N′-(5-Bromo-2-hydr­oxy-3-methoxy­benzyl­idene)isonicotinohydrazide

Peng, S.-J.; Hou, H.-Y.

doi:10.1107/S1600536808029607

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1995

doi:10.1107/S1600536808029607

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N′-(5-Bromo-2-hydroxy-3-methoxybenzylidene)isonicotinohydrazide

San-Jun Peng ^a ^* and Hai-Yun Hou ^b

^aCollege of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410076, People's Republic of China, and ^bCollege of Environmental and Chemical Engineering, Xi'an Polytechnic University, Xi'an 710048, People's Republic of China
^*Correspondence e-mail: sanjunpeng@163.com

(Received 12 September 2008; accepted 16 September 2008; online 24 September 2008)

The title compound, C₁₄H₁₂BrN₃O₃, was prepared by reaction of 5-bromo-3-methoxysalicylaldehyde and isonicotinohydrazide in methanol. The molecule is not planar and adopts a trans configuration with respect to the C=N bond. There is an intramolecular O—H⋯N hydrogen bond in the molecule. The dihedral angle between the benzene and pyridine rings is 12.2 (2)°. In the crystal structure, molecules are linked through intermolecular N—H⋯N hydrogen bonds, forming chains running along the c-axis direction.

Related literature

For bond-length data, see: Allen et al. (1987 ). For background on the biological properties of hydrazones, see: El-Tabl et al. (2008 ), Chen et al. (2008 ); Alvarez et al. (2008 ); Ventura & Martins (2008 ); Kalinowski et al. (2008 ). For related structures, see: Peng & Hou (2008 ); Shan et al. (2008 ); Fun et al. (2008 ); Yehye et al. (2008 ); Ejsmont et al. (2008 ); Han et al. (2006 ); Lu et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₂BrN₃O₃
M_r = 350.18
Monoclinic, P 2₁ /c
a = 7.4937 (9) Å
b = 15.8843 (19) Å
c = 11.7994 (14) Å
β = 99.776 (2)°
V = 1384.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.98 mm⁻¹
T = 298 (2) K
0.20 × 0.18 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.587, T_max = 0.616 (expected range = 0.557–0.584)
8003 measured reflections
3013 independent reflections
2299 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.076
S = 1.03
3013 reflections
195 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N3ⁱ	0.889 (10)	2.255 (13)	3.126 (3)	166 (3)
O1—H1⋯N1	0.82	1.93	2.643 (2)	145
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808029607/sj2539sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029607/sj2539Isup2.hkl

checkCIF report

Comment top

Hydrazones derived from the reactions of aldehydes with hydrazides show potential biological properties (El-Tabl et al., 2008; Chen et al., 2008; Alvarez et al., 2008; Ventura & Martins, 2008; Kalinowski et al., 2008). In the last few years, a large number of hydrazones have been reported (Peng & Hou, 2008; Shan et al., 2008; Fun et al., 2008; Yehye et al., 2008; Ejsmont et al., 2008). As a continuation of our work in this area (Peng & Hou, 2008) we report here the crystal structure of the title compound, (I), Fig. 1.

In the molecule of the title compound (I) the C7═N1 length of 1.275 (3) Å indicates a typical C═N bond. The molecule exists in a trans configuration with respect to the methylidene unit (C7═N1), as observed in other similar compounds (Han et al., 2006; Lu et al., 2008). There is an intramolecular O—H···N hydrogen bond in the molecule. The dihedral angle between the benzene and pyridine rings is 12.2 (2)°, indicating the molecule is not planar. The bond lengths are in normal ranges (Allen et al., 1987).

In the crystal structure, molecules are linked through intermolecular N—H···N hydrogen bonds (Table 1), forming chains running along the c direction (Fig. 2).

Related literature top

For bond-length data, see: Allen et al. (1987). For background on the biological properties of hydrazones, see: El-Tabl et al. (2008), Chen et al. (2008); Alvarez et al. (2008); Ventura & Martins (2008);Kalinowski et al. (2008). For related structures, see: Peng & Hou (2008); Shan et al. (2008); Fun et al. (2008); Yehye et al. (2008); Ejsmont et al. (2008),; Han et al. (2006); Lu et al. (2008).

Experimental top

5-Bromo-3-methoxysalicylaldehyde (0.231 g, 1 mmol) was dissolved in methanol (50 ml), then isonicotinohydrazide (0.137 g, 1 mmol) was added slowly to the solution, and the mixture was heated at reflux with continuous stirring for 1 h. The solution was cooled to room temperature, yielding colorless crystallites. Recrystallization from an absolute methanol yielded block-like single crystals of the compound.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms; the intramolecular hydrogen bond is drawn as a dashed line.
	Fig. 2. The packing diagram of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines and hydrogen atoms not involved in these interactions have been omitted..

N'-(5-Bromo-2-hydroxy-3-methoxybenzylidene)isonicotinohydrazide top

Crystal data top

C₁₄H₁₂BrN₃O₃	F(000) = 704
M_r = 350.18	D_x = 1.680 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3223 reflections
a = 7.4937 (9) Å	θ = 2.5–29.2°
b = 15.8843 (19) Å	µ = 2.98 mm⁻¹
c = 11.7994 (14) Å	T = 298 K
β = 99.776 (2)°	Block, colorless
V = 1384.1 (3) Å³	0.20 × 0.18 × 0.18 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3013 independent reflections
Radiation source: fine-focus sealed tube	2299 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.587, T_max = 0.616	k = −17→20
8003 measured reflections	l = −15→11

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0328P)² + 0.5984P] where P = (F_o² + 2F_c²)/3
3013 reflections	(Δ/σ)_max = 0.001
195 parameters	Δρ_max = 0.39 e Å⁻³
1 restraint	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₄H₁₂BrN₃O₃	V = 1384.1 (3) Å³
M_r = 350.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4937 (9) Å	µ = 2.98 mm⁻¹
b = 15.8843 (19) Å	T = 298 K
c = 11.7994 (14) Å	0.20 × 0.18 × 0.18 mm
β = 99.776 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3013 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2299 reflections with I > 2σ(I)
T_min = 0.587, T_max = 0.616	R_int = 0.023
8003 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.39 e Å⁻³
3013 reflections	Δρ_min = −0.41 e Å⁻³
195 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
Br1	0.28353 (5)	0.417081 (18)	1.029574 (19)	0.06245 (12)
O1	0.1144 (2)	0.35958 (10)	0.51873 (12)	0.0457 (4)
H1	0.1510	0.3985	0.4832	0.069*
O2	0.0357 (2)	0.24186 (10)	0.65725 (13)	0.0473 (4)
O3	0.2696 (3)	0.49630 (11)	0.27412 (14)	0.0651 (6)
N1	0.2592 (2)	0.50906 (11)	0.49603 (15)	0.0366 (4)
N2	0.3058 (3)	0.57618 (11)	0.43355 (15)	0.0368 (4)
N3	0.3899 (3)	0.77447 (12)	0.10697 (16)	0.0422 (5)
C1	0.2305 (3)	0.45105 (13)	0.67791 (17)	0.0322 (5)
C2	0.1524 (3)	0.37588 (13)	0.63313 (16)	0.0314 (4)
C3	0.1127 (3)	0.31267 (13)	0.70889 (17)	0.0328 (5)
C4	0.1548 (3)	0.32447 (14)	0.82630 (17)	0.0352 (5)
H4	0.1314	0.2823	0.8765	0.042*
C5	0.2323 (3)	0.39986 (14)	0.86841 (17)	0.0370 (5)
C6	0.2695 (3)	0.46250 (14)	0.79697 (17)	0.0375 (5)
H6	0.3208	0.5127	0.8274	0.045*
C7	0.2776 (3)	0.51825 (13)	0.60474 (18)	0.0376 (5)
H7	0.3220	0.5689	0.6378	0.045*
C8	0.3013 (3)	0.56400 (14)	0.31958 (18)	0.0379 (5)
C9	0.3367 (3)	0.64012 (13)	0.25079 (17)	0.0321 (5)
C10	0.2656 (3)	0.63897 (14)	0.13450 (18)	0.0408 (5)
H10	0.1991	0.5929	0.1022	0.049*
C11	0.2945 (3)	0.70697 (15)	0.0670 (2)	0.0449 (6)
H11	0.2445	0.7055	−0.0107	0.054*
C12	0.4597 (3)	0.77448 (14)	0.2190 (2)	0.0395 (5)
H12	0.5287	0.8207	0.2484	0.047*
C13	0.4358 (3)	0.71018 (13)	0.29379 (18)	0.0350 (5)
H13	0.4853	0.7138	0.3714	0.042*
C14	0.0108 (3)	0.17267 (14)	0.7293 (2)	0.0473 (6)
H14A	0.1255	0.1566	0.7732	0.071*
H14B	−0.0397	0.1261	0.6828	0.071*
H14C	−0.0701	0.1886	0.7805	0.071*
H2	0.331 (4)	0.6240 (12)	0.472 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1005 (3)	0.0644 (2)	0.02233 (13)	−0.01755 (16)	0.01035 (12)	−0.00145 (11)
O1	0.0749 (12)	0.0384 (9)	0.0233 (7)	−0.0087 (8)	0.0068 (7)	−0.0007 (6)
O2	0.0711 (11)	0.0338 (8)	0.0357 (8)	−0.0121 (8)	0.0053 (8)	0.0022 (7)
O3	0.1248 (17)	0.0381 (9)	0.0351 (9)	−0.0254 (10)	0.0207 (10)	−0.0054 (8)
N1	0.0502 (12)	0.0317 (10)	0.0292 (9)	0.0001 (8)	0.0104 (8)	0.0049 (7)
N2	0.0560 (12)	0.0280 (9)	0.0282 (9)	−0.0011 (9)	0.0123 (8)	0.0047 (7)
N3	0.0509 (12)	0.0379 (10)	0.0394 (10)	0.0030 (9)	0.0122 (9)	0.0087 (8)
C1	0.0411 (12)	0.0296 (10)	0.0269 (10)	0.0031 (9)	0.0082 (9)	0.0025 (8)
C2	0.0386 (12)	0.0318 (11)	0.0234 (9)	0.0049 (9)	0.0043 (8)	0.0006 (8)
C3	0.0373 (12)	0.0300 (11)	0.0313 (10)	0.0017 (9)	0.0062 (9)	0.0005 (9)
C4	0.0412 (13)	0.0364 (12)	0.0296 (10)	0.0030 (10)	0.0105 (9)	0.0059 (9)
C5	0.0477 (13)	0.0427 (13)	0.0215 (10)	−0.0004 (10)	0.0078 (9)	−0.0016 (9)
C6	0.0511 (14)	0.0339 (11)	0.0279 (10)	−0.0022 (10)	0.0079 (9)	−0.0036 (9)
C7	0.0523 (14)	0.0302 (11)	0.0309 (11)	−0.0003 (10)	0.0089 (10)	0.0000 (9)
C8	0.0502 (14)	0.0349 (12)	0.0296 (10)	−0.0024 (10)	0.0100 (10)	0.0013 (9)
C9	0.0390 (12)	0.0307 (11)	0.0290 (10)	0.0036 (9)	0.0123 (9)	0.0016 (8)
C10	0.0545 (15)	0.0368 (12)	0.0306 (11)	−0.0033 (11)	0.0059 (10)	−0.0002 (9)
C11	0.0582 (16)	0.0452 (14)	0.0301 (11)	0.0021 (12)	0.0042 (10)	0.0042 (10)
C12	0.0425 (13)	0.0334 (12)	0.0437 (12)	−0.0004 (10)	0.0108 (10)	0.0014 (10)
C13	0.0401 (12)	0.0361 (12)	0.0295 (10)	0.0031 (9)	0.0080 (9)	0.0001 (9)
C14	0.0624 (16)	0.0335 (12)	0.0482 (14)	−0.0057 (11)	0.0158 (12)	0.0047 (11)

Geometric parameters (Å, º) top

Br1—C5	1.895 (2)	C4—C5	1.386 (3)
O1—C2	1.356 (2)	C4—H4	0.9300
O1—H1	0.8200	C5—C6	1.363 (3)
O2—C3	1.360 (3)	C6—H6	0.9300
O2—C14	1.421 (3)	C7—H7	0.9300
O3—C8	1.207 (3)	C8—C9	1.505 (3)
N1—C7	1.275 (3)	C9—C10	1.385 (3)
N1—N2	1.375 (2)	C9—C13	1.386 (3)
N2—C8	1.353 (3)	C10—C11	1.381 (3)
N2—H2	0.889 (10)	C10—H10	0.9300
N3—C11	1.330 (3)	C11—H11	0.9300
N3—C12	1.336 (3)	C12—C13	1.381 (3)
C1—C2	1.394 (3)	C12—H12	0.9300
C1—C6	1.397 (3)	C13—H13	0.9300
C1—C7	1.454 (3)	C14—H14A	0.9600
C2—C3	1.409 (3)	C14—H14B	0.9600
C3—C4	1.380 (3)	C14—H14C	0.9600

C2—O1—H1	109.5	N1—C7—H7	119.4
C3—O2—C14	117.41 (17)	C1—C7—H7	119.4
C7—N1—N2	117.18 (18)	O3—C8—N2	122.6 (2)
C8—N2—N1	117.15 (18)	O3—C8—C9	121.04 (19)
C8—N2—H2	127 (2)	N2—C8—C9	116.37 (18)
N1—N2—H2	116 (2)	C10—C9—C13	117.73 (19)
C11—N3—C12	116.57 (19)	C10—C9—C8	116.78 (19)
C2—C1—C6	119.70 (19)	C13—C9—C8	125.48 (19)
C2—C1—C7	122.19 (18)	C11—C10—C9	119.3 (2)
C6—C1—C7	118.10 (19)	C11—C10—H10	120.4
O1—C2—C1	122.99 (18)	C9—C10—H10	120.4
O1—C2—C3	117.65 (18)	N3—C11—C10	123.6 (2)
C1—C2—C3	119.35 (18)	N3—C11—H11	118.2
O2—C3—C4	124.68 (19)	C10—C11—H11	118.2
O2—C3—C2	115.10 (18)	N3—C12—C13	124.1 (2)
C4—C3—C2	120.20 (19)	N3—C12—H12	118.0
C3—C4—C5	119.18 (19)	C13—C12—H12	118.0
C3—C4—H4	120.4	C12—C13—C9	118.7 (2)
C5—C4—H4	120.4	C12—C13—H13	120.7
C6—C5—C4	121.76 (19)	C9—C13—H13	120.7
C6—C5—Br1	119.16 (16)	O2—C14—H14A	109.5
C4—C5—Br1	119.06 (16)	O2—C14—H14B	109.5
C5—C6—C1	119.8 (2)	H14A—C14—H14B	109.5
C5—C6—H6	120.1	O2—C14—H14C	109.5
C1—C6—H6	120.1	H14A—C14—H14C	109.5
N1—C7—C1	121.2 (2)	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3ⁱ	0.89 (1)	2.26 (1)	3.126 (3)	166 (3)
O1—H1···N1	0.82	1.93	2.643 (2)	145

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂BrN₃O₃
M_r	350.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.4937 (9), 15.8843 (19), 11.7994 (14)
β (°)	99.776 (2)
V (Å³)	1384.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.98
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.587, 0.616
No. of measured, independent and observed [I > 2σ(I)] reflections	8003, 3013, 2299
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.076, 1.03
No. of reflections	3013
No. of parameters	195
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)	0.39, −0.41

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3ⁱ	0.889 (10)	2.255 (13)	3.126 (3)	166 (3)
O1—H1···N1	0.82	1.93	2.643 (2)	144.9

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The corresponding author gratefully acknowledges Changsha University of Science and Technology for research grants.

References

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