Benzyl­tributyl­ammonium 6,7-dihydroxy­naphthalene-2-sulfonate

Kazuya Uta; Jin Mizuguchi

doi:10.1107/S160053680900018X

. 2009 Jan 17;65(Pt 2):o323. doi: 10.1107/S160053680900018X

Benzyltributylammonium 6,7-dihydroxynaphthalene-2-sulfonate

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

PMCID: PMC2968267 PMID: 21581928

Abstract

The title molecular salt, C₁₉H₃₄N⁺·C₁₀H₇O₅S⁻, is a charge-control agent used for toners in electrophotography. There are two formula units in the asymmetric unit. Both anions form inversion dimers connected by pairs of O—H⋯O hydrogen bonds between the –OH group of one anion and a sulfonic O atom of the neighboring one. The two dimers A and B are characterized by a step between the least-squares planes of the naphthalene atoms of 0.85 and 2.30 Å. Further O—H⋯O bonds link the dimers into a two-dimensional network propagating in (110) such that dimer A is hydrogen-bonded to four B units and vice versa. One of the tert-butyl chains in one of the cations is disordered over two sets of sites in a 0.56:0.44 ratio.

Related literature

For the function of charge-control agents, see: Nash et al. (2001 ▶). For background and related structures, see: Mizuguchi et al. (2007 ▶); Uta & Mizuguchi (2009a ▶,b ▶); Sato et al. (2009 ▶); Uta et al. (2009 ▶).

Experimental

Crystal data

C₁₉H₃₄N·C₁₀H₇O₅S
M _r = 515.70
Triclinic,
a = 8.6720 (2) Å
b = 17.1110 (3) Å
c = 18.8201 (4) Å
α = 86.4785 (11)°
β = 83.9245 (12)°
γ = 85.4033 (11)°
V = 2764.08 (10) Å³
Z = 4
Cu Kα radiation
μ = 1.35 mm⁻¹
T = 296.1 K
0.38 × 0.33 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.650, T _max = 0.817
22714 measured reflections
9189 independent reflections
6913 reflections with F ² > 2σ(F ²)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.211
S = 1.12
9189 reflections
659 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 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 General, I. DOI: 10.1107/S160053680900018X/hb2892sup1.cif

e-65-0o323-sup1.cif^{(44.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900018X/hb2892Isup2.hkl

e-65-0o323-Isup2.hkl^{(449.4KB, 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⋯O3ⁱ	0.82	1.85	2.670 (3)	174
O5—H5O⋯O8ⁱⁱ	0.82	1.83	2.625 (3)	163
O9—H9O⋯O2	0.82	1.85	2.650 (3)	165
O10—H10O⋯O6ⁱⁱⁱ	0.82	1.93	2.705 (3)	158

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

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, 2009a), 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 was characterized by a hydrogen-bonded dimer of the anions through O—H···O hydrogen bonding. In addition to these isomers, we have newly studied a similar ammonium sulfonate which includes two hydroxy groups in the naphthalene sulfonate as in the title compound: benzyltributylammonium 4,6-dihydroxynaphthalene-2-sulfonate which forms a two-dimensional hydrogen-bond network (Uta & Mizuguchi, 2009b).

There are two independent molecules in the asymmetric unit. The ions have no crystallographically imposed symmetry. Both anions form inversion dimers (A: composed of two anions of C20—C21/S2/O1—O5; B: composed of two anions of C49—C58/S1/O6—O9) through O—H···O intermoleclar hydrogen bonds (Table 1) between the –OH group of one anion and the sulfonic O atom of the neighboring one (Figs. 2 and 4). Dimer units A and B are characterized by a step of about 0.85 and 2.30Å (Figs. 3 and 5, respectively). Then, units A and B constitute a two-dimentional O—H···O hydrogen-bond network. Unit A is hydrogen-bonded to four units B and vice versa, as shown in Fig. 6. The present network is quite similart to that of benzyltributylammonium 4,6-dihydroxynaphthalene-2-sulfonate (Uta & Mizuguchi, 2009b) and ensures a 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 of (I) were obtained in the form of plates.