A novel two-dimensional framework based on unprecedented cadmium(II) chains

The bent ligand 4-[(1H-1,2,4-triazol-1-yl)meth­yl]benzoic acid (HL) has been used to create the novel two-dimensional coordination polymer poly[[mu]₂-aqua-[mu]₂-chlorido-{[mu]₂-4-[(1H-1,2,4-triazol-1­-yl)meth­yl]benzoato}cadmium(II)], [Cd(C₁₀H₈N₃O₂)Cl(H₂O)]_n, under hydro­thermal reaction of HL with cadmium chloride. The crystallographically unique Cd atom is seven-coordinated in an approximately penta­gonal-bipy­ramidal environment of two carboxyl­ate O atoms, two water O atoms, two Cl atoms and one triazole N atom. A notable feature is the presence of zigzag ...Cd...Cd... inorganic chains, in which neighboring Cd^II ions are doubly bridged by pairs of [mu]₂-Cl atoms and [mu]₂-H₂O ligands in an alternating fashion. To the authors' knowledge, this is the first example containing this bridging mode in a cadmium(II) framework. The chains are connected to one another through the bridging L^- ligand into a two-dimensional undulating network. All of the two-dimensional nets stack exactly together in an ...AA... stacking sequence along the crystallographic b axis. Neighboring layers are further linked into a three-dimensional framework via inter­layer hydrogen-bonding inter­actions.

S1. Comment

The rational design and synthesis of supramolecular complexes are of great interest not only because of their potential applications in heterogenous catalysis (Wu & Lin, 2007), magnetism (Maspoch et al., 2004), gas adsorption and separation (Rowsell & Yaghi, 2005), and luminescent materials (Dong et al., 2007), but also owing to their intriguing structures (Wan et al., 2008). In principle, some control over the type and topology of the product generated from the self-assembly of organic ligands and inorganic metal ions can be achieved by the functionality of the ligand (Munakata et al., 1997). It is well known that 1,2,4-triazole and its derivatives are useful building blocks for the construction of metal–organic frameworks because they unite the coordination modes of pyrazole and imidazole. They exhibit the particularly useful property of acting as bridging ligands between two metal centers, which can afford diverse supramolecular complexes (Haasnoot, 2000).

Although derivatives of the 1,2,4-triazole ligand, especially the amino-substituted (Keij et al., 1984; Shakir et al., 2003), aryl-substituted (Klingele & Brooker, 2003; Wang et al., 2007) and alkyl-substituted (Bradford et al., 2004; Yi et al., 2004) ones, have been well studied, very little attention has been paid to carboxylate-substituted 1,2,4-triazole ligands (Ding et al., 2008). Previously, we reported a study of the M^II (M = Co and Zn) coordination chemistry of the carboxylate-substituted 1,2,4-triazole 4-[(1H-1,2,4-triazol-1-yl)methyl]benzoic acid (HL; Zhao et al., 2007). As an extension of this study, we investigated the self-assembly reaction of L^- with cadmium chloride under hydrothermal conditions and the novel supramolecular complex, [Cd(C₁₀H₈N₃O₂)Cl(H₂O)]_n, (I), was isolated.

Compound (I) crystallizes in the triclinic space group P1 with only one unique seven-coordinated Cd^II center. Each Cd^II ion lies in a pseudo-pentagonal–bipyramidal coordination environment with two O atoms (O1 and O2) from the carboxylate group, two O atoms [O3 and O3ⁱⁱⁱ; symmetry code: (iii) -x + 2, -y, -z] from water molecules and one Cl atom (Cl1) in the equatorial plane, and one N atom [N1ⁱ; symmetry code: (i) -x + 2, -y + 1, -z + 1] and one Cl atom [Cl1ⁱⁱ; symmetry code (ii): -x + 1, -y, -z] in the axial positions (Fig. 1 and Table 1). All the Cd—O, Cd—Cl and Cd—N bonds are consistent with values reported for Cd–carboxylate, [Cd₂(µ₂-OH₂)₂], [Cd₂(µ₂-Cl)₂] and Cd–triazole complexes (Yong et al., 2005; Liu et al., 2006; Yi et al., 2004).

