Crystal structure of 1-(4-formyl­benzyl­idene)thio­semicarbazone

Rosa Carballo; Arantxa Pino-Cuevas; Ezequiel M Vázquez-López

doi:10.1107/S1600536814017255

. 2014 Aug 6;70(Pt 9):o970. doi: 10.1107/S1600536814017255

Crystal structure of 1-(4-formylbenzylidene)thiosemicarbazone

Rosa Carballo ^a, Arantxa Pino-Cuevas ^a, Ezequiel M Vázquez-López ^a,^*

PMCID: PMC4186181 PMID: 25309285

Abstract

The asymmetric unit of the title compound, C₉H₉N₃OS, contains two approximately planar molecules (r.m.s. deviations for 14 non-H atoms = 0.094 and 0.045 Å), with different conformations. In one of them, the C=O group is syn to the S atom and in the other it is anti. Each molecule features an intramolecular N—H⋯N hydrogen bond, which generates an S(5) ring. In the crystal, molecules are linked by N—H⋯O and N—H⋯S hydrogen bonds, generating discrete networks; the syn molecules form [010] chains and the anti molecules form (100) sheets.

Keywords: crystal structure, thiosemicarbazone, hydrogen bonds

Related literature

For further synthetic details, see: Jagst et al. (2005 ▶). For structure–biological activity relationships in thiosemicarbazones, see: Lukmantara et al. (2013 ▶). For their biological properties, see: Serda et al. (2012 ▶). graphic file with name e-70-0o970-scheme1.jpg

Experimental

Crystal data

C₉H₉N₃OS
M _r = 207.25
Monoclinic,
a = 12.3888 (9) Å
b = 11.7972 (8) Å
c = 14.9428 (11) Å
β = 110.286 (1)°
V = 2048.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.51 × 0.44 × 0.33 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.693, T _max = 0.746
19018 measured reflections
4920 independent reflections
3344 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.119
S = 1.03
4920 reflections
277 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814017255/hb7254sup1.cif

e-70-0o970-sup1.cif^{(578.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017255/hb7254Isup2.hkl

e-70-0o970-Isup2.hkl^{(269.8KB, hkl)}

Click here for additional data file.^{(3.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814017255/hb7254Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

ORTEP . DOI: 10.1107/S1600536814017255/hb7254fig1.tif

ORTEP view of the two molecules of the title compound. Displacement ellipsoids shown at the 50% probability level.

Click here for additional data file.^{(1.6MB, tif)}

. DOI: 10.1107/S1600536814017255/hb7254fig2.tif

View of the crystal packing showing the two different chains.

CCDC reference: 1016158

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
N1A—H1NA⋯N3A	0.84 (3)	2.32 (2)	2.630 (2)	102.0 (19)
N1A—H1NA⋯O1A ⁱ	0.84 (3)	2.41 (3)	3.190 (3)	154 (2)
N1A—H2NA⋯S1A ⁱⁱ	0.87 (3)	2.52 (3)	3.391 (2)	172 (2)
N2A—H3NA⋯S1B ⁱⁱⁱ	0.84 (2)	2.50 (2)	3.3270 (19)	166.1 (19)
N1B—H1NB⋯N3B	0.91 (3)	2.21 (3)	2.619 (3)	106 (3)
N1B—H2NB⋯O1B ^iv	0.88 (3)	2.01 (3)	2.857 (3)	161 (3)
N2B—H3NB⋯S1A ^v	0.84 (2)	2.58 (2)	3.409 (2)	171 (2)

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

Acknowledgments

This research was supported by the European Rural Development Fund and the Spanish Ministry of Education and Science through project CTQ2010–19386/BQU.

supplementary crystallographic information

S1. Chemical context

The study of the thiosemicarbazones is interesting because they are compounds which show diverse biological properties (Serda et al., 2012) and pharmacological activities (Lukmantara et al., 2013). Also the thiosemicarbazones are of interest from a supramolecular point of view since they can be functionalized to give different supramolecular arrays by hydrogen bonds.

S2. Structural commentary

We report here the synthesis and structural characterization of (4-formylbenzylidine)-thiosemicarbazone (Fig.1). The two molecules in the asymmetric unit are structurally different due to the different orientation of the carbonyl group respect to the thiosemicarbazone chain. The thiosemicarbazone moiety in both molecules shows an E conformation with the sulfur atom trans to the iminic nitrogen N3 atom. The molecules labeled as B are linked into lineal chains by N—H···O hydrogen bonds with a d(N···O) of 2.857 (3) Å but the molecules labeled as A use the same kind of hydrogen bond with a longer d(N···O) of 3.190 (3) Å to form helical chains (Fig. 2). The two types of chains are packed by N—H···S hydrogen bonds with d(N—S) in the range 3.32-3.41 Å and (NHS) angles close to linearity (between 166 and 172°).

S3. Supramolecular features

S4. Database survey

S5. Synthesis and crystallization

A solution of thiosemicarbazide (342mg, 3.72 mmol) in 50 ml of water was slowly added at 50°C to a solution of terephthaldicarboxaldehyde (500 mg, 3.73 mmol) in 100 ml water. Then the mixture was stirred at 50°C for 30 mins. Once cooled to room temperature, the yellow solid was filtered off and vacuum dried. Yellow prisms were obtained by recrystallization from EtOH/H₂O (1:1) solution. Yield: 78%. M.pt: 212–214°C. IR data (KBr, cm^-1): 3452w, 3328m, 3152m ν(NH); 2974w, 2863w ν(C—H aldehyde); 1686s ν(C=O); 1533s, 1281m ν(C=N), 830m, 793m ν(C=S). ¹H NMR data (DMSO-d₆, ppm): 10.60 (s, 1H, N(2)—H); 10.01 (s, 1H, C(1)—H); 8.32 (s, 1H, N(2)—H); 8.15 (s, 1H, N(2)—H); 8.09 (s, 1H, C(8)—H); 8.02 (d, 2H, J = 8.2 Hz, C(3,7)-H); 7.91 (d, 2H, J = 8.2 Hz, C(4,6)-H).