1-(4-Bromo-phen-yl)-1-(4-nitro-benzo-yl)thio-urea.

The title compound, C(14)H(10)BrN(3)O(3)S, crystallizes as two concomitant polymorphs that differ in colour (one yellow and one colourless). Only the structure of the colourless form could be determined. The mol-ecule exists in the thio-amide form with an intra-molecular N-H⋯O=C hydrogen bond across the thio-urea system. Mol-ecules are linked into layers parallel to (120) by Br⋯O(nitro) contacts [3.103 (1) Å], classical hydrogen bonds from the other NH function to the S atom and N(nitro)⋯O=C contacts. The layers are linked by weak C-H⋯O(nitro) hydrogen bonds to produce the observed three-dimensional network.

Related literature

For general background to thio­urea complexe, see: Ugur et al. (2006 ▶). For the biological activity of thio­urea derivatives, see: Glasser & Doughty (1964 ▶); Huebner et al. (1953 ▶); Manjula et al. (2009 ▶); Zheng et al. (2004 ▶). For related structures, see: Saeed et al. (2008a ▶,b ▶,c ▶).

Experimental

Crystal data

C14H10BrN3O3S

M = 380.22

Triclinic,

a = 7.0112 (3) Å

b = 8.9697 (5) Å

c = 11.9693 (6) Å

α = 87.386 (5)°

β = 75.044 (4)°

γ = 87.511 (4)°

V = 726.08 (6) Å3

Z = 2

Mo Kα radiation

μ = 2.99 mm−1

T = 100 K

0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T min = 0.945, T max = 1.000 (expected range = 0.520–0.550)

24890 measured reflections

4234 independent reflections

3438 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.051

S = 0.96

4234 reflections

207 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.81 e Å−3

Δρmin = −0.80 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025884/im2125sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025884/im2125Isup2.hkl

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

C14H10BrN3O3S	Z = 2
Mr = 380.22	F(000) = 380
Triclinic, P1	Dx = 1.739 Mg m−3
Hall symbol: -P 1	Melting point: 454 K
a = 7.0112 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9697 (5) Å	Cell parameters from 13461 reflections
c = 11.9693 (6) Å	θ = 2.3–31.7°
α = 87.386 (5)°	µ = 2.99 mm−1
β = 75.044 (4)°	T = 100 K
γ = 87.511 (4)°	Block, colourless
V = 726.08 (6) Å3	0.3 × 0.2 × 0.2 mm

Oxford Diffraction Xcalibur Eos diffractometer	4234 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3438 reflections with I > 2σ(I)
graphite	Rint = 0.025
Detector resolution: 16.1419 pixels mm-1	θmax = 30.0°, θmin = 2.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −12→12
Tmin = 0.945, Tmax = 1.000	l = −16→16
24890 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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ2(Fo2) + (0.0305P)2] where P = (Fo2 + 2Fc2)/3
4234 reflections	(Δ/σ)max = 0.002
207 parameters	Δρmax = 0.81 e Å−3
2 restraints	Δρmin = −0.79 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.=============================================================================Short contacts:3.1027 (0.0010) Br - O2_$5 2.9569 (0.0014) N3 - O1_$6176.07 (0.05) C4 - Br - O2_$5 117.45 (0.08) Br - O2_$5 - N3_$5 88.60 (0.07) C12 - N3 - O1_$6 133.52 (0.08) N3 - O1_$6 - C8_$6Operators for generating equivalent atoms: $5 x - 2, y + 1, z + 1 $6 - x + 1, -y + 1, -z=============================================================================Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)0.3935 (0.0035) x + 6.9720 (0.0023) y - 6.7731 (0.0052) z = 1.9340 (0.0046)* -0.0103 (0.0010) C1 * -0.0015 (0.0010) C2 * 0.0088 (0.0011) C3 * 0.0055 (0.0012) C4 * 0.0052 (0.0011) C5 * 0.0019 (0.0010) C6 * -0.0096 (0.0006) BrRms deviation of fitted atoms = 0.00694.0311 (0.0033) x + 7.2756 (0.0034) y - 0.4894 (0.0028) z = 5.0905 (0.0022)Angle to previous plane (with approximate e.s.d.) = 38.42 (0.04)* 0.0108 (0.0009) C8 * -0.1154 (0.0007) O1 * 0.1064 (0.0009) N2 * 0.0391 (0.0010) C7 * -0.1107 (0.0006) S * 0.0699 (0.0006) N1Rms deviation of fitted atoms = 0.0851- 1.1638 (0.0036) x + 5.3585 (0.0037) y - 9.2611 (0.0039) z = 0.3293 (0.0031)Angle to previous plane (with approximate e.s.d.) = 56.27 (0.04)* -0.0141 (0.0009) C9 * 0.0107 (0.0009) C10 * 0.0018 (0.0009) C11 * -0.0108 (0.0009) C12 * 0.0072 (0.0009) C13 * 0.0053 (0.0009) C14Rms deviation of fitted atoms = 0.00921.5803 (0.0099) x - 4.5675 (0.0126) y + 10.0071 (0.0113) z = 0.2418 (0.0080)Angle to previous plane (with approximate e.s.d.) = 6.52 (0.17)* 0.0000 (0.0000) N3 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) O3Rms deviation of fitted atoms = 0.0000

