Ethyl 4-hy-droxy-6-(4-hy-droxy-phen-yl)-4-trifluoro-methyl-2-sulfanyl-idene-1,3-diazinane-5-carboxyl-ate ethanol monosolvate.

The title compound, C(14)H(15)F(3)N(2)O(4)S·C(2)H(5)OH, was prepared by reaction of 4-hy-droxy-benzaldehyde, ethyl 4,4,4-trifluoro-3-oxobutano-ate and thio-urea. The hexa-hydro-pyrimidine ring adopts a half-chair conformation, the mean plane formed by the ring atoms excluding the C atom bonded to the eth-oxy-carbonyl group has an r.m.s. deviation of 0.0333 Å, and the dihedral angle between this plane and the benzene ring is 56.76 (5)°. The mol-ecular conformation is stabilized by an intra-molecular O-H⋯O hydrogen bond, generating an S(6) ring. The crystal structure is stabilized by inter-molecular O-H⋯O, O-H⋯S, N-H⋯O and N-H⋯S hydrogen bonds. The ethyl group of the ester unit is disordered over two positions, with an occupancy ratio of 0.757 (10):0.243 (10).

Related literature

For the bioactivity of dihydro­pyrimidines, see: Brier et al. (2004 ▶); Cochran et al. (2005 ▶); Moran et al. (2007 ▶); Zorkun et al. (2006 ▶). For the bioactivity of organofluorine compounds, see: Hermann et al. (2003 ▶); Ulrich (2004 ▶). For a related structure, see: Song et al. (2010 ▶).

Experimental

Crystal data

C14H15F3N2O4S·C2H6O

M = 410.41

Monoclinic,

a = 14.7204 (14) Å

b = 9.9772 (12) Å

c = 14.7357 (15) Å

β = 119.716 (11)°

V = 1879.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 113 K

0.20 × 0.16 × 0.10 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ▶) T min = 0.955, T max = 0.977

23471 measured reflections

4486 independent reflections

3815 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.092

S = 1.03

4486 reflections

280 parameters

24 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrystalClear (Rigaku, 2009 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015376/om2424sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015376/om2424Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811015376/om2424Isup3.cml

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

C14H15F3N2O4S·C2H6O	F(000) = 856
Mr = 410.41	Dx = 1.450 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.7204 (14) Å	Cell parameters from 6768 reflections
b = 9.9772 (12) Å	θ = 2.0–27.9°
c = 14.7357 (15) Å	µ = 0.23 mm−1
β = 119.716 (11)°	T = 113 K
V = 1879.6 (3) Å3	Prism, colorless
Z = 4	0.20 × 0.16 × 0.10 mm

