(E)-N′-(3,5-Dibromo-2-hydroxy­benzyl­idene)nicotinohydrazide

Su, Y.-Q.; Li, C.; Wang, P.

doi:10.1107/S1600536810006276

organic compounds

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Volume 66| Part 3| March 2010| Page o670

doi:10.1107/S1600536810006276

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(E)-N′-(3,5-Dibromo-2-hydroxybenzylidene)nicotinohydrazide

Yong-Qing Su,^a ^* Cong Li ^a and Ping Wang ^a

^aFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, People's Republic of China
^*Correspondence e-mail: yongqing_su@163.com

(Received 11 February 2010; accepted 17 February 2010; online 20 February 2010)

In the title Schiff base compound, C₁₃H₉Br₂N₃O₂, there is an intramolecular O-H⋯N hydrogen bond involving the hydroxyl substituent and the adjacent hydrazine N atom. The molecule is almost planar, the dihedral angle between the benzene ring and the pyridine ring being 5.7 (2)°. In the crystal structure, symmetry-related molecules are linked via N—H⋯O hydrogen bonds, forming chains propagating in [001].

Related literature

For related literature on Schiff bases, see: Archibald et al. (1994 ); Harada et al. (1999 ); Ogawa et al. (1998 ). For similar structures, see: Mohd Lair et al. (2009 ); Li et al. (2010 ); Sun et al. (2009 ); Wang et al. (2010 ); Wen et al. (2009 ).

Experimental

Crystal data

C₁₃H₉Br₂N₃O₂
M_r = 399.05
Monoclinic, P 2₁ /c
a = 17.013 (4) Å
b = 8.091 (2) Å
c = 10.153 (3) Å
β = 92.194 (13)°
V = 1396.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.81 mm⁻¹
T = 298 K
0.23 × 0.21 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.349, T_max = 0.390
8024 measured reflections
3023 independent reflections
1933 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 1.00
3023 reflections
185 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.89	2.609 (4)	146
N2—H2⋯O2ⁱ	0.91 (2)	2.14 (2)	3.017 (4)	162 (3)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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/S1600536810006276/su2163sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006276/su2163Isup2.hkl

checkCIF report

Comment top

Schiff bases have received much attention in recent years (Ogawa et al., 1998; Archibald et al., 1994; Harada et al., 1999). Recently, we reported on the crystal structures of two new Schiff bases (Li et al., 2010; Wang et al., 2010). As a further investigation of the structures of Schiff base compounds the title compound was prepared by the reaction of 3,5-dibromo-2-hydroxybenzaldehyde with nicotinic acid hydrazide in methanol; its crystal structure is reported on here.

In the title compound (Fig. 1), there is an intramolecular O-H···N hydrogen bond involving the hydroxyl substituent and the adjacent hydrazine N-atom, N2 (Table 1). The benzene ring is inclined to the pyridine ring by 5.7 (2)°. All the bond lengths are comparable with those observed in similar Schiff bases reported on previously (Wen et al., 2009; Mohd Lair et al., 2009; Sun et al., 2009).

In the crystal structure, symmetry related molecules are linked via intermolecular N—H···O hydrogen bonds so forming chains running along the c axis (Table 1, Fig. 2).

Related literature top

For related literature on Schiff bases, see: Archibald et al. (1994); Harada et al. (1999); Ogawa et al. (1998). For similar structures, see: Mohd Lair et al. (2009); Li et al. (2010); Sun et al. (2009); Wang et al. (2010); Wen et al. (2009).

Experimental top

3,5-Dibromo-2-hydroxybenzaldehyde (1.0 mmol, 280 mg) and nicotinic acid hydrazide (1.0 mmol, 137 mg) were dissolved in methanol (30 mL). The mixture was stirred at room temperature for about 1 h to give a colorless solution. After allowing the solution to evaporate slowly in air for 8 days, colorless block-like crystals, suitable for X-ray analysis, were formed.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular O-H···N hydrogen bond is shown as a dashed line.
	Fig. 2. The crystal packing of the title compound viewed along the b-axis. The intra- and intermolecular hydrogen bonds are shown as dashed lines (see Table 1 for details).

(E)-N'-(3,5-Dibromo-2-hydroxybenzylidene)nicotinohydrazide top

Crystal data top

C₁₃H₉Br₂N₃O₂	F(000) = 776
M_r = 399.05	D_x = 1.898 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2084 reflections
a = 17.013 (4) Å	θ = 2.4–25.2°
b = 8.091 (2) Å	µ = 5.81 mm⁻¹
c = 10.153 (3) Å	T = 298 K
β = 92.194 (13)°	Block, colourless
V = 1396.6 (6) Å³	0.23 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3023 independent reflections
Radiation source: fine-focus sealed tube	1933 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.0°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −19→21
T_min = 0.349, T_max = 0.390	k = −10→10
8024 measured reflections	l = −12→8

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0589P)²] where P = (F_o² + 2F_c²)/3
3023 reflections	(Δ/σ)_max = 0.001
185 parameters	Δρ_max = 0.64 e Å⁻³
1 restraint	Δρ_min = −0.69 e Å⁻³

Crystal data top

C₁₃H₉Br₂N₃O₂	V = 1396.6 (6) Å³
M_r = 399.05	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.013 (4) Å	µ = 5.81 mm⁻¹
b = 8.091 (2) Å	T = 298 K
c = 10.153 (3) Å	0.23 × 0.21 × 0.20 mm
β = 92.194 (13)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3023 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1933 reflections with I > 2σ(I)
T_min = 0.349, T_max = 0.390	R_int = 0.036
8024 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.64 e Å⁻³
3023 reflections	Δρ_min = −0.69 e Å⁻³
185 parameters

Special details top

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 > 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
Br1	0.38611 (2)	1.15620 (7)	0.38681 (5)	0.0731 (2)
Br2	0.44353 (2)	0.85756 (6)	0.88313 (4)	0.06341 (18)
N1	0.11733 (17)	0.8462 (3)	0.5380 (3)	0.0393 (7)
N2	0.04257 (16)	0.7852 (4)	0.5483 (3)	0.0402 (7)
N3	−0.16645 (18)	0.5160 (4)	0.5780 (3)	0.0501 (8)
O1	0.22622 (14)	1.0061 (3)	0.4163 (2)	0.0514 (7)
H1	0.1820	0.9696	0.4270	0.077*
O2	0.01730 (14)	0.8169 (3)	0.3293 (2)	0.0508 (7)
C1	0.2459 (2)	0.8814 (4)	0.6310 (3)	0.0383 (8)
C2	0.27257 (19)	0.9725 (4)	0.5231 (3)	0.0377 (8)
C3	0.3494 (2)	1.0292 (4)	0.5283 (3)	0.0437 (9)
C4	0.4001 (2)	0.9964 (4)	0.6347 (3)	0.0455 (9)
H4	0.4512	1.0374	0.6373	0.055*
C5	0.3737 (2)	0.9026 (4)	0.7363 (3)	0.0403 (8)
C6	0.2980 (2)	0.8450 (4)	0.7371 (3)	0.0430 (9)
H6	0.2813	0.7823	0.8076	0.052*
C7	0.1655 (2)	0.8224 (4)	0.6360 (3)	0.0396 (8)
H7	0.1490	0.7673	0.7104	0.048*
C8	−0.00388 (19)	0.7712 (4)	0.4372 (3)	0.0366 (8)
C9	−0.08166 (19)	0.6936 (4)	0.4557 (3)	0.0358 (8)
C10	−0.1424 (2)	0.7215 (5)	0.3642 (4)	0.0492 (9)
H10	−0.1347	0.7889	0.2917	0.059*
C11	−0.2145 (2)	0.6488 (5)	0.3811 (4)	0.0541 (11)
H11	−0.2561	0.6666	0.3207	0.065*
C12	−0.2236 (2)	0.5493 (5)	0.4894 (4)	0.0510 (10)
H12	−0.2727	0.5025	0.5011	0.061*
C13	−0.0972 (2)	0.5869 (4)	0.5595 (3)	0.0417 (9)
H13	−0.0563	0.5637	0.6200	0.050*
H2	0.024 (2)	0.764 (6)	0.629 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0414 (3)	0.1045 (4)	0.0730 (3)	−0.0128 (2)	−0.0014 (2)	0.0354 (3)
Br2	0.0494 (3)	0.0779 (3)	0.0609 (3)	0.0041 (2)	−0.0244 (2)	0.0057 (2)
N1	0.0304 (16)	0.0528 (18)	0.0347 (16)	−0.0058 (13)	0.0011 (12)	−0.0056 (13)
N2	0.0285 (16)	0.0596 (19)	0.0324 (16)	−0.0048 (14)	−0.0016 (12)	−0.0034 (14)
N3	0.0425 (19)	0.057 (2)	0.0510 (19)	−0.0091 (15)	0.0009 (15)	0.0027 (15)
O1	0.0355 (15)	0.079 (2)	0.0393 (14)	−0.0054 (13)	−0.0059 (11)	0.0100 (13)
O2	0.0404 (15)	0.082 (2)	0.0301 (14)	−0.0050 (13)	−0.0007 (11)	0.0079 (13)
C1	0.0308 (19)	0.044 (2)	0.040 (2)	−0.0013 (15)	−0.0025 (15)	−0.0067 (16)
C2	0.0319 (19)	0.047 (2)	0.0344 (18)	0.0030 (15)	−0.0022 (14)	−0.0012 (16)
C3	0.035 (2)	0.051 (2)	0.045 (2)	−0.0012 (16)	−0.0013 (16)	0.0044 (17)
C4	0.030 (2)	0.051 (2)	0.055 (2)	−0.0002 (17)	−0.0051 (17)	−0.0015 (19)
C5	0.036 (2)	0.044 (2)	0.041 (2)	0.0035 (16)	−0.0078 (15)	−0.0012 (17)
C6	0.043 (2)	0.047 (2)	0.039 (2)	0.0002 (17)	−0.0033 (16)	−0.0008 (16)
C7	0.037 (2)	0.044 (2)	0.037 (2)	−0.0012 (15)	−0.0033 (16)	−0.0010 (15)
C8	0.0315 (19)	0.043 (2)	0.0347 (19)	0.0033 (15)	−0.0029 (15)	−0.0034 (16)
C9	0.0322 (19)	0.043 (2)	0.0318 (18)	0.0028 (15)	−0.0015 (14)	−0.0087 (15)
C10	0.042 (2)	0.066 (3)	0.038 (2)	−0.0023 (19)	−0.0067 (17)	0.0071 (19)
C11	0.034 (2)	0.077 (3)	0.050 (2)	0.0003 (19)	−0.0100 (17)	−0.011 (2)
C12	0.037 (2)	0.056 (2)	0.061 (3)	−0.0079 (18)	0.0017 (18)	−0.012 (2)
C13	0.038 (2)	0.047 (2)	0.039 (2)	−0.0013 (17)	−0.0042 (16)	0.0019 (16)

Geometric parameters (Å, º) top

Br1—C3	1.892 (4)	C3—C4	1.382 (4)
Br2—C5	1.905 (3)	C4—C5	1.370 (5)
N1—C7	1.278 (4)	C4—H4	0.9300
N1—N2	1.372 (4)	C5—C6	1.371 (5)
N2—C8	1.357 (4)	C6—H6	0.9300
N2—H2	0.901 (10)	C7—H7	0.9300
N3—C12	1.326 (4)	C8—C9	1.483 (5)
N3—C13	1.330 (4)	C9—C10	1.381 (5)
O1—C2	1.344 (4)	C9—C13	1.396 (5)
O1—H1	0.8200	C10—C11	1.377 (5)
O2—C8	1.223 (4)	C10—H10	0.9300
C1—C6	1.401 (5)	C11—C12	1.376 (5)
C1—C2	1.409 (5)	C11—H11	0.9300
C1—C7	1.452 (5)	C12—H12	0.9300
C2—C3	1.384 (5)	C13—H13	0.9300

C7—N1—N2	117.1 (3)	C1—C6—H6	120.3
C8—N2—N1	118.6 (3)	N1—C7—C1	120.0 (3)
C8—N2—H2	122 (3)	N1—C7—H7	120.0
N1—N2—H2	119 (3)	C1—C7—H7	120.0
C12—N3—C13	116.5 (3)	O2—C8—N2	122.5 (3)
C2—O1—H1	109.5	O2—C8—C9	122.4 (3)
C6—C1—C2	119.6 (3)	N2—C8—C9	115.1 (3)
C6—C1—C7	118.3 (3)	C10—C9—C13	116.7 (3)
C2—C1—C7	122.1 (3)	C10—C9—C8	119.6 (3)
O1—C2—C3	119.2 (3)	C13—C9—C8	123.6 (3)
O1—C2—C1	122.4 (3)	C11—C10—C9	119.6 (4)
C3—C2—C1	118.4 (3)	C11—C10—H10	120.2
C4—C3—C2	121.7 (3)	C9—C10—H10	120.2
C4—C3—Br1	118.9 (3)	C12—C11—C10	118.5 (4)
C2—C3—Br1	119.4 (3)	C12—C11—H11	120.8
C5—C4—C3	118.9 (3)	C10—C11—H11	120.8
C5—C4—H4	120.6	N3—C12—C11	124.0 (4)
C3—C4—H4	120.6	N3—C12—H12	118.0
C4—C5—C6	121.9 (3)	C11—C12—H12	118.0
C4—C5—Br2	118.9 (3)	N3—C13—C9	124.6 (3)
C6—C5—Br2	119.2 (3)	N3—C13—H13	117.7
C5—C6—C1	119.4 (3)	C9—C13—H13	117.7
C5—C6—H6	120.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.89	2.609 (4)	146
N2—H2···O2ⁱ	0.91 (2)	2.14 (2)	3.017 (4)	162 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉Br₂N₃O₂
M_r	399.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	17.013 (4), 8.091 (2), 10.153 (3)
β (°)	92.194 (13)
V (Å³)	1396.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.81
Crystal size (mm)	0.23 × 0.21 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.349, 0.390
No. of measured, independent and observed [I > 2σ(I)] reflections	8024, 3023, 1933
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.00
No. of reflections	3023
No. of parameters	185
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.69

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), 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
O1—H1···N1	0.82	1.89	2.609 (4)	146
N2—H2···O2ⁱ	0.91 (2)	2.14 (2)	3.017 (4)	162 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors would like to acknowledge the support provided by the Yunnan Province Science and Technology Department, the Program of Yunnan Province's Young-middle aged Reserve Scientific and Technological Principal Culture Plan (grant No. 2006PY01–50) and the fund of Yunnan Province's Applied Research Plan (grant No. 2006E0032M).

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