Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614015411/yp3074sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015411/yp3074Isup2.hkl |
CCDC reference: 1011543
The use of late transition metal complexes anchored on nitrogen-donor ligands as catalysts in olefin oligomerization and polymerization reactions has witnessed enormous growth since their discovery by Brookhart and co-workers (Brookhart et al., 1995; Ittel et al., 2000). For the past decade, we have been investigating the use of nickel(II), palladium(II) and cobalt(II) complexes of pyrazole and pyrazolyl ligands as catalysts in ethylene and higher olefin polymerization and oligomerization reactions (Ojwach et al., 2005; Mkoyi et al., 2013; Ainooson et al., 2011). We recently reported that [(pyrazolylmethyl)pyridine]nickel(II) complexes not only produce highly active ethylene oligomerization reactions, but also promote tandem Friedel–Crafts alkylation of the toluene solvent used (Ojwach et al., 2009; Budhai et al., 2013; Benade et al., 2011). In our continuing efforts to develop efficient olefin transformation catalysts of late transition metal complexes, the title compound, (I), was synthesized. Activation of the compound to form an active ethylene oligomerization or polymerization catalyst unfortunately resulted in very low activities. We describe herein the solid-state structure and the gas-phase density functional theory (DFT) structure of this cobalt(II) complex.
3,5-Diphenyl-1H-pyrazole was synthesized by reacting dibenzoylmethane and hydrazine according to a previously described method (Kitajima et al., 1992). The title compound was prepared by adding a solution of CoCl2 (0.100 g, 0.770 mmol) in dichloromethane (15 ml) to a solution of 3,5-diphenyl-1H-pyrazole (0.340 g, 1.54 mmol) in dichloromethane (15 ml). The resulting blue solution was stirred for 24 h at room temperature. Slow evaporation of the reaction mixture afforded (I). Recrystallization of (I) from dichloromethane–hexane [Solvent ratio?] yielded blue crystals suitable for single-crystal X-ray diffraction (yield 0.38 g, 87%). IR (ATR, cm-1): 1079 (C—C), 1567 (C═N). ESI–MS: m/z (%) 612 [(M + 0.5CH2Cl2)+, 88%]. Analysis, calculated for C30H24Cl2CoN4.0.5CH2Cl2: C 59.77, H 4.11, N 9.14%; found: C 58.94, H 4.22, N 9.25%. µeff = 4.26 BM.
Crystal data, data collection and structure refinement details are summarized in Table 1. Pyrazole N-bound and solvent H atoms were located and allowed to refine isotropically. All other H atoms were placed in geometrically calculated positions, with aromatic C—H = 0.93 Å and Uiso(H) = 1.2Ueq.
The solid-state structure of (I) (Fig. 1) shows that the CoII centre adopts a distorted tetrahedral coordination geometry. Two of the coordination sites are occupied by two independent monodentate N-donor pyrazole-based ligands, and the third and fourth coordination sites are occupied by two chloride ligands. Table 2 gives selected geometric parameters which illustrate the distorted tetrahedral geometry. The planes of the phenyl rings of the ligand are not coplanar with the plane of the pyrazole ring. The C8—C7—C6—C5 and C8—C9—C10—C11 torsion angles of one pyrazole ligand are 19.8 (2) and -35.5 (3)°, respectively, while the C23—C22—C21—C20 and C23—C24—C25—C26 torsion angles of the second ligand are 20.1 (2) and 29.5 (2)°, respectively. These torsion angles illustrate the out-of-plane rotation of the phenyl rings relative to the pyrazole rings.
The metal chelate crystallizes as the dichloromethane hemisolvate. The C atom of the solvent molecule is located on a twofold rotation axis. The solvent molecule occupies a void of volume 104 Å3. There is a short Cl···Cl contact between dichloromethane atom Cl1s and atom Cl2 of the metal chelate. However, the solvent molecule is not involved in any meaningful intermolecular interactions.
