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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1381.
Published online 2008 July 5. doi:  10.1107/S1600536808019648
PMCID: PMC2962014

2′-(3-Bromo-5-chloro-2-hydroxy­benzyl­idene)isonicotinohydrazide methanol solvate

Abstract

The title Schiff base compound, C13H9BrClN3O2·CH4O, was derived from the condensation reaction of 3-bromo-5-chloro­salicylaldehyde with isonicotinohydrazide. The dihedral angle between the benzene and pyridine rings is 5.9 (2)°. In the crystal structure, mol­ecules are linked through N—H(...)O, O—H(...)O, and O—H(...)Br inter­molecular hydrogen bonds, forming dimers and chains. There is also an intramolecular O—H(...)N hydrogen bond.

Related literature

For related structures, see: Tang, (2006 [triangle]); Tang, (2007a [triangle],b [triangle],c [triangle],d [triangle]). For reference structural data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-o1381-scheme1.jpg

Experimental

Crystal data

  • C13H9BrClN3O2·CH4O
  • M r = 386.63
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1381-efi1.jpg
  • a = 7.531 (1) Å
  • b = 8.735 (1) Å
  • c = 12.130 (2) Å
  • α = 80.853 (2)°
  • β = 77.781 (2)°
  • γ = 86.721 (2)°
  • V = 769.73 (19) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.86 mm−1
  • T = 298 (2) K
  • 0.32 × 0.32 × 0.30 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.461, T max = 0.481 (expected range = 0.407–0.424)
  • 4529 measured reflections
  • 3254 independent reflections
  • 2438 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.093
  • S = 1.01
  • 3254 reflections
  • 205 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019648/at2582sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019648/at2582Isup2.hkl

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

Acknowledgments

Financial support from the Jiaying University research fund is gratefully acknowledged.

supplementary crystallographic information

Comment

Recently, the author has reported the structures of several Schiff base compounds (Tang, 2006; Tang, 2007a,b,c,d) and, in continuation of work in this area, reports herein the crystal structure of the title new Schiff base compound, (I).

In the title compound (Fig. 1), the dihedral angle between the benzene ring and the pyridine ring is 5.9 (2)°. The torsion angles C1—C7—N1—N2, C7—N1—N2—C8, and N1—N2—C8—C9 are 0.4 (2), 2.3 (2), and 1.9 (2)°, respectively. All the bond lengths are within normal values (Allen et al., 1987).

In the crystal structure of the compound, molecules are linked through N–H···O, O–H···O, and O–H···Br intermolecular hydrogen bonds (Table 1), forming dimers (Fig. 2).

Experimental

3-Bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.5 mg) and isonicotinohydrazide (0.1 mmol, 13.7 mg) were dissolved in a methanol solution (20 ml). The mixture was stirred at reflux for 10 min to give a clear colourless solution. Colourless block-like crystals of the compound were formed by slow evaporation of the solvent over several days.

Refinement

H2 was located from a difference Fourier map and refined isotropically, with Uiso restrained to 0.08Å2. Other H atoms were constrained to ideal geometries, with d(C–H) = 0.93–0.96 Å, d(O–H) = 0.82 Å, and with Uiso(H) = 1.2Ueq(C), 1.5Ueq(C14, O1 and O3).

Figures

Fig. 1.
The molecular structure of the compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Molecular packing of (I) with hydrogen bonds drawn as dashed lines.

Crystal data

C13H9BrClN3O2·C1H4O1Z = 2
Mr = 386.63F000 = 388
Triclinic, P1Dx = 1.668 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.531 (1) ÅCell parameters from 1404 reflections
b = 8.735 (1) Åθ = 2.5–24.3º
c = 12.130 (2) ŵ = 2.86 mm1
α = 80.853 (2)ºT = 298 (2) K
β = 77.781 (2)ºBlock, colourless
γ = 86.721 (2)º0.32 × 0.32 × 0.30 mm
V = 769.73 (19) Å3

Data collection

Bruker SMART CCD area-detector diffractometer3254 independent reflections
Radiation source: fine-focus sealed tube2438 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
T = 298(2) Kθmax = 27.0º
ω scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.461, Tmax = 0.481k = −11→10
4529 measured reflectionsl = −15→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093  w = 1/[σ2(Fo2) + (0.0424P)2 + 0.2117P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
3254 reflectionsΔρmax = 0.44 e Å3
205 parametersΔρmin = −0.36 e Å3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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 > 2sigma(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
Br11.13987 (5)0.60600 (4)0.27243 (3)0.04953 (14)
Cl11.14281 (14)0.21720 (11)−0.04331 (7)0.0585 (3)
O10.9336 (4)0.3429 (3)0.42960 (18)0.0492 (6)
H10.88050.26940.47180.074*
O20.6850 (4)0.1108 (3)0.6960 (2)0.0613 (7)
O30.7162 (4)0.6702 (3)0.4708 (2)0.0648 (7)
H30.81290.62130.46780.097*
N10.7910 (4)0.0712 (3)0.4821 (2)0.0422 (7)
N20.7009 (4)−0.0439 (3)0.5622 (2)0.0435 (7)
N30.3580 (4)−0.3481 (4)0.9325 (3)0.0541 (8)
C10.9409 (4)0.1661 (4)0.2938 (3)0.0376 (7)
C20.9789 (4)0.3099 (3)0.3219 (2)0.0356 (7)
C31.0695 (4)0.4184 (3)0.2357 (3)0.0371 (7)
C41.1193 (4)0.3917 (3)0.1240 (3)0.0383 (7)
H41.17880.46700.06740.046*
C51.0792 (4)0.2518 (4)0.0983 (3)0.0388 (7)
C60.9935 (4)0.1387 (4)0.1807 (3)0.0406 (8)
H60.97030.04390.16150.049*
C70.8466 (4)0.0454 (4)0.3797 (3)0.0423 (8)
H70.8271−0.04990.35990.051*
C80.6508 (4)−0.0112 (4)0.6708 (3)0.0392 (7)
C90.5474 (4)−0.1341 (3)0.7577 (3)0.0353 (7)
C100.5137 (5)−0.2802 (4)0.7393 (3)0.0432 (8)
H100.5524−0.30980.66750.052*
C110.4218 (5)−0.3815 (4)0.8288 (3)0.0533 (9)
H110.4032−0.48060.81550.064*
C120.3884 (5)−0.2064 (5)0.9486 (3)0.0601 (10)
H120.3433−0.17881.02040.072*
C130.4825 (5)−0.0977 (4)0.8658 (3)0.0507 (9)
H130.5023−0.00050.88250.061*
C140.6322 (7)0.6375 (5)0.3861 (4)0.0809 (14)
H14A0.51140.68200.39670.121*
H14B0.62640.52720.39020.121*
H14C0.70070.68080.31270.121*
H20.689 (6)−0.136 (2)0.543 (3)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0660 (3)0.0388 (2)0.0409 (2)−0.01820 (16)0.00010 (16)−0.00617 (14)
Cl10.0847 (7)0.0584 (5)0.0301 (4)−0.0171 (5)0.0016 (4)−0.0118 (4)
O10.0672 (17)0.0464 (14)0.0289 (12)−0.0191 (12)0.0035 (11)−0.0019 (10)
O20.088 (2)0.0386 (13)0.0523 (15)−0.0236 (13)0.0019 (13)−0.0050 (11)
O30.073 (2)0.0651 (18)0.0574 (17)−0.0025 (15)−0.0088 (15)−0.0168 (14)
N10.0448 (16)0.0384 (15)0.0373 (16)−0.0112 (12)−0.0042 (12)0.0104 (12)
N20.0547 (18)0.0384 (15)0.0331 (15)−0.0216 (14)−0.0030 (13)0.0063 (12)
N30.059 (2)0.0546 (19)0.0415 (17)−0.0192 (15)0.0025 (14)0.0047 (14)
C10.0376 (18)0.0377 (17)0.0344 (17)−0.0055 (14)−0.0053 (14)0.0028 (13)
C20.0383 (18)0.0375 (17)0.0292 (16)−0.0064 (14)−0.0041 (13)−0.0017 (13)
C30.0421 (19)0.0339 (16)0.0331 (16)−0.0103 (14)−0.0024 (14)−0.0028 (13)
C40.0418 (19)0.0351 (17)0.0322 (16)−0.0098 (14)0.0003 (14)0.0048 (13)
C50.0451 (19)0.0439 (18)0.0256 (15)−0.0084 (15)−0.0029 (14)−0.0028 (13)
C60.046 (2)0.0361 (17)0.0405 (18)−0.0097 (14)−0.0095 (15)−0.0049 (14)
C70.047 (2)0.0376 (17)0.0394 (19)−0.0157 (15)−0.0047 (15)0.0022 (14)
C80.0424 (19)0.0341 (17)0.0374 (18)−0.0089 (14)−0.0042 (14)0.0037 (14)
C90.0334 (17)0.0346 (16)0.0349 (17)−0.0086 (13)−0.0030 (13)0.0014 (13)
C100.052 (2)0.0387 (18)0.0335 (17)−0.0125 (15)0.0030 (15)−0.0025 (14)
C110.062 (2)0.0433 (19)0.049 (2)−0.0178 (18)0.0004 (18)0.0006 (16)
C120.068 (3)0.072 (3)0.035 (2)−0.022 (2)0.0059 (18)−0.0078 (18)
C130.061 (2)0.0446 (19)0.043 (2)−0.0167 (17)0.0042 (17)−0.0090 (16)
C140.095 (4)0.077 (3)0.078 (3)−0.012 (3)−0.025 (3)−0.019 (3)

Geometric parameters (Å, °)

Br1—C31.897 (3)C4—C51.373 (4)
Cl1—C51.753 (3)C4—H40.9300
O1—C21.351 (3)C5—C61.370 (4)
O1—H10.8200C6—H60.9300
O2—C81.209 (4)C7—H70.9300
O3—C141.388 (5)C8—C91.503 (4)
O3—H30.8200C9—C101.377 (4)
N1—C71.276 (4)C9—C131.380 (4)
N1—N21.380 (3)C10—C111.374 (4)
N2—C81.363 (4)C10—H100.9300
N2—H20.890 (10)C11—H110.9300
N3—C111.320 (5)C12—C131.373 (5)
N3—C121.323 (5)C12—H120.9300
C1—C61.400 (4)C13—H130.9300
C1—C21.412 (4)C14—H14A0.9600
C1—C71.457 (4)C14—H14B0.9600
C2—C31.383 (4)C14—H14C0.9600
C3—C41.380 (4)
C2—O1—H1109.5N1—C7—H7120.2
C14—O3—H3109.5C1—C7—H7120.2
C7—N1—N2118.9 (3)O2—C8—N2122.1 (3)
C8—N2—N1116.0 (3)O2—C8—C9121.6 (3)
C8—N2—H2124 (3)N2—C8—C9116.3 (3)
N1—N2—H2120 (3)C10—C9—C13117.2 (3)
C11—N3—C12115.9 (3)C10—C9—C8125.7 (3)
C6—C1—C2119.4 (3)C13—C9—C8117.0 (3)
C6—C1—C7118.9 (3)C11—C10—C9118.7 (3)
C2—C1—C7121.6 (3)C11—C10—H10120.6
O1—C2—C3119.5 (3)C9—C10—H10120.6
O1—C2—C1122.3 (3)N3—C11—C10124.7 (3)
C3—C2—C1118.2 (3)N3—C11—H11117.6
C4—C3—C2122.3 (3)C10—C11—H11117.6
C4—C3—Br1118.4 (2)N3—C12—C13124.1 (3)
C2—C3—Br1119.3 (2)N3—C12—H12118.0
C5—C4—C3118.6 (3)C13—C12—H12118.0
C5—C4—H4120.7C12—C13—C9119.3 (3)
C3—C4—H4120.7C12—C13—H13120.4
C6—C5—C4121.6 (3)C9—C13—H13120.4
C6—C5—Cl1119.6 (2)O3—C14—H14A109.5
C4—C5—Cl1118.8 (2)O3—C14—H14B109.5
C5—C6—C1119.9 (3)H14A—C14—H14B109.5
C5—C6—H6120.1O3—C14—H14C109.5
C1—C6—H6120.1H14A—C14—H14C109.5
N1—C7—C1119.6 (3)H14B—C14—H14C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O3i0.890 (10)2.005 (15)2.876 (4)166 (4)
O3—H3···Br10.823.053.641 (3)131
O3—H3···O10.822.623.268 (4)137
O3—H3···O1ii0.822.553.114 (4)127
O1—H1···N10.821.872.590 (3)146

Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2582).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2002). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tang, C.-B. (2006). Acta Cryst. E62, m2629–m2630.
  • Tang, C.-B. (2007a). Acta Cryst. E63, m2654.
  • Tang, C.-B. (2007b). Acta Cryst. E63, m2785–m2786.
  • Tang, C.-B. (2007c). Acta Cryst. E63, o4545.
  • Tang, C.-B. (2007d). Acta Cryst. E63, o4841.

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