Ethyl 4-(2-bromo-5-fluoro­phen­yl)-6-methyl-1-phenyl-2-thioxo-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate

Fun, H.-K.; Jebas, S.R.; Babu, M.; Patil, P.S.; Kalluraya, B.; Dharmaprakash, S.M.

doi:10.1107/S1600536808021685

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages o1526-o1527

doi:10.1107/S1600536808021685

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Ethyl 4-(2-bromo-5-fluorophenyl)-6-methyl-1-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate

Hoong-Kun Fun,^a ^* Samuel Robinson Jebas,^a ‡ M. Babu,^b P. S. Patil,^c B. Kalluraya ^b and S. M. Dharmaprakash ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India, and ^cDepartment of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 8 July 2008; accepted 12 July 2008; online 19 July 2008)

In the title molecule, C₂₀H₁₈BrFN₂O₂S, the pyrimidine ring adopts a flattened envelope conformation. The halogenated benzene ring is orthogonal to the planar part of the pyrimidine ring [dihedral angle = 89.05 (4)°], while the other phenyl ring is oriented at an angle of 85.14 (5)°. The ethoxy group is disordered over two orientations with site occpancies of ca 0.869 (4) and 0.131 (4). Intramolecular C—H⋯Br and C—H⋯O hydrogen bonds generate S(5) and S(6) ring motifs. The crystal structure is stabilized by intermolecular N—H⋯S, C—H⋯F, C—H⋯O and C—H⋯Br hydrogen bonds.

Related literature

For the biological activity of pyrimidinone derivatives, see: Atwal (1990 ); Matsuda & Hirao (1965 ); Sadanandam et al. (1992 ). For the synthetic procedure, see: Steele et al. (1998 ); Manjual et al. (2004 ); Kappe (1993 ); Wipf & Cunningham (1995 ). For bond-length data, see: Allen et al. (1987 ). For ring conformations, see: Cremer & Pople (1975 ). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₀H₁₈BrFN₂O₂S
M_r = 449.33
Triclinic, $[P \overline 1]$
a = 10.0455 (1) Å
b = 10.2969 (1) Å
c = 10.3714 (1) Å
α = 64.286 (1)°
β = 83.110 (1)°
γ = 78.796 (1)°
V = 947.36 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.31 mm⁻¹
T = 100 (2) K
0.41 × 0.35 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.451, T_max = 0.631
30132 measured reflections
5490 independent reflections
4895 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.084
S = 1.04
5490 reflections
267 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯S1ⁱ	0.85	2.51	3.327 (2)	162
C1—H1⋯F1ⁱⁱ	0.95	2.52	3.370 (2)	148
C7—H7⋯Br1	1.00	2.69	3.265 (2)	117
C20—H20⋯O1ⁱⁱⁱ	0.95	2.44	3.368 (3)	164
C21—H21A⋯O2	0.98	2.11	2.737 (3)	120
C21—H21B⋯Br1ⁱⁱⁱ	0.98	2.91	3.886 (2)	171
Symmetry codes: (i) -x+2, -y+1, -z; (ii) -x+2, -y, -z; (iii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021685/ci2628sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021685/ci2628Isup2.hkl

checkCIF report

Comment top

3,4-Dihydropyrimidinones have drawn wide-spread attention due to their pharmaceutical applications. A variety of these derivatives have been screened for antihypertension (Atwal, 1990), antibacterial (Matsuda & Hirao, 1965) and anti-inflammatory activities (Sadanandam et al., 1992). The common synthetic routes to these compounds generally involve multi step transformations, which are essentially based on the Biginelli condensation methodology (Steele et al., 1998). These pyrimidinones are also associated with calcium channel blocking activity (Manjual et al., 2004). In 1893, Biginelli reported the first synthesis of dihydropyrimidines by a simple one-pot condensation reaction of ethyl acetoacetate, benzaldehyde and urea. In the following decades the original cyclo-condensation reaction has been extended widely to include variations in all three components, allowing access to a large number of muti functionalized dihydropyrimidinone derivatives (Kappe, 1993). Biginelli reaction has recently attracted a great deal of attention and several improved procedures for the preparation of dihydropyrimidinones have been reported within the past few years. Several solid-phase modifications of the Biginelli reaction suitable for the combinatorial chemistry have also been described (Wipf & Cunningham, 1995).

Bond lengths and angles in the title molecule (Fig. 1) are found to have normal values (Allen et al., 1987). The pyrimidine ring adopts a flattened envelope conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.067 (2) Å, θ = 132.5 (16)° and ϕ = 237 (2)°. The C1-C6 and C15-C20 phenyl rings form dihedral angles of 89.05 (4)° and 85.14 (5)°, respectively, with the N1/N2/C7/C8/C13/C14 plane. Intramolecular C—H···Br and C—H···O hydrogen bonds generate S(5) and S(6) ring motifs (Bernstein et al., 1995), respectively.

The crystal structure is stabilized by intermolecular N—H···S, C—H···F, C—H···O and C—H···Br hydrogen bonds (Table 1 and Fig.2).

Related literature top

For the biological activity of pyrimidinone derivatives, see: Atwal (1990); Matsuda & Hirao (1965); Sadanandam et al. (1992). For the synthetic procedure, see: Steele et al. (1998); Manjual et al. (2004); Kappe (1993); Wipf & Cunningham (1995). For bond-length data, see: Allen et al. (1987). For ring conformations, see: Cremer & Pople (1975). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental top

A mixture of 2-bromo-5-fluorobenzaldehyde (0.01 mol, 2.0301 g), ethyl acetoacetate [0.015 mol, 2 g (2 ml)], phenylthiourea (0.01 mol, 1.5215 g) and concentrated H₂SO₄ (2 drops) in absolute alcohol (10 ml) taken in a beaker (100 ml) was put inside a microwave oven for 4 minutes at 160 Watts (25% MW power). The reaction mixture was then allowed to stand at room temperature and the product formed was filtered, washed with ethanol followed by water and dried. Further purification was done by recrystallization from ethanol (yield = 77%, m.p = 442–445 K). Composition calculated (found): C 53.45 (53.34), H 4.008 (3.92), N 6.236 (6.15), S 7.1269 (7.03)%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Both disorder components are shown.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines. Only the major disorder component is shown.

Ethyl 4-(2-bromo-5-fluorophenyl)-6-methyl-1-phenyl-2-thioxo-1,2,3,4- tetrahydropyrimidine-5-carboxylate top

Crystal data top

C₂₀H₁₈BrFN₂O₂S	Z = 2
M_r = 449.33	F(000) = 456
Triclinic, P1	D_x = 1.575 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0455 (1) Å	Cell parameters from 9996 reflections
b = 10.2969 (1) Å	θ = 2.2–37.5°
c = 10.3714 (1) Å	µ = 2.31 mm⁻¹
α = 64.286 (1)°	T = 100 K
β = 83.110 (1)°	Block, colourless
γ = 78.796 (1)°	0.41 × 0.35 × 0.22 mm
V = 947.36 (2) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5490 independent reflections
Radiation source: fine-focus sealed tube	4895 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
T_min = 0.451, T_max = 0.631	k = −14→14
30132 measured reflections	l = −14→14

Refinement top

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0443P)² + 0.6872P] where P = (F_o² + 2F_c²)/3
5490 reflections	(Δ/σ)_max = 0.001
267 parameters	Δρ_max = 1.01 e Å⁻³
15 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

C₂₀H₁₈BrFN₂O₂S	γ = 78.796 (1)°
M_r = 449.33	V = 947.36 (2) Å³
Triclinic, P1	Z = 2
a = 10.0455 (1) Å	Mo Kα radiation
b = 10.2969 (1) Å	µ = 2.31 mm⁻¹
c = 10.3714 (1) Å	T = 100 K
α = 64.286 (1)°	0.41 × 0.35 × 0.22 mm
β = 83.110 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5490 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4895 reflections with I > 2σ(I)
T_min = 0.451, T_max = 0.631	R_int = 0.029
30132 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	15 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.05	Δρ_max = 1.01 e Å⁻³
5490 reflections	Δρ_min = −0.66 e Å⁻³
267 parameters

