Ca5(Au3Si2)2 crystallizes in the monoclinic Cm space group. There are ten inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 12-coordinate geometry to one Au(1), one Au(7), two equivalent Au(2), two equivalent Au(6), three equivalent Au(12), and three equivalent Si(5) atoms. In the second Ca site, Ca(2) is bonded in a 12-coordinate geometry to one Au(5), two equivalent Au(4), three equivalent Au(10), one Si(7), two equivalent Si(8), and three equivalent Si(3) atoms. In the third Ca site, Ca(3) is bonded in a 12-coordinate geometry to one Au(6), two equivalent Au(1), two equivalent Au(5), three equivalent Au(11), one Si(8), and three equivalent Si(4) atoms. In the fourth Ca site, Ca(4) is bonded in a 12-coordinate geometry to one Au(2), one Au(3), two equivalent Au(7), three equivalent Au(8), two equivalent Si(6), and three equivalent Si(1) atoms. In the fifth Ca site, Ca(5) is bonded in a 12-coordinate geometry to one Au(4), two equivalent Au(3), three equivalent Au(9), one Si(6), two equivalent Si(7), and three equivalent Si(2) atoms. In the sixth Ca site, Ca(6) is bonded in a 12-coordinate geometry to one Au(8), two equivalent Au(12), three equivalent Au(2), three equivalent Au(7), one Si(5), and two equivalent Si(1) atoms. In the seventh Ca site, Ca(7) is bonded in a 12-coordinate geometry to one Au(11), two equivalent Au(10), three equivalent Au(5), one Si(3), two equivalent Si(4), and three equivalent Si(8) atoms. In the eighth Ca site, Ca(8) is bonded in a 11-coordinate geometry to one Au(12), two equivalent Au(11), two equivalent Au(6), three equivalent Au(1), one Si(4), and two equivalent Si(5) atoms. In the ninth Ca site, Ca(9) is bonded in a 12-coordinate geometry to one Au(9), two equivalent Au(8), three equivalent Au(3), one Si(1), two equivalent Si(2), and three equivalent Si(6) atoms. In the tenth Ca site, Ca(10) is bonded in a 12-coordinate geometry to one Au(10), two equivalent Au(9), three equivalent Au(4), one Si(2), two equivalent Si(3), and three equivalent Si(7) atoms. There are twelve inequivalent Au sites. In the first Au site, Au(1) is bonded in a 10-coordinate geometry to one Ca(1), two equivalent Ca(3), three equivalent Ca(8), one Au(11), two equivalent Au(6), and one Si(5) atom. In the second Au site, Au(2) is bonded in a 10-coordinate geometry to one Ca(4), two equivalent Ca(1), three equivalent Ca(6), one Au(12), two equivalent Au(7), and one Si(1) atom. In the third Au site, Au(3) is bonded in a 10-coordinate geometry to one Ca(4), two equivalent Ca(5), three equivalent Ca(9), one Au(9), one Si(2), and two equivalent Si(6) atoms. In the fourth Au site, Au(4) is bonded in a 10-coordinate geometry to one Ca(5), two equivalent Ca(2), three equivalent Ca(10), one Au(10), one Si(3), and two equivalent Si(7) atoms. In the fifth Au site, Au(5) is bonded in a 10-coordinate geometry to one Ca(2), two equivalent Ca(3), three equivalent Ca(7), one Au(11), one Si(4), and two equivalent Si(8) atoms. In the sixth Au site, Au(6) is bonded in a 6-coordinate geometry to one Ca(3), two equivalent Ca(1), two equivalent Ca(8), one Au(12), two equivalent Au(1), and one