3,4,5-Trimethoxy­benzohydrazidium chloride

Aamer Saeed; Amara Mumtaz; Hummera Rafique; Kazuma Gotoh; Hiroyuki Ishida

doi:10.1107/S1600536808036301

. 2008 Nov 13;64(Pt 12):o2336. doi: 10.1107/S1600536808036301

3,4,5-Trimethoxybenzohydrazidium chloride

Aamer Saeed ^a,^*, Amara Mumtaz ^a, Hummera Rafique ^a, Kazuma Gotoh ^b, Hiroyuki Ishida ^b

PMCID: PMC2959913 PMID: 21581311

Abstract

The title compound, C₁₀H₁₅N₂O₄ ⁺·Cl⁻, was obtained as an unexpected by-product during the synthesis of 1-[2-(substituted aryl)]-3-methylpyrazol-5-ones. The hydrazide group is essentially planar, with an r.s.m. deviation of 0.020 (2) Å, and is oriented at a dihedral angle of 30.52 (3)° with respect to the benzene ring. In the crystal structure, the cations and anions are linked through N—H⋯O and N—H⋯Cl hydrogen bonds, forming a molecular tape running along the b axis.

Related literature

For general background, see: Jin et al. (2006 ▶); Song et al. (2005 ▶); Yang et al. (2007 ▶). For a related structure, see: Zareef et al. (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₀H₁₅N₂O₄ ⁺·Cl⁻
M _r = 262.69
Monoclinic,
a = 38.587 (3) Å
b = 4.8202 (3) Å
c = 13.5915 (10) Å
β = 108.459 (2)°
V = 2397.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 223 (1) K
0.29 × 0.28 × 0.05 mm

Data collection

Rigaku R-AXIS RAPIDII diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 1999 ▶) T _min = 0.930, T _max = 0.984
15536 measured reflections
3483 independent reflections
2987 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.111
S = 1.06
3483 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036301/hk2567sup1.cif

e-64-o2336-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036301/hk2567Isup2.hkl

e-64-o2336-Isup2.hkl^{(170.9KB, 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
N1—H1⋯O4ⁱ	0.876 (19)	2.007 (19)	2.8200 (13)	154.0 (18)
N2—H2NA⋯Cl1ⁱⁱ	0.90	2.25	3.1169 (11)	162
N2—H2NB⋯Cl1	0.90	2.20	3.0937 (11)	171
N2—H2NC⋯Cl1ⁱⁱⁱ	0.90	2.30	3.1724 (12)	164

Open in a new tab

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

supplementary crystallographic information

Comment

3,4,5-Trimethoxybenzohydrazide is an intermediate toward variety of hetero- cyclic systems. Thioether derivatives bearing 1,3,4-thiadiazole and 3,4,5-tri- methoxyphenyl moieties and N-substituted benzylidene-3,4,5-trimethoxybenzo- hydrazide and 3-acetyl-2-substituted phenyl-5-(3,4,5-trimethoxyphenyl)-2,3 -dihydro-1,3,4-oxadiazole derivatives were proved to have good anti-cancer and anti-tumor bioactivities (Song et al., 2005; Jin et al., 2006). 4-Alkyl(aryl)- thioquinazoline derivatives synthesized from gallic acid were highly effective against cancer cell lines (Yang et al., 2007). The title compound was obtained as an unexpected by-product during synthesis of 1-[2-(substituted aryl)]-3 -methylpyrazol-5-ones, and we report herein its crystal structure.

In the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges, and may be compared with the corresponding ones in 3,4,5-trimethoxybenzohydrazide hemihydrate (Zareef et al., 2006). The (N1/N2/O4/C7) plane is oriented with respect to ring A (C1-C6) at a dihedral angle of 30.52 (3)°, which is larger than the corresponding one [9.27 (10)°] in 3,4,5-trimethoxybenzohydrazide hemihydrate.

In the crystal structure, the molecules are linked through N-H···O and N-H···Cl hydrogen bonds, forming a molecular tape running along the b axis (Fig. 2). No significant interaction is observed between the tapes (Fig. 3).

Experimental

A mixture of 3,4,5-trimethoxybenzohydrazide (0.01 mol) and ethyl acetoacetate (0.01 mol) was refluxed in methanol (25 ml), containing concentrated hydrochloric acid (1 ml) for 8 h in a water-bath. The resulting solution was then concentrated and cooled at room temperature. The solid thus separated was washed with methanol, dried and recrystallized with acetone. Anal. calcd. for C₁₀H₁₅Cl_N2_O4: C 45.72, H 5.76, N 10.66%; found: C 45.57, H 5.64, N 10.69%.