High-Pressure Synthesis, Crystal Structures, and Properties of ScRhO3and InRhO3 PerovskitesAlexei A. Belik,*, Yoshitaka Matsushita, Masahiko Tanaka, and Eiji Takayama-Muromachi

International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki,Tsukuba, Ibaraki 305-0044, JapanSPring-8 Oce, NIMS, Kohto 1-1-1, Sayo-cho, Hyogo 679-5148, JapanNational Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan

*S Supporting Information

ABSTRACT: ScRhO3 and InRhO3 perovskites were synthesized at a high pressure of 6GPa and a high temperature of 1500 K. Crystal structures of ScRhO3 and InRhO3 werestudied with synchrotron X-ray powder diraction at 293 and 134 K. ScRhO3 and InRhO3have a rarely observed monoclinic superstructure of the GdFeO3-type structure (spacegroup P21/n, a = 7.45660 , b = 7.43524 , c = 7.52191 , and = 93.2930 for ScRhO3and a = 7.59020 , b = 7.58377 , c = 7.59010 , and = 91.4154 for InRhO3 at 293 K).InRhO3 has pseudo-orthorhombic lattice parameters of a = 10.8658 , b = 7.5837 , andc = 10.6006 . ScRhO3 and InRhO3 are nonmagnetic, and no phase transitions weredetected between 2 and 873 K. Crystallographic trends and distortions of ScRhO3,InRhO3, and RRhO3 (R = rare earths, Y, and Bi) are discussed.

1. INTRODUCTION

ABO3 perovskites form a very large and important class ofcompounds and materials.1 The stability and distortions ofperovskites are often understood using the Goldschmidttolerance factor,2 t = (rA + rO)/[2

1/2(rB + rO)], where rA, rB,and rO are the ionic radii of the A, B, and oxygen ions,respectively, in perovskite ABO3. The perovskite structure isstable within the limits of t between 0.77 and 0.99 if the A andB ionic radii are based on octahedral coordination.3 Therefore,the A site of perovskites is usually occupied by large cationssuch as rare earth, Bi, and alkali earth cations (when the B sitecontains transition metals with rB = 0.5 to 0.7 ).

4 With smallercations at the A site, the perovskite structure becomes unstable(at ambient pressure), and other structural types are formed,5

for example, the bixbyite structure (ScFeO3)6 and the

hexagonal YMnO3-type structure (h-ScMnO37,8 and h-

InMnO3).9

There has been increased interest in recent years in highlydistorted or exotic perovskites in order to nd new physicalproperties and eects and unusual behavior.10 One way toobtain new exotic perovskites is to introduce small cations(such as Sc3+, In3+, Mn2+, and others) into the A site. This canbe done using the high-pressure, high-temperature preparationmethod; this method gave, for example, ScVO3 (8 GPa),

11

ScMnO3 (12.5 GPa),12 (In1xMnx)MnO3 (

1/9 x 1/3) (6GPa),13 MnVO3 (4.58 GPa),

14,15 Mn2FeSbO6 (6 GPa),16 and

even Mn2O3 (20 GPa)17 perovskites and perovskite-related

LiNbO3-type compounds, (In1xMx)MO3 (M = Mn0.5Fe0.5) (6GPa)18 and Mn2FeNbO6 (7 GPa).

19 InCrO3 (6.5 GPa),20

InRhO3 (6.5 GPa),20 and ScCrO3 (4.5 GPa)

21 perovskites wererst prepared long ago. However, only the lattice parameters ofInRhO3 were reported (a = 5.435 , b = 7.586 , and c = 5.301),20 and no information about its real crystal structure andproperties is known.In this work, we prepared InRhO3 and a new perovskite

ScRhO3 and investigated their structural and magneticproperties. Both ScRhO3 and InRhO3 have a rare monoclinicsuperstructure of the GdFeO3-type with lattice parameters of a= 7.45660 , b = 7.43524 , c = 7.52191 , and =93.2930(1) (for ScRhO3) and space group P21/n, and they areisostructural with the 1:3 B-site-ordered Sr(Na0.25Sb0.75)O3.

22

InRhO3 has pseudo-orthorhombic lattice parameters. There-fore, their structures are dierent from the orthorhombicGdFeO3-type structures of RRhO3 perovskites (R representsrare-earth cations, Y, and Bi).2333 Both InRhO3 and ScRhO3are nonmagnetic, similar to the RRhO3 perovskites (R = Y, La,Sm, Lu, and Bi).30,33

2. EXPERIMENTAL SECTIONScRhO3 and InRhO3 were prepared from stoichiometric mixtures ofIn2O3 (99.99%), Sc2O3 (99.9%), and Rh2O3 (99.9%). The mixtures(corresponding to the total weight of about 0.45 g for eachcompound) were placed in Au capsules and treated at 6 GPa in abelt-type high-pressure apparatus at 1500 K for 2 h. (The heating rateto the desired temperature was 10 min.) After heat treatment, thesamples were quenched to room temperature (RT), and the pressure

Received: July 9, 2013

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was slowly released. The resultant samples were dark-brown densepellets.

X-ray powder diraction (XRPD) data of ScRhO3 and InRhO3 werecollected at RT on a Rigaku Ultima III diractometer using Cu Kradiation (2 range of 10100, step width of 0.02, and countingtime of 10 s/step). Synchrotron XRPD data were measured at RT and134 K on a large DebyeScherrer camera at the BL15XU beamline ofSPring-8.34 The data were collected between 2 and 60 at a 0.003interval in 2. The incident beam was monochromatized at 0.65297 .The samples were packed into Lindenmann glass capillaries (innerdiameter 0.1 mm), which were rotated during the measurement. Theabsorption coecient was measured. The Rietveld analysis wasperformed with RIETAN-2000.35 For identied impurities, we renedonly scale factors and lattice parameters, xing their structuralparameters.

Magnetic susceptibilities ( = M/H) of ScRhO3 and InRhO3 weremeasured on a SQUID magnetometer (Quantum Design, MPMS)between 2 and 300 K in dierent applied elds under both zero-eld-cooled (ZFC) and eld-cooled on cooling (FCC) conditions.Isothermal magnetization measurements were performed between 0and 70 kOe at 5 and 300 K. All of the magnetization data werecorrected for contributions from diamagnetic sample holders(obtained in separate experiments) and core diamagnetism (dia/106 = 12.6 (O2), 22 (Rh3+), 6 (Sc3+), and 19 (In3+) cm3/mol)36 because negative total magnetization was observed at highertemperatures. The specic heat, Cp(T), was measured from 300 to 2 Kin a zero magnetic eld by a pulse relaxation method using acommercial calorimeter (Quantum Design PPMS).

Dierential scanning calorimetry (DSC) curves of ScRhO3(powder) and InRhO3 (powder) were recorded on a Mettler ToledoDSC1 STARe system at a heating/cooling rate of 10 K/min between293 and 873 K in open aluminum capsules. Two runs were performedto check the reproducibility. The rst heating DSC curve showedsharp anomalies at 361 K in ScRhO3 and at 406 K in InRhO3.However, no anomalies were found on the rst cooling curve and thesecond heatingcooling curves. XRPD measurements after the DSCexperiments showed that the perovskite phases of ScRhO3 and InRhO3remained unchanged. Therefore, the DSC anomalies on the rstheating curve most probably originated from irreversible trans-formations in impurities or annealing eects.

3. RESULTS AND DISCUSSION

All reections on synchrotron XRPD patterns with intensitiesabove 1% were indexed using TREOR37 in an orthorhombicsystem for InRhO3 (a = 5.4329 , b = 7.5837 , and c = 5.3003) and a monoclinic system for ScRhO3 (a = 5.4457 , b =7.4353 , c = 5.1414 , and = 90.5005). The orthorhombiclattice parameters of InRhO3 were in very good agreement withthe reported values.20 The observed reection conditions of k +

l = 2n for 0kl and h = 2n for hk0 in InRhO3 aorded twopossible space groups, centrosymmetric Pnma (No. 62) andnoncentrosymmetric Pn21a (No. 33).

38 The structure param-eters of LuRhO3

33 in space group Pnma were used as the initialones for the renement of InRhO3. Attempts to rene thestructure of InRhO3 in space group Pn21a did not improve thetting results. The observed reection conditions of k = 2n for0k0 in ScRhO3 aorded two possible space groups,centrosymmetric P21/m (No. 11) and noncentrosymmetricP21 (No. 4).

38 The structure parameters of Ca2MnSbO639 in

space group P21/m were used as the initial ones for therenement of ScRhO3. Attempts to rene the structure ofScRhO3 in space group P21 did not improve the tting results.Note that the initial substructure model for ScRhO3 could alsobe deduced from the obtained structural parameters of InRhO3in Pnma by a groupsubgroup transformation of Pnma > P21/m.Good ts and reliable structural parameters were obtained in

space group Pnma for InRhO3 (Rwp = 6.69%, Rp = 4.71%, RB =2.37%, and RF = 1.33%) and in space group P21/m for ScRhO3(Rwp = 5.92%, Rp = 4.14%, RB = 3.63%, and RF = 2.13%)(Supporting Information). However, both samples containedmany weak additional reections. Some additional reections inInRhO3 were found to originate from InOOH and Rhimpurities. Remaining additional reections in InRhO3 (exceptfor three extremely weak reections with d = 2.880, 2.822, and1.995 ) could be indexed in orthorhombic symmetry with the2a b 2c superstructure. Many additional reections inScRhO3 could be indexed in monoclinic symmetry with the (a + c) b (a c) superstructure. However, someunindexed weak reections remained in ScRhO3; they couldnot be indexed in any reasonable superstructure. Therefore,they most probably originated from unknown impurities.The (a + c) b (a c) superstructure of the P21/m

substructure of ScRhO3 can result in space groups P21/m andP21/n (the substructures and superstructures have groupsubgroup relations with each other). Attempts to apply theP21/m superstructure resulted in poor tting of somesuperstructure reections (actually two models with dierentorigin shifts were checked). However, superstructure reectionscould be perfectly t with the P21/n superstructure model.Therefore, the crystal structure of ScRhO3 was rened in theP21/n superstructure model. Note that there is another P21/nsuperstructure model (with a dierent origin shift) where allsites are in general 4e positions. However, that model gave

Table 1. Structural Parameters of ScRhO3 at Room Temperaturea

site Wycko position x y z B (2)

Sc1 4e 0.20568(18) 0.2426(4) 0.77502(18) 0.44(3)Sc2 4e 0.22445(19) 0.2328(3) 0.28865(18) 0.30(3)Rh1 2a 0 0 0 0.22(3)Rh2 2b 0 0 0.5 0.22(3)Rh3 2c 0.5 0 0.5 0.34(3)Rh4 2d 0.5 0 0 0.22(3)O1 4e 0.2581(6) 0.4629(6) 0.6075(5) 0.22(9)O2 4e 0.6021(6) 0.5481(6) 0.7545(6) 0.25(10)O3 4e 0.1108(4) 0.2524(11) 0.0355(4) 0.10(10)O4 4e 0.0416(6) 0.5982(6) 0.2525(7) 0.21(10)O5 4e 0.4630(5) 0.2500(14) 0.8904(4) 0.45(7)O6 4e 0.7533(7) 0.4074(6) 0.0469(6) 0.38(10)

aThe occupation factor for all sites is unity. Space group P21/n (No. 14; unique axis b, cell choice 2). Z = 8, a = 7.45660(1) , b = 7.43524(1) , c =7.52191(1) , = 93.2930(1), and V = 416.3385(9) 3. Rwp = 4.61%, Rp = 3.19%, RB = 1.19%, and RF = 0.80%. cal = 6.249 g/cm

3.

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larger R values and poor tting of some superstructurereections (Supporting Information).Our attempts to construct an orthorhombic 2a b 2c

superstructure model for InRhO3 [with a = 10.8658 , b =7.5837 , and c = 10.6006 and maximum space group Bmam(standard setting is Cmma) or Bmmm (standard setting isCmmm) based on the observed reection conditions] failed.Attempts to solve the structure of InRhO3 by direct methodswith EXPO40 in orthorhombic superstructures also failed.However, the structure of InRhO3 could be solved with EXPOin space group P21/n (where all Rh sites were in specialcentrosymmetric positions). Therefore, we used the obtainedstructural parameters of ScRhO3 in space group P21/n as theinitial ones for the renement of InRhO3. All superstructurereections of InRhO3 could be perfectly t with the P21/nsuperstructure model. We note that the same situation wasobserved in Sr(Na0.25Sb0.75)O3,

22 where a substructure modelwas the Pnma GdFeO3-type model (with 2

1/2ap 2ap 21/2ap

lattice parameters, where ap is the parameter of the cubicperovskite subcell) and a superstructure model had P21/nsymmetry and 2ap 2ap 2ap lattice parameters instead oforthorhombic symmetry and 2(21/2)ap 2ap 2(2

1/2)ap latticeparematers.The rened structural parameters, R values, selected bond

lengths, bond angles, and bond-valence sums (BVS)41 ofScRhO3 and InRhO3 are listed in Tables 14. For InRhO3,Table 2 gives structure parameters with xed lattice parameters

(obtained from the Pnma lattice parameters). This model gavemore reliable RhO bond lengths. A model with the renedlattice parameters is given in the Supporting Information.Superstructure reections were very weak in InRhO3 (

g(In2) = 1. These results showed that the Sc/Rh ratio inScRhO3 and the In/Rh ratio in InRhO3 were very close to 1:1.Figure 3 shows the lattice parameters as a function of ionic

radius (for 8-fold coordination)4 for all RRhO3 compounds (R

= Sc, In, Y,26 rare earths,23,2527,31,33 and Bi33). We used thelattice parameters of the substructure models for this gure.The lattice parameters and unit cell volume of ScRhO3 followthe general monotonic behavior observed in RRhO3 com-pounds (R = Y and LaLu), but both InRhO3 and BiRhO3exhibit a strong deviation from monotonic behavior. It isinteresting that all lattice parameters and unit cell volumes forInRhO3 and BiRhO3 show opposite deviations from theexpected values (which are based on the ionic radius). Thepeculiar behavior of both InRhO3 and BiRhO3 can be explainedby the signicant hybridization of InO42,43 and BiO bonds,resulting in more covalent bonds in comparison to RO (R = Yand LaLu) bonds. The same behavior of the latticeparameters was observed in ScCrO3, InCrO3, and RCrO3 (R= Y and LaLu) (Supporting Information).The substructure of InRhO3 has an orthorhombic GdFeO3-

type structure similar to that of the RRhO3 perovskites (R is arare earth cation, Y, or Bi).2333 The substructure of ScRhO3

Figure 1. Portions (2 = 630) of experimental (black crosses),calculated (red line), and dierence (blue line) synchrotron XRPDpatterns of (a) ScRhO3 and (b) InRhO3. The bars show possible Braggreection positions for the perovskite phases (black bars) and InOOH(green bars) and Rh (blue bars) impurities in InRhO3. Insets giveenlarged images (2 = 2028).

Figure 2. Crystal structure of ScRhO3 along (a) the a axis and (b) theb axis.

Figure 3. Lattice parameters and unit cell volume of RRhO3compounds (R = Sc, In, Y,26 rare earths,23,2527,31,33 and Bi33) as afunction of the ionic radius (in 8-fold coordination).4 Arrows show theideal lattice parameters for InRhO3 and BiRhO3 (or expected latticeparameters from the monotonic trends in the family).

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has a small monoclinic distortion of the GdFeO3-type structure;this P21/m distortion was observed in doped CaMnO3-basedmanganites, (Ca0.85La0.15)MnO3,

44 (Ca0.85Tb0.15)MnO3,45

(Ca0.3Nd0.7)MnO3,46,47 CaMn1xWxO3,

48 and Ca2MnSbO6.39

The Pnma-to-P21/m transition in CaMnO3-based manganites isoften observed at low temperatures and associated withmagnetic and charge ordering. We emphasize that themonoclinic angle in the substructure of ScRhO3 is betweenthe a (= 21/2ap) and c (= 2

1/2ap) lattice parameters. It isdierent from monoclinic angles between the 21/2ap and 2aplattice parameters observed in B-site rock-salt-ordered perov-skites.16,49,50

The superstructure found in both ScRhO3 and InRhO3 wasobserved only, to the best of our knowledge, in 1:3 B-site-ordered Sr(Na0.25Sb0.75)O3.

22 The tilt angles for each RhO6octahedron in ScRhO3 and InRhO3 can be calculated withequations given in ref 22, and the results can be found in theSupporting Information. However, for the purpose ofcomparison, we compare tilt angles of ScRhO3 and InRhO3calculated for the substructure models with those of RRhO3perovskites (R is a rare earth cation, Y, or Bi).2333 The tiltsystem of Pnma is a+bb (ref 51) according to Glazersnotation.52 The tilt system of P21/m is similar, a

+bc.51 Theonly dierence is that the rotation along the c axis should notbe the same as the rotation along the b axis. The tilt system ofthe P21/n superstructure cannot be written in Glazers notation,but the octahedral tilt system should be basically the same asthat of the substructures.22 A weak superstructure could appearfrom the independent tilting of octahedra in dierent layers(Figure 2b).The octahedral tilt angles in Pnma can be estimated from the

atomic coordinates of the O2 atom. We used the formulas forthe tilt angles as dened in ref 53: in-phase tilt angle O2 =arctan(1 + 2xO2 2zO2) and out-of-phase tilt angle O2 =arctan(25/2yO2) (for our coordinates in space group Pnma). Theout-of-phase tilt angle can also be calculated from the atomiccoordinates of the O1 atom: O1 = arctan(2

3/2zO1).54 A tilt

angle can be calculated from the lattice parameters, lattice =arccos(21/2c2/(ab)).55 Figure 4 shows dierent tilt angles as afunction of ionic radius (for 8-fold coordination)4 for allRRhO3 compounds (R = Sc, In, Y,

26 rare earths,23,2527,31,33

and Bi33). In-phase tilt angle O2 monotonically increases with

decreasing the R3+ ionic radius (except for BiRhO3). Out-of-phase tilt angles O2 and O1 are close to each other (againexcept for BiRhO3) with an anomaly from the monotonicbehavior on InRhO3. Tilt angle lattice shows strong anomaliesin InRhO3 and BiRhO3 because of their anomalous latticeparameters (Figure 3).All tilt angles of ScRhO3 were larger that those of InRhO3

(Figure 4 and Supporting Information). This is an expectedresult because ScRhO3 with smaller Sc

3+ ions at the A siteshould have larger distortions. However, the dierence in tiltangles is not very signicant, and the oxygen coordination ofSc3+ and In3+ ions is similar in ScRhO3 and InRhO3 with sixshort bond lengths and two much longer bond lengths (Tables3 and 4).The Goldschmidt tolerance factor of ScRhO3 is 0.735, and

that of InRhO3 is 0.753 (with the ionic radius for 6-foldcoordination). Therefore, ScRhO3 and InRhO3 should not bestable at ambient pressure.3 The high-pressure, high-temper-ature method is needed to stabilize them under ambientconditions. So far, ScVO3,

11 ScCrO3,10,21 ScMnO3,

12 ScRhO3,InCrO3,

10,20 (In1xMnx)MnO3,13 and InRhO3 simple perov-

skites could be prepared by the high-pressure, high-temperaturemethod. ScVO3, ScCrO3, and InCrO3 crystallize in the PnmaGdFeO3-type structure (2

1/2ap 2ap 21/2ap) at RT with one

crystallographic site for V3+ and Cr3+. ScMnO3 crystallizes inthe B-site-ordered GdFeO3-type structure with space groupP21/n (2

1/2ap 21/2ap 2ap)

12 similar to (In1xMnx)MnO3(1/9 x 1/3)

13 with two crystallographic Mn sites havingquite dierent JahnTeller distortions. ScRhO3 and InRhO3have the most complicated superstructure of the originalGdFeO3-type structure with space group P21/n (2ap 2ap 2ap) among ScMO3 and InMO3 compounds. For ScRhO3,small Sc3+ ions at the A site and strong bending of the RhO6RhO6 chains (with the average RhORh bond angle of132.2) should contribute to its unusual structural distortion.Bond angles are larger in ScVO3 (VOV = 136.5),11ScCrO3 (CrOCr = 137.9),

10 and ScMnO3 (MnOMn = 135.0).12 In-phase tilt angle O2 is the largest inScRhO3 and InRhO3 among known ScMO3 and InMO3compounds (Supporting Information).Synchrotron XRPD data at 134 K (a = 7.45257(1) , b =

7.43103(1) , c = 7.51929(1) , and = 93.2603(1) forScRhO3; a = 5.42927(2) , b = 7.57701(2) , and c =5.29713(1) in Pnma and a = 7.58254(3) , b = 7.57701(1), c = 7.58786(1) , and = 91.4115(1) in P21/n forInRhO3) showed that the crystal symmetry of ScRhO3 andInRhO3 did not change. Specic heat measurements between 2and 300 K (Figure 5) and DSC measurements between 293and 873 K also showed no anomalies. All of these facts indicatethe absence of low-temperature phase transitions and high-temperature phase transitions up to 873 K in ScRhO3 andInRhO3. We note that specic heat measurements by the pulserelaxation method sometimes cannot detect structural phasetransitions, for example, in PbPd2O4.

56

The specic heat between 5 and 19 K for ScRhO3 and 3 and19 K for InRhO3 could be t by the equation (inset of Figure 5)

= + +C T T T T( )p 13

25

(1)

where the rst term is associated with the electroniccontribution and the second and third terms describe thelattice contribution. The tted parameters were = 0.52(4)mJ/mol K2, 1 = 0.0589(5) mJ/mol K

4, and 2 = 2.88(14)

Figure 4. Dierent tilt angles as a function of the ionic radius (in 8-fold coordination) in RRhO3 compounds (R = Sc, In, Y, rareearths,31,33 and Bi33). See the text for denitions of the tilt angles.5355

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105 mJ/mol K6 for ScRhO3 and = 0.387(15) mJ/mol K2, 1

= 0.0778(3) mJ/mol K4, and 2 = 1.107(8) 104 mJ/mol K6

for InRhO3. The existence of the T term with very small valuesof the coecient could originate from the presence ofimpurities (such as metallic Rh in InRhO3). The values of 1gave Debye temperatures, D = (234NkB/1)1/3 (N isAvogadros number and kB is Boltzmanns constant), of 320K for ScRhO3 and 292 K for InRhO3, which are comparable tothe Debye temperatures of other perovskites: BiRhO3 (D 236 K),33 LuRhO3 (D 271 K),33 and SrVO3 (D 322K).57

Figure 6 shows the versus T curves of ScRhO3 and InRhO3at 50 kOe and M versus H curves at 5 and 300 K. There wasbasically no dierence between the ZFC and FCC curves. Noanomalies were observed on the versus T curves, and thecurves could be t with the equation

= +

TT

( )0.125

0eff

2

(2)

where 0 is a temperature-independent term, eff is the eectivemagnetic moment in the Bohr magneton B, and is theCurieWeiss temperature. The tting parameters were 0 =6.48(9) 105 cm3/mol, eff = 0.173(1)B/f.u., and =5.4(1) K for ScRhO3 and 0 = 5.64(9) 105 cm3/mol, eff =0.155(2)B/f.u., and = 7.8(3) K for InRhO3. Similareective magnetic moments were observed in RRhO3 (R = La,Lu, and Bi).30,33 The small eective magnetic moments suggestthat the weak magnetism of ScRhO3 and InRhO3 comes fromtraces of paramagnetic impurities or defects. ScRhO3 andInRhO3 are nonmagnetic, and this is in agreement with thenonmagnetic low-spin state of Rh3+ ions (t62g).In conclusion, we prepared InRhO3 and new perovskite

ScRhO3 and investigated their structural and magneticproperties. Both InRhO3 and ScRhO3 are nonmagnetic similarto the RRhO3 perovskites (R = Y, La, Sm, Lu, and Bi),

30,33 andthey show no phase transitions between 2 and 873 K. From thispoint of view, they are not very interesting in comparison tosimilar compounds ScMO3 and InMO3 containing othertransition metals. However, they have a rare superstructure ofthe GdFeO3-type with space group P21/n and latticeparameters 2ap 2ap 2ap. Therefore, exotic perovskiteswith small cations at the A site continue to provide interestingstructural or physical properties.

ASSOCIATED CONTENT*S Supporting InformationStructural parameters of ScRhO3 and InRhO3 in dierentstructural models, tting results, laboratory X-ray powderdiraction patterns, additional structural gures, DSC curves,tilt angle calculations, lattice parameters, and unit cell volumesof RCrO3 (R = Sc, In, Y, and LaLu) compounds. Thismaterial is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATIONCorresponding Author*E-mail: alexei.belik@nims.go.jp.NotesThe authors declare no competing nancial interest.

ACKNOWLEDGMENTSThis work was supported by the World Premier InternationalResearch Center Initiative (WPI Initiative, MEXT, Japan), theJapan Society for the Promotion of Science (JSPS) through its

Figure 5. Specic heat data of ScRhO3 (black circles) and InRhO3(blue squares) at zero magnetic eld plotted as Cp/T vs T (lines aredrawn for eye). The inset gives the Cp/T vs T

2 curves (symbols) withthe tting results by eq 1 (lines).

Figure 6. (Top) vs T curves of ScRhO3 (black circles) and InRhO3(blue squares) at 50 kOe in the eld-cooled regime on cooling. Linesshow tting results with eq 2. (Bottom) M vs H curves for ScRhO3 at5 K (black circles) and 300 K (white circles, right- and left-hand axes)and for InRhO3 at 5 K (blue squares). Lines are drawn to guide theeye.

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dx.doi.org/10.1021/ic401760m | Inorg. Chem. XXXX, XXX, XXXXXXF

Funding Program for World-Leading Innovative R&D onScience and Technology (FIRST Program), and Grants-in-Aidfor Scientic Research (22246083 and 21540330) from JSPS,Japan. The synchrotron radiation experiments were performedat SPring-8 with the approval of the Japan SynchrotronRadiation Research Institute (proposal numbers 2011B4512and 2012A4507). We thank Dr. A. M. Abakumov forconsultations related to superstructures in perovskites.

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dx.doi.org/10.1021/ic401760m | Inorg. Chem. XXXX, XXX, XXXXXXG