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

Shafiq, Z.; Yaqub, M.; Tahir, M.N.; Nawaz, M.H.; Iqbal, M.S.

doi:10.1107/S1600536809042809

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2830

https://doi.org/10.1107/S1600536809042809

Open

access

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

Zahid Shafiq,^a Muhammad Yaqub,^a M. Nawaz Tahir,^b ^* Mian Hasnain Nawaz ^a and M. Saeed Iqbal ^c

^aDepartment of Chemistry, Bahauddin Zakariya University, Multan 60800, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 17 October 2009; accepted 18 October 2009; online 23 October 2009)

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 R₂²(8) loops. These dimers are reinforced by C—H⋯O interactions.

Related literature

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

Experimental

Crystal data

C₉H₉FN₂O
M_r = 180.18
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.044
wR(F²) = 0.148
S = 1.00
2124 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.86	2.14	2.989 (2)	168
C8—H8A⋯O1ⁱ	0.96	2.52	3.204 (3)	129
Symmetry code: (i) -x, -y+2, -z+1.

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042809/hb5150Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

	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.

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

Crystal data top

C₉H₉FN₂O	Z = 2
M_r = 180.18	F(000) = 188
Triclinic, P1	D_x = 1.384 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8466 (5) Å	Cell parameters from 2124 reflections
b = 7.0258 (6) Å	θ = 3.1–28.3°
c = 9.9419 (8) Å	µ = 0.11 mm⁻¹
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 top

Bruker Kappa APEXII CCD diffractometer	2124 independent reflections
Radiation source: fine-focus sealed tube	1320 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.3°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→9
T_min = 0.986, T_max = 0.990	l = −13→12
19438 measured 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0721P)² + 0.1041P] where P = (F_o² + 2F_c²)/3
2124 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₉FN₂O	γ = 73.977 (4)°
M_r = 180.18	V = 432.50 (6) Å³
Triclinic, P1	Z = 2
a = 6.8466 (5) Å	Mo Kα radiation
b = 7.0258 (6) Å	µ = 0.11 mm⁻¹
c = 9.9419 (8) Å	T = 296 K
α = 70.558 (5)°	0.28 × 0.12 × 0.10 mm
β = 81.267 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2124 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1320 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.990	R_int = 0.028
19438 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.00	Δρ_max = 0.23 e Å⁻³
2124 reflections	Δρ_min = −0.20 e Å⁻³
119 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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)
C1	0.1524 (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)
C4	0.1727 (3)	0.1578 (3)	0.0688 (3)	0.0600 (8)
C5	0.3447 (3)	0.2084 (4)	0.0867 (3)	0.0734 (10)
C6	0.3367 (3)	0.3417 (3)	0.1637 (2)	0.0582 (7)
C7	0.1417 (2)	0.5780 (3)	0.30417 (18)	0.0395 (5)
C8	0.3324 (3)	0.5870 (4)	0.3542 (3)	0.0689 (8)
C9	−0.2381 (3)	0.9408 (3)	0.4233 (2)	0.0462 (6)
H2	−0.14795	0.43732	0.24433	0.0496*
H2A	0.05215	0.83756	0.43242	0.0507*
H4	0.17812	0.06689	0.01769	0.0720*
H5	0.46934	0.15168	0.04599	0.0882*
H6	0.45566	0.37230	0.17538	0.0698*
H8A	0.30519	0.60432	0.44755	0.1034*
H8B	0.38093	0.70226	0.28885	0.1034*
H8C	0.43388	0.46005	0.35838	0.1034*
H9	−0.34809	0.91844	0.39133	0.0554*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0472 (7)	0.0812 (9)	0.0917 (9)	−0.0205 (6)	−0.0071 (6)	−0.0522 (7)
O1	0.0416 (7)	0.0611 (9)	0.0844 (10)	−0.0063 (6)	0.0031 (6)	−0.0510 (8)
N1	0.0379 (7)	0.0397 (8)	0.0486 (8)	−0.0064 (6)	−0.0014 (6)	−0.0256 (7)
N2	0.0350 (7)	0.0458 (8)	0.0558 (9)	−0.0057 (6)	−0.0034 (6)	−0.0312 (7)
C1	0.0353 (8)	0.0386 (9)	0.0457 (10)	−0.0038 (7)	−0.0042 (7)	−0.0217 (8)
C2	0.0348 (8)	0.0458 (10)	0.0482 (10)	−0.0059 (7)	0.0000 (7)	−0.0247 (8)
C3	0.0392 (9)	0.0480 (10)	0.0543 (11)	−0.0110 (8)	−0.0071 (7)	−0.0248 (9)
C4	0.0485 (11)	0.0681 (13)	0.0841 (15)	−0.0068 (9)	−0.0018 (10)	−0.0570 (12)
C5	0.0407 (10)	0.0940 (18)	0.112 (2)	−0.0058 (10)	0.0056 (11)	−0.0791 (16)
C6	0.0332 (9)	0.0723 (14)	0.0886 (15)	−0.0071 (9)	−0.0009 (9)	−0.0558 (12)
C7	0.0357 (8)	0.0408 (9)	0.0470 (10)	−0.0046 (7)	−0.0058 (7)	−0.0224 (8)
C8	0.0423 (10)	0.0802 (15)	0.1084 (18)	0.0019 (10)	−0.0197 (11)	−0.0673 (14)
C9	0.0356 (9)	0.0491 (10)	0.0638 (12)	−0.0082 (7)	−0.0003 (8)	−0.0330 (9)

Geometric parameters (Å, º) top

F1—C3	1.355 (2)	C4—C5	1.372 (3)
O1—C9	1.223 (3)	C5—C6	1.379 (3)
N1—N2	1.380 (2)	C7—C8	1.490 (3)
N1—C7	1.278 (2)	C2—H2	0.9300
N2—C9	1.332 (3)	C4—H4	0.9300
N2—H2A	0.8600	C5—H5	0.9300
C1—C2	1.389 (3)	C6—H6	0.9300
C1—C7	1.485 (3)	C8—H8A	0.9600
C1—C6	1.388 (3)	C8—H8B	0.9600
C2—C3	1.365 (3)	C8—H8C	0.9600
C3—C4	1.364 (3)	C9—H9	0.9300

N2—N1—C7	117.88 (15)	O1—C9—N2	123.78 (19)
N1—N2—C9	117.74 (15)	C1—C2—H2	120.00
C9—N2—H2A	121.00	C3—C2—H2	120.00
N1—N2—H2A	121.00	C3—C4—H4	121.00
C6—C1—C7	120.83 (15)	C5—C4—H4	121.00
C2—C1—C7	120.92 (16)	C4—C5—H5	119.00
C2—C1—C6	118.24 (18)	C6—C5—H5	119.00
C1—C2—C3	119.28 (19)	C1—C6—H6	120.00
C2—C3—C4	123.5 (2)	C5—C6—H6	120.00
F1—C3—C2	118.80 (18)	C7—C8—H8A	109.00
F1—C3—C4	117.74 (18)	C7—C8—H8B	109.00
C3—C4—C5	117.2 (2)	C7—C8—H8C	109.00
C4—C5—C6	121.4 (2)	H8A—C8—H8B	110.00
C1—C6—C5	120.5 (2)	H8A—C8—H8C	109.00
N1—C7—C1	115.92 (14)	H8B—C8—H8C	109.00
N1—C7—C8	124.86 (19)	O1—C9—H9	118.00
C1—C7—C8	119.20 (17)	N2—C9—H9	118.00

C7—N1—N2—C9	178.74 (16)	C2—C1—C7—C8	164.42 (19)
N2—N1—C7—C1	−179.88 (14)	C6—C1—C7—N1	164.85 (17)
N2—N1—C7—C8	1.7 (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—C3	0.1 (3)	C1—C2—C3—C4	−0.2 (3)
C7—C1—C2—C3	179.02 (17)	F1—C3—C4—C5	179.6 (2)
C2—C1—C6—C5	0.4 (3)	C2—C3—C4—C5	−0.2 (4)
C7—C1—C6—C5	−178.6 (2)	C3—C4—C5—C6	0.7 (4)
C2—C1—C7—N1	−14.1 (3)	C4—C5—C6—C1	−0.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	2.14	2.989 (2)	168
C8—H8A···O1ⁱ	0.96	2.52	3.204 (3)	129

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₉FN₂O
M_r	180.18
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.8466 (5), 7.0258 (6), 9.9419 (8)
α, β, γ (°)	70.558 (5), 81.267 (5), 73.977 (4)
V (Å³)	432.50 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.28 × 0.12 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.986, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	19438, 2124, 1320
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.148, 1.00
No. of reflections	2124
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	2.14	2.989 (2)	168
C8—H8A···O1ⁱ	0.96	2.52	3.204 (3)	129

Symmetry code: (i) −x, −y+2, −z+1.

Acknowledgements

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.

References

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