Ethyl (2Z)-2-(3-methoxy-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(24)H(22)N(2)O(4)S, the central pyrimidine ring is significantly puckered, assuming a conformation inter-mediate between a boat and a screw boat. The nearly planar thia-zole ring (r.m.s. deviation = 0.0258 Å) is fused with the pyriamidine ring, making a dihedral angle of 9.83 (7)°. The carboxyl group is in an extended conformation with an anti-periplanar orientation with respect to the dihydropyrimidine ring. The benzene ring linked at the chiral C atom is perpendicular to the pyrimidine ring [dihedral angle = 85.21 (8)°] whereas the phenyl ring is nearly coplanar, making a dihedral angle of 13.20 (8)°. An intra-molecular C-H⋯S hydrogen bond is observed. The crystal packing is influenced by weak inter-molecular C-H⋯π inter-actions and π-π stacking between the thia-zole and phenyl rings [centroid-centroid distance = 3.9656 (10) Å], which stack the mol-ecules along the c axis.

Related literature

For related structures, see: Jotani & Baldaniya (2008 ▶); Sridhar et al. (2006 ▶); Fischer et al. (2007 ▶); Baldaniya & Jotani (2008 ▶); Jotani et al. (2009 ▶). For the biological activity of dihydro­pyrimidines, see: Wichmann et al. (1999 ▶); Kappe (2000 ▶); Mayer et al. (1999 ▶). For a description of the Cambridge Structural Database, see: Allen, (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C24H22N2O4S

M = 434.50

Monoclinic,

a = 33.0445 (6) Å

b = 9.5013 (2) Å

c = 13.8845 (2) Å

β = 101.548 (1)°

V = 4271.01 (13) Å3

Z = 8

Mo Kα radiation

μ = 0.19 mm−1

T = 293 K

0.30 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.946, T max = 0.973

27172 measured reflections

6222 independent reflections

4099 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.113

S = 0.93

6222 reflections

284 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.23 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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004812/ng2731sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004812/ng2731Isup2.hkl

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

C24H22N2O4S	F(000) = 1824
Mr = 434.50	Dx = 1.351 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 5670 reflections
a = 33.0445 (6) Å	θ = 3.0–30.0°
b = 9.5013 (2) Å	µ = 0.19 mm−1
c = 13.8845 (2) Å	T = 293 K
β = 101.548 (1)°	Plate, colorless
V = 4271.01 (13) Å3	0.30 × 0.20 × 0.15 mm
Z = 8

Bruker APEXII CCD diffractometer	6222 independent reflections
Radiation source: fine-focus sealed tube	4099 reflections with I > 2σ(I)
graphite	Rint = 0.035
ω and φ scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −46→46
Tmin = 0.946, Tmax = 0.973	k = −13→13
27172 measured reflections	l = −19→19

