Poly[μ-aqua-diaqua(μ3-1H-benzimid­azole-5-carboxylato-κ3N3:O,O′)(μ2-1H-benzimidazole-5-carboxylato-κ3N3:O:O′)-μ5-sulfato-μ4-sulfato-tri­cadmium]

Chen, L.-C.; Huo, S.-M.; Chen, H.-Z.; Yang, Y.-Q.; Zeng, R.-H.

doi:10.1107/S1600536811034477

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1312-m1313

doi:10.1107/S1600536811034477

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Poly[μ-aqua-diaqua(μ₃-1H-benzimidazole-5-carboxylato-κ³N³:O,O′)(μ₂-1H-benzimidazole-5-carboxylato-κ³N³:O:O′)-μ₅-sulfato-μ₄-sulfato-tricadmium]

Lai-Chen Chen,^a Shu-Min Huo,^a Hao-Zhao Chen,^a Ya-Qing Yang ^a and Rong-Hua Zeng ^a,^b ^*

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^bKey Laboratory of Technology of Electrochemical Energy Storage and Power Generation in Guangdong Universities, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: zrh321@yahoo.com.cn

(Received 11 August 2011; accepted 22 August 2011; online 27 August 2011)

The asymmetric unit of the title compound, [Cd₃(C₈H₅N₂O₂)₂(SO₄)₂(H₂O)₃]_n, contains three Cd^II ions, two sulfate anions, two 1H-benzimidazole-5-carboxylate (H₂bic) ligands and three coordinated water molecules. One Cd^II ion is six-coordinated and exhibits a distorted octahedral geometry, while the other two Cd^II ions are seven-coordinated, displaying a distorted pentagonal–bipyramidal geometry. The Cd^II ions are bridged by two types of sulfate anions, producing inorganic chains along [100]. These chains are further connected by the H₂bic ligands, leading to a three-dimensional framework. N—H⋯O and O—H⋯O hydrogen bonds and π–π interactions between the imidazole and benzene rings [centroid–centroid distances = 3.953 (2), 3.507 (2), 3.407 (2) and 3.561 (2) Å] further stabilize the crystal structure.

Related literature

For background to 1H-benzimidazole-5-carboxylate complexes, see: Gao et al. (2011 ); Guo et al. (2007 ); Peng, Ma et al. (2010 ); Peng, Qiu et al. (2010 ); Yao et al. (2008 ).

Experimental

Crystal data

[Cd₃(C₈H₅N₂O₂)₂(SO₄)₂(H₂O)₃]
M_r = 905.65
Triclinic, $[P \overline 1]$
a = 6.5932 (8) Å
b = 13.0463 (16) Å
c = 13.5933 (16) Å
α = 104.313 (1)°
β = 96.662 (1)°
γ = 97.646 (1)°
V = 1109.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.13 mm⁻¹
T = 298 K
0.30 × 0.27 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.454, T_max = 0.508
5772 measured reflections
3935 independent reflections
3593 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.067
S = 1.06
3935 reflections
361 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O10ⁱ	0.86	1.98	2.836 (4)	176
N4—H4A⋯O7ⁱⁱ	0.86	1.98	2.716 (4)	143
O1W—H1W⋯O3ⁱⁱⁱ	0.85	1.91	2.736 (4)	163
O1W—H2W⋯O2^iv	0.85	1.91	2.734 (4)	165
O2W—H3W⋯O3^v	0.85	1.99	2.770 (4)	153
O2W—H4W⋯O10^v	0.85	2.01	2.687 (4)	136
O3W—H5W⋯O8ⁱ	0.85	2.23	2.925 (4)	139
O3W—H6W⋯O4^vi	0.85	2.09	2.918 (4)	166
Symmetry codes: (i) -x+2, -y+1, -z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y, -z; (v) -x+2, -y+1, -z+1; (vi) x+1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811034477/hy2460sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034477/hy2460Isup2.hkl

checkCIF report

Comment top

There is currently much interest in employing N-heterocyclic carboxylic acids as multidentate ligands to design metal coordination polymers. This is because they have versatile coordination modes and can form high-dimensional polymers through hydrogen-bonding interactions in the process of self-assembly. 1H-Benzimidazole-5-carboxylic acid (H₂bic), having two N atoms of an aromatic group and one carboxylate group, is a good candidate for preparing novel coordination polymers. Up to now, one-, two- and three-dimensional coordination polymers constructed from the H₂bic ligand have been reported (Gao et al., 2011; Guo et al., 2007; Peng et al., 2010a,b; Yao et al., 2008). Herein we report the synthesis and crystal structure of the title complex.

As is shown in Fig. 1, the asymmetric unit of the title compound consists of three crystallographically independent Cd^II ions, two SO₄^2- anions, two H₂bic ligands and three coordinated water molecules. The Cd2 atom is six-coordinated by one O atom and one N atom from two different H₂bic ligands, two O atoms from two SO₄^2- anions and two water molecules, forming a distorted octahedral geometry. Both Cd1 and Cd3 atoms are seven-coordinated, displaying a distorted pentagonal-bipyramidal geometry. The Cd1 atom is coordinated by two O atoms from one H₂bic ligand, four O atoms from four SO₄^2- anions and one water molecule, while Cd3 atom is surrounded by one O atom and one N atom from two H₂bic ligands, four O atoms from three SO₄^2- anions and one water molecule. The Cd—O bond lengths range from 2.266 (3) to 2.532 (3) Å and the Cd—N distances vary from 2.230 (3) to 2.272 (3) Å.

In the title compound, the SO₄^2- anions adopt two coordination modes. One is a µ₄-mode, bridging four Cd^II ions and the other is a µ₅-mode, bridging five Cd^II ions. As is described in Fig. 2, the Cd^II ions are bridged by the two types of SO₄^2- anions, producing a one-dimensional inorganic chain along [1 0 0]. These chains are further bridged by the carboxylate and imidazole groups of the H₂bic ligands, resulting in a three-dimensional framework (Fig. 3). To the best of our knowledge, the title compound is the first three-dimensional transition metal coordination polymer based on H₂bic ligand. N—H···O and O—H···O hydrogen bonds (Table 1) and π–π interactions between the imidazole and benzene rings [centroid–centroid distances = 3.953 (2), 3.507 (2), 3.407 (2) and 3.561 (2) Å] further stabilize the crystal structure.

Related literature top

For background to 1H-benzimidazole-5-carboxylate complexes, see: Gao et al. (2011); Guo et al. (2007); Peng et al. (2010a,b); Yao et al. (2008).

Experimental top

A mixture of CdSO₄ (0.208 g, 1 mmol), H₂bic (0.162 g, 1 mmol) and water (10 ml) was stirred vigorously for 30 min and then sealed in a 20 ml Teflon-lined stainless-steel autoclave. The autoclave was heated and maintained at 433 K for 3 days, and then cooled to room temperature at 5 K h^-1. Colorless block crystals were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) x-1, y, z; (ii) -x+2, -y+1, -z+1; (iii) x, y-1, z; (iv) -x+2, -y, -z; (v) x+1, y, z.]
	Fig. 2. The one-dimensional chain extending along [1 0 0], formed by Cd atoms and sulfate anions.
	Fig. 3. A view of the three-dimensional structure of the title compound.

Poly[µ-aqua-diaqua(µ₃-1H-benzimidazole-5-carboxylato- κ³N³:O,O')(µ₂-1H-benzimidazole-5- carboxylato-κ³N³:O:O')-µ₅-sulfato-µ₄-sulfato- tricadmium] top

Crystal data top

[Cd₃(C₈H₅N₂O₂)₂(SO₄)₂(H₂O)₃]	Z = 2
M_r = 905.65	F(000) = 872
Triclinic, P1	D_x = 2.711 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5932 (8) Å	Cell parameters from 3917 reflections
b = 13.0463 (16) Å	θ = 2.5–25.2°
c = 13.5933 (16) Å	µ = 3.13 mm⁻¹
α = 104.313 (1)°	T = 298 K
β = 96.662 (1)°	Block, colorless
γ = 97.646 (1)°	0.30 × 0.27 × 0.25 mm
V = 1109.3 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	3935 independent reflections
Radiation source: fine-focus sealed tube	3593 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
T_min = 0.454, T_max = 0.508	k = −13→15
5772 measured reflections	l = −16→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0305P)² + 1.2679P] where P = (F_o² + 2F_c²)/3
3935 reflections	(Δ/σ)_max = 0.001
361 parameters	Δρ_max = 0.56 e Å⁻³
1 restraint	Δρ_min = −0.71 e Å⁻³

