2. Experimental Crystal data

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data reports ISSN 2056-9890 Crystal structure of 8-hydroxyquinolinium 2-carboxy-6-nitrobenzoate monohydrate M. Divya Bharathi, a G. Ahila, a J. Mohana, a G. Chakkaravarthi b * and G.

$Crystal data C 9 H 8 NO + C 8 H 4 NO 6 H 2 O M r = 374.30 Monoclinic, P2 1 =c a = 14.4283 (5) Å b = 13.8196 (5) Å c = 8.0483 (3) Å = 101.441 (2) 2.2. Data collection Bruker Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.$

1 data reports ISSN Crystal structure of 8-hydroxyquinolinium 2-carboxy-6-nitrobenzoate monohydrate M. Divya Bharathi, a G. Ahila, a J. Mohana, a G. Chakkaravarthi b * and G. Anbalagan a * a Department of Physics, Presidency College, Chennai , India, and b Department of Physics, CPCL Polytechnic College, Chennai , India. 2. Experimental 2.1. Crystal data C 9 H 8 NO + C 8 H 4 NO 6 H 2 O M r = Monoclinic, P2 1 =c a = (5) Å b = (5) Å c = (3) Å = (2) 2.2. Data collection Bruker Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.968, T max = V = (10) Å 3 Z =4 Mo K radiation = 0.13 mm 1 T = 295 K mm measured reflections 7431 independent reflections 4272 reflections with I > 2(I) R int = *Correspondence chakkaravarthi_2005@yahoo.com, anbu24663@yahoo.co.in Received 17 March 2015; accepted 20 March 2015 Edited by W. T. A. Harrison, University of Aberdeen, Scotland In the title hydrated salt, C 9 H 8 NO + C 8 H 4 NO 6 H 2 O, the deprotonated carboxylate group is almost normal to its attached benzene ring [dihedral angle = (8) ], whereas the protonated carboxylate group is close to parallel [dihedral angle = (9) ]. In the crystal, the components are linked by N HO and O HO hydrogen bonds, generating [001] chains. The packing is consolidated by C HO and [centroid-to-centroid distances = (9) and (9) Å] interactions, which result in a three-dimensional network. Keywords: crystal structure; 8-hydroxyquinolinium; 2-carboxy-6-nitrobenzoate; hydrogen bonding; interactions Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 260 parameters 5 restraints Table 1 Hydrogen-bond geometry (Å, ). H atoms treated by a mixture of independent and constrained refinement max = 0.50 e Å 3 min = 0.38 e Å 3 D HA D H HA DA D HA N2 H2O3 i 0.89 (1) 2.00 (1) (16) 151 (2) O5 H5AO8 ii 0.82 (1) 1.78 (1) (18) 171 (3) O7 H7O3 iii 0.84 (1) 1.82 (1) (15) 168 (2) O8 H8BO (1) 2.07 (1) (17) 163 (2) O8 H8AO4 ii 0.83 (1) 2.01 (1) (18) 170 (2) C11 H11O1 iv (2) 156 C12 H12O6 i (2) 155 C16 H16O2 v (2) 160 Symmetry codes: (i) x þ 1; y 1 2 ; z þ 3 2 ; (ii) x; y þ 3 2 ; z þ 1 2 ; (iii) x; y þ 1 2 ; z þ 1 2 ; (iv) x þ 1; y þ 1; z þ 1; (v) x; y; z þ 1. CCDC reference: 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). 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. Acknowledgements The authors thank SAIF, IIT Madras for the data collection. Supporting information for this paper is available from the IUCr electronic archives (Reference: HB7385). References Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Castañeda, R., Antal, S. A., Draguta, S., Timofeeva, T. V. & Khrustalev, V. N. (2014). Acta Cryst. E70, o924 o925. doi: /s x Bharathi et al. o261

2 data reports Font, M., Monge, A., Ruiz, I. & Heras, B. (1997). Drug Des. Discov. 14, Kafka, S., Pevec, A., Proisl, K., Kimmel, R. & Košmrlj, J. (2012). Acta Cryst. E68, o3199 o3200. Li, Z.-S. & Chai, J.-S. (2007). Acta Cryst. E63, o2857 o2859. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, Sloboda, A. E., Powell, D., Poletto, J. F., Pickett, W. C., Gibbons, J. J., Bell, D. H., Oronsky, A. L. & Kerwar, S. S. (1991). J. Rheumatol. 18, Spek, A. L. (2009). Acta Cryst. D65, o262 Bharathi et al. C 9 H 8 NO + C 8 H 4 NO 6 H 2 O

3 supporting information [doi: /s x] Crystal structure of 8-hydroxyquinolinium 2-carboxy-6-nitrobenzoate monohydrate M. Divya Bharathi, G. Ahila, J. Mohana, G. Chakkaravarthi and G. Anbalagan 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 C 9 H 8 N O + - cation, C 8 H 4 N O 6 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 (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 Cg1 i = (9); Cg2 Cg2 ii = (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. sup-1

4 Figure 1 The molecular structure of (I), with 30% probability displacement ellipsoids for non-h atoms. sup-2

5 Figure 2 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. 8-Hydroxyquinolinium 2-carboxy-6-nitrobenzoate monohydrate Crystal data C 9 H 8 NO + C 8 H 4 NO 6 H 2 O M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (5) Å b = (5) Å c = (3) Å β = (2) V = (10) Å 3 Z = 4 F(000) = 776 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 9900 reflections θ = µ = 0.13 mm 1 T = 295 K Block, colourless mm sup-3

6 Data collection Bruker Kappa APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω and φ scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.968, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 260 parameters 5 restraints Primary atom site location: structure-invariant direct methods measured reflections 7431 independent reflections 4272 reflections with I > 2σ(I) R int = θ max = 36.1, θ min = 2.1 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0619P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.50 e Å 3 Δρ min = 0.38 e Å 3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq C (9) (9) (18) (2) C (10) (10) (19) (3) C (11) (12) (2) (3) H * C (11) (12) (2) (4) H * C (11) (12) (2) (3) H * C (10) (10) (19) (3) C (10) (10) (18) (3) C (11) (11) (19) (3) C (11) (10) (19) (3) C (13) (12) (2) (4) H * C (13) (14) (2) (4) sup-4

7 H * C (11) (14) (2) (4) H * C (9) (10) (18) (3) C (10) (10) (19) (3) C (11) (13) (2) (3) H * C (13) (15) (2) (4) H * C (13) (12) (2) (4) H * N (10) (10) (18) (3) N (9) (9) (17) (3) H (15) (8) (3) (6)* O (12) (11) (18) (4) O (13) (13) (2) (5) O (7) (8) (15) (2) O (8) (8) (15) (2) O (10) (11) (18) (3) H5A (18) (15) (3) 0.070* O (9) (10) (17) (3) O (9) (8) (17) (3) H (13) (15) (3) 0.057* O (9) (10) (16) (3) H8A (15) (18) (18) 0.059* H8B (16) (13) (3) 0.059* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (5) (5) (6) (4) (5) (5) C (6) (6) (7) (5) (5) (5) C (7) (8) (8) (6) (6) (6) C (7) (8) (9) (6) (7) (7) C (7) (7) (8) (6) (6) (6) C (6) (6) (7) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (7) (7) (7) (5) (5) (5) C (7) (6) (7) (5) (5) (5) C (9) (7) (8) (6) (7) (6) C (8) (9) (10) (7) (7) (8) C (7) (9) (9) (6) (6) (7) C (6) (6) (6) (4) (5) (5) C (7) (6) (7) (5) (5) (5) C (7) (9) (8) (6) (6) (7) C (8) (10) (9) (7) (7) (8) C (9) (7) (9) (7) (7) (7) N (7) (7) (7) (5) (5) (5) sup-5

