Na3GaSe3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent Ga(1), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to two equivalent Se(2) and two equivalent Se(3) atoms. Ga(1) is bonded to two equivalent Na(2), one Se(2), one Se(3), and two equivalent Se(1) atoms to form distorted face-sharing GaNa2Se4 tetrahedra. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a 3-coordinate geometry to one Na(1), two equivalent Na(2), and two equivalent Ga(1) atoms. In the second Se site, Se(2) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom. In the third Se site, Se(3) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom.
Na3GaSe3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. The Na(1)-Se(1) bond length is 2.93 Å. There is one shorter (3.04 Å) and one longer (3.10 Å) Na(1)-Se(2) bond length. There is one shorter (2.93 Å) and one longer (3.35 Å) Na(1)-Se(3) bond length. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent Ga(1), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. There is one shorter (3.26 Å) and one longer (3.29 Å) Na(2)-Ga(1) bond length. There is one shorter (3.32 Å) and one longer (3.42 Å) Na(2)-Se(1) bond length. There is one shorter (2.91 Å) and one longer (3.09 Å) Na(2)-Se(2) bond length. There is one shorter (2.88 Å) and one longer (3.04 Å) Na(2)-Se(3) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to two equivalent Se(2) and two equivalent Se(3) atoms. There is one shorter (2.97 Å) and one longer (3.00 Å) Na(3)-Se(2) bond length. There is one shorter (2.96 Å) and one longer (3.04 Å) Na(3)-Se(3) bond length. Ga(1) is bonded to two equivalent Na(2), one Se(2), one Se(3), and two equivalent Se(1) atoms to form distorted face-sharing GaNa2Se4 tetrahedra. The Ga(1)-Se(2) bond length is 2.37 Å. The Ga(1)-Se(3) bond length is 2.37 Å. There is one shorter (2.43 Å) and one longer (2.48 Å) Ga(1)-Se(1) bond length. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a 3-coordinate geometry to one Na(1), two equivalent Na(2), and two equivalent Ga(1) atoms. In the second Se site, Se(2) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom. In the third Se site, Se(3) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ga(1) atom.