Na2MgNb2O6 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. Mg(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Nb site, Nb(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom. In the sixth O site, O(6) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids.
Na2MgNb2O6 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.65 Å. The Na(1)-O(2) bond length is 2.81 Å. The Na(1)-O(3) bond length is 2.40 Å. The Na(1)-O(4) bond length is 2.30 Å. The Na(1)-O(5) bond length is 2.34 Å. The Na(1)-O(6) bond length is 2.29 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Na(2)-O(1) bond length is 2.31 Å. The Na(2)-O(2) bond length is 2.34 Å. The Na(2)-O(3) bond length is 2.28 Å. The Na(2)-O(4) bond length is 2.67 Å. The Na(2)-O(5) bond length is 2.87 Å. The Na(2)-O(6) bond length is 2.42 Å. Mg(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Mg(1)-O(1) bond length is 2.14 Å. The Mg(1)-O(2) bond length is 2.12 Å. The Mg(1)-O(3) bond length is 2.08 Å. The Mg(1)-O(4) bond length is 2.15 Å. The Mg(1)-O(5) bond length is 2.13 Å. The Mg(1)-O(6) bond length is 2.08 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Nb(1)-O(1) bond length is 2.15 Å. The Nb(1)-O(2) bond length is 1.94 Å. The Nb(1)-O(3) bond length is 2.07 Å. The Nb(1)-O(4) bond length is 2.07 Å. The Nb(1)-O(5) bond length is 2.38 Å. The Nb(1)-O(6) bond length is 2.12 Å. In the second Nb site, Nb(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Nb(2)-O(1) bond length is 2.07 Å. The Nb(2)-O(2) bond length is 2.40 Å. The Nb(2)-O(3) bond length is 2.11 Å. The Nb(2)-O(4) bond length is 2.15 Å. The Nb(2)-O(5) bond length is 1.94 Å. The Nb(2)-O(6) bond length is 2.07 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom. In the sixth O site, O(6) is bonded to one Na(1), one Na(2), one Mg(1), one Nb(1), and one Nb(2) atom to form a mixture of distorted corner and edge-sharing ONa2MgNb2 trigonal bipyramids.