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

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

doi:10.1107/S2414314618000457

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180045

https://doi.org/10.1107/S2414314618000457

Open

access

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

Gamal A. El-Hiti,^a ^* Keith Smith,^b Amany S. Hegazy,^b Mohammed B. Alshammari ^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 ^cChemistry Department, College of Sciences and Humanities, Prince Sattam bin Abdulaziz University, PO Box 83, Al-Kharij 11942, Saudi Arabia
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by J. Simpson, University of Otago, New Zealand (Received 3 January 2018; accepted 8 January 2018; online 12 January 2018)

The bromomethylphenyl and dimethylthiourea groups of the molecule of the title compound, C₁₀H₁₃BrN₂S, are inclined to one another at an interplanar angle of 55.13 (6)°. In the crystal, molecules are stacked along the b axis and intermolecular N—H⋯S contacts form chains of molecules along [010].

Keywords: crystal structure; hydrogen bonding; thiourea; synthesis.

CCDC reference: 1815356

Structure description

Thioureas show various biological activities (Yao et al., 2012 ; Kocyigit-Kaymakcioglu et al., 2013 ; Korkmaz et al., 2015 ; Yang et al., 2015 ; Tahir et al., 2015 ; Shakeel et al., 2016 ) and therefore their syntheses are always of interest (Kong et al., 2015 ; Nguyen et al., 2014 ; Maki et al., 2014 ; Chau et al. 2014 ; Maddani & Prabhu, 2010 ). The X-ray crystal structures of some 1-(2-bromophenyl)-3,3-dimethylthiourea derivatives have been published recently (El-Hiti et al., 2014 , 2017 ): as part of our ongoing studies in this area, we now describe the synthesis and structure of the title compound.

The asymmetric unit comprises one molecule of the title compound (Fig. 1). The molecule is not planar, as indicated by an intramolecular interplanar angle of 55.13 (6) between the bromomethylphenyl and dimethylthiourea groups.

Figure 1
ORTEP representation (50% probability) of the asymmetric unit of C₁₀H₁₃BrN₂S.

In the crystal, molecules are stacked along the b-axis and N—H⋯S intermolecular contacts, Table 1, form chains of molecules along [010], Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.86	2.60	3.309 (2)	140
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Crystal packing showing N—H⋯S contacts as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Synthesis and crystallization

The title compound was synthesized by the reaction of equimolar quantities of 2-bromo-4-methylphenyl isothiocyanate and dimethylamine in dry dichloromethane at 20°C for 1 h. Water was added and the organic layer was separated, dried over anhydrous magnesium sulfate and evaporated under vacuum. The crude product was recrystallized using a solvent mixture of diethyl ether and hexane (1:2 by volume) to give colourless crystals of the title compound, m.p. 174–175°C (lit. 173–175°C; Smith et al., 1996 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₃BrN₂S
M_r	273.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.2617 (7), 8.0222 (4), 12.7397 (7)
β (°)	112.380 (6)
V (Å³)	1158.76 (12)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	6.22
Crystal size (mm)	0.22 × 0.12 × 0.05

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.926, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	7605, 2318, 2035
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.115, 1.06
No. of reflections	2318
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.64
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS2013 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1815356

Crystal structure: contains datablocks I, shelx. DOI: https://doi.org/10.1107/S2414314618000457/sj4152sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000457/sj4152Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000457/sj4152Isup3.cml

checkCIF report

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, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

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

Crystal data top

C₁₀H₁₃BrN₂S	F(000) = 552
M_r = 273.19	D_x = 1.566 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 12.2617 (7) Å	Cell parameters from 3751 reflections
b = 8.0222 (4) Å	θ = 4.2–73.6°
c = 12.7397 (7) Å	µ = 6.22 mm⁻¹
β = 112.380 (6)°	T = 296 K
V = 1158.76 (12) Å³	Block, colourless
Z = 4	0.22 × 0.12 × 0.05 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	2035 reflections with I > 2σ(I)
ω scans	R_int = 0.030
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	θ_max = 74.1°, θ_min = 4.3°
T_min = 0.926, T_max = 0.976	h = −14→15
7605 measured reflections	k = −9→9
2318 independent reflections	l = −12→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.072P)² + 0.3056P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2318 reflections	Δρ_max = 0.54 e Å⁻³
130 parameters	Δρ_min = −0.64 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
Br1	0.26065 (3)	0.22909 (5)	0.48048 (3)	0.06494 (17)
S1	0.18412 (6)	0.22540 (8)	0.06795 (5)	0.0495 (2)
C2	0.1250 (2)	0.1405 (3)	0.3645 (2)	0.0454 (5)
N1	0.24617 (18)	0.0533 (3)	0.26170 (17)	0.0477 (5)
H1	0.2981	−0.0043	0.3139	0.057*
C1	0.1340 (2)	0.0699 (3)	0.26865 (19)	0.0416 (5)
N2	0.3930 (2)	0.0961 (3)	0.19709 (19)	0.0511 (5)
C8	0.2794 (2)	0.1197 (3)	0.18062 (19)	0.0422 (5)
C6	0.0329 (2)	0.0058 (3)	0.1861 (2)	0.0473 (6)
H6	0.0372	−0.0438	0.1218	0.057*
C10	0.4382 (3)	0.1476 (5)	0.1115 (3)	0.0662 (8)
H10A	0.3850	0.1113	0.0380	0.099*
H10B	0.5144	0.0984	0.1281	0.099*
H10C	0.4450	0.2668	0.1120	0.099*
C5	−0.0743 (2)	0.0146 (4)	0.1981 (2)	0.0495 (6)
H5	−0.1414	−0.0287	0.1415	0.059*
C3	0.0176 (3)	0.1482 (4)	0.3771 (2)	0.0524 (6)
H3	0.0137	0.1948	0.4424	0.063*
C4	−0.0834 (2)	0.0873 (4)	0.2936 (2)	0.0509 (6)
C9	0.4791 (2)	0.0276 (4)	0.3016 (3)	0.0614 (7)
H9A	0.4670	0.0750	0.3655	0.092*
H9B	0.5573	0.0538	0.3063	0.092*
H9C	0.4699	−0.0912	0.3019	0.092*
C7	−0.2015 (3)	0.0970 (5)	0.3057 (4)	0.0756 (9)
H7A	−0.1911	0.0734	0.3828	0.113*
H7B	−0.2545	0.0169	0.2562	0.113*
H7C	−0.2337	0.2069	0.2857	0.113*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0668 (3)	0.0716 (3)	0.0472 (2)	−0.01503 (14)	0.01142 (17)	−0.00997 (12)
S1	0.0580 (4)	0.0512 (4)	0.0351 (3)	−0.0007 (3)	0.0132 (3)	0.0014 (2)
C2	0.0495 (13)	0.0465 (13)	0.0379 (11)	−0.0033 (10)	0.0139 (10)	−0.0002 (9)
N1	0.0414 (10)	0.0630 (13)	0.0398 (10)	0.0077 (9)	0.0166 (9)	0.0107 (9)
C1	0.0420 (11)	0.0471 (12)	0.0380 (11)	0.0036 (9)	0.0179 (9)	0.0049 (9)
N2	0.0460 (11)	0.0609 (13)	0.0501 (11)	−0.0049 (10)	0.0226 (9)	0.0027 (10)
C8	0.0458 (12)	0.0453 (12)	0.0360 (11)	−0.0041 (9)	0.0161 (9)	−0.0058 (9)
C6	0.0494 (13)	0.0545 (14)	0.0372 (11)	0.0016 (11)	0.0155 (10)	−0.0024 (10)
C10	0.0652 (17)	0.081 (2)	0.0662 (18)	−0.0097 (16)	0.0408 (15)	−0.0004 (16)
C5	0.0405 (12)	0.0562 (14)	0.0474 (13)	0.0003 (10)	0.0117 (10)	0.0027 (11)
C3	0.0627 (15)	0.0547 (15)	0.0486 (13)	0.0032 (12)	0.0311 (12)	−0.0037 (11)
C4	0.0475 (13)	0.0550 (15)	0.0549 (14)	0.0060 (11)	0.0248 (11)	0.0075 (11)
C9	0.0436 (13)	0.0743 (19)	0.0638 (17)	−0.0032 (13)	0.0178 (12)	0.0084 (15)
C7	0.0566 (17)	0.091 (3)	0.090 (2)	0.0030 (16)	0.0412 (17)	0.000 (2)

Geometric parameters (Å, º) top

Br1—C2	1.893 (2)	C10—H10B	0.9600
S1—C8	1.693 (2)	C10—H10C	0.9600
C2—C3	1.388 (4)	C5—C4	1.392 (4)
C2—C1	1.388 (3)	C5—H5	0.9300
N1—C8	1.355 (3)	C3—C4	1.379 (4)
N1—C1	1.418 (3)	C3—H3	0.9300
N1—H1	0.8600	C4—C7	1.515 (4)
C1—C6	1.383 (4)	C9—H9A	0.9600
N2—C8	1.340 (3)	C9—H9B	0.9600
N2—C9	1.456 (4)	C9—H9C	0.9600
N2—C10	1.459 (3)	C7—H7A	0.9600
C6—C5	1.382 (4)	C7—H7B	0.9600
C6—H6	0.9300	C7—H7C	0.9600
C10—H10A	0.9600

