catena-Poly[[zinc-bis­(μ-2-sulfido-1H-benzimidazol-3-ium-5-carboxyl­ato)-κ2O:S;κ2S:O] trihydrate]

Li, Y.-P.; Sun, D.-J.; Zang, H.; Han, L.-Y.; Su, G.-F.

doi:10.1107/S1600536811006532

metal-organic compounds

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Volume 67| Part 4| April 2011| Page m397

doi:10.1107/S1600536811006532

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catena-Poly[[zinc-bis(μ-2-sulfido-1H-benzimidazol-3-ium-5-carboxylato)-κ²O:S;κ²S:O] trihydrate]

Ya-Ping Li,^a Da-Jun Sun,^b ^* Hu Zang,^c Li-Ying Han ^d and Guan-Fang Su ^a

^aDepartment of Ophthalmology, the Second Hospital of Jilin University, Changchun 130041, People's Republic of China, ^bDepartment of Vascular Surgery, the China–Japan Union Hospital of Jilin University, Changchun 130033, People's Republic of China, ^cDepartment of Orthopedics, the China–Japan Union Hospital of Jilin University, Changchun 130033, People's Republic of China, and ^dDepartment of Gynecology, The Second Hospital of Jilin University, Changchun 130041, People's Republic of China
^*Correspondence e-mail: li_yp2002@yahoo.com.cn

(Received 28 December 2010; accepted 21 February 2011; online 5 March 2011)

In the title compound, {[Zn(C₈H₅N₂O₂S)₂]·3H₂O}_n, the Zn^II atom, lying on a twofold rotation axis, is four-coordinated by two S atoms and two O atoms from four 2-sulfido-1H-benzimidazol-3-ium-5-carboxylate (H₂mbidc) ligands in a distorted tetrahedral geometry. Two H₂mbidc ligands bridge two Zn^II atoms, generating a double-chain along [ $[\overline{1}]$ 01]. Adjacent chains are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional supramolecular network. One of the two water molecules also lies on a twofold rotation axis.

Related literature

For coordination polymers with helical chain structures, see: Chen & Liu (2002 ); Cui et al. (2003 ); Hu et al. (2008 ); Ngo & Lin (2002 ); Xiao et al. (2007 ); Yan et al. (2005 ).

Experimental

Crystal data

[Zn(C₈H₅N₂O₂S)₂]·3H₂O
M_r = 505.86
Monoclinic, P 2/n
a = 8.031 (1) Å
b = 9.732 (3) Å
c = 12.436 (7) Å
β = 96.584 (9)°
V = 965.6 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.749, T_max = 0.802
4749 measured reflections
1710 independent reflections
1267 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.099
S = 0.98
1710 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1W	0.86	1.88	2.738 (5)	174
N2—H2⋯O1ⁱ	0.86	1.98	2.812 (4)	163
O1W—H1A⋯O2ⁱⁱ	0.84	2.21	2.907 (4)	140
O2W—H2A⋯O1	0.82	2.02	2.837 (4)	177
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y+1, 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: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811006532/hy2396sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006532/hy2396Isup2.hkl

checkCIF report

Comment top

In recent years, the synthesis of novel coordination polymers with helical structures has attracted much attention owing to the fundamental role of helicity in biology and their potential utilization in advanced materials (Cui et al., 2003; Ngo & Lin, 2002; Yan et al., 2005). In general, the V-shaped organic ligands have already been proven to be efficient for the generation of helical complexes (Chen & Liu, 2002; Hu et al., 2008; Xiao et al., 2007). 2-Mercapto-1H-benzo[d]imidazole-5-carboxylic acid (H₃mbidc) is a rigid V-shaped ligand, in which the S atom can coordinate to a variety of metal ions and the carboxylate group can adopt rich coordination modes, meeting the requirements of the coordination geometries of metal ions in assembly process. We selected H₃mbidc as a bridging ligand and Zn^II ion as a metal center, generating a new double-chain coordination polymer, whose structure is reported here.

In the title compound (Fig. 1), the Zn^II atom is four-coordinated by two S atoms and two carboxylate O atoms from four individual H₂mbidc ligands in a distorted tetrahedral coordination geometry. The Cd—O and Cd—S bond lengths are 1.987 (3) and 2.3159 (12) Å. Each H₂mbidc ligand bridges two neighboring Zn^II atoms, generating a double-chain (Fig. 2). Furthermore, N—H···O and O—H···O hydrogen bonds (Table 1) link the chains together, resulting in a supramolecular structure.

Related literature top

For coordination polymers with helical chain structures, see: Chen & Liu (2002); Cui et al. (2003); Hu et al. (2008); Ngo & Lin (2002); Xiao et al. (2007); Yan et al. (2005).

