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Heterometallic Copper–Vanadium Compounds: Crystal Structures of Polymers [Cu(im)4(V2O4(mand)2)]n and [Cu(im)4(V2O4((S)-mand)2)]n·2nH2O (im = imidazole, mand = mandelato2−)
Journal of Chemical Crystallography ( IF 0.4 ) Pub Date : 2019-10-17 , DOI: 10.1007/s10870-019-00810-8
Mária Šimuneková 1 , Peter Schwendt 1 , Róbert Gyepes 2 , Lukáš Krivosudský 1, 3
Affiliation  

Abstract Two new 1D polymeric heterometallic copper–vanadium compounds were prepared. The polymers are constructed from [Cu( im ) 4 ] 2+ cations that are coordinated to two terminal oxido ligands of [V 2 O 4 ( mand ) 2 ] 2− anions. The stronger coordination in [Cu( im ) 4 V 2 O 4 ( mand ) 2 ] n ( 1 ) that contains the racemic mandelato ligand is manifested by a shorter Cu‒O bond distance 2.4095(12) Å, while the weaker interaction in [Cu( im ) 4 (V 2 O 4 (( S )- mand ) 2 )] n ·2 n H 2 O ( 2 ) is exhibited by Cu‒O bond distances 2.4547(16) Å and 2.5413(16) Å. The vanadate anion in compound 2 carries only the ( S )-enantiomer of the initial mandelic acid and differs from the anion in 1 in parallel cis orientation of the phenyl groups of the mandelato ligand. FT-IR spectroscopy was used for the confirmation of the coordination mode of mandelato ligand. Strong bands corresponding to the vibrations of carboxyl groups can be observed around 1650 and at 1344 cm −1 . The stretching vibration of deprotonated hydroxyl group in the mandelato ligand occurs at 1045 and 1065 cm −1 for 1 and 2 , respectively. In addition, the very strong, characteristic band corresponding to ν (V=O) vibration can be observed at 931 cm −1 for 1 and 925 cm −1 for 2 , as well as in Raman spectrum. Graphic Abstract The polymeric structures of two new vanadium-copper heterometallic complexes are constructed from [Cu( imidazole ) 4 ] 2+ cations that are coordinated to two terminal oxido ligands of [V 2 O 4 ( mandelato ) 2 ] 2− anions with different orientation of the phenyl groups depending on the chirality of the mandelato ligand.

中文翻译:

异金属铜-钒化合物:聚合物的晶体结构 [Cu(im)4(V2O4(mand)2)]n 和 [Cu(im)4(V2O4((S)-mand)2)]n·2nH2O (im =咪唑,mand = mandelato2−)

摘要 制备了两种新的一维聚合异金属铜钒化合物。该聚合物由与[V 2 O 4 (mand ) 2 ] 2- 阴离子的两个末端氧化配体配位的[Cu(im) 4 ] 2+ 阳离子构成。含有外消旋 mandelato 配体的 [Cu(im) 4 V 2 O 4 (mand) 2 ] n ( 1 ) 配位越强,Cu-O 键距越短 2.4095(12) Å,相互作用越弱[Cu(im) 4 (V 2 O 4 (( S )-mand ) 2 )] n ·2 n H 2 O ( 2 ) 表现为 Cu-O 键距离 2.4547(16) Å 和 2.5413(16) Å . 化合物 2 中的钒酸根阴离子仅携带初始扁桃酸的 (S)-对映异构体,并且与 1 中的阴离子不同,其平行顺式取向的扁桃酸配体的苯基。FT-IR光谱用于确认mandelato配体的配位模式。可以在 1650 附近和 1344 cm -1 观察到对应于羧基振动的强带。mandelato 配体中去质子化的羟基的伸缩振动分别发生在 1 和 2 的 1045 和 1065 cm -1 处。此外,在 1 的 931 cm -1 和 2 的 925 cm -1 以及拉曼光谱中,可以观察到对应于 ν (V=O) 振动的非常强的特征带。图形摘要 两种新型钒-铜异质金属配合物的聚合物结构是由 [Cu(imidazole ) 4 ] 2+ 阳离子与 [V 2 O 4 ( mandelato ) 2 ] 2- 阴离子的两个末端氧化物配体配位的。苯基的取向取决于曼德拉托配体的手性。
更新日期:2019-10-17
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