N′-(4-Bromo­benzyl­idene)isonicotino­hydrazide

Li, L.-M.; Jian, F.-F.

doi:10.1107/S1600536808036271

organic compounds

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Volume 64| Part 12| December 2008| Page o2320

doi:10.1107/S1600536808036271

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N′-(4-Bromobenzylidene)isonicotinohydrazide

Li-Min Li ^a and Fang-Fang Jian ^a ^*

^aMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 22 October 2008; accepted 6 November 2008; online 13 November 2008)

The title compound, C₁₃H₁₀BrN₃O, was prepared by the reaction of isonicotinohydrazide and 4-bromobenzaldehyde. The dihedral angle between the benzene and pyridine rings is 8.60 (12)°. The crystal packing is stabilized by intermolecular C—H⋯O and N—H⋯O hydogen-bonding interactions.

Related literature

For background on Schiff bases, see: Chiu et al. (1998 ). For comparative bond-length data, see: Cimerman et al. (1997 ).

Experimental

Crystal data

C₁₃H₁₀BrN₃O
M_r = 304.15
Monoclinic, P 2₁ /c
a = 18.715 (9) Å
b = 6.517 (3) Å
c = 10.126 (5) Å
β = 95.512 (9)°
V = 1229.3 (11) Å³
Z = 4
Mo Kα radiation
μ = 3.33 mm⁻¹
T = 273 (2) K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
7721 measured reflections
2992 independent reflections
1914 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.01
2992 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.55 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	2.966 (3)	161
C12—H12A⋯O1ⁱ	0.93	2.60	3.377 (3)	142
Symmetry code: (i) $[x, -y+{\script{7\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036271/at2659sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036271/at2659Isup2.hkl

checkCIF report

Comment top

Schiff bases have received considerable attention in the literature. They are attractive from several points of view, such as the possibility of analytical application (Cimerman et al., 1997). As part of our search for new schiff base compounds we synthesized the title compound (I), and herein we report the crstal structure of (I).

In (I) (Fig. 1),

As seen in Fig. 1, the C12—N3 bond length of 1.276 (3)Å is comparable with C—N double bond [1.284 (2) Å] reported (Chiu et al., 1998). In the title molecule, the benzene ring (C6–C10) is essentialy planar with a maximum deviation of 0.009 (2) Å for C6 and C9, while the pyridine ring is planar, with a maximum deviation of 0.012 (2) Å for C3. The dihedral angle between the benzene and pyridine rings is 8.60 (12)°.

The crystal packing is stabilized by intermolecular C—H···O and N—H···O hydogen-bonding interactions.

Related literature top

For background on Schiff bases, see: Chiu et al. (1998). For comparative bond-length data, see: Cimerman et al. (1997).

Experimental top

A mixture of the isonicotinohydrazide (0.1 mol), and 4-bromobenzaldehyde (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.082 mol, yield 82%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Computing details top

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).

Figures top

Fig. 1. An ORTEP view of the title compound (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.

N'-(4-Bromobenzylidene)isonicotinohydrazide top

Crystal data top

C₁₃H₁₀BrN₃O	F(000) = 608
M_r = 304.15	D_x = 1.643 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2167 reflections
a = 18.715 (9) Å	θ = 3.3–24.3°
b = 6.517 (3) Å	µ = 3.33 mm⁻¹
c = 10.126 (5) Å	T = 273 K
β = 95.512 (9)°	Block, yellow
V = 1229.3 (11) Å³	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1914 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 28.4°, θ_min = 2.2°
ϕ and ω scans	h = −18→25
7721 measured reflections	k = −7→8
2992 independent reflections	l = −13→13

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0429P)² + 0.1134P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2992 reflections	Δρ_max = 0.39 e Å⁻³
164 parameters	Δρ_min = −0.55 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: 0.0072 (10)

Crystal data top

C₁₃H₁₀BrN₃O	V = 1229.3 (11) Å³
M_r = 304.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.715 (9) Å	µ = 3.33 mm⁻¹
b = 6.517 (3) Å	T = 273 K
c = 10.126 (5) Å	0.25 × 0.20 × 0.18 mm
β = 95.512 (9)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1914 reflections with I > 2σ(I)
7721 measured reflections	R_int = 0.034
2992 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.01	Δρ_max = 0.39 e Å⁻³
2992 reflections	Δρ_min = −0.55 e Å⁻³
164 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
Br	0.038461 (17)	0.64201 (4)	0.85386 (4)	0.08031 (18)
N3	0.25010 (10)	1.5120 (3)	0.93706 (17)	0.0390 (4)
N2	0.29511 (10)	1.6713 (3)	0.90925 (18)	0.0386 (4)
H2A	0.3079	1.6847	0.8304	0.046*
O1	0.30311 (10)	1.7983 (3)	1.11880 (16)	0.0529 (4)
C7	0.10215 (13)	0.8680 (3)	0.8543 (3)	0.0457 (6)
C10	0.19040 (12)	1.2072 (3)	0.8503 (2)	0.0369 (5)
N1	0.46415 (11)	2.2729 (3)	0.8926 (2)	0.0545 (6)
C4	0.36913 (11)	1.9665 (3)	0.9610 (2)	0.0349 (5)
C13	0.31906 (12)	1.8058 (3)	1.0047 (2)	0.0362 (5)
C9	0.19163 (13)	1.0539 (4)	0.7549 (2)	0.0446 (6)
H9A	0.2229	1.0656	0.6893	0.054*
C12	0.23656 (13)	1.3861 (3)	0.8414 (2)	0.0417 (5)
H12A	0.2570	1.4094	0.7626	0.050*
C3	0.37459 (13)	2.1531 (3)	1.0273 (2)	0.0448 (6)
H3B	0.3471	2.1787	1.0972	0.054*
C5	0.41305 (13)	1.9365 (4)	0.8605 (2)	0.0455 (6)
H5A	0.4115	1.8140	0.8133	0.055*
C11	0.14423 (13)	1.1841 (4)	0.9499 (2)	0.0438 (6)
H11A	0.1429	1.2844	1.0150	0.053*
C8	0.14730 (14)	0.8850 (3)	0.7560 (3)	0.0488 (6)
H8A	0.1480	0.7843	0.6911	0.059*
C6	0.10088 (13)	1.0151 (4)	0.9526 (2)	0.0473 (6)
H6A	0.0708	0.9994	1.0199	0.057*
C2	0.42134 (14)	2.3003 (4)	0.9882 (3)	0.0515 (6)
H2B	0.4229	2.4263	1.0315	0.062*
C1	0.45933 (14)	2.0919 (4)	0.8314 (3)	0.0552 (7)
H1B	0.4891	2.0684	0.7646	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0729 (3)	0.04607 (19)	0.1216 (4)	−0.01855 (14)	0.0075 (2)	−0.00034 (16)
N3	0.0430 (11)	0.0399 (10)	0.0350 (10)	−0.0045 (8)	0.0083 (8)	0.0038 (9)
N2	0.0456 (11)	0.0415 (10)	0.0301 (10)	−0.0063 (8)	0.0103 (8)	0.0034 (8)
O1	0.0674 (12)	0.0593 (10)	0.0341 (9)	−0.0110 (9)	0.0160 (8)	−0.0036 (8)
C7	0.0409 (13)	0.0333 (12)	0.0618 (16)	0.0013 (9)	−0.0016 (12)	0.0032 (11)
C10	0.0383 (12)	0.0367 (11)	0.0352 (12)	0.0003 (9)	0.0013 (10)	0.0032 (10)
N1	0.0568 (14)	0.0567 (14)	0.0492 (13)	−0.0143 (11)	0.0019 (11)	0.0077 (11)
C4	0.0363 (12)	0.0387 (12)	0.0294 (11)	0.0036 (9)	0.0022 (9)	0.0023 (9)
C13	0.0380 (13)	0.0390 (11)	0.0321 (12)	0.0051 (9)	0.0055 (10)	0.0024 (10)
C9	0.0509 (14)	0.0462 (13)	0.0375 (13)	0.0051 (11)	0.0081 (11)	−0.0005 (11)
C12	0.0469 (14)	0.0440 (13)	0.0355 (12)	−0.0016 (10)	0.0102 (11)	0.0037 (11)
C3	0.0457 (14)	0.0457 (14)	0.0437 (13)	0.0035 (10)	0.0086 (11)	−0.0041 (11)
C5	0.0482 (14)	0.0493 (13)	0.0400 (13)	−0.0052 (11)	0.0097 (11)	−0.0050 (11)
C11	0.0472 (14)	0.0443 (13)	0.0403 (13)	−0.0005 (10)	0.0060 (11)	−0.0057 (10)
C8	0.0571 (16)	0.0396 (13)	0.0487 (15)	0.0076 (11)	0.0005 (13)	−0.0090 (11)
C6	0.0431 (14)	0.0510 (14)	0.0489 (14)	−0.0025 (11)	0.0103 (11)	0.0065 (12)
C2	0.0532 (16)	0.0402 (13)	0.0596 (16)	−0.0022 (11)	−0.0029 (14)	−0.0006 (12)
C1	0.0541 (16)	0.0706 (18)	0.0428 (14)	−0.0117 (13)	0.0139 (12)	0.0010 (13)

Geometric parameters (Å, º) top

Br—C7	1.894 (2)	C4—C13	1.500 (3)
N3—C12	1.276 (3)	C9—C8	1.379 (3)
N3—N2	1.383 (2)	C9—H9A	0.9300
N2—C13	1.349 (3)	C12—H12A	0.9300
N2—H2A	0.8600	C3—C2	1.382 (3)
O1—C13	1.222 (3)	C3—H3B	0.9300
C7—C8	1.371 (4)	C5—C1	1.382 (3)
C7—C6	1.384 (3)	C5—H5A	0.9300
C10—C9	1.391 (3)	C11—C6	1.370 (3)
C10—C11	1.398 (3)	C11—H11A	0.9300
C10—C12	1.459 (3)	C8—H8A	0.9300
N1—C2	1.326 (3)	C6—H6A	0.9300
N1—C1	1.331 (3)	C2—H2B	0.9300
C4—C5	1.382 (3)	C1—H1B	0.9300
C4—C3	1.388 (3)

C12—N3—N2	114.10 (18)	C10—C12—H12A	118.6
C13—N2—N3	120.59 (18)	C4—C3—C2	119.3 (2)
C13—N2—H2A	119.7	C4—C3—H3B	120.4
N3—N2—H2A	119.7	C2—C3—H3B	120.4
C8—C7—C6	121.4 (2)	C4—C5—C1	118.9 (2)
C8—C7—Br	119.52 (19)	C4—C5—H5A	120.6
C6—C7—Br	119.09 (19)	C1—C5—H5A	120.6
C9—C10—C11	118.4 (2)	C6—C11—C10	120.6 (2)
C9—C10—C12	118.8 (2)	C6—C11—H11A	119.7
C11—C10—C12	122.8 (2)	C10—C11—H11A	119.7
C2—N1—C1	116.1 (2)	C7—C8—C9	118.9 (2)
C5—C4—C3	117.3 (2)	C7—C8—H8A	120.5
C5—C4—C13	123.5 (2)	C9—C8—H8A	120.5
C3—C4—C13	119.2 (2)	C11—C6—C7	119.5 (2)
O1—C13—N2	123.8 (2)	C11—C6—H6A	120.3
O1—C13—C4	121.6 (2)	C7—C6—H6A	120.3
N2—C13—C4	114.59 (18)	N1—C2—C3	124.0 (2)
C8—C9—C10	121.2 (2)	N1—C2—H2B	118.0
C8—C9—H9A	119.4	C3—C2—H2B	118.0
C10—C9—H9A	119.4	N1—C1—C5	124.4 (2)
N3—C12—C10	122.9 (2)	N1—C1—H1B	117.8
N3—C12—H12A	118.6	C5—C1—H1B	117.8

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	2.966 (3)	161
C12—H12A···O1ⁱ	0.93	2.60	3.377 (3)	142

Symmetry code: (i) x, −y+7/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀BrN₃O
M_r	304.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	18.715 (9), 6.517 (3), 10.126 (5)
β (°)	95.512 (9)
V (Å³)	1229.3 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.33
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7721, 2992, 1914
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.01
No. of reflections	2992
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.55

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

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	2.966 (3)	161
C12—H12A···O1ⁱ	0.93	2.60	3.377 (3)	142

Symmetry code: (i) x, −y+7/2, z−1/2.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chiu, P., Chen, B. & Cheng, K. F. (1998). Tetrahedron Lett. 39, 9229–9232. Web of Science CSD CrossRef CAS Google Scholar
Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2320

doi:10.1107/S1600536808036271

Open

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