skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Preparation of praseodymium(III) chloranilate and the crystal structures of Pr/sub 2/(C/sub 6/Cl/sub 2/O/sub 4/)/sub 3/. 8C/sub 2/H/sub 5/OH and Na/sub 3/(C/sub 6/H/sub 2/O(OH)(SO/sub 3/)/sub 2/). H/sub 2/O

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00163a022· OSTI ID:5105434

The crystal structure of Pr/sub 2/(C/sub 6/Cl/sub 2/O/sub 4/)/sub 3/ x 8C/sub 2/H/sub 5/OH (1), a complex obtained by slow hydrolysis of o-chloranil (C/sub 6/Cl/sub 4/O/sub 2/) in acidic ethanol solution, has been determined by single-crystal x-ray diffraction techniques with data collected by counter methods. The structure of Na/sub 3/(C/sub 6/H/sub 2/O(OH)(SO/sub 3/)/sub 2/) x H/sub 2/O (2), the tranion of tiron, has also been determined by x-ray crystallography. Crystals of 1 form in triclinic space group P1 with a = 8.990 (1) Angstrom, b = 10.503 (2) Angstrom, c = 13.598 (1) Angstrom, ..cap alpha.. = 99.02 (1)/sup 0/, ..beta.. = 91.50 (1)/sup 0/, ..gamma.. = 94.44 (1)/sup 0/. The observed density of 1.643 g cm/sup -3/ is in agreement with the calculated value of 1.671 g cm/sup -3/ for one unit of Pr/sub 2/(C/sub 6/Cl/sub 2/O/sub 4/)/sub 3/ x 8C/sub 2/H/sub 5/OH per unit cell. The crystal structure is a three-dimensional network of alternating (C/sub 6/Cl/sub 2/O/sub 4/)/sup 2 -/ and Pr/sup 3 +/ ions in which the chloranilate rings lie about crystallographic inversion centers. Crystals of 2 form from aqueous solution in orthorhombic space group Pnma with a = 16.018 (2) Angstrom, b = 6.972 (2) Angstrom, and c = 9.700 (1) Angstrom. The (C/sub 6/H/sub 2/O(OH)(SO/sub 3/)/sub 2/)/sup 3 -/ species exhibits rigorous C/sub s/ symmetry, with only the two symmetry-related oxygen atoms of each SO/sub 3/ moiety lying out of the plane of the anion. There are no unusual aspects of the molecular geometry of 2. Full-matrix least-squares refinement of the structure has converged with R and R/sub w/ indices (on /F/) of 0.034 and 0.045 with use of the 805 observations with F/sub 0//sup 2/ > 3sigma(F/sub 0//sup 2/0. 5 figures, 10 tables

Research Organization:
Univ. of California, Berkeley
DOE Contract Number:
AC03-76SF00098
OSTI ID:
5105434
Journal Information:
Inorg. Chem.; (United States), Vol. 22:21
Country of Publication:
United States
Language:
English