Crystal data top

[Cd₃(C₈H₅N₂O₂)₂(SO₄)₂(H₂O)₃]	γ = 97.646 (1)°
M_r = 905.65	V = 1109.3 (2) Å³
Triclinic, P1	Z = 2
a = 6.5932 (8) Å	Mo Kα radiation
b = 13.0463 (16) Å	µ = 3.13 mm⁻¹
c = 13.5933 (16) Å	T = 298 K
α = 104.313 (1)°	0.30 × 0.27 × 0.25 mm
β = 96.662 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3935 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3593 reflections with I > 2σ(I)
T_min = 0.454, T_max = 0.508	R_int = 0.020
5772 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	1 restraint
wR(F²) = 0.067	H-atom parameters constrained
S = 1.06	Δρ_max = 0.56 e Å⁻³
3935 reflections	Δρ_min = −0.71 e Å⁻³
361 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.61304 (4)	0.48371 (2)	0.37140 (2)	0.01777 (9)
Cd2	0.84093 (4)	0.24373 (2)	0.30872 (2)	0.01851 (9)
Cd3	1.17453 (4)	0.31863 (2)	0.10959 (2)	0.01829 (9)
S1	0.66513 (14)	0.33480 (8)	0.11673 (7)	0.0152 (2)
S2	1.12894 (14)	0.49174 (7)	0.36347 (7)	0.0135 (2)
N1	1.0207 (5)	0.2733 (3)	−0.0571 (2)	0.0197 (7)
C6	1.0162 (6)	0.3440 (3)	−0.1108 (3)	0.0225 (9)
H6	1.0520	0.4177	−0.0821	0.027*
C8	0.9189 (6)	0.0704 (3)	−0.1153 (3)	0.0154 (8)
H8	0.9361	0.0589	−0.0502	0.018*
C7	0.9513 (6)	0.1732 (3)	−0.1279 (3)	0.0156 (8)
C3	0.8338 (6)	0.0033 (3)	−0.3013 (3)	0.0218 (9)
H3	0.8002	−0.0553	−0.3589	0.026*
C4	0.8563 (7)	0.1046 (4)	−0.3146 (3)	0.0246 (9)
H4	0.8338	0.1158	−0.3797	0.030*
C5	0.9148 (6)	0.1906 (3)	−0.2263 (3)	0.0191 (8)
C2	0.8598 (6)	−0.0150 (3)	−0.2030 (3)	0.0161 (8)
C16	0.6557 (7)	0.8881 (3)	0.4017 (3)	0.0226 (9)
H16	0.6714	0.8841	0.4695	0.027*
C9	0.6064 (6)	0.6877 (3)	0.3474 (3)	0.0195 (9)
C10	0.6106 (6)	0.7927 (3)	0.3226 (3)	0.0183 (8)
C15	0.6775 (7)	0.9878 (3)	0.3828 (3)	0.0240 (9)
H15	0.7064	1.0506	0.4361	0.029*
O6	0.8233 (4)	0.2704 (2)	0.1470 (2)	0.0239 (6)
O5	0.5458 (5)	0.3615 (2)	0.2041 (2)	0.0259 (7)
O8	0.7711 (5)	0.4300 (2)	0.0964 (2)	0.0303 (7)
O4	0.5783 (5)	0.6023 (2)	0.2762 (2)	0.0275 (7)
O3	0.6395 (5)	0.6846 (2)	0.4412 (2)	0.0257 (6)
O9	0.9346 (4)	0.4272 (2)	0.3769 (2)	0.0198 (6)
O10	1.0948 (5)	0.6016 (2)	0.3744 (2)	0.0238 (6)
O12	1.1865 (5)	0.4465 (2)	0.2640 (2)	0.0276 (7)
O7	0.5172 (5)	0.2693 (2)	0.0280 (2)	0.0295 (7)
C11	0.5815 (6)	0.7939 (3)	0.2201 (3)	0.0182 (8)
H11	0.5493	0.7311	0.1668	0.022*
C12	0.6033 (6)	0.8950 (3)	0.2021 (3)	0.0170 (8)
C14	0.6545 (6)	0.9901 (3)	0.2807 (3)	0.0190 (8)
O11	1.2984 (4)	0.4879 (2)	0.4437 (2)	0.0231 (6)
N2	0.9543 (5)	0.2985 (3)	−0.2121 (3)	0.0234 (8)
H2	0.9420	0.3318	−0.2591	0.028*
N4	0.5920 (5)	0.9255 (3)	0.1113 (2)	0.0188 (7)
H4A	0.5611	0.8834	0.0501	0.023*
C1	0.8336 (6)	−0.1274 (3)	−0.1935 (3)	0.0188 (9)
O1	0.8145 (5)	−0.1439 (2)	−0.1085 (2)	0.0266 (7)
N3	0.6749 (5)	1.0765 (3)	0.2371 (2)	0.0191 (7)
C13	0.6382 (6)	1.0324 (3)	0.1363 (3)	0.0222 (9)
H13	0.6441	1.0719	0.0881	0.027*
O2	0.8337 (4)	−0.2035 (2)	−0.2739 (2)	0.0245 (7)
O2W	0.9522 (5)	0.2349 (2)	0.4699 (2)	0.0254 (7)
H3W	1.0790	0.2374	0.4926	0.030*
H4W	0.8920	0.2573	0.5212	0.030*
O3W	1.3093 (5)	0.4879 (2)	0.0835 (2)	0.0305 (7)
H5W	1.3544	0.5197	0.0409	0.037*
H6W	1.3685	0.5238	0.1434	0.037*
O1W	0.5431 (4)	0.3032 (2)	0.3864 (2)	0.0199 (6)
H1W	0.5114	0.3053	0.4457	0.024*
H2W	0.4386	0.2693	0.3422	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01897 (17)	0.01555 (16)	0.02043 (16)	0.00466 (12)	0.00520 (12)	0.00592 (12)
Cd2	0.02124 (17)	0.01475 (16)	0.01756 (16)	0.00124 (12)	0.00324 (12)	0.00147 (12)
Cd3	0.02241 (17)	0.01492 (16)	0.01583 (16)	0.00122 (12)	0.00240 (12)	0.00221 (12)
S1	0.0164 (5)	0.0140 (5)	0.0139 (5)	0.0007 (4)	0.0021 (4)	0.0026 (4)
S2	0.0122 (5)	0.0131 (5)	0.0142 (5)	0.0008 (4)	0.0014 (4)	0.0027 (4)
N1	0.0241 (19)	0.0117 (17)	0.0215 (18)	0.0023 (14)	0.0020 (14)	0.0019 (14)
C6	0.025 (2)	0.017 (2)	0.025 (2)	0.0022 (17)	0.0028 (17)	0.0066 (17)
C8	0.020 (2)	0.0149 (19)	0.0127 (18)	0.0044 (16)	0.0034 (15)	0.0046 (15)
C7	0.0140 (19)	0.016 (2)	0.0164 (19)	0.0009 (15)	0.0028 (15)	0.0039 (16)
C3	0.025 (2)	0.025 (2)	0.013 (2)	0.0055 (18)	0.0035 (16)	−0.0011 (17)
C4	0.028 (2)	0.030 (2)	0.016 (2)	0.0043 (19)	−0.0018 (17)	0.0100 (18)
C5	0.014 (2)	0.023 (2)	0.023 (2)	0.0033 (16)	0.0021 (16)	0.0121 (18)
C2	0.0133 (19)	0.017 (2)	0.019 (2)	0.0032 (15)	0.0044 (15)	0.0044 (16)
C16	0.028 (2)	0.024 (2)	0.015 (2)	0.0016 (18)	0.0019 (17)	0.0057 (17)
C9	0.012 (2)	0.022 (2)	0.028 (2)	0.0039 (16)	0.0050 (16)	0.0122 (18)
C10	0.016 (2)	0.020 (2)	0.020 (2)	0.0022 (16)	0.0036 (16)	0.0070 (17)
C15	0.029 (2)	0.018 (2)	0.021 (2)	0.0003 (18)	−0.0004 (18)	0.0010 (17)
O6	0.0229 (16)	0.0247 (16)	0.0279 (16)	0.0078 (13)	0.0035 (12)	0.0120 (13)
O5	0.0269 (17)	0.0300 (17)	0.0221 (15)	0.0058 (13)	0.0104 (12)	0.0059 (13)
O8	0.0300 (18)	0.0241 (17)	0.0386 (18)	−0.0016 (14)	0.0098 (14)	0.0131 (14)
O4	0.0368 (18)	0.0162 (16)	0.0282 (16)	0.0029 (13)	−0.0001 (13)	0.0069 (13)
O3	0.0304 (17)	0.0252 (13)	0.0252 (16)	0.0019 (13)	0.0018 (13)	0.0162 (12)
O9	0.0146 (14)	0.0201 (15)	0.0229 (15)	0.0000 (11)	0.0066 (11)	0.0023 (12)
O10	0.0342 (17)	0.0156 (15)	0.0225 (15)	0.0078 (13)	0.0019 (12)	0.0056 (12)
O12	0.0308 (17)	0.0274 (17)	0.0192 (15)	−0.0008 (13)	0.0144 (13)	−0.0055 (13)
O7	0.0321 (18)	0.0283 (17)	0.0203 (15)	−0.0002 (14)	−0.0061 (13)	−0.0002 (13)
C11	0.020 (2)	0.016 (2)	0.0157 (19)	0.0039 (16)	0.0024 (15)	−0.0004 (16)
C12	0.016 (2)	0.015 (2)	0.019 (2)	0.0006 (16)	−0.0027 (15)	0.0063 (16)
C14	0.018 (2)	0.015 (2)	0.024 (2)	0.0021 (16)	0.0027 (16)	0.0072 (17)
O11	0.0161 (14)	0.0306 (17)	0.0241 (15)	0.0053 (12)	−0.0008 (12)	0.0112 (13)
N2	0.030 (2)	0.0241 (19)	0.0231 (19)	0.0060 (16)	0.0047 (15)	0.0174 (16)
N4	0.0263 (19)	0.0163 (17)	0.0121 (16)	0.0033 (14)	0.0012 (13)	0.0018 (13)
C1	0.012 (2)	0.016 (2)	0.025 (2)	−0.0006 (15)	−0.0027 (16)	0.0043 (17)
O1	0.0368 (18)	0.0158 (15)	0.0251 (16)	0.0014 (13)	−0.0025 (13)	0.0067 (12)
N3	0.0206 (18)	0.0134 (17)	0.0201 (17)	−0.0015 (14)	−0.0009 (14)	0.0030 (14)
C13	0.025 (2)	0.022 (2)	0.021 (2)	0.0019 (18)	−0.0012 (17)	0.0124 (18)
O2	0.0189 (15)	0.0184 (15)	0.0302 (16)	0.0021 (12)	0.0015 (12)	−0.0032 (13)
O2W	0.0279 (17)	0.0284 (17)	0.0182 (14)	0.0057 (13)	0.0020 (12)	0.0035 (13)
O3W	0.0418 (19)	0.0237 (16)	0.0221 (16)	−0.0005 (14)	−0.0026 (13)	0.0057 (13)
O1W	0.0180 (15)	0.0215 (15)	0.0164 (14)	−0.0008 (12)	0.0041 (11)	−0.0001 (11)

Geometric parameters (Å, º) top

Cd1—O4	2.266 (3)	C3—C4	1.368 (6)
Cd1—O9	2.335 (3)	C3—C2	1.410 (5)
Cd1—O5	2.386 (3)	C3—H3	0.9300
Cd1—O11ⁱ	2.398 (3)	C4—C5	1.401 (6)
Cd1—O1W	2.403 (3)	C4—H4	0.9300
Cd1—O11ⁱⁱ	2.437 (3)	C5—N2	1.358 (5)
Cd1—O3	2.532 (3)	C2—C1	1.494 (5)
Cd2—N3ⁱⁱⁱ	2.229 (3)	C16—C15	1.380 (6)
Cd2—O2W	2.264 (3)	C16—C10	1.399 (6)
Cd2—O6	2.301 (3)	C16—H16	0.9300
Cd2—O9	2.312 (3)	C9—O4	1.259 (5)
Cd2—O2^iv	2.349 (3)	C9—O3	1.280 (5)
Cd2—O1W	2.461 (3)	C9—C10	1.487 (5)
Cd3—N1	2.271 (3)	C10—C11	1.390 (5)
Cd3—O1^iv	2.287 (3)	C15—C14	1.388 (6)
Cd3—O12	2.321 (3)	C15—H15	0.9300
Cd3—O3W	2.394 (3)	C11—C12	1.392 (5)
Cd3—O6	2.462 (3)	C11—H11	0.9300
Cd3—O5^v	2.551 (3)	C12—N4	1.384 (5)
S1—O8	1.445 (3)	C12—C14	1.394 (6)
S1—O7	1.460 (3)	C14—N3	1.396 (5)
S1—O5	1.495 (3)	N2—H2	0.8600
S1—O6	1.506 (3)	N4—C13	1.335 (5)
S2—O12	1.451 (3)	N4—H4A	0.8600
S2—O10	1.454 (3)	C1—O1	1.243 (5)
S2—O11	1.483 (3)	C1—O2	1.282 (5)
S2—O9	1.493 (3)	N3—C13	1.328 (5)
N1—C6	1.312 (5)	C13—H13	0.9300
N1—C7	1.399 (5)	O2W—H3W	0.8500
C6—N2	1.347 (5)	O2W—H4W	0.8500
C6—H6	0.9300	O3W—H5W	0.8500
C8—C7	1.386 (5)	O3W—H6W	0.8501
C8—C2	1.391 (5)	O1W—H1W	0.8501
C8—H8	0.9300	O1W—H2W	0.8500
C7—C5	1.410 (5)

O4—Cd1—O9	113.71 (10)	C4—C3—H3	119.0
O4—Cd1—O5	80.91 (10)	C2—C3—H3	119.0
O9—Cd1—O5	83.30 (10)	C3—C4—C5	117.3 (4)
O4—Cd1—O11ⁱ	99.81 (10)	C3—C4—H4	121.3
O9—Cd1—O11ⁱ	145.80 (9)	C5—C4—H4	121.3
O5—Cd1—O11ⁱ	109.59 (10)	N2—C5—C4	132.6 (4)
O4—Cd1—O1W	149.15 (10)	N2—C5—C7	106.2 (3)
O9—Cd1—O1W	75.24 (9)	C4—C5—C7	121.2 (4)
O5—Cd1—O1W	70.61 (10)	C8—C2—C3	120.7 (4)
O11ⁱ—Cd1—O1W	79.48 (9)	C8—C2—C1	119.8 (3)
O4—Cd1—O11ⁱⁱ	130.86 (10)	C3—C2—C1	119.5 (3)
O9—Cd1—O11ⁱⁱ	80.54 (9)	C15—C16—C10	122.4 (4)
O5—Cd1—O11ⁱⁱ	148.10 (10)	C15—C16—H16	118.8
O11ⁱ—Cd1—O11ⁱⁱ	72.16 (10)	C10—C16—H16	118.8
O1W—Cd1—O11ⁱⁱ	78.73 (9)	O4—C9—O3	120.0 (4)
O4—Cd1—O3	54.20 (9)	O4—C9—C10	120.0 (4)
O9—Cd1—O3	113.17 (10)	O3—C9—C10	119.9 (4)
O5—Cd1—O3	135.11 (9)	C11—C10—C16	121.2 (4)
O11ⁱ—Cd1—O3	80.54 (10)	C11—C10—C9	118.7 (4)
O1W—Cd1—O3	152.12 (9)	C16—C10—C9	120.0 (3)
O11ⁱⁱ—Cd1—O3	76.75 (9)	C16—C15—C14	116.9 (4)
N3ⁱⁱⁱ—Cd2—O2W	101.12 (11)	C16—C15—H15	121.5
N3ⁱⁱⁱ—Cd2—O6	88.53 (11)	C14—C15—H15	121.5
O2W—Cd2—O6	164.12 (11)	S1—O6—Cd2	117.49 (16)
N3ⁱⁱⁱ—Cd2—O9	166.27 (11)	S1—O6—Cd3	116.06 (15)
O2W—Cd2—O9	84.74 (10)	Cd2—O6—Cd3	110.03 (11)
O6—Cd2—O9	88.70 (10)	S1—O5—Cd1	135.31 (18)
N3ⁱⁱⁱ—Cd2—O2^iv	94.34 (11)	S1—O5—Cd3ⁱ	101.40 (14)
O2W—Cd2—O2^iv	85.19 (10)	Cd1—O5—Cd3ⁱ	117.53 (11)
O6—Cd2—O2^iv	81.50 (10)	C9—O4—Cd1	99.4 (2)
O9—Cd2—O2^iv	98.54 (10)	C9—O3—Cd1	86.4 (2)
N3ⁱⁱⁱ—Cd2—O1W	93.74 (11)	S2—O9—Cd2	124.43 (15)
O2W—Cd2—O1W	82.80 (10)	S2—O9—Cd1	124.10 (16)
O6—Cd2—O1W	109.37 (9)	Cd2—O9—Cd1	101.86 (10)
O9—Cd2—O1W	74.54 (9)	S2—O12—Cd3	156.42 (19)
O2^iv—Cd2—O1W	166.62 (10)	C10—C11—C12	115.8 (4)
N1—Cd3—O1^iv	92.82 (11)	C10—C11—H11	122.1
N1—Cd3—O12	140.73 (11)	C12—C11—H11	122.1
O1^iv—Cd3—O12	119.93 (11)	N4—C12—C11	131.1 (4)
N1—Cd3—O3W	86.41 (11)	N4—C12—C14	105.8 (3)
O1^iv—Cd3—O3W	153.63 (11)	C11—C12—C14	123.1 (4)
O12—Cd3—O3W	73.50 (10)	C15—C14—C12	120.5 (4)
N1—Cd3—O6	85.14 (11)	C15—C14—N3	130.6 (4)
O1^iv—Cd3—O6	81.41 (10)	C12—C14—N3	108.9 (3)
O12—Cd3—O6	79.61 (10)	S2—O11—Cd1^v	108.68 (15)
O3W—Cd3—O6	124.68 (10)	S2—O11—Cd1ⁱⁱ	142.21 (17)
N1—Cd3—O5^v	135.91 (11)	Cd1^v—O11—Cd1ⁱⁱ	107.84 (10)
O1^iv—Cd3—O5^v	86.67 (10)	C6—N2—C5	107.6 (3)
O12—Cd3—O5^v	71.83 (10)	C6—N2—H2	126.2
O3W—Cd3—O5^v	75.92 (10)	C5—N2—H2	126.2
O6—Cd3—O5^v	137.90 (9)	C13—N4—C12	107.3 (3)
O8—S1—O7	112.03 (19)	C13—N4—H4A	126.4
O8—S1—O5	112.00 (18)	C12—N4—H4A	126.4
O7—S1—O5	106.71 (18)	O1—C1—O2	122.5 (4)
O8—S1—O6	108.93 (18)	O1—C1—C2	119.3 (3)
O7—S1—O6	110.12 (18)	O2—C1—C2	118.2 (4)
O5—S1—O6	106.92 (16)	C1—O1—Cd3^iv	112.1 (2)
O12—S2—O10	111.20 (18)	C13—N3—C14	104.9 (3)
O12—S2—O11	107.91 (18)	C13—N3—Cd2^vi	123.2 (3)
O10—S2—O11	110.38 (17)	C14—N3—Cd2^vi	128.5 (3)
O12—S2—O9	110.49 (17)	N3—C13—N4	113.1 (3)
O10—S2—O9	108.24 (17)	N3—C13—H13	123.4
O11—S2—O9	108.60 (16)	N4—C13—H13	123.4
C6—N1—C7	105.7 (3)	C1—O2—Cd2^iv	116.4 (2)
C6—N1—Cd3	122.0 (3)	Cd2—O2W—H3W	123.0
C7—N1—Cd3	131.4 (2)	Cd2—O2W—H4W	123.8
N1—C6—N2	112.8 (4)	H3W—O2W—H4W	107.7
N1—C6—H6	123.6	Cd3—O3W—H5W	145.3
N2—C6—H6	123.6	Cd3—O3W—H6W	102.8
C7—C8—C2	117.9 (3)	H5W—O3W—H6W	107.7
C7—C8—H8	121.1	Cd1—O1W—Cd2	95.76 (9)
C2—C8—H8	121.1	Cd1—O1W—H1W	108.5
C8—C7—N1	131.6 (3)	Cd2—O1W—H1W	130.5
C8—C7—C5	120.8 (4)	Cd1—O1W—H2W	108.6
N1—C7—C5	107.6 (3)	Cd2—O1W—H2W	104.1
C4—C3—C2	122.0 (4)	H1W—O1W—H2W	107.7

O1^iv—Cd3—N1—C6	−163.5 (3)	O4—Cd1—O3—C9	−0.5 (2)
O12—Cd3—N1—C6	48.4 (4)	O9—Cd1—O3—C9	102.9 (2)
O3W—Cd3—N1—C6	−9.9 (3)	O5—Cd1—O3—C9	−1.6 (3)
O6—Cd3—N1—C6	115.4 (3)	O11ⁱ—Cd1—O3—C9	−109.9 (2)
O5^v—Cd3—N1—C6	−75.3 (4)	O1W—Cd1—O3—C9	−154.6 (2)
O1^iv—Cd3—N1—C7	3.3 (3)	O11ⁱⁱ—Cd1—O3—C9	176.3 (2)
O12—Cd3—N1—C7	−144.9 (3)	O12—S2—O9—Cd2	32.9 (2)
O3W—Cd3—N1—C7	156.9 (4)	O10—S2—O9—Cd2	154.85 (17)
O6—Cd3—N1—C7	−77.9 (3)	O11—S2—O9—Cd2	−85.3 (2)
O5^v—Cd3—N1—C7	91.4 (4)	O12—S2—O9—Cd1	−107.1 (2)
C7—N1—C6—N2	−1.6 (5)	O10—S2—O9—Cd1	14.9 (2)
Cd3—N1—C6—N2	168.1 (3)	O11—S2—O9—Cd1	134.77 (18)
C2—C8—C7—N1	−176.2 (4)	N3ⁱⁱⁱ—Cd2—O9—S2	−142.1 (4)
C2—C8—C7—C5	3.3 (6)	O2W—Cd2—O9—S2	101.78 (19)
C6—N1—C7—C8	−178.1 (4)	O6—Cd2—O9—S2	−63.74 (19)
Cd3—N1—C7—C8	13.5 (6)	O2^iv—Cd2—O9—S2	17.5 (2)
C6—N1—C7—C5	2.4 (4)	O1W—Cd2—O9—S2	−174.3 (2)
Cd3—N1—C7—C5	−166.0 (3)	N3ⁱⁱⁱ—Cd2—O9—Cd1	4.9 (5)
C2—C3—C4—C5	2.4 (6)	O2W—Cd2—O9—Cd1	−111.23 (11)
C3—C4—C5—N2	178.4 (4)	O6—Cd2—O9—Cd1	83.25 (11)
C3—C4—C5—C7	0.8 (6)	O2^iv—Cd2—O9—Cd1	164.46 (10)
C8—C7—C5—N2	178.1 (3)	O1W—Cd2—O9—Cd1	−27.26 (9)
N1—C7—C5—N2	−2.3 (4)	O4—Cd1—O9—S2	26.4 (2)
C8—C7—C5—C4	−3.7 (6)	O5—Cd1—O9—S2	103.35 (19)
N1—C7—C5—C4	175.8 (4)	O11ⁱ—Cd1—O9—S2	−141.33 (17)
C7—C8—C2—C3	−0.1 (6)	O1W—Cd1—O9—S2	175.0 (2)
C7—C8—C2—C1	176.9 (3)	O11ⁱⁱ—Cd1—O9—S2	−104.26 (19)
C4—C3—C2—C8	−2.8 (6)	O3—Cd1—O9—S2	−33.2 (2)
C4—C3—C2—C1	−179.9 (4)	O4—Cd1—O9—Cd2	−120.77 (11)
C15—C16—C10—C11	−1.3 (6)	O5—Cd1—O9—Cd2	−43.79 (10)
C15—C16—C10—C9	174.8 (4)	O11ⁱ—Cd1—O9—Cd2	71.53 (19)
O4—C9—C10—C11	0.5 (6)	O1W—Cd1—O9—Cd2	27.87 (10)
O3—C9—C10—C11	177.8 (4)	O11ⁱⁱ—Cd1—O9—Cd2	108.61 (11)
O4—C9—C10—C16	−175.7 (4)	O3—Cd1—O9—Cd2	179.70 (8)
O3—C9—C10—C16	1.6 (6)	O10—S2—O12—Cd3	−132.4 (5)
C10—C16—C15—C14	−0.5 (6)	O11—S2—O12—Cd3	106.4 (5)
O8—S1—O6—Cd2	118.20 (19)	O9—S2—O12—Cd3	−12.2 (6)
O7—S1—O6—Cd2	−118.58 (19)	N1—Cd3—O12—S2	93.6 (5)
O5—S1—O6—Cd2	−3.0 (2)	O1^iv—Cd3—O12—S2	−48.9 (5)
O8—S1—O6—Cd3	−15.0 (2)	O3W—Cd3—O12—S2	155.9 (5)
O7—S1—O6—Cd3	108.25 (19)	O6—Cd3—O12—S2	24.8 (5)
O5—S1—O6—Cd3	−136.19 (17)	O5^v—Cd3—O12—S2	−123.9 (5)
N3ⁱⁱⁱ—Cd2—O6—S1	103.62 (19)	C16—C10—C11—C12	1.0 (6)
O2W—Cd2—O6—S1	−128.4 (3)	C9—C10—C11—C12	−175.1 (3)
O9—Cd2—O6—S1	−62.93 (18)	C10—C11—C12—N4	177.6 (4)
O2^iv—Cd2—O6—S1	−161.77 (19)	C10—C11—C12—C14	1.0 (6)
O1W—Cd2—O6—S1	10.2 (2)	C16—C15—C14—C12	2.5 (6)
N3ⁱⁱⁱ—Cd2—O6—Cd3	−120.60 (13)	C16—C15—C14—N3	−177.2 (4)
O2W—Cd2—O6—Cd3	7.4 (4)	N4—C12—C14—C15	179.8 (4)
O9—Cd2—O6—Cd3	72.85 (12)	C11—C12—C14—C15	−2.8 (6)
O2^iv—Cd2—O6—Cd3	−25.99 (11)	N4—C12—C14—N3	−0.4 (4)
O1W—Cd2—O6—Cd3	145.96 (10)	C11—C12—C14—N3	176.9 (4)
N1—Cd3—O6—S1	−60.98 (18)	O12—S2—O11—Cd1^v	24.1 (2)
O1^iv—Cd3—O6—S1	−154.58 (19)	O10—S2—O11—Cd1^v	−97.64 (18)
O12—Cd3—O6—S1	82.68 (18)	O9—S2—O11—Cd1^v	143.85 (14)
O3W—Cd3—O6—S1	21.2 (2)	O12—S2—O11—Cd1ⁱⁱ	−171.4 (3)
O5^v—Cd3—O6—S1	130.18 (16)	O10—S2—O11—Cd1ⁱⁱ	66.9 (3)
N1—Cd3—O6—Cd2	162.54 (14)	O9—S2—O11—Cd1ⁱⁱ	−51.6 (3)
O1^iv—Cd3—O6—Cd2	68.94 (12)	N1—C6—N2—C5	0.1 (5)
O12—Cd3—O6—Cd2	−53.79 (12)	C4—C5—N2—C6	−176.5 (4)
O3W—Cd3—O6—Cd2	−115.24 (12)	C7—C5—N2—C6	1.4 (4)
O5^v—Cd3—O6—Cd2	−6.3 (2)	C11—C12—N4—C13	−175.9 (4)
O8—S1—O5—Cd1	−44.7 (3)	C14—C12—N4—C13	1.1 (4)
O7—S1—O5—Cd1	−167.6 (2)	C8—C2—C1—O1	17.5 (5)
O6—S1—O5—Cd1	74.6 (3)	C3—C2—C1—O1	−165.4 (4)
O8—S1—O5—Cd3ⁱ	106.28 (17)	C8—C2—C1—O2	−161.8 (3)
O7—S1—O5—Cd3ⁱ	−16.65 (19)	C3—C2—C1—O2	15.2 (5)
O6—S1—O5—Cd3ⁱ	−134.47 (15)	O2—C1—O1—Cd3^iv	7.8 (5)
O4—Cd1—O5—S1	72.8 (2)	C2—C1—O1—Cd3^iv	−171.5 (3)
O9—Cd1—O5—S1	−42.5 (2)	C15—C14—N3—C13	179.3 (4)
O11ⁱ—Cd1—O5—S1	170.1 (2)	C12—C14—N3—C13	−0.5 (4)
O1W—Cd1—O5—S1	−119.2 (3)	C15—C14—N3—Cd2^vi	19.9 (6)
O11ⁱⁱ—Cd1—O5—S1	−102.4 (3)	C12—C14—N3—Cd2^vi	−159.9 (3)
O3—Cd1—O5—S1	73.8 (3)	C14—N3—C13—N4	1.3 (5)
O4—Cd1—O5—Cd3ⁱ	−74.72 (14)	Cd2^vi—N3—C13—N4	162.0 (3)
O9—Cd1—O5—Cd3ⁱ	169.89 (14)	C12—N4—C13—N3	−1.5 (5)
O11ⁱ—Cd1—O5—Cd3ⁱ	22.53 (15)	O1—C1—O2—Cd2^iv	−93.2 (4)
O1W—Cd1—O5—Cd3ⁱ	93.22 (14)	C2—C1—O2—Cd2^iv	86.1 (4)
O11ⁱⁱ—Cd1—O5—Cd3ⁱ	110.02 (18)	O4—Cd1—O1W—Cd2	86.1 (2)
O3—Cd1—O5—Cd3ⁱ	−73.80 (18)	O9—Cd1—O1W—Cd2	−25.60 (9)
O3—C9—O4—Cd1	−0.9 (4)	O5—Cd1—O1W—Cd2	62.39 (10)
C10—C9—O4—Cd1	176.4 (3)	O11ⁱ—Cd1—O1W—Cd2	177.65 (10)
O9—Cd1—O4—C9	−101.8 (2)	O11ⁱⁱ—Cd1—O1W—Cd2	−108.66 (10)
O5—Cd1—O4—C9	179.7 (3)	O3—Cd1—O1W—Cd2	−137.43 (17)
O11ⁱ—Cd1—O4—C9	71.2 (3)	N3ⁱⁱⁱ—Cd2—O1W—Cd1	−146.77 (11)
O1W—Cd1—O4—C9	157.1 (2)	O2W—Cd2—O1W—Cd1	112.47 (11)
O11ⁱⁱ—Cd1—O4—C9	−3.6 (3)	O6—Cd2—O1W—Cd1	−57.02 (12)
O3—Cd1—O4—C9	0.5 (2)	O9—Cd2—O1W—Cd1	25.96 (9)
O4—C9—O3—Cd1	0.8 (4)	O2^iv—Cd2—O1W—Cd1	86.2 (4)
C10—C9—O3—Cd1	−176.5 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O10^vii	0.86	1.98	2.836 (4)	176
N4—H4A···O7^viii	0.86	1.98	2.716 (4)	143
O1W—H1W···O3^ix	0.85	1.91	2.736 (4)	163
O1W—H2W···O2^x	0.85	1.91	2.734 (4)	165
O2W—H3W···O3ⁱⁱ	0.85	1.99	2.770 (4)	153
O2W—H4W···O10ⁱⁱ	0.85	2.01	2.687 (4)	136
O3W—H5W···O8^vii	0.85	2.23	2.925 (4)	139
O3W—H6W···O4^v	0.85	2.09	2.918 (4)	166

Symmetry codes: (ii) −x+2, −y+1, −z+1; (v) x+1, y, z; (vii) −x+2, −y+1, −z; (viii) −x+1, −y+1, −z; (ix) −x+1, −y+1, −z+1; (x) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Cd₃(C₈H₅N₂O₂)₂(SO₄)₂(H₂O)₃]
M_r	905.65
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.5932 (8), 13.0463 (16), 13.5933 (16)
α, β, γ (°)	104.313 (1), 96.662 (1), 97.646 (1)
V (Å³)	1109.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.13
Crystal size (mm)	0.30 × 0.27 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.454, 0.508
No. of measured, independent and observed [I > 2σ(I)] reflections	5772, 3935, 3593
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.067, 1.06
No. of reflections	3935
No. of parameters	361
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.71

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SAINT, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O10ⁱ	0.86	1.98	2.836 (4)	176
N4—H4A···O7ⁱⁱ	0.86	1.98	2.716 (4)	143
O1W—H1W···O3ⁱⁱⁱ	0.85	1.91	2.736 (4)	163
O1W—H2W···O2^iv	0.85	1.91	2.734 (4)	165
O2W—H3W···O3^v	0.85	1.99	2.770 (4)	153
O2W—H4W···O10^v	0.85	2.01	2.687 (4)	136
O3W—H5W···O8ⁱ	0.85	2.23	2.925 (4)	139
O3W—H6W···O4^vi	0.85	2.09	2.918 (4)	166

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

Acknowledgements

The authors acknowledge the Undergraduates' Innovating Experimentation Project of Guangdong Province, the Undergraduates' Innovating Experimentation Project of South China Normal University and the Students' Extracurricular Scientific Research Project of South China Normal University for supporting this work.

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