Experimental top

A mixture of H₃mbidc (0.971 g, 5 mmol), NaOH (0.4 g, 10 mmol) and ZnCl₂ (1.36 g, 10 mmol) in water (50 ml) was boiled for 20 min with stirring. Then the mixture was cooled to room temperature. The resulting solution was filtered and allowed to stand. After a week, colorless crystals of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Dashed lines denote hydrogen bonds. [Symmetry codes: (i) 1 - x, 1 - y, 2 - z; (ii) 3/2 - x, y, 3/2 - z; (iii) 1/2 + x, 1 - y, -1/2 + z.]
	Fig. 2. A view of the double-chain structure in the title compound.

catena-Poly[[zinc-bis(µ-2-sulfido-1H-benzimidazol-3-ium-5-carboxylato)-κ²O:S;κ²S:O] trihydrate] top

Crystal data top

[Zn(C₈H₅N₂O₂S)₂]·3H₂O	F(000) = 516
M_r = 505.86	D_x = 1.740 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 4749 reflections
a = 8.031 (1) Å	θ = 1.3–26.0°
b = 9.732 (3) Å	µ = 1.54 mm⁻¹
c = 12.436 (7) Å	T = 293 K
β = 96.584 (9)°	Block, colorless
V = 965.6 (6) Å³	0.20 × 0.18 × 0.15 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1710 independent reflections
Radiation source: fine-focus sealed tube	1267 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.749, T_max = 0.802	k = −9→11
4749 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0471P)² + 0.5228P] where P = (F_o² + 2F_c²)/3
1710 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Zn(C₈H₅N₂O₂S)₂]·3H₂O	V = 965.6 (6) Å³
M_r = 505.86	Z = 2
Monoclinic, P2/n	Mo Kα radiation
a = 8.031 (1) Å	µ = 1.54 mm⁻¹
b = 9.732 (3) Å	T = 293 K
c = 12.436 (7) Å	0.20 × 0.18 × 0.15 mm
β = 96.584 (9)°

Data collection top

Bruker APEXII CCD diffractometer	1710 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1267 reflections with I > 2σ(I)
T_min = 0.749, T_max = 0.802	R_int = 0.049
4749 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 0.98	Δρ_max = 0.42 e Å⁻³
1710 reflections	Δρ_min = −0.28 e Å⁻³
137 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.7500	0.20862 (7)	0.7500	0.0295 (2)
S1	0.46579 (13)	0.94066 (11)	1.22275 (9)	0.0366 (3)
O1	0.9750 (3)	0.4579 (3)	0.7829 (2)	0.0360 (7)
O2	0.8006 (3)	0.3368 (3)	0.8738 (2)	0.0323 (7)
N1	0.6753 (4)	0.9126 (3)	1.0706 (2)	0.0283 (8)
H1	0.6905	0.9997	1.0655	0.034*
N2	0.5899 (4)	0.7152 (3)	1.1261 (2)	0.0298 (8)
H2	0.5423	0.6551	1.1630	0.036*
C1	0.5795 (4)	0.8514 (4)	1.1382 (3)	0.0266 (9)
C2	0.7452 (4)	0.8136 (4)	1.0112 (3)	0.0258 (9)
C3	0.6897 (4)	0.6859 (4)	1.0445 (3)	0.0249 (9)
C4	0.7307 (4)	0.5650 (4)	0.9970 (3)	0.0269 (9)
H4	0.6920	0.4807	1.0191	0.032*
C5	0.8334 (4)	0.5746 (4)	0.9136 (3)	0.0261 (9)
C6	0.8901 (5)	0.7016 (4)	0.8817 (3)	0.0325 (10)
H6	0.9578	0.7048	0.8259	0.039*
C7	0.8494 (5)	0.8233 (4)	0.9299 (3)	0.0348 (10)
H7	0.8900	0.9075	0.9089	0.042*
C8	0.8752 (5)	0.4488 (4)	0.8531 (3)	0.0280 (9)
O1W	0.7018 (4)	1.1927 (3)	1.0612 (2)	0.0472 (8)
H1A	0.7766	1.2210	1.0243	0.071*
H1B	0.6896	1.2530	1.1073	0.071*
O2W	1.2500	0.6297 (5)	0.7500	0.0456 (11)
H2A	1.1720	0.5777	0.7590	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0350 (4)	0.0257 (4)	0.0303 (4)	0.000	0.0144 (3)	0.000
S1	0.0409 (7)	0.0283 (7)	0.0448 (6)	−0.0041 (5)	0.0230 (5)	−0.0092 (5)
O1	0.0392 (16)	0.0356 (18)	0.0363 (16)	−0.0035 (14)	0.0184 (13)	−0.0098 (14)
O2	0.0401 (16)	0.0301 (18)	0.0289 (15)	−0.0035 (13)	0.0129 (12)	−0.0031 (12)
N1	0.0341 (19)	0.0180 (18)	0.0353 (18)	−0.0021 (15)	0.0148 (15)	−0.0016 (15)
N2	0.0358 (19)	0.025 (2)	0.0323 (18)	−0.0004 (16)	0.0181 (15)	0.0008 (16)
C1	0.026 (2)	0.026 (2)	0.029 (2)	0.0005 (18)	0.0077 (17)	−0.0018 (17)
C2	0.026 (2)	0.022 (2)	0.030 (2)	0.0017 (17)	0.0081 (16)	−0.0006 (17)
C3	0.026 (2)	0.030 (2)	0.0206 (18)	0.0023 (17)	0.0088 (16)	0.0013 (17)
C4	0.029 (2)	0.023 (2)	0.030 (2)	0.0004 (17)	0.0091 (17)	0.0042 (17)
C5	0.028 (2)	0.031 (2)	0.0209 (19)	0.0029 (18)	0.0067 (16)	−0.0017 (17)
C6	0.033 (2)	0.038 (3)	0.029 (2)	−0.003 (2)	0.0162 (17)	0.003 (2)
C7	0.042 (2)	0.028 (3)	0.039 (2)	−0.0067 (19)	0.021 (2)	0.0044 (19)
C8	0.025 (2)	0.035 (3)	0.024 (2)	0.0016 (19)	−0.0012 (17)	−0.0022 (18)
O1W	0.064 (2)	0.0356 (19)	0.0453 (18)	−0.0104 (16)	0.0178 (15)	−0.0048 (15)
O2W	0.046 (3)	0.037 (3)	0.058 (3)	0.000	0.023 (2)	0.000

