A new three-dimensional Cd^II supra­molecular framework constructed from the 1-[(1H-tetra­zol-5-yl)methyl]-1,4-di­azoniabi­cyclo­[2.2.2]octane ligand

A new tetra­zole–metal supra­molecular compound, di-μ-chlorido-bis­(tri­chlorido­­{1-[(1H-tetra­zol-5-yl-κN²)methyl]-1,4-diazo­nia­bi­cyclo­[2.2.2]octane}cadmium(II)), [Cd₂(C₈H₁₆N₆)₂Cl₈], has been synthesized and structurally characterized by single-crystal X-ray diffraction. In the structure, each Cd^II cation is coordinated by five Cl atoms (two bridging and three terminal) and by one N atom from the 1-[(1H-tetra­zol-5-yl)methyl]-1,4-diazo­nia­bi­cyclo­[2.2.2]octane ligand, adopting a slightly distorted octa­hedral coordination geometry. The bridging bi­cyclo­[2.2.2]octane and chloride ligands link the Cd^II cations into one-dimensional ribbon-like N—H...Cl hydrogen-bonded chains along the b axis. An extensive hydrogen-bonding network formed by N—H...Cl and C—H...Cl hydrogen bonds, and inter­chain π–π stacking inter­actions between adjacent tetra­zole rings, consolidate the crystal packing, linking the poymeric chains into a three-dimensional supra­molecular network.

S1. Introduction

A great deal of attention has been paid to the crystal engineering of metal–organic frameworks (MOFs) in recent years, due to a combination of their fascinating molecular structures and their potential applications, such as gas storage, heterogeneous catalysis, magnetism, fluorescence, electrical conductivity, magnetism and optics (Nouar et al., 2008; Rodríguez et al., 2005; Ye et al., 2005, 2006). The generation of supra­molecular frameworks rests on the coordination geometry of the metal ions and the structural characteristics of the organic ligands (Kasai et al., 2000). It has also been shown that organic ligands with a tetra­zole functional group are particularly useful for the construction of such supra­molecular frameworks (Demko & Sharpless, 2002; Haasnoot, 2000; Ding et al., 2009; Zhao et al., 2008). Supra­molecular polymers with one-, two- and three-dimensional frameworks involving Cd^II ions have been the subject of much inter­est owing to their potential applications in catalysis and optics (Fujita et al., 1994). The Cd^II cation, being a d¹⁰ ion, exhibits a variety of coordination numbers and geometries. The organic ligands, as well as the anions, are observed to control the structural dimensionalities and stereochemistry of a Cd^II centre (Laskar et al., 2002; Wang et al., 1999).

In the case of transition metal chloride complexes, the M—Cl groups (M is a transition metal) can act as good hydrogen-bond acceptors (Gillon et al., 2000; Luque et al., 2002). We continue to investigate the effect of organic ligands and anions in fabricating multidimensional polymers, especially in tetra­zole–metal supra­molecular frameworks. In the present paper, we report the synthesis and structural characterization of an unusual compound, (I), based on the unique 1-[(1H-tetra­zol-5-yl)methyl]-1,4-diazo­niabi­cyclo­[2.2.2]o­ctane ligand. Strong hydrogen-bond and π–π stacking inter­actions serve to stabilize the structure of (I).

S2. Experimental

S2.1. Synthesis and crystallization

Chloro­aceto­nitrile (0.05 mol, 3.775 g) was added to a CH₃CN solution (30 ml) of 1,4-di­aza­bicyclo­[2.2.2]o­ctane (DABCO; 0.05 mol, 5.6 g) with stirring, and the resulting mixture stirred for 2 h at room temperature. 1-Cyano­methyl-4-aza-1-azoniabi­cyclo­[2.2.2]o­ctane chloride, (1), quickly formed as a white solid and was filtered off, washed with aceto­nitrile and dried (yield 80%).

1-[(1H-Tetra­zol-5-yl)methyl]-1,4-di­aza­bicyclo­[2.2.2]o­ctane, (2), was prepared using a modification of the procedure of Demko & Sharpless (2001). In brief, a mixture of (1) (0.03 mol, 5.648 g), sodium azide (0.035 mol, 2.275 g) and zinc chloride (0.015 mol, 2.045 g) in deionized water [Volume?] was reacted at 373 K in a three-necked flask equipped with a reflux condenser and a mechanical stirrer. After refluxing for 36 h, the mixture was cooled to room temperature, the pH was adjusted to 1.0 with concentrated HCl and the reaction mixture was stirred for 1 h. The white precipitate which formed, i.e. (2), was filtered off and dried under vacuum at 353 K for 24 h (yield 4.5 g, 64.5%).

For the synthesis of the title compound, (I), an aqueous solution (15 ml) of (2) (2 mmol, 0.465 g) was added slowly to an aqueous solution [Volume?] of cadmium chloride (2 mmol, 0.367 g) and concentrated HCl (1 ml), affording a colourless solution. Upon standing at room temperature for several days to allow slow solvent evaporation, suitable colourless single crystals of (I) were obtained. The IR spectrum of (I) is available in the Supporting information. [Can some peak assignments be made and included here?]

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and N—H = 0.86 or 0.91 Å, and with U_iso(H) = 1.2U_eq(C,N).

S3. Results and discussion

Single-crystal X-ray diffraction reveals that the title compound, (I), crystallizes in the triclinic space group P1. The asymmetric unit is shown in Fig. 1. The Cl1—Cd1—Cl2, Cl1—Cd1—N5 and Cl1—Cd2—Cl4 angles are 96.12 (5), 87.86 (8) and 93.78 (4)°, respectively, indicating that the Cd1 atom, coordinated by five Cl atoms (two bridging and three terminal) and by one N atom from the tetra­zole ring of the 1-[(1H-tetra­zol-5-yl)methyl]-1,4-diazo­niabi­cyclo­[2.2.2]o­ctane ligand, has a slightly distorted o­cta­hedral coordination geometry. The Cd1—N5 bond distance of 2.646 (4) Å is longer than in other tetra­zole–metal complexes (Dang & Caiyun, 2013; Su et al., 2009). The N1—C7—C8 bond angle between the DABCO and tetra­zole rings is 114.2 (3)°. The two bridging chloride ligands and the two Cd^II cations form a plane that is almost square. This phenomenon is similar to what has been reported for other cadmium halides (Matsunaga et al., 2005; Chandrasekhar & Senapati, 2010; Shi et al., 2004). This gives rise to a Cd···Cd distance of 3.827 (2) Å. A wide variation is observed in the Cd—Cl bond lengths, with values ranging from 2.5270 (11) to 2.7237 (14) Å, along with significant angular distortions of the Cd o­cta­hedra. The Cd—Cl bond lengths are in good agreement [Despite the wide variation?] with those previously found in other chloridocadmate(II) compounds (Wu, 2014; Chen & Beatty, 2007; Corradi et al., 1995).

Another inter­esting feature is that there are many hydrogen bonds of the N—H···Cl and C—H···Cl types in the structure of (I). These are formed between the C or N atoms of the bi­cyclo­[2.2.2]o­ctane ligand as donors and the chloride ligands as acceptors. As shown in Fig. 3 [Should this be Fig. 2?], each pair of ligands inter­links two [Cd₂Cl₈]^4- anions to form infinite chains through inter­molecular N2—H2C···Cl1, N2—H2C···Cl3 and N2—H2C···Cl4 hydrogen bonds. Adjacent chains are then connected by a C6—H6A···Cl1 hydrogen bond and a weak π–π stacking inter­action into a two-dimensional network.

Compound (I) also differs from another Cd^II complex, viz. {[Cd₃Cl₆(deatrz)₂(H₂O)₂]·2H₂O}_n (deatrz is 4-amino-3,5-di­ethyl-1,2,4-triazole; Yi et al., 2004), where neighbouring Cd^II atoms of the centrosymmetric trinuclear species are linked by one bridging triazole ligand and two chloride ligands, forming a one-dimensional chain along the a axis. As shown in Fig. 2, in our notation, the letters A and B denote the tetra­zole rings in the one-dimensional [hydrogen-bonded?] chain, and the letters C and D denote the four-membered Cd₂Cl₂ rings. Inter­estingly, the planes of A and B, and the planes of C and D, are strictly parallel, with respective distances of 7.273 (3) and 7.106 (1) Å. The dihedral angle between the planes of the tetra­zole and the four-membered Cd₂Cl₂ rings is 69.433 (1)°.

It is worth mentioning that there is a weak π–π stacking inter­action between adjacent tetra­zole rings (Fig. 3) characterized by a centroid-to-centroid distance of 3.716 (1) Å. It is noteworthy that the present ribbon-like structure connected by hydrogen-bond inter­actions and a π–π stacking inter­action is different from the one-dimensional triple-stranded hinged chain constructed from the 4-[(imidazol-1-yl)methyl]-1-(tetra­zol-5-yl)benzene (L) ligand in [Cd(L)₂(H₂O)₂].3H₂O (Su et al., 2009), where each L ligand links two Cd^II atoms to form an infinite one-dimensional chain, and the hinged chains pack together via O—H···N, O—H ···O and C—H···N hydrogen bonds to generate a three-dimensional structure.

A better insight into the nature of this network can be obtained by consideration of the packing arrangement. In the packing arrangement of (I), the layers stack up effectively and co-operatively to form a three-dimensional supra­molecular framework via N6—H6C···Cl3, C4—H4C···Cl2, C4—H4D···Cl3 and C6—H6B···Cl4 hydrogen bonds and weak π–π stacking inter­actions, as illustrated in Fig. 4. These hydrogen-bonding inter­actions and π–π stacking inter­actions lead to a self-assembled molecular [supra­molecular?] conformation and contribute to the stabilization of the crystal structure.

In conclusion, to the best of our knowledge, complex (I) is a new cadmium(II) supra­molecular polymer of a new ligand with a slightly distorted o­cta­hedral geometry. This analysis suggests that tetra­zole–metal complexes will continue to be a rich source of inter­esting supra­molecular polymers.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The local coordination environment of the Cd^II atom in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (vi) -x+1, -y+2, -z+1.]
	Fig. 2. The infinite one-dimensional hydrogen-bonded? chain of (I). The tetrazole rings labelled A and B, and the Cd2Cl2 rings labelled C and D, are discussed in the text. [Dashed lines indicate hydrogen bonds.]
	Fig. 3. An illustration of the hydrogen-bonding [purple dashed lines] and π–π stacking [black dashed lines] interactions in (I). Nonparticipating H atoms have been omitted for clarity.
	Fig. 4. An illustration of the three-dimensional network of (I), along the a axis. [Thin purple lines denote hydrogen bonds and black dashed lines indicate π–π interactions.]

Di-µ-chlorido-bis(trichlorido{1-[(1H-tetrazol-5-yl-κN²)methyl]-1,4-diazoniabicyclo[2.2.2]octane}cadmium(II))

Crystal data

[Cd2(C8H16N6)2Cl8]	Z = 1
Mr = 900.96	F(000) = 444
Triclinic, P1	Dx = 2.049 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0015 (16) Å	Cell parameters from 4863 reflections
b = 9.5135 (19) Å	θ = 3.1–27.5°
c = 9.846 (2) Å	µ = 2.22 mm^−1
α = 96.90 (3)°	T = 293 K
β = 98.16 (3)°	Block, colourless
γ = 96.51 (3)°	0.28 × 0.26 × 0.22 mm
V = 730.0 (3) Å^3

Data collection

Rigaku SCXmini diffractometer	2311 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.0°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→11
Tmin = 0.542, Tmax = 0.613	l = −11→10
4252 measured reflections	3 standard reflections every 180 reflections
2525 independent reflections	intensity decay: none

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0576P)^2] where P = (Fo^2 + 2Fc^2)/3
2525 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.57 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
Cd1	0.41362 (3)	0.83531 (3)	0.36660 (3)	0.02203 (13)
Cl2	0.14222 (15)	0.66282 (12)	0.28128 (13)	0.0460 (3)
Cl3	0.50886 (12)	0.68132 (10)	0.55779 (10)	0.0267 (2)
Cl4	0.27680 (11)	1.01294 (9)	0.52583 (9)	0.0223 (2)
Cl1	0.38534 (12)	0.97879 (10)	0.16651 (9)	0.0259 (2)
N1	0.8427 (4)	0.2694 (3)	0.1852 (3)	0.0171 (6)
N2	1.1189 (4)	0.1882 (3)	0.2814 (3)	0.0216 (7)
H2C	1.2190	0.1593	0.3162	0.026*
N5	0.5974 (5)	0.6738 (3)	0.2266 (4)	0.0304 (8)
N4	0.6664 (5)	0.6863 (4)	0.1158 (4)	0.0322 (8)
N3	0.7086 (4)	0.5585 (3)	0.0632 (3)	0.0284 (8)
N6	0.5969 (4)	0.5367 (3)	0.2467 (3)	0.0258 (7)
H6C	0.5594	0.4993	0.3137	0.031*
C4	0.8996 (5)	0.3361 (4)	0.3345 (4)	0.0241 (8)
H4C	0.9292	0.4384	0.3390	0.029*
H4D	0.8074	0.3193	0.3872	0.029*
C3	1.0522 (5)	0.2714 (5)	0.3958 (4)	0.0300 (9)
H3A	1.1399	0.3464	0.4446	0.036*
H3B	1.0195	0.2091	0.4613	0.036*
C5	0.9927 (5)	0.0588 (4)	0.2205 (4)	0.0283 (9)
H5A	0.9839	−0.0068	0.2881	0.034*
H5B	1.0294	0.0097	0.1400	0.034*
C6	0.8203 (5)	0.1091 (4)	0.1790 (4)	0.0239 (8)
H6A	0.7713	0.0648	0.0858	0.029*
H6B	0.7431	0.0807	0.2414	0.029*
C7	0.6731 (5)	0.3100 (4)	0.1270 (4)	0.0233 (8)
H7A	0.6484	0.2745	0.0287	0.028*
H7B	0.5855	0.2630	0.1709	0.028*
C8	0.6639 (5)	0.4681 (4)	0.1462 (4)	0.0208 (8)
C1	0.9790 (5)	0.3126 (4)	0.1010 (4)	0.0232 (8)
H1A	0.9856	0.4140	0.0945	0.028*
H1B	0.9515	0.2606	0.0079	0.028*
C2	1.1492 (5)	0.2788 (4)	0.1717 (4)	0.0276 (9)
H2A	1.2066	0.2289	0.1040	0.033*
H2B	1.2214	0.3669	0.2126	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02316 (18)	0.02035 (19)	0.02214 (18)	0.00287 (12)	0.00121 (12)	0.00406 (12)
Cl2	0.0435 (7)	0.0366 (6)	0.0481 (7)	−0.0149 (5)	−0.0060 (5)	0.0008 (5)
Cl3	0.0239 (5)	0.0261 (5)	0.0323 (5)	0.0033 (4)	0.0050 (4)	0.0120 (4)
Cl4	0.0216 (5)	0.0228 (5)	0.0235 (5)	0.0039 (4)	0.0048 (4)	0.0045 (4)
Cl1	0.0263 (5)	0.0317 (5)	0.0213 (5)	0.0070 (4)	0.0031 (4)	0.0071 (4)
N1	0.0159 (15)	0.0164 (15)	0.0194 (15)	0.0035 (12)	0.0029 (12)	0.0028 (12)
N2	0.0141 (15)	0.0285 (17)	0.0245 (16)	0.0093 (13)	0.0024 (12)	0.0081 (14)
N5	0.034 (2)	0.0280 (19)	0.0318 (19)	0.0085 (15)	0.0067 (15)	0.0085 (15)
N4	0.037 (2)	0.033 (2)	0.033 (2)	0.0102 (16)	0.0135 (16)	0.0150 (16)
N3	0.0314 (19)	0.0296 (18)	0.0300 (18)	0.0142 (15)	0.0103 (15)	0.0114 (15)
N6	0.0320 (19)	0.0242 (17)	0.0254 (17)	0.0090 (14)	0.0081 (14)	0.0114 (14)
C4	0.0196 (19)	0.035 (2)	0.0175 (18)	0.0066 (17)	0.0024 (15)	0.0008 (16)
C3	0.024 (2)	0.044 (3)	0.023 (2)	0.0123 (18)	0.0026 (16)	0.0026 (18)
C5	0.024 (2)	0.024 (2)	0.037 (2)	0.0055 (16)	0.0035 (17)	0.0032 (18)
C6	0.024 (2)	0.0171 (19)	0.028 (2)	0.0005 (15)	−0.0030 (16)	0.0058 (16)
C7	0.0161 (18)	0.026 (2)	0.027 (2)	0.0058 (15)	−0.0017 (15)	0.0019 (16)
C8	0.0174 (18)	0.0250 (19)	0.0209 (19)	0.0087 (15)	0.0006 (14)	0.0041 (15)
C1	0.022 (2)	0.027 (2)	0.025 (2)	0.0052 (16)	0.0106 (16)	0.0102 (16)
C2	0.0192 (19)	0.032 (2)	0.036 (2)	0.0056 (16)	0.0099 (17)	0.0118 (18)

