The mononuclear cobalt(II) complex Co^II(DMBDIZ)₂(NCS)₂, where DMBDIZ is 2,6-di­methyl­benzo[1,2-d:4,5-d']­di­imidazole

In the title mononuclear cobalt complex, bis(2,6-di­methyl-1H,7H-benzo­[1,2-d:4,5-d']­di­imidazole-[kappa]N³)­bis­(thio­cyanato-[kappa]N)cobalt(II), [Co^II(NCS)₂(DMBDIZ)₂] or [Co(NCS)₂(C₁₀H₁₀N₄)₂], the cobalt(II) ion is coordinated to four N atoms, from two thio­cyanate anions and two DMBDIZ ligands, in a distorted tetrahedral geometry. In the DMBDIZ ligand, the two imine N atoms are positioned cis with respect to one another. The crystal packing of the complex is dominated by both hydrogen bonding, involving two N-H...N and two N-H...S interactions, and aromatic [pi]-[pi] stacking.

S1. Comment

The supramolecular architecture created by non-covalent forces has become increasingly important in crystal engineering. Current interests focus on designing multidentate aromatic nitrogen heterocycles (Stang & Olenyuk, 1997; Steel, 1990) and polycarboxylic acid ligands (Eddaoudi et al., 2002; Abrahams et al., 1999). In order to construct novel frameworks through both coordination and hydrogen bonding, we have recently become interested in the synthesis of metal complexes with DMBDIZ (2,6-dimethyl-benzo[1,2 - d:4,5 - d']diimidazole). This ligand is not only capable of adopting various coordination modes, but can also form multiple hydrogen bonds, which may provide a tool in crystal-engineering design for assembling building blocks into multi-dimensional structures (Aakeröy et al., 2001; Holman et al., 2001). We present here the crystal structure of a mononuclear cobalt complex, (I), which forms a three-dimensional network through hydrogen bonding and aromatic π–π stacking.

As shown in Fig. 1, the cobalt ion has a distorted tetrahedral geometry, with four N-binding sites, one from the each of the two DMBDIZ ligands and two from the N-bonded thiocyanate anions. The N9—Co1 and N10—Co1 bond distances are slightly different and the C21—N10—Co1 and C22—N9—Co1 angles are notably different (Table 1) indicating that the environments of the two thiocyanate anions are not the same, which is also consistent with the IR spectrum, which shows two peaks due to the N-bonded thiocyanate anions. Both DMBDIZ ligands are planar; the dihedral angle between the two planes is 63.39 (7)° and the bond lengths all are within the expected range for a delocalized imidazole system (Tomlin et al., 2000).

The geometry of the imidazole rings is asymmetrical about the line passing through the apical C atoms (C1/C10 and C11/C20 in the two ligands), as the N1—C2/N2—C2 and N7—C12/N8—C12 bond lengths are different, thereby indicating that N2 and N8 are amines. Thus, the imine N atoms are located cis with respect to one another in the two DMDBIZ ligands.

The hydrogen-bonded network of this cis isomer leads to an efficient crystal packing. Since only one N atom in each ligand takes part in the metal coordination, the second imine N atom acts as an H-atom acceptor, forming a hydrogen bond with the NH moiety of an adjacent ligand. In total, each complex is connected to the adjacent complex molecules via eight hydrogen bonds (see Table 2).

As shown in Fig. 2, the complexes are linked into a one-dimensional chain along the c axis though hydrogen bonds between the DMDBIZ ligands and the thiocyanate anions [N8—H8A···S1ⁱ and N2—H2A···S2^iv]. Furthermore, these chains are linked into a three-dimensional network through intermolecular hydrogen bonds between the DMDBIZ ligands [N3—H3A···N1ⁱⁱⁱ and N6—H6A···N7ⁱⁱ] along the a and b axes. The two pairs of DMDBIZ ligands formed through S···H—N hydrogen bonds are each arranged in an antiparallel fashion with mean distances between the DMDBIZ planes of 3.419 (5) and 3.556 (3), indicative of an aromatic π–π-stacking interaction (Ho et al., 1999).

S2. Experimental

DMDBIZ was synthesized from 1,2,4,5-benzentetraamine according to the literature procedure of Arient et al. (1960). 1,2,4,5-Benzentetramine was synthesized from 2-dichlorobenzene by a three-step reaction (Cai et al., 2002). The free ligand DMBDIZ (0.25 mmol) and Co(ClO₄)₂·6H₂O (0.125 mmol) were each dissolved in 10 ml of ethanol; the Co^II salt solution was added slowly to the ligand solution and a slight excess of NH₄SCN in ethanol was directly added. The resulting blue solution was allowed to stand at room temperature. Large dark-blue crystals formed slowly during several days (yield: 80%). Elemental analysis gave C 48.8, H 3.3, N 25.0%; calculated 48.2, 3.6, 25.5%) IR spectrum (KBr, cm^-1): 2082 ν(CN), 2052 ν(CN).

S3. Refinement

All H atoms were located and were placed in idealized positions using a riding model (C—H = 0.93 and 0.96 Å).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering scheme.
	Fig. 2. The crystal packing of (I), showing the hydrogen bonding viewed along the b axis.

(I)

Crystal data

[Co(NCS)2(C10H10N4)2]	Z = 2
Mr = 547.53	F(000) = 562
Triclinic, P1	Dx = 1.571 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9459 (13) Å	Cell parameters from 1139 reflections
b = 7.9698 (12) Å	θ = 2.8–21.6°
c = 20.111 (3) Å	µ = 0.96 mm^−1
α = 80.527 (3)°	T = 293 K
β = 84.183 (3)°	Block, dark-blue
γ = 67.291 (3)°	0.30 × 0.25 × 0.20 mm
V = 1157.8 (3) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3999 independent reflections
Radiation source: fine-focus sealed tube	2919 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
Tmin = 0.762, Tmax = 0.832	k = −5→9
5908 measured reflections	l = −23→23

