Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005510/bm1451sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005510/bm1451Isup2.hkl |
CCDC reference: 166974
Potassium hydrido-tris[3-(cyclohexyl)pyrazol-1-yl]borate (1.00 g, 2.0 mmol) and CuCl2 (0.14 g, 1.0 mmol) were refluxed in CH3OH (50 cm3) for 1 h. The resultant red precipitate was filtered, washed with CH3OH and dried in vacuo. Brown crystals of the complex were grown by diffusion of CH3OH into a solution of the compound in CH2Cl2. The powdered crystals retain some of the lattice solvent upon drying, with different samples analysing reproducibly as the hemi-dichloromethane solvate. Found C 63.1, H 8.0, N 16.4%. Calculated for C54H80B2CuN12·0.5CH2Cl2 C 63.8, H 8.0, N 16.4%.
The dichloromethane molecule is disordered over four orientations: C36–Cl38, occupancy 0.3; C39–Cl41, occupancy 0.2; C42–Cl44, occupancy 0.2; and C45–Cl47, occupancy 0.3. A l l C—Cl distances were restrained to 1.78 (2) Å, and non-bonded Cl···Cl contacts within each disorder orientation to 2.91 (2) Å.
Slightly high displacement parameters on individual C atoms in all three cyclohexyl rings may be evidence for libration of these groups in the crystal. However, since the metric parameters in all three of these substituents are typical for a saturated six-membered ring, these groups are not conformationally disordered.
All ordered non-H atoms were refined anisotropically, while H atoms were placed in calculated positions and refined using a riding model. The C—H distances employed for the final refinement were 0.95 Å for the pyrazole H atoms, 0.99 Å for the cyclohexyl CH2 groups and 1.00 Å for the cyclohexyl tertiary C–H bonds, while the B—H distances were 1.00 Å.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1996); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.
[Cu(C27H40BN6)2]·2CH2Cl2 | F(000) = 1222 |
Mr = 1152.31 | Dx = 1.261 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.0758 (2) Å | Cell parameters from 33672 reflections |
b = 18.3961 (3) Å | θ = 2.7–27.5° |
c = 13.0405 (2) Å | µ = 0.58 mm−1 |
β = 104.6939 (12)° | T = 150 K |
V = 3034.22 (8) Å3 | Rectangular prism, brown |
Z = 2 | 0.86 × 0.40 × 0.37 mm |
Nonius KappaCCD area detector diffractometer | 6916 independent reflections |
Radiation source: fine-focus sealed tube | 5524 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
Area detector scans | h = −16→16 |
Absorption correction: multi-scan (Blessing, 1995) | k = −20→23 |
Tmin = 0.634, Tmax = 0.813 | l = −16→16 |
33672 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.173 | w = 1/[σ2(Fo2) + (0.0947P)2 + 1.9928P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
6916 reflections | Δρmax = 0.93 e Å−3 |
363 parameters | Δρmin = −0.62 e Å−3 |
12 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (3) |
[Cu(C27H40BN6)2]·2CH2Cl2 | V = 3034.22 (8) Å3 |
