Redetermination of 1-cyclo-hexyl-3-(2-furo-yl)thio-urea.

The title compound, C(12)H(16)N(2)O(2)S, was synthesized from furoyl isothio-cyanate and cyclo-hexyl-amine in dry acetone, and the crystal structure redetermined. The thio-urea group is in the thio-amide form. The structure [Otazo-Sánchez et al. (2001 ▶). J. Chem. Soc. Perkin Trans. 2, pp. 2211-2218] has been redetermined in order to establish the intra- and inter-molecular inter-actions. The trans-cis geometry of the thio-urea group is stabilized by intra-molecular hydrogen bonding between the carbonyl and cis-thio-amide groups, resulting in a pseudo-S(6) planar ring which makes a dihedral angle of 3.24 (6)° with the 2-furoyl group and a torsion angle of -84.3 (2)° with the cyclo-hexyl group. There is also an intra-molecular hydrogen bond between the furan O atom and the other thio-amide H atom. In the crystal structure, mol-ecules are linked by inter-molecular N-H⋯O hydrogen bonds, forming chains along [010].

Related literature

For general background to the applications of aroylthio­ureas in coordination chemistry and mol­ecular electronics, see: Aly et al. (2007 ▶); Koch (2001 ▶); Duque et al. (2009 ▶); Estévez-Hernández et al. (2006 ▶). For related structures, see: Estévez-Hernández et al. (2008 ▶). For the synthesis, see: Otazo-Sánchez et al. (2001 ▶).

Experimental

Crystal data

C12H16N2O2S

M = 252.33

Orthorhombic,

a = 7.2667 (5) Å

b = 10.2058 (7) Å

c = 34.239 (3) Å

V = 2539.3 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.25 mm−1

T = 100 K

0.37 × 0.34 × 0.23 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T min = 0.914, T max = 0.946

30412 measured reflections

2232 independent reflections

2175 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.072

S = 1.20

2232 reflections

160 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013693/bq2204sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013693/bq2204Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H16N2O2S	F(000) = 1072
Mr = 252.33	Dx = 1.32 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9926 reflections
a = 7.2667 (5) Å	θ = 2.9–25.1°
b = 10.2058 (7) Å	µ = 0.25 mm−1
c = 34.239 (3) Å	T = 100 K
V = 2539.3 (3) Å3	Prism, colourless
Z = 8	0.37 × 0.34 × 0.23 mm

Bruker APEXII CCD diffractometer	2232 independent reflections
Radiation source: fine-focus sealed tube	2175 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 8.333 pixels mm-1	θmax = 25.0°, θmin = 2.4°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −12→12
Tmin = 0.914, Tmax = 0.946	l = −40→40
30412 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ2(Fo2) + (0.0145P)2 + 2.5358P] where P = (Fo2 + 2Fc2)/3
2232 reflections	(Δ/σ)max = 0.001
160 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
S1	0.02582 (6)	0.83305 (4)	0.380695 (12)	0.01791 (12)
O1	0.23646 (16)	0.91176 (11)	0.51723 (3)	0.0176 (3)
O2	0.20639 (16)	1.18582 (10)	0.45356 (3)	0.0175 (3)
N1	0.15353 (19)	0.96757 (14)	0.44114 (4)	0.0150 (3)
N2	0.0950 (2)	1.08928 (14)	0.38546 (4)	0.0166 (3)
C1	0.2661 (2)	1.03689 (15)	0.50384 (5)	0.0145 (3)
C2	0.3595 (2)	1.10760 (16)	0.53071 (5)	0.0179 (4)
H2A	0.3978	1.1963	0.5284	0.022*
C3	0.3890 (2)	1.02359 (17)	0.56302 (5)	0.0188 (4)
H3A	0.4499	1.0451	0.5867	0.023*
C4	0.3138 (2)	0.90723 (17)	0.55358 (5)	0.0194 (4)
H4A	0.3145	0.8321	0.57	0.023*
C5	0.2064 (2)	1.07079 (15)	0.46440 (5)	0.0142 (3)
C6	0.0933 (2)	0.97236 (16)	0.40230 (5)	0.0149 (3)
C7	0.0241 (2)	1.11541 (16)	0.34625 (5)	0.0158 (3)
H7A	−0.0859	1.0584	0.3418	0.019*
C8	0.1656 (2)	1.08560 (17)	0.31451 (5)	0.0195 (4)
H8A	0.2762	1.1408	0.3184	0.023*
H8B	0.2035	0.9926	0.3162	0.023*
C9	0.0824 (3)	1.11309 (17)	0.27440 (5)	0.0213 (4)
H9A	−0.023	1.0535	0.2699	0.026*
H9B	0.1756	1.0956	0.254	0.026*
C10	0.0172 (2)	1.25554 (18)	0.27119 (5)	0.0223 (4)
H10A	0.1247	1.3149	0.2726	0.027*
H10B	−0.0434	1.269	0.2456	0.027*
C11	−0.1176 (2)	1.28941 (17)	0.30388 (5)	0.0218 (4)
H11A	−0.2326	1.2389	0.3002	0.026*
H11B	−0.1486	1.3838	0.3025	0.026*
C12	−0.0375 (2)	1.25877 (16)	0.34414 (5)	0.0175 (4)
H12A	−0.1316	1.2756	0.3644	0.021*
H12B	0.0689	1.3168	0.3493	0.021*
H1	0.167 (3)	0.894 (2)	0.4510 (5)	0.021*
H2	0.139 (3)	1.1503 (19)	0.3985 (6)	0.021*

	U11	U22	U33	U12	U13	U23
S1	0.0206 (2)	0.0144 (2)	0.0188 (2)	−0.00266 (17)	−0.00123 (16)	−0.00125 (16)
O1	0.0224 (6)	0.0128 (6)	0.0175 (5)	−0.0014 (5)	−0.0014 (5)	0.0024 (5)
O2	0.0222 (6)	0.0114 (6)	0.0190 (6)	0.0007 (5)	−0.0007 (5)	0.0007 (5)
N1	0.0179 (7)	0.0112 (7)	0.0159 (7)	0.0005 (6)	−0.0013 (6)	0.0024 (6)
N2	0.0196 (7)	0.0143 (7)	0.0158 (7)	−0.0012 (6)	−0.0026 (6)	−0.0005 (6)
C1	0.0139 (8)	0.0112 (8)	0.0185 (8)	0.0022 (6)	0.0037 (7)	0.0011 (6)
C2	0.0188 (8)	0.0137 (8)	0.0213 (8)	0.0013 (7)	0.0014 (7)	−0.0031 (7)
C3	0.0172 (8)	0.0234 (9)	0.0159 (8)	0.0036 (7)	−0.0010 (7)	−0.0028 (7)
C4	0.0219 (9)	0.0221 (9)	0.0141 (8)	0.0032 (7)	−0.0005 (7)	0.0036 (7)
C5	0.0101 (8)	0.0145 (8)	0.0179 (8)	0.0013 (6)	0.0026 (6)	−0.0013 (6)
C6	0.0105 (8)	0.0167 (8)	0.0174 (8)	0.0009 (6)	0.0005 (6)	0.0001 (6)
C7	0.0157 (8)	0.0159 (8)	0.0159 (8)	−0.0002 (7)	−0.0018 (7)	−0.0002 (6)
C8	0.0195 (8)	0.0181 (8)	0.0211 (8)	0.0036 (7)	0.0016 (7)	0.0005 (7)
C9	0.0236 (9)	0.0216 (9)	0.0187 (8)	0.0011 (7)	0.0032 (7)	−0.0021 (7)
C10	0.0257 (9)	0.0244 (9)	0.0169 (8)	0.0026 (8)	−0.0001 (7)	0.0038 (7)
C11	0.0251 (9)	0.0207 (8)	0.0196 (8)	0.0057 (7)	−0.0019 (7)	0.0019 (7)
C12	0.0191 (8)	0.0170 (8)	0.0165 (8)	0.0029 (7)	−0.0002 (7)	−0.0006 (6)

