Preparation of pyrite concentrate powder from the Thackaringa mine for qu­antitative phase analysis using X-ray diffraction

The quantitative phase analysis using X-ray diffraction of pyrite ore concentrate samples extracted from the Thackaringa mine is problematic due to poor particle statistics, microabsorption and preferred orientation. The influence of sample preparation on these issues has been evaluated, with ball milling of the powder found most suitable for accurate and precise quantitative phase analysis. The milling duration and other aspects of sample preparation have been explored, resulting in accurate phase reflection intensities when particle sizes are below 5 µm. Quantitative phase analysis on those samples yielded precise phase fractions with standard deviations below 0.3 wt%. Some discrepancy between the elemental composition obtained using X-ray powder diffraction data and that determined using wavelength-dispersive X-ray fluorescence was found, and is thought to arise from unaccounted for crystalline phase substitution and the possible presence of an amorphous phase. This study provides a methodology for the precise and accurate quantitative phase analysis of X-ray powder diffraction data of pyrite ore concentrate from the Thackaringa mine and a discussion of the limitations of the method. The optimization process reveals the importance of confirming reproducibility on new samples, with as much prior knowledge as possible.

1. Introduction

With recent shifts towards mining of lower grade ore deposits (West, 2011; Summerfield, 2020), mineral characterization that is both precise and accurate is becoming increasingly valuable. Deteriorating ore quality has led to more complex multiphase mineral compositions, which require representative crystalline phase information for the design of effective strategies for the post-processing and elemental recovery of newly tapped sources. X-ray diffraction (XRD) is one of the most common techniques used for the characterization of mineral samples, being simple and relatively fast.

Quantitative phase analysis (QPA) from whole-pattern fitting using the Rietveld method (Rietveld, 1969; Werner et al., 1979) is routinely used to extract information such as phase identification, weight fractions and unit-cell parameters of crystalline phases within a powder sample. The accuracy and reliability of QPA results depend strongly on sample preparation (Dermatas et al., 2007; Madsen et al., 2019). One important requirement is that the irradiated sample volume contains a sufficient number of randomly oriented crystallites. This may be prevented by poor particle statistics, preferred orientation and microabsorption, well known factors discussed in the literature (Klug & Alexander, 1954; Bish & Reynolds, 1989; Moore & Reynolds, 1997; Zhang et al., 2003; Dermatas et al., 2007; Kleeberg et al., 2008; Madsen et al., 2019). A number of preparation techniques have been developed to resolve those issues in multiphase samples (Klug & Alexander, 1954; Bish & Reynolds, 1989; Moore & Reynolds, 1997; Hillier, 1999; Monecke et al., 2001; Dermatas et al., 2007; Kleeberg et al., 2008).

Because the optimal method of sample preparation depends on sample characteristics such as composition, phase distribution, particle size and morphology, the preparation is often devised by trial and error and has not been considered for pyrite ore concentrates. In this work we evaluate and optimize the sample preparation for powder XRD of pyrite ore concentrate from the Thackaringa mine, Broken Hill (NSW, Australia), and estimate absolute and relative uncertainties on phase weight fractions extracted by QPA.

2. Materials and methods

2.1. Sample preparation

The pyrite concentrate used in this study was produced from ore originating from the Thackaringa mine in Broken Hill, New South Wales, Australia, taken from a pyrite–quartz–albite gneiss at the `Pyrite Hill' site in February 2019, containing approximately 20% pyrite by weight. The raw ore obtained by reverse cycle drilling was crushed and treated by gravity separation, followed by a scavenger float on the gravity tails. The gravity and float concentrates were combined to form the pyrite concentrate sample. The resulting coarse powder was stored under water at room temperature prior to handling.

Approximately 1 kg aliquots of this powder were washed with deionized water, vacuum filtered and dried at approximately 353 K for 3–5 h, then stored in closed containers at 258 K. Ore content variation is artificially introduced between aliquots due to manual sampling. To minimize this ore content variation, all measured samples were taken from the same aliquot roughly homogenized by rotation of the container. Samples were hand ground using an agate mortar and pestle for 25 min. Samples were ball milled using a tungsten carbide (WC) jar and balls in an ESSA LM1-P vibratory ball mill, where 15 g of material was milled for 1, 2, 3, 5, 7 or 10 min. Magnetic separation of antiferromagnetic pyrrhotite from pyrite ore concentrate was performed by vigorously shaking 10 g sample aliquots in an inverted sample vial with a neodymium magnet on top of the vial.

For comparison purposes, 15 g of pyrite ore concentrate was milled using a jar of alumina rods in a McCrone micronizing mill in 7 ml of propan-2-ol for 30 min. The sample was rinsed from the container with additional propan-2-ol (5–10 ml), which was then evaporated by heating to 353 K for 1 h.

2.2. XRD measurement

XRD measurements were performed using a Malvern Panalytical Empyrean II diffractometer with a Co Kα X-ray source (λ = 1.7891 Å) and point detector in Bragg–Brentano geometry in the 10–120° 2θ range with the sample rotated at 30 rev min⁻¹ during measurement. Apart from the grease-prepared samples described below, all powders were partly top loaded into 30 mm diameter × 1 mm deep stainless steel holders, covered with a glass slide and turned vertical with slight tapping to reorient the grains. Loading and vertical taps were repeated until the holder was full, after which the glass slide was removed from the horizontal holder and a razor blade taken across the surface. The grease-prepared samples used silicone high-vacuum grease (Chem Supply) to coat the base of a `zero background' oriented silicon sample holder (Malvern Panalytical) onto which the sample was sprinkled in line with the lip of the holder, before gentle tapping to deposit a relatively thin layer of sample onto the grease.

The proportion of amorphous content was estimated by the external standard method (O'Connor & Raven, 1988; Scarlett & Madsen, 2018). Crystalline α-Al₂O₃ (Baikalox, CR1, Baikowski) powder was loaded into sample holders and measured identically to the pyrite concentrate samples. The crystallinity of the alumina standard was assumed to be 99.0 (6)% according to previous amorphous content determination of this material (Cline et al., 2011). The overall profile scale factor was obtained by the Rietveld method as described in Section 2.3 using the ICDD (International Centre for Diffraction Data, Newtown Square, Pennsylvania, USA; https://www.icdd.com) 01-070-7019 (Pillet et al., 2001) crystal structure for α-Al₂O₃; refined unit-cell and atomic parameters for this phase are given in Table S5 in the supporting information. The mass attenuation coefficients of the standard and concentrate were calculated according to their elemental composition using the database of Chantler (2001).

2.3. XRD analysis

Crystalline phases in the XRD data of the pyrite concentrate powder were identified using Malvern Panalytical's Highscore semi-quantitative analysis software with the ICDD PDF4+2021 database and the ICSD [Inorganic Crystal Structure Database, FIZ-Karlsruhe, Germany, and the National Institute of Standards and Technology (NIST), USA; https://icsd.fiz-karlsruhe.de/index.xhtml] release 2020.1. QPA was performed using the Rietveld method (Rietveld, 1969) as implemented in the GSAS-II software (Toby & Von Dreele, 2013). The instrumental peak shape was modelled using a pseudo-Voigt function with W, X, Y, instrumental zero and asymmetry parameters determined from data for a silicon standard (Malvern Panalytical) and fixed in all subsequent refinements of sample data. The background was modelled with a seven-coefficient Chebyshev 1 polynomial and the vertical sample displacement refined.

The crystal structures used as starting structures in the phase refinements were ICDD 04-014-3191 (Wu et al., 2004) for pyrite (FeS₂), ICSD 162490 (Antao et al., 2008) for quartz (SiO₂), ICSD 68913 (Armbruster et al., 1990) for albite (NaAlSi₃O₈), ICDD 00-029-0723 (Morimoto et al., 1975) for pyrrhotite (Fe₇S₈) and ICSD 64987 (Shintani et al., 1975) for rutile (TiO₂). Each phase had its unit cell, crystallite size and phase fraction refined. Refinement of the triclinic unit cell of albite proved unstable, so the unit-cell parameters of albite were not refined for samples milled for 0, 1, 2 and 3 min but could be refined at the last refinement step for the 5, 7 and 10 min milled samples. A March–Dollase parameter was included in the refinements to correct for the severe preferred orientation observed for albite, with the direction [013] yielding better agreement between calculated and observed patterns, as consistent with previous analysis (Kleeberg et al., 2008). For rutile, given its low phase fraction (<1 wt%), it was necessary to fix the crystallite size to an appropriate value (0.08 µm) for refinement of the samples milled for 0 min to avoid refinement divergence, but the parameter could be refined for samples milled for 1, 2, 3, 5, 7 and 10 min. Refinement of coordinates and isotropic atomic displacement parameters (ADPs) for quartz, albite, pyrrhotite and rutile often resulted in refinement instability or non-sensible chemical composition, so these were not refined. Atomic coordinates and ADPs for the pyrite phase in the grease-prepared samples and those samples milled for 5, 7 and 10 min could be refined, with negligible change to phase fraction and crystallite size values when those were refined.

2.4. Neutron diffraction (ND)

ND measurements were performed on the Wombat high-intensity neutron powder diffractometer (Studer et al., 2006) at the Australian Nuclear Science and Technology Organisation's Centre for Neutron Scattering, Lucas Heights (NSW, Australia). Powder samples were loaded into 9 mm diameter vanadium cans and suspended in the neutron beam of wavelength 1.5430 (1) or 2.4144 (3) Å determined using the La¹¹B₆ Standard Reference Material (SRM) 660b from NIST. Rietveld refinements using neutron diffraction data have been attempted, but the precise determination of phase weight fractions in those data was prevented by difficulty in observing reflections from minor phases as a result of un­favourable neutron scattering cross sections and instrumental broadening.

2.5. Wavelength-dispersive X-ray fluorescence (WD-XRF)

WD-XRF measurements were performed using a Malvern Panalytical Axios Advanced WDXRF instrument with a Rh Kα X-ray source (λ = 0.615 Å). Samples of 10–12 g were prepared by milling for 7 min as per Section 2.1. A 10:1 mass ratio of sample to Ceridust 3620 (polyethylene wax, used as a binding agent) was mixed and pressed into a pellet, and a 1074.7 mm² area was illuminated during measurement. Two types of WD-XRF analyses were made: semiquantitative multi-elemental analysis, and quantitative analysis calibrated for Fe, S and Si.

The multi-elemental analysis provides semiquantitative elemental ratios for elements between Be and U using a fundamental parameters matrix correction (Omnian) calibrated in-house by Malvern Panalytical. In this analysis, lighter elements are slightly overestimated, probably as a result of the stronger X-ray attenuation of the pyrite concentrate compared with that of the standard (Rousseau, 2006), noting that ratios between elements with close Z are less affected. The automatic peak search and match were corrected by visual inspection of the spectra. Peaks for rhodium and phosphorus, arising from the source X-ray tube and Ceridust binder, respectively, were excluded from the analysis.

The quantitative calibrated analysis measured the Fe, S and Si content using empirical calibration curves from mixtures that matched the composition and sample preparation method of the concentrate, comprising three standards of 70:30, 80:20 and 90:10 ratios of FeS₂:SiO₂. These standards were produced using pyrite (iron disulfide, 99.8%, Sigma Aldrich) and acid-washed quartz (laboratory grade, Chem Supply), where 10 g of coarse quartz was first milled for 1 min and ground together with the appropriate mass of pyrite in an agate mortar before shaking in a glass vial. Pellets of this mixture were then milled and pressed identically to the pyrite concentrate samples for WD-XRF measurements. Calibration curves were obtained by linear regression between measured Kα peak intensities for Fe, S and Si and the corresponding weighed concentrations of standard mixtures.

2.6. Scanning electron microscopy and energy-dispersive spectroscopy (SEM-EDS)

For particle surface imaging, samples were sprinkled onto a two-sided tape-covered mount. For particle cross-section imaging and elemental mapping, powder samples were covered in epoxy resin precursors, evacuated for 10 min and left to cure overnight. Particles were exposed by abrading the surface of cured resin samples for 1 to 5 min using P800 sandpaper; the samples were then cleaned under sonication in a distilled water bath, polished for 5 min using P1200 sandpaper and cleaned in the same manner once more. Dried resin samples were mounted using aluminium tape and coated with 10 nm of carbon using a Safematic CCU-010 compact coating unit immediately prior to analysis. SEM imaging was performed with an ST Instruments TM4000Plus tabletop microscope using a backscattered electron (BSE) detector paired with a Bruker QUANTAX energy-dispersive X-ray spectrometry (EDS) detector. Ten SEM images were taken of each pyrite concentrate powder ball milled for different times.

2.7. Inductively coupled plasma mass spectrometry (ICP-MS)

Approximately 1 g of sample was microwave digested in aqua regia mixture (3HCl + 2HNO₃) to ensure all soluble materials were dissolved. It was noted that the sample contained some insoluble particles, most likely silicates. ICP-MS measurements were performed on the extracted solution using a Perkin Elmer NexIon 300D instrument.

2.8. Particle size analysis

Particle size distribution analysis was performed using a Malvern Panalytical Mastersizer 3000 laser dispersion instrument. Approximately 5 × 10⁻⁴ g ml⁻¹ of untreated pyrite ore concentrate was used for dispersion in deionized water. Aliquots of sample were added slowly until the instrument reached the required particle obscuration rate (the rate at which specified surface can be accurately calculated and the risk from deposited particles is reduced). The samples were automatically sonicated and dispersed by the instrument during measurements, with blank measurements taken between each individual sample. Measurements were replicated three times for each sample to determine experimental uncertainty.

2.9. Sieve analysis

Sieve analysis was performed on unground pyrite concentrate using a series of Cole–Parmer stainless steel standard test sieves (ASTM E11 approved) with mesh sizes of 75, 106, 250, 600 and 1000 µm, using a Laarman LMSM 75–240 V/50 Hz horizontal sieve shaker for 1 h. The particle size distribution was obtained by weighing the material collected in each sieve [Fig. S2(a)]. Phase fractions in each portion were obtained from QPA using XRD following the optimized sample preparation outlined above.

3. Results and discussion

3.1. Qualitative analysis of samples

Before QPA was performed, the crystalline phases present in the sample needed to be identified. A powder diffraction pattern was initially obtained from XRD using a sample prepared by hand grinding in an agate mortar and top loading into a flat horizontal sample holder. This preparation was later found inappropriate for accurate QPA, as shown in Section 3.2, with ball milling necessary to obtain phase reflection intensities closer to those expected from published crystal structures. This gradual process was necessary to devise an optimal measurement strategy, with knowledge of the sample mineral content and particle distribution informing the preparation methods. XRD data for the pyrite concentrate sample ball milled for 7 min were used to identify crystalline phases present (Table 1 and Fig. 1), with elemental compositions corroborated with XRF and SEM-EDS.

Table 1
Crystalline phases identified from XRD data of pyrite powder concentrate ball milled for 7 min

Phase name	Formula	Matching crystal structure reference
Pyrite	FeS2	Wu et al. (2004)
Quartz α	SiO2	Antao et al. (2008)
Albite, low	NaAlSi3O8	Armbruster et al. (1990)
Pyrrhotite, 4M	Fe7S8	Morimoto et al. (1975)
Rutile	TiO2	Shintani et al. (1975)

Figure 1 Phase identification using the Highscore software analysis of XRD data of pyrite concentrate powder ball milled for 7 min. Data are shown as a black line and all peaks can be indexed to one of five crystalline phases.

Five crystalline phases were identified from the XRD data, with all reflections indexed by this phase composition. Qualitatively, pyrite was found to be the major phase, with albite and quartz as minor phases. Pyrrhotite and rutile were present as trace phases. Observed reflection intensities for albite were closest to those expected for the low albite polymorph (Armbruster et al., 1990). The 4M polymorph of pyrrhotite (Morimoto et al., 1975) was identified from the XRD pattern of a magnetically separated sample (Fig. S1).

The elemental composition of the pyrite concentrate obtained from semi-quantitative WD-XRF (for samples milled for 7 min, Table 2) and SEM-EDS (for as-received unground samples) was used to corroborate the phase identification obtained using the XRD data. Several representative images of the sample and the corresponding elemental compositions are shown in Fig. 2.

Table 2
Mean elemental weight fractions of pyrite concentrate powder ball milled for 7 min determined using semi-quantitative WD-XRF data, and standard deviations from five repeat samples

The Kα peak of oxygen was visible but O was excluded from the analysis due to the lack of accuracy for this element. The presence of trace elements with overlapping energies, such as As Kα and Pb Lα, or W Lβ and Au Lα, was confirmed by ICP-MS (Table S1). Other elements are below the detection/quantification limit of the technique (Loubser & Verryn, 2008; Kadachi & Al-Eshaikh, 2012). Elemental fractions were obtained from fundamental parameter analysis.

Element	Wt%	Element	Wt%
S	52.2 (6)	Mg	0.032 (4)
Fe	35.8 (3)	K	0.03 (10)
Si	4.51 (10)	Zr	0.01 (2)
Al	0.95 (2)	W	<0.01
Na	0.74 (4)	As	<0.01
Ti	0.57 (4)	Pb	<0.01
Co	0.45 (2)	Nd	<0.01
Ni	0.058 (8)	Y	<0.01
Ca	0.042 (13)

Figure 2 (a) SEM BSE image and (b) the corresponding elemental mapping (EDS) of unground pyrite concentrate powder encased in resin. (c)–(f) Individual maps for Al, Si, Fe and S, respectively. Ten areas and the corresponding elemental maps were measured and are shown in Fig. S3, and this area was chosen as representative.

SEM imaging reveals phases separated into distinct particles of a relatively broad size distribution ranging from 1000 µm down to 1 µm. The measured composition of individual grains obtained using SEM-EDS is in agreement with the phase identification from XRD. The majority contain exclusively Fe and S, corresponding to the pyrite and pyrrhotite phases. The second most common compositions were silicates containing either Si and O, or Na, Al, Si and O, corresponding to the quartz and albite phases, respectively. A small number of aluminosilicate particles containing K or Ca (Fig. S3) suggests the presence of alkaline and plagioclase feldspars, noting significant miscibility between those minerals and albite, forming the feldspar family (Iddings, 1898; Zambonini & Washington, 1923). Other aluminosilicate particles con­taining Mg with lamellar morphology (Fig. S3) may suggest the presence of magnesium-rich mica, as observed in the ore before flotation (Plimer, 1977). No reflections for alumino­silicates other than albite were visible in the diffraction patterns as a result of their low amount, later confirmed using WD-XRF. SEM-EDS reveals Ti and O in isolated particles (light green in Fig. S3), confirming the presence of the rutile phase. Co is known to substitute for Fe in pyrite, and although no Co was detected in particles other than the iron sulfides, SEM-EDS has little discrimination between Fe and Co due to the overlap of Fe Kβ (7058 eV) and Co Kα (6923 eV) (Deslattes et al., 2005) transition energies. A few isolated oxide particles containing Zr, or a mixture of La, Ce and Nd, were sometimes observed using BSE imaging. However, no Zr or lanthanoid oxides were visible using XRD, presumably because of their very low amount as confirmed by WD-XRF (Table 2).

All elements >0.5 wt% as determined using WD-XRF (S, Fe, Si, Al, Na, Ti) correspond to phase compositions detected using XRD. Other elements (Co, Ni, Ca, Mg, K, Zr, Nb, Y) consistent with those detected by SEM-EDS were identified by WD-XRF but did not correspond to the composition of crystalline phases identified using XRD, presumably because these elements are present as substituents within visible phases or belong to impurity phases below the detection limit of the method. The higher energy resolution of WD-XRF compared with SEM-EDS enabled the confirmation of Co in the presence of Fe in the sample and also revealed trace amounts of Ni, possibly as a third substituent for Fe in the pyrite phase, in the molar ratio Fe:Co:Ni = 0.987 (8): 0.012 (10):0.002 (4). Trace amounts of Ca, K and Mg, alongside Na and Al, in the molar ratio Al:Na:Ca:K:Mg = 1.00 (2):0.91 (5):0.030 (9):0.02 (7):0.037 (5) are consistent with the presence of albite and the absence of other feldspars in the XRD data, and consistent with previous mineralogical analysis of samples from the Thackaringa mine (Plimer, 1977). The presence of trace amounts of Zr and Nb confirms the absence of visible zirconia and lanthanoid oxide phases in the XRD data. Trace amounts of As, Pb and Y may be present, but the signal is at the detection limit of the method (Fig. S4). As can substitute for S in FeS₂, Pb may be a small impurity as PbS, commonly associated with pyrite (Abraitis et al., 2004), and Y is a common impurity in lanthanoid minerals. We note the presence of W, probably as contamination from the WC jars used in the milling process.

3.2. Influence of preparation methods on quantitative phase analysis from XRD

For comparison with milled samples, we first prepared pyrite concentrate samples for XRD by hand grinding powder for 30 min in an agate mortar and top loading into sample holders. As expected, XRD data for hand-ground preparations lacked reproducibility as a result of poor particle statistics, microabsorption and preferred orientation (Fig. S5). Reflection intensities differed slightly from those calculated for published crystal structures of pyrite and quartz, and differed greatly for albite (Fig. 3). Albite is known to be susceptible to preferred orientation due to its plate-like morphology and polysynthetic twinning (Heidelbach et al., 2000; Jiang et al., 2000; Kleeberg et al., 2008; Vance, 1961; Donnay, 1940), with preferred orientation strong along the [001] direction and relatively weaker along the [010] direction in flat-plate sample preparations (Kleeberg et al., 2008). Although preferred orientation in albite may be better represented by complex models such as spherical harmonics, considering reflections for this phase have low intensity, a single March–Dollase parameter was selected as an approximation to reduce the number of refined parameters. The best agreement between measured and calculated reflection intensities was obtained with a correction along the [013] unique axis by trial and error for the 0 and 1 min samples, roughly approximating the preferred orientation determined by Kleeberg and co-workers, noting that a range of [0kl] unique axes when l > k adequately modelled the observed intensities. The choice of unique axis becomes insignificant as milling time increases and preferred orientation becomes negligible (the March–Dollase parameter is close to 1). For consistency, refinement of preferred orientation along the [013] unique axis was used in model descriptions of all sample data.

Figure 3 Rietveld refinement profiles using XRD data of pyrite concentrate powder as (a) an unground control, and prepared by (b) hand grinding, (c) grease loading and (d) 7 min ball milling. The relative percentage differences between the observed (Io) and calculated (Ic) intensities are shown beneath each profile. Rietveld refinement residuals for each sample preparation are given in Table S2.

Several methods for the preparation of samples for XRD analysis have been suggested to correct for this effect, such as side loading of samples or sprinkling onto grease (Kleeberg et al., 2008; Unruh & Forbes, 2019). We note that top and side loading amplified different sets of reflections for albite, with the cluster of reflections at 32.6° the most susceptible, but neither method prevented preferred orientation. Loading onto grease substantially reduced preferred orientation in the albite phase (Fig. 3), where the March–Dollase parameter refined to a value closer to 1, indicating a more random orientation of the powder. However, the patterns still lacked reproducibility, with this more evident for pyrite reflections, suggesting that the relatively small amount of powder in the grease preparation and the large particle size may lead to poor particle statistics. Fig. 3 shows typical Rietveld refinement profiles using XRD data of pyrite concentrate powder prepared by four different methods. Refinement residuals and the March–Dollase correction value for albite are given in Table S2.

Although pyrite is relatively soft (around 6 on the Mohs scale) (Craig & Vokes, 1993), it was later confirmed by SEM and laser diffraction that the particles remained relatively large after hand grinding in an agate mortar, perhaps due to the presence of harder quartz particles (around 7 on the Mohs scale) (Deer et al., 1962). Large crystallites are a well known source of systematic errors in powder diffraction (Moore & Reynolds, 1997). Neutron diffraction measurements with area detectors confirmed the poor particle statistics, even in larger pyrite concentrate samples, compared with XRD (Fig. S6). Although sieving is sometimes suggested to remove large crystallites (Brindley, 1945), pyrite concentrate powders are found to have a phase distribution that is correlated with grain size [Fig. S2(b)], with pyrite more represented in larger grains, so sieving would result in a modification of the sample composition. Grain size reduction has been shown to be effective in improving particle statistics and reducing preferred orientation and microabsorption (Madsen et al., 2019; Kleeberg et al., 2008; Klug & Alexander, 1954). A homogeneous size distribution of fine particles (<10 µm) has been stated as ideal (Brindley, 1945; Klug & Alexander, 1954). However, excessive milling can lead to the introduction of particle strain or induce chemical reactions, such as oxidation of ultrafine particles (Karim et al., 2016; Dettrick et al., 2019), and can also introduce structural defects, potentially causing further difficulty in QPA using XRD (Sakher et al., 2018; Madsen et al., 2019; O'Connor & Chang, 1986; Hillier, 2003; Dermatas et al., 2007).

Better agreement between observed and modelled reflection intensity, and improved pattern reproducibility across preparations, were obtained after ball milling the pyrite concentrate (Fig. 3), suggesting the suitability of this method of pyrite concentrate sample preparation for QPA using XRD. Because the optimal milling procedure is dependent on sample characteristics (O'Connor & Chang, 1986), the milling preparation was optimized for pyrite concentrate powder and the accuracy and precision of the QPA results were determined.

3.3. Optimization of sample milling time

The particle size distribution of pyrite concentrate powder ball milled for different times was investigated by SEM imaging and laser diffraction (Fig. 4 and Table 3).

Table 3
Volume moment mean diameter D[4,3] from laser diffraction of ball-milled pyrite concentrate powder samples

Milling time (min)	Mean particle size D[4,3] (µm)
0	129 (3)
1	42 (3)
2	10.5 (2)
3	5.62 (14)
5	3.83 (8)
7	2.72 (11)
10	2.19 (11)

Figure 4 Representative SEM BSE images of pyrite concentrate powder samples ball milled for 0, 1, 5 and 10 min.

The SEM and laser diffraction data follow the expected trend of a reduction in particle size with increasing milling time, where the reduction rate decreases as the milling time is further increased (O'Connor & Chang, 1986). Powders milled for 5 and 10 min contain particles of <3 µm diameter in larger agglomerates, possibly due to triboelectric effects introduced by friction in the dry milling procedure (Mirkowska et al., 2016; Landauer & Foerst, 2019), with a small portion of particles of diameter >10 µm. Laser diffraction reveals a multimodal particle size distribution (Fig. S18), probably resulting from differential grinding according to mineral hardness.

The pyrite concentrate powder milled for different times was examined using XRD, with the final phase composition calculated from Rietveld refinement using five separate XRD measurements of samples from the same batch of milled powder. Pattern simulations (Fig. S7) showed negligible changes in intensity when Co, Ni and As were substituted into the crystal structure of FeS₂, or when Mg, Ca and K were substituted into NaAlSi₃O₈, according to semi-quantitative WD-XRF elemental ratios, suggesting that XRD is not sensitive to those substitutions. Given this lack of sensitivity, the refinement of atomic occupancies was not attempted and pure phase compositions were used for QPA.

The average results and reproducibility over the five repeat analyses are first qualitatively assessed before comparison with the composition obtained from calibrated WD-XRF. Standard deviations in refined parameters obtained for five replicates (Figs. 5 and 6) reveal a clear improvement in the reproducibility of XRD data when the sample milling time is increased. The discrepancy between observed and calculated patterns (Figs. S9–S15), as reflected in the weighted profile reliability factor R_wp (Fig. S8, Table S3), also decreases with increased milling time, with a plateau reached after about 7 min. Fig. 6 shows that the mean refined value of the March–Dollase parameter to correct for preferred orientation of the albite phase approaches 1, indicative of minimal preferred orientation in the phase, as the milling time increases. Excluding measurements with unground powder, the unit-cell parameter changes were within 0.002% (Table S4), suggesting chemical stability of the phases.

Figure 5 (a) Mean phase fractions and (b) mean crystallite sizes for phases determined using XRD of five pyrite concentrate powder samples milled for different times. For the 0 min milling time sample, the crystallite size of rutile was fixed to 0.1 µm to prevent correlations between crystallite size and weight fraction parameters. Error bars represent sample standard deviations of the mean values for the five repeats at each milling time. Values of the Rietveld refinement residual Rwp are plotted in Fig. S8 and given in Table S3 with other residuals. Typical refinement profiles are shown in Fig. S9–15.

Figure 6 The mean March–Dollase ratio for the albite phase obtained from Rietveld refinements using XRD data of five pyrite concentrate powders milled for different times. A March–Dollase ratio of 1 indicates random powder orientation with respect to the chosen unique reflection direction [013]. Reflection intensities in very low milling time samples with poor particle statistics may also be partially modelled by this parameter. Error bars represent sample standard deviations of the mean values for the five repeats at each milling time. Values are given in Table S3.

Particle size reduction causes reflection broadening, as indicated by the reduction in the refined crystallite size with milling time [Fig. 7(b), Fig. S16]. Peak broadening may cause difficulty in discriminating reflections for minor phases such as rutile and pyrrhotite [Fig. 7(a)], with significant broadening for the pyrrhotite phase causing overlap of five proximal pyrrhotite reflections in the data [Fig. 7(b)] and refined crystallite sizes below 0.05 µm. This is probably due to pyrrhotite having a much lower hardness (around 3.5–4.5 on the Mohs scale) (Chen et al., 2020) than the other phases. Reflection overlap from broadening may explain the increase in uncertainty observed for the pyrrhotite weight fraction when the milling time is increased from 7 to 10 min (Fig. 5). Milling times longer than 10 min were not investigated.

Figure 7 XRD data, shown as solid lines for clarity, of pyrite concentrate powder milled for 1 and 5 min, showing broadening of (a) the pyrite overlapped reflections 312 and 321, and (b) the pyrrhotite overlapped reflections 402, 223, , and 313.

The preparation was compared with that obtained using the McCrone XRD-Mill vibratory rod mill under propan-2-ol, a particle size reduction method recommended for XRD sample preparation (Whitfield et al., 2019). Mean particle sizes equivalent to those obtained after 7 min in the ESSA mill were obtained after 30 min in the McCrone mill (Fig. S18). Although laser diffraction revealed a narrower particle size distribution using the McCrone mill, under-ground particles of around 10 µm remained. Comparison of XRD data for samples ground using the two different mills revealed slightly sharper reflections for the McCrone preparation (Fig. S19), resulting in smaller refined crystallite sizes for most phases (Table S6). Refined parameters were comparable between the two preparations, although we note that further optimization of the faster ESSA ball mill method may be achieved by considering factors such as the number, size and shape of the balls, as well as the amount of powder, number of rotations per minute, milling medium, ball and jar materials etc.

A strong correlation exists between particle size and refined parameters (Fig. S16), as expected from the influence of particle statistics and microabsorption, noting a substantial underestimation of pyrite weight fraction when the particle size is high. Microabsorption (Brindley, 1945) is expected to be problematic in pyrite concentrate samples due to the presence of phases with different mass attenuation coefficients (MACs) (FeS₂ MAC = 100 cm² g⁻¹, SiO₂ MAC = 54 cm² g⁻¹ at 1.79 Å); we note that although corrections exist (Brindley, 1945; Rousseau, 2006) they are often unsatisfactory (Scarlett & Madsen, 2018). Although further particle size reduction may reduce microabsorption, it may also induce excessive broadening of reflections. Shorter-wavelength instruments may be desirable for those samples. A milling time of around 7 min, corresponding to mean particle sizes close to 3 µm, was considered a suitable compromise for the preparation of pyrite concentrate samples for XRD using Co Kα wavelength.

3.4. Comparison of XRD results with elemental analysis

To confirm the validity of the refined phase fractions from XRD analysis, the results were compared with elemental analysis determined using WD-XRF. The precision of QPA from XRD was assessed by repeating the measurement and analysis over five samples taken from 1 kg aliquots of the pyrite concentrate that were subjected to 7 min milling and compared with WD-XRF analyses of the samples (Tables 4 and 5).

Table 4
Mean phase fractions obtained from Rietveld analysis using XRD data from five samples of the same pyrite ore concentrate aliquot, each individually milled for 7 min

Sample standard deviations of the mean values from the five repeats are indicated. Note the similarity to the estimated standard deviations from Rietveld analysis.

Phase	Pyrite	Albite	Quartz	Pyrrhotite	Rutile
Mean phase fraction (wt%)	82.7 (3)	8.4 (2)	4.94 (12)	3.07 (10)	0.92 (2)

Table 5
Comparison of the mean elemental weight fractions obtained using XRD and calibrated WD-XRF weight fractions for five pyrite concentrate samples from the same aliquot, each individually ball milled for 7 min

WD-XRF data were empirically calibrated using standard mixtures to correct for matrix effects (Rousseau, 2006). Sample standard deviations of the mean values from the five repeats are indicated.

	Wt%
Element	XRD	WD-XRF
S	45.4 (2)	47.2 (2)
Fe	40.3 (2)	42.04 (14)
Si	5.00 (11)	4.03 (10)

Table 4 shows the mean phase fractions obtained from QPA of five pyrite ore samples milled for 7 min. The standard deviations for the refined phase fractions over the five repeats lie below 0.3 wt%, confirming the good reproducibility of this preparation method. The elemental composition calculated from the refined phase fractions obtained from XRD is compared with that obtained using WD-XRF in Table 5. We note that calibration with a matrix-matching standard (Souders & Sylvester, 2010; Rousseau, 2006) was necessary in the WD-XRF method, with the major elements Fe, S and Si calibrated using FeS₂/SiO₂ mixtures in a composition range close to that of the pyrite concentrate sample. The elemental weight fractions for these elements obtained from the two methods are within 2 wt% (Table 5). Although in general agreement, the amount of Fe and S is slightly overestimated and Si slightly underestimated by XRD. The bias is much larger than the standard deviations across repeats (Table 5), suggesting a systematic, rather than statistical, error. Some of these discrepancies could be ascribed to elements not included in the composition of refined phases, such as Mg, K and Ca in albite, and Co, Ni and As in pyrite, or impurities containing Pb, Nd, Y and Zr in amounts too small to be visible in XRD. However, the difference should be smaller than 0.5 wt% according to multi-elemental WD-XRF data (Table 2). An overestimation of heavier elements may point to uncorrected microabsorption, despite empirical calibration being used in the XRF analysis, perhaps resulting from a different particle size distribution in the ore sample compared with purchased synthetic standards. Although particle size reduction decreases the effect of microabsorption, and samples were ball milled identically in preparations for both XRD and XRF analyses, microabsorption may still be non-negligible (Scarlett et al., 2002; Whitfield, 2016) and the degree of microabsorption may differ between characterization methods considering the different wavelengths used.

The presence of an unaccounted for amorphous phase may also explain the differences between elemental compositions determined by XRD and WD-XRF, with this phase either present in the original material or induced by high-intensity ball milling. The external standard method (O'Connor & Raven, 1988) returned −9.0 (5) wt% amorphous content. This physically unrealistic negative value reveals a bias of the method, consistent with a previous investigation (Scarlett & Madsen, 2018) which showed that amorphous content estimation is notoriously inaccurate in complex samples susceptible to microabsorption, as is the case for pyrite ore concentrate samples. Correlations between refined ADPs and scale factors of the alumina standard [correlation factors were 0.81 and 0.66 for U_iso(Al) and U_iso(O), respectively] further contribute to inaccuracies (Madsen et al., 2011).

Although the exact amount cannot be determined accurately, the absence of broad features in the background of the XRD patterns (Fig. S17) comparable to the fully crystalline standard suggests that the amount of amorphous phases is low in the concentrate. A bias can also be introduced from imperfectly modelled reflection intensity and peak shape. Crystal structures with calculated intensity ratios close to those observed were selected from the literature but some uncertainty remains, for example in the choice of polytype for albite being complicated by preferred orientation for this phase in pyrite concentrate samples. Both pyrite and albite are known to have a strong tendency to accept impurities, as suggested by multi-elemental XRF and SEM-EDS, with different compositional variances generating slightly different Bragg positions which, when superimposed, can result in slightly abnormal peak shapes that can hamper correct intensity refinement. Although refined parameters such as particle size or strain, March–Dollase correction, atomic positions and ADPs can model those differences, resulting in reasonable agreement between observed and calculated patterns, a systematic error may remain in refined weight fractions. The observed compositional bias may be the result of a combination of all previously identified sources of errors. Nevertheless, the QPA of pyrite concentrate powder ball milled to 3 µm particle size (7 min milling time) produces weight fractions within 2 wt% of those determined using calibrated WD-XRF, with standard deviations <0.3 wt%, confirming the reproducibility of the method and making it suitable at least for comparative analysis.

4. Conclusions

The quantitative phase analysis using XRD of pyrite ore concentrate powder extracted from the Thackaringa mine in Australia was problematic due to the presence of large particles, hard impurities and preferred orientation of the albite phase. Milling of the powder to particle sizes around 3 µm yielded reproducible results across preparations and was found to be suitable for the quantitative phase analysis of pyrite concentrate using XRD. Complementary techniques were necessary for the detection of trace elements and minerals. Refined phase fractions using XRD data for all phases are significantly correlated with the mean volume particle size.

Milling resulted in a slight broadening of XRD reflections, without appreciable phase transformation, although substantial broadening of the pyrrhotite phase was observed which may influence the phase quantification after 10 min milling.

The elemental composition obtained from XRD of pyrite concentrate powder milled for 7 min, with a mean volume particle size around 3 µm, was in general agreement with that obtained from WD-XRF. However, we note that some discrepancy remains, perhaps as a result of unaccounted elemental substitutions or amorphous phases.

The study provides a useful methodology for the precise QPA of pyrite ore concentrates using XRD, as long as the analyst is aware of the possible drawbacks of the methods as highlighted in this article. Researchers are urged not to rely on a single preparation or analysis technique for the QPA of pyrite ores and to assess reproducibility and accuracy for each new sample composition with as much knowledge about the sample as possible.

Supporting information

Computing details

(QPAPBMXGreaseSuspendedSamplePrep_publ)

Crystal data

a = Å	β = °
b = Å	γ = °
c = Å	Specimen preparation: Prepared at 298 K and 101.3 kPa, cooled at N/A K min^−1
α = °

(QPAPBMXGreaseSuspendedSamplePrep_overall)

Crystal data

a = Å	α = °
b = Å	β = °
c = Å	γ = °

Refinement

Least-squares matrix: full	(Δ/σ)max = 1.315
30 parameters

(QPAPBMXGreaseSuspendedSamplePrep_phase_2)

Crystal data

AlNaO8Si3	β = 116.5999°
Mr = 262.22	γ = 87.8097°
Triclinic, C1	V = 665.11 Å^3
a = 8.138925 Å	Z = 4
b = 12.799307 Å	Dx = 2.619 Mg m^−3
c = 7.160071 Å	T = 300 K
α = 94.2255°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.206(13), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7460	O1—Al1^xi	1.7460
Al1—O3^ii	1.7425	O1—Si1^iii	1.6002
Al1—O5	1.7372	O1—Na1^xii	2.6726
Al1—O7	1.7472	O1—Na1^iii	2.5302
Si1—O1^iii	1.6002	O2—Si2^x	1.6305
Si1—O4^ii	1.6011	O2—Si3	1.6496
Si1—O6	1.6244	O2—Na1	2.3708
Si1—O8	1.6190	O3—Al1^xiii	1.7425
Si2—O2^iv	1.6305	O3—Si2	1.5947
Si2—O3	1.5947	O3—Na1^ix	2.4545
Si2—O6^v	1.6207	O4—Si1^xiii	1.6011
Si2—O8^vi	1.6171	O4—Si3	1.6208
Si3—O2	1.6496	O5—Al1	1.7372
Si3—O4	1.6208	O5—Si3^xiv	1.5965
Si3—O5^vii	1.5965	O6—Si1	1.6244
Si3—O7^vi	1.6024	O6—Si2^xv	1.6207
Na1—O1^viii	2.6726	O7—Al1	1.7472
Na1—O1^iii	2.5302	O7—Si3^vi	1.6024
Na1—O2	2.3708	O7—Na1^iv	2.4364
Na1—O3^ix	2.4545	O8—Si1	1.6190
Na1—O7^x	2.4364	O8—Si2^vi	1.6171
O1^i—Al1—O3^ii	102.839	O6^v—Si2—O8^vi	110.392
O1^i—Al1—O5	116.078	O2—Si3—O4	107.348
O3^ii—Al1—O5	112.16	O2—Si3—O5^vii	105.916
O1^i—Al1—O7	103.947	O4—Si3—O5^vii	110.171
O3^ii—Al1—O7	111.136	O2—Si3—O7^vi	108.553
O5—Al1—O7	110.225	O4—Si3—O7^vi	110.204
O1^iii—Si1—O4^ii	109.382	O5^vii—Si3—O7^vi	114.325
O1^iii—Si1—O6	112.467	Al1^xi—O1—Si1^iii	141.36
O4^ii—Si1—O6	108.286	Si2^x—O2—Si3	130.051
O1^iii—Si1—O8	107.201	Si2^x—O2—Na1	120.258
O4^ii—Si1—O8	111.41	Si3—O2—Na1	108.874
O6—Si1—O8	108.124	Al1^xiii—O3—Si2	139.443
O2^iv—Si2—O3	111.07	Si1^xiii—O4—Si3	161.159
O2^iv—Si2—O6^v	104.318	Al1—O5—Si3^xiv	129.66
O3—Si2—O6^v	112.142	Si1—O6—Si2^xv	135.75
O2^iv—Si2—O8^vi	106.953	Al1—O7—Si3^vi	133.908
O3—Si2—O8^vi	111.607	Si1—O8—Si2^vi	151.752

