metal-organic compounds
Dichlorido(2-chloro-9-mesityl-1,10-phenanthroline-κ2N,N′)cobalt(II) dichloromethane hemisolvate
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
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 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
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell 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
10.1107/S1600536808007320/dn2321sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808007320/dn2321Isup2.hkl
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%.
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).
Data collection: APEX2 (Bruker, 2004); cell
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).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. |
[CoCl2(C21H17ClN2)]·0.5CH2Cl2 | Z = 4 |
Mr = 505.11 | F(000) = 1024 |
Triclinic, P1 | Dx = 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 |
Bruker APEXII diffractometer | 9215 independent reflections |
Radiation source: fine-focus sealed tube | 5134 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 26.8°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −12→9 |
Tmin = 0.688, Tmax = 1.000 | k = −19→18 |
13275 measured reflections | l = −19→17 |
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(Fo2) + (0.0717P)2] where P = (Fo2 + 2Fc2)/3 |
9215 reflections | (Δ/σ)max = 0.002 |
520 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
[CoCl2(C21H17ClN2)]·0.5CH2Cl2 | γ = 74.515 (1)° |
Mr = 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)° |
Bruker APEXII diffractometer | 9215 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 5134 reflections with I > 2σ(I) |
Tmin = 0.688, Tmax = 1.000 | Rint = 0.025 |
13275 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.44 e Å−3 |
9215 reflections | Δρmin = −0.69 e Å−3 |
520 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
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 |
Mr | 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) |
Tmin, Tmax | 0.688, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13275, 9215, 5134 |
Rint | 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 |
Δρmax, Δρmin (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).
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. |
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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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).