Crystal structure of ethyl 5-(3-fluoro-phen-yl)-2-[(4-fluoro-phen-yl)methyl-idene]-7-methyl-3-oxo-2H,3H,5H-[1,3]thia-zolo[3,2-a]pyrimidine-6-carboxyl-ate.

In the title mol-ecule, C23H18F2N2O3S, the pyrimidine ring is in a half-chair conformation and the 3-fluoro-phenyl group is in the axial position. The thia-zole ring (r.m.s. deviation = 0.0252 Å) forms dihedral angles of 84.8 (7) and 9.6 (7)° with the 3-fluoro-substituted and 4-fluoro-substituted benzene rings, respectively. In the crystal, weak C-H⋯F and C-H⋯O hydrogen bonds connect mol-ecules, forming zigzag chains along the b axis. In addition π-π stacking inter-actions with a centroid-centroid distance of 3.7633 (9) Å connect these chains into ladders via inversion-related 4-fluoro-phenyl groups.

Related literature

For the pharmacological properties of pyrimidine derivatives, see: Alam et al. (2010 ▶); Kulakov et al. (2009 ▶); Ashok et al. (2007 ▶). For examples of compounds with weak inter­molecular inter­actions, see: Prasanna & Guru Row (2001 ▶); Yamazaki et al. (2009 ▶). For related structures, see: Fischer et al. (2007 ▶); Zhao et al. (2011 ▶); Nagarajaiah & Begum (2011 ▶).

Experimental

Crystal data

C23H18F2N2O3S

M = 440.45

Monoclinic,

a = 9.4358 (5) Å

b = 10.7862 (6) Å

c = 20.2246 (11) Å

β = 92.159 (1)°

V = 2056.93 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 100 K

0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.964, T max = 0.968

15631 measured reflections

4480 independent reflections

3890 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.104

S = 1.06

4480 reflections

282 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.23 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/S1600536814023010/lh5711sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023010/lh5711Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814023010/lh5711Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814023010/lh5711fig1.tif

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

Click here for additional data file.

. DOI: 10.1107/S1600536814023010/lh5711fig2.tif

Part of the crystal structure showing inter­molecular inter­actions with dotted lines. H-atoms not involved in hydrogen bonds have been excluded.

CCDC reference: 1029845

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

C23H18F2N2O3S	F(000) = 912
Mr = 440.45	Dx = 1.422 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4480 reflections
a = 9.4358 (5) Å	θ = 2.1–27.0°
b = 10.7862 (6) Å	µ = 0.20 mm−1
c = 20.2246 (11) Å	T = 100 K
β = 92.159 (1)°	Block, yellow
V = 2056.93 (19) Å3	0.18 × 0.16 × 0.16 mm
Z = 4

Bruker SMART APEX diffractometer	4480 independent reflections
Radiation source: fine-focus sealed tube	3890 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→12
Tmin = 0.964, Tmax = 0.968	k = −13→11
15631 measured reflections	l = −25→25

