PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1995.
Published online 2008 September 24. doi:  10.1107/S1600536808029607
PMCID: PMC2959402

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

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-64-o1995-scheme1.jpg

Experimental

Crystal data

  • C14H12BrN3O3
  • M r = 350.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1995-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.076
  • S = 1.03
  • 3013 reflections
  • 195 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H2 was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å, and with Uiso set at 0.08 Å2. Other H atoms were placed in calculated positions with C—H distances of 0.93–0.96 Å, O—H distance of 0.82 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).

Figures

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..

Crystal data

C14H12BrN3O3F(000) = 704
Mr = 350.18Dx = 1.680 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3223 reflections
a = 7.4937 (9) Åθ = 2.5–29.2°
b = 15.8843 (19) ŵ = 2.98 mm1
c = 11.7994 (14) ÅT = 298 K
β = 99.776 (2)°Block, colorless
V = 1384.1 (3) Å30.20 × 0.18 × 0.18 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer3013 independent reflections
Radiation source: fine-focus sealed tube2299 reflections with I > 2σ(I)
graphiteRint = 0.023
ω scansθmax = 27.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −9→9
Tmin = 0.587, Tmax = 0.616k = −17→20
8003 measured reflectionsl = −15→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0328P)2 + 0.5984P] where P = (Fo2 + 2Fc2)/3
3013 reflections(Δ/σ)max = 0.001
195 parametersΔρmax = 0.39 e Å3
1 restraintΔρmin = −0.41 e Å3

Special details

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)

xyzUiso*/Ueq
Br10.28353 (5)0.417081 (18)1.029574 (19)0.06245 (12)
O10.1144 (2)0.35958 (10)0.51873 (12)0.0457 (4)
H10.15100.39850.48320.069*
O20.0357 (2)0.24186 (10)0.65725 (13)0.0473 (4)
O30.2696 (3)0.49630 (11)0.27412 (14)0.0651 (6)
N10.2592 (2)0.50906 (11)0.49603 (15)0.0366 (4)
N20.3058 (3)0.57618 (11)0.43355 (15)0.0368 (4)
N30.3899 (3)0.77447 (12)0.10697 (16)0.0422 (5)
C10.2305 (3)0.45105 (13)0.67791 (17)0.0322 (5)
C20.1524 (3)0.37588 (13)0.63313 (16)0.0314 (4)
C30.1127 (3)0.31267 (13)0.70889 (17)0.0328 (5)
C40.1548 (3)0.32447 (14)0.82630 (17)0.0352 (5)
H40.13140.28230.87650.042*
C50.2323 (3)0.39986 (14)0.86841 (17)0.0370 (5)
C60.2695 (3)0.46250 (14)0.79697 (17)0.0375 (5)
H60.32080.51270.82740.045*
C70.2776 (3)0.51825 (13)0.60474 (18)0.0376 (5)
H70.32200.56890.63780.045*
C80.3013 (3)0.56400 (14)0.31958 (18)0.0379 (5)
C90.3367 (3)0.64012 (13)0.25079 (17)0.0321 (5)
C100.2656 (3)0.63897 (14)0.13450 (18)0.0408 (5)
H100.19910.59290.10220.049*
C110.2945 (3)0.70697 (15)0.0670 (2)0.0449 (6)
H110.24450.7055−0.01070.054*
C120.4597 (3)0.77448 (14)0.2190 (2)0.0395 (5)
H120.52870.82070.24840.047*
C130.4358 (3)0.71018 (13)0.29379 (18)0.0350 (5)
H130.48530.71380.37140.042*
C140.0108 (3)0.17267 (14)0.7293 (2)0.0473 (6)
H14A0.12550.15660.77320.071*
H14B−0.03970.12610.68280.071*
H14C−0.07010.18860.78050.071*
H20.331 (4)0.6240 (12)0.472 (2)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.1005 (3)0.0644 (2)0.02233 (13)−0.01755 (16)0.01035 (12)−0.00145 (11)
O10.0749 (12)0.0384 (9)0.0233 (7)−0.0087 (8)0.0068 (7)−0.0007 (6)
O20.0711 (11)0.0338 (8)0.0357 (8)−0.0121 (8)0.0053 (8)0.0022 (7)
O30.1248 (17)0.0381 (9)0.0351 (9)−0.0254 (10)0.0207 (10)−0.0054 (8)
N10.0502 (12)0.0317 (10)0.0292 (9)0.0001 (8)0.0104 (8)0.0049 (7)
N20.0560 (12)0.0280 (9)0.0282 (9)−0.0011 (9)0.0123 (8)0.0047 (7)
N30.0509 (12)0.0379 (10)0.0394 (10)0.0030 (9)0.0122 (9)0.0087 (8)
C10.0411 (12)0.0296 (10)0.0269 (10)0.0031 (9)0.0082 (9)0.0025 (8)
C20.0386 (12)0.0318 (11)0.0234 (9)0.0049 (9)0.0043 (8)0.0006 (8)
C30.0373 (12)0.0300 (11)0.0313 (10)0.0017 (9)0.0062 (9)0.0005 (9)
C40.0412 (13)0.0364 (12)0.0296 (10)0.0030 (10)0.0105 (9)0.0059 (9)
C50.0477 (13)0.0427 (13)0.0215 (10)−0.0004 (10)0.0078 (9)−0.0016 (9)
C60.0511 (14)0.0339 (11)0.0279 (10)−0.0022 (10)0.0079 (9)−0.0036 (9)
C70.0523 (14)0.0302 (11)0.0309 (11)−0.0003 (10)0.0089 (10)0.0000 (9)
C80.0502 (14)0.0349 (12)0.0296 (10)−0.0024 (10)0.0100 (10)0.0013 (9)
C90.0390 (12)0.0307 (11)0.0290 (10)0.0036 (9)0.0123 (9)0.0016 (8)
C100.0545 (15)0.0368 (12)0.0306 (11)−0.0033 (11)0.0059 (10)−0.0002 (9)
C110.0582 (16)0.0452 (14)0.0301 (11)0.0021 (12)0.0042 (10)0.0042 (10)
C120.0425 (13)0.0334 (12)0.0437 (12)−0.0004 (10)0.0108 (10)0.0014 (10)
C130.0401 (12)0.0361 (12)0.0295 (10)0.0031 (9)0.0080 (9)0.0001 (9)
C140.0624 (16)0.0335 (12)0.0482 (14)−0.0057 (11)0.0158 (12)0.0047 (11)

Geometric parameters (Å, °)

Br1—C51.895 (2)C4—C51.386 (3)
O1—C21.356 (2)C4—H40.9300
O1—H10.8200C5—C61.363 (3)
O2—C31.360 (3)C6—H60.9300
O2—C141.421 (3)C7—H70.9300
O3—C81.207 (3)C8—C91.505 (3)
N1—C71.275 (3)C9—C101.385 (3)
N1—N21.375 (2)C9—C131.386 (3)
N2—C81.353 (3)C10—C111.381 (3)
N2—H20.889 (10)C10—H100.9300
N3—C111.330 (3)C11—H110.9300
N3—C121.336 (3)C12—C131.381 (3)
C1—C21.394 (3)C12—H120.9300
C1—C61.397 (3)C13—H130.9300
C1—C71.454 (3)C14—H14A0.9600
C2—C31.409 (3)C14—H14B0.9600
C3—C41.380 (3)C14—H14C0.9600
C2—O1—H1109.5N1—C7—H7119.4
C3—O2—C14117.41 (17)C1—C7—H7119.4
C7—N1—N2117.18 (18)O3—C8—N2122.6 (2)
C8—N2—N1117.15 (18)O3—C8—C9121.04 (19)
C8—N2—H2127 (2)N2—C8—C9116.37 (18)
N1—N2—H2116 (2)C10—C9—C13117.73 (19)
C11—N3—C12116.57 (19)C10—C9—C8116.78 (19)
C2—C1—C6119.70 (19)C13—C9—C8125.48 (19)
C2—C1—C7122.19 (18)C11—C10—C9119.3 (2)
C6—C1—C7118.10 (19)C11—C10—H10120.4
O1—C2—C1122.99 (18)C9—C10—H10120.4
O1—C2—C3117.65 (18)N3—C11—C10123.6 (2)
C1—C2—C3119.35 (18)N3—C11—H11118.2
O2—C3—C4124.68 (19)C10—C11—H11118.2
O2—C3—C2115.10 (18)N3—C12—C13124.1 (2)
C4—C3—C2120.20 (19)N3—C12—H12118.0
C3—C4—C5119.18 (19)C13—C12—H12118.0
C3—C4—H4120.4C12—C13—C9118.7 (2)
C5—C4—H4120.4C12—C13—H13120.7
C6—C5—C4121.76 (19)C9—C13—H13120.7
C6—C5—Br1119.16 (16)O2—C14—H14A109.5
C4—C5—Br1119.06 (16)O2—C14—H14B109.5
C5—C6—C1119.8 (2)H14A—C14—H14B109.5
C5—C6—H6120.1O2—C14—H14C109.5
C1—C6—H6120.1H14A—C14—H14C109.5
N1—C7—C1121.2 (2)H14B—C14—H14C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···N3i0.89 (1)2.26 (1)3.126 (3)166 (3)
O1—H1···N10.821.932.643 (2)145.

Symmetry codes: (i) x, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2539).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19.
  • Alvarez, C., Alvarez, R., Corchete, P., Lopez, J. L., Perez-Melero, C., Pelaez, R. & Medarde, M. (2008). Bioorg. Med. Chem.16, 5952–5961. [PubMed]
  • Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, J., Liu, F., Song, B.-A., Yang, S., Hu, D.-Y., Jin, H.-H., Chen, Z. & Xue, W. (2008). Chin. J. Org. Chem.28, 894–898.
  • Ejsmont, K., Zareef, M., Arfan, M., Bashir, S. A. & Zaleski, J. (2008). Acta Cryst. E64, o1128. [PMC free article] [PubMed]
  • El-Tabl, A. S., El-Saied, F. A. & Al-Hakimi, A. N. (2008). J. Coord. Chem.61, 2380–2401.
  • Fun, H.-K., Patil, P. S., Rao, J. N., Kalluraya, B. & Chantrapromma, S. (2008). Acta Cryst. E64, o1707. [PMC free article] [PubMed]
  • Han, J.-R., Wang, X.-F., Zhen, X.-L., Tian, X. & Liu, S.-X. (2006). Acta Cryst. E62, o5572–o5573.
  • Kalinowski, D. S., Sharpe, P. C., Bernhardt, P. V. & Richardson, D. R. (2008). J. Med. Chem.51, 331–344. [PubMed]
  • Lu, J.-F., Min, S.-T., Ji, X.-H. & Dang, Z.-H. (2008). Acta Cryst. E64, o1695. [PMC free article] [PubMed]
  • Peng, S.-J. & Hou, H.-Y. (2008). Acta Cryst. E64, o1864. [PMC free article] [PubMed]
  • Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008). Acta Cryst. E64, o1363. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Ventura, C. & Martins, F. (2008). J. Med. Chem.51, 612–624. [PubMed]
  • Yehye, W. A., Ariffin, A. & Ng, S. W. (2008). Acta Cryst. E64, o960. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography