Syntheses and structural determination of binuclear nine-coordinate (NH4)4[SmIII2(Httha)2]·16H2O and 2-D ladder-like binuclear nine-coordinate (NH4)4[SmIII2(dtpa)2]·10H2O

Two rare-earth metal coordination compounds, (NH4)4[SmIII2(Httha)2]·16H2O (1) (H6ttha = triethylenetetramine-N,N,N′,N′′,N′′′,N′′′-hexaacetic acid) and (NH4)4[SmIII2(dtpa)2]·10H2O (2) (H5dtpa = diethylenetriamine-N,N,N′,N′′,N′′-pentaacetic acid), have been synthesized through reflux and characterized by FT-IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction techniques. SmIII of (NH4)4[SmIII2(Httha)2]·16H2O (1) is nine-coordinate, forming tricapped trigonal prismatic coordination with three amine nitrogens and six oxygens, in which four oxygens are from one ttha and two from the other ttha. (NH4)4[SmIII2(Httha)2]·16H2O (1) crystallizes in the monoclinic crystal system with P2(1)/c space group. The crystal data are: a = 13.9340(13) Å, b = 22.890(3) Å, c = 20.708(2) (14) Å, β = 99.521(2)°, and V = 6513.7(13) Å3. There are two –NH+– groups in the [SmIII2(Httha)2]4−. The polymeric (NH4)4[SmIII2(dtpa)2]·10H2O (2) also is nine-coordinate with tricapped trigonal prismatic conformation and crystallizes in the triclinic crystal system with P–1 space group. The cell dimensions are: a = 9.8240(8) Å, b = 10.0329(9) Å, c = 13.0941(11) Å, β = 77.1640(10)°, and V = 1227.30(18) Å3. In (NH4)4[SmIII2(dtpa)2]·10H2O, there are two types of ammonium cations, which connect [SmIII2(dtpa)2]4− and lattice water through hydrogen bonds, leading to a 2-D ladder-like layer structure. Two SmIII coordination compounds, (NH4)4[SmIII2(Httha)2]·16H2O (I) (H6ttha = triethylenetetramine-N,N,N′,N′′,N′′′,N′′′-hexaacetic acid) and (NH4)4[SmIII2(dtpa)2]·10H2O (II) (H5dtpa = diethylenetriamine-N,N,N′,N′′,N′′-pentaacetic acid), were synthesized. The complex (I) takes binuclear molecule structural nine-coordinate tricapped trigonal prismatic conformation. The complex (II) also takes binuclear molecule structural nine-coordinate tricapped trigonal prismatic conformation, but forms polymeric 2-D ladder-like layer structure through hydrogen bonds.

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