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

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.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](N-C) = 0.007 Å
• R factor = 0.031
• wR factor = 0.083
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ag1    --  Cl1     ..      28.09 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ag1    --  S2      ..      15.22 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ag1    --  Cl1_a   ..      11.56 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ag1    --  S2_c    ..      10.67 su

Alert level C
            Value of measurement temperature given =   294.000
            Value of melting point given =     0.000
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.23

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.50
           From the CIF: _reflns_number_total               1161
           Count of symmetry unique reflns          724
           Completeness (_total/calc)            160.36%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       437
           Fraction of Friedel pairs measured     0.604
           Are heavy atom types Z>Si present        yes
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.20 Ratio

   0 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

H atoms were positioned geometrically and treated as riding, with N-H = 0.86 Å and U_iso(H) = 1.2U_eq(N), and C-H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

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

	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)]

Crystal data

[AgCl(C2H2N2S2)]	F(000) = 496
Mr = 261.50	Dx = 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) Å^3	Block, colourless
Z = 4	0.23 × 0.13 × 0.06 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0526P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
1161 reflections	Δρmax = 1.22 e Å^−3
73 parameters	Δρmin = −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)

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Ag1—S2^i	2.5454 (14)	S2—C1	1.694 (5)
Ag1—S2	2.5695 (15)	S2—Ag1^iv	2.5453 (14)
Ag1—Cl1^ii	2.5897 (15)	N1—C1	1.323 (6)
Ag1—Cl1	2.6514 (15)	N1—N2	1.361 (6)
Cl1—Ag1^iii	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
S2^i—Ag1—S2	120.49 (3)	C1—N1—N2	118.6 (4)
S2^i—Ag1—Cl1^ii	116.15 (5)	C1—N1—H1	120.7
S2—Ag1—Cl1^ii	104.77 (4)	N2—N1—H1	120.7
S2^i—Ag1—Cl1	102.24 (5)	C2—N2—N1	109.3 (4)
S2—Ag1—Cl1	110.84 (5)	N1—C1—S2	126.8 (4)
Cl1^ii—Ag1—Cl1	100.56 (5)	N1—C1—S1	108.1 (4)
Ag1^iii—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)
S2^i—Ag1—Cl1—Ag1^iii	−60.05 (5)	N2—N1—C1—S2	−179.1 (4)
S2—Ag1—Cl1—Ag1^iii	69.61 (5)	N2—N1—C1—S1	0.2 (6)
Cl1^ii—Ag1—Cl1—Ag1^iii	180.0	Ag1^iv—S2—C1—N1	−172.7 (5)
S2^i—Ag1—S2—C1	−158.63 (19)	Ag1—S2—C1—N1	2.7 (5)
Cl1^ii—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)
S2^i—Ag1—S2—Ag1^iv	13.55 (10)	C2—S1—C1—N1	−0.5 (4)
Cl1^ii—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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1^ii	0.86	2.38	3.197 (4)	158

Symmetry code: (ii) x−1, y, z.