S1—C6	1.6760 (16)	C7—C8	1.527 (2)
O1—C4	1.3665 (19)	C7—C12	1.532 (2)
O1—C1	1.3739 (19)	C7—H7A	1
O2—C5	1.2313 (19)	C8—C9	1.527 (2)
N1—C5	1.376 (2)	C8—H8A	0.99
N1—C6	1.401 (2)	C8—H8B	0.99
N1—H1	0.83 (2)	C9—C10	1.533 (2)
N2—C6	1.325 (2)	C9—H9A	0.99
N2—C7	1.462 (2)	C9—H9B	0.99
N2—H2	0.83 (2)	C10—C11	1.527 (2)
C1—C2	1.352 (2)	C10—H10A	0.99
C1—C5	1.460 (2)	C10—H10B	0.99
C2—C3	1.416 (2)	C11—C12	1.529 (2)
C2—H2A	0.95	C11—H11A	0.99
C3—C4	1.346 (2)	C11—H11B	0.99
C3—H3A	0.95	C12—H12A	0.99
C4—H4A	0.95	C12—H12B	0.99
C4—O1—C1	105.71 (13)	C9—C8—C7	109.70 (14)
C5—N1—C6	127.62 (14)	C9—C8—H8A	109.7
C5—N1—H1	115.0 (13)	C7—C8—H8A	109.7
C6—N1—H1	117.2 (13)	C9—C8—H8B	109.7
C6—N2—C7	124.08 (14)	C7—C8—H8B	109.7
C6—N2—H2	116.5 (13)	H8A—C8—H8B	108.2
C7—N2—H2	119.4 (13)	C8—C9—C10	111.18 (14)
C2—C1—O1	110.36 (14)	C8—C9—H9A	109.4
C2—C1—C5	130.70 (15)	C10—C9—H9A	109.4
O1—C1—C5	118.84 (13)	C8—C9—H9B	109.4
C1—C2—C3	106.52 (15)	C10—C9—H9B	109.4
C1—C2—H2A	126.7	H9A—C9—H9B	108
C3—C2—H2A	126.7	C11—C10—C9	111.13 (14)
C4—C3—C2	106.57 (15)	C11—C10—H10A	109.4
C4—C3—H3A	126.7	C9—C10—H10A	109.4
C2—C3—H3A	126.7	C11—C10—H10B	109.4
C3—C4—O1	110.83 (15)	C9—C10—H10B	109.4
C3—C4—H4A	124.6	H10A—C10—H10B	108
O1—C4—H4A	124.6	C10—C11—C12	111.76 (14)
O2—C5—N1	123.74 (15)	C10—C11—H11A	109.3
O2—C5—C1	120.34 (14)	C12—C11—H11A	109.3
N1—C5—C1	115.92 (14)	C10—C11—H11B	109.3
N2—C6—N1	116.20 (14)	C12—C11—H11B	109.3
N2—C6—S1	125.06 (12)	H11A—C11—H11B	107.9
N1—C6—S1	118.74 (12)	C11—C12—C7	110.44 (13)
N2—C7—C8	112.33 (13)	C11—C12—H12A	109.6
N2—C7—C12	108.69 (13)	C7—C12—H12A	109.6
C8—C7—C12	110.71 (13)	C11—C12—H12B	109.6
N2—C7—H7A	108.3	C7—C12—H12B	109.6
C8—C7—H7A	108.3	H12A—C12—H12B	108.1
C12—C7—H7A	108.3
C4—O1—C1—C2	0.37 (17)	C7—N2—C6—S1	5.0 (2)
C4—O1—C1—C5	177.02 (14)	C5—N1—C6—N2	3.2 (2)
O1—C1—C2—C3	−0.65 (18)	C5—N1—C6—S1	−176.93 (13)
C5—C1—C2—C3	−176.78 (16)	C6—N2—C7—C8	−84.29 (19)
C1—C2—C3—C4	0.68 (19)	C6—N2—C7—C12	152.86 (15)
C2—C3—C4—O1	−0.47 (19)	N2—C7—C8—C9	179.24 (14)
C1—O1—C4—C3	0.08 (18)	C12—C7—C8—C9	−59.05 (18)
C6—N1—C5—O2	0.4 (3)	C7—C8—C9—C10	57.79 (19)
C6—N1—C5—C1	−179.07 (15)	C8—C9—C10—C11	−55.4 (2)
C2—C1—C5—O2	−14.7 (3)	C9—C10—C11—C12	53.9 (2)
O1—C1—C5—O2	169.45 (14)	C10—C11—C12—C7	−55.05 (19)
C2—C1—C5—N1	164.83 (17)	N2—C7—C12—C11	−178.47 (13)
O1—C1—C5—N1	−11.0 (2)	C8—C7—C12—C11	57.71 (18)
C7—N2—C6—N1	−175.11 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.83 (2)	2.329 (19)	2.7342 (17)	110.8 (16)
N1—H1···O2i	0.83 (2)	2.32 (2)	3.0799 (18)	153.0 (18)
N2—H2···O2	0.83 (2)	1.983 (19)	2.6574 (18)	138.0 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.83 (2)	2.329 (19)	2.7342 (17)	110.8 (16)
N1—H1⋯O2i	0.83 (2)	2.32 (2)	3.0799 (18)	153.0 (18)
N2—H2⋯O2	0.83 (2)	1.983 (19)	2.6574 (18)	138.0 (18)

Symmetry code: (i) .