(N4-n-Butyl­pyridine-4-carbothio­amide-κN4)chloridobis(dimethyl­glyoximato-κ2N,N′)cobalt(III) hemihydrate

Revathi, C.; Dayalan, A.; SethuSankar, K.

doi:10.1107/S1600536809022661

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages m795-m796

doi:10.1107/S1600536809022661

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(N⁴-n-Butylpyridine-4-carbothioamide-κN⁴)chloridobis(dimethylglyoximato-κ²N,N′)cobalt(III) hemihydrate

C. Revathi,^a A. Dayalan ^a ^* and K. SethuSankar ^b

^aLoyola College (Autonomous), Chennai 600 034, Tamil Nadu, India, and ^bRKM Vivekananda College (Autonomous), Chennai 600 004, Tamil Nadu, India
^*Correspondence e-mail: revloy@gmail.com

(Received 29 April 2009; accepted 12 June 2009; online 20 June 2009)

The title compound, trans-[Co(C₄H₇N₂O₂)₂Cl(C₁₀H₁₄N₂S)]·0.5H₂O, contains two independent molecules in the asymmetric unit in which the Co^III 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).

Related literature

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 & Kohnel (1964 ); Ramesh et al. (2008 ).

Experimental

Crystal data

[Co(C₄H₇N₂O₂)₂Cl(C₁₀H₁₄N₂S)]·0.5H₂O
M_r = 526.90
Monoclinic, P 2₁ /n
a = 11.1976 (5) Å
b = 14.7889 (7) Å
c = 28.8482 (14) Å
β = 95.748 (2)°
V = 4753.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.742, T_max = 0.853
50767 measured reflections
10297 independent reflections
7510 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.168
S = 1.06
10297 reflections
606 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4	1.20 (6)	1.32 (6)	2.491 (4)	162 (5)
O2—H2⋯O3	1.12 (6)	1.39 (6)	2.469 (4)	158 (5)
O8—H8⋯O5	1.17 (8)	1.34 (8)	2.486 (5)	165 (6)
O7—H7⋯O6	0.98 (7)	1.52 (7)	2.490 (5)	171 (7)

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022661/lh2818sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022661/lh2818Isup2.hkl

checkCIF report

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 Co^III 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.

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

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)]·0.5H₂O	F(000) = 2192
M_r = 526.90	D_x = 1.473 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5420 reflections
a = 11.1976 (5) Å	θ = 2.5–26.0°
b = 14.7889 (7) Å	µ = 0.96 mm⁻¹
c = 28.8482 (14) Å	T = 293 K
β = 95.748 (2)°	Needle, brown
V = 4753.2 (4) Å³	0.3 × 0.2 × 0.2 mm
Z = 8

Data collection top

Bruker Kappa-APEX2 diffractometer	10297 independent reflections
Radiation source: fine-focus sealed tube	7510 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 0 pixels mm^-1	θ_max = 26.9°, θ_min = 1.4°
ω and ϕ scans	h = −14→10
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −18→18
T_min = 0.742, T_max = 0.853	l = −36→36
50767 measured reflections

Refinement top

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)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.168	w = 1/[σ²(F_o²) + (0.0927P)² + 3.9112P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.009
10297 reflections	Δρ_max = 0.96 e Å⁻³
606 parameters	Δρ_min = −0.82 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0023 (3)

