CaNiIn4 crystallizes in the monoclinic Cm space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 15-coordinate geometry to two equivalent Ni(1), one In(2), one In(3), one In(6), two equivalent In(1), two equivalent In(4), two equivalent In(5), two equivalent In(7), and two equivalent In(8) atoms. In the second Ca site, Ca(2) is bonded in a 15-coordinate geometry to two equivalent Ni(2), one In(1), one In(5), one In(7), two equivalent In(2), two equivalent In(3), two equivalent In(4), two equivalent In(6), and two equivalent In(8) atoms. In the third Ca site, Ca(1) is bonded in a 15-coordinate geometry to two equivalent Ni(1), one In(2), one In(3), one In(6), two equivalent In(1), two equivalent In(4), two equivalent In(5), two equivalent In(7), and two equivalent In(8) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 9-coordinate geometry to two equivalent Ca(1), one In(1), one In(2), one In(7), two equivalent In(3), and two equivalent In(6) atoms. In the second Ni site, Ni(2) is bonded in a 9-coordinate geometry to two equivalent Ca(2), one In(3), one In(5), one In(6), two equivalent In(1), and two equivalent In(7) atoms. There are ten inequivalent In sites. In the first In site, In(1) is bonded in a 5-coordinate geometry to one Ca(2), two equivalent Ca(1), one Ni(1), two equivalent Ni(2), and one In(8) atom. In the second In site, In(2) is bonded in a 2-coordinate geometry to one Ca(1), two equivalent Ca(2), one Ni(1), two equivalent In(4), and two equivalent In(8) atoms. In the third In site, In(3) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Ni(2), two equivalent Ni(1), and one In(4) atom. In the fourth In site, In(4) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(3), one In(7), two equivalent In(2), and two equivalent In(5) atoms. In the fifth In site, In(5) is bonded in a 2-coordinate geometry to one Ca(2), two equivalent Ca(1), one Ni(2), two equivalent In(4), and two equivalent In(8) atoms. In the sixth In site, In(6) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Ni(2), two equivalent Ni(1), and one In(8) atom. In the seventh In site, In(7) is bonded in a 5-coordinate geometry to one Ca(2), two equivalent Ca(1), one Ni(1), two equivalent Ni(2), and one In(4) atom. In the eighth In site, In(8) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(1), one In(6), two equivalent In(2), and two equivalent In(5) atoms. In the ninth In site, In(4) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(3), one In(7), two equivalent In(2), and two equivalent In(5) atoms. In the tenth In site, In(8) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(1), one In(6), two equivalent In(2), and two equivalent In(5) atoms.
CaNiIn4 crystallizes in the monoclinic Cm space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 15-coordinate geometry to two equivalent Ni(1), one In(2), one In(3), one In(6), two equivalent In(1), two equivalent In(4), two equivalent In(5), two equivalent In(7), and two equivalent In(8) atoms. Both Ca(1)-Ni(1) bond lengths are 3.31 Å. The Ca(1)-In(2) bond length is 3.19 Å. The Ca(1)-In(3) bond length is 3.44 Å. The Ca(1)-In(6) bond length is 3.52 Å. Both Ca(1)-In(1) bond lengths are 3.18 Å. Both Ca(1)-In(4) bond lengths are 3.47 Å. Both Ca(1)-In(5) bond lengths are 3.66 Å. Both Ca(1)-In(7) bond lengths are 3.18 Å. Both Ca(1)-In(8) bond lengths are 3.48 Å. In the second Ca site, Ca(2) is bonded in a 15-coordinate geometry to two equivalent Ni(2), one In(1), one In(5), one In(7), two equivalent In(2), two equivalent In(3), two equivalent In(4), two equivalent In(6), and two equivalent In(8) atoms. Both Ca(2)-Ni(2) bond lengths are 3.31 Å. The Ca(2)-In(1) bond length is 3.44 Å. The Ca(2)-In(5) bond length is 3.29 Å. The Ca(2)-In(7) bond length is 3.44 Å. Both Ca(2)-In(2) bond lengths are 3.69 Å. Both Ca(2)-In(3) bond