catena-Poly[[zinc-bis­(μ-2-sulfido-1H-benzimidazol-3-ium-5-carboxyl­ato)-κ² O:S;κ² S:O] trihydrate]

Abstract

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 [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,

• a = 8.031 (1) Å

• b = 9.732 (3) Å

• c = 12.436 (7) Å

• β = 96.584 (9)°

• V = 965.6 (6) ų

• 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[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms on C and N were positioned geometrically and refined as riding atoms, with C—H = 0.93 and N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C,N). H atoms of water molecules were located in a difference Fourier map and refined as riding atoms, with U_iso(H) = 1.5U_eq(O).

Figures

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.

Crystal data

[Zn(C8H5N2O2S)2]·3H2O	F(000) = 516
Mr = 505.86	Dx = 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

Bruker APEXII CCD diffractometer	1710 independent reflections
Radiation source: fine-focus sealed tube	1267 reflections with I > 2σ(I)
graphite	Rint = 0.049
φ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
Tmin = 0.749, Tmax = 0.802	k = −9→11
4749 measured reflections	l = −14→14

Refinement

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(Fo2) + (0.0471P)2 + 0.5228P] where P = (Fo2 + 2Fc2)/3
1710 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···O1iv	0.86	1.98	2.812 (4)	163
O1W—H1A···O2v	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.