Acta Cryst. (2008). E64, o1128 [ doi:10.1107/S1600536808014645 ]
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-HO hydrogen bonds.
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.
The occupancy factors for the disordered fluorine and hydrogen (H5 and H9) atoms were refined using free variables. The H5 nad H9 were included in the refinement at geometrically idealized positions with C-H distances 0.96 A and their parameters are not refinement. The remaining H atoms were located in a difference map and freely refined.
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).
![[Figure 1]](./bq2073fig1thm.gif)
| Fig. 1. View of the title molecule with anisotropic displacement parameters shown at the 50% probability level. [Symmetry code: (i) -x, -y, -z]. |
![[Figure 2]](./bq2073fig2thm.gif)
| Fig. 2. The packing diagram of the title compound. Dashed lines indicate hydrogen bonds. |
| C14H11FN2O2 | F(000) = 268 |
| Mr = 258.25 | Dx = 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 |
| Oxford Diffraction Xcalibur diffractometer | 1060 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.044 |
| graphite | θmax = 26.5°, θmin = 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 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(Fo2) + (0.0555P)2 + 1.578P] where P = (Fo2 + 2Fc2)/3 |
| 1205 reflections | (Δ/σ)max < 0.001 |
| 118 parameters | Δρmax = 0.28 e Å−3 |
| 0 restraints | Δρmin = −0.28 e Å−3 |
| C14H11FN2O2 | V = 587.3 (2) Å3 |
| Mr = 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)° |
| Oxford Diffraction Xcalibur diffractometer | 1060 reflections with I > 2σ(I) |
| 3819 measured reflections | Rint = 0.044 |
| 1205 independent reflections | θmax = 26.5° |
| R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.094 | Δρmax = 0.28 e Å−3 |
| S = 1.07 | Δρmin = −0.28 e Å−3 |
| 1205 reflections | Absolute structure: ? |
| 118 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | 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)* |
| 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) |
| 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 codes: (i) −x+1, −y+1, −z+1. |
| 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: (ii) x−1, y, z; (i) −x+1, −y+1, −z+1; (iii) x−1, y+1, z. |
| 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. |
The authors are grateful to the late Professor Dr Rashid Iqbal for his tremendous contribution to this research project.
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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.