NaSi crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to two equivalent Si(1) and three equivalent Si(2) atoms. In the second Na site, Na(2) is bonded in a 3-coordinate geometry to three equivalent Si(1) and three equivalent Si(2) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), three equivalent Na(2), one Si(1), and two equivalent Si(2) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to three equivalent Na(1), three equivalent Na(2), one Si(2), and two equivalent Si(1) atoms.
NaSi crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to two equivalent Si(1) and three equivalent Si(2) atoms. Both Na(1)-Si(1) bond lengths are 3.04 Å. There are a spread of Na(1)-Si(2) bond distances ranging from 2.87-3.29 Å. In the second Na site, Na(2) is bonded in a 3-coordinate geometry to three equivalent Si(1) and three equivalent Si(2) atoms. There are a spread of Na(2)-Si(1) bond distances ranging from 2.99-3.26 Å. There are a spread of Na(2)-Si(2) bond distances ranging from 3.08-3.38 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), three equivalent Na(2), one Si(1), and two equivalent Si(2) atoms. The Si(1)-Si(1) bond length is 2.41 Å. There is one shorter (2.38 Å) and one longer (2.40 Å) Si(1)-Si(2) bond length. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to three equivalent Na(1), three equivalent Na(2), one Si(2), and two equivalent Si(1) atoms. The Si(2)-Si(2) bond length is 2.45 Å.