Poly[[(1,10-phenanthroline){μ3-2,2′,2′′-[1,3,5-triazine-2,4,6-triyltris(sulfane­diyl)]triacetato}­cadmium] 0.42-hydrate]

Chi, C.-J.; Peng, Y.-Q.; Zeng, S.-Y.; Sun, D.-Z.

doi:10.1107/S1600536811019210

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m826-m827

doi:10.1107/S1600536811019210

Open

access

Poly[[(1,10-phenanthroline){μ₃-2,2′,2′′-[1,3,5-triazine-2,4,6-triyltris(sulfanediyl)]triacetato}cadmium] 0.42-hydrate]

Chun-Jing Chi,^a Yan-Qiang Peng,^a Su-Yuan Zeng ^a and De-Zhi Sun ^a ^*

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: sundezhi@lcu.edu.cn

(Received 9 May 2011; accepted 20 May 2011; online 4 June 2011)

The asymmetric unit of the title complex, {[Cd(C₉H₇N₃O₆S₃)(C₁₂H₈N₂)]·0.42H₂O}_n, contains a Cd^II atom, one doubly deprotonated 2,2′,2′′-[1,3,5-triazine-2,4,6-triyltris(sulfanediyl)]triacetic acid ligand (HTTTA²⁻), a 1,10-phenanthroline (phen) ligand and a fractionally occupied water molecule [site occupancy = 0.421 (15)]. The Cd^II atom is six-coordinated within a distorted octahedral coordination geometry. Six coordination arises from four O atoms derived from three different HTTTA²⁻ ligands, and two N atoms of the chelating phen molecule. The incompletely deprotonated triazine ligand adopts a μ₃-η¹:η¹:η² coordination mode, resulting in the formation of chains along the c axis based on Cd₂O₂ dimeric units. Adjacent chains are stacked through π–π stacking [3.533 (2) Å between phen and triazine rings] and C—H⋯O interactions, forming supramolecular sheets in the ab plane. Intra-and intermolecular O—H⋯O hydrogen bonds are also observed.

Related literature

For background to metal-organic frameworks, see: Rao et al. (2004 ); Rowsell & Yaghi (2005 ); Wu et al. (2009 ). For similar structures, see: Lu et al. (2010 ); Wang et al. (2007 ).

Experimental

Crystal data

[Cd(C₉H₇N₃O₆S₃)(C₁₂H₈N₂)]·0.42H₂O
M_r = 649.53
Triclinic, $[P \overline 1]$
a = 10.618 (2) Å
b = 10.987 (2) Å
c = 12.601 (2) Å
α = 95.815 (3)°
β = 114.197 (2)°
γ = 113.909 (2)°
V = 1161.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 298 K
0.30 × 0.28 × 0.26 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.691, T_max = 0.720
6114 measured reflections
4024 independent reflections
3322 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.071
S = 1.07
4024 reflections
343 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—O1	2.447 (2)
Cd1—O1ⁱ	2.274 (2)
Cd1—O4ⁱ	2.490 (3)
Cd1—O5ⁱⁱ	2.295 (2)
Cd1—N4	2.331 (3)
Cd1—N5	2.320 (3)
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) -x+1, -y+1, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O6ⁱⁱⁱ	0.82	1.68	2.439 (4)	154
O7—H71⋯O2^iv	0.75 (2)	2.35 (12)	2.984 (11)	142 (18)
C15—H15⋯O2^v	0.93	2.50	3.294 (6)	143
C17—H17⋯O2^v	0.93	2.57	3.353 (6)	142
Symmetry codes: (iii) x, y+1, z; (iv) -x+2, -y+2, -z+2; (v) x-1, y-1, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019210/tk2743sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019210/tk2743Isup2.hkl

checkCIF report

Comment top

The assembly of coordination architectures has attracted much attention in recent years due to their potential applications in separation, sorption, hydrogen storage, and catalysis, as well as due to their intriguing topologies such as molecular ladders, grids, rings, boxes, honeycombs, and diamondoids (Rowsell & Yaghi, 2005). Flexible multi-functional carboxylic acids are widely investigated in this regard (Rao et al., 2004; Rowsell & Yaghi 2005; Wu et al., 2009). Previous reports of an alkaline earth and a series of lanthanide coordination complexes based on H₃TTTA, 2,2',2''-[1,3,5-triazine-2,4,6-triyltris(sulfanediyl)]tris-acetic acid, have appeared (Lu, et al., 2010; Wang, et al., 2007). Herein, we obtained a new Cd^II complex assembled from this flexible ligand.

As shown in Fig.1, the asymmetric unit consists of one Cd^II ion, one HTTTA^2- dianion, a chelating 1,10-phenanthroline (phen) ligand and approximately half a disordered water molecule (site occupancy = 0.421 (15)). The Cd center is six-coordinated defined by four oxygen atoms derived from three different HTTTA^2- anions, and two nitrogen atoms of a chelating phen molecule; Table 1. The N5—Cd1—N4 angle is acute at 71.86 (9)° and consequently, the coordination geometry around the metal center is much distorted. The HTTTA^2- ligands act as µ₃-bridges, connecting neighboring Cd centers to generate 1-D chains along the c axis. The H atom of the carboxylic group of the HTTTA^2- ligand was assigned to O3 according to the long C7—O3 distance of 1.283 (4) Å as well as O3—H3···O6 hydrogen bonding interactions, Table 2. Within the chains, Cd₂O₂ units are formed through the η²-bridged carboxylate oxygen atoms O1, with the Cd1···Cd1ⁱ distance and Cd1—O1—Cd1ⁱ (symmetry code: i, 1 - x, 2 - y, 2 - z.) angle being 3.829 (3) Å and 108.3 (3) °, respectively.

Neighboring chains are connected to each other through weak intermolecular π–π stacking interactions between phen and triazine rings with the average interplanar separation of 3.533 (2) Å. As a result, two-dimensional supramolecular sheets are formed along the ab plane, Fig. 2. These sheets are reinforced via nonclassical weak C—H···O interactions Table 2.

Related literature top

For background to metal-organic frameworks, see: Rao et al. (2004); Rowsell & Yaghi (2005); Wu et al. (2009). For similar structures, see: Lu et al. (2010); Wang et al. (2007).

Experimental top

A mixture of 2,2',2''-((1,3,5-triazine-2,4,6-triyl)tris(sulfanediyl))triacetic acid (0.010 g, 0.025 mmol), phenanthroline (0.008 g, 0.05 mmol) and Cd(OAc)₂.6H₂O (0.013 g, 0.025 mmol) in 10 mL H₂O was placed in a Parr Teflon-lined stainless steel vessel and heated to 80 °C for 24 h. The reaction system was cooled to room temperature slowly and yellow blocks were obtained. After filtration, the crystals were washed with water and dried in air. (Yield 64% based on Cd(OAc)₂.6H₂O). Calcd.: C 38.80, H 2.44, N 10.78; C₂₁H_15.84CdN₅O_6.42S₃ requires: C 38.43, H 2.70, N 10.42 %. IR (KBr pellet): 3421 (m,br), 2908 (w), 1591 (m), 1517 (vw), 1425 (m), 1381 (m), 1266 (m), 1246 (m), 1222 (m), 855 (m), 785 (w), 730 (m), 669 (w) cm^-1.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); 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 top

Fig. 1. A view of the asymmetric unit of the title complex extended to show i) the coordination geometry about the Cd1 atom and ii) the coordinating mode of the µ₃-ligand. The figure shows atom labels and 30% probability displacement ellipsoids for non-hydrogen atoms. Only the H3 atom is shown with the others omitted for clarity. Symmetry codes: (i) 2 - x, 1 - y, 1 - z and (ii) x, 1/2 - y, 1/2 + z.

Fig. 2. The two-dimensional sheet in the title complex connected by C—H···O and π-π stacking interactions (dashed blue lines). Hydrogen atoms are omitted for clarity.

Poly[[(1,10-phenanthroline){µ₃-2,2',2''-[1,3,5-triazine-2,4,6- triyltris(sulfanediyl)]triacetato}cadmium] 0.42-hydrate] top

Crystal data top

[Cd(C₉H₇N₃O₆S₃)(C₁₂H₈N₂)]·0.42H₂O	Z = 2
M_r = 649.53	F(000) = 648
Triclinic, P1	D_x = 1.858 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.618 (2) Å	Cell parameters from 3004 reflections
b = 10.987 (2) Å	θ = 2.3–27.8°
c = 12.601 (2) Å	µ = 1.26 mm⁻¹
α = 95.815 (3)°	T = 298 K
β = 114.197 (2)°	Block, yellow
γ = 113.909 (2)°	0.30 × 0.28 × 0.26 mm
V = 1161.1 (4) Å³

