Na3MnCoNiO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the second Na site, Na(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaO6 octahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-17°. In the third Na site, Na(3) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form NaO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Co(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. Mn(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Na(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-13°. Co(1) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with three equivalent Na(2)O6 octahedra, corners with three equivalent Na(3)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-17°. Ni(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Na(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), two equivalent Mn(1), and one Co(1) atom to form ONa3Mn2Co octahedra that share corners with three equivalent O(5)Na3CoNi2 octahedra, corners with three equivalent O(4)Na3Mn2Ni octahedra,  an edgeedge with one O(5)Na3CoNi2 octahedra,  an edgeedge with one O(4)Na3Mn2Ni octahedra, edges with two equivalent O(3)Na3Co2Ni octahedra, edges with two equivalent O(1)Na3Mn2Co octahedra, edges with two equivalent O(2)Na3MnNi2 octahedra, and edges with four equivalent O(6)Na3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(2), one Mn(1), and two equivalent Ni(1) atoms to form distorted ONa3MnNi2 octahedra that share corners with three equivalent O(5)Na3CoNi2 octahedra, corners with three equivalent O(6)Na3MnCo2 octahedra,  an edgeedge with one O(5)Na3CoNi2 octahedra,  an edgeedge with one O(6)Na3MnCo2 octahedra, edges with two equivalent O(3)Na3Co2Ni octahedra, edges with two equivalent O(1)Na3Mn2Co octahedra, edges with two equivalent O(2)Na3MnNi2 octahedra, and edges with four equivalent O(4)Na3Mn2Ni octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(3), two equivalent Co(1), and one Ni(1) atom to form ONa3Co2Ni octahedra that share corners with three equivalent O(4)Na3Mn2Ni octahedra, corners with three equivalent O(6)Na3MnCo2 octahedra,  an edgeedge with one O(4)Na3Mn2Ni octahedra,  an edgeedge with one O(6)Na3MnCo2 octahedra, edges with two equivalent O(3)Na3Co2Ni octahedra, edges with two equivalent O(1)Na3Mn2Co octahedra, edges with two equivalent O(2)Na3MnNi2 octahedra, and edges with four equivalent O(5)Na3CoNi2 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the fourth O site, O(4) is bonded to one Na(2), two equivalent Na(3), two equivalent Mn(1), and one Ni(1) atom to form ONa3Mn2Ni octahedra that share corners with three equivalent O(3)Na3Co2Ni octahedra, corners with three equivalent O(1)Na3Mn2Co octahedra,  an edgeedge with one O(3)Na3Co2Ni octahedra,  an edgeedge with one O(1)Na3Mn2Co octahedra, edges with two equivalent O(5)Na3CoNi2 octahedra, edges with two equivalent O(4)Na3Mn2Ni octahedra, edges with two equivalent O(6)Na3MnCo2 octahedra, and edges with four equivalent O(2)Na3MnNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fifth O site, O(5) is bonded to one Na(3), two equivalent Na(1), one Co(1), and two equivalent Ni(1) atoms to form ONa3CoNi2 octahedra that share corners with three equivalent O(1)Na3Mn2Co octahedra, corners with three equivalent O(2)Na3MnNi2 octahedra,  an edgeedge with one O(1)Na3Mn2Co octahedra,  an edgeedge with one O(2)Na3MnNi2 octahedra, edges with two equivalent O(5)Na3CoNi2 octahedra, edges with two equivalent O(4)Na3Mn2Ni octahedra, edges with two equivalent O(6)Na3MnCo2 octahedra, and edges with four equivalent O(3)Na3Co2Ni octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the sixth O site, O(6) is bonded to one Na(1), two equivalent Na(2), one Mn(1), and two equivalent Co(1) atoms to form distorted ONa3MnCo2 octahedra that share corners with three equivalent O(3)Na3Co2Ni octahedra, corners with three equivalent O(2)Na3MnNi2 octahedra,  an edgeedge with one O(3)Na3Co2Ni octahedra,  an edgeedge with one O(2)Na3MnNi2 octahedra, edges with two equivalent O(5)Na3CoNi2 octahedra, edges with two equivalent O(4)Na3Mn2Ni octahedra, edges with two equivalent O(6)Na3MnCo2 octahedra, and edges with four equivalent O(1)Na3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 1-12°.
Na3MnCoNiO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. The Na(1)-O(3) bond length is 2.29 Å. The Na(1)-O(6) bond length is 2.44 Å. Both Na(1)-O(1) bond lengths are 2.44 Å. Both Na(1)-O(5) bond lengths are 2.31 Å. In the second Na site, Na(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaO6 octahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-17°. The Na(2)-O(1) bond length is 2.35 Å. The Na(2)-O(4) bond length is 2.32 Å. Both Na(2)-O(2) bond lengths are 2.34 Å. Both Na(2)-O(6) bond lengths are 2.37 Å. In the third Na site, Na(3) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form NaO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Co(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. The Na(3)-O(2) bond length is 2.46 Å. The Na(3)-O(5) bond length is 2.41 Å. Both Na(3)-O(3) bond lengths are 2.34 Å. Both Na(3)-O(4) bond lengths are 2.46 Å. Mn(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Na(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-13°. The Mn(1)-O(2) bond length is 1.93 Å. The Mn(1)-O(6) bond length is 1.96 Å. Both Mn(1)-O(1) bond lengths are 2.00 Å. Both Mn(1)-O(4) bond lengths are 2.00 Å. Co(1) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with three equivalent Na(2)O6 octahedra, corners with three equivalent Na(3)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra,  an edgeedge with one Na(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-17°. The Co(1)-O(1) bond length is 2.20 Å. The Co(1)-O(5) bond length is 1.87 Å. Both Co(1)-O(3) bond lengths are 2.03 Å. Both Co(1)-O(6) bond lengths are 2.11 Å. Ni(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Na(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. The Ni(1)-O(3) bond length is 2.10 Å. The Ni(1)-O(4) bond length is 2.14 Å. Both Ni(1)-O(2) bond lengths are 2.09 Å. Both Ni(1)-O(5) bond lengths are 2.13 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), two equivalent Mn(1), and one Co(1) atom to form ONa3Mn2Co octahedra that share corners with three equivalent O(5)Na3CoNi2 octahedra, corners with three equivalent O(4)Na3Mn2Ni octahedra,  an edgeedge with one O(5)Na3CoNi2 octahedra,  an edgeedge with one O(4)Na3Mn2Ni octahedra, edges with two equivalent O(3)Na3Co2Ni octahedra, edges with two equivalent O(1)Na3Mn2Co octahedra, edges with two equivalent O(2)Na3MnNi2 octahedra, and edges with four equivalent O(6)Na3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(2), one Mn(1), and two equivalent Ni(1) atoms to form distorted ONa3MnNi2 octahedra that share corners with three equivalent O(5)Na3CoNi2 octahedra, corners with three equivalent O(6)Na3MnCo2 octahedra,  an edgeedge with one O(5)Na3CoNi2 octahedra,  an edgeedge with one O(6)Na3MnCo2 octahedra, edges with two equivalent O(3)Na3Co2Ni octahedra, edges with two equivalent O(1)Na3Mn2Co octahedra, edges with two equivalent O(2)Na3MnNi2 octahedra, and edges with four equivalent O(4)Na3Mn2Ni octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(3), two equivalent Co(1), and one Ni(1) atom to form ONa3Co2Ni octahedra that share corners with three equivalent O(4)Na3Mn2Ni octahedra, corners with three equivalent O(6)Na3MnCo2 octahedra,  an edgeedge with one O(4)Na3Mn2Ni octahedra,  an edgeedge with one O(6)Na3MnCo2 octahedra, edges with two equivalent O(3)Na3Co2Ni octahedra, edges with two equivalent O(1)Na3Mn2Co octahedra, edges with two equivalent O(2)Na3MnNi2 octahedra, and edges with four equivalent O(5)Na3CoNi2 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the fourth O site, O(4) is bonded to one Na(2), two equivalent Na(3), two equivalent Mn(1), and one Ni(1) atom to form ONa3Mn2Ni octahedra that share corners with three equivalent O(3)Na3Co2Ni octahedra, corners with three equivalent O(1)Na3Mn2Co octahedra,  an edgeedge with one O(3)Na3Co2Ni octahedra,  an edgeedge with one O(1)Na3Mn2Co octahedra, edges with two equivalent O(5)Na3CoNi2 octahedra, edges with two equivalent O(4)Na3Mn2Ni octahedra, edges with two equivalent O(6)Na3MnCo2 octahedra, and edges with four equivalent O(2)Na3MnNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fifth O site, O(5) is bonded to one Na(3), two equivalent Na(1), one Co(1), and two equivalent Ni(1) atoms to form ONa3CoNi2 octahedra that share corners with three equivalent O(1)Na3Mn2Co octahedra, corners with three equivalent O(2)Na3MnNi2 octahedra,  an edgeedge with one O(1)Na3Mn2Co octahedra,  an edgeedge with one O(2)Na3MnNi2 octahedra, edges with two equivalent O(5)Na3CoNi2 octahedra, edges with two equivalent O(4)Na3Mn2Ni octahedra, edges with two equivalent O(6)Na3MnCo2 octahedra, and edges with four equivalent O(3)Na3Co2Ni octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the sixth O site, O(6) is bonded to one Na(1), two equivalent Na(2), one Mn(1), and two equivalent Co(1) atoms to form distorted ONa3MnCo2 octahedra that share corners with three equivalent O(3)Na3Co2Ni octahedra, corners with three equivalent O(2)Na3MnNi2 octahedra,  an edgeedge with one O(3)Na3Co2Ni octahedra,  an edgeedge with one O(2)Na3MnNi2 octahedra, edges with two equivalent O(5)Na3CoNi2 octahedra, edges with two equivalent O(4)Na3Mn2Ni octahedra, edges with two equivalent O(6)Na3MnCo2 octahedra, and edges with four equivalent O(1)Na3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 1-12°.