Na10Zn4O9 crystallizes in the monoclinic C2 space group. There are twelve inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(5), and two equivalent O(9) atoms. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), one O(7), and one O(9) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Na(6)O4 tetrahedra,  a cornercorner with one Na(7)O4 tetrahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra,  an edgeedge with one Na(12)O4 tetrahedra,  an edgeedge with one Na(6)O4 tetrahedra,  an edgeedge with one Zn(1)O4 tetrahedra, and  an edgeedge with one Zn(2)O4 tetrahedra. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(5), and one O(7) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms. In the sixth Na site, Na(6) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form NaO4 tetrahedra that share  a cornercorner with one Na(12)O4 tetrahedra,  a cornercorner with one Na(7)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra, corners with two equivalent Zn(1)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and  an edgeedge with one Na(2)O5 trigonal bipyramid. In the seventh Na site, Na(7) is bonded to one O(1), one O(6), and two equivalent O(8) atoms to form distorted NaO4 tetrahedra that share  a cornercorner with one Na(6)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Zn(3)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and  an edgeedge with one Na(7)O4 tetrahedra. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. In the ninth Na site, Na(9) is bonded in a 3-coordinate geometry to one O(3), one O(4), one O(5), and one O(8) atom. In the tenth Na site, Na(10) is bonded in a 4-coordinate geometry to one O(5), one O(7), one O(8), and one O(9) atom. In the eleventh Na site, Na(11) is bonded in a 4-coordinate geometry to one O(6), one O(7), one O(8), and one O(9) atom. In the twelfth Na site, Na(12) is bonded to two equivalent O(7) and two equivalent O(9) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(6)O4 tetrahedra, corners with two equivalent Zn(1)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, and edges with two equivalent Na(2)O5 trigonal bipyramids. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(4), one O(9), and two equivalent O(2) atoms to form ZnO4 tetrahedra that share  a cornercorner with one Na(12)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra, corners with two equivalent Na(6)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid,  an edgeedge with one Zn(1)O4 tetrahedra, and  an edgeedge with one Na(2)O5 trigonal bipyramid. In the second Zn site, Zn(2) is bonded to one O(1), one O(5), one O(6), and one O(9) atom to form ZnO4 tetrahedra that share  a cornercorner with one Na(12)O4 tetrahedra,  a cornercorner with one Na(6)O4 tetrahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra, corners with two equivalent Na(7)O4 tetrahedra,  an edgeedge with one Zn(3)O4 tetrahedra, and  an edgeedge with one Na(2)O5 trigonal bipyramid. In the third Zn site, Zn(3) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form ZnO4 tetrahedra that share  a cornercorner with one Na(6)O4 tetrahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra, corners with two equivalent Na(7)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and  an edgeedge with one Zn(2)O4 tetrahedra. In the fourth Zn site, Zn(4) is bonded in a trigonal planar geometry to one O(3), one O(7), and one O(8) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), one Na(5), one Na(7), one Zn(2), and one Zn(3) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Na(2), one Na(3), one Na(4), one Na(6), one Na(8), and two equivalent Zn(1) atoms. In the third O site, O(3) is bonded to one Na(2), one Na(3), one Na(4), one Na(6), one Na(8), one Na(9), and one Zn(4) atom to form distorted ONa6Zn pentagonal bipyramids that share  a cornercorner with one O(3)Na6Zn pentagonal bipyramid and  a cornercorner with one O(6)Na3Zn2 trigonal bipyramid. In the fourth O site, O(4) is bonded in a 7-coordinate geometry to one Na(1), one Na(3), one Na(5), one Na(8), one Na(9), one Zn(1), and one Zn(3) atom. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(1), one Na(10), one Na(4), one Na(9), one Zn(2), and one Zn(3) atom. In the sixth O site, O(6) is bonded to one Na(11), one Na(6), one Na(7), one Zn(2), and one Zn(3) atom to form distorted corner-sharing ONa3Zn2 trigonal bipyramids. In the seventh O site, O(7) is bonded in a 7-coordinate geometry to one Na(10), one Na(11), one Na(12), one Na(2), one Na(4), one Na(6), and one Zn(4) atom. In the eighth O site, O(8) is bonded in a 7-coordinate geometry to one Na(10), one Na(11), one Na(5), one Na(9), two equivalent Na(7), and one Zn(4) atom. In the ninth O site, O(9) is bonded in a 7-coordinate geometry to one Na(1), one Na(10), one Na(11), one Na(12), one Na(2), one Zn(1), and one Zn(2) atom.
Na10Zn4O9 crystallizes in the monoclinic C2 space group. There are twelve inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(5), and two equivalent O(9) atoms. Both Na(1)-O(4) bond lengths are 2.55 Å. Both Na(1)-O(5) bond lengths are 2.67 Å. Both Na(1)-O(9) bond lengths are 2.86 Å. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), one O(7), and one O(9) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Na(6)O4 tetrahedra,  a cornercorner with one Na(7)O4 tetrahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra,  an edgeedge with one Na(12)O4 tetrahedra,  an edgeedge with one Na(6)O4 tetrahedra,  an edgeedge with one Zn(1)O4 tetrahedra, and  an edgeedge with one Zn(2)O4 tetrahedra. The Na(2)-O(1) bond length is 2.37 Å. The Na(2)-O(2) bond length is 2.37 Å. The Na(2)-O(3) bond length is 2.59 Å. The Na(2)-O(7) bond length is 2.43 Å. The Na(2)-O(9) bond length is 2.52 Å. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Na(3)-O(1) bond length is 2.29 Å. The Na(3)-O(2) bond length is 2.66 Å. The Na(3)-O(3) bond length is 2.34 Å. The Na(3)-O(4) bond length is 2.24 Å. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(5), and one O(7) atom. The Na(4)-O(2) bond length is 2.23 Å. The Na(4)-O(3) bond length is 2.27 Å. The Na(4)-O(5) bond length is 2.18 Å. The Na(4)-O(7) bond length is 2.59 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms. Both Na(5)-O(1) bond lengths are 2.43 Å. Both Na(5)-O(4) bond lengths are 2.47 Å. Both Na(5)-O(8) bond lengths are 2.77 Å. In the sixth Na site, Na(6) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form NaO4 tetrahedra that share  a cornercorner with one Na(12)O4 tetrahedra,  a cornercorner with one Na(7)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra, corners with two equivalent Zn(1)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and  an edgeedge with one Na(2)O5 trigonal bipyramid. The Na(6)-O(2) bond length is 2.27 Å. The Na(6)-O(3) bond length is 2.28 Å. The Na(6)-O(6) bond length is 2.25 Å. The Na(6)-O(7) bond length is 2.31 Å. In the seventh Na site, Na(7) is bonded to one O(1), one O(6), and two equivalent O(8) atoms to form distorted NaO4 tetrahedra that share  a cornercorner with one Na(6)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Zn(3)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and  an edgeedge with one Na(7)O4 tetrahedra. The Na(7)-O(1) bond length is 2.30 Å. The Na(7)-O(6) bond length is 2.28 Å. There is one shorter (2.31 Å) and one longer (2.36 Å) Na(7)-O(8) bond length. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Na(8)-O(2) bond lengths are 2.66 Å. Both Na(8)-O(3) bond lengths are 2.31 Å. Both Na(8)-O(4) bond lengths are 2.62 Å. In the ninth Na site, Na(9) is bonded in a 3-coordinate geometry to one O(3), one O(4), one O(5), and one O(8) atom. The Na(9)-O(3) bond length is 2.39 Å. The Na(9)-O(4) bond length is 2.46 Å. The Na(9)-O(5) bond length is 2.68 Å. The Na(9)-O(8) bond length is 2.30 Å. In the tenth Na site, Na(10) is bonded in a 4-coordinate geometry to one O(5), one O(7), one O(8), and one O(9) atom. The Na(10)-O(5) bond length is 2.46 Å. The Na(10)-O(7) bond length is 2.34 Å. The Na(10)-O(8) bond length is 2.32 Å. The Na(10)-O(9) bond length is 2.47 Å. In the eleventh Na site, Na(11) is bonded in a 4-coordinate geometry to one O(6), one O(7), one O(8), and one O(9) atom. The Na(11)-O(6) bond length is 2.24 Å. The Na(11)-O(7) bond length is 2.57 Å. The Na(11)-O(8) bond length is 2.41 Å. The Na(11)-O(9) bond length is 2.24 Å. In the twelfth Na site, Na(12) is bonded to two equivalent O(7) and two equivalent O(9) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(6)O4 tetrahedra, corners with two equivalent Zn(1)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, and edges with two equivalent Na(2)O5 trigonal bipyramids. Both Na(12)-O(7) bond lengths are 2.33 Å. Both Na(12)-O(9) bond lengths are 2.44 Å. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(4), one O(9), and two equivalent O(2) atoms to form ZnO4 tetrahedra that share  a cornercorner with one Na(12)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra, corners with two equivalent Na(6)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid,  an edgeedge with one Zn(1)O4 tetrahedra, and  an edgeedge with one Na(2)O5 trigonal bipyramid. The Zn(1)-O(4) bond length is 1.98 Å. The Zn(1)-O(9) bond length is 1.95 Å. There is one shorter (2.02 Å) and one longer (2.04 Å) Zn(1)-O(2) bond length. In the second Zn site, Zn(2) is bonded to one O(1), one O(5), one O(6), and one O(9) atom to form ZnO4 tetrahedra that share  a cornercorner with one Na(12)O4 tetrahedra,  a cornercorner with one Na(6)O4 tetrahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(3)O4 tetrahedra, corners with two equivalent Na(7)O4 tetrahedra,  an edgeedge with one Zn(3)O4 tetrahedra, and  an edgeedge with one Na(2)O5 trigonal bipyramid. The Zn(2)-O(1) bond length is 2.04 Å. The Zn(2)-O(5) bond length is 1.95 Å. The Zn(2)-O(6) bond length is 2.00 Å. The Zn(2)-O(9) bond length is 1.97 Å. In the third Zn site, Zn(3) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form ZnO4 tetrahedra that share  a cornercorner with one Na(6)O4 tetrahedra,  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra, corners with two equivalent Na(7)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and  an edgeedge with one Zn(2)O4 tetrahedra. The Zn(3)-O(1) bond length is 2.04 Å. The Zn(3)-O(4) bond length is 1.96 Å. The Zn(3)-O(5) bond length is 1.94 Å. The Zn(3)-O(6) bond length is 1.99 Å. In the fourth Zn site, Zn(4) is bonded in a trigonal planar geometry to one O(3), one O(7), and one O(8) atom. The Zn(4)-O(3) bond length is 1.90 Å. The Zn(4)-O(7) bond length is 1.95 Å. The Zn(4)-O(8) bond length is 1.89 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), one Na(5), one Na(7), one Zn(2), and one Zn(3) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Na(2), one Na(3), one Na(4), one Na(6), one Na(8), and two equivalent Zn(1) atoms. In the third O site, O(3) is bonded to one Na(2), one Na(3), one Na(4), one Na(6), one Na(8), one Na(9), and one Zn(4) atom to form distorted ONa6Zn pentagonal bipyramids that share  a cornercorner with one O(3)Na6Zn pentagonal bipyramid and  a cornercorner with one O(6)Na3Zn2 trigonal bipyramid. In the fourth O site, O(4) is bonded in a 7-coordinate geometry to one Na(1), one Na(3), one Na(5), one Na(8), one Na(9), one Zn(1), and one Zn(3) atom. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(1), one Na(10), one Na(4), one Na(9), one Zn(2), and one Zn(3) atom. In the sixth O site, O(6) is bonded to one Na(11), one Na(6), one Na(7), one Zn(2), and one Zn(3) atom to form distorted corner-sharing ONa3Zn2 trigonal bipyramids. In the seventh O site, O(7) is bonded in a 7-coordinate geometry to one Na(10), one Na(11), one Na(12), one Na(2), one Na(4), one Na(6), and one Zn(4) atom. In the eighth O site, O(8) is bonded in a 7-coordinate geometry to one Na(10), one Na(11), one Na(5), one Na(9), two equivalent Na(7), and one Zn(4) atom. In the ninth O site, O(9) is bonded in a 7-coordinate geometry to one Na(1), one Na(10), one Na(11), one Na(12), one Na(2), one Zn(1), and one Zn(2) atom.