicates in the

CSD. The bicubic Zn₇O₈core seems to be common as well.

Eleven structures have been found, including [Zn₇(C₂H₅)₆(ꢁ₂-

OCH₂Ph)₈]. Other similar complexes possessing the [Zn₇(ꢁ₃-

FUW; Tang et al., 2006) and [Al(L-ꢀ⁴O,O⁰,N,N⁰)(OCMe₂-

COOMe-ꢀ²O,O⁰)] (QADCUW; Kan et al., 2016), where

ligands L are dianionic salen-like tetradentate ligands, and

[Al(L⁰-ꢀ³O,O⁰,N)(OCHMeCOOⁱPr-ꢀ²O,O⁰)] [L⁰is a bis-

(phenoxide) derivative of pyridine; ZOVYAM; Klitzke et al.,

2014) and [Al{O-2-(Me₂NCH₂)-4-Me-6-(CPh₃)C₆H₂-ꢀ²O,N}-

(OCHMeCOOCHMeCOOⁱPr-ꢀ²O,O⁰)(THF)]⁺[B(C₆F₅)₄]^ꢁꢄ-

0.5(cyclopentane) (YIBWUC; Dagorne et al., 2007). The ^ꢁO–

CR₂-COO–Alkyl ligand exhibits the ꢀO coordination mode in

one case and the ꢁ₂-ꢀ²O,O⁰:ꢀO coordination mode in four of

OR)₈R⁰₆] structural motif are EMEYA/ZNOMEZ (R = Me

0

´

and OR = OMe; Lewinski et al., 2003; Ziegler & Weiss, 1970),

KOHSEG (R = Me and OR⁰= OCH₂CH₂OMe; Polarz et al.,

2005), ICEVUI [R = Et and OR⁰= OCH₂–C₃H₅(C₃H₅is

cyclopropyl); Boyle et al., 2004], MIGXIJ (R = CH₂I and OR⁰=

OMe; Charette et al., 2002), MOZNET (R = Et and OR⁰=

OMe; Ishimori et al., 1976), YIGHAY/YIGHAY01 (R = Et

and OR⁰= OEt; Jana et al., 2007; Redshaw et al., 2010)

and YOKXUS ({Zn₇Me₆(ꢁ₃-OMe)₆[ꢁ₃-OZnMe(^tBuN CH–

CH N^tBu-ꢀ²N,N⁰)]₂}ꢄtoluene; Lewinski et al., 2008).

the ﬁve complexes. The structure of [(BHT)AlMe(OCH₂

-

COOEt)]₂, (2), remains the sole example of a dimeric complex

possessing the Al₂O₂rhomboid core and incorporating both

aryloxy and glycolate ligands.

The structure of (2) seems to be structurally analogous to

the Mg complex [(BHT)Mg(THF)(ꢁ-OCH₂COOEt)]₂(Nif-

ant’ev et al., 2017d), where the CH₃ligand is replaced with the

THF molecule. However, the Mg₂O₄C₄core of the latter is not

ﬂat, unlike that in (2). Both complexes demonstrate good

(Mg) or moderate (Al, see below) catalytic activity in the ROP

of "-CL without activation by alcohol.

Three remaining structures for metal–organic framework

(MOF) applications have more complex structures:

[Zn₇(H₂L)₃(OMe)₂]ꢄH₂O (FORTOX) and [Cd₂{Zn₇L(HL)₂-

(OH)₂}(Py)₂(H₂O)]ꢄDMF (FORTIR) (Liu et al., 2014), and

[Zn₇L⁰₃(OH)₂]ꢄ6DMFꢄ2H₂O (HAKZUR; Fang et al., 2016),

where L and L⁰are ꢁ₅-coordinated hexaanionic (L) or

tetraanionic (L⁰) salen-like hexadentate ligands. A sole

example of a similar Mg₇O₈bicubic core was found in the

Table 5

Catalytic experimental data for "-caprolactone polymerization using Mg(BHT)₂(THF)₂as precatalyst (BHT is the 2,6-di-tert-butyl-4-methylphenoxide

anion and THF is tetrahydrofuran) and different initiators ROH (["-CL] = 2 M, 293 K).

M_nis the number average molecular mass and Conv. is a monomer-to-polymer conversion value.

a

b

c

Run

Catalyst

ROH activator

"-CL/ROH

Reaction time (min)

Conv. (%)

>99

11

89

>99

>98

35

98

33

M_n,theo.

M_{n, NMR}

M_n,GPC

Ð_M

1

2

3

4

5

6

7

8

9

(1)

(2)

(3)

ⁱPrOH

100

60

20

360

20

60

11470

1330

10230

11300

7240

8820

4100

11290

3870

12940

n.d.

13120

n.d.

1.30

n.d.

1.76

1.24

1.37

2.14

3.45

2.82

3.22

^tBuOH

14110

12170

7050

9130

n.d.

23800

11200

6940

7740

8200

16400

6400

^tBuCH₂OH

Cholesterol

Cyclohexyl-protected furanose

75

No

100

n.d.

7530

60

Notes: (a) theoretically calculated M_n,theo= M_"-CLꢂ ["-CL]₀/[I]₀ꢂ conversion + M_ROH, where M_"-CLis the molecular mass of "-CL, M_ROHis the molecular mass of the initiator and

["-CL]₀/[I]₀is the monomer-to-initiator initial concentration ratio; (b) determined from ¹H NMR spectra by analysis of the signal integration of the RO and PCL fragments, see the

supporting information; (c) determined by GPC versus polystyrene standards and corrected by a factor of 0.56 (Save et al., 2002), where Ð_Mis a polydispersity index determined as Ð_M

M_w/M_n, where M_wis weight average molecular mass.

=

ꢀ

Acta Cryst. (2018). C74, 548–557

Minyaev et al.

Ring-opening polymerization of "-caprolactone 555

research papers

heptanuclear complex [Mg₇(ꢁ₃-O)₈(L⁰⁰-ꢀ²O,N)₆] (QUFBAW;

Ghosh et al., 2015) [L⁰⁰= O-2,4-^tBu₂C₆H₂-6-(–CH N-C₆H₄-4-

OMe)].

analysis of the catalysts) and partially supported by the TIPS

RAS State Plan (analysis of the obtained polymers).

Funding information

3.4. Results of the ROP of "-CL

Funding for this research was provided by: Russian Science

Foundation (grant No. 16-13-10344); TIPS RAS State Plan.

In ROP experiments catalyzed by (1) activated by primary

and secondary ROH initiators (Figs. 1 and 2), we observed

nearly quantitative "-CL conversions after 20 min into PCL

polymers with a narrow molecular weight distribution (Table 5,

runs 1 and 4–6). The OR/"-CL unit ratios in polymers deter-

mined by end-group analysis of the ¹H NMR spectra are close

to the starting monomer/initiator ratios. These facts conﬁrm

the living character of the ROP initiated by different BHT–

Mg–OR complexes with sterically unhindered initiators. In the

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4. Concluding remarks

The structure of a new packing polymorph of Mg(BHT)₂-

(THF)₂has been determined. Formed in situ, its BHT–Mg

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^tBuOH, ^tBuCH₂OH, cholesterol and a bis(cyclohexyl)-

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Acknowledgements

This work was supported by the Russian Science Foundation

(design and synthesis of the catalysts and polymers, X-ray

ꢀ

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ꢀ

Acta Cryst. (2018). C74, 548–557

Minyaev et al.

Ring-opening polymerization of "-caprolactone 557

supporting information

Acta Cryst. (2018). C74, 548-557 [https://doi.org/10.1107/S2053229618005090]

Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-

opening polymerization of ∊-caprolactone with initiators of different natures

Mikhail E. Minyaev, Ilya E. Nifant'ev, Andrey V. Shlyakhtin, Pavel V. Ivchenko and Konstantin A.

Lyssenko

Computing details

For all structures, data collection: APEX2 (Bruker, 2008). Cell refinement: APEX2 (Bruker, 2008) for Mg; SAINT

(Bruker, 2008) for Al, Zn. Data reduction: APEX2 (Bruker, 2008) for Mg; SAINT (Bruker, 2008) for Al, Zn. For all

structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure:

SHELXL2017 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for

publication: SHELXTL (Sheldrick, 2008).

Bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(tetrahydrofuran-κO)magnesium (Mg)

Crystal data

[Mg(C₁₅H₂₃O)₂(C₄H₈O)₂]

M_r= 607.18

F(000) = 2004

D_x= 1.099 Mg m⁻³

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 999 reflections

θ = 3–25°

Monoclinic, P2₁

a = 16.847 (3) Å

b = 15.6786 (18) Å

c = 21.787 (2) Å

β = 106.954 (4)°

V = 5504.9 (12) Å³

Z = 6

µ = 0.08 mm⁻¹

T = 120 K

Block, colourless

0.48 × 0.40 × 0.37 mm

Data collection

Bruker SMART APEXII

diffractometer

Radiation source: fine-focus sealed tube

Graphite monochromator

ω scans

69149 measured reflections

29225 independent reflections

20602 reflections with I > 2σ(I)

R_int= 0.036

θ

_max= 29.0°, θ_min= 1.0°

Absorption correction: multi-scan

(SADABS; Bruker, 2008)

h = −22→22

k = −21→21

l = −29→29

T

_min= 0.951, T_max= 0.975

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.047

wR(F²) = 0.122

S = 0.98

29225 reflections

1238 parameters

17 restraints

Hydrogen site location: inferred from

neighbouring sites

H-atom parameters constrained

w = 1/[σ²(F_o²) + (0.0599P)²]

where P = (F_o²+ 2F_c²)/3

(Δ/σ)_max= 0.001

Acta Cryst. (2018). C74, 548-557

sup-1

supporting information

Δρ_max= 0.27 e Å⁻³

Δρ_min= −0.20 e Å⁻³

Absolute structure: Refined as an inversion twin

Absolute structure parameter: 0.07 (15)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full

covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and

torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.

