Crystal structure of 2-amino-5-methyl-sulfanyl-1,3,4-thia-diazol-3-ium chloride monohydrate.

The title salt, C3H6N3S2 (+)·Cl(-)·H2O, crystallized with two organic cations, two chloride anions and two water mol-ecules in the asymmetric unit. The methyl C atoms deviate from their respective bound ring planes by 0.081 and 0.002 Å. In the crystal, the components are connected via N-H⋯O, N-H⋯Cl and O-H⋯Cl hydrogen bonds, forming sheets lying parallel to (100). The sheets are linked into bilayers by O-H⋯Cl hydrogen bonds involving the chloride ions and water mol-ecules. Within the bilayers there are π-π inter-actions [inter-centroid distances = 3.4654 (4) and 3.4789 (4) Å] involving inversion-related cations.

Related literature

For the medicinal importance and biological activity of thia­diazol isomers, see: Demirbas et al. (2009 ▶). For applications of 1,3,4 thia­diazo­les in agriculture, see: Wei et al. (2006 ▶). For C—N bond lengths in the 2-amino-5-methyl­sulfanyl-1,3,4-thia­diazol-3-ium cation, see: Mrad et al. (2012 ▶).

Experimental

Crystal data

C3H6N3S2 +·Cl−·H2O

M = 201.69

Monoclinic,

a = 13.3826 (2) Å

b = 9.4258 (1) Å

c = 13.5762 (2) Å

β = 99.453 (1)°

V = 1689.27 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.89 mm−1

T = 110 K

0.42 × 0.31 × 0.15 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer

Absorption correction: analytical [CrysAlis PRO (Agilent, 2012 ▶), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995 ▶)] T min = 0.769, T max = 0.894

65950 measured reflections

8394 independent reflections

7745 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.054

S = 1.12

8394 reflections

224 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.28 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814015864/su2749sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015864/su2749Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814015864/su2749Isup3.tif

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814015864/su2749Isup4.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814015864/su2749fig1.tif

A view of mol­ecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S1600536814015864/su2749fig2.tif

A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details).

Click here for additional data file.

b . DOI: 10.1107/S1600536814015864/su2749fig3.tif

A partial view along the b axis of the crystal packing of the title compound, showing the inter­molecular π–π stacking inter­actions between inversion-related organic cations.

CCDC reference: 1012703

Additional supporting information: crystallographic information; 3D view; checkCIF report

C3H6N3S2+·Cl−·H2O	F(000) = 832
Mr = 201.69	Dx = 1.586 Mg m−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yac	Cell parameters from 30742 reflections
a = 13.3826 (2) Å	θ = 2.9–37.8°
b = 9.4258 (1) Å	µ = 0.89 mm−1
c = 13.5762 (2) Å	T = 110 K
β = 99.453 (1)°	Prism, colorless
V = 1689.27 (4) Å3	0.42 × 0.31 × 0.15 mm
Z = 8

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	8394 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	7745 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.4508 pixels mm-1	θmax = 36.7°, θmin = 2.9°
ω scans	h = −22→22
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	k = −15→15
Tmin = 0.769, Tmax = 0.894	l = −22→22
65950 measured reflections

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)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.054	w = 1/[σ2(Fo2) + (0.0211P)2 + 0.370P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.003
8394 reflections	Δρmax = 0.47 e Å−3
224 parameters	Δρmin = −0.28 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00111 (13)

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 > 2σ(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.