Special details top

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.718042 (18)	0.65172 (2)	−0.42386 (2)	0.02506 (6)
S1	0.96029 (4)	0.37018 (5)	0.22541 (4)	0.01943 (9)
F1	1.01209 (13)	0.03875 (13)	−0.17700 (14)	0.0324 (3)
O1	0.50168 (14)	0.40666 (18)	−0.20152 (16)	0.0313 (3)
N1	0.81604 (15)	0.43472 (17)	0.00399 (15)	0.0196 (3)
H1N1	0.8781	0.4859	−0.0370	0.023*
N2	0.73979 (14)	0.26404 (16)	0.21844 (15)	0.0163 (3)
C1	0.87086 (17)	0.2259 (2)	−0.13630 (19)	0.0209 (3)
H1	0.8684	0.1647	−0.0365	0.025*
C2	0.94486 (18)	0.1774 (2)	−0.2313 (2)	0.0236 (3)
C3	0.95266 (18)	0.2600 (2)	−0.3770 (2)	0.0231 (3)
H3	1.0052	0.2215	−0.4387	0.028*
C4	0.88166 (17)	0.4003 (2)	−0.43062 (19)	0.0204 (3)
H4	0.8841	0.4596	−0.5308	0.024*
C5	0.80672 (16)	0.45529 (19)	−0.33865 (19)	0.0184 (3)
C6	0.79770 (16)	0.37081 (19)	−0.19184 (18)	0.0175 (3)
C7	0.71816 (17)	0.42662 (19)	−0.08487 (18)	0.0176 (3)
H7	0.6680	0.5269	−0.1394	0.021*
C8	0.61745 (16)	0.32950 (19)	0.00875 (19)	0.0182 (3)
C9	0.50415 (18)	0.3362 (2)	−0.0741 (2)	0.0221 (3)
C13	0.63308 (16)	0.24993 (19)	0.15063 (19)	0.0178 (3)
C14	0.83214 (16)	0.35640 (18)	0.14314 (17)	0.0158 (3)
C15	0.73718 (16)	0.19955 (18)	0.37368 (17)	0.0165 (3)
C16	0.81160 (19)	0.0635 (2)	0.4482 (2)	0.0250 (4)
H16	0.8712	0.0153	0.3985	0.030*
C17	0.7980 (2)	−0.0018 (2)	0.5970 (2)	0.0339 (5)
H17	0.8481	−0.0955	0.6498	0.041*
C18	0.7111 (2)	0.0701 (3)	0.6680 (2)	0.0335 (5)
H18	0.7008	0.0245	0.7694	0.040*
C19	0.6396 (2)	0.2069 (3)	0.5931 (2)	0.0290 (4)
H19	0.5817	0.2561	0.6429	0.035*
C20	0.65228 (17)	0.2732 (2)	0.44396 (19)	0.0206 (3)
H20	0.6033	0.3676	0.3914	0.025*
C21	0.5474 (2)	0.1379 (2)	0.2489 (2)	0.0261 (4)
H21A	0.5000	0.1072	0.1922	0.039*
H21B	0.4807	0.1805	0.3027	0.039*
H21C	0.6057	0.0531	0.3159	0.039*
O2	0.40143 (16)	0.26503 (19)	0.00591 (18)	0.0270 (4)	0.869 (4)
C11	0.2885 (2)	0.2674 (3)	−0.0718 (3)	0.0290 (5)	0.869 (4)
H11A	0.2726	0.3622	−0.1566	0.035*	0.869 (4)
H11B	0.2050	0.2570	−0.0093	0.035*	0.869 (4)
C12	0.3186 (3)	0.1458 (3)	−0.1191 (3)	0.0319 (5)	0.869 (4)
H12A	0.2419	0.1492	−0.1712	0.048*	0.869 (4)
H12B	0.3329	0.0519	−0.0350	0.048*	0.869 (4)
H12C	0.4006	0.1568	−0.1819	0.048*	0.869 (4)
O2A	0.4326 (11)	0.2257 (8)	−0.0408 (13)	0.0270 (4)	0.131 (4)
C11A	0.3310 (13)	0.2655 (15)	−0.1426 (13)	0.018 (3)	0.131 (4)
H11C	0.3703	0.2613	−0.2331	0.021*	0.131 (4)
H11D	0.2784	0.3638	−0.1632	0.021*	0.131 (4)
C12A	0.247 (2)	0.147 (2)	−0.060 (2)	0.047 (5)	0.131 (4)
H12D	0.1690	0.1610	−0.1156	0.071*	0.131 (4)
H12E	0.2146	0.1512	0.0314	0.071*	0.131 (4)
H12F	0.3024	0.0519	−0.0417	0.071*	0.131 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02414 (10)	0.02346 (10)	0.02129 (10)	0.00017 (6)	0.00032 (6)	−0.00558 (7)
S1	0.02016 (19)	0.0262 (2)	0.01355 (19)	−0.01177 (15)	0.00010 (14)	−0.00673 (16)
F1	0.0345 (6)	0.0264 (6)	0.0341 (7)	0.0048 (5)	−0.0013 (5)	−0.0146 (5)
O1	0.0241 (7)	0.0465 (9)	0.0253 (7)	−0.0044 (6)	−0.0057 (5)	−0.0162 (7)
N1	0.0233 (7)	0.0245 (7)	0.0142 (7)	−0.0131 (6)	0.0005 (5)	−0.0076 (6)
N2	0.0161 (6)	0.0205 (7)	0.0137 (6)	−0.0080 (5)	0.0022 (5)	−0.0072 (5)
C1	0.0198 (8)	0.0302 (9)	0.0189 (8)	−0.0095 (7)	0.0022 (6)	−0.0144 (7)
C2	0.0215 (8)	0.0237 (9)	0.0272 (9)	−0.0014 (6)	−0.0021 (7)	−0.0127 (8)
C3	0.0197 (8)	0.0279 (9)	0.0271 (9)	−0.0068 (7)	0.0052 (6)	−0.0167 (8)
C4	0.0186 (7)	0.0270 (9)	0.0190 (8)	−0.0086 (6)	0.0022 (6)	−0.0116 (7)
C5	0.0160 (7)	0.0203 (8)	0.0194 (8)	−0.0038 (6)	−0.0017 (6)	−0.0083 (7)
C6	0.0155 (7)	0.0232 (8)	0.0177 (8)	−0.0049 (6)	−0.0016 (5)	−0.0111 (7)
C7	0.0185 (7)	0.0219 (8)	0.0145 (7)	−0.0044 (6)	−0.0018 (5)	−0.0090 (6)
C8	0.0160 (7)	0.0229 (8)	0.0204 (8)	−0.0053 (6)	0.0006 (6)	−0.0130 (7)
C9	0.0187 (8)	0.0247 (9)	0.0289 (9)	−0.0017 (6)	−0.0039 (6)	−0.0167 (8)
C13	0.0155 (7)	0.0221 (8)	0.0205 (8)	−0.0068 (6)	0.0028 (6)	−0.0127 (7)
C14	0.0171 (7)	0.0176 (7)	0.0146 (7)	−0.0062 (6)	0.0020 (5)	−0.0077 (6)
C15	0.0163 (7)	0.0185 (7)	0.0140 (7)	−0.0073 (6)	0.0011 (5)	−0.0046 (6)
C16	0.0263 (9)	0.0183 (8)	0.0283 (10)	−0.0045 (7)	−0.0025 (7)	−0.0070 (7)
C17	0.0405 (11)	0.0222 (9)	0.0298 (11)	−0.0139 (8)	−0.0113 (9)	0.0036 (8)
C18	0.0395 (11)	0.0444 (12)	0.0150 (9)	−0.0294 (10)	0.0002 (7)	−0.0021 (8)
C19	0.0257 (9)	0.0476 (12)	0.0210 (9)	−0.0191 (8)	0.0087 (7)	−0.0181 (9)
C20	0.0169 (7)	0.0270 (9)	0.0192 (8)	−0.0065 (6)	0.0025 (6)	−0.0107 (7)
C21	0.0262 (9)	0.0348 (10)	0.0230 (9)	−0.0188 (8)	0.0058 (7)	−0.0134 (8)
O2	0.0213 (7)	0.0337 (9)	0.0305 (9)	−0.0104 (6)	−0.0044 (6)	−0.0144 (7)
C11	0.0200 (10)	0.0367 (13)	0.0351 (14)	−0.0058 (9)	−0.0053 (9)	−0.0179 (11)
C12	0.0316 (12)	0.0354 (13)	0.0353 (13)	−0.0111 (10)	−0.0007 (10)	−0.0187 (11)
O2A	0.0213 (7)	0.0337 (9)	0.0305 (9)	−0.0104 (6)	−0.0044 (6)	−0.0144 (7)
C11A	0.016 (5)	0.032 (6)	0.006 (5)	−0.007 (4)	−0.003 (4)	−0.007 (4)
C12A	0.037 (8)	0.059 (9)	0.038 (8)	−0.026 (7)	−0.014 (6)	−0.003 (6)

Geometric parameters (Å, º) top

Br1—C5	1.8982 (17)	C15—C20	1.383 (2)
S1—C14	1.6867 (16)	C16—C17	1.392 (3)
F1—C2	1.353 (2)	C16—H16	0.95
O1—C9	1.201 (2)	C17—C18	1.386 (4)
N1—C14	1.325 (2)	C17—H17	0.95
N1—C7	1.463 (2)	C18—C19	1.377 (3)
N1—H1N1	0.85	C18—H18	0.95
N2—C14	1.378 (2)	C19—C20	1.394 (3)
N2—C13	1.412 (2)	C19—H19	0.95
N2—C15	1.450 (2)	C20—H20	0.95
C1—C2	1.371 (2)	C21—H21A	0.98
C1—C6	1.424 (3)	C21—H21B	0.98
C1—H1	0.95	C21—H21C	0.98
C2—C3	1.377 (3)	O2—C11	1.459 (3)
C3—C4	1.380 (3)	C11—C12	1.499 (3)
C3—H3	0.95	C11—H11A	0.99
C4—C5	1.388 (2)	C11—H11B	0.99
C4—H4	0.95	C12—H12A	0.98
C5—C6	1.390 (2)	C12—H12B	0.98
C6—C7	1.537 (2)	C12—H12C	0.98
C7—C8	1.510 (2)	O2A—C11A	1.431 (12)
C7—H7	1.00	C11A—C12A	1.501 (15)
C8—C13	1.349 (2)	C11A—H11C	0.99
C8—C9	1.481 (2)	C11A—H11D	0.99
C9—O2A	1.359 (3)	C12A—H12D	0.98
C9—O2	1.361 (2)	C12A—H12E	0.98
C13—C21	1.505 (2)	C12A—H12F	0.98
C15—C16	1.382 (2)

C14—N1—C7	127.83 (14)	C15—C16—C17	119.04 (18)
C14—N1—H1N1	113.1	C15—C16—H16	120.5
C7—N1—H1N1	118.5	C17—C16—H16	120.5
C14—N2—C13	121.82 (14)	C18—C17—C16	119.8 (2)
C14—N2—C15	118.93 (13)	C18—C17—H17	120.1
C13—N2—C15	118.34 (13)	C16—C17—H17	120.1
C2—C1—C6	117.93 (17)	C19—C18—C17	120.74 (18)
C2—C1—H1	121.0	C19—C18—H18	119.6
C6—C1—H1	121.0	C17—C18—H18	119.6
F1—C2—C1	117.18 (17)	C18—C19—C20	119.90 (19)
F1—C2—C3	118.70 (16)	C18—C19—H19	120.1
C1—C2—C3	124.11 (18)	C20—C19—H19	120.1
C2—C3—C4	117.87 (16)	C15—C20—C19	119.04 (18)
C2—C3—H3	121.1	C15—C20—H20	120.5
C4—C3—H3	121.1	C19—C20—H20	120.5
C3—C4—C5	120.24 (17)	C13—C21—H21A	109.5
C3—C4—H4	119.9	C13—C21—H21B	109.5
C5—C4—H4	119.9	H21A—C21—H21B	109.5
C4—C5—C6	121.62 (16)	C13—C21—H21C	109.5
C4—C5—Br1	116.51 (13)	H21A—C21—H21C	109.5
C6—C5—Br1	121.87 (13)	H21B—C21—H21C	109.5
C5—C6—C1	118.20 (15)	C9—O2—C11	116.68 (18)
C5—C6—C7	123.85 (15)	O2—C11—C12	110.62 (19)
C1—C6—C7	117.90 (15)	O2—C11—H11A	109.5
N1—C7—C8	109.92 (14)	C12—C11—H11A	109.5
N1—C7—C6	107.99 (13)	O2—C11—H11B	109.5
C8—C7—C6	112.44 (13)	C12—C11—H11B	109.5
N1—C7—H7	108.8	H11A—C11—H11B	108.1
C8—C7—H7	108.8	C11—C12—H12A	109.5
C6—C7—H7	108.8	C11—C12—H12B	109.5
C13—C8—C9	126.36 (16)	H12A—C12—H12B	109.5
C13—C8—C7	121.87 (14)	C11—C12—H12C	109.5
C9—C8—C7	111.77 (15)	H12A—C12—H12C	109.5
O1—C9—O2A	107.4 (5)	H12B—C12—H12C	109.5
O1—C9—O2	123.54 (17)	C9—O2A—C11A	111.1 (8)
O1—C9—C8	121.38 (17)	O2A—C11A—C12A	99.2 (10)
O2A—C9—C8	124.7 (5)	O2A—C11A—H11C	111.9
O2—C9—C8	114.94 (16)	C12A—C11A—H11C	111.9
C8—C13—N2	120.36 (15)	O2A—C11A—H11D	111.9
C8—C13—C21	125.54 (15)	C12A—C11A—H11D	111.9
N2—C13—C21	114.07 (15)	H11C—C11A—H11D	109.6
N1—C14—N2	117.58 (14)	C11A—C12A—H12D	109.5
N1—C14—S1	121.21 (12)	C11A—C12A—H12E	109.5
N2—C14—S1	121.21 (12)	H12D—C12A—H12E	109.5
C16—C15—C20	121.44 (16)	C11A—C12A—H12F	109.5
C16—C15—N2	120.12 (15)	H12D—C12A—H12F	109.5
C20—C15—N2	118.31 (15)	H12E—C12A—H12F	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1ⁱ	0.85	2.51	3.327 (2)	162
C1—H1···F1ⁱⁱ	0.95	2.52	3.370 (2)	148
C7—H7···Br1	1.00	2.69	3.265 (2)	117
C20—H20···O1ⁱⁱⁱ	0.95	2.44	3.368 (3)	164
C21—H21A···O2	0.98	2.11	2.737 (3)	120
C21—H21B···Br1ⁱⁱⁱ	0.98	2.91	3.886 (2)	171

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y, −z; (iii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈BrFN₂O₂S
M_r	449.33
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.0455 (1), 10.2969 (1), 10.3714 (1)
α, β, γ (°)	64.286 (1), 83.110 (1), 78.796 (1)
V (Å³)	947.36 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.31
Crystal size (mm)	0.41 × 0.35 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.451, 0.631
No. of measured, independent and observed [I > 2σ(I)] reflections	30132, 5490, 4895
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.084, 1.05
No. of reflections	5490
No. of parameters	267
No. of restraints	15
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.66

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1ⁱ	0.85	2.51	3.327 (2)	162
C1—H1···F1ⁱⁱ	0.95	2.52	3.370 (2)	148
C7—H7···Br1	1.00	2.69	3.265 (2)	117
C20—H20···O1ⁱⁱⁱ	0.95	2.44	3.368 (3)	164
C21—H21A···O2	0.98	2.11	2.737 (3)	120
C21—H21B···Br1ⁱⁱⁱ	0.98	2.91	3.886 (2)	171

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y, −z; (iii) −x+1, −y+1, −z.

Footnotes

‡Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

Acknowledgements

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks the Universiti Sains Malaysia for a postdoctoral research fellowship.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Volume 64| Part 8| August 2008| Pages o1526-o1527

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl 4-(2-bromo-5-fluoro­phen­yl)-6-methyl-1-phenyl-2-thioxo-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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Acknowledgements

References

organic compounds

Ethyl 4-(2-bromo-5-fluorophenyl)-6-methyl-1-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate