Fe4Zn9 is gamma-brass-like structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 13-coordinate geometry to one Fe(3), one Fe(4), one Fe(6), one Zn(2), one Zn(7), two equivalent Zn(1), two equivalent Zn(4), two equivalent Zn(6), and two equivalent Zn(9) atoms. In the second Fe site, Fe(2) is bonded in a 13-coordinate geometry to one Fe(4), one Fe(5), one Zn(10), one Zn(11), one Zn(2), one Zn(3), one Zn(4), one Zn(6), one Zn(9), two equivalent Zn(1), and two equivalent Zn(5) atoms. In the third Fe site, Fe(3) is bonded in a 13-coordinate geometry to one Fe(1), two equivalent Fe(5), one Zn(10), one Zn(2), one Zn(7), one Zn(8), two equivalent Zn(3), two equivalent Zn(4), and two equivalent Zn(5) atoms. In the fourth Fe site, Fe(4) is bonded in a 12-coordinate geometry to one Fe(1), one Fe(6), two equivalent Fe(2), two equivalent Fe(5), one Zn(10), one Zn(2), two equivalent Zn(1), and two equivalent Zn(9) atoms. In the fifth Fe site, Fe(5) is bonded in a 12-coordinate geometry to one Fe(2), one Fe(3), one Fe(4), one Fe(5), one Fe(6), one Zn(10), one Zn(11), one Zn(3), one Zn(4), one Zn(5), one Zn(8), and one Zn(9) atom. In the sixth Fe site, Fe(6) is bonded in a 12-coordinate geometry to one Fe(1), one Fe(4), two equivalent Fe(5), one Zn(7), one Zn(8), two equivalent Zn(11), two equivalent Zn(6), and two equivalent Zn(9) atoms. There are eleven inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(4), two equivalent Fe(2), one Zn(11), one Zn(3), one Zn(4), one Zn(5), one Zn(7), one Zn(8), and one Zn(9) atom. In the second Zn site, Zn(2) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(3), one Fe(4), two equivalent Fe(2), one Zn(10), one Zn(8), two equivalent Zn(3), and two equivalent Zn(6) atoms. In the third Zn site, Zn(3) is bonded in a 11-coordinate geometry to one Fe(2), one Fe(3), one Fe(5), one Zn(1), one Zn(2), one Zn(4), one Zn(6), one Zn(8), one Zn(9), and two equivalent Zn(11) atoms. In the fourth Zn site, Zn(4) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(2), one Fe(3), one Fe(5), one Zn(1), one Zn(11), one Zn(3), one Zn(5), one Zn(6), and two equivalent Zn(9) atoms. In the fifth Zn site, Zn(5) is bonded in a 11-coordinate geometry to one Fe(3), one Fe(5), two equivalent Fe(2), one Zn(1), one Zn(10), one Zn(11), one Zn(4), one Zn(6), one Zn(7), and one Zn(9) atom. In the sixth Zn site, Zn(6) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(2), one Fe(6), one Zn(10), one Zn(2), one Zn(3), one Zn(4), one Zn(5), one Zn(9), and two equivalent Zn(11) atoms. In the seventh Zn site, Zn(7) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(3), one Fe(6), one Zn(10), one Zn(8), two equivalent Zn(1), two equivalent Zn(11), and two equivalent Zn(5) atoms. In the eighth Zn site, Zn(8) is bonded in a 12-coordinate geometry to one Fe(3), one Fe(6), two equivalent Fe(5), one Zn(2), one Zn(7), two equivalent Zn(1), two equivalent Zn(11), and two equivalent Zn(3) atoms. In the ninth Zn site, Zn(9) is bonded in a 12-coordinate geometry to one Fe(1), one Fe(2), one Fe(4), one Fe(5), one Fe(6), one Zn(1), one Zn(11), one Zn(3), one Zn(5), one Zn(6), and two equivalent Zn(4) atoms. In the tenth Zn site, Zn(10) is bonded in a 12-coordinate geometry to one Fe(3), one Fe(4), two equivalent Fe(2), two equivalent Fe(5), one Zn(2), one Zn(7), two equivalent Zn(5), and two equivalent Zn(6) atoms. In the eleventh Zn site, Zn(11) is bonded in a 13-coordinate geometry to one Fe(2), one Fe(5), one Fe(6), one Zn(1), one Zn(4), one Zn(5), one Zn(7), one Zn(8), one Zn(9), two equivalent Zn(3), and two equivalent Zn(6) atoms.
Fe4Zn9 is gamma-brass-like structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 13-coordinate geometry to one Fe(3), one Fe(4), one Fe(6), one Zn(2), one Zn(7), two equivalent Zn(1), two equivalent Zn(4), two equivalent Zn(6), and two equivalent Zn(9) atoms. The Fe(1)-Fe(3) bond length is 2.68 Å. The Fe(1)-Fe(4) bond length is 2.55 Å. The Fe(1)-Fe(6) bond length is 2.53 Å. The Fe(1)-Zn(2) bond length is 2.91 Å. The Fe(1)-Zn(7) bond length is 2.86 Å. Both Fe(1)-Zn(1) bond lengths are 2.90 Å. Both Fe(1)-Zn(4) bond lengths are 2.59 Å. Both Fe(1)-Zn(6) bond lengths are 2.77 Å. Both Fe(1)-Zn(9) bond lengths are 2.68 Å. In the second Fe site, Fe(2) is bonded in a 13-coordinate geometry to one Fe(4), one Fe(5), one Zn(10), one Zn(11), one Zn(2), one Zn(3), one Zn(4), one Zn(6), one Zn(9), two equivalent Zn(1), and two equivalent Zn(5) atoms. The Fe(2)-Fe(4) bond length is 2.53 Å. The Fe(2)-Fe(5) bond length is 2.51 Å. The Fe(2)-Zn(10) bond length is 2.66 Å. The Fe(2)-Zn(11) bond length is 2.65 Å. The Fe(2)-Zn(2) bond length is 2.84 Å. The Fe(2)-Zn(3) bond length is 2.96 Å. The Fe(2)-Zn(4) bond length is 2.76 Å. The Fe(2)-Zn(6) bond length is 2.64 Å. The Fe(2)-Zn(9) bond length is 2.66 Å. There is one shorter (2.74 Å) and one longer (2.96 Å) Fe(2)-Zn(1) bond length. There is one shorter (2.65 Å) and one longer (2.76 Å) Fe(2)-Zn(5) bond length. In the third Fe site, Fe(3) is bonded in a 13-coordinate geometry to one Fe(1), two equivalent Fe(5), one Zn(10), one Zn(2), one Zn(7), one Zn(8), two equivalent Zn(3), two equivalent Zn(4), and two equivalent Zn(5) atoms. Both Fe(3)-Fe(5) bond lengths are 2.56 Å. The Fe(3)-Zn(10) bond length is 2.70 Å. The Fe(3)-Zn(2) bond length is 2.61 Å. The Fe(3)-Zn(7) bond length is 2.57 Å. The Fe(3)-Zn(8) bond length is 2.69 Å. Both Fe(3)-Zn(3) bond lengths are 2.76 Å. Both Fe(3)-Zn(4) bond lengths are 2.88 Å. Both Fe(3)-Zn(5) bond lengths are 2.85 Å. In the fourth Fe site, Fe(4) is bonded in a 12-coordinate geometry to one Fe(1), one Fe(6), two equivalent Fe(2), two equivalent Fe(5), one Zn(10), one Zn(2), two equivalent Zn(1), and two equivalent Zn(9) atoms. The Fe(4)-Fe(6) bond length is 2.65 Å. Both Fe(4)-Fe(5) bond lengths are 2.68 Å. The Fe(4)-Zn(10) bond length is 2.62 Å. The Fe(4)-Zn(2) bond length is 2.67 Å. Both Fe(4)-Zn(1) bond lengths are 2.62 Å. Both Fe(4)-Zn(9) bond lengths are 2.62 Å. In the fifth Fe site, Fe(5) is bonded in a 12-coordinate geometry to one Fe(2), one Fe(3), one Fe(4), one Fe(5), one Fe(6), one Zn(10), one Zn(11), one Zn(3), one Zn(4), one Zn(5), one Zn(8), and one Zn(9) atom. The Fe(5)-Fe(5) bond length is 2.64 Å. The Fe(5)-Fe(6) bond length is 2.60 Å. The Fe(5)-Zn(10) bond length is 2.59 Å. The Fe(5)-Zn(11) bond length is 2.71 Å. The Fe(5)-Zn(3) bond length is 2.70 Å. The Fe(5)-Zn(4) bond length is 2.75 Å. The Fe(5)-Zn(5) bond length is 2.65 Å. The Fe(5)-Zn(8) bond length is 2.61 Å. The Fe(5)-Zn(9) bond length is 2.57 Å. In the sixth Fe site, Fe(6) is bonded in a 12-coordinate geometry to one Fe(1), one Fe(4), two equivalent Fe(5), one Zn(7), one Zn(8), two equivalent Zn(11), two equivalent Zn(6), and two equivalent Zn(9) atoms. The Fe(6)-Zn(7) bond length is 2.85 Å. The Fe(6)-Zn(8) bond length is 2.54 Å. Both Fe(6)-Zn(11) bond lengths are 2.68 Å. Both Fe(6)-Zn(6) bond lengths are 2.74 Å. Both Fe(6)-Zn(9) bond lengths are 2.57 Å. There are eleven inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(4), two equivalent Fe(2), one Zn(11), one Zn(3), one Zn(4), one Zn(5), one Zn(7), one Zn(8), and one Zn(9) atom. The Zn(1)-Zn(11) bond length is 2.58 Å. The Zn(1)-Zn(3) bond length is 2.69 Å. The Zn(1)-Zn(4) bond length is 2.62 Å. The Zn(1)-Zn(5) bond length is 2.61 Å. The Zn(1)-Zn(7) bond length is 2.68 Å. The Zn(1)-Zn(8) bond length is 2.69 Å. The Zn(1)-Zn(9) bond length is 2.56 Å. In the second Zn site, Zn(2) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(3), one Fe(4), two equivalent Fe(2), one Zn(10), one Zn(8), two equivalent Zn(3), and two equivalent Zn(6) atoms. The Zn(2)-Zn(10) bond length is 2.56 Å. The Zn(2)-Zn(8) bond length is 2.65 Å. Both Zn(2)-Zn(3) bond lengths are 2.61 Å. Both Zn(2)-Zn(6) bond lengths are 2.62 Å. In the third Zn site, Zn(3) is bonded in a 11-coordinate geometry to one Fe(2), one Fe(3), one Fe(5), one Zn(1), one Zn(2), one Zn(4), one Zn(6), one Zn(8), one Zn(9), and two equivalent Zn(11) atoms. The Zn(3)-Zn(4) bond length is 2.68 Å. The Zn(3)-Zn(6) bond length is 2.79 Å. The Zn(3)-Zn(8) bond length is 2.56 Å. The Zn(3)-Zn(9) bond length is 2.69 Å. There is one shorter (2.59 Å) and one longer (2.88 Å) Zn(3)-Zn(11) bond length. In the fourth Zn site, Zn(4) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(2), one Fe(3), one Fe(5), one Zn(1), one Zn(11), one Zn(3), one Zn(5), one Zn(6), and two equivalent Zn(9) atoms. The Zn(4)-Zn(11) bond length is 2.98 Å. The Zn(4)-Zn(5) bond length is 2.61 Å. The Zn(4)-Zn(6) bond length is 2.72 Å. There is one shorter (2.58 Å) and one longer (2.65 Å) Zn(4)-Zn(9) bond length. In the fifth Zn site, Zn(5) is bonded in a 11-coordinate geometry to one Fe(3), one Fe(5), two equivalent Fe(2), one Zn(1), one Zn(10), one Zn(11), one Zn(4), one Zn(6), one Zn(7), and one Zn(9) atom. The Zn(5)-Zn(10) bond length is 2.55 Å. The Zn(5)-Zn(11) bond length is 2.88 Å. The Zn(5)-Zn(6) bond length is 2.72 Å. The Zn(5)-Zn(7) bond length is 2.71 Å. The Zn(5)-Zn(9) bond length is 2.68 Å. In the sixth Zn site, Zn(6) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(2), one Fe(6), one Zn(10), one Zn(2), one Zn(3), one Zn(4), one Zn(5), one Zn(9), and two equivalent Zn(11) atoms. The Zn(6)-Zn(10) bond length is 2.67 Å. The Zn(6)-Zn(9) bond length is 2.57 Å. There is one shorter (2.85 Å) and one longer (2.87 Å) Zn(6)-Zn(11) bond length. In the seventh Zn site, Zn(7) is bonded in a 11-coordinate geometry to one Fe(1), one Fe(3), one Fe(6), one Zn(10), one Zn(8), two equivalent Zn(1), two equivalent Zn(11), and two equivalent Zn(5) atoms. The Zn(7)-Zn(10) bond length is 2.67 Å. The Zn(7)-Zn(8) bond length is 2.59 Å. Both Zn(7)-Zn(11) bond lengths are 2.89 Å. In the eighth Zn site, Zn(8) is bonded in a 12-coordinate geometry to one Fe(3), one Fe(6), two equivalent Fe(5), one Zn(2), one Zn(7), two equivalent Zn(1), two equivalent Zn(11), and two equivalent Zn(3) atoms. Both Zn(8)-Zn(11) bond lengths are 2.75 Å. In the ninth Zn site, Zn(9) is bonded in a 12-coordinate geometry to one Fe(1), one Fe(2), one Fe(4), one Fe(5), one Fe(6), one Zn(1), one Zn(11), one Zn(3), one Zn(5), one Zn(6), and two equivalent Zn(4) atoms. The Zn(9)-Zn(11) bond length is 2.76 Å. In the tenth Zn site, Zn(10) is bonded in a 12-coordinate geometry to one Fe(3), one Fe(4), two equivalent Fe(2), two equivalent Fe(5), one Zn(2), one Zn(7), two equivalent Zn(5), and two equivalent Zn(6) atoms. In the eleventh Zn site, Zn(11) is bonded in a 13-coordinate geometry to one Fe(2), one Fe(5), one Fe(6), one Zn(1), one Zn(4), one Zn(5), one Zn(7), one Zn(8), one Zn(9), two equivalent Zn(3), and two equivalent Zn(6) atoms.