(Diamino­methyl­idene)sulfonium chloride–thio­urea (3/2)

Zouihri, H.

doi:10.1107/S1600536811052809

organic compounds

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Volume 68| Part 2| February 2012| Page o257

doi:10.1107/S1600536811052809

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(Diaminomethylidene)sulfonium chloride–thiourea (3/2)

Hafid Zouihri ^a ^*

^aLaboratoire Privé de Cristallographie (L.P.C), Kénitra, Morocco.
^*Correspondence e-mail: hafid.zouihri@gmail.com

(Received 7 December 2011; accepted 7 December 2011; online 7 January 2012)

The asymetric unit of the title salt, 3CH₅N₂S⁺·3Cl⁻·2CH₄N₂S, contains two molecules of thiourea, three (diaminomethylidene)sulfonium cations and three chloride anions. The crystal packing is stabilized by N—H⋯Cl, N—H⋯S, S—H⋯Cl and S—H⋯S hydrogen bonds, forming a three-dimensional network.

Related literature

For applications of thiourea salts, see: Xing et al. (1987 ); Velsko et al. (1990 ).

Experimental

Crystal data

3CH₅N₂S⁺·3Cl⁻·2CH₄N₂S
M_r = 489.98
Monoclinic, P 2₁ /c
a = 16.3469 (6) Å
b = 8.9579 (3) Å
c = 16.1505 (5) Å
β = 109.105 (2)°
V = 2234.72 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 100 K
0.45 × 0.32 × 0.29 mm

Data collection

Bruker APEXII CCD detector diffractometer
25994 measured reflections
4885 independent reflections
4190 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.068
S = 1.06
4885 reflections
300 parameters
15 restraints
All H-atom parameters refined
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S3	0.82 (2)	2.76 (2)	3.5403 (17)	161.9 (18)
N1—H2N⋯Cl1	0.848 (18)	2.474 (18)	3.2683 (16)	156.2 (18)
N10—H17N⋯Cl3ⁱ	0.86 (2)	2.45 (2)	3.2261 (17)	152 (2)
N10—H18N⋯Cl1ⁱⁱ	0.85 (2)	2.35 (2)	3.2019 (14)	175 (2)
N2—H3N⋯Cl1	0.815 (18)	2.624 (18)	3.3656 (16)	152.0 (17)
N2—H4N⋯Cl1ⁱⁱ	0.86 (2)	2.45 (2)	3.3060 (17)	174.5 (17)
N3—H5N⋯Cl2	0.86 (2)	2.51 (2)	3.3333 (16)	161 (2)
N3—H6N⋯Cl1ⁱⁱⁱ	0.86 (2)	2.47 (2)	3.2799 (16)	157 (2)
N4—H7N⋯Cl3	0.84 (2)	2.43 (2)	3.2422 (17)	163 (2)
N4—H8N⋯Cl1ⁱⁱⁱ	0.84 (2)	2.57 (2)	3.3327 (16)	151 (2)
N4—H8N⋯S1^iv	0.84 (2)	2.83 (2)	3.3571 (16)	123 (2)
N5—H9N⋯S1	0.85 (2)	2.62 (2)	3.4493 (18)	166 (2)
N5—H10N⋯Cl2^v	0.91 (2)	2.35 (2)	3.2262 (16)	161 (2)
N6—H11N⋯Cl2^vi	0.88 (2)	2.47 (2)	3.3555 (17)	176 (1)
N6—H12N⋯Cl2^v	0.88 (2)	2.65 (2)	3.4328 (15)	149 (2)
N7—H13N⋯Cl2	0.86 (2)	2.37 (2)	3.2219 (15)	177 (1)
N7—H14N⋯Cl3^vii	0.85 (2)	2.42 (2)	3.2066 (17)	154 (2)
N8—H15N⋯S3^viii	0.85 (2)	2.44 (2)	3.2649 (16)	164 (2)
N8—H16N⋯Cl3^vii	0.87 (2)	2.39 (2)	3.2036 (17)	156 (2)
N9—H19N⋯Cl3ⁱ	0.84 (2)	2.38 (2)	3.1674 (17)	157 (2)
N9—H20N⋯S1^vii	0.872 (19)	2.38 (2)	3.2412 (16)	167.7 (19)
S2—H2S⋯Cl2	1.253 (19)	2.315 (19)	3.5612 (6)	172.9 (14)
S4—H4S⋯S3^viii	1.24 (2)	2.69 (2)	3.8755 (8)	159.2 (15)
S5—H5S⋯S1^vii	1.29 (2)	2.64 (2)	3.8691 (7)	159.3 (16)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) x, y+1, z; (vi) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (viii) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052809/bt5746sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052809/bt5746Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052809/bt5746Isup3.cml

checkCIF report

Comment top

Various semi-organic NLO materials of thiourea were found to have higher mechanical strentgh, chemical stability, large nonlinearity, high resistance to laser induced damage, low angular sensitivity and good mechanical hardness [Xing, et al. 1987 and Velsko, et al. 1990]. Herein we present the crystal structure of the title compound (I).

The assymetric unit of the title salt compound contains two molecules of thiourea (A and B), three cations of (diaminomethylidene)sulfonium (C, D and E) and three chloride anions.

The dihedral angles between the five molecules of the asymmetric unit are: A/B = 11,96 (9)°, A/C = 75,67 (9)°, A/D = 84,56 (9)°, A/E = 85,02 (9)°, B/C = 71.4 (3)°, B/D = 88,34 (9)° and B/E = 73,21 (9)° (Fig. 1).

In the crystal, the components are linked by a combination of thirteen N—H···Cl, five N—H···S, one S—H···Cl and two S—H···S hydrogen bonds into a three-dimensional structure. (Fig. 2 and Table. 1).

Related literature top

For applications of thiourea salts, see: Xing et al. (1987); Velsko et al. (1990).

Experimental top

The title compound was synthetized at ambient temperature by a mixture of 5 mmol s of thiourea and 5 mmol of HCl in ethanolic solution. The solution was slowly evaporated until solvent completely dried and white crystalline salt was obtained.

Suitable transparent crystals for X-ray mesearment were grown from the final product in aqueous solution by slow evaporation method.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular view of the title compound showing the atom-labeling scheme. Displace- ment ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Projection of the title compound along the c axis, H-bonds are represented by dashed lines.

(Diaminomethylidene)sulfonium chloride–thiourea (3/2) top

Crystal data top

3CH₅N₂S⁺·3Cl⁻·2CH₄N₂S	F(000) = 1016
M_r = 489.98	D_x = 1.456 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 257 reflections
a = 16.3469 (6) Å	θ = 1.9–26.7°
b = 8.9579 (3) Å	µ = 0.89 mm⁻¹
c = 16.1505 (5) Å	T = 100 K
β = 109.105 (2)°	Prism, colourless
V = 2234.72 (13) Å³	0.45 × 0.32 × 0.29 mm
Z = 4

Data collection top

Bruker APEXII CCD detector diffractometer	4190 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 27.0°, θ_min = 1.3°
ω and ϕ scans	h = −19→20
25994 measured reflections	k = −11→11
4885 independent reflections	l = −20→20

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.030P)² + 0.6051P] where P = (F_o² + 2F_c²)/3
4885 reflections	(Δ/σ)_max = 0.001
300 parameters	Δρ_max = 0.45 e Å⁻³
15 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

3CH₅N₂S⁺·3Cl⁻·2CH₄N₂S	V = 2234.72 (13) Å³
M_r = 489.98	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.3469 (6) Å	µ = 0.89 mm⁻¹
b = 8.9579 (3) Å	T = 100 K
c = 16.1505 (5) Å	0.45 × 0.32 × 0.29 mm
β = 109.105 (2)°

Data collection top

Bruker APEXII CCD detector diffractometer	4190 reflections with I > 2σ(I)
25994 measured reflections	R_int = 0.036
4885 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	15 restraints
wR(F²) = 0.068	All H-atom parameters refined
S = 1.06	Δρ_max = 0.45 e Å⁻³
4885 reflections	Δρ_min = −0.39 e Å⁻³
300 parameters

Special details top

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 > σ(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.

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

	x	y	z	U_iso*/U_eq
C1	0.38413 (9)	0.58264 (16)	0.27012 (9)	0.0213 (3)
C2	0.25156 (10)	0.52767 (18)	0.50586 (9)	0.0248 (3)
C3	0.11263 (10)	0.86257 (17)	0.22690 (10)	0.0243 (3)
C4	0.07611 (10)	0.32825 (17)	0.03972 (10)	0.0256 (3)
C5	0.56391 (11)	0.66084 (17)	0.01498 (10)	0.0274 (3)
Cl1	0.36083 (2)	0.16969 (4)	0.21733 (2)	0.02368 (9)
Cl2	0.14816 (2)	0.26513 (4)	0.30590 (2)	0.02530 (9)
Cl3	0.25954 (3)	0.95922 (5)	0.52321 (3)	0.03198 (10)
H10N	0.1886 (13)	1.0337 (17)	0.2623 (13)	0.049 (6)*
H11N	−0.0063 (10)	0.887 (2)	0.2194 (12)	0.039 (5)*
H12N	0.0483 (13)	1.0283 (18)	0.2478 (13)	0.047 (6)*
H13N	0.1429 (12)	0.326 (2)	0.1616 (10)	0.038 (5)*
H14N	0.1828 (11)	0.408 (2)	0.1057 (12)	0.039 (5)*
H15N	0.0337 (12)	0.357 (2)	−0.0832 (11)	0.045 (6)*
H16N	0.1202 (11)	0.429 (2)	−0.0372 (12)	0.039 (5)*
H17N	0.6669 (11)	0.561 (2)	0.0740 (13)	0.044 (6)*
H18N	0.6263 (13)	0.628 (2)	0.1350 (11)	0.045 (6)*
H19N	0.6042 (11)	0.582 (2)	−0.0693 (12)	0.042 (6)*
H1N	0.2689 (14)	0.552 (2)	0.2609 (13)	0.048 (6)*
H20N	0.5209 (13)	0.667 (2)	−0.1093 (12)	0.035 (5)*
H2N	0.3116 (12)	0.413 (2)	0.2562 (12)	0.034 (5)*
H2S	0.1772 (14)	0.501 (2)	0.3670 (14)	0.063 (7)*
H3N	0.4498 (11)	0.418 (2)	0.2606 (11)	0.028 (5)*
H4N	0.5001 (12)	0.556 (2)	0.2727 (12)	0.033 (5)*
H4S	−0.0549 (15)	0.234 (2)	−0.0260 (15)	0.065 (7)*
H5N	0.2310 (11)	0.331 (2)	0.4620 (10)	0.033 (5)*
H5S	0.4337 (15)	0.768 (2)	−0.0474 (15)	0.068 (7)*
H6N	0.2823 (13)	0.341 (2)	0.5582 (11)	0.052 (6)*
H7N	0.2821 (12)	0.7027 (17)	0.5739 (12)	0.036 (5)*
H8N	0.3128 (12)	0.567 (2)	0.6237 (10)	0.042 (6)*
H9N	0.2319 (10)	0.890 (2)	0.2464 (12)	0.038 (5)*
N1	0.31308 (10)	0.50667 (17)	0.26422 (10)	0.0286 (3)
N10	0.62646 (10)	0.61272 (18)	0.08312 (9)	0.0349 (3)
N2	0.45314 (10)	0.50807 (17)	0.26805 (10)	0.0295 (3)
N3	0.25464 (10)	0.38179 (17)	0.50862 (10)	0.0341 (3)
N4	0.28862 (11)	0.60913 (18)	0.57553 (10)	0.0362 (4)
N5	0.18693 (10)	0.93523 (17)	0.24771 (11)	0.0355 (3)
N6	0.04351 (10)	0.93486 (16)	0.23118 (10)	0.0320 (3)
N7	0.14216 (10)	0.35255 (17)	0.11049 (9)	0.0307 (3)
N8	0.07441 (10)	0.37960 (17)	−0.03649 (9)	0.0307 (3)
N9	0.56308 (10)	0.63381 (18)	−0.06456 (9)	0.0317 (3)
S1	0.38657 (3)	0.77282 (4)	0.28160 (3)	0.02625 (10)
S2	0.19881 (3)	0.62081 (5)	0.40844 (3)	0.03084 (11)
S3	0.10697 (3)	0.67952 (4)	0.19506 (3)	0.02933 (10)
S4	−0.00958 (3)	0.22533 (6)	0.05196 (4)	0.04788 (14)
S5	0.48080 (3)	0.76310 (6)	0.03389 (3)	0.04573 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0220 (8)	0.0232 (7)	0.0164 (7)	0.0000 (6)	0.0031 (6)	−0.0008 (5)
C2	0.0248 (8)	0.0286 (8)	0.0211 (8)	0.0015 (6)	0.0077 (6)	0.0016 (6)
C3	0.0261 (8)	0.0229 (7)	0.0215 (7)	0.0010 (6)	0.0045 (6)	0.0007 (6)
C4	0.0254 (8)	0.0247 (8)	0.0275 (8)	−0.0002 (6)	0.0099 (7)	−0.0041 (6)
C5	0.0271 (9)	0.0276 (8)	0.0276 (8)	−0.0040 (7)	0.0093 (7)	−0.0006 (6)
Cl1	0.0267 (2)	0.02205 (18)	0.02225 (18)	−0.00058 (14)	0.00803 (15)	−0.00263 (13)
Cl2	0.0296 (2)	0.02340 (18)	0.02352 (19)	−0.00071 (15)	0.00952 (16)	−0.00253 (14)
Cl3	0.0266 (2)	0.0341 (2)	0.0364 (2)	0.00110 (16)	0.01196 (17)	−0.00136 (17)
N1	0.0235 (8)	0.0219 (7)	0.0418 (8)	−0.0027 (6)	0.0126 (6)	−0.0068 (6)
N10	0.0344 (9)	0.0496 (9)	0.0197 (7)	0.0044 (7)	0.0076 (6)	0.0011 (6)
N2	0.0250 (8)	0.0211 (7)	0.0433 (9)	−0.0008 (6)	0.0122 (6)	−0.0021 (6)
N3	0.0438 (10)	0.0277 (8)	0.0246 (8)	0.0012 (7)	0.0027 (7)	0.0029 (6)
N4	0.0482 (10)	0.0320 (8)	0.0220 (7)	−0.0004 (7)	0.0027 (7)	−0.0004 (6)
N5	0.0243 (8)	0.0257 (7)	0.0560 (10)	−0.0006 (6)	0.0124 (7)	−0.0089 (7)
N6	0.0255 (8)	0.0237 (7)	0.0463 (9)	0.0012 (6)	0.0113 (7)	−0.0020 (6)
N7	0.0317 (8)	0.0394 (8)	0.0207 (7)	−0.0071 (7)	0.0082 (6)	−0.0012 (6)
N8	0.0270 (8)	0.0418 (8)	0.0218 (7)	−0.0056 (7)	0.0060 (6)	−0.0018 (6)
N9	0.0287 (8)	0.0426 (9)	0.0212 (7)	0.0079 (7)	0.0047 (6)	0.0034 (6)
S1	0.0223 (2)	0.01955 (19)	0.0319 (2)	−0.00003 (15)	0.00212 (16)	−0.00217 (15)
S2	0.0373 (2)	0.0297 (2)	0.0220 (2)	0.00586 (17)	0.00489 (17)	0.00139 (16)
S3	0.0255 (2)	0.02236 (19)	0.0326 (2)	0.00159 (15)	−0.00071 (17)	−0.00544 (16)
S4	0.0410 (3)	0.0524 (3)	0.0473 (3)	−0.0191 (2)	0.0104 (2)	0.0089 (2)
S5	0.0439 (3)	0.0502 (3)	0.0446 (3)	0.0125 (2)	0.0165 (2)	−0.0067 (2)

Geometric parameters (Å, º) top

C1—N1	1.322 (2)	N4—H8N	0.841 (15)
C1—N2	1.321 (2)	N5—H10N	0.911 (15)
C2—N4	1.311 (2)	N5—H9N	0.847 (14)
C2—N3	1.308 (2)	N6—H11N	0.884 (14)
C3—N6	1.324 (2)	N6—H12N	0.875 (15)
C3—N5	1.321 (2)	N7—H14N	0.851 (14)
C4—N7	1.308 (2)	N7—H13N	0.855 (14)
C4—N8	1.306 (2)	N8—H16N	0.873 (14)
C5—N10	1.306 (2)	N8—H15N	0.851 (15)
C5—N9	1.303 (2)	N9—H19N	0.840 (15)
N1—H1N	0.81 (2)	N9—H20N	0.87 (2)
N1—H2N	0.84 (2)	S1—C1	1.7127 (15)
N10—H18N	0.850 (15)	S2—H2S	1.25 (2)
N10—H17N	0.857 (15)	S2—C2	1.7398 (15)
N2—H4N	0.861 (19)	S3—C3	1.7120 (16)
N2—H3N	0.811 (19)	S4—H4S	1.24 (2)
N3—H6N	0.862 (15)	S4—C4	1.7414 (16)
N3—H5N	0.855 (14)	S5—H5S	1.29 (2)
N4—H7N	0.844 (15)	S5—C5	1.7464 (17)

C2—S2—H2S	92.4 (10)	C1—N2—H3N	119.1 (13)
C5—S5—H5S	94.6 (10)	C1—N2—H4N	119.4 (12)
C4—S4—H4S	94.9 (10)	H3N—N2—H4N	121.4 (18)
N2—C1—N1	118.37 (15)	C3—N5—H9N	119.5 (13)
N2—C1—S1	121.06 (12)	C3—N5—H10N	119.3 (13)
N1—C1—S1	120.56 (12)	H9N—N5—H10N	121.2 (18)
N8—C4—N7	121.45 (15)	C4—N7—H13N	123.0 (13)
N8—C4—S4	121.58 (13)	C4—N7—H14N	117.6 (13)
N7—C4—S4	116.97 (12)	H13N—N7—H14N	118.9 (18)
N9—C5—N10	121.48 (16)	C1—N1—H2N	120.1 (12)
N9—C5—S5	120.81 (13)	C1—N1—H1N	119.4 (15)
N10—C5—S5	117.71 (13)	H2N—N1—H1N	119.9 (19)
N5—C3—N6	118.38 (15)	C5—N9—H20N	120.2 (12)
N5—C3—S3	120.21 (12)	C5—N9—H19N	116.2 (13)
N6—C3—S3	121.41 (13)	H20N—N9—H19N	123.6 (18)
N3—C2—N4	121.66 (15)	C3—N6—H12N	119.5 (14)
N3—C2—S2	120.80 (12)	C3—N6—H11N	119.5 (12)
N4—C2—S2	117.53 (13)	H12N—N6—H11N	120.9 (18)
C2—N3—H5N	119.8 (13)	C5—N10—H17N	117.8 (13)
C2—N3—H6N	117.5 (14)	C5—N10—H18N	121.4 (14)
H5N—N3—H6N	123 (2)	H17N—N10—H18N	120.7 (19)
C2—N4—H8N	119.2 (14)	C4—N8—H15N	121.5 (14)
C2—N4—H7N	120.5 (13)	C4—N8—H16N	115.9 (13)
H8N—N4—H7N	119.7 (19)	H15N—N8—H16N	122.2 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S3	0.82 (2)	2.76 (2)	3.5403 (17)	161.9 (18)
N1—H2N···Cl1	0.848 (18)	2.474 (18)	3.2683 (16)	156.2 (18)
N10—H17N···Cl3ⁱ	0.86 (2)	2.45 (2)	3.2261 (17)	152 (2)
N10—H18N···Cl1ⁱⁱ	0.85 (2)	2.35 (2)	3.2019 (14)	175 (2)
N2—H3N···Cl1	0.815 (18)	2.624 (18)	3.3656 (16)	152.0 (17)
N2—H4N···Cl1ⁱⁱ	0.86 (2)	2.45 (2)	3.3060 (17)	174.5 (17)
N3—H5N···Cl2	0.86 (2)	2.51 (2)	3.3333 (16)	161 (2)
N3—H6N···Cl1ⁱⁱⁱ	0.86 (2)	2.47 (2)	3.2799 (16)	157 (2)
N4—H7N···Cl3	0.84 (2)	2.43 (2)	3.2422 (17)	163 (2)
N4—H8N···Cl1ⁱⁱⁱ	0.84 (2)	2.57 (2)	3.3327 (16)	151 (2)
N4—H8N···S1^iv	0.84 (2)	2.83 (2)	3.3571 (16)	123 (2)
N5—H9N···S1	0.85 (2)	2.62 (2)	3.4493 (18)	166 (2)
N5—H10N···Cl2^v	0.91 (2)	2.35 (2)	3.2262 (16)	161 (2)
N6—H11N···Cl2^vi	0.88 (2)	2.47 (2)	3.3555 (17)	176 (1)
N6—H12N···Cl2^v	0.88 (2)	2.65 (2)	3.4328 (15)	149 (2)
N7—H13N···Cl2	0.86 (2)	2.37 (2)	3.2219 (15)	177 (1)
N7—H14N···Cl3^vii	0.85 (2)	2.42 (2)	3.2066 (17)	154 (2)
N8—H15N···S3^viii	0.85 (2)	2.44 (2)	3.2649 (16)	164 (2)
N8—H16N···Cl3^vii	0.87 (2)	2.39 (2)	3.2036 (17)	156 (2)
N9—H19N···Cl3ⁱ	0.84 (2)	2.38 (2)	3.1674 (17)	157 (2)
N9—H20N···S1^vii	0.872 (19)	2.38 (2)	3.2412 (16)	167.7 (19)
S2—H2S···Cl2	1.253 (19)	2.315 (19)	3.5612 (6)	172.9 (14)
S4—H4S···S3^viii	1.24 (2)	2.69 (2)	3.8755 (8)	159.2 (15)
S5—H5S···S1^vii	1.29 (2)	2.64 (2)	3.8691 (7)	159.3 (16)

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

Experimental details

Crystal data
Chemical formula	3CH₅N₂S⁺·3Cl⁻·2CH₄N₂S
M_r	489.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	16.3469 (6), 8.9579 (3), 16.1505 (5)
β (°)	109.105 (2)
V (Å³)	2234.72 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.45 × 0.32 × 0.29

Data collection
Diffractometer	Bruker APEXII CCD detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	25994, 4885, 4190
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.068, 1.06
No. of reflections	4885
No. of parameters	300
No. of restraints	15
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.39

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S3	0.82 (2)	2.76 (2)	3.5403 (17)	161.9 (18)
N1—H2N···Cl1	0.848 (18)	2.474 (18)	3.2683 (16)	156.2 (18)
N10—H17N···Cl3ⁱ	0.859 (19)	2.445 (19)	3.2261 (17)	151.6 (17)
N10—H18N···Cl1ⁱⁱ	0.850 (17)	2.354 (17)	3.2019 (14)	175 (2)
N2—H3N···Cl1	0.815 (18)	2.624 (18)	3.3656 (16)	152.0 (17)
N2—H4N···Cl1ⁱⁱ	0.86 (2)	2.45 (2)	3.3060 (17)	174.5 (17)
N3—H5N···Cl2	0.856 (16)	2.511 (16)	3.3333 (16)	161.4 (16)
N3—H6N···Cl1ⁱⁱⁱ	0.862 (17)	2.470 (17)	3.2799 (16)	156.8 (16)
N4—H7N···Cl3	0.844 (15)	2.427 (16)	3.2422 (17)	162.6 (17)
N4—H8N···Cl1ⁱⁱⁱ	0.838 (16)	2.573 (17)	3.3327 (16)	151.3 (15)
N4—H8N···S1^iv	0.838 (16)	2.829 (16)	3.3571 (16)	122.7 (15)
N5—H9N···S1	0.846 (18)	2.622 (18)	3.4493 (18)	166.1 (16)
N5—H10N···Cl2^v	0.911 (16)	2.353 (17)	3.2262 (16)	160.6 (19)
N6—H11N···Cl2^vi	0.884 (18)	2.473 (18)	3.3555 (17)	175.9 (14)
N6—H12N···Cl2^v	0.875 (17)	2.654 (18)	3.4328 (15)	148.9 (19)
N7—H13N···Cl2	0.855 (16)	2.368 (16)	3.2219 (15)	176.9 (14)
N7—H14N···Cl3^vii	0.853 (19)	2.420 (19)	3.2066 (17)	153.6 (16)
N8—H15N···S3^viii	0.851 (18)	2.437 (19)	3.2649 (16)	164.4 (17)
N8—H16N···Cl3^vii	0.873 (19)	2.385 (19)	3.2036 (17)	156.3 (16)
N9—H19N···Cl3ⁱ	0.841 (19)	2.375 (19)	3.1674 (17)	157.4 (17)
N9—H20N···S1^vii	0.872 (19)	2.38 (2)	3.2412 (16)	167.7 (19)
S2—H2S···Cl2	1.253 (19)	2.315 (19)	3.5612 (6)	172.9 (14)
S4—H4S···S3^viii	1.24 (2)	2.69 (2)	3.8755 (8)	159.2 (15)
S5—H5S···S1^vii	1.29 (2)	2.64 (2)	3.8691 (7)	159.3 (16)

Acknowledgements

The author thanks the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

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