Novel ternary cerium-rich intermetallic compound Ce11Ru3.83In9: Crystal structure and low-temperature physical properties

Accepted Manuscript Novel ternary cerium-rich intermetallic compound Ce11Ru3.83In9: Crystal structure and low-temperature physical properties V. Gribanova, E. Murashova, D. Gnida, Zh. Kurenbaeva, S. Nesterenko, A. Tursina, D. Kaczorowski, A. Gribanov PII:

S0925-8388(17)30957-X

DOI:

10.1016/j.jallcom.2017.03.168

Reference:

JALCOM 41206

To appear in:

Journal of Alloys and Compounds

Received Date: 28 December 2016 Revised Date:

13 March 2017

Accepted Date: 15 March 2017

Please cite this article as: V. Gribanova, E. Murashova, D. Gnida, Z. Kurenbaeva, S. Nesterenko, A. Tursina, D. Kaczorowski, A. Gribanov, Novel ternary cerium-rich intermetallic compound Ce11Ru3.83In9: Crystal structure and low-temperature physical properties, Journal of Alloys and Compounds (2017), doi: 10.1016/j.jallcom.2017.03.168. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Novel Ternary Cerium-Rich Intermetallic Compound Ce11Ru3.83In9: Crystal Structure and Low-Temperature Physical Properties

D. Kaczorowski2, A. Gribanov1 1

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V. Gribanova1*, E. Murashova1, D. Gnida2, Zh. Kurenbaeva1, S. Nesterenko1, A. Tursina1,

Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia 2

Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław, Poland

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Abstract

The formation of a novel intermetallic compound with high content of cerium, Ce11Ru3.83In9, was

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established in a systematic investigation of the Ce-Ru-In ternary system. The crystal structure of this phase was revealed by a single-crystal X-ray diffraction experiment to be of the Nd11Pd4In9type: orthorhombic space group Cmmm, the lattice parameters a=14.9523(10) Å, b=22.0133(15) Å, c=3.8240(2) Å, Z = 2. By means of low-temperature magnetic susceptibility, magnetization, electrical resistivity and magnetoresistivity measurements, Ce11Ru3.83In9 was found to exhibit

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localized magnetism due to trivalent Ce ions, with a ferromagnetic-like long-range ordering below 6.3 K. The likely nature of the magnetic structure is a ferrimagnetic arrangement of the cerium magnetic moments sited in the five independent sublattices in the crystallographic unit cell. The characteristic feature of Ce11Ru3.83In9, reported before also for the isostructural phases

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Ce11Ni4In9 and Ce11Pd4In9, is strong crystalline electric field effect. The novel compound exhibits

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metallic conductivity with some contribution of spin-flip Kondo scattering.

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Corresponding authors: [email protected]

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1. Introduction Since several decades, cerium-based intermetallics have attracted much attention due to variety of their physical properties, which result from the hybridization between cerium 4f

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electrons and conduction electrons. Particular interest has been recently focused on ternary phases from the Ce-T-X systems (T = d-electron transition metal, X = Al, Ga, In, Si, Ge, Sn), being rich in various chemical compositions, specific crystal structures, crystal chemistry peculiarities, and nontrivial physical properties [1].

Until recently, six ternaries have been reported to form in the Ce-Ru-In system: Ce3Ru2In3

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[2], Ce16Ru8In37 [3], Ce2Ru2In3 [4], Ce3Ru2In2 [4], Ce16Ru8+xIn3-x (0
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Ce-Ru interatomic distances being less than the sum of the covalent radii (2.89 Å). No data on the physical properties of these compounds has been reported in the literature up to now. As an outcome of our systematic study on the Ce-Ru-In system, a novel ternary compound with high content of cerium, Ce11Ru3.83In9, has recently been identified [7]. It belongs to a large isotypic series of RE11T4In9 phases (RE = rare earth, T = Ni, Co, Pd), which crystallize with an orthorhombic structure of the Nd11Pd4In9-type [8-13]. In this paper, we report on the

2. Experimental

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2.1. Synthesis

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preparation of Ce11Ru3.83In9, its crystal structure and physical properties.

Polycrystalline sample of Ce11Ru3.83In9 was prepared by arc-melting stoichiometric amounts of the high purity elemental constituents (99.95 wt.% Ce, 99.97 wt.% In, 99.96 wt.%

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Ru) on a water-cooled copper hearth under purified argon atmosphere. To promote homogeneity, the melting was repeated several times with the button turned over between each step. The final weight loss was less than 0.5 wt.%. Subsequently, the alloy was vacuum-sealed in a quartz tube and annealed at 650 °C for 30 days. The heat treatment was finished with quenching in cold water.

2.2. Single crystal X-ray diffraction For the structural studies, a suitable single crystal was picked up from the surface of the 2

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melted alloy. The single-crystal X-ray diffraction (SCXRD) experiment was carried out at 25°C on a Nonius Kappa diffractometer equipped with a CCD (Charge Coupled Device) detector and using graphite monochromated MoKα radiation (λ = 0.71073 Å). The crystal structure was solved by direct methods and then refined by full matrix least-squares on F2 using the SHELX package

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of programs [14]. All the atomic sites were refined in anisotropic approximation and their parameters were standardized with the aid of the program STRUCTURE TIDY [15].

2.3. Powder X-ray diffraction

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The powder X-ray diffraction (PXRD) data were collected at room temperature employing a STOE STADI P transmission diffractometer equipped with a linear position

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sensitive detector (monochromated CuKα1 radiation, λ = 1.54056 Å; 10° ≤ 2θ ≤ 90°, step 0.01°, counting time 10 seconds/point). The lattice parameters were calculated using the STOEWinXpow program package [16]. Quantitative Rietveld refinement of the PXRD pattern was performed with the FULLPROF program [17, 18]. Absorption correction was performed with the program SADABS [19]. As a starting model for the PXRD refinement, the atomic order obtained from the SCXRD experiment was assumed. The crystal structure and coordination polyhedra

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were visualized using the DIAMOND program [20].

2.4. Scanning electron microscopy and energy dispersive X-ray spectroscopy The chemical composition of the prepared sample was controlled on a Carl Zeiss LEO EVO 50VXP scanning electron microscope (SEM) equipped with an Oxford Instruments INCA

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Energy 450 energy dispersive X-ray (EDX) spectrometer. The accuracy of the EDX experiment

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was better than 0.9 at.%.

2.5. Physical measurements

Magnetic measurements were performed in the temperature range 1.72 – 400 K and in

external fields up to 5 T using a Quantum Design SQUID magnetometer. The electrical resistivity was measured over the temperature interval 0.38 – 300 K and in magnetic fields up to 9 T employing a Quantum Design PPMS platform and standard ac four-probe technique.

3. Results and discussion 3

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3.1. Crystal structure The EDX analysis of several spots at the specimen’s surface showed the same composition Ce47.6Ru15.6In36.8 (at.%), which corresponds to the nominal composition Ce11Ru3.83In9. The SEM image (Fig. 1) revealed practically single phase material with trace

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amount of a secondary phase being Ce3Ru2In2 (Ce43.5Ru29.1In27.4). From the Rietveld refinement of the PXRD data, the content of Ce3Ru2In2 was estimated to be less than 5 % of the total mass of the sample.

The SCXRD experiment indicated that Ce11Ru3.83In9 is isostructural to the orthorhombic

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compound Nd11Pd4In9 (space group Cmmm) [8]. Details on the performed measurement and the data analysis are given in Table 1. The refined atomic coordinates and the equivalent

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displacement parameters are listed in Table 2, while the main interatomic distances are gathered in Table 3. Each crystallographic site is occupied by a unique atom sort. The refinement of the occupancy factors revealed that all the sites but that of ruthenium atoms are fully occupied. For the Ru site, the occupation of 0.96(1) was found (nonetheless, in the following, the ideal Ce11Ru4In9 formula will be used for the sake of simplicity). This feature contrasts with the full occupancy of the T site reported for all the other RE11T4In9 phases [8-10].

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The structural model derived from the SCXRD intensities was corroborated by the powder X-ray diffraction experiment. The obtained PXRD pattern is shown in Fig. 2 together with the results of the Rietveld refinement. The calculated lattice parameters: a = 14.886(1) Å, b = 21.877(2) Å, c = 3.8030(3) Å are in satisfactory agreement with those found from the single

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crystal (Table 1).

In the crystal structure of Ce11Ru4In9 there are five independent positions occupied by Ce atoms (Fig. 3). The Ce1, Ce2 and Ce5 atoms are located inside distorted tetragonal prisms with

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two, three and two additional atoms (coordination number CN = 10, 11 and 10), respectively. In turn, the environment of the Ce3 and Ce4 atoms can be described as pentagonal prisms (CN = 10). The Ru atoms are placed inside trigonal prisms made of Ce atoms with additional In atoms centering the lateral sides (CN = 9). The coordination polyhedra of the In1 and In2 atoms are tetragonal prisms with two additional atoms (CN = 10). Finally, the In3 atoms are coordinated with 12 atoms (CN = 12), which form cuboctahedra. The crystal structure of Ce11Ru4In9 may be considered as a three-dimensional framework, made by the Ce atoms. The smaller Ru and In atoms are situated in the voids of the skeleton. The 4

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projection of the unit cell on the (ab) plane is displayed in Fig. 4a. One can easily recognize fragments of the AlB2-type (slightly distorted trigonal prisms) as well as more or less distorted units of the CsCl-type. The Ru atoms fill solely trigonal prisms. All the other voids are centered by In atoms. Similar arrangements of the AlB2- and CsCl-like fragments can be discerned for the

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representatives of homologous series REm+nT2nXm (X = In or B, m and n are numbers of CsCl and AlB2 units, respectively): Cr3AlB4, Mo2FeB2, W2CoB2, Mn2AlB2, o-La2Ni2In, and Lu5Ni2In4 [10]. Alike in all these compounds, the entire space in the crystal structure of Ce11Ru4In9 can be filled with the truncated polyhedra of the smaller atoms In1, In2, In3 and Ru.

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In the crystal structures of intermetallics with high contents of T and X elements, RE atoms are usually located inside the voids of the basic framework, which consists of smaller T

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and X atoms. In contrast, for the Ce-rich intermetallic under consideration, the formation of a basic skeleton with the large Ce atoms may be emphasized as an essential structural feature. Another example of similar formation of the main structural skeleton can be found in Ref. 21 for the recently reported novel Ce-rich stannide Ce13Ru2Sn5. In Fig. 4 we compared both intermetallics. As can be inferred from the figure, the main structural units in both structures are four trigonal prisms connected with a distorted cube through common faces. The trigonal prisms

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are similar to those constituting the AlB2 structure type, while the distorted cubes can be attributed to the CsCl- or W-type in dependence on the type of centering atoms. In Ce11Ru4In9, the trigonal prisms encompass the Ru atoms, while the In atoms are located inside the deformed cubes of the CsCl-type. In Ce13Ru2Sn5, the trigonal prisms are centered by the Sn atoms and the

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distorted cubes are centered with the Ce atoms of which they are constructed, forming the structural units of the W-type. Furthermore, in the case of Ce11Ru4In9, the remaining space in the crystal structure is filled by the distorted tetragonal prisms centered by the In atoms, while in

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Ce13Ru2Sn5, the centering atoms are the Ce, Ru, and In atoms. This way, in the Ce-richer phase Ce13Ru2Sn5, the Ce atoms not only create the basic skeleton but also occupy the voids which may lead to additional deformations and brings about the abnormally short interatomic distances between the Ce and Ru atoms: dCe-Ru = 2.7612, 2.7693 and 2.7925 Å. On the contrary, in the unit cell of Ce11Ru4In9, the shortest Ce-Ru distance is 2.8892(15) Å that is a value close to the sum of the respective atomic radii. Based on the experimental results for the three RE11Co4In9, RE11Ni4In9, and RE11Pd4In9 series with various RE atoms, the authors of Ref. 10 noticed a common relationship between the 5

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unit cell volume and the RE atom radius, namely the larger the RE radius, the greater the cell volume. Another correlation of this type is seen in the RE11T4In9 series with RE = Ce and T = Ni, Ru, Pd: an increase in the atomic radii (rNi (1.246 Å) → rRu (1.34 Å) → rPd (1.376 Å) [22]) is Ni-, Ru- and Pd-bearing phase, respectively).

3.2. Physical properties

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accompanied by an expansion of the unit cell (V = 1247.4(2) Å3 < 1258.7(1) Å3 < 1307(1) Å3 for

The results of magnetic measurements of Ce11Ru4In9 are summarized in Fig. 5. The

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compound is a Curie-Weiss (CW) paramagnet with strongly curvilinear temperature variation of the reciprocal magnetic susceptibility in extended temperature range. The standard description of C , is possible only above 200 K (Fig. 5a), and the leastT −θ

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χ(T) in terms of the CW law, χ (T ) =

squares fitting parameters are C = 8.8605 emu/mol and θ = −185.7 K. Assuming that all the Ce atoms in the unit cell of Ce11Ru4In9 contribute equally to the magnetic properties of the compound, one finds the effective magnetic moment µeff =

8C = 2.54 µB/Ce-atom, i.e. equal to

the Russell-Saunders prediction for free trivalent Ce ion. At the same time, however, the derived

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paramagnetic Curie temperature θ is abnormally large, and hardly explainable for a compound with stable 4f1 electronic state. Below 200 K, χ(T) markedly deviates from the CW law most likely because of strong crystalline electric field (CEF) effect with exceptionally large CEF splitting of the 2F5/2 ground multiplet of the Ce3+ ions. It is worth noting that similar non-linear

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behavior of χ(T) has been found below 200 K for the isostructural compounds Ce11Ni4In9 [11] and Ce11Pd4In9 [23], thus large CEF splitting may be a characteristic feature of all these

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materials.

Alternatively, the χ(T) data can be analyzed in terms of a modified CW (MCW) formula,

χ (T ) = χ 0 +

C , where χ0 accounts for possible temperature-independent contribution due to T −θ

some delocalized f electrons of cerium. Shown in Fig. 5a is the fit of the MCW function to the experimental data above 50 K with the free parameters: C = 4.0709 emu/(K mol), θ = −41.5 K and χ0 = 6.198 x 10-3 emu/mol. In turn, restricting the data evaluation to the temperature range usually considered for Ce intermetallics (T > 100 K) yielded: C = 4.9509 emu/(K mol), θ = −69.4 K and χ0 = 4.778 x 10-3 emu/mol. In both analyzes the negative paramagnetic Curie temperature

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attains a value comparable to those observed for Ce-based Kondo systems with enhanced Kondo temperature of the order of several kelvins. On the other hand, the obtained Curie constants C lead to fairly unrealistic values of the effective magnetic moment (µeff = 1.72 µB/Ce-atom and 1.88 µB/Ce-atom for T > 50 K and T > 100 K, respectively), if all the Ce atoms are assumed to

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contribute equally to the magnetism of Ce11Ru4In9. This finding may give rise to a conjecture that some Ce sites in the unit cell of this compound do not carry localized magnetic moments. Within this scenario, the MCW derived values of the parameter C imply five or six magnetic Ce3+ sites with µeff = 2.54 µB, depending on the temperature range considered (T > 50 K and T > 100 K,

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respectively), with the remaining sites being nonmagnetic (i.e. having a 4f0 ground state and possibly exhibiting valence fluctuations). It should be noted, however, that the crystallochemical

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features of Ce11Ru4In9 do not support such a speculation. As stated in Sec. 3.1, the interatomic distances between Ce atoms and their neighbors have standard values for all five inequivalent Ce sites, thus any deviation from stable Ce3+ state seems unlikely.

As can be inferred from the upper inset to Fig. 5a, Ce11Ru4In9 undergoes a ferromagneticlike phase transition at TC = 6.3 K. The ferromagnetic character of the low-temperature state is corroborated by pronounced bifurcation of the σ(T) curves taken in a weak magnetic field of 0.01

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T upon cooling the specimen in zero and finite magnetic field as well as by the occurrence of clear hysteresis in the σ(H) data below 0.4 T, accompanied by a small remanence of 1.7 emu/g (Fig. 5b). Remarkably, very similar behavior of the low temperature magnetization was found for Ce11Ni4In9 [11] and Ce11Pd4In9 [23], and both compounds were reported as ferromagnets with the

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Curie temperature TC = 16.5 and 18.6 K, respectively. Actually, the ordered state in Ce11Ru4In9 is probably not a simple ferromagnetic

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alignment of the cerium magnetic moments but rather a ferrimagnetic one, as presumed from the characteristic variation of the magnetization measured at 1.75 K as a function of the magnetic field strength (the lower inset to Fig. 5a). The magnetization first rapidly increases with increasing field up to 4 emu/g in µ0H = 1 T, and then varies quasi-linearly reaching 5.6 emu/g in the terminal field of 5 T. The latter value corresponds to the magnetic moment of about 3 µB/f.u. that is µ5T = 0.27 µB per Ce atom, assuming that all the cerium atoms participate in the magnetic ordering. Such a small magnitude of µ5T, being just a minor fraction of the theoretical ordered magnetic moment of the Ce3+ ion (2.14 µB) but also markedly less that the value expected for a ground CEF doublet in Ce-based intermetallics, may be attributed to a complex magnetic 7

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structure with a net ferromagnetic component, formation of which can be promoted by the crystal structure of Ce11Ru4In9 with as many as five nonequivalent sites of the Ce atoms. Shown in Fig. 6a is the temperature variation of the electrical resistivity of Ce11Ru4In9. The compound exhibits metallic-like conductivity, however the magnitude of the resistivity is

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considerably enhanced within the entire temperature range studied (ρ300K = 412 µΩcm, ρ0.38K = 302 µΩcm), and hence the residual resistivity ratio RRR = ρ300K/ρ0.38K is only 1.4. For comparison, for the polycrystalline sample of Ce11Pd4In9 these values are: ρ300K = 114 µΩcm,

ρ0.38K = 1.6 µΩcm, RRR = 71 [23] (no resistivity data have been reported yet for the Ni-bearing

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analog). The large values of ρ(T) may arise from the presence in the specimen studied of some microstructural defects (cracks). Furthermore, to some extent, the resistivity of Ce11Ru4In9 may

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be enhanced due to the existence of the atom vacancies in the unit cell of this compound (see above).

Remarkably, the ρ(T) variation of Ce11Ru4In9 is strongly curvilinear, at odds with the proportionality ρ ~ T expected for simple metals at high enough temperature. Similarly curved

ρ(T) was observed for Ce11Pd4In9 [23], and interpreted as a manifestation of the sizeable CEF effect which accompanies spin-flip Kondo scattering conduction electrons on localized cerium

also for Ce11Ru4In9.

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magnetic moments. In view of the afore-discussed χ(T) data, such a rationale seems appropriate At low temperatures, ρ(T) of Ce11Ru4In9 forms a shallow minimum, which is followed by a drop of the resistivity below TC = 6.3 K. The onset of the magnetic order is associated with an

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inflection on the temperature dependence of the temperature derivative of the resistivity (the inset to Fig. 6a). In magnetic fields applied perpendicular to the electric current, the minimum quickly

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disappears, and the anomaly in ρ(T) marking the magnetic phase transition gradually moves towards higher temperatures with increasing the field strength, as expected for ferro- or ferrimagnets (Fig. 6b). Simultaneously, the magnitude of the resistivity decreases, most significantly in the vicinity of TC, again in a ferromagnetic-like manner. Magnetic field dependence of the transverse magnetoresistance (MR), defined as

∆ρ

ρ

=

ρ (T , H ) − ρ (T , H = 0 ) ∆ρ , is presented in Fig. 7. Below TC, the overall shape of (T) is ρ (T , H = 0) ρ

typical of ferromagnetic metals. As can be inferred from the upper panel of Fig. 7, in magnetic fields µeffH << kBT, MR is approximately proportional to HlnH [24, 25]. In turn, as shown in Fig.

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8, at temperatures (T – TC)/TC >> 1 and in magnetic fields µ0H << TC, MR of Ce11Ru4In9 is proportional to H2 and obeys the scaling relation [23]:

 H2 = f  T −T* ρ 

∆ρ

(

)

2

  with the parameter T* = 9.5 K, which is fairly close to the Curie  

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temperature obtained from the magnetic data. Some discrepancy between T* and TC may be related to the Kondo screening interactions, which possibly possess in Ce11Ru4In9 a similar

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magnitude to that in Ce11Pd4In9 [23].

4. Conclusions

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The new intermetallic compound Ce11Ru4In9 has a crystal structure of the Nd11Pd4In9-type with five independent crystallographic cerium sites in the unit cell. All the Ce ions possess a 4f1 electronic configuration that gives rise to the local-moment magnetism. The compound orders magnetically at TC = 6.3 K with a complex magnetic structure bearing a sizable ferromagnetic component. In the paramagnetic state, the magnetic and electrical transport properties of

Acknowledgments

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Ce11Ru4In9 are influenced by enormously strong crystalline electric field effect.

This work was financially supported by the Russian Foundation for Basic Research (RFBR)

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under grant No. 15-03-04434a. The X-ray part of this research was supported by the Russian Ministry of Science and Education, grant No. RFMEFI61616X0069. The authors acknowledge

3313.

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the European Synchrotron Radiation Facility for access to the ID22 station, experiment MA-

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Figure captions Fig. 1. Local SEM-images of the prepared alloy (marked are points and areas measured by EDX. Points 1, 2 - Ce3Ru2In2.; points 3, 4, 5 - Ce11Ru3.83In9).

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Fig. 2. Experimental powder diffraction pattern (red circles), calculated diffraction pattern (black solid line), and the difference curve (bottom line) for Ce11Ru4In9 analyzed in terms of Rietveld refinement. 1 – Bragg positions of Ce11Ru4In9; 2 – Bragg positions of Ce3Ru2In2.

Fig. 3. Coordination polyhedra of the atoms Ce1–Ce5 (white), Ru (red), and In1–In3 (green) in

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the crystal structure of Ce11Ru4In9.

Fig. 4. Packing of trigonal prisms, distorted tetragonal prisms and distorted cubes in the crystal

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structures of Ce11Ru4In9 (a) and Ce13Ru2Sn5 (b), visualized as a combination of the AlB2- and CsCl-type fragments.

Fig. 5. (a) Temperature dependence of the reciprocal magnetic susceptibility of Ce11Ru4In9. Solid and dashed lines represent the CW and MCW fits, respectively, as described in the text. Upper inset: low-temperature magnetization data measured in a magnetic field 0f 0.1 T. Lower inset:

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field variation of the magnetization taken at 1.72 K with increasing (full circles) and decreasing (open circles) magnetic field strength. (b) Low-temperature dependence of the magnetization in Ce11Ru4In9 measured in a weak magnetic field of 0.01 T upon cooling the sample in zero (circles, ZFC) and finite (triangles, FC) external magnetic field. Inset: zoom into the weak-field

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magnetization data from panel (a).

Fig. 6. (a) Temperature variation of the electrical resistivity of Ce11Ru4In9. Inset: temperature

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dependence of the temperature derivative of the resistivity in the vicinity of the magnetic phase transition. (b) Low-temperature dependencies of the electrical resistivity of Ce11Ru4In9 measured in external magnetic field of different strength, applied perpendicular to electric current. Fig. 7. Field variations of the transverse magnetoresistivity of Ce11Ru4In9 measured at several temperatures in the magnetically ordered (upper panel) and paramagnetic (lower panel) regions. Solid curves in the upper panel emphasize a ferromagnetic-like behaviour (see the text). Fig. 8. Scaling of the transverse magnetoresistivity data of Ce11Ru4In9, appropriate for a ferromagnetic-like metal in its paramagnetic state (cf. the text) 12

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Table 1. Crystallographic data and structure refinement parameters for single-crystalline Ce11Ru4In9.

Composition, EDX, at.%

Ce47.6Ru15.6In36.8

Crystal size, mm

0.03 x 0.03 x 0.05 MoKα; 0.71073

Space group

Cmmm (No.65)

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Radiation, λ, Å

Unit cell dimensions, Å

a = 14.9523(10) b = 22.0133(15)

Volume of cell, Å3, Z

1258.7(1), 2

Molar mass, g/mol

4506.42

3

θ range, °

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Index range

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Calculated density, g/cm Absorption coefficient, mm-1 F (000)

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c = 3.8240(2)

Reflections measured

11.9 45.95 3792

3.7 ≤ θ ≤ 27.49 -19 ≤ h ≤ 19 -28 ≤ k ≤ 28 -4 ≤ l ≤ 4 5414 866 (0.059)

Reflections with I > 2σ(I) (Rσ)

748 (0.039)

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Independent reflections (Rint)

Refined parameters GOF on F2

45 1.123 0.041/ 0.052

wR2 / wR2 (all data)

0.094 / 0.099

Largest diff. peak and hole, e/ Å3

2.471 / -2.656

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R1 / R1 (all data)

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Table 2. Atomic coordinates and equivalent isotropic displacement parameters for Ce11Ru4In9. Atom

Wyckoff position

x/a

y/b

z/c

Ce1

8p

0.24670(6)

0.17079(4)

0

0.0176(3)

Ce2

4i

0

0.16050(6)

0

0.0177(3)

Ce3

4i

0

0.37495(6)

0

0.0151(3)

Ce4

4g

0.31405(9)

0

0

0.0153(3)

Ce5

2a

0

0

0

0.0171(4)

Ru*

8q

0.34441(11)

0.09621(9)

1/2

0.0297(6)

In1

8q

0.10144(8)

0.26519(5)

1/2

0.0185(3)

In2

8q

0.15082(8)

0.06955(5)

1/2

0.0181(3)

In3

2c

1/2

0

1/2

0.0162(5)

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* 0.96(1) occupation of site

Ueq., Å2

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2.9130(15) 3.2678(12) 3.2859(12) 3.489(2) 3.5624(13) 3.6957(10)

Ce2

In1 Ce5 In2 Ce1

4x 1x 4x 2x

3.3567(13) 3.5331(14) 3.5706(13) 3.6957(10)

Ce3

Ru In3 In1

4x 2x 4x

3.0774(14) 3.3516(11) 3.4344(13)

Ce4

Ru In3 In2

4x 2x 4x

2.8892(15) 3.3744(11) 3.4578(13)

Ce5

In2 Ce2

8x 2x

3.3294(10) 3.5331(14)

Ru

Ce4 Ce1 In2 Ce3 In3 In1

2x 2x 1x 2x 1x 1x

2.8892(15) 2.9130(15) 2.954(2) 3.0774(14) 3.1461(18) 3.157(2)

In1

In1 Ru Ce1 Ce2 Ce3 Ce1

1x 1x 2x 2x 2x 2x

3.034(2) 3.157(2) 3.2859(12) 3.3567(13) 3.4344(13) 3.5624(13)

In2

Ru In2 Ce1 Ce5 Ce4 Ce2

1x 1x 2x 2x 2x 2x

2.954(2) 3.062(2) 3.2678(12) 3.3294(10) 3.4578(13) 3.5706(13)

In3

Ru Ce3 Ce4

4x 4x 4x

3.1461(18) 3.3516(11) 3.3744(11)

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2x 2x 2x 1x 2x 1x

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Ru In2 In1 Ce1 In1 Ce2

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Ce1

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Table 3. Selected interatomic distances (Å) in the crystal structure of Ce11Ru4In9.

1

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1. Ce11Ru3.83In9 with the high cerium content crystallizes in Nd11Pd4In9 structure type. 2. Ce ions possess a 4f1 electronic state that gives rise to the local-moment magnetism.

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3. Ce11Ru3.83In9 exhibits localized magnetism with a ferromagnetic behavior below 6.3 K.