Metal-containing ligands for mixed-metal polymers: novel Cu(II)-Ag(I) mixed-metal coordination polymers generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O and silver(I) salts.
Metal-containing ligands for mixed-metal polymers: novel Cu(II)-Ag(I) mixed-metal coordination polymers generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O and silver(I) salts.
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DOI：
10.1021/ic991475y
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发表时间：
2000-04
影响因子：
4.6
通讯作者：
Y. Dong;M. D. Smith;H. zur Loye
中科院分区：
文献类型：
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作者：
Y. Dong;M. D. Smith;H. zur Loye
合成了一个含Cu（II）配体和两个Cu（II）-Ag（I）混合金属配位聚合物。通过2-甲基吡嗪-5-羧酸钠与CuCl（2）·2 H2O在水中的反应，得到作为具有两个未配位的氮供体的分子配合物的[Cu（2-甲基吡嗪-5-羧酸）2（H2O）]·3 H2O（1）。化合物1以三斜晶系空间群P1结晶，其中a = 10.498（2）A，B = 11.000（2）A，c = 8.1424（16）A，α = 98.33（3）度，β = 101.83（3）度，γ = 66.68（3）度，并且Z = 2。研究了1与银（I）盐的反应。合成了两种Cu（II）-Ag（I）混合金属配位聚合物，即Ag[Cu（2-methylpyrazine-5-carboxylic acid）2.（H2O）2]（BF 4）（2）和Ag[Cu（2-甲基吡嗪-5-羧酸酯）2。（H_2O）_2]（NO_3）（3）。化合物2以单斜空间群C2/c结晶，其中a = 25.827（5）A，B = 9.6430（19）A，c = 7.4525（15）A，β = 94.74（3）度，并且Z = 4。化合物3也以单斜空间群C2/c结晶，其中a = 25.855（5）A，B = 9.782（2）A，c = 7.1201（14）A，β = 96.90（3）度，并且Z = 4。2和3的主要结构特征是锯齿形Cu（II）-Ag（I）混合金属链，其中交替的Cu（II）和Ag（I）中心通过2-甲基吡嗪-5-羧酸酯间隔基连接。化合物3证明了硝酸根离子的作用，其中一种新的[Ag+]离子在硝酸根离子的作用下，NO3-]配位链作为连接体将一维锯齿链交联成三维网络。此外，一个相同的链间O-H…O氢键系统已被发现在2和3中，并已被证明在指导结晶状态下的一维混合金属聚合物链的排列中发挥重要作用。测量了2和3的磁化率，发现其符合居里定律（2的μ eff = 1.85，3的μ eff = 1.83）。
One Cu(II)-containing ligand and two Cu(II)-Ag(I) mixed-metal coordination polymers have been synthesized. [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O (1) was obtained as a molecular complex with two uncoordinated nitrogen donors by the reaction of 2-methylpyrazine-5-carboxylate sodium with CuCl(2).2H2O in water. Compound 1 crystallized in the triclinic space group P1, with a = 10.498(2) A, b = 11.000(2) A, c = 8.1424(16) A, alpha = 98.33(3) degrees, beta = 101.83(3) degrees, gamma = 66.68(3) degrees, and Z = 2. Reactions of 1 with silver(I) salts have been studied. Two Cu(II)-Ag(I) mixed-metal coordination polymers, namely, Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](BF4) (2) and Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](NO3) (3), have been generated by treating 1 with AgBF4 and AgNO3, respectively. Compound 2 crystallized in the monoclinic space group C2/c, with a = 25.827(5) A, b = 9.6430(19) A, c = 7.4525(15) A, beta = 94.74(3) degrees, and Z = 4. Compound 3 also crystallized in the monoclinic space group C2/c, with a = 25.855(5) A, b = 9.782(2) A, c = 7.1201(14) A, beta = 96.90(3) degrees, and Z = 4. The main structural feature in both 2 and 3 is a zigzag Cu(II)-Ag(I) mixed-metal chain, in which the alternating Cu(II) and Ag(I) centers are linked by 2-methylpyrazine-5-carboxylate spacers. The effect of the nitrate counterion was illustrated by compound 3, in which a novel [Ag+...NO3-] coordination chain has been found which acts as the connector to cross-link the one-dimensional zigzag chains into a three-dimensional network. In addition, an identical interchain O-H...O hydrogen bonding system has been found in both 2 and 3 and has been shown to play a significant role in directing the alignment of the one-dimensional mixed-metal polymer chains in the crystalline state. The magnetic susceptibilities of 2 and 3 were measured and found to follow the Curie law (mu eff = 1.85 for 2 and 1.83 for 3).