Literature DB >> 24940276

1-(2-Bromo-4-chloro-phen-yl)-3,3-di-methyl-thio-urea.

Gamal A El-Hiti¹, Keith Smith², Amany S Hegazy², Mohammad Hayal Alotaibi³, Benson M Kariuki².

Abstract

In the title compound, C9H10BrClN2S, the di-methyl-thio-urea 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 mol-ecules into chains along [010]. Weak C-H⋯Cl inter-actions further link these chains into layers parallel to the ab plane.

Entities: Chemical Disease Gene Species

Year: 2014 PMID： 24940276 PMCID： PMC4051011 DOI： 10.1107/S1600536814011350

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

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 = 293.61 Monoclinic, 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[F 2 > 2σ(F 2)] = 0.028 wR(F 2) = 0.077 S = 1.04 2245 reflections 130 parameters H-atom parameters constrained Δρmax = 0.33 e Å−3 Δρmin = −0.39 e Å−3 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 ▶). Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814011350/cv5457sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814011350/cv5457Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S1600536814011350/cv5457Isup3.cml CCDC reference: 1003616 Additional supporting information: crystallographic information; 3D view; checkCIF report

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

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 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)

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.

	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)

	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)

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)

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

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) ; (ii) .

3 in total

1 in total

1. Crystal structures of three N,N,N'-tris-ubstituted thio-ureas for reactivity-controlled nanocrystal synthesis.

Authors: Evert Dhaene; Isabel Van Driessche; Klaartje De Buysser; Kristof Van Hecke
Journal: Acta Crystallogr E Crystallogr Commun Date: 2022-01-14