N-[Eth­yl(2-hy­droxy­eth­yl)carbamo­thio­yl]-2-methyl­benzamide

Bohari M Yamin; Sara Maira M Hizam; Siti Fairus M Yusoff; Siti Aishah Hasbullah

doi:10.1107/S1600536814008952

. 2014 Apr 26;70(Pt 5):o602. doi: 10.1107/S1600536814008952

N-[Ethyl(2-hydroxyethyl)carbamothioyl]-2-methylbenzamide

Bohari M Yamin ^a, Sara Maira M Hizam ^b, Siti Fairus M Yusoff ^b, Siti Aishah Hasbullah ^b,^*

PMCID: PMC4011282 PMID: 24860396

Abstract

The title compound, C₁₃H₁₈N₂O₂S, adopts a cis conformation between the methylbenzoyl and thiono groups across their thiourea C—N bond. However, the methylbenzoyl group and N₂CS thiourea moiety are twisted by 15.03 (3)°. In the molecule there is an N—H⋯O hydrogen bond. In the crystal, molecules are linked by O—H⋯O interactions, generating chains extending along the c-axis direction.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For related structures of thiourea derivatives, see: Awang et al. (2013 ▶); Sapari et al. (2013 ▶). graphic file with name e-70-0o602-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₈N₂O₂S
M _r = 266.35
Monoclinic,
a = 11.393 (4) Å
b = 8.989 (3) Å
c = 14.467 (5) Å
β = 109.940 (9)°
V = 1392.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.35 × 0.34 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.924, T _max = 0.986
28196 measured reflections
2583 independent reflections
2005 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.088
S = 1.06
2583 reflections
169 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814008952/lr2125sup1.cif

e-70-0o602-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008952/lr2125Isup2.hkl

e-70-0o602-Isup2.hkl^{(126.9KB, hkl)}

Click here for additional data file.^{(5.2KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814008952/lr2125Isup3.cml

CCDC reference: 998473

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
N1—H1A⋯O2	0.86	1.98	2.750 (2)	149
O2—H2A⋯O1ⁱ	0.81 (2)	1.91 (2)	2.716 (2)	171 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would like to thank Universiti Kebangsaan Malaysia and the Ministry of Science and Technology, Malaysia, for research grants GUP-2103-022, DIP-2012-11, LRGS/BU/2011/USM-UKM/PG-02 and the Centre of Research and Instrumentation (CRIM) for research facilities.

supplementary crystallographic information

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

An acetone (30 ml) solution of 2-(ethylamino)ethanol (0.18 g, 2 mmol) was added to a round-bottomed flask containing 2-methylbenzoyl isothiocyanate (0.31 g,2 mmol). The mixture was refluxed for 3h. After cooling the solution was filtered off and the filtrate was left to evaporate at room temperature. The solid formed was washed with water and cold ethanol. Crystals suitable for X-ray study were obtained by recrystallization from DMSO.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C—H= 0.93-0.97Å and N–H = 0.86Å with U_iso(H)= 1.2U_eq[C (methylene and aromatic),N] and 1.5 U_eq [C (methyl)]. The hydroxyl hydrogen atom was located from Fourier map and refined isotropically with O—H restraint to 0.81Å with esd of 0.01.

3. Results and discussion

The carbonoylthiourea derivatives with a secondary amine group at the terminal thiourea moiety are expected to adopt a cis conformation with respect to the position of the carbonoyl against the thiono group. Such a configuration will allow the ligand to chelate with metals in bidentate manner. Thus, 2,4-dichloro-N-[ethyl(hydroxyethyl)carbamothioyl]benzamide (Sapari et al.,2013) and N[ethyl(hydroxyethyl)carbamothioyl]-2-iodo-benzamide (Awang et al., 2013) adopt the said conformation. The title compound is analogous to the two compounds but having a methyl group attached at position-2 of the benzene ring (Fig.1). However, the title molecule maintains a cis conformation between the carbonyl and thiono groups across the C8—N1 bond and twisted by torsion angle of O1—C8—N1—C9 and S1—C9—N1—C8 of 7.1 (3)and 47.1 (2)° respectively. Both S1/N1/N2/C9 thiourea moiety and (C1—C8) benzyl fragments are planar with maximum deviation of 0.031 (2)Å for C4 atom from the least square plane of the benzyl fragment. The two planes make dihedral angle of 15.03 (3)°. The bond lengths and angles are in normal ranges (Allen et al.,1987) and comparable to those in the two analogs. There is an intramolecular hydrogen bond N1–H1A···O2 between the amido hydrogen and hydroxyl oxygen atom. In the crystal structure, the molecules are linked by O2–H2A···O1 intermolecular hydrogen bond (see Table 1 for symmetry codes) to form one-dimensional chains along the c-axis direction (Fig.2). In addition, there is a C—H.. π bond between H12B and (C1—C6) centroid (-x,1-y,-z) with the H12B···C_g distance of 2.84Å and C12—H12B—C_g angle, 137°.