The cobalt(II) complex forms an interesting dimeric supramolecular structure, supported by complementary hydrogen bonding between the pyrazole NH group and the chloride ligand of an adjacent molecule. This arrangement leads to a ten-membered hydrogen-bonded ring. The dimer has crystallographically imposed inversion symmetry (Ci). Although hydrogen-bond length does not neccessarily correlate linearly with bond strength, due to packing constraints in the lattice (Steiner, 1997), the hydrogen-bond length in (I) (Table 3) is significantly shorter (by 0.422 Å) than the sum of the van der Waals radii of the interacting atoms [Standard reference?]. This would imply that it is a moderately strong interaction. The dimeric structures are linked by weak C—H···Cl interactions between o-phenyl atom H11 and atom Cl2. These weak interactions link the dimers into a two-dimensional network perpendicular to the c axis.
The structures of the monomer and dimer of the metal chelate in vacuo were calculated using density functional theory (DFT) at the PBE/6-311G level of theory (Perdew et al., 1996, 1997; McLean & Chandler, 1980; Raghavachari et al., 1980; Wachters, 1970; Hay, 1977; Raghavachari & Trucks, 1989) using GAUSSIAN09 (Frisch et al., 2009). X-ray coordinates were used for the input structure. Normal geometry convergence criteria were applied with no symmetry constraints imposed. A lack of negative eigenvalues for the geometry-optimized structures suggests that they are true minima on the global potential energy surface. The experimental (solid-state) and simulated (in vacuo) structures were compared using structural overlays (least-squares fits), calculated using Mercury (Macrae et al., 2008). The similarity of the calculated and experimental structures is illustrated by r.m.s. deviations (RMSDs) for all non-H atoms (Fig. 3).
The most notable difference between the experimental and simulated structures is the coordination environment. The geometry of the CoII cation could reasonably be described as distorted tetrahedral for the experimental structure, but the simulated structure approaches a square-planar geometry. This is particularly evident when looking at the N1—Co1—Cl2 and N3—Co1—Cl1 bond angles (Table 2), which are closer to the ideal angle for a square-planar geometry (180°) rather than a tetrahedral geometry. Similarly, the N3—Co1—N1, N3—Co1—Cl2, N1—Co1—Cl1 and Cl2—Co1—Cl1 bond angles of the DFT-calculated structure approach 90°, the ideal angle for a square-planar geometry. However, despite the differences in the geometry of the metal ion, the dimeric structure retains its Ci symmetry in vacuo.
The partial charge distribution [non-bonding orbital (NBO) charges, measured in electrons] shows that the H atom of the pyrazole NH group carries the largest partial positive charge (0.444 e), while the chloride ligands carry the most negative partial charge (-0.613 e). Therefore, if a hydrogen bond is to be considered a simple electrostatic interaction then the simulations clearly explain the formation of the complementary N—H···Cl hydrogen bonds.
Interestingly, the RMSD for the dimeric structure (0.818 Å) is approximately equal to the RMSD for the monomeric structure (0.813 Å). This is an unexpected result, as usually the RMSD would be signifcantly larger when more atoms are used for the least-squares fits, and it would suggest that the dimerization process requires a degree of conformational distortion to allow for optimal hydrogen bonding. The simulations show that the optimized geometry of the dimeric structure in vacuo is 144 kJ mol-1 lower in energy than the solid-state structure. Seemingly, the stability gained through the hydrogen-bonded interactions is large enough to compensate for the fact that the individual monomers, which constitute the dimeric structure, are no longer in their lowest energy conformation. This point is further illustrated by the fact that the RMSD for an overlay of the experimental monomer and a monomer from the DFT-calculated dimer is 0.723 Å, smaller than that for the isolated monomer in vacuo. Similar distortions from the lowest-energy structures have been reported for other hydrogen-bonded dimeric structures (Akerman & Chiazzari, 2014). [Does this also shed light on the lack of catalytic activity?]
Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT-Plus (Bruker, 2012); data reduction: SAINT-Plus (Bruker, 2012); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).
