Adedamola Abraham Opalade, Nikolay Gerasimchuk*, Oleksandr Hietsoi and Olga Gerasimchuk,
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These were RED, the main product [Ni(PyrCO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>](H<sub>2</sub>O), and two differently colored polymorphs GREEN [Ni(PyrCO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] and VIOLET [Ni(PyrCO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>], with only minor amounts of the <i>fac</i>-Na[Ni(PyrCO)<sub>3</sub>] tris-cyanoximate. Two other complexes, dimeric [Ni<sub>2</sub>(PyrCO)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>]·2C<sub>3</sub>H<sub>7</sub>OH and tris-cyanoximate [Ni{HPyrCO}(PyrCO)<sub>2</sub>]·2CH<sub>3</sub>CN, contained outer-sphere solvent molecules of crystallization and were obtained as the result of direct interaction of starting compounds in narrow tubes. All isolated complexes were characterized using IR, solid-state UV–visible spectroscopy, TG/DSC analysis, and X-ray crystallography. Data showed the formation of five-membered chelate rings in all structures and adoption of the <i>trans</i>-geometry of cyanoxime in all crystallohydrate complexes. Heating of the RED, GREEN, and VIOLET crystallohydrates led to irreversible dehydration and the formation of an anhydrous brown complex, [Ni(PyrCO)<sub>2</sub>]. Variable temperature magnetochemical studies of RED trihydrate confirmed a lack of interactions between isolated Ni(II) centers, while there was an antiferromagnetic interaction between metal ions in the linear chain in the polymeric anhydrous compound. Full line shape analysis of solid-state electronic spectra allowed calculation of the Racah Repulsion Parameter (B) and Nephelauxetic Constant (β). In three crystallohydrates, there were six-coordinated high-spin Ni<sup>2+</sup> complexes with different degrees of rhombic (with axial elongation) distortions and, therefore, ligands’ crystal field strength. The final product of the thermal decomposition of all complexes under inert gas protection was metallic Ni sponge.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Remarkable Structural Diversity of N-Pyrrolidine-cyanoxime and its Ni(II) Complexes\",\"authors\":\"Adedamola Abraham Opalade, Nikolay Gerasimchuk*, Oleksandr Hietsoi and Olga Gerasimchuk, \",\"doi\":\"10.1021/acs.cgd.4c00496\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A novel cyanoxime, 2-oximino-2-cyano-N-pyrrolidine-acetamide (further HPyrCO), was synthesized and characterized by spectroscopic methods, thermal analysis, and X-ray crystallography. 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Variable temperature magnetochemical studies of RED trihydrate confirmed a lack of interactions between isolated Ni(II) centers, while there was an antiferromagnetic interaction between metal ions in the linear chain in the polymeric anhydrous compound. Full line shape analysis of solid-state electronic spectra allowed calculation of the Racah Repulsion Parameter (B) and Nephelauxetic Constant (β). In three crystallohydrates, there were six-coordinated high-spin Ni<sup>2+</sup> complexes with different degrees of rhombic (with axial elongation) distortions and, therefore, ligands’ crystal field strength. 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引用次数: 0
摘要
研究人员合成了一种新型氰肟，即 2-氧亚氨基-2-氰基-N-吡咯烷乙酰胺（HPyrCO），并通过光谱方法、热分析和 X 射线晶体学对其进行了表征。其结构显示出八个独立的分子，不对称单元中分子间存在复杂的氢键，氰肟采用反式反构型。此后，从水溶液中获得了一系列与这种新氰肟类配位的 Ni（II）配位化合物结晶水合物，并在过滤主产物和从母液中结晶出新产物后，从同一体系中分离出了四种配合物。它们是红色的主产品[Ni(PyrCO)2(H2O)2](H2O)，以及两种不同颜色的多晶体绿色[Ni(PyrCO)2(H2O)2]和紫色[Ni(PyrCO)2(H2O)2]，只有少量的面-Na[Ni(PyrCO)3]三氰肟酸。另外两种复合物，即二聚体[Ni2(PyrCO)4(H2O)2]-2C3H7OH 和三氰基氧化合物[Ni{HPyrCO}(PyrCO)2]-2CH3CN，含有结晶的外层溶剂分子，是起始化合物在窄管中直接作用的结果。利用红外光谱、固态紫外-可见光谱、TG/DSC 分析和 X 射线晶体学对所有分离出的复合物进行了表征。数据显示，所有结构中都形成了五元螯合环，所有结晶水合物中都采用了氰肟的反式几何结构。加热红色、绿色和紫色结晶水合物会导致不可逆脱水，并形成无水棕色复合物 [Ni(PyrCO)2]。对 RED 三水合物的变温磁化学研究证实，孤立的 Ni(II) 中心之间缺乏相互作用，而在聚合无水化合物中，线性链上的金属离子之间存在反铁磁相互作用。通过对固态电子能谱进行全线形分析，可以计算出拉卡斥力参数（B）和奈菲劳斯常数（β）。在三种结晶水合物中，存在六配位的高自旋 Ni2+ 复合物，它们具有不同程度的菱形（轴向伸长）畸变，因此配体的晶体场强也不同。所有配合物在惰性气体保护下热分解的最终产物都是金属海绵镍。
Remarkable Structural Diversity of N-Pyrrolidine-cyanoxime and its Ni(II) Complexes
A novel cyanoxime, 2-oximino-2-cyano-N-pyrrolidine-acetamide (further HPyrCO), was synthesized and characterized by spectroscopic methods, thermal analysis, and X-ray crystallography. The structure revealed eight independent molecules with elaborate intermolecular H-bonding in the asymmetric unit and adoption of the trans-anti configuration of the cyanoxime. Henceforth, a series of Ni(II) coordination compounds, crystallohydrates, with this new cyanoxime was obtained from aqueous solutions, with four complexes isolated from the same system after filtration of the main product and subsequent crystallization of new products from the mother liquor. These were RED, the main product [Ni(PyrCO)2(H2O)2](H2O), and two differently colored polymorphs GREEN [Ni(PyrCO)2(H2O)2] and VIOLET [Ni(PyrCO)2(H2O)2], with only minor amounts of the fac-Na[Ni(PyrCO)3] tris-cyanoximate. Two other complexes, dimeric [Ni2(PyrCO)4(H2O)2]·2C3H7OH and tris-cyanoximate [Ni{HPyrCO}(PyrCO)2]·2CH3CN, contained outer-sphere solvent molecules of crystallization and were obtained as the result of direct interaction of starting compounds in narrow tubes. All isolated complexes were characterized using IR, solid-state UV–visible spectroscopy, TG/DSC analysis, and X-ray crystallography. Data showed the formation of five-membered chelate rings in all structures and adoption of the trans-geometry of cyanoxime in all crystallohydrate complexes. Heating of the RED, GREEN, and VIOLET crystallohydrates led to irreversible dehydration and the formation of an anhydrous brown complex, [Ni(PyrCO)2]. Variable temperature magnetochemical studies of RED trihydrate confirmed a lack of interactions between isolated Ni(II) centers, while there was an antiferromagnetic interaction between metal ions in the linear chain in the polymeric anhydrous compound. Full line shape analysis of solid-state electronic spectra allowed calculation of the Racah Repulsion Parameter (B) and Nephelauxetic Constant (β). In three crystallohydrates, there were six-coordinated high-spin Ni2+ complexes with different degrees of rhombic (with axial elongation) distortions and, therefore, ligands’ crystal field strength. The final product of the thermal decomposition of all complexes under inert gas protection was metallic Ni sponge.
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The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.
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