Ferromagnetism and Chirality in Two-Dimensional Cyanide-Bridged Bimetallic Compounds

(a) Universitat de València.

(b) Université de Neuchâtel.

Coronado, E., Delhaès, P., Gatteschi, D., Miller, J. S., Eds. Molecular Magnetism:  From Molecular Assemblies to the Devices; NATO ASI Series E321; Kluwer Academic Publishers:  Dordrecht, 1996.

10.1016/S0010-8545(00)00233-2

10.1038/35044035

10.1021/ja0002619

10.1038/37323

10.1021/ic00020a029

10.1021/ic980306v

10.1021/ic9904135

10.1021/ic0008870

10.1002/(SICI)1521-3773(19990601)38:11%3C1601::AID-ANIE1601%3E3.0.CO;2-%23

10.1002/1521-3773(20020215)41:4%3C586::AID-ANIE586%3E3.0.CO;2-6

While our work was in progress, a 3D cyanide-bridged Cr−Mn system based on chiral propane-1,2-diamine was reported:  Inoue, K.; Imai, H.; Ghalsasi, P. S.; Kikuchi, K.; Ohba, M.; Okawa, H.; Yakhmi, J. V. Angew. Chem. Int. Ed.2001, 40, 4242−4245.10.1002/1521-3773(20011119)40:22%3C4242:AID-ANIE4242%3E3.0.CO;2-H

10.1016/S0020-1693(96)05525-9

10.1002/1099-0682(200207)2002:7%3C1603::AID-EJIC1603%3E3.0.CO;2-T

Single crystals of compounds 1 and 2 were grown by slow diffusion of the precursors in a water/acetonitrile mixture. Anal. Calcd for C48H88Fe2N24Ni3O2 (1):  C, 43.64; H, 6.71; N, 25.44. Found:  C, 43.56; H, 6.49; N, 25.26. IR (KBr, cm-1):  ν = 3339, 3277 (N−H); 2919, 2847 (C−H); 2105 (C⋮N). Anal. Calcd for C48H88Fe2N24Ni3O2 (2):  C, 43.64; H, 6.71; N, 25.44. Found:  C, 43.46; H, 6.63; N, 25.34. IR (KBr, cm-1):  ν = 3334, 3283 (N−H); 2924, 2858 (C−H); 2105 (C⋮N).

Crystallographic data for 1:  C48H88Fe2Ni3N24O2, M = 1321.25, P1, a = 9.0917(8) Å, b = 12.6682(12) Å, c = 14.9606(14) Å, α = 99.107(11)°, β = 93.897(11)°, γ = 109.239(11)°, V = 1593.0(3) Å3, Z = 1, ρcalcd = 1.377 Mg m-3. λ(Mo Kα) = 0.71073 Å, T = 153(2) K. R1 (I > 2σ(I)) = 0.0329, wR2 = 0.0583 (all data) with R1 = ∑||Fo| − |Fc||/∑|Fo| and wR2 = (∑w(Fo2 − Fc2)2/∑w(Fo2)2)0.5. The absolute structure parameter was −0.02(2). Crystallographic data for 2:  C48H88Fe2Ni3N24O2, M = 1321.25, P1, a = 9.0858(10) Å, b = 12.6638(15) Å, c = 14.9822(16) Å, α = 98.900(10)°, β = 93.950(10)°, γ = 109.45(10)°, V = 1592.4(3) Å3, Z = 1, ρcalcd = 1.378 Mg m-3. λ(Mo Kα) = 0.71073 Å, T = 153(2) K, μ = 1.371 mm-1, R1 (I > 2σ(I)) = 0.0604, wR2 = 0.1507 (all data) with R1 = ∑||Fo| − |Fc||/∑|Fo| and wR2 = (∑w(Fo2 − Fc2)2/∑w(Fo2)2)0.5. The absolute crystal structure was determined by the Flack method (Flack number = 0.00(4)).

Closely related structures with (12, 3) topology in which the [Fe(CN)6]3- anions binds to three adjacent nickel centers, either in fac or mer arrangements, have been reported in similar 2D bimetallic systems:  Kou, H.Z.; Gao, S.; Bu, W.M.; Liao, D.Z.; Ma, B.Q.; Jiang, Z.H.; Yan, S.P.; Fan, Y.G.; Wang G−L. J. Chem. Soc., Dalton. Trans.1999, 2477−2480. Kou, H.Z.; Bu, W.M.; Gao, S.; Liao, D.Z.; Jiang, Z.H.; Yan, S.P.; Fan, Y.G.; Wang, G.L.J. Chem. Soc., Dalton. Trans.2000, 2996−3000.

10.1016/S0304-8853(98)00180-2