Ethyl 4-hy­droxy-6-(4-hy­droxy­phen­yl)-4-trifluoro­methyl-2-sulfanyl­idene-1,3-diazinane-5-carboxyl­ate ethanol monosolvate

Yang, F.-L.; Fa, W.-J.

doi:10.1107/S1600536811015376

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages o1280-o1281

doi:10.1107/S1600536811015376

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Ethyl 4-hydroxy-6-(4-hydroxyphenyl)-4-trifluoromethyl-2-sulfanylidene-1,3-diazinane-5-carboxylate ethanol monosolvate

Feng-Ling Yang ^a ^* and Wen-Jun Fa ^b

^aCollege of Chemistry and Chemical Engineering, Pingdingshan University, Pingdingshan, Henan Province 467000, People's Republic of China, and ^bInstitute of Surface Micro and Nano Materials, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China
^*Correspondence e-mail: actaeli@gmail.com

(Received 18 April 2011; accepted 23 April 2011; online 29 April 2011)

The title compound, C₁₄H₁₅F₃N₂O₄S·C₂H₅OH, was prepared by reaction of 4-hydroxybenzaldehyde, ethyl 4,4,4-trifluoro-3-oxobutanoate and thiourea. The hexahydropyrimidine ring adopts a half-chair conformation, the mean plane formed by the ring atoms excluding the C atom bonded to the ethoxycarbonyl 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 molecular conformation is stabilized by an intramolecular O—H⋯O hydrogen bond, generating an S(6) ring. The crystal structure is stabilized by intermolecular 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_r = 410.41
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.092
S = 1.03
4486 reflections
280 parameters
24 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.27 e Å⁻³

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⋯O1^iv	0.814 (14)	2.368 (15)	3.1701 (15)	168.7 (14)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) -x+1, -y+1, -z+1; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

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

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

Supporting information file. DOI: 10.1107/S1600536811015376/om2424Isup3.cml

checkCIF report

Comment top

Dihydropyrimidine (DHPM) derivatives can be used as potential calcium channel blockers (Zorkun et al., 2006), inhibitors of mitotic kinesin Eg5 for treating cancer (Cochran et al., 2005; Brier et al., 2004) and as TRPA1 modulators for treating pain (Moran et al., 2007). In addition, compounds that contain fluorine have special bioactivity, e.g. flumioxazin is a widely used herbicide (Hermann et al., 2003; Ulrich, 2004). This led us to focus our attention on the synthesis and bioactivity of these important fused perfluoroalkylated heterocyclic compounds. During the synthesis of DHPM derivatives, the title compound, an intermediate C₁₄H₁₅F₃N₂O₄S.C₂H₅OH was isolated and the structure confirmed by X-ray diffraction.

In the structure of the title molecule, the 1,3-diazinane ring adopts a half-chair conformation, the mean plane formed by the ring atoms excluding the C atom bonded to the ethoxy carbonyl group has an r.m.s. deviation of 0.0333 Å, the dihedral angle between the mean plane and benzene ring is 56.76 (5)°. The molecular conformation is stabilized by intramolecular O—H···O hydrogen bond, generating an S(6) ring. The crystal structure is stabilized by intermolecular hydrogen bonds (O—H···O, O—H···S, N—H···O and N—H···S). The ethyl group of the ester unit is disordered over two positions, with a site-occupancy ratio of 0.757 (10):0.243 (10). For a crystal structure related to the title compound, see: Song et al., 2010.

Related literature top

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 top

The title compound was synthesized by refluxing for 3 h a stirred solution of 4-hydroxybenzaldehyde (2.45 g, 20 mmol), ethyl 4,4,4-trifluoro-3-oxobutanoate (4.42 g, 24 mmol) and thiourea (2.28 g, 30 mmol) in 20 ml of anhydrous ethanol. The reaction was catalyzed by sulfamic acid (0.6 g). The solvent was evaporated in vacuo and the residue was washed with water. The title compound was recrystallized by slow evaporation of a 50% aqueous ethanol solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2009); cell refinement: CrystalClear (Rigaku, 2009); data reduction: CrystalClear (Rigaku, 2009); 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 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular configuration and atom numbering scheme with displacement ellipsoids drawn at the 30% probability level.

Ethyl 4-hydroxy-6-(4-hydroxyphenyl)-4-trifluoromethyl-2-sulfanylidene- 1,3-diazinane-5-carboxylate ethanol monosolvate top

Crystal data top

C₁₄H₁₅F₃N₂O₄S·C₂H₆O	F(000) = 856
M_r = 410.41	D_x = 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

Data collection top

Rigaku Saturn CCD area-detector diffractometer	4486 independent reflections
Radiation source: rotating anode	3815 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.047
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.9°, θ_min = 2.6°
ω and ϕ scans	h = −18→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −13→13
T_min = 0.955, T_max = 0.977	l = −19→19
23471 measured reflections

Refinement top

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(F_o²) + (0.0506P)²] where P = (F_o² + 2F_c²)/3
4486 reflections	(Δ/σ)_max = 0.004
280 parameters	Δρ_max = 0.47 e Å⁻³
24 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₁₅F₃N₂O₄S·C₂H₆O	V = 1879.6 (3) Å³
M_r = 410.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.7204 (14) Å	µ = 0.23 mm⁻¹
b = 9.9772 (12) Å	T = 113 K
c = 14.7357 (15) Å	0.20 × 0.16 × 0.10 mm
β = 119.716 (11)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	4486 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	3815 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.977	R_int = 0.047
23471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	24 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.47 e Å⁻³
4486 reflections	Δρ_min = −0.27 e Å⁻³
280 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.814 (14)	2.368 (15)	3.1701 (15)	168.7 (14)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅F₃N₂O₄S·C₂H₆O
M_r	410.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	14.7204 (14), 9.9772 (12), 14.7357 (15)
β (°)	119.716 (11)
V (Å³)	1879.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.20 × 0.16 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2009)
T_min, T_max	0.955, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	23471, 4486, 3815
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.03
No. of reflections	4486
No. of parameters	280
No. of restraints	24
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.27

Computer programs: CrystalClear (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.814 (14)	2.368 (15)	3.1701 (15)	168.7 (14)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the Natural Science Foundation of Henan Province, China (grant No. 082300420110) and the Natural Science Foundation of Henan Province Education Department, China (grant No. 2007150036).

References

Brier, S., Lemaire, D., Debonis, S., Forest, E. & Kozielski, F. (2004). Biochemistry, 43, 13072–13082. Web of Science CrossRef PubMed CAS Google Scholar
Cochran, J. C., Gatial, J. E., Kapoor, T. M. & Gilbert, S. P. (2005). J. Biol. Chem. 280, 12658–12667. Web of Science CrossRef PubMed CAS Google Scholar
Hermann, B., Erwin, H. & Hansjorg, K. (2003). US Patent No. 2 003 176 284. Google Scholar
Moran, M. M., Fanger, C., Chong, J. A., McNamara, C., Zhen, X. G. & Mandel-Brehm, J. (2007). WO Patent No. 2 007 073 505. Google Scholar
Rigaku (2009). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, X.-P., Li, G.-C., Wu, C.-Z. & Yang, F.-L. (2010). Acta Cryst. E66, o1083. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ulrich, H. (2004). US Patent No. 2 004 033 897. Google Scholar
Zorkun, I. S., Sarac, S., Celebi, S. & Erol, K. (2006). Bioorg. Med. Chem. 14, 8582–8589. Web of Science CrossRef PubMed CAS Google Scholar

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages o1280-o1281

doi:10.1107/S1600536811015376

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl 4-hy­dr­oxy-6-(4-hy­dr­oxy­phen­yl)-4-tri­fluoro­methyl-2-sulfanyl­­idene-1,3-diazinane-5-carboxyl­ate ethanol monosolvate

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Experimental

Crystal data

Data collection

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Supporting information

Acknowledgements

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organic compounds

Ethyl 4-hydroxy-6-(4-hydroxyphenyl)-4-trifluoromethyl-2-sulfanylidene-1,3-diazinane-5-carboxylate ethanol monosolvate