4-Bromo-N-(diethyl-carbamothio-yl)-benzamide.

The synthesis of the title compound, C(12)H(15)BrN(2)OS, involves the reaction of 4-bromo-benzoyl chloride with potassium thio-cyanate in dry acetone, followed by condensation of 4-bromo-benzoyl isothio-cyanate with diethyl-amine. The carbonyl and thio-carbonyl bond lengths indicate that these correspond to double bonds. The short C-N bond lengths reveal the effects of resonance in this part of the mol-ecule. The conformation of the mol-ecule with respect to the thio-carbonyl and carbonyl units is twisted, with torsion angles of -5.7 (3) and 87.2 (2)°. The N atom of the diethyl-amine group is sp(2)-hybridized: the sum of the angles around the N atom is 359.97 (14)°. The two diethyl groups are twisted in + and - anti-periplanar conformations with angles of -179.89 and 179.92°. In the crystal structure, the mol-ecules form infinite chains via an inter-molecular N-H⋯O inter-action.

Related literature

For the synthesis, see: Özer et al. (2009 ▶); Arslan, Flörke & Külcü (2003 ▶), and references therein. For general background, see: Koch (2001 ▶); El Aamrani et al. (1998 ▶, 1999 ▶); Arslan et al. (2006 ▶); Arslan, Flörke & Külcü (2007 ▶); Arslan, Flörke, Külcü & Binzet (2007 ▶); Yuan et al. (2001 ▶); Zhang et al. (2004 ▶); Weiqun et al. (2004 ▶). For related compounds, see: Arslan, Külcü & Flörke (2003 ▶); Arslan et al. (2004 ▶); Khawar Rauf et al. (2009a ▶,b ▶); Khawar Rauf, Bolte & Anwar (2009 ▶); Khawar Rauf, Bolte & Rauf (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C12H15BrN2OS

M = 315.23

Monoclinic,

a = 6.9955 (9) Å

b = 18.680 (2) Å

c = 10.0816 (13) Å

β = 95.361 (3)°

V = 1311.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 3.28 mm−1

T = 120 (2) K

0.38 × 0.37 × 0.11 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.329, T max = 0.714

10831 measured reflections

3117 independent reflections

2730 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.064

S = 1.06

3117 reflections

158 parameters

1 restraint

<span class="Disease">H atomsn> treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003183/at2713sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003183/at2713Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H15BrN2OS	F(000) = 640
Mr = 315.23	Dx = 1.596 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 891 reflections
a = 6.9955 (9) Å	θ = 2.3–28.2°
b = 18.680 (2) Å	µ = 3.28 mm−1
c = 10.0816 (13) Å	T = 120 K
β = 95.361 (3)°	Prism, colourless
V = 1311.7 (3) Å3	0.38 × 0.37 × 0.11 mm
Z = 4

Bruker SMART APEX diffractometer	3117 independent reflections
Radiation source: sealed tube	2730 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→7
Tmin = 0.329, Tmax = 0.714	k = −24→24
10831 measured reflections	l = −13→13

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)] = 0.025	Hydrogen site location: difference Fourier map
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0328P)2 + 0.2678P] where P = (Fo2 + 2Fc2)/3
3117 reflections	(Δ/σ)max = 0.001
158 parameters	Δρmax = 0.59 e Å−3
1 restraint	Δρmin = −0.26 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.18884 (3)	0.416437 (9)	0.341437 (19)	0.02229 (7)
S1	0.41112 (7)	0.90370 (2)	0.43285 (5)	0.02424 (11)
O1	0.4748 (2)	0.73637 (7)	0.62427 (13)	0.0265 (3)
N1	0.5090 (2)	0.76602 (7)	0.41132 (14)	0.0176 (3)
H1	0.478 (3)	0.7585 (12)	0.3242 (7)	0.035 (6)*
N2	0.7563 (2)	0.84313 (7)	0.48486 (15)	0.0184 (3)
C1	0.5705 (3)	0.83737 (9)	0.44671 (17)	0.0180 (4)
C2	0.8900 (3)	0.78163 (9)	0.49166 (19)	0.0230 (4)
H2A	0.8245	0.7391	0.5248	0.028*
H2B	1.0018	0.7926	0.5561	0.028*
C3	0.9600 (3)	0.76427 (10)	0.3581 (2)	0.0290 (4)
H3A	1.0476	0.7233	0.3674	0.043*
H3B	1.0277	0.8058	0.3258	0.043*
H3C	0.8501	0.7525	0.2943	0.043*
C4	0.8433 (3)	0.91336 (9)	0.51931 (19)	0.0219 (4)
H4A	0.7698	0.9512	0.4681	0.026*
H4B	0.9764	0.9142	0.4935	0.026*
C5	0.8459 (3)	0.92934 (10)	0.66664 (19)	0.0265 (4)
H5A	0.9048	0.9763	0.6855	0.040*
H5B	0.9204	0.8925	0.7176	0.040*
H5C	0.7141	0.9296	0.6922	0.040*
C6	0.4567 (3)	0.72010 (9)	0.50554 (17)	0.0172 (3)
C7	0.3850 (2)	0.64814 (9)	0.45935 (17)	0.0166 (3)
C8	0.3120 (3)	0.60335 (10)	0.55234 (18)	0.0197 (4)
H8A	0.3030	0.6200	0.6406	0.024*
C9	0.2519 (3)	0.53439 (9)	0.51763 (18)	0.0203 (4)
H9A	0.2013	0.5039	0.5812	0.024*
C10	0.2670 (2)	0.51082 (9)	0.38901 (18)	0.0180 (3)
C11	0.3388 (3)	0.55432 (9)	0.29424 (18)	0.0204 (4)
H11A	0.3481	0.5372	0.2063	0.025*
C12	0.3970 (3)	0.62334 (9)	0.32955 (18)	0.0190 (4)
H12A	0.4453	0.6539	0.2651	0.023*

	U11	U22	U33	U12	U13	U23
Br1	0.02598 (11)	0.01446 (10)	0.02654 (11)	−0.00248 (6)	0.00300 (7)	−0.00079 (6)
S1	0.0274 (3)	0.0178 (2)	0.0274 (3)	0.00464 (17)	0.00185 (19)	−0.00387 (17)
O1	0.0459 (9)	0.0198 (6)	0.0141 (6)	−0.0039 (6)	0.0046 (6)	−0.0019 (5)
N1	0.0241 (8)	0.0153 (7)	0.0131 (7)	−0.0018 (6)	0.0007 (6)	−0.0016 (5)
N2	0.0240 (8)	0.0130 (7)	0.0184 (8)	−0.0006 (6)	0.0028 (6)	−0.0016 (5)
C1	0.0277 (10)	0.0139 (8)	0.0127 (8)	−0.0025 (7)	0.0040 (7)	−0.0005 (6)
C2	0.0242 (10)	0.0171 (8)	0.0270 (10)	0.0023 (7)	−0.0025 (8)	0.0019 (7)
C3	0.0293 (11)	0.0264 (10)	0.0313 (11)	0.0090 (8)	0.0034 (8)	−0.0025 (8)
C4	0.0259 (10)	0.0172 (8)	0.0230 (10)	−0.0052 (7)	0.0040 (7)	−0.0023 (7)
C5	0.0317 (11)	0.0246 (9)	0.0228 (10)	−0.0065 (8)	0.0009 (8)	−0.0063 (7)
C6	0.0206 (9)	0.0157 (8)	0.0155 (9)	0.0023 (6)	0.0021 (7)	−0.0007 (6)
C7	0.0174 (8)	0.0150 (7)	0.0172 (9)	0.0017 (6)	0.0007 (7)	−0.0006 (6)
C8	0.0244 (9)	0.0205 (8)	0.0146 (9)	0.0001 (7)	0.0035 (7)	−0.0009 (7)
C9	0.0211 (9)	0.0197 (8)	0.0207 (9)	−0.0022 (7)	0.0042 (7)	0.0041 (7)
C10	0.0165 (9)	0.0138 (7)	0.0233 (9)	0.0007 (6)	0.0002 (7)	−0.0008 (6)
C11	0.0275 (10)	0.0178 (8)	0.0164 (9)	−0.0017 (7)	0.0038 (7)	−0.0023 (7)
C12	0.0243 (9)	0.0164 (8)	0.0168 (9)	−0.0011 (7)	0.0051 (7)	0.0016 (6)

Br1—C10	1.8944 (17)	C4—H4A	0.9900
S1—C1	1.6638 (18)	C4—H4B	0.9900
O1—C6	1.230 (2)	C5—H5A	0.9800
N1—C6	1.355 (2)	C5—H5B	0.9800
N1—C1	1.435 (2)	C5—H5C	0.9800
N1—H1	0.896 (5)	C6—C7	1.494 (2)
N2—C1	1.325 (2)	C7—C8	1.389 (2)
N2—C4	1.474 (2)	C7—C12	1.398 (2)
N2—C2	1.479 (2)	C8—C9	1.390 (2)
C2—C3	1.511 (3)	C8—H8A	0.9500
C2—H2A	0.9900	C9—C10	1.383 (3)
C2—H2B	0.9900	C9—H9A	0.9500
C3—H3A	0.9800	C10—C11	1.384 (2)
C3—H3B	0.9800	C11—C12	1.389 (2)
C3—H3C	0.9800	C11—H11A	0.9500
C4—C5	1.513 (3)	C12—H12A	0.9500
C6—N1—C1	120.52 (14)	C4—C5—H5A	109.5
C6—N1—H1	122.0 (15)	C4—C5—H5B	109.5
C1—N1—H1	115.4 (15)	H5A—C5—H5B	109.5
C1—N2—C4	120.85 (14)	C4—C5—H5C	109.5
C1—N2—C2	123.33 (14)	H5A—C5—H5C	109.5
C4—N2—C2	115.79 (15)	H5B—C5—H5C	109.5
N2—C1—N1	114.24 (15)	O1—C6—N1	121.04 (16)
N2—C1—S1	126.53 (13)	O1—C6—C7	121.79 (16)
N1—C1—S1	119.20 (13)	N1—C6—C7	117.11 (15)
N2—C2—C3	112.43 (15)	C8—C7—C12	119.34 (16)
N2—C2—H2A	109.1	C8—C7—C6	117.74 (15)
C3—C2—H2A	109.1	C12—C7—C6	122.84 (16)
N2—C2—H2B	109.1	C7—C8—C9	120.67 (16)
C3—C2—H2B	109.1	C7—C8—H8A	119.7
H2A—C2—H2B	107.8	C9—C8—H8A	119.7
C2—C3—H3A	109.5	C10—C9—C8	118.91 (16)
C2—C3—H3B	109.5	C10—C9—H9A	120.5
H3A—C3—H3B	109.5	C8—C9—H9A	120.5
C2—C3—H3C	109.5	C9—C10—C11	121.67 (16)
H3A—C3—H3C	109.5	C9—C10—Br1	119.22 (13)
H3B—C3—H3C	109.5	C11—C10—Br1	119.11 (13)
N2—C4—C5	111.95 (15)	C10—C11—C12	119.01 (16)
N2—C4—H4A	109.2	C10—C11—H11A	120.5
C5—C4—H4A	109.2	C12—C11—H11A	120.5
N2—C4—H4B	109.2	C11—C12—C7	120.39 (16)
C5—C4—H4B	109.2	C11—C12—H12A	119.8
H4A—C4—H4B	107.9	C7—C12—H12A	119.8
C4—N2—C1—N1	177.55 (14)	N1—C6—C7—C8	−173.35 (16)
C2—N2—C1—N1	−0.4 (2)	O1—C6—C7—C12	−167.57 (18)
C4—N2—C1—S1	−0.6 (3)	N1—C6—C7—C12	9.7 (2)
C2—N2—C1—S1	−178.51 (14)	C12—C7—C8—C9	0.3 (3)
C6—N1—C1—N2	87.2 (2)	C6—C7—C8—C9	−176.75 (16)
C6—N1—C1—S1	−94.57 (18)	C7—C8—C9—C10	0.4 (3)
C1—N2—C2—C3	82.9 (2)	C8—C9—C10—C11	−0.5 (3)
C4—N2—C2—C3	−95.12 (19)	C8—C9—C10—Br1	179.13 (13)
C1—N2—C4—C5	92.2 (2)	C9—C10—C11—C12	0.0 (3)
C2—N2—C4—C5	−89.7 (2)	Br1—C10—C11—C12	−179.64 (13)
C1—N1—C6—O1	−5.7 (3)	C10—C11—C12—C7	0.7 (3)
C1—N1—C6—C7	176.95 (15)	C8—C7—C12—C11	−0.8 (3)
O1—C6—C7—C8	9.3 (3)	C6—C7—C12—C11	176.06 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.90 (1)	2.02 (1)	2.882 (2)	162 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.896 (5)	2.016 (9)	2.882 (2)	162 (2)

Symmetry code: (i) .