Na2MgZn5(AsO4)6 crystallizes in the monoclinic C2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted square co-planar geometry to two equivalent O(7) and two equivalent O(8) atoms. In the second Na site, Na(2) is bonded in a distorted square co-planar geometry to two equivalent O(7) and two equivalent O(8) atoms. Mg(1) is bonded to two equivalent O(11), two equivalent O(4), and two equivalent O(9) atoms to form MgO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, corners with two equivalent As(4)O4 tetrahedra, and edges with two equivalent Zn(1)O6 octahedra. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(9) atom to form ZnO6 octahedra that share  a cornercorner with one As(3)O4 tetrahedra,  a cornercorner with one As(4)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one Zn(2)O6 octahedra. In the second Zn site, Zn(2) is bonded to one O(1), one O(10), one O(2), one O(3), one O(6), and one O(8) atom to form ZnO6 octahedra that share  a cornercorner with one As(3)O4 tetrahedra,  a cornercorner with one As(4)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra,  an edgeedge with one Zn(1)O6 octahedra, and  an edgeedge with one Zn(3)O6 octahedra. In the third Zn site, Zn(3) is bonded to two equivalent O(10), two equivalent O(12), and two equivalent O(3) atoms to form ZnO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, corners with two equivalent As(3)O4 tetrahedra, and edges with two equivalent Zn(2)O6 octahedra. There are four inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(10), one O(11), and one O(7) atom to form AsO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Zn(3)O6 octahedra, corners with two equivalent Zn(1)O6 octahedra, and corners with two equivalent Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-62°. In the second As site, As(2) is bonded to one O(12), one O(2), one O(8), and one O(9) atom to form AsO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Zn(3)O6 octahedra, corners with two equivalent Zn(1)O6 octahedra, and corners with two equivalent Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-62°. In the third As site, As(3) is bonded to two equivalent O(3) and two equivalent O(5) atoms to form AsO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with two equivalent Zn(2)O6 octahedra, and corners with two equivalent Zn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. In the fourth As site, As(4) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form AsO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent Zn(1)O6 octahedra, and corners with two equivalent Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one As(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one As(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Zn(2), one Zn(3), and one As(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one Zn(1), and one As(4) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Zn(1) and one As(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Zn(2) and one As(4) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Zn(1), and one As(1) atom to form a mixture of distorted corner and edge-sharing ONa2ZnAs trigonal pyramids. In the eighth O site, O(8) is bonded to one Na(1), one Na(2), one Zn(2), and one As(2) atom to form a mixture of distorted corner and edge-sharing ONa2ZnAs trigonal pyramids. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Mg(1), one Zn(1), and one As(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Zn(2), one Zn(3), and one As(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Mg(1) and one As(1) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Zn(3) and one As(2) atom.
Na2MgZn5(AsO4)6 crystallizes in the monoclinic C2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted square co-planar geometry to two equivalent O(7) and two equivalent O(8) atoms. Both Na(1)-O(7) bond lengths are 2.42 Å. Both Na(1)-O(8) bond lengths are 2.36 Å. In the second Na site, Na(2) is bonded in a distorted square co-planar geometry to two equivalent O(7) and two equivalent O(8) atoms. Both Na(2)-O(7) bond lengths are 2.36 Å. Both Na(2)-O(8) bond lengths are 2.43 Å. Mg(1) is bonded to two equivalent O(11), two equivalent O(4), and two equivalent O(9) atoms to form MgO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, corners with two equivalent As(4)O4 tetrahedra, and edges with two equivalent Zn(1)O6 octahedra. Both Mg(1)-O(11) bond lengths are 2.09 Å. Both Mg(1)-O(4) bond lengths are 2.18 Å. Both Mg(1)-O(9) bond lengths are 2.15 Å. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(9) atom to form ZnO6 octahedra that share  a cornercorner with one As(3)O4 tetrahedra,  a cornercorner with one As(4)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one Zn(2)O6 octahedra. The Zn(1)-O(1) bond length is 2.09 Å. The Zn(1)-O(2) bond length is 2.15 Å. The Zn(1)-O(4) bond length is 2.17 Å. The Zn(1)-O(5) bond length is 2.06 Å. The Zn(1)-O(7) bond length is 2.04 Å. The Zn(1)-O(9) bond length is 2.13 Å. In the second Zn site, Zn(2) is bonded to one O(1), one O(10), one O(2), one O(3), one O(6), and one O(8) atom to form ZnO6 octahedra that share  a cornercorner with one As(3)O4 tetrahedra,  a cornercorner with one As(4)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra,  an edgeedge with one Zn(1)O6 octahedra, and  an edgeedge with one Zn(3)O6 octahedra. The Zn(2)-O(1) bond length is 2.15 Å. The Zn(2)-O(10) bond length is 2.12 Å. The Zn(2)-O(2) bond length is 2.09 Å. The Zn(2)-O(3) bond length is 2.17 Å. The Zn(2)-O(6) bond length is 2.06 Å. The Zn(2)-O(8) bond length is 2.04 Å. In the third Zn site, Zn(3) is bonded to two equivalent O(10), two equivalent O(12), and two equivalent O(3) atoms to form ZnO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, corners with two equivalent As(3)O4 tetrahedra, and edges with two equivalent Zn(2)O6 octahedra. Both Zn(3)-O(10) bond lengths are 2.16 Å. Both Zn(3)-O(12) bond lengths are 2.08 Å. Both Zn(3)-O(3) bond lengths are 2.19 Å. There are four inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(10), one O(11), and one O(7) atom to form AsO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Zn(3)O6 octahedra, corners with two equivalent Zn(1)O6 octahedra, and corners with two equivalent Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-62°. The As(1)-O(1) bond length is 1.74 Å. The As(1)-O(10) bond length is 1.74 Å. The As(1)-O(11) bond length is 1.72 Å. The As(1)-O(7) bond length is 1.72 Å. In the second As site, As(2) is bonded to one O(12), one O(2), one O(8), and one O(9) atom to form AsO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Zn(3)O6 octahedra, corners with two equivalent Zn(1)O6 octahedra, and corners with two equivalent Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-62°. The As(2)-O(12) bond length is 1.73 Å. The As(2)-O(2) bond length is 1.73 Å. The As(2)-O(8) bond length is 1.72 Å. The As(2)-O(9) bond length is 1.74 Å. In the third As site, As(3) is bonded to two equivalent O(3) and two equivalent O(5) atoms to form AsO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with two equivalent Zn(2)O6 octahedra, and corners with two equivalent Zn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. Both As(3)-O(3) bond lengths are 1.74 Å. Both As(3)-O(5) bond lengths are 1.74 Å. In the fourth As site, As(4) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form AsO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent Zn(1)O6 octahedra, and corners with two equivalent Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. Both As(4)-O(4) bond lengths are 1.73 Å. Both As(4)-O(6) bond lengths are 1.74 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one As(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one As(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Zn(2), one Zn(3), and one As(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one Zn(1), and one As(4) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Zn(1) and one As(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Zn(2) and one As(4) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Zn(1), and one As(1) atom to form a mixture of distorted corner and edge-sharing ONa2ZnAs trigonal pyramids. In the eighth O site, O(8) is bonded to one Na(1), one Na(2), one Zn(2), and one As(2) atom to form a mixture of distorted corner and edge-sharing ONa2ZnAs trigonal pyramids. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Mg(1), one Zn(1), and one As(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Zn(2), one Zn(3), and one As(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Mg(1) and one As(1) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Zn(3) and one As(2) atom.