(E)-4-Methyl-N′-[(4-oxo-4H-chromen-3-yl)methyl­idene]benzohydrazide

Yoshinobu Ishikawa; Kohzoh Watanabe

doi:10.1107/S1600536814008113

. 2014 Apr 16;70(Pt 5):o565. doi: 10.1107/S1600536814008113

(E)-4-Methyl-N′-[(4-oxo-4H-chromen-3-yl)methylidene]benzohydrazide

Yoshinobu Ishikawa ^a,^*, Kohzoh Watanabe ^a

PMCID: PMC4011241 PMID: 24860370

Abstract

In the title chromone-tethered benzohydrazide derivative, C₁₈H₁₄N₂O₃, the 4H-chromen-4-one and the –CH=N–NH–CO– units are each essentially planar, with the largest deviations from thei planes being 0.052 (2) and 0.003 (2) Å, respectively. The dihedral angles between the 4H-chromen-4-one and the –CH=N–NH–CO– units, the 4H-chromen-4-one unit and the benzene ring of the 4-tolyl group, and the benzene ring of the 4-tolyl group and the –CH=N–NH–CO– unit are 8.09 (7), 9.94 (5) and 17.97 (8)°, respectively. In the crystal, the molecules form two types of centrosymmetric dimers: one by N—H⋯O hydrogen bonds and the other by π–π stacking interactions between the 4H-chromen-4-one unit and the 4-tolyl group [centroid–centroid distance = 3.641 (5) Å]. These dimers form one-dimensional assemblies extending along the a-axis direction. Additional π–π stacking interactions between two 4H-chromen-4-one units [centroid–centroid distance = 3.591 (5) Å] and two 4-tolyl groups [centroid–centroid distance = 3.792 (5) Å] organize the molecules into a three-dimensional network.

Related literature

For the biological activity of related compounds, see: Khan et al. (2009 ▶); Tu et al. (2013 ▶). For a related structure, see: Ishikawa & Watanabe (2014 ▶). graphic file with name e-70-0o565-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₄N₂O₃
M _r = 306.32
Triclinic,
a = 7.759 (10) Å
b = 8.543 (7) Å
c = 11.047 (15) Å
α = 103.55 (11)°
β = 95.53 (12)°
γ = 94.60 (9)°
V = 704.6 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.50 × 0.40 × 0.15 mm

Data collection

Rigaku AFC-7R diffractometer
3953 measured reflections
3235 independent reflections
2434 reflections with F ² > 2σ(F ²)
R _int = 0.016
3 standard reflections every 150 reflections intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.187
S = 1.09
3235 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999 ▶); cell refinement: WinAFC Diffractometer Control Software; data reduction: WinAFC Diffractometer Control Software; program(s) used to solve structure: SIR2008 (Burla et al., 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536814008113/gk2609sup1.cif

e-70-0o565-sup1.cif^{(35.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008113/gk2609Isup2.hkl

e-70-0o565-Isup2.hkl^{(158.7KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814008113/gk2609Isup3.cml

CCDC reference: 996675

Additional supporting information: 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—H2⋯O2ⁱ	0.88	2.22	3.012 (4)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

We acknowledge the University of Shizuoka for instrumental support.

supplementary crystallographic information

1. Comment

Schiff bases derived from 3-formyl chromones have attracted much attention due to their biological functions such as enzyme inhibition (Khan et al., 2009; Tu et al., 2013). We herein report the crystal structure of the title compound, which was prepared by the condensation reaction of 3-formylchromone with 4-methylbenzoylhydrazide in ethanol. The structure (Figure 1) shows that the atoms of both the 4H-chromen-4-one and the –CH=N–NH–CO– segments are essentially coplanar, and the largest deviations are 0.052 (2) for C2 and 0.003 (2) Å for C11, respectively. The dihedral angles between the 4H-chromen-4-one segment and the –CH=N–NH–CO– segment, the 4H-chromen-4-one segment and the benzene ring of the 4-methylbenzene segment, and the benzene ring of the 4-methylbenzene segment and the –CH=N–NH–CO– segment are 8.09 (7), 9.94 (5), and 17.97 (8)°, respectively. In the crystal, the molecules related by inversion center (symmetry code: –x + 2, –y, –z + 2) are linked by N–H···O hydrogen bonds to form a dimer. There is also an extensive sytem of π···π stacking interactions between inversion related molecules involving both the 4H-chromen-4-one unit and the 4-tolyl group.

2. Experimental

4-Methylbenzoylhydrazide (1.00 mmol), 3-formylchromone (1.00 mmol), and a few drops of acetic acid were dissolved in 25 ml of ethanol, and the mixture was stirred for 6 h at room temperature. The precipitate was collected, washed with ethanol, and dried in vacuo (yield 55.0%). ¹H NMR (400 MHz, CDCl₃): δ = 3.87 (s, 3H), 6.96 (d, 2H, J = 8.3 Hz), 7.41 (t, 1H, J = 7.6 Hz), 7.53 (d, 1H, J = 8.3 Hz), 7.72 (t, 1H, J = 7.6 Hz), 7.90 (d, 2H, J = 7.9 Hz), 8.13 (d, 1H, J = 8.3 Hz), 8.56 (s, 1H), 8.84 (s, 1H), 9.77 (s, 1H). DART-MS calcd for [C₁₈H₁₄N₂O₃ + H⁺]: 307.321, found 307.156. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an acetonitrile solution of the title compound at room temperature.