Methyl 2-(2-bromo-benzyl-idene)-5-(4-hy-droxy-phen-yl)-7-methyl-3-oxo-2,3-dihydro-5H-1,3-thia-zolo[3,2-a]pyrimidine-6-carboxyl-ate.

In the title compound, C(22)H(17)BrN(2)O(4)S, the central dihydropyrimidine ring, with a chiral C atom, is significantly puckered and adopts a half-chair conformation with the chiral C atom displaced from the mean plane of the remaining ring atoms by 0.305 (6) Å. The hydroxy-phenyl ring is positioned axially to the pyrimidine ring and almost bisects it, the dihedral angle between the mean-planes of the two rings being 89.78 (12)°. The meth-oxy-carbonyl group is disordered over two sites with an occupancy ratio of 0.568 (5):0.432 (5), resulting in a major and a minor conformer. In the crystal, O-H⋯N and C-H⋯S inter-actions result in sheets along the c axis. The supra-molecular assembly is stabilized by π-π stacking inter-actions between the 2-bromo-benzyl-idene and thia-zolopyrimidine rings [centroid-centroid distance = 3.632 (1) Å]. In addition, C-H⋯π inter-actions are also observed in the crystal structure.

Related literature

For therapeutic and medicinal properties of thia­zolopyrimidine derivatives, see: Kappe (2000 ▶); Ozair et al. (2010 ▶). For a related structure, see: Nagarajaiah & Begum (2011 ▶).

Experimental

Crystal data

C22H17BrN2O4S

M = 485.35

Monoclinic,

a = 9.851 (2) Å

b = 23.461 (6) Å

c = 9.416 (2) Å

β = 111.229 (5)°

V = 2028.5 (8) Å3

Z = 4

Mo Kα radiation

μ = 2.16 mm−1

T = 296 K

0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer

Absorption correction: multi-scan (SADABS, Bruker, 1998 ▶) T min = 0.697, T max = 0.724

12267 measured reflections

4409 independent reflections

2563 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.178

S = 1.04

4409 reflections

286 parameters

H-atom parameters constrained

Δρmax = 1.04 e Å−3

Δρmin = −0.87 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 (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812013311/pv2521sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812013311/pv2521Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812013311/pv2521Isup3.cml

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

C22H17BrN2O4S	F(000) = 984
Mr = 485.35	Dx = 1.589 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4409 reflections
a = 9.851 (2) Å	θ = 2.2–27.0°
b = 23.461 (6) Å	µ = 2.16 mm−1
c = 9.416 (2) Å	T = 296 K
β = 111.229 (5)°	Block, yellow
V = 2028.5 (8) Å3	0.18 × 0.16 × 0.16 mm
Z = 4

Bruker SMART APEX CCD detector diffractometer	4409 independent reflections
Radiation source: fine-focus sealed tube	2563 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω scans	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS, Bruker, 1998)	h = −12→7
Tmin = 0.697, Tmax = 0.724	k = −28→29
12267 measured reflections	l = −11→12

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.178	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0878P)2] where P = (Fo2 + 2Fc2)/3
4409 reflections	(Δ/σ)max < 0.001
286 parameters	Δρmax = 1.04 e Å−3
0 restraints	Δρmin = −0.87 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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	Occ. (<1)
Br1	0.94209 (7)	0.12175 (2)	0.43004 (8)	0.0693 (3)
S1	0.69429 (13)	−0.08352 (5)	0.61655 (13)	0.0406 (3)
O1	0.5280 (4)	−0.00179 (13)	0.2404 (4)	0.0585 (10)
O4	0.6120 (3)	−0.20100 (12)	−0.1933 (3)	0.0375 (7)
H4	0.5719	−0.1881	−0.2794	0.056*
N1	0.4855 (4)	−0.08217 (14)	0.3536 (4)	0.0380 (9)
N2	0.4767 (4)	−0.15870 (15)	0.5130 (4)	0.0376 (9)
C1	0.2725 (5)	−0.2232 (2)	0.4575 (6)	0.0498 (12)
H1A	0.1688	−0.2180	0.4190	0.075*
H1B	0.3083	−0.2233	0.5668	0.075*
H1C	0.2955	−0.2589	0.4216	0.075*
C2	0.6896 (5)	−0.02716 (17)	0.4936 (5)	0.0395 (11)
C3	0.5627 (6)	−0.03336 (18)	0.3500 (5)	0.0430 (12)
C5	0.3714 (5)	−0.1052 (2)	0.2168 (5)	0.0434 (12)
H5	0.3047	−0.0741	0.1666	0.052*
C6	0.2857 (5)	−0.1505 (2)	0.2668 (5)	0.0455 (12)
C7	0.3424 (5)	−0.17558 (19)	0.4030 (5)	0.0406 (11)
C9	0.5358 (5)	−0.11320 (17)	0.4837 (5)	0.0348 (10)
C10	0.4374 (5)	−0.12880 (17)	0.1052 (5)	0.0374 (10)
C11	0.5353 (5)	−0.17425 (18)	0.1479 (5)	0.0379 (10)
H11	0.5612	−0.1893	0.2456	0.045*
C12	0.5942 (5)	−0.19733 (17)	0.0490 (5)	0.0348 (10)
H12	0.6610	−0.2270	0.0803	0.042*
C13	0.5535 (5)	−0.17610 (17)	−0.0963 (5)	0.0347 (10)
C14	0.4570 (5)	−0.13072 (17)	−0.1407 (5)	0.0387 (11)
H14	0.4306	−0.1158	−0.2386	0.046*
C15	0.4003 (6)	−0.1078 (2)	−0.0394 (5)	0.0466 (12)
H15	0.3356	−0.0774	−0.0699	0.056*
C16	0.7832 (6)	0.01649 (18)	0.5097 (6)	0.0474 (13)
H16	0.7560	0.0414	0.4274	0.057*
C17	0.9172 (6)	0.03188 (19)	0.6303 (6)	0.0490 (13)
C18	0.9740 (6)	0.0014 (2)	0.7658 (6)	0.0521 (13)
H18	0.9223	−0.0296	0.7817	0.063*
C19	1.1042 (6)	0.0158 (2)	0.8764 (7)	0.0606 (15)
H19	1.1399	−0.0052	0.9660	0.073*
C20	1.1822 (6)	0.0617 (3)	0.8549 (8)	0.0702 (18)
H20	1.2711	0.0711	0.9295	0.084*
C21	1.1297 (7)	0.0930 (2)	0.7252 (8)	0.0658 (17)
H21	1.1810	0.1246	0.7121	0.079*
C22	1.0006 (6)	0.0778 (2)	0.6137 (7)	0.0571 (15)
O2A	0.0777 (8)	−0.2032 (3)	0.1381 (8)	0.0398 (15)	0.568 (5)
O3A	0.1029 (9)	−0.1203 (3)	0.0273 (9)	0.0478 (18)	0.568 (5)
C8A	0.1483 (11)	−0.1543 (4)	0.1338 (13)	0.0344 (18)	0.568 (5)
C4A	−0.0570 (9)	−0.2119 (4)	0.0135 (11)	0.055 (2)	0.568 (5)
H4A1	−0.0980	−0.2479	0.0256	0.083*	0.568 (5)
H4A2	−0.0397	−0.2118	−0.0805	0.083*	0.568 (5)
H4A3	−0.1237	−0.1818	0.0119	0.083*	0.568 (5)
O2B	0.0944 (12)	−0.1436 (4)	0.0420 (13)	0.0398 (15)	0.432 (5)
O3B	0.0726 (12)	−0.2187 (4)	0.1889 (12)	0.0478 (18)	0.432 (5)
C8B	0.1406 (17)	−0.1798 (6)	0.1675 (17)	0.0344 (18)	0.432 (5)
C4B	−0.0390 (12)	−0.1602 (5)	−0.0732 (13)	0.055 (2)	0.432 (5)
H4B1	−0.0667	−0.1323	−0.1532	0.083*	0.432 (5)
H4B2	−0.1135	−0.1629	−0.0302	0.083*	0.432 (5)
H4B3	−0.0269	−0.1966	−0.1139	0.083*	0.432 (5)

