5-Benzoyl-4-hydr­oxy-6-(4-nitro­phen­yl)-4-trifluoro­meth­yl-3,4,5,6-tetrahydro­pyrimidin-2(1H)-one monohydrate

Feng-Ling Yang; Jing Zhang; Chang-Sheng Yao

doi:10.1107/S160053680804124X

. 2008 Dec 10;65(Pt 1):o87–o88. doi: 10.1107/S160053680804124X

5-Benzoyl-4-hydroxy-6-(4-nitrophenyl)-4-trifluoromethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one monohydrate

Feng-Ling Yang ^a,^*, Jing Zhang ^b, Chang-Sheng Yao ^c,^d

PMCID: PMC2967995 PMID: 21581725

Abstract

The asymmetric unit of the title compound, C₁₈H₁₄F₃N₃O₅·H₂O, contains two independent formula units. The two heterocyclic molecules differ in the orientations of the benzoylphenyl group with respect to the tetrahydropyrimidine ring [C—C—C—C torsion angles of 64.5 (3) and 67.1 (3)°]. In both molecules the pyrimidine ring adopts a half-chair conformation. The molecules are linked into a two-dimensional network parallel to (001) by N—H⋯O and O—H⋯O hydrogen bonds.

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 ▶).

Experimental

Crystal data

C₁₈H₁₄F₃N₃O₅·H₂O
M _r = 427.34
Orthorhombic,
a = 14.389 (3) Å
b = 9.0391 (18) Å
c = 28.141 (6) Å
V = 3660.1 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 113 (2) K
0.32 × 0.22 × 0.20 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2002 ▶) T _min = 0.958, T _max = 0.973
28524 measured reflections
4437 independent reflections
4222 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.107
S = 1.06
4437 reflections
575 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2002 ▶); 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680804124X/ci2728sup1.cif

e-65-00o87-sup1.cif^{(32.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680804124X/ci2728Isup2.hkl

e-65-00o87-Isup2.hkl^{(217.4KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O11	0.92 (4)	2.11 (4)	2.903 (3)	144 (3)
N1—H1⋯O11ⁱ	0.95 (3)	2.08 (4)	3.011 (3)	167 (3)
N5—H5⋯O12ⁱⁱ	0.89 (4)	2.05 (4)	2.907 (3)	163 (3)
N4—H4⋯O12ⁱⁱⁱ	0.85 (4)	2.17 (4)	3.019 (3)	176 (3)
O5—H5A⋯O6^iv	0.89 (4)	1.78 (4)	2.678 (3)	178 (4)
O10—H10A⋯O1^v	0.85 (2)	1.82 (2)	2.672 (3)	178 (4)
O12—H12A⋯O5	0.85 (4)	2.13 (4)	2.817 (3)	137 (3)
O12—H12A⋯O2	0.85 (4)	2.32 (4)	3.026 (3)	140 (3)
O11—H11A⋯O10^vi	0.82 (4)	2.22 (4)	2.815 (3)	129 (3)
O11—H11A⋯O7^vi	0.82 (4)	2.27 (4)	3.009 (3)	150 (3)
O11—H11B⋯O6^vii	0.83 (4)	2.05 (4)	2.853 (3)	163 (4)
O12—H12B⋯O1^viii	0.82 (4)	2.12 (4)	2.840 (3)	147 (3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

The authors thank the Natural Science Foundation of Henan Province (grant No. 082300420110) and the Natural Science Foundation of Henan Province Education Department (grant No. 2007150036) for financial support.

supplementary crystallographic information

Comment

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). Besides, compounds that contain fluorine have special bioactivity, for example, flumioxazin is a widely used herbicide (Hermann et al., 2003; Ulrich,2004). This led us to pay much attention to the synthesis and bioactivity of these important fused perfluoroalkylated heterocyclic compounds. During the synthesis of DHPM derivatives, the title compound, an intermediate, was isolated and confirmed by X-ray diffraction to elucidate the reaction mechanism. We report here the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig.1) contains two independent molecules which differ in the orientations of benzoylphenyl group with respect to the tetrahydropyrimidine ring. In both molecules, the pyrimidine ring adopts a half-chair conformation. The bulky substituents on the heterocyclic ring are in trans position, which must be attributed to the steric effect. The dihedral angles between C5-C10 and C12-C17 phenyl rings is 60.0 (1)° and that between C23-C28 and C30-C35 rings is 65.2 (1)°.

The crystal packing shows that the molecules are linked into a two-dimensional network parallel to the (001) by N—H···O and O—H···O hydrogen bonds (Table 1 and Fig. 2).

Experimental

The title compound was synthesized by the reaction of 4-nitro-benzaldehyde (1 mmol), 4,4,4-trifluoro-1-phenylbutane-1,3-dione (1 mmol) and urea (1 mmol), catalyzed by 4-methylbenzenesulfonic acid, at 363 K for a certain time (monitered by TLC). After cooling, the reaction mixture was washed with water and recrystallized from ethanol, to obtain single crystals suitable for X-ray diffraction.