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

Smith, G.

doi:10.1107/S1600536812046247

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3349

doi:10.1107/S1600536812046247

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

Graham Smith ^a ^*

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 30 October 2012; accepted 8 November 2012; online 14 November 2012)

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 ).

Experimental

Crystal data

C₉H₈N⁺·C₉H₅INO₄S⁻·0.8H₂O
M_r = 494.69
Orthorhombic, P c a 2₁
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[F² > 2σ(F²)] = 0.040
wR(F²) = 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)

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
Symmetry codes: (i) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+2, z+{\script{1\over 2}}]$ ; (iii) x, y+1, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046247/su2523sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536812046247/su2523Isup3.cml

checkCIF report

Comment top

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) °].

Related literature top

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);

Experimental top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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 (Spek, 2009).

Figures top

	Fig. 1. Molecular configuration and atom naming for the individual cation, the disordered anion components (A and B) and the water species in the title compound. The minor-occupancy B anion is shown with broken bonds and displacement ellipsoids are drawn at the 30% probability level. The intra- and inter-species hydrogen bonds are shown as a dashed lines.
	Fig. 2. The stacking of the cation and anion rings down the b axis in the crystal of the title compound.
	Fig. 3. A perspective view of the crystal packing of the title compound viewed along the a axis, showing the inter-chain water hydrogen-bonding associations (dashed lines; see Table for details; symmetry codes: (i) -x+1, -y+1, z+1/2; (ii) -x+1, -y+2, z+1/2; (iii) x, y+1, z).

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

Crystal data top

C₉H₈N⁺·C₉H₅INO₄S⁻·0.8H₂O	F(000) = 976
M_r = 494.69	D_x = 1.855 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1806 reflections
a = 16.2403 (5) Å	θ = 3.4–28.9°
b = 7.1539 (3) Å	µ = 1.96 mm⁻¹
c = 15.2458 (5) Å	T = 200 K
V = 1771.28 (11) Å³	Flat prism, yellow
Z = 4	0.32 × 0.25 × 0.12 mm

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	3207 independent reflections
Radiation source: fine-focus sealed tube	2709 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 16.077 pixels mm^-1	θ_max = 28.9°, θ_min = 3.4°
ω scans	h = −22→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −6→9
T_min = 0.906, T_max = 0.980	l = −19→19
6143 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0181P)² + 3.2291P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.004
3207 reflections	Δρ_max = 0.65 e Å⁻³
244 parameters	Δρ_min = −0.66 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 789 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (3)

Crystal data top

C₉H₈N⁺·C₉H₅INO₄S⁻·0.8H₂O	V = 1771.28 (11) Å³
M_r = 494.69	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 16.2403 (5) Å	µ = 1.96 mm⁻¹
b = 7.1539 (3) Å	T = 200 K
c = 15.2458 (5) Å	0.32 × 0.25 × 0.12 mm

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.082	Δρ_max = 0.65 e Å⁻³
S = 1.18	Δρ_min = −0.66 e Å⁻³
3207 reflections	Absolute structure: Flack (1983), 789 Friedel pairs
244 parameters	Absolute structure parameter: 0.01 (3)
1 restraint

