Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112020884/eg3092sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020884/eg3092Isup2.hkl |
CCDC reference: 889372
For related literature, see: Bondi (1964); Caballero et al. (2001); Cotton et al. (1961); Douthwaite et al. (1999, 2001, 2002); Herrmann et al. (1996); Mukerjee et al. (2000); Sheldrick (2008); Unger et al. (2007).
The bisimidazolium salt was previously deprotonated by sodium hexamethyldisilazan in tetrahydrofuran and the formation of the free carbene could be independently confirmed (Douthwaite et al., 1999). The corresponding nickel and palladium NHC complexes have been described in the literature (Douthwaite et al., 2001, 2002) and the addition of sulfur leads to the dithiones (Caballero et al., 2001; Herrmann et al., 1996). However, in this instance, the addition of bis(triphenylphosphane)cobalt(II) chloride (Cotton et al., 1961) did not lead to the expected formation of the biscarbene complex, and instead we isolated the N-coordinated complex, (I). [Recrystallisation from which solvent?] The crystal selected was fixed in a capillary with perfluorinated ether and transferred to the diffractometer.
H atoms were constrained to an ideal geometry using the standard riding model implemented in SHELXL97 (Sheldrick, 2008). H atoms were fixed with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms, or C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms.
Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
[CoCl2(C7H12N2)2] | F(000) = 1576 |
Mr = 378.20 | Dx = 1.368 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7031 reflections |
a = 14.1054 (1) Å | θ = 1.5–25.4° |
b = 14.5470 (1) Å | µ = 1.23 mm−1 |
c = 18.7059 (2) Å | T = 173 K |
β = 106.9542 (3)° | Fragment, blue |
V = 3671.47 (5) Å3 | 0.33 × 0.33 × 0.05 mm |
Z = 8 |
Nonius KappaCCD area-detector diffractometer | 6741 independent reflections |
Radiation source: Nonius FR 591 rotating-anode | 5547 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
Detector resolution: 18 pixels mm-1 | θmax = 25.4°, θmin = 1.5° |
ϕ and ω rotation scans | h = −17→17 |
Absorption correction: multi-scan [applied during the scaling procedure (DENZO; Otwinowski & Minor, 1997)] | k = −17→17 |
Tmin = 0.857, Tmax = 1.000 | l = −22→21 |
74460 measured reflections |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.03 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo2) + (0.0321P)2 + 2.5029P] where P = (Fo2 + 2Fc2)/3 |
6741 reflections | (Δ/σ)max = 0.001 |
391 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
0 constraints |
[CoCl2(C7H12N2)2] | V = 3671.47 (5) Å3 |
Mr = 378.20 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.1054 (1) Å | µ = 1.23 mm−1 |
b = 14.5470 (1) Å | T = 173 K |
c = 18.7059 (2) Å | 0.33 × 0.33 × 0.05 mm |
β = 106.9542 (3)° |
Nonius KappaCCD area-detector diffractometer | 6741 independent reflections |
Absorption correction: multi-scan [applied during the scaling procedure (DENZO; Otwinowski & Minor, 1997)] | 5547 reflections with I > 2σ(I) |
Tmin = 0.857, Tmax = 1.000 | Rint = 0.056 |
74460 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.28 e Å−3 |
6741 reflections | Δρmin = −0.30 e Å−3 |
391 parameters |
Experimental. Diffractometer operator E. Herdtweck scan speed 2 × 30 s per film repetition 1 dx 40 933 films measured in 8 data sets set 1: phi-scan with delta_phi = 1.0 set 2 to 9: omega-scans with delta_omega = 1.0 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating R_factor_obs 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 | 0.30046 (2) | 0.148881 (19) | 0.296068 (16) | 0.02443 (8) | |
Cl1 | 0.22349 (4) | 0.16251 (4) | 0.17244 (3) | 0.03311 (14) | |
Cl2 | 0.33651 (4) | 0.00521 (3) | 0.34197 (3) | 0.03122 (13) | |
N1 | 0.43252 (13) | 0.21302 (11) | 0.32086 (9) | 0.0244 (4) | |
N2 | 0.55196 (13) | 0.31650 (11) | 0.34675 (10) | 0.0246 (4) | |
N3 | 0.21723 (13) | 0.20424 (12) | 0.35646 (10) | 0.0276 (4) | |
N4 | 0.12648 (13) | 0.29509 (12) | 0.40414 (10) | 0.0283 (4) | |
C1 | 0.45390 (16) | 0.30200 (14) | 0.32959 (12) | 0.0258 (5) | |
H11 | 0.4059 | 0.3493 | 0.3244 | 0.031* | |
C2 | 0.52234 (16) | 0.16891 (14) | 0.33325 (12) | 0.0266 (5) | |
H21 | 0.5310 | 0.1043 | 0.3309 | 0.032* | |
C3 | 0.59633 (16) | 0.23173 (14) | 0.34928 (12) | 0.0273 (5) | |
H31 | 0.6653 | 0.2197 | 0.3601 | 0.033* | |
C4 | 0.60243 (17) | 0.40801 (14) | 0.36558 (13) | 0.0296 (5) | |
C5 | 0.6005 (2) | 0.43318 (17) | 0.44427 (14) | 0.0441 (7) | |
H51 | 0.5317 | 0.4379 | 0.4453 | 0.066* | |
H52 | 0.6340 | 0.4923 | 0.4587 | 0.066* | |
H53 | 0.6348 | 0.3855 | 0.4794 | 0.066* | |
C6 | 0.54547 (18) | 0.47873 (15) | 0.30912 (15) | 0.0380 (6) | |
H61 | 0.5412 | 0.4580 | 0.2584 | 0.057* | |
H62 | 0.5800 | 0.5379 | 0.3187 | 0.057* | |
H63 | 0.4785 | 0.4857 | 0.3140 | 0.057* | |
C7 | 0.70808 (18) | 0.40011 (17) | 0.36149 (16) | 0.0433 (6) | |
H71 | 0.7450 | 0.3567 | 0.3996 | 0.065* | |
H72 | 0.7401 | 0.4606 | 0.3704 | 0.065* | |
H73 | 0.7074 | 0.3780 | 0.3119 | 0.065* | |
C8 | 0.17982 (16) | 0.28800 (15) | 0.35556 (12) | 0.0283 (5) | |
H81 | 0.1895 | 0.3367 | 0.3246 | 0.034* | |
C9 | 0.18704 (17) | 0.15609 (15) | 0.40924 (14) | 0.0338 (5) | |
H91 | 0.2030 | 0.0938 | 0.4228 | 0.041* | |
C10 | 0.13101 (18) | 0.21144 (15) | 0.43887 (14) | 0.0364 (6) | |
H101 | 0.1008 | 0.1955 | 0.4764 | 0.044* | |
C11 | 0.07807 (17) | 0.38122 (15) | 0.42007 (14) | 0.0332 (5) | |
C12 | 0.0119 (2) | 0.35709 (18) | 0.46857 (18) | 0.0528 (8) | |
H112 | 0.0527 | 0.3337 | 0.5169 | 0.079* | |
H121 | −0.0358 | 0.3099 | 0.4436 | 0.079* | |
H123 | −0.0237 | 0.4122 | 0.4765 | 0.079* | |
C13 | 0.0174 (2) | 0.42239 (19) | 0.34635 (16) | 0.0549 (8) | |
H131 | 0.0614 | 0.4389 | 0.3164 | 0.082* | |
H132 | −0.0168 | 0.4776 | 0.3560 | 0.082* | |
H133 | −0.0315 | 0.3773 | 0.3191 | 0.082* | |
C14 | 0.15973 (19) | 0.44627 (16) | 0.46138 (15) | 0.0421 (6) | |
H141 | 0.1990 | 0.4173 | 0.5079 | 0.063* | |
H142 | 0.1303 | 0.5033 | 0.4730 | 0.063* | |
H143 | 0.2027 | 0.4602 | 0.4300 | 0.063* | |
Co2 | 0.19130 (2) | 0.49803 (2) | 0.164679 (19) | 0.03167 (9) | |
Cl3 | 0.26847 (5) | 0.49558 (4) | 0.28981 (4) | 0.03938 (15) | |
Cl4 | 0.14925 (5) | 0.63903 (4) | 0.11322 (4) | 0.04224 (16) | |
N21 | 0.06229 (14) | 0.42985 (13) | 0.14949 (12) | 0.0372 (5) | |
N22 | −0.05722 (14) | 0.33495 (12) | 0.15524 (12) | 0.0338 (5) | |
N23 | 0.28478 (14) | 0.44774 (12) | 0.11119 (11) | 0.0311 (4) | |
N24 | 0.39698 (13) | 0.36514 (12) | 0.07875 (10) | 0.0263 (4) | |
C21 | 0.03877 (17) | 0.34402 (15) | 0.15985 (13) | 0.0304 (5) | |
H211 | 0.0847 | 0.2945 | 0.1695 | 0.036* | |
C22 | −0.0240 (2) | 0.47894 (18) | 0.13973 (19) | 0.0544 (8) | |
H221 | −0.0305 | 0.5435 | 0.1322 | 0.065* | |
C23 | −0.09782 (19) | 0.42161 (17) | 0.14242 (17) | 0.0512 (7) | |
H231 | −0.1649 | 0.4378 | 0.1366 | 0.061* | |
C24 | −0.11329 (18) | 0.24870 (16) | 0.15900 (14) | 0.0367 (6) | |
C25 | −0.1646 (3) | 0.2181 (2) | 0.07967 (19) | 0.0751 (10) | |
H251 | −0.2071 | 0.2678 | 0.0527 | 0.113* | |
H252 | −0.2050 | 0.1636 | 0.0806 | 0.113* | |
H253 | −0.1147 | 0.2031 | 0.0544 | 0.113* | |
C26 | −0.0416 (2) | 0.17655 (19) | 0.2015 (2) | 0.0747 (11) | |
H261 | −0.0783 | 0.1210 | 0.2067 | 0.112* | |
H262 | −0.0062 | 0.2002 | 0.2512 | 0.112* | |
H263 | 0.0061 | 0.1618 | 0.1742 | 0.112* | |
C27 | −0.1904 (2) | 0.26807 (18) | 0.19910 (17) | 0.0511 (7) | |
H271 | −0.1575 | 0.2901 | 0.2498 | 0.077* | |
H272 | −0.2271 | 0.2115 | 0.2017 | 0.077* | |
H273 | −0.2366 | 0.3151 | 0.1717 | 0.077* | |
C28 | 0.33406 (17) | 0.36882 (15) | 0.12037 (13) | 0.0327 (5) | |
H281 | 0.3258 | 0.3208 | 0.1525 | 0.039* | |
C29 | 0.31812 (19) | 0.49622 (15) | 0.06028 (14) | 0.0358 (6) | |
H291 | 0.2963 | 0.5559 | 0.0421 | 0.043* | |
C30 | 0.38653 (19) | 0.44621 (15) | 0.04013 (13) | 0.0362 (6) | |
H301 | 0.4210 | 0.4639 | 0.0056 | 0.043* | |
C31 | 0.46122 (17) | 0.28457 (15) | 0.07408 (12) | 0.0277 (5) | |
C32 | 0.5314 (2) | 0.31228 (17) | 0.02940 (14) | 0.0399 (6) | |
H321 | 0.4928 | 0.3297 | −0.0214 | 0.060* | |
H322 | 0.5747 | 0.2604 | 0.0271 | 0.060* | |
H323 | 0.5718 | 0.3646 | 0.0537 | 0.060* | |
C33 | 0.52081 (19) | 0.25800 (18) | 0.15311 (13) | 0.0415 (6) | |
H331 | 0.5605 | 0.3107 | 0.1776 | 0.062* | |
H332 | 0.5648 | 0.2066 | 0.1511 | 0.062* | |
H333 | 0.4755 | 0.2396 | 0.1815 | 0.062* | |
C34 | 0.39420 (19) | 0.20611 (16) | 0.03560 (15) | 0.0406 (6) | |
H341 | 0.3566 | 0.2250 | −0.0150 | 0.061* | |
H342 | 0.3482 | 0.1906 | 0.0642 | 0.061* | |
H343 | 0.4347 | 0.1522 | 0.0329 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02411 (17) | 0.02136 (15) | 0.02917 (17) | −0.00051 (12) | 0.00988 (13) | −0.00353 (12) |
Cl1 | 0.0332 (3) | 0.0353 (3) | 0.0291 (3) | 0.0058 (2) | 0.0064 (2) | 0.0001 (2) |
Cl2 | 0.0380 (3) | 0.0206 (3) | 0.0396 (3) | 0.0014 (2) | 0.0185 (3) | 0.0011 (2) |
N1 | 0.0258 (10) | 0.0212 (9) | 0.0270 (10) | −0.0003 (7) | 0.0088 (8) | −0.0001 (7) |
N2 | 0.0256 (10) | 0.0204 (9) | 0.0283 (10) | −0.0007 (7) | 0.0087 (8) | 0.0007 (7) |
N3 | 0.0262 (10) | 0.0251 (9) | 0.0332 (11) | −0.0016 (8) | 0.0117 (8) | −0.0063 (8) |
N4 | 0.0273 (10) | 0.0234 (9) | 0.0372 (11) | 0.0000 (8) | 0.0144 (9) | −0.0065 (8) |
C1 | 0.0255 (12) | 0.0234 (11) | 0.0293 (12) | 0.0018 (9) | 0.0092 (9) | 0.0002 (9) |
C2 | 0.0293 (13) | 0.0219 (11) | 0.0287 (12) | 0.0033 (9) | 0.0086 (10) | 0.0002 (9) |
C3 | 0.0249 (12) | 0.0281 (12) | 0.0290 (12) | 0.0043 (9) | 0.0082 (10) | 0.0020 (9) |
C4 | 0.0314 (13) | 0.0222 (11) | 0.0359 (13) | −0.0069 (9) | 0.0110 (10) | 0.0008 (9) |
C5 | 0.0572 (18) | 0.0350 (14) | 0.0399 (15) | −0.0149 (12) | 0.0139 (13) | −0.0064 (11) |
C6 | 0.0354 (14) | 0.0269 (12) | 0.0515 (16) | −0.0029 (10) | 0.0123 (12) | 0.0099 (11) |
C7 | 0.0283 (14) | 0.0367 (14) | 0.0641 (18) | −0.0053 (11) | 0.0123 (13) | 0.0037 (12) |
C8 | 0.0300 (13) | 0.0259 (11) | 0.0308 (12) | 0.0000 (9) | 0.0116 (10) | −0.0029 (9) |
C9 | 0.0336 (14) | 0.0237 (11) | 0.0493 (15) | −0.0008 (10) | 0.0203 (12) | 0.0011 (10) |
C10 | 0.0404 (15) | 0.0277 (12) | 0.0502 (15) | −0.0034 (10) | 0.0276 (12) | 0.0005 (11) |
C11 | 0.0314 (13) | 0.0267 (12) | 0.0441 (14) | 0.0034 (10) | 0.0152 (11) | −0.0086 (10) |
C12 | 0.0538 (18) | 0.0392 (15) | 0.082 (2) | 0.0004 (13) | 0.0449 (17) | −0.0150 (14) |
C13 | 0.0525 (18) | 0.0488 (17) | 0.0564 (18) | 0.0212 (14) | 0.0049 (14) | −0.0115 (14) |
C14 | 0.0408 (15) | 0.0309 (13) | 0.0563 (17) | −0.0018 (11) | 0.0167 (13) | −0.0149 (12) |
Co2 | 0.02576 (18) | 0.02496 (17) | 0.0472 (2) | 0.00152 (12) | 0.01513 (15) | 0.00222 (13) |
Cl3 | 0.0365 (3) | 0.0385 (3) | 0.0454 (4) | 0.0056 (3) | 0.0156 (3) | 0.0042 (3) |
Cl4 | 0.0346 (3) | 0.0261 (3) | 0.0686 (4) | 0.0032 (2) | 0.0191 (3) | 0.0102 (3) |
N21 | 0.0264 (11) | 0.0289 (11) | 0.0567 (13) | 0.0027 (8) | 0.0130 (10) | 0.0066 (9) |
N22 | 0.0253 (11) | 0.0257 (10) | 0.0503 (13) | 0.0010 (8) | 0.0110 (9) | 0.0029 (9) |
N23 | 0.0292 (11) | 0.0274 (10) | 0.0382 (11) | −0.0012 (8) | 0.0121 (9) | −0.0013 (8) |
N24 | 0.0291 (10) | 0.0254 (9) | 0.0265 (10) | −0.0013 (8) | 0.0116 (8) | −0.0009 (8) |
C21 | 0.0244 (13) | 0.0262 (12) | 0.0415 (14) | 0.0020 (9) | 0.0110 (10) | 0.0009 (10) |
C22 | 0.0331 (16) | 0.0328 (14) | 0.097 (2) | 0.0060 (12) | 0.0189 (15) | 0.0150 (15) |
C23 | 0.0282 (15) | 0.0353 (14) | 0.091 (2) | 0.0063 (11) | 0.0188 (15) | 0.0119 (14) |
C24 | 0.0322 (14) | 0.0260 (12) | 0.0536 (16) | −0.0055 (10) | 0.0151 (12) | −0.0036 (11) |
C25 | 0.082 (3) | 0.079 (2) | 0.069 (2) | −0.038 (2) | 0.0299 (19) | −0.0321 (19) |
C26 | 0.0395 (18) | 0.0327 (16) | 0.152 (4) | −0.0001 (13) | 0.028 (2) | 0.0272 (18) |
C27 | 0.0489 (18) | 0.0402 (15) | 0.074 (2) | −0.0062 (13) | 0.0342 (16) | −0.0022 (14) |
C28 | 0.0353 (14) | 0.0309 (13) | 0.0357 (13) | 0.0032 (10) | 0.0164 (11) | 0.0053 (10) |
C29 | 0.0441 (15) | 0.0232 (12) | 0.0419 (14) | −0.0016 (10) | 0.0152 (12) | 0.0024 (10) |
C30 | 0.0473 (16) | 0.0285 (12) | 0.0380 (14) | −0.0029 (11) | 0.0209 (12) | 0.0028 (10) |
C31 | 0.0294 (12) | 0.0276 (11) | 0.0281 (12) | 0.0010 (9) | 0.0114 (10) | −0.0023 (9) |
C32 | 0.0471 (16) | 0.0393 (14) | 0.0424 (15) | 0.0004 (12) | 0.0273 (13) | −0.0052 (11) |
C33 | 0.0433 (16) | 0.0479 (15) | 0.0335 (14) | 0.0150 (12) | 0.0115 (12) | 0.0032 (12) |
C34 | 0.0424 (15) | 0.0300 (13) | 0.0503 (16) | −0.0010 (11) | 0.0148 (13) | −0.0076 (11) |
Co1—N1 | 2.0128 (17) | Co2—N23 | 2.0110 (19) |
Co1—N3 | 2.0191 (17) | Co2—N21 | 2.0185 (19) |
Co1—Cl1 | 2.2587 (6) | Co2—Cl4 | 2.2699 (6) |
Co1—Cl2 | 2.2604 (6) | Co2—Cl3 | 2.2757 (7) |
N1—C1 | 1.328 (3) | N21—C21 | 1.321 (3) |
N1—C2 | 1.378 (3) | N21—C22 | 1.377 (3) |
N2—C1 | 1.342 (3) | N22—C21 | 1.338 (3) |
N2—C3 | 1.377 (3) | N22—C23 | 1.376 (3) |
N2—C4 | 1.502 (3) | N22—C24 | 1.496 (3) |
N3—C8 | 1.326 (3) | N23—C28 | 1.327 (3) |
N3—C9 | 1.375 (3) | N23—C29 | 1.374 (3) |
N4—C8 | 1.342 (3) | N24—C28 | 1.342 (3) |
N4—C10 | 1.372 (3) | N24—C30 | 1.368 (3) |
N4—C11 | 1.498 (3) | N24—C31 | 1.499 (3) |
C1—H11 | 0.9500 | C21—H211 | 0.9500 |
C2—C3 | 1.353 (3) | C22—C23 | 1.346 (4) |
C2—H21 | 0.9500 | C22—H221 | 0.9500 |
C3—H31 | 0.9500 | C23—H231 | 0.9500 |
C4—C7 | 1.519 (3) | C24—C26 | 1.513 (4) |
C4—C6 | 1.525 (3) | C24—C25 | 1.516 (4) |
C4—C5 | 1.525 (3) | C24—C27 | 1.517 (3) |
C5—H51 | 0.9800 | C25—H251 | 0.9800 |
C5—H52 | 0.9800 | C25—H252 | 0.9800 |
C5—H53 | 0.9800 | C25—H253 | 0.9800 |
C6—H61 | 0.9800 | C26—H261 | 0.9800 |
C6—H62 | 0.9800 | C26—H262 | 0.9800 |
C6—H63 | 0.9800 | C26—H263 | 0.9800 |
C7—H71 | 0.9800 | C27—H271 | 0.9800 |
C7—H72 | 0.9800 | C27—H272 | 0.9800 |
C7—H73 | 0.9800 | C27—H273 | 0.9800 |
C8—H81 | 0.9500 | C28—H281 | 0.9500 |
C9—C10 | 1.355 (3) | C29—C30 | 1.347 (3) |
C9—H91 | 0.9500 | C29—H291 | 0.9500 |
C10—H101 | 0.9500 | C30—H301 | 0.9500 |
C11—C14 | 1.517 (3) | C31—C33 | 1.522 (3) |
C11—C13 | 1.518 (4) | C31—C34 | 1.522 (3) |
C11—C12 | 1.520 (3) | C31—C32 | 1.524 (3) |
C12—H112 | 0.9800 | C32—H321 | 0.9800 |
C12—H121 | 0.9800 | C32—H322 | 0.9800 |
C12—H123 | 0.9800 | C32—H323 | 0.9800 |
C13—H131 | 0.9800 | C33—H331 | 0.9800 |
C13—H132 | 0.9800 | C33—H332 | 0.9800 |
C13—H133 | 0.9800 | C33—H333 | 0.9800 |
C14—H141 | 0.9800 | C34—H341 | 0.9800 |
C14—H142 | 0.9800 | C34—H342 | 0.9800 |
C14—H143 | 0.9800 | C34—H343 | 0.9800 |
N1—Co1—N3 | 109.65 (7) | N23—Co2—N21 | 116.50 (8) |
N1—Co1—Cl1 | 109.36 (5) | N23—Co2—Cl4 | 104.23 (6) |
N3—Co1—Cl1 | 110.70 (6) | N21—Co2—Cl4 | 105.72 (6) |
N1—Co1—Cl2 | 104.51 (5) | N23—Co2—Cl3 | 108.64 (6) |
N3—Co1—Cl2 | 105.03 (5) | N21—Co2—Cl3 | 106.16 (6) |
Cl1—Co1—Cl2 | 117.25 (2) | Cl4—Co2—Cl3 | 115.96 (3) |
C1—N1—C2 | 105.57 (17) | C21—N21—C22 | 105.0 (2) |
C1—N1—Co1 | 129.92 (15) | C21—N21—Co2 | 134.32 (16) |
C2—N1—Co1 | 124.51 (14) | C22—N21—Co2 | 119.33 (16) |
C1—N2—C3 | 107.08 (17) | C21—N22—C23 | 106.42 (19) |
C1—N2—C4 | 125.46 (17) | C21—N22—C24 | 128.23 (19) |
C3—N2—C4 | 127.28 (18) | C23—N22—C24 | 125.3 (2) |
C8—N3—C9 | 105.77 (18) | C28—N23—C29 | 105.16 (19) |
C8—N3—Co1 | 130.82 (15) | C28—N23—Co2 | 130.16 (16) |
C9—N3—Co1 | 123.42 (14) | C29—N23—Co2 | 124.40 (15) |
C8—N4—C10 | 107.13 (18) | C28—N24—C30 | 106.52 (18) |
C8—N4—C11 | 125.24 (19) | C28—N24—C31 | 125.32 (18) |
C10—N4—C11 | 127.49 (18) | C30—N24—C31 | 128.09 (18) |
N1—C1—N2 | 111.32 (18) | N21—C21—N22 | 112.13 (19) |
N1—C1—H11 | 124.3 | N21—C21—H211 | 123.9 |
N2—C1—H11 | 124.3 | N22—C21—H211 | 123.9 |
C3—C2—N1 | 109.55 (18) | C23—C22—N21 | 109.7 (2) |
C3—C2—H21 | 125.2 | C23—C22—H221 | 125.1 |
N1—C2—H21 | 125.2 | N21—C22—H221 | 125.1 |
C2—C3—N2 | 106.48 (19) | C22—C23—N22 | 106.7 (2) |
C2—C3—H31 | 126.8 | C22—C23—H231 | 126.7 |
N2—C3—H31 | 126.8 | N22—C23—H231 | 126.7 |
N2—C4—C7 | 109.03 (18) | N22—C24—C26 | 109.0 (2) |
N2—C4—C6 | 108.52 (18) | N22—C24—C25 | 108.0 (2) |
C7—C4—C6 | 110.05 (19) | C26—C24—C25 | 111.5 (3) |
N2—C4—C5 | 107.37 (17) | N22—C24—C27 | 109.43 (19) |
C7—C4—C5 | 111.1 (2) | C26—C24—C27 | 109.5 (2) |
C6—C4—C5 | 110.6 (2) | C25—C24—C27 | 109.4 (2) |
C4—C5—H51 | 109.5 | C24—C25—H251 | 109.5 |
C4—C5—H52 | 109.5 | C24—C25—H252 | 109.5 |
H51—C5—H52 | 109.5 | H251—C25—H252 | 109.5 |
C4—C5—H53 | 109.5 | C24—C25—H253 | 109.5 |
H51—C5—H53 | 109.5 | H251—C25—H253 | 109.5 |
H52—C5—H53 | 109.5 | H252—C25—H253 | 109.5 |
C4—C6—H61 | 109.5 | C24—C26—H261 | 109.5 |
C4—C6—H62 | 109.5 | C24—C26—H262 | 109.5 |
H61—C6—H62 | 109.5 | H261—C26—H262 | 109.5 |
C4—C6—H63 | 109.5 | C24—C26—H263 | 109.5 |
H61—C6—H63 | 109.5 | H261—C26—H263 | 109.5 |
H62—C6—H63 | 109.5 | H262—C26—H263 | 109.5 |
C4—C7—H71 | 109.5 | C24—C27—H271 | 109.5 |
C4—C7—H72 | 109.5 | C24—C27—H272 | 109.5 |
H71—C7—H72 | 109.5 | H271—C27—H272 | 109.5 |
C4—C7—H73 | 109.5 | C24—C27—H273 | 109.5 |
H71—C7—H73 | 109.5 | H271—C27—H273 | 109.5 |
H72—C7—H73 | 109.5 | H272—C27—H273 | 109.5 |
N3—C8—N4 | 111.20 (19) | N23—C28—N24 | 111.7 (2) |
N3—C8—H81 | 124.4 | N23—C28—H281 | 124.2 |
N4—C8—H81 | 124.4 | N24—C28—H281 | 124.2 |
C10—C9—N3 | 109.3 (2) | C30—C29—N23 | 109.6 (2) |
C10—C9—H91 | 125.3 | C30—C29—H291 | 125.2 |
N3—C9—H91 | 125.3 | N23—C29—H291 | 125.2 |
C9—C10—N4 | 106.6 (2) | C29—C30—N24 | 107.1 (2) |
C9—C10—H101 | 126.7 | C29—C30—H301 | 126.5 |
N4—C10—H101 | 126.7 | N24—C30—H301 | 126.5 |
N4—C11—C14 | 107.50 (18) | N24—C31—C33 | 108.29 (17) |
N4—C11—C13 | 108.55 (19) | N24—C31—C34 | 108.13 (18) |
C14—C11—C13 | 111.1 (2) | C33—C31—C34 | 111.1 (2) |
N4—C11—C12 | 108.68 (19) | N24—C31—C32 | 108.98 (18) |
C14—C11—C12 | 110.3 (2) | C33—C31—C32 | 109.7 (2) |
C13—C11—C12 | 110.6 (2) | C34—C31—C32 | 110.61 (19) |
C11—C12—H112 | 109.5 | C31—C32—H321 | 109.5 |
C11—C12—H121 | 109.5 | C31—C32—H322 | 109.5 |
H112—C12—H121 | 109.5 | H321—C32—H322 | 109.5 |
C11—C12—H123 | 109.5 | C31—C32—H323 | 109.5 |
H112—C12—H123 | 109.5 | H321—C32—H323 | 109.5 |
H121—C12—H123 | 109.5 | H322—C32—H323 | 109.5 |
C11—C13—H131 | 109.5 | C31—C33—H331 | 109.5 |
C11—C13—H132 | 109.5 | C31—C33—H332 | 109.5 |
H131—C13—H132 | 109.5 | H331—C33—H332 | 109.5 |
C11—C13—H133 | 109.5 | C31—C33—H333 | 109.5 |
H131—C13—H133 | 109.5 | H331—C33—H333 | 109.5 |
H132—C13—H133 | 109.5 | H332—C33—H333 | 109.5 |
C11—C14—H141 | 109.5 | C31—C34—H341 | 109.5 |
C11—C14—H142 | 109.5 | C31—C34—H342 | 109.5 |
H141—C14—H142 | 109.5 | H341—C34—H342 | 109.5 |
C11—C14—H143 | 109.5 | C31—C34—H343 | 109.5 |
H141—C14—H143 | 109.5 | H341—C34—H343 | 109.5 |
H142—C14—H143 | 109.5 | H342—C34—H343 | 109.5 |
Cl1—Co1—N1—C1 | 78.18 (18) | C10—N4—C11—C14 | 105.8 (3) |
Cl1—Co1—N1—C2 | −102.57 (16) | C8—N4—C10—C9 | −0.4 (3) |
Cl2—Co1—N1—C1 | −155.51 (17) | C11—N4—C10—C9 | −176.3 (2) |
Cl2—Co1—N1—C2 | 23.74 (17) | C10—N4—C8—N3 | 0.8 (3) |
N3—Co1—N1—C1 | −43.4 (2) | C11—N4—C8—N3 | 176.9 (2) |
N3—Co1—N1—C2 | 135.88 (16) | C8—N4—C11—C13 | 50.8 (3) |
Cl1—Co1—N3—C8 | −56.1 (2) | C8—N4—C11—C14 | −69.5 (3) |
Cl1—Co1—N3—C9 | 123.24 (17) | C8—N4—C11—C12 | 171.1 (2) |
Cl2—Co1—N3—C8 | 176.49 (19) | C10—N4—C11—C13 | −134.0 (2) |
Cl2—Co1—N3—C9 | −4.23 (19) | C10—N4—C11—C12 | −13.7 (3) |
N1—Co1—N3—C8 | 64.7 (2) | Co2—N21—C22—C23 | −170.4 (2) |
N1—Co1—N3—C9 | −116.03 (18) | C22—N21—C21—N22 | 1.8 (3) |
Cl3—Co2—N21—C21 | −64.6 (2) | Co2—N21—C21—N22 | 167.99 (18) |
Cl3—Co2—N21—C22 | 100.1 (2) | C21—N21—C22—C23 | −1.6 (3) |
Cl4—Co2—N21—C21 | 171.7 (2) | C21—N22—C24—C25 | −96.7 (3) |
Cl4—Co2—N21—C22 | −23.6 (2) | C21—N22—C24—C26 | 24.6 (3) |
N23—Co2—N21—C21 | 56.5 (3) | C23—N22—C21—N21 | −1.2 (3) |
N23—Co2—N21—C22 | −138.8 (2) | C24—N22—C21—N21 | 175.9 (2) |
Cl3—Co2—N23—C28 | 53.7 (2) | C21—N22—C23—C22 | 0.2 (3) |
Cl3—Co2—N23—C29 | −119.31 (19) | C24—N22—C23—C22 | −177.1 (2) |
Cl4—Co2—N23—C28 | 178.0 (2) | C23—N22—C24—C25 | 80.0 (3) |
Cl4—Co2—N23—C29 | 4.9 (2) | C23—N22—C24—C26 | −158.8 (3) |
N21—Co2—N23—C28 | −66.0 (2) | C21—N22—C24—C27 | 144.4 (3) |
N21—Co2—N23—C29 | 120.93 (19) | C23—N22—C24—C27 | −39.0 (3) |
Co1—N1—C2—C3 | −179.36 (14) | C28—N23—C29—C30 | −0.2 (3) |
Co1—N1—C1—N2 | 179.37 (14) | Co2—N23—C29—C30 | 174.27 (17) |
C2—N1—C1—N2 | 0.0 (2) | Co2—N23—C28—N24 | −173.54 (15) |
C1—N1—C2—C3 | 0.1 (2) | C29—N23—C28—N24 | 0.5 (3) |
C3—N2—C4—C7 | 20.1 (3) | C30—N24—C28—N23 | −0.6 (3) |
C4—N2—C1—N1 | −175.54 (19) | C28—N24—C31—C34 | 67.2 (3) |
C3—N2—C4—C5 | −100.4 (3) | C30—N24—C31—C32 | 10.9 (3) |
C3—N2—C4—C6 | 140.0 (2) | C31—N24—C28—N23 | −177.82 (19) |
C3—N2—C1—N1 | −0.1 (2) | C28—N24—C30—C29 | 0.4 (3) |
C1—N2—C4—C5 | 74.2 (3) | C31—N24—C30—C29 | 177.5 (2) |
C1—N2—C3—C2 | 0.1 (2) | C28—N24—C31—C32 | −172.5 (2) |
C4—N2—C3—C2 | 175.5 (2) | C28—N24—C31—C33 | −53.2 (3) |
C1—N2—C4—C6 | −45.4 (3) | C30—N24—C31—C34 | −109.4 (3) |
C1—N2—C4—C7 | −165.3 (2) | C30—N24—C31—C33 | 130.2 (2) |
Co1—N3—C8—N4 | 178.52 (15) | N1—C2—C3—N2 | −0.1 (2) |
C9—N3—C8—N4 | −0.9 (3) | N3—C9—C10—N4 | −0.1 (3) |
Co1—N3—C9—C10 | −178.85 (16) | N21—C22—C23—N22 | 0.9 (4) |
C8—N3—C9—C10 | 0.6 (3) | N23—C29—C30—N24 | −0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H11···Cl3 | 0.95 | 2.82 | 3.767 (2) | 172 |
C3—H31···Cl4i | 0.95 | 2.78 | 3.704 (2) | 166 |
C8—H81···Cl3 | 0.95 | 2.73 | 3.618 (2) | 157 |
C21—H211···Cl1 | 0.95 | 2.73 | 3.669 (2) | 169 |
C23—H231···Cl2ii | 0.95 | 2.75 | 3.671 (3) | 164 |
C28—H281···Cl1 | 0.95 | 2.80 | 3.643 (2) | 148 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CoCl2(C7H12N2)2] |
Mr | 378.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 14.1054 (1), 14.5470 (1), 18.7059 (2) |
β (°) | 106.9542 (3) |
V (Å3) | 3671.47 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.23 |
Crystal size (mm) | 0.33 × 0.33 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan [applied during the scaling procedure (DENZO; Otwinowski & Minor, 1997)] |
Tmin, Tmax | 0.857, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 74460, 6741, 5547 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.076, 1.03 |
No. of reflections | 6741 |
No. of parameters | 391 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.30 |
Computer programs: COLLECT (Nonius, 2001), DENZO (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994, SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010) and PLATON (Spek, 2009), PLATON (Spek, 2009).
