N′-(2-Fluoro­benzo­yl)benzohydrazide

Ejsmont, K.; Zareef, M.; Arfan, M.; Bashir, S.A.; Zaleski, J.

doi:10.1107/S1600536808014645

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1128

doi:10.1107/S1600536808014645

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N′-(2-Fluorobenzoyl)benzohydrazide

Krzysztof Ejsmont,^a Muhammad Zareef,^b ^* Muhammad Arfan,^b Sarfaraz A. Bashir ^c and Jacek Zaleski ^a

^aInstitute of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland, ^bDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^cDepartment of Environmental Sciences, International Islamic University, Islamabad 45320, Pakistan
^*Correspondence e-mail: mzareef71@yahoo.com

(Received 1 April 2008; accepted 14 May 2008; online 21 May 2008)

In the crystal structure of the title compound, C₁₄H₁₁FN₂O₂, the molecule is centrosymmetric. The F atom is disordered over four positions, on the two ortho positions of each ring, with occupancies of 0.287:0.213 (5). In the crystal structure, molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Silva et al. (2006 ); Chopra et al. (2006 ); de Souza et al. (2007 ); Ahmad et al. (2001 ); Al-Soud, et al. (2004 ); Al-Talib et al. (1990 ); El-Emam et al. (2004 ); Yousif et al. (1986 ); Zareef & Iqbal (2007 ); Zheng et al. (2003 ).

Experimental

Crystal data

C₁₄H₁₁FN₂O₂
M_r = 258.25
Monoclinic, P 2₁ /c
a = 4.7698 (10) Å
b = 5.2435 (10) Å
c = 23.913 (5) Å
β = 100.89 (3)°
V = 587.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 90.0 (1) K
0.25 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: none
3819 measured reflections
1205 independent reflections
1060 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.094
S = 1.07
1205 reflections
118 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.84 (2)	2.05 (2)	2.8549 (16)	160.4 (16)
N1—H1⋯O3ⁱⁱ	0.84 (2)	2.325 (16)	2.6302 (14)	101.8 (14)
C8—H8⋯O3ⁱⁱⁱ	0.945 (17)	2.416 (16)	3.2687 (17)	150.0 (12)
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+1; (iii) x-1, y+1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2002 $[Oxford Diffraction (2002). CrysAlis CCD. Oxford Diffraction, Wrocław, Poland.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis RED. Oxford Diffraction, Wrocław, Poland.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014645/bq2073sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014645/bq2073Isup2.hkl

checkCIF report

Comment top

N,N'-Diacylhydrazines are very important intermediates especially for the synthesis of various biological active five member heterocyclic compounds such as 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4-oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In view of the versatility of these compounds, we have synthesized the title compound, (I), using a literature method (Zareef et al., 2007) and reported its crystal structure. The geometry of (I) is normal and (Table 1) compares well with those found in other crystal structures (Silva et al., 2006; Chopra et al., 2006; Souza et al., 2007). The title molecule, C₁₄H₁₁N₂O₂F, is non-planar. The dihedral angle between the benzene rings and CONHNHCO group is 34.5 (5) °. The disorder of the title molecule is realised by the presents of two positions for F atom with occupancy factors of 0.3 for F10 and 0.2 for F10'. The molecules are linked into a three-dimensional framework by a combination of two N–H···O and one weak C–H···O hydrogen bonds.

Related literature top

For related literature, see: Silva et al. (2006); Chopra et al. (2006); de Souza et al. (2007); Ahmad et al. (2001); Al-Soud, Al-Deeri & Al-Mosoudi (2004); Al-Talib, Tastoush & Odeh (1990); El-Emam, Al–Deeb, Al–Omar & Lehmann (2004); Yousif et al. (1986); Zareef & Iqbal (2007); Zheng et al. (2003).

Experimental top

For the synthesis of title compound (I), benzoyl chloride (5.1 mmol) was added in portions to a suspension of 2-fluorobenzoic hydrazide (5.0 mmol) in dry acetonitrile (50 ml), and the reaction mixture was stirred for 9 h at 296 K. Then, the resulting mixture was concentrated, and the solid product filtered and recrystallized from aqueous ethanol to afford the title compound (yield; 87%). Suitable crystals were grown from a solution of (I) in ethanol by slow evaporation at room temperature.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title molecule with anisotropic displacement parameters shown at the 50% probability level. [Symmetry code: (i) -x, -y, -z].
	Fig. 2. The packing diagram of the title compound. Dashed lines indicate hydrogen bonds.

