Dichlorido(2-chloro-9-mesityl-1,10-phenanthroline-κ2N,N′)cobalt(II) dichloro­methane hemisolvate

Yang, Y.; Yang, P.; Zhang, C.; Wu, B.

doi:10.1107/S1600536808007320

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m623

doi:10.1107/S1600536808007320

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Dichlorido(2-chloro-9-mesityl-1,10-phenanthroline-κ²N,N′)cobalt(II) dichloromethane hemisolvate

Yue Yang,^a,^b Peiju Yang,^a Cui Zhang ^a,^b and Biao Wu ^a ^*

^aState Key Laboratory for Oxo Synthesis & Selective Oxidation, Lanzhou Institute of Chemical Physics, CAS, Lanzhou 730000, People's Republic of China, and ^bGraduate University of the Chinese Academy of Sciences, Beijing 100049, People's Republic of China
^*Correspondence e-mail: wubiao@lzb.ac.cn

(Received 21 February 2008; accepted 17 March 2008; online 4 April 2008)

The title compound, [CoCl₂(C₂₁H₁₇ClN₂)]·0.5CH₂Cl₂, crystallizes from dichloromethane as a 2:1 solvate [CoCl₂L]₂·CH₂Cl₂ (L is 2-chloro-9-mesityl-1,10-phenanthroline). There are two independent CoCl₂L molecules in the asymmetric unit and both molecules have similar conformations. They are connected by a weak C—H⋯π interaction involving the mesityl ring. The cobalt center is four-coordinated by the two N-atom donors of the bidentate ligand and two chloride ions in a distorted tetrahedral geometry. The packing of the molecules is stabilized by weak slipped π–π stacking interactions between symmetry-related phenanthroline groups.

Related literature

For related literature, see: Britovsek et al. (1998 ); Garas & Vagg (2000 ); Gibson & Spitzmesser (2003 ); Sauvage (1990 ); Small & Brookhart (1998 ).

Experimental

Crystal data

[CoCl₂(C₂₁H₁₇ClN₂)]·0.5CH₂Cl₂
M_r = 505.11
Triclinic, $[P \overline 1]$
a = 9.8830 (3) Å
b = 15.3591 (5) Å
c = 15.6544 (5) Å
α = 79.964 (1)°
β = 78.094 (1)°
γ = 74.515 (1)°
V = 2222.75 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 293 (2) K
0.45 × 0.36 × 0.25 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.688, T_max = 1.000 (expected range = 0.501–0.729)
13275 measured reflections
9215 independent reflections
5134 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.159
S = 1.02
9215 reflections
520 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯Cg1ⁱ	0.93	2.59	3.470 (5)	157
Symmetry code: (i) x-1, y, z. Cg1 is the centroid of the mesityl ring.

Table 2
Possible π–π stacking interactions (Å, °)

	Centroid–centroid	α	CgI-perp	CgJ-perp	slippage
Cg2 – Cg2ⁱ	3.877 (3)	0.0	3.712	3.712	1.12
Cg2 – Cg3ⁱ	3.923 (3)	0.49	3.712	3.701	1.23
Cg4 – Cg4ⁱⁱ	3.992 (3)	0.02	3.490	3.490	1.94
Symmetry codes: (i) -x, 2-y, -z; (ii) 2-x, -y, 1-z. CgI –CgJ = distance between ring centroids; α = dihedral angle between planes I and J; CgI–perp = perpendicular distance of Cg(I) from ring J; CgJ-perp = perpendicular distance of Cg(J) from ring I; slippage = distance between Cg(I) and perpendicular projection of Cg(J) on ring I. Cg2 is the centroid of atoms N1,C1–C4,C12; Cg3 is the centroid of atoms C4–C7,C11,C12; Cg4 is the centroid of atoms N3,C22–C25,C33.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007320/dn2321sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007320/dn2321Isup2.hkl

checkCIF report

Comment top

Since Co^II complexes have been found to have high catalytic activities for the ethylene polymerization, much research interest has been inspired in cobalt metal catalysis systems over the past decade (Small & Brookhart, 1998; Britovsek et al.,1998). Research in this area frequently involves the design of new ancillary ligands to support and activate the metal center toward polymerization (Gibson & Spitzmesser, 2003). 1,10-Phenanthroline and its derivatives are well established ligands in transition metal coordination chemistry because their steric and electronic environment can be conveniently tailored by varying the substituents (Sauvage,1990). The title complex is one of cobalt^II dihalide complexes which we have designed and its crystal structure is presented here.