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
3999 reflections	(Δ/σ)max < 0.001
320 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.29 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	−0.00747 (7)	1.00223 (8)	0.22422 (3)	0.03069 (19)
S2	0.0456 (2)	1.4466 (2)	0.32652 (6)	0.0592 (4)
S1	0.54062 (17)	0.48438 (19)	0.22645 (7)	0.0565 (4)
N8	−0.3380 (4)	1.5256 (5)	−0.08470 (17)	0.0341 (8)
H8A	−0.3797	1.5266	−0.1227	0.041*
N6	−0.1967 (4)	0.9129 (5)	0.05407 (16)	0.0311 (8)
H6A	−0.2173	0.8388	0.0323	0.037*
N7	−0.2509 (4)	1.6296 (5)	−0.00461 (16)	0.0315 (8)
N5	−0.1202 (4)	1.0173 (5)	0.13703 (15)	0.0287 (8)
N4	−0.1211 (4)	0.9348 (5)	0.31333 (15)	0.0294 (8)
N3	−0.2848 (4)	0.8526 (5)	0.39730 (16)	0.0336 (8)
H3A	−0.3757	0.8323	0.4189	0.040*
N2	0.2252 (5)	0.6993 (5)	0.55108 (16)	0.0385 (9)
H2A	0.1974	0.6572	0.5910	0.046*
N1	0.3891 (4)	0.7881 (5)	0.46712 (16)	0.0352 (9)
C6	−0.0192 (5)	0.8803 (5)	0.37115 (18)	0.0272 (9)
C18	−0.2295 (5)	1.4445 (5)	0.01743 (19)	0.0269 (9)
C17	−0.1719 (5)	1.3340 (5)	0.07744 (19)	0.0292 (9)
H17A	−0.1369	1.3755	0.1123	0.035*
C12	−0.3140 (5)	1.6682 (6)	−0.0647 (2)	0.0322 (10)
C19	−0.1374 (5)	0.8744 (6)	0.1170 (2)	0.0311 (10)
C13	−0.2851 (5)	1.3788 (6)	−0.0345 (2)	0.0290 (9)
C7	0.1544 (5)	0.8756 (6)	0.3796 (2)	0.0326 (10)
H7B	0.2220	0.9134	0.3441	0.039*
C16	−0.1692 (5)	1.1580 (6)	0.08302 (19)	0.0280 (9)
C15	−0.2191 (5)	1.0956 (5)	0.0300 (2)	0.0269 (9)
C5	−0.1212 (5)	0.8251 (6)	0.4253 (2)	0.0317 (10)
C9	−0.2781 (5)	0.9150 (6)	0.3323 (2)	0.0329 (10)
N10	0.0169 (5)	1.2276 (5)	0.23768 (19)	0.0434 (9)
N9	0.2335 (5)	0.8059 (6)	0.21789 (18)	0.0419 (9)
C4	−0.0582 (5)	0.7616 (6)	0.4893 (2)	0.0361 (11)
H4A	−0.1262	0.7255	0.5250	0.043*
C22	0.3616 (6)	0.6701 (7)	0.2221 (2)	0.0357 (11)
C14	−0.2810 (5)	1.2030 (6)	−0.0300 (2)	0.0320 (10)
H14A	−0.3170	1.1608	−0.0644	0.038*
C8	0.2204 (5)	0.8119 (6)	0.4433 (2)	0.0320 (10)
C21	0.0295 (6)	1.3174 (6)	0.2755 (2)	0.0387 (11)
C2	0.3833 (5)	0.7216 (6)	0.5312 (2)	0.0354 (10)
C3	0.1149 (6)	0.7560 (6)	0.4959 (2)	0.0338 (10)
C10	−0.4293 (6)	0.9612 (7)	0.2879 (2)	0.0459 (12)
H10B	−0.4574	0.8545	0.2876	0.069*
H10C	−0.3948	1.0024	0.2429	0.069*
H10D	−0.5347	1.0570	0.3039	0.069*
C20	−0.1002 (6)	0.6923 (6)	0.1568 (2)	0.0415 (11)
H20A	−0.0388	0.6833	0.1967	0.062*
H20B	−0.0242	0.5989	0.1303	0.062*
H20C	−0.2132	0.6759	0.1693	0.062*
C1	0.5312 (6)	0.6731 (7)	0.5786 (2)	0.0486 (13)
H1B	0.5665	0.7760	0.5774	0.073*
H1C	0.6344	0.5701	0.5657	0.073*
H1D	0.4885	0.6418	0.6235	0.073*
C11	−0.3557 (6)	1.8458 (6)	−0.1093 (2)	0.0433 (11)
H11A	−0.2487	1.8759	−0.1162	0.065*
