CRYSTAL STRUCTURE OF THE TmNi5
Сrystal structure of the TmNi5 compound has been investigated by means of X-ray single crystal method (Oxford Diffraction X’calibur four-circle diffractometer, MoKα radiation) for the first time: CaCu5-type structure, Pearson symbol hP6, space group P6/mmm, a = 4.8684(12), c = 3.9541(7) Å, R1 = 0.05...
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| Дата: | 2022 |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465841397071872 |
|---|---|
| author | Belan, Bohdana Dzevenko, Mariya Gladyshevskii, Roman Daszkiewicz, Marek |
| author_facet | Belan, Bohdana Dzevenko, Mariya Gladyshevskii, Roman Daszkiewicz, Marek |
| author_institution_txt_mv | [
{
"author": "Bohdana Belan",
"institution": "Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya St. 6, 79005 Lviv, Ukraine "
},
{
"author": "Mariya Dzevenko",
"institution": "Department of Analytical Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya St. 6, 79005 Lviv, Ukraine "
},
{
"author": "Roman Gladyshevskii",
"institution": "Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya St. 6, 79005 Lviv, Ukraine "
},
{
"author": "Marek Daszkiewicz",
"institution": "Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P. O. Box 1410, 50-950 Wrocław 2, Poland"
}
] |
| author_sort | Belan, Bohdana |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:49Z |
| description | Сrystal structure of the TmNi5 compound has been investigated by means of X-ray single crystal method (Oxford Diffraction X’calibur four-circle diffractometer, MoKα radiation) for the first time: CaCu5-type structure, Pearson symbol hP6, space group P6/mmm, a = 4.8684(12), c = 3.9541(7) Å, R1 = 0.0529, wR2 = 0.1835 for 80 reflections. Similarly to intermetallic compounds with high transition metal content, atoms in the title structure have rather high coordination numbers: 20 for thulium and 12 for nickel. |
| doi_str_mv | 10.33609/2708-129X.88.06.2022.121-126 |
| first_indexed | 2025-09-24T17:43:45Z |
| format | Article |
| fulltext |
121
UDC 548.736.4+546.669:546.747:546.28 doi: 10.33609/2708-129X.88.06.2022.121-126
CRYSTAL STRUCTURE OF THE TmNi5
Bohdana Belan1, Marek Daszkiewicz2, Mariya Dzevenko3, Roman Gladyshevskii1
Department of Inorganic Chemistry,
1Ivan Franko National University of L’viv, Kyryla and Mefodia Str. 6,
79005 L’viv, Ukraine
2Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
P. O. Box 1410, 50-950 Wrocław 2, Poland
3Kruty Heroes Lviv Lyceum with Intensive Military and Physical Training,
Pasichna Str. 68, 79038 L’viv, Ukraine
*e-mail: bohdanabelan@gmail.com
Сrystal structure of the TmNi5 compound has been investigated by means of X-ray
single crystal method (Oxford Diffraction X’calibur four-circle diffractometer, MoKα radia-
tion) for the first time: CaCu5-type structure, Pearson symbol hP6, space group P6/mmm,
a = 4.8684(12), c = 3.9541(7) Å, R1 = 0.0529, wR2 = 0.1835 for 80 reflections. Similarly to
intermetallic compounds with high transition metal content, atoms in the title structure have
rather high coordination numbers: 20 for thulium and 12 for nickel.
Key words: thulium, nickel, crystal structure, single crystal method.
INTRODUCTION. The most efficient me
thod of new compound discovering is the com-
plex investigation of component interaction in
ternary system and construction the isother-
mal section. Such investigations always start
from the study the binary systems bounding
the investigated ternary system. So far as, the
character of component interactions in bound-
ing binary systems have a great influence on
interaction in ternary system. As it is shown by
our research group systematic research of the
phase relations and the crystal chemistry in
the ternary systems with rare earth, transition
metal and silicon the great influence have the
binary RE-T system (RE – rare earth metals,
T – transition metal). Unfortunately, these bi-
nary systems have not yet been fully investigat-
ed and crystal structure not of all binary com-
pounds have been determined. Good example
of this is the Tm-Ni system, where compound
TmNi5 with the CaCu5-type structure exist
[1–5]. However, according to the literature
data, a detailed study of the crystal structure
of this compound has not previously been per-
formed. Therefore, we present the results of the
complete crystal structure investigation of the
TmNi5 compound.
EXPERIMENT AND DISCUSSION OF THE
RESULTS. Starting materials for the prepa-
ration of the alloys were ingots of the thuli-
um and nickel with nominal purities Tm ≥
99.88 wt.%, and Ni ≥ 99.99 wt.%. The samples
122 ISSN 2708-129X. Укр. хім. журн., 2022
CRYSTAL STRUCTURE OF THE TmNi5INORGANIC CHEMISTRY
were synthesized by arc-melting under a puri-
fied argon atmosphere, using Ti as a getter and
a tungsten electrode. To achieve high efficien-
cy of the interaction between the components,
the sample was melted twice. The ingot was
annealed at 600°C in an evacuated quartz am-
poule for 720 h and subsequently quenched in
cold water. The weight loss during the prepara-
tion of the sample was less than 1 % of the total
mass, which was 2 g. After annealing no reac-
tion with quartz was observed and the irregu-
larly shaped single crystals were grown on the
surface of the specimen. Single crystals exhibit
metallic lustre while ground powders are grey.
The crystal structures of the TmNi5 com-
pound were investigated by X-ray single-crys-
tal diffraction. X-ray diffraction was performed
at room temperature on an Oxford Diffraction
X’calibur four-circle diffractometer (MoKα ra-
diation). The structures were solved by direct
methods and refined by the SHELX-2018/3
program package [6] with anisotropic atomic
displacement parameters. The crystallograph-
ic data and details on the data collection for
TmNi5 are listed in Table 1. The final atomic
positional and displacement parameters of the
compounds are listed in the Table 2. All the
crystallographic positions are fully occupied.
Table 1
Crystal data and structure refinement details for TmNi5.
Empirical formula TmNi5
Formula weight 462
T, K 295(2)
Space group P6/mmm
Pearson code hP6
Unit cell dimensions, Å a = 4.8684(12), c = 3.9541(7)
Volume, Å3 81.16(4)
No. formula units per unit cell 1
Calculated density, g∙cm–3 9.46
Absorption coefficient, mm-1 55.137
F(000), e 209
Crystal color metallic
Crystal size, mm 0.027×0.023×0.018
θ range for data collection 4.795–31.996
Index ranges –6≤h≤7, ±7, ±5
Measured reflections 2395
Independent reflections / Rint 81 / 0.0858
Reflections with I > 2 σ(I) / Rσ 80 / 0.0220
Data / restraints / parameters 81 / 0 / 9
Goodness-of-fit on F2 1.386
Final R1 / wR2 [I > 2 σ(I)] 0.0529 / 0.1835
Final R1 / wR2 (all data) 0.0514 / 0.1827
Largest diff. peak / hole, e Å−3 2.772 / –4.079
123https://ucj.org.ua
Bohdana Belan, Marek Daszkiewicz, Mariya Dzevenko, Roman Gladyshevskii UCJ № 6 / Vol. 88
Table 2
Atomic coordinates and thermal displacement parameters for TmNi5.
Atom Wyckoff Site x y z Ueq, Å
2
Tm 1a 0 0 0 0.0194(12)
Ni1 2c 2/3 1/3 0 0.0168(14)
Ni2 3g 1/2 0 1/2 0.0265(15)
Atom U11 U22 U33 U12 U13 = U23
Tm 0.0253(13) 0.0253(13) 0.0076(14) 0.0126(7) 0
Ni1 0.0239(19) 0.0239(19) 0.003(2) 0.0119(9) 0
Ni2 0.038(2) 0.026(3) 0.012(2) 0.0132(13) 0
Interatomic distances (δ), reduced values
of interatomic distances (Δ = 100(d − ∑r)/ ∑r,
where ∑r is the sum of the respective atomic
radii) and coordination numbers of atoms for
TmNi5 are listed in Table 3. Most of interatomic
distances in the structure of our compound are
in good agreement with the atomic sizes. The
Tm-Ni1 and Ni1-Ni2 interatomic distances are
rather short in comparison with the sum of the
respective atomic radii.
Table 3
Interatomic distances (d, Å), Δ values and coordination numbers of the atoms
for TmNi5 (rTm = 1.746 Å, rNi = 1.246 Å [8]).
Atom d (Å) Δ (%) CN Atom d (Å) Δ (%) CN
Tm 6 Ni1 2.8107(7) -6.0 18 Ni2 4 Ni1 2.4257(4) -2.7 12
12 Ni2 3.1359(5) 4.8 4 Ni2 2.4342(6) -2.3
4 Tm 3.1359(5) 4.8
Ni1 6 Ni2 2.4257(4) -2.7 12
3 Ni1 2.8107(7) 12.8
3 Tm 2.8107(7) -6.0
The projection of the crystal structure of
TmNi5 on the ab plane and the coordina-
tion polyhedra (CP) of the atoms are shown
in Fig. 1. All CP are typical for the structure
of compounds with CaCu5-type structure.
The coordination polyhedron of the thulium
atoms [Tm(Ni16Ni212)] is hexagonal prism
with Ni-capped lateral sides. The Ni1 atom
is surrounded by 12-vertices polyhedron
[Ni1(Ni26Ni13Tm3)]. The Ni2 atoms are loca
ted inside the icosahedra [Ni2(Ni14Ni24Tm4)].
124 ISSN 2708-129X. Укр. хім. журн., 2022
CRYSTAL STRUCTURE OF THE TmNi5INORGANIC CHEMISTRY
The structure of TmNi5 compound (Fig. 2)
can be considered as a packing of trigonal bypi
ramids from nickel atoms which are connected
by common apexes along the c direction and in
the bc plane. Six such bypiramids build up ring
units, which in turn form a hexagonal atomic
network. Tm atoms fill holes in the hexagonal
rings.
Fig. 2. The hexagonal rings of trigonal bypira-
mids in the TmNi5 structure.
Binary RENi5 compounds with CaCu5-type
exist in all the systems with rare-earth metals
and nickel [7]. Fig.3 displays variations of the
linear parameter (V/N) (where V is a volume
of the unit cell, N is a number of atoms per unit
cell) depending on the size of the RE3+ ion (ac-
cording to Shannon [9]) for the series of the
isostructural compounds. The trend observed
confirms the effect of the lanthanide contrac-
tion.
Fig. 3. Dependence of the parameter (V/N) on
RE3+ radii in the RENi5 compounds.
Fig. 1. A projection of the TmNi5 unit cell on the ab plane and a view of the coordination polyhedra
of the atoms.
125https://ucj.org.ua
Bohdana Belan, Marek Daszkiewicz, Mariya Dzevenko, Roman Gladyshevskii UCJ № 6 / Vol. 88
CONCLUSIONS. The crystal structure of
binary TmNi5 have been investigated in detail
using single crystal X-ray data for the first time.
This compound is isotypical to CaCu5-type
structure. All three crystallographic positions
(1a, 2c and 3g) are fully occupied by Tm and Ni
respectively. The coordination polyhedral are
typical for rare earth binary compounds with
high content of nickel.
ACKNOWLEDGMENTS. This study
was performed under the project
“New substances, materials, types of
matter and approaches to energy saving and
environmental protection”, state registration
number: 0121U113567 (21-01-2022).
КРИСТАЛІЧНА СТРУКТУРА СПОЛУКИ TmNi5
Б. Белан1*, М. Дашкевич2, М. Дзевенко3,
Р. Гладишевський1
1Львівський національний університет іме-
ні Івана Франка, вул. Кирила і Мефодія, 6,
Львів 79005, Україна
2Інститут низькотемпературних і струк-
турних досліджень, Польська академія наук,
П. О. Бокс 1410, Вроцлав 2, 50-950, Польща
3Львівський ліцей з посиленою військово-фі-
зичною підготовкою імені Героїв Крут, ву-
лиця Пасічна, 68, Львів 79000, Україна
*е-mail: bohdanabelan@gmail.com
Із літератури відомо про існування
сполуки складу TmNi5 у подвійній систе-
мі Tm-Ni. Однак детального дослідження
кристалічної структури цієї сполуки досі
не проводили. Оскільки нам вдалося от-
римати монокристал, ми вперше провели
повне дослідження кристалічної структури
сполуки TmNi5. Зразок синтезовано мето-
дом електродугового плавлення. Моно
кристал відібрано зі зразка, відпаленого
за температури 600 °C упродовж 720 год.
Масив експериментальних інтенсивностей
відбить отримано на автоматичному моно
кристальному дифрактометрі X’calibur fo
ur-circle Oxford Diffraction (MoKα промін-
ня). Структуру визначено прямими ме-
тодами за допомогою комплексу програм
SHELX-2018/3. Параметри теплового змі-
щення всіх атомів уточнено в анізотропно-
му наближенні. Сполука кристалізується в
структурному типу CaCu5, символ Пірсо-
на символ hP6, просторова група P6/mmm
(№ 191), a = 4,8684(12), c = 3,9541(7) Å,
R = 0,0529, wR = 0,1835 для 80 рефлексів. Усі
кристалографічні позиції в структурі до-
сліджуваної сполуки зайнято повністю.
Міжатомні віддалі у структурі сполуки
TmNi5 добре узгоджуються із сумами атом-
них радіусів компонентів. Атоми тулію ха-
рактеризуються координаційним числом
20, а менші за розміром атоми нікелю – 12.
Координаційні поліедри атомів у структурі
сполуки TmNi5 є типовими для представ-
ників структурного типу CaCu5. Коорди-
наційними багатогранниками атомів тулію
[Tm(Ni16Ni212)] є гексагональні призми з
бічними сторонами, центрованими атома-
ми нікелю. Координаційними багатогран-
никами для атомів Нікелю є: 12-вершинни-
ки [Ni1(Ni26Ni13Tm3)] для атомів Ni1 та іко-
саедри [Ni2(Ni14Ni24Tm4)] для атомів Ni2.
Структуру сполуки TmNi5 можна пред-
ставити як укладку тригональних біпіра-
мід з атомів нікелю, які з’єднані по-шість
спільними гранями вздовж напрямку c та в
126 ISSN 2708-129X. Укр. хім. журн., 2022
CRYSTAL STRUCTURE OF THE TmNi5INORGANIC CHEMISTRY
площині bc. Простір між біпірамідами за-
повнений атомами тулію.
Бінарні сполуки складу RENi5 з типом
структури CaCu5 існують у подвійних сис
темах RE-Ni з усіма рідкісноземельними
металами.
Ключові слова: тулій, нікель, кристаліч-
на структура, метод монокристалу.
REFERENCES
1. Krypyakevych P.I, Gladyshevskii E.I. The
compounds EuNi5, TuNi5 and LuNi5 and
their crystal structures. Dopov. Akad. Nauk
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2. Bayanov A.P. Enthalpies of formation of
compounds of the rare earth elements,
calculated on the basis of their crystal che
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3. Rykhal' R.M., Zarechnyuk O.S., Protasov
V.S., Romaka V.A. Isothermal sections of
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systems in the range of 0-0.333 atomic
parts of rare-earth metals at 1070 K. Do-
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4. Vasilechko L.O., Grin Y.M., Yarmolyuk
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of the Tm-Ni-Ge System at 670 K and 870
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6. Sheldrick G.M. Crystal Structure Refine-
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4218
7. Villars P., Cenzual K., Eds. Pearson’s Crys-
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01551
Стаття надійшла 22.07.2022.
|
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| institution | Ukrainian Chemistry Journal |
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| last_indexed | 2026-07-23T01:08:26Z |
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| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
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| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4592026-07-22T08:23:49Z CRYSTAL STRUCTURE OF THE TmNi5 Belan, Bohdana Dzevenko, Mariya Gladyshevskii, Roman Daszkiewicz, Marek thulium, nickel, crystal structure, single crystal method. Сrystal structure of the TmNi5 compound has been investigated by means of X-ray single crystal method (Oxford Diffraction X’calibur four-circle diffractometer, MoKα radiation) for the first time: CaCu5-type structure, Pearson symbol hP6, space group P6/mmm, a = 4.8684(12), c = 3.9541(7) Å, R1 = 0.0529, wR2 = 0.1835 for 80 reflections. Similarly to intermetallic compounds with high transition metal content, atoms in the title structure have rather high coordination numbers: 20 for thulium and 12 for nickel. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-07-27 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/459 10.33609/2708-129X.88.06.2022.121-126 Ukrainian Chemistry Journal; Vol. 88 No. 6 (2022): Ukrainian Chemistry Journal; 121-126 Украинский химический журнал; ##issue.vol## 88 ##issue.no## 6 (2022): Ukrainian Chemistry Journal; 121-126 Український хімічний журнал; Том 88 № 6 (2022): Український хімічний журнал; 121-126 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/459/235 Copyright (c) 2022 Bohdana Belan, Mariya Dzevenko, Roman Gladyshevskii, Marek Daszkiewicz https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Belan, Bohdana Dzevenko, Mariya Gladyshevskii, Roman Daszkiewicz, Marek CRYSTAL STRUCTURE OF THE TmNi5 |
| title | CRYSTAL STRUCTURE OF THE TmNi5 |
| title_full | CRYSTAL STRUCTURE OF THE TmNi5 |
| title_fullStr | CRYSTAL STRUCTURE OF THE TmNi5 |
| title_full_unstemmed | CRYSTAL STRUCTURE OF THE TmNi5 |
| title_short | CRYSTAL STRUCTURE OF THE TmNi5 |
| title_sort | crystal structure of the tmni5 |
| topic_facet | thulium nickel crystal structure single crystal method. |
| url | https://ucj.org.ua/index.php/journal/article/view/459 |
| work_keys_str_mv | AT belanbohdana crystalstructureofthetmni5 AT dzevenkomariya crystalstructureofthetmni5 AT gladyshevskiiroman crystalstructureofthetmni5 AT daszkiewiczmarek crystalstructureofthetmni5 |