Poly[μ2-chlorido-(μ2-3H+-1,3,4-thia­diazo­lium-2-thiol­ato-κ2S:S)silver(I)]

Wang, J.-G.; Qin, J.-H.; Hu, P.-Z.

doi:10.1107/S1600536809012975

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m507

doi:10.1107/S1600536809012975

Open

access

Poly[μ₂-chlorido-(μ₂-3H⁺-1,3,4-thiadiazolium-2-thiolato-κ²S:S)silver(I)]

Jian-Ge Wang,^a Jian-Hua Qin ^a ^* and Pu-Zhou Hu ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: jh_q128105@126.com

(Received 23 February 2009; accepted 6 April 2009; online 10 April 2009)

In the title compound, [AgCl(C₂H₂N₂S₂)]_n, the Ag^I ion has a distorted tetrahedral geometry, defined by two S atoms of two symmetry-related 1,3,4-thiadiazolium-2-thiolate ligands and two chloride ions. The Ag^I ions are bridged into a two-dimensional network parallel to the ab plane by chloride ions and thiadiazole ligands. In the network, the Ag^I ions are separated by 4.0316 (12) Å along the a axis and by 4.8822 (13) Å along the b axis. N—H⋯Cl hydrogen bonds are observed within the network.

Related literature

For bond-length data, see: Dinger et al. (1998 ); Wei et al. (2008 ).

Experimental

Crystal data

[AgCl(C₂H₂N₂S₂)]
M_r = 261.50
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.0316 (9) Å
b = 8.473 (2) Å
c = 18.368 (4) Å
V = 627.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 4.19 mm⁻¹
T = 294 K
0.23 × 0.13 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.446, T_max = 0.786
4169 measured reflections
1161 independent reflections
1085 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.083
S = 1.09
1161 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 1.22 e Å⁻³
Δρ_min = −0.65 e Å⁻³
Absolute structure: Flack (1983 ), 438 Friedel pairs
Flack parameter: 0.05 (6)

Table 1
Selected bond lengths (Å)

Ag1—S2ⁱ	2.5454 (14)
Ag1—S2	2.5695 (15)
Ag1—Cl1ⁱⁱ	2.5897 (15)
Ag1—Cl1	2.6514 (15)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1ⁱⁱ	0.86	2.38	3.197 (4)	158
Symmetry code: (ii) x-1, y, z.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012975/ci2771sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012975/ci2771Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound consists of one Ag^I ion, one 1,3,4-thiadiazolium-2-thiolate ligand, and one Cl atom. As depicted in Fig. 1, the Ag^I ion is coordinated by two S atoms from two thiadiazole ligands and two Cl atoms in a distorted tetrahedral geometry. The Ag—S and Ag—Cl bond distances (Table 1) are within the range expected for such coordination bonds (Dinger et al., 1998; Wei et al., 2008). The thiadiazole ligand shows a monodentate bridging mode. The adjacent Ag^I atoms are bridged by Cl atoms to form chains, which are cross-linked by thiadiazole ligands to form a two-dimensional network parallel to the ab plane (Fig. 2). In the network, the Ag atoms are separated by 4.0316 (12) Å along the a axis and 4.8822 (13) Å along the b axis. Intramolecular N—H···Cl hydrogen bonds are observed in the network (Table 2).

Related literature top

For bond-length data, see: Dinger et al. (1998); Wei et al. (2008).

Experimental top

1,3,4-Thiadiazolium-2-thiolate (0.5 mmol) was added at room temperature to a ammonia solution (10 ml) of AgCl (0.5 mmol). After the addition, a colourless precipitate immediately formed and the suspension was stirred for 2 h. The precipitate was filtered off and washed with MeCN. Single crystals suitable for X-ray analysis were obtained by slow diffusion of Et₂O into a water solution of the solid.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 local coordination of the Ag^I atom in the title compound. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (A) 2 -x, y - 1/2, 1/2 - z; (B) x - 1, y, z.
	Fig. 2. A view of the two-dimensional network parallel to the ab plane.

Poly[µ₂-chlorido-(µ₂-3H⁺-1,3,4-thiadiazolium-2-thiolato- κ²S:S)silver(I)] top

Crystal data top

[AgCl(C₂H₂N₂S₂)]	F(000) = 496
M_r = 261.50	D_x = 2.768 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1870 reflections
a = 4.0316 (9) Å	θ = 3.3–27.2°
b = 8.473 (2) Å	µ = 4.19 mm⁻¹
c = 18.368 (4) Å	T = 294 K
V = 627.4 (2) Å³	Block, colourless
Z = 4	0.23 × 0.13 × 0.06 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1161 independent reflections
Radiation source: fine-focus sealed tube	1085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −4→4
T_min = 0.446, T_max = 0.786	k = −10→10
4169 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0526P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1161 reflections	Δρ_max = 1.22 e Å⁻³
73 parameters	Δρ_min = −0.65 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 438 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (6)

Crystal data top

[AgCl(C₂H₂N₂S₂)]	V = 627.4 (2) Å³
M_r = 261.50	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.0316 (9) Å	µ = 4.19 mm⁻¹
b = 8.473 (2) Å	T = 294 K
c = 18.368 (4) Å	0.23 × 0.13 × 0.06 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1161 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1085 reflections with I > 2σ(I)
T_min = 0.446, T_max = 0.786	R_int = 0.035
4169 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 1.22 e Å⁻³
S = 1.09	Δρ_min = −0.65 e Å⁻³
1161 reflections	Absolute structure: Flack (1983), 438 Friedel pairs
73 parameters	Absolute structure parameter: 0.05 (6)
0 restraints

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

	x	y	z	U_iso*/U_eq
Ag1	0.97702 (12)	−0.03604 (5)	0.18414 (2)	0.04254 (19)
Cl1	1.4870 (4)	−0.08711 (14)	0.09609 (6)	0.0323 (3)
S1	0.6628 (4)	0.55205 (15)	0.14333 (7)	0.0346 (3)
S2	0.9323 (4)	0.25800 (16)	0.21696 (7)	0.0356 (4)
N1	0.6067 (12)	0.2855 (5)	0.0889 (2)	0.0350 (12)
H1	0.6188	0.1852	0.0823	0.042*
N2	0.4580 (15)	0.3800 (5)	0.0387 (2)	0.0420 (13)
C1	0.7324 (12)	0.3512 (6)	0.1482 (2)	0.0266 (11)
C2	0.4723 (15)	0.5228 (6)	0.0601 (3)	0.0329 (12)
H2	0.3863	0.6056	0.0327	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0574 (3)	0.0311 (3)	0.0391 (3)	0.0042 (2)	−0.0090 (2)	0.00192 (16)
Cl1	0.0369 (7)	0.0237 (6)	0.0365 (6)	−0.0013 (6)	−0.0016 (6)	−0.0009 (5)
S1	0.0485 (8)	0.0187 (6)	0.0364 (7)	0.0010 (6)	−0.0108 (6)	−0.0037 (6)
S2	0.0546 (9)	0.0215 (6)	0.0307 (7)	0.0065 (6)	−0.0107 (6)	−0.0034 (5)
N1	0.059 (3)	0.019 (2)	0.026 (2)	0.003 (2)	−0.007 (2)	−0.0031 (18)
N2	0.065 (4)	0.027 (3)	0.034 (2)	0.003 (3)	−0.015 (3)	0.0008 (19)
C1	0.032 (3)	0.023 (3)	0.025 (2)	0.000 (2)	0.004 (2)	−0.001 (2)
C2	0.044 (3)	0.026 (3)	0.028 (2)	0.002 (3)	−0.008 (2)	0.001 (2)

Geometric parameters (Å, º) top

Ag1—S2ⁱ	2.5454 (14)	S2—C1	1.694 (5)
Ag1—S2	2.5695 (15)	S2—Ag1^iv	2.5453 (14)
Ag1—Cl1ⁱⁱ	2.5897 (15)	N1—C1	1.323 (6)
Ag1—Cl1	2.6514 (15)	N1—N2	1.361 (6)
Cl1—Ag1ⁱⁱⁱ	2.5897 (15)	N1—H1	0.86
S1—C1	1.727 (5)	N2—C2	1.273 (7)
S1—C2	1.729 (5)	C2—H2	0.93

