Na2PdSe2 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent Pd(1), two equivalent Se(2), and three equivalent Se(1) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent Pd(1), three equivalent Se(1), and three equivalent Se(2) atoms. Pd(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Se(1), and two equivalent Se(2) atoms. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 8-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and two equivalent Pd(1) atoms. In the second Se site, Se(2) is bonded to two equivalent Na(1), three equivalent Na(2), and two equivalent Pd(1) atoms to form a mixture of distorted edge and corner-sharing SeNa5Pd2 pentagonal bipyramids.
Na2PdSe2 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent Pd(1), two equivalent Se(2), and three equivalent Se(1) atoms. Both Na(1)-Pd(1) bond lengths are 3.13 Å. There is one shorter (2.93 Å) and one longer (2.97 Å) Na(1)-Se(2) bond length. There are two shorter (2.95 Å) and one longer (3.05 Å) Na(1)-Se(1) bond length. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent Pd(1), three equivalent Se(1), and three equivalent Se(2) atoms. Both Na(2)-Pd(1) bond lengths are 3.28 Å. There are two shorter (3.15 Å) and one longer (3.34 Å) Na(2)-Se(1) bond length. There is one shorter (3.00 Å) and two longer (3.04 Å) Na(2)-Se(2) bond lengths. Pd(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Se(1), and two equivalent Se(2) atoms. Both Pd(1)-Se(1) bond lengths are 2.49 Å. Both Pd(1)-Se(2) bond lengths are 2.49 Å. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 8-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and two equivalent Pd(1) atoms. In the second Se site, Se(2) is bonded to two equivalent Na(1), three equivalent Na(2), and two equivalent Pd(1) atoms to form a mixture of distorted edge and corner-sharing SeNa5Pd2 pentagonal bipyramids.