Methyl (E)-2-[(3-chloro-4-cyano-phenyl)-imino]-4-(4-chloro-phen-yl)-6-methyl-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C(20)H(16)Cl(2)N(4)O(2), the dihedral angles between the planes of the chloro-phenyl, chloro-cyano-phenyl-imine and ester groups and the plane of the six-membered tetra-hydro-pyrimidine ring are 86.9 (2), 72.6 (2) and 7.9 (2)°, respectively. The Cl atom substituent on the cyano-phenyl ring is disordered over two rotationally related sites [occupancy factors 0.887 (2):0.113 (2)], while the mol-ecular conformation is stabilized by the presence of an intra-molecular aromatic C-H⋯π inter-action. Both N-H groups participate in separate inter-molecular hydrogen-bonding associations with centrosymmetric cyclic motifs [graph sets R(2) (2)(8) and R(2) (2)(12)], resulting in ribbons parallel to [010]. Further weak C-H⋯O hydrogen bonds link these ribbons into a two-dimensional mol-ecular assembly.

Related literature

For crystal structures of the dihydro­pyrimidines, see: Nayak et al. (2010 ▶); Nayak, Venugopala, Govender et al. (2011 ▶); Nayak, Venugopala, Chopra & Guru Row (2011 ▶). For background on the applications of dihydro­pyrimidines, see: Kappe (2000 ▶). For graph-set analysis, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C20H16Cl2N4O2

M = 415.27

Monoclinic,

a = 11.905 (8) Å

b = 13.729 (9) Å

c = 12.782 (8) Å

β = 108.366 (14)°

V = 1983 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.35 mm−1

T = 173 K

0.23 × 0.12 × 0.03 mm

Data collection

Bruker Kappa DUO APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.924, T max = 0.990

9454 measured reflections

3497 independent reflections

2324 reflections with I > 2σ(I)

R int = 0.029

Standard reflections: 0

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.130

S = 1.01

3497 reflections

259 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.37 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: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and PARST (Nardelli, 1995 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812039451/zs2233sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039451/zs2233Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812039451/zs2233Isup3.cml

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

C20H16Cl2N4O2	F(000) = 856
Mr = 415.27	Dx = 1.391 Mg m−3
Monoclinic, P2/c	Melting point: 431(2) K
Hall symbol: -P 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 11.905 (8) Å	Cell parameters from 650 reflections
b = 13.729 (9) Å	θ = 1.5–25.0°
c = 12.782 (8) Å	µ = 0.35 mm−1
β = 108.366 (14)°	T = 173 K
V = 1983 (2) Å3	Plate, yellow
Z = 4	0.23 × 0.12 × 0.03 mm

Bruker Kappa DUO APEXII diffractometer	3497 independent reflections
Radiation source: fine-focus sealed tube	2324 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
0.5° φ scans and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→13
Tmin = 0.924, Tmax = 0.990	k = −16→16
9454 measured reflections	l = −7→15