lengths are 3.18 Å. Both Ca(2)-In(4) bond lengths are 3.48 Å. Both Ca(2)-In(6) bond lengths are 3.17 Å. Both Ca(2)-In(8) bond lengths are 3.47 Å. In the third Ca site, Ca(1) is bonded in a 15-coordinate geometry to two equivalent Ni(1), one In(2), one In(3), one In(6), two equivalent In(1), two equivalent In(4), two equivalent In(5), two equivalent In(7), and two equivalent In(8) atoms. Both Ca(1)-Ni(1) bond lengths are 3.31 Å. The Ca(1)-In(2) bond length is 3.19 Å. The Ca(1)-In(3) bond length is 3.44 Å. The Ca(1)-In(6) bond length is 3.52 Å. Both Ca(1)-In(1) bond lengths are 3.18 Å. Both Ca(1)-In(4) bond lengths are 3.47 Å. Both Ca(1)-In(5) bond lengths are 3.66 Å. Both Ca(1)-In(7) bond lengths are 3.18 Å. Both Ca(1)-In(8) bond lengths are 3.48 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 9-coordinate geometry to two equivalent Ca(1), one In(1), one In(2), one In(7), two equivalent In(3), and two equivalent In(6) atoms. The Ni(1)-In(1) bond length is 2.55 Å. The Ni(1)-In(2) bond length is 2.57 Å. The Ni(1)-In(7) bond length is 2.55 Å. Both Ni(1)-In(3) bond lengths are 2.69 Å. Both Ni(1)-In(6) bond lengths are 2.70 Å. In the second Ni site, Ni(2) is bonded in a 9-coordinate geometry to two equivalent Ca(2), one In(3), one In(5), one In(6), two equivalent In(1), and two equivalent In(7) atoms. The Ni(2)-In(3) bond length is 2.55 Å. The Ni(2)-In(5) bond length is 2.46 Å. The Ni(2)-In(6) bond length is 2.62 Å. Both Ni(2)-In(1) bond lengths are 2.69 Å. Both Ni(2)-In(7) bond lengths are 2.69 Å. There are ten inequivalent In sites. In the first In site, In(1) is bonded in a 5-coordinate geometry to one Ca(2), two equivalent Ca(1), one Ni(1), two equivalent Ni(2), and one In(8) atom. The In(1)-In(8) bond length is 3.13 Å. In the second In site, In(2) is bonded in a 2-coordinate geometry to one Ca(1), two equivalent Ca(2), one Ni(1), two equivalent In(4), and two equivalent In(8) atoms. Both In(2)-In(4) bond lengths are 3.03 Å. Both In(2)-In(8) bond lengths are 3.02 Å. In the third In site, In(3) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Ni(2), two equivalent Ni(1), and one In(4) atom. The In(3)-In(4) bond length is 3.13 Å. In the fourth In site, In(4) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(3), one In(7), two equivalent In(2), and two equivalent In(5) atoms. Both In(4)-Ca(2) bond lengths are 3.48 Å. The In(4)-In(3) bond length is 3.13 Å. The In(4)-In(7) bond length is 3.10 Å. Both In(4)-In(2) bond lengths are 3.03 Å. Both In(4)-In(5) bond lengths are 3.06 Å. In the fifth In site, In(5) is bonded in a 2-coordinate geometry to one Ca(2), two equivalent Ca(1), one Ni(2), two equivalent In(4), and two equivalent In(8) atoms. Both In(5)-In(8) bond lengths are 3.07 Å. In the sixth In site, In(6) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Ni(2), two equivalent Ni(1), and one In(8) atom. The In(6)-In(8) bond length is 3.01 Å. In the seventh In site, In(7) is bonded in a 5-coordinate geometry to one Ca(2), two equivalent Ca(1), one Ni(1), two equivalent Ni(2), and one In(4) atom. In the eighth In site, In(8) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(1), one In(6), two equivalent In(2), and two equivalent In(5) atoms. The In(8)-In(1) bond length is 3.13 Å. Both In(8)-In(5) bond lengths are 3.07 Å. In the ninth In site, In(4) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(3), one In(7), two equivalent In(2), and two equivalent In(5) atoms. The In(4)-In(7) bond length is 3.10 Å. Both In(4)-In(5) bond lengths are 3.06 Å. In the tenth In site, In(8) is bonded in a 10-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one In(1), one In(6), two equivalent In(2), and two equivalent In(5) atoms. Both In(8)-Ca(2) bond lengths are 3.47 Å. The In(8)-In(6) bond length is 3.01 Å. Both In(8)-In(2) bond lengths are 3.02 Å.