mer-Bis(1,4-dibenzoyl­thio­semi­carb­azidato-[kappa]³O,N,O')cobalt(II)

The title complex, [Co(C₁₅H₁₂N₃O₂S)₂], consists of an octa­hedrally coordinated Co^II ion, with two crystallographically independent 1,4-dibenzoyl­thio­semicarbazidate ligands in a tridentate mer coordination [Co-O = 2.064 (3)-2.132 (3) Å and Co-N = 2.037 (3)-2.043 (3) Å]. There are inter­molecular N-H...S hydrogen bonds involving one ligand and strong [pi]-­[pi] stacking inter­actions involving the other ligand, resulting in a three-dimensional supra­molecular framework. The hydrogen bonds and [pi]-[pi] inter­actions, as well as different intra­molecular aryl-benzamide H-C...H(-N) distances, give rise to a difference in conformation between the two ligands.

S1. Comment

Thiosemicarbazones and their metal-complexes are of great pharmacological interest owing to their various biological activities, including antibacterial, antimalarial, antiviral and antitumor (Quiroga & Ranninger, 2004; Kasuga et al., 2003; Easmon et al., 2001). These activities are greatly affected by the electronics, redox properties, number and position of substituent groups attached to the ligands, and the backbone conformation of the ligands or their metal complexes (Dearling et al., 2002; Maurer et al., 2002). Supramolecular interactions might also play an important role in their biological activities. Intermolecular interactions, especially pairs of N—H···N and N—H···S hydrogen bonds, often give rise to distortions of the conformation of the ligand backbone. Furthermore, these intermolecular interactions might allow the complexes to interact with various biological molecules containing complementary hydrogen-bonding motifs (e.g. purines, pyrimidines and peptide bonds) (Blower et al., 2003). Therefore, it is of interest to obtain a deeper insight into the structure-function relationship, particularly those containing supramolecular interactions, such as hydrogen bonding, π–π stacking, C—H···π and electrostatic interactions.

Hitherto, a large number of thiosemicarbazone ligands have been synthesized and structurally characterized; however, only a few 1,4-bisacylthiosemicarbazone ligands have been reported (Yamin & Yusof, 2003; Yusof et al., 2003; Ali et al., 2004 or 2003???). In the present study, the structure of the title cobalt complex, (I), with 1,4-dibenzoylthiosemicarbazidate (bhctb) has been determined; this represents the first example of a transition metal complex of such ligands.

Complex (I) contains a Co^II ion and two crystallographically independent bhctb ligands. The Co^II ion is in a slightly distorted octahedral coordination of two bhctb ligands (Fig. 1 and Table 1). Both of the tridentate bhctb ligands adopt a mer-coordinated mode with the Co^II center through one N atom and two carbonyl O atoms, Co(ONO)(ONO), forming one five-membered and one six-membered chelate ring. Owing to the spatial restrictions of the bhctb ligands, the bond angles in the Co coordination environment deviate from 90 and 180° by as much as 15.96 (11) and 20.34 (11)°, respectively.

Interestingly, there is a distinct difference between the conformations of the two crystallographically independent bhctb ligands. One bhctb ligand (containing N1–N3, denoted L1) exhibits greater coplanar characteristics, with a dihedral angle of 10.38 (25)° between the two phenyl groups, whereas the other bhctb ligand (containing N4–N6, denoted L2) is contorted, with a larger dihedral angle [28.03 (11)°]. This significant difference is ascribed to the intramolecular H···H repulsion, intermolecular hydrogen bonds and π–π interactions. The H(—C_aryl)···H(—N_benzamide) distances in L2 [H6A···H26 = 2.18 (3) Å and H4A···H20 = 2.294 (15) Å] are notably longer than those in L1 [H1A···H1 = 2.01 (2) Å and H3A···H11 = 1.998 (17) Å], implying a lower repulsion in L2. There are two N—H···S hydrogen bonds [N···S = 3.505 (3) Å], related by a twofold axis, binding the two L2 ligands into a dimer (Fig. 2). The presence of N—H···S hydrogen bonds and the lower H···H repulsion contibute to the conformational stabilization of L2. Furthermore, there are strong π–π stacking interactions between the L1 ligands, which are consistent with the greater coplanarity of the rings in L1. Each L1 ligand interacts with three adjacent L1 ligands at distances between 3.158 (5) and 3.379 (7) Å, resulting in a three-dimensional supramolecular framework (Fig. 3).

Related literature

For related literature, see: Ali et al. (2004); Blower et al. (2003); Dearling et al. (2002); Easmon et al. (2001); Kasuga et al. (2003); Maurer et al. (2002); Quiroga & Ranninger (2004); Yamin & Yusof (2003); Yusof et al. (2003).

S2. Experimental

1,4-Dibenzoylthiosemicarbazide (0.0293 g, 0.1 mmol) and cobalt(II) chloride hexahydrate (0.0476 g, 0.2 mmol) were dissolved in a mixed solvent of 8 ml of methanol and 4 ml of chloroform. Et₃N (0.014 ml) was then added and stirred for 2 h at room temperature. The resulting red mixture was filtered, and the filtered solution was allowed to evaporate in air at room temperature. Red rod-shaped crystals were separated from the filtered solution after seven days.

S3. Refinement

H atoms attached to C and N atoms were positioned geometrically and refined using a riding model [C—H = 0.93 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C,N)].

Computing details

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1993); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of (I), with displacement ellipsoids set at the 30% probability level. H atoms have been omitted for clarity. Co, O, N and S atoms are labeled.
	Fig. 2. A pair of N—H···S hydrogen bonds binding two L2 b h ct b molecules into a dimer. Hydrogen bonds are denoted by dashed lines. Most of the H atoms have been omitted for clarity. [Symmetry code: (i) -x + 1, y, -z + 3/2.]
	Fig. 3. A view of the three-dimensional supramolecular framework formed from π–π stacking interactions involving L1 ligands. The Co atoms and L2 ligands have been omitted for clarity.

mer-Bis(1,4-dibenzoylthiosemicarbazidato-κ³O,N,O')cobalt(II)

Crystal data

[Co(C15H12N3O2S)2]	F(000) = 2696
Mr = 655.62	Dx = 1.508 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.493 (5) Å	Cell parameters from 15074 reflections
b = 12.355 (3) Å	θ = 3.0–27.5°
c = 19.539 (4) Å	µ = 0.79 mm^−1
β = 102.43 (3)°	T = 298 K
V = 5774 (2) Å^3	Rod, red
Z = 8	0.32 × 0.28 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3364 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.095
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
Oscillation scans	h = −31→31
25840 measured reflections	k = −16→13
6613 independent reflections	l = −25→25

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0404P)^2] where P = (Fo^2 + 2Fc^2)/3
6613 reflections	(Δ/σ)max = 0.002
388 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.547854 (18)	0.25500 (4)	0.55496 (3)	0.04003 (15)
S1	0.63367 (4)	0.58786 (9)	0.53533 (8)	0.0705 (4)
S2	0.46598 (4)	−0.03193 (8)	0.65355 (6)	0.0493 (3)
N1	0.62810 (11)	0.3658 (3)	0.49216 (17)	0.0494 (8)
H1A	0.6490	0.4149	0.4801	0.059*
N2	0.58602 (12)	0.3913 (3)	0.52894 (17)	0.0496 (8)
N3	0.54503 (11)	0.5235 (3)	0.58233 (17)	0.0502 (8)
H3A	0.5416	0.5923	0.5867	0.060*
N4	0.55264 (11)	0.1025 (2)	0.69515 (17)	0.0473 (8)
H4A	0.5508	0.0735	0.7346	0.057*
N5	0.50671 (12)	0.1251 (2)	0.58365 (19)	0.0526 (8)
N6	0.46000 (12)	0.0923 (3)	0.52805 (17)	0.0533 (8)
H6A	0.4400	0.0363	0.5318	0.064*
O1	0.60298 (9)	0.1924 (2)	0.49615 (14)	0.0518 (7)
O2	0.50648 (10)	0.3637 (2)	0.60598 (16)	0.0606 (8)
O3	0.60641 (9)	0.2198 (2)	0.64782 (14)	0.0549 (7)
O4	0.48091 (9)	0.2328 (2)	0.46619 (14)	0.0518 (7)
C1	0.71585 (14)	0.3058 (3)	0.4242 (2)	0.0476 (9)
H1	0.7134	0.3785	0.4356	0.057*
C2	0.75824 (15)	0.2711 (3)	0.3932 (2)	0.0530 (10)
H2	0.7848	0.3202	0.3848	0.064*
C3	0.76151 (15)	0.1654 (4)	0.3750 (2)	0.0565 (11)
H3	0.7903	0.1427	0.3541	0.068*
C4	0.72274 (17)	0.0922 (3)	0.3870 (2)	0.0607 (11)
H4	0.7248	0.0201	0.3741	0.073*
C5	0.68031 (15)	0.1267 (3)	0.4188 (2)	0.0528 (10)
H5	0.6537	0.0773	0.4268	0.063*
C6	0.67696 (13)	0.2331 (3)	0.43855 (18)	0.0405 (8)
C7	0.63356 (13)	0.2623 (3)	0.47731 (18)	0.0421 (9)
C8	0.58896 (16)	0.4914 (3)	0.5470 (2)	0.0528 (10)
C9	0.50832 (15)	0.4633 (3)	0.6097 (2)	0.0488 (10)
C10	0.47019 (14)	0.5214 (3)	0.6471 (2)	0.0475 (9)
C11	0.46801 (15)	0.6305 (3)	0.6555 (2)	0.0477 (9)
H11	0.4917	0.6747	0.6365	0.057*
C12	0.43122 (15)	0.6770 (3)	0.6917 (2)	0.0528 (10)
H12	0.4304	0.7517	0.6969	0.063*
C13	0.39624 (17)	0.6134 (4)	0.7195 (2)	0.0655 (12)
H13	0.3716	0.6443	0.7442	0.079*
C14	0.3975 (2)	0.5035 (4)	0.7110 (3)	0.099 (2)
H14	0.3737	0.4592	0.7298	0.119*
C15	0.43422 (19)	0.4587 (4)	0.6747 (3)	0.094 (2)
H15	0.4346	0.3840	0.6687	0.113*
C16	0.69224 (14)	0.1849 (3)	0.7724 (2)	0.0526 (10)
H16	0.7060	0.1776	0.7318	0.063*
C17	0.72860 (18)	0.1995 (3)	0.8351 (3)	0.0671 (12)
H17	0.7669	0.1991	0.8375	0.081*
C18	0.7086 (2)	0.2147 (4)	0.8946 (3)	0.0772 (14)
H18	0.7333	0.2263	0.9373	0.093*
C19	0.6524 (2)	0.2130 (4)	0.8914 (3)	0.0739 (13)
H19	0.6390	0.2245	0.9319	0.089*
C20	0.61512 (16)	0.1943 (3)	0.8285 (2)	0.0511 (10)
H20	0.5769	0.1908	0.8269	0.061*
C21	0.63513 (13)	0.1810 (3)	0.76822 (19)	0.0387 (8)
C22	0.59693 (14)	0.1695 (3)	0.6987 (2)	0.0431 (9)
C23	0.50784 (16)	0.0702 (3)	0.6378 (2)	0.0523 (10)
C24	0.45024 (14)	0.1539 (3)	0.4716 (2)	0.0435 (9)
C25	0.40037 (14)	0.1249 (3)	0.4165 (2)	0.0415 (8)
C26	0.35352 (15)	0.0767 (3)	0.4325 (2)	0.0553 (11)
H26	0.3530	0.0592	0.4786	0.066*
C27	0.30786 (16)	0.0550 (3)	0.3798 (3)	0.0631 (12)
H27	0.2760	0.0250	0.3908	0.076*
C28	0.30866 (17)	0.0768 (3)	0.3114 (2)	0.0609 (12)
H28	0.2779	0.0602	0.2759	0.073*
C29	0.35532 (17)	0.1235 (4)	0.2958 (2)	0.0627 (11)
H29	0.3564	0.1377	0.2493	0.075*
C30	0.40017 (15)	0.1493 (3)	0.3478 (2)	0.0516 (10)
H30	0.4309	0.1837	0.3367	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0426 (2)	0.0419 (3)	0.0374 (3)	−0.0051 (2)	0.01273 (19)	0.0005 (2)
S1	0.0608 (7)	0.0494 (7)	0.1097 (11)	−0.0110 (5)	0.0367 (7)	−0.0012 (7)
S2	0.0562 (6)	0.0479 (6)	0.0437 (7)	−0.0145 (4)	0.0107 (4)	−0.0008 (5)
N1	0.0401 (16)	0.065 (2)	0.047 (2)	0.0054 (15)	0.0177 (14)	0.0037 (17)
N2	0.0504 (18)	0.053 (2)	0.046 (2)	−0.0011 (15)	0.0123 (15)	0.0032 (16)
N3	0.0490 (17)	0.0494 (18)	0.056 (2)	0.0061 (15)	0.0202 (16)	−0.0064 (16)
N4	0.0500 (17)	0.0523 (19)	0.037 (2)	−0.0061 (15)	0.0036 (14)	−0.0076 (15)
N5	0.063 (2)	0.0465 (19)	0.054 (2)	0.0017 (15)	0.0256 (17)	0.0018 (17)
N6	0.0468 (17)	0.069 (2)	0.039 (2)	−0.0057 (16)	−0.0017 (15)	−0.0082 (18)
O1	0.0491 (14)	0.0639 (17)	0.0464 (18)	−0.0072 (13)	0.0188 (12)	0.0007 (13)
O2	0.0726 (17)	0.0463 (17)	0.070 (2)	0.0015 (13)	0.0306 (15)	−0.0118 (15)
O3	0.0518 (14)	0.0753 (19)	0.0373 (17)	−0.0020 (13)	0.0090 (12)	0.0106 (14)
O4	0.0434 (13)	0.0614 (18)	0.0506 (18)	−0.0075 (13)	0.0103 (12)	−0.0113 (14)
C1	0.050 (2)	0.050 (2)	0.047 (3)	−0.0047 (18)	0.0183 (18)	−0.0036 (19)
C2	0.051 (2)	0.066 (3)	0.046 (3)	−0.0042 (19)	0.0199 (18)	−0.002 (2)
C3	0.054 (2)	0.074 (3)	0.045 (3)	0.009 (2)	0.0197 (19)	−0.008 (2)
C4	0.071 (3)	0.056 (3)	0.058 (3)	0.004 (2)	0.020 (2)	−0.010 (2)
C5	0.053 (2)	0.057 (3)	0.050 (3)	−0.0067 (19)	0.0156 (19)	0.002 (2)
C6	0.0369 (17)	0.052 (2)	0.031 (2)	0.0017 (16)	0.0054 (14)	0.0008 (17)
C7	0.0391 (18)	0.057 (2)	0.030 (2)	−0.0017 (18)	0.0070 (15)	0.0010 (18)
C8	0.059 (2)	0.052 (3)	0.045 (3)	0.0036 (19)	0.0051 (19)	0.0047 (19)
C9	0.053 (2)	0.047 (2)	0.046 (3)	0.0041 (19)	0.0099 (18)	−0.009 (2)
C10	0.046 (2)	0.048 (2)	0.048 (3)	−0.0052 (17)	0.0102 (18)	−0.0085 (19)
C11	0.055 (2)	0.048 (2)	0.043 (2)	−0.0061 (18)	0.0157 (18)	−0.0037 (19)
C12	0.067 (2)	0.044 (2)	0.051 (3)	0.0027 (19)	0.020 (2)	−0.0027 (19)
C13	0.067 (3)	0.071 (3)	0.066 (3)	0.005 (2)	0.029 (2)	−0.007 (2)
C14	0.097 (4)	0.070 (3)	0.155 (6)	−0.025 (3)	0.084 (4)	−0.012 (3)
C15	0.097 (4)	0.053 (3)	0.158 (6)	−0.013 (3)	0.086 (4)	−0.019 (3)
C16	0.053 (2)	0.059 (3)	0.044 (3)	−0.0062 (19)	0.0076 (19)	0.005 (2)
C17	0.060 (2)	0.072 (3)	0.061 (4)	−0.016 (2)	−0.005 (2)	0.003 (2)
C18	0.098 (4)	0.070 (3)	0.049 (3)	−0.026 (3)	−0.015 (3)	−0.001 (2)
C19	0.107 (4)	0.070 (3)	0.047 (3)	−0.019 (3)	0.022 (3)	−0.009 (2)
C20	0.064 (2)	0.046 (2)	0.046 (3)	−0.0113 (19)	0.017 (2)	−0.0053 (19)
C21	0.0480 (19)	0.0322 (19)	0.034 (2)	−0.0051 (15)	0.0053 (16)	−0.0004 (15)
C22	0.0447 (19)	0.047 (2)	0.039 (2)	0.0047 (18)	0.0104 (17)	−0.0016 (18)
C23	0.067 (3)	0.049 (2)	0.048 (3)	0.0141 (19)	0.026 (2)	0.004 (2)
C24	0.046 (2)	0.053 (2)	0.032 (2)	0.0091 (18)	0.0108 (17)	−0.0075 (18)
C25	0.0442 (19)	0.039 (2)	0.041 (2)	0.0007 (16)	0.0082 (16)	−0.0006 (17)
C26	0.058 (2)	0.057 (3)	0.048 (3)	−0.007 (2)	0.006 (2)	0.013 (2)
C27	0.053 (2)	0.059 (3)	0.073 (4)	−0.016 (2)	0.005 (2)	0.009 (2)
C28	0.061 (3)	0.055 (3)	0.056 (3)	−0.004 (2)	−0.012 (2)	−0.002 (2)
C29	0.068 (3)	0.078 (3)	0.038 (3)	−0.003 (2)	0.000 (2)	−0.002 (2)
C30	0.058 (2)	0.055 (2)	0.042 (3)	−0.0052 (19)	0.0104 (19)	−0.0001 (19)

Geometric parameters (Å, º)

Co1—N5	2.037 (3)	C6—C7	1.476 (4)
Co1—N2	2.043 (3)	C9—C10	1.489 (5)
Co1—O2	2.064 (3)	C10—C11	1.360 (5)
Co1—O1	2.100 (2)	C10—C15	1.369 (5)
Co1—O3	2.102 (3)	C11—C12	1.384 (5)
Co1—O4	2.132 (3)	C11—H11	0.9300
S1—C8	1.667 (4)	C12—C13	1.360 (5)
S2—C23	1.695 (4)	C12—H12	0.9300
N1—C7	1.325 (4)	C13—C14	1.370 (6)
N1—N2	1.413 (4)	C13—H13	0.9300
N1—H1A	0.8600	C14—C15	1.376 (6)
N2—C8	1.284 (5)	C14—H14	0.9300
N3—C9	1.361 (4)	C15—H15	0.9300
N3—C8	1.454 (5)	C16—C17	1.363 (6)
N3—H3A	0.8600	C16—C21	1.385 (4)
N4—C22	1.354 (4)	C16—H16	0.9300
N4—C23	1.445 (5)	C17—C18	1.368 (6)
N4—H4A	0.8600	C17—H17	0.9300
N5—C23	1.252 (5)	C18—C19	1.365 (6)
N5—N6	1.455 (4)	C18—H18	0.9300
N6—C24	1.319 (5)	C19—C20	1.383 (6)
N6—H6A	0.8600	C19—H19	0.9300
O1—C7	1.250 (4)	C20—C21	1.380 (5)
O2—C9	1.233 (4)	C20—H20	0.9300
O3—C22	1.236 (4)	C21—C22	1.481 (5)
O4—C24	1.249 (4)	C24—C25	1.487 (5)
C1—C2	1.378 (5)	C25—C30	1.375 (5)
C1—C6	1.380 (5)	C25—C26	1.386 (5)
C1—H1	0.9300	C26—C27	1.373 (5)
C2—C3	1.361 (5)	C26—H26	0.9300
C2—H2	0.9300	C27—C28	1.368 (6)
C3—C4	1.368 (5)	C27—H27	0.9300
C3—H3	0.9300	C28—C29	1.372 (5)
C4—C5	1.387 (5)	C28—H28	0.9300
C4—H4	0.9300	C29—C30	1.364 (5)
C5—C6	1.378 (5)	C29—H29	0.9300
C5—H5	0.9300	C30—H30	0.9300
N5—Co1—N2	176.46 (12)	C11—C10—C15	118.0 (4)
N5—Co1—O2	93.23 (11)	C11—C10—C9	125.6 (3)
N2—Co1—O2	83.24 (12)	C15—C10—C9	116.4 (4)
N5—Co1—O1	105.96 (11)	C10—C11—C12	121.3 (4)
N2—Co1—O1	77.57 (11)	C10—C11—H11	119.4
O2—Co1—O1	160.80 (10)	C12—C11—H11	119.4
N5—Co1—O3	83.42 (12)	C13—C12—C11	120.1 (4)
N2—Co1—O3	96.99 (11)	C13—C12—H12	120.0
O2—Co1—O3	91.87 (11)	C11—C12—H12	120.0
O1—Co1—O3	89.80 (10)	C12—C13—C14	119.4 (4)
N5—Co1—O4	77.47 (13)	C12—C13—H13	120.3
N2—Co1—O4	102.52 (12)	C14—C13—H13	120.3
O2—Co1—O4	96.04 (10)	C13—C14—C15	119.8 (4)
O1—Co1—O4	88.84 (10)	C13—C14—H14	120.1
O3—Co1—O4	159.66 (11)	C15—C14—H14	120.1
C7—N1—N2	116.5 (3)	C10—C15—C14	121.5 (4)
C7—N1—H1A	121.8	C10—C15—H15	119.2
N2—N1—H1A	121.8	C14—C15—H15	119.2
C8—N2—N1	110.5 (3)	C17—C16—C21	120.9 (4)
C8—N2—Co1	136.7 (3)	C17—C16—H16	119.5
N1—N2—Co1	111.5 (2)	C21—C16—H16	119.5
C9—N3—C8	131.0 (3)	C16—C17—C18	119.8 (4)
C9—N3—H3A	114.5	C16—C17—H17	120.1
C8—N3—H3A	114.5	C18—C17—H17	120.1
C22—N4—C23	132.4 (3)	C19—C18—C17	120.1 (5)
C22—N4—H4A	113.8	C19—C18—H18	119.9
C23—N4—H4A	113.8	C17—C18—H18	119.9
C23—N5—N6	110.5 (3)	C18—C19—C20	120.6 (4)
C23—N5—Co1	137.5 (3)	C18—C19—H19	119.7
N6—N5—Co1	111.7 (2)	C20—C19—H19	119.7
C24—N6—N5	115.8 (3)	C21—C20—C19	119.4 (4)
C24—N6—H6A	122.1	C21—C20—H20	120.3
N5—N6—H6A	122.1	C19—C20—H20	120.3
C7—O1—Co1	113.8 (2)	C20—C21—C16	119.0 (4)
C9—O2—Co1	131.5 (3)	C20—C21—C22	121.6 (3)
C22—O3—Co1	125.9 (2)	C16—C21—C22	119.2 (3)
C24—O4—Co1	113.8 (2)	O3—C22—N4	123.6 (4)
C2—C1—C6	120.3 (4)	O3—C22—C21	119.9 (3)
C2—C1—H1	119.8	N4—C22—C21	116.5 (3)
C6—C1—H1	119.8	N5—C23—N4	112.4 (4)
C3—C2—C1	120.4 (3)	N5—C23—S2	130.7 (4)
C3—C2—H2	119.8	N4—C23—S2	116.9 (3)
C1—C2—H2	119.8	O4—C24—N6	121.1 (3)
C2—C3—C4	120.4 (3)	O4—C24—C25	122.8 (3)
C2—C3—H3	119.8	N6—C24—C25	116.1 (3)
C4—C3—H3	119.8	C30—C25—C26	119.0 (4)
C3—C4—C5	119.3 (4)	C30—C25—C24	118.9 (3)
C3—C4—H4	120.4	C26—C25—C24	122.1 (4)
C5—C4—H4	120.4	C27—C26—C25	119.7 (4)
C6—C5—C4	120.9 (4)	C27—C26—H26	120.1
C6—C5—H5	119.5	C25—C26—H26	120.1
C4—C5—H5	119.5	C28—C27—C26	120.8 (4)
C5—C6—C1	118.6 (3)	C28—C27—H27	119.6
C5—C6—C7	118.0 (3)	C26—C27—H27	119.6
C1—C6—C7	123.3 (3)	C27—C28—C29	119.2 (4)
O1—C7—N1	120.5 (3)	C27—C28—H28	120.4
O1—C7—C6	121.7 (3)	C29—C28—H28	120.4
N1—C7—C6	117.8 (3)	C30—C29—C28	120.5 (4)
N2—C8—N3	112.9 (3)	C30—C29—H29	119.7
N2—C8—S1	130.6 (3)	C28—C29—H29	119.7
N3—C8—S1	116.4 (3)	C29—C30—C25	120.6 (4)
O2—C9—N3	122.7 (3)	C29—C30—H30	119.7
O2—C9—C10	119.4 (3)	C25—C30—H30	119.7
N3—C9—C10	117.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···S2^i	0.86	2.65	3.505 (3)	172

Symmetry code: (i) −x+1, y, −z+3/2.