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1A	0.5706 (6)	0.4412 (12)	0.3693 (6)	0.020 (2)*	0.630
C2A	0.6389 (9)	0.4939 (16)	0.3279 (9)	0.025 (3)*	0.630
C3A	0.6447 (7)	0.4807 (15)	0.2359 (9)	0.019 (2)*	0.630
C4A	0.5784 (8)	0.4161 (17)	0.1888 (8)	0.026 (3)*	0.630
C5A	0.4375 (7)	0.2937 (15)	0.1920 (9)	0.023 (3)*	0.630
C6A	0.3681 (8)	0.2443 (17)	0.2377 (9)	0.030 (2)*	0.630
C7A	0.3664 (8)	0.2600 (17)	0.3288 (10)	0.026 (2)*	0.630
C8A	0.4325 (10)	0.3261 (17)	0.3750 (8)	0.026 (3)*	0.630
C9A	0.5015 (8)	0.3760 (17)	0.3272 (8)	0.021 (3)*	0.630
C10A	0.5084 (11)	0.356 (3)	0.2307 (12)	0.022 (5)*	0.630
C8B	0.6037 (15)	0.466 (3)	0.3434 (14)	0.020 (4)*	0.370
C9B	0.5273 (13)	0.388 (3)	0.3220 (12)	0.013 (4)*	0.370
C10B	0.4986 (15)	0.362 (3)	0.2426 (16)	0.006 (6)*	0.370
C3B	0.3682 (13)	0.254 (3)	0.2889 (17)	0.029 (4)*	0.370
C4B	0.4180 (12)	0.288 (3)	0.2210 (14)	0.020 (4)*	0.370
C5B	0.5542 (14)	0.390 (3)	0.1688 (15)	0.032 (5)*	0.370
C6B	0.6308 (13)	0.451 (3)	0.1885 (15)	0.030 (4)*	0.370
C7B	0.6552 (12)	0.496 (3)	0.2747 (15)	0.022 (4)*	0.370
N1B	0.4736 (11)	0.341 (2)	0.3879 (10)	0.022 (3)*	0.370
C2B	0.4005 (15)	0.285 (3)	0.3719 (14)	0.028 (5)*	0.370
I7	0.30996 (2)	0.75195 (7)	0.45473 (4)	0.0259 (1)
S5	0.38785 (10)	0.7547 (3)	0.09027 (10)	0.0232 (4)
O8	0.4943 (2)	0.8886 (6)	0.4574 (4)	0.0265 (11)
O51	0.3101 (3)	0.6580 (7)	0.0999 (3)	0.0327 (16)
O52	0.3807 (3)	0.9388 (7)	0.0506 (3)	0.0280 (16)
O53	0.4497 (3)	0.6391 (7)	0.0466 (3)	0.0323 (16)
N1	0.6037 (3)	0.9565 (7)	0.3285 (4)	0.0220 (17)
C2	0.6580 (4)	0.9911 (9)	0.2656 (5)	0.027 (2)
C3	0.6418 (4)	0.9684 (9)	0.1760 (5)	0.0233 (19)
C4	0.5659 (4)	0.9043 (9)	0.1505 (4)	0.0223 (19)
C5	0.4255 (4)	0.7936 (7)	0.1981 (4)	0.0150 (17)
C6	0.3719 (4)	0.7600 (9)	0.2665 (4)	0.0183 (17)
C7	0.3948 (4)	0.7926 (7)	0.3545 (4)	0.0147 (17)
C8	0.4722 (4)	0.8578 (8)	0.3737 (4)	0.0173 (17)
C9	0.5289 (4)	0.8920 (8)	0.3042 (4)	0.0157 (17)
C10	0.5063 (4)	0.8627 (8)	0.2143 (4)	0.0167 (17)
O1W	0.2775 (5)	1.2846 (9)	0.0055 (5)	0.057 (3)	0.800
H4A	0.58090	0.41330	0.12790	0.0310*	0.630
H5A	0.43630	0.28440	0.13110	0.0270*	0.630
H6A	0.32210	0.20010	0.20780	0.0360*	0.630
H7A	0.31910	0.22470	0.35900	0.0310*	0.630
H8A	0.43110	0.33690	0.43570	0.0310*	0.630
H1A	0.56960	0.44830	0.42560	0.0240*	0.630
H2A	0.68320	0.53980	0.35990	0.0300*	0.630
H3A	0.69290	0.51530	0.20730	0.0220*	0.630
H1B	0.48960	0.34940	0.44150	0.0260*	0.370
H2B	0.36610	0.26310	0.41960	0.0330*	0.370
H3B	0.31450	0.21280	0.28100	0.0350*	0.370
H4B	0.40210	0.26440	0.16340	0.0240*	0.370
H5B	0.53800	0.36630	0.11140	0.0380*	0.370
H6B	0.66890	0.46380	0.14340	0.0360*	0.370
H7B	0.70690	0.54790	0.28460	0.0270*	0.370
H8B	0.61840	0.49450	0.40080	0.0250*	0.370
H2	0.71010	1.03290	0.28190	0.0320*
H3	0.68190	0.99650	0.13450	0.0280*
H4	0.55400	0.88840	0.09130	0.0270*
H6	0.31940	0.71470	0.25440	0.0220*
H8	0.54190	0.92330	0.45790	0.0390*
H11W	0.30700	1.18390	0.01810	0.0850*	0.800
H12W	0.28600	1.39490	0.03310	0.0850*	0.800