	x	y	z	Uiso*/Ueq
S7	0.127439 (13)	1.268596 (18)	0.444671 (12)	0.01782 (3)
Cl2	0.386288 (13)	0.472130 (17)	0.838806 (12)	0.01897 (3)
S1	0.129775 (12)	1.086700 (17)	0.628112 (12)	0.01498 (3)
S9	0.353350 (12)	0.596116 (17)	0.572019 (12)	0.01549 (3)
S15	0.370685 (15)	0.777122 (18)	0.392656 (13)	0.02012 (3)
Cl1	0.112933 (13)	0.978631 (17)	0.878768 (12)	0.01911 (3)
O18	0.39361 (4)	0.11409 (5)	0.40860 (4)	0.01921 (9)
O17	0.10727 (4)	0.60603 (5)	0.44691 (4)	0.01852 (9)
N12	0.38085 (4)	0.49199 (6)	0.40204 (4)	0.01616 (9)
N3	0.12906 (4)	0.87190 (6)	0.51663 (4)	0.01608 (9)
N6	0.13116 (5)	0.81093 (7)	0.68457 (4)	0.01909 (10)
N11	0.37722 (4)	0.38126 (6)	0.46775 (4)	0.01566 (9)
N14	0.35554 (5)	0.32153 (6)	0.63065 (4)	0.01771 (9)
N4	0.12853 (4)	0.98357 (6)	0.45103 (4)	0.01622 (9)
C10	0.36248 (5)	0.41383 (6)	0.55932 (5)	0.01406 (9)
C5	0.12929 (5)	1.10218 (7)	0.49890 (5)	0.01482 (9)
C13	0.36960 (5)	0.61102 (7)	0.44630 (5)	0.01494 (10)
C2	0.13012 (5)	0.90405 (7)	0.61203 (5)	0.01490 (10)
C16	0.38878 (6)	0.72871 (9)	0.26821 (5)	0.02396 (13)
H16B	0.4528	0.6771	0.2715	0.036*
H16A	0.3906	0.8146	0.2279	0.036*
H16C	0.3327	0.6681	0.2376	0.036*
C8	0.13379 (6)	1.21799 (9)	0.31782 (5)	0.02475 (13)
H8B	0.1962	1.1643	0.3161	0.037*
H8A	0.1335	1.3033	0.2765	0.037*
H8C	0.0751	1.1589	0.2919	0.037*
H18B	0.4504 (11)	0.0902 (15)	0.3960 (11)	0.045 (4)*
H18A	0.3831 (10)	0.0703 (14)	0.4546 (10)	0.033 (3)*
H6A	0.1303 (9)	0.8410 (13)	0.7431 (9)	0.028 (3)*
H14B	0.3640 (10)	0.2376 (14)	0.6235 (10)	0.033 (3)*
H14A	0.3506 (9)	0.3519 (14)	0.6907 (9)	0.031 (3)*
H6B	0.1286 (10)	0.7247 (14)	0.6724 (10)	0.036 (3)*
H17B	0.0504 (11)	0.5876 (15)	0.4157 (11)	0.045 (4)*
H17A	0.1117 (10)	0.5630 (15)	0.4979 (10)	0.037 (3)*
H3	0.1242 (9)	0.7870 (14)	0.4929 (9)	0.033 (3)*
H11	0.3851 (10)	0.2905 (15)	0.4467 (10)	0.043 (4)*

