Crystal structure of ethyl 6-(chloro-meth-yl)-4-(4-chloro-phen-yl)-2-oxo-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C14H14Cl2N2O3, the chloro-phenyl ring makes a dihedral angle of 87.08 (9)° with the tetra-hydro-pyrimidine ring. There is a short intra-molecular C-H⋯O contact present. In the crystal, mol-ecules 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).

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 = 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

Δρmax = 0.64 e Å−3

Δρmin = −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.

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

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

Click here for additional data file.

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

Click here for additional data file.

. 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.

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

C14H14Cl2N2O3	Z = 2
Mr = 329.17	F(000) = 340
Triclinic, P1	Dx = 1.431 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4698 (3) Å	Cell parameters from 4865 reflections
b = 9.1436 (3) Å	θ = 2.5–30.1°
c = 12.6085 (4) Å	µ = 0.44 mm−1
α = 107.147 (2)°	T = 295 K
β = 99.941 (2)°	Block, colourless
γ = 105.331 (2)°	0.30 × 0.25 × 0.20 mm
V = 763.71 (5) Å3

Bruker APEXII CCD diffractometer	3945 independent reflections
Radiation source: fine-focus sealed tube	2911 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 0 pixels mm-1	θmax = 31.0°, θmin = 2.5°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
Tmin = 0.897, Tmax = 0.917	l = −18→17
20157 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0628P)2 + 0.6453P] where P = (Fo2 + 2Fc2)/3
3945 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.64 e Å−3
26 restraints	Δρmin = −0.53 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.8422 (5)	0.1384 (4)	0.5387 (2)	0.0651 (8)
C2	0.7145 (5)	−0.0099 (4)	0.4712 (3)	0.0725 (9)
H2	0.6712	−0.0878	0.5031	0.087*
C3	0.6488 (4)	−0.0442 (3)	0.3538 (2)	0.0598 (7)
H3	0.5588	−0.1453	0.3073	0.072*
C4	0.7137 (3)	0.0674 (3)	0.30506 (18)	0.0361 (4)
C5	0.8424 (5)	0.2165 (4)	0.3761 (3)	0.0699 (9)
H5	0.8876	0.2950	0.3452	0.084*
C6	0.9060 (6)	0.2518 (4)	0.4938 (3)	0.0895 (12)
H6	0.9925	0.3537	0.5414	0.107*
C7	0.6508 (3)	0.0279 (2)	0.17587 (17)	0.0306 (4)
H7	0.7032	0.1280	0.1613	0.037*
C8	0.6382 (3)	−0.2509 (2)	0.06968 (18)	0.0342 (4)
C9	0.3408 (3)	−0.1913 (2)	0.06544 (17)	0.0315 (4)
C10	0.4341 (3)	−0.0329 (2)	0.12644 (16)	0.0300 (4)
C11	0.1275 (3)	−0.2650 (3)	0.0111 (2)	0.0454 (5)
H11A	0.0752	−0.1799	0.0068	0.055*
H11B	0.0673	−0.3162	0.0593	0.055*
C12	0.3328 (3)	0.0848 (3)	0.15276 (18)	0.0360 (4)
N1	0.7306 (2)	−0.0910 (2)	0.11509 (15)	0.0338 (4)
H1	0.8450	−0.0555	0.1081	0.041*