Data collection top

Bruker APEX CCD area-detector diffractometer	4024 independent reflections
Radiation source: fine-focus sealed tube	3322 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→6
T_min = 0.691, T_max = 0.720	k = −11→13
6114 measured reflections	l = −14→14

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0324P)²] where P = (F_o² + 2F_c²)/3
4024 reflections	(Δ/σ)_max = 0.001
343 parameters	Δρ_max = 0.44 e Å⁻³
3 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Cd(C₉H₇N₃O₆S₃)(C₁₂H₈N₂)]·0.42H₂O	γ = 113.909 (2)°
M_r = 649.53	V = 1161.1 (4) Å³
Triclinic, P1	Z = 2
a = 10.618 (2) Å	Mo Kα radiation
b = 10.987 (2) Å	µ = 1.26 mm⁻¹
c = 12.601 (2) Å	T = 298 K
α = 95.815 (3)°	0.30 × 0.28 × 0.26 mm
β = 114.197 (2)°

Data collection top

Bruker APEX CCD area-detector diffractometer	4024 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3322 reflections with I > 2σ(I)
T_min = 0.691, T_max = 0.720	R_int = 0.018
6114 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	3 restraints
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.44 e Å⁻³
4024 reflections	Δρ_min = −0.47 e Å⁻³
343 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.42035 (3)	0.85652 (2)	1.06635 (2)	0.03328 (10)
C1	0.4810 (4)	0.6039 (3)	0.8043 (3)	0.0323 (8)
C2	0.4472 (4)	0.6269 (3)	0.6212 (3)	0.0359 (8)
C3	0.3023 (4)	0.4203 (3)	0.6345 (3)	0.0356 (8)
C4	0.7363 (4)	0.8372 (3)	0.9962 (3)	0.0331 (8)
H4A	0.8205	0.8656	1.0798	0.040*
H4B	0.7782	0.8275	0.9424	0.040*
C5	0.6972 (4)	0.9555 (3)	0.9826 (3)	0.0346 (8)
C6	0.6109 (4)	0.8984 (3)	0.6309 (3)	0.0426 (9)
H6A	0.6908	0.9023	0.7073	0.051*
H6B	0.6661	0.9586	0.5955	0.051*
C7	0.5189 (4)	0.9579 (4)	0.6602 (3)	0.0385 (8)
C8	0.1498 (4)	0.1658 (4)	0.6678 (3)	0.0418 (9)
H8A	0.1936	0.2377	0.7438	0.050*
H8B	0.0417	0.0990	0.6446	0.050*
C9	0.2466 (4)	0.0902 (3)	0.6898 (3)	0.0362 (8)
C10	0.1914 (4)	0.7138 (4)	0.7677 (3)	0.0456 (9)
H10	0.2475	0.8042	0.7672	0.055*
C11	0.0686 (5)	0.6091 (5)	0.6563 (3)	0.0555 (11)
H11	0.0439	0.6302	0.5833	0.067*
C12	−0.0148 (4)	0.4762 (4)	0.6546 (3)	0.0501 (10)
H12	−0.0969	0.4063	0.5806	0.060*
C13	0.0238 (4)	0.4452 (4)	0.7654 (3)	0.0374 (8)
C14	−0.0603 (4)	0.3101 (4)	0.7722 (4)	0.0484 (10)
H14	−0.1414	0.2364	0.7003	0.058*
C15	−0.0245 (4)	0.2871 (4)	0.8809 (4)	0.0458 (9)
H15	−0.0817	0.1981	0.8832	0.055*
C16	0.1006 (4)	0.3981 (3)	0.9934 (3)	0.0350 (8)
C17	0.1391 (4)	0.3790 (4)	1.1094 (4)	0.0418 (9)
H17	0.0825	0.2921	1.1153	0.050*
C18	0.2594 (4)	0.4883 (4)	1.2119 (3)	0.0415 (9)
H18	0.2871	0.4769	1.2890	0.050*
C19	0.3412 (4)	0.6180 (4)	1.2008 (3)	0.0385 (8)
H19	0.4236	0.6922	1.2720	0.046*
C20	0.1881 (3)	0.5322 (3)	0.9908 (3)	0.0278 (7)
C21	0.1479 (4)	0.5563 (3)	0.8738 (3)	0.0296 (7)
N1	0.5244 (3)	0.6901 (3)	0.7429 (2)	0.0339 (7)
N2	0.3350 (4)	0.4923 (3)	0.5603 (3)	0.0425 (7)
N3	0.3688 (3)	0.4680 (3)	0.7551 (2)	0.0365 (7)
N4	0.2304 (3)	0.6890 (3)	0.8734 (2)	0.0344 (6)
N5	0.3072 (3)	0.6407 (3)	1.0937 (2)	0.0311 (6)
O1	0.5578 (3)	0.9325 (2)	0.9501 (2)	0.0360 (5)
O2	0.8069 (3)	1.0707 (3)	1.0042 (3)	0.0579 (7)
O3	0.3680 (3)	0.8904 (3)	0.5892 (2)	0.0601 (8)
H3	0.3281	0.9298	0.6119	0.072*
O4	0.5906 (3)	1.0653 (3)	0.7466 (2)	0.0525 (7)