Rigaku Saturn CCD area-detector diffractometer	4486 independent reflections
Radiation source: rotating anode	3815 reflections with I > 2σ(I)
multilayer	Rint = 0.047
Detector resolution: 14.63 pixels mm-1	θmax = 27.9°, θmin = 2.6°
ω and φ scans	h = −18→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −13→13
Tmin = 0.955, Tmax = 0.977	l = −19→19
23471 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0506P)2] where P = (Fo2 + 2Fc2)/3
4486 reflections	(Δ/σ)max = 0.004
280 parameters	Δρmax = 0.47 e Å−3
24 restraints	Δρmin = −0.27 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	Occ. (<1)
S1	0.42068 (2)	0.59475 (3)	0.35546 (2)	0.01745 (10)
F1	0.79908 (6)	0.50693 (8)	0.56642 (6)	0.0289 (2)
F2	0.74838 (6)	0.31639 (8)	0.59449 (6)	0.0272 (2)
F3	0.85429 (6)	0.32318 (9)	0.53355 (6)	0.0293 (2)
O1	0.65426 (7)	0.24640 (9)	0.38459 (7)	0.0190 (2)
H1	0.6926 (15)	0.2229 (18)	0.3589 (15)	0.056 (6)*
O2	0.79221 (7)	0.28215 (9)	0.31283 (7)	0.0234 (2)
O3	0.85300 (8)	0.49263 (10)	0.32835 (9)	0.0356 (3)
O4	0.68310 (8)	0.73637 (10)	−0.05667 (8)	0.0264 (2)
H4	0.7053 (15)	0.6801 (19)	−0.0829 (14)	0.048 (6)*
N1	0.58962 (8)	0.44198 (11)	0.41833 (8)	0.0161 (2)
N2	0.52429 (9)	0.53998 (11)	0.25624 (8)	0.0171 (2)
C1	0.51772 (9)	0.52182 (12)	0.34218 (9)	0.0154 (3)
C2	0.67753 (10)	0.38150 (12)	0.41637 (10)	0.0156 (3)
C3	0.77017 (10)	0.38279 (13)	0.52882 (10)	0.0199 (3)
C4	0.70305 (9)	0.46428 (12)	0.34352 (9)	0.0153 (3)
H4A	0.7255	0.5564	0.3730	0.018*
C5	0.78765 (10)	0.40048 (13)	0.32782 (10)	0.0183 (3)
C6	0.9245 (3)	0.4501 (3)	0.2899 (4)	0.0349 (8)	0.757 (10)
H6A	0.8925	0.3759	0.2391	0.042*	0.757 (10)
H6B	0.9914	0.4179	0.3490	0.042*	0.757 (10)
C7	0.9440 (2)	0.5681 (4)	0.2384 (2)	0.0371 (9)	0.757 (10)
H7A	0.9920	0.5418	0.2134	0.056*	0.757 (10)
H7B	0.9751	0.6413	0.2890	0.056*	0.757 (10)
H7C	0.8777	0.5981	0.1791	0.056*	0.757 (10)
C6'	0.9536 (7)	0.4377 (10)	0.3420 (11)	0.034 (2)	0.243 (10)
H6'A	0.9568	0.3387	0.3462	0.041*	0.243 (10)
H6'B	1.0158	0.4770	0.4028	0.041*	0.243 (10)
C7'	0.9382 (8)	0.4894 (18)	0.2394 (9)	0.056 (3)	0.243 (10)
H7'A	0.9987	0.4651	0.2320	0.083*	0.243 (10)
H7'B	0.9309	0.5872	0.2373	0.083*	0.243 (10)
H7'C	0.8748	0.4497	0.1820	0.083*	0.243 (10)
C8	0.60150 (10)	0.47359 (12)	0.23647 (9)	0.0157 (3)
H8A	0.5765	0.3807	0.2107	0.019*
C9	0.61729 (10)	0.54638 (12)	0.15579 (9)	0.0158 (3)
C10	0.63212 (10)	0.47113 (13)	0.08457 (9)	0.0171 (3)
H10A	0.6260	0.3763	0.0842	0.021*
C11	0.65560 (10)	0.53228 (13)	0.01436 (10)	0.0179 (3)
H11A	0.6675	0.4794	−0.0323	0.021*
C12	0.66173 (10)	0.67134 (13)	0.01224 (10)	0.0179 (3)
C13	0.64511 (11)	0.74801 (13)	0.08177 (10)	0.0215 (3)
H13A	0.6479	0.8430	0.0799	0.026*