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0628P)2 + 0.7735P] where P = (Fo2 + 2Fc2)/3
3497 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl2A	1.27478 (8)	0.07230 (7)	0.07772 (9)	0.0732 (3)	0.8872 (16)
C14A	1.0144 (2)	0.26844 (18)	−0.0167 (2)	0.0429 (7)	0.8872 (16)
C15A	1.1235 (3)	0.2245 (2)	0.0335 (2)	0.0511 (7)	0.8872 (16)
H15A	1.1837	0.2590	0.0874	0.061*	0.8872 (16)
C16A	1.1443 (2)	0.1307 (2)	0.0047 (2)	0.0490 (7)	0.8872 (16)
C17A	1.0592 (2)	0.07963 (17)	−0.0761 (2)	0.0387 (6)	0.8872 (16)
C18A	0.9496 (2)	0.12388 (18)	−0.1256 (2)	0.0424 (6)	0.8872 (16)
H18A	0.8900	0.0898	−0.1806	0.051*	0.8872 (16)
C19A	0.9270 (2)	0.21625 (19)	−0.0957 (2)	0.0435 (6)	0.8872 (16)
H19A	0.8514	0.2448	−0.1291	0.052*	0.8872 (16)
C20A	1.0824 (3)	−0.0174 (2)	−0.1067 (2)	0.0449 (7)	0.8872 (16)
N4A	1.0998 (2)	−0.09457 (18)	−0.1320 (2)	0.0584 (7)	0.8872 (16)
Cl2B	0.8417 (6)	0.0473 (6)	−0.1826 (7)	0.0732 (3)	0.1128 (16)
C14B	1.0144 (2)	0.26844 (18)	−0.0167 (2)	0.0429 (7)	0.1128 (16)
C15B	1.1235 (3)	0.2245 (2)	0.0335 (2)	0.0511 (7)	0.1128 (16)
H15B	1.1837	0.2590	0.0874	0.061*	0.1128 (16)
C16B	1.1443 (2)	0.1307 (2)	0.0047 (2)	0.0490 (7)	0.1128 (16)
H16B	1.2182	0.1007	0.0410	0.059*	0.1128 (16)
C17B	1.0592 (2)	0.07963 (17)	−0.0761 (2)	0.0387 (6)	0.1128 (16)
C18B	0.9496 (2)	0.12388 (18)	−0.1256 (2)	0.0424 (6)	0.1128 (16)
C19B	0.9270 (2)	0.21625 (19)	−0.0957 (2)	0.0435 (6)	0.1128 (16)
H19B	0.8514	0.2448	−0.1291	0.052*	0.1128 (16)
C20B	1.0824 (3)	−0.0174 (2)	−0.1067 (2)	0.0449 (7)	0.1128 (16)
N4B	1.0998 (2)	−0.09457 (18)	−0.1320 (2)	0.0584 (7)	0.1128 (16)
Cl1	0.35886 (9)	0.15552 (9)	−0.18125 (10)	0.1015 (4)
O1	0.67082 (15)	0.36934 (13)	0.30483 (14)	0.0440 (5)
O2	0.6947 (2)	0.53124 (14)	0.30330 (18)	0.0635 (6)
N1	0.88569 (18)	0.31127 (15)	0.12045 (18)	0.0418 (5)
H1	0.9209	0.2541	0.1288	0.050*
N2	0.89937 (19)	0.47517 (14)	0.08817 (18)	0.0445 (6)
H2	0.9239	0.5226	0.0544	0.053*
N3	0.9962 (2)	0.36677 (15)	0.0096 (2)	0.0480 (6)
C1	0.6064 (3)	0.3833 (2)	0.3825 (2)	0.0545 (8)
H1A	0.6603	0.4078	0.4523	0.082*
H1B	0.5725	0.3211	0.3952	0.082*
H1C	0.5426	0.4305	0.3525	0.082*
C2	0.7139 (2)	0.4517 (2)	0.2724 (2)	0.0429 (6)
C3	0.7800 (2)	0.42850 (18)	0.1967 (2)	0.0393 (6)
C4	0.8352 (2)	0.49915 (19)	0.1574 (2)	0.0405 (6)
C5	0.8350 (3)	0.60622 (18)	0.1828 (2)	0.0478 (7)
H5A	0.7538	0.6311	0.1557	0.072*
H5B	0.8843	0.6411	0.1466	0.072*
H5C	0.8667	0.6161	0.2627	0.072*
C6	0.7861 (2)	0.32283 (18)	0.1639 (2)	0.0398 (6)
H6	0.8027	0.2821	0.2320	0.048*
C7	0.6733 (2)	0.28406 (18)	0.0795 (2)	0.0403 (6)
C8	0.6315 (3)	0.1926 (2)	0.0943 (3)	0.0552 (8)
H8	0.6691	0.1570	0.1597	0.066*
C9	0.5350 (3)	0.1527 (2)	0.0139 (3)	0.0697 (10)
H9	0.5076	0.0894	0.0234	0.084*
C10	0.4795 (3)	0.2057 (3)	−0.0795 (3)	0.0625 (9)
C11	0.5174 (3)	0.2981 (2)	−0.0955 (3)	0.0589 (8)
H11	0.4778	0.3345	−0.1598	0.071*
C12	0.6147 (3)	0.3362 (2)	−0.0151 (2)	0.0496 (7)
H12	0.6420	0.3994	−0.0250	0.060*
C13	0.9271 (2)	0.38082 (17)	0.0692 (2)	0.0400 (6)

