Ethyl 2-isopropyl-amino-5-methyl-4-oxo-3-phenyl-3,4-dihydro-thieno[2,3-d]pyrimidine-6-carboxyl-ate.

The title compound, C(19)H(21)N(3)O(3)S, was synthesized via an aza-Wittig reaction of a functionalized imino-phospho-rane with phenyl isocyanate under mild conditions. In the mol-ecule, the fused thienopyrimidine ring system makes a dihedral angle of 66.30 (11)° with the phenyl ring. An intra-molecular C-H⋯O hydrogen bond occurs. The terminal -OCH(2)CH(3) group is disordered over two sites with refined occupancies of 0.537 (13) and 0.463 (13). The crystal packing is stabilized by inter-molecular C-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For the biological and pharmaceutical activity of pyrimidinone derivatives, see: Modica et al. (2004 ▶); Panico et al. (2001 ▶). For related structures, see: Zheng et al. (2007 ▶); Hu et al. (2007 ▶); Xu (2008 ▶); Xu et al. (2006 ▶).

Experimental

Crystal data

C19H21N3O3S

M = 371.45

Orthorhombic,

a = 8.5995 (14) Å

b = 13.673 (2) Å

c = 15.912 (3) Å

V = 1871.0 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 298 K

0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.943, T max = 0.981

12706 measured reflections

4636 independent reflections

4149 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.123

S = 1.10

4636 reflections

271 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 1984 Friedel pairs

Flack parameter: 0.09 (8)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045449/bt5115sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045449/bt5115Isup2.hkl

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

C19H21N3O3S	F(000) = 784
Mr = 371.45	Dx = 1.319 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4510 reflections
a = 8.5995 (14) Å	θ = 2.6–26.5°
b = 13.673 (2) Å	µ = 0.20 mm−1
c = 15.912 (3) Å	T = 298 K
V = 1871.0 (5) Å3	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Bruker SMART 4K CCD area-detector diffractometer	4636 independent reflections
Radiation source: fine-focus sealed tube	4149 reflections with I > 2σ(I)
graphite	Rint = 0.061
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→11
Tmin = 0.943, Tmax = 0.981	k = −18→17
12706 measured reflections	l = −21→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.123	w = 1/[σ2(Fo2) + (0.0601P)2] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
4636 reflections	Δρmax = 0.33 e Å−3
271 parameters	Δρmin = −0.21 e Å−3
6 restraints	Absolute structure: Flack (1983), 1984 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.09 (8)

