5-Hy­droxy-2-nitro­benzaldehyde thio­semicarbazone (HNBATSC)

M Sivasankar Reddy; Y Sarala; M Jagadeesh; Samar K Das; Varada Reddy Ammireddy

doi:10.1107/S1600536814015098

. 2014 Jul 2;70(Pt 8):o846. doi: 10.1107/S1600536814015098

5-Hydroxy-2-nitrobenzaldehyde thiosemicarbazone (HNBATSC)

M Sivasankar Reddy ^a,^*, Y Sarala ^b, M Jagadeesh ^a, Samar K Das ^c, Varada Reddy Ammireddy ^a

PMCID: PMC4158534 PMID: 25249898

Abstract

The asymmetric unit of the title compound, C₈H₈N₄O₃S, consists of two independent molecules. Each molecule is approximately planar with dihedral angles of 8.71 (3) and 1.50 (2)° between the aromatic ring and the thiosemicarbazide moiety while the NO₂ group makes dihedral angles of 29.27 (3) and 17.78 (3)° with the benzene ring. In the crystal, the molecules are linked by N—H⋯S, O—H⋯O and N—H⋯O hydrogen bonds, forming two-dimensional networks parallel to (100).

Keywords: Thiosemicarbazone, Evolution of molecular structure, Crystallographic studies, Triclinic symmetry, crystal structure

Related literature

For the crystal structures of similar Schiff base compounds see: Chattopadhyay et al. (1988 ▶). For the structure of 2-hydroxy-5-nitrobenzaldehyde thiosemicarbazone, see: Alhadi et al. (2008 ▶). For general background to the biological activity and anti-tumour activity of benzaldehyde thiosemicarbazone derivatives, see: Hamre et al. (1950 ▶); Brockman et al. (1956 ▶). graphic file with name e-70-0o846-scheme1.jpg

Experimental

Crystal data

C₈H₈N₄O₃S
M _r = 240.24
Triclinic,
a = 7.1328 (13) Å
b = 8.0738 (15) Å
c = 17.868 (3) Å
α = 102.142 (16)°
β = 94.325 (15)°
γ = 95.212 (15)°
V = 997.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T _min = 0.796, T _max = 1.000
7083 measured reflections
4063 independent reflections
1973 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.137
S = 0.99
4063 reflections
321 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814015098/ds2241sup1.cif

e-70-0o846-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015098/ds2241Isup2.hkl

e-70-0o846-Isup2.hkl^{(199.1KB, hkl)}

Click here for additional data file.^{(3.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814015098/ds2241Isup3.cml

CCDC reference: 1010403

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H8B⋯S1ⁱ	0.80 (6)	2.59 (6)	3.323 (5)	153 (6)
N7—H7N⋯S1ⁱⁱ	1.07 (4)	2.22 (4)	3.264 (4)	162 (3)
N3—H3N⋯S2ⁱⁱⁱ	0.95 (4)	2.41 (4)	3.324 (4)	160 (4)
N4—H4B⋯S2^iv	0.86 (4)	2.51 (4)	3.373 (4)	180 (4)
O4—H4O⋯O5ⁱⁱⁱ	0.76 (5)	2.27 (6)	2.960 (5)	153 (7)
C3—H3⋯O9^v	0.93	2.57	3.491 (6)	168
C7—H7⋯O5^v	0.93	2.79	3.295 (5)	115
N4—H4A⋯O7ⁱⁱⁱ	0.87 (4)	2.48 (4)	3.066 (5)	125 (3)
O6—H6O⋯O4^vi	1.01 (5)	1.81 (5)	2.810 (5)	170 (4)
N8—H8A⋯O9ⁱⁱ	0.98 (5)	2.39 (4)	3.002 (5)	120 (3)
C13—H13⋯O10ⁱⁱ	0.93	2.67	3.506 (5)	150

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

Acknowledgments

MSR is grateful to the UGC, Government of India, New Delhi for financial assistance in the form of a meritorious research fellowship. The authors also thank the School of Chemistry, UGC Networking Resource centre, University of Hyderabad, for providing the single-crystal X-ray diffractometer facility. Special thanks are due to Dr Bharat Kumar Tripuramallu, School of Chemistry, University of Hyderabad, for his valuable suggestions and help in processing the data.

supplementary crystallographic information

S1. Comment

Benzaldehydethiosemicarbazone derivatives show in vitro anti-bacterial, anti-oxidant and anti-tubercular activities. Thiosemicarbazones have also been used as second line drugs in the chemotherapy of leprosy. Since then, several workers have reported the anti-microbial activity of thiosemicarbazones against selected plant pathogenic and saprophytic fungi. The anti-viral effect of thiosemicarbazones was first demonstrated (Hamre et al., 1950). They explained that p-aminobenzaldehyde-3-thiosemicarbazone and several of its derivatives were active against vaccinia virus in mice. Antitumor activity against leukemia in mice was first reported (Brockman et al., 1956).

We reported here the synthesis and structural characterization of a Schiff base, 5-hydroxy-2-nitrobenzaldehydethiosemicarbazone (Fig. 1). Due to the presence of potential hydrogen donor sites in the molecule, supramolecular hydrogen bonding interactions in the domain of thiosemicarbazones are observed. Intermolecular N—H···S interactions through R²₂(8) synthons result in the formation of 1D chains (Fig. 2). These 1D chains, with the aid of O—H···O interactions, form 2D corrugated sheets (Fig.3).

S2. Experimental

5-Hydroxy-2-nitrobenzaldehydethiosemicarbazone (0.33 g, 2 mmol) and thiosemicarbazide (0.18 g, 2 mmol) were separately dissolved in 20 ml of ethanol and subsequently they were mixed. The resulting mixture (40 ml) was refluxed for 5 hrs. The precipitate, formed during this time, was filtered and washed with a small amount of ethanol. The purity of the product HNBATSC was checked by TLC. Finally HNBATSC was dissolved in acetonitrile and then slowly it was evaporated for the removal of acetonitrile to obtain white crystals.

S2.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.