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The metallic lustrous compounds Na 2 K 3 [SnP 3 ], Na 2 Cs 3 [SnP 3 ], and Na 2 K 3 [SnBi 3 ] were prepared from melts of mixtures of the elements. The isotypic compounds Na 2 K 3 [SnP 3 ] and Na 2 Cs 3 [SnP 3 ] crystallize in the orthorhombic system, space group Cmca (No 64), Z = 8, with lattice constants a = 1996.1 (4)/2047.9(4) pm, b = 669.5(1)/686.5(2) pm, c = 1494.5(2)/1617.8(3) pm. The structure is characterized by dimeric units [Sn 2 P 6 ]  10-  of edge-sharing [SnP 4 ] tetrahe­dra, which are coordinated by the alkali cations. Na 2 K 3 [SnBi 3 ] crystallizes in the orthorhombic system, space group Ibca (No 73), Z = 8, with lattice constants a = 718.2(1) pm , b -1692.6(2) pm, c = 2159.5(2) pm. In the anionic partial structure [SnBi 4 ] tetrahedra are connected via common corners to infinite  1  ∞ [SnBi 3 ] 5-  Zweier single chains. The sodium and potassium cat­ ions separate the chains from each other. Neglecting the distortions caused by covalent bonding and different radii both structure types can be classified as superstructure defect variants of the Li 3 Bi structure. Different orderings in the occupation of the tetrahedral voids lead to the variants in the anionic assemblies.

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Dimere und polymere Pnictidostannat(IV)-Anionen -Darstellung und Kristallstrukturen von Na 2 K 3 [SnP 3 ], Na 2 Cs 3 [SnP 3 ] und Na 2 K 3 [SnBi 3 ] / Dimeric and Polymeric Pnictidostannate(IV) Anions -Preparation and Crystal Structures of Na 2 K 3 [SnP 3 ], Na 2 Cs 3 [SnP 3 ] and Na 2 K 3 [SnBi 3 ]