A novel 18-membered metallocycle in {2,5-bis­[3-(1H-1,3-imid­azol-1-ylmethyl)phenyl]-1,3,4-oxa­diazole}dichloridocobalt(II)

The title mol­ecular complex, [CoCl₂(C₂₂H₁₈N₆O)], features a novel 18-membered Co-containing metallocycle. The Co^II atom lies in a fairly regular tetra­hedral geometry defined by two imidazole N-atom donors from one 2,5-bis­[3-(1H-1,3-imidazol-1-ylmethyl)phenyl]-1,3,4-oxadiazole (L) ligand and two chloride anions. The coordinating orientation of the L ligand plays an important role in constructing the metallocycle complex. The complexes form a three-dimensional supra­molecular assembly via nonclassical C-H...Cl and C-H...N hydrogen bonds and [pi]-[pi] inter­actions.

S1. Comment

Supramolecular compounds are currently an active field of chemistry due to their novel structural topologies and potential applications in gas storage (Yaghi et al., 2003; Rowsell & Yaghi, 2005) and their magnetic (Zhao et al., 2003; Wang et al., 2006; Neville et al., 2008), catalytic (Wu & Lin, 2007) and optical properties (Wang et al., 2007; Huang et al., 2007). Recently, many high-dimensional supramolecular networks, extended from low-dimensional metal-containing molecules through hydrogen bonds, have been achieved by carefully selecting as building blocks organic ligands containing appropriate functional groups (Yaghi et al., 1998; Cho et al., 2006; Ma & Lin, 2008; Cheng et al., 2001; Choi et al., 1999; Choi & Suh, 1999). However, other superamolecular interactions, such as π–π stacking and non-classical hydrogen bonds, have been somewhat less well documented. Recently, Nichol & Clegg (2006) reported a series of structures of organic complexes formed by weak intermolecular interactions (C—H···X hydrogen bonding and π–π stacking) between acid and base when classical hydrogen bonding is not possible.

In metal–organic frameworks, the geometry of the organic ligands is one of the most important factors in determining the structure of the framework. Recently, our group reported a study of the M^II (M = Cu, Cd, Mn and Co) coordination chemistry of 2,5-bis(3-(1H-1,2,4-triazole-1-ylmethyl)phenyl)-1,3,4-oxadiazole (L2; Zhao et al., 2009). In that study, the divergent arrangement of L2 favours the formation of discrete bird-like spiro-metallocyclic complexes. In order to investigate further how the coordinating orientations of related organic ligands affect the structures of supramolecular complexes, we synthesized the ligand L, 2,5-bis(3-(1H-1,3-imidazole-1-ylmethyl)phenyl)-1,3,4-oxadiazole, and its complex, (I), with cobalt(II), the structure of which we report here.

Compound (I) crystallizes in the triclinic crystal system (space group P1) with two CoLCl₂ molecules per unit cell and one in the asymmetric unit (Z = 2). The Co^II atom is coordinated to two imidazole N-donors from one chelating L ligand and two Cl^- anions in a tetrahedral geometry (Fig. 1, Table 1). The two phenyl rings and central oxadiazole ring of L are almost coplanar and the two terminal triazole rings are nearly perpendicular to the Ph-Ox-Ph unit, with dihedral angles of 90.0 (2) and 80.6 (2)°, respectively. The two flexible imidazolemethylene arms of each L ligand are bent markedly inwards and converge at the Co^II centre to form a metallocycle consisting of 18 atoms. The distances across the ring are Co1···O1 = 6.287 (21) Å and C19···C4 = 8.239 (31) Å. The coordination behaviour of the imidazole ligand L is similar to that of the related triazole ligand L2 (Zhao et al., 2009), which is also coordinated to a single metal centre to form a large ring with corresponding dimensions of ca 6.6 and 8.3 Å, respectively. Therefore, the minor change in the central five-membered ring results in very little change in the coordinating orientation of the ligands; both are ideally oriented to form large metallocycles.

The complexes assemble into a three-dimensional supramolecular network through non-classical C—H···Cl and C—H···N hydrogen bonds and π–π interactions. Two hydrogen bonds, C19—H19B···Cl1ⁱ and C6—H6···Cl1ⁱⁱ [symmetry codes: (i) -x, -y + 2, -z + 1; (ii) -x + 1, -y + 2, -z], link the discrete molecules into one-dimensional chains along the crystallographic c axis (Fig. 2). These parallel chains extend into a two-dimensional sheet in the ac plane via hydrogen bond C22—H22···Cl2ⁱⁱⁱ [symmetry code: (iii) x + 1, y, z]. Thallapally et al. (2007) defined a C—H···Cl contact as short, medium or long using the criteria H···Cl < 2.6 Å, 2.6–3.0 Å and > 3.0 Å, respectively. The H···Cl distances in (I) (Table 2) belong to the intermediate class of contact. The packing within the layers is also reinforced by π–π interactions between parallel imidazole rings, with centroid-to-centroid distances of 3.308 (4) and 3.530 (6) Å.

The two-dimensional sheets are connected to each other along the b axis via C—H···N hydrogen bonds (Fig. 3). The C—H···N contacts and C—H···N angles (Table 2) are within typically observed ranges (Alshahateet et al., 2004). The Ph-Ox-Ph ring systems protrude from either side of the layers and interleave in a parallel fashion, with centroid-to-centroid contacts of 3.314 (65) and 3.401 (49) Å.

In summary, a three-dimensional supramolecular compound driven by C—H···Cl and C—H···N hydrogen bonds has been successfully synthesized from an 18-membered Co-containing metallocyclic complex. This study demonstrates that non-classical classical hydrogen bonds play an important role in constructing high-dimensional supramolecular compounds, which may provide a new method for constructing novel functional materials.

Related literature

For related literature, see: Alshahateet et al. (2004); Cheng et al. (2001); Cho et al. (2006); Choi & Suh (1999); Choi, Lee & Suh (1999); Huang et al. (2007); Ma & Lin (2008); Neville et al. (2008); Nichol & Clegg (2006); Rowsell & Yaghi (2005); Thallapally (2007); Wang et al. (2006, 2007); Wu & Lin (2007); Yaghi et al. (1998, 2003); Zhao et al. (2003, 2009).

S2. Experimental

KOH (2.80 g, 50 mmol) was added with stirring to a solution of bis(3-bromomethylphenyl)oxadiazole (2.04 g, 5 mmol) and imidazole (0.69 g, 10 mmol) in tetrahydrofuran (THF; 50 ml) at ambient temperature. The mixture was stirred for 12 h at ambient temperature (monitored by thin-layer chromatography). After removal of the solvent under vacuum, the residue was purified on silica gel by column chromatography using THF as eluent to afford L as a yellow solid (0.87 g, 2.27 mmol; yield 45%). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3405 (m), 1546 (s), 1504 (s), 1445 (m), 1283 (m), 1231 (s), 1188 (m), 1107 (m), 1074 (s), 983 (w), 907 (m), 818 (m), 721 (vs), 661 (m), 627 (m), 428 (w); ¹H NMR (300 MHz, CDCl₃, TMS, δ, p.p.m.): 8.11–8.08 (d, 2H, m-C₆H₄), 8.03 (s, 2H, m-C₆H₄), 7.79 (s, 2H, -C₃H₃N₂), 7.57–7.52 (t, 2H, m-C₆H₄), 7.35–7.33 (d, 2H, m-C₆H₄), 7.15 (s, 2H, -C₃H₃N₂), 6.97 (s, 2H, -C3H₃N₂), 5.26 (s, 4H, -CH₂-); elemental analysis, calculated for C₂₂H₁₈N₆O: C 69.11, H 4.71, N 21.99%; found: C 69.20, H 4.77, N 22.01%.

A solution of CoCl₂.2H₂O (5.47 mg, 0.023 mmol) in CH₃OH (5 ml) was layered onto a solution of L (8.3 mg, 0.022 mmol) in CH₂Cl₂ (8 ml). The system was left for about two weeks at room temperature and blue crystals of (I) were obtained (yield 8.33 mg, 74%). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3109 (m), 1548 (m), 1522 (m), 1490 (w), 1429 (vs), 1327 (m), 1097 (w), 1069 (s), 952 (w), 803 (w), 763 (m), 723 (vs), 684 (w), 658 (m), 631 (w).

