K4In9Si14 crystallizes in the orthorhombic Ama2 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to two equivalent Si(1), two equivalent Si(2), two equivalent Si(4), and two equivalent Si(5) atoms. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent In(5), two equivalent Si(3), two equivalent Si(6), two equivalent Si(7), and two equivalent Si(8) atoms. In the third K site, K(3) is bonded in a 8-coordinate geometry to two equivalent Si(1), two equivalent Si(2), two equivalent Si(4), and two equivalent Si(5) atoms. In the fourth K site, K(4) is bonded in a 8-coordinate geometry to two equivalent In(1), two equivalent In(2), two equivalent In(3), two equivalent In(4), one Si(3), one Si(8), and two equivalent Si(2) atoms. There are five inequivalent In sites. In the first In site, In(1) is bonded in a 5-coordinate geometry to one K(4), one In(1), one Si(1), one Si(2), and one Si(3) atom. In the second In site, In(2) is bonded in a 5-coordinate geometry to one K(4), one In(2), one Si(4), one Si(5), and one Si(6) atom. In the third In site, In(3) is bonded in a 5-coordinate geometry to one K(4), one In(4), one Si(2), one Si(4), and one Si(7) atom. In the fourth In site, In(4) is bonded in a 5-coordinate geometry to one K(4), one In(3), one Si(1), one Si(5), and one Si(8) atom. In the fifth In site, In(5) is bonded to two equivalent K(2), one Si(3), one Si(8), and two equivalent Si(2) atoms to form distorted corner-sharing InK2Si4 tetrahedra. There are ten inequivalent Si sites. In the first Si site, Si(1) is bonded in a 6-coordinate geometry to one K(1), one K(3), one In(1), one In(4), one Si(1), and one Si(9) atom. In the second Si site, Si(2) is bonded in a 7-coordinate geometry to one K(1), one K(3), one K(4), one In(1), one In(3), one In(5), and one Si(5) atom. In the third Si site, Si(3) is bonded in a 7-coordinate geometry to one K(4), two equivalent K(2), one In(5), two equivalent In(1), and one Si(7) atom. In the fourth Si site, Si(4) is bonded in a 6-coordinate geometry to one K(1), one K(3), one In(2), one In(3), one Si(4), and one Si(9) atom. In the fifth Si site, Si(5) is bonded in a 6-coordinate geometry to one K(1), one K(3), one In(2), one In(4), one Si(10), and one Si(2) atom. In the sixth Si site, Si(6) is bonded in a 6-coordinate geometry to two equivalent K(2), two equivalent In(2), one Si(10), and one Si(8) atom. In the seventh Si site, Si(7) is bonded in a 6-coordinate geometry to two equivalent K(2), two equivalent In(3), one Si(10), and one Si(3) atom. In the eighth Si site, Si(8) is bonded in a 7-coordinate geometry to one K(4), two equivalent K(2), one In(5), two equivalent In(4), and one Si(6) atom. In the ninth Si site, Si(9) is bonded in a tetrahedral geometry to two equivalent Si(1) and two equivalent Si(4) atoms. In the tenth Si site, Si(10) is bonded in a tetrahedral geometry to one Si(6), one Si(7), and two equivalent Si(5) atoms.
K4In9Si14 crystallizes in the orthorhombic Ama2 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to two equivalent Si(1), two equivalent Si(2), two equivalent Si(4), and two equivalent Si(5) atoms. Both K(1)-Si(1) bond lengths are 3.64 Å. Both K(1)-Si(2) bond lengths are 3.62 Å. Both K(1)-Si(4) bond lengths are 3.62 Å. Both K(1)-Si(5) bond lengths are 3.65 Å. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent In(5), two equivalent Si(3), two equivalent Si(6), two equivalent Si(7), and two equivalent Si(8) atoms. Both K(2)-In(5) bond lengths are 3.93 Å. Both K(2)-Si(3) bond lengths are 3.60 Å. Both K(2)-Si(6) bond lengths are 3.61 Å. Both K(2)-Si(7) bond lengths are 3.63 Å. Both K(2)-Si(8) bond lengths are 3.60 Å. In the third K site, K(3) is bonded in a 8-coordinate geometry to two equivalent Si(1), two equivalent Si(2), two equivalent Si(4), and two equivalent Si(5) atoms. Both K(3)-Si(1) bond lengths are 3.60 Å. Both K(3)-Si(2) bond