Na2Gd4NOCl9 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Cl(1), one Cl(2), one Cl(5), one Cl(7), one Cl(8), and one Cl(9) atom to form a mixture of distorted corner and edge-sharing NaCl6 pentagonal pyramids. In the second Na site, Na(2) is bonded to one Cl(1), one Cl(2), one Cl(4), one Cl(7), one Cl(8), and one Cl(9) atom to form a mixture of distorted corner and edge-sharing NaCl6 pentagonal pyramids. There are four inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 2-coordinate geometry to one N(1), one O(1), one Cl(1), one Cl(3), one Cl(4), one Cl(5), one Cl(6), one Cl(8), and one Cl(9) atom. In the second Gd site, Gd(2) is bonded in a 2-coordinate geometry to one N(1), one O(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), one Cl(6), one Cl(8), and one Cl(9) atom. In the third Gd site, Gd(3) is bonded in a 8-coordinate geometry to one N(1), one O(1), one Cl(1), one Cl(2), one Cl(6), one Cl(7), one Cl(8), and one Cl(9) atom. In the fourth Gd site, Gd(4) is bonded in a 8-coordinate geometry to one N(1), one O(1), one Cl(3), one Cl(4), one Cl(5), one Cl(7), one Cl(8), and one Cl(9) atom. N(1) is bonded to one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom to form NGd4 tetrahedra that share edges with two equivalent O(1)Gd4 tetrahedra. O(1) is bonded to one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom to form OGd4 tetrahedra that share edges with two equivalent N(1)Gd4 tetrahedra. There are nine inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a see-saw-like geometry to one Na(1), one Na(2), one Gd(1), and one Gd(3) atom. In the second Cl site, Cl(2) is bonded in a see-saw-like geometry to one Na(1), one Na(2), one Gd(2), and one Gd(3) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to one Gd(1), one Gd(2), and one Gd(4) atom. In the fourth Cl site, Cl(4) is bonded in a distorted see-saw-like geometry to one Na(2), one Gd(1), one Gd(2), and one Gd(4) atom. In the fifth Cl site, Cl(5) is bonded in a distorted see-saw-like geometry to one Na(1), one Gd(1), one Gd(2), and one Gd(4) atom. In the sixth Cl site, Cl(6) is bonded in a distorted T-shaped geometry to one Gd(1), one Gd(2), and one Gd(3) atom. In the seventh Cl site, Cl(7) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Gd(3), and one Gd(4) atom. In the eighth Cl site, Cl(8) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom. In the ninth Cl site, Cl(9) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom.
Na2Gd4NOCl9 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Cl(1), one Cl(2), one Cl(5), one Cl(7), one Cl(8), and one Cl(9) atom to form a mixture of distorted corner and edge-sharing NaCl6 pentagonal pyramids. The Na(1)-Cl(1) bond length is 2.85 Å. The Na(1)-Cl(2) bond length is 2.99 Å. The Na(1)-Cl(5) bond length is 2.90 Å. The Na(1)-Cl(7) bond length is 2.83 Å. The Na(1)-Cl(8) bond length is 2.84 Å. The Na(1)-Cl(9) bond length is 2.86 Å. In the second Na site, Na(2) is bonded to one Cl(1), one Cl(2), one Cl(4), one Cl(7), one Cl(8), and one Cl(9) atom to form a mixture of distorted corner and edge-sharing NaCl6 pentagonal pyramids. The Na(2)-Cl(1) bond length is 3.01 Å. The Na(2)-Cl(2) bond length is 2.82 Å. The Na(2)-Cl(4) bond length is 2.92 Å. The Na(2)-Cl(7) bond length is 2.85 Å. The Na(2)-Cl(8) bond length is 2.86 Å. The Na(2)-Cl(9) bond length is 2.83 Å. There are four inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 2-coordinate geometry to one N(1), one O(1), one Cl(1), one Cl(3), one Cl(4), one Cl(5), one Cl(6), one Cl(8), and one Cl(9) atom. The Gd(1)-N(1) bond length is 2.27 Å. The Gd(1)-O(1) bond length is 2.24 Å. The Gd(1)-Cl(1) bond length is 2.88 Å. The Gd(1)-Cl(3) bond length is 2.90 Å. The Gd(1)-Cl(4) bond length is 2.85 Å. The Gd(1)-Cl(5) bond length is 3.27 Å. The Gd(1)-Cl(6) bond length is 2.90 Å. The Gd(1)-Cl(8) bond length is 3.27 Å. The Gd(1)-Cl(9) bond length is 3.34 Å. In the second Gd site, Gd(2) is bonded in a 2-coordinate geometry to one N(1), one O(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), one Cl(6), one Cl(8), and one Cl(9) atom. The Gd(2)-N(1) bond length is 2.20 Å. The Gd(2)-O(1) bond length is 2.33 Å. The Gd(2)-Cl(2) bond length is 2.83 Å. The Gd(2)-Cl(3) bond length is 2.97 Å. The Gd(2)-Cl(4) bond length is 3.27 Å. The Gd(2)-Cl(5) bond length is 2.81 Å. The Gd(2)-Cl(6) bond length is 2.96 Å. The Gd(2)-Cl(8) bond length is 3.33 Å. The Gd(2)-Cl(9) bond length is 3.28 Å. In the third Gd site, Gd(3) is bonded in a 8-coordinate geometry to one N(1), one O(1), one Cl(1), one Cl(2), one Cl(6), one Cl(7), one Cl(8), and one Cl(9) atom. The Gd(3)-N(1) bond length is 2.25 Å. The Gd(3)-O(1) bond length is 2.30 Å. The Gd(3)-Cl(1) bond length is 2.88 Å. The Gd(3)-Cl(2) bond length is 2.88 Å. The Gd(3)-Cl(6) bond length is 2.75 Å. The Gd(3)-Cl(7) bond length is 2.87 Å. The Gd(3)-Cl(8) bond length is 3.12 Å. The Gd(3)-Cl(9) bond length is 3.14 Å. In the fourth Gd site, Gd(4) is bonded in a 8-coordinate geometry to one N(1), one O(1), one Cl(3), one Cl(4), one Cl(5), one Cl(7), one Cl(8), and one Cl(9) atom. The Gd(4)-N(1) bond length is 2.26 Å. The Gd(4)-O(1) bond length is 2.32 Å. The Gd(4)-Cl(3) bond length is 2.79 Å. The Gd(4)-Cl(4) bond length is 2.83 Å. The Gd(4)-Cl(5) bond length is 2.82 Å. The Gd(4)-Cl(7) bond length is 2.91 Å. The Gd(4)-Cl(8) bond length is 3.05 Å. The Gd(4)-Cl(9) bond length is 3.02 Å. N(1) is bonded to one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom to form NGd4 tetrahedra that share edges with two equivalent O(1)Gd4 tetrahedra. O(1) is bonded to one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom to form OGd4 tetrahedra that share edges with two equivalent N(1)Gd4 tetrahedra. There are nine inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a see-saw-like geometry to one Na(1), one Na(2), one Gd(1), and one Gd(3) atom. In the second Cl site, Cl(2) is bonded in a see-saw-like geometry to one Na(1), one Na(2), one Gd(2), and one Gd(3) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to one Gd(1), one Gd(2), and one Gd(4) atom. In the fourth Cl site, Cl(4) is bonded in a distorted see-saw-like geometry to one Na(2), one Gd(1), one Gd(2), and one Gd(4) atom. In the fifth Cl site, Cl(5) is bonded in a distorted see-saw-like geometry to one Na(1), one Gd(1), one Gd(2), and one Gd(4) atom. In the sixth Cl site, Cl(6) is bonded in a distorted T-shaped geometry to one Gd(1), one Gd(2), and one Gd(3) atom. In the seventh Cl site, Cl(7) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Gd(3), and one Gd(4) atom. In the eighth Cl site, Cl(8) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom. In the ninth Cl site, Cl(9) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Gd(1), one Gd(2), one Gd(3), and one Gd(4) atom.