Ba2LiSi3 crystallizes in the orthorhombic Fddd space group. Li(1) is bonded in a trigonal planar geometry to two equivalent Ba(2), four equivalent Ba(1), one Si(2), and two equivalent Si(1) atoms. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to four equivalent Li(1), two equivalent Si(2), and six equivalent Si(1) atoms to form distorted BaLi4Si8 cuboctahedra that share edges with six equivalent Ba(2)Li2Si10 cuboctahedra, edges with six equivalent Ba(1)Li4Si8 cuboctahedra, faces with three equivalent Ba(1)Li4Si8 cuboctahedra, and faces with five equivalent Ba(2)Li2Si10 cuboctahedra. In the second Ba site, Ba(2) is bonded to two equivalent Li(1), four equivalent Si(2), and six equivalent Si(1) atoms to form distorted BaLi2Si10 cuboctahedra that share edges with six equivalent Ba(2)Li2Si10 cuboctahedra, edges with six equivalent Ba(1)Li4Si8 cuboctahedra, faces with three equivalent Ba(2)Li2Si10 cuboctahedra, and faces with five equivalent Ba(1)Li4Si8 cuboctahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a distorted single-bond geometry to one Li(1), three equivalent Ba(1), and three equivalent Ba(2) atoms. In the second Si site, Si(2) is bonded in a distorted single-bond geometry to one Li(1), two equivalent Ba(1), and four equivalent Ba(2) atoms.
Ba2LiSi3 crystallizes in the orthorhombic Fddd space group. Li(1) is bonded in a trigonal planar geometry to two equivalent Ba(2), four equivalent Ba(1), one Si(2), and two equivalent Si(1) atoms. Both Li(1)-Ba(2) bond lengths are 3.51 Å. All Li(1)-Ba(1) bond lengths are 3.53 Å. The Li(1)-Si(2) bond length is 2.66 Å. Both Li(1)-Si(1) bond lengths are 2.68 Å. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to four equivalent Li(1), two equivalent Si(2), and six equivalent Si(1) atoms to form distorted BaLi4Si8 cuboctahedra that share edges with six equivalent Ba(2)Li2Si10 cuboctahedra, edges with six equivalent Ba(1)Li4Si8 cuboctahedra, faces with three equivalent Ba(1)Li4Si8 cuboctahedra, and faces with five equivalent Ba(2)Li2Si10 cuboctahedra. Both Ba(1)-Si(2) bond lengths are 3.58 Å. There are a spread of Ba(1)-Si(1) bond distances ranging from 3.51-3.61 Å. In the second Ba site, Ba(2) is bonded to two equivalent Li(1), four equivalent Si(2), and six equivalent Si(1) atoms to form distorted BaLi2Si10 cuboctahedra that share edges with six equivalent Ba(2)Li2Si10 cuboctahedra, edges with six equivalent Ba(1)Li4Si8 cuboctahedra, faces with three equivalent Ba(2)Li2Si10 cuboctahedra, and faces with five equivalent Ba(1)Li4Si8 cuboctahedra. There are two shorter (3.43 Å) and two longer (3.57 Å) Ba(2)-Si(2) bond lengths. There are a spread of Ba(2)-Si(1) bond distances ranging from 3.38-3.62 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded in a distorted single-bond geometry to one Li(1), three equivalent Ba(1), and three equivalent Ba(2) atoms. In the second Si site, Si(2) is bonded in a distorted single-bond geometry to one Li(1), two equivalent Ba(1), and four equivalent Ba(2) atoms.