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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2266.
Published online 2009 August 29. doi:  10.1107/S1600536809033595
PMCID: PMC2969942

Ethyl 5-methyl-4-oxo-3-phenyl-2-propyl­amino-3,4-dihydro­thieno[2,3-d]pyrimidine-6-carboxyl­ate

Abstract

The title compound, C19H21N3O3S, was synthesized via the aza-Wittig reaction of functionalized imino­phospho­rane with phenyl isocyanate under mild conditions. In the mol­ecule, 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 intra­molecular C—H(...)O hydrogen bond is present. The crystal packing is stabilized by inter­molecular 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 [triangle]); Panico et al. (2001 [triangle]). For the biological activity of thienopyrimidine derivatives, see: Ding et al. (2004 [triangle]).

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Object name is e-65-o2266-scheme1.jpg

Experimental

Crystal data

  • C19H21N3O3S
  • M r = 371.45
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2266-efi1.jpg
  • 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 [triangle]) 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 [triangle]), 1861 Freidel pairs
  • Flack parameter: 0.08 (10)

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

We gratefully acknowledge financial support of this work by the Key Science Research Project of Hubei Provincial Department of Education (No. D20092406) and the Science Research Project of Yunyang Medical College (No. 2007QDJ14).

supplementary crystallographic information

Comment

The derivatives of thienopyrimidine are of great importance because of their remarked biological properties (Ding et al., 2004). We have recently focused on the synthesis of fused heterocyclic systems containing a fused pyrimidinone ring moiety using aza-Wittig reaction. The title compound, may be used as a new precursor for obtaining bioactive molecules and its structure is reported here, Fig.1. The bond lengths and angles are unexceptional. The thienopyrimidinone rings are closer to coplanarity with maximum deviations 0.072 (2)Å and -0.058 (2)Å for C10 and N1, respectively. The phenyl ring is twisted with respect to the pyrimidinone ring, with a dihedral angle of 60.11 (9)°. Intramolecular C—H···O and intermolecular C—H···O, N—H···O hydrogen bonds interactions are present, which stabilize the conformation of the molecule and the crystal structure (Table 1).

Experimental

To a solution of diethyl 5-((phenylimino)methyleneamino)- 3-methylthiophene-2,4-dicarboxylate(3 mmol) in anhydrous dichloromethane (15 ml) was added propan-1-amine (3 mmol). After stirring the reaction mixture for 1 h, the solvent was removed and anhydrous ethanol (10 ml) with several drops of EtONa in EtOH was added. The mixture was stirred for 5 h at room temperature. The solution was concentrated under reduced pressure and the residue was recrystallized from ethanol to give the title compound in a yield of 78%. Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from a mixed solvent of ethanol and dichloromethane (1:1 v/v) at room temperature.

Refinement

All H-atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å, Uiso=1.2Ueq (C) for Csp2, N—H = 0.88 Å, Uiso=1.2Ueq (N) for NH, C—H = 0.97 Å, Uiso = 1.2Ueq (C) for CH2, C—H = 0.96 Å, Uiso = 1.5Ueq (C) for CH3.

Figures

Fig. 1.
ORTEP drawing and atom labelling scheme of the title compound with thermal ellipsoids drawn at the 50% probability level.

Crystal data

C19H21N3O3SF(000) = 784
Mr = 371.45Dx = 1.331 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 4659 reflections
a = 8.1682 (2) Åθ = 2.5–28.0°
b = 14.1247 (3) ŵ = 0.20 mm1
c = 16.0672 (5) ÅT = 298 K
V = 1853.73 (8) Å3Block, colourless
Z = 40.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer4472 independent reflections
Radiation source: fine-focus sealed tube4226 reflections with I > 2σ(I)
graphiteRint = 0.031
[var phi] and ω scansθmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→5
Tmin = 0.969, Tmax = 0.980k = −18→18
10064 measured reflectionsl = −21→21

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.136w = 1/[σ2(Fo2) + (0.0772P)2 + 0.1133P] where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
4472 reflectionsΔρmax = 0.39 e Å3
241 parametersΔρmin = −0.37 e Å3
0 restraintsAbsolute structure: Flack (1983), 1861 Freidel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.08 (10)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.2534 (2)0.22884 (14)0.48554 (12)0.0322 (4)
C20.3341 (3)0.15050 (17)0.45355 (15)0.0412 (5)
H20.37940.10520.48870.049*
C30.3457 (3)0.14132 (19)0.36796 (15)0.0515 (6)
H30.40080.08950.34570.062*
C40.2783 (4)0.2063 (2)0.31554 (15)0.0545 (6)
H40.28640.19840.25820.065*
C50.1984 (3)0.28367 (18)0.34767 (15)0.0502 (6)
H50.15300.32830.31190.060*
C60.1848 (3)0.29565 (16)0.43303 (13)0.0388 (5)
H60.13040.34790.45470.047*
C70.3242 (3)0.32075 (14)0.61007 (13)0.0347 (4)
C80.3275 (3)0.32060 (16)0.69897 (13)0.0358 (4)
C90.2629 (3)0.24251 (15)0.74015 (12)0.0374 (4)
C100.1679 (2)0.17242 (14)0.62462 (12)0.0342 (4)
C110.3990 (3)0.38959 (15)0.75391 (13)0.0362 (4)
C120.3869 (3)0.36077 (15)0.83528 (14)0.0407 (5)
C13−0.0094 (3)0.03243 (17)0.62828 (15)0.0483 (6)
H13A−0.11880.02600.60550.058*
H13B−0.02010.04880.68670.058*
C140.0757 (4)−0.0588 (2)0.6213 (2)0.0725 (9)
H14A0.0157−0.10560.65320.087*
H14B0.1834−0.05260.64620.087*
C150.0958 (7)−0.0951 (3)0.5329 (3)0.1005 (15)
H15A−0.0083−0.11610.51210.151*
H15B0.1716−0.14710.53250.151*
H15C0.1368−0.04520.49810.151*
C160.4758 (4)0.47961 (18)0.72536 (16)0.0507 (6)
H16A0.39200.52270.70750.076*
H16B0.54860.46670.67980.076*
H16C0.53630.50740.77040.076*
C170.4320 (3)0.41350 (18)0.91026 (15)0.0443 (5)
C180.4227 (5)0.4121 (2)1.05795 (16)0.0689 (9)
H18A0.36880.47331.05860.083*
H18B0.53910.42181.06620.083*
C190.3562 (5)0.3512 (3)1.12406 (18)0.0761 (9)
H19A0.24110.34191.11510.114*
H19B0.37310.38091.17710.114*
H19C0.41100.29111.12310.114*
N10.2447 (2)0.24077 (12)0.57496 (10)0.0340 (4)
N20.1836 (2)0.16896 (13)0.70577 (11)0.0393 (4)
N30.0749 (2)0.10894 (14)0.58518 (13)0.0422 (4)
