1-(2-Chloro-5-nitro-phen-yl)-3-(2,2-di-methyl-propion-yl)thio-urea.

With the exception of the C atoms of two of the methyl groups of the tert-butyl substituent, all of the non-H atoms of the title compound, C(12)H(14)ClN(3)O(3)S, lie on a mirror plane. The 2-chloro-5-nitro-phenyl and 2,2-dimethyl-propionyl substituents are, respectively, cis and trans relative to the thio-carbonyl S atom across the two C-N bonds. Intra-molecular N-H⋯O and C-H⋯S hydrogen bonds form S(6) ring motifs, also in the mirror plane. Despite the presence of two N-H subsituents, no inter-molecular hydrogen bonds are observed in the crystal structure. Weak π-π contacts [centroid-centroid distances of 4.2903 (17) Å] involving adjacent aromatic rings link the mol-ecules in a head-to-tail fashion above and below the mol-ecular plane.

Related literature

For the use of thio­urea derivatives in organic synthesis, see: Eynde & Watte (2003 ▶); Fu et al. (1999 ▶); Rashdan et al. (2006 ▶); Maryanoff et al. (1986 ▶); Wang et al. (2005 ▶); Saeed et al. (2008 ▶); and in analysis, see: Koch (2001 ▶). For their bioactivity and pharmaceutical applications, see: Upadhyaya & Srivastava (1982 ▶); Krishnamurthy et al. (1999 ▶); Blum & Hayes (1979 ▶); DeBeer et al. (1936 ▶). For related structures, see: Saeed & Flörke (2007a ▶,b ▶); Yusof et al. (2006 ▶, 2008 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C12H14ClN3O3S

M = 315.77

Orthorhombic,

a = 9.529 (2) Å

b = 6.546 (2) Å

c = 22.166 (6) Å

V = 1382.7 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.44 mm−1

T = 89 K

0.36 × 0.09 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.833, T max = 0.974

12525 measured reflections

1434 independent reflections

1166 reflections with I > 2σ(I)

R int = 0.069

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.092

S = 1.09

1434 reflections

130 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2 and SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024672/lh2851sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024672/lh2851Isup2.hkl

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

C12H14ClN3O3S	F(000) = 656
Mr = 315.77	Dx = 1.517 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2410 reflections
a = 9.529 (2) Å	θ = 2.3–24.6°
b = 6.546 (2) Å	µ = 0.44 mm−1
c = 22.166 (6) Å	T = 89 K
V = 1382.7 (7) Å3	Needle, colourless
Z = 4	0.36 × 0.09 × 0.06 mm

Bruker APEXII CCD area-detector diffractometer	1434 independent reflections
Radiation source: fine-focus sealed tube	1166 reflections with I > 2σ(I)
graphite	Rint = 0.069
ω scans	θmax = 25.7°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −11→11
Tmin = 0.833, Tmax = 0.974	k = −6→8
12525 measured reflections	l = −26→26

