Ethyl 4-(3-bromo-phen-yl)-6-methyl-2-oxo-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C(14)H(15)BrN(2)O(3), the dihydro-pyrimidin-one ring adopts a boat conformation. In the crystal, adjacent mol-ecules are linked through N-H⋯O hydrogen bonds forming an R(2) (2)(8) ring motif and generating a zigzag chain extending in [010].

Related literature

For general background to and the pharmaceutical applications of pyrimidino­nes, see: Biginelli (1891 ▶); Atwal (1990 ▶); Kappe (2000 ▶). For a related structure, see: Fun et al. (2009 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C14H15BrN2O3

M = 339.19

Monoclinic,

a = 12.5184 (11) Å

b = 7.3412 (5) Å

c = 17.0426 (15) Å

β = 115.086 (6)°

V = 1418.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 2.91 mm−1

T = 293 K

0.25 × 0.23 × 0.2 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.488, T max = 0.559

13419 measured reflections

3541 independent reflections

2597 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.092

S = 1.02

3541 reflections

183 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.57 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049019/bt5419sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049019/bt5419Isup2.hkl

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

C14H15BrN2O3	F(000) = 688
Mr = 339.19	Dx = 1.588 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 754 reflections
a = 12.5184 (11) Å	θ = 1.8–28.4°
b = 7.3412 (5) Å	µ = 2.91 mm−1
c = 17.0426 (15) Å	T = 293 K
β = 115.086 (6)°	Block, colourless
V = 1418.5 (2) Å3	0.25 × 0.23 × 0.2 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	3541 independent reflections
Radiation source: fine-focus sealed tube	2597 reflections with I > 2σ(I)
graphite	Rint = 0.033
ω and φ scans	θmax = 28.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −16→14
Tmin = 0.488, Tmax = 0.559	k = −9→9
13419 measured reflections	l = −22→22

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.4545P] where P = (Fo2 + 2Fc2)/3
3541 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.57 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
Br1	0.44441 (3)	−0.16428 (4)	0.393184 (18)	0.06851 (13)
O1	−0.01129 (13)	0.45992 (18)	0.25987 (9)	0.0366 (3)
O2	0.19555 (17)	0.5721 (2)	−0.01580 (10)	0.0542 (4)
O3	0.20747 (13)	0.2739 (2)	0.01176 (9)	0.0398 (3)
N1	0.07460 (14)	0.3000 (2)	0.18856 (10)	0.0300 (3)
H1A	0.0413	0.2007	0.1932	0.036*
N2	0.07540 (15)	0.6114 (2)	0.18553 (10)	0.0328 (4)
H2A	0.0724	0.7129	0.2097	0.039*
C1	0.37388 (19)	0.3902 (3)	0.25000 (14)	0.0394 (5)
H1	0.3602	0.5013	0.2212	0.047*
C2	0.4823 (2)	0.3559 (3)	0.31773 (15)	0.0471 (5)
H2	0.5408	0.4446	0.3338	0.056*
C3	0.5056 (2)	0.1925 (3)	0.36196 (14)	0.0455 (5)
H3	0.5785	0.1701	0.4077	0.055*
C4	0.41681 (19)	0.0634 (3)	0.33589 (13)	0.0390 (5)
C5	0.30810 (18)	0.0945 (3)	0.26915 (12)	0.0349 (4)
H5	0.2498	0.0056	0.2536	0.042*
C6	0.28529 (16)	0.2598 (3)	0.22473 (11)	0.0287 (4)
C7	0.16221 (16)	0.2905 (2)	0.15251 (11)	0.0271 (4)
H7	0.1428	0.1848	0.1138	0.033*
C8	0.04431 (16)	0.4545 (2)	0.21425 (11)	0.0285 (4)
C9	0.11175 (17)	0.6132 (2)	0.11857 (11)	0.0293 (4)
C10	0.15120 (16)	0.4584 (2)	0.09844 (11)	0.0281 (4)
C11	0.18583 (17)	0.4468 (3)	0.02604 (11)	0.0329 (4)
C12	0.2432 (2)	0.2459 (4)	−0.05813 (13)	0.0446 (5)
H12A	0.3109	0.3214	−0.0493	0.054*
H12B	0.1793	0.2784	−0.1132	0.054*
C13	0.2736 (3)	0.0503 (4)	−0.05805 (18)	0.0688 (8)
H13A	0.3368	0.0196	−0.0033	0.103*
H13B	0.2979	0.0279	−0.1036	0.103*
H13C	0.2059	−0.0231	−0.0672	0.103*
C14	0.1005 (2)	0.7953 (3)	0.07619 (13)	0.0397 (5)
H14A	0.1762	0.8535	0.0982	0.060*
H14B	0.0463	0.8696	0.0885	0.060*
H14C	0.0716	0.7794	0.0147	0.060*