In the extended structure, neighboring Cd^II centers are doubly bridged by µ₂-Cl atoms and µ₂-OH₂ molecules, alternately, to form a square [Cd₂(µ₂-Cl)₂] core with a Cd···Cd contact of 3.703 (15) Å and a rhomboidal [Cd₂(µ₂-OH₂)₂] core with a Cd···Cd contact of 4.028 (12) Å, respectively. These adjacent units are almost perpendicular (the dihedral angle is 82.1° [s.u. value available?]) and arrange alternately to form a zigzag chain extending along the crystallographic a axis (Fig. 2). In the previously reported Cd coordination polymers, the adjacent [Cd₂(µ₂-Cl)₂] units are mostly doubly bridged by µ₂-Cl atoms (Huang et al., 1998; Yi et al., 2004; Barros-Garcia et al., 2004). In those cases, no bridging water molecules were observed, whereas in this study, the adjacent [Cd₂(µ₂-Cl)₂] units are doubly bridged by µ₂-OH₂ molecules. As far as we know, (I) is the first complex containing both µ₂-Cl and µ₂-OH₂ bridges between two Cd^II ions.

These inorganic chains are doubly bridged by the chelating carboxylate group and terminal N_triazole of ligand L^- into a novel two-dimensional network (Fig. 3). When viewed down the crystallographic a direction, parallelogram-like cavities are found, which are composed of two Cd^II centers and two bent L^- ligands; the distance between two diagonal Cd^II centers is 12.40 (s.u.?) Å (Fig. 4). The two-dimensional network is strengthened by intralayer hydrogen bonds (O—H···O) consisting of the H atom of the water molecule and an O atom of the carboxylate group. These two-dimensional layers are arranged in the crystal in an ···AA··· fashion and are further linked into a three-dimensional framework via interlayer hydrogen-bonding interactions along the crystallographic b axis (Fig. 4 and Table 2). The hydrogen-bonding system involves an uncoordinated N atom of the triazole ring and the H atom of a water molecule in a neighboring layer.

In summary, the most interesting feature in (I) is the presence of zigzag Cd^II chains formed by µ₂-Cl and µ₂-OH₂ bridges. This behavior may offer a route to new types of Cl-bridged structures.

Related literature

For related literature, see: Barros-Garcia, Bernalte-Garcia, Higes-Rolando, Luna-Giles, Pedrero-Marin & Vinuelas-Zahinos (2004); Bradford et al. (2004); Ding et al. (2008); Dong et al. (2007); Haasnoot (2000); Huang et al. (1998); Keij et al. (1984); Klingele & Brooker (2003); Liu et al. (2006); Maspoch et al. (2004); Munakata et al. (1997); Rowsell & Yaghi (2005); Shakir et al. (2003); Wan et al. (2008); Wang et al. (2007); Wu & Lin (2007); Yi et al. (2004); Yong et al. (2005); Zhao et al. (2007).

S2. Experimental

All the solvents and reagents for synthesis were commercially available and used as received.

A mixture of 4-methylbenzoic acid (2.72 g, 20.0 mmol), succinbromimide (3.56 g, 20.0 mmol), benzoyl peroxide (0.050 g, 206.0 mm mol) and carbon tetrachloride (40 ml) was refluxed for 5 h. After cooling to room temperature, a pink precipitate was obtained by filtration and subsequently washed with carbon tetrachloride and water. Recrystallization in dichloromethane provided a white solid, 4-bromomethyl benzoic acid, in 88.3% yield.

KOH (3.02 g, 5.0 mmol) was added with stirring to a solution of 4-bromomethyl benzoic acid (2.15 g, 1 mmol) and 1H-1,2,4-triazole (0.70 g, 1 mmol) in water (60 ml). The mixture was stirred for 12 h, then acidified with hydrochloric acid to adjust the pH value to 2, and the white precipitate was filtered off and recrystallized in methanol to provide the product HL (yield 89.2%). ¹H NMR (300 MHz, DMSO-d₆, p.p.m): δ 12.99 (s, 1H, COOH), 8.68 (s, 1H, CH), 8.02 (s, 1H, CH), 7.92–7.32 (m, 4H, p-C₆H₄), 5.50 (s, 2H, CH₂). IR (KBr, cm^-1): 3455, 3119, 2950, 2362, 1913, 1694, 1516, 1432, 1275, 1142, 1013, 917, 731, 675.

