Na2In crystallizes in the orthorhombic C222_1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent Na(3), two equivalent In(1), and two equivalent In(2) atoms. In the second Na site, Na(2) is bonded in a 12-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), two equivalent In(1), and four equivalent In(2) atoms. In the third Na site, Na(3) is bonded in a 13-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), three equivalent Na(5), two equivalent In(2), and three equivalent In(1) atoms. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), two equivalent In(1), and two equivalent In(2) atoms. In the fifth Na site, Na(5) is bonded in a 3-coordinate geometry to one Na(2), three equivalent Na(3), one In(2), and two equivalent In(1) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to one Na(1), one Na(2), two equivalent Na(4), two equivalent Na(5), three equivalent Na(3), one In(1), and two equivalent In(2) atoms to form a mixture of distorted corner and face-sharing InNa9In3 cuboctahedra. In the second In site, In(2) is bonded in a 11-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(3), two equivalent Na(4), one In(2), and two equivalent In(1) atoms.
Na2In crystallizes in the orthorhombic C222_1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent Na(3), two equivalent In(1), and two equivalent In(2) atoms. Both Na(1)-Na(3) bond lengths are 3.36 Å. Both Na(1)-In(1) bond lengths are 3.40 Å. Both Na(1)-In(2) bond lengths are 3.30 Å. In the second Na site, Na(2) is bonded in a 12-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), two equivalent In(1), and four equivalent In(2) atoms. Both Na(2)-Na(3) bond lengths are 3.50 Å. Both Na(2)-Na(4) bond lengths are 3.28 Å. Both Na(2)-Na(5) bond lengths are 3.54 Å. Both Na(2)-In(1) bond lengths are 3.27 Å. There are two shorter (3.36 Å) and two longer (3.57 Å) Na(2)-In(2) bond lengths. In the third Na site, Na(3) is bonded in a 13-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), three equivalent Na(5), two equivalent In(2), and three equivalent In(1) atoms. The Na(3)-Na(3) bond length is 3.94 Å. There is one shorter (3.50 Å) and one longer (3.54 Å) Na(3)-Na(4) bond length. There are a spread of Na(3)-Na(5) bond distances ranging from 3.51-3.77 Å. There is one shorter (3.64 Å) and one longer (3.67 Å) Na(3)-In(2) bond length. There are a spread of Na(3)-In(1) bond distances ranging from 3.32-3.65 Å. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), two equivalent In(1), and two equivalent In(2) atoms. There is one shorter (3.18 Å) and one longer (3.28 Å) Na(4)-In(1) bond length. There is one shorter (3.23 Å) and one longer (3.28 Å) Na(4)-In(2) bond length. In the fifth Na site, Na(5) is bonded in a 3-coordinate geometry to one Na(2), three equivalent Na(3), one In(2), and two equivalent In(1) atoms. The Na(5)-In(2) bond length is 3.27 Å. There is one shorter (3.35 Å) and one longer (3.44 Å) Na(5)-In(1) bond length. There are two inequivalent In sites. In the first In site, In(1) is bonded to one Na(1), one Na(2), two equivalent Na(4), two equivalent Na(5), three equivalent Na(3), one In(1), and two equivalent In(2) atoms to form a mixture of distorted corner and face-sharing InNa9In3 cuboctahedra. The In(1)-In(1) bond length is 3.07 Å. There is one shorter (3.06 Å) and one longer (3.15 Å) In(1)-In(2) bond length. In the second In site, In(2) is bonded in a 11-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(3), two equivalent Na(4), one In(2), and two equivalent In(1) atoms. The In(2)-In(2) bond length is 3.13 Å.