	U11	U22	U33	U12	U13	U23
Cl2A	0.0432 (5)	0.0708 (6)	0.0957 (7)	0.0139 (4)	0.0076 (5)	−0.0130 (5)
C14A	0.0484 (16)	0.0313 (14)	0.0634 (18)	−0.0036 (13)	0.0384 (15)	−0.0031 (13)
C15A	0.0442 (16)	0.0458 (16)	0.0676 (19)	−0.0057 (14)	0.0237 (15)	−0.0131 (14)
C16A	0.0393 (15)	0.0455 (16)	0.0652 (18)	0.0060 (13)	0.0207 (14)	−0.0046 (14)
C17A	0.0473 (16)	0.0295 (13)	0.0491 (15)	0.0024 (12)	0.0290 (13)	−0.0010 (12)
C18A	0.0447 (16)	0.0343 (14)	0.0514 (16)	−0.0026 (12)	0.0197 (13)	−0.0027 (12)
C19A	0.0426 (15)	0.0337 (14)	0.0596 (17)	0.0016 (13)	0.0238 (14)	0.0004 (13)
C20A	0.0529 (17)	0.0394 (16)	0.0462 (16)	0.0063 (13)	0.0214 (13)	0.0014 (13)
N4A	0.0752 (18)	0.0419 (15)	0.0620 (16)	0.0152 (13)	0.0273 (14)	−0.0020 (12)
Cl2B	0.0432 (5)	0.0708 (6)	0.0957 (7)	0.0139 (4)	0.0076 (5)	−0.0130 (5)
C14B	0.0484 (16)	0.0313 (14)	0.0634 (18)	−0.0036 (13)	0.0384 (15)	−0.0031 (13)
C15B	0.0442 (16)	0.0458 (16)	0.0676 (19)	−0.0057 (14)	0.0237 (15)	−0.0131 (14)
C16B	0.0393 (15)	0.0455 (16)	0.0652 (18)	0.0060 (13)	0.0207 (14)	−0.0046 (14)
C17B	0.0473 (16)	0.0295 (13)	0.0491 (15)	0.0024 (12)	0.0290 (13)	−0.0010 (12)
C18B	0.0447 (16)	0.0343 (14)	0.0514 (16)	−0.0026 (12)	0.0197 (13)	−0.0027 (12)
C19B	0.0426 (15)	0.0337 (14)	0.0596 (17)	0.0016 (13)	0.0238 (14)	0.0004 (13)
C20B	0.0529 (17)	0.0394 (16)	0.0462 (16)	0.0063 (13)	0.0214 (13)	0.0014 (13)
N4B	0.0752 (18)	0.0419 (15)	0.0620 (16)	0.0152 (13)	0.0273 (14)	−0.0020 (12)
Cl1	0.0658 (6)	0.1042 (8)	0.1193 (8)	−0.0215 (6)	0.0072 (6)	−0.0381 (7)
O1	0.0411 (10)	0.0440 (11)	0.0553 (11)	0.0003 (9)	0.0270 (9)	0.0015 (9)
O2	0.0846 (16)	0.0439 (12)	0.0850 (15)	0.0025 (11)	0.0598 (14)	−0.0096 (11)
N1	0.0393 (12)	0.0288 (11)	0.0661 (14)	0.0043 (9)	0.0293 (11)	−0.0007 (10)
N2	0.0528 (14)	0.0280 (11)	0.0687 (15)	−0.0037 (10)	0.0420 (13)	−0.0065 (10)
N3	0.0545 (14)	0.0296 (11)	0.0752 (16)	−0.0041 (11)	0.0423 (13)	−0.0089 (11)
C1	0.0521 (17)	0.064 (2)	0.0577 (18)	−0.0015 (15)	0.0325 (15)	0.0001 (15)
C2	0.0380 (14)	0.0409 (15)	0.0544 (16)	0.0038 (12)	0.0213 (13)	−0.0015 (13)
C3	0.0371 (14)	0.0342 (14)	0.0518 (16)	0.0005 (12)	0.0214 (12)	−0.0028 (12)
C4	0.0381 (14)	0.0353 (14)	0.0538 (16)	0.0002 (12)	0.0225 (13)	−0.0072 (12)
C5	0.0488 (16)	0.0350 (14)	0.0701 (19)	−0.0037 (13)	0.0339 (15)	−0.0100 (13)
C6	0.0392 (14)	0.0331 (13)	0.0563 (16)	0.0023 (11)	0.0283 (13)	0.0018 (12)
C7	0.0374 (14)	0.0331 (14)	0.0599 (17)	0.0009 (12)	0.0287 (13)	−0.0054 (13)
C8	0.0443 (16)	0.0344 (15)	0.089 (2)	0.0015 (13)	0.0237 (16)	0.0053 (15)
C9	0.0474 (18)	0.0366 (17)	0.123 (3)	−0.0069 (15)	0.024 (2)	−0.0123 (19)
C10	0.0458 (18)	0.061 (2)	0.081 (2)	−0.0060 (17)	0.0200 (17)	−0.0222 (19)
C11	0.0559 (19)	0.071 (2)	0.0545 (18)	−0.0044 (17)	0.0248 (16)	−0.0050 (16)
C12	0.0520 (17)	0.0454 (16)	0.0595 (18)	−0.0070 (14)	0.0290 (15)	−0.0006 (14)
C13	0.0384 (14)	0.0288 (13)	0.0592 (16)	−0.0039 (11)	0.0246 (13)	−0.0074 (12)

Cl2A—C16A	1.736 (3)	N3—C13	1.300 (3)
C14A—C15A	1.392 (4)	C1—H1A	0.9800
C14A—C19A	1.398 (4)	C1—H1B	0.9800
C14A—N3	1.424 (3)	C1—H1C	0.9800
C15A—C16A	1.382 (4)	C2—C3	1.461 (3)
C15A—H15A	0.9500	C3—C4	1.355 (3)
C16A—C17A	1.388 (4)	C3—C6	1.518 (4)
C17A—C18A	1.397 (4)	C4—C5	1.506 (4)
C17A—C20A	1.439 (4)	C5—H5A	0.9800
C18A—C19A	1.375 (4)	C5—H5B	0.9800
C18A—H18A	0.9500	C5—H5C	0.9800
C19A—H19A	0.9500	C6—C7	1.530 (4)
C20A—N4A	1.146 (3)	C6—H6	1.0000
Cl1—C10	1.747 (3)	C7—C8	1.385 (4)
O1—C2	1.359 (3)	C7—C12	1.389 (4)
O1—C1	1.446 (3)	C8—C9	1.389 (4)
O2—C2	1.207 (3)	C8—H8	0.9500
N1—C13	1.337 (3)	C9—C10	1.376 (5)
N1—C6	1.468 (3)	C9—H9	0.9500
N1—H1	0.8800	C10—C11	1.383 (5)
N2—C13	1.377 (3)	C11—C12	1.386 (4)
N2—C4	1.378 (3)	C11—H11	0.9500
N2—H2	0.8800	C12—H12	0.9500
C15A—C14A—C19A	119.0 (2)	C2—C3—C6	118.3 (2)
C15A—C14A—N3	119.4 (3)	C3—C4—N2	120.0 (2)
C19A—C14A—N3	121.5 (3)	C3—C4—C5	125.8 (2)
C16A—C15A—C14A	120.0 (3)	N2—C4—C5	114.3 (2)
C16A—C15A—H15A	120.0	C4—C5—H5A	109.5
C14A—C15A—H15A	120.0	C4—C5—H5B	109.5
C15A—C16A—C17A	121.3 (3)	H5A—C5—H5B	109.5
C15A—C16A—Cl2A	119.5 (2)	C4—C5—H5C	109.5
C17A—C16A—Cl2A	119.1 (2)	H5A—C5—H5C	109.5
C16A—C17A—C18A	118.4 (2)	H5B—C5—H5C	109.5
C16A—C17A—C20A	120.9 (3)	N1—C6—C3	108.84 (19)
C18A—C17A—C20A	120.7 (2)	N1—C6—C7	109.2 (2)
C19A—C18A—C17A	120.8 (3)	C3—C6—C7	114.8 (2)
C19A—C18A—H18A	119.6	N1—C6—H6	107.9
C17A—C18A—H18A	119.6	C3—C6—H6	107.9
C18A—C19A—C14A	120.5 (3)	C7—C6—H6	107.9
C18A—C19A—H19A	119.8	C8—C7—C12	118.8 (3)
C14A—C19A—H19A	119.8	C8—C7—C6	119.5 (3)
N4A—C20A—C17A	179.3 (4)	C12—C7—C6	121.6 (2)
C2—O1—C1	115.6 (2)	C7—C8—C9	120.3 (3)
C13—N1—C6	125.1 (2)	C7—C8—H8	119.8
C13—N1—H1	117.5	C9—C8—H8	119.8
C6—N1—H1	117.5	C10—C9—C8	119.5 (3)
C13—N2—C4	123.3 (2)	C10—C9—H9	120.3
C13—N2—H2	118.3	C8—C9—H9	120.3
C4—N2—H2	118.3	C9—C10—C11	121.6 (3)
C13—N3—C14A	116.7 (2)	C9—C10—Cl1	119.7 (3)
O1—C1—H1A	109.5	C11—C10—Cl1	118.8 (3)
O1—C1—H1B	109.5	C10—C11—C12	118.1 (3)
H1A—C1—H1B	109.5	C10—C11—H11	120.9
O1—C1—H1C	109.5	C12—C11—H11	120.9
H1A—C1—H1C	109.5	C11—C12—C7	121.6 (3)
