Ethyl 4-(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)-6-methyl-2-oxo-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C(18)H(19)ClN(4)O(3), the dihydro-pyrimidin-one ring adopts a flattened boat conformation. The dihedral angle between the phenyl and pyrazole rings is 43.39 (6)°. An intra-molecular C-H⋯O contact generates an S(8) ring motif that stabilizes the mol-ecular conformation and precludes the carbonyl O atom of the ester group from forming inter-molecular inter-actions. Mol-ecules are linked into centrosymmetric dimers by pairs of N-H⋯O hydrogen bonds and the dimers are linked into infinite chains along [101] by N-H⋯N hydrogen bonds.

Related literature

For medicinal applications of pyrimidinone derivatives, see: Atwal (1990 ▶); Desai et al. (2006 ▶); Wipf & Cunningham (1995 ▶); Bedia et al. (2006 ▶). For a related structure, see: Fun et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C18H19ClN4O3

M = 374.82

Triclinic,

a = 7.9083 (2) Å

b = 10.2600 (2) Å

c = 10.9075 (3) Å

α = 93.394 (1)°

β = 99.379 (1)°

γ = 90.203 (1)°

V = 871.58 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.25 mm−1

T = 110 K

0.56 × 0.26 × 0.21 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.875, T max = 0.950

18224 measured reflections

5048 independent reflections

4355 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.099

S = 1.05

5048 reflections

257 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016365/tk2442sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016365/tk2442Isup2.hkl

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

C18H19ClN4O3	Z = 2
Mr = 374.82	F(000) = 392
Triclinic, P1	Dx = 1.428 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9083 (2) Å	Cell parameters from 9944 reflections
b = 10.2600 (2) Å	θ = 2.6–35.8°
c = 10.9075 (3) Å	µ = 0.25 mm−1
α = 93.394 (1)°	T = 110 K
β = 99.379 (1)°	Block, colourless
γ = 90.203 (1)°	0.56 × 0.26 × 0.21 mm
V = 871.58 (4) Å3

Bruker SMART APEXII CCD area-detector diffractometer	5048 independent reflections
Radiation source: fine-focus sealed tube	4355 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 30.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
Tmin = 0.875, Tmax = 0.950	k = −14→14
18224 measured reflections	l = −15→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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.3283P] where P = (Fo2 + 2Fc2)/3
5048 reflections	(Δ/σ)max < 0.001
257 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 110.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.16502 (4)	0.27288 (3)	0.28593 (3)	0.01867 (8)
O1	0.09492 (11)	0.60474 (9)	0.13406 (8)	0.01980 (18)
O2	0.64558 (11)	0.20298 (9)	0.00629 (8)	0.02096 (19)
O3	0.77714 (11)	0.29869 (9)	0.18745 (8)	0.02079 (19)
N1	0.40982 (13)	0.25693 (10)	0.48878 (9)	0.01486 (19)
N2	0.57439 (13)	0.29637 (10)	0.53670 (9)	0.01546 (19)
N3	0.36526 (13)	0.54573 (10)	0.21278 (9)	0.01470 (19)
N4	0.21476 (13)	0.43462 (10)	0.03761 (9)	0.0162 (2)
C1	0.41198 (18)	0.06888 (12)	0.61334 (11)	0.0202 (2)
H1A	0.5286	0.0600	0.6116	0.024*
C2	0.3256 (2)	−0.01924 (13)	0.67359 (12)	0.0253 (3)
H2A	0.3844	−0.0884	0.7115	0.030*
C3	0.1527 (2)	−0.00483 (14)	0.67768 (12)	0.0265 (3)
H3A	0.0951	−0.0654	0.7165	0.032*
C4	0.06518 (18)	0.09986 (14)	0.62404 (12)	0.0254 (3)
H4A	−0.0503	0.1106	0.6289	0.030*
C5	0.14923 (16)	0.18874 (13)	0.56301 (11)	0.0202 (2)
H5A	0.0910	0.2594	0.5276	0.024*
C6	0.32146 (16)	0.17084 (11)	0.55550 (10)	0.0161 (2)
C7	0.36219 (14)	0.30274 (11)	0.37349 (10)	0.0143 (2)
C8	0.49610 (14)	0.37464 (11)	0.34481 (10)	0.0132 (2)
C9	0.62520 (14)	0.36737 (11)	0.45051 (10)	0.0144 (2)
C10	0.50187 (14)	0.44856 (11)	0.22960 (10)	0.0135 (2)
H10A	0.6117	0.4960	0.2419	0.016*
C11	0.21883 (15)	0.53209 (11)	0.13033 (10)	0.0150 (2)
C12	0.35013 (15)	0.35289 (11)	0.02438 (10)	0.0146 (2)
C13	0.49312 (14)	0.35937 (11)	0.11231 (10)	0.0140 (2)
C14	0.65113 (15)	0.28596 (11)	0.10717 (11)	0.0155 (2)
C15	0.80143 (17)	0.13146 (13)	−0.00265 (12)	0.0223 (3)
H15A	0.8243	0.0716	0.0635	0.027*
H15B	0.8983	0.1912	0.0039	0.027*
C16	0.7726 (2)	0.05757 (18)	−0.12749 (15)	0.0387 (4)
H16A	0.8746	0.0112	−0.1390	0.058*
H16B	0.7456	0.1177	−0.1918	0.058*
H16C	0.6793	−0.0034	−0.1314	0.058*
C17	0.31577 (17)	0.26349 (13)	−0.09159 (12)	0.0201 (2)
H17A	0.207 (3)	0.2792 (18)	−0.1382 (18)	0.034 (5)*
H17B	0.316 (3)	0.175 (2)	−0.0718 (18)	0.038 (5)*
H17C	0.398 (2)	0.2794 (18)	−0.1447 (17)	0.034 (5)*
C18	0.79965 (15)	0.42889 (12)	0.47221 (12)	0.0187 (2)
H18A	0.8530	0.4188	0.5566	0.028*
H18B	0.7902	0.5201	0.4575	0.028*
H18C	0.8679	0.3874	0.4164	0.028*
H1N3	0.367 (2)	0.6038 (15)	0.2734 (15)	0.016 (4)*
H1N4	0.120 (2)	0.4247 (17)	−0.0173 (17)	0.026 (4)*

