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Title: Neutron diffraction analysis of the structure of H/sub 3/Ni/sub 4/(C/sub 5/H/sub 5/)/sub 4/

Abstract

The structure of H/sub 3/Ni/sub 4/Cp/sub 4/ (Cp=n/sup 5/-C/sub 5/H/sub 5/), an unusual paramagnetic metal cluster complex, has been analyzed by single-crystal neutron diffraction techniques at low temperature (81 K). As predicted from an earlier x-ray diffraction study, the hydrogen atoms bridge three faces of the Ni/sub 4/ tetrahedral core. Although the Ni/sub 4/ cluster itself is an essentially undistorted tetrahedron (with Ni-Ni edges of 2.469 (6) A), the individual Ni/sub 3/H linkages are unsymmetrical. The H atoms are slightly displaced away from the unique apical Ni atom: Ni-H distances involving the apical Ni atom average to 1.716 (3) A, while those involving the basal Ni atoms average to 1.678 (6) A. The overall mean Ni-H distance is 1.691 (8) A, and the H atoms are situated an average of 0.907 (6) A above the Ni/sub 3/ faces. Other average distances and angles in the molecule follow: H-H = 2.316 (6) A, Ni-C = 2.132 (5) A, Ni-H-Ni = 93.9 (3)/sup 0/, H-Ni-H = 86.1 (6)/sup 0/. The title compound crystallizes in space group C2/c with the following cell parameters at 81 K: a = 28.312 (13) A, b = 9.234 (5) A, c = 14.783 (7) A, BETA =more » 103.35 (2)/sup 0/, V = 3760 (3) A/sup 3/, Z = 8. The structure has been refined to yield final agreement factors of R/sub f/ reverse arrow 0.107 and R/sub wf/ = 0.067 for 2616 reflections having I > 1.5 sigma (I). (5 tables, 4 figures)« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Univ. of Southern California, Los Angeles
OSTI Identifier:
5844278
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Am. Chem. Soc.; (United States); Journal Volume: 101:19
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ORGANOMETALLIC COMPOUNDS; STRUCTURAL CHEMICAL ANALYSIS; HYDROGEN; LOW TEMPERATURE; METALS; NEUTRON DIFFRACTION; NICKEL; NICKEL COMPOUNDS; COHERENT SCATTERING; CRYOGENIC FLUIDS; DIFFRACTION; ELEMENTS; FLUIDS; NONMETALS; ORGANIC COMPOUNDS; SCATTERING; TRANSITION ELEMENT COMPOUNDS; TRANSITION ELEMENTS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Koetzle, T.F., Muller, J., Tipton, D.L., Hart, D.W., and Bau, R. Neutron diffraction analysis of the structure of H/sub 3/Ni/sub 4/(C/sub 5/H/sub 5/)/sub 4/. United States: N. p., 1979. Web. doi:10.1021/ja00513a030.
Koetzle, T.F., Muller, J., Tipton, D.L., Hart, D.W., & Bau, R. Neutron diffraction analysis of the structure of H/sub 3/Ni/sub 4/(C/sub 5/H/sub 5/)/sub 4/. United States. doi:10.1021/ja00513a030.
Koetzle, T.F., Muller, J., Tipton, D.L., Hart, D.W., and Bau, R. Wed . "Neutron diffraction analysis of the structure of H/sub 3/Ni/sub 4/(C/sub 5/H/sub 5/)/sub 4/". United States. doi:10.1021/ja00513a030.
@article{osti_5844278,
title = {Neutron diffraction analysis of the structure of H/sub 3/Ni/sub 4/(C/sub 5/H/sub 5/)/sub 4/},
author = {Koetzle, T.F. and Muller, J. and Tipton, D.L. and Hart, D.W. and Bau, R.},
abstractNote = {The structure of H/sub 3/Ni/sub 4/Cp/sub 4/ (Cp=n/sup 5/-C/sub 5/H/sub 5/), an unusual paramagnetic metal cluster complex, has been analyzed by single-crystal neutron diffraction techniques at low temperature (81 K). As predicted from an earlier x-ray diffraction study, the hydrogen atoms bridge three faces of the Ni/sub 4/ tetrahedral core. Although the Ni/sub 4/ cluster itself is an essentially undistorted tetrahedron (with Ni-Ni edges of 2.469 (6) A), the individual Ni/sub 3/H linkages are unsymmetrical. The H atoms are slightly displaced away from the unique apical Ni atom: Ni-H distances involving the apical Ni atom average to 1.716 (3) A, while those involving the basal Ni atoms average to 1.678 (6) A. The overall mean Ni-H distance is 1.691 (8) A, and the H atoms are situated an average of 0.907 (6) A above the Ni/sub 3/ faces. Other average distances and angles in the molecule follow: H-H = 2.316 (6) A, Ni-C = 2.132 (5) A, Ni-H-Ni = 93.9 (3)/sup 0/, H-Ni-H = 86.1 (6)/sup 0/. The title compound crystallizes in space group C2/c with the following cell parameters at 81 K: a = 28.312 (13) A, b = 9.234 (5) A, c = 14.783 (7) A, BETA = 103.35 (2)/sup 0/, V = 3760 (3) A/sup 3/, Z = 8. The structure has been refined to yield final agreement factors of R/sub f/ reverse arrow 0.107 and R/sub wf/ = 0.067 for 2616 reflections having I > 1.5 sigma (I). (5 tables, 4 figures)},
doi = {10.1021/ja00513a030},
journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 101:19,
place = {United States},
year = {Wed Sep 12 00:00:00 EDT 1979},
month = {Wed Sep 12 00:00:00 EDT 1979}
}