Si(5) atom. In the seventh Au site, Au(7) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(4), three equivalent Ca(6), one Au(8), two equivalent Au(2), and one Si(1) atom. In the eighth Au site, Au(8) is bonded in a 10-coordinate geometry to one Ca(6), two equivalent Ca(9), three equivalent Ca(4), one Au(7), one Si(6), and two equivalent Si(1) atoms. In the ninth Au site, Au(9) is bonded in a 10-coordinate geometry to one Ca(9), two equivalent Ca(10), three equivalent Ca(5), one Au(3), one Si(7), and two equivalent Si(2) atoms. In the tenth Au site, Au(10) is bonded in a 10-coordinate geometry to one Ca(10), two equivalent Ca(7), three equivalent Ca(2), one Au(4), one Si(8), and two equivalent Si(3) atoms. In the eleventh Au site, Au(11) is bonded in a 10-coordinate geometry to one Ca(7), two equivalent Ca(8), three equivalent Ca(3), one Au(1), one Au(5), and two equivalent Si(4) atoms. In the twelfth Au site, Au(12) is bonded in a 10-coordinate geometry to one Ca(8), two equivalent Ca(6), three equivalent Ca(1), one Au(2), one Au(6), and two equivalent Si(5) atoms. There are eight inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to one Ca(9), two equivalent Ca(6), three equivalent Ca(4), one Au(2), one Au(7), and two equivalent Au(8) atoms. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to one Ca(10), two equivalent Ca(9), three equivalent Ca(5), one Au(3), two equivalent Au(9), and one Si(6) atom. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one Ca(7), two equivalent Ca(10), three equivalent Ca(2), one Au(4), two equivalent Au(10), and one Si(7) atom. In the fourth Si site, Si(4) is bonded in a 10-coordinate geometry to one Ca(8), two equivalent Ca(7), three equivalent Ca(3), one Au(5), two equivalent Au(11), and one Si(8) atom. In the fifth Si site, Si(5) is bonded in a 4-coordinate geometry to one Ca(6), two equivalent Ca(8), three equivalent Ca(1), one Au(1), one Au(6), and two equivalent Au(12) atoms. In the sixth Si site, Si(6) is bonded in a 10-coordinate geometry to one Ca(5), two equivalent Ca(4), three equivalent Ca(9), one Au(8), two equivalent Au(3), and one Si(2) atom. In the seventh Si site, Si(7) is bonded in a 10-coordinate geometry to one Ca(2), two equivalent Ca(5), three equivalent Ca(10), one Au(9), two equivalent Au(4), and one Si(3) atom. In the eighth Si site, Si(8) is bonded in a 10-coordinate geometry to one Ca(3), two equivalent Ca(2), three equivalent Ca(7), one Au(10), two equivalent Au(5), and one Si(4) atom.
Ca5(Au3Si2)2 crystallizes in the monoclinic Cm space group. There are ten inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 12-coordinate geometry to one Au(1), one Au(7), two equivalent Au(2), two equivalent Au(6), three equivalent Au(12), and three equivalent Si(5) atoms. The Ca(1)-Au(1) bond length is 3.40 Å. The Ca(1)-Au(7) bond length is 3.16 Å. Both Ca(1)-Au(2) bond lengths are 3.30 Å. Both Ca(1)-Au(6) bond lengths are 3.13 Å. There is one shorter (3.01 Å) and two longer (3.19 Å) Ca(1)-Au(12) bond lengths. There is one shorter (3.11 Å) and two longer (3.43 Å) Ca(1)-Si(5) bond lengths. In the second Ca site, Ca(2) is