Abstract

The structural features of the phases formed during crystallization of mixed copper and nickel complexes with nitrilotris(methylenephosphonic acid) [Cu_xNi_(1 – x){N(CH₂PO₃)₃}]Na₄ · nH₂O (x = 0–1) and the character of the M ← O(P) coordination bond have been investigated. The copper-dominant phase [(Cu,Ni){N(CH₂PO₃)₃}]Na₄ · 13H₂O (sp. gr. P\(\bar {1}\), Z = 2, a = 10.0096(2)–10.0118(2) Å, b = 11.0311(3)–11.0330(2) Å, c = 12.2893(2)–12.3038(3) Å, α = 84.7180(10)°–84.785(2)°, β = 79.504(2)°–79.544(2)°, γ = 66.971(2)°–67.058(2)°) is characterized by the trigonal bipyramidal coordination of the metal atom (oxygen atoms of three different PO₃ groups of the ligand molecule lie in the pyramid-base plane, and a nitrogen atom and the oxygen atom of the neighboring ligand molecule occupy opposite vertices). The nickel-containing phase [Ni(H₂O){N(CH₂PO₃)₃}]Na₄ · 11H₂O (sp. gr. C2/c, Z = 4, a = 11.9924(2)–12.05510(10) Å, b = 18.6049(3)–18.7152(2) Å, c = 21.0724(4)–21.1266(2) Å, β = 104.096(2)°–104.4960(10)°) is characterized by octahedral coordination of the Ni atom (oxygen atoms of different PO₃ groups of the ligand molecule are located at three meridian octahedron vertices, and a nitrogen atom, a water molecule, and the oxygen atom of the neighboring ligand molecule occupy the rest three vertices). The dependence of the interatomic distances and bond angles in the coordination sphere of the metal atom on the Cu : Ni ratio has been studied. It is shown that the transition from the trigonal bipyramidal coordination to the octahedral coordination is accompanied by a sharp increase in the ionicity of the M ← O(P) coordination bond.

中文翻译：

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[Cu x Ni（1-x）{N（CH 2 PO 3）3}] Na 4·n H 2 O（x = 0-1）的相的晶体化学特征和配位键的性质）

摘要

铜和镍与次氮基三（亚甲基膦酸）[Cu _x Ni _{（1-  x）} {N（CH ₂ PO ₃）₃ }] Na ₄ · n H ₂ O（x的混合物）的结晶过程中形成的相的结构特征= 0–1）和M ←O（P）配位键的性质已被研究。铜主导阶段[（铜，镍）{N（CH ₂ PO ₃）₃ }]的Na ₄ ·13H ₂ O（比重= P \（\巴{1} \） ，Ž = 2，a = 10.0096（2）–10.0118（2）Å，b = 11.0311（3）–11.0330（2）Å，c = 12.2893（2）–12.3038（3）Å，α= 84.7180（10）°–84.785（2 ）°，β= 79.504（2）°–79.544（2）°，γ= 66.971（2）°–67.058（2）°）的特征在于金属原子（三个不同PO _3的氧原子）的三角双锥体配位配体分子的两个基团位于金字塔基平面上，并且相邻配体分子的氮原子和氧原子占据相反的顶点。含镍的相[镍（H ₂ O）{N（CH ₂ PO ₃）₃ }]的Na ₄ ·11H ₂ O（比重= c ^ 2 / Ç，ž= 4，a = 11.9924（2）–12.05510（10）Å，b = 18.6049（3）–18.7152（2）Å，c = 21.0724（4）–21.1266（2）Å，β= 104.096（2）°– 104.4960（10）°）的特征在于Ni原子的八面体配位（配体分子的不同PO ₃基团的氧原子位于三个子午八面体顶点，并且氮原子，水分子和氧原子的氧原子位于相邻的配体分子占据其余三个顶点）。研究了金属原子配位原子中原子间距离和键角对Cu：Ni比的依赖性。结果表明，从三角双锥体配位到八面体配位的转变伴随着离子的离子性急剧增加。M ←O（P）配位键。