1,5-Bis[(E)-1-(2-hydroxyphenyl)ethyl­idene]thiocarbonohydrazide mono­hydrate

Md Abu Affan; Dayang N A Chee; Fasihuddin B Ahmad; Edward R T Tiekink

doi:10.1107/S1600536810004241

. 2010 Feb 6;66(Pt 3):o555. doi: 10.1107/S1600536810004241

1,5-Bis[(E)-1-(2-hydroxyphenyl)ethylidene]thiocarbonohydrazide monohydrate

Md Abu Affan ^a,^‡, Dayang N A Chee ^a, Fasihuddin B Ahmad ^a, Edward R T Tiekink ^b,^*

PMCID: PMC2983601 PMID: 21580324

Abstract

In the title compound, C₁₇H₁₈N₄O₂S·H₂O, the thiourea derivative is almost planar, with an r.m.s. deviation for the non-H atoms of 0.057 Å. The hydroxyl groups lie to the same side of the molecule as the thione S atom, a conformation that allows the formation of intramolecular O—H⋯S and O—H⋯N hydrogen bonds. In the crystal structure, the thiourea and water molecules self-assemble into a two-dimensional array by a combination of O_water—H⋯O_hydroxyl, N—H⋯O_water and O_water—H⋯S hydrogen bonds and C—H⋯π interactions.

Related literature

For background and recent studies of the biological activity of organotin compounds, see: Gielen & Tiekink (2005 ▶); Affan et al. (2009 ▶). For the structure of the ketone analogue of the title compound, see: Zukerman-Schpector et al. (2009 ▶).

Experimental

Crystal data

C₁₇H₁₈N₄O₂S·H₂O
M _r = 360.43
Monoclinic,
a = 15.8654 (3) Å
b = 7.3938 (1) Å
c = 16.3697 (3) Å
β = 115.922 (1)°
V = 1727.06 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.44 × 0.13 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.905, T _max = 1
15464 measured reflections
3968 independent reflections
3136 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.102
S = 1.03
3968 reflections
246 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004241/hb5327sup1.cif

e-66-0o555-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004241/hb5327Isup2.hkl

e-66-0o555-Isup2.hkl^{(190.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N2	0.83 (2)	1.79 (2)	2.5191 (17)	147 (2)
O1—H1O⋯S1	0.83 (2)	2.86 (2)	3.5126 (13)	138 (2)
O2—H2O⋯N4	0.82 (2)	1.81 (2)	2.542 (2)	148 (2)
O2—H2O⋯S1	0.82 (2)	2.96 (2)	3.6220 (15)	139 (2)
O3—H3O⋯O1	0.84 (2)	1.91 (2)	2.7525 (18)	174 (2)
O3—H4O⋯S1ⁱ	0.82 (2)	2.76 (2)	3.5089 (14)	154 (2)
N1—H1N⋯O3ⁱⁱ	0.87 (2)	2.04 (2)	2.8169 (19)	150 (2)
N3—H3N⋯O3ⁱⁱ	0.88 (2)	2.04 (2)	2.854 (2)	154 (2)
C11—H11C⋯Cg1ⁱⁱⁱ	0.98	2.61	3.4497 (17)	144

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

Acknowledgments

The authors express their gratitude to the Ministry of Science, Technology and Innovation (MOSTI) for a research grant (No. 06-01-09-SF0046), and to Universiti Malaysia Sarawak (UNIMAS) for financial support.

supplementary crystallographic information

Comment

The molecule in the title hydrate, (I), was synthesised as part of an on-going study into biological studies of organotin compounds (Gielen & Tiekink, 2005; Affan et al., 2009). The thiourea derivative in (I) is effectively planar with the maximum deviation of any of the torsion angles from 0 or 180° being 4.6 (2)° for N4—C10—C12—C13 and -174.62 (15)° for C11—C10—C12—C13. The r.m.s. deviation for all non-hydrogen atoms in the thiourea molecule = 0.057 Å. The conformation about each of the C1═N2 [1.290 (2) Å] and C10═N4 [1.2956 (19) Å] double bonds is E. Finally, the hydroxyl groups are orientated to the same side of the molecule as the thione-S atom. The described molecular conformation is stabilised by intramolecular O_hydroxyl—H···N_imine and O_hydroxyl—H···S_thione hydrogen bonds, Table 1. Allowing for substitution of the thione by a ketone group, the described molecular conformation for the thiourea molecule in (I) resembles that in the recently reported ketone derivative (Zukerman-Schpector et al., 2009).

In addition to the intramolecular hydrogen bonds, the crystal structure features O_water—H···O_hydroxyl, N—H···O_water and O_water—H···S hydrogen bonds, Table 1. The N—H atoms of one molecule connect to a water molecule which in turn forms a hydrogen bond with a hydroxyl-O1 atom of a second thiourea derivative. These interactions give rise to a supramolecular chain with base vector [101]. However, this does not take into account a second donor hydrogen bond involving the water molecule. This forms a hydrogen bond with a thione-S atom of a third thiourea derivative, Fig. 2. The latter interactions link chains into a 2-D array with additional stabilisation afforded by C—H···π, Table 1, and π···π interactions. The latter occur between the benzene rings: ring centroid(C4–C9)···ring centroid(C12–C17)ⁱ distance = 3.7821 (10) Å, with a dihedral angle between the least-squares plane through the rings of 2.25 (7)°; symmetry operation i: 1 - x, -y, 1 - z.

Experimental

A mixture of thiocarbohydrazone (0.53 g, 0.005 mol) and 2-hydroxyacetophenone (1.36 g, 0.01 mol) in absolute ethanol was heated under reflux for 4–5 h in the presence of 1–2 drops of glacial acetic acid. The reaction mixture was allowed to cool to room temperature for 1 h. The light-yellow precipitate was filtered off and washed several times using absolute ethanol, and was purified by recrystallization from hot absolute ethanol and dried under vacuum over P₂O₅. Colourless prisms of (I) were obtained by slow evaporation of acetone solution at room temperature. Yield: 1.66 g, 88.0%. m.p. = 494–496 K. IR (KBr): ν_OH (3561–3391), ν_NH 3230, ν_C_═_N 1619, ν_N—N 963, ν_C_═_S 857 cm^-1.