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The title compound, [Cu(C27H40BN6)2]·2CH2Cl2, contains a four-coordinate CuII ion lying on a crystallographic inversion centre, giving rise to a near-regular square-planar stereochemistry. There is an axial contact of 2.71 Å between the Cu ion and ligand B-H group, although this is unlikely to correspond to a significant `agostic' interaction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005510/bm1451sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005510/bm1451Isup2.hkl
Contains datablock I

CCDC reference: 166974

Comment top

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.

Related literature top

For related literature, see: Canty et al. (1986); Chia et al. (2000); Dias & Gorden (1996); Dias, Lu, Gorden & Jin (1996); Ghosh, Bonanno & Parkin (1998); Ghosh, Hascall, Dowling & Parkin (1998); Halcrow et al. (1997, 1998); Han et al. (1993); Hannay et al. (1994); Hartmann et al. (1993); Kiani et al. (1997); Kitajima et al. (1988); Kremer-Aach, Kläui, Bell, Strerath, Wunderlich & Mootz (1997); Liu et al. (2000); Marsh (1989); Murphy et al. (1979); Trofimenko (1999); Trofimenko et al. (1989); Yoon & Parkin (1995).

Experimental top

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%.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Molecular structure of the complex with 35% probability displacement ellipsoids, showing the atom numbering scheme employed. For clarity, all C-bound H atoms have been omitted. [Symmetry code: (i) -x, -y, 1 - z].
Bis(hydridotris-{3-cyclohexylpyrazol-1-yl}borato)copper(II) bis(dichloromethane) solvate top
Crystal data top
[Cu(C27H40BN6)2]·2CH2Cl2F(000) = 1222
Mr = 1152.31Dx = 1.261 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.0758 (2) ÅCell parameters from 33672 reflections
b = 18.3961 (3) Åθ = 2.7–27.5°
c = 13.0405 (2) ŵ = 0.58 mm1
β = 104.6939 (12)°T = 150 K
V = 3034.22 (8) Å3Rectangular prism, brown
Z = 20.86 × 0.40 × 0.37 mm
Data collection top
Nonius KappaCCD area detector
diffractometer
6916 independent reflections
Radiation source: fine-focus sealed tube5524 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.7°
Area detector scansh = 1616
Absorption correction: multi-scan
(Blessing, 1995)
k = 2023
Tmin = 0.634, Tmax = 0.813l = 1616
33672 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H 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 reflectionsΔρmax = 0.93 e Å3
363 parametersΔρmin = 0.62 e Å3
12 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (3)
Crystal data top
[Cu(C27H40BN6)2]·2CH2Cl2V = 3034.22 (8) Å3
Mr = 1152.31Z = 2
Monoclinic, P21/cMo Kα radiation
a = 13.0758 (2) ŵ = 0.58 mm1
b = 18.3961 (3) ÅT = 150 K
c = 13.0405 (2) Å0.86 × 0.40 × 0.37 mm
β = 104.6939 (12)°
Data collection top
Nonius KappaCCD area detector
diffractometer
6916 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
5524 reflections with I > 2σ(I)
Tmin = 0.634, Tmax = 0.813Rint = 0.057
33672 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05812 restraints
wR(F2) = 0.173H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.93 e Å3
6916 reflectionsΔρmin = 0.62 e Å3
363 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.00000.00000.50000.03185 (16)
N20.04459 (15)0.05708 (10)0.39021 (14)0.0347 (4)
N30.11584 (16)0.11128 (11)0.42616 (15)0.0373 (4)
C40.1333 (2)0.14750 (15)0.3432 (2)0.0483 (6)
H40.18000.18760.34680.058*
C50.0720 (2)0.11666 (16)0.2511 (2)0.0505 (7)
H50.06790.13140.18030.061*
C60.01749 (19)0.05938 (13)0.28349 (17)0.0377 (5)
C70.0574 (2)0.00495 (13)0.21961 (18)0.0381 (5)
H70.11070.00700.26020.046*
C80.0021 (3)0.0646 (2)0.2058 (4)0.0908 (15)
H8A0.03350.08470.27620.109*
H8B0.05250.05470.16710.109*
C90.0817 (3)0.1206 (2)0.1438 (4)0.1036 (18)
H9A0.04360.16530.13330.124*
H9B0.13270.13340.18540.124*
C100.1400 (4)0.0916 (3)0.0390 (3)0.0969 (16)
H10A0.19330.12760.00280.116*
H10B0.09000.08360.00560.116*
C110.1943 (4)0.0210 (3)0.0513 (3)0.0962 (17)
H11A0.25040.03030.08830.115*
H11B0.22830.00110.01980.115*
C120.1171 (3)0.0349 (2)0.1136 (3)0.0796 (12)
H12A0.06630.04900.07230.096*
H12B0.15630.07900.12460.096*
N130.15272 (16)0.01636 (10)0.56927 (15)0.0352 (4)
N140.21297 (16)0.04502 (11)0.58778 (15)0.0374 (4)
C150.3114 (2)0.02788 (16)0.6420 (2)0.0479 (6)
H150.36830.06100.66510.057*
C160.3160 (2)0.04621 (16)0.6586 (2)0.0529 (7)
H160.37580.07380.69460.063*
C170.2148 (2)0.07247 (14)0.61165 (19)0.0406 (5)
C180.1729 (2)0.14897 (14)0.6040 (2)0.0427 (5)
H180.09880.14660.61140.051*
C190.2351 (3)0.19715 (17)0.6926 (2)0.0629 (8)
H19A0.23530.17500.76190.075*
H19B0.30920.20060.68770.075*
C200.1870 (4)0.27351 (18)0.6864 (3)0.0722 (10)
H20A0.23120.30430.74280.087*
H20B0.11550.27040.69880.087*
C210.1794 (3)0.30832 (16)0.5800 (3)0.0588 (7)
H21A0.14320.35580.57680.071*
H21B0.25140.31710.57120.071*
C220.1186 (3)0.25986 (17)0.4908 (3)0.0684 (9)
H22A0.04440.25540.49530.082*
H22B0.11820.28230.42170.082*
C230.1689 (3)0.18403 (17)0.4974 (2)0.0653 (9)
H23A0.24140.18810.48780.078*
H23B0.12700.15310.43970.078*