[CoCl2(C15H12N2)2]·0.5CH2Cl2 | F(000) = 2512 |
Mr = 612.85 | Dx = 1.463 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 4835 reflections |
a = 13.7980 (9) Å | θ = 1.8–26.0° |
b = 20.8958 (16) Å | µ = 0.93 mm−1 |
c = 19.2954 (15) Å | T = 100 K |
V = 5563.3 (7) Å3 | Needle, blue |
Z = 8 | 0.20 × 0.12 × 0.06 mm |
Bruker APEXII CCD area-detector diffractometer | 5453 independent reflections |
Radiation source: Incoatec microsource | 4835 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω and ϕ scans | θmax = 26.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −8→16 |
Tmin = 0.835, Tmax = 0.946 | k = −23→25 |
26832 measured reflections | l = −23→20 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0229P)2 + 3.9174P] where P = (Fo2 + 2Fc2)/3 |
5453 reflections | (Δ/σ)max = 0.002 |
360 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[CoCl2(C15H12N2)2]·0.5CH2Cl2 | V = 5563.3 (7) Å3 |
Mr = 612.85 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 13.7980 (9) Å | µ = 0.93 mm−1 |
b = 20.8958 (16) Å | T = 100 K |
c = 19.2954 (15) Å | 0.20 × 0.12 × 0.06 mm |
Bruker APEXII CCD area-detector diffractometer | 5453 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 4835 reflections with I > 2σ(I) |
Tmin = 0.835, Tmax = 0.946 | Rint = 0.029 |
26832 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.29 e Å−3 |
5453 reflections | Δρmin = −0.25 e Å−3 |
360 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | ||
C1 | 0.32505 (12) | 0.33872 (7) | 0.38532 (8) | 0.0170 (3) | |
H1 | 0.3846 | 0.3530 | 0.4047 | 0.020* | |
C1S | 0.5000 | 0.51886 (15) | 0.2500 | 0.0416 (8) | |
C2 | 0.28674 (12) | 0.36961 (8) | 0.32782 (9) | 0.0199 (4) | |
H2 | 0.3198 | 0.4052 | 0.3084 | 0.024* | |
C3 | 0.20017 (12) | 0.34882 (8) | 0.29834 (9) | 0.0204 (4) | |
H3 | 0.1740 | 0.3703 | 0.2592 | 0.024* | |
C4 | 0.15231 (12) | 0.29637 (8) | 0.32656 (8) | 0.0190 (3) | |
H4 | 0.0940 | 0.2814 | 0.3061 | 0.023* | |
C5 | 0.18965 (11) | 0.26579 (8) | 0.38467 (8) | 0.0166 (3) | |
H5 | 0.1560 | 0.2304 | 0.4041 | 0.020* | |
C6 | 0.27641 (11) | 0.28664 (7) | 0.41499 (8) | 0.0142 (3) | |
C7 | 0.31432 (11) | 0.25201 (7) | 0.47570 (8) | 0.0139 (3) | |
C8 | 0.29079 (11) | 0.18950 (7) | 0.49673 (8) | 0.0157 (3) | |
H8 | 0.2457 | 0.1614 | 0.4753 | 0.019* | |
C9 | 0.34617 (11) | 0.17703 (7) | 0.55457 (8) | 0.0143 (3) | |
