Ethyl 2-(2-acetoxy-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 mol-ecule, C(25)H(22)N(2)O(5)S, the atoms of the thia-zolopyrimidine ring system, with the exception of the phenyl-bearing C atom [deviation = 0.177 (2) Å], are essentially planar [r.m.s deviation = 0.100 (2) °] and the mean plane of these atoms forms dihedral angles of 89.86 (10) and 7.97 (8)° with the phenyl and benzene rings, respectively. In the crystal, co-operative C-H⋯O and C-H⋯π inter-actions lead to a supra-molecular chain along the a axis. These chains are connected via π-π inter-actions [centroid-centroid = 3.7523 (13) Å].

Related literature

For background to the pharmacological activity of thia­zolo[3,2-a]pyrimidine derivatives, see: Winter et al. (1962 ▶); Atwal et al. (1990 ▶); Kappe (2000 ▶); Adams et al. (2005 ▶). For related structures, see: Jotani & Baldaniya (2007 ▶, 2008 ▶); Baldaniya & Jotani (2008 ▶); Jotani et al. (2009 ▶). For additional geometric analysis, see: Cremer & Pople (1975 ▶). Semi-empirical Quantum Chemical Calculations were performed with the n class="Chemical">MOPAC2009 program (Stewart, 2009 ▶).

Experimental

Crystal data

C25H22N2O5S

M = 462.51

Triclinic,

a = 8.4236 (3) Å

b = 9.6807 (3) Å

c = 14.3345 (5) Å

α = 87.939 (2)°

β = 89.680 (2)°

γ = 75.287 (2)°

V = 1129.86 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.18 mm−1

T = 293 K

0.47 × 0.35 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.920, T max = 0.965

20701 measured reflections

3969 independent reflections

3438 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.137

S = 1.06

3969 reflections

301 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.31 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: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007853/lh5004sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007853/lh5004Isup2.hkl

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

C25H22N2O5S	Z = 2
Mr = 462.51	F(000) = 484
Triclinic, P1	Dx = 1.359 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4236 (3) Å	Cell parameters from 5176 reflections
b = 9.6807 (3) Å	θ = 2.2–31.3°
c = 14.3345 (5) Å	µ = 0.18 mm−1
α = 87.939 (2)°	T = 293 K
β = 89.680 (2)°	Block, yellow
γ = 75.287 (2)°	0.47 × 0.35 × 0.20 mm
V = 1129.86 (7) Å3

Bruker SMART APEX CCD diffractometer	3969 independent reflections
Radiation source: fine-focus sealed tube	3438 reflections with I > 2σ(I)
graphite	Rint = 0.024
ω and φ scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.920, Tmax = 0.965	k = −11→11
20701 measured reflections	l = −17→17

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0721P)2 + 0.4966P] where P = (Fo2 + 2Fc2)/3
3969 reflections	(Δ/σ)max = 0.002
301 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.31 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	0.19582 (7)	0.35035 (6)	0.10853 (4)	0.0550 (2)
O1	0.8697 (2)	0.4977 (2)	0.28339 (16)	0.0886 (6)
O2	0.87965 (18)	0.27940 (18)	0.33559 (11)	0.0604 (4)
O3	0.44199 (18)	0.03161 (15)	0.25695 (11)	0.0563 (4)
O4	−0.00662 (19)	−0.14186 (16)	0.17321 (11)	0.0590 (4)
O5	−0.1285 (3)	−0.0711 (3)	0.30616 (14)	0.1097 (9)
N1	0.4187 (2)	0.4897 (2)	0.14656 (13)	0.0568 (5)
N2	0.45080 (18)	0.25926 (16)	0.21508 (10)	0.0387 (4)
C1	0.3732 (2)	0.3754 (2)	0.16117 (13)	0.0447 (5)
C2	0.5865 (2)	0.2654 (2)	0.27852 (12)	0.0383 (4)
H2	0.6743	0.1775	0.2736	0.046*
C3	0.6520 (2)	0.3922 (2)	0.24663 (13)	0.0433 (4)
C4	0.5692 (3)	0.4949 (2)	0.18730 (15)	0.0524 (5)
C5	0.5251 (2)	0.2766 (2)	0.37843 (12)	0.0377 (4)
C6	0.4075 (3)	0.3956 (2)	0.40504 (15)	0.0496 (5)
H6	0.3675	0.4700	0.3618	0.060*
C7	0.3486 (3)	0.4053 (3)	0.49501 (17)	0.0640 (6)
H7	0.2689	0.4858	0.5121	0.077*
C8	0.4071 (3)	0.2968 (3)	0.55903 (16)	0.0664 (7)
H8	0.3666	0.3029	0.6196	0.080*
C9	0.5252 (4)	0.1794 (3)	0.53393 (16)	0.0690 (7)
H9	0.5663	0.1062	0.5779	0.083*
C10	0.5843 (3)	0.1683 (2)	0.44344 (15)	0.0552 (5)
H10	0.6640	0.0875	0.4267	0.066*
C11	0.8095 (3)	0.3985 (2)	0.28807 (14)	0.0492 (5)
C12	1.0308 (3)	0.2780 (3)	0.38364 (18)	0.0651 (6)
H12A	1.1119	0.2944	0.3392	0.078*
H12B	1.0113	0.3533	0.4284	0.078*
C13	1.0905 (4)	0.1404 (4)	0.4313 (3)	0.1057 (12)
H13A	1.0139	0.1285	0.4789	0.158*
H13B	1.1952	0.1352	0.4593	0.158*
H13C	1.1019	0.0661	0.3872	0.158*
C14	0.6204 (4)	0.6257 (3)	0.1538 (2)	0.0819 (9)
H14A	0.7278	0.6218	0.1777	0.123*
H14B	0.5436	0.7094	0.1755	0.123*
H14C	0.6227	0.6296	0.0868	0.123*
C15	0.3839 (2)	0.1429 (2)	0.21508 (13)	0.0409 (4)
C16	0.2306 (2)	0.1780 (2)	0.15845 (12)	0.0417 (4)
C17	0.1391 (2)	0.0840 (2)	0.15492 (13)	0.0445 (4)
H17	0.1848	−0.0036	0.1852	0.053*
C18	−0.0194 (2)	0.0952 (2)	0.11188 (13)	0.0437 (4)
C19	−0.0947 (2)	−0.0168 (2)	0.12602 (14)	0.0463 (5)
C20	−0.2463 (3)	−0.0123 (3)	0.08936 (16)	0.0563 (5)
H20	−0.2943	−0.0877	0.1009	0.068*
C21	−0.3265 (3)	0.1051 (3)	0.03518 (16)	0.0563 (6)
H21	−0.4290	0.1089	0.0099	0.068*
C22	−0.2554 (3)	0.2161 (3)	0.01856 (15)	0.0555 (5)
H22	−0.3092	0.2948	−0.0184	0.067*
C23	−0.1045 (3)	0.2112 (2)	0.05660 (15)	0.0516 (5)
H23	−0.0580	0.2876	0.0450	0.062*
C24	−0.0289 (3)	−0.1560 (3)	0.26542 (18)	0.0612 (6)
C25	0.0891 (4)	−0.2840 (3)	0.3062 (2)	0.0810 (8)
H25A	0.1858	−0.2582	0.3265	0.122*
H25B	0.1185	−0.3553	0.2599	0.122*
H25C	0.0396	−0.3214	0.3585	0.122*

	U11	U22	U33	U12	U13	U23
S1	0.0523 (3)	0.0583 (4)	0.0560 (3)	−0.0191 (3)	−0.0217 (2)	0.0164 (3)
O1	0.0699 (12)	0.0833 (13)	0.1248 (17)	−0.0447 (11)	−0.0285 (11)	0.0212 (12)
O2	0.0430 (8)	0.0730 (11)	0.0683 (10)	−0.0222 (7)	−0.0161 (7)	0.0111 (8)
O3	0.0549 (9)	0.0473 (8)	0.0666 (10)	−0.0140 (7)	−0.0186 (7)	0.0120 (7)
O4	0.0563 (9)	0.0499 (9)	0.0684 (10)	−0.0095 (7)	−0.0008 (7)	−0.0001 (7)
O5	0.1234 (19)	0.1067 (17)	0.0643 (12)	0.0321 (15)	0.0107 (12)	0.0131 (11)
N1	0.0579 (11)	0.0560 (11)	0.0592 (11)	−0.0222 (9)	−0.0177 (9)	0.0186 (9)
N2	0.0374 (8)	0.0434 (9)	0.0353 (8)	−0.0103 (7)	−0.0055 (6)	0.0019 (6)
C1	0.0444 (11)	0.0503 (11)	0.0394 (10)	−0.0129 (9)	−0.0074 (8)	0.0067 (8)
C2	0.0333 (9)	0.0426 (10)	0.0384 (9)	−0.0083 (7)	−0.0053 (7)	0.0013 (8)
C3	0.0408 (10)	0.0516 (11)	0.0400 (10)	−0.0163 (9)	0.0025 (8)	−0.0018 (8)
C4	0.0555 (12)	0.0577 (13)	0.0483 (11)	−0.0237 (10)	−0.0045 (9)	0.0095 (9)
C5	0.0342 (9)	0.0437 (10)	0.0373 (9)	−0.0139 (8)	−0.0059 (7)	0.0011 (8)
C6	0.0470 (11)	0.0524 (12)	0.0470 (11)	−0.0083 (9)	−0.0027 (9)	−0.0003 (9)
C7	0.0581 (14)	0.0772 (16)	0.0566 (14)	−0.0151 (12)	0.0098 (11)	−0.0174 (12)
C8	0.0754 (16)	0.0904 (19)	0.0425 (12)	−0.0371 (15)	0.0078 (11)	−0.0091 (12)
C9	0.0877 (18)	0.0779 (17)	0.0437 (12)	−0.0279 (15)	−0.0091 (12)	0.0177 (11)
C10	0.0588 (13)	0.0547 (13)	0.0485 (12)	−0.0088 (10)	−0.0059 (10)	0.0078 (10)
C11	0.0420 (11)	0.0611 (13)	0.0471 (11)	−0.0179 (10)	0.0036 (9)	−0.0022 (10)
C12	0.0417 (12)	0.0902 (18)	0.0647 (15)	−0.0188 (12)	−0.0125 (10)	−0.0020 (13)
C13	0.088 (2)	0.102 (2)	0.128 (3)	−0.0310 (19)	−0.055 (2)	0.030 (2)
C14	0.092 (2)	0.0854 (19)	0.0819 (18)	−0.0525 (17)	−0.0265 (15)	0.0380 (15)
C15	0.0426 (10)	0.0446 (11)	0.0357 (9)	−0.0116 (8)	−0.0018 (8)	−0.0004 (8)
C16	0.0420 (10)	0.0487 (11)	0.0336 (9)	−0.0100 (8)	−0.0038 (7)	−0.0010 (8)
C17	0.0452 (11)	0.0487 (11)	0.0399 (10)	−0.0125 (9)	−0.0057 (8)	0.0006 (8)
C18	0.0439 (10)	0.0515 (11)	0.0365 (9)	−0.0129 (9)	−0.0018 (8)	−0.0051 (8)
C19	0.0461 (11)	0.0487 (11)	0.0443 (11)	−0.0118 (9)	−0.0001 (8)	−0.0040 (9)
C20	0.0498 (12)	0.0614 (14)	0.0629 (13)	−0.0231 (10)	−0.0017 (10)	−0.0055 (11)
C21	0.0424 (11)	0.0719 (15)	0.0565 (13)	−0.0172 (10)	−0.0071 (9)	−0.0070 (11)
C22	0.0530 (12)	0.0635 (14)	0.0487 (12)	−0.0126 (11)	−0.0120 (9)	0.0030 (10)
C23	0.0533 (12)	0.0564 (12)	0.0483 (11)	−0.0205 (10)	−0.0099 (9)	0.0038 (9)
C24	0.0591 (14)	0.0552 (14)	0.0684 (15)	−0.0133 (11)	−0.0091 (12)	0.0029 (11)
C25	0.0785 (18)	0.0565 (15)	0.105 (2)	−0.0147 (13)	−0.0237 (16)	0.0202 (14)

