Benzyl­tributyl­ammonium 4,6-dihydroxy­naphthalene-2-sulfonate

Kazuya Uta; Jin Mizuguchi

doi:10.1107/S1600536809000415

. 2009 Jan 17;65(Pt 2):o322. doi: 10.1107/S1600536809000415

Benzyltributylammonium 4,6-dihydroxynaphthalene-2-sulfonate

Kazuya Uta ^a, Jin Mizuguchi ^a,^*

PMCID: PMC2968369 PMID: 21581927

Abstract

The title molecular salt, C₁₉H₃₄N⁺·C₁₀H₇O₅S⁻, is a charge-control agent used for toners in electrophotography with a high melting point of 508 K. In the crystal structure, the anions form inversion dimers, linked by pairs of O—H⋯O hydrogen bonds. Further O—H⋯O links between dimers generate anionic sheets propagating in (010). One of the n-butyl chains of the cation is disordered over two sets of sites in a 0.53:0.47 ratio.

Related literature

For background on charge-control agents, see: Nash et al. (2001 ▶) and Uta et al. (2009 ▶). For the structures of benzyltributylammonium 4-hydroxynaphthalene-1-sulfonate, benzyltributylammonium 6-hydroxynaphthalene-2-sulfonate, benzyltributylammonium 4-hydroxynaphthalene-2-sulfonate and benzyltributylammonium 7-hydroxynaphthalene-1-sulfonate, see: Mizuguchi et al. (2007 ▶), Uta et al. (2009 ▶), Uta & Mizuguchi (2009 ▶) and Sato et al. (2009 ▶), respectively.

Experimental

Crystal data

C₁₉H₃₄N⁺·C₁₀H₇O₅S⁻
M _r = 515.70
Orthorhombic,
a = 18.6976 (3) Å
b = 15.3045 (2) Å
c = 19.7287 (3) Å
V = 5645.51 (14) Å³
Z = 8
Cu Kα radiation
μ = 1.32 mm⁻¹
T = 296.1 K
0.50 × 0.45 × 0.40 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.425, T _max = 0.517 (expected range = 0.485–0.590)
49979 measured reflections
5149 independent reflections
2937 reflections with F ² > 2σ(F ²)
R _int = 0.070

Refinement

R[F ² > 2σ(F ²)] = 0.196
wR(F ²) = 0.547
S = 1.49
5149 reflections
332 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −1.55 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2006 ▶); program(s) used to solve structure: SIR2004 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000415/hb2891sup1.cif

e-65-0o322-sup1.cif^{(28.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000415/hb2891Isup2.hkl

e-65-0o322-Isup2.hkl^{(252.3KB, 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
O4—H4O⋯O2ⁱ	0.82	1.94	2.758 (6)	172
O5—H5O⋯O3ⁱⁱ	0.82	1.87	2.623 (6)	153

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

Acknowledgments

The authors express their sincere thanks to Mr O. Yamate at Orient Chemical Industries, Ltd for the sample preparation.

supplementary crystallographic information

Comment

Compound (I) is a charge-control-agent used for toners in electrophotography. The background of the present study has been set out in our previous paper (Uta et al., 2009). We have previously investigated the crystal structure of the following four isomers in connection with the mechanism of their high melting points: benzyltributylammonium 4-hydroxynaphthalene-1-sulfonate (Mizuguchi et al., 2007), benzyltributylammonium 6-hydroxynaphthalene-2-sulfonate (Uta et al., 2009, benzyltributylammonium 4-hydroxynaphthalene-2-sulfonate (Uta & Mizuguchi, 2009), and benzyltributylammonium 7-hydroxynaphthalene-1-sulfonate (Sato et al., 2009). The melting points of these isomers are 462, 433, 451 and 439 K, respectively. Except for benzyltributylammonium 4-hydroxynaphthalene-2-sulfonate, the anions in the ammonium sulfates form chains of O—H···O intermolecular hydrogen bonds between the –OH group of one anion and the sulfonic O atom of the neighboring one. The present hydrogen-bond network is found to be responsible for the high thermal stability of these compounds. On the other hand, benzyltributylammonium 4-hydroxynaphthalene-2-sulfonate which forms a two-dimensional hydrogen-bond network (Uta & Mizuguchi, 2009). The present paper deals with the structure of the title compound, (I), which includes two hydroxy groups in the naphthalene sulfonate (Fig. 1).

The ions in (I) have no crystallographically imposed symmetry. Fig. 2 shows a pseudo-dimer unit connected by O—H···O intermolecular hydrogen-bonded between the OH group of one anion and the sulfonic O atom of the neighboring one. Then, the dimer units consitute a two-dimensional hydrogen-bond network as shown in Fig. 3. There are four hydrogen bonds per molecule in the network, which contibutes to the high thermal stability of compound (I) as characterized by a melting point of 478 K.

Experimental

The title compound was obtained from Orient Chemical Industries Ltd., and was recrystallized from an methanol solution. After 48 h, a number of colourless crystals were obtained in the form of blocks of (I).