Crystal structure of 8-hy­droxy­quinolin­ium 2-carboxy-6-nitro­benzoate mono­hydrate

M Divya Bharathi; G Ahila; J Mohana; G Chakkaravarthi; G Anbalagan

doi:10.1107/S205698901500571X

. 2015 Mar 25;71(Pt 4):o261–o262. doi: 10.1107/S205698901500571X

Crystal structure of 8-hydroxyquinolinium 2-carboxy-6-nitrobenzoate monohydrate

M Divya Bharathi ^a, G Ahila ^a, J Mohana ^a, G Chakkaravarthi ^b,^*, G Anbalagan ^a,^*

PMCID: PMC4438817 PMID: 26029446

Abstract

In the title hydrated salt, C₉H₈NO⁺·C₈H₄NO₆ ⁻·H₂O, the deprotonated carboxylate group is almost normal to its attached benzene ring [dihedral angle = 83.56 (8)°], whereas the protonated carboxylate group is close to parallel [dihedral angle = 24.56 (9)°]. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, generating [001] chains. The packing is consolidated by C—H⋯O and π–π [centroid-to-centroid distances = 3.6408 (9) and 3.6507 (9) Å] interactions, which result in a three-dimensional network.

Keywords: crystal structure, 8-hydroxyquinolinium, 2-carboxy-6-nitrobenzoate, hydrogen bonding, π–π interactions

Related literature

For the biological activity of quinoline derivatives, see: Font et al. (1997 ▸); Sloboda et al. (1991 ▸). For similar structures, see: Castañeda et al. (2014 ▸); Kafka et al. (2012 ▸); Li & Chai (2007 ▸).

Experimental

Crystal data

C₉H₈NO⁺·C₈H₄NO₆ ⁻·H₂O
M _r = 374.30
Monoclinic,
a = 14.4283 (5) Å
b = 13.8196 (5) Å
c = 8.0483 (3) Å
β = 101.441 (2)°
V = 1572.89 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 295 K
0.26 × 0.22 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T _min = 0.968, T _max = 0.977
58922 measured reflections
7431 independent reflections
4272 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.176
S = 1.02
7431 reflections
260 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: SAINT (Bruker, 2004 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901500571X/hb7385sup1.cif

e-71-0o261-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500571X/hb7385Isup2.hkl

e-71-0o261-Isup2.hkl^{(356.3KB, hkl)}

Click here for additional data file.^{(6.4KB, cml)}

Supporting information file. DOI: 10.1107/S205698901500571X/hb7385Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S205698901500571X/hb7385fig1.tif

The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.

Click here for additional data file.^{(1.9MB, tif)}

c . DOI: 10.1107/S205698901500571X/hb7385fig2.tif

The packing of (I), viewed down c axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

CCDC reference: 1055171

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H2O3ⁱ	0.89(1)	2.00(1)	2.8112(16)	151(2)
O5H5AO8ⁱⁱ	0.82(1)	1.78(1)	2.5928(18)	171(3)
O7H7O3ⁱⁱⁱ	0.84(1)	1.82(1)	2.6482(15)	168(2)
O8H8BO4	0.83(1)	2.07(1)	2.8683(17)	163(2)
O8H8AO4ⁱⁱ	0.83(1)	2.01(1)	2.8288(18)	170(2)
C11H11O1^iv	0.93	2.42	3.295(2)	156
C12H12O6ⁱ	0.93	2.48	3.343(2)	155
C16H16O2^v	0.93	2.52	3.413(2)	160

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

Acknowledgments

The authors thank SAIF, IIT Madras for the data collection.

supplementary crystallographic information

S1. Chemical context

The quinoline nucleus is found in many synthetic and natural products having a wide range of pharmacological activities such as anti-viral (Font et al., 1997), and anti-inflammatory (Sloboda et al., 1991) activities.

S2. Structural commentary

We herewith report the crystal structure of the title compound (I), (Fig.1). The asymmetric unit of the title compound consists of C₉ H₈ N O⁺ cation, C₈ H₄ N O₆^- anion and a water molecule. The geometric parameters of the title compound are comparable to the reported structures [Castañeda et al., 2014; Kafka et al., 2012; Li & Chai (2007)]. The benzene ring (C1—C6) of anion makes the dihedral angle of 58.18 (6)° with the quinolinium ring (C9—C12/N2/C13—C17) of cation.

S3. Supramolecular features

The molecular structure is stabilized by weak intramolecular N—H···O and O—H···O hydrogen bonds (Table 1). The crystal structure is formed by weak intermolecular N—H···O, O—H···O and C—H···O hydrogen bonds (Table 1 & Fig. 2) by linking the adjacent anions and cations by bridging water molecules through O—H···O hydrogen bonds into infinite two-dimensional network along [1 0 0] plane. The crystal structure is further stabilized by weak C—H···π (Table 1) and π–π [Cg1···Cg1ⁱ = 3.6507 (9); Cg2···Cg2ⁱⁱ = 3.6507 (9)Å; (i) -x,1-y,1-z; (ii) x,1/2-y,1/2+z; Cg1 and Cg2 are the centroids of the rings (C1—C6) and (N2/C12/C11/C10/C9/C13)] interactions.

S4. Synthesis and crystallization

The title compound was synthesized by taking at 1:1 ratio of 8-hydroxyquinoline and of 3-nitrophthalic acid was dissolved in a mixed solvent of methanol and water. The salt was formed while adding the base instanstaouly. The solution was stirred for about 2 h to get a homogenous solution. The solution was filtered off and kept aside for slow evaporation at room temperature which yields single crystals suitable for X-ray diffraction.

S5. Refinement

C-bound H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms for O atoms were located from Fourier map and refined with O—H = 0.82 (1)Å and Uiso(H) = 1.5 Ueq(O). H atom for N atom was located from Fourier map and refined freely with N—H = 0.88 (1)Å.