8-Hy­droxy-5,7-dimethyl­quinolin-1-ium hydrogen sulfate

Kaliyaperumal Thanigaimani; Nuridayanti Che Khalib; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S1600536812049483

. 2012 Dec 8;69(Pt 1):o42–o43. doi: 10.1107/S1600536812049483

8-Hydroxy-5,7-dimethylquinolin-1-ium hydrogen sulfate

Kaliyaperumal Thanigaimani ^a, Nuridayanti Che Khalib ^a, Suhana Arshad ^a, Ibrahim Abdul Razak ^a,^*,^‡

PMCID: PMC3588270 PMID: 23476427

Abstract

The quinoline ring system of the title salt, C₁₁H₁₂NO⁺·HSO₄ ⁻, is essentially planar, with a maximum deviation of 0.054 (2) Å for all non H atoms. In the crystal, the cations and anions are linked via N—H⋯O, O—H⋯O and weak C—H⋯O hydrogen bonds, and are stacked respectively in columns along the a axis. π–π stacking interactions, with centroid–centroid distances of 3.5473 (12) and 3.6926 (12) Å, are also observed. The crystal studied was an inversion twin with refined components of 0.43 (7):0.57 (7).

Related literature

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

Experimental

Crystal data

C₁₁H₁₂NO⁺·HSO₄ ⁻
M _r = 271.28
Orthorhombic,
a = 6.6750 (9) Å
b = 11.6952 (14) Å
c = 14.7283 (18) Å
V = 1149.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 100 K
0.41 × 0.17 × 0.15 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.889, T _max = 0.956
9735 measured reflections
3341 independent reflections
3142 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.103
S = 1.05
3341 reflections
178 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ▶), 1410 Friedel pairs
Flack parameter: 0.43 (7)

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

Supplementary Material

Click here for additional data file.^{(22.5KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812049483/is5225sup1.cif

e-69-00o42-sup1.cif^{(22.5KB, cif)}

Click here for additional data file.^{(163.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049483/is5225Isup2.hkl

e-69-00o42-Isup2.hkl^{(163.9KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812049483/is5225Isup3.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—H1N1⋯O3ⁱ	0.91 (2)	1.90 (2)	2.7753 (17)	161 (2)
O5—H1O5⋯O2ⁱⁱ	0.79 (3)	1.91 (3)	2.698 (2)	172 (2)
O1—H1O1⋯O4ⁱ	0.97 (4)	1.64 (4)	2.601 (2)	172 (3)
C3—H3A⋯O5ⁱⁱⁱ	0.95	2.46	3.3448 (19)	154
C11—H11C⋯O3ⁱⁱ	0.98	2.50	3.445 (3)	161

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and USM Short Term Grant No. 304/PFIZIK/6312078 to conduct this work. KT thanks The Academy of Sciences for the Developing World and USM for a TWAS–USM fellowship.

supplementary crystallographic information

Comment

Recently, hydrogen-bonding patterns involving quinoline and its derivatives with organic acid have been investigated (Loh et al., 2010a,b). 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) and biologically active compounds (Markees et al., 1970). Herein we report the synthesis of 8-hydroxy-5,7-dimethylquinolin-1-ium hydrogen sulfate.

The asymmetric unit of the title compound (Fig. 1) consists of one 8-hydroxy-5,7-dimethylquinolin-1-ium cation and one hydrogen sulfate anion. One proton is transferred from the hydroxyl group of sulfuric acid to the atom N1 of 8-hydroxy-5,7-dimethylquinoline during the crystallization, resulting in the formation of salt. The quinoline ring system (C1–C9/N1) is essentially planar with a maximum deviation of 0.054 (2) Å at atom C8. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the cations are linked by the anions via intermolecular N1—H1N1···O3ⁱ, O5—H1O5···O2ⁱⁱ, O1—H1O1···O4ⁱ, C3—H3A···O5ⁱⁱⁱ and C11—H11C···O3ⁱⁱ hydrogen bonds (symmetry codes in Table 1) into a three-dimensional network. Furthermore, the crystal structure is stabilized by the following π–π interactions: (a) between pyridine (N1/C1–C5, centroid Cg1) and benzene (C1/C5–C9, centroid Cg2) rings Cg1···Cg2 (1/2 + x, 1/2 - y, 2 - z) 3.5473 (12) Å and (b) between benzene rings (C1/C5–C9, centroid Cg2) Cg2···Cg2 (-1/2 + x, 1/2 - y, 2 - z) 3.6926 (12) Å. The crystal studied was an inversion twin, with a ratio of the twin components of 0.43 (7):0.57 (7).

Experimental

A few drops of sulfuric acid were added to a hot methanol solution (20 ml) of 8-hydroxy-5,7-dimethylquinoline (36 mg, Aldrich) which had been warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound (I) appeared after a few days.