(Na)2NaSi34 crystallizes in the trigonal R-3m space group. The structure consists of six 7440-23-5 atoms inside a NaSi34 framework. In the NaSi34 framework, Na(2) is bonded in a 20-coordinate geometry to two equivalent Si(3), six equivalent Si(2), and twelve equivalent Si(5) atoms. There are six inequivalent Si sites. In the first Si site, Si(1) is bonded to one Si(3) and three equivalent Si(4) atoms to form corner-sharing SiSi4 tetrahedra. In the second Si site, Si(2) is bonded in a 5-coordinate geometry to one Na(2), one Si(3), one Si(6), and two equivalent Si(5) atoms. In the third Si site, Si(3) is bonded in a distorted pentagonal planar geometry to one Na(2), one Si(1), and three equivalent Si(2) atoms. In the fourth Si site, Si(4) is bonded to one Si(1), one Si(6), and two equivalent Si(5) atoms to form corner-sharing SiSi4 tetrahedra. In the fifth Si site, Si(5) is bonded in a 5-coordinate geometry to one Na(2), one Si(2), one Si(4), and two equivalent Si(5) atoms. In the sixth Si site, Si(6) is bonded to one Si(2), one Si(4), and two equivalent Si(6) atoms to form corner-sharing SiSi4 tetrahedra.
(Na)2NaSi34 crystallizes in the trigonal R-3m space group. The structure consists of six 7440-23-5 atoms inside a NaSi34 framework. In the NaSi34 framework, Na(2) is bonded in a 20-coordinate geometry to two equivalent Si(3), six equivalent Si(2), and twelve equivalent Si(5) atoms. Both Na(2)-Si(3) bond lengths are 3.19 Å. All Na(2)-Si(2) bond lengths are 3.26 Å. All Na(2)-Si(5) bond lengths are 3.36 Å. There are six inequivalent Si sites. In the first Si site, Si(1) is bonded to one Si(3) and three equivalent Si(4) atoms to form corner-sharing SiSi4 tetrahedra. The Si(1)-Si(3) bond length is 2.34 Å. All Si(1)-Si(4) bond lengths are 2.36 Å. In the second Si site, Si(2) is bonded in a 5-coordinate geometry to one Na(2), one Si(3), one Si(6), and two equivalent Si(5) atoms. The Si(2)-Si(3) bond length is 2.35 Å. The Si(2)-Si(6) bond length is 2.36 Å. Both Si(2)-Si(5) bond lengths are 2.37 Å. In the third Si site, Si(3) is bonded in a distorted pentagonal planar geometry to one Na(2), one Si(1), and three equivalent Si(2) atoms. In the fourth Si site, Si(4) is bonded to one Si(1), one Si(6), and two equivalent Si(5) atoms to form corner-sharing SiSi4 tetrahedra. The Si(4)-Si(6) bond length is 2.39 Å. Both Si(4)-Si(5) bond lengths are 2.35 Å. In the fifth Si site, Si(5) is bonded in a 5-coordinate geometry to one Na(2), one Si(2), one Si(4), and two equivalent Si(5) atoms. There is one shorter (2.35 Å) and one longer (2.40 Å) Si(5)-Si(5) bond length. In the sixth Si site, Si(6) is bonded to one Si(2), one Si(4), and two equivalent Si(6) atoms to form corner-sharing SiSi4 tetrahedra. Both Si(6)-Si(6) bond lengths are 2.35 Å.