TY - JOUR
T1 - Polymorphism and Related Magnetic Behavior in Decamethylferrocenium Salts of Transition-Metal Maleonitriledithiolates
AU - Fettouhi, Mohammed
AU - Ouahab, Lahcène
AU - Hagiwara, Massa
AU - Codjovi, Epiphane
AU - Kahn, Olivier
AU - Constant-Machado, H.
AU - Varret, François
PY - 1995/8/1
Y1 - 1995/8/1
N2 - Several decamethylferrocenium/transition-metal maleonitriledithiolate compounds have been synthesized and structurally characterized. The compounds [Fe(cp*)2]x[M(mnt)2]y(CH3CN)z (M = Cu(II), Co(HI), Fe(III)) crystallize in the triclinic space group P1 (No. 2). For M = Co(III) two solid-state phases have been isolated. a-[Fe(cp*)2]2[Co(mnt)2]2(CH3CN)2 (Fe2Co2A): a = 9.894(4) Å, b = 12.942(6) Å, c = 15.056(6) Å, a = 110.13(3)°, ß = 98.41(4)°, ? = 107.78(3)°, V = 1657 Å3, Mr = 1413.3, dc = 1.419 g/cm3, Z = 1, and R = 0.061 for 2351 reflections with I = 3s(I). ß-[Fe(cp*)2]2[Co(mnt)2]2 (Fe2Co2B): a = 9.576(8) Å, b = 12.849(4) Å, c = 13.641(7) Å, a = 108.13(4)°, ß = 90.91(6)°, ? = 103.54(4)°, V = 1544 Å3, Mr = 1331.2, dc = 1.431 g/cm3, Z = 1, and R = 0.043 for 2407 reflections with I = 3s(I). The isostructural a modification is observed for M = Fe(III). a-[Fe(cp*)2]2[Fe(mnt)2]2(CH3CN)2 (Fe2Fe2A): a = 9.905(7) Å, b = 12.966(5) Å, c = 15.142(3) Å, a = 109.77(2)°, ß = 98.64(4)°, ? = 108.06(6)°, V = 1668 Å3, Mr = 1407.2, dc = 1.401 g/cm3, Z = 1, and R = 0.063 for 3125 reflections with I = 3s(I). The dimeric anionic species show a square pyramidal coordination for the metal (the apical M-S bonds are Co-S = 2.39, 2.35 Å and Fe-S = 2.49 Å). Orthogonal arrangement of adjacent cations is observed in the decamethylferrocenium chains of the two a compounds, while a parallel packing exists in the ß modification. [Fe(cp*)2]2Cu(mnt)2 (Fe2Cu): a = 9.713(5) Å, b = 11.407(4) Å, c = 11.958(5) Å, a = 100.90(2)°, ß = 113.20(5)°, ? = 92.66(3)°, V = 1185 Å3, Mr = 996.5, dc = 1.396 g/cm3, Z = 1, and R = 0.041 for 2724 reflections with I = 3s(I). The dianion [Cu(mnt)2]2− exhibits a planar monomelic structure and the mixed anion-cation stacks adopt a … A2−D+D+A2−D+D+A2− … arrangement with short anion-cation distances: d(Fe-S) = 5.54 Å and d(Fe-Cu) = 6.37 Å. The magnetic properties of all the compounds have been investigated. In both Fe2Co2A and Fe2Co2B the decamethylferrocenium cations have been found to be magnetically isolated. In Fe2Fe2A, a strong antiferromagnetic interaction within the {[Fe(mnt)]2}2− dimeric unit has been characterized. In Fe2Cu, finally, each [Cu(mnt)2]2− is found to interact antiferromagnetically with two adjacent [Fe(Cp*)2]+ cations.
AB - Several decamethylferrocenium/transition-metal maleonitriledithiolate compounds have been synthesized and structurally characterized. The compounds [Fe(cp*)2]x[M(mnt)2]y(CH3CN)z (M = Cu(II), Co(HI), Fe(III)) crystallize in the triclinic space group P1 (No. 2). For M = Co(III) two solid-state phases have been isolated. a-[Fe(cp*)2]2[Co(mnt)2]2(CH3CN)2 (Fe2Co2A): a = 9.894(4) Å, b = 12.942(6) Å, c = 15.056(6) Å, a = 110.13(3)°, ß = 98.41(4)°, ? = 107.78(3)°, V = 1657 Å3, Mr = 1413.3, dc = 1.419 g/cm3, Z = 1, and R = 0.061 for 2351 reflections with I = 3s(I). ß-[Fe(cp*)2]2[Co(mnt)2]2 (Fe2Co2B): a = 9.576(8) Å, b = 12.849(4) Å, c = 13.641(7) Å, a = 108.13(4)°, ß = 90.91(6)°, ? = 103.54(4)°, V = 1544 Å3, Mr = 1331.2, dc = 1.431 g/cm3, Z = 1, and R = 0.043 for 2407 reflections with I = 3s(I). The isostructural a modification is observed for M = Fe(III). a-[Fe(cp*)2]2[Fe(mnt)2]2(CH3CN)2 (Fe2Fe2A): a = 9.905(7) Å, b = 12.966(5) Å, c = 15.142(3) Å, a = 109.77(2)°, ß = 98.64(4)°, ? = 108.06(6)°, V = 1668 Å3, Mr = 1407.2, dc = 1.401 g/cm3, Z = 1, and R = 0.063 for 3125 reflections with I = 3s(I). The dimeric anionic species show a square pyramidal coordination for the metal (the apical M-S bonds are Co-S = 2.39, 2.35 Å and Fe-S = 2.49 Å). Orthogonal arrangement of adjacent cations is observed in the decamethylferrocenium chains of the two a compounds, while a parallel packing exists in the ß modification. [Fe(cp*)2]2Cu(mnt)2 (Fe2Cu): a = 9.713(5) Å, b = 11.407(4) Å, c = 11.958(5) Å, a = 100.90(2)°, ß = 113.20(5)°, ? = 92.66(3)°, V = 1185 Å3, Mr = 996.5, dc = 1.396 g/cm3, Z = 1, and R = 0.041 for 2724 reflections with I = 3s(I). The dianion [Cu(mnt)2]2− exhibits a planar monomelic structure and the mixed anion-cation stacks adopt a … A2−D+D+A2−D+D+A2− … arrangement with short anion-cation distances: d(Fe-S) = 5.54 Å and d(Fe-Cu) = 6.37 Å. The magnetic properties of all the compounds have been investigated. In both Fe2Co2A and Fe2Co2B the decamethylferrocenium cations have been found to be magnetically isolated. In Fe2Fe2A, a strong antiferromagnetic interaction within the {[Fe(mnt)]2}2− dimeric unit has been characterized. In Fe2Cu, finally, each [Cu(mnt)2]2− is found to interact antiferromagnetically with two adjacent [Fe(Cp*)2]+ cations.
UR - http://www.scopus.com/inward/record.url?scp=33751156767&partnerID=8YFLogxK
U2 - 10.1021/ic00120a020
DO - 10.1021/ic00120a020
M3 - Article
AN - SCOPUS:33751156767
SN - 0020-1669
VL - 34
SP - 4152
EP - 4159
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 16
ER -