Co1—N1 | 2.0128 (17) | Co2—N23 | 2.0110 (19) |
Co1—N3 | 2.0191 (17) | Co2—N21 | 2.0185 (19) |
Co1—Cl1 | 2.2587 (6) | Co2—Cl4 | 2.2699 (6) |
Co1—Cl2 | 2.2604 (6) | Co2—Cl3 | 2.2757 (7) |
N1—Co1—N3 | 109.65 (7) | N23—Co2—N21 | 116.50 (8) |
N1—Co1—Cl1 | 109.36 (5) | N23—Co2—Cl4 | 104.23 (6) |
N3—Co1—Cl1 | 110.70 (6) | N21—Co2—Cl4 | 105.72 (6) |
N1—Co1—Cl2 | 104.51 (5) | N23—Co2—Cl3 | 108.64 (6) |
N3—Co1—Cl2 | 105.03 (5) | N21—Co2—Cl3 | 106.16 (6) |
Cl1—Co1—Cl2 | 117.25 (2) | Cl4—Co2—Cl3 | 115.96 (3) |
Cl1—Co1—N1—C1 | 78.18 (18) | Cl3—Co2—N21—C21 | −64.6 (2) |
Cl1—Co1—N1—C2 | −102.57 (16) | Cl3—Co2—N21—C22 | 100.1 (2) |
Cl2—Co1—N1—C1 | −155.51 (17) | Cl4—Co2—N21—C21 | 171.7 (2) |
Cl2—Co1—N1—C2 | 23.74 (17) | Cl4—Co2—N21—C22 | −23.6 (2) |
Cl1—Co1—N3—C8 | −56.1 (2) | Cl3—Co2—N23—C28 | 53.7 (2) |
Cl1—Co1—N3—C9 | 123.24 (17) | Cl3—Co2—N23—C29 | −119.31 (19) |
Cl2—Co1—N3—C8 | 176.49 (19) | Cl4—Co2—N23—C28 | 178.0 (2) |
Cl2—Co1—N3—C9 | −4.23 (19) | Cl4—Co2—N23—C29 | 4.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H11···Cl3 | 0.9500 | 2.8200 | 3.767 (2) | 172.00 |
C3—H31···Cl4i | 0.9500 | 2.7800 | 3.704 (2) | 166.00 |
C8—H81···Cl3 | 0.9500 | 2.7300 | 3.618 (2) | 157.00 |
C21—H211···Cl1 | 0.9500 | 2.7300 | 3.669 (2) | 169.00 |
C23—H231···Cl2ii | 0.9500 | 2.7500 | 3.671 (3) | 164.00 |
C28—H281···Cl1 | 0.9500 | 2.8000 | 3.643 (2) | 148.00 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2. |
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We have previously reported the syntheses of hexakis(1-isopropylimidazole)calcium(II) dichloride, [Ca(iPrIm)6]Cl2, and di-µ-chlorido-bis[tris(1-tert-butylimidazole)chloridocalcium(II)], [(tBuIm)3CaCl(µ2-Cl)2ClCa(tBuIm)3], as well as the complex triaquatris(1-isopropylimidazole)magnesium(II) dichloride, [Mg(iPrIm)6(H2O)3]Cl2 (Unger et al., 2007). In these cases, we synthesized the complexes from the respective imidazoles and alkaline earth metal salts. We report here the synthesis of bis(1-tert-butyl-1H-imidazole-κN3)dichloridocobalt(II), (I), starting from the bis-imidazolium salt.
The CoII cation of (I) is coordinated in a distorted tetrahedral geometry by two chloride ligands [Co—Cl = 2.2588 (6) and 2.2603 (5) Å] and two 1-tert-butyl-1H-imidazole ligands, which coordinate via N atoms [Co—N = 2.013 (2) and 2.019 (2) Å]. These bond lengths are not significantly longer than in the analogous methyl-substituted complex bis(methylimidazole)CoCl2 (Mukerjee et al., 2000). Even the N—Co—N angle is comparable [tBu = 109.65 (7)° versus Me = 110.6 (1)°], which shows that the steric demand of the larger tert-butyl group has no influence on the coordination geometry. The most obvious difference is that in the methyl-substituted case, the H atoms on C2 of the imidazole ligand point in different directions, while in the tert-butyl case, both H atoms are oriented on the same side of the complex. By quenching the reaction with elemental sulfur we could show that the free carbene is formed under the reaction conditions but decomposes relatively quickly. The H atoms in the methylene bridge are acidic and not stable towards the base potassium bis(trimethylsilyl)amide (KHMDS), as we found large amounts of tert-butylimidazole in the solution. These form the observed product, which crystallized from the tetrahydrofuran solution.
In the asymmetric unit of (I) there are two crystallographically independent molecules, A (including atom Co1) and B (atom Co2) (Fig. 1). They are related by a noncrystallographic inversion centre. As can be seen from the Cl—Co—N—C torsion angles (Table 1), the core geometry of molecules A and B differs only slightly. As a consequence of their acidity, imidazole atoms H11, H31, H81, H211, H231 and H281 take part in C—H···Cl contacts (Table 2 and Figs. 2 and 3). Six contacts are shorter than the sum of the relevant van der Waals radii (2.95 Å; Bondi, 1964).
The most striking feature of (I) in the solid state is a head-to-tail arrangement of molecules A and B. Atoms Cl1 and Cl3 of both molecules take part in bifurcated hydrogen-bond bridges (Fig. 2). These dimers connect to form an infinite double layer parallel to the ab plane via Cl2···H231 and Cl4···H31 contacts (Fig. 3).