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

(QPAPBMXGreaseSuspendedSamplePrep_phase_0)

Crystal data

FeS2	V = 159.16 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.007 Mg m^−3
a = 5.41928 (5) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.379(4), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.0115 (7)*
S2	0.38435 (13)	0.38435	0.38435	0.0087 (6)*

Bond lengths (Å)

Fe1—S2^i	2.2636 (2)	Fe1—S2^vi	2.2636 (7)
Fe1—S2^ii	2.2636 (2)	S2—Fe1^vii	2.2636 (2)
Fe1—S2^iii	2.2636 (2)	S2—Fe1^viii	2.2636 (2)
Fe1—S2^iv	2.2636 (2)	S2—Fe1^ix	2.2636 (7)
Fe1—S2^v	2.2636 (2)	S2—S2^x	2.1712 (8)

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

(QPAPBMXGreaseSuspendedSamplePrep_phase_3)

Crystal data

Fe7S8	β = 117.25 (2)°
Mr = 647.41	V = 933.0 (2) Å^3
Monoclinic, C2/c	Z = 4
a = 11.937 (11) Å	Dx = 4.609 Mg m^−3
b = 6.8622 (15) Å	T = 300 K
c = 12.812 (13) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.061(4), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.494	Fe5—S2^v	2.4442
S1—Fe5	2.4125	Fe5—S4	2.3841
S1—Fe7^ii	2.3889	Fe5—S6	2.3608
S1—Fe7^iii	2.4406	S6—Fe3^viii	2.4502
S1—Fe8	2.4064	S6—Fe5	2.3608
S2—Fe3	2.3743	S6—Fe7	2.4324
S2—Fe3^iv	2.3236	S6—Fe7^iii	2.3899
S2—Fe5^v	2.4442	Fe7—S1^ix	2.3889
S2—Fe7^vi	2.3660	Fe7—S1^iii	2.4406
S2—Fe8^iv	2.4110	Fe7—S2^x	2.3660
Fe3—S1^i	2.494	Fe7—S6	2.4324
Fe3—S2	2.3743	Fe7—S6^iii	2.3899
Fe3—S2^iv	2.3236	Fe8—S1	2.4064
Fe3—S6^vii	2.4502	Fe8—S1^i	2.4064
S4—Fe5	2.3841	Fe8—S2^iv	2.4110
Fe5—S1	2.4125	Fe8—S2^viii	2.4110

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(QPAPBMXGreaseSuspendedSamplePrep_phase_4)

Crystal data

O2Ti	V = 62.61 (6) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.238 Mg m^−3
a = 4.597 (3) Å	T = 300 K
c = 2.963 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.100, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	1.9824	Ti1—O1^v	1.9501
Ti1—O1^i	1.9501	O1—Ti1	1.9824
Ti1—O1^ii	1.9501	O1—Ti1^vi	1.9501
Ti1—O1^iii	1.9824	O1—Ti1^vii	1.9501
Ti1—O1^iv	1.9501
O1—Ti1—O1^i	90	O1^iii—Ti1—O1^iv	90
O1—Ti1—O1^ii	90	O1—Ti1—O1^v	90
O1^i—Ti1—O1^ii	98.87	O1^i—Ti1—O1^v	180
O1—Ti1—O1^iii	180	O1^ii—Ti1—O1^v	81.13
O1^i—Ti1—O1^iii	90	O1^iii—Ti1—O1^v	90
O1^ii—Ti1—O1^iii	90	O1^iv—Ti1—O1^v	98.87
O1—Ti1—O1^iv	90	Ti1—O1—Ti1^vi	130.565
O1^i—Ti1—O1^iv	81.13	Ti1—O1—Ti1^vii	130.565
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	98.87

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

(QPAPBMXGreaseSuspendedSamplePrep_phase_1)

Crystal data

O2Si	V = 113.09 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.647 Mg m^−3
a = 4.9149 (5) Å	T = 300 K
c = 5.4057 (4) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.244(15), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.010*
O1	0.41460	0.26780	0.78543	0.010*

Geometric parameters (Å, º)

Si1—O1	1.6053	O1—Si1	1.6053
Si1—O1^i	1.6116	O1—Si1^iv	1.6116
Si1—O1^ii	1.6114	O1—Si1^v	1.6114
Si1—O1^iii	1.6054
O1—Si1—O1^i	110.256	O1^ii—Si1—O1^iii	110.262
O1—Si1—O1^ii	108.745	Si1—O1—Si1^iv	143.832
O1^i—Si1—O1^ii	109.685	Si1—O1—Si1^v	143.836
O1—Si1—O1^iii	109.161	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.725

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

(QPAPBMXGreaseSuspendedSamplePrep_pwd_0)

Crystal data

a = Å	β = °
b = Å	γ = °
c = Å	Kα1,2 radiation
α = °	T = 300 K

Data collection

Panalytical_Reflection_Transmission diffractometer	2θmin = 10.017°, 2θmax = 89.993°, 2θstep = 0.013°
Radiation source: Co-Ka, Graded_Flat

Refinement

Rp = 0.081	6092 data points
Rwp = 0.114	Profile function: Finger-Cox-Jephcoat function parameters U, V, W, X, Y, SH/L: peak variance(Gauss) = Utan(Th)^2+Vtan(Th)+W: peak HW(Lorentz) = X/cos(Th)+Ytan(Th); SH/L = S/L+H/L U, V, W in (centideg)^2, X & Y in centideg 0.000, 0.000, 3.345, 2.239, -0.670, 0.034,
Rexp = 0.064	Background function: Background function: "chebyschev-1" function with 7 terms: 181.2(5), -233.0(9), 140.3(8), -64.2(7), 23.5(7), -5.0(5), 3.5(5),

 

(QPAPBMXHandGrindSamplePrep_phase_2)

Crystal data

AlNaO8Si3	β = 116.5972°
Mr = 262.22	γ = 87.7872°
Triclinic, C1	V = 664.64 Å^3
a = 8.141789 Å	Z = 4
b = 12.787902 Å	Dx = 2.621 Mg m^−3
c = 7.158828 Å	T = 300 K
α = 94.2429°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 1.000, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7455	O1—Al1^xi	1.7455
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7356	O1—Na1^xii	2.6716
Al1—O7	1.7471	O1—Na1^iii	2.5304
Si1—O1^iii	1.5999	O2—Si2^x	1.6297
Si1—O4^ii	1.6013	O2—Si3	1.6483
Si1—O6	1.6228	O2—Na1	2.3717
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6297	O3—Si2	1.5949
Si2—O3	1.5949	O3—Na1^ix	2.4534
Si2—O6^v	1.6202	O4—Si1^xiii	1.6013
Si2—O8^vi	1.6169	O4—Si3	1.6208
Si3—O2	1.6483	O5—Al1	1.7356
Si3—O4	1.6208	O5—Si3^xiv	1.5965
Si3—O5^vii	1.5965	O6—Si1	1.6228
Si3—O7^vi	1.6022	O6—Si2^xv	1.6202
Na1—O1^viii	2.6716	O7—Al1	1.7471
Na1—O1^iii	2.5304	O7—Si3^vi	1.6022
Na1—O2	2.3717	O7—Na1^iv	2.4350
Na1—O3^ix	2.4534	O8—Si1	1.6191
Na1—O7^x	2.4350	O8—Si2^vi	1.6169
O1^i—Al1—O3^ii	102.855	O6^v—Si2—O8^vi	110.428
O1^i—Al1—O5	116.061	O2—Si3—O4	107.334
O3^ii—Al1—O5	112.147	O2—Si3—O5^vii	105.864
O1^i—Al1—O7	103.957	O4—Si3—O5^vii	110.228
O3^ii—Al1—O7	111.182	O2—Si3—O7^vi	108.58
O5—Al1—O7	110.191	O4—Si3—O7^vi	110.176
O1^iii—Si1—O4^ii	109.397	O5^vii—Si3—O7^vi	114.331
O1^iii—Si1—O6	112.462	Al1^xi—O1—Si1^iii	141.388
O4^ii—Si1—O6	108.255	Si2^x—O2—Si3	129.999
O1^iii—Si1—O8	107.195	Si2^x—O2—Na1	120.298
O4^ii—Si1—O8	111.458	Si3—O2—Na1	108.885
O6—Si1—O8	108.103	Al1^xiii—O3—Si2	139.47
O2^iv—Si2—O3	111.114	Si1^xiii—O4—Si3	161.161
O2^iv—Si2—O6^v	104.247	Al1—O5—Si3^xiv	129.633
O3—Si2—O6^v	112.16	Si1—O6—Si2^xv	135.712
O2^iv—Si2—O8^vi	106.957	Al1—O7—Si3^vi	133.928
O3—Si2—O8^vi	111.575	Si1—O8—Si2^vi	151.749

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

(QPAPBMXHandGrindSamplePrep_phase_0)

Crystal data

FeS2	V = 159.13 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.007 Mg m^−3
a = 5.41900 (5) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.389(5), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.0281 (10)*
S2	0.38871 (17)	0.38871	0.38871	0.0310 (8)*

Bond lengths (Å)

Fe1—S2^i	2.2725 (2)	Fe1—S2^vi	2.2725 (8)
Fe1—S2^ii	2.2725 (2)	S2—Fe1^vii	2.2725 (2)
Fe1—S2^iii	2.2725 (2)	S2—Fe1^viii	2.2725 (2)
Fe1—S2^iv	2.2725 (2)	S2—Fe1^ix	2.2725 (8)
Fe1—S2^v	2.2725 (2)	S2—S2^x	2.0892 (10)

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

(QPAPBMXHandGrindSamplePrep_phase_3)

Crystal data

Fe7S8	β = 117.08 (7)°
Mr = 647.41	V = 939.0 (4) Å^3
Monoclinic, C2/c	Z = 4
a = 11.93 (4) Å	Dx = 4.579 Mg m^−3
b = 6.860 (5) Å	T = 300 K
c = 12.89 (4) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.0230(14), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4986	Fe5—S2^v	2.4477
S1—Fe5	2.4174	Fe5—S4	2.3913
S1—Fe7^ii	2.3925	Fe5—S6	2.3667
S1—Fe7^iii	2.4473	S6—Fe3^viii	2.4552
S1—Fe8	2.413	S6—Fe5	2.3667
S2—Fe3	2.3821	S6—Fe7	2.4369
S2—Fe3^iv	2.3308	S6—Fe7^iii	2.3964
S2—Fe5^v	2.4477	Fe7—S1^ix	2.3925
S2—Fe7^vi	2.3716	Fe7—S1^iii	2.4473
S2—Fe8^iv	2.4155	Fe7—S2^x	2.3716
Fe3—S1^i	2.4986	Fe7—S6	2.4369
Fe3—S2	2.3821	Fe7—S6^iii	2.3964
Fe3—S2^iv	2.3308	Fe8—S1	2.413
Fe3—S6^vii	2.4552	Fe8—S1^i	2.413
S4—Fe5	2.3913	Fe8—S2^iv	2.4155
Fe5—S1	2.4174	Fe8—S2^viii	2.4155

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(QPAPBMXHandGrindSamplePrep_phase_4)

Crystal data

O2Ti	V = 62.58 (2) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.240 Mg m^−3
a = 4.5962 (7) Å	T = 300 K
c = 2.9622 (7) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 1.000, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	1.9821	Ti1—O1^v	1.9497
Ti1—O1^i	1.9497	O1—Ti1	1.9821
Ti1—O1^ii	1.9497	O1—Ti1^vi	1.9497
Ti1—O1^iii	1.9821	O1—Ti1^vii	1.9497
Ti1—O1^iv	1.9497
O1—Ti1—O1^i	90	O1^iii—Ti1—O1^iv	90
O1—Ti1—O1^ii	90	O1—Ti1—O1^v	90
O1^i—Ti1—O1^ii	98.866	O1^i—Ti1—O1^v	180
O1—Ti1—O1^iii	180	O1^ii—Ti1—O1^v	81.134
O1^i—Ti1—O1^iii	90	O1^iii—Ti1—O1^v	90
O1^ii—Ti1—O1^iii	90	O1^iv—Ti1—O1^v	98.866
O1—Ti1—O1^iv	90	Ti1—O1—Ti1^vi	130.567
O1^i—Ti1—O1^iv	81.134	Ti1—O1—Ti1^vii	130.567
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	98.866

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

(QPAPBMXHandGrindSamplePrep_phase_1)

Crystal data

O2Si	V = 113.03 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.648 Mg m^−3
a = 4.9135 (3) Å	T = 300 K
c = 5.4058 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.263(14), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.006
O1	0.41460	0.26780	0.78543	0.011

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0073	0.0059	0.0053	0.0029	0.0003	0.0006
O1	0.0120	0.0105	0.0118	0.0065	−0.0029	−0.0040

Geometric parameters (Å, º)

Si1—O1	1.6049	O1—Si1	1.6049
Si1—O1^i	1.6114	O1—Si1^iv	1.6114
Si1—O1^ii	1.6111	O1—Si1^v	1.6111
Si1—O1^iii	1.6050
O1—Si1—O1^i	110.262	O1^ii—Si1—O1^iii	110.268
O1—Si1—O1^ii	108.732	Si1—O1—Si1^iv	143.832
O1^i—Si1—O1^ii	109.697	Si1—O1—Si1^v	143.836
O1—Si1—O1^iii	109.164	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.712

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

 

(QPABAT3_phase_2)

Crystal data

AlNaO8Si3	β = 116.6°
Mr = 262.22	γ = 87.71°
Triclinic, C1	V = 664.01 Å^3
a = 8.137 Å	Z = 4
b = 12.785 Å	Dx = 2.623 Mg m^−3
c = 7.1583 Å	T = 300 K
α = 94.26°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.111(8), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7452	O1—Al1^xi	1.7452
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7351	O1—Na1^xii	2.6689
Al1—O7	1.7456	O1—Na1^iii	2.5308
Si1—O1^iii	1.5999	O2—Si2^x	1.6301
Si1—O4^ii	1.6000	O2—Si3	1.6472
Si1—O6	1.6223	O2—Na1	2.3704
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6301	O3—Si2	1.5944
Si2—O3	1.5944	O3—Na1^ix	2.4532
Si2—O6^v	1.6184	O4—Si1^xiii	1.6000
Si2—O8^vi	1.6168	O4—Si3	1.6198
Si3—O2	1.6472	O5—Al1	1.7351
Si3—O4	1.6198	O5—Si3^xiv	1.5968
Si3—O5^vii	1.5968	O6—Si1	1.6223
Si3—O7^vi	1.6020	O6—Si2^xv	1.6184
Na1—O1^viii	2.6689	O7—Al1	1.7456
Na1—O1^iii	2.5308	O7—Si3^vi	1.6020
Na1—O2	2.3704	O7—Na1^iv	2.4338
Na1—O3^ix	2.4532	O8—Si1	1.6191
Na1—O7^x	2.4338	O8—Si2^vi	1.6168
O1^i—Al1—O3^ii	102.836	O6^v—Si2—O8^vi	110.422
O1^i—Al1—O5	116.047	O2—Si3—O4	107.269
O3^ii—Al1—O5	112.215	O2—Si3—O5^vii	105.914
O1^i—Al1—O7	104.004	O4—Si3—O5^vii	110.224
O3^ii—Al1—O7	111.151	O2—Si3—O7^vi	108.565
O5—Al1—O7	110.14	O4—Si3—O7^vi	110.208
O1^iii—Si1—O4^ii	109.433	O5^vii—Si3—O7^vi	114.328
O1^iii—Si1—O6	112.47	Al1^xi—O1—Si1^iii	141.397
O4^ii—Si1—O6	108.187	Si2^x—O2—Si3	130.019
O1^iii—Si1—O8	107.176	Si2^x—O2—Na1	120.351
O4^ii—Si1—O8	111.446	Si3—O2—Na1	108.811
O6—Si1—O8	108.16	Al1^xiii—O3—Si2	139.461
O2^iv—Si2—O3	111.144	Si1^xiii—O4—Si3	161.151
O2^iv—Si2—O6^v	104.24	Al1—O5—Si3^xiv	129.689
O3—Si2—O6^v	112.114	Si1—O6—Si2^xv	135.676
O2^iv—Si2—O8^vi	106.97	Al1—O7—Si3^vi	133.943
O3—Si2—O8^vi	111.591	Si1—O8—Si2^vi	151.747

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

(QPABAT3_phase_0)

Crystal data

FeS2	V = 159.17 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.006 Mg m^−3
a = 5.41941 (3) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.1809(10), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.0051 (3)*
S2	0.38468 (9)	0.38468	0.38468	0.0058 (3)*

Bond lengths (Å)

Fe1—S2^i	2.2644 (1)	Fe1—S2^vi	2.2644 (4)
Fe1—S2^ii	2.2644 (1)	S2—Fe1^vii	2.2644 (1)
Fe1—S2^iii	2.2644 (1)	S2—Fe1^viii	2.2644 (1)
Fe1—S2^iv	2.2644 (1)	S2—Fe1^ix	2.2644 (4)
Fe1—S2^v	2.2644 (1)	S2—S2^x	2.1650 (6)

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

(QPABAT3_phase_3)

Crystal data

Fe7S8	β = 117.25 (6)°
Mr = 647.41	V = 934.4 (4) Å^3
Monoclinic, C2/c	Z = 4
a = 11.95 (3) Å	Dx = 4.602 Mg m^−3
b = 6.857 (4) Å	T = 300 K
c = 12.83 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.0305(25), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4939	Fe5—S2^v	2.4460
S1—Fe5	2.4144	Fe5—S4	2.3853
S1—Fe7^ii	2.3887	Fe5—S6	2.3618
S1—Fe7^iii	2.4436	S6—Fe3^viii	2.4507
S1—Fe8	2.4075	S6—Fe5	2.3618
S2—Fe3	2.3774	S6—Fe7	2.4353
S2—Fe3^iv	2.3243	S6—Fe7^iii	2.3907
S2—Fe5^v	2.4460	Fe7—S1^ix	2.3887
S2—Fe7^vi	2.3665	Fe7—S1^iii	2.4436
S2—Fe8^iv	2.4115	Fe7—S2^x	2.3665
Fe3—S1^i	2.4939	Fe7—S6	2.4353
Fe3—S2	2.3774	Fe7—S6^iii	2.3907
Fe3—S2^iv	2.3243	Fe8—S1	2.4075
Fe3—S6^vii	2.4507	Fe8—S1^i	2.4075
S4—Fe5	2.3853	Fe8—S2^iv	2.4115
Fe5—S1	2.4144	Fe8—S2^viii	2.4115

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(QPABAT3_phase_4)

Crystal data

O2Ti	V = 62.62 (3) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.238 Mg m^−3
a = 4.5980 (13) Å	T = 300 K
c = 2.9619 (13) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.073(10), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006*
O1	0.32861	0.32861	0.00000	0.005*

Geometric parameters (Å, º)

Ti1—O1	2.1368	Ti1—O1^v	1.8534
Ti1—O1^i	1.8534	O1—Ti1	2.1368
Ti1—O1^ii	1.8534	O1—Ti1^vi	1.8534
Ti1—O1^iii	2.1368	O1—Ti1^vii	1.8534
Ti1—O1^iv	1.8534
O1^i—Ti1—O1^ii	106.075	O1^ii—Ti1—O1^v	73.925
O1^i—Ti1—O1^iv	73.925	O1^iv—Ti1—O1^v	106.075
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	106.075
O1^i—Ti1—O1^v	180

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

(QPABAT3_phase_1)

Crystal data

O2Si	V = 113.08 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.647 Mg m^−3
a = 4.9143 (5) Å	T = 300 K
c = 5.4067 (5) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.145(6), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.020*
O1	0.41460	0.26780	0.78543	0.017*

Geometric parameters (Å, º)

Si1—O1	1.6051	O1—Si1	1.6051
Si1—O1^i	1.6117	O1—Si1^iv	1.6117
Si1—O1^ii	1.6114	O1—Si1^v	1.6114
Si1—O1^iii	1.6053
O1—Si1—O1^i	110.262	O1^ii—Si1—O1^iii	110.268
O1—Si1—O1^ii	108.73	Si1—O1—Si1^iv	143.833
O1^i—Si1—O1^ii	109.698	Si1—O1—Si1^v	143.836
O1—Si1—O1^iii	109.165	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.71

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

 

(QPABAT1ug3_phase_2)

Crystal data

AlNaO8Si3	β = 116.6°
Mr = 262.22	γ = 87.71°
Triclinic, C1	V = 664.01 Å^3
a = 8.137 Å	Z = 4
b = 12.785 Å	Dx = 2.623 Mg m^−3
c = 7.1583 Å	T = 300 K
α = 94.26°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.233(12), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7452	O1—Al1^xi	1.7452
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7351	O1—Na1^xii	2.6689
Al1—O7	1.7456	O1—Na1^iii	2.5308
Si1—O1^iii	1.5999	O2—Si2^x	1.6301
Si1—O4^ii	1.6000	O2—Si3	1.6472
Si1—O6	1.6223	O2—Na1	2.3704
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6301	O3—Si2	1.5944
Si2—O3	1.5944	O3—Na1^ix	2.4532
Si2—O6^v	1.6184	O4—Si1^xiii	1.6000
Si2—O8^vi	1.6168	O4—Si3	1.6198
Si3—O2	1.6472	O5—Al1	1.7351
Si3—O4	1.6198	O5—Si3^xiv	1.5968
Si3—O5^vii	1.5968	O6—Si1	1.6223
Si3—O7^vi	1.6020	O6—Si2^xv	1.6184
Na1—O1^viii	2.6689	O7—Al1	1.7456
Na1—O1^iii	2.5308	O7—Si3^vi	1.6020
Na1—O2	2.3704	O7—Na1^iv	2.4338
Na1—O3^ix	2.4532	O8—Si1	1.6191
Na1—O7^x	2.4338	O8—Si2^vi	1.6168
O1^i—Al1—O3^ii	102.836	O6^v—Si2—O8^vi	110.422
O1^i—Al1—O5	116.047	O2—Si3—O4	107.269
O3^ii—Al1—O5	112.215	O2—Si3—O5^vii	105.914
O1^i—Al1—O7	104.004	O4—Si3—O5^vii	110.224
O3^ii—Al1—O7	111.151	O2—Si3—O7^vi	108.565
O5—Al1—O7	110.14	O4—Si3—O7^vi	110.208
O1^iii—Si1—O4^ii	109.433	O5^vii—Si3—O7^vi	114.328
O1^iii—Si1—O6	112.47	Al1^xi—O1—Si1^iii	141.397
O4^ii—Si1—O6	108.187	Si2^x—O2—Si3	130.019
O1^iii—Si1—O8	107.176	Si2^x—O2—Na1	120.351
O4^ii—Si1—O8	111.446	Si3—O2—Na1	108.811
O6—Si1—O8	108.16	Al1^xiii—O3—Si2	139.461
O2^iv—Si2—O3	111.144	Si1^xiii—O4—Si3	161.151
O2^iv—Si2—O6^v	104.24	Al1—O5—Si3^xiv	129.689
O3—Si2—O6^v	112.114	Si1—O6—Si2^xv	135.676
O2^iv—Si2—O8^vi	106.97	Al1—O7—Si3^vi	133.943
O3—Si2—O8^vi	111.591	Si1—O8—Si2^vi	151.747

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

(QPABAT1ug3_phase_0)

Crystal data

FeS2	V = 159.17 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.006 Mg m^−3
a = 5.41945 (8) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.373(14), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.010*
S2	0.3903 (4)	0.3903	0.3903	0.010*

Bond lengths (Å)

Fe1—S2^i	2.2761 (6)	Fe1—S2^vi	2.276 (2)
Fe1—S2^ii	2.2761 (6)	S2—Fe1^vii	2.2761 (6)
Fe1—S2^iii	2.2761 (6)	S2—Fe1^viii	2.2761 (6)
Fe1—S2^iv	2.2761 (6)	S2—Fe1^ix	2.276 (2)
Fe1—S2^v	2.2761 (6)	S2—S2^x	2.060 (3)

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

(QPABAT1ug3_phase_3)

Crystal data

Fe7S8	β = 117.18 (5)°
Mr = 647.41	V = 933.3 (5) Å^3
Monoclinic, C2/c	Z = 4
a = 11.92 (2) Å	Dx = 4.607 Mg m^−3
b = 6.870 (4) Å	T = 300 K
c = 12.81 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.15(6), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4960	Fe5—S2^v	2.4431
S1—Fe5	2.4118	Fe5—S4	2.3849
S1—Fe7^ii	2.3906	Fe5—S6	2.3614
S1—Fe7^iii	2.4384	S6—Fe3^viii	2.4516
S1—Fe8	2.4072	S6—Fe5	2.3614
S2—Fe3	2.3724	S6—Fe7	2.4298
S2—Fe3^iv	2.3251	S6—Fe7^iii	2.3913
S2—Fe5^v	2.4431	Fe7—S1^ix	2.3906
S2—Fe7^vi	2.3676	Fe7—S1^iii	2.4384
S2—Fe8^iv	2.4120	Fe7—S2^x	2.3676
Fe3—S1^i	2.4960	Fe7—S6	2.4298
Fe3—S2	2.3724	Fe7—S6^iii	2.3913
Fe3—S2^iv	2.3251	Fe8—S1	2.4072
Fe3—S6^vii	2.4516	Fe8—S1^i	2.4072
S4—Fe5	2.3849	Fe8—S2^iv	2.4120
Fe5—S1	2.4118	Fe8—S2^viii	2.4120

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(QPABAT1ug3_phase_1)

Crystal data

O2Si	V = 113.15 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.645 Mg m^−3
a = 4.9161 (6) Å	T = 300 K
c = 5.4061 (5) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.37(6), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.006
O1	0.41460	0.26780	0.78543	0.011

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0073	0.0059	0.0053	0.0029	0.0003	0.0006
O1	0.0120	0.0105	0.0118	0.0065	−0.0029	−0.0040

Geometric parameters (Å, º)

Si1—O1	1.6056	O1—Si1	1.6056
Si1—O1^i	1.6118	O1—Si1^iv	1.6118
Si1—O1^ii	1.6116	O1—Si1^v	1.6116
Si1—O1^iii	1.6057
O1—Si1—O1^i	110.252	O1^ii—Si1—O1^iii	110.258
O1—Si1—O1^ii	108.753	Si1—O1—Si1^iv	143.831
O1^i—Si1—O1^ii	109.678	Si1—O1—Si1^v	143.835
O1—Si1—O1^iii	109.158	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.733

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

(QPABAT1ug3_phase_4)

Crystal data

O2Ti	V = 65.14 (17) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.074 Mg m^−3
a = 4.746 (8) Å	T = 300 K
c = 2.892 (7) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.100, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	2.0466	Ti1—O1^v	1.9506
Ti1—O1^i	1.9506	O1—Ti1	2.0466
Ti1—O1^ii	1.9506	O1—Ti1^vi	1.9506
Ti1—O1^iii	2.0466	O1—Ti1^vii	1.9506
Ti1—O1^iv	1.9506
O1^i—Ti1—O1^ii	95.681	O1^ii—Ti1—O1^v	84.319
O1^i—Ti1—O1^iv	84.319	O1^iv—Ti1—O1^v	95.681
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	95.681
O1^i—Ti1—O1^v	180

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

 

(NEW1minmill_phase_0)

Crystal data

FeS2	V = 159.20 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.005 Mg m^−3
a = 5.41977 (4) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.2413(26), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.010*
S2	0.38589	0.38589	0.38589	0.010*

Bond lengths (Å)

Fe1—S2^i	2.2669	Fe1—S2^vi	2.2669
Fe1—S2^ii	2.2669	S2—Fe1^vii	2.2669
Fe1—S2^iii	2.2669	S2—Fe1^viii	2.2669
Fe1—S2^iv	2.2669	S2—Fe1^ix	2.2669
Fe1—S2^v	2.2669	S2—S2^x	2.1425

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

(NEW1minmill_phase_2)

Crystal data

AlNaO8Si3	β = 116.6°
Mr = 262.22	γ = 87.71°
Triclinic, C1	V = 664.01 Å^3
a = 8.137 Å	Z = 4
b = 12.785 Å	Dx = 2.623 Mg m^−3
c = 7.1583 Å	T = 300 K
α = 94.26°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.177(14), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7452	O1—Al1^xi	1.7452
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7351	O1—Na1^xii	2.6689
Al1—O7	1.7456	O1—Na1^iii	2.5308
Si1—O1^iii	1.5999	O2—Si2^x	1.6301
Si1—O4^ii	1.6000	O2—Si3	1.6472
Si1—O6	1.6223	O2—Na1	2.3704
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6301	O3—Si2	1.5944
Si2—O3	1.5944	O3—Na1^ix	2.4532
Si2—O6^v	1.6184	O4—Si1^xiii	1.6000
Si2—O8^vi	1.6168	O4—Si3	1.6198
Si3—O2	1.6472	O5—Al1	1.7351
Si3—O4	1.6198	O5—Si3^xiv	1.5968
Si3—O5^vii	1.5968	O6—Si1	1.6223
Si3—O7^vi	1.6020	O6—Si2^xv	1.6184
Na1—O1^viii	2.6689	O7—Al1	1.7456
Na1—O1^iii	2.5308	O7—Si3^vi	1.6020
Na1—O2	2.3704	O7—Na1^iv	2.4338
Na1—O3^ix	2.4532	O8—Si1	1.6191
Na1—O7^x	2.4338	O8—Si2^vi	1.6168
O1^i—Al1—O3^ii	102.836	O6^v—Si2—O8^vi	110.422
O1^i—Al1—O5	116.047	O2—Si3—O4	107.269
O3^ii—Al1—O5	112.215	O2—Si3—O5^vii	105.914
O1^i—Al1—O7	104.004	O4—Si3—O5^vii	110.224
O3^ii—Al1—O7	111.151	O2—Si3—O7^vi	108.565
O5—Al1—O7	110.14	O4—Si3—O7^vi	110.208
O1^iii—Si1—O4^ii	109.433	O5^vii—Si3—O7^vi	114.328
O1^iii—Si1—O6	112.47	Al1^xi—O1—Si1^iii	141.397
O4^ii—Si1—O6	108.187	Si2^x—O2—Si3	130.019
O1^iii—Si1—O8	107.176	Si2^x—O2—Na1	120.351
O4^ii—Si1—O8	111.446	Si3—O2—Na1	108.811
O6—Si1—O8	108.16	Al1^xiii—O3—Si2	139.461
O2^iv—Si2—O3	111.144	Si1^xiii—O4—Si3	161.151
O2^iv—Si2—O6^v	104.24	Al1—O5—Si3^xiv	129.689
O3—Si2—O6^v	112.114	Si1—O6—Si2^xv	135.676
O2^iv—Si2—O8^vi	106.97	Al1—O7—Si3^vi	133.943
O3—Si2—O8^vi	111.591	Si1—O8—Si2^vi	151.747

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

(NEW1minmill_phase_4)

Crystal data

Fe7S8	β = 117.12 (3)°
Mr = 647.41	V = 933.9 (3) Å^3
Monoclinic, C2/c	Z = 4
a = 11.904 (12) Å	Dx = 4.605 Mg m^−3
b = 6.878 (2) Å	T = 300 K
c = 12.814 (15) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.071(6), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4981	Fe5—S2^v	2.4412
S1—Fe5	2.4104	Fe5—S4	2.3866
S1—Fe7^ii	2.3924	Fe5—S6	2.3628
S1—Fe7^iii	2.4370	S6—Fe3^viii	2.4529
S1—Fe8	2.4087	S6—Fe5	2.3628
S2—Fe3	2.3713	S6—Fe7	2.4277
S2—Fe3^iv	2.3269	S6—Fe7^iii	2.3926
S2—Fe5^v	2.4412	Fe7—S1^ix	2.3924
S2—Fe7^vi	2.3692	Fe7—S1^iii	2.4370
S2—Fe8^iv	2.4136	Fe7—S2^x	2.3692
Fe3—S1^i	2.4981	Fe7—S6	2.4277
Fe3—S2	2.3713	Fe7—S6^iii	2.3926
Fe3—S2^iv	2.3269	Fe8—S1	2.4087
Fe3—S6^vii	2.4529	Fe8—S1^i	2.4087
S4—Fe5	2.3866	Fe8—S2^iv	2.4136
Fe5—S1	2.4104	Fe8—S2^viii	2.4136

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(NEW1minmill_phase_1)

Crystal data

O2Si	V = 113.15 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.645 Mg m^−3
a = 4.9162 (4) Å	T = 300 K
c = 5.4061 (4) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.220(14), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.006
O1	0.41460	0.26780	0.78543	0.011

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0073	0.0059	0.0053	0.0029	0.0003	0.0006
O1	0.0120	0.0105	0.0118	0.0065	−0.0029	−0.0040

Geometric parameters (Å, º)

Si1—O1	1.6056	O1—Si1	1.6056
Si1—O1^i	1.6119	O1—Si1^iv	1.6119
Si1—O1^ii	1.6116	O1—Si1^v	1.6116
Si1—O1^iii	1.6058
O1—Si1—O1^i	110.252	O1^ii—Si1—O1^iii	110.258
O1—Si1—O1^ii	108.754	Si1—O1—Si1^iv	143.831
O1^i—Si1—O1^ii	109.677	Si1—O1—Si1^v	143.835
O1—Si1—O1^iii	109.158	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.734

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

(NEW1minmill_phase_3)

Crystal data

O2Ti	V = 62.62 (5) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.237 Mg m^−3
a = 4.599 (3) Å	T = 300 K
c = 2.960 (2) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.100, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	1.9835	Ti1—O1^v	1.9495
Ti1—O1^i	1.9495	O1—Ti1	1.9835
Ti1—O1^ii	1.9495	O1—Ti1^vi	1.9495
Ti1—O1^iii	1.9835	O1—Ti1^vii	1.9495
Ti1—O1^iv	1.9495
O1—Ti1—O1^i	90	O1^iii—Ti1—O1^iv	90
O1—Ti1—O1^ii	90	O1—Ti1—O1^v	90
O1^i—Ti1—O1^ii	98.787	O1^i—Ti1—O1^v	180
O1—Ti1—O1^iii	180	O1^ii—Ti1—O1^v	81.213
O1^i—Ti1—O1^iii	90	O1^iii—Ti1—O1^v	90
O1^ii—Ti1—O1^iii	90	O1^iv—Ti1—O1^v	98.787
O1—Ti1—O1^iv	90	Ti1—O1—Ti1^vi	130.606
O1^i—Ti1—O1^iv	81.213	Ti1—O1—Ti1^vii	130.606
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	98.787

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

 

(NEW2minmill_phase_0)

Crystal data

FeS2	V = 159.18 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.006 Mg m^−3
a = 5.41951 (3) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.2643(21), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.0063 (4)*
S2	0.38541 (12)	0.38541	0.38541	0.0053 (4)*

Bond lengths (Å)

Fe1—S2^i	2.2659 (2)	Fe1—S2^vi	2.2659 (6)
Fe1—S2^ii	2.2659 (2)	S2—Fe1^vii	2.2659 (2)
Fe1—S2^iii	2.2659 (2)	S2—Fe1^viii	2.2659 (2)
Fe1—S2^iv	2.2659 (2)	S2—Fe1^ix	2.2659 (6)
Fe1—S2^v	2.2659 (2)	S2—S2^x	2.1513 (8)

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

(NEW2minmill_phase_2)

Crystal data

AlNaO8Si3	β = 116.6°
Mr = 262.22	γ = 87.71°
Triclinic, C1	V = 664.01 Å^3
a = 8.137 Å	Z = 4
b = 12.785 Å	Dx = 2.623 Mg m^−3
c = 7.1583 Å	T = 300 K
α = 94.26°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.171(12), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7452	O1—Al1^xi	1.7452
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7351	O1—Na1^xii	2.6689
Al1—O7	1.7456	O1—Na1^iii	2.5308
Si1—O1^iii	1.5999	O2—Si2^x	1.6301
Si1—O4^ii	1.6000	O2—Si3	1.6472
Si1—O6	1.6223	O2—Na1	2.3704
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6301	O3—Si2	1.5944
Si2—O3	1.5944	O3—Na1^ix	2.4532
Si2—O6^v	1.6184	O4—Si1^xiii	1.6000
Si2—O8^vi	1.6168	O4—Si3	1.6198
Si3—O2	1.6472	O5—Al1	1.7351
Si3—O4	1.6198	O5—Si3^xiv	1.5968
Si3—O5^vii	1.5968	O6—Si1	1.6223
Si3—O7^vi	1.6020	O6—Si2^xv	1.6184
Na1—O1^viii	2.6689	O7—Al1	1.7456
Na1—O1^iii	2.5308	O7—Si3^vi	1.6020
Na1—O2	2.3704	O7—Na1^iv	2.4338
Na1—O3^ix	2.4532	O8—Si1	1.6191
Na1—O7^x	2.4338	O8—Si2^vi	1.6168
O1^i—Al1—O3^ii	102.836	O6^v—Si2—O8^vi	110.422
O1^i—Al1—O5	116.047	O2—Si3—O4	107.269
O3^ii—Al1—O5	112.215	O2—Si3—O5^vii	105.914
O1^i—Al1—O7	104.004	O4—Si3—O5^vii	110.224
O3^ii—Al1—O7	111.151	O2—Si3—O7^vi	108.565
O5—Al1—O7	110.14	O4—Si3—O7^vi	110.208
O1^iii—Si1—O4^ii	109.433	O5^vii—Si3—O7^vi	114.328
O1^iii—Si1—O6	112.47	Al1^xi—O1—Si1^iii	141.397
O4^ii—Si1—O6	108.187	Si2^x—O2—Si3	130.019
O1^iii—Si1—O8	107.176	Si2^x—O2—Na1	120.351
O4^ii—Si1—O8	111.446	Si3—O2—Na1	108.811
O6—Si1—O8	108.16	Al1^xiii—O3—Si2	139.461
O2^iv—Si2—O3	111.144	Si1^xiii—O4—Si3	161.151
O2^iv—Si2—O6^v	104.24	Al1—O5—Si3^xiv	129.689
O3—Si2—O6^v	112.114	Si1—O6—Si2^xv	135.676
O2^iv—Si2—O8^vi	106.97	Al1—O7—Si3^vi	133.943
O3—Si2—O8^vi	111.591	Si1—O8—Si2^vi	151.747

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

(NEW2minmill_phase_4)

Crystal data

Fe7S8	β = 117.20 (4)°
Mr = 647.41	V = 934.1 (3) Å^3
Monoclinic, C2/c	Z = 4
a = 11.927 (18) Å	Dx = 4.603 Mg m^−3
b = 6.869 (3) Å	T = 300 K
c = 12.82 (2) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.049(4), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4961	Fe5—S2^v	2.4434
S1—Fe5	2.4121	Fe5—S4	2.3859
S1—Fe7^ii	2.3906	Fe5—S6	2.3624
S1—Fe7^iii	2.4403	S6—Fe3^viii	2.4517
S1—Fe8	2.4082	S6—Fe5	2.3624
S2—Fe3	2.3743	S6—Fe7	2.4317
S2—Fe3^iv	2.3254	S6—Fe7^iii	2.3915
S2—Fe5^v	2.4434	Fe7—S1^ix	2.3906
S2—Fe7^vi	2.3678	Fe7—S1^iii	2.4403
S2—Fe8^iv	2.4128	Fe7—S2^x	2.3678
Fe3—S1^i	2.4961	Fe7—S6	2.4317
Fe3—S2	2.3743	Fe7—S6^iii	2.3915
Fe3—S2^iv	2.3254	Fe8—S1	2.4082
Fe3—S6^vii	2.4517	Fe8—S1^i	2.4082
S4—Fe5	2.3859	Fe8—S2^iv	2.4128
Fe5—S1	2.4121	Fe8—S2^viii	2.4128

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(NEW2minmill_phase_1)

Crystal data

O2Si	V = 113.08 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.647 Mg m^−3
a = 4.9149 (4) Å	T = 300 K
c = 5.4057 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.220(12), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.006
O1	0.41460	0.26780	0.78543	0.011

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0073	0.0059	0.0053	0.0029	0.0003	0.0006
O1	0.0120	0.0105	0.0118	0.0065	−0.0029	−0.0040

Geometric parameters (Å, º)

Si1—O1	1.6053	O1—Si1	1.6053
Si1—O1^i	1.6116	O1—Si1^iv	1.6116
Si1—O1^ii	1.6113	O1—Si1^v	1.6113
Si1—O1^iii	1.6054
O1—Si1—O1^i	110.256	O1^ii—Si1—O1^iii	110.262
O1—Si1—O1^ii	108.745	Si1—O1—Si1^iv	143.832
O1^i—Si1—O1^ii	109.685	Si1—O1—Si1^v	143.836
O1—Si1—O1^iii	109.161	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.725

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

(NEW2minmill_phase_3)

Crystal data

O2Ti	V = 62.59 (3) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.239 Mg m^−3
a = 4.5979 (16) Å	T = 300 K
c = 2.9608 (14) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.13(4), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	1.9828	Ti1—O1^v	1.9495
Ti1—O1^i	1.9495	O1—Ti1	1.9828
Ti1—O1^ii	1.9495	O1—Ti1^vi	1.9495
Ti1—O1^iii	1.9828	O1—Ti1^vii	1.9495
Ti1—O1^iv	1.9495
O1—Ti1—O1^i	90	O1^iii—Ti1—O1^iv	90
O1—Ti1—O1^ii	90	O1—Ti1—O1^v	90
O1^i—Ti1—O1^ii	98.82	O1^i—Ti1—O1^v	180
O1—Ti1—O1^iii	180	O1^ii—Ti1—O1^v	81.18
O1^i—Ti1—O1^iii	90	O1^iii—Ti1—O1^v	90
O1^ii—Ti1—O1^iii	90	O1^iv—Ti1—O1^v	98.82
O1—Ti1—O1^iv	90	Ti1—O1—Ti1^vi	130.59
O1^i—Ti1—O1^iv	81.18	Ti1—O1—Ti1^vii	130.59
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	98.82

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

 

(NEW3minmill_phase_0)

Crystal data

FeS2	V = 159.17 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.006 Mg m^−3
a = 5.41948 (3) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.2508(19), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.010*
S2	0.38680	0.38680	0.38680	0.010*

Bond lengths (Å)

Fe1—S2^i	2.2687	Fe1—S2^vi	2.2687
Fe1—S2^ii	2.2687	S2—Fe1^vii	2.2687
Fe1—S2^iii	2.2687	S2—Fe1^viii	2.2687
Fe1—S2^iv	2.2687	S2—Fe1^ix	2.2687
Fe1—S2^v	2.2687	S2—S2^x	2.1252

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

(NEW3minmill_phase_2)

Crystal data

AlNaO8Si3	β = 116.6°
Mr = 262.22	γ = 87.71°
Triclinic, C1	V = 664.01 Å^3
a = 8.137 Å	Z = 4
b = 12.785 Å	Dx = 2.623 Mg m^−3
c = 7.1583 Å	T = 300 K
α = 94.26°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.143(10), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7452	O1—Al1^xi	1.7452
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7351	O1—Na1^xii	2.6689
Al1—O7	1.7456	O1—Na1^iii	2.5308
Si1—O1^iii	1.5999	O2—Si2^x	1.6301
Si1—O4^ii	1.6000	O2—Si3	1.6472
Si1—O6	1.6223	O2—Na1	2.3704
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6301	O3—Si2	1.5944
Si2—O3	1.5944	O3—Na1^ix	2.4532
Si2—O6^v	1.6184	O4—Si1^xiii	1.6000
Si2—O8^vi	1.6168	O4—Si3	1.6198
Si3—O2	1.6472	O5—Al1	1.7351
Si3—O4	1.6198	O5—Si3^xiv	1.5968
Si3—O5^vii	1.5968	O6—Si1	1.6223
Si3—O7^vi	1.6020	O6—Si2^xv	1.6184
Na1—O1^viii	2.6689	O7—Al1	1.7456
Na1—O1^iii	2.5308	O7—Si3^vi	1.6020
Na1—O2	2.3704	O7—Na1^iv	2.4338
Na1—O3^ix	2.4532	O8—Si1	1.6191
Na1—O7^x	2.4338	O8—Si2^vi	1.6168
O1^i—Al1—O3^ii	102.836	O6^v—Si2—O8^vi	110.422
O1^i—Al1—O5	116.047	O2—Si3—O4	107.269
O3^ii—Al1—O5	112.215	O2—Si3—O5^vii	105.914
O1^i—Al1—O7	104.004	O4—Si3—O5^vii	110.224
O3^ii—Al1—O7	111.151	O2—Si3—O7^vi	108.565
O5—Al1—O7	110.14	O4—Si3—O7^vi	110.208
O1^iii—Si1—O4^ii	109.433	O5^vii—Si3—O7^vi	114.328
O1^iii—Si1—O6	112.47	Al1^xi—O1—Si1^iii	141.397
O4^ii—Si1—O6	108.187	Si2^x—O2—Si3	130.019
O1^iii—Si1—O8	107.176	Si2^x—O2—Na1	120.351
O4^ii—Si1—O8	111.446	Si3—O2—Na1	108.811
O6—Si1—O8	108.16	Al1^xiii—O3—Si2	139.461
O2^iv—Si2—O3	111.144	Si1^xiii—O4—Si3	161.151
O2^iv—Si2—O6^v	104.24	Al1—O5—Si3^xiv	129.689
O3—Si2—O6^v	112.114	Si1—O6—Si2^xv	135.676
O2^iv—Si2—O8^vi	106.97	Al1—O7—Si3^vi	133.943
O3—Si2—O8^vi	111.591	Si1—O8—Si2^vi	151.747

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

(NEW3minmill_phase_4)

Crystal data

Fe7S8	β = 117.23 (4)°
Mr = 647.41	V = 934.8 (4) Å^3
Monoclinic, C2/c	Z = 4
a = 11.93 (2) Å	Dx = 4.600 Mg m^−3
b = 6.868 (3) Å	T = 300 K
c = 12.83 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.040(3), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4960	Fe5—S2^v	2.4441
S1—Fe5	2.4127	Fe5—S4	2.3865
S1—Fe7^ii	2.3906	Fe5—S6	2.3630
S1—Fe7^iii	2.4419	S6—Fe3^viii	2.4518
S1—Fe8	2.4088	S6—Fe5	2.3630
S2—Fe3	2.3758	S6—Fe7	2.4333
S2—Fe3^iv	2.3255	S6—Fe7^iii	2.3916
S2—Fe5^v	2.4441	Fe7—S1^ix	2.3906
S2—Fe7^vi	2.3678	Fe7—S1^iii	2.4419
S2—Fe8^iv	2.4132	Fe7—S2^x	2.3678
Fe3—S1^i	2.4960	Fe7—S6	2.4333
Fe3—S2	2.3758	Fe7—S6^iii	2.3916
Fe3—S2^iv	2.3255	Fe8—S1	2.4088
Fe3—S6^vii	2.4518	Fe8—S1^i	2.4088
S4—Fe5	2.3865	Fe8—S2^iv	2.4132
Fe5—S1	2.4127	Fe8—S2^viii	2.4132

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(NEW3minmill_phase_1)

Crystal data

O2Si	V = 113.09 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.647 Mg m^−3
a = 4.9151 (4) Å	T = 300 K
c = 5.4055 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.205(11), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.006
O1	0.41460	0.26780	0.78543	0.011

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0073	0.0059	0.0053	0.0029	0.0003	0.0006
O1	0.0120	0.0105	0.0118	0.0065	−0.0029	−0.0040

Geometric parameters (Å, º)

Si1—O1	1.6053	O1—Si1	1.6053
Si1—O1^i	1.6116	O1—Si1^iv	1.6116
Si1—O1^ii	1.6114	O1—Si1^v	1.6114
Si1—O1^iii	1.6055
O1—Si1—O1^i	110.254	O1^ii—Si1—O1^iii	110.26
O1—Si1—O1^ii	108.749	Si1—O1—Si1^iv	143.831
O1^i—Si1—O1^ii	109.682	Si1—O1—Si1^v	143.835
O1—Si1—O1^iii	109.16	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.729

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

(NEW3minmill_phase_3)

Crystal data

O2Ti	V = 62.58 (2) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.241 Mg m^−3
a = 4.5969 (7) Å	T = 300 K
c = 2.9612 (7) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.200, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	1.9824	Ti1—O1^v	1.9495
Ti1—O1^i	1.9495	O1—Ti1	1.9824
Ti1—O1^ii	1.9495	O1—Ti1^vi	1.9495
Ti1—O1^iii	1.9824	O1—Ti1^vii	1.9495
Ti1—O1^iv	1.9495
O1—Ti1—O1^i	90	O1^iii—Ti1—O1^iv	90
O1—Ti1—O1^ii	90	O1—Ti1—O1^v	90
O1^i—Ti1—O1^ii	98.838	O1^i—Ti1—O1^v	180
O1—Ti1—O1^iii	180	O1^ii—Ti1—O1^v	81.162
O1^i—Ti1—O1^iii	90	O1^iii—Ti1—O1^v	90
O1^ii—Ti1—O1^iii	90	O1^iv—Ti1—O1^v	98.838
O1—Ti1—O1^iv	90	Ti1—O1—Ti1^vi	130.581
O1^i—Ti1—O1^iv	81.162	Ti1—O1—Ti1^vii	130.581
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	98.838

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

 

(NEW5minmill_phase_0)

Crystal data

FeS2	V = 159.20 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.005 Mg m^−3
a = 5.41973 (3) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.2144(14), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.0079 (3)*
S2	0.38533 (11)	0.38533	0.38533	0.0097 (3)*

Bond lengths (Å)

Fe1—S2^i	2.2658 (2)	Fe1—S2^vi	2.2658 (5)
Fe1—S2^ii	2.2658 (2)	S2—Fe1^vii	2.2658 (2)
Fe1—S2^iii	2.2658 (2)	S2—Fe1^viii	2.2658 (2)
Fe1—S2^iv	2.2658 (2)	S2—Fe1^ix	2.2658 (5)
Fe1—S2^v	2.2658 (2)	S2—S2^x	2.1528 (7)

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

(NEW5minmill_phase_2)

Crystal data

AlNaO8Si3	β = 116.6°
Mr = 262.22	γ = 87.71°
Triclinic, C1	V = 664.01 Å^3
a = 8.137 Å	Z = 4
b = 12.785 Å	Dx = 2.623 Mg m^−3
c = 7.1583 Å	T = 300 K
α = 94.26°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.129(9), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7452	O1—Al1^xi	1.7452
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7351	O1—Na1^xii	2.6689
Al1—O7	1.7456	O1—Na1^iii	2.5308
Si1—O1^iii	1.5999	O2—Si2^x	1.6301
Si1—O4^ii	1.6000	O2—Si3	1.6472
Si1—O6	1.6223	O2—Na1	2.3704
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6301	O3—Si2	1.5944
Si2—O3	1.5944	O3—Na1^ix	2.4532
Si2—O6^v	1.6184	O4—Si1^xiii	1.6000
Si2—O8^vi	1.6168	O4—Si3	1.6198
Si3—O2	1.6472	O5—Al1	1.7351
Si3—O4	1.6198	O5—Si3^xiv	1.5968
Si3—O5^vii	1.5968	O6—Si1	1.6223
Si3—O7^vi	1.6020	O6—Si2^xv	1.6184
Na1—O1^viii	2.6689	O7—Al1	1.7456
Na1—O1^iii	2.5308	O7—Si3^vi	1.6020
Na1—O2	2.3704	O7—Na1^iv	2.4338
Na1—O3^ix	2.4532	O8—Si1	1.6191
Na1—O7^x	2.4338	O8—Si2^vi	1.6168
O1^i—Al1—O3^ii	102.836	O6^v—Si2—O8^vi	110.422
O1^i—Al1—O5	116.047	O2—Si3—O4	107.269
O3^ii—Al1—O5	112.215	O2—Si3—O5^vii	105.914
O1^i—Al1—O7	104.004	O4—Si3—O5^vii	110.224
O3^ii—Al1—O7	111.151	O2—Si3—O7^vi	108.565
O5—Al1—O7	110.14	O4—Si3—O7^vi	110.208
O1^iii—Si1—O4^ii	109.433	O5^vii—Si3—O7^vi	114.328
O1^iii—Si1—O6	112.47	Al1^xi—O1—Si1^iii	141.397
O4^ii—Si1—O6	108.187	Si2^x—O2—Si3	130.019
O1^iii—Si1—O8	107.176	Si2^x—O2—Na1	120.351
O4^ii—Si1—O8	111.446	Si3—O2—Na1	108.811
O6—Si1—O8	108.16	Al1^xiii—O3—Si2	139.461
O2^iv—Si2—O3	111.144	Si1^xiii—O4—Si3	161.151
O2^iv—Si2—O6^v	104.24	Al1—O5—Si3^xiv	129.689
O3—Si2—O6^v	112.114	Si1—O6—Si2^xv	135.676
O2^iv—Si2—O8^vi	106.97	Al1—O7—Si3^vi	133.943
O3—Si2—O8^vi	111.591	Si1—O8—Si2^vi	151.747

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

(NEW5minmill_phase_4)

Crystal data

Fe7S8	β = 117.28 (6)°
Mr = 647.41	V = 934.2 (4) Å^3
Monoclinic, C2/c	Z = 4
a = 11.94 (3) Å	Dx = 4.603 Mg m^−3
b = 6.860 (4) Å	T = 300 K
c = 12.83 (3) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.0309(25), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4941	Fe5—S2^v	2.4444
S1—Fe5	2.4128	Fe5—S4	2.3857
S1—Fe7^ii	2.3888	Fe5—S6	2.3623
S1—Fe7^iii	2.4435	S6—Fe3^viii	2.4504
S1—Fe8	2.4080	S6—Fe5	2.3623
S2—Fe3	2.3773	S6—Fe7	2.4351
S2—Fe3^iv	2.3241	S6—Fe7^iii	2.3902
S2—Fe5^v	2.4444	Fe7—S1^ix	2.3888
S2—Fe7^vi	2.3663	Fe7—S1^iii	2.4435
S2—Fe8^iv	2.4122	Fe7—S2^x	2.3663
Fe3—S1^i	2.4941	Fe7—S6	2.4351
Fe3—S2	2.3773	Fe7—S6^iii	2.3902
Fe3—S2^iv	2.3241	Fe8—S1	2.4080
Fe3—S6^vii	2.4504	Fe8—S1^i	2.4080
S4—Fe5	2.3857	Fe8—S2^iv	2.4122
Fe5—S1	2.4128	Fe8—S2^viii	2.4122

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(NEW5minmill_phase_1)

Crystal data

O2Si	V = 113.12 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.646 Mg m^−3
a = 4.9154 (4) Å	T = 300 K
c = 5.4060 (4) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.183(9), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.006
O1	0.41460	0.26780	0.78543	0.011

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0073	0.0059	0.0053	0.0029	0.0003	0.0006
O1	0.0120	0.0105	0.0118	0.0065	−0.0029	−0.0040

Geometric parameters (Å, º)

Si1—O1	1.6054	O1—Si1	1.6054
Si1—O1^i	1.6117	O1—Si1^iv	1.6117
Si1—O1^ii	1.6115	O1—Si1^v	1.6115
Si1—O1^iii	1.6056
O1—Si1—O1^i	110.255	O1^ii—Si1—O1^iii	110.26
O1—Si1—O1^ii	108.748	Si1—O1—Si1^iv	143.832
O1^i—Si1—O1^ii	109.683	Si1—O1—Si1^v	143.835
O1—Si1—O1^iii	109.16	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.728

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

(NEW5minmill_phase_3)

Crystal data

O2Ti	V = 62.64 (3) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.236 Mg m^−3
a = 4.5996 (11) Å	T = 300 K
c = 2.9608 (10) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.150, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	1.9835	Ti1—O1^v	1.9498
Ti1—O1^i	1.9498	O1—Ti1	1.9835
Ti1—O1^ii	1.9498	O1—Ti1^vi	1.9498
Ti1—O1^iii	1.9835	O1—Ti1^vii	1.9498
Ti1—O1^iv	1.9498
O1—Ti1—O1^i	90	O1^iii—Ti1—O1^iv	90
O1—Ti1—O1^ii	90	O1—Ti1—O1^v	90
O1^i—Ti1—O1^ii	98.799	O1^i—Ti1—O1^v	180
O1—Ti1—O1^iii	180	O1^ii—Ti1—O1^v	81.201
O1^i—Ti1—O1^iii	90	O1^iii—Ti1—O1^v	90
O1^ii—Ti1—O1^iii	90	O1^iv—Ti1—O1^v	98.799
O1—Ti1—O1^iv	90	Ti1—O1—Ti1^vi	130.601
O1^i—Ti1—O1^iv	81.201	Ti1—O1—Ti1^vii	130.601
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	98.799

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

 

(NEW10minmill_phase_0)

Crystal data

FeS2	V = 159.21 (1) Å^3
Mr = 119.97	Z = 4
Cubic, Pa3	Dx = 5.005 Mg m^−3
a = 5.41988 (3) Å	T = 300 K

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.1814(11), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Fe1	0.00000	0.00000	0.00000	0.0087 (3)*
S2	0.38482 (10)	0.38482	0.38482	0.0087 (3)*

Bond lengths (Å)

Fe1—S2^i	2.2648 (1)	Fe1—S2^vi	2.2648 (5)
Fe1—S2^ii	2.2648 (1)	S2—Fe1^vii	2.2648 (1)
Fe1—S2^iii	2.2648 (1)	S2—Fe1^viii	2.2648 (1)
Fe1—S2^iv	2.2648 (1)	S2—Fe1^ix	2.2648 (5)
Fe1—S2^v	2.2648 (1)	S2—S2^x	2.1625 (6)

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

(NEW10minmill_phase_2)

Crystal data

AlNaO8Si3	β = 116.6°
Mr = 262.22	γ = 87.71°
Triclinic, C1	V = 664.01 Å^3
a = 8.137 Å	Z = 4
b = 12.785 Å	Dx = 2.623 Mg m^−3
c = 7.1583 Å	T = 300 K
α = 94.26°

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.099(8), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Al1	0.00887	0.16846	0.20805	0.007
Si1	0.00375	0.82051	0.23737	0.006
Si2	0.69162	0.11021	0.31466	0.006
Si3	0.68129	0.88190	0.36076	0.006
Na1	0.26799	0.98865	0.14650	0.031
O1	0.00490	0.13103	0.96660	0.012
O2	0.59176	0.99756	0.28040	0.008
O3	0.81230	0.10966	0.19010	0.014
O4	0.82000	0.85101	0.25870	0.018
O5	0.01288	0.30238	0.27060	0.011
O6	0.02329	0.69368	0.22910	0.011
O7	0.20780	0.10896	0.38900	0.011
O8	0.18400	0.86817	0.43620	0.012

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0074	0.0068	0.0061	−0.0009	0.0031	0.0004
Si1	0.0068	0.0065	0.0055	0.0011	0.0030	0.0008
Si2	0.0061	0.0055	0.0073	−0.0002	0.0025	0.0004
Si3	0.0060	0.0055	0.0074	0.0006	0.0028	0.0009
Na1	0.0136	0.0471	0.0315	−0.0050	0.0084	−0.0219
O1	0.0164	0.0122	0.0074	−0.0002	0.0067	0.0014
O2	0.0074	0.0056	0.0119	0.0003	0.0033	0.0020
O3	0.0117	0.0130	0.0162	−0.0040	0.0093	−0.0017
O4	0.0134	0.0179	0.0216	0.0046	0.0129	0.0020
O5	0.0103	0.0076	0.0150	−0.0020	0.0052	−0.0009
O6	0.0101	0.0071	0.0145	0.0022	0.0034	0.0012
O7	0.0120	0.0129	0.0080	0.0024	0.0013	0.0015
O8	0.0140	0.0140	0.0084	−0.0026	−0.0002	−0.0006

Geometric parameters (Å, º)

Al1—O1^i	1.7452	O1—Al1^xi	1.7452
Al1—O3^ii	1.7429	O1—Si1^iii	1.5999
Al1—O5	1.7351	O1—Na1^xii	2.6689
Al1—O7	1.7456	O1—Na1^iii	2.5308
Si1—O1^iii	1.5999	O2—Si2^x	1.6301
Si1—O4^ii	1.6000	O2—Si3	1.6472
Si1—O6	1.6223	O2—Na1	2.3704
Si1—O8	1.6191	O3—Al1^xiii	1.7429
Si2—O2^iv	1.6301	O3—Si2	1.5944
Si2—O3	1.5944	O3—Na1^ix	2.4532
Si2—O6^v	1.6184	O4—Si1^xiii	1.6000
Si2—O8^vi	1.6168	O4—Si3	1.6198
Si3—O2	1.6472	O5—Al1	1.7351
Si3—O4	1.6198	O5—Si3^xiv	1.5968
Si3—O5^vii	1.5968	O6—Si1	1.6223
Si3—O7^vi	1.6020	O6—Si2^xv	1.6184
Na1—O1^viii	2.6689	O7—Al1	1.7456
Na1—O1^iii	2.5308	O7—Si3^vi	1.6020
Na1—O2	2.3704	O7—Na1^iv	2.4338
Na1—O3^ix	2.4532	O8—Si1	1.6191
Na1—O7^x	2.4338	O8—Si2^vi	1.6168
O1^i—Al1—O3^ii	102.836	O6^v—Si2—O8^vi	110.422
O1^i—Al1—O5	116.047	O2—Si3—O4	107.269
O3^ii—Al1—O5	112.215	O2—Si3—O5^vii	105.914
O1^i—Al1—O7	104.004	O4—Si3—O5^vii	110.224
O3^ii—Al1—O7	111.151	O2—Si3—O7^vi	108.565
O5—Al1—O7	110.14	O4—Si3—O7^vi	110.208
O1^iii—Si1—O4^ii	109.433	O5^vii—Si3—O7^vi	114.328
O1^iii—Si1—O6	112.47	Al1^xi—O1—Si1^iii	141.397
O4^ii—Si1—O6	108.187	Si2^x—O2—Si3	130.019
O1^iii—Si1—O8	107.176	Si2^x—O2—Na1	120.351
O4^ii—Si1—O8	111.446	Si3—O2—Na1	108.811
O6—Si1—O8	108.16	Al1^xiii—O3—Si2	139.461
O2^iv—Si2—O3	111.144	Si1^xiii—O4—Si3	161.151
O2^iv—Si2—O6^v	104.24	Al1—O5—Si3^xiv	129.689
O3—Si2—O6^v	112.114	Si1—O6—Si2^xv	135.676
O2^iv—Si2—O8^vi	106.97	Al1—O7—Si3^vi	133.943
O3—Si2—O8^vi	111.591	Si1—O8—Si2^vi	151.747

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

(NEW10minmill_phase_4)

Crystal data

Fe7S8	β = 117.23 (8)°
Mr = 647.41	V = 934.4 (6) Å^3
Monoclinic, C2/c	Z = 4
a = 11.95 (4) Å	Dx = 4.602 Mg m^−3
b = 6.850 (5) Å	T = 300 K
c = 12.84 (5) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.0294(29), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
S1	0.01800	0.38330	0.11960	0.010*
S2	0.02910	0.11420	0.63900	0.010*
Fe3	0.10860	0.10250	0.49980	0.010*
S4	0.23410	0.13550	0.38260	0.010*
Fe5	0.24180	0.36600	0.24680	0.010*
S6	0.26790	0.13400	0.12360	0.010*
Fe7	0.38720	0.15000	0.01260	0.010*
Fe8	0.00000	0.14720	0.25000	0.010*

Bond lengths (Å)

S1—Fe3^i	2.4932	Fe5—S2^v	2.4471
S1—Fe5	2.4156	Fe5—S4	2.3851
S1—Fe7^ii	2.3880	Fe5—S6	2.3615
S1—Fe7^iii	2.4444	S6—Fe3^viii	2.4506
S1—Fe8	2.4072	S6—Fe5	2.3615
S2—Fe3	2.3783	S6—Fe7	2.4359
S2—Fe3^iv	2.3245	S6—Fe7^iii	2.3908
S2—Fe5^v	2.4471	Fe7—S1^ix	2.3880
S2—Fe7^vi	2.3663	Fe7—S1^iii	2.4444
S2—Fe8^iv	2.4108	Fe7—S2^x	2.3663
Fe3—S1^i	2.4932	Fe7—S6	2.4359
Fe3—S2	2.3783	Fe7—S6^iii	2.3908
Fe3—S2^iv	2.3245	Fe8—S1	2.4072
Fe3—S6^vii	2.4506	Fe8—S1^i	2.4072
S4—Fe5	2.3851	Fe8—S2^iv	2.4108
Fe5—S1	2.4156	Fe8—S2^viii	2.4108

Symmetry codes: (i) −x, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z+3/2; (vii) x, −y, z+3/2; (viii) x, −y, z+1/2; (ix) x+1/2, y−1/2, z; (x) x+1/2, −y+1/2, z+1/2.

(NEW10minmill_phase_1)

Crystal data

O2Si	V = 113.16 (1) Å^3
Mr = 60.08	Z = 3
Trigonal, P3221	Dx = 2.645 Mg m^−3
a = 4.9161 (5) Å	T = 300 K
c = 5.4064 (5) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.151(8), 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Si1	0.47000	0.00000	0.66670	0.006
O1	0.41460	0.26780	0.78543	0.011

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0073	0.0059	0.0053	0.0029	0.0003	0.0006
O1	0.0120	0.0105	0.0118	0.0065	−0.0029	−0.0040

Geometric parameters (Å, º)

Si1—O1	1.6056	O1—Si1	1.6056
Si1—O1^i	1.6119	O1—Si1^iv	1.6119
Si1—O1^ii	1.6117	O1—Si1^v	1.6117
Si1—O1^iii	1.6058
O1—Si1—O1^i	110.253	O1^ii—Si1—O1^iii	110.259
O1—Si1—O1^ii	108.751	Si1—O1—Si1^iv	143.831
O1^i—Si1—O1^ii	109.68	Si1—O1—Si1^v	143.835
O1—Si1—O1^iii	109.159	Si1^iv—O1—Si1^v	0.009
O1^i—Si1—O1^iii	108.731

Symmetry codes: (i) −y+1, x−y, z−1/3; (ii) −x+1, y−x, −z+5/3; (iii) x−y, −y, −z+4/3; (iv) y−x+1, −x+1, z+1/3; (v) −x+1, y−x+1, −z+5/3.

(NEW10minmill_phase_3)

Crystal data

O2Ti	V = 62.62 (2) Å^3
Mr = 79.9	Z = 2
Tetragonal, P42/mnm	Dx = 4.238 Mg m^−3
a = 4.5991 (7) Å	T = 300 K
c = 2.9603 (7) Å

Refinement

Profile function: Crystallite size in microns with "isotropic" model: parameters: Size, G/L mix 0.200, 1.000, Microstrain, "isotropic" model (10^6 * delta Q/Q) parameters: Mustrain, G/L mix 0.000, 1.000,

Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1]

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

	x	y	z	Uiso*/Ueq
Ti1	0.00000	0.00000	0.00000	0.006
O1	0.30493	0.30493	0.00000	0.006

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0070	0.0070	0.0047	−0.0002	0.0000	0.0000
O1	0.0060	0.0060	0.0045	−0.0019	0.0000	0.0000

Geometric parameters (Å, º)

Ti1—O1	1.9833	Ti1—O1^v	1.9495
Ti1—O1^i	1.9495	O1—Ti1	1.9833
Ti1—O1^ii	1.9495	O1—Ti1^vi	1.9495
Ti1—O1^iii	1.9833	O1—Ti1^vii	1.9495
Ti1—O1^iv	1.9495
O1—Ti1—O1^i	90	O1^iii—Ti1—O1^iv	90
O1—Ti1—O1^ii	90	O1—Ti1—O1^v	90
O1^i—Ti1—O1^ii	98.795	O1^i—Ti1—O1^v	180
O1—Ti1—O1^iii	180	O1^ii—Ti1—O1^v	81.205
O1^i—Ti1—O1^iii	90	O1^iii—Ti1—O1^v	90
O1^ii—Ti1—O1^iii	90	O1^iv—Ti1—O1^v	98.795
O1—Ti1—O1^iv	90	Ti1—O1—Ti1^vi	130.602
O1^i—Ti1—O1^iv	81.205	Ti1—O1—Ti1^vii	130.602
O1^ii—Ti1—O1^iv	180	Ti1^vi—O1—Ti1^vii	98.795

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