Crystal structure of ethyl 2-(2-fluoro-benzyl-idene)-5-(4-fluoro-phen-yl)-7-methyl-3-oxo-2,3-di-hydro-5H-1,3-thia-zolo[3,2-a]pyrimidine-6-carb-oxy-late.

In the title mol-ecule, C23H18F2N2O3S, the 4-fluoro-substituted and 2-fluoro-substituted benzene rings form dihedral angles of 88.16 (8) and 23.1 (1)°, respectively, with the thia-zole ring. The pyrimidine ring adopts a flattened sofa conformation with the sp (3)-hydridized C atom forming the flap. In the crystal, pairs of weak C-H⋯O hydrogen bonds link mol-ecules related by twofold rotation axes, forming R (2) 2(10) rings, which are in turn linked by weak C-H⋯N inter-actions to form chains of rings along [010]. In addition, weak C-H⋯π(arene) inter-actions link the chains into layers parallel to (001) and π-π inter-actions with a centroid-centroid distance of 3.836 (10) Å connect these layers into a three-dimensional network.

Related literature

For the biological activity of fused pyrimidine derivatives, see: Alam et al. (2010a ▶,b ▶); Jotani et al. (2009 ▶). For the biological activity of fluoro-substituted compounds, see: Guru Row (1999 ▶); Yamazaki et al. (2009 ▶). For related structures, see: Krishnamurthy et al. (2014 ▶); Nagarajaiah & Begum (2011 ▶). For hydrogen-bond graph-set motifs motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C23H18F2N2O3S

M = 440.45

Monoclinic,

a = 24.746 (5) Å

b = 9.6879 (17) Å

c = 16.757 (3) Å

β = 92.022 (5)°

V = 4014.7 (13) Å3

Z = 8

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.963, T max = 0.967

9957 measured reflections

3520 independent reflections

3169 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.112

S = 1.03

3520 reflections

282 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; 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 DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814025008/lh5738sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814025008/lh5738Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814025008/lh5738Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814025008/lh5738fig1.tif

The mol­ecular structure of the title compound drawn with 50% probability level ellipsoids. H atoms are presented as small spheres of arbitrary radius.

Click here for additional data file.

. DOI: 10.1107/S1600536814025008/lh5738fig2.tif

Part of the crystal structure with hydrogen bonds shown as dashed lines. For clarity H atoms not involved in hydrogen bonding are not shown.

CCDC reference: 1034132

Additional supporting information: crystallographic information; 3D view; checkCIF report

C23H18F2N2O3S	F(000) = 1824
Mr = 440.45	Dx = 1.457 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3520 reflections
a = 24.746 (5) Å	θ = 1.7–25.0°
b = 9.6879 (17) Å	µ = 0.21 mm−1
c = 16.757 (3) Å	T = 100 K
β = 92.022 (5)°	Block, yellow
V = 4014.7 (13) Å3	0.18 × 0.16 × 0.16 mm
Z = 8

Bruker SMART APEX CCD diffractometer	3520 independent reflections
Radiation source: fine-focus sealed tube	3169 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −29→29
Tmin = 0.963, Tmax = 0.967	k = −11→11
9957 measured reflections	l = −16→19