S2ⁱ—Ag1—S2	120.49 (3)	C1—N1—N2	118.6 (4)
S2ⁱ—Ag1—Cl1ⁱⁱ	116.15 (5)	C1—N1—H1	120.7
S2—Ag1—Cl1ⁱⁱ	104.77 (4)	N2—N1—H1	120.7
S2ⁱ—Ag1—Cl1	102.24 (5)	C2—N2—N1	109.3 (4)
S2—Ag1—Cl1	110.84 (5)	N1—C1—S2	126.8 (4)
Cl1ⁱⁱ—Ag1—Cl1	100.56 (5)	N1—C1—S1	108.1 (4)
Ag1ⁱⁱⁱ—Cl1—Ag1	100.56 (5)	S2—C1—S1	125.1 (3)
C1—S1—C2	88.6 (2)	N2—C2—S1	115.4 (4)
C1—S2—Ag1^iv	106.32 (18)	N2—C2—H2	122.3
C1—S2—Ag1	108.09 (18)	S1—C2—H2	122.3
Ag1^iv—S2—Ag1	145.29 (5)

S2ⁱ—Ag1—Cl1—Ag1ⁱⁱⁱ	−60.05 (5)	N2—N1—C1—S2	−179.1 (4)
S2—Ag1—Cl1—Ag1ⁱⁱⁱ	69.61 (5)	N2—N1—C1—S1	0.2 (6)
Cl1ⁱⁱ—Ag1—Cl1—Ag1ⁱⁱⁱ	180.0	Ag1^iv—S2—C1—N1	−172.7 (5)
S2ⁱ—Ag1—S2—C1	−158.63 (19)	Ag1—S2—C1—N1	2.7 (5)
Cl1ⁱⁱ—Ag1—S2—C1	−25.46 (19)	Ag1^iv—S2—C1—S1	8.2 (4)
Cl1—Ag1—S2—C1	82.19 (19)	Ag1—S2—C1—S1	−176.5 (3)
S2ⁱ—Ag1—S2—Ag1^iv	13.55 (10)	C2—S1—C1—N1	−0.5 (4)
Cl1ⁱⁱ—Ag1—S2—Ag1^iv	146.72 (12)	C2—S1—C1—S2	178.8 (4)
Cl1—Ag1—S2—Ag1^iv	−105.63 (12)	N1—N2—C2—S1	−0.9 (7)
C1—N1—N2—C2	0.4 (8)	C1—S1—C2—N2	0.8 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱⁱ	0.86	2.38	3.197 (4)	158

Symmetry code: (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[AgCl(C₂H₂N₂S₂)]
M_r	261.50
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	4.0316 (9), 8.473 (2), 18.368 (4)
V (Å³)	627.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.19
Crystal size (mm)	0.23 × 0.13 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.446, 0.786
No. of measured, independent and observed [I > 2σ(I)] reflections	4169, 1161, 1085
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.09
No. of reflections	1161
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.22, −0.65
Absolute structure	Flack (1983), 438 Friedel pairs
Absolute structure parameter	0.05 (6)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ag1—S2ⁱ	2.5454 (14)	Ag1—Cl1ⁱⁱ	2.5897 (15)
Ag1—S2	2.5695 (15)	Ag1—Cl1	2.6514 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱⁱ	0.86	2.38	3.197 (4)	158

Symmetry code: (ii) x−1, y, z.

Acknowledgements

The authors thank Luoyang Normal University for supporting this work.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dinger, M. B., Henderson, W., Nicholson, B. K. & Robinson, W. T. (1998). J. Organomet. Chem. 560, 169–181. Web of Science CSD CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wei, X. Y., Di, D., Chu, W., Zhu, Q. L. & Huang, R. D. (2008). Inorg. Chim. Acta, 361, 1819–1826. Web of Science CSD CrossRef CAS Google Scholar