Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9

research papers

Crystal structures and spectroscopic characteriza-

tion of MBr (CNXyl) (M = Fe and Co, n = 4; M = Ni,

2

n

n = 2; Xyl = 2,6-dimethylphenyl), and of formally

ISSN 2053-2296

zero-valent iron as a cocrystal of Fe(CNXyl) and

5

Fe (CNXyl)

2

9

a

b

Received 20 June 2019

Accepted 5 July 2019

William W. Brennessel, * Benjamin E. Kucera, Victor G. Young Jr and John E.

b

Ellis

Edited by P. Fanwick, Purdue University, USA

a

b

Department of Chemistry, 120 Trustee Road, University of Rochester, Rochester, NY 14627, USA, and Department of

Chemistry, 207 Pleasant Street SE, University of Minnesota, Minneapolis, MN 55455, USA. *Correspondence e-mail:

william.brennessel@rochester.edu

Keywords: 2,6-dimethylphenyl isocyanide;

xylyl isocyanide; crystal structure; iron; cobalt;

nickel; IR spectroscopy; NMR.

Structures and spectroscopic characterization of the divalent complexes cis-

dibromidotetrakis(2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771-

solvate, [FeBr (C H N) ]ꢀ0.771CH Cl or cis-FeBr (CNXyl) ꢀ0.771CH Cl (Xyl =

CCDC references: 1938762; 1938761;

1938760; 1938759; 1938758; 1938757

2

9

4

2

4

2

,6-dimethylphenyl), trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)-

Supporting information: this article has

iron(II), [FeBr (C H N) ] or trans-FeBr (CNXyl) , trans-dibromidotetrakis(2,6-

2

supporting information at journals.iucr.org/c

9

4

2

4

dimethylphenyl isocyanide)cobalt(II), [CoBr (C H N) ] or trans-CoBr (CNXyl) ,

2

9

4

and trans-dibromidobis(2,6-dimethylphenyl isocyanide)nickel(II), [NiBr (C H N) ]

2

9

2

or trans-NiBr (CNXyl) , are presented. Additionally, crystals grown from a cold

2

diethyl ether solution of zero-valent Fe(CNXyl)₅produced a structure

containing a cocrystallization of mononuclear Fe(CNXyl) and the previously

5

unknown dinuclear [Fe(CNXyl) ] (ꢀ -CNXyl) , namely pentakis(2,6-dimethyl-

3

2

3

phenyl isocyanide)iron(0) tris(ꢀ -2,6-dimethylphenyl isocyanide)bis[tris(2,6-

2

dimethylphenyl isocyanide)iron(0)], [Fe(C H N) ][Fe (C H N) ]. The (M)C—

9

5

2

9

N—C(Xyl) angles of the isocyanide ligand are nearly linear for the metals in the

2 oxidation state, for which the ligands function essentially as pure donors. The

CN stretching frequencies for these divalent metal isocyanides are at or above

+

ꢁ

II

that of the free ligand. Relative to Fe , in the structure containing iron in the

formally zero-valent oxidation state, the Fe—C bond lengths have shortened,

the C N bond lengths have elongated, the (M)C—N—C(Xyl) angles of the

terminal CNXyl ligands are more bent, and the ꢁCN stretching frequencies have

shifted to lower energies, all indicative of substantial M(dꢂ)!ꢂ* backbonding.

1

. Introduction

Access to isolable low-valent transition-metal complexes

directly from higher-valent precursors often requires em-

ploying a synthetic strategy that minimizes or avoids the

formation of unstable intermediates. One successful method

involves having an electron source double as a coordinating

ꢁ

ligand. In the synthesis of [Ta(CO)₆] (CO is carbon

monoxide), a naphthalene radical anion serves this purpose

(Dewey et al., 1983). Six equivalents of the naphthalene radical

anion reduce the Ta center in TaCl from an oxidation state of

5

+

V to that of formally ꢁI. During the reduction and before

CO is introduced, naphthalene also coordinates and stabilizes

the metal center, as conﬁrmed by the isolation of highly air-

ꢁ

sensitive but thermally stable [Ta(C H ) ] (C H is naph-

8 3

10

8

thalene) (Brennessel et al., 2002a). In an analogous reaction in

the cobalt system, for which naphthalene alone appears to be

ineffective in the stabilization of low-valent cobalt, the

#

2019 International Union of Crystallography

Acta Cryst. (2019). C75

https://doi.org/10.1107/S205322961900963X 1 of 10

research papers

ꢁ

homoleptic carbonyl anion [Co(CO) ] is formed in very low

4

Teﬂon cannula to the dropping funnel, to which had been

added CH Cl (10 ml). The reaction ﬂask was placed in an ice–

water bath and the POCl solution was added dropwise, which

ꢁ

yield (<20%) {[Co(C H ) ] has not been isolated as a pure

8 2

10

2

substance from this reaction to date in the absence of CO; see

Brennessel et al. (2006) and Brennessel & Ellis (2012)}.

3

resulted in an orange–brown slurry upon completion of the

addition. The reaction mixture was stirred for an additional

hour, and then transferred to a 1000 ml separatory funnel. The

product was washed and separated three times with a buffer

solution (pH 6.27) prepared from K HPO ꢀ3H O (3.027 g)

2

4

2

and KH PO (15.54 g) in H O (300 ml). (The ﬁrst wash pro-

2

4

2

duced a slight warming.) The resultant organic fraction was

then washed and separated three times with a saturated brine

solution prepared from NaCl in H O (300 ml). The product

2

was transferred to a ﬂask containing Na SO , stirred for

4

2

30 min, and ﬁltered via gravity through a one-inch plug of

Na SO . After the solvent had been removed under vacuum,

2

4

the orange solid was dissolved in petroleum ether and ﬁltered

to remove the colored impurity. Removal of the solvent under

vacuum left a ﬂuffy pale-yellow solid (yield 17.6 g, 78%).

ꢁ1

IR [tetrahydrofuran (THF), ꢁCN, cm ]: 2117 (vs); IR

ꢁ

1

(

3

Nujol mull, ꢁCN, cm ): 2114 (vs); m.p. 345–347 K; H NMR

300 MHz, CDCl , 293 K, ꢃ, ppm): 7.27 (CDCl ), 7.09–7.22 (m,

3

13

1

H, m- and p-CNXyl), 2.43 (s, 6H, CH₃); C{ H} NMR

Another method to access stable low-valent species, which

is an offshoot of the aforementioned method, involves starting

with the metal already in the desired reduced oxidation state.

(

75.4 MHz, CDCl , 293 K, ꢃ, ppm): 167.7 (CNXyl), 135.1 (o),

3

ꢂ130 (ipso), 128.8 (p), 127.9 (m), 77.2 (CDCl ), 19.1 (CH ).

3

ꢁ

[

Ta(CO) ] can be obtained quantitatively from the reaction

6

ꢁ

of carbon monoxide with [Ta(C H ) ] , for which [Ta-

10

8 3

ꢁ ꢁI

C H ) ] acts as a source of Ta monoatomic anions in the

10 8 3

(

synthesis (Brennessel et al., 2002a). The same strategy has

ꢁ

been employed to prepare [Co(CNXyl) ] in high yields, ca

4

ꢁ

83%, by the reaction of [Co(C H ) ] (C H is anthracene)

with four equivalents of CNXyl (Brennessel et al., 2002b).

14

10 2

14 10

ꢁ

However, treatment of the related ferrate, i.e. [Fe(C H ) ]

10 2

14

(Brennessel et al., 2007), with CNXyl did not afford the

desired homoleptic iron isocyanide products (Brennessel,

2ꢁ

2

009). Direct access to isoelectronic [Fe(CNXyl)₄] required

a more conventional naphthalene radical anion mediated

reduction of FeBr (CNXyl) (Brennessel & Ellis, 2007). This

2

4

article reports on the structures and spectroscopic character-

izations of several CNXyl (denoted 1) complexes of divalent

iron (as the dichloromethane 0.771-solvate, 2a, and in the

unsolvated form, 2b), cobalt (4), and nickel (5), and the

unexpected structure of a cocrystal of two homoleptic CNXyl

compounds of zero-valent iron, i.e. Fe(CNXyl)₅and the

previously unknown dinuclear [Fe(CNXyl) ] (ꢀ -CNXyl) (3)

2.1.2. cis-FeBr (CNXyl) ꢀ0.771CH Cl (2a) and trans-

2

4

2

FeBr (CNXyl) (2b). CNXyl (1.217 g, 9.27 mmol) in toluene

2

4

(20 ml) was added to FeBr (0.500 g, 2.32 mmol) in toluene

2

(100 ml). The reaction mixture was heated to 358 K for 1 h,

which produced a purple solution with obvious solids. After

cooling to room temperature, the mixture was ﬁltered. The

bright-orange cake of cis compound 2a was dried under

vacuum (yield 0.715 g, 42%). The solvent was removed under

vacuum from the red–purple ﬁltrate, which was then ﬁltered,

washed with pentane (2 ꢃ 20 ml), and dried under vacuum,

yielding light-blue–purple trans compound 2b (yield 0.728 g,

3

2

3

(see Schemes).

2

. Experimental

.1. Synthesis and crystallization

.1.1. 2,6-Dimethylphenyl isocyanide (CNXyl) (1). This

2

4

2%). Although no attempts to obtain bulk elemental

analyses on these compounds were carried out, they were

obtained as spectroscopically pure substances. Single crystals

2

synthesis was modeled after published ones (Malatesta, 1947;

Ugi & Meyr, 1960). Unpuriﬁed CH Cl (300 ml) and NEt

3

of each were obtained by evaporation from CH

cis-FeBr (CNXyl) (2a): IR (ꢁCN, Nujol mull, cm ): 2146

(s), 2127 (s); H NMR (300 MHz, CD Cl , 293 K, ꢃ, ppm):

7.11–7.19 (m, 12H, m- and p-CNXyl), 5.32 (CD Cl ), 2.62 (s,

Cl solutions.

2

ꢁ1

(105 ml, 755 mmol) were added to a 500 ml ﬂask containing

N-(2,6-dimethylphenyl)formamide (25.6 g, 172 mmol) that

2

4

1

2

had a dropping funnel attached. POCl (17.6 ml, 189 mmol),

3

2

1

3

1

previously puriﬁed by vacuum distillation, was added via a

12H, CH

3

), 2.48 (s, 12H, CH

3

); C{ H} NMR (75.4 MHz,

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CD Cl , 293 K, ꢃ, ppm): 173.2 (CNXyl), 136.4, 135.6, 129.2,

product was dried under vacuum, yielding a bright-green

powder (yield 1.633 g, 96%).

2

1

28.8, 128.4, 54.0 (quintet, CD Cl ), 19.3 (CH ), 19.2 (CH ).

2 2 3 3

ꢁ

1

ꢁ1

trans-FeBr (CNXyl) (2b): IR (ꢁCN, THF, cm ): 2181 (sh),

IR (ꢁCN, CH Cl , cm ): 2182 (vs); IR (ꢁCN, Nujol mull,

2

4

2

1

ꢁ1

2130 (vs); H NMR (300 MHz, CD Cl , 293 K, ꢃ, ppm): 7.14–

cm ): 2180 (sh), 2168 (vs); m.p. 475 K.

2.1.5. trans-NiBr (CNXyl)₂(5). This compound was pre-

2

7

.20 (m, 12H, m- and p-CNXyl), 5.32 (CD Cl ), 2.61 (s, 24H,

2

1

3

1

CH ); C{ H} NMR (75.4 MHz, CD Cl , 293 K, ꢃ, ppm): 174.7

pared previously by a different method (Yamamoto et al.,

1991). Toluene (80 ml) was added to a ﬂask containing NiBr₂

(1.030 g, 4.71 mmol) and CNXyl (1.287 g, 9.81 mmol). The

suspension was heated at 353–358 K for 12 h, although most

particulates had dissolved and/or reacted after 6 h. The red–

brown slurry was cooled slowly to room temperature, after

which half of the toluene was removed under vacuum before

ﬁltering. The ﬁlter cake was dried for a few hours at room

temperature, affording a dull-orange ﬁbrous solid (yield

1.577 g, 70%). The solvent was then removed under vacuum

from the ﬁltrate, providing another 0.357 g of product, giving a

total of 1.934 g (85%). Although no attempts to obtain bulk

elemental analyses on this compound were carried out, it was

obtained as a spectroscopically pure substance.

3

2

(

CNXyl), 136.3, 128.9, 128.3, 54.0 (quintet, CD Cl ), 19.2

2 2

CH ). The solution prepared for NMR analysis was stored in

3

1

the NMR tube for one month, after which a H NMR spec-

trum revealed that it had mostly converted to cis isomer 2a.

2

.1.3. Fe(CNXyl) ꢀFe (l -CNXyl) (CNXyl) (3). The mono-

5

2

3

6

nuclear part of 3 was synthesized based on the literature

preparation (Bassett et al., 1979), and the spectroscopic data

matched those reported previously. Bright-red single crystals

of cocrystal 3 were grown from a saturated diethyl ether

solution at 243 K.

ꢁ1

IR (toluene, ꢁCN, cm ): 2191 (vs); IR (Nujol mull, ꢁCN,

ꢁ1

1

cm ): 2196 (vs); H NMR (300 MHz, CDCl , 293 K, ꢃ, ppm):

3

7

.24–7.30 (m, 2H, p-CNXyl), 7.12–7.15 (m, 4H, m-CNXyl),

13

2.48 (s, 12H, CH₃); C NMR (75.4 MHz, CDCl , 293 K, ꢃ,

3

ppm): 136.7 (d, J = 161.8 Hz, o-CNXyl), 135.1 (vbr, ipso-

CNXyl), 130.5 (d, J = 161.2 Hz, p-CNXyl), 128.3 (d, J =

166.4 Hz, m-CNXyl), 77.2 (CDCl ), 18.8 (q, J = 126.9 Hz,

CH₃).

3

2.2. Refinement

Crystal data, data collection and structure reﬁnement

details are summarized in Table 1. In 1, the cocrystallized

dichloromethane solvent was modeled as disordered over a

crystallographic twofold axis (0.50:0.50), and additionally over

two general positions [0.593 (9) and 0.192 (9)]. The occu-

pancies of the general positions were not required to sum to

unity because it had been determined that there had been

solvent loss during the mounting procedure. This loss was

conﬁrmed by a signiﬁcant increase in R1 (strong data) when

the occupancies were forced to sum to unity, as well as by

examining the results of the SQUEEZE (Spek, 2015) routine

of PLATON (Spek, 2009), which showed 150 electrons versus

the expected 168. Analogous bond lengths and angles between

the two positions of the dichloromethane solvent disorder

were restrained to be similar. Anisotropic displacement

parameters for proximal (including symmetry-equivalent)

atoms were constrained to be equivalent. Additionally,

anisotropic displacement parameters for all atoms of the

major component were restrained to be similar.

ꢁ

1

Fe(CNXyl) (3, mononuclear part): IR (ꢁCN, THF, cm ):

5

1

033 (sh), 1975 (vs br), 1871 (sh); H NMR (300 MHz, C D ,

2

6

93 K, ꢃ, ppm): 7.16 (C D ), 6.78 (s, 15H, m- and p-CNXyl),

.43 (s, 30H, CH₃); C{ H} NMR (75.4 MHz, C D , 293 K, ꢃ,

6

13

1

6

ppm): 197.0 (CNXyl), 133.7 (o-CNXyl), 132.5 (ipso-CNXyl),

28.4 (t, C D ), 128.2 (m-CNXyl), 125.5 (p-CNXyl), 19.7

CH₃).