S1—C16	1.747 (2)	C9—H9	0.9300
S1—C1	1.752 (2)	C10—H10	0.9300
O1—C11	1.194 (3)	C12—C13	1.447 (4)
O2—C11	1.321 (3)	C12—H12A	0.9700
O2—C12	1.448 (3)	C12—H12B	0.9700
O3—C15	1.204 (2)	C13—H13A	0.9600
O4—C24	1.341 (3)	C13—H13B	0.9600
O4—C19	1.402 (2)	C13—H13C	0.9600
O5—C24	1.183 (3)	C14—H14A	0.9600
N1—C1	1.270 (3)	C14—H14B	0.9600
N1—C4	1.412 (3)	C14—H14C	0.9600
N2—C1	1.363 (2)	C15—C16	1.487 (3)
N2—C15	1.382 (2)	C16—C17	1.336 (3)
N2—C2	1.479 (2)	C17—C18	1.451 (3)
C2—C5	1.518 (2)	C17—H17	0.9300
C2—C3	1.523 (3)	C18—C23	1.391 (3)
C2—H2	0.9800	C18—C19	1.397 (3)
C3—C4	1.339 (3)	C19—C20	1.373 (3)
C3—C11	1.473 (3)	C20—C21	1.380 (3)
C4—C14	1.501 (3)	C20—H20	0.9300
C5—C10	1.373 (3)	C21—C22	1.370 (3)
C5—C6	1.379 (3)	C21—H21	0.9300
C6—C7	1.377 (3)	C22—C23	1.375 (3)
C6—H6	0.9300	C22—H22	0.9300
C7—C8	1.364 (4)	C23—H23	0.9300
C7—H7	0.9300	C24—C25	1.481 (3)
C8—C9	1.365 (4)	C25—H25A	0.9600
C8—H8	0.9300	C25—H25B	0.9600
C9—C10	1.385 (3)	C25—H25C	0.9600
C16—S1—C1	91.39 (9)	C12—C13—H13A	109.5
C11—O2—C12	116.05 (18)	C12—C13—H13B	109.5
C24—O4—C19	118.48 (17)	H13A—C13—H13B	109.5
C1—N1—C4	116.62 (18)	C12—C13—H13C	109.5
C1—N2—C15	116.40 (16)	H13A—C13—H13C	109.5
C1—N2—C2	121.05 (16)	H13B—C13—H13C	109.5
C15—N2—C2	122.13 (15)	C4—C14—H14A	109.5
N1—C1—N2	126.93 (18)	C4—C14—H14B	109.5
N1—C1—S1	121.26 (15)	H14A—C14—H14B	109.5
N2—C1—S1	111.80 (14)	C4—C14—H14C	109.5
N2—C2—C5	109.63 (14)	H14A—C14—H14C	109.5
N2—C2—C3	107.89 (15)	H14B—C14—H14C	109.5
C5—C2—C3	112.53 (15)	O3—C15—N2	123.80 (17)
N2—C2—H2	108.9	O3—C15—C16	126.21 (18)
C5—C2—H2	108.9	N2—C15—C16	109.98 (16)
C3—C2—H2	108.9	C17—C16—C15	119.85 (18)
C4—C3—C11	121.68 (19)	C17—C16—S1	129.76 (16)
C4—C3—C2	122.34 (18)	C15—C16—S1	110.33 (14)
C11—C3—C2	115.93 (17)	C16—C17—C18	130.97 (19)
C3—C4—N1	122.26 (19)	C16—C17—H17	114.5
C3—C4—C14	126.5 (2)	C18—C17—H17	114.5
N1—C4—C14	111.25 (19)	C23—C18—C19	116.47 (18)
C10—C5—C6	118.94 (18)	C23—C18—C17	124.65 (19)
C10—C5—C2	120.72 (17)	C19—C18—C17	118.87 (18)
C6—C5—C2	120.33 (17)	C20—C19—C18	122.2 (2)
C7—C6—C5	120.7 (2)	C20—C19—O4	119.12 (19)
C7—C6—H6	119.6	C18—C19—O4	118.50 (18)
C5—C6—H6	119.6	C19—C20—C21	119.4 (2)
C8—C7—C6	120.0 (2)	C19—C20—H20	120.3
C8—C7—H7	120.0	C21—C20—H20	120.3
C6—C7—H7	120.0	C22—C21—C20	120.1 (2)
C7—C8—C9	119.8 (2)	C22—C21—H21	119.9
C7—C8—H8	120.1	C20—C21—H21	119.9
C9—C8—H8	120.1	C21—C22—C23	120.0 (2)
C8—C9—C10	120.5 (2)	C21—C22—H22	120.0
C8—C9—H9	119.8	C23—C22—H22	120.0
C10—C9—H9	119.8	C22—C23—C18	121.9 (2)
C5—C10—C9	120.0 (2)	C22—C23—H23	119.1
C5—C10—H10	120.0	C18—C23—H23	119.1
C9—C10—H10	120.0	O5—C24—O4	121.8 (2)
O1—C11—O2	121.8 (2)	O5—C24—C25	126.7 (3)
O1—C11—C3	126.4 (2)	O4—C24—C25	111.4 (2)
O2—C11—C3	111.81 (18)	C24—C25—H25A	109.5
C13—C12—O2	108.6 (2)	C24—C25—H25B	109.5
C13—C12—H12A	110.0	H25A—C25—H25B	109.5
O2—C12—H12A	110.0	C24—C25—H25C	109.5
C13—C12—H12B	110.0	H25A—C25—H25C	109.5
O2—C12—H12B	110.0	H25B—C25—H25C	109.5
H12A—C12—H12B	108.4
C4—N1—C1—N2	2.8 (3)	C12—O2—C11—C3	−176.56 (17)
C4—N1—C1—S1	−175.81 (16)	C4—C3—C11—O1	9.3 (4)
C15—N2—C1—N1	−175.5 (2)	C2—C3—C11—O1	−168.3 (2)
C2—N2—C1—N1	11.7 (3)	C4—C3—C11—O2	−172.59 (19)
C15—N2—C1—S1	3.2 (2)	C2—C3—C11—O2	9.8 (2)
C2—N2—C1—S1	−169.56 (13)	C11—O2—C12—C13	−179.7 (2)
C16—S1—C1—N1	177.52 (19)	C1—N2—C15—O3	177.60 (18)
C16—S1—C1—N2	−1.30 (15)	C2—N2—C15—O3	−9.7 (3)
C1—N2—C2—C5	103.91 (19)	C1—N2—C15—C16	−3.7 (2)
C15—N2—C2—C5	−68.5 (2)	C2—N2—C15—C16	168.97 (15)
C1—N2—C2—C3	−18.9 (2)	O3—C15—C16—C17	3.7 (3)
C15—N2—C2—C3	168.69 (16)	N2—C15—C16—C17	−174.93 (17)
N2—C2—C3—C4	15.1 (3)	O3—C15—C16—S1	−178.82 (17)
C5—C2—C3—C4	−106.0 (2)	N2—C15—C16—S1	2.55 (19)
N2—C2—C3—C11	−167.40 (15)	C1—S1—C16—C17	176.4 (2)
C5—C2—C3—C11	71.5 (2)	C1—S1—C16—C15	−0.73 (14)
C11—C3—C4—N1	179.53 (19)	C15—C16—C17—C18	174.58 (18)
C2—C3—C4—N1	−3.1 (3)	S1—C16—C17—C18	−2.3 (3)
C11—C3—C4—C14	0.7 (4)	C16—C17—C18—C23	5.5 (3)
C2—C3—C4—C14	178.1 (2)	C16—C17—C18—C19	−174.4 (2)
C1—N1—C4—C3	−7.1 (3)	C23—C18—C19—C20	−1.4 (3)
C1—N1—C4—C14	171.9 (2)	C17—C18—C19—C20	178.47 (19)
N2—C2—C5—C10	114.6 (2)	C23—C18—C19—O4	173.64 (17)
C3—C2—C5—C10	−125.3 (2)	C17—C18—C19—O4	−6.5 (3)
N2—C2—C5—C6	−64.7 (2)	C24—O4—C19—C20	−89.8 (2)
C3—C2—C5—C6	55.3 (2)	C24—O4—C19—C18	94.9 (2)
C10—C5—C6—C7	−0.7 (3)	C18—C19—C20—C21	1.3 (3)
C2—C5—C6—C7	178.63 (19)	O4—C19—C20—C21	−173.78 (19)
C5—C6—C7—C8	0.3 (4)	C19—C20—C21—C22	−0.2 (3)
C6—C7—C8—C9	0.6 (4)	C20—C21—C22—C23	−0.6 (3)
C7—C8—C9—C10	−1.1 (4)	C21—C22—C23—C18	0.4 (3)
C6—C5—C10—C9	0.3 (3)	C19—C18—C23—C22	0.6 (3)
C2—C5—C10—C9	−179.1 (2)	C17—C18—C23—C22	−179.28 (19)
C8—C9—C10—C5	0.6 (4)	C19—O4—C24—O5	5.5 (4)
C12—O2—C11—O1	1.7 (3)	C19—O4—C24—C25	−172.2 (2)

Cg1 is the centroid of the S1/C1/N2/C15/C16 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O5i	0.98	2.58	3.532 (3)	163
C12—H12a···Cg1i	0.97	2.98	3.902 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S1/C1/N2/C15/C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O5i	0.98	2.58	3.532 (3)	163
C12—H12a⋯Cg1i	0.97	2.98	3.902 (3)	160

Symmetry code: (i) .