N2	0.4415 (2)	−0.2989 (2)	0.05067 (17)	0.0375 (4)
H2A	0.3781	−0.4009	0.0285	0.045*
O1	0.7187 (2)	−0.35121 (19)	0.04214 (16)	0.0488 (4)
O2	0.1610 (2)	0.0561 (2)	0.13615 (16)	0.0508 (4)
O3	0.4586 (2)	0.23490 (19)	0.20251 (17)	0.0554 (5)
C13	0.374 (3)	0.3618 (16)	0.2478 (12)	0.086 (4)	0.654 (17)
H13A	0.2924	0.3745	0.1847	0.103*	0.654 (17)
H13B	0.2959	0.3318	0.2971	0.103*	0.654 (17)
C14	0.5303 (12)	0.5098 (7)	0.3121 (11)	0.116 (4)	0.654 (17)
H14A	0.6081	0.4964	0.3752	0.174*	0.654 (17)
H14B	0.4803	0.5955	0.3415	0.174*	0.654 (17)
H14C	0.6076	0.5371	0.2627	0.174*	0.654 (17)
C13A	0.394 (4)	0.368 (3)	0.2319 (11)	0.070 (7)	0.346 (17)
H13C	0.2598	0.3357	0.1900	0.084*	0.346 (17)
H13D	0.4684	0.4531	0.2098	0.084*	0.346 (17)
C14A	0.414 (4)	0.428 (3)	0.3506 (12)	0.127 (10)	0.346 (17)
H14D	0.3199	0.3533	0.3697	0.190*	0.346 (17)
H14E	0.3937	0.5314	0.3713	0.190*	0.346 (17)
H14F	0.5409	0.4415	0.3920	0.190*	0.346 (17)
Cl1	0.92366 (19)	0.18204 (17)	0.68608 (7)	0.1114 (4)
Cl2	0.07043 (8)	−0.41074 (8)	−0.12863 (5)	0.0522 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0719 (18)	0.085 (2)	0.0334 (12)	0.0407 (17)	0.0004 (12)	0.0089 (13)
C2	0.095 (2)	0.079 (2)	0.0475 (16)	0.0299 (19)	0.0186 (15)	0.0296 (15)
C3	0.0751 (18)	0.0529 (15)	0.0402 (13)	0.0083 (13)	0.0088 (12)	0.0163 (11)
C4	0.0315 (10)	0.0396 (11)	0.0348 (10)	0.0151 (8)	0.0040 (8)	0.0098 (8)
C5	0.076 (2)	0.0498 (15)	0.0523 (16)	−0.0029 (14)	−0.0110 (14)	0.0120 (12)
C6	0.099 (3)	0.069 (2)	0.0506 (18)	0.0008 (19)	−0.0216 (17)	−0.0003 (16)
C7	0.0246 (9)	0.0292 (9)	0.0363 (10)	0.0085 (7)	0.0058 (7)	0.0110 (8)
C8	0.0261 (9)	0.0363 (10)	0.0398 (10)	0.0112 (8)	0.0095 (8)	0.0122 (8)
C9	0.0228 (8)	0.0364 (10)	0.0361 (10)	0.0107 (7)	0.0095 (7)	0.0124 (8)
C10	0.0255 (9)	0.0331 (9)	0.0325 (9)	0.0112 (7)	0.0066 (7)	0.0126 (8)
C11	0.0262 (10)	0.0453 (12)	0.0516 (13)	0.0079 (9)	0.0099 (9)	0.0027 (10)
C12	0.0343 (10)	0.0374 (10)	0.0370 (10)	0.0163 (8)	0.0061 (8)	0.0123 (8)
N1	0.0207 (7)	0.0351 (9)	0.0416 (9)	0.0079 (6)	0.0086 (6)	0.0094 (7)
N2	0.0237 (8)	0.0284 (8)	0.0552 (11)	0.0069 (6)	0.0101 (7)	0.0096 (7)
O1	0.0303 (8)	0.0385 (8)	0.0734 (12)	0.0151 (6)	0.0150 (7)	0.0103 (8)
O2	0.0333 (8)	0.0521 (10)	0.0681 (11)	0.0229 (7)	0.0135 (7)	0.0155 (8)
O3	0.0431 (9)	0.0336 (8)	0.0738 (12)	0.0180 (7)	−0.0026 (8)	0.0034 (8)
C13	0.071 (6)	0.051 (6)	0.116 (9)	0.039 (4)	0.008 (6)	−0.001 (5)
C14	0.100 (5)	0.041 (3)	0.171 (9)	0.017 (3)	0.030 (5)	−0.003 (4)
C13A	0.077 (14)	0.052 (10)	0.063 (8)	0.048 (10)	−0.016 (7)	−0.009 (7)
C14A	0.18 (2)	0.138 (18)	0.075 (9)	0.115 (18)	0.028 (9)	0.000 (9)
Cl1	0.1383 (10)	0.1531 (11)	0.0355 (4)	0.0742 (8)	0.0001 (5)	0.0144 (5)
Cl2	0.0426 (3)	0.0510 (4)	0.0510 (3)	0.0153 (3)	−0.0023 (2)	0.0100 (3)

C1—C6	1.342 (5)	C11—Cl2	1.766 (2)
C1—C2	1.352 (5)	C11—H11A	0.9700
C1—Cl1	1.739 (3)	C11—H11B	0.9700
C2—C3	1.388 (4)	C12—O2	1.207 (3)
C2—H2	0.9300	C12—O3	1.330 (3)
C3—C4	1.366 (3)	N1—H1	0.8600
C3—H3	0.9300	N2—H2A	0.8600
C4—C5	1.369 (3)	O3—C13A	1.4000 (10)
C4—C7	1.518 (3)	O3—C13	1.482 (8)
C5—C6	1.387 (4)	C13—C14	1.430 (19)
C5—H5	0.9300	C13—H13A	0.9700
C6—H6	0.9300	C13—H13B	0.9700
C7—N1	1.461 (2)	C14—H14A	0.9600
C7—C10	1.513 (2)	C14—H14B	0.9600
C7—H7	0.9800	C14—H14C	0.9600
C8—O1	1.225 (2)	C13A—C14A	1.4000 (10)
C8—N1	1.333 (3)	C13A—H13C	0.9700
C8—N2	1.373 (2)	C13A—H13D	0.9700
C9—C10	1.341 (3)	C14A—H14D	0.9600
C9—N2	1.379 (2)	C14A—H14E	0.9600
C9—C11	1.498 (3)	C14A—H14F	0.9600
C10—C12	1.466 (3)
C6—C1—C2	121.0 (3)	Cl2—C11—H11A	109.2
C6—C1—Cl1	119.8 (3)	C9—C11—H11B	109.2
C2—C1—Cl1	119.2 (3)	Cl2—C11—H11B	109.2
C1—C2—C3	119.1 (3)	H11A—C11—H11B	107.9
C1—C2—H2	120.5	O2—C12—O3	122.43 (19)
C3—C2—H2	120.5	O2—C12—C10	127.3 (2)
C4—C3—C2	121.3 (3)	O3—C12—C10	110.28 (17)
C4—C3—H3	119.4	C8—N1—C7	124.46 (16)
C2—C3—H3	119.4	C8—N1—H1	117.8
C3—C4—C5	118.0 (2)	C7—N1—H1	117.8
C3—C4—C7	121.6 (2)	C8—N2—C9	123.10 (17)
C5—C4—C7	120.4 (2)	C8—N2—H2A	118.5
C4—C5—C6	120.8 (3)	C9—N2—H2A	118.4
C4—C5—H5	119.6	C12—O3—C13A	120.4 (14)
C6—C5—H5	119.6	C12—O3—C13	114.8 (8)
C1—C6—C5	119.8 (3)	C13A—O3—C13	10.8 (18)
C1—C6—H6	120.1	C14—C13—O3	107.3 (12)
C5—C6—H6	120.1	C14—C13—H13A	110.3
N1—C7—C10	109.45 (15)	O3—C13—H13A	110.3
N1—C7—C4	110.73 (15)	C14—C13—H13B	110.3
C10—C7—C4	113.47 (16)	O3—C13—H13B	110.3
N1—C7—H7	107.7	H13A—C13—H13B	108.5
C10—C7—H7	107.7	O3—C13A—C14A	110.7 (9)
C4—C7—H7	107.7	O3—C13A—H13C	109.5
O1—C8—N1	123.56 (18)	C14A—C13A—H13C	109.5
O1—C8—N2	120.66 (19)	O3—C13A—H13D	109.5
N1—C8—N2	115.73 (17)	C14A—C13A—H13D	109.5
C10—C9—N2	120.01 (17)	H13C—C13A—H13D	108.1
C10—C9—C11	124.57 (18)	C13A—C14A—H14D	109.5
N2—C9—C11	115.41 (18)	C13A—C14A—H14E	109.5
C9—C10—C12	122.35 (17)	H14D—C14A—H14E	109.5
C9—C10—C7	119.80 (17)	C13A—C14A—H14F	109.5
C12—C10—C7	117.78 (17)	H14D—C14A—H14F	109.5
C9—C11—Cl2	112.02 (15)	H14E—C14A—H14F	109.5
C9—C11—H11A	109.2
C6—C1—C2—C3	−0.1 (5)	C10—C9—C11—Cl2	138.10 (19)
Cl1—C1—C2—C3	179.6 (3)	N2—C9—C11—Cl2	−42.8 (3)
C1—C2—C3—C4	1.4 (5)	C9—C10—C12—O2	8.7 (4)
C2—C3—C4—C5	−1.7 (5)	C7—C10—C12—O2	−168.2 (2)
C2—C3—C4—C7	176.7 (3)	C9—C10—C12—O3	−173.0 (2)
C3—C4—C5—C6	0.7 (5)	C7—C10—C12—O3	10.1 (3)
C7—C4—C5—C6	−177.7 (3)	O1—C8—N1—C7	−163.2 (2)
C2—C1—C6—C5	−0.8 (6)	N2—C8—N1—C7	19.2 (3)
Cl1—C1—C6—C5	179.4 (3)	C10—C7—N1—C8	−31.1 (3)
C4—C5—C6—C1	0.5 (6)	C4—C7—N1—C8	94.8 (2)
C3—C4—C7—N1	−68.6 (3)	O1—C8—N2—C9	−171.1 (2)
C5—C4—C7—N1	109.8 (3)	N1—C8—N2—C9	6.6 (3)
C3—C4—C7—C10	55.0 (3)	C10—C9—N2—C8	−16.8 (3)
C5—C4—C7—C10	−126.6 (3)	C11—C9—N2—C8	164.1 (2)
N2—C9—C10—C12	−174.98 (18)	O2—C12—O3—C13A	−3.8 (9)
C11—C9—C10—C12	4.0 (3)	C10—C12—O3—C13A	177.8 (9)
N2—C9—C10—C7	1.8 (3)	O2—C12—O3—C13	6.6 (7)
C11—C9—C10—C7	−179.16 (19)	C10—C12—O3—C13	−171.8 (7)
N1—C7—C10—C9	19.3 (3)	C12—O3—C13—C14	171.9 (10)
C4—C7—C10—C9	−105.0 (2)	C13A—O3—C13—C14	−65 (9)
N1—C7—C10—C12	−163.80 (17)	C12—O3—C13A—C14A	103 (2)
C4—C7—C10—C12	72.0 (2)	C13—O3—C13A—C14A	42 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1i	0.86	2.04	2.885 (2)	166
N1—H1···O2ii	0.86	2.23	3.070 (2)	166
C11—H11B···O1iii	0.97	2.50	3.069 (3)	117
C11—H11A···O2	0.97	2.14	2.814 (3)	126

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

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