(E)-3,4-Dihydroxy­benzaldehyde 4-ethyl­thio­semicarbazone

Safa’a Fares Kayed; Yang Farina; Ibrahim Baba; Jim Simpson

doi:10.1107/S1600536808009148

. 2008 Apr 10;64(Pt 5):o824–o825. doi: 10.1107/S1600536808009148

(E)-3,4-Dihydroxybenzaldehyde 4-ethylthiosemicarbazone

Safa’a Fares Kayed ^a, Yang Farina ^a, Ibrahim Baba ^a, Jim Simpson ^b,^*

PMCID: PMC2961087 PMID: 21202314

Abstract

The title compound, C₁₀H₁₃N₃O₂S, was prepared by condensation of 3,4-dihydroxybenzaldehyde with 4-ethyl-3-thiosemicarbazide. The molecule adopts an E configuration with respect to the C=N bond. One of the OH substituents on the dihydroxybenzene ring is disordered over the two possible 3-positions on either side of the ordered 4-hydroxy group. The occupancy of the major disorder component refined to 0.633 (7). The molecule is essentially planar, with an r.m.s. deviation through all non-H atoms of 0.0862 Å. An intramolecular N—H⋯N hydrogen bond forms between the outer amine residue and the imine N atom, generating an S(5) ring motif and contributing to the planarity of the molecule. In the crystal structure, an extensive network of classical O—H⋯O, O—H⋯S and N—H⋯S hydrogen bonds and weak C—H⋯O and S⋯O [3.301 (3) Å] interactions link molecules into sheets running approximately parallel to the ab plane.

Related literature

For related structures, see: Swesi et al. (2006 ▶); Kovala-Demertzi et al. (2004 ▶); Jian & Li (2006 ▶). For reference structural data, see: Allen et al. (1987 ▶). For ring motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₁₃N₃O₂S
M _r = 239.29
Monoclinic,
a = 10.6549 (12) Å
b = 12.9020 (16) Å
c = 8.6375 (11) Å
β = 107.910 (4)°
V = 1129.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 91 (2) K
0.44 × 0.11 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.818, T _max = 0.975
12327 measured reflections
1998 independent reflections
1507 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.168
S = 1.05
1998 reflections
165 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.41 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: APEX2 (Bruker 2006 ▶); cell refinement: APEX2 and SAINT (Bruker 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000; molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶) and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009148/hg2389sup1.cif

e-64-0o824-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009148/hg2389Isup2.hkl

e-64-0o824-Isup2.hkl^{(98.3KB, 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—H3B⋯N1	0.88	2.23	2.626 (4)	107
O5—H5A⋯S1ⁱ	0.84	2.82	3.106 (9)	102
C2—H2⋯O5ⁱⁱ	0.95	2.65	3.335 (8)	129
N2—H2A⋯S1ⁱⁱⁱ	0.88	2.52	3.392 (4)	172
O4—H4⋯O4^iv	0.84	2.16	2.988 (5)	169
C9—H9A⋯O3^v	0.99	2.46	2.985 (5)	113

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

Acknowledgments

We thank the Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grant UKM-ST-01-FRGS0022–2006. We also thank the University of Otago for purchase of the diffractometer.

supplementary crystallographic information

Comment

For example the structure of the related molecule 2,3-dihydroxybenzaldehyde thiosemicarbazone hemihydrate has been reported by Swesi et al. (2006) as have the structures of a phenylthiocarbazole with a single hydroxy-substituent on the benzylidene ring (Jian & Li, 2006) and of a palladium(II) complex of an ethylthiosemicarbonate ligand deprotonated at the phenolate ring (Kovala-Demertzi et al., 2004).

The molecule adopts an E configuration with respect to the C=N bond and bond distances and angles are normal (Allen et al., 1987). One of the OH substituents on the dihydroxy benzene ring is disordered over the two possible 3-positions (labelled O3 and O5) on either side of the ordered O4 hydroxo group. Occupancy of the O3 and H5 atoms of the major disorder component refines to 0.633 (7). The molecule is essentially planar with an r.m.s. deviation through all non-hydrogen atoms of 0.0862 Å. An intramolecular N3—H3B···N1 hydrogen bond forms between the outer amine residue and the imine N atom generating an S(5) ring motif (Bernstein et al., 1995) which contributes to the planarity of the molecule.

In the crystal structure N2—H2A···S1 hydrogen bonds, Table 1, generate centrosymmetric R²₂(8) rings. Other classical O—H···O and O—H···S hydrogen bonds combine with weak C—H···O and S1···O4ⁱ interactions (d(S1···O4) = 3.301 (3) Å; i = -1 + x, 1/2 - y, 1/2 + z) to form sheets running approximately parallel to the ac diagonal, Fig 2.

Experimental

The title compound C₁₀H₁₃N₃O₂S was prepared by heating an ethanolic (35 ml) solution of 3,4-dihydroxybenzaldehyde (1.4 g, 10 mmol) and 4-ethyl-3-thiosemicarbazide (1.2 g, 10 mmol) under reflux for 1 h. The resulting product was isolated and recrystallized from ethanol to afford red block-shaped crystals in 71% yield (m.p. 464–467 K).