Cs3NaPb4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to three equivalent Pb(2) and four equivalent Pb(1) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Pb(1) and six equivalent Pb(2) atoms. Na(1) is bonded in a distorted hexagonal planar geometry to two equivalent Pb(2) and four equivalent Pb(1) atoms. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 10-coordinate geometry to one Cs(2), four equivalent Cs(1), two equivalent Na(1), one Pb(1), and two equivalent Pb(2) atoms. In the second Pb site, Pb(2) is bonded in a 10-coordinate geometry to three equivalent Cs(1), three equivalent Cs(2), one Na(1), one Pb(2), and two equivalent Pb(1) atoms.
Cs3NaPb4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to three equivalent Pb(2) and four equivalent Pb(1) atoms. There is one shorter (3.85 Å) and two longer (4.30 Å) Cs(1)-Pb(2) bond lengths. There are two shorter (4.12 Å) and two longer (4.15 Å) Cs(1)-Pb(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Pb(1) and six equivalent Pb(2) atoms. Both Cs(2)-Pb(1) bond lengths are 4.36 Å. There are two shorter (4.19 Å) and four longer (4.35 Å) Cs(2)-Pb(2) bond lengths. Na(1) is bonded in a distorted hexagonal planar geometry to two equivalent Pb(2) and four equivalent Pb(1) atoms. Both Na(1)-Pb(2) bond lengths are 3.26 Å. All Na(1)-Pb(1) bond lengths are 3.32 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 10-coordinate geometry to one Cs(2), four equivalent Cs(1), two equivalent Na(1), one Pb(1), and two equivalent Pb(2) atoms. The Pb(1)-Pb(1) bond length is 3.22 Å. Both Pb(1)-Pb(2) bond lengths are 3.11 Å. In the second Pb site, Pb(2) is bonded in a 10-coordinate geometry to three equivalent Cs(1), three equivalent Cs(2), one Na(1), one Pb(2), and two equivalent Pb(1) atoms. The Pb(2)-Pb(2) bond length is 3.05 Å.