Synthesis and Crystal Structure of Two Cyano-Bridged dimeric 4f-3d Complexes
来源期刊：JOURNAL OF RARE EARTHS2002年第5期
论文作者：金祥林 高松 寇会忠
Key words：rare earths; hexacyanochromate(Ⅲ) anion; hexacyanocobaltate(III) anion; cyano-bridge;
Abstract: Two cyano-bridged dimeric 4f-3d complexes [Nd(DMF)4(H2O)3Co(CN)6]*H2O (A) and [Sm(pyr)4(H2O)3Cr(CN)6]*2H2O (B) (DMF=N,N-dimethylformamide, pyr=2-pyrrolidone) were prepared and structurally characterized. Single-crystal X-ray diffraction analysis revealed that the complexes contain cyano-bridged [M(CN)6]3 and [Ln(L)4(H2O)3]3+ groups. The Ln3+ is eight-coordinate, and is coordinated by seven oxygen atoms of three water molecules and four organic ligands (DMF or pyr). Each terminal CN ligand of the [M(CN)6]3- entity is hydrogen-bonded to some oxygen atoms of the coordinated water molecules yielding a hydrogen-bonded three-dimensional network. Crystal data for A: monoclinic, space group P2(1)/n, a= 1.7525(4) nm, b=0.8879(2) nm, c=1.9876(4) nm, β=95.92(3)°, V=3.0763(12) nm3, Z=4, Dc= 1.563 mg*m-3. Complex B crystallizes in the P1 space group, with lattice parameters of a=1.22720(4) nm, b=1.45550(8) nm, c=0.91310(4) nm, α=92.5869(17)°, β= 90.9569(12)°, γ=89.822(3)°, V=1.62908(13) nm3, Z=2, Dc=1.608 mg*m-3.
金祥林1，高松1，寇会忠2
(1.State Key Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871, China;
2.Department of Chemistry, Tsinghua University, Beijing 100084, China；State Key Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871, China)
Abstract:Two cyano-bridged dimeric 4f-3d complexes [Nd(DMF)4(H2O)3Co(CN)6]*H2O (A) and [Sm(pyr)4(H2O)3Cr(CN)6]*2H2O (B) (DMF=N,N-dimethylformamide, pyr=2-pyrrolidone) were prepared and structurally characterized. Single-crystal X-ray diffraction analysis revealed that the complexes contain cyano-bridged [M(CN)6]3 and [Ln(L)4(H2O)3]3+ groups. The Ln3+ is eight-coordinate, and is coordinated by seven oxygen atoms of three water molecules and four organic ligands (DMF or pyr). Each terminal CN ligand of the [M(CN)6]3- entity is hydrogen-bonded to some oxygen atoms of the coordinated water molecules yielding a hydrogen-bonded three-dimensional network. Crystal data for A: monoclinic, space group P2(1)/n, a= 1.7525(4) nm, b=0.8879(2) nm, c=1.9876(4) nm, β=95.92(3)°, V=3.0763(12) nm3, Z=4, Dc= 1.563 mg*m-3. Complex B crystallizes in the P1 space group, with lattice parameters of a=1.22720(4) nm, b=1.45550(8) nm, c=0.91310(4) nm, α=92.5869(17)°, β= 90.9569(12)°, γ=89.822(3)°, V=1.62908(13) nm3, Z=2, Dc=1.608 mg*m-3.
Key words:rare earths; hexacyanochromate(Ⅲ) anion; hexacyanocobaltate(III) anion; cyano-bridge;
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