Low-dimensional compounds containing cyanido groups. XXI. Crystal structure, spectroscopic, thermal and magnetic properties of two polymorphous modifications of [Cu(men)_2Pt(CN)_4]_n complex (men = N-methyl-1,2-diaminoethane)

Vavra M.; Poto?ňák I.; ?i?már E.; Kajňaková M.; Du?ek M.; Schmidt H.; Ozerov M.; Zvyagin S.A.; Dlháň L.; Bo?a R.

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Low-dimensional compounds containing cyanido groups. XXI. Crystal structure, spectroscopic, thermal and magnetic properties of two polymorphous modifications of [Cu(men)_2Pt(CN)_4]_n complex (men = N-methyl-1,2-diaminoethane)

机译：含有氰基的低维化合物。二十一[Cu（men）_2Pt（CN）_4] _n配合物（men = N-甲基-1,2-二氨基乙烷）的两种多晶型修饰的晶体结构，光谱，热和磁性能

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Violet (1) and blue (2) polymorphous modifications of [Cu(men) _2Pt(CN)_4]_n (men = N-methyl-1,2-diaminoethane) have been prepared and investigated by IR and UV-vis spectroscopy, thermal analysis, measurement of magnetic data and X-ray structural analysis. Both modifications are formed by similar but differently packed zigzag chains, which consist of [Cu(men)_2]~(2+) moieties bridged by two trans arranged cyanido groups of [Pt(CN)_4]~(2-) units. The Cu(II) atoms in both structures are hexacoordinated by four nitrogen atoms in the equatorial plane from two molecules of bidentate men ligands with the average Cu-N(Me) and Cu-N(H2) bond lengths of 2.046(8) and 2.008(8), respectively, and by two nitrogen atoms from bridging cyanido groups in the axial positions at average distance of 2.50(7). Broad nearly symmetric bands observed in the UV-vis spectra of 1 and 2 of 2B1g → 2Eg transitions are consistent with a deformed octahedral coordination of the CuN6 chromophoric groups. One and two ν(CN) absorption bands observed in the IR spectra of 1 and 2, respectively, are in agreement with different local symmetries of [Pt(CN)_4]~(2-) units and different Cu-N(cyanido) bond lengths in these polymorphs and are subject of discussion on the spectral-structural correlations in 1D compounds. The complexes are stable up to 238 °C when their two-stage thermal decompositions start and ending up with a mixture of CuO and metallic Pt as the most probable final thermal decomposition products. The temperature dependence of the magnetic susceptibility suggests the presence of a weak antiferromagnetic exchange coupling between Cu(II) atoms in 1, J/hc = -0.17 cm~(-1) and in 2, J/hc = -1.3 cm~(-)1.

机译：[Cu（men）_2Pt（CN）_4] _n（men = N-methyl-1,2，diaminoethane）的紫色（1）和蓝色（2）多晶型修饰物已经制备并通过红外和紫外-可见光谱研究，热分析，磁数据测量和X射线结构分析。两种修饰都是由相似但不同堆积的之字形链形成的，它们由[Cu（men）_2]〜（2+）部分与[Pt（CN）_4]〜（2-）单元的两个反式排列的氰基桥接而成。两种结构中的Cu（II）原子在赤道平面中由两个双齿男人配体的四氮原子六配位，平均Cu-N（Me）和Cu-N（H2）键长为2.046（8），分别为2.008（8）和由两个氮原子桥接的氰基基团在轴向位置平均距离为2.50（7）。在2B1g→2Eg跃迁的1和2的UV-vis光谱中观察到的近似对称的宽谱带与CuN6发色团的变形八面体配位相一致。分别在1和2的红外光谱中观察到的一个和两个ν（CN）吸收带与[Pt（CN）_4]〜（2-）单元的不同局部对称性和不同的Cu-N（氰基）一致这些多晶型物的键长，是关于一维化合物的光谱结构相关性的讨论主题。当络合物的两阶段热分解开始和结束时，最可能的最终热分解产物是CuO和金属Pt的混合物，它们在高达238°C的温度下稳定。磁化率的温度依赖性表明，在1，J / hc = -0.17 cm〜（-1）和2，在J / hc = -1.3 cm〜（2）中，Cu（II）原子之间存在弱的反铁磁交换耦合。 -）1。

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来源
《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |2011年第2期|共10页
作者
Vavra M.; Poto?ňák I.; ?i?már E.; Kajňaková M.; Du?ek M.; Schmidt H.; Ozerov M.; Zvyagin S.A.; Dlháň L.; Bo?a R.;
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正文语种 eng
中图分类无机化学;
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1D crystal structure; Antiferromagnetic exchange; Infrared spectroscopy; N-methyl-1; 2-diaminoethane; Polymorphous modifications; Spectral-structural correlations; Tetracyanidoplatinate(II);

机译：一维晶体结构;反铁磁交换;红外光谱;N-甲基-1;2-二氨基乙烷;多晶型修饰;光谱结构相关;四氰基铂盐（II）;

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Low-dimensional compounds containing cyanido groups. XXI. Crystal structure, spectroscopic, thermal and magnetic properties of two polymorphous modifications of [Cu(men)_2Pt(CN)_4]_n complex (men = N-methyl-1,2-diaminoethane)

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