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
S	0.23307 (5)	0.59552 (4)	0.59750 (3)	0.01794 (7)
Br	−0.60756 (2)	1.070560 (16)	0.782568 (13)	0.02754 (5)
O1	0.14426 (13)	0.61950 (11)	0.23224 (8)	0.0212 (2)
O2	1.06603 (14)	0.23725 (12)	−0.03589 (9)	0.0267 (2)
O3	0.84622 (15)	0.09309 (11)	−0.06698 (9)	0.0266 (2)
N1	0.03832 (16)	0.71824 (12)	0.44897 (10)	0.0159 (2)
H01	0.015 (2)	0.7119 (19)	0.3861 (13)	0.030 (5)*
N2	0.31103 (16)	0.56699 (12)	0.37204 (9)	0.0152 (2)
H02	0.4011 (19)	0.5244 (16)	0.3860 (13)	0.015 (4)*
N3	0.89393 (17)	0.20238 (13)	−0.02463 (9)	0.0190 (2)
C1	−0.10821 (18)	0.79834 (14)	0.53147 (11)	0.0151 (3)
C2	−0.3000 (2)	0.79948 (15)	0.52021 (13)	0.0220 (3)
H2	−0.3305	0.7441	0.4616	0.026*
C3	−0.4475 (2)	0.88188 (16)	0.59493 (14)	0.0259 (3)
H3	−0.5792	0.8833	0.5874	0.031*
C4	−0.4023 (2)	0.96140 (15)	0.67991 (12)	0.0205 (3)
C5	−0.2115 (2)	0.96202 (15)	0.69167 (12)	0.0217 (3)
H5	−0.1817	1.0176	0.7503	0.026*
C6	−0.0636 (2)	0.88033 (15)	0.61667 (12)	0.0199 (3)
H6	0.0683	0.8805	0.6237	0.024*
C7	0.18736 (18)	0.63277 (14)	0.46887 (11)	0.0143 (2)
C8	0.28512 (19)	0.56083 (14)	0.26223 (11)	0.0159 (3)
C9	0.44489 (18)	0.47137 (14)	0.18279 (10)	0.0146 (2)
C10	0.39423 (19)	0.35787 (15)	0.12081 (11)	0.0180 (3)
H10	0.2593	0.3415	0.1258	0.022*
C11	0.5409 (2)	0.26914 (15)	0.05200 (11)	0.0181 (3)
H11	0.5087	0.1905	0.0103	0.022*
C12	0.73630 (19)	0.29840 (14)	0.04574 (11)	0.0160 (3)
C13	0.79035 (19)	0.41304 (14)	0.10333 (11)	0.0157 (3)
H13	0.9256	0.4315	0.0956	0.019*
C14	0.64264 (19)	0.50033 (14)	0.17260 (11)	0.0154 (3)
H14	0.6760	0.5798	0.2131	0.018*

	U11	U22	U33	U12	U13	U23
S	0.01960 (16)	0.02092 (16)	0.01264 (15)	0.00527 (13)	−0.00323 (12)	−0.00443 (12)
Br	0.02540 (8)	0.02009 (8)	0.02847 (8)	0.00880 (5)	0.00799 (6)	−0.00562 (6)
O1	0.0190 (5)	0.0291 (5)	0.0137 (4)	0.0107 (4)	−0.0025 (4)	−0.0006 (4)
O2	0.0192 (5)	0.0311 (6)	0.0256 (5)	0.0075 (4)	0.0012 (4)	−0.0064 (4)
O3	0.0329 (6)	0.0246 (5)	0.0218 (5)	0.0078 (4)	−0.0055 (4)	−0.0115 (4)
N1	0.0155 (5)	0.0186 (5)	0.0125 (5)	0.0045 (4)	−0.0019 (4)	−0.0041 (4)
N2	0.0139 (5)	0.0178 (5)	0.0127 (5)	0.0066 (4)	−0.0019 (4)	−0.0021 (4)
N3	0.0230 (6)	0.0211 (6)	0.0111 (5)	0.0081 (5)	−0.0022 (4)	−0.0024 (4)
C1	0.0143 (6)	0.0139 (6)	0.0139 (6)	0.0031 (5)	0.0016 (5)	−0.0022 (5)
C2	0.0184 (7)	0.0199 (7)	0.0282 (8)	0.0044 (5)	−0.0060 (6)	−0.0106 (6)
C3	0.0143 (7)	0.0210 (7)	0.0409 (9)	0.0034 (5)	−0.0035 (6)	−0.0112 (6)
C4	0.0198 (7)	0.0134 (6)	0.0216 (7)	0.0039 (5)	0.0066 (5)	−0.0024 (5)
C5	0.0259 (7)	0.0191 (7)	0.0194 (7)	0.0051 (6)	−0.0044 (6)	−0.0066 (5)
C6	0.0159 (6)	0.0217 (7)	0.0220 (7)	0.0033 (5)	−0.0045 (5)	−0.0063 (5)
C7	0.0143 (6)	0.0124 (6)	0.0142 (6)	−0.0009 (5)	0.0004 (5)	−0.0023 (5)
C8	0.0170 (6)	0.0160 (6)	0.0120 (6)	0.0019 (5)	0.0007 (5)	0.0000 (5)
C9	0.0171 (6)	0.0161 (6)	0.0087 (5)	0.0048 (5)	−0.0009 (5)	0.0004 (5)
C10	0.0161 (6)	0.0227 (7)	0.0149 (6)	0.0029 (5)	−0.0040 (5)	−0.0011 (5)
C11	0.0232 (7)	0.0181 (6)	0.0129 (6)	0.0029 (5)	−0.0045 (5)	−0.0036 (5)
C12	0.0185 (6)	0.0170 (6)	0.0099 (5)	0.0073 (5)	−0.0002 (5)	−0.0007 (5)
C13	0.0141 (6)	0.0196 (6)	0.0123 (6)	0.0036 (5)	−0.0019 (5)	−0.0006 (5)
C14	0.0183 (6)	0.0164 (6)	0.0106 (6)	0.0031 (5)	−0.0025 (5)	−0.0017 (5)

