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Acta Cryst. (2009). E65, o2392-o2393    [ doi:10.1107/S1600536809035752 ]

(E)-N'-(3,4-Dimethoxybenzylidene)-2,4-dihydroxybenzohydrazide methanol solvate

Q.-L. Zhang, L.-Z. Yin, X.-M. Deng, S.-C. Liu and D.-G. Song

Abstract top

The title compound, C16H16N2O5·CH3OH, was obtained from a condensation reaction of 3,4-dimethoxybenzaldehyde and 2,4-dihydroxybenzohydrazide. The non-H atoms of the Schiff base molecule are approximately coplanar (r.m.s. deviation = 0.043 Å) and the dihedral angle between the two benzene rings is 1.6 (1)°. The molecule adopts an E configuration with respect to the C=N double bond. An intramolecular O-H...O hydrogen bond is observed. The Schiff base and methanol molecules are linked into a two-dimensional network parallel to (10\overline{1}) by intermolecular N-H...O, O-H...N and O-H...O hydrogen bonds.

Comment top

Hydrazones and Schiff bases have been attracted much attention for their excellent biological properties, especially for their potential pharmacological and antitumor properties (Kucukguzel et al., 2006; Khattab et al., 2005; Karthikeyan et al., 2006; Okabe et al., 1993). Recently, a large number of hydrazone derivatives have been prepared and structurally characterized (Shan et al., 2008; Fun et al., 2008; Ma et al., 2008; Diao et al., 2008a,b; Ejsmont et al., 2008). As part of the ongoing study, we report herein the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The compound consists of a Schiff base molecule and a methanol molecule. The dihedral angle between the two benzene rings is 1.6 (1)°. The Schiff base molecule displays an E configuration about the C═N bond. The bond lengths are typical (Allen et al., 1987). The molecules are linked into a two-dimensional network parallel to the (101) by intermolecular N—H···O, O—H···N, and O—H···O hydrogen bonds (Fig. 2 and Table 1).

Related literature top

For background to Schiff base compounds, hydrazone compounds and their biological properties, see: Kucukguzel et al. (2006); Khattab et al. (2005); Karthikeyan et al. (2006); Okabe et al. (1993). For bond-length data, see: Allen et al. (1987). For related structures, see: Shan et al. (2008); Fun et al. (2008); Ma et al. (2008); Diao et al. (2008a,b); Ejsmont et al. (2008).

Experimental top

3,4-Dimethoxybenzaldehyde (1.0 mmol, 166.2 mg) was dissolved in methanol (50 ml), then 2,4-dihydroxybenzohydrazide (1.0 mmol, 168.2 mg) was added slowly into the solution, and the mixture was kept at reflux with continuous stirring for 1 h. After the solution had cooled to room temperature colourless crystallites appeared. The crystallites were filtered and washed with methanol for three times. Recrystallization from an absolute methanol yielded block-shaped single crystals of the title compound.

Refinement top

Atom H1A was located from a difference Fourier map and refined isotropically, with the N-H distance restrained to 0.90 (1) Å. Other H atoms were placed in calculated positions with C-H = 0.93-0.96 Å and O-H = 0.82 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O and Cmethyl). A rotating group model was used for methyl and hydroxyl groups.

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
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates an intramolecular hydrogen bond.
[Figure 2] Fig. 2. The molecular packing of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.
(E)-N'-(3,4-Dimethoxybenzylidene)-2,4-dihydroxybenzohydrazide methanol solvate top
Crystal data top
C16H16N2O5·CH4OF(000) = 736
Mr = 348.35Dx = 1.343 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1327 reflections
a = 8.497 (1) Åθ = 2.3–24.5°
b = 17.431 (2) ŵ = 0.10 mm−1
c = 11.933 (2) ÅT = 298 K
β = 102.93 (2)°Block, colourless
V = 1722.6 (4) Å30.25 × 0.23 × 0.23 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3732 independent reflections
Radiation source: fine-focus sealed tube2017 reflections with I > 2σ(I)
graphiteRint = 0.043
ω scansθmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −10→10
Tmin = 0.975, Tmax = 0.977k = −20→22
10465 measured reflectionsl = −15→7
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0522P)2 + 0.0211P]
where P = (Fo2 + 2Fc2)/3
3732 reflections(Δ/σ)max = 0.001
235 parametersΔρmax = 0.15 e Å−3
1 restraintΔρmin = −0.19 e Å−3
Crystal data top
C16H16N2O5·CH4OV = 1722.6 (4) Å3
Mr = 348.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.497 (1) ŵ = 0.10 mm−1
b = 17.431 (2) ÅT = 298 K
c = 11.933 (2) Å0.25 × 0.23 × 0.23 mm
β = 102.93 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3732 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2017 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.977Rint = 0.043
10465 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.129Δρmax = 0.15 e Å−3
S = 1.02Δρmin = −0.19 e Å−3
3732 reflectionsAbsolute structure: ?
235 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
N10.9655 (2)0.08862 (10)0.61461 (15)0.0408 (4)
N20.8536 (2)0.03538 (10)0.56016 (14)0.0414 (4)
O11.2219 (2)0.05972 (9)0.95309 (12)0.0623 (5)
H11.15610.03160.91180.093*
O21.52034 (18)0.28449 (9)0.94432 (11)0.0499 (4)
H21.54420.31490.89840.075*
O31.01873 (19)0.01674 (9)0.77490 (12)0.0544 (4)
O40.42243 (18)−0.17176 (9)0.40757 (13)0.0562 (4)
O50.29676 (18)−0.13286 (8)0.19882 (13)0.0582 (5)
O60.6296 (2)0.37824 (9)0.81028 (13)0.0639 (5)
H60.59490.42220.80070.096*
C11.1618 (2)0.13446 (11)0.77945 (16)0.0379 (5)
C21.2479 (3)0.12222 (12)0.89285 (17)0.0419 (5)
C31.3640 (3)0.17364 (13)0.94638 (17)0.0445 (5)
H31.41780.16551.02230.053*
C41.4008 (2)0.23680 (12)0.88820 (17)0.0393 (5)
C51.3173 (3)0.25089 (12)0.77654 (17)0.0461 (6)
H51.34010.29420.73750.055*
C61.2005 (2)0.20011 (12)0.72414 (17)0.0442 (6)
H6A1.14500.20980.64900.053*
C71.0444 (2)0.07663 (12)0.72359 (17)0.0401 (5)
C80.7848 (2)0.05124 (12)0.45725 (18)0.0412 (5)
H80.81520.09560.42420.049*
C90.6598 (2)0.00287 (11)0.38858 (17)0.0373 (5)
C100.6063 (2)−0.06345 (11)0.43485 (17)0.0408 (5)
H100.6532−0.07810.50980.049*
C110.4845 (2)−0.10693 (11)0.36970 (18)0.0414 (5)
C120.4150 (2)−0.08531 (12)0.25628 (18)0.0434 (5)
C130.4679 (3)−0.02028 (12)0.21043 (18)0.0479 (6)
H130.4218−0.00570.13530.057*
C140.5908 (3)0.02357 (12)0.27733 (17)0.0443 (5)
H140.62670.06740.24630.053*
C150.4975 (3)−0.19856 (14)0.5184 (2)0.0648 (7)
H15A0.6088−0.21000.52090.097*
H15B0.4437−0.24410.53530.097*
H15C0.4912−0.15970.57430.097*
C160.2220 (3)−0.11211 (15)0.0836 (2)0.0661 (7)
H16A0.1795−0.06100.08260.099*
H16B0.1358−0.14730.05390.099*
H16C0.3004−0.11410.03690.099*
C170.6766 (4)0.35311 (16)0.7103 (2)0.0814 (9)
H17A0.78120.37360.70930.122*
H17B0.59950.37050.64360.122*
H17C0.68120.29810.70990.122*
H1A0.979 (2)0.1297 (8)0.5719 (15)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0420 (10)0.0382 (11)0.0393 (11)−0.0067 (9)0.0028 (8)−0.0003 (8)
N20.0418 (10)0.0372 (11)0.0433 (11)−0.0048 (8)0.0056 (8)−0.0044 (8)
O10.0787 (13)0.0582 (11)0.0429 (10)−0.0152 (9)−0.0014 (8)0.0154 (8)
O20.0562 (10)0.0511 (10)0.0370 (9)−0.0089 (8)−0.0011 (7)−0.0071 (7)
O30.0647 (11)0.0474 (10)0.0475 (10)−0.0106 (8)0.0049 (8)0.0089 (7)
O40.0589 (10)0.0405 (9)0.0654 (11)−0.0096 (8)0.0057 (8)0.0064 (8)
O50.0585 (10)0.0475 (10)0.0598 (11)−0.0110 (8)−0.0056 (8)−0.0038 (8)
O60.0943 (14)0.0413 (10)0.0577 (11)−0.0014 (10)0.0201 (9)−0.0022 (8)
C10.0427 (12)0.0373 (12)0.0311 (12)0.0030 (10)0.0031 (9)0.0000 (9)
C20.0522 (13)0.0417 (13)0.0321 (12)0.0043 (11)0.0099 (10)0.0038 (10)
C30.0528 (13)0.0486 (14)0.0286 (12)0.0043 (11)0.0012 (10)−0.0003 (10)
C40.0408 (12)0.0401 (13)0.0340 (12)0.0023 (10)0.0023 (9)−0.0099 (10)
C50.0559 (14)0.0419 (14)0.0354 (13)−0.0025 (11)−0.0005 (10)0.0033 (10)
C60.0521 (13)0.0445 (14)0.0297 (12)−0.0002 (11)−0.0043 (10)0.0016 (10)
C70.0419 (12)0.0399 (13)0.0367 (13)0.0026 (10)0.0048 (10)0.0000 (10)
C80.0415 (12)0.0352 (12)0.0453 (14)−0.0023 (10)0.0063 (10)−0.0015 (10)
C90.0368 (12)0.0316 (12)0.0419 (13)−0.0005 (9)0.0053 (9)−0.0040 (9)
C100.0418 (12)0.0368 (13)0.0416 (13)0.0029 (10)0.0047 (10)−0.0026 (10)
C110.0424 (12)0.0294 (12)0.0530 (14)0.0006 (10)0.0116 (10)−0.0015 (10)
C120.0414 (12)0.0339 (12)0.0513 (15)−0.0027 (10)0.0026 (10)−0.0103 (10)
C130.0506 (14)0.0445 (14)0.0446 (14)−0.0028 (11)0.0022 (11)−0.0019 (11)
C140.0482 (13)0.0377 (13)0.0449 (14)−0.0052 (10)0.0059 (10)0.0011 (10)
C150.0699 (17)0.0456 (15)0.0781 (19)−0.0015 (13)0.0147 (14)0.0184 (13)
C160.0569 (15)0.0674 (18)0.0628 (18)−0.0137 (14)−0.0104 (12)−0.0078 (13)
C170.114 (3)0.072 (2)0.0633 (19)−0.0190 (18)0.0304 (17)−0.0166 (15)
Geometric parameters (Å, °) top
N1—C71.339 (3)C5—H50.93
N1—N21.382 (2)C6—H6A0.93
N1—H1A0.901 (9)C8—C91.456 (3)
N2—C81.267 (2)C8—H80.93
O1—C21.350 (2)C9—C141.374 (3)
O1—H10.82C9—C101.400 (3)
O2—C41.367 (2)C10—C111.375 (3)
O2—H20.82C10—H100.93
O3—C71.254 (2)C11—C121.402 (3)
O4—C111.366 (2)C12—C131.377 (3)
O4—C151.413 (3)C13—C141.393 (3)
O5—C121.363 (2)C13—H130.93
O5—C161.426 (3)C14—H140.93
O6—C171.410 (3)C15—H15A0.96
O6—H60.82C15—H15B0.96
C1—C61.397 (3)C15—H15C0.96
C1—C21.403 (3)C16—H16A0.96
C1—C71.469 (3)C16—H16B0.96
C2—C31.380 (3)C16—H16C0.96
C3—C41.374 (3)C17—H17A0.96
C3—H30.93C17—H17B0.96
C4—C51.384 (3)C17—H17C0.96
C5—C61.372 (3)
C7—N1—N2119.58 (17)C10—C9—C8121.09 (19)
C7—N1—H1A125.0 (14)C11—C10—C9120.1 (2)
N2—N1—H1A115.4 (13)C11—C10—H10119.9
C8—N2—N1115.41 (17)C9—C10—H10119.9
C2—O1—H1109.5O4—C11—C10124.5 (2)
C4—O2—H2109.5O4—C11—C12115.55 (18)
C11—O4—C15117.13 (17)C10—C11—C12119.9 (2)
C12—O5—C16116.74 (18)O5—C12—C13124.7 (2)
C17—O6—H6109.5O5—C12—C11115.22 (19)
C6—C1—C2116.94 (18)C13—C12—C11120.03 (19)
C6—C1—C7123.76 (18)C12—C13—C14119.6 (2)
C2—C1—C7119.21 (18)C12—C13—H13120.2
O1—C2—C3117.58 (19)C14—C13—H13120.2
O1—C2—C1121.59 (19)C9—C14—C13120.9 (2)
C3—C2—C1120.83 (19)C9—C14—H14119.6
C4—C3—C2120.42 (19)C13—C14—H14119.6
C4—C3—H3119.8O4—C15—H15A109.5
C2—C3—H3119.8O4—C15—H15B109.5
O2—C4—C3117.89 (18)H15A—C15—H15B109.5
O2—C4—C5121.9 (2)O4—C15—H15C109.5
C3—C4—C5120.2 (2)H15A—C15—H15C109.5
C6—C5—C4119.1 (2)H15B—C15—H15C109.5
C6—C5—H5120.4O5—C16—H16A109.5
C4—C5—H5120.4O5—C16—H16B109.5
C5—C6—C1122.43 (19)H16A—C16—H16B109.5
C5—C6—H6A118.8O5—C16—H16C109.5
C1—C6—H6A118.8H16A—C16—H16C109.5
O3—C7—N1120.01 (19)H16B—C16—H16C109.5
O3—C7—C1121.63 (19)O6—C17—H17A109.5
N1—C7—C1118.35 (19)O6—C17—H17B109.5
N2—C8—C9122.7 (2)H17A—C17—H17B109.5
N2—C8—H8118.7O6—C17—H17C109.5
C9—C8—H8118.7H17A—C17—H17C109.5
C14—C9—C10119.45 (18)H17B—C17—H17C109.5
C14—C9—C8119.44 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.90 (1)2.22 (1)3.108 (2)170 (2)
O6—H6···N2ii0.822.553.133 (2)129
O6—H6···O3ii0.822.022.807 (2)161
O2—H2···O6iii0.821.792.599 (2)171
O1—H1···O30.821.802.534 (2)148
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.90 (1)2.22 (1)3.108 (2)170 (2)
O6—H6···N2ii0.822.553.133 (2)129
O6—H6···O3ii0.822.022.807 (2)161
O2—H2···O6iii0.821.792.599 (2)171
O1—H1···O30.821.802.534 (2)148
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x+1, y, z.
references
References top

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