S3. Refinement

H atoms were placed in idealized positions and treated as riding, with C—H = 0.95 (CH) or 0.99 Å (CH₂), and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small circles of arbitrary radii.
	Fig. 2. The two-dimensional sheet of (I) constructed by C—H···Cl hydrogen bonds (green dashed lines) and π–π stacking interactions (orange dashed lines). Some H atoms have been omitted. [Symmetry codes: (i) -x, -y + 2, -z + 1; (ii) -x + 1, -y + 2, -z; (iii) x + 1, y, z.] [Please note that colour will not be available in the printed version of the journal. Please revise plot and/or caption accordingly.]
	Fig. 3. The C—H···N hydrogen bonds (dashed lines) cross-linking the two-dimensional sheets of (I) into the extended three-dimensional supramolecular structure.

dichlorido{2,5-bis[3-(1H-1,3-imidazol-1-ylmethyl)phenyl]-1,3,4-oxadiazole}cobalt(II)

Crystal data

[CoCl2(C22H18N6O)]	Z = 2
Mr = 512.25	F(000) = 522
Triclinic, P1	Dx = 1.525 Mg m^−3
Hall symbol: -p1	Mo Kα radiation, λ = 0.71073 Å
a = 7.313 (3) Å	Cell parameters from 1372 reflections
b = 11.056 (5) Å	θ = 2.7–23.4°
c = 14.572 (7) Å	µ = 1.04 mm^−1
α = 74.376 (6)°	T = 173 K
β = 79.570 (7)°	Plate, blue
γ = 87.592 (7)°	0.45 × 0.15 × 0.05 mm
V = 1115.9 (9) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4068 independent reflections
Radiation source: fine-focus sealed tube	2984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan SADABS (Bruker, 2003)	h = −7→8
Tmin = 0.653, Tmax = 0.950	k = −13→12
5791 measured reflections	l = −17→17

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0637P)^2] where P = (Fo^2 + 2Fc^2)/3
4068 reflections	(Δ/σ)max = 0.001
289 parameters	Δρmax = 0.78 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.3232 (7)	0.9687 (4)	0.3880 (3)	0.0277 (11)
H1	0.4307	1.0132	0.3491	0.033*
C2	0.3064 (7)	0.9054 (4)	0.4824 (3)	0.0271 (11)
H2	0.3986	0.8974	0.5220	0.033*
C3	0.0463 (7)	0.8888 (4)	0.4324 (3)	0.0218 (10)
H3	−0.0772	0.8661	0.4318	0.026*
C4	0.0497 (7)	0.7773 (4)	0.6059 (3)	0.0264 (11)
H4A	−0.0843	0.7967	0.6193	0.032*
H4B	0.1093	0.8000	0.6549	0.032*
C5	0.0714 (6)	0.6359 (4)	0.6173 (3)	0.0207 (10)
C6	−0.0184 (7)	0.5560 (4)	0.7026 (3)	0.0260 (11)
H6	−0.0915	0.5898	0.7505	0.031*
C7	−0.0019 (7)	0.4273 (4)	0.7183 (3)	0.0274 (11)
H7	−0.0639	0.3732	0.7770	0.033*
C8	0.1039 (7)	0.3770 (4)	0.6492 (3)	0.0265 (11)
H8	0.1163	0.2886	0.6605	0.032*
C9	0.1923 (6)	0.4571 (4)	0.5630 (3)	0.0224 (10)
C10	0.1757 (6)	0.5871 (4)	0.5475 (3)	0.0213 (10)
H10	0.2366	0.6417	0.4887	0.026*
C11	0.2958 (6)	0.4041 (4)	0.4881 (3)	0.0219 (10)
C12	0.4522 (6)	0.3999 (4)	0.3501 (3)	0.0241 (10)
C13	0.5552 (6)	0.4504 (4)	0.2529 (3)	0.0246 (10)
C14	0.6415 (7)	0.3689 (4)	0.1997 (3)	0.0320 (12)
H14	0.6305	0.2805	0.2261	0.038*
C15	0.7419 (8)	0.4184 (4)	0.1091 (3)	0.0370 (13)
H15	0.8025	0.3638	0.0730	0.044*
C16	0.7563 (7)	0.5474 (4)	0.0695 (3)	0.0329 (12)
H16	0.8245	0.5802	0.0061	0.039*
C17	0.6725 (6)	0.6286 (4)	0.1214 (3)	0.0242 (10)
C18	0.5714 (7)	0.5792 (4)	0.2136 (3)	0.0255 (10)
H18	0.5129	0.6341	0.2500	0.031*
C19	0.6926 (7)	0.7696 (4)	0.0812 (3)	0.0288 (11)
H19A	0.7677	0.8028	0.1192	0.035*
H19B	0.7590	0.7894	0.0133	0.035*
C20	0.3877 (8)	0.8363 (4)	0.0237 (3)	0.0336 (12)
H20	0.4061	0.8056	−0.0323	0.040*
C21	0.2334 (7)	0.8945 (4)	0.0587 (3)	0.0322 (12)
H21	0.1244	0.9123	0.0306	0.039*
C22	0.4293 (7)	0.8844 (4)	0.1533 (3)	0.0277 (11)
H22	0.4860	0.8935	0.2048	0.033*
Cl1	0.2329 (2)	1.22077 (10)	0.16874 (8)	0.0395 (4)
Cl2	−0.1948 (2)	1.00762 (14)	0.22185 (11)	0.0486 (4)
Co1	0.10971 (9)	1.02726 (5)	0.22118 (4)	0.0239 (2)
N1	0.1589 (5)	0.9580 (3)	0.3574 (2)	0.0218 (8)
N2	0.1308 (5)	0.8550 (3)	0.5100 (2)	0.0223 (9)
N3	0.3212 (6)	0.2870 (3)	0.4897 (3)	0.0271 (9)
N4	0.4237 (5)	0.2846 (3)	0.3990 (3)	0.0254 (9)
N5	0.5104 (6)	0.8308 (3)	0.0848 (3)	0.0256 (9)
N6	0.2607 (6)	0.9232 (3)	0.1406 (3)	0.0269 (9)
O1	0.3778 (4)	0.4815 (2)	0.4024 (2)	0.0237 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.024 (3)	0.027 (2)	0.030 (3)	−0.004 (2)	−0.003 (2)	−0.004 (2)
C2	0.032 (3)	0.021 (2)	0.030 (3)	0.004 (2)	−0.010 (2)	−0.0074 (19)
C3	0.030 (3)	0.015 (2)	0.020 (2)	0.003 (2)	−0.004 (2)	−0.0049 (17)
C4	0.039 (3)	0.019 (2)	0.020 (2)	0.004 (2)	−0.002 (2)	−0.0062 (18)
C5	0.024 (3)	0.019 (2)	0.022 (2)	0.0068 (19)	−0.0106 (19)	−0.0082 (18)
C6	0.030 (3)	0.025 (2)	0.022 (2)	0.006 (2)	−0.006 (2)	−0.0060 (18)
C7	0.034 (3)	0.027 (2)	0.018 (2)	0.003 (2)	−0.004 (2)	−0.0023 (19)
C8	0.032 (3)	0.019 (2)	0.028 (2)	0.001 (2)	−0.008 (2)	−0.0031 (19)
C9	0.026 (3)	0.021 (2)	0.023 (2)	0.005 (2)	−0.008 (2)	−0.0100 (18)
C10	0.025 (3)	0.020 (2)	0.018 (2)	0.002 (2)	−0.0070 (19)	−0.0016 (17)
C11	0.022 (3)	0.016 (2)	0.028 (2)	−0.0010 (19)	−0.0058 (19)	−0.0057 (18)
C12	0.023 (3)	0.024 (2)	0.027 (2)	0.008 (2)	−0.005 (2)	−0.0110 (19)
C13	0.023 (3)	0.026 (2)	0.026 (2)	0.005 (2)	−0.005 (2)	−0.0087 (19)
C14	0.035 (3)	0.023 (2)	0.040 (3)	0.007 (2)	−0.006 (2)	−0.011 (2)
C15	0.052 (4)	0.033 (3)	0.028 (3)	0.006 (3)	0.000 (2)	−0.016 (2)
C16	0.036 (3)	0.034 (3)	0.025 (2)	0.008 (2)	0.003 (2)	−0.008 (2)
C17	0.022 (3)	0.028 (2)	0.023 (2)	0.009 (2)	−0.0041 (19)	−0.0090 (19)
C18	0.023 (3)	0.027 (2)	0.027 (2)	0.009 (2)	−0.004 (2)	−0.0107 (19)
C19	0.026 (3)	0.030 (2)	0.029 (2)	0.003 (2)	0.000 (2)	−0.009 (2)
C20	0.047 (4)	0.029 (3)	0.029 (3)	0.011 (2)	−0.010 (2)	−0.014 (2)
C21	0.039 (3)	0.028 (2)	0.033 (3)	0.013 (2)	−0.014 (2)	−0.011 (2)
C22	0.034 (3)	0.025 (2)	0.026 (2)	0.006 (2)	−0.006 (2)	−0.0117 (19)
Cl1	0.0612 (9)	0.0237 (6)	0.0272 (6)	−0.0001 (6)	0.0089 (6)	−0.0067 (5)
Cl2	0.0293 (8)	0.0645 (9)	0.0599 (9)	0.0054 (7)	−0.0121 (7)	−0.0278 (7)
Co1	0.0273 (4)	0.0226 (3)	0.0208 (3)	0.0062 (3)	−0.0033 (3)	−0.0055 (2)
N1	0.026 (2)	0.0153 (17)	0.0233 (19)	0.0028 (16)	−0.0045 (17)	−0.0034 (15)
N2	0.031 (2)	0.0156 (17)	0.0211 (19)	0.0044 (17)	−0.0037 (17)	−0.0073 (15)
N3	0.031 (2)	0.024 (2)	0.023 (2)	0.0031 (18)	−0.0010 (17)	−0.0051 (16)
N4	0.028 (2)	0.0209 (19)	0.026 (2)	0.0076 (17)	−0.0038 (17)	−0.0059 (16)
N5	0.032 (2)	0.0201 (18)	0.0219 (19)	0.0043 (17)	0.0014 (17)	−0.0065 (15)
N6	0.033 (3)	0.0216 (19)	0.025 (2)	0.0039 (18)	−0.0050 (17)	−0.0051 (16)
O1	0.0307 (19)	0.0183 (15)	0.0211 (15)	0.0037 (14)	−0.0037 (14)	−0.0048 (12)

Geometric parameters (Å, º)

C1—C2	1.352 (6)	C13—C18	1.385 (6)
C1—N1	1.375 (6)	C13—C14	1.401 (6)
C1—H1	0.9500	C14—C15	1.369 (7)
C2—N2	1.369 (6)	C14—H14	0.9500
C2—H2	0.9500	C15—C16	1.388 (6)
C3—N1	1.318 (5)	C15—H15	0.9500
C3—N2	1.344 (5)	C16—C17	1.380 (6)
C3—H3	0.9500	C16—H16	0.9500
C4—N2	1.462 (5)	C17—C18	1.389 (6)
C4—C5	1.532 (6)	C17—C19	1.514 (6)
C4—H4A	0.9900	C18—H18	0.9500
C4—H4B	0.9900	C19—N5	1.467 (6)
C5—C10	1.374 (6)	C19—H19A	0.9900
C5—C6	1.385 (6)	C19—H19B	0.9900
C6—C7	1.383 (6)	C20—C21	1.362 (7)
C6—H6	0.9500	C20—N5	1.363 (6)
C7—C8	1.380 (6)	C20—H20	0.9500
C7—H7	0.9500	C21—N6	1.365 (6)
C8—C9	1.392 (6)	C21—H21	0.9500
C8—H8	0.9500	C22—N6	1.316 (6)
C9—C10	1.397 (6)	C22—N5	1.332 (6)
C9—C11	1.454 (6)	C22—H22	0.9500
C10—H10	0.9500	Cl1—Co1	2.2370 (16)
C11—N3	1.295 (5)	Cl2—Co1	2.2447 (19)
C11—O1	1.360 (5)	Co1—N1	2.018 (4)
C12—N4	1.287 (5)	Co1—N6	2.018 (4)
C12—O1	1.368 (5)	N3—N4	1.403 (5)
C12—C13	1.452 (6)
C2—C1—N1	108.7 (4)	C16—C15—H15	119.6
C2—C1—H1	125.6	C17—C16—C15	120.7 (4)
N1—C1—H1	125.6	C17—C16—H16	119.7
C1—C2—N2	106.7 (4)	C15—C16—H16	119.7
C1—C2—H2	126.7	C16—C17—C18	119.0 (4)
N2—C2—H2	126.7	C16—C17—C19	121.5 (4)
N1—C3—N2	110.4 (4)	C18—C17—C19	119.5 (4)
N1—C3—H3	124.8	C13—C18—C17	120.5 (4)
N2—C3—H3	124.8	C13—C18—H18	119.7
N2—C4—C5	113.9 (3)	C17—C18—H18	119.7
N2—C4—H4A	108.8	N5—C19—C17	111.2 (4)
C5—C4—H4A	108.8	N5—C19—H19A	109.4
N2—C4—H4B	108.8	C17—C19—H19A	109.4
C5—C4—H4B	108.8	N5—C19—H19B	109.4
H4A—C4—H4B	107.7	C17—C19—H19B	109.4
C10—C5—C6	119.9 (4)	H19A—C19—H19B	108.0
C10—C5—C4	122.8 (4)	C21—C20—N5	106.4 (4)
C6—C5—C4	117.3 (4)	C21—C20—H20	126.8
C7—C6—C5	120.3 (4)	N5—C20—H20	126.8
C7—C6—H6	119.9	C20—C21—N6	108.9 (5)
C5—C6—H6	119.9	C20—C21—H21	125.5
C8—C7—C6	120.5 (4)	N6—C21—H21	125.5
C8—C7—H7	119.8	N6—C22—N5	111.5 (4)
C6—C7—H7	119.8	N6—C22—H22	124.2
C7—C8—C9	119.3 (4)	N5—C22—H22	124.2
C7—C8—H8	120.3	N1—Co1—N6	106.49 (15)
C9—C8—H8	120.3	N1—Co1—Cl1	106.12 (11)
C8—C9—C10	120.0 (4)	N6—Co1—Cl1	106.71 (12)
C8—C9—C11	119.4 (4)	N1—Co1—Cl2	108.87 (12)
C10—C9—C11	120.6 (4)	N6—Co1—Cl2	110.45 (12)
C5—C10—C9	120.0 (4)	Cl1—Co1—Cl2	117.60 (6)
C5—C10—H10	120.0	C3—N1—C1	106.7 (4)
C9—C10—H10	120.0	C3—N1—Co1	127.4 (3)
N3—C11—O1	111.7 (4)	C1—N1—Co1	125.8 (3)
N3—C11—C9	128.5 (4)	C3—N2—C2	107.5 (4)
O1—C11—C9	119.8 (3)	C3—N2—C4	126.0 (4)
N4—C12—O1	112.0 (4)	C2—N2—C4	126.5 (4)
N4—C12—C13	129.2 (4)	C11—N3—N4	106.7 (3)
O1—C12—C13	118.8 (3)	C12—N4—N3	106.4 (3)
C18—C13—C14	120.0 (4)	C22—N5—C20	107.2 (4)
