Inorg. Chem. 1999, 38, 3435-3438
3435
Notes
Table 1. Cell Parameters for M3M′3Sb4 (M ) Zr, Hf; M′ ) Ni, Pt)
M3Ni3Sb4 (M ) Zr, Hf) and Zr3Pt3Sb4. Ternary
Antimonides with the Y3Au3Sb4 Structure
compd
a (Å)
V (Å3)
Zr3Ni3Sb4
Hf3Ni3Sb4
Zr3Pt3Sb4
9.066(2)
9.016(1)
9.359(1)
745.1(4)
732.8(4)
819.8(4)
Meitian Wang, Robert McDonald,† and Arthur Mar*
Department of Chemistry, University of Alberta, Edmonton,
Alberta, Canada T6G 2G2
Table 2. Crystallographic Data for Zr3Ni3Sb4
T6d-I4h3d (No. 220)
λ ) 0.710 73 Å
ReceiVed February 3, 1999
Zr3Ni3Sb4
fw 936.79
a ) 9.0617(6) Åa
V ) 744.10(9) Å3 a
Z ) 4
Fcalcd ) 8.362 g cm-3
Introduction
µ(Mo KR) ) 255.9 cm-1
R(F) for Fo2 > 2σ(Fo )b ) 0.027
2
Although Y3Au3Sb4 was identified more than two decades
ago,1 its claim to fame lies in serving as the structure type
adopted by many ternary pnictides M3M′3Pn4 (Pn ) As, Sb,
Bi) and a few stannides M3M′3Sn4 which have been the object
of recent intense scrutiny because of their interesting electronic
properties. The known compounds in this family generally
consist of M ) f-element and M′ ) late transition metal (groups
9-11): U3M′3Sb4 (M′ ) Co, Rh, Ir),2,3 U3Ni3-xAs4,4 M3Ni3-
Sb4 (M ) U, Th),2,3,5 M3Ni3Sn4 (M ) U, Th),5-7 U3Pd3Sb4,2,5
M3Pt3Sb4 (M ) Ce-Nd, U),2,5,8-10 M3Pt3Bi4 (M ) La, Ce),11-13
U3Pt3Sn4,5 M3Cu3Sb4 (M ) Y, La-Nd, Sm, Gd-Er, U),5,14-17
U3Cu3Sn4,5 M3Au3Sb4 (M ) Y, La-Nd, Sm, Gd-Lu),1,8,9,18
and U3Au3Sn4.5 Some of these have been found to be Kondo
insulators,8-13 superconductors,7 magnetoresistive materials,13
and thermoelectric materials,10,16 the properties originating from
the f-electrons of the M component. Since doping is a common
strategy for modifying electronic properties, the occurrence of
isostructural compounds expands the range in which this is
possible. We report here the preparation of Zr3Ni3Sb4, Hf3Ni3-
2
T ) 22 °C
Rw(Fo )c ) 0.065
a Based on 24 centered reflections in the range 16° e 2θ(Mo KR)
e 32° and obtained from a refinement constrained so that a ) b ) c
and R ) â ) γ ) 90°. a R(F) ) ∑||Fo| - |Fc||/∑|Fo|. b Rw(Fo ) )
2
2
4
2
[∑[w(Fo - Fc2)2/∑wFo ]1/2; w-1 ) [σ2(Fo ) + 6.72p] where p )
2
[max(Fo ,0) + 2Fc2]/3.
Sb4, and Zr3Pt3Sb4, which represent the first members of this
structural family that do not contain an f-element or Y for the
M component.
Experimental Section
Synthesis. Reactions were carried out on a ∼0.25-g scale by arc-
melting mixtures of the elemental powders (Zr, 99.7%; Hf, 99.8%; Ni,
99.9%; Pt, 99.9%; all from Cerac) pressed into pellets. Each pellet was
melted twice in a Centorr 5TA tri-arc furnace under argon (gettered
by melting a titanium pellet) at slightly greater than atmospheric
pressure. Single crystals of Zr3Ni3Sb4 were originally found after arc-
melting a mixture of Zr, Ni, and Sb in a 1:2:4.5 ratio and annealing in
a Ta tube at 1000 °C for 5 days. EDX (energy-dispersive X-ray) analysis
of these black block-shaped crystals on a Hitachi F2700 scanning
electron microscope confirmed the presence of all three elements in
roughly the expected proportions (23(2)% Zr, 34(2)% Ni, 43(2)% Sb).
The X-ray powder patterns, obtained on an Enraf-Nonius FR552 Guinier
camera (Cu KR1 radiation; Si standard), revealed the presence of Zr3-
Ni3Sb4 as well as NiSb and Sb. A single crystal from this reaction was
used for the structure determination described below.
Subsequently Zr3Ni3Sb4, Hf3Ni3Sb4, and Zr3Pt3Sb4 could be prepared
by arc-melting mixtures of the elements in stoichiometric proportions,
with 2% excess Sb added to compensate for the weight loss suffered
as a result of slight vaporization of Sb (2-4%). We were unable to
prepare Hf3Pt3Sb4, nor were we successful in substituting M ) Nb, Ta
or M′ ) Co, Pd under these conditions. The cell parameters refined
with the use of the program POLSQ19 are listed in Table 1.
Structure Determination. Intensity data were collected at room
temperature with the θ-2θ scan technique in the range 11° e 2θ(Mo
KR) e 70° on an Enraf-Nonius CAD-4 diffractometer. Crystal data
and further details of the data collection are given in Table 2 and the
CIF. Calculations were carried out with the use of the SHELXTL
(Version 5.1) package.20 Conventional atomic scattering factors and
anomalous dispersion corrections were used.21 Intensity data were
processed and face-indexed absorption corrections were applied in
XPREP. The unique space group consistent with the cubic symmetry
† Faculty Service Officer, Structure Determination Laboratory.
(1) Dwight, A. E. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst.
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(2) Dwight, A. E. J. Nucl. Mater. 1979, 79, 417.
(3) Buschow, K. H. J.; de Mooij, D. B.; Palstra, T. T. M.; Nieuwenhuys,
G. J.; Mydosh, J. A. Philips J. Res. 1985, 40, 313.
(4) Troc, R.; Kaczorowski, D.; Noe¨l, H.; Guerin, R. J. Less-Common Met.
1990, 157, L1.
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T.; Sakurai, J.; Hiraoka, T. J. Phys. Soc. Jpn. 1990, 59, 4412.
(6) Yethiraj, M.; Robinson, R. A.; Rhyne, J. J.; Gotaas, J. A.; Buschow,
K. H. J. J. Magn. Magn. Mater. 1989, 79, 355.
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(19) POLSQ: Program for least-squares unit cell refinement. Modified by
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(20) Sheldrick, G. M. SHELXTL, version 5.1; Bruker Analytical X-ray
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10.1021/ic990144i CCC: $18.00 © 1999 American Chemical Society
Published on Web 06/24/1999