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Acta Cryst. (2008). E64, o2320    [ doi:10.1107/S1600536808036271 ]

N'-(4-Bromobenzylidene)isonicotinohydrazide

L.-M. Li and F.-F. Jian

Abstract top

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.

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.

Refinement top

H atoms were fixed geometrically and allowed to ride on their attached atoms, with N—H = 0.86 Å and C—H = 0.93 Å, and with Uiso=1.2–Ueq(C,N).

All H atoms were placed in idealized positions and refined with riding constraints, with N—H = 0.86 Å and C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C,N).

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
[Figure 1] 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
C13H10BrN3OF(000) = 608
Mr = 304.15Dx = 1.643 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2167 reflections
a = 18.715 (9) Åθ = 3.3–24.3°
b = 6.517 (3) ŵ = 3.33 mm−1
c = 10.126 (5) ÅT = 273 K
β = 95.512 (9)°Block, yellow
V = 1229.3 (11) Å30.25 × 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 tubeRint = 0.034
graphiteθmax = 28.4°, θmin = 2.2°
φ and ω scansh = −18→25
7721 measured reflectionsk = −7→8
2992 independent reflectionsl = −13→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0429P)2 + 0.1134P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2992 reflectionsΔρmax = 0.39 e Å−3
164 parametersΔρmin = −0.55 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0072 (10)
Crystal data top
C13H10BrN3OV = 1229.3 (11) Å3
Mr = 304.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 18.715 (9) ŵ = 3.33 mm−1
b = 6.517 (3) ÅT = 273 K
c = 10.126 (5) Å0.25 × 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 reflectionsRint = 0.034
2992 independent reflectionsθmax = 28.4°
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.094Δρmax = 0.39 e Å−3
S = 1.01Δρmin = −0.55 e Å−3
2992 reflectionsAbsolute structure: ?
164 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Br0.038461 (17)0.64201 (4)0.85386 (4)0.08031 (18)
N30.25010 (10)1.5120 (3)0.93706 (17)0.0390 (4)
N20.29511 (10)1.6713 (3)0.90925 (18)0.0386 (4)
H2A0.30791.68470.83040.046*
O10.30311 (10)1.7983 (3)1.11880 (16)0.0529 (4)
C70.10215 (13)0.8680 (3)0.8543 (3)0.0457 (6)
C100.19040 (12)1.2072 (3)0.8503 (2)0.0369 (5)
N10.46415 (11)2.2729 (3)0.8926 (2)0.0545 (6)
C40.36913 (11)1.9665 (3)0.9610 (2)0.0349 (5)
C130.31906 (12)1.8058 (3)1.0047 (2)0.0362 (5)
C90.19163 (13)1.0539 (4)0.7549 (2)0.0446 (6)
H9A0.22291.06560.68930.054*
C120.23656 (13)1.3861 (3)0.8414 (2)0.0417 (5)
H12A0.25701.40940.76260.050*
C30.37459 (13)2.1531 (3)1.0273 (2)0.0448 (6)
H3B0.34712.17871.09720.054*
C50.41305 (13)1.9365 (4)0.8605 (2)0.0455 (6)
H5A0.41151.81400.81330.055*
C110.14423 (13)1.1841 (4)0.9499 (2)0.0438 (6)
H11A0.14291.28441.01500.053*
C80.14730 (14)0.8850 (3)0.7560 (3)0.0488 (6)
H8A0.14800.78430.69110.059*
C60.10088 (13)1.0151 (4)0.9526 (2)0.0473 (6)
H6A0.07080.99941.01990.057*
C20.42134 (14)2.3003 (4)0.9882 (3)0.0515 (6)
H2B0.42292.42631.03150.062*
C10.45933 (14)2.0919 (4)0.8314 (3)0.0552 (7)
