Ba2CaNi2CuF14 crystallizes in the triclinic P1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to one F(11), one F(18), one F(2), one F(22), one F(24), one F(27), one F(3), one F(5), one F(9), and two equivalent F(4) atoms. In the second Ba site, Ba(2) is bonded in a 12-coordinate geometry to one F(12), one F(13), one F(14), one F(15), one F(16), one F(19), one F(21), one F(23), one F(7), one F(8), and two equivalent F(28) atoms. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one F(1), one F(13), one F(14), one F(16), one F(2), one F(20), one F(23), one F(25), one F(3), and two equivalent F(10) atoms. In the fourth Ba site, Ba(4) is bonded in a 11-coordinate geometry to one F(11), one F(17), one F(21), one F(22), one F(26), one F(27), one F(6), one F(7), one F(9), and two equivalent F(12) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one F(11), one F(18), one F(22), one F(26), one F(27), one F(5), one F(6), and one F(9) atom. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one F(1), one F(13), one F(14), one F(15), one F(16), one F(23), one F(25), and one F(8) atom. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one F(11), one F(12), one F(19), one F(26), one F(7), and one F(9) atom to form NiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the second Ni site, Ni(2) is bonded to one F(14), one F(16), one F(17), one F(21), one F(28), and one F(8) atom to form NiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the third Ni site, Ni(3) is bonded to one F(1), one F(10), one F(13), one F(2), one F(23), and one F(24) atom to form NiF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. In the fourth Ni site, Ni(4) is bonded to one F(18), one F(20), one F(22), one F(27), one F(3), and one F(4) atom to form NiF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(15), one F(17), one F(19), one F(21), one F(6), and one F(7) atom to form CuF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra and corners with two equivalent Ni(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the second Cu site, Cu(2) is bonded to one F(2), one F(20), one F(24), one F(25), one F(3), and one F(5) atom to form CuF6 octahedra that share corners with two equivalent Ni(3)F6 octahedra and corners with two equivalent Ni(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. There are twenty-eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ba(3), one Ca(2), and one Ni(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Ni(3), and one Cu(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Ni(4), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Ni(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ca(1), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ba(4), one Ca(1), and one Cu(1) atom. In the seventh F site, F(7) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(4), one Ni(1), and one Cu(1) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ba(2), one Ca(2), and one Ni(2) atom. In the ninth F site, F(9) is bonded to one Ba(1), one Ba(4), one Ca(1), and one Ni(1) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the tenth F site, F(10) is bonded in a distorted single-bond geometry to two equivalent Ba(3) and one Ni(3) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Ni(1) atom. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(4), and one Ni(1) atom. In the thirteenth F site, F(13) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Ni(3) atom. In the fourteenth F site, F(14) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Ni(2) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ca(2), and one Cu(1) atom. In the sixteenth F site, F(16) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Ni(2) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the seventeenth F site, F(17) is bonded in a 2-coordinate geometry to one Ba(4), one Ni(2), and one Cu(1) atom. In the eighteenth F site, F(18) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Ni(4) atom. In the nineteenth F site, F(19) is bonded in a 2-coordinate geometry to one Ba(2), one Ni(1), and one Cu(1) atom. In the twentieth F site, F(20) is bonded in a 2-coordinate geometry to one Ba(3), one Ni(4), and one Cu(2) atom. In the twenty-first F site, F(21) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(4), one Ni(2), and one Cu(1) atom. In the twenty-second F site, F(22) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Ni(4) atom. In the twenty-third F site, F(23) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Ni(3) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the twenty-fourth F site, F(24) is bonded in a 2-coordinate geometry to one Ba(1), one Ni(3), and one Cu(2) atom. In the twenty-fifth F site, F(25) is bonded in a distorted trigonal planar geometry to one Ba(3), one Ca(2), and one Cu(2) atom. In the twenty-sixth F site, F(26) is bonded in a 3-coordinate geometry to one Ba(4), one Ca(1), and one Ni(1) atom. In the twenty-seventh F site, F(27) is bonded to one Ba(1), one Ba(4), one Ca(1), and one Ni(4) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the twenty-eighth F site, F(28) is bonded in a distorted single-bond geometry to two equivalent Ba(2) and one Ni(2) atom.