Crystal data top

[Co(C₄H₇N₂O₂)₂Cl(C₁₀H₁₄N₂S)]·0.5H₂O	V = 4753.2 (4) Å³
M_r = 526.90	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.1976 (5) Å	µ = 0.96 mm⁻¹
b = 14.7889 (7) Å	T = 293 K
c = 28.8482 (14) Å	0.3 × 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)
T_min = 0.742, T_max = 0.853	R_int = 0.044
50767 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	1 restraint
wR(F²) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.96 e Å⁻³
10297 reflections	Δρ_min = −0.82 e Å⁻³
606 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.6540 (3)	0.4012 (2)	0.14607 (12)	0.0391 (8)
C2	0.5817 (3)	0.3183 (3)	0.13929 (13)	0.0395 (8)
C3	0.7787 (4)	0.2495 (3)	−0.01437 (14)	0.0480 (9)
C4	0.8518 (3)	0.3305 (3)	−0.00758 (13)	0.0432 (9)
C5	0.6493 (4)	0.4620 (3)	0.18669 (13)	0.0548 (11)
H5A	0.6895	0.5177	0.1811	0.082*
H5B	0.6884	0.4335	0.2140	0.082*
H5C	0.5671	0.4742	0.1913	0.082*
C6	0.4897 (4)	0.2917 (3)	0.17091 (16)	0.0579 (12)
H6A	0.4253	0.3348	0.1682	0.087*
H6B	0.5259	0.2903	0.2025	0.087*
H6C	0.4587	0.2329	0.1623	0.087*
C7	0.7738 (6)	0.1895 (4)	−0.05624 (19)	0.091 (2)
H7A	0.7375	0.1328	−0.0494	0.137*
H7B	0.8537	0.1790	−0.0644	0.137*
H7C	0.7270	0.2180	−0.0818	0.137*
C8	0.9383 (4)	0.3614 (3)	−0.04059 (15)	0.0570 (11)
H8A	0.9657	0.4213	−0.0323	0.085*
H8B	0.8991	0.3618	−0.0717	0.085*
H8C	1.0056	0.3209	−0.0389	0.085*
C9	0.8419 (4)	0.1681 (3)	0.10754 (17)	0.0542 (11)
H9	0.7787	0.1375	0.0911	0.065*
C10	0.9260 (4)	0.1193 (3)	0.13510 (17)	0.0587 (12)
H10	0.9197	0.0567	0.1368	0.070*
C11	1.0198 (4)	0.1636 (3)	0.16024 (14)	0.0486 (10)
C12	1.0274 (4)	0.2554 (3)	0.15450 (16)	0.0536 (10)
H12	1.0911	0.2873	0.1698	0.064*
C13	0.9412 (4)	0.3003 (3)	0.12621 (14)	0.0458 (9)
H13	0.9481	0.3626	0.1227	0.055*
C14	1.1118 (4)	0.1146 (4)	0.19326 (17)	0.0641 (12)
C15	1.1459 (6)	−0.0284 (5)	0.2383 (2)	0.0906 (19)
H15A	1.1778	0.0094	0.2641	0.109*
H15B	1.0891	−0.0699	0.2501	0.109*
C16	1.2409 (7)	−0.0793 (5)	0.2233 (2)	0.113 (3)
H16A	1.2700	−0.1194	0.2485	0.136*
H16B	1.3056	−0.0376	0.2186	0.136*
C17	1.2186 (6)	−0.1359 (5)	0.1797 (2)	0.0895 (18)
H17A	1.1807	−0.0978	0.1551	0.107*
H17B	1.2957	−0.1545	0.1704	0.107*
C18	1.1436 (6)	−0.2176 (5)	0.1829 (3)	0.107 (2)
H18A	1.1685	−0.2491	0.2114	0.161*
H18B	1.1528	−0.2564	0.1569	0.161*
H18C	1.0610	−0.2002	0.1827	0.161*
C19	0.8873 (4)	0.4019 (3)	0.40245 (15)	0.0548 (11)
C20	0.9481 (4)	0.4264 (3)	0.36220 (16)	0.0510 (10)
C21	0.7077 (4)	0.1755 (3)	0.26363 (13)	0.0442 (9)
C22	0.6402 (3)	0.1546 (3)	0.30342 (14)	0.0441 (9)
C23	0.9121 (6)	0.4454 (4)	0.44954 (18)	0.0843 (18)
H23A	0.8644	0.4167	0.4712	0.126*
H23B	0.8920	0.5085	0.4473	0.126*
H23C	0.9956	0.4389	0.4602	0.126*
C24	1.0394 (5)	0.4994 (3)	0.3627 (2)	0.0781 (16)
H24A	1.0620	0.5080	0.3317	0.117*
H24B	1.1088	0.4828	0.3831	0.117*
H24C	1.0063	0.5545	0.3734	0.117*
C25	0.6947 (5)	0.1242 (3)	0.21891 (16)	0.0650 (13)
H25A	0.7317	0.1575	0.1956	0.098*
H25B	0.6111	0.1157	0.2089	0.098*
H25C	0.7330	0.0663	0.2234	0.098*
C26	0.5420 (4)	0.0867 (3)	0.3009 (2)	0.0681 (13)
H26A	0.5214	0.0740	0.3317	0.102*
H26B	0.5682	0.0321	0.2871	0.102*
H26C	0.4731	0.1102	0.2823	0.102*
C27	0.9110 (3)	0.1502 (2)	0.38996 (12)	0.0374 (8)
H27	0.8439	0.1560	0.4063	0.045*
C28	0.9965 (3)	0.0876 (3)	0.40509 (12)	0.0375 (8)
H28	0.9862	0.0517	0.4309	0.045*
C29	1.0991 (3)	0.0776 (2)	0.38179 (12)	0.0361 (8)
C30	1.1068 (4)	0.1332 (3)	0.34363 (14)	0.0447 (9)
H30	1.1735	0.1293	0.3270	0.054*