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	Occ. (<1)
C1	0.2137 (2)	0.27871 (14)	0.47156 (12)	0.0406 (4)
C2	0.2947 (3)	0.21627 (15)	0.41948 (14)	0.0488 (5)
H2	0.3578	0.1675	0.4417	0.059*
C3	0.2800 (3)	0.22783 (18)	0.33286 (15)	0.0606 (6)
H3	0.3351	0.1869	0.2969	0.073*
C4	0.1855 (4)	0.2987 (2)	0.30019 (16)	0.0694 (8)
H4	0.1765	0.3056	0.2423	0.083*
C5	0.1040 (4)	0.3595 (2)	0.35261 (17)	0.0716 (8)
H5	0.0385	0.4070	0.3303	0.086*
C6	0.1196 (3)	0.35009 (17)	0.43916 (15)	0.0552 (6)
H6	0.0663	0.3921	0.4749	0.066*
C7	0.2851 (2)	0.34531 (13)	0.61047 (13)	0.0395 (4)
C8	0.2038 (2)	0.27158 (14)	0.72863 (12)	0.0408 (4)
C9	0.1490 (2)	0.18802 (14)	0.68884 (12)	0.0376 (4)
C10	0.1562 (2)	0.18457 (13)	0.59891 (13)	0.0391 (4)
C11	0.4070 (3)	0.50790 (14)	0.60896 (14)	0.0464 (5)
H11	0.3291	0.5270	0.6508	0.056*
C12	0.4122 (4)	0.5855 (2)	0.5416 (2)	0.0834 (10)
H12A	0.4823	0.5656	0.4979	0.125*
H12B	0.4476	0.6460	0.5655	0.125*
H12C	0.3101	0.5944	0.5185	0.125*
C13	0.5612 (3)	0.4960 (2)	0.6528 (2)	0.0693 (7)
H13A	0.5529	0.4459	0.6948	0.104*
H13B	0.5899	0.5566	0.6790	0.104*
H13C	0.6392	0.4779	0.6125	0.104*
C14	0.0844 (2)	0.11758 (14)	0.74560 (13)	0.0400 (4)
C15	0.0934 (2)	0.14955 (14)	0.82673 (14)	0.0446 (5)
C16	0.0151 (3)	0.02200 (17)	0.71855 (17)	0.0597 (6)
H16A	−0.0409	−0.0065	0.7647	0.089*
H16B	0.0966	−0.0216	0.7012	0.089*
H16C	−0.0547	0.0328	0.6724	0.089*
C17	0.0542 (3)	0.09639 (19)	0.90376 (15)	0.0544 (6)
C18'	0.0196 (9)	0.1295 (7)	1.0546 (4)	0.065 (2)	0.463 (13)
H18C	−0.0535	0.0755	1.0519	0.078*	0.463 (13)
H18D	−0.0262	0.1809	1.0885	0.078*	0.463 (13)
C19'	0.1698 (11)	0.0955 (10)	1.0941 (7)	0.099 (4)	0.463 (13)
H19D	0.2073	0.0388	1.0648	0.148*	0.463 (13)
H19E	0.1519	0.0792	1.1520	0.148*	0.463 (13)
H19F	0.2457	0.1468	1.0907	0.148*	0.463 (13)
O3'	0.0508 (11)	0.1657 (6)	0.9710 (4)	0.0593 (17)	0.463 (13)
C18	0.0891 (12)	0.0864 (5)	1.0496 (3)	0.070 (2)	0.537 (13)
H18A	0.1427	0.0240	1.0484	0.084*	0.537 (13)
H18B	−0.0205	0.0748	1.0601	0.084*	0.537 (13)
C19	0.1567 (16)	0.1515 (7)	1.1163 (5)	0.106 (3)	0.537 (13)
H19A	0.2569	0.1746	1.0984	0.160*	0.537 (13)
H19B	0.1676	0.1154	1.1676	0.160*	0.537 (13)
H19C	0.0889	0.2063	1.1253	0.160*	0.537 (13)
O3	0.1105 (10)	0.1383 (5)	0.9708 (3)	0.0599 (15)	0.537 (13)
N1	0.22489 (19)	0.26857 (11)	0.56226 (10)	0.0390 (4)
N2	0.2725 (2)	0.34924 (12)	0.69284 (11)	0.0414 (4)
N3	0.3553 (2)	0.41720 (12)	0.56877 (12)	0.0464 (4)
H3A	0.387 (3)	0.4055 (18)	0.5245 (18)	0.056*
O1	0.1063 (2)	0.11958 (11)	0.55348 (10)	0.0530 (4)
O2	0.0060 (2)	0.01385 (13)	0.90784 (12)	0.0684 (5)
S1	0.17644 (7)	0.26585 (4)	0.83568 (3)	0.05191 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0506 (11)	0.0394 (10)	0.0320 (9)	−0.0100 (9)	0.0019 (8)	−0.0027 (8)
C2	0.0563 (12)	0.0467 (10)	0.0435 (11)	−0.0021 (9)	−0.0007 (9)	−0.0103 (9)
C3	0.0789 (16)	0.0605 (13)	0.0425 (12)	−0.0130 (12)	0.0112 (12)	−0.0177 (12)
C4	0.102 (2)	0.0714 (17)	0.0345 (12)	−0.0149 (17)	−0.0017 (13)	0.0018 (11)
C5	0.099 (2)	0.0705 (16)	0.0456 (15)	0.0111 (15)	−0.0045 (14)	0.0150 (13)
C6	0.0710 (15)	0.0511 (12)	0.0434 (13)	0.0092 (11)	0.0073 (11)	0.0047 (10)
C7	0.0475 (11)	0.0334 (9)	0.0375 (10)	−0.0033 (8)	0.0027 (8)	−0.0061 (7)
C8	0.0475 (11)	0.0422 (10)	0.0327 (9)	−0.0002 (9)	0.0015 (8)	−0.0026 (8)
C9	0.0428 (10)	0.0340 (8)	0.0359 (9)	−0.0008 (8)	−0.0028 (8)	0.0014 (7)
C10	0.0460 (10)	0.0325 (8)	0.0389 (10)	0.0009 (8)	−0.0033 (8)	−0.0008 (7)
C11	0.0578 (13)	0.0343 (9)	0.0472 (12)	−0.0073 (9)	0.0111 (10)	−0.0077 (8)
C12	0.122 (3)	0.0458 (13)	0.082 (2)	−0.0179 (16)	0.0038 (19)	0.0125 (14)
C13	0.0615 (15)	0.0708 (16)	0.0756 (19)	−0.0120 (13)	−0.0005 (14)	−0.0171 (15)
C14	0.0424 (10)	0.0358 (9)	0.0418 (11)	0.0007 (8)	0.0007 (8)	0.0052 (8)
C15	0.0475 (11)	0.0414 (10)	0.0449 (12)	−0.0033 (8)	−0.0007 (9)	0.0060 (9)
C16	0.0805 (17)	0.0412 (12)	0.0573 (15)	−0.0124 (11)	0.0060 (13)	0.0022 (11)
C17	0.0591 (14)	0.0637 (14)	0.0403 (12)	−0.0082 (11)	−0.0004 (10)	0.0081 (11)
C18'	0.082 (5)	0.059 (4)	0.053 (4)	0.003 (3)	0.020 (3)	0.003 (3)
C19'	0.099 (6)	0.128 (10)	0.070 (7)	0.009 (7)	−0.001 (5)	0.028 (7)
O3'	0.083 (5)	0.055 (4)	0.040 (2)	−0.004 (3)	0.006 (3)	0.007 (2)
C18	0.107 (6)	0.071 (4)	0.032 (3)	−0.005 (4)	−0.004 (3)	0.013 (3)
C19	0.193 (10)	0.073 (5)	0.054 (4)	−0.001 (5)	−0.024 (5)	0.003 (3)
O3	0.090 (4)	0.050 (3)	0.0398 (19)	0.000 (2)	−0.002 (2)	0.0111 (18)
N1	0.0515 (9)	0.0339 (7)	0.0315 (8)	−0.0024 (7)	0.0007 (7)	−0.0029 (7)
N2	0.0549 (10)	0.0348 (8)	0.0345 (9)	−0.0057 (7)	0.0030 (7)	−0.0040 (7)
N3	0.0623 (11)	0.0403 (8)	0.0365 (9)	−0.0117 (8)	0.0130 (8)	−0.0084 (7)
O1	0.0762 (11)	0.0409 (7)	0.0420 (9)	−0.0149 (7)	−0.0053 (8)	−0.0033 (6)
O2	0.0874 (13)	0.0600 (10)	0.0578 (11)	−0.0188 (10)	0.0060 (10)	0.0144 (9)
S1	0.0734 (4)	0.0499 (3)	0.0324 (2)	−0.0140 (3)	0.0024 (2)	−0.0019 (2)

C1—C6	1.369 (3)	C13—H13A	0.9600
C1—C2	1.379 (3)	C13—H13B	0.9600
C1—N1	1.453 (2)	C13—H13C	0.9600
C2—C3	1.393 (3)	C14—C15	1.365 (3)
C2—H2	0.9300	C14—C16	1.499 (3)
C3—C4	1.367 (4)	C15—C17	1.464 (3)
C3—H3	0.9300	C15—S1	1.749 (2)
C4—C5	1.371 (4)	C16—H16A	0.9600
C4—H4	0.9300	C16—H16B	0.9600
C5—C6	1.390 (3)	C16—H16C	0.9600
C5—H5	0.9300	C17—O2	1.204 (3)
C6—H6	0.9300	C17—O3	1.303 (7)
C7—N2	1.316 (3)	C17—O3'	1.429 (8)
C7—N3	1.331 (3)	C18'—O3'	1.445 (7)
C7—N1	1.399 (2)	C18'—C19'	1.510 (8)
C8—N2	1.342 (2)	C18'—H18C	0.9700
C8—C9	1.389 (3)	C18'—H18D	0.9700
C8—S1	1.721 (2)	C19'—H19D	0.9600
C9—C14	1.433 (3)	C19'—H19E	0.9600
C9—C10	1.433 (3)	C19'—H19F	0.9600
C10—O1	1.223 (2)	C18—O3	1.453 (6)
C10—N1	1.417 (2)	C18—C19	1.502 (7)
C11—N3	1.464 (3)	C18—H18A	0.9700
C11—C13	1.508 (4)	C18—H18B	0.9700
C11—C12	1.509 (4)	C19—H19A	0.9600
C11—H11	0.9800	C19—H19B	0.9600
C12—H12A	0.9600	C19—H19C	0.9600
C12—H12B	0.9600	N3—H3A	0.77 (3)
C12—H12C	0.9600
C6—C1—C2	120.9 (2)	H13B—C13—H13C	109.5
C6—C1—N1	118.77 (19)	C15—C14—C9	111.03 (18)
C2—C1—N1	120.30 (19)	C15—C14—C16	125.0 (2)
C1—C2—C3	118.6 (2)	C9—C14—C16	123.99 (19)
C1—C2—H2	120.7	C14—C15—C17	128.3 (2)
C3—C2—H2	120.7	C14—C15—S1	113.04 (16)
C4—C3—C2	120.7 (2)	C17—C15—S1	118.50 (17)
C4—C3—H3	119.7	C14—C16—H16A	109.5
C2—C3—H3	119.7	C14—C16—H16B	109.5
C3—C4—C5	120.2 (2)	H16A—C16—H16B	109.5
C3—C4—H4	119.9	C14—C16—H16C	109.5
C5—C4—H4	119.9	H16A—C16—H16C	109.5
C4—C5—C6	119.8 (2)	H16B—C16—H16C	109.5
C4—C5—H5	120.1	O2—C17—O3	119.7 (3)
C6—C5—H5	120.1	O2—C17—O3'	125.0 (3)
C1—C6—C5	119.8 (2)	O3—C17—O3'	26.4 (3)
C1—C6—H6	120.1	O2—C17—C15	126.1 (2)
C5—C6—H6	120.1	O3—C17—C15	112.4 (3)
N2—C7—N3	120.23 (18)	O3'—C17—C15	107.6 (3)
N2—C7—N1	123.12 (18)	O3'—C18'—C19'	109.3 (6)
N3—C7—N1	116.64 (17)	O3'—C18'—H18C	109.8
N2—C8—C9	127.35 (18)	C19'—C18'—H18C	109.8
N2—C8—S1	121.07 (14)	O3'—C18'—H18D	109.8
C9—C8—S1	111.57 (14)	C19'—C18'—H18D	109.8
C8—C9—C14	113.40 (18)	H18C—C18'—H18D	108.3
C8—C9—C10	117.90 (18)	C17—O3'—C18'	117.8 (5)
C14—C9—C10	128.62 (19)	O3—C18—C19	105.8 (5)
O1—C10—N1	119.46 (18)	O3—C18—H18A	110.6
O1—C10—C9	126.79 (19)	C19—C18—H18A	110.6
N1—C10—C9	113.72 (17)	O3—C18—H18B	110.6
N3—C11—C13	112.19 (19)	C19—C18—H18B	110.6
N3—C11—C12	107.1 (2)	H18A—C18—H18B	108.7
C13—C11—C12	112.2 (2)	C18—C19—H19A	109.5
N3—C11—H11	108.4	C18—C19—H19B	109.5
C13—C11—H11	108.4	H19A—C19—H19B	109.5
C12—C11—H11	108.4	C18—C19—H19C	109.5
C11—C12—H12A	109.5	H19A—C19—H19C	109.5
C11—C12—H12B	109.5	H19B—C19—H19C	109.5
H12A—C12—H12B	109.5	C17—O3—C18	116.4 (5)
C11—C12—H12C	109.5	C7—N1—C10	122.44 (16)
H12A—C12—H12C	109.5	C7—N1—C1	119.84 (16)
H12B—C12—H12C	109.5	C10—N1—C1	117.29 (15)
C11—C13—H13A	109.5	C7—N2—C8	115.24 (17)
C11—C13—H13B	109.5	C7—N3—C11	123.06 (18)
H13A—C13—H13B	109.5	C7—N3—H3A	117.6 (19)
C11—C13—H13C	109.5	C11—N3—H3A	117.7 (19)
H13A—C13—H13C	109.5	C8—S1—C15	90.95 (10)
C6—C1—C2—C3	0.6 (3)	O3—C17—O3'—C18'	−72.8 (10)
N1—C1—C2—C3	179.51 (18)	C15—C17—O3'—C18'	−177.9 (5)
C1—C2—C3—C4	−1.0 (4)	C19'—C18'—O3'—C17	85.6 (13)
C2—C3—C4—C5	0.1 (4)	O2—C17—O3—C18	−9.1 (7)
C3—C4—C5—C6	1.0 (5)	O3'—C17—O3—C18	100.6 (13)
C2—C1—C6—C5	0.5 (4)	C15—C17—O3—C18	−174.9 (5)
N1—C1—C6—C5	−178.4 (2)	C19—C18—O3—C17	−177.4 (12)
C4—C5—C6—C1	−1.4 (4)	N2—C7—N1—C10	−5.2 (3)
N2—C8—C9—C14	178.76 (19)	N3—C7—N1—C10	175.90 (18)
S1—C8—C9—C14	−0.3 (2)	N2—C7—N1—C1	167.00 (19)
N2—C8—C9—C10	−4.3 (3)	N3—C7—N1—C1	−11.9 (3)
S1—C8—C9—C10	176.67 (15)	O1—C10—N1—C7	−179.60 (19)
C8—C9—C10—O1	−176.0 (2)	C9—C10—N1—C7	2.4 (3)
C14—C9—C10—O1	0.5 (4)	O1—C10—N1—C1	8.0 (3)
C8—C9—C10—N1	1.9 (3)	C9—C10—N1—C1	−170.04 (17)
C14—C9—C10—N1	178.34 (18)	C6—C1—N1—C7	−62.7 (3)
C8—C9—C14—C15	−0.6 (3)	C2—C1—N1—C7	118.4 (2)
C10—C9—C14—C15	−177.1 (2)	C6—C1—N1—C10	109.9 (2)
C8—C9—C14—C16	179.0 (2)	C2—C1—N1—C10	−69.0 (3)
C10—C9—C14—C16	2.4 (4)	N3—C7—N2—C8	−178.13 (19)
C9—C14—C15—C17	−173.8 (2)	N1—C7—N2—C8	3.0 (3)
C16—C14—C15—C17	6.7 (4)	C9—C8—N2—C7	1.7 (3)
C9—C14—C15—S1	1.2 (2)	S1—C8—N2—C7	−179.30 (16)
C16—C14—C15—S1	−178.38 (19)	N2—C7—N3—C11	−6.7 (3)
C14—C15—C17—O2	−0.3 (4)	N1—C7—N3—C11	172.24 (19)
S1—C15—C17—O2	−175.0 (2)	C13—C11—N3—C7	81.3 (3)
C14—C15—C17—O3	164.5 (5)	C12—C11—N3—C7	−155.1 (2)
S1—C15—C17—O3	−10.3 (5)	N2—C8—S1—C15	−178.33 (18)
C14—C15—C17—O3'	−167.9 (5)	C9—C8—S1—C15	0.79 (16)
S1—C15—C17—O3'	17.4 (5)	C14—C15—S1—C8	−1.14 (17)
O2—C17—O3'—C18'	14.3 (9)	C17—C15—S1—C8	174.36 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···O2	0.96	2.33	3.015 (3)	128
C6—H6···O2i	0.93	2.58	3.479 (3)	164
N3—H3A···O1ii	0.77 (3)	2.28 (3)	2.949 (2)	145 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯O2	0.96	2.33	3.015 (3)	128
C6—H6⋯O2i	0.93	2.58	3.479 (3)	164
N3—H3A⋯O1ii	0.77 (3)	2.28 (3)	2.949 (2)	145 (2)

Symmetry codes: (i) ; (ii) .