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) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0461P)2 + 0.3426P] where P = (Fo2 + 2Fc2)/3
1434 reflections	(Δ/σ)max < 0.001
130 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.1946 (3)	0.2500	0.36075 (12)	0.0163 (6)
O1	0.3187 (2)	0.2500	0.34713 (8)	0.0217 (5)
N1	0.1523 (3)	0.2500	0.42088 (10)	0.0184 (5)
H1N	0.070 (4)	0.2500	0.4268 (16)	0.037 (11)*
C2	0.2314 (3)	0.2500	0.47417 (11)	0.0143 (6)
S1	0.14289 (7)	0.2500	0.53901 (3)	0.0192 (2)
N2	0.3713 (2)	0.2500	0.46466 (10)	0.0143 (5)
H2N	0.397 (3)	0.2500	0.4222 (15)	0.030 (9)*
C4	0.4846 (3)	0.2500	0.50580 (12)	0.0130 (6)
C5	0.6210 (3)	0.2500	0.48174 (11)	0.0147 (6)
Cl1	0.64439 (7)	0.2500	0.40389 (3)	0.0181 (2)
C6	0.7399 (3)	0.2500	0.51801 (12)	0.0168 (6)
H6	0.8305	0.2500	0.5002	0.020*
C7	0.7261 (3)	0.2500	0.58025 (12)	0.0183 (6)
H7	0.8060	0.2500	0.6059	0.022*
C8	0.5911 (3)	0.2500	0.60368 (11)	0.0167 (6)
N3	0.5743 (3)	0.2500	0.67027 (10)	0.0204 (5)
O2	0.6808 (2)	0.2500	0.70124 (9)	0.0286 (5)
O3	0.4544 (2)	0.2500	0.69074 (9)	0.0317 (6)
C9	0.4711 (3)	0.2500	0.56877 (11)	0.0147 (6)
H9	0.3810	0.2500	0.5871	0.018*
C10	0.0727 (3)	0.2500	0.31561 (11)	0.0170 (6)
C11	0.1330 (3)	0.2500	0.25185 (13)	0.0308 (8)
H11A	0.059 (4)	0.2500	0.2261 (16)	0.037*
H11B	0.188 (2)	0.132 (3)	0.2442 (10)	0.037*
C12	−0.0158 (2)	0.0571 (3)	0.32488 (9)	0.0229 (5)
H12A	−0.0897	0.0515	0.2942	0.034*
H12B	−0.0585	0.0602	0.3651	0.034*
H12C	0.0442	−0.0638	0.3213	0.034*

	U11	U22	U33	U12	U13	U23
C1	0.0149 (14)	0.0200 (15)	0.0142 (14)	0.000	−0.0001 (11)	0.000
O1	0.0135 (10)	0.0360 (12)	0.0155 (9)	0.000	0.0018 (8)	0.000
N1	0.0109 (13)	0.0317 (14)	0.0125 (11)	0.000	0.0003 (10)	0.000
C2	0.0129 (13)	0.0185 (14)	0.0113 (13)	0.000	−0.0021 (10)	0.000
S1	0.0149 (4)	0.0307 (4)	0.0121 (3)	0.000	0.0020 (3)	0.000
N2	0.0124 (12)	0.0196 (12)	0.0110 (11)	0.000	−0.0008 (9)	0.000
C4	0.0134 (13)	0.0108 (13)	0.0146 (13)	0.000	−0.0025 (10)	0.000
C5	0.0183 (14)	0.0129 (13)	0.0128 (13)	0.000	−0.0007 (11)	0.000
Cl1	0.0149 (4)	0.0262 (4)	0.0132 (3)	0.000	0.0020 (2)	0.000
C6	0.0128 (14)	0.0169 (14)	0.0209 (14)	0.000	0.0010 (11)	0.000
C7	0.0190 (15)	0.0148 (14)	0.0210 (14)	0.000	−0.0057 (12)	0.000
C8	0.0213 (15)	0.0150 (14)	0.0139 (13)	0.000	−0.0018 (11)	0.000
N3	0.0258 (14)	0.0213 (13)	0.0142 (12)	0.000	−0.0011 (10)	0.000
O2	0.0284 (12)	0.0391 (13)	0.0182 (10)	0.000	−0.0114 (9)	0.000
O3	0.0266 (12)	0.0527 (15)	0.0157 (10)	0.000	0.0031 (9)	0.000
C9	0.0165 (14)	0.0122 (13)	0.0154 (13)	0.000	−0.0002 (11)	0.000
C10	0.0147 (14)	0.0258 (15)	0.0104 (13)	0.000	−0.0018 (11)	0.000
C11	0.0193 (17)	0.062 (2)	0.0115 (14)	0.000	−0.0013 (13)	0.000
C12	0.0222 (11)	0.0220 (11)	0.0245 (10)	0.0000 (9)	−0.0078 (8)	−0.0021 (9)

C1—O1	1.221 (3)	C7—C8	1.387 (4)
C1—N1	1.392 (3)	C7—H7	0.9500
C1—C10	1.533 (4)	C8—C9	1.380 (4)
N1—C2	1.401 (3)	C8—N3	1.485 (3)
N1—H1N	0.80 (4)	N3—O2	1.226 (3)
C2—N2	1.349 (3)	N3—O3	1.229 (3)
C2—S1	1.667 (3)	C9—H9	0.9500
N2—C4	1.414 (3)	C10—C11	1.526 (4)
N2—H2N	0.97 (3)	C10—C12	1.533 (3)
C4—C9	1.402 (3)	C10—C12i	1.533 (3)
C4—C5	1.405 (4)	C11—H11A	0.91 (4)
C5—C6	1.389 (4)	C11—H11B	0.95 (2)
C5—Cl1	1.740 (3)	C12—H12A	0.9800
C6—C7	1.386 (4)	C12—H12B	0.9800
C6—H6	0.9500	C12—H12C	0.9800
O1—C1—N1	121.1 (2)	C9—C8—C7	123.9 (2)
O1—C1—C10	124.9 (2)	C9—C8—N3	117.9 (2)
N1—C1—C10	113.9 (2)	C7—C8—N3	118.2 (2)
C1—N1—C2	130.6 (2)	O2—N3—O3	124.3 (2)
C1—N1—H1N	116 (3)	O2—N3—C8	117.9 (2)
C2—N1—H1N	113 (3)	O3—N3—C8	117.8 (2)
N2—C2—N1	113.6 (2)	C8—C9—C4	118.8 (2)
N2—C2—S1	129.4 (2)	C8—C9—H9	120.6
N1—C2—S1	117.0 (2)	C4—C9—H9	120.6
C2—N2—C4	130.8 (2)	C11—C10—C12	109.35 (14)
C2—N2—H2N	113.7 (19)	C11—C10—C12i	109.35 (14)
C4—N2—H2N	115.5 (19)	C12—C10—C12i	111.0 (2)
C9—C4—C5	117.6 (2)	C11—C10—C1	108.6 (2)
C9—C4—N2	124.9 (2)	C12—C10—C1	109.25 (14)
C5—C4—N2	117.5 (2)	C12i—C10—C1	109.25 (14)
C6—C5—C4	122.3 (2)	C10—C11—H11A	107 (2)
C6—C5—Cl1	118.0 (2)	C10—C11—H11B	111.9 (14)
C4—C5—Cl1	119.7 (2)	H11A—C11—H11B	108.5 (18)
C7—C6—C5	119.9 (2)	C10—C12—H12A	109.5
C7—C6—H6	120.0	C10—C12—H12B	109.5
C5—C6—H6	120.0	H12A—C12—H12B	109.5
C6—C7—C8	117.4 (2)	C10—C12—H12C	109.5
C6—C7—H7	121.3	H12A—C12—H12C	109.5
C8—C7—H7	121.3	H12B—C12—H12C	109.5
O1—C1—N1—C2	0.0	C6—C7—C8—N3	180.0
C10—C1—N1—C2	180.0	C9—C8—N3—O2	180.0
C1—N1—C2—N2	0.0	C7—C8—N3—O2	0.000 (1)
C1—N1—C2—S1	180.0	C9—C8—N3—O3	0.000 (1)
N1—C2—N2—C4	180.0	C7—C8—N3—O3	180.0
S1—C2—N2—C4	0.000 (1)	C7—C8—C9—C4	0.000 (1)
C2—N2—C4—C9	0.000 (1)	N3—C8—C9—C4	180.0
C2—N2—C4—C5	180.0	C5—C4—C9—C8	0.000 (1)
C9—C4—C5—C6	0.0	N2—C4—C9—C8	180.0
N2—C4—C5—C6	180.0	O1—C1—C10—C11	0.0
C9—C4—C5—Cl1	180.0	N1—C1—C10—C11	180.0
N2—C4—C5—Cl1	0.0	O1—C1—C10—C12	119.21 (15)
C4—C5—C6—C7	0.000 (1)	N1—C1—C10—C12	−60.79 (15)
Cl1—C5—C6—C7	180.0	O1—C1—C10—C12i	−119.21 (15)
C5—C6—C7—C8	0.000 (1)	N1—C1—C10—C12i	60.79 (15)
C6—C7—C8—C9	0.000 (1)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···S1	0.95	2.51	3.197 (3)	130
N2—H2N···O1	0.97 (3)	1.82 (3)	2.653 (3)	141 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯S1	0.95	2.51	3.197 (3)	130
N2—H2N⋯O1	0.97 (3)	1.82 (3)	2.653 (3)	141 (3)