N'-(2-Fluorobenzoyl)benzohydrazide top

Crystal data top

C₁₄H₁₁FN₂O₂	F(000) = 268
M_r = 258.25	D_x = 1.460 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1205 reflections
a = 4.7698 (10) Å	θ = 3.5–26.5°
b = 5.2435 (10) Å	µ = 0.11 mm⁻¹
c = 23.913 (5) Å	T = 90 K
β = 100.89 (3)°	Plate, colourless
V = 587.3 (2) Å³	0.25 × 0.20 × 0.10 mm
Z = 2

Data collection top

Oxford Diffraction Xcalibur diffractometer	1060 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 26.5°, θ_min = 3.5°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	h = −5→5
ω scans	k = −4→6
3819 measured reflections	l = −30→30
1205 independent reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0555P)² + 1.578P] where P = (F_o² + 2F_c²)/3
1205 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₄H₁₁FN₂O₂	V = 587.3 (2) Å³
M_r = 258.25	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.7698 (10) Å	µ = 0.11 mm⁻¹
b = 5.2435 (10) Å	T = 90 K
c = 23.913 (5) Å	0.25 × 0.20 × 0.10 mm
β = 100.89 (3)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	1060 reflections with I > 2σ(I)
3819 measured reflections	R_int = 0.044
1205 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.28 e Å⁻³
1205 reflections	Δρ_min = −0.28 e Å⁻³
118 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)
N1	0.4363 (2)	0.5857 (2)	0.47949 (4)	0.0183 (3)
C2	0.5853 (2)	0.6622 (2)	0.44055 (5)	0.0166 (3)
O3	0.83154 (17)	0.58840 (19)	0.44180 (4)	0.0255 (3)
C4	0.4404 (2)	0.8420 (2)	0.39624 (5)	0.0163 (3)
C5	0.5167 (3)	0.8362 (2)	0.34288 (5)	0.0193 (3)
H5	0.6561	0.7149	0.3356	0.023*	0.77 (6)
C6	0.3958 (3)	1.0022 (3)	0.30033 (5)	0.0228 (3)
C7	0.1997 (3)	1.1812 (2)	0.31099 (5)	0.0237 (3)
C8	0.1226 (3)	1.1921 (2)	0.36398 (6)	0.0235 (3)
C9	0.2420 (2)	1.0224 (2)	0.40602 (5)	0.0189 (3)
H9	0.1862	1.0290	0.4425	0.023*	0.73 (6)
F10	0.1593 (5)	1.0332 (5)	0.45796 (13)	0.0224 (10)	0.287 (5)
F10'	0.6956 (8)	0.6688 (8)	0.33028 (14)	0.0240 (13)	0.213 (5)
H1	0.258 (4)	0.605 (3)	0.4759 (7)	0.037 (5)*
H6	0.456 (3)	0.995 (3)	0.2630 (7)	0.030 (4)*
H7	0.114 (3)	1.296 (3)	0.2808 (7)	0.034 (4)*
H8	−0.007 (3)	1.315 (3)	0.3730 (6)	0.030 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0108 (5)	0.0275 (6)	0.0168 (5)	0.0041 (4)	0.0032 (4)	0.0053 (4)
C2	0.0118 (6)	0.0233 (6)	0.0149 (5)	0.0003 (4)	0.0029 (4)	−0.0014 (4)
O3	0.0128 (5)	0.0416 (6)	0.0234 (5)	0.0072 (4)	0.0066 (3)	0.0104 (4)
C4	0.0112 (5)	0.0201 (6)	0.0170 (6)	−0.0023 (4)	0.0011 (4)	−0.0004 (4)
C5	0.0167 (6)	0.0225 (6)	0.0185 (6)	0.0016 (5)	0.0030 (5)	−0.0002 (5)
C6	0.0233 (7)	0.0274 (7)	0.0171 (6)	−0.0013 (5)	0.0028 (5)	0.0017 (5)
C7	0.0205 (6)	0.0231 (6)	0.0251 (6)	−0.0002 (5)	−0.0019 (5)	0.0073 (5)
C8	0.0192 (6)	0.0191 (6)	0.0324 (7)	0.0032 (5)	0.0052 (5)	0.0007 (5)
C9	0.0171 (6)	0.0202 (6)	0.0200 (6)	−0.0013 (5)	0.0050 (5)	−0.0017 (4)
F10	0.0267 (15)	0.0234 (14)	0.0195 (16)	0.0052 (10)	0.0104 (10)	−0.0014 (10)
F10'	0.026 (2)	0.029 (2)	0.0184 (18)	0.0116 (15)	0.0068 (14)	0.0018 (13)

Geometric parameters (Å, º) top

N1—C2	1.3354 (16)	C6—C7	1.3824 (19)
N1—N1ⁱ	1.384 (2)	C6—H6	0.989 (15)
N1—H1	0.84 (2)	C7—C8	1.3856 (19)
C2—O3	1.2315 (14)	C7—H7	0.971 (17)
C2—C4	1.4875 (16)	C8—C9	1.3822 (18)
C4—C9	1.3890 (17)	C8—H8	0.945 (17)
C4—C5	1.3916 (17)	C9—F10	1.373 (4)
C5—F10'	1.299 (5)	C9—H9	0.9600
C5—C6	1.3797 (18)	F10—H9	0.4136
C5—H5	0.9600	F10'—H5	0.3448

C2—N1—N1ⁱ	117.97 (12)	C5—C6—C7	119.69 (12)
C2—N1—H1	123.5 (11)	C5—C6—H6	119.3 (10)
N1ⁱ—N1—H1	116.7 (12)	C7—C6—H6	121.0 (10)
O3—C2—N1	121.31 (11)	C6—C7—C8	120.16 (12)
O3—C2—C4	121.94 (11)	C6—C7—H7	119.4 (10)
N1—C2—C4	116.75 (10)	C8—C7—H7	120.4 (10)
C9—C4—C5	118.28 (11)	C9—C8—C7	119.64 (12)
C9—C4—C2	123.46 (11)	C9—C8—H8	118.0 (9)
C5—C4—C2	118.20 (10)	C7—C8—H8	122.3 (9)
F10'—C5—C6	117.16 (18)	F10—C9—C8	118.83 (14)
F10'—C5—C4	121.64 (17)	F10—C9—C4	120.10 (14)
C6—C5—C4	121.15 (11)	C8—C9—C4	121.07 (11)
C6—C5—H5	119.4	C8—C9—H9	119.4
C4—C5—H5	119.5	C4—C9—H9	119.5

N1ⁱ—N1—C2—O3	−1.9 (2)	F10'—C5—C6—C7	178.7 (2)
N1ⁱ—N1—C2—C4	178.67 (12)	C4—C5—C6—C7	1.29 (19)
O3—C2—C4—C9	−147.25 (13)	C5—C6—C7—C8	−0.64 (19)
N1—C2—C4—C9	32.16 (16)	C6—C7—C8—C9	−0.29 (19)
O3—C2—C4—C5	29.97 (17)	C7—C8—C9—F10	−178.88 (16)
N1—C2—C4—C5	−150.62 (11)	C7—C8—C9—C4	0.61 (19)
C9—C4—C5—F10'	−178.3 (2)	C5—C4—C9—F10	179.49 (16)
C2—C4—C5—F10'	4.3 (3)	C2—C4—C9—F10	−3.3 (2)
C9—C4—C5—C6	−0.97 (18)	C5—C4—C9—C8	0.01 (18)
C2—C4—C5—C6	−178.33 (11)	C2—C4—C9—C8	177.23 (11)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱⁱ	0.84 (2)	2.05 (2)	2.8549 (16)	160.4 (16)
N1—H1···O3ⁱ	0.84 (2)	2.325 (16)	2.6302 (14)	101.8 (14)
C8—H8···O3ⁱⁱⁱ	0.945 (17)	2.416 (16)	3.2687 (17)	150.0 (12)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁FN₂O₂
M_r	258.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	90
a, b, c (Å)	4.7698 (10), 5.2435 (10), 23.913 (5)
β (°)	100.89 (3)
V (Å³)	587.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3819, 1205, 1060
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.07
No. of reflections	1205
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.84 (2)	2.05 (2)	2.8549 (16)	160.4 (16)
N1—H1···O3ⁱⁱ	0.84 (2)	2.325 (16)	2.6302 (14)	101.8 (14)
C8—H8···O3ⁱⁱⁱ	0.945 (17)	2.416 (16)	3.2687 (17)	150.0 (12)

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

Acknowledgements

The authors are grateful to the late Professor Dr Rashid Iqbal for his great contribution to this research project.

References

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