Journal
JOURNAL OF SOLID STATE CHEMISTRY
Volume 221, Issue -, Pages 79-84Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jssc.2014.09.021
Keywords
Hg-Hg timer; Homometallic interaction; Mercury nitroprusside; Layered solid
Funding
- CONACyT [2011-01-174247, FON.INST./75/2012, 154626]
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The pentacyanonitrosylferrate complex anion, [Fe(CN)(5)NO](2-), forms an insoluble solid with Hg(I) ion, of formula unit Hg-2[Fe(CN)(5)NO]center dot 2H(2)O, whose crystal structure and related properties are unknown. This contribution reports the preparation of that compound by the precipitation method and its structural study from X-ray powder patterns complemented with spectroscopic information from IR, Raman, and UV-vis techniques. The crystal structure was solved ab initio and then refined using the Rietveld method. The solid crystallizes with a triclinic unit cell, in the P-1 space group, with cell parameters a=10.1202(12), b=10.1000(13), c=7.4704(11) Alpha; alpha=110.664(10), beta=110.114(10), gamma=104.724(8)degrees. Within the unit cell, two formula units are accommodated (Z=2). It adopts a layered structure related with the coordination of the equatorial CN groups at their N end to the Hg atoms while the axial CN ligand remains unlinked. Within the layers neighboring Hg-2[Fe(CN)(5)NO] building units remain linked through four relatively strong Hg-Hg interactions, with an interatomic distance of 2.549(3) angstrom. The charge donation from the equatorial CN groups through their 5 sigma orbitals results into an increase for the electron density on the Hg atoms, which strengths the Hg-Hg bond. In the Raman spectrum, that metal-metal bond is detected as a stretching vibration band at 167 cm(-1). The available free volume between neighboring layers accommodates two water molecules, which are stabilized within the framework through hydrogen bonds with the N end of the unlinked axial CN group. The removal of these weakly bonded water molecules results in structural disorder for the material 3D framework. (C) 2014 Elsevier Inc. All rights reserved.
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