Na3MgMo(OF)3 crystallizes in the trigonal R3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent F(1) atoms. In the second Na site, Na(2) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 octahedra that share corners with three equivalent Na(3)O3F3 octahedra, corners with six equivalent Mo(1)O3F3 octahedra, edges with three equivalent Mg(1)O3F3 octahedra, and  a faceface with one Na(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 34-60°. In the third Na site, Na(3) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 octahedra that share corners with three equivalent Na(2)O3F3 octahedra, corners with three equivalent Mg(1)O3F3 octahedra, edges with three equivalent Mo(1)O3F3 octahedra,  a faceface with one Na(2)O3F3 octahedra, and  a faceface with one Mg(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. Mg(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form MgO3F3 octahedra that share corners with three equivalent Na(3)O3F3 octahedra, corners with three equivalent Mo(1)O3F3 octahedra, edges with three equivalent Na(2)O3F3 octahedra,  a faceface with one Na(3)O3F3 octahedra, and  a faceface with one Mo(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 33-38°. Mo(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form MoO3F3 octahedra that share corners with three equivalent Mg(1)O3F3 octahedra, corners with six equivalent Na(2)O3F3 octahedra, edges with three equivalent Na(3)O3F3 octahedra, and  a faceface with one Mg(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 33-60°. O(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one Mo(1) atom. F(1) is bonded to one Na(1), one Na(2), one Na(3), one Mg(1), and one Mo(1) atom to form a mixture of distorted corner and edge-sharing FNa3MgMo trigonal bipyramids.
Na3MgMo(OF)3 crystallizes in the trigonal R3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent F(1) atoms. All Na(1)-O(1) bond lengths are 2.27 Å. All Na(1)-F(1) bond lengths are 2.67 Å. In the second Na site, Na(2) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 octahedra that share corners with three equivalent Na(3)O3F3 octahedra, corners with six equivalent Mo(1)O3F3 octahedra, edges with three equivalent Mg(1)O3F3 octahedra, and  a faceface with one Na(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 34-60°. All Na(2)-O(1) bond lengths are 2.53 Å. All Na(2)-F(1) bond lengths are 2.42 Å. In the third Na site, Na(3) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 octahedra that share corners with three equivalent Na(2)O3F3 octahedra, corners with three equivalent Mg(1)O3F3 octahedra, edges with three equivalent Mo(1)O3F3 octahedra,  a faceface with one Na(2)O3F3 octahedra, and  a faceface with one Mg(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. All Na(3)-O(1) bond lengths are 2.24 Å. All Na(3)-F(1) bond lengths are 2.36 Å. Mg(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form MgO3F3 octahedra that share corners with three equivalent Na(3)O3F3 octahedra, corners with three equivalent Mo(1)O3F3 octahedra, edges with three equivalent Na(2)O3F3 octahedra,  a faceface with one Na(3)O3F3 octahedra, and  a faceface with one Mo(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 33-38°. All Mg(1)-O(1) bond lengths are 2.11 Å. All Mg(1)-F(1) bond lengths are 2.09 Å. Mo(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form MoO3F3 octahedra that share corners with three equivalent Mg(1)O3F3 octahedra, corners with six equivalent Na(2)O3F3 octahedra, edges with three equivalent Na(3)O3F3 octahedra, and  a faceface with one Mg(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 33-60°. All Mo(1)-O(1) bond lengths are 1.96 Å. All Mo(1)-F(1) bond lengths are 2.32 Å. O(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one Mo(1) atom. F(1) is bonded to one Na(1), one Na(2), one Na(3), one Mg(1), and one Mo(1) atom to form a mixture of distorted corner and edge-sharing FNa3MgMo trigonal bipyramids.