An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F²against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F²,

conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F²> σ(F²) is used

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F²

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

Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

x

y

z

U_iso*/U_eq

Occ. (<1)

Mg1

O1A

C1A

C2A

C3A

H3A

C4A

C5A

H5A

C6A

C7A

0.17592 (5)

0.20462 (10)

0.22385 (13)

0.19674 (14)

0.21622 (14)

0.196822

0.26265 (14)

0.29009 (14)

0.322360

0.27261 (14)

0.14616 (17)

0.06190 (17)

0.032959

0.27788 (5)

0.21640 (10)

0.16511 (15)

0.07843 (15)

0.02827 (15)

−0.028928

0.05811 (15)

0.14227 (15)

0.163535

0.19696 (14)

0.03859 (16)

0.0843 (2)

0.081997

0.09003 (4)

0.16622 (7)

0.21712 (10)

0.21239 (11)

0.26792 (11)

0.264581

0.32782 (11)

0.33133 (11)

0.371735

0.27851 (11)

0.14826 (11)

0.12368 (13)

0.156681

0.01458 (16)

0.0186 (3)

0.0147 (4)

0.0174 (5)

0.0178 (5)

0.021*

0.0175 (5)

0.0185 (5)

0.022*

0.0160 (5)

0.0264 (6)

0.0368 (7)

0.055*

C8A

H8A

H8B

0.028188

0.055973

0.084668

0.055*

H8C

0.070930

0.143925

0.114053

0.055*

C9A

H9A

H9B

0.1283 (2)

0.094656

0.180842

0.098154

0.19456 (19)

0.209079

0.159990

0.245345

0.28155 (16)

0.263464

0.252041

−0.05665 (18)

−0.063019

−0.087349

−0.080170

0.04316 (16)

0.102612

0.020668

0.009095

0.00094 (16)

−0.057335

0.021825

0.15546 (13)

0.185034

0.172454

0.113461

0.09819 (12)

0.092667

0.057111

0.112964

0.38607 (11)

0.372745

0.415765

0.0417 (8)

0.063*

0.0322 (7)

0.048*

0.0233 (5)

0.035*

H9C

C10A

H10A

H10B

H10C

C11A

H11A

H11B

H11C

C12A

C13A

H13A

H13B

H13C

0.341403

0.001234

0.407510

0.035*

0.30524 (14)

0.35577 (17)

0.377356

0.402133

0.319862

0.28902 (15)

0.30896 (17)

0.367312

0.268783

0.303435

0.28699 (11)

0.35697 (12)

0.359530

0.370790

0.384956

0.0190 (5)

0.0295 (6)

0.044*

Acta Cryst. (2018). C74, 548-557

sup-2

supporting information

C14A

H14A

H14B

H14C

C15A

H15A

H15B

H15C

O2A

0.23293 (16)

0.198484

0.255079

0.199221

0.36377 (15)

0.333225

0.35324 (16)

0.343431

0.411434

0.345716

0.30458 (16)

0.296225

0.27005 (12)

0.225895

0.273987

0.299494

0.24538 (12)

0.200064

0.0246 (6)

0.037*

0.0249 (6)

0.037*

0.410231

0.385083

0.264332

0.363076

0.257730

0.251878

0.037*

0.17724 (10)

0.18788 (14)

0.11733 (14)

0.12829 (15)

0.081180

0.20528 (15)

0.27348 (15)

0.326520

0.26779 (14)

0.03165 (14)

−0.00309 (15)

0.034914

−0.008860

−0.057501

−0.03380 (15)

−0.015008

−0.086738

−0.041135

0.03941 (17)

0.080095

−0.014601

0.057683

0.21425 (17)

0.266248

0.214861

0.167419

0.35116 (13)

0.3468 (2)

0.316927

0.403184

0.317621

0.23572 (10)

0.17449 (14)

0.14383 (14)

0.07743 (15)

0.056485

0.04013 (15)

0.07282 (14)

0.048810

0.13970 (14)

0.18638 (15)

0.17668 (17)

0.203499

0.115981

0.204378

0.14667 (18)

0.151933

0.176639

0.086257

0.28087 (17)

0.308929

0.308890

0.284951

−0.03141 (17)

−0.062106

−0.007424

−0.070893

0.17313 (13)

0.2298 (2)

0.282518

0.01027 (7)

−0.02957 (10)

−0.07949 (10)

−0.11847 (11)

−0.150529

−0.11268 (11)

−0.06606 (11)

−0.062083

−0.02450 (10)

−0.09245 (11)

−0.03510 (11)

0.002813

−0.026565

−0.044903

−0.15050 (11)

−0.188877

−0.157467

−0.141965

−0.10896 (12)

−0.073141

−0.116612

−0.147641

−0.15714 (12)

−0.137934

−0.198533

−0.163647

0.02010 (10)

0.07634 (15)

0.059762

0.0178 (3)

0.0142 (4)

0.0161 (5)

0.0186 (5)

0.022*

0.0207 (5)

0.0186 (5)

0.022*

0.0160 (5)

0.0187 (5)

0.0254 (6)

0.038*

0.0272 (6)

0.041*

0.0282 (6)

0.042*

0.0273 (6)

0.041*

0.0170 (5)

0.0265 (7)

0.040*

0.0284 (8)

0.043*

0.0341 (9)

0.051*

C16A

C17A

C18A

H18A

C19A

C20A

H20A

C21A

C22A

C23A

H23A

H23B

H23C

C24A

H24A

H24B

H24C

C25A

H25A

H25B

H25C

C26A

H26A

H26B

H26C

C27A

C28A

H28A

H28B

H28C

C29A

H29A

H29B

H29C

C30A

H30A

H30B

H30C

C28B

0.741 (3)

0.259 (3)

0.243815

0.199438

0.0971 (2)

0.064573

0.060124

0.118092

0.2227 (2)

0.185364

0.242822

0.271734

0.102642

0.102586

0.05057 (17)

0.017009

0.072372

0.4064 (2)

0.421046

0.376229

0.457078

0.3935 (2)

0.400583

0.447886

0.359037

0.3593 (6)

0.081717

−0.02217 (17)

−0.056247

0.004032

−0.041369

0.0920 (2)

0.051*

0.0265 (7)

0.1647 (7)

Acta Cryst. (2018). C74, 548-557

sup-3

supporting information

H28D

H28E

H28F

C29B

H29D

H29E

H29F

C30B

H30D

H30E

H30F

O3A

C31A

H31A

H31B

C32A

H32A

H32B

C33A

H33A

H33B

C34A

H34A

H34B

O4A

C35A

H35A

H35B

C36A

H36A

H36B

C37A

H37A

H37B

C38A

H38A

H38B

Mg2

0.413099

0.355170

0.314665

0.4315 (4)

0.436230

0.430288

0.479305

0.3625 (7)

0.362193

0.415471

0.187343

0.104464

0.196938

0.1327 (6)

0.143696

0.071050

0.157661

0.2680 (3)

0.274944

0.288303

0.117225

0.102665

0.101854

0.0137 (5)

−0.029349

0.020722

0.040*

0.0284 (8)

0.043*

0.0341 (9)

0.051*

0.259 (3)

0.045780

0.0065 (5)

−0.038218

0.035032

0.316975

0.301170

0.014199

0.051*

0.21528 (10)

0.22131 (17)

0.272203

0.172627

0.22412 (17)

0.281599

0.188751

0.19046 (17)

0.129032

0.211663

0.22418 (18)

0.191799

0.39920 (10)

0.47038 (15)

0.465192

0.471146

0.55161 (15)

0.573289

0.596714

0.52283 (16)

0.523285

0.559228

0.43306 (16)

0.398803

0.08075 (8)

0.12539 (12)

0.162049

0.142119

0.08740 (12)

0.096614

0.097496

0.01743 (12)

0.002905

−0.011447

0.02059 (12)

−0.016430

0.021086

0.09549 (8)

0.04862 (13)

0.005186

0.059623

0.05082 (14)

0.009674

0.059604

0.10549 (14)

0.131510

0.088860

0.14453 (13)

0.173569

0.0204 (4)

0.0254 (6)

0.030*

0.0252 (6)

0.030*

0.0276 (6)

0.033*

0.0278 (6)

0.033*

0.283127

0.433435

0.033*

0.06468 (10)

0.00794 (16)

0.013287

0.32664 (11)

0.38130 (18)

0.370900

0.442112

0.3588 (2)

0.333430

0.410156

0.2943 (2)

0.305157

0.235172

0.3098 (2)

0.359261

0.0223 (4)

0.0294 (6)

0.035*

0.0354 (7)

0.042*

0.0395 (7)

0.047*

0.0309 (6)

0.037*

0.020174

−0.07942 (16)

−0.112361

−0.108563

−0.06624 (17)

−0.104540

−0.074344

0.02379 (16)

0.028414

0.047659

0.258875

0.170227

0.037*

0.48928 (5)

0.46410 (10)

0.44362 (14)

0.39177 (14)

0.37384 (15)

0.339640

0.40371 (15)

0.45252 (15)

0.472451

0.78096 (5)

0.71592 (10)

0.66282 (15)

0.69130 (14)

0.63517 (15)

0.654603

0.55210 (15)

0.52463 (15)

0.467613

0.24224 (3)

0.16788 (7)

0.11796 (11)

0.05679 (11)

0.00495 (11)

−0.035416

0.00962 (11)

0.06924 (11)

0.073329

0.01475 (17)

0.0176 (3)

0.0163 (5)

0.0159 (5)

0.0203 (5)

0.024*

0.0208 (5)

0.0217 (5)

0.026*

O1C

C1C

C2C

C3C

H3G

C4C

C5C

H5G

C6C

C7C

0.47381 (15)

0.35692 (15)

0.57710 (15)

0.78313 (15)

0.12375 (11)

0.04690 (11)

0.0194 (5)

0.0196 (5)

Acta Cryst. (2018). C74, 548-557

sup-4

supporting information

C8C

H8G

0.42852 (17)

0.405763

0.84818 (16)

0.906143

0.06002 (13)

0.055018

0.0283 (6)

0.042*

H8H

0.460480

0.839128

0.029519

0.042*

H8I

0.464843

0.840627

0.103876

0.042*

C9C

H9H

0.30162 (15)

0.279878

0.79980 (16)

0.858120

0.09097 (12)

0.084301

0.0238 (5)

0.036*

H9I

0.334519

0.792613

0.135860

0.036*

H9J

0.255344

0.759251

0.080735

0.036*

C10C

H10G

H10H

H10I

C11C

H11G

H11H

H11I

C12C

C13C

H13G

H13H

H13I

C14C

H14G

H14H

H14I

C15C

H15G

H15H

H15I

O2C

C16C

C17C

C18C

H18G

C19C

C20C

H20G

C21C

C22C

C23C

H23G

H23H

H23I

C24C

H24G

H24H

H24I

C25C

0.30240 (17)

0.280329

0.256343

0.335803

0.38602 (16)

0.327366

0.398563

0.420697

0.53072 (17)

0.5520 (2)

0.500642

0.586901

0.581861

0.61309 (16)

0.638984

0.650543

0.602021

0.48823 (18)