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I7	0.0229 (2)	0.0360 (2)	0.0189 (2)	−0.0052 (2)	0.0053 (2)	−0.0028 (2)
S5	0.0250 (8)	0.0290 (8)	0.0156 (6)	−0.0017 (8)	−0.0034 (6)	0.0023 (7)
O8	0.025 (2)	0.036 (2)	0.0184 (18)	−0.0057 (18)	−0.006 (3)	−0.007 (3)
O51	0.030 (3)	0.043 (3)	0.025 (2)	−0.017 (2)	−0.010 (2)	0.003 (2)
O52	0.028 (3)	0.031 (3)	0.025 (2)	0.000 (2)	−0.003 (2)	0.010 (2)
O53	0.045 (3)	0.031 (3)	0.021 (2)	0.006 (3)	0.000 (2)	−0.009 (2)
N1	0.017 (3)	0.022 (3)	0.027 (3)	−0.005 (2)	−0.003 (2)	−0.001 (3)
C2	0.018 (3)	0.023 (4)	0.041 (4)	0.002 (3)	−0.007 (3)	0.007 (3)
C3	0.018 (3)	0.017 (3)	0.035 (4)	0.006 (3)	0.005 (3)	0.003 (3)
C4	0.028 (4)	0.016 (3)	0.023 (3)	0.005 (3)	0.004 (3)	0.004 (3)
C5	0.025 (3)	0.008 (3)	0.012 (3)	0.000 (2)	0.001 (2)	0.000 (2)
C6	0.018 (3)	0.019 (3)	0.018 (3)	−0.003 (3)	−0.002 (2)	0.004 (3)
C7	0.013 (3)	0.011 (3)	0.020 (3)	−0.001 (2)	0.006 (2)	0.001 (2)
C8	0.020 (3)	0.014 (3)	0.018 (3)	0.001 (2)	0.001 (3)	−0.004 (3)
C9	0.013 (3)	0.009 (3)	0.025 (3)	0.000 (2)	0.001 (2)	−0.001 (2)
C10	0.018 (3)	0.012 (3)	0.020 (3)	−0.001 (2)	0.000 (3)	0.008 (3)
O1W	0.070 (5)	0.027 (4)	0.073 (5)	0.023 (4)	−0.034 (4)	−0.010 (4)

Geometric parameters (Å, º) top

I7—C7	2.078 (6)	C8A—C9A	1.38 (2)
S5—O52	1.454 (5)	C8B—C9B	1.40 (3)
S5—O51	1.447 (5)	C9A—C10A	1.48 (2)
S5—O53	1.462 (5)	C9B—C10B	1.31 (3)
S5—C5	1.776 (6)	C2A—H2A	0.9300
O8—C8	1.344 (8)	C2B—H2B	0.9300
O8—H8	0.8100	C3A—H3A	0.9300
O1W—H12W	0.9000	C3B—H3B	0.9300
O1W—H11W	0.8900	C4A—H4A	0.9300
N1A—C2A	1.331 (17)	C4B—H4B	0.9300
N1A—C9A	1.374 (16)	C5A—H5A	0.9300
N1B—C9B	1.37 (3)	C5B—H5B	0.9300
N1B—C2B	1.28 (3)	C6A—H6A	0.9300
N1A—H1A	0.8600	C6B—H6B	0.9300
N1B—H1B	0.8600	C7A—H7A	0.9300
N1—C2	1.326 (9)	C7B—H7B	0.9300
N1—C9	1.351 (8)	C8A—H8A	0.9300
C2A—C3A	1.409 (19)	C8B—H8B	0.9300
C2B—C3B	1.39 (3)	C2—C3	1.401 (11)
C3A—C4A	1.374 (17)	C3—C4	1.371 (9)
C3B—C4B	1.34 (3)	C4—C10	1.404 (9)
C4A—C10A	1.37 (2)	C5—C6	1.380 (9)
C4B—C10B	1.45 (3)	C5—C10	1.424 (9)
C5A—C10A	1.37 (2)	C6—C7	1.412 (9)
C5A—C6A	1.371 (18)	C7—C8	1.372 (9)
C5B—C6B	1.35 (3)	C8—C9	1.425 (9)
C5B—C10B	1.46 (3)	C9—C10	1.434 (9)
C6A—C7A	1.39 (2)	C2—H2	0.9300
C6B—C7B	1.41 (3)	C3—H3	0.9300
C7A—C8A	1.37 (2)	C4—H4	0.9300
C7B—C8B	1.36 (3)	C6—H6	0.9300

O51—S5—O52	113.9 (3)	C4B—C3B—H3B	122.00
O51—S5—O53	112.1 (3)	C10A—C4A—H4A	120.00
O51—S5—C5	106.3 (3)	C3A—C4A—H4A	120.00
O52—S5—O53	112.2 (3)	C3B—C4B—H4B	122.00
O52—S5—C5	105.7 (3)	C10B—C4B—H4B	122.00
O53—S5—C5	105.9 (3)	C10A—C5A—H5A	118.00
C8—O8—H8	108.00	C6A—C5A—H5A	118.00
H11W—O1W—H12W	122.00	C10B—C5B—H5B	122.00
C2A—N1A—C9A	123.7 (10)	C6B—C5B—H5B	122.00
C2B—N1B—C9B	121.9 (17)	C5A—C6A—H6A	120.00
C9A—N1A—H1A	118.00	C7A—C6A—H6A	120.00
C2A—N1A—H1A	118.00	C5B—C6B—H6B	119.00
C9B—N1B—H1B	119.00	C7B—C6B—H6B	119.00
C2B—N1B—H1B	119.00	C8A—C7A—H7A	119.00
C2—N1—C9	117.6 (6)	C6A—C7A—H7A	119.00
N1A—C2A—C3A	120.6 (12)	C8B—C7B—H7B	120.00
N1B—C2B—C3B	125 (2)	C6B—C7B—H7B	120.00
C2A—C3A—C4A	119.4 (11)	C7A—C8A—H8A	121.00
C2B—C3B—C4B	117 (2)	C9A—C8A—H8A	122.00
C3A—C4A—C10A	120.7 (13)	C9B—C8B—H8B	122.00
C3B—C4B—C10B	116 (2)	C7B—C8B—H8B	122.00
C6A—C5A—C10A	123.8 (14)	N1—C2—C3	124.0 (6)
C6B—C5B—C10B	116 (2)	C2—C3—C4	119.0 (6)
C5A—C6A—C7A	120.1 (12)	C3—C4—C10	119.6 (6)
C5B—C6B—C7B	123 (2)	C6—C5—C10	120.7 (6)
C6A—C7A—C8A	121.7 (12)	S5—C5—C6	117.1 (5)
C6B—C7B—C8B	120.7 (19)	S5—C5—C10	122.2 (5)
C7A—C8A—C9A	117.0 (12)	C5—C6—C7	121.6 (6)
C7B—C8B—C9B	115.4 (19)	I7—C7—C8	119.9 (4)
C8A—C9A—C10A	124.0 (13)	I7—C7—C6	120.1 (5)
N1A—C9A—C10A	115.8 (12)	C6—C7—C8	120.0 (6)
N1A—C9A—C8A	120.2 (11)	O8—C8—C9	120.4 (5)
N1B—C9B—C8B	119.4 (17)	O8—C8—C7	120.2 (5)
C8B—C9B—C10B	126 (2)	C7—C8—C9	119.5 (6)
N1B—C9B—C10B	115 (2)	N1—C9—C10	122.8 (6)
C4A—C10A—C9A	119.6 (15)	C8—C9—C10	121.3 (6)
C4A—C10A—C5A	126.7 (16)	N1—C9—C8	115.8 (6)
C5A—C10A—C9A	113.3 (14)	C4—C10—C9	117.0 (6)
C5B—C10B—C9B	118 (2)	C4—C10—C5	126.1 (6)
C4B—C10B—C5B	116 (2)	C5—C10—C9	116.9 (6)
C4B—C10B—C9B	126 (2)	N1—C2—H2	118.00
C3A—C2A—H2A	120.00	C3—C2—H2	118.00
N1A—C2A—H2A	120.00	C4—C3—H3	121.00
C3B—C2B—H2B	117.00	C2—C3—H3	120.00
N1B—C2B—H2B	118.00	C3—C4—H4	120.00
C2A—C3A—H3A	120.00	C10—C4—H4	120.00
C4A—C3A—H3A	120.00	C5—C6—H6	119.00
C2B—C3B—H3B	122.00	C7—C6—H6	119.00

O53—S5—C5—C6	−130.4 (5)	C8A—C9A—C10A—C4A	177.6 (14)
O53—S5—C5—C10	51.8 (5)	N1—C2—C3—C4	−0.9 (10)
O52—S5—C5—C6	110.4 (5)	C2—C3—C4—C10	−0.1 (9)
O51—S5—C5—C6	−11.0 (5)	C3—C4—C10—C5	−179.3 (6)
O51—S5—C5—C10	171.1 (5)	C3—C4—C10—C9	0.5 (9)
O52—S5—C5—C10	−67.4 (5)	S5—C5—C6—C7	−177.8 (5)
C2A—N1A—C9A—C10A	3.5 (18)	C10—C5—C6—C7	0.0 (9)
C9A—N1A—C2A—C3A	−1.6 (17)	S5—C5—C10—C4	−1.5 (8)
C2A—N1A—C9A—C8A	−179.2 (11)	S5—C5—C10—C9	178.7 (4)
C9—N1—C2—C3	1.4 (9)	C6—C5—C10—C4	−179.2 (6)
C2—N1—C9—C8	−179.6 (5)	C6—C5—C10—C9	1.0 (8)
C2—N1—C9—C10	−0.9 (9)	C5—C6—C7—I7	177.1 (4)
N1A—C2A—C3A—C4A	1.3 (17)	C5—C6—C7—C8	−0.5 (9)
C2A—C3A—C4A—C10A	−3 (2)	I7—C7—C8—O8	2.6 (7)
C3A—C4A—C10A—C5A	178.0 (15)	I7—C7—C8—C9	−177.6 (4)
C3A—C4A—C10A—C9A	5 (2)	C6—C7—C8—O8	−179.9 (5)
C6A—C5A—C10A—C4A	−176.6 (16)	C6—C7—C8—C9	0.0 (8)
C6A—C5A—C10A—C9A	−4 (2)	O8—C8—C9—N1	−0.4 (8)
C10A—C5A—C6A—C7A	1 (2)	O8—C8—C9—C10	−179.1 (5)
C5A—C6A—C7A—C8A	0.7 (19)	C7—C8—C9—N1	179.8 (5)
C6A—C7A—C8A—C9A	−0.3 (19)	C7—C8—C9—C10	1.1 (9)
C7A—C8A—C9A—C10A	−2 (2)	N1—C9—C10—C4	0.0 (9)
C7A—C8A—C9A—N1A	−179.1 (11)	N1—C9—C10—C5	179.8 (5)
N1A—C9A—C10A—C4A	−5 (2)	C8—C9—C10—C4	178.6 (6)
C8A—C9A—C10A—C5A	4 (2)	C8—C9—C10—C5	−1.5 (8)
N1A—C9A—C10A—C5A	−179.0 (13)

Hydrogen-bond geometry (Å, º) top

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···N1	0.81	2.23	2.693 (7)	117
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
C4—H4···O53	0.93	2.55	3.110 (8)	119
C6—H6···O51	0.93	2.39	2.827 (8)	108
C8A—H8A···O53ⁱ	0.93	2.58	3.251 (14)	130

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

Experimental details

Crystal data
Chemical formula	C₉H₈N⁺·C₉H₅INO₄S⁻·0.8H₂O
M_r	494.69
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	200
a, b, c (Å)	16.2403 (5), 7.1539 (3), 15.2458 (5)
V (Å³)	1771.28 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.96
Crystal size (mm)	0.32 × 0.25 × 0.12

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.906, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	6143, 3207, 2709
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.082, 1.18
No. of reflections	3207
No. of parameters	244
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.66
Absolute structure	Flack (1983), 789 Friedel pairs
Absolute structure parameter	0.01 (3)

Computer programs: CrysAlis PRO (Agilent, 2012), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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

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

Acknowledgements

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

References

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