Quinolinium 8-hy­droxy-7-iodo­quinoline-5-sulfonate 0.8-hydrate

Graham Smith

doi:10.1107/S1600536812046247

. 2012 Nov 14;68(Pt 12):o3349. doi: 10.1107/S1600536812046247

Quinolinium 8-hydroxy-7-iodoquinoline-5-sulfonate 0.8-hydrate

Graham Smith ^a,^*

PMCID: PMC3588950 PMID: 23476186

Abstract

In the crystal structure of the title hydrated quinolinium salt of ferron (8-hydroxy-7-iodoquinoline-5-sulfonic acid), C₉H₇N⁺·C₉H₅INO₄S⁻·0.8H₂O, the quinolinium cation is fully disordered over two sites (occupancy factors fixed at 0.63 and 0.37) lying essentially within a common plane and with the ferron anions forming π–π-associated stacks down the b axis [minimum ring centroid separation = 3.462 (6) Å]. The cations and anions are linked into chains extending along c through hydroxy O—H⋯O and quinolinium N—H⋯O hydrogen bonds to sulfonate O-atom acceptors which are also involved in water O—H⋯O hydrogen-bonding interactions along b, giving a two-dimensional network.

Related literature

For the crystal structure of ferron, see: Balasubramanian & Muthiah (1996 ▶). For analytical applications of ferron, see: Vogel (1964 ▶). For the crystal structures of other non-zwitterionic compounds of ferron, see: Hemamalini et al. (2004 ▶); Smith et al. (2004 ▶, 2007 ▶). graphic file with name e-68-o3349-scheme1.jpg

Experimental

Crystal data

C₉H₈N⁺·C₉H₅INO₄S⁻·0.8H₂O
M _r = 494.69
Orthorhombic,
a = 16.2403 (5) Å
b = 7.1539 (3) Å
c = 15.2458 (5) Å
V = 1771.28 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.96 mm⁻¹
T = 200 K
0.32 × 0.25 × 0.12 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.906, T _max = 0.980
6143 measured reflections
3207 independent reflections
2709 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.082
S = 1.18
3207 reflections
244 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.66 e Å⁻³
Absolute structure: Flack (1983 ▶), 789 Friedel pairs
Flack parameter: 0.01 (3)

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Click here for additional data file.^{(28.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046247/su2523sup1.cif

e-68-o3349-sup1.cif^{(28.7KB, cif)}

Click here for additional data file.^{(154.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046247/su2523Isup2.hkl

e-68-o3349-Isup2.hkl^{(154.2KB, hkl)}

Click here for additional data file.^{(6.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812046247/su2523Isup3.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
N1A—H1A⋯O53ⁱ	0.86	1.97	2.783 (10)	157
N1B—H1B⋯O53ⁱ	0.86	1.88	2.725 (16)	166
O8—H8⋯O52ⁱⁱ	0.81	2.13	2.769 (7)	135
O1W—H11W⋯O52	0.89	2.18	3.066 (9)	179
O1W—H12W⋯O51ⁱⁱⁱ	0.90	2.18	3.080 (8)	178

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

Acknowledgments

The author acknowledges financial support from the Science and Engineering Faculty and the University Library, Queensland University of Technology.

supplementary crystallographic information

Comment

Ferron (8-hydroxy-7-iodoquinoline-5-sulfonic acid) is a bidentate complexing agent which has analytical applications as a selective colour reagent for the detection of iron(III) but not iron(II) (Vogel, 1964). The crystal structure of ferron (Balasubramanian & Muthiah, 1996) has shown that the molecule exists as a sulfonate-quinolinium zwitterion. As a sulfonic acid, ferron is potentially capable of protonating most Lewis bases, but the crystal structures of only a small number of such salts have been reported. With 8-hydroxyquinoline, a 1:1 sesquihydrate is formed (Smith et al., 2004) and with bifunctional 4,4^'-bipyridine (Hemamalini et al., 2004) a monoprotonated 1:1 dihydrate is found. A common structural feature in these ferron proton-transfer salts is the presence of R²₂(10) cyclic hydrogen-bonded ferron···ferron dimers involving the 8-hydroxy donor and hetero-N acceptor groups. Reaction of ferron with quinoline gave the title chemically stable 1:1 hydrated salt, whose crystal structure is reported on herein.

In the title compound, Fig. 1, the quinolinium cation is fully disordered over two sites A and B with occupancy factors fixed at 0.63 and 0.37, lying essentially within a common plane. These cations are linked to the anions through both quinolinium N—H···O and hydroxyl O—H···O and hydrogen bonds to sulfonate O-atom acceptors (Table 1), forming chains extending along c. Water O—H···O_sulfonate hydrogen-bonding interactions together with cation–anion ring π–π associations [minimum ring centroid separation = 3.462 (6) Å] link the chains down the b axial direction, giving a two-dimensional network structure (Figs. 2 and 3). The ferron–ferron dimeric association is not present. In the crystal, there are relatively short intra-anionic I7···O51^iv interactions [3.027 (5) Å] [symmetry code (iv): x + 1/2,-y, z].

With the ferron anion, the short intra-anionic O8—H8···N1 association [2.693 (7) Å] is present, similar to that found in other non-zwitterionic compounds of ferron (Hemamalini et al., 2004; Smith et al., 2004, 2007). Also the common aromatic ring C6–H6···O51_sulfonate association [2.827 (8) Å] maintains the S5–O51 bond close to the extended plane of the aromatic ring [torsion angle C10—C5—S5—O51, 171.1 (5) °].

Experimental

The title compound was synthesized by heating a solution containing 1 mmol of 8-hydroxy-7-iodoquinoline-5-sulfonic acid (ferron) and 1 mmol of quinoline in 50 ml of 50% ethanol-water for 10 min under reflux. After concentration to ca. 40 ml, partial room temperature evaporation of the hot-filtered solution gave yellow flat prisms of the title compound (m.p. 460.6–462.3 K) from which a specimen was cleaved for the X-ray analysis.