N240.31560 (18)0.19170 (12)0.53375 (18)0.0484 (5)
N250.23294 (17)0.18148 (11)0.57858 (16)0.0427 (5)
C260.3609 (2)0.25391 (15)0.5748 (2)0.0479 (6)
C270.3088 (3)0.28317 (15)0.6471 (2)0.0536 (7)
H270.32610.32640.68760.064*
C280.2278 (2)0.23616 (14)0.6468 (2)0.0475 (6)
H280.17700.24090.68710.057*
C290.4491 (2)0.28526 (17)0.5344 (2)0.0531 (7)
H290.50970.25030.55170.064*
C300.4143 (3)0.2941 (3)0.4130 (3)0.0748 (10)
H30A0.39450.24590.38000.090*
H30B0.35120.32580.39400.090*
C310.5007 (3)0.3264 (3)0.3701 (3)0.0792 (11)
H31A0.56050.29180.38160.095*
H31B0.47380.33390.29280.095*
C320.5389 (4)0.3967 (2)0.4214 (3)0.0826 (11)
H32A0.48140.43310.40260.099*
H32B0.59860.41430.39440.099*
C330.5747 (3)0.3896 (2)0.5414 (3)0.0826 (11)
H33A0.63770.35780.56080.099*
H33B0.59480.43800.57320.099*
C340.4876 (3)0.3578 (2)0.5860 (3)0.0717 (10)
H34A0.42760.39230.57370.086*
H34B0.51450.35100.66340.086*
B350.1577 (2)0.11847 (15)0.5481 (2)0.0387 (6)
H350.09660.12560.58010.046*
C360.327 (2)0.0219 (12)0.370 (2)0.119 (12)*0.30
H36A0.25210.03710.35160.142*0.30
H36B0.34030.00950.43370.142*0.30
Cl370.4107 (4)0.0987 (2)0.3949 (4)0.0835 (16)*0.30
Cl380.3564 (5)0.0250 (2)0.2640 (3)0.0762 (9)*0.30
C390.348 (2)0.0057 (15)0.3794 (16)0.077 (9)*0.20
H39A0.29510.01320.42120.092*0.20
H39B0.39360.04930.38790.092*0.20
Cl400.2804 (7)0.0061 (4)0.2408 (6)0.096 (3)*0.20
Cl410.4286 (12)0.0749 (7)0.4294 (12)0.116 (7)*0.20
C420.376 (2)0.0219 (17)0.4008 (17)0.115 (11)*0.20
H42A0.44070.00190.44930.137*0.20
H42B0.35280.06530.43400.137*0.20
Cl430.2749 (7)0.0439 (5)0.3690 (7)0.122 (2)*0.20
Cl440.3975 (6)0.0432 (4)0.2759 (5)0.0864 (17)*0.20
C450.3417 (12)0.0115 (9)0.3890 (10)0.048 (3)*0.30
H45A0.37390.03190.42950.057*0.30
H45B0.27580.02280.41010.057*0.30
Cl460.4295 (5)0.0854 (5)0.4242 (6)0.0632 (13)*0.30
Cl470.3082 (6)0.0101 (3)0.2489 (4)0.0763 (11)*0.30
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0367 (2)0.0361 (2)0.0229 (2)0.00078 (14)0.00797 (14)0.00044 (14)
N20.0406 (10)0.0368 (10)0.0264 (9)0.0020 (8)0.0078 (7)0.0007 (7)
N30.0445 (10)0.0371 (10)0.0297 (10)0.0034 (8)0.0085 (8)0.0012 (8)
C40.0618 (16)0.0466 (14)0.0356 (13)0.0129 (12)0.0102 (11)0.0034 (11)
C50.0684 (17)0.0529 (15)0.0296 (12)0.0152 (13)0.0115 (11)0.0038 (11)
C60.0466 (13)0.0415 (12)0.0260 (10)0.0020 (10)0.0106 (9)0.0007 (9)
C70.0469 (13)0.0429 (13)0.0247 (10)0.0036 (10)0.0098 (9)0.0028 (9)
C80.060 (2)0.061 (2)0.130 (4)0.0093 (16)0.015 (2)0.044 (2)
C90.067 (2)0.070 (2)0.153 (5)0.0061 (18)0.010 (2)0.064 (3)
C100.095 (3)0.141 (4)0.066 (2)0.058 (3)0.041 (2)0.064 (3)
C110.107 (3)0.097 (3)0.054 (2)0.043 (3)0.037 (2)0.017 (2)
C120.092 (3)0.071 (2)0.0538 (19)0.026 (2)0.0228 (17)0.0152 (17)
N130.0401 (10)0.0376 (10)0.0280 (9)0.0030 (8)0.0092 (8)0.0023 (7)
N140.0431 (10)0.0381 (10)0.0298 (9)0.0040 (8)0.0074 (8)0.0029 (8)
C150.0452 (14)0.0505 (14)0.0415 (14)0.0058 (11)0.0010 (11)0.0006 (12)
C160.0456 (14)0.0484 (15)0.0561 (16)0.0008 (11)0.0028 (12)0.0060 (13)
C170.0435 (12)0.0405 (13)0.0354 (12)0.0018 (10)0.0058 (9)0.0002 (10)
C180.0429 (13)0.0407 (13)0.0435 (13)0.0009 (10)0.0091 (10)0.0019 (10)
C190.092 (2)0.0460 (16)0.0422 (15)0.0077 (15)0.0014 (14)0.0039 (12)
C200.111 (3)0.0481 (17)0.0511 (18)0.0135 (17)0.0084 (17)0.0055 (14)
C210.0668 (18)0.0420 (15)0.071 (2)0.0006 (13)0.0230 (15)0.0023 (14)
C220.104 (3)0.0465 (16)0.0496 (17)0.0133 (16)0.0098 (17)0.0074 (13)
C230.105 (3)0.0474 (16)0.0402 (15)0.0122 (16)0.0115 (15)0.0029 (12)
N240.0524 (12)0.0460 (12)0.0453 (12)0.0081 (10)0.0095 (10)0.0048 (10)
N250.0506 (12)0.0407 (11)0.0351 (10)0.0032 (9)0.0074 (9)0.0037 (9)
C260.0546 (15)0.0451 (14)0.0368 (13)0.0085 (11)0.0016 (11)0.0064 (11)
C270.0782 (19)0.0428 (14)0.0349 (13)0.0107 (13)0.0051 (12)0.0026 (11)
C280.0670 (17)0.0405 (13)0.0323 (12)0.0018 (12)0.0077 (11)0.0042 (10)
C290.0538 (15)0.0556 (16)0.0452 (15)0.0118 (12)0.0039 (11)0.0018 (12)
C300.068 (2)0.104 (3)0.0498 (18)0.0263 (19)0.0093 (15)0.0022 (18)
C310.077 (2)0.106 (3)0.056 (2)0.015 (2)0.0186 (17)0.009 (2)
C320.096 (3)0.072 (2)0.089 (3)0.002 (2)0.040 (2)0.022 (2)
C330.093 (3)0.074 (2)0.085 (3)0.033 (2)0.030 (2)0.011 (2)
C340.081 (2)0.069 (2)0.065 (2)0.0315 (18)0.0195 (17)0.0110 (17)
B350.0444 (14)0.0395 (14)0.0311 (12)0.0007 (11)0.0073 (10)0.0035 (10)
Geometric parameters (Å, º) top
Cu1—N21.9788 (18)C22—C231.535 (4)
Cu1—N131.995 (2)C22—H22A0.9900
N2—C61.347 (3)C22—H22B0.9900
N2—N31.364 (3)C23—H23A0.9900
N3—C41.339 (3)C23—H23B0.9900
N3—B351.551 (3)N24—C261.336 (3)
C4—C51.385 (4)N24—N251.366 (3)
C4—H40.9500N25—C281.356 (3)
C5—C61.397 (3)N25—B351.507 (3)
C5—H50.9500C26—C271.403 (4)
C6—C71.497 (3)C26—C291.500 (4)
C7—C81.503 (4)C27—C281.367 (4)
C7—C121.509 (4)C27—H270.9500
C7—H71.0000C28—H280.9500
C8—C91.539 (5)C29—C341.522 (4)
C8—H8A0.9900C29—C301.540 (4)
C8—H8B0.9900C29—H291.0000
C9—C101.484 (7)C30—C311.504 (5)
C9—H9A0.9900C30—H30A0.9900
C9—H9B0.9900C30—H30B0.9900
C10—C111.508 (7)C31—C321.484 (6)
C10—H10A0.9900C31—H31A0.9900
C10—H10B0.9900C31—H31B0.9900
C11—C121.523 (5)C32—C331.521 (6)
C11—H11A0.9900C32—H32A0.9900
C11—H11B0.9900C32—H32B0.9900
