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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 Na 2 Mn 2 Te 3  (space group  C 2/ c ,  a  = 1653.68(2),  b  = 1482.57(2),  c  = 773.620(10) pm,  β  = 117.52°,  Z  = 8,  R 1 = 0.0225) and Na 2 Mn 3 Te 4  (space group  C 2/ m ,  a  = 1701.99(3),  b  = 438.741(8),  c  = 691.226(12) pm,  β  = 90.3171(8)°,  Z  = 2,  R 1 = 0.0270) are both based on a hexagonal close packed Te 2−  arrangement. Na 2 Mn 2 Te 3  is isotypic with Na 2 Mn 2 S 3  and Na 2 Mn 2 Se 3  and contains layers of [MnTe 4 ] tetrahedra, which are connected  via  common edges to form tetramers [Mn 4 Te 6 ]. These tetramers are further connected  via μ  3 -Te atoms. Na 2 Mn 3 Te 4  crystallizes in a new structure type, recently also reported for the selenido salt Na 2 Mn 3 Se 4 . Mn(2) forms ribbons of vertex-sharing dinuclear units∞  1   [    Te    2  /  2MnTe   2MnTe    2  /  2    ]    $_\infty ^1[{\rm{T}}{{\rm{e}}_{2/2}}{\rm{MnT}}{{\rm{e}}_2}{\rm{MnT}}{{\rm{e}}_{2/2}}]$    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)Te 6 ] chains of octahedra. Similar to Na 2 Mn 2 Te 3 , the Na +  cations are octahedrally coordinated and the cations occupy tetrahedral (Mn 2+ ) and octahedral (Na + , Mn 2+ ) voids in the close Te 2−  packing. The isotypic K/Rb salts Na 2  A MnTe 3  crystallize in a new structure type (orthorhombic, space group  Pmc 2 1 ,  a  = 1069.70(4)/1064.34(2),  b  = 1350.24(5)/1350.47(3),  c  = 1238.82(4)/1236.94(3) pm,  Z  = 4,  R 1 = 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   [    Mn    IITe    4  /  2    ]    $_\infty ^1[{\rm{M}}{{\rm{n}}^{{\rm{II}}}}{\rm{T}}{{\rm{e}}_{4/2}}]$    separated by free ditelluride dumbbells [Te 2 ] 2−  and a second layer containing a complex chain of edge- and vertex-sharing [Mn II Te 4 ] tetrahedra, in which Mn(II) is coordinated to  μ  1 - and  μ  2 -Te 2−  ligands and an  η  1 -ditellurido ligand. The cesium salt NaCsMnTe 2  (orthorhombic, space group  Cccm ,  a  = 694.21(2),  b  = 1536.57(4),  c  = 664.47(2) pm,  Z  = 4,  R 1 = 0.0131) likewise forms a new structure type, which is an ordered superstructure of ThCr 2 Si 2 . Linear chains∞  1   [    MnTe    4  /  2    ]    $_\infty ^1[{\rm{MnT}}{{\rm{e}}_{4/2}}]$    of edge-sharing tetrahedra are connected with similar chains∞  1   [    NaTe    4  /  2    ]    $_\infty ^1[{\rm{NaT}}{{\rm{e}}_{4/2}}]$    to form [NaMnTe 2 ] layers. The larger alkali cations Cs +  between the layers exhibit a cubic (CN = 8) coordination.

The new sodium tellurido manganates(II) Na 2 Mn 2 Te 3 , Na 2 Mn 3 Te 4 , Na 2 A MnTe 3 ( A =K, Rb), and NaCsMnTe 2