NaMnTe2 crystallizes in the trigonal P3m1 space group. Na(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form NaTe6 octahedra that share corners with six equivalent Mn(1)Te4 tetrahedra, edges with six equivalent Na(1)Te6 octahedra, and edges with three equivalent Mn(1)Te4 tetrahedra. Mn(1) is bonded to one Te(1) and three equivalent Te(2) atoms to form MnTe4 tetrahedra that share corners with six equivalent Na(1)Te6 octahedra, corners with six equivalent Mn(1)Te4 tetrahedra, and edges with three equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 18-51°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to three equivalent Na(1) and one Mn(1) atom. In the second Te site, Te(2) is bonded to three equivalent Na(1) and three equivalent Mn(1) atoms to form distorted edge-sharing TeNa3Mn3 octahedra.
NaMnTe2 crystallizes in the trigonal P3m1 space group. Na(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form NaTe6 octahedra that share corners with six equivalent Mn(1)Te4 tetrahedra, edges with six equivalent Na(1)Te6 octahedra, and edges with three equivalent Mn(1)Te4 tetrahedra. All Na(1)-Te(1) bond lengths are 3.18 Å. All Na(1)-Te(2) bond lengths are 3.35 Å. Mn(1) is bonded to one Te(1) and three equivalent Te(2) atoms to form MnTe4 tetrahedra that share corners with six equivalent Na(1)Te6 octahedra, corners with six equivalent Mn(1)Te4 tetrahedra, and edges with three equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 18-51°. The Mn(1)-Te(1) bond length is 2.53 Å. All Mn(1)-Te(2) bond lengths are 2.73 Å. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to three equivalent Na(1) and one Mn(1) atom. In the second Te site, Te(2) is bonded to three equivalent Na(1) and three equivalent Mn(1) atoms to form distorted edge-sharing TeNa3Mn3 octahedra.