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CRYSTAL ENGINEERING
MATERIALS
ISSN: 2052-5206

Study on the structural phase transitions in NaSICON-type compounds using Ag3Sc2(PO4)3 as a model system

aDepartment of Chemistry and Physics of Materials, Materials Science and Mineralogy Group, University of Salzburg, Jakob-Haringerstrasse 2A, Salzburg 5020, Austria, bInstitut für Festkörper- und Materialphysik, Technische Universität Dresden, Haeckelstrasse 3, Dresden 01069, Germany, and cInstitute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, Graz 8010, Austria
*Correspondence e-mail: guenther.redhammer@sbg.ac.at

Edited by C. M. Reddy, IISER Kolkata, India (Received 11 March 2020; accepted 9 November 2020; online 24 December 2020)

NaSICON (Na Super-Ionic CONducting) structured materials are among the most promising solid electrolytes for Li-ion batteries and `beyond Li-ion' batteries (e.g. Na and K) due to their superior ionic conductivities. Although this material has been well known for decades, its exact phase behaviour is still poorly understood. Herein, a starting material of Na3Sc2(PO4)3 single crystals is used, grown by flux methodology, where Na is subsequently chemically replaced by Ag, in order to take advantage of the higher scattering contrast of Ag. It is found that the NaSICON-type com­pound shows two phase transitions from a low-tem­per­ature monoclinic α-phase to a monoclinic β-phase at about 180 K and to a rhombohedral γ-phase at about 290 K. The framework of [Sc2(PO4)3]3− is rigid and does not change significantly with tem­per­ature and change of symmetry. The main driving force for the phase transitions is related to order–disorder phenomena of the conducting cations. The sensitivity of the phase behaviour on the ordering of these ions suggests that small com­positional changes can have a great impact on the phase behaviour and, hence, on the ionic conductivity of NaSICON-structured materials.

1. Introduction

NaSICON (Na Super-Ionic CONducting)-type com­pounds, with the general formula AxMM′(TO4)3 (Masquelier & Croguennec, 2013[Masquelier, C. & Croguennec, L. (2013). Chem. Rev. 113, 6552-6591.]), are promising materials for Li-ion and `beyond Li-ion' batteries. They are built from a framework of corner-sharing tetrahedra (T-sites) and octahedra (M-sites), with well-connected large interstitial voids that can host alkali-metal ions (Goodenough et al., 1976[Goodenough, J. B., Hong, H. Y. P. & Kafalas, J. A. (1976). Mater. Res. Bull. 11, 203-220.]). This three-dimensional (3D) alkali-metal ion sublattice enables a fast-ionic transport when used as a solid electrolyte and enables the insertion/extraction of ions during charge and discharge when used as an electrode material.

Due to the high potential for these materials to be used in battery applications, it is important to understand their structural properties so that a fundamental understanding of the origin of their superior properties can be gained. Generally, the mobility and site preference of alkali ions, as well as their dependence on tem­per­ature, are strongly connected to their phase behaviour. The symmetry of the high-tem­per­ature γ-polymorph (space group R[\overline{3}]c) of NaSICON-type materials, e.g. A3M2(PO4)3-type com­pounds (M = Sc, Cr, Fe and V), undergoes a reduction towards an orthorhombic, monoclinic or triclinic symmetry with decreasing tem­per­ature. For example, a phase transition sequence is observed in Na3V2(PO4)3 from an ordered monoclinic α-form to the classical disordered rhombohedral R[\overline{3}]c structure with two intermediate incommensurately modulated phases β and β′, whose structures are still not resolved (Chotard et al., 2015[Chotard, J.-N., Rousse, G., David, R., Mentré, O., Courty, M. & Masquelier, C. (2015). Chem. Mater. 27, 5982-5987.]). Similar phase-transition sequences from a low-tem­per­ature monoclinic to a disordered rhombohedral structure are observed in Na3Sc2(PO4)3 (NSP). In spite of numerous investigations, the structural phase relationships are still surprisingly an enigma. At tem­per­atures above 500 K, the com­pound shows the γ-structure with R[\overline{3}]c symmetry. Two phase changes at about 340 K (monoclinic α → rhombohedral β) and 440 K (β → superionic rhombohedral γ) have been reported in polycrystalline materials (Boehm et al., 1981[Boehm, L., Delbecq, C. J., Hutchinson, E. & Susman, S. (1981). Solid State Ionics, 5, 311-314.]; Delbecq et al., 1981[Delbecq, C. J., Marshall, S. A. & Susman, S. (1981). Phys. Status Solidi B, 106, 731-734.]; Boilot et al., 1981[Boilot, J. P., Collin, G. & Comès, R. (1981). Solid State Ionics, 5, 307-309.]). However, samples synthesized under different conditions, as well as single-crystalline versus polycrystalline material, seem to behave differently, and three different space groups have been suggested for the room-tem­per­ature (α) modification (Kim et al., 2017[Kim, Y. H., Arunkumar, P., Kim, B. Y., Unithrattil, S., Kim, E., Moon, S.-H., Hyun, J. Y., Kim, K. H., Lee, D., Lee, J.-S. & Im, W. B. (2017). Nat. Mater. 16, 543-550.]; Moon et al., 2016[Moon, S.-H., Kim, Y. H., Cho, D.-C., Shin, E.-C., Lee, D., Im, W. B. & Lee, J.-S. (2016). Solid State Ionics, 289, 55-71.]; Guin et al., 2017[Guin, M., Dashjav, E., Kumar, C. M. N., Tietz, F. & Guillon, O. (2017). Solid State Sci. 67, 30-36.]; Wang et al., 2016[Wang, X. C., Zhao, Z. Y., Wu, Q. S., Wang, C., Wang, Q., Yanyan, L. & Wang, Y. H. (2016). J. Mater. Chem. C, 4, 8795-8801.]), making the situation even more opaque.

The mobility and site preference of alkali-metal ions are key to understanding the phase-transition sequences. Even small site preferences and small occupations of possible sites within the voids of the framework can reduce symmetry. Nevertheless, an accurate study on the interplay of the site preference and the phase behaviour is limited by the low X-ray scattering intensity of Li+ and Na+.

In order to shed light on this interplay, we replaced Na+ by the much heavier Ag+ using an ion-exchange reaction. This ion exchange allows for the investigation of the crystal structure and its tem­per­ature dependence between 100 and 520 K by means of X-ray diffraction.

2. Experimental

2.1. Synthesis

The polycrystalline Na3Sc2(PO4)3 sample material was syn­thesized using a ceramic sintering process and was used to evaluate the extent and speed of Na+–Ag+ ion exchange. The exchange experiments on the single crystals were then designed with these results in mind. Following the procedure proposed by Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]), a stoichiometric mixture of 3 moles NaPO3 and 1 mole Sc2O3 (lab-code HB) was carefully ground and initially heated in a muffle furnace at 673 K for 4 h to decom­pose the starting materials. The obtained material was ground again in an agate mortar, pelletized and reheated in open platinum crucibles in a resistance furnace to 1573 K at a rate of 100 K h−1. The sample was kept at this tem­per­ature for 20 h, after which the furnace was turned off. The sample was left to cool in the furnace until it reached room tem­per­ature.

