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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2830.
Published online 2009 October 23. doi:  10.1107/S1600536809042809
PMCID: PMC2971114

N′-[(E)-1-(3-Fluoro­phen­yl)ethyl­idene]formohydrazide

Abstract

In the title compound, C9H9FN2O, the dihedral angle between the fluoro­benzene ring and the mean plane of the side chain is 15.59 (14)°. In the crystal, the mol­ecules form inversion dimers linked by pairs of N—H(...)O hydrogen bonds, resulting in R 2 2(8) loops. These dimers are reinforced by C—H(...)O inter­actions.

Related literature

For related structures, see: Shafiq et al. (2009a [triangle],b [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

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Object name is e-65-o2830-scheme1.jpg

Experimental

Crystal data

  • C9H9FN2O
  • M r = 180.18
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2830-efi1.jpg
  • a = 6.8466 (5) Å
  • b = 7.0258 (6) Å
  • c = 9.9419 (8) Å
  • α = 70.558 (5)°
  • β = 81.267 (5)°
  • γ = 73.977 (4)°
  • V = 432.50 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 296 K
  • 0.28 × 0.12 × 0.10 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.986, T max = 0.990
  • 19438 measured reflections
  • 2124 independent reflections
  • 1320 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.148
  • S = 1.00
  • 2124 reflections
  • 119 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809042809/hb5150sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042809/hb5150Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore, and for technical support, respectively.

supplementary crystallographic information

Comment

Recently we have reported the crystal structures of (II) N'-[(1E)-1-(4-Chlorophenyl)ethylidene]formohydrazide (Shafiq et al., 2009a), (III) N'-[(E)-(5-Methylfuran-2-yl)methylidene]formohydrazide (Shafiq et al., 2009b). The title compound (I, Fig. 1) has been prepared in continuation of synthesizing various formohydrazide derivatives.

In (I), the groups A (C1—C6/F1) and B (C7/C8/N1/N2/C9) are planar with maximum r. m. s. deviations of 0.0022 and 0.0146 Å, respectively from their mean squares planes. The dihedral angle between A/B is 15.59 (14)°.

The molecules of (I) consist of dimers similar to (II) and (III) due to N–H···O type of intermolecular H-bondings forming R22(8) ring motifs (Bernstein et al., 1995). The difference between (I) and (II) is the substitution of Cl and F-atom on the para and meta positions of benzene ring, respectively. Due to this change there exist two R21(7) ring motifs in dimers due to C–H···O and N—H···O H-bondings (Table 1).

Experimental

To a hot stirred solution of formic hydrazide (1.0 g, 0.017 mol) in ethanol (15 ml) was added 1-(3-fluorophenyl)ethanone (2.043 ml, 0.017 mol). The resultant mixture was then heated under reflux. The reaction mixture was refluxed about 12 h and monitored through TLC. After the completion of reaction, the mixture was cooled to room temperature. The solid was collected by suction filtration. The product obtained was washed with hot ethanol and 1,4-dioxan and dried. Colourless needles of (I) were obtained by recrystallization of the crude product in 1,4-dioxan after two days.

Refinement

The H-atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl C).

Figures

Fig. 1.
View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by circles of arbitrary radius.
Fig. 2.
The partial packing of (I), which shows that molecules form dimers.

Crystal data

C9H9FN2OZ = 2
Mr = 180.18F(000) = 188
Triclinic, P1Dx = 1.384 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.8466 (5) ÅCell parameters from 2124 reflections
b = 7.0258 (6) Åθ = 3.1–28.3°
c = 9.9419 (8) ŵ = 0.11 mm1
α = 70.558 (5)°T = 296 K
β = 81.267 (5)°Cut needle, colourless
γ = 73.977 (4)°0.28 × 0.12 × 0.10 mm
V = 432.50 (6) Å3

Data collection

Bruker Kappa APEXII CCD diffractometer2124 independent reflections
Radiation source: fine-focus sealed tube1320 reflections with I > 2σ(I)
graphiteRint = 0.028
Detector resolution: 7.40 pixels mm-1θmax = 28.3°, θmin = 3.1°
ω scansh = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −9→9
Tmin = 0.986, Tmax = 0.990l = −13→12
19438 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0721P)2 + 0.1041P] where P = (Fo2 + 2Fc2)/3
2124 reflections(Δ/σ)max < 0.001
119 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.20 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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)

xyzUiso*/Ueq
F1−0.17799 (17)0.19897 (19)0.11146 (13)0.0654 (5)
O1−0.27158 (19)1.0743 (2)0.48303 (16)0.0571 (5)
N1−0.0361 (2)0.6861 (2)0.32755 (15)0.0397 (4)
N2−0.0531 (2)0.8255 (2)0.40149 (15)0.0423 (5)
C10.1524 (2)0.4305 (3)0.22398 (18)0.0385 (5)
C2−0.0221 (3)0.3804 (3)0.20534 (18)0.0414 (5)
C3−0.0068 (3)0.2466 (3)0.12916 (19)0.0443 (6)
C40.1727 (3)0.1578 (3)0.0688 (3)0.0600 (8)
C50.3447 (3)0.2084 (4)0.0867 (3)0.0734 (10)
C60.3367 (3)0.3417 (3)0.1637 (2)0.0582 (7)
C70.1417 (2)0.5780 (3)0.30417 (18)0.0395 (5)
C80.3324 (3)0.5870 (4)0.3542 (3)0.0689 (8)
C9−0.2381 (3)0.9408 (3)0.4233 (2)0.0462 (6)
H2−0.147950.437320.244330.0496*
H2A0.052150.837560.432420.0507*
H40.178120.066890.017690.0720*
H50.469340.151680.045990.0882*
H60.455660.372300.175380.0698*
H8A0.305190.604320.447550.1034*
H8B0.380930.702260.288850.1034*
H8C0.433880.460050.358380.1034*
H9−0.348090.918440.391330.0554*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0472 (7)0.0812 (9)0.0917 (9)−0.0205 (6)−0.0071 (6)−0.0522 (7)
O10.0416 (7)0.0611 (9)0.0844 (10)−0.0063 (6)0.0031 (6)−0.0510 (8)
N10.0379 (7)0.0397 (8)0.0486 (8)−0.0064 (6)−0.0014 (6)−0.0256 (7)
N20.0350 (7)0.0458 (8)0.0558 (9)−0.0057 (6)−0.0034 (6)−0.0312 (7)
C10.0353 (8)0.0386 (9)0.0457 (10)−0.0038 (7)−0.0042 (7)−0.0217 (8)
C20.0348 (8)0.0458 (10)0.0482 (10)−0.0059 (7)0.0000 (7)−0.0247 (8)
C30.0392 (9)0.0480 (10)0.0543 (11)−0.0110 (8)−0.0071 (7)−0.0248 (9)
C40.0485 (11)0.0681 (13)0.0841 (15)−0.0068 (9)−0.0018 (10)−0.0570 (12)
C50.0407 (10)0.0940 (18)0.112 (2)−0.0058 (10)0.0056 (11)−0.0791 (16)
C60.0332 (9)0.0723 (14)0.0886 (15)−0.0071 (9)−0.0009 (9)−0.0558 (12)
C70.0357 (8)0.0408 (9)0.0470 (10)−0.0046 (7)−0.0058 (7)−0.0224 (8)
C80.0423 (10)0.0802 (15)0.1084 (18)0.0019 (10)−0.0197 (11)−0.0673 (14)
C90.0356 (9)0.0491 (10)0.0638 (12)−0.0082 (7)−0.0003 (8)−0.0330 (9)

Geometric parameters (Å, °)

F1—C31.355 (2)C4—C51.372 (3)
O1—C91.223 (3)C5—C61.379 (3)
N1—N21.380 (2)C7—C81.490 (3)
N1—C71.278 (2)C2—H20.9300
N2—C91.332 (3)C4—H40.9300
N2—H2A0.8600C5—H50.9300
C1—C21.389 (3)C6—H60.9300
C1—C71.485 (3)C8—H8A0.9600
C1—C61.388 (3)C8—H8B0.9600
C2—C31.365 (3)C8—H8C0.9600
C3—C41.364 (3)C9—H90.9300
N2—N1—C7117.88 (15)O1—C9—N2123.78 (19)
N1—N2—C9117.74 (15)C1—C2—H2120.00
C9—N2—H2A121.00C3—C2—H2120.00
N1—N2—H2A121.00C3—C4—H4121.00
C6—C1—C7120.83 (15)C5—C4—H4121.00
C2—C1—C7120.92 (16)C4—C5—H5119.00
C2—C1—C6118.24 (18)C6—C5—H5119.00
C1—C2—C3119.28 (19)C1—C6—H6120.00
C2—C3—C4123.5 (2)C5—C6—H6120.00
F1—C3—C2118.80 (18)C7—C8—H8A109.00
F1—C3—C4117.74 (18)C7—C8—H8B109.00
C3—C4—C5117.2 (2)C7—C8—H8C109.00
C4—C5—C6121.4 (2)H8A—C8—H8B110.00
C1—C6—C5120.5 (2)H8A—C8—H8C109.00
N1—C7—C1115.92 (14)H8B—C8—H8C109.00
N1—C7—C8124.86 (19)O1—C9—H9118.00
C1—C7—C8119.20 (17)N2—C9—H9118.00
C7—N1—N2—C9178.74 (16)C2—C1—C7—C8164.42 (19)
N2—N1—C7—C1−179.88 (14)C6—C1—C7—N1164.85 (17)
N2—N1—C7—C81.7 (3)C6—C1—C7—C8−16.6 (3)
N1—N2—C9—O1−177.46 (17)C1—C2—C3—F1−179.92 (16)
C6—C1—C2—C30.1 (3)C1—C2—C3—C4−0.2 (3)
C7—C1—C2—C3179.02 (17)F1—C3—C4—C5179.6 (2)
C2—C1—C6—C50.4 (3)C2—C3—C4—C5−0.2 (4)
C7—C1—C6—C5−178.6 (2)C3—C4—C5—C60.7 (4)
C2—C1—C7—N1−14.1 (3)C4—C5—C6—C1−0.8 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.862.142.989 (2)168
C8—H8A···O1i0.962.523.204 (3)129

Symmetry codes: (i) −x, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5150).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Shafiq, Z., Yaqub, M., Tahir, M. N., Nawaz, M. H. & Iqbal, M. S. (2009a). Acta Cryst. E65, o2494. [PMC free article] [PubMed]
  • Shafiq, Z., Yaqub, M., Tahir, M. N., Nawaz, M. H. & Iqbal, M. S. (2009b). Acta Cryst. E65, o2495. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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