Tris(3,5-di­methyl-1H-pyrazole-1-thio­carboxamidato-κ²N²,N)­cobalt(III)

In the crystal structure of the title complex, [Co(C₆H₈N₃S)₃], the Co^III atom is octahedrally coordinated by three monodeprotonated bidentate 3,5-di­methyl-1H-pyrazole-1-thio­carbox­amide ligands with two thio­carbox­amide N atoms in axial positions. The asymmetric unit contains two mol­ecules (A and B) and these mol­ecules are arranged in chains in an alternating fashion connected by N—H...S interactions.

S1. Comment

The complexing properties of pyrazole (py) derivatives have been the subject of extensive research (Trofimenko, 1972, 1986, 1993). Much of this interest stems from the biological activity of these molecules, which has been attributed to their chelating properties. This has stimulated research into the mode of coordination and the factors which influence it, especially with regard to the ambidentate nature of some of these molecules. The other subject of these investigations are the supramolecular structures of the complexes containing pyrazole moieties. The rigidity of the pyrazole ring and the possibility of attaching different chemical groups to the base fragment have made these molecules a convenient choice in attempts to control the manner of association of molecules in the solid state. Thus, pyrazole-based ligands containing hydrogen-bond donor and acceptor sites in the same molecule have been used to mediate intermolecular interactions (Smithson et al., 2003), and particulary to influence the metal–metal distance (Meyer et al., 1998). As part of our research on the coordination chemistry of pyrazole-derived ligands (Jaćimović et al., 1999; Tomić et al., 2000), this paper reports the crystal structure of a new cobalt(III) complex, (I), of the ligand 3,5-dimethylpyrazole-1-thiocarboxamide. Recently, the crystal structures of the Co^III, (II) (Barik et al., 2000), and Ni^II (Barik et al., 1999) complexes of the closely related ligand 1-(N-ethylthiocarbamoyl)-3,5-dimethylpyrazole have been reported. In the Co^III complex (II), three molecules of the ligand coordinate to the metal atom in a bidentate manner in an octahedral fashion, leading to a trans arrangement of the ligands. In the square-planar Ni^II complex, the ligands are cis coordinated via the ring N and thiol S atoms. Thus, the ambidentate nature of the ligand has been confirmed and the mode of binding has been explained in terms of the HSAB model (Pearson, 1963, 1987). The difference between the ligand in (I) and (II) is to do with the different atom attached to the coordinated thiocarboxamide N atom; in (I), the attached atom is an H atom, while in (II) it is the C atom of an ethyl group. The aim of the present work is to investigate how a variation in the type and disposition of hydrogen-bond donors/acceptors in novel complex (I) and its counterpart (II) influence the packing of the molecules, when the ligands otherwise have similar structural characteristics and overall shape.

The crystallographic asymmetric unit of (I) consists of two complex molecules. Three monodeprotonated molecules of the thiocarboxamide (thiocarb) ligand coordinate to the Co^III atom through the pyrazole-ring N atoms (N3, N6 and N9) and the thiocarboxamide N atoms (N1, N4 and N7). The coordination could be best described as distorted octahedral with thiocarboxamide atoms N1 and N4 in the axial (ax) positions (Fig. 1). Each type of N-donor atom is in a meridional arrangement. The two independent molecules (A and B) have similar bond distances and angles around the metal atom, indicating a similar overall shape of the two coordination polyhedra (Table 1). Comparison of the bond distances (Å) in the coordination polyhedron of compound (I) with the distances observed in (II) [Co—N_ax = 1.933 (2) versus 1.933 (2) Å, Co—N_eq = 1.922 (2)/1.937 (2) versus 1.933 (2)/1.937 (2) Å] shows that in (I) the octahedron is more compressed along the axial bonds. In the equatorial plane of (I), the Co—N_py bond which is trans to the Co—N_thiocarb bond is significantly longer than the other bonding distances in the polyhedron. In (II), where all coordinated pyrazole and thiocarboxamide N atoms are in trans positions, the difference in the bond distances is not so pronounced. If we look at the orientation of the ethyl group in (II) and consider the possible alternative disposition of the thio and pyrazole N atoms in the coordination polyhedron, it is obvious that the ligands are oriented in such way as to avoid close contact of the ethyl groups. This suggests that while in (II) it is the steric effects which govern the configuration of the complex, in (I) there is no such influence and it could be supposed that the electronic properties of the ligand and the metal atom are the main factors in determining the mode of coordination. Following location of all the atoms of the cobalt complex, residual electron density was observed, suggesting the presence of solvent molecules. However, attempts to refine the positions of these molecules failed. To correct for the contribution of the solvent molecules, the SQUEEZE procedure of PLATON (van der Sluis & Spek, 1990) was used and the solvent-free model was used in the final refinement.

