Methyl 5-(4-acet-oxy-phen-yl)-2-(2-bromo-benzyl-idine)-7-methyl-3-oxo-2,3-di-hydro-5H-1,3-thia-zolo[3,2-a]pyrimidine-6-carboxyl-ate.

In the title mol-ecule, C24H19BrN2O5S, the pyrimidine ring is in a flattened half-chair conformation and the 4-acet-oxy-phenyl group is substituted axially to this ring. The thia-zole ring is essentially planar [with a maximum deviation of 0.012 (2) Å for the N atom] and forms dihedral angles of 17.65 (13) and 88.95 (11)° with the bromo- and acet-oxy-substituted benzene rings, respectively. The dihedral angle between the benzene rings is 81.84 (13) Å. In the crystal, pairs of weak C-H⋯O hydrogen bonds lead to the formation of inversion dimers. A weak C-H⋯π inter-action and π-π stacking inter-actions with centroid-centroid distances of 3.5903 (14) Å are observed.

Related literature

For the biological activity of di­hydro­pyrimidines, see: Alam et al. (2010 ▶); Kappe (2000 ▶); Atwal et al. (1991 ▶); Rovnyak et al. (1992 ▶). For related structures, see: Nagarajaiah et al. (2011 ▶, 2012 ▶). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C24H19BrN2O5S

M = 527.38

Triclinic,

a = 7.6018 (5) Å

b = 11.9648 (7) Å

c = 14.0877 (9) Å

α = 106.425 (1)°

β = 104.700 (2)°

γ = 106.296 (1)°

V = 1099.75 (12) Å3

Z = 2

Mo Kα radiation

μ = 2.00 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 = 0.714, T max = 0.740

9029 measured reflections

4777 independent reflections

3989 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.096

S = 1.05

4777 reflections

301 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.61 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/S1600536813019132/lh5628sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019132/lh5628Isup2.hkl

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

C24H19BrN2O5S	Z = 2
Mr = 527.38	F(000) = 536
Triclinic, P1	Dx = 1.593 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6018 (5) Å	Cell parameters from 4777 reflections
b = 11.9648 (7) Å	θ = 2.8–27.0°
c = 14.0877 (9) Å	µ = 2.00 mm−1
α = 106.425 (1)°	T = 296 K
β = 104.700 (2)°	Block, yellow
γ = 106.296 (1)°	0.18 × 0.16 × 0.16 mm
V = 1099.75 (12) Å3

Bruker SMART APEX CCD detector diffractometer	4777 independent reflections
Radiation source: fine-focus sealed tube	3989 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −7→9
Tmin = 0.714, Tmax = 0.740	k = −15→15
9029 measured reflections	l = −17→16

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0443P)2 + 0.7937P] where P = (Fo2 + 2Fc2)/3
4777 reflections	(Δ/σ)max < 0.001
301 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.61 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
C1	0.3032 (4)	0.5765 (2)	0.84902 (18)	0.0216 (5)
H1A	0.4212	0.6045	0.9093	0.032*
H1B	0.2507	0.4862	0.8164	0.032*
H1C	0.2083	0.6040	0.8716	0.032*
C2	0.3542 (3)	0.5692 (2)	0.42420 (17)	0.0137 (4)
C3	0.4784 (3)	0.6889 (2)	0.51728 (17)	0.0135 (4)
C4	0.6434 (4)	0.9217 (2)	1.08072 (18)	0.0294 (6)
H4A	0.7732	0.9210	1.1031	0.044*
H4B	0.5811	0.9043	1.1291	0.044*
H4C	0.6517	1.0030	1.0800	0.044*
C5	0.5037 (3)	0.7934 (2)	0.70450 (16)	0.0125 (4)
H5	0.6450	0.8395	0.7254	0.015*
C6	0.4688 (3)	0.7494 (2)	0.79134 (17)	0.0139 (4)
C7	0.3495 (3)	0.6308 (2)	0.77040 (17)	0.0141 (4)
C8	0.5830 (3)	0.8511 (2)	0.89783 (17)	0.0164 (5)
C9	0.3027 (3)	0.5690 (2)	0.59347 (17)	0.0129 (4)
C10	0.2005 (3)	0.8465 (2)	0.67420 (17)	0.0164 (5)
H10	0.1380	0.7744	0.6844	0.020*
C11	0.3962 (3)	0.8789 (2)	0.68289 (16)	0.0129 (4)
C12	0.4888 (3)	0.9866 (2)	0.66788 (18)	0.0169 (5)
H12	0.6196	1.0090	0.6737	0.020*
C13	0.3871 (4)	1.0614 (2)	0.64419 (18)	0.0196 (5)
H13	0.4489	1.1333	0.6336	0.024*
C14	0.1933 (4)	1.0274 (2)	0.63663 (17)	0.0177 (5)
C15	0.0973 (3)	0.9204 (2)	0.65043 (19)	0.0190 (5)
H15	−0.0339	0.8980	0.6440	0.023*
C16	0.0214 (4)	1.1615 (2)	0.6767 (2)	0.0237 (5)
C17	−0.0856 (4)	1.2323 (2)	0.6298 (2)	0.0259 (6)
H17A	−0.1463	1.2671	0.6763	0.039*
H17B	−0.1848	1.1760	0.5620	0.039*
H17C	0.0057	1.2991	0.6213	0.039*
C18	0.3621 (3)	0.5584 (2)	0.32793 (17)	0.0145 (4)
H18	0.4543	0.6275	0.3266	0.017*
C19	0.2483 (3)	0.4550 (2)	0.22544 (18)	0.0163 (5)
C20	0.1439 (3)	0.3325 (2)	0.21514 (19)	0.0180 (5)
H20	0.1464	0.3160	0.2760	0.022*
C21	0.0370 (4)	0.2353 (2)	0.1167 (2)	0.0244 (5)
H21	−0.0314	0.1550	0.1121	0.029*
C22	0.0323 (4)	0.2580 (3)	0.0253 (2)	0.0322 (6)
H22	−0.0401	0.1931	−0.0408	0.039*
C23	0.1350 (5)	0.3770 (3)	0.0321 (2)	0.0355 (7)
H23	0.1331	0.3922	−0.0293	0.043*
C24	0.2407 (4)	0.4736 (2)	0.13075 (19)	0.0257 (6)
Br1	0.37745 (6)	0.63467 (3)	0.13393 (2)	0.04578 (13)
N1	0.4376 (3)	0.68110 (17)	0.60657 (14)	0.0122 (4)
N2	0.2509 (3)	0.53974 (17)	0.66529 (14)	0.0150 (4)
O1	0.5953 (2)	0.78204 (15)	0.51788 (12)	0.0176 (3)
O2	0.7097 (2)	0.94816 (15)	0.91182 (13)	0.0216 (4)
O3	0.5290 (3)	0.82642 (16)	0.97517 (13)	0.0251 (4)
O4	0.0946 (3)	1.10282 (16)	0.60848 (13)	0.0243 (4)
O5	0.0390 (4)	1.1543 (2)	0.76119 (17)	0.0451 (6)
S1	0.20567 (8)	0.46190 (5)	0.46166 (4)	0.01442 (13)

	U11	U22	U33	U12	U13	U23
C1	0.0278 (13)	0.0208 (12)	0.0168 (11)	0.0060 (10)	0.0100 (10)	0.0095 (9)
C2	0.0122 (11)	0.0147 (10)	0.0162 (10)	0.0067 (9)	0.0051 (9)	0.0073 (9)
C3	0.0142 (11)	0.0164 (11)	0.0136 (10)	0.0087 (9)	0.0055 (8)	0.0076 (9)
C4	0.0452 (17)	0.0241 (13)	0.0095 (11)	0.0075 (12)	0.0061 (11)	0.0022 (10)
C5	0.0119 (10)	0.0130 (10)	0.0105 (9)	0.0036 (8)	0.0030 (8)	0.0036 (8)
C6	0.0152 (11)	0.0178 (11)	0.0109 (10)	0.0093 (9)	0.0047 (8)	0.0055 (9)
C7	0.0158 (11)	0.0173 (11)	0.0124 (10)	0.0081 (9)	0.0065 (9)	0.0070 (9)
C8	0.0202 (12)	0.0189 (11)	0.0129 (10)	0.0118 (10)	0.0047 (9)	0.0067 (9)
C9	0.0119 (10)	0.0137 (10)	0.0130 (10)	0.0062 (9)	0.0031 (8)	0.0051 (8)
C10	0.0162 (11)	0.0138 (10)	0.0167 (11)	0.0028 (9)	0.0054 (9)	0.0057 (9)
C11	0.0150 (11)	0.0131 (10)	0.0081 (9)	0.0044 (9)	0.0032 (8)	0.0021 (8)
C12	0.0165 (11)	0.0170 (11)	0.0180 (11)	0.0059 (9)	0.0087 (9)	0.0061 (9)
C13	0.0283 (13)	0.0149 (11)	0.0195 (11)	0.0085 (10)	0.0119 (10)	0.0090 (9)
C14	0.0257 (13)	0.0187 (11)	0.0119 (10)	0.0139 (10)	0.0058 (9)	0.0055 (9)
C15	0.0138 (11)	0.0199 (11)	0.0216 (11)	0.0062 (9)	0.0040 (9)	0.0079 (9)
C16	0.0229 (13)	0.0229 (12)	0.0249 (13)	0.0114 (11)	0.0065 (10)	0.0075 (10)
C17	0.0267 (14)	0.0229 (13)	0.0294 (13)	0.0148 (11)	0.0075 (11)	0.0085 (11)
C18	0.0148 (11)	0.0145 (10)	0.0152 (10)	0.0067 (9)	0.0055 (9)	0.0058 (9)
C19	0.0153 (11)	0.0206 (11)	0.0150 (10)	0.0100 (10)	0.0059 (9)	0.0061 (9)
C20	0.0148 (11)	0.0212 (12)	0.0186 (11)	0.0080 (10)	0.0076 (9)	0.0060 (9)
C21	0.0181 (12)	0.0206 (12)	0.0249 (13)	0.0029 (10)	0.0067 (10)	0.0005 (10)
C22	0.0327 (15)	0.0285 (14)	0.0182 (12)	0.0047 (12)	0.0028 (11)	−0.0027 (11)
C23	0.0506 (18)	0.0353 (16)	0.0148 (12)	0.0130 (14)	0.0091 (12)	0.0072 (11)
C24	0.0346 (15)	0.0217 (12)	0.0172 (12)	0.0082 (11)	0.0081 (11)	0.0059 (10)
Br1	0.0837 (3)	0.02598 (16)	0.01761 (15)	0.00523 (15)	0.01693 (15)	0.01100 (11)
N1	0.0133 (9)	0.0127 (9)	0.0109 (8)	0.0053 (7)	0.0046 (7)	0.0046 (7)
N2	0.0154 (9)	0.0158 (9)	0.0133 (9)	0.0043 (8)	0.0053 (7)	0.0063 (7)
O1	0.0202 (8)	0.0156 (8)	0.0158 (8)	0.0038 (7)	0.0076 (7)	0.0063 (6)
O2	0.0247 (9)	0.0173 (8)	0.0163 (8)	0.0032 (7)	0.0052 (7)	0.0041 (7)
O3	0.0368 (11)	0.0193 (8)	0.0110 (8)	0.0030 (8)	0.0080 (7)	0.0027 (7)
O4	0.0357 (10)	0.0278 (9)	0.0220 (9)	0.0226 (8)	0.0133 (8)	0.0143 (7)
O5	0.0676 (16)	0.0675 (16)	0.0336 (11)	0.0522 (14)	0.0300 (11)	0.0293 (11)
S1	0.0143 (3)	0.0142 (3)	0.0112 (2)	0.0025 (2)	0.0034 (2)	0.0038 (2)

