1-(2-Bromo-4-chloro­phen­yl)-3,3-di­methyl­thio­urea

El-Hiti, G.A.; Smith, K.; Hegazy, A.S.; Alotaibi, M.H.; Kariuki, B.M.

doi:10.1107/S1600536814011350

organic compounds

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Volume 70| Part 6| June 2014| Page o704

doi:10.1107/S1600536814011350

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1-(2-Bromo-4-chlorophenyl)-3,3-dimethylthiourea

Gamal A. El-Hiti,^a ^* Keith Smith,^b Amany S. Hegazy,^b Mohammad Hayal Alotaibi ^c and Benson M. Kariuki ^b ^*

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, and ^cPetrochemical Research Institute, King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia
^*Correspondence e-mail: gelhiti@ksu.edu.sa, kariukib@cardiff.ac.uk

(Received 9 May 2014; accepted 16 May 2014; online 24 May 2014)

In the title compound, C₉H₁₀BrClN₂S, the dimethylthiourea group is twisted from the benzene ring plane by 54.38 (6)°. In the crystal, the amino groups are involved in the formation of N—H⋯S hydrogen bonds, which link the molecules into chains along [010]. Weak C—H⋯Cl interactions further link these chains into layers parallel to the ab plane.

CCDC reference: 1003616

Related literature

For related compounds, see: Maddani & Prabhu (2010 ); Yahyazadeh & Ghasemi (2013 ); Zhao et al. (2013 ). For convenient routes for modifying urea derivatives via organolithium intermediates, see: Smith et al. (1996 , 1999 , 2009 , 2010 , 2012 , 2014 ). For the structures of related compounds, see: Zhao et al. (2008 ); Ramnathan et al. (1996 ).

Experimental

Crystal data

C₉H₁₀BrClN₂S
M_r = 293.61
Monoclinic, P 2₁ /n
a = 12.1369 (3) Å
b = 7.9431 (2) Å
c = 13.2230 (4) Å
β = 115.386 (3)°
V = 1151.67 (6) Å³
Z = 4
Cu Kα radiation
μ = 8.40 mm⁻¹
T = 296 K
0.28 × 0.20 × 0.09 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ) T_min = 0.580, T_max = 1.000
4291 measured reflections
2245 independent reflections
2078 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.077
S = 1.04
2245 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.86	2.67	3.349 (2)	137
C9—H9B⋯Cl1ⁱⁱ	0.96	2.81	3.696 (2)	153
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z.

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1003616

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814011350/cv5457sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814011350/cv5457Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814011350/cv5457Isup3.cml

checkCIF report

Structural commentary top

Recently, various thiourea derivatives have been synthesised and showed broad interesting properties (Maddani & Prabhu, 2010; Yahyazadeh & Ghasemi, 2013; Zhao et al., 2013). In a continuation of our research focused on new synthetic routes towards novel substituted urea derivatives (Smith et al., 1996, 1999, 2009, 2010, 2012, 2014) we have synthesized 3-(2-bromo-4-chlorophenyl)-1,1-dimethylthiourea (I) in a high yield (Smith et al., 1996). We have prepared the material again and crystallized it in high purity in order to obtain its crystal structure, which we present herein.

In (I) (Fig. 1), all bond lengths and angles are normal and correspond well to those observed in the related compounds (Zhao et al., 2008; Ramnathan et al., 1996). The non-hydrogen atoms in (I) fall into two planes with an interplaner angle of 54.38 (6)° between the bromo-chlorophenyl and dimethylthiourea groups. Each molecule is involved in N—H···S contacts (Table 1) with two neigbouring molecules, with one as an acceptor and the other as a donor, leading to the formation of zig-zag-chains in [010] (Fig 2). The bromo-chlorophenyl and dimethylthiourea groups of adjacent molecules are parallel in the stack forming chains of alternating S···Br···S groups with a separation of 4.07Å and 4.11Å between the atoms.

Synthesis and crystallization top

To a stirred solution of 2-bromo-4-chloro-1-isothiocyanatobenzene (12.43 g, 50.0 mmol) in anhydrous dioxane (120 ml) dimethylamine (7.10 g of 33% solution in ethanol, 52.0 mmol) was slowly added in a drop-wise manner over 5 min. The reaction mixture was stirred at room temperature for an extra 1 h. The solid obtained was collected by filtration and washed with dioxane (2 x 20 ml) and dried. Recrystallization from ethyl acetate gave 3-(2-bromo-4-chlorophenyl)-1,1-dimethylthiourea (13.80 g, 47.0 mmol; 94%) as yellow crystals, m.p. 193–194 °C [lit. 184–185 °C (ethyl acetate); Smith et al. (1996)]. ¹H NMR (500 MHz, CDCl₃, δ, p.p.m.) 7.97 (d, J = 8.8 Hz, 1 H, H-6), 7.59 (d, J = 2.3 Hz, 1 H, H-3), 7.32 (dd, J = 2.3, 8.8 Hz, 1 H, H-5), 7.17 (br, exch., 1 H, NH), 3.43 [s, 6 H, N(CH₃)₂]. ¹³C NMR (125 MHz, CDCl₃, δ, p.p.m.) 181.2 (s, C=S), 136.6 (s, C-1), 131.8 (d, C-3), 131.0 (s, C-4), 127.8 (d, C-6), 127.7 (d, C-5), 118.1 (s, C-2), 41.3 [q, N(CH₃)₂]. AP⁺—MS (m/z, %): 297 ([MH⁸¹Br³⁷Cl]⁺, 34), 295 ([MH⁸¹Br³⁵Cl and MH⁷⁹Br³⁷Cl]⁺, 100), 293 ([MH⁷⁹Br³⁵Cl]⁺, 80), 263 (12), 215 (22), 213 (50). HRMS (AP⁺): Calculated for C₉H₁₁⁷⁹Br³⁵ClN₂S [MH] 292.9515; found, 292.9515.

Refinement top

H atoms were positioned geometrically and refined using a riding model with Uĩso(H) = 1.2 times Ueq for the atom they are bonded to except for the methyl groups where 1.5 times Ueq was used with free rotation about the C—C bond.

Related literature top

For related compounds, see: Maddani & Prabhu (2010); Yahyazadeh & Ghasemi (2013); Zhao et al. (2013). For convenient routes for modifying urea derivatives via organolithium intermediates, see: Smith et al. (1996, 1999, 2009, 2010, 2012, 2014). For the X-ray structures of related compounds, see: Zhao et al. (2008); Ramnathan et al. (1996).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. View of (I) showing atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A portion of the crystal packing viewed along the a axis. N—H···S contacts are shown as dotted lines.

1-(2-Bromo-4-chlorophenyl)-3,3-dimethylthiourea top

Crystal data top

C₉H₁₀BrClN₂S	F(000) = 584
M_r = 293.61	D_x = 1.693 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.5418 Å
a = 12.1369 (3) Å	Cell parameters from 2078 reflections
b = 7.9431 (2) Å	θ = 4.1–75.5°
c = 13.2230 (4) Å	µ = 8.40 mm⁻¹
β = 115.386 (3)°	T = 296 K
V = 1151.67 (6) Å³	Plate, colourless
Z = 4	0.28 × 0.20 × 0.09 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2245 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2078 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.015
ω scans	θ_max = 73.5°, θ_min = 4.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −13→14
T_min = 0.580, T_max = 1.000	k = −9→6
4291 measured reflections	l = −16→15

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0429P)² + 0.4682P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max = 0.002
S = 1.04	Δρ_max = 0.33 e Å⁻³
2245 reflections	Δρ_min = −0.39 e Å⁻³
130 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0048 (3)

Crystal data top

C₉H₁₀BrClN₂S	V = 1151.67 (6) Å³
M_r = 293.61	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 12.1369 (3) Å	µ = 8.40 mm⁻¹
b = 7.9431 (2) Å	T = 296 K
c = 13.2230 (4) Å	0.28 × 0.20 × 0.09 mm
β = 115.386 (3)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2245 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	2078 reflections with I > 2σ(I)
T_min = 0.580, T_max = 1.000	R_int = 0.015
4291 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
2245 reflections	Δρ_min = −0.39 e Å⁻³
130 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro (Agilent, 2014). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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

	x	y	z	U_iso*/U_eq
C1	0.85876 (18)	0.0661 (3)	0.22866 (16)	0.0377 (4)
C2	0.85637 (19)	0.1344 (3)	0.13058 (16)	0.0404 (4)
C3	0.9605 (2)	0.1405 (3)	0.11271 (19)	0.0495 (5)
H3	0.9581	0.1851	0.0468	0.059*
C4	1.0675 (2)	0.0794 (3)	0.1942 (2)	0.0523 (5)
C5	1.0726 (2)	0.0087 (3)	0.29241 (19)	0.0497 (5)
H5	1.1455	−0.0334	0.3465	0.060*
C6	0.96763 (19)	0.0022 (3)	0.30797 (17)	0.0440 (5)
H6	0.9699	−0.0460	0.3729	0.053*
C7	0.72784 (18)	0.1177 (3)	0.32603 (16)	0.0379 (4)
C8	0.5801 (3)	0.1471 (4)	0.4043 (2)	0.0638 (7)
H8A	0.5786	0.0517	0.4483	0.096*
H8B	0.5006	0.1978	0.3710	0.096*
H8C	0.6383	0.2278	0.4515	0.096*
C9	0.5176 (2)	0.0190 (4)	0.2169 (2)	0.0569 (6)
H9A	0.5032	0.0890	0.1533	0.085*
H9B	0.4443	0.0110	0.2274	0.085*
H9C	0.5416	−0.0913	0.2045	0.085*
Br1	0.70976 (2)	0.22178 (4)	0.01974 (2)	0.05768 (14)
Cl1	1.19895 (7)	0.08827 (15)	0.17270 (8)	0.0936 (3)
N1	0.74917 (15)	0.0536 (3)	0.24110 (14)	0.0442 (4)
H1	0.6901	−0.0001	0.1897	0.053*
N2	0.61441 (17)	0.0925 (3)	0.31655 (16)	0.0470 (4)
S1	0.83592 (5)	0.22395 (7)	0.43366 (4)	0.04637 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0377 (9)	0.0420 (10)	0.0314 (9)	−0.0038 (8)	0.0129 (7)	−0.0039 (8)
C2	0.0436 (10)	0.0403 (10)	0.0335 (9)	−0.0009 (8)	0.0128 (8)	−0.0013 (8)
C3	0.0570 (13)	0.0531 (13)	0.0436 (11)	−0.0046 (10)	0.0264 (10)	0.0013 (10)
C4	0.0437 (11)	0.0644 (15)	0.0526 (12)	−0.0043 (10)	0.0242 (10)	−0.0078 (11)
C5	0.0395 (10)	0.0595 (14)	0.0420 (11)	0.0018 (9)	0.0098 (9)	−0.0050 (10)
C6	0.0451 (10)	0.0495 (12)	0.0327 (9)	0.0004 (9)	0.0123 (8)	0.0013 (8)
C7	0.0420 (10)	0.0375 (10)	0.0312 (9)	0.0047 (8)	0.0128 (8)	0.0048 (7)
C8	0.0684 (15)	0.0766 (18)	0.0611 (15)	0.0111 (14)	0.0416 (13)	0.0006 (13)
C9	0.0376 (10)	0.0679 (16)	0.0603 (14)	0.0018 (10)	0.0164 (10)	−0.0056 (12)
Br1	0.05856 (19)	0.0600 (2)	0.04035 (17)	0.01302 (11)	0.00771 (12)	0.00683 (10)
Cl1	0.0558 (4)	0.1432 (9)	0.0976 (6)	−0.0020 (4)	0.0480 (4)	−0.0011 (6)
N1	0.0376 (8)	0.0595 (11)	0.0339 (8)	−0.0088 (8)	0.0138 (7)	−0.0088 (8)
N2	0.0435 (9)	0.0547 (11)	0.0451 (9)	0.0054 (8)	0.0213 (8)	−0.0008 (8)
S1	0.0545 (3)	0.0447 (3)	0.0308 (3)	0.0000 (2)	0.0096 (2)	−0.00197 (19)

Geometric parameters (Å, º) top

C1—C6	1.384 (3)	C7—N2	1.343 (3)
C1—C2	1.395 (3)	C7—N1	1.355 (3)
C1—N1	1.412 (3)	C7—S1	1.690 (2)
C2—C3	1.383 (3)	C8—N2	1.457 (3)
C2—Br1	1.887 (2)	C8—H8A	0.9600
C3—C4	1.372 (3)	C8—H8B	0.9600
C3—H3	0.9300	C8—H8C	0.9600
C4—C5	1.392 (3)	C9—N2	1.459 (3)
C4—Cl1	1.738 (2)	C9—H9A	0.9600
C5—C6	1.375 (3)	C9—H9B	0.9600
C5—H5	0.9300	C9—H9C	0.9600
C6—H6	0.9300	N1—H1	0.8600

C6—C1—C2	118.68 (18)	N1—C7—S1	122.03 (16)
C6—C1—N1	121.79 (18)	N2—C8—H8A	109.5
C2—C1—N1	119.39 (18)	N2—C8—H8B	109.5
C3—C2—C1	121.09 (19)	H8A—C8—H8B	109.5
C3—C2—Br1	118.76 (16)	N2—C8—H8C	109.5
C1—C2—Br1	120.14 (15)	H8A—C8—H8C	109.5
C4—C3—C2	118.7 (2)	H8B—C8—H8C	109.5
C4—C3—H3	120.7	N2—C9—H9A	109.5
C2—C3—H3	120.7	N2—C9—H9B	109.5
C3—C4—C5	121.6 (2)	H9A—C9—H9B	109.5
C3—C4—Cl1	118.89 (19)	N2—C9—H9C	109.5
C5—C4—Cl1	119.51 (19)	H9A—C9—H9C	109.5
C6—C5—C4	118.8 (2)	H9B—C9—H9C	109.5
C6—C5—H5	120.6	C7—N1—C1	126.45 (17)
C4—C5—H5	120.6	C7—N1—H1	116.8
C5—C6—C1	121.2 (2)	C1—N1—H1	116.8
C5—C6—H6	119.4	C7—N2—C8	120.9 (2)
C1—C6—H6	119.4	C7—N2—C9	122.72 (18)
N2—C7—N1	114.77 (18)	C8—N2—C9	116.3 (2)
N2—C7—S1	123.19 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.67	3.3488 (19)	137
C9—H9B···Cl1ⁱⁱ	0.96	2.81	3.696 (2)	153

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.67	3.3488 (19)	136.9
C9—H9B···Cl1ⁱⁱ	0.96	2.81	3.696 (2)	153.2

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

Acknowledgements

The authors thank the College of Applied Medical Sciences Research Center and the Deanship of Scientific Research at King Saud University for funding this research.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o704

doi:10.1107/S1600536814011350

Open

access