C10 | 0.35515 (11) | 0.11975 (7) | 0.59828 (8) | 0.0149 (3) | |
C11 | 0.27413 (12) | 0.08122 (7) | 0.61126 (8) | 0.0177 (3) | |
H11 | 0.2129 | 0.0923 | 0.5922 | 0.021* | |
C12 | 0.28349 (13) | 0.02673 (8) | 0.65198 (9) | 0.0206 (4) | |
H12 | 0.2284 | 0.0007 | 0.6609 | 0.025* | |
C13 | 0.37299 (13) | 0.01010 (8) | 0.67974 (9) | 0.0215 (4) | |
H13 | 0.3790 | −0.0273 | 0.7074 | 0.026* | |
C14 | 0.45366 (13) | 0.04824 (8) | 0.66705 (9) | 0.0207 (4) | |
H14 | 0.5148 | 0.0369 | 0.6860 | 0.025* | |
C15 | 0.44488 (12) | 0.10297 (8) | 0.62664 (8) | 0.0171 (3) | |
H15 | 0.5000 | 0.1291 | 0.6183 | 0.020* | |
C16 | 0.27288 (12) | 0.56116 (8) | 0.37405 (9) | 0.0189 (3) | |
H16 | 0.3374 | 0.5460 | 0.3787 | 0.023* | |
C17 | 0.25198 (13) | 0.60959 (8) | 0.32697 (9) | 0.0215 (4) | |
H17 | 0.3024 | 0.6277 | 0.2998 | 0.026* | |
C18 | 0.15729 (13) | 0.63167 (8) | 0.31952 (9) | 0.0231 (4) | |
H18 | 0.1433 | 0.6648 | 0.2873 | 0.028* | |
C19 | 0.08346 (12) | 0.60546 (8) | 0.35903 (9) | 0.0225 (4) | |
H19 | 0.0188 | 0.6202 | 0.3535 | 0.027* | |
C20 | 0.10401 (12) | 0.55754 (8) | 0.40671 (9) | 0.0184 (3) | |
H20 | 0.0534 | 0.5401 | 0.4342 | 0.022* | |
C21 | 0.19875 (11) | 0.53473 (7) | 0.41458 (8) | 0.0160 (3) | |
C22 | 0.21675 (11) | 0.48260 (7) | 0.46387 (8) | 0.0156 (3) | |
C23 | 0.15326 (11) | 0.43827 (7) | 0.49217 (8) | 0.0162 (3) | |
H23 | 0.0855 | 0.4353 | 0.4839 | 0.019* | |
C24 | 0.20855 (11) | 0.39889 (7) | 0.53528 (8) | 0.0148 (3) | |
C25 | 0.17748 (11) | 0.34307 (7) | 0.57646 (8) | 0.0153 (3) | |
C26 | 0.09988 (12) | 0.30532 (8) | 0.55428 (9) | 0.0185 (3) | |
H26 | 0.0651 | 0.3169 | 0.5137 | 0.022* | |
C27 | 0.07335 (12) | 0.25110 (8) | 0.59117 (9) | 0.0235 (4) | |
H27 | 0.0203 | 0.2258 | 0.5759 | 0.028* | |
C28 | 0.12390 (13) | 0.23364 (8) | 0.65022 (10) | 0.0251 (4) | |
H28 | 0.1062 | 0.1961 | 0.6749 | 0.030* | |
C29 | 0.20046 (13) | 0.27114 (8) | 0.67327 (9) | 0.0227 (4) | |
H29 | 0.2353 | 0.2592 | 0.7137 | 0.027* | |
C30 | 0.22614 (12) | 0.32621 (8) | 0.63722 (9) | 0.0192 (3) | |
H30 | 0.2771 | 0.3525 | 0.6540 | 0.023* | |
Cl1 | 0.48310 (3) | 0.342643 (19) | 0.65612 (2) | 0.01995 (9) | |
Cl1S | 0.51433 (3) | 0.47199 (2) | 0.32554 (2) | 0.03041 (11) | |
Cl2 | 0.53993 (3) | 0.413550 (18) | 0.48609 (2) | 0.01836 (9) | |
Co1 | 0.424708 (15) | 0.366007 (10) | 0.550060 (11) | 0.01355 (6) | |
N1 | 0.38080 (9) | 0.27707 (6) | 0.51942 (7) | 0.0144 (3) | |
N2 | 0.40041 (10) | 0.22977 (6) | 0.56598 (7) | 0.0148 (3) | |
N3 | 0.30251 (9) | 0.41756 (6) | 0.53376 (7) | 0.0147 (3) | |
N4 | 0.30528 (10) | 0.46864 (6) | 0.48989 (7) | 0.0150 (3) | |
H1S | 0.4408 (18) | 0.5437 (13) | 0.2557 (15) | 0.072 (9)* | |
H101 | 0.4319 (12) | 0.2399 (8) | 0.6020 (10) | 0.015 (5)* | |
H102 | 0.3583 (14) | 0.4898 (9) | 0.4837 (10) | 0.020 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0186 (8) | 0.0153 (8) | 0.0170 (8) | 0.0002 (6) | −0.0004 (6) | −0.0037 (7) |
C1S | 0.076 (2) | 0.0272 (16) | 0.0217 (15) | 0.000 | −0.0016 (16) | 0.000 |
C2 | 0.0241 (9) | 0.0159 (8) | 0.0198 (9) | −0.0006 (7) | 0.0017 (7) | 0.0024 (7) |
C3 | 0.0244 (9) | 0.0216 (9) | 0.0151 (8) | 0.0059 (7) | −0.0016 (7) | 0.0026 (7) |
C4 | 0.0162 (8) | 0.0218 (9) | 0.0191 (9) | 0.0021 (7) | −0.0022 (6) | −0.0022 (7) |
C5 | 0.0179 (8) | 0.0144 (8) | 0.0176 (8) | 0.0015 (6) | 0.0018 (6) | −0.0011 (6) |
C6 | 0.0174 (8) | 0.0122 (7) | 0.0131 (8) | 0.0028 (6) | 0.0015 (6) | −0.0027 (6) |
C7 | 0.0141 (7) | 0.0141 (8) | 0.0134 (8) | 0.0022 (6) | 0.0015 (6) | −0.0025 (6) |
C8 | 0.0175 (8) | 0.0142 (8) | 0.0154 (8) | −0.0004 (6) | −0.0025 (6) | −0.0021 (6) |
C9 | 0.0155 (7) | 0.0123 (7) | 0.0149 (8) | 0.0014 (6) | 0.0028 (6) | −0.0026 (6) |
C10 | 0.0199 (8) | 0.0126 (8) | 0.0123 (8) | 0.0021 (6) | −0.0002 (6) | −0.0032 (6) |
C11 | 0.0192 (8) | 0.0160 (8) | 0.0180 (8) | −0.0005 (6) | −0.0028 (7) | −0.0031 (7) |
C12 | 0.0264 (9) | 0.0148 (8) | 0.0205 (9) | −0.0042 (7) | 0.0013 (7) | −0.0015 (7) |
C13 | 0.0339 (10) | 0.0140 (8) | 0.0168 (8) | 0.0039 (7) | −0.0005 (7) | 0.0014 (7) |
C14 | 0.0229 (9) | 0.0231 (9) | 0.0163 (8) | 0.0078 (7) | −0.0025 (7) | 0.0001 (7) |
C15 | 0.0181 (8) | 0.0177 (8) | 0.0153 (8) | 0.0008 (6) | 0.0011 (6) | −0.0026 (7) |
C16 | 0.0178 (8) | 0.0188 (8) | 0.0201 (9) | 0.0012 (6) | 0.0012 (7) | −0.0036 (7) |
C17 | 0.0242 (9) | 0.0205 (9) | 0.0196 (9) | −0.0029 (7) | 0.0024 (7) | 0.0003 (7) |
C18 | 0.0302 (10) | 0.0175 (8) | 0.0216 (9) | 0.0023 (7) | −0.0025 (7) | 0.0008 (7) |
C19 | 0.0217 (9) | 0.0198 (9) | 0.0261 (10) | 0.0044 (7) | −0.0035 (7) | −0.0021 (7) |
C20 | 0.0184 (8) | 0.0165 (8) | 0.0203 (9) | −0.0017 (6) | 0.0012 (7) | −0.0024 (7) |
C21 | 0.0191 (8) | 0.0129 (8) | 0.0159 (8) | −0.0006 (6) | −0.0004 (6) | −0.0039 (6) |
C22 | 0.0162 (8) | 0.0140 (8) | 0.0165 (8) | 0.0015 (6) | −0.0003 (6) | −0.0044 (6) |
C23 | 0.0137 (7) | 0.0173 (8) | 0.0176 (8) | −0.0004 (6) | 0.0006 (6) | −0.0036 (7) |
C24 | 0.0154 (8) | 0.0145 (8) | 0.0146 (8) | −0.0015 (6) | 0.0013 (6) | −0.0037 (6) |
C25 | 0.0152 (7) | 0.0138 (8) | 0.0169 (8) | 0.0006 (6) | 0.0051 (6) | −0.0021 (6) |
C26 | 0.0172 (8) | 0.0185 (8) | 0.0196 (9) | 0.0008 (7) | −0.0006 (7) | −0.0011 (7) |
C27 | 0.0220 (9) | 0.0191 (9) | 0.0293 (10) | −0.0049 (7) | 0.0026 (7) | −0.0025 (7) |
C28 | 0.0299 (10) | 0.0171 (8) | 0.0282 (10) | −0.0002 (7) | 0.0085 (8) | 0.0042 (7) |
C29 | 0.0243 (9) | 0.0250 (9) | 0.0187 (9) | 0.0043 (7) | 0.0028 (7) | 0.0021 (7) |
C30 | 0.0176 (8) | 0.0220 (9) | 0.0181 (9) | −0.0008 (7) | 0.0017 (7) | −0.0028 (7) |
Cl1 | 0.0230 (2) | 0.0197 (2) | 0.0172 (2) | −0.00119 (16) | −0.00586 (16) | −0.00122 (16) |
Cl1S | 0.0284 (2) | 0.0312 (2) | 0.0317 (3) | −0.00108 (19) | −0.00016 (19) | 0.0107 (2) |
Cl2 | 0.01646 (19) | 0.01701 (19) | 0.0216 (2) | −0.00379 (15) | 0.00254 (15) | −0.00040 (16) |
Co1 | 0.01353 (11) | 0.01202 (11) | 0.01510 (12) | −0.00101 (8) | −0.00092 (8) | −0.00044 (8) |
N1 | 0.0163 (7) | 0.0126 (6) | 0.0143 (7) | 0.0001 (5) | −0.0004 (5) | −0.0001 (5) |
N2 | 0.0174 (7) | 0.0135 (7) | 0.0133 (7) | 0.0000 (5) | −0.0033 (6) | 0.0003 (5) |
N3 | 0.0161 (7) | 0.0121 (6) | 0.0160 (7) | −0.0017 (5) | 0.0012 (5) | −0.0006 (5) |
N4 | 0.0137 (7) | 0.0121 (7) | 0.0191 (7) | −0.0021 (5) | 0.0011 (5) | −0.0001 (5) |
C1—C2 | 1.388 (2) | C17—C18 | 1.393 (2) |
C1—C6 | 1.401 (2) | C17—H17 | 0.9500 |
C1—H1 | 0.9500 | C18—C19 | 1.385 (3) |
C1S—Cl1S | 1.7671 (17) | C18—H18 | 0.9500 |
C1S—Cl1Si | 1.7671 (17) | C19—C20 | 1.389 (2) |
C1S—H1S | 0.97 (2) | C19—H19 | 0.9500 |
C2—C3 | 1.393 (2) | C20—C21 | 1.400 (2) |
C2—H2 | 0.9500 | C20—H20 | 0.9500 |
C3—C4 | 1.391 (2) | C21—C22 | 1.467 (2) |
C3—H3 | 0.9500 | C22—N4 | 1.353 (2) |
C4—C5 | 1.390 (2) | C22—C23 | 1.387 (2) |
C4—H4 | 0.9500 | C23—C24 | 1.397 (2) |
C5—C6 | 1.402 (2) | C23—H23 | 0.9500 |
C5—H5 | 0.9500 | C24—N3 | 1.354 (2) |
C6—C7 | 1.473 (2) | C24—C25 | 1.475 (2) |
C7—N1 | 1.352 (2) | C25—C30 | 1.396 (2) |
C7—C8 | 1.406 (2) | C25—C26 | 1.397 (2) |
C8—C9 | 1.377 (2) | C26—C27 | 1.387 (2) |
C8—H8 | 0.9500 | C26—H26 | 0.9500 |
C9—N2 | 1.350 (2) | C27—C28 | 1.385 (3) |
C9—C10 | 1.469 (2) | C27—H27 | 0.9500 |
C10—C15 | 1.398 (2) | C28—C29 | 1.388 (3) |
C10—C11 | 1.400 (2) | C28—H28 | 0.9500 |
