STEREOCHEMISTRY OF ETHYLENEDIAMINETETRAACETATO COMPLEXES .I. STRUCTURE OF CRYSTALLINE MN3(HY)210H2O + CONFIGURATION OF 7-COORDINATE MN)OH2)Y-2 ION1-3
STEREOCHEMISTRY OF ETHYLENEDIAMINETETRAACETATO COMPLEXES .I. STRUCTURE OF CRYSTALLINE MN3(HY)210H2O + CONFIGURATION OF 7-COORDINATE MN)OH2)Y-2 ION1-3
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DOI：
10.1021/ic50011a006
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发表时间：
1964-01-01
影响因子：
4.6
通讯作者：
SILVERTON, JV
中科院分区：
文献类型：
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作者：
RICHARDS, S;HOARD, JL;SILVERTON, JV
对Mn3 (HY) 2·10H2O单斜晶体0<(sin)/< 0.95的{hkl) x射线数据进行分析，得出了明确的结构结构测定。单元胞含有两个3()2·10H2O；除反转中心的两个Mn外，所有原子均占据C62h-P2i/n的四倍一般位置（表1）。原子排列可以按如下方式排列：六轴七坐标Mn (OH2) Y~ 2离子（图1）分布在一般位置（图2），并通过沿序列将质子（酸性氢）添加到相邻的06和原子（图1）氢键对上，转化为平行于b的准无限链[Mn (OH2) YH] m-™（图2）。这种键合非常紧密，03—O7= 2.469±0.010 A，至少是准对称的。锰占据反转中心呈八面体配位；配位基包括两个Os型羧酸氧（图1）、两个与羧酸Oe原子在2.708±0.019 a的氢键键的水分子和两个在2.698±0.010 Á的氢键键的水分子。使02个原子羧化。所有的水分子，包括两组不与锰络合的水分子，都参与了氢键（表四）。CN和CC键长平均为1.471±0.007 a和1.519±0.008 a，除此之外，个别数据显示的内部一致性值得注意（表II）。CO键长似乎反映了羧酸盐显示的双齿络合强度的定量变化。六轴七坐标Mn (OH2) Y基团的环、键角较好地符合准对称C2-2（表V）。这种理想对称性的偏离体现在松散的内部配位基团（表六）和弱的Mn-0和Mn-N络合键（表三）中。表7和图1和图3描述了理想的Mn (OH2) Y~ 2离子的配位基，在适当的h溶液中，Mn (OH2) Y~ 2离子被认为是最可能的种。
Analysis of {hkl) X-ray data for 0<(sin)/< 0.95 from monoclinic crystals of Mn3 (HY) 2· 10H2O yields definitive struc" ture determination. The unit cell contains two 3 () 2· 10H2O; all atoms, save two Mn at inversion centers, occupy fourfold general positions of C62h-P2i/n (Table I). The atomic arrangement can be put together as follows: Sexadentate seven-coordinate Mn (OH2) Y~ 2 ions (Fig. 1) are distributed in general positions (Fig. 2) and are converted into quasiinfinite chains [Mn (OH2) YH] m-™ parallel to b (Fig. 2) by the addition of protons (the acid hydrogens) to hydrogen bond contiguous pairs of 06 and atoms (Fig. 1) along the sequence. This bonding isvery tight, 03——O7= 2.469±0.010 A., and is atleast quasi-symmetric. Manganese occupying inversion centers displays octahedral coordination; the coordination group comprises two carboxylate oxygens of Os type (Fig. 1), two water molecules which are hydrogen bonded at 2.708±0.019 A. to carboxylate Oe atoms, and two water molecules which are hydrogen bonded at 2.698±0.010 Á. to carboxylate 02 atoms. All water molecules, including two sets not complexed to manganese, are involved in hydrogen bonding (Table IV). CN and CC bond lengths average 1.471±0.007 and 1.519±0.008 A. and are otherwise notable for the internal consistency dis-played by the individual data (Table II). CO bond lengths seem to reflect quantitative variations in the strength of the bidentate complexing displayed by carboxylate. Ring, bond angles conform rather well to the quasi-symmetry C2-2 for the sexadentate seven-coordinate Mn (OH2) Y group (Table V). Departure from this ideal symmetry is manifest in the loosely packed inner coordination group (Table VI) and in the weak Mn-0 and Mn-N complexing bonds (Table III). Table VII and Fig. 1 and 3 describe the coordination group of the idealized Mn (OH2) Y~ 2 ion which is regarded as the most prob-able species in solutions of appropriatepH.