Diisopropyl­ammonium methane­sulfonate

Guido J Reiss; Michaela K Meyer

doi:10.1107/S1600536811029382

. 2011 Jul 30;67(Pt 8):o2169. doi: 10.1107/S1600536811029382

Diisopropylammonium methanesulfonate

Guido J Reiss ^a,^*, Michaela K Meyer ^a

PMCID: PMC3213604 PMID: 22091181

Abstract

The title molecular salt, C₆H₁₆N⁺·CH₃SO₃ ⁻, has been determined at 150 K. Two diisopropylammonium cations (dipH) and two anions form N—H⋯O hydrogen-bonded cyclic dimers lying around centers of symmetry. Only two of the three O atoms of the methanesulfonate anion are involved in hydrogen bonding, resulting in slightly longer S—O bond lengths. The title structure represents an example of a sulfonate anion that is part of a hydrogen-bonding R ₄ ⁴(12) graph-set motif, which is well known for related dipH acetates. Additionally, the Raman and the IR spectroscopic data for the title compound are presented.

Related literature

For simple dipH salts, see: Bajorat & Reiss (2007 ▶); Reiss (1998 ▶, 2002 ▶); Reiss (2010a ▶,b ▶); Reiss & Engel (2004 ▶); Reiss & Meyer (2010 ▶); Sada et al. (2004 ▶), Summers et al. (1998 ▶). For spectroscopic data for sulfonate salts, see: Thomson (1972 ▶); Genceli Guner et al. (2010 ▶). For graph-set analysis, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C₆H₁₆N⁺·CH₃SO₃ ⁻
M _r = 197.29
Monoclinic,
a = 8.88154 (13) Å
b = 8.53537 (13) Å
c = 14.5784 (2) Å
β = 101.8161 (15)°
V = 1081.73 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 150 K
0.65 × 0.25 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.951, T _max = 1.000
25064 measured reflections
3149 independent reflections
2782 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.060
S = 1.03
3149 reflections
146 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811029382/qm2018sup1.cif

e-67-o2169-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811029382/qm2018Isup2.hkl

e-67-o2169-Isup2.hkl^{(154.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811029382/qm2018Isup3.mol

Supplementary material file. DOI: 10.1107/S1600536811029382/qm2018Isup4.cml

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

Table 1. Selected geometric parameters (Å, °).

S1—O2	1.4433 (9)
S1—O1	1.4596 (8)
S1—O3	1.4600 (8)
S1—C1	1.7560 (12)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O1	0.885 (13)	1.944 (13)	2.8168 (11)	168.5 (12)
N1—H12⋯O3ⁱ	0.891 (13)	1.919 (13)	2.7944 (11)	166.9 (12)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank E. Hammes for technical support.

supplementary crystallographic information

Comment

More than one hundred structures are listed to date in the Cambridge Crystallographic Database, which include a diisopropylammonium cation (dipH). In most cases the dipH cation is the counter cation of bigger anionic species e.g. anionic complexes and clusters. A limited number of structures are reported that are solely constructed by small classical anions and the dipH cation. In these cases the structure type is strongly dependent on the geometry and the ability of these anions to form hydrogen bonds. The structures reported so far range from a quasi-molecular (dipH)₂[SiF₆] (Reiss, 1998), over cyclic dimers for some acetates (e.g.: Sada et al., 2004) and e.g. a substituted phosphate (Summers et al., 1998), to one-dimensional polymers for the halogenides and some pseudo-halogenides (literature cited in Reiss & Meyer, 2010). Even a two-dimensional hydrogen bonded network for the (dipH)₂SO₄ (Reiss & Engel, 2004) and three-dimensional networks for dipH[IrCl₆] (Reiss, 2002) and (dipH)₂[CdCl₄] (Reiss, 2010a) have been reported. The asymmetric unit of the title compound, which crystallizes in the centrosymmetric space group P2₁/n, consists of one formular unit. The structure is composed of centrosymmetric, hydrogen bonded, cyclic dimers which are composed of two dipH cations and two methanesulfonate anions arranged as rings (Fig. 1). The graph set (Etter et al., 1990) for these hydrogen bonded dimers is R₄⁴(12). All N–C, C–C, S–O, and S–C bond lengths are generally within the expected range. The two S–O bond lengths of the oxygen atoms involved in hydrogen bonding (O1 and O3) are longer than the third one which is in accord to our anticipation (Table 1). The N–H···O hydrogen bonds with donor-acceptor distances close to 2.79–2.82 Å (Table 2) are in the range of medium strong hydrogen bonds. The R₄⁴(12) hydrogen bonding motif is well known for dipH acetates (Reiss & Meyer, 2010, Sada et al. 2004). Combinations of the dipH cation with structurally similar anions like [NO₃]^– (Reiss, 2010b), [ClO₄]^- (Bajorat & Reiss, 2007) and various substituted carboxylate anions can be described as the generalized synthon: {dipH}⁺{O₂XR_y}^- (X = C, Cl, N; y = 1,2, R = O, C). The title structure is a further example with this supramolecular synthon and the typical cyclic dimer.

Experimental

Diisopropylammonium methanesulfonate, ((CH₃)₂CH)₂NH₂[CH₃SO₃] was prepared by the reaction of 0.72 g (7.12 mmol) diisopropylamine and 1.48 g (15.40 mmol) methanesulfonic acid at room temperature. From colourless solution small block-shaped crystals were obtained within a few days. A Raman spectrum was measured using a Bruker MULTIRAM spectrometer; Nd:YAG-Laser at 1064 nm; RT-InGaAS-detector; 4000–70 cm^-1: 3022(sh), 2986(ν(C–H), s), 2944(ν(C–H), vs), 2784(ν(N–H), w), 1462 (δ(C–H, m), 1429(δ(C–H, m), 1350(w), 1315(w), 1227(w), 1183(w), 1158(w), 1099 (w), 1044 (ν(S–O),vs), 958 (w), 914(w), 808(s), 778(ν(C–S), s), 558(δ(S–O), s), 528(m), 470(m), 392(w), 348(ρ(S–O), br), 83(m). IR data collected on a Digilab FT3400 spectrometer using a MIRacle ATR unit (Pike Technologies); 4000–560 cm^-1: 3019(ν(C–H), s), 2988 (sh), 2941(m), 2870(ν(C–H), s), 2781(ν(N–H), m), 2514(m), 1625(w), 1601(w), 1483(δ(C–H, m), 1416(w), 1397(m), 1331(w), 1314(w), 1206(vs), 1177(sh), 1153(ν_s(S–O), vs), 1100(m), 1040(ν_a(S–O), vs), 977(w), 954(w), 837(w), 805(w), 776(ν(C–S), s), 551(δ(S–O)s). Band assignments for Raman and IR spectroscopic data were made by comparing results of earlier work done on sodium- and caesium methanesulfonate (Thomson, 1972), magnesium sulfonate (Genceli Guner et al., 2010) and dipHCl (Reiss & Meyer 2010).