C3—C2—C1	121.1 (2)	H10B—C10—H10C	109.5
C3—C2—Br1	118.91 (19)	C6—C5—C4	121.0 (2)
C1—C2—Br1	119.99 (19)	C6—C5—H5	119.5
C8—N1—C1	126.2 (2)	C4—C5—H5	119.5
C8—N1—H1	116.9	C4—C3—C2	120.5 (2)
C1—N1—H1	116.9	C4—C3—H3	119.7
C6—C1—C2	118.2 (2)	C2—C3—H3	119.7
C6—C1—N1	121.8 (2)	C3—C4—C5	118.4 (2)
C2—C1—N1	119.8 (2)	C3—C4—C7	121.0 (3)
C8—N2—C9	123.0 (2)	C5—C4—C7	120.5 (3)
C8—N2—C10	120.7 (2)	N2—C9—H9A	109.5
C9—N2—C10	116.1 (2)	N2—C9—H9B	109.5
N2—C8—N1	114.9 (2)	H9A—C9—H9B	109.5
N2—C8—S1	122.94 (19)	N2—C9—H9C	109.5
N1—C8—S1	122.14 (19)	H9A—C9—H9C	109.5
C5—C6—C1	120.7 (2)	H9B—C9—H9C	109.5
C5—C6—H6	119.6	C4—C7—H7A	109.5
C1—C6—H6	119.6	C4—C7—H7B	109.5
N2—C10—H10A	109.5	H7A—C7—H7B	109.5
N2—C10—H10B	109.5	C4—C7—H7C	109.5
H10A—C10—H10B	109.5	H7A—C7—H7C	109.5
N2—C10—H10C	109.5	H7B—C7—H7C	109.5
H10A—C10—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.60	3.309 (2)	140

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Footnotes

‡Additional corresponding author, e-mail: kariukib@cardiff.ac.uk.

Funding information

The project was supported by King Saud University, Deanship of Scientific Research, Research Chairs and Cardiff University.

References

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Cambridge Soft (2001). CHEMDRAW Ultra. Cambridge Soft Corporation, Cambridge, Massachusetts, USA. Google Scholar
Chau, C.-M., Chuan, T.-J. & Liu, K.-L. (2014). RSC Adv. 4, 1276–1282. Web of Science CrossRef CAS Google Scholar
El-Hiti, G. A., Smith, K., Hegazy, A. S., Alotaibi, M. H. & Kariuki, B. M. (2014). Acta Cryst. E70, o704. CSD CrossRef IUCr Journals Google Scholar
El-Hiti, G. A., Smith, K., Hegazy, A. S., Alotaibi, M. H. & Kariuki, B. M. (2017). Z. Kristallogr. New Cryst. Struct. 232, 31–32. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kocyigit-Kaymakcioglu, B., Celen, A. O., Tabanca, N., Ali, A., Khan, S. I., Khan, I. A. & Wedge, D. E. (2013). Molecules, 18, 3562–3576. Web of Science CAS PubMed Google Scholar
Kong, X., Yao, Z., He, Z., Xu, W. & Yao, J. (2015). Med. Chem. Commun. 6, 867–870. Web of Science CrossRef CAS Google Scholar
Korkmaz, N., Obaidi, O. A., Senturk, M., Astley, D., Ekinci, D. & Supuran, C. T. (2015). J. Enzyme Inhib. Med. Chem. 30, 75–80. Web of Science CrossRef CAS PubMed Google Scholar
Maddani, M. R. & Prabhu, K. R. (2010). J. Org. Chem. 75, 2327–2332. Web of Science CrossRef CAS PubMed Google Scholar
Maki, T., Tsuritani, T. & Yasukata, T. (2014). Org. Lett. 16, 1868–1871. Web of Science CrossRef CAS PubMed Google Scholar
Nguyen, T. B., Ermolenko, L. & Al-Mourabit, A. (2014). Synthesis, 46, 3172–3179. Web of Science CrossRef CAS Google Scholar
Shakeel, A., Altaf, A. A., Qureshi, A. M. & Badshan, A. (2016). J. Drug Des. Med. Chem. 2, 10–20. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, K., Shukla, A. P. & Matthews, I. (1996). Sulfur Lett. 20, 121–137. CAS Google Scholar
Tahir, S., Badshah, A., Hussain, R. A., Tahir, M. N., Tabassum, S., Patujo, J. A. & Rauf, M. K. (2015). J. Mol. Struct. 1099, 215–225. Web of Science CrossRef CAS Google Scholar
Yang, M., Pickard, A. J., Qiao, X., Gueble, M. J., Day, C. S., Kucera, G. L. & Bierbach, U. (2015). Inorg. Chem. 54, 3316–3324. Web of Science CSD CrossRef CAS PubMed Google Scholar
Yao, J., Chen, J., He, Z., Sun, W. & Xu, W. (2012). Bioorg. Med. Chem. 20, 2923–2929. Web of Science CrossRef CAS PubMed Google Scholar