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

Hafid Zouihri

doi:10.1107/S1600536811052809

. 2012 Jan 7;68(Pt 2):o257. doi: 10.1107/S1600536811052809

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

Hafid Zouihri ^a,^*

PMCID: PMC3274950 PMID: 22346903

Abstract

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,
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[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 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

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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052809/bt5746sup1.cif

e-68-0o257-sup1.cif^{(23.4KB, cif)}

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

e-68-0o257-Isup2.hkl^{(239.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811052809/bt5746Isup3.cml

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—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)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.