Issue 45, 2013

Coordination polymers of alkali metal trithiocyanurates: structure determinations and ionic conductivity measurements using single crystals

Abstract

Six novel crystalline coordination polymers composed of alkali metal ions and trithiocyanurate anions (C3N3S3H2 = ttcH2) were synthesized. Single crystals were used both for structure determinations by X-ray diffraction and ionic conductivity measurements by AC impedance methods. The structures are: (i) sodium trithiocyanurate trihydrate, Na(ttcH2)(H2O)3 in space group P21; (ii) potassium trithiocyanurate hydrate, K(ttcH2)(H2O) in P[1 with combining macron]; (iii) rubidium trithiocyanurate hydrate, Rb(ttcH2)(H2O) in P[1 with combining macron]; (iv) rubidium trithiocyanurate hydrate, Rb3(ttcH2)2(ttcH3)2(H2O)5(OH) in P[1 with combining macron]; and (v, vi) two anhydrous polymorphs of caesium trithiocyanurates, Cs(ttcH2) in P[1 with combining macron] and Cc. With the exception of the sodium phase, which is layered, all of these compounds consist of three dimensional coordination networks. In all systems, the inorganic regions are interleaved by arrays of ttcH2 anions. The most interesting feature of this system is the thiol-rich environment formed between the trithiocyanurate layers, where alkali metal ions are located. Water molecules, where present, are always coordinated to a cation. Among these crystals, K(ttcH2)(H2O) exhibited proton conductivity under atmospheric conditions (25 ± 0.2 °C): 1.1 × 10−5 S cm−1 in the direction perpendicular to the bc plane and 3.1 × 10−6 S cm−1 along the c axis.

Graphical abstract: Coordination polymers of alkali metal trithiocyanurates: structure determinations and ionic conductivity measurements using single crystals

Supplementary files

Article information

Article type
Paper
Submitted
15 jun 2013
Accepted
16 jul 2013
First published
17 jul 2013

CrystEngComm, 2013,15, 9400-9407

Coordination polymers of alkali metal trithiocyanurates: structure determinations and ionic conductivity measurements using single crystals

S. Tominaka, S. Henke and A. K. Cheetham, CrystEngComm, 2013, 15, 9400 DOI: 10.1039/C3CE41150H

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