Crystal structure of ethyl 2-acetyl-3,7-dimethyl-5-(thio-phen-2-yl)-5H-thia-zolo[3,2-a]pyrimidine-6-carboxyl-ate.

In the title compound, C17H18N2O3S2, the pyrimidine ring adopts a shallow sofa conformation, with the C atom bearing the axially-oriented thio-phene ring as the flap [deviation = 0.439 (3) Å]. The plane of the thio-phene ring lies almost normal to the pyrimidine ring, making a dihedral angle of 79.36 (19)°. In the crystal, pairs of very weak C-H⋯O hydrogen bonds link the mol-ecules related by twofold rotation axes, forming R 2 (2)(18) rings, which are in turn linked by another C-H⋯O inter-action, forming chains of rings along [010]. In addition, weak C-H⋯π(thio-phene) inter-actions link the chains into layers parallel to [001] and π-π inter-actions with a centroid-centroid distance of 3.772 (10) Å connect these layers into a three-dimensional network.

Related literature

For the biological activities of fused pyrimidine derivatives, see: Atwal et al. (1991 ▸); Kappe et al. (1997 ▸); Singh et al. (2011 ▸); Ozair et al. (2010 ▸); Hayam et al. (2010 ▸). For related structures, see: Prasad et al. (2014 ▸); Nagarajaiah et al. (2012 ▸).

Experimental

Crystal data

C17H18N2O3S2

M = 362.45

Monoclinic,

a = 7.8835 (10) Å

b = 14.4041 (19) Å

c = 15.231 (2) Å

β = 94.940 (4)°

V = 1723.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.33 mm−1

T = 100 K

0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▸) T min = 0.944, T max = 0.950

12021 measured reflections

3038 independent reflections

1984 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.189

S = 1.00

3038 reflections

221 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.28 e Å−3

Data collection: SMART (Bruker,1998 ▸); cell refinement: SAINT-Plus (Bruker,1998 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and CAMERON (Watkin et al., 1996 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010981/hb7433sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010981/hb7433Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015010981/hb7433Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015010981/hb7433fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015010981/hb7433fig2.tif

Unit-cell packing of the title compound showing C—H⋯O inter­actions as dotted lines. H atoms not involved in hydrogen bonding have been excluded.

Click here for additional data file.

. DOI: 10.1107/S2056989015010981/hb7433fig3.tif

Unit-cell packing depicting the C—H⋯π and π–π inter­actions with dotted lines.

CCDC reference: 1405373

Additional supporting information: crystallographic information; 3D view; checkCIF report

C17H18N2O3S2	F(000) = 760
Mr = 362.45	Dx = 1.397 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3038 reflections
a = 7.8835 (10) Å	θ = 2.6–25.0°
b = 14.4041 (19) Å	µ = 0.33 mm−1
c = 15.231 (2) Å	T = 100 K
β = 94.940 (4)°	Block, yellow
V = 1723.2 (4) Å3	0.18 × 0.16 × 0.16 mm
Z = 4

Bruker SMART APEX CCD diffractometer	3038 independent reflections
Radiation source: fine-focus sealed tube	1984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→9
Tmin = 0.944, Tmax = 0.950	k = −17→17
12021 measured reflections	l = −17→18

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.189	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.1059P)2 + 1.4984P] where P = (Fo2 + 2Fc2)/3
3038 reflections	(Δ/σ)max < 0.001
221 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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 > 2σ(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
S1	0.41155 (14)	0.67664 (8)	0.10428 (8)	0.0478 (4)
S2	0.86975 (15)	0.38590 (8)	0.30180 (7)	0.0514 (4)
N1	0.6122 (4)	0.5389 (2)	0.11268 (19)	0.0343 (8)
C6	0.5337 (5)	0.3792 (3)	0.1355 (2)	0.0384 (10)
O1	0.8379 (4)	0.7993 (2)	0.0552 (2)	0.0610 (9)
C9	0.4445 (5)	0.5583 (3)	0.1190 (2)	0.0378 (10)
N2	0.3249 (4)	0.5002 (3)	0.1340 (2)	0.0472 (9)
C3	0.7148 (5)	0.6131 (3)	0.0965 (2)	0.0345 (9)
C13	0.6889 (5)	0.5373 (3)	0.2994 (2)	0.0378 (10)
H13	0.6144	0.5869	0.2815	0.045*
O2	0.4904 (5)	0.2161 (2)	0.1141 (3)	0.0753 (11)
C2	0.6282 (5)	0.6938 (3)	0.0902 (3)	0.0386 (10)
C16	0.5843 (6)	0.2820 (3)	0.1255 (3)	0.0482 (11)
C17	0.9012 (5)	0.5964 (3)	0.0884 (3)	0.0521 (12)
H17A	0.9151	0.5420	0.0511	1.000*
H17B	0.9592	0.5855	0.1470	1.000*
H17C	0.9508	0.6509	0.0618	1.000*
C12	0.7368 (5)	0.4638 (3)	0.2456 (2)	0.0359 (9)
C7	0.3696 (6)	0.4072 (3)	0.1363 (3)	0.0434 (10)
C5	0.6754 (5)	0.4494 (3)	0.1488 (2)	0.0359 (9)
H5	0.7734	0.4286	0.1162	0.043*
C10	0.8235 (8)	0.1808 (3)	0.1127 (4)	0.0683 (15)
H10A	0.7431	0.1448	0.0724	0.082*
H10B	0.9319	0.1866	0.0849	0.082*
C14	0.7725 (6)	0.5240 (3)	0.3865 (3)	0.0499 (11)
H14	0.7602	0.5662	0.4335	0.060*
C4	0.6955 (6)	0.7881 (3)	0.0792 (3)	0.0447 (11)
C1	0.2188 (6)	0.3437 (3)	0.1387 (3)	0.0592 (13)
H1A	0.1198	0.3796	0.1538	1.000*
H1B	0.2444	0.2954	0.1832	1.000*
H1C	0.1940	0.3149	0.0808	1.000*
C8	0.5863 (7)	0.8697 (3)	0.0997 (4)	0.0686 (15)
H8A	0.5407	0.8599	0.1569	1.000*
H8B	0.4920	0.8758	0.0538	1.000*
H8C	0.6552	0.9264	0.1019	1.000*
C15	0.8682 (6)	0.4481 (3)	0.3959 (3)	0.0484 (11)
H15	0.9293	0.4306	0.4499	0.058*
O3	0.7530 (4)	0.2735 (2)	0.1262 (2)	0.0560 (8)
C11	0.8530 (10)	0.1323 (5)	0.1948 (4)	0.110 (3)
H11A	0.8940	0.0694	0.1839	0.166*
H11B	0.7466	0.1286	0.2235	0.166*
H11C	0.9387	0.1656	0.2332	0.166*

	U11	U22	U33	U12	U13	U23
S1	0.0422 (7)	0.0400 (7)	0.0619 (7)	0.0079 (5)	0.0093 (5)	0.0074 (5)
S2	0.0591 (8)	0.0471 (7)	0.0467 (7)	0.0086 (5)	−0.0026 (5)	0.0011 (5)
N1	0.0349 (19)	0.0318 (18)	0.0364 (18)	0.0033 (15)	0.0036 (14)	0.0039 (14)
C6	0.043 (2)	0.038 (2)	0.033 (2)	−0.0054 (19)	−0.0006 (17)	−0.0010 (17)
O1	0.061 (2)	0.047 (2)	0.075 (2)	−0.0107 (16)	0.0111 (18)	0.0040 (16)
C9	0.037 (2)	0.039 (2)	0.037 (2)	0.0067 (19)	0.0031 (17)	0.0017 (18)
N2	0.038 (2)	0.048 (2)	0.057 (2)	−0.0058 (18)	0.0122 (17)	−0.0046 (18)
C3	0.038 (2)	0.036 (2)	0.029 (2)	−0.0036 (19)	0.0006 (16)	0.0010 (16)
C13	0.048 (2)	0.035 (2)	0.030 (2)	−0.0105 (18)	−0.0020 (18)	−0.0038 (17)
O2	0.077 (3)	0.041 (2)	0.106 (3)	−0.0134 (19)	−0.006 (2)	−0.0007 (19)
C2	0.041 (2)	0.036 (2)	0.039 (2)	−0.0001 (18)	0.0054 (18)	0.0045 (18)
C16	0.062 (3)	0.036 (2)	0.045 (3)	−0.009 (2)	−0.005 (2)	−0.0013 (19)
C17	0.036 (2)	0.051 (3)	0.070 (3)	0.001 (2)	0.008 (2)	0.008 (2)
C12	0.036 (2)	0.031 (2)	0.040 (2)	0.0005 (17)	0.0011 (17)	0.0016 (17)
C7	0.051 (3)	0.039 (3)	0.041 (2)	−0.006 (2)	0.0069 (19)	0.0014 (18)
C5	0.042 (2)	0.032 (2)	0.034 (2)	0.0055 (18)	0.0034 (17)	−0.0009 (16)
C10	0.085 (4)	0.042 (3)	0.078 (4)	0.013 (3)	0.008 (3)	−0.014 (3)
C14	0.057 (3)	0.051 (3)	0.042 (2)	0.000 (2)	0.004 (2)	−0.009 (2)
C4	0.055 (3)	0.040 (2)	0.039 (2)	−0.004 (2)	0.003 (2)	0.0020 (19)
C1	0.051 (3)	0.057 (3)	0.070 (3)	−0.022 (2)	0.013 (2)	0.001 (2)
C8	0.087 (4)	0.038 (3)	0.083 (4)	0.008 (3)	0.019 (3)	−0.005 (2)
C15	0.052 (3)	0.054 (3)	0.038 (2)	−0.001 (2)	−0.0011 (19)	0.003 (2)
O3	0.060 (2)	0.0390 (18)	0.067 (2)	0.0087 (15)	−0.0048 (16)	−0.0080 (15)
C11	0.157 (7)	0.091 (5)	0.086 (5)	0.063 (5)	0.027 (4)	0.017 (4)

S1—C9	1.736 (4)	C17—H17B	0.9902
S1—C2	1.757 (4)	C17—H17C	0.9902
S2—C15	1.692 (4)	C12—C5	1.525 (5)
S2—C12	1.714 (4)	C7—C1	1.502 (6)
N1—C9	1.363 (5)	C5—H5	1.0000
N1—C3	1.375 (5)	C10—C11	1.433 (7)
N1—C5	1.471 (5)	C10—O3	1.467 (5)
C6—C7	1.355 (6)	C10—H10A	0.9900
C6—C16	1.468 (6)	C10—H10B	0.9900
C6—C5	1.508 (6)	C14—C15	1.328 (6)
O1—C4	1.221 (5)	C14—H14	0.9500
C9—N2	1.296 (5)	C4—C8	1.506 (6)
N2—C7	1.385 (5)	C1—H1A	0.9828
C3—C2	1.348 (5)	C1—H1B	0.9828
C3—C17	1.505 (6)	C1—H1C	0.9828
C13—C12	1.410 (5)	C8—H8A	0.9913
C13—C14	1.442 (6)	C8—H8B	0.9913
C13—H13	0.9500	C8—H8C	0.9913
O2—C16	1.207 (5)	C15—H15	0.9500
C2—C4	1.472 (6)	C11—H11A	0.9800
C16—O3	1.335 (5)	C11—H11B	0.9800
C17—H17A	0.9902	C11—H11C	0.9800
C9—S1—C2	91.04 (19)	C6—C5—C12	113.0 (3)
C15—S2—C12	91.6 (2)	N1—C5—H5	109.1
C9—N1—C3	116.3 (3)	C6—C5—H5	109.1
C9—N1—C5	116.9 (3)	C12—C5—H5	109.1
C3—N1—C5	124.2 (3)	C11—C10—O3	110.9 (4)
C7—C6—C16	123.5 (4)	C11—C10—H10A	109.5
C7—C6—C5	119.8 (4)	O3—C10—H10A	109.5
C16—C6—C5	116.7 (4)	C11—C10—H10B	109.4
N2—C9—N1	127.2 (4)	O3—C10—H10B	109.5
N2—C9—S1	123.7 (3)	H10A—C10—H10B	108.0
N1—C9—S1	109.1 (3)	C15—C14—C13	114.8 (4)
C9—N2—C7	116.2 (4)	C15—C14—H14	122.6
C2—C3—N1	112.4 (3)	C13—C14—H14	122.6
C2—C3—C17	128.6 (4)	O1—C4—C2	120.4 (4)
N1—C3—C17	119.0 (3)	O1—C4—C8	121.0 (4)
C12—C13—C14	108.1 (4)	C2—C4—C8	118.6 (4)
C12—C13—H13	126.0	C7—C1—H1A	109.8
C14—C13—H13	125.9	C7—C1—H1B	109.7
C3—C2—C4	128.2 (4)	H1A—C1—H1B	109.2
C3—C2—S1	111.2 (3)	C7—C1—H1C	109.8
C4—C2—S1	120.5 (3)	H1A—C1—H1C	109.2
O2—C16—O3	121.8 (4)	H1B—C1—H1C	109.2
O2—C16—C6	126.6 (5)	C4—C8—H8A	110.6
O3—C16—C6	111.5 (4)	C4—C8—H8B	110.6
C3—C17—H17A	110.5	H8A—C8—H8B	108.3
C3—C17—H17B	110.5	C4—C8—H8C	110.6
H17A—C17—H17B	108.4	H8A—C8—H8C	108.3
C3—C17—H17C	110.5	H8B—C8—H8C	108.3
H17A—C17—H17C	108.4	C14—C15—S2	112.9 (3)
H17B—C17—H17C	108.4	C14—C15—H15	123.5
C13—C12—C5	125.8 (3)	S2—C15—H15	123.5
C13—C12—S2	112.6 (3)	C16—O3—C10	118.1 (4)
C5—C12—S2	121.6 (3)	C10—C11—H11A	109.5
C6—C7—N2	121.9 (4)	C10—C11—H11B	109.5
C6—C7—C1	125.3 (4)	H11A—C11—H11B	109.5
N2—C7—C1	112.8 (4)	C10—C11—H11C	109.5
N1—C5—C6	108.3 (3)	H11A—C11—H11C	109.5
N1—C5—C12	108.2 (3)	H11B—C11—H11C	109.5
C3—N1—C9—N2	−179.9 (4)	C5—C6—C7—N2	11.1 (6)
C5—N1—C9—N2	−17.4 (6)	C16—C6—C7—C1	8.2 (6)
C3—N1—C9—S1	−0.2 (4)	C5—C6—C7—C1	−169.4 (4)
C5—N1—C9—S1	162.2 (2)	C9—N2—C7—C6	9.1 (6)
C2—S1—C9—N2	179.7 (4)	C9—N2—C7—C1	−170.4 (4)
C2—S1—C9—N1	0.0 (3)	C9—N1—C5—C6	33.4 (4)
N1—C9—N2—C7	−6.0 (6)	C3—N1—C5—C6	−165.7 (3)
S1—C9—N2—C7	174.4 (3)	C9—N1—C5—C12	−89.4 (4)
C9—N1—C3—C2	0.4 (5)	C3—N1—C5—C12	71.5 (4)
C5—N1—C3—C2	−160.6 (3)	C7—C6—C5—N1	−31.2 (5)
C9—N1—C3—C17	−179.8 (3)	C16—C6—C5—N1	151.0 (3)
C5—N1—C3—C17	19.2 (5)	C7—C6—C5—C12	88.6 (4)
N1—C3—C2—C4	175.6 (4)	C16—C6—C5—C12	−89.2 (4)
C17—C3—C2—C4	−4.2 (7)	C13—C12—C5—N1	20.6 (5)
N1—C3—C2—S1	−0.4 (4)	S2—C12—C5—N1	−162.0 (3)
C17—C3—C2—S1	179.8 (3)	C13—C12—C5—C6	−99.3 (4)
C9—S1—C2—C3	0.2 (3)	S2—C12—C5—C6	78.1 (4)
C9—S1—C2—C4	−176.1 (3)	C12—C13—C14—C15	−1.3 (5)
C7—C6—C16—O2	2.5 (7)	C3—C2—C4—O1	16.3 (7)
C5—C6—C16—O2	−179.8 (4)	S1—C2—C4—O1	−168.1 (3)
C7—C6—C16—O3	179.4 (4)	C3—C2—C4—C8	−162.5 (4)
C5—C6—C16—O3	−2.8 (5)	S1—C2—C4—C8	13.1 (5)
C14—C13—C12—C5	178.8 (4)	C13—C14—C15—S2	0.7 (5)
C14—C13—C12—S2	1.3 (4)	C12—S2—C15—C14	0.1 (4)
C15—S2—C12—C13	−0.8 (3)	O2—C16—O3—C10	−0.2 (6)
C15—S2—C12—C5	−178.5 (3)	C6—C16—O3—C10	−177.3 (3)
C16—C6—C7—N2	−171.2 (4)	C11—C10—O3—C16	−87.9 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···O1i	0.98	2.64	3.598 (6)	166
C13—H13···O2ii	0.95	2.63	3.269 (8)	125
C11—H11A···Cg1iii	0.98	2.89	3.693 (2)	139

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the S2/C12C15 ring.

DHA	DH	HA	D A	DHA
C1H1CO1i	0.98	2.64	3.598(6)	166
C13H13O2ii	0.95	2.63	3.269(8)	125
C11H11A Cg1iii	0.98	2.89	3.693(2)	139

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