4-(4-Bromo-phen-yl)-5-oxo-1,2,3,4,5,6,7,8-octa-hydro-quinazoline-2-thione.

The title compound, C(14)H(13)BrN(2)OS, was synthesized from the multicomponent reaction between thio-urea, 4-bromo-benzaldehyde and cyclo-hexane-1,3-dione. The crystal packing is stabilized by inter-molecular N-H⋯O, N-H⋯S, C-H⋯O and C-H⋯S hydrogen bonds. Br⋯O inter-actions [3.183 (3) Å] are also observed in the crystal structure.

Related literature

For the pharmaceutical applications of 4-aryl-5-oxo-1,2,3,4,5,6,7,8-octa­hydro­quinazoline-2-thio­nes, see: Kappe & Stadler (2004 ▶); Sarac et al. (1997 ▶, 1999 ▶); Yarima et al., (2003 ▶). For background information on halogen bonding, see: Damodharana et al. (2004 ▶); Sureshan et al. (2001 ▶); Yang et al. (2008 ▶).

Experimental

Crystal data

C14H13BrN2OS

M = 337.23

Triclinic,

a = 7.0395 (11) Å

b = 8.1859 (13) Å

c = 13.286 (2) Å

α = 105.329 (2)°

β = 91.279 (2)°

γ = 103.854 (2)°

V = 713.9 (2) Å3

Z = 2

Mo Kα radiation

μ = 3.02 mm−1

T = 293 K

0.25 × 0.25 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.429, T max = 0.547

3953 measured reflections

2744 independent reflections

1880 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.117

S = 1.04

2744 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.60 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028761/zl2225sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028761/zl2225Isup2.hkl

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

C14H13BrN2OS	Z = 2
Mr = 337.23	F(000) = 340
Triclinic, P1	Dx = 1.569 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0395 (11) Å	Cell parameters from 1089 reflections
b = 8.1859 (13) Å	θ = 2.7–23.6°
c = 13.286 (2) Å	µ = 3.02 mm−1
α = 105.329 (2)°	T = 293 K
β = 91.279 (2)°	Block, colourless
γ = 103.854 (2)°	0.25 × 0.25 × 0.20 mm
V = 713.9 (2) Å3

Bruker APEXII area-detector diffractometer	2744 independent reflections
Radiation source: fine-focus sealed tube	1880 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (APEX2; Bruker, 2004)	h = −8→8
Tmin = 0.429, Tmax = 0.547	k = −10→10
3953 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H-atom parameters constrained
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0382P)2 + 0.8552P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2744 reflections	Δρmax = 0.42 e Å−3
174 parameters	Δρmin = −0.60 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0058 (17)

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	0.08077 (11)	0.17375 (8)	−0.08352 (4)	0.0927 (3)
S1	0.81565 (14)	0.62120 (13)	0.47136 (8)	0.0395 (3)
N2	0.4706 (4)	0.6637 (4)	0.4168 (2)	0.0322 (7)
H2	0.4223	0.6000	0.4568	0.039*
C8	0.6646 (5)	0.7134 (5)	0.4188 (3)	0.0294 (8)
C7	0.3316 (5)	0.7096 (4)	0.3511 (3)	0.0291 (8)
H7	0.2139	0.7176	0.3881	0.035*
C6	0.4253 (5)	0.8861 (4)	0.3369 (3)	0.0282 (8)
C5	0.6241 (5)	0.9449 (4)	0.3455 (3)	0.0287 (8)
C1	0.3007 (5)	0.9915 (4)	0.3130 (3)	0.0303 (8)
C4	0.7274 (5)	1.1109 (5)	0.3220 (3)	0.0352 (9)
H4A	0.8475	1.0964	0.2906	0.042*
H4B	0.7626	1.2047	0.3867	0.042*
C2	0.3965 (5)	1.1566 (5)	0.2867 (3)	0.0396 (9)
H2A	0.4084	1.2547	0.3484	0.047*
H2B	0.3129	1.1722	0.2328	0.047*
C3	0.5987 (5)	1.1589 (5)	0.2486 (3)	0.0402 (9)
H3A	0.5851	1.0768	0.1796	0.048*
H3B	0.6606	1.2749	0.2426	0.048*
N1	0.7383 (4)	0.8485 (4)	0.3772 (2)	0.0350 (7)
H1	0.8622	0.8751	0.3703	0.042*
C9	0.2714 (5)	0.5708 (4)	0.2475 (3)	0.0321 (8)
C12	0.1586 (8)	0.3298 (5)	0.0523 (3)	0.0557 (12)
C14	0.0763 (6)	0.4943 (6)	0.2134 (4)	0.0598 (13)
H14	−0.0197	0.5240	0.2564	0.072*
C10	0.4095 (6)	0.5213 (6)	0.1814 (3)	0.0482 (11)
H10	0.5424	0.5704	0.2027	0.058*
C11	0.3538 (7)	0.4003 (6)	0.0842 (3)	0.0545 (12)
H11	0.4483	0.3674	0.0411	0.065*
C13	0.0205 (8)	0.3738 (7)	0.1163 (4)	0.0802 (18)
H13	−0.1120	0.3228	0.0947	0.096*
O1	0.1229 (4)	0.9472 (3)	0.3167 (2)	0.0426 (7)

	U11	U22	U33	U12	U13	U23
Br1	0.1179 (6)	0.0830 (5)	0.0453 (3)	−0.0032 (4)	0.0010 (3)	−0.0098 (3)
S1	0.0319 (6)	0.0473 (6)	0.0477 (6)	0.0135 (4)	0.0060 (4)	0.0239 (5)
N2	0.0243 (17)	0.0368 (17)	0.0377 (17)	0.0038 (13)	0.0046 (13)	0.0172 (14)
C8	0.027 (2)	0.036 (2)	0.0277 (18)	0.0093 (16)	0.0019 (14)	0.0123 (15)
C7	0.0207 (18)	0.0322 (19)	0.0358 (19)	0.0052 (15)	0.0042 (15)	0.0127 (15)
C6	0.0252 (19)	0.0285 (18)	0.0306 (18)	0.0044 (15)	0.0049 (14)	0.0099 (14)
C5	0.0245 (19)	0.0284 (18)	0.0348 (19)	0.0065 (15)	0.0069 (15)	0.0114 (15)
C1	0.026 (2)	0.0326 (19)	0.0319 (19)	0.0073 (15)	0.0046 (15)	0.0079 (15)
C4	0.026 (2)	0.031 (2)	0.050 (2)	0.0026 (16)	0.0055 (17)	0.0165 (17)
C2	0.030 (2)	0.039 (2)	0.053 (2)	0.0100 (17)	0.0058 (18)	0.0179 (18)
C3	0.034 (2)	0.041 (2)	0.051 (2)	0.0052 (18)	0.0070 (18)	0.0251 (19)
N1	0.0208 (16)	0.0410 (18)	0.0496 (19)	0.0077 (13)	0.0072 (14)	0.0231 (15)
C9	0.030 (2)	0.0297 (19)	0.038 (2)	0.0042 (16)	0.0037 (16)	0.0161 (16)
C12	0.073 (3)	0.040 (2)	0.041 (2)	−0.003 (2)	0.007 (2)	0.0044 (19)
C14	0.034 (2)	0.074 (3)	0.050 (3)	−0.002 (2)	0.006 (2)	−0.003 (2)
C10	0.037 (2)	0.054 (3)	0.049 (3)	0.010 (2)	0.0076 (19)	0.008 (2)
C11	0.067 (3)	0.051 (3)	0.044 (3)	0.014 (2)	0.015 (2)	0.010 (2)
C13	0.045 (3)	0.092 (4)	0.064 (3)	−0.013 (3)	0.000 (3)	−0.017 (3)
O1	0.0251 (15)	0.0507 (17)	0.0573 (18)	0.0117 (12)	0.0069 (12)	0.0221 (14)

Br1—C12	1.895 (4)	C4—H4B	0.9700
Br1—O1i	3.183 (3)	C2—C3	1.519 (5)
S1—C8	1.678 (4)	C2—H2A	0.9700
N2—C8	1.326 (4)	C2—H2B	0.9700
N2—C7	1.474 (4)	C3—H3A	0.9700
N2—H2	0.8600	C3—H3B	0.9700
C8—N1	1.364 (4)	N1—H1	0.8600
C7—C6	1.500 (5)	C9—C14	1.376 (5)
C7—C9	1.510 (5)	C9—C10	1.386 (5)
C7—H7	0.9800	C12—C13	1.356 (6)
C6—C5	1.358 (5)	C12—C11	1.366 (7)
C6—C1	1.453 (5)	C14—C13	1.383 (6)
C5—N1	1.382 (4)	C14—H14	0.9300
C5—C4	1.495 (5)	C10—C11	1.384 (6)
C1—O1	1.222 (4)	C10—H10	0.9300
C1—C2	1.492 (5)	C11—H11	0.9300
C4—C3	1.504 (5)	C13—H13	0.9300
C4—H4A	0.9700
C12—Br1—O1i	154.81 (16)	C1—C2—H2B	108.9
C8—N2—C7	124.8 (3)	C3—C2—H2B	108.9
C8—N2—H2	117.6	H2A—C2—H2B	107.7
C7—N2—H2	117.6	C4—C3—C2	111.6 (3)
N2—C8—N1	116.3 (3)	C4—C3—H3A	109.3
N2—C8—S1	123.1 (3)	C2—C3—H3A	109.3
N1—C8—S1	120.6 (3)	C4—C3—H3B	109.3
N2—C7—C6	108.5 (3)	C2—C3—H3B	109.3
N2—C7—C9	111.0 (3)	H3A—C3—H3B	108.0
C6—C7—C9	112.0 (3)	C8—N1—C5	123.3 (3)
N2—C7—H7	108.4	C8—N1—H1	118.3
C6—C7—H7	108.4	C5—N1—H1	118.3
C9—C7—H7	108.4	C14—C9—C10	117.5 (4)
C5—C6—C1	120.8 (3)	C14—C9—C7	121.0 (3)
C5—C6—C7	120.1 (3)	C10—C9—C7	121.4 (3)
C1—C6—C7	119.1 (3)	C13—C12—C11	120.5 (4)
C6—C5—N1	119.4 (3)	C13—C12—Br1	119.9 (4)
C6—C5—C4	122.9 (3)	C11—C12—Br1	119.6 (3)
N1—C5—C4	117.7 (3)	C9—C14—C13	121.1 (4)
O1—C1—C6	120.6 (3)	C9—C14—H14	119.4
O1—C1—C2	121.3 (3)	C13—C14—H14	119.4
C6—C1—C2	118.1 (3)	C11—C10—C9	121.4 (4)
C5—C4—C3	110.8 (3)	C11—C10—H10	119.3
C5—C4—H4A	109.5	C9—C10—H10	119.3
C3—C4—H4A	109.5	C12—C11—C10	119.3 (4)
C5—C4—H4B	109.5	C12—C11—H11	120.3
C3—C4—H4B	109.5	C10—C11—H11	120.3
H4A—C4—H4B	108.1	C12—C13—C14	120.2 (5)
C1—C2—C3	113.4 (3)	C12—C13—H13	119.9
C1—C2—H2A	108.9	C14—C13—H13	119.9
C3—C2—H2A	108.9
C7—N2—C8—N1	16.5 (5)	C1—C2—C3—C4	−50.8 (5)
C7—N2—C8—S1	−164.9 (3)	N2—C8—N1—C5	7.6 (5)
C8—N2—C7—C6	−31.3 (4)	S1—C8—N1—C5	−171.1 (3)
C8—N2—C7—C9	92.1 (4)	C6—C5—N1—C8	−12.3 (5)
N2—C7—C6—C5	24.8 (4)	C4—C5—N1—C8	167.8 (3)
C9—C7—C6—C5	−98.0 (4)	N2—C7—C9—C14	126.7 (4)
N2—C7—C6—C1	−155.8 (3)	C6—C7—C9—C14	−111.9 (4)
C9—C7—C6—C1	81.3 (4)	N2—C7—C9—C10	−56.1 (4)
C1—C6—C5—N1	174.5 (3)	C6—C7—C9—C10	65.3 (4)
C7—C6—C5—N1	−6.1 (5)	O1i—Br1—C12—C13	63.0 (6)
C1—C6—C5—C4	−5.6 (5)	O1i—Br1—C12—C11	−115.5 (5)
C7—C6—C5—C4	173.8 (3)	C10—C9—C14—C13	−0.7 (7)
C5—C6—C1—O1	−171.9 (3)	C7—C9—C14—C13	176.6 (5)
C7—C6—C1—O1	8.8 (5)	C14—C9—C10—C11	0.5 (6)
C5—C6—C1—C2	6.5 (5)	C7—C9—C10—C11	−176.8 (4)
C7—C6—C1—C2	−172.9 (3)	C13—C12—C11—C10	−1.9 (7)
C6—C5—C4—C3	−23.7 (5)	Br1—C12—C11—C10	176.6 (3)
N1—C5—C4—C3	156.2 (3)	C9—C10—C11—C12	0.8 (7)
O1—C1—C2—C3	−159.6 (4)	C11—C12—C13—C14	1.8 (9)
C6—C1—C2—C3	22.0 (5)	Br1—C12—C13—C14	−176.8 (4)
C5—C4—C3—C2	50.7 (4)	C9—C14—C13—C12	−0.4 (9)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···S1ii	0.97	2.98	3.781 (4)	140
N2—H2···S1iii	0.86	2.55	3.380 (3)	161
N1—H1···O1iv	0.86	2.00	2.832 (4)	164
C4—H4A···O1iv	0.97	2.59	3.361 (4)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯S1i	0.97	2.98	3.781 (4)	140
N2—H2⋯S1ii	0.86	2.55	3.380 (3)	161
N1—H1⋯O1iii	0.86	2.00	2.832 (4)	164
C4—H4A⋯O1iii	0.97	2.59	3.361 (4)	137

Symmetry codes: (i) ; (ii) ; (iii) .