The presence of both hydrogen-bond donors and acceptors makes the title molecule potentially suitable for the formation of an extended three-dimensional structure. However, due to ommision of the solvent molecules it was not possible to analyse the hydrogen-bonding interactions fully. In (I), both independent molecules form the same patern of intermolecular hydrogen bonds (Table 2). As was expected, the association of molecules is governed by N—H···S interactions and results in the formation of a chain consisting of alternating A and B molecules (Fig. 2). A weak C—H···S interaction (C11B—H30···S2A = 2.82 Å and 154°) connects neighbouring chains. To gain additional insight into the factors important for the supramolecular arrangment of this kind of complex, we will compare the present structure with that of compound (II). In (II), all H atoms are bonded to pyrazole or to the methyl C atom. Such an arrangement of donor and acceptor atoms leads to the formation of an extended structure, which could be described as an assosiation of molecules into sheets along the bc plane, and the conection of these sheets along the ab plane (C11—H16···S3 = 2.84 Å and 154°; C3—H4···S2 = 2.84 Å and 143°). Only H atoms bonded to pyrazole C atoms participate in these interactions. Fig. 3 shows the part of the unit cell with the designated contacts leading to the assosiation of molecules. With regard to the difference in the structure of the ligand in (I) and (II), it is interesting to note that, as a consequence of the stronger N—H···S bonds and the absence of stericaly more demanding ethyl groups, in the title complex, molecules are packed more tightly. The distances between the closest Co atoms are 6.802 and 11.797 Å for (I) and (II), respectively.

S2. Experimental

The title complex was synthesized by mixing a hot methanol solution of Co(OAc)₂·4H₂O (0.124 g, 0.5 mmol) and a hot methanol solution of 3,5-dimethylpyrazole-1-thiocarboxamide (0.16 g, 1 mmol). The reaction mixture, which had an intensive red colour, was warmedd and allowed to crystallize. After 10 h, the resulting solution was filtered and the pink crystals obtained were washed with methanol. Found/calulated (%): C 41.30/41.45, H 4.38/4.78, N 22.60/24.17.

S3. Refinement

H atoms attached to C atoms were included in idealized positions (C—H = 0.93 Å), while those attached to N atoms were located in a difference map. All H atoms were refined using a riding model. There are two solvent-accesible voids per unit cell. The symmetry-unique void is located at 0,0,0. PLATON (Spek, 2003) estimated that solvent-accesible region to occupy 406 Å and account for 86 e per unit cell.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1971), PLUTON (Spek, 1991), PLATON (Spek, 2003; Farrugia, 2000), ORTEP-3 (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1983, 1995) and WinGX (Farrugia, 1999).

Figures

	Fig. 1. View of the part of the asymmetric unit of (II), showing one molecule and the atom-numbering scheme.
	Fig. 2. The assosiation of molecules into a chain running along the a axis. H atoms not involved in hydrogen bonds have been omitted for clarity.
	Fig. 3. Part of the crystal structure of (II), showing the intermolecular contacts which govern the associations of molecules in the crystal. Ethyl groups and H atoms not involved in hydrogen bonds have been omitted for clarity.

(I)

Crystal data

[Co(C6H8N3S)3]	F(000) = 2160
Mr = 521.60	Dx = 1.413 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 96 reflections
a = 8.750 (2) Å	θ = 3.9–25.4°
b = 18.390 (4) Å	µ = 0.98 mm^−1
c = 30.485 (6) Å	T = 293 K
β = 91.49 (3)°	Prismatic, pink
V = 4903.8 (18) Å^3	0.31 × 0.25 × 0.22 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	Rint = 0.024
ϕ and ω scans	θmax = 26.4°, θmin = 1.3°
16028 measured reflections	h = −10→10
9487 independent reflections	k = −22→19
6904 reflections with I > 2σ(I)	l = −37→37

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.0693P)^2 + 3.7975P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.141	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 0.87 e Å^−3
9487 reflections	Δρmin = −0.52 e Å^−3
571 parameters

