Ba68Pd32Ox, with x 13 5

inorganic papers

i64

Structure Reports

Online ISSN 1600-5368

Ba

Pd

O

, with

x

'

13.5

Malin MaÊrtensson, Emma Wikstad, Helen Blomqvist, Mikael Kritikos and Lars Eriksson*

Division of Structural Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm, Sweden

Correspondence e-mail: lerik@struc.su.se

Key indicators Single-crystal X-ray study

T= 293 K

Mean(Ba±O) = 0.003 AÊ Disorder in solvent or counterion

Rfactor = 0.029

wRfactor = 0.041

Data-to-parameter ratio = 15.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, barium palladium oxide, Ba68Pd32Ox,x'

13.5 is a medium-sized cubic suboxide. Two of the four crystallographically independent Ba atoms form a network of face-sharing octahedra with O atoms occupying the central position of these octahedra, giving a network resembling the pyrochlore structure. Two of three O-atom positions are fully occupied and the third partially occupied. The remainder of the Ba atoms and the Pd atoms are distributed in another network residing in the channels of the network of face-sharing O±Ba6octahedra.

Comment

The title compound was synthesized as part of a search for intermetallic compounds for use as hydrogen storage mate-rials. The compound is composed of a network of face-sharing O±Ba6octahedra with the residual Ba atoms and all Pd atoms

located in the tunnels of the octahedra network. O atoms were assigned to model quite large residual densities in the centre of the octahedra. This network of O±Ba6is closely related to

the pyrochlore structure (Gaertner, 1930). Removing the O1 atom (Fig. 1) gives a good resemblance between the

pyro-chlore Nb±O6 octahedra and the network of O2±Ba26

octa-hedra in the title compound. Barium suboxides, with similar arrangements of O±Ba octahedra, have been observed earlier (RoÈhr, 1995). The main difference in the present compound are the slightly longer BaÐO and BaÐBa distances. This may be due to partial occupation of the O-atom positions giving a weaker attraction but may also be an effect of the excess Ba and Pd in the structure. In addition to the network of O±Ba6

octahedra as shown in Fig. 2, one can construct a comple-mentary network of tetrahedraly coordinated Ba3 around Ba4 with an extra tetrahedron of Pd1 around Ba4 connected to

each other through squares of 2 Ba3 and 2 Pd2. This

additional network is shown in Fig. 3. It must be emphasized that the only indication that the title compound contains oxygen is the much better ®t of the diffraction data when the model includes O atoms. Removing the O atoms from the structure model gives a pure intermetallic compound with the composition Ba68Pd32. This is, however, probably not correct.

The oxygen stoichiometry cannot be stated with particularly high accuracy as it is a result from re®nement.

Experimental

The compound was crystallized from a solid-state reaction between a mixture of BaH2(Ba rods 99.9+%, Aldrich Chemical Company Inc.;

heated under 50 bar of H2pressure at 723 K for 4 h) and Pd (powder

< 60mm, claimed purity 99.9+%, Chempur) in a nominal molar ratio Ba:Pd = 2:1 mixed and heated (T'973 K) in an Al2O3crucible in a

stainless-steel reactor under a H2pressure of 35 bar. All materials

were handled in an argon-®lled glove-box. The reason for using

hydrogen was that the initial intention was to synthesize hydrides. The most probable sources of oxygen are either residual impurities in the glove-box atmosphere or a solid-state reaction with the crucible material (Al2O3). Assuming the conditions of Ellingham diagrams

(Wulfsberg, 1987) to be true, one can imagine that the reduction of Al2O3 with Ba metal would be spontaneous at the synthesis

temperature, thus a possible source of oxygen is the crucible material. Small single crystals were obtained from the solidi®ed reaction product.

Crystal data

Ba2.125PdO0.422

Mr= 404.91

Cubic,F43m a= 15.878 (1) AÊ V= 4003.0 (4) AÊ3

Z= 32

Dx= 5.340 Mg mÿ3

MoKradiation

Cell parameters from 32 re¯ections

= 15.0±19.2

= 19.89 mmÿ1

T= 293 (2) K

Prism, metallic light grey 0.140.090.07 mm

Data collection

Stoe AED-4 diffractometer

!/2scans

Absorption correction: numerical (X-RED; Stoe & Cie, 1997) Tmin= 0.060,Tmax= 0.259

1671 measured re¯ections 336 independent re¯ections 270 re¯ections withI> 2(I)

Rint= 0.079

max= 27.9

h=ÿ1!20

k=ÿ1!20

l=ÿ1!20

3 standard re¯ections frequency: 240 min intensity decay: 1%

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.029}

wR(F2_{) = 0.042}

S= 1.16 336 re¯ections 22 parameters w= 1/[2_(F

o2) + (0.01P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 1.65 e AÊÿ3

min=ÿ1.32 e AÊÿ3

Absolute structure: Flack (1983), 45 Friedel pairs

Flack parameter =ÿ0.08 (11) Figure 2

Slightly more than the unit cell content with the network of O±Ba6

octahedra shown blue around O1, green around O2 and red around O3. Pd atoms are yellow and Ba grey. The Ba atoms that form the octahedra

Figure 3

The unit-cell content with the complementary network to the O±Ba6

network. The Ba atoms are shown as grey circles and Pd with yellow circles. The orientation of this picture is equivalent to Fig. 2.

Figure 1

Part of the network of O±Ba6octahedra. The octahedra with O1 in its

inorganic papers

i66

Table 1

Selected distances (AÊ).

Ba1ÐO1i _{2.7999 (16)}

Ba1ÐO3 3.00 (4) Ba1ÐPd2ii _{3.255 (2)}

Ba1ÐBa1iii _{3.960 (2)}

Ba1ÐBa2iv _{4.3277 (6)}

Ba2ÐO2i _{2.7029 (13)}

Ba2ÐO3v _{2.82 (3)}

Ba2ÐPd1vi _{3.280 (2)}

Ba2ÐBa2vii _{3.8225 (18)}

Ba2ÐBa3 4.2849 (11) Ba3ÐPd2viii _{3.2825 (17)}

Ba3ÐBa4 4.1393 (18) Ba3ÐBa1ix _{4.3567 (11)}

Ba3ÐBa3x _{4.468 (3)}

Ba4ÐPd1 2.888 (3)

Symmetry codes: (i) x;yÿ1

2;zÿ12; (ii) x;1ÿy;1ÿz; (iii) 12‡z;1ÿx;12ÿy; (iv)

1ÿy;1

2‡z;12ÿx; (v) xÿ12;12ÿy;ÿz; (vi) x;12ÿy;12ÿz; (vii) 12ÿy;z;12ÿx; (viii)

xÿ1;1ÿy;1ÿz; (ix)y;z;xÿ1; (x)x;ÿy;ÿz.

The O atoms in the centre of the barium octahedra were located from difference-density maps. Without the O atoms, residual densi-ties of 12.2, 7.4 and 2.9 e AÊÿ3_{were located in the centre of the Ba}

octahedra. Adding the O atoms further decreased the conventional R1 from 0.040 to 0.029. All O atoms were re®ned with a common isotropic displacement parameter and the occupancy of O3 was left free to re®ne. Adding hydrogen as central atoms to describe the residual intensities invariably led to negative displacement para-meters and the only reasonable model that ®tted the diffraction data was the one described with the O atoms in the centre of the octa-hedra. The corresponding re®nement of the occupancy parameters of O1 and O2 did not yield any signi®cant deviation from full occupancy, thus they were ®xed at full occupancy. The use of a common isotropic

displacement parameter was found to be the model that gave the most stable re®nement. No chemical analysis of the O content was performed; thus the only indication of the presence of O atoms is the better ®t to the structural data.

Data collection:DIF4 (Stoe & Cie, 1988); cell re®nement:DIF4; data reduction:REDU4 (Stoe & Cie, 1988); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

DIAMOND(Bergerhoff, 1996).

References

Bergerhoff, G. (1996).DIAMOND. Gerhard-Domagk-Straûe 1, 53121 Bonn, Germany.

Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Gaertner, H. R. von (1930). Zentralblatt fuer Mineralogie, Geologie und Paleontologie, Abt. A., pp. 1±30. Stuttgart: E. Schweizerbart'sche Verlags-buchhandlung.

RoÈhr, C. (1995).Z. Anorg. Allg. Chem.621, 1496±1500. Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Stoe & Cie (1988).AED-2,DIF4 (Version 7.04) andREDU4 (Version 6.2).

Stoe & Cie GmbH, Darmstadt, Germany.

Stoe & Cie (1997).X-RED. Version 1.09. Stoe & Cie GmbH, Darmstadt, Germany.

supporting information

Acta Cryst. (2001). E57, i64–i66 [doi:10.1107/S1600536801010935]

Ba

Pd

O

, with

x

[\simeq] 13.5

Malin M

å

rtensson, Emma Wikstad, Helen Blomqvist, Mikael Kritikos and Lars Eriksson

S1. Comment

The title compound was synthesized as part of a search for intermetallic compounds for use as hydrogen storage

materials. The compound is composed of a network of face sharing O–Ba6 octahedra with the residual Ba atoms and all

Pd atoms located in the tunnels of the octahedra network. O atoms were assigned to model quite large residual densities

in the centre of the octahedra. This network of O—Ba6 is closely related to the pyrochlore structure (Gaertner, 1930).

Removing the O1 atom (Fig. 1) gives a good resemblance between the pyrochlore Nb—O6 octahedra and the network of

O2—Ba26 octahedra in the title compound. Barium suboxides, with similar arrangements of O—Ba octahedra, have been

observed earlier (Röhr, 1995). The main difference in the present compound are the slightly longer Ba—O and Ba—Ba

distances. This may be due to partial occupation of the O-atom positions giving a weaker attraction but may also be an

effect of the excess Ba and Pd in the structure. In addition to the network of O—Ba6 octahedra as shown in Fig. 2, one

can construct a complementary network of tetrahedraly coordinated Ba3 around Ba4 with an extra tetrahedron of Pd1

around Ba4 connected to each other through squares of 2 × Ba3 and 2 × Pd2. This additional network is shown in Fig. 3.

It must be emphasized that the only indication that the title compound contains oxygen is the much better fit of the

diffraction data when the model includes O atoms. Removing the O atoms from the structure model gives a pure

intermetallic compound with the composition Ba68Pd32. This is, however, probably not correct. The oxygen stoichiometry

cannot be stated with particularly high accuracy as it is a result from refinement.

S2. Experimental

The compound was crystallized from a solid-state reaction between a mixture of BaH2 (Ba rods 99.9+%, Aldrich

Chemical Company Inc.; heated under 50 bar of H2 pressure at 723 K for 4 h) and Pd (powder < 60 µm, claimed purity

99.9+%, Chempur) in a nominal molar ratio Ba:Pd = 2:1 mixed and heated (T ≈ 973 K) in an Al2O3 crucible in a stainless-steel reactor under a H2 pressure of 35 bar. All materials were handled in an argon-filled glove-box. The reason

for using hydrogen was that the initial intention was to synthesize hydrides. The most probable sources of oxygen are

either residual impurities in the glove-box atmosphere or a solid-state reaction with the crucible material (Al2O3).

Assuming the conditions of Ellingham diagrams (Wulfsberg, 1987) to be true, one can imagine that the reduction of Al2O3

with Ba metal would be spontaneous at the synthesis temperature, thus a possible source of oxygen is the crucible

material. Small single crystals were obtained from the solidified reaction product.

S3. Refinement

The O atoms in the center of barium octahedra were located from difference-density maps. Without the O atoms, residual

densities of 12.2, 7.4 and 2.9 e Å-3 _{were located in the center of the Ba octahedra. Adding the O atoms further decreased}

the conventional R1 from 0.040 to 0.029. A l l O atoms were refined with a common isotropic displacement parameter

supporting information

sup-2

invariably led to negative displacement parameters and the only reasonable model that fitted the diffraction data was the

one described with the oxygen atoms in the center of the octahedra. The corresponding refinement of the occupancy

parameters of O1 and O2 did not yield any significant deviation from full occupancy, thus they were locked at full

occupancy. The use of a common isotropic displacement parameter was found to be the model that gave the most stable

refinement. No chemical analysis of the O content were done, thus the only indication of the presence of O atoms is the

better fit to the structural data.

Figure 1

Part of the network of O—Ba6 octahedra. The octahedra with O1 in its centre is blue and the ones with O3 in the centres

are red. The Pd atoms are shown as yellow unconnected circles and the Ba atoms are shown with small grey circles at the

Figure 2

Slightly more than the unit-cell content with the network of O—Ba6 octahedra shown blue around O1, green around O2

supporting information

sup-4

Figure 3

The unit-cell content with the complementary network to the O–Ba6 network. The Ba atoms are shown as grey circles and

Pd with yellow circles. The orientation of picture is equivalent to Fig. 2.

barium palladium oxide

Crystal data

Ba2.125PdO0.422

Mr = 404.91 Cubic, F43m a = 15.878 (1) Å

V = 4003.0 (4) Å3

Z = 32

F(000) = 5344

Dx = 5.340 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 32 reflections

θ = 15.0–19.2°

µ = 19.89 mm−1

T = 293 K

Prism, metallic light grey 0.14 × 0.09 × 0.07 mm

Data collection

Stoe AED4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: numerical (X-RED; Stoe & Cie, 1997)

Tmin = 0.060, Tmax = 0.259 1671 measured reflections

336 independent reflections 270 reflections with I > 2σ(I)

Rint = 0.079

θmax = 27.9°, θmin = 2.2°

h = −1→20

k = −1→20

l = −1→20

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.029}

wR(F2_{) = 0.042}

S = 1.16 336 reflections 22 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

w = 1/[σ2_(F

o2) + (0.01P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 1.65 e Å−3 Δρmin = −1.32 e Å−3

Absolute structure: Flack (1983), XXXX Friedel pairs

Absolute structure parameter: −0.08 (11)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) is used} only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq Occ. (<1)

Ba1 0.92634 (10) 0.2500 0.2500 0.0160 (5)

Ba2 0.32977 (8) 0.0000 0.0000 0.0153 (5)

Ba3 0.09949 (6) 0.09949 (6) 0.09949 (6) 0.0128 (4)

Ba4 0.2500 0.2500 0.2500 0.0119 (7)

Pd1 0.35502 (11) 0.35502 (11) 0.35502 (11) 0.0140 (5) Pd2 0.89303 (10) 0.89303 (10) 0.89303 (10) 0.0114 (6)

O1 0.7500 0.7500 0.7500 0.011 (5)*

O2 0.5000 0.5000 0.5000 0.011 (5)*

O3 0.879 (2) 0.379 (2) 0.121 (2) 0.011 (5)* 0.34 (3)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Ba1 0.0113 (9) 0.0184 (6) 0.0184 (6) 0.000 0.000 −0.0105 (7)

Ba2 0.0087 (8) 0.0187 (5) 0.0187 (5) 0.000 0.000 0.0000 (10)

Ba3 0.0128 (4) 0.0128 (4) 0.0128 (4) 0.0015 (5) 0.0015 (5) 0.0015 (5)

Ba4 0.0119 (7) 0.0119 (7) 0.0119 (7) 0.000 0.000 0.000

Pd1 0.0140 (5) 0.0140 (5) 0.0140 (5) −0.0032 (7) −0.0032 (7) −0.0032 (7) Pd2 0.0114 (6) 0.0114 (6) 0.0114 (6) −0.0014 (7) −0.0014 (7) −0.0014 (7)

Geometric parameters (Å, º)

Ba1—O1i _{2.7999 (16) Ba3—Ba3}xxv _{4.468 (3)}

Ba1—O3 3.00 (4) Ba4—Pd1 2.888 (3)

supporting information

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Ba1—Pd2iii _{3.255 (2) Ba4—Pd1}xxvi _{2.888 (3)}

Ba1—Pd2i _{3.255 (2) Ba4—Pd1}xxvii _{2.888 (3)}

Ba1—Ba1iv _{3.960 (2) Ba4—Ba3}xxvii _{4.1393 (18)}

Ba1—Ba1v _{3.960 (2) Ba4—Ba3}xxvi _{4.1393 (18)}

Ba1—Ba1vi _{3.960 (2) Ba4—Ba3}ii _{4.1393 (18)}

Ba1—Ba1vii _{3.960 (2) Pd1—Ba2}xxviii _{3.280 (2)}

Ba1—Ba2viii _{4.3277 (6) Pd1—Ba2}xxix _{3.280 (2)}

Ba1—Ba2ix _{4.3277 (6) Pd1—Ba2}xxx _{3.280 (2)}

Ba1—Ba2x _{4.3277 (6) Pd2—Ba1}xxviii _{3.255 (2)}

Ba2—O2i _{2.7029 (13) Pd2—Ba1}xxx _{3.255 (2)}

Ba2—O3xi _{2.82 (3) Pd2—Ba1}xxix _{3.255 (2)}

Ba2—O3xii _{2.82 (3) Pd2—Ba3}xxxi _{3.2825 (17)}

Ba2—Pd1ii _{3.280 (2) Pd2—Ba3}xxxii _{3.2825 (17)}

Ba2—Pd1i _{3.280 (2) Pd2—Ba3}xxxiii _{3.2825 (17)}

Ba2—Ba2xiii _{3.8225 (18) O1—Ba1}xxxiv _{2.7999 (16)}

Ba2—Ba2xiv _{3.8225 (18) O1—Ba1}xxx _{2.7999 (16)}

Ba2—Ba2vi _{3.8225 (18) O1—Ba1}xxviii _{2.7999 (16)}

Ba2—Ba2vii _{3.8225 (18) O1—Ba1}xxix _{2.7999 (16)}

Ba2—Ba3xv _{4.2849 (11) O1—Ba1}xxxv _{2.7999 (16)}

Ba2—Ba3 4.2849 (11) O1—Ba1xxxvi _{2.7999 (16)}

Ba2—Ba1xvi _{4.3277 (6) O2—Ba2}xxxvii _{2.7029 (13)}

Ba3—Pd2xvii _{3.2825 (17) O2—Ba2}xxviii _{2.7029 (13)}

Ba3—Pd2xviii _{3.2825 (17) O2—Ba2}xxxviii _{2.7029 (13)}

Ba3—Pd2xix _{3.2825 (17) O2—Ba2}xxix _{2.7029 (13)}

Ba3—Ba4 4.1393 (18) O2—Ba2iv _{2.7029 (13)}

Ba3—Ba2xx _{4.2849 (11) O2—Ba2}xxx _{2.7029 (13)}

Ba3—Ba2xxi _{4.2849 (11) O3—Ba2}viii _{2.82 (3)}

Ba3—Ba1xxii _{4.3567 (11) O3—Ba2}xxxix _{2.82 (3)}

Ba3—Ba1xxiii _{4.3567 (11) O3—Ba2}x _{2.82 (3)}

Ba3—Ba1xxiv _{4.3567 (11) O3—Ba1}v _{3.00 (4)}

Ba3—Ba3xv _{4.468 (3) O3—Ba1}vi _{3.00 (4)}

O1i_{—Ba1—O3 75.6 (8) Ba2—Ba3—Ba2}xx _{119.556 (6)}

O1i_—Ba1—O3ii _{75.6 (8) Pd2}xvii_—Ba3—Ba2xxi _{67.311 (13)}

O3—Ba1—O3ii _{151.3 (16) Pd2}xviii_—Ba3—Ba2xxi _{151.51 (7)}

O1i_—Ba1—Pd2iii _{80.65 (4) Pd2}xix_—Ba3—Ba2xxi _{67.311 (13)}

O3—Ba1—Pd2iii _{87.69 (13) Ba4—Ba3—Ba2}xxi _{86.16 (3)}

O3ii_—Ba1—Pd2iii _{87.69 (13) Ba2—Ba3—Ba2}xxi _{119.556 (6)}

O1i_—Ba1—Pd2i _{80.65 (4) Ba2}xx_—Ba3—Ba2xxi _{119.556 (6)}

O3—Ba1—Pd2i _{87.69 (13) Pd2}xvii_—Ba3—Ba1xxii _{123.422 (14)}

O3ii_—Ba1—Pd2i _{87.69 (13) Pd2}xviii_—Ba3—Ba1xxii _{123.422 (14)} Pd2iii_—Ba1—Pd2i _{161.30 (9) Pd2}xix_—Ba3—Ba1xxii _{47.94 (4)}