S—C7	1.6683 (13)	C9—C14	1.3948 (18)
Br—C4	1.9011 (13)	C9—C10	1.3963 (19)
O1—C8	1.2254 (15)	C10—C11	1.3860 (17)
O2—N3	1.2316 (15)	C11—C12	1.3882 (19)
O3—N3	1.2212 (15)	C12—C13	1.3818 (19)
N1—C7	1.3337 (16)	C13—C14	1.3852 (16)
N1—C1	1.4226 (15)	N1—H01	0.815 (14)
N2—C8	1.3763 (17)	N2—H02	0.774 (12)
N2—C7	1.3938 (15)	C2—H2	0.9500
N3—C12	1.4751 (15)	C3—H3	0.9500
C1—C2	1.3848 (19)	C5—H5	0.9500
C1—C6	1.3898 (19)	C6—H6	0.9500
C2—C3	1.3903 (18)	C10—H10	0.9500
C3—C4	1.377 (2)	C11—H11	0.9500
C4—C5	1.381 (2)	C13—H13	0.9500
C5—C6	1.3898 (18)	C14—H14	0.9500
C8—C9	1.4982 (16)
C7—N1—C1	127.15 (11)	C13—C12—C11	122.97 (11)
C8—N2—C7	128.71 (11)	C13—C12—N3	118.24 (11)
O3—N3—O2	124.19 (11)	C11—C12—N3	118.78 (12)
O3—N3—C12	118.26 (11)	C12—C13—C14	118.42 (12)
O2—N3—C12	117.54 (11)	C13—C14—C9	119.91 (12)
C2—C1—C6	119.98 (12)	C7—N1—H01	116.8 (12)
C2—C1—N1	117.26 (12)	C1—N1—H01	114.9 (12)
C6—C1—N1	122.66 (12)	C8—N2—H02	118.6 (11)
C1—C2—C3	119.77 (13)	C7—N2—H02	112.5 (11)
C4—C3—C2	119.81 (13)	C1—C2—H2	120.1
C3—C4—C5	121.04 (12)	C3—C2—H2	120.1
C3—C4—Br	118.99 (10)	C4—C3—H3	120.1
C5—C4—Br	119.97 (11)	C2—C3—H3	120.1
C4—C5—C6	119.22 (13)	C4—C5—H5	120.4
C5—C6—C1	120.18 (13)	C6—C5—H5	120.4
N1—C7—N2	115.54 (11)	C5—C6—H6	119.9
N1—C7—S	126.05 (10)	C1—C6—H6	119.9
N2—C7—S	118.38 (9)	C11—C10—H10	120.0
O1—C8—N2	123.94 (12)	C9—C10—H10	120.0
O1—C8—C9	122.94 (12)	C10—C11—H11	120.9
N2—C8—C9	113.11 (11)	C12—C11—H11	120.9
C14—C9—C10	120.52 (11)	C12—C13—H13	120.8
C14—C9—C8	119.93 (12)	C14—C13—H13	120.8
C10—C9—C8	119.54 (12)	C13—C14—H14	120.0
C11—C10—C9	119.96 (12)	C9—C14—H14	120.0
C10—C11—C12	118.15 (12)
C7—N1—C1—C2	−140.03 (14)	O1—C8—C9—C14	130.59 (14)
C7—N1—C1—C6	43.7 (2)	N2—C8—C9—C14	−50.80 (16)
C6—C1—C2—C3	−0.5 (2)	O1—C8—C9—C10	−50.40 (18)
N1—C1—C2—C3	−176.90 (13)	N2—C8—C9—C10	128.21 (13)
C1—C2—C3—C4	−0.2 (2)	C14—C9—C10—C11	2.54 (19)
C2—C3—C4—C5	0.6 (2)	C8—C9—C10—C11	−176.47 (11)
C2—C3—C4—Br	−178.99 (11)	C9—C10—C11—C12	−0.99 (19)
C3—C4—C5—C6	−0.3 (2)	C10—C11—C12—C13	−1.09 (19)
Br—C4—C5—C6	179.32 (10)	C10—C11—C12—N3	178.37 (11)
C4—C5—C6—C1	−0.4 (2)	O3—N3—C12—C13	173.49 (11)
C2—C1—C6—C5	0.8 (2)	O2—N3—C12—C13	−5.83 (17)
N1—C1—C6—C5	177.03 (12)	O3—N3—C12—C11	−6.00 (17)
C1—N1—C7—N2	−179.75 (12)	O2—N3—C12—C11	174.68 (12)
C1—N1—C7—S	2.0 (2)	C11—C12—C13—C14	1.60 (19)
C8—N2—C7—N1	−10.14 (19)	N3—C12—C13—C14	−177.87 (11)
C8—N2—C7—S	168.29 (11)	C12—C13—C14—C9	−0.02 (18)
C7—N2—C8—O1	2.3 (2)	C10—C9—C14—C13	−2.02 (19)
C7—N2—C8—C9	−176.27 (12)	C8—C9—C14—C13	176.98 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01···O1	0.82 (1)	2.03 (2)	2.688 (2)	138 (2)
N2—H02···Si	0.77 (1)	2.79 (1)	3.553 (1)	169 (1)
C5—H5···O3ii	0.95	2.38	3.293 (2)	162
C3—H3···Siii	0.95	2.93	3.474 (2)	118
C14—H14···Si	0.95	2.89	3.167 (1)	98
C14—H14···Briv	0.95	3.15	3.899 (1)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H01⋯O1	0.82 (1)	2.03 (2)	2.688 (2)	138 (2)
N2—H02⋯Si	0.77 (1)	2.79 (1)	3.553 (1)	169 (1)
C5—H5⋯O3ii	0.95	2.38	3.293 (2)	162
C3—H3⋯Siii	0.95	2.93	3.474 (2)	118
C14—H14⋯Si	0.95	2.89	3.167 (1)	98
C14—H14⋯Briv	0.95	3.15	3.899 (1)	137

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