C12—H12A0.9900C33—C341.520 (5)
C12—H12B0.9900C33—H33A0.9900
N13—C171.342 (3)C33—H33B0.9900
N13—N141.363 (3)C34—H34A0.9900
N14—C151.340 (3)C34—H34B0.9900
N14—B351.557 (3)B35—H351.0000
C15—C161.379 (4)C36—Cl381.754 (18)
C15—H150.9500C36—Cl371.764 (17)
C16—C171.396 (4)C36—H36A0.9900
C16—H160.9500C36—H36B0.9900
C17—C181.504 (4)C39—Cl401.812 (18)
C18—C191.519 (4)C39—Cl411.841 (19)
C18—C231.521 (4)C39—H39A0.9900
C18—H181.0000C39—H39B0.9900
C19—C201.533 (4)C42—Cl431.764 (19)
C19—H19A0.9900C42—Cl441.766 (19)
C19—H19B0.9900C42—H42A0.9900
C20—C211.507 (5)C42—H42B0.9900
C20—H20A0.9900C45—Cl461.763 (12)
C20—H20B0.9900C45—Cl471.812 (12)
C21—C221.521 (5)C45—H45A0.9900
C21—H21A0.9900C45—H45B0.9900
C21—H21B0.9900
N2—Cu1—N2i180.00H21A—C21—H21B108.1
N2—Cu1—N13i92.13 (8)C21—C22—C23110.9 (3)
N2—Cu1—N1387.87 (8)C21—C22—H22A109.5
N13i—Cu1—N13180.00C23—C22—H22A109.5
C6—N2—N3108.05 (18)C21—C22—H22B109.5
C6—N2—Cu1135.70 (16)C23—C22—H22B109.5
N3—N2—Cu1116.12 (14)H22A—C22—H22B108.0
C4—N3—N2109.14 (19)C18—C23—C22110.6 (3)
C4—N3—B35134.3 (2)C18—C23—H23A109.5
N2—N3—B35116.59 (18)C22—C23—H23A109.5
N3—C4—C5108.5 (2)C18—C23—H23B109.5
N3—C4—H4125.8C22—C23—H23B109.5
C5—C4—H4125.8H23A—C23—H23B108.1
C4—C5—C6105.9 (2)C26—N24—N25105.3 (2)
C4—C5—H5127.0C28—N25—N24110.8 (2)
C6—C5—H5127.0C28—N25—B35127.3 (2)
N2—C6—C5108.4 (2)N24—N25—B35121.8 (2)
N2—C6—C7121.2 (2)N24—C26—C27110.9 (2)
C5—C6—C7130.4 (2)N24—C26—C29119.4 (3)
C6—C7—C8111.7 (2)C27—C26—C29129.5 (3)
C6—C7—C12112.3 (2)C28—C27—C26105.3 (2)
C8—C7—C12110.7 (3)C28—C27—H27127.4
C6—C7—H7107.3C26—C27—H27127.4
C8—C7—H7107.3N25—C28—C27107.7 (3)
C12—C7—H7107.3N25—C28—H28126.2
C7—C8—C9110.5 (3)C27—C28—H28126.2
C7—C8—H8A109.5C26—C29—C34112.3 (3)
C9—C8—H8A109.5C26—C29—C30110.4 (2)
C7—C8—H8B109.5C34—C29—C30109.9 (3)
C9—C8—H8B109.5C26—C29—H29108.0
H8A—C8—H8B108.1C34—C29—H29108.0
C10—C9—C8111.4 (4)C30—C29—H29108.0
C10—C9—H9A109.4C31—C30—C29111.7 (3)
C8—C9—H9A109.4C31—C30—H30A109.3
C10—C9—H9B109.4C29—C30—H30A109.3
C8—C9—H9B109.4C31—C30—H30B109.3
H9A—C9—H9B108.0C29—C30—H30B109.3
C9—C10—C11110.9 (3)H30A—C30—H30B107.9
C9—C10—H10A109.5C32—C31—C30112.1 (4)
C11—C10—H10A109.5C32—C31—H31A109.2
C9—C10—H10B109.5C30—C31—H31A109.2
C11—C10—H10B109.5C32—C31—H31B109.2
H10A—C10—H10B108.0C30—C31—H31B109.2
C10—C11—C12111.8 (4)H31A—C31—H31B107.9
C10—C11—H11A109.3C31—C32—C33111.7 (3)
C12—C11—H11A109.3C31—C32—H32A109.3
C10—C11—H11B109.3C33—C32—H32A109.3
C12—C11—H11B109.3C31—C32—H32B109.3
H11A—C11—H11B107.9C33—C32—H32B109.3
C7—C12—C11111.2 (3)H32A—C32—H32B107.9
C7—C12—H12A109.4C34—C33—C32111.2 (3)
C11—C12—H12A109.4C34—C33—H33A109.4
C7—C12—H12B109.4C32—C33—H33A109.4
C11—C12—H12B109.4C34—C33—H33B109.4
H12A—C12—H12B108.0C32—C33—H33B109.4
C17—N13—N14107.6 (2)H33A—C33—H33B108.0
C17—N13—Cu1137.18 (17)C33—C34—C29111.3 (3)
N14—N13—Cu1115.00 (15)C33—C34—H34A109.4
C15—N14—N13109.5 (2)C29—C34—H34A109.4
C15—N14—B35133.0 (2)C33—C34—H34B109.4
N13—N14—B35117.47 (19)C29—C34—H34B109.4
N14—C15—C16108.2 (2)H34A—C34—H34B108.0
N14—C15—H15125.9N25—B35—N3111.9 (2)
C16—C15—H15125.9N25—B35—N14111.3 (2)
C15—C16—C17106.0 (2)N3—B35—N14106.25 (19)
C15—C16—H16127.0N25—B35—H35109.1
C17—C16—H16127.0N3—B35—H35109.1
N13—C17—C16108.7 (2)N14—B35—H35109.1
N13—C17—C18121.4 (2)Cl38—C36—Cl37106.8 (11)
C16—C17—C18129.9 (2)Cl38—C36—H36A110.4
C17—C18—C19112.3 (2)Cl37—C36—H36A110.4
C17—C18—C23112.7 (2)Cl38—C36—H36B110.4
C19—C18—C23109.7 (2)Cl37—C36—H36B110.4
C17—C18—H18107.3H36A—C36—H36B108.6
C19—C18—H18107.3Cl40—C39—Cl41110.3 (13)
C23—C18—H18107.3Cl40—C39—H39A109.6
C18—C19—C20111.2 (3)Cl41—C39—H39A109.6
C18—C19—H19A109.4Cl40—C39—H39B109.6
C20—C19—H19A109.4Cl41—C39—H39B109.6
C18—C19—H19B109.4H39A—C39—H39B108.1
C20—C19—H19B109.4Cl43—C42—Cl44102.8 (12)
H19A—C19—H19B108.0Cl43—C42—H42A111.2
C21—C20—C19111.7 (3)Cl44—C42—H42A111.2
C21—C20—H20A109.3Cl43—C42—H42B111.2
C19—C20—H20A109.3Cl44—C42—H42B111.2
C21—C20—H20B109.3H42A—C42—H42B109.1
C19—C20—H20B109.3Cl46—C45—Cl47114.0 (8)
H20A—C20—H20B107.9Cl46—C45—H45A108.8
C20—C21—C22110.8 (3)Cl47—C45—H45A108.8
C20—C21—H21A109.5Cl46—C45—H45B108.8
C22—C21—H21A109.5Cl47—C45—H45B108.8
C20—C21—H21B109.5H45A—C45—H45B107.7
C22—C21—H21B109.5
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Cu(C27H40BN6)2]·2CH2Cl2
Mr1152.31
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)13.0758 (2), 18.3961 (3), 13.0405 (2)
β (°) 104.6939 (12)
V3)3034.22 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.58
Crystal size (mm)0.86 × 0.40 × 0.37
Data collection
DiffractometerNonius KappaCCD area detector
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.634, 0.813
No. of measured, independent and
observed [I > 2σ(I)] reflections
33672, 6916, 5524
Rint0.057
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.173, 1.04
No. of reflections6916
No. of parameters363
No. of restraints12
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Cu1—N21.9788 (18)Cu1—N131.995 (2)
N2—Cu1—N2i180.00N2—Cu1—N1387.87 (8)
N2—Cu1—N13i92.13 (8)N13i—Cu1—N13180.00
Symmetry code: (i) x, y, z+1.
 

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