NaSc(BH4)4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded to two equivalent H(3) and four equivalent H(5) atoms to form distorted NaH6 octahedra that share corners with two equivalent B(1)H4 tetrahedra, corners with four equivalent B(2)H4 tetrahedra, and edges with two equivalent Na(1)H6 octahedra. Sc(1) is bonded to two equivalent H(1), two equivalent H(6), four equivalent H(2), and four equivalent H(4) atoms to form ScH12 cuboctahedra that share faces with two equivalent B(1)H4 tetrahedra and faces with two equivalent B(2)H4 tetrahedra. There are two inequivalent B sites. In the first B site, B(1) is bonded to one H(1), one H(3), and two equivalent H(2) atoms to form BH4 tetrahedra that share  a cornercorner with one Na(1)H6 octahedra and  a faceface with one Sc(1)H12 cuboctahedra. The corner-sharing octahedral tilt angles are 74°. In the second B site, B(2) is bonded to one H(5), one H(6), and two equivalent H(4) atoms to form BH4 tetrahedra that share corners with two equivalent Na(1)H6 octahedra and  a faceface with one Sc(1)H12 cuboctahedra. The corner-sharing octahedral tilt angles are 72°. There are six inequivalent H sites. In the first H site, H(3) is bonded in a distorted water-like geometry to one Na(1) and one B(1) atom. In the second H site, H(4) is bonded in a distorted single-bond geometry to one Sc(1) and one B(2) atom. In the third H site, H(5) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one B(2) atom. In the fourth H site, H(6) is bonded in a distorted single-bond geometry to one Sc(1) and one B(2) atom. In the fifth H site, H(1) is bonded in a distorted single-bond geometry to one Sc(1) and one B(1) atom. In the sixth H site, H(2) is bonded in a distorted single-bond geometry to one Sc(1) and one B(1) atom.
NaSc(BH4)4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded to two equivalent H(3) and four equivalent H(5) atoms to form distorted NaH6 octahedra that share corners with two equivalent B(1)H4 tetrahedra, corners with four equivalent B(2)H4 tetrahedra, and edges with two equivalent Na(1)H6 octahedra. Both Na(1)-H(3) bond lengths are 2.38 Å. All Na(1)-H(5) bond lengths are 2.53 Å. Sc(1) is bonded to two equivalent H(1), two equivalent H(6), four equivalent H(2), and four equivalent H(4) atoms to form ScH12 cuboctahedra that share faces with two equivalent B(1)H4 tetrahedra and faces with two equivalent B(2)H4 tetrahedra. Both Sc(1)-H(1) bond lengths are 2.17 Å. Both Sc(1)-H(6) bond lengths are 2.17 Å. All Sc(1)-H(2) bond lengths are 2.16 Å. All Sc(1)-H(4) bond lengths are 2.21 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to one H(1), one H(3), and two equivalent H(2) atoms to form BH4 tetrahedra that share  a cornercorner with one Na(1)H6 octahedra and  a faceface with one Sc(1)H12 cuboctahedra. The corner-sharing octahedral tilt angles are 74°. The B(1)-H(1) bond length is 1.24 Å. The B(1)-H(3) bond length is 1.20 Å. Both B(1)-H(2) bond lengths are 1.24 Å. In the second B site, B(2) is bonded to one H(5), one H(6), and two equivalent H(4) atoms to form BH4 tetrahedra that share corners with two equivalent Na(1)H6 octahedra and  a faceface with one Sc(1)H12 cuboctahedra. The corner-sharing octahedral tilt angles are 72°. The B(2)-H(5) bond length is 1.21 Å. The B(2)-H(6) bond length is 1.24 Å. Both B(2)-H(4) bond lengths are 1.23 Å. There are six inequivalent H sites. In the first H site, H(3) is bonded in a distorted water-like geometry to one Na(1) and one B(1) atom. In the second H site, H(4) is bonded in a distorted single-bond geometry to one Sc(1) and one B(2) atom. In the third H site, H(5) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one B(2) atom. In the fourth H site, H(6) is bonded in a distorted single-bond geometry to one Sc(1) and one B(2) atom. In the fifth H site, H(1) is bonded in a distorted single-bond geometry to one Sc(1) and one B(1) atom. In the sixth H site, H(2) is bonded in a distorted single-bond geometry to one Sc(1) and one B(1) atom.