N-(Biphenyl-4-ylcarbon­yl)-N′-(2-pyridylmeth­yl)thio­urea

Bohari M Yamin; Hidayah Deris; Zaw Myint Malik; Sammer Yousuf

doi:10.1107/S1600536807067499

. 2008 Jan 4;64(Pt 2):o360. doi: 10.1107/S1600536807067499

N-(Biphenyl-4-ylcarbonyl)-N′-(2-pyridylmethyl)thiourea

Bohari M Yamin ^a, Hidayah Deris ^a, Zaw Myint Malik ^a, Sammer Yousuf ^b,^*

PMCID: PMC2960299 PMID: 21201392

Abstract

In the title compound, C₂₀H₁₇N₃OS, the dihedral angle between the benzene rings of the biphenyl fragment is 36.84 (9)°. The trans–cis geometry of the thiourea unit is stabilized by intramolecular N—H⋯O and N—H⋯N hydrogen bonds between the H atom of the cis thioamide and the carbonyl O and pyridine N atoms, respectively. In the crystal structure, intermolecular N—H⋯S hydrogen bonds form centrosymmetric dimers extending along the b axis.

Related literature

For the crystal structure of the biphenyl-4-carbonylthiourea analogue, see: Arif & Yamin (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₀H₁₇N₃OS
M _r = 347.43
Triclinic,
a = 7.467 (2) Å
b = 9.364 (2) Å
c = 13.184 (3) Å
α = 101.529 (5)°
β = 99.113 (4)°
γ = 101.543 (5)°
V = 865.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 273 (2) K
0.45 × 0.37 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.915, T _max = 0.965
8243 measured reflections
3036 independent reflections
2561 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.101
S = 1.05
3036 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807067499/at2519sup1.cif

e-64-0o360-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067499/at2519Isup2.hkl

e-64-0o360-Isup2.hkl^{(149KB, 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—H2⋯O1	0.86	1.99	2.6681 (19)	135
N2—H2⋯N3	0.86	2.24	2.6488 (19)	109
N1—H1⋯S1ⁱ	0.86	2.79	3.4759 (17)	138

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Ministry of Higher Education of Malaysia for the Fundamental Research Grant UKM-ST-01-FRGS-0003–2006 and Universiti Kebangsaan Malaysian for the research facilities.

supplementary crystallographic information

Comment

The title compound, (I), analogous to N-(biphenyl-4-carbonyl)-N'- (2-chlorophenyl)thiourea (II) (Arif & Yamin, 2007) except the 2-chlorobenzene group is replaced by the 2-methyl-pyridine group (Fig.1). The molecule maintains its trans-cis configuration with respect to the position of the biphenyl-4-carbonyl and 2-methyl-pyridin groups relative the thiono sulfur atom across the C14—N1 and C14—N2 bonds, respectively. Other bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable to those in (II). However, the dihedral angle between the benzene rings of the biphenyl fragment, (C1—C6) and (C7—C12) of 36,84 (9)° is larger than that (20.71 (17)°) in (II). Both the central C13/O1/N1/C14/S1/N2/C15 fragment and pyridine ring (N3/C16—C20), are planar with a maximum deviation of 0.032 (2)Å for atom N1 atom from the least square plane of the central fragment. The central fragment makes dihedral angles with the (C7—C12) benzene and (N3/C16—C20) pyridine rings of 16.39 (8) and 13.21 (6)°, respectively. The trans-cis geometry of the thiourea moiety is stabilized by the relatively strong N2—H2···O1 and a weak N2—H2···N3 intramolecular hydrogen bonds (Table 2). In the crystal structure, the molecules are linked by N1—H1···S1 intermolecular hydrogen bonds to form centrosymmetric dimers and are arranged parallel to b axis (Fig.2). In (II), the molecule is stabilized by van der Waal and π-π interactions.

Experimental

The mixrure of biphenyl 1–4 carbonyl chloride (5.417 g, 0.025 mol), with the equimolar amount of ammonium thiocyanate (1.903 g, 0.025 mol) and 2-picolylamine (2.704 g, 0.025 mol) in 30 ml dry acetone was refluxed with stirring for 4 h. The solution was filtered and left to evaporate at room temperature. The black precipitate obtained after a few days, was washed with water and cold ethanol (80%; m.p 416.4–419.2 K). Suitable crystals for X-ray investigation were obtained byrecrystallization from mixture of dichloromethane and n-Hexane (1:3 v/v).