	U11	U22	U33	U12	U13	U23
Br1	0.0843 (2)	0.04469 (16)	0.06112 (18)	0.01772 (13)	0.01586 (15)	0.02071 (12)
O1	0.0494 (8)	0.0265 (7)	0.0486 (8)	0.0023 (6)	0.0348 (7)	0.0010 (6)
O2	0.0830 (12)	0.0447 (10)	0.0545 (9)	0.0032 (8)	0.0483 (9)	0.0133 (8)
O3	0.0568 (9)	0.0381 (8)	0.0374 (7)	−0.0002 (7)	0.0322 (7)	−0.0014 (6)
N1	0.0377 (8)	0.0216 (7)	0.0397 (8)	−0.0004 (6)	0.0250 (7)	0.0030 (6)
N2	0.0496 (10)	0.0197 (7)	0.0374 (8)	−0.0007 (6)	0.0267 (8)	−0.0020 (6)
C1	0.0426 (11)	0.0347 (10)	0.0429 (11)	−0.0015 (9)	0.0202 (9)	0.0064 (9)
C2	0.0382 (11)	0.0504 (14)	0.0514 (12)	−0.0075 (10)	0.0178 (10)	0.0000 (10)
C3	0.0401 (11)	0.0548 (14)	0.0389 (11)	0.0097 (10)	0.0140 (9)	0.0021 (10)
C4	0.0519 (12)	0.0331 (11)	0.0352 (9)	0.0121 (9)	0.0216 (9)	0.0059 (8)
C5	0.0441 (11)	0.0278 (9)	0.0354 (9)	0.0015 (8)	0.0195 (9)	−0.0002 (8)
C6	0.0362 (9)	0.0273 (9)	0.0291 (8)	0.0036 (7)	0.0202 (8)	0.0001 (7)
C7	0.0356 (9)	0.0219 (8)	0.0289 (8)	−0.0002 (7)	0.0186 (7)	−0.0004 (7)
C8	0.0327 (9)	0.0247 (9)	0.0312 (8)	0.0001 (7)	0.0165 (8)	0.0016 (7)
C9	0.0334 (9)	0.0258 (9)	0.0289 (8)	−0.0037 (7)	0.0133 (7)	0.0021 (7)
C10	0.0330 (9)	0.0269 (9)	0.0261 (8)	−0.0017 (7)	0.0142 (7)	0.0019 (7)
C11	0.0358 (10)	0.0356 (10)	0.0284 (8)	−0.0012 (8)	0.0146 (8)	0.0015 (8)
C12	0.0493 (12)	0.0619 (15)	0.0323 (10)	0.0057 (11)	0.0266 (9)	−0.0014 (10)
C13	0.099 (2)	0.0677 (19)	0.0591 (15)	0.0209 (16)	0.0522 (16)	−0.0020 (14)
C14	0.0533 (12)	0.0255 (9)	0.0433 (11)	0.0000 (8)	0.0235 (10)	0.0065 (8)