O1i_—Ba1—Ba1iv _{45.0 Ba4—Ba3—Ba1}xxii _{74.39 (3)}

O3—Ba1—Ba1iv _{108.0 (7) Ba2—Ba3—Ba1}xxii _{60.099 (5)}

O3ii_—Ba1—Ba1iv _{48.7 (6) Ba2}xx_—Ba3—Ba1xxii _{160.55 (5)}

Pd2iii_—Ba1—Ba1iv _{52.54 (3) Ba2}xxi_—Ba3—Ba1xxii _{60.099 (5)} Pd2i_—Ba1—Ba1iv _{112.24 (4) Pd2}xvii_—Ba3—Ba1xxiii _{123.422 (14)}

O3—Ba1—Ba1v _{48.7 (6) Pd2}xix_—Ba3—Ba1xxiii _{123.422 (14)}

O3ii_—Ba1—Ba1v _{108.0 (7) Ba4—Ba3—Ba1}xxiii _{74.39 (3)}

Pd2iii_—Ba1—Ba1v _{52.54 (3) Ba2—Ba3—Ba1}xxiii _{60.099 (5)}

Pd2i_—Ba1—Ba1v _{112.24 (4) Ba2}xx_—Ba3—Ba1xxiii _{60.099 (5)}

Ba1iv_—Ba1—Ba1v _{60.0 Ba2}xxi_—Ba3—Ba1xxiii _{160.55 (5)}

O1i_—Ba1—Ba1vi _{45.0 Ba1}xxii_—Ba3—Ba1xxiii _{113.04 (2)}

O3—Ba1—Ba1vi _{48.7 (6) Pd2}xvii_—Ba3—Ba1xxiv _{47.94 (4)}

O3ii_—Ba1—Ba1vi _{108.0 (7) Pd2}xviii_—Ba3—Ba1xxiv _{123.422 (14)} Pd2iii_—Ba1—Ba1vi _{112.24 (4) Pd2}xix_—Ba3—Ba1xxiv _{123.422 (14)}

Pd2i_—Ba1—Ba1vi _{52.54 (3) Ba4—Ba3—Ba1}xxiv _{74.39 (3)}

Ba1iv_—Ba1—Ba1vi _{90.0 Ba2—Ba3—Ba1}xxiv _{160.55 (5)}

Ba1v_—Ba1—Ba1vi _{60.0 Ba2}xx_—Ba3—Ba1xxiv _{60.099 (5)}

O1i_—Ba1—Ba1vii _{45.0 Ba2}xxi_—Ba3—Ba1xxiv _{60.099 (5)}

O3—Ba1—Ba1vii _{108.0 (7) Ba1}xxii_—Ba3—Ba1xxiv _{113.04 (2)}

O3ii_—Ba1—Ba1vii _{48.7 (6) Ba1}xxiii_—Ba3—Ba1xxiv _{113.04 (2)} Pd2iii_—Ba1—Ba1vii _{112.24 (4) Pd2}xvii_—Ba3—Ba3xv _{92.93 (5)} Pd2i_—Ba1—Ba1vii _{52.54 (3) Pd2}xviii_—Ba3—Ba3xv _{47.11 (4)}

Ba1iv_—Ba1—Ba1vii _{60.0 Pd2}xix_—Ba3—Ba3xv _{47.11 (4)}

Ba1v_—Ba1—Ba1vii _{90.0 Ba4—Ba3—Ba3}xv _144.7

Ba1vi_—Ba1—Ba1vii _{60.0 Ba2—Ba3—Ba3}xv _{58.58 (3)}

O1i_—Ba1—Ba2viii _{105.68 (2) Ba2}xx_—Ba3—Ba3xv _{110.04 (2)}

O3—Ba1—Ba2viii _{40.4 (6) Ba2}xxi_—Ba3—Ba3xv _{110.04 (2)}

O3ii_—Ba1—Ba2viii _{153.62 (9) Ba1}xxii_—Ba3—Ba3xv _{86.66 (2)} Pd2iii_—Ba1—Ba2viii _{118.664 (16) Ba1}xxiii_—Ba3—Ba3xv _{86.66 (2)} Pd2i_—Ba1—Ba2viii _{66.93 (2) Ba1}xxiv_—Ba3—Ba3xv _{140.87 (3)} Ba1iv_—Ba1—Ba2viii _{147.11 (2) Pd2}xvii_—Ba3—Ba3xxv _{47.11 (4)} Ba1v_—Ba1—Ba2viii _{89.09 (2) Pd2}xviii_—Ba3—Ba3xxv _{47.11 (4)} Ba1vi_—Ba1—Ba2viii _{62.776 (19) Pd2}xix_—Ba3—Ba3xxv _{92.93 (5)}

Ba1vii_—Ba1—Ba2viii _{113.456 (15) Ba4—Ba3—Ba3}xxv _144.7

O1i_—Ba1—Ba2ix _{105.68 (2) Ba2—Ba3—Ba3}xxv _{110.04 (2)}

O3—Ba1—Ba2ix _{153.62 (9) Ba2}xx_—Ba3—Ba3xxv _{58.58 (3)}

O3ii_—Ba1—Ba2ix _{40.4 (6) Ba2}xxi_—Ba3—Ba3xxv _{110.04 (2)}

Pd2iii_—Ba1—Ba2ix _{118.664 (16) Ba1}xxii_—Ba3—Ba3xxv _{140.87 (3)} Pd2i_—Ba1—Ba2ix _{66.93 (2) Ba1}xxiii_—Ba3—Ba3xxv _{86.66 (2)} Ba1iv_—Ba1—Ba2ix _{89.09 (2) Ba1}xxiv_—Ba3—Ba3xxv _{86.66 (2)}

Ba1v_—Ba1—Ba2ix _{147.11 (2) Ba3}xv_—Ba3—Ba3xxv _60.0

Ba1vi_—Ba1—Ba2ix _{113.456 (15) Pd1—Ba4—Pd1}ii _109.5

Ba1vii_—Ba1—Ba2ix _{62.776 (19) Pd1—Ba4—Pd1}xxvi _109.5

Ba2viii_—Ba1—Ba2ix _{117.64 (4) Pd1}ii_—Ba4—Pd1xxvi _109.5

O1i_—Ba1—Ba2x _{105.68 (2) Pd1—Ba4—Pd1}xxvii _109.5

O3—Ba1—Ba2x _{40.4 (6) Pd1}ii_—Ba4—Pd1xxvii _109.5

O3ii_—Ba1—Ba2x _{153.62 (9) Pd1}xxvi_—Ba4—Pd1xxvii _109.5

Pd2iii_—Ba1—Ba2x _{66.93 (2) Pd1—Ba4—Ba3 180.00 (3)}

Pd2i_—Ba1—Ba2x _{118.664 (16) Pd1}ii_{—Ba4—Ba3 70.5}

Ba1iv_—Ba1—Ba2x _{113.456 (15) Pd1}xxvi_{—Ba4—Ba3 70.5}

Ba1v_—Ba1—Ba2x _{62.776 (19) Pd1}xxvii_{—Ba4—Ba3 70.5}

Ba1vi_—Ba1—Ba2x _{89.09 (2) Pd1—Ba4—Ba3}xxvii _70.5

supporting information

sup-8

Ba2viii_—Ba1—Ba2x _{52.42 (3) Pd1}xxvi_—Ba4—Ba3xxvii _70.5 Ba2ix_—Ba1—Ba2x _{148.64 (4) Pd1}xxvii_—Ba4—Ba3xxvii _{180.00 (3)}

O2i_—Ba2—O3xi _{73.8 (9) Ba3—Ba4—Ba3}xxvii _109.5

O2i_—Ba2—O3xii _{73.8 (9) Pd1—Ba4—Ba3}xxvi _70.5

O3xi_—Ba2—O3xii _{147.5 (18) Pd1}ii_—Ba4—Ba3xxvi _70.5

O2i_—Ba2—Pd1ii _{82.98 (4) Pd1}xxvi_—Ba4—Ba3xxvi _{180.00 (3)}

O3xi_—Ba2—Pd1ii _{88.04 (10) Pd1}xxvii_—Ba4—Ba3xxvi _70.5

O3xii_—Ba2—Pd1ii _{88.04 (10) Ba3—Ba4—Ba3}xxvi _109.5

O2i_—Ba2—Pd1i _{82.98 (4) Ba3}xxvii_—Ba4—Ba3xxvi _109.5

O3xi_—Ba2—Pd1i _{88.04 (10) Pd1—Ba4—Ba3}ii _70.5

O3xii_—Ba2—Pd1i _{88.04 (10) Pd1}ii_—Ba4—Ba3ii _{180.00 (8)}

Pd1ii_—Ba2—Pd1i _{165.96 (9) Pd1}xxvi_—Ba4—Ba3ii _70.5

O2i_—Ba2—Ba2xiii _{45.0 Pd1}xxvii_—Ba4—Ba3ii _70.5

O3xi_—Ba2—Ba2xiii _{106.4 (7) Ba3—Ba4—Ba3}ii _109.5

O3xii_—Ba2—Ba2xiii _{47.3 (6) Ba3}xxvii_—Ba4—Ba3ii _109.5

Pd1ii_—Ba2—Ba2xiii _{54.36 (4) Ba3}xxvi_—Ba4—Ba3ii _109.5

Pd1i_—Ba2—Ba2xiii _{114.20 (4) Ba4—Pd1—Ba2}xxviii _{137.72 (4)}

O2i_—Ba2—Ba2xiv _{45.0 Ba4—Pd1—Ba2}xxix _{137.72 (4)}

O3xi_—Ba2—Ba2xiv _{47.3 (6) Ba2}xxviii_—Pd1—Ba2xxix _{71.28 (7)}

O3xii_—Ba2—Ba2xiv _{106.4 (7) Ba4—Pd1—Ba2}xxx _{137.72 (4)}

Pd1ii_—Ba2—Ba2xiv _{54.36 (4) Ba2}xxviii_—Pd1—Ba2xxx _{71.28 (7)} Pd1i_—Ba2—Ba2xiv _{114.20 (4) Ba2}xxix_—Pd1—Ba2xxx _{71.28 (7)} Ba2xiii_—Ba2—Ba2xiv _{60.0 Ba1}xxviii_—Pd2—Ba1xxx _{74.93 (7)}

O2i_—Ba2—Ba2vi _{45.0 Ba1}xxviii_—Pd2—Ba1xxix _{74.93 (7)}

O3xi_—Ba2—Ba2vi _{106.4 (7) Ba1}xxx_—Pd2—Ba1xxix _{74.93 (7)}

O3xii_—Ba2—Ba2vi _{47.3 (6) Ba1}xxviii_—Pd2—Ba3xxxi _{135.74 (2)} Pd1ii_—Ba2—Ba2vi _{114.20 (4) Ba1}xxx_—Pd2—Ba3xxxi _{83.58 (4)} Pd1i_—Ba2—Ba2vi _{54.36 (4) Ba1}xxix_—Pd2—Ba3xxxi _{135.74 (2)} Ba2xiii_—Ba2—Ba2vi _{60.0 Ba1}xxviii_—Pd2—Ba3xxxii _{83.58 (4)}

Ba2xiv_—Ba2—Ba2vi _{90.0 Ba1}xxx_—Pd2—Ba3xxxii _{135.74 (2)}

O2i_—Ba2—Ba2vii _{45.0 Ba1}xxix_—Pd2—Ba3xxxii _{135.74 (2)}

O3xi_—Ba2—Ba2vii _{47.3 (6) Ba3}xxxi_—Pd2—Ba3xxxii _{85.78 (8)} O3xii_—Ba2—Ba2vii _{106.4 (7) Ba1}xxviii_—Pd2—Ba3xxxiii _{135.74 (2)} Pd1ii_—Ba2—Ba2vii _{114.20 (4) Ba1}xxx_—Pd2—Ba3xxxiii _{135.74 (2)} Pd1i_—Ba2—Ba2vii _{54.36 (4) Ba1}xxix_—Pd2—Ba3xxxiii _{83.58 (4)} Ba2xiii_—Ba2—Ba2vii _{90.0 Ba3}xxxi_—Pd2—Ba3xxxiii _{85.78 (8)} Ba2xiv_—Ba2—Ba2vii _{60.0 Ba3}xxxii_—Pd2—Ba3xxxiii _{85.78 (8)}

Ba2vi_—Ba2—Ba2vii _{60.0 Ba1}xxxiv_—O1—Ba1xxx _90.0

O2i_—Ba2—Ba3xv _{148.58 (3) Ba1}xxxiv_—O1—Ba1xxviii _180.0

O3xi_—Ba2—Ba3xv _{103.8 (7) Ba1}xxx_—O1—Ba1xxviii _90.0

O3xii_—Ba2—Ba3xv _{103.8 (7) Ba1}xxxiv_—O1—Ba1xxix _90.0

Pd1ii_—Ba2—Ba3xv _{128.44 (6) Ba1}xxx_—O1—Ba1xxix _90.0

Pd1i_—Ba2—Ba3xv _{65.59 (4) Ba1}xxviii_—O1—Ba1xxix _90.0

Ba2xiii_—Ba2—Ba3xv _{149.778 (3) Ba1}xxxiv_—O1—Ba1xxxv _90.0 Ba2xiv_—Ba2—Ba3xv _{149.778 (3) Ba1}xxx_—O1—Ba1xxxv _90.0 Ba2vi_—Ba2—Ba3xv _{110.04 (2) Ba1}xxviii_—O1—Ba1xxxv _90.0 Ba2vii_—Ba2—Ba3xv _{110.04 (2) Ba1}xxix_—O1—Ba1xxxv _180.0

O3xi_{—Ba2—Ba3 103.8 (7) Ba1}xxx_—O1—Ba1xxxvi _180.0

O3xii_{—Ba2—Ba3 103.8 (7) Ba1}xxviii_—O1—Ba1xxxvi _90.0

Pd1ii_{—Ba2—Ba3 65.59 (4) Ba1}xxix_—O1—Ba1xxxvi _90.0

Pd1i_{—Ba2—Ba3 128.44 (6) Ba1}xxxv_—O1—Ba1xxxvi _90.0

Ba2xiii_{—Ba2—Ba3 110.04 (2) Ba2}xxxvii_—O2—Ba2xxviii _180.0 Ba2xiv_{—Ba2—Ba3 110.04 (2) Ba2}xxxvii_—O2—Ba2xxxviii _90.0 Ba2vi_{—Ba2—Ba3 149.778 (3) Ba2}xxviii_—O2—Ba2xxxviii _90.0 Ba2vii_{—Ba2—Ba3 149.778 (3) Ba2}xxxvii_—O2—Ba2xxix _90.0

Ba3xv_{—Ba2—Ba3 62.85 (5) Ba2}xxviii_—O2—Ba2xxix _90.0

O2i_—Ba2—Ba1xvi _{107.018 (16) Ba2}xxxviii_—O2—Ba2xxix _90.0

O3xi_—Ba2—Ba1xvi _{43.6 (7) Ba2}xxxvii_—O2—Ba2iv _90.0

O3xii_—Ba2—Ba1xvi _{152.63 (9) Ba2}xxviii_—O2—Ba2iv _90.0 Pd1ii_—Ba2—Ba1xvi _{119.33 (2) Ba2}xxxviii_—O2—Ba2iv _90.0

Pd1i_—Ba2—Ba1xvi _{65.27 (2) Ba2}xxix_—O2—Ba2iv _180.0

Ba2xiii_—Ba2—Ba1xvi _{148.818 (19) Ba2}xxxvii_—O2—Ba2xxx _90.0 Ba2xiv_—Ba2—Ba1xvi _{90.91 (2) Ba2}xxviii_—O2—Ba2xxx _90.0 Ba2vi_—Ba2—Ba1xvi _{113.456 (15) Ba2}xxxviii_—O2—Ba2xxx _180.0 Ba2vii_—Ba2—Ba1xvi _{63.792 (15) Ba2}xxix_—O2—Ba2xxx _90.0

Ba3xv_—Ba2—Ba1xvi _{60.774 (19) Ba2}iv_—O2—Ba2xxx _90.0

Ba3—Ba2—Ba1xvi _{89.36 (2) Ba2}viii_—O3—Ba2xxxix _{85.3 (13)}

Pd2xvii_—Ba3—Pd2xviii _{94.07 (7) Ba2}viii_—O3—Ba2x _{85.3 (13)} Pd2xvii_—Ba3—Pd2xix _{94.07 (7) Ba2}xxxix_—O3—Ba2x _{85.3 (13)} Pd2xviii_—Ba3—Pd2xix _{94.07 (7) Ba2}viii_—O3—Ba1v _{178.1 (17)}

Pd2xvii_{—Ba3—Ba4 122.33 (5) Ba2}xxxix_—O3—Ba1v _{96.02 (7)}

Pd2xviii_{—Ba3—Ba4 122.33 (5) Ba2}x_—O3—Ba1v _{96.02 (7)}

Pd2xix_{—Ba3—Ba4 122.33 (5) Ba2}viii_—O3—Ba1vi _{96.02 (7)}

Pd2xvii_{—Ba3—Ba2 151.51 (7) Ba2}xxxix_—O3—Ba1vi _{96.02 (7)}

Pd2xviii_{—Ba3—Ba2 67.311 (13) Ba2}x_—O3—Ba1vi _{178.1 (17)}

Pd2xix_{—Ba3—Ba2 67.311 (13) Ba1}v_—O3—Ba1vi _{82.6 (12)}

Ba4—Ba3—Ba2 86.16 (3) Ba2viii_{—O3—Ba1 96.02 (7)}

Pd2xvii_—Ba3—Ba2xx _{67.311 (13) Ba2}xxxix_{—O3—Ba1 178.1 (17)} Pd2xviii_—Ba3—Ba2xx _{67.311 (13) Ba2}x_{—O3—Ba1 96.02 (7)}

Pd2xix_—Ba3—Ba2xx _{151.51 (7) Ba1}v_{—O3—Ba1 82.6 (12)}

Ba4—Ba3—Ba2xx _{86.16 (3) Ba1}vi_{—O3—Ba1 82.6 (12)}

Symmetry codes: (i) x, y−1/2, z−1/2; (ii) x, −y+1/2, −z+1/2; (iii) x, −y+1, −z+1; (iv) z+1/2, −x+1, −y+1/2; (v) −y+1, z, −x+1; (vi) z+1/2, x−1/2, y; (vii)

y+1/2, z, x−1/2; (viii) −y+1, z+1/2, −x+1/2; (ix) z+1, −x+1/2, −y+1/2; (x) z+1, x, y; (xi) x−1/2, −y+1/2, −z; (xii) x−1/2, y−1/2, z; (xiii) −y+1/2, z, −x+1/2; (xiv) z+1/2, −x+1/2, −y; (xv) x, −y, −z; (xvi) z, −x+1, −y; (xvii) x−1, −y+1, −z+1; (xviii) −x+1, y−1, −z+1; (xix) −x+1, −y+1, z−1; (xx) y, z, x; (xxi) z, x, y; (xxii) y, z, x−1; (xxiii) z, x−1, y; (xxiv) x−1, y, z; (xxv) −x, −y, z; (xxvi) −x+1/2, y, −z+1/2; (xxvii) −x+1/2, −y+1/2, z; (xxviii) y+1/2, z+1/2, x; (xxix) z+1/2,