(2E)-2-(4-Fluoro­benzyl­idene)hydrazinecarboxamide

Fun, H.-K.; Chia, T.S.; Malladi, S.; Isloor, A.M.; Shivananda, K.N.

doi:10.1107/S1600536811040797

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages o2885-o2886

doi:10.1107/S1600536811040797

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(2E)-2-(4-Fluorobenzylidene)hydrazinecarboxamide

Hoong-Kun Fun,^a ^*‡ Tze Shyang Chia,^a Shridhar Malladi,^b Arun M. Isloor ^b and Kammasandra N. Shivananda ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bMedicinal Chemistry Section, Department of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India, and ^cSchulich Faculty of Chemistry, Technion Israel Institute of Technology, Haifa 32000, Israel
^*Correspondence e-mail: hkfun@usm.my

(Received 3 October 2011; accepted 4 October 2011; online 8 October 2011)

In the title compound, C₈H₈FN₃O, the semicarbazide group is close to being planar, with a maximum deviation of 0.020 (1) Å, and subtends a dihedral angle of 16.63 (9)° with its attached fluorobenzene ring. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming layers lying parallel to the bc plane.

Related literature

For background to semicarbazides and semicarbazones, see: Dogan et al. (1999 ); Pandeya & Dimmock (1993 ); Pandeya et al. (1998 ); Sriram et al. (2004 ); Yogeeswari et al. (2004 ); For further synthetic details, see: Furniss et al. (1978 ). For related structures, see: Fun et al. (2009a ,b ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₈FN₃O
M_r = 181.17
Monoclinic, P 2₁ /c
a = 16.522 (2) Å
b = 4.4381 (6) Å
c = 11.9457 (15) Å
β = 103.478 (3)°
V = 851.80 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.72 × 0.18 × 0.12 mm

Data collection

Bruker APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.923, T_max = 0.987
8746 measured reflections
2418 independent reflections
1657 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.209
S = 1.00
2418 reflections
130 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯O1ⁱ	0.88 (2)	2.07 (2)	2.8954 (19)	158 (2)
N2—H1N2⋯O1ⁱⁱ	0.92 (2)	2.00 (2)	2.9155 (19)	179 (2)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811040797/hb6436sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040797/hb6436Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811040797/hb6436Isup3.cml

checkCIF report

Comment top

The semicarbazides, which are the raw material of semicarbazones, have been known to possess biological activities against many of the most common species of bacteria (Dogan et al., 1999). Semicarbazones are of much interest due to their wide spectrum of antibacterial activities (Pandeya & Dimmock, 1993). Recently some workers have reviewed the bioactivity of semicarbazones and they have exhibited anticonvulsant (Pandeya et al., 1998; Yogeeswari et al., 2004) and antitubercular (Sriram et al., 2004) properties. Accordingly and by considering the biological potential of semicarbazones, herein, we have synthesized the title compound to study its crystal structure.

The molecular structure of the title compound is shown in Fig. 1. The semicarbazone group (O1/N1–N3/C8) is essentially planar with maximum deviation of 0.020 (1) Å for atom N2. This plane makes dihedral angle of 16.63 (9)° with its terminal benzene ring (C1–C6). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Fun et al., 2009a,b).

In the crystal structure (Fig. 2), the molecules are interconnected by N3—H1N3···O1 and N2—H1N2···O1 hydrogen bonds (Table 1) forming two-dimensional networks parallel to bc plane.

Related literature top

For background to semicarbazides and semicarbazones, see: Dogan et al. (1999); Pandeya & Dimmock (1993); Pandeya et al. (1998); Sriram et al. (2004); Yogeeswari et al. (2004); For further synthetic details, see: Furniss et al. (1978). For related structures, see: Fun et al. (2009a,b). For reference bond lengths, see: Allen et al. (1987).

Experimental top

Semicarbazide hydrochloride (0.86 g, 7.70 mmol) and freshly recrystallized sodium acetate (0.77 g, 9.40 mmol) were dissolved in water (10 ml) following a literature procedure (Furniss et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. To this, 4-fluorobenzaldehyde (0.896 g, 7.23 mmol) was added and the mixture was shaken well. A little alcohol was added to dissolve the turbidity. The mixture was shaken for a further 10 minutes and allowed to stand. The title compound crystallizes out on standing for 6 h. The separated crystals were filtered, washed with cold water and recrystallized from ethanol to yield colourless needles. Yield: 0.98 g, 75.38%. M.p.: 506–508 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with atom labels with 50% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound. The dashed lines represent the hydrogen bonds.

