Trinuclear N,N-Bridged Copper(II) Complexes Involving a Cu3OH Core: [Cu3(3-OH)L3A(H2<
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- 作者：Sacramento Ferrer ; Jaap G. Haasnoot ; Jan Reedijk ; Edgar Mü ; ller ; Marina Biagini Cingi ; Maurizio Lanfranchi ; Anna Maria Manotti Lanfredi ; and Joan Ribas
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：May 1, 2000
- 年：2000
- 卷：39
- 期：9
- 页码：1859 - 1867
- 全文大小：155K
- 年卷期：v.39,no.9(May 1, 2000)
- ISSN：1520-510X
文摘
The reaction of Haat [Haat = (3-acetylamino-1,2,4-triazole)] with aquated Cu(CF3SO3)2, Cu(NO3)2, and Cu(ClO4)2, respectively, in water results in the trinuclear complexes [Cu3(OH)(aat)3(CF3SO3)(H2O)2](CF3SO3) (1),[Cu3(OH)(aat)3(NO3)(H2O)2](NO3)·(H2O)2 (2), and [Cu3(OH)(aat)3(ClO4)(H2O)2](ClO4) (3). The synthesis, X-raystructure, and magnetic and spectroscopic properties of the three title complexes are described. The cation of thethree complexes is trinuclear with a Cu3OH skeleton which has the N-N diazine grouping of a triazole ring asbridge between each pair of copper atoms. The Cu3OH units have an average Cu-O distance of 1.991(6) (1),2.000(6) (2), and 2.007(6) (3) Å, an average Cu-Cu' distance of 3.355(2) (1), 3.341(1) (2), and 3.371(3) (3) Å,and an average Cu-O-Cu' angle of 114.6(3)
(1), 112.4(2) (2), and 115.4(3) (3). The existence of the Cu3OHfragment is confirmed by a pseudotetrahedral oxygen environment, by detection of the OH hydrogen atom, andby stoichiometry. In the trinuclear unit the metal ions show, in the first approximation, a pseudo-square-planarpyramidal environment forming a CuN2O3 chromophore; three of the basal positions are occupied by N,N,O aatligand atoms, the fourth one is occupied by the oxygen of the central OH group, and the apical site is occupiedby an oxygen atom from a water molecule in the case of two of the copper(II) atoms and by an oxygen atom fromthe coordinating anion in the case of the third metal ion. The three compounds exhibit strong antiferromagneticinteraction, with similar J constants [J = -197.7 (1), J = -190.9 (2), J = -198.2 (3) cm-1], reaching completespin coupling at ca. 75 K (1)/55 K (2)/95 K (3). At very low temperature the magnetic moment (magneticsusceptibility) falls below that expected for one unpaired electron. Magnetic parameters are discussed on thebasis of the structural results and compared with those reported in the literature for related trimeric Cu(II) compoundswith N-O or N-N peripheral bridges. Solid state EPR spectra of the three complexes recorded at liquid Ntemperature show axial signals. Crystal data: C14H20Cu3F6N12O12S2 (1) (Mw = 917.16) crystallizes in the monoclinicspace group, P21/c, Z = 4, with cell dimensions a = 13.080(2) Å, b = 17.202(2) Å, c = 13.840(2) Å, 
=92.40(1), and V = 3111.3(7) Å3, Dcalcd = 1.958 Mg m-3; the final agreement values were R1 = 0.0582 and wR2= 0.1462 for 7107 unique reflections. C12H24Cu3N14O14 (2) (Mw = 779.07) crystallizes in the triclinic spacegroup, P
, Z = 2, with cell dimensions a = 9.647(2) Å, b = 9.985(2) Å, c = 15.314(2) Å, 
= 84.080(10), = 87.694(10), 
= 65.030(10), and V = 1330.1(4) Å3, Dcalcd = 1.945 Mg m-3; the final agreement values wereR1 = 0.0397 and wR2 = 0.0950 for 7728 unique reflections. C12H20Cl2Cu3N12O14 (3) (Mw = 817.92) crystallizesin the monoclinic space group, P21/a, Z = 4, with cell dimensions a = 14.238(5) Å, b = 16.387(6) Å, c =11.678(4) Å, = 90.45(2), and V = 2724.6(18) Å3, Dcalcd = 1.994 Mg m-3; the final agreement values were R1= 0.0616 and wR2 = 0.1279 for 4038 unique reflections.
(1), 112.4(2) (2), and 115.4(3) (3). The existence of the Cu3OHfragment is confirmed by a pseudotetrahedral oxygen environment, by detection of the OH hydrogen atom, andby stoichiometry. In the trinuclear unit the metal ions show, in the first approximation, a pseudo-square-planarpyramidal environment forming a CuN2O3 chromophore; three of the basal positions are occupied by N,N,O aatligand atoms, the fourth one is occupied by the oxygen of the central OH group, and the apical site is occupiedby an oxygen atom from a water molecule in the case of two of the copper(II) atoms and by an oxygen atom fromthe coordinating anion in the case of the third metal ion. The three compounds exhibit strong antiferromagneticinteraction, with similar J constants [J = -197.7 (1), J = -190.9 (2), J = -198.2 (3) cm-1], reaching completespin coupling at ca. 75 K (1)/55 K (2)/95 K (3). At very low temperature the magnetic moment (magneticsusceptibility) falls below that expected for one unpaired electron. Magnetic parameters are discussed on thebasis of the structural results and compared with those reported in the literature for related trimeric Cu(II) compoundswith N-O or N-N peripheral bridges. Solid state EPR spectra of the three complexes recorded at liquid Ntemperature show axial signals. Crystal data: C14H20Cu3F6N12O12S2 (1) (Mw = 917.16) crystallizes in the monoclinicspace group, P21/c, Z = 4, with cell dimensions a = 13.080(2) Å, b = 17.202(2) Å, c = 13.840(2) Å, =92.40(1), and V = 3111.3(7) Å3, Dcalcd = 1.958 Mg m-3; the final agreement values were R1 = 0.0582 and wR2= 0.1462 for 7107 unique reflections. C12H24Cu3N14O14 (2) (Mw = 779.07) crystallizes in the triclinic spacegroup, P, Z = 2, with cell dimensions a = 9.647(2) Å, b = 9.985(2) Å, c = 15.314(2) Å, = 84.080(10), = 87.694(10), = 65.030(10), and V = 1330.1(4) Å3, Dcalcd = 1.945 Mg m-3; the final agreement values wereR1 = 0.0397 and wR2 = 0.0950 for 7728 unique reflections. C12H20Cl2Cu3N12O14 (3) (Mw = 817.92) crystallizesin the monoclinic space group, P21/a, Z = 4, with cell dimensions a = 14.238(5) Å, b = 16.387(6) Å, c =11.678(4) Å, = 90.45(2), and V = 2724.6(18) Å3, Dcalcd = 1.994 Mg m-3; the final agreement values were R1= 0.0616 and wR2 = 0.1279 for 4038 unique reflections.