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Acta Cryst. (2008). E64, m623    [ doi:10.1107/S1600536808007320 ]

Dichlorido(2-chloro-9-mesityl-1,10-phenanthroline-[kappa]2N,N')cobalt(II) dichloromethane hemisolvate

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

Abstract top

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...[pi] 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 [pi]-[pi] stacking interactions between symmetry-related phenanthroline groups.

Comment top

Since CoII 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 cobaltII 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]+. 1H 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%.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl), 0.97Å (methylene) or 0.93 Å (aromatic) with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(methyl).

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
[Figure 1] 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)]·0.5CH2Cl2Z = 4
Mr = 505.11F000 = 1024
Triclinic, P1Dx = 1.509 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.8830 (3) ÅCell parameters from 2211 reflections
b = 15.3591 (5) Åθ = 2.4–20.6º
c = 15.6544 (5) ŵ = 1.26 mm−1
α = 79.964 (1)ºT = 293 (2) K
β = 78.094 (1)ºPrism, blue
γ = 74.515 (1)º0.45 × 0.36 × 0.25 mm
V = 2222.75 (12) Å3
Data collection top
Bruker APEXII
diffractometer		9215 independent reflections
Radiation source: fine-focus sealed tube5134 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 293(2) Kθmax = 26.8º
ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		h = −12→9
Tmin = 0.688, Tmax = 1.000k = −19→18
13275 measured reflectionsl = −19→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.159  w = 1/[σ2(Fo2) + (0.0717P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.002
9215 reflectionsΔρmax = 0.44 e Å−3
520 parametersΔρmin = −0.69 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CoCl2(C21H17ClN2)]·0.5CH2Cl2γ = 74.515 (1)º
Mr = 505.11V = 2222.75 (12) Å3
Triclinic, P1Z = 4
a = 9.8830 (3) ÅMo Kα
b = 15.3591 (5) ŵ = 1.26 mm−1
c = 15.6544 (5) ÅT = 293 (2) K
α = 79.964 (1)º0.45 × 0.36 × 0.25 mm
β = 78.094 (1)º
Data collection top
Bruker APEXII
diffractometer		9215 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)		5134 reflections with I > 2σ(I)
Tmin = 0.688, Tmax = 1.000Rint = 0.025
13275 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056520 parameters
wR(F2) = 0.159H-atom parameters constrained
S = 1.02Δρmax = 0.44 e Å−3
9215 reflectionsΔρmin = −0.69 e Å−3
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
xyzUiso*/Ueq
Co10.32238 (6)0.79829 (4)0.05811 (4)0.04711 (18)
Co20.80414 (6)0.23178 (4)0.34801 (4)0.0570 (2)
Cl10.41735 (14)0.98271 (9)−0.08111 (9)0.0757 (4)
Cl20.31739 (13)0.86836 (8)0.17136 (8)0.0665 (3)
Cl30.52745 (12)0.71461 (9)−0.00237 (9)0.0693 (4)
Cl40.7295 (2)0.02459 (11)0.43135 (13)0.1119 (6)
Cl50.66100 (16)0.23526 (12)0.25601 (12)0.0995 (5)
Cl60.72549 (15)0.27227 (9)0.48148 (9)0.0774 (4)
Cl70.7761 (2)−0.26354 (17)0.52141 (14)0.1424 (8)
Cl80.6046 (3)−0.16227 (19)0.3978 (2)0.2024 (14)
N10.2218 (3)0.8907 (2)−0.0376 (2)0.0470 (8)
N20.1439 (3)0.7478 (2)0.0720 (2)0.0404 (8)
N30.9359 (4)0.1022 (2)0.3618 (2)0.0610 (10)
N40.9946 (3)0.2638 (2)0.2955 (2)0.0459 (8)
C10.2594 (5)0.9605 (3)−0.0895 (3)0.0565 (12)
C20.1767 (5)1.0170 (3)−0.1498 (3)0.0645 (13)
H20.20791.0651−0.18600.077*
C30.0504 (5)1.0002 (3)−0.1544 (3)0.0630 (13)
H3−0.00621.0377−0.19340.076*
C40.0039 (5)0.9259 (3)−0.1000 (3)0.0495 (11)
C5−0.1263 (5)0.9048 (3)−0.1012 (3)0.0559 (11)
H5−0.18650.9408−0.13900.067*
C6−0.1641 (5)0.8330 (3)−0.0479 (3)0.0570 (12)
H6−0.24930.8194−0.05040.068*
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)
H8−0.19700.68830.07120.072*
C9−0.0219 (5)0.6555 (3)0.1258 (3)0.0561 (12)
H9−0.04470.60570.16360.067*
C100.1054 (4)0.6791 (3)0.1273 (3)0.0439 (10)
C110.0545 (4)0.7974 (3)0.0149 (3)0.0416 (9)
C120.0954 (4)0.8733 (3)−0.0432 (3)0.0453 (10)
C130.1957 (4)0.6275 (3)0.1945 (3)0.0426 (10)
C140.1613 (5)0.6522 (3)0.2786 (3)0.0534 (11)
C150.2371 (5)0.6000 (4)0.3422 (3)0.0643 (13)
H150.21430.61690.39860.077*
C160.3449 (5)0.5241 (3)0.3256 (3)0.0636 (13)
C170.3784 (4)0.5010 (3)0.2401 (3)0.0590 (12)
H170.45140.45010.22740.071*
C180.3066 (4)0.5515 (3)0.1736 (3)0.0468 (10)
C190.0407 (6)0.7335 (4)0.3020 (3)0.0854 (17)
H19A0.03110.73920.36320.128*
H19B−0.04650.72500.29070.128*
H19C0.06120.78780.26700.128*
C200.4251 (6)0.4690 (4)0.3969 (4)0.101 (2)
H20A0.48820.50180.40850.152*
H20B0.47940.41180.37810.152*
H20C0.35880.45840.44950.152*
C210.3423 (5)0.5227 (3)0.0829 (3)0.0688 (14)
H21A0.41690.46790.08190.103*
H21B0.37340.57010.04110.103*
H21C0.25930.51190.06790.103*
C220.9067 (6)0.0232 (3)0.3965 (3)0.0731 (15)
C231.0084 (9)−0.0587 (4)0.4057 (4)0.094 (2)
H230.9818−0.11250.43060.113*
C241.1494 (8)−0.0579 (4)0.3770 (4)0.091 (2)
H241.2194−0.11180.38280.109*
C251.1888 (6)0.0243 (3)0.3387 (3)0.0717 (15)
C261.3299 (6)0.0325 (4)0.3070 (4)0.0821 (17)
H261.4042−0.01940.30920.099*
C271.3598 (6)0.1128 (4)0.2739 (4)0.0818 (17)
H271.45440.11550.25470.098*
C281.2495 (5)0.1951 (3)0.2671 (3)0.0598 (12)
C291.2745 (5)0.2805 (4)0.2325 (3)0.0695 (14)
H291.36660.28730.21070.083*
C301.1608 (5)0.3536 (3)0.2314 (3)0.0642 (13)
H301.17630.41090.20870.077*
C311.0218 (4)0.3453 (3)0.2633 (3)0.0478 (10)
C321.1082 (5)0.1893 (3)0.2975 (3)0.0511 (11)
C331.0767 (5)0.1025 (3)0.3340 (3)0.0558 (12)
C340.8998 (4)0.4272 (3)0.2636 (3)0.0459 (10)
C350.8679 (5)0.4817 (3)0.3307 (3)0.0503 (11)
C360.7599 (5)0.5611 (3)0.3259 (3)0.0579 (12)
H360.73840.59830.37010.069*
C370.6836 (5)0.5861 (3)0.2567 (3)0.0577 (12)
C380.7163 (5)0.5302 (3)0.1918 (3)0.0574 (12)
H380.66480.54580.14570.069*
C390.8230 (5)0.4519 (3)0.1937 (3)0.0537 (11)
C400.9502 (5)0.4564 (3)0.4063 (3)0.0662 (13)
H40A0.94470.39650.43450.099*
H40B0.91020.49940.44790.099*
H40C1.04810.45730.38440.099*
C410.5680 (5)0.6738 (3)0.2527 (4)0.0894 (18)
H41A0.52160.68520.31130.134*
H41B0.49950.66840.21970.134*
H41C0.60980.72340.22450.134*
C420.8605 (6)0.3948 (4)0.1182 (3)0.0828 (16)
H42A0.77960.40590.08930.124*
H42B0.88660.33140.14070.124*
H42C0.93900.41100.07690.124*
C430.6125 (7)−0.2104 (6)0.5048 (6)0.152 (3)
H43A0.5746−0.16300.54310.182*
H43B0.5526−0.25340.52090.182*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0409 (3)0.0501 (3)0.0512 (4)−0.0109 (3)−0.0104 (3)−0.0055 (3)
Co20.0542 (4)0.0565 (4)0.0653 (4)−0.0192 (3)−0.0143 (3)−0.0068 (3)
Cl10.0669 (8)0.0820 (9)0.0832 (9)−0.0381 (7)−0.0056 (7)−0.0007 (7)
Cl20.0776 (8)0.0572 (7)0.0661 (8)−0.0037 (6)−0.0261 (7)−0.0147 (6)
Cl30.0477 (7)0.0725 (8)0.0851 (9)−0.0073 (6)−0.0034 (6)−0.0230 (7)
Cl40.1371 (15)0.0841 (11)0.1283 (15)−0.0663 (10)−0.0125 (12)0.0002 (10)
Cl50.0840 (10)0.1128 (12)0.1225 (13)−0.0340 (9)−0.0530 (10)−0.0117 (10)
Cl60.0909 (10)0.0705 (8)0.0697 (8)−0.0218 (7)−0.0053 (7)−0.0116 (7)
Cl70.1138 (15)0.187 (2)0.1112 (15)−0.0117 (14)−0.0297 (12)−0.0040 (14)
Cl80.218 (3)0.149 (2)0.278 (4)−0.063 (2)−0.165 (3)0.049 (2)
N10.045 (2)0.047 (2)0.047 (2)−0.0096 (16)−0.0074 (16)−0.0038 (17)
N20.0408 (18)0.0408 (18)0.0384 (18)−0.0072 (15)−0.0076 (15)−0.0043 (15)
N30.086 (3)0.045 (2)0.056 (2)−0.019 (2)−0.016 (2)−0.0078 (18)
N40.048 (2)0.044 (2)0.047 (2)−0.0085 (17)−0.0143 (16)−0.0060 (16)
C10.060 (3)0.056 (3)0.051 (3)−0.019 (2)−0.002 (2)0.001 (2)
C20.080 (4)0.051 (3)0.059 (3)−0.019 (3)−0.011 (3)0.007 (2)
C30.073 (3)0.056 (3)0.059 (3)−0.008 (3)−0.026 (3)0.003 (2)
C40.056 (3)0.042 (2)0.049 (3)−0.008 (2)−0.012 (2)−0.002 (2)
C50.057 (3)0.054 (3)0.057 (3)−0.004 (2)−0.026 (2)−0.003 (2)
C60.051 (3)0.056 (3)0.069 (3)−0.008 (2)−0.028 (2)−0.006 (2)
C70.046 (2)0.048 (2)0.052 (3)−0.011 (2)−0.012 (2)−0.003 (2)
C80.046 (3)0.061 (3)0.077 (3)−0.020 (2)−0.020 (2)0.003 (3)
C90.052 (3)0.054 (3)0.065 (3)−0.022 (2)−0.019 (2)0.010 (2)
C100.041 (2)0.046 (2)0.043 (2)−0.0092 (19)−0.0081 (19)−0.0029 (19)
C110.036 (2)0.044 (2)0.044 (2)−0.0037 (18)−0.0097 (19)−0.0082 (19)
C120.042 (2)0.045 (2)0.045 (2)−0.0051 (19)−0.007 (2)−0.0073 (19)
C130.046 (2)0.044 (2)0.042 (2)−0.0171 (19)−0.0109 (19)−0.0014 (19)
C140.058 (3)0.057 (3)0.046 (3)−0.020 (2)−0.003 (2)−0.007 (2)
C150.076 (3)0.081 (4)0.041 (3)−0.034 (3)−0.008 (3)−0.001 (3)
C160.070 (3)0.069 (3)0.058 (3)−0.031 (3)−0.028 (3)0.015 (3)
C170.044 (3)0.048 (3)0.085 (4)−0.009 (2)−0.020 (3)0.002 (2)
C180.041 (2)0.046 (2)0.052 (3)−0.012 (2)−0.006 (2)−0.003 (2)
C190.099 (4)0.077 (4)0.071 (4)−0.010 (3)0.010 (3)−0.030 (3)
C200.102 (5)0.123 (5)0.085 (4)−0.042 (4)−0.056 (4)0.044 (4)
C210.079 (3)0.061 (3)0.060 (3)−0.009 (3)−0.002 (3)−0.017 (2)
C220.107 (4)0.055 (3)0.065 (3)−0.027 (3)−0.019 (3)−0.007 (3)
C230.163 (7)0.044 (3)0.075 (4)−0.028 (4)−0.019 (4)−0.006 (3)
C240.144 (6)0.048 (3)0.072 (4)0.006 (4)−0.031 (4)−0.012 (3)
C250.098 (4)0.057 (3)0.057 (3)0.006 (3)−0.031 (3)−0.017 (2)
C260.075 (4)0.078 (4)0.086 (4)0.021 (3)−0.033 (3)−0.025 (3)
C270.057 (3)0.094 (4)0.093 (4)0.006 (3)−0.021 (3)−0.035 (4)
C280.050 (3)0.068 (3)0.059 (3)0.003 (2)−0.017 (2)−0.020 (2)
C290.058 (3)0.079 (4)0.076 (4)−0.024 (3)−0.011 (3)−0.011 (3)
C300.056 (3)0.062 (3)0.077 (4)−0.022 (3)−0.012 (3)−0.002 (3)
C310.049 (3)0.051 (3)0.046 (2)−0.011 (2)−0.017 (2)−0.005 (2)
C320.053 (3)0.055 (3)0.048 (3)−0.010 (2)−0.014 (2)−0.011 (2)
C330.066 (3)0.051 (3)0.052 (3)−0.003 (2)−0.024 (2)−0.011 (2)
C340.051 (2)0.045 (2)0.044 (2)−0.016 (2)−0.016 (2)0.0045 (19)
C350.055 (3)0.054 (3)0.046 (3)−0.019 (2)−0.014 (2)−0.002 (2)
C360.060 (3)0.050 (3)0.064 (3)−0.017 (2)−0.005 (3)−0.010 (2)
C370.048 (3)0.050 (3)0.073 (3)−0.015 (2)−0.017 (2)0.007 (2)
C380.050 (3)0.055 (3)0.071 (3)−0.016 (2)−0.026 (2)0.007 (2)
C390.061 (3)0.059 (3)0.048 (3)−0.023 (2)−0.017 (2)0.000 (2)
C400.075 (3)0.073 (3)0.059 (3)−0.022 (3)−0.027 (3)−0.006 (3)
C410.064 (3)0.060 (3)0.134 (5)−0.002 (3)−0.022 (3)0.002 (3)
C420.101 (4)0.087 (4)0.067 (3)−0.013 (3)−0.036 (3)−0.013 (3)
C430.092 (5)0.168 (8)0.167 (8)−0.005 (5)−0.021 (5)0.014 (7)
Geometric parameters (Å, °) top
Co1—N22.067 (3)C19—H19A0.9600
Co1—N12.090 (3)C19—H19B0.9600
Co1—Cl32.2130 (12)C19—H19C0.9600
Co1—Cl22.2146 (13)C20—H20A0.9600
Co2—N42.043 (3)C20—H20B0.9600
Co2—N32.071 (4)C20—H20C0.9600
Co2—Cl52.2028 (16)C21—H21A0.9600
Co2—Cl62.2092 (15)C21—H21B0.9600
Cl1—C11.719 (5)C21—H21C0.9600
Cl4—C221.719 (6)C22—C231.391 (8)
Cl7—C431.656 (7)C23—C241.376 (8)
Cl8—C431.717 (8)C23—H230.9300
N1—C11.315 (5)C24—C251.418 (8)
N1—C121.369 (5)C24—H240.9300
N2—C101.329 (5)C25—C331.403 (6)
N2—C111.375 (5)C25—C261.412 (7)
N3—C221.319 (6)C26—C271.336 (7)
N3—C331.371 (6)C26—H260.9300
N4—C311.341 (5)C27—C281.436 (7)
N4—C321.373 (5)C27—H270.9300
C1—C21.402 (6)C28—C291.395 (7)
C2—C31.359 (6)C28—C321.401 (6)
C2—H20.9300C29—C301.361 (7)
C3—C41.421 (6)C29—H290.9300
C3—H30.9300C30—C311.393 (6)
C4—C121.397 (6)C30—H300.9300
C4—C51.412 (6)C31—C341.492 (6)
C5—C61.350 (6)C32—C331.443 (6)
C5—H50.9300C34—C351.389 (6)
C6—C71.428 (6)C34—C391.400 (6)
C6—H60.9300C35—C361.392 (6)
C7—C111.405 (5)C35—C401.510 (6)
C7—C81.406 (6)C36—C371.388 (6)
C8—C91.355 (6)C36—H360.9300
C8—H80.9300C37—C381.376 (6)
C9—C101.404 (6)C37—C411.517 (6)
C9—H90.9300C38—C391.372 (6)
C10—C131.500 (5)C38—H380.9300
C11—C121.442 (5)C39—C421.520 (6)
C13—C141.384 (6)C40—H40A0.9600
C13—C181.405 (5)C40—H40B0.9600
C14—C151.380 (6)C40—H40C0.9600
C14—C191.516 (6)C41—H41A0.9600
C15—C161.375 (7)C41—H41B0.9600
C15—H150.9300C41—H41C0.9600
C16—C171.396 (6)C42—H42A0.9600
C16—C201.505 (7)C42—H42B0.9600
C17—C181.386 (6)C42—H42C0.9600
C17—H170.9300C43—H43A0.9700
C18—C211.504 (6)C43—H43B0.9700
N2—Co1—N181.74 (13)C16—C20—H20C109.5
N2—Co1—Cl3117.08 (9)H20A—C20—H20C109.5
N1—Co1—Cl3110.81 (10)H20B—C20—H20C109.5
N2—Co1—Cl2111.88 (9)C18—C21—H21A109.5
N1—Co1—Cl2109.88 (10)C18—C21—H21B109.5
Cl3—Co1—Cl2119.14 (5)H21A—C21—H21B109.5
N4—Co2—N381.41 (15)C18—C21—H21C109.5
N4—Co2—Cl5117.29 (11)H21A—C21—H21C109.5
N3—Co2—Cl5108.36 (12)H21B—C21—H21C109.5
N4—Co2—Cl6111.17 (10)N3—C22—C23124.5 (6)
N3—Co2—Cl6107.10 (11)N3—C22—Cl4116.2 (4)
Cl5—Co2—Cl6122.82 (7)C23—C22—Cl4119.3 (5)
C1—N1—C12117.8 (4)C24—C23—C22118.1 (5)
C1—N1—Co1130.8 (3)C24—C23—H23120.9
C12—N1—Co1111.4 (3)C22—C23—H23120.9
C10—N2—C11118.7 (3)C23—C24—C25120.5 (5)
C10—N2—Co1129.9 (3)C23—C24—H24119.7
C11—N2—Co1111.3 (2)C25—C24—H24119.7
C22—N3—C33117.0 (4)C33—C25—C26119.0 (5)
C22—N3—Co2130.8 (4)C33—C25—C24115.9 (6)
C33—N3—Co2112.0 (3)C26—C25—C24125.0 (5)
C31—N4—C32117.9 (4)C27—C26—C25121.9 (5)
C31—N4—Co2129.3 (3)C27—C26—H26119.1
C32—N4—Co2112.8 (3)C25—C26—H26119.1
N1—C1—C2123.2 (4)C26—C27—C28121.6 (5)
N1—C1—Cl1117.5 (4)C26—C27—H27119.2
C2—C1—Cl1119.2 (4)C28—C27—H27119.2
C3—C2—C1118.8 (4)C29—C28—C32118.0 (4)
C3—C2—H2120.6C29—C28—C27124.0 (5)
C1—C2—H2120.6C32—C28—C27118.0 (5)
C2—C3—C4120.6 (4)C30—C29—C28118.3 (5)
C2—C3—H3119.7C30—C29—H29120.8
C4—C3—H3119.7C28—C29—H29120.8
C12—C4—C5120.7 (4)C29—C30—C31122.0 (5)
C12—C4—C3115.8 (4)C29—C30—H30119.0