C31	1.0177 (4)	0.1937 (3)	0.33005 (14)	0.0430 (9)
H31	1.0254	0.2296	0.3040	0.052*
C32	1.1937 (3)	0.0082 (3)	0.39541 (13)	0.0397 (8)
C33	1.2757 (4)	−0.0957 (3)	0.45690 (15)	0.0512 (10)
H33A	1.2829	−0.0937	0.4907	0.061*
H33B	1.3549	−0.0859	0.4469	0.061*
C34	1.2308 (4)	−0.1880 (3)	0.44078 (18)	0.0555 (11)
H34A	1.1529	−0.1982	0.4518	0.067*
H34B	1.2202	−0.1887	0.4070	0.067*
C35	1.3131 (4)	−0.2642 (3)	0.45739 (17)	0.0588 (11)
H35A	1.3197	−0.2665	0.4912	0.071*
H35B	1.3925	−0.2527	0.4480	0.071*
C36	1.2683 (5)	−0.3549 (4)	0.4380 (2)	0.0869 (18)
H36A	1.1937	−0.3695	0.4499	0.130*
H36B	1.3265	−0.4008	0.4471	0.130*
H36C	1.2564	−0.3516	0.4046	0.130*
N1	0.7222 (3)	0.4142 (2)	0.11309 (10)	0.0356 (6)
N2	0.6040 (3)	0.2735 (2)	0.10299 (10)	0.0359 (6)
N3	0.7116 (3)	0.2353 (2)	0.01918 (11)	0.0403 (7)
N4	0.8335 (3)	0.3740 (2)	0.02985 (10)	0.0355 (6)
N5	0.8476 (3)	0.2575 (2)	0.10354 (10)	0.0347 (6)
N6	1.0805 (4)	0.0297 (3)	0.20319 (16)	0.0767 (13)
N7	0.8069 (3)	0.3394 (2)	0.39383 (11)	0.0465 (8)
N8	0.9133 (3)	0.3797 (2)	0.32561 (12)	0.0444 (8)
N9	0.7812 (3)	0.2424 (2)	0.27193 (10)	0.0388 (7)
N10	0.6723 (3)	0.2043 (2)	0.33924 (11)	0.0409 (7)
N11	0.9195 (3)	0.20336 (19)	0.35282 (10)	0.0331 (6)
N12	1.1953 (3)	−0.0228 (2)	0.43840 (12)	0.0465 (8)
O1	0.7913 (3)	0.48767 (17)	0.11270 (9)	0.0465 (6)
O2	0.5463 (3)	0.19640 (18)	0.09123 (11)	0.0504 (7)
O3	0.6361 (3)	0.1655 (2)	0.01808 (11)	0.0589 (8)
O4	0.8906 (2)	0.45087 (19)	0.04153 (10)	0.0470 (6)
O5	0.7379 (3)	0.3099 (2)	0.42581 (10)	0.0642 (9)
O6	0.9561 (3)	0.3945 (2)	0.28445 (11)	0.0569 (8)
O7	0.8475 (3)	0.2714 (2)	0.23890 (10)	0.0545 (7)
O8	0.6170 (3)	0.1955 (2)	0.37864 (11)	0.0570 (8)
O9	0.5206 (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)
S1	1.22943 (19)	0.16153 (15)	0.21468 (9)	0.1222 (8)
S2	1.28739 (11)	−0.02367 (9)	0.35816 (4)	0.0642 (3)
Cl1	0.57535 (8)	0.39973 (6)	0.02391 (3)	0.0401 (2)
Cl2	0.65579 (9)	0.39511 (7)	0.31055 (4)	0.0494 (3)
Co1	0.71972 (4)	0.32373 (3)	0.066535 (15)	0.02991 (14)
Co2	0.79476 (4)	0.29152 (3)	0.333079 (16)	0.03392 (14)
H1	0.829 (5)	0.480 (4)	0.076 (2)	0.092 (17)*
H2	0.566 (5)	0.181 (4)	0.055 (2)	0.090 (18)*
H8	0.670 (6)	0.244 (5)	0.406 (3)	0.13 (2)*
H7	0.890 (6)	0.323 (5)	0.254 (3)	0.13 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.051 (2)	0.039 (2)	0.0281 (17)	0.0090 (16)	0.0051 (15)	0.0082 (15)
C2	0.0390 (19)	0.046 (2)	0.0340 (19)	0.0050 (16)	0.0060 (15)	0.0135 (16)
C3	0.060 (2)	0.046 (2)	0.039 (2)	0.0048 (19)	0.0079 (18)	−0.0063 (17)
C4	0.044 (2)	0.047 (2)	0.040 (2)	0.0068 (17)	0.0091 (16)	0.0049 (17)
C5	0.077 (3)	0.055 (3)	0.032 (2)	0.011 (2)	0.006 (2)	0.0002 (18)
C6	0.055 (2)	0.071 (3)	0.051 (3)	0.008 (2)	0.020 (2)	0.021 (2)
C7	0.138 (6)	0.084 (4)	0.056 (3)	−0.013 (4)	0.031 (3)	−0.029 (3)
C8	0.055 (2)	0.076 (3)	0.043 (2)	0.004 (2)	0.0205 (19)	0.004 (2)
C9	0.054 (2)	0.039 (2)	0.067 (3)	−0.0056 (19)	−0.009 (2)	0.010 (2)
C10	0.059 (3)	0.039 (2)	0.075 (3)	−0.0016 (19)	−0.008 (2)	0.018 (2)
C11	0.046 (2)	0.056 (3)	0.043 (2)	0.0080 (19)	0.0039 (17)	0.0119 (19)
C12	0.048 (2)	0.053 (3)	0.057 (3)	−0.0051 (19)	−0.0082 (19)	0.005 (2)
C13	0.046 (2)	0.039 (2)	0.051 (2)	−0.0044 (17)	−0.0002 (18)	0.0059 (18)
C14	0.062 (3)	0.073 (3)	0.056 (3)	0.011 (2)	−0.002 (2)	0.009 (2)
C15	0.114 (5)	0.095 (5)	0.060 (3)	0.035 (4)	−0.003 (3)	0.008 (3)
C16	0.132 (6)	0.127 (6)	0.073 (4)	0.057 (5)	−0.023 (4)	−0.020 (4)
