5-(4-Fluoro­phen­yl)-5-methyl­imidazolidine-2,4-dione

Kashif, M.K.; Hussain, A.; Khawar Rauf, M.; Ebihara, M.; Hameed, S.

doi:10.1107/S1600536807067803

organic compounds

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Volume 64| Part 2| February 2008| Page o444

doi:10.1107/S1600536807067803

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5-(4-Fluorophenyl)-5-methylimidazolidine-2,4-dione

M. Kaleem Kashif,^a Abid Hussain,^a M. Khawar Rauf,^b Masahiro Ebihara ^b and Shahid Hameed ^a ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
^*Correspondence e-mail: shameed@qau.edu.pk

(Received 30 November 2007; accepted 19 December 2007; online 16 January 2008)

In the title compound, C₁₀H₉FN₂O₂, the dihedral angle between the hydantoin unit and the benzene ring is 65.55 (5)°. The atoms in the hydantoin ring are coplanar, with a mean deviation of 0.015 Å and a maximum deviation of 0.075 (2) Å for one carbonyl O atom. N—H⋯O hydrogen bonds link the molecules into one-dimensional chains, with one carbonyl group acting as a bifurcated acceptor and the other accepting no hydrogen bonds.

Related literature

For related literature, see: Ahmad et al. (2000 , 2002 ); Balavoine et al. (2007 ); Mullica et al. (1998 ); Park et al. (2007 ); Rajic et al. (2006 ); Sheppeck et al. (2007 ).

Experimental

Crystal data

C₁₀H₉FN₂O₂
M_r = 208.19
Orthorhombic, P b c a
a = 7.096 (2) Å
b = 11.348 (3) Å
c = 22.661 (7) Å
V = 1824.7 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 123 (2) K
0.34 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: none
13516 measured reflections
2083 independent reflections
2054 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.094
S = 1.22
2083 reflections
145 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88 (2)	2.04 (2)	2.8834 (17)	160.5 (18)
N2—H2⋯O1ⁱⁱ	0.89 (2)	1.96 (2)	2.8318 (17)	165.9 (17)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ); cell refinement: CrystalClear; data reduction: TEXSAN (Rigaku/MSC, 2004 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97 and TEXSAN.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067803/bi2269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067803/bi2269Isup2.hkl

checkCIF report

Comment top

Active research is being carried out in this laboratory on the synthesis of sulfonyl cyclic ureas and their evaluation as hypoglycemic agents (Ahmad et al., 2002; Ahmad et al., 2000). Imidazolidine-2,4-diones, a class of cyclic urea molecules, exhibit diverse biological activities like anti-cancer (Sheppeck et al., 2007), anti-viral (Rajic et al., 2006), COX-2 inhibitors (Park et al., 2007) and hormone receptor antagonists (Balavoine et al., 2007). The title compound (Fig. 1) was synthesized as an intermediate for onward conversion to sulfonyl derivatives for hypoglycemic assay. It contains a hydantoin ring attached to a methyl and p-flourophenyl group at the chiral centre C1. All bond distances are in agreement with experimental values found in similar compounds. The atoms in the hydantoin ring are planar as expected (Mullica et al., 1998) with a mean standard deviation of 0.015 Å. The C2—O1 and C3—O2 bond distances are 1.2320 (17) Å and 1.2080 (17) Å, respectively, which are close to the standard value for C?O (1.20 Å). The dihedral angle subtended by the p-flourophenyl group at the chiral centre C(1) is 65.55 (5)°.

Related literature top

For related literature, see: Ahmad et al. (2000, 2002); Balavoine et al. (2007); Mullica et al. (1998); Park et al. (2007); Rajic et al. (2006); Sheppeck et al. (2007).

Experimental top

4-Fluoroacetophenone (0.1 mol) and ammonium carbonate (0.6 mol) were placed in a 100 ml round bottom flask. Potassium cyanide (0.1 mol) was dissolved in aqueous ethanol (60%) and added to the reaction flask. The mixture was heated on an oil bath at 328–333 K until the reaction was completed (monitored by TLC). After cooling to room temperature, the reaction mixture was concentrated and acidified using conc. HCl. The resulting precipitate was filtered, dissolved in saturated NaOH(aq) solution and extracted with diethyl ether (25 ml). The aqueous layer was acidified to precipitate the title compound, which was filtered, dried and recrystallized from ethanol/water. Yield: 75%; m.p. 485–488 K; R_f (pet. ether/ethyl acetate 1:2) 0.58.

IR (KBr, ν_max, cm^-1): 3412, 3245, 3058, 2989, 1773, 1719, 1602, 1378, 1274, 838; ¹H-NMR (acetone-d6) δ: 1.80 (3H, s), 7.18 (2H, m), 7.64 (2H, m), 7.71 (1H, bs), 9.72 (1H, bs); EIMS (m/z, %): 208 (M⁺, 20), 193 (65), 165 (5), 137 (36), 122 (100), 95 (25); Elemental analysis calculated: C 57.69, H 4.36, N 13.46; found: C 57.62, H 4.38, N 13.60%.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: TEXSAN (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and TEXSAN (Rigaku/MSC, 2004).

Figures top

Fig. 1. Molecular structure showing displacement ellipsoids at the 30% probability level for non-H atoms.

5-(4-Fluorophenyl)-5-methylimidazolidine-2,4-dione top

Crystal data top

C₁₀H₉FN₂O₂	F(000) = 864
M_r = 208.19	D_x = 1.516 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5426 reflections
a = 7.096 (2) Å	θ = 3.0–27.5°
b = 11.348 (3) Å	µ = 0.12 mm⁻¹
c = 22.661 (7) Å	T = 123 K
V = 1824.7 (10) Å³	Block, colorless
Z = 8	0.34 × 0.30 × 0.20 mm

Data collection top

Rigaku Mercury CCD diffractometer	2054 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 14.62 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −9→8
13516 measured reflections	k = −14→13
2083 independent reflections	l = −17→29

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ²(F_o²) + (0.028P)² + 1.2798P] where P = (F_o² + 2F_c²)/3
2083 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₀H₉FN₂O₂	V = 1824.7 (10) Å³
M_r = 208.19	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.096 (2) Å	µ = 0.12 mm⁻¹
b = 11.348 (3) Å	T = 123 K
c = 22.661 (7) Å	0.34 × 0.30 × 0.20 mm

Data collection top

Rigaku Mercury CCD diffractometer	2054 reflections with I > 2σ(I)
13516 measured reflections	R_int = 0.026
2083 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	Δρ_max = 0.31 e Å⁻³
2083 reflections	Δρ_min = −0.16 e Å⁻³
145 parameters