Mr = 1152.31 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.0758 (2) Å | µ = 0.58 mm−1 |
b = 18.3961 (3) Å | T = 150 K |
c = 13.0405 (2) Å | 0.86 × 0.40 × 0.37 mm |
β = 104.6939 (12)° |
Nonius KappaCCD area detector diffractometer | 6916 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5524 reflections with I > 2σ(I) |
Tmin = 0.634, Tmax = 0.813 | Rint = 0.057 |
33672 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 12 restraints |
wR(F2) = 0.173 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.93 e Å−3 |
6916 reflections | Δρmin = −0.62 e Å−3 |
363 parameters |
Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings |
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. Structure solution was achieved by direct methods using SHELXS97 (Sheldrick, 1990), while least squares refinement used SHELXL97 (Sheldrick, 1997). The highest residual electron density peak of 0.93 e.Å-3 is located within the disordered region. The asymmetric unit contains half a complex molecule [Cu1 lying on an inversion centre] and one molecule of dichloromethane on a general position. The solvent molecule is disordered over four orientations: C36—Cl38, occupancy 0.3 C39—Cl41, occupancy 0.2 C42—Cl44, occupancy 0.2 C45—Cl47, occupancy 0.3 A l l C—Cl distances were restrained to 1.78 (2) Å, and non-bonded Cl···Cl contacts within each disorder orientation to 2.91 (2) Å. All crystallographically ordered non-H atoms were refined anisotropically. The highest residual peak of electron density, of 0.93 e.Å-3, is located within this disordered region. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.0000 | 0.0000 | 0.5000 | 0.03185 (16) | |
N2 | 0.04459 (15) | 0.05708 (10) | 0.39021 (14) | 0.0347 (4) | |
N3 | 0.11584 (16) | 0.11128 (11) | 0.42616 (15) | 0.0373 (4) | |
C4 | 0.1333 (2) | 0.14750 (15) | 0.3432 (2) | 0.0483 (6) | |
H4 | 0.1800 | 0.1876 | 0.3468 | 0.058* | |
C5 | 0.0720 (2) | 0.11666 (16) | 0.2511 (2) | 0.0505 (7) | |
H5 | 0.0679 | 0.1314 | 0.1803 | 0.061* | |
C6 | 0.01749 (19) | 0.05938 (13) | 0.28349 (17) | 0.0377 (5) | |
C7 | −0.0574 (2) | 0.00495 (13) | 0.21961 (18) | 0.0381 (5) | |
H7 | −0.1107 | −0.0070 | 0.2602 | 0.046* | |
C8 | −0.0021 (3) | −0.0646 (2) | 0.2058 (4) | 0.0908 (15) | |
H8A | 0.0335 | −0.0847 | 0.2762 | 0.109* | |
H8B | 0.0525 | −0.0547 | 0.1671 | 0.109* | |
C9 | −0.0817 (3) | −0.1206 (2) | 0.1438 (4) | 0.1036 (18) | |
H9A | −0.0436 | −0.1653 | 0.1333 | 0.124* | |
H9B | −0.1327 | −0.1334 | 0.1854 | 0.124* | |
C10 | −0.1400 (4) | −0.0916 (3) | 0.0390 (3) | 0.0969 (16) | |
H10A | −0.1933 | −0.1276 | 0.0028 | 0.116* | |
H10B | −0.0900 | −0.0836 | −0.0056 | 0.116* | |
C11 | −0.1943 (4) | −0.0210 (3) | 0.0513 (3) | 0.0962 (17) | |
H11A | −0.2504 | −0.0303 | 0.0883 | 0.115* | |
H11B | −0.2283 | −0.0011 | −0.0198 | 0.115* | |
C12 | −0.1171 (3) | 0.0349 (2) | 0.1136 (3) | 0.0796 (12) | |
H12A | −0.0663 | 0.0490 | 0.0723 | 0.096* | |
H12B | −0.1563 | 0.0790 | 0.1246 | 0.096* | |
N13 | 0.15272 (16) | −0.01636 (10) | 0.56927 (15) | 0.0352 (4) | |
N14 | 0.21297 (16) | 0.04502 (11) | 0.58778 (15) | 0.0374 (4) | |
C15 | 0.3114 (2) | 0.02788 (16) | 0.6420 (2) | 0.0479 (6) | |
H15 | 0.3683 | 0.0610 | 0.6651 | 0.057* | |
C16 | 0.3160 (2) | −0.04621 (16) | 0.6586 (2) | 0.0529 (7) | |
H16 | 0.3758 | −0.0738 | 0.6946 | 0.063* | |
C17 | 0.2148 (2) | −0.07247 (14) | 0.61165 (19) | 0.0406 (5) | |
C18 | 0.1729 (2) | −0.14897 (14) | 0.6040 (2) | 0.0427 (5) | |
H18 | 0.0988 | −0.1466 | 0.6114 | 0.051* | |
C19 | 0.2351 (3) | −0.19715 (17) | 0.6926 (2) | 0.0629 (8) | |
H19A | 0.2353 | −0.1750 | 0.7619 | 0.075* | |
H19B | 0.3092 | −0.2006 | 0.6877 | 0.075* | |
C20 | 0.1870 (4) | −0.27351 (18) | 0.6864 (3) | 0.0722 (10) | |
H20A | 0.2312 | −0.3043 | 0.7428 | 0.087* | |
H20B | 0.1155 | −0.2704 | 0.6988 | 0.087* | |
C21 | 0.1794 (3) | −0.30832 (16) | 0.5800 (3) | 0.0588 (7) | |
H21A | 0.1432 | −0.3558 | 0.5768 | 0.071* | |
H21B | 0.2514 | −0.3171 | 0.5712 | 0.071* | |
C22 | 0.1186 (3) | −0.25986 (17) | 0.4908 (3) | 0.0684 (9) | |
H22A | 0.0444 | −0.2554 | 0.4953 | 0.082* | |
H22B | 0.1182 | −0.2823 | 0.4217 | 0.082* | |
C23 | 0.1689 (3) | −0.18403 (17) | 0.4974 (2) | 0.0653 (9) | |
H23A | 0.2414 | −0.1881 | 0.4878 | 0.078* | |
H23B | 0.1270 | −0.1531 | 0.4397 | 0.078* | |
N24 | 0.31560 (18) | 0.19170 (12) | 0.53375 (18) | 0.0484 (5) | |
N25 | 0.23294 (17) | 0.18148 (11) | 0.57858 (16) | 0.0427 (5) | |
C26 | 0.3609 (2) | 0.25391 (15) | 0.5748 (2) | 0.0479 (6) | |
C27 | 0.3088 (3) | 0.28317 (15) | 0.6471 (2) | 0.0536 (7) | |
H27 | 0.3261 | 0.3264 | 0.6876 | 0.064* | |
C28 | 0.2278 (2) | 0.23616 (14) | 0.6468 (2) | 0.0475 (6) | |
H28 | 0.1770 | 0.2409 | 0.6871 | 0.057* | |
C29 | 0.4491 (2) | 0.28526 (17) | 0.5344 (2) | 0.0531 (7) | |
H29 | 0.5097 | 0.2503 | 0.5517 | 0.064* | |
C30 | 0.4143 (3) | 0.2941 (3) | 0.4130 (3) | 0.0748 (10) | |
H30A | 0.3945 | 0.2459 | 0.3800 | 0.090* | |
H30B | 0.3512 | 0.3258 | 0.3940 | 0.090* | |
C31 | 0.5007 (3) | 0.3264 (3) | 0.3701 (3) | 0.0792 (11) | |
H31A | 0.5605 | 0.2918 | 0.3816 | 0.095* | |
H31B | 0.4738 | 0.3339 | 0.2928 | 0.095* | |
C32 | 0.5389 (4) | 0.3967 (2) | 0.4214 (3) | 0.0826 (11) | |
H32A | 0.4814 | 0.4331 | 0.4026 | 0.099* | |
H32B | 0.5986 | 0.4143 | 0.3944 | 0.099* | |
C33 | 0.5747 (3) | 0.3896 (2) | 0.5414 (3) | 0.0826 (11) | |
H33A | 0.6377 | 0.3578 | 0.5608 | 0.099* | |
H33B | 0.5948 | 0.4380 | 0.5732 | 0.099* | |
C34 | 0.4876 (3) | 0.3578 (2) | 0.5860 (3) | 0.0717 (10) | |
H34A | 0.4276 | 0.3923 | 0.5737 | 0.086* | |
H34B | 0.5145 | 0.3510 | 0.6634 | 0.086* | |
B35 | 0.1577 (2) | 0.11847 (15) | 0.5481 (2) | 0.0387 (6) | |
H35 | 0.0966 | 0.1256 | 0.5801 | 0.046* | |
C36 | 0.327 (2) | −0.0219 (12) | 0.370 (2) | 0.119 (12)* | 0.30 |
H36A | 0.2521 | −0.0371 | 0.3516 | 0.142* | 0.30 |
H36B | 0.3403 | 0.0095 | 0.4337 | 0.142* | 0.30 |
Cl37 | 0.4107 (4) | −0.0987 (2) | 0.3949 (4) | 0.0835 (16)* | 0.30 |
Cl38 | 0.3564 (5) | 0.0250 (2) | 0.2640 (3) | 0.0762 (9)* | 0.30 |
C39 | 0.348 (2) | 0.0057 (15) | 0.3794 (16) | 0.077 (9)* | 0.20 |
H39A | 0.2951 | 0.0132 | 0.4212 | 0.092* | 0.20 |
H39B | 0.3936 | 0.0493 | 0.3879 | 0.092* | 0.20 |
Cl40 | 0.2804 (7) | −0.0061 (4) | 0.2408 (6) | 0.096 (3)* | 0.20 |
Cl41 | 0.4286 (12) | −0.0749 (7) | 0.4294 (12) | 0.116 (7)* | 0.20 |
C42 | 0.376 (2) | 0.0219 (17) | 0.4008 (17) | 0.115 (11)* | 0.20 |
H42A | 0.4407 | 0.0019 | 0.4493 | 0.137* | 0.20 |
H42B | 0.3528 | 0.0653 | 0.4340 | 0.137* | 0.20 |
Cl43 | 0.2749 (7) | −0.0439 (5) | 0.3690 (7) | 0.122 (2)* | 0.20 |
Cl44 | 0.3975 (6) | 0.0432 (4) | 0.2759 (5) | 0.0864 (17)* | 0.20 |
C45 | 0.3417 (12) | −0.0115 (9) | 0.3890 (10) | 0.048 (3)* | 0.30 |
H45A | 0.3739 | 0.0319 | 0.4295 | 0.057* | 0.30 |
H45B | 0.2758 | −0.0228 | 0.4101 | 0.057* | 0.30 |
Cl46 | 0.4295 (5) | −0.0854 (5) | 0.4242 (6) | 0.0632 (13)* | 0.30 |
Cl47 | 0.3082 (6) | 0.0101 (3) | 0.2489 (4) | 0.0763 (11)* | 0.30 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0367 (2) | 0.0361 (2) | 0.0229 (2) | −0.00078 (14) | 0.00797 (14) | −0.00044 (14) |
N2 | 0.0406 (10) | 0.0368 (10) | 0.0264 (9) | −0.0020 (8) | 0.0078 (7) | −0.0007 (7) |
N3 | 0.0445 (10) | 0.0371 (10) | 0.0297 (10) | −0.0034 (8) | 0.0085 (8) | −0.0012 (8) |
C4 | 0.0618 (16) | 0.0466 (14) | 0.0356 (13) | −0.0129 (12) | 0.0102 (11) | 0.0034 (11) |
C5 | 0.0684 (17) | 0.0529 (15) | 0.0296 (12) | −0.0152 (13) | 0.0115 (11) | 0.0038 (11) |
C6 | 0.0466 (13) | 0.0415 (12) | 0.0260 (10) | −0.0020 (10) | 0.0106 (9) | −0.0007 (9) |
C7 | 0.0469 (13) | 0.0429 (13) | 0.0247 (10) | −0.0036 (10) | 0.0098 (9) | −0.0028 (9) |
C8 | 0.060 (2) | 0.061 (2) | 0.130 (4) | 0.0093 (16) | −0.015 (2) | −0.044 (2) |
C9 | 0.067 (2) | 0.070 (2) | 0.153 (5) | 0.0061 (18) | −0.010 (2) | −0.064 (3) |
C10 | 0.095 (3) | 0.141 (4) | 0.066 (2) | −0.058 (3) | 0.041 (2) | −0.064 (3) |
C11 | 0.107 (3) | 0.097 (3) | 0.054 (2) | −0.043 (3) | −0.037 (2) | 0.017 (2) |
C12 | 0.092 (3) | 0.071 (2) | 0.0538 (19) | −0.026 (2) | −0.0228 (17) | 0.0152 (17) |
N13 | 0.0401 (10) | 0.0376 (10) | 0.0280 (9) | −0.0030 (8) | 0.0092 (8) | −0.0023 (7) |
N14 | 0.0431 (10) | 0.0381 (10) | 0.0298 (9) | −0.0040 (8) | 0.0074 (8) | −0.0029 (8) |
C15 | 0.0452 (14) | 0.0505 (14) | 0.0415 (14) | −0.0058 (11) | −0.0010 (11) | 0.0006 (12) |
C16 | 0.0456 (14) | 0.0484 (15) | 0.0561 (16) | 0.0008 (11) | −0.0028 (12) | 0.0060 (13) |
C17 | 0.0435 (12) | 0.0405 (13) | 0.0354 (12) | 0.0018 (10) | 0.0058 (9) | −0.0002 (10) |
C18 | 0.0429 (13) | 0.0407 (13) | 0.0435 (13) | 0.0009 (10) | 0.0091 (10) | −0.0019 (10) |
C19 | 0.092 (2) | 0.0460 (16) | 0.0422 (15) | −0.0077 (15) | 0.0014 (14) | 0.0039 (12) |
C20 | 0.111 (3) | 0.0481 (17) | 0.0511 (18) | −0.0135 (17) | 0.0084 (17) | 0.0055 (14) |
C21 | 0.0668 (18) | 0.0420 (15) | 0.071 (2) | 0.0006 (13) | 0.0230 (15) | −0.0023 (14) |
C22 | 0.104 (3) | 0.0465 (16) | 0.0496 (17) | −0.0133 (16) | 0.0098 (17) | −0.0074 (13) |
C23 | 0.105 (3) | 0.0474 (16) | 0.0402 (15) | −0.0122 (16) | 0.0115 (15) | −0.0029 (12) |
N24 | 0.0524 (12) | 0.0460 (12) | 0.0453 (12) | −0.0081 (10) | 0.0095 (10) | −0.0048 (10) |
N25 | 0.0506 (12) | 0.0407 (11) | 0.0351 (10) | −0.0032 (9) | 0.0074 (9) | −0.0037 (9) |
C26 | 0.0546 (15) | 0.0451 (14) | 0.0368 (13) | −0.0085 (11) | −0.0016 (11) | 0.0064 (11) |
C27 | 0.0782 (19) | 0.0428 (14) | 0.0349 (13) | −0.0107 (13) | 0.0051 (12) | −0.0026 (11) |
C28 | 0.0670 (17) | 0.0405 (13) | 0.0323 (12) | −0.0018 (12) | 0.0077 (11) | −0.0042 (10) |
C29 | 0.0538 (15) | 0.0556 (16) | 0.0452 (15) | −0.0118 (12) | 0.0039 (11) | 0.0018 (12) |
C30 | 0.068 (2) | 0.104 (3) | 0.0498 (18) | −0.0263 (19) | 0.0093 (15) | −0.0022 (18) |
C31 | 0.077 (2) | 0.106 (3) | 0.056 (2) | −0.015 (2) | 0.0186 (17) | 0.009 (2) |
C32 | 0.096 (3) | 0.072 (2) | 0.089 (3) | −0.002 (2) | 0.040 (2) | 0.022 (2) |
C33 | 0.093 (3) | 0.074 (2) | 0.085 (3) | −0.033 (2) | 0.030 (2) | −0.011 (2) |
C34 | 0.081 (2) | 0.069 (2) | 0.065 (2) | −0.0315 (18) | 0.0195 (17) | −0.0110 (17) |
B35 | 0.0444 (14) | 0.0395 (14) | 0.0311 (12) | −0.0007 (11) | 0.0073 (10) | −0.0035 (10) |
Cu1—N2 | 1.9788 (18) | C22—C23 | 1.535 (4) |
Cu1—N13 | 1.995 (2) | C22—H22A | 0.9900 |
N2—C6 | 1.347 (3) | C22—H22B | 0.9900 |
N2—N3 | 1.364 (3) | C23—H23A | 0.9900 |
N3—C4 | 1.339 (3) | C23—H23B | 0.9900 |
N3—B35 | 1.551 (3) | N24—C26 | 1.336 (3) |
C4—C5 | 1.385 (4) | N24—N25 | 1.366 (3) |
C4—H4 | 0.9500 | N25—C28 | 1.356 (3) |
C5—C6 | 1.397 (3) | N25—B35 | 1.507 (3) |
C5—H5 | 0.9500 | C26—C27 | 1.403 (4) |
C6—C7 | 1.497 (3) | C26—C29 | 1.500 (4) |
C7—C8 | 1.503 (4) | C27—C28 | 1.367 (4) |
C7—C12 | 1.509 (4) | C27—H27 | 0.9500 |
C7—H7 | 1.0000 | C28—H28 | 0.9500 |
C8—C9 | 1.539 (5) | C29—C34 | 1.522 (4) |
C8—H8A | 0.9900 | C29—C30 | 1.540 (4) |
C8—H8B | 0.9900 | C29—H29 | 1.0000 |
C9—C10 | 1.484 (7) | C30—C31 | 1.504 (5) |
C9—H9A | 0.9900 | C30—H30A | 0.9900 |
C9—H9B | 0.9900 | C30—H30B | 0.9900 |
C10—C11 | 1.508 (7) | C31—C32 | 1.484 (6) |
C10—H10A | 0.9900 | C31—H31A | 0.9900 |
C10—H10B | 0.9900 | C31—H31B | 0.9900 |
C11—C12 | 1.523 (5) | C32—C33 | 1.521 (6) |
C11—H11A | 0.9900 | C32—H32A | 0.9900 |
C11—H11B | 0.9900 | C32—H32B | 0.9900 |
C12—H12A | 0.9900 | C33—C34 | 1.520 (5) |
C12—H12B | 0.9900 | C33—H33A | 0.9900 |
N13—C17 | 1.342 (3) | C33—H33B | 0.9900 |
N13—N14 | 1.363 (3) | C34—H34A | 0.9900 |
N14—C15 | 1.340 (3) | C34—H34B | 0.9900 |
N14—B35 | 1.557 (3) | B35—H35 | 1.0000 |
C15—C16 | 1.379 (4) | C36—Cl38 | 1.754 (18) |
C15—H15 | 0.9500 | C36—Cl37 | 1.764 (17) |
C16—C17 | 1.396 (4) | C36—H36A | 0.9900 |
C16—H16 | 0.9500 | C36—H36B | 0.9900 |
C17—C18 | 1.504 (4) | C39—Cl40 | 1.812 (18) |
C18—C19 | 1.519 (4) | C39—Cl41 | 1.841 (19) |
C18—C23 | 1.521 (4) | C39—H39A | 0.9900 |
C18—H18 | 1.0000 | C39—H39B | 0.9900 |
C19—C20 | 1.533 (4) | C42—Cl43 | 1.764 (19) |
C19—H19A | 0.9900 | C42—Cl44 | 1.766 (19) |
C19—H19B | 0.9900 | C42—H42A | 0.9900 |
C20—C21 | 1.507 (5) | C42—H42B | 0.9900 |
C20—H20A | 0.9900 | C45—Cl46 | 1.763 (12) |
C20—H20B | 0.9900 | C45—Cl47 | 1.812 (12) |
C21—C22 | 1.521 (5) | C45—H45A | 0.9900 |
C21—H21A | 0.9900 | C45—H45B | 0.9900 |
C21—H21B | 0.9900 | ||
N2—Cu1—N2i | 180.00 | H21A—C21—H21B | 108.1 |
N2—Cu1—N13i | 92.13 (8) | C21—C22—C23 | 110.9 (3) |
N2—Cu1—N13 | 87.87 (8) | C21—C22—H22A | 109.5 |
N13i—Cu1—N13 | 180.00 | C23—C22—H22A | 109.5 |
C6—N2—N3 | 108.05 (18) | C21—C22—H22B | 109.5 |
C6—N2—Cu1 | 135.70 (16) | C23—C22—H22B | 109.5 |
N3—N2—Cu1 | 116.12 (14) | H22A—C22—H22B | 108.0 |
C4—N3—N2 | 109.14 (19) | C18—C23—C22 | 110.6 (3) |
C4—N3—B35 | 134.3 (2) | C18—C23—H23A | 109.5 |
N2—N3—B35 | 116.59 (18) | C22—C23—H23A | 109.5 |
N3—C4—C5 | 108.5 (2) | C18—C23—H23B | 109.5 |
N3—C4—H4 | 125.8 | C22—C23—H23B | 109.5 |
C5—C4—H4 | 125.8 | H23A—C23—H23B | 108.1 |
C4—C5—C6 | 105.9 (2) | C26—N24—N25 | 105.3 (2) |
C4—C5—H5 | 127.0 | C28—N25—N24 | 110.8 (2) |
C6—C5—H5 | 127.0 | C28—N25—B35 | 127.3 (2) |
N2—C6—C5 | 108.4 (2) | N24—N25—B35 | 121.8 (2) |
N2—C6—C7 | 121.2 (2) | N24—C26—C27 | 110.9 (2) |
C5—C6—C7 | 130.4 (2) | N24—C26—C29 | 119.4 (3) |
C6—C7—C8 | 111.7 (2) | C27—C26—C29 | 129.5 (3) |
C6—C7—C12 | 112.3 (2) | C28—C27—C26 | 105.3 (2) |
C8—C7—C12 | 110.7 (3) | C28—C27—H27 | 127.4 |
C6—C7—H7 | 107.3 | C26—C27—H27 | 127.4 |
C8—C7—H7 | 107.3 | N25—C28—C27 | 107.7 (3) |
C12—C7—H7 | 107.3 | N25—C28—H28 | 126.2 |
C7—C8—C9 | 110.5 (3) | C27—C28—H28 | 126.2 |
C7—C8—H8A | 109.5 | C26—C29—C34 | 112.3 (3) |
C9—C8—H8A | 109.5 | C26—C29—C30 | 110.4 (2) |
C7—C8—H8B | 109.5 | C34—C29—C30 | 109.9 (3) |
C9—C8—H8B | 109.5 | C26—C29—H29 | 108.0 |
H8A—C8—H8B | 108.1 | C34—C29—H29 | 108.0 |
C10—C9—C8 | 111.4 (4) | C30—C29—H29 | 108.0 |
C10—C9—H9A | 109.4 | C31—C30—C29 | 111.7 (3) |
C8—C9—H9A | 109.4 | C31—C30—H30A | 109.3 |
C10—C9—H9B | 109.4 | C29—C30—H30A | 109.3 |
C8—C9—H9B | 109.4 | C31—C30—H30B | 109.3 |
H9A—C9—H9B | 108.0 | C29—C30—H30B | 109.3 |
C9—C10—C11 | 110.9 (3) | H30A—C30—H30B | 107.9 |
C9—C10—H10A | 109.5 | C32—C31—C30 | 112.1 (4) |
C11—C10—H10A | 109.5 | C32—C31—H31A | 109.2 |
C9—C10—H10B | 109.5 | C30—C31—H31A | 109.2 |
C11—C10—H10B | 109.5 | C32—C31—H31B | 109.2 |
H10A—C10—H10B | 108.0 | C30—C31—H31B | 109.2 |
C10—C11—C12 | 111.8 (4) | H31A—C31—H31B | 107.9 |
C10—C11—H11A | 109.3 | C31—C32—C33 | 111.7 (3) |
C12—C11—H11A | 109.3 | C31—C32—H32A | 109.3 |
C10—C11—H11B | 109.3 | C33—C32—H32A | 109.3 |
C12—C11—H11B | 109.3 | C31—C32—H32B | 109.3 |
H11A—C11—H11B | 107.9 | C33—C32—H32B | 109.3 |
C7—C12—C11 | 111.2 (3) | H32A—C32—H32B | 107.9 |
C7—C12—H12A | 109.4 | C34—C33—C32 | 111.2 (3) |
C11—C12—H12A | 109.4 | C34—C33—H33A | 109.4 |
C7—C12—H12B | 109.4 | C32—C33—H33A | 109.4 |
C11—C12—H12B | 109.4 | C34—C33—H33B | 109.4 |
H12A—C12—H12B | 108.0 | C32—C33—H33B | 109.4 |
C17—N13—N14 | 107.6 (2) | H33A—C33—H33B | 108.0 |
C17—N13—Cu1 | 137.18 (17) | C33—C34—C29 | 111.3 (3) |
N14—N13—Cu1 | 115.00 (15) | C33—C34—H34A | 109.4 |
C15—N14—N13 | 109.5 (2) | C29—C34—H34A | 109.4 |
C15—N14—B35 | 133.0 (2) | C33—C34—H34B | 109.4 |
N13—N14—B35 | 117.47 (19) | C29—C34—H34B | 109.4 |
N14—C15—C16 | 108.2 (2) | H34A—C34—H34B | 108.0 |
N14—C15—H15 | 125.9 | N25—B35—N3 | 111.9 (2) |
C16—C15—H15 | 125.9 | N25—B35—N14 | 111.3 (2) |
C15—C16—C17 | 106.0 (2) | N3—B35—N14 | 106.25 (19) |
C15—C16—H16 | 127.0 | N25—B35—H35 | 109.1 |
C17—C16—H16 | 127.0 | N3—B35—H35 | 109.1 |
N13—C17—C16 | 108.7 (2) | N14—B35—H35 | 109.1 |
N13—C17—C18 | 121.4 (2) | Cl38—C36—Cl37 | 106.8 (11) |
C16—C17—C18 | 129.9 (2) | Cl38—C36—H36A | 110.4 |
C17—C18—C19 | 112.3 (2) | Cl37—C36—H36A | 110.4 |
C17—C18—C23 | 112.7 (2) | Cl38—C36—H36B | 110.4 |
C19—C18—C23 | 109.7 (2) | Cl37—C36—H36B | 110.4 |
C17—C18—H18 | 107.3 | H36A—C36—H36B | 108.6 |
C19—C18—H18 | 107.3 | Cl40—C39—Cl41 | 110.3 (13) |
C23—C18—H18 | 107.3 | Cl40—C39—H39A | 109.6 |
C18—C19—C20 | 111.2 (3) | Cl41—C39—H39A | 109.6 |
C18—C19—H19A | 109.4 | Cl40—C39—H39B | 109.6 |
C20—C19—H19A | 109.4 | Cl41—C39—H39B | 109.6 |
C18—C19—H19B | 109.4 | H39A—C39—H39B | 108.1 |
C20—C19—H19B | 109.4 | Cl43—C42—Cl44 | 102.8 (12) |
H19A—C19—H19B | 108.0 | Cl43—C42—H42A | 111.2 |
C21—C20—C19 | 111.7 (3) | Cl44—C42—H42A | 111.2 |
C21—C20—H20A | 109.3 | Cl43—C42—H42B | 111.2 |
C19—C20—H20A | 109.3 | Cl44—C42—H42B | 111.2 |
C21—C20—H20B | 109.3 | H42A—C42—H42B | 109.1 |
C19—C20—H20B | 109.3 | Cl46—C45—Cl47 | 114.0 (8) |
H20A—C20—H20B | 107.9 | Cl46—C45—H45A | 108.8 |
C20—C21—C22 | 110.8 (3) | Cl47—C45—H45A | 108.8 |
C20—C21—H21A | 109.5 | Cl46—C45—H45B | 108.8 |
C22—C21—H21A | 109.5 | Cl47—C45—H45B | 108.8 |
C20—C21—H21B | 109.5 | H45A—C45—H45B | 107.7 |
C22—C21—H21B | 109.5 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C27H40BN6)2]·2CH2Cl2 |
Mr | 1152.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 13.0758 (2), 18.3961 (3), 13.0405 (2) |
β (°) | 104.6939 (12) |
V (Å3) | 3034.22 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.58 |
Crystal size (mm) | 0.86 × 0.40 × 0.37 |
Data collection | |
Diffractometer | Nonius KappaCCD area detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.634, 0.813 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33672, 6916, 5524 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.173, 1.04 |
No. of reflections | 6916 |
No. of parameters | 363 |
No. of restraints | 12 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.93, −0.62 |
Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1996), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), local program.
