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Acta Cryst. (2009). E65, m795-m796    [ doi:10.1107/S1600536809022661 ]

(N4-n-Butylpyridine-4-carbothioamide-[kappa]N4)chloridobis(dimethylglyoximato-[kappa]2N,N')cobalt(III) hemihydrate

C. Revathi, A. Dayalan and K. SethuSankar

Abstract top

The title compound, trans-[Co(C4H7N2O2)2Cl(C10H14N2S)]·0.5H2O, contains two independent molecules in the asymmetric unit in which the CoIII ions are coordinated in slightly distorted octahedral coordination environments. The bis-chelating glyoximate ligands, which occupy equatorial sites, are linked by interligand O-H...O hydrogen bonds. The dihedral angles between the mean planes of the glyoximate ligands in each molecule are 2.07 (8) and 1.60 (1)°. The asymmetric unit contains a solvent water molecule which is disordered over two sites with refined occupancies 0.64 (2) and 0.36 (2).

Comment top

The study of simple models of the B12 coenzyme such as the cobaloximes, [RCo(dmgH)2L] where R= alkyl group, dmgH-= dimethylglyoximate and L=neutral ligand, has furnished significant amounts of data that have provided a foundation for understanding the behaviour of cobaloximes (Trogler et al., 1974). Compared to other cobalamins and other model systems, cobaloximes have shorter Co-L bonds where L= pyridine or a substituted pyridine group. It is known that such a metal coenzyme is related to a number of 1,2-intramolecular rearangement enzymatic reactions (Dolphin et al., 1982). Early X-ray diffraction analysis has shown that the coenzyme has a bulky corrin ring in the equatorial position (Bresciani-Pahor et al., 1985) the deadenosyl group and 5,6-dimethylbenzimidazole group as the axial ligands. The flexiblity of the equatorial oxime ligands is quite similar to that of corrin in neutral co-factor (Geno & Halpern, 1987). In the title compond the coordination about the CoIII ion is slightly distorted octahedral with the the N-n-Butyl-4-pyridinecarbothioamide and chloride ligands occupy the axial positions and the two dimethyl glyoximato ligands occupy the equatorial sites. The axial bonds are essentially perpendicular (see coordination bond angles) to the equatorial glyoximate least-squares planes (with maximum deviation from the planes of 0.054 (2) and 0.072 (2)Å for O3 and O8 respectively). In one molecule the n-butyl group is in an extended conformation, while in the other it has a coiled conformation as described by the torsion angles N12-C33-C34-C35 = 177.7 (4) and N6-C15-C16-C17 = -51.0 (4) °, respectively. The dihedral angle between the mean planes of the glyoximato ligands in each molecule are 2.07 (8)° and 1.60 (1)° (cf. Englert et al., 1999;2000). There is one weak C-H···Cl interaction in involving chlorine atom of one molecule and an H atom from the other independent molecule [H28···Cl1i = 2.72Å; C28-H28-Cl1i = 156° and C28···Cl1i = 3.591 (4)Å; symmetry code (i): 3/2-x, -1/2+y, 1/2-z].

Related literature top

For a related structure, see: Kavitha et al. (2008). For background, see: Trogler et al. (1974); Dolphin (1982); Bresciani-Pahor et al. (1985); Geno & Halpern (1987); Englert et al. (1999, 2000). For the synthetic prodedure, see: Schrauzer et al. (1964); Ramesh et al. (2008).

Experimental top

The title compound was synthesized by a literature method (Schrauzer & Kohnel, 1964), using H[Co(dmgH)2Cl2] as the starting material (Ramesh et al., 2008). The dichloro cobaloxime was mixed with N-n-Bu-4-PCT in 1:1 molar ratio in about 60 ml of absolute ethanol and allowed to stir for 3hrs with warming. The resulting brown coloured complex was filtered and washed with absolute ethanol and ether and dried over vacuum desiccator. Crystals of the complex were grown in ethanol by slow evaporation. The purity of the complex was ascertained by UV-Vis, IR and NMR.

Refinement top

H atoms were visible in difference Fourier maps but those bonded to H atoms were placed idealized positions and included in the refinement in a riding-model approximation with C—H(aromatic) = 0.93Å and Uiso(H) = 1.2UeqC; C—H(methyl) = 0.96A%, and Uiso(H) = 1.5UeqC.A%. H atoms bonded to O atoms in the complex molecules were refined independently with isotropic displacement parameters. The H atoms of the disordered water atoms were not located and are not included in the refinement but are however included in the molecular formula. They were not considered in the hydrogen bonding motif.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altornare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit with 30% probability ellipsoids. Hydrogen atoms and the solvent water is omitted for clarity. Dashed lines indicate hydrogen bonds.
(N4-n-Butylpyridine-4-carbothioamide- κN4)chloridobis(dimethylglyoximato-κ2N,N')cobalt(III) hemihydrate top
Crystal data top
[Co(C4H7N2O2)2Cl(C10H14N2S)]·0.5H2OF(000) = 2192
Mr = 526.90Dx = 1.473 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5420 reflections
a = 11.1976 (5) Åθ = 2.5–26.0°
b = 14.7889 (7) ŵ = 0.96 mm−1
c = 28.8482 (14) ÅT = 293 K
β = 95.748 (2)°Needle, brown
V = 4753.2 (4) Å30.3 × 0.2 × 0.2 mm
Z = 8
Data collection top
Bruker Kappa-APEX2
diffractometer		10297 independent reflections
Radiation source: fine-focus sealed tube7510 reflections with I > 2σ(I)
graphiteRint = 0.044
Detector resolution: 0 pixels mm-1θmax = 26.9°, θmin = 1.4°
ω and φ scansh = −14→10
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		k = −18→18
Tmin = 0.742, Tmax = 0.853l = −36→36
50767 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)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168 w = 1/[σ2(Fo2) + (0.0927P)2 + 3.9112P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.009
10297 reflectionsΔρmax = 0.96 e Å−3
606 parametersΔρmin = −0.82 e Å−3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0023 (3)
Crystal data top
[Co(C4H7N2O2)2Cl(C10H14N2S)]·0.5H2OV = 4753.2 (4) Å3
Mr = 526.90Z = 8
Monoclinic, P21/nMo Kα radiation
a = 11.1976 (5) ŵ = 0.96 mm−1
b = 14.7889 (7) ÅT = 293 K
c = 28.8482 (14) Å0.3 × 0.2 × 0.2 mm
β = 95.748 (2)°
Data collection top
Bruker Kappa-APEX2
diffractometer		10297 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		7510 reflections with I > 2σ(I)
Tmin = 0.742, Tmax = 0.853Rint = 0.044
50767 measured reflectionsθmax = 26.9°
Refinement top
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168Δρmax = 0.96 e Å−3
S = 1.06Δρmin = −0.82 e Å−3
10297 reflectionsAbsolute structure: ?
606 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.6540 (3)0.4012 (2)0.14607 (12)0.0391 (8)
C20.5817 (3)0.3183 (3)0.13929 (13)0.0395 (8)
C30.7787 (4)0.2495 (3)−0.01437 (14)0.0480 (9)
C40.8518 (3)0.3305 (3)−0.00758 (13)0.0432 (9)
C50.6493 (4)0.4620 (3)0.18669 (13)0.0548 (11)
H5A0.68950.51770.18110.082*
H5B0.68840.43350.21400.082*
H5C0.56710.47420.19130.082*
C60.4897 (4)0.2917 (3)0.17091 (16)0.0579 (12)
H6A0.42530.33480.16820.087*
H6B0.52590.29030.20250.087*
H6C0.45870.23290.16230.087*
C70.7738 (6)0.1895 (4)−0.05624 (19)0.091 (2)
H7A0.73750.1328−0.04940.137*
H7B0.85370.1790−0.06440.137*
H7C0.72700.2180−0.08180.137*
C80.9383 (4)0.3614 (3)−0.04059 (15)0.0570 (11)
H8A0.96570.4213−0.03230.085*
H8B0.89910.3618−0.07170.085*
H8C1.00560.3209−0.03890.085*
C90.8419 (4)0.1681 (3)0.10754 (17)0.0542 (11)
H90.77870.13750.09110.065*
C100.9260 (4)0.1193 (3)0.13510 (17)0.0587 (12)
H100.91970.05670.13680.070*
C111.0198 (4)0.1636 (3)0.16024 (14)0.0486 (10)
C121.0274 (4)0.2554 (3)0.15450 (16)0.0536 (10)
H121.09110.28730.16980.064*
C130.9412 (4)0.3003 (3)0.12621 (14)0.0458 (9)
H130.94810.36260.12270.055*
C141.1118 (4)0.1146 (4)0.19326 (17)0.0641 (12)
C151.1459 (6)−0.0284 (5)0.2383 (2)0.0906 (19)
H15A1.17780.00940.26410.109*
H15B1.0891−0.06990.25010.109*
C161.2409 (7)−0.0793 (5)0.2233 (2)0.113 (3)
