2-Cyano­quinolin-1-ium nitrate

Wan-Sin Loh; Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536810039243

. 2010 Oct 9;66(Pt 11):o2726–o2727. doi: 10.1107/S1600536810039243

2-Cyanoquinolin-1-ium nitrate

Wan-Sin Loh ^a,^‡, Madhukar Hemamalini ^a, Hoong-Kun Fun ^a,^*,^§

PMCID: PMC3009375 PMID: 21588937

Abstract

A proton is transferred from the nitric acid to the N atom of 2-cyanoquinoline during crystallization, resulting in the formation of the title salt, C₁₀H₇N₂ ⁺·NO₃ ⁻. The quinolinium ring system is approximately planar, with a maximum deviation of 0.013 (3) Å. In the crystal, a very asymmetric bifurcated N—H⋯(O,O) hydrogen bond to two O atoms of an adjacent nitrate anion occurs, generating an R ₂ ¹(4) ring motif. C—H⋯O hydrogen bonds link the ions into sheets stacking along the a axis.

Related literature

For background to and the biological activities of quinoline derivatives, see: Loh, Quah et al. (2010a ▶,b ▶); Loh et al. (2010 ▶); Sasaki et al. (1998 ▶); Reux et al. (2009 ▶); Morimoto et al. (1991 ▶); Michael (1997 ▶); Markees et al. (1970 ▶); Campbell et al. (1988 ▶). For the hydrogen-bond motif, see: Bernstein et al. (1995 ▶). For related structures, see: Loh, Quah et al. (2010a ▶,b ▶); Loh et al. (2010 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₀H₇N₂ ⁺·NO₃ ⁻
M _r = 217.19
Monoclinic,
a = 3.6969 (1) Å
b = 17.7031 (3) Å
c = 14.6029 (2) Å
β = 95.802 (1)°
V = 950.81 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.44 × 0.18 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.951, T _max = 0.992
16184 measured reflections
2758 independent reflections
2103 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.122
S = 1.05
2758 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810039243/hb5669sup1.cif

e-66-o2726-sup1.cif^{(16KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039243/hb5669Isup2.hkl

e-66-o2726-Isup2.hkl^{(135.4KB, 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—H1N1⋯O1	0.95	2.56	3.2376 (15)	128
N1—H1N1⋯O3	0.95	1.60	2.5432 (14)	172
C5—H5A⋯O3ⁱ	0.943 (16)	2.497 (16)	3.2835 (16)	141.0 (15)
C7—H7A⋯O2ⁱⁱ	0.976 (16)	2.473 (16)	3.3641 (16)	151.8 (12)
C8—H8A⋯O2ⁱⁱⁱ	0.977 (18)	2.391 (19)	3.3355 (17)	162.4 (15)

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (grant No. 1001/PFIZIK/811160). WSL thanks USM for the award of a USM fellowship. MH thanks USM for the award of a postdoctoral fellowship.

supplementary crystallographic information

Comment

Recently, hydrogen-bonding patterns involving quinoline and its derivatives with organic acid have been investigated (Loh at al., 2010a,b; Loh et al., 2010). Syntheses of the quinoline derivatives were discussed earlier (Sasaki et al., 1998; Reux et al., 2009). Quinolines and their derivatives are very important compounds because of their wide occurrence in natural products (Morimoto et al., 1991; Michael, 1997) and biologically active compounds (Markees et al., 1970; Campbell et al., 1988). Heterocyclic molecules containing cyano group are useful as drug intermediates. Herein we report the synthesis of 2-cyanoquinolin-1-ium nitrate.

The asymmetric unit of the title compound (Fig. 1) consists of one 2-cyanoquinolin-1-ium cation (C1–C10/N1/N2) and one nitrate anion (N3/O1–O3). One proton is transferred from the hydroxyl group of nitrate to the atom N1 of 2-cyanoquinoline during the crystallization, resulting in the formation of salt. The quinoline ring system (C1–C9/N1) is approximately planar with a maximum deviation of 0.013 (3) Å at atom C6. The R₂¹(4) ring motif (Fig. 1; Bernstein et al., 1995) indicates a bifurcated hydrogen bond from N1–H1N1 to the two acceptors (O1/O3). Bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to the related structures (Loh et al., 2010a,b; Loh et al., 2010).

In the crystal packing (Fig. 2), intermolecular N1—H1N1···O1, N1—H1N1···O3, C5—H5A···O3, C7—H7A···O2 and C8—H8A···O2 hydrogen bonds (Table 1) link the molecules into two-dimensional planes stacking along the a axis.

Experimental

A few drops of nitric acid were added to a hot methanol solution (20 ml) of quinoline-2-carbonitrile (39 mg, Aldrich) which had been warmed over a magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly to room temperature. Colourless plates of (I) appeared after a few days.