S-Benzyl­thio­uronium 3-nitro­benzene­sulfonate

Hoong-Kun Fun; Samuel Robinson Jebas; Ibrahim Abdul Razak; E Deepak D’Silva; P S Patil; S M Dharmaprakash

doi:10.1107/S1600536808016115

. 2008 Jun 7;64(Pt 7):o1195–o1196. doi: 10.1107/S1600536808016115

S-Benzylthiouronium 3-nitrobenzenesulfonate

Hoong-Kun Fun ^a,^*, Samuel Robinson Jebas ^a,^‡, Ibrahim Abdul Razak ^a, E Deepak D’Silva ^b, P S Patil ^b, S M Dharmaprakash ^b

PMCID: PMC2961859 PMID: 21202837

Abstract

In the title compound, C₈H₁₁N₂S⁺·C₆H₄NO₅S⁻, the asymmetric unit is composed of two crystallographically independent S-benzylthiouronium cations and two independent nitrobenzenesulfonate anions. An intramolecular hydrogen bond generates an S(5)S(5) ring motif. The crystal packing is stabilized by intramolecular C—H⋯O and intermolecular C—H⋯O, N—H⋯O and N—H⋯S hydrogen bonds which, along with short S⋯O [3.034 (2) Å] and N⋯O [2.796 (3) Å] contacts, form a two-dimensional network parallel to the ab plane.

Related literature

For related literature on nonlinear optical materials, see: Chantrapromma et al. (2005 ▶, 2006 ▶); Fun et al. (2006 ▶); Patil, Dharmaprakash et al. (2007 ▶); Patil, Fun et al. (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₈H₁₁N₂S⁺·C₆H₄NO₅S⁻
M _r = 369.41
Triclinic,
a = 6.0397 (1) Å
b = 7.7856 (1) Å
c = 17.4680 (2) Å
α = 81.366 (1)°
β = 89.322 (1)°
γ = 87.057 (1)°
V = 811.01 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 100.0 (1) K
0.32 × 0.19 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.894, T _max = 0.986
19026 measured reflections
8874 independent reflections
7378 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.112
S = 1.03
8874 reflections
433 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ▶), 4108 Friedel pairs
Flack parameter: −0.03 (5)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016115/su2055sup1.cif

e-64-o1195-sup1.cif^{(27.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016115/su2055Isup2.hkl

e-64-o1195-Isup2.hkl^{(425.3KB, hkl)}

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
N3—H1N3⋯O4ⁱ	0.86	1.97	2.796 (3)	162
N3—H1N3⋯S1ⁱ	0.86	2.84	3.694 (3)	170
N3—H2N3⋯O3ⁱⁱ	0.86	2.05	2.898 (3)	171
N4—H1N4⋯O3ⁱ	0.86	2.26	3.080 (3)	160
N4—H2N4⋯O5ⁱⁱⁱ	0.86	2.37	3.126 (3)	146
N5—H1N5⋯O10ⁱ	0.86	1.91	2.764 (3)	176
N5—H1N5⋯S2ⁱ	0.86	2.85	3.642 (3)	154
N5—H2N5⋯O9ⁱⁱ	0.86	1.94	2.783 (3)	168
N6—H1N6⋯O1ⁱⁱⁱ	0.86	2.27	3.072 (3)	156
N6—H2N6⋯O8ⁱⁱⁱ	0.86	2.07	2.787 (3)	141
C6—H6A⋯O4	0.93	2.56	2.900 (3)	102
C8—H8A⋯O10	0.93	2.57	2.896 (4)	101
C19—H19B⋯O4ⁱⁱⁱ	0.97	2.51	3.331 (4)	142
C27—H27B⋯O8ⁱⁱⁱ	0.97	2.53	3.259 (4)	132

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for Science Fund grant No. 305/PFIZIK/613312. HKF and IAR also thank the Malaysian Government and Universiti Sains Malaysia for FRGS grant No. 203/PFIZIK/671064. SRJ thanks the Universiti Sains Malaysia for a post-doctoral research fellowship. This work was supported by the Department of Science and Technology (DST) and the Government of India (grant No. SR/S2/LOP-17/2006).

supplementary crystallographic information

Comment

In continuation of our research on nonlinear optical (NLO) materials (Chantrapromma et al., 2005, 2006; Fun et al., 2006; Patil, Dharmaprakash et al. (2007); Patil, Fun et al. (2007), the crystal structure determination of the title compound, (I), was undertaken in order to obtain detailed information on its three-dimensional structure and crystal packing. Since the title compound crystallizes in a non-centrosymmetric space group, it should exhibit second-order nonlinear optical properties.

In the asymmetric unit of (I) there are two crystallographically independent s-benzylthiuronium cations and two independent m-nitrobenzene sulfonate anions (Fig. 1). Bond lengths and angles are found to have normal values (Allen et al., 1987). The dihedral angle formed by the mean plane of ring (C13–C18) with the mean planes through rings (C21–C26), (C1–C6) and (C7–C12) are 57.6 (2)°, 49.9 (2)° and 46.98 (1)°, respectively. The dihedral angle formed by the mean planes of rings (C1–C6) and (C7–C12) are 3.07 (1)°, indicating that they are almost coplanar.

An intramolecular hydrogen bond generates a S(5)S(5) ring motif (Bernstein et al., 1995). The crystal packing (Fig. 2) is stabilized by intramolecular C—H···O, intermolecular C—H···O, N—H···O and N—H···S hydrogen bonds which together with short S···O and N···O contacts, in the range 2.796 (3)–3.282 (3) Å [symmetry code: x, 1+y, z; 1+x, 1+y, z], form a two-dimensional network parrallel to the ab plane.

Experimental

Compound (I) was synthesized by mixing solutions of the sodium salt of m-nitrobenzene sulfonic acid (0.5 g) in 5 ml of distilled water with 5 drops of 0.1 N HCl and S-benzylthiuronium chloride (1 g) in 5 ml of distilled water. The mixing immediately yielded a precipitate when the reaction container was placed in ice cold water. The resulting precipitate was filtered and dried. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of an ethanol solution at room temperature.