Synthesis and Crystal Structure of a Mononuclear Cobalt(III) Complex with 2-[(2-Hydroxymethylphenyl)iminomethyl]phenol and Dimethylaminopyridine

IF 0.1 Q4 CRYSTALLOGRAPHY
N. Sato, Ko Yoneda, Y. Yamada, Masayuki Koikawa
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引用次数: 0

Abstract

Single-molecule magnets (SMMs) are intensively discussed as high-density storage, quantum computing, or spintronic technology.1–3 We have reported the weak SMM ability of a tetranuclear Co complex, [Co4(L1-H)4Cl2(CH3OH)2], but found that the stability of the complex depends on the coordinating solvent molecules.4 To improve the stability, we are working on the synthesis of new Co complexes in which the coordination solvents are replaced with various monodentate ligands. While an attempt was made to prepare a tetranuclear Co complex coordinated with dmpa, we obtained single crystals of [Co(L1-H)(HL1-H)dmpa]·CH3CN (1). Here, we report on the synthesis and the crystal structure of 1 (Fig. 1). The ligand H2L1-H was obtained by a literature method.5 An acetonitrile solution (10 mL) containing bis(acetylacetonato) diaquacobalt(II) (0.182 g, 0.5 mmol), H2L1-H (0.113 g, 0.5 mmol), and triethylamine (0.055 g, 0.5 mmol) was stirred at ca. 80°C for 30 min. To the obtained solution was added 4-dimethylaminopyridine (0.122 g, 1.0 mmol) with stirring. The orange precipitate was filtered off, and the filtrate was allowed to stand at room temperature. Reddish brown crystals suitable for X-ray analysis were obtained after 3 days. Yield, 0.009 g (3.0%). Measurements were made on a Rigaku VariMax Saturn CCD 724+ diffractometer with graphite-monochromated Mo-Kα radiation at 113 K. An empirical analytical absorption correction was applied. The structure was solved by direct methods (SIR92) and expanded using Fourier techniques. The nonhydrogen atoms were refined anisotropically. The alcoholic hydrogen atom, H3A, was found from Fourier peaks. The other hydrogen atoms were located at the calculated positions and refined using the riding model. The final cycle of a full-matrix least-squares refinement on F2 using SHELXL-2016 was based on observed reflections and variable parameters and converged with unweighted and weighted agreement factors of R1 (0.0483) and wR2 (0.1226).6 Details of the X-ray structure determination are listed in Table 1. An ORTEP drawing of the title complex 1 is shown in Fig. 2, and selected bond lengths and angles are provided in Table 2. The crystal structure of 1 consists of a Co atom, dianionic (L1-H)2–, monoanionic (HL1-H)–, and neutral dmpa ligands. The first ligand, (L1-H)2–, is coordinated to Co1 as a tridentate ligand with mer-manner. This coordination mode is similar to that of Co(III) units in the previously reported [Co4(L1-H)4Cl2(CH3OH)2]. The second ligand, (HL1-H)–, is bound to Co(III) as a bidentate chelate by phenoxo oxygen and imino nitrogen atoms. Only the tridentate coordination mode of (HL1-H)–, such as [Co(HL1-H)2]NO3, has been reported so far. This is the first example of the structurally analyzed bidentate coordination mode of H2L1-H. The remaining coordination site is occupied by the dmpa. The coordination geometry around the central Co atom is an octahedral with mer-N3O3 coordination environment. The bond distances between Co1 and the coordinating oxygen atoms are in the range of 1.8803(16) – 1.9083(16)Å and those for coordinating nitrogen atoms are in the range of 1.9352(19) – 1.9705(19)Å. These distances are common for Co(III) complexes.7 To confirm the oxidation state assignment, the bond valence sum (BVS) calculation was applied for Co1.9,1
2-[(2-羟甲基苯基)亚甲基]苯酚-二甲氨基吡啶单核钴配合物的合成与晶体结构
单分子磁体(SMMs)作为高密度存储、量子计算或自旋电子技术被广泛讨论。我们已经报道了四核Co配合物[Co4(L1-H)4Cl2(CH3OH)2]的弱SMM能力,但发现配合物的稳定性取决于配位溶剂分子为了提高稳定性,我们正在研究用各种单齿配体代替配位溶剂的新型钴配合物的合成。在尝试制备与dmpa配位的四核Co配合物时,我们得到了[Co(L1-H)(HL1-H)dmpa]·CH3CN(1)的单晶。在这里,我们报道了1的合成和晶体结构(图1)。通过文献法得到了配体H2L1-H取10 mL的乙腈溶液,其中含有二(乙酰丙酮)二水产化钡(II) (0.182 g, 0.5 mmol)、h2l - h (0.113 g, 0.5 mmol)和三乙胺(0.055 g, 0.5 mmol),在约80℃下搅拌30 min,在得到的溶液中加入4-二甲氨基吡啶(0.122 g, 1.0 mmol)并搅拌。过滤掉橙色沉淀物,滤液在室温下静置。3天后得到适合x射线分析的红棕色晶体。收率:0.009 g(3.0%)。测量是在Rigaku VariMax土星CCD 724+衍射仪上进行的,在113 K下使用石墨-单铬化Mo-Kα辐射。采用经验分析吸收校正。用直接法(SIR92)求解该结构,并用傅里叶技术展开。非氢原子是各向异性细化的。从傅里叶峰中发现醇性氢原子H3A。其他氢原子被定位在计算的位置,并使用骑乘模型进行细化。使用SHELXL-2016对F2进行全矩阵最小二乘精化的最终周期基于观测反射和可变参数,并收敛于未加权和加权一致因子R1(0.0483)和wR2 (0.1226)x射线结构测定的细节列于表1。标题配合物1的ORTEP图如图2所示,选择的键长和键角如表2所示。1的晶体结构由一个Co原子、二阴离子(L1-H)2 -、单阴离子(h1 - h) -和中性配体组成。第一个配体(L1-H)2 -与Co1配位为三叉戟配体。这种配位模式类似于先前报道的[Co4(L1-H)4Cl2(CH3OH)2]中Co(III)单元的配位模式。第二个配体(h_1 - h) -通过苯氧和亚氮原子与Co(III)作为双齿螯合物结合。(h1 - h) -的三叉戟配位模式,如[Co(h1 - h)2]NO3,目前仅有报道。这是对H2L1-H的双齿配位模式进行结构分析的第一个例子。其余的协调位置由dmpa占用。中心Co原子周围的配位几何是一个具有mer-N3O3配位环境的八面体。Co1与配位氧原子的键距为1.8803(16)~ 1.9083(16)Å,配位氮原子的键距为1.9352(19)~ 1.9705(19)Å。这些距离对于Co(III)配合物来说是常见的为了确定氧化态归属,对Co1.9,1进行了键价和(BVS)计算
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
0.60
自引率
50.00%
发文量
17
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