N′-(2,6-Difluoro­benzyl­idene)pyridine-4-carbohydrazide

Fun, H.-K.; Quah, C.K.; Shetty, D.N.; Narayana, B.; Sarojini, B.K.

doi:10.1107/S1600536812016716

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1484

doi:10.1107/S1600536812016716

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N′-(2,6-Difluorobenzylidene)pyridine-4-carbohydrazide

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Divya N. Shetty,^b B. Narayana ^b and B. K. Sarojini ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and ^cDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India
^*Correspondence e-mail: hkfun@usm.my

(Received 5 April 2012; accepted 17 April 2012; online 21 April 2012)

In the title compound, C₁₃H₉F₂N₃O, the pyridine ring forms a dihedral angle of 16.92 (7)° with the benzene ring. In the crystal, molecules are linked via N—H⋯O, C—H⋯O and C—H⋯F, with the same O atom accepting two bonds.

Related literature

For related structures, see: Chen (2006 ); Nie et al. (2006 ). For standard bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₃H₉F₂N₃O
M_r = 261.23
Monoclinic, P 2₁ /c
a = 6.8462 (1) Å
b = 24.7903 (5) Å
c = 8.3719 (1) Å
β = 125.249 (1)°
V = 1160.36 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.68 × 0.26 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.923, T_max = 0.988
22044 measured reflections
4531 independent reflections
3819 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.117
S = 1.06
4531 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.88 (2)	2.00 (2)	2.8554 (12)	163.4 (16)
C1—H1A⋯F1ⁱⁱ	0.93	2.54	3.4622 (13)	169
C7—H7A⋯O1ⁱ	0.93	2.45	3.2253 (13)	141
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z+1.

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/S1600536812016716/bv2204sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016716/bv2204Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016716/bv2204Isup3.cml

checkCIF report

Comment top

In view of the importance of isoniazid and its various Schiff base derivatives (Chen, 2006; Nie et al., 2006), the synthesis and crystal structure of the title Schiff base is reported.

In the title molecule (Fig. 1), the pyridine ring (N1/C1-C5) forms a dihedral angle of 16.92 (7)° with the benzene ring (C8-C13). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable with related structures (Chen, 2006; Nie et al., 2006).

In the crystal structure, Fig. 2, molecules are linked via intermolecular C1–H1A···F1 and bifurcated N2–H1N2···O1 and C7–H7A···O1 hydrogen bonds (Table 1) into two-dimensional planes parallel to (010).

Related literature top

For related structures, see: Chen (2006); Nie et al. (2006). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

A mixture of isoniazid (1.4 g, 0.01 mol) and 2,6-difluorobenzaldehyde (1.4 ml, 0.01 mol) in 15 ml of absolute alcohol containing 2 drops of hydrochloric acid was refluxed for about 3 h. On cooling, the solid was separated, which was then filtered and recrystallized from DMF. The single crystal was grown from DMF by the slow evaporation method. (m.p. > 523 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 showing 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal structure of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

N'-(2,6-Difluorobenzylidene)pyridine-4-carbohydrazide top

Crystal data top

C₁₃H₉F₂N₃O	F(000) = 536
M_r = 261.23	D_x = 1.495 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8606 reflections
a = 6.8462 (1) Å	θ = 3.1–33.5°
b = 24.7903 (5) Å	µ = 0.12 mm⁻¹
c = 8.3719 (1) Å	T = 100 K
β = 125.249 (1)°	Plate, colourless
V = 1160.36 (3) Å³	0.68 × 0.26 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4531 independent reflections
Radiation source: fine-focus sealed tube	3819 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 33.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
T_min = 0.923, T_max = 0.988	k = −38→38
22044 measured reflections	l = −12→12