O5	0.3310 (3)	0.1012 (3)	0.7971 (2)	0.0483 (6)
O6	0.2284 (3)	0.0185 (3)	0.5955 (2)	0.0665 (8)
S1	0.57763 (10)	0.66671 (9)	0.96406 (7)	0.0340 (2)
S2	0.49678 (13)	0.72178 (10)	0.52847 (9)	0.0503 (3)
S3	0.14725 (13)	0.24605 (10)	0.55044 (9)	0.0552 (3)
O7	0.9389 (12)	0.8880 (13)	0.7511 (12)	0.098 (5)	0.421 (15)
H71	0.97 (2)	0.876 (19)	0.813 (8)	0.17 (10)*	0.421 (15)
H72	0.95 (3)	0.85 (2)	0.711 (15)	0.3 (2)*	0.421 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03706 (16)	0.02399 (14)	0.03189 (15)	0.01304 (11)	0.01291 (11)	0.01064 (10)
C1	0.0352 (19)	0.0324 (19)	0.0380 (19)	0.0237 (16)	0.0181 (15)	0.0130 (15)
C2	0.047 (2)	0.035 (2)	0.037 (2)	0.0277 (18)	0.0229 (17)	0.0142 (16)
C3	0.040 (2)	0.0288 (18)	0.037 (2)	0.0221 (16)	0.0128 (16)	0.0106 (15)
C4	0.0322 (18)	0.0341 (19)	0.0313 (18)	0.0170 (15)	0.0137 (15)	0.0098 (15)
C5	0.047 (2)	0.0301 (19)	0.0312 (18)	0.0199 (18)	0.0213 (16)	0.0127 (15)
C6	0.052 (2)	0.034 (2)	0.047 (2)	0.0192 (18)	0.0299 (18)	0.0166 (17)
C7	0.047 (2)	0.0312 (19)	0.0337 (19)	0.0173 (18)	0.0175 (17)	0.0140 (16)
C8	0.043 (2)	0.033 (2)	0.043 (2)	0.0192 (17)	0.0150 (17)	0.0107 (16)
C9	0.0319 (19)	0.0278 (18)	0.035 (2)	0.0100 (15)	0.0105 (16)	0.0074 (15)
C10	0.050 (2)	0.046 (2)	0.039 (2)	0.0238 (19)	0.0170 (18)	0.0214 (18)
C11	0.056 (3)	0.071 (3)	0.034 (2)	0.036 (2)	0.0135 (19)	0.019 (2)
C12	0.036 (2)	0.057 (3)	0.032 (2)	0.019 (2)	0.0042 (16)	−0.0011 (18)
C13	0.0286 (18)	0.041 (2)	0.0357 (19)	0.0166 (16)	0.0120 (15)	0.0046 (16)
C14	0.031 (2)	0.033 (2)	0.051 (2)	0.0029 (17)	0.0125 (17)	−0.0060 (17)
C15	0.034 (2)	0.028 (2)	0.062 (3)	0.0072 (16)	0.0226 (18)	0.0067 (18)
C16	0.0305 (18)	0.0285 (18)	0.052 (2)	0.0161 (15)	0.0241 (16)	0.0120 (16)
C17	0.049 (2)	0.0315 (19)	0.070 (3)	0.0250 (18)	0.043 (2)	0.0268 (19)
C18	0.056 (2)	0.044 (2)	0.043 (2)	0.031 (2)	0.0327 (19)	0.0223 (18)
C19	0.050 (2)	0.034 (2)	0.0316 (19)	0.0229 (18)	0.0183 (17)	0.0114 (15)
C20	0.0267 (17)	0.0246 (17)	0.0386 (19)	0.0158 (14)	0.0185 (15)	0.0098 (14)
C21	0.0256 (17)	0.0306 (18)	0.0361 (18)	0.0160 (15)	0.0161 (14)	0.0099 (15)
N1	0.0421 (17)	0.0325 (16)	0.0294 (15)	0.0190 (14)	0.0186 (13)	0.0116 (13)
N2	0.057 (2)	0.0333 (17)	0.0352 (16)	0.0241 (15)	0.0195 (15)	0.0104 (13)
N3	0.0386 (16)	0.0305 (16)	0.0365 (17)	0.0182 (14)	0.0144 (13)	0.0100 (13)
N4	0.0360 (16)	0.0339 (16)	0.0315 (15)	0.0178 (13)	0.0142 (13)	0.0127 (13)
N5	0.0327 (15)	0.0268 (15)	0.0326 (15)	0.0152 (13)	0.0150 (12)	0.0085 (12)
O1	0.0432 (14)	0.0350 (13)	0.0465 (14)	0.0261 (12)	0.0274 (12)	0.0215 (11)
O2	0.0495 (17)	0.0328 (15)	0.084 (2)	0.0135 (13)	0.0330 (15)	0.0213 (14)
O3	0.0507 (17)	0.0477 (16)	0.0560 (17)	0.0255 (14)	0.0089 (14)	−0.0075 (13)
O4	0.0543 (16)	0.0355 (14)	0.0496 (16)	0.0102 (13)	0.0257 (13)	−0.0012 (12)
O5	0.0434 (15)	0.0679 (18)	0.0361 (14)	0.0318 (14)	0.0164 (12)	0.0213 (13)
O6	0.078 (2)	0.075 (2)	0.0409 (16)	0.0550 (18)	0.0101 (14)	0.0029 (15)
S1	0.0398 (5)	0.0301 (5)	0.0326 (5)	0.0182 (4)	0.0167 (4)	0.0131 (4)
S2	0.0826 (8)	0.0418 (5)	0.0415 (5)	0.0332 (5)	0.0399 (5)	0.0174 (4)
S3	0.0654 (7)	0.0296 (5)	0.0379 (5)	0.0169 (5)	0.0052 (5)	0.0089 (4)
O7	0.076 (6)	0.102 (8)	0.076 (8)	0.033 (5)	0.014 (5)	0.025 (6)