C1—C7	1.500 (3)	C11—C12	1.385 (3)
C1—H1A	0.9600	C12—C13	1.391 (3)
C1—H1B	0.9600	C12—H12	0.9300
C1—H1C	0.9600	C13—C14	1.381 (4)
C2—C18	1.344 (3)	C13—H13	0.9300
C2—C3	1.487 (3)	C14—C15	1.378 (3)
C2—S1	1.754 (2)	C14—O4	1.402 (3)
C3—O1	1.211 (3)	C15—H15	0.9300
C3—N1	1.391 (3)	C16—O5	1.195 (3)
C4—O3	1.448 (3)	C16—O4	1.354 (3)
C4—H4A	0.9600	C16—C17	1.497 (3)
C4—H4B	0.9600	C17—H17A	0.9600
C4—H4C	0.9600	C17—H17B	0.9600
C5—N1	1.478 (3)	C17—H17C	0.9600
C5—C6	1.515 (3)	C18—C19	1.456 (3)
C5—C11	1.525 (3)	C18—H18	0.9300
C5—H5	0.9800	C19—C24	1.403 (3)
C6—C7	1.352 (3)	C19—C20	1.403 (3)
C6—C8	1.483 (3)	C20—C21	1.387 (3)
C7—N2	1.417 (3)	C20—H20	0.9300
C8—O2	1.209 (3)	C21—C22	1.382 (4)
C8—O3	1.335 (3)	C21—H21	0.9300
C9—N2	1.275 (3)	C22—C23	1.381 (4)
C9—N1	1.370 (3)	C22—H22	0.9300
C9—S1	1.750 (2)	C23—C24	1.384 (4)
C10—C15	1.391 (3)	C23—H23	0.9300
C10—C11	1.391 (3)	C24—Br1	1.898 (3)
C10—H10	0.9300
C7—C1—H1A	109.5	C14—C13—H13	120.4
C7—C1—H1B	109.5	C12—C13—H13	120.4
H1A—C1—H1B	109.5	C15—C14—C13	121.7 (2)
C7—C1—H1C	109.5	C15—C14—O4	121.2 (2)
H1A—C1—H1C	109.5	C13—C14—O4	117.1 (2)
H1B—C1—H1C	109.5	C14—C15—C10	118.7 (2)
C18—C2—C3	119.9 (2)	C14—C15—H15	120.7
C18—C2—S1	129.72 (18)	C10—C15—H15	120.7
C3—C2—S1	110.36 (16)	O5—C16—O4	123.4 (2)
O1—C3—N1	123.4 (2)	O5—C16—C17	126.0 (2)
O1—C3—C2	126.8 (2)	O4—C16—C17	110.6 (2)
N1—C3—C2	109.76 (19)	C16—C17—H17A	109.5
O3—C4—H4A	109.5	C16—C17—H17B	109.5
O3—C4—H4B	109.5	H17A—C17—H17B	109.5
H4A—C4—H4B	109.5	C16—C17—H17C	109.5
O3—C4—H4C	109.5	H17A—C17—H17C	109.5
H4A—C4—H4C	109.5	H17B—C17—H17C	109.5
H4B—C4—H4C	109.5	C2—C18—C19	129.8 (2)
N1—C5—C6	108.19 (17)	C2—C18—H18	115.1
N1—C5—C11	109.45 (16)	C19—C18—H18	115.1
C6—C5—C11	113.06 (18)	C24—C19—C20	116.4 (2)
N1—C5—H5	108.7	C24—C19—C18	120.8 (2)
C6—C5—H5	108.7	C20—C19—C18	122.8 (2)
C11—C5—H5	108.7	C21—C20—C19	121.8 (2)
C7—C6—C8	126.3 (2)	C21—C20—H20	119.1
C7—C6—C5	122.34 (19)	C19—C20—H20	119.1
C8—C6—C5	111.35 (19)	C22—C21—C20	119.9 (2)
C6—C7—N2	121.6 (2)	C22—C21—H21	120.1
C6—C7—C1	127.3 (2)	C20—C21—H21	120.1
N2—C7—C1	111.08 (19)	C23—C22—C21	120.1 (2)
O2—C8—O3	123.7 (2)	C23—C22—H22	119.9
O2—C8—C6	122.5 (2)	C21—C22—H22	119.9
O3—C8—C6	113.8 (2)	C22—C23—C24	119.6 (3)
N2—C9—N1	126.87 (19)	C22—C23—H23	120.2
N2—C9—S1	121.52 (17)	C24—C23—H23	120.2
N1—C9—S1	111.59 (16)	C23—C24—C19	122.2 (2)
C15—C10—C11	120.8 (2)	C23—C24—Br1	117.3 (2)
