(E)-2-[2-(4-Chloro­benzyl­idene)hydrazin-1-yl]-4-{[3-(dimethyl­aza­nium­yl)prop­yl]amino}­quinazolin-1-ium bis­(perchlorate)

Nan Jiang; Jian Zuo; Haiyan Wang; Ming Han; Xin Zhai

doi:10.1107/S1600536812018272

. 2012 Apr 28;68(Pt 5):o1557–o1558. doi: 10.1107/S1600536812018272

(E)-2-[2-(4-Chlorobenzylidene)hydrazin-1-yl]-4-{[3-(dimethylazaniumyl)propyl]amino}quinazolin-1-ium bis(perchlorate)

Nan Jiang ^a, Jian Zuo ^b, Haiyan Wang ^a, Ming Han ^a, Xin Zhai ^a,^*

PMCID: PMC3344656 PMID: 22590418

Abstract

In the title compound, C₂₀H₂₅ClN₆ ²⁺·2ClO₄ ⁻, the organic cation is roughly planar, as shown by the dihedral angle of 3.78 (3)° between the quinazoline and chlorophenyl rings. The quinazoline ring is itself approximately planar, with an average deviation of 0.018 (4) Å. The organic cation adopts an E configuration with respect to the C= N double bond of the hyrazinyl group. The (dimethylazaniumyl)propylamino side chain is disordered over two sets of sites with occupancies of 0.768 (10) and 0.232 (10). In the crystal, two cations and four anions are linked by strong N—H⋯O hydrogen bonds. Weak C—H⋯O hydrogen bonds exist among these aggregates.

Related literature

For antitumor background to the title compound, see: Abouzid & Shouman (2008 ▶); Zhang et al. (2008 ▶); An et al. (2010 ▶); Horiuchi et al. (2009) ▶. For the structures of closely related compounds, see: Fun et al. (2010 ▶); Ferreira et al. (2009 ▶); de Souza et al. (2010 ▶); Loh et al. (2011 ▶).

Experimental

Crystal data

C₂₀H₂₅ClN₆ ²⁺·2ClO₄ ⁻
M _r = 583.81
Triclinic,
a = 10.4533 (18) Å
b = 10.5018 (18) Å
c = 12.626 (2) Å
α = 104.745 (9)°
β = 91.146 (10)°
γ = 96.21 (1)°
V = 1330.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.18 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.907, T _max = 0.932
12435 measured reflections
4889 independent reflections
3979 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.071
wR(F ²) = 0.219
S = 1.09
4889 reflections
371 parameters
62 restraints
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812018272/im2363sup1.cif

e-68-o1557-sup1.cif^{(34.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018272/im2363Isup2.hkl

e-68-o1557-Isup2.hkl^{(239.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812018272/im2363Isup3.cml

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—H1A⋯O3	0.91	2.19	2.990 (5)	147
N5—H5C⋯O2	0.86	2.11	2.922 (4)	157
N4—H4C⋯O1ⁱ	0.86	2.14	2.964 (4)	160
N2—H2D⋯O7	0.86	2.10	2.873 (5)	149
C19—H19⋯O2ⁱⁱ	0.93	2.48	3.316 (5)	150
C1—H1D⋯O6ⁱⁱⁱ	0.96	2.56	3.445 (8)	153
C1—H1C⋯O6^iv	0.96	2.62	3.555 (10)	166

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

Acknowledgments

The authors thank Dalian University of Technology for providing research facilities. This work was supported by the National S & T Major Project of China (No. 2009ZX09301–012) and the S & T Project of Liaoning Province (No. LJQ201107).

supplementary crystallographic information

Comment

The target compound was designed and synthesized as part of on-going studies aimed at developing antitumor agents based on 4-aminoquinazoline and 4-aminoquinoline nuclei. These have aroused increasing attentions for excellent antitumor potency in recent years, such as gefitinib, the traditional immunostimulatory agents CQ and their derivatives (Abouzid et al., 2008; Zhang et al., 2008; An et al., 2010). With the aim to improve the electron affinity and better biological interactions, a hydrazone fragment was introduced (Horiuchi et al., 2009).

The crystal structure of the title compound is given in Fig. 1. The quinazoline ring is approximately planar, with an average deviation of 0.018 (4) Å. The dihedral angle between the quinazoline ring and the chlorophenyl ring is 3.78 (3) °. The (dimethylazaniumyl)propylamino side chain of the compound is disordered over two sites with occupancies of 0.768 (10) and 0.232 (10), respectively. The cationic part of the compound establishes strong N–H···O hydrogen bonds (N5—H5C–O2, N2—H2D–O7, N1—H1A–O3, N4—H4C–O1, Table 1) with the perchlorate anions. The resulting aggregates of two cations and four anions are linked by weak C–H···O hydrogen bonds (C1—H1C–O6, C1—H1D–O6, C19—H19–O2, Table 1) in the crystal structure (Fig. 2).

Experimental

Using 2-aminobenzoic acid and urea as the starting materials, (E)-N-(2-(2-(4-chlorobenzylidene)hydrazinyl) quinazolin-4-yl)-N',N'-dimethylpropane-1,3-diamine was prepared according to literature methods (Abouzid et al., 2008; Horiuchi et al., 2009). The compound was purified by silica gel column chromatography (CH₂Cl₂/Methanol 15:1). 70% Perchloric acid (24 mmol, 1.96 ml) was added to a solution of the compound (20 mmol, 7.7 g) in acetone (50 ml) at room temperature. Then the reaction mixture was stirred at 313 K for 3 h. After cooling to ambient temperature, the resulting precipitate was filtered and washed with acetone. The resulting solids were dissolved in methanol for 15 days to yield the title compound as colorless single crystals (70% yield).