supplementary materials
N'-(2-Fluorobenzylidene)acetohydrazide
The title compound, C9H9FN2O, was prepared by the reaction between 2-fluorobenzophenone and acetohydrazide. In the crystal structure, inversion dimers linked by pairs of N-H
O hydrogen bonds occur, generating R22(8) loops.
A mixture of 2-fluorobenzophenone (0.05 mol) and acethydrazide (0.05 mol)
was stirred in refluxing ethanol(30 ml) for 4 h to afford the title compound
(yield 70%). Colourless blocks of (I)
were obtained by recrystallization from ethanol at room temperature.
All H atoms were fixed geometrically and allowed to ride on their attached
atoms, with C—H and N—H distances in the range 0.93-0.97Å and 0.86 Å,
respectively, and with Uiso(H) = 1.2Ueq of the parent atoms.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: SHELXTL (Sheldrick, 2008).
N'-(2-Fluorobenzylidene)acetohydrazide
top
Crystal data top
| C9H9FN2O | F(000) = 376 |
| Mr = 180.18 | Dx = 1.355 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1515 reflections |
| a = 5.3227 (11) Å | θ = 3.2–27.5° |
| b = 8.4603 (17) Å | µ = 0.11 mm−1 |
| c = 19.656 (4) Å | T = 293 K |
| β = 93.70 (3)° | Block, colourless |
| V = 883.3 (3) Å3 | 0.30 × 0.30 × 0.20 mm |
| Z = 4 | |
Data collection top
Bruker SMART CCD
diffractometer | 1515 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.036 |
| graphite | θmax = 27.5°, θmin = 3.2° |
| ω scans | h = −6→6 |
| 7687 measured reflections | k = −9→10 |
| 2010 independent reflections | l = −25→25 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
| wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0696P)2 + 0.0888P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 2010 reflections | Δρmax = 0.14 e Å−3 |
| 119 parameters | Δρmin = −0.21 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.035 (6) |
Crystal data top
| C9H9FN2O | V = 883.3 (3) Å3 |
| Mr = 180.18 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 5.3227 (11) Å | µ = 0.11 mm−1 |
| b = 8.4603 (17) Å | T = 293 K |
| c = 19.656 (4) Å | 0.30 × 0.30 × 0.20 mm |
| β = 93.70 (3)° | |
Data collection top
Bruker SMART CCD
diffractometer | 1515 reflections with I > 2σ(I) |
| 7687 measured reflections | Rint = 0.036 |
| 2010 independent reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
| wR(F2) = 0.128 | Δρmax = 0.14 e Å−3 |
| S = 1.04 | Δρmin = −0.21 e Å−3 |
| 2010 reflections | Absolute structure: ? |
| 119 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| N2 | 0.4557 (2) | 0.26752 (14) | 0.01843 (6) | 0.0474 (3) | |
| O1 | 0.04461 (18) | 0.48232 (13) | −0.09198 (5) | 0.0578 (3) | |
| N1 | 0.2546 (2) | 0.35774 (14) | −0.00633 (6) | 0.0505 (3) | |
| H1A | 0.1453 | 0.3885 | 0.0212 | 0.061* | |
| C1 | 0.6693 (3) | 0.15209 (16) | 0.11622 (7) | 0.0479 (3) | |
| C8 | 0.2245 (2) | 0.39930 (17) | −0.07282 (7) | 0.0473 (3) | |
| C7 | 0.4679 (3) | 0.24649 (16) | 0.08270 (7) | 0.0477 (3) | |
| H7A | 0.3469 | 0.2919 | 0.1086 | 0.057* | |
| F1 | 0.5354 (2) | 0.23104 (15) | 0.22231 (5) | 0.0865 (4) | |
| C9 | 0.4142 (3) | 0.3418 (2) | −0.11987 (7) | 0.0583 (4) | |
| H9A | 0.3699 | 0.3789 | −0.1652 | 0.087* | |
| H9B | 0.4168 | 0.2284 | −0.1197 | 0.087* | |
| H9C | 0.5777 | 0.3812 | −0.1049 | 0.087* | |
| C6 | 0.8398 (3) | 0.0646 (2) | 0.08064 (8) | 0.0592 (4) | |
| H6A | 0.8267 | 0.0649 | 0.0332 | 0.071* | |
| C2 | 0.6989 (3) | 0.1453 (2) | 0.18648 (7) | 0.0586 (4) | |
| C5 | 1.0271 (3) | −0.0222 (2) | 0.11457 (10) | 0.0708 (5) | |
| H5A | 1.1397 | −0.0794 | 0.0900 | 0.085* | |
| C3 | 0.8824 (4) | 0.0594 (2) | 0.22135 (9) | 0.0756 (5) | |
| H3A | 0.8947 | 0.0580 | 0.2688 | 0.091* | |
| C4 | 1.0489 (3) | −0.0250 (2) | 0.18462 (10) | 0.0756 (5) | |
| H4A | 1.1760 | −0.0839 | 0.2072 | 0.091* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| N2 | 0.0448 (6) | 0.0508 (6) | 0.0460 (6) | 0.0032 (5) | −0.0023 (5) | 0.0011 (5) |
| O1 | 0.0518 (6) | 0.0700 (7) | 0.0507 (6) | 0.0133 (5) | −0.0049 (4) | 0.0030 (5) |
| N1 | 0.0475 (6) | 0.0591 (7) | 0.0447 (6) | 0.0106 (5) | 0.0006 (5) | 0.0019 (5) |
| C1 | 0.0475 (7) | 0.0482 (7) | 0.0471 (7) | −0.0069 (6) | −0.0046 (5) | 0.0041 (5) |
| C8 | 0.0434 (7) | 0.0520 (7) | 0.0455 (7) | −0.0015 (6) | −0.0035 (5) | −0.0004 (5) |
| C7 | 0.0482 (7) | 0.0490 (7) | 0.0455 (7) | −0.0010 (6) | 0.0006 (5) | −0.0021 (5) |
| F1 | 0.0899 (8) | 0.1230 (10) | 0.0462 (5) | 0.0075 (6) | 0.0006 (5) | −0.0129 (5) |
| C9 | 0.0538 (8) | 0.0733 (10) | 0.0478 (7) | 0.0058 (7) | 0.0039 (6) | 0.0000 (7) |
| C6 | 0.0601 (9) | 0.0623 (9) | 0.0545 (8) | 0.0069 (7) | −0.0007 (6) | 0.0061 (7) |
| C2 | 0.0588 (9) | 0.0683 (10) | 0.0475 (7) | −0.0101 (7) | −0.0058 (6) | 0.0002 (6) |
| C5 | 0.0599 (10) | 0.0664 (11) | 0.0850 (12) | 0.0100 (8) | −0.0034 (8) | 0.0118 (9) |
| C3 | 0.0764 (11) | 0.0912 (13) | 0.0558 (9) | −0.0153 (10) | −0.0222 (8) | 0.0153 (8) |
| C4 | 0.0619 (10) | 0.0734 (12) | 0.0880 (12) | −0.0051 (8) | −0.0233 (9) | 0.0253 (10) |
Geometric parameters (Å, °) top
| N2—C7 | 1.2732 (18) | C9—H9A | 0.9600 |
| N2—N1 | 1.3775 (16) | C9—H9B | 0.9600 |
| O1—C8 | 1.2269 (17) | C9—H9C | 0.9600 |
| N1—C8 | 1.3529 (17) | C6—C5 | 1.376 (2) |
| N1—H1A | 0.8600 | C6—H6A | 0.9300 |
| C1—C2 | 1.3809 (19) | C2—C3 | 1.366 (2) |
| C1—C6 | 1.394 (2) | C5—C4 | 1.375 (3) |
| C1—C7 | 1.4595 (19) | C5—H5A | 0.9300 |
| C8—C9 | 1.494 (2) | C3—C4 | 1.379 (3) |
| C7—H7A | 0.9300 | C3—H3A | 0.9300 |
| F1—C2 | 1.363 (2) | C4—H4A | 0.9300 |
| | | |
| C7—N2—N1 | 114.63 (11) | H9A—C9—H9C | 109.5 |
| C8—N1—N2 | 121.75 (11) | H9B—C9—H9C | 109.5 |
| C8—N1—H1A | 119.1 | C5—C6—C1 | 121.01 (15) |
| N2—N1—H1A | 119.1 | C5—C6—H6A | 119.5 |
| C2—C1—C6 | 116.37 (14) | C1—C6—H6A | 119.5 |
| C2—C1—C7 | 120.46 (13) | F1—C2—C3 | 118.90 (14) |
| C6—C1—C7 | 123.17 (12) | F1—C2—C1 | 117.35 (14) |
| O1—C8—N1 | 119.12 (13) | C3—C2—C1 | 123.74 (16) |
| O1—C8—C9 | 122.79 (13) | C4—C5—C6 | 120.45 (17) |
| N1—C8—C9 | 118.08 (12) | C4—C5—H5A | 119.8 |
| N2—C7—C1 | 120.89 (13) | C6—C5—H5A | 119.8 |
| N2—C7—H7A | 119.6 | C2—C3—C4 | 118.43 (16) |
| C1—C7—H7A | 119.6 | C2—C3—H3A | 120.8 |
| C8—C9—H9A | 109.5 | C4—C3—H3A | 120.8 |
| C8—C9—H9B | 109.5 | C5—C4—C3 | 120.00 (16) |
| H9A—C9—H9B | 109.5 | C5—C4—H4A | 120.0 |
| C8—C9—H9C | 109.5 | C3—C4—H4A | 120.0 |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.86 | 2.08 | 2.915 (2) | 163 |
| Symmetry codes: (i) −x, −y+1, −z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.86 | 2.08 | 2.915 (2) | 163 |
| Symmetry codes: (i) −x, −y+1, −z. |
The authors would like to thank the National Natural Science Foundation of
Shandong Province (Y2008B29) and Yuandu Scholar of Weifang City for support.
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153.
Girgis, A. S. (2006). J. Chem. Res. pp. 81–85.
Li, Y.-F. & Jian, F.-F. (2008). Acta Cryst. E64, o2409.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./hb5371fig1thm.gif)
Schiff bases have important applications in analytical chemistry (Cimerman et al., 1997). As part of our search for new Schiff bases with similar applications, we synthesized the title compound, (I), and report its crystal structure herein (Fig. 1).
All the bond lengths and angles in (I) are within normal ranges (Li & Jian, 2008). The C7=N2 bond length of 1.2732 (18)Å is slight shorter than the C=N double bond [1.281 (2) Å] reported (Girgis, 2006) in a related compound.
In the crystal structure, adjacent molecules are linked into a centro-symmetric supra-molecular dimer by intermolecular N—H···O hydrogen bonding (Table 1).