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)] = 0.043	H-atom parameters constrained
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.049P)2 + 2.3025P] where P = (Fo2 + 2Fc2)/3
S = 0.93	(Δ/σ)max < 0.001
6222 reflections	Δρmax = 0.24 e Å−3
284 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00104 (16)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
S1	0.235672 (11)	0.12268 (4)	0.10790 (3)	0.05063 (12)
N1	0.18618 (4)	0.34110 (13)	0.11604 (10)	0.0487 (3)
N2	0.15837 (3)	0.11297 (12)	0.11518 (9)	0.0373 (2)
O1	0.14512 (3)	−0.11959 (11)	0.12997 (10)	0.0571 (3)
O2	0.04874 (4)	0.27636 (13)	0.15987 (10)	0.0672 (4)
O3	0.06592 (4)	0.49424 (12)	0.12836 (10)	0.0629 (3)
O4	0.37128 (4)	−0.07609 (15)	0.09922 (11)	0.0733 (4)
C1	0.18927 (4)	0.20741 (15)	0.11242 (11)	0.0406 (3)
C2	0.11507 (4)	0.15838 (14)	0.10056 (10)	0.0368 (3)
H2	0.1018	0.1070	0.1470	0.044*
C3	0.11429 (4)	0.31329 (14)	0.12389 (10)	0.0381 (3)
C4	0.14806 (4)	0.39460 (15)	0.13134 (11)	0.0432 (3)
C5	0.16927 (4)	−0.02682 (15)	0.12298 (11)	0.0411 (3)
C6	0.21375 (4)	−0.04258 (15)	0.12057 (11)	0.0416 (3)
C7	0.15201 (5)	0.54599 (17)	0.16009 (15)	0.0617 (5)
H7A	0.1494	0.6032	0.1022	0.093*
H7B	0.1785	0.5619	0.2018	0.093*
H7C	0.1306	0.5704	0.1948	0.093*
C8	0.07349 (5)	0.35749 (15)	0.14060 (11)	0.0426 (3)
C9	0.02824 (6)	0.5474 (2)	0.15207 (18)	0.0759 (6)
H9A	0.0321	0.5645	0.2222	0.091*
H9B	0.0063	0.4787	0.1340	0.091*
C10	0.01708 (7)	0.6780 (2)	0.09834 (18)	0.0874 (7)
H10A	0.0398	0.7426	0.1124	0.131*
H10B	−0.0066	0.7186	0.1182	0.131*
H10C	0.0106	0.6587	0.0291	0.131*
C11	0.09283 (4)	0.12247 (14)	−0.00271 (11)	0.0394 (3)
C12	0.10440 (5)	0.18604 (18)	−0.08289 (12)	0.0504 (4)
H12	0.1246	0.2555	−0.0730	0.060*
C13	0.08613 (5)	0.1470 (2)	−0.17714 (13)	0.0638 (5)
H13	0.0945	0.1883	−0.2306	0.077*
C14	0.05548 (6)	0.0471 (2)	−0.19211 (15)	0.0670 (5)
H14	0.0431	0.0210	−0.2558	0.080*
C15	0.04305 (5)	−0.0141 (2)	−0.11405 (16)	0.0651 (5)
H15	0.0221	−0.0809	−0.1246	0.078*
C16	0.06171 (5)	0.02327 (16)	−0.01906 (13)	0.0509 (4)
H16	0.0532	−0.0188	0.0340	0.061*
C17	0.23076 (4)	−0.16995 (17)	0.12650 (11)	0.0459 (3)
H17	0.2127	−0.2427	0.1335	0.055*
C18	0.27255 (4)	−0.21580 (16)	0.12404 (11)	0.0452 (3)
C19	0.30375 (5)	−0.12586 (17)	0.11084 (12)	0.0506 (4)
H19	0.2983	−0.0302	0.1020	0.061*
C20	0.34317 (5)	−0.1759 (2)	0.11051 (12)	0.0533 (4)
C21	0.35128 (5)	−0.3184 (2)	0.12200 (12)	0.0588 (4)
H21	0.3776	−0.3529	0.1219	0.071*
C22	0.32012 (5)	−0.4086 (2)	0.13349 (13)	0.0597 (4)
H22	0.3255	−0.5045	0.1406	0.072*
C23	0.28096 (5)	−0.35955 (17)	0.13471 (12)	0.0520 (4)
H23	0.2602	−0.4220	0.1426	0.062*
C24	0.41086 (5)	−0.1219 (3)	0.08662 (16)	0.0806 (6)
H24A	0.4245	−0.1705	0.1447	0.121*
H24B	0.4270	−0.0419	0.0755	0.121*
H24C	0.4077	−0.1843	0.0312	0.121*

