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Structure and Thermolysis of Lithium Methanesulfonate

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Thomas Stomberg at Altana AG
Thomas Stomberg
Walter Frank
Walter Frank
Walter Frank
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Abstract

So far, lithium has been the only alkali metal with no extensively characterized methane-sulfonate. Colourless, notoriously twinned platelets of LiCH3SO3 (1) were obtained from an aqueous solution of Li2CO3 and methanesulfonic acid at RT. 1 crystallizes in the monoclinic space group C2/m with a = 7.8586(16) Å, b = 7.4889(15) Å, c = 6.5454(13) Å, β = 90.234(15)°, V = 385.21(13) Å3, Z = 4, R1 = 0.025 and wR2 = 0.072. The Li+ ion is tetrahedrally surrounded by O atoms of four anions. One anion links four cations in a 1κO:2κO:3κO’:4κO’’ mode, constructing a 2D network within the ab plane. Along the c axis, these layers are connected by van der Waals interactions. In nitrogen (air), 1 melts at about 641 K and decomposes when reaching 670 K (658 K), leaving Li2CO3 as the residue.
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T. Tr el la a nd W. Fran k
Institut für Anorganische Chemie und Strukturchemie II
Heinrich-Heine-Universität Düsseldorf
D-40225 Düsseldorf
E-Mail: wfrank@hhu.de
Structure and Thermolysis of Lithium Methanesulfonate
Regarding catalysis and crystal engineering, the properties of methanesulfonates as biodegradable Lewis acids[1,2] and as
components of layered inorganic-organic hybrid materials[3] have been increasingly investigated during the last decade. They
are throughout excellently water-soluble, stable up to about 400 °C in anhydrous state and practically inert against hydrolyzing,
oxidizing or reducing agents.[4]
So far, lithium has been the only alkali metal with no extensively characterized methanesulfonate.[5-8] Colourless, notoriously
twinned platelets of lithium methanesulfonate,LiCH3SO3(1), were obtained from an aqueous solution of lithium carbonate
and a stoichiometric amount of methanesulfonic acid at room temperature. 1crystallizes in the monoclinic space group C2/m
with a= 7.8586(16) Å, b= 7.4889(15) Å, c= 6.5454(13) Å, β= 90.234(15)°, V= 385.21(13) Å3,Z= 4; structure determination:
R1= 0.025 and wR2= 0.072.
Fig. 1. Vibration spectra of 1.
Fig. 2. Building unit of the hydrophilic layers.
Fig. 3. View along [110]; displaying the separation of the solid
into organic-inorganic layers.
Fig. 4. DTA/TG diagram of 1. 298-923 K, 5 K/min, N2.
The Li+ion is tetrahedrally surrounded by oxygen atoms of
four anions with tetrahedral angles of 86.43° to 115.53°. One
anion links four cations in a 1κO:2κO:3κO’:4κO’’ mode,
constructing a two-dimensional network parallel to the ab
plane (Fig. 2).
Remarkable for a methanesulfonate, 1shows a distinct melting
point of about 641 K. In nitrogen (air), it decomposes when
reaching 670 K (658 K), leaving Li2CO3as the residue.
Along the caxis, these layers are connected by van der Waals
interactions between the anions’ methyl groups (Fig. 3).
17. Vortragstagung Innovative Materialsynthesen, Dresden, 15th-17th September 2014
References:
[1] M. Wang, G. F. Tian, Z. G. Song, H. Jiang, Chin. Chem. Lett. 2009, 20, 1034. [5] R. J. Capwell, K. H. Rhee, K. S. Seshadri, Spectrochim. Acta 1968, 24A, 955.
[2] Z. Song, X. Sun, L. Liu, Y. Cui, Res. Chem. Intermed. 2013, 39, 2123. [6] C. H. Wei, B. E. Hingerty, Acta Crystallogr. 1981, B37, 1992.
[3] T. Trella, W. Frank, Acta Crystallogr. 2012, E68, m1136. [7] J. Volk, W. Frank, Z. Krist. Suppl. 2012, 32, 111.
[4] M. D. Gernon, M. Wu, T. Buszta, P. Janney, Green Chem. 1999, 1, 127. [8] J. K. Brandon, I. D. Brown, Can. J. Chem. 1967, 45, 1385.
DTA
TG
... The structures of the lithium and potassium salts of methanesulfonic acid have been previously determined; however, as far as we are aware, neither has been deposited in a recognized database, [20]. Brief descriptions are provided in conference abstracts (Li [21], K [22]), and the atomic coordinates of the Li salt are given in a thesis [23]; those of the K salt are unavailable. The structure is an essential requirement for the periodic-DFT calculations that we will use to assign the spectra; accordingly, we have re-determined both structures. ...
... There is an apparent second smaller mixed ring (highlighted by the small circle in figure 2); however, this is deceiving because as figure 3 shows, the methyl and sulfonate groups 'interdigitate' to minimize the interactions. [21,23,26] and the infrared spectrum of the K salt [30] have been reported previously. The present spectra are in general agreement with the literature spectra but have an extended transition energy range, and the INS spectra are previously unreported. ...
Structure and vibrational spectroscopy of lithium and potassium methanesulfonates
Article
Full-text available
  • Jul 2020
In this work, we have determined the structures of lithium methanesulfonate, Li(CH3SO3), and potassium methanesulfonate, K(CH3SO3), and analysed their vibrational spectra. The lithium salt crystallizes in the monoclinic space group C2/m with two formula units in the primitive cell. The potassium salt is more complex, crystallizing in I4/m with 12 formula units in the primitive cell. The lithium ion is fourfold coordinated in a distorted tetrahedron, while the potassium salt exhibits three types of coordination: six-, seven- and ninefold. Vibrational spectroscopy of the compounds (including the 6Li and 7Li isotopomers) confirms that the correlation previously found, that in the infrared spectra there is a clear distinction between coordinated and not coordinated forms of the methanesulfonate ion, is also valid here. The lithium salt shows a clear splitting of the asymmetric S-O stretch mode, indicating a bonding interaction, while there is no splitting in the spectrum of the potassium salt, consistent with a purely ionic material.
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  • Jan 1967
  • CAN J CHEM
  • 127-172
  • M D Gernon
  • M Wu
  • T Buszta
  • P Janney
  • Green Chem
M. D. Gernon, M. Wu, T. Buszta, P. Janney, Green Chem. 1999, 1, 127. [8] J. K. Brandon, I. D. Brown, Can. J. Chem. 1967, 45, 1385.
  • Feb 1981
  • Z Song
  • X Sun
  • L Liu
  • Y Cui
Z. Song, X. Sun, L. Liu, Y. Cui, Res. Chem. Intermed. 2013, 39, 2123. [6] C. H. Wei, B. E. Hingerty, Acta Crystallogr. 1981, B37, 1992.
  • Jan 2009
  • 1034
  • M Wang
  • G F Tian
  • Z G Song
  • H Jiang
M. Wang, G. F. Tian, Z. G. Song, H. Jiang, Chin. Chem. Lett. 2009, 20, 1034.
  • Jan 1968
  • Spectrochim Acta
  • 955
  • R J Capwell
  • K H Rhee
  • K S Seshadri
R. J. Capwell, K. H. Rhee, K. S. Seshadri, Spectrochim. Acta 1968, 24A, 955.
  • Jan 2012
  • Acta Crystallogr
  • 1136
  • T Trella
  • W Frank
T. Trella, W. Frank, Acta Crystallogr. 2012, E68, m1136.