H11B	−0.4524	1.9404	−0.0887	0.065*
H11C	−0.3930	1.8360	−0.1520	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0349 (3)	0.0345 (4)	0.0248 (3)	−0.0162 (3)	−0.0019 (2)	−0.0018 (3)
S2	0.0952 (11)	0.0582 (9)	0.0383 (7)	−0.0429 (9)	−0.0101 (7)	−0.0056 (7)
S1	0.0449 (8)	0.0568 (9)	0.0552 (8)	−0.0046 (7)	−0.0029 (6)	−0.0093 (7)
N8	0.041 (2)	0.032 (2)	0.0287 (19)	−0.0139 (18)	−0.0046 (16)	−0.0014 (17)
N6	0.039 (2)	0.0272 (19)	0.0311 (19)	−0.0148 (17)	−0.0033 (15)	−0.0064 (16)
N7	0.036 (2)	0.029 (2)	0.033 (2)	−0.0164 (17)	−0.0025 (15)	−0.0012 (16)
N5	0.0343 (19)	0.030 (2)	0.0244 (18)	−0.0141 (16)	−0.0027 (14)	−0.0039 (16)
N4	0.0293 (19)	0.036 (2)	0.0259 (18)	−0.0186 (17)	−0.0005 (14)	0.0017 (16)
N3	0.0251 (19)	0.046 (2)	0.031 (2)	−0.0181 (17)	0.0026 (15)	0.0014 (17)
N2	0.038 (2)	0.055 (3)	0.0209 (18)	−0.0187 (19)	−0.0013 (15)	0.0018 (17)
N1	0.0294 (19)	0.048 (2)	0.029 (2)	−0.0157 (18)	−0.0003 (15)	−0.0057 (18)
C6	0.029 (2)	0.032 (2)	0.023 (2)	−0.0142 (19)	−0.0005 (16)	−0.0021 (18)
C18	0.026 (2)	0.026 (2)	0.029 (2)	−0.0105 (18)	0.0017 (17)	−0.0041 (18)
C17	0.034 (2)	0.030 (2)	0.026 (2)	−0.014 (2)	−0.0036 (17)	−0.0050 (19)
C12	0.032 (2)	0.029 (2)	0.035 (2)	−0.013 (2)	0.0014 (18)	−0.003 (2)
C19	0.030 (2)	0.033 (2)	0.032 (2)	−0.014 (2)	0.0003 (18)	−0.003 (2)
C13	0.028 (2)	0.032 (2)	0.028 (2)	−0.0122 (19)	−0.0024 (17)	−0.0023 (19)
C7	0.036 (2)	0.040 (3)	0.025 (2)	−0.021 (2)	0.0067 (18)	−0.003 (2)
C16	0.028 (2)	0.030 (2)	0.028 (2)	−0.0120 (19)	−0.0013 (17)	−0.0058 (19)
C15	0.023 (2)	0.027 (2)	0.033 (2)	−0.0120 (18)	0.0033 (17)	−0.0058 (19)
C5	0.029 (2)	0.038 (3)	0.032 (2)	−0.016 (2)	0.0042 (18)	−0.006 (2)
C9	0.035 (2)	0.038 (3)	0.029 (2)	−0.017 (2)	0.0028 (18)	−0.008 (2)
N10	0.051 (2)	0.043 (2)	0.043 (2)	−0.024 (2)	0.0004 (18)	−0.006 (2)
N9	0.037 (2)	0.047 (3)	0.037 (2)	−0.011 (2)	−0.0016 (17)	−0.0051 (19)
C4	0.033 (2)	0.051 (3)	0.029 (2)	−0.024 (2)	0.0062 (18)	−0.001 (2)
C22	0.035 (3)	0.053 (3)	0.026 (2)	−0.025 (3)	−0.0015 (19)	−0.006 (2)
C14	0.043 (3)	0.030 (2)	0.028 (2)	−0.018 (2)	−0.0066 (18)	−0.004 (2)
C8	0.033 (2)	0.036 (2)	0.028 (2)	−0.013 (2)	0.0003 (18)	−0.007 (2)
C21	0.039 (3)	0.039 (3)	0.036 (3)	−0.016 (2)	−0.005 (2)	0.007 (2)
C2	0.030 (2)	0.045 (3)	0.031 (2)	−0.015 (2)	−0.0003 (18)	−0.005 (2)
C3	0.035 (2)	0.040 (3)	0.026 (2)	−0.014 (2)	0.0037 (18)	−0.006 (2)
C10	0.033 (3)	0.068 (3)	0.040 (3)	−0.024 (3)	−0.004 (2)	−0.004 (3)
C20	0.057 (3)	0.035 (3)	0.037 (3)	−0.024 (2)	−0.008 (2)	0.002 (2)
C1	0.041 (3)	0.064 (3)	0.040 (3)	−0.019 (3)	−0.010 (2)	−0.001 (3)
C11	0.052 (3)	0.036 (3)	0.043 (3)	−0.019 (2)	−0.008 (2)	−0.001 (2)

Geometric parameters (Å, º)

Co1—N4	2.011 (3)	C18—C17	1.376 (5)
Co1—N5	2.014 (3)	C18—C13	1.419 (5)
Co1—N9	1.958 (4)	C17—C16	1.380 (5)
Co1—N10	1.943 (4)	C17—H17A	0.9300
S1—C22	1.606 (5)	C12—C11	1.483 (6)
S2—C21	1.614 (5)	C19—C20	1.472 (6)
N1—C2	1.314 (5)	C13—C14	1.377 (5)
N2—C2	1.347 (5)	C7—C8	1.375 (6)
N3—C9	1.323 (5)	C7—H7B	0.9300
N4—C9	1.327 (5)	C16—C15	1.399 (5)
N5—C19	1.327 (5)	C15—C14	1.372 (6)
N6—C19	1.342 (5)	C5—C4	1.373 (6)
N7—C12	1.299 (5)	C9—C10	1.465 (6)
N8—C12	1.351 (5)	C4—C3	1.378 (5)
N9—C22	1.163 (5)	C4—H4A	0.9300
N10—C21	1.162 (5)	C14—H14A	0.9300
N8—C13	1.371 (5)	C8—C3	1.405 (5)
N8—H8A	0.8600	C2—C1	1.481 (6)
N6—C15	1.404 (5)	C10—H10B	0.9600
N6—H6A	0.8600	C10—H10C	0.9600
N7—C18	1.417 (5)	C10—H10D	0.9600
N5—C16	1.392 (5)	C20—H20A	0.9600
N4—C6	1.396 (5)	C20—H20B	0.9600
N3—C5	1.393 (5)	C20—H20C	0.9600
N3—H3A	0.8600	C1—H1B	0.9600
N2—C3	1.389 (5)	C1—H1C	0.9600
N2—H2A	0.8600	C1—H1D	0.9600
N1—C8	1.402 (5)	C11—H11A	0.9600
C6—C7	1.392 (5)	C11—H11B	0.9600
C6—C5	1.405 (5)	C11—H11C	0.9600
N4—Co1—N5	120.65 (13)	C14—C15—N6	131.3 (4)
N9—Co1—N4	105.60 (14)	C16—C15—N6	104.8 (3)
N9—Co1—N5	103.63 (14)	C4—C5—N3	132.6 (4)
N10—Co1—N9	110.31 (16)	C4—C5—C6	123.2 (4)
N10—Co1—N4	101.89 (14)	N3—C5—C6	104.2 (3)
N10—Co1—N5	114.40 (15)	N3—C9—N4	111.8 (3)
C12—N8—C13	108.8 (3)	N3—C9—C10	123.4 (4)
C12—N8—H8A	125.6	N4—C9—C10	124.7 (4)
C13—N8—H8A	125.6	C21—N10—Co1	147.6 (4)
C19—N6—C15	107.8 (3)	C22—N9—Co1	167.4 (4)
C19—N6—H6A	126.1	N9—C22—S1	178.7 (4)
C15—N6—H6A	126.1	N10—C21—S2	178.5 (4)
C12—N7—C18	105.6 (3)	C5—C4—C3	114.0 (4)
C19—N5—C16	106.2 (3)	C5—C4—H4A	123.0
C19—N5—Co1	123.1 (3)	C3—C4—H4A	123.0
C16—N5—Co1	130.1 (3)	C15—C14—C13	113.9 (4)
C9—N4—C6	106.0 (3)	C15—C14—H14A	123.0
C9—N4—Co1	134.4 (3)	C13—C14—H14A	123.0
C6—N4—Co1	119.4 (2)	C7—C8—N1	129.7 (4)
C9—N3—C5	109.2 (3)	C7—C8—C3	120.5 (4)
C9—N3—H3A	125.4	N1—C8—C3	109.8 (3)
C5—N3—H3A	125.4	N1—C2—N2	112.9 (4)
C2—N2—C3	108.3 (3)	N1—C2—C1	125.5 (4)
C2—N2—H2A	125.9	N2—C2—C1	121.7 (4)
C3—N2—H2A	125.9	C4—C3—N2	131.4 (4)
C2—N1—C8	105.0 (3)	C4—C3—C8	124.5 (4)
C7—C6—N4	129.8 (3)	N2—C3—C8	104.1 (3)
C7—C6—C5	121.4 (4)	C9—C10—H10B	109.5
N4—C6—C5	108.7 (3)	C9—C10—H10C	109.5
C17—C18—N7	131.0 (4)	H10B—C10—H10C	109.5
C17—C18—C13	120.8 (4)	C9—C10—H10D	109.5
N7—C18—C13	108.2 (3)	H10B—C10—H10D	109.5
C18—C17—C16	116.2 (4)	H10C—C10—H10D	109.5
C18—C17—H17A	121.9	C19—C20—H20A	109.5
C16—C17—H17A	121.9	C19—C20—H20B	109.5
N7—C12—N8	112.8 (4)	H20A—C20—H20B	109.5
N7—C12—C11	126.0 (4)	C19—C20—H20C	109.5
N8—C12—C11	121.2 (4)	H20A—C20—H20C	109.5
N5—C19—N6	112.1 (4)	H20B—C20—H20C	109.5
N5—C19—C20	126.5 (4)	C2—C1—H1B	109.5
N6—C19—C20	121.5 (4)	C2—C1—H1C	109.5
N8—C13—C14	131.9 (4)	H1B—C1—H1C	109.5
N8—C13—C18	104.5 (3)	C2—C1—H1D	109.5
