X-ray powder diffraction beamline at D10B of LNLS: application to the Ba2FeReO6 double perovskite

Ferreira, F.F.; Granado, E.; Carvalho, W. Jr; Kycia, S.W.; Bruno, D.; Droppa, R. Jr

doi:10.1107/S0909049505039208

research papers

JOURNAL OF
SYNCHROTRON
RADIATION

ISSN: 1600-5775

Volume 13| Part 1| January 2006| Pages 46-53

doi:10.1107/S0909049505039208

X-ray powder diffraction beamline at D10B of LNLS: application to the Ba₂FeReO₆ double perovskite

Fabio Furlan Ferreira,^a Eduardo Granado,^b,^a ^* Wilson Carvalho Jr,^a Stefan W. Kycia,^a Daniele Bruno ^a and Roosevelt Droppa Jr ^a

^aLaboratório Nacional de Luz Síncrotron, Caixa Postal 6192, CEP 13084-971, Campinas, SP, Brazil, and ^bInstituto de Física `Gleb Wataghin', UNICAMP, CEP 13083-970, Campinas, SP, Brazil
^*Correspondence e-mail: granado@lnls.br

(Received 19 October 2005; accepted 25 November 2005)

A new beamline, fully dedicated to X-ray powder diffraction (XPD) measurements, has been installed after the exit port B of the bending magnet D10 at the Brazilian Synchrotron Light Laboratory (LNLS) and commissioned. The technical characteristics of the beamline are described and some performance indicators are listed, such as the incoming photon flux and the angular/energy resolutions obtainable under typical experimental conditions. The results of a Rietveld refinement for a standard sample of Y₂O₃ using high-resolution data are shown. The refined parameters match those found in the literature, within experimental error. High-resolution XPD measurements on Ba₂FeReO₆ demonstrate a slight departure from the ideal cubic double-perovskite structure at low temperatures, not detected by previous powder diffraction experiments. The onset of the structural transition coincides with the ferrimagnetic ordering temperature, T_c ≃ 315 K. Subtle structural features, such as those reported here for Ba₂FeReO₆, as well as the determination and/or refinement of complex crystal structures in polycrystalline samples are ideal candidate problems to be investigated on this beamline.

Keywords: X-ray powder diffraction; high resolution; structural phase transitions; energy resolution; Rietveld refinement; LNLS.

1. Introduction

During the last two decades, synchrotron X-ray powder diffraction (S-XPD) has become a well established technique, being suitable for applications in a number of research fields, such as materials science, condensed matter physics, nanoscience and protein crystallography. The large photon flux and almost parallel beam optics inherent to this technique allow superior instrumental resolution and/or counting statistics when compared with neutron or conventional-source X-ray diffraction under typical experimental conditions. Such characteristics of S-XPD can contribute to the investigation of three broad classes of problems. First of all, when the probed sample presents phases of good crystallinity, the narrow instrumental resolution of the Bragg peaks obtainable by S-XPD is desirable to minimize Bragg peak overlaps, leading to reliable crystal structure solutions and/or refinements. Another typical case for S-XPD is when the scattering by the phase(s) of interest is quite low and cannot be detected by standard techniques. For such problems, the advantage of the large photon flux of a synchrotron source is readily realised, although a compromise with the instrumental resolution is necessary in many cases. Last, but not least, the energy tunability of a synchrotron X-ray beam allows for the study of anomalous scattering, in which the contrast between the scattering factors of different elements can be conveniently tuned.

This paper reports on the construction and commissioning of a fully dedicated X-ray powder diffraction (XPD) beamline at the Brazilian Synchrotron Light Laboratory (LNLS). The beamline was installed after the exit port B of the bending magnet D10. It was built as a response to the demands of an ever growing X-ray powder diffraction community in Brazil and, more generally, in Latin America. The performance of this beamline is illustrated by a preliminary high-resolution XPD study on Ba₂FeReO₆, which reveals deviations from the ideal cubic double-perovskite structure at low temperatures. The high resolution attainable in this beamline is shown to be essential to detect the slight tetragonal distortion in this case.

2. Instrumentation

2.1. Beamline optics

Fig. 1 shows (a) the layout of the XPD beamline at LNLS and (b) a photograph of the diffractometer inside the experimental hutch. The source is a 1.67 T bending magnet of the LNLS ring operating at 1.37 GeV (Craievich & Rodrigues, 1997 ; Rodrigues et al., 1998 ), with a typical initial average current of about 270 mA and 20 h lifetime (September 2004). The critical energy of the emitted photons is 2.08 keV. The beamline operates in the energy range 4.5–15 keV (2.76–0.83 Å) with a maximum horizontal acceptance of about 10 mrad.

Figure 1
(a) Layout of the XPD beamline at the LNLS. (b) Picture of the experimental hutch, showing the 4 + 2 circle diffractometer and a closed-cycle He cryostat at the sample position.

A Rh-coated ULE (Ultra-Low Expansion, Corning¹) glass curved mirror, which is used to filter high-energy photons and vertically focus/collimate the beam, is located at approximately 7 m from the synchrotron source. The angle between the incident beam and the mirror is typically 4.5 mrad, which determines the cut-off energy of ∼15 keV. The mirror is mounted in a home-made chamber (Neuenschwander & Tavares, 2001 ), operating at ∼10⁻⁷ Pa, separated by two 125 µm beryllium windows from the front-end and the monochromator. Three independent Parker motors, with a Heidenhain encoder, allow for the adjustment of the mirror positions (height, vertical and horizontal angles), while a Phytron motor, with a potentiometer-like encoder, bends the mirror. Their positions are read by a 12-bit AD card (bending) and Heidenhain encoder (three axes). Home-made software, named SPEGULO, controls the position of the mirror.

Monochromatization is carried out using a double-bounce Si(111) monochromator, with water refrigeration in the first crystal while the second one is bent for sagittal focusing (Giles et al., 2003 ). The whole monochromator system is mounted onto a commercial Huber goniometer under high vacuum (typically 10⁻⁵ Pa), providing good energy stability and reproducibility (better than 0.2 eV after cycling between 7 keV and 13 keV).

Four sets of four-blade slits may be used. Two of them are computer-controlled by 3-WinDCM software (Piton & Duarte, 1998 ). The one positioned before the mirror is water-cooled and limits the horizontal and vertical divergence of the incoming white beam, while a second set is placed before the diffractometer and defines the beam size at the sample position. The two other sets of slits are manually operated and are placed at the 2θ arm of the diffractometer, defining resolution and/or reducing background scattering (Le Bolloc'h et al., 2002 ). To minimize unwanted beam attenuation and air scattering, a vacuum path with Kapton windows is positioned between the last set of computer-controlled slits and the diffractometer. Another vacuum path is positioned between the sample and the detector, at the diffractometer 2θ arm.

2.2. Diffractometer

A Huber 4 + 2 circle diffractometer equipped with a Eulerian cradle (model 513) is located inside the experimental hutch, ∼13 m from the monochromator. The diffractometer is mounted on a lifting/laterally translating table which allows the correct positioning of the X-ray beam in its center. The minimum angular step of the 2θ arm is 0.0001°.

Flat-plates or capillary tube samples may be attached to a goniometer head (model 1001) with four adjustable axes. The diffractometer is operated using the SPEC software (Certified Scientific Software, 1992 ) in a PC-based Linux environment.

Routine powder diffraction experiments are performed using the Huber diffractometer in either high-resolution (with analyzer crystals) or high-intensity (medium resolution) modes. In the high-resolution mode, Si(111), Ge(111) or Ge(220) analyzer crystals may be employed. This mode is particularly useful in minimizing the superposition of neighboring Bragg peaks, allowing for more reliable solutions and/or refinements of crystalline structures. In high-intensity mode, a (002) highly oriented pyrolitic graphite (HOPG) analyzer may be employed, or, alternatively, no analyzer is used.

In this beamline, most experiments are performed in reflection (θ–2θ) geometry. This is due to the relatively large wavelengths obtainable with useful intensities in the dipole sources of LNLS (≳1 Å), leading to small penetration depths for most inorganic samples. In special cases, transmission experiments using capillary tubes may also be performed. The 2θ arm may be varied by up to ∼150° under normal operational conditions. For room-temperature measurements, the sample may be attached to a spinning system, greatly reducing the unwanted effects of poor grain statistics that might be important in some cases.

For investigations involving special thermal environments, a commercial closed-cycle He cryostat (Advanced Research Materials), with vibration damping and temperature control (10–450 K), and a home-made furnace (293–1273 K) are available. The integration of these systems to the diffractometer allows for the sample to oscillate or rotate along θ (up to a few degrees in amplitude) during each step in 2θ, fairly improving grain statistics.

2.3. Detection system

The detection system is composed of two high-throughput Cyberstar X1000 (Oxford Danfysik) X-ray detectors; one captures air scattering to monitor the incident flux and the other detects the sample-diffracted photons. These detectors allow for count rates up to 10⁶ counts s⁻¹, with a very good linear response up to ∼3 × 10⁵ counts s⁻¹. The incident flux may also be monitored by a home-made proportional counter.

A 5 cm-long proportional linear detector (MBraun), suitable for instantaneous measurements of a limited angular region of a powder diffraction profile, has been purchased and integrated in the beamline. It operates under high pressure (7.5 × 10⁵ Pa) using a mixture of argon and methane, and shows a spatial resolution better than 70 µm and ∼50% quantum efficiency (λ = 1.5 Å). Also, a home-made motorized imaging-plate system, which may be attached to the furnace, permits the fast acquisition of full patterns, suitable for phase transition studies. Finally, an X-ray eye (Photonic Science), which is a simple high-efficiency X-ray-sensitive CCD video camera, is used to focus the beam onto the sample position as well as to check the alignment of the sample with respect to the beam.

2.4. Commissioning results

In order to evaluate the energy resolution of the beam, rocking curves of the (111) and (333) reflections of a Si single crystal were recorded for several values of the radius of curvature of the mirror, with λ = 1.2012 Å. Using the corresponding rocking widths, it was possible to calculate the wavelength distribution width, Δλ/λ, for the different curvatures, as shown in Fig. 2. The determination of the wavelength distribution width took into account a deconvolution of the peak widths as shown below,

$[{{\Delta\lambda}\over\lambda}={{\Delta{E}}\over{E}}=\left\{{{\left({w_{333}^2-w_{111}^2}\right)-\left({w_{{\rm{D}}333}^2-w_{{\rm{D}}111}^2}\right)}\over{\left[{\tan\left({\theta_{\rm{m}}}\right)-\tan\left({\theta_2}\right)}\right]^2-\left[{\tan\left({\theta_{\rm{m}}}\right)-\tan\left({\theta_1}\right)}\right]^2}}\right\}^{1/2},\eqno(1)]$

where w₁₁₁ and w₃₃₃ are the measured rocking widths and w_D111 and w_D333 are the Darwin widths of the (111) and (333) reflections of a Si crystal. θ₁ and θ₂ are the angles of the (111) and (333) reflections; θ_m is the monochromator angle. The term in the denominator considers a set-up in non-dispersive mode.

Figure 2
Vertical size (full width at half-maximum) and wavelength resolution of the beam at the sample position as a function of the curvature of the mirror in relative units [0% and 100% correspond to minimum (21.7 km) and maximum (1.7 km) allowed curvatures, respectively]. Lines are guides to the eyes.

The vertical size of the beam was obtained by translating the crystal across the beam, and measuring the transmitted signal (see Fig. 2). The configuration that is closest to parallel beam (Parrish et al., 1986 ) was achieved with Δλ/λ ≃ 2.5 × 10⁻⁴ and a vertical beam size of about 1.5 mm (FWHM). When the beam was focused onto the sample position, its vertical size was about 0.8 mm and Δλ/λ = 3.9 × 10⁻⁴. A good compromise is obtained with a vertical size of 1.0 mm and Δλ/λ = 2.8 × 10⁻⁴.

Fig. 3 shows the photon flux of the beamline for wavelengths between 0.83 Å and 2.76 Å, measured using a 100%-efficient Si photodetector coupled to a Keithley picoamperemeter. The X-ray beam was focused onto the sample position with a cross section of approximately 2 mm (H) × 0.8 mm (V). Both the mirror and the sagittal crystal were adjusted to maximize the current at each energy. The maximum flux was reached at about 1.8 Å (∼8.4 × 10¹⁰ photons s⁻¹ at 200 mA). In the low-energy region the fast decrease in the photon flux is mainly due to air absorption. In a typical (non-anomalous) X-ray powder diffraction experiment, the energy is kept between 1.2 and 1.4 Å allowing one to obtain more structural information than at 1.8 Å, with no significant decrease in the photon flux.

Figure 3
Photon flux of the beamline at the sample position as a function of wavelength.

The beamline performance was evaluated by means of measurements of powder diffraction profiles of NIST standard samples: LaB₆ (SRM 660a), Si (SRM 640c) and Al₂O₃ (SRM 676). For such measurements a Ge(111) analyzer crystal was employed, with λ = 1.77141 Å and λ = 1.37791 Å. Here, the mirror curvature was 45% (see Fig. 2), leading to a beam at the sample position with dimensions 2 mm (H) × 1.0 mm (V). The use of a Ge(111) analyzer crystal leads to a sharp instrumental angular resolution, Γ_2θ ≃ 0.01° at low angles, and efficiently removes unwanted fluorescence and air-scattering background, at the expense of a significant signal reduction. In this configuration the integrated intensity is ∼30 times smaller when compared with a high-intensity set-up (no analyzer, instrumental angular resolution Γ_2θ = 0.08°). Fig. 4(a) shows the linewidths (FWHM) of the Bragg peaks of each standard sample as a function of 2θ, based on a set of GSAS (Larson & Von Dreele, 2000 ; Toby, 2001 ) profile terms obtained in a Rietveld refinement (Rietveld, 1969 ). Fig. 4(b) shows the same results in terms of the wavenumber transfer Q. As certified by NIST (NIST, 2000), LaB₆ is an almost strain-free sample. Thus, the linewidths obtained for this sample may be taken as a good estimate of the instrumental resolution. Although considerations of particle size and strain broadening effects (see Balzar et al., 2004 , and references therein) are beyond the scope of the present work, it is readily realised in Fig. 4 that they significantly contribute to the total linewidths for the Si and Al₂O₃ standard samples, illustrating the high resolution power of the beamline when analyzer crystals are employed.

Figure 4
Bragg peak widths [full width at half-maximum in (a) 2θ and (b) Q] as a function of (a) 2θ and (b) Q for selected standard samples. The set of experimental parameters used here are given in the text.

Fig. 5 shows a comparison between measured and calculated X-ray powder diffraction profiles for Y₂O₃, after a Rietveld refinement (Rietveld, 1969) using the program GSAS (Larson & Von Dreele, 2001 ). For this specific measurement, a Ge(111) analyzer was employed, the chosen step width was 0.0025° in 2θ, and the intensity of the strongest Bragg peak was ∼49000 counts s⁻¹ at 200 mA against a background level of ∼8 counts s⁻¹. The wavelength was λ = 1.37794 Å and the total collection time was ∼8 h. The sample was mounted onto the spinning system, operating at a rate of ∼120 r.p.m. The peak profiles were modeled using a modified pseudo-Voigt function (Finger et al., 1994 ) which takes into account the reflection asymmetry due to axial divergence. In the refinement, the degree of linear polarization of the incoming photons was kept fixed at 95%. The inset illustrates the fit for two particular reflections, (222) and (622), at 2θ ≃ 26.01° and 51.06°, respectively. Table 1 summarizes some of the refined structural parameters and goodness-of-fit indicators. Comparison of these data with reported structural values (Paton & Maslen, 1965 ; Bonnet & Delapalme, 1975 ) shows an agreement within experimental errors.

Table 1
Structural parameters of an Y₂O₃ standard sample obtained from a Rietveld refinement using high-resolution data (see Fig. 5). Goodness-of-fit indicators are also given. Errors in parentheses are statistical only, and represent one standard deviation

Atom	#	Oxidation state	Site	x	y	z	B_iso (Å²)
Y	1	+3	8b	0.25	0.25	0.25	0.60 (2)
Y	2	+3	24d	0.467505 (20)	0	0.25	0.55 (2)
O	1	−2	48e	0.10870 (17)	0.34777 (17)	0.11949 (17)	0.66 (4)

a (Å)	R_pb	R_wpb	R_F²	χ²
10.60389 (1)	7.87%	25.80%	3.23%	1.40

Figure 5
Observed (cross symbols) and calculated (solid line) high-resolution X-ray powder diffraction intensities for Y₂O₃. The difference profile is also given. The wavelength was λ = 1.37794 Å.

3. Case study: reinvestigation of the crystal structure of Ba₂FeReO₆ double perovskite

A scientific application of the high resolution attainable at this beamline is described here in an investigation of the crystal structure of Ba₂FeReO₆. Double perovskites with formula A₂Fe(Mo,Re)O₆ (A = Ca, Sr, Ba) show interesting electronic and magnetic properties. Most members of the family present a half-metallic state with large tunneling magnetoresistance at room temperature (Kobayashi et al., 1998 , 1999 ; Maignan et al., 1999 ; Prellier et al., 2000 ; Gopalakrishnan et al., 2000 ; Dai et al., 2001 ), being promising candidates for applications in the field of spin electronics.

Intriguing structural effects have been observed for this family, generally related to magnetic and/or electronic phenomena. For example, the compound Sr₂FeMoO₆ displays a simultaneous structural and magnetic transition from a tetragonal ferrimagnetic to a cubic paramagnetic phase at ∼410 K (Ritter et al., 2000 ). Another interesting case is the compound Ca₂FeReO₆ with monoclinic symmetry (space group P2₁/n), which shows a competition between two inequivalent ground states with the same space group, leading to a concomitant structural, magnetic and metal–insulator phase transition at ∼135–150 K (Kato et al., 2002 ; Granado et al., 2002 ; Oikawa et al., 2003 ; De Teresa et al., 2004 ).

To the best of our knowledge, the mechanism coupling magnetic and structural degrees of freedom in these double perovskites is not fully elucidated. Perhaps an indication of the non-trivial nature of this phenomenon is the fact that the strong magnetic effects on the crystal structure of Ca₂FeReO₆ were not observed in Ca₂FeMoO₆ with the same monoclinic symmetry. Such comparison led to the suggestion that the Re 5d electrons may be strongly correlated in these double perovskites electrons (Granado et al., 2002; Iwasawa et al., 2005 ), in opposition to the Mo 4d electrons. To clarify this issue, it is paramount to characterize the phenomenon for different compounds of this family. Of particular interest are those examples where the paramagnetic phase shows cubic symmetry, such as the above-mentioned Sr₂FeMoO₆ (Ritter et al., 2000), and Ba₂FeReO₆. For these cases the possible lattice distortion occurring below the magnetic ordering temperature may be entirely driven by the magnetism. Considering the strong magneto-elastic effects observed in Ca₂FeReO₆, it is interesting to note that the compound Ba₂FeReO₆ has been reported to keep an undistorted cubic structure (see Fig. 6) even below T_c, based upon conventional X-ray powder diffraction measurements (Rammeh et al., 2004 ).

Figure 6
Representation of the crystal structure of Ba₂FeReO₆ in the paramagnetic phase. Green: FeO₆ octahedra; blue: ReO₆ octahedra; red: Ba ions.

Here, the crystal structure of Ba₂FeReO₆ is reinvestigated by high-resolution S-XPD. It is shown that a small structural distortion, not previously detected, actually takes place below the ferrimagnetic ordering temperature, T_c ≃ 315 K (Prellier et al., 2000). This observation, made possible by the high resolution attainable in the XPD beamline, indicates that the orbital degree of freedom is manifested in this metallic compound.

The preparation procedures and characterization of the ceramic sample of Ba₂FeReO₆ used in this work are described elsewhere (Prellier et al., 2000; Gopalakrishnan et al., 2000). The high-resolution S-XPD experiments were performed on Ba₂FeReO₆ using monochromatic beams with λ = 1.37728 Å or λ = 1.77137 Å, and employing the Ge(111) analyzer crystal before a scintillation detector. A flat-plate geometry was employed, and the Cu sample holder was attached to the closed-cycle cryostat (see §2.2). The data were collected between 15° and 150° with steps of 0.01° in 2θ. In order to improve grain statistics, the θ angle, to which the cryostat was coupled, was rocked by 0.5–1.0° at each step. Crystal structure refinements were carried out using the program GSAS with the EXPGUI platform (Larson & Von Dreele, 2000; Toby, 2001). An impurity phase of Fe₃O₄ was detected (0.8% weight fraction), and included in the refinement.

Fig. 7 shows the observed S-XPD intensities of Ba₂FeReO₆ at (a) 14 K and (b) 400 K in a selected angular interval (cross symbols). For T = 14 K, the crystal structure of this compound was refined using a tetragonal double-perovskite model (I4/mmm symmetry), while for T = 400 K a cubic model (Pm $[\bar3]$ m symmetry) was employed. The Fe and Re cationic disorder was refined using the data taken at 400 K, and was found to be 3.7% of Re ions in the Fe site, and vice versa, attesting for the good quality of our sample. The refined structural parameters at 14 K and 400 K are shown in Table 2. In the tetragonal phase with the I4/mmm symmetry used in the structural model at 14 K, either the FeO₆ or ReO₆ octahedra (or both) are contracted along the c axis, and are not rotated with respect to the cubic structure. Unfortunately, our experimental errors on the determination of the oxygen positions (∼0.01 Å) do not allow us to unambiguously determine which octahedra (FeO₆ or ReO₆) are actually distorted (see Table 2). In any case, the small magnitude of the distortion is suggestive of orbital phenomena caused by either the Fe 3d:t_2g or Re 5d:t_2g valence electrons.

Table 2
Structural parameters of Ba₂FeReO₆ obtained from Rietveld refinements using high-resolution data at 14 K and 400 K (see Fig. 7). Selected bond distances and goodness-of-fit indicators are also given. Errors in parentheses are statistical only, and represent one standard deviation

Temperature	14 K	400 K
Space group	I4/mmm (#139)	$[Pm\bar3m]$ (#225)
a (Å)	5.68278 (2)	8.063328 (13)
c (Å)	8.02337 (5)	–

Fe	2a (0, 0, 0)	4a (0, 0, 0)
Re	2b (0, 0, 1/2)	4b (1/2, 1/2, 1/2)
B_iso (Fe,Re) (Å²)	0.66 (2)	0.79 (2)

Ba	4d (1/2, 0, 1/4)	8c (1/4, 1/4, 1/4)
B_iso (Ba) (Å²)	0.26 (2)	0.57 (2)

O1	8h (x, x, 0)	24e (x, 0, 0)
x	0.2569 (13)	0.2608 (9)
O2	4e (0, 0, z)	–
z	0.255 (2)	–
B_iso (O1,O2) (Å²)	0.1 (1)	0.7 (1)

d(Fe—O1) (Å)	2.065 (11)	2.103 (8)
d(Fe—O2) (Å)	2.044 (17)	–
d(Re—O1) (Å)	1.953 (11)	1.929 (8)
d(Re—O2) (Å)	1.968 (17)	–
R_pb	15.1%	13.0%
R_wpb	37.5%	28.8%
χ²	1.89	1.68

Figure 7
Observed (cross symbols) and calculated (solid line) high-resolution X-ray powder diffraction intensities in a selected angular interval for Ba₂FeReO₆ at (a) 14 K with the Rietveld refinement performed under a tetragonal model (space group I4/mmm), and (b) 400 K with the refinement under a cubic model (space group Pm $[\bar3]$ m). The difference profiles are also given. Short vertical bars correspond to the calculated Bragg peak positions. The wavelength was λ = 1.37728 Å. The total collection time for each profile (15° ≤ 2θ ≤ 150°) was ∼4 h.

In order to establish the structural transition temperature and attempt to correlate structural and magnetic properties, the crystal structure of Ba₂FeReO₆ was also studied at intermediate temperatures. During the refinements a difficulty arose. While the tetragonal distortion was clearly established at 14 K (see Fig. 7), the situation was less clear for temperatures approaching the transition, where the splitting of some Bragg peaks caused by the distortion could not be clearly resolved. As a consequence, the tetragonal distortion could not be reliably obtained directly from the Rietveld refinement above ∼200 K. Fig. 8(a) shows the relative difference of goodness-of-fit for the Rietveld refinements using the tetragonal and cubic symmetries, (χ_cubic² − χ_tetrag²)/χ_tetrag², as a function of temperature, indicating that the structural transition occurs close to the magnetic-ordering temperature, T_c ≃ 315 K (Prellier et al., 2000). Fig. 8(b) shows the tetragonal distortion, a − c/2^1/2, also suggesting that the structural transition takes place close to T_c.

Figure 8
Temperature-dependencies of (a) the relative difference in the goodness-of-fit factor obtained for Rietveld refinements under cubic $[Pm\bar3m]$ and tetragonal I4/mmm symmetries, $[(\chi\,_{\rm{cubic}}^2-\chi\,_{\rm{tetrag}}^2)/\chi\,_{\rm{tetrag}}^2]$ for Ba₂FeReO₆, (b) tetragonal distortion, a-c/2^1/2 (solid circles), and (c) linewidth of the (004) Bragg peak above 200 K. All measurements were taken on warming. The dashed vertical line indicates the ferrimagnetic ordering temperature for Ba₂FeReO₆ (Prellier et al. (2000

), while the dotted curve in (b) is a guide to the eyes.

In the temperature range where the tetragonal distortion of Ba₂FeReO₆ could not be reliably extracted from the Rietveld method (T > 200 K), the structural transition was probed by an investigation of the signal at the scattering angle corresponding to 2d ≃ 4.02 Å. In fact, for the tetragonal phase both the (220) and (004) Bragg peaks contribute to the diffracted intensities at this region, centered at slightly different angular positions. However, for extreme cases where the separation of the (220) and (004) peaks is much smaller than the peak widths, the deviation from cubic metrics is only manifested by a broadening of the resulting peak. Fig. 8(c) shows the temperature-dependence of the width of the scattering at the (004) position (fitted by a single Lorentzian line-shape), taken on cooling, with λ = 1.77137 Å. It can be seen that this peak broadens significantly below T_c ≃ 315 K, clearly indicating that the tetragonal-to-cubic transition occurs at this temperature. A similar analysis for the cubic (111) Bragg reflection (2d ≃ 9.28 Å) does not show this effect (see Fig. 8c), as expected, since this peak does not of course split under a tetragonal distortion.

The observations described above for Ba₂FeReO₆ indicate that the coupling between lattice and spin degrees of freedom is general for this family and not restricted to Ca₂FeReO₆ (Granado et al., 2002). Since the magnetic and structural transition temperatures appear to coincide, a strong spin–orbit coupling caused by unquenched Re 5d orbital moments is the most likely mechanism leading to the concomitant spin-structural transition in Ba₂FeReO₆. Further work is necessary to establish the impact of the small tetragonal deformation below T_c on the overall physical properties of this compound.

4. Summary

In summary, the XPD beamline at LNLS has been successfully constructed and commissioned. This facility shall be very useful in cases where it is necessary to reduce overlap between neighboring Bragg peaks in powder diffractograms, i.e. in structures with large unit cells or with small lattice distortions. Alternatively, high intensities may be obtained, allowing for weak Bragg peaks to be easily detected. The different set-ups readily available in this beamline pave the way for investigations on a broad range of materials, which may be carried out under different sample environments. Crystal structure refinements and/or determinations are liable to be performed using powder diffraction data taken at this beamline. The use of this facility has been demonstrated by an investigation of the crystal structure of the Ba₂FeReO₆ double perovskite, revealing small lattice distortions coupled to the magnetic order not previously observed in conventional X-ray powder diffraction experiments.

Supporting information

Crystal structure: contains datablocks I, II, III, global, T14KBST_phase_2, T14KBST_phase_3, T400KBST_phase_1, T400KBST_phase_2, T14KBST_p_01, T400KBST_p_01, T14KBST_overall, T400KBST_overall. DOI: 10.1107/S0909049505039208/ml5212sup1.cif

Rietveld powder data: contains datablock I. DOI: 10.1107/S0909049505039208/ml5212Isup2.rtv

Rietveld powder data: contains datablock II. DOI: 10.1107/S0909049505039208/ml5212IIsup3.rtv

Rietveld powder data: contains datablock III. DOI: 10.1107/S0909049505039208/ml5212IIIsup4.rtv

Structure factors: contains datablock I. DOI: 10.1107/S0909049505039208/ml5212Isup5.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0909049505039208/ml5212IIsup6.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0909049505039208/ml5212IIIsup7.hkl

Computing details top

Data collection: SPEC (Certified Scientific Software, 1992) for (I). Data reduction: POWF 2.11 (Virginia Tech, 2001-2003) for (I). For all compounds, program(s) used to solve structure: GSAS (Larson & Von Dreele, 2001). Program(s) used to refine structure: GSAS for (I).

Figures top

(T14KBST_phase_2) iron oxide top

Crystal data top

Fe₃O₄	Z = 8
M_r = 231.54	Synchrotron radiation, λ = 1.377285 Å
Cubic, Fd3m	T = 14 K
Hall symbol: F d -3 m	Particle morphology: powder
a = 8.3814 (5) Å	flat_sheet, 20 × 10 mm
V = 588.78 (10) Å³

Data collection top

Huber 4+2 circle diffractometer	Data collection mode: reflection
Radiation source: synchrotron, LNLS D10B-XPD beamline	Scan method: step
Si 111 monochromator	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Specimen mounting: copper sample holder

Refinement top

Least-squares matrix: full	13520 data points
R_p = 0.168	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(LX) = 0.000 #5(LY) = 19.847 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 8.917 #2(GV) = 4.299 #3(GW) = -0.168 #4(LX) = 0.000 #5(LY) = 7.306 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
R_wp = 0.267	24 parameters
R_exp = 0.195	0 restraints
R(F²) = 0.18130	(Δ/σ)_max = 0.02
χ² = 1.904	Background function: GSAS Background function number 2 with 10 terms. Cosine Fourier series 1: 1.69071 2: -2.03612 3: -3.99352 4: -3.60868 5: -3.03652 6: -2.11781 7: -1.58570 8: -1.02935 9: -0.776166 10: -0.281473

Crystal data top

Fe₃O₄	Z = 8
M_r = 231.54	Synchrotron radiation, λ = 1.377285 Å
Cubic, Fd3m	T = 14 K
a = 8.3814 (5) Å	flat_sheet, 20 × 10 mm
V = 588.78 (10) Å³

Data collection top

Huber 4+2 circle diffractometer	Scan method: step
Specimen mounting: copper sample holder	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Data collection mode: reflection

Refinement top

R_p = 0.168	χ² = 1.904
R_wp = 0.267	13520 data points
R_exp = 0.195	24 parameters
R(F²) = 0.18130	0 restraints

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

	x	y	z	U_iso*/U_eq
Fe1	0.125	0.125	0.125	−0.001 (4)*
Fe2	0.5	0.5	0.5	−0.001 (4)*
O	0.2583	0.2583	0.2583	−0.001 (4)*

Geometric parameters (Å, º) top

Fe1—O	1.9351 (1)	Fe2—O^vii	2.0282 (1)
Fe1—Oⁱ	1.9351 (1)	Fe2—O^viii	2.0282 (1)
Fe1—Oⁱⁱ	1.9351 (1)	Fe2—O^ix	2.0282 (1)
Fe1—Oⁱⁱⁱ	1.9351 (1)	O—Fe1	1.9351 (1)
Fe2—O^iv	2.0282 (1)	O—Fe2^vii	2.0282 (1)
Fe2—O^v	2.0282 (1)	O—Fe2^viii	2.0282 (1)
Fe2—O^vi	2.0282 (1)	O—Fe2^ix	2.0282 (1)

O—Fe1—O^x	109.471 (2)	O^v—Fe2—O^ix	93.9965
O—Fe1—O^xi	109.471 (4)	O^vi—Fe2—O^xiii	93.9965
O—Fe1—O^xii	109.471 (2)	O^vi—Fe2—O^xiv	93.9965
O^x—Fe1—O^xi	109.471 (2)	O^vi—Fe2—O^ix	179.9802
O^x—Fe1—O^xii	109.471 (4)	O^xiii—Fe2—O^xiv	86.0035
O^xi—Fe1—O^xii	109.471 (2)	O^xiii—Fe2—O^ix	86.0035
O^iv—Fe2—O^v	86.0035	O^xiv—Fe2—O^ix	86.0035
O^iv—Fe2—O^vi	86.0035	Fe1—O—Fe2^xv	122.484 (2)
O^iv—Fe2—O^xiii	179.9802	Fe1—O—Fe2^viii	122.4840 (12)
O^iv—Fe2—O^xiv	93.9965	Fe1—O—Fe2^xvi	122.4840 (12)
O^iv—Fe2—O^ix	93.9965	Fe2^xv—O—Fe2^viii	93.8613
O^v—Fe2—O^vi	86.0035	Fe2^xv—O—Fe2^xvi	93.8613
O^v—Fe2—O^xiii	93.9965	Fe2^viii—O—Fe2^xvi	93.8613
O^v—Fe2—O^xiv	179.9802

Symmetry codes: (i) −z+1/4, x, −y+1/4; (ii) −z+1/4, −x+1/4, y; (iii) z, −x−3/4, −y−3/4; (iv) x+1/4, y+1/4, −z+1; (v) −z+1, x+1/4, y+1/4; (vi) y+1/4, −z+1, x+1/4; (vii) −x+3/4, −y+3/4, z; (viii) z, −x+3/4, −y+3/4; (ix) −y+3/4, z, −x+3/4; (x) −z−3/4, x−1, −y−7/4; (xi) −z−3/4, −x−3/4, y−2; (xii) z−1, −x+1/4, −y−3/4; (xiii) −x+3/4, −y+7/4, z−1; (xiv) z−1, −x+7/4, −y+3/4; (xv) −x+7/4, −y+3/4, z−1; (xvi) −y+7/4, z−1, −x+3/4.

(T14KBST_phase_3) top

Crystal data top

Ba₂FeReO₆	V = 259.11 (1) Å³
M_r = 306.36	Z = 4
Tetragonal, I4/mmm	Synchrotron radiation, λ = 1.377285 Å
Hall symbol: I 4/m m m	T = 14 K
a = 5.68278 (2) Å	Particle morphology: powder
c = 8.02337 (5) Å	flat_sheet, 20 × 10 mm

Data collection top

Huber 4+2 circle diffractometer	Data collection mode: reflection
Radiation source: synchrotron, LNLS D10B-XPD beamline	Scan method: step
Si 111 monochromator	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Specimen mounting: copper sample holder

Refinement top

Least-squares matrix: full	13520 data points
R_p = 0.168	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(LX) = 0.000 #5(LY) = 19.847 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 8.917 #2(GV) = 4.299 #3(GW) = -0.168 #4(LX) = 0.000 #5(LY) = 7.306 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
R_wp = 0.267	24 parameters
R_exp = 0.195	0 restraints
R(F²) = 0.18130	(Δ/σ)_max = 0.02
χ² = 1.904	Background function: GSAS Background function number 2 with 10 terms. Cosine Fourier series 1: 1.69071 2: -2.03612 3: -3.99352 4: -3.60868 5: -3.03652 6: -2.11781 7: -1.58570 8: -1.02935 9: -0.776166 10: -0.281473

Crystal data top

Ba₂FeReO₆	V = 259.11 (1) Å³
M_r = 306.36	Z = 4
Tetragonal, I4/mmm	Synchrotron radiation, λ = 1.377285 Å
a = 5.68278 (2) Å	T = 14 K
c = 8.02337 (5) Å	flat_sheet, 20 × 10 mm

Data collection top

Huber 4+2 circle diffractometer	Scan method: step
Specimen mounting: copper sample holder	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Data collection mode: reflection

Refinement top

R_p = 0.168	χ² = 1.904
R_wp = 0.267	13520 data points
R_exp = 0.195	24 parameters
R(F²) = 0.18130	0 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
FE1	0.0	0.0	0.0	0.00840 (17)*	0.9646
RE2	0.0	0.0	0.5	0.00840 (17)*	0.9646
BA3	0.5	0.0	0.25	0.00325 (16)*
O4	0.2570 (13)	0.2570 (13)	0.0	0.0011 (10)*
O5	0.0	0.0	0.255 (2)	0.0011 (10)*
FE6	0.0	0.0	0.5	0.00840 (17)*	0.0354
RE7	0.0	0.0	0.0	0.00840 (17)*	0.0354

Geometric parameters (Å, º) top

FE1—BA3ⁱ	3.4781 (1)	BA3—O5^xxviii	2.8417 (2)
FE1—BA3	3.4781 (1)	BA3—FE6	3.4781 (1)
FE1—BA3ⁱⁱ	3.4781 (1)	BA3—FE6^xviii	3.4781 (1)
FE1—BA3ⁱⁱⁱ	3.4781 (1)	BA3—FE6^xxi	3.4781 (1)
FE1—BA3^iv	3.4781 (1)	BA3—FE6^xxii	3.4781 (1)
FE1—BA3^v	3.4781 (1)	BA3—RE7	3.4781 (1)
FE1—BA3^vi	3.4781 (1)	BA3—RE7^xviii	3.4781 (1)
FE1—BA3^vii	3.4781 (1)	BA3—RE7^xix	3.4781 (1)
FE1—O4	2.065 (11)	BA3—RE7^xx	3.4781 (1)
FE1—O4ⁱⁱⁱ	2.065 (11)	O4—FE1	2.065 (11)
FE1—O4^viii	2.065 (11)	O4—RE2^xxii	1.953 (11)
FE1—O4^ix	2.065 (11)	O4—BA3	2.8396 (2)
FE1—O5	2.044 (17)	O4—BA3ⁱⁱⁱ	2.8396 (2)
FE1—O5^iv	2.044 (17)	O4—BA3^v	2.8396 (2)
RE2—BA3ⁱ	3.4781 (1)	O4—BA3^vii	2.8396 (2)
RE2—BA3	3.4781 (1)	O4—FE6^xxii	1.953 (11)
RE2—BA3ⁱⁱ	3.4781 (1)	O4—RE7	2.065 (11)
RE2—BA3ⁱⁱⁱ	3.4781 (1)	O5—FE1	2.044 (17)
RE2—BA3^x	3.4781 (1)	O5—RE2	1.968 (17)
RE2—BA3^xi	3.4781 (1)	O5—BA3ⁱ	2.8417 (2)
RE2—BA3^xii	3.4781 (1)	O5—BA3	2.8417 (2)
RE2—BA3^xiii	3.4781 (1)	O5—BA3ⁱⁱ	2.8417 (2)
RE2—O4^xiv	1.953 (11)	O5—BA3ⁱⁱⁱ	2.8417 (2)
RE2—O4^xv	1.953 (11)	O5—FE6	1.968 (17)
RE2—O4^xvi	1.953 (11)	O5—RE7	2.044 (17)
RE2—O4^xvii	1.953 (11)	FE6—BA3ⁱ	3.4781 (1)
RE2—O5	1.968 (17)	FE6—BA3	3.4781 (1)
RE2—O5^x	1.968 (17)	FE6—BA3ⁱⁱ	3.4781 (1)
BA3—FE1	3.4781 (1)	FE6—BA3ⁱⁱⁱ	3.4781 (1)
BA3—FE1^xviii	3.4781 (1)	FE6—BA3^x	3.4781 (1)
BA3—FE1^xix	3.4781 (1)	FE6—BA3^xi	3.4781 (1)
BA3—FE1^xx	3.4781 (1)	FE6—BA3^xii	3.4781 (1)
BA3—RE2	3.4781 (1)	FE6—BA3^xiii	3.4781 (1)
BA3—RE2^xviii	3.4781 (1)	FE6—O4^xiv	1.953 (11)
BA3—RE2^xxi	3.4781 (1)	FE6—O4^xv	1.953 (11)
BA3—RE2^xxii	3.4781 (1)	FE6—O4^xvi	1.953 (11)
BA3—BA3ⁱⁱ	4.0183 (1)	FE6—O4^xvii	1.953 (11)
BA3—BA3ⁱⁱⁱ	4.0183 (1)	FE6—O5	1.968 (17)
BA3—BA3^xxiii	4.0183 (1)	FE6—O5^x	1.968 (17)
BA3—BA3^xxiv	4.0183 (1)	RE7—BA3ⁱ	3.4781 (1)
BA3—BA3^v	4.0117 (1)	RE7—BA3	3.4781 (1)
BA3—BA3^xi	4.0117 (1)	RE7—BA3ⁱⁱ	3.4781 (1)
BA3—O4	2.8396 (2)	RE7—BA3ⁱⁱⁱ	3.4781 (1)
BA3—O4^xxiv	2.8396 (2)	RE7—BA3^iv	3.4781 (1)
BA3—O4^xxv	2.8396 (2)	RE7—BA3^v	3.4781 (1)
BA3—O4^ix	2.8396 (2)	RE7—BA3^vi	3.4781 (1)
BA3—O4^xix	2.8396 (2)	RE7—BA3^vii	3.4781 (1)
BA3—O4^xv	2.8396 (2)	RE7—O4	2.065 (11)
BA3—O4^xvi	2.8396 (2)	RE7—O4ⁱⁱⁱ	2.065 (11)
BA3—O4^xxvi	2.8396 (2)	RE7—O4^viii	2.065 (11)
BA3—O5	2.8417 (2)	RE7—O4^ix	2.065 (11)
BA3—O5^xviii	2.8417 (2)	RE7—O5	2.044 (17)
BA3—O5^xxvii	2.8417 (2)	RE7—O5^iv	2.044 (17)

BA3ⁱ—FE1—BA3	109.5606 (4)	BA3ⁱⁱ—BA3—O5^xviii	134.995 (5)
BA3ⁱ—FE1—BA3ⁱⁱ	70.5734 (2)	BA3ⁱⁱ—BA3—O5^xxvii	45.005 (5)
BA3ⁱ—FE1—BA3ⁱⁱⁱ	70.5734 (2)	BA3ⁱⁱⁱ—BA3—BA3^xxiii	180.0
BA3ⁱ—FE1—BA3^iv	70.4394 (4)	BA3ⁱⁱⁱ—BA3—BA3^xxiv	90.0
BA3ⁱ—FE1—BA3^v	180.0	BA3ⁱⁱⁱ—BA3—BA3^v	90.0
BA3ⁱ—FE1—BA3^vi	109.4265 (2)	BA3ⁱⁱⁱ—BA3—BA3^xi	90.0
BA3ⁱ—FE1—BA3^vii	109.4265 (2)	BA3ⁱⁱⁱ—BA3—O4	44.964 (4)
BA3ⁱ—FE1—O4	125.2867 (1)	BA3ⁱⁱⁱ—BA3—O4^xxiv	88.9 (2)
BA3ⁱ—FE1—O4ⁱⁱⁱ	54.7133 (1)	BA3ⁱⁱⁱ—BA3—O4^xxv	135.036 (4)
BA3ⁱ—FE1—O4^viii	54.7133 (1)	BA3ⁱⁱⁱ—BA3—O4^ix	91.1 (2)
BA3ⁱ—FE1—O4^ix	125.2867 (1)	BA3ⁱⁱⁱ—BA3—O4^xix	135.036 (4)
BA3ⁱ—FE1—O5	54.7803 (2)	BA3ⁱⁱⁱ—BA3—O4^xv	88.9 (2)
BA3ⁱ—FE1—O5^iv	125.2197 (2)	BA3ⁱⁱⁱ—BA3—O4^xvi	44.964 (4)
BA3—FE1—BA3ⁱⁱ	70.5734 (2)	BA3ⁱⁱⁱ—BA3—O4^xxvi	91.1 (2)
BA3—FE1—BA3ⁱⁱⁱ	70.5734 (2)	BA3ⁱⁱⁱ—BA3—O5	45.005 (5)
BA3—FE1—BA3^iv	180.0	BA3ⁱⁱⁱ—BA3—O5^xviii	134.995 (5)
BA3—FE1—BA3^v	70.4394 (4)	BA3ⁱⁱⁱ—BA3—O5^xxvii	134.995 (5)
BA3—FE1—BA3^vi	109.4266 (2)	BA3^xxiii—BA3—BA3^xxiv	90.0
BA3—FE1—BA3^vii	109.4265 (2)	BA3^xxiii—BA3—BA3^v	90.0
BA3—FE1—O4	54.7133 (1)	BA3^xxiii—BA3—BA3^xi	90.0
BA3—FE1—O4ⁱⁱⁱ	125.2867 (1)	BA3^xxiii—BA3—O4	135.036 (4)
BA3—FE1—O4^viii	125.2867 (1)	BA3^xxiii—BA3—O4^xxiv	91.1 (2)
BA3—FE1—O4^ix	54.7133 (1)	BA3^xxiii—BA3—O4^xxv	44.964 (4)
BA3—FE1—O5	54.7803 (2)	BA3^xxiii—BA3—O4^ix	88.9 (2)
BA3—FE1—O5^iv	125.2197 (2)	BA3^xxiii—BA3—O4^xix	44.964 (4)
BA3ⁱⁱ—FE1—BA3ⁱⁱⁱ	109.5606 (4)	BA3^xxiii—BA3—O4^xv	91.1 (2)
BA3ⁱⁱ—FE1—BA3^iv	109.4265 (2)	BA3^xxiii—BA3—O4^xvi	135.036 (4)
BA3ⁱⁱ—FE1—BA3^v	109.4265 (2)	BA3^xxiii—BA3—O4^xxvi	88.9 (2)
BA3ⁱⁱ—FE1—BA3^vi	70.4394 (4)	BA3^xxiii—BA3—O5	134.995 (5)
BA3ⁱⁱ—FE1—BA3^vii	180.0	BA3^xxiii—BA3—O5^xviii	45.005 (5)
BA3ⁱⁱ—FE1—O4	125.2867 (1)	BA3^xxiii—BA3—O5^xxvii	45.005 (5)
BA3ⁱⁱ—FE1—O4ⁱⁱⁱ	125.2867 (1)	BA3^xxiv—BA3—BA3^v	90.0
BA3ⁱⁱ—FE1—O4^viii	54.7133 (1)	BA3^xxiv—BA3—BA3^xi	90.0
BA3ⁱⁱ—FE1—O4^ix	54.7133 (1)	BA3^xxiv—BA3—O4	88.9 (2)
BA3ⁱⁱ—FE1—O5	54.7803 (2)	BA3^xxiv—BA3—O4^xxiv	44.964 (4)
BA3ⁱⁱ—FE1—O5^iv	125.2197 (2)	BA3^xxiv—BA3—O4^xxv	91.1 (2)
BA3ⁱⁱⁱ—FE1—BA3^iv	109.4266 (2)	BA3^xxiv—BA3—O4^ix	135.036 (4)
BA3ⁱⁱⁱ—FE1—BA3^v	109.4265 (2)	BA3^xxiv—BA3—O4^xix	88.9 (2)
BA3ⁱⁱⁱ—FE1—BA3^vi	180.0	BA3^xxiv—BA3—O4^xv	135.036 (4)
BA3ⁱⁱⁱ—FE1—BA3^vii	70.4394 (4)	BA3^xxiv—BA3—O4^xvi	91.1 (2)
BA3ⁱⁱⁱ—FE1—O4	54.7133 (1)	BA3^xxiv—BA3—O4^xxvi	44.964 (4)
BA3ⁱⁱⁱ—FE1—O4ⁱⁱⁱ	54.7133 (1)	BA3^xxiv—BA3—O5	134.995 (5)
BA3ⁱⁱⁱ—FE1—O4^viii	125.2867 (1)	BA3^xxiv—BA3—O5^xviii	45.005 (5)
BA3ⁱⁱⁱ—FE1—O4^ix	125.2867 (1)	BA3^xxiv—BA3—O5^xxvii	134.995 (5)
BA3ⁱⁱⁱ—FE1—O5	54.7803 (2)	BA3^v—BA3—BA3^xi	180.0
BA3ⁱⁱⁱ—FE1—O5^iv	125.2197 (2)	BA3^v—BA3—O4	45.058 (4)
BA3^iv—FE1—BA3^v	109.5606 (4)	BA3^v—BA3—O4^xxiv	45.058 (4)
BA3^iv—FE1—BA3^vi	70.5734 (2)	BA3^v—BA3—O4^xxv	45.058 (4)
BA3^iv—FE1—BA3^vii	70.5734 (2)	BA3^v—BA3—O4^ix	45.058 (4)
BA3^iv—FE1—O4	125.2867 (1)	BA3^v—BA3—O4^xix	134.941 (4)
BA3^iv—FE1—O4ⁱⁱⁱ	54.7133 (1)	BA3^v—BA3—O4^xv	134.941 (4)
BA3^iv—FE1—O4^viii	54.7133 (1)	BA3^v—BA3—O4^xvi	134.941 (4)
BA3^iv—FE1—O4^ix	125.2867 (1)	BA3^v—BA3—O4^xxvi	134.941 (4)
BA3^iv—FE1—O5	125.2197 (2)	BA3^v—BA3—O5	90.8 (3)
BA3^iv—FE1—O5^iv	54.7803 (2)	BA3^v—BA3—O5^xviii	90.8 (3)
BA3^v—FE1—BA3^vi	70.5734 (2)	BA3^v—BA3—O5^xxvii	89.2 (3)
BA3^v—FE1—BA3^vii	70.5734 (2)	BA3^xi—BA3—O4	134.941 (4)
BA3^v—FE1—O4	54.7133 (1)	BA3^xi—BA3—O4^xxiv	134.941 (4)
BA3^v—FE1—O4ⁱⁱⁱ	125.2867 (1)	BA3^xi—BA3—O4^xxv	134.941 (4)
BA3^v—FE1—O4^viii	125.2867 (1)	BA3^xi—BA3—O4^ix	134.941 (4)
BA3^v—FE1—O4^ix	54.7133 (1)	BA3^xi—BA3—O4^xix	45.058 (4)
BA3^v—FE1—O5	125.2197 (2)	BA3^xi—BA3—O4^xv	45.058 (4)
BA3^v—FE1—O5^iv	54.7803 (2)	BA3^xi—BA3—O4^xvi	45.058 (4)
BA3^vi—FE1—BA3^vii	109.5606 (4)	BA3^xi—BA3—O4^xxvi	45.058 (4)
BA3^vi—FE1—O4	125.2867 (1)	BA3^xi—BA3—O5	89.2 (3)
BA3^vi—FE1—O4ⁱⁱⁱ	125.2867 (1)	BA3^xi—BA3—O5^xviii	89.2 (3)
BA3^vi—FE1—O4^viii	54.7133 (1)	BA3^xi—BA3—O5^xxvii	90.8 (3)
BA3^vi—FE1—O4^ix	54.7133 (1)	O4—BA3—O4^xxiv	58.2 (4)
BA3^vi—FE1—O5	125.2197 (2)	O4—BA3—O4^xxv	90.117 (8)
BA3^vi—FE1—O5^iv	54.7803 (2)	O4—BA3—O4^ix	61.9 (4)
BA3^vii—FE1—O4	54.7133 (1)	O4—BA3—O4^xix	177.7 (4)
BA3^vii—FE1—O4ⁱⁱⁱ	54.7133 (1)	O4—BA3—O4^xv	119.932 (5)
BA3^vii—FE1—O4^viii	125.2867 (1)	O4—BA3—O4^xvi	89.927 (9)
BA3^vii—FE1—O4^ix	125.2867 (1)	O4—BA3—O4^xxvi	119.932 (5)
BA3^vii—FE1—O5	125.2197 (2)	O4—BA3—O5	61.5 (3)
BA3^vii—FE1—O5^iv	54.7803 (2)	O4—BA3—O5^xviii	119.7 (4)
O4—FE1—O4ⁱⁱⁱ	90.0	O4—BA3—O5^xxvii	120.3 (4)
O4—FE1—O4^viii	179.9802	O4^xxiv—BA3—O4^xxv	61.9 (4)
O4—FE1—O4^ix	90.0	O4^xxiv—BA3—O4^ix	90.117 (8)
O4—FE1—O5	90.0	O4^xxiv—BA3—O4^xix	119.932 (5)
O4—FE1—O5^iv	90.0	O4^xxiv—BA3—O4^xv	177.7 (4)
O4ⁱⁱⁱ—FE1—O4^viii	90.0	O4^xxiv—BA3—O4^xvi	119.932 (5)
O4ⁱⁱⁱ—FE1—O4^ix	179.972	O4^xxiv—BA3—O4^xxvi	89.927 (9)
O4ⁱⁱⁱ—FE1—O5	90.0	O4^xxiv—BA3—O5	119.7 (4)
O4ⁱⁱⁱ—FE1—O5^iv	90.0	O4^xxiv—BA3—O5^xviii	61.5 (3)
O4^viii—FE1—O4^ix	90.0	O4^xxiv—BA3—O5^xxvii	120.3 (4)
O4^viii—FE1—O5	90.0	O4^xxv—BA3—O4^ix	58.2 (4)
O4^viii—FE1—O5^iv	90.0	O4^xxv—BA3—O4^xix	89.927 (9)
O4^ix—FE1—O5	90.0	O4^xxv—BA3—O4^xv	119.932 (5)
O4^ix—FE1—O5^iv	90.0	O4^xxv—BA3—O4^xvi	177.7 (4)
O5—FE1—O5^iv	180.0	O4^xxv—BA3—O4^xxvi	119.932 (5)
BA3ⁱ—RE2—BA3	109.5606 (4)	O4^xxv—BA3—O5	119.7 (4)
BA3ⁱ—RE2—BA3ⁱⁱ	70.5734 (2)	O4^xxv—BA3—O5^xviii	61.5 (3)
BA3ⁱ—RE2—BA3ⁱⁱⁱ	70.5734 (2)	O4^xxv—BA3—O5^xxvii	58.4 (3)
BA3ⁱ—RE2—BA3^x	70.4394 (4)	O4^ix—BA3—O4^xix	119.932 (5)
BA3ⁱ—RE2—BA3^xi	180.0	O4^ix—BA3—O4^xv	89.927 (9)
BA3ⁱ—RE2—BA3^xii	109.4265 (2)	O4^ix—BA3—O4^xvi	119.932 (5)
BA3ⁱ—RE2—BA3^xiii	109.4266 (2)	O4^ix—BA3—O4^xxvi	177.7 (4)
BA3ⁱ—RE2—O4^xiv	54.7133 (1)	O4^ix—BA3—O5	61.5 (3)
BA3ⁱ—RE2—O4^xv	125.2867 (1)	O4^ix—BA3—O5^xviii	119.7 (4)
BA3ⁱ—RE2—O4^xvi	125.2867 (1)	O4^ix—BA3—O5^xxvii	58.4 (3)
BA3ⁱ—RE2—O4^xvii	54.7133 (1)	O4^xix—BA3—O4^xv	61.9 (4)
BA3ⁱ—RE2—O5	54.7803 (2)	O4^xix—BA3—O4^xvi	90.117 (8)
BA3ⁱ—RE2—O5^x	125.2197 (2)	O4^xix—BA3—O4^xxvi	58.2 (4)
BA3—RE2—BA3ⁱⁱ	70.5734 (2)	O4^xix—BA3—O5	120.3 (4)
BA3—RE2—BA3ⁱⁱⁱ	70.5734 (2)	O4^xix—BA3—O5^xviii	58.4 (3)
BA3—RE2—BA3^x	180.0	O4^xix—BA3—O5^xxvii	61.5 (3)
BA3—RE2—BA3^xi	70.4394 (4)	O4^xv—BA3—O4^xvi	58.2 (4)
BA3—RE2—BA3^xii	109.4265 (2)	O4^xv—BA3—O4^xxvi	90.117 (8)
BA3—RE2—BA3^xiii	109.4265 (2)	O4^xv—BA3—O5	58.4 (3)
BA3—RE2—O4^xiv	125.2867 (1)	O4^xv—BA3—O5^xviii	120.3 (4)
BA3—RE2—O4^xv	54.7133 (1)	O4^xv—BA3—O5^xxvii	61.5 (3)
BA3—RE2—O4^xvi	54.7133 (1)	O4^xvi—BA3—O4^xxvi	61.9 (4)
BA3—RE2—O4^xvii	125.2867 (1)	O4^xvi—BA3—O5	58.4 (3)
BA3—RE2—O5	54.7803 (2)	O4^xvi—BA3—O5^xviii	120.3 (4)
BA3—RE2—O5^x	125.2197 (2)	O4^xvi—BA3—O5^xxvii	119.7 (4)
BA3ⁱⁱ—RE2—BA3ⁱⁱⁱ	109.5606 (4)	O4^xxvi—BA3—O5	120.3 (4)
BA3ⁱⁱ—RE2—BA3^x	109.4265 (2)	O4^xxvi—BA3—O5^xviii	58.4 (3)
BA3ⁱⁱ—RE2—BA3^xi	109.4266 (2)	O4^xxvi—BA3—O5^xxvii	119.7 (4)
BA3ⁱⁱ—RE2—BA3^xii	70.4394 (4)	O5—BA3—O5^xviii	178.5 (7)
BA3ⁱⁱ—RE2—BA3^xiii	180.0	O5—BA3—O5^xxvii	90.010 (9)
BA3ⁱⁱ—RE2—O4^xiv	54.7133 (1)	O5^xviii—BA3—O5^xxvii	90.010 (9)
BA3ⁱⁱ—RE2—O4^xv	54.7133 (1)	FE1—O4—RE2^xxii	180.0
BA3ⁱⁱ—RE2—O4^xvi	125.2867 (1)	FE1—O4—BA3	88.9 (2)
BA3ⁱⁱ—RE2—O4^xvii	125.2867 (1)	FE1—O4—BA3ⁱⁱⁱ	88.9 (2)
BA3ⁱⁱ—RE2—O5	54.7803 (2)	FE1—O4—BA3^v	88.9 (2)
BA3ⁱⁱ—RE2—O5^x	125.2197 (2)	FE1—O4—BA3^vii	88.9 (2)
BA3ⁱⁱⁱ—RE2—BA3^x	109.4265 (2)	FE1—O4—FE6^xxii	180.0
BA3ⁱⁱⁱ—RE2—BA3^xi	109.4265 (2)	FE1—O4—RE7	0.0
BA3ⁱⁱⁱ—RE2—BA3^xii	180.0	RE2^xxii—O4—BA3	91.1 (2)
BA3ⁱⁱⁱ—RE2—BA3^xiii	70.4394 (4)	RE2^xxii—O4—BA3ⁱⁱⁱ	91.1 (2)
BA3ⁱⁱⁱ—RE2—O4^xiv	125.2867 (1)	RE2^xxii—O4—BA3^v	91.1 (2)
BA3ⁱⁱⁱ—RE2—O4^xv	125.2867 (1)	RE2^xxii—O4—BA3^vii	91.1 (2)
BA3ⁱⁱⁱ—RE2—O4^xvi	54.7133 (1)	RE2^xxii—O4—FE6^xxii	0.0
BA3ⁱⁱⁱ—RE2—O4^xvii	54.7133 (1)	RE2^xxii—O4—RE7	180.0
BA3ⁱⁱⁱ—RE2—O5	54.7803 (2)	BA3—O4—BA3ⁱⁱⁱ	90.073 (9)
BA3ⁱⁱⁱ—RE2—O5^x	125.2197 (2)	BA3—O4—BA3^v	89.883 (8)
BA3^x—RE2—BA3^xi	109.5606 (4)	BA3—O4—BA3^vii	177.7 (4)
BA3^x—RE2—BA3^xii	70.5734 (2)	BA3—O4—FE6^xxii	91.1 (2)
BA3^x—RE2—BA3^xiii	70.5734 (2)	BA3—O4—RE7	88.9 (2)
BA3^x—RE2—O4^xiv	54.7133 (1)	BA3ⁱⁱⁱ—O4—BA3^v	177.7 (4)
BA3^x—RE2—O4^xv	125.2867 (1)	BA3ⁱⁱⁱ—O4—BA3^vii	89.883 (8)
BA3^x—RE2—O4^xvi	125.2867 (1)	BA3ⁱⁱⁱ—O4—FE6^xxii	91.1 (2)
BA3^x—RE2—O4^xvii	54.7133 (1)	BA3ⁱⁱⁱ—O4—RE7	88.9 (2)
BA3^x—RE2—O5	125.2197 (2)	BA3^v—O4—BA3^vii	90.073 (9)
BA3^x—RE2—O5^x	54.7803 (2)	BA3^v—O4—FE6^xxii	91.1 (2)
BA3^xi—RE2—BA3^xii	70.5734 (2)	BA3^v—O4—RE7	88.9 (2)
BA3^xi—RE2—BA3^xiii	70.5734 (2)	BA3^vii—O4—FE6^xxii	91.1 (2)
BA3^xi—RE2—O4^xiv	125.2867 (1)	BA3^vii—O4—RE7	88.9 (2)
BA3^xi—RE2—O4^xv	54.7133 (1)	FE6^xxii—O4—RE7	180.0
BA3^xi—RE2—O4^xvi	54.7133 (1)	FE1—O5—RE2	180.0
BA3^xi—RE2—O4^xvii	125.2867 (1)	FE1—O5—BA3ⁱ	89.2 (3)
BA3^xi—RE2—O5	125.2197 (2)	FE1—O5—BA3	89.2 (3)
BA3^xi—RE2—O5^x	54.7803 (2)	FE1—O5—BA3ⁱⁱ	89.2 (3)
BA3^xii—RE2—BA3^xiii	109.5606 (4)	FE1—O5—BA3ⁱⁱⁱ	89.2 (3)
BA3^xii—RE2—O4^xiv	54.7133 (1)	FE1—O5—FE6	180.0
BA3^xii—RE2—O4^xv	54.7133 (1)	FE1—O5—RE7	0.0
BA3^xii—RE2—O4^xvi	125.2867 (1)	RE2—O5—BA3ⁱ	90.8 (3)
BA3^xii—RE2—O4^xvii	125.2867 (1)	RE2—O5—BA3	90.8 (3)
BA3^xii—RE2—O5	125.2197 (2)	RE2—O5—BA3ⁱⁱ	90.8 (3)
BA3^xii—RE2—O5^x	54.7803 (2)	RE2—O5—BA3ⁱⁱⁱ	90.8 (3)
BA3^xiii—RE2—O4^xiv	125.2867 (1)	RE2—O5—FE6	0.0
BA3^xiii—RE2—O4^xv	125.2867 (1)	RE2—O5—RE7	180.0
BA3^xiii—RE2—O4^xvi	54.7133 (1)	BA3ⁱ—O5—BA3	178.5 (7)
BA3^xiii—RE2—O4^xvii	54.7133 (1)	BA3ⁱ—O5—BA3ⁱⁱ	89.990 (9)
BA3^xiii—RE2—O5	125.2197 (2)	BA3ⁱ—O5—BA3ⁱⁱⁱ	89.990 (9)
BA3^xiii—RE2—O5^x	54.7803 (2)	BA3ⁱ—O5—FE6	90.8 (3)
O4^xiv—RE2—O4^xv	90.0	BA3ⁱ—O5—RE7	89.2 (3)
O4^xiv—RE2—O4^xvi	180.0	BA3—O5—BA3ⁱⁱ	89.990 (9)
O4^xiv—RE2—O4^xvii	90.0	BA3—O5—BA3ⁱⁱⁱ	89.990 (9)
O4^xiv—RE2—O5	90.0	BA3—O5—FE6	90.8 (3)
O4^xiv—RE2—O5^x	90.0	BA3—O5—RE7	89.2 (3)
O4^xv—RE2—O4^xvi	90.0	BA3ⁱⁱ—O5—BA3ⁱⁱⁱ	178.5 (7)
O4^xv—RE2—O4^xvii	180.0	BA3ⁱⁱ—O5—FE6	90.8 (3)
O4^xv—RE2—O5	90.0	BA3ⁱⁱ—O5—RE7	89.2 (3)
O4^xv—RE2—O5^x	90.0	BA3ⁱⁱⁱ—O5—FE6	90.8 (3)
O4^xvi—RE2—O4^xvii	90.0	BA3ⁱⁱⁱ—O5—RE7	89.2 (3)
O4^xvi—RE2—O5	90.0	FE6—O5—RE7	180.0
O4^xvi—RE2—O5^x	90.0	BA3ⁱ—FE6—BA3	109.5606 (4)
O4^xvii—RE2—O5	90.0	BA3ⁱ—FE6—BA3ⁱⁱ	70.5734 (2)
O4^xvii—RE2—O5^x	90.0	BA3ⁱ—FE6—BA3ⁱⁱⁱ	70.5734 (2)
O5—RE2—O5^x	180.0	BA3ⁱ—FE6—BA3^x	70.4394 (4)
FE1—BA3—FE1^xviii	109.5606 (4)	BA3ⁱ—FE6—BA3^xi	180.0
FE1—BA3—FE1^xix	109.4265 (2)	BA3ⁱ—FE6—BA3^xii	109.4265 (2)
FE1—BA3—FE1^xx	109.4266 (2)	BA3ⁱ—FE6—BA3^xiii	109.4266 (2)
FE1—BA3—RE2	70.4394 (4)	BA3ⁱ—FE6—O4^xiv	54.7133 (1)
FE1—BA3—RE2^xviii	180.0	BA3ⁱ—FE6—O4^xv	125.2867 (1)
FE1—BA3—RE2^xxi	70.5734 (2)	BA3ⁱ—FE6—O4^xvi	125.2867 (1)
FE1—BA3—RE2^xxii	70.5734 (2)	BA3ⁱ—FE6—O4^xvii	54.7133 (1)
FE1—BA3—BA3ⁱⁱ	54.7133 (1)	BA3ⁱ—FE6—O5	54.7803 (2)
FE1—BA3—BA3ⁱⁱⁱ	54.7133 (1)	BA3ⁱ—FE6—O5^x	125.2197 (2)
FE1—BA3—BA3^xxiii	125.2867 (1)	BA3—FE6—BA3ⁱⁱ	70.5734 (2)
FE1—BA3—BA3^xxiv	125.2867 (1)	BA3—FE6—BA3ⁱⁱⁱ	70.5734 (2)
FE1—BA3—BA3^v	54.7803 (2)	BA3—FE6—BA3^x	180.0
FE1—BA3—BA3^xi	125.2197 (2)	BA3—FE6—BA3^xi	70.4394 (4)
FE1—BA3—O4	36.4 (2)	BA3—FE6—BA3^xii	109.4265 (2)
FE1—BA3—O4^xxiv	89.43 (12)	BA3—FE6—BA3^xiii	109.4265 (2)
FE1—BA3—O4^xxv	89.43 (12)	BA3—FE6—O4^xiv	125.2867 (1)
FE1—BA3—O4^ix	36.4 (2)	BA3—FE6—O4^xv	54.7133 (1)
FE1—BA3—O4^xix	145.8 (2)	BA3—FE6—O4^xvi	54.7133 (1)
FE1—BA3—O4^xv	89.27 (12)	BA3—FE6—O4^xvii	125.2867 (1)
FE1—BA3—O4^xvi	89.27 (12)	BA3—FE6—O5	54.7803 (2)
FE1—BA3—O4^xxvi	145.8 (2)	BA3—FE6—O5^x	125.2197 (2)
FE1—BA3—O5	36.0 (3)	BA3ⁱⁱ—FE6—BA3ⁱⁱⁱ	109.5606 (4)
FE1—BA3—O5^xviii	145.6 (3)	BA3ⁱⁱ—FE6—BA3^x	109.4265 (2)
FE1—BA3—O5^xxvii	89.6 (2)	BA3ⁱⁱ—FE6—BA3^xi	109.4266 (2)
FE1^xviii—BA3—FE1^xix	109.4265 (2)	BA3ⁱⁱ—FE6—BA3^xii	70.4394 (4)
FE1^xviii—BA3—FE1^xx	109.4265 (2)	BA3ⁱⁱ—FE6—BA3^xiii	180.0
FE1^xviii—BA3—RE2	180.0	BA3ⁱⁱ—FE6—O4^xiv	54.7133 (1)
FE1^xviii—BA3—RE2^xviii	70.4394 (4)	BA3ⁱⁱ—FE6—O4^xv	54.7133 (1)
FE1^xviii—BA3—RE2^xxi	70.5734 (2)	BA3ⁱⁱ—FE6—O4^xvi	125.2867 (1)
FE1^xviii—BA3—RE2^xxii	70.5734 (2)	BA3ⁱⁱ—FE6—O4^xvii	125.2867 (1)
FE1^xviii—BA3—BA3ⁱⁱ	125.2867 (1)	BA3ⁱⁱ—FE6—O5	54.7803 (2)
FE1^xviii—BA3—BA3ⁱⁱⁱ	125.2867 (1)	BA3ⁱⁱ—FE6—O5^x	125.2197 (2)
FE1^xviii—BA3—BA3^xxiii	54.7133 (1)	BA3ⁱⁱⁱ—FE6—BA3^x	109.4265 (2)
FE1^xviii—BA3—BA3^xxiv	54.7133 (1)	BA3ⁱⁱⁱ—FE6—BA3^xi	109.4265 (2)
FE1^xviii—BA3—BA3^v	54.7803 (2)	BA3ⁱⁱⁱ—FE6—BA3^xii	180.0
FE1^xviii—BA3—BA3^xi	125.2197 (2)	BA3ⁱⁱⁱ—FE6—BA3^xiii	70.4394 (4)
FE1^xviii—BA3—O4	89.43 (12)	BA3ⁱⁱⁱ—FE6—O4^xiv	125.2867 (1)
FE1^xviii—BA3—O4^xxiv	36.4 (2)	BA3ⁱⁱⁱ—FE6—O4^xv	125.2867 (1)
FE1^xviii—BA3—O4^xxv	36.4 (2)	BA3ⁱⁱⁱ—FE6—O4^xvi	54.7133 (1)
FE1^xviii—BA3—O4^ix	89.43 (12)	BA3ⁱⁱⁱ—FE6—O4^xvii	54.7133 (1)
FE1^xviii—BA3—O4^xix	89.27 (12)	BA3ⁱⁱⁱ—FE6—O5	54.7803 (2)
FE1^xviii—BA3—O4^xv	145.8 (2)	BA3ⁱⁱⁱ—FE6—O5^x	125.2197 (2)
FE1^xviii—BA3—O4^xvi	145.8 (2)	BA3^x—FE6—BA3^xi	109.5606 (4)
FE1^xviii—BA3—O4^xxvi	89.27 (12)	BA3^x—FE6—BA3^xii	70.5734 (2)
FE1^xviii—BA3—O5	145.6 (3)	BA3^x—FE6—BA3^xiii	70.5734 (2)
FE1^xviii—BA3—O5^xviii	36.0 (3)	BA3^x—FE6—O4^xiv	54.7133 (1)
FE1^xviii—BA3—O5^xxvii	89.6 (2)	BA3^x—FE6—O4^xv	125.2867 (1)
FE1^xix—BA3—FE1^xx	109.5606 (4)	BA3^x—FE6—O4^xvi	125.2867 (1)
FE1^xix—BA3—RE2	70.5734 (2)	BA3^x—FE6—O4^xvii	54.7133 (1)
FE1^xix—BA3—RE2^xviii	70.5734 (2)	BA3^x—FE6—O5	125.2197 (2)
FE1^xix—BA3—RE2^xxi	70.4394 (4)	BA3^x—FE6—O5^x	54.7803 (2)
FE1^xix—BA3—RE2^xxii	180.0	BA3^xi—FE6—BA3^xii	70.5734 (2)
FE1^xix—BA3—BA3ⁱⁱ	54.7133 (1)	BA3^xi—FE6—BA3^xiii	70.5734 (2)
FE1^xix—BA3—BA3ⁱⁱⁱ	125.2867 (1)	BA3^xi—FE6—O4^xiv	125.2867 (1)
FE1^xix—BA3—BA3^xxiii	54.7133 (1)	BA3^xi—FE6—O4^xv	54.7133 (1)
FE1^xix—BA3—BA3^xxiv	125.2867 (1)	BA3^xi—FE6—O4^xvi	54.7133 (1)
FE1^xix—BA3—BA3^v	125.2197 (2)	BA3^xi—FE6—O4^xvii	125.2867 (1)
FE1^xix—BA3—BA3^xi	54.7803 (2)	BA3^xi—FE6—O5	125.2197 (2)
FE1^xix—BA3—O4	145.8 (2)	BA3^xi—FE6—O5^x	54.7803 (2)
FE1^xix—BA3—O4^xxiv	145.8 (2)	BA3^xii—FE6—BA3^xiii	109.5606 (4)
FE1^xix—BA3—O4^xxv	89.27 (12)	BA3^xii—FE6—O4^xiv	54.7133 (1)
FE1^xix—BA3—O4^ix	89.27 (12)	BA3^xii—FE6—O4^xv	54.7133 (1)
FE1^xix—BA3—O4^xix	36.4 (2)	BA3^xii—FE6—O4^xvi	125.2867 (1)
FE1^xix—BA3—O4^xv	36.4 (2)	BA3^xii—FE6—O4^xvii	125.2867 (1)
FE1^xix—BA3—O4^xvi	89.43 (12)	BA3^xii—FE6—O5	125.2197 (2)
FE1^xix—BA3—O4^xxvi	89.43 (12)	BA3^xii—FE6—O5^x	54.7803 (2)
FE1^xix—BA3—O5	89.6 (2)	BA3^xiii—FE6—O4^xiv	125.2867 (1)
FE1^xix—BA3—O5^xviii	89.6 (2)	BA3^xiii—FE6—O4^xv	125.2867 (1)
FE1^xix—BA3—O5^xxvii	36.0 (3)	BA3^xiii—FE6—O4^xvi	54.7133 (1)
FE1^xx—BA3—RE2	70.5734 (2)	BA3^xiii—FE6—O4^xvii	54.7133 (1)
FE1^xx—BA3—RE2^xviii	70.5734 (2)	BA3^xiii—FE6—O5	125.2197 (2)
FE1^xx—BA3—RE2^xxi	180.0	BA3^xiii—FE6—O5^x	54.7803 (2)
FE1^xx—BA3—RE2^xxii	70.4394 (4)	O4^xiv—FE6—O4^xv	90.0
FE1^xx—BA3—BA3ⁱⁱ	125.2867 (1)	O4^xiv—FE6—O4^xvi	180.0
FE1^xx—BA3—BA3ⁱⁱⁱ	54.7133 (1)	O4^xiv—FE6—O4^xvii	90.0
FE1^xx—BA3—BA3^xxiii	125.2867 (1)	O4^xiv—FE6—O5	90.0
FE1^xx—BA3—BA3^xxiv	54.7133 (1)	O4^xiv—FE6—O5^x	90.0
FE1^xx—BA3—BA3^v	125.2197 (2)	O4^xv—FE6—O4^xvi	90.0
FE1^xx—BA3—BA3^xi	54.7803 (2)	O4^xv—FE6—O4^xvii	180.0
FE1^xx—BA3—O4	89.27 (12)	O4^xv—FE6—O5	90.0
FE1^xx—BA3—O4^xxiv	89.27 (12)	O4^xv—FE6—O5^x	90.0
FE1^xx—BA3—O4^xxv	145.8 (2)	O4^xvi—FE6—O4^xvii	90.0
FE1^xx—BA3—O4^ix	145.8 (2)	O4^xvi—FE6—O5	90.0
FE1^xx—BA3—O4^xix	89.43 (12)	O4^xvi—FE6—O5^x	90.0
FE1^xx—BA3—O4^xv	89.43 (12)	O4^xvii—FE6—O5	90.0
FE1^xx—BA3—O4^xvi	36.4 (2)	O4^xvii—FE6—O5^x	90.0
FE1^xx—BA3—O4^xxvi	36.4 (2)	O5—FE6—O5^x	180.0
FE1^xx—BA3—O5	89.6 (2)	BA3ⁱ—RE7—BA3	109.5606 (4)
FE1^xx—BA3—O5^xviii	89.6 (2)	BA3ⁱ—RE7—BA3ⁱⁱ	70.5734 (2)
FE1^xx—BA3—O5^xxvii	145.6 (3)	BA3ⁱ—RE7—BA3ⁱⁱⁱ	70.5734 (2)
RE2—BA3—RE2^xviii	109.5606 (4)	BA3ⁱ—RE7—BA3^iv	70.4394 (4)
RE2—BA3—RE2^xxi	109.4265 (2)	BA3ⁱ—RE7—BA3^v	180.0
RE2—BA3—RE2^xxii	109.4265 (2)	BA3ⁱ—RE7—BA3^vi	109.4265 (2)
RE2—BA3—BA3ⁱⁱ	54.7133 (1)	BA3ⁱ—RE7—BA3^vii	109.4265 (2)
RE2—BA3—BA3ⁱⁱⁱ	54.7133 (1)	BA3ⁱ—RE7—O4	125.2867 (1)
RE2—BA3—BA3^xxiii	125.2867 (1)	BA3ⁱ—RE7—O4ⁱⁱⁱ	54.7133 (1)
RE2—BA3—BA3^xxiv	125.2867 (1)	BA3ⁱ—RE7—O4^viii	54.7133 (1)
RE2—BA3—BA3^v	125.2197 (2)	BA3ⁱ—RE7—O4^ix	125.2867 (1)
RE2—BA3—BA3^xi	54.7803 (2)	BA3ⁱ—RE7—O5	54.7803 (2)
RE2—BA3—O4	90.57 (12)	BA3ⁱ—RE7—O5^iv	125.2197 (2)
RE2—BA3—O4^xxiv	143.6 (2)	BA3—RE7—BA3ⁱⁱ	70.5734 (2)
RE2—BA3—O4^xxv	143.6 (2)	BA3—RE7—BA3ⁱⁱⁱ	70.5734 (2)
RE2—BA3—O4^ix	90.57 (12)	BA3—RE7—BA3^iv	180.0
RE2—BA3—O4^xix	90.73 (12)	BA3—RE7—BA3^v	70.4394 (4)
RE2—BA3—O4^xv	34.2 (2)	BA3—RE7—BA3^vi	109.4266 (2)
RE2—BA3—O4^xvi	34.2 (2)	BA3—RE7—BA3^vii	109.4265 (2)
RE2—BA3—O4^xxvi	90.73 (12)	BA3—RE7—O4	54.7133 (1)
RE2—BA3—O5	34.5 (3)	BA3—RE7—O4ⁱⁱⁱ	125.2867 (1)
RE2—BA3—O5^xviii	144.0 (3)	BA3—RE7—O4^viii	125.2867 (1)
RE2—BA3—O5^xxvii	90.4 (2)	BA3—RE7—O4^ix	54.7133 (1)
RE2^xviii—BA3—RE2^xxi	109.4266 (2)	BA3—RE7—O5	54.7803 (2)
RE2^xviii—BA3—RE2^xxii	109.4265 (2)	BA3—RE7—O5^iv	125.2197 (2)
RE2^xviii—BA3—BA3ⁱⁱ	125.2867 (1)	BA3ⁱⁱ—RE7—BA3ⁱⁱⁱ	109.5606 (4)
RE2^xviii—BA3—BA3ⁱⁱⁱ	125.2867 (1)	BA3ⁱⁱ—RE7—BA3^iv	109.4265 (2)
RE2^xviii—BA3—BA3^xxiii	54.7133 (1)	BA3ⁱⁱ—RE7—BA3^v	109.4265 (2)
RE2^xviii—BA3—BA3^xxiv	54.7133 (1)	BA3ⁱⁱ—RE7—BA3^vi	70.4394 (4)
RE2^xviii—BA3—BA3^v	125.2197 (2)	BA3ⁱⁱ—RE7—BA3^vii	180.0
RE2^xviii—BA3—BA3^xi	54.7803 (2)	BA3ⁱⁱ—RE7—O4	125.2867 (1)
RE2^xviii—BA3—O4	143.6 (2)	BA3ⁱⁱ—RE7—O4ⁱⁱⁱ	125.2867 (1)
RE2^xviii—BA3—O4^xxiv	90.57 (12)	BA3ⁱⁱ—RE7—O4^viii	54.7133 (1)
RE2^xviii—BA3—O4^xxv	90.57 (12)	BA3ⁱⁱ—RE7—O4^ix	54.7133 (1)
RE2^xviii—BA3—O4^ix	143.6 (2)	BA3ⁱⁱ—RE7—O5	54.7803 (2)
RE2^xviii—BA3—O4^xix	34.2 (2)	BA3ⁱⁱ—RE7—O5^iv	125.2197 (2)
RE2^xviii—BA3—O4^xv	90.73 (12)	BA3ⁱⁱⁱ—RE7—BA3^iv	109.4266 (2)
RE2^xviii—BA3—O4^xvi	90.73 (12)	BA3ⁱⁱⁱ—RE7—BA3^v	109.4265 (2)
RE2^xviii—BA3—O4^xxvi	34.2 (2)	BA3ⁱⁱⁱ—RE7—BA3^vi	180.0
RE2^xviii—BA3—O5	144.0 (3)	BA3ⁱⁱⁱ—RE7—BA3^vii	70.4394 (4)
RE2^xviii—BA3—O5^xviii	34.5 (3)	BA3ⁱⁱⁱ—RE7—O4	54.7133 (1)
RE2^xviii—BA3—O5^xxvii	90.4 (2)	BA3ⁱⁱⁱ—RE7—O4ⁱⁱⁱ	54.7133 (1)
RE2^xxi—BA3—RE2^xxii	109.5606 (4)	BA3ⁱⁱⁱ—RE7—O4^viii	125.2867 (1)
RE2^xxi—BA3—BA3ⁱⁱ	54.7133 (1)	BA3ⁱⁱⁱ—RE7—O4^ix	125.2867 (1)
RE2^xxi—BA3—BA3ⁱⁱⁱ	125.2867 (1)	BA3ⁱⁱⁱ—RE7—O5	54.7803 (2)
RE2^xxi—BA3—BA3^xxiii	54.7133 (1)	BA3ⁱⁱⁱ—RE7—O5^iv	125.2197 (2)
RE2^xxi—BA3—BA3^xxiv	125.2867 (1)	BA3^iv—RE7—BA3^v	109.5606 (4)
RE2^xxi—BA3—BA3^v	54.7803 (2)	BA3^iv—RE7—BA3^vi	70.5734 (2)
RE2^xxi—BA3—BA3^xi	125.2197 (2)	BA3^iv—RE7—BA3^vii	70.5734 (2)
RE2^xxi—BA3—O4	90.73 (12)	BA3^iv—RE7—O4	125.2867 (1)
RE2^xxi—BA3—O4^xxiv	90.73 (12)	BA3^iv—RE7—O4ⁱⁱⁱ	54.7133 (1)
RE2^xxi—BA3—O4^xxv	34.2 (2)	BA3^iv—RE7—O4^viii	54.7133 (1)
RE2^xxi—BA3—O4^ix	34.2 (2)	BA3^iv—RE7—O4^ix	125.2867 (1)
RE2^xxi—BA3—O4^xix	90.57 (12)	BA3^iv—RE7—O5	125.2197 (2)
RE2^xxi—BA3—O4^xv	90.57 (12)	BA3^iv—RE7—O5^iv	54.7803 (2)
RE2^xxi—BA3—O4^xvi	143.6 (2)	BA3^v—RE7—BA3^vi	70.5734 (2)
RE2^xxi—BA3—O4^xxvi	143.6 (2)	BA3^v—RE7—BA3^vii	70.5734 (2)
RE2^xxi—BA3—O5	90.4 (2)	BA3^v—RE7—O4	54.7133 (1)
RE2^xxi—BA3—O5^xviii	90.4 (2)	BA3^v—RE7—O4ⁱⁱⁱ	125.2867 (1)
RE2^xxi—BA3—O5^xxvii	34.5 (3)	BA3^v—RE7—O4^viii	125.2867 (1)
RE2^xxii—BA3—BA3ⁱⁱ	125.2867 (1)	BA3^v—RE7—O4^ix	54.7133 (1)
RE2^xxii—BA3—BA3ⁱⁱⁱ	54.7133 (1)	BA3^v—RE7—O5	125.2197 (2)
RE2^xxii—BA3—BA3^xxiii	125.2867 (1)	BA3^v—RE7—O5^iv	54.7803 (2)
RE2^xxii—BA3—BA3^xxiv	54.7133 (1)	BA3^vi—RE7—BA3^vii	109.5606 (4)
RE2^xxii—BA3—BA3^v	54.7803 (2)	BA3^vi—RE7—O4	125.2867 (1)
RE2^xxii—BA3—BA3^xi	125.2197 (2)	BA3^vi—RE7—O4ⁱⁱⁱ	125.2867 (1)
RE2^xxii—BA3—O4	34.2 (2)	BA3^vi—RE7—O4^viii	54.7133 (1)
RE2^xxii—BA3—O4^xxiv	34.2 (2)	BA3^vi—RE7—O4^ix	54.7133 (1)
RE2^xxii—BA3—O4^xxv	90.73 (12)	BA3^vi—RE7—O5	125.2197 (2)
RE2^xxii—BA3—O4^ix	90.73 (12)	BA3^vi—RE7—O5^iv	54.7803 (2)
RE2^xxii—BA3—O4^xix	143.6 (2)	BA3^vii—RE7—O4	54.7133 (1)
RE2^xxii—BA3—O4^xv	143.6 (2)	BA3^vii—RE7—O4ⁱⁱⁱ	54.7133 (1)
RE2^xxii—BA3—O4^xvi	90.57 (12)	BA3^vii—RE7—O4^viii	125.2867 (1)
RE2^xxii—BA3—O4^xxvi	90.57 (12)	BA3^vii—RE7—O4^ix	125.2867 (1)
RE2^xxii—BA3—O5	90.4 (2)	BA3^vii—RE7—O5	125.2197 (2)
RE2^xxii—BA3—O5^xviii	90.4 (2)	BA3^vii—RE7—O5^iv	54.7803 (2)
RE2^xxii—BA3—O5^xxvii	144.0 (3)	O4—RE7—O4ⁱⁱⁱ	90.0
BA3ⁱⁱ—BA3—BA3ⁱⁱⁱ	90.0	O4—RE7—O4^viii	179.9802
BA3ⁱⁱ—BA3—BA3^xxiii	90.0	O4—RE7—O4^ix	90.0
BA3ⁱⁱ—BA3—BA3^xxiv	180.0	O4—RE7—O5	90.0
BA3ⁱⁱ—BA3—BA3^v	90.0	O4—RE7—O5^iv	90.0
BA3ⁱⁱ—BA3—BA3^xi	90.0	O4ⁱⁱⁱ—RE7—O4^viii	90.0
BA3ⁱⁱ—BA3—O4	91.1 (2)	O4ⁱⁱⁱ—RE7—O4^ix	179.972
BA3ⁱⁱ—BA3—O4^xxiv	135.036 (4)	O4ⁱⁱⁱ—RE7—O5	90.0
BA3ⁱⁱ—BA3—O4^xxv	88.9 (2)	O4ⁱⁱⁱ—RE7—O5^iv	90.0
BA3ⁱⁱ—BA3—O4^ix	44.964 (4)	O4^viii—RE7—O4^ix	90.0
BA3ⁱⁱ—BA3—O4^xix	91.1 (2)	O4^viii—RE7—O5	90.0
BA3ⁱⁱ—BA3—O4^xv	44.964 (4)	O4^viii—RE7—O5^iv	90.0
BA3ⁱⁱ—BA3—O4^xvi	88.9 (2)	O4^ix—RE7—O5	90.0
BA3ⁱⁱ—BA3—O4^xxvi	135.036 (4)	O4^ix—RE7—O5^iv	90.0
BA3ⁱⁱ—BA3—O5	45.005 (5)	O5—RE7—O5^iv	180.0

Symmetry codes: (i) x−1, y, z; (ii) −y, x−1, z; (iii) −y, x, z; (iv) −x, −y, −z; (v) −x+1, −y, −z; (vi) y, −x, −z; (vii) y, −x+1, −z; (viii) −x, −y, z; (ix) y, −x, z; (x) −x, −y, −z+1; (xi) −x+1, −y, −z+1; (xii) y, −x, −z+1; (xiii) y, −x+1, −z+1; (xiv) x−1/2, y−1/2, z+1/2; (xv) −y+1/2, x−1/2, z+1/2; (xvi) −x+1/2, −y+1/2, z+1/2; (xvii) y−1/2, −x+1/2, z+1/2; (xviii) x+1, y, z; (xix) x+1/2, y−1/2, z+1/2; (xx) x+1/2, y+1/2, z+1/2; (xxi) x+1/2, y−1/2, z−1/2; (xxii) x+1/2, y+1/2, z−1/2; (xxiii) −y+1, x−1, z; (xxiv) −y+1, x, z; (xxv) −x+1, −y, z; (xxvi) y+1/2, −x+1/2, z+1/2; (xxvii) −x−1/2, −y−3/2, −z−1/2; (xxviii) −x−1/2, −y−1/2, −z−1/2.

(T400KBST_phase_1) top

Crystal data top

Ba2FeReO₆	Z = 8
M_r = 306.36	? radiation, λ = 1.377287 Å
Cubic, Fm3m	T = 400 K
Hall symbol: F m 3 m	Particle morphology: powder
a = 8.063327 (13) Å	flat_sheet, 20 × 10 mm
V = 524.26 (1) Å³

Data collection top

Huber 4+2 circle diffractometer	Data collection mode: reflection
Radiation source: synchrotron, LNLS D10B-XPD beamline	Scan method: step
Si 111 monochromator	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Specimen mounting: copper sample holder

Refinement top

Least-squares matrix: full	13520 data points
R_p = 0.149	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 1.637 #2(GV) = 2.828 #3(GW) = 0.012 #4(LX) = 0.000 #5(LY) = 8.663 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(LX) = 0.000 #5(LY) = 12.919 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
R_wp = 0.221	25 parameters
R_exp = 0.170	0 restraints
R(F²) = 0.12564	(Δ/σ)_max = 0.02
χ² = 1.690	Background function: GSAS Background function number 2 with 10 terms. Cosine Fourier series 1: 5.36654 2: 1.01816 3: -5.78612 4: -0.425017 5: -3.39798 6: -0.251197 7: -1.97797 8: 0.272396 9: -0.804030 10: 0.197454

Crystal data top

Ba2FeReO₆	Z = 8
M_r = 306.36	? radiation, λ = 1.377287 Å
Cubic, Fm3m	T = 400 K
a = 8.063327 (13) Å	flat_sheet, 20 × 10 mm
V = 524.26 (1) Å³

Data collection top

Huber 4+2 circle diffractometer	Scan method: step
Specimen mounting: copper sample holder	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Data collection mode: reflection

Refinement top

R_p = 0.149	χ² = 1.690
R_wp = 0.221	13520 data points
R_exp = 0.170	25 parameters
R(F²) = 0.12564	0 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.25	0.25	0.25	0.0073 (2)*
Fe	0.0	0.0	0.0	0.0101 (2)*	0.9646
Re	0.5	0.0	0.0	0.0101 (2)*	0.9646
RE5	0.0	0.0	0.0	0.0100 (2)*	0.0354
FE6	0.5	0.0	0.0	0.0100 (2)*	0.0354
O7	0.2608 (9)	0.0	0.0	0.0091 (12)*

Geometric parameters (Å, º) top

Ba—Fe	3.4915	Re—O7	1.929 (8)
Ba—Feⁱ	3.4915	Re—O7^xxvii	1.929 (8)
Ba—Feⁱⁱ	3.4915	Re—O7^xxviii	1.929 (8)
Ba—Feⁱⁱⁱ	3.4915	Re—O7^ix	1.929 (8)
Ba—Re	3.4915	Re—O7^xxix	1.929 (8)
Ba—Re^iv	3.4915	Re—O7^xiii	1.929 (8)
Ba—Re^v	3.4915	RE5—Ba	3.4915
Ba—Reⁱ	3.4915	RE5—Ba^xiv	3.4915
Ba—RE5	3.4915	RE5—Ba^xv	3.4915
Ba—RE5ⁱ	3.4915	RE5—Ba^xvi	3.4915
Ba—RE5ⁱⁱ	3.4915	RE5—Ba^xvii	3.4915
Ba—RE5ⁱⁱⁱ	3.4915	RE5—Ba^xviii	3.4915
Ba—FE6	3.4915	RE5—Ba^xix	3.4915
Ba—FE6^iv	3.4915	RE5—Ba^xx	3.4915
Ba—FE6^v	3.4915	RE5—O7	2.103 (8)
Ba—FE6ⁱ	3.4915	RE5—O7^iv	2.103 (8)
Ba—O7	2.8521 (2)	RE5—O7^v	2.103 (8)
Ba—O7^iv	2.8521 (2)	RE5—O7^xix	2.103 (8)
Ba—O7^v	2.8521 (2)	RE5—O7^xxi	2.103 (8)
Ba—O7ⁱ	2.8521 (2)	RE5—O7^xxii	2.103 (8)
Ba—O7^vi	2.8521 (2)	FE6—Ba	3.4915
Ba—O7^vii	2.8521 (2)	FE6—Ba^xiv	3.4915
Ba—O7^viii	2.8521 (2)	FE6—Ba^xxiii	3.4915
Ba—O7^ix	2.8521 (2)	FE6—Ba^xvi	3.4915
Ba—O7^x	2.8521 (2)	FE6—Ba^xxiv	3.4915
Ba—O7^xi	2.8521 (2)	FE6—Ba^xxv	3.4915
Ba—O7^xii	2.8521 (2)	FE6—Ba^xix	3.4915
Ba—O7^xiii	2.8521 (2)	FE6—Ba^xxvi	3.4915
Fe—Ba	3.4915	FE6—O7	1.929 (8)
Fe—Ba^xiv	3.4915	FE6—O7^xxvii	1.929 (8)
Fe—Ba^xv	3.4915	FE6—O7^xxviii	1.929 (8)
Fe—Ba^xvi	3.4915	FE6—O7^ix	1.929 (8)
Fe—Ba^xvii	3.4915	FE6—O7^xxix	1.929 (8)
Fe—Ba^xviii	3.4915	FE6—O7^xiii	1.929 (8)
Fe—Ba^xix	3.4915	O7—Ba	2.8521 (2)
Fe—Ba^xx	3.4915	O7—Ba^xiv	2.8521 (2)
Fe—O7	2.103 (8)	O7—Ba^xvi	2.8521 (2)
Fe—O7^iv	2.103 (8)	O7—Ba^xix	2.8521 (2)
Fe—O7^v	2.103 (8)	O7—Fe	2.103 (8)
Fe—O7^xix	2.103 (8)	O7—Re	1.929 (8)
Fe—O7^xxi	2.103 (8)	O7—RE5	2.103 (8)
Fe—O7^xxii	2.103 (8)	O7—FE6	1.929 (8)
Re—Ba	3.4915	O7—O7^iv	2.974 (11)
Re—Ba^xiv	3.4915	O7—O7^v	2.974 (11)
Re—Ba^xxiii	3.4915	O7—O7^xix	2.974 (11)
Re—Ba^xvi	3.4915	O7—O7^xxii	2.974 (11)
Re—Ba^xxiv	3.4915	O7—O7^xxviii	2.728 (11)
Re—Ba^xxv	3.4915	O7—O7^ix	2.728 (11)
Re—Ba^xix	3.4915	O7—O7^xxix	2.728 (11)
Re—Ba^xxvi	3.4915	O7—O7^xiii	2.728 (11)

O7—Fe—O7^iv	90.0	O7—RE5—O7^xxi	180.0
O7—Fe—O7^v	90.0	O7—RE5—O7^xxii	90.0
O7—Fe—O7^xix	90.0	O7^iv—RE5—O7^v	90.0
O7—Fe—O7^xxi	180.0	O7^iv—RE5—O7^xix	90.0
O7—Fe—O7^xxii	90.0	O7^iv—RE5—O7^xxi	90.0
O7^iv—Fe—O7^v	90.0	O7^iv—RE5—O7^xxii	180.0
O7^iv—Fe—O7^xix	90.0	O7^v—RE5—O7^xix	180.0
O7^iv—Fe—O7^xxi	90.0	O7^v—RE5—O7^xxi	90.0
O7^iv—Fe—O7^xxii	180.0	O7^v—RE5—O7^xxii	90.0
O7^v—Fe—O7^xix	180.0	O7^xix—RE5—O7^xxi	90.0
O7^v—Fe—O7^xxi	90.0	O7^xix—RE5—O7^xxii	90.0
O7^v—Fe—O7^xxii	90.0	O7^xxi—RE5—O7^xxii	90.0
O7^xix—Fe—O7^xxi	90.0	O7—FE6—O7^xxvii	179.9604
O7^xix—Fe—O7^xxii	90.0	O7—FE6—O7^xxviii	90.0
O7^xxi—Fe—O7^xxii	90.0	O7—FE6—O7^ix	90.0
O7—Re—O7^xxvii	179.9604	O7—FE6—O7^xxix	90.0
O7—Re—O7^xxviii	90.0	O7—FE6—O7^xiii	90.0
O7—Re—O7^ix	90.0	O7^xxvii—FE6—O7^xxviii	90.0
O7—Re—O7^xxix	90.0	O7^xxvii—FE6—O7^ix	90.0
O7—Re—O7^xiii	90.0	O7^xxvii—FE6—O7^xxix	90.0
O7^xxvii—Re—O7^xxviii	90.0	O7^xxvii—FE6—O7^xiii	90.0
O7^xxvii—Re—O7^ix	90.0	O7^xxviii—FE6—O7^ix	180.0
O7^xxvii—Re—O7^xxix	90.0	O7^xxviii—FE6—O7^xxix	90.0
O7^xxvii—Re—O7^xiii	90.0	O7^xxviii—FE6—O7^xiii	90.0
O7^xxviii—Re—O7^ix	180.0	O7^ix—FE6—O7^xxix	90.0
O7^xxviii—Re—O7^xxix	90.0	O7^ix—FE6—O7^xiii	90.0
O7^xxviii—Re—O7^xiii	90.0	O7^xxix—FE6—O7^xiii	180.0
O7^ix—Re—O7^xxix	90.0	Fe—O7—Re	180.0
O7^ix—Re—O7^xiii	90.0	Fe—O7—RE5	0.0
O7^xxix—Re—O7^xiii	180.0	Fe—O7—FE6	180.0
O7—RE5—O7^iv	90.0	Re—O7—RE5	180.0
O7—RE5—O7^v	90.0	Re—O7—FE6	0.0
O7—RE5—O7^xix	90.0	RE5—O7—FE6	180.0

Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y+1/2, z; (iv) z, x, y; (v) y, z, x; (vi) y, −z+1/2, −x+1/2; (vii) −z, −x+1/2, y+1/2; (viii) z+1/2, x, y+1/2; (ix) y+1/2, −z, −x+1/2; (x) −x+1/2, y, −z+1/2; (xi) y+1/2, z+1/2, x; (xii) −x+1/2, y+1/2, −z; (xiii) −z+1/2, −x+1/2, y; (xiv) x, y, −z; (xv) −z, x, y; (xvi) y, −z, x; (xvii) −z, x, −y; (xviii) −y, −z, x; (xix) y, −z, −x; (xx) −x, −y, −z; (xxi) −x, y, −z; (xxii) −z, −x, y; (xxiii) −z+1, x, y; (xxiv) −z+1, x, −y; (xxv) −y+1, −z, x; (xxvi) −x+1, −y, −z; (xxvii) −x+1, y, −z; (xxviii) y+1/2, z, x−1/2; (xxix) z+1/2, x−1/2, y.

(T400KBST_phase_2) iron oxide top

Crystal data top

Fe₃O₄	Z = 8
M_r = 231.54	? radiation, λ = 1.377287 Å
Cubic, Fd3m	T = 400 K
Hall symbol: F d -3 m	Particle morphology: powder
a = 8.3985 (5) Å	flat_sheet, 20 × 10 mm
V = 592.38 (10) Å³

Data collection top

Huber 4+2 circle diffractometer	Data collection mode: reflection
Radiation source: synchrotron, LNLS D10B-XPD beamline	Scan method: step
Si 111 monochromator	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Specimen mounting: copper sample holder

Refinement top

Least-squares matrix: full	13520 data points
R_p = 0.149	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 1.637 #2(GV) = 2.828 #3(GW) = 0.012 #4(LX) = 0.000 #5(LY) = 8.663 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(LX) = 0.000 #5(LY) = 12.919 #6(trns) = 0.000 #7(asym) = 0.0000 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
R_wp = 0.221	25 parameters
R_exp = 0.170	0 restraints
R(F²) = 0.12564	(Δ/σ)_max = 0.02
χ² = 1.690	Background function: GSAS Background function number 2 with 10 terms. Cosine Fourier series 1: 5.36654 2: 1.01816 3: -5.78612 4: -0.425017 5: -3.39798 6: -0.251197 7: -1.97797 8: 0.272396 9: -0.804030 10: 0.197454

Crystal data top

Fe₃O₄	Z = 8
M_r = 231.54	? radiation, λ = 1.377287 Å
Cubic, Fd3m	T = 400 K
a = 8.3985 (5) Å	flat_sheet, 20 × 10 mm
V = 592.38 (10) Å³

Data collection top

Huber 4+2 circle diffractometer	Scan method: step
Specimen mounting: copper sample holder	2θ_min = 15.003°, 2θ_max = 150.193°, 2θ_step = 0.01°
Data collection mode: reflection

Refinement top

R_p = 0.149	χ² = 1.690
R_wp = 0.221	13520 data points
R_exp = 0.170	25 parameters
R(F²) = 0.12564	0 restraints

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

	x	y	z	U_iso*/U_eq
Fe1	0.125	0.125	0.125	−0.016 (4)*
Fe2	0.5	0.5	0.5	−0.016 (4)*
O	0.246 (10)	0.246 (10)	0.246 (10)	−0.016 (4)*

Geometric parameters (Å, º) top

Fe1—O	1.76 (15)	Fe2—O^vii	2.14 (9)
Fe1—Oⁱ	1.76 (15)	Fe2—O^viii	2.14 (9)
Fe1—Oⁱⁱ	1.76 (15)	Fe2—O^ix	2.14 (9)
Fe1—Oⁱⁱⁱ	1.76 (15)	O—Fe1	1.76 (15)
Fe2—O^iv	2.14 (9)	O—Fe2^vii	2.14 (9)
Fe2—O^v	2.14 (9)	O—Fe2^viii	2.14 (9)
Fe2—O^vi	2.14 (9)	O—Fe2^ix	2.14 (9)

O—Fe1—O^x	109.471 (2)	O^v—Fe2—O^ix	88 (4)
O—Fe1—O^xi	109.471 (4)	O^vi—Fe2—O^xiii	88 (4)
O—Fe1—O^xii	109.471 (2)	O^vi—Fe2—O^xiv	88 (4)
O^x—Fe1—O^xi	109.471 (2)	O^vi—Fe2—O^ix	179.9557
O^x—Fe1—O^xii	109.471 (4)	O^xiii—Fe2—O^xiv	92 (4)
O^xi—Fe1—O^xii	109.471 (2)	O^xiii—Fe2—O^ix	92 (4)
O^iv—Fe2—O^v	92 (4)	O^xiv—Fe2—O^ix	92 (4)
O^iv—Fe2—O^vi	92 (4)	Fe1—O—Fe2^xv	127 (3)
O^iv—Fe2—O^xiii	179.9557	Fe1—O—Fe2^viii	127 (3)
O^iv—Fe2—O^xiv	88 (4)	Fe1—O—Fe2^xvi	127 (3)
O^iv—Fe2—O^ix	88 (4)	Fe2^xv—O—Fe2^viii	88 (5)
O^v—Fe2—O^vi	92 (4)	Fe2^xv—O—Fe2^xvi	88 (5)
O^v—Fe2—O^xiii	88 (4)	Fe2^viii—O—Fe2^xvi	88 (5)
O^v—Fe2—O^xiv	179.9557

Experimental details

	(T14KBST_phase_2)	(T14KBST_phase_3)	(T400KBST_phase_1)	(T400KBST_phase_2)
Crystal data
Chemical formula	Fe₃O₄	Ba₂FeReO₆	Ba2FeReO₆	Fe₃O₄
M_r	231.54	306.36	306.36	231.54
Crystal system, space group	Cubic, Fd3m	Tetragonal, I4/mmm	Cubic, Fm3m	Cubic, Fd3m
Temperature (K)	14	14	400	400
a, b, c (Å)	8.3814 (5), 8.3814, 8.3814	5.68278 (2), 5.682775, 8.02337 (5)	8.063327 (13), 8.063327, 8.063327	8.3985 (5), 8.3985, 8.3985
α, β, γ (°)	90, 90, 90	90, 90, 90	90, 90, 90	90, 90, 90
V (Å³)	588.78 (10)	259.11 (1)	524.26 (1)	592.38 (10)
Z	8	4	8	8
Radiation type	Synchrotron, λ = 1.377285 Å	Synchrotron, λ = 1.377285 Å	?, λ = 1.377287 Å	?, λ = 1.377287 Å
Specimen shape, size (mm)	Flat_sheet, 20 × 10	Flat_sheet, 20 × 10	Flat_sheet, 20 × 10	Flat_sheet, 20 × 10

Data collection
Diffractometer	Huber 4+2 circle diffractometer	Huber 4+2 circle diffractometer	Huber 4+2 circle diffractometer	Huber 4+2 circle diffractometer
Specimen mounting	Copper sample holder	Copper sample holder	Copper sample holder	Copper sample holder
Data collection mode	Reflection	Reflection	Reflection	Reflection
Scan method	Step	Step	Step	Step
2θ values (°)	2θ_min = 15.003 2θ_max = 150.193 2θ_step = 0.01	2θ_min = 15.003 2θ_max = 150.193 2θ_step = 0.01	2θ_min = 15.003 2θ_max = 150.193 2θ_step = 0.01	2θ_min = 15.003 2θ_max = 150.193 2θ_step = 0.01

Refinement
R factors and goodness of fit	R_p = 0.168, R_wp = 0.267, R_exp = 0.195, R(F²) = 0.18130, χ² = 1.904	R_p = 0.168, R_wp = 0.267, R_exp = 0.195, R(F²) = 0.18130, χ² = 1.904	R_p = 0.149, R_wp = 0.221, R_exp = 0.170, R(F²) = 0.12564, χ² = 1.690	R_p = 0.149, R_wp = 0.221, R_exp = 0.170, R(F²) = 0.12564, χ² = 1.690
No. of data points	13520	13520	13520	13520
No. of parameters	24	24	25	25

Computer programs: SPEC (Certified Scientific Software, 1992), POWF 2.11 (Virginia Tech, 2001-2003), GSAS (Larson & Von Dreele, 2001), GSAS.

Footnotes

¹Identification of commercial equipment in the text is not intended to imply recommendation or endorsement by the authors or the respective institutions.

Acknowledgements

Thanks are due to the LNLS technical staff (Carlos R. Scorzato, Edson G. L. Silva, Evandro Blumer, Hélio Gazetta Filho, João R. Costa, João V. O. Neto, Milton B. da Silva, Thiago C. de Freitas, Wagner S. Veira and members of the Projects Group), which has been contributing to the progress of the beamline. Also, we thank Iris Torriani, Guinter Kellerman, Daniel Vega and Oscar Agüero, who helped with valuable discussions. This work was partially supported by FINEP and ABTLuS. EG thanks CNPq for a research grant.

References

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Volume 13| Part 1| January 2006| Pages 46-53

doi:10.1107/S0909049505039208

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