Geometric parameters (Å, º) top

Cd1—O1	2.447 (2)	C9—O6	1.253 (4)
Cd1—O1ⁱ	2.274 (2)	C10—N4	1.316 (4)
Cd1—O4ⁱ	2.490 (3)	C10—C11	1.397 (5)
Cd1—O5ⁱⁱ	2.295 (2)	C10—H10	0.9300
Cd1—N4	2.331 (3)	C11—C12	1.359 (5)
Cd1—N5	2.320 (3)	C11—H11	0.9300
C1—N1	1.340 (4)	C12—C13	1.405 (5)
C1—N3	1.341 (4)	C12—H12	0.9300
C1—S1	1.742 (3)	C13—C21	1.405 (4)
C2—N2	1.336 (4)	C13—C14	1.422 (5)
C2—N1	1.341 (4)	C14—C15	1.344 (5)
C2—S2	1.742 (3)	C14—H14	0.9300
C3—N3	1.320 (4)	C15—C16	1.433 (5)
C3—N2	1.348 (4)	C15—H15	0.9300
C3—S3	1.761 (3)	C16—C20	1.400 (4)
C4—C5	1.522 (4)	C16—C17	1.410 (5)
C4—S1	1.800 (3)	C17—C18	1.354 (5)
C4—H4A	0.9700	C17—H17	0.9300
C4—H4B	0.9700	C18—C19	1.393 (5)
C5—O2	1.228 (4)	C18—H18	0.9300
C5—O1	1.265 (4)	C19—N5	1.325 (4)
C6—C7	1.512 (5)	C19—H19	0.9300
C6—S2	1.790 (4)	C20—N5	1.349 (4)
C6—H6A	0.9700	C20—C21	1.443 (4)
C6—H6B	0.9700	C21—N4	1.365 (4)
C7—O4	1.220 (4)	O1—Cd1ⁱ	2.274 (2)
C7—O3	1.283 (4)	O3—H3	0.8201
C8—C9	1.526 (5)	O4—Cd1ⁱ	2.490 (3)
C8—S3	1.793 (4)	O5—Cd1ⁱⁱ	2.295 (2)
C8—H8A	0.9700	O7—H71	0.75 (2)
C8—H8B	0.9700	O7—H72	0.75 (2)
C9—O5	1.237 (4)

O1ⁱ—Cd1—O5ⁱⁱ	107.00 (9)	C11—C10—H10	118.9
O1ⁱ—Cd1—N5	154.48 (9)	C12—C11—C10	120.0 (3)
O5ⁱⁱ—Cd1—N5	90.50 (9)	C12—C11—H11	120.0
O1ⁱ—Cd1—N4	107.24 (9)	C10—C11—H11	120.0
O5ⁱⁱ—Cd1—N4	131.23 (10)	C11—C12—C13	119.5 (3)
N5—Cd1—N4	71.86 (9)	C11—C12—H12	120.2
O1ⁱ—Cd1—O1	71.65 (9)	C13—C12—H12	120.2
O5ⁱⁱ—Cd1—O1	79.40 (8)	C12—C13—C21	117.2 (3)
N5—Cd1—O1	131.20 (8)	C12—C13—C14	123.2 (3)
N4—Cd1—O1	79.61 (9)	C21—C13—C14	119.6 (3)
O1ⁱ—Cd1—O4ⁱ	82.53 (8)	C15—C14—C13	121.1 (3)
O5ⁱⁱ—Cd1—O4ⁱ	84.79 (9)	C15—C14—H14	119.5
N5—Cd1—O4ⁱ	80.69 (9)	C13—C14—H14	119.5
N4—Cd1—O4ⁱ	133.26 (9)	C14—C15—C16	120.8 (3)
O1—Cd1—O4ⁱ	143.94 (8)	C14—C15—H15	119.6
N1—C1—N3	126.4 (3)	C16—C15—H15	119.6
N1—C1—S1	119.5 (2)	C20—C16—C17	117.5 (3)
N3—C1—S1	114.1 (2)	C20—C16—C15	120.0 (3)
N2—C2—N1	126.4 (3)	C17—C16—C15	122.5 (3)
N2—C2—S2	114.1 (2)	C18—C17—C16	119.4 (3)
N1—C2—S2	119.4 (2)	C18—C17—H17	120.3
N3—C3—N2	127.3 (3)	C16—C17—H17	120.3
N3—C3—S3	121.0 (3)	C17—C18—C19	119.3 (3)
N2—C3—S3	111.6 (2)	C17—C18—H18	120.4
C5—C4—S1	117.4 (2)	C19—C18—H18	120.4
C5—C4—H4A	108.0	N5—C19—C18	123.1 (3)
S1—C4—H4A	108.0	N5—C19—H19	118.4
C5—C4—H4B	108.0	C18—C19—H19	118.4
S1—C4—H4B	108.0	N5—C20—C16	122.6 (3)
H4A—C4—H4B	107.2	N5—C20—C21	118.6 (3)
O2—C5—O1	123.5 (3)	C16—C20—C21	118.8 (3)
O2—C5—C4	116.3 (3)	N4—C21—C13	122.4 (3)
O1—C5—C4	120.2 (3)	N4—C21—C20	117.9 (3)
C7—C6—S2	116.0 (3)	C13—C21—C20	119.7 (3)
C7—C6—H6A	108.3	C1—N1—C2	113.5 (3)
S2—C6—H6A	108.3	C2—N2—C3	113.0 (3)
C7—C6—H6B	108.3	C3—N3—C1	113.3 (3)
S2—C6—H6B	108.3	C10—N4—C21	118.7 (3)
H6A—C6—H6B	107.4	C10—N4—Cd1	125.7 (2)
O4—C7—O3	124.8 (4)	C21—N4—Cd1	115.45 (19)
O4—C7—C6	119.2 (3)	C19—N5—C20	118.0 (3)
O3—C7—C6	116.0 (3)	C19—N5—Cd1	125.7 (2)
C9—C8—S3	113.0 (3)	C20—N5—Cd1	116.0 (2)
C9—C8—H8A	109.0	C5—O1—Cd1ⁱ	101.51 (19)
S3—C8—H8A	109.0	C5—O1—Cd1	124.8 (2)
C9—C8—H8B	109.0	Cd1ⁱ—O1—Cd1	108.35 (9)
S3—C8—H8B	109.0	C7—O3—H3	109.3
H8A—C8—H8B	107.8	C7—O4—Cd1ⁱ	136.9 (2)
O5—C9—O6	126.1 (3)	C9—O5—Cd1ⁱⁱ	143.1 (2)
O5—C9—C8	118.0 (3)	C1—S1—C4	101.33 (16)
O6—C9—C8	115.9 (3)	C2—S2—C6	101.51 (17)
N4—C10—C11	122.2 (3)	C3—S3—C8	103.00 (16)
N4—C10—H10	118.9	H71—O7—H72	110 (6)

S1—C4—C5—O2	−179.5 (3)	N5—Cd1—N4—C10	178.2 (3)
S1—C4—C5—O1	0.1 (4)	O1—Cd1—N4—C10	−41.9 (3)
S2—C6—C7—O4	165.6 (3)	O4ⁱ—Cd1—N4—C10	121.1 (3)
S2—C6—C7—O3	−15.3 (4)	O1ⁱ—Cd1—N4—C21	−150.7 (2)
S3—C8—C9—O5	139.6 (3)	O5ⁱⁱ—Cd1—N4—C21	76.5 (2)
S3—C8—C9—O6	−42.5 (4)	N5—Cd1—N4—C21	2.5 (2)
N4—C10—C11—C12	−0.2 (6)	O1—Cd1—N4—C21	142.4 (2)
C10—C11—C12—C13	−0.2 (6)	O4ⁱ—Cd1—N4—C21	−54.7 (3)
C11—C12—C13—C21	0.7 (5)	C18—C19—N5—C20	−0.4 (5)
C11—C12—C13—C14	178.1 (4)	C18—C19—N5—Cd1	174.1 (2)
C12—C13—C14—C15	−176.4 (4)	C16—C20—N5—C19	−0.2 (5)
C21—C13—C14—C15	0.9 (6)	C21—C20—N5—C19	178.8 (3)
C13—C14—C15—C16	−0.5 (6)	C16—C20—N5—Cd1	−175.2 (2)
C14—C15—C16—C20	−0.4 (5)	C21—C20—N5—Cd1	3.8 (4)
C14—C15—C16—C17	178.4 (4)	O1ⁱ—Cd1—N5—C19	−85.7 (3)
C20—C16—C17—C18	−1.4 (5)	O5ⁱⁱ—Cd1—N5—C19	48.4 (3)
C15—C16—C17—C18	179.7 (3)	N4—Cd1—N5—C19	−177.9 (3)
C16—C17—C18—C19	0.9 (5)	O1—Cd1—N5—C19	124.7 (3)
C17—C18—C19—N5	0.0 (5)	O4ⁱ—Cd1—N5—C19	−36.2 (3)
C17—C16—C20—N5	1.1 (5)	O1ⁱ—Cd1—N5—C20	88.9 (3)
C15—C16—C20—N5	−180.0 (3)	O5ⁱⁱ—Cd1—N5—C20	−137.0 (2)
C17—C16—C20—C21	−177.9 (3)	N4—Cd1—N5—C20	−3.3 (2)
C15—C16—C20—C21	1.0 (5)	O1—Cd1—N5—C20	−60.7 (2)
C12—C13—C21—N4	−0.9 (5)	O4ⁱ—Cd1—N5—C20	138.4 (2)
C14—C13—C21—N4	−178.4 (3)	O2—C5—O1—Cd1ⁱ	4.0 (4)
C12—C13—C21—C20	177.2 (3)	C4—C5—O1—Cd1ⁱ	−175.6 (2)
C14—C13—C21—C20	−0.3 (5)	O2—C5—O1—Cd1	−118.2 (3)
N5—C20—C21—N4	−1.5 (4)	C4—C5—O1—Cd1	62.2 (4)
C16—C20—C21—N4	177.5 (3)	O1ⁱ—Cd1—O1—C5	119.1 (3)
N5—C20—C21—C13	−179.7 (3)	O5ⁱⁱ—Cd1—O1—C5	7.1 (2)
C16—C20—C21—C13	−0.6 (5)	N5—Cd1—O1—C5	−74.2 (3)
N3—C1—N1—C2	−2.2 (5)	N4—Cd1—O1—C5	−128.6 (3)
S1—C1—N1—C2	176.4 (2)	O4ⁱ—Cd1—O1—C5	72.6 (3)
N2—C2—N1—C1	1.0 (5)	O5ⁱⁱ—Cd1—O1—Cd1ⁱ	−112.05 (11)
S2—C2—N1—C1	−176.7 (2)	N5—Cd1—O1—Cd1ⁱ	166.69 (9)
N1—C2—N2—C3	0.3 (5)	N4—Cd1—O1—Cd1ⁱ	112.23 (11)
S2—C2—N2—C3	178.2 (2)	O4ⁱ—Cd1—O1—Cd1ⁱ	−46.50 (17)
N3—C3—N2—C2	−0.8 (5)	O3—C7—O4—Cd1ⁱ	54.0 (5)
S3—C3—N2—C2	177.1 (2)	C6—C7—O4—Cd1ⁱ	−127.0 (3)
N2—C3—N3—C1	−0.2 (5)	O6—C9—O5—Cd1ⁱⁱ	48.3 (6)
S3—C3—N3—C1	−177.8 (2)	C8—C9—O5—Cd1ⁱⁱ	−134.1 (3)
N1—C1—N3—C3	1.8 (5)	N1—C1—S1—C4	−7.9 (3)
S1—C1—N3—C3	−176.8 (2)	N3—C1—S1—C4	170.9 (2)
C11—C10—N4—C21	0.0 (6)	C5—C4—S1—C1	80.6 (3)
C11—C10—N4—Cd1	−175.6 (3)	N2—C2—S2—C6	167.5 (3)
C13—C21—N4—C10	0.5 (5)	N1—C2—S2—C6	−14.5 (3)
C20—C21—N4—C10	−177.6 (3)	C7—C6—S2—C2	−71.7 (3)
C13—C21—N4—Cd1	176.6 (2)	N3—C3—S3—C8	−11.5 (3)
C20—C21—N4—Cd1	−1.5 (4)	N2—C3—S3—C8	170.4 (3)
O1ⁱ—Cd1—N4—C10	25.0 (3)	C9—C8—S3—C3	−95.0 (3)
O5ⁱⁱ—Cd1—N4—C10	−107.7 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O6ⁱⁱⁱ	0.82	1.68	2.439 (4)	154
O7—H71···O2^iv	0.75 (2)	2.35 (12)	2.984 (11)	142 (18)
C15—H15···O2^v	0.93	2.50	3.294 (6)	143
C17—H17···O2^v	0.93	2.57	3.353 (6)	142

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

Experimental details

Crystal data
Chemical formula	[Cd(C₉H₇N₃O₆S₃)(C₁₂H₈N₂)]·0.42H₂O
M_r	649.53
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.618 (2), 10.987 (2), 12.601 (2)
α, β, γ (°)	95.815 (3), 114.197 (2), 113.909 (2)
V (Å³)	1161.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.30 × 0.28 × 0.26

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.691, 0.720
No. of measured, independent and observed [I > 2σ(I)] reflections	6114, 4024, 3322
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.071, 1.07
No. of reflections	4024
No. of parameters	343
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.47

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—O1	2.447 (2)	Cd1—O5ⁱⁱ	2.295 (2)
Cd1—O1ⁱ	2.274 (2)	Cd1—N4	2.331 (3)
Cd1—O4ⁱ	2.490 (3)	Cd1—N5	2.320 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O6ⁱⁱⁱ	0.82	1.68	2.439 (4)	154
O7—H71···O2^iv	0.75 (2)	2.35 (12)	2.984 (11)	142 (18)
C15—H15···O2^v	0.93	2.50	3.294 (6)	143
C17—H17···O2^v	0.93	2.57	3.353 (6)	142

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

Acknowledgements

This project was supported by the Foundation of Shandong Natural Science (grant No. ZR2010BL020).

References

Bruker (2000). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lu, Q., Wang, D. & Wang, S. (2010). Acta Cryst. C66, m351–m354. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rao, C. N. R., Natarajan, S. & Vaidhyanathan, R. (2004). Angew. Chem. Int. Ed. 43, 1466–1496. Web of Science CrossRef CAS Google Scholar
Rowsell, J. L. C. & Yaghi, O. M. (2005). Angew. Chem. Int. Ed. 44, 4670–4679. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, S. N., Sun, R., Wang, X. S., Li, Y. Z., Pan, Y., Bai, J. F., Scheer, M. & You, X. Z. (2007). CrystEngComm, 9, 1051–1061. Web of Science CSD CrossRef Google Scholar
Wu, S., Ma, L., Long, L., Zheng, L. & Lin, W. (2009). Inorg. Chem. 48, 2436–2442. Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.