	U11	U22	U33	U12	U13	U23
Cl1	0.01327 (13)	0.02560 (15)	0.01588 (13)	−0.00443 (10)	−0.00218 (9)	0.00376 (10)
O1	0.0153 (4)	0.0211 (4)	0.0210 (4)	0.0060 (3)	−0.0022 (3)	−0.0012 (3)
O2	0.0159 (4)	0.0277 (5)	0.0182 (4)	0.0091 (3)	0.0006 (3)	−0.0024 (3)
O3	0.0145 (4)	0.0270 (5)	0.0195 (4)	0.0048 (3)	−0.0011 (3)	0.0009 (3)
N1	0.0128 (4)	0.0176 (4)	0.0136 (4)	−0.0006 (3)	−0.0002 (3)	0.0026 (3)
N2	0.0128 (4)	0.0175 (4)	0.0149 (4)	0.0011 (3)	−0.0010 (3)	0.0006 (3)
N3	0.0139 (4)	0.0149 (4)	0.0140 (4)	0.0030 (3)	−0.0013 (3)	0.0004 (3)
N4	0.0122 (5)	0.0200 (5)	0.0149 (4)	0.0032 (4)	−0.0019 (4)	−0.0010 (4)
C1	0.0254 (6)	0.0195 (5)	0.0158 (5)	0.0032 (5)	0.0035 (4)	0.0025 (4)
C2	0.0378 (8)	0.0200 (6)	0.0182 (6)	0.0003 (5)	0.0033 (5)	0.0047 (5)
C3	0.0361 (8)	0.0271 (6)	0.0160 (6)	−0.0124 (6)	0.0031 (5)	0.0039 (5)
C4	0.0224 (6)	0.0350 (7)	0.0190 (6)	−0.0072 (5)	0.0037 (5)	0.0033 (5)
C5	0.0192 (6)	0.0236 (6)	0.0179 (5)	−0.0001 (4)	0.0027 (4)	0.0033 (4)
C6	0.0201 (6)	0.0164 (5)	0.0115 (5)	−0.0015 (4)	0.0021 (4)	0.0010 (4)
C7	0.0132 (5)	0.0161 (5)	0.0129 (5)	0.0009 (4)	−0.0002 (4)	0.0014 (4)
C8	0.0110 (5)	0.0147 (5)	0.0133 (5)	0.0017 (4)	0.0004 (4)	0.0009 (4)
C9	0.0125 (5)	0.0150 (5)	0.0147 (5)	0.0022 (4)	−0.0002 (4)	−0.0004 (4)
C10	0.0100 (5)	0.0159 (5)	0.0141 (5)	0.0011 (4)	0.0000 (4)	0.0026 (4)
C11	0.0145 (5)	0.0155 (5)	0.0147 (5)	0.0006 (4)	0.0006 (4)	0.0030 (4)
C12	0.0132 (5)	0.0168 (5)	0.0139 (5)	0.0017 (4)	0.0023 (4)	0.0020 (4)
C13	0.0125 (5)	0.0164 (5)	0.0132 (5)	0.0019 (4)	0.0017 (4)	0.0021 (4)
C14	0.0142 (5)	0.0180 (5)	0.0148 (5)	0.0018 (4)	0.0027 (4)	0.0044 (4)
C15	0.0179 (6)	0.0280 (6)	0.0212 (6)	0.0107 (5)	0.0032 (5)	0.0016 (5)
C16	0.0343 (8)	0.0504 (10)	0.0292 (8)	0.0220 (7)	0.0025 (6)	−0.0105 (7)
C17	0.0182 (6)	0.0246 (6)	0.0157 (5)	0.0029 (5)	−0.0008 (4)	−0.0031 (4)
C18	0.0120 (5)	0.0226 (6)	0.0200 (6)	0.0000 (4)	−0.0010 (4)	0.0007 (4)

