Abstract
The title compound, C15H13N3O4·CH4O, was synthesized from the reaction of 4-methoxybenzaldehyde with 4-nitrobenzohydrazide in methanol. The benzene rings of the Schiff base molecule are nearly coplanar, making a dihedral angle of 7.0 (3)°. The methanol solvent molecules are linked to the Schiff base molecules by N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds, forming chains running parallel to the b axis.
Related literature
For related structures, see: Brückner et al. (2000 ▶); Diao (2007 ▶); Diao et al. (2007 ▶, 2008 ▶); Harrop et al. (2003 ▶); Huang et al. (2007 ▶); Li et al. (2007 ▶); Ren et al. (2002 ▶).
Experimental
Crystal data
C15H13N3O4·CH4O
M r = 331.33
Monoclinic,
a = 14.719 (3) Å
b = 6.631 (2) Å
c = 18.002 (3) Å
β = 113.17 (3)°
V = 1615.3 (7) Å3
Z = 4
Mo Kα radiation
μ = 0.10 mm−1
T = 298 (2) K
0.27 × 0.23 × 0.23 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.973, T max = 0.977
9171 measured reflections
3351 independent reflections
1493 reflections with I > 2σ(I)
R int = 0.065
Refinement
R[F 2 > 2σ(F 2)] = 0.057
wR(F 2) = 0.172
S = 0.95
3351 reflections
224 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρmax = 0.17 e Å−3
Δρmin = −0.17 e Å−3
Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supplementary Material
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005813/rz2199sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005813/rz2199Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Table 1. Hydrogen-bond geometry (Å, °).
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
---|---|---|---|---|
N2—H2A⋯O5 | 0.897 (10) | 2.049 (13) | 2.921 (3) | 164 (3) |
O5—H5⋯N3i | 0.82 | 2.56 | 3.167 (3) | 133 |
O5—H5⋯O3i | 0.82 | 2.10 | 2.863 (3) | 154 |
Symmetry code: (i) .
Acknowledgments
This project is supported by a research grant from Dalian Medical University.
supplementary crystallographic information
Comment
Schiff base compounds have been found to have potential pharmacological and antitumor properties (Brückner et al., 2000; Harrop et al., 2003; Ren et al., 2002). Recently, a few Schiff base compounds derived from the reaction of aldehydes with benzohydrazides have been reported (Diao et al., 2008; Diao et al., 2007; Diao, 2007; Li et al., 2007; Huang et al., 2007). As a further study of such compounds, we report here the structure of the title compound.
The title compound (Fig. 1) consists of a Schiff base molecule and a lattice methanol molecule. The Schiff base molecule is nearly planar with the dihedral angle between the two phenyl rings of 7.0 (3)°. The dihedral angle between the C1—C6 phenyl ring and the O1/N1/O2 nitryl plane is 5.1 (3)°. The torsion angles C9—C8—N3—N2 and C4—C7—N2—N3 are 1.4 (3) and 1.6 (3)°, respectively. The methanol molecules are linked to the Schiff base molecules by N–H···O, O–H···N and O–H···O hydrogen bonds (Table 1) forming chains running parallel to the b axis.
Experimental
4-Methoxybenzaldehyde (0.1 mmol, 13.6 mg) and 4-nitrobenzohydrazide (0.1 mmol, 18.1 mg) were dissolved in methanol (20 ml). The mixture was stirred at reflux for 1 h and cooled to room temperature. After keeping the solution in air for five days, yellow block-like crystals were formed on slow evaporation of the solvent.
Refinement
H2A 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 and constrained to ride on their parent atoms, with C–H distances of 0.93–0.96 Å, O–H distance of 0.82 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O and methyl C).
Figures
Fig. 1.
The structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
Crystal data
C15H13N3O4·CH4O | F000 = 696 |
Mr = 331.33 | Dx = 1.362 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 670 reflections |
a = 14.719 (3) Å | θ = 2.4–24.5º |
b = 6.631 (2) Å | µ = 0.10 mm−1 |
c = 18.002 (3) Å | T = 298 (2) K |
β = 113.17 (3)º | Block, yellow |
V = 1615.3 (7) Å3 | 0.27 × 0.23 × 0.23 mm |
Z = 4 |
Data collection
Bruker SMART CCD area-detector diffractometer | 3351 independent reflections |
Radiation source: fine-focus sealed tube | 1493 reflections with I > 2σ(I) |
Monochromator: graphite | Rint = 0.065 |
T = 298(2) K | θmax = 26.5º |
ω scans | θmin = 1.5º |
Absorption correction: multi-scan(SADABS; Bruker, 2000) | h = −18→18 |
Tmin = 0.973, Tmax = 0.977 | k = −8→7 |
9171 measured reflections | l = −17→22 |
Refinement
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.172 | w = 1/[σ2(Fo2) + (0.07P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
3351 reflections | Δρmax = 0.17 e Å−3 |
224 parameters | Δρmin = −0.17 e Å−3 |
1 restraint | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0051 (12) |
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)
x | y | z | Uiso*/Ueq | ||
N1 | 0.3893 (2) | 0.1141 (5) | 0.43054 (18) | 0.0628 (8) | |
N2 | 0.37993 (17) | 0.4842 (3) | 0.09474 (14) | 0.0480 (6) | |
N3 | 0.38196 (16) | 0.5979 (3) | 0.03071 (14) | 0.0481 (6) | |
O1 | 0.35466 (19) | −0.0546 (4) | 0.41861 (15) | 0.0913 (9) | |
O2 | 0.4269 (2) | 0.1901 (4) | 0.49761 (15) | 0.0915 (9) | |
O3 | 0.38954 (18) | 0.7649 (3) | 0.16870 (13) | 0.0712 (7) | |
O4 | 0.37929 (16) | 0.8238 (3) | −0.31725 (12) | 0.0643 (6) | |
O5 | 0.34226 (17) | 0.0632 (3) | 0.04415 (13) | 0.0643 (6) | |
H5 | 0.3646 | −0.0390 | 0.0708 | 0.096* | |
C1 | 0.3883 (2) | 0.2315 (4) | 0.36036 (17) | 0.0474 (8) | |
C2 | 0.4211 (2) | 0.4269 (5) | 0.37219 (18) | 0.0587 (8) | |
H2 | 0.4442 | 0.4847 | 0.4234 | 0.070* | |
C3 | 0.4188 (2) | 0.5348 (5) | 0.30657 (18) | 0.0570 (8) | |
H3 | 0.4402 | 0.6680 | 0.3136 | 0.068* | |
C4 | 0.38535 (19) | 0.4503 (4) | 0.23005 (16) | 0.0433 (7) | |
C5 | 0.3527 (2) | 0.2511 (4) | 0.22030 (18) | 0.0500 (8) | |
H5A | 0.3303 | 0.1916 | 0.1695 | 0.060* | |
C6 | 0.3537 (2) | 0.1412 (4) | 0.28616 (18) | 0.0520 (8) | |
H6 | 0.3311 | 0.0088 | 0.2799 | 0.062* | |
C7 | 0.3851 (2) | 0.5799 (4) | 0.16214 (17) | 0.0484 (7) | |
C8 | 0.3756 (2) | 0.4971 (4) | −0.03121 (18) | 0.0492 (7) | |
H8 | 0.3686 | 0.3578 | −0.0305 | 0.059* | |
C9 | 0.37877 (19) | 0.5910 (4) | −0.10321 (16) | 0.0432 (7) | |
C10 | 0.3555 (2) | 0.4751 (5) | −0.17273 (17) | 0.0525 (8) | |
H10 | 0.3393 | 0.3398 | −0.1717 | 0.063* | |
C11 | 0.3559 (2) | 0.5571 (4) | −0.24324 (18) | 0.0535 (8) | |
H11 | 0.3389 | 0.4783 | −0.2895 | 0.064* | |
C12 | 0.3818 (2) | 0.7574 (4) | −0.24426 (17) | 0.0475 (7) | |
C13 | 0.4075 (2) | 0.8738 (4) | −0.17570 (17) | 0.0497 (8) | |
H13 | 0.4263 | 1.0075 | −0.1762 | 0.060* | |
C14 | 0.4054 (2) | 0.7901 (4) | −0.10576 (17) | 0.0495 (8) | |
H14 | 0.4221 | 0.8695 | −0.0597 | 0.059* | |
C15 | 0.3969 (2) | 1.0303 (5) | −0.3251 (2) | 0.0705 (10) | |
H15A | 0.3480 | 1.1096 | −0.3156 | 0.106* | |
H15B | 0.3933 | 1.0560 | −0.3787 | 0.106* | |
H15C | 0.4614 | 1.0657 | −0.2864 | 0.106* | |
C16 | 0.2426 (3) | 0.0315 (5) | −0.0070 (2) | 0.0854 (11) | |
H16A | 0.2053 | 0.0016 | 0.0250 | 0.128* | |
H16B | 0.2380 | −0.0796 | −0.0425 | 0.128* | |
H16C | 0.2166 | 0.1508 | −0.0383 | 0.128* | |
H2A | 0.377 (2) | 0.3496 (16) | 0.0892 (19) | 0.080* |
Atomic displacement parameters (Å2)
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0707 (18) | 0.072 (2) | 0.0519 (19) | 0.0074 (16) | 0.0308 (16) | 0.0221 (16) |
N2 | 0.0678 (16) | 0.0380 (13) | 0.0453 (15) | −0.0013 (12) | 0.0298 (13) | 0.0086 (12) |
N3 | 0.0634 (15) | 0.0436 (14) | 0.0426 (15) | 0.0012 (12) | 0.0266 (13) | 0.0089 (12) |
O1 | 0.1079 (19) | 0.0897 (19) | 0.0742 (18) | −0.0230 (16) | 0.0335 (15) | 0.0321 (15) |
O2 | 0.137 (2) | 0.096 (2) | 0.0475 (16) | 0.0115 (16) | 0.0432 (16) | 0.0156 (15) |
O3 | 0.128 (2) | 0.0367 (12) | 0.0565 (14) | −0.0021 (12) | 0.0437 (14) | 0.0032 (10) |
O4 | 0.0934 (16) | 0.0610 (14) | 0.0450 (13) | −0.0019 (12) | 0.0342 (12) | 0.0065 (11) |
O5 | 0.0883 (16) | 0.0432 (13) | 0.0554 (15) | −0.0041 (12) | 0.0218 (13) | 0.0050 (10) |
C1 | 0.0540 (18) | 0.0532 (19) | 0.0393 (18) | 0.0052 (15) | 0.0230 (15) | 0.0101 (15) |
C2 | 0.081 (2) | 0.060 (2) | 0.0378 (18) | −0.0057 (18) | 0.0263 (16) | −0.0037 (15) |
C3 | 0.080 (2) | 0.0474 (18) | 0.0464 (19) | −0.0068 (16) | 0.0277 (17) | 0.0011 (15) |
C4 | 0.0526 (17) | 0.0442 (17) | 0.0360 (17) | 0.0037 (14) | 0.0208 (14) | 0.0049 (13) |
C5 | 0.0615 (19) | 0.0465 (18) | 0.0440 (18) | −0.0040 (15) | 0.0229 (16) | −0.0025 (14) |
C6 | 0.0664 (19) | 0.0466 (18) | 0.050 (2) | −0.0042 (15) | 0.0306 (16) | 0.0039 (15) |
C7 | 0.0634 (19) | 0.0404 (18) | 0.0434 (18) | −0.0016 (15) | 0.0231 (16) | 0.0035 (15) |
C8 | 0.0605 (19) | 0.0452 (17) | 0.0458 (18) | −0.0016 (15) | 0.0253 (16) | 0.0052 (15) |
C9 | 0.0489 (16) | 0.0420 (16) | 0.0404 (17) | −0.0004 (14) | 0.0194 (14) | 0.0058 (13) |
C10 | 0.0657 (19) | 0.0420 (17) | 0.052 (2) | −0.0042 (14) | 0.0247 (16) | −0.0003 (15) |
C11 | 0.072 (2) | 0.0487 (19) | 0.0405 (18) | −0.0036 (16) | 0.0231 (16) | −0.0042 (15) |
C12 | 0.0551 (18) | 0.0543 (19) | 0.0362 (17) | 0.0042 (15) | 0.0214 (15) | 0.0052 (15) |
C13 | 0.0638 (19) | 0.0410 (17) | 0.0476 (18) | −0.0050 (14) | 0.0254 (16) | 0.0036 (14) |
C14 | 0.0620 (19) | 0.0472 (19) | 0.0417 (18) | −0.0036 (15) | 0.0231 (15) | 0.0004 (14) |
C15 | 0.087 (2) | 0.066 (2) | 0.067 (2) | −0.0062 (19) | 0.040 (2) | 0.0200 (18) |
C16 | 0.092 (3) | 0.075 (3) | 0.087 (3) | −0.002 (2) | 0.032 (2) | 0.000 (2) |
Geometric parameters (Å, °)
N1—O1 | 1.213 (3) | C5—H5A | 0.9300 |
N1—O2 | 1.222 (3) | C6—H6 | 0.9300 |
N1—C1 | 1.479 (4) | C8—C9 | 1.455 (4) |
N2—C7 | 1.345 (3) | C8—H8 | 0.9300 |
N2—N3 | 1.388 (3) | C9—C14 | 1.383 (4) |
N2—H2A | 0.897 (10) | C9—C10 | 1.392 (4) |
N3—C8 | 1.271 (3) | C10—C11 | 1.383 (4) |
O3—C7 | 1.232 (3) | C10—H10 | 0.9300 |
O4—C12 | 1.372 (3) | C11—C12 | 1.384 (4) |
O4—C15 | 1.411 (3) | C11—H11 | 0.9300 |
O5—C16 | 1.407 (4) | C12—C13 | 1.376 (4) |
O5—H5 | 0.8200 | C13—C14 | 1.388 (4) |
C1—C6 | 1.366 (4) | C13—H13 | 0.9300 |
C1—C2 | 1.370 (4) | C14—H14 | 0.9300 |
C2—C3 | 1.370 (4) | C15—H15A | 0.9600 |
C2—H2 | 0.9300 | C15—H15B | 0.9600 |
C3—C4 | 1.386 (4) | C15—H15C | 0.9600 |
C3—H3 | 0.9300 | C16—H16A | 0.9600 |
C4—C5 | 1.392 (4) | C16—H16B | 0.9600 |
C4—C7 | 1.493 (4) | C16—H16C | 0.9600 |
C5—C6 | 1.387 (4) | ||
O1—N1—O2 | 123.4 (3) | C9—C8—H8 | 118.7 |
O1—N1—C1 | 118.2 (3) | C14—C9—C10 | 118.0 (3) |
O2—N1—C1 | 118.4 (3) | C14—C9—C8 | 123.2 (3) |
C7—N2—N3 | 118.7 (2) | C10—C9—C8 | 118.8 (3) |
C7—N2—H2A | 123 (2) | C11—C10—C9 | 121.3 (3) |
N3—N2—H2A | 118 (2) | C11—C10—H10 | 119.3 |
C8—N3—N2 | 115.1 (2) | C9—C10—H10 | 119.3 |
C12—O4—C15 | 118.0 (2) | C10—C11—C12 | 119.3 (3) |
C16—O5—H5 | 109.5 | C10—C11—H11 | 120.3 |
C6—C1—C2 | 122.6 (3) | C12—C11—H11 | 120.3 |
C6—C1—N1 | 118.6 (3) | O4—C12—C13 | 125.0 (3) |
C2—C1—N1 | 118.7 (3) | O4—C12—C11 | 114.6 (3) |
C1—C2—C3 | 118.2 (3) | C13—C12—C11 | 120.4 (3) |
C1—C2—H2 | 120.9 | C12—C13—C14 | 119.5 (3) |
C3—C2—H2 | 120.9 | C12—C13—H13 | 120.2 |
C2—C3—C4 | 121.6 (3) | C14—C13—H13 | 120.2 |
C2—C3—H3 | 119.2 | C9—C14—C13 | 121.3 (3) |
C4—C3—H3 | 119.2 | C9—C14—H14 | 119.3 |
C3—C4—C5 | 118.6 (3) | C13—C14—H14 | 119.3 |
C3—C4—C7 | 117.8 (3) | O4—C15—H15A | 109.5 |
C5—C4—C7 | 123.6 (3) | O4—C15—H15B | 109.5 |
C6—C5—C4 | 120.2 (3) | H15A—C15—H15B | 109.5 |
C6—C5—H5A | 119.9 | O4—C15—H15C | 109.5 |
C4—C5—H5A | 119.9 | H15A—C15—H15C | 109.5 |
C1—C6—C5 | 118.7 (3) | H15B—C15—H15C | 109.5 |
C1—C6—H6 | 120.7 | O5—C16—H16A | 109.5 |
C5—C6—H6 | 120.7 | O5—C16—H16B | 109.5 |
O3—C7—N2 | 122.6 (3) | H16A—C16—H16B | 109.5 |
O3—C7—C4 | 120.8 (3) | O5—C16—H16C | 109.5 |
N2—C7—C4 | 116.6 (2) | H16A—C16—H16C | 109.5 |
N3—C8—C9 | 122.6 (3) | H16B—C16—H16C | 109.5 |
N3—C8—H8 | 118.7 |
Hydrogen-bond geometry (Å, °)
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5 | 0.897 (10) | 2.049 (13) | 2.921 (3) | 164 (3) |
O5—H5···N3i | 0.82 | 2.56 | 3.167 (3) | 133 |
O5—H5···O3i | 0.82 | 2.10 | 2.863 (3) | 154 |
Symmetry codes: (i) x, y−1, z.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2199).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005813/rz2199sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005813/rz2199Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report