1-(3-Bromo­phen­yl)thio­urea

Fun, H.-K.; Quah, C.K.; Nayak, P.S.; Narayana, B.; Sarojini, B.K.

doi:10.1107/S1600536812031601

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2462

https://doi.org/10.1107/S1600536812031601

Open

access

1-(3-Bromophenyl)thiourea

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Prakash S. Nayak,^b B. Narayana ^b and B. K. Sarojini ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and ^cDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India
^*Correspondence e-mail: hkfun@usm.my

(Received 8 July 2012; accepted 11 July 2012; online 18 July 2012)

In the title compound, C₇H₇BrN₂S, the thiourea moiety is nearly planar (r.m.s. deviation = 0.004 Å) and it forms a dihedral angle of 66.72 (15)° with the benzene ring. The C—N—C—N2 torsion angle is 15.1 (4)°. In the crystal, molecules are linked via N—H⋯S and N—H⋯N hydrogen bonds into sheets lying parallel to (101).

Related literature

For general background to and related structures of the title compound, see: Fun et al. (2012 ); Sarojini et al. (2007 ). For standard bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₇H₇BrN₂S
M_r = 231.12
Triclinic, $[P \overline 1]$
a = 5.5308 (8) Å
b = 8.5316 (12) Å
c = 9.4249 (14) Å
α = 103.500 (3)°
β = 90.878 (3)°
γ = 97.232 (4)°
V = 428.54 (11) Å³
Z = 2
Mo Kα radiation
μ = 4.97 mm⁻¹
T = 100 K
0.23 × 0.16 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.396, T_max = 0.716
5292 measured reflections
1481 independent reflections
1354 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.067
S = 1.09
1481 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯S1ⁱ	1.05	2.28	3.307 (3)	166
N2—H1N2⋯S1ⁱⁱ	0.96	2.40	3.349 (3)	168
N2—H2N2⋯Br1ⁱⁱⁱ	0.92	2.71	3.468 (2)	141
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y, -z+2; (iii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812031601/hb6892sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031601/hb6892Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031601/hb6892Isup3.cml

checkCIF report

Comment top

In continuation of our work on synthesis of thiourea derivatives (Fun et al., 2012; Sarojini et al., 2007), the title compound was prepared and its crystal structure is reported here.

In the title molecule (Fig. 1), the thiourea moiety (S1/N1/N2/C7) is nearly planar (r.m.s. deviation = 0.004 Å) and it forms a dihedral angle of 66.72 (15)° with the benzene ring (C1–C6). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Fun et al., 2012; Sarojini et al., 2007).

In the crystal structure, Fig. 2, molecules are linked via N1—H1N1···S1, N2—H1N2···S1 and N2—H2N2···Br1 hydrogen bonds (Table 1) into two-dimensional sheets parallel to (101).

Related literature top

For general background to and related structures of the title compound, see: Fun et al. (2012); Sarojini et al. (2007). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

3-Bromoaniline (1.39 g, 0.0081 mol) was refluxed with potassium thiocyanate (1.4 g, 0.0142 mol) in 20 ml of water and 1.6 ml of conc. HCl for 3 h. The reaction mixture was then cooled to room temperature and stirred overnight. The precipitated product was then filtered, washed with water, dried and recrystallised from ethyl acetate as colourless plates (m.p. = 389–391 K).

Structure description top

In continuation of our work on synthesis of thiourea derivatives (Fun et al., 2012; Sarojini et al., 2007), the title compound was prepared and its crystal structure is reported here.

In the crystal structure, Fig. 2, molecules are linked via N1—H1N1···S1, N2—H1N2···S1 and N2—H2N2···Br1 hydrogen bonds (Table 1) into two-dimensional sheets parallel to (101).

