3,5,6-Trimethyl­thieno[2,3-d]pyrimidin-4(3H)-one

Abstract

In the title compound, C₉H₁₀N₂OS, the thienopyrimidine ring system is almost planar [greatest deviation from the mean plane = 0.0318 (13) Å for the S atom]. The crystal packing features C—H⋯O hydrogen bonds and π–π stacking inter­actions between inversion-related pairs of mol­ecules with a centroid–centroid distance of 3.530 (3) Å.

Related literature  

For the synthesis, properties and biological activity of pyrim­idinone derivatives, see: Litvinov (2004 ▶); Al-Taisan et al. (2010 ▶). For the crystal and mol­ecular structures of related compounds, see: Tashkhodzhaev et al. (2002 ▶).

Experimental  

Crystal data  

• C₉H₁₀N₂OS

• M _r = 194.25

• Monoclinic,

• a = 8.027 (3) Å

• b = 10.706 (5) Å

• c = 10.907 (3) Å

• β = 97.333 (3)°

• V = 929.7 (6) ų

• Z = 4

• Cu Kα radiation

• μ = 2.77 mm⁻¹

• T = 293 K

• 0.42 × 0.36 × 0.28 mm

Data collection  

• Oxford Diffraction Xcalibur Ruby diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.324, T _max = 1.000

• 2983 measured reflections

• 1588 independent reflections

• 1208 reflections with I > 2σ(I)

• R _int = 0.029

Refinement  

• R[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 0.151

• S = 1.05

• 1588 reflections

• 122 parameters

• H-atom parameters constrained

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812035416/aa2064Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.93	2.32	3.250 (4)	173

Symmetry code: (i) .

supplementary crystallographic information

Comment

The derivatives of thienopyrimidine are of interest because of their interesting pharmacological and biological activities (Litvinov, 2004). The title compound, C₉H₁₀N₂OS, may be used for obtaining bioactive molecules. The asymmetric unit of the title compound consists of a single molecule (Fig.1). The thienopyrimidine ring system (N1/C2/N3/C4/C5/C6/C7/C8/S1) is ideal planar with greatest deviation from mean plane 0.0318 (12) Å for the S1). The crystal packing is stabilized by intermolecular hydrogen bonds (Table 1) and π-π stacking interactions between inversion-related pair of molecules with a centroid-centroid (N1/C2/N3/C4/C5/C6/C7/C8/S1) distance of 3.530 (3) Å.

Experimental

To a suspension of 5,6-trimethylthieno(2,3 - d)pyrimidin-4-one (181 mg, 0.1 mmol) in 50 ml e thanol sodium hydride (24 mg, 1 mmol) was added. The mixture was stirred at room temperature for 30 min. Then a solution of methyl iodide(142 mg, 1 mmol) in ethanol was added drop wise. The solution was stirred at 353–363 K for 4 h, then the solution was evaporated under reduced pressure and the residue was treated by distilled water. The precipitate was filtered and dried. Yield of 84% (174 mg). Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from chloroform at room temperature.

Refinement

All H atoms were placed in geometrically idealized positions (C—H 0.96 (methyl) and C—H 0.93 Å (phenyl) and treated as riding on their parent atoms, with U(H) set to 1.2 to 1.5U(C).

Figures

Fig. 1.

The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom numbering scheme.

Fig. 2.

A packing diagram for title compound. C—H···O hydrogen bonds are shown as dashed lines.

Crystal data

C9H10N2OS	F(000) = 408
Mr = 194.25	Dx = 1.388 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 185 reflections
a = 8.027 (3) Å	θ = 4.1–43.7°
b = 10.706 (5) Å	µ = 2.77 mm−1
c = 10.907 (3) Å	T = 293 K
β = 97.333 (3)°	Block, colourless
V = 929.7 (6) Å3	0.42 × 0.36 × 0.28 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer	1588 independent reflections
Radiation source: fine-focus sealed tube	1208 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 10.2576 pixels mm-1	θmax = 67.2°, θmin = 5.6°
ω scans	h = −8→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −12→12
Tmin = 0.324, Tmax = 1.000	l = −13→11
2983 measured reflections

Refinement

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-atom parameters constrained
wR(F2) = 0.151	w = 1/[σ2(Fo2) + (0.1022P)2 + 0.0132P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1588 reflections	Δρmax = 0.27 e Å−3
122 parameters	Δρmin = −0.22 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0070 (14)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3074 (3)	0.1156 (2)	0.4761 (3)	0.0448 (7)
C2	0.4524 (4)	0.1684 (3)	0.6555 (3)	0.0559 (8)
H2	0.5198	0.2239	0.7052	0.067*
C3	0.3198 (3)	−0.0372 (3)	0.6401 (2)	0.0467 (7)
C4	0.2664 (3)	−0.0020 (2)	0.5153 (2)	0.0396 (6)
C5	0.1683 (3)	−0.0728 (2)	0.4196 (2)	0.0446 (7)
C6	0.1362 (4)	−0.0066 (3)	0.3125 (2)	0.0498 (7)
C7	0.4735 (4)	0.0352 (4)	0.8380 (3)	0.0693 (10)
H7A	0.3808	0.0084	0.8791	0.104*
H7B	0.5195	0.1109	0.8754	0.104*
H7C	0.5584	−0.0285	0.8454	0.104*
C8	0.1125 (4)	−0.2045 (3)	0.4345 (3)	0.0615 (8)
H8A	0.0263	−0.2062	0.4879	0.092*
H8B	0.2062	−0.2539	0.4699	0.092*
H8C	0.0690	−0.2379	0.3551	0.092*
C9	0.0413 (4)	−0.0454 (4)	0.1917 (3)	0.0694 (9)
H9A	−0.0690	−0.0091	0.1831	0.104*
H9B	0.0319	−0.1348	0.1890	0.104*
H9C	0.0998	−0.0173	0.1254	0.104*
N1	0.4025 (3)	0.2028 (2)	0.5443 (2)	0.0537 (6)
N2	0.4153 (3)	0.0576 (2)	0.7075 (2)	0.0505 (6)
O1	0.2922 (3)	−0.13487 (19)	0.69116 (18)	0.0595 (6)
S1	0.22443 (10)	0.14187 (7)	0.32561 (6)	0.0543 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0458 (16)	0.0418 (14)	0.0482 (15)	0.0049 (11)	0.0116 (12)	−0.0006 (11)
C2	0.0553 (19)	0.0501 (17)	0.062 (2)	0.0007 (13)	0.0055 (14)	−0.0163 (14)
C3	0.0443 (16)	0.0495 (16)	0.0468 (15)	0.0075 (12)	0.0074 (12)	−0.0022 (12)
C4	0.0368 (14)	0.0398 (14)	0.0430 (14)	0.0064 (10)	0.0081 (11)	0.0000 (10)
C5	0.0427 (16)	0.0448 (15)	0.0470 (15)	0.0027 (11)	0.0083 (12)	−0.0010 (11)
C6	0.0476 (17)	0.0553 (17)	0.0458 (15)	0.0063 (13)	0.0036 (12)	−0.0013 (12)
C7	0.073 (2)	0.088 (3)	0.0436 (17)	0.0157 (18)	−0.0037 (15)	−0.0115 (15)
C8	0.067 (2)	0.0505 (17)	0.067 (2)	−0.0105 (14)	0.0080 (16)	−0.0035 (14)
C9	0.072 (2)	0.083 (2)	0.0512 (18)	−0.0023 (18)	−0.0023 (15)	−0.0075 (16)
N1	0.0568 (15)	0.0428 (13)	0.0613 (16)	0.0001 (11)	0.0071 (12)	−0.0060 (11)
N2	0.0519 (14)	0.0564 (15)	0.0419 (13)	0.0091 (11)	0.0006 (10)	−0.0089 (10)
O1	0.0688 (15)	0.0553 (13)	0.0531 (12)	0.0013 (10)	0.0025 (10)	0.0164 (9)
S1	0.0631 (6)	0.0502 (5)	0.0493 (5)	0.0040 (3)	0.0068 (3)	0.0099 (3)

Geometric parameters (Å, º)

C1—N1	1.365 (4)	C6—C9	1.494 (4)
C1—C4	1.382 (4)	C6—S1	1.739 (3)
C1—S1	1.714 (3)	C7—N2	1.461 (4)
C2—N1	1.282 (4)	C7—H7A	0.9600
C2—N2	1.364 (4)	C7—H7B	0.9600
C2—H2	0.9300	C7—H7C	0.9600
C3—O1	1.218 (3)	C8—H8A	0.9600
C3—N2	1.419 (4)	C8—H8B	0.9600
C3—C4	1.424 (4)	C8—H8C	0.9600
C4—C5	1.441 (3)	C9—H9A	0.9600
C5—C6	1.362 (4)	C9—H9B	0.9600
C5—C8	1.495 (4)	C9—H9C	0.9600
N1—C1—C4	126.3 (3)	N2—C7—H7C	109.5
N1—C1—S1	122.1 (2)	H7A—C7—H7C	109.5
C4—C1—S1	111.6 (2)	H7B—C7—H7C	109.5
N1—C2—N2	125.8 (3)	C5—C8—H8A	109.5
N1—C2—H2	117.1	C5—C8—H8B	109.5
N2—C2—H2	117.1	H8A—C8—H8B	109.5
O1—C3—N2	119.6 (3)	C5—C8—H8C	109.5
O1—C3—C4	127.9 (3)	H8A—C8—H8C	109.5
N2—C3—C4	112.4 (2)	H8B—C8—H8C	109.5
C1—C4—C3	118.9 (2)	C6—C9—H9A	109.5
C1—C4—C5	112.6 (2)	C6—C9—H9B	109.5
C3—C4—C5	128.5 (2)	H9A—C9—H9B	109.5
C6—C5—C4	112.0 (2)	C6—C9—H9C	109.5
C6—C5—C8	123.8 (3)	H9A—C9—H9C	109.5
C4—C5—C8	124.2 (2)	H9B—C9—H9C	109.5
C5—C6—C9	129.1 (3)	C2—N1—C1	113.8 (3)
C5—C6—S1	112.0 (2)	C2—N2—C3	122.6 (2)
C9—C6—S1	118.9 (2)	C2—N2—C7	119.2 (3)
N2—C7—H7A	109.5	C3—N2—C7	118.2 (3)
N2—C7—H7B	109.5	C1—S1—C6	91.90 (13)
H7A—C7—H7B	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.93	2.32	3.250 (4)	173

Symmetry code: (i) −x+1, y+1/2, −z+3/2.