3-(2-Hy­droxy­phen­yl)-1-{(E)-[1-(pyrazin-2-yl)ethyl­idene]amino}­thio­urea monohydrate

Erna Normaya; Yang Farina; Siti Nadiah Abd Halim; Edward R T Tiekink

doi:10.1107/S1600536811010038

. 2011 Mar 23;67(Pt 4):o943–o944. doi: 10.1107/S1600536811010038

3-(2-Hydroxyphenyl)-1-{(E)-[1-(pyrazin-2-yl)ethylidene]amino}thiourea monohydrate

Erna Normaya ^a, Yang Farina ^b,^‡, Siti Nadiah Abd Halim ^c, Edward R T Tiekink ^c,^*

PMCID: PMC3099853 PMID: 21754211

Abstract

In the title compound, C₁₃H₁₃N₅OS·H₂O, the thiourea molecules closely resemble each other and are approximately planar; the dihedral angles formed between the terminal benzene rings are 7.88 (8) and 7.20 (8)°, respectively. The observed planarity correlates with the presence of bifurcated N—H⋯(O,N) hydrogen bonds. In the crystal, the molecules are connected into supramolecular double chains via a combination of N—H⋯S (linking the two independent molecules), O—H⋯O and O—H⋯N (linking dimeric aggregates into a supramolecular chain via hydroxy–water, water–water and water–pyrazine interactions) and O—H⋯S hydrogen bonds (connecting two chains). The chains are further connected by C—H⋯N and C—H⋯S interactions.

Related literature

For biological activity of thiourea derivatives, see: Venkatachalam et al. (2004 ▶). For related structures, see: Gunasekaran et al. (2010 ▶); Dzulkifli et al. (2011 ▶). For additional geometric analysis, see: Spek (2009 ▶).

Experimental

Crystal data

C₁₃H₁₃N₅OS·H₂O
M _r = 305.36
Triclinic,
a = 7.9808 (5) Å
b = 11.7557 (8) Å
c = 16.4160 (11) Å
α = 99.638 (1)°
β = 94.128 (1)°
γ = 109.200 (1)°
V = 1420.54 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.18 × 0.14 × 0.11 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.656, T _max = 0.746
18244 measured reflections
6505 independent reflections
5267 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.110
S = 1.04
6505 reflections
411 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶), DIAMOND (Brandenburg, 2006 ▶) and Qmol (Gans & Shalloway, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010038/hg5012sup1.cif

e-67-0o943-sup1.cif^{(26KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010038/hg5012Isup2.hkl

e-67-0o943-Isup2.hkl^{(311.9KB, 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—H1n⋯O1	0.88 (1)	2.11 (2)	2.5720 (15)	112 (1)
N1—H1n⋯N3	0.88 (1)	2.04 (2)	2.5435 (18)	116 (1)
N6—H6n⋯O2	0.87 (1)	2.11 (2)	2.5676 (15)	112 (1)
N6—H6n⋯N8	0.87 (1)	2.02 (2)	2.5358 (17)	117 (1)
O1—H1o⋯O1w	0.83 (1)	1.86 (1)	2.6820 (15)	170 (2)
O2—H2o⋯O2wⁱ	0.83 (1)	1.83 (1)	2.6481 (16)	169 (2)
O1w—H1w⋯N9ⁱⁱ	0.84 (1)	1.96 (1)	2.7958 (17)	169 (2)
O1w—H2w⋯S2ⁱⁱⁱ	0.83 (2)	2.82 (2)	3.4648 (13)	136 (2)
O2w—H3w⋯N4	0.84 (1)	2.02 (1)	2.8547 (17)	171 (2)
O2w—H4w⋯O1w	0.85 (2)	2.00 (2)	2.8357 (18)	169 (2)
N2—H2n⋯S2^iv	0.87 (1)	2.67 (1)	3.4802 (12)	156 (1)
N7—H7n⋯S1^v	0.87 (1)	2.58 (1)	3.4508 (12)	176 (2)
C16—H16⋯N5^vi	0.95	2.58	3.517 (2)	172
C22—H22a⋯S1^v	0.98	2.79	3.4454 (16)	125

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

Acknowledgments

We thank to University Kebangsaan Malaysia, the International Islamic University Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grant GUP-NBT-08–27-112. The authors also thank the University of Malaya for support of the crystallographic facility and acknowledge an UMRG grant (RG125/10AFR).

supplementary crystallographic information

Comment

Thiourea derivatives have biological potential (Venkatachalam et al., 2004) and attract continuing structural studies (Gunasekaran et al., 2010; Dzulkifli et al., 2011).

The title compound (I), Fig. 1, features two independent thiourea derivatives and two water molecules of crystallization in the asymmetric unit. As seen from the overlay diagram, Fig. 2, there are small differences between the independent thiourea molecules. These relate to the relative orientations of the terminal benzene rings; the r.m.s. deviation of bond distances = 0.0032 Å (Spek, 2009). The similarity between the molecules is seen in the dihedral angle formed between the rings = 7.88 (8) ° for the S1-containing molecule and 7.20 (8) ° for the other. The planarity of each molecule is readily explained in terms of bifurcated intramolecular N—H···O,N hydrogen bonds, Table 1.

The most prominent feature of the crystal packing is the formation of supramolecular double chains along [111]. The two molecules comprising the asymmetric unit are connected via an eight-membered {···HNC═S}₂ synthon and the resulting dimeric aggregates are connected by two molecules of water via a sequence of O—H···O hydrogen bonds. Thus, the hydroxyl group of one molecule is connected to a water molecule which hydrogen bonds to the second water molecule which in turn links the second hydroxyl group. Hydrogen bonds between the water molecules and pyrazine-N atoms close two fused 16-membered {···HOH···NC₃N₂CNC₂OH···O} synthons. This arrangement is stabilized by the intramolecular interactions outlined above. The result is a supramolecular chain, Fig. 3. Pairs of chains are linked via water-O—H···S hydrogen bonds leading to a double chain, Fig. 4. The chains are consolidated in the crystal packing by C—H···N and C—H···S interactions, Table 1 and Fig. 5.

Experimental

The reaction of 2-acetylpyrazine with methyl hydrazinecarbodithioate (II) formed (E)-methyl-2-(1-(pyrazin-2-yl)ethylidene)hydrazinecarbodithioate (III). The condensation reaction of (III) with 2-phenolamine produced the title compound, (I), i.e. (E)-N-(2-hydroxyphenyl)-2-(1-(pyrazin-2- yl)ethylidene)hydrazinecarbothioamide (yield:73.3%, M.pt. 469—471 K).

Slow recrystallization of its butanol solution afforded yellow crystals of (I). Elemental anal. (calc.): C, 51.80 (51.13); H, 4.91 (4.95), N, 24.10 (22.94) %. FT—IR (ν_max; cm^-1): (O—H) 3459, (N—H) 3209, (C\b C) 3016, (CH₃) 2925, (C═N) 1609, (C≐C aromatic) 1555, (C—N) 1366, (pyrazyl) 1162, (N —N) 1121 and (C═S) 1023.