H16A1.2700−0.11940.24850.136*
H16B1.3056−0.03760.21860.136*
C171.2186 (6)−0.1359 (5)0.1797 (2)0.0895 (18)
H17A1.1807−0.09780.15510.107*
H17B1.2957−0.15450.17040.107*
C181.1436 (6)−0.2176 (5)0.1829 (3)0.107 (2)
H18A1.1685−0.24910.21140.161*
H18B1.1528−0.25640.15690.161*
H18C1.0610−0.20020.18270.161*
C190.8873 (4)0.4019 (3)0.40245 (15)0.0548 (11)
C200.9481 (4)0.4264 (3)0.36220 (16)0.0510 (10)
C210.7077 (4)0.1755 (3)0.26363 (13)0.0442 (9)
C220.6402 (3)0.1546 (3)0.30342 (14)0.0441 (9)
C230.9121 (6)0.4454 (4)0.44954 (18)0.0843 (18)
H23A0.86440.41670.47120.126*
H23B0.89200.50850.44730.126*
H23C0.99560.43890.46020.126*
C241.0394 (5)0.4994 (3)0.3627 (2)0.0781 (16)
H24A1.06200.50800.33170.117*
H24B1.10880.48280.38310.117*
H24C1.00630.55450.37340.117*
C250.6947 (5)0.1242 (3)0.21891 (16)0.0650 (13)
H25A0.73170.15750.19560.098*
H25B0.61110.11570.20890.098*
H25C0.73300.06630.22340.098*
C260.5420 (4)0.0867 (3)0.3009 (2)0.0681 (13)
H26A0.52140.07400.33170.102*
H26B0.56820.03210.28710.102*
H26C0.47310.11020.28230.102*
C270.9110 (3)0.1502 (2)0.38996 (12)0.0374 (8)
H270.84390.15600.40630.045*
C280.9965 (3)0.0876 (3)0.40509 (12)0.0375 (8)
H280.98620.05170.43090.045*
C291.0991 (3)0.0776 (2)0.38179 (12)0.0361 (8)
C301.1068 (4)0.1332 (3)0.34363 (14)0.0447 (9)
H301.17350.12930.32700.054*
C311.0177 (4)0.1937 (3)0.33005 (14)0.0430 (9)
H311.02540.22960.30400.052*
C321.1937 (3)0.0082 (3)0.39541 (13)0.0397 (8)
C331.2757 (4)−0.0957 (3)0.45690 (15)0.0512 (10)
H33A1.2829−0.09370.49070.061*
H33B1.3549−0.08590.44690.061*
C341.2308 (4)−0.1880 (3)0.44078 (18)0.0555 (11)
H34A1.1529−0.19820.45180.067*
H34B1.2202−0.18870.40700.067*
C351.3131 (4)−0.2642 (3)0.45739 (17)0.0588 (11)
H35A1.3197−0.26650.49120.071*
H35B1.3925−0.25270.44800.071*
C361.2683 (5)−0.3549 (4)0.4380 (2)0.0869 (18)
H36A1.1937−0.36950.44990.130*
H36B1.3265−0.40080.44710.130*
H36C1.2564−0.35160.40460.130*
N10.7222 (3)0.4142 (2)0.11309 (10)0.0356 (6)
N20.6040 (3)0.2735 (2)0.10299 (10)0.0359 (6)
N30.7116 (3)0.2353 (2)0.01918 (11)0.0403 (7)
N40.8335 (3)0.3740 (2)0.02985 (10)0.0355 (6)
N50.8476 (3)0.2575 (2)0.10354 (10)0.0347 (6)
N61.0805 (4)0.0297 (3)0.20319 (16)0.0767 (13)
N70.8069 (3)0.3394 (2)0.39383 (11)0.0465 (8)
N80.9133 (3)0.3797 (2)0.32561 (12)0.0444 (8)
N90.7812 (3)0.2424 (2)0.27193 (10)0.0388 (7)
N100.6723 (3)0.2043 (2)0.33924 (11)0.0409 (7)
N110.9195 (3)0.20336 (19)0.35282 (10)0.0331 (6)
N121.1953 (3)−0.0228 (2)0.43840 (12)0.0465 (8)
O10.7913 (3)0.48767 (17)0.11270 (9)0.0465 (6)
O20.5463 (3)0.19640 (18)0.09123 (11)0.0504 (7)
O30.6361 (3)0.1655 (2)0.01808 (11)0.0589 (8)
O40.8906 (2)0.45087 (19)0.04153 (10)0.0470 (6)
O50.7379 (3)0.3099 (2)0.42581 (10)0.0642 (9)
O60.9561 (3)0.3945 (2)0.28445 (11)0.0569 (8)
O70.8475 (3)0.2714 (2)0.23890 (10)0.0545 (7)
O80.6170 (3)0.1955 (2)0.37864 (11)0.0570 (8)
O90.5206 (13)0.4306 (11)0.4152 (10)0.117 (9)0.36 (2)
O9'0.563 (2)0.4610 (14)0.4517 (9)0.258 (10)0.64 (2)
S11.22943 (19)0.16153 (15)0.21468 (9)0.1222 (8)
S21.28739 (11)−0.02367 (9)0.35816 (4)0.0642 (3)
Cl10.57535 (8)0.39973 (6)0.02391 (3)0.0401 (2)
Cl20.65579 (9)0.39511 (7)0.31055 (4)0.0494 (3)
Co10.71972 (4)0.32373 (3)0.066535 (15)0.02991 (14)
Co20.79476 (4)0.29152 (3)0.333079 (16)0.03392 (14)
H10.829 (5)0.480 (4)0.076 (2)0.092 (17)*
H20.566 (5)0.181 (4)0.055 (2)0.090 (18)*
H80.670 (6)0.244 (5)0.406 (3)0.13 (2)*
H70.890 (6)0.323 (5)0.254 (3)0.13 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.051 (2)0.039 (2)0.0281 (17)0.0090 (16)0.0051 (15)0.0082 (15)
C20.0390 (19)0.046 (2)0.0340 (19)0.0050 (16)0.0060 (15)0.0135 (16)
C30.060 (2)0.046 (2)0.039 (2)0.0048 (19)0.0079 (18)−0.0063 (17)
C40.044 (2)0.047 (2)0.040 (2)0.0068 (17)0.0091 (16)0.0049 (17)
C50.077 (3)0.055 (3)0.032 (2)0.011 (2)0.006 (2)0.0002 (18)
C60.055 (2)0.071 (3)0.051 (3)0.008 (2)0.020 (2)0.021 (2)
C70.138 (6)0.084 (4)0.056 (3)−0.013 (4)0.031 (3)−0.029 (3)
C80.055 (2)0.076 (3)0.043 (2)0.004 (2)0.0205 (19)0.004 (2)
C90.054 (2)0.039 (2)0.067 (3)−0.0056 (19)−0.009 (2)0.010 (2)
C100.059 (3)0.039 (2)0.075 (3)−0.0016 (19)−0.008 (2)0.018 (2)
C110.046 (2)0.056 (3)0.043 (2)0.0080 (19)0.0039 (17)0.0119 (19)
C120.048 (2)0.053 (3)0.057 (3)−0.0051 (19)−0.0082 (19)0.005 (2)
C130.046 (2)0.039 (2)0.051 (2)−0.0044 (17)−0.0002 (18)0.0059 (18)
C140.062 (3)0.073 (3)0.056 (3)0.011 (2)−0.002 (2)0.009 (2)
C150.114 (5)0.095 (5)0.060 (3)0.035 (4)−0.003 (3)0.008 (3)
C160.132 (6)0.127 (6)0.073 (4)0.057 (5)−0.023 (4)−0.020 (4)
C170.090 (4)0.094 (5)0.083 (4)0.018 (4)0.000 (3)−0.022 (4)
C180.077 (4)0.123 (6)0.123 (6)−0.002 (4)0.016 (4)−0.013 (5)
C190.070 (3)0.041 (2)0.049 (2)0.020 (2)−0.015 (2)−0.0140 (19)
C200.050 (2)0.0300 (19)0.070 (3)0.0063 (17)−0.010 (2)−0.0070 (19)
C210.053 (2)0.039 (2)0.039 (2)0.0093 (18)−0.0025 (17)−0.0019 (16)
C220.042 (2)0.037 (2)0.052 (2)0.0029 (16)0.0001 (17)0.0060 (18)
C230.116 (5)0.067 (3)0.062 (3)0.021 (3)−0.029 (3)−0.028 (3)
C240.069 (3)0.042 (3)0.120 (5)−0.004 (2)−0.008 (3)−0.015 (3)
C250.091 (4)0.054 (3)0.047 (3)0.004 (2)−0.006 (2)−0.014 (2)
C260.058 (3)0.059 (3)0.086 (4)−0.012 (2)−0.002 (2)0.008 (3)
C270.0402 (18)0.042 (2)0.0309 (18)0.0037 (16)0.0081 (14)0.0000 (15)
C280.0417 (19)0.042 (2)0.0288 (17)0.0010 (16)0.0030 (14)0.0023 (15)
C290.0375 (18)0.0343 (18)0.0368 (18)0.0001 (15)0.0051 (14)−0.0064 (15)
C300.045 (2)0.040 (2)0.052 (2)0.0029 (17)0.0173 (17)0.0030 (18)
C310.050 (2)0.0361 (19)0.045 (2)0.0023 (16)0.0187 (17)0.0075 (16)
C320.0373 (18)0.0371 (19)0.044 (2)−0.0007 (15)−0.0009 (15)−0.0043 (16)
C330.048 (2)0.054 (2)0.049 (2)0.0111 (19)−0.0052 (18)0.004 (2)
C340.046 (2)0.051 (2)0.069 (3)0.0056 (19)−0.002 (2)0.007 (2)
C350.058 (3)0.056 (3)0.062 (3)0.007 (2)0.000 (2)0.009 (2)
C360.088 (4)0.051 (3)0.119 (5)0.007 (3)0.000 (4)0.001 (3)
N10.0434 (16)0.0311 (15)0.0319 (15)−0.0013 (12)0.0025 (12)0.0033 (12)
N20.0349 (15)0.0338 (15)0.0393 (16)−0.0028 (12)0.0060 (12)0.0079 (13)
N30.0486 (17)0.0327 (16)0.0391 (17)−0.0030 (13)0.0017 (14)−0.0028 (13)
N40.0390 (15)0.0349 (16)0.0333 (15)−0.0028 (13)0.0069 (12)0.0044 (12)
N50.0363 (15)0.0330 (15)0.0353 (15)−0.0023 (12)0.0066 (12)0.0036 (12)
N60.092 (3)0.061 (3)0.074 (3)0.022 (2)−0.009 (2)0.017 (2)
N70.062 (2)0.0415 (19)0.0356 (17)0.0155 (16)0.0042 (15)−0.0054 (14)
