Crystal structure of ethyl 6-(chloro­meth­yl)-4-(4-chloro­phen­yl)-2-oxo-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate

S Bharanidharan; H Saleem; B Gunasekaran; M Syed Ali Padusha; M Suresh

doi:10.1107/S1600536814023046

. 2014 Oct 24;70(Pt 11):o1185–o1186. doi: 10.1107/S1600536814023046

Crystal structure of ethyl 6-(chloromethyl)-4-(4-chlorophenyl)-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate

S Bharanidharan ^a, H Saleem ^a, B Gunasekaran ^b,^*, M Syed Ali Padusha ^c, M Suresh ^d

PMCID: PMC4257316 PMID: 25484820

Abstract

In the title compound, C₁₄H₁₄Cl₂N₂O₃, the chlorophenyl ring makes a dihedral angle of 87.08 (9)° with the tetrahydropyrimidine ring. There is a short intramolecular C—H⋯O contact present. In the crystal, molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R ² ₂(8) ring motif. The dimers are linked via a second pair of N—H⋯O hydrogen bonds, this time enclosing an R ⁴ ₄(20) ring motif, forming ribbons along [100]. The ribbons are linked via C—H⋯O hydrogen bonds, forming sheets lying parallel to (001). The terminal ethyl group is disordered over two positions with an occupancy ratio of 0.654 (17):0.346 (17).

Keywords: crystal structure, tetrahydropyrimidine, inversion dimers, anticarcinogenic, antihypertensive, calcium channel modulators.

Related literature

For the many biological activities of dihydropyrimidinone derivatives, see: Atwal et al. (1991 ▶); Jauk et al. (2000 ▶); Kato (1984 ▶); Wipf & Cunningham (1995 ▶); Bedia et al. (2006 ▶); For related structures, see: Nayak et al. (2009 ▶); Yuvaraj et al. (2010 ▶);

Experimental

Crystal data

C₁₄H₁₄Cl₂N₂O₃
M _r = 329.17
Triclinic,
a = 7.4698 (3) Å
b = 9.1436 (3) Å
c = 12.6085 (4) Å
α = 107.147 (2)°
β = 99.941 (2)°
γ = 105.331 (2)°
V = 763.71 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 295 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.897, T _max = 0.917
20157 measured reflections
3945 independent reflections
2911 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.153
S = 1.03
3945 reflections
211 parameters
26 restraints
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814023046/su5005sup1.cif

e-70-o1185-sup1.cif^{(25.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023046/su5005Isup2.hkl

e-70-o1185-Isup2.hkl^{(189.4KB, hkl)}

Click here for additional data file.^{(5.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814023046/su5005Isup3.cml

Click here for additional data file.^{(486.7KB, tif)}

. DOI: 10.1107/S1600536814023046/su5005fig1.tif

The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(323KB, tif)}

a . DOI: 10.1107/S1600536814023046/su5005fig2.tif

The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1030125

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H2AO1ⁱ	0.86	2.04	2.885(2)	166
N1H1O2ⁱⁱ	0.86	2.23	3.070(2)	166
C11H11BO1ⁱⁱⁱ	0.97	2.50	3.069(3)	117
C11H11AO2	0.97	2.14	2.814(3)	126

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

Acknowledgments

SB thanks Professor K. Ramamurthi, Department of Physics and Nanotechnology, SRM University, Chennai, for his guidance and valuable suggestions.

supplementary crystallographic information

S1. Comment

Dihydropyrimidinones (DHPM) and their derivatives are important on account of their wide range of applications in therapeutic and pharmacology, namely because of their anticarcinogenic (Kato, 1984), antihypertensive (Atwal et al., 1991) and calcium channel modulators (Jauk et al., 2000) activities. These derivatives have also been screened for anti-bacterial (Wipf & Cunningham, 1995), and anti-tuberculosis activity (Bedia et al., 2006).

The geometric parameters of the title molecule (Fig. 1) agree well with those reported fro similar structures (Nayak et al., 2009; Yuvaraj et al., 2010). The chlorophenyl ring makes a dihedral angles of 87.08 (9) ° with the tetrahydropyrimidine ring. There is a short intramolecular C—H···O contact (Table 1).

In the crystal, molecules are linked via a pair of N—H···O hydrogen bonds forming inversion dimers with an R²₂(8) ring motif. The dimers are linked via a second pair of N—H···O hydrogen bonds, this time enclosing an R⁴₄(20) ring motif, forming ribbons along [100]. The ribbons are linked via C—H···O hydrogen bonds forming sheets lying parallel to (001); see Table 1 and Fig. 2 for details.

S2. Experimental

A mixture of ethyl-4-chloro acetoacetate (4.1 ml, 0.025 mol), 4-chlorobenzaldehyde (3.6 g, 0.025 mol), and urea (4.5 g, 0.075 mol) in ethanol (5 ml) was heated under reflux in the presence of concentrated HCl (1 mL) for 5 h (monitored by TLC). The reaction mixture, after being cooled to room temperature, was poured onto crushed ice and stirred for 5–10 min. The solid was separated and filtered under suction, washed with ice-cold water (50 ml), and then recrystallized from hot ethanol to afford pure product [m.p. 437 K; yield 76%].