H3A0.055 (3)0.121 (2)0.5323 (18)0.051*
O10.3846 (2)0.38072 (11)0.56420 (9)0.0453 (4)
O20.4921 (3)0.49108 (14)0.91163 (11)0.0578 (5)
O30.3935 (3)0.36454 (14)0.97886 (11)0.0609 (5)
S10.29211 (8)0.25028 (4)0.84614 (3)0.04848 (17)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0379 (9)0.0327 (10)0.0261 (9)−0.0042 (7)0.0009 (7)0.0019 (7)
C20.0486 (12)0.0380 (12)0.0369 (11)0.0050 (9)−0.0041 (9)0.0002 (9)
C30.0667 (15)0.0487 (14)0.0391 (12)0.0029 (11)0.0069 (11)−0.0120 (10)
C40.0743 (17)0.0613 (16)0.0278 (10)−0.0083 (14)0.0003 (11)−0.0038 (10)
C50.0619 (13)0.0515 (13)0.0372 (11)−0.0084 (11)−0.0076 (11)0.0142 (11)
C60.0430 (11)0.0356 (11)0.0378 (11)0.0019 (9)−0.0006 (9)0.0052 (8)
C70.0427 (11)0.0287 (9)0.0327 (10)0.0026 (8)0.0031 (8)−0.0027 (8)
C80.0447 (11)0.0326 (10)0.0301 (10)−0.0012 (9)0.0029 (8)−0.0024 (8)
C90.0489 (11)0.0390 (11)0.0242 (8)0.0002 (10)−0.0013 (8)0.0001 (8)
C100.0439 (11)0.0290 (10)0.0297 (10)−0.0004 (8)0.0015 (8)0.0028 (8)
C110.0412 (10)0.0328 (10)0.0344 (11)0.0030 (8)0.0017 (8)−0.0056 (8)
C120.0498 (11)0.0389 (11)0.0334 (11)−0.0011 (9)0.0002 (9)−0.0048 (9)
C130.0618 (14)0.0451 (13)0.0381 (12)−0.0169 (11)0.0044 (11)0.0009 (10)
C140.079 (2)0.0551 (17)0.083 (2)−0.0100 (15)−0.0015 (17)0.0234 (16)
C150.139 (4)0.053 (2)0.109 (3)−0.005 (2)0.043 (3)−0.018 (2)
C160.0734 (17)0.0381 (12)0.0406 (13)−0.0103 (11)0.0032 (11)−0.0060 (10)
C170.0517 (12)0.0460 (13)0.0354 (11)0.0043 (10)−0.0032 (10)−0.0104 (10)
C180.104 (2)0.0697 (19)0.0329 (13)−0.0100 (18)−0.0062 (14)−0.0123 (12)
C190.101 (2)0.086 (2)0.0413 (15)0.000 (2)−0.0002 (16)−0.0025 (15)
N10.0460 (8)0.0304 (8)0.0258 (8)−0.0008 (7)0.0016 (6)0.0007 (6)
N20.0547 (11)0.0356 (9)0.0276 (8)−0.0092 (8)−0.0007 (8)0.0024 (7)
N30.0570 (11)0.0387 (10)0.0309 (9)−0.0101 (8)−0.0060 (8)0.0028 (8)
O10.0673 (10)0.0378 (9)0.0308 (8)−0.0124 (8)0.0093 (7)0.0004 (6)
O20.0789 (12)0.0515 (11)0.0429 (10)−0.0127 (9)−0.0058 (9)−0.0113 (8)
O30.0943 (14)0.0570 (11)0.0313 (9)−0.0150 (10)−0.0040 (9)−0.0089 (8)
S10.0721 (4)0.0474 (3)0.0259 (2)−0.0128 (3)−0.0033 (2)0.0012 (2)