Cu1—N2 | 1.9788 (18) | Cu1—N13 | 1.995 (2) |
N2—Cu1—N2i | 180.00 | N2—Cu1—N13 | 87.87 (8) |
N2—Cu1—N13i | 92.13 (8) | N13i—Cu1—N13 | 180.00 |
Symmetry code: (i) −x, −y, −z+1. |
The complexes [CuTp2] [Tp- = hydrido-tris(pyrazol-1-yl)borate] and [CuTp*2] [Tp*- = hydridotris(3,5-dimethylpyrazol-1-yl)borate] adopt distorted octahedral molecular structures in their crystals, with the expected Jahn-Teller elongation along one N—Cu—N axis (Murphy et al., 1979; Kitajima et al., 1988; Marsh, 1989). However, some analogous CuII complexes containing more sterically hindered pyrazolylborate derivatives, which have not been crystallographically characterized, have been proposed to adopt tetrahedral stereochemistries. This suggestion appears to have been made largely on the basis of their brown colouration, which is often a characteristic of tetrahedral CuII centres (Trofimenko et al., 1989; Hannay et al., 1994; Trofimenko, 1999); and because CoII or ZnII complexes of the same ligands have been shown to contain tetrahedral metal ions by crystallography (Trofimenko et al., 1989; Hartmann et al., 1993). We have prepared several compounds of this type during our own studies of copper/hydrido-tris[pyrazol-1-yl]borate chemistry (Halcrow et al., 1997, 1998; Chia et al., 2000; Liu et al., 2000), and report here the single-crystal structure of one such species, (I). \sch
Brown prisms of formula I·2CH2Cl2 were grown from CH2Cl2/CH3OH; the compound crystallizes in the space group P21/a (alternate setting of P21/c). The asymmetric unit of the crystals contains half a molecule of the complex, with Cu1 lying on the inversion centre 1/2 - x, -y, -z; and one disordered molecule of CH2Cl2, lying on a general position. The four-coordinate Cu ion is strictly planar due to the crystallographic inversion symmetry, with N—Cu—N angles that deviate only slightly from a regular square plane owing to the bite angle of the chelating ligand. The Cu—N bond lengths in (I) compare well with those derived by EXAFS for the closely related, brown-coloured (and presumed tetrahedral) complex [Cu(pz0TpiPr)2] (II; [pz0TpiPr]- = tetrakis(3-isopropylpyrazol-1-yl)borate], of 1.93 (2) and 1.94 (2) Å (Hannay et al., 1994). Hence, given the steric similarity between the 3-cyclohexylpyrazole ligating groups in (I), and the 3-isopropyl donors in (II), it seems likely that the latter compound in fact also has a square-planar, rather than tetrahedral, CuII centre. The caveat must be added, however, that different tetrahedral hydrido-tris(pyrazol-1-yl)borate-containing CuII complexes have been shown to exhibit Cu—N bonds in the range 1.928 (3)–2.127 (3) Å (Han et al., 1993; Yoon & Parkin, 1995), so that Cu—N distances are not an infallible guide to coordination geometry in these compounds. Adjacent molecules in the extended lattice of this structure interact through van der Waals contacts only.
The upper and lower faces of the ligand square plane in (I) are efficiently shielded by the ligand cyclohexyl substituents, which would prevent the approach of exogenous ligands to this CuII centre. However, H35 is oriented towards Cu1 in a geometry that is suggestive of an 'agostic' interaction, with Cu1···H35 = 2.71 Å and B35—H35···Cu1 = 94.1°. This Cu···H distance is longer than for other B—H···M (M = first row transition ion) interactions that have been crystallographically characterized, for which M···H distances of ≤2.4 Å are typical (see e.g. Dias et al., 1996; Kremer-Aach et al., 1997; Kiani et al., 1997; Ghosh, Bonanno & Parkin, 1998; Ghosh, Hascall et al., 1998). The only previous CuII/pyrazolylborate complex we are aware of, where an agostic B—H···Cu interaction was proposed, is [Cu(Bp(CF3)2)2] ([Bp(CF3)2]- = dihydrido-bis{3,5-bis(trifluoromethyl)pyrazol-1-yl}borate] for which a Cu···H distance of 2.58 Å was measured crystallographically (Dias & Gorden, 1996). Therefore, given the long Cu1···H35 distance it seems likely that there is no significant bonding interaction between Cu1 and H35 in (I), beyond possibly a weak electrostatic attraction between the hydridic H atom and the positively charged void perpendicular to the square plane of ligand donor atoms.
Complex (I) represents only the second structurally authenticated example of a square-planar, homoleptic complex of a hydrido-tris[pyrazol-1-yl]borate derivative, after [PdTp2] [Tp- = hydrido-tris(pyrazol-1-yl)borate; Canty et al., 1986]. Interestingly, in the Pd complex the ligand conformation is substantially different from that in (I), in that the axial sites above and below the coordination plane are occupied by the non-coordinated pyrazole rings, rather than the hydridic B—H groups. This is the conformation usually (but not exclusively) adopted in the crystal by κ2-hydrido-tris[pyrazol-1-yl]borate derivatives, which are quite common in heteroleptic RhI, IrI, PdII, PtII and AuIII complexes of these ligands (Trofimenko, 1999). However, this conformation is impossible for (I), since it would lead to substantial steric repulsions between the axial pendant pyrazole ring of one ligand, and the cyclohexyl substituents on the coordinated pyrazole rings of the other. Hence the ligand conformation in (I), which brings Cu1 and H35 into close proximity, is probably imposed on steric grounds.