C5—C4—C3123.5 (4)C31—C30—H30119.0
C6—C5—C4120.5 (4)N4—C31—C30120.9 (4)
C6—C5—H5119.7N4—C31—C34118.4 (4)
C4—C5—H5119.7C30—C31—C34120.7 (4)
C5—C6—C7121.0 (4)N4—C32—C28122.9 (4)
C5—C6—H6119.5N4—C32—C33116.9 (4)
C7—C6—H6119.5C28—C32—C33120.2 (4)
C11—C7—C8117.4 (4)N3—C33—C25123.9 (5)
C11—C7—C6119.6 (4)N3—C33—C32116.8 (4)
C8—C7—C6123.1 (4)C25—C33—C32119.3 (5)
C9—C8—C7119.1 (4)C35—C34—C39120.1 (4)
C9—C8—H8120.4C35—C34—C31119.9 (4)
C7—C8—H8120.4C39—C34—C31119.9 (4)
C8—C9—C10121.3 (4)C34—C35—C36118.5 (4)
C8—C9—H9119.3C34—C35—C40120.9 (4)
C10—C9—H9119.3C36—C35—C40120.7 (4)
N2—C10—C9120.9 (4)C37—C36—C35121.8 (4)
N2—C10—C13120.1 (3)C37—C36—H36119.1
C9—C10—C13119.0 (4)C35—C36—H36119.1
N2—C11—C7122.5 (4)C38—C37—C36118.5 (4)
N2—C11—C12118.3 (3)C38—C37—C41121.1 (5)
C7—C11—C12119.1 (4)C36—C37—C41120.4 (5)
N1—C12—C4123.8 (4)C39—C38—C37121.5 (4)
N1—C12—C11117.2 (4)C39—C38—H38119.2
C4—C12—C11119.0 (4)C37—C38—H38119.2
C14—C13—C18120.9 (4)C38—C39—C34119.6 (4)
C14—C13—C10118.8 (4)C38—C39—C42119.7 (4)
C18—C13—C10120.1 (4)C34—C39—C42120.6 (4)
C15—C14—C13118.7 (4)C35—C40—H40A109.5
C15—C14—C19120.0 (4)C35—C40—H40B109.5
C13—C14—C19121.3 (4)H40A—C40—H40B109.5
C16—C15—C14122.8 (4)C35—C40—H40C109.5
C16—C15—H15118.6H40A—C40—H40C109.5
C14—C15—H15118.6H40B—C40—H40C109.5
C15—C16—C17117.5 (4)C37—C41—H41A109.5
C15—C16—C20121.1 (5)C37—C41—H41B109.5
C17—C16—C20121.4 (5)H41A—C41—H41B109.5
C18—C17—C16122.1 (4)C37—C41—H41C109.5
C18—C17—H17118.9H41A—C41—H41C109.5
C16—C17—H17118.9H41B—C41—H41C109.5
C17—C18—C13118.0 (4)C39—C42—H42A109.5
C17—C18—C21120.7 (4)C39—C42—H42B109.5
C13—C18—C21121.3 (4)H42A—C42—H42B109.5
C14—C19—H19A109.5C39—C42—H42C109.5
C14—C19—H19B109.5H42A—C42—H42C109.5
H19A—C19—H19B109.5H42B—C42—H42C109.5
C14—C19—H19C109.5Cl7—C43—Cl8113.2 (5)
H19A—C19—H19C109.5Cl7—C43—H43A108.9
H19B—C19—H19C109.5Cl8—C43—H43A108.9
C16—C20—H20A109.5Cl7—C43—H43B108.9
C16—C20—H20B109.5Cl8—C43—H43B108.9
H20A—C20—H20B109.5H43A—C43—H43B107.8
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9···Cg1i0.932.593.470 (5)157
Symmetry codes: (i) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9···Cg1i0.932.593.470 (5)157
Symmetry codes: (i) x−1, y, z.
Table 2
Possible π–π stacking interactions (Å, °) top
Centroid–centroidαCgI-perpCgJ-perpslippage
Cg2 – Cg2i3.877 (3)0.03.7123.7121.12
Cg2 – Cg3i3.923 (3)0.493.7123.7011.23
Cg4 – Cg4ii3.992 (3)0.023.4903.4901.94
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 top

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

references
References top

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