Ethyl 5-methyl-4-oxo-3-phenyl-2-propyl-amino-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 the aza-Wittig reaction of functionalized imino-phospho-rane with phenyl isocyanate under mild conditions. In the mol-ecule, the fused thienopyrimidine ring system is essentially planar, with a maximum deviation of 0.072 (2) Å, and makes a dihedral angle of 60.11 (9)° with the phenyl ring. An intra-molecular C-H⋯O hydrogen bond is present. The crystal packing is stabilized by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For the preparation and biological and pharmaceutical activities of pyrimidinone derivatives, see: Modica et al. (2004 ▶); Panico et al. (2001 ▶). For the biological activity of thienopyrimidine derivatives, see: Ding et al. (2004 ▶).

Experimental

Crystal data

C19H21N3O3S

M = 371.45

Orthorhombic,

a = 8.1682 (2) Å

b = 14.1247 (3) Å

c = 16.0672 (5) Å

V = 1853.73 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 298 K

0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.969, T max = 0.980

10064 measured reflections

4472 independent reflections

4226 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.136

S = 1.13

4472 reflections

241 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.37 e Å−3

Absolute structure: Flack (1983 ▶), 1861 Freidel pairs

Flack parameter: 0.08 (10)

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/S1600536809033595/at2864sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033595/at2864Isup2.hkl

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

C19H21N3O3S	F(000) = 784
Mr = 371.45	Dx = 1.331 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4659 reflections
a = 8.1682 (2) Å	θ = 2.5–28.0°
b = 14.1247 (3) Å	µ = 0.20 mm−1
c = 16.0672 (5) Å	T = 298 K
V = 1853.73 (8) Å3	Block, colourless
Z = 4	0.16 × 0.12 × 0.10 mm

Bruker SMART 4K CCD area-detector diffractometer	4472 independent reflections
Radiation source: fine-focus sealed tube	4226 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→5
Tmin = 0.969, Tmax = 0.980	k = −18→18
10064 measured reflections	l = −21→21

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)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.136	w = 1/[σ2(Fo2) + (0.0772P)2 + 0.1133P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
4472 reflections	Δρmax = 0.39 e Å−3
241 parameters	Δρmin = −0.37 e Å−3
0 restraints	Absolute structure: Flack (1983), 1861 Freidel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.08 (10)

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
C1	0.2534 (2)	0.22884 (14)	0.48554 (12)	0.0322 (4)
C2	0.3341 (3)	0.15050 (17)	0.45355 (15)	0.0412 (5)
H2	0.3794	0.1052	0.4887	0.049*
C3	0.3457 (3)	0.14132 (19)	0.36796 (15)	0.0515 (6)
H3	0.4008	0.0895	0.3457	0.062*
C4	0.2783 (4)	0.2063 (2)	0.31554 (15)	0.0545 (6)
H4	0.2864	0.1984	0.2582	0.065*
C5	0.1984 (3)	0.28367 (18)	0.34767 (15)	0.0502 (6)
H5	0.1530	0.3283	0.3119	0.060*
C6	0.1848 (3)	0.29565 (16)	0.43303 (13)	0.0388 (5)
H6	0.1304	0.3479	0.4547	0.047*
C7	0.3242 (3)	0.32075 (14)	0.61007 (13)	0.0347 (4)
C8	0.3275 (3)	0.32060 (16)	0.69897 (13)	0.0358 (4)
C9	0.2629 (3)	0.24251 (15)	0.74015 (12)	0.0374 (4)
C10	0.1679 (2)	0.17242 (14)	0.62462 (12)	0.0342 (4)
C11	0.3990 (3)	0.38959 (15)	0.75391 (13)	0.0362 (4)
C12	0.3869 (3)	0.36077 (15)	0.83528 (14)	0.0407 (5)
C13	−0.0094 (3)	0.03243 (17)	0.62828 (15)	0.0483 (6)
H13A	−0.1188	0.0260	0.6055	0.058*
H13B	−0.0201	0.0488	0.6867	0.058*
C14	0.0757 (4)	−0.0588 (2)	0.6213 (2)	0.0725 (9)
H14A	0.0157	−0.1056	0.6532	0.087*
H14B	0.1834	−0.0526	0.6462	0.087*
C15	0.0958 (7)	−0.0951 (3)	0.5329 (3)	0.1005 (15)
H15A	−0.0083	−0.1161	0.5121	0.151*
H15B	0.1716	−0.1471	0.5325	0.151*
H15C	0.1368	−0.0452	0.4981	0.151*
C16	0.4758 (4)	0.47961 (18)	0.72536 (16)	0.0507 (6)
H16A	0.3920	0.5227	0.7075	0.076*
H16B	0.5486	0.4667	0.6798	0.076*
H16C	0.5363	0.5074	0.7704	0.076*
C17	0.4320 (3)	0.41350 (18)	0.91026 (15)	0.0443 (5)
C18	0.4227 (5)	0.4121 (2)	1.05795 (16)	0.0689 (9)
H18A	0.3688	0.4733	1.0586	0.083*
H18B	0.5391	0.4218	1.0662	0.083*
C19	0.3562 (5)	0.3512 (3)	1.12406 (18)	0.0761 (9)
H19A	0.2411	0.3419	1.1151	0.114*
H19B	0.3731	0.3809	1.1771	0.114*
H19C	0.4110	0.2911	1.1231	0.114*
N1	0.2447 (2)	0.24077 (12)	0.57496 (10)	0.0340 (4)
N2	0.1836 (2)	0.16896 (13)	0.70577 (11)	0.0393 (4)
N3	0.0749 (2)	0.10894 (14)	0.58518 (13)	0.0422 (4)
H3A	0.055 (3)	0.121 (2)	0.5323 (18)	0.051*
O1	0.3846 (2)	0.38072 (11)	0.56420 (9)	0.0453 (4)
O2	0.4921 (3)	0.49108 (14)	0.91163 (11)	0.0578 (5)
O3	0.3935 (3)	0.36454 (14)	0.97886 (11)	0.0609 (5)
S1	0.29211 (8)	0.25028 (4)	0.84614 (3)	0.04848 (17)

	U11	U22	U33	U12	U13	U23
C1	0.0379 (9)	0.0327 (10)	0.0261 (9)	−0.0042 (7)	0.0009 (7)	0.0019 (7)
C2	0.0486 (12)	0.0380 (12)	0.0369 (11)	0.0050 (9)	−0.0041 (9)	0.0002 (9)
C3	0.0667 (15)	0.0487 (14)	0.0391 (12)	0.0029 (11)	0.0069 (11)	−0.0120 (10)
C4	0.0743 (17)	0.0613 (16)	0.0278 (10)	−0.0083 (14)	0.0003 (11)	−0.0038 (10)
C5	0.0619 (13)	0.0515 (13)	0.0372 (11)	−0.0084 (11)	−0.0076 (11)	0.0142 (11)
C6	0.0430 (11)	0.0356 (11)	0.0378 (11)	0.0019 (9)	−0.0006 (9)	0.0052 (8)
C7	0.0427 (11)	0.0287 (9)	0.0327 (10)	0.0026 (8)	0.0031 (8)	−0.0027 (8)
C8	0.0447 (11)	0.0326 (10)	0.0301 (10)	−0.0012 (9)	0.0029 (8)	−0.0024 (8)
C9	0.0489 (11)	0.0390 (11)	0.0242 (8)	0.0002 (10)	−0.0013 (8)	0.0001 (8)
C10	0.0439 (11)	0.0290 (10)	0.0297 (10)	−0.0004 (8)	0.0015 (8)	0.0028 (8)
C11	0.0412 (10)	0.0328 (10)	0.0344 (11)	0.0030 (8)	0.0017 (8)	−0.0056 (8)
C12	0.0498 (11)	0.0389 (11)	0.0334 (11)	−0.0011 (9)	0.0002 (9)	−0.0048 (9)
C13	0.0618 (14)	0.0451 (13)	0.0381 (12)	−0.0169 (11)	0.0044 (11)	0.0009 (10)
C14	0.079 (2)	0.0551 (17)	0.083 (2)	−0.0100 (15)	−0.0015 (17)	0.0234 (16)
C15	0.139 (4)	0.053 (2)	0.109 (3)	−0.005 (2)	0.043 (3)	−0.018 (2)
C16	0.0734 (17)	0.0381 (12)	0.0406 (13)	−0.0103 (11)	0.0032 (11)	−0.0060 (10)
C17	0.0517 (12)	0.0460 (13)	0.0354 (11)	0.0043 (10)	−0.0032 (10)	−0.0104 (10)
C18	0.104 (2)	0.0697 (19)	0.0329 (13)	−0.0100 (18)	−0.0062 (14)	−0.0123 (12)
C19	0.101 (2)	0.086 (2)	0.0413 (15)	0.000 (2)	−0.0002 (16)	−0.0025 (15)
N1	0.0460 (8)	0.0304 (8)	0.0258 (8)	−0.0008 (7)	0.0016 (6)	0.0007 (6)
N2	0.0547 (11)	0.0356 (9)	0.0276 (8)	−0.0092 (8)	−0.0007 (8)	0.0024 (7)
N3	0.0570 (11)	0.0387 (10)	0.0309 (9)	−0.0101 (8)	−0.0060 (8)	0.0028 (8)
O1	0.0673 (10)	0.0378 (9)	0.0308 (8)	−0.0124 (8)	0.0093 (7)	0.0004 (6)
O2	0.0789 (12)	0.0515 (11)	0.0429 (10)	−0.0127 (9)	−0.0058 (9)	−0.0113 (8)
O3	0.0943 (14)	0.0570 (11)	0.0313 (9)	−0.0150 (10)	−0.0040 (9)	−0.0089 (8)
S1	0.0721 (4)	0.0474 (3)	0.0259 (2)	−0.0128 (3)	−0.0033 (2)	0.0012 (2)

C1—C6	1.384 (3)	C12—S1	1.751 (2)
C1—C2	1.387 (3)	C13—N3	1.456 (3)
C1—N1	1.448 (2)	C13—C14	1.468 (4)
C2—C3	1.385 (3)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.362 (4)	C14—C15	1.519 (5)
C3—H3	0.9300	C14—H14A	0.9700
C4—C5	1.373 (4)	C14—H14B	0.9700
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.386 (3)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C6—H6	0.9300	C16—H16A	0.9600
C7—O1	1.226 (3)	C16—H16B	0.9600
C7—N1	1.420 (3)	C16—H16C	0.9600
C7—C8	1.429 (3)	C17—O2	1.201 (3)
C8—C9	1.390 (3)	C17—O3	1.339 (3)
C8—C11	1.439 (3)	C18—O3	1.457 (3)
C9—N2	1.343 (3)	C18—C19	1.471 (5)
C9—S1	1.723 (2)	C18—H18A	0.9700
C10—N2	1.311 (3)	C18—H18B	0.9700
C10—N3	1.335 (3)	C19—H19A	0.9600
C10—N1	1.401 (3)	C19—H19B	0.9600
C11—C12	1.373 (3)	C19—H19C	0.9600
C11—C16	1.490 (3)	N3—H3A	0.88 (3)
C12—C17	1.463 (3)
C6—C1—C2	120.7 (2)	C13—C14—C15	114.8 (3)
C6—C1—N1	120.37 (18)	C13—C14—H14A	108.6
C2—C1—N1	118.93 (18)	C15—C14—H14A	108.6
C3—C2—C1	118.4 (2)	C13—C14—H14B	108.6
C3—C2—H2	120.8	C15—C14—H14B	108.6
C1—C2—H2	120.8	H14A—C14—H14B	107.6
C4—C3—C2	121.5 (2)	C14—C15—H15A	109.5
C4—C3—H3	119.2	C14—C15—H15B	109.5
C2—C3—H3	119.2	H15A—C15—H15B	109.5
C3—C4—C5	119.7 (2)	C14—C15—H15C	109.5
C3—C4—H4	120.1	H15A—C15—H15C	109.5
C5—C4—H4	120.1	H15B—C15—H15C	109.5
C4—C5—C6	120.5 (2)	C11—C16—H16A	109.5
C4—C5—H5	119.8	C11—C16—H16B	109.5
C6—C5—H5	119.8	H16A—C16—H16B	109.5
C1—C6—C5	119.2 (2)	C11—C16—H16C	109.5
C1—C6—H6	120.4	H16A—C16—H16C	109.5
C5—C6—H6	120.4	H16B—C16—H16C	109.5
O1—C7—N1	119.66 (19)	O2—C17—O3	123.5 (2)
O1—C7—C8	126.5 (2)	O2—C17—C12	125.6 (2)
N1—C7—C8	113.87 (18)	O3—C17—C12	110.8 (2)
C9—C8—C7	118.0 (2)	O3—C18—C19	107.5 (3)
C9—C8—C11	113.54 (18)	O3—C18—H18A	110.2
C7—C8—C11	128.3 (2)	C19—C18—H18A	110.2
N2—C9—C8	126.94 (19)	O3—C18—H18B	110.2
N2—C9—S1	121.50 (16)	C19—C18—H18B	110.2
C8—C9—S1	111.54 (16)	H18A—C18—H18B	108.5
N2—C10—N3	120.16 (19)	C18—C19—H19A	109.5
N2—C10—N1	123.25 (18)	C18—C19—H19B	109.5
N3—C10—N1	116.58 (18)	H19A—C19—H19B	109.5
C12—C11—C8	110.74 (19)	C18—C19—H19C	109.5
C12—C11—C16	125.2 (2)	H19A—C19—H19C	109.5
C8—C11—C16	124.04 (19)	H19B—C19—H19C	109.5
C11—C12—C17	127.9 (2)	C10—N1—C7	121.80 (16)
C11—C12—S1	113.03 (16)	C10—N1—C1	120.45 (16)
C17—C12—S1	118.88 (17)	C7—N1—C1	117.67 (16)
N3—C13—C14	113.0 (2)	C10—N2—C9	115.30 (18)
N3—C13—H13A	109.0	C10—N3—C13	122.80 (19)
C14—C13—H13A	109.0	C10—N3—H3A	115.4 (19)
N3—C13—H13B	109.0	C13—N3—H3A	121.2 (19)
C14—C13—H13B	109.0	C17—O3—C18	116.2 (2)
H13A—C13—H13B	107.8	C9—S1—C12	91.12 (11)
C6—C1—C2—C3	0.6 (3)	S1—C12—C17—O3	1.2 (3)
N1—C1—C2—C3	−178.1 (2)	N2—C10—N1—C7	−10.4 (3)
C1—C2—C3—C4	−0.9 (4)	N3—C10—N1—C7	169.45 (18)
C2—C3—C4—C5	0.8 (4)	N2—C10—N1—C1	166.03 (19)
C3—C4—C5—C6	−0.5 (4)	N3—C10—N1—C1	−14.1 (3)
C2—C1—C6—C5	−0.3 (3)	O1—C7—N1—C10	−177.29 (19)
N1—C1—C6—C5	178.4 (2)	C8—C7—N1—C10	4.1 (3)
C4—C5—C6—C1	0.2 (4)	O1—C7—N1—C1	6.2 (3)
O1—C7—C8—C9	−175.2 (2)	C8—C7—N1—C1	−172.42 (17)
N1—C7—C8—C9	3.3 (3)	C6—C1—N1—C10	120.7 (2)
O1—C7—C8—C11	0.8 (4)	C2—C1—N1—C10	−60.5 (3)
N1—C7—C8—C11	179.28 (19)	C6—C1—N1—C7	−62.7 (3)
C7—C8—C9—N2	−6.1 (3)	C2—C1—N1—C7	116.0 (2)
C11—C8—C9—N2	177.4 (2)	N3—C10—N2—C9	−172.1 (2)
C7—C8—C9—S1	175.14 (16)	N1—C10—N2—C9	7.7 (3)
C11—C8—C9—S1	−1.4 (2)	C8—C9—N2—C10	0.5 (3)
C9—C8—C11—C12	0.4 (3)	S1—C9—N2—C10	179.13 (17)
C7—C8—C11—C12	−175.7 (2)	N2—C10—N3—C13	−1.6 (3)
C9—C8—C11—C16	−179.8 (2)	N1—C10—N3—C13	178.5 (2)
C7—C8—C11—C16	4.1 (4)	C14—C13—N3—C10	−100.7 (3)
C8—C11—C12—C17	−174.6 (2)	O2—C17—O3—C18	2.3 (4)
C16—C11—C12—C17	5.6 (4)	C12—C17—O3—C18	−176.2 (3)
C8—C11—C12—S1	0.8 (2)	C19—C18—O3—C17	173.9 (3)
C16—C11—C12—S1	−179.1 (2)	N2—C9—S1—C12	−177.32 (19)
N3—C13—C14—C15	−60.7 (4)	C8—C9—S1—C12	1.53 (17)
C11—C12—C17—O2	−2.1 (4)	C11—C12—S1—C9	−1.33 (19)
S1—C12—C17—O2	−177.2 (2)	C17—C12—S1—C9	174.47 (19)
C11—C12—C17—O3	176.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2i	0.93	2.58	3.359 (3)	142
C2—H2···O2ii	0.93	2.50	3.432 (3)	177
N3—H3A···O1iii	0.88 (3)	2.08 (3)	2.863 (3)	147 (3)
C16—H16C···O2	0.96	2.31	3.000 (3)	128

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2i	0.93	2.58	3.359 (3)	142
C2—H2⋯O2ii	0.93	2.50	3.432 (3)	177
N3—H3A⋯O1iii	0.88 (3)	2.08 (3)	2.863 (3)	147 (3)
C16—H16C⋯O2	0.96	2.31	3.000 (3)	128

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