Zeitschrift fur Naturforschung, B: Chemical Sciences (2019)
Update date:2022-08-10
Topics:
Langenmaier, Michael
R?hr, Caroline
A series of new sodium and mixed Na/A (A = K, Rb, Cs) tellurido manganates have been synthesized from melts of the pure elements (or MnTe) at maximum temperatures of 600-1000°C. The monoclinic crystal structures of the two pure sodium salts Na2Mn2Te3 (space group C2/c, a = 1653.68(2), b = 1482.57(2), c = 773.620(10) pm, β = 117.52°, Z = 8, R1 = 0.0225) and Na2Mn3Te4 (space group C2/m, a = 1701.99(3), b = 438.741(8), c = 691.226(12) pm, β = 90.3171(8)°, Z = 2, R1 = 0.0270) are both based on a hexagonal close packed Te2- arrangement. Na2Mn2Te3 is isotypic with Na2Mn2S3 and Na2Mn2Se3 and contains layers of [MnTe4] tetrahedra, which are connected via common edges to form tetramers [Mn4Te6]. These tetramers are further connected via μ3-Te atoms. Na2Mn3Te4 crystallizes in a new structure type, recently also reported for the selenido salt Na2Mn3Se4. Mn(2) forms ribbons of vertex-sharing dinuclear units ∞1[Te2/2MnTe2MnTe2/2] USD_infty ^1[{rm{T}}{{rm{e}}_{2/2}}{rm{MnT}}{{rm{e}}_2}{rm{MnT}}{{rm{e}}_{2/2}}]USD running along the short b axis of the monoclinic cell. The Te atoms of these ribbons are also the ligands of edge-sharing [Mn(1)Te6] chains of octahedra. Similar to Na2Mn2Te3, the Na+ cations are octahedrally coordinated and the cations occupy tetrahedral (Mn2+) and octahedral (Na+, Mn2+) voids in the close Te2- packing. The isotypic K/Rb salts Na2AMnTe3 crystallize in a new structure type (orthorhombic, space group Pmc21, a = 1069.70(4)/1064.34(2), b = 1350.24(5)/1350.47(3), c = 1238.82(4)/1236.94(3) pm, Z = 4, R1 = 0.0445/0.0210). In contrast to the simple formula indicating a Mn(III) compound, the complex structure contains one layer consisting of undulated chains of edge-sharing tetrahedra ∞1[MnIITe4/2] USD_infty ^1[{rm{M}}{{rm{n}}^{{rm{II}}}}{rm{T}}{{rm{e}}_{4/2}}]USD separated by free ditelluride dumbbells [Te2]2- and a second layer containing a complex chain of edge- A nd vertex-sharing [MnIITe4] tetrahedra, in which Mn(II) is coordinated to μ1- A nd μ2-Te2- ligands and an η1-ditellurido ligand. The cesium salt NaCsMnTe2 (orthorhombic, space group Cccm, a = 694.21(2), b = 1536.57(4), c = 664.47(2) pm, Z = 4, R1 = 0.0131) likewise forms a new structure type, which is an ordered superstructure of ThCr2Si2. Linear chains ∞1[MnTe4/2] USD_infty ^1[{rm{MnT}}{{rm{e}}_{4/2}}]USD of edge-sharing tetrahedra are connected with similar chains ∞1[NaTe4/2] USD_infty ^1[{rm{NaT}}{{rm{e}}_{4/2}}]USD to form [NaMnTe2] layers. The larger alkali cations Cs+ between the layers exhibit a cubic (CN = 8) coordination.
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