Ba2CaNi2CuF14 crystallizes in the triclinic P1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to one F(11), one F(18), one F(2), one F(22), one F(24), one F(27), one F(3), one F(5), one F(9), and two equivalent F(4) atoms. The Ba(1)-F(11) bond length is 2.98 Å. The Ba(1)-F(18) bond length is 2.67 Å. The Ba(1)-F(2) bond length is 2.84 Å. The Ba(1)-F(22) bond length is 3.13 Å. The Ba(1)-F(24) bond length is 2.95 Å. The Ba(1)-F(27) bond length is 2.77 Å. The Ba(1)-F(3) bond length is 2.90 Å. The Ba(1)-F(5) bond length is 2.80 Å. The Ba(1)-F(9) bond length is 2.71 Å. There is one shorter (2.77 Å) and one longer (2.96 Å) Ba(1)-F(4) bond length. In the second Ba site, Ba(2) is bonded in a 12-coordinate geometry to one F(12), one F(13), one F(14), one F(15), one F(16), one F(19), one F(21), one F(23), one F(7), one F(8), and two equivalent F(28) atoms. The Ba(2)-F(12) bond length is 3.33 Å. The Ba(2)-F(13) bond length is 3.03 Å. The Ba(2)-F(14) bond length is 3.12 Å. The Ba(2)-F(15) bond length is 2.80 Å. The Ba(2)-F(16) bond length is 2.83 Å. The Ba(2)-F(19) bond length is 2.88 Å. The Ba(2)-F(21) bond length is 2.96 Å. The Ba(2)-F(23) bond length is 2.75 Å. The Ba(2)-F(7) bond length is 2.87 Å. The Ba(2)-F(8) bond length is 2.68 Å. There is one shorter (2.78 Å) and one longer (2.95 Å) Ba(2)-F(28) bond length. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one F(1), one F(13), one F(14), one F(16), one F(2), one F(20), one F(23), one F(25), one F(3), and two equivalent F(10) atoms. The Ba(3)-F(1) bond length is 2.74 Å. The Ba(3)-F(13) bond length is 3.15 Å. The Ba(3)-F(14) bond length is 3.06 Å. The Ba(3)-F(16) bond length is 2.78 Å. The Ba(3)-F(2) bond length is 2.84 Å. The Ba(3)-F(20) bond length is 2.93 Å. The Ba(3)-F(23) bond length is 2.77 Å. The Ba(3)-F(25) bond length is 2.81 Å. The Ba(3)-F(3) bond length is 2.80 Å. There is one shorter (2.76 Å) and one longer (2.94 Å) Ba(3)-F(10) bond length. In the fourth Ba site, Ba(4) is bonded in a 11-coordinate geometry to one F(11), one F(17), one F(21), one F(22), one F(26), one F(27), one F(6), one F(7), one F(9), and two equivalent F(12) atoms. The Ba(4)-F(11) bond length is 3.10 Å. The Ba(4)-F(17) bond length is 2.96 Å. The Ba(4)-F(21) bond length is 2.90 Å. The Ba(4)-F(22) bond length is 3.03 Å. The Ba(4)-F(26) bond length is 2.66 Å. The Ba(4)-F(27) bond length is 2.75 Å. The Ba(4)-F(6) bond length is 2.82 Å. The Ba(4)-F(7) bond length is 3.03 Å. The Ba(4)-F(9) bond length is 2.76 Å. There is one shorter (2.78 Å) and one longer (2.94 Å) Ba(4)-F(12) bond length. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one F(11), one F(18), one F(22), one F(26), one F(27), one F(5), one F(6), and one F(9) atom. The Ca(1)-F(11) bond length is 2.35 Å. The Ca(1)-F(18) bond length is 2.38 Å. The Ca(1)-F(22) bond length is 2.42 Å. The Ca(1)-F(26) bond length is 2.35 Å. The Ca(1)-F(27) bond length is 2.55 Å. The Ca(1)-F(5) bond length is 2.31 Å. The Ca(1)-F(6) bond length is 2.29 Å. The Ca(1)-F(9) bond length is 2.43 Å. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one F(1), one F(13), one F(14), one F(15), one F(16), one F(23), one F(25), and one F(8) atom. The Ca(2)-F(1) bond length is 2.38 Å. The Ca(2)-F(13) bond length is 2.34 Å. The Ca(2)-F(14) bond length is 2.42 Å. The Ca(2)-F(15) bond length is 2.27 Å. The Ca(2)-F(16) bond length is 2.51 Å. The Ca(2)-F(23) bond length is 2.47 Å. The Ca(2)-F(25) bond length is 2.30 Å. The Ca(2)-F(8) bond length is 2.39 Å. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one F(11), one F(12), one F(19), one F(26), one F(7), and one F(9) atom to form NiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Ni(1)-F(11) bond length is 1.93 Å. The Ni(1)-F(12) bond length is 1.89 Å. The Ni(1)-F(19) bond length is 2.04 Å. The Ni(1)-F(26) bond length is 1.90 Å. The Ni(1)-F(7) bond length is 1.97 Å. The Ni(1)-F(9) bond length is 2.05 Å. In the second Ni site, Ni(2) is bonded to one F(14), one F(16), one F(17), one F(21), one F(28), and one F(8) atom to form NiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Ni(2)-F(14) bond length is 1.90 Å. The Ni(2)-F(16) bond length is 1.98 Å. The Ni(2)-F(17) bond length is 1.97 Å. The Ni(2)-F(21) bond length is 1.93 Å. The Ni(2)-F(28) bond length is 1.87 Å. The Ni(2)-F(8) bond length is 1.86 Å. In the third Ni site, Ni(3) is bonded to one F(1), one F(10), one F(13), one F(2), one F(23), and one F(24) atom to form NiF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. The Ni(3)-F(1) bond length is 1.83 Å. The Ni(3)-F(10) bond length is 1.83 Å. The Ni(3)-F(13) bond length is 1.91 Å. The Ni(3)-F(2) bond length is 1.92 Å. The Ni(3)-F(23) bond length is 2.02 Å. The Ni(3)-F(24) bond length is 2.01 Å. In the fourth Ni site, Ni(4) is bonded to one F(18), one F(20), one F(22), one F(27), one F(3), and one F(4) atom to form NiF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. The Ni(4)-F(18) bond length is 1.86 Å. The Ni(4)-F(20) bond length is 2.00 Å. The Ni(4)-F(22) bond length is 1.90 Å. The Ni(4)-F(27) bond length is 1.97 Å. The Ni(4)-F(3) bond length is 1.92 Å. The Ni(4)-F(4) bond length is 1.87 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(15), one F(17), one F(19), one F(21), one F(6), and one F(7) atom to form CuF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra and corners with two equivalent Ni(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Cu(1)-F(15) bond length is 1.90 Å. The Cu(1)-F(17) bond length is 1.96 Å. The Cu(1)-F(19) bond length is 1.92 Å. The Cu(1)-F(21) bond length is 2.29 Å. The Cu(1)-F(6) bond length is 1.89 Å. The Cu(1)-F(7) bond length is 2.13 Å. In the second Cu site, Cu(2) is bonded to one F(2), one F(20), one F(24), one F(25), one F(3), and one F(5) atom to form CuF6 octahedra that share corners with two equivalent Ni(3)F6 octahedra and corners with two equivalent Ni(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. The Cu(2)-F(2) bond length is 2.37 Å. The Cu(2)-F(20) bond length is 1.93 Å. The Cu(2)-F(24) bond length is 1.91 Å. The Cu(2)-F(25) bond length is 1.89 Å. The Cu(2)-F(3) bond length is 2.38 Å. The Cu(2)-F(5) bond length is 1.87 Å. There are twenty-eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ba(3), one Ca(2), and one Ni(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Ni(3), and one Cu(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one Ni(4), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Ni(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ca(1), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ba(4), one Ca(1), and one Cu(1) atom. In the seventh F site, F(7) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(4), one Ni(1), and one Cu(1) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ba(2), one Ca(2), and one Ni(2) atom. In the ninth F site, F(9) is bonded to one Ba(1), one Ba(4), one Ca(1), and one Ni(1) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the tenth F site, F(10) is bonded in a distorted single-bond geometry to two equivalent Ba(3) and one Ni(3) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Ni(1) atom. In the twelfth F site, F(12) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(4), and one Ni(1) atom. In the thirteenth F site, F(13) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Ni(3) atom. In the fourteenth F site, F(14) is bonded in a 2-coordinate geometry to one Ba(2), one Ba(3), one Ca(2), and one Ni(2) atom. In the fifteenth F site, F(15) is bonded in a distorted trigonal planar geometry to one Ba(2), one Ca(2), and one Cu(1) atom. In the sixteenth F site, F(16) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Ni(2) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the seventeenth F site, F(17) is bonded in a 2-coordinate geometry to one Ba(4), one Ni(2), and one Cu(1) atom. In the eighteenth F site, F(18) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Ni(4) atom. In the nineteenth F site, F(19) is bonded in a 2-coordinate geometry to one Ba(2), one Ni(1), and one Cu(1) atom. In the twentieth F site, F(20) is bonded in a 2-coordinate geometry to one Ba(3), one Ni(4), and one Cu(2) atom. In the twenty-first F site, F(21) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(4), one Ni(2), and one Cu(1) atom. In the twenty-second F site, F(22) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(4), one Ca(1), and one Ni(4) atom. In the twenty-third F site, F(23) is bonded to one Ba(2), one Ba(3), one Ca(2), and one Ni(3) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the twenty-fourth F site, F(24) is bonded in a 2-coordinate geometry to one Ba(1), one Ni(3), and one Cu(2) atom. In the twenty-fifth F site, F(25) is bonded in a distorted trigonal planar geometry to one Ba(3), one Ca(2), and one Cu(2) atom. In the twenty-sixth F site, F(26) is bonded in a 3-coordinate geometry to one Ba(4), one Ca(1), and one Ni(1) atom. In the twenty-seventh F site, F(27) is bonded to one Ba(1), one Ba(4), one Ca(1), and one Ni(4) atom to form distorted corner-sharing FBa2CaNi tetrahedra. In the twenty-eighth F site, F(28) is bonded in a distorted single-bond geometry to two equivalent Ba(2) and one Ni(2) atom.