Zheng Y-Q, Lin J-L, Kong Z-P
Municipal Key Laboratory of Solid State Chemistry & Materials Science, Institute for Solid State Chemistry, Ningbo University, Ningbo 315211, P. R. China.
Inorg Chem. 2004 Apr 19;43(8):2590-6. doi: 10.1021/ic0301268.
Reactions of 4,4'-bipyridine (bpy) with Mn(C(4)H(4)O(4)).4H(2)O and Mn(C(5)H(6)O(4)).4H(2)O in methanolic aqueous solutions yielded [Mn(bpy)(H(2)O)(C(4)H(4)O(4))].0.5bpy (1) and Mn(bpy)(C(5)H(6)O(4)) (2), respectively, and reactions of freshly prepared Mn(OH)(2)(-)(2)(x)(CO(3))(x).yH(2)O, adipic acid and 4,4'-bipyridine in a methanolic aqueous solution afforded Mn(bpy)(C(6)H(8)O(4)) (3). The six-coordinate Mn atoms in 1 are interlinked by flexible succinato ligands to form layers, which are sustained by rigid bpy ligands into an 3D open framework with the free bpy molecules in tunnels. The ribbonlike chains in 2 result from Mn atoms bridged by glutarato ligands and are connected by bpy ligands into open layers. In 3, the Mn atoms are bridged by both bpy and adipato ligands to form 3D nanoporous frameworks and 2-fold interpenetration of the resulting 3D frameworks completes the crystal structure. In comparison with 1 and 2, compound 3 displays significant antiferromagnetic behavior at low temperature. The antiferromagnetic exchange becomes stronger from 1 through 2 to 3, and the antiferromagnetic ordering of Mn(2+) centers is related to the syn-syn bridging mode of the terminal carboxylate groups of alpha,omega-dicarboxylate anions. Crystal data: C(19)H(18)MnN(3)O(5) (1), monoclinic P2(1)/c, a= 11.686(2) A, b = 17.847(2) A, c = 8.852(1) A, beta = 99.67(1) degrees, V = 1819.9(4) A(3), Z = 4, D(c) = 1.545 g.cm(-3); C(15)H(14)MnN(2)O(4) (2), triclinic P, a = 8.145(2) A, b = 9.574(2) A, c = 10.180(1) A, alpha = 108.01(3) degrees, beta = 93.55(3) degrees, gamma = 105.30(1) degrees, V = 719.2(2) A(3), Z = 2, D(c) = 1.576 g.cm(-3); C(15)H(14)MnN(2)O(4) (3), triclinic P, a = 8.544(1) A, b= 8.881(1) A, c = 10.949(2) A, alpha = 108.81(1) degrees, beta = 95.40(1) degrees, gamma = 101.94(1) degrees, V = 757.7(2) A(3), Z = 2, D(c) = 1.557 g.cm(-3).
4,4'-联吡啶（bpy）与Mn(C₄H₄O₄)·4H₂O和Mn(C₅H₆O₄)·4H₂O在甲醇水溶液中的反应分别生成了[Mn(bpy)(H₂O)(C₄H₄O₄)]·0.5bpy（1）和Mn(bpy)(C₅H₆O₄)（2），并且新制备的Mn(OH)₂⁻²ˣ(CO₃)ˣ·yH₂O、己二酸和4,4'-联吡啶在甲醇水溶液中的反应得到了Mn(bpy)(C₆H₈O₄)（3）。1中的六配位Mn原子通过柔性的琥珀酸根配体相互连接形成层状结构，这些层状结构由刚性的bpy配体支撑形成三维开放框架，隧道中有游离的bpy分子。2中的带状链由戊二酸根配体桥连的Mn原子形成，并通过bpy配体连接成开放层。在3中，Mn原子由bpy和己二酸根配体桥连形成三维纳米多孔框架，所得三维框架的2倍互穿完成了晶体结构。与1和2相比，化合物3在低温下表现出显著的反铁磁行为。从1到2再到3，反铁磁交换作用变强，并且Mn²⁺中心的反铁磁有序与α,ω-二羧酸根阴离子末端羧酸根基团的顺-顺桥连模式有关。晶体数据：C₁₉H₁₈MnN₃O₅（1），单斜晶系P2(1)/c，a = 11.686(2) Å，b = 17.847(2) Å，c = 8.852(1) Å，β = 99.67(1)°，V = 1819.9(4) ų，Z = 4，D(c) = 1.545 g·cm⁻³；C₁₅H₁₄MnN₂O₄（2），三斜晶系P，a = 8.145(2) Å，b = 9.574(2) Å，c = 10.180(1) Å，α = 108.01(3)°，β = 93.55(3)°，γ = 105.30(1)°，V = 719.2(2) ų，Z = 2，D(c) = 1.576 g·cm⁻³；C₁₅H₁₄MnN₂O₄（3），三斜晶系P，a = 8.544(1) Å，b = 8.881(1) Å，c = 10.949(2) Å，α = 108.81(1)°，β = 95.40(1)°，γ = 101.94(1)°，V = 757.7(2) ų，Z = 2，D(c) = 1.557 g·cm⁻³。
