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

In the title compound, C(14)H(14)F(4)N(2)O(3)S, the hexa-hydro-pyrimidine ring adopts a half-chair conformation. The mol-ecular conformation is stabilized by an intra-molecular O-H⋯O hydrogen bond, generating an S(6) ring. The crystal structure features O-H⋯S and N-H⋯S hydrogen bonds.

Related literature

For the bioactivity of dihydro­pyrimidines, see: Atwal et al. (1989 ▶); Kappe et al. (1997 ▶); Brier et al. (2004 ▶); Cochran et al. (2005 ▶). For the bioactivity of organofluorine compounds, see: Konz (1997 ▶); Hass (2004 ▶). For a related structure, see: Li et al. (2011 ▶).

Experimental

Crystal data

C14H14F4N2O3S

M = 366.33

Monoclinic,

a = 11.0091 (12) Å

b = 9.9741 (10) Å

c = 14.6890 (16) Å

β = 109.269 (12)°

V = 1522.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.27 mm−1

T = 113 K

0.20 × 0.19 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ▶) T min = 0.947, T max = 0.968

18960 measured reflections

3627 independent reflections

2979 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.084

S = 1.01

3627 reflections

227 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 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: CrystalStructure (Rigaku, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007465/fj2501sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007465/fj2501Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007465/fj2501Isup3.cml

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

C14H14F4N2O3S	F(000) = 752
Mr = 366.33	Dx = 1.598 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5440 reflections
a = 11.0091 (12) Å	θ = 2.0–27.9°
b = 9.9741 (10) Å	µ = 0.27 mm−1
c = 14.6890 (16) Å	T = 113 K
β = 109.269 (12)°	Prism, colorless
V = 1522.6 (3) Å3	0.20 × 0.19 × 0.12 mm
Z = 4

Rigaku Saturn CCD area-detector diffractometer	3627 independent reflections
Radiation source: rotating anode	2979 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.042
Detector resolution: 14.63 pixels mm-1	θmax = 27.9°, θmin = 2.0°
ω and φ scans	h = −14→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −13→13
Tmin = 0.947, Tmax = 0.968	l = −19→18
18960 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.050P)2] where P = (Fo2 + 2Fc2)/3
3627 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.44 e Å−3
0 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
S1	1.09867 (3)	0.59272 (4)	0.13111 (2)	0.01692 (10)
F1	0.63627 (8)	0.49595 (8)	−0.01023 (6)	0.0223 (2)
F2	0.70354 (8)	0.30439 (8)	−0.04289 (6)	0.0208 (2)
F3	0.56928 (7)	0.31300 (9)	0.03576 (6)	0.0211 (2)
F4	0.77930 (9)	0.74276 (9)	0.59153 (6)	0.0287 (2)
O1	0.81420 (9)	0.24372 (9)	0.15081 (7)	0.0161 (2)
H1	0.7778	0.2236	0.1910	0.024*
O2	0.64286 (9)	0.28689 (10)	0.25049 (7)	0.0214 (2)
O3	0.55299 (9)	0.49304 (10)	0.22282 (7)	0.0200 (2)
N1	0.89236 (10)	0.43819 (12)	0.10096 (8)	0.0139 (2)
N2	0.96704 (11)	0.54349 (13)	0.24822 (8)	0.0156 (2)
C1	0.97865 (12)	0.52093 (13)	0.16191 (9)	0.0138 (3)
C2	0.78397 (12)	0.37743 (13)	0.12011 (9)	0.0131 (3)
C3	0.67215 (13)	0.37300 (14)	0.02481 (10)	0.0159 (3)
C4	0.74924 (12)	0.46406 (13)	0.19506 (9)	0.0132 (3)
H4	0.7220	0.5551	0.1673	0.016*
C5	0.64259 (13)	0.40290 (14)	0.22563 (9)	0.0154 (3)
C6	0.44550 (14)	0.44909 (18)	0.25374 (11)	0.0270 (4)
H6A	0.4297	0.3523	0.2400	0.032*
H6B	0.3666	0.4985	0.2169	0.032*
C7	0.47442 (16)	0.47361 (19)	0.35960 (12)	0.0333 (4)
H7A	0.5492	0.4200	0.3963	0.050*
H7B	0.3998	0.4479	0.3781	0.050*
H7C	0.4931	0.5689	0.3736	0.050*
C8	0.87196 (12)	0.47696 (14)	0.28305 (9)	0.0138 (3)
H8	0.9039	0.3849	0.3058	0.017*
C9	0.85100 (12)	0.55238 (14)	0.36593 (9)	0.0136 (3)
C10	0.84025 (13)	0.47892 (14)	0.44373 (10)	0.0160 (3)
H10	0.8506	0.3843	0.4449	0.019*
C11	0.81454 (13)	0.54231 (15)	0.51951 (10)	0.0174 (3)
H11	0.8055	0.4924	0.5720	0.021*
C12	0.80260 (13)	0.67954 (15)	0.51632 (10)	0.0183 (3)
C13	0.81342 (14)	0.75668 (15)	0.44131 (10)	0.0216 (3)
H13	0.8051	0.8515	0.4417	0.026*
C14	0.83700 (14)	0.69099 (14)	0.36509 (10)	0.0184 (3)
H14	0.8436	0.7414	0.3120	0.022*
H2A	1.0172 (14)	0.5927 (16)	0.2825 (11)	0.015 (4)*
H1A	0.9054 (15)	0.4242 (17)	0.0489 (12)	0.026 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.01646 (18)	0.01854 (18)	0.01832 (18)	−0.00502 (13)	0.00919 (14)	−0.00420 (14)
F1	0.0232 (4)	0.0197 (5)	0.0198 (4)	0.0034 (3)	0.0016 (3)	0.0036 (3)
F2	0.0202 (4)	0.0267 (5)	0.0166 (4)	−0.0024 (3)	0.0075 (3)	−0.0088 (3)
F3	0.0137 (4)	0.0288 (5)	0.0210 (4)	−0.0066 (3)	0.0061 (3)	−0.0033 (4)
F4	0.0441 (6)	0.0261 (5)	0.0230 (5)	−0.0029 (4)	0.0206 (4)	−0.0098 (4)
O1	0.0198 (5)	0.0124 (5)	0.0183 (5)	0.0014 (4)	0.0093 (4)	0.0014 (4)
O2	0.0211 (5)	0.0190 (5)	0.0266 (6)	−0.0008 (4)	0.0114 (4)	0.0025 (4)
O3	0.0160 (5)	0.0229 (6)	0.0235 (5)	0.0035 (4)	0.0097 (4)	0.0004 (4)
N1	0.0138 (6)	0.0172 (6)	0.0128 (6)	−0.0028 (4)	0.0071 (5)	−0.0034 (5)
N2	0.0146 (6)	0.0196 (6)	0.0125 (6)	−0.0063 (5)	0.0044 (5)	−0.0045 (5)
C1	0.0134 (7)	0.0128 (6)	0.0149 (7)	0.0019 (5)	0.0044 (5)	−0.0002 (5)
C2	0.0131 (6)	0.0126 (7)	0.0148 (6)	−0.0001 (5)	0.0061 (5)	−0.0005 (5)
C3	0.0157 (7)	0.0160 (7)	0.0178 (7)	−0.0005 (5)	0.0078 (6)	−0.0022 (5)
C4	0.0141 (7)	0.0137 (6)	0.0124 (6)	0.0007 (5)	0.0054 (5)	−0.0006 (5)
C5	0.0143 (7)	0.0185 (7)	0.0127 (6)	−0.0006 (5)	0.0034 (5)	−0.0025 (5)
C6	0.0152 (7)	0.0367 (9)	0.0330 (9)	0.0005 (6)	0.0133 (7)	−0.0020 (7)
C7	0.0292 (9)	0.0453 (11)	0.0317 (9)	0.0066 (8)	0.0185 (8)	0.0055 (8)
C8	0.0134 (6)	0.0149 (7)	0.0134 (6)	−0.0005 (5)	0.0049 (5)	0.0000 (5)
C9	0.0109 (6)	0.0158 (7)	0.0133 (6)	−0.0016 (5)	0.0028 (5)	−0.0013 (5)
C10	0.0170 (7)	0.0141 (7)	0.0166 (7)	−0.0004 (5)	0.0051 (5)	0.0002 (5)
C11	0.0181 (7)	0.0222 (7)	0.0129 (6)	−0.0017 (6)	0.0064 (6)	0.0023 (6)
C12	0.0202 (7)	0.0217 (8)	0.0152 (7)	−0.0024 (6)	0.0092 (6)	−0.0064 (6)
C13	0.0294 (8)	0.0133 (7)	0.0243 (8)	−0.0019 (6)	0.0119 (6)	−0.0028 (6)
C14	0.0242 (8)	0.0161 (7)	0.0169 (7)	−0.0020 (6)	0.0097 (6)	0.0009 (6)

S1—C1	1.6905 (13)	C4—H4	1.0000
F1—C3	1.3381 (16)	C6—C7	1.501 (2)
F2—C3	1.3428 (15)	C6—H6A	0.9900
F3—C3	1.3367 (15)	C6—H6B	0.9900
F4—C12	1.3678 (15)	C7—H7A	0.9800
O1—C2	1.4120 (15)	C7—H7B	0.9800
O1—H1	0.8400	C7—H7C	0.9800
O2—C5	1.2130 (16)	C8—C9	1.5122 (18)
O3—C5	1.3252 (16)	C8—H8	1.0000
O3—C6	1.4675 (16)	C9—C14	1.3906 (19)
N1—C1	1.3504 (17)	C9—C10	1.3950 (18)
N1—C2	1.4462 (16)	C10—C11	1.3881 (19)
N1—H1A	0.835 (16)	C10—H10	0.9500
N2—C1	1.3345 (17)	C11—C12	1.374 (2)
N2—C8	1.4668 (16)	C11—H11	0.9500
N2—H2A	0.785 (16)	C12—C13	1.381 (2)
C2—C3	1.5296 (18)	C13—C14	1.3936 (19)
C2—C4	1.5436 (17)	C13—H13	0.9500
C4—C5	1.5167 (18)	C14—H14	0.9500
C4—C8	1.5363 (18)
C2—O1—H1	109.5	C7—C6—H6A	109.5
C5—O3—C6	117.11 (11)	O3—C6—H6B	109.5
C1—N1—C2	124.90 (11)	C7—C6—H6B	109.5
C1—N1—H1A	114.4 (11)	H6A—C6—H6B	108.1
C2—N1—H1A	120.7 (11)	C6—C7—H7A	109.5
C1—N2—C8	123.93 (12)	C6—C7—H7B	109.5
C1—N2—H2A	116.6 (10)	H7A—C7—H7B	109.5
C8—N2—H2A	119.4 (10)	C6—C7—H7C	109.5
N2—C1—N1	117.77 (12)	H7A—C7—H7C	109.5
N2—C1—S1	120.74 (10)	H7B—C7—H7C	109.5
N1—C1—S1	121.49 (10)	N2—C8—C9	111.83 (11)
O1—C2—N1	109.59 (10)	N2—C8—C4	105.97 (10)
O1—C2—C3	107.38 (11)	C9—C8—C4	113.17 (10)
N1—C2—C3	107.50 (10)	N2—C8—H8	108.6
O1—C2—C4	112.87 (10)	C9—C8—H8	108.6
N1—C2—C4	108.58 (11)	C4—C8—H8	108.6
C3—C2—C4	110.79 (10)	C14—C9—C10	119.37 (13)
F3—C3—F1	107.59 (10)	C14—C9—C8	122.23 (12)
F3—C3—F2	107.24 (11)	C10—C9—C8	118.35 (12)
F1—C3—F2	107.32 (11)	C11—C10—C9	120.83 (13)
F3—C3—C2	111.15 (10)	C11—C10—H10	119.6
F1—C3—C2	111.82 (11)	C9—C10—H10	119.6
F2—C3—C2	111.49 (10)	C12—C11—C10	117.96 (13)
C5—C4—C8	109.66 (10)	C12—C11—H11	121.0
C5—C4—C2	112.60 (11)	C10—C11—H11	121.0
C8—C4—C2	106.91 (10)	F4—C12—C11	118.22 (12)
C5—C4—H4	109.2	F4—C12—C13	118.43 (13)
C8—C4—H4	109.2	C11—C12—C13	123.34 (13)
C2—C4—H4	109.2	C12—C13—C14	117.84 (14)
O2—C5—O3	125.76 (12)	C12—C13—H13	121.1
O2—C5—C4	123.20 (12)	C14—C13—H13	121.1
O3—C5—C4	111.03 (11)	C9—C14—C13	120.64 (13)
O3—C6—C7	110.79 (13)	C9—C14—H14	119.7
O3—C6—H6A	109.5	C13—C14—H14	119.7
C8—N2—C1—N1	4.3 (2)	C2—C4—C5—O2	49.06 (18)
C8—N2—C1—S1	−175.06 (10)	C8—C4—C5—O3	109.10 (13)
C2—N1—C1—N2	3.4 (2)	C2—C4—C5—O3	−132.01 (12)
C2—N1—C1—S1	−177.24 (10)	C5—O3—C6—C7	91.06 (16)
C1—N1—C2—O1	−99.95 (14)	C1—N2—C8—C9	−161.16 (12)
C1—N1—C2—C3	143.65 (13)	C1—N2—C8—C4	−37.41 (17)
C1—N1—C2—C4	23.75 (17)	C5—C4—C8—N2	−176.87 (11)
O1—C2—C3—F3	59.68 (13)	C2—C4—C8—N2	60.79 (13)
N1—C2—C3—F3	177.53 (10)	C5—C4—C8—C9	−53.96 (15)
C4—C2—C3—F3	−63.98 (14)	C2—C4—C8—C9	−176.31 (10)
O1—C2—C3—F1	179.95 (10)	N2—C8—C9—C14	44.36 (17)
N1—C2—C3—F1	−62.21 (13)	C4—C8—C9—C14	−75.23 (16)
C4—C2—C3—F1	56.28 (14)	N2—C8—C9—C10	−138.31 (12)
O1—C2—C3—F2	−59.90 (13)	C4—C8—C9—C10	102.10 (14)
N1—C2—C3—F2	57.94 (14)	C14—C9—C10—C11	0.66 (19)
C4—C2—C3—F2	176.43 (10)	C8—C9—C10—C11	−176.75 (12)
O1—C2—C4—C5	−54.01 (14)	C9—C10—C11—C12	−1.3 (2)
N1—C2—C4—C5	−175.72 (10)	C10—C11—C12—F4	−178.98 (12)
C3—C2—C4—C5	66.45 (14)	C10—C11—C12—C13	0.8 (2)
O1—C2—C4—C8	66.48 (13)	F4—C12—C13—C14	−179.92 (13)
N1—C2—C4—C8	−55.23 (13)	C11—C12—C13—C14	0.3 (2)
C3—C2—C4—C8	−173.07 (10)	C10—C9—C14—C13	0.5 (2)
C6—O3—C5—O2	0.9 (2)	C8—C9—C14—C13	177.79 (13)
C6—O3—C5—C4	−178.03 (11)	C12—C13—C14—C9	−1.0 (2)
C8—C4—C5—O2	−69.83 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	2.06	2.7767 (13)	144
O1—H1···S1i	0.84	2.83	3.3796 (10)	124
N1—H1A···S1ii	0.835 (16)	2.635 (17)	3.4566 (12)	168.1 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84	2.06	2.7767 (13)	144
O1—H1⋯S1i	0.84	2.83	3.3796 (10)	124
N1—H1A⋯S1ii	0.835 (16)	2.635 (17)	3.4566 (12)	168.1 (15)

Symmetry codes: (i) ; (ii) .