H1B0.48912.06840.76460.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.0729 (3)0.04607 (19)0.1216 (4)−0.01855 (14)0.0075 (2)−0.00034 (16)
N30.0430 (11)0.0399 (10)0.0350 (10)−0.0045 (8)0.0083 (8)0.0038 (9)
N20.0456 (11)0.0415 (10)0.0301 (10)−0.0063 (8)0.0103 (8)0.0034 (8)
O10.0674 (12)0.0593 (10)0.0341 (9)−0.0110 (9)0.0160 (8)−0.0036 (8)
C70.0409 (13)0.0333 (12)0.0618 (16)0.0013 (9)−0.0016 (12)0.0032 (11)
C100.0383 (12)0.0367 (11)0.0352 (12)0.0003 (9)0.0013 (10)0.0032 (10)
N10.0568 (14)0.0567 (14)0.0492 (13)−0.0143 (11)0.0019 (11)0.0077 (11)
C40.0363 (12)0.0387 (12)0.0294 (11)0.0036 (9)0.0022 (9)0.0023 (9)
C130.0380 (13)0.0390 (11)0.0321 (12)0.0051 (9)0.0055 (10)0.0024 (10)
C90.0509 (14)0.0462 (13)0.0375 (13)0.0051 (11)0.0081 (11)−0.0005 (11)
C120.0469 (14)0.0440 (13)0.0355 (12)−0.0016 (10)0.0102 (11)0.0037 (11)
C30.0457 (14)0.0457 (14)0.0437 (13)0.0035 (10)0.0086 (11)−0.0041 (11)
C50.0482 (14)0.0493 (13)0.0400 (13)−0.0052 (11)0.0097 (11)−0.0050 (11)
C110.0472 (14)0.0443 (13)0.0403 (13)−0.0005 (10)0.0060 (11)−0.0057 (10)
C80.0571 (16)0.0396 (13)0.0487 (15)0.0076 (11)0.0005 (13)−0.0090 (11)
C60.0431 (14)0.0510 (14)0.0489 (14)−0.0025 (11)0.0103 (11)0.0065 (12)
C20.0532 (16)0.0402 (13)0.0596 (16)−0.0022 (11)−0.0029 (14)−0.0006 (12)
C10.0541 (16)0.0706 (18)0.0428 (14)−0.0117 (13)0.0139 (12)0.0010 (13)
Geometric parameters (Å, °) top
Br—C71.894 (2)C4—C131.500 (3)
N3—C121.276 (3)C9—C81.379 (3)
N3—N21.383 (2)C9—H9A0.9300
N2—C131.349 (3)C12—H12A0.9300
N2—H2A0.8600C3—C21.382 (3)
O1—C131.222 (3)C3—H3B0.9300
C7—C81.371 (4)C5—C11.382 (3)
C7—C61.384 (3)C5—H5A0.9300
C10—C91.391 (3)C11—C61.370 (3)
C10—C111.398 (3)C11—H11A0.9300
C10—C121.459 (3)C8—H8A0.9300
N1—C21.326 (3)C6—H6A0.9300
N1—C11.331 (3)C2—H2B0.9300
C4—C51.382 (3)C1—H1B0.9300
C4—C31.388 (3)
C12—N3—N2114.10 (18)C10—C12—H12A118.6
C13—N2—N3120.59 (18)C4—C3—C2119.3 (2)
C13—N2—H2A119.7C4—C3—H3B120.4
N3—N2—H2A119.7C2—C3—H3B120.4
C8—C7—C6121.4 (2)C4—C5—C1118.9 (2)
C8—C7—Br119.52 (19)C4—C5—H5A120.6
C6—C7—Br119.09 (19)C1—C5—H5A120.6
C9—C10—C11118.4 (2)C6—C11—C10120.6 (2)
C9—C10—C12118.8 (2)C6—C11—H11A119.7
C11—C10—C12122.8 (2)C10—C11—H11A119.7
C2—N1—C1116.1 (2)C7—C8—C9118.9 (2)
C5—C4—C3117.3 (2)C7—C8—H8A120.5
C5—C4—C13123.5 (2)C9—C8—H8A120.5
C3—C4—C13119.2 (2)C11—C6—C7119.5 (2)
O1—C13—N2123.8 (2)C11—C6—H6A120.3
O1—C13—C4121.6 (2)C7—C6—H6A120.3
N2—C13—C4114.59 (18)N1—C2—C3124.0 (2)
C8—C9—C10121.2 (2)N1—C2—H2B118.0
C8—C9—H9A119.4C3—C2—H2B118.0
C10—C9—H9A119.4N1—C1—C5124.4 (2)
N3—C12—C10122.9 (2)N1—C1—H1B117.8
N3—C12—H12A118.6C5—C1—H1B117.8
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.862.142.966 (3)161
C12—H12A···O1i0.932.603.377 (3)142
Symmetry codes: (i) x, −y+7/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.862.142.966 (3)161
C12—H12A···O1i0.932.603.377 (3)142
Symmetry codes: (i) x, −y+7/2, z−1/2.
references
References top

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Chiu, P., Chen, B. & Cheng, K. F. (1998). Tetrahedron Lett. 39, 9229–9232.

Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.