Na6GaAs3 crystallizes in the triclinic P1 space group. There are twenty-four inequivalent Na sites. In the first Na site, Na(1) is bonded to one As(1), one As(12), one As(3), and one As(9) atom to form distorted NaAs4 tetrahedra that share  a cornercorner with one Na(10)As4 tetrahedra,  a cornercorner with one Na(15)As4 tetrahedra,  a cornercorner with one Na(19)As4 tetrahedra,  an edgeedge with one Na(15)As4 tetrahedra, and  an edgeedge with one Na(24)NaAs4 tetrahedra. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one As(2), one As(5), one As(7), and one As(8) atom. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one Ga(4), one As(12), one As(2), one As(3), and one As(9) atom. In the fourth Na site, Na(4) is bonded in a 3-coordinate geometry to one As(12), one As(2), one As(7), and one As(8) atom. In the fifth Na site, Na(5) is bonded in a 3-coordinate geometry to one As(2), one As(5), and one As(6) atom. In the sixth Na site, Na(6) is bonded in a 4-coordinate geometry to one Na(22), one As(11), one As(4), one As(5), and one As(6) atom. In the seventh Na site, Na(7) is bonded in a 5-coordinate geometry to one Ga(2), one As(2), one As(3), one As(7), and one As(8) atom. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one As(2), one As(5), one As(6), and one As(7) atom. In the ninth Na site, Na(9) is bonded in a 4-coordinate geometry to one As(12), one As(3), one As(4), and one As(9) atom. In the tenth Na site, Na(10) is bonded to one As(1), one As(10), one As(4), and one As(5) atom to form distorted NaAs4 tetrahedra that share  a cornercorner with one Na(1)As4 tetrahedra,  a cornercorner with one Na(23)As4 tetrahedra,  a cornercorner with one Na(24)NaAs4 tetrahedra, and  an edgeedge with one Na(24)NaAs4 tetrahedra. In the eleventh Na site, Na(11) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one As(10), one As(12), one As(3), and one As(4) atom. In the twelfth Na site, Na(12) is bonded in a 3-coordinate geometry to one As(1), one As(10), one As(4), and one As(6) atom. In the thirteenth Na site, Na(13) is bonded in a 4-coordinate geometry to one As(12), one As(3), one As(7), and one As(9) atom. In the fourteenth Na site, Na(14) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one As(1), one As(10), one As(3), and one As(9) atom. In the fifteenth Na site, Na(15) is bonded to one As(12), one As(3), one As(8), and one As(9) atom to form distorted NaAs4 tetrahedra that share  a cornercorner with one Na(1)As4 tetrahedra,  a cornercorner with one Na(23)As4 tetrahedra,  a cornercorner with one Na(24)NaAs4 tetrahedra,  an edgeedge with one Na(1)As4 tetrahedra, and  an edgeedge with one Na(19)As4 tetrahedra. In the sixteenth Na site, Na(16) is bonded in a 4-coordinate geometry to one Na(22), one As(1), one As(10), one As(4), and one As(9) atom. In the seventeenth Na site, Na(17) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one As(11), one As(6), one As(7), and one As(8) atom. In the eighteenth Na site, Na(18) is bonded in a 3-coordinate geometry to one Na(22), one Ga(3), one As(10), one As(11), and one As(5) atom. In the nineteenth Na site, Na(19) is bonded to one As(2), one As(7), one As(8), and one As(9) atom to form a mixture of distorted corner and edge-sharing NaAs4 tetrahedra. In the twentieth Na site, Na(20) is bonded in a 3-coordinate geometry to one Na(22), one As(1), one As(11), and one As(5) atom. In the twenty-first Na site, Na(21) is bonded in a 4-coordinate geometry to one As(11), one As(2), one As(7), and one As(8) atom. In the twenty-second Na site, Na(22) is bonded in a 10-coordinate geometry to one Na(16), one Na(18), one Na(20), one Na(24), one Na(6), one Ga(1), one As(1), one As(10), one As(11), and one As(4) atom. In the twenty-third Na site, Na(23) is bonded to one As(11), one As(5), one As(6), and one As(8) atom to form distorted corner-sharing NaAs4 tetrahedra. In the twenty-fourth Na site, Na(24) is bonded to one Na(22), one As(1), one As(10), one As(12), and one As(4) atom to form a mixture of distorted corner and edge-sharing NaNaAs4 tetrahedra. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 6-coordinate geometry to one Na(11), one Na(14), one Na(22), one As(1), one As(10), and one As(4) atom. In the second Ga site, Ga(2) is bonded in a 3-coordinate geometry to one Na(17), one Na(7), one Na(8), one As(2), one As(7), and one As(8) atom. In the third Ga site, Ga(3) is bonded in a 7-coordinate geometry to one Na(17), one Na(18), one Na(8), one As(11), one As(5), one As(6), and one As(7) atom. In the fourth Ga site, Ga(4) is bonded in a 6-coordinate geometry to one Na(11), one Na(14), one Na(3), one As(10), one As(12), one As(3), and one As(9) atom. There are twelve inequivalent As sites. In the first As site, As(1) is bonded in a 9-coordinate geometry to one Na(1), one Na(10), one Na(12), one Na(14), one Na(16), one Na(20), one Na(22), one Na(24), and one Ga(1) atom. In the second As site, As(2) is bonded in a 9-coordinate geometry to one Na(19), one Na(2), one Na(21), one Na(3), one Na(4), one Na(5), one Na(7), one Na(8), and one Ga(2) atom. In the third As site, As(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(11), one Na(13), one Na(14), one Na(15), one Na(3), one Na(7), one Na(9), and one Ga(4) atom. In the fourth As site, As(4) is bonded in a 9-coordinate geometry to one Na(10), one Na(11), one Na(12), one Na(16), one Na(22), one Na(24), one Na(6), one Na(9), and one Ga(1) atom. In the fifth As site, As(5) is bonded in a 9-coordinate geometry to one Na(10), one Na(18), one Na(2), one Na(20), one Na(23), one Na(5), one Na(6), one Na(8), and one Ga(3) atom. In the sixth As site, As(6) is bonded in a 7-coordinate geometry to one Na(12), one Na(17), one Na(23), one Na(5), one Na(6), one Na(8), and one Ga(3) atom. In the seventh As site, As(7) is bonded in a 10-coordinate geometry to one Na(13), one Na(17), one Na(19), one Na(2), one Na(21), one Na(4), one Na(7), one Na(8), one Ga(2), and one Ga(3) atom. In the eighth As site, As(8) is bonded in a 9-coordinate geometry to one Na(15), one Na(17), one Na(19), one Na(2), one Na(21), one Na(23), one Na(4), one Na(7), and one Ga(2) atom. In the ninth As site, As(9) is bonded in a 9-coordinate geometry to one Na(1), one Na(13), one Na(14), one Na(15), one Na(16), one Na(19), one Na(3), one Na(9), and one Ga(4) atom. In the tenth As site, As(10) is bonded in a 10-coordinate geometry to one Na(10), one Na(11), one Na(12), one Na(14), one Na(16), one Na(18), one Na(22), one Na(24), one Ga(1), and one Ga(4) atom. In the eleventh As site, As(11) is bonded in a 8-coordinate geometry to one Na(17), one Na(18), one Na(20), one Na(21), one Na(22), one Na(23), one Na(6), and one Ga(3) atom. In the twelfth As site, As(12) is bonded in a 9-coordinate geometry to one Na(1), one Na(11), one Na(13), one Na(15), one Na(24), one Na(3), one Na(4), one Na(9), and one Ga(4) atom.
Na6GaAs3 crystallizes in the triclinic P1 space group. There are twenty-four inequivalent Na sites. In the first Na site, Na(1) is bonded to one As(1), one As(12), one As(3), and one As(9) atom to form distorted NaAs4 tetrahedra that share  a cornercorner with one Na(10)As4 tetrahedra,  a cornercorner with one Na(15)As4 tetrahedra,  a cornercorner with one Na(19)As4 tetrahedra,  an edgeedge with one Na(15)As4 tetrahedra, and  an edgeedge with one Na(24)NaAs4 tetrahedra. The Na(1)-As(1) bond length is 3.12 Å. The Na(1)-As(12) bond length is 3.03 Å. The Na(1)-As(3) bond length is 2.93 Å. The Na(1)-As(9) bond length is 3.06 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one As(2), one As(5), one As(7), and one As(8) atom. The Na(2)-As(2) bond length is 3.08 Å. The Na(2)-As(5) bond length is 3.16 Å. The Na(2)-As(7) bond length is 2.94 Å. The Na(2)-As(8) bond length is 2.95 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one Ga(4), one As(12), one As(2), one As(3), and one As(9) atom. The Na(3)-Ga(4) bond length is 3.24 Å. The Na(3)-As(12) bond length is 3.04 Å. The Na(3)-As(2) bond length is 2.98 Å. The Na(3)-As(3) bond length is 3.26 Å. The Na(3)-As(9) bond length is 3.08 Å. In the fourth Na site, Na(4) is bonded in a 3-coordinate geometry to one As(12), one As(2), one As(7), and one As(8) atom. The Na(4)-As(12) bond length is 2.93 Å. The Na(4)-As(2) bond length is 2.93 Å. The Na(4)-As(7) bond length is 3.44 Å. The Na(4)-As(8) bond length is 3.04 Å. In the fifth Na site, Na(5) is bonded in a 3-coordinate geometry to one As(2), one As(5), and one As(6) atom. The Na(5)-As(2) bond length is 2.94 Å. The Na(5)-As(5) bond length is 2.96 Å. The Na(5)-As(6) bond length is 2.87 Å. In the sixth Na site, Na(6) is bonded in a 4-coordinate geometry to one Na(22), one As(11), one As(4), one As(5), and one As(6) atom. The Na(6)-Na(22) bond length is 3.29 Å. The Na(6)-As(11) bond length is 2.96 Å. The Na(6)-As(4) bond length is 3.08 Å. The Na(6)-As(5) bond length is 3.27 Å. The Na(6)-As(6) bond length is 3.05 Å. In the seventh Na site, Na(7) is bonded in a 5-coordinate geometry to one Ga(2), one As(2), one As(3), one As(7), and one As(8) atom. The Na(7)-Ga(2) bond length is 3.31 Å. The Na(7)-As(2) bond length is 3.05 Å. The Na(7)-As(3) bond length is 3.18 Å. The Na(7)-As(7) bond length is 3.32 Å. The Na(7)-As(8) bond length is 3.06 Å. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one As(2), one As(5), one As(6), and one As(7) atom. The Na(8)-Ga(2) bond length is 3.00 Å. The Na(8)-Ga(3) bond length is 3.03 Å. The Na(8)-As(2) bond length is 3.21 Å. The Na(8)-As(5) bond length is 3.16 Å. The Na(8)-As(6) bond length is 2.98 Å. The Na(8)-As(7) bond length is 3.01 Å. In the ninth Na site, Na(9) is bonded in a 4-coordinate geometry to one As(12), one As(3), one As(4), and one As(9) atom. The Na(9)-As(12) bond length is 3.02 Å. The Na(9)-As(3) bond length is 2.97 Å. The Na(9)-As(4) bond length is 2.99 Å. The Na(9)-As(9) bond length is 3.30 Å. In the tenth Na site, Na(10) is bonded to one As(1), one As(10), one As(4), and one As(5) atom to form distorted NaAs4 tetrahedra that share  a cornercorner with one Na(1)As4 tetrahedra,  a cornercorner with one Na(23)As4 tetrahedra,  a cornercorner with one Na(24)NaAs4 tetrahedra, and  an edgeedge with one Na(24)NaAs4 tetrahedra. The Na(10)-As(1) bond length is 3.12 Å. The Na(10)-As(10) bond length is 3.18 Å. The Na(10)-As(4) bond length is 3.00 Å. The Na(10)-As(5) bond length is 3.00 Å. In the eleventh Na site, Na(11) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one As(10), one As(12), one As(3), and one As(4) atom. The Na(11)-Ga(1) bond length is 3.01 Å. The Na(11)-Ga(4) bond length is 3.03 Å. The Na(11)-As(10) bond length is 2.99 Å. The Na(11)-As(12) bond length is 3.19 Å. The Na(11)-As(3) bond length is 3.00 Å. The Na(11)-As(4) bond length is 3.19 Å. In the twelfth Na site, Na(12) is bonded in a 3-coordinate geometry to one As(1), one As(10), one As(4), and one As(6) atom. The Na(12)-As(1) bond length is 3.06 Å. The Na(12)-As(10) bond length is 3.42 Å. The Na(12)-As(4) bond length is 2.99 Å. The Na(12)-As(6) bond length is 3.13 Å. In the thirteenth Na site, Na(13) is bonded in a 4-coordinate geometry to one As(12), one As(3), one As(7), and one As(9) atom. The Na(13)-As(12) bond length is 3.10 Å. The Na(13)-As(3) bond length is 3.35 Å. The Na(13)-As(7) bond length is 3.19 Å. The Na(13)-As(9) bond length is 2.98 Å. In the fourteenth Na site, Na(14) is bonded in a 6-coordinate geometry to one Ga(1), one Ga(4), one As(1), one As(10), one As(3), and one As(9) atom. The Na(14)-Ga(1) bond length is 3.02 Å. The Na(14)-Ga(4) bond length is 3.02 Å. The Na(14)-As(1) bond length is 3.19 Å. The Na(14)-As(10) bond length is 2.97 Å. The Na(14)-As(3) bond length is 3.02 Å. The Na(14)-As(9) bond length is 3.19 Å. In the fifteenth Na site, Na(15) is bonded to one As(12), one As(3), one As(8), and one As(9) atom to form distorted NaAs4 tetrahedra that share  a cornercorner with one Na(1)As4 tetrahedra,  a cornercorner with one Na(23)As4 tetrahedra,  a cornercorner with one Na(24)NaAs4 tetrahedra,  an edgeedge with one Na(1)As4 tetrahedra, and  an edgeedge with one Na(19)As4 tetrahedra. The Na(15)-As(12) bond length is 3.12 Å. The Na(15)-As(3) bond length is 3.11 Å. The Na(15)-As(8) bond length is 2.98 Å. The Na(15)-As(9) bond length is 3.03 Å. In the sixteenth Na site, Na(16) is bonded in a 4-coordinate geometry to one Na(22), one As(1), one As(10), one As(4), and one As(9) atom. The Na(16)-Na(22) bond length is 3.14 Å. The Na(16)-As(1) bond length is 3.04 Å. The Na(16)-As(10) bond length is 2.96 Å. The Na(16)-As(4) bond length is 3.29 Å. The Na(16)-As(9) bond length is 2.99 Å. In the seventeenth Na site, Na(17) is bonded in a 6-coordinate geometry to one Ga(2), one Ga(3), one As(11), one As(6), one As(7), and one As(8) atom. The Na(17)-Ga(2) bond length is 3.11 Å. The Na(17)-Ga(3) bond length is 3.07 Å. The Na(17)-As(11) bond length is 3.24 Å. The Na(17)-As(6) bond length is 2.98 Å. The Na(17)-As(7) bond length is 3.09 Å. The Na(17)-As(8) bond length is 3.21 Å. In the eighteenth Na site, Na(18) is bonded in a 3-coordinate geometry to one Na(22), one Ga(3), one As(10), one As(11), and one As(5) atom. The Na(18)-Na(22) bond length is 3.31 Å. The Na(18)-Ga(3) bond length is 3.33 Å. The Na(18)-As(10) bond length is 3.07 Å. The Na(18)-As(11) bond length is 3.05 Å. The Na(18)-As(5) bond length is 3.14 Å. In the nineteenth Na site, Na(19) is bonded to one As(2), one As(7), one As(8), and one As(9) atom to form a mixture of distorted corner and edge-sharing NaAs4 tetrahedra. The Na(19)-As(2) bond length is 3.01 Å. The Na(19)-As(7) bond length is 3.13 Å. The Na(19)-As(8) bond length is 3.14 Å. The Na(19)-As(9) bond length is 3.00 Å. In the twentieth Na site, Na(20) is bonded in a 3-coordinate geometry to one Na(22), one As(1), one As(11), and one As(5) atom. The Na(20)-Na(22) bond length is 3.34 Å. The Na(20)-As(1) bond length is 2.98 Å. The Na(20)-As(11) bond length is 2.94 Å. The Na(20)-As(5) bond length is 2.99 Å. In the twenty-first Na site, Na(21) is bonded in a 4-coordinate geometry to one As(11), one As(2), one As(7), and one As(8) atom. The Na(21)-As(11) bond length is 3.02 Å. The Na(21)-As(2) bond length is 3.33 Å. The Na(21)-As(7) bond length is 2.95 Å. The Na(21)-As(8) bond length is 3.02 Å. In the twenty-second Na site, Na(22) is bonded in a 10-coordinate geometry to one Na(16), one Na(18), one Na(20), one Na(24), one Na(6), one Ga(1), one As(1), one As(10), one As(11), and one As(4) atom. The Na(22)-Na(24) bond length is 3.25 Å. The Na(22)-Ga(1) bond length is 3.24 Å. The Na(22)-As(1) bond length is 3.03 Å. The Na(22)-As(10) bond length is 3.27 Å. The Na(22)-As(11) bond length is 3.01 Å. The Na(22)-As(4) bond length is 3.07 Å. In the twenty-third Na site, Na(23) is bonded to one As(11), one As(5), one As(6), and one As(8) atom to form distorted corner-sharing NaAs4 tetrahedra. The Na(23)-As(11) bond length is 2.96 Å. The Na(23)-As(5) bond length is 3.00 Å. The Na(23)-As(6) bond length is 2.93 Å. The Na(23)-As(8) bond length is 3.18 Å. In the twenty-fourth Na site, Na(24) is bonded to one Na(22), one As(1), one As(10), one As(12), and one As(4) atom to form a mixture of distorted corner and edge-sharing NaNaAs4 tetrahedra. The Na(24)-As(1) bond length is 3.03 Å. The Na(24)-As(10) bond length is 2.93 Å. The Na(24)-As(12) bond length is 3.11 Å. The Na(24)-As(4) bond length is 3.07 Å. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 6-coordinate geometry to one Na(11), one Na(14), one Na(22), one As(1), one As(10), and one As(4) atom. The Ga(1)-As(1) bond length is 2.52 Å. The Ga(1)-As(10) bond length is 2.62 Å. The Ga(1)-As(4) bond length is 2.54 Å. In the second Ga site, Ga(2) is bonded in a 3-coordinate geometry to one Na(17), one Na(7), one Na(8), one As(2), one As(7), and one As(8) atom. The Ga(2)-As(2) bond length is 2.57 Å. The Ga(2)-As(7) bond length is 2.57 Å. The Ga(2)-As(8) bond length is 2.52 Å. In the third Ga site, Ga(3) is bonded in a 7-coordinate geometry to one Na(17), one Na(18), one Na(8), one As(11), one As(5), one As(6), and one As(7) atom. The Ga(3)-As(11) bond length is 2.51 Å. The Ga(3)-As(5) bond length is 2.52 Å. The Ga(3)-As(6) bond length is 2.59 Å. The Ga(3)-As(7) bond length is 3.10 Å. In the fourth Ga site, Ga(4) is bonded in a 6-coordinate geometry to one Na(11), one Na(14), one Na(3), one As(10), one As(12), one As(3), and one As(9) atom. The Ga(4)-As(10) bond length is 3.15 Å. The Ga(4)-As(12) bond length is 2.53 Å. The Ga(4)-As(3) bond length is 2.62 Å. The Ga(4)-As(9) bond length is 2.54 Å. There are twelve inequivalent As sites. In the first As site, As(1) is bonded in a 9-coordinate geometry to one Na(1), one Na(10), one Na(12), one Na(14), one Na(16), one Na(20), one Na(22), one Na(24), and one Ga(1) atom. In the second As site, As(2) is bonded in a 9-coordinate geometry to one Na(19), one Na(2), one Na(21), one Na(3), one Na(4), one Na(5), one Na(7), one Na(8), and one Ga(2) atom. In the third As site, As(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(11), one Na(13), one Na(14), one Na(15), one Na(3), one Na(7), one Na(9), and one Ga(4) atom. In the fourth As site, As(4) is bonded in a 9-coordinate geometry to one Na(10), one Na(11), one Na(12), one Na(16), one Na(22), one Na(24), one Na(6), one Na(9), and one Ga(1) atom. In the fifth As site, As(5) is bonded in a 9-coordinate geometry to one Na(10), one Na(18), one Na(2), one Na(20), one Na(23), one Na(5), one Na(6), one Na(8), and one Ga(3) atom. In the sixth As site, As(6) is bonded in a 7-coordinate geometry to one Na(12), one Na(17), one Na(23), one Na(5), one Na(6), one Na(8), and one Ga(3) atom. In the seventh As site, As(7) is bonded in a 10-coordinate geometry to one Na(13), one Na(17), one Na(19), one Na(2), one Na(21), one Na(4), one Na(7), one Na(8), one Ga(2), and one Ga(3) atom. In the eighth As site, As(8) is bonded in a 9-coordinate geometry to one Na(15), one Na(17), one Na(19), one Na(2), one Na(21), one Na(23), one Na(4), one Na(7), and one Ga(2) atom. In the ninth As site, As(9) is bonded in a 9-coordinate geometry to one Na(1), one Na(13), one Na(14), one Na(15), one Na(16), one Na(19), one Na(3), one Na(9), and one Ga(4) atom. In the tenth As site, As(10) is bonded in a 10-coordinate geometry to one Na(10), one Na(11), one Na(12), one Na(14), one Na(16), one Na(18), one Na(22), one Na(24), one Ga(1), and one Ga(4) atom. In the eleventh As site, As(11) is bonded in a 8-coordinate geometry to one Na(17), one Na(18), one Na(20), one Na(21), one Na(22), one Na(23), one Na(6), and one Ga(3) atom. In the twelfth As site, As(12) is bonded in a 9-coordinate geometry to one Na(1), one Na(11), one Na(13), one Na(15), one Na(24), one Na(3), one Na(4), one Na(9), and one Ga(4) atom.