4-[(E)-2-(2-Chloro­benzyl­idene)hydrazin-1-yl]quinolin-1-ium chloride dihydrate

Edward R T Tiekink; Solange M S V Wardell; James L Wardell; Marcelle de Lima Ferreira; Marcus V N de Souza; Carlos R Kaiser

doi:10.1107/S1600536812022660

. 2012 May 23;68(Pt 6):o1850–o1851. doi: 10.1107/S1600536812022660

4-[(E)-2-(2-Chlorobenzylidene)hydrazin-1-yl]quinolin-1-ium chloride dihydrate

Edward R T Tiekink ^a,^*, Solange M S V Wardell ^b, James L Wardell ^c,^‡, Marcelle de Lima Ferreira ^d, Marcus V N de Souza ^d, Carlos R Kaiser ^e

PMCID: PMC3379418 PMID: 22719616

Abstract

In the title hydrated salt, C₁₆H₁₃ClN₃ ⁺·Cl⁻·2H₂O, a small twist is evident in the cation so that the chlorobenzene ring is not coplanar with the central hydrazinyl group [the N—C—C—C torsion angle = −4.8 (12)°]. The conformation about the imine N=C bond [1.284 (10) Å] is E. The components of the structure are connected into a three-dimensional architecture via O—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonds. One water H atom is disposed over two sites of equal occupancy.

Related literature

For the biological activity, including the anti-tubercular and anti-tumour activity, of compounds containing the quinolinyl nucleus, see: de Souza et al. (2009 ▶); Candea et al. (2009 ▶); Montenegro et al. (2011 ▶, 2012 ▶). For related structures, see: Howie et al. (2010 ▶); de Souza et al. (2010 ▶, 2012 ▶); Ferreira et al. (2012 ▶); Wardell et al. (2012 ▶). graphic file with name e-68-o1850-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₃ClN₃ ⁺·Cl⁻·2H₂O
M _r = 354.23
Monoclinic,
a = 4.5946 (3) Å
b = 20.1550 (19) Å
c = 18.2192 (17) Å
β = 96.660 (5)°
V = 1675.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 120 K
0.33 × 0.02 × 0.01 mm

Data collection

Bruker–Nonius Roper CCD camera on a κ-goniostat diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.786, T _max = 1.000
14027 measured reflections
2924 independent reflections
1565 reflections with I > 2σ(I)
R _int = 0.146

Refinement

R[F ² > 2σ(F ²)] = 0.096
wR(F ²) = 0.223
S = 1.06
2924 reflections
229 parameters
11 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT (Hooft, 1998 ▶); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812022660/kj2202sup1.cif

e-68-o1850-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812022660/kj2202Isup2.hkl

e-68-o1850-Isup2.hkl^{(140.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812022660/kj2202Isup3.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—H1n⋯Cl2	0.88 (5)	2.32 (5)	3.192 (7)	173 (6)
O1w—H1w⋯Cl2	0.84 (6)	2.37 (6)	3.207 (7)	177 (11)
N2—H2n⋯Cl2ⁱ	0.88 (6)	2.49 (6)	3.349 (7)	166 (7)
O1w—H2w⋯Cl2ⁱⁱ	0.84 (5)	2.42 (7)	3.192 (7)	154 (8)
O2w—H3w⋯O1wⁱⁱⁱ	0.84 (7)	1.96 (7)	2.801 (9)	174 (10)
O2w—H4w⋯O2w^iv	0.84 (8)	2.08 (10)	2.804 (10)	144 (11)
O2w—H5w⋯O2wⁱⁱⁱ	0.83 (12)	2.05 (13)	2.804 (10)	151 (10)

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

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil). Support from the Ministry of Higher Education, Malaysia, High-Impact Research scheme (UM.C/HIR/MOHE/SC/12) is gratefully acknowledged.

supplementary crystallographic information

Comment

A wide range of pharmacological activities have been noted for compounds containing the quinoline nucleus (de Souza et al., 2009), including anti-tubercular (Candea et al., 2009) and anti-tumour (Montenegro et al., 2012) activities. Recently, we have focused attention on arylaldehyde 7-chloroquinoline-4-hydrazone derivatives (Candea et al., 2009; Montenegro et al., 2011). Complementing synthetic studies are crystallographic investigations of these hydrazones (Howie et al., 2010; de Souza et al., 2010; Ferreira et al., 2012; de Souza et al., 2012). We have recently turned our attention to arylaldehyde quinoline-4-hydrazone derivatives (Wardell et al., 2012) and now wish to report the crystal structure of the title hydrated salt, (I).

The asymmetric unit of (I), Fig. 1, comprises a 4-[(E)-2-[(2-Chlorophenyl)methylidene]hydrazin-1-yl]quinolin-1-ium cation, a chloride anion and two lattice water molecules. The quinolinyl residue is co-planar with the central hydrazinyl group [the N3—N2—C3—C2 torsional angle is -1.3 (11)°], but the chlorobenzene ring is slightly twisted out of this plane [N3—C10—C11—C16 = -4.8 (12)°]. The conformation about the N3═C10 bond [1.284 (10) Å] is E. The molecular structure of (I) resembles very closely that of the 2,4-dichloro analogue (Wardell et al., 2012).

The crystal packing in (I) is dominated by hydrogen bonding interactions, Table 1. The water molecules aggregate into chains along the a axis, Fig. 2. One of the O2w—H atoms forms a hydrogen bond to the O1w—O atom. The remaining H atom on O2w is disordered over two positions of equal weight. These interact with adjacent O2w-water molecules as shown in Fig. 2. The two H atoms of O1w form hydrogen bonds with translationally related Cl anions, Fig. 2. Finally, each Cl anion is connected in turn to two quinolinium-H atoms to connect the components of (I) into a three-dimensional architecture, Fig. 3.

Experimental

A solution of 4-hydrazinoquinoline hydrochloride 1 (1.03 mmol) and 2-chlorobenzaldehyde 2 (1.24 mmol) in ethanol (5 ml) was stirred for 8 h at room temperature and then rotary evaporated. The solid residue was washed with cold Et₂O (3 \x 10 ml), and recrystallized from EtOH to give the title salt as a dihydrate; M.pt 554–555 K. ¹H NMR (400 MHz, DMSO-d₆) δ: 14.38 (ls, 1H, NH), 13.07 (ls, 1H, NH), 9.29 (s, 1H, H3'), 8.87 (d, J = 8.4 Hz, 1H, H5), 8.72 (d, J = 6.8 Hz, 1H, H2), (t, J = 7.7 Hz, 1H, H7'), 8.11 (d, J = 8.4 Hz, 1H, H8), 8.04 (t, J = 8.4 Hz, 1H, H7), 7.83 (t, J = 8.4 Hz, 1H, H6), 7.71 (d, J = 6.8 Hz, 1H, H3), 7.60 (d, J = 7.3 Hz, 1H, H8'), 7.57 – 7.47 (m, 2H, H6' and H9').