C14	0.62449 (11)	0.68552 (13)	0.15354 (10)	0.0194 (3)
H14A	0.6151	0.7382	0.2020	0.023*
O5	0.74901 (7)	0.56068 (11)	0.84823 (8)	0.0276 (2)
H5	0.7076	0.5158	0.7956	0.041*
C15	0.84625 (12)	0.57515 (17)	0.84999 (13)	0.0359 (4)
H15A	0.8351	0.6201	0.7854	0.043*
H15B	0.8774	0.4859	0.8539	0.043*
C16	0.91849 (13)	0.65741 (19)	0.94378 (15)	0.0484 (5)
H16A	0.9857	0.6682	0.9460	0.073*
H16B	0.9295	0.6120	1.0074	0.073*
H16C	0.8873	0.7457	0.9391	0.073*
H1A	0.5812 (12)	0.4270 (16)	0.4708 (13)	0.037 (5)*
H2A	0.4826 (11)	0.5934 (14)	0.2148 (11)	0.018 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.01884 (18)	0.01825 (17)	0.01816 (17)	0.00402 (12)	0.01138 (14)	0.00283 (12)
F1	0.0287 (5)	0.0258 (4)	0.0222 (4)	−0.0028 (4)	0.0051 (4)	−0.0062 (3)
F2	0.0265 (5)	0.0362 (5)	0.0191 (4)	0.0057 (4)	0.0116 (4)	0.0094 (3)
F3	0.0191 (4)	0.0438 (5)	0.0235 (4)	0.0123 (4)	0.0093 (4)	0.0032 (4)
O1	0.0237 (5)	0.0137 (5)	0.0235 (5)	−0.0001 (4)	0.0147 (4)	−0.0010 (4)
O2	0.0242 (5)	0.0206 (5)	0.0291 (5)	0.0010 (4)	0.0160 (4)	−0.0031 (4)
O3	0.0276 (6)	0.0282 (6)	0.0643 (8)	−0.0086 (5)	0.0330 (6)	−0.0118 (5)
O4	0.0427 (6)	0.0200 (5)	0.0283 (5)	0.0029 (4)	0.0267 (5)	0.0046 (4)
N1	0.0176 (6)	0.0183 (5)	0.0151 (5)	0.0028 (4)	0.0100 (5)	0.0027 (4)
N2	0.0167 (6)	0.0204 (6)	0.0145 (5)	0.0046 (5)	0.0080 (5)	0.0033 (4)
C1	0.0169 (6)	0.0133 (6)	0.0158 (6)	−0.0025 (5)	0.0080 (5)	−0.0010 (5)
C2	0.0159 (6)	0.0148 (6)	0.0165 (6)	0.0006 (5)	0.0084 (5)	0.0000 (5)
C3	0.0199 (7)	0.0216 (7)	0.0195 (6)	0.0037 (5)	0.0108 (6)	0.0014 (5)
C4	0.0167 (6)	0.0143 (6)	0.0161 (6)	−0.0005 (5)	0.0090 (5)	−0.0008 (5)
C5	0.0145 (6)	0.0229 (7)	0.0159 (6)	−0.0009 (5)	0.0063 (5)	−0.0011 (5)
C6	0.0241 (17)	0.0424 (15)	0.050 (2)	−0.0031 (12)	0.0270 (17)	−0.0049 (16)
C7	0.0250 (12)	0.062 (2)	0.0300 (12)	−0.0070 (13)	0.0177 (10)	0.0034 (13)
C6'	0.012 (4)	0.041 (4)	0.050 (6)	0.001 (3)	0.015 (4)	0.002 (4)
C7'	0.039 (5)	0.081 (8)	0.058 (5)	−0.005 (5)	0.033 (4)	0.002 (5)
C8	0.0175 (6)	0.0158 (6)	0.0154 (6)	−0.0005 (5)	0.0095 (5)	−0.0012 (5)
C9	0.0155 (6)	0.0167 (6)	0.0147 (6)	0.0008 (5)	0.0072 (5)	0.0009 (5)
C10	0.0196 (7)	0.0142 (6)	0.0179 (6)	−0.0006 (5)	0.0096 (6)	−0.0004 (5)
C11	0.0209 (7)	0.0184 (6)	0.0160 (6)	0.0000 (5)	0.0105 (6)	−0.0023 (5)
C12	0.0193 (7)	0.0190 (7)	0.0173 (6)	0.0018 (5)	0.0106 (6)	0.0034 (5)
C13	0.0292 (8)	0.0137 (6)	0.0251 (7)	0.0012 (5)	0.0161 (6)	0.0002 (5)
C14	0.0253 (7)	0.0172 (6)	0.0196 (6)	0.0010 (5)	0.0140 (6)	−0.0018 (5)
O5	0.0236 (5)	0.0372 (6)	0.0255 (5)	−0.0044 (4)	0.0149 (5)	−0.0081 (4)
C15	0.0264 (8)	0.0492 (10)	0.0368 (9)	−0.0002 (7)	0.0193 (8)	0.0010 (8)
C16	0.0275 (9)	0.0468 (11)	0.0586 (12)	−0.0065 (8)	0.0120 (9)	−0.0034 (9)

