(E)-1-[1-(6-Bromo-2-oxo-2H-chromen-3-yl)ethyl­idene]thio­semicarbazide

Afsheen Arshad; Hasnah Osman; Kit Lam Chan; Jia Hao Goh; Hoong-Kun Fun

doi:10.1107/S1600536810019240

. 2010 May 29;66(Pt 6):o1491–o1492. doi: 10.1107/S1600536810019240

(E)-1-[1-(6-Bromo-2-oxo-2H-chromen-3-yl)ethylidene]thiosemicarbazide

Afsheen Arshad ^a, Hasnah Osman ^a,^‡, Kit Lam Chan ^b, Jia Hao Goh ^c,^§, Hoong-Kun Fun ^c,^*,^¶

PMCID: PMC2979475 PMID: 21579554

Abstract

The title compound, C₁₂H₁₀BrN₃O₂S, exists in an E configuration with respect to the C=N bond. The approximately planar 2H-chromene ring system [maximum deviation = 0.059 (1) Å] is inclined at a dihedral angle of 17.50 (5)° with respect to the mean plane through the thiosemicarbazide unit and an intramolecular N—H⋯N hydrogen bond generates an S(5) ring. In the crystal structure, adjacent molecules are linked by N—H⋯S hydrogen bonds, forming [010] chains built up from R ₂ ²(8) loops, such that each S atom accepts two such bonds. These chains are further interconnected into sheets parallel to the ab plane via short Br⋯O interactions [3.0732 (13) Å] and a π–π aromatic stacking interaction [3.7870 (8) Å] is also observed.

Related literature

For general background to and applications of the title thiosemicarbazide compound, see: Anderson et al. (2002 ▶); Chulian et al. (2009 ▶); Desai et al. (1984 ▶); Finn et al. (2004 ▶); Hofmanová et al. (1998 ▶); Hoult & Payá (1996 ▶); Kimura et al. (1985 ▶); Laffitte et al. (2002 ▶); Mitscher (2002 ▶); Moffett (1964 ▶); Pillai et al. (1999 ▶); Shukla et al. (1984 ▶); Tassies et al. (2002 ▶); Weber et al. (1998 ▶). For the preparation, see: Moamen et al. (2009 ▶). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For a related structure, see: Arshad et al. (2010 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₂H₁₀BrN₃O₂S
M _r = 340.20
Triclinic,
a = 6.3796 (6) Å
b = 8.1260 (7) Å
c = 13.3756 (12) Å
α = 106.697 (2)°
β = 95.095 (2)°
γ = 98.925 (2)°
V = 649.57 (10) Å³
Z = 2
Mo Kα radiation
μ = 3.33 mm⁻¹
T = 100 K
0.73 × 0.20 × 0.15 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.196, T _max = 0.637
19355 measured reflections
5036 independent reflections
4733 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.084
S = 1.17
5036 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810019240/hb5461sup1.cif

e-66-o1491-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810019240/hb5461Isup2.hkl

e-66-o1491-Isup2.hkl^{(246.6KB, 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—H2N3⋯N1	0.82 (3)	2.15 (3)	2.6004 (17)	114 (3)
N2—H1N2⋯S1ⁱ	0.73 (3)	2.70 (3)	3.4094 (13)	165 (3)
N3—H1N3⋯S1ⁱⁱ	0.81 (2)	2.49 (2)	3.3010 (13)	175.6 (19)

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for a Short-term Grant (No. 304/PKIMIA/639004) to conduct this research. AA thanks the Pakistan Government and PCSIR for financial scholarship support. HKF and JHG thank USM for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

Thiosemicarbazide compounds exhibit various biological activities such as anti-bacterial, anti-fungal and especially anti-tuberculosis (Shukla et al., 1984, Desai et al., 1984). Apart from this, coumarins constitute an important class of compounds found throughout the plant kingdom and are known to have diverse activities such as anti-coagulants (Anderson et al., 2002, Tassies et al., 2002), anti-bacterial (Mitscher, 2002, Laffitte et al., 2002), anti-fungal (Moffett, 1964) and cytotoxicity (Weber et al., 1998) properties. The coumarin moiety and related derivatives are also reported to have importance as vasodilators (Hoult & Payá, 1996), anti-mutagenic agents (Pillai et al., 1999), scavengers of reactive oxygen species (Finn et al., 2004), as well as lipoxygenese and cyclooxygenese inhibitors (Kimura et al., 1985, Hofmanová et al., 1998). The title compound exhibits very good anti-bacterial activity against Escherichia coli and Bacillus. subtilus (Chulian et al., 2009). The objective of this study is to synthesize new derivatives of coumarin-thiosemicarbazide compounds. We present in this paper the crystal structure of this title compound.

The title thiosemicarbazide compound (Fig. 1) exists in a cis configuration with respect to the Schiff base C10═N1 bond [N1═C10 = 1.2890 (15) Å; torsion angle C9–C10–N1–N2 = 178.83 (10)°]. The 2H-chromene ring system (C1-C9/O1) is approximately planar, with a maximum deviation of 0.059 (1) Å at atom C9. The mean plane through the thiosemicarbazide moiety (N1/N2/C11/N3/S1) forms dihedral angle of 17.50 (5)° with the 2H-chromene ring system. Bond lengths and angles are consistent to a closely related structure (Arshad et al., 2010).

In the crystal structure, pairs of intermolecular N2—H1N2···S1 and N3—H1N3···S1 hydrogen bonds (Table 1) form bifurcated acceptor hydrogen bonds which generate two different R²₂(8) hydrogen bond ring motifs with zig-zag formation (Fig. 2, Bernstein et al., 1995). These hydrogen bonds link adjacent molecules into two-molecule wide chains along the b axis. Intermolecular short Br···O interactions [Br1···O2ⁱⁱⁱ = 3.0732 (13) Å; (iii) x+1, y-1, z] interconnect these chains into two-dimensional planes parallel to the ab plane (Fig. 3). The crystal structure is further stabilized by weak Cg1···Cg1 interactions involving the centroid of the C2-C7 benzene ring [Cg1···Cg1^iv = 3.7870 (8) Å; (iv) -x+1, -y, -z].

Experimental

Coumarin thiosemicarbazone was prepared by cyclocondensation of 5-bromosalicylaldehyde with ethylacetoacetate and the resulting acetyl coumarin intermediate was then treated with thiosemicarbazide to get the title compound as reported in the literature with some modifications (Moamen et al., 2009). The methanol solution of thiosemicarbazide (5.00 mmol) was added to a solution of 6-bromo-(3-acethylcoumarin) (5.00 mmol) in hot methanol (10 ml) while stirring. The resulting solution was refluxed for 1 h and then pH of the solution was adjusted to 4–5 by adding glacial acetic acid. The solution was again refluxed for 4 h. The title compound was recrystallized from ethyl acetate:ethanol (2:1) to give yellow needles of (I).