The asymmetric unit contains two independent CoCl₂L molecules with similar conformation and a CH₂Cl₂ solvent molecule (Fig. 1). The two CoCl₂L units are connected by a weak C—H···π interaction involving the mesityl ring (Table 1). The cobalt center is four-coordinated by the two nitrogen donors of the bidentate ligand and two chloride ions forming a distorted tetrahedron, with the dihedral angle of the N—Co—N and Cl—Co—Cl planes being 88.53/88.52°. The dihedral angle between the phenanthroline moiety and the attached mesityl substituent is 85.51/83.42°.

The packing of the molecules is stabilized by weak slipped π-π stacking interactions between symmetry related phenanthroline rings (Table 2).

Related literature top

For related literature, see: Britovsek et al. (1998); Garas & Vagg (2000); Gibson & Spitzmesser (2003); Sauvage (1990); Small & Brookhart (1998).

Experimental top

The ligand 2-chloro-9-mesityl-1,10-phenanthroline was synthesized according to a modified procedure (Garas & Vagg, 2000) as a pale yellow solid in 62.0% yield. M.p.: 515–516 K. ESI-MS: m/z 333.3 [M+H]^{+. 1}H NMR (CDCl₃, δ/p.p.m.): 8.28 (1H, d, J = 8.4 Hz, H4), 8.20 (1H, d, J = 8.8 Hz, H7), 7.86 (1H, d, J = 8.8 Hz, H3), 7.80 (1H, d, J = 8.8 Hz, H8), 7.61 (1H, d, J = 8.8 Hz, H5), 7.59 (1H, d, J = 8.8 Hz, H6), 6.97 (2H, s, Ph—H), 2.35 (3H, s, p-CH3), 2.13 (6H, s, o-CH3). And the title compound was readily synthesized in excellent yield through the following method: a solution of CoCl₂.6H₂O (0.80 g, 0.0034 mol) and the ligand (1.12 g, 0.0034 mol) in tetrahydrofuran was stirred at room temperature for 12 h, giving a light green suspension. The precipitate was collected, washed repeatedly with diethyl ether and dried under vacuum to yield the title compound (1.48 g, 95.6%). Mp: > 573 K. Anal. Calcd for C₂₁H₁₇N₂CoCl₃ (462.66): C 54.52, H 3.70, N 6.05%; Found: C 54.46, H 3.68, N 6.10%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms and the solvent molecule have been omitted for clarity.

Dichlorido(2-chloro-9-mesityl-1,10-phenanthroline-κ²N,N')cobalt(II) dichloromethane hemisolvate top

Crystal data top

[CoCl₂(C₂₁H₁₇ClN₂)]·0.5CH₂Cl₂	Z = 4
M_r = 505.11	F(000) = 1024
Triclinic, P1	D_x = 1.509 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8830 (3) Å	Cell parameters from 2211 reflections
b = 15.3591 (5) Å	θ = 2.4–20.6°
c = 15.6544 (5) Å	µ = 1.26 mm⁻¹
α = 79.964 (1)°	T = 293 K
β = 78.094 (1)°	Prism, blue
γ = 74.515 (1)°	0.45 × 0.36 × 0.25 mm
V = 2222.75 (12) Å³

Data collection top

Bruker APEXII diffractometer	9215 independent reflections
Radiation source: fine-focus sealed tube	5134 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 26.8°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→9
T_min = 0.688, T_max = 1.000	k = −19→18
13275 measured reflections	l = −19→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0717P)²] where P = (F_o² + 2F_c²)/3
9215 reflections	(Δ/σ)_max = 0.002
520 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[CoCl₂(C₂₁H₁₇ClN₂)]·0.5CH₂Cl₂	γ = 74.515 (1)°
M_r = 505.11	V = 2222.75 (12) Å³
Triclinic, P1	Z = 4
a = 9.8830 (3) Å	Mo Kα radiation
b = 15.3591 (5) Å	µ = 1.26 mm⁻¹
c = 15.6544 (5) Å	T = 293 K
α = 79.964 (1)°	0.45 × 0.36 × 0.25 mm
β = 78.094 (1)°

Data collection top

Bruker APEXII diffractometer	9215 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	5134 reflections with I > 2σ(I)
T_min = 0.688, T_max = 1.000	R_int = 0.025
13275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.02	Δρ_max = 0.44 e Å⁻³
9215 reflections	Δρ_min = −0.69 e Å⁻³
520 parameters

Special details top

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 F² against 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.

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

	x	y	z	U_iso*/U_eq
Co1	0.32238 (6)	0.79829 (4)	0.05811 (4)	0.04711 (18)
Co2	0.80414 (6)	0.23178 (4)	0.34801 (4)	0.0570 (2)
Cl1	0.41735 (14)	0.98271 (9)	−0.08111 (9)	0.0757 (4)
Cl2	0.31739 (13)	0.86836 (8)	0.17136 (8)	0.0665 (3)
Cl3	0.52745 (12)	0.71461 (9)	−0.00237 (9)	0.0693 (4)
Cl4	0.7295 (2)	0.02459 (11)	0.43135 (13)	0.1119 (6)
Cl5	0.66100 (16)	0.23526 (12)	0.25601 (12)	0.0995 (5)
Cl6	0.72549 (15)	0.27227 (9)	0.48148 (9)	0.0774 (4)
Cl7	0.7761 (2)	−0.26354 (17)	0.52141 (14)	0.1424 (8)
Cl8	0.6046 (3)	−0.16227 (19)	0.3978 (2)	0.2024 (14)
N1	0.2218 (3)	0.8907 (2)	−0.0376 (2)	0.0470 (8)
N2	0.1439 (3)	0.7478 (2)	0.0720 (2)	0.0404 (8)
N3	0.9359 (4)	0.1022 (2)	0.3618 (2)	0.0610 (10)
N4	0.9946 (3)	0.2638 (2)	0.2955 (2)	0.0459 (8)
C1	0.2594 (5)	0.9605 (3)	−0.0895 (3)	0.0565 (12)
C2	0.1767 (5)	1.0170 (3)	−0.1498 (3)	0.0645 (13)
H2	0.2079	1.0651	−0.1860	0.077*
C3	0.0504 (5)	1.0002 (3)	−0.1544 (3)	0.0630 (13)
H3	−0.0062	1.0377	−0.1934	0.076*
C4	0.0039 (5)	0.9259 (3)	−0.1000 (3)	0.0495 (11)
C5	−0.1263 (5)	0.9048 (3)	−0.1012 (3)	0.0559 (11)
H5	−0.1865	0.9408	−0.1390	0.067*
C6	−0.1641 (5)	0.8330 (3)	−0.0479 (3)	0.0570 (12)
H6	−0.2493	0.8194	−0.0504	0.068*
C7	−0.0754 (4)	0.7777 (3)	0.0121 (3)	0.0486 (10)
C8	−0.1120 (5)	0.7038 (3)	0.0705 (3)	0.0597 (12)
H8	−0.1970	0.6883	0.0712	0.072*
C9	−0.0219 (5)	0.6555 (3)	0.1258 (3)	0.0561 (12)
H9	−0.0447	0.6057	0.1636	0.067*
C10	0.1054 (4)	0.6791 (3)	0.1273 (3)	0.0439 (10)
C11	0.0545 (4)	0.7974 (3)	0.0149 (3)	0.0416 (9)
C12	0.0954 (4)	0.8733 (3)	−0.0432 (3)	0.0453 (10)
C13	0.1957 (4)	0.6275 (3)	0.1945 (3)	0.0426 (10)
C14	0.1613 (5)	0.6522 (3)	0.2786 (3)	0.0534 (11)
C15	0.2371 (5)	0.6000 (4)	0.3422 (3)	0.0643 (13)
H15	0.2143	0.6169	0.3986	0.077*
C16	0.3449 (5)	0.5241 (3)	0.3256 (3)	0.0636 (13)
C17	0.3784 (4)	0.5010 (3)	0.2401 (3)	0.0590 (12)
H17	0.4514	0.4501	0.2274	0.071*
C18	0.3066 (4)	0.5515 (3)	0.1736 (3)	0.0468 (10)
C19	0.0407 (6)	0.7335 (4)	0.3020 (3)	0.0854 (17)
H19A	0.0311	0.7392	0.3632	0.128*
H19B	−0.0465	0.7250	0.2907	0.128*
H19C	0.0612	0.7878	0.2670	0.128*
C20	0.4251 (6)	0.4690 (4)	0.3969 (4)	0.101 (2)
H20A	0.4882	0.5018	0.4085	0.152*
H20B	0.4794	0.4118	0.3781	0.152*
H20C	0.3588	0.4584	0.4495	0.152*
C21	0.3423 (5)	0.5227 (3)	0.0829 (3)	0.0688 (14)
H21A	0.4169	0.4679	0.0819	0.103*
H21B	0.3734	0.5701	0.0411	0.103*
H21C	0.2593	0.5119	0.0679	0.103*
C22	0.9067 (6)	0.0232 (3)	0.3965 (3)	0.0731 (15)
C23	1.0084 (9)	−0.0587 (4)	0.4057 (4)	0.094 (2)
H23	0.9818	−0.1125	0.4306	0.113*
C24	1.1494 (8)	−0.0579 (4)	0.3770 (4)	0.091 (2)
H24	1.2194	−0.1118	0.3828	0.109*
C25	1.1888 (6)	0.0243 (3)	0.3387 (3)	0.0717 (15)
C26	1.3299 (6)	0.0325 (4)	0.3070 (4)	0.0821 (17)
H26	1.4042	−0.0194	0.3092	0.099*
C27	1.3598 (6)	0.1128 (4)	0.2739 (4)	0.0818 (17)
H27	1.4544	0.1155	0.2547	0.098*
C28	1.2495 (5)	0.1951 (3)	0.2671 (3)	0.0598 (12)
C29	1.2745 (5)	0.2805 (4)	0.2325 (3)	0.0695 (14)
H29	1.3666	0.2873	0.2107	0.083*
C30	1.1608 (5)	0.3536 (3)	0.2314 (3)	0.0642 (13)
H30	1.1763	0.4109	0.2087	0.077*
C31	1.0218 (4)	0.3453 (3)	0.2633 (3)	0.0478 (10)
C32	1.1082 (5)	0.1893 (3)	0.2975 (3)	0.0511 (11)
C33	1.0767 (5)	0.1025 (3)	0.3340 (3)	0.0558 (12)
C34	0.8998 (4)	0.4272 (3)	0.2636 (3)	0.0459 (10)
C35	0.8679 (5)	0.4817 (3)	0.3307 (3)	0.0503 (11)
C36	0.7599 (5)	0.5611 (3)	0.3259 (3)	0.0579 (12)
H36	0.7384	0.5983	0.3701	0.069*
C37	0.6836 (5)	0.5861 (3)	0.2567 (3)	0.0577 (12)
C38	0.7163 (5)	0.5302 (3)	0.1918 (3)	0.0574 (12)
H38	0.6648	0.5458	0.1457	0.069*
C39	0.8230 (5)	0.4519 (3)	0.1937 (3)	0.0537 (11)
C40	0.9502 (5)	0.4564 (3)	0.4063 (3)	0.0662 (13)
H40A	0.9447	0.3965	0.4345	0.099*
H40B	0.9102	0.4994	0.4479	0.099*
H40C	1.0481	0.4573	0.3844	0.099*
C41	0.5680 (5)	0.6738 (3)	0.2527 (4)	0.0894 (18)
H41A	0.5216	0.6852	0.3113	0.134*
H41B	0.4995	0.6684	0.2197	0.134*
H41C	0.6098	0.7234	0.2245	0.134*
C42	0.8605 (6)	0.3948 (4)	0.1182 (3)	0.0828 (16)
H42A	0.7796	0.4059	0.0893	0.124*
H42B	0.8866	0.3314	0.1407	0.124*
H42C	0.9390	0.4110	0.0769	0.124*
C43	0.6125 (7)	−0.2104 (6)	0.5048 (6)	0.152 (3)
H43A	0.5746	−0.1630	0.5431	0.182*
H43B	0.5526	−0.2534	0.5209	0.182*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0409 (3)	0.0501 (3)	0.0512 (4)	−0.0109 (3)	−0.0104 (3)	−0.0055 (3)
Co2	0.0542 (4)	0.0565 (4)	0.0653 (4)	−0.0192 (3)	−0.0143 (3)	−0.0068 (3)
Cl1	0.0669 (8)	0.0820 (9)	0.0832 (9)	−0.0381 (7)	−0.0056 (7)	−0.0007 (7)
Cl2	0.0776 (8)	0.0572 (7)	0.0661 (8)	−0.0037 (6)	−0.0261 (7)	−0.0147 (6)
Cl3	0.0477 (7)	0.0725 (8)	0.0851 (9)	−0.0073 (6)	−0.0034 (6)	−0.0230 (7)
Cl4	0.1371 (15)	0.0841 (11)	0.1283 (15)	−0.0663 (10)	−0.0125 (12)	0.0002 (10)
Cl5	0.0840 (10)	0.1128 (12)	0.1225 (13)	−0.0340 (9)	−0.0530 (10)	−0.0117 (10)
Cl6	0.0909 (10)	0.0705 (8)	0.0697 (8)	−0.0218 (7)	−0.0053 (7)	−0.0116 (7)
Cl7	0.1138 (15)	0.187 (2)	0.1112 (15)	−0.0117 (14)	−0.0297 (12)	−0.0040 (14)
Cl8	0.218 (3)	0.149 (2)	0.278 (4)	−0.063 (2)	−0.165 (3)	0.049 (2)
N1	0.045 (2)	0.047 (2)	0.047 (2)	−0.0096 (16)	−0.0074 (16)	−0.0038 (17)
N2	0.0408 (18)	0.0408 (18)	0.0384 (18)	−0.0072 (15)	−0.0076 (15)	−0.0043 (15)
N3	0.086 (3)	0.045 (2)	0.056 (2)	−0.019 (2)	−0.016 (2)	−0.0078 (18)
N4	0.048 (2)	0.044 (2)	0.047 (2)	−0.0085 (17)	−0.0143 (16)	−0.0060 (16)
C1	0.060 (3)	0.056 (3)	0.051 (3)	−0.019 (2)	−0.002 (2)	0.001 (2)
C2	0.080 (4)	0.051 (3)	0.059 (3)	−0.019 (3)	−0.011 (3)	0.007 (2)
C3	0.073 (3)	0.056 (3)	0.059 (3)	−0.008 (3)	−0.026 (3)	0.003 (2)
C4	0.056 (3)	0.042 (2)	0.049 (3)	−0.008 (2)	−0.012 (2)	−0.002 (2)
C5	0.057 (3)	0.054 (3)	0.057 (3)	−0.004 (2)	−0.026 (2)	−0.003 (2)
C6	0.051 (3)	0.056 (3)	0.069 (3)	−0.008 (2)	−0.028 (2)	−0.006 (2)
C7	0.046 (2)	0.048 (2)	0.052 (3)	−0.011 (2)	−0.012 (2)	−0.003 (2)
C8	0.046 (3)	0.061 (3)	0.077 (3)	−0.020 (2)	−0.020 (2)	0.003 (3)
C9	0.052 (3)	0.054 (3)	0.065 (3)	−0.022 (2)	−0.019 (2)	0.010 (2)
C10	0.041 (2)	0.046 (2)	0.043 (2)	−0.0092 (19)	−0.0081 (19)	−0.0029 (19)
C11	0.036 (2)	0.044 (2)	0.044 (2)	−0.0037 (18)	−0.0097 (19)	−0.0082 (19)
C12	0.042 (2)	0.045 (2)	0.045 (2)	−0.0051 (19)	−0.007 (2)	−0.0073 (19)
C13	0.046 (2)	0.044 (2)	0.042 (2)	−0.0171 (19)	−0.0109 (19)	−0.0014 (19)
C14	0.058 (3)	0.057 (3)	0.046 (3)	−0.020 (2)	−0.003 (2)	−0.007 (2)
C15	0.076 (3)	0.081 (4)	0.041 (3)	−0.034 (3)	−0.008 (3)	−0.001 (3)
C16	0.070 (3)	0.069 (3)	0.058 (3)	−0.031 (3)	−0.028 (3)	0.015 (3)
C17	0.044 (3)	0.048 (3)	0.085 (4)	−0.009 (2)	−0.020 (3)	0.002 (2)
C18	0.041 (2)	0.046 (2)	0.052 (3)	−0.012 (2)	−0.006 (2)	−0.003 (2)
C19	0.099 (4)	0.077 (4)	0.071 (4)	−0.010 (3)	0.010 (3)	−0.030 (3)
C20	0.102 (5)	0.123 (5)	0.085 (4)	−0.042 (4)	−0.056 (4)	0.044 (4)
C21	0.079 (3)	0.061 (3)	0.060 (3)	−0.009 (3)	−0.002 (3)	−0.017 (2)
C22	0.107 (4)	0.055 (3)	0.065 (3)	−0.027 (3)	−0.019 (3)	−0.007 (3)
C23	0.163 (7)	0.044 (3)	0.075 (4)	−0.028 (4)	−0.019 (4)	−0.006 (3)
C24	0.144 (6)	0.048 (3)	0.072 (4)	0.006 (4)	−0.031 (4)	−0.012 (3)
C25	0.098 (4)	0.057 (3)	0.057 (3)	0.006 (3)	−0.031 (3)	−0.017 (2)
C26	0.075 (4)	0.078 (4)	0.086 (4)	0.021 (3)	−0.033 (3)	−0.025 (3)
C27	0.057 (3)	0.094 (4)	0.093 (4)	0.006 (3)	−0.021 (3)	−0.035 (4)
C28	0.050 (3)	0.068 (3)	0.059 (3)	0.003 (2)	−0.017 (2)	−0.020 (2)
C29	0.058 (3)	0.079 (4)	0.076 (4)	−0.024 (3)	−0.011 (3)	−0.011 (3)
C30	0.056 (3)	0.062 (3)	0.077 (4)	−0.022 (3)	−0.012 (3)	−0.002 (3)
C31	0.049 (3)	0.051 (3)	0.046 (2)	−0.011 (2)	−0.017 (2)	−0.005 (2)
C32	0.053 (3)	0.055 (3)	0.048 (3)	−0.010 (2)	−0.014 (2)	−0.011 (2)
C33	0.066 (3)	0.051 (3)	0.052 (3)	−0.003 (2)	−0.024 (2)	−0.011 (2)
C34	0.051 (2)	0.045 (2)	0.044 (2)	−0.016 (2)	−0.016 (2)	0.0045 (19)
C35	0.055 (3)	0.054 (3)	0.046 (3)	−0.019 (2)	−0.014 (2)	−0.002 (2)
C36	0.060 (3)	0.050 (3)	0.064 (3)	−0.017 (2)	−0.005 (3)	−0.010 (2)
C37	0.048 (3)	0.050 (3)	0.073 (3)	−0.015 (2)	−0.017 (2)	0.007 (2)
C38	0.050 (3)	0.055 (3)	0.071 (3)	−0.016 (2)	−0.026 (2)	0.007 (2)
C39	0.061 (3)	0.059 (3)	0.048 (3)	−0.023 (2)	−0.017 (2)	0.000 (2)
C40	0.075 (3)	0.073 (3)	0.059 (3)	−0.022 (3)	−0.027 (3)	−0.006 (3)
C41	0.064 (3)	0.060 (3)	0.134 (5)	−0.002 (3)	−0.022 (3)	0.002 (3)
C42	0.101 (4)	0.087 (4)	0.067 (3)	−0.013 (3)	−0.036 (3)	−0.013 (3)
C43	0.092 (5)	0.168 (8)	0.167 (8)	−0.005 (5)	−0.021 (5)	0.014 (7)