	U11	U22	U33	U12	U13	U23
S7	0.02231 (7)	0.01564 (6)	0.01558 (6)	−0.00113 (5)	0.00333 (5)	−0.00038 (5)
Cl2	0.02398 (7)	0.01862 (7)	0.01352 (6)	0.00121 (5)	0.00077 (5)	−0.00314 (5)
S1	0.01744 (6)	0.01459 (6)	0.01294 (6)	−0.00041 (5)	0.00259 (5)	−0.00314 (5)
S9	0.01931 (7)	0.01389 (6)	0.01357 (6)	0.00047 (5)	0.00357 (5)	−0.00272 (5)
S15	0.02861 (8)	0.01529 (7)	0.01681 (7)	−0.00147 (6)	0.00476 (6)	0.00022 (5)
Cl1	0.02353 (7)	0.01790 (6)	0.01740 (6)	−0.00308 (5)	0.00778 (5)	−0.00374 (5)
O18	0.0268 (2)	0.01509 (19)	0.0167 (2)	0.00361 (17)	0.00633 (18)	0.00171 (16)
O17	0.0251 (2)	0.0155 (2)	0.01450 (19)	−0.00279 (17)	0.00197 (17)	0.00079 (15)
N12	0.0187 (2)	0.0157 (2)	0.0147 (2)	−0.00090 (17)	0.00432 (17)	−0.00181 (17)
N3	0.0205 (2)	0.0144 (2)	0.0132 (2)	−0.00115 (17)	0.00220 (17)	−0.00289 (16)
N6	0.0265 (3)	0.0163 (2)	0.0143 (2)	−0.0013 (2)	0.00311 (19)	−0.00122 (18)
N11	0.0194 (2)	0.0141 (2)	0.0139 (2)	−0.00025 (17)	0.00404 (17)	−0.00234 (16)
N14	0.0241 (2)	0.0152 (2)	0.0137 (2)	0.00121 (19)	0.00275 (18)	−0.00082 (17)
N4	0.0190 (2)	0.0158 (2)	0.0137 (2)	−0.00094 (17)	0.00235 (17)	−0.00223 (17)
C10	0.0144 (2)	0.0141 (2)	0.0135 (2)	0.00004 (17)	0.00170 (18)	−0.00237 (17)
C5	0.0149 (2)	0.0160 (2)	0.0135 (2)	−0.00038 (18)	0.00204 (18)	−0.00209 (18)
C13	0.0159 (2)	0.0150 (2)	0.0140 (2)	−0.00095 (18)	0.00286 (18)	−0.00155 (18)
C2	0.0153 (2)	0.0154 (2)	0.0139 (2)	−0.00111 (18)	0.00202 (18)	−0.00291 (18)
C16	0.0260 (3)	0.0305 (4)	0.0159 (3)	0.0014 (3)	0.0047 (2)	0.0019 (2)
C8	0.0297 (3)	0.0296 (4)	0.0161 (3)	−0.0003 (3)	0.0069 (2)	0.0003 (2)

S7—C5	1.7312 (7)	N3—H3	0.861 (13)
S7—C8	1.8024 (7)	N6—C2	1.3176 (9)
S1—C2	1.7355 (6)	N6—H6A	0.846 (12)
S1—C5	1.7593 (6)	N6—H6B	0.829 (13)
S9—C10	1.7331 (6)	N11—C10	1.3264 (8)
S9—C13	1.7613 (6)	N11—H11	0.913 (14)
S15—C13	1.7278 (7)	N14—C10	1.3164 (9)
S15—C16	1.8043 (8)	N14—H14B	0.808 (13)
O18—H18B	0.836 (15)	N14—H14A	0.876 (13)
O18—H18A	0.780 (14)	N4—C5	1.2923 (8)
O17—H17B	0.827 (15)	C16—H16B	0.9800
O17—H17A	0.796 (14)	C16—H16A	0.9800
N12—C13	1.2932 (8)	C16—H16C	0.9800
N12—N11	1.3791 (8)	C8—H8B	0.9800
N3—C2	1.3280 (8)	C8—H8A	0.9800
N3—N4	1.3781 (8)	C8—H8C	0.9800
C5—S7—C8	99.61 (3)	N11—C10—S9	110.27 (5)
C2—S1—C5	87.51 (3)	N4—C5—S7	124.86 (5)
C10—S9—C13	87.75 (3)	N4—C5—S1	115.35 (5)
C13—S15—C16	100.21 (3)	S7—C5—S1	119.78 (4)
H18B—O18—H18A	108.1 (13)	N12—C13—S15	125.50 (5)
H17B—O17—H17A	105.6 (13)	N12—C13—S9	115.05 (5)
C13—N12—N11	109.69 (5)	S15—C13—S9	119.45 (4)
C2—N3—N4	117.01 (5)	N6—C2—N3	125.04 (6)
C2—N3—H3	124.4 (8)	N6—C2—S1	124.52 (5)
N4—N3—H3	118.4 (8)	N3—C2—S1	110.44 (5)
C2—N6—H6A	118.6 (8)	S15—C16—H16B	109.5
C2—N6—H6B	120.6 (9)	S15—C16—H16A	109.5
H6A—N6—H6B	120.6 (12)	H16B—C16—H16A	109.5
C10—N11—N12	117.23 (5)	S15—C16—H16C	109.5
C10—N11—H11	123.5 (9)	H16B—C16—H16C	109.5
N12—N11—H11	119.3 (9)	H16A—C16—H16C	109.5
C10—N14—H14B	122.1 (9)	S7—C8—H8B	109.5
C10—N14—H14A	119.6 (8)	S7—C8—H8A	109.5
H14B—N14—H14A	117.7 (12)	H8B—C8—H8A	109.5
C5—N4—N3	109.70 (5)	S7—C8—H8C	109.5
N14—C10—N11	125.16 (6)	H8B—C8—H8C	109.5
N14—C10—S9	124.57 (5)	H8A—C8—H8C	109.5
C13—N12—N11—C10	0.74 (8)	C2—S1—C5—S7	179.35 (4)
C2—N3—N4—C5	0.04 (8)	N11—N12—C13—S15	179.19 (5)
N12—N11—C10—N14	178.94 (6)	N11—N12—C13—S9	−0.16 (7)
N12—N11—C10—S9	−0.95 (7)	C16—S15—C13—N12	0.81 (7)
C13—S9—C10—N14	−179.23 (6)	C16—S15—C13—S9	−179.87 (4)
C13—S9—C10—N11	0.67 (5)	C10—S9—C13—N12	−0.29 (5)
N3—N4—C5—S7	−179.17 (5)	C10—S9—C13—S15	−179.68 (4)
N3—N4—C5—S1	−0.44 (7)	N4—N3—C2—N6	−179.72 (6)
C8—S7—C5—N4	−3.94 (7)	N4—N3—C2—S1	0.37 (7)
C8—S7—C5—S1	177.38 (4)	C5—S1—C2—N6	179.60 (6)
C2—S1—C5—N4	0.55 (5)	C5—S1—C2—N3	−0.49 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O17	0.861 (13)	1.818 (13)	2.6778 (7)	176.4 (12)
N6—H6A···Cl1	0.846 (12)	2.296 (12)	3.1178 (6)	164.2 (11)
N6—H6B···Cl2i	0.829 (13)	2.392 (13)	3.2139 (7)	171.4 (13)
N11—H11···O18	0.914 (14)	1.751 (14)	2.6632 (7)	176.7 (13)
N14—H14A···Cl2	0.877 (12)	2.289 (12)	3.1287 (6)	160.3 (11)
N14—H14B···Cl1ii	0.807 (13)	2.461 (13)	3.2648 (6)	173.6 (13)
O17—H17A···Cl2i	0.796 (14)	2.373 (14)	3.1593 (5)	169.8 (14)
O17—H17B···Cl2iii	0.826 (15)	2.340 (15)	3.1649 (6)	175.5 (14)
O18—H18A···Cl1ii	0.780 (13)	2.414 (13)	3.1708 (5)	163.8 (13)
O18—H18B···Cl1iv	0.837 (15)	2.318 (15)	3.1517 (6)	174.1 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O17	0.861 (13)	1.818 (13)	2.6778 (7)	176.4 (12)
N6—H6A⋯Cl1	0.846 (12)	2.296 (12)	3.1178 (6)	164.2 (11)
N6—H6B⋯Cl2i	0.829 (13)	2.392 (13)	3.2139 (7)	171.4 (13)
N11—H11⋯O18	0.914 (14)	1.751 (14)	2.6632 (7)	176.7 (13)
N14—H14A⋯Cl2	0.877 (12)	2.289 (12)	3.1287 (6)	160.3 (11)
N14—H14B⋯Cl1ii	0.807 (13)	2.461 (13)	3.2648 (6)	173.6 (13)
O17—H17A⋯Cl2i	0.796 (14)	2.373 (14)	3.1593 (5)	169.8 (14)
O17—H17B⋯Cl2iii	0.826 (15)	2.340 (15)	3.1649 (6)	175.5 (14)
O18—H18A⋯Cl1ii	0.780 (13)	2.414 (13)	3.1708 (5)	163.8 (13)
O18—H18B⋯Cl1iv	0.837 (15)	2.318 (15)	3.1517 (6)	174.1 (14)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .