3,4-Dihydroxy­benzaldehyde 4-phenyl­thio­semicarbazone

Kong Wai Tan; Yang Farina; Chew Hee Ng; Mohd Jamil Maah; Seik Weng Ng

doi:10.1107/S1600536808013287

. 2008 May 10;64(Pt 6):o1035. doi: 10.1107/S1600536808013287

3,4-Dihydroxybenzaldehyde 4-phenylthiosemicarbazone

Kong Wai Tan ^a, Yang Farina ^b, Chew Hee Ng ^c,^*, Mohd Jamil Maah ^d, Seik Weng Ng ^d

PMCID: PMC2961546 PMID: 21202558

Abstract

Molecules of the title compound, C₁₄H₁₃N₃O₂S, are linked by intermolecular O—H⋯O hydrogen bonds into centrosymmetric dimers forming R ₂ ²(4) rings which are further linked by O—H⋯S hydrogen bonds and weaker N—H⋯S and N—H⋯O hydrogen bonds to form a three-dimensional network.

Related literature

For the structure of 2,3-dihydroxybenzaldehyde thiosemicarbazone hemihydrate, see: Swesi et al. (2006 ▶). For metal derivatives of the title compound, see: Zhu et al. (1997 ▶). The graph-set notation is given by Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₃N₃O₂S
M _r = 287.33
Monoclinic,
a = 9.7261 (2) Å
b = 13.1863 (3) Å
c = 10.7732 (3) Å
β = 99.055 (2)°
V = 1364.46 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 (2) K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.909, T _max = 0.953
16724 measured reflections
3132 independent reflections
2358 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.115
S = 1.04
3132 reflections
197 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013287/lh2625sup1.cif

e-64-o1035-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013287/lh2625Isup2.hkl

e-64-o1035-Isup2.hkl^{(153.7KB, 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
O1—H1o⋯O2ⁱ	0.85 (1)	2.03 (2)	2.737 (2)	141 (2)
O2—H2o⋯S1ⁱⁱ	0.85 (1)	2.34 (1)	3.134 (1)	156 (2)
N2—H2n⋯S1ⁱⁱⁱ	0.85 (1)	2.73 (1)	3.487 (2)	150 (2)
N2—H2n⋯O1^iv	0.85 (1)	2.56 (2)	3.022 (2)	115 (2)

Open in a new tab

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

Acknowledgments

We thank the University of Malaya (P0265/2007 A) for supporting this study; KWT thanks the Ministry of Higher Education for an SLAI scholarship in this research.

supplementary crystallographic information

Comment

A previous study of the Schiff bases derived by condensing substituted benzaldehydes with 4-phenylthiosemicarbazides reported the 2,3-dihydroxy compound, which crystallizes as a hemihydrate. The compound features extensive hydrogen bond (Swesi et al., 2006). In the title 3,4-dihydroxy isomer the 4-hydroxy group functions as hydrogen-bond donor to the 3-hydroxy group of a symmetry-related molecule forming R₂²(4) rings (Bernstein et al., 1995). In addition, the 3-hydroxy group is a donor to the sulfur atom of another molecule; the hydrogen bonding arrangement furnishes a three-dimensional network motif. The amino groups are involved in weaker hydrogen bond interactions.

Further work will investigate the formation of metal deratives of the ligand; some metal complexes have been reported by others but these have not characterized by crystallography yet (Zhu et al., 1997).

Experimental

4-Phenylthiosemicarbazide (0.17 g, 1 mmol) and 3,4-dihydroxybenzaldehyde (0.14 g, 1 mmol) were heated in ethanol (20 ml) for 3 h. Slow evaporation of the solvent yielded yellow crystals.