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

Mohammad Hossein Mosslemin; Mohammad Reza Nateghi; Hesamaddin Sadoughi; Asal Lamei

doi:10.1107/S1600536809017097

. 2009 May 20;65(Pt 6):o1339. doi: 10.1107/S1600536809017097

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

Mohammad Hossein Mosslemin ^a,^*, Mohammad Reza Nateghi ^a, Hesamaddin Sadoughi ^a, Asal Lamei ^a

PMCID: PMC2969779 PMID: 21583192

Abstract

The asymmetric unit of the title compound, C₁₆H₁₂ClF₃N₂O₃S·H₂O, contains two crystallographically independent organic molecules and two water molecules. The organic species are linked by an intermolecular O—H⋯O hydrogen bond, while the water molecules are connected to them through intermolecular O—H⋯N hydrogen bonds. The thiophene and phenyl rings are oriented at dihedral angles of 62.35 (4) in the first independent molecule and 60.74 (5)° in the second, while the pyrimidine rings adopt twisted conformations in both molecules. Intramolecular N—H⋯F interactions result in the formation of two five-membered rings having envelope conformations. In the crystal structure, further intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into chains.

Related literature

For related structures, see: Paraskar et al. (2003 ▶); Peng & Deng (2001 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₂ClF₃N₂O₃S·H₂O
M _r = 422.81
Orthorhombic,
a = 9.1156 (6) Å
b = 14.1582 (7) Å
c = 27.6012 (17) Å
V = 3562.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 298 K
0.5 × 0.3 × 0.2 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.860, T _max = 0.923
19595 measured reflections
9251 independent reflections
7478 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.146
S = 1.07
9251 reflections
511 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.47 e Å⁻³
Absolute structure: Flack (1983 ▶), 4326 Friedel pairs
Flack parameter: 0.18 (8)

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017097/hk2682sup1.cif

e-65-o1339-sup1.cif^{(29.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017097/hk2682Isup2.hkl

e-65-o1339-Isup2.hkl^{(443.4KB, 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
N1—H1A⋯F3	0.86	2.38	2.719 (4)	104
N1—H1A⋯O7ⁱ	0.86	2.37	3.022 (4)	132
N2—H2A⋯O7	0.86	2.15	2.914 (4)	147
O2—H2B⋯O6ⁱⁱ	0.89 (4)	1.85 (4)	2.694 (4)	156 (3)
N3—H3A⋯F4	0.86	2.41	2.733 (4)	103
N3—H3A⋯O8ⁱⁱⁱ	0.86	2.34	3.007 (4)	134
N4—H4A⋯O8	0.86	2.14	2.921 (4)	151
O5—H5⋯O3	0.98 (6)	1.72 (6)	2.686 (4)	169 (6)
O7—H7A⋯O6ⁱⁱⁱ	0.84 (7)	2.27 (7)	2.879 (4)	130 (5)
O7—H7B⋯O4^iv	0.86 (6)	2.36 (6)	2.996 (5)	131 (5)
O7—H7B⋯O5^iv	0.86 (6)	2.18 (6)	2.859 (4)	135 (5)
O8—H8A⋯O3^v	0.75 (5)	2.21 (5)	2.897 (4)	153 (4)
O8—H8B⋯O1ⁱ	0.83 (5)	2.22 (6)	2.968 (5)	150 (5)
O8—H8B⋯O2ⁱ	0.83 (5)	2.27 (6)	2.861 (4)	128 (5)

Open in a new tab

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

Acknowledgments

The authors are grateful to Islamic Azad University, Yazd Branch, for financial support.

supplementary crystallographic information

Comment

In recent years, several modified and improved procedures for one-pot synthesis of dihydropyrimidine-2(1H)-ones have been reported (Paraskar et al., 2003; Peng & Deng, 2001). However, in spite of their potential utility, many of these methods suffer from drawback like longer reaction times, unsatisfactory yields and cumbersome product isolation procedures. We report herein the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound contains two crystallographically independent molecules and two water molecules (Fig. 1 ), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (S1/C1–C4), C (C11–C16) and D (S2/C17–C20), F (C27–C32) are, of course, planar and they are oriented at dihedral angles of A/C = 62.35 (4)° and D/F = 60.74 (5)°. Rings B (N1/N2/C6/C7/C9/C10) and E (N3/N4/C22/C23/C25/C26) adopt twisted conformations. Intramolecular N—H···F interactions (Table 1) result in the formations of two five-membered rings G (N1/F3/C7/C8/H1A) and H (N3/F4/C23/C24/H3A) having envelope conformations with atoms C8 and C24 displaced by 0.594 (4) and -0.603 (5) Å from the planes of the other rings atoms. Intramolecular O—H···O hydrogen bond (Table 1) link the two molecules, while the water molecules are connected to them through the intramolecular N—H···O hydrogen bonds (Table 1).

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, a mixture of 1-(2-thenoyl)-3,3,3-trifluoroacetone (0.222 g, 1 mmol), 4-chlorobenzaldehyde (0.141 g, 1 mmol), urea (0.18 g, 3 mmol) and ammonium chloride (0.005 g, 0.1 mmol) were heated at 373 K under stirring for 20 min. After cooling, the reaction mixture was poured onto crushed ice (20 g). The separated solid was filtered, washed with cold water (20 ml) and recrystallized from ethylacetate–hexane (1:3) to afford pure product (yield; 78%, 0.330 g).