Ethyl 4-(4-chloro-phen-yl)-6-methyl-2-thioxo-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C(14)H(15)ClN(2)O(2)S, the tetra-hydro-pyrimidine ring adopts a twisted boat conformation with the carbonyl group in an s-trans conformation with respect to the C=C double bond of the six-membered tetra-hydro-pyrimidine ring. The mol-ecular conformation is determined by an intra-molecular C-H⋯π inter-action. The crystal structure is further stabilized by inter-molecular N-H⋯O mol-ecular chains and centrosymmetric N-H⋯S dimers.

Related literature

For background to the applications of poly-functionalized dihydro­pyrimidines, see: Corey & Cheng (1995 ▶); Hurst & Hull (1961 ▶); Jauk et al. (2000 ▶); Kappe (2000 ▶); Mayer et al. (1999 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C14H15ClN2O2S

M = 310.80

Triclinic,

a = 7.3420 (3) Å

b = 9.4895 (4) Å

c = 12.0425 (5) Å

α = 73.823 (4)°

β = 88.512 (3)°

γ = 70.264 (4)°

V = 756.32 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.39 mm−1

T = 292 K

0.24 × 0.22 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Eos (Nova) detector

Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T min = 0.902, T max = 0.933

16944 measured reflections

2960 independent reflections

2232 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.161

S = 1.09

2960 reflections

183 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1993 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037453/sj2653sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037453/sj2653Isup2.hkl

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

C14H15ClN2O2S	Z = 2
Mr = 310.80	F(000) = 324
Triclinic, P1	Dx = 1.365 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 7.3420 (3) Å	Cell parameters from 340 reflections
b = 9.4895 (4) Å	θ = 1.0–28.0°
c = 12.0425 (5) Å	µ = 0.39 mm−1
α = 73.823 (4)°	T = 292 K
β = 88.512 (3)°	Block, colorless
γ = 70.264 (4)°	0.24 × 0.22 × 0.18 mm
V = 756.32 (6) Å3

Oxford Diffraction Xcalibur with Eos (Nova) detector diffractometer	2960 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2232 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 16.0839 pixels mm-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −11→11
Tmin = 0.902, Tmax = 0.933	l = −14→14
16944 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.094P)2 + 0.1394P] where P = (Fo2 + 2Fc2)/3
2960 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

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.

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
S1	0.19746 (10)	0.59669 (9)	0.54217 (7)	0.0474 (3)
Cl1	0.98420 (16)	0.22640 (13)	1.09156 (8)	0.0841 (4)
N2	0.5115 (3)	0.6617 (3)	0.57987 (18)	0.0368 (5)
H2	0.5687	0.6038	0.5368	0.044*
C3	0.5079 (4)	0.8759 (3)	0.6529 (2)	0.0337 (6)
N1	0.2287 (3)	0.8143 (3)	0.6307 (2)	0.0395 (5)
H1	0.1099	0.8288	0.6463	0.047*
C4	0.6301 (4)	0.7183 (3)	0.6403 (2)	0.0343 (6)
H4	0.7360	0.7320	0.5922	0.041*
O2	0.5259 (3)	1.0762 (3)	0.7252 (2)	0.0562 (6)
O1	0.7882 (3)	0.9466 (2)	0.64949 (19)	0.0501 (5)
C1	0.3222 (4)	0.6937 (3)	0.5869 (2)	0.0352 (6)
C9	0.7198 (3)	0.5977 (3)	0.7561 (2)	0.0330 (6)
C2	0.3137 (4)	0.9158 (3)	0.6519 (2)	0.0352 (6)
C5	0.6218 (4)	0.9691 (3)	0.6732 (2)	0.0373 (6)
C14	0.6506 (4)	0.6140 (4)	0.8616 (2)	0.0467 (7)
H14	0.5469	0.7027	0.8633	0.056*
C6	0.6261 (5)	1.1724 (4)	0.7526 (3)	0.0571 (8)
H6A	0.7528	1.1073	0.7916	0.069*
H6B	0.6434	1.2452	0.6821	0.069*
C8	0.1693 (4)	1.0610 (4)	0.6676 (3)	0.0520 (8)
H8A	0.2170	1.1461	0.6395	0.078*
H8B	0.1488	1.0468	0.7485	0.078*
H8C	0.0490	1.0840	0.6251	0.078*
C10	0.8750 (4)	0.4642 (4)	0.7572 (3)	0.0472 (7)
H10	0.9247	0.4523	0.6873	0.057*
C12	0.8839 (4)	0.3695 (4)	0.9625 (3)	0.0499 (7)
C11	0.9569 (4)	0.3507 (4)	0.8560 (3)	0.0489 (7)
H11	1.0597	0.2617	0.8539	0.059*
C13	0.7329 (5)	0.5008 (4)	0.9644 (3)	0.0532 (8)
H13	0.6856	0.5140	1.0345	0.064*
C7	0.5083 (6)	1.2561 (6)	0.8271 (5)	0.1004 (17)
H7A	0.5077	1.1839	0.9009	0.151*
H7B	0.3781	1.3084	0.7922	0.151*
H7C	0.5608	1.3317	0.8379	0.151*

	U11	U22	U33	U12	U13	U23
S1	0.0396 (4)	0.0547 (5)	0.0629 (5)	−0.0215 (3)	0.0076 (3)	−0.0340 (4)
Cl1	0.0859 (7)	0.0806 (7)	0.0595 (6)	−0.0202 (6)	−0.0165 (5)	0.0120 (5)
N2	0.0311 (12)	0.0444 (13)	0.0402 (11)	−0.0104 (10)	0.0019 (9)	−0.0236 (10)
C3	0.0304 (13)	0.0358 (14)	0.0366 (13)	−0.0117 (11)	0.0014 (10)	−0.0124 (11)
N1	0.0330 (12)	0.0468 (13)	0.0508 (13)	−0.0190 (10)	0.0131 (10)	−0.0271 (11)
C4	0.0300 (13)	0.0409 (14)	0.0386 (13)	−0.0156 (11)	0.0079 (10)	−0.0179 (11)
O2	0.0448 (12)	0.0589 (14)	0.0878 (16)	−0.0276 (10)	0.0155 (11)	−0.0453 (13)
O1	0.0322 (11)	0.0551 (13)	0.0722 (14)	−0.0202 (9)	0.0073 (9)	−0.0265 (11)
C1	0.0369 (14)	0.0388 (14)	0.0316 (12)	−0.0127 (11)	0.0040 (10)	−0.0134 (11)
C9	0.0277 (13)	0.0393 (14)	0.0378 (13)	−0.0141 (11)	0.0041 (10)	−0.0171 (11)
C2	0.0341 (14)	0.0353 (14)	0.0376 (13)	−0.0123 (11)	0.0015 (10)	−0.0121 (11)
C5	0.0404 (16)	0.0338 (14)	0.0371 (13)	−0.0120 (12)	0.0017 (11)	−0.0098 (11)
C14	0.0449 (17)	0.0473 (16)	0.0463 (16)	−0.0090 (13)	0.0060 (13)	−0.0195 (14)
C6	0.056 (2)	0.0570 (19)	0.079 (2)	−0.0327 (16)	0.0092 (17)	−0.0356 (18)
C8	0.0314 (15)	0.0469 (17)	0.082 (2)	−0.0096 (13)	0.0046 (14)	−0.0304 (17)
C10	0.0379 (15)	0.0524 (18)	0.0508 (17)	−0.0091 (13)	0.0088 (13)	−0.0224 (15)
C12	0.0429 (16)	0.0570 (18)	0.0457 (16)	−0.0185 (14)	−0.0079 (13)	−0.0056 (14)
C11	0.0324 (15)	0.0459 (17)	0.0593 (18)	−0.0023 (13)	0.0021 (13)	−0.0147 (15)
C13	0.060 (2)	0.062 (2)	0.0397 (16)	−0.0214 (16)	0.0062 (14)	−0.0179 (15)
C7	0.079 (3)	0.130 (4)	0.152 (4)	−0.063 (3)	0.045 (3)	−0.103 (4)

S1—C1	1.688 (3)	C2—C8	1.486 (4)
Cl1—C12	1.735 (3)	C14—C13	1.382 (4)
N2—C1	1.324 (3)	C14—H14	0.9300
N2—C4	1.464 (3)	C6—C7	1.441 (5)
N2—H2	0.8600	C6—H6A	0.9700
C3—C2	1.345 (3)	C6—H6B	0.9700
C3—C5	1.474 (4)	C8—H8A	0.9600
C3—C4	1.510 (3)	C8—H8B	0.9600
N1—C1	1.359 (3)	C8—H8C	0.9600
N1—C2	1.390 (3)	C10—C11	1.349 (4)
N1—H1	0.8600	C10—H10	0.9300
C4—C9	1.528 (4)	C12—C13	1.365 (5)
C4—H4	0.9800	C12—C11	1.411 (4)
O2—C5	1.330 (3)	C11—H11	0.9300
O2—C6	1.455 (3)	C13—H13	0.9300
O1—C5	1.208 (3)	C7—H7A	0.9600
C9—C14	1.386 (4)	C7—H7B	0.9600
C9—C10	1.386 (4)	C7—H7C	0.9600
C1—N2—C4	124.5 (2)	C7—C6—O2	107.4 (3)
C1—N2—H2	117.7	C7—C6—H6A	110.2
C4—N2—H2	117.7	O2—C6—H6A	110.2
C2—C3—C5	126.0 (2)	C7—C6—H6B	110.2
C2—C3—C4	119.9 (2)	O2—C6—H6B	110.2
C5—C3—C4	113.9 (2)	H6A—C6—H6B	108.5
C1—N1—C2	123.8 (2)	C2—C8—H8A	109.5
C1—N1—H1	118.1	C2—C8—H8B	109.5
C2—N1—H1	118.1	H8A—C8—H8B	109.5
N2—C4—C3	109.1 (2)	C2—C8—H8C	109.5
N2—C4—C9	110.3 (2)	H8A—C8—H8C	109.5
C3—C4—C9	113.21 (19)	H8B—C8—H8C	109.5
N2—C4—H4	108.0	C11—C10—C9	122.5 (3)
C3—C4—H4	108.0	C11—C10—H10	118.7
C9—C4—H4	108.0	C9—C10—H10	118.7
C5—O2—C6	118.1 (2)	C13—C12—C11	120.0 (3)
N2—C1—N1	116.0 (2)	C13—C12—Cl1	119.6 (2)
N2—C1—S1	123.59 (19)	C11—C12—Cl1	120.5 (2)
N1—C1—S1	120.36 (19)	C10—C11—C12	118.9 (3)
C14—C9—C10	117.7 (3)	C10—C11—H11	120.6
C14—C9—C4	122.9 (2)	C12—C11—H11	120.6
C10—C9—C4	119.5 (2)	C12—C13—C14	119.8 (3)
C3—C2—N1	118.7 (2)	C12—C13—H13	120.1
C3—C2—C8	128.3 (2)	C14—C13—H13	120.1
N1—C2—C8	112.9 (2)	C6—C7—H7A	109.5
O1—C5—O2	123.2 (2)	C6—C7—H7B	109.5
O1—C5—C3	123.5 (2)	H7A—C7—H7B	109.5
O2—C5—C3	113.2 (2)	C6—C7—H7C	109.5
C13—C14—C9	121.2 (3)	H7A—C7—H7C	109.5
C13—C14—H14	119.4	H7B—C7—H7C	109.5
C9—C14—H14	119.4
C1—N2—C4—C3	−31.3 (3)	C1—N1—C2—C8	163.8 (3)
C1—N2—C4—C9	93.6 (3)	C6—O2—C5—O1	1.1 (4)
C2—C3—C4—N2	24.4 (3)	C6—O2—C5—C3	178.3 (2)
C5—C3—C4—N2	−159.3 (2)	C2—C3—C5—O1	−163.6 (3)
C2—C3—C4—C9	−98.8 (3)	C4—C3—C5—O1	20.4 (4)
C5—C3—C4—C9	77.4 (3)	C2—C3—C5—O2	19.2 (4)
C4—N2—C1—N1	15.8 (4)	C4—C3—C5—O2	−156.7 (2)
C4—N2—C1—S1	−165.7 (2)	C10—C9—C14—C13	−0.3 (4)
C2—N1—C1—N2	9.3 (4)	C4—C9—C14—C13	178.6 (3)
C2—N1—C1—S1	−169.2 (2)	C5—O2—C6—C7	−169.1 (3)
N2—C4—C9—C14	−103.7 (3)	C14—C9—C10—C11	1.1 (4)
C3—C4—C9—C14	18.9 (3)	C4—C9—C10—C11	−177.8 (3)
N2—C4—C9—C10	75.2 (3)	C9—C10—C11—C12	−1.0 (5)
C3—C4—C9—C10	−162.3 (2)	C13—C12—C11—C10	0.0 (5)
C5—C3—C2—N1	179.7 (2)	Cl1—C12—C11—C10	179.8 (2)
C4—C3—C2—N1	−4.6 (4)	C11—C12—C13—C14	0.8 (5)
C5—C3—C2—C8	1.6 (5)	Cl1—C12—C13—C14	−179.0 (2)
C4—C3—C2—C8	177.3 (3)	C9—C14—C13—C12	−0.7 (5)
C1—N1—C2—C3	−14.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	2.25	3.077 (3)	161
N2—H2···S1ii	0.86	2.49	3.323 (3)	164
C14—H14···Cg1	0.93	2.67	3.146 (4)	113

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.86	2.25	3.077 (3)	161
N2—H2⋯S1ii	0.86	2.49	3.323 (3)	164
C14—H14⋯Cg1	0.93	2.67	3.146 (4)	113

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C2=C3 double bond.