N-Cyclo-hexyl-N'-(4-nitro-benzo-yl)thio-urea.

In the title compound, C(14)H(17)N(3)O(3)S, the nitro group is twisted slightly by 2.6 (3)° from the benzene ring plane and the thio-ureido group makes a dihedral angle of 52.06 (4)° with the benzene ring. The cyclo-hexyl ring displays a chair conformation. An intra-molecular N-H⋯O inter-action is present. In the crystal, inter-molecular N-H⋯S hydrogen bonds link the mol-ecules into centrosymmetric dimers. π-π inter-actions between inversion-related benzene rings (centroid-centroid distance = 4.044 Å) and C-H⋯π inter-actions (H⋯centroid distance = 3.116 Å) between one methyl-ene cyclo-hexyl H atom and the benzene ring are also present.

Related literature

For general background to the chemistry and biological activity of thio­urea derivatives and their use as organic synthons or as complexing agents, see: Glasser & Doughty (1964 ▶); Jain & Rao (2003 ▶); Zeng et al. (2003 ▶); Xu et al. (2004 ▶); Zheng et al. (2004 ▶); D’hooghe et al. (2005 ▶); Saeed et al. (2008 ▶, 2009 ▶, 2010 ▶).

Experimental

Crystal data

C14H17N3O3S

M = 307.37

Monoclinic,

a = 10.7865 (7) Å

b = 6.9218 (4) Å

c = 20.6788 (13) Å

β = 101.493 (1)°

V = 1512.96 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 294 K

0.43 × 0.32 × 0.26 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.909, T max = 0.943

10042 measured reflections

3683 independent reflections

3177 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.108

S = 1.04

3683 reflections

200 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810012249/bh2277sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012249/bh2277Isup2.hkl

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

C14H17N3O3S	F(000) = 648
Mr = 307.37	Dx = 1.349 Mg m−3
Monoclinic, P21/c	Melting point: 389 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.7865 (7) Å	Cell parameters from 10042 reflections
b = 6.9218 (4) Å	θ = 1.9–28.3°
c = 20.6788 (13) Å	µ = 0.23 mm−1
β = 101.493 (1)°	T = 294 K
V = 1512.96 (16) Å3	Block, yellow
Z = 4	0.43 × 0.32 × 0.26 mm

Bruker SMART 1000 CCD diffractometer	3683 independent reflections
Radiation source: fine-focus sealed tube	3177 reflections with I > 2σ(I)
graphite	Rint = 0.017
ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
Tmin = 0.909, Tmax = 0.943	k = −9→5
10042 measured reflections	l = −27→21