S1—C1	1.6987 (13)	C7—H7C	0.9800
F1—C3	1.3373 (15)	C6'—C7'	1.504 (14)
F2—C3	1.3364 (15)	C6'—H6'A	0.9900
F3—C3	1.3440 (15)	C6'—H6'B	0.9900
O1—C2	1.4123 (15)	C7'—H7'A	0.9800
O1—H1	0.853 (19)	C7'—H7'B	0.9800
O2—C5	1.2090 (15)	C7'—H7'C	0.9800
O3—C5	1.3279 (16)	C8—C9	1.5063 (17)
O3—C6	1.483 (3)	C8—H8A	1.0000
O3—C6'	1.497 (9)	C9—C10	1.3927 (17)
O4—C12	1.3666 (15)	C9—C14	1.3939 (17)
O4—H4	0.835 (18)	C10—C11	1.3844 (17)
N1—C1	1.3551 (16)	C10—H10A	0.9500
N1—C2	1.4410 (16)	C11—C12	1.3917 (18)
N1—H1A	0.855 (17)	C11—H11A	0.9500
N2—C1	1.3294 (16)	C12—C13	1.3940 (18)
N2—C8	1.4640 (16)	C13—C14	1.3849 (18)
N2—H2A	0.814 (14)	C13—H13A	0.9500
C2—C3	1.5380 (18)	C14—H14A	0.9500
C2—C4	1.5413 (17)	O5—C15	1.4261 (16)
C4—C5	1.5149 (17)	O5—H5	0.8400
C4—C8	1.5472 (17)	C15—C16	1.503 (2)
C4—H4A	1.0000	C15—H15A	0.9900
C6—C7	1.504 (4)	C15—H15B	0.9900
C6—H6A	0.9900	C16—H16A	0.9800
C6—H6B	0.9900	C16—H16B	0.9800
C7—H7A	0.9800	C16—H16C	0.9800
C7—H7B	0.9800
C2—O1—H1	107.7 (13)	O3—C6'—H6'A	112.7
C5—O3—C6	116.66 (15)	C7'—C6'—H6'A	112.7
C5—O3—C6'	114.4 (4)	O3—C6'—H6'B	112.7
C6—O3—C6'	26.4 (4)	C7'—C6'—H6'B	112.7
C12—O4—H4	108.2 (13)	H6'A—C6'—H6'B	110.2
C1—N1—C2	124.76 (11)	C6'—C7'—H7'A	109.5
C1—N1—H1A	116.6 (11)	C6'—C7'—H7'B	109.5
C2—N1—H1A	118.6 (11)	H7'A—C7'—H7'B	109.5
C1—N2—C8	123.93 (11)	C6'—C7'—H7'C	109.5
C1—N2—H2A	114.8 (10)	H7'A—C7'—H7'C	109.5
C8—N2—H2A	121.3 (10)	H7'B—C7'—H7'C	109.5
N2—C1—N1	118.24 (11)	N2—C8—C9	112.19 (10)
N2—C1—S1	120.92 (10)	N2—C8—C4	106.10 (10)
N1—C1—S1	120.84 (9)	C9—C8—C4	112.61 (10)
O1—C2—N1	109.49 (10)	N2—C8—H8A	108.6
O1—C2—C3	107.76 (10)	C9—C8—H8A	108.6
N1—C2—C3	107.48 (10)	C4—C8—H8A	108.6
O1—C2—C4	112.54 (10)	C10—C9—C14	118.48 (12)
N1—C2—C4	108.72 (10)	C10—C9—C8	118.55 (11)
C3—C2—C4	110.72 (10)	C14—C9—C8	122.83 (11)
F2—C3—F1	107.49 (10)	C11—C10—C9	121.06 (12)
F2—C3—F3	106.79 (10)	C11—C10—H10A	119.5
F1—C3—F3	107.01 (11)	C9—C10—H10A	119.5
F2—C3—C2	111.90 (11)	C10—C11—C12	119.94 (12)
F1—C3—C2	112.59 (10)	C10—C11—H11A	120.0
F3—C3—C2	110.75 (10)	C12—C11—H11A	120.0
C5—C4—C2	112.57 (10)	O4—C12—C11	122.09 (12)
C5—C4—C8	108.75 (10)	O4—C12—C13	118.32 (12)
C2—C4—C8	107.24 (10)	C11—C12—C13	119.58 (12)
C5—C4—H4A	109.4	C14—C13—C12	119.94 (12)
C2—C4—H4A	109.4	C14—C13—H13A	120.0
C8—C4—H4A	109.4	C12—C13—H13A	120.0
O2—C5—O3	124.85 (12)	C13—C14—C9	120.96 (12)
O2—C5—C4	124.23 (12)	C13—C14—H14A	119.5
O3—C5—C4	110.86 (11)	C9—C14—H14A	119.5
O3—C6—C7	108.6 (2)	C15—O5—H5	109.5
O3—C6—H6A	110.0	O5—C15—C16	108.56 (13)
C7—C6—H6A	110.0	O5—C15—H15A	110.0
O3—C6—H6B	110.0	C16—C15—H15A	110.0
C7—C6—H6B	110.0	O5—C15—H15B	110.0
H6A—C6—H6B	108.4	C16—C15—H15B	110.0
C6—C7—H7A	109.5	H15A—C15—H15B	108.4
C6—C7—H7B	109.5	C15—C16—H16A	109.5
H7A—C7—H7B	109.5	C15—C16—H16B	109.5
C6—C7—H7C	109.5	H16A—C16—H16B	109.5
H7A—C7—H7C	109.5	C15—C16—H16C	109.5
H7B—C7—H7C	109.5	H16A—C16—H16C	109.5
O3—C6'—C7'	95.3 (7)	H16B—C16—H16C	109.5
C8—N2—C1—N1	3.16 (18)	C8—C4—C5—O2	−75.56 (15)
C8—N2—C1—S1	−175.89 (9)	C2—C4—C5—O3	−139.51 (11)
C2—N1—C1—N2	4.26 (18)	C8—C4—C5—O3	101.80 (12)
C2—N1—C1—S1	−176.69 (9)	C5—O3—C6—C7	147.6 (2)
C1—N1—C2—O1	−100.03 (14)	C6'—O3—C6—C7	−120.7 (11)
C1—N1—C2—C3	143.19 (12)	C5—O3—C6'—C7'	119.4 (7)
C1—N1—C2—C4	23.29 (16)	C6—O3—C6'—C7'	18.2 (10)
O1—C2—C3—F2	−59.19 (13)	C1—N2—C8—C9	−159.43 (11)
N1—C2—C3—F2	58.73 (13)	C1—N2—C8—C4	−36.07 (16)
C4—C2—C3—F2	177.35 (10)	C5—C4—C8—N2	−178.07 (10)
O1—C2—C3—F1	179.61 (10)	C2—C4—C8—N2	59.94 (12)
N1—C2—C3—F1	−62.47 (13)	C5—C4—C8—C9	−54.97 (13)
C4—C2—C3—F1	56.15 (14)	C2—C4—C8—C9	−176.96 (10)
O1—C2—C3—F3	59.84 (13)	N2—C8—C9—C10	−141.94 (12)
N1—C2—C3—F3	177.76 (10)	C4—C8—C9—C10	98.43 (13)
C4—C2—C3—F3	−63.63 (14)	N2—C8—C9—C14	42.35 (16)
O1—C2—C4—C5	−52.75 (14)	C4—C8—C9—C14	−77.28 (15)
N1—C2—C4—C5	−174.22 (10)	C14—C9—C10—C11	1.30 (18)
C3—C2—C4—C5	67.91 (13)	C8—C9—C10—C11	−174.60 (11)
O1—C2—C4—C8	66.82 (13)	C9—C10—C11—C12	−1.85 (19)
N1—C2—C4—C8	−54.65 (13)	C10—C11—C12—O4	−178.99 (12)
C3—C2—C4—C8	−172.52 (10)	C10—C11—C12—C13	0.62 (19)
C6—O3—C5—O2	11.0 (3)	O4—C12—C13—C14	−179.24 (12)
C6'—O3—C5—O2	−18.2 (6)	C11—C12—C13—C14	1.14 (19)
C6—O3—C5—C4	−166.3 (2)	C12—C13—C14—C9	−1.7 (2)
C6'—O3—C5—C4	164.5 (6)	C10—C9—C14—C13	0.48 (19)
C2—C4—C5—O2	43.13 (17)	C8—C9—C14—C13	176.20 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.853 (19)	1.987 (19)	2.7383 (13)	146.3 (17)
O1—H1···S1i	0.853 (19)	3.029 (19)	3.4858 (11)	115.8 (15)
O4—H4···O5ii	0.835 (18)	1.873 (19)	2.7066 (14)	175.6 (19)
O5—H5···S1iii	0.84	2.36	3.1970 (11)	175
N1—H1A···S1iii	0.855 (17)	2.583 (18)	3.4307 (12)	171.5 (14)
N2—H2A···O1iv	0.814 (14)	2.368 (15)	3.1701 (15)	168.7 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.853 (19)	1.987 (19)	2.7383 (13)	146.3 (17)
O1—H1⋯S1i	0.853 (19)	3.029 (19)	3.4858 (11)	115.8 (15)
O4—H4⋯O5ii	0.835 (18)	1.873 (19)	2.7066 (14)	175.6 (19)
O5—H5⋯S1iii	0.84	2.36	3.1970 (11)	175
N1—H1A⋯S1iii	0.855 (17)	2.583 (18)	3.4307 (12)	171.5 (14)
N2—H2A⋯O1iv	0.814 (14)	2.368 (15)	3.1701 (15)	168.7 (14)

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