N-(2-Bromo­phen­yl)thio­urea

Saleem, H.F.; Yamin, B.M.

doi:10.1107/S1600536810008305

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o789

doi:10.1107/S1600536810008305

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N-(2-Bromophenyl)thiourea

Halima F. Saleem ^a and Bohari M. Yamin ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi Selangor, Malaysia
^*Correspondence e-mail: bohari@ukm.my

(Received 26 February 2010; accepted 4 March 2010; online 10 March 2010)

In the title compound, C₇H₇BrN₂S, the thiourea unit is almost perpendicular to the bromobenzene fragment, making a dihedral angle of 80.82 (16)°. The crystal structure is stabilized by N—H⋯S intermolecular hydrogen bonds, which form linear chains along the ab diagonal.

Related literature

For bond-length data, see: Allen et al. (1987 ). For related structures, see: Steiner (1998 ); Shen & Xu (2004 ); Wang et al. (1991 ). For the antiviral activity of phenylthioureas, see: D'Cruz & Uckun (2005 ); Frank & Smith (1955 ); Mao et al. (2000 ); Sudbeck et al. (1998 ).

Experimental

Crystal data

C₇H₇BrN₂S
M_r = 231.12
Monoclinic, C 2/c
a = 15.181 (3) Å
b = 7.7952 (16) Å
c = 15.312 (3) Å
β = 90.803 (4)°
V = 1811.8 (6) Å³
Z = 8
Mo Kα radiation
μ = 4.71 mm⁻¹
T = 298 K
0.44 × 0.27 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.231, T_max = 0.625
5817 measured reflections
1972 independent reflections
1327 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.129
S = 1.06
1972 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.86	2.54	3.354 (3)	161
N2—H2A⋯S1ⁱⁱ	0.85	2.53	3.368 (3)	168
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810008305/dn2543sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008305/dn2543Isup2.hkl

checkCIF report

Comment top

The number of publications including patents on the application of thiourea compounds in the field of pharmaceutical is increasing at a considerable rate. The antivarial activities of a series of phenylthioureas as none-nucleoside inhibitors HIV-1 reverse transcriptase (NNRTIs) with efficacy against multi-drug resistant viruses (Sudbeck et al., 1998; Mao et al., 2000; D'Cruz & Uckun, 2005) are some of the interesting examples. Several N-thiourea compounds of the type H₂NC(S)NHR are now commercially available.

The title compound (I) is analagous to phenylthiourea (II, Shen et al., 2004), o-fluorophenylthiourea (III, Steiner, 1998) and p-bromophenylthiourea(IV, Wang et al., 1991). The thiourea moiety, S1/N1/N2/C7, and the 2-bromoaniline fragment, Br1/N1/(C1—C6) are each planar with maximum deviation of 0.024 (5)Å for C2 atom from the least square plane. The two planes are perpendicular to each other with dihedral angle of 80.82 (16)° compare to 68.57° in (IV). The thiourea moiety maintains its cis-trans geometry. The bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable to those in (II), (III) and (IV). In contrast to its fluoro- analog ,the molecule is stablized only by pairs of N1—H1A···S1 and N2—H2A···S1 (symmetry codes as in Table 1) intermolecular hydrogen bonds to form linear chains along the diagnal of the ab face (Fig.2).

Related literature top

For bond-length data, see: Allen et al. (1987). For related structures, see: Steiner (1998); Shen & Xu (2004); Wang et al. (1991). For the antiviral activity of phenylthioureas, see: D'Cruz & Uckun (2005); Frank & Smith (1955); Mao et al. (2000); Sudbeck et al. (1998).

Experimental top

The compound was prepared by the method described by Frank & Smith (1955) with a slight modification. Ammonium thiocyante (0.38 g, 0.005 mol) in 15 ml acetone was added into 20 ml acetone solution of containing benzoylchloride (0.70 g, 0.005 mole). The solution was filtered and the filtrate was kept into a 100 ml two neck round bottom flask. o-Bromoaniline (0.86 g, 0.005 mole) was added into the flask and the mixture was refluxed for 2 hours. The final solution was poured into a baker containing some ice cubes. The precipitate formed was filtered. The precipitate was then added into a beaker containing 50 ml aqueous solution of sodium hydroxide (7 g). The solution was heated to boiling for 10 minutes. After a week on standing at room temperature some colourless crystals were obtained and found suitable for X-ray investigation. The yield was 81% and melting point; 428.1-429.3 K.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The nolecular structure of (I), with the atom labeling scheme. Displacement ellipsods are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. A packing diagram of (I) viewed down the b axis. Hydrogen bonds are shown by dashed lines. Hydrogen atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry codes: (i) -x+1/2, -y+3/2, -z+1; (ii) -x, -y+1, -z+1.]

N-(2-Bromophenyl)thiourea top

Crystal data top

C₇H₇BrN₂S	F(000) = 912
M_r = 231.12	D_x = 1.695 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1400 reflections
a = 15.181 (3) Å	θ = 2.6–27.0°
b = 7.7952 (16) Å	µ = 4.71 mm⁻¹
c = 15.312 (3) Å	T = 298 K
β = 90.803 (4)°	Block, colourless
V = 1811.8 (6) Å³	0.44 × 0.27 × 0.11 mm
Z = 8

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1972 independent reflections
Radiation source: fine-focus sealed tube	1327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 83.66 pixels mm^-1	θ_max = 27.0°, θ_min = 2.6°
ω scan	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −5→9
T_min = 0.231, T_max = 0.625	l = −19→19
5817 measured reflections

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0664P)² + 1.1624P] where P = (F_o² + 2F_c²)/3
1972 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

C₇H₇BrN₂S	V = 1811.8 (6) Å³
M_r = 231.12	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.181 (3) Å	µ = 4.71 mm⁻¹
b = 7.7952 (16) Å	T = 298 K
c = 15.312 (3) Å	0.44 × 0.27 × 0.11 mm
β = 90.803 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1972 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1327 reflections with I > 2σ(I)
T_min = 0.231, T_max = 0.625	R_int = 0.028
5817 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.06	Δρ_max = 0.61 e Å⁻³
1972 reflections	Δρ_min = −0.65 e Å⁻³
100 parameters

Special details top

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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.10527 (4)	1.16677 (8)	0.59724 (3)	0.0909 (3)
S1	0.13874 (6)	0.57559 (13)	0.47185 (6)	0.0488 (3)
N1	0.16731 (19)	0.7869 (4)	0.60361 (19)	0.0498 (8)
H1A	0.2173	0.7961	0.5790	0.060*
N2	0.0356 (2)	0.6495 (5)	0.6038 (2)	0.0660 (11)
H2A	−0.0030	0.5879	0.5780	0.079*
H2B	0.0218	0.7159	0.6460	0.079*
C1	0.1703 (3)	0.7627 (6)	0.7636 (3)	0.0565 (10)
H1	0.1868	0.6482	0.7587	0.068*
C2	0.1620 (3)	0.8362 (6)	0.8439 (3)	0.0648 (12)
H2	0.1754	0.7731	0.8939	0.078*
C3	0.1338 (3)	1.0031 (7)	0.8512 (3)	0.0661 (12)
H3	0.1267	1.0510	0.9063	0.079*
C4	0.1163 (3)	1.0993 (6)	0.7788 (3)	0.0645 (11)
H4	0.0972	1.2122	0.7845	0.077*
C5	0.1267 (2)	1.0289 (5)	0.6969 (2)	0.0511 (9)
C6	0.1536 (2)	0.8622 (5)	0.6873 (2)	0.0447 (9)
C7	0.1116 (2)	0.6777 (4)	0.5653 (2)	0.0422 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1262 (6)	0.0874 (4)	0.0595 (3)	0.0326 (3)	0.0145 (3)	0.0182 (3)
S1	0.0499 (5)	0.0498 (5)	0.0472 (5)	−0.0151 (4)	0.0139 (4)	−0.0146 (4)
N1	0.0425 (17)	0.0608 (19)	0.0465 (17)	−0.0151 (15)	0.0159 (14)	−0.0186 (15)
N2	0.0445 (18)	0.087 (3)	0.067 (2)	−0.0264 (18)	0.0218 (16)	−0.036 (2)
C1	0.052 (2)	0.057 (2)	0.060 (2)	0.004 (2)	0.0012 (19)	−0.008 (2)
C2	0.072 (3)	0.077 (3)	0.045 (2)	−0.010 (2)	0.005 (2)	0.007 (2)
C3	0.080 (3)	0.076 (3)	0.042 (2)	−0.014 (3)	0.011 (2)	−0.013 (2)
C4	0.084 (3)	0.056 (2)	0.054 (2)	0.001 (2)	0.016 (2)	−0.014 (2)
C5	0.056 (2)	0.055 (2)	0.0418 (19)	−0.0019 (19)	0.0074 (17)	−0.0036 (17)
C6	0.0402 (19)	0.054 (2)	0.0403 (19)	−0.0100 (17)	0.0091 (15)	−0.0098 (16)
C7	0.0391 (19)	0.044 (2)	0.0440 (18)	−0.0072 (15)	0.0077 (15)	−0.0072 (15)

