(E)-4-Meth­oxy-N′-[(6-methyl-4-oxo-4H-chromen-3-yl)methyl­idene]benzo­hydrazide monohydrate

Yoshinobu Ishikawa; Kohzoh Watanabe

doi:10.1107/S1600536814013713

. 2014 Jun 18;70(Pt 7):o784. doi: 10.1107/S1600536814013713

(E)-4-Methoxy-N′-[(6-methyl-4-oxo-4H-chromen-3-yl)methylidene]benzohydrazide monohydrate

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

PMCID: PMC4120634 PMID: 25161570

Abstract

In the title hydrate, C₁₉H₁₆N₂O₄·H₂O, the 4H-chromen-4-one segment is slightly twisted, with a dihedral angle between the two six-membered rings of 3.30 (5)°. The dihedral angles between the plane of the pyranone ring and the hydrazide plane and between the planes of the pyranone ring and the benzene ring of the p-methoxybenzene unit are 26.69 (4) and 2.23 (3)°, respectively. The molecule is connected to the solvent water molecule by an N—H⋯O hydrogen bond. In the crystal, there are π–π stacking interactions between centrosymmetrically related pyranone rings [centroid–centroid distance = 3.5394 (9) Å], as well as bridges formed by the water molecules via O—H⋯O hydrogen bonds.

Related literature

For the biological activity of related compounds, see: Khan et al. (2009 ▶); Tu et al. (2013 ▶). For related structures, see: Ishikawa & Watanabe (2014a ▶,b ▶). graphic file with name e-70-0o784-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₆N₂O₄·H₂O
M _r = 354.36
Triclinic,
a = 7.6228 (13) Å
b = 10.809 (3) Å
c = 11.260 (2) Å
α = 116.339 (14)°
β = 94.258 (14)°
γ = 96.190 (16)°
V = 818.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.48 × 0.35 × 0.13 mm

Data collection

Rigaku AFC-7R diffractometer
4581 measured reflections
3748 independent reflections
3219 reflections with F ² > 2σ(F ²)
R _int = 0.008
3 standard reflections every 150 reflections intensity decay: −0.9%

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.104
S = 1.04
3748 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.27 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/S1600536814013713/mw2124sup1.cif

e-70-0o784-sup1.cif^{(40.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013713/mw2124Isup2.hkl

e-70-0o784-Isup2.hkl^{(183.8KB, hkl)}

Click here for additional data file.^{(7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814013713/mw2124Isup3.cml

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
O5—H17⋯O3ⁱ	0.86	1.99	2.8465 (13)	178
O5—H18⋯O2ⁱⁱ	0.87	1.96	2.8274 (16)	176
N2—H6⋯O5	0.88	2.07	2.9341 (14)	166

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We acknowledge the University of Shizuoka for instrumental support.

supplementary crystallographic information

S1. Comment

Schiff base derivatives of 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 obtained from the condensation reaction of 6-methyl-3-formylchromone with 4-methoxybenzoylhydrazide in benzene.

The 4H-chromen-4-one segment segment is slightly twisted with a dihedral angle between the two 6-membered rings of 3.30 (5)°. The dihedral angles between the pyranone ring and the hydrazide plane (C11/N1/N2/C12) and between the pyranone ring and the benzene ring of the p-methoxybenzene unit are 26.69 (4) and 2.23 (3)°, respectively. The molecule is connected to the solvent water molecule byan N–H···O hydrogen bond.

In the crystal, there are π-π stacking interactions between centrosymmetrically-related pyranone rings [centroid–centroidⁱ distance = 3.5394 (9) Å, i: –x + 1, –y + 1, –z + 1] as well as bridges formed by the water molecules via O–H···O hydrogen bonds (Fig. 2).

S2. Experimental

4-Methoxybenzoylhydrazide (1.00 mmol), 6-methyl-3-formylchromone (1.00 mmol), and a few drops of acetic acid were dissolved in 25 mL of benzene and the mixture was refluxed with a Dean-Stark apparatus for 6 h. After cooling, the precipitates were collected, washed with n-hexane, and dried (yield 68.9%). ¹H NMR (400 MHz, DMSO-d₆): δ = 2.45 (s, 3H), 3.84 (s, 3H), 7.06 (d, 1H, J = 8.8 Hz), 7.63 (d, 1H, J = 8.3 Hz), 7.69 (dd, 1H, J = 2.5 and 8.3 Hz), 7.93 (d, 1H, J = 8.8 Hz), 7.94 (d, 1H, J = 2.5 Hz), 8.63 (s, 1H), 8.79 (s, 1H), 11.82 (s, 1H). DART-MS calcd for [C₁₉H₁₆N₂O₄ + H⁺]: 337.119, found 337.194. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an N,N-dimethylformamide solution of the title compound at room temperature.