	U11	U22	U33	U12	U13	U23
Br1	0.0943 (5)	0.0404 (3)	0.1033 (6)	−0.0081 (3)	0.0720 (4)	−0.0062 (3)
S1	0.0530 (7)	0.0361 (6)	0.0348 (6)	−0.0079 (5)	0.0185 (5)	−0.0037 (5)
O1	0.089 (3)	0.0330 (17)	0.056 (2)	0.0130 (18)	0.029 (2)	0.0096 (17)
O4	0.0459 (19)	0.0332 (16)	0.0337 (16)	0.0035 (13)	0.0147 (15)	−0.0014 (13)
N1	0.050 (2)	0.0355 (19)	0.030 (2)	0.0093 (17)	0.0166 (17)	−0.0013 (16)
N2	0.044 (2)	0.041 (2)	0.0301 (19)	−0.0043 (18)	0.0160 (17)	−0.0071 (16)
C1	0.043 (3)	0.051 (3)	0.060 (3)	−0.008 (2)	0.025 (2)	−0.016 (3)
C2	0.061 (3)	0.026 (2)	0.041 (3)	0.004 (2)	0.031 (2)	−0.0029 (19)
C3	0.066 (3)	0.023 (2)	0.049 (3)	0.011 (2)	0.031 (3)	−0.002 (2)
C5	0.049 (3)	0.041 (2)	0.036 (3)	0.015 (2)	0.010 (2)	0.000 (2)
C6	0.038 (3)	0.054 (3)	0.043 (3)	0.009 (2)	0.013 (2)	−0.017 (2)
C7	0.043 (3)	0.040 (2)	0.045 (3)	0.004 (2)	0.023 (2)	−0.010 (2)
C9	0.044 (3)	0.034 (2)	0.030 (2)	0.006 (2)	0.019 (2)	−0.0039 (19)
C10	0.045 (3)	0.031 (2)	0.033 (2)	0.0082 (19)	0.011 (2)	−0.0016 (18)
C11	0.048 (3)	0.037 (2)	0.028 (2)	0.007 (2)	0.012 (2)	0.0058 (19)
C12	0.041 (3)	0.029 (2)	0.035 (2)	0.0046 (19)	0.014 (2)	0.0005 (18)
C13	0.042 (3)	0.030 (2)	0.033 (2)	−0.0039 (19)	0.016 (2)	−0.0048 (18)
C14	0.052 (3)	0.034 (2)	0.029 (2)	0.005 (2)	0.014 (2)	0.0027 (19)
C15	0.064 (3)	0.041 (2)	0.031 (2)	0.021 (2)	0.012 (2)	0.004 (2)
C16	0.069 (4)	0.024 (2)	0.061 (3)	0.004 (2)	0.038 (3)	−0.005 (2)
C17	0.058 (3)	0.030 (2)	0.071 (4)	−0.003 (2)	0.038 (3)	−0.015 (2)
C18	0.062 (3)	0.037 (3)	0.063 (3)	−0.010 (2)	0.030 (3)	−0.016 (3)
C19	0.066 (4)	0.052 (3)	0.063 (4)	0.004 (3)	0.023 (3)	−0.014 (3)
C20	0.055 (4)	0.071 (4)	0.091 (5)	−0.017 (3)	0.035 (3)	−0.050 (4)
C21	0.081 (5)	0.049 (3)	0.092 (5)	−0.014 (3)	0.060 (4)	−0.031 (3)
C22	0.069 (4)	0.037 (3)	0.086 (4)	−0.008 (3)	0.053 (3)	−0.023 (3)
O2A	0.031 (3)	0.038 (4)	0.048 (3)	−0.006 (3)	0.012 (3)	0.003 (3)
O3A	0.055 (4)	0.027 (3)	0.055 (4)	−0.004 (3)	0.013 (3)	0.002 (3)
C8A	0.037 (4)	0.019 (5)	0.045 (5)	0.015 (5)	0.013 (4)	0.001 (5)
C4A	0.036 (4)	0.057 (4)	0.063 (5)	0.000 (3)	0.006 (4)	0.013 (4)
O2B	0.031 (3)	0.038 (4)	0.048 (3)	−0.006 (3)	0.012 (3)	0.003 (3)
O3B	0.055 (4)	0.027 (3)	0.055 (4)	−0.004 (3)	0.013 (3)	0.002 (3)
C8B	0.037 (4)	0.019 (5)	0.045 (5)	0.015 (5)	0.013 (4)	0.001 (5)
C4B	0.036 (4)	0.057 (4)	0.063 (5)	0.000 (3)	0.006 (4)	0.013 (4)

