1-(Biphenyl-4-ylmethyl­idene)thio­semicarbazide monohydrate

Rafael Mendoza-Meroño; Laura Menéndez-Taboada; Eva Fernández-Zapico; Santiago García-Granda

doi:10.1107/S1600536810011888

. 2010 Apr 10;66(Pt 5):o1029. doi: 10.1107/S1600536810011888

1-(Biphenyl-4-ylmethylidene)thiosemicarbazide monohydrate

Rafael Mendoza-Meroño ^a, Laura Menéndez-Taboada ^a, Eva Fernández-Zapico ^a, Santiago García-Granda ^a,^*

PMCID: PMC2979168 PMID: 21579093

Abstract

In the title compound, C₁₄H₁₃N₃S·H₂O, the thiosemicarbazide group is nearly planar, with a maximum deviation of 0.072 (2) Å from the ideal least-squares plane, and shows an E conformation. In the crystal packing, the water molecules are involved in an extensive intermolecular N—H⋯O hydrogen-bond network, assisted by O—H⋯S interactions, which link the independent molecules into chains extended along b axis. An intramolecular hydrogen N—H⋯N bond helps to stabilize the molecular conformation.

Related literature

For the biological activity and potential medical applications of thiosemicarbazides, see: West et al. (1991 ▶). For thiosemicarbazides as ligands, see: Kowol et al. (2007 ▶).

Experimental

Crystal data

C₁₄H₁₃N₃S·H₂O
M _r = 273.36
Monoclinic,
a = 14.428 (5) Å
b = 6.350 (5) Å
c = 15.276 (4) Å
β = 99.750 (5)°
V = 1379.3 (12) Å³
Z = 4
Cu Kα radiation
μ = 2.05 mm⁻¹
T = 293 K
0.28 × 0.22 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Gemini S diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.659, T _max = 1.000
8823 measured reflections
2652 independent reflections
2208 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.145
S = 1.12
2652 reflections
233 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011888/vm2023sup1.cif

e-66-o1029-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011888/vm2023Isup2.hkl

e-66-o1029-Isup2.hkl^{(130.2KB, 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
N2—H14⋯O1	0.92 (3)	1.91 (3)	2.819 (3)	172 (3)
N3—H15⋯N1	0.91 (3)	2.14 (3)	2.585 (3)	110 (2)
N3—H16⋯S1ⁱ	0.86 (4)	2.59 (4)	3.422 (3)	163 (3)
O1—H17⋯S1ⁱⁱ	0.86 (5)	2.44 (5)	3.287 (3)	169 (4)
O1—H18⋯S1ⁱⁱⁱ	0.77 (5)	2.60 (5)	3.352 (3)	164 (5)

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

Acknowledgments

Financial support by the Agencia Española de Cooperación Internacional y Desarrollo (AECID), FEDER funding, Spanish MICINN (MAT2006–01997 and Factoría de Cristalización Consolider Ingenio 2010), Gobierno del Principado de Asturias (PCTI) and Banco Santander is acknowledged. Special thanks go to Professor José Manuel Concellón for his support and scientific advice.

supplementary crystallographic information

Comment

Thiosemicarbazides, a class of compounds possessing a wide spectrum of potential medicinal applications, have been studied for their antitumoral, antiviral, antibacterial, antimalarial, antifungal, anti-inflammatory and anti-HIV activities (West et al., 1991). These properties are thought to arise from the metal-chelating ability of these ligands. In almost all cases, the ligands are bidentate and bind to the metal through the S and hydrazinic N atoms, although there are examples of them acting as monodentate ligands binding only through sulfur (Kowol et al., 2007).

The title compound C₁₄H₁₃N₃S.H₂O was synthesized and its crystal structure is reported here. This compound is likely to have biomedical properties similar to other nitrogen-sulfur donor ligands. The asymmetric unit consists of a single molecule (I), shown in Figure 1. The thiosemicarbazide adopts an E conformation with a trans configuration observed about the C=N bond. The thiosemicarbazide moiety is planar, the C(14)—N(2) (1.341 (3) Å) and N(1)—N(2) (1.371 (3) Å) bond lengths imply significant electron delocalization and the C13/N1/N2/C14/S1 fragment is close to planar (max. deviation = 0.072 (2) Å). The dihedral angle between benzene ring C7/C8/C9/C10/C11/C12 and the moiety C13/N1/N2/C14/S1 is 4.67 (1)°. This value suggests that they are nearly coplanar, and π-electrons are delocalized in the benzaldehyde thiosemicarbazide fragment.

The water molecules are involved in an extensive intermolecular N(2)—H(14)···O(1) hydrogen bonds and O(1)—H(17)···S(1) interactions (Table 1), which link the molecules into chains extended along the b axis. Sulfur atom S(1) is also involved in N(3)—H(16)···S(1) intermolecular interactions, favoring the crystal grown in the ac plane. An intramolecular N(3)—H(15)···N(1) hydrogen bond (Table 1) contributes to stabilize the molecular conformation. The intermolecular distance value between ring centroids in the b axis direction (6.350 Å), suggests that there is no π-stacking interaction between parallel molecules (Figure 2).

Experimental

A solution of 4-biphenylcarboxaldehyde (1.822 g, 0.01 mol) and thiosemicarbazide (0.91 g, 0.01 mol) in absolute methanol (50 ml) was refluxing for 4 h, in the presence of p-toluenesulfonic acid (0.005 g) as catalyst, with continuous stirring. Completeness of the reaction was TLC controlled indicating the disappearance of the aldehyde spot. On cooling to room temperature the precipitate was filtered off, washed with copious cold methanol and dried in air (yield: 1.581 g, 61%; m.p. 475 K). Yellow single crystals compound were obtained after recrystallization from a solution of chloroform/methanol (3:7 v/v) after 10 days at room temperature.