4-Methyl-N-[2-(pyridin-2-yl)ethyl­carbamo­thio­yl]benzamide

Farook Adam; Nadiah Ameram; Naser Eltaher Eltayeb

doi:10.1107/S1600536814016377

. 2014 Jul 31;70(Pt 8):o885. doi: 10.1107/S1600536814016377

4-Methyl-N-[2-(pyridin-2-yl)ethylcarbamothioyl]benzamide

Farook Adam ^a,^*, Nadiah Ameram ^a, Naser Eltaher Eltayeb ^b,^‡

PMCID: PMC4158510 PMID: 25249927

Abstract

In the title compound, C₁₆H₁₇N₃OS, the dihedral angle between the planes of the benzene and pyridine rings is 71.33 (15)°. An intramolecular N—H⋯O hydrogen bond is present. In the crystal, weak aromatic C—H⋯O hydrogen bonds link the molecules into chains extending along a.

Keywords: crystal structure, hydrogen bonding, thiourea compounds, thiocarbonyl groups, benzamide

Related literature

For related structures, see: Saeed & Flörke (2007 ▶); Yusof et al. (2008 ▶, 2011 ▶); Shoukat et al. (2007 ▶); Hassan et al. (2008a ▶,b ▶,c ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For graph-set analysis, see Bernstein et al. (1995 ▶). graphic file with name e-70-0o885-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₇N₃OS
M _r = 299.39
Monoclinic,
a = 16.0467 (12) Å
b = 4.8824 (4) Å
c = 23.0403 (18) Å
β = 124.997 (5)°
V = 1478.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 100 K
0.47 × 0.20 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.903, T _max = 0.980
12777 measured reflections
3409 independent reflections
2221 reflections with I > 2σ(I)
R _int = 0.082

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.182
S = 1.04
3409 reflections
199 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 datablock(s) I. DOI: 10.1107/S1600536814016377/zs2306sup1.cif

e-70-0o885-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016377/zs2306Isup2.hkl

e-70-0o885-Isup2.hkl^{(167.2KB, hkl)}

Click here for additional data file.^{(5.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814016377/zs2306Isup3.cml

CCDC reference: 1014035

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
N2—H1N2⋯O2	0.87 (4)	1.90 (3)	2.645 (3)	143 (3)
C14—H14A⋯O2ⁱ	0.95	2.51	3.421 (4)	161

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Universiti Sains Malaysia for a research grant (No. PKIMIA846017) which partially supported this work.

supplementary crystallographic information

S1. Comment

In the title compound, C₁₆H₁₇N₃SO (Fig. 1), the bond lengths and angles are generally normal compared to those in N-alkyl-N-benzoylthiourea compounds (Allen et al., 1987). The bond lengths of the carbonyl and thiocarbonyl groups [C7—O2 = 1.229 (5) Å and C8—S1 = 1.677 (4) Å, respectively] have typical C═O and C═S double-bond character (Yusof et al. 2011). However, the thiocarbonyl is longer compared to the typical C═S bond which is 1.660 (2) Å. The C—N bond lengths for the title compound [C7—N1 = 1.375 (4) Å, C8—N1 = 1.397 (4) Å, C9—N2 = 1.460 (4) Å, C11—N3 = 1.335 (4), C15—N3 = 1.351 (4) Å] are all shorter than the average C—N single bond length [1.472 (5) Å], thus showing varying degrees of single bond character (Yusof et al. 2008). These bond features in the structure are presumed as a result of the intramolecular H-bonding interactions "locking" the molecule into a planar six-membered ring structure and are consistent with the expected delocalization in the title compound, confimed by the C9—N2—C8 and C8—N1—C7 bond angles [125.0 (3) and 128.8 (3)°, respectively], showing sp² hybridization on the N2 and N1 atoms. The molecule maintains its cis–trans configuration with respect to the position of the methyl benzene and ethyl pyridine groups relative to the thiocarbonyl sulfur atom across the N1—C7 and N2—C8 bonds, respectively (Hassan et al. (2008b,2008c)). The conformation of the molecule with respect to the thiocarbonyl and carbonyl moieties is twisted, as refleced by the torsion angles [C8–N1–C7–O2, C7–N1–C8–N2 and C7—N1—C8—S1: 2.1 (5), -4.4 (4) and 175.9 (2)°, respectively. The angle between the benzene and pyridine rings is 71.33 (15)°. The N2 H-atom forms bifurcated intramolecular interactions with both a carbonyl O-atom and the pyridine N-atom (Table 1): a hydrogen bond with O2 (N2—H···O2) and an interaction with N3 (N2—H···N3), giving cyclic motifs [graph sets S6 (Bernstein et al., 1995)]. Present also are weak intramolecular C1—H···O2 and C9—H···S1 interactions [graph set S(5)]. In the crystal, molecules are connected through weak intermolecular C14—H···O2 hydrogen-bonding interactions, giving one-dimensional chain structures extending along x (Fig. 2). The N1—H1N1 group has no acceptor in the crystal.

S2. Experimental

S2.1. Synthesis and crystallization

Freshly prepared substituted p-benzoyl chloride (13 mmol) was added dropwise to a stirred acetone solution (30 ml) of ammonium thiocyanate (13 mmol). The mixture was stirred for 10 min. A solution of 2-(2-aminethylpyridine) in acetone was added and the reaction mixture was refluxed for 3 h., after which the solution was poured into a beaker containing some ice cubes. The resulting precipitate was collected by filtration, washed several times with a cold ethanol/water mixture and purified by recrystallization from ethanol (Hassan et al., 2008a). Yield 65%; white transparent crystals, m.p. 126.3 °C. Anal Calc. for C16 H17 N3 O S: C, 64.9; H, 5.6; N, 15.9; S, 8.2%. Found: C, 64.8; H, 5.7; N, 14.8; S, 8.7%.

S2.2. Refinement

The H-atoms on the N atoms were located in a difference-Fourier and were fully refined. All other H-atoms were positioned geometrically and refined using a riding model with C—H = 0.95–0.99 Å and U_iso(H) = 1.2U_eq(aromatic C), 1.5U_eq(methyl C) and 1.2U_eq(methylene C).