	U11	U22	U33	U12	U13	U23
S1	0.03193 (18)	0.0440 (2)	0.0776 (3)	0.00373 (15)	0.01474 (17)	0.00509 (18)
N1	0.0357 (6)	0.0366 (7)	0.0741 (9)	−0.0006 (5)	0.0117 (6)	0.0037 (6)
N2	0.0287 (5)	0.0328 (6)	0.0502 (7)	0.0034 (4)	0.0072 (4)	0.0033 (5)
O1	0.0435 (6)	0.0346 (6)	0.0973 (9)	0.0032 (5)	0.0237 (6)	0.0075 (5)
O2	0.0542 (7)	0.0474 (7)	0.1104 (10)	0.0035 (6)	0.0416 (7)	0.0055 (6)
O3	0.0529 (7)	0.0417 (6)	0.1035 (10)	0.0146 (5)	0.0386 (6)	0.0074 (6)
O4	0.0429 (6)	0.0804 (9)	0.1015 (10)	0.0056 (6)	0.0259 (6)	0.0009 (8)
C1	0.0314 (6)	0.0387 (8)	0.0508 (8)	0.0015 (6)	0.0063 (6)	0.0034 (6)
C2	0.0287 (6)	0.0331 (7)	0.0503 (8)	0.0036 (5)	0.0120 (5)	0.0034 (6)
C3	0.0365 (7)	0.0325 (7)	0.0464 (8)	0.0055 (5)	0.0109 (6)	0.0019 (6)
C4	0.0397 (7)	0.0324 (7)	0.0571 (9)	0.0033 (6)	0.0087 (6)	0.0029 (6)
C5	0.0360 (7)	0.0346 (7)	0.0533 (8)	0.0060 (6)	0.0104 (6)	0.0037 (6)
C6	0.0337 (7)	0.0416 (8)	0.0501 (8)	0.0059 (6)	0.0093 (6)	0.0036 (6)
C7	0.0529 (10)	0.0340 (8)	0.0951 (14)	−0.0007 (7)	0.0073 (9)	−0.0062 (8)
C8	0.0427 (7)	0.0383 (8)	0.0497 (8)	0.0064 (6)	0.0168 (6)	0.0002 (6)
C9	0.0631 (11)	0.0580 (12)	0.1196 (17)	0.0211 (9)	0.0493 (12)	0.0010 (11)
C10	0.0741 (14)	0.0789 (15)	0.1087 (17)	0.0371 (12)	0.0170 (12)	−0.0026 (13)
C11	0.0289 (6)	0.0341 (7)	0.0551 (8)	0.0075 (5)	0.0081 (6)	−0.0022 (6)
C12	0.0399 (8)	0.0559 (10)	0.0548 (9)	0.0037 (7)	0.0080 (7)	−0.0002 (7)
C13	0.0489 (9)	0.0858 (14)	0.0555 (10)	0.0150 (9)	0.0071 (8)	−0.0010 (9)
C14	0.0511 (10)	0.0773 (13)	0.0652 (12)	0.0198 (9)	−0.0063 (8)	−0.0185 (10)
C15	0.0399 (8)	0.0525 (10)	0.0941 (15)	0.0035 (8)	−0.0075 (9)	−0.0161 (10)
C16	0.0366 (7)	0.0409 (8)	0.0733 (11)	0.0023 (6)	0.0062 (7)	−0.0022 (7)
C17	0.0378 (7)	0.0429 (8)	0.0576 (9)	0.0083 (6)	0.0111 (6)	0.0028 (7)
C18	0.0397 (7)	0.0486 (9)	0.0469 (8)	0.0140 (6)	0.0078 (6)	0.0005 (6)
C19	0.0414 (8)	0.0504 (9)	0.0605 (10)	0.0125 (7)	0.0116 (7)	0.0005 (7)
C20	0.0401 (8)	0.0688 (11)	0.0517 (9)	0.0100 (8)	0.0109 (7)	−0.0019 (8)
C21	0.0454 (9)	0.0744 (12)	0.0569 (10)	0.0266 (9)	0.0105 (7)	−0.0012 (8)
C22	0.0580 (10)	0.0561 (10)	0.0651 (11)	0.0262 (8)	0.0124 (8)	0.0025 (8)
C23	0.0487 (9)	0.0512 (9)	0.0568 (9)	0.0146 (7)	0.0122 (7)	0.0012 (7)
C24	0.0394 (9)	0.1200 (19)	0.0849 (14)	0.0135 (11)	0.0187 (9)	0.0131 (12)