C17	0.090 (4)	0.094 (5)	0.083 (4)	0.018 (4)	0.000 (3)	−0.022 (4)
C18	0.077 (4)	0.123 (6)	0.123 (6)	−0.002 (4)	0.016 (4)	−0.013 (5)
C19	0.070 (3)	0.041 (2)	0.049 (2)	0.020 (2)	−0.015 (2)	−0.0140 (19)
C20	0.050 (2)	0.0300 (19)	0.070 (3)	0.0063 (17)	−0.010 (2)	−0.0070 (19)
C21	0.053 (2)	0.039 (2)	0.039 (2)	0.0093 (18)	−0.0025 (17)	−0.0019 (16)
C22	0.042 (2)	0.037 (2)	0.052 (2)	0.0029 (16)	0.0001 (17)	0.0060 (18)
C23	0.116 (5)	0.067 (3)	0.062 (3)	0.021 (3)	−0.029 (3)	−0.028 (3)
C24	0.069 (3)	0.042 (3)	0.120 (5)	−0.004 (2)	−0.008 (3)	−0.015 (3)
C25	0.091 (4)	0.054 (3)	0.047 (3)	0.004 (2)	−0.006 (2)	−0.014 (2)
C26	0.058 (3)	0.059 (3)	0.086 (4)	−0.012 (2)	−0.002 (2)	0.008 (3)
C27	0.0402 (18)	0.042 (2)	0.0309 (18)	0.0037 (16)	0.0081 (14)	0.0000 (15)
C28	0.0417 (19)	0.042 (2)	0.0288 (17)	0.0010 (16)	0.0030 (14)	0.0023 (15)
C29	0.0375 (18)	0.0343 (18)	0.0368 (18)	0.0001 (15)	0.0051 (14)	−0.0064 (15)
C30	0.045 (2)	0.040 (2)	0.052 (2)	0.0029 (17)	0.0173 (17)	0.0030 (18)
C31	0.050 (2)	0.0361 (19)	0.045 (2)	0.0023 (16)	0.0187 (17)	0.0075 (16)
C32	0.0373 (18)	0.0371 (19)	0.044 (2)	−0.0007 (15)	−0.0009 (15)	−0.0043 (16)
C33	0.048 (2)	0.054 (2)	0.049 (2)	0.0111 (19)	−0.0052 (18)	0.004 (2)
C34	0.046 (2)	0.051 (2)	0.069 (3)	0.0056 (19)	−0.002 (2)	0.007 (2)
C35	0.058 (3)	0.056 (3)	0.062 (3)	0.007 (2)	0.000 (2)	0.009 (2)
C36	0.088 (4)	0.051 (3)	0.119 (5)	0.007 (3)	0.000 (4)	0.001 (3)
N1	0.0434 (16)	0.0311 (15)	0.0319 (15)	−0.0013 (12)	0.0025 (12)	0.0033 (12)
N2	0.0349 (15)	0.0338 (15)	0.0393 (16)	−0.0028 (12)	0.0060 (12)	0.0079 (13)
N3	0.0486 (17)	0.0327 (16)	0.0391 (17)	−0.0030 (13)	0.0017 (14)	−0.0028 (13)
N4	0.0390 (15)	0.0349 (16)	0.0333 (15)	−0.0028 (13)	0.0069 (12)	0.0044 (12)
N5	0.0363 (15)	0.0330 (15)	0.0353 (15)	−0.0023 (12)	0.0066 (12)	0.0036 (12)
N6	0.092 (3)	0.061 (3)	0.074 (3)	0.022 (2)	−0.009 (2)	0.017 (2)
N7	0.062 (2)	0.0415 (19)	0.0356 (17)	0.0155 (16)	0.0042 (15)	−0.0054 (14)
N8	0.0500 (18)	0.0311 (16)	0.0513 (19)	0.0065 (14)	0.0022 (15)	0.0021 (14)
N9	0.0497 (17)	0.0362 (16)	0.0315 (15)	0.0042 (14)	0.0088 (13)	0.0021 (13)
N10	0.0433 (17)	0.0425 (17)	0.0382 (17)	0.0051 (14)	0.0099 (13)	0.0057 (14)
N11	0.0403 (15)	0.0281 (14)	0.0313 (15)	0.0018 (12)	0.0053 (12)	−0.0008 (12)
N12	0.0441 (17)	0.0459 (19)	0.0483 (19)	0.0084 (15)	−0.0002 (14)	0.0053 (15)
O1	0.0613 (17)	0.0344 (14)	0.0440 (15)	−0.0121 (12)	0.0056 (13)	−0.0032 (12)
O2	0.0487 (16)	0.0403 (15)	0.0625 (19)	−0.0163 (12)	0.0079 (14)	0.0053 (13)
O3	0.073 (2)	0.0419 (16)	0.0602 (19)	−0.0208 (15)	0.0010 (16)	−0.0103 (14)
O4	0.0496 (15)	0.0447 (15)	0.0475 (15)	−0.0196 (13)	0.0094 (12)	0.0037 (12)
O5	0.089 (2)	0.070 (2)	0.0364 (16)	0.0175 (18)	0.0160 (16)	−0.0037 (15)
O6	0.0630 (18)	0.0475 (17)	0.0631 (19)	−0.0028 (14)	0.0211 (15)	0.0125 (14)
O7	0.074 (2)	0.0575 (19)	0.0352 (15)	0.0007 (16)	0.0202 (14)	0.0040 (13)
O8	0.0560 (17)	0.068 (2)	0.0516 (18)	0.0074 (15)	0.0273 (14)	0.0159 (15)
O9	0.071 (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)
S1	0.1044 (13)	0.1075 (15)	0.1419 (18)	−0.0176 (11)	−0.0507 (13)	0.0240 (13)
S2	0.0658 (7)	0.0746 (8)	0.0535 (7)	0.0232 (6)	0.0127 (6)	0.0032 (6)
Cl1	0.0417 (5)	0.0443 (5)	0.0342 (4)	0.0051 (4)	0.0029 (3)	0.0077 (4)
Cl2	0.0552 (6)	0.0440 (5)	0.0482 (5)	0.0141 (4)	0.0019 (4)	0.0042 (4)
Co1	0.0343 (2)	0.0272 (2)	0.0284 (2)	−0.00359 (18)	0.00409 (18)	0.00201 (18)
Co2	0.0419 (3)	0.0305 (3)	0.0297 (3)	0.0035 (2)	0.00545 (19)	0.00001 (19)

Geometric parameters (Å, º) top

C1—N1	1.293 (4)	C24—H24B	0.9600
C1—C2	1.471 (5)	C24—H24C	0.9600
C1—C5	1.483 (5)	C25—H25A	0.9600
C2—N2	1.284 (5)	C25—H25B	0.9600
C2—C6	1.496 (5)	C25—H25C	0.9600
C3—N3	1.300 (5)	C26—H26A	0.9600
C3—C4	1.453 (6)	C26—H26B	0.9600
C3—C7	1.495 (6)	C26—H26C	0.9600
C4—N4	1.291 (5)	C27—N11	1.340 (4)
C4—C8	1.496 (5)	C27—C28	1.371 (5)
C5—H5A	0.9600	C27—H27	0.9300
C5—H5B	0.9600	C28—C29	1.395 (5)
C5—H5C	0.9600	C28—H28	0.9300
C6—H6A	0.9600	C29—C30	1.383 (5)
C6—H6B	0.9600	C29—C32	1.499 (5)
C6—H6C	0.9600	C30—C31	1.368 (5)
C7—H7A	0.9600	C30—H30	0.9300
C7—H7B	0.9600	C31—N11	1.343 (5)
C7—H7C	0.9600	C31—H31	0.9300
C8—H8A	0.9600	C32—N12	1.321 (5)
C8—H8B	0.9600	C32—S2	1.644 (4)
C8—H8C	0.9600	C33—N12	1.469 (5)
C9—N5	1.330 (5)	C33—C34	1.512 (6)
C9—C10	1.374 (6)	C33—H33A	0.9700
C9—H9	0.9300	C33—H33B	0.9700
C10—C11	1.381 (6)	C34—C35	1.503 (6)
C10—H10	0.9300	C34—H34A	0.9700
C11—C12	1.371 (6)	C34—H34B	0.9700
C11—C14	1.516 (6)	C35—C36	1.519 (7)
C12—C13	1.371 (6)	C35—H35A	0.9700
C12—H12	0.9300	C35—H35B	0.9700
C13—N5	1.337 (5)	C36—H36A	0.9600
C13—H13	0.9300	C36—H36B	0.9600
C14—N6	1.343 (7)	C36—H36C	0.9600
C14—S1	1.560 (5)	N1—O1	1.335 (4)
C15—C16	1.407 (8)	N1—Co1	1.894 (3)
C15—N6	1.467 (6)	N2—O2	1.338 (4)
C15—H15A	0.9700	N2—Co1	1.900 (3)
C15—H15B	0.9700	N3—O3	1.333 (4)
C16—C17	1.510 (8)	N3—Co1	1.887 (3)
C16—H16A	0.9700	N4—O4	1.331 (4)
C16—H16B	0.9700	N4—Co1	1.889 (3)
C17—C18	1.480 (9)	N5—Co1	1.960 (3)
C17—H17A	0.9700	N7—O5	1.334 (5)
C17—H17B	0.9700	N7—Co2	1.882 (3)
C18—H18A	0.9600	N8—O6	1.343 (4)
C18—H18B	0.9600	N8—Co2	1.888 (3)
C18—H18C	0.9600	N9—O7	1.336 (4)
C19—N7	1.297 (6)	N9—Co2	1.900 (3)
C19—C20	1.450 (7)	N10—O8	1.354 (4)
C19—C23	1.504 (6)	N10—Co2	1.904 (3)
C20—N8	1.288 (5)	N11—Co2	1.954 (3)
C20—C24	1.486 (6)	O1—H1	1.20 (6)
C21—N9	1.293 (5)	O2—H2	1.12 (6)
C21—C22	1.469 (6)	O3—H2	1.39 (6)
C21—C25	1.492 (6)	O4—H1	1.32 (6)
C22—N10	1.290 (5)	O5—H8	1.34 (8)
C22—C26	1.485 (6)	O7—H7	0.98 (7)
C23—H23A	0.9600	O8—H8	1.17 (8)
C23—H23B	0.9600	Cl1—Co1	2.2341 (10)
C23—H23C	0.9600	Cl2—Co2	2.2334 (10)
C24—H24A	0.9600

N1—C1—C2	112.6 (3)	H26B—C26—H26C	109.5
N1—C1—C5	124.2 (4)	N11—C27—C28	123.2 (3)
C2—C1—C5	123.3 (3)	N11—C27—H27	118.4
N2—C2—C1	112.9 (3)	C28—C27—H27	118.4
N2—C2—C6	124.3 (4)	C27—C28—C29	120.0 (3)
C1—C2—C6	122.8 (4)	C27—C28—H28	120.0
N3—C3—C4	113.1 (3)	C29—C28—H28	120.0
N3—C3—C7	121.9 (4)	C30—C29—C28	116.2 (3)
C4—C3—C7	125.0 (4)	C30—C29—C32	121.1 (3)
N4—C4—C3	112.9 (3)	C28—C29—C32	122.7 (3)
N4—C4—C8	123.2 (4)	C31—C30—C29	121.0 (3)
C3—C4—C8	123.9 (4)	C31—C30—H30	119.5
C1—C5—H5A	109.5	C29—C30—H30	119.5
C1—C5—H5B	109.5	N11—C31—C30	122.6 (3)
H5A—C5—H5B	109.5	N11—C31—H31	118.7
C1—C5—H5C	109.5	C30—C31—H31	118.7
H5A—C5—H5C	109.5	N12—C32—C29	115.3 (3)
H5B—C5—H5C	109.5	N12—C32—S2	124.3 (3)
C2—C6—H6A	109.5	C29—C32—S2	120.4 (3)
C2—C6—H6B	109.5	N12—C33—C34	112.2 (3)
H6A—C6—H6B	109.5	N12—C33—H33A	109.2
C2—C6—H6C	109.5	C34—C33—H33A	109.2
H6A—C6—H6C	109.5	N12—C33—H33B	109.2
H6B—C6—H6C	109.5	C34—C33—H33B	109.2
C3—C7—H7A	109.5	H33A—C33—H33B	107.9
C3—C7—H7B	109.5	C35—C34—C33	113.9 (4)
H7A—C7—H7B	109.5	C35—C34—H34A	108.8
C3—C7—H7C	109.5	C33—C34—H34A	108.8
H7A—C7—H7C	109.5	C35—C34—H34B	108.8
H7B—C7—H7C	109.5	C33—C34—H34B	108.8
C4—C8—H8A	109.5	H34A—C34—H34B	107.7
C4—C8—H8B	109.5	C34—C35—C36	112.0 (4)
H8A—C8—H8B	109.5	C34—C35—H35A	109.2
C4—C8—H8C	109.5	C36—C35—H35A	109.2
H8A—C8—H8C	109.5	C34—C35—H35B	109.2
H8B—C8—H8C	109.5	C36—C35—H35B	109.2
N5—C9—C10	122.4 (4)	H35A—C35—H35B	107.9
N5—C9—H9	118.8	C35—C36—H36A	109.5
C10—C9—H9	118.8	C35—C36—H36B	109.5
C9—C10—C11	119.7 (4)	H36A—C36—H36B	109.5
C9—C10—H10	120.1	C35—C36—H36C	109.5
C11—C10—H10	120.1	H36A—C36—H36C	109.5
C12—C11—C10	117.4 (4)	H36B—C36—H36C	109.5
C12—C11—C14	120.2 (4)	C1—N1—O1	120.9 (3)
C10—C11—C14	122.5 (4)	C1—N1—Co1	116.7 (3)
C13—C12—C11	120.2 (4)	O1—N1—Co1	122.5 (2)
C13—C12—H12	119.9	C2—N2—O2	121.2 (3)
C11—C12—H12	119.9	C2—N2—Co1	116.7 (3)
N5—C13—C12	122.1 (4)	O2—N2—Co1	122.1 (2)
N5—C13—H13	118.9	C3—N3—O3	121.3 (3)
C12—C13—H13	118.9	C3—N3—Co1	115.9 (3)
N6—C14—C11	113.9 (4)	O3—N3—Co1	122.6 (2)
N6—C14—S1	124.0 (4)	C4—N4—O4	121.7 (3)
C11—C14—S1	122.0 (4)	C4—N4—Co1	116.4 (3)
C16—C15—N6	116.1 (5)	O4—N4—Co1	121.9 (2)
C16—C15—H15A	108.3	C9—N5—C13	118.1 (3)
N6—C15—H15A	108.3	C9—N5—Co1	120.3 (3)
C16—C15—H15B	108.3	C13—N5—Co1	121.6 (3)
N6—C15—H15B	108.3	C14—N6—C15	124.9 (5)
H15A—C15—H15B	107.4	C19—N7—O5	122.6 (4)
C15—C16—C17	119.1 (6)	C19—N7—Co2	115.5 (3)
C15—C16—H16A	107.5	O5—N7—Co2	121.9 (3)
C17—C16—H16A	107.5	C20—N8—O6	122.1 (4)
C15—C16—H16B	107.5	C20—N8—Co2	115.8 (3)
C17—C16—H16B	107.5	O6—N8—Co2	122.1 (3)
H16A—C16—H16B	107.0	C21—N9—O7	120.2 (3)
C18—C17—C16	116.6 (7)	C21—N9—Co2	117.0 (3)
C18—C17—H17A	108.1	O7—N9—Co2	122.8 (3)
C16—C17—H17A	108.1	C22—N10—O8	120.2 (3)
C18—C17—H17B	108.1	C22—N10—Co2	117.2 (3)
C16—C17—H17B	108.1	O8—N10—Co2	122.6 (3)
H17A—C17—H17B	107.3	C27—N11—C31	117.1 (3)
C17—C18—H18A	109.5	C27—N11—Co2	121.2 (2)
C17—C18—H18B	109.5	C31—N11—Co2	121.7 (2)
H18A—C18—H18B	109.5	C32—N12—C33	123.1 (3)
C17—C18—H18C	109.5	N1—O1—H1	101 (3)
H18A—C18—H18C	109.5	N2—O2—H2	106 (3)
H18B—C18—H18C	109.5	N3—O3—H2	105 (2)
N7—C19—C20	113.4 (4)	N4—O4—H1	101 (2)
N7—C19—C23	122.7 (5)	N7—O5—H8	106 (3)
C20—C19—C23	123.9 (5)	N9—O7—H7	102 (4)
N8—C20—C19	113.3 (4)	N10—O8—H8	105 (3)
N8—C20—C24	123.2 (5)	N3—Co1—N4	81.56 (13)
C19—C20—C24	123.5 (4)	N3—Co1—N1	177.86 (13)
N9—C21—C22	112.6 (3)	N4—Co1—N1	99.01 (13)
N9—C21—C25	123.7 (4)	N3—Co1—N2	98.28 (13)
C22—C21—C25	123.7 (4)	N4—Co1—N2	179.43 (13)
N10—C22—C21	112.4 (3)	N1—Co1—N2	81.13 (13)
N10—C22—C26	124.8 (4)	N3—Co1—N5	91.58 (13)
C21—C22—C26	122.7 (4)	N4—Co1—N5	90.24 (12)
C19—C23—H23A	109.5	N1—Co1—N5	90.48 (12)
C19—C23—H23B	109.5	N2—Co1—N5	90.30 (12)
H23A—C23—H23B	109.5	N3—Co1—Cl1	88.31 (10)
C19—C23—H23C	109.5	N4—Co1—Cl1	89.16 (9)
H23A—C23—H23C	109.5	N1—Co1—Cl1	89.63 (9)
H23B—C23—H23C	109.5	N2—Co1—Cl1	90.29 (9)
C20—C24—H24A	109.5	N5—Co1—Cl1	179.40 (9)
C20—C24—H24B	109.5	N7—Co2—N8	81.99 (15)
H24A—C24—H24B	109.5	N7—Co2—N9	179.39 (15)
C20—C24—H24C	109.5	N8—Co2—N9	98.62 (14)
H24A—C24—H24C	109.5	N7—Co2—N10	98.81 (15)
H24B—C24—H24C	109.5	N8—Co2—N10	178.35 (14)
C21—C25—H25A	109.5	N9—Co2—N10	80.58 (13)
C21—C25—H25B	109.5	N7—Co2—N11	89.81 (13)
H25A—C25—H25B	109.5	N8—Co2—N11	90.22 (13)
C21—C25—H25C	109.5	N9—Co2—N11	90.19 (12)
H25A—C25—H25C	109.5	N10—Co2—N11	91.23 (13)
H25B—C25—H25C	109.5	N7—Co2—Cl2	89.78 (10)
C22—C26—H26A	109.5	N8—Co2—Cl2	88.30 (10)
C22—C26—H26B	109.5	N9—Co2—Cl2	90.23 (10)
H26A—C26—H26B	109.5	N10—Co2—Cl2	90.26 (10)
C22—C26—H26C	109.5	N11—Co2—Cl2	178.50 (9)
H26A—C26—H26C	109.5

N1—C1—C2—N2	2.5 (5)	O3—N3—Co1—N5	92.6 (3)
C5—C1—C2—N2	−176.8 (3)	C3—N3—Co1—Cl1	87.6 (3)
N1—C1—C2—C6	−175.7 (3)	O3—N3—Co1—Cl1	−87.9 (3)
C5—C1—C2—C6	4.9 (6)	C4—N4—Co1—N3	0.8 (3)
N3—C3—C4—N4	−1.7 (5)	O4—N4—Co1—N3	179.7 (3)
C7—C3—C4—N4	175.3 (5)	C4—N4—Co1—N1	−177.1 (3)
N3—C3—C4—C8	178.9 (4)	O4—N4—Co1—N1	1.8 (3)
C7—C3—C4—C8	−4.1 (7)	C4—N4—Co1—N2	−73 (15)
N5—C9—C10—C11	0.8 (7)	O4—N4—Co1—N2	106 (15)
C9—C10—C11—C12	−3.1 (7)	C4—N4—Co1—N5	92.3 (3)
C9—C10—C11—C14	176.7 (4)	O4—N4—Co1—N5	−88.7 (3)
C10—C11—C12—C13	2.7 (7)	C4—N4—Co1—Cl1	−87.6 (3)
C14—C11—C12—C13	−177.2 (4)	O4—N4—Co1—Cl1	91.3 (3)
C11—C12—C13—N5	0.2 (7)	C1—N1—Co1—N3	76 (4)
C12—C11—C14—N6	166.6 (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—N4	0.6 (3)
C10—C11—C14—S1	168.9 (4)	C1—N1—Co1—N2	1.8 (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—N5	91.0 (3)
C23—C19—C20—N8	179.4 (4)	C1—N1—Co1—Cl1	92.2 (3)
N7—C19—C20—C24	176.9 (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—N3	0.5 (3)
C25—C21—C22—N10	175.7 (4)	C2—N2—Co1—N4	−105 (15)
N9—C21—C22—C26	173.9 (4)	O2—N2—Co1—N4	74 (15)
C25—C21—C22—C26	−7.2 (6)	C2—N2—Co1—N1	−0.3 (3)
N11—C27—C28—C29	0.7 (6)	O2—N2—Co1—N1	178.4 (3)
C27—C28—C29—C30	−0.4 (5)	C2—N2—Co1—N5	90.1 (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—C31	177.1 (4)	O2—N2—Co1—Cl1	88.8 (3)
C29—C30—C31—N11	0.7 (6)	C9—N5—Co1—N3	−42.2 (3)
C30—C29—C32—N12	162.2 (4)	C13—N5—Co1—N3	139.4 (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—N4	57.8 (3)
C28—C29—C32—S2	159.9 (3)	C9—N5—Co1—N1	137.3 (3)
N12—C33—C34—C35	177.7 (4)	C13—N5—Co1—N1	−41.2 (3)
C33—C34—C35—C36	−176.5 (4)	C9—N5—Co1—N2	56.1 (3)
C2—C1—N1—O1	177.8 (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—Cl1	59 (10)
C5—C1—N1—Co1	176.5 (3)	C19—N7—Co2—N8	−2.8 (3)
C1—C2—N2—O2	−179.8 (3)	O5—N7—Co2—N8	177.8 (3)
C6—C2—N2—O2	−1.6 (5)	C19—N7—Co2—N9	178 (100)
C1—C2—N2—Co1	−1.1 (4)	O5—N7—Co2—N9	−2 (14)
C6—C2—N2—Co1	177.1 (3)	C19—N7—Co2—N10	178.6 (3)
C4—C3—N3—O3	178.0 (3)	O5—N7—Co2—N10	−0.8 (3)
C7—C3—N3—O3	0.9 (7)	C19—N7—Co2—N11	87.4 (3)
C4—C3—N3—Co1	2.4 (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—Cl2	89.5 (3)
C8—C4—N4—O4	0.6 (6)	C20—N8—Co2—N7	1.8 (3)
C3—C4—N4—Co1	0.3 (4)	O6—N8—Co2—N7	−176.4 (3)
C8—C4—N4—Co1	179.6 (3)	C20—N8—Co2—N9	−178.2 (3)
C10—C9—N5—C13	2.1 (7)	O6—N8—Co2—N9	3.6 (3)
C10—C9—N5—Co1	−176.4 (4)	C20—N8—Co2—N10	121 (5)
C12—C13—N5—C9	−2.7 (6)	O6—N8—Co2—N10	−57 (5)
C12—C13—N5—Co1	175.9 (3)	C20—N8—Co2—N11	−88.0 (3)
C11—C14—N6—C15	−172.2 (5)	O6—N8—Co2—N11	93.8 (3)
S1—C14—N6—C15	5.6 (8)	C20—N8—Co2—Cl2	91.8 (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—O5	1.4 (6)	O7—N9—Co2—N7	−180 (100)
C20—C19—N7—Co2	3.3 (4)	C21—N9—Co2—N8	178.0 (3)
C23—C19—N7—Co2	−177.9 (3)	O7—N9—Co2—N8	1.0 (3)
C19—C20—N8—O6	177.7 (3)	C21—N9—Co2—N10	−3.4 (3)
C24—C20—N8—O6	−0.9 (6)	O7—N9—Co2—N10	179.6 (3)
C19—C20—N8—Co2	−0.6 (4)	C21—N9—Co2—N11	87.8 (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—O7	2.7 (6)	O7—N9—Co2—Cl2	89.3 (3)
C22—C21—N9—Co2	4.5 (4)	C22—N10—Co2—N7	−178.5 (3)
C25—C21—N9—Co2	−174.4 (3)	O8—N10—Co2—N7	3.6 (3)
C21—C22—N10—O8	178.3 (3)	C22—N10—Co2—N8	63 (5)
C26—C22—N10—O8	1.4 (6)	O8—N10—Co2—N8	−115 (5)
C21—C22—N10—Co2	0.4 (4)	C22—N10—Co2—N9	1.5 (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—N11	93.6 (3)
C30—C31—N11—C27	−0.4 (6)	C22—N10—Co2—Cl2	91.7 (3)
C30—C31—N11—Co2	179.2 (3)	O8—N10—Co2—Cl2	−86.2 (3)
C29—C32—N12—C33	175.5 (3)	C27—N11—Co2—N7	52.7 (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—N8	134.7 (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—N1	104 (3)	C31—N11—Co2—N9	53.7 (3)
O3—N3—Co1—N1	−72 (4)	C27—N11—Co2—N10	−46.1 (3)
C3—N3—Co1—N2	177.6 (3)	C31—N11—Co2—N10	134.3 (3)
O3—N3—Co1—N2	2.1 (3)	C27—N11—Co2—Cl2	127 (3)
C3—N3—Co1—N5	−91.8 (3)	C31—N11—Co2—Cl2	−52 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	1.20 (6)	1.32 (6)	2.491 (4)	162 (5)
O2—H2···O3	1.12 (6)	1.39 (6)	2.469 (4)	158 (5)
O8—H8···O5	1.17 (8)	1.34 (8)	2.486 (5)	165 (6)
O7—H7···O6	0.98 (7)	1.52 (7)	2.490 (5)	171 (7)

Experimental details

Crystal data
Chemical formula	[Co(C₄H₇N₂O₂)₂Cl(C₁₀H₁₄N₂S)]·0.5H₂O
M_r	526.90
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.1976 (5), 14.7889 (7), 28.8482 (14)
β (°)	95.748 (2)
V (Å³)	4753.2 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Bruker Kappa-APEX2 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.742, 0.853
No. of measured, independent and observed [I > 2σ(I)] reflections	50767, 10297, 7510
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.637

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.168, 1.06
No. of reflections	10297
No. of parameters	606
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.82

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT (Bruker, 2004), SIR92 (Altornare et al., 1993), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	1.20 (6)	1.32 (6)	2.491 (4)	162 (5)
O2—H2···O3	1.12 (6)	1.39 (6)	2.469 (4)	158 (5)
O8—H8···O5	1.17 (8)	1.34 (8)	2.486 (5)	165 (6)
O7—H7···O6	0.98 (7)	1.52 (7)	2.490 (5)	171 (7)

Acknowledgements

The authors are grateful to Rev. Fr A. Albert Muthumai, 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

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bresciani-Pahor, N., Forcolin, M., Marzilli, L. G., Randaccio, L., Summers, M. F. & Toscano, P. J. (1985). Coord. Chem. Rev. 63, 1–125. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolphin, D. (1982). Editor. B₁₂, Vols. 1 and 2. New York: Wiley. Google Scholar
Englert, U., Heger, G., Kummerle, E. & Wang, R. (1999). Z. Kristallogr. 214, 71–74 CrossRef CAS Google Scholar
Englert, U., Kirch, M. & Knur, N. (2000). Z. Kristallogr. 215, 260–263. Web of Science CSD CrossRef CAS Google Scholar
Geno, M. K. & Halpern, J. (1987). J. Am. Chem. Soc. 109, 1238–1240. CrossRef CAS Web of Science Google Scholar
Kavitha, T., Revathi, C., Hemalatha, M., Dayalan, A. & Ponnuswamy, M. N. (2008). Acta Cryst. E64, o114. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ramesh, P., SubbiahPandi, A., Jothi, P., Revathi, C. & Dayalan, A. (2008). Acta Cryst. E64, m300–m301. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Schrauzer, G. N. & Kohnel, K. (1964). Chem. Ber. 97, 3056. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Trogler, W. C., Stewart, R. C., Epps, L. A. & Marzilli, L. G. (1974). Inorg. Chem. 13, 1564–1569. CrossRef CAS Web of Science Google Scholar

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