Ethyl 6-methyl-2-sulfanyl-idene-4-[4-(trifluoro-meth-yl)phen-yl]-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

The title compound, C(15)H(15)F(3)N(2)O(2)S, adopts a conformation with an intra-molecular C-H⋯π inter-action. The dihedral angles between the planes of the 4-(trifluoro-meth-yl)phenyl and ester groups with the plane of the six-membered tetra-hydro-pyrimidine ring are 81.8 (1) and 16.0 (1)°, respectively. In the crystal structure, inter-molecular N-H⋯S hydrogen bonds link pairs of mol-ecules into dimers and N-H⋯O inter-actions generate hydrogen-bonded mol-ecular chains along the crystallographic a axis.

Related literature

For applications of multi-functionalized dihydro­pyrimidines, see: Jauk et al. (2000 ▶); Kappe (2000 ▶); Mayer et al. (1999 ▶). For structural analysis, see: Nayak et al. (2009 ▶, 2010 ▶).

Experimental

Crystal data

C15H15F3N2O2S

M = 344.36

Triclinic,

a = 7.2682 (3) Å

b = 9.3205 (2) Å

c = 12.4779 (3) Å

α = 74.199 (2)°

β = 88.092 (3)°

γ = 69.377 (3)°

V = 759.39 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.26 mm−1

T = 120 K

0.28 × 0.22 × 0.17 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with an Eos (Nova) detector

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.932, T max = 0.958

16986 measured reflections

2982 independent reflections

2670 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.085

S = 1.05

2982 reflections

268 parameters

All H-atom parameters refined

Δρmax = 0.33 e Å−3

Δρmin = −0.26 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (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 ▶) and PARST (Nardelli, 1995 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811019441/si2356sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811019441/si2356Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811019441/si2356Isup3.cml

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

C15H15F3N2O2S	Z = 2
Mr = 344.36	F(000) = 356
Triclinic, P1	Dx = 1.506 Mg m−3
Hall symbol: -P 1	Melting point: 471(2) K
a = 7.2682 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3205 (2) Å	Cell parameters from 467 reflections
c = 12.4779 (3) Å	θ = 1.0–27.9°
α = 74.199 (2)°	µ = 0.26 mm−1
β = 88.092 (3)°	T = 120 K
γ = 69.377 (3)°	Block, colorless
V = 759.39 (5) Å3	0.28 × 0.22 × 0.17 mm

Oxford Diffraction Xcalibur diffractometer with an Eos (Nova) detector	2982 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2670 reflections with I > 2σ(I)
graphite	Rint = 0.034
Detector resolution: 16.0839 pixels mm-1	θmax = 26.0°, θmin = 2.4°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −11→11
Tmin = 0.932, Tmax = 0.958	l = −15→15
16986 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	All H-atom parameters refined
S = 1.05	w = 1/[σ2(Fo2) + (0.0385P)2 + 0.4675P] where P = (Fo2 + 2Fc2)/3
2982 reflections	(Δ/σ)max < 0.001
268 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.34d Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.30321 (6)	0.90692 (5)	0.45283 (3)	0.01866 (12)
O2	−0.02059 (15)	0.41096 (13)	0.28311 (9)	0.0192 (2)
N2	−0.01311 (19)	0.83739 (15)	0.42302 (10)	0.0152 (3)
N1	0.2762 (2)	0.67834 (15)	0.37360 (10)	0.0152 (3)
C3	−0.0065 (2)	0.61577 (17)	0.35436 (12)	0.0137 (3)
O1	−0.28789 (15)	0.54256 (13)	0.35999 (9)	0.0202 (2)
C9	−0.2190 (2)	0.89964 (17)	0.25202 (12)	0.0142 (3)
C4	−0.1317 (2)	0.77821 (17)	0.36488 (12)	0.0139 (3)
C5	−0.1193 (2)	0.52013 (17)	0.33520 (12)	0.0146 (3)
C14	−0.1469 (2)	0.87476 (19)	0.15166 (13)	0.0179 (3)
C1	0.1797 (2)	0.80426 (17)	0.41397 (12)	0.0144 (3)
C2	0.1916 (2)	0.57285 (17)	0.35621 (12)	0.0139 (3)
F3	−0.42949 (18)	1.20109 (14)	−0.14515 (8)	0.0412 (3)
C6	−0.1217 (2)	0.31314 (19)	0.25754 (14)	0.0189 (3)
C10	−0.3740 (2)	1.04101 (18)	0.25052 (13)	0.0170 (3)
F2	−0.64945 (16)	1.33939 (13)	−0.05806 (9)	0.0389 (3)
C11	−0.4529 (2)	1.15589 (19)	0.15063 (13)	0.0199 (3)
C13	−0.2264 (2)	0.98893 (19)	0.05111 (13)	0.0202 (3)
C8	0.3400 (2)	0.42067 (19)	0.34389 (15)	0.0196 (3)
C12	−0.3786 (2)	1.12940 (19)	0.05093 (13)	0.0198 (3)
C7	0.0075 (3)	0.2226 (2)	0.18351 (16)	0.0249 (4)
F1	−0.3667 (2)	1.36503 (15)	−0.07403 (10)	0.0514 (4)
C15	−0.4567 (3)	1.2573 (2)	−0.05606 (14)	0.0280 (4)
H4	−0.246 (2)	0.7766 (19)	0.4098 (13)	0.010 (4)*
H2N	−0.075 (3)	0.907 (2)	0.4538 (15)	0.016 (4)*
H1N	0.393 (3)	0.652 (2)	0.3721 (16)	0.024 (5)*
H10	−0.424 (3)	1.059 (2)	0.3189 (15)	0.016 (4)*
H6B	−0.139 (3)	0.241 (2)	0.3277 (15)	0.016 (4)*
H14	−0.045 (3)	0.779 (2)	0.1506 (15)	0.023 (5)*
H13	−0.179 (3)	0.971 (2)	−0.0173 (16)	0.024 (5)*
H6A	−0.251 (3)	0.384 (2)	0.2200 (16)	0.025 (5)*
H11	−0.557 (3)	1.253 (2)	0.1503 (16)	0.026 (5)*
H7A	0.021 (3)	0.296 (3)	0.1166 (18)	0.034 (5)*
H7B	−0.054 (3)	0.152 (2)	0.1647 (17)	0.035 (5)*
H7C	0.132 (3)	0.156 (3)	0.2222 (18)	0.037 (6)*
H8B	0.292 (3)	0.332 (3)	0.3678 (17)	0.037 (6)*
H8C	0.456 (3)	0.395 (3)	0.3874 (19)	0.042 (6)*
H8A	0.367 (3)	0.431 (3)	0.265 (2)	0.049 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0165 (2)	0.0207 (2)	0.0237 (2)	−0.00844 (16)	0.00304 (15)	−0.01173 (16)
O2	0.0148 (5)	0.0196 (6)	0.0303 (6)	−0.0092 (5)	0.0051 (4)	−0.0143 (5)
N2	0.0131 (6)	0.0161 (6)	0.0180 (6)	−0.0042 (5)	0.0007 (5)	−0.0088 (5)
N1	0.0104 (7)	0.0178 (6)	0.0199 (6)	−0.0062 (5)	0.0035 (5)	−0.0080 (5)
C3	0.0144 (7)	0.0134 (7)	0.0133 (7)	−0.0049 (6)	0.0012 (5)	−0.0038 (5)
O1	0.0127 (6)	0.0223 (6)	0.0293 (6)	−0.0079 (5)	0.0048 (4)	−0.0114 (5)
C9	0.0124 (7)	0.0151 (7)	0.0175 (7)	−0.0074 (6)	0.0006 (6)	−0.0052 (6)
C4	0.0125 (7)	0.0162 (7)	0.0154 (7)	−0.0061 (6)	0.0027 (6)	−0.0072 (6)
C5	0.0141 (7)	0.0128 (7)	0.0147 (7)	−0.0032 (6)	−0.0009 (6)	−0.0023 (5)
C14	0.0161 (8)	0.0186 (8)	0.0205 (8)	−0.0053 (6)	0.0023 (6)	−0.0089 (6)
C1	0.0162 (7)	0.0156 (7)	0.0113 (7)	−0.0061 (6)	0.0016 (5)	−0.0030 (5)
C2	0.0156 (7)	0.0141 (7)	0.0124 (7)	−0.0061 (6)	0.0011 (5)	−0.0032 (5)
F3	0.0453 (7)	0.0503 (7)	0.0175 (5)	−0.0100 (6)	−0.0023 (5)	−0.0018 (5)
C6	0.0178 (8)	0.0185 (8)	0.0255 (8)	−0.0103 (7)	0.0016 (6)	−0.0089 (7)
C10	0.0144 (7)	0.0193 (8)	0.0193 (8)	−0.0063 (6)	0.0044 (6)	−0.0084 (6)
F2	0.0303 (6)	0.0363 (6)	0.0314 (6)	0.0008 (5)	−0.0071 (5)	0.0045 (5)
C11	0.0156 (8)	0.0165 (8)	0.0253 (8)	−0.0040 (6)	0.0003 (6)	−0.0043 (6)
C13	0.0219 (8)	0.0254 (8)	0.0166 (7)	−0.0109 (7)	0.0042 (6)	−0.0081 (6)
C8	0.0135 (8)	0.0174 (8)	0.0287 (9)	−0.0043 (6)	0.0014 (7)	−0.0092 (7)
C12	0.0176 (8)	0.0220 (8)	0.0201 (8)	−0.0092 (6)	−0.0020 (6)	−0.0031 (6)
C7	0.0233 (9)	0.0267 (9)	0.0333 (10)	−0.0137 (8)	0.0069 (7)	−0.0166 (8)
F1	0.0618 (9)	0.0444 (7)	0.0454 (7)	−0.0363 (7)	−0.0147 (6)	0.0168 (6)
C15	0.0277 (9)	0.0293 (9)	0.0243 (9)	−0.0120 (8)	−0.0022 (7)	−0.0005 (7)

S1—C1	1.6863 (15)	F3—C15	1.334 (2)
O2—C5	1.3369 (18)	C6—C7	1.502 (2)
O2—C6	1.4557 (18)	C6—H6B	0.982 (18)
N2—C1	1.3323 (19)	C6—H6A	0.98 (2)
N2—C4	1.4725 (18)	C10—C11	1.385 (2)
N2—H2N	0.829 (19)	C10—H10	0.949 (18)
N1—C1	1.3572 (19)	F2—C15	1.336 (2)
N1—C2	1.3940 (19)	C11—C12	1.389 (2)
N1—H1N	0.80 (2)	C11—H11	0.95 (2)
C3—C2	1.351 (2)	C13—C12	1.384 (2)
C3—C5	1.472 (2)	C13—H13	0.946 (19)
C3—C4	1.506 (2)	C8—H8B	0.98 (2)
O1—C5	1.2128 (18)	C8—H8C	0.94 (2)
C9—C14	1.388 (2)	C8—H8A	0.99 (2)
C9—C10	1.396 (2)	C12—C15	1.494 (2)
C9—C4	1.534 (2)	C7—H7A	0.95 (2)
C4—H4	0.988 (17)	C7—H7B	1.00 (2)
C14—C13	1.389 (2)	C7—H7C	0.95 (2)
C14—H14	0.941 (19)	F1—C15	1.348 (2)
C2—C8	1.493 (2)
C5—O2—C6	117.51 (12)	O2—C6—H6A	108.1 (11)
C1—N2—C4	123.64 (13)	C7—C6—H6A	112.1 (11)
C1—N2—H2N	119.0 (13)	H6B—C6—H6A	109.9 (15)
C4—N2—H2N	116.5 (13)	C11—C10—C9	120.59 (14)
C1—N1—C2	123.78 (13)	C11—C10—H10	120.0 (10)
C1—N1—H1N	118.1 (14)	C9—C10—H10	119.4 (10)
C2—N1—H1N	116.8 (14)	C10—C11—C12	119.70 (15)
C2—C3—C5	125.59 (13)	C10—C11—H11	120.2 (12)
C2—C3—C4	119.99 (13)	C12—C11—H11	120.1 (11)
C5—C3—C4	114.30 (12)	C12—C13—C14	119.71 (15)
C14—C9—C10	118.99 (14)	C12—C13—H13	119.8 (11)
C14—C9—C4	122.22 (13)	C14—C13—H13	120.5 (11)
C10—C9—C4	118.79 (13)	C2—C8—H8B	111.7 (12)
N2—C4—C3	109.18 (12)	C2—C8—H8C	109.6 (13)
N2—C4—C9	109.86 (11)	H8B—C8—H8C	108.3 (18)
C3—C4—C9	113.06 (12)	C2—C8—H8A	110.1 (14)
N2—C4—H4	106.2 (9)	H8B—C8—H8A	106.3 (18)
C3—C4—H4	112.9 (9)	H8C—C8—H8A	110.7 (19)
C9—C4—H4	105.4 (9)	C13—C12—C11	120.31 (15)
O1—C5—O2	123.28 (13)	C13—C12—C15	120.14 (15)
O1—C5—C3	123.34 (13)	C11—C12—C15	119.47 (15)
O2—C5—C3	113.31 (12)	C6—C7—H7A	109.3 (12)
C9—C14—C13	120.70 (15)	C6—C7—H7B	109.3 (12)
C9—C14—H14	120.4 (11)	H7A—C7—H7B	109.4 (17)
C13—C14—H14	118.9 (11)	C6—C7—H7C	109.8 (13)
N2—C1—N1	116.24 (13)	H7A—C7—H7C	111.7 (18)
N2—C1—S1	123.24 (11)	H7B—C7—H7C	107.3 (17)
N1—C1—S1	120.50 (11)	F3—C15—F2	106.80 (14)
C3—C2—N1	118.64 (13)	F3—C15—F1	106.00 (15)
C3—C2—C8	128.19 (14)	F2—C15—F1	106.29 (15)
N1—C2—C8	113.16 (13)	F3—C15—C12	112.93 (15)
O2—C6—C7	106.10 (12)	F2—C15—C12	112.89 (14)
O2—C6—H6B	108.8 (10)	F1—C15—C12	111.43 (14)
C7—C6—H6B	111.6 (10)
C1—N2—C4—C3	32.85 (18)	C5—C3—C2—N1	178.91 (13)
C1—N2—C4—C9	−91.67 (16)	C4—C3—C2—N1	3.2 (2)
C2—C3—C4—N2	−24.38 (18)	C5—C3—C2—C8	−2.4 (2)
C5—C3—C4—N2	159.44 (12)	C4—C3—C2—C8	−178.11 (14)
C2—C3—C4—C9	98.24 (16)	C1—N1—C2—C3	15.8 (2)
C5—C3—C4—C9	−77.94 (15)	C1—N1—C2—C8	−163.11 (14)
C14—C9—C4—N2	105.73 (15)	C5—O2—C6—C7	170.73 (13)
C10—C9—C4—N2	−73.24 (16)	C14—C9—C10—C11	−1.0 (2)
C14—C9—C4—C3	−16.51 (19)	C4—C9—C10—C11	177.99 (13)
C10—C9—C4—C3	164.51 (13)	C9—C10—C11—C12	0.8 (2)
C6—O2—C5—O1	−1.3 (2)	C9—C14—C13—C12	0.3 (2)
C6—O2—C5—C3	−178.35 (12)	C14—C13—C12—C11	−0.5 (2)
C2—C3—C5—O1	161.70 (15)	C14—C13—C12—C15	176.18 (15)
C4—C3—C5—O1	−22.4 (2)	C10—C11—C12—C13	0.0 (2)
C2—C3—C5—O2	−21.2 (2)	C10—C11—C12—C15	−176.74 (15)
C4—C3—C5—O2	154.72 (12)	C13—C12—C15—F3	25.8 (2)
C10—C9—C14—C13	0.5 (2)	C11—C12—C15—F3	−157.42 (15)
C4—C9—C14—C13	−178.50 (13)	C13—C12—C15—F2	147.12 (15)
C4—N2—C1—N1	−17.6 (2)	C11—C12—C15—F2	−36.1 (2)
C4—N2—C1—S1	163.99 (11)	C13—C12—C15—F1	−93.35 (19)
C2—N1—C1—N2	−8.8 (2)	C11—C12—C15—F1	83.40 (19)
C2—N1—C1—S1	169.61 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.80 (2)	2.20 (2)	2.9868 (19)	169.8 (18)
N2—H2N···S1ii	0.830 (19)	2.462 (19)	3.2830 (14)	170 (2)
C14—H14···Cg1	0.94 (2)	2.655 (2)	3.129 (2)	112

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.80 (2)	2.20 (2)	2.9868 (19)	169.8 (18)
N2—H2N⋯S1ii	0.830 (19)	2.462 (19)	3.2830 (14)	170 (2)
C14—H14⋯Cg1	0.94 (2)	2.655 (2)	3.129 (2)	112

Symmetry codes: (i) ; (ii) .