Na3LaTi2Nb2O12 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), and four equivalent O(3) atoms to form distorted NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Nb(1)O6 octahedra. In the second Na site, Na(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. La(1) is bonded in a 12-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), and four equivalent O(4) atoms. Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 8-22°. Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NbO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 8-22°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Na(3), one La(1), one Ti(1), and one Nb(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Na(3), one La(1), one Ti(1), and one Nb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), two equivalent Na(2), one Ti(1), and one Nb(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(3), two equivalent La(1), one Ti(1), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one La(1), one Ti(1), and one Nb(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one La(1), one Ti(1), and one Nb(1) atom.
Na3LaTi2Nb2O12 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), and four equivalent O(3) atoms to form distorted NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Nb(1)O6 octahedra. Both Na(1)-O(1) bond lengths are 2.92 Å. Both Na(1)-O(2) bond lengths are 2.91 Å. Both Na(1)-O(5) bond lengths are 2.54 Å. Both Na(1)-O(6) bond lengths are 2.92 Å. There are two shorter (2.61 Å) and two longer (2.99 Å) Na(1)-O(3) bond lengths. In the second Na site, Na(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms. Both Na(2)-O(1) bond lengths are 2.78 Å. Both Na(2)-O(2) bond lengths are 2.78 Å. Both Na(2)-O(5) bond lengths are 2.79 Å. There are two shorter (2.62 Å) and two longer (2.97 Å) Na(2)-O(3) bond lengths. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. Both Na(3)-O(1) bond lengths are 2.66 Å. Both Na(3)-O(2) bond lengths are 2.66 Å. Both Na(3)-O(4) bond lengths are 2.66 Å. Both Na(3)-O(6) bond lengths are 2.69 Å. La(1) is bonded in a 12-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), and four equivalent O(4) atoms. Both La(1)-O(1) bond lengths are 2.80 Å. Both La(1)-O(2) bond lengths are 2.81 Å. Both La(1)-O(5) bond lengths are 2.75 Å. Both La(1)-O(6) bond lengths are 2.52 Å. There are two shorter (2.49 Å) and two longer (3.10 Å) La(1)-O(4) bond lengths. Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 8-22°. The Ti(1)-O(1) bond length is 2.01 Å. The Ti(1)-O(2) bond length is 1.93 Å. The Ti(1)-O(3) bond length is 2.01 Å. The Ti(1)-O(4) bond length is 1.94 Å. The Ti(1)-O(5) bond length is 1.98 Å. The Ti(1)-O(6) bond length is 1.98 Å. Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NbO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 8-22°. The Nb(1)-O(1) bond length is 1.97 Å. The Nb(1)-O(2) bond length is 2.04 Å. The Nb(1)-O(3) bond length is 1.93 Å. The Nb(1)-O(4) bond length is 2.11 Å. The Nb(1)-O(5) bond length is 2.00 Å. The Nb(1)-O(6) bond length is 2.03 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Na(3), one La(1), one Ti(1), and one Nb(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Na(3), one La(1), one Ti(1), and one Nb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), two equivalent Na(2), one Ti(1), and one Nb(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(3), two equivalent La(1), one Ti(1), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one La(1), one Ti(1), and one Nb(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one La(1), one Ti(1), and one Nb(1) atom.