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0629P)2 + 4.1702P] where P = (Fo2 + 2Fc2)/3
3520 reflections	(Δ/σ)max = 0.001
282 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.34 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	0.565115 (17)	0.43828 (4)	0.65490 (3)	0.02504 (15)
F1	0.43031 (4)	1.13600 (11)	0.77686 (7)	0.0351 (3)
O3	0.36126 (5)	0.76825 (13)	0.48959 (7)	0.0266 (3)
O1	0.56122 (5)	0.78762 (12)	0.54420 (7)	0.0244 (3)
N1	0.50281 (5)	0.61793 (14)	0.58253 (8)	0.0194 (3)
N2	0.45904 (6)	0.41667 (14)	0.62854 (9)	0.0238 (3)
F2	0.75173 (5)	0.66324 (14)	0.56697 (9)	0.0542 (4)
C6	0.40531 (7)	0.59402 (17)	0.56217 (10)	0.0201 (4)
O2	0.30987 (5)	0.59424 (14)	0.53122 (10)	0.0430 (4)
C5	0.45256 (6)	0.69513 (16)	0.56176 (10)	0.0196 (4)
H5	0.4553	0.7335	0.5067	0.023*
C3	0.55343 (7)	0.67752 (17)	0.57664 (9)	0.0200 (4)
C10	0.35362 (7)	0.64859 (18)	0.52739 (11)	0.0245 (4)
C15	0.44806 (7)	1.05927 (17)	0.64716 (11)	0.0257 (4)
H15	0.4531	1.1518	0.6302	0.031*
C2	0.59521 (7)	0.58692 (18)	0.61561 (10)	0.0227 (4)
C11	0.44590 (6)	0.81437 (17)	0.61988 (10)	0.0197 (4)
C17	0.64788 (7)	0.62041 (19)	0.61580 (10)	0.0254 (4)
H17	0.6564	0.7051	0.5906	0.031*
C7	0.40961 (7)	0.46736 (17)	0.59525 (10)	0.0221 (4)
C16	0.45294 (6)	0.94976 (17)	0.59459 (11)	0.0228 (4)
H16	0.4612	0.9674	0.5406	0.027*
C9	0.50089 (7)	0.49166 (17)	0.61977 (10)	0.0214 (4)
C12	0.43361 (6)	0.78875 (17)	0.69901 (10)	0.0210 (4)
H12	0.4287	0.6964	0.7165	0.025*
C13	0.42838 (7)	0.89693 (18)	0.75269 (10)	0.0236 (4)
H13	0.4201	0.8801	0.8068	0.028*
C14	0.43566 (7)	1.02957 (18)	0.72492 (11)	0.0250 (4)
C1	0.36551 (7)	0.36219 (19)	0.60085 (11)	0.0292 (4)
H1A	0.3303	0.4078	0.5942	0.044*
H1B	0.3681	0.3171	0.6532	0.044*
H1C	0.3692	0.2929	0.5588	0.044*
C18	0.69365 (7)	0.5428 (2)	0.64997 (11)	0.0285 (4)
C8	0.31251 (7)	0.8348 (2)	0.45669 (12)	0.0315 (4)
H8A	0.2865	0.8508	0.4993	0.038*
H8B	0.2950	0.7755	0.4152	0.038*
C19	0.74540 (7)	0.5658 (2)	0.62342 (11)	0.0299 (4)
C20	0.79025 (8)	0.4941 (2)	0.65104 (12)	0.0368 (5)
H20	0.8249	0.5135	0.6311	0.044*
C21	0.78402 (8)	0.3936 (3)	0.70814 (13)	0.0425 (5)
H21	0.8143	0.3413	0.7271	0.051*
C4	0.32924 (9)	0.9693 (2)	0.42117 (15)	0.0472 (6)
H4A	0.3483	1.0250	0.4621	0.071*
H4B	0.2971	1.0192	0.4011	0.071*
H4C	0.3533	0.9519	0.3771	0.071*
C22	0.73389 (9)	0.3693 (3)	0.73753 (16)	0.0636 (8)
H22	0.7296	0.3010	0.7775	0.076*
C23	0.68945 (9)	0.4436 (3)	0.70917 (14)	0.0552 (7)
H23	0.6551	0.4263	0.7308	0.066*

	U11	U22	U33	U12	U13	U23
S1	0.0253 (3)	0.0241 (3)	0.0257 (3)	0.00599 (16)	0.00118 (18)	0.00482 (17)
F1	0.0385 (6)	0.0243 (6)	0.0427 (7)	0.0029 (5)	0.0040 (5)	−0.0127 (5)
O3	0.0179 (6)	0.0298 (7)	0.0321 (7)	0.0029 (5)	0.0001 (5)	0.0065 (5)
O1	0.0208 (6)	0.0234 (6)	0.0292 (7)	0.0007 (5)	0.0034 (5)	0.0021 (5)
N1	0.0193 (7)	0.0177 (7)	0.0214 (7)	0.0029 (5)	0.0020 (6)	0.0010 (6)
N2	0.0266 (8)	0.0207 (7)	0.0243 (8)	0.0006 (6)	0.0026 (6)	0.0014 (6)
F2	0.0245 (6)	0.0584 (8)	0.0795 (10)	−0.0091 (6)	−0.0015 (6)	0.0307 (7)
C6	0.0198 (8)	0.0212 (8)	0.0195 (8)	−0.0013 (7)	0.0029 (6)	−0.0030 (7)
O2	0.0199 (7)	0.0314 (7)	0.0774 (11)	−0.0033 (6)	−0.0031 (7)	0.0116 (7)
C5	0.0171 (8)	0.0194 (8)	0.0221 (8)	0.0026 (6)	0.0005 (6)	0.0022 (7)
C3	0.0209 (8)	0.0214 (8)	0.0180 (8)	0.0017 (7)	0.0033 (6)	−0.0018 (7)
C10	0.0217 (9)	0.0222 (8)	0.0298 (9)	−0.0001 (7)	0.0032 (7)	−0.0030 (7)
C15	0.0207 (9)	0.0168 (8)	0.0399 (11)	0.0003 (6)	0.0035 (8)	0.0025 (7)
C2	0.0243 (9)	0.0264 (9)	0.0176 (8)	0.0055 (7)	0.0023 (7)	−0.0019 (7)
C11	0.0136 (7)	0.0204 (8)	0.0251 (9)	0.0011 (6)	0.0000 (6)	0.0001 (7)
C17	0.0239 (9)	0.0308 (9)	0.0217 (9)	0.0036 (7)	0.0014 (7)	−0.0013 (7)
C7	0.0233 (9)	0.0227 (8)	0.0206 (8)	−0.0002 (7)	0.0049 (7)	−0.0033 (7)
C16	0.0183 (8)	0.0228 (9)	0.0274 (9)	0.0012 (6)	0.0026 (7)	0.0030 (7)
C9	0.0257 (9)	0.0202 (8)	0.0186 (8)	0.0043 (7)	0.0026 (7)	−0.0011 (7)
C12	0.0181 (8)	0.0177 (8)	0.0271 (9)	0.0007 (6)	0.0005 (7)	0.0032 (7)
C13	0.0196 (8)	0.0265 (9)	0.0248 (9)	0.0028 (7)	0.0009 (7)	−0.0009 (7)
C14	0.0186 (8)	0.0215 (8)	0.0349 (10)	0.0028 (7)	0.0002 (7)	−0.0081 (7)
C1	0.0291 (10)	0.0265 (9)	0.0322 (10)	−0.0059 (8)	0.0049 (8)	0.0019 (8)
C18	0.0211 (9)	0.0402 (10)	0.0241 (9)	0.0053 (8)	−0.0003 (7)	−0.0038 (8)
C8	0.0185 (9)	0.0344 (10)	0.0412 (11)	0.0042 (7)	−0.0049 (8)	0.0055 (9)
C19	0.0240 (9)	0.0342 (10)	0.0312 (10)	−0.0031 (8)	−0.0018 (7)	0.0000 (8)
C20	0.0177 (9)	0.0523 (13)	0.0402 (11)	−0.0006 (8)	−0.0014 (8)	−0.0022 (10)
C21	0.0252 (10)	0.0627 (14)	0.0392 (12)	0.0123 (10)	−0.0038 (9)	0.0083 (11)
C4	0.0290 (11)	0.0514 (13)	0.0612 (15)	0.0061 (9)	0.0010 (10)	0.0276 (12)
C22	0.0288 (12)	0.102 (2)	0.0601 (16)	0.0125 (13)	0.0013 (11)	0.0483 (16)
C23	0.0227 (11)	0.094 (2)	0.0489 (14)	0.0123 (11)	0.0073 (9)	0.0370 (14)

S1—C9	1.7532 (17)	C17—H17	0.9500
S1—C2	1.7596 (18)	C7—C1	1.498 (2)
F1—C14	1.359 (2)	C16—H16	0.9500
O3—C10	1.338 (2)	C12—C13	1.390 (2)
O3—C8	1.459 (2)	C12—H12	0.9500
O1—C3	1.216 (2)	C13—C14	1.381 (3)
N1—C9	1.375 (2)	C13—H13	0.9500
N1—C3	1.386 (2)	C1—H1A	0.9800
N1—C5	1.482 (2)	C1—H1B	0.9800
N2—C9	1.278 (2)	C1—H1C	0.9800
N2—C7	1.414 (2)	C18—C23	1.387 (3)
F2—C19	1.349 (2)	C18—C19	1.389 (3)
C6—C7	1.349 (2)	C8—C4	1.497 (3)
C6—C10	1.484 (2)	C8—H8A	0.9900
C6—C5	1.526 (2)	C8—H8B	0.9900
O2—C10	1.208 (2)	C19—C20	1.376 (3)
C5—C11	1.524 (2)	C20—C21	1.378 (3)
C5—H5	1.0000	C20—H20	0.9500
C3—C2	1.489 (2)	C21—C22	1.371 (3)
C15—C14	1.380 (3)	C21—H21	0.9500
C15—C16	1.387 (2)	C4—H4A	0.9800
C15—H15	0.9500	C4—H4B	0.9800
C2—C17	1.343 (3)	C4—H4C	0.9800
C11—C16	1.391 (2)	C22—C23	1.385 (3)
C11—C12	1.393 (2)	C22—H22	0.9500
C17—C18	1.460 (2)	C23—H23	0.9500
C9—S1—C2	91.35 (8)	C11—C12—H12	119.7
C10—O3—C8	115.66 (13)	C14—C13—C12	117.86 (16)
C9—N1—C3	116.66 (14)	C14—C13—H13	121.1
C9—N1—C5	120.90 (13)	C12—C13—H13	121.1
C3—N1—C5	121.74 (13)	F1—C14—C15	118.47 (16)
C9—N2—C7	116.77 (14)	F1—C14—C13	118.26 (16)
C7—C6—C10	122.66 (15)	C15—C14—C13	123.26 (16)
C7—C6—C5	122.46 (15)	C7—C1—H1A	109.5
C10—C6—C5	114.81 (14)	C7—C1—H1B	109.5
N1—C5—C11	109.96 (13)	H1A—C1—H1B	109.5
N1—C5—C6	108.16 (13)	C7—C1—H1C	109.5
C11—C5—C6	112.57 (13)	H1A—C1—H1C	109.5
N1—C5—H5	108.7	H1B—C1—H1C	109.5
C11—C5—H5	108.7	C23—C18—C19	115.70 (17)
C6—C5—H5	108.7	C23—C18—C17	124.10 (17)
O1—C3—N1	123.73 (15)	C19—C18—C17	120.21 (17)
O1—C3—C2	126.49 (15)	O3—C8—C4	107.36 (15)
N1—C3—C2	109.78 (14)	O3—C8—H8A	110.2
O2—C10—O3	123.02 (16)	C4—C8—H8A	110.2
O2—C10—C6	125.85 (17)	O3—C8—H8B	110.2
O3—C10—C6	111.13 (14)	C4—C8—H8B	110.2
C14—C15—C16	117.88 (16)	H8A—C8—H8B	108.5
C14—C15—H15	121.1	F2—C19—C20	118.49 (17)
C16—C15—H15	121.1	F2—C19—C18	117.92 (16)
C17—C2—C3	121.14 (16)	C20—C19—C18	123.58 (19)
C17—C2—S1	128.34 (14)	C19—C20—C21	118.82 (18)
C3—C2—S1	110.49 (12)	C19—C20—H20	120.6
C16—C11—C12	119.46 (16)	C21—C20—H20	120.6
C16—C11—C5	120.17 (15)	C22—C21—C20	119.71 (19)
C12—C11—C5	120.36 (14)	C22—C21—H21	120.1
C2—C17—C18	128.02 (18)	C20—C21—H21	120.1
C2—C17—H17	116.0	C8—C4—H4A	109.5
C18—C17—H17	116.0	C8—C4—H4B	109.5
C6—C7—N2	122.16 (15)	H4A—C4—H4B	109.5
C6—C7—C1	126.68 (16)	C8—C4—H4C	109.5
N2—C7—C1	111.15 (15)	H4A—C4—H4C	109.5
C15—C16—C11	120.87 (16)	H4B—C4—H4C	109.5
C15—C16—H16	119.6	C21—C22—C23	120.3 (2)
C11—C16—H16	119.6	C21—C22—H22	119.8
N2—C9—N1	126.81 (15)	C23—C22—H22	119.8
N2—C9—S1	121.49 (13)	C22—C23—C18	121.8 (2)
N1—C9—S1	111.69 (12)	C22—C23—H23	119.1
C13—C12—C11	120.67 (15)	C18—C23—H23	119.1
C13—C12—H12	119.7
C9—N1—C5—C11	104.58 (16)	C9—N2—C7—C6	−5.9 (2)
C3—N1—C5—C11	−65.51 (19)	C9—N2—C7—C1	172.94 (15)
C9—N1—C5—C6	−18.7 (2)	C14—C15—C16—C11	−0.5 (2)
C3—N1—C5—C6	171.21 (14)	C12—C11—C16—C15	0.2 (2)
C7—C6—C5—N1	14.5 (2)	C5—C11—C16—C15	−178.72 (15)
C10—C6—C5—N1	−168.64 (13)	C7—N2—C9—N1	1.3 (2)
C7—C6—C5—C11	−107.15 (18)	C7—N2—C9—S1	−177.66 (12)
C10—C6—C5—C11	69.67 (18)	C3—N1—C9—N2	−176.87 (16)
C9—N1—C3—O1	178.82 (15)	C5—N1—C9—N2	12.6 (3)
C5—N1—C3—O1	−10.7 (2)	C3—N1—C9—S1	2.14 (18)
C9—N1—C3—C2	−1.3 (2)	C5—N1—C9—S1	−168.43 (11)
C5—N1—C3—C2	169.20 (13)	C2—S1—C9—N2	177.27 (15)
C8—O3—C10—O2	3.5 (3)	C2—S1—C9—N1	−1.80 (12)
C8—O3—C10—C6	−176.91 (14)	C16—C11—C12—C13	−0.1 (2)
C7—C6—C10—O2	7.4 (3)	C5—C11—C12—C13	178.90 (14)
C5—C6—C10—O2	−169.38 (18)	C11—C12—C13—C14	0.1 (2)
C7—C6—C10—O3	−172.13 (15)	C16—C15—C14—F1	−179.44 (14)
C5—C6—C10—O3	11.1 (2)	C16—C15—C14—C13	0.5 (3)
O1—C3—C2—C17	−2.0 (3)	C12—C13—C14—F1	179.61 (14)
N1—C3—C2—C17	178.08 (15)	C12—C13—C14—C15	−0.4 (3)
O1—C3—C2—S1	179.75 (14)	C2—C17—C18—C23	−21.2 (3)
N1—C3—C2—S1	−0.14 (17)	C2—C17—C18—C19	158.67 (19)
C9—S1—C2—C17	−176.98 (17)	C10—O3—C8—C4	177.01 (17)
C9—S1—C2—C3	1.09 (12)	C23—C18—C19—F2	−178.7 (2)
N1—C5—C11—C16	108.87 (17)	C17—C18—C19—F2	1.4 (3)
C6—C5—C11—C16	−130.46 (16)	C23—C18—C19—C20	1.8 (3)
N1—C5—C11—C12	−70.07 (18)	C17—C18—C19—C20	−178.07 (18)
C6—C5—C11—C12	50.6 (2)	F2—C19—C20—C21	−179.40 (19)
C3—C2—C17—C18	−179.02 (16)	C18—C19—C20—C21	0.0 (3)
S1—C2—C17—C18	−1.1 (3)	C19—C20—C21—C22	−1.5 (4)
C10—C6—C7—N2	−179.71 (15)	C20—C21—C22—C23	1.0 (4)
C5—C6—C7—N2	−3.1 (2)	C21—C22—C23—C18	1.0 (5)
C10—C6—C7—C1	1.6 (3)	C19—C18—C23—C22	−2.3 (4)
C5—C6—C7—C1	178.17 (16)	C17—C18—C23—C22	177.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2i	0.99	2.48	3.119 (2)	122
C15—H15···N2ii	0.95	2.57	3.488 (2)	162
C8—H8B···Cgiii	0.99	2.96	3.911 (2)	162

Table 1

Hydrogen-bond geometry (, )

Cg is the centroid of the C11C16 ring.

DHA	DH	HA	D A	DHA
C8H8AO2i	0.99	2.48	3.119(2)	122
C15H15N2ii	0.95	2.57	3.488(2)	162
C8H8B Cg iii	0.99	2.96	3.911(2)	162

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