Na3InAs2 crystallizes in the monoclinic P2_1/c space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to one In(2), one As(1), one As(2), and two equivalent As(4) atoms to form a mixture of distorted corner and edge-sharing NaInAs4 tetrahedra. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one In(1), two equivalent In(2), two equivalent As(2), and two equivalent As(3) atoms. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one In(2), one As(1), one As(2), one As(3), and two equivalent As(4) atoms. In the fourth Na site, Na(4) is bonded to one In(2), one As(1), one As(2), and two equivalent As(3) atoms to form a mixture of distorted corner and edge-sharing NaInAs4 tetrahedra. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one In(1), one In(2), one As(3), two equivalent As(1), and two equivalent As(4) atoms. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to two equivalent In(2), one As(1), one As(3), one As(4), and two equivalent As(2) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one As(3), one As(4), and two equivalent As(1) atoms. In the second In site, In(2) is bonded in a 12-coordinate geometry to one Na(1), one Na(3), one Na(4), one Na(5), two equivalent Na(2), two equivalent Na(6), one As(3), one As(4), and two equivalent As(2) atoms. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one Na(1), one Na(3), one Na(4), one Na(6), two equivalent Na(5), and two equivalent In(1) atoms. In the second As site, As(2) is bonded in a 9-coordinate geometry to one Na(1), one Na(3), one Na(4), two equivalent Na(2), two equivalent Na(6), and two equivalent In(2) atoms. In the third As site, As(3) is bonded in a 9-coordinate geometry to one Na(3), one Na(5), one Na(6), two equivalent Na(2), two equivalent Na(4), one In(1), and one In(2) atom. In the fourth As site, As(4) is bonded in a 9-coordinate geometry to one Na(6), two equivalent Na(1), two equivalent Na(3), two equivalent Na(5), one In(1), and one In(2) atom.
Na3InAs2 crystallizes in the monoclinic P2_1/c space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to one In(2), one As(1), one As(2), and two equivalent As(4) atoms to form a mixture of distorted corner and edge-sharing NaInAs4 tetrahedra. The Na(1)-In(2) bond length is 3.46 Å. The Na(1)-As(1) bond length is 2.88 Å. The Na(1)-As(2) bond length is 2.92 Å. Both Na(1)-As(4) bond lengths are 2.95 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one In(1), two equivalent In(2), two equivalent As(2), and two equivalent As(3) atoms. The Na(2)-In(1) bond length is 3.35 Å. There is one shorter (3.27 Å) and one longer (3.52 Å) Na(2)-In(2) bond length. There is one shorter (3.08 Å) and one longer (3.24 Å) Na(2)-As(2) bond length. There is one shorter (3.00 Å) and one longer (3.16 Å) Na(2)-As(3) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one In(2), one As(1), one As(2), one As(3), and two equivalent As(4) atoms. The Na(3)-In(2) bond length is 3.46 Å. The Na(3)-As(1) bond length is 3.13 Å. The Na(3)-As(2) bond length is 3.16 Å. The Na(3)-As(3) bond length is 3.15 Å. There is one shorter (3.17 Å) and one longer (3.46 Å) Na(3)-As(4) bond length. In the fourth Na site, Na(4) is bonded to one In(2), one As(1), one As(2), and two equivalent As(3) atoms to form a mixture of distorted corner and edge-sharing NaInAs4 tetrahedra. The Na(4)-In(2) bond length is 3.42 Å. The Na(4)-As(1) bond length is 2.90 Å. The Na(4)-As(2) bond length is 2.86 Å. There is one shorter (2.93 Å) and one longer (2.94 Å) Na(4)-As(3) bond length. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one In(1), one In(2), one As(3), two equivalent As(1), and two equivalent As(4) atoms. The Na(5)-In(1) bond length is 3.44 Å. The Na(5)-In(2) bond length is 3.49 Å. The Na(5)-As(3) bond length is 3.29 Å. There is one shorter (3.00 Å) and one longer (3.09 Å) Na(5)-As(1) bond length. There is one shorter (3.18 Å) and one longer (3.41 Å) Na(5)-As(4) bond length. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to two equivalent In(2), one As(1), one As(3), one As(4), and two equivalent As(2) atoms. There is one shorter (3.42 Å) and one longer (3.50 Å) Na(6)-In(2) bond length. The Na(6)-As(1) bond length is 3.31 Å. The Na(6)-As(3) bond length is 3.30 Å. The Na(6)-As(4) bond length is 2.94 Å. There is one shorter (3.17 Å) and one longer (3.28 Å) Na(6)-As(2) bond length. There are two inequivalent In sites. In the first In site, In(1) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one As(3), one As(4), and two equivalent As(1) atoms. The In(1)-As(3) bond length is 2.72 Å. The In(1)-As(4) bond length is 2.71 Å. There is one shorter (2.68 Å) and one longer (2.74 Å) In(1)-As(1) bond length. In the second In site, In(2) is bonded in a 12-coordinate geometry to one Na(1), one Na(3), one Na(4), one Na(5), two equivalent Na(2), two equivalent Na(6), one As(3), one As(4), and two equivalent As(2) atoms. The In(2)-As(3) bond length is 2.74 Å. The In(2)-As(4) bond length is 2.69 Å. There is one shorter (2.70 Å) and one longer (2.78 Å) In(2)-As(2) bond length. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one Na(1), one Na(3), one Na(4), one Na(6), two equivalent Na(5), and two equivalent In(1) atoms. In the second As site, As(2) is bonded in a 9-coordinate geometry to one Na(1), one Na(3), one Na(4), two equivalent Na(2), two equivalent Na(6), and two equivalent In(2) atoms. In the third As site, As(3) is bonded in a 9-coordinate geometry to one Na(3), one Na(5), one Na(6), two equivalent Na(2), two equivalent Na(4), one In(1), and one In(2) atom. In the fourth As site, As(4) is bonded in a 9-coordinate geometry to one Na(6), two equivalent Na(1), two equivalent Na(3), two equivalent Na(5), one In(1), and one In(2) atom.