8 N (6) (6) (7) (4) (5) (5) O (10) (8) (7) (7) (7) (6) O (11) (12) (9) (9) (8) (8) O (5) (5) (6) (4) (4) (4) O (6) (5) (6) (4) (5) (4) O (7) (8) (7) (6) (6) (6) O (7) (7) (7) (6) (5) (6) O (6) (5) (7) (4) (5) (5) O (7) (7) (6) (5) (5) (5) Geometric parameters (Å, º) C1 C (2) C11 C (3) C1 C (19) C11 H C1 C (18) C12 N (2) C2 C (2) C12 H C2 C (2) C13 N (18) C3 C (2) C13 C (19) C3 H C14 O (18) C4 C (2) C14 C (2) C4 H C15 C (3) C5 C (2) C15 H C5 H C16 C (3) C6 N (19) C16 H C7 O (17) C17 H C7 O (17) N1 O (18) C8 O (19) N1 O (19) C8 O (19) N2 H (9) C9 C (2) O5 H5A (10) C9 C (19) O7 H (9) C9 C (2) O8 H8A (10) C10 C (3) O8 H8B (10) C10 H C6 C1 C (12) C10 C11 C (15) C6 C1 C (12) C10 C11 H C2 C1 C (12) C12 C11 H C3 C2 C (14) N2 C12 C (16) C3 C2 C (13) N2 C12 H C1 C2 C (12) C11 C12 H C4 C3 C (14) N2 C13 C (13) C4 C3 H N2 C13 C (13) C2 C3 H C9 C13 C (13) C5 C4 C (14) O7 C14 C (14) C5 C4 H O7 C14 C (13) C3 C4 H C15 C14 C (14) C4 C5 C (15) C14 C15 C (15) C4 C5 H C14 C15 H sup-6

9 C6 C5 H C16 C15 H C5 C6 C (14) C17 C16 C (16) C5 C6 N (13) C17 C16 H C1 C6 N (12) C15 C16 H O4 C7 O (13) C16 C17 C (15) O4 C7 C (12) C16 C17 H O3 C7 C (12) C9 C17 H O6 C8 O (15) O1 N1 O (15) O6 C8 C (14) O1 N1 C (13) O5 C8 C (13) O2 N1 C (14) C10 C9 C (14) C12 N2 C (14) C10 C9 C (14) C12 N2 H (14) C13 C9 C (14) C13 N2 H (14) C11 C10 C (15) C8 O5 H5A (19) C11 C10 H C14 O7 H (17) C9 C10 H H8A O8 H8B 105 (2) C6 C1 C2 C3 2.4 (2) C9 C10 C11 C (3) C7 C1 C2 C (13) C10 C11 C12 N2 0.1 (3) C6 C1 C2 C (13) C10 C9 C13 N2 0.3 (2) C7 C1 C2 C8 2.0 (2) C17 C9 C13 N (14) C1 C2 C3 C4 0.0 (2) C10 C9 C13 C (14) C8 C2 C3 C (15) C17 C9 C13 C (2) C2 C3 C4 C5 2.1 (3) N2 C13 C14 O7 2.0 (2) C3 C4 C5 C6 1.7 (3) C9 C13 C14 O (14) C4 C5 C6 C1 0.8 (2) N2 C13 C14 C (14) C4 C5 C6 N (15) C9 C13 C14 C (2) C2 C1 C6 C5 2.9 (2) O7 C14 C15 C (17) C7 C1 C6 C (14) C13 C14 C15 C (2) C2 C1 C6 N (13) C14 C15 C16 C (3) C7 C1 C6 N1 1.6 (2) C15 C16 C17 C9 1.0 (3) C6 C1 C7 O (16) C10 C9 C17 C (17) C2 C1 C7 O (17) C13 C9 C17 C (2) C6 C1 C7 O (18) C5 C6 N1 O (16) C2 C1 C7 O (16) C1 C6 N1 O1 0.7 (2) C3 C2 C8 O (16) C5 C6 N1 O2 2.0 (2) C1 C2 C8 O (2) C1 C6 N1 O (17) C3 C2 C8 O (2) C11 C12 N2 C (3) C1 C2 C8 O (14) C9 C13 N2 C (2) C13 C9 C10 C (2) C14 C13 N2 C (15) C17 C9 C10 C (17) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N2 H2 O3 i 0.89 (1) 2.00 (1) (16) 151 (2) O5 H5A O8 ii 0.82 (1) 1.78 (1) (18) 171 (3) O7 H7 O3 iii 0.84 (1) 1.82 (1) (15) 168 (2) sup-7

10 O8 H8B O (1) 2.07 (1) (17) 163 (2) O8 H8A O4 ii 0.83 (1) 2.01 (1) (18) 170 (2) C11 H11 O1 iv (2) 156 C12 H12 O6 i (2) 155 C16 H16 O2 v (2) 160 Symmetry codes: (i) x+1, y 1/2, z+3/2; (ii) x, y+3/2, z+1/2; (iii) x, y+1/2, z+1/2; (iv) x+1, y+1, z+1; (v) x, y, z+1. sup-8

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