Special details

Experimental. KappaCCD Nonius diffractometer. 713 frames ϕ and ω scans. Rotation/frame=1°. Crystal-detector distance=60.0 mm. Measuring time=90 s/°.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1A	0.66322 (5)	0.13390 (3)	0.739624 (15)	0.03680 (14)
S1A	0.99735 (14)	−0.00778 (7)	0.67658 (4)	0.0643 (3)
S3A	0.62574 (11)	0.24630 (6)	0.61296 (3)	0.0475 (2)
S2A	0.30766 (13)	0.17536 (7)	0.83741 (4)	0.0633 (3)
N2A	0.7076 (4)	−0.00395 (17)	0.70777 (9)	0.0461 (8)
N8A	0.7287 (3)	0.26208 (16)	0.69725 (9)	0.0390 (7)
N9A	0.7427 (3)	0.23134 (16)	0.73828 (9)	0.0387 (7)
N3A	0.5981 (3)	0.03584 (16)	0.72888 (9)	0.0425 (7)
N5A	0.5945 (3)	0.12408 (17)	0.82824 (9)	0.0429 (7)
N4A	0.4817 (3)	0.16686 (17)	0.76640 (10)	0.0425 (7)
H1	0.401	0.1846	0.7544	0.051*
N1A	0.8463 (4)	0.09710 (18)	0.71636 (10)	0.0453 (8)
H2	0.9388	0.125	0.7146	0.054*
N6A	0.7137 (3)	0.11051 (16)	0.80073 (9)	0.0417 (7)
N7A	0.5923 (3)	0.16026 (16)	0.68099 (9)	0.0427 (8)
H3	0.5541	0.1244	0.6665	0.051*
C1A	0.8488 (5)	0.0319 (2)	0.70113 (11)	0.0467 (9)
C13A	0.6472 (4)	0.2188 (2)	0.66502 (12)	0.0435 (9)
C15A	0.8471 (4)	0.3413 (2)	0.73895 (13)	0.0481 (9)
H4	0.8963	0.3831	0.749	0.058*
C2A	0.6492 (6)	−0.0718 (2)	0.69680 (13)	0.0566 (11)
C16A	0.8152 (4)	0.2791 (2)	0.76403 (12)	0.0451 (9)
C14A	0.7930 (5)	0.3291 (2)	0.69732 (13)	0.0501 (10)
C7A	0.4617 (4)	0.1570 (2)	0.80830 (12)	0.0445 (9)
C3A	0.5045 (6)	−0.0720 (2)	0.71136 (13)	0.0585 (11)
H5	0.4361	−0.1106	0.7086	0.07*
C6A	0.3289 (5)	0.0197 (3)	0.75130 (18)	0.0718 (14)
H6	0.3468	0.0288	0.782	0.108*
H7	0.2524	−0.0173	0.7476	0.108*
H8	0.2943	0.0636	0.7372	0.108*
C4A	0.4736 (5)	−0.0049 (2)	0.73128 (13)	0.0508 (10)
C10A	0.8240 (5)	0.0793 (2)	0.82508 (13)	0.0494 (10)
C9A	0.7744 (5)	0.0729 (2)	0.86808 (14)	0.0602 (12)
H9	0.8303	0.0528	0.8914	0.072*
C5A	0.7313 (7)	−0.1291 (3)	0.67326 (19)	0.0895 (17)
H10	0.6644	−0.1698	0.6682	0.134*
H11	0.8187	−0.1443	0.6906	0.134*
H12	0.7642	−0.1104	0.6456	0.134*
C18A	0.8565 (5)	0.2649 (2)	0.81054 (13)	0.0567 (11)
H13	0.7718	0.2424	0.8246	0.085*
H14	0.881	0.31	0.825	0.085*
H15	0.9435	0.2332	0.8123	0.085*
C8A	0.6326 (5)	0.1007 (2)	0.87022 (13)	0.0562 (11)
C12A	0.9743 (5)	0.0574 (3)	0.80766 (16)	0.0695 (13)
H16	0.9605	0.017	0.7881	0.104*
H17	1.0419	0.0437	0.8316	0.104*
H18	1.0176	0.0975	0.7921	0.104*
C11A	0.5332 (6)	0.1065 (3)	0.90942 (15)	0.0864 (17)
H19	0.581	0.0816	0.9338	0.13*
H20	0.4356	0.0848	0.9028	0.13*
H21	0.5194	0.1568	0.9168	0.13*
C17A	0.7980 (7)	0.3789 (3)	0.65858 (16)	0.0799 (16)
H22	0.8472	0.4236	0.6671	0.12*
H23	0.6957	0.3889	0.6481	0.12*
H24	0.8542	0.3562	0.6357	0.12*
Co1B	0.14117 (5)	0.18155 (3)	0.572863 (14)	0.03497 (14)
S3B	0.14600 (11)	0.21677 (6)	0.71531 (3)	0.0494 (3)
S1B	0.47934 (13)	0.01318 (6)	0.60692 (4)	0.0603 (3)
S2B	−0.22917 (13)	0.29209 (8)	0.49629 (4)	0.0707 (4)
N3B	0.0738 (3)	0.08297 (16)	0.56384 (9)	0.0384 (7)
N9B	0.2251 (3)	0.27331 (16)	0.59273 (9)	0.0401 (7)
N8B	0.2147 (3)	0.28100 (17)	0.63791 (9)	0.0428 (7)
N5B	0.0580 (3)	0.23626 (16)	0.49046 (9)	0.0390 (7)
N1B	0.3280 (3)	0.13382 (17)	0.58599 (9)	0.0419 (7)
H25	0.4119	0.1598	0.5968	0.05*
N2B	0.1846 (3)	0.03337 (16)	0.57680 (9)	0.0413 (7)
N7B	0.0908 (3)	0.17431 (17)	0.63361 (9)	0.0444 (8)
H26	0.0609	0.1326	0.6436	0.053*
N6B	0.1737 (3)	0.19613 (16)	0.51066 (9)	0.0356 (7)
N4B	−0.0464 (3)	0.22841 (17)	0.55688 (9)	0.0414 (7)
H27	−0.1256	0.2371	0.5766	0.05*
C13B	0.1485 (4)	0.2204 (2)	0.66028 (12)	0.0419 (9)
C15B	0.3187 (5)	0.3802 (2)	0.61326 (15)	0.0548 (11)
H28	0.3618	0.4263	0.6117	0.066*
C10B	0.2777 (4)	0.1847 (2)	0.48043 (12)	0.0421 (9)
C16B	0.2896 (4)	0.3334 (2)	0.57796 (12)	0.0481 (9)
C1B	0.3302 (4)	0.0638 (2)	0.58975 (11)	0.0429 (9)
C7B	−0.0703 (4)	0.2519 (2)	0.51735 (12)	0.0430 (9)
C9B	0.2290 (5)	0.2188 (2)	0.44129 (12)	0.0502 (10)
H29	0.2818	0.2192	0.4152	0.06*
C11B	0.0004 (5)	0.2958 (3)	0.41697 (14)	0.0678 (13)
H30	0.0513	0.2992	0.3895	0.102*
H31	−0.0121	0.3436	0.429	0.102*
H32	−0.0981	0.2737	0.4123	0.102*
C12B	0.4228 (5)	0.1434 (3)	0.48851 (14)	0.0616 (12)
H33	0.494	0.1731	0.5049	0.092*
H34	0.4659	0.1304	0.461	0.092*
H35	0.4017	0.1001	0.5049	0.092*
C8B	0.0928 (4)	0.2510 (2)	0.44787 (11)	0.0456 (9)
C18B	0.3297 (6)	0.3458 (3)	0.53104 (14)	0.0680 (13)
H36	0.402	0.3097	0.5222	0.102*
H37	0.3738	0.3933	0.5281	0.102*
H38	0.239	0.3424	0.5128	0.102*
C4B	−0.0517 (4)	0.0453 (2)	0.55306 (11)	0.0464 (9)
C17B	0.2822 (7)	0.3750 (3)	0.69608 (15)	0.0776 (15)
H39	0.3275	0.4226	0.6961	0.116*
H40	0.3437	0.343	0.7141	0.116*
H41	0.1812	0.3779	0.7076	0.116*
C6B	−0.1984 (4)	0.0795 (3)	0.53796 (14)	0.0592 (11)
H42	−0.2419	0.1058	0.5618	0.089*
H43	−0.2684	0.0424	0.5281	0.089*
H44	−0.1794	0.1124	0.5142	0.089*
C2B	0.1260 (5)	−0.0359 (2)	0.57426 (12)	0.0519 (10)
C14B	0.2730 (5)	0.3465 (2)	0.65033 (14)	0.0514 (10)
C30	0.2095 (6)	−0.1028 (2)	0.58799 (16)	0.0695 (13)
H45	0.1461	−0.1445	0.5823	0.104*
H46	0.2346	−0.1002	0.6188	0.104*
H47	0.3017	−0.1068	0.5718	0.104*
C3B	−0.0193 (5)	−0.0287 (2)	0.55899 (12)	0.0529 (10)
H48	−0.0871	−0.0667	0.5533	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1A	0.0355 (3)	0.0412 (3)	0.0337 (3)	−0.0010 (2)	0.00162 (19)	−0.0031 (2)
S1A	0.0739 (8)	0.0711 (8)	0.0487 (6)	0.0286 (6)	0.0152 (5)	−0.0032 (6)
S3A	0.0445 (5)	0.0528 (6)	0.0452 (5)	0.0001 (5)	0.0000 (4)	0.0055 (5)
S2A	0.0571 (7)	0.0717 (8)	0.0622 (7)	−0.0010 (6)	0.0239 (5)	−0.0099 (6)
N2A	0.063 (2)	0.0435 (19)	0.0315 (16)	0.0061 (16)	−0.0004 (14)	−0.0016 (14)
N8A	0.0453 (17)	0.0347 (17)	0.0370 (16)	0.0029 (14)	0.0004 (13)	−0.0006 (13)
N9A	0.0348 (15)	0.0428 (17)	0.0387 (16)	−0.0015 (13)	0.0011 (12)	−0.0072 (14)
N3A	0.0483 (18)	0.0405 (17)	0.0386 (16)	0.0039 (15)	−0.0001 (14)	−0.0021 (14)
N5A	0.0457 (18)	0.0459 (18)	0.0372 (16)	−0.0073 (15)	0.0020 (13)	0.0033 (14)
N4A	0.0341 (16)	0.0491 (19)	0.0444 (18)	0.0002 (14)	0.0014 (13)	0.0029 (15)
N1A	0.0438 (17)	0.052 (2)	0.0405 (17)	0.0017 (15)	0.0057 (14)	−0.0055 (15)
N6A	0.0425 (17)	0.0439 (18)	0.0386 (16)	−0.0011 (14)	−0.0019 (13)	−0.0030 (14)
N7A	0.0553 (19)	0.0332 (16)	0.0404 (17)	−0.0218 (15)	0.0178 (14)	−0.0132 (14)
C1A	0.056 (2)	0.055 (3)	0.0291 (18)	0.010 (2)	0.0028 (16)	0.0003 (18)
C13A	0.0301 (18)	0.057 (3)	0.043 (2)	0.0099 (18)	−0.0002 (15)	−0.0141 (19)
C15A	0.049 (2)	0.041 (2)	0.055 (2)	−0.0025 (18)	0.0018 (18)	−0.0047 (19)
C2A	0.084 (3)	0.049 (3)	0.037 (2)	0.004 (2)	−0.008 (2)	−0.0056 (19)
C16A	0.0359 (19)	0.052 (2)	0.048 (2)	−0.0018 (17)	0.0019 (16)	−0.0185 (19)
C14A	0.053 (2)	0.047 (2)	0.050 (2)	0.0013 (19)	0.0018 (18)	0.0008 (19)
C7A	0.043 (2)	0.044 (2)	0.047 (2)	−0.0058 (17)	0.0057 (17)	−0.0067 (18)
C3A	0.080 (3)	0.048 (3)	0.047 (2)	−0.008 (2)	−0.013 (2)	0.006 (2)
C6A	0.053 (3)	0.060 (3)	0.102 (4)	−0.018 (2)	0.006 (3)	−0.004 (3)
C4A	0.058 (3)	0.042 (2)	0.052 (2)	−0.007 (2)	−0.0105 (19)	0.0032 (19)
C10A	0.059 (2)	0.039 (2)	0.049 (2)	−0.0018 (19)	−0.0166 (19)	−0.0017 (18)
C9A	0.076 (3)	0.051 (3)	0.052 (3)	−0.007 (2)	−0.023 (2)	0.006 (2)
C5A	0.131 (5)	0.051 (3)	0.087 (4)	0.004 (3)	0.019 (3)	−0.024 (3)
C18A	0.071 (3)	0.051 (2)	0.048 (2)	−0.014 (2)	−0.002 (2)	−0.010 (2)
C8A	0.075 (3)	0.055 (3)	0.038 (2)	−0.016 (2)	−0.002 (2)	0.0025 (19)
C12A	0.057 (3)	0.076 (3)	0.074 (3)	0.019 (2)	−0.020 (2)	−0.007 (3)
C11A	0.104 (4)	0.113 (4)	0.042 (3)	−0.015 (4)	0.007 (3)	0.007 (3)
C17A	0.116 (4)	0.053 (3)	0.070 (3)	−0.030 (3)	−0.011 (3)	0.008 (2)
Co1B	0.0324 (2)	0.0459 (3)	0.0265 (2)	−0.0043 (2)	−0.00137 (18)	0.0020 (2)
S3B	0.0487 (6)	0.0651 (7)	0.0343 (5)	0.0083 (5)	−0.0005 (4)	−0.0062 (5)
S1B	0.0595 (7)	0.0619 (7)	0.0591 (7)	0.0125 (5)	−0.0054 (5)	0.0101 (5)
S2B	0.0525 (6)	0.0976 (10)	0.0618 (7)	0.0232 (6)	−0.0053 (5)	0.0196 (7)
N3B	0.0394 (16)	0.0450 (18)	0.0309 (15)	−0.0050 (14)	0.0017 (12)	0.0035 (13)
N9B	0.0425 (17)	0.0465 (19)	0.0309 (15)	−0.0038 (14)	−0.0035 (12)	0.0009 (13)
N8B	0.0455 (17)	0.0469 (19)	0.0356 (16)	0.0078 (15)	−0.0055 (13)	−0.0071 (14)
N5B	0.0401 (16)	0.0477 (18)	0.0289 (15)	−0.0023 (14)	−0.0035 (12)	0.0048 (13)
N1B	0.0394 (16)	0.048 (2)	0.0380 (16)	−0.0041 (14)	−0.0089 (13)	0.0055 (14)
N2B	0.0482 (18)	0.0422 (18)	0.0335 (16)	−0.0040 (15)	0.0027 (13)	0.0021 (14)
N7B	0.0533 (19)	0.0473 (19)	0.0318 (15)	−0.0166 (15)	−0.0163 (14)	0.0149 (14)
N6B	0.0337 (15)	0.0433 (17)	0.0300 (15)	−0.0039 (13)	0.0019 (12)	0.0018 (13)
N4B	0.0340 (15)	0.058 (2)	0.0322 (16)	0.0018 (14)	0.0020 (12)	−0.0003 (14)
C13B	0.0362 (19)	0.052 (2)	0.0380 (19)	0.0085 (17)	0.0048 (15)	0.0048 (18)
C15B	0.055 (2)	0.038 (2)	0.071 (3)	−0.0005 (19)	−0.009 (2)	−0.008 (2)
C10B	0.040 (2)	0.049 (2)	0.0372 (19)	−0.0071 (17)	0.0079 (16)	−0.0016 (17)
C16B	0.051 (2)	0.049 (2)	0.044 (2)	−0.0042 (19)	−0.0068 (17)	0.0007 (19)
C1B	0.041 (2)	0.059 (3)	0.0282 (18)	0.0001 (18)	0.0022 (15)	0.0058 (17)
C7B	0.0372 (19)	0.053 (2)	0.039 (2)	0.0045 (17)	0.0013 (15)	0.0048 (18)
C9B	0.058 (3)	0.062 (3)	0.0320 (19)	−0.015 (2)	0.0090 (17)	0.0004 (18)
C11B	0.070 (3)	0.090 (4)	0.043 (2)	−0.010 (3)	−0.008 (2)	0.026 (2)
C12B	0.048 (2)	0.080 (3)	0.058 (3)	0.008 (2)	0.016 (2)	0.004 (2)
C8B	0.049 (2)	0.054 (2)	0.0338 (19)	−0.0151 (19)	−0.0037 (16)	0.0055 (17)
C18B	0.093 (4)	0.057 (3)	0.053 (3)	−0.033 (3)	−0.001 (2)	0.009 (2)
C4B	0.046 (2)	0.063 (3)	0.0302 (18)	−0.016 (2)	0.0027 (16)	−0.0024 (18)
C17B	0.109 (4)	0.067 (3)	0.056 (3)	−0.007 (3)	−0.008 (3)	−0.021 (2)
C6B	0.044 (2)	0.080 (3)	0.053 (2)	−0.017 (2)	−0.0057 (18)	−0.005 (2)
C2B	0.076 (3)	0.046 (2)	0.034 (2)	−0.005 (2)	0.0115 (19)	−0.0011 (18)
C14B	0.052 (2)	0.050 (2)	0.051 (2)	0.005 (2)	−0.0077 (19)	−0.008 (2)
C30	0.091 (4)	0.047 (3)	0.070 (3)	−0.001 (3)	0.013 (3)	0.001 (2)
C3B	0.068 (3)	0.053 (3)	0.037 (2)	−0.024 (2)	0.0060 (19)	−0.0071 (19)

Geometric parameters (Å, º)

Co1A—N1A	1.894 (3)	Co1B—N1B	1.889 (3)
Co1A—N4A	1.904 (3)	Co1B—N4B	1.906 (3)
Co1A—N3A	1.917 (3)	Co1B—N7B	1.919 (3)
Co1A—N9A	1.923 (3)	Co1B—N3B	1.924 (3)
Co1A—N7A	1.938 (3)	Co1B—N9B	1.932 (3)
Co1A—N6A	1.951 (3)	Co1B—N6B	1.944 (3)
S1A—C1A	1.683 (4)	S3B—C13B	1.680 (4)
S3A—C13A	1.671 (4)	S1B—C1B	1.675 (4)
S2A—C7A	1.668 (4)	S2B—C7B	1.687 (4)
N2A—N3A	1.378 (4)	N3B—C4B	1.332 (5)
N2A—C2A	1.386 (5)	N3B—N2B	1.381 (4)
N2A—C1A	1.420 (5)	N9B—C16B	1.324 (5)
N8A—C14A	1.355 (5)	N9B—N8B	1.390 (4)
N8A—N9A	1.375 (4)	N8B—C14B	1.358 (5)
N8A—C13A	1.439 (5)	N8B—C13B	1.435 (5)
N9A—C16A	1.328 (4)	N5B—C8B	1.369 (4)
N3A—C4A	1.326 (5)	N5B—N6B	1.385 (4)
N5A—N6A	1.378 (4)	N5B—C7B	1.436 (4)
N5A—C8A	1.382 (5)	N1B—C1B	1.293 (5)
N5A—C7A	1.432 (5)	N1B—H25	0.9287
N4A—C7A	1.306 (5)	N2B—C2B	1.375 (5)
N4A—H1	0.85	N2B—C1B	1.438 (5)
N1A—C1A	1.286 (5)	N7B—C13B	1.271 (5)
N1A—H2	0.96	N7B—H26	0.87
N6A—C10A	1.332 (5)	N6B—C10B	1.328 (4)
N7A—C13A	1.281 (5)	N4B—C7B	1.292 (4)
N7A—H3	0.86	N4B—H27	0.94
C15A—C14A	1.362 (5)	C15B—C14B	1.358 (6)
C15A—C16A	1.408 (6)	C15B—C16B	1.396 (5)
C15A—H4	0.93	C15B—H28	0.93
C2A—C3A	1.353 (6)	C10B—C9B	1.404 (5)
C2A—C5A	1.472 (6)	C10B—C12B	1.495 (5)
C16A—C18A	1.477 (5)	C16B—C18B	1.499 (6)
C14A—C17A	1.496 (6)	C9B—C8B	1.350 (6)
C3A—C4A	1.405 (6)	C9B—H29	0.93
C3A—H5	0.93	C11B—C8B	1.477 (6)
C6A—C4A	1.490 (6)	C11B—H30	0.96
C6A—H6	0.96	C11B—H31	0.96
C6A—H7	0.96	C11B—H32	0.96
C6A—H8	0.96	C12B—H33	0.96
C10A—C9A	1.396 (6)	C12B—H34	0.96
C10A—C12A	1.486 (6)	C12B—H35	0.96
C9A—C8A	1.346 (6)	C18B—H36	0.96
C9A—H9	0.93	C18B—H37	0.96
C5A—H10	0.96	C18B—H38	0.96
C5A—H11	0.96	C4B—C3B	1.401 (6)
C5A—H12	0.96	C4B—C6B	1.492 (6)
C18A—H13	0.96	C17B—C14B	1.491 (6)
C18A—H14	0.96	C17B—H39	0.96
C18A—H15	0.96	C17B—H40	0.96
C8A—C11A	1.500 (6)	C17B—H41	0.96
C12A—H16	0.96	C6B—H42	0.96
C12A—H17	0.96	C6B—H43	0.96
C12A—H18	0.96	C6B—H44	0.96
C11A—H19	0.96	C2B—C3B	1.349 (6)
C11A—H20	0.96	C2B—C30	1.485 (6)
C11A—H21	0.96	C30—H45	0.96
C17A—H22	0.96	C30—H46	0.96
C17A—H23	0.96	C30—H47	0.96
C17A—H24	0.96	C3B—H48	0.93
N1A—Co1A—N4A	176.13 (13)	N1B—Co1B—N4B	177.37 (12)
N1A—Co1A—N3A	81.40 (14)	N1B—Co1B—N7B	89.00 (13)
N4A—Co1A—N3A	97.19 (13)	N4B—Co1B—N7B	93.45 (13)
N1A—Co1A—N9A	90.87 (13)	N1B—Co1B—N3B	81.53 (13)
N4A—Co1A—N9A	91.06 (13)	N4B—Co1B—N3B	97.52 (13)
N3A—Co1A—N9A	168.27 (12)	N7B—Co1B—N3B	89.73 (12)
N1A—Co1A—N7A	89.85 (13)	N1B—Co1B—N9B	91.12 (13)
N4A—Co1A—N7A	93.74 (13)	N4B—Co1B—N9B	90.18 (13)
N3A—Co1A—N7A	89.49 (12)	N7B—Co1B—N9B	81.55 (12)
N9A—Co1A—N7A	81.64 (12)	N3B—Co1B—N9B	168.72 (12)
N1A—Co1A—N6A	96.10 (13)	N1B—Co1B—N6B	97.05 (12)
N4A—Co1A—N6A	80.29 (13)	N4B—Co1B—N6B	80.52 (12)
N3A—Co1A—N6A	90.84 (13)	N7B—Co1B—N6B	173.80 (13)
N9A—Co1A—N6A	98.79 (13)	N3B—Co1B—N6B	92.45 (12)
N7A—Co1A—N6A	174.02 (13)	N9B—Co1B—N6B	96.96 (12)
N3A—N2A—C2A	109.5 (3)	C4B—N3B—N2B	107.2 (3)
N3A—N2A—C1A	116.0 (3)	C4B—N3B—Co1B	140.6 (3)
C2A—N2A—C1A	134.4 (3)	N2B—N3B—Co1B	111.8 (2)
C14A—N8A—N9A	110.2 (3)	C16B—N9B—N8B	106.9 (3)
C14A—N8A—C13A	134.6 (3)	C16B—N9B—Co1B	141.6 (3)
N9A—N8A—C13A	115.1 (3)	N8B—N9B—Co1B	111.4 (2)
C16A—N9A—N8A	107.2 (3)	C14B—N8B—N9B	109.4 (3)
C16A—N9A—Co1A	140.4 (3)	C14B—N8B—C13B	135.1 (3)
N8A—N9A—Co1A	112.3 (2)	N9B—N8B—C13B	115.4 (3)
C4A—N3A—N2A	107.9 (3)	C8B—N5B—N6B	110.4 (3)
C4A—N3A—Co1A	139.8 (3)	C8B—N5B—C7B	134.3 (3)
N2A—N3A—Co1A	111.8 (2)	N6B—N5B—C7B	115.3 (3)
N6A—N5A—C8A	109.8 (3)	C1B—N1B—Co1B	119.5 (3)
N6A—N5A—C7A	115.9 (3)	C1B—N1B—H25	118.1
C8A—N5A—C7A	134.3 (3)	Co1B—N1B—H25	120.5
C7A—N4A—Co1A	120.6 (3)	C2B—N2B—N3B	109.7 (3)
C7A—N4A—H1	110	C2B—N2B—C1B	134.6 (3)
Co1A—N4A—H1	129	N3B—N2B—C1B	115.6 (3)
C1A—N1A—Co1A	119.4 (3)	C13B—N7B—Co1B	118.3 (3)
C1A—N1A—H2	117.1	C13B—N7B—H26	119
Co1A—N1A—H2	123.5	Co1B—N7B—H26	118.5
C10A—N6A—N5A	106.7 (3)	C10B—N6B—N5B	106.4 (3)
C10A—N6A—Co1A	140.3 (3)	C10B—N6B—Co1B	140.9 (3)
N5A—N6A—Co1A	112.7 (2)	N5B—N6B—Co1B	112.5 (2)
C13A—N7A—Co1A	116.5 (2)	C7B—N4B—Co1B	120.5 (2)
C13A—N7A—H3	126.7	C7B—N4B—H27	115.7
Co1A—N7A—H3	113.1	Co1B—N4B—H27	123.8
N1A—C1A—N2A	111.0 (3)	N7B—C13B—N8B	111.9 (3)
N1A—C1A—S1A	125.8 (3)	N7B—C13B—S3B	126.6 (3)
N2A—C1A—S1A	123.2 (3)	N8B—C13B—S3B	121.4 (3)
N7A—C13A—N8A	112.9 (3)	C14B—C15B—C16B	108.0 (4)
N7A—C13A—S3A	125.5 (3)	C14B—C15B—H28	126
N8A—C13A—S3A	121.5 (3)	C16B—C15B—H28	126
C14A—C15A—C16A	107.7 (4)	N6B—C10B—C9B	108.7 (3)
C14A—C15A—H4	126.2	N6B—C10B—C12B	124.1 (3)
C16A—C15A—H4	126.2	C9B—C10B—C12B	127.2 (3)
C3A—C2A—N2A	105.4 (4)	N9B—C16B—C15B	108.8 (4)
C3A—C2A—C5A	129.1 (5)	N9B—C16B—C18B	124.3 (3)
N2A—C2A—C5A	125.5 (5)	C15B—C16B—C18B	126.8 (4)
N9A—C16A—C15A	108.3 (3)	N1B—C1B—N2B	110.6 (3)
N9A—C16A—C18A	123.5 (4)	N1B—C1B—S1B	126.2 (3)
C15A—C16A—C18A	128.1 (3)	N2B—C1B—S1B	123.2 (3)
N8A—C14A—C15A	106.6 (3)	N4B—C7B—N5B	110.8 (3)
N8A—C14A—C17A	125.2 (4)	N4B—C7B—S2B	127.8 (3)
C15A—C14A—C17A	128.2 (4)	N5B—C7B—S2B	121.3 (3)
N4A—C7A—N5A	110.3 (3)	C8B—C9B—C10B	108.6 (3)
N4A—C7A—S2A	128.5 (3)	C8B—C9B—H29	125.7
N5A—C7A—S2A	121.2 (3)	C10B—C9B—H29	125.7
C2A—C3A—C4A	109.3 (4)	C8B—C11B—H30	109.5
C2A—C3A—H5	125.3	C8B—C11B—H31	109.5
C4A—C3A—H5	125.3	H30—C11B—H31	109.5
C4A—C6A—H6	109.5	C8B—C11B—H32	109.5
C4A—C6A—H7	109.5	H30—C11B—H32	109.5
H6—C6A—H7	109.5	H31—C11B—H32	109.5
C4A—C6A—H8	109.5	C10B—C12B—H33	109.5
H6—C6A—H8	109.5	C10B—C12B—H34	109.5
H7—C6A—H8	109.5	H33—C12B—H34	109.5
N3A—C4A—C3A	107.8 (4)	C10B—C12B—H35	109.5
N3A—C4A—C6A	124.0 (4)	H33—C12B—H35	109.5
C3A—C4A—C6A	128.2 (4)	H34—C12B—H35	109.5
N6A—C10A—C9A	108.7 (4)	C9B—C8B—N5B	105.9 (3)
N6A—C10A—C12A	123.5 (4)	C9B—C8B—C11B	128.4 (4)
C9A—C10A—C12A	127.7 (4)	N5B—C8B—C11B	125.7 (4)
C8A—C9A—C10A	108.9 (4)	C16B—C18B—H36	109.5
C8A—C9A—H9	125.6	C16B—C18B—H37	109.5
C10A—C9A—H9	125.6	H36—C18B—H37	109.5
C2A—C5A—H10	109.5	C16B—C18B—H38	109.5
C2A—C5A—H11	109.5	H36—C18B—H38	109.5
H10—C5A—H11	109.5	H37—C18B—H38	109.5
C2A—C5A—H12	109.5	N3B—C4B—C3B	108.1 (4)
H10—C5A—H12	109.5	N3B—C4B—C6B	123.7 (4)
H11—C5A—H12	109.5	C3B—C4B—C6B	128.3 (4)
C16A—C18A—H13	109.5	C14B—C17B—H39	109.5
C16A—C18A—H14	109.5	C14B—C17B—H40	109.5
H13—C18A—H14	109.5	H39—C17B—H40	109.5
C16A—C18A—H15	109.5	C14B—C17B—H41	109.5
H13—C18A—H15	109.5	H39—C17B—H41	109.5
H14—C18A—H15	109.5	H40—C17B—H41	109.5
C9A—C8A—N5A	105.9 (4)	C4B—C6B—H42	109.5
C9A—C8A—C11A	128.3 (4)	C4B—C6B—H43	109.5
N5A—C8A—C11A	125.8 (4)	H42—C6B—H43	109.5
C10A—C12A—H16	109.5	C4B—C6B—H44	109.5
C10A—C12A—H17	109.5	H42—C6B—H44	109.5
H16—C12A—H17	109.5	H43—C6B—H44	109.5
C10A—C12A—H18	109.5	C3B—C2B—N2B	106.0 (4)
H16—C12A—H18	109.5	C3B—C2B—C30	129.1 (4)
H17—C12A—H18	109.5	N2B—C2B—C30	124.9 (4)
C8A—C11A—H19	109.5	N8B—C14B—C15B	106.8 (3)
C8A—C11A—H20	109.5	N8B—C14B—C17B	125.7 (4)
H19—C11A—H20	109.5	C15B—C14B—C17B	127.5 (4)
C8A—C11A—H21	109.5	C2B—C30—H45	109.5
H19—C11A—H21	109.5	C2B—C30—H46	109.5
H20—C11A—H21	109.5	H45—C30—H46	109.5
C14A—C17A—H22	109.5	C2B—C30—H47	109.5
C14A—C17A—H23	109.5	H45—C30—H47	109.5
H22—C17A—H23	109.5	H46—C30—H47	109.5
C14A—C17A—H24	109.5	C2B—C3B—C4B	109.0 (4)
H22—C17A—H24	109.5	C2B—C3B—H48	125.5
H23—C17A—H24	109.5	C4B—C3B—H48	125.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4A—H1···S3B	0.85	2.57	3.414 (3)	171
N7A—H3···S1B	0.86	2.80	3.644 (3)	168
N1A—H2···S3B^i	0.96	2.48	3.424 (3)	169
N1B—H25···S3A	0.93	2.50	3.410 (3)	168
N7B—H26···S1A^ii	0.87	2.83	3.695 (3)	174
N4B—H27···S3A^ii	0.94	2.47	3.394 (3)	165
C11B—H30···S2A^iii	0.96	2.82	3.706 (5)	154

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, −y+1/2, z−1/2.