Geometric parameters (Å, °)

C1—C61.384 (3)C12—S11.751 (2)
C1—C21.387 (3)C13—N31.456 (3)
C1—N11.448 (2)C13—C141.468 (4)
C2—C31.385 (3)C13—H13A0.9700
C2—H20.9300C13—H13B0.9700
C3—C41.362 (4)C14—C151.519 (5)
C3—H30.9300C14—H14A0.9700
C4—C51.373 (4)C14—H14B0.9700
C4—H40.9300C15—H15A0.9600
C5—C61.386 (3)C15—H15B0.9600
C5—H50.9300C15—H15C0.9600
C6—H60.9300C16—H16A0.9600
C7—O11.226 (3)C16—H16B0.9600
C7—N11.420 (3)C16—H16C0.9600
C7—C81.429 (3)C17—O21.201 (3)
C8—C91.390 (3)C17—O31.339 (3)
C8—C111.439 (3)C18—O31.457 (3)
C9—N21.343 (3)C18—C191.471 (5)
C9—S11.723 (2)C18—H18A0.9700
C10—N21.311 (3)C18—H18B0.9700
C10—N31.335 (3)C19—H19A0.9600
C10—N11.401 (3)C19—H19B0.9600
C11—C121.373 (3)C19—H19C0.9600
C11—C161.490 (3)N3—H3A0.88 (3)
C12—C171.463 (3)
C6—C1—C2120.7 (2)C13—C14—C15114.8 (3)
C6—C1—N1120.37 (18)C13—C14—H14A108.6
C2—C1—N1118.93 (18)C15—C14—H14A108.6
C3—C2—C1118.4 (2)C13—C14—H14B108.6
C3—C2—H2120.8C15—C14—H14B108.6
C1—C2—H2120.8H14A—C14—H14B107.6
C4—C3—C2121.5 (2)C14—C15—H15A109.5
C4—C3—H3119.2C14—C15—H15B109.5
C2—C3—H3119.2H15A—C15—H15B109.5
C3—C4—C5119.7 (2)C14—C15—H15C109.5
C3—C4—H4120.1H15A—C15—H15C109.5
C5—C4—H4120.1H15B—C15—H15C109.5
C4—C5—C6120.5 (2)C11—C16—H16A109.5
C4—C5—H5119.8C11—C16—H16B109.5
C6—C5—H5119.8H16A—C16—H16B109.5
C1—C6—C5119.2 (2)C11—C16—H16C109.5
C1—C6—H6120.4H16A—C16—H16C109.5
C5—C6—H6120.4H16B—C16—H16C109.5
O1—C7—N1119.66 (19)O2—C17—O3123.5 (2)
O1—C7—C8126.5 (2)O2—C17—C12125.6 (2)
N1—C7—C8113.87 (18)O3—C17—C12110.8 (2)
C9—C8—C7118.0 (2)O3—C18—C19107.5 (3)
C9—C8—C11113.54 (18)O3—C18—H18A110.2
C7—C8—C11128.3 (2)C19—C18—H18A110.2
N2—C9—C8126.94 (19)O3—C18—H18B110.2
N2—C9—S1121.50 (16)C19—C18—H18B110.2
C8—C9—S1111.54 (16)H18A—C18—H18B108.5
N2—C10—N3120.16 (19)C18—C19—H19A109.5
N2—C10—N1123.25 (18)C18—C19—H19B109.5
N3—C10—N1116.58 (18)H19A—C19—H19B109.5
C12—C11—C8110.74 (19)C18—C19—H19C109.5
C12—C11—C16125.2 (2)H19A—C19—H19C109.5
C8—C11—C16124.04 (19)H19B—C19—H19C109.5
C11—C12—C17127.9 (2)C10—N1—C7121.80 (16)
C11—C12—S1113.03 (16)C10—N1—C1120.45 (16)
C17—C12—S1118.88 (17)C7—N1—C1117.67 (16)
N3—C13—C14113.0 (2)C10—N2—C9115.30 (18)
N3—C13—H13A109.0C10—N3—C13122.80 (19)
C14—C13—H13A109.0C10—N3—H3A115.4 (19)
N3—C13—H13B109.0C13—N3—H3A121.2 (19)
C14—C13—H13B109.0C17—O3—C18116.2 (2)
H13A—C13—H13B107.8C9—S1—C1291.12 (11)
C6—C1—C2—C30.6 (3)S1—C12—C17—O31.2 (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—C7169.45 (18)
C2—C3—C4—C50.8 (4)N2—C10—N1—C1166.03 (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—C5178.4 (2)C8—C7—N1—C104.1 (3)
C4—C5—C6—C10.2 (4)O1—C7—N1—C16.2 (3)
O1—C7—C8—C9−175.2 (2)C8—C7—N1—C1−172.42 (17)
N1—C7—C8—C93.3 (3)C6—C1—N1—C10120.7 (2)
O1—C7—C8—C110.8 (4)C2—C1—N1—C10−60.5 (3)
N1—C7—C8—C11179.28 (19)C6—C1—N1—C7−62.7 (3)
C7—C8—C9—N2−6.1 (3)C2—C1—N1—C7116.0 (2)
C11—C8—C9—N2177.4 (2)N3—C10—N2—C9−172.1 (2)
C7—C8—C9—S1175.14 (16)N1—C10—N2—C97.7 (3)
C11—C8—C9—S1−1.4 (2)C8—C9—N2—C100.5 (3)
C9—C8—C11—C120.4 (3)S1—C9—N2—C10179.13 (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—C13178.5 (2)
C7—C8—C11—C164.1 (4)C14—C13—N3—C10−100.7 (3)
C8—C11—C12—C17−174.6 (2)O2—C17—O3—C182.3 (4)
C16—C11—C12—C175.6 (4)C12—C17—O3—C18−176.2 (3)
C8—C11—C12—S10.8 (2)C19—C18—O3—C17173.9 (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—C121.53 (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—C9174.47 (19)
C11—C12—C17—O3176.3 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.583.359 (3)142
C2—H2···O2ii0.932.503.432 (3)177
N3—H3A···O1iii0.88 (3)2.08 (3)2.863 (3)147 (3)
C16—H16C···O20.962.313.000 (3)128

Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x−1/2, −y+1/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2864).

References

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