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0546P)2 + 0.9996P] where P = (Fo2 + 2Fc2)/3
4480 reflections	(Δ/σ)max = 0.001
282 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.23 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	0.88687 (4)	0.19204 (3)	0.034764 (17)	0.01589 (11)
F2	0.38224 (11)	−0.20262 (10)	0.14390 (5)	0.0344 (3)
N1	1.02387 (12)	0.21900 (11)	−0.07291 (6)	0.0130 (2)
O1	0.95802 (11)	0.05123 (9)	−0.13566 (5)	0.0168 (2)
O3	1.32012 (11)	0.35754 (11)	−0.18945 (5)	0.0234 (3)
N2	1.08494 (13)	0.36112 (12)	0.01251 (6)	0.0178 (3)
F1	0.83639 (12)	0.28603 (11)	−0.33642 (5)	0.0364 (3)
C6	1.20222 (15)	0.37625 (13)	−0.09169 (7)	0.0168 (3)
C2	0.86191 (15)	0.08022 (13)	−0.02757 (7)	0.0136 (3)
C17	0.77697 (14)	−0.01947 (13)	−0.02952 (7)	0.0145 (3)
H17	0.7813	−0.0677	−0.0687	0.017*
C9	1.01253 (15)	0.27081 (13)	−0.01116 (7)	0.0138 (3)
C11	0.99691 (15)	0.34259 (14)	−0.17420 (7)	0.0160 (3)
C5	1.10183 (15)	0.28309 (13)	−0.12475 (7)	0.0144 (3)
H5	1.1592	0.2205	−0.1485	0.017*
C18	0.67908 (15)	−0.06573 (13)	0.01880 (7)	0.0157 (3)
C21	0.48097 (17)	−0.15811 (16)	0.10318 (8)	0.0240 (3)
C7	1.19145 (15)	0.40940 (13)	−0.02781 (8)	0.0175 (3)
C16	0.96568 (17)	0.28569 (15)	−0.23478 (8)	0.0202 (3)
H16	1.0110	0.2107	−0.2466	0.024*
C3	0.94988 (14)	0.11093 (13)	−0.08497 (7)	0.0135 (3)
C20	0.48715 (17)	−0.20784 (15)	0.04067 (9)	0.0236 (3)
H20	0.4247	−0.2726	0.0267	0.028*
C19	0.58648 (16)	−0.16121 (14)	−0.00123 (8)	0.0195 (3)
H19	0.5921	−0.1946	−0.0445	0.023*
C23	0.67034 (16)	−0.01971 (15)	0.08349 (8)	0.0202 (3)
H23	0.7331	0.0442	0.0983	0.024*
C15	0.86709 (17)	0.34154 (16)	−0.27702 (7)	0.0243 (4)
C10	1.31041 (16)	0.42857 (15)	−0.13541 (8)	0.0235 (3)
O2	1.37971 (16)	0.52124 (13)	−0.12605 (8)	0.0448 (4)
C13	0.83007 (17)	0.50531 (16)	−0.20222 (9)	0.0266 (4)
H13	0.7836	0.5800	−0.1908	0.032*
C12	0.92960 (16)	0.45299 (15)	−0.15833 (8)	0.0206 (3)
H12	0.9519	0.4926	−0.1173	0.025*
C1	1.28965 (17)	0.49369 (16)	0.01043 (9)	0.0253 (4)
H1A	1.3665	0.5199	−0.0177	0.038*
H1B	1.3296	0.4498	0.0493	0.038*
H1C	1.2373	0.5667	0.0248	0.038*
C22	0.57151 (17)	−0.06610 (15)	0.12598 (8)	0.0235 (3)
H22	0.5663	−0.0352	0.1698	0.028*
C14	0.79808 (17)	0.44933 (16)	−0.26257 (8)	0.0265 (4)
H14	0.7303	0.4846	−0.2930	0.032*
C8	1.41942 (18)	0.39730 (18)	−0.23844 (9)	0.0309 (4)
H8A	1.5130	0.4160	−0.2170	0.037*
H8B	1.3840	0.4728	−0.2615	0.037*
C4	1.4318 (2)	0.29285 (19)	−0.28635 (9)	0.0358 (4)
H4A	1.4729	0.2205	−0.2635	0.054*
H4B	1.4931	0.3178	−0.3221	0.054*
H4C	1.3375	0.2717	−0.3050	0.054*

	U11	U22	U33	U12	U13	U23
S1	0.01805 (19)	0.01604 (19)	0.01374 (18)	−0.00094 (13)	0.00276 (13)	−0.00157 (13)
F2	0.0247 (5)	0.0389 (6)	0.0406 (6)	−0.0027 (4)	0.0143 (4)	0.0164 (5)
N1	0.0131 (6)	0.0139 (6)	0.0121 (5)	−0.0001 (4)	0.0003 (4)	0.0014 (4)
O1	0.0185 (5)	0.0175 (5)	0.0147 (5)	−0.0020 (4)	0.0024 (4)	−0.0026 (4)
O3	0.0197 (6)	0.0269 (6)	0.0238 (6)	−0.0057 (5)	0.0057 (4)	0.0064 (5)
N2	0.0167 (6)	0.0160 (6)	0.0206 (6)	−0.0004 (5)	−0.0012 (5)	−0.0029 (5)
F1	0.0456 (7)	0.0419 (6)	0.0206 (5)	−0.0067 (5)	−0.0127 (5)	0.0051 (4)
C6	0.0127 (7)	0.0136 (7)	0.0238 (7)	−0.0002 (5)	−0.0023 (6)	0.0026 (6)
C2	0.0131 (6)	0.0147 (7)	0.0131 (6)	0.0026 (5)	−0.0002 (5)	0.0006 (5)
C17	0.0130 (7)	0.0154 (7)	0.0152 (7)	0.0028 (5)	0.0000 (5)	0.0014 (5)
C9	0.0133 (6)	0.0139 (6)	0.0143 (6)	0.0030 (5)	−0.0002 (5)	0.0009 (5)
C11	0.0126 (7)	0.0176 (7)	0.0178 (7)	−0.0033 (5)	0.0008 (5)	0.0060 (6)
C5	0.0120 (6)	0.0147 (7)	0.0167 (7)	−0.0012 (5)	0.0022 (5)	0.0025 (5)
C18	0.0132 (7)	0.0133 (7)	0.0207 (7)	0.0033 (5)	0.0014 (5)	0.0053 (6)
C21	0.0165 (7)	0.0255 (8)	0.0306 (8)	0.0042 (6)	0.0085 (6)	0.0141 (7)
C7	0.0125 (7)	0.0124 (7)	0.0273 (8)	0.0010 (5)	−0.0025 (6)	−0.0005 (6)
C16	0.0215 (8)	0.0192 (7)	0.0198 (7)	−0.0027 (6)	0.0003 (6)	0.0050 (6)
C3	0.0116 (6)	0.0144 (7)	0.0142 (6)	0.0012 (5)	−0.0017 (5)	0.0020 (5)
C20	0.0157 (7)	0.0179 (8)	0.0373 (9)	−0.0015 (6)	0.0006 (6)	0.0084 (7)
C19	0.0164 (7)	0.0169 (7)	0.0252 (8)	0.0022 (6)	0.0001 (6)	0.0041 (6)
C23	0.0191 (7)	0.0193 (7)	0.0222 (7)	0.0007 (6)	0.0021 (6)	0.0044 (6)
C15	0.0247 (8)	0.0309 (9)	0.0169 (7)	−0.0095 (7)	−0.0038 (6)	0.0071 (7)
C10	0.0166 (7)	0.0215 (8)	0.0323 (9)	−0.0025 (6)	0.0007 (6)	0.0042 (7)
O2	0.0439 (8)	0.0382 (8)	0.0535 (9)	−0.0277 (7)	0.0159 (7)	−0.0068 (7)
C13	0.0195 (8)	0.0275 (9)	0.0329 (9)	0.0055 (6)	0.0019 (7)	0.0090 (7)
C12	0.0186 (7)	0.0208 (8)	0.0226 (7)	0.0010 (6)	0.0010 (6)	0.0039 (6)
C1	0.0181 (8)	0.0214 (8)	0.0361 (9)	−0.0035 (6)	−0.0021 (7)	−0.0083 (7)
C22	0.0237 (8)	0.0254 (8)	0.0217 (8)	0.0044 (6)	0.0059 (6)	0.0072 (6)
C14	0.0171 (7)	0.0336 (9)	0.0285 (8)	−0.0019 (6)	−0.0037 (6)	0.0160 (7)
C8	0.0229 (8)	0.0393 (10)	0.0311 (9)	−0.0082 (7)	0.0091 (7)	0.0114 (8)
C4	0.0371 (10)	0.0491 (12)	0.0219 (8)	−0.0069 (9)	0.0088 (7)	0.0084 (8)

S1—C9	1.7531 (14)	C21—C22	1.378 (2)
S1—C2	1.7542 (14)	C7—C1	1.493 (2)
F2—C21	1.3544 (17)	C16—C15	1.378 (2)
N1—C3	1.3758 (18)	C16—H16	0.9500
N1—C9	1.3761 (18)	C20—C19	1.382 (2)
N1—C5	1.4753 (17)	C20—H20	0.9500
O1—C3	1.2154 (17)	C19—H19	0.9500
O3—C10	1.341 (2)	C23—C22	1.385 (2)
O3—C8	1.4538 (18)	C23—H23	0.9500
N2—C9	1.2728 (19)	C15—C14	1.370 (3)
N2—C7	1.4171 (19)	C10—O2	1.206 (2)
F1—C15	1.3636 (19)	C13—C14	1.385 (2)
C6—C7	1.348 (2)	C13—C12	1.388 (2)
C6—C10	1.487 (2)	C13—H13	0.9500
C6—C5	1.519 (2)	C12—H12	0.9500
C2—C17	1.341 (2)	C1—H1A	0.9800
C2—C3	1.4897 (18)	C1—H1B	0.9800
C17—C18	1.4578 (19)	C1—H1C	0.9800
C17—H17	0.9500	C22—H22	0.9500
C11—C16	1.392 (2)	C14—H14	0.9500
C11—C12	1.393 (2)	C8—C4	1.493 (3)
C11—C5	1.5222 (19)	C8—H8A	0.9900
C5—H5	1.0000	C8—H8B	0.9900
C18—C19	1.401 (2)	C4—H4A	0.9800
C18—C23	1.405 (2)	C4—H4B	0.9800
C21—C20	1.376 (2)	C4—H4C	0.9800
C9—S1—C2	91.59 (7)	C19—C20—H20	120.8
C3—N1—C9	116.66 (12)	C20—C19—C18	121.37 (15)
C3—N1—C5	122.30 (11)	C20—C19—H19	119.3
C9—N1—C5	120.84 (12)	C18—C19—H19	119.3
C10—O3—C8	116.91 (13)	C22—C23—C18	120.98 (15)
C9—N2—C7	116.55 (12)	C22—C23—H23	119.5
C7—C6—C10	123.20 (14)	C18—C23—H23	119.5
C7—C6—C5	121.96 (13)	F1—C15—C14	118.29 (15)
C10—C6—C5	114.84 (13)	F1—C15—C16	118.06 (16)
C17—C2—C3	120.36 (13)	C14—C15—C16	123.65 (15)
C17—C2—S1	129.53 (11)	O2—C10—O3	123.27 (15)
C3—C2—S1	110.09 (10)	O2—C10—C6	127.00 (16)
C2—C17—C18	130.38 (13)	O3—C10—C6	109.72 (13)
C2—C17—H17	114.8	C14—C13—C12	120.42 (16)
C18—C17—H17	114.8	C14—C13—H13	119.8
N2—C9—N1	126.38 (13)	C12—C13—H13	119.8
N2—C9—S1	122.40 (11)	C13—C12—C11	120.25 (15)
N1—C9—S1	111.18 (10)	C13—C12—H12	119.9
C16—C11—C12	119.77 (14)	C11—C12—H12	119.9
C16—C11—C5	120.22 (13)	C7—C1—H1A	109.5
C12—C11—C5	120.00 (13)	C7—C1—H1B	109.5
N1—C5—C6	108.45 (11)	H1A—C1—H1B	109.5
N1—C5—C11	109.58 (11)	C7—C1—H1C	109.5
C6—C5—C11	112.94 (12)	H1A—C1—H1C	109.5
N1—C5—H5	108.6	H1B—C1—H1C	109.5
C6—C5—H5	108.6	C21—C22—C23	118.42 (15)
C11—C5—H5	108.6	C21—C22—H22	120.8
C19—C18—C23	118.12 (13)	C23—C22—H22	120.8
C19—C18—C17	117.51 (13)	C15—C14—C13	117.95 (15)
C23—C18—C17	124.36 (14)	C15—C14—H14	121.0
F2—C21—C20	118.31 (15)	C13—C14—H14	121.0
F2—C21—C22	118.93 (15)	O3—C8—C4	106.72 (14)
C20—C21—C22	122.76 (14)	O3—C8—H8A	110.4
C6—C7—N2	122.33 (13)	C4—C8—H8A	110.4
C6—C7—C1	126.18 (14)	O3—C8—H8B	110.4
N2—C7—C1	111.43 (13)	C4—C8—H8B	110.4
C15—C16—C11	117.95 (15)	H8A—C8—H8B	108.6
C15—C16—H16	121.0	C8—C4—H4A	109.5
C11—C16—H16	121.0	C8—C4—H4B	109.5
O1—C3—N1	123.41 (12)	H4A—C4—H4B	109.5
O1—C3—C2	126.46 (13)	C8—C4—H4C	109.5
N1—C3—C2	110.13 (12)	H4A—C4—H4C	109.5
C21—C20—C19	118.32 (15)	H4B—C4—H4C	109.5
C21—C20—H20	120.8
C9—S1—C2—C17	179.32 (14)	C9—N1—C3—O1	−174.93 (13)
C9—S1—C2—C3	−2.35 (10)	C5—N1—C3—O1	10.2 (2)
C3—C2—C17—C18	−177.86 (13)	C9—N1—C3—C2	4.85 (17)
S1—C2—C17—C18	0.3 (2)	C5—N1—C3—C2	−169.99 (12)
C7—N2—C9—N1	−2.8 (2)	C17—C2—C3—O1	−2.5 (2)
C7—N2—C9—S1	174.64 (10)	S1—C2—C3—O1	178.97 (12)
C3—N1—C9—N2	170.94 (14)	C17—C2—C3—N1	177.70 (13)
C5—N1—C9—N2	−14.1 (2)	S1—C2—C3—N1	−0.80 (14)
C3—N1—C9—S1	−6.71 (15)	F2—C21—C20—C19	179.07 (13)
C5—N1—C9—S1	168.21 (10)	C22—C21—C20—C19	−1.5 (2)
C2—S1—C9—N2	−172.76 (13)	C21—C20—C19—C18	0.0 (2)
C2—S1—C9—N1	5.00 (11)	C23—C18—C19—C20	1.2 (2)
C3—N1—C5—C6	−164.71 (12)	C17—C18—C19—C20	−177.90 (14)
C9—N1—C5—C6	20.67 (17)	C19—C18—C23—C22	−1.0 (2)
C3—N1—C5—C11	71.60 (16)	C17—C18—C23—C22	178.08 (14)
C9—N1—C5—C11	−103.03 (14)	C11—C16—C15—F1	179.95 (13)
C7—C6—C5—N1	−13.70 (19)	C11—C16—C15—C14	−0.2 (2)
C10—C6—C5—N1	167.22 (12)	C8—O3—C10—O2	−0.4 (2)
C7—C6—C5—C11	107.95 (16)	C8—O3—C10—C6	178.65 (13)
C10—C6—C5—C11	−71.13 (16)	C7—C6—C10—O2	−16.7 (3)
C16—C11—C5—N1	−101.02 (15)	C5—C6—C10—O2	162.33 (17)
C12—C11—C5—N1	77.65 (16)	C7—C6—C10—O3	164.23 (14)
C16—C11—C5—C6	137.96 (14)	C5—C6—C10—O3	−16.70 (18)
C12—C11—C5—C6	−43.37 (17)	C14—C13—C12—C11	−0.9 (2)
C2—C17—C18—C19	169.68 (15)	C16—C11—C12—C13	1.0 (2)
C2—C17—C18—C23	−9.4 (2)	C5—C11—C12—C13	−177.68 (14)
C10—C6—C7—N2	178.12 (13)	F2—C21—C22—C23	−178.84 (14)
C5—C6—C7—N2	−0.9 (2)	C20—C21—C22—C23	1.7 (2)
C10—C6—C7—C1	−5.0 (2)	C18—C23—C22—C21	−0.4 (2)
C5—C6—C7—C1	175.96 (14)	F1—C15—C14—C13	−179.84 (14)
C9—N2—C7—C6	10.3 (2)	C16—C15—C14—C13	0.4 (2)
C9—N2—C7—C1	−166.99 (13)	C12—C13—C14—C15	0.2 (2)
C12—C11—C16—C15	−0.4 (2)	C10—O3—C8—C4	169.32 (15)
C5—C11—C16—C15	178.24 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···F1i	0.95	2.53	3.437 (2)	159
C13—H13···F1ii	0.95	2.56	3.513 (2)	178
C14—H14···O1ii	0.95	2.36	3.303 (2)	172

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C19H19F1i	0.95	2.53	3.437(2)	159
C13H13F1ii	0.95	2.56	3.513(2)	178
C14H14O1ii	0.95	2.36	3.303(2)	172

Symmetry codes: (i) ; (ii) .