Ethyl 2-[(Z)-3-chloro-benzyl-idene]-7-methyl-3-oxo-5-phenyl-2,3-dihydro-5H-1,3-thia-zolo[3,2-a]pyrimidine-6-carboxyl-ate.

In the title compound, C(23)H(19)ClN(2)O(3)S, the central pyrimidine ring is significantly puckered, assuming almost a screw boat conformation. In addition to the usual inter-molecular C-H⋯O hydrogen bonding, short intra-molecular C-H⋯S contacts and π-π stacking inter-actions [centroid-centroid distance = 3.762 (2) Å] contribute to the crystal packing.

Related literature

For the crystal structures of similar compounds, see: Jotani & Baldaniya (2006 ▶, 2007 ▶); Sridhar et al., (2006 ▶); Fischer et al. (2007 ▶). For the biological activities, see: Kappe (2000 ▶); Rovnyak et al. (1995 ▶); Monks et al. (1991 ▶); Winter et al. (1962 ▶). For related literature, see: Allen, (2002 ▶); Bernstein et al. (1995 ▶); Cremer & Pople, (1975 ▶).

Experimental

Crystal data

C23H19ClN2O3S

M = 438.92

Triclinic,

a = 8.2650 (3) Å

b = 10.3291 (4) Å

c = 13.5655 (5) Å

α = 94.129 (2)°

β = 100.837 (2)°

γ = 111.812 (2)°

V = 1043.15 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 293 (2) K

0.47 × 0.35 × 0.2 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.867, T max = 0.936

18826 measured reflections

3677 independent reflections

3111 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.124

S = 1.06

3677 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808007356/rk2081sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007356/rk2081Isup2.hkl

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

C23H19ClN2O3S	Z = 2
Mr = 438.92	F000 = 456
Triclinic, P1	Dx = 1.397 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 8.2650 (3) Å	Cell parameters from 3579 reflections
b = 10.3291 (4) Å	θ = 2.4–25.0º
c = 13.5655 (5) Å	µ = 0.31 mm−1
α = 94.129 (2)º	T = 293 (2) K
β = 100.837 (2)º	Plate, yellow
γ = 111.812 (2)º	0.47 × 0.35 × 0.2 mm
V = 1043.15 (7) Å3

Bruker KappaAPEXII CCD diffractometer	3677 independent reflections
Radiation source: Fine–focus sealed tube	3111 reflections with I > 2σ(I)
Monochromator: Graphite	Rint = 0.024
T = 293(2) K	θmax = 25.0º
ω and φ scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2004)	h = −9→9
Tmin = 0.867, Tmax = 0.936	k = −12→12
18826 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: Difmap
Least-squares matrix: Full	Hydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.041	H-atom parameters constrained
wR(F2) = 0.124	w = 1/[σ2(Fo2) + (0.0643P)2 + 0.3244P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.007
3677 reflections	Δρmax = 0.22 e Å−3
273 parameters	Δρmin = −0.25 e Å−3
Primary atom site location: Direct	Extinction correction: None

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	0.30130 (8)	0.19021 (5)	0.22916 (4)	0.06087 (19)
Cl1	1.00143 (9)	0.23402 (9)	−0.04622 (5)	0.0932 (3)
N1	0.0766 (2)	0.24166 (16)	0.32599 (13)	0.0579 (4)
N2	0.2084 (2)	0.40286 (15)	0.22081 (11)	0.0471 (4)
O1	0.3663 (2)	0.52920 (15)	0.11435 (11)	0.0657 (4)
O2	−0.0956 (2)	0.62159 (17)	0.26634 (16)	0.0856 (6)
O3	−0.2281 (3)	0.4916 (2)	0.37203 (18)	0.1084 (7)
C1	0.1793 (3)	0.28444 (18)	0.26598 (14)	0.0497 (4)
C2	0.1416 (2)	0.50926 (18)	0.25273 (14)	0.0450 (4)
H2	0.0929	0.5415	0.1923	0.054*
C3	−0.0077 (2)	0.44015 (19)	0.30586 (14)	0.0503 (4)
C4	−0.0276 (3)	0.3192 (2)	0.34291 (15)	0.0545 (5)
C5	0.3266 (3)	0.4282 (2)	0.15758 (14)	0.0502 (4)
C6	0.3964 (3)	0.3146 (2)	0.15427 (14)	0.0525 (5)
C7	−0.1590 (3)	0.2496 (3)	0.4043 (2)	0.0770 (7)
H7A	−0.1239	0.3051	0.4704	0.115*
H7B	−0.1614	0.1571	0.4111	0.115*
H7C	−0.2760	0.2420	0.3707	0.115*
C8	−0.1222 (3)	0.5170 (2)	0.32026 (17)	0.0598 (5)
C9	−0.1899 (4)	0.7149 (3)	0.2770 (3)	0.1048 (11)
H9A	−0.2618	0.7134	0.2112	0.126*
H9B	−0.2695	0.6817	0.3222	0.126*
C10	−0.0642 (5)	0.8562 (3)	0.3169 (3)	0.1099 (10)
H10A	−0.1276	0.9165	0.3232	0.165*
H10B	0.0139	0.8890	0.2718	0.165*
H10C	0.0054	0.8577	0.3825	0.165*
C11	0.2941 (2)	0.63460 (17)	0.32116 (13)	0.0427 (4)
C12	0.3852 (3)	0.6173 (2)	0.41182 (15)	0.0600 (5)
H12	0.3526	0.5284	0.4313	0.072*
C13	0.5242 (3)	0.7309 (3)	0.47383 (17)	0.0704 (6)
H13	0.5879	0.7179	0.5339	0.085*
C14	0.5688 (3)	0.8626 (2)	0.44719 (19)	0.0709 (6)
H14	0.6613	0.9397	0.4895	0.085*
C15	0.4773 (4)	0.8804 (2)	0.3587 (2)	0.0813 (7)
H15	0.5068	0.9702	0.3408	0.098*
C16	0.3416 (3)	0.7672 (2)	0.29520 (17)	0.0640 (5)
H16	0.2815	0.7806	0.2342	0.077*
C17	0.5194 (3)	0.3207 (2)	0.10123 (15)	0.0572 (5)
H17	0.5494	0.3961	0.0651	0.069*
C18	0.6139 (3)	0.2279 (2)	0.09120 (14)	0.0573 (5)
C19	0.5795 (3)	0.1033 (3)	0.13257 (17)	0.0684 (6)
H19	0.4902	0.0744	0.1686	0.082*
C20	0.6773 (4)	0.0225 (3)	0.12037 (19)	0.0801 (7)
H20	0.6543	−0.0597	0.1491	0.096*
C21	0.8079 (4)	0.0619 (3)	0.06648 (18)	0.0763 (7)
H21	0.8734	0.0072	0.0584	0.092*
C22	0.8402 (3)	0.1837 (3)	0.02458 (16)	0.0677 (6)
C23	0.7458 (3)	0.2672 (2)	0.03618 (15)	0.0608 (5)
H23	0.7704	0.3494	0.0073	0.073*

	U11	U22	U33	U12	U13	U23
S1	0.0788 (4)	0.0511 (3)	0.0654 (3)	0.0353 (3)	0.0227 (3)	0.0169 (2)
Cl1	0.0854 (5)	0.1389 (7)	0.0814 (4)	0.0718 (5)	0.0248 (3)	0.0110 (4)
N1	0.0634 (10)	0.0453 (9)	0.0625 (10)	0.0157 (8)	0.0188 (8)	0.0127 (8)
N2	0.0545 (9)	0.0406 (8)	0.0479 (8)	0.0202 (7)	0.0130 (7)	0.0064 (6)
O1	0.0892 (10)	0.0631 (9)	0.0723 (9)	0.0459 (8)	0.0416 (8)	0.0308 (7)
O2	0.0723 (10)	0.0714 (10)	0.1448 (17)	0.0428 (8)	0.0596 (11)	0.0413 (11)
O3	0.1136 (15)	0.1288 (17)	0.1383 (18)	0.0757 (14)	0.0846 (14)	0.0613 (14)
C1	0.0559 (11)	0.0402 (9)	0.0495 (10)	0.0167 (8)	0.0089 (8)	0.0058 (8)
C2	0.0469 (9)	0.0414 (9)	0.0494 (10)	0.0191 (8)	0.0133 (8)	0.0083 (7)
C3	0.0432 (9)	0.0455 (10)	0.0538 (11)	0.0090 (8)	0.0112 (8)	0.0032 (8)
C4	0.0492 (10)	0.0471 (10)	0.0570 (11)	0.0080 (8)	0.0134 (8)	0.0041 (8)
C5	0.0608 (11)	0.0499 (10)	0.0464 (10)	0.0273 (9)	0.0151 (8)	0.0099 (8)
C6	0.0641 (11)	0.0518 (10)	0.0480 (10)	0.0311 (9)	0.0104 (9)	0.0082 (8)
C7	0.0740 (15)	0.0635 (14)	0.0905 (17)	0.0127 (11)	0.0392 (13)	0.0200 (12)
C8	0.0462 (10)	0.0597 (12)	0.0715 (13)	0.0167 (9)	0.0195 (9)	0.0058 (10)
C9	0.0828 (18)	0.088 (2)	0.180 (3)	0.0567 (16)	0.061 (2)	0.038 (2)
C10	0.112 (2)	0.086 (2)	0.150 (3)	0.0586 (19)	0.037 (2)	0.0105 (19)
C11	0.0403 (8)	0.0421 (9)	0.0494 (10)	0.0171 (7)	0.0170 (7)	0.0064 (7)
C12	0.0666 (12)	0.0487 (11)	0.0581 (12)	0.0187 (9)	0.0066 (10)	0.0087 (9)
C13	0.0690 (14)	0.0758 (15)	0.0564 (12)	0.0245 (12)	0.0022 (10)	0.0014 (11)
C14	0.0588 (12)	0.0558 (13)	0.0766 (15)	0.0026 (10)	0.0148 (11)	−0.0080 (11)
C15	0.0806 (16)	0.0443 (12)	0.0954 (18)	0.0020 (11)	0.0115 (14)	0.0139 (12)
C16	0.0650 (13)	0.0484 (11)	0.0705 (13)	0.0143 (10)	0.0104 (10)	0.0174 (10)
C17	0.0714 (13)	0.0622 (12)	0.0508 (11)	0.0388 (10)	0.0160 (9)	0.0127 (9)
C18	0.0697 (12)	0.0682 (13)	0.0441 (10)	0.0422 (11)	0.0064 (9)	0.0055 (9)
C19	0.0897 (16)	0.0763 (14)	0.0588 (12)	0.0526 (13)	0.0189 (11)	0.0164 (11)
C20	0.109 (2)	0.0881 (17)	0.0676 (14)	0.0677 (16)	0.0141 (14)	0.0181 (12)
C21	0.0910 (17)	0.0959 (18)	0.0632 (13)	0.0684 (15)	0.0039 (12)	0.0043 (13)
C22	0.0688 (13)	0.0962 (17)	0.0486 (11)	0.0526 (13)	0.0013 (9)	−0.0021 (11)
C23	0.0686 (13)	0.0753 (14)	0.0477 (11)	0.0430 (11)	0.0056 (9)	0.0059 (9)

S1—C6	1.743 (2)	C10—H10A	0.9600
S1—C1	1.750 (2)	C10—H10B	0.9600
Cl1—C22	1.734 (3)	C10—H10C	0.9600
N1—C1	1.269 (2)	C11—C16	1.370 (3)
N1—C4	1.413 (3)	C11—C12	1.376 (3)
N2—C1	1.369 (2)	C12—C13	1.378 (3)
N2—C5	1.384 (2)	C12—H12	0.9300
N2—C2	1.474 (2)	C13—C14	1.366 (3)
O1—C5	1.202 (2)	C13—H13	0.9300
O2—C8	1.322 (3)	C14—C15	1.357 (4)
O2—C9	1.461 (3)	C14—H14	0.9300
O3—C8	1.190 (3)	C15—C16	1.372 (3)
C2—C3	1.518 (3)	C15—H15	0.9300
C2—C11	1.517 (2)	C16—H16	0.9300
C2—H2	0.9800	C17—C18	1.458 (3)
C3—C4	1.345 (3)	C17—H17	0.9300
C3—C8	1.473 (3)	C18—C23	1.390 (3)
C4—C7	1.495 (3)	C18—C19	1.395 (3)
C5—C6	1.489 (3)	C19—C20	1.382 (3)
C6—C17	1.338 (3)	C19—H19	0.9300
C7—H7A	0.9600	C20—C21	1.370 (4)
C7—H7B	0.9600	C20—H20	0.9300
C7—H7C	0.9600	C21—C22	1.374 (4)
C9—C10	1.432 (4)	C21—H21	0.9300
C9—H9A	0.9700	C22—C23	1.380 (3)
C9—H9B	0.9700	C23—H23	0.9300
C6—S1—C1	91.75 (9)	H10A—C10—H10B	109.5
C1—N1—C4	116.63 (16)	C9—C10—H10C	109.5
C1—N2—C5	116.72 (15)	H10A—C10—H10C	109.5
C1—N2—C2	120.56 (15)	H10B—C10—H10C	109.5
C5—N2—C2	121.87 (14)	C16—C11—C12	118.73 (17)
C8—O2—C9	118.6 (2)	C16—C11—C2	120.90 (17)
N1—C1—N2	126.94 (18)	C12—C11—C2	120.36 (16)
N1—C1—S1	121.68 (15)	C11—C12—C13	120.4 (2)
N2—C1—S1	111.37 (14)	C11—C12—H12	119.8
N2—C2—C3	108.40 (14)	C13—C12—H12	119.8
N2—C2—C11	109.88 (14)	C14—C13—C12	120.0 (2)
C3—C2—C11	111.85 (14)	C14—C13—H13	120.0
N2—C2—H2	108.9	C12—C13—H13	120.0
C3—C2—H2	108.9	C15—C14—C13	119.6 (2)
C11—C2—H2	108.9	C15—C14—H14	120.2
C4—C3—C8	121.80 (18)	C13—C14—H14	120.2
C4—C3—C2	121.61 (17)	C14—C15—C16	120.7 (2)
C8—C3—C2	116.49 (17)	C14—C15—H15	119.7
C3—C4—N1	122.24 (17)	C16—C15—H15	119.7
C3—C4—C7	125.8 (2)	C11—C16—C15	120.4 (2)
N1—C4—C7	111.97 (18)	C11—C16—H16	119.8
O1—C5—N2	123.64 (17)	C15—C16—H16	119.8
O1—C5—C6	126.67 (18)	C6—C17—C18	130.16 (19)
N2—C5—C6	109.69 (16)	C6—C17—H17	114.9
C17—C6—C5	120.14 (18)	C18—C17—H17	114.9
C17—C6—S1	129.37 (15)	C23—C18—C19	118.59 (19)
C5—C6—S1	110.45 (14)	C23—C18—C17	117.16 (19)
C4—C7—H7A	109.5	C19—C18—C17	124.2 (2)
C4—C7—H7B	109.5	C20—C19—C18	120.3 (2)
H7A—C7—H7B	109.5	C20—C19—H19	119.8
C4—C7—H7C	109.5	C18—C19—H19	119.8
H7A—C7—H7C	109.5	C21—C20—C19	120.9 (2)
H7B—C7—H7C	109.5	C21—C20—H20	119.6
O3—C8—O2	122.0 (2)	C19—C20—H20	119.6
O3—C8—C3	126.6 (2)	C20—C21—C22	118.8 (2)
O2—C8—C3	111.39 (17)	C20—C21—H21	120.6
C10—C9—O2	110.2 (2)	C22—C21—H21	120.6
C10—C9—H9A	109.6	C21—C22—C23	121.7 (2)
O2—C9—H9A	109.6	C21—C22—Cl1	119.69 (17)
C10—C9—H9B	109.6	C23—C22—Cl1	118.6 (2)
O2—C9—H9B	109.6	C22—C23—C18	119.7 (2)
H9A—C9—H9B	108.1	C22—C23—H23	120.2
C9—C10—H10A	109.5	C18—C23—H23	120.2
C9—C10—H10B	109.5
C4—N1—C1—N2	4.5 (3)	C9—O2—C8—C3	−176.0 (2)
C4—N1—C1—S1	−174.31 (14)	C4—C3—C8—O3	7.8 (4)
C5—N2—C1—N1	−179.82 (18)	C2—C3—C8—O3	−168.5 (2)
C2—N2—C1—N1	10.6 (3)	C4—C3—C8—O2	−171.50 (19)
C5—N2—C1—S1	−0.9 (2)	C2—C3—C8—O2	12.2 (3)
C2—N2—C1—S1	−170.54 (12)	C8—O2—C9—C10	117.2 (3)
C6—S1—C1—N1	−179.77 (17)	N2—C2—C11—C16	120.27 (19)
C6—S1—C1—N2	1.29 (14)	C3—C2—C11—C16	−119.3 (2)
C1—N2—C2—C3	−20.5 (2)	N2—C2—C11—C12	−61.0 (2)
C5—N2—C2—C3	170.42 (15)	C3—C2—C11—C12	59.4 (2)
C1—N2—C2—C11	101.98 (18)	C16—C11—C12—C13	−1.6 (3)
C5—N2—C2—C11	−67.1 (2)	C2—C11—C12—C13	179.69 (19)
N2—C2—C3—C4	18.8 (2)	C11—C12—C13—C14	2.2 (3)
C11—C2—C3—C4	−102.5 (2)	C12—C13—C14—C15	−1.1 (4)
N2—C2—C3—C8	−164.91 (16)	C13—C14—C15—C16	−0.6 (4)
C11—C2—C3—C8	73.8 (2)	C12—C11—C16—C15	−0.1 (3)
C8—C3—C4—N1	177.36 (17)	C2—C11—C16—C15	178.6 (2)
C2—C3—C4—N1	−6.5 (3)	C14—C15—C16—C11	1.2 (4)
C8—C3—C4—C7	−1.9 (3)	C5—C6—C17—C18	176.23 (19)
C2—C3—C4—C7	174.21 (19)	S1—C6—C17—C18	−1.3 (4)
C1—N1—C4—C3	−6.4 (3)	C6—C17—C18—C23	−175.3 (2)
C1—N1—C4—C7	173.01 (18)	C6—C17—C18—C19	5.1 (4)
C1—N2—C5—O1	−178.87 (18)	C23—C18—C19—C20	1.2 (3)
C2—N2—C5—O1	−9.4 (3)	C17—C18—C19—C20	−179.2 (2)
C1—N2—C5—C6	0.0 (2)	C18—C19—C20—C21	−0.9 (4)
C2—N2—C5—C6	169.41 (15)	C19—C20—C21—C22	0.0 (4)
O1—C5—C6—C17	1.8 (3)	C20—C21—C22—C23	0.5 (3)
N2—C5—C6—C17	−176.99 (17)	C20—C21—C22—Cl1	−178.66 (18)
O1—C5—C6—S1	179.79 (17)	C21—C22—C23—C18	−0.2 (3)
N2—C5—C6—S1	1.0 (2)	Cl1—C22—C23—C18	178.96 (15)
C1—S1—C6—C17	176.5 (2)	C19—C18—C23—C22	−0.6 (3)
C1—S1—C6—C5	−1.29 (14)	C17—C18—C23—C22	179.71 (18)
C9—O2—C8—O3	4.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···O1i	0.93	2.49	3.287 (3)	143
C19—H19···S1	0.93	2.50	3.210 (3)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23⋯O1i	0.93	2.49	3.287 (3)	143
C19—H19⋯S1	0.93	2.50	3.210 (3)	133

Symmetry code: (i) .