Earth Alkaline Tetrathiosquarates: Syntheses and Crystal Structures of MgC4S4 · 6 H2O and CaC4S4 · 4 H2O |
| |
Authors: | Johannes Beck Prof Dr Younis Ben‐Amer |
| |
Institution: | 1. Bonn, Institut für Anorganische Chemie der Universit?tInst. f. Anorg. Chemie d. Universit?t, Gerhard‐Domagk‐Str. 1, D‐53121 Bonn;2. Bonn, Institut für Anorganische Chemie der Universit?t |
| |
Abstract: | Concentrated aqueous solutions of magnesium chloride and calcium nitrate, respectively, allow on addition of the potassium salt of tetrathiosquarate, K2C4S4 · H2O, the isolation of the earth alkaline salts MgC4S4 · 6 H2O ( 1 ) and CaC4S4 · 4 H2O ( 2 ) as orange and red crystals. The crystal structure determinations ( 1 : monoclinic, C2/c, a = 17.2280(7), b = 5.9185(2), c = 13.1480(4) Å, β = 104.730(3)°, Z = 4; 2 : monoclinic, P21/m, a = 7.8515(3), b = 12.7705(5), c = 10.6010(4) Å, β = 93.228(2)°, Z = 4) show the presence of C4S42? ions with almost undistorted D4h symmetry having average C–C and C–S bond lengths of 1.451Å and 1.659Å for 1 and 1.451Å and 1.655Å for 2 . The structure of 1 contains discrete, octahedral Mg(H2O)6]2+ complexes. Several O–H····O and O–H····S bridges with H····O and H····S distances of less than 2.50Å connect cations and anions. The structure of 2 is built of concatenated, edge‐sharing Ca(H2O)6S2 polyhedra. The Ca2+ ions have the coordination number eight, C4S42? act as a chelating ligands towards Ca2+ with Ca–S distances of 3.14Å. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds. |
| |
Keywords: | Tetrathiosquarate Cyclobutene‐1 2‐dithiolate‐3 4‐dithione(2– ) Magnesium Calcium Hydrogen bonds Vibrational spectra Crystal structure |
|
|