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Earth Alkaline Tetrathiosquarates: Syntheses and Crystal Structures of MgC 4 S 4 · 6 H 2 O and CaC 4 S 4 · 4 H 2 O
Author(s) -
Beck Johannes,
BenAmer Younis
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200600334
Subject(s) - monoclinic crystal system , chemistry , octahedron , alkaline earth metal , crystal structure , crystallography , infrared spectroscopy , bond length , alkali metal , stereochemistry , organic chemistry
Abstract Concentrated aqueous solutions of magnesium chloride and calcium nitrate, respectively, allow on addition of the potassium salt of tetrathiosquarate, K 2 C 4 S 4 · H 2 O, the isolation of the earth alkaline salts MgC 4 S 4 · 6 H 2 O ( 1 ) and CaC 4 S 4 · 4 H 2 O ( 2 ) as orange and red crystals. The crystal structure determinations ( 1 : monoclinic, C 2/ c , a = 17.2280(7), b = 5.9185(2), c = 13.1480(4) Å, β = 104.730(3)°, Z = 4; 2 : monoclinic, P 2 1 / m , a = 7.8515(3), b = 12.7705(5), c = 10.6010(4) Å, β = 93.228(2)°, Z = 4) show the presence of C 4 S 4 2− ions with almost undistorted D 4 h 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(H 2 O) 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(H 2 O) 6 S 2 polyhedra. The Ca 2+ ions have the coordination number eight, C 4 S 4 2− act as a chelating ligands towards Ca 2+ with Ca–S distances of 3.14Å. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds.