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

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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.028
• wR factor = 0.077
• Data-to-parameter ratio = 17.3

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S1. Structural commentary

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.

S2. Synthesis and crystallization

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.

S3. Refinement

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

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

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

	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

Crystal data

C9H10BrClN2S	F(000) = 584
Mr = 293.61	Dx = 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) Å^3	Plate, colourless
Z = 4	0.28 × 0.20 × 0.09 mm

Data collection

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	Rint = 0.015
ω scans	θmax = 73.5°, θmin = 4.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −13→14
Tmin = 0.580, Tmax = 1.000	k = −9→6
4291 measured reflections	l = −16→15

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.86	2.67	3.3488 (19)	137
C9—H9B···Cl1^ii	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.