Na1Mo6Se8 crystallizes in the trigonal R-3 space group. Na(1) is bonded in a body-centered cubic geometry to two equivalent Se(2) and six equivalent Se(1) atoms. Mo(1) is bonded to one Se(2) and four equivalent Se(1) atoms to form a mixture of distorted corner and edge-sharing MoSe5 square pyramids. There are two inequivalent Se sites. In the first Se site, Se(2) is bonded in a 4-coordinate geometry to one Na(1) and three equivalent Mo(1) atoms. In the second Se site, Se(1) is bonded to one Na(1) and four equivalent Mo(1) atoms to form a mixture of distorted corner and edge-sharing SeNaMo4 trigonal bipyramids.
Na1Mo6Se8 crystallizes in the trigonal R-3 space group. Na(1) is bonded in a body-centered cubic geometry to two equivalent Se(2) and six equivalent Se(1) atoms. Both Na(1)-Se(2) bond lengths are 2.80 Å. All Na(1)-Se(1) bond lengths are 3.25 Å. Mo(1) is bonded to one Se(2) and four equivalent Se(1) atoms to form a mixture of distorted corner and edge-sharing MoSe5 square pyramids. The Mo(1)-Se(2) bond length is 2.53 Å. There are a spread of Mo(1)-Se(1) bond distances ranging from 2.57-2.74 Å. There are two inequivalent Se sites. In the first Se site, Se(2) is bonded in a 4-coordinate geometry to one Na(1) and three equivalent Mo(1) atoms. In the second Se site, Se(1) is bonded to one Na(1) and four equivalent Mo(1) atoms to form a mixture of distorted corner and edge-sharing SeNaMo4 trigonal bipyramids.