8-Ammonio­naphthalene-2-sulfonate monohydrate: the zwitterionic hydrate of 1,7-Cleve’s acid

Graham Smith; Urs D Wermuth; David J Young

doi:10.1107/S1600536809030396

. 2009 Aug 8;65(Pt 9):o2110. doi: 10.1107/S1600536809030396

8-Ammonionaphthalene-2-sulfonate monohydrate: the zwitterionic hydrate of 1,7-Cleve’s acid

Graham Smith ^a,^*, Urs D Wermuth ^a, David J Young ^b

PMCID: PMC2969967 PMID: 21577525

Abstract

The structure of 8-amino-2-naphthalenesulfonic acid monohydrate (1,7-Cleve’s acid hydrate), C₁₀H₉NO₃S·H₂O, shows the presence of a sulfonate–aminium group zwitterion, both groups and the water molecule of solvation giving cyclic R ₃ ³(8) O—H⋯O and N—H⋯O intermolecular hydrogen-bonding interactions, forming chains which extend down the a axis of the unit cell. Additional peripheral associations, including weak aromatic ring π–π interactions [centroid–centroid distance = 3.6299 (15) Å], result in a two-dimensional sheet structure.

Related literature

1,7-Cleve’s acid and 1,6-Cleve’s acid have important industrialchemical applications as azo dye precursors, see: O’Neil (2001 ▶). For the preliminary crystal data for a number of aminonaphthalenesulfonic acids, see: Corbridge et al. (1966 ▶). For the strutures of 5-amino-2-naphthalenesulfonic acid (1,6-Cleve’s acid) and the 1:1 adduct of 1,7-Cleve’s acid with strychnine, see: Smith et al. (2004 ▶, 2007 ▶).

Experimental

Crystal data

C₁₀H₉NO₃S·H₂O
M _r = 241.27
Orthorhombic,
a = 7.1616 (3) Å
b = 16.4608 (7) Å
c = 8.9059 (3) Å
V = 1049.88 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 297 K
0.35 × 0.20 × 0.05 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.950, T _max = 0.990
5904 measured reflections
2252 independent reflections
1830 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.076
S = 0.91
2252 reflections
165 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ▶), 974 Friedel pairs
Flack parameter: 0.06 (8)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030396/tk2500sup1.cif

e-65-o2110-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030396/tk2500Isup2.hkl

e-65-o2110-Isup2.hkl^{(108.5KB, hkl)}

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
O1W—H11W⋯O23ⁱ	0.82 (4)	1.98 (4)	2.798 (3)	176 (3)
O1W—H12W⋯O22ⁱⁱ	0.90 (3)	1.91 (3)	2.796 (3)	169 (3)
N8—H81⋯O23ⁱⁱⁱ	0.88 (3)	1.95 (3)	2.817 (2)	171 (2)
N8—H82⋯O21ⁱⁱ	0.89 (4)	1.96 (3)	2.793 (3)	154 (3)
N8—H83⋯O1W	0.98 (4)	1.82 (4)	2.725 (3)	152 (4)

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

Acknowledgments

The authors acknowledge financial support from the Australian Research Council, the School of Physical and Chemical Sciences, Queensland University of Technology, and the School of Biomolecular and Physical Sciences, Griffith University.

supplementary crystallographic information

Comment

8-Amino-2-naphthalenesulfonic acid (1-naphthylamine-7-sulfonic acid: 1,7-Cleve's acid) is a compound which along with 1,6-Cleve's acid has important industrial chemical applications as an azo dye precursor (O'Neil, 2001). Although the preliminary crystal data for a number of aminonaphthalenesulfonic acids were reported by Corbridge et al. (1966), the crystal structures of very few have been determined. We reported the structure of 5-amino-2-naphthalenesulfonic acid (1,6-Cleve's acid) (Smith et al., 2004) which, together with the 1:1 adduct of 1,7-Cleve's acid with strychnine (Smith et al., 2007) represent the only crystallographically characterized examples. In both of these structures the molecules exist as sulfonate–amino group zwitterions as is commonly the case with the aminosulfonic acids.

The crystals used for the determination of the structure reported here, the hydrate C₁₀H₉NO₃S.H₂O (I), were obtained from the attempted preparation of a co-crystal with picrylsulfonic acid in ethanol-water solvent, the usual reported form of the acid is the same monohydrate. The unit-cell parameters and space group reported for this compound (Corbridge et al., 1964) (orthorhombic, a = 8.91, b = 16.44, c = 7.14 Å, space group P2₁cn (non-standard setting) are comparable to those determined here for (I).

The molecules of 1,7-Cleve's acid monohydrate in (I), like those of the isomeric anhydrous 1,6-Cleve's acid (Smith et al., 2004), not unexpectedly show the presence of a sulfonate–aminium group zwitterion (Fig. 1). However, the presence of the water molecule of solvation in (I) results in significantly different hydrogen-bonding characteristics. Whereas with 1,6-Cleve's acid, the aminium protons give interactions with the sulfonate-O acceptors of three separate acid species, giving a 3-D structure, in (I) the structure is 2-D (Fig. 2). The primary intermolecular sulfonate–aminium group interaction involves the water molecule in a cyclic R₃³(8) association resulting in chains extending down the a direction in the unit cell. Additional peripheral interactions (Table 1) together with weak intermolecular π–π aromatic ring associations [minimum ring centroid separation, 3.6299 (15) Å for the six-membered ring C5–C10], give the structure extension across c (Fig. 3).

Experimental

The title compound (I) was isolated as the only product from the attempted preparation of an adduct compound of 8-amino-2-naphthalenesulfonic acid (1-naphthylamine-7-sulfonic acid) with picrylsulfonic acid, by heating together for 10 min under reflux 1 mmol quantities of the two reagents in 40 ml of 50% ethanol-water. The crystals formed as colourless flat prisms after partial room-temperature evaporation of the hot-filtered solution.