NaPdF3 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(4), one F(5), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share  a cornercorner with one Na(3)F6 octahedra,  a cornercorner with one Pd(3)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 65-72°. In the second Na site, Na(2) is bonded in a body-centered cubic geometry to two equivalent F(1), two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms. In the third Na site, Na(3) is bonded to two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms to form NaF6 octahedra that share corners with two equivalent Na(1)F6 octahedra and edges with two equivalent Pd(3)F6 octahedra. The corner-sharing octahedral tilt angles are 72°. There are three inequivalent Pd sites. In the first Pd site, Pd(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(2), one F(3), and one F(6) atom. In the second Pd site, Pd(2) is bonded in a square co-planar geometry to two equivalent F(4) and two equivalent F(5) atoms. In the third Pd site, Pd(3) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(6) atoms to form PdF6 octahedra that share corners with two equivalent Na(1)F6 octahedra and edges with two equivalent Na(3)F6 octahedra. The corner-sharing octahedral tilt angles are 65°. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), one Na(3), one Pd(1), and one Pd(3) atom to form distorted FNa2Pd2 tetrahedra that share  a cornercorner with one F(2)Na3Pd tetrahedra, corners with two equivalent F(4)Na2Pd2 tetrahedra, corners with two equivalent F(5)Na3Pd tetrahedra, corners with three equivalent F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(4)Na2Pd2 tetrahedra,  an edgeedge with one F(2)Na3Pd tetrahedra, and  an edgeedge with one F(5)Na3Pd tetrahedra. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Pd(1) atom to form FNa3Pd tetrahedra that share  a cornercorner with one F(1)Na2Pd2 tetrahedra,  a cornercorner with one F(2)Na3Pd tetrahedra, corners with two equivalent F(4)Na2Pd2 tetrahedra, corners with two equivalent F(5)Na3Pd tetrahedra,  an edgeedge with one F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(4)Na2Pd2 tetrahedra,  an edgeedge with one F(2)Na3Pd tetrahedra, and  an edgeedge with one F(5)Na3Pd tetrahedra. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Pd(1) atom. In the fourth F site, F(4) is bonded to one Na(1), one Na(2), one Pd(2), and one Pd(3) atom to form FNa2Pd2 tetrahedra that share corners with two equivalent F(1)Na2Pd2 tetrahedra, corners with two equivalent F(2)Na3Pd tetrahedra, corners with three equivalent F(4)Na2Pd2 tetrahedra, corners with three equivalent F(5)Na3Pd tetrahedra,  an edgeedge with one F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(2)Na3Pd tetrahedra, and  an edgeedge with one F(5)Na3Pd tetrahedra. In the fifth F site, F(5) is bonded to one Na(1), one Na(2), one Na(3), and one Pd(2) atom to form FNa3Pd tetrahedra that share corners with two equivalent F(1)Na2Pd2 tetrahedra, corners with two equivalent F(2)Na3Pd tetrahedra, corners with three equivalent F(4)Na2Pd2 tetrahedra, corners with three equivalent F(5)Na3Pd tetrahedra,  an edgeedge with one F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(4)Na2Pd2 tetrahedra, and  an edgeedge with one F(2)Na3Pd tetrahedra. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Na(3), one Pd(1), and one Pd(3) atom.
NaPdF3 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(4), one F(5), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share  a cornercorner with one Na(3)F6 octahedra,  a cornercorner with one Pd(3)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 65-72°. The Na(1)-F(4) bond length is 2.43 Å. The Na(1)-F(5) bond length is 2.36 Å. There is one shorter (2.24 Å) and one longer (2.25 Å) Na(1)-F(2) bond length. There is one shorter (2.22 Å) and one longer (2.24 Å) Na(1)-F(3) bond length. In the second Na site, Na(2) is bonded in a body-centered cubic geometry to two equivalent F(1), two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms. Both Na(2)-F(1) bond lengths are 2.57 Å. Both Na(2)-F(2) bond lengths are 2.47 Å. Both Na(2)-F(4) bond lengths are 2.47 Å. Both Na(2)-F(5) bond lengths are 2.33 Å. In the third Na site, Na(3) is bonded to two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms to form NaF6 octahedra that share corners with two equivalent Na(1)F6 octahedra and edges with two equivalent Pd(3)F6 octahedra. The corner-sharing octahedral tilt angles are 72°. Both Na(3)-F(1) bond lengths are 2.20 Å. Both Na(3)-F(5) bond lengths are 2.28 Å. Both Na(3)-F(6) bond lengths are 2.26 Å. There are three inequivalent Pd sites. In the first Pd site, Pd(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(2), one F(3), and one F(6) atom. The Pd(1)-F(1) bond length is 1.98 Å. The Pd(1)-F(2) bond length is 1.96 Å. The Pd(1)-F(3) bond length is 1.96 Å. The Pd(1)-F(6) bond length is 1.99 Å. In the second Pd site, Pd(2) is bonded in a square co-planar geometry to two equivalent F(4) and two equivalent F(5) atoms. Both Pd(2)-F(4) bond lengths are 2.01 Å. Both Pd(2)-F(5) bond lengths are 1.99 Å. In the third Pd site, Pd(3) is bonded to two equivalent F(1), two equivalent F(4), and two equivalent F(6) atoms to form PdF6 octahedra that share corners with two equivalent Na(1)F6 octahedra and edges with two equivalent Na(3)F6 octahedra. The corner-sharing octahedral tilt angles are 65°. Both Pd(3)-F(1) bond lengths are 2.15 Å. Both Pd(3)-F(4) bond lengths are 2.19 Å. Both Pd(3)-F(6) bond lengths are 2.18 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), one Na(3), one Pd(1), and one Pd(3) atom to form distorted FNa2Pd2 tetrahedra that share  a cornercorner with one F(2)Na3Pd tetrahedra, corners with two equivalent F(4)Na2Pd2 tetrahedra, corners with two equivalent F(5)Na3Pd tetrahedra, corners with three equivalent F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(4)Na2Pd2 tetrahedra,  an edgeedge with one F(2)Na3Pd tetrahedra, and  an edgeedge with one F(5)Na3Pd tetrahedra. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Pd(1) atom to form FNa3Pd tetrahedra that share  a cornercorner with one F(1)Na2Pd2 tetrahedra,  a cornercorner with one F(2)Na3Pd tetrahedra, corners with two equivalent F(4)Na2Pd2 tetrahedra, corners with two equivalent F(5)Na3Pd tetrahedra,  an edgeedge with one F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(4)Na2Pd2 tetrahedra,  an edgeedge with one F(2)Na3Pd tetrahedra, and  an edgeedge with one F(5)Na3Pd tetrahedra. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Pd(1) atom. In the fourth F site, F(4) is bonded to one Na(1), one Na(2), one Pd(2), and one Pd(3) atom to form FNa2Pd2 tetrahedra that share corners with two equivalent F(1)Na2Pd2 tetrahedra, corners with two equivalent F(2)Na3Pd tetrahedra, corners with three equivalent F(4)Na2Pd2 tetrahedra, corners with three equivalent F(5)Na3Pd tetrahedra,  an edgeedge with one F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(2)Na3Pd tetrahedra, and  an edgeedge with one F(5)Na3Pd tetrahedra. In the fifth F site, F(5) is bonded to one Na(1), one Na(2), one Na(3), and one Pd(2) atom to form FNa3Pd tetrahedra that share corners with two equivalent F(1)Na2Pd2 tetrahedra, corners with two equivalent F(2)Na3Pd tetrahedra, corners with three equivalent F(4)Na2Pd2 tetrahedra, corners with three equivalent F(5)Na3Pd tetrahedra,  an edgeedge with one F(1)Na2Pd2 tetrahedra,  an edgeedge with one F(4)Na2Pd2 tetrahedra, and  an edgeedge with one F(2)Na3Pd tetrahedra. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Na(3), one Pd(1), and one Pd(3) atom.