C15—C10—H10	119.6	C19—C24—Br1	120.52 (18)
C11—C10—H10	119.6	C9—N1—C3	116.59 (18)
C12—C11—C10	119.3 (2)	C9—N1—C5	120.26 (18)
C12—C11—C5	120.8 (2)	C3—N1—C5	122.05 (18)
C10—C11—C5	119.8 (2)	C9—N2—C7	116.48 (19)
C11—C12—C13	120.4 (2)	C8—O3—C4	115.0 (2)
C11—C12—H12	119.8	C16—O4—C14	118.97 (19)
C13—C12—H12	119.8	C9—S1—C2	91.67 (11)
C14—C13—C12	119.1 (2)
C18—C2—C3—O1	−1.9 (4)	C19—C20—C21—C22	0.3 (4)
S1—C2—C3—O1	−179.35 (19)	C20—C21—C22—C23	0.5 (4)
C18—C2—C3—N1	176.6 (2)	C21—C22—C23—C24	−0.7 (5)
S1—C2—C3—N1	−0.9 (2)	C22—C23—C24—C19	0.2 (5)
N1—C5—C6—C7	−16.1 (3)	C22—C23—C24—Br1	−179.8 (2)
C11—C5—C6—C7	105.3 (2)	C20—C19—C24—C23	0.5 (4)
N1—C5—C6—C8	162.92 (17)	C18—C19—C24—C23	179.5 (3)
C11—C5—C6—C8	−75.7 (2)	C20—C19—C24—Br1	−179.49 (17)
C8—C6—C7—N2	−178.3 (2)	C18—C19—C24—Br1	−0.4 (3)
C5—C6—C7—N2	0.6 (3)	N2—C9—N1—C3	176.5 (2)
C8—C6—C7—C1	1.2 (4)	S1—C9—N1—C3	−2.1 (2)
C5—C6—C7—C1	−179.9 (2)	N2—C9—N1—C5	−15.3 (3)
C7—C6—C8—O2	168.1 (2)	S1—C9—N1—C5	166.10 (15)
C5—C6—C8—O2	−10.9 (3)	O1—C3—N1—C9	−179.5 (2)
C7—C6—C8—O3	−13.6 (3)	C2—C3—N1—C9	2.0 (3)
C5—C6—C8—O3	167.38 (18)	O1—C3—N1—C5	12.5 (3)
C15—C10—C11—C12	0.2 (3)	C2—C3—N1—C5	−166.05 (18)
C15—C10—C11—C5	−177.5 (2)	C6—C5—N1—C9	22.8 (3)
N1—C5—C11—C12	−102.4 (2)	C11—C5—N1—C9	−100.8 (2)
C6—C5—C11—C12	137.0 (2)	C6—C5—N1—C3	−169.64 (18)
N1—C5—C11—C10	75.3 (2)	C11—C5—N1—C3	66.8 (2)
C6—C5—C11—C10	−45.4 (3)	N1—C9—N2—C7	−2.9 (3)
C10—C11—C12—C13	−0.1 (3)	S1—C9—N2—C7	175.63 (15)
C5—C11—C12—C13	177.53 (19)	C6—C7—N2—C9	10.2 (3)
C11—C12—C13—C14	0.5 (3)	C1—C7—N2—C9	−169.4 (2)
C12—C13—C14—C15	−1.0 (3)	O2—C8—O3—C4	−4.2 (3)
C12—C13—C14—O4	−177.54 (19)	C6—C8—O3—C4	177.6 (2)
C13—C14—C15—C10	1.0 (3)	O5—C16—O4—C14	1.3 (4)
O4—C14—C15—C10	177.5 (2)	C17—C16—O4—C14	−177.5 (2)
C11—C10—C15—C14	−0.6 (3)	C15—C14—O4—C16	63.7 (3)
C3—C2—C18—C19	−176.1 (2)	C13—C14—O4—C16	−119.7 (2)
S1—C2—C18—C19	0.8 (4)	N2—C9—S1—C2	−177.4 (2)
C2—C18—C19—C24	163.0 (2)	N1—C9—S1—C2	1.26 (17)
C2—C18—C19—C20	−18.0 (4)	C18—C2—S1—C9	−177.3 (2)
C24—C19—C20—C21	−0.7 (3)	C3—C2—S1—C9	−0.18 (16)
C18—C19—C20—C21	−179.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1i	0.93	2.60	3.343 (4)	138
C10—H10···Cgii	0.93	2.61	3.513 (4)	147

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C5–C7/C9/N1/N2 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O1i	0.93	2.60	3.343 (4)	138
C10—H10⋯Cg ii	0.93	2.61	3.513 (4)	147

Symmetry codes: (i) ; (ii) .