S1—C1	1.7439 (14)	C10—H10B	0.9600
S1—C6	1.7528 (15)	C10—H10C	0.9600
N1—C1	1.2761 (19)	C11—C16	1.380 (2)
N1—C4	1.4134 (18)	C11—C12	1.386 (2)
N2—C1	1.3655 (17)	C12—C13	1.378 (2)
N2—C5	1.3747 (17)	C12—H12	0.9300
N2—C2	1.4693 (16)	C13—C14	1.374 (3)
O1—C5	1.2059 (17)	C13—H13	0.9300
O2—C8	1.1928 (18)	C14—C15	1.364 (3)
O3—C8	1.3277 (17)	C14—H14	0.9300
O3—C9	1.4413 (18)	C15—C16	1.386 (2)
O4—C20	1.358 (2)	C15—H15	0.9300
O4—C24	1.422 (2)	C16—H16	0.9300
C2—C3	1.5084 (19)	C17—C18	1.4551 (19)
C2—C11	1.513 (2)	C17—H17	0.9300
C2—H2	0.9800	C18—C19	1.379 (2)
C3—C4	1.3441 (19)	C18—C23	1.396 (2)
C3—C8	1.4740 (19)	C19—C20	1.388 (2)
C4—C7	1.491 (2)	C19—H19	0.9300
C5—C6	1.4842 (19)	C20—C21	1.383 (3)
C6—C17	1.330 (2)	C21—C22	1.373 (3)
C7—H7A	0.9600	C21—H21	0.9300
C7—H7B	0.9600	C22—C23	1.379 (2)
C7—H7C	0.9600	C22—H22	0.9300
C9—C10	1.457 (3)	C23—H23	0.9300
C9—H9A	0.9700	C24—H24A	0.9600
C9—H9B	0.9700	C24—H24B	0.9600
C10—H10A	0.9600	C24—H24C	0.9600
C1—S1—C6	91.48 (7)	H10A—C10—H10C	109.5
C1—N1—C4	116.41 (12)	H10B—C10—H10C	109.5
C1—N2—C5	116.84 (11)	C16—C11—C12	118.81 (14)
C1—N2—C2	121.08 (11)	C16—C11—C2	120.96 (13)
C5—N2—C2	121.81 (11)	C12—C11—C2	120.20 (13)
C8—O3—C9	117.58 (13)	C13—C12—C11	120.45 (16)
C20—O4—C24	117.87 (16)	C13—C12—H12	119.8
N1—C1—N2	125.93 (13)	C11—C12—H12	119.8
N1—C1—S1	122.60 (11)	C14—C13—C12	119.96 (18)
N2—C1—S1	111.43 (10)	C14—C13—H13	120.0
N2—C2—C3	108.35 (11)	C12—C13—H13	120.0
N2—C2—C11	109.85 (10)	C15—C14—C13	120.32 (17)
C3—C2—C11	113.42 (11)	C15—C14—H14	119.8
N2—C2—H2	108.4	C13—C14—H14	119.8
C3—C2—H2	108.4	C14—C15—C16	119.98 (17)
C11—C2—H2	108.4	C14—C15—H15	120.0
C4—C3—C8	126.55 (13)	C16—C15—H15	120.0
C4—C3—C2	121.85 (12)	C11—C16—C15	120.45 (16)
C8—C3—C2	111.55 (12)	C11—C16—H16	119.8
C3—C4—N1	122.20 (13)	C15—C16—H16	119.8
C3—C4—C7	127.00 (14)	C6—C17—C18	131.48 (15)
N1—C4—C7	110.74 (13)	C6—C17—H17	114.3
O1—C5—N2	123.05 (12)	C18—C17—H17	114.3
O1—C5—C6	127.03 (13)	C19—C18—C23	118.83 (14)
N2—C5—C6	109.91 (12)	C19—C18—C17	123.77 (14)
C17—C6—C5	119.90 (13)	C23—C18—C17	117.40 (15)
C17—C6—S1	130.03 (11)	C18—C19—C20	121.03 (15)
C5—C6—S1	110.06 (10)	C18—C19—H19	119.5
C4—C7—H7A	109.5	C20—C19—H19	119.5
C4—C7—H7B	109.5	O4—C20—C21	125.14 (15)
H7A—C7—H7B	109.5	O4—C20—C19	115.18 (16)
C4—C7—H7C	109.5	C21—C20—C19	119.68 (16)
H7A—C7—H7C	109.5	C22—C21—C20	119.45 (15)
H7B—C7—H7C	109.5	C22—C21—H21	120.3
O2—C8—O3	122.74 (13)	C20—C21—H21	120.3
O2—C8—C3	122.77 (13)	C21—C22—C23	121.21 (16)
O3—C8—C3	114.43 (13)	C21—C22—H22	119.4
O3—C9—C10	108.86 (16)	C23—C22—H22	119.4
O3—C9—H9A	109.9	C22—C23—C18	119.79 (17)
C10—C9—H9A	109.9	C22—C23—H23	120.1
O3—C9—H9B	109.9	C18—C23—H23	120.1
C10—C9—H9B	109.9	O4—C24—H24A	109.5
H9A—C9—H9B	108.3	O4—C24—H24B	109.5
C9—C10—H10A	109.5	H24A—C24—H24B	109.5
C9—C10—H10B	109.5	O4—C24—H24C	109.5
H10A—C10—H10B	109.5	H24A—C24—H24C	109.5
C9—C10—H10C	109.5	H24B—C24—H24C	109.5
C4—N1—C1—N2	4.8 (2)	C4—C3—C8—O2	−158.39 (16)
C4—N1—C1—S1	−172.62 (11)	C2—C3—C8—O2	19.1 (2)
C5—N2—C1—N1	−171.96 (14)	C4—C3—C8—O3	24.3 (2)
C2—N2—C1—N1	14.0 (2)	C2—C3—C8—O3	−158.23 (13)
C5—N2—C1—S1	5.71 (16)	C8—O3—C9—C10	−156.88 (18)
C2—N2—C1—S1	−168.38 (10)	N2—C2—C11—C16	113.42 (13)
C6—S1—C1—N1	172.96 (14)	C3—C2—C11—C16	−125.17 (14)
C6—S1—C1—N2	−4.80 (11)	N2—C2—C11—C12	−64.54 (16)
C1—N2—C2—C3	−22.21 (17)	C3—C2—C11—C12	56.87 (16)
C5—N2—C2—C3	164.00 (12)	C16—C11—C12—C13	−2.3 (2)
C1—N2—C2—C11	102.20 (14)	C2—C11—C12—C13	175.70 (14)
C5—N2—C2—C11	−71.60 (16)	C11—C12—C13—C14	1.7 (3)
N2—C2—C3—C4	15.01 (18)	C12—C13—C14—C15	−0.1 (3)
C11—C2—C3—C4	−107.23 (15)	C13—C14—C15—C16	−0.8 (3)
N2—C2—C3—C8	−162.59 (11)	C12—C11—C16—C15	1.4 (2)
C11—C2—C3—C8	75.16 (15)	C2—C11—C16—C15	−176.60 (13)
C8—C3—C4—N1	178.44 (14)	C14—C15—C16—C11	0.1 (2)
C2—C3—C4—N1	1.2 (2)	C5—C6—C17—C18	178.62 (15)
C8—C3—C4—C7	1.4 (3)	S1—C6—C17—C18	−0.4 (3)
C2—C3—C4—C7	−175.82 (15)	C6—C17—C18—C19	−2.3 (3)
C1—N1—C4—C3	−12.3 (2)	C6—C17—C18—C23	178.40 (16)
C1—N1—C4—C7	165.13 (14)	C23—C18—C19—C20	−1.6 (2)
C1—N2—C5—O1	177.02 (14)	C17—C18—C19—C20	179.12 (15)
C2—N2—C5—O1	−8.9 (2)	C24—O4—C20—C21	7.8 (3)
C1—N2—C5—C6	−3.43 (18)	C24—O4—C20—C19	−172.72 (16)
C2—N2—C5—C6	170.62 (12)	C18—C19—C20—O4	−178.46 (15)
O1—C5—C6—C17	0.0 (2)	C18—C19—C20—C21	1.1 (2)
N2—C5—C6—C17	−179.57 (13)	O4—C20—C21—C22	179.52 (16)
O1—C5—C6—S1	179.16 (14)	C19—C20—C21—C22	0.1 (2)
N2—C5—C6—S1	−0.38 (15)	C20—C21—C22—C23	−0.6 (3)
C1—S1—C6—C17	−178.02 (15)	C21—C22—C23—C18	0.0 (3)
C1—S1—C6—C5	2.89 (11)	C19—C18—C23—C22	1.0 (2)
C9—O3—C8—O2	8.2 (3)	C17—C18—C23—C22	−179.63 (15)
C9—O3—C8—C3	−174.50 (16)

Cg3 is the centroid of the C11–C16 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···S1	0.93	2.54	3.2561 (15)	134
C10—H10B···Cg3i	0.96	2.87	3.755 (3)	153
C21—H21···Cg3ii	0.93	2.79	3.602 (2)	147

Cg1···Cg4iii

3.9656 (10)

Table 1

Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯S1	0.93	2.54	3.2561 (15)	134
C10—H10B⋯Cg3i	0.96	2.87	3.755 (3)	153
C21—H21⋯Cg3ii	0.93	2.79	3.602 (2)	147

Symmetry codes: (i) ; (ii) .