Cl1—C7	1.7070 (12)	C5—C6	1.3899 (17)
O1—C11	1.2378 (14)	C5—H5A	0.9300
O2—C14	1.3456 (14)	C7—C8	1.3760 (16)
O2—C15	1.4505 (14)	C8—C9	1.4158 (15)
O3—C14	1.2157 (14)	C8—C10	1.5125 (15)
N1—C7	1.3641 (14)	C9—C18	1.4924 (16)
N1—N2	1.3712 (13)	C10—C13	1.5202 (15)
N1—C6	1.4268 (15)	C10—H10A	0.9800
N2—C9	1.3334 (15)	C12—C13	1.3570 (15)
N3—C11	1.3468 (14)	C12—C17	1.5047 (16)
N3—C10	1.4695 (14)	C13—C14	1.4685 (15)
N3—H1N3	0.862 (16)	C15—C16	1.5020 (19)
N4—C11	1.3760 (15)	C15—H15A	0.9700
N4—C12	1.3828 (14)	C15—H15B	0.9700
N4—H1N4	0.883 (18)	C16—H16A	0.9600
C1—C2	1.3886 (18)	C16—H16B	0.9600
C1—C6	1.3932 (17)	C16—H16C	0.9600
C1—H1A	0.9300	C17—H17A	0.95 (2)
C2—C3	1.383 (2)	C17—H17B	0.95 (2)
C2—H2A	0.9300	C17—H17C	0.956 (19)
C3—C4	1.387 (2)	C18—H18A	0.9600
C3—H3A	0.9300	C18—H18B	0.9600
C4—C5	1.3887 (18)	C18—H18C	0.9600
C4—H4A	0.9300
C14—O2—C15	115.79 (9)	C8—C10—C13	112.92 (9)
C7—N1—N2	110.16 (9)	N3—C10—H10A	107.5
C7—N1—C6	130.02 (10)	C8—C10—H10A	107.5
N2—N1—C6	119.60 (9)	C13—C10—H10A	107.5
C9—N2—N1	105.46 (9)	O1—C11—N3	122.70 (10)
C11—N3—C10	125.12 (9)	O1—C11—N4	120.82 (10)
C11—N3—H1N3	117.1 (10)	N3—C11—N4	116.45 (10)
C10—N3—H1N3	115.4 (10)	C13—C12—N4	119.61 (10)
C11—N4—C12	124.24 (10)	C13—C12—C17	127.57 (10)
C11—N4—H1N4	117.5 (11)	N4—C12—C17	112.82 (10)
C12—N4—H1N4	118.3 (11)	C12—C13—C14	125.95 (10)
C2—C1—C6	119.05 (12)	C12—C13—C10	120.88 (10)
C2—C1—H1A	120.5	C14—C13—C10	113.16 (9)
C6—C1—H1A	120.5	O3—C14—O2	122.46 (11)
C3—C2—C1	120.45 (12)	O3—C14—C13	122.92 (11)
C3—C2—H2A	119.8	O2—C14—C13	114.63 (10)
C1—C2—H2A	119.8	O2—C15—C16	106.46 (10)
C2—C3—C4	120.08 (13)	O2—C15—H15A	110.4
C2—C3—H3A	120.0	C16—C15—H15A	110.4
C4—C3—H3A	120.0	O2—C15—H15B	110.4
C3—C4—C5	120.28 (13)	C16—C15—H15B	110.4
C3—C4—H4A	119.9	H15A—C15—H15B	108.6
C5—C4—H4A	119.9	C15—C16—H16A	109.5
C4—C5—C6	119.22 (12)	C15—C16—H16B	109.5
C4—C5—H5A	120.4	H16A—C16—H16B	109.5
C6—C5—H5A	120.4	C15—C16—H16C	109.5
C5—C6—C1	120.82 (12)	H16A—C16—H16C	109.5
C5—C6—N1	120.71 (11)	H16B—C16—H16C	109.5
C1—C6—N1	118.47 (11)	C12—C17—H17A	111.0 (11)
N1—C7—C8	108.70 (10)	C12—C17—H17B	111.1 (12)
N1—C7—Cl1	123.11 (9)	H17A—C17—H17B	106.9 (16)
C8—C7—Cl1	128.18 (9)	C12—C17—H17C	110.3 (11)
C7—C8—C9	103.79 (10)	H17A—C17—H17C	106.4 (16)
C7—C8—C10	128.17 (10)	H17B—C17—H17C	111.0 (17)
C9—C8—C10	128.00 (10)	C9—C18—H18A	109.5
N2—C9—C8	111.88 (10)	C9—C18—H18B	109.5
N2—C9—C18	120.43 (10)	H18A—C18—H18B	109.5
C8—C9—C18	127.69 (11)	C9—C18—H18C	109.5
N3—C10—C8	111.17 (9)	H18A—C18—H18C	109.5
N3—C10—C13	110.10 (9)	H18B—C18—H18C	109.5
C7—N1—N2—C9	0.68 (12)	C11—N3—C10—C8	−103.04 (12)
C6—N1—N2—C9	175.80 (10)	C11—N3—C10—C13	22.87 (15)
C6—C1—C2—C3	−0.95 (19)	C7—C8—C10—N3	57.33 (15)
C1—C2—C3—C4	−1.6 (2)	C9—C8—C10—N3	−120.05 (12)
C2—C3—C4—C5	1.8 (2)	C7—C8—C10—C13	−67.00 (15)
C3—C4—C5—C6	0.54 (19)	C9—C8—C10—C13	115.62 (12)
C4—C5—C6—C1	−3.09 (18)	C10—N3—C11—O1	166.80 (11)
C4—C5—C6—N1	177.20 (11)	C10—N3—C11—N4	−15.22 (16)
C2—C1—C6—C5	3.29 (18)	C12—N4—C11—O1	177.43 (11)
C2—C1—C6—N1	−176.99 (11)	C12—N4—C11—N3	−0.59 (17)
C7—N1—C6—C5	−46.54 (17)	C11—N4—C12—C13	5.61 (18)
N2—N1—C6—C5	139.45 (11)	C11—N4—C12—C17	−174.82 (11)
C7—N1—C6—C1	133.75 (13)	N4—C12—C13—C14	−175.52 (11)
N2—N1—C6—C1	−40.27 (15)	C17—C12—C13—C14	5.0 (2)
N2—N1—C7—C8	−0.59 (13)	N4—C12—C13—C10	4.26 (17)
C6—N1—C7—C8	−175.05 (11)	C17—C12—C13—C10	−175.23 (11)
N2—N1—C7—Cl1	−179.88 (8)	N3—C10—C13—C12	−16.61 (15)
C6—N1—C7—Cl1	5.67 (17)	C8—C10—C13—C12	108.30 (12)
N1—C7—C8—C9	0.25 (12)	N3—C10—C13—C14	163.20 (9)
Cl1—C7—C8—C9	179.49 (9)	C8—C10—C13—C14	−71.89 (12)
N1—C7—C8—C10	−177.62 (10)	C15—O2—C14—O3	−1.48 (17)
Cl1—C7—C8—C10	1.62 (18)	C15—O2—C14—C13	178.58 (10)
N1—N2—C9—C8	−0.52 (12)	C12—C13—C14—O3	177.86 (12)
N1—N2—C9—C18	178.99 (10)	C10—C13—C14—O3	−1.93 (17)
C7—C8—C9—N2	0.18 (13)	C12—C13—C14—O2	−2.20 (17)
C10—C8—C9—N2	178.06 (10)	C10—C13—C14—O2	178.00 (10)
C7—C8—C9—C18	−179.29 (11)	C14—O2—C15—C16	−173.84 (12)
C10—C8—C9—C18	−1.41 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···N2i	0.863 (16)	2.233 (16)	3.0601 (14)	160.7 (14)
N4—H1N4···O1ii	0.882 (17)	1.960 (17)	2.8418 (13)	176.8 (17)
C18—H18C···O3	0.96	2.59	3.2850 (15)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯N2i	0.863 (16)	2.233 (16)	3.0601 (14)	160.7 (14)
N4—H1N4⋯O1ii	0.882 (17)	1.960 (17)	2.8418 (13)	176.8 (17)
C18—H18C⋯O3	0.96	2.59	3.2850 (15)	129

Symmetry codes: (i) ; (ii) .