bonded in a 12-coordinate geometry to one Au(5), two equivalent Au(4), three equivalent Au(10), one Si(7), two equivalent Si(8), and three equivalent Si(3) atoms. The Ca(2)-Au(5) bond length is 3.01 Å. Both Ca(2)-Au(4) bond lengths are 3.14 Å. There is one shorter (3.05 Å) and two longer (3.15 Å) Ca(2)-Au(10) bond lengths. The Ca(2)-Si(7) bond length is 3.10 Å. Both Ca(2)-Si(8) bond lengths are 3.33 Å. There is one shorter (3.13 Å) and two longer (3.36 Å) Ca(2)-Si(3) bond lengths. In the third Ca site, Ca(3) is bonded in a 12-coordinate geometry to one Au(6), two equivalent Au(1), two equivalent Au(5), three equivalent Au(11), one Si(8), and three equivalent Si(4) atoms. The Ca(3)-Au(6) bond length is 3.24 Å. Both Ca(3)-Au(1) bond lengths are 3.26 Å. Both Ca(3)-Au(5) bond lengths are 3.23 Å. There is one shorter (2.99 Å) and two longer (3.19 Å) Ca(3)-Au(11) bond lengths. The Ca(3)-Si(8) bond length is 3.22 Å. There is one shorter (3.18 Å) and two longer (3.41 Å) Ca(3)-Si(4) bond lengths. In the fourth Ca site, Ca(4) is bonded in a 12-coordinate geometry to one Au(2), one Au(3), two equivalent Au(7), three equivalent Au(8), two equivalent Si(6), and three equivalent Si(1) atoms. The Ca(4)-Au(2) bond length is 3.19 Å. The Ca(4)-Au(3) bond length is 3.04 Å. Both Ca(4)-Au(7) bond lengths are 3.05 Å. There is one shorter (3.06 Å) and two longer (3.14 Å) Ca(4)-Au(8) bond lengths. Both Ca(4)-Si(6) bond lengths are 3.35 Å. There is one shorter (3.08 Å) and two longer (3.33 Å) Ca(4)-Si(1) bond lengths. In the fifth Ca site, Ca(5) is bonded in a 12-coordinate geometry to one Au(4), two equivalent Au(3), three equivalent Au(9), one Si(6), two equivalent Si(7), and three equivalent Si(2) atoms. The Ca(5)-Au(4) bond length is 3.01 Å. Both Ca(5)-Au(3) bond lengths are 3.11 Å. There is one shorter (3.04 Å) and two longer (3.15 Å) Ca(5)-Au(9) bond lengths. The Ca(5)-Si(6) bond length is 3.10 Å. Both Ca(5)-Si(7) bond lengths are 3.34 Å. There is one shorter (3.13 Å) and two longer (3.35 Å) Ca(5)-Si(2) bond lengths. In the sixth Ca site, Ca(6) is bonded in a 12-coordinate geometry to one Au(8), two equivalent Au(12), three equivalent Au(2), three equivalent Au(7), one Si(5), and two equivalent Si(1) atoms. The Ca(6)-Au(8) bond length is 3.40 Å. Both Ca(6)-Au(12) bond lengths are 3.29 Å. There are two shorter (3.01 Å) and one longer (3.26 Å) Ca(6)-Au(2) bond length. There are two shorter (3.09 Å) and one longer (3.57 Å) Ca(6)-Au(7) bond length. The Ca(6)-Si(5) bond length is 3.17 Å. Both Ca(6)-Si(1) bond lengths are 3.18 Å. In the seventh Ca site, Ca(7) is bonded in a 12-coordinate geometry to one Au(11), two equivalent Au(10), three equivalent Au(5), one Si(3), two equivalent Si(4), and three equivalent Si(8) atoms. The Ca(7)-Au(11) bond length is 3.12 Å. Both Ca(7)-Au(10) bond lengths are 3.13 Å. There are two shorter (3.13 Å) and one longer (3.33 Å) Ca(7)-Au(5) bond length. The Ca(7)-Si(3) bond length is 3.17 Å. Both Ca(7)-Si(4) bond lengths are 3.01 Å. There are two shorter (3.06 Å) and one longer (3.19 Å) Ca(7)-Si(8) bond length. In the eighth Ca site, Ca(8) is bonded in a 11-coordinate geometry to one Au(12), two equivalent Au(11), two equivalent Au(6), three equivalent Au(1), one Si(4), and two equivalent Si(5) atoms. The Ca(8)-Au(12) bond length is 3.21 Å. Both Ca(8)-Au(11) bond lengths are 3.24 Å. Both Ca(8)-Au(6) bond lengths are 3.08 Å. There are two shorter (3.03 Å) and one longer (3.21 Å) Ca(8)-Au(1) bond length. The Ca(8)-Si(4) bond length is 3.24 Å. Both Ca(8)-Si(5) bond lengths are 3.16 Å. In the ninth Ca site, Ca(9) is bonded in a 12-coordinate geometry to one Au(9), two equivalent Au(8), three equivalent Au(3), one Si(1), two equivalent Si(2), and three equivalent Si(6) atoms. The Ca(9)-Au(9) bond length is 3.29 Å. Both Ca(9)-Au(8) bond lengths are 3.14 Å. There are two shorter (3.16 Å) and one longer (3.30 Å) Ca(9)-Au(3) bond length. The Ca(9)-Si(1) bond length is 3.08 Å. Both Ca(9)-Si(2) bond lengths are 3.03 Å. There are two shorter (3.03 Å) and one longer (3.22 Å) Ca(9)-Si(6) bond length. In the tenth Ca site, Ca(10) is bonded in a 12-coordinate geometry to one Au(10), two equivalent Au(9), three equivalent Au(4), one Si(2), two equivalent Si(3), and three equivalent Si(7) atoms. The Ca(10)-Au(10) bond length is 3.25 Å. Both Ca(10)-Au(9) bond lengths are 3.12 Å. There are two shorter (3.14 Å) and one longer (3.30 Å) Ca(10)-Au(4) bond length. The Ca(10)-Si(2) bond length is 3.18 Å. Both Ca(10)-Si(3) bond lengths are 3.01 Å. There are two shorter (3.03 Å) and one longer (3.22 Å) Ca(10)-Si(7) bond length. There are twelve inequivalent Au sites. In the first Au site, Au(1) is bonded in a 10-coordinate geometry to one Ca(1), two equivalent Ca(3), three equivalent Ca(8), one Au(11), two equivalent Au(6), and one Si(5) atom. The Au(1)-Au(11) bond length is 2.83 Å. Both Au(1)-Au(6) bond lengths are 2.80 Å. The Au(1)-Si(5) bond length is 2.62 Å. In the second Au site, Au(2) is bonded in a 10-coordinate geometry to one Ca(4), two equivalent Ca(1), three equivalent Ca(6), one Au(12), two equivalent Au(7), and one Si(1) atom. The Au(2)-Au(12) bond length is 2.87 Å. Both Au(2)-Au(7) bond lengths are 2.77 Å. The Au(2)-Si(1) bond length is 2.66 Å. In the third Au site, Au(3) is bonded in a 10-coordinate geometry to one Ca(4), two equivalent Ca(5), three equivalent Ca(9), one Au(9), one Si(2), and two equivalent Si(6) atoms. The Au(3)-Au(9) bond length is 3.14 Å. The Au(3)-Si(2) bond length is 2.65 Å. Both Au(3)-Si(6) bond lengths are 2.59 Å. In the fourth Au site, Au(4) is bonded in a 10-coordinate geometry to one Ca(5), two equivalent Ca(2), three equivalent Ca(10), one Au(10), one Si(3), and two equivalent Si(7) atoms. The Au(4)-Au(10) bond length is 3.16 Å. The Au(4)-Si(3) bond length is 2.64 Å. Both Au(4)-Si(7) bond lengths are 2.59 Å. In the fifth Au site, Au(5) is bonded in a 10-coordinate geometry to one Ca(2), two equivalent Ca(3), three equivalent Ca(7), one Au(11), one Si(4), and two equivalent Si(8) atoms. The Au(5)-Au(11) bond length is 3.09 Å. The Au(5)-Si(4) bond length is 2.62 Å. Both Au(5)-Si(8) bond lengths are 2.59 Å. In the sixth Au site, Au(6) is bonded in a 6-coordinate geometry to one Ca(3), two equivalent Ca(1), two equivalent Ca(8), one Au(12), two equivalent Au(1), and one Si(5) atom. The Au(6)-Au(12) bond length is 3.08 Å. The Au(6)-Si(5) bond length is 2.47 Å. In the seventh Au site, Au(7) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(4), three equivalent Ca(6), one Au(8), two equivalent Au(2), and one Si(1) atom. The Au(7)-Au(8) bond length is 3.20 Å. The Au(7)-Si(1) bond length is 2.48 Å. In the eighth Au site, Au(8) is bonded in a 10-coordinate geometry to one Ca(6), two equivalent Ca(9), three equivalent Ca(4), one Au(7), one Si(6), and two equivalent Si(1) atoms. The Au(8)-Si(6) bond length is 2.62 Å. Both Au(8)-Si(1) bond lengths are 2.55 Å. In the ninth Au site, Au(9) is bonded in a 10-coordinate geometry to one Ca(9), two equivalent Ca(10), three equivalent Ca(5), one Au(3), one Si(7), and two equivalent Si(2) atoms. The Au(9)-Si(7) bond length is 2.65 Å. Both Au(9)-Si(2) bond lengths are 2.59 Å. In the tenth Au site, Au(10) is bonded in a 10-coordinate geometry to one Ca(10), two equivalent Ca(7), three equivalent Ca(2), one Au(4), one Si(8), and two equivalent Si(3) atoms. The Au(10)-Si(8) bond length is 2.64 Å. Both Au(10)-Si(3) bond lengths are 2.59 Å. In the eleventh Au site, Au(11) is bonded in a 10-coordinate geometry to one Ca(7), two equivalent Ca(8), three equivalent Ca(3), one Au(1), one Au(5), and two equivalent Si(4) atoms. Both Au(11)-Si(4) bond lengths are 2.52 Å. In the twelfth Au site, Au(12) is bonded in a 10-coordinate geometry to one Ca(8), two equivalent Ca(6), three equivalent Ca(1), one Au(2), one Au(6), and two equivalent Si(5) atoms. Both Au(12)-Si(5) bond lengths are 2.47 Å. There are eight inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to one Ca(9), two equivalent Ca(6), three equivalent Ca(4), one Au(2), one Au(7), and two equivalent Au(8) atoms. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to one Ca(10), two equivalent Ca(9), three equivalent Ca(5), one Au(3), two equivalent Au(9), and one Si(6) atom. The Si(2)-Si(6) bond length is 2.57 Å. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one Ca(7), two equivalent Ca(10), three equivalent Ca(2), one Au(4), two equivalent Au(10), and one Si(7) atom. The Si(3)-Si(7) bond length is 2.55 Å. In the fourth Si site, Si(4) is bonded in a 10-coordinate geometry to one Ca(8), two equivalent Ca(7), three equivalent Ca(3), one Au(5), two equivalent Au(11), and one Si(8) atom. The Si(4)-Si(8) bond length is 2.55 Å. In the fifth Si site, Si(5) is bonded in a 4-coordinate geometry to one Ca(6), two equivalent Ca(8), three equivalent Ca(1), one Au(1), one Au(6), and two equivalent Au(12) atoms. In the sixth Si site, Si(6) is bonded in a 10-coordinate geometry to one Ca(5), two equivalent Ca(4), three equivalent Ca(9), one Au(8), two equivalent Au(3), and one Si(2) atom. In the seventh Si site, Si(7) is bonded in a 10-coordinate geometry to one Ca(2), two equivalent Ca(5), three equivalent Ca(10), one Au(9), two equivalent Au(4), and one Si(3) atom. In the eighth Si site, Si(8) is bonded in a 10-coordinate geometry to one Ca(3), two equivalent Ca(2), three equivalent Ca(7), one Au(10), two equivalent Au(5), and one Si(4) atom.