Geometric parameters (Å, º)

Cd1—Cl1	2.5270 (11)	N6—H6C	0.8600
Cd1—Cl2	2.5411 (14)	C4—C3	1.511 (5)
Cd1—Cl3	2.6036 (12)	C4—H4C	0.9700
Cd1—Cl4	2.6043 (12)	C4—H4D	0.9700
Cd1—N5	2.646 (4)	C3—H3A	0.9700
Cd1—Cl4^i	2.7237 (14)	C3—H3B	0.9700
Cl4—Cd1^i	2.7237 (13)	C5—C6	1.528 (5)
N1—C7	1.507 (4)	C5—H5A	0.9700
N1—C1	1.511 (4)	C5—H5B	0.9700
N1—C6	1.509 (4)	C6—H6A	0.9700
N1—C4	1.513 (5)	C6—H6B	0.9700
N2—C2	1.490 (5)	C7—C8	1.505 (5)
N2—C3	1.495 (5)	C7—H7A	0.9700
N2—C5	1.504 (5)	C7—H7B	0.9700
N2—H2C	0.9100	C1—C2	1.525 (5)
N5—N4	1.302 (5)	C1—H1A	0.9700
N5—N6	1.343 (4)	C1—H1B	0.9700
N4—N3	1.361 (5)	C2—H2A	0.9700
N3—C8	1.311 (5)	C2—H2B	0.9700
N6—C8	1.330 (5)
Cl1—Cd1—Cl2	96.12 (5)	H4C—C4—H4D	108.2
Cl1—Cd1—Cl3	167.29 (3)	N2—C3—C4	108.8 (3)
Cl2—Cd1—Cl3	91.36 (4)	N2—C3—H3A	109.9
Cl1—Cd1—Cl4	93.78 (4)	C4—C3—H3A	109.9
Cl2—Cd1—Cl4	95.79 (4)	N2—C3—H3B	109.9
Cl3—Cd1—Cl4	95.67 (4)	C4—C3—H3B	109.9
Cl1—Cd1—N5	87.86 (8)	H3A—C3—H3B	108.3
Cl2—Cd1—N5	92.52 (8)	N2—C5—C6	108.0 (3)
Cl3—Cd1—N5	81.54 (8)	N2—C5—H5A	110.1
Cl4—Cd1—N5	171.30 (8)	C6—C5—H5A	110.1
Cl1—Cd1—Cl4^i	91.07 (4)	N2—C5—H5B	110.1
Cl2—Cd1—Cl4^i	171.51 (4)	C6—C5—H5B	110.1
Cl3—Cd1—Cl4^i	80.78 (4)	H5A—C5—H5B	108.4
Cl4—Cd1—Cl4^i	88.23 (4)	N1—C6—C5	109.8 (3)
N5—Cd1—Cl4^i	83.19 (8)	N1—C6—H6A	109.7
Cd1—Cl4—Cd1^i	91.77 (4)	C5—C6—H6A	109.7
C7—N1—C1	111.5 (3)	N1—C6—H6B	109.7
C7—N1—C6	107.0 (3)	C5—C6—H6B	109.7
C1—N1—C6	108.8 (3)	H6A—C6—H6B	108.2
C7—N1—C4	111.7 (3)	C8—C7—N1	114.2 (3)
C1—N1—C4	109.1 (3)	C8—C7—H7A	108.7
C6—N1—C4	108.7 (3)	N1—C7—H7A	108.7
C2—N2—C3	110.1 (3)	C8—C7—H7B	108.7
C2—N2—C5	109.8 (3)	N1—C7—H7B	108.7
C3—N2—C5	109.6 (3)	H7A—C7—H7B	107.6
C2—N2—H2C	109.1	N3—C8—N6	108.9 (3)
C3—N2—H2C	109.1	N3—C8—C7	126.4 (3)
C5—N2—H2C	109.1	N6—C8—C7	124.6 (3)
N4—N5—N6	106.0 (3)	N1—C1—C2	108.7 (3)
N4—N5—Cd1	133.3 (3)	N1—C1—H1A	110.0
N6—N5—Cd1	118.9 (2)	C2—C1—H1A	110.0
N5—N4—N3	110.5 (3)	N1—C1—H1B	110.0
C8—N3—N4	105.8 (3)	C2—C1—H1B	110.0
C8—N6—N5	108.8 (3)	H1A—C1—H1B	108.3
C8—N6—H6C	125.6	N2—C2—C1	109.4 (3)
N5—N6—H6C	125.6	N2—C2—H2A	109.8
C3—C4—N1	109.6 (3)	C1—C2—H2A	109.8
C3—C4—H4C	109.8	N2—C2—H2B	109.8
N1—C4—H4C	109.8	C1—C2—H2B	109.8
C3—C4—H4D	109.8	H2A—C2—H2B	108.3
N1—C4—H4D	109.8
Cl1—Cd1—Cl4—Cd1^i	−90.95 (4)	C2—N2—C5—C6	−67.3 (4)
Cl2—Cd1—Cl4—Cd1^i	172.50 (3)	C3—N2—C5—C6	53.8 (4)
Cl3—Cd1—Cl4—Cd1^i	80.55 (4)	C7—N1—C6—C5	173.3 (3)
Cl4^i—Cd1—Cl4—Cd1^i	0.0	C1—N1—C6—C5	52.7 (4)
Cl1—Cd1—N5—N4	11.4 (4)	C4—N1—C6—C5	−66.0 (4)
Cl2—Cd1—N5—N4	107.4 (4)	N2—C5—C6—N1	11.6 (4)
Cl3—Cd1—N5—N4	−161.6 (4)	C1—N1—C7—C8	−70.5 (4)
Cl1—Cd1—N5—N6	−151.3 (3)	C6—N1—C7—C8	170.6 (3)
Cl2—Cd1—N5—N6	−55.2 (3)	C4—N1—C7—C8	51.8 (4)
Cl3—Cd1—N5—N6	35.8 (3)	N4—N3—C8—N6	−0.1 (4)
N6—N5—N4—N3	0.7 (4)	N4—N3—C8—C7	175.5 (3)
Cd1—N5—N4—N3	−163.5 (3)	N5—N6—C8—N3	0.6 (4)
N5—N4—N3—C8	−0.4 (4)	N5—N6—C8—C7	−175.1 (3)
N4—N5—N6—C8	−0.8 (4)	N1—C7—C8—N3	86.8 (5)
Cd1—N5—N6—C8	166.1 (2)	N1—C7—C8—N6	−98.2 (4)
C7—N1—C4—C3	169.7 (3)	C7—N1—C1—C2	175.7 (3)
C1—N1—C4—C3	−66.7 (4)	C6—N1—C1—C2	−66.4 (4)
C6—N1—C4—C3	51.8 (4)	C4—N1—C1—C2	52.0 (4)
C2—N2—C3—C4	52.6 (4)	C3—N2—C2—C1	−67.1 (4)
C5—N2—C3—C4	−68.3 (4)	C5—N2—C2—C1	53.7 (4)
N1—C4—C3—N2	12.4 (4)	N1—C1—C2—N2	11.8 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl1^ii	0.91	2.71	3.301 (3)	123
N2—H2C···Cl3^iii	0.91	2.57	3.205 (3)	127
N2—H2C···Cl4^ii	0.91	2.64	3.278 (3)	128
N6—H6C···Cl3^iv	0.86	2.31	3.122 (3)	156
C4—H4C···Cl2^v	0.97	2.74	3.608 (4)	149
C4—H4D···Cl3^iv	0.97	2.66	3.569 (4)	156
C6—H6A···Cl1^vi	0.97	2.58	3.521 (4)	163
C6—H6B···Cl4^iv	0.97	2.58	3.412 (4)	145

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