Na4Eu2PbP4 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one Pb(1), one P(2), one P(3), and one P(4) atom. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one P(3), one P(4), and two equivalent P(2) atoms. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one P(3), one P(4), and two equivalent P(1) atoms. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one P(1), one P(2), one P(3), and one P(4) atom. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 3-coordinate geometry to one Pb(1), one P(1), one P(2), one P(4), and two equivalent P(3) atoms. In the second Eu site, Eu(2) is bonded in a 3-coordinate geometry to one Pb(1), one P(4), two equivalent P(1), and two equivalent P(2) atoms. Pb(1) is bonded in a 7-coordinate geometry to one Na(1), one Eu(1), one Eu(2), one P(1), one P(2), one P(3), and one P(4) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 7-coordinate geometry to one Na(4), two equivalent Na(3), one Eu(1), two equivalent Eu(2), and one Pb(1) atom. In the second P site, P(2) is bonded in a 8-coordinate geometry to one Na(1), one Na(4), two equivalent Na(2), one Eu(1), two equivalent Eu(2), and one Pb(1) atom. In the third P site, P(3) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), two equivalent Eu(1), and one Pb(1) atom. In the fourth P site, P(4) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Eu(1), one Eu(2), and one Pb(1) atom.
Na4Eu2PbP4 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one Pb(1), one P(2), one P(3), and one P(4) atom. The Na(1)-Pb(1) bond length is 3.42 Å. The Na(1)-P(2) bond length is 3.13 Å. The Na(1)-P(3) bond length is 3.05 Å. The Na(1)-P(4) bond length is 2.86 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one P(3), one P(4), and two equivalent P(2) atoms. The Na(2)-P(3) bond length is 2.83 Å. The Na(2)-P(4) bond length is 3.29 Å. There is one shorter (2.90 Å) and one longer (3.00 Å) Na(2)-P(2) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one P(3), one P(4), and two equivalent P(1) atoms. The Na(3)-P(3) bond length is 2.83 Å. The Na(3)-P(4) bond length is 3.14 Å. There is one shorter (2.90 Å) and one longer (3.13 Å) Na(3)-P(1) bond length. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one P(1), one P(2), one P(3), and one P(4) atom. The Na(4)-P(1) bond length is 2.94 Å. The Na(4)-P(2) bond length is 2.92 Å. The Na(4)-P(3) bond length is 3.02 Å. The Na(4)-P(4) bond length is 3.34 Å. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 3-coordinate geometry to one Pb(1), one P(1), one P(2), one P(4), and two equivalent P(3) atoms. The Eu(1)-Pb(1) bond length is 3.40 Å. The Eu(1)-P(1) bond length is 3.05 Å. The Eu(1)-P(2) bond length is 3.31 Å. The Eu(1)-P(4) bond length is 2.96 Å. There is one shorter (3.07 Å) and one longer (3.32 Å) Eu(1)-P(3) bond length. In the second Eu site, Eu(2) is bonded in a 3-coordinate geometry to one Pb(1), one P(4), two equivalent P(1), and two equivalent P(2) atoms. The Eu(2)-Pb(1) bond length is 3.38 Å. The Eu(2)-P(4) bond length is 2.91 Å. There is one shorter (3.02 Å) and one longer (3.47 Å) Eu(2)-P(1) bond length. There is one shorter (3.04 Å) and one longer (3.27 Å) Eu(2)-P(2) bond length. Pb(1) is bonded in a 7-coordinate geometry to one Na(1), one Eu(1), one Eu(2), one P(1), one P(2), one P(3), and one P(4) atom. The Pb(1)-P(1) bond length is 2.62 Å. The Pb(1)-P(2) bond length is 2.70 Å. The Pb(1)-P(3) bond length is 2.61 Å. The Pb(1)-P(4) bond length is 2.65 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 7-coordinate geometry to one Na(4), two equivalent Na(3), one Eu(1), two equivalent Eu(2), and one Pb(1) atom. In the second P site, P(2) is bonded in a 8-coordinate geometry to one Na(1), one Na(4), two equivalent Na(2), one Eu(1), two equivalent Eu(2), and one Pb(1) atom. In the third P site, P(3) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), two equivalent Eu(1), and one Pb(1) atom. In the fourth P site, P(4) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Eu(1), one Eu(2), and one Pb(1) atom.