Crystallographic and vibrational spectroscopic studies of octakis(DMSO)lanthanoid(III) iodides

Alireza Abbasi, Emiliana Damian Risberg, Lars Eriksson, J. Mink, Ingmar Persson, Magnus Sandström, Yurii V. Sidorov, Mikhail Yu Skripkin, Ann Sofi Ullström

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Abstract

The octakis(DMSO) (DMSO = dimethylsulfoxide) neodymium(III), samarium(III), gadolinium(III), dysprosium(III), erbium(III), and lutetium(III) iodides crystallize in the monoclinic space group P21/n (No. 14) with Z = 4, while the octakis(DMSO) iodides of the larger lanthanum(III), cerium(III), and praseodymium(III) ions crystallize in the orthorhombic space group Pbca (No. 61), Z = 8. In all [Ln(OS(Me2)8]I3 compounds the lanthanoid(III) ions coordinate eight DMSO oxygen atoms in a distorted square antiprism. Up to three of the DMSO ligands were found to be disordered and were described by two alternative configurations related by a twist around the metal-oxygen (Ln-O) bond. To resolve the atomic positions and achieve reliable Ln-O bond distances, complete semirigid DMSO molecules with restrained geometry and partial occupancy were refined for the alternative sites. This disorder model was also applied on previously collected data for the monoclinic octakis(DMSO)yttrium(III) iodide. At ambient temperature, the eight Ln-O bond distances are distributed over a range of about 0.1 Å. The average value increases from Ln-O 2.30, 2.34, 2.34, 2.36, 2.38, 2.40 to 2.43 Å (Ln = Lu, Er, Y, Dy, Gd, Sm, and Nd) for the monoclinic [Ln(OSMe2) 8]I3 structures, and from 2.44, 2.47 to 2.49 Å (Ln = Pr, Ce, and La) for the orthorhombic structures, respectively. The average of the La-O and Nd-O bond distances remained unchanged at 100 K, 2.49 and 2.43 Å, respectively. Despite longer bond distances and larger Ln-O-S angles, the cell volumes are smaller for the orthorhombic structures (Ln = Pr, Ce, and La) than for the monoclinic structure with Ln = Nd, showing a more efficient packing arrangement. Raman and IR absorption spectra for the [Ln(OS(CH 3)2)8]I3 (Ln = La, Ce, Pr, Nd, Gd, Tb, Dy, Er, Lu, and Y) compounds, also deuterated for La and Y, have been recorded and analyzed by means of normal coordinate methods. The force constants for the Ln-O and S-O stretching modes in the complexes increase with decreasing Ln-O bond distance and show increasing polarization of the bonds for the smaller and heavier lanthanoid(III) ions.

Original languageEnglish
Pages (from-to)7731-7741
Number of pages11
JournalInorganic Chemistry
Volume46
Issue number19
DOIs
Publication statusPublished - Sep 17 2007

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Lanthanoid Series Elements
Iodides
Dimethyl Sulfoxide
iodides
Ions
lutetium
ions
dysprosium
praseodymium
samarium
neodymium
gadolinium
Praseodymium
cerium
yttrium
Dysprosium
Lutetium
lanthanum
erbium
Erbium

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Abbasi, A., Risberg, E. D., Eriksson, L., Mink, J., Persson, I., Sandström, M., ... Ullström, A. S. (2007). Crystallographic and vibrational spectroscopic studies of octakis(DMSO)lanthanoid(III) iodides. Inorganic Chemistry, 46(19), 7731-7741. https://doi.org/10.1021/ic7006588

Crystallographic and vibrational spectroscopic studies of octakis(DMSO)lanthanoid(III) iodides. / Abbasi, Alireza; Risberg, Emiliana Damian; Eriksson, Lars; Mink, J.; Persson, Ingmar; Sandström, Magnus; Sidorov, Yurii V.; Skripkin, Mikhail Yu; Ullström, Ann Sofi.

In: Inorganic Chemistry, Vol. 46, No. 19, 17.09.2007, p. 7731-7741.

Research output: Contribution to journalArticle

Abbasi, A, Risberg, ED, Eriksson, L, Mink, J, Persson, I, Sandström, M, Sidorov, YV, Skripkin, MY & Ullström, AS 2007, 'Crystallographic and vibrational spectroscopic studies of octakis(DMSO)lanthanoid(III) iodides', Inorganic Chemistry, vol. 46, no. 19, pp. 7731-7741. https://doi.org/10.1021/ic7006588
Abbasi, Alireza ; Risberg, Emiliana Damian ; Eriksson, Lars ; Mink, J. ; Persson, Ingmar ; Sandström, Magnus ; Sidorov, Yurii V. ; Skripkin, Mikhail Yu ; Ullström, Ann Sofi. / Crystallographic and vibrational spectroscopic studies of octakis(DMSO)lanthanoid(III) iodides. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 19. pp. 7731-7741.
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abstract = "The octakis(DMSO) (DMSO = dimethylsulfoxide) neodymium(III), samarium(III), gadolinium(III), dysprosium(III), erbium(III), and lutetium(III) iodides crystallize in the monoclinic space group P21/n (No. 14) with Z = 4, while the octakis(DMSO) iodides of the larger lanthanum(III), cerium(III), and praseodymium(III) ions crystallize in the orthorhombic space group Pbca (No. 61), Z = 8. In all [Ln(OS(Me2)8]I3 compounds the lanthanoid(III) ions coordinate eight DMSO oxygen atoms in a distorted square antiprism. Up to three of the DMSO ligands were found to be disordered and were described by two alternative configurations related by a twist around the metal-oxygen (Ln-O) bond. To resolve the atomic positions and achieve reliable Ln-O bond distances, complete semirigid DMSO molecules with restrained geometry and partial occupancy were refined for the alternative sites. This disorder model was also applied on previously collected data for the monoclinic octakis(DMSO)yttrium(III) iodide. At ambient temperature, the eight Ln-O bond distances are distributed over a range of about 0.1 {\AA}. The average value increases from Ln-O 2.30, 2.34, 2.34, 2.36, 2.38, 2.40 to 2.43 {\AA} (Ln = Lu, Er, Y, Dy, Gd, Sm, and Nd) for the monoclinic [Ln(OSMe2) 8]I3 structures, and from 2.44, 2.47 to 2.49 {\AA} (Ln = Pr, Ce, and La) for the orthorhombic structures, respectively. The average of the La-O and Nd-O bond distances remained unchanged at 100 K, 2.49 and 2.43 {\AA}, respectively. Despite longer bond distances and larger Ln-O-S angles, the cell volumes are smaller for the orthorhombic structures (Ln = Pr, Ce, and La) than for the monoclinic structure with Ln = Nd, showing a more efficient packing arrangement. Raman and IR absorption spectra for the [Ln(OS(CH 3)2)8]I3 (Ln = La, Ce, Pr, Nd, Gd, Tb, Dy, Er, Lu, and Y) compounds, also deuterated for La and Y, have been recorded and analyzed by means of normal coordinate methods. The force constants for the Ln-O and S-O stretching modes in the complexes increase with decreasing Ln-O bond distance and show increasing polarization of the bonds for the smaller and heavier lanthanoid(III) ions.",
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T1 - Crystallographic and vibrational spectroscopic studies of octakis(DMSO)lanthanoid(III) iodides

AU - Abbasi, Alireza

AU - Risberg, Emiliana Damian

AU - Eriksson, Lars

AU - Mink, J.

AU - Persson, Ingmar

AU - Sandström, Magnus

AU - Sidorov, Yurii V.

AU - Skripkin, Mikhail Yu

AU - Ullström, Ann Sofi

PY - 2007/9/17

Y1 - 2007/9/17

N2 - The octakis(DMSO) (DMSO = dimethylsulfoxide) neodymium(III), samarium(III), gadolinium(III), dysprosium(III), erbium(III), and lutetium(III) iodides crystallize in the monoclinic space group P21/n (No. 14) with Z = 4, while the octakis(DMSO) iodides of the larger lanthanum(III), cerium(III), and praseodymium(III) ions crystallize in the orthorhombic space group Pbca (No. 61), Z = 8. In all [Ln(OS(Me2)8]I3 compounds the lanthanoid(III) ions coordinate eight DMSO oxygen atoms in a distorted square antiprism. Up to three of the DMSO ligands were found to be disordered and were described by two alternative configurations related by a twist around the metal-oxygen (Ln-O) bond. To resolve the atomic positions and achieve reliable Ln-O bond distances, complete semirigid DMSO molecules with restrained geometry and partial occupancy were refined for the alternative sites. This disorder model was also applied on previously collected data for the monoclinic octakis(DMSO)yttrium(III) iodide. At ambient temperature, the eight Ln-O bond distances are distributed over a range of about 0.1 Å. The average value increases from Ln-O 2.30, 2.34, 2.34, 2.36, 2.38, 2.40 to 2.43 Å (Ln = Lu, Er, Y, Dy, Gd, Sm, and Nd) for the monoclinic [Ln(OSMe2) 8]I3 structures, and from 2.44, 2.47 to 2.49 Å (Ln = Pr, Ce, and La) for the orthorhombic structures, respectively. The average of the La-O and Nd-O bond distances remained unchanged at 100 K, 2.49 and 2.43 Å, respectively. Despite longer bond distances and larger Ln-O-S angles, the cell volumes are smaller for the orthorhombic structures (Ln = Pr, Ce, and La) than for the monoclinic structure with Ln = Nd, showing a more efficient packing arrangement. Raman and IR absorption spectra for the [Ln(OS(CH 3)2)8]I3 (Ln = La, Ce, Pr, Nd, Gd, Tb, Dy, Er, Lu, and Y) compounds, also deuterated for La and Y, have been recorded and analyzed by means of normal coordinate methods. The force constants for the Ln-O and S-O stretching modes in the complexes increase with decreasing Ln-O bond distance and show increasing polarization of the bonds for the smaller and heavier lanthanoid(III) ions.

AB - The octakis(DMSO) (DMSO = dimethylsulfoxide) neodymium(III), samarium(III), gadolinium(III), dysprosium(III), erbium(III), and lutetium(III) iodides crystallize in the monoclinic space group P21/n (No. 14) with Z = 4, while the octakis(DMSO) iodides of the larger lanthanum(III), cerium(III), and praseodymium(III) ions crystallize in the orthorhombic space group Pbca (No. 61), Z = 8. In all [Ln(OS(Me2)8]I3 compounds the lanthanoid(III) ions coordinate eight DMSO oxygen atoms in a distorted square antiprism. Up to three of the DMSO ligands were found to be disordered and were described by two alternative configurations related by a twist around the metal-oxygen (Ln-O) bond. To resolve the atomic positions and achieve reliable Ln-O bond distances, complete semirigid DMSO molecules with restrained geometry and partial occupancy were refined for the alternative sites. This disorder model was also applied on previously collected data for the monoclinic octakis(DMSO)yttrium(III) iodide. At ambient temperature, the eight Ln-O bond distances are distributed over a range of about 0.1 Å. The average value increases from Ln-O 2.30, 2.34, 2.34, 2.36, 2.38, 2.40 to 2.43 Å (Ln = Lu, Er, Y, Dy, Gd, Sm, and Nd) for the monoclinic [Ln(OSMe2) 8]I3 structures, and from 2.44, 2.47 to 2.49 Å (Ln = Pr, Ce, and La) for the orthorhombic structures, respectively. The average of the La-O and Nd-O bond distances remained unchanged at 100 K, 2.49 and 2.43 Å, respectively. Despite longer bond distances and larger Ln-O-S angles, the cell volumes are smaller for the orthorhombic structures (Ln = Pr, Ce, and La) than for the monoclinic structure with Ln = Nd, showing a more efficient packing arrangement. Raman and IR absorption spectra for the [Ln(OS(CH 3)2)8]I3 (Ln = La, Ce, Pr, Nd, Gd, Tb, Dy, Er, Lu, and Y) compounds, also deuterated for La and Y, have been recorded and analyzed by means of normal coordinate methods. The force constants for the Ln-O and S-O stretching modes in the complexes increase with decreasing Ln-O bond distance and show increasing polarization of the bonds for the smaller and heavier lanthanoid(III) ions.

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