8-Hy­droxy­quinolin-1-ium nitrate

Abstract

In the title salt, C₉H₈NO⁺·NO₃ ⁻, the quinoline ring system is essentially planar with a maximum deviation of 0.043 (1) Å. In the crystal, an R ₂ ²(7) ring motif is formed by inter­molecular N—H⋯O and C—H⋯O hydrogen bonds between the cation and the anion. In addition, inter­molecular O—H⋯O and C—H⋯O hydrogen bonds link the two ions, generating an R ₂ ²(8) ring motif. These sets of ring motifs are further linked into a ribbon along the a axis via inter­molecular C—H⋯O hydrogen bonds.

Related literature

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

Experimental

Crystal data

• C₉H₈NO⁺·NO₃ ⁻

• M _r = 208.17

• Monoclinic,

• a = 11.3186 (2) Å

• b = 6.7568 (1) Å

• c = 14.5006 (2) Å

• β = 128.882 (1)°

• V = 863.27 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.13 mm⁻¹

• T = 100 K

• 0.33 × 0.21 × 0.15 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.959, T _max = 0.981

• 9590 measured reflections

• 1978 independent reflections

• 1754 reflections with I > 2σ(I)

• R _int = 0.023

Refinement

• R[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 0.095

• S = 1.08

• 1978 reflections

• 144 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.22 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

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⋯O4i	0.874 (18)	1.944 (18)	2.8112 (12)	171.6 (15)
O1—H1O1⋯O4ii	0.86 (3)	1.83 (3)	2.6794 (16)	169 (2)
C2—H2A⋯O3iii	0.93	2.53	3.106 (2)	120
C2—H2A⋯O3i	0.93	2.31	3.0247 (14)	133
C8—H8A⋯O2ii	0.93	2.40	3.249 (2)	152

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

supplementary crystallographic information

Comment

Recently, hydrogen-bonding patterns involving quinoline and its derivatives with organic acid have been investigated (Loh et al., 2010a,b,c,d). 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). Herein we report the synthesis of 8-hydroxyquinolin-1-ium nitrate.

The asymmetric unit of the title compound (Fig. 1) consists of one 8-hydroxyquinolin-1-ium cation (C1–C10/N1/N2) and one nitrate anion (O2–O4/N2). One proton is transferred from the hydroxyl group of nitric acid to the atom N1 of 8-hydroxyquinoline during the crystallization, resulting in the formation of salt. The quinoline ring system (C1–C9/N1) is approximately planar with a maximum deviation of 0.043 (1) Å at atom C4. 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,c,d).

In the crystal packing (Fig. 2), R₂²(7) ring motifs are formed by intermolecular N1—H1N1···O4 and C2—H2A···O3 hydrogen bonds (Table 1). In addition, pairs of intermolecular O1—H1O1···O4 and C8—H8A···O2 hydrogen bonds (Table 1) link the cations and anions together to generate another set of R₂²(8) ring motifs. These sets of ring motifs are further linked into ribbons along the a axis via intermolecular C2—H2A···O3 hydrogen bonds (Table 1).

Experimental

A few drops of nitric acid were added to a hot methanol solution (20 ml) of 8-hydroxyquinoline (29 mg, Merck) which had been warmed over a magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly to room temperature. Crystals of the title compound appeared after a few days.

Refinement

Atoms H1N1 and H1O1 were located from the difference Fourier map and were refined freely [N—H = 0.874 (18) Å and O—H = 0.86 (2) Å]. The remaining H atoms were positioned geometrically with the bond length of C—H being 0.93 Å and were refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.

Fig. 2.

The crystal structure of the title compound, viewed along the b axis.

Crystal data

C9H8NO+·NO3−	F(000) = 432
Mr = 208.17	Dx = 1.602 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5491 reflections
a = 11.3186 (2) Å	θ = 3.5–37.4°
b = 6.7568 (1) Å	µ = 0.13 mm−1
c = 14.5006 (2) Å	T = 100 K
β = 128.882 (1)°	Block, colourless
V = 863.27 (2) Å3	0.33 × 0.21 × 0.15 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1978 independent reflections
Radiation source: fine-focus sealed tube	1754 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
Tmin = 0.959, Tmax = 0.981	k = −8→8
9590 measured reflections	l = −18→18

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0472P)2 + 0.3584P] where P = (Fo2 + 2Fc2)/3
1978 reflections	(Δ/σ)max < 0.001
144 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.07908 (9)	0.09986 (13)	0.12784 (7)	0.0167 (2)
N1	−0.13600 (11)	0.10475 (14)	0.15595 (8)	0.0139 (2)
C1	0.01506 (13)	0.11333 (16)	0.25398 (10)	0.0138 (2)
C2	−0.24612 (13)	0.10646 (17)	0.16438 (10)	0.0163 (2)
H2A	−0.3465	0.0953	0.0961	0.020*
C3	−0.21344 (13)	0.12476 (17)	0.27446 (10)	0.0171 (2)
H3A	−0.2913	0.1279	0.2795	0.021*
C4	−0.06498 (13)	0.13802 (17)	0.37464 (10)	0.0158 (2)
H4A	−0.0424	0.1546	0.4479	0.019*
C5	0.05450 (13)	0.12672 (16)	0.36803 (10)	0.0144 (2)
C6	0.21000 (13)	0.12812 (17)	0.46913 (10)	0.0171 (2)
H6A	0.2383	0.1339	0.5447	0.020*
C7	0.31841 (13)	0.12080 (18)	0.45453 (10)	0.0186 (3)
H7A	0.4204	0.1209	0.5210	0.022*
C8	0.27878 (13)	0.11312 (18)	0.34078 (11)	0.0177 (2)
H8A	0.3547	0.1114	0.3334	0.021*
C9	0.12859 (13)	0.10813 (16)	0.24054 (10)	0.0148 (2)
O2	0.52824 (10)	0.47945 (18)	0.24518 (8)	0.0321 (3)
O3	0.53907 (10)	0.42125 (15)	0.39694 (8)	0.0239 (2)
O4	0.74765 (9)	0.44023 (13)	0.41965 (7)	0.0179 (2)
N2	0.60151 (11)	0.44742 (16)	0.35208 (9)	0.0177 (2)
H1N1	−0.1627 (19)	0.091 (2)	0.0852 (16)	0.028 (4)*
H1O1	0.145 (2)	0.056 (3)	0.1211 (17)	0.042 (5)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0159 (4)	0.0230 (4)	0.0140 (4)	0.0024 (3)	0.0108 (3)	0.0012 (3)
N1	0.0159 (5)	0.0145 (5)	0.0124 (4)	0.0001 (4)	0.0095 (4)	−0.0002 (3)
C1	0.0161 (5)	0.0114 (5)	0.0137 (5)	0.0003 (4)	0.0094 (4)	0.0003 (4)
C2	0.0153 (5)	0.0169 (5)	0.0167 (5)	−0.0007 (4)	0.0100 (4)	−0.0008 (4)
C3	0.0189 (5)	0.0183 (6)	0.0200 (5)	−0.0007 (4)	0.0150 (5)	−0.0012 (4)
C4	0.0216 (6)	0.0138 (5)	0.0150 (5)	0.0000 (4)	0.0130 (5)	−0.0003 (4)
C5	0.0183 (5)	0.0114 (5)	0.0146 (5)	−0.0001 (4)	0.0108 (5)	0.0000 (4)
C6	0.0198 (5)	0.0163 (5)	0.0133 (5)	0.0006 (4)	0.0095 (5)	−0.0004 (4)
C7	0.0152 (5)	0.0191 (6)	0.0160 (5)	0.0010 (4)	0.0071 (4)	−0.0004 (4)
C8	0.0163 (5)	0.0186 (6)	0.0203 (6)	0.0008 (4)	0.0126 (5)	0.0003 (4)
C9	0.0184 (5)	0.0132 (5)	0.0147 (5)	0.0010 (4)	0.0113 (5)	0.0010 (4)
O2	0.0186 (4)	0.0607 (7)	0.0157 (4)	0.0030 (4)	0.0101 (4)	0.0078 (4)
O3	0.0169 (4)	0.0395 (5)	0.0197 (4)	−0.0012 (4)	0.0137 (4)	0.0007 (4)
O4	0.0121 (4)	0.0260 (5)	0.0155 (4)	0.0000 (3)	0.0087 (3)	−0.0005 (3)
N2	0.0141 (4)	0.0238 (5)	0.0159 (5)	0.0002 (4)	0.0098 (4)	−0.0006 (4)

Geometric parameters (Å, °)

O1—C9	1.3558 (13)	C4—H4A	0.9300
O1—H1O1	0.86 (2)	C5—C6	1.4170 (15)
N1—C2	1.3266 (15)	C6—C7	1.3707 (16)
N1—C1	1.3770 (14)	C6—H6A	0.9300
N1—H1N1	0.874 (18)	C7—C8	1.4126 (16)
C1—C9	1.4160 (16)	C7—H7A	0.9300
C1—C5	1.4196 (15)	C8—C9	1.3790 (16)
C2—C3	1.3995 (16)	C8—H8A	0.9300
C2—H2A	0.9300	O2—N2	1.2343 (13)
C3—C4	1.3701 (16)	O3—N2	1.2372 (13)
C3—H3A	0.9300	O4—N2	1.2899 (12)
C4—C5	1.4166 (16)
C9—O1—H1O1	114.7 (13)	C4—C5—C1	117.82 (10)
C2—N1—C1	122.28 (10)	C6—C5—C1	118.93 (10)
C2—N1—H1N1	117.2 (11)	C7—C6—C5	119.40 (10)
C1—N1—H1N1	120.5 (11)	C7—C6—H6A	120.3
N1—C1—C9	120.19 (10)	C5—C6—H6A	120.3
N1—C1—C5	118.95 (10)	C6—C7—C8	121.52 (11)
C9—C1—C5	120.86 (10)	C6—C7—H7A	119.2
N1—C2—C3	120.99 (10)	C8—C7—H7A	119.2
N1—C2—H2A	119.5	C9—C8—C7	120.63 (11)
C3—C2—H2A	119.5	C9—C8—H8A	119.7
C4—C3—C2	119.03 (10)	C7—C8—H8A	119.7
C4—C3—H3A	120.5	O1—C9—C8	125.09 (10)
C2—C3—H3A	120.5	O1—C9—C1	116.28 (10)
C3—C4—C5	120.81 (10)	C8—C9—C1	118.62 (10)
C3—C4—H4A	119.6	O2—N2—O3	122.01 (10)
C5—C4—H4A	119.6	O2—N2—O4	119.39 (9)
C4—C5—C6	123.24 (10)	O3—N2—O4	118.60 (9)
C2—N1—C1—C9	179.06 (10)	C4—C5—C6—C7	−178.64 (11)
C2—N1—C1—C5	−0.72 (16)	C1—C5—C6—C7	1.38 (16)
C1—N1—C2—C3	2.44 (17)	C5—C6—C7—C8	0.40 (18)
N1—C2—C3—C4	−0.98 (17)	C6—C7—C8—C9	−1.52 (18)
C2—C3—C4—C5	−2.14 (17)	C7—C8—C9—O1	−179.71 (11)
C3—C4—C5—C6	−176.26 (11)	C7—C8—C9—C1	0.77 (17)
C3—C4—C5—C1	3.72 (16)	N1—C1—C9—O1	1.69 (15)
N1—C1—C5—C4	−2.31 (15)	C5—C1—C9—O1	−178.53 (10)
C9—C1—C5—C4	177.91 (10)	N1—C1—C9—C8	−178.75 (10)
N1—C1—C5—C6	177.67 (10)	C5—C1—C9—C8	1.03 (16)
C9—C1—C5—C6	−2.11 (16)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O4i	0.874 (18)	1.944 (18)	2.8112 (12)	171.6 (15)
O1—H1O1···O4ii	0.86 (3)	1.83 (3)	2.6794 (16)	169 (2)
C2—H2A···O3iii	0.93	2.53	3.106 (2)	120
C2—H2A···O3i	0.93	2.31	3.0247 (14)	133
C8—H8A···O2ii	0.93	2.40	3.249 (2)	152

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2.