C11—C12 | 1.389 (2) | C29—C30 | 1.391 (2) |
C11—H11 | 0.9500 | C29—H29 | 0.9500 |
C12—C13 | 1.390 (2) | C30—H30 | 0.9500 |
C12—H12 | 0.9500 | Cl1—Co1 | 2.2530 (5) |
C13—C14 | 1.391 (3) | Cl2—Co1 | 2.2446 (4) |
C13—H13 | 0.9500 | Co1—N3 | 2.0253 (13) |
C14—C15 | 1.389 (2) | Co1—N1 | 2.0422 (13) |
C14—H14 | 0.9500 | N1—N2 | 1.3626 (18) |
C15—H15 | 0.9500 | N2—H101 | 0.846 (18) |
C16—C17 | 1.390 (2) | N3—N4 | 1.3629 (18) |
C16—C21 | 1.401 (2) | N4—H102 | 0.863 (19) |
C16—H16 | 0.9500 | ||
C2—C1—C6 | 120.35 (15) | C17—C18—H18 | 119.9 |
C2—C1—H1 | 119.8 | C18—C19—C20 | 119.97 (16) |
C6—C1—H1 | 119.8 | C18—C19—H19 | 120.0 |
Cl1S—C1S—Cl1Si | 112.68 (17) | C20—C19—H19 | 120.0 |
Cl1S—C1S—H1S | 107.2 (17) | C19—C20—C21 | 120.52 (16) |
Cl1Si—C1S—H1S | 107.1 (17) | C19—C20—H20 | 119.7 |
C1—C2—C3 | 120.53 (15) | C21—C20—H20 | 119.7 |
C1—C2—H2 | 119.7 | C20—C21—C16 | 119.16 (15) |
C3—C2—H2 | 119.7 | C20—C21—C22 | 118.76 (15) |
C4—C3—C2 | 119.56 (15) | C16—C21—C22 | 122.07 (14) |
C4—C3—H3 | 120.2 | N4—C22—C23 | 106.28 (14) |
C2—C3—H3 | 120.2 | N4—C22—C21 | 123.61 (14) |
C5—C4—C3 | 120.15 (15) | C23—C22—C21 | 130.10 (15) |
C5—C4—H4 | 119.9 | C22—C23—C24 | 106.44 (14) |
C3—C4—H4 | 119.9 | C22—C23—H23 | 126.8 |
C4—C5—C6 | 120.69 (15) | C24—C23—H23 | 126.8 |
C4—C5—H5 | 119.7 | N3—C24—C23 | 109.90 (14) |
C6—C5—H5 | 119.7 | N3—C24—C25 | 121.17 (14) |
C1—C6—C5 | 118.69 (14) | C23—C24—C25 | 128.90 (14) |
C1—C6—C7 | 122.44 (14) | C30—C25—C26 | 118.90 (15) |
C5—C6—C7 | 118.84 (14) | C30—C25—C24 | 120.80 (14) |
N1—C7—C8 | 109.67 (14) | C26—C25—C24 | 120.28 (15) |
N1—C7—C6 | 123.16 (14) | C27—C26—C25 | 120.41 (16) |
C8—C7—C6 | 127.16 (14) | C27—C26—H26 | 119.8 |
C9—C8—C7 | 106.35 (14) | C25—C26—H26 | 119.8 |
C9—C8—H8 | 126.8 | C28—C27—C26 | 120.29 (16) |
C7—C8—H8 | 126.8 | C28—C27—H27 | 119.9 |
N2—C9—C8 | 106.57 (14) | C26—C27—H27 | 119.9 |
N2—C9—C10 | 121.64 (14) | C27—C28—C29 | 119.87 (16) |
C8—C9—C10 | 131.75 (14) | C27—C28—H28 | 120.1 |
C15—C10—C11 | 119.52 (15) | C29—C28—H28 | 120.1 |
C15—C10—C9 | 120.23 (14) | C28—C29—C30 | 120.05 (16) |
C11—C10—C9 | 120.24 (14) | C28—C29—H29 | 120.0 |
C12—C11—C10 | 119.88 (15) | C30—C29—H29 | 120.0 |
C12—C11—H11 | 120.1 | C29—C30—C25 | 120.42 (16) |
C10—C11—H11 | 120.1 | C29—C30—H30 | 119.8 |
C11—C12—C13 | 120.35 (16) | C25—C30—H30 | 119.8 |
C11—C12—H12 | 119.8 | N3—Co1—N1 | 101.08 (5) |
C13—C12—H12 | 119.8 | N3—Co1—Cl2 | 105.60 (4) |
C12—C13—C14 | 120.00 (15) | N1—Co1—Cl2 | 116.98 (4) |
C12—C13—H13 | 120.0 | N3—Co1—Cl1 | 123.64 (4) |
C14—C13—H13 | 120.0 | N1—Co1—Cl1 | 99.89 (4) |
C15—C14—C13 | 120.05 (16) | Cl2—Co1—Cl1 | 110.008 (17) |
C15—C14—H14 | 120.0 | C7—N1—N2 | 105.38 (12) |
C13—C14—H14 | 120.0 | C7—N1—Co1 | 137.26 (11) |
C14—C15—C10 | 120.21 (15) | N2—N1—Co1 | 114.22 (10) |
C14—C15—H15 | 119.9 | C9—N2—N1 | 111.99 (13) |
C10—C15—H15 | 119.9 | C9—N2—H101 | 128.5 (12) |
C17—C16—C21 | 120.02 (15) | N1—N2—H101 | 117.6 (12) |
C17—C16—H16 | 120.0 | C24—N3—N4 | 105.41 (13) |
C21—C16—H16 | 120.0 | C24—N3—Co1 | 129.83 (11) |
C16—C17—C18 | 120.20 (16) | N4—N3—Co1 | 119.32 (10) |
C16—C17—H17 | 119.9 | C22—N4—N3 | 111.97 (13) |
C18—C17—H17 | 119.9 | C22—N4—H102 | 127.2 (12) |
C19—C18—C17 | 120.13 (16) | N3—N4—H102 | 120.7 (12) |
C19—C18—H18 | 119.9 |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H102···Cl2ii | 0.86 (2) | 2.53 (2) | 3.292 (1) | 148 (2) |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [CoCl2(C15H12N2)2]·0.5CH2Cl2 |
Mr | 612.85 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 100 |
a, b, c (Å) | 13.7980 (9), 20.8958 (16), 19.2954 (15) |
V (Å3) | 5563.3 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.20 × 0.12 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2012) |
Tmin, Tmax | 0.835, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26832, 5453, 4835 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.061, 1.03 |
No. of reflections | 5453 |
No. of parameters | 360 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.25 |
Computer programs: APEX2 (Bruker, 2012), SAINT-Plus (Bruker, 2012), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H102···Cl2i | 0.86 (2) | 2.53 (2) | 3.292 (1) | 148 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Bond/angle | Experimental length/angle | Calculated length/angle (monomer) | Calculated length/angle (dimer) |
Co1—Cl1 | 2.2530 (5) | 2.222 | 2.265 |
Co1—Cl2 | 2.2446 (4) | 2.220 | 2.292 |
Co1—N3 | 2.0253 (13) | 1.893 | 1.872 |
Co1—N1 | 2.0422 (13) | 1.901 | 1.875 |
N3—Co1—N1 | 101.08 (5) | 92.51 | 94.61 |
N3—Co1—Cl2 | 105.60 (4) | 90.18 | 91.88 |
N1—Co1—Cl2 | 116.98 (4) | 151.77 | 159.66 |
N3—Co1—Cl1 | 123.64 (4) | 158.29 | 140.02 |
N1—Co1—Cl1 | 99.89 (4) | 90.13 | 91.39 |
Cl2—Co1—Cl1 | 110.01 (2) | 97.60 | 95.96 |