Näther Christian, Jess Inke
Institut für Anorganische Chemie, Universität Kiel, Max-Eyth Str. 2, 24118 Kiel, Germany.
Acta Crystallogr E Crystallogr Commun. 2023 Feb 7;79(Pt 3):136-141. doi: 10.1107/S2056989023000920. eCollection 2023 Feb 1.
The reactions of Zn(NO) 6HO and Cd(NO) 4HO with KSeCN and 4-meth-yl-pyridine (CHN; 4-picoline) lead to the formation of crystals of bis-(4-methyl-pyridine-κ)bis-(seleno-cyanato-κ)zinc(II), [Cd(NCSe)(CHN)] (), and -poly[[bis-(4-methyl-pyridine-κ)cadmium(II)]-di-μ-seleno-cyanato-κ :;κ :], [Cd(NCSe)(CHN)] (), suitable for single-crystal X-ray diffraction. The asymmetric unit of compound consists of one Zn cation that is located on a twofold rotation axis as well as one seleno-cyanate anion and one 4-methyl-pyridine ligand in general positions. The Zn cations are tetra-hedrally coordinated by two terminal N-bonding thio-cyanate anions and two 4-methyl-pyridine ligands, forming discrete complexes. The asymmetric unit of compound consists of two crystallographically independent Cd cations, of which one is located on a twofold rotation axis and the second on a center of inversion, as well as two crystallographically independent seleno-cyanate anions and two crystallographically independent 4-methyl-pyridine ligands in general positions. The Cd cations are octa-hedrally coordinated by two N- and two S-bonding seleno-cyanate anions and two 4-methyl-pyridine ligands and are linked into chains by pairs of seleno-cyanate anions. Within the chains, the Cd cations show an alternating -- and - coordination and therefore, the chains are corrugated. PXRD investigations prove that the Zn compound was obtained as a pure phase and that the Cd compound contains a very small amount of an additional and unknown phase. In the IR spectrum of , the CN stretching vibration of the seleno-cyanate anion is observed at 2072 cm, whereas in the it is shifted to 2094 cm, in agreement with the crystal structures.
硝酸锌六水合物（Zn(NO₃)₂·6H₂O）和硝酸镉四水合物（Cd(NO₃)₂·4H₂O）与硒氰酸钾（KSeCN）和4-甲基吡啶（C₅H₇N；4-皮考啉）反应，生成了双（4-甲基吡啶-κ）双（硒氰酸根-κ）锌（II）[Zn(NCSe)₂(C₅H₇N)₂]（化合物1）和聚[[双（4-甲基吡啶-κ）镉（II）]-二-μ-硒氰酸根-κ:N;κ:N]，[Cd(NCSe)₂(C₅H₇N)₂]ₙ（化合物2）的晶体，适合进行单晶X射线衍射分析。化合物1的不对称单元由一个位于二重旋转轴上的锌阳离子以及一个硒氰酸根阴离子和一个处于一般位置的4-甲基吡啶配体组成。锌阳离子通过两个末端N键合的硫氰酸根阴离子和两个4-甲基吡啶配体进行四面体配位，形成离散的配合物。化合物2的不对称单元由两个晶体学独立的镉阳离子组成，其中一个位于二重旋转轴上，另一个位于对称中心，还有两个晶体学独立的硒氰酸根阴离子和两个处于一般位置的晶体学独立的4-甲基吡啶配体。镉阳离子通过两个N键合和两个S键合的硒氰酸根阴离子以及两个4-甲基吡啶配体进行八面体配位，并通过成对的硒氰酸根阴离子连接成链。在链内，镉阳离子呈现交替的 - - 和 - 配位，因此链是波纹状的。粉末X射线衍射（PXRD）研究证明，锌化合物以纯相形式获得，而镉化合物含有极少量的额外未知相。在化合物1的红外光谱中，硒氰酸根阴离子的C≡N伸缩振动在2072 cm⁻¹处观察到，而在化合物2中它移至2094 cm⁻¹，这与晶体结构一致。