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.108	w = 1/[σ2(Fo2) + (0.057P)2 + 0.3039P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.002
3683 reflections	Δρmax = 0.25 e Å−3
200 parameters	Δρmin = −0.20 e Å−3
0 restraints	Extinction correction: SAINT (Bruker, 2006), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.0071 (14)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
S1	1.03975 (3)	0.73010 (6)	0.436999 (18)	0.05209 (13)
O1	0.47704 (13)	0.08216 (19)	0.65091 (7)	0.0781 (4)
O2	0.44185 (17)	0.3242 (2)	0.70892 (8)	0.1000 (5)
O3	0.67743 (10)	0.91616 (15)	0.49838 (6)	0.0595 (3)
N1	0.48457 (12)	0.2530 (2)	0.66423 (7)	0.0597 (3)
N2	0.83598 (10)	0.70331 (17)	0.49038 (5)	0.0439 (2)
N3	0.83313 (11)	0.94898 (16)	0.41468 (6)	0.0474 (3)
C1	0.55199 (11)	0.3817 (2)	0.62577 (6)	0.0469 (3)
C2	0.56593 (15)	0.5738 (2)	0.64356 (7)	0.0554 (3)
H2	0.5347	0.6211	0.6792	0.066*
C3	0.62757 (15)	0.6938 (2)	0.60694 (7)	0.0543 (3)
H3	0.6368	0.8244	0.6174	0.065*
C4	0.67605 (11)	0.61980 (19)	0.55443 (6)	0.0429 (3)
C5	0.66178 (11)	0.42564 (19)	0.53834 (6)	0.0437 (3)
H5	0.6951	0.3766	0.5035	0.052*
C6	0.59808 (12)	0.30409 (19)	0.57394 (7)	0.0461 (3)
H6	0.5868	0.1740	0.5631	0.055*
C7	0.72985 (13)	0.76095 (18)	0.51229 (6)	0.0440 (3)
C8	0.89672 (11)	0.80319 (18)	0.44630 (6)	0.0404 (3)
C9	0.87497 (12)	1.07460 (18)	0.36608 (6)	0.0450 (3)
H9	0.9669	1.0915	0.3785	0.054*
C10	0.81166 (18)	1.2697 (2)	0.36788 (8)	0.0581 (4)
H10A	0.8380	1.3263	0.4114	0.070*
H10B	0.7206	1.2526	0.3598	0.070*
C11	0.84568 (19)	1.4059 (2)	0.31634 (8)	0.0675 (4)
H11A	0.7997	1.5262	0.3168	0.081*
H11B	0.9354	1.4348	0.3275	0.081*
C12	0.81434 (18)	1.3191 (3)	0.24797 (8)	0.0660 (4)
H12A	0.7234	1.3052	0.2346	0.079*
H12B	0.8429	1.4054	0.2170	0.079*
C13	0.87599 (18)	1.1253 (3)	0.24606 (8)	0.0650 (4)
H13A	0.9671	1.1419	0.2539	0.078*
H13B	0.8492	1.0695	0.2025	0.078*
C14	0.84263 (16)	0.9873 (2)	0.29742 (7)	0.0567 (4)
H14A	0.7529	0.9581	0.2866	0.068*
H14B	0.8888	0.8673	0.2967	0.068*
H2N	0.8739 (16)	0.605 (3)	0.5076 (8)	0.056 (4)*
H3N	0.7671 (16)	0.977 (2)	0.4261 (8)	0.054 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.04215 (19)	0.0602 (2)	0.0569 (2)	0.00659 (13)	0.01688 (14)	0.01451 (15)
O1	0.0819 (8)	0.0661 (8)	0.0935 (9)	−0.0121 (6)	0.0350 (7)	0.0161 (7)
O2	0.1244 (13)	0.0977 (10)	0.1022 (10)	−0.0046 (9)	0.0809 (10)	0.0102 (8)
O3	0.0656 (6)	0.0483 (5)	0.0731 (7)	0.0133 (5)	0.0342 (5)	0.0136 (5)
N1	0.0497 (7)	0.0726 (9)	0.0615 (7)	0.0012 (6)	0.0222 (6)	0.0175 (6)
N2	0.0459 (5)	0.0424 (6)	0.0467 (6)	0.0050 (4)	0.0169 (4)	0.0081 (4)
N3	0.0476 (6)	0.0455 (6)	0.0535 (6)	0.0053 (5)	0.0207 (5)	0.0107 (5)
C1	0.0406 (6)	0.0552 (7)	0.0471 (6)	0.0039 (5)	0.0143 (5)	0.0114 (6)
C2	0.0654 (8)	0.0587 (8)	0.0488 (7)	0.0079 (7)	0.0275 (6)	0.0022 (6)
C3	0.0688 (9)	0.0463 (7)	0.0536 (7)	0.0041 (6)	0.0261 (7)	−0.0004 (6)
C4	0.0429 (6)	0.0454 (6)	0.0426 (6)	0.0039 (5)	0.0139 (5)	0.0048 (5)
C5	0.0419 (6)	0.0474 (7)	0.0448 (6)	0.0050 (5)	0.0161 (5)	0.0005 (5)
C6	0.0424 (6)	0.0444 (6)	0.0531 (7)	0.0024 (5)	0.0136 (5)	0.0039 (5)
C7	0.0475 (6)	0.0434 (6)	0.0439 (6)	0.0018 (5)	0.0159 (5)	0.0026 (5)
C8	0.0424 (6)	0.0409 (6)	0.0391 (6)	−0.0020 (5)	0.0105 (5)	0.0002 (5)
C9	0.0463 (6)	0.0417 (6)	0.0494 (7)	−0.0014 (5)	0.0154 (5)	0.0079 (5)
C10	0.0789 (10)	0.0421 (7)	0.0566 (8)	0.0046 (6)	0.0211 (7)	0.0018 (6)
C11	0.0914 (12)	0.0421 (7)	0.0679 (10)	−0.0033 (8)	0.0134 (8)	0.0105 (7)
C12	0.0729 (10)	0.0653 (10)	0.0565 (8)	−0.0053 (8)	0.0048 (7)	0.0172 (7)
C13	0.0809 (10)	0.0681 (10)	0.0510 (8)	−0.0059 (8)	0.0253 (7)	0.0041 (7)
C14	0.0738 (9)	0.0459 (7)	0.0563 (8)	−0.0025 (6)	0.0269 (7)	−0.0018 (6)

S1—C8	1.6707 (13)	C5—H5	0.9300
O1—N1	1.2132 (19)	C6—H6	0.9300
O2—N1	1.2162 (19)	C9—C10	1.5173 (19)
O3—C7	1.2213 (15)	C9—C14	1.518 (2)
N1—C1	1.4785 (17)	C9—H9	0.9800
N2—C7	1.3717 (16)	C10—C11	1.521 (2)
N2—C8	1.4058 (16)	C10—H10A	0.9700
N2—H2N	0.835 (18)	C10—H10B	0.9700
N3—C8	1.3182 (16)	C11—C12	1.511 (2)
N3—C9	1.4665 (15)	C11—H11A	0.9700
N3—H3N	0.817 (17)	C11—H11B	0.9700
C1—C6	1.3774 (18)	C12—C13	1.501 (3)
C1—C2	1.379 (2)	C12—H12A	0.9700
C2—C3	1.380 (2)	C12—H12B	0.9700
C2—H2	0.9300	C13—C14	1.524 (2)
C3—C4	1.3932 (17)	C13—H13A	0.9700
C3—H3	0.9300	C13—H13B	0.9700
C4—C5	1.3857 (18)	C14—H14A	0.9700
C4—C7	1.5008 (17)	C14—H14B	0.9700
C5—C6	1.3869 (17)
O1—N1—O2	123.31 (14)	C10—C9—C14	110.89 (12)
O1—N1—C1	118.89 (13)	N3—C9—H9	108.9
O2—N1—C1	117.78 (15)	C10—C9—H9	108.9
C7—N2—C8	126.77 (11)	C14—C9—H9	108.9
C7—N2—H2N	117.8 (12)	C9—C10—C11	111.20 (13)
C8—N2—H2N	115.1 (12)	C9—C10—H10A	109.4
C8—N3—C9	126.38 (11)	C11—C10—H10A	109.4
C8—N3—H3N	115.9 (11)	C9—C10—H10B	109.4
C9—N3—H3N	117.4 (11)	C11—C10—H10B	109.4
C6—C1—C2	123.12 (12)	H10A—C10—H10B	108.0
C6—C1—N1	118.42 (13)	C12—C11—C10	111.65 (13)
C2—C1—N1	118.46 (12)	C12—C11—H11A	109.3
C1—C2—C3	118.19 (12)	C10—C11—H11A	109.3
C1—C2—H2	120.9	C12—C11—H11B	109.3
C3—C2—H2	120.9	C10—C11—H11B	109.3
C2—C3—C4	120.20 (13)	H11A—C11—H11B	108.0
C2—C3—H3	119.9	C13—C12—C11	111.23 (14)
C4—C3—H3	119.9	C13—C12—H12A	109.4
C5—C4—C3	120.17 (12)	C11—C12—H12A	109.4
C5—C4—C7	121.95 (11)	C13—C12—H12B	109.4
C3—C4—C7	117.52 (12)	C11—C12—H12B	109.4
C4—C5—C6	120.26 (12)	H12A—C12—H12B	108.0
C4—C5—H5	119.9	C12—C13—C14	111.98 (13)
C6—C5—H5	119.9	C12—C13—H13A	109.2
C1—C6—C5	118.04 (12)	C14—C13—H13A	109.2
C1—C6—H6	121.0	C12—C13—H13B	109.2
C5—C6—H6	121.0	C14—C13—H13B	109.2
O3—C7—N2	123.77 (12)	H13A—C13—H13B	107.9
O3—C7—C4	119.66 (11)	C9—C14—C13	111.10 (12)
N2—C7—C4	116.56 (11)	C9—C14—H14A	109.4
N3—C8—N2	115.75 (11)	C13—C14—H14A	109.4
N3—C8—S1	125.16 (10)	C9—C14—H14B	109.4
N2—C8—S1	119.09 (9)	C13—C14—H14B	109.4
N3—C9—C10	108.03 (11)	H14A—C14—H14B	108.0
N3—C9—C14	111.11 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O3	0.817 (17)	1.981 (17)	2.6507 (17)	138.8 (14)
N2—H2N···S1i	0.84 (2)	2.67 (2)	3.4999 (12)	171.3 (16)
C6—H6···O3ii	0.93	2.54	3.3041 (17)	140
C9—H9···S1	0.98	2.82	3.1555 (13)	101

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O3	0.817 (17)	1.981 (17)	2.6507 (17)	138.8 (14)
N2—H2N⋯S1i	0.84 (2)	2.67 (2)	3.4999 (12)	171.3 (16)

Symmetry code: (i) .