K2Na3SiP3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent Si(1), one P(3), two equivalent P(1), and two equivalent P(2) atoms. In the second K site, K(2) is bonded in a 4-coordinate geometry to two equivalent P(3) and three equivalent P(1) atoms. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent Si(1), two equivalent P(3), and three equivalent P(2) atoms. In the second Na site, Na(2) is bonded to one P(1), one P(3), and two equivalent P(2) atoms to form corner-sharing NaP4 tetrahedra. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to two equivalent Si(1), one P(2), two equivalent P(1), and two equivalent P(3) atoms. Si(1) is bonded in a distorted trigonal planar geometry to two equivalent K(1), two equivalent Na(1), two equivalent Na(3), one P(1), one P(2), and one P(3) atom. There are three inequivalent P sites. In the first P site, P(3) is bonded in a 9-coordinate geometry to one K(1), two equivalent K(2), one Na(2), two equivalent Na(1), two equivalent Na(3), and one Si(1) atom. In the second P site, P(1) is bonded in a 9-coordinate geometry to two equivalent K(1), three equivalent K(2), one Na(2), two equivalent Na(3), and one Si(1) atom. In the third P site, P(2) is bonded in a 9-coordinate geometry to two equivalent K(1), one Na(3), two equivalent Na(2), three equivalent Na(1), and one Si(1) atom.
K2Na3SiP3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent Si(1), one P(3), two equivalent P(1), and two equivalent P(2) atoms. Both K(1)-Si(1) bond lengths are 3.36 Å. The K(1)-P(3) bond length is 3.24 Å. Both K(1)-P(1) bond lengths are 3.32 Å. Both K(1)-P(2) bond lengths are 3.33 Å. In the second K site, K(2) is bonded in a 4-coordinate geometry to two equivalent P(3) and three equivalent P(1) atoms. Both K(2)-P(3) bond lengths are 3.43 Å. There are two shorter (3.38 Å) and one longer (3.75 Å) K(2)-P(1) bond length. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent Si(1), two equivalent P(3), and three equivalent P(2) atoms. Both Na(1)-Si(1) bond lengths are 3.20 Å. Both Na(1)-P(3) bond lengths are 3.17 Å. There is one shorter (2.93 Å) and two longer (3.25 Å) Na(1)-P(2) bond lengths. In the second Na site, Na(2) is bonded to one P(1), one P(3), and two equivalent P(2) atoms to form corner-sharing NaP4 tetrahedra. The Na(2)-P(1) bond length is 2.97 Å. The Na(2)-P(3) bond length is 2.93 Å. Both Na(2)-P(2) bond lengths are 2.96 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to two equivalent Si(1), one P(2), two equivalent P(1), and two equivalent P(3) atoms. Both Na(3)-Si(1) bond lengths are 3.21 Å. The Na(3)-P(2) bond length is 3.03 Å. Both Na(3)-P(1) bond lengths are 3.26 Å. Both Na(3)-P(3) bond lengths are 3.21 Å. Si(1) is bonded in a distorted trigonal planar geometry to two equivalent K(1), two equivalent Na(1), two equivalent Na(3), one P(1), one P(2), and one P(3) atom. The Si(1)-P(1) bond length is 2.20 Å. The Si(1)-P(2) bond length is 2.20 Å. The Si(1)-P(3) bond length is 2.18 Å. There are three inequivalent P sites. In the first P site, P(3) is bonded in a 9-coordinate geometry to one K(1), two equivalent K(2), one Na(2), two equivalent Na(1), two equivalent Na(3), and one Si(1) atom. In the second P site, P(1) is bonded in a 9-coordinate geometry to two equivalent K(1), three equivalent K(2), one Na(2), two equivalent Na(3), and one Si(1) atom. In the third P site, P(2) is bonded in a 9-coordinate geometry to two equivalent K(1), one Na(3), two equivalent Na(2), three equivalent Na(1), and one Si(1) atom.