N80.0500 (18)0.0311 (16)0.0513 (19)0.0065 (14)0.0022 (15)0.0021 (14)
N90.0497 (17)0.0362 (16)0.0315 (15)0.0042 (14)0.0088 (13)0.0021 (13)
N100.0433 (17)0.0425 (17)0.0382 (17)0.0051 (14)0.0099 (13)0.0057 (14)
N110.0403 (15)0.0281 (14)0.0313 (15)0.0018 (12)0.0053 (12)−0.0008 (12)
N120.0441 (17)0.0459 (19)0.0483 (19)0.0084 (15)−0.0002 (14)0.0053 (15)
O10.0613 (17)0.0344 (14)0.0440 (15)−0.0121 (12)0.0056 (13)−0.0032 (12)
O20.0487 (16)0.0403 (15)0.0625 (19)−0.0163 (12)0.0079 (14)0.0053 (13)
O30.073 (2)0.0419 (16)0.0602 (19)−0.0208 (15)0.0010 (16)−0.0103 (14)
O40.0496 (15)0.0447 (15)0.0475 (15)−0.0196 (13)0.0094 (12)0.0037 (12)
O50.089 (2)0.070 (2)0.0364 (16)0.0175 (18)0.0160 (16)−0.0037 (15)
O60.0630 (18)0.0475 (17)0.0631 (19)−0.0028 (14)0.0211 (15)0.0125 (14)
O70.074 (2)0.0575 (19)0.0352 (15)0.0007 (16)0.0202 (14)0.0040 (13)
O80.0560 (17)0.068 (2)0.0516 (18)0.0074 (15)0.0273 (14)0.0159 (15)
O90.071 (9)0.089 (10)0.20 (2)0.009 (7)0.048 (10)−0.003 (11)
O9'0.34 (2)0.181 (15)0.24 (2)0.073 (15)−0.035 (18)0.031 (15)
S10.1044 (13)0.1075 (15)0.1419 (18)−0.0176 (11)−0.0507 (13)0.0240 (13)
S20.0658 (7)0.0746 (8)0.0535 (7)0.0232 (6)0.0127 (6)0.0032 (6)
Cl10.0417 (5)0.0443 (5)0.0342 (4)0.0051 (4)0.0029 (3)0.0077 (4)
Cl20.0552 (6)0.0440 (5)0.0482 (5)0.0141 (4)0.0019 (4)0.0042 (4)
Co10.0343 (2)0.0272 (2)0.0284 (2)−0.00359 (18)0.00409 (18)0.00201 (18)
Co20.0419 (3)0.0305 (3)0.0297 (3)0.0035 (2)0.00545 (19)0.00001 (19)
Geometric parameters (Å, °) top
C1—N11.293 (4)C24—H24B0.9600
C1—C21.471 (5)C24—H24C0.9600
C1—C51.483 (5)C25—H25A0.9600
C2—N21.284 (5)C25—H25B0.9600
C2—C61.496 (5)C25—H25C0.9600
C3—N31.300 (5)C26—H26A0.9600
C3—C41.453 (6)C26—H26B0.9600
C3—C71.495 (6)C26—H26C0.9600
C4—N41.291 (5)C27—N111.340 (4)
C4—C81.496 (5)C27—C281.371 (5)
C5—H5A0.9600C27—H270.9300
C5—H5B0.9600C28—C291.395 (5)
C5—H5C0.9600C28—H280.9300
C6—H6A0.9600C29—C301.383 (5)
C6—H6B0.9600C29—C321.499 (5)
C6—H6C0.9600C30—C311.368 (5)
C7—H7A0.9600C30—H300.9300
C7—H7B0.9600C31—N111.343 (5)
C7—H7C0.9600C31—H310.9300
C8—H8A0.9600C32—N121.321 (5)
C8—H8B0.9600C32—S21.644 (4)
C8—H8C0.9600C33—N121.469 (5)
C9—N51.330 (5)C33—C341.512 (6)
C9—C101.374 (6)C33—H33A0.9700
C9—H90.9300C33—H33B0.9700
C10—C111.381 (6)C34—C351.503 (6)
C10—H100.9300C34—H34A0.9700
C11—C121.371 (6)C34—H34B0.9700
C11—C141.516 (6)C35—C361.519 (7)
C12—C131.371 (6)C35—H35A0.9700
C12—H120.9300C35—H35B0.9700
C13—N51.337 (5)C36—H36A0.9600
C13—H130.9300C36—H36B0.9600
C14—N61.343 (7)C36—H36C0.9600
C14—S11.560 (5)N1—O11.335 (4)
C15—C161.407 (8)N1—Co11.894 (3)
C15—N61.467 (6)N2—O21.338 (4)
C15—H15A0.9700N2—Co11.900 (3)
C15—H15B0.9700N3—O31.333 (4)
C16—C171.510 (8)N3—Co11.887 (3)
C16—H16A0.9700N4—O41.331 (4)
C16—H16B0.9700N4—Co11.889 (3)
C17—C181.480 (9)N5—Co11.960 (3)
C17—H17A0.9700N7—O51.334 (5)
C17—H17B0.9700N7—Co21.882 (3)
C18—H18A0.9600N8—O61.343 (4)
C18—H18B0.9600N8—Co21.888 (3)
C18—H18C0.9600N9—O71.336 (4)
C19—N71.297 (6)N9—Co21.900 (3)
C19—C201.450 (7)N10—O81.354 (4)
C19—C231.504 (6)N10—Co21.904 (3)
C20—N81.288 (5)N11—Co21.954 (3)
C20—C241.486 (6)O1—H11.20 (6)
C21—N91.293 (5)O2—H21.12 (6)
C21—C221.469 (6)O3—H21.39 (6)
C21—C251.492 (6)O4—H11.32 (6)
C22—N101.290 (5)O5—H81.34 (8)
C22—C261.485 (6)O7—H70.98 (7)
C23—H23A0.9600O8—H81.17 (8)
C23—H23B0.9600Cl1—Co12.2341 (10)
C23—H23C0.9600Cl2—Co22.2334 (10)
C24—H24A0.9600
N1—C1—C2112.6 (3)H26B—C26—H26C109.5
N1—C1—C5124.2 (4)N11—C27—C28123.2 (3)
C2—C1—C5123.3 (3)N11—C27—H27118.4
N2—C2—C1112.9 (3)C28—C27—H27118.4
N2—C2—C6124.3 (4)C27—C28—C29120.0 (3)
C1—C2—C6122.8 (4)C27—C28—H28120.0
N3—C3—C4113.1 (3)C29—C28—H28120.0
N3—C3—C7121.9 (4)C30—C29—C28116.2 (3)
C4—C3—C7125.0 (4)C30—C29—C32121.1 (3)
N4—C4—C3112.9 (3)C28—C29—C32122.7 (3)
N4—C4—C8123.2 (4)C31—C30—C29121.0 (3)
C3—C4—C8123.9 (4)C31—C30—H30119.5
C1—C5—H5A109.5C29—C30—H30119.5
C1—C5—H5B109.5N11—C31—C30122.6 (3)
H5A—C5—H5B109.5N11—C31—H31118.7
C1—C5—H5C109.5C30—C31—H31118.7
H5A—C5—H5C109.5N12—C32—C29115.3 (3)
H5B—C5—H5C109.5N12—C32—S2124.3 (3)
C2—C6—H6A109.5C29—C32—S2120.4 (3)
C2—C6—H6B109.5N12—C33—C34112.2 (3)
H6A—C6—H6B109.5N12—C33—H33A109.2
C2—C6—H6C109.5C34—C33—H33A109.2
H6A—C6—H6C109.5N12—C33—H33B109.2
H6B—C6—H6C109.5C34—C33—H33B109.2
C3—C7—H7A109.5H33A—C33—H33B107.9
C3—C7—H7B109.5C35—C34—C33113.9 (4)
H7A—C7—H7B109.5C35—C34—H34A108.8
C3—C7—H7C109.5C33—C34—H34A108.8
H7A—C7—H7C109.5C35—C34—H34B108.8
H7B—C7—H7C109.5C33—C34—H34B108.8
C4—C8—H8A109.5H34A—C34—H34B107.7
C4—C8—H8B109.5C34—C35—C36112.0 (4)
H8A—C8—H8B109.5C34—C35—H35A109.2
C4—C8—H8C109.5C36—C35—H35A109.2
H8A—C8—H8C109.5C34—C35—H35B109.2
H8B—C8—H8C109.5C36—C35—H35B109.2
N5—C9—C10122.4 (4)H35A—C35—H35B107.9
N5—C9—H9118.8C35—C36—H36A109.5
C10—C9—H9118.8C35—C36—H36B109.5
C9—C10—C11119.7 (4)H36A—C36—H36B109.5
C9—C10—H10120.1C35—C36—H36C109.5
C11—C10—H10120.1H36A—C36—H36C109.5
C12—C11—C10117.4 (4)H36B—C36—H36C109.5
C12—C11—C14120.2 (4)C1—N1—O1120.9 (3)
C10—C11—C14122.5 (4)C1—N1—Co1116.7 (3)
C13—C12—C11120.2 (4)O1—N1—Co1122.5 (2)
C13—C12—H12119.9C2—N2—O2121.2 (3)
C11—C12—H12119.9C2—N2—Co1116.7 (3)
N5—C13—C12122.1 (4)O2—N2—Co1122.1 (2)
N5—C13—H13118.9C3—N3—O3121.3 (3)
C12—C13—H13118.9C3—N3—Co1115.9 (3)
N6—C14—C11113.9 (4)O3—N3—Co1122.6 (2)
N6—C14—S1124.0 (4)C4—N4—O4121.7 (3)
C11—C14—S1122.0 (4)C4—N4—Co1116.4 (3)
C16—C15—N6116.1 (5)O4—N4—Co1121.9 (2)
C16—C15—H15A108.3C9—N5—C13118.1 (3)
N6—C15—H15A108.3C9—N5—Co1120.3 (3)
C16—C15—H15B108.3C13—N5—Co1121.6 (3)
N6—C15—H15B108.3C14—N6—C15124.9 (5)
H15A—C15—H15B107.4C19—N7—O5122.6 (4)
C15—C16—C17119.1 (6)C19—N7—Co2115.5 (3)
C15—C16—H16A107.5O5—N7—Co2121.9 (3)
C17—C16—H16A107.5C20—N8—O6122.1 (4)
C15—C16—H16B107.5C20—N8—Co2115.8 (3)
C17—C16—H16B107.5O6—N8—Co2122.1 (3)
H16A—C16—H16B107.0C21—N9—O7120.2 (3)
C18—C17—C16116.6 (7)C21—N9—Co2117.0 (3)
C18—C17—H17A108.1O7—N9—Co2122.8 (3)
C16—C17—H17A108.1C22—N10—O8120.2 (3)
C18—C17—H17B108.1C22—N10—Co2117.2 (3)
C16—C17—H17B108.1O8—N10—Co2122.6 (3)
H17A—C17—H17B107.3C27—N11—C31117.1 (3)
C17—C18—H18A109.5C27—N11—Co2121.2 (2)
C17—C18—H18B109.5C31—N11—Co2121.7 (2)
H18A—C18—H18B109.5C32—N12—C33123.1 (3)
C17—C18—H18C109.5N1—O1—H1101 (3)
H18A—C18—H18C109.5N2—O2—H2106 (3)
H18B—C18—H18C109.5N3—O3—H2105 (2)
N7—C19—C20113.4 (4)N4—O4—H1101 (2)
N7—C19—C23122.7 (5)N7—O5—H8106 (3)
C20—C19—C23123.9 (5)N9—O7—H7102 (4)
N8—C20—C19113.3 (4)N10—O8—H8105 (3)
N8—C20—C24123.2 (5)N3—Co1—N481.56 (13)
C19—C20—C24123.5 (4)N3—Co1—N1177.86 (13)
N9—C21—C22112.6 (3)N4—Co1—N199.01 (13)
N9—C21—C25123.7 (4)N3—Co1—N298.28 (13)
C22—C21—C25123.7 (4)N4—Co1—N2179.43 (13)
N10—C22—C21112.4 (3)N1—Co1—N281.13 (13)
N10—C22—C26124.8 (4)N3—Co1—N591.58 (13)
C21—C22—C26122.7 (4)N4—Co1—N590.24 (12)
C19—C23—H23A109.5N1—Co1—N590.48 (12)
C19—C23—H23B109.5N2—Co1—N590.30 (12)
H23A—C23—H23B109.5N3—Co1—Cl188.31 (10)
C19—C23—H23C109.5N4—Co1—Cl189.16 (9)
H23A—C23—H23C109.5N1—Co1—Cl189.63 (9)
H23B—C23—H23C109.5N2—Co1—Cl190.29 (9)
C20—C24—H24A109.5N5—Co1—Cl1179.40 (9)
C20—C24—H24B109.5N7—Co2—N881.99 (15)
H24A—C24—H24B109.5N7—Co2—N9179.39 (15)
C20—C24—H24C109.5N8—Co2—N998.62 (14)
H24A—C24—H24C109.5N7—Co2—N1098.81 (15)
H24B—C24—H24C109.5N8—Co2—N10178.35 (14)
C21—C25—H25A109.5N9—Co2—N1080.58 (13)
C21—C25—H25B109.5N7—Co2—N1189.81 (13)
H25A—C25—H25B109.5N8—Co2—N1190.22 (13)
C21—C25—H25C109.5N9—Co2—N1190.19 (12)
H25A—C25—H25C109.5N10—Co2—N1191.23 (13)
H25B—C25—H25C109.5N7—Co2—Cl289.78 (10)
C22—C26—H26A109.5N8—Co2—Cl288.30 (10)
C22—C26—H26B109.5N9—Co2—Cl290.23 (10)
H26A—C26—H26B109.5N10—Co2—Cl290.26 (10)
C22—C26—H26C109.5N11—Co2—Cl2178.50 (9)
H26A—C26—H26C109.5
N1—C1—C2—N22.5 (5)O3—N3—Co1—N592.6 (3)
C5—C1—C2—N2−176.8 (3)C3—N3—Co1—Cl187.6 (3)
N1—C1—C2—C6−175.7 (3)O3—N3—Co1—Cl1−87.9 (3)
C5—C1—C2—C64.9 (6)C4—N4—Co1—N30.8 (3)
N3—C3—C4—N4−1.7 (5)O4—N4—Co1—N3179.7 (3)
C7—C3—C4—N4175.3 (5)C4—N4—Co1—N1−177.1 (3)
N3—C3—C4—C8178.9 (4)O4—N4—Co1—N11.8 (3)
C7—C3—C4—C8−4.1 (7)C4—N4—Co1—N2−73 (15)
N5—C9—C10—C110.8 (7)O4—N4—Co1—N2106 (15)
C9—C10—C11—C12−3.1 (7)C4—N4—Co1—N592.3 (3)
C9—C10—C11—C14176.7 (4)O4—N4—Co1—N5−88.7 (3)
C10—C11—C12—C132.7 (7)C4—N4—Co1—Cl1−87.6 (3)
C14—C11—C12—C13−177.2 (4)O4—N4—Co1—Cl191.3 (3)
C11—C12—C13—N50.2 (7)C1—N1—Co1—N376 (4)
C12—C11—C14—N6166.6 (5)O1—N1—Co1—N3−105 (3)
C10—C11—C14—N6−13.2 (7)C1—N1—Co1—N4−178.7 (3)
C12—C11—C14—S1−11.3 (6)O1—N1—Co1—N40.6 (3)
C10—C11—C14—S1168.9 (4)C1—N1—Co1—N21.8 (3)
N6—C15—C16—C17−51.0 (11)O1—N1—Co1—N2−178.8 (3)
C15—C16—C17—C18−71.2 (9)C1—N1—Co1—N5−88.4 (3)
N7—C19—C20—N8−1.8 (5)O1—N1—Co1—N591.0 (3)
C23—C19—C20—N8179.4 (4)C1—N1—Co1—Cl192.2 (3)
N7—C19—C20—C24176.9 (4)O1—N1—Co1—Cl1−88.4 (3)
C23—C19—C20—C24−1.9 (7)C2—N2—Co1—N3−178.2 (3)
N9—C21—C22—N10−3.2 (5)O2—N2—Co1—N30.5 (3)
C25—C21—C22—N10175.7 (4)C2—N2—Co1—N4−105 (15)
N9—C21—C22—C26173.9 (4)O2—N2—Co1—N474 (15)
C25—C21—C22—C26−7.2 (6)C2—N2—Co1—N1−0.3 (3)
N11—C27—C28—C290.7 (6)O2—N2—Co1—N1178.4 (3)
C27—C28—C29—C30−0.4 (5)C2—N2—Co1—N590.1 (3)
C27—C28—C29—C32−177.7 (3)O2—N2—Co1—N5−91.2 (3)
C28—C29—C30—C31−0.2 (6)C2—N2—Co1—Cl1−89.9 (3)
C32—C29—C30—C31177.1 (4)O2—N2—Co1—Cl188.8 (3)
C29—C30—C31—N110.7 (6)C9—N5—Co1—N3−42.2 (3)
C30—C29—C32—N12162.2 (4)C13—N5—Co1—N3139.4 (3)
C28—C29—C32—N12−20.7 (5)C9—N5—Co1—N4−123.7 (3)
C30—C29—C32—S2−17.2 (5)C13—N5—Co1—N457.8 (3)
C28—C29—C32—S2159.9 (3)C9—N5—Co1—N1137.3 (3)
N12—C33—C34—C35177.7 (4)C13—N5—Co1—N1−41.2 (3)
C33—C34—C35—C36−176.5 (4)C9—N5—Co1—N256.1 (3)
C2—C1—N1—O1177.8 (3)C13—N5—Co1—N2−122.4 (3)
C5—C1—N1—O1−2.9 (5)C9—N5—Co1—Cl1−122 (10)
C2—C1—N1—Co1−2.8 (4)C13—N5—Co1—Cl159 (10)
C5—C1—N1—Co1176.5 (3)C19—N7—Co2—N8−2.8 (3)
C1—C2—N2—O2−179.8 (3)O5—N7—Co2—N8177.8 (3)
C6—C2—N2—O2−1.6 (5)C19—N7—Co2—N9178 (100)
C1—C2—N2—Co1−1.1 (4)O5—N7—Co2—N9−2(14)
C6—C2—N2—Co1177.1 (3)C19—N7—Co2—N10178.6 (3)
C4—C3—N3—O3178.0 (3)O5—N7—Co2—N10−0.8 (3)
C7—C3—N3—O30.9 (7)C19—N7—Co2—N1187.4 (3)
C4—C3—N3—Co12.4 (5)O5—N7—Co2—N11−92.0 (3)
C7—C3—N3—Co1−174.7 (4)C19—N7—Co2—Cl2−91.2 (3)
C3—C4—N4—O4−178.7 (3)O5—N7—Co2—Cl289.5 (3)
C8—C4—N4—O40.6 (6)C20—N8—Co2—N71.8 (3)
C3—C4—N4—Co10.3 (4)O6—N8—Co2—N7−176.4 (3)
C8—C4—N4—Co1179.6 (3)C20—N8—Co2—N9−178.2 (3)
C10—C9—N5—C132.1 (7)O6—N8—Co2—N93.6 (3)
C10—C9—N5—Co1−176.4 (4)C20—N8—Co2—N10121 (5)
C12—C13—N5—C9−2.7 (6)O6—N8—Co2—N10−57 (5)
C12—C13—N5—Co1175.9 (3)C20—N8—Co2—N11−88.0 (3)
C11—C14—N6—C15−172.2 (5)O6—N8—Co2—N1193.8 (3)
S1—C14—N6—C155.6 (8)C20—N8—Co2—Cl291.8 (3)
C16—C15—N6—C14−86.9 (8)O6—N8—Co2—Cl2−86.4 (3)
C20—C19—N7—O5−177.4 (3)C21—N9—Co2—N7−3(14)
C23—C19—N7—O51.4 (6)O7—N9—Co2—N7−180 (100)
C20—C19—N7—Co23.3 (4)C21—N9—Co2—N8178.0 (3)
C23—C19—N7—Co2−177.9 (3)O7—N9—Co2—N81.0 (3)
C19—C20—N8—O6177.7 (3)C21—N9—Co2—N10−3.4 (3)
C24—C20—N8—O6−0.9 (6)O7—N9—Co2—N10179.6 (3)
C19—C20—N8—Co2−0.6 (4)C21—N9—Co2—N1187.8 (3)
C24—C20—N8—Co2−179.2 (3)O7—N9—Co2—N11−89.2 (3)
C22—C21—N9—O7−178.4 (3)C21—N9—Co2—Cl2−93.6 (3)
C25—C21—N9—O72.7 (6)O7—N9—Co2—Cl289.3 (3)
C22—C21—N9—Co24.5 (4)C22—N10—Co2—N7−178.5 (3)
C25—C21—N9—Co2−174.4 (3)O8—N10—Co2—N73.6 (3)
C21—C22—N10—O8178.3 (3)C22—N10—Co2—N863 (5)
C26—C22—N10—O81.4 (6)O8—N10—Co2—N8−115 (5)
C21—C22—N10—Co20.4 (4)C22—N10—Co2—N91.5 (3)
C26—C22—N10—Co2−176.5 (3)O8—N10—Co2—N9−176.4 (3)
C28—C27—N11—C31−0.2 (5)C22—N10—Co2—N11−88.5 (3)
C28—C27—N11—Co2−179.9 (3)O8—N10—Co2—N1193.6 (3)
C30—C31—N11—C27−0.4 (6)C22—N10—Co2—Cl291.7 (3)
C30—C31—N11—Co2179.2 (3)O8—N10—Co2—Cl2−86.2 (3)
C29—C32—N12—C33175.5 (3)C27—N11—Co2—N752.7 (3)
S2—C32—N12—C33−5.2 (6)C31—N11—Co2—N7−126.9 (3)
C34—C33—N12—C32−78.5 (5)C27—N11—Co2—N8134.7 (3)
C3—N3—Co1—N4−1.8 (3)C31—N11—Co2—N8−44.9 (3)
O3—N3—Co1—N4−177.4 (3)C27—N11—Co2—N9−126.7 (3)
C3—N3—Co1—N1104 (3)C31—N11—Co2—N953.7 (3)
O3—N3—Co1—N1−72 (4)C27—N11—Co2—N10−46.1 (3)
C3—N3—Co1—N2177.6 (3)C31—N11—Co2—N10134.3 (3)
O3—N3—Co1—N22.1 (3)C27—N11—Co2—Cl2127 (3)
C3—N3—Co1—N5−91.8 (3)C31—N11—Co2—Cl2−52 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O41.20 (6)1.32 (6)2.491 (4)162 (5)
O2—H2···O31.12 (6)1.39 (6)2.469 (4)158 (5)
O8—H8···O51.17 (8)1.34 (8)2.486 (5)165 (6)
O7—H7···O60.98 (7)1.52 (7)2.490 (5)171 (7)
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O41.20 (6)1.32 (6)2.491 (4)162 (5)
O2—H2···O31.12 (6)1.39 (6)2.469 (4)158 (5)
O8—H8···O51.17 (8)1.34 (8)2.486 (5)165 (6)
O7—H7···O60.98 (7)1.52 (7)2.490 (5)171 (7)
Acknowledgements top

The authors are grateful to Rev. Fr A. Albert Muthumali, SJ, Principal, Loyola College (Autonomous), Chennai, India, for providing the necessary facilities. Dr Babu Vargheese, SAIF, IIT, Madras, India is thanked for collecting and reducing the X-ray intensity data.

references
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