From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries
Abstract
Here the Pt–Pr phase diagram has been explored well, recent work on rare-earth metal cluster halides with endohedral transition metal atoms has provided a new binary intermetallic that is nonexistent in the known phase diagram: The binary Pt3Pr4 (1) crystallizes in a new structure type (mP56, P21/c, a = 12.353(2) Å, b = 7.4837(9) Å, c = 17.279(2) Å, β = 118.003(7)°, Z = 8) with six crystallographically independent Pt as well as eight Pr positions. The subsequent detailed investigation has led to another previously unreported, binary phase with the Ga2Gd3 structure type, Pt2–xPr3 (2, tI80, I4/mcm, a = 11.931(9) Å, c = 14.45(1) Å, Z = 16), that is practically overlapping with the rhombohedral Pt2Pr3 existing in the phase diagram. Application of different tin containing fluxes to reproduce the newly detected phases brought about two almost iso-compositional ternary compounds with Sn, Pt4Sn6Pr2.91 (3), and Pt4Sn6Pr3 (4), as well as Pt12Sn24Pr4.84 (5). 3 is a representative of the Pt4Ge6Ce3 type (oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(2) Å), while 4 represents a new variant of the prolific T4E6R3 family (T = transition metal, E = main group (semi)metal, R = rare-earth metal; Pt4Sn6Pr3: oP52, Pnma, a = 27.623(1) Å, b = 4.5958(2) Å, c = 9.3499(5) Å). Pt12Sn24Pr5–x (5) crystallizes as a variant of the Ni8Sn16Gd3 type (cI82, Im$$\bar{3}$$, a = 12.274(1) Å, Z = 2). Electronic structure calculations provide hints on the origin of the structural changes (pseudo-polymorphism) for PtxPr3 with x = 1.97 and 2.00, respectively, and reveal that heteroatomic Pt–Pr bonding strongly dominates in both binaries while the addition of the reactive metal tin leads to dominating Pt–Sn bonding interactions in the ternaries; Pt–Pt bonding interactions are strong but represent a minority in the binaries and are not present at all in the ternaries.
- Authors:
-
[3];
[3];
[4]
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Univ. zu Koln, Koln (Germany)
- Ames Lab. and Iowa State Univ., Ames, IA (United States); Stockholm Univ., Stockholm (Sweden)
- Ames Lab. and Iowa State Univ., Ames, IA (United States); Univ. zu Koln, Koln (Germany)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1471222
- Report Number(s):
- IS-J-9752
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 16; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Rhodehouse, Melissa L., Bell, Thomas, Smetana, Volodymyr, Mudring, Anja -Verena, and Meyer, Gerd H. From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.8b01121.
Rhodehouse, Melissa L., Bell, Thomas, Smetana, Volodymyr, Mudring, Anja -Verena, & Meyer, Gerd H. From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries. United States. https://doi.org/10.1021/acs.inorgchem.8b01121
Rhodehouse, Melissa L., Bell, Thomas, Smetana, Volodymyr, Mudring, Anja -Verena, and Meyer, Gerd H. Fri .
"From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries". United States. https://doi.org/10.1021/acs.inorgchem.8b01121. https://www.osti.gov/servlets/purl/1471222.
@article{osti_1471222,
title = {From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2–xPr3 to Pt/Sn/Pr Ternaries},
author = {Rhodehouse, Melissa L. and Bell, Thomas and Smetana, Volodymyr and Mudring, Anja -Verena and Meyer, Gerd H.},
abstractNote = {Here the Pt–Pr phase diagram has been explored well, recent work on rare-earth metal cluster halides with endohedral transition metal atoms has provided a new binary intermetallic that is nonexistent in the known phase diagram: The binary Pt3Pr4 (1) crystallizes in a new structure type (mP56, P21/c, a = 12.353(2) Å, b = 7.4837(9) Å, c = 17.279(2) Å, β = 118.003(7)°, Z = 8) with six crystallographically independent Pt as well as eight Pr positions. The subsequent detailed investigation has led to another previously unreported, binary phase with the Ga2Gd3 structure type, Pt2–xPr3 (2, tI80, I4/mcm, a = 11.931(9) Å, c = 14.45(1) Å, Z = 16), that is practically overlapping with the rhombohedral Pt2Pr3 existing in the phase diagram. Application of different tin containing fluxes to reproduce the newly detected phases brought about two almost iso-compositional ternary compounds with Sn, Pt4Sn6Pr2.91 (3), and Pt4Sn6Pr3 (4), as well as Pt12Sn24Pr4.84 (5). 3 is a representative of the Pt4Ge6Ce3 type (oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(2) Å), while 4 represents a new variant of the prolific T4E6R3 family (T = transition metal, E = main group (semi)metal, R = rare-earth metal; Pt4Sn6Pr3: oP52, Pnma, a = 27.623(1) Å, b = 4.5958(2) Å, c = 9.3499(5) Å). Pt12Sn24Pr5–x (5) crystallizes as a variant of the Ni8Sn16Gd3 type (cI82, Im$\bar{3}$, a = 12.274(1) Å, Z = 2). Electronic structure calculations provide hints on the origin of the structural changes (pseudo-polymorphism) for PtxPr3 with x = 1.97 and 2.00, respectively, and reveal that heteroatomic Pt–Pr bonding strongly dominates in both binaries while the addition of the reactive metal tin leads to dominating Pt–Sn bonding interactions in the ternaries; Pt–Pt bonding interactions are strong but represent a minority in the binaries and are not present at all in the ternaries.},
doi = {10.1021/acs.inorgchem.8b01121},
journal = {Inorganic Chemistry},
number = 16,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 5 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Gadolinium sesquichloride, an unusual example of metal-metal bonding
journal, March 1970
- Lokken, Donald A.; Corbett, John D.
- Journal of the American Chemical Society, Vol. 92, Issue 6
Rare earth metal-metal halide systems. XV. Crystal structure of gadolinium sesquichloride. Phase with unique metal chains
journal, March 1973
- Lokken, Donald A.; Corbett, John D.
- Inorganic Chemistry, Vol. 12, Issue 3
Metallreiche Verbindungen der Seltenen Erden Gd2Cl3, Gd2Br3 und Tb2Cl3
journal, January 1979
- Simon, A.; Holzer, N.; Mattusch, Hj.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 456, Issue 1
Cluster Complexes as anti-Werner Complexes
journal, December 2008
- Meyer, Gerd
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 634, Issue 15
Encapsulation of the platinum and neighboring metals within cluster iodides of rare-earth elements
journal, June 1990
- Payne, Martin W.; Corbett, John D.
- Inorganic Chemistry, Vol. 29, Issue 12
Condensed metal cluster iodides centered by noble metals. Six examples of cubic R3I3Z phases (R = La, Pr; Z = Os, Ir, Pt)
journal, December 1991
- Dorhout, Peter K.; Payne, Martin W.; Corbett, John D.
- Inorganic Chemistry, Vol. 30, Issue 26
Reduced Praseodymium Cluster Bromides Stabilized by Transition Metals
journal, March 1994
- Llusar, Rosa; Corbett, John D.
- Inorganic Chemistry, Vol. 33, Issue 5
An analysis of the ammonium chloride route to anhydrous rare-earth metal chlorides
journal, November 1982
- Meyer, Gerd; Ax, Peter
- Materials Research Bulletin, Vol. 17, Issue 11
Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination
journal, January 2015
- Krause, Lennard; Herbst-Irmer, Regine; Sheldrick, George M.
- Journal of Applied Crystallography, Vol. 48, Issue 1
SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
Crystal structure refinement with SHELXL
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
Explicit, First-Principles Tight-Binding Theory
journal, December 1984
- Andersen, O. K.; Jepsen, O.
- Physical Review Letters, Vol. 53, Issue 27
Minimal basis sets in the linear muffin-tin orbital method: Application to the diamond-structure crystals C, Si, and Ge
journal, August 1986
- Lambrecht, Walter R. L.; Andersen, O. K.
- Physical Review B, Vol. 34, Issue 4
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993
- Dronskowski, Richard; Bloechl, Peter E.
- The Journal of Physical Chemistry, Vol. 97, Issue 33
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
R 3 T 2 compounds ( R = rare earth or Y; T = Rh, Pd, Pt) with the rhombohedral Er 3 Ni 2 structure type
journal, August 1977
- Le Roy, J.; Moreau, J. -M.; Paccard, D.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 33, Issue 8
The Crystal Structure of Two Novel Compounds: CeAlSi2andCe3Al4Si6
journal, December 1996
- Flandorfer, Hans; Rogl, Peter
- Journal of Solid State Chemistry, Vol. 127, Issue 2
Crystal structure of the novel compound Ce3Pt4Al6
journal, January 2008
- Tursina, A. I.; Gribanov, A. V.; Bukhan’Ko, N. G.
- Chemistry of Metals and Alloys, Vol. 1, Issue 1
Crystal structure of the compound Ce3Pt4Ge6
journal, February 1992
- Gribanov, A. V.; Sologub, O. L.; Salamakha, P. S.
- Journal of Alloys and Compounds, Vol. 179, Issue 1-2
The Stannides La 3 Pd 4 Sn 6 , Ce 3 Pd 4 Sn 6 , and Pr 3 Pd 4 Sn 6 : A New Structure Type with a Complex Three-Dimensional [Pd 4 Sn 6 ] Polyanion
journal, February 2000
- Niepmann, Dirk; Pöttgen, Rainer; Künnen, Bernd
- Chemistry of Materials, Vol. 12, Issue 2
Neue Germanide mit geordneter Ce3Pt4Ge6-Struktur – Die VerbindungenLn3Pt4Ge6 (Ln: Pr–Dy)
journal, June 2006
- Imre, Anette; Hellmann, Andrea; Mewis, Albrecht
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 632, Issue 7
Crystal structure of Y3Pt4Ge6: An intergrowth of BaAl4 and YIrGe2 slabs
journal, December 1990
- Venturini, G.; Malaman, B.
- Journal of the Less Common Metals, Vol. 167, Issue 1
Kristallstruktur von Gd3Ga2 und isotypen Verbindungen
journal, January 1986
- Yatsenko, S. P.; Hladyschewsky, R. E.; Sitschewitsch, O. M.
- Journal of the Less Common Metals, Vol. 115, Issue 1
Eight-Coordinate Endohedral Rhenium, Osmium and Iridium Atoms in Rare-Earth Halide Cluster Complexes
journal, May 2010
- Zimmermann, Sina; Brühmann, Matthias; Casper, Frederick
- European Journal of Inorganic Chemistry, Vol. 2010, Issue 18
Electronic and structural properties of the novel chain compound tantalum telluride silicide, Ta4Te4Si
journal, October 1990
- Li, Jing; Hoffmann, Roald; Badding, Michael E.
- Inorganic Chemistry, Vol. 29, Issue 20
{Os5Lu20}I24, the First Extended Cluster Complex of Lutetium with Eight-Coordinate Endohedral Osmium Atoms in Two Different Environments
journal, August 2011
- Brühmann, Matthias; Mudring, Anja-Verena; Valldor, Martin
- European Journal of Inorganic Chemistry, Vol. 2011, Issue 26
R12Pt7In (R=Ce, Pr, Nd, Gd, Ho)—new derivatives of the Gd3Ga2-type
journal, January 2004
- Galadzhun, Ya. V.; Zaremba, V. I.; Kalychak, Ya. M.
- Journal of Solid State Chemistry, Vol. 177, Issue 1
Structure cristalline des composés intermétalliques T 4 Co 3 ( T = Y, Gd, Tb, Dy, Ho, Er et Tm)
journal, April 1969
- Lemaire, R.; Schweizer, J.; Yakinthos, J.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 4
The phase diagram of the La—Rh system
journal, December 1992
- Palenzona, A.
- Journal of Alloys and Compounds, Vol. 190, Issue 1
The alloy systems Ln-Sb
journal, November 1986
- Abdusalyamova, M. N.; Burnashev, O. R.; Mironov, K. Y.
- Journal of the Less Common Metals, Vol. 125
The crystal structure of Ce 4 Ru 3
journal, January 1992
- Fornasini, M. L.; Palenzona, A.
- Zeitschrift für Kristallographie, Vol. 200, Issue 1-2
A ternary alloy with PbCl2-type structure: TiNiSi(E)
journal, May 1965
- Shoemaker, C. B.; Shoemaker, D. P.
- Acta Crystallographica, Vol. 18, Issue 5
Synthesis, Structure and Properties of the High-pressure Modifications of the Ternary Compounds REPtSn (RE = La, Pr, Sm)
journal, December 2006
- Riecken, Jan F.; Rodewald, Ute Ch.; Heymann, Gunter
- Zeitschrift für Naturforschung B, Vol. 61, Issue 12
Gold Polar Intermetallics: Structural Versatility through Exclusive Bonding Motifs
journal, October 2017
- Smetana, Volodymyr; Rhodehouse, Melissa; Meyer, Gerd
- Accounts of Chemical Research, Vol. 50, Issue 11
Four Polyanionic Compounds in the K–Au–Ga System: A Case Study in Exploratory Synthesis and of the Art of Structural Analysis
journal, January 2012
- Smetana, Volodymyr; Corbett, John D.; Miller, Gordon J.
- Inorganic Chemistry, Vol. 51, Issue 3
Three Alkali-Metal–Gold–Gallium Systems. Ternary Tunnel Structures and Some Problems with Poorly Ordered Cations
journal, April 2012
- Smetana, Volodymyr; Miller, Gordon J.; Corbett, John D.
- Inorganic Chemistry, Vol. 51, Issue 14
Near-threshold laser spectroscopy of iridium and platinum negative ions: Electron affinities and the threshold law
journal, December 1999
- Bilodeau, René C.; Scheer, Michael; Haugen, Harold K.
- Physical Review A, Vol. 61, Issue 1
Electron affinity of tin measured by photodetachment microscopy
journal, June 2013
- Vandevraye, M.; Drag, C.; Blondel, C.
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 46, Issue 12
Atomic negative ions: structure, dynamics and collisions
journal, May 2004
- Andersen, T.
- Physics Reports, Vol. 394, Issue 4-5
Electronegativity values from thermochemical data
journal, June 1961
- Allred, A. L.
- Journal of Inorganic and Nuclear Chemistry, Vol. 17, Issue 3-4
Transformation of AeIn 4 Indides (Ae = Ba, Sr) into an AeAu 2 In 2 Structure Type Through Gold Substitution
journal, May 2007
- Dai, Jing-Cao; Corbett, John D.
- Inorganic Chemistry, Vol. 46, Issue 11
Ba 2 AuTl 7 : An Intermetallic Compound with a Novel Condensed Structure
journal, April 2004
- Liu, Shengfeng; Corbett, John D.
- Inorganic Chemistry, Vol. 43, Issue 8
SrAu 4 In 4 and Sr 4 Au 9 In 13 : Polar Intermetallic Structures with Cations in Augmented Hexagonal Prismatic Environments
journal, March 2008
- Palasyuk, Andriy; Dai, Jing-Cao; Corbett, John D.
- Inorganic Chemistry, Vol. 47, Issue 8
Single Crystal X-ray Structure Investigation and Electronic Structure Studies of La-Deficient Nickel Stannide La4.87Ni12Sn24 Grown from Sn Flux
journal, February 2003
- Zhuravleva, Marina A.; Bilc, Daniel; Mahanti, S. D.
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 629, Issue 2
Crystallographic, magnetic and electrical characteristics of some R5−xNi12Sn24+x intermetallics
journal, March 2010
- Romaka, V. V.; Hlil, E. K.; Romaka, L.
- Journal of Alloys and Compounds, Vol. 493, Issue 1-2
Mixed valent stannide EuRuSn3 – Structure, magnetic properties, and Mössbauer spectroscopic investigation
journal, February 2010
- Harmening, Thomas; Hermes, Wilfried; Eul, Matthias
- Solid State Sciences, Vol. 12, Issue 2
R�ntgenographische Untersuchungen im System: Platin-Quecksilber
journal, January 1953
- Bauer, E.; Nowotny, H.; Stempfl, A.
- Monatshefte f�r Chemie, Vol. 84, Issue 4
Cs2Pt: A Platinide(-II) Exhibiting Complete Charge Separation
journal, October 2003
- Karpov, Andrey; Nuss, Jürgen; Wedig, Ulrich
- Angewandte Chemie International Edition, Vol. 42, Issue 39
Cesium Platinide Hydride 4Cs 2 Pt⋅CsH: An Intermetallic Double Salt Featuring Metal Anions
journal, October 2016
- Smetana, Volodymyr; Mudring, Anja-Verena
- Angewandte Chemie International Edition, Vol. 55, Issue 47
Synthesis, Structure, and Bonding Analysis of the Polar Intermetallic Phase Ca 2 Pt 2 Cd
journal, August 2012
- Samal, Saroj L.; Corbett, John D.
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 638, Issue 12-13
Cluster Chemistry in Electron-Poor Ae–Pt–Cd Systems (Ae = Ca, Sr, Ba): (Sr,Ba)Pt 2 Cd 4 , Ca 6 Pt 8 Cd 16 , and Its Known Antitype Er 6 Pd 16 Sb 8
journal, February 2013
- Samal, Saroj L.; Gulo, Fakhili; Corbett, John D.
- Inorganic Chemistry, Vol. 52, Issue 5
Substantial Cd–Cd Bonding in Ca 6 PtCd 11 : A Condensed Intermetallic Phase Built of Pentagonal Cd 7 and Rectangular Cd 4/2 Pt Pyramids
journal, August 2013
- Gulo, Fakhili; Samal, Saroj L.; Corbett, John D.
- Inorganic Chemistry, Vol. 52, Issue 17
Gold in the Layered Structures of R 3 Au 7 Sn 3 : From Relativity to Versatility
journal, September 2016
- Provino, Alessia; Steinberg, Simon; Smetana, Volodymyr
- Crystal Growth & Design, Vol. 16, Issue 10
Covalent radii revisited
journal, January 2008
- Cordero, Beatriz; Gómez, Verónica; Platero-Prats, Ana E.
- Dalton Transactions, Issue 21
Na8Au9.8(4)Ga7.2 and Na17Au5.87(2)Ga46.63: The diversity of pseudo 5-fold symmetries in the Na–Au–Ga system
journal, November 2013
- Smetana, Volodymyr; Corbett, John D.; Miller, Gordon J.
- Journal of Solid State Chemistry, Vol. 207
Works referencing / citing this record:
Tb 3 Pd 2 , Er 3 Pd 2 and Er 6 Co 5– x : structural variations and bonding in rare-earth-richer binary intermetallics
journal, August 2018
- Bell, Thomas; Celania, Chris R.; Smetana, Volodymyr
- Acta Crystallographica Section C Structural Chemistry, Vol. 74, Issue 9