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

Yang Farina; Jim Simpson

doi:10.1107/S1600536808034326

. 2008 Oct 25;64(Pt 11):o2184–o2185. doi: 10.1107/S1600536808034326

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

Yang Farina ^a,^*, Jim Simpson ^b

PMCID: PMC2959612 PMID: 21581043

Abstract

The title compound, C₉H₁₁N₃O₂S, adopts an E configuration with respect to the C=N bond. The molecule is approximately planar, with an r.m.s. deviation from the mean plane through all 15 non-H atoms of 0.152 Å; the dihedral angle between the benzene ring plane and the least-squares plane through the thiosemicarbazone unit is 12.48 (7)°. A weak intramolecular N—H⋯N interaction contributes to the planarity of the semicarbazone unit. Centrosymmetric pairs of O—H⋯O and N—H⋯S hydrogen bonds form chains along c, generating R ₂ ²(10) and R ₂ ²(8) ring motifs, respectively. In the crystal structure, these chains are further linked by intermolecular O—H⋯S and C—H⋯O interactions, forming stacks down the c axis.

Related literature

For the biological activity of thiosemicarbazones, see: de Sousa et al. (2007 ▶). For related structures, see: Kayed et al. (2008 ▶); Tan et al. (2008a ▶,b ▶). For hydrogen-bonding patterns, see: Bernstein et al. (1995 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M _r = 225.27
Monoclinic,
a = 6.8502 (9) Å
b = 14.911 (2) Å
c = 10.6299 (13) Å
β = 107.894 (6)°
V = 1033.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 92 (2) K
0.23 × 0.15 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.799, T _max = 0.962
17952 measured reflections
3696 independent reflections
2974 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.112
S = 1.07
3696 reflections
149 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.32 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 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN (Hunter & Simpson, 1999 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2003 ▶) and publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034326/pv2112sup1.cif

e-64-o2184-sup1.cif^{(15KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034326/pv2112Isup2.hkl

e-64-o2184-Isup2.hkl^{(181.2KB, 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—H3N⋯N1	0.879 (9)	2.220 (18)	2.6282 (17)	108.0 (14)
O3—H3⋯O4ⁱ	0.837 (9)	2.070 (14)	2.8071 (14)	146.5 (19)
O4—H4⋯S1ⁱⁱ	0.836 (9)	2.369 (10)	3.1899 (11)	167.1 (19)
N2—H2N⋯S1ⁱⁱⁱ	0.876 (9)	2.785 (12)	3.5766 (13)	150.9 (15)
C9—H9A⋯O4^iv	0.98	2.56	3.435 (2)	148

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

Acknowledgments

We thank the Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grants UKM-ST-01-FRGS0022–2006 and UKM-GUP-NBT-08–27-112 and Mr M. A. I. Yim for preparing the title compound. We also thank the University of Otago for purchase of the diffractometer.

supplementary crystallographic information

Comment

Thiosemicarbazones are a class of compounds that have been extensively investigated because of their biological activity (de Sousa et al., 2007). As a continuation of our work on thiosemicarbazone compounds as potential ligands in transition metal chemistry (Kayed et al., 2008; Tan et al., 2008a,b) we report here the structure of the title compound, (I).

The molecule of (I) (Fig. 1) is approximately planar with a dihedral angle of 12.48 (7)° between the phenyl ring plane and the least squares plane through the C7/N1/N2/C8/S2/N3 thiosemicarbazone moiety. The planarity of this section of the molecule is aided by a weak intramolecular N3—H3N···N1 interaction. The molecule adopts an E configuration with respect to the C═N bond and bond distances are normal (Allen et al., 1987).

Pairs of O3—H3···O4 hydrogen bonds generate a centrosymmetric R²₂(10) ring motif (Bernstein et al., 1995) and, together with the R²₂(8) ring generated by N2—H2N···S1 interactions, form an unusual molecular trimer. The crystal structure is further stabilized by O4—H4···S1 and C9—H9A···O4 contacts, Table 1, Fig. 2.

Experimental

A 1:1 mixture of 3,4-dihydroxybenzaldehyde and N-methylhydrazinecarbothioamide was heated under reflux in ethanol for 2 hours. The solid product which separated upon cooling was filtered and recrystallised from methanol to afford colourless blocks of (I) in 54% yield (m.p. 418-419 K).