Crystal structure of N-[(4-eth­oxy­phen­yl)carbamo­thio­yl]cyclo­hexa­ne­carboxamide

G Vimala; J Haribabu; S Srividya; R Karvembu; A SubbiahPandi

doi:10.1107/S205698901501806X

. 2015 Oct 7;71(Pt 11):o820–o821. doi: 10.1107/S205698901501806X

Crystal structure of N-[(4-ethoxyphenyl)carbamothioyl]cyclohexanecarboxamide

G Vimala ^a, J Haribabu ^b, S Srividya ^b, R Karvembu ^b, A SubbiahPandi ^a,^*

PMCID: PMC4645074 PMID: 26594545

Abstract

The asymmetric unit of the title compound, C₁₆H₂₂N₂O₂S, contains two crystallographically independent molecules (A and B). In molecule A, the cyclohexane ring is disordered over two orientations [occupancy ratio 0.841 (10):0.159 (10)]. In each molecule, the central carbonyl thiourea unit is nearly planar (r.m.s. deviations for all non-H atoms of 0.034 Å in molecule A and 0.094 Å in molecule B). In both molecules, the cyclohexane ring adopts a chair conformation. The mean plane of the cyclohexane ring makes dihedral angles of 35.8 (4) (molecule A) and 20.7 (3)° (molecule B) with that of the benzene ring. Each molecule features an intramolecular N—H⋯O hydrogen bond, which closes an S(6) ring motif. In the crystal, molecules are linked via pairs of weak N—H⋯S interactions, forming inversion dimers with an R ₂ ²(8) ring motif for both molecules. The crystal structure also features weak C—H⋯π ring interactions.

Keywords: crystals structure, thiourea derivatives, biological properties, anticorrosion properties, cyclohexanecarboxamide, C—H⋯π interactions

Related literature

For the biological and anticorrosion properties of thiourea derivatives, see: Hu et al. (2011 ▸); Sun et al. (2006 ▸); Shen et al. (2006 ▸). For related structure see: Vimala et al. (2015 ▸); Gangadharan et al. (2015 ▸). graphic file with name e-71-0o820-scheme1.jpg

Experimental

Crystal data

C₁₆H₂₂N₂O₂S
M _r = 306.41
Triclinic
a = 10.2273 (7) Å
b = 12.0946 (7) Å
c = 15.2099 (10) Å
α = 70.792 (3)°
β = 89.100 (3)°
γ = 69.737 (3)°
V = 1656.42 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T _min = 0.942, T _max = 0.961
35699 measured reflections
5827 independent reflections
3444 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.205
S = 1.10
5827 reflections
503 parameters
97 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: APEX2 and SAINT (Bruker, 2008 ▸); data reduction: SAINT and XPREP (Bruker, 2008 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901501806X/jj2193sup1.cif

e-71-0o820-sup1.cif^{(1.2MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901501806X/jj2193Isup2.hkl

e-71-0o820-Isup2.hkl^{(463.3KB, hkl)}

Click here for additional data file.^{(6KB, cml)}

Supporting information file. DOI: 10.1107/S205698901501806X/jj2193Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S205698901501806X/jj2193fig1.tif

The molecular structure of the major component of the title compound, with displacement ellipsoids drawn at 30% probability level.

Click here for additional data file.^{(1.1MB, tif)}

a b . DOI: 10.1107/S205698901501806X/jj2193fig2.tif

A view of the packing of (I) along the a axis, showing N—H⋯O intramolecular hydrogen bonds and molecules linked by weak N—H⋯S intermolecular interactions along the b axis.

CCDC reference: 1427899

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C3AC8A ring.

DHA	DH	HA	D A	DHA
C2BH2DO2B ⁱ	0.97	2.57	3.264(10)	128
N1BH3O2B	0.86(2)	1.91(3)	2.641(4)	142(4)
N1AH1O2A	0.87(2)	1.90(3)	2.628(4)	140(4)
N2BH4S1A ⁱⁱ	0.84(2)	2.68(2)	3.469(3)	157(3)
N2AH2S1B ⁱⁱⁱ	0.85(2)	2.73(3)	3.430(3)	140(3)
C12H12C Cg1^iv	0.90	2.49(2)	3.42(1)	159

Open in a new tab

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

Acknowledgments

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

S1. Comment

The design and synthesis of thioureas are of considerable interest because of their use in agriculture, medicine and analytical chemistry (Hu et al., 2011). Thiourea derivatives are driven by their potential as biological active compounds (Sun et al., 2006) and in material applications such as with their anti corrosion prperties (Shen et al., 2006). In view of their biological importance, the crystal structure of the title compound, C₁₆H₂₂N₂O₂S, (I), has been determined herein.

The title compound, (I), contains two crystallographically independent molecules (A and B) in the asymmetric unit (Fig1.). In molecule A, the cyclohexane ring is disordered over two positions [occupancy ratio 0.533 (2): 0.467 (2)]. In each molecule, the central carbonyl thiourea unit is nearly planar (r.m.s. deviations for all non-H atoms of -0.034 Å for C6A and -0.094 Å for C6B. For molecule A, the cyclohexane ring (C11A—C16A) adopts a chairconformation [puckering parameters, q = 0.627 (1) Å, θ = 6.8°, φ = 279 (2)°], while for molecule B, the cyclohexane ring (C11B—C16B) also adopts a chair conformation [puckering, q = 0.546 (6) Å, θ = 179.3°, φ = 219 (2)°;]. The mean plane of the cyclohexane ring makes a dihedral angle of 35.8 (4)° (C3A—C8A) and 20.7 (3)° (C3B—C8B) with that of the benzene ring. Each molecule features an intramolecular N—H···O hydrogen bond (Table 1), which closes an S(6) ring motif. In the crystal, the molecules are linked via pairs of N—H···S weak intermolecular interactions, forming inversion dimers with an R²₂(8) ring motif (Bernstein et al. 1995) for both molecules (Fig. 2). The crystal structure is further stabilized by a weak C—H···π ring interactions (Table 1).

S2. Experimental

A mixture of 6-chlorol-3-formylchromone (1 mmol), cyanoacetylindole (1 mmol) and ammonium acetate (1 mmol) in DMF and a catalytic amount of SnCl2.2H2O (0.020 mol %) was added and refluxed for about 3 hrs. After completition of the reaction, the solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel (3:97% ethylacetate and petether) to afford a pure product. The purified compound was recrystalized from ethanol by using the slow evaporation method. The yield of the isolated product was 92%, giving block-like crystals suitable for X ray diffraction.