Special details top

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
C1	0.13701 (19)	0.06340 (11)	0.10194 (6)	0.0127 (3)
N1	0.09007 (16)	0.16162 (10)	0.06286 (5)	0.0141 (2)
H1	−0.025 (3)	0.1859 (17)	0.0547 (9)	0.028 (5)*
C2	0.23589 (19)	0.19597 (12)	0.02932 (6)	0.0135 (3)
O1	0.23772 (14)	0.27474 (9)	−0.00808 (4)	0.0167 (2)
N2	0.38961 (17)	0.12558 (10)	0.04332 (5)	0.0151 (3)
H2	0.504 (3)	0.1445 (16)	0.0305 (8)	0.024 (5)*
C3	0.34432 (19)	0.04077 (11)	0.08415 (6)	0.0129 (3)
O2	0.44614 (15)	−0.03631 (8)	0.10246 (4)	0.0177 (2)
C4	0.13117 (18)	0.09904 (11)	0.16706 (6)	0.0118 (3)
C5	0.08781 (19)	0.21387 (12)	0.18428 (6)	0.0150 (3)
H5	0.0607	0.2719	0.1553	0.018*
C6	0.0841 (2)	0.24367 (12)	0.24395 (6)	0.0175 (3)
H6	0.0542	0.3217	0.2560	0.021*
C7	0.1246 (2)	0.15835 (13)	0.28513 (6)	0.0170 (3)
C8	0.1685 (2)	0.04404 (12)	0.26982 (6)	0.0158 (3)
H8	0.1954	−0.0134	0.2992	0.019*
C9	0.17244 (19)	0.01526 (12)	0.21023 (6)	0.0139 (3)
H9	0.2037	−0.0628	0.1987	0.017*
C10	0.0141 (2)	−0.04446 (12)	0.08893 (6)	0.0183 (3)
H10A	−0.1179	−0.0258	0.0975	0.027*
H10B	0.0549	−0.1105	0.1137	0.027*
H10C	0.0267	−0.0660	0.0472	0.027*
F1	0.12297 (14)	0.18871 (8)	0.34320 (4)	0.0258 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0126 (6)	0.0140 (6)	0.0116 (6)	−0.0001 (5)	−0.0008 (5)	0.0028 (5)
N1	0.0104 (5)	0.0188 (6)	0.0132 (5)	0.0008 (4)	−0.0007 (4)	0.0057 (4)
C2	0.0120 (6)	0.0168 (6)	0.0115 (6)	−0.0011 (5)	−0.0016 (5)	−0.0003 (5)
O1	0.0127 (5)	0.0210 (5)	0.0166 (5)	0.0002 (4)	0.0000 (4)	0.0079 (4)
N2	0.0112 (6)	0.0183 (6)	0.0159 (6)	0.0004 (4)	0.0011 (4)	0.0053 (5)
C3	0.0145 (6)	0.0138 (6)	0.0105 (6)	−0.0007 (5)	0.0001 (5)	−0.0003 (5)
O2	0.0183 (5)	0.0163 (5)	0.0186 (5)	0.0042 (4)	0.0014 (4)	0.0030 (4)
C4	0.0092 (6)	0.0147 (6)	0.0115 (6)	−0.0016 (5)	0.0008 (5)	0.0009 (5)
C5	0.0145 (6)	0.0137 (6)	0.0169 (6)	−0.0010 (5)	0.0012 (5)	0.0026 (5)
C6	0.0172 (7)	0.0145 (6)	0.0209 (7)	−0.0014 (5)	0.0052 (5)	−0.0037 (5)
C7	0.0155 (7)	0.0229 (7)	0.0125 (6)	−0.0043 (5)	0.0030 (5)	−0.0042 (5)
C8	0.0147 (6)	0.0194 (6)	0.0132 (6)	−0.0015 (5)	0.0001 (5)	0.0037 (5)
C9	0.0136 (6)	0.0133 (6)	0.0148 (6)	0.0002 (5)	0.0007 (5)	0.0009 (5)
C10	0.0200 (7)	0.0196 (7)	0.0152 (6)	−0.0070 (5)	−0.0006 (5)	−0.0002 (5)
F1	0.0347 (5)	0.0288 (5)	0.0140 (4)	−0.0055 (4)	0.0051 (4)	−0.0061 (4)

Geometric parameters (Å, º) top

C1—N1	1.4620 (17)	C5—C6	1.394 (2)
C1—C4	1.5306 (18)	C5—H5	0.950
C1—C10	1.5316 (19)	C6—C7	1.375 (2)
C1—C3	1.5468 (19)	C6—H6	0.950
N1—C2	1.3417 (18)	C7—F1	1.3604 (16)
N1—H1	0.88 (2)	C7—C8	1.378 (2)
C2—O1	1.2320 (17)	C8—C9	1.3897 (19)
C2—N2	1.3887 (18)	C8—H8	0.950
N2—C3	1.3732 (17)	C9—H9	0.950
N2—H2	0.89 (2)	C10—H10A	0.980
C3—O2	1.2080 (17)	C10—H10B	0.980
C4—C5	1.3946 (19)	C10—H10C	0.980
C4—C9	1.3952 (18)

N1—C1—C4	112.11 (11)	C6—C5—C4	120.14 (13)
N1—C1—C10	111.28 (11)	C6—C5—H5	119.9
C4—C1—C10	112.42 (11)	C4—C5—H5	119.9
N1—C1—C3	100.68 (10)	C7—C6—C5	118.92 (13)
C4—C1—C3	108.71 (10)	C7—C6—H6	120.5
C10—C1—C3	111.03 (11)	C5—C6—H6	120.5
C2—N1—C1	112.89 (11)	F1—C7—C6	118.45 (13)
C2—N1—H1	120.3 (13)	F1—C7—C8	118.92 (13)
C1—N1—H1	125.2 (13)	C6—C7—C8	122.62 (13)
O1—C2—N1	127.49 (13)	C7—C8—C9	118.05 (12)
O1—C2—N2	124.48 (12)	C7—C8—H8	121.0
N1—C2—N2	108.02 (11)	C9—C8—H8	121.0
C3—N2—C2	111.91 (11)	C8—C9—C4	121.13 (12)
C3—N2—H2	127.1 (12)	C8—C9—H9	119.4
C2—N2—H2	120.3 (12)	C4—C9—H9	119.4
O2—C3—N2	126.79 (13)	C1—C10—H10A	109.5
O2—C3—C1	126.84 (12)	C1—C10—H10B	109.5
N2—C3—C1	106.37 (11)	H10A—C10—H10B	109.5
C5—C4—C9	119.13 (12)	C1—C10—H10C	109.5
C5—C4—C1	121.51 (12)	H10A—C10—H10C	109.5
C9—C4—C1	119.35 (12)	H10B—C10—H10C	109.5

C4—C1—N1—C2	113.75 (13)	C10—C1—C4—C5	−127.12 (14)
C10—C1—N1—C2	−119.38 (13)	C3—C1—C4—C5	109.54 (14)
C3—C1—N1—C2	−1.65 (14)	N1—C1—C4—C9	179.95 (12)
C1—N1—C2—O1	178.84 (13)	C10—C1—C4—C9	53.70 (17)
C1—N1—C2—N2	−0.49 (15)	C3—C1—C4—C9	−69.63 (15)
O1—C2—N2—C3	−176.54 (13)	C9—C4—C5—C6	−0.6 (2)
N1—C2—N2—C3	2.81 (16)	C1—C4—C5—C6	−179.82 (12)
C2—N2—C3—O2	176.10 (13)	C4—C5—C6—C7	0.3 (2)
C2—N2—C3—C1	−3.79 (15)	C5—C6—C7—F1	179.19 (12)
N1—C1—C3—O2	−176.71 (13)	C5—C6—C7—C8	−0.1 (2)
C4—C1—C3—O2	65.37 (17)	F1—C7—C8—C9	−178.99 (12)
C10—C1—C3—O2	−58.79 (17)	C6—C7—C8—C9	0.3 (2)
N1—C1—C3—N2	3.18 (13)	C7—C8—C9—C4	−0.7 (2)
C4—C1—C3—N2	−114.74 (12)	C5—C4—C9—C8	0.9 (2)
C10—C1—C3—N2	121.09 (12)	C1—C4—C9—C8	−179.95 (12)
N1—C1—C4—C5	−0.87 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88 (2)	2.04 (2)	2.8834 (17)	160.5 (18)
N2—H2···O1ⁱⁱ	0.89 (2)	1.96 (2)	2.8318 (17)	165.9 (17)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉FN₂O₂
M_r	208.19
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	7.096 (2), 11.348 (3), 22.661 (7)
V (Å³)	1824.7 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.34 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13516, 2083, 2054
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.094, 1.22
No. of reflections	2083
No. of parameters	145
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.16

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2001), SIR97 (Altomare et al., 1999), ORTEPII (Johnson, 1976), SHELXL97 (Sheldrick, 1997) and TEXSAN (Rigaku/MSC, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88 (2)	2.04 (2)	2.8834 (17)	160.5 (18)
N2—H2···O1ⁱⁱ	0.89 (2)	1.96 (2)	2.8318 (17)	165.9 (17)

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

Acknowledgements

MKR is grateful to the Higher Education Commission of Pakistan for financial support under the International Support Initiative Program for a Doctoral Fellowship at Gifu University, Japan.

References

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