0.437704

0.473783

0.526164

0.47794 (9)

0.47035 (14)

0.39140 (14)

0.38813 (15)

0.335976

0.45755 (16)

0.53330 (16)

0.581132

0.54191 (14)

0.30943 (13)

0.23198 (16)

0.231738

0.232852

0.182027

0.29958 (18)

0.299002

0.247358

0.79911 (18)

0.857319

0.758303

0.791893

0.49366 (16)

0.498243

0.434634

0.510308

0.54106 (17)

0.44641 (19)

0.412949

0.425656

0.440423

0.5913 (2)

0.588816

0.566075

0.650873

0.54488 (16)

0.510105

0.604116

0.522854

0.73893 (10)

0.67951 (14)

0.64271 (14)

0.57683 (15)

0.551144

0.54732 (16)

0.58659 (16)

0.567793

0.65251 (15)

0.67441 (13)

0.63238 (19)

0.641635

0.571025

0.657717

0.77083 (16)

0.782245

0.790418

−0.02220 (12)

−0.025738

−0.032978

−0.051894

−0.04824 (11)

−0.072873

−0.033868

−0.075371

0.18729 (12)

0.18130 (14)

0.168149

0.222826

0.149106

0.20685 (12)

0.172034

0.245734

0.215211

0.24100 (12)

0.228893

0.247338

0.280932

0.31926 (7)

0.36146 (10)

0.35805 (10)

0.40066 (11)

0.397360

0.44750 (12)

0.45229 (11)

0.484673

0.41145 (10)

0.31074 (10)

0.32136 (14)

0.365790

0.0314 (6)

0.047*

0.0251 (6)

0.038*

0.0275 (6)

0.0479 (9)

0.072*

0.0346 (7)

0.052*

0.0305 (6)

0.046*

0.0168 (3)

0.0150 (5)

0.0164 (5)

0.0218 (5)

0.026*

0.0250 (6)

0.0236 (5)

0.028*

0.0181 (5)

0.0266 (7)

0.040*

0.0292 (7)

0.044*

0.900 (3)

0.313007

0.292056

0.31950 (15)

0.363597

0.289490

0.346098

0.30562 (17)

0.801241

0.6559 (2)

0.311012

0.24079 (11)

0.044*

0.0272 (7)

Acta Cryst. (2018). C74, 548-557

sup-5

supporting information

H25G

H25H

H25I

C23D

H23J

H23K

H23L

C24D

H24J

H24K

H24L

C25D

H25J

H25K

H25L

C26C

H26G

H26H

H26I

C27C

C28C

H28G

H28H

H28I

0.253017

0.309492

0.351911

0.2645 (14)

0.249378

0.301363

0.214284

0.3147 (16)

0.258750

0.348517

0.340108

0.2602 (14)

0.217462

0.233742

0.297900

0.45155 (19)

0.398358

0.455331

0.677040

0.594198

0.684462

0.7197 (15)

0.777570

0.722441

0.687793

0.7228 (15)

0.730359

0.690161

0.778799

0.5948 (10)

0.610907

0.569474

0.553119

0.47610 (19)

0.446515

0.500201

0.435616

0.69677 (16)

0.6616 (2)

0.693278

0.601060

0.212290

0.234846

0.230571

0.3537 (10)

0.337591

0.397716

0.353078

0.2507 (8)

0.221260

0.229254

0.263247

0.2804 (11)

0.240919

0.310630

0.270281

0.49314 (13)

0.476433

0.535398

0.497039

0.42256 (11)

0.48195 (12)

0.488076

0.475412

0.520029

0.041*

0.0266 (7)

0.040*

0.0292 (7)

0.044*

0.0272 (7)

0.041*

0.0368 (7)

0.055*

0.900 (3)

0.100 (3)

0.497071

0.055*

0.62675 (15)

0.69326 (16)

0.745144

0.702785

0.674039

0.0199 (5)

0.0328 (7)

0.049*

0.668167

C29C

H29G

H29H

H29I

C30C

H30G

H30H

H30I

0.61635 (16)

0.669418

0.598521

0.574485

0.66154 (15)

0.714853

0.622403

0.669553

0.44741 (10)

0.44378 (17)

0.394523

0.494142

0.43824 (16)

0.380208

0.472967

0.47121 (16)

0.532628

0.449521

0.43757 (17)

0.469546

0.79185 (17)

0.821258

0.798132

0.816834

0.68227 (18)

0.711801

0.704716

0.621051

0.90238 (10)

0.97125 (15)

0.964495

0.970927

1.05433 (16)

1.074749

1.099401

1.02920 (16)

1.029831

1.067349

0.93968 (16)

0.907159

0.940656

0.83053 (11)

0.8176 (2)

0.868559

0.43533 (13)

0.441395

0.474075

0.398669

0.36560 (11)

0.373547

0.326371

0.360544

0.24898 (8)

0.20274 (12)

0.164923

0.188081

0.23796 (13)

0.227461

0.0302 (6)

0.045*

0.0259 (6)

0.039*

0.0208 (4)

0.0259 (6)

0.031*

0.0284 (6)

0.034*

0.0286 (6)

0.034*

0.0259 (6)

0.031*

O3C

C31C

H31G

H31H

C32C

H32G

H32H

C33C

H33G

H33H

C34C

H34G

H34H

O4C

0.227007

0.30870 (13)

0.323604

0.336267

0.30778 (12)

0.345937

0.378439

0.306751

0.031*

0.60087 (10)

0.63864 (16)

0.631805

0.23673 (8)

0.18536 (13)

0.157454

0.0224 (4)

0.0319 (7)

0.038*

C35C

H35G

Acta Cryst. (2018). C74, 548-557

sup-6

supporting information

H35H

C36C

H36G

H36H

C37C

H37G

H37H

C38C

H38G

H38H

Mg3

O1E

C1E

C2E

C3E

H3M

C4E

C5E

H5M

C6E

C7E

0.614449

0.72996 (18)

0.739823

0.766309

0.74501 (17)

0.775005

0.777874

0.65845 (16)

0.654455

0.767490

0.8026 (2)

0.742552

0.817193

0.8625 (2)

0.914323

0.833832

0.88518 (18)

0.874530

0.158840

0.22180 (15)

0.235911

0.194897

0.27908 (14)

0.272350

0.318864

0.28313 (13)

0.326919

0.038*

0.0446 (8)

0.053*

0.0372 (7)

0.045*

0.0290 (6)

0.035*

0.646008

0.946030

0.272419

0.035*

0.84127 (5)

0.84189 (10)

0.85372 (14)

0.93401 (14)

0.94041 (15)

0.993735

0.87273 (16)

0.79523 (15)

0.748367

0.78389 (14)

1.01802 (14)

1.06339 (18)

1.116508

0.26654 (5)

0.22858 (10)

0.17093 (14)

0.13763 (14)

0.07375 (15)

0.050991

0.04224 (16)

0.07789 (15)

0.057998

0.14151 (14)

0.16896 (15)

0.21803 (19)

0.239275

0.42775 (3)

0.34672 (7)

0.30520 (10)

0.30924 (10)

0.26562 (11)

0.268852

0.21804 (11)

0.21307 (11)

0.180258

0.25435 (10)

0.35449 (11)

0.31366 (14)

0.341317

0.01572 (19)

0.0174 (3)

0.0144 (4)

0.0161 (5)

0.0196 (5)

0.023*

0.0223 (5)

0.0206 (5)

0.025*

0.0167 (5)

0.0177 (5)

0.0345 (7)

0.052*

C8E

H8M

H8N

1.029152

0.266223

0.292562

0.052*

H8O

1.073427

0.179861

0.281087

0.052*

C9E

H9M

H9N

1.01425 (16)

1.070720

0.986078

0.22701 (19)

0.241981

0.197097

0.41014 (13)

0.435626

0.437336

0.0314 (6)

0.047*

H9O

0.983550

0.279081

0.393051

0.047*

C10E

H10M

H10N

H10O

C11E

H11M

H11N

H11O

C12E

C13E

H13M

H13N

H13O

C14E

H14M

H14N

H14O

C15E

H15M

1.07265 (16)

1.123870

1.086349

1.042555

0.88206 (17)

0.933153

0.884715

0.834343

0.69729 (14)

0.63240 (15)

0.579020

0.626031

0.650972

0.66347 (15)

0.701295

0.658921

0.608590

0.70275 (17)

0.742848

0.09300 (17)

0.114087

0.059101

0.38563 (13)

0.416091

0.352319

0.408357

0.17243 (12)

0.191831

0.132056

0.163927

0.24325 (11)

0.18378 (11)

0.178066

0.189906

0.145647

0.30041 (11)

0.339175

0.306631

0.291953

0.23043 (13)

0.267271

0.0299 (6)

0.045*

0.0301 (6)

0.045*

0.0195 (5)

0.0280 (6)

0.042*

0.0262 (6)

0.039*

0.0323 (6)

0.048*

0.057378

−0.02746 (18)

−0.059543

−0.001827

−0.066087

0.18177 (15)

0.14472 (18)

0.173350

0.083457

0.153859

0.16605 (18)

0.191144

0.104535

0.192403

0.27782 (17)

0.304564

Acta Cryst. (2018). C74, 548-557

sup-7

supporting information

H15N

H15O

O2E

0.648102

0.720762

0.304032

0.286014

0.223909

0.191933

0.048*

0.87487 (10)

0.89840 (14)

0.94776 (14)

0.96889 (14)

1.002005

0.94358 (14)

0.89729 (14)

0.879765

0.87520 (14)

0.97575 (15)

0.89988 (17)

0.868339

0.864511

0.918411

1.03031 (16)

1.049302

0.997910

1.078435

1.02830 (18)

0.995160

1.045773

1.077395

0.96306 (16)

0.950470

0.929362

0.20255 (10)

0.14983 (14)

0.18083 (14)

0.12492 (15)

0.145701

0.04003 (15)

0.01044 (15)

−0.047409

0.06160 (15)

0.27471 (15)

0.33385 (16)

0.321102

0.324800

0.393368

0.29726 (16)

0.356433

0.290598

0.259080

0.29358 (17)

0.282597

0.353446

0.256692

−0.01719 (16)

−0.076443

−0.000176

−0.012133

0.02167 (16)

−0.07489 (17)

−0.085375

−0.102739

−0.098090

0.03319 (16)

0.094098

0.50252 (7)

0.55264 (10)

0.61378 (11)

0.66584 (11)

0.706138

0.66137 (11)

0.60160 (11)

0.597842

0.54666 (11)

0.62351 (11)

0.61012 (13)

0.640350

0.566137

0.615320

0.58007 (12)

0.587889

0.534999

0.589671

0.69287 (12)

0.722269

0.696339

0.704097

0.71948 (11)

0.705770

0.747263

0.0193 (4)

0.0156 (5)

0.0164 (5)

0.0180 (5)

0.022*

0.0180 (5)

0.0178 (5)

0.021*

0.0174 (5)

0.0195 (5)

0.0284 (6)

0.043*

0.0252 (5)

0.038*

0.0309 (6)

0.046*

0.0250 (6)

0.037*

C16E

C17E

C18E

H18M

C19E

C20E

H20M

C21E

C22E

C23E

H23M

H23N

H23O

C24E

H24M

H24N

H24O

C25E

H25M

H25N

H25O

C26E

H26M

H26N

H26O

C27E

C28E

H28M

H28N

H28O

C29E

H29M

H29N

H29O

C30E

H30M

H30N

H30O

O3E

1.022022

0.743179

0.037*

0.82595 (15)

0.81384 (19)

0.782310

0.868140

0.783366

0.87288 (17)

0.881830

0.840185

0.926583

0.73893 (16)

0.710516

0.706663

0.744343

0.72870 (10)

0.69061 (17)

0.698848

0.713461

0.726779

0.681833

0.60041 (19)

0.48212 (11)

0.48802 (12)

0.518624

0.503210

0.445985

0.43195 (11)

0.426343

0.390972

0.446509

0.45858 (13)

0.491673

0.419136

0.449982

0.43645 (8)

0.48615 (14)

0.518373

0.508047

0.528618

0.487236

0.44951 (19)

0.0227 (5)

0.0344 (7)

0.052*

0.0254 (6)

0.038*

0.0353 (7)

0.053*

0.0267 (4)

0.0447 (8)

0.054*

0.0518 (13)

0.008758

0.004061

0.0624 (2)

0.055972

0.033964

0.123149

0.30804 (12)

0.2868 (2)

0.333025

0.233028

0.305021

C31E

H31M

H31N

H31P

H31Q

C32E

0.809 (6)

0.191 (6)

0.809 (6)

0.224472

0.2772 (3)

Acta Cryst. (2018). C74, 548-557

sup-8

supporting information

H32M

H32N

C32F

H32P

H32Q

C33E

H33M

H33N

H33P

H33Q

C34E

H34M

H34N

O4E

C35E

H35M

H35N

C36E

H36M

H36N

C37E

H37M

H37N

C38E

H38M

H38N

0.564641

0.589055

0.6086 (7)

0.614213

0.566099

0.58647 (19)

0.549235

0.561549

0.562664

0.547602

0.67171 (16)

0.673140

0.686864

0.87436 (11)

0.88202 (18)

0.848767

0.940658

0.84882 (17)

0.787393

0.869488

0.88378 (17)

0.941683

0.286217

0.219956

0.3330 (12)

0.388267

0.298102

0.3462 (3)

0.325667

0.397554

0.294108

0.394513

0.36607 (19)

0.356814

0.477814

0.429683

0.4705 (3)

0.493401

0.482031

0.39872 (17)

0.357354

0.412111

0.374721

0.384336

0.39269 (14)

0.348077

0.404695

0.41964 (8)

0.35987 (13)

0.322356

0.359561

0.35929 (13)

0.345485

0.062*

0.0518 (13)

0.062*

0.0567 (10)

0.068*

0.0344 (7)

0.041*

0.0211 (4)

0.0282 (6)

0.034*

0.0307 (6)

0.037*

0.0290 (6)

0.035*

0.809 (6)

0.191 (6)

0.809 (6)

0.191 (6)

0.426089

0.39055 (10)

0.42680 (16)

0.393951

0.427443

0.51645 (17)

0.517206

0.554238

0.54225 (16)

0.562697

0.330910

0.42958 (13)

0.438888

0.441030

0.46561 (12)

0.502720

0.481454

0.849637

0.87957 (17)

0.929753

0.587506

0.035*

0.0262 (6)

0.031*

0.45984 (16)

0.453406

0.459822

0.830143

0.031*

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

Mg1

O1A

C1A

C2A

C3A

C4A

C5A

C6A

C7A

C8A

C9A

C10A

C11A

C12A

C13A

C14A

C15A

O2A

0.0163 (4)

0.0231 (9)

0.0142 (11)

0.0192 (12)

0.0205 (12)

0.0193 (12)

0.0185 (12)

0.0151 (11)

0.0386 (15)

0.0300 (15)

0.072 (2)

0.0144 (4)

0.0186 (8)

0.0172 (11)

0.0179 (11)

0.0155 (11)

0.0168 (11)

0.0206 (12)

0.0167 (11)

0.0224 (13)

0.0477 (18)

0.0289 (15)

0.0168 (12)

0.0219 (12)

0.0177 (11)

0.0247 (14)

0.0187 (12)

0.0237 (13)

0.0154 (8)

0.0133 (4)

0.0145 (8)

0.0142 (11)

0.0156 (12)

0.0186 (12)

0.0178 (12)

0.0161 (12)

0.0174 (11)

0.0155 (12)

0.0248 (15)

0.0199 (14)

0.0202 (13)

0.0159 (12)

0.0185 (12)

0.0201 (13)

0.0251 (14)

0.0281 (14)

0.0148 (8)

−0.0007 (3)

0.0047 (3)

0.0060 (7)

0.0062 (8)

0.0057 (9)

0.0075 (9)

0.0078 (9)

0.0044 (9)

0.0064 (9)

0.0034 (11)

−0.0043 (12)

0.0069 (14)

0.0175 (13)

0.0048 (10)

0.0051 (9)

0.0001 (11)

0.0113 (11)

0.0096 (11)

0.0059 (7)

−0.0021 (3)

0.0003 (7)

0.0001 (9)

−0.0012 (9)

−0.0003 (9)

0.0021 (9)

−0.0027 (9)

−0.0030 (9)

−0.0018 (10)

0.0025 (13)

−0.0047 (12)

−0.0054 (10)

0.0027 (10)

−0.0043 (10)

−0.0071 (11)

−0.0041 (10)

−0.0037 (11)

−0.0023 (6)

−0.0029 (7)

−0.0007 (9)

−0.0044 (10)

−0.0015 (10)

0.0017 (9)

−0.0011 (10)

−0.0027 (9)

−0.0160 (12)

−0.0187 (14)

−0.0302 (16)

−0.0100 (13)

0.0004 (11)

−0.0044 (10)

−0.0099 (12)

0.0005 (11)

−0.0102 (11)

0.0032 (7)

0.063 (2)

0.0309 (14)

0.0204 (12)

0.0382 (16)

0.0320 (14)

0.0240 (13)

0.0236 (8)

Acta Cryst. (2018). C74, 548-557

sup-9

supporting information

C16A

C17A

C18A

C19A

C20A

C21A

C22A

C23A

C24A

C25A

C26A

C27A

C28A

C29A

C30A

C28B

C29B

C30B

O3A

C31A

C32A

C33A

C34A

O4A

C35A

C36A

C37A

C38A

Mg2

0.0210 (11)

0.0210 (12)

0.0220 (12)

0.0257 (13)

0.0220 (12)

0.0203 (12)

0.0194 (12)

0.0223 (13)

0.0213 (13)

0.0315 (14)

0.0333 (15)

0.0157 (11)

0.0154 (15)

0.0207 (17)

0.038 (2)

0.0118 (10)

0.0141 (11)

0.0171 (11)

0.0191 (12)

0.0159 (11)

0.0146 (10)

0.0209 (12)

0.0343 (14)

0.0404 (16)

0.0246 (13)

0.0218 (13)

0.0193 (11)

0.0333 (18)

0.0288 (18)

0.035 (2)

0.0104 (10)

0.0133 (11)

0.0161 (12)

0.0175 (12)

0.0192 (12)

0.0130 (11)

0.0150 (11)

0.0201 (13)

0.0172 (12)

0.0267 (14)

0.0276 (14)

0.0170 (11)

0.0287 (18)

0.031 (2)

0.0004 (9)

0.0005 (9)

0.0055 (9)

0.0053 (9)

0.0047 (9)

0.0068 (10)

0.0082 (10)

0.0047 (9)

0.0039 (9)

0.0070 (10)

0.0018 (10)

0.0056 (11)

0.0102 (11)

0.0063 (9)

0.0034 (13)

−0.0002 (14)

0.0141 (15)

0.0034 (13)

−0.0002 (14)

0.0141 (15)

0.0092 (7)

0.0074 (11)

0.0086 (11)

0.0058 (11)

0.0167 (12)

0.0067 (7)

0.0059 (11)

0.0062 (12)

0.0158 (13)

0.0152 (12)

0.0046 (3)

0.0059 (7)

0.0081 (9)

0.0066 (9)

0.0038 (10)

0.0079 (10)

0.0088 (10)

0.0052 (10)

0.0058 (10)

0.0109 (12)

0.0087 (10)

0.0005 (12)

0.0070 (11)

0.0044 (11)

0.0035 (15)

−0.0008 (11)

0.0109 (12)

0.0054 (6)

0.0080 (9)

0.0060 (9)

0.0006 (8)

0.0018 (9)

−0.0012 (10)

0.0021 (10)

0.0028 (10)

−0.0004 (9)

0.0037 (10)

−0.0018 (11)

0.0031 (12)

0.0101 (12)

0.0015 (12)

0.0011 (10)

−0.0028 (15)

0.0071 (14)

−0.0128 (18)

−0.0028 (15)

0.0071 (14)

−0.0128 (18)

−0.0016 (7)

−0.0029 (11)

0.0001 (11)

−0.0028 (12)

−0.0046 (12)

0.0027 (8)

0.0068 (12)

0.0061 (13)

0.0014 (14)

0.0024 (13)

0.0004 (3)

0.0033 (7)

0.0024 (9)

0.0037 (9)

0.0036 (10)

0.0018 (10)

0.0093 (11)

0.0068 (10)

0.0062 (10)

−0.0022 (11)

0.0095 (10)

0.0118 (12)

0.0035 (11)

0.0166 (12)

0.0370 (17)

0.0196 (14)

0.0074 (13)

−0.0024 (7)

−0.0003 (9)

−0.0017 (9)

−0.0021 (9)

−0.0044 (10)

−0.0009 (9)

0.0002 (9)

−0.0002 (9)

−0.0060 (11)

−0.0044 (11)

0.0064 (11)

−0.0107 (11)

0.0007 (9)

−0.0138 (15)

−0.0033 (14)

0.0017 (16)

−0.0138 (15)

−0.0033 (14)

0.0017 (16)

−0.0019 (7)

−0.0055 (10)

−0.0002 (10)

0.0051 (11)

−0.0014 (11)

−0.0026 (7)

−0.0007 (12)

−0.0097 (14)

−0.0006 (16)

−0.0066 (12)

0.0020 (3)

−0.0006 (6)

0.0004 (9)

0.0042 (9)

0.0001 (10)

−0.0022 (10)

0.0008 (10)

0.0016 (9)

0.0035 (10)

0.0070 (11)

0.0036 (11)

0.0052 (11)

−0.0025 (10)

0.0008 (10)

0.0028 (12)

−0.0010 (12)

0.0048 (10)

0.0022 (6)

0.032 (2)

0.0287 (18)

0.031 (2)

0.0154 (15)

0.0207 (17)

0.038 (2)

0.0333 (18)

0.0288 (18)

0.035 (2)

0.032 (2)

0.0289 (9)

0.0355 (15)

0.0302 (14)

0.0329 (14)

0.0431 (16)

0.0182 (9)

0.0244 (14)

0.0213 (14)

0.0225 (14)

0.0269 (14)

0.0160 (4)

0.0218 (8)

0.0171 (11)

0.0163 (11)

0.0208 (12)

0.0244 (13)

0.0278 (13)

0.0235 (13)

0.0220 (12)

0.0334 (15)

0.0212 (12)

0.0378 (16)

0.0330 (14)

0.0412 (16)

0.079 (2)

0.0150 (8)

0.0159 (12)

0.0160 (12)

0.0229 (13)

0.0208 (13)

0.0284 (9)

0.0282 (14)

0.0423 (17)

0.054 (2)

0.0444 (17)

0.0149 (4)

0.0174 (8)

0.0169 (11)

0.0164 (11)

0.0235 (12)

0.0217 (12)

0.0185 (12)

0.0204 (12)

0.0171 (11)

0.0217 (13)

0.0219 (12)

0.0277 (14)

0.0251 (13)

0.0239 (13)

0.0334 (16)

0.0495 (18)

0.0199 (13)

0.0163 (8)

0.0140 (11)

0.0174 (11)

0.0187 (9)

0.0240 (13)

0.0295 (14)

0.0254 (14)

0.0239 (14)

0.0210 (9)

0.0339 (15)

0.0407 (17)

0.0453 (18)

0.0262 (14)

0.0136 (4)

0.0141 (8)

0.0170 (11)

0.0162 (11)

0.0155 (12)

0.0172 (12)

0.0200 (12)

0.0141 (12)

0.0195 (12)

0.0307 (15)

0.0291 (14)

0.0232 (14)

0.0171 (12)

0.0150 (12)

0.0237 (15)

0.0204 (14)

0.0189 (13)

0.0142 (8)

0.0135 (11)

0.0133 (11)

O1C

C1C

C2C

C3C

C4C

C5C

C6C

C7C

C8C

C9C

C10C

C11C

C12C

C13C

C14C

C15C

O2C

0.0288 (15)

0.0528 (18)

0.0201 (8)

0.0197 (11)

0.0194 (12)

C16C

C17C

−0.0012 (9)

−0.0015 (9)

Acta Cryst. (2018). C74, 548-557

sup-10

supporting information

C18C

C19C

C20C

C21C

C22C

C23C

C24C

C25C

C23D

C24D

C25D

C26C

C27C

C28C

C29C

C30C

O3C

C31C

C32C

C33C

C34C

O4C

C35C

C36C

C37C

C38C

Mg3

0.0244 (13)

0.0321 (14)

0.0285 (14)

0.0218 (12)

0.0151 (11)

0.0206 (14)

0.0221 (15)

0.0186 (14)

0.0206 (14)

0.0221 (15)

0.0186 (14)

0.0446 (17)

0.0187 (12)

0.0246 (14)

0.0256 (14)

0.0209 (13)

0.0271 (9)

0.0333 (14)

0.0267 (14)

0.0273 (14)

0.0305 (14)

0.0183 (9)

0.0274 (15)

0.0245 (15)

0.0223 (14)

0.0239 (13)

0.0174 (4)

0.0203 (12)

0.0231 (13)

0.0251 (13)

0.0210 (12)

0.0211 (12)

0.0304 (15)

0.0202 (15)

0.0451 (19)

0.0304 (15)

0.0202 (15)

0.0451 (19)

0.0333 (16)

0.0242 (13)

0.0518 (19)

0.0309 (15)

0.0372 (15)

0.0149 (8)

0.0165 (12)

0.0154 (12)

0.0226 (13)

0.0205 (13)

0.0273 (10)

0.0454 (17)

0.062 (2)

0.0232 (13)

0.0206 (13)

0.0165 (12)

0.0119 (11)

0.0194 (12)

0.0314 (16)

0.0472 (19)

0.0170 (14)

0.0314 (16)

0.0472 (19)

0.0170 (14)

0.0351 (16)

0.0160 (12)

0.0180 (13)

0.0321 (15)

0.0201 (13)

0.0220 (9)

0.0267 (14)

0.0430 (17)

0.0350 (16)

0.0299 (14)

0.0224 (9)

0.0281 (15)

0.051 (2)

0.0425 (18)

0.0327 (15)

0.0138 (4)

0.0146 (8)

0.0125 (11)

0.0135 (11)

0.0206 (12)

0.0174 (12)

0.0145 (12)

0.0142 (11)

0.0191 (12)

0.0385 (17)

0.0345 (16)

0.0311 (15)

0.0285 (14)

0.0150 (12)

0.0195 (13)

0.0217 (13)

0.0338 (15)

0.0155 (8)

−0.0039 (10)

0.0009 (11)

0.0026 (11)

−0.0014 (10)

−0.0024 (10)

−0.0042 (12)

0.0024 (12)

−0.0049 (13)

−0.0042 (12)

0.0024 (12)

−0.0049 (13)

0.0011 (14)

−0.0009 (10)

−0.0016 (13)

−0.0092 (12)

0.0038 (11)

0.0026 (7)

0.0040 (11)

0.0006 (11)

−0.0017 (11)

0.0028 (11)

−0.0031 (7)

−0.0042 (13)

−0.0040 (15)

−0.0097 (13)

−0.0061 (12)

0.0008 (3)

0.0032 (7)

−0.0001 (9)

0.0014 (9)

0.0051 (10)

0.0016 (11)

−0.0019 (10)

0.0013 (9)

0.0006 (10)

−0.0094 (13)

−0.0036 (12)

0.0036 (12)

0.0009 (12)

0.0044 (10)

0.0024 (12)

−0.0027 (12)

0.0098 (12)

−0.0005 (7)

−0.0007 (9)

−0.0027 (9)

−0.0019 (10)

−0.0003 (10)

0.0108 (10)

0.0092 (11)

0.0054 (10)

0.0054 (9)

0.0070 (9)

0.0118 (12)

0.0130 (13)

0.0037 (11)

0.0118 (12)

0.0130 (13)

0.0037 (11)

0.0158 (13)

0.0038 (9)

−0.0002 (11)

0.0053 (11)

0.0066 (10)

0.0095 (7)

0.0069 (11)

0.0102 (12)

0.0077 (12)

0.0139 (12)

0.0070 (7)

0.0162 (12)

0.0172 (14)

0.0051 (12)

0.0039 (11)

0.0048 (3)

0.0064 (6)

0.0064 (9)

0.0059 (9)

0.0105 (10)

0.0090 (10)

0.0045 (10)

0.0044 (9)

0.0083 (9)

0.0184 (13)

0.0071 (11)

0.0041 (11)

0.0118 (12)

0.0004 (9)

−0.0009 (10)

0.0065 (10)

0.0018 (12)

0.0049 (7)

0.0064 (9)

0.0077 (9)

0.0050 (9)

0.0073 (9)

0.0024 (10)

0.0068 (10)

0.0047 (10)

−0.0019 (9)

0.0000 (10)

0.0024 (13)

0.0010 (13)

−0.0015 (13)

0.0024 (13)

0.0010 (13)

−0.0015 (13)

0.0197 (13)

−0.0010 (10)

0.0039 (13)

−0.0103 (12)

0.0046 (11)

0.0035 (7)

0.0058 (11)

0.0039 (11)

−0.0075 (12)

−0.0018 (11)

0.0015 (7)

0.0057 (13)

−0.0055 (17)

0.0081 (14)

−0.0024 (12)

−0.0022 (3)

−0.0023 (6)

0.0015 (9)

0.0013 (9)

0.0000 (9)

−0.0055 (10)

−0.0030 (9)

0.0026 (9)

0.0005 (10)

0.0030 (13)

−0.0153 (13)

0.0021 (12)

−0.0129 (12)

−0.0007 (9)

−0.0020 (11)

−0.0059 (11)

0.0063 (12)

0.0022 (7)

0.0440 (18)

0.0276 (14)

0.0162 (5)

O1E

C1E

C2E

C3E

C4E

C5E

C6E

C7E

0.0210 (8)

0.0173 (8)

0.0203 (11)

0.0207 (12)

0.0232 (12)

0.0308 (13)

0.0267 (13)

0.0202 (12)

0.0162 (11)

0.0380 (16)

0.0204 (13)

0.0247 (14)

0.0351 (15)

0.0187 (12)

0.0216 (13)

0.0198 (12)

0.0327 (15)

0.0230 (9)

0.0115 (10)

0.0146 (11)

0.0175 (11)

0.0200 (12)

0.0196 (12)

0.0151 (11)

0.0200 (11)

0.0314 (15)

0.0389 (16)

0.0313 (15)

0.0284 (14)

0.0219 (12)

0.0385 (16)

0.0375 (15)

0.0254 (14)

0.0190 (9)

C8E

C9E

C10E

C11E

C12E

C13E

C14E

C15E

O2E

C16E

C17E

C18E

C19E

0.0151 (11)

0.0173 (11)

0.0195 (12)

0.0212 (12)

0.0192 (12)

0.0169 (11)

0.0199 (12)

0.0184 (12)

0.0139 (11)

0.0167 (11)

0.0147 (11)

0.0156 (11)

−0.0008 (9)

−0.0024 (9)

−0.0027 (9)

0.0018 (9)

Acta Cryst. (2018). C74, 548-557

sup-11

supporting information

C20E

C21E

C22E

C23E

C24E

C25E

C26E

C27E

C28E

C29E

C30E

O3E

C31E

C32E

C32F

C33E

C34E

O4E

0.0191 (12)

0.0166 (11)

0.0246 (13)

0.0401 (16)

0.0289 (14)

0.0431 (16)

0.0355 (15)

0.0253 (13)

0.0508 (18)

0.0407 (15)

0.0258 (14)

0.0194 (9)

0.0333 (16)

0.0252 (19)

0.0245 (17)

0.0223 (14)

0.0290 (9)

0.0166 (11)

0.0218 (12)

0.0170 (12)

0.0205 (13)

0.0210 (12)

0.0251 (14)

0.0200 (13)

0.0251 (13)

0.0303 (15)

0.0201 (12)

0.0515 (19)

0.0345 (11)

0.068 (2)

0.058 (3)

0.078 (3)

0.0372 (16)

0.0155 (8)

0.0232 (13)

0.0267 (14)

0.0166 (12)

0.0198 (13)

0.0195 (12)

0.0152 (11)

0.0170 (12)

0.0270 (14)

0.0275 (14)

0.0218 (13)

0.0182 (12)

0.0169 (12)

0.0195 (14)

0.0173 (12)

0.0234 (14)

0.0272 (10)

0.0414 (18)

0.079 (3)

−0.0045 (9)

−0.0051 (10)

−0.0056 (10)

0.0022 (12)

−0.0098 (11)

−0.0150 (13)

−0.0023 (11)

−0.0113 (11)

−0.0225 (14)

−0.0096 (12)

−0.0107 (14)

0.0056 (8)

0.0104 (16)

−0.005 (2)

0.0106 (17)

0.0106 (13)

−0.0007 (7)

−0.0052 (12)

−0.0018 (12)

0.0014 (11)

−0.0004 (11)

0.0084 (9)

0.0068 (9)

0.0066 (10)

0.0135 (12)

0.0113 (11)

0.0051 (12)

0.0058 (11)

0.0050 (10)

0.0063 (12)

0.0115 (11)

−0.0010 (11)

0.0083 (7)

0.0241 (14)

0.027 (2)

−0.0024 (9)

−0.0030 (9)

−0.0027 (9)

−0.0046 (11)

−0.0028 (11)

−0.0068 (11)

0.0022 (10)

−0.0034 (10)

−0.0038 (11)

−0.0064 (10)

−0.0015 (13)

−0.0022 (8)

0.0014 (17)

−0.010 (2)

0.079 (3)

0.067 (3)

0.027 (2)

−0.010 (2)

0.002 (2)

0.0119 (16)

0.0039 (12)

0.0084 (7)

0.0131 (12)

0.0045 (12)

0.0123 (12)

0.0066 (11)

0.0402 (17)

0.0197 (9)

0.0259 (14)

0.0343 (16)

0.0387 (16)

0.0245 (13)

−0.0012 (14)

−0.0026 (7)

0.0005 (11)

0.0076 (12)

−0.0016 (11)

−0.0063 (10)

C35E

C36E

C37E

C38E

0.0379 (16)

0.0282 (14)

0.0328 (15)

0.0330 (14)

Geometric parameters (Å, º)

Mg1—O1A

Mg1—O2A

Mg1—O3A

Mg1—O4A

O1A—C1A

C1A—C2A

C1A—C6A

C2A—C3A

C2A—C7A

C3A—C4A

C3A—H3A

C4A—C5A

C4A—C11A

C5A—C6A

C5A—H5A

C6A—C12A

C7A—C8A

C7A—C9A

C7A—C10A

C8A—H8A

C8A—H8B

C8A—H8C

C9A—H9A

1.8575 (17)

C22C—C25D

C22C—C23C

C22C—C24C

C23C—H23G

C23C—H23H

C23C—H23I

C24C—H24G

C24C—H24H

C24C—H24I

C25C—H25G

C25C—H25H

C25C—H25I

C23D—H23J

C23D—H23K

C23D—H23L

C24D—H24J

C24D—H24K

C24D—H24L

C25D—H25J

C25D—H25K

C25D—H25L

C26C—H26G

C26C—H26H

1.538 (4)

1.8653 (16)

2.0438 (18)

2.0595 (18)

1.331 (3)

1.428 (3)

1.440 (3)

1.399 (3)

1.541 (3)

1.392 (3)

0.9500

1.393 (3)

1.510 (3)

1.396 (3)

0.9500

1.536 (3)

1.540 (4)

1.542 (4)

0.9800

1.538 (3)

1.539 (3)

0.9800

Acta Cryst. (2018). C74, 548-557

sup-12

supporting information

C9A—H9B

C9A—H9C

0.9800

1.540 (3)

1.541 (3)

1.546 (3)

0.9800

C26C—H26I

C27C—C29C

C27C—C30C

C27C—C28C

C28C—H28G

C28C—H28H

C28C—H28I

C29C—H29G

C29C—H29H

C29C—H29I

C30C—H30G

C30C—H30H

C30C—H30I

O3C—C34C

O3C—C31C

C31C—C32C

C31C—H31G

C31C—H31H

C32C—C33C

C32C—H32G

C32C—H32H

C33C—C34C

C33C—H33G

C33C—H33H

C34C—H34G

C34C—H34H

O4C—C35C

O4C—C38C

C35C—C36C

C35C—H35G

C35C—H35H

C36C—C37C

C36C—H36G

C36C—H36H

C37C—C38C

C37C—H37G

C37C—H37H

C38C—H38G

C38C—H38H

Mg3—O2E

0.9800

1.536 (4)

1.536 (3)

1.545 (3)

0.9800

1.461 (3)

1.466 (3)

1.528 (3)

0.9900

1.530 (4)

0.9900

1.512 (4)

0.9900

1.454 (3)

1.458 (3)

1.530 (4)

0.9900

1.522 (4)

0.9900

1.528 (4)

0.9900

C10A—H10A

C10A—H10B

C10A—H10C

C11A—H11A

C11A—H11B

C11A—H11C

C12A—C14A

C12A—C15A

C12A—C13A

C13A—H13A

C13A—H13B

C13A—H13C

C14A—H14A

C14A—H14B

C14A—H14C

C15A—H15A

C15A—H15B

C15A—H15C

O2A—C16A

C16A—C21A

C16A—C17A

C17A—C18A

C17A—C22A

C18A—C19A

C18A—H18A

C19A—C20A

C19A—C26A

C20A—C21A

C20A—H20A

C21A—C27A

C22A—C23A

C22A—C25A

C22A—C24A

C23A—H23A

C23A—H23B

C23A—H23C

C24A—H24A

C24A—H24B

C24A—H24C

C25A—H25A

C25A—H25B

C25A—H25C

C26A—H26A

C26A—H26B

C26A—H26C

C27A—C30A

0.9800

1.341 (3)

1.427 (3)

1.440 (3)

1.389 (3)

1.540 (3)

1.395 (3)

0.9500

1.391 (3)

1.518 (3)

1.407 (3)

0.9500

1.548 (3)

1.534 (3)

1.539 (3)

1.546 (3)

0.9800

0.9900

1.8554 (17)

1.8660 (17)

2.0444 (18)

2.0653 (18)

1.334 (3)

1.429 (3)

1.437 (3)

1.406 (3)

1.550 (3)

Mg3—O1E

Mg3—O4E

Mg3—O3E

O1E—C1E

C1E—C2E

C1E—C6E

C2E—C3E

C2E—C7E

0.9800

1.531 (3)

Acta Cryst. (2018). C74, 548-557

sup-13

supporting information

C27A—C28A

C27A—C29B

C27A—C28B

C27A—C29A

C27A—C30B

C28A—H28A

C28A—H28B

C28A—H28C

C29A—H29A

C29A—H29B

C29A—H29C

C30A—H30A

C30A—H30B

C30A—H30C

C28B—H28D

C28B—H28E

C28B—H28F

C29B—H29D

C29B—H29E

C29B—H29F

C30B—H30D

C30B—H30E

C30B—H30F

O3A—C34A

O3A—C31A

C31A—C32A

C31A—H31A

C31A—H31B

C32A—C33A

C32A—H32A

C32A—H32B

C33A—C34A

C33A—H33A

C33A—H33B

C34A—H34A

C34A—H34B

O4A—C38A

O4A—C35A

C35A—C36A

C35A—H35A

C35A—H35B

C36A—C37A

C36A—H36A

C36A—H36B

C37A—C38A

C37A—H37A

C37A—H37B

C38A—H38A

1.533 (3)

1.537 (4)

1.539 (3)

1.539 (4)

0.9800

C3E—C4E

C3E—H3M

C4E—C5E

C4E—C11E

C5E—C6E

C5E—H5M

C6E—C12E

C7E—C9E

C7E—C10E

C7E—C8E

C8E—H8M

C8E—H8N

C8E—H8O

C9E—H9M

C9E—H9N

1.389 (3)

0.9500

1.395 (3)

1.516 (3)

1.393 (3)

0.9500

1.543 (3)

1.532 (3)

1.537 (3)

0.9800

1.533 (3)

1.539 (3)

1.544 (3)

0.9800

C9E—H9O

C10E—H10M

C10E—H10N

C10E—H10O

C11E—H11M

C11E—H11N

C11E—H11O

C12E—C14E

C12E—C15E

C12E—C13E

C13E—H13M

C13E—H13N

C13E—H13O

C14E—H14M

C14E—H14N

C14E—H14O

C15E—H15M

C15E—H15N

C15E—H15O

O2E—C16E

C16E—C21E

C16E—C17E

C17E—C18E

C17E—C22E

C18E—C19E

C18E—H18M

C19E—C20E

C19E—C26E

C20E—C21E

C20E—H20M

C21E—C27E

C22E—C23E

C22E—C24E

0.9800

1.462 (3)

1.464 (3)

1.527 (3)

0.9900

1.531 (4)

0.9900

1.512 (4)

0.9900

1.334 (3)

1.433 (3)

1.434 (3)

1.395 (3)

1.541 (3)

1.392 (3)

0.9500

1.388 (3)

1.508 (3)

1.398 (3)

0.9500

0.9900

1.454 (3)

1.457 (3)

1.528 (4)

0.9900

1.529 (4)

0.9900

1.527 (4)

0.9900

1.542 (3)

1.537 (4)

1.541 (3)

Acta Cryst. (2018). C74, 548-557

sup-14

supporting information

C38A—H38B

Mg2—O1C

Mg2—O2C

Mg2—O3C

Mg2—O4C

O1C—C1C

C1C—C6C

C1C—C2C

C2C—C3C

C2C—C7C

C3C—C4C

C3C—H3G

C4C—C5C

C4C—C11C

C5C—C6C

C5C—H5G

C6C—C12C

C7C—C10C

C7C—C8C

0.9900

C22E—C25E

C23E—H23M

C23E—H23N

C23E—H23O

C24E—H24M

C24E—H24N

C24E—H24O

C25E—H25M

C25E—H25N

C25E—H25O

C26E—H26M

C26E—H26N

C26E—H26O

C27E—C29E

C27E—C28E

C27E—C30E

C28E—H28M

C28E—H28N

C28E—H28O

C29E—H29M

C29E—H29N

C29E—H29O

C30E—H30M

C30E—H30N

C30E—H30O

O3E—C31E

1.541 (3)

0.9800

1.535 (3)

1.538 (3)

1.543 (4)

0.9800

1.449 (3)

1.458 (3)

1.504 (4)

1.509 (4)

0.9900

1.517 (4)

0.9900

1.513 (5)

0.9900

1.512 (4)

0.9900

1.461 (3)

1.463 (3)

1.8557 (17)

1.8639 (17)

2.0502 (18)

2.0699 (18)

1.333 (3)

1.430 (3)

1.435 (3)

1.394 (3)

1.546 (3)

1.389 (3)

0.9500

1.388 (3)

1.516 (3)

1.403 (3)

0.9500

1.543 (3)

1.538 (3)

1.541 (3)

1.543 (3)

0.9800

1.541 (4)

1.544 (4)

0.9800

C7C—C9C

C8C—H8G

C8C—H8H

C8C—H8I

C9C—H9H

C9C—H9I

C9C—H9J

C10C—H10G

C10C—H10H

C10C—H10I

C11C—H11G

C11C—H11H

C11C—H11I

C12C—C15C

C12C—C13C

C12C—C14C

C13C—H13G

C13C—H13H

C13C—H13I

C14C—H14G

C14C—H14H

C14C—H14I

C15C—H15G

C15C—H15H

C15C—H15I

O2C—C16C

C16C—C17C

C16C—C21C

C17C—C18C

O3E—C34E

C31E—C32E

C31E—C32F

C31E—H31M

C31E—H31N

C31E—H31P

C31E—H31Q

C32E—C33E

C32E—H32M

C32E—H32N

C32F—C33E

C32F—H32P

C32F—H32Q

C33E—C34E

C33E—H33M

C33E—H33N

C33E—H33P

C33E—H33Q

C34E—H34M

C34E—H34N

O4E—C35E

0.9800

1.341 (3)

1.432 (3)

1.433 (3)

1.401 (3)

O4E—C38E

Acta Cryst. (2018). C74, 548-557

sup-15

supporting information

C17C—C22C

C18C—C19C

C18C—H18G

C19C—C20C

C19C—C26C

C20C—C21C

C20C—H20G

C21C—C27C

C22C—C25C

C22C—C23D

C22C—C24D

1.545 (3)

1.388 (3)

0.9500

1.393 (4)

1.518 (3)

1.399 (3)

0.9500

1.543 (3)

1.534 (2)

1.537 (4)

C35E—C36E

C35E—H35M

C35E—H35N

C36E—C37E

C36E—H36M

C36E—H36N

C37E—C38E

C37E—H37M

C37E—H37N

C38E—H38M

C38E—H38N

1.512 (4)

0.9900

1.526 (4)

0.9900

1.524 (4)

0.9900

O1A—Mg1—O2A

O1A—Mg1—O3A

O2A—Mg1—O3A

O1A—Mg1—O4A

O2A—Mg1—O4A

O3A—Mg1—O4A

C1A—O1A—Mg1

O1A—C1A—C2A

O1A—C1A—C6A

C2A—C1A—C6A

C3A—C2A—C1A

C3A—C2A—C7A

C1A—C2A—C7A

C4A—C3A—C2A

C4A—C3A—H3A

C2A—C3A—H3A

C3A—C4A—C5A

C3A—C4A—C11A

C5A—C4A—C11A

C4A—C5A—C6A

C4A—C5A—H5A

C6A—C5A—H5A

C5A—C6A—C1A

C5A—C6A—C12A

C1A—C6A—C12A

C8A—C7A—C9A

C8A—C7A—C2A

C9A—C7A—C2A

C8A—C7A—C10A

C9A—C7A—C10A

C2A—C7A—C10A

C7A—C8A—H8A

C7A—C8A—H8B

H8A—C8A—H8B

C7A—C8A—H8C

H8A—C8A—H8C

125.31 (8)

124.33 (8)

98.36 (7)

98.34 (7)

116.34 (8)

89.26 (7)

174.09 (15)

121.33 (19)

119.9 (2)

118.8 (2)

118.9 (2)

119.0 (2)

122.1 (2)

123.2 (2)

118.4

H23G—C23C—H23H

C22C—C23C—H23I

H23G—C23C—H23I

H23H—C23C—H23I

C22C—C24C—H24G

C22C—C24C—H24H

H24G—C24C—H24H

C22C—C24C—H24I

H24G—C24C—H24I

H24H—C24C—H24I

C22C—C25C—H25G

C22C—C25C—H25H

H25G—C25C—H25H

C22C—C25C—H25I

H25G—C25C—H25I

H25H—C25C—H25I

C22C—C23D—H23J

C22C—C23D—H23K

H23J—C23D—H23K

C22C—C23D—H23L

H23J—C23D—H23L

H23K—C23D—H23L

C22C—C24D—H24J

C22C—C24D—H24K

H24J—C24D—H24K

C22C—C24D—H24L

H24J—C24D—H24L

H24K—C24D—H24L

C22C—C25D—H25J

C22C—C25D—H25K

H25J—C25D—H25K

C22C—C25D—H25L

H25J—C25D—H25L

H25K—C25D—H25L

C19C—C26C—H26G

C19C—C26C—H26H

109.5

118.4

117.2 (2)

120.8 (2)

122.1 (2)

123.3 (2)

118.3

118.6 (2)

119.7 (2)

121.7 (2)

107.4 (2)

109.7 (2)

111.9 (2)

110.9 (2)

106.0 (2)

110.9 (2)

109.5

Acta Cryst. (2018). C74, 548-557

sup-16

supporting information

H8B—C8A—H8C

109.5

H26G—C26C—H26H

109.5

C7A—C9A—H9A

C7A—C9A—H9B

H9A—C9A—H9B

C7A—C9A—H9C

H9A—C9A—H9C

H9B—C9A—H9C

109.5

C19C—C26C—H26I

H26G—C26C—H26I

H26H—C26C—H26I

C29C—C27C—C30C

C29C—C27C—C21C

C30C—C27C—C21C

C29C—C27C—C28C

C30C—C27C—C28C

C21C—C27C—C28C

C27C—C28C—H28G

C27C—C28C—H28H

H28G—C28C—H28H

C27C—C28C—H28I

H28G—C28C—H28I

H28H—C28C—H28I

C27C—C29C—H29G

C27C—C29C—H29H

H29G—C29C—H29H

C27C—C29C—H29I

H29G—C29C—H29I

H29H—C29C—H29I

C27C—C30C—H30G

C27C—C30C—H30H

H30G—C30C—H30H

C27C—C30C—H30I

H30G—C30C—H30I

H30H—C30C—H30I

C34C—O3C—C31C

C34C—O3C—Mg2

109.5

112.4 (2)

108.4 (2)

111.15 (19)

106.7 (2)

105.6 (2)

112.5 (2)

109.5

C7A—C10A—H10A

C7A—C10A—H10B

H10A—C10A—H10B

C7A—C10A—H10C

H10A—C10A—H10C

H10B—C10A—H10C

C4A—C11A—H11A

C4A—C11A—H11B

H11A—C11A—H11B

C4A—C11A—H11C

H11A—C11A—H11C

H11B—C11A—H11C

C6A—C12A—C14A

C6A—C12A—C15A

C14A—C12A—C15A

C6A—C12A—C13A

C14A—C12A—C13A

C15A—C12A—C13A

C12A—C13A—H13A

C12A—C13A—H13B

H13A—C13A—H13B

C12A—C13A—H13C

H13A—C13A—H13C

H13B—C13A—H13C

C12A—C14A—H14A

C12A—C14A—H14B

H14A—C14A—H14B

C12A—C14A—H14C

H14A—C14A—H14C

H14B—C14A—H14C

C12A—C15A—H15A

C12A—C15A—H15B

H15A—C15A—H15B

C12A—C15A—H15C

H15A—C15A—H15C

H15B—C15A—H15C

C16A—O2A—Mg1

O2A—C16A—C21A

O2A—C16A—C17A

C21A—C16A—C17A

C18A—C17A—C16A

109.5

110.80 (19)

110.23 (19)

110.6 (2)

112.5 (2)

105.9 (2)

106.6 (2)

109.5

108.36 (18)

124.33 (14)

125.52 (14)

106.21 (19)

110.5

108.7

103.2 (2)

111.1

109.1

101.6 (2)

111.4

C31C—O3C—Mg2

O3C—C31C—C32C

O3C—C31C—H31G

C32C—C31C—H31G

O3C—C31C—H31H

C32C—C31C—H31H

H31G—C31C—H31H

C31C—C32C—C33C

C31C—C32C—H32G

C33C—C32C—H32G

C31C—C32C—H32H

C33C—C32C—H32H

H32G—C32C—H32H

C34C—C33C—C32C

C34C—C33C—H33G

C32C—C33C—H33G

C34C—C33C—H33H

C32C—C33C—H33H

109.5

153.76 (14)

121.66 (19)

119.43 (19)

118.91 (19)

119.0 (2)

111.4

Acta Cryst. (2018). C74, 548-557

sup-17

supporting information

C18A—C17A—C22A

C16A—C17A—C22A

C17A—C18A—C19A

C17A—C18A—H18A

C19A—C18A—H18A

C20A—C19A—C18A

C20A—C19A—C26A

C18A—C19A—C26A

C19A—C20A—C21A

C19A—C20A—H20A

C21A—C20A—H20A

C20A—C21A—C16A

C20A—C21A—C27A

C16A—C21A—C27A

C23A—C22A—C25A

C23A—C22A—C17A

C25A—C22A—C17A

C23A—C22A—C24A

C25A—C22A—C24A

C17A—C22A—C24A

C22A—C23A—H23A

C22A—C23A—H23B

H23A—C23A—H23B

C22A—C23A—H23C

H23A—C23A—H23C

H23B—C23A—H23C

C22A—C24A—H24A

C22A—C24A—H24B

H24A—C24A—H24B

C22A—C24A—H24C

H24A—C24A—H24C

H24B—C24A—H24C

C22A—C25A—H25A

C22A—C25A—H25B

H25A—C25A—H25B

C22A—C25A—H25C

H25A—C25A—H25C

H25B—C25A—H25C

C19A—C26A—H26A

C19A—C26A—H26B

H26A—C26A—H26B

C19A—C26A—H26C

H26A—C26A—H26C

H26B—C26A—H26C

C30A—C27A—C28A

C29B—C27A—C28B

C30A—C27A—C29A

C28A—C27A—C29A

119.8 (2)

121.14 (19)

123.0 (2)

118.5

H33G—C33C—H33H

109.3

104.2 (2)

110.9

O3C—C34C—C33C

O3C—C34C—H34G

C33C—C34C—H34G

O3C—C34C—H34H

C33C—C34C—H34H

H34G—C34C—H34H

C35C—O4C—C38C

C35C—O4C—Mg2

C38C—O4C—Mg2

O4C—C35C—C36C

O4C—C35C—H35G

C36C—C35C—H35G

O4C—C35C—H35H

C36C—C35C—H35H

H35G—C35C—H35H

C37C—C36C—C35C

C37C—C36C—H36G

C35C—C36C—H36G

C37C—C36C—H36H

C35C—C36C—H36H

H36G—C36C—H36H

C36C—C37C—C38C

C36C—C37C—H37G

C38C—C37C—H37G

C36C—C37C—H37H

C38C—C37C—H37H

H37G—C37C—H37H

O4C—C38C—C37C

O4C—C38C—H38G

C37C—C38C—H38G

O4C—C38C—H38H

C37C—C38C—H38H

H38G—C38C—H38H

O2E—Mg3—O1E

118.5

117.4 (2)

121.6 (2)

121.0 (2)

123.2 (2)

118.4

110.9

108.9

105.29 (19)

126.95 (15)

127.77 (15)

102.8 (2)

111.2

109.1

103.5 (2)

111.1

109.0

104.9 (2)

110.8

108.8

106.0 (2)

110.5

108.7

125.01 (8)

124.69 (8)

98.32 (8)

98.22 (8)

116.48 (8)

89.38 (8)

154.25 (15)

122.12 (19)

119.3 (2)

118.5 (2)

114.8 (2)

126.58 (19)

123.3 (2)

118.4

118.4 (2)

115.9 (2)

125.61 (19)

111.4 (2)

111.57 (19)

108.7 (2)

106.0 (2)

106.6 (2)

112.48 (19)

109.5

O2E—Mg3—O4E

O1E—Mg3—O4E

O2E—Mg3—O3E

O1E—Mg3—O3E

O4E—Mg3—O3E

C1E—O1E—Mg3

O1E—C1E—C2E

O1E—C1E—C6E

C2E—C1E—C6E

C3E—C2E—C1E

C3E—C2E—C7E

C1E—C2E—C7E

109.0 (2)

103.7 (5)

108.9 (2)

105.6 (2)

C4E—C3E—C2E

Acta Cryst. (2018). C74, 548-557

sup-18

supporting information

C29B—C27A—C30B

C28B—C27A—C30B

C30A—C27A—C21A

C28A—C27A—C21A

C29B—C27A—C21A

C28B—C27A—C21A

C29A—C27A—C21A

C30B—C27A—C21A

C27A—C28A—H28A

C27A—C28A—H28B

H28A—C28A—H28B

C27A—C28A—H28C

H28A—C28A—H28C

H28B—C28A—H28C

C27A—C29A—H29A

C27A—C29A—H29B

H29A—C29A—H29B

C27A—C29A—H29C

H29A—C29A—H29C

H29B—C29A—H29C

C27A—C30A—H30A

C27A—C30A—H30B

H30A—C30A—H30B

C27A—C30A—H30C

H30A—C30A—H30C

H30B—C30A—H30C

C27A—C28B—H28D

C27A—C28B—H28E

H28D—C28B—H28E

C27A—C28B—H28F

H28D—C28B—H28F

H28E—C28B—H28F

C27A—C29B—H29D

C27A—C29B—H29E

H29D—C29B—H29E

C27A—C29B—H29F

H29D—C29B—H29F

H29E—C29B—H29F

C27A—C30B—H30D

C27A—C30B—H30E

H30D—C30B—H30E

C27A—C30B—H30F

H30D—C30B—H30F

H30E—C30B—H30F

C34A—O3A—C31A

C34A—O3A—Mg1

102.7 (6)

107.4 (6)

106.9 (2)

116.9 (2)

117.8 (4)

113.9 (4)

109.4 (2)

110.3 (5)

109.5

C4E—C3E—H3M

C2E—C3E—H3M

C3E—C4E—C5E

C3E—C4E—C11E

C5E—C4E—C11E

C6E—C5E—C4E

C6E—C5E—H5M

C4E—C5E—H5M

C5E—C6E—C1E

C5E—C6E—C12E

C1E—C6E—C12E

C9E—C7E—C10E

C9E—C7E—C8E

C10E—C7E—C8E

C9E—C7E—C2E

C10E—C7E—C2E

C8E—C7E—C2E

C7E—C8E—H8M

C7E—C8E—H8N

H8M—C8E—H8N

C7E—C8E—H8O

H8M—C8E—H8O

H8N—C8E—H8O

C7E—C9E—H9M

C7E—C9E—H9N

H9M—C9E—H9N

C7E—C9E—H9O

H9M—C9E—H9O

H9N—C9E—H9O

C7E—C10E—H10M

C7E—C10E—H10N

H10M—C10E—H10N

C7E—C10E—H10O

H10M—C10E—H10O

H10N—C10E—H10O

C4E—C11E—H11M

C4E—C11E—H11N

H11M—C11E—H11N

C4E—C11E—H11O

H11M—C11E—H11O

H11N—C11E—H11O

C14E—C12E—C15E

C14E—C12E—C6E

C15E—C12E—C6E

C14E—C12E—C13E

C15E—C12E—C13E

C6E—C12E—C13E

C12E—C13E—H13M

118.3

117.5 (2)

121.7 (2)

120.8 (2)

122.6 (2)

118.7

119.5 (2)

119.6 (2)

120.92 (19)

105.6 (2)

107.6 (2)

108.0 (2)

116.79 (19)

110.7 (2)

107.84 (19)

109.5

108.27 (17)

123.21 (14)

127.25 (14)

106.42 (19)

111.1 (2)

111.43 (19)

109.0 (2)

106.3 (2)

112.55 (19)

109.5

C31A—O3A—Mg1

O3A—C31A—C32A

Acta Cryst. (2018). C74, 548-557

sup-19

supporting information

O3A—C31A—H31A

C32A—C31A—H31A

O3A—C31A—H31B

C32A—C31A—H31B

H31A—C31A—H31B

C31A—C32A—C33A

C31A—C32A—H32A

C33A—C32A—H32A

C31A—C32A—H32B

C33A—C32A—H32B

H32A—C32A—H32B

C34A—C33A—C32A

C34A—C33A—H33A

C32A—C33A—H33A

C34A—C33A—H33B

C32A—C33A—H33B

H33A—C33A—H33B

O3A—C34A—C33A

O3A—C34A—H34A

C33A—C34A—H34A

O3A—C34A—H34B

C33A—C34A—H34B

H34A—C34A—H34B

C38A—O4A—C35A

C38A—O4A—Mg1

110.4

108.6

103.5 (2)

111.1

109.0

101.8 (2)

111.4

109.3

104.1 (2)

110.9

109.0

105.51 (19)

127.50 (15)

126.88 (15)

106.5 (2)

110.4

108.6

104.8 (2)

110.8

C12E—C13E—H13N

109.5

H13M—C13E—H13N

C12E—C13E—H13O

H13M—C13E—H13O

H13N—C13E—H13O

C12E—C14E—H14M

C12E—C14E—H14N

H14M—C14E—H14N

C12E—C14E—H14O

H14M—C14E—H14O

H14N—C14E—H14O

C12E—C15E—H15M

C12E—C15E—H15N

H15M—C15E—H15N

C12E—C15E—H15O

H15M—C15E—H15O

H15N—C15E—H15O

C16E—O2E—Mg3

O2E—C16E—C21E

O2E—C16E—C17E

C21E—C16E—C17E

C18E—C17E—C16E

C18E—C17E—C22E

C16E—C17E—C22E

C19E—C18E—C17E

C19E—C18E—H18M

C17E—C18E—H18M

C20E—C19E—C18E

C20E—C19E—C26E

C18E—C19E—C26E

C19E—C20E—C21E

C19E—C20E—H20M

C21E—C20E—H20M

C20E—C21E—C16E

C20E—C21E—C27E

C16E—C21E—C27E

C23E—C22E—C24E

C23E—C22E—C25E

C24E—C22E—C25E

C23E—C22E—C17E

C24E—C22E—C17E

C25E—C22E—C17E

C22E—C23E—H23M

C22E—C23E—H23N

H23M—C23E—H23N

C22E—C23E—H23O

H23M—C23E—H23O

H23N—C23E—H23O

109.5

174.41 (15)

121.0 (2)

120.2 (2)

118.7 (2)

118.9 (2)

119.5 (2)

121.5 (2)

122.9 (2)

118.5

C35A—O4A—Mg1

O4A—C35A—C36A

O4A—C35A—H35A

C36A—C35A—H35A

O4A—C35A—H35B

C36A—C35A—H35B

H35A—C35A—H35B

C35A—C36A—C37A

C35A—C36A—H36A

C37A—C36A—H36A

C35A—C36A—H36B

C37A—C36A—H36B

H36A—C36A—H36B

C38A—C37A—C36A

C38A—C37A—H37A

C36A—C37A—H37A

C38A—C37A—H37B

C36A—C37A—H37B

H37A—C37A—H37B

O4A—C38A—C37A

O4A—C38A—H38A

C37A—C38A—H38A

O4A—C38A—H38B

118.5

117.5 (2)

120.9 (2)

121.5 (2)

123.2 (2)

118.4

118.6 (2)

119.1 (2)

122.3 (2)

110.9 (2)

106.2 (2)

106.5 (2)

110.24 (19)

110.36 (19)

112.6 (2)

109.5

108.9

102.9 (2)

111.2

109.1

103.1 (2)

111.2

109.5

111.2

109.5

Acta Cryst. (2018). C74, 548-557

sup-20

Article Doi

Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-opening polymerization of ?-caprolactone with initiators of different natures

DOI: 10.1107/S2053229618005090

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Authors:

Article abstract of DOI:10.1107/S2053229618005090

Full text of DOI:10.1107/S2053229618005090

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