PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o909.
Published online 2009 March 28. doi:  10.1107/S1600536809010575
PMCID: PMC2968970

N′-(3-Bromo-5-chloro-2-hydroxy­benzyl­idene)-3,4,5-trihydroxy­benzohydrazide methanol solvate

Abstract

The benzohydrazide mol­ecule of the title compound, C14H10BrClN2O5·CH3OH, is non-planar, the two aromatic rings at either side of the –C(=O)–NH–N=CH– unit being twisted by 5.9 (1)°. The benzohydrazide mol­ecule is linked to the solvent mol­ecule by an O—H(...)O hydrogen bond. Mol­ecules are connected by further O—H(...)O hydrogen bonds and an N—H(...)O link into a two-dimensional array.

Related literature

For the the parent N′-(2-hydroxy­benzyl­idene)benzohydrazide, see: Lyubchova et al. (1995 [triangle]). For other N′-(2-hydr­oxy-5-nitro­benzyl­idene)benzohydrazides, see: Ali et al. (2005 [triangle]); Lyubchova et al. (1995 [triangle]); Xu & Liu (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o909-scheme1.jpg

Experimental

Crystal data

  • C14H10BrClN2O5·CH4O
  • M r = 433.64
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o909-efi1.jpg
  • a = 21.6157 (3) Å
  • b = 12.7408 (2) Å
  • c = 17.0803 (2) Å
  • β = 136.641 (1)°
  • V = 3229.57 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 2.75 mm−1
  • T = 123 K
  • 0.20 × 0.15 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.610, T max = 0.771
  • 15301 measured reflections
  • 3714 independent reflections
  • 3407 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.068
  • S = 1.03
  • 3714 reflections
  • 251 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [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: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010575/tk2400sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809010575/tk2400Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

3-Bromo-5-chloro-2-hydroxybenzaldehyde (0.47 g, 2 mmol) and 3,4,5-trihydroxybenzoylhydrazide (0.36 g, 2 mmol) were heated in ethanol (50 ml) for several hours. The solvent was removed and the product recrystallized from methanol.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H 0.95 Å, U(H) = 1.2U(C)], and were included in the refinement in the riding model approximation.

The amino and hydroxy H-atoms were located in a difference Fourier map, and were refined with distance restraints of N–H 0.88±0.01 Å and O–H 0.84±0.01 Å, respectively; their temperature factors were refined isotropically.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C14H10BrClNO5.CH3OH at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C14H10BrClN2O5·CH4OF(000) = 1744
Mr = 433.64Dx = 1.784 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8789 reflections
a = 21.6157 (3) Åθ = 2.7–28.3°
b = 12.7408 (2) ŵ = 2.75 mm1
c = 17.0803 (2) ÅT = 123 K
β = 136.641 (1)°Polyhedral, tan
V = 3229.57 (8) Å30.20 × 0.15 × 0.10 mm
Z = 8

Data collection

Bruker SMART APEX diffractometer3714 independent reflections
Radiation source: fine-focus sealed tube3407 reflections with I > 2σ(I)
graphiteRint = 0.016
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −28→26
Tmin = 0.610, Tmax = 0.771k = −16→16
15301 measured reflectionsl = −22→21

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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0429P)2 + 3.4447P] where P = (Fo2 + 2Fc2)/3
3714 reflections(Δ/σ)max = 0.001
251 parametersΔρmax = 0.43 e Å3
6 restraintsΔρmin = −0.35 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.044783 (12)0.783092 (13)0.137916 (14)0.02172 (7)
Cl10.01420 (3)0.35175 (3)0.10946 (4)0.02369 (10)
N10.18779 (9)0.61375 (11)0.54542 (11)0.0148 (3)
N20.23179 (9)0.58418 (11)0.65407 (11)0.0154 (3)
O10.13116 (9)0.74001 (9)0.37133 (11)0.0211 (3)
O20.20939 (8)0.74133 (9)0.69379 (10)0.0187 (2)
O30.36037 (9)0.69205 (10)1.09583 (10)0.0219 (3)
O40.37603 (8)0.47725 (9)1.12740 (10)0.0189 (2)
O50.31633 (9)0.34724 (9)0.95863 (10)0.0205 (3)
O60.15053 (8)0.88367 (9)0.75713 (10)0.0196 (2)
C10.10878 (11)0.64859 (12)0.31698 (13)0.0155 (3)
C20.06644 (11)0.65171 (12)0.20499 (14)0.0156 (3)
C30.03858 (11)0.56163 (13)0.14173 (13)0.0172 (3)
H3A0.00880.56550.06520.021*
C40.05469 (11)0.46540 (12)0.19171 (14)0.0168 (3)
C50.09940 (10)0.45814 (12)0.30364 (13)0.0158 (3)
H5A0.11170.39140.33730.019*
C60.12644 (10)0.54979 (12)0.36718 (13)0.0151 (3)
C70.17192 (10)0.53678 (12)0.48399 (13)0.0155 (3)
H70.19070.46840.51630.019*
C80.23645 (10)0.64897 (12)0.72065 (13)0.0147 (3)
C90.27436 (10)0.60244 (12)0.82779 (13)0.0143 (3)
C100.30257 (11)0.66835 (12)0.91445 (13)0.0161 (3)
H100.29970.74240.90560.019*
C110.33473 (11)0.62583 (12)1.01356 (13)0.0156 (3)
C120.34227 (10)0.51690 (12)1.02835 (13)0.0146 (3)
C130.31234 (10)0.45163 (12)0.94055 (13)0.0147 (3)
C140.27745 (10)0.49359 (12)0.84020 (13)0.0146 (3)
H140.25570.44860.78000.018*
C150.06333 (12)0.92150 (14)0.65359 (15)0.0237 (4)
H15A0.04450.97810.67150.036*
H15B0.01960.86400.61600.036*
H15C0.06640.94820.60270.036*
H10.154 (2)0.731 (3)0.4365 (15)0.087 (13)*
H30.3635 (18)0.6613 (19)1.1413 (18)0.044 (7)*
H40.3783 (17)0.4119 (8)1.129 (2)0.036 (7)*
H50.3065 (15)0.3125 (16)0.9101 (15)0.030 (6)*
H60.1634 (16)0.8331 (14)0.741 (2)0.037 (7)*
H20.2604 (14)0.5242 (11)0.6799 (18)0.029 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.02904 (11)0.01747 (10)0.01845 (10)0.00031 (6)0.01720 (9)0.00285 (6)
Cl10.0373 (2)0.01580 (19)0.01895 (19)−0.00382 (16)0.02079 (19)−0.00522 (14)
N10.0169 (6)0.0172 (6)0.0109 (6)0.0006 (5)0.0103 (5)0.0013 (5)
N20.0205 (6)0.0142 (6)0.0119 (6)0.0032 (5)0.0120 (6)0.0031 (5)
O10.0321 (7)0.0152 (5)0.0161 (6)0.0006 (5)0.0175 (6)−0.0016 (5)
O20.0293 (6)0.0135 (5)0.0186 (6)0.0039 (5)0.0191 (5)0.0034 (4)
O30.0374 (7)0.0154 (5)0.0171 (6)−0.0039 (5)0.0212 (6)−0.0038 (5)
O40.0294 (6)0.0154 (6)0.0142 (5)0.0022 (5)0.0166 (5)0.0019 (4)
O50.0378 (7)0.0109 (5)0.0182 (6)0.0028 (5)0.0221 (6)0.0017 (4)
O60.0251 (6)0.0178 (6)0.0186 (6)0.0016 (5)0.0168 (5)−0.0013 (5)
C10.0184 (7)0.0151 (7)0.0154 (7)−0.0006 (6)0.0131 (7)−0.0020 (6)
C20.0186 (7)0.0153 (7)0.0153 (7)0.0015 (6)0.0130 (7)0.0026 (6)
C30.0185 (7)0.0226 (8)0.0135 (7)−0.0012 (6)0.0126 (7)−0.0011 (6)
C40.0202 (7)0.0170 (7)0.0169 (7)−0.0017 (6)0.0147 (7)−0.0037 (6)
C50.0184 (7)0.0153 (7)0.0164 (7)0.0005 (6)0.0136 (6)0.0007 (6)
C60.0164 (7)0.0182 (7)0.0129 (7)0.0004 (6)0.0113 (6)0.0003 (6)
C70.0173 (7)0.0156 (7)0.0135 (7)0.0006 (6)0.0112 (6)0.0017 (6)
C80.0165 (7)0.0151 (7)0.0138 (7)−0.0016 (6)0.0114 (6)−0.0007 (5)
C90.0158 (7)0.0158 (7)0.0126 (7)0.0010 (6)0.0107 (6)0.0009 (6)
C100.0212 (8)0.0123 (7)0.0166 (8)−0.0005 (6)0.0144 (7)−0.0003 (6)
C110.0198 (7)0.0148 (7)0.0140 (7)−0.0021 (6)0.0129 (6)−0.0030 (6)
C120.0168 (7)0.0167 (7)0.0123 (7)0.0009 (6)0.0112 (6)0.0013 (6)
C130.0180 (7)0.0121 (7)0.0168 (7)0.0016 (6)0.0136 (6)0.0006 (6)
C140.0189 (7)0.0136 (7)0.0144 (7)0.0005 (6)0.0131 (6)−0.0005 (5)
C150.0247 (8)0.0219 (8)0.0214 (8)0.0000 (7)0.0158 (7)−0.0015 (7)

Geometric parameters (Å, °)

Br1—C21.8852 (15)C3—C41.386 (2)
Cl1—C41.7460 (16)C3—H3A0.9500
N1—C71.287 (2)C4—C51.382 (2)
N1—N21.3870 (18)C5—C61.400 (2)
N2—C81.348 (2)C5—H5A0.9500
N2—H20.874 (10)C6—C71.457 (2)
O1—C11.3415 (19)C7—H70.9500
O1—H10.832 (10)C8—C91.480 (2)
O2—C81.2438 (19)C9—C141.397 (2)
O3—C111.3642 (19)C9—C101.398 (2)
O3—H30.828 (10)C10—C111.390 (2)
O4—C121.3619 (18)C10—H100.9500
O4—H40.833 (10)C11—C121.399 (2)
O5—C131.3538 (18)C12—C131.396 (2)
O5—H50.820 (10)C13—C141.383 (2)
O6—C151.437 (2)C14—H140.9500
O6—H60.828 (10)C15—H15A0.9800
C1—C21.397 (2)C15—H15B0.9800
C1—C61.410 (2)C15—H15C0.9800
C2—C31.379 (2)
C7—N1—N2113.63 (13)C6—C7—H7118.5
C8—N2—N1121.35 (13)O2—C8—N2122.77 (14)
C8—N2—H2121.2 (15)O2—C8—C9121.61 (14)
N1—N2—H2117.2 (15)N2—C8—C9115.61 (13)
C1—O1—H1112 (3)C14—C9—C10119.97 (14)
C11—O3—H3111.6 (19)C14—C9—C8120.49 (14)
C12—O4—H4112.6 (18)C10—C9—C8119.44 (14)
C13—O5—H5111.9 (17)C11—C10—C9120.15 (14)
C15—O6—H6107.8 (17)C11—C10—H10119.9
O1—C1—C2118.05 (14)C9—C10—H10119.9
O1—C1—C6123.52 (14)O3—C11—C10118.85 (14)
C2—C1—C6118.42 (14)O3—C11—C12121.39 (14)
C3—C2—C1121.82 (14)C10—C11—C12119.75 (14)
C3—C2—Br1119.27 (12)O4—C12—C13121.65 (14)
C1—C2—Br1118.90 (12)O4—C12—C11118.63 (14)
C2—C3—C4118.86 (14)C13—C12—C11119.67 (14)
C2—C3—H3A120.6O5—C13—C14123.32 (14)
C4—C3—H3A120.6O5—C13—C12115.94 (14)
C5—C4—C3121.40 (14)C14—C13—C12120.69 (14)
C5—C4—Cl1119.65 (12)C13—C14—C9119.64 (14)
C3—C4—Cl1118.92 (12)C13—C14—H14120.2
C4—C5—C6119.62 (14)C9—C14—H14120.2
C4—C5—H5A120.2O6—C15—H15A109.5
C6—C5—H5A120.2O6—C15—H15B109.5
C5—C6—C1119.81 (14)H15A—C15—H15B109.5
C5—C6—C7116.89 (14)O6—C15—H15C109.5
C1—C6—C7123.30 (14)H15A—C15—H15C109.5
N1—C7—C6122.97 (14)H15B—C15—H15C109.5
N1—C7—H7118.5
C7—N1—N2—C8−165.52 (15)N1—N2—C8—C9172.04 (14)
O1—C1—C2—C3−177.88 (15)O2—C8—C9—C14159.38 (15)
C6—C1—C2—C32.7 (2)N2—C8—C9—C14−19.4 (2)
O1—C1—C2—Br10.8 (2)O2—C8—C9—C10−17.1 (2)
C6—C1—C2—Br1−178.63 (11)N2—C8—C9—C10164.18 (15)
C1—C2—C3—C4−1.2 (2)C14—C9—C10—C110.8 (2)
Br1—C2—C3—C4−179.92 (12)C8—C9—C10—C11177.25 (14)
C2—C3—C4—C5−1.3 (2)C9—C10—C11—O3−178.92 (15)
C2—C3—C4—Cl1176.64 (12)C9—C10—C11—C122.6 (2)
C3—C4—C5—C62.2 (2)O3—C11—C12—O40.0 (2)
Cl1—C4—C5—C6−175.66 (12)C10—C11—C12—O4178.42 (14)
C4—C5—C6—C1−0.7 (2)O3—C11—C12—C13177.72 (14)
C4—C5—C6—C7179.02 (14)C10—C11—C12—C13−3.9 (2)
O1—C1—C6—C5178.92 (15)O4—C12—C13—O52.0 (2)
C2—C1—C6—C5−1.7 (2)C11—C12—C13—O5−175.63 (14)
O1—C1—C6—C7−0.8 (2)O4—C12—C13—C14179.35 (14)
C2—C1—C6—C7178.61 (14)C11—C12—C13—C141.7 (2)
N2—N1—C7—C6−179.99 (14)O5—C13—C14—C9178.84 (15)
C5—C6—C7—N1−169.07 (15)C12—C13—C14—C91.7 (2)
C1—C6—C7—N110.7 (2)C10—C9—C14—C13−3.0 (2)
N1—N2—C8—O2−6.7 (2)C8—C9—C14—C13−179.38 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O5i0.83 (1)2.03 (3)2.607 (2)126 (3)
O3—H3···O6ii0.83 (1)2.05 (1)2.856 (2)165 (3)
O4—H4···O1iii0.83 (1)2.20 (1)3.027 (2)173 (2)
O5—H5···O2iii0.82 (1)1.79 (1)2.608 (2)176 (2)
O6—H6···O20.83 (1)2.04 (1)2.843 (2)164 (2)
N2—H2···O6iii0.87 (1)2.25 (1)3.112 (2)169 (2)

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+3/2, −z+2; (iii) −x+1/2, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2400).

References

  • Ali, H. M., Puvaneswary, S. & Ng, S. W. (2005). Acta Cryst. E61, o3464–o3465.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lyubchova, A., Cossé-Barbi, A., Doucet, J. P., Robert, F., Souron, J.-P. & Quarton, M. (1995). Acta Cryst. C51, 1893–1895.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.
  • Xu, H.-M. & Liu, S.-X. (2006). Acta Cryst. E62, o3026–o3027.

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