For general background to and related structures of the title compound, see: Fun et al. (2012); Sarojini et al. (2007). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal structure of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

1-(3-Bromophenyl)thiourea top

Crystal data top

C₇H₇BrN₂S	Z = 2
M_r = 231.12	F(000) = 228
Triclinic, P1	D_x = 1.791 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5308 (8) Å	Cell parameters from 3285 reflections
b = 8.5316 (12) Å	θ = 2.9–29.6°
c = 9.4249 (14) Å	µ = 4.97 mm⁻¹
α = 103.500 (3)°	T = 100 K
β = 90.878 (3)°	Plate, colourless
γ = 97.232 (4)°	0.23 × 0.16 × 0.07 mm
V = 428.54 (11) Å³

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	1481 independent reflections
Radiation source: fine-focus sealed tube	1354 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.396, T_max = 0.716	k = −10→10
5292 measured reflections	l = −11→11

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0373P)² + 0.1495P] where P = (F_o² + 2F_c²)/3
1481 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₇H₇BrN₂S	γ = 97.232 (4)°
M_r = 231.12	V = 428.54 (11) Å³
Triclinic, P1	Z = 2
a = 5.5308 (8) Å	Mo Kα radiation
b = 8.5316 (12) Å	µ = 4.97 mm⁻¹
c = 9.4249 (14) Å	T = 100 K
α = 103.500 (3)°	0.23 × 0.16 × 0.07 mm
β = 90.878 (3)°

Data collection top

Bruker SMART APEXII DUO CCD diffractometer	1481 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1354 reflections with I > 2σ(I)
T_min = 0.396, T_max = 0.716	R_int = 0.034
5292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.09	Δρ_max = 0.44 e Å⁻³
1481 reflections	Δρ_min = −0.48 e Å⁻³
100 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 > 2sigma(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	0.80456 (5)	0.08100 (4)	0.30695 (3)	0.02513 (13)
S1	0.39118 (12)	0.25378 (9)	1.02969 (8)	0.01925 (18)
N1	0.7109 (4)	0.3643 (3)	0.8568 (3)	0.0188 (5)
H1N1	0.6478	0.4767	0.8945	0.023*
N2	0.7347 (4)	0.1050 (3)	0.8821 (3)	0.0201 (5)
H1N2	0.6763	0.0004	0.8990	0.024*
H2N2	0.8746	0.1112	0.8318	0.024*
C1	1.0878 (5)	0.4459 (4)	0.7452 (3)	0.0208 (6)
H1A	1.1426	0.5220	0.8340	0.025*
C2	1.2308 (5)	0.4300 (4)	0.6236 (3)	0.0241 (7)
H2A	1.3836	0.4966	0.6297	0.029*
C3	1.1532 (5)	0.3180 (4)	0.4929 (3)	0.0220 (6)
H3A	1.2529	0.3057	0.4108	0.026*
C4	0.9281 (5)	0.2254 (4)	0.4859 (3)	0.0185 (6)
C5	0.7812 (5)	0.2390 (3)	0.6044 (3)	0.0174 (6)
H5A	0.6265	0.1744	0.5972	0.021*
C6	0.8650 (5)	0.3495 (4)	0.7348 (3)	0.0183 (6)
C7	0.6287 (5)	0.2392 (3)	0.9158 (3)	0.0164 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02112 (19)	0.0317 (2)	0.01968 (19)	0.00583 (13)	−0.00184 (11)	−0.00064 (13)
S1	0.0192 (4)	0.0159 (4)	0.0237 (4)	0.0044 (3)	0.0047 (3)	0.0055 (3)
N1	0.0211 (12)	0.0164 (13)	0.0189 (13)	0.0044 (10)	0.0024 (10)	0.0029 (10)
N2	0.0210 (12)	0.0149 (13)	0.0256 (13)	0.0053 (10)	0.0052 (10)	0.0057 (10)
C1	0.0207 (15)	0.0199 (16)	0.0220 (15)	0.0030 (12)	−0.0053 (12)	0.0055 (12)
C2	0.0155 (15)	0.0282 (18)	0.0283 (17)	−0.0024 (13)	−0.0029 (13)	0.0092 (14)
C3	0.0163 (15)	0.0281 (17)	0.0224 (15)	0.0058 (13)	0.0008 (12)	0.0061 (13)
C4	0.0181 (14)	0.0192 (16)	0.0185 (14)	0.0064 (12)	−0.0030 (11)	0.0036 (12)
C5	0.0161 (14)	0.0140 (15)	0.0230 (15)	0.0033 (11)	−0.0007 (11)	0.0052 (11)
C6	0.0194 (14)	0.0198 (15)	0.0179 (15)	0.0065 (12)	0.0011 (11)	0.0069 (12)
C7	0.0169 (14)	0.0135 (14)	0.0176 (14)	0.0007 (11)	−0.0044 (11)	0.0025 (11)