C14—C13—C18	123.6 (4)	H1B—C1—H1D	109.5
C8—C7—C6	116.3 (4)	H1C—C1—H1D	109.5
C8—C7—H7B	121.8	C12—C11—H11A	109.5
C6—C7—H7B	121.8	C12—C11—H11B	109.5
C17—C16—N5	129.4 (3)	H11A—C11—H11B	109.5
C17—C16—C15	121.6 (4)	C12—C11—H11C	109.5
N5—C16—C15	109.1 (3)	H11A—C11—H11C	109.5
C14—C15—C16	123.8 (4)	H11B—C11—H11C	109.5
N10—Co1—N5—C19	175.6 (3)	N5—C16—C15—C14	177.6 (4)
N9—Co1—N5—C19	55.5 (3)	C17—C16—C15—N6	179.2 (3)
N4—Co1—N5—C19	−62.2 (3)	N5—C16—C15—N6	−0.5 (4)
N10—Co1—N5—C16	5.8 (4)	C19—N6—C15—C14	−177.9 (4)
N9—Co1—N5—C16	−114.3 (3)	C19—N6—C15—C16	0.0 (4)
N4—Co1—N5—C16	128.0 (3)	C9—N3—C5—C4	−179.3 (5)
N10—Co1—N4—C9	118.0 (4)	C9—N3—C5—C6	1.1 (5)
N9—Co1—N4—C9	−126.7 (4)	C7—C6—C5—C4	−0.7 (7)
N5—Co1—N4—C9	−9.9 (4)	N4—C6—C5—C4	179.3 (4)
N10—Co1—N4—C6	−68.0 (3)	C7—C6—C5—N3	179.0 (4)
N9—Co1—N4—C6	47.2 (3)	N4—C6—C5—N3	−1.1 (4)
N5—Co1—N4—C6	164.0 (3)	C5—N3—C9—N4	−0.7 (5)
C9—N4—C6—C7	−179.4 (4)	C5—N3—C9—C10	−179.0 (4)
Co1—N4—C6—C7	5.1 (6)	C6—N4—C9—N3	0.0 (5)
C9—N4—C6—C5	0.7 (4)	Co1—N4—C9—N3	174.5 (3)
Co1—N4—C6—C5	−174.8 (3)	C6—N4—C9—C10	178.3 (4)
C12—N7—C18—C17	−178.3 (4)	Co1—N4—C9—C10	−7.2 (7)
C12—N7—C18—C13	0.0 (4)	N9—Co1—N10—C21	−87.7 (7)
N7—C18—C17—C16	179.1 (4)	N4—Co1—N10—C21	24.0 (7)
C13—C18—C17—C16	1.0 (6)	N5—Co1—N10—C21	155.9 (6)
C18—N7—C12—N8	0.4 (4)	N10—Co1—N9—C22	134.8 (16)
C18—N7—C12—C11	−178.8 (4)	N4—Co1—N9—C22	25.5 (16)
C13—N8—C12—N7	−0.7 (5)	N5—Co1—N9—C22	−102.3 (16)
C13—N8—C12—C11	178.6 (4)	N3—C5—C4—C3	−179.7 (4)
C16—N5—C19—N6	−0.9 (4)	C6—C5—C4—C3	−0.2 (6)
Co1—N5—C19—N6	−172.8 (2)	C16—C15—C14—C13	1.8 (6)
C16—N5—C19—C20	179.7 (4)	N6—C15—C14—C13	179.3 (4)
Co1—N5—C19—C20	7.8 (6)	N8—C13—C14—C15	−179.5 (4)
C15—N6—C19—N5	0.6 (4)	C18—C13—C14—C15	0.4 (6)
C15—N6—C19—C20	−180.0 (4)	C6—C7—C8—N1	178.8 (4)
C12—N8—C13—C14	−179.4 (4)	C6—C7—C8—C3	−0.1 (6)
C12—N8—C13—C18	0.7 (4)	C2—N1—C8—C7	−179.2 (4)
C17—C18—C13—N8	178.1 (3)	C2—N1—C8—C3	−0.3 (5)
N7—C18—C13—N8	−0.4 (4)	C8—N1—C2—N2	0.3 (5)
C17—C18—C13—C14	−1.9 (6)	C8—N1—C2—C1	180.0 (4)
N7—C18—C13—C14	179.6 (4)	C3—N2—C2—N1	−0.3 (5)
N4—C6—C7—C8	−179.1 (4)	C3—N2—C2—C1	−179.9 (4)
C5—C6—C7—C8	0.8 (6)	C5—C4—C3—N2	−179.1 (4)
C18—C17—C16—N5	−179.2 (4)	C5—C4—C3—C8	1.0 (6)
C18—C17—C16—C15	1.1 (6)	C2—N2—C3—C4	−179.9 (5)
C19—N5—C16—C17	−178.9 (4)	C2—N2—C3—C8	0.1 (5)
Co1—N5—C16—C17	−7.8 (6)	C7—C8—C3—C4	−0.8 (7)
C19—N5—C16—C15	0.8 (4)	N1—C8—C3—C4	−179.9 (4)
Co1—N5—C16—C15	171.9 (3)	C7—C8—C3—N2	179.2 (4)
C17—C16—C15—C14	−2.7 (6)	N1—C8—C3—N2	0.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8A···S1^i	0.86	2.59	3.439 (4)	172
N6—H6A···N7^ii	0.86	2.05	2.899 (4)	170
N3—H3A···N1^iii	0.86	2.14	3.001 (4)	177
N2—H2A···S2^iv	0.86	2.70	3.458 (4)	148

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