.1.4. trans-CoBr (CNXyl)₄(4). This compound was pre-

pared previously by a different method (Yamamoto &

1

(

6

2

Yamazaki, 1977a). To a clear blue solution of CoBr (0.500 g,

2

(

.29 mmol) in THF (30 ml) was added a solution of CNXyl

1.199 g, 9.14 mmol) in THF (20 ml) at room temperature,

which caused a green solid to precipitate immediately. After

an additional 3 h of stirring, the slurry was ﬁltered, and the

Methyl H atoms on C17 in 2a, C8, C9, and C17 in 2b, and C9

in 4 were modeled as rotationally disordered.

ꢄ

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Table 1

Experimental details.

1

2a

2b

Crystal data

Chemical formula

C

9

H

9

N

[FeBr (C

2

805.87

Monoclinic, C2/c

173

16.8177 (13), 15.8912 (12),

9

H

9

N)

4

]ꢀ0.771CH

Cl

2 2

2 9 9 4

[FeBr (C H N) ]

740.36

Orthorhombic, Pbca

173

14.4246 (13), 14.0229 (13),

M

r

131.17

Monoclinic, I2/a

100

14.5535 (6), 7.5199 (2), 14.6333 (7)

Crystal system, space group

Temperature (K)

˚

a, b, c (A)

1

4.1334 (11)

16.3444 (15)

90, 90, 90

3306.1 (5)

4

Mo Kꢄ

2.90

ꢅ

ꢄ, ꢅ, ꢆ ( )

90, 113.548 (5), 90

1468.12 (11)

8

Cu Kꢄ

0.54

0.15 ꢃ 0.12 ꢃ 0.06

90, 92.9182 (10), 90

3772.3 (5)

˚

3

V (A )

Z

Radiation type

4

Mo Kꢄ

2.66

0.44 ꢃ 0.16 ꢃ 0.08

ꢁ

1

ꢀ

Crystal size (mm)

(mm

)

0.25 ꢃ 0.20 ꢃ 0.15

Data collection

Diffractometer

XtaLAB Synergy, Dualﬂex,

HyPix

Bruker SMART CCD

platform

Siemens SMART CCD

platform

Absorption correction

Multi-scan (CrysAlis PRO; Rigaku

OD, 2018)

0.927, 0.968

Multi-scan (SADABS; Sheldrick,

2014)

0.662, 0.746

Multi-scan (SADABS; Sheldrick,

2014)

0.592, 0.746

Tmin, Tmax

No. of measured, independent and

observed [I > 2ꢇ(I)] reﬂections

6065, 1521, 1375

15633, 4323, 3646

25764, 3790, 3151

R

int

0.032

0.634

0.020

0.650

0.023

0.650

˚

ꢁ1

)

(sin ꢈ/ꢉ)max (A

Reﬁnement

2

R[F > 2ꢇ(F )], wR(F ), S

No. of reﬂections

0.040, 0.117, 1.11

1521

93

0

H-atom parameters constrained

0.025, 0.066, 1.03

4323

230

20

H-atom parameters constrained

0.48, ꢁ0.31

0.025, 0.065, 1.03

3790

198

0

H-atom parameters constrained

No. of parameters

No. of restraints

H-atom treatment

˚

ꢁ3

)

Áꢊmax, Áꢊmin (e A

0.20, ꢁ0.21

0.32, ꢁ0.52

3

4

5

Crystal data

Chemical formula

[Fe(C

2003.95

Monoclinic, P2

173

24.901 (3), 14.2838 (19), 30.954 (4)

9

H

9

N)

5

][Fe

2

(C

9

H

9

N)

9

]

[Co(C

743.44

9

H

9

N)

4

]

[NiBr

480.87

2 9 9 2

(C H N) ]

M

r

Crystal system, space group

Temperature (K)

˚

a, b, c (A)

1

/n

Orthorhombic, Pbca

173

14.5902 (14), 14.0206 (13),

1

Monoclinic, P2 /n

173

20.433 (7), 4.5010 (15), 21.285 (7)

1

6.2747 (15)

ꢅ

ꢄ, ꢅ, ꢆ ( )

90, 96.654 (2), 90

10935 (3)

90, 90, 90

3329.2 (5)

90, 105.682 (5), 90

1884.7 (11)

˚

3

V (A )

Z

Radiation type

4

Mo Kꢄ

0.45

0.36 ꢃ 0.28 ꢃ 0.08

Mo Kꢄ

2.95

0.25 ꢃ 0.15 ꢃ 0.10

Mo Kꢄ

5.27

0.50 ꢃ 0.10 ꢃ 0.05

ꢁ

1

ꢀ

(mm

Crystal size (mm)

)

Data collection

Diffractometer

Bruker SMART CCD

platform

Multi-scan (SADABS; Sheldrick,

Siemens SMART CCD

platform

Multi-scan (SADABS; Sheldrick,

2014)

0.676, 0.746

Siemens SMART CCD

platform

Multi-scan (SADABS; Sheldrick,

2014)

0.592, 0.746

Absorption correction

2014)

Tmin, Tmax

0.662, 0.746

75619, 19257, 10377

No. of measured, independent and

observed [I > 2ꢇ(I)] reﬂections

36969, 3815, 3240

9617, 3287, 2241

R

int

0.086

0.595

0.037

0.649

0.074

0.596

˚

ꢁ1

)

(sin ꢈ/ꢉ)max (A

Reﬁnement

2

R[F > 2ꢇ(F )], wR(F ), S

No. of reﬂections

0.063, 0.153, 1.03

19257

1316

0

H-atom parameters constrained

0.027, 0.057, 1.08

3815

200

0

H-atom parameters constrained

0.061, 0.109, 1.14

3287

215

0

H-atom parameters constrained

No. of parameters

No. of restraints

H-atom treatment

˚

ꢁ3

)

Áꢊmax, Áꢊmin (e A

0.44, ꢁ0.47

0.28, ꢁ0.45

0.94, ꢁ0.62

Computer programs: CrysAlis PRO (Rigaku OD, 2018), SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXT (Sheldrick, 2015a), SHELXS97 (Sheldrick, 2008), SHELXL2018

(Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009) and SHELXTL (Sheldrick, 2008).

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Table 2

Selected geometric parameters (A, ) for 1.

Table 3

Selected geometric parameters (A, ) for 2a.

˚

ꢅ

˚

ꢅ

N1—C1

1.1608 (15)

179.47 (11)

Fe1—C10

Fe1—C1

Fe1—Br1

1.8325 (17)

1.8791 (17)

2.4785 (3)

C1—N1

C10—N2

1.153 (2)

1.161 (2)

C1—N1—C2

i

C10 —Fe1—C10

96.49 (10)

88.99 (7)

92.97 (7)

177.05 (10)

176.96 (5)

86.02 (5)

C1—Fe1—Br1

i

C1 —Fe1—Br1

Br1—Fe1—Br1

C1—N1—C2

C10—N2—C11

89.17 (5)

88.77 (5)

91.520 (15)

177.85 (18)

163.00 (17)

i

C10 —Fe1—C1

i

C10—Fe1—C1

i

C1—Fe1—C1

H atoms were placed geometrically and treated as riding

2

atoms, with methylene C—H = 0.99 A and Csp —H = 0.95 A,

˚

i

C10 —Fe1—Br1

C10—Fe1—Br1

˚

with U (H) = 1.2U (C), and methyl C—H = 0.98 A, with

iso

eq

U (H) = 1.5U (C).

iso

˚

For 1, the maximum residual peak of 0.20 e A and the

1

2

eq

Symmetry code: (i) ꢁx þ 1; y; ꢁz þ .

ꢁ

ꢁ3

ꢁ

ꢁ3

˚

deepest hole of ꢁ0.21 e A are found 0.74 and 1.35 A from

powders were dissolved in dichloromethane and the solutions

were left open to the air to evaporate. Single crystals grown

from the orange solution were identiﬁed by X-ray diffraction

atoms C9 and C6, respectively.

For 2a, the maximum residual peak of 0.48 e A and the

ꢁ

ꢁ3

˚

ꢁ

ꢁ3

˚

deepest hole of ꢁ0.31 e A are found 1.09 and 0.42 A from

atoms Cl1 and Cl2 , respectively.

For 2b, the maximum residual peak of 0.32 e A and the

0

as cis-FeBr

2

(CNXyl)

4

ꢀ0.771CH

2 2

Cl , 2a, and those grown from

(CNXyl) ,

2 4

ꢁ

ꢁ3

the purple solution were shown to be trans-FeBr

2b.

˚

ꢁ

ꢁ3

˚

deepest hole of ꢁ0.52 e A are found 0.25 and 0.49 A from

The asymmetric unit of 2a contains one-half of an iron

complex (Fig. 3 and Table 3), located along a crystallographic

twofold axis that includes the Fe atom, plus cocrystallized

dichloromethane solvent, also located along a twofold axis.

The solvent was modeled as disordered over the axis

(0.50:0.50) and additionally over two general positions

atoms H9F and Br1, respectively.

For 3, the maximum residual peak of 0.44 e A and the

ꢁ

ꢁ3

˚

ꢁ

ꢁ3

˚

deepest hole of ꢁ0.47 e A are found 1.11 and 0.88 A from

atoms H60A and Fe3, respectively.

For 4, the maximum residual peak of 0.28 e A and the

ꢁ

ꢁ3

˚

ꢁ

ꢁ3

˚

deepest hole of ꢁ0.44 e A are found 0.72 and 0.46 A from

[

0.579 (9):0.192 (9)]. The ratio does not sum to unity because it

atoms C3 and Br1, respectively.

For 5, the maximum residual peak of 0.94 e A and the

ꢁ

ꢁ3

was found that the solvent, which packed in channels along

[001] (Fig. 4), had partially escaped from the crystals during

the mounting procedure. The structure of 2a is isomorphous

with its chlorido analog (Perry et al., 2010), whose solvent

channels were occupied by n-hexane, also of partial occu-

pancy.

˚

ꢁ

ꢁ3

˚

deepest hole of ꢁ0.62 e A are found 1.14 and 1.17 A from

atoms Ni1 and Br1, respectively.

3

. Results and discussion

The trans isomer of FeBr (CNXyl) , 2b (Fig. 5 and Table 4),

2

4

The isocyanide molecule used for ligating metals in this study,

i.e. CNXyl, 1, crystallized in the space group I2/a with one

molecule in the asymmetric unit (Fig. 1). The structure was

intially reported in its primitive setting of one-half the volume

with two molecules in the asymmetric unit (Mathieson et al.,

crystallized as large purple blocks. The molecule is located on

a crystallographic inversion center that coincides with the Fe

atom. A three-dimensional network is generated by pairs of

offset parallel stacked arene rings (centroid–centroid

˚

distance = 3.61 A). The previously reported chlorido analog

2001). Despite the potential for parameter correlations

between symmetry-related atoms, the reported bond lengths

closely match those of 1. A second structure containing CNXyl

was recently published in which CNXyl was cocrystallized with

an iminodisilirane of interest (Tashkandi et al., 2019). In 1, the

terminal C—N bond length and linear C—N—C angle

ꢁ

1

(

Table 2), as well as the solution IR ꢁCN stretch of 2117 cm

1

3

and the C NMR resonance for the isocyanide C atom of ꢃ

67.7 ppm, are consistent with a C N triple bond. The mol-

ecules of 1 are aligned along [001], with pairs of offset parallel-

1

˚

stacked molecules (centroid–centroid distance = 3.64 A)

potentially linked by overlapped ꢂ systems in the C

N

˚

moieties (3.47 A) and C—Hꢀ ꢀ ꢀcentroid (Hꢀ ꢀ ꢀcentroid =

˚

2

(

.73 A), donor!electron-deﬁcient-ring-center interactions

Fig. 2).

The addition of four equivalents of CNXyl to anhydrous

FeBr in toluene resulted in a purple solution with solids. The

2

solids were ﬁltered off, dried, and washed, which resulted in an

orange powder. The solvent was removed from the red–purple

ﬁltrate, to leave a light-blue–purple powder. Separately, both

Figure 1

Anisotropic displacement ellipsoid plot of 1 drawn at the 50% probability

level.

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Fe/Co/Ni complexes of 2,6-dimethylphenyl isocyanide 5 of 10

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Table 4

Selected geometric parameters (A, ) for 2b.

˚

ꢅ

Fe1—C10

Fe1—C1

Fe1—Br1

1.8748 (16)

1.8842 (16)

2.4665 (3)

C1—N1

C10—N2

1.156 (2)

i

C1 —Fe1—Br1

C1—Fe1—Br1

Br1—Fe1—Br1

C1—N1—C2

C10—Fe1—C10

C10—Fe1—C1

180.0

91.43 (7)

180.0

91.52 (5)

88.49 (5)

86.81 (5)

93.19 (5)

180.0

167.90 (17)

171.99 (17)

i

C1 —Fe1—C1

C10—Fe1—Br1

i

C10 —Fe1—Br1

C10—N2—C11

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

(Drew et al., 1986) is not isomorphous or even isostructural,

but has similar unit-cell constants of 13.853 (8), 13.853 (8), and

˚

.803 (8) A and 90, 90, and 90 (cf. Table 1).

ꢅ

8

Figure 3

Anisotropic displacement ellipsoid plot of 2a, drawn at the 50%

probability level and with solvent molecules and H atoms omitted. The

symmetry equivalent portion is generated by a twofold axis at (ꢁx + 1, y,

The IR stretches for 2a and 2b of ꢁCN = 2137 (average of

ꢁ

1

two bands) and 2130 cm , respectively, compared to that of

ꢁ

1

2

the free ligand, 2117 cm , indicate a strengthening of the

N bonds through coordination to the metal. Indeed, it has

been demonstrated that the lone pair on the isocyanide C

ꢁz + ) (symmetry code A).

C

atom of the free ligand is antibonding with respect to the

N bond, and that through coordination to a metal center,

C

more bonding character is achieved, thus strengthening this

bond (Crabtree, 1994). Although the average Fe—C bond

lengths vary slightly between 2a and 2b, the average C

N

bond lengths and C—N—C angles are the same (Tables 3

and 4). However, because of the cis geometry of 2a, two

CNXyl ligands (one unique due to symmetry) are trans to an

isocyanide ligand and the other two CNXyl ligands (again, one

unique) are trans to the bromido ligands. The isocyanide

ligands trans to the other isocyanides have the same Fe—C

and C N bond lengths and C—N—C angles as those found in

2b (Table 4), but those trans to a bromido ligand show

evidence of backbonding (Table 3), speciﬁcally shorter Fe—C

Figure 2

Anisotropic displacement ellipsoid plots of 1, drawn at the 50%

probability level. Symmetry equivalent molecules were generated by

3

1

3

2

1

2

1

2

the operations (ꢁx + , ꢁy + , ꢁz + ), (ꢁx + , y, ꢁz + 1), and (x, ꢁy + ,

2

z + ). (a) View down [001] which shows the parallel stacking. Pairs of

2

1

2

molecules of the same bond type (i.e. solid or hollow) are offset parallel

˚

stacked at centroid–centroid distances of 3.64 A. The centroid–centroid

distance between non-overlapping rings (i.e. different bond types) is

˚

.65 A. (b) Side view that depicts the centroid–centroid offsets. (c) The

4

pairs of molecules whose rings do not overlap have overlaps of their

˚

C

N groups at a distance of 3.47 A and a C Nꢀ ꢀ ꢀN C pseudo-torsion

ꢅ

angle of 78.5 (2) . (d) In addition to the possible ꢂ–ꢂ interaction of the

Figure 4

Packing plot of 2a, with H atoms omitted. Disordered solvent of partial

occupancy is located in channels along [001].

C

centroid distance = 2.73 A).

N segments, there may be C—Hꢀ ꢀ ꢀcentroid interactions (Hꢀ ꢀ ꢀ

˚

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Table 5

Selected geometric parameters (A, ) for 3.

˚

ꢅ

Fe1—C28

Fe1—C1

Fe1—C19

Fe1—C37

Fe1—C10

N1—C1

N2—C10

N3—C19

N4—C28

N5—C37

Fe2—C64

Fe2—C55

Fe2—C46

Fe2—C91

Fe2—C73

Fe2—C82

1.805 (4)

1.816 (4)

1.819 (4)

1.821 (5)

1.829 (4)

1.196 (5)

1.183 (5)

1.177 (5)

1.192 (5)

1.178 (5)

1.832 (5)

1.840 (4)

1.852 (4)

1.967 (4)

1.974 (4)

Fe2—Fe3

Fe3—C100

Fe3—C109

Fe3—C118

Fe3—C73

Fe3—C82

Fe3—C91

N6—C46

N7—C55

N8—C64

N9—C73

N10—C82

N11—C91

N12—C100

N13—C109

N14—C118

2.4764 (8)

1.838 (5)

1.856 (4)

1.860 (4)

1.962 (4)

1.978 (4)

2.022 (4)

1.180 (5)

1.178 (5)

1.245 (4)

1.237 (4)

1.235 (4)

1.190 (5)

1.176 (4)

1.179 (4)

C28—Fe1—C1

C28—Fe1—C19

C1—Fe1—C19

C28—Fe1—C37

C1—Fe1—C37

C19—Fe1—C37

C28—Fe1—C10

C1—Fe1—C10

C19—Fe1—C10

C37—Fe1—C10

C1—N1—C2

C10—N2—C11

C19—N3—C20

C28—N4—C29

C37—N5—C38

C64—Fe2—C55

C64—Fe2—C46

C55—Fe2—C46

C64—Fe2—C91

C55—Fe2—C91

C46—Fe2—C91

C64—Fe2—C73

C55—Fe2—C73

C46—Fe2—C73

C91—Fe2—C73

C64—Fe2—C82

C55—Fe2—C82

128.78 (18)

88.02 (17)

90.78 (17)

85.38 (17)

92.23 (17)

173.24 (17)

119.54 (18)

111.66 (17)

90.29 (17)

94.22 (17)

162.9 (4)

C46—Fe2—C82

C91—Fe2—C82

C73—Fe2—C82

C100—Fe3—C109

C100—Fe3—C118

C109—Fe3—C118

C100—Fe3—C73

C109—Fe3—C73

C118—Fe3—C73

C100—Fe3—C82

C109—Fe3—C82

C118—Fe3—C82

C73—Fe3—C82

C100—Fe3—C91

C109—Fe3—C91

C118—Fe3—C91

C73—Fe3—C91

C82—Fe3—C91

C46—N6—C47

C55—N7—C56

C64—N8—C65

C73—N9—C74

C82—N10—C83

C91—N11—C92

C100—N12—C101

C109—N13—C110

C118—N14—C119

96.16 (16)

84.02 (15)

87.43 (16)

93.56 (16)

93.66 (16)

90.28 (16)

94.61 (16)

171.46 (16)

91.68 (15)

84.51 (16)

90.63 (16)

178.00 (16)

87.67 (16)

166.97 (16)

87.99 (15)

99.28 (16)

83.49 (15)

82.53 (16)

164.1 (4)

165.8 (4)

165.4 (4)

132.9 (3)

133.0 (3)

133.7 (3)

165.2 (4)

168.6 (4)

162.7 (4)

Figure 5

Anisotropic displacement ellipsoid plot of 2b, drawn at the 50%

probability level and with H atoms omitted. The symmetry-equivalent

portion is generated by the inversion operation (ꢁx, ꢁy + 1, ꢁz + 1)

(symmetry code A). Structures 2b and 4 are isomorphous (see supporting

information for an ellipsoid plot of 4).

166.4 (4)

178.7 (4)

158.6 (4)

164.6 (4)

that of the literature procedure (Bassett et al., 1979), by

reduction of a mixture of FeBr and ﬁve equivalents of CNXyl

in THF with sodium amalgam {which is too weak of a reducing

2

agent in THF to generate [Fe(CNXyl) ] }. As the goal of the

2

ꢁ

93.53 (17)

93.81 (17)

95.13 (17)

85.33 (16)

93.71 (17)

171.16 (17)

88.00 (16)

177.63 (17)

86.57 (16)

84.61 (16)

168.76 (17)

90.74 (16)

4

synthesis was to obtain a crystal structure, after conﬁrming the

but longer C N bond lengths, and more bent (i.e. nonlinear)

C—N—C angles. This exact phenomenon was noted for the

1

chlorido analog (Perry et al., 2010). Interestingly, a H NMR

spectrum taken approximately one month later on the exact

same solution of 2b in CD Cl showed that it had converted

almost entirely to 2a.

2

Although 2a and 2b can be synthesized simultaneously and

subsequently separated by solubility differences, when

employed as precursors to low-valent species, it is unnecessary

to worry about isomer segregation. A mixture of 2a and 2b

formed in situ in THF was used successfully to generate

K [Fe(CNXyl) ] by reduction with four equivalents of

2

4

+

ꢁ

K C H (Brennessel & Ellis, 2007).

1

0

8

While a few structures of homoleptic isocyanide complexes

t

of zero-valent iron have been reported, namely Fe(CN Bu) ,

5

[

Fe(CNEt) ] (ꢀ -CNEt)

(Bassett et al., 1979), and

Fe(CNPh) ] (ꢀ -CNPh) (Ruiz et al., 1992), we wanted to

3

2

3

Figure 6

[

evaluate a structure of Fe(CNXyl) for direct comparison with

3

2

3

Anisotropic displacement ellipsoid plot of the monomeric part of 3,

drawn at the 50% probability level and with H atoms omitted. The

orientation was chosen to feature the axial ligands of the trigonal–

bipyramidal complex vertically (ligands containing atoms N3 and N5).

5

2ꢁ

divalent iron complexes 2a and 2b and [Fe(CNXyl) ] .

4

Therefore, we synthesized Fe(CNXyl) in a manner similar to

5

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Fe/Co/Ni complexes of 2,6-dimethylphenyl isocyanide 7 of 10

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Table 6

Selected average structural and spectroscopic data.

˚

M—C (A)

˚

N (A)

ꢅ

ꢁ1 a

C

C—N—C ( )

ꢁCN (cm

)

ꢃ(M—C) (ppm)

b

2117 (vs) , 2114 (vs)

c

d

1

2

3

[

4

5

–

1.856 (2)

1.1608 (15)

e

1.157 (3)

179.47 (11)

e

167.7

e

c

f

a

b

, L5

, L9t

, L9b

Fe(CNXyl)

170.4 (3)

169.9 (3)

2146 (s), 2147 (s)

2181 (sh), 2130 (vs)

2033 (sh), 1975 (vs br), 1871 (sh)

173.2

b

f

1.880 (2)

1.818 (4)

1.846 (5)

1.980 (9)

1.765 (6)

1.867 (3)

1.84 (1)

1.156 (3)

1.185 (4)

1.180 (2)

1.239 (3)

1.237 (8)

1.151 (3)

1.15 (1)

174.7

g

h

b

i

166 (3)

197.0

g

165.3 (8)

133.2 (3)

143.8 (6)

171.7 (3)

179 (1)

–

g

2ꢁ,k

b

l

4

]

1670 (vs, br)

238.7

m

j

2182 (vs) , 2180 (sh), 2168 (vs)

c

–

n

2191 (vs) , 2196 (vs)

c

m

4 8 3

Notes: (a) vs = very strong, s = strong, sh = shoulder, and br = broad; (b) tetrahydrofuran (THF, C H O); (c) Nujol (heavy mineral oil) mull; (d) deuterated chloroform (CDCl ); (e) the

two individual values in the asymmetric unit differ signiﬁcantly, depending on which ligand is trans (see Table 3 for individual bond lengths and angles); (f) deuterated dichloromethane

(CD

axial ligand (N3) angle differs greatly from the others [178.8 (4) ] (see Table 5 for individual angles); (i) deuterated benzene (C

2

Cl

2

); (g) L5 = mononuclear Fe(CNXyl)

5

, L9t = dinuclear Fe

ꢅ

2

(CNXyl)

9

, with terminal isocyanide ligands, and L9b = dinuclear Fe

); (j) dichloromethane (CH

2

(CNXyl)

9

, with bridging isocyanide ligands; (h) one

Cl ); (k) Brennessel & Ellis

2

6

D

6

2

4 8 6 5 3

(2007); (l) deuterated THF (C D O); (m) not resolved; (n) toluene (C H CH ).

product by IR and NMR spectroscopies, the isolated solid was

dissolved in a minimal amount of diethyl ether and left in a

243 K freezer for approximately one month. The single crys-

tals analyzed proved to be [Fe(CNXyl) ][Fe(CNXyl) ] (ꢀ -

5

3 2

2

CNXyl) , 3 (Figs. 6 and 7), a structure containing a 1:1

3

cocrystallization of both forms (see examples above) of zero-

valent iron. Surprisingly, despite the large number of arene

rings in the asymmetric unit (14), only one obvious ꢂ–ꢂ

interaction occurs, an offset parallel stacking between rings

˚

C11–C18 and C47–C54 (centroid–centroid distance = 3.77 A).

As expected for the lower oxidation state of iron in 3

compared to isomers 2, the average Fe—C bond length to the

terminal isocyanide ligands is shorter, the C N bond length

has increased, and the C—N—C angle has decreased (Tables 5

and 6). Spectroscopically, the IR ꢁCN stretches have shifted to

13

lower energy and the C NMR resonance for the isocyanide C

atom has shifted downﬁeld. For direct comparison with 2 and

2

, [Fe(CNXyl)₄] has also been included in Table 6.

ꢁ

3

Structure 4 is the isomorphous cobalt analog of 2b (Fig. S1

in the supporting information and Table 7). Although cobalt

has a slightly smaller radius and is slightly less electropositive

than iron, for the three metrics that we have been considering,

the M—C and C N bond lengths are the same, and the C—

N—C angles are very similar (Table 6). The IR ꢁCN stretches

ꢁ1

between the two are different, but that of 4, i.e. 2170 cm ,

matches that of the iodido analog, CoI (CNXyl) (Leach et al.,

2

4

1

994). Just as the isomers of 2 were used to access

2ꢁ

[Fe(CNXyl)₄] (Brennessel & Ellis, 2007) and CoI (CNXyl)

ꢁ

could be used to generate [Co(CNXyl) ] (Leach et al., 1994),

2

4

to afford [Co(CNXyl) ] in good yield (Brennessel, 2009).

was also successfully reduced by naphthalene radical anion

ꢁ

4

Moving further to the right of the periodic table, we

examined the reaction of CNXyl with nickel. Not unsurprising,

even in the presence of excess CNXyl, the species formed was

II

the four-coordinate square-planar Ni complex trans-

NiBr (CNXyl) , 5 (Fig. 8 and Table 8). The asymmetric unit

2

contains one-half each of two independent molecules located

at crystallographic inversion centers that coincide with the

metals. The angle between the planes of the two molecules is

75.8 (2) . Each independent molecule stacks with symmetry

equivalents of itself along [010] (Fig. 9), such that the distance

Figure 7

Plot of the dinuclear part of 3, with H atoms omitted, showing (a) an

anisotropic displacement ellipsoid plot drawn at the 50% probability level

and (b) drawn in the same orientation as small spheres for labeling clarity.

ꢅ

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Table 7

Selected geometric parameters (A, ) for 4.

Table 8

Selected geometric parameters (A, ) for 5.

˚

ꢅ

˚

ꢅ

Co1—C10

Co1—C1

Co1—Br1

1.8718 (17)

1.8800 (17)

2.6846 (3)

C1—N1

C10—N2

1.152 (2)

1.149 (2)

Ni1—C1

Ni1—Br1

C1—N1

1.844 (8)

2.3079 (9)

1.146 (8)

Ni2—C10

Ni2—Br2

C10—N2

1.845 (8)

2.3020 (9)

1.161 (9)

i

C10 —Co1—C10

C10—Co1—C1

i

ii

180.0

91.03 (7)

180.0

86.28 (5)

84.85 (5)

C10—Co1—Br1

C1—Co1—Br1

93.72 (5)

95.15 (5)

180.0

169.55 (17)

173.77 (18)

C1—Ni1—C1

C1—Ni1—Br1

180.0

C10—Ni2—C10

C10—Ni2—Br2

ii

180.0

90.3 (2)

180.0

178.0 (7)

90.1 (2)

180.0

179.4 (8)

i

C1 —Co1—C1

i

Br1 —Co1—Br1

i

Br1—Ni1—Br1

C1—N1—C2

Br2—Ni2—Br2

C10—N2—C11

i

C10—Co1—Br1

i

C1—Co1—Br1

C1—N1—C2

C10—N2—C11

Symmetry codes: (i) ꢁx þ 2; ꢁy; ꢁz þ 2; (ii) ꢁx þ 2; ꢁy þ 2; ꢁz þ 1.

Symmetry code: (i) ꢁx þ 2; ꢁy þ 1; ꢁz þ 1.

CNXyl resulted in equal amounts of the cis and trans isomers,

while the reaction of CoBr and CNXyl resulted solely in the

between neighboring symmetry-equivalent atoms is the b-axis

˚

unit-cell dimension [4.5010 (15) A]. Selected bond lengths and

2

trans form. When NiBr was reacted with CNXyl, the product

2

angles for 5 are found in Table 8.

A few brief attempts were made to synthesize the known

was four-coordinate square planar and trans, with only two

CNXyl ligands present. Crystallization of the homoleptic zero-

zero-valent nickel complex Ni(CNXyl) from 5, by reducing it

4

valent iron complex Fe(CNXyl) from a cold diethyl ether

5

in the presence of excess CNXyl in THF. Unfortunately,

ꢁ

solution led to a structure with two forms cocrystallized as

[Fe(CNXyl) ][Fe(CNXyl) ] (ꢀ -CNXyl) . Comparison of the

1

although the correct IR ꢁCN stretches of 2033 and 1997 cm

Hahn et al., 2004) were seen in the spectrum, the amount of

5

3 2

2

3

(

bond lengths and angles and the spectroscopic data between

the divalent and zero-valent species conﬁrmed the expected

back-bonding of the isocyanide ligands. The divalent iron and

cobalt complexes were shown to be appropriate precursors to

product was negligible, perhaps due to polymerization of the

isocyanide ligand. And unlike in the iron and cobalt systems,

ꢁ

II

for which percursors in the low oxidation states of Fe and

ꢁI

0

ꢁII

ꢁI

Co are not commercially available, Ni is readily available as

Ni(CO) and Ni(cod) (cod = cycloocta-1,5-diene). In fact, the

ﬁrst synthesis of Ni(CNXyl) was obtained from the former

low-valent Fe and Co isocyanide complexes in good yield,

presumably due to their having the ligand set coordinated in

both the starting and product materials, which allowed for

stabilization of intermediate oxidation states during the

reductive process. In contrast, the divalent nickel species only

contained two CNXyl ligands, requiring two more to coordi-

4

2

4

(

Yamamoto & Yamazaki, 1977b) and the synthesis from which

the crystal structure was obtained used the latter (Hahn et al.,

004). No attempts were made, however, to strategically

2

improve the synthesis of Ni(CNXyl) from 5.

4

nate to afford the zero-valent Ni(CNXyl) complex. In this last

4

In conclusion, the crystal structures of several divalent di-

bromido metal complexes ligated by isocyanide CNXyl were

presented. In the iron system, the reaction of FeBr with

case, the yield was extremely poor. Further studies with

different isocyanide ligands and different metals may be

beneﬁcial for accessing lower formal oxidation states of

2

Figure 8

Anisotropic displacement ellipsoid plot of the two independent molecules

of 5, drawn at the 50% probability level and with H atoms omitted. Both

independent molecules in the asymmetric unit lie on crystallographic

inversion centers that coincide with the Ni atoms. The symmetry-

equivalent parts of the molecules are generated by the operators (ꢁx + 2,

Figure 9

Anisotropic displacement ellipsoid packing plot of 5, drawn at the 50%

probability level and with H atoms omitted. Each independent nickel

molecule is parallel stacked along [010] with its symmetry equivalents at

˚

distances of 4.5010 (15) A, i.e. the b-axis unit-cell dimension. The angle

ꢅ

ꢁ

y, ꢁz + 2) (Ni1) and (ꢁx + 2, ꢁy + 2, ꢁz + 1) (Ni2) (symmetry code A).

between the Ni1 and Ni2 molecular planes is 75.8 (2) .

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Fe/Co/Ni complexes of 2,6-dimethylphenyl isocyanide 9 of 10

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metals, with the added beneﬁt that the isocyanide ligand is also

a great spectroscopic probe.

Brennessel, W. W., Young, V. G. Jr & Ellis, J. E. (2006). Angew. Chem.

Int. Ed. 45 , 7268–7271.

Bruker (2003). SAINT and SMART . Bruker AXS Inc., Madison,

Wisconsin, USA.

Acknowledgements

Crabtree, R. H. (1994). The Organometallic Chemistry of the

Transition Metals , 2nd ed., p 79. New York: John Wiley & Sons.

Dewey, C. G., Ellis, J. E., Fjare, K. L., Pfahl, K. M. & Warnock, G. F. P.

The authors acknowledge the US National Science Founda-

tion, and the donors of the Petroleum Research Fund, admi-

nistered by the American Chemical Society, for funding. The

University of Minnesota Chemistry Department is acknowl-

edged for providing and supporting the graduate level course

in X-ray crystallography. Students from this course, Kevin J.

Erickson, Emily L. Que, Airon Soegianto, Pratik Verma, and

Daniel J. Wherritt, are thanked for their assistance with the

various crystal structures in this article. Data for the structure

of CNXyl were collected on an instrument purchased with

funding from the NSF.

(1983). Organometallics , 2 , 388–391.

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. &

Puschmann, H. (2009). J. Appl. Cryst. 42 , 339–341.

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J. Organomet. Chem. 314 , 163–172.

Hahn, F. E., M u¨ nder, M. & Fr o¨ hlich, R. (2004). Z. Naturforsch. Teil B ,

59 , 850–854.

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N. J. (1994). J. Am. Chem. Soc. 116 , 8566–8574.

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Oxfordshire, England.

Ruiz, J., Riera, V., Vivanco, M., Garcia-Granda, S. & Pertierra, P.

Funding information

Funding for the instrument used to analyse 1 was provided by:

National Science Foundation (grant No. CHE-1725028).

(1992). Organometallics , 11 , 2734–2736.

Sheldrick, G. M. (2008). Acta Cryst. A 64 , 112–122.

Sheldrick, G. M. (2014). SADABS . University of G o¨ ttingen,

Germany.

Sheldrick, G. M. (2015 a ). Acta Cryst. A 71 , 3–8.

Sheldrick, G. M. (2015 b ). Acta Cryst. C 71 , 3–8.

Spek, A. L. (2009). Acta Cryst. D 65 , 148–155.

Spek, A. L. (2015). Acta Cryst. C 71 , 9–18.

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Chem. Soc. Jpn , 64 , 3376–3383.

References

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&

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USA.

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600.

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Ed. 46 , 6132–6136.

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C31–C33.

Brennessel, W. W., Young, V. G. Jr & Ellis, J. E. (2002 b ). Angew.

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4139.

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1

0 of 10 Brennessel et al. Fe/Co/Ni complexes of 2,6-dimethylphenyl isocyanide

Acta Cryst. (2019). C75

supporting information

Acta Cryst. (2019). C75 [https://doi.org/10.1107/S205322961900963X]

Crystal structures and spectroscopic characterization of MBr (CNXyl) (M = Fe

2

n

and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-

valent iron as a cocrystal of Fe(CNXyl) and Fe (CNXyl)

5

2

9

William W. Brennessel, Benjamin E. Kucera, Victor G. Young and John E. Ellis

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2018) for (1); SMART (Bruker, 2003) for (2a), (2b), (3), (4), (5). Cell

refinement: CrysAlis PRO (Rigaku OD, 2018) for (1); SAINT (Bruker, 2003) for (2a), (2b), (3), (4), (5). Data reduction:

CrysAlis PRO (Rigaku OD, 2018) for (1); SAINT (Bruker, 2003) for (2a), (2b), (3), (4), (5). Program(s) used to solve

structure: SHELXT (Sheldrick, 2015a) for (1); SHELXS97 (Sheldrick, 2008) for (2a), (2b), (3), (4), (5). For all structures,

program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b). Molecular graphics: OLEX2 (Dolomanov et al.,

2

009) for (1); SHELXTL (Sheldrick, 2008) for (2a), (2b), (3), (4), (5). Software used to prepare material for publication:

OLEX2 (Dolomanov et al., 2009) for (1); SHELXTL (Sheldrick, 2008) for (2a), (2b), (3), (4), (5).

2,6-Dimethylphenyl isocyanide (1)

Crystal data

C

M

9

H

9

N

F(000) = 560

= 1.187 Mg m

−3

r

= 131.17

D

x

Monoclinic, I2/a

a = 14.5535 (6) Å

b = 7.5199 (2) Å

c = 14.6333 (7) Å

β = 113.548 (5)°

V = 1468.12 (11) Å

Z = 8

Cu Kα radiation, λ = 1.54184 Å

Cell parameters from 3228 reflections

θ = 6.6–77.2°

µ = 0.54 mm

T = 100 K

−1

3

Plate, colourless

0.15 × 0.12 × 0.06 mm

Data collection

XtaLAB Synergy, Dualflex, HyPix

diffractometer

Radiation source: micro-focus sealed X-ray

tube, PhotonJet (Cu) X-ray Source

Mirror monochromator

6065 measured reflections

1521 independent reflections

1375 reflections with I > 2σ(I)

R

int = 0.032

θ

max = 77.7°, θmin = 6.6°

ω scans

h = −17→18

k = −7→9

Absorption correction: multi-scan

(CrysAlis PRO; Rigaku OD, 2018)

l = −18→17

T

min = 0.927, Tmax = 0.968

Acta Cryst. (2019). C75

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supporting information

Refinement

2

Refinement on F

Secondary atom site location: difference Fourier

Least-squares matrix: full

map

2

R[F > 2σ(F )] = 0.040

Hydrogen site location: inferred from

neighbouring sites

2

wR(F ) = 0.117

S = 1.11

H-atom parameters constrained

2

1521 reflections

93 parameters

0 restraints

w = 1/[σ (F

where P = (F

o

) + (0.0648P) + 0.6454P]

2

o

+ 2F )/3

c

(Δ/σ)max < 0.001

Δρmax = 0.20 e Å

Δρmin = −0.21 e Å

−

3

Primary atom site location: dual

−

3

Special details

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

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

x

y

z

Uiso*/Ueq

N1

C1

C2

C3

C4

H4

0.19375 (7)

0.14211 (9)

0.25634 (8)

0.21774 (8)

0.28185 (8)

0.259422

0.52937 (12)

0.40998 (16)

0.67397 (14)

0.84592 (15)

0.98676 (14)

1.102821

0.37062 (7)

0.36776 (9)

0.37500 (7)

0.37156 (8)

0.37771 (8)

0.376752

0.0216 (3)

0.0287 (3)

0.0194 (3)

0.0206 (3)

0.0218 (3)

0.026*

C5

H5

0.37863 (8)

0.420152

0.95713 (14)

1.053264

0.38524 (8)

0.388885

0.0226 (3)

0.027*

C6

H6

0.41410 (8)

0.479072

0.78494 (14)

0.766913

0.38740 (8)

0.392141

0.0212 (3)

0.025*

C7

C8

0.35330 (8)

0.11209 (8)

0.066418

0.098978

0.103281

0.38993 (8)

0.387081

0.457847

0.63899 (14)

0.87498 (15)

0.821831

1.000251

0.821439

0.45156 (14)

0.389722

0.453512

0.38252 (8)

0.36144 (8)

0.300578

0.360303

0.416947

0.38439 (8)

0.440587

0.389713

0.0201 (3)

0.0242 (3)

0.036*

0.0240 (3)

0.036*

H8A

H8B

H8C

C9

H9A

H9B

H9C

0.348271

0.391761

0.324053

0.036*

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

N1

C1

C2

C3

C4

C5

0.0226 (5)

0.0295 (6)

0.0234 (6)

0.0242 (6)

0.0269 (6)

0.0267 (6)

0.0205 (5)

0.0240 (6)

0.0189 (5)

0.0217 (6)

0.0173 (5)

0.0192 (5)

0.0228 (5)

0.0008 (4)

−0.0018 (5)

−0.0033 (4)

0.0010 (4)

0.0022 (4)

−0.0036 (4)

0.0102 (4)

0.0150 (5)

0.0090 (4)

0.0093 (4)

0.0102 (4)

0.0114 (4)

0.0010 (3)

0.0009 (5)

−0.0001 (4)

0.0004 (4)

0.0002 (4)

0.0348 (6)

0.0169 (5)

0.0170 (5)

0.0216 (5)

0.0232 (5)

Acta Cryst. (2019). C75

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supporting information

C6

C7

C8

C9

0.0211 (5)

0.0239 (5)

0.0242 (6)

0.0261 (6)

0.0228 (5)

0.0192 (5)

0.0244 (5)

0.0187 (5)

0.0214 (5)

0.0178 (5)

0.0255 (5)

0.0274 (6)

−0.0008 (4)

0.0007 (4)

0.0026 (4)

0.0015 (4)

0.0103 (4)

0.0089 (4)

0.0115 (4)

0.0110 (4)

0.0000 (4)

0.0002 (4)

0.0006 (4)

Geometric parameters (Å, º)

N1—C1

N1—C2

C2—C3

C2—C7

C3—C4

C3—C8

C4—H4

C4—C5

C5—H5

C5—C6

1.1608 (15)

C6—H6

C6—C7

C7—C9

C8—H8A

C8—H8B

C8—H8C

C9—H9A

C9—H9B

C9—H9C

0.9300

1.4035 (13)

1.4026 (15)

1.3959 (15)

1.3904 (15)

1.5006 (15)

0.9300

1.3861 (16)

0.9300

1.3897 (15)

1.3936 (15)

1.5033 (14)

0.9600

C1—N1—C2

C3—C2—N1

C7—C2—N1

C7—C2—C3

C2—C3—C8

C4—C3—C2

C4—C3—C8

C3—C4—H4

C5—C4—C3

C5—C4—H4

C4—C5—H5

C4—C5—C6

C6—C5—H5

C5—C6—H6

C5—C6—C7

C7—C6—H6

179.47 (11)

117.99 (9)

118.35 (9)

123.66 (10)

121.17 (10)

116.81 (10)

122.01 (10)

119.4

121.13 (10)

119.4

119.7

120.53 (10)

119.7

C2—C7—C9

C6—C7—C2

C6—C7—C9

121.21 (10)

117.18 (10)

121.61 (10)

109.5

C3—C8—H8A

C3—C8—H8B

C3—C8—H8C

H8A—C8—H8B

H8A—C8—H8C

H8B—C8—H8C

C7—C9—H9A

C7—C9—H9B

C7—C9—H9C

H9A—C9—H9B

H9A—C9—H9C

H9B—C9—H9C

109.5

120.67 (10)

119.7

109.5

N1—C2—C3—C4

N1—C2—C3—C8

N1—C2—C7—C6

N1—C2—C7—C9

C2—C3—C4—C5

C3—C2—C7—C6

C3—C2—C7—C9

178.95 (9)

−1.20 (15)

−179.59 (9)

0.90 (15)

1.01 (16)

0.41 (16)

C3—C4—C5—C6

C4—C5—C6—C7

C5—C6—C7—C2

C5—C6—C7—C9

C7—C2—C3—C4

C7—C2—C3—C8

C8—C3—C4—C5

−0.37 (17)

−0.31 (17)

0.29 (16)

179.80 (10)

−1.05 (16)

178.79 (9)

−178.83 (10)

−179.10 (10)

cis-Dibromidotetrakis(2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771-solvate (2a)

Crystal data

[

M

FeBr

2

(C

9

H

9 4

N) ]·0.771CH

2

Cl

2

Monoclinic, C2/c

a = 16.8177 (13) Å

r

= 805.87

Acta Cryst. (2019). C75

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supporting information

b = 15.8912 (12) Å

c = 14.1334 (11) Å

β = 92.9182 (10)°

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 1861 reflections

θ = 2.4–27.5°

3

−1

V = 3772.3 (5) Å

µ = 2.66 mm

Z = 4

T = 173 K

F(000) = 1634

Needle, orange

0.44 × 0.16 × 0.08 mm

−3

D

x

= 1.419 Mg m

Data collection

Bruker SMART CCD platform

diffractometer

4323 independent reflections

3646 reflections with I > 2σ(I)

Radiation source: normal-focus sealed tube

ω scans

R

int = 0.020

θ

max = 27.5°, θmin = 1.8°

Absorption correction: multi-scan

h = −21→21

k = −19→20

l = −18→17

(SADABS; Sheldrick, 2014)

T

min = 0.662, Tmax = 0.746

15633 measured reflections

Refinement

2

Refinement on F

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

Least-squares matrix: full

R[F > 2σ(F )] = 0.025

2

wR(F ) = 0.066

S = 1.03

H-atom parameters constrained

2

4

2

323 reflections

30 parameters

0 restraints

w = 1/[σ (F

where P = (F

o

) + (0.0376P) + 1.3322P]

2

o

+ 2F )/3

c

(Δ/σ)max = 0.001

Δρmax = 0.48 e Å

Δρmin = −0.31 e Å

−

3

Primary atom site location: structure-invariant

direct methods

−

3

Special details

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.

Refinement. During the mounting procedure there was a partial desolvation of the crystal. The cocrystallized

dichloromethane solvent, which is modeled as disordered (see below), is found in channels along the [001] direction. The

occupancies of the two components of the disorder were refined independently and summed to an occupancy of

0

.771 (13) relative to one iron complex. A test using the SQUEEZE routine of program PLATON (Spek, 2015), also

showed less than full occupancy of solvent in the channel: 168 electrons were expected, but only 150 were reported.