(2E)-2-(4-Fluorobenzylidene)hydrazinecarboxamide top

Crystal data top

C₈H₈FN₃O	F(000) = 376
M_r = 181.17	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2666 reflections
a = 16.522 (2) Å	θ = 2.5–29.4°
b = 4.4381 (6) Å	µ = 0.11 mm⁻¹
c = 11.9457 (15) Å	T = 296 K
β = 103.478 (3)°	Needle, colourless
V = 851.80 (19) Å³	0.72 × 0.18 × 0.12 mm
Z = 4

Data collection top

Bruker APEX DUO CCD diffractometer	2418 independent reflections
Radiation source: fine-focus sealed tube	1657 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 29.9°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −23→23
T_min = 0.923, T_max = 0.987	k = −6→6
8746 measured reflections	l = −16→15

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.209	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.1446P)² + 0.0418P] where P = (F_o² + 2F_c²)/3
2418 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₈FN₃O	V = 851.80 (19) Å³
M_r = 181.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.522 (2) Å	µ = 0.11 mm⁻¹
b = 4.4381 (6) Å	T = 296 K
c = 11.9457 (15) Å	0.72 × 0.18 × 0.12 mm
β = 103.478 (3)°

Data collection top

Bruker APEX DUO CCD diffractometer	2418 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1657 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.987	R_int = 0.024
8746 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.209	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.31 e Å⁻³
2418 reflections	Δρ_min = −0.21 e Å⁻³
130 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
F1	0.51936 (9)	1.2636 (4)	1.15848 (18)	0.1170 (6)
O1	1.01013 (7)	0.7059 (3)	0.87156 (9)	0.0508 (3)
N1	0.83497 (7)	0.8821 (3)	0.97516 (10)	0.0448 (3)
N2	0.90494 (8)	0.7354 (3)	0.96093 (11)	0.0470 (3)
N3	0.91237 (8)	1.0690 (3)	0.81619 (11)	0.0493 (4)
C1	0.71134 (11)	0.8578 (5)	1.18840 (15)	0.0637 (5)
H1A	0.7461	0.7333	1.2413	0.076*
C2	0.63885 (11)	0.9701 (6)	1.21288 (16)	0.0705 (5)
H2A	0.6244	0.9217	1.2814	0.085*
C3	0.58977 (12)	1.1518 (5)	1.1342 (2)	0.0740 (6)
C4	0.60851 (13)	1.2285 (6)	1.0325 (2)	0.0855 (7)
H4A	0.5735	1.3543	0.9805	0.103*
C5	0.68021 (11)	1.1161 (5)	1.00849 (17)	0.0669 (5)
H5A	0.6937	1.1662	0.9394	0.080*
C6	0.73235 (9)	0.9300 (4)	1.08559 (13)	0.0493 (4)
C7	0.80796 (9)	0.8014 (4)	1.06141 (13)	0.0504 (4)
H7A	0.8371	0.6560	1.1109	0.060*
C8	0.94581 (8)	0.8362 (3)	0.88136 (11)	0.0405 (3)
H1N3	0.9423 (12)	1.145 (5)	0.7725 (18)	0.064 (5)*
H1N2	0.9306 (12)	0.599 (5)	1.0133 (16)	0.061 (5)*
H2N3	0.8717 (14)	1.181 (5)	0.8357 (19)	0.074 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0854 (10)	0.1393 (14)	0.1524 (15)	0.0374 (9)	0.0807 (10)	0.0080 (10)
O1	0.0544 (6)	0.0586 (7)	0.0499 (6)	0.0023 (4)	0.0334 (5)	−0.0022 (4)
N1	0.0447 (6)	0.0544 (7)	0.0417 (6)	0.0019 (5)	0.0228 (5)	−0.0006 (5)
N2	0.0490 (7)	0.0566 (7)	0.0446 (7)	0.0073 (5)	0.0296 (5)	0.0048 (5)
N3	0.0569 (7)	0.0541 (7)	0.0457 (7)	−0.0004 (5)	0.0299 (6)	0.0032 (5)
C1	0.0563 (9)	0.0936 (13)	0.0502 (9)	0.0081 (8)	0.0304 (7)	0.0076 (8)
C2	0.0662 (10)	0.0974 (15)	0.0620 (10)	−0.0021 (9)	0.0438 (9)	−0.0068 (10)
C3	0.0558 (10)	0.0863 (14)	0.0938 (15)	0.0098 (8)	0.0457 (10)	−0.0057 (11)
C4	0.0695 (12)	0.1019 (16)	0.0965 (17)	0.0321 (11)	0.0423 (12)	0.0232 (13)
C5	0.0631 (10)	0.0820 (12)	0.0656 (11)	0.0196 (8)	0.0353 (8)	0.0179 (9)
C6	0.0457 (7)	0.0643 (9)	0.0448 (7)	0.0019 (6)	0.0244 (6)	−0.0001 (6)
C7	0.0482 (8)	0.0673 (9)	0.0425 (8)	0.0090 (6)	0.0245 (6)	0.0085 (6)
C8	0.0461 (7)	0.0452 (7)	0.0361 (6)	−0.0067 (5)	0.0215 (5)	−0.0085 (5)

Geometric parameters (Å, º) top

F1—C3	1.3568 (19)	C1—H1A	0.9300
O1—C8	1.2393 (16)	C2—C3	1.355 (3)
N1—C7	1.2661 (18)	C2—H2A	0.9300
N1—N2	1.3714 (16)	C3—C4	1.365 (3)
N2—C8	1.3634 (17)	C4—C5	1.376 (2)
N2—H1N2	0.90 (2)	C4—H4A	0.9300
N3—C8	1.3333 (18)	C5—C6	1.379 (2)
N3—H1N3	0.87 (2)	C5—H5A	0.9300
N3—H2N3	0.91 (2)	C6—C7	1.4621 (19)
C1—C2	1.390 (2)	C7—H7A	0.9300
C1—C6	1.389 (2)

C7—N1—N2	115.71 (12)	C3—C4—C5	118.7 (2)
C8—N2—N1	119.96 (12)	C3—C4—H4A	120.6
C8—N2—H1N2	118.4 (12)	C5—C4—H4A	120.6
N1—N2—H1N2	120.3 (12)	C4—C5—C6	120.79 (17)
C8—N3—H1N3	115.9 (13)	C4—C5—H5A	119.6
C8—N3—H2N3	120.3 (14)	C6—C5—H5A	119.6
H1N3—N3—H2N3	120 (2)	C5—C6—C1	118.85 (14)
C2—C1—C6	120.56 (17)	C5—C6—C7	122.08 (14)
C2—C1—H1A	119.7	C1—C6—C7	119.06 (15)
C6—C1—H1A	119.7	N1—C7—C6	121.99 (14)
C3—C2—C1	118.24 (16)	N1—C7—H7A	119.0
C3—C2—H2A	120.9	C6—C7—H7A	119.0
C1—C2—H2A	120.9	O1—C8—N3	123.66 (12)
F1—C3—C2	118.27 (19)	O1—C8—N2	119.18 (13)
F1—C3—C4	118.9 (2)	N3—C8—N2	117.15 (12)
C2—C3—C4	122.86 (16)

C7—N1—N2—C8	−170.19 (13)	C4—C5—C6—C7	178.57 (19)
C6—C1—C2—C3	−0.3 (3)	C2—C1—C6—C5	0.3 (3)
C1—C2—C3—F1	−179.4 (2)	C2—C1—C6—C7	−178.40 (17)
C1—C2—C3—C4	0.0 (4)	N2—N1—C7—C6	−177.87 (13)
F1—C3—C4—C5	179.6 (2)	C5—C6—C7—N1	8.7 (3)
C2—C3—C4—C5	0.2 (4)	C1—C6—C7—N1	−172.65 (16)
C3—C4—C5—C6	−0.1 (4)	N1—N2—C8—O1	178.19 (12)
C4—C5—C6—C1	−0.1 (3)	N1—N2—C8—N3	−3.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···O1ⁱ	0.88 (2)	2.07 (2)	2.8954 (19)	158 (2)
N2—H1N2···O1ⁱⁱ	0.92 (2)	2.00 (2)	2.9155 (19)	179 (2)

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₈H₈FN₃O
M_r	181.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	16.522 (2), 4.4381 (6), 11.9457 (15)
β (°)	103.478 (3)
V (Å³)	851.80 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.72 × 0.18 × 0.12

Data collection
Diffractometer	Bruker APEX DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.923, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	8746, 2418, 1657
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.701

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.209, 1.00
No. of reflections	2418
No. of parameters	130
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.21

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···O1ⁱ	0.88 (2)	2.07 (2)	2.8954 (19)	158 (2)
N2—H1N2···O1ⁱⁱ	0.92 (2)	2.00 (2)	2.9155 (19)	179 (2)

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and TSC thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSC thanks the Malaysian Government and USM for the award of the post of Research Officer under the Structure Determination of kDa Outer Membrane Proteins From S. typhi by X-ray Protein Crystallography Grant (No. 1001/PSKBP/8630013). AMI thanks Professor Sandeep Sanchethi, Director, National Institute of Technology-Karnataka, India, for providing research facilities and the Board for Research in Nuclear Sciences, Department of Atomic Energy, Government of India, for the Young Scientist award.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2009). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dogan, H. N., Duran, A. & Yemni, E. (1999). Drug Metab. Drug Interact. 15, 187–195. CAS Google Scholar
Fun, H.-K., Goh, J. H., Padaki, M., Malladi, S. & Isloor, A. M. (2009a). Acta Cryst. E65, o1591–o1592. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fun, H.-K., Yeap, C. S., Padaki, M., Malladi, S. & Isloor, A. M. (2009b). Acta Cryst. E65, o1619–o1620. Web of Science CSD CrossRef IUCr Journals Google Scholar
Furniss, B. S., Hannaford, A. J., Rogers, V., Smith, P. W. G. & Tatchell, A. R. (1978). Vogel's Textbook of Practical Organic Chemistry, 4th ed., p. 1112. London: ELBS. Google Scholar
Pandeya, S. N. & Dimmock, J. R. (1993). Pharmazie, 48, 659–666. CAS PubMed Web of Science Google Scholar
Pandeya, S. N., Misra, V., Singh, P. N. & Rupainwar, D. C. (1998). Pharmacology, 37, 17–22. CAS 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
Sriram, D., Yogeeswari, P. & Thirumurugan, R. S. (2004). Bioorg. Med. Chem. Lett. 14, 3923–3924. Web of Science CrossRef PubMed CAS Google Scholar
Yogeeswari, P., Sriram, D., Pandeya, S. N. & Stables, J. P. (2004). Farmaco, 59, 609–613. CrossRef PubMed CAS Google Scholar