Sodium p-toluenesulfinate tetra­hydrate

Richard Betz; Thomas Gerber

doi:10.1107/S1600536811021738

. 2011 Jun 11;67(Pt 7):m898. doi: 10.1107/S1600536811021738

Sodium p-toluenesulfinate tetrahydrate

Richard Betz ^a,^*, Thomas Gerber ^a

PMCID: PMC3152039 PMID: 21836887

Abstract

The title compound, Na⁺·C₇H₇O₂S⁻·4H₂O, is the hydrate of the sodium salt of para-toluenesulfinic acid. The molecular geometry around the sulfur atom is tetrahedral with X–S–Y angles spanning a range of 102.23 (6)–110.04 (6)°. In the crystal, the water molecules connect the sodium cations into chains along the b axis via O—H⋯O hydrogen bonds. An intermolecular O—H⋯π interaction is also observed.

Related literature

For the crystal structure of sodium para-toluenesulfonate, see: Reinke & Rudershausen (1999 ▶). For details of graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

Na⁺·C₇H₇O₂S⁻·4H₂O
M _r = 250.24
Monoclinic,
a = 15.9432 (19) Å
b = 6.1825 (7) Å
c = 12.2668 (15) Å
β = 100.166 (5)°
V = 1190.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 200 K
0.53 × 0.39 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.826, T _max = 1.000
10741 measured reflections
2846 independent reflections
2554 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.087
S = 1.11
2846 reflections
162 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811021738/dn2695sup1.cif

e-67-0m898-sup1.cif^{(16.8KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536811021738/dn2695Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021738/dn2695Isup3.hkl

e-67-0m898-Isup3.hkl^{(139.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021738/dn2695Isup4.cdx

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H31⋯O1	0.81 (1)	1.98 (1)	2.7885 (14)	173 (2)
O3—H32⋯O2ⁱ	0.81 (1)	2.02 (1)	2.8059 (16)	166 (2)
O4—H41⋯O2	0.80 (1)	2.16 (1)	2.9038 (15)	154 (2)
O4—H42⋯O3ⁱⁱ	0.81 (1)	1.99 (1)	2.7884 (15)	173 (2)
O5—H51⋯O1ⁱⁱⁱ	0.80 (1)	1.99 (1)	2.7760 (15)	167 (2)
O5—H52⋯O2^iv	0.80 (1)	2.16 (1)	2.9319 (15)	163 (2)
O6—H61⋯O1^v	0.80 (1)	2.21 (2)	2.9528 (17)	154 (2)
O6—H62⋯Cg^vi	0.79 (1)	2.89 (2)	3.3782 (17)	122 (2)

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

Acknowledgments

The authors thank Mrs Jaci Neil-Schutte for helpful discussions.

supplementary crystallographic information

Comment

Multidentate ligands play a major role in the synthesis of coordination polymers and metal-organic framework compounds (MOFs). Especially derivatives of benzoic acid have found widespread use in this aspect and a variety of these coordination polymers have been characterized in solution and in the solid state. Owing to the desire to synthesize functionalized MOFs whose poresizes or even complete architectural set-ups might easily be influenced upon variation of external parameters such as pH value or the presence and concentration of molecules that might reside inside the pores of these MOFs, chelating ligands related to benzoic acid but with the ability to change their bonding behaviour are necessary. In this aspect, para-toluenesulfinic acid seemed of interest since it may act as neutral or anionic ligand, and even the sulfur atom may show donor action. In order to gather structural information to allow for the tailored synthesis of MOFs based on para-toluenesulfinic acid, we determined the crystal structure of its sodium salt. The crystal structure of the sodium salt of para-toluenesulfonic acid is apparent in the literature (Reinke & Rudershausen, 1999).

Taking into account the lone pair on the sulfur atom, the latter is present in a pseudo-tetrahedral molecular geometry. The X–S–Y angles span a range of 102.23 (6)–110.04 (6) °. The least-squares planes defined by the atoms of the aromatic system on the one hand and the SOO group on the other hand intersect at an angle of 64.47 (6) °. The sodium cation is coordinated by six water molecules (two of them symmetry-generated) of which two act as bridging ligands to the neighbouring sodium cation and thus foster the formation of a "sodium-acqua-polymer" chain along the crystallographic b axis (Fig. 2). The angles between two trans-orientated water molecules in the resultant [Na(H₂O)₆]⁺ octahedra were found adopting values between 163.96 (5) ° and 173.68 (4) °.

The crystal structure is dominated by hydrogen bonds. Except for one of the hydrogen atoms on one water molecule that is part of a O–H···π interaction, all of the water molecules take part in O–H···O hydrogen bonding. Each of the sulfinic acid group's O atoms acts as multifold acceptor. In terms of graph set analysis (Etter et al. (1990); Bernstein et al. (1995)), the description of the hydrogen bonding systems necessitates a DDDDDDDD descriptor on the unitary level. In total, the components of the crystal structure are connected to double layers perpendicular to the crystallographic a axis with the hydrophobic aromatic moieties forming the outer surfaces of these layers. π-Stacking is not a prominent feature of the crystal structure with the shortest distance between two aromatic systems found at 5.5359 (11) Å.

Experimental

The compound was obtained commercially (KEG). Crystals suitable for the X-ray diffraction study were obtained upon free evaporation of an aqueous solution thereof.