A mixture of HL (20.3 mg, 0.10 mmol), CdCl₂ (23.8 mg, 0.10 mmol) and deionized water (2 ml) was sealed in a 5 ml test tube, heated at 453 K for 40 h and cooled slowly to room temperature over 50 h. Colorless crystals were isolated in 80% yield (based on HL). IR (KBr, cm^-1): 3446, 3119, 1590, 1541, 1393, 1281, 1216, 1117, 1132, 997, 785, 761, 677, 639. Elemental analysis calculated for C₁₀H₁₀CdClN₃O₃: C 32.60, H 2.71, N 11.41%; found: C 32.64, H 2.68, N 11.43%.

S3. Refinement

H atoms were placed in geometrically idealized positions and included as riding atoms with C—H distances of 0.97 (CH₂) or 0.93 Å (CH), O—H distances of 0.97 Å and U_iso(H) values of 1.2U_eq(C,O). The phenyl ring was disordered over two positions that refined to a ratio of 0.48 (4)/0.52 (4).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (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) (displacement ellipsoids are shown with 30% probability). [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 1, -y, -z; (iii) -x + 2, -y, -z.]
	Fig. 2. The zigzag chain in (I), showing the alternating Cl and H2O bridging of the Cd^II centers.
	Fig. 3. A view of the two-dimensional supramolecular framework of (I) in approximately the ac plane.
	Fig. 4. A perspective view along the a axis of the three-dimensional hydrogen-bonded network in (I) (hydrogen-bonding interactions are shown as dashed lines).

poly[µ₂-aqua-µ₂-chlorido-{m₂-4-[(1H-1,2,4-triazol-1- yl)methyl]benzoato}cadmium(II)]

Crystal data

[Cd(C10H8N3O2)Cl(H2O)]	Z = 2
Mr = 368.06	F(000) = 360
Triclinic, P1	Dx = 2.012 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.977 (3) Å	Cell parameters from 2230 reflections
b = 8.052 (4) Å	θ = 2.6–28.0°
c = 13.091 (6) Å	µ = 2.02 mm^−1
α = 101.516 (6)°	T = 298 K
β = 96.291 (6)°	Plan, colourless
γ = 96.612 (6)°	0.45 × 0.11 × 0.05 mm
V = 607.6 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2089 independent reflections
Radiation source: fine-focus sealed tube	1993 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→6
Tmin = 0.463, Tmax = 0.906	k = −8→9
2928 measured reflections	l = −12→15

