1-(3-Chloro-phen-yl)-4,4,6-trimethyl-3,4-dihydro-pyrimidine-2(1H)-thione.

In the title compound, C(13)H(15)ClN(2)S, the dihydro-pyrimidine ring is essentially planar, with a maximum deviation from the least-squares plane of 0.122 (3) Å for the unsubstitued olefinic C atom. The dihedral angle between the dihydro-pyrimidine and benzene rings is 86.62 (13)°. The crystal structure is stabilized by inter-molecular N-H⋯S hydrogen bonds, which form centrosymmetric dimers arranged along the c axis.

Related literature

For related structures, see: Yamin et al. (2005 ▶); Ismail et al. (2007 ▶); Saeed & Bolte, (2010 ▶). For the biological activity of dihydro­pyrimidinone/thione derivatives, see: Alam et al. (2005 ▶); Kappe (2000 ▶); Sriram et al. (2006 ▶); Leite et al. (2006 ▶). For graph-set theory, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C13H15ClN2S

M = 266.78

Monoclinic,

a = 8.398 (2) Å

b = 14.930 (4) Å

c = 11.468 (3) Å

β = 103.909 (4)°

V = 1395.7 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.40 mm−1

T = 298 K

0.40 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.855, T max = 0.934

8215 measured reflections

2598 independent reflections

2212 reflections with I > 2/s(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.133

S = 1.10

2598 reflections

157 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.14 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1995 ▶) and PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810054292/dn2640sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054292/dn2640Isup2.hkl

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

C13H15ClN2S	F(000) = 560
Mr = 266.78	Dx = 1.270 Mg m−3
Monoclinic, P21/c	Melting point = 427.6–429.6 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.398 (2) Å	Cell parameters from 2921 reflections
b = 14.930 (4) Å	θ = 2.2–25.5°
c = 11.468 (3) Å	µ = 0.40 mm−1
β = 103.909 (4)°	T = 298 K
V = 1395.7 (6) Å3	Block, colourless
Z = 4	0.40 × 0.19 × 0.17 mm

Bruker SMART APEX CCD area-detector diffractometer	2598 independent reflections
Radiation source: fine-focus sealed tube	2212 reflections with I > 2/s(I)
graphite	Rint = 0.021
Detector resolution: 83.66 pixels mm-1	θmax = 25.5°, θmin = 2.2°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −13→18
Tmin = 0.855, Tmax = 0.934	l = −12→13
8215 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0696P)2 + 0.4092P] where P = (Fo2 + 2Fc2)/3
2598 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.14 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 > σ(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
Cl1	0.26790 (8)	0.97009 (5)	−0.03961 (6)	0.0647 (2)
S1	0.77220 (7)	1.01839 (4)	0.36163 (5)	0.0496 (2)
N1	0.8934 (2)	0.87127 (13)	0.47479 (18)	0.0508 (5)
H1A	0.9700	0.9086	0.5030	0.061*
N2	0.6306 (2)	0.85790 (12)	0.35950 (17)	0.0467 (5)
C1	0.7657 (3)	0.90982 (15)	0.40192 (19)	0.0408 (5)
C2	0.6333 (3)	0.76397 (16)	0.3814 (3)	0.0598 (7)
C3	0.7636 (4)	0.72845 (18)	0.4552 (3)	0.0693 (8)
H3	0.7690	0.6664	0.4621	0.083*
C4	0.9012 (3)	0.78148 (16)	0.5276 (2)	0.0602 (7)
C5	0.4926 (4)	0.7110 (2)	0.3124 (4)	0.1029 (13)
H5A	0.5133	0.6484	0.3283	0.154*
H5B	0.4787	0.7222	0.2281	0.154*
H5C	0.3947	0.7281	0.3360	0.154*
C7	1.0658 (5)	0.7413 (2)	0.5222 (5)	0.1179 (16)
H7A	1.0740	0.7392	0.4401	0.177*
H7B	1.0745	0.6818	0.5547	0.177*
H7C	1.1528	0.7777	0.5682	0.177*
C8	0.4808 (3)	0.90016 (15)	0.2952 (2)	0.0450 (5)
C9	0.4507 (3)	0.91237 (15)	0.1734 (2)	0.0448 (5)
H9	0.5261	0.8933	0.1311	0.054*
C10	0.3064 (3)	0.95355 (15)	0.1145 (2)	0.0468 (5)
C11	0.1924 (3)	0.98094 (17)	0.1755 (3)	0.0571 (7)
H11	0.0959	1.0088	0.1351	0.069*
C12	0.2238 (3)	0.96636 (19)	0.2971 (3)	0.0644 (7)
H12	0.1467	0.9837	0.3389	0.077*
C13	0.3679 (3)	0.92637 (18)	0.3583 (2)	0.0578 (6)
H13	0.3887	0.9173	0.4408	0.069*
C6	0.8890 (7)	0.7904 (3)	0.6570 (3)	0.137 (2)
H6A	0.9756	0.8284	0.7001	0.206*
H6B	0.8989	0.7323	0.6940	0.206*
H6C	0.7849	0.8161	0.6590	0.206*

	U11	U22	U33	U12	U13	U23
Cl1	0.0586 (4)	0.0726 (5)	0.0561 (4)	−0.0055 (3)	0.0005 (3)	0.0109 (3)
S1	0.0455 (4)	0.0420 (3)	0.0541 (4)	−0.0027 (2)	−0.0022 (3)	0.0110 (3)
N1	0.0452 (11)	0.0431 (11)	0.0568 (11)	0.0034 (8)	−0.0022 (9)	0.0078 (9)
N2	0.0430 (10)	0.0391 (10)	0.0546 (11)	−0.0009 (8)	0.0050 (8)	0.0046 (8)
C1	0.0399 (11)	0.0419 (12)	0.0397 (11)	0.0035 (9)	0.0077 (9)	0.0014 (9)
C2	0.0618 (16)	0.0402 (13)	0.0743 (17)	−0.0030 (11)	0.0104 (13)	0.0033 (12)
C3	0.082 (2)	0.0373 (13)	0.081 (2)	0.0015 (13)	0.0059 (16)	0.0088 (13)
C4	0.0760 (18)	0.0425 (13)	0.0546 (14)	0.0126 (12)	0.0010 (12)	0.0076 (11)
C5	0.082 (2)	0.0519 (17)	0.158 (4)	−0.0206 (16)	−0.004 (2)	0.008 (2)
C7	0.080 (2)	0.064 (2)	0.185 (5)	0.0305 (18)	−0.015 (2)	−0.003 (3)
C8	0.0378 (11)	0.0412 (12)	0.0534 (13)	−0.0050 (9)	0.0056 (9)	−0.0017 (10)
C9	0.0393 (11)	0.0438 (12)	0.0520 (13)	−0.0049 (9)	0.0123 (10)	−0.0022 (10)
C10	0.0412 (12)	0.0414 (11)	0.0533 (13)	−0.0084 (10)	0.0025 (10)	0.0012 (10)
C11	0.0412 (13)	0.0535 (15)	0.0714 (17)	0.0033 (11)	0.0035 (12)	−0.0057 (12)
C12	0.0506 (15)	0.0716 (19)	0.0732 (19)	0.0066 (12)	0.0195 (14)	−0.0122 (14)
C13	0.0538 (15)	0.0655 (17)	0.0546 (14)	0.0006 (12)	0.0142 (12)	−0.0055 (12)
C6	0.270 (6)	0.082 (3)	0.058 (2)	−0.033 (3)	0.035 (3)	0.0098 (19)

Cl1—C10	1.736 (3)	C7—H7A	0.9600
S1—C1	1.690 (2)	C7—H7B	0.9600
N1—C1	1.323 (3)	C7—H7C	0.9600
N1—C4	1.466 (3)	C8—C9	1.372 (3)
N1—H1A	0.8541	C8—C13	1.380 (3)
N2—C1	1.364 (3)	C9—C10	1.382 (3)
N2—C2	1.424 (3)	C9—H9	0.9300
N2—C8	1.441 (3)	C10—C11	1.376 (4)
C2—C3	1.323 (4)	C11—C12	1.372 (4)
C2—C5	1.483 (4)	C11—H11	0.9300
C3—C4	1.480 (4)	C12—C13	1.381 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C6	1.518 (5)	C13—H13	0.9300
C4—C7	1.522 (4)	C6—H6A	0.9600
C5—H5A	0.9600	C6—H6B	0.9600
C5—H5B	0.9600	C6—H6C	0.9600
C5—H5C	0.9600
C1—N1—C4	127.4 (2)	H7A—C7—H7B	109.5
C1—N1—H1A	112.2	C4—C7—H7C	109.5
C4—N1—H1A	119.1	H7A—C7—H7C	109.5
C1—N2—C2	121.35 (19)	H7B—C7—H7C	109.5
C1—N2—C8	118.85 (18)	C9—C8—C13	121.0 (2)
C2—N2—C8	119.75 (18)	C9—C8—N2	120.2 (2)
N1—C1—N2	117.2 (2)	C13—C8—N2	118.8 (2)
N1—C1—S1	121.01 (17)	C8—C9—C10	118.8 (2)
N2—C1—S1	121.78 (15)	C8—C9—H9	120.6
C3—C2—N2	118.9 (2)	C10—C9—H9	120.6
C3—C2—C5	123.9 (2)	C11—C10—C9	121.3 (2)
N2—C2—C5	117.0 (2)	C11—C10—Cl1	119.56 (19)
C2—C3—C4	124.0 (2)	C9—C10—Cl1	119.16 (19)
C2—C3—H3	118.0	C12—C11—C10	118.8 (2)
C4—C3—H3	118.0	C12—C11—H11	120.6
N1—C4—C3	107.8 (2)	C10—C11—H11	120.6
N1—C4—C6	108.5 (2)	C11—C12—C13	121.0 (2)
C3—C4—C6	111.6 (3)	C11—C12—H12	119.5
N1—C4—C7	107.1 (3)	C13—C12—H12	119.5
C3—C4—C7	111.2 (3)	C8—C13—C12	119.0 (2)
C6—C4—C7	110.5 (3)	C8—C13—H13	120.5
C2—C5—H5A	109.5	C12—C13—H13	120.5
C2—C5—H5B	109.5	C4—C6—H6A	109.5
H5A—C5—H5B	109.5	C4—C6—H6B	109.5
C2—C5—H5C	109.5	H6A—C6—H6B	109.5
H5A—C5—H5C	109.5	C4—C6—H6C	109.5
H5B—C5—H5C	109.5	H6A—C6—H6C	109.5
C4—C7—H7A	109.5	H6B—C6—H6C	109.5
C4—C7—H7B	109.5
C4—N1—C1—N2	−8.0 (4)	C2—C3—C4—C6	100.9 (4)
C4—N1—C1—S1	173.1 (2)	C2—C3—C4—C7	−135.3 (3)
C2—N2—C1—N1	−7.0 (3)	C1—N2—C8—C9	88.4 (3)
C8—N2—C1—N1	170.6 (2)	C2—N2—C8—C9	−94.0 (3)
C2—N2—C1—S1	171.87 (19)	C1—N2—C8—C13	−92.8 (3)
C8—N2—C1—S1	−10.5 (3)	C2—N2—C8—C13	84.9 (3)
C1—N2—C2—C3	7.4 (4)	C13—C8—C9—C10	1.5 (3)
C8—N2—C2—C3	−170.1 (3)	N2—C8—C9—C10	−179.65 (19)
C1—N2—C2—C5	−168.4 (3)	C8—C9—C10—C11	−1.0 (3)
C8—N2—C2—C5	14.1 (4)	C8—C9—C10—Cl1	179.51 (17)
N2—C2—C3—C4	6.8 (4)	C9—C10—C11—C12	−0.3 (4)
C5—C2—C3—C4	−177.7 (3)	Cl1—C10—C11—C12	179.2 (2)
C1—N1—C4—C3	19.4 (4)	C10—C11—C12—C13	1.1 (4)
C1—N1—C4—C6	−101.6 (3)	C9—C8—C13—C12	−0.7 (4)
C1—N1—C4—C7	139.1 (3)	N2—C8—C13—C12	−179.6 (2)
C2—C3—C4—N1	−18.2 (4)	C11—C12—C13—C8	−0.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1i	0.85	2.58	3.404 (2)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1i	0.85	2.58	3.404 (2)	162

Symmetry code: (i) .