The cocrystallized dichloromethane solvent was modeled as disordered over a crystallographic two-fold axis (0.50:0.50),

and additionally over two general positions (0.579 (9) and 0.192 (9), see above response to alert PLAT077 for an

explanation of why the two numbers do not sum to 1.000). Analogous bond lengths and angles between the two positions

of the dichloromethane solvent disordere were restrained to be similar. Anisotropic displacement parameters for proximal

(including symmetry equivalent) atoms were constrained to be equivalent. Additionally, anisotropic displacement

parameters for all atoms of the major component were restrained to be similar.

2

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

x

y

z

Uiso*/Ueq

Occ. (<1)

Fe1

Br1

C1

0.500000

0.22824 (2)

0.11942 (2)

0.22520 (10)

0.22521 (9)

0.250000

0.02214 (8)

0.03483 (7)

0.0264 (3)

0.0309 (3)

0.40420 (2)

0.45319 (9)

0.42660 (9)

0.29733 (2)

0.12645 (12)

0.04962 (10)

N1

Acta Cryst. (2019). C75

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supporting information

C2

C3

C4

H4A

C5

H5A

C6

H6A

C7

0.39319 (11)

0.41615 (13)

0.37932 (17)

0.393109

0.32403 (18)

0.299385

0.30326 (17)

0.264967

0.33798 (14)

0.47627 (15)

0.474795

0.463744

0.529541

0.31701 (18)

0.297795

0.275227

0.22826 (12)

0.16724 (14)

0.17251 (19)

0.133019

0.2332 (2)

0.234244

0.29288 (19)

0.334674

0.29235 (15)

0.10095 (16)

0.056186

0.077275

0.126070

0.35630 (18)

0.327473

0.393571

−0.04309 (12)

−0.10721 (14)

−0.19825 (16)

−0.245145

−0.22106 (17)

−0.283042

−0.15603 (19)

−0.173779

−0.06463 (16)

−0.07896 (19)

−0.126714

−0.017445

−0.074263

0.0082 (2)

0.063952

0.0348 (4)

0.0432 (5)

0.0632 (7)

0.076*

0.0722 (9)

0.087*

0.0687 (8)

0.082*

0.0499 (5)

0.0610 (7)

0.091*

0.0738 (8)

0.111*

C8

H8A

H8B

H8C

C9

H9A

H9B

H9C

C10

N2

C11

C12

C13

H13A

C14

H14A

C15

H15A

C16

C17

H17A

H17B

H17C

H17D

H17E

H17F

C18

H18A

H18B

H18C

Cl1

−0.018524

0.026807

0.364306

0.389593

0.111*

0.42775 (10)

0.38106 (9)

0.32158 (10)

0.26934 (10)

0.20789 (11)

0.170436

0.20098 (11)

0.158679

0.25476 (12)

0.249421

0.31685 (11)

0.27863 (12)

0.236722

0.330863

0.274360

0.324574

0.230434

0.286937

0.37621 (14)

0.362542

0.429634

0.375161

0.5113 (5)

0.5096 (9)

0.464105

0.30503 (11)

0.35035 (10)

0.38481 (11)

0.44403 (11)

0.47249 (12)

0.511977

0.44380 (13)

0.463631

0.38675 (12)

0.368456

0.35549 (12)

0.47510 (13)

0.516159

0.501814

0.427536

0.447514

0.461858

0.536137

0.29283 (15)

0.277862

0.317589

0.242179

0.4486 (7)

0.3872 (6)

0.347616

0.29015 (11)

0.32005 (10)

0.37402 (13)

0.33280 (13)

0.38735 (14)

0.361295

0.47894 (14)

0.515018

0.51853 (14)

0.581887

0.46705 (13)

0.23332 (14)

0.216789

0.229207

0.189211

0.206683

0.194264

0.234260

0.50771 (15)

0.572153

0.509368

0.468101

0.6584 (7)

0.7698 (10)

0.767632

0.0257 (3)

0.0299 (3)

0.0292 (4)

0.0318 (4)

0.0371 (4)

0.045*

0.0404 (5)

0.048*

0.0404 (5)

0.049*

0.0343 (4)

0.0430 (5)

0.065*

0.0498 (5)

0.075*

0.1084 (12)

0.094 (8)

0.113*

0.5

0.290 (5)

0.096 (4)

C19

H19A

H19B

Cl2

0.559526

0.354894

0.780593

0.113*

0.4993 (4)

0.4834 (9)

0.471 (3)

0.414493

0.501982

0.4653 (6)

0.4791 (9)

0.3923 (15)

0.376005

0.8629 (8)

0.6060 (13)

0.6878 (17)

0.686380

0.1084 (12)

0.094 (8)

0.113*

Cl1′

C19′

H19C

H19D

0.343358

0.666233

0.113*

Acta Cryst. (2019). C75

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supporting information

Cl2′

0.5042 (11)

0.4174 (13)

0.8087 (14)

0.1084 (12)

0.096 (4)

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

Fe1

Br1

C1

N1

C2

C3

C4

C5

C6

C7

C8

C9

C10

N2

C11

C12

C13

C14

C15

C16

C17

C18

Cl1

C19

Cl2

Cl1′

C19′

Cl2′

0.02145 (15)

0.03405 (10)

0.0249 (8)

0.0327 (7)

0.0373 (9)

0.0458 (11)

0.0738 (16)

0.0807 (19)

0.0723 (17)

0.0536 (13)

0.0578 (15)

0.0805 (19)

0.0263 (8)

0.0302 (7)

0.0274 (8)

0.0330 (9)

0.0327 (9)

0.0354 (10)

0.0435 (11)

0.0351 (9)

0.0461 (11)

0.0563 (13)

0.085 (2)

0.02663 (17)

0.03661 (11)

0.0276 (8)

0.0360 (8)

0.0448 (11)

0.0521 (12)

0.0849 (19)

0.102 (2)

0.0808 (19)

0.0547 (13)

0.0572 (14)

0.0667 (16)

0.0308 (9)

0.0324 (8)

0.0305 (9)

0.0318 (9)

0.0364 (10)

0.0451 (11)

0.0481 (12)

0.0380 (10)

0.0458 (11)

0.0602 (14)

0.068 (3)

0.01831 (16)

0.03405 (11)

0.0268 (9)

0.0236 (8)

0.0215 (9)

0.0319 (10)

0.0309 (12)

0.0307 (12)

0.0499 (15)

0.0400 (12)

0.0685 (17)

0.0730 (19)

0.0199 (8)

0.0278 (8)

0.0302 (9)

0.0309 (9)

0.0426 (11)

0.0419 (11)

0.0309 (10)

0.0303 (10)

0.0377 (11)

0.0337 (11)

0.169 (5)

0.000

0.00083 (12)

0.00382 (7)

0.0027 (7)

−0.0020 (6)

−0.0054 (7)

0.0022 (8)

0.0034 (11)

−0.0225 (12)

−0.0258 (13)

−0.0115 (10)

0.0085 (12)

−0.0076 (15)

0.0007 (6)

0.0057 (6)

0.0072 (7)

0.0044 (7)

0.0055 (8)

0.0145 (8)

0.0128 (8)

0.0069 (8)

0.0090 (9)

0.0089 (9)

−0.022 (2)

−0.037 (11)

−0.022 (2)

−0.037 (11)

−0.022 (2)

0.000

−0.01018 (7)

0.0007 (6)

−0.0015 (6)

−0.0091 (8)

−0.0174 (10)

−0.0353 (16)

−0.0364 (17)

−0.0086 (15)

0.0011 (11)

−0.0023 (12)

0.0321 (15)

−0.0024 (7)

0.0025 (6)

0.0002 (7)

0.0007 (7)

0.0050 (8)

0.0004 (9)

−0.0011 (9)

0.0000 (8)

0.0136 (9)

0.0147 (11)

−0.006 (2)

0.018 (6)

0.00266 (7)

0.0006 (7)

0.0000 (6)

0.0023 (8)

−0.0081 (9)

−0.0162 (12)

0.0196 (14)

0.0245 (14)

0.0121 (10)

−0.0241 (13)

0.0016 (15)

0.0039 (7)

0.0004 (6)

−0.0050 (7)

−0.0040 (7)

−0.0060 (8)

−0.0112 (9)

−0.0039 (9)

−0.0007 (8)

0.0060 (9)

0.0107 (10)

−0.002 (2)

−0.047 (10)

−0.002 (2)

−0.047 (10)

−0.002 (2)

0.059 (14)

0.085 (2)

0.059 (14)

0.085 (2)

0.051 (5)

0.068 (3)

0.051 (5)

0.17 (2)

0.169 (5)

0.17 (2)

−0.006 (2)

0.018 (6)

0.068 (3)

0.169 (5)

−0.006 (2)

Geometric parameters (Å, º)

i

Fe1—C10

1.8325 (17)

C11—C16

1.401 (3)

Fe1—C10

Fe1—C1

1.8325 (17)

1.8791 (17)

2.4785 (3)

1.153 (2)

1.400 (2)

1.395 (3)

1.401 (3)

1.402 (3)

1.500 (3)

C12—C13

C12—C17

C13—C14

C13—H13A

C14—C15

C14—H14A

C15—C16

C15—H15A

C16—C18

C17—H17A

C17—H17B

1.396 (2)

1.506 (3)

1.383 (3)

0.9500

1.379 (3)

0.9500

1.394 (3)

0.9500

1.503 (3)

0.9800

i

Fe1—Br1

i

C1—N1

N1—C2

C2—C3

C2—C7

C3—C4

C3—C8

0.9800

Acta Cryst. (2019). C75

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supporting information

C4—C5

C4—H4A

C5—C6

C5—H5A

C6—C7

C6—H6A

C7—C9

C8—H8A

C8—H8B

C8—H8C

C9—H9A

C9—H9B

C9—H9C

C10—N2

N2—C11

C11—C12

1.367 (4)

0.9500

1.378 (4)

0.9500

1.390 (3)

0.9500

1.502 (4)

0.9800

C17—H17C

C17—H17D

C17—H17E

C17—H17F

C18—H18A

C18—H18B

C18—H18C

Cl1—C19

0.9800

1.854 (12)

1.823 (10)

0.9900

C19—Cl2

C19—H19A

C19—H19B

Cl1′—C19′

C19′—Cl2′

C19′—H19C

C19′—H19D

0.9900

1.817 (16)

1.813 (15)

0.9900

0.9800

1.161 (2)

1.400 (2)

1.394 (2)

0.9900

i

C10 —Fe1—C10

96.49 (10)

88.99 (7)

92.97 (7)

88.99 (7)

177.05 (10)

176.96 (5)

86.02 (5)

89.17 (5)

88.77 (5)

86.02 (5)

176.96 (5)

88.77 (5)

89.17 (5)

91.520 (15)

177.55 (15)

177.85 (18)

118.21 (18)

124.50 (18)

117.29 (18)

115.5 (2)

121.35 (19)

123.1 (2)

121.5 (2)

119.3

N2—C10—Fe1

C10—N2—C11

C12—C11—N2

C12—C11—C16

N2—C11—C16

175.84 (15)

163.00 (17)

119.25 (16)

123.50 (16)

117.23 (16)

117.15 (17)

121.21 (16)

121.63 (17)

120.67 (18)

119.7

120.80 (17)

119.6

121.04 (18)

119.5

i

C10 —Fe1—C1

C10—Fe1—C1

i

C10 —Fe1—C1

i

C10—Fe1—C1

i

C1—Fe1—C1

C11—C12—C13

C11—C12—C17

C13—C12—C17

C14—C13—C12

C14—C13—H13A

C12—C13—H13A

C15—C14—C13

C15—C14—H14A

C13—C14—H14A

C14—C15—C16

C14—C15—H15A

C16—C15—H15A

C15—C16—C11

C15—C16—C18

C11—C16—C18

C12—C17—H17A

C12—C17—H17B

H17A—C17—H17B

C12—C17—H17C

H17A—C17—H17C

H17B—C17—H17C

H17D—C17—H17E

H17D—C17—H17F

H17E—C17—H17F

C16—C18—H18A

C16—C18—H18B

i

C10 —Fe1—Br1

C10—Fe1—Br1

C1—Fe1—Br1

i

C1 —Fe1—Br1

i

C10 —Fe1—Br1

i

C10—Fe1—Br1

C1—Fe1—Br1

C1 —Fe1—Br1

i

Br1—Fe1—Br1

N1—C1—Fe1

C1—N1—C2

C3—C2—N1

C3—C2—C7

N1—C2—C7

C2—C3—C4

C2—C3—C8

C4—C3—C8

C5—C4—C3

C5—C4—H4A

C3—C4—H4A

C4—C5—C6

C4—C5—H5A

C6—C5—H5A

C5—C6—C7

C5—C6—H6A

119.5

116.81 (18)

122.47 (17)

120.71 (16)

109.5

119.3

121.4 (2)

119.3

120.5 (3)

119.8

109.5

Acta Cryst. (2019). C75

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supporting information

C7—C6—H6A

C6—C7—C2

C6—C7—C9

119.8

H18A—C18—H18B

C16—C18—H18C

H18A—C18—H18C

H18B—C18—H18C

Cl2—C19—Cl1

Cl2—C19—H19A

Cl1—C19—H19A

Cl2—C19—H19B

Cl1—C19—H19B

H19A—C19—H19B

Cl2′—C19′—Cl1′

Cl2′—C19′—H19C

Cl1′—C19′—H19C

Cl2′—C19′—H19D

Cl1′—C19′—H19D

H19C—C19′—H19D

109.5

105.2 (5)

110.7

108.8

113.2 (14)

108.9

107.7

116.7 (2)

122.1 (2)

121.28 (19)

109.5

C2—C7—C9

C3—C8—H8A

C3—C8—H8B

H8A—C8—H8B

C3—C8—H8C

H8A—C8—H8C

H8B—C8—H8C

C7—C9—H9A

C7—C9—H9B

H9A—C9—H9B

C7—C9—H9C

H9A—C9—H9C

H9B—C9—H9C

109.5

N1—C2—C3—C4

C7—C2—C3—C4

N1—C2—C3—C8

C7—C2—C3—C8

C2—C3—C4—C5

C8—C3—C4—C5

C3—C4—C5—C6

C4—C5—C6—C7

C5—C6—C7—C2

C5—C6—C7—C9

C3—C2—C7—C6

N1—C2—C7—C6

C3—C2—C7—C9

N1—C2—C7—C9

C10—N2—C11—C12

178.63 (18)

−0.6 (3)

−1.3 (3)

179.5 (2)

−0.8 (3)

179.1 (2)

1.3 (4)

−0.5 (4)

−0.8 (4)

180.0 (3)

1.4 (3)

C10—N2—C11—C16

N2—C11—C12—C13

C16—C11—C12—C13

N2—C11—C12—C17

C16—C11—C12—C17

C11—C12—C13—C14

C17—C12—C13—C14

C12—C13—C14—C15

C13—C14—C15—C16

C14—C15—C16—C11

C14—C15—C16—C18

C12—C11—C16—C15

N2—C11—C16—C15

C12—C11—C16—C18

N2—C11—C16—C18

27.6 (7)

175.94 (16)

−2.3 (3)

−3.5 (3)

178.28 (18)

1.3 (3)

−179.29 (18)

0.3 (3)

−0.9 (3)

0.0 (3)

−179.6 (2)

1.7 (3)

−177.9 (2)

−179.4 (2)

1.4 (3)

−176.60 (17)

−178.75 (19)

3.0 (3)

−150.8 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

trans-Dibromidotetrakis(2,6-dimethylphenyl isocyanide)iron(II) (2b)

Crystal data

−3

[

FeBr

2

(C

9 9 4

H N) ]

D

x

= 1.487 Mg m

M

r

= 740.36

Mo Kα radiation, λ = 0.71073 Å

Orthorhombic, Pbca

a = 14.4246 (13) Å

b = 14.0229 (13) Å

c = 16.3444 (15) Å

Cell parameters from 2048 reflections

θ = 2.4–27.4°

µ = 2.90 mm

T = 173 K

−1

3

V = 3306.1 (5) Å

Block, blue-violet

Z = 4

0.25 × 0.20 × 0.15 mm

F(000) = 1504

Acta Cryst. (2019). C75

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supporting information

Data collection

Siemens SMART CCD platform

diffractometer

3790 independent reflections

3151 reflections with I > 2σ(I)

Radiation source: normal-focus sealed tube

ω scans

R

int = 0.023

θ

max = 27.5°, θmin = 2.4°

Absorption correction: multi-scan

h = −17→18

k = −18→18

l = −21→21

(SADABS; Sheldrick, 2014)

T

min = 0.592, Tmax = 0.746

2

5764 measured reflections

Refinement

2

Refinement on F

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

Least-squares matrix: full

R[F > 2σ(F )] = 0.025

2

wR(F ) = 0.065

S = 1.03

H-atom parameters constrained

2

3

1

0

790 reflections

98 parameters

restraints

w = 1/[σ (F

where P = (F

o

) + (0.031P) + 2.1282P]

2

o

+ 2F )/3

c

(Δ/σ)max < 0.001

Δρmax = 0.32 e Å

Δρmin = −0.52 e Å

−

3

Primary atom site location: structure-invariant

direct methods

−

3

Special details

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

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

x

y

z

Uiso*/Ueq

Occ. (<1)

Fe1

Br1

C1

N1

C2

C3

C4

H4A

C5

H5A

C6

H6A

C7

C8

H8A

H8B

H8C

H8D

H8E

H8F

0.000000

0.500000

0.01608 (8)

0.02887 (7)

0.0193 (3)

0.0230 (3)

0.0209 (3)

0.0225 (4)

0.0263 (4)

0.032*

0.0283 (4)

0.034*

0.0263 (4)

0.032*

0.0231 (3)

0.0314 (4)

0.047*

0.15064 (2)

−0.06328 (12)

−0.10460 (10)

−0.15108 (12)

−0.16043 (12)

−0.19996 (13)

−0.206190

−0.23023 (13)

−0.255244

−0.22434 (12)

−0.248075

−0.18419 (12)

−0.13120 (14)

−0.105081

−0.185127

−0.084299

0.50738 (2)

0.56121 (11)

0.60276 (10)

0.67006 (12)

0.65280 (12)

0.72519 (13)

0.716791

0.80895 (13)

0.858165

0.82168 (12)

0.878373

0.75256 (12)

0.56026 (13)

0.518397

0.529337

0.572607

0.42887 (2)

0.41390 (10)

0.36485 (9)

0.31575 (10)

0.23198 (11)

0.18514 (11)

0.127727

0.22070 (12)

0.187406

0.30484 (12)

0.328791

0.35443 (11)

0.19373 (12)

0.235850

0.168706

0.151663

0.5

−0.144590

−0.064544

−0.165373

0.561831

0.550890

0.507620

0.134963

0.202107

0.219149

0.047*

Acta Cryst. (2019). C75

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supporting information

C9

−0.17650 (15)

−0.146411

−0.139490

−0.238583

−0.203245

0.76572 (15)

0.709744

0.822717

0.773257

0.827402

0.44568 (12)

0.469840

0.457396

0.469151

0.461085

0.0346 (5)

0.052*

H9A

H9B

H9C

H9D

H9E

H9F

0.5

−0.210166

−0.111073

0.714429

0.763888

0.473529

0.461774

C10

N2

C11

C12

C13

H13A

C14

H14A

C15

H15A

C16

−0.02539 (12)

−0.04306 (11)

−0.06811 (12)

−0.09778 (13)

−0.12441 (14)

−0.144915

−0.12147 (14)

−0.139892

−0.09205 (13)

−0.091054

−0.06396 (12)

−0.10146 (17)

−0.056456

−0.086430

−0.163889

0.37964 (11)

0.30496 (10)

0.22107 (11)

0.14231 (13)

0.06187 (13)

0.006661

0.06116 (13)

0.005522

0.14043 (13)

0.138693

0.22243 (12)

0.14458 (17)

0.191126

0.081254

0.162832

0.45537 (10)

0.42980 (9)

0.38876 (10)

0.43430 (11)

0.39012 (13)

0.418526

0.30577 (13)

0.276866

0.26284 (11)

0.204738

0.30311 (11)

0.52657 (12)

0.547128

0.548182

0.544300

0.0201 (3)

0.0237 (3)

0.0205 (3)

0.0264 (4)

0.0330 (4)

0.040*

0.0340 (4)

0.041*

0.0277 (4)

0.033*

0.0217 (3)

0.0408 (5)

0.061*

C17

H17A

H17B

H17C

H17D

H17E

H17F

C18

H18A

H18B

H18C

0.5

−0.148061

−0.118087

−0.040628

−0.03274 (13)

0.031277

0.099016

0.208888

0.127310

0.31020 (13)

0.325211

0.545946

0.544891

0.548773

0.25826 (12)

0.273649

0.061*

0.0292 (4)

0.044*

−0.073117

−0.036025

0.363829

0.298833

0.272696

0.199171

0.044*

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

Fe1

Br1

C1

N1

C2

C3

C4

C5

C6

C7

C8

C9

C10

N2

C11

0.02056 (17)

0.02599 (11)

0.0228 (9)

0.0239 (8)

0.0185 (8)

0.0220 (9)

0.0250 (10)

0.0241 (9)

0.0213 (9)

0.0183 (8)

0.0351 (11)

0.0366 (12)

0.0228 (9)

0.0260 (8)

0.0195 (8)

0.01488 (15)

0.03546 (11)

0.0182 (7)

0.0242 (7)

0.0224 (8)

0.0231 (8)

0.0331 (9)

0.0272 (9)

0.0218 (8)

0.0267 (8)

0.0289 (9)

0.0408 (11)

0.0212 (8)

0.0217 (7)

0.0186 (7)

0.01281 (15)

0.02516 (11)

0.0171 (8)

0.0210 (7)

0.0219 (8)

0.0225 (9)

0.0209 (9)

0.0336 (10)

0.0356 (10)

0.0242 (9)

0.0302 (10)

0.0266 (10)

0.0161 (8)

0.0236 (7)

0.0235 (9)

0.00096 (12)

−0.00284 (12)

0.00558 (7)

−0.0004 (7)

−0.0039 (6)

−0.0048 (7)

−0.0035 (7)

−0.0054 (7)

−0.0039 (8)

0.0006 (7)

−0.0006 (7)

−0.0087 (8)

−0.0019 (9)

−0.0036 (7)

−0.0027 (6)

−0.0018 (7)

0.00069 (12)

0.00650 (7)

−0.0007 (6)

0.0047 (6)

0.0081 (6)

0.0042 (6)

0.0079 (7)

0.0132 (8)

0.0037 (7)

0.0024 (7)

−0.0033 (8)

−0.0034 (8)

0.0022 (6)

−0.0029 (6)

−0.0046 (6)

0.00368 (7)

−0.0021 (6)

−0.0017 (6)

−0.0028 (6)

−0.0040 (7)

−0.0016 (7)

0.0002 (7)

−0.0010 (7)

−0.0045 (7)

0.0002 (8)

0.0001 (9)

0.0020 (6)

0.0005 (6)

0.0007 (6)

Acta Cryst. (2019). C75

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supporting information

C12

C13

C14

C15

C16

C17

C18

0.0259 (9)

0.0336 (11)

0.0333 (11)

0.0264 (10)

0.0175 (8)

0.0476 (14)

0.0268 (10)

0.0265 (8)

0.0225 (8)

0.0253 (9)

0.0327 (9)

0.0246 (8)

0.0477 (12)

0.0325 (9)

0.0268 (9)

0.0430 (12)

0.0434 (12)

0.0238 (9)

0.0228 (8)

0.0271 (10)

0.0283 (10)

−0.0020 (7)

−0.0075 (8)

−0.0042 (8)

0.0024 (8)

0.0021 (6)

−0.0098 (10)

0.0012 (8)

−0.0017 (8)

−0.0012 (9)

−0.0046 (9)

−0.0017 (8)

−0.0006 (7)

−0.0004 (10)

0.0018 (8)

0.0027 (7)

0.0031 (8)

−0.0125 (8)

−0.0083 (7)

−0.0015 (7)

0.0086 (9)

0.0057 (8)

Geometric parameters (Å, º)

Fe1—C10

1.8748 (16)

C9—H9C

C9—H9D

C9—H9E

C9—H9F

C10—N2

N2—C11

0.9800

i

Fe1—C10

1.8748 (16)

1.8842 (16)

2.4665 (3)

1.156 (2)

1.409 (2)

1.397 (2)

1.402 (2)

1.393 (2)

1.501 (2)

1.381 (3)

0.9500

1.389 (3)

0.9500

1.390 (2)

0.9500

1.507 (3)

0.9800

i

Fe1—C1

Fe1—Br1

1.156 (2)

1.402 (2)

1.399 (2)

1.401 (2)

1.393 (3)

1.509 (3)

1.379 (3)

0.9500

1.381 (3)

0.9500

1.386 (2)

0.9500

1.502 (2)

0.9800

i

C1—N1

N1—C2

C2—C3

C2—C7

C3—C4

C3—C8

C4—C5

C4—H4A

C5—C6

C5—H5A

C6—C7

C11—C12

C11—C16

C12—C13

C12—C17

C13—C14

C13—H13A

C14—C15

C14—H14A

C15—C16

C15—H15A

C16—C18

C17—H17A

C17—H17B

C17—H17C

C17—H17D

C17—H17E

C17—H17F

C18—H18A

C18—H18B

C18—H18C

C6—H6A

C7—C9

C8—H8A

C8—H8B

C8—H8C

C8—H8D

C8—H8E

C8—H8F

C9—H9A

C9—H9B

0.9800

i

C10—Fe1—C10

180.0

H9D—C9—H9E

H9D—C9—H9F

H9E—C9—H9F

N2—C10—Fe1

C10—N2—C11

C12—C11—C16

C12—C11—N2

C16—C11—N2

C13—C12—C11

C13—C12—C17

109.5

177.84 (16)

171.99 (17)

123.74 (16)

119.13 (16)

117.10 (15)

116.59 (17)

121.68 (17)

i

C10—Fe1—C1

C10 —Fe1—C1

88.57 (7)

91.43 (7)

88.57 (7)

180.0

91.52 (5)

88.49 (5)

86.81 (5)

93.19 (5)

i

C10—Fe1—C1

i

C10 —Fe1—C1

i

C1 —Fe1—C1

C10—Fe1—Br1

i

C10 —Fe1—Br1

i

C1 —Fe1—Br1

C1—Fe1—Br1

Acta Cryst. (2019). C75

sup-11

supporting information

i

C10—Fe1—Br1

88.49 (5)

91.51 (5)

93.19 (5)

86.81 (5)

180.0

175.50 (15)

167.90 (17)

123.50 (15)

119.23 (15)

117.26 (15)

116.86 (16)

121.07 (16)

122.06 (15)

121.18 (17)

119.4

C11—C12—C17

C14—C13—C12

121.72 (17)

121.02 (18)

119.5

120.76 (17)

119.6

121.09 (17)

119.5

i

C10 —Fe1—Br1

i

C1 —Fe1—Br1

C14—C13—H13A

C12—C13—H13A

C13—C14—C15

C13—C14—H14A

C15—C14—H14A

C14—C15—C16

C14—C15—H15A

C16—C15—H15A

C15—C16—C11

i

C1—Fe1—Br1

i

Br1—Fe1—Br1

N1—C1—Fe1

C1—N1—C2

C3—C2—C7

C3—C2—N1

C7—C2—N1

C4—C3—C2

C4—C3—C8

C2—C3—C8

C5—C4—C3

C5—C4—H4A

C3—C4—H4A

C4—C5—C6

C4—C5—H5A

C6—C5—H5A

C5—C6—C7

C5—C6—H6A

C7—C6—H6A

C6—C7—C2

C6—C7—C9

C2—C7—C9

C3—C8—H8A

C3—C8—H8B

119.5

116.80 (16)

122.41 (17)

120.77 (16)

109.5

141.1

56.3

109.5

56.3

141.1

56.3

109.5

56.3

141.1

109.5

C15—C16—C18

C11—C16—C18

C12—C17—H17A

C12—C17—H17B

H17A—C17—H17B

C12—C17—H17C

H17A—C17—H17C

H17B—C17—H17C

C12—C17—H17D

H17A—C17—H17D

H17B—C17—H17D

H17C—C17—H17D

C12—C17—H17E

H17A—C17—H17E

H17B—C17—H17E

H17C—C17—H17E

H17D—C17—H17E

C12—C17—H17F

H17A—C17—H17F

H17B—C17—H17F

H17C—C17—H17F

H17D—C17—H17F

H17E—C17—H17F

C16—C18—H18A

C16—C18—H18B

H18A—C18—H18B

C16—C18—H18C

H18A—C18—H18C

H18B—C18—H18C

119.4

120.42 (16)

119.8

120.87 (17)

119.6

117.02 (16)

121.50 (17)

121.48 (16)

109.5

H8A—C8—H8B

C3—C8—H8C

H8A—C8—H8C

H8B—C8—H8C

H8D—C8—H8E

H8D—C8—H8F

H8E—C8—H8F

C7—C9—H9A

C7—C9—H9B

H9A—C9—H9B

C7—C9—H9C

H9A—C9—H9C

H9B—C9—H9C

C1—N1—C2—C3

C1—N1—C2—C7

C7—C2—C3—C4

N1—C2—C3—C4

C7—C2—C3—C8

N1—C2—C3—C8

C2—C3—C4—C5

154.1 (8)

−24.8 (9)

4.0 (3)

−174.72 (16)

−174.87 (17)

6.4 (3)

N1—C2—C7—C9

−4.2 (3)

−0.1 (3)

178.14 (17)

−179.69 (19)

−1.4 (3)

C16—C11—C12—C13

N2—C11—C12—C13

C16—C11—C12—C17

N2—C11—C12—C17

C11—C12—C13—C14

C17—C12—C13—C14

−0.1 (3)

179.4 (2)

−1.5 (3)

Acta Cryst. (2019). C75

sup-12

supporting information

C8—C3—C4—C5

C3—C4—C5—C6

C4—C5—C6—C7

C5—C6—C7—C2

C5—C6—C7—C9

C3—C2—C7—C6

N1—C2—C7—C6

C3—C2—C7—C9

177.44 (17)

−1.9 (3)

2.9 (3)

−0.5 (3)

179.43 (17)

−3.0 (3)

C12—C13—C14—C15

−0.1 (3)

0.6 (3)

−0.8 (3)

−179.21 (17)

0.6 (3)

−177.71 (15)

179.04 (17)

0.7 (3)

C13—C14—C15—C16

C14—C15—C16—C11

C14—C15—C16—C18

C12—C11—C16—C15

N2—C11—C16—C15

C12—C11—C16—C18

N2—C11—C16—C18

175.72 (15)

177.00 (17)

Symmetry code: (i) −x, −y+1, −z+1.

Pentakis(2,6-dimethylphenyl isocyanide)iron(0) tris(µ

2

-2,6-dimethylphenyl isocyanide)bis[tris(2,6-dimethylphenyl

isocyanide)iron(0)] (3)

Crystal data

[

M

Fe(C

= 2003.95

Monoclinic, P2

9

H

9

N)

5

][Fe

2

(C

9 9 9

H N) ]

F(000) = 4232

−3

r

D = 1.217 Mg m

x

1

/n

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 4028 reflections

θ = 2.2–25.0°

a = 24.901 (3) Å

b = 14.2838 (19) Å

c = 30.954 (4) Å

β = 96.654 (2)°

−1

µ = 0.45 mm

T = 173 K

Plate, red

3

V = 10935 (3) Å

Z = 4

0.36 × 0.28 × 0.08 mm

Data collection

Bruker SMART CCD platform

diffractometer

19257 independent reflections

10377 reflections with I > 2σ(I)

Radiation source: normal-focus sealed tube

ω scans

R

int = 0.086

θ

max = 25.0°, θmin = 1.3°

Absorption correction: multi-scan

h = −29→29

k = −16→16

l = −36→36

(SADABS; Sheldrick, 2014)

T

min = 0.662, Tmax = 0.746

75619 measured reflections

Refinement

2

Refinement on F

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

Least-squares matrix: full

R[F > 2σ(F )] = 0.063

2

wR(F ) = 0.153

S = 1.02

H-atom parameters constrained

2

19257 reflections

1316 parameters

0 restraints

w = 1/[σ (F

where P = (F

o

) + (0.0675P) ]

2

o

+ 2F )/3

c

(Δ/σ)max = 0.001

Δρmax = 0.44 e Å

Δρmin = −0.47 e Å

−

3

Primary atom site location: structure-invariant

direct methods

−

3

Special details

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.

Acta Cryst. (2019). C75

sup-13

supporting information

2

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

x

y

z

Uiso*/Ueq

Fe1

N1

N2

N3

N4

N5

C1

C2

C3

C4

H4A

C5

H5A

C6

H6A

C7

C8

H8A

H8B

H8C

C9

H9A

H9B

H9C

C10

C11

C12

C13

H13A

C14

H14A

C15

H15A

C16

C17

H17A

H17B

H17C

C18

H18A

H18B

H18C

C19

C20

C21

0.22105 (2)

0.31653 (14)

0.21434 (14)

0.14953 (14)

0.13589 (14)

0.27948 (13)

0.27835 (17)

0.36379 (16)

0.38571 (18)

0.4334 (2)

0.449717

0.4571 (2)

0.489931

0.4345 (2)

0.451290

0.38719 (19)

0.3592 (2)

0.344875

0.44139 (4)

0.3460 (2)

0.3871 (2)

0.2785 (2)

0.5677 (2)

0.6227 (3)

0.3861 (3)

0.3255 (3)

0.2355 (3)

0.2192 (4)

0.158986

0.2884 (5)

0.275914

0.3753 (5)

0.422063

0.3959 (3)

0.1581 (3)

0.183389

0.109307

0.131294

0.4909 (3)

0.532089

0.518323

0.483925

0.4112 (3)

0.3458 (3)

0.2937 (3)

0.2535 (4)

0.217141

0.2654 (4)

0.237742

0.3165 (4)

0.323654

0.3588 (3)

0.2813 (4)

0.246552

0.246331

0.342790

0.4142 (3)

0.431227

0.471104

0.376004

0.3418 (3)

0.2052 (3)

0.2142 (4)

0.03639 (2)

0.00409 (10)

0.12960 (12)

0.00842 (11)

−0.00815 (12)

0.05564 (11)

0.01537 (12)

−0.01425 (13)

−0.00936 (14)

−0.02749 (18)

−0.024901

−0.0489 (2)

−0.060662

−0.05379 (16)

−0.069389

−0.03621 (14)

0.01352 (18)

0.039305

0.03866 (16)

0.0470 (9)

0.0543 (10)

0.0503 (9)

0.0536 (9)

0.0491 (9)

0.0425 (10)

0.0458 (11)

0.0580 (12)

0.0795 (16)

0.095*

0.0890 (19)

0.107*

0.0792 (16)

0.095*

0.0546 (12)

0.0833 (16)

0.125*

0.385871

0.329546

0.3605 (2)

0.383129

0.356197

0.022359

−0.006227

−0.04256 (16)

−0.058207

−0.014139

0.125*

0.0835 (17)

0.125*

0.324944

−0.059448

0.125*

0.21768 (16)

0.19994 (19)

0.1519 (2)

0.1386 (2)

0.106560

0.1712 (3)

0.161165

0.2178 (2)

0.239792

0.23395 (19)

0.1167 (2)

0.084003

0.136486

0.106461

0.09343 (14)

0.16815 (14)

0.16517 (16)

0.20327 (19)

0.202681

0.0438 (10)

0.0520 (12)

0.0617 (13)

0.0816 (16)

0.098*

0.0914 (19)

0.110*

0.0780 (16)

0.094*

0.0575 (12)

0.0759 (15)

0.114*

0.2420 (2)

0.267830

0.24370 (16)

0.270716

0.20627 (15)

0.12288 (16)

0.127904

0.102558

0.110536

0.20696 (15)

0.237008

0.189529

0.28582 (19)

0.298918

0.279020

0.0652 (13)

0.098*

0.313127

0.194804

0.098*

0.17827 (16)

0.11466 (17)

0.0596 (2)

0.01932 (12)

−0.00479 (13)

−0.00154 (14)

0.0407 (10)

0.0466 (11)

0.0606 (13)

Acta Cryst. (2019). C75

sup-14

supporting information

C22

H22A

C23

H23A

C24

H24A

C25

0.0260 (2)

−0.011713

0.0484 (3)

0.025658

0.1018 (3)

0.115507

0.1374 (2)

0.0371 (2)

−0.000313

0.058738

0.038043

0.1970 (2)

0.205654

0.216401

0.207939

0.16981 (17)

0.10708 (15)

0.11309 (16)

0.08544 (19)

0.088677

0.0534 (2)

0.035772

0.04705 (19)

0.024339

0.07315 (17)

0.14722 (19)

0.135167

0.143655

0.185134

0.1390 (5)

0.142358

0.0589 (5)

0.007596

0.0533 (4)

−0.002024

0.1244 (3)

0.3001 (4)

0.308239

0.354030

0.295465

0.1167 (4)

0.053260

0.129506

0.162113

0.5161 (3)

0.6224 (3)

0.7203 (3)

0.7720 (3)

0.838300

0.7290 (4)

0.765711

0.6341 (4)

0.605667

0.5786 (3)

0.7643 (3)

0.742277

0.832521

0.746762

0.4748 (3)

0.453215

0.458960

0.444142

0.5492 (3)

0.7164 (3)

0.7422 (3)

0.8368 (4)

0.859020

0.8990 (4)

0.962978

0.8698 (4)

0.913409

0.7762 (3)

0.6708 (4)

0.641838

0.701042

0.622669

0.7401 (4)

−0.01518 (16)

−0.013234

−0.03170 (18)

−0.040891

−0.03480 (17)

−0.046533

−0.02172 (14)

0.01536 (17)

0.002230

0.008097

0.047023

−0.02383 (19)

−0.032966

0.004932

−0.044856

0.00845 (13)

−0.04069 (13)

−0.03803 (14)

−0.07186 (16)

−0.071667

−0.10564 (16)

−0.128621

−0.10619 (15)

−0.129292

−0.07361 (14)

−0.00035 (15)

0.026925

0.0777 (17)

0.093*

0.099 (2)

0.119*

0.0875 (18)

0.105*

0.0623 (13)

0.0859 (17)

0.129*

0.0902 (18)

0.135*

C26

H26A

H26B

H26C

C27

H27A

H27B

H27C

C28

C29

C30

C31

H31A

C32

0.135*

0.0427 (10)

0.0423 (10)

0.0461 (10)

0.0614 (13)

0.074*

0.0675 (14)

0.081*

0.0669 (14)

0.080*

0.0506 (11)

0.0637 (13)

0.096*

H32A

C33

H33A

C34

C35

H35A

H35B

H35C

C36

H36A

H36B

H36C

C37

C38

C39

C40

H40A

C41

−0.002163

−0.001199

0.0651 (2)

0.056710

0.035084

−0.07404 (16)

−0.104124

−0.057484

−0.060793

0.04894 (12)

0.06727 (15)

0.11051 (17)

0.1201 (2)

0.148536

0.0890 (3)

0.096563

0.0476 (2)

0.0739 (15)

0.111*

0.098180

0.111*

0.25862 (16)

0.29086 (16)

0.28553 (17)

0.2947 (2)

0.291032

0.3090 (2)

0.314814

0.3151 (2)

0.325212

0.30636 (17)

0.2726 (2)

0.237639

0.270815

0.300807

0.0425 (10)

0.0479 (11)

0.0622 (13)

0.0900 (19)

0.108*

0.094 (2)

0.113*

0.0842 (18)

0.101*

0.0598 (13)

0.0864 (17)

0.130*

H41A

C42

H42A

C43

0.026827

0.03605 (17)

0.14287 (17)

0.133016

0.171093

0.145769

C44

H44A

H44B

H44C

C45

0.3144 (2)

−0.00862 (17)

0.0819 (16)

Acta Cryst. (2019). C75

sup-15

supporting information

H45A

H45B

H45C

Fe2

Fe3

N6

N7

N8

N9

N10

N11

N12

N13

N14

C46

C47

C48

C49

H49A

C50

H50A

C51

H51A

C52

C53

H53A

H53B

H53C

C54

H54A

H54B

H54C

C55

C56

C57

C58

H58A

C59

H59A

C60

H60A

C61

0.320106

0.282256

0.346027

0.792980

0.705059

0.698808

0.29471 (4)

0.21657 (4)

0.1993 (2)

0.3945 (2)

0.4578 (2)

0.2150 (2)

0.1446 (2)

0.4306 (2)

0.0050 (3)

0.2235 (2)

0.2318 (2)

0.2319 (3)

0.1720 (3)

0.2094 (3)

0.1801 (3)

0.204073

0.1173 (4)

0.096081

0.0853 (3)

0.043329

0.1117 (3)

0.2801 (3)

0.333099

0.302274

0.251188

0.0807 (4)

0.075600

0.126488

0.019533

0.3540 (3)

0.4209 (3)

0.3703 (4)

0.3932 (6)

0.360233

0.4613 (6)

0.473225

0.5152 (4)

0.564951

0.4934 (4)

0.2922 (4)

0.316192

0.267540

0.242109

0.5446 (4)

0.596451

−0.027726

−0.020659

−0.006455

0.23064 (2)

0.22556 (2)

0.20430 (10)

0.30715 (11)

0.17140 (12)

0.14245 (11)

0.30016 (11)

0.24689 (10)

0.22404 (10)

0.29755 (10)

0.16143 (10)

0.21639 (12)

0.17897 (14)

0.13688 (14)

0.11257 (16)

0.084023

0.1289 (2)

0.111222

0.1705 (2)

0.181367

0.19757 (17)

0.12026 (14)

0.140453

0.091572

0.117877

0.24386 (18)

0.256864

0.260137

0.123*

0.48319 (2)

0.57102 (2)

0.37587 (14)

0.44465 (14)

0.45217 (14)

0.48951 (13)

0.51659 (12)

0.57460 (13)

0.57532 (12)

0.66447 (12)

0.65374 (13)

0.41850 (17)

0.32775 (16)

0.31731 (16)

0.26981 (18)

0.260780

0.2357 (2)

0.204364

0.2466 (2)

0.221760

0.29269 (18)

0.35431 (17)

0.358936

0.03793 (16)

0.03666 (15)

0.0464 (9)

0.0488 (9)

0.0513 (9)

0.0449 (8)

0.0410 (8)

0.0418 (8)

0.0429 (8)

0.0418 (8)

0.0451 (9)

0.0412 (10)

0.0480 (11)

0.0493 (11)

0.0632 (13)

0.076*

0.0765 (16)

0.092*

0.0781 (17)

0.094*

0.0595 (13)

0.0592 (13)

0.089*

0.338660

0.389532

0.3044 (2)

0.270476

0.328062

0.089*

0.0861 (17)

0.129*

0.322395

0.244893

0.129*

0.46174 (16)

0.41949 (19)

0.3740 (2)

0.3514 (2)

0.320550

0.3726 (3)

0.356554

0.4153 (3)

0.427635

0.4415 (2)

0.3520 (2)

0.343778

0.318904

0.378916

0.27856 (14)

0.34382 (14)

0.35267 (16)

0.3898 (2)

0.397044

0.4155 (2)

0.441313

0.40802 (19)

0.427021

0.36932 (18)

0.32309 (18)

0.293399

0.333198

0.323433

0.0436 (10)

0.0529 (12)

0.0699 (15)

0.096 (2)

0.116*

0.105 (2)

0.126*

0.089 (2)

0.107*

0.0751 (15)

0.0885 (17)

0.133*

C62

H62A

H62B

H62C

C63

0.4892 (3)

0.497263

0.3580 (2)

0.378483

0.106 (2)

0.160*

H63A

Acta Cryst. (2019). C75

sup-16

supporting information

H63B

H63C

C64

C65

C66

C67

H67A

C68

H68A

C69

H69A

C70

0.481753

0.520204

0.569510

0.502119

0.3933 (3)

0.5475 (3)

0.5576 (3)

0.6481 (4)

0.658124

0.7228 (4)

0.783834

0.7118 (3)

0.764863

0.6225 (3)

0.4754 (4)

0.493357

0.455455

0.423615

0.6066 (3)

0.666999

0.573458

0.568871

0.2299 (3)

0.1606 (3)

0.2004 (3)

0.1432 (4)

0.168436

0.0513 (4)

0.012933

0.0150 (3)

−0.047955

0.0688 (3)

0.3018 (3)

0.307093

0.330641

0.333775

0.0334 (3)

−0.030871

0.073652

0.034382

0.1951 (3)

0.1323 (3)

0.0582 (3)

0.0423 (4)

−0.006804

0.0962 (4)

0.084753

0.1669 (4)

0.203257

0.1867 (3)

0.328408

0.359595

0.160*

0.46387 (15)

0.44089 (15)

0.42878 (16)

0.41855 (17)

0.409979

0.42074 (19)

0.413849

0.43256 (19)

0.433379

0.44349 (17)

0.4263 (2)

0.441062

0.388631

0.447602

0.19426 (13)

0.15406 (15)

0.10934 (15)

0.09363 (18)

0.063270

0.1215 (2)

0.110052

0.1655 (2)

0.184082

0.18319 (16)

0.07893 (15)

0.052122

0.071971

0.092856

0.0421 (10)

0.0485 (11)

0.0543 (12)

0.0696 (15)

0.083*

0.0756 (16)

0.091*

0.0702 (14)

0.084*

0.0570 (12)

0.0806 (16)

0.121*

C71

H71A

H71B

H71C

C72

H72A

H72B

H72C

C73

C74

C75

C76

H76A

C77

0.4572 (2)

0.459957

0.491818

0.23141 (15)

0.246485

0.236741

0.0721 (14)

0.108*

0.428772

0.242300

0.108*

0.50909 (15)

0.50691 (16)

0.53932 (17)

0.55468 (19)

0.576890

0.5387 (2)

0.551050

0.50454 (19)

0.492598

0.48717 (17)

0.55509 (19)

0.594497

0.542865

0.538218

0.18069 (12)

0.10838 (13)

0.07920 (13)

0.04648 (15)

0.026375

0.04234 (16)

0.020459

0.07014 (15)

0.066515

0.10344 (14)

0.08107 (14)

0.082549

0.106940

0.054960

0.0380 (9)

0.0442 (10)

0.0494 (11)

0.0627 (13)

0.075*

0.0701 (14)

0.084*

0.0609 (13)

0.073*

0.0492 (11)

0.0631 (13)

0.095*

H77A

C78

H78A

C79

C80

H80A

H80B

H80C

C81

H81A

H81B

H81C

C82

C83

C84

C85

H85A

C86

0.44740 (18)

0.436754

0.415330

0.13308 (16)

0.124927

0.130247

0.0645 (13)

0.097*

0.464362

0.163272

0.097*

0.51861 (15)

0.47746 (15)

0.44111 (17)

0.40438 (19)

0.378699

0.4045 (2)

0.379091

0.44209 (19)

0.442713

0.26791 (13)

0.32913 (13)

0.32149 (14)

0.35142 (18)

0.346257

0.38833 (17)

0.408354

0.39578 (15)

0.421546

0.0392 (10)

0.0407 (10)

0.0511 (11)

0.0678 (14)

0.081*

0.0716 (15)

0.086*

0.0606 (13)

0.073*

H86A

C87

H87A

C88

0.47908 (17)

0.36669 (13)

0.0471 (11)

Acta Cryst. (2019). C75

sup-17

supporting information

C89

0.44298 (19)

0.415480

0.478823

0.435846

0.52158 (18)

0.505490

−0.0044 (3)

−0.053418

−0.033182

0.033106

0.2613 (3)

0.315231

0.28213 (15)

0.282190

0.283187

0.255558

0.37707 (14)

0.390309

0.0662 (13)

0.099*

0.0571 (12)

0.086*

H89A

H89B

H89C

C90

H90A

H90B

H90C

C91

C92

C93

C94

H94A

C95

0.535707

0.551136

0.280928

0.236064

0.350237

0.397418

0.086*

0.55543 (16)

0.62725 (15)

0.65795 (17)

0.70859 (18)

0.730385

0.72785 (18)

0.763051

0.69658 (18)

0.709858

0.64535 (17)

0.63644 (18)

0.666245

0.619572

0.609520

0.3523 (3)

0.4684 (3)

0.4774 (3)

0.5188 (3)

0.525246

0.5510 (3)

0.577369

0.5452 (3)

0.569395

0.5041 (3)

0.4466 (3)

0.443052

0.384785

0.491798

0.23772 (12)

0.24936 (13)

0.29009 (13)

0.29143 (15)

0.318559

0.25394 (17)

0.255498

0.21466 (15)

0.189345

0.21135 (14)

0.33134 (14)

0.354920

0.326920

0.339018

0.0407 (10)

0.0387 (10)

0.0435 (10)

0.0548 (12)

0.066*

0.0586 (13)

0.070*

0.0548 (12)

0.066*

0.0461 (11)

0.0623 (13)

0.093*

H95A

C96

H96A

C97

C98

H98A

H98B

H98C

C99

0.60969 (18)

0.625660

0.4994 (3)

0.536929

0.16868 (13)

0.146932

0.0589 (12)

0.088*

H99A

H99B

H99C

C100

C101

C102

C103

H10I

C104

H10J

C105

H10K

C106

C107

H10A

H10B

H10C

C108

H10D

H10E

H10F

C109

C110

C111

C112

0.573795

0.606390

0.524075

0.434211

0.172435

0.158888

0.088*

0.57287 (15)

0.58373 (16)

0.60646 (16)

0.61455 (19)

0.630117

0.6005 (2)

0.605780

0.57881 (19)

0.569599

0.57010 (17)

0.62318 (17)

0.634405

0.592630

0.653424

0.0881 (3)

−0.0894 (3)

−0.1047 (3)

−0.1973 (3)

−0.210193

−0.2711 (3)

−0.333778

−0.2533 (3)

−0.304400

−0.1616 (3)

−0.0248 (3)

−0.049012

0.018109

0.22227 (12)

0.23737 (14)

0.28053 (14)

0.29358 (16)

0.322457

0.26565 (19)

0.275521

0.22317 (18)

0.204103

0.20767 (15)

0.31054 (13)

0.339822

0.311445

0.299956

0.0401 (10)

0.0440 (10)

0.0498 (11)

0.0615 (13)

0.074*

0.0696 (14)

0.084*

0.0641 (13)

0.077*

0.0497 (11)

0.0560 (12)

0.084*

0.008661

0.54868 (18)

0.545873

0.573227

−0.1427 (3)

−0.201659

−0.100140

−0.113831

0.2221 (2)

0.2357 (3)

0.2082 (3)

0.2209 (3)

0.16158 (14)

0.145285

0.148636

0.0613 (13)

0.092*

0.512845

0.160480

0.092*

0.62735 (16)

0.71351 (15)

0.71744 (16)

0.76614 (17)

0.27036 (12)

0.32387 (13)

0.36749 (13)

0.39254 (14)

0.0362 (9)

0.0414 (10)

0.0460 (10)

0.0585 (12)

Acta Cryst. (2019). C75

sup-18

supporting information

H11G

C113

H11H

C114

H11I

0.770084

0.80947 (18)

0.842658

0.80446 (17)

0.834599

0.75648 (16)

0.66989 (18)

0.649506

0.646300

0.683072

0.75213 (17)

0.783074

0.718548

0.201568

0.2612 (3)

0.270596

0.2878 (3)

0.314846

0.2760 (3)

0.1664 (4)

0.125409

0.216766

0.129966

0.3015 (3)

0.340481

0.336351

0.244344

0.2327 (3)

0.2018 (3)

0.2659 (3)

0.2317 (4)

0.272001

0.1404 (4)

0.119403

0.0796 (3)

0.017105

0.1090 (3)

0.3655 (3)

0.400123

0.368867

0.393138

0.0411 (3)

−0.015825

0.069641

0.025192

0.422107

0.37547 (16)

0.393386

0.33233 (15)

0.320771

0.30557 (13)

0.38705 (14)

0.365677

0.395198

0.412956

0.25807 (13)

0.252724

0.250040

0.070*

0.0637 (13)

0.076*

0.0553 (12)

0.066*

0.0426 (10)

0.0693 (14)

0.104*

0.0521 (11)

0.078*

C115

C116

H11A

H11B

H11C

C117

H11D

H11E

H11F

C118

C119

C120

C121

H12G

C122

H12H

C123

H12I

C124

C125

H12A

H12B

H12C

C126

H12D

H12E

H12F

0.751935

0.240556

0.078*

0.61970 (15)

0.69374 (16)

0.73373 (17)

0.77412 (18)

0.802780

0.7735 (2)

0.801121

0.73283 (19)

0.732875

0.69179 (16)

0.73311 (19)

0.761435

0.739699

0.697791

0.18491 (12)

0.13607 (12)

0.12729 (13)

0.10388 (14)

0.098111

0.08887 (15)

0.072490

0.09752 (14)

0.087044

0.12146 (13)

0.14131 (15)

0.128617

0.173102

0.131430

0.0363 (9)

0.0436 (10)

0.0495 (11)

0.0611 (13)

0.073*

0.0663 (14)

0.080*

0.0586 (12)

0.070*

0.0473 (11)

0.0636 (13)

0.095*

0.64974 (17)

0.651205

0.613844

0.13299 (14)

0.115510

0.127071

0.0575 (12)

0.086*

0.656689

0.163933

0.086*

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

Fe1

N1

N2

N3

N4

N5

C1

C2

C3

C4

C5

C6

0.0395 (3)

0.044 (2)

0.066 (3)

0.052 (2)

0.049 (2)

0.041 (2)

0.045 (3)

0.041 (3)

0.055 (3)

0.060 (3)

0.054 (3)

0.081 (4)

0.0383 (3)

0.053 (2)

0.054 (2)

0.046 (2)

0.047 (2)

0.052 (2)

0.040 (3)

0.061 (3)

0.066 (3)

0.093 (4)

0.122 (6)

0.099 (5)

0.0386 (3)

0.0002 (3)

0.0076 (19)

0.0042 (19)

−0.002 (2)

−0.0060 (19)

−0.0014 (19)

−0.007 (2)

−0.001 (2)

0.019 (3)

0.0059 (3)

0.0041 (17)

0.0147 (19)

0.0087 (18)

0.0005 (19)

0.0005 (17)

0.000 (2)

0.004 (2)

0.012 (2)

0.011 (3)

0.028 (3)

−0.0026 (3)

−0.0067 (17)

0.0036 (19)

−0.0046 (18)

0.000 (2)

−0.0074 (19)

−0.002 (2)

−0.010 (2)

−0.012 (2)

−0.018 (3)

−0.030 (4)

0.002 (3)

0.044 (2)

0.046 (2)

0.054 (2)

0.063 (2)

0.053 (2)

0.041 (2)

0.035 (2)

0.054 (3)

0.086 (4)

0.096 (5)

0.061 (3)

0.020 (3)

0.003 (4)

−0.031 (4)

0.024 (3)

Acta Cryst. (2019). C75

sup-19

supporting information

C7

C8

C9

0.058 (3)

0.096 (4)

0.121 (5)

0.042 (2)

0.066 (3)

0.072 (4)

0.079 (4)

0.086 (4)

0.065 (3)

0.078 (4)

0.073 (3)

0.042 (2)

0.054 (3)

0.060 (3)

0.068 (4)

0.127 (6)

0.131 (6)

0.090 (4)

0.062 (3)

0.101 (5)

0.046 (3)

0.039 (2)

0.037 (2)

0.063 (3)

0.070 (3)

0.063 (3)

0.046 (3)

0.072 (3)

0.078 (4)

0.037 (2)

0.035 (2)

0.040 (3)

0.067 (4)

0.053 (3)

0.059 (4)

0.043 (3)

0.089 (4)

0.080 (4)

0.0358 (3)

0.0334 (3)

0.041 (2)

0.054 (2)

0.049 (2)

0.042 (2)

0.044 (2)

0.043 (2)

0.038 (2)

0.067 (3)

0.061 (4)

0.065 (4)

0.045 (3)

0.050 (3)

0.058 (3)

0.097 (4)

0.119 (5)

0.099 (4)

0.059 (3)

0.076 (4)

0.067 (3)

0.038 (3)

0.043 (3)

0.078 (4)

0.109 (5)

0.103 (5)

0.059 (4)

0.047 (3)

0.115 (5)

0.058 (3)

0.037 (2)

0.044 (3)

0.048 (3)

0.072 (4)

0.075 (4)

0.049 (3)

0.050 (3)

0.061 (3)

0.052 (3)

0.040 (3)

0.061 (3)

0.079 (4)

0.046 (4)

0.051 (4)

0.051 (3)

0.107 (5)

0.090 (4)

0.0380 (3)

0.0406 (3)

0.049 (2)

0.044 (2)

0.045 (2)

0.048 (2)

0.039 (2)

0.036 (2)

0.045 (2)

0.040 (3)

0.096 (4)

0.067 (4)

0.044 (3)

0.043 (3)

0.065 (3)

0.080 (4)

0.081 (4)

0.052 (3)

0.053 (3)

0.075 (4)

0.058 (3)

0.043 (2)

0.042 (3)

0.053 (3)

0.061 (4)

0.073 (4)

0.052 (3)

0.084 (4)

0.118 (5)

0.044 (2)

0.045 (3)

0.055 (3)

0.075 (3)

0.058 (3)

0.060 (3)

0.056 (3)

0.069 (3)

0.081 (4)

0.039 (2)

0.066 (3)

0.087 (4)

0.125 (5)

0.180 (7)

0.140 (6)

0.081 (4)

0.067 (4)

0.073 (4)

0.0397 (3)

0.0358 (3)

0.048 (2)

0.059 (2)

0.043 (2)

0.041 (2)

0.045 (2)

0.047 (2)

−0.009 (3)

0.022 (3)

−0.003 (3)

0.006 (2)

0.015 (2)

0.006 (3)

0.015 (4)

0.023 (3)

0.020 (3)

−0.002 (3)

0.012 (3)

0.002 (2)

−0.017 (2)

−0.007 (3)

−0.037 (4)

−0.072 (5)

−0.037 (4)

−0.021 (3)

0.012 (3)

0.013 (3)

−0.003 (2)

0.005 (2)

0.000 (2)

0.011 (2)

0.010 (2)

0.024 (3)

0.023 (3)

0.004 (2)

0.020 (2)

0.027 (3)

0.028 (3)

0.032 (4)

0.018 (3)

0.022 (3)

0.014 (3)

0.016 (3)

0.010 (2)

0.004 (2)

0.003 (2)

−0.005 (3)

−0.014 (4)

0.012 (4)

0.015 (3)

0.022 (3)

0.043 (4)

0.001 (2)

0.010 (2)

0.014 (2)

0.017 (3)

−0.003 (3)

−0.005 (3)

0.002 (2)

0.008 (3)

−0.001 (3)

0.0047 (19)

−0.005 (2)

0.009 (3)

0.018 (4)

0.003 (4)

−0.001 (4)

−0.010 (2)

0.027 (3)

−0.001 (3)

0.0031 (2)

0.0032 (2)

0.0006 (17)

0.0078 (19)

0.0007 (18)

0.0003 (17)

0.0093 (16)

0.0034 (16)

0.0098 (16)

−0.005 (2)

0.005 (3)

0.015 (3)

−0.006 (2)

0.007 (2)

0.011 (3)

0.032 (3)

0.047 (4)

0.024 (3)

0.008 (2)

0.002 (3)

0.001 (2)

0.003 (2)

0.016 (3)

0.027 (3)

0.018 (4)

−0.004 (3)

0.000 (2)

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

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

Fe2

Fe3

N6

0.024 (4)

−0.017 (3)

0.000 (2)

0.001 (2)

0.000 (2)

0.012 (3)

0.005 (3)

0.019 (3)

0.005 (3)

0.005 (2)

−0.012 (3)

−0.006 (2)

−0.003 (2)

−0.018 (3)

−0.006 (2)

−0.004 (2)

−0.032 (3)

−0.054 (4)

−0.030 (4)

0.011 (4)

−0.004 (3)

0.004 (2)

−0.002 (2)

−0.007 (2)

−0.012 (3)

−0.010 (3)

0.002 (3)

0.000 (2)

0.003 (3)

−0.021 (3)

0.028 (3)

−0.016 (4)

−0.012 (3)

0.0001 (3)

−0.0028 (3)

−0.0037 (18)

0.0021 (18)

0.0017 (18)

0.0035 (17)

−0.0024 (16)

−0.0060 (17)

0.0027 (18)

−0.0019 (3)

−0.0029 (3)

−0.0008 (17)

−0.0066 (18)

0.0026 (19)

−0.0042 (17)

0.0019 (17)

−0.0077 (16)

−0.0014 (18)

N7

N8

N9

N10

N11

N12

Acta Cryst. (2019). C75

sup-20

Article Doi

Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9

DOI: 10.1107/S205322961900963X

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Article abstract of DOI:10.1107/S205322961900963X

Full text of DOI:10.1107/S205322961900963X

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