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0784P)^2 + 0.8048P] where P = (Fo^2 + 2Fc^2)/3
2089 reflections	(Δ/σ)max = 0.001
200 parameters	Δρmax = 1.29 e Å^−3
0 restraints	Δρmin = −1.05 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	Occ. (<1)
Cd1	0.76745 (5)	0.08660 (4)	0.08984 (2)	0.02337 (17)
C1	0.6661 (9)	0.1343 (6)	0.2946 (4)	0.0280 (10)
C2	0.6392 (8)	0.1822 (6)	0.4084 (4)	0.0266 (10)	0.48 (4)
C3	0.784 (3)	0.131 (3)	0.4842 (11)	0.025 (4)	0.48 (4)
H3	0.8988	0.0687	0.4636	0.030*	0.48 (4)
C4	0.758 (4)	0.173 (3)	0.5891 (12)	0.032 (4)	0.48 (4)
H4	0.8488	0.1318	0.6380	0.038*	0.48 (4)
C5	0.5991 (8)	0.2743 (6)	0.6223 (4)	0.0279 (10)	0.48 (4)
C6	0.456 (4)	0.328 (3)	0.5494 (15)	0.031 (4)	0.48 (4)
H6	0.3463	0.3950	0.5713	0.038*	0.48 (4)
C7	0.475 (4)	0.280 (3)	0.4426 (16)	0.035 (4)	0.48 (4)
H7	0.3755	0.3143	0.3936	0.041*	0.48 (4)
C8	0.5722 (9)	0.3222 (7)	0.7374 (4)	0.0328 (11)
H8A	0.4414	0.3824	0.7447	0.039*
H8B	0.5436	0.2186	0.7639	0.039*
C9	0.8292 (9)	0.5968 (6)	0.8156 (4)	0.0298 (10)
H9	0.7383	0.6708	0.7911	0.036*
C10	1.0985 (9)	0.4959 (6)	0.8887 (4)	0.0296 (11)
H10	1.2370	0.4897	0.9267	0.036*
N3	0.9452 (7)	0.3617 (5)	0.8469 (3)	0.0303 (9)
C2'	0.6392 (8)	0.1822 (6)	0.4084 (4)	0.0266 (10)	0.52 (4)
C3'	0.826 (3)	0.211 (4)	0.4835 (13)	0.043 (4)	0.52 (4)
H3'	0.9681	0.2017	0.4623	0.052*	0.52 (4)
C4'	0.810 (3)	0.253 (4)	0.5888 (12)	0.045 (5)	0.52 (4)
H4'	0.9395	0.2676	0.6379	0.054*	0.52 (4)
C5'	0.5991 (8)	0.2743 (6)	0.6223 (4)	0.0279 (10)	0.52 (4)
C6'	0.417 (3)	0.253 (4)	0.5462 (14)	0.037 (4)	0.52 (4)
H6'	0.2762	0.2706	0.5668	0.044*	0.52 (4)
C7'	0.431 (3)	0.207 (3)	0.4410 (15)	0.038 (4)	0.52 (4)
H7'	0.3021	0.1916	0.3918	0.045*	0.52 (4)
Cl1	0.44209 (19)	0.21404 (13)	−0.01978 (9)	0.0256 (3)
N1	1.0330 (7)	0.6439 (5)	0.8705 (3)	0.0282 (9)
N2	0.7731 (7)	0.4303 (5)	0.8006 (3)	0.0276 (9)
O1	0.5067 (7)	0.1470 (5)	0.2261 (3)	0.0395 (9)
O2	0.8462 (7)	0.0853 (6)	0.2702 (3)	0.0459 (10)
O3	1.1155 (5)	−0.0387 (4)	0.0938 (3)	0.0245 (7)
H3A	1.0923	−0.1468	0.1158	0.029*
H3B	1.2341	0.0372	0.1436	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0205 (2)	0.0250 (2)	0.0225 (2)	0.00216 (15)	−0.00027 (15)	0.00234 (15)
C1	0.029 (3)	0.028 (2)	0.026 (2)	0.0026 (19)	0.001 (2)	0.0060 (19)
C2	0.021 (2)	0.032 (2)	0.024 (2)	0.0010 (18)	−0.0025 (19)	0.0041 (19)
C3	0.017 (7)	0.037 (9)	0.020 (5)	0.008 (6)	−0.009 (4)	0.004 (6)
C4	0.026 (9)	0.044 (10)	0.025 (6)	0.010 (7)	−0.007 (5)	0.008 (7)
C5	0.022 (2)	0.032 (2)	0.026 (2)	−0.0053 (19)	0.0017 (19)	0.0027 (19)
C6	0.040 (9)	0.031 (9)	0.025 (6)	0.016 (7)	0.004 (6)	0.003 (7)
C7	0.033 (10)	0.043 (11)	0.030 (7)	0.017 (8)	−0.002 (6)	0.010 (8)
C8	0.026 (3)	0.043 (3)	0.023 (2)	−0.008 (2)	0.001 (2)	0.001 (2)
C9	0.029 (3)	0.030 (2)	0.029 (2)	0.007 (2)	−0.003 (2)	0.005 (2)
C10	0.028 (3)	0.030 (2)	0.029 (3)	0.006 (2)	−0.003 (2)	0.003 (2)
N3	0.033 (2)	0.026 (2)	0.030 (2)	0.0040 (17)	−0.0033 (17)	0.0047 (17)
C2'	0.021 (2)	0.032 (2)	0.024 (2)	0.0010 (18)	−0.0025 (19)	0.0041 (19)
C3'	0.028 (7)	0.061 (13)	0.037 (7)	0.002 (8)	0.009 (5)	−0.001 (8)
C4'	0.023 (7)	0.080 (15)	0.022 (6)	0.001 (8)	−0.007 (5)	−0.003 (8)
C5'	0.022 (2)	0.032 (2)	0.026 (2)	−0.0053 (19)	0.0017 (19)	0.0027 (19)
C6'	0.018 (6)	0.058 (13)	0.034 (7)	0.012 (8)	0.000 (5)	0.005 (9)
C7'	0.030 (7)	0.052 (12)	0.030 (6)	0.004 (8)	−0.002 (5)	0.010 (9)
Cl1	0.0219 (6)	0.0250 (5)	0.0283 (6)	0.0023 (4)	−0.0024 (4)	0.0058 (4)
N1	0.027 (2)	0.027 (2)	0.027 (2)	0.0043 (16)	−0.0030 (17)	0.0010 (17)
N2	0.026 (2)	0.030 (2)	0.024 (2)	0.0016 (16)	0.0020 (16)	0.0024 (16)
O1	0.040 (2)	0.052 (2)	0.0246 (18)	0.0135 (18)	−0.0044 (16)	0.0062 (16)
O2	0.039 (2)	0.072 (3)	0.0274 (19)	0.021 (2)	0.0054 (17)	0.0044 (19)
O3	0.0198 (17)	0.0270 (16)	0.0260 (17)	0.0043 (13)	−0.0021 (13)	0.0063 (13)

Geometric parameters (Å, º)

Cd1—N1^i	2.284 (4)	C8—N2	1.462 (6)
Cd1—O2	2.358 (4)	C8—H8A	0.9700
Cd1—O3	2.414 (3)	C8—H8B	0.9700
Cd1—O1	2.507 (4)	C9—N2	1.314 (6)
Cd1—Cl1^ii	2.5364 (15)	C9—N1	1.318 (7)
Cd1—O3^iii	2.546 (3)	C9—H9	0.9300
Cd1—Cl1	2.7075 (14)	C10—N3	1.316 (6)
C1—O2	1.241 (6)	C10—N1	1.353 (6)
C1—O1	1.263 (6)	C10—H10	0.9300
C1—C2	1.494 (7)	N3—N2	1.364 (6)
C2—C7	1.39 (2)	C3'—C4'	1.37 (2)
C2—C3	1.399 (14)	C3'—H3'	0.9300
C3—C4	1.38 (2)	C4'—H4'	0.9300
C3—H3	0.9300	C6'—C7'	1.37 (3)
C4—C5	1.372 (17)	C6'—H6'	0.9300
C4—H4	0.9300	C7'—H7'	0.9300
C5—C6	1.379 (19)	Cl1—Cd1^ii	2.5364 (15)
C5—C8	1.510 (7)	N1—Cd1^i	2.284 (4)
C6—C7	1.39 (3)	O3—Cd1^iii	2.546 (3)
C6—H6	0.9300	O3—H3A	0.9700
C7—H7	0.9300	O3—H3B	0.9700
N1^i—Cd1—O2	86.89 (15)	C5—C6—H6	120.1
N1^i—Cd1—O3	91.10 (13)	C7—C6—H6	120.1
O2—Cd1—O3	78.83 (12)	C2—C7—C6	121.0 (16)
N1^i—Cd1—O1	95.23 (14)	C2—C7—H7	119.5
O2—Cd1—O1	53.35 (13)	C6—C7—H7	119.5
O3—Cd1—O1	131.14 (11)	N2—C8—C5	112.5 (4)
N1^i—Cd1—Cl1^ii	172.00 (10)	N2—C8—H8A	109.1
O2—Cd1—Cl1^ii	100.50 (12)	C5—C8—H8A	109.1
O3—Cd1—Cl1^ii	87.38 (9)	N2—C8—H8B	109.1
O1—Cd1—Cl1^ii	91.67 (9)	C5—C8—H8B	109.1
N1^i—Cd1—O3^iii	90.17 (13)	H8A—C8—H8B	107.8
O2—Cd1—O3^iii	150.04 (12)	N2—C9—N1	110.1 (4)
O3—Cd1—O3^iii	71.43 (12)	N2—C9—H9	124.9
O1—Cd1—O3^iii	156.48 (11)	N1—C9—H9	124.9
Cl1^ii—Cd1—O3^iii	81.90 (8)	N3—C10—N1	112.8 (4)
N1^i—Cd1—Cl1	87.03 (11)	N3—C10—H10	123.6
O2—Cd1—Cl1	132.10 (10)	N1—C10—H10	123.6
O3—Cd1—Cl1	148.76 (8)	C10—N3—N2	103.4 (4)
O1—Cd1—Cl1	80.05 (9)	C4'—C3'—H3'	118.9
Cl1^ii—Cd1—Cl1	90.20 (4)	C3'—C4'—H4'	120.1
O3^iii—Cd1—Cl1	77.39 (8)	C7'—C6'—H6'	118.4
O2—C1—O1	121.8 (5)	C6'—C7'—H7'	120.3
O2—C1—C2	118.9 (4)	Cd1^ii—Cl1—Cd1	89.80 (4)
O1—C1—C2	119.3 (4)	C9—N1—C10	104.2 (4)
C7—C2—C3	118.0 (11)	C9—N1—Cd1^i	126.2 (3)
C7—C2—C1	121.7 (9)	C10—N1—Cd1^i	129.4 (3)
C3—C2—C1	120.4 (7)	C9—N2—N3	109.5 (4)
C4—C3—C2	120.6 (12)	C9—N2—C8	128.7 (4)
C4—C3—H3	119.7	N3—N2—C8	121.5 (4)
C2—C3—H3	119.7	C1—O1—Cd1	88.4 (3)
C5—C4—C3	120.8 (12)	C1—O2—Cd1	95.9 (3)
C5—C4—H4	119.6	Cd1—O3—Cd1^iii	108.57 (12)
C3—C4—H4	119.6	Cd1—O3—H3A	110.0
C4—C5—C6	119.7 (11)	Cd1^iii—O3—H3A	110.0
C4—C5—C8	120.9 (8)	Cd1—O3—H3B	110.0
C6—C5—C8	119.3 (9)	Cd1^iii—O3—H3B	110.0
C5—C6—C7	119.8 (15)	H3A—O3—H3B	108.4
O2—C1—C2—C7	162.2 (15)	N1—C9—N2—C8	−174.6 (4)
O1—C1—C2—C7	−16.8 (15)	C10—N3—N2—C9	0.3 (5)
O2—C1—C2—C3	−16.7 (14)	C10—N3—N2—C8	175.3 (4)
O1—C1—C2—C3	164.3 (12)	C5—C8—N2—C9	83.0 (7)
C7—C2—C3—C4	2.0 (17)	C5—C8—N2—N3	−91.0 (5)
C1—C2—C3—C4	−179.0 (10)	O2—C1—O1—Cd1	−7.6 (5)
C2—C3—C4—C5	−4 (2)	C2—C1—O1—Cd1	171.3 (4)
C3—C4—C5—C6	3.6 (18)	N1^i—Cd1—O1—C1	−78.0 (3)
C3—C4—C5—C8	−179.2 (10)	O2—Cd1—O1—C1	4.2 (3)
C4—C5—C6—C7	−0.8 (19)	O3—Cd1—O1—C1	18.1 (3)
C8—C5—C6—C7	−178.2 (11)	Cl1^ii—Cd1—O1—C1	106.1 (3)
C3—C2—C7—C6	0.7 (19)	O3^iii—Cd1—O1—C1	179.5 (2)
C1—C2—C7—C6	−178.3 (11)	Cl1—Cd1—O1—C1	−164.0 (3)
C5—C6—C7—C2	−1 (2)	O1—C1—O2—Cd1	8.1 (5)
C4—C5—C8—N2	65.4 (14)	C2—C1—O2—Cd1	−170.8 (4)
C6—C5—C8—N2	−117.3 (13)	N1^i—Cd1—O2—C1	94.5 (3)
N1—C10—N3—N2	−0.5 (5)	O3—Cd1—O2—C1	−173.7 (4)
N1^i—Cd1—Cl1—Cd1^ii	172.49 (10)	O1—Cd1—O2—C1	−4.3 (3)
O2—Cd1—Cl1—Cd1^ii	−104.40 (16)	Cl1^ii—Cd1—O2—C1	−88.5 (3)
O3—Cd1—Cl1—Cd1^ii	85.27 (16)	O3^iii—Cd1—O2—C1	179.5 (2)
O1—Cd1—Cl1—Cd1^ii	−91.66 (10)	Cl1—Cd1—O2—C1	11.4 (4)
Cl1^ii—Cd1—Cl1—Cd1^ii	0.0	N1^i—Cd1—O3—Cd1^iii	−89.81 (14)
O3^iii—Cd1—Cl1—Cd1^ii	81.66 (8)	O2—Cd1—O3—Cd1^iii	−176.42 (17)
N2—C9—N1—C10	−0.3 (6)	O1—Cd1—O3—Cd1^iii	172.27 (12)
N2—C9—N1—Cd1^i	174.9 (3)	Cl1^ii—Cd1—O3—Cd1^iii	82.34 (10)
N3—C10—N1—C9	0.5 (6)	O3^iii—Cd1—O3—Cd1^iii	0.0
N3—C10—N1—Cd1^i	−174.5 (3)	Cl1—Cd1—O3—Cd1^iii	−3.7 (2)
N1—C9—N2—N3	0.0 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N3^iv	0.97	1.89	2.854 (5)	177
O3—H3B···O1^v	0.97	1.87	2.824 (5)	167

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