Br1—C4	1.892 (2)	C4—C5	1.373 (3)
O1—C8	1.245 (2)	C5—C6	1.394 (3)
O2—C11	1.202 (2)	C5—H5	0.9300
O3—C11	1.341 (2)	C6—C7	1.527 (3)
O3—C12	1.453 (2)	C7—C10	1.510 (2)
N1—C8	1.328 (2)	C7—H7	0.9800
N1—C7	1.469 (2)	C9—C10	1.340 (3)
N1—H1A	0.8600	C9—C14	1.497 (3)
N2—C8	1.371 (2)	C10—C11	1.474 (2)
N2—C9	1.396 (2)	C12—C13	1.486 (4)
N2—H2A	0.8600	C12—H12A	0.9700
C1—C2	1.382 (3)	C12—H12B	0.9700
C1—C6	1.388 (3)	C13—H13A	0.9600
C1—H1	0.9300	C13—H13B	0.9600
C2—C3	1.380 (3)	C13—H13C	0.9600
C2—H2	0.9300	C14—H14A	0.9600
C3—C4	1.383 (3)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C11—O3—C12	116.02 (16)	O1—C8—N1	123.16 (16)
C8—N1—C7	123.15 (15)	O1—C8—N2	120.97 (16)
C8—N1—H1A	118.4	N1—C8—N2	115.85 (16)
C7—N1—H1A	118.4	C10—C9—N2	118.96 (16)
C8—N2—C9	122.68 (15)	C10—C9—C14	127.08 (17)
C8—N2—H2A	118.7	N2—C9—C14	113.95 (17)
C9—N2—H2A	118.7	C9—C10—C11	122.34 (16)
C2—C1—C6	120.4 (2)	C9—C10—C7	118.95 (15)
C2—C1—H1	119.8	C11—C10—C7	118.71 (16)
C6—C1—H1	119.8	O2—C11—O3	122.56 (17)
C3—C2—C1	121.3 (2)	O2—C11—C10	126.29 (19)
C3—C2—H2	119.3	O3—C11—C10	111.15 (16)
C1—C2—H2	119.3	O3—C12—C13	107.72 (19)
C2—C3—C4	117.7 (2)	O3—C12—H12A	110.2
C2—C3—H3	121.1	C13—C12—H12A	110.2
C4—C3—H3	121.1	O3—C12—H12B	110.2
C5—C4—C3	122.09 (19)	C13—C12—H12B	110.2
C5—C4—Br1	118.33 (17)	H12A—C12—H12B	108.5
C3—C4—Br1	119.58 (16)	C12—C13—H13A	109.5
C4—C5—C6	119.84 (19)	C12—C13—H13B	109.5
C4—C5—H5	120.1	H13A—C13—H13B	109.5
C6—C5—H5	120.1	C12—C13—H13C	109.5
C1—C6—C5	118.62 (18)	H13A—C13—H13C	109.5
C1—C6—C7	123.28 (17)	H13B—C13—H13C	109.5
C5—C6—C7	118.07 (17)	C9—C14—H14A	109.5
N1—C7—C10	109.00 (14)	C9—C14—H14B	109.5
N1—C7—C6	110.31 (14)	H14A—C14—H14B	109.5
C10—C7—C6	114.35 (15)	C9—C14—H14C	109.5
N1—C7—H7	107.6	H14A—C14—H14C	109.5
C10—C7—H7	107.6	H14B—C14—H14C	109.5
C6—C7—H7	107.6
C6—C1—C2—C3	−0.1 (3)	C9—N2—C8—N1	14.2 (3)
C1—C2—C3—C4	0.4 (4)	C8—N2—C9—C10	−20.2 (3)
C2—C3—C4—C5	−0.8 (3)	C8—N2—C9—C14	159.42 (18)
C2—C3—C4—Br1	179.20 (17)	N2—C9—C10—C11	177.02 (16)
C3—C4—C5—C6	0.8 (3)	C14—C9—C10—C11	−2.5 (3)
Br1—C4—C5—C6	−179.11 (14)	N2—C9—C10—C7	−3.8 (3)
C2—C1—C6—C5	0.1 (3)	C14—C9—C10—C7	176.64 (18)
C2—C1—C6—C7	177.96 (19)	N1—C7—C10—C9	28.6 (2)
C4—C5—C6—C1	−0.5 (3)	C6—C7—C10—C9	−95.4 (2)
C4—C5—C6—C7	−178.46 (17)	N1—C7—C10—C11	−152.22 (15)
C8—N1—C7—C10	−36.2 (2)	C6—C7—C10—C11	83.8 (2)
C8—N1—C7—C6	90.2 (2)	C12—O3—C11—O2	−0.3 (3)
C1—C6—C7—N1	−111.5 (2)	C12—O3—C11—C10	−179.66 (16)
C5—C6—C7—N1	66.4 (2)	C9—C10—C11—O2	8.7 (3)
C1—C6—C7—C10	11.8 (2)	C7—C10—C11—O2	−170.5 (2)
C5—C6—C7—C10	−170.39 (16)	C9—C10—C11—O3	−171.96 (17)
C7—N1—C8—O1	−165.42 (17)	C7—C10—C11—O3	8.9 (2)
C7—N1—C8—N2	16.2 (2)	C11—O3—C12—C13	174.7 (2)
C9—N2—C8—O1	−164.23 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.86	2.04	2.868 (2)	161
N2—H2A···O1ii	0.86	2.12	2.948 (2)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.86	2.04	2.868 (2)	161
N2—H2A⋯O1ii	0.86	2.12	2.948 (2)	162

Symmetry codes: (i) ; (ii) .