lengths are 3.60 Å. Both K(3)-Si(4) bond lengths are 3.61 Å. Both K(3)-Si(5) bond lengths are 3.61 Å. In the fourth K site, K(4) is bonded in a 8-coordinate geometry to two equivalent In(1), two equivalent In(2), two equivalent In(3), two equivalent In(4), one Si(3), one Si(8), and two equivalent Si(2) atoms. Both K(4)-In(1) bond lengths are 3.40 Å. Both K(4)-In(2) bond lengths are 3.42 Å. Both K(4)-In(3) bond lengths are 3.40 Å. Both K(4)-In(4) bond lengths are 3.40 Å. The K(4)-Si(3) bond length is 3.73 Å. The K(4)-Si(8) bond length is 3.71 Å. Both K(4)-Si(2) bond lengths are 3.63 Å. There are five inequivalent In sites. In the first In site, In(1) is bonded in a 5-coordinate geometry to one K(4), one In(1), one Si(1), one Si(2), and one Si(3) atom. The In(1)-In(1) bond length is 2.87 Å. The In(1)-Si(1) bond length is 2.70 Å. The In(1)-Si(2) bond length is 2.69 Å. The In(1)-Si(3) bond length is 2.68 Å. In the second In site, In(2) is bonded in a 5-coordinate geometry to one K(4), one In(2), one Si(4), one Si(5), and one Si(6) atom. The In(2)-In(2) bond length is 2.82 Å. The In(2)-Si(4) bond length is 2.69 Å. The In(2)-Si(5) bond length is 2.67 Å. The In(2)-Si(6) bond length is 2.66 Å. In the third In site, In(3) is bonded in a 5-coordinate geometry to one K(4), one In(4), one Si(2), one Si(4), and one Si(7) atom. The In(3)-In(4) bond length is 2.85 Å. The In(3)-Si(2) bond length is 2.68 Å. The In(3)-Si(4) bond length is 2.69 Å. The In(3)-Si(7) bond length is 2.67 Å. In the fourth In site, In(4) is bonded in a 5-coordinate geometry to one K(4), one In(3), one Si(1), one Si(5), and one Si(8) atom. The In(4)-Si(1) bond length is 2.70 Å. The In(4)-Si(5) bond length is 2.68 Å. The In(4)-Si(8) bond length is 2.68 Å. In the fifth In site, In(5) is bonded to two equivalent K(2), one Si(3), one Si(8), and two equivalent Si(2) atoms to form distorted corner-sharing InK2Si4 tetrahedra. The In(5)-Si(3) bond length is 2.68 Å. The In(5)-Si(8) bond length is 2.68 Å. Both In(5)-Si(2) bond lengths are 2.68 Å. There are ten inequivalent Si sites. In the first Si site, Si(1) is bonded in a 6-coordinate geometry to one K(1), one K(3), one In(1), one In(4), one Si(1), and one Si(9) atom. The Si(1)-Si(1) bond length is 2.41 Å. The Si(1)-Si(9) bond length is 2.45 Å. In the second Si site, Si(2) is bonded in a 7-coordinate geometry to one K(1), one K(3), one K(4), one In(1), one In(3), one In(5), and one Si(5) atom. The Si(2)-Si(5) bond length is 2.37 Å. In the third Si site, Si(3) is bonded in a 7-coordinate geometry to one K(4), two equivalent K(2), one In(5), two equivalent In(1), and one Si(7) atom. The Si(3)-Si(7) bond length is 2.39 Å. In the fourth Si site, Si(4) is bonded in a 6-coordinate geometry to one K(1), one K(3), one In(2), one In(3), one Si(4), and one Si(9) atom. The Si(4)-Si(4) bond length is 2.40 Å. The Si(4)-Si(9) bond length is 2.45 Å. In the fifth Si site, Si(5) is bonded in a 6-coordinate geometry to one K(1), one K(3), one In(2), one In(4), one Si(10), and one Si(2) atom. The Si(5)-Si(10) bond length is 2.45 Å. In the sixth Si site, Si(6) is bonded in a 6-coordinate geometry to two equivalent K(2), two equivalent In(2), one Si(10), and one Si(8) atom. The Si(6)-Si(10) bond length is 2.46 Å. The Si(6)-Si(8) bond length is 2.38 Å. In the seventh Si site, Si(7) is bonded in a 6-coordinate geometry to two equivalent K(2), two equivalent In(3), one Si(10), and one Si(3) atom. The Si(7)-Si(10) bond length is 2.46 Å. In the eighth Si site, Si(8) is bonded in a 7-coordinate geometry to one K(4), two equivalent K(2), one In(5), two equivalent In(4), and one Si(6) atom. In the ninth Si site, Si(9) is bonded in a tetrahedral geometry to two equivalent Si(1) and two equivalent Si(4) atoms. In the tenth Si site, Si(10) is bonded in a tetrahedral geometry to one Si(6), one Si(7), and two equivalent Si(5) atoms.