Na6GaP3 crystallizes in the triclinic P1 space group. There are twenty-four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one P(3), one P(4), one P(8), and one P(9) atom. In the second Na site, Na(2) is bonded to one Na(6), one P(1), one P(12), one P(2), and one P(7) atom to form distorted NaNaP4 tetrahedra that share  a cornercorner with one Na(18)P4 tetrahedra,  a cornercorner with one Na(7)P4 tetrahedra,  an edgeedge with one Na(23)NaP4 tetrahedra, and  an edgeedge with one Na(7)P4 tetrahedra. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one Na(6), one P(2), one P(3), one P(4), and one P(8) atom. In the fourth Na site, Na(4) is bonded in a 3-coordinate geometry to one P(3), one P(5), and one P(9) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one P(11), one P(12), one P(2), and one P(6) atom. In the sixth Na site, Na(6) is bonded in a 10-coordinate geometry to one Na(14), one Na(15), one Na(2), one Na(3), one Na(8), one Ga(4), one P(12), one P(2), one P(3), and one P(7) atom. In the seventh Na site, Na(7) is bonded to one P(12), one P(2), one P(4), and one P(7) atom to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. In the eighth Na site, Na(8) is bonded in a 4-coordinate geometry to one Na(6), one P(12), one P(2), one P(6), and one P(7) atom. In the ninth Na site, Na(9) is bonded in a 3-coordinate geometry to one P(1), one P(11), one P(5), and one P(6) atom. In the tenth Na site, Na(10) is bonded in a 4-coordinate geometry to one Na(19), one P(10), one P(5), one P(6), and one P(9) atom. In the eleventh Na site, Na(11) is bonded in a distorted trigonal planar geometry to one Na(19), one P(1), one P(10), and one P(9) atom. In the twelfth Na site, Na(12) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one P(3), one P(5), one P(8), and one P(9) atom. In the thirteenth Na site, Na(13) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one P(10), one P(4), one P(5), and one P(8) atom. In the fourteenth Na site, Na(14) is bonded in a 3-coordinate geometry to one Na(6), one P(12), one P(3), one P(4), and one P(8) atom. In the fifteenth Na site, Na(15) is bonded in a 4-coordinate geometry to one Na(6), one P(3), one P(4), one P(7), and one P(8) atom. In the sixteenth Na site, Na(16) is bonded in a 4-coordinate geometry to one P(12), one P(2), one P(7), and one P(8) atom. In the seventeenth Na site, Na(17) is bonded in a 4-coordinate geometry to one Na(19), one P(1), one P(11), one P(6), and one P(7) atom. In the eighteenth Na site, Na(18) is bonded to one P(1), one P(11), one P(6), and one P(9) atom to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. In the nineteenth Na site, Na(19) is bonded in a 10-coordinate geometry to one Na(10), one Na(11), one Na(17), one Na(22), one Na(23), one Ga(1), one P(1), one P(10), one P(11), and one P(6) atom. In the twentieth Na site, Na(20) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one P(1), one P(11), one P(2), and one P(7) atom. In the twenty-first Na site, Na(21) is bonded in a 3-coordinate geometry to one P(10), one P(3), one P(4), and one P(8) atom. In the twenty-second Na site, Na(22) is bonded in a 3-coordinate geometry to one Na(19), one P(10), one P(11), and one P(9) atom. In the twenty-third Na site, Na(23) is bonded to one Na(19), one P(1), one P(11), one P(12), and one P(6) atom to form distorted NaNaP4 tetrahedra that share  a cornercorner with one Na(18)P4 tetrahedra,  a cornercorner with one Na(7)P4 tetrahedra,  an edgeedge with one Na(2)NaP4 tetrahedra, and  an edgeedge with one Na(18)P4 tetrahedra. In the twenty-fourth Na site, Na(24) is bonded in a 4-coordinate geometry to one P(10), one P(4), one P(5), and one P(9) atom. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 6-coordinate geometry to one Na(19), one Na(20), one Na(5), one P(1), one P(11), and one P(6) atom. In the second Ga site, Ga(2) is bonded in a 3-coordinate geometry to one Na(12), one Na(13), one P(3), one P(4), and one P(8) atom. In the third Ga site, Ga(3) is bonded in a 3-coordinate geometry to one Na(12), one Na(13), one P(10), one P(5), and one P(9) atom. In the fourth Ga site, Ga(4) is bonded in a 3-coordinate geometry to one Na(20), one Na(5), one Na(6), one P(12), one P(2), and one P(7) atom. There are twelve inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Na(11), one Na(17), one Na(18), one Na(19), one Na(2), one Na(20), one Na(23), one Na(9), and one Ga(1) atom. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Na(16), one Na(2), one Na(20), one Na(3), one Na(5), one Na(6), one Na(7), one Na(8), and one Ga(4) atom. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(12), one Na(14), one Na(15), one Na(21), one Na(3), one Na(4), one Na(6), and one Ga(2) atom. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one Na(1), one Na(13), one Na(14), one Na(15), one Na(21), one Na(24), one Na(3), one Na(7), and one Ga(2) atom. In the fifth P site, P(5) is bonded in a 7-coordinate geometry to one Na(10), one Na(12), one Na(13), one Na(24), one Na(4), one Na(9), and one Ga(3) atom. In the sixth P site, P(6) is bonded in a 9-coordinate geometry to one Na(10), one Na(17), one Na(18), one Na(19), one Na(23), one Na(5), one Na(8), one Na(9), and one Ga(1) atom. In the seventh P site, P(7) is bonded in a 9-coordinate geometry to one Na(15), one Na(16), one Na(17), one Na(2), one Na(20), one Na(6), one Na(7), one Na(8), and one Ga(4) atom. In the eighth P site, P(8) is bonded in a 9-coordinate geometry to one Na(1), one Na(12), one Na(13), one Na(14), one Na(15), one Na(16), one Na(21), one Na(3), and one Ga(2) atom. In the ninth P site, P(9) is bonded in a 9-coordinate geometry to one Na(1), one Na(10), one Na(11), one Na(12), one Na(18), one Na(22), one Na(24), one Na(4), and one Ga(3) atom. In the tenth P site, P(10) is bonded in a 8-coordinate geometry to one Na(10), one Na(11), one Na(13), one Na(19), one Na(21), one Na(22), one Na(24), and one Ga(3) atom. In the eleventh P site, P(11) is bonded in a 9-coordinate geometry to one Na(17), one Na(18), one Na(19), one Na(20), one Na(22), one Na(23), one Na(5), one Na(9), and one Ga(1) atom. In the twelfth P site, P(12) is bonded in a 9-coordinate geometry to one Na(14), one Na(16), one Na(2), one Na(23), one Na(5), one Na(6), one Na(7), one Na(8), and one Ga(4) atom.
Na6GaP3 crystallizes in the triclinic P1 space group. There are twenty-four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one P(3), one P(4), one P(8), and one P(9) atom. The Na(1)-P(3) bond length is 2.97 Å. The Na(1)-P(4) bond length is 2.86 Å. The Na(1)-P(8) bond length is 2.85 Å. The Na(1)-P(9) bond length is 3.13 Å. In the second Na site, Na(2) is bonded to one Na(6), one P(1), one P(12), one P(2), and one P(7) atom to form distorted NaNaP4 tetrahedra that share  a cornercorner with one Na(18)P4 tetrahedra,  a cornercorner with one Na(7)P4 tetrahedra,  an edgeedge with one Na(23)NaP4 tetrahedra, and  an edgeedge with one Na(7)P4 tetrahedra. The Na(2)-Na(6) bond length is 3.14 Å. The Na(2)-P(1) bond length is 3.07 Å. The Na(2)-P(12) bond length is 2.92 Å. The Na(2)-P(2) bond length is 2.85 Å. The Na(2)-P(7) bond length is 2.96 Å. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one Na(6), one P(2), one P(3), one P(4), and one P(8) atom. The Na(3)-Na(6) bond length is 3.22 Å. The Na(3)-P(2) bond length is 3.04 Å. The Na(3)-P(3) bond length is 2.98 Å. The Na(3)-P(4) bond length is 2.98 Å. The Na(3)-P(8) bond length is 3.20 Å. In the fourth Na site, Na(4) is bonded in a 3-coordinate geometry to one P(3), one P(5), and one P(9) atom. The Na(4)-P(3) bond length is 2.89 Å. The Na(4)-P(5) bond length is 2.81 Å. The Na(4)-P(9) bond length is 2.88 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one P(11), one P(12), one P(2), and one P(6) atom. The Na(5)-Ga(1) bond length is 2.93 Å. The Na(5)-Ga(4) bond length is 2.96 Å. The Na(5)-P(11) bond length is 2.92 Å. The Na(5)-P(12) bond length is 3.09 Å. The Na(5)-P(2) bond length is 2.93 Å. The Na(5)-P(6) bond length is 3.07 Å. In the sixth Na site, Na(6) is bonded in a 10-coordinate geometry to one Na(14), one Na(15), one Na(2), one Na(3), one Na(8), one Ga(4), one P(12), one P(2), one P(3), and one P(7) atom. The Na(6)-Na(14) bond length is 3.24 Å. The Na(6)-Na(15) bond length is 3.17 Å. The Na(6)-Na(8) bond length is 3.02 Å. The Na(6)-Ga(4) bond length is 3.17 Å. The Na(6)-P(12) bond length is 2.96 Å. The Na(6)-P(2) bond length is 3.14 Å. The Na(6)-P(3) bond length is 2.93 Å. The Na(6)-P(7) bond length is 2.98 Å. In the seventh Na site, Na(7) is bonded to one P(12), one P(2), one P(4), and one P(7) atom to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. The Na(7)-P(12) bond length is 3.02 Å. The Na(7)-P(2) bond length is 3.01 Å. The Na(7)-P(4) bond length is 2.92 Å. The Na(7)-P(7) bond length is 2.93 Å. In the eighth Na site, Na(8) is bonded in a 4-coordinate geometry to one Na(6), one P(12), one P(2), one P(6), and one P(7) atom. The Na(8)-P(12) bond length is 2.92 Å. The Na(8)-P(2) bond length is 2.88 Å. The Na(8)-P(6) bond length is 2.92 Å. The Na(8)-P(7) bond length is 3.25 Å. In the ninth Na site, Na(9) is bonded in a 3-coordinate geometry to one P(1), one P(11), one P(5), and one P(6) atom. The Na(9)-P(1) bond length is 2.99 Å. The Na(9)-P(11) bond length is 3.34 Å. The Na(9)-P(5) bond length is 3.03 Å. The Na(9)-P(6) bond length is 2.90 Å. In the tenth Na site, Na(10) is bonded in a 4-coordinate geometry to one Na(19), one P(10), one P(5), one P(6), and one P(9) atom. The Na(10)-Na(19) bond length is 3.20 Å. The Na(10)-P(10) bond length is 2.86 Å. The Na(10)-P(5) bond length is 2.93 Å. The Na(10)-P(6) bond length is 3.08 Å. The Na(10)-P(9) bond length is 3.18 Å. In the eleventh Na site, Na(11) is bonded in a distorted trigonal planar geometry to one Na(19), one P(1), one P(10), and one P(9) atom. The Na(11)-Na(19) bond length is 3.24 Å. The Na(11)-P(1) bond length is 2.92 Å. The Na(11)-P(10) bond length is 2.85 Å. The Na(11)-P(9) bond length is 2.90 Å. In the twelfth Na site, Na(12) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one P(3), one P(5), one P(8), and one P(9) atom. The Na(12)-Ga(2) bond length is 2.94 Å. The Na(12)-Ga(3) bond length is 2.96 Å. The Na(12)-P(3) bond length is 3.09 Å. The Na(12)-P(5) bond length is 2.90 Å. The Na(12)-P(8) bond length is 2.95 Å. The Na(12)-P(9) bond length is 3.07 Å. In the thirteenth Na site, Na(13) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one P(10), one P(4), one P(5), and one P(8) atom. The Na(13)-Ga(2) bond length is 3.04 Å. The Na(13)-Ga(3) bond length is 2.99 Å. The Na(13)-P(10) bond length is 3.14 Å. The Na(13)-P(4) bond length is 3.12 Å. The Na(13)-P(5) bond length is 2.90 Å. The Na(13)-P(8) bond length is 3.03 Å. In the fourteenth Na site, Na(14) is bonded in a 3-coordinate geometry to one Na(6), one P(12), one P(3), one P(4), and one P(8) atom. The Na(14)-P(12) bond length is 2.85 Å. The Na(14)-P(3) bond length is 2.84 Å. The Na(14)-P(4) bond length is 2.96 Å. The Na(14)-P(8) bond length is 3.35 Å. In the fifteenth Na site, Na(15) is bonded in a 4-coordinate geometry to one Na(6), one P(3), one P(4), one P(7), and one P(8) atom. The Na(15)-P(3) bond length is 2.91 Å. The Na(15)-P(4) bond length is 3.06 Å. The Na(15)-P(7) bond length is 2.97 Å. The Na(15)-P(8) bond length is 3.00 Å. In the sixteenth Na site, Na(16) is bonded in a 4-coordinate geometry to one P(12), one P(2), one P(7), and one P(8) atom. The Na(16)-P(12) bond length is 3.01 Å. The Na(16)-P(2) bond length is 3.27 Å. The Na(16)-P(7) bond length is 2.89 Å. The Na(16)-P(8) bond length is 3.05 Å. In the seventeenth Na site, Na(17) is bonded in a 4-coordinate geometry to one Na(19), one P(1), one P(11), one P(6), and one P(7) atom. The Na(17)-Na(19) bond length is 3.02 Å. The Na(17)-P(1) bond length is 2.93 Å. The Na(17)-P(11) bond length is 2.88 Å. The Na(17)-P(6) bond length is 3.22 Å. The Na(17)-P(7) bond length is 2.92 Å. In the eighteenth Na site, Na(18) is bonded to one P(1), one P(11), one P(6), and one P(9) atom to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. The Na(18)-P(1) bond length is 3.02 Å. The Na(18)-P(11) bond length is 3.08 Å. The Na(18)-P(6) bond length is 2.91 Å. The Na(18)-P(9) bond length is 2.94 Å. In the nineteenth Na site, Na(19) is bonded in a 10-coordinate geometry to one Na(10), one Na(11), one Na(17), one Na(22), one Na(23), one Ga(1), one P(1), one P(10), one P(11), and one P(6) atom. The Na(19)-Na(22) bond length is 3.21 Å. The Na(19)-Na(23) bond length is 3.12 Å. The Na(19)-Ga(1) bond length is 3.15 Å. The Na(19)-P(1) bond length is 2.94 Å. The Na(19)-P(10) bond length is 2.98 Å. The Na(19)-P(11) bond length is 3.15 Å. The Na(19)-P(6) bond length is 2.95 Å. In the twentieth Na site, Na(20) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one P(1), one P(11), one P(2), and one P(7) atom. The Na(20)-Ga(1) bond length is 2.95 Å. The Na(20)-Ga(4) bond length is 2.94 Å. The Na(20)-P(1) bond length is 3.11 Å. The Na(20)-P(11) bond length is 2.90 Å. The Na(20)-P(2) bond length is 2.95 Å. The Na(20)-P(7) bond length is 3.07 Å. In the twenty-first Na site, Na(21) is bonded in a 3-coordinate geometry to one P(10), one P(3), one P(4), and one P(8) atom. The Na(21)-P(10) bond length is 2.94 Å. The Na(21)-P(3) bond length is 3.29 Å. The Na(21)-P(4) bond length is 2.92 Å. The Na(21)-P(8) bond length is 2.87 Å. In the twenty-second Na site, Na(22) is bonded in a 3-coordinate geometry to one Na(19), one P(10), one P(11), and one P(9) atom. The Na(22)-P(10) bond length is 2.97 Å. The Na(22)-P(11) bond length is 2.95 Å. The Na(22)-P(9) bond length is 3.04 Å. In the twenty-third Na site, Na(23) is bonded to one Na(19), one P(1), one P(11), one P(12), and one P(6) atom to form distorted NaNaP4 tetrahedra that share  a cornercorner with one Na(18)P4 tetrahedra,  a cornercorner with one Na(7)P4 tetrahedra,  an edgeedge with one Na(2)NaP4 tetrahedra, and  an edgeedge with one Na(18)P4 tetrahedra. The Na(23)-P(1) bond length is 2.92 Å. The Na(23)-P(11) bond length is 2.85 Å. The Na(23)-P(12) bond length is 3.06 Å. The Na(23)-P(6) bond length is 2.98 Å. In the twenty-fourth Na site, Na(24) is bonded in a 4-coordinate geometry to one P(10), one P(4), one P(5), and one P(9) atom. The Na(24)-P(10) bond length is 2.86 Å. The Na(24)-P(4) bond length is 3.17 Å. The Na(24)-P(5) bond length is 2.84 Å. The Na(24)-P(9) bond length is 2.88 Å. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 6-coordinate geometry to one Na(19), one Na(20), one Na(5), one P(1), one P(11), and one P(6) atom. The Ga(1)-P(1) bond length is 2.40 Å. The Ga(1)-P(11) bond length is 2.49 Å. The Ga(1)-P(6) bond length is 2.42 Å. In the second Ga site, Ga(2) is bonded in a 3-coordinate geometry to one Na(12), one Na(13), one P(3), one P(4), and one P(8) atom. The Ga(2)-P(3) bond length is 2.44 Å. The Ga(2)-P(4) bond length is 2.40 Å. The Ga(2)-P(8) bond length is 2.44 Å. In the third Ga site, Ga(3) is bonded in a 3-coordinate geometry to one Na(12), one Na(13), one P(10), one P(5), and one P(9) atom. The Ga(3)-P(10) bond length is 2.39 Å. The Ga(3)-P(5) bond length is 2.45 Å. The Ga(3)-P(9) bond length is 2.39 Å. In the fourth Ga site, Ga(4) is bonded in a 3-coordinate geometry to one Na(20), one Na(5), one Na(6), one P(12), one P(2), and one P(7) atom. The Ga(4)-P(12) bond length is 2.41 Å. The Ga(4)-P(2) bond length is 2.49 Å. The Ga(4)-P(7) bond length is 2.42 Å. There are twelve inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Na(11), one Na(17), one Na(18), one Na(19), one Na(2), one Na(20), one Na(23), one Na(9), and one Ga(1) atom. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Na(16), one Na(2), one Na(20), one Na(3), one Na(5), one Na(6), one Na(7), one Na(8), and one Ga(4) atom. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(12), one Na(14), one Na(15), one Na(21), one Na(3), one Na(4), one Na(6), and one Ga(2) atom. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one Na(1), one Na(13), one Na(14), one Na(15), one Na(21), one Na(24), one Na(3), one Na(7), and one Ga(2) atom. In the fifth P site, P(5) is bonded in a 7-coordinate geometry to one Na(10), one Na(12), one Na(13), one Na(24), one Na(4), one Na(9), and one Ga(3) atom. In the sixth P site, P(6) is bonded in a 9-coordinate geometry to one Na(10), one Na(17), one Na(18), one Na(19), one Na(23), one Na(5), one Na(8), one Na(9), and one Ga(1) atom. In the seventh P site, P(7) is bonded in a 9-coordinate geometry to one Na(15), one Na(16), one Na(17), one Na(2), one Na(20), one Na(6), one Na(7), one Na(8), and one Ga(4) atom. In the eighth P site, P(8) is bonded in a 9-coordinate geometry to one Na(1), one Na(12), one Na(13), one Na(14), one Na(15), one Na(16), one Na(21), one Na(3), and one Ga(2) atom. In the ninth P site, P(9) is bonded in a 9-coordinate geometry to one Na(1), one Na(10), one Na(11), one Na(12), one Na(18), one Na(22), one Na(24), one Na(4), and one Ga(3) atom. In the tenth P site, P(10) is bonded in a 8-coordinate geometry to one Na(10), one Na(11), one Na(13), one Na(19), one Na(21), one Na(22), one Na(24), and one Ga(3) atom. In the eleventh P site, P(11) is bonded in a 9-coordinate geometry to one Na(17), one Na(18), one Na(19), one Na(20), one Na(22), one Na(23), one Na(5), one Na(9), and one Ga(1) atom. In the twelfth P site, P(12) is bonded in a 9-coordinate geometry to one Na(14), one Na(16), one Na(2), one Na(23), one Na(5), one Na(6), one Na(7), one Na(8), and one Ga(4) atom.