S-Benzyl­thiouronium 4-anilinobenzene­sulfonate

Hoong-Kun Fun; Suchada Chantrapromma; E Deepak D’Silva; P S Patil; S M Dharmaprakash

doi:10.1107/S160053680802727X

. 2008 Aug 30;64(Pt 9):o1858–o1859. doi: 10.1107/S160053680802727X

S-Benzylthiouronium 4-anilinobenzenesulfonate

Hoong-Kun Fun ^a,^*, Suchada Chantrapromma ^b,^‡, E Deepak D’Silva ^c, P S Patil ^d,^§, S M Dharmaprakash ^c

PMCID: PMC2960486 PMID: 21201828

Abstract

In the title compound, C₈H₁₁N₂S⁺·C₁₂H₁₀NO₃S⁻, the NH group of the S-benzylthiuronium is protonated and the interplanar angle between the phenyl ring and the CH₂—S=C(NH₂)₂ unit is 47.44 (10)°. In the 4-anilinobenzenesulfonate anion, the interplanar angle between the two rings is 44.07 (8)°. In the crystal structure, anions are linked into chains along the c-axis direction by N—H⋯O hydrogen bonds, while additional N—H⋯O interactions link the cations to the anions in chains along the b-axis direction. These chains are further interconnected into a two-dimensional network parallel to the bc plane by C—H⋯O interactions. C—H⋯π contacts are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to the applications of S-benzylthiuronium chloride and sodium diphenylamine-4-sulfonate, see, for example: Liao et al. (2004 ▶); Liu et al. (2006a ▶,b ▶); Mostafa (2006 ▶).

Experimental

Crystal data

C₁₂H₁₀NO₃S⁺·C₈H₁₁N₂S⁻
M _r = 415.54
Monoclinic,
a = 14.4918 (4) Å
b = 9.2024 (2) Å
c = 16.3944 (4) Å
β = 113.529 (1)°
V = 2004.57 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100.0 (1) K
0.24 × 0.07 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.879, T _max = 0.992
45812 measured reflections
5838 independent reflections
4320 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.107
S = 1.07
5838 reflections
337 parameters
All H-atom parameters refined
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.43 e Å⁻³

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/S160053680802727X/sj2532sup1.cif

e-64-o1858-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802727X/sj2532Isup2.hkl

e-64-o1858-Isup2.hkl^{(285.8KB, 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
N1—H1N1⋯O1ⁱ	0.85 (2)	1.99 (2)	2.836 (2)	173.0 (18)
N2—H1N2⋯O3ⁱⁱ	0.92 (3)	2.04 (3)	2.9561 (19)	172 (3)
N3—H1N3⋯O1	0.809 (19)	2.015 (19)	2.8204 (19)	174 (2)
N2—H2N2⋯O3ⁱⁱⁱ	0.839 (19)	2.015 (19)	2.8069 (19)	157.2 (19)
N3—H2N3⋯O2ⁱⁱ	0.91 (2)	1.96 (2)	2.8633 (17)	173 (2)
C9—H9⋯O1	0.97 (2)	2.463 (18)	2.8563 (18)	103.8 (13)
C19—H19B⋯O2^iv	0.97 (2)	2.57 (2)	3.332 (2)	134.8 (14)
C4—H4⋯Cg2^v	0.947 (19)	3.22 (2)	3.943 (2)	134.7 (14)
C17—H17⋯Cg1ⁱⁱⁱ	0.99 (2)	2.92 (2)	3.471 (2)	116.0 (15)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg1 and Cg2 are the centroids of C7–C12 and C13–C18 benzene rings, respectively.

Acknowledgments

This work is supported by the Department of Science and Technology (DST), Government of India, under grant No. SR/S2/LOP-17/2006. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

S-benzylthiouronium chloride is a useful compound in pharmaceutical and biomedical science (Mostafa, 2006) and also in electrochemistry (Liao et al., 2004) whereas sodium diphenylamine-4-sulfonate is extensively used in nanomaterial studies (Liu et al., (2006a, b). Both compounds have the potential to form hydrogen bonds. As part of our investigations into solid state hydrogen bonding, the title compound (I) was synthesized and herein we report its crystal structure.

The molecular structure of the title compound consists of a C₈H₁₁N₂S⁺ cation and a C₁₂H₁₀NO₃S^- anion (Fig. 1). An NH group of the S-benzylthiouronium unit was protonated to become a NH₂ moiety. Neither the cation and the anion are planar as can be seen from the interplanar angle between the C13–C18 benzene ring and the least-squares plane through the S2/C20/N2/N3 unit being 47.44 (10)°. In the diphenylamine-4-sulfonate anion, the interplanar angle between the the two benzene rings (C1–C6 and C7–C12) is 44.07 (8)°. The C13–C18 benzene ring makes dihedral angles of 71.72 (9)° and 29.45 (9)° with the C1–C6 and C7–C12 benzene rings, respectively. The cation is linked to the anion by an N—H···O hydrogen bond (Fig. 1). The conformation of the dimethylamino group with respect to the S-benzyl substituent is reflected in the torsion angles C20–S2–C19–C18 = -177.78 (11)° and C19–S2–C20–N2 = 14.60 (17)°. Bond lengths and angles in (I) are in normal ranges (Allen et al., 1987).

In the crystal packing (Fig. 2 and Table 1), the anions are linked into chains along the c direction by N1—H1N1···O1 hydrogen bonds whereas the cations are linked with the anions into chains along the b direction by N2—H1N2···O3, N2—H2N2···O3 and N3—H2N3···O2 hydrogen bonds. These chains are further inter-connected into a two dimensional network parallel to the bc plane by C19—H19B···O2 interactions. C—H···π interactions were also observed in the crystal (Table 1); Cg₁ and Cg₂ are the centroids of C7–C12 and C13–C18 benzene rings, respectively.

Experimental

The title compound was synthesized by mixing solutions of the sodium salt of diphenylamine sulfonate (0.54 g) in distilled water (5 ml) with 5 drops of 1 M HCl and S-benzylthiouronium chloride (1.0 g) in distilled water (5 ml). The mixed solution immediately yields a precipitate in ice cold water. This was filtered and dried. Colorless block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from methanol by slow evaporation of the solvent at room temperature.