236
L. Romaka et al. / Journal of Alloys and Compounds 470 (2009) 233–236
Table 8
X-ray analysis shows the formation of ZrxNi1−xSb substitutional
Crystal data and structure refinement for Zr5Ni0.9Sb3
solid solution based on NiSb binary compound (NiAs-type) up to
about 5 at.% of Zr. The cell parameters change from a = 0.3934 nm,
c = 0.5138 nm (for NiSb) to a = 0.3959(1) nm, c = 0.5141(2) nm (for
Zr5Ni45Sb50 composition).
Formula
Space group
a (nm)
c (nm)
V (nm3)
Z
ꢀcalc (g cm−3
2ꢁ range
No. of reflection
No. of variables
RB, Rp, Rwp
Zr5Ni0.91(2)Sb3
P63/mcm (No. 193)
0.85881(5)
0.58049(3)
0.37078(4)
2
For examination the process of solid solution formation
between Zr5NiSb3 (Hf5CuSn3 structure type) and Zr5Sb3
(Mn5Si3-type) or Zr5Sb4 (Ti5Ga4-type) additional alloys in
the Zr5Sb3–Zr5NiSb3–Zr5Sb4 region were prepared. X-ray phase
analysis of obtained samples showed the existence of solid solution
formed by the nickel insertion into the Zr5Sb3 binary to the final
composition Zr59Ni6Sb35 (a = 0.8429(5) nm, c = 0.5759(5) nm).
Compared with the previously studied Zr–Fe–Sb (four interme-
diate compounds) and Zr–Cu–Sb (three intermediate compounds)
systems, the Zr–Ni–Sb system presents a higher number of com-
pounds. The isostructural compounds only with W5Si3-type appear
in all three systems. On the other hand it worth to note the
close analogy between the crystal structure, stoichiometries of the
ternary phases in the Zr–Fe–Sb and Zr–Ni–Sb systems, especially in
the Zr-rich region.
)
7.831
20◦ ≤ (Cu K␣1) ≤ 100◦
85
22
0.049, 0.097, 0.125
Table 9
Atomic and thermal parameters for Zr5Ni0.9Sb3 compound
Atom
Wyckoff position
x/a
y/b
z/c
Biso × 102 (nm2)
Zr1
Zr2
Nia
Sb
6g
4d
2b
6g
0.2611(3)
1/3
0
0
2/3
0
1/4
0
0
0.73(7)
0.59(7)
0.17(2)
0.50(6)
0.6121(2)
0
1/4
a
Occupation 0.91(2).
References
[1] R.V. Skolozdra, Stannides of Rare Earths and Transition Metals, Svit, Lviv,
Ukraine, 1993, p. 195.
[2] O.A. Avetysan, Y.M. Goryachev, S.B. Kalchenko, R.V. Skolozdra, Y.V. Stadnyk, Ukr.
Phys. J. 36 (1991) 773.
Table 10
Atomic and thermal parameters for Zr3NiSb7 compound
[3] Yu. Stadnyk, Yu. Gorelenko, A. Tkachuk, A. Goryn, V. Davydov, O. Bodak, J. Alloys
Compd. 329 (2001) 37.
[4] A.V. Tkachuk, Y.K. Gorelenko, Y.V. Stadnyk, O.I. Bodak, J. Alloys Compd. 317–318
(2001) 280.
[5] A. Tkachuk, Y. Gorelenko, Y. Stadnyk, B. Padlyak, A. Jankowska-Frydel, O. Bodak,
V. Sechovsky, J. Alloys Compd. 319 (2001) 74.
[6] G. Melnyk, A. Leithe-Jasper, P. Rogl, R. Skolozdra, J. Phase Equilib. 20 (5) (1999)
497.
[7] Y. Stadnyk, L. Romaka, A. Horyn, A. Tkachuk, Y. Gorelenko, P. Rogl, J. Alloys
Compd. 387 (2005) 251.
[8] N.O. Koblyuk, L.P. Romaka, O.I. Bodak, J. Alloys Compd. 309 (2000) 176.
[9] N. Melnychenko, L. Romaka, Yu. Stadnyk, D. Fruchart, O. Bodak, J. Alloys Compd.
352 (2003) 89.
[10] N. Melnychenko-Koblyuk, L. Romaka, L. Akselrud, V.V. Romaka, Y. Stadnyk, J.
[11] T.B. Massalski, Binary Alloy Phase Diagrams, ASM, Metals Park, OH, 1990.
[12] P. Villars, L.D. Calvert, Pearson’s Handbook of Crystallographic Data for Inter-
metallic Phases, ASM, Metals Park, OH, 1991.
Atom
Wyckoff
position
x/a
y/b
z/c
Biso × 102 (nm2)
Zr1
Zr2
Zr3
Ni
Sb1
Sb2
Sb3
Sb4
Sb5
Sb6
Sb7
4c
4c
4c
4c
4c
4c
4c
4c
4c
4c
4c
0.34664(4)
0.37045(4)
0.39237(4)
0.43680(5)
0.02147(3)
0.03748(2)
0.07123(3)
0.09131(3)
0.22833(3)
0.24792(2)
0.28995(3)
1/4
1/4
1/4
1/4
1/4
1/4
1/4
1/4
1/4
0.19076(5)
0.47072(5)
0.90990(5)
0.68908(6)
0.29766(3)
0.07626(3)
0.56057(3)
0.82504(3)
0.35390(3)
0.00788(14)
0.00721(13)
0.00782(14)
0.00903(18)
0.00871(11)
0.00790(10)
0.00977(11)
0.00823(10)
0.00918(11)
0.00875(11)
0.01218(11)
difference X-ray patterns of Zr5Ni0.53Sb2.47 and Zr5Ni0.9Sb3 com-
pounds are shown in Figs. 4 and 5, respectively.
[13] E. Garcia, J.D. Corbett, J. Solid State Chem. 73 (1988) 452.
[14] B. Hunter. LHPM-Rietica, Version 1.7.7, International Union of Crystallography
Commission on Powder Diffraction Newsletter, no. 20 (summer), 1998.
[15] G.M. Sheldrick, SHELXTL Version 5. 1, University of Go¨ttingen, Germany,
1997.
[16] G.A. Melnyk, D. Fruchart, L.P. Romaka, J.V. Stadnyk, R.V. Skolozdra, J. Tobola, J.
Alloys Compd. 267 (1998) L1.
[17] Y.U. Kwon, S.C. Sevov, J.D. Corbett, Chem. Mater. 2 (1990) 550–556.
[18] E. Garcia, H.C. Ku, R.N. Shelton, J.D. Corbett, Solid State Commun. 65 (7) (1988)
757.
The new antimony-rich compound at composition
∼Zr30Ni10Sb60 was found and its crystal structure was solved
by single crystal method. Single crystal used for structure refine-
ment was isolated from a crushed ingot of the annealed Zr27Ni9Sb64
sample. Zr3NiSb7 antimonide crystallizes in the orthorhombic
space group Pnma (Z = 4, a = 1.75165(19) nm, b = 0.39266(4) nm,
c = 1.43968(15) nm), and represents a new structure type. The
refined atomic and thermal parameters are listed in Table 10. The
detailed description and analysis of crystal structure investigation
of Zr3NiSb7 compound will be published in our next manuscript.
[19] H. Kleinke, Z. Anorg, Allg. Chem. 624 (1998) 1272.
[20] M. Wang, R. McDonald, A. Mar, Inorg. Chem. 38 (1999) 3435.
[21] N. Koblyuk, G. Melnyk, L. Romaka, O. Bodak, D. Fruchart, J. Alloys Compd.
317–318 (2001) 284.
[22] J. Soltys, K. Turek, Acta Phys. Pol. Ser. A 47A (3) (1975) 335.