Geometric parameters (Å, º) top

Zn1—O2	1.987 (3)	C2—C3	1.400 (5)
Zn1—S1ⁱ	2.3159 (12)	C3—C4	1.374 (5)
S1—C1	1.707 (4)	C4—C5	1.400 (5)
O1—C8	1.254 (4)	C4—H4	0.9300
O2—C8	1.284 (5)	C5—C6	1.391 (5)
N1—C1	1.342 (4)	C5—C8	1.494 (5)
N1—C2	1.373 (5)	C6—C7	1.384 (6)
N1—H1	0.8600	C6—H6	0.9300
N2—C1	1.338 (5)	C7—H7	0.9300
N2—C3	1.392 (4)	O1W—H1A	0.84
N2—H2	0.8600	O1W—H1B	0.83
C2—C7	1.388 (5)	O2W—H2A	0.82

O2—Zn1—O2ⁱⁱ	102.22 (17)	C4—C3—N2	132.5 (4)
O2—Zn1—S1ⁱ	111.74 (8)	C4—C3—C2	122.2 (3)
O2ⁱⁱ—Zn1—S1ⁱ	114.66 (8)	N2—C3—C2	105.3 (3)
O2—Zn1—S1ⁱⁱⁱ	114.66 (8)	C3—C4—C5	116.9 (4)
O2ⁱⁱ—Zn1—S1ⁱⁱⁱ	111.74 (8)	C3—C4—H4	121.5
S1ⁱ—Zn1—S1ⁱⁱⁱ	102.30 (6)	C5—C4—H4	121.5
C1—S1—Zn1ⁱ	103.48 (14)	C6—C5—C4	120.7 (4)
C8—O2—Zn1	115.9 (2)	C6—C5—C8	119.0 (3)
C1—N1—C2	109.0 (3)	C4—C5—C8	120.2 (4)
C1—N1—H1	125.5	C7—C6—C5	122.4 (3)
C2—N1—H1	125.5	C7—C6—H6	118.8
C1—N2—C3	109.5 (3)	C5—C6—H6	118.8
C1—N2—H2	125.3	C6—C7—C2	116.7 (4)
C3—N2—H2	125.3	C6—C7—H7	121.6
N2—C1—N1	108.8 (3)	C2—C7—H7	121.6
N2—C1—S1	128.2 (3)	O1—C8—O2	123.3 (4)
N1—C1—S1	123.1 (3)	O1—C8—C5	119.4 (4)
N1—C2—C7	131.5 (4)	O2—C8—C5	117.2 (3)
N1—C2—C3	107.4 (3)	H1A—O1W—H1B	107.0
C7—C2—C3	121.0 (4)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+3/2, y, −z+3/2; (iii) x+1/2, −y+1, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1W	0.86	1.88	2.738 (5)	174
N2—H2···O1^iv	0.86	1.98	2.812 (4)	163
O1W—H1A···O2^v	0.84	2.21	2.907 (4)	140
O2W—H2A···O1	0.82	2.02	2.837 (4)	177

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

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₅N₂O₂S)₂]·3H₂O
M_r	505.86
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	293
a, b, c (Å)	8.031 (1), 9.732 (3), 12.436 (7)
β (°)	96.584 (9)
V (Å³)	965.6 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.54
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.749, 0.802
No. of measured, independent and observed [I > 2σ(I)] reflections	4749, 1710, 1267
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.099, 0.98
No. of reflections	1710
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1W	0.86	1.88	2.738 (5)	174
N2—H2···O1ⁱ	0.86	1.98	2.812 (4)	163
O1W—H1A···O2ⁱⁱ	0.84	2.21	2.907 (4)	140
O2W—H2A···O1	0.82	2.02	2.837 (4)	177

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

References

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