Br1—C22	1.915 (6)	C13—C14	1.387 (6)
S1—C2	1.747 (4)	C14—C15	1.377 (7)
S1—C9	1.753 (5)	C14—H14	0.9300
O1—C3	1.215 (5)	C15—H15	0.9300
O4—C13	1.374 (5)	C16—C17	1.441 (7)
O4—H4	0.8200	C16—H16	0.9300
N1—C9	1.355 (5)	C17—C18	1.392 (7)
N1—C3	1.382 (6)	C17—C22	1.397 (7)
N1—C5	1.472 (6)	C18—C19	1.370 (7)
N2—C9	1.293 (5)	C18—H18	0.9300
N2—C7	1.410 (6)	C19—C20	1.378 (8)
C1—C7	1.497 (6)	C19—H19	0.9300
C1—H1A	0.9600	C20—C21	1.357 (9)
C1—H1B	0.9600	C20—H20	0.9300
C1—H1C	0.9600	C21—C22	1.371 (8)
C2—C16	1.349 (6)	C21—H21	0.9300
C2—C3	1.479 (7)	O2A—C8A	1.348 (11)
C5—C10	1.527 (6)	O2A—C4A	1.432 (11)
C5—C6	1.534 (7)	O3A—C8A	1.232 (12)
C5—H5	0.9800	C4A—H4A1	0.9600
C6—C7	1.336 (7)	C4A—H4A2	0.9600
C6—C8A	1.477 (12)	C4A—H4A3	0.9600
C6—C8B	1.556 (17)	O2B—C8B	1.391 (17)
C10—C15	1.367 (6)	O2B—C4B	1.423 (15)
C10—C11	1.396 (6)	O3B—C8B	1.192 (17)
C11—C12	1.374 (6)	C4B—H4B1	0.9600
C11—H11	0.9300	C4B—H4B2	0.9600
C12—C13	1.373 (6)	C4B—H4B3	0.9600
C12—H12	0.9300
C2—S1—C9	91.4 (2)	C15—C14—C13	119.7 (4)
C13—O4—H4	109.5	C15—C14—H14	120.1
C9—N1—C3	116.3 (4)	C13—C14—H14	120.1
C9—N1—C5	120.5 (4)	C10—C15—C14	121.3 (4)
C3—N1—C5	122.4 (4)	C10—C15—H15	119.3
C9—N2—C7	116.8 (4)	C14—C15—H15	119.3
C7—C1—H1A	109.5	C2—C16—C17	132.3 (5)
C7—C1—H1B	109.5	C2—C16—H16	113.9
H1A—C1—H1B	109.5	C17—C16—H16	113.9
C7—C1—H1C	109.5	C18—C17—C22	116.2 (5)
H1A—C1—H1C	109.5	C18—C17—C16	122.8 (5)
H1B—C1—H1C	109.5	C22—C17—C16	120.9 (5)
C16—C2—C3	119.6 (4)	C19—C18—C17	121.6 (5)
C16—C2—S1	130.3 (4)	C19—C18—H18	119.2
C3—C2—S1	110.0 (3)	C17—C18—H18	119.2
O1—C3—N1	122.6 (5)	C18—C19—C20	120.0 (6)
O1—C3—C2	127.0 (4)	C18—C19—H19	120.0
N1—C3—C2	110.5 (4)	C20—C19—H19	120.0
N1—C5—C10	110.8 (4)	C21—C20—C19	120.3 (6)
N1—C5—C6	108.5 (4)	C21—C20—H20	119.9
C10—C5—C6	112.2 (4)	C19—C20—H20	119.9
N1—C5—H5	108.4	C20—C21—C22	119.5 (6)
C10—C5—H5	108.4	C20—C21—H21	120.2
C6—C5—H5	108.4	C22—C21—H21	120.3
C7—C6—C8A	136.4 (6)	C21—C22—C17	122.4 (6)
C7—C6—C5	121.0 (4)	C21—C22—Br1	116.3 (4)
C8A—C6—C5	102.7 (5)	C17—C22—Br1	121.3 (4)
C7—C6—C8B	110.8 (7)	C8A—O2A—C4A	115.6 (8)
C5—C6—C8B	127.6 (7)	O3A—C8A—O2A	122.4 (10)
C6—C7—N2	122.4 (4)	O3A—C8A—C6	127.0 (9)
C6—C7—C1	125.0 (5)	O2A—C8A—C6	110.5 (8)
N2—C7—C1	112.6 (4)	O2A—C4A—H4A1	109.5
N2—C9—N1	126.2 (4)	O2A—C4A—H4A2	109.5
N2—C9—S1	122.0 (3)	H4A1—C4A—H4A2	109.5
N1—C9—S1	111.8 (3)	O2A—C4A—H4A3	109.5
C15—C10—C11	118.0 (4)	H4A1—C4A—H4A3	109.5
C15—C10—C5	121.9 (4)	H4A2—C4A—H4A3	109.5
C11—C10—C5	120.1 (4)	C8B—O2B—C4B	114.1 (10)
C12—C11—C10	121.5 (4)	O3B—C8B—O2B	125.5 (14)
C12—C11—H11	119.2	O3B—C8B—C6	133.4 (12)
C10—C11—H11	119.2	O2B—C8B—C6	100.8 (10)
C13—C12—C11	119.3 (4)	O2B—C4B—H4B1	109.5
C13—C12—H12	120.3	O2B—C4B—H4B2	109.5
C11—C12—H12	120.3	H4B1—C4B—H4B2	109.5
C12—C13—O4	117.8 (4)	O2B—C4B—H4B3	109.5
C12—C13—C14	120.0 (4)	H4B1—C4B—H4B3	109.5
O4—C13—C14	122.2 (4)	H4B2—C4B—H4B3	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···N2i	0.82	1.96	2.782 (4)	178
C4B—H4B1···S1ii	0.96	2.80	3.621 (12)	144
C1—H1C···Cg1iii	0.96	2.78	3.585 (5)	142

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C10–C15 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯N2i	0.82	1.96	2.782 (4)	178
C4B—H4B1⋯S1ii	0.96	2.80	3.621 (12)	144
C1—H1C⋯Cg1iii	0.96	2.78	3.585 (5)	142

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