C18—C13—C12	120.0 (4)	C22—N5—C19	125.6 (4)
C14—C13—C12	119.9 (4)	C20—N5—C19	127.1 (4)
C15—C14—C13	119.1 (4)	C22—N6—C21	106.0 (4)
C15—C14—H14	120.5	C22—N6—Co1	122.1 (3)
C13—C14—H14	120.5	C21—N6—Co1	131.2 (3)
C14—C15—C16	120.8 (4)	C11—O1—C12	103.2 (3)
C14—C15—H15	119.6
N1—C1—C2—N2	0.2 (5)	N6—Co1—N1—C3	−105.9 (4)
N2—C4—C5—C10	7.1 (6)	Cl1—Co1—N1—C3	140.7 (3)
N2—C4—C5—C6	−173.5 (4)	Cl2—Co1—N1—C3	13.2 (4)
C10—C5—C6—C7	0.6 (7)	N6—Co1—N1—C1	70.1 (4)
C4—C5—C6—C7	−178.8 (4)	Cl1—Co1—N1—C1	−43.3 (4)
C5—C6—C7—C8	0.0 (7)	Cl2—Co1—N1—C1	−170.8 (3)
C6—C7—C8—C9	−0.8 (7)	N1—C3—N2—C2	−0.1 (5)
C7—C8—C9—C10	1.0 (7)	N1—C3—N2—C4	−179.5 (4)
C7—C8—C9—C11	−176.8 (4)	C1—C2—N2—C3	−0.1 (5)
C6—C5—C10—C9	−0.5 (7)	C1—C2—N2—C4	179.3 (4)
C4—C5—C10—C9	179.0 (4)	C5—C4—N2—C3	86.0 (5)
C8—C9—C10—C5	−0.3 (7)	C5—C4—N2—C2	−93.3 (5)
C11—C9—C10—C5	177.4 (4)	O1—C11—N3—N4	−1.2 (5)
C8—C9—C11—N3	−0.7 (7)	C9—C11—N3—N4	177.6 (4)
C10—C9—C11—N3	−178.4 (4)	O1—C12—N4—N3	1.0 (5)
C8—C9—C11—O1	178.0 (4)	C13—C12—N4—N3	178.1 (4)
C10—C9—C11—O1	0.2 (7)	C11—N3—N4—C12	0.1 (5)
N4—C12—C13—C18	−179.1 (5)	N6—C22—N5—C20	0.6 (5)
O1—C12—C13—C18	−2.2 (6)	N6—C22—N5—C19	−175.4 (4)
N4—C12—C13—C14	−0.5 (8)	C21—C20—N5—C22	0.0 (5)
O1—C12—C13—C14	176.5 (4)	C21—C20—N5—C19	175.9 (4)
C18—C13—C14—C15	0.3 (7)	C17—C19—N5—C22	97.8 (5)
C12—C13—C14—C15	−178.4 (5)	C17—C19—N5—C20	−77.4 (5)
C13—C14—C15—C16	−1.0 (8)	N5—C22—N6—C21	−0.9 (5)
C14—C15—C16—C17	1.2 (8)	N5—C22—N6—Co1	−172.4 (3)
C15—C16—C17—C18	−0.8 (8)	C20—C21—N6—C22	0.9 (5)
C15—C16—C17—C19	177.6 (5)	C20—C21—N6—Co1	171.3 (3)
C14—C13—C18—C17	0.2 (7)	N1—Co1—N6—C22	−38.8 (4)
C12—C13—C18—C17	178.8 (4)	Cl1—Co1—N6—C22	74.2 (4)
C16—C17—C18—C13	0.1 (7)	Cl2—Co1—N6—C22	−156.9 (3)
C19—C17—C18—C13	−178.3 (4)	N1—Co1—N6—C21	152.1 (4)
C16—C17—C19—N5	127.3 (5)	Cl1—Co1—N6—C21	−94.9 (4)
C18—C17—C19—N5	−54.4 (6)	Cl2—Co1—N6—C21	34.0 (4)
N5—C20—C21—N6	−0.5 (5)	N3—C11—O1—C12	1.7 (5)
N2—C3—N1—C1	0.2 (5)	C9—C11—O1—C12	−177.2 (4)
N2—C3—N1—Co1	176.9 (3)	N4—C12—O1—C11	−1.6 (5)
C2—C1—N1—C3	−0.3 (5)	C13—C12—O1—C11	−179.1 (4)
C2—C1—N1—Co1	−177.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O1	0.95	2.47	2.803 (5)	101
C10—H10···N2	0.95	2.53	2.880 (5)	102
C10—H10···O1	0.95	2.52	2.841 (5)	100
C2—H2···N4^i	0.95	2.48	3.198 (6)	133
C2—H2···N3^i	0.95	2.84	3.399 (6)	118
C22—H22···Cl2^ii	0.95	2.78	3.529 (5)	136
C6—H6···Cl1^iii	0.95	2.75	3.629 (5)	155
C19—H19B···Cl1^iv	0.99	2.68	3.557 (5)	148

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