(2E)-2-[2-(Cyclo­hexyl­carbamothio­yl)hydrazinylidene]­propanoic acid

Md Abu Affan; Md Abdus Salam; Fasihuddin B Ahmad; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811014449

. 2011 Apr 22;67(Pt 5):o1193. doi: 10.1107/S1600536811014449

(2E)-2-[2-(Cyclohexylcarbamothioyl)hydrazinylidene]propanoic acid

Md Abu Affan ^a,^‡, Md Abdus Salam ^a, Fasihuddin B Ahmad ^a, Seik Weng Ng ^b, Edward R T Tiekink ^b,^*

PMCID: PMC3089072 PMID: 21754495

Abstract

In the title thiourea derivative, C₁₀H₁₇N₃O₂S, the carboxyl group and the least-squares plane through the cyclohexyl ring are twisted out of the plane through the central CN₃S residue; the respective dihedral angles are 7.18 (8) and 62.29 (4)°. The conformation about the azomethine bond [1.275 (2) Å] is E. The NH groups are anti, with one forming an intramolecular N—H⋯N hydrogen bond. The main feature of the crystal structure is the formation of linear supramolecular chains along [110] mediated by alternating pairs of O—H⋯O and pairs of N—H⋯S hydrogen bonds.

Related literature

For related thiourea structures, see: Normaya et al. (2011 ▶); Salam et al. (2011 ▶).

Experimental

Crystal data

C₁₀H₁₇N₃O₂S
M _r = 243.33
Monoclinic,
a = 8.9204 (2) Å
b = 6.0350 (2) Å
c = 22.4750 (6) Å
β = 90.051 (3)°
V = 1209.93 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.687, T _max = 1.000
7394 measured reflections
2723 independent reflections
2251 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.143
S = 0.98
2723 reflections
158 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014449/hb5851sup1.cif

e-67-o1193-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014449/hb5851Isup2.hkl

e-67-o1193-Isup2.hkl^{(133.7KB, 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—H3⋯N1	0.87 (1)	2.20 (2)	2.574 (2)	106 (2)
O1—H1⋯O2ⁱ	0.85 (1)	1.80 (1)	2.6416 (17)	172 (3)
N2—H2⋯S1ⁱⁱ	0.89 (1)	2.65 (1)	3.5384 (15)	176 (2)

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

Acknowledgments

This work was supported financially by the Ministry of Science, Technology and Innovation (MOSTI) under a research grant (No. 06-01-09-SF0046). The authors thank Universiti Malaysia Sarawak (UNIMAS) for the facilities to carry out the research work. The authors also thank the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

In continuation of structural investigations into conformation and hydrogen bonding in thiourea derivatives (Normaya et al. 2011; Salam et al., 2011), the title compound, (I), was investigated.

The central CN₃S chromophore in (I), Fig. 1, is planar (r.m.s. = 0.0039 Å). The carboxylate residue is slightly twisted out this plane (dihedral angle = 7.18 (8) °), and, by contrast, the least-squares plane through the cyclohexyl group (which has the conformation of a chair) is twisted significantly out of the central plane (dihedral angle = 62.29 (4) °). The H atoms of the NH groups are anti, and the conformation about the azomethine bond [1.275 (2) Å] is E. The N3—H forms an intramolecular hydrogen bond with the imino-N3 atom, Table 1. Finally, the thione and carboxylic acid groups lie to opposite sides of the molecule. This arrangements enables the formation of linear supramolecular chains via hydrogen bonds along [110] in the crystal packing, Fig. 2 and Table 1. The carboxylic acid residues self-associate via a centrosymmetric eight-membered {···HOC═O}₂ synthon. Similarly, the thiourea entity with the NH atom not involved in the intramolecular N—H···N interaction, self-associates via a centrosymmetric eight-membered {···HNC═ S}₂ synthon. Chains lie in the ab plane with the cyclohexyl rings inter-digitating along the c axis, Fig. 3.

Experimental

Cyclohexylisothiocyanate (0.706 g, 5 mmol) and hydrazine hydrate (0.250 g, 5 mmol), each dissolved in 10 ml e thanol were mixed with constant stirring. The stirring was continued for 30 min and the white product that formed, N(4)-cyclohexylthiosemicarbazide, was washed with ethanol and dried in vacuo. A solution of this (0.51 g, 3 mmol) in 10 ml me thanol was refluxed with a methanolic solution of pyruvic acid (0.261 g, 3 mmol) for 5 h after the addition of 1–2 drops of glacial acetic acid. On cooling the solution to room temperature, white precipitate separated, which were filtered and washed with methanol. The white precipitate was recrystallized from methanol to yield colourless prisms and dried in vacuo over silica gel. (M.pt. 465–467 K. Yield 0.621 g (80%). Anal. Found: C, 49.31; H, 7.01; N, 17.18%. C₁₀H₁₇N₃O₂S requires: C, 49.36; H, 7.04; N, 17.26%. FT—IR (KBr, cm^-1) ν_max: 3322 (m, OH), 3197 (s, NH), 2922, 2851 (s, cyclohexyl), 1692 (m, C═O), 1619 (w, C═N), 980 (m, N—N), 1249, 873 (w, C═S).