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The solvothermal reaction of MnCl 2 ·4 H 2 O, K 2 Se 3  and Se in trans-cyclohexane-1,2-diamine (chxn) at 433 K yields dark blue crystals of [Mn(chxn) 3 ]Se 6  (1), and the reaction of MnCl 2  ・4 H 2 O, K 2 Se 3  and Te under similar conditions gives dark blue crystals of [Mn(chxn) 3 ] 2 [H 2 chxn](TeSe 2 ) 2 Se (2). While compound (1) crystallises in the orthorhombic space group Pbcn with the lattice parameters a = 13.7017(9), b = 19.9073(8) and c = 10.8058(5)Å , compound (2) crystallises in the monoclinic space group P2 1  with the lattice parameters a = 9.4396(6), b = 24.2450(2), c = 12.8170(8) Å and β =91.6(1)◦. In both structures discrete complex cations and polychalcogenide anions are found. In (1) the Se 6  2−  anions form a pseudo-layer arrangement with nearly rectangular pores. The complex cations are encapsulated by the arrangement of the Se 6  2−  anions. Some short distances between the amino groups of the ligands and the anions indicate weak hydrogen bonding. In compound (2) two independent [Mn(chxn) 3 ] 2+  and one unique H 2 chxn dications, two unique TeSe 2  2−  as well as one Se 2−  dianion coexist. The two complex cations exhibit different conformations. One of the two TeSe 2  2−  anions has the di-protonated chxn molecule in the neighbourhood and short Se···H separations indicate weak hydrogen bonding. The isolated Se 2−  ion is located above the ring of the di-protonated trans-cyclohexane-1,2-diamine molecule and again a short Se···H separation may be due to a weak hydrogen bond. Compound (1) decomposes in a single step when heated in an Ar atmosphere. In contrast, the thermal decomposition of compound (2) is complex and at least five different steps can be identified.

zeitschrift für naturforschung b

Syntheses and Crystal Structures of the Two New Polychalcogenides [Mn(C 6 H 14 N 2 ) 3 ]Se 6  and [Mn(C 6 H 14 N 2 ) 3 ] 2 [C 6 H 16 N 2 ](TeSe 2 ) 2 Se