Large single crystals of NSP were synthesized using the two-step process described by Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]) and Sotofte & Fu (1988[Sotofte, I. & Fu, D. C. (1988). Solid State Ionics, 26, 307-310.]). In the first step, phase-pure ScPO4 was synthesized from 0.5 moles Sc2O3 and 1 mole (NH4)H2(PO4) by preheating the mixture at 673 K for 4 h, regrinding, pelletizing and then annealing at 1473 K for 20 h. Single crystals were grown using the flux method: 1 mole ScPO4 was mixed with 6 moles Na4P2O7 as the high-tem­per­ature flux. The mixture was placed in a platinum crucible, covered with a lid, heated to 1373 K at a rate of 100 K h−1 and held at this tem­per­ature for 5 h to allow the melt to homogenize. The sample was then cooled slowly to 1173 K at a rate of 3 K h−1, before final cooling to room temperature at a rate of 450 K h−1 (furnace cooled). The solidified melt was washed several times in hot water to dissolve the flux and to obtain single crystals, which had good cuboid shapes of up to 0.5 mm in size.

The Ag3Sc2(PO4)3 (ASP) sample material (poly- and single crystalline) was obtained via ion exchange from Na3Sc2(PO4)3. For this, 250 mg of the as-grown polycrystalline NSP sample material was immersed in 50 ml of a 1 molar aqueous AgNO3 solution for various lengths of time to observe the rate of Na+–Ag+ exchange. Based on these results, the single crystals were then immersed in the same com­position solution for 12 h to guarantee full Na+–Ag+ exchange.

2.2. Scanning electron microscopy (SEM)

Crystallite morphology and semiquantitative chemical analyses were evaluated by means of Field Emission Scanning Electron Microscopy (FE-SEM) using a Zeiss Ultra Plus II microscope coupled with an Oxford Instruments X-MAX 50 mm2 SDD Energy Dispersive X-ray spectrometer (EDX). Samples were mounted on standard Al-sample holders with adhesive graphite tabs and coated with carbon to enhance electric conductivity. Synthesis materials were analysed at different magnifications with a 20 kV acceleration voltage and working distances of 4–9 mm (using SE or InLens detectors). The EDX analyses (mapping) were performed to confirm com­plete Na+ –Ag+ replacement.

2.3. Thermal analysis

Low-tem­per­ature caloric measurements were made at Salzburg University by E. Dachs on a Quantum Design Physical Property Measurement System (PPMS) equipped with the relaxation calorimeter option of the PPMS system. Data were collected three times (and averaged for each step) at 180 different tem­per­atures between 2 and 300 K, using a logarithmic spacing with increasing data density toward lower tem­per­atures. Additional Cp data sets were collected between 151 and 302 K in 1 K steps. More details on the PPMS technique can be found in the literature (Dachs & Bertoldi, 2005[Dachs, E. & Bertoldi, C. (2005). Eur. J. Mineral. 17, 251-259.]; Dachs & Benisek, 2011[Dachs, E. & Benisek, A. (2011). Cryogenics, 51, 460-464.]). High-tem­per­ature heat capacity was recorded between 250 and 573 K by A. Benisek (Salzburg University) in a step scanning mode with a power-com­pensated PerkinElmer Diamond Differential Scanning Calorimeter (DSC). The DSC heat capacity measurements were carried out under an argon flow during heating and cooling, with a heating rate of 10 K min−1. A single crystal of corundum was measured as a calibration standard. For more details on measurements and calibration, see, for example, Benisek et al. (2010[Benisek, A., Dachs, E. & Kroll, H. (2010). Eur. J. Mineral. 22, 403-410.]) and Dachs et al. (2012[Dachs, E., Geiger, C. A. & Benisek, A. (2012). Am. Mineral. 97, 1771-1782.], 2018[Dachs, E., Benisek, A. & Redhammer, G. (2018). J. Chem. Thermodyn. 120, 123-140.]).

2.4. Powder X-ray diffraction (PXRD)

PXRD data were collected at room tem­per­ature in coupled ΘΘ mode on a Bruker D8 Advance with a DaVinci Design diffractometer equipped with a solid-state Lynxeye detector and an automatic sample changer. Data were acquired using Cu Kα1,2 radiation between 10 and 90° 2Θ, with a step size of 0.01°, an integration time of 1 s and with the divergence slit and the receiving slits opened at 0.3 and 2.5°, respectively. A primary and secondary side 2.5° Soller slit was used to minimize axial divergence and a detector window opening angle of 2.95° was chosen. Refinement of the lattice parameters from PXRD data collected on samples from time-dependent Na+–Ag+ exchange experiments was performed with TOPAS (Version 4.2; Bruker, 2012[Bruker (2012). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]). For Rietveld analyses, the background was modelled with a Chebychev function of 10th order and the fundamental parameter approach was used to describe the peak shape of the Bragg reflections. The structural models applied to Na3Sc2(PO4)3 were taken from Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]). A model was determined from the single-crystal X-ray diffraction data for Ag3Sc2(PO4)3 in this study as the data from the literature (Atovmyan et al., 1983[Atovmyan, L. O., Bukun, N. G., Kovalenko, V. I., Korosteleva, A. I., Tkachev, V. V. & Ukshe, E. A. (1983). Sov. Electrochem. 19, 829-833.]) did not match well.

2.5. Single-crystal X-ray diffraction

Single-crystal X-ray diffraction data were collected on a Bruker SMART APEX CCD diffractometer. The single crystals were selected on the basis of their optical properties (sharp extinctions, regular shape and homogeneity in colour) and glued on top of a glass capillary (0.1 mm in diameter). Intensity data were collected on four different crystals at room tem­per­ature with graphite-monochromated Mo Kα X-ray radiation (50 kV, 20 mA). The crystal-to-detector distance was 30 mm and the detector was positioned at −28° 2θ and −40° 2θ using an ω-scan mode strategy at four different φ positions (0, 90, 180 and 270°). A total of 666 frames with Δω = 0.3° were acquired for each run. Low-tem­per­ature data sets were recorded down to tem­per­atures between 300 and 90 K using a Bruker Cryojet evaporating low-tem­per­ature device with liquid nitrogen as the cooling medium. Two data sets (300 and 520 K) were collected at the TU Dresden on a Bruker AXS Kappa APEXII CCD diffractometer with graphite-monochromated Mo Kα X-ray radiation (50 kV, 30 mA), equipped with a standard calibrated Nonius FR559 Crystal Heater (Tuinstra & Storm, 1978[Tuinstra, F. & Fraase Storm, G. M. (1978). J. Appl. Cryst. 11, 257-259.]). The crystal-to-detector distance was 50 mm and the detector was positioned at 2θ positions of 30 and 45° for the measurements using an ω-scan mode at four different φ positions (0, 90, 180 and 270°).

3D data were integrated and corrected for Lorentz, polarization and background effects using APEX3 software (Bruker, 2015[Bruker (2015). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA.]). Structure solutions, using direct methods and subsequent weighted full-matrix least-squares refinements on F2, were carried out with SHELX2012 (Sheldrick, 2015[Bruker (2015). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA.]), as implemented in the program suite WinGX2014.1 (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]). Experimental data are given in Table 1[link].

Table 1
Experimental details

Experiments were carried out with Mo Kα radiation using a Bruker SMART APEX diffractometer. Absorption was corrected for by multi-scan methods (APEX2; Bruker, 2012[Bruker (2012). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]).

  T = 100 K T = 200 K T = 300 K T = 520 K
Crystal data
Chemical formula Ag3.06Sc2(PO4)3 Ag3.03Sc2(PO4)3 Ag3.05Sc2(PO4)3 Ag3.02Sc2(PO4)3
Mr 704.90 701.67 703.49 700.59
Crystal system, space group Monoclinic, C2/c Monoclinic, C2/c Trigonal, R[\overline{3}]c:H Trigonal, R[\overline{3}]c:H
Temperature (K) 100 200 295 520
a, b, c (Å) 15.467 (3), 8.9627 (14), 9.1186 (15) 15.5374 (2), 8.9703 (1), 22.5718 (3) 8.9756 (4), 8.9756 (4), 22.6248 (10) 8.9671 (8), 8.9671 (8), 22.7622 (19)
α, β, γ (°) 90, 124.1439 (15), 90 90, 89.9984 (4), 90 90, 90, 120 90, 90, 120
V3) 1046.2 (3) 3145.95 (7) 1578.49 (16) 1585.1 (3)
Z 4 12 6 6
μ (mm−1) 7.38 7.15 7.31 7.24
Crystal size (mm) 0.14 × 0.14 × 0.09 0.14 × 0.14 × 0.09 0.14 × 0.14 × 0.09 0.12 × 0.12 × 0.08
 
Data collection
Tmin, Tmax 0.38, 0.52 0.51, 0.65 0.38, 0.52 0.417, 0.581
No. of measured, independent and observed [I > 2σ(I)] reflections 5927, 1407, 1355 50538, 6307, 2271 7548, 496, 472 4628, 924, 700
Rint 0.032 0.038 0.027 0.038
(sin θ/λ)max−1) 0.706 0.769 0.701 0.873
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.087, 1.22 0.032, 0.107, 1.04 0.018, 0.044, 1.11 0.033, 0.071, 1.07
No. of reflections 1407 6307 496 924
No. of parameters 140 380 60 60
No. of restraints 12 42 0 0
Δρmax, Δρmin (e Å−3) 1.16, −1.19 1.08, −0.92 0.39, −0.36 0.78, −0.64
Computer programs: APEX2 (Bruker, 2012[Bruker (2012). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]), APEX3 (Bruker, 2015[Bruker (2015). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), ORTEP for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).
†Unconstrained refinements were used so the different Ag content results in uncertainity in determining the Ag content from the single crystal data. Over the whole T-range it is in between 3.02 and 3.06 atoms per formula unit.

3. Results and discussion

3.1. Synthesis and exchange experiments

Single-phase polycrystalline NSP was obtained in the single-step synthesis at 1573 K. The as-synthesized NSP samples are white with a very pale-blue tint. Indexing of the PXRD data yields a monoclinic cell [a = 15.7168 (4), b = 8.9328 (1) and c = 9.0408 (2) Å, and β = 126.035 (3)°] that can be most accurately structurally refined with C2/c symmetry, as proposed pre­viously (Guin et al., 2017[Guin, M., Dashjav, E., Kumar, C. M. N., Tietz, F. & Guillon, O. (2017). Solid State Sci. 67, 30-36.]; Redhammer et al., 2020[Redhammer, G. J., Tippelt, G., Benisek, A., Topa, D. & Rettenwander, D. (2021). In preparation.]; Ladenstein et al., 2020[Ladenstein, L., Lunghammer, S., Wang, E. Y., Miara, L. J., Wilkening, M., Redhammer, G. J. & Rettenwander, D. (2020). J. Phys. Energy, 2, 035003.]). The recognition of a monoclinic cell at room tem­per­ature contrasts with findings in the recent literature where more general R[\overline{3}]c (Liu et al., 2018[Liu, D., Jin, Y. H., Lv, Y., Ju, G. F., Wang, C. L., Chen, L., Luo, W. W. & Hu, Y. H. (2018). J. Am. Ceram. Soc. 101, 5627-5639.]) symmetry is reported.

The NSP became pale-yellow immediately on coming into contact with the AgNO3 solution due to the Ag+–Na+ exchange reaction. The PXRD data clearly indicate that the main portion of NSP transforms to ASP within a period of 1 min of immersion in the Ag-bearing solution (see Fig. S1 in the supporting information). The diffraction pattern of ASP can be indexed on the basis of a trigonal R[\overline{3}]c unit cell and Rietveld refined with a = 8.9708 (3) and c = 22.6129 (6) Å. Only minor amounts of an impurity phase, i.e. Ag(PO4)3, were observed. The a-lattice parameter increases by about 0.1% (∼0.009 Å) as immersion times extend beyond 1 min. After 10 h of treatment, only a minor increase can be observed that follows a simple power law, as shown in Fig. 1[link](a). Similar observations are made for the c-lattice parameter, i.e. within 1 min, the lattice parameter increased by about 0.06% (∼0.0135 Å) and no significant change can be observed after 10 h (cf. Table S1 in the supporting information).

[Figure 1]
Figure 1
The change of lattice parameters a and c with immersion time of Na3Sc2(PO4)3 polycrystalline material in 1 molar AgNO3 solution.

Comparison of the lattice parameters of untreated NSP with those of ASP highlights the fact that the replacement of Na+ (rIV = 1.02 Å) by Ag+ (rIV = 1.15 Å) mainly affects the c-lattice parameter and expands it by 1.6%, while the a-lattice parameter is increased by only 0.5%. The replacement of Na+ by Ag+ thus has distinct effects on, and results in rearrangements in, the Sc2(PO4)3 framework.

Based on the above observations of a very fast ion-exchange reaction, a leaching time of 12 h was taken to be sufficient for com­plete ion exchange in the single crystals. The highly transparent and cuboid-shaped crystals do not show any morphological change due to the Na+–Ag+ exchange, i.e. no cracks or defoliation of the crystals are observed. A secondary electron image of typical exchanged ASP crystals is shown in Fig. 2[link]. The single crystals are cube-shaped with mostly well-developed faces. They average around 100 µm in size with individual crystals up to 300 µm.

[Figure 2]
Figure 2
Secondary electron image, taken on a scanning electron microscope (SEM), showing the typical morphology of the Ag3Sc2(PO4)3 crystals, which were obtained from a flux-grown Na3Sc2(PO4)3 material via ion exchange. EDX spot analyses and mapping on the surface and on cross sections of some selected crystals (cut in the middle and cutting faces analysed) yield no indications of Na+, but rather a homogenous distribution of Ag+ on and throughout the crystals. Details of these measurements are reported in Ladenstein et al. (2020[Ladenstein, L., Lunghammer, S., Wang, E. Y., Miara, L. J., Wilkening, M., Redhammer, G. J. & Rettenwander, D. (2020). J. Phys. Energy, 2, 035003.]).

3.2. Thermal analysis

Heat capacity measurements (Fig. 3[link]) on a small amount (27 mg) of unground single crystals reveal two events in the tem­per­ature evolution: one very prominent peak centred at 177 (1) K and a second, rather broad, peak at 292 (1) K. PPMS (low tem­per­ature) and DSC measurements correlate well in the overlapping tem­per­ature range. The two peaks correspond to two structural phase transitions (see below). A DSC run on a larger sample mass of polycrystalline ASP (immersion time 6 h) revealed, however, a somewhat different behaviour (see inset in Fig. 3[link]). Here, the peak at around room tem­per­ature is much smaller and is shifted towards 304 K. Nevertheless, all the observed peaks exhibit a lambda (λ) shape, typical for order–disorder transitions (Benisek et al., 2018[Benisek, A., Dachs, E. & Grodzicki, M. (2018). Phys. Chem. Chem. Phys. 20, 19441-19446.]; Benisek & Dachs, 2018[Benisek, A. & Dachs, E. (2018). J. Alloys Compd. 735, 1344-1349.]). The phase transition energy, determined by integrating the area beyond the peaks, amounts to 739 (3) J g−1 for the transition at 177 K and 445 (5) J g−1 for the 304 K transition. As the phase transitions are associated with an increase in tem­per­ature in the sample material, the reactions are endothermic and the high-tem­per­ature phases having a higher entropy are thus more disordered and have a higher symmetry.

[Figure 3]
Figure 3
Heat capacity of small single crystals of Ag3Sc2(PO4)3 between 2 and 550 K. The inset depicts the heat capacity of the polycrystalline sample.

3.3. Structural characterization

3.3.1. The high-tem­per­ature γ-form

At room tem­per­ature, the observed single-crystal X-ray diffraction intensity data can be indexed on the basis of a rhombohedral unit cell, with a = 8.9756 (4) and c = 22.6248 (10) Å, and analysis of the systematic extinctions yields the space group R[\overline{3}]c (No. 167), with Z = 6. Structure solutions using direct methods (Sheldrick, 2015[Bruker (2015). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA.]) and charge-flipping methods, as applied in the JANA2006 software (Petříček et al., 2014[Petříček, V., Dušek, M. & Palatinus, L. (2014). Z. Kristallogr. 229, 345-352.]), converged on one structural model, which is very similar to the commonly observed skeleton structure of γ-type NaSICON com­pounds (e.g. Redhammer et al., 2016[Redhammer, G. J., Rettenwander, D., Pristat, S., Dashjav, E., Kumar, C. M. N., Topa, D. & Tietz, F. (2016). Solid State Sci. 60, 99-107.]; Monchak et al., 2016[Monchak, M., Hupfer, T., Senyshyn, A., Boysen, H., Chernyshov, D., Hansen, T., Schell, K. G., Bucharsky, E. C., Hoffmann, M. J. & Ehrenberg, H. (2016). Inorg. Chem. 55, 2941-2945.], and references therein). The octahedrally coordinated Sc3+ are in the 12c position (site symmetry 3.), the tetrahedrally coordinated P5+ in the 18e position (site symmetry 0.2) and the two independent O atoms in general 36f positions. Two ScO6 octa­hedra, which share all their corners with PO4 tetrahedra, and three PO4 tetrahedra, sharing all their corners with neighbouring ScO6 octahedra, build a basic repeat unit with an [Sc2(PO4)3]3− com­position, which is known as the lantern unit (Masquelier & Croguennec, 2013[Masquelier, C. & Croguennec, L. (2013). Chem. Rev. 113, 6552-6591.]) and is depicted in Fig. 4[link](a). Each lantern unit is connected to six others, thus generating a 3D framework with large interstitial voids that accommodate the Ag+ (or more generally the alkali) cations. These lanterns are stacked parallel to the [001] direction within the common rhombohedral structure space group R[\overline{3}]c.

[Figure 4]
Figure 4
Polyhedral drawings of the structure of NASICON-type com­pounds. Alkali-metal positions have been omitted to highlight the 3D skeleton structure. (a) The basic lantern unit and (b) a section of the Ag3Sc2(PO4)3 R[\overline{3}]c structure, viewed along [100]. Anisotropic atomic displacement parameters are drawn at the 95% probability level.

For Na3Sc2(PO4)3, Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]) reported a disorder of the tetrahedra with highly anisotropic vibration amplitudes of the P cations and also for the anions. In addition, they observed broad Raman bands for PO4 modes. From this, they concluded that the rotational terms for the PO4 tetrahedra exist and result in some positional disorder. For ASP in the γ-phase, the Sc atoms show highly isotropic displacement parameters (Umax to Umin of the principal mean-square atomic displacement are 0.0088 and 0.0073 Å2, respectively, at 300 K). Indeed, the P atoms display some higher anisotropic vibration (Umax = 0.0149 Å, Umin = 0.0089 and Umax/Umin ≃ 2.4), which could be interpreted as a sign of some minor positional disorder. Increasing the tem­per­ature to 500 K increases the overall size of the thermal vibration, while the anisotropy is somewhat reduced, with Umax/Umin ≃ 2.2. The O atoms show larger anisotropic atomic displacement, with Umax/Umin of 3.8 and 2.4 for the O1 and O2 atoms, respectively. As expected, ADPmax values are perpendicular to the M—O—P bonds.

In the γ-phase, the Ag+ cations are reported to occupy two different cavities: M1 is at the 6b position (0,0,0) with site symmetry [\overline{3}] and corresponds to an empty octahedral site in the cubic close-packed arrangement of corundum. The M2 site is located at the 18e position (x, [1 \over 3], [1 \over 12]) (Catti et al., 2004[Catti, M., Comotti, A., Di Blas, S. & Ibberson, R. M. (2004). J. Mater. Chem. 14, 835-839.]). However, some slight displacements to the general 36f positions are observed (Redhammer et al., 2016[Redhammer, G. J., Rettenwander, D., Pristat, S., Dashjav, E., Kumar, C. M. N., Topa, D. & Tietz, F. (2016). Solid State Sci. 60, 99-107.]). In ASP, the Ag+ ions are distinctly disordered within the cavities of the framework. The normal 6b M1 site turned out to be unoccupied during refinement and the Ag+ ions are shifted mainly along y away from the [ \overline{3}] axis to the general position 36f at [0.017 (2), 0.0807 (6), 0.0019 (2)], which is denoted as the Ag11 site. It is still close to the 6b position and has an occupancy of 1.012 (7) Ag+ per formula unit (pfu). The electron density around the 18e position is best modelled by a split model with two positions: the regular 18e position Ag2, which is located at the twofold axis and is occupied by 1.14 (1) Ag+ pfu, and a position denoted Ag22 that is displaced from Ag2 towards the 6b site by about 0.55 Å and is occupied by 0.84 (1) Ag+ pfu. However, the best-fit model for the observed electron density requires a further `site' for Ag+ between the Ag22 and Ag11 positions. Due to the low occupancy [0.052 (6) pfu], only isotropic displacement parameters could be refined. For all other Ag+ sites, full anisotropic refinement of the atomic displacement parameters is possible and yields highly anisotropic cigar-shaped vibration ellipsoids, which are oriented along the most probable ion-diffusion path and partly overlap each other, as can be seen in Fig. 5[link](a). This indeed suggests a more or less continuous distribution of Ag+. Similar observations were made by Atovmyan & Tkachev (1995[Atovmyan, L. O. & Tkachev, V. V. (1995). Koord. Khim. 21, 585-587.]); however, their Ag positions do not exactly match those found herein and, applying their structural model, we were neither able to reproduce our powder nor our single-crystal intensity data. Regardless of the observed differences, the above authors observed a displacement of Ag+ from M1 at 6b, as well as from the regular M2 position. Moreover, the ions are less disordered, as found in our study. In summary, the site-occupation factors indicate 3.03 Ag+ per formula unit, which is very close to the expected value.

[Figure 5]
Figure 5
(a) The Ag3Sc2(PO4)3 structure at 300 K in the R[\overline{3}]c phase, with anisotropic atomic displacement ellipsoids at the 95% probability level, com­pared to the calculated bond-valence electron landscape maps [at the 0.02 (dark blue), 0.20 (green) and 0.45 eV (yellow) level above minimum] (b) without and (c) with the experimentally obtained Ag+ positions.

For the 298 K data set, refinements with anharmonic anisotropic atomic displacement parameters were also performed using the JANA2006 software. Using third-order (Ag11 and Ag2) and fourth-order (Ag22) anharmonic anisotropic displacement parameters (ADPs), com­parably low reliability factors are obtained without needing the intermediate Ag12 `site'. The obtained joint probability density functions of both refinement models are very similar to each other, but those with harmonic ADPs appear to be smoother and thus the harmonic model is preferred here.

Alkali-metal ions can jump between two adjacent sites by bypassing a bottleneck. The bottleneck is defined by two triangles, which have one common MO6 edge and expand to the O1 and O2 atoms of a tetrahedron opposite to the MO6 octahedron (Kohler & Schulz, 1985[Kohler, H. & Schulz, H. (1985). Mater. Res. Bull. 20, 1461-1471.]) (cf Fig. S2 in the supporting information). A measure of the size of this bottleneck is the area of the two triangles T1 (e.g. O2—O2ii—O1x; see Table 2[link] for symmetry codes i–xv) and T2 (e.g. O2—O2ii—O2xi), as illustrated in Fig. 6[link]. There is a direct correlation between the area and the activation energy for the jump processes, denoted Ea (Guin & Tietz, 2015[Guin, M. & Tietz, F. (2015). J. Power Sources, 273, 1056-1064.]; Losilla et al., 2000[Losilla, E. R., Aranda, M. A. G., Bruque, S., Sanz, J., París, M. A., Campo, J. & West, A. R. (2000). Chem. Mater. 12, 2134-2142.]). For ASP, the T1 and T2 areas at room tem­per­ature are 5.495 and 5.952 Å2, respectively. These are at the upper end of the range com­piled by Guin & Tietz (2015[Guin, M. & Tietz, F. (2015). J. Power Sources, 273, 1056-1064.]) for Na-bearing NaSICON-type com­pounds, suggesting that the substitution of Na+ by Ag+ opens up the structure and, therefore, also the bottlenecks.

Table 2
Selected geometric parameters (Å) for Ag3Sc2(PO4)3 at different tem­per­atures

T = 100 K
Sc1—O4i 2.035 (5) P2—O2iv 1.513 (4)
Sc1—O2i 2.038 (4) P2—O6 1.554 (4)
Sc1—O3 2.071 (4) Ag1⋯Ag1B 0.61 (7)
Sc1—O5ii 2.089 (4) Ag1⋯Ag1A 0.70 (3)
Sc1—O1 2.141 (4) Ag1A⋯Ag1Aiii 1.71 (5)
Sc1—O6 2.150 (4) Ag1A⋯Ag3Bv 2.27 (2)
P1—O5iii 1.514 (4) Ag1B⋯Ag3A 1.19 (7)
P1—O3 1.527 (4) Ag2⋯Ag2A 0.98 (6)
P1—O4 1.539 (5) Ag3A⋯Ag3B 1.30 (3)
P1—O1iv 1.554 (4)    
 
T = 200 K
Sc1—O5 2.045 (4) P4—O13 1.522 (4)
Sc1—O13 2.049 (4) P4—O14 1.547 (4)
Sc1—O8vi 2.052 (4) P5—O17 1.524 (4)
Sc1—O9 2.124 (4) P5—O16 1.525 (4)
Sc1—O15 2.133 (3) P5—O15 1.535 (4)
Sc1—O1 2.136 (4) P5—O18 1.537 (4)
Sc2—O2i 2.044 (3) Ag1A⋯Ag1B 0.628 (6)
Sc2—O16vii 2.047 (4) Ag1A⋯Ag6Bx 2.800 (15)
Sc2—O10viii 2.051 (4) Ag1B⋯Ag7C 2.748 (18)
Sc2—O3ix 2.126 (4) Ag1B⋯Ag7B 2.977 (14)
Sc2—O12x 2.132 (3) Ag2A⋯Ag2B 0.620 (5)
Sc2—O18 2.135 (3) Ag2A⋯Ag6C 2.906 (14)
Sc3—O11x 2.047 (4) Ag2B⋯Ag7Bviii 2.632 (17)
Sc3—O4 2.048 (4) Ag2B⋯Ag7Aviii 2.837 (15)
Sc3—O17xi 2.052 (4) Ag3A⋯Ag3B 0.607 (6)
Sc3—O14xii 2.124 (3) Ag3A⋯Ag6A 2.865 (10)
Sc3—O6vi 2.127 (4) Ag3B⋯Ag7A 2.654 (11)
Sc3—O7x 2.129 (4) Ag3B⋯Ag7Cviii 2.977 (10)
P1—O4 1.527 (5) Ag4⋯Ag4vi 0.564 (13)
P1—O2 1.534 (4) Ag4⋯Ag6A 2.812 (11)
P1—O1 1.540 (4) Ag5A⋯Ag5B 0.628 (4)
P1—O3 1.543 (4) Ag5A⋯Ag6Bxiii 2.862 (14)
P2—O8 1.525 (4) Ag5B⋯Ag6C 2.822 (17)
P2—O5 1.533 (4) Ag6A⋯Ag6Cxi 0.897 (9)
P2—O7 1.536 (4) Ag6A⋯Ag6Bxi 0.981 (7)
P2—O6 1.541 (4) Ag6B⋯Ag6C 0.899 (7)
P3—O10 1.526 (4) Ag7A⋯Ag7B 0.695 (9)
P3—O11 1.536 (4) Ag7A⋯Ag7Cviii 0.704 (9)
P3—O9 1.538 (4) Ag7B⋯Ag7C 0.674 (9)
P3—O12 1.541 (3)    
 
T = 300 K
Sc1—O1xi 2.0505 (12) Ag11⋯Ag11xv 0.668 (3)
Sc1—O2 2.1324 (11) Ag11⋯Ag21 1.35 (3)
P1—O1xi 1.5261 (12) Ag21⋯Ag22 1.18 (3)
P1—O2xiv 1.5398 (11) Ag22⋯Ag2 0.501 (12)
 
T = 520 K
Sc1—O1xi 2.0542 (14) Ag11⋯Ag11xv 0.748 (3)
Sc1—O2 2.1334 (13) Ag11⋯Ag21 1.310 (19)
P1—O1xi 1.5215 (14) Ag21⋯Ag22 1.03 (2)
P1—O2xiv 1.5360 (14) Ag22⋯Ag2 0.623 (11)
Symmetry codes: (i) −x + [1 \over 2], −y + [1 \over 2], −z; (ii) −x, y, −z + [1 \over 2]; (iii) −x + [1 \over 2], −y + [1 \over 2], −z + 1; (iv) −x + [1 \over 2], y + [1 \over 2], −z + [1 \over 2]; (v) x, −y, z + [1 \over 2]; (vi) −x + 1, y, −z + [1 \over 2]; (vii) −x + [1 \over 2], −y + [3 \over 2], −z; (viii) −x + 1, −y + 1, −z; (ix) x[1 \over 2], y + [1 \over 2], z; (x) x − [1 \over 2], y − [1 \over 2], z; (xi) x, y − 1, z; (xii) −x + 1, y − 1, −z + [1 \over 2]; (xiii) −x + [3 \over 2], y − [1 \over 2], −z + [1 \over 2]; (xiv) −x + [2 \over 3], −y + [1 \over 3], −z + [1 \over 3]; (xv) x − y, x, −z.
[Figure 6]
Figure 6
Part of the NaSICON structure of Ag3Sc2(PO4)3 at 298 K (R[\overline{3}]c), viewed along [100], showing a lantern unit and some neighbouring polyhedra for γ-ASP. The atom nomenclature and equivalent atoms are as in the text. [Symmetry codes: (i) −y + 1, x − y, z; (ii) −y, x − y, z; (iii) y − 1, x, −z + [1 \over 2]; (iv) x − y, −y, −z + [1 \over 2]; (v) −x + [1 \over 3], −y − [1 \over 3], −z + [2 \over 3]; (vi) −x + [1 \over 3], −y + [2 \over 3], −z + [2 \over 3]; (vii) y, x, −z + [1 \over 2]; (viii) −y + [1 \over 3], −x + [2 \over 3], z + [1 \over 6]; (ix) −x + y + [1 \over 3], y + [2 \over 3], z + [1 \over 6]; (x) −x + [1 \over 3], −x + y − [1 \over 3], −z + [1 \over 6]; (xi) x − y, x, −z; (xii) −x + y, −x, z; (xiii) −x − 1, −x, z; (xiv) x, y − 1, z; (xv) y, −x + y, −z; (xvi) y − [1 \over 3], −x + y + [1 \over 3], −z + [1 \over 3].]

There is direct evidence in the room-tem­per­ature structural data that the 3D ion-diffusion pathway is through these bottlenecks. Considering the shortest Ag+ jump distances, the pathway is along …Ag11–Ag11–Ag21–Ag22–Ag2–Ag22–Ag21…, with jump distances of 0.667 (3)–1.352 (2)–1.186 (2)–0.500 (2)–0.500 (2)–1.186 (2) Å, respectively. Interestingly, this diffusion pathway bypasses the regular M1 and M2 sites and allows very short jump distances. The experimentally observed diffusion pathways are further confirmed by bond-valence electron landscape (BVEL) map calculations (Katcho et al., 2019[Katcho, N. A., Carrete, J., Reynaud, M., Rousse, G., Casas-Cabanas, M., Mingo, N., Rodríguez-Carvajal, J. & Carrasco, J. (2019). J. Appl. Cryst. 52, 148-157.]) (see Fig. 5[link]). From these BVEL maps, the activation energies for Ag+ diffusion along the different crystallographic sites are estimated to be below 0.2 eV.

To test for any changes in Ag+ distribution, part of the sample material was annealed for 72 h at 573 K and rapidly quenched to room temperature. Analysis of the intensity data from three experiments at this annealing tem­per­ature yield very similar results (see Table S2 in the supporting information for details). Thus, the distinct disorder of the Ag+ ions is not removed even at a low annealing tem­per­ature, when cationic ordering is usually reached. Hence, the results highlight this intrinsic property of the R[\overline{3}]c structure of ASP.

In situ measurements at 520 K reveal no significant changes to the distribution of Ag+; only a slightly higher occupancy of the Ag21 position at the expense of Ag2 is observed (see Table S2 in the supporting information). During an increase in tem­per­ature, the Sc—O1i and Sc—O2 bond lengths expanded somewhat (Table 2[link] and Table S3 in the supporting information), causing the average 〈Sc—O〉 to increase from 2.090 (2) to 2.094 (2) Å, the polyhedral volume to increase and the bond-angle distortion to be reduced. For the PO4 tetrahedra, a small reduction of the bond lengths by ∼0.004 Å is observed with increasing tem­per­ature, but the polyhedral distortion parameters remain very similar at room temperature and 520 K (Table S3 in the supporting information). A shortening of the P—O distances in NaSICON-type com­pounds has already been described by Kohler & Schulz (1985[Kohler, H. & Schulz, H. (1985). Mater. Res. Bull. 20, 1461-1471.]) in their study of NZSP com­pounds. Generally, alterations in structural parameters within the first coordination sphere around Sc and P are small; however, there are some more evident variations within the second coordination sphere, i.e. within the con­nection of individual polyhedra. The lantern unit is stretched parallel to the c direction, expressed by an increase of the Sc—Sciv distance from 4.602 (2) to 4.622 (2) Å (Fig. 6[link]). This is facilitated by an increase of the Sc—O1i bond length and a slight closing of the intra-lantern M—O1—P angle, e.g. the Sc—O1i—Pii in Fig. 6[link]. These changes directly influence the c-lattice parameters and are responsible for the distinct increase with tem­per­ature.

The inter-lantern M—O2—P angle (e.g. Sciv—O2iv—Pv in Fig. 6[link]) increases with tem­per­ature by 0.9 (1)°. The rotation of the M and P polyhedra is linked to an opening of the bottleneck and an increase in the inter-lantern O1⋯O2 and O1⋯O2 distances. Additionally, this is achieved by an opening of the O2—Sc—O2ii octahedral bond angle and an increase of the O2–O2ii octahedral edge by ∼0.014 (2) Å. At 520 K, the T1 and T2 areas are 5.555 and 6.071 Å2, respectively, reflecting the higher ionic conductivity with increasing tem­per­ature, as observed previously (Ladenstein et al., 2020[Ladenstein, L., Lunghammer, S., Wang, E. Y., Miara, L. J., Wilkening, M., Redhammer, G. J. & Rettenwander, D. (2020). J. Phys. Energy, 2, 035003.]).

The 520 K data for ASP can be directly com­pared to NSP, which also has an R[\overline{3}]c structure at 500 K (Ladenstein et al., 2020[Ladenstein, L., Lunghammer, S., Wang, E. Y., Miara, L. J., Wilkening, M., Redhammer, G. J. & Rettenwander, D. (2020). J. Phys. Energy, 2, 035003.]). One distinct difference is that NSP contains a more com­pressed lantern unit along the c direction, with an Sc⋯Sciv separation of 4.556 (2) Å, which is ∼0.066 (2) Å less than in ASP. The intra-lantern M—O1—P angle (Sc—O1i—Pii) is also distinctly lower by as much as 1.85 (5)° (cf Table S3 in the supporting information). Furthermore, within the ScO6 octahedron, significant changes are induced by the Na+–Ag+ exchange: the Sc—O2 bonds are evidently longer in ASP com­pared to NSP [2.133 (1) and 2.112 (2) Å at 520 and 500 K, respectively]. Moreover, the Sc—O1 bonds are more elongated, which leads to an increase of <Sc—O> by 0.013 (2) Å, an increase of the polyhedral volume, a slight increase in the polyhedral distortion index and a lower, i.e. more regular, bond-angle configuration in ASP. For the tetrahedral site, the P—O distances are more similar to each other than Sc—O, but again the P—O2 bond lengths are noticeably longer by 0.015 (3) Å in ASP, while the P—O1 bond lengths remain constant [−0.005 (3) Å]. Overall, the PO4 tetrahedron in ASP appears to be similar to that in NSP, with a slightly larger polyhedral volume, a larger distortion index and a lower bond-angle variance. The M—O2—P inter-lantern angle is not affected by the Na+–Ag+ substitution. Nevertheless, the construction of the octahedral–tetrahedral connection changes with the Sciv—O2iv—O1vi angle, which involves the O2iv–O1vi tetrahedral edge. The decrease in this angle from ASP to NSP of 1.1° has a direct influence on the bottleneck size for alkali-ion migration; it is more closed in NSP, with T1 and T2 areas of 5.384 and 5.598 Å2, respectively, at 500 K. These values com­pare well with those given in Guin & Tietz (2015[Guin, M. & Tietz, F. (2015). J. Power Sources, 273, 1056-1064.]) and allow fast ion movement with low activation energies.

3.3.2. The intermediate C2/c β-form

ASP undergoes a phase transition between 300 and 270 K, as is shown by the calculated precession images of the (h0l) plane (see Fig. 7[link]). This polymorph is preserved down to 180 K.

[Figure 7]
Figure 7
Calculated precession images of the (h0l) plane of Ag3Sc2(PO4)3 at tem­per­atures of 300, 200 and 100 K, supporting a structural phase transition between these tem­per­atures.

Indexing of all the observed intensity data is possible using a tri-twinned monoclinic unit cell, with a = 15.5374 (2), b = 8.9703 (1) and c = 22.5718 (3) Å, and β = 89.998 (4)° at 200 K. The unit-cell parameters of the monoclinic and rhombohedral cells are related to each other by amonoc = 2arombsin60 °, bmonoc = bromb and cmonoc = cromb. Intensity statistics and systematic extinctions provide strong evidence for the space group C2/c, with Z = 4. Structure solution yields a structural model with a framework very similar to the ordered low-tem­per­ature structure reported for Na3V2(PO4)3 by Chotard et al. (2015[Chotard, J.-N., Rousse, G., David, R., Mentré, O., Courty, M. & Masquelier, C. (2015). Chem. Mater. 27, 5982-5987.]). It should be noted that full indexing of the data can also be achieved on the basis of a trigonal cell, with a = b = 18.060 (8) and c = 22.661 (11) Å, in the space group P[\overline{3}]c1; however, no definitive structure solution was possible. As outlined in more detail in the supporting information, models assuming (in)commensurate modulations were also tested, but did not yield satisfactory results and it is thus assumed that tri-twinning best describes the observed data. This is a very similar situation to the case of NSP (Ladenstein et al., 2020[Ladenstein, L., Lunghammer, S., Wang, E. Y., Miara, L. J., Wilkening, M., Redhammer, G. J. & Rettenwander, D. (2020). J. Phys. Energy, 2, 035003.]) and details on this com­pound are given in a com­panion paper (Redhammer et al., 2020[Redhammer, G. J., Tippelt, G., Benisek, A., Topa, D. & Rettenwander, D. (2021). In preparation.]).

The monoclinic β-form of ASP shows three independent Sc-atom positions, five independent P-atom positions and 18 independent O-atom positions, all of them on general positions 8f, except for P5, which resides at a 4e Wykoff position. The individual ScO6 octahedra are similar to each other in the β-form, with 〈Sc—O〉 bond lengths of 2.095, 2.094 and 2.088 Å at 270 K. There are also no significant differences in the volume and polyhedral distortion indices. The Sc1O6 octahedron has the largest average Sc—O bond length and appears to be more regular than the others. No significant changes occur within the first coordination sphere of Sc3+ during transition from the β- to the γ-form. In NSP, the three individual octahedra have almost the same 〈Sc—O〉 bond lengths and polyhedral volumes at 300 K. However, a significant bond-angle variance leads to a polyhedral distortion (see Table S3 in the supporting information). Hence, the replacement of the smaller Na+ ion by the larger Ag+ ion yields more regular local environments around Sc. The bond angles narrow with decreasing tem­per­ature from 270 to 180 K. The five PO4 tetrahedra are mutually similar in size and distortion, with 〈P—O〉 values ranging between 1.529 and 1.535 Å, whereby the P1 and P4 tetrahedra appear to be the largest and smallest, respectively. The tetrahedra are remarkably regular, with smaller distortion indices and a small bond-angle variance (Table S3 in the supporting information). In addition, there is almost no change to the tetrahedron observed within the stability range of the β-phase. Similar to the octahedral sites, the average 〈P—O〉 bond lengths of the tetrahedral site are larger for ASP (about 0.008 Å) com­pared to NSP at 270 and 300 K. Moreover, the slightly smaller 〈P—O〉 distances invoke larger bond-angle variances in NSP.

The overall topology of the β-form is closely related to the γ-form. The interconnection of individual polyhedra, i.e. between the three distinct ScO6 octahedra and the five distinct PO4 tetrahedra, which allows for a larger degree of freedom for structural adjustments, largely resembles the γ-phase. Two different lantern units can be discerned: one is built up by two Sc1O6 octahedra, two P2 tetrahedra and one P4 tetrahedron, whereas the second consists of Sc2O6 and Sc3O6 octahedra, and P1, P3 and P5 tetrahedra. Within these lantern units, the M—O—P angles range between 152.8 (2) and 153.7 (2)° at 180 K, with an average value of 153.3 (2)°, which is similar to that at 300 K in the γ-phase. There are no trends evident with increasing tem­per­ature: the distance between two next-neighbour Sc1 atoms is 4.5910 (13) Å at 180 K and increases slightly to 4.6020 (12) Å at 270 K; the Sc2⋯Sc3 separation is smaller and varies between 4.5897 (11) and 4.5930 (14) Å, with no clear tem­per­ature dependence, but increases to 4.5977 (8) Å during the phase transition; and the inter-lantern unit M—O—P angles all range between 145.7 (2) and 146.5 (2), i.e. within the estimated standard deviations. Hence, there is neither a clear variation with tem­per­ature nor a significant alteration in the M—O—P angles. The structure of ASP at 270 K can be com­pared with that of NSP at 300 K. Both com­positions are in the C2/c β-structural state. The Sc—O bond lengths are larger in the high-tem­per­ature ASP structure and the polyhedral distortion is distinctly smaller, which is most prominent in the bond-angle variance (Table S3 in the supporting information). The same is true for the PO4 tetrahedra, where 〈P—O〉 distances are ∼0.008 Å longer on average in ASP. It is evident that the variation in the Sc⋯Sc distances within the lantern units, as well as the intra- and inter-lantern unit M—O—P angles, are ∼0.1 Å smaller in NSP. Hence, the lantern units in NSP are more com­pressed and that leads to a distinctly smaller c-lattice parameter.

Using a similar approach to refine ASP as used for the NSP C2/c β-phase (Ladenstein et al., 2020[Ladenstein, L., Lunghammer, S., Wang, E. Y., Miara, L. J., Wilkening, M., Redhammer, G. J. & Rettenwander, D. (2020). J. Phys. Energy, 2, 035003.]), it turns out that an adequate modelling of alkali ions is only possible by using split atomic positions for Ag1 to Ag5 (except for Ag4, which is close to a 4e special position and, thus, displays a split character by nature) to describe the highly anisotropic behaviour of the Ag atoms. High densities are evident on residual electron-density maps [with the refined Sc2(PO4)3 framework and the Ag1–Ag5 positions] that form a highly anisotropic `star'-like shape centred around [2 \over 3], 0, [1 \over 8] (Ag6) and [1 \over 2], [1 \over 2], 0 (Ag7). Modelling of this pattern was only possible by splitting both positions into three com­ponents, indicating a highly anisotropic nature of the Ag+ occupation around the entire Ag6 and Ag7 positions (see Fig. 8[link]). All positions other than Ag6 are only partly filled: the Ag1–Ag5 positions are filled by about [2 \over 3] and the Ag7 position is [1 \over 2] filled. In this work, the occupation of all the split positions were then added together to describe the entire site. Generally, the Ag+ ions in the β-phase are more centred in their positions than in the γ-phase, where there is a more continuous Ag+-ion distribution. Interestingly, the refined site occupations do not show any significant change with tem­per­ature. The total Ag+ occupation is 3.02 (1) Ag+ pfu, which is similar to that obtained for the γ-phase.

[Figure 8]
Figure 8
Displacement ellipsoid plot (95% probability level) for the Ag+ ions in Ag3Sc2(PO4)3 at 200 K viewed down [001].

Bottleneck sizes between octahedral edges and opposite tetrahedra vary significantly due to the larger number of distinct Sc and P sites. Since the bottleneck size affects ion mobility, and ion mobility is related to the ordering phenomena in NaSICON materials, slightly different order–disorder transition tem­per­atures can be expected, which explains the broad peak observed in the DSC data. Moreover, as tem­per­ature increases, the bottlenecks open up and Ag+ disorder increases, leading to a phase transition to the γ-phase at 300 K. Possible Ag+–Ag+ jump distances are significantly larger and range between 2.63 (14) and 2.862 (12) Å for Ag+ ions in distinct sites, and between 0.618 (18) and 0.899 (17) Å within the split positions of a specific site (see Table 2[link]).

3.3.3. The low-tem­per­ature C2/c α-form

It is evident from the heat capacity Cp measurements that a phase transition occurs around 177 K. Indeed, simulated precession images clearly show that the structure has changed between 180 and 150 K (see Fig. 7[link]c).

Low-tem­per­ature data at 100 K were used for modelling and can be indexed on the basis of a smaller monoclinic cell, with a = 15.467 (3), b = 8.9627 (4) and c = 9.1186 (15) Å, and β = 124.1439 (15)° in the space group C2/c, with Z = 4. Weak additional Bragg peaks again arise from twinning (see the supporting information for more details). Here the unit-cell parameters of this smaller monoclinic cell are related to those of the rhombohedral cell by amonoc = 2arombsin60°, bmonoc = bromb and [{c}_{\rm monoc} = {c}_{\rm romb}/3\cos\left(\beta -90\right)]. Space-group determination suggested both C2/c and acentric Cc symmetry; however, any attempts to refine the structure in the space group Cc failed to give proper R values (wR2 > 20%). The structure of the [Sc2(PO4)3]3− framework, as obtained from the structure solutions in C2/c, corresponds to that proposed by Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]) for NSP, by Subramanian et al. (1985[Subramanian, M. A., Rudolf, P. R. & Clearfield, A. (1985). J. Solid State Chem. 60, 172-181.]) for Na3Zr1.5Sc0.5(P1.5Si1.5O12) and by Hong (1976[Hong, H. Y. P. (1976). Mater. Res. Bull. 11, 173-182.]) for Na3Zr2(Si2PO12). In the final refinements, the atomic coordinates where chosen to be equivalent to these published structures. The low-tem­per­ature α-form (Fig. 9[link]) shows one independent Sc3+ site on the general 8f position (site symmetry 1), two independent P5+ sites (P1 on the 8f and P2 on the 4e position with site symmetry 1 and 2, respectively) and six independent O-atom positions, all on 8f. Among the atomic displacement parameters, Sc again appears to vibrate almost isotropically and the two distinct P5+ have Umax/Umin values of 2.0 and 1.8 for P1 and P2, respectively, while the O atoms again are rather anisotropic, with values between 1.6 (O4) and 4.4 (O5). The slight anisotropy of P5+ appears to be an intrinsic property of ASP, even at low tem­per­ature. Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]) stated that vibrational motions of the P atoms are symmetric for NSP in the monoclinic form and, thus, no positional disorder is present at low tem­per­ature.

[Figure 9]
Figure 9
Part of the NaSICON structure of Ag3Sc2(PO4)3 at 298 K (C2/c), viewed down [010], showing a lantern unit and some neighbouring polyhedra for α-ASP. The atom nomenclature and equivalent atoms are as used in the text. [Symmetry codes: (xvii) x, y, z − 1; (xviii) −x + [1 \over 2], −y + [1 \over 2], −z; (xix) −x + 1, y, −z − [1 \over 2]; (xx) x + [1 \over 2], −y + [1 \over 2], z − [1 \over 2]; (xxi) −x + [1 \over 2], −y + [1 \over 2], −z − 1; (xxii) −x + 1, y, −z + [1 \over 2]; (xxiii) −x + 1, −y + 1, −z.]

The ScO6 octahedra within the first coordination sphere in the framework of the α and β phases of ASP are remarkably alike with respect to the average bond lengths and distortion indices. This also applies to the PO4 tetrahedra. However, the tetrahedra show a higher bond-angle variance and also higher distortion with similar volumes and average P—O bond lengths. Over the entire tem­per­ature range and in the different phases, the tetrahedra deviate most from an ideal configuration in the low-tem­per­ature α-phase. While the above-mentioned differences are com­paratively small, more pro­nounced changes occur in the arrangement of polyhedra relative to each other within and between the lantern units during the phase transition. The intra-lantern Sc—O—P angles for Scxvii—O5xviii—P1xvii are ∼153° in the β-phase and ∼159.6 (1)° in the α-phase (see Fig. 9[link] for symmetry codes xvii–xxiii). The Scxvii—O4xix—P1xix angles narrow to 139.5 (1)° with the Sc⋯Sc distance remaining almost constant at 4.600 (2) Å at 100 K, which is close to the value of 4.598 (1) Å at 298 K. Also, the inter-lantern Sc—O—P angles differ significantly: they cluster around 146° in the β-phase, whereas in the low-tem­per­ature α-phase, they deviate at 100 K with values of 154.1 (2), 141.5 (2) and 150.5 (2)° for the Scxvii—O3xx—P1xx, Scxxi—O6xxi—P1xxi and Sc—O1—P1 angles, respectively. These rearrangements of the polyhedral interconnections directly influence the size of the bottlenecks. Two different bottlenecks can be identified and are determined by the triangles defined by the O1xx—O6xx edge of the Sc octahedron and the O3xxi and O5xx corners of the opposite tetrahedron (cf Fig. 9[link]). One of the bottlenecks is narrower than the other in the α-phase. The area of the smaller triangle O1xx—O6xx—O5xx—O1xx is 5.184 Å2 at 100 K, which is ∼0.3 Å2 less than the smallest area in the β-phase, potentially hampering ion diffusion. The area of the second triangle O1xx—O6xx—O3xxi—O1xx is 6.204 Å2 at 100 K.

Assuming full occupation, Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]) reported three different Na+ sites for the C2/c α-phase of NSP: two on the general 8f position, both half occupied, and one at the special 4e position (Na2 at 0, 0.1093, [1 \over 4]). Large residual densities were found at very similar positions during structure solution of ASP at 100 K in this study. As already observed for the β- and γ-phases, the Ag-atom positions appear to be highly anisotropic and a split-site refinement was necessary. At 100 K, the regular Ag1 position, which can be com­pared to that used by Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]), has a site-occupancy factor (s.o.f.) of 0.811 (5); however, distinct residual densities were found at distances of ∼0.6 Å. To account for this, a split Ag1A site, with an s.o.f. of 0.105 (5), and an Ag1B site, with a very low s.o.f. of 0.015 (3) at a small second residual opposite to Ag1, were introduced. For the latter, only an isotropic refinement of the atomic displacement parameters was possible. The Ag2 ions reside at the 4e position with an s.o.f of 0.496 (2) and, thus, the site appears to be nearly fully occupied, which is similar to the findings of Collin et al. (1986[Collin, G., Comes, R., Boilot, J. P. & Colomban, P. (1986). J. Phys. Chem. Solids, 47, 843-854.]). Both regular Ag1 and Ag2 positions exhibit small atomic displacement parameters, with Ueq ∼ 0.0123 Å, which is indicative of well-located Ag+ ions. A further small residual peak was detected ∼1 Å offset from the regular Ag2 position and is labelled the Ag2A site; thus, a small s.o.f. of 0.012 (2) at 100 K. The Ag3 site had to be split into two com­ponents, which are separated by as much as 1.3 Å, have s.o.f. values of 0.048 (3) and 0.044 (3), and are labelled Ag3A and Ag3B, respectively. These positions thus show a very low occupation with more than 90% of the split site unoccupied. This is in contrast to NSP, where the corresponding Na3 site was assumed to be 50% filled. The Ag1 and Ag2 sites in ASP are clearly filled to the same extent as the Ag3 site(s). The pathways for Ag+–Ag+ jumps have a less distinct 3D character in the low-tem­per­ature α-phase when com­pared to the β- and γ