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 August 1; 64(Pt 8): o1630.
Published online 2008 July 31. doi:  10.1107/S1600536808021764
PMCID: PMC2962239

N′-(2-Bromo­benzyl­idene)-3,4,5-tri­methoxy­benzohydrazide methanol solvate

Abstract

The title compound, C17H17BrN2O4·CH4O, was synthesized by the condensation of 3,4,5-trimethoxy­benzohydrazide and 2-bromo­benzaldehyde. The two aromatic rings are approximately planar, the dihedral angle being 3.08 (9)°. The mol­ecules are linked by inter­molecular N—H(...)O and O—H(...)O hydrogen bonds into chains along the a axis.

Related literature

For related literature, see: Constable & Holmes (1987 [triangle]); Ganjali et al. (2006 [triangle]); Gardner et al. (1991 [triangle]); Jing et al. (2006 [triangle]); Kuriakose et al. (2007 [triangle]); Patole et al. (2003 [triangle]); Zhou et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1630-scheme1.jpg

Experimental

Crystal data

  • C17H17BrN2O4·CH4O
  • M r = 425.28
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1630-efi1.jpg
  • a = 12.9234 (7) Å
  • b = 4.9159 (3) Å
  • c = 29.3975 (17) Å
  • V = 1867.63 (19) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.23 mm−1
  • T = 173 (2) K
  • 0.36 × 0.35 × 0.33 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.455, T max = 0.479
  • 8158 measured reflections
  • 3799 independent reflections
  • 3206 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.080
  • S = 1.04
  • 3799 reflections
  • 240 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.26 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1720 Friedel pairs
  • Flack parameter: −0.008 (8)

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2003 [triangle]); data reduction: SAINT-Plus; 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 I, global. DOI: 10.1107/S1600536808021764/wn2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021764/wn2271Isup2.hkl

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

Acknowledgments

The authors thank the Natural Science Youth Foundation of South China University of Technology for financial assistance (E5050570).

supplementary crystallographic information

Comment

Hydrazones are acknowledged to possess a diverse range of bioactivities; these include antibacterial, antiviral, antineoplastic, and anti-inflammatory (Constable & Holmes, 1987; Ganjali et al., 2006; Gardner et al., 1991; Patole et al., 2003). In addition, many hydrazones have also been used as ligands because they can readily form stable complexes with most metal ions (Kuriakose et al., 2007; Zhou et al., 2005). We report here the synthesis and crystal structure of the title compound, obtained by the condensation of 3,4,5-trimethoxybenzohydrazide and 2-bromobenzaldehyde.

The asymmetric unit of the title compound comprises one N'-(2-bromobenzylidene)-3,4,5-trimethoxybenzohydrazide and a methanol solvent molecule (Fig. 1). The two aromatic rings are approximately planar, with a dihedral angle of 3.08 (9)°. Similar geometry has been observed in related hydrazone analogues (Jing et al., 2006). The methanol molecules in the crystal structure are linked to N'-(2-bromobenzylidene)-3,4,5-trimethoxybenzohydrazide through intermolecular N—H···O and O—H···O hydrogen bonds into chains along the a axis (Fig. 2).

Experimental

A mixture of 3,4,5-trimethoxybenzohydrazide (1 mmol) and 2-bromobenzaldehyde (1 mmol) in anhydrous ethanol (10 ml) was refluxed for 2 h. When the solution was cooled to room temperature, some white needles separated out. After filtration, colorless single crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement

All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with N—H = 0.88 Å, O—H = 0.84 Å, Csp2—H = 0.95 Å, C(methyl)—H = 0.98 Å and Uiso(H) = xUeq(C, N, O), where x = 1.5 for the methyl and hydroxyl groups, x = 1.2 for all other H atoms.

Figures

Fig. 1.
The structure of the two independent molecules in the asymmetric unit of the title compound, with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are represented by spheres of arbitrary radius.
Fig. 2.
The packing of the title compound, viewed down the b axis. The dashed lines represent the hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

Crystal data

C17H17BrN2O4·CH4OF000 = 872
Mr = 425.28Dx = 1.512 Mg m3
Orthorhombic, Pna21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 4139 reflections
a = 12.9234 (7) Åθ = 2.8–26.8º
b = 4.9159 (3) ŵ = 2.23 mm1
c = 29.3975 (17) ÅT = 173 (2) K
V = 1867.63 (19) Å3Block, colorless
Z = 40.36 × 0.35 × 0.33 mm

Data collection

Bruker SMART 1000 CCD diffractometer3799 independent reflections
Radiation source: fine-focus sealed tube3206 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 173(2) Kθmax = 27.0º
ω scansθmin = 1.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)h = −15→16
Tmin = 0.455, Tmax = 0.479k = −2→6
8158 measured reflectionsl = −34→37

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.030  w = 1/[σ2(Fo2) + 0.8008P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.080(Δ/σ)max = 0.001
S = 1.04Δρmax = 0.33 e Å3
3799 reflectionsΔρmin = −0.26 e Å3
240 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1720 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.008 (8)
Secondary atom site location: difference Fourier map

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
Br10.61656 (2)1.31840 (7)0.659414 (16)0.03707 (11)
C10.5590 (2)0.7908 (6)0.89278 (10)0.0193 (6)
C20.6409 (2)0.9755 (6)0.89566 (11)0.0195 (6)
H20.65931.08310.87010.023*
C30.6953 (2)1.0008 (6)0.93627 (11)0.0207 (7)
C40.6698 (2)0.8389 (6)0.97327 (10)0.0186 (6)
C50.5855 (2)0.6608 (6)0.97056 (11)0.0215 (7)
C60.5308 (2)0.6357 (6)0.93023 (11)0.0211 (7)
H60.47420.51290.92820.025*
C70.4968 (2)0.7557 (6)0.85047 (11)0.0212 (7)
C80.5282 (3)0.9221 (7)0.73624 (12)0.0276 (7)
H80.59620.99520.73770.033*
C90.4707 (3)0.9235 (7)0.69320 (11)0.0254 (7)
C100.4991 (2)1.0835 (6)0.65573 (14)0.0264 (7)
C110.4448 (3)1.0814 (8)0.61551 (12)0.0337 (8)
H110.46571.19550.59110.040*
C120.3603 (3)0.9139 (8)0.61066 (13)0.0362 (9)
H120.32350.90840.58270.043*
C130.3292 (3)0.7520 (8)0.64720 (12)0.0344 (9)
H130.27090.63570.64410.041*
C140.3830 (3)0.7604 (8)0.68790 (14)0.0312 (8)
H140.35980.65300.71270.037*
C150.8028 (3)1.3547 (7)0.90665 (12)0.0254 (7)
H15A0.82761.24780.88070.038*
H15B0.85771.47790.91680.038*
H15C0.74221.46110.89750.038*
C160.7819 (3)0.6441 (7)1.02794 (14)0.0378 (9)
H16A0.74020.47921.02420.057*
H16B0.80030.66601.06010.057*
H16C0.84510.62891.00970.057*
C170.4812 (3)0.3298 (7)1.00811 (13)0.0294 (8)
H17A0.41600.42111.00060.044*
H17B0.47480.24071.03780.044*
H17C0.49680.19320.98480.044*
C180.2740 (4)0.2319 (9)0.78016 (15)0.0461 (11)
H18A0.31830.22810.75310.069*
H18B0.20920.13600.77370.069*
H18C0.30960.14260.80550.069*
N20.4860 (2)0.8218 (6)0.77170 (9)0.0247 (6)
N10.5432 (2)0.8335 (6)0.81116 (9)0.0254 (6)
H1A0.60790.88970.81090.030*
O10.77516 (17)1.1759 (4)0.94291 (7)0.0240 (5)
O20.72395 (17)0.8738 (5)1.01327 (8)0.0247 (5)
O30.56273 (16)0.5255 (5)1.00977 (8)0.0279 (5)
O40.40936 (17)0.6632 (5)0.85149 (8)0.0282 (5)
O50.25214 (18)0.5045 (5)0.79189 (9)0.0319 (6)
H50.29730.56150.81010.048*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.03845 (18)0.03817 (18)0.03459 (19)−0.00184 (16)0.0079 (2)0.0056 (2)
C10.0208 (15)0.0234 (15)0.0137 (16)0.0046 (13)−0.0037 (12)−0.0005 (12)
C20.0212 (15)0.0209 (15)0.0165 (16)0.0034 (13)−0.0004 (12)0.0008 (12)
C30.0181 (14)0.0212 (16)0.0228 (17)0.0016 (13)0.0009 (13)−0.0054 (13)
C40.0209 (15)0.0203 (15)0.0144 (16)0.0027 (13)−0.0023 (12)−0.0036 (12)
C50.0218 (15)0.0231 (17)0.0195 (17)0.0003 (13)−0.0024 (13)0.0030 (13)
C60.0201 (15)0.0238 (16)0.0194 (17)0.0007 (13)−0.0051 (12)0.0003 (13)
C70.0206 (15)0.0247 (16)0.0183 (16)0.0010 (13)−0.0012 (13)−0.0004 (12)
C80.0235 (16)0.0360 (18)0.0232 (18)−0.0025 (15)−0.0004 (14)0.0030 (15)
C90.0271 (17)0.0318 (17)0.0172 (17)0.0048 (15)−0.0029 (13)−0.0024 (13)
C100.0313 (15)0.0282 (14)0.0196 (17)0.0088 (12)0.0059 (18)−0.0007 (16)
C110.047 (2)0.037 (2)0.0170 (18)0.0092 (18)0.0041 (16)0.0035 (15)
C120.047 (2)0.043 (2)0.0192 (19)0.0102 (19)−0.0100 (16)−0.0003 (16)
C130.0344 (18)0.042 (2)0.027 (2)−0.0003 (16)−0.0079 (16)−0.0059 (14)
C140.033 (2)0.040 (2)0.021 (2)0.0007 (18)−0.0008 (15)0.0053 (14)
C150.0242 (16)0.0260 (18)0.0260 (19)−0.0014 (15)0.0021 (14)−0.0016 (14)
C160.040 (2)0.036 (2)0.037 (2)0.0072 (19)−0.0187 (18)−0.0032 (17)
C170.0250 (17)0.0339 (19)0.0294 (19)−0.0035 (16)0.0007 (14)0.0083 (16)
C180.057 (3)0.046 (2)0.036 (2)0.011 (2)−0.004 (2)−0.0082 (19)
N20.0217 (13)0.0366 (16)0.0159 (14)−0.0002 (12)−0.0058 (11)0.0011 (12)
N10.0185 (13)0.0413 (18)0.0162 (14)−0.0031 (13)−0.0030 (10)0.0024 (12)
O10.0251 (11)0.0277 (12)0.0193 (12)−0.0046 (10)−0.0042 (9)0.0012 (9)
O20.0305 (12)0.0285 (12)0.0150 (12)−0.0001 (10)−0.0068 (10)−0.0019 (9)
O30.0277 (12)0.0379 (13)0.0181 (12)−0.0087 (11)−0.0042 (10)0.0067 (10)
O40.0232 (11)0.0409 (14)0.0205 (13)−0.0073 (11)−0.0049 (10)0.0038 (10)
O50.0230 (12)0.0402 (14)0.0326 (14)0.0039 (11)−0.0045 (11)−0.0067 (11)

Geometric parameters (Å, °)

Br1—C101.911 (3)C12—H120.9500
C1—C61.388 (4)C13—C141.384 (5)
C1—C21.397 (4)C13—H130.9500
C1—C71.491 (4)C14—H140.9500
C2—C31.391 (4)C15—O11.427 (4)
C2—H20.9500C15—H15A0.9800
C3—O11.358 (4)C15—H15B0.9800
C3—C41.388 (4)C15—H15C0.9800
C4—O21.379 (4)C16—O21.422 (4)
C4—C51.400 (5)C16—H16A0.9800
C5—O31.363 (4)C16—H16B0.9800
C5—C61.386 (4)C16—H16C0.9800
C6—H60.9500C17—O31.428 (4)
C7—O41.218 (4)C17—H17A0.9800
C7—N11.357 (4)C17—H17B0.9800
C8—N21.276 (4)C17—H17C0.9800
C8—C91.467 (4)C18—O51.412 (5)
C8—H80.9500C18—H18A0.9800
C9—C141.398 (5)C18—H18B0.9800
C9—C101.402 (5)C18—H18C0.9800
C10—C111.375 (5)N2—N11.377 (4)
C11—C121.375 (6)N1—H1A0.8800
C11—H110.9500O5—H50.8400
C12—C131.396 (5)
C6—C1—C2120.5 (3)C14—C13—H13119.9
C6—C1—C7117.1 (3)C12—C13—H13119.9
C2—C1—C7122.3 (3)C13—C14—C9121.4 (4)
C3—C2—C1119.5 (3)C13—C14—H14119.3
C3—C2—H2120.2C9—C14—H14119.3
C1—C2—H2120.2O1—C15—H15A109.5
O1—C3—C4115.6 (3)O1—C15—H15B109.5
O1—C3—C2124.3 (3)H15A—C15—H15B109.5
C4—C3—C2120.1 (3)O1—C15—H15C109.5
O2—C4—C3118.5 (3)H15A—C15—H15C109.5
O2—C4—C5121.4 (3)H15B—C15—H15C109.5
C3—C4—C5119.9 (3)O2—C16—H16A109.5
O3—C5—C6124.7 (3)O2—C16—H16B109.5
O3—C5—C4115.2 (3)H16A—C16—H16B109.5
C6—C5—C4120.1 (3)O2—C16—H16C109.5
C5—C6—C1119.7 (3)H16A—C16—H16C109.5
C5—C6—H6120.2H16B—C16—H16C109.5
C1—C6—H6120.2O3—C17—H17A109.5
O4—C7—N1122.4 (3)O3—C17—H17B109.5
O4—C7—C1121.5 (3)H17A—C17—H17B109.5
N1—C7—C1116.1 (3)O3—C17—H17C109.5
N2—C8—C9119.3 (3)H17A—C17—H17C109.5
N2—C8—H8120.3H17B—C17—H17C109.5
C9—C8—H8120.3O5—C18—H18A109.5
C14—C9—C10116.5 (3)O5—C18—H18B109.5
C14—C9—C8120.3 (3)H18A—C18—H18B109.5
C10—C9—C8123.2 (3)O5—C18—H18C109.5
C11—C10—C9122.6 (3)H18A—C18—H18C109.5
C11—C10—Br1117.3 (3)H18B—C18—H18C109.5
C9—C10—Br1120.1 (3)C8—N2—N1116.2 (3)
C12—C11—C10119.9 (3)C7—N1—N2117.9 (3)
C12—C11—H11120.0C7—N1—H1A121.1
C10—C11—H11120.0N2—N1—H1A121.1
C11—C12—C13119.4 (3)C3—O1—C15118.2 (2)
C11—C12—H12120.3C4—O2—C16115.3 (2)
C13—C12—H12120.3C5—O3—C17117.4 (3)
C14—C13—C12120.2 (4)C18—O5—H5109.5
C6—C1—C2—C30.9 (4)C14—C9—C10—C11−0.5 (5)
C7—C1—C2—C3179.4 (3)C8—C9—C10—C11179.6 (3)
C1—C2—C3—O1−179.2 (3)C14—C9—C10—Br1179.1 (2)
C1—C2—C3—C41.5 (4)C8—C9—C10—Br1−0.9 (4)
O1—C3—C4—O22.0 (4)C9—C10—C11—C12−1.2 (5)
C2—C3—C4—O2−178.6 (3)Br1—C10—C11—C12179.2 (3)
O1—C3—C4—C5177.0 (3)C10—C11—C12—C131.5 (5)
C2—C3—C4—C5−3.6 (4)C11—C12—C13—C140.0 (6)
O2—C4—C5—O3−0.7 (4)C12—C13—C14—C9−1.8 (6)
C3—C4—C5—O3−175.6 (3)C10—C9—C14—C131.9 (5)
O2—C4—C5—C6178.2 (3)C8—C9—C14—C13−178.1 (3)
C3—C4—C5—C63.3 (4)C9—C8—N2—N1−178.4 (3)
O3—C5—C6—C1177.8 (3)O4—C7—N1—N24.1 (5)
C4—C5—C6—C1−1.0 (5)C1—C7—N1—N2−175.7 (3)
C2—C1—C6—C5−1.2 (5)C8—N2—N1—C7173.1 (3)
C7—C1—C6—C5−179.7 (3)C4—C3—O1—C15−177.9 (3)
C6—C1—C7—O421.3 (4)C2—C3—O1—C152.7 (4)
C2—C1—C7—O4−157.2 (3)C3—C4—O2—C16−117.3 (3)
C6—C1—C7—N1−159.0 (3)C5—C4—O2—C1667.8 (4)
C2—C1—C7—N122.5 (4)C6—C5—O3—C174.7 (5)
N2—C8—C9—C14−15.7 (5)C4—C5—O3—C17−176.5 (3)
N2—C8—C9—C10164.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O5i0.882.012.871 (4)164
O5—H5···O40.841.962.794 (3)175

Symmetry codes: (i) x+1/2, −y+3/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2271).

References

  • Bruker (2001). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Constable, E. C. & Holmes, J. M. (1987). Inorg. Chim. Acta, 126, 195–197.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Ganjali, M. R., Faridbod, F., Norouzi, P. & Adib, M. (2006). Sens. Actuators B, 120, 119–124.
  • Gardner, T. S., Weins, R. & Lee, J. (1991). J. Org. Chem.26, 1514–1530.
  • Jing, Z.-L., Zhao, Y.-L., Chen, X. & Yu, M. (2006). Acta Cryst. E62, o4087–o4088.
  • Kuriakose, M., Kurup, M. R. P. & Suresh, E. (2007). Spectrochim. Acta Part A, 66, 898–903.
  • Patole, J., Sandbhor, U., Padhye, S., Deobagkar, D. N., Anson, C. E. & Powell, A. (2003). Bioorg. Med. Chem. Lett.13, 51–55. [PubMed]
  • Sheldrick, G. M. (2003). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhou, Y. Z., Li, J. F., Tu, S. J. & Zhang, M. (2005). Chin. J. Struct. Chem.24, 1193–1197.

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