Complementarity and countercomplementarity in polynuclear copper(II) complexes with R2NCH2CH(OH)CH2NR2 (R = H, CH3): crystal structures and magnetic study.

The syntheses, structural characterization and magnetic behavior of five new copper(II) polynuclear compounds with formulae [Cu4(mu2-CH3COO)2(mu-bdmap)2(micro(1,5)-dca)2(dca)2(H2O)2] 1, [Cu2(mu2-CH3COO)(mu-bdap)(mu(1,1,5)-dca)(mu(1,3)-dca)]n 2, [Cu4(mu2-CH3COO)2(mu-bdmap)2(mu(1,1)-NCS)2(NCS)2] 3, [Cu2(mu2-CH3COO)(mu-bdap)(NCS)2] 4 and [Cu2(mu(1,3)-N3)(mu-bdmap)(N3)2]n 5 in which bdmapH is 1,3-bis(dimethylamino)-2-propanol, bdapH is 1,3-bis(amino)-2-propanol and dca is the anionic dicyanamide ligand, are reported herein. Tetranuclear complex 1 crystallizes in the monoclinic system, space group P2(1)/n, with unit cell parameters a = 8.284(8), b = 21.52(1), c = 11.432(3) A, beta = 105.19(2) degrees , Z = 2. Bi-dimensional complex 2 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.184(5), b = 8.792(2), c = 10.887(2) A, alpha = 75.65(2), beta = 76.55(3), gamma = 74.36(3) degrees , Z = 2. Tetranuclear complex 3 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.455(4), b = 9.114(9), c = 12.744(8) A, alpha = 104.62(8), beta = 99.86(6), gamma = 106.10(8) degrees, Z = 1. Dinuclear complex 4 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.15(1), b = 8.18(2), c = 11.44(1) A, alpha = 69.39(2), beta = 80.36(2), gamma = 80.37(2) degrees , Z = 2. One-dimensional complex 5 crystallizes in the orthorhombic system, space group P2(1)2(1)2(1), with unit cell parameters a = 20.45(4), b = 11.36(3), c = 6.43(1) A, Z = 4. The magnetic behavior of all the complexes has been checked giving a bulk antiferromagnetic coupling in all the cases with |J| values in the range 109-144 cm(-1) for 1-4. Compound 5 is diamagnetic in the 2-300 K range of temperatures. The found J values 1-5 for can be justified from the structural data taking into account the orbital countercomplementarity for 1-4 and the orbital complementarity for 5.

[1]  X. Solans,et al.  Syntheses and magneto-structural study of several polynuclear copper(II) complexes derived from 1,3-Bis(dimethylamino)-2-propanolato. , 2004, Inorganic chemistry.

[2]  F. Lloret,et al.  Hexanuclear manganese(III) single-molecule magnets. , 2004, Angewandte Chemie.

[3]  D. Gatteschi,et al.  Quantentunneln der Magnetisierung und verwandte Phänomene in molekularen Materialien , 2003 .

[4]  D. Gatteschi.  Single-molecule Magnets , 2000 .

[5]  J. Cano,et al.  Countercomplementarity and strong ferromagnetic coupling in a linear mixed mu-acetato, mu-hydroxo trinuclear copper(II) complex. Synthesis, structure, magnetic properties, EPR, and theoretical studies. , 2000, Inorganic chemistry.

[6]  Louis J. Farrugia,et al.  ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI) , 1997 .

[7]  Suning Wang,et al.  Synthesis and characterization of SrCu2(O2CR)3(bdmap)3 and Bi2(O2CCH3)4(bdmap)2(H2O) (R = CH3, CF3; bdmap = 1,3-bis(dimethylamino)-2-propanolato) , 1996 .

[8]  A. Caneschi,et al.  Structure and Magnetic Properties of a Heptanuclear Nickel(II) Compound: [Ni(7)(&mgr;-NO(2))(8)(&mgr;(2)-OH)(2)(&mgr;(3)-OH)(2)(OHpn)(2)(Opn)(2)](2).7H(2)O. , 1996, Inorganic chemistry.

[9]  Suning Wang,et al.  Homonuclear copper(II) complexes with multidentate amino alcohol ligands. Synthesis and characterization of a hexanuclear copper compound with a propeller structure: CuII6(bdmap)3Cl6(O)(OH) (bdmap = 1,3-bis(dimethylamino)-2-propanolato) , 1993 .

[10]  Suning Wang,et al.  Synthesis and crystal structure of a dinuclear yttrium(III)- (lanthanide(III)-) copper(II) complex with an unusual 2-methyl-2,4,6-tris(trifluoromethyl)-1,3-dioxane-4,6-diolato ligand , 1993 .

[11]  Suning Wang,et al.  Molecular copper-barium compounds. Syntheses, crystal structures, and magnetic properties of two sandwich copper-barium complexes: BaCu4(bdmap)4(PyO)4(O2CCF3)2.0.5THF and BaCu4(deae)4(PyO)4(O2CCF3)2 (bdmap = 1,3-bis(dimethylamino)-2-propanolato, PyO = deprotonated 2-hydroxypyridine, deae = 2-(diethy , 1993 .

[12]  J. Ribas,et al.  The first ferromagnetic tetranuclear nickel(II) complex with a .mu.-azido bridge. Structure and magnetic properties of [Ni4(.mu.-N3)4(2-oxo-1,3-diaminopropane)2(2-hydroxo-1,3-diaminopropane)2](ClO4)2 , 1993 .

[13]  D. Gatteschi,et al.  MAGNETIC PROPERTIES OF HIGH NUCLEARITY SPIN CLUSTERS. A FAST AND EFFICIENTPROCEDURE FOR THE CALCULATION OF THE ENERGY LEVELS , 1993 .

[14]  Suning Wang,et al.  Homonuclear and heteronuclear metal complexes with a cyclic tetracopper(II) unit. Syntheses, crystal structures, and magnetic properties of [CuII4(dmap)3(OH)(O2CCH3)2(HO2CCH3)(H2O)][PF6]2, [CuII4(dmap)2(O2CCH3)4][PF6]2, [CuII4(dmap)2(O2CCH3)2(OH)2][HgII(O2CCH3)Cl2]2[HgIICl2], and [CuII4(dmap)2(O2CCH , 1992 .

[15]  V. McKee,et al.  Further insight into magnetostructural correlations in binuclear copper(II) species related to methemocyanin: x-ray crystal structure of 1,2-.mu.-nitrito complex , 1985 .

[16]  V. McKee,et al.  Hemocyanin models: synthesis, structure, and magnetic properties of a binucleating copper(II) system , 1984 .

[17]  D. Hodgson,et al.  Relation between the singlet-triplet splitting and the copper-oxygen-copper bridge angle in hydroxo-bridged copper dimers , 1976 .