H1B—C1—H1C	109.5	C11—C12—H12	119.2
O2—C2—O1	121.6 (2)	C7—C12—H12	119.2
O2—C2—C3	127.6 (2)	N3—C13—N1	125.5 (2)
O1—C2—C3	110.7 (2)	N3—C13—N2	118.3 (2)
C4—C3—C2	121.0 (2)	N1—C13—N2	116.1 (2)
C4—C3—C6	120.7 (2)
C19A—C14A—C15A—C16A	0.1 (4)	C13—N1—C6—C3	−29.3 (3)
N3—C14A—C15A—C16A	−176.8 (2)	C13—N1—C6—C7	96.7 (3)
C14A—C15A—C16A—C17A	1.9 (4)	C4—C3—C6—N1	18.4 (3)
C14A—C15A—C16A—Cl2A	−173.4 (2)	C2—C3—C6—N1	−161.1 (2)
C15A—C16A—C17A—C18A	−2.3 (4)	C4—C3—C6—C7	−104.4 (3)
Cl2A—C16A—C17A—C18A	173.05 (19)	C2—C3—C6—C7	76.1 (3)
C15A—C16A—C17A—C20A	179.0 (2)	N1—C6—C7—C8	101.1 (3)
Cl2A—C16A—C17A—C20A	−5.7 (4)	C3—C6—C7—C8	−136.3 (2)
C16A—C17A—C18A—C19A	0.6 (4)	N1—C6—C7—C12	−75.4 (3)
C20A—C17A—C18A—C19A	179.4 (2)	C3—C6—C7—C12	47.1 (3)
C17A—C18A—C19A—C14A	1.3 (4)	C12—C7—C8—C9	2.1 (4)
C15A—C14A—C19A—C18A	−1.7 (4)	C6—C7—C8—C9	−174.6 (2)
N3—C14A—C19A—C18A	175.2 (2)	C7—C8—C9—C10	−1.5 (5)
C15A—C14A—N3—C13	−108.4 (3)	C8—C9—C10—C11	0.0 (5)
C19A—C14A—N3—C13	74.8 (3)	C8—C9—C10—Cl1	179.5 (2)
C1—O1—C2—O2	−3.0 (4)	C9—C10—C11—C12	0.8 (5)
C1—O1—C2—C3	178.4 (2)	Cl1—C10—C11—C12	−178.7 (2)
O2—C2—C3—C4	4.3 (5)	C10—C11—C12—C7	−0.2 (4)
O1—C2—C3—C4	−177.2 (2)	C8—C7—C12—C11	−1.2 (4)
O2—C2—C3—C6	−176.2 (3)	C6—C7—C12—C11	175.3 (2)
O1—C2—C3—C6	2.3 (3)	C14A—N3—C13—N1	10.1 (4)
C2—C3—C4—N2	178.5 (2)	C14A—N3—C13—N2	−174.5 (2)
C6—C3—C4—N2	−1.0 (4)	C6—N1—C13—N3	−163.9 (3)
C2—C3—C4—C5	−1.0 (4)	C6—N1—C13—N2	20.6 (4)
C6—C3—C4—C5	179.5 (3)	C4—N2—C13—N3	−174.4 (3)
C13—N2—C4—C3	−10.6 (4)	C4—N2—C13—N1	1.4 (4)
C13—N2—C4—C5	168.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4Ai	0.88	2.21	2.981 (4)	147
N2—H2···N3ii	0.88	2.09	2.966 (4)	172
C15A—H15A···O1iii	0.95	2.39	3.322 (4)	169
C12—H12···Cg1	0.95	2.85	3.290 (2)	109

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the mid-point of the C3=C4 bond.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4A i	0.88	2.21	2.981 (4)	147
N2—H2⋯N3ii	0.88	2.09	2.966 (4)	172
C15A—H15A⋯O1iii	0.95	2.39	3.322 (4)	169
C12—H12⋯Cg1	0.95	2.85	3.290 (2)	109

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