Geometric parameters (Å, º) top

Br1—C5	1.891 (4)	C1—C6	1.421 (6)
S1—C7	1.693 (4)	C1—H1	0.9300
N1—C7	1.331 (4)	C2—C3	1.375 (7)
N1—C6	1.428 (4)	C2—H2	0.9300
N1—H1A	0.8551	C3—C4	1.361 (6)
N2—C7	1.320 (4)	C3—H3	0.9300
N2—H2A	0.8506	C4—C5	1.380 (5)
N2—H2B	0.8562	C4—H4	0.9300
C1—C2	1.364 (6)	C5—C6	1.371 (5)

C7—N1—C6	124.0 (3)	C2—C3—H3	119.6
C7—N1—H1A	115.0	C3—C4—C5	119.8 (4)
C6—N1—H1A	120.1	C3—C4—H4	120.1
C7—N2—H2A	119.1	C5—C4—H4	120.1
C7—N2—H2B	117.4	C6—C5—C4	120.8 (4)
H2A—N2—H2B	121.2	C6—C5—Br1	120.0 (3)
C2—C1—C6	119.6 (4)	C4—C5—Br1	119.1 (3)
C2—C1—H1	120.2	C5—C6—C1	118.6 (3)
C6—C1—H1	120.2	C5—C6—N1	122.2 (4)
C1—C2—C3	120.2 (4)	C1—C6—N1	119.1 (3)
C1—C2—H2	119.9	N2—C7—N1	117.6 (3)
C3—C2—H2	119.9	N2—C7—S1	121.6 (3)
C4—C3—C2	120.9 (4)	N1—C7—S1	120.8 (3)
C4—C3—H3	119.6

C6—C1—C2—C3	2.9 (6)	Br1—C5—C6—N1	0.6 (5)
C1—C2—C3—C4	−1.9 (7)	C2—C1—C6—C5	−2.1 (6)
C2—C3—C4—C5	0.0 (7)	C2—C1—C6—N1	176.5 (4)
C3—C4—C5—C6	0.8 (6)	C7—N1—C6—C5	−103.7 (4)
C3—C4—C5—Br1	−178.2 (3)	C7—N1—C6—C1	77.7 (5)
C4—C5—C6—C1	0.2 (6)	C6—N1—C7—N2	6.2 (6)
Br1—C5—C6—C1	179.2 (3)	C6—N1—C7—S1	−172.3 (3)
C4—C5—C6—N1	−178.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.54	3.354 (3)	161
N2—H2A···S1ⁱⁱ	0.85	2.53	3.368 (3)	168

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₇BrN₂S
M_r	231.12
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	15.181 (3), 7.7952 (16), 15.312 (3)
β (°)	90.803 (4)
V (Å³)	1811.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.71
Crystal size (mm)	0.44 × 0.27 × 0.11

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.231, 0.625
No. of measured, independent and observed [I > 2σ(I)] reflections	5817, 1972, 1327
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.129, 1.06
No. of reflections	1972
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.65

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-32 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.54	3.354 (3)	160.5
N2—H2A···S1ⁱⁱ	0.85	2.53	3.368 (3)	167.6

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, −y+1, −z+1.

Acknowledgements

The authors thank the Ministry of Higher Education of Malaysia and Universiti Kebangsaan Malaysia for the research grant UKM-GUP-NBT-68–27/110. A scholarship from the Libyan Government to SFH is greatly appreciated.

References

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