Crystal structure of quinolinium 2-carboxy-6-nitro­benzoate monohydrate

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

doi:10.1107/S2056989015006052

. 2015 Apr 2;71(Pt 5):o270–o271. doi: 10.1107/S2056989015006052

Crystal structure of quinolinium 2-carboxy-6-nitrobenzoate monohydrate

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

PMCID: PMC4420104 PMID: 25995899

Abstract

In the anion of the title hydrated molecular salt, C₉H₈N⁺·C₈H₄NO₆ ⁻·H₂O, the protonated carboxyl and nitro groups makes dihedral angles of 27.56 (5) and 6.86 (8)°, respectively, with the attached benzene ring, whereas the deprotonated carboxy group is almost orthogonal to it with a dihedral angle of 80.21 (1)°. In the crystal, the components are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating [001] chains. The packing is consolidated by weak C—H⋯N and C—H⋯O interactions as well as aromatic π–π stacking [centroid-to-centroid distances: 3.7023 (8) & 3.6590 (9)Å] interactions, resulting in a three-dimensional network.

Keywords: crystal structure, molecular salt, quinolinium, 2-carboxy-6-nitrobenzoate, hydrogen bonding, π–π stacking 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 ▸); Divya Bharathi et al. (2015 ▸).

Experimental

Crystal data

C₉H₈N⁺·C₈H₄NO₆ ⁻·H₂O
M _r = 358.30
Monoclinic,
a = 14.7622 (8) Å
b = 14.2461 (8) Å
c = 7.6395 (4) Å
β = 104.434 (2)°
V = 1555.90 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 295 K
0.26 × 0.24 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T _min = 0.969, T _max = 0.979
32650 measured reflections
4728 independent reflections
3394 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.115
S = 1.04
4728 reflections
248 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.20 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/S2056989015006052/hb7390sup1.cif

e-71-0o270-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015006052/hb7390Isup2.hkl

e-71-0o270-Isup2.hkl^{(226.9KB, hkl)}

Click here for additional data file.^{(8.6KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015006052/hb7390Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015006052/hb7390fig1.tif

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

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S2056989015006052/hb7390fig2.tif

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

CCDC reference: 1015219

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O7H7AO4	0.83(1)	1.92(1)	2.7416(14)	171(19)
O7H7BO4ⁱ	0.84(1)	2.02(1)	2.8459(14)	169(18)
O1H1AO7ⁱⁱ	0.84(1)	1.75(1)	2.5818(14)	173(2)
N2H2AO3ⁱⁱⁱ	0.91(1)	1.74(1)	2.6425(14)	176(18)
C16H16O4ⁱⁱⁱ	0.93	2.49	3.1166(17)	125
C16H16O2^iv	0.93	2.39	3.1278(17)	136
C12H12N1	0.93	2.61	3.4866(19)	157

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

Acknowledgments

The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

S1. Chemical context

The quinoline derivatives are known to exhibit wide range of pharmacological activities such as antibacterial (Benzerka, et al.2012), anti-viral (Font et al., 1997) and anti-inflammatory (Sloboda et al., 1991). In view of the above importance, we have synthesized the title compound and report herein on its crystal structure.

S2. Structural commentary

The ORTEP diagram of the title compound (I) is shown in Fig.1. The asymmetric unit of the title compound consists of C₉ H₈ N⁺ cation, C₈ H₄ N O₆^- anion and a water molecule. The geometric parameters of (I) (Fig. 1) are well agreed with the similar reported structures [Castañeda et al., 2014; Kafka et al., 2012; Li & Chai (2007)].

The quinolinium ring system is planar [r.m.s deviation = 0.0133 (12)Å] and protonated at N2 atom. In the anion, the carboxyl (O1/C7/O2), nitro (O5/N1/O6) and carboxy (O3/C8/O4) groups are inclined at an angle of 27.56 (5), 6.86 (8) and 80.21 (1)°, respectively with the attached benzene ring (C1—C6). The dihedral angle between the quinolinium ring system and benzene ring is 89.91 (5)°.

S3. Supramolecular features

The molecular structure is stabilized by weak intramolecular O—H···O and C—H···N hydrogen bonds (Table 1). The crystal structure is stabilized by weak intermolecular N—H···O, O—H···O and C—H···O hydrogen bonds (Table 1 & Fig. 2) which link adjacent anions and cations through water molecules into infinite one-dimensional chains along [001]. The crystal structure is further stabilized by weak π···π [Cg1···Cg1ⁱ = 3.7023 (8); Cg3···Cg2ⁱⁱ = 3.6590 (9)Å; (i) 1-x,-y,-z; (ii) x,1/2-y,-1/2+z; Cg1, Cg2 and Cg3 are the centroids of the rings (C1—C6), (C13/C14/C15/C16/c17/N2) and (C9—C13/c17), respectively] interactions.

S4. Synthesis and crystallization

Quinoline (3.22 g, 0.99 mol) was dissolved in hot water (25 ml) and after half an hour, a solution of 3-nitrophthalic acid (5.278 g, 0.38 mol) in methanol (25 ml) was added and stirred for about one hour. A white colour powder was formed. The product was dissolved in aqueous methanol solution (210 ml). Single crystals suitable for X-ray diffraction were obtained from the slow evaporation method at room temperature within a few days.

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 Uiso(H) = 1.5 Ueq(O). Distance restraints were applied for the distance O—H = 0.82 (1)Å. H atom for N atom was located from Fourier map and refined freely with distance restraint N—H = 0.88 (1)Å.