BaSi2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to two equivalent Si(3), three equivalent Si(2), and six equivalent Si(1) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to two equivalent Si(2), three equivalent Si(3), and four equivalent Si(1) atoms. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 8-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), one Si(1), one Si(2), and one Si(3) atom. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), one Si(3), and two equivalent Si(1) atoms. In the third Si site, Si(3) is bonded in a 8-coordinate geometry to two equivalent Ba(1), three equivalent Ba(2), one Si(2), and two equivalent Si(1) atoms.
BaSi2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to two equivalent Si(3), three equivalent Si(2), and six equivalent Si(1) atoms. There is one shorter (3.73 Å) and one longer (3.85 Å) Ba(1)-Si(3) bond length. There are two shorter (3.49 Å) and one longer (3.56 Å) Ba(1)-Si(2) bond length. There are a spread of Ba(1)-Si(1) bond distances ranging from 3.46-3.56 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to two equivalent Si(2), three equivalent Si(3), and four equivalent Si(1) atoms. There is one shorter (3.40 Å) and one longer (3.60 Å) Ba(2)-Si(2) bond length. There is one shorter (3.41 Å) and two longer (3.66 Å) Ba(2)-Si(3) bond lengths. All Ba(2)-Si(1) bond lengths are 3.47 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a 8-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), one Si(1), one Si(2), and one Si(3) atom. The Si(1)-Si(1) bond length is 2.39 Å. The Si(1)-Si(2) bond length is 2.38 Å. The Si(1)-Si(3) bond length is 2.40 Å. In the second Si site, Si(2) is bonded in a 8-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), one Si(3), and two equivalent Si(1) atoms. The Si(2)-Si(3) bond length is 2.41 Å. In the third Si site, Si(3) is bonded in a 8-coordinate geometry to two equivalent Ba(1), three equivalent Ba(2), one Si(2), and two equivalent Si(1) atoms.