Geometric parameters (Å, º) top

Co1—N2	2.067 (3)	C19—H19A	0.9600
Co1—N1	2.090 (3)	C19—H19B	0.9600
Co1—Cl3	2.2130 (12)	C19—H19C	0.9600
Co1—Cl2	2.2146 (13)	C20—H20A	0.9600
Co2—N4	2.043 (3)	C20—H20B	0.9600
Co2—N3	2.071 (4)	C20—H20C	0.9600
Co2—Cl5	2.2028 (16)	C21—H21A	0.9600
Co2—Cl6	2.2092 (15)	C21—H21B	0.9600
Cl1—C1	1.719 (5)	C21—H21C	0.9600
Cl4—C22	1.719 (6)	C22—C23	1.391 (8)
Cl7—C43	1.656 (7)	C23—C24	1.376 (8)
Cl8—C43	1.717 (8)	C23—H23	0.9300
N1—C1	1.315 (5)	C24—C25	1.418 (8)
N1—C12	1.369 (5)	C24—H24	0.9300
N2—C10	1.329 (5)	C25—C33	1.403 (6)
N2—C11	1.375 (5)	C25—C26	1.412 (7)
N3—C22	1.319 (6)	C26—C27	1.336 (7)
N3—C33	1.371 (6)	C26—H26	0.9300
N4—C31	1.341 (5)	C27—C28	1.436 (7)
N4—C32	1.373 (5)	C27—H27	0.9300
C1—C2	1.402 (6)	C28—C29	1.395 (7)
C2—C3	1.359 (6)	C28—C32	1.401 (6)
C2—H2	0.9300	C29—C30	1.361 (7)
C3—C4	1.421 (6)	C29—H29	0.9300
C3—H3	0.9300	C30—C31	1.393 (6)
C4—C12	1.397 (6)	C30—H30	0.9300
C4—C5	1.412 (6)	C31—C34	1.492 (6)
C5—C6	1.350 (6)	C32—C33	1.443 (6)
C5—H5	0.9300	C34—C35	1.389 (6)
C6—C7	1.428 (6)	C34—C39	1.400 (6)
C6—H6	0.9300	C35—C36	1.392 (6)
C7—C11	1.405 (5)	C35—C40	1.510 (6)
C7—C8	1.406 (6)	C36—C37	1.388 (6)
C8—C9	1.355 (6)	C36—H36	0.9300
C8—H8	0.9300	C37—C38	1.376 (6)
C9—C10	1.404 (6)	C37—C41	1.517 (6)
C9—H9	0.9300	C38—C39	1.372 (6)
C10—C13	1.500 (5)	C38—H38	0.9300
C11—C12	1.442 (5)	C39—C42	1.520 (6)
C13—C14	1.384 (6)	C40—H40A	0.9600
C13—C18	1.405 (5)	C40—H40B	0.9600
C14—C15	1.380 (6)	C40—H40C	0.9600
C14—C19	1.516 (6)	C41—H41A	0.9600
C15—C16	1.375 (7)	C41—H41B	0.9600
C15—H15	0.9300	C41—H41C	0.9600
C16—C17	1.396 (6)	C42—H42A	0.9600
C16—C20	1.505 (7)	C42—H42B	0.9600
C17—C18	1.386 (6)	C42—H42C	0.9600
C17—H17	0.9300	C43—H43A	0.9700
C18—C21	1.504 (6)	C43—H43B	0.9700

N2—Co1—N1	81.74 (13)	C16—C20—H20C	109.5
N2—Co1—Cl3	117.08 (9)	H20A—C20—H20C	109.5
N1—Co1—Cl3	110.81 (10)	H20B—C20—H20C	109.5
N2—Co1—Cl2	111.88 (9)	C18—C21—H21A	109.5
N1—Co1—Cl2	109.88 (10)	C18—C21—H21B	109.5
Cl3—Co1—Cl2	119.14 (5)	H21A—C21—H21B	109.5
N4—Co2—N3	81.41 (15)	C18—C21—H21C	109.5
N4—Co2—Cl5	117.29 (11)	H21A—C21—H21C	109.5
N3—Co2—Cl5	108.36 (12)	H21B—C21—H21C	109.5
N4—Co2—Cl6	111.17 (10)	N3—C22—C23	124.5 (6)
N3—Co2—Cl6	107.10 (11)	N3—C22—Cl4	116.2 (4)
Cl5—Co2—Cl6	122.82 (7)	C23—C22—Cl4	119.3 (5)
C1—N1—C12	117.8 (4)	C24—C23—C22	118.1 (5)
C1—N1—Co1	130.8 (3)	C24—C23—H23	120.9
C12—N1—Co1	111.4 (3)	C22—C23—H23	120.9
C10—N2—C11	118.7 (3)	C23—C24—C25	120.5 (5)
C10—N2—Co1	129.9 (3)	C23—C24—H24	119.7
C11—N2—Co1	111.3 (2)	C25—C24—H24	119.7
C22—N3—C33	117.0 (4)	C33—C25—C26	119.0 (5)
C22—N3—Co2	130.8 (4)	C33—C25—C24	115.9 (6)
C33—N3—Co2	112.0 (3)	C26—C25—C24	125.0 (5)
C31—N4—C32	117.9 (4)	C27—C26—C25	121.9 (5)
C31—N4—Co2	129.3 (3)	C27—C26—H26	119.1
C32—N4—Co2	112.8 (3)	C25—C26—H26	119.1
N1—C1—C2	123.2 (4)	C26—C27—C28	121.6 (5)
N1—C1—Cl1	117.5 (4)	C26—C27—H27	119.2
C2—C1—Cl1	119.2 (4)	C28—C27—H27	119.2
C3—C2—C1	118.8 (4)	C29—C28—C32	118.0 (4)
C3—C2—H2	120.6	C29—C28—C27	124.0 (5)
C1—C2—H2	120.6	C32—C28—C27	118.0 (5)
C2—C3—C4	120.6 (4)	C30—C29—C28	118.3 (5)
C2—C3—H3	119.7	C30—C29—H29	120.8
C4—C3—H3	119.7	C28—C29—H29	120.8
C12—C4—C5	120.7 (4)	C29—C30—C31	122.0 (5)
C12—C4—C3	115.8 (4)	C29—C30—H30	119.0
C5—C4—C3	123.5 (4)	C31—C30—H30	119.0
C6—C5—C4	120.5 (4)	N4—C31—C30	120.9 (4)
C6—C5—H5	119.7	N4—C31—C34	118.4 (4)
C4—C5—H5	119.7	C30—C31—C34	120.7 (4)
C5—C6—C7	121.0 (4)	N4—C32—C28	122.9 (4)
C5—C6—H6	119.5	N4—C32—C33	116.9 (4)
C7—C6—H6	119.5	C28—C32—C33	120.2 (4)
C11—C7—C8	117.4 (4)	N3—C33—C25	123.9 (5)
C11—C7—C6	119.6 (4)	N3—C33—C32	116.8 (4)
C8—C7—C6	123.1 (4)	C25—C33—C32	119.3 (5)
C9—C8—C7	119.1 (4)	C35—C34—C39	120.1 (4)
C9—C8—H8	120.4	C35—C34—C31	119.9 (4)
C7—C8—H8	120.4	C39—C34—C31	119.9 (4)
C8—C9—C10	121.3 (4)	C34—C35—C36	118.5 (4)
C8—C9—H9	119.3	C34—C35—C40	120.9 (4)
C10—C9—H9	119.3	C36—C35—C40	120.7 (4)
N2—C10—C9	120.9 (4)	C37—C36—C35	121.8 (4)
N2—C10—C13	120.1 (3)	C37—C36—H36	119.1
C9—C10—C13	119.0 (4)	C35—C36—H36	119.1
N2—C11—C7	122.5 (4)	C38—C37—C36	118.5 (4)
N2—C11—C12	118.3 (3)	C38—C37—C41	121.1 (5)
C7—C11—C12	119.1 (4)	C36—C37—C41	120.4 (5)
N1—C12—C4	123.8 (4)	C39—C38—C37	121.5 (4)
N1—C12—C11	117.2 (4)	C39—C38—H38	119.2
C4—C12—C11	119.0 (4)	C37—C38—H38	119.2
C14—C13—C18	120.9 (4)	C38—C39—C34	119.6 (4)
C14—C13—C10	118.8 (4)	C38—C39—C42	119.7 (4)
C18—C13—C10	120.1 (4)	C34—C39—C42	120.6 (4)
C15—C14—C13	118.7 (4)	C35—C40—H40A	109.5
C15—C14—C19	120.0 (4)	C35—C40—H40B	109.5
C13—C14—C19	121.3 (4)	H40A—C40—H40B	109.5
C16—C15—C14	122.8 (4)	C35—C40—H40C	109.5
C16—C15—H15	118.6	H40A—C40—H40C	109.5
C14—C15—H15	118.6	H40B—C40—H40C	109.5
C15—C16—C17	117.5 (4)	C37—C41—H41A	109.5
C15—C16—C20	121.1 (5)	C37—C41—H41B	109.5
C17—C16—C20	121.4 (5)	H41A—C41—H41B	109.5
C18—C17—C16	122.1 (4)	C37—C41—H41C	109.5
C18—C17—H17	118.9	H41A—C41—H41C	109.5
C16—C17—H17	118.9	H41B—C41—H41C	109.5
C17—C18—C13	118.0 (4)	C39—C42—H42A	109.5
C17—C18—C21	120.7 (4)	C39—C42—H42B	109.5
C13—C18—C21	121.3 (4)	H42A—C42—H42B	109.5
C14—C19—H19A	109.5	C39—C42—H42C	109.5
C14—C19—H19B	109.5	H42A—C42—H42C	109.5
H19A—C19—H19B	109.5	H42B—C42—H42C	109.5
C14—C19—H19C	109.5	Cl7—C43—Cl8	113.2 (5)
H19A—C19—H19C	109.5	Cl7—C43—H43A	108.9
H19B—C19—H19C	109.5	Cl8—C43—H43A	108.9
C16—C20—H20A	109.5	Cl7—C43—H43B	108.9
C16—C20—H20B	109.5	Cl8—C43—H43B	108.9
H20A—C20—H20B	109.5	H43A—C43—H43B	107.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cg1ⁱ	0.93	2.59	3.470 (5)	157

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₂₁H₁₇ClN₂)]·0.5CH₂Cl₂
M_r	505.11
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.8830 (3), 15.3591 (5), 15.6544 (5)
α, β, γ (°)	79.964 (1), 78.094 (1), 74.515 (1)
V (Å³)	2222.75 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.45 × 0.36 × 0.25

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.688, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13275, 9215, 5134
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.159, 1.02
No. of reflections	9215
No. of parameters	520
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.69

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cg1ⁱ	0.93	2.59	3.470 (5)	157

Symmetry code: (i) x−1, y, z.

Possible π–π stacking interactions (Å, °) top

	Centroid–centroid	α	CgI-perp	CgJ-perp	slippage
Cg2 – Cg2ⁱ	3.877 (3)	0.0	3.712	3.712	1.12
Cg2 – Cg3ⁱ	3.923 (3)	0.49	3.712	3.701	1.23
Cg4 – Cg4ⁱⁱ	3.992 (3)	0.02	3.490	3.490	1.94

Symmetry codes: (i) -x, 2-y, -z; (ii) 2-x, -y, 1-z. CgI -CgJ = distance between ring Centroids; α = dihedral angle between Planes I and J; CgI–perp = perpendicular distance of Cg(I) from ring J; CgJ–perp = perpendicular distance of Cg(J) from ring I; slippage = distance between Cg(I) and perpendicular projection of Cg(J) on Ring I. Cg2 is the centroid of atoms N1,C1–C4,C12; Cg3 is the centroid of atoms C4–C7,C11,C12; Cg4 is the centroid of atoms N3,C22–C25,C33.

Acknowledgements

The authors thank the Bairen Jihua Programme of the Chinese Academy of Sciences for funding.

References

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