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0562P)² + 0.3643P] where P = (F_o² + 2F_c²)/3
4531 reflections	(Δ/σ)_max = 0.001
176 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₃H₉F₂N₃O	V = 1160.36 (3) Å³
M_r = 261.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.8462 (1) Å	µ = 0.12 mm⁻¹
b = 24.7903 (5) Å	T = 100 K
c = 8.3719 (1) Å	0.68 × 0.26 × 0.10 mm
β = 125.249 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4531 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3819 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.988	R_int = 0.029
22044 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.50 e Å⁻³
4531 reflections	Δρ_min = −0.23 e Å⁻³
176 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 > 2sigma(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	0.41487 (12)	0.82429 (3)	−0.46332 (9)	0.02284 (14)
F2	0.74397 (12)	0.94647 (3)	0.06279 (9)	0.02428 (15)
O1	0.88240 (14)	0.69293 (3)	−0.10748 (11)	0.01802 (15)
N1	1.26302 (17)	0.60373 (4)	0.54592 (13)	0.02081 (18)
N2	0.85867 (15)	0.75837 (3)	0.07264 (12)	0.01533 (15)
N3	0.73916 (15)	0.79285 (3)	−0.08611 (12)	0.01499 (15)
C1	1.20146 (17)	0.69340 (4)	0.41379 (14)	0.01558 (17)
H1A	1.2365	0.7300	0.4362	0.019*
C2	1.30695 (18)	0.65690 (4)	0.56804 (15)	0.01889 (18)
H2A	1.4143	0.6701	0.6940	0.023*
C3	1.11063 (19)	0.58554 (4)	0.36284 (16)	0.01903 (19)
H3A	1.0787	0.5487	0.3448	0.023*
C4	0.99779 (17)	0.61841 (4)	0.19868 (15)	0.01578 (17)
H4A	0.8951	0.6039	0.0741	0.019*
C5	1.04182 (16)	0.67368 (4)	0.22471 (13)	0.01332 (16)
C6	0.92010 (16)	0.70905 (4)	0.04740 (14)	0.01366 (16)
C7	0.71196 (16)	0.84069 (4)	−0.04226 (14)	0.01461 (16)
H7A	0.7767	0.8489	0.0877	0.018*
C8	0.58232 (16)	0.88247 (4)	−0.19069 (14)	0.01341 (16)
C9	0.43387 (17)	0.87443 (4)	−0.39305 (14)	0.01554 (17)
C10	0.30493 (19)	0.91512 (4)	−0.52600 (15)	0.01971 (19)
H10A	0.2063	0.9079	−0.6594	0.024*
C11	0.3256 (2)	0.96720 (4)	−0.45622 (16)	0.0218 (2)
H11A	0.2382	0.9950	−0.5441	0.026*
C12	0.47472 (19)	0.97845 (4)	−0.25729 (16)	0.02061 (19)
H12A	0.4914	1.0134	−0.2107	0.025*
C13	0.59696 (17)	0.93600 (4)	−0.13148 (14)	0.01623 (17)
H1N2	0.870 (3)	0.7667 (7)	0.180 (3)	0.034 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0293 (3)	0.0157 (3)	0.0164 (3)	0.0010 (2)	0.0091 (3)	−0.0034 (2)
F2	0.0308 (3)	0.0188 (3)	0.0156 (3)	0.0007 (2)	0.0089 (3)	−0.0043 (2)
O1	0.0264 (4)	0.0163 (3)	0.0134 (3)	0.0014 (3)	0.0126 (3)	−0.0004 (2)
N1	0.0226 (4)	0.0217 (4)	0.0176 (4)	0.0037 (3)	0.0113 (3)	0.0052 (3)
N2	0.0211 (4)	0.0142 (3)	0.0117 (3)	0.0042 (3)	0.0100 (3)	0.0025 (3)
N3	0.0182 (3)	0.0143 (3)	0.0135 (3)	0.0027 (3)	0.0097 (3)	0.0029 (3)
C1	0.0165 (4)	0.0160 (4)	0.0139 (4)	0.0004 (3)	0.0086 (3)	−0.0003 (3)
C2	0.0183 (4)	0.0226 (4)	0.0133 (4)	0.0022 (3)	0.0077 (4)	0.0013 (3)
C3	0.0222 (4)	0.0154 (4)	0.0204 (5)	0.0021 (3)	0.0128 (4)	0.0037 (3)
C4	0.0175 (4)	0.0146 (4)	0.0158 (4)	0.0003 (3)	0.0100 (3)	0.0003 (3)
C5	0.0154 (4)	0.0135 (3)	0.0130 (4)	0.0014 (3)	0.0093 (3)	0.0011 (3)
C6	0.0154 (4)	0.0136 (3)	0.0127 (4)	0.0001 (3)	0.0085 (3)	0.0004 (3)
C7	0.0162 (4)	0.0149 (4)	0.0131 (4)	0.0010 (3)	0.0086 (3)	0.0009 (3)
C8	0.0155 (4)	0.0124 (3)	0.0138 (4)	0.0007 (3)	0.0093 (3)	0.0005 (3)
C9	0.0180 (4)	0.0139 (4)	0.0149 (4)	−0.0001 (3)	0.0096 (3)	−0.0009 (3)
C10	0.0225 (4)	0.0199 (4)	0.0143 (4)	0.0025 (3)	0.0092 (4)	0.0032 (3)
C11	0.0269 (5)	0.0168 (4)	0.0210 (5)	0.0048 (3)	0.0135 (4)	0.0061 (4)
C12	0.0266 (5)	0.0135 (4)	0.0224 (5)	0.0020 (3)	0.0146 (4)	0.0015 (3)
C13	0.0192 (4)	0.0146 (4)	0.0150 (4)	−0.0003 (3)	0.0099 (3)	−0.0012 (3)

Geometric parameters (Å, º) top

F1—C9	1.3488 (11)	C4—C5	1.3928 (13)
F2—C13	1.3550 (12)	C4—H4A	0.9300
O1—C6	1.2334 (11)	C5—C6	1.4963 (13)
N1—C3	1.3399 (14)	C7—C8	1.4601 (13)
N1—C2	1.3410 (14)	C7—H7A	0.9300
N2—C6	1.3485 (12)	C8—C9	1.3983 (13)
N2—N3	1.3826 (11)	C8—C13	1.3998 (13)
N2—H1N2	0.884 (18)	C9—C10	1.3790 (14)
N3—C7	1.2864 (12)	C10—C11	1.3901 (15)
C1—C2	1.3897 (14)	C10—H10A	0.9300
C1—C5	1.3936 (13)	C11—C12	1.3897 (16)
C1—H1A	0.9300	C11—H11A	0.9300
C2—H2A	0.9300	C12—C13	1.3783 (14)
C3—C4	1.3872 (14)	C12—H12A	0.9300
C3—H3A	0.9300

C3—N1—C2	116.95 (9)	N2—C6—C5	114.91 (8)
C6—N2—N3	118.36 (8)	N3—C7—C8	121.88 (9)
C6—N2—H1N2	121.3 (11)	N3—C7—H7A	119.1
N3—N2—H1N2	119.4 (11)	C8—C7—H7A	119.1
C7—N3—N2	113.49 (8)	C9—C8—C13	114.68 (8)
C2—C1—C5	118.26 (9)	C9—C8—C7	126.14 (8)
C2—C1—H1A	120.9	C13—C8—C7	119.14 (9)
C5—C1—H1A	120.9	F1—C9—C10	117.80 (9)
N1—C2—C1	123.84 (9)	F1—C9—C8	118.65 (8)
N1—C2—H2A	118.1	C10—C9—C8	123.55 (9)
C1—C2—H2A	118.1	C9—C10—C11	118.53 (10)
N1—C3—C4	123.81 (9)	C9—C10—H10A	120.7
N1—C3—H3A	118.1	C11—C10—H10A	120.7
C4—C3—H3A	118.1	C12—C11—C10	121.09 (9)
C3—C4—C5	118.45 (9)	C12—C11—H11A	119.5
C3—C4—H4A	120.8	C10—C11—H11A	119.5
C5—C4—H4A	120.8	C13—C12—C11	117.68 (9)
C4—C5—C1	118.67 (9)	C13—C12—H12A	121.2
C4—C5—C6	118.35 (8)	C11—C12—H12A	121.2
C1—C5—C6	122.96 (8)	F2—C13—C12	118.28 (9)
O1—C6—N2	124.30 (9)	F2—C13—C8	117.29 (8)
O1—C6—C5	120.79 (8)	C12—C13—C8	124.43 (9)

C6—N2—N3—C7	−172.82 (9)	N3—C7—C8—C9	14.15 (15)
C3—N1—C2—C1	1.03 (16)	N3—C7—C8—C13	−167.93 (9)
C5—C1—C2—N1	−0.46 (15)	C13—C8—C9—F1	178.07 (8)
C2—N1—C3—C4	−0.28 (16)	C7—C8—C9—F1	−3.93 (15)
N1—C3—C4—C5	−0.99 (15)	C13—C8—C9—C10	−1.87 (14)
C3—C4—C5—C1	1.52 (14)	C7—C8—C9—C10	176.13 (10)
C3—C4—C5—C6	179.93 (9)	F1—C9—C10—C11	−178.93 (9)
C2—C1—C5—C4	−0.85 (14)	C8—C9—C10—C11	1.00 (16)
C2—C1—C5—C6	−179.18 (9)	C9—C10—C11—C12	0.75 (17)
N3—N2—C6—O1	2.02 (14)	C10—C11—C12—C13	−1.46 (17)
N3—N2—C6—C5	−178.14 (8)	C11—C12—C13—F2	179.64 (9)
C4—C5—C6—O1	−34.71 (13)	C11—C12—C13—C8	0.49 (16)
C1—C5—C6—O1	143.63 (10)	C9—C8—C13—F2	−178.05 (9)
C4—C5—C6—N2	145.45 (9)	C7—C8—C13—F2	3.79 (13)
C1—C5—C6—N2	−36.22 (13)	C9—C8—C13—C12	1.10 (15)
N2—N3—C7—C8	−177.64 (8)	C7—C8—C13—C12	−177.05 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1ⁱ	0.88 (2)	2.00 (2)	2.8554 (12)	163.4 (16)
C1—H1A···F1ⁱⁱ	0.93	2.54	3.4622 (13)	169
C7—H7A···O1ⁱ	0.93	2.45	3.2253 (13)	141

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

Experimental details

Crystal data
Chemical formula	C₁₃H₉F₂N₃O
M_r	261.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.8462 (1), 24.7903 (5), 8.3719 (1)
β (°)	125.249 (1)
V (Å³)	1160.36 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.68 × 0.26 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.923, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	22044, 4531, 3819
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.777

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.117, 1.06
No. of reflections	4531
No. of parameters	176
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.23

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
N2—H1N2···O1ⁱ	0.88 (2)	2.00 (2)	2.8554 (12)	163.4 (16)
C1—H1A···F1ⁱⁱ	0.9300	2.5400	3.4622 (13)	169.00
C7—H7A···O1ⁱ	0.9300	2.4500	3.2253 (13)	141.00

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

The authors would like to thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). BN thanks the UGC SAP for financial assistance for the purchase of chemicals. DNS thanks Mangalore University for research facilities.

References

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