Syntheses and Structure of Nine-Coordinate Gd~Ⅲ Complexes,Na[Gd~Ⅲ(edta)(H_2O)_3]·5H_2O and Na_4[Gd~Ⅲ

来源 :Journal of Rare Earths | 被引量 : 0次 | 上传用户:HUZHAOHUA333
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The crystal and molecular structures of the Na[Gd Ⅲ(edta)(H_2O)_3]·5H_2O (edta=ethylenediaminetetraacetic acid) and Na_4[Gd Ⅲ(dtpa)(H_2O)]_2·14H_2O (dtpa=diethylenetriaminepentaacetic acid) complexes were determined by single-crystal X-ray structure analyses. The crystal of the Na[Gd Ⅲ(edta)(H_2O)_3]·5H_2O belongs to orthorhombic crystal system and Fdd2 space group. The crystal data are as follows: a =1.9424(7)nm,b =3.5496(12)nm,c =1.2125(4)nm,V =8.360(5)nm 3,Z =16,M =612.63,D _c=1.947 g·cm (-3),μ =3.274 mm (-1) and F (000)=4880. The final R and wR values are 0.0295 and 0.0677 for 3102 [ I>2.0σ(I) ] unique reflections,and 0.0328 and 0.0695 for all 8269 reflections,respectively. The [Gd Ⅲ(edta)(H_2O)_3]-complex anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which the nine coordinate atoms,two N and seven O are from one edta ligand and three coordinate water molecules. The crystal of the Na_4[Gd Ⅲ(dtpa)(H_2O)]_2·14H_2O belongs to monoclinic crystal system and P2(1)/n space group. The crystal data are as follows: a =1.4894(6)nm,b =1.7987(7)nm, c =1.9600(7)nm,β =99.496(7),V =5.179(3)nm3,Z=4,M =1471.44,D _c=1.841 g·cm (-3),μ =2.676 mm (-1) and F (000)=2872. The final R and wR are 0.0435 and 0.0979 for 8929 [ I>2.0σ(I) ] unique reflections,and 0.0820 and 0.1167 for all 20717 reflections,respectively. The total complex moleculue is composed of two close parts in structure. The [Gd Ⅲ(dtpa)(H_2O)] (2-) complex anion in the every part has a nine-coordinate structure with distorted monocapped square antiprismatic prism,in which the dtpa coordinates with central Gd Ⅲ ion acting as a octadentate ligand with three N atoms and five O atoms,and one water as the ninth ligand directly coordinates with central Gd Ⅲ ion. The crystal and molecular structures of the Na [Gd Ⅲ (edta) (H_2O) _3] · 5H_2O (edta = ethylenediaminetetraacetic acid) and Na_4 [Gd Ⅲ (dtpa) (H_2O)] _2 · 14H_2O determined by single-crystal X-ray structure analyzes. The crystal of the Na [Gd III (edta) (H 2 O) _3] · 5H 2 O belongs to orthorhombic crystal system and Fdd 2 space group. (4) nm, V = 8.360 (5) nm 3, Z = 16, M = 612.63, Dc = 1.947 g · cm -3, μ = 3.274 mm (-1) and F (000) = 4880. The final R and wR values ​​are 0.0295 and 0.0677 for 3102 [I> 2.0σ (I)] unique reflections, and 0.0328 and 0.0695 for all 8269 reflections, respectively. The [Gd III (edta) (H_2O) _3] -pleplex anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which the nine coordinate atoms, two N and seven O are from one edta ligand and three coordinate water molecules. crystal of the Na_4 [Gd Ⅲ (dtpa) (H_2O)] _ 2 · 14H_2O belongs to monoclin The crystal data is as follows: a = 1.4894 (6) nm, b = 1.7987 (7) nm, c = 1.9600 (7) nm, , V = 5.179 (3) nm3, Z = 4, M = 1471.44, D _c = 1.841 g · cm -3, μ = 2.676 mm -1 and F 000 000 = 2872. The final R and wR are 0.0435 and 0.0979 for 8929 [I> 2.0σ (I)] unique reflections, and 0.0820 and 0.1167 for all 20717 reflections, respectively. The total complex is composed of two close parts in a structure. The [Gd III (dtpa) ( H 2 O]] (2-) complex anion in the each part has a nine-coordinate structure with distorted monocapped square antiprismatic prism, in which the dtpa coordinates with central Gd III ion acting as an octadentate ligand with three N atoms and five O atoms, and one water as the ninth ligand directly coordinates with central Gd III ion.
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