Geometric parameters (Å, º) top

Br1—C4	1.900 (3)	C1—C2	1.393 (4)
S1—C7	1.707 (3)	C1—H1A	0.9500
N1—C7	1.348 (4)	C2—C3	1.395 (4)
N1—C6	1.433 (4)	C2—H2A	0.9500
N1—H1N1	1.0468	C3—C4	1.380 (4)
N2—C7	1.327 (4)	C3—H3A	0.9500
N2—H1N2	0.9608	C4—C5	1.383 (4)
N2—H2N2	0.9156	C5—C6	1.395 (4)
C1—C6	1.381 (4)	C5—H5A	0.9500

C7—N1—C6	123.6 (2)	C2—C3—H3A	120.9
C7—N1—H1N1	119.2	C3—C4—C5	122.0 (3)
C6—N1—H1N1	116.9	C3—C4—Br1	120.0 (2)
C7—N2—H1N2	127.4	C5—C4—Br1	117.9 (2)
C7—N2—H2N2	116.3	C4—C5—C6	118.6 (3)
H1N2—N2—H2N2	116.2	C4—C5—H5A	120.7
C6—C1—C2	119.0 (3)	C6—C5—H5A	120.7
C6—C1—H1A	120.5	C1—C6—C5	121.0 (3)
C2—C1—H1A	120.5	C1—C6—N1	120.6 (3)
C1—C2—C3	121.1 (3)	C5—C6—N1	118.3 (3)
C1—C2—H2A	119.5	N2—C7—N1	118.5 (3)
C3—C2—H2A	119.5	N2—C7—S1	121.2 (2)
C4—C3—C2	118.3 (3)	N1—C7—S1	120.3 (2)
C4—C3—H3A	120.9

C6—C1—C2—C3	−0.5 (4)	C2—C1—C6—N1	−178.9 (2)
C1—C2—C3—C4	1.4 (4)	C4—C5—C6—C1	1.3 (4)
C2—C3—C4—C5	−1.0 (4)	C4—C5—C6—N1	179.3 (2)
C2—C3—C4—Br1	176.0 (2)	C7—N1—C6—C1	−123.6 (3)
C3—C4—C5—C6	−0.3 (4)	C7—N1—C6—C5	58.4 (4)
Br1—C4—C5—C6	−177.34 (19)	C6—N1—C7—N2	15.1 (4)
C2—C1—C6—C5	−0.9 (4)	C6—N1—C7—S1	−164.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1ⁱ	1.05	2.28	3.307 (3)	166
N2—H1N2···S1ⁱⁱ	0.96	2.40	3.349 (3)	168
N2—H2N2···Br1ⁱⁱⁱ	0.92	2.71	3.468 (2)	141

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

Experimental details

Crystal data
Chemical formula	C₇H₇BrN₂S
M_r	231.12
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.5308 (8), 8.5316 (12), 9.4249 (14)
α, β, γ (°)	103.500 (3), 90.878 (3), 97.232 (4)
V (Å³)	428.54 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.97
Crystal size (mm)	0.23 × 0.16 × 0.07

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.396, 0.716
No. of measured, independent and observed [I > 2σ(I)] reflections	5292, 1481, 1354
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.067, 1.09
No. of reflections	1481
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.48

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1ⁱ	1.05	2.28	3.307 (3)	166
N2—H1N2···S1ⁱⁱ	0.96	2.40	3.349 (3)	168
N2—H2N2···Br1ⁱⁱⁱ	0.92	2.71	3.468 (2)	141

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

The authors thank Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). BN thanks the UGC for financial assistance through SAP and a BSR one-time grant for the purchase of chemicals.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fun, H.-K., Quah, C. K., Nayak, P. S., Narayana, B. & Sarojini, B. K. (2012). Acta Cryst. E68, o2423. CSD CrossRef IUCr Journals Google Scholar
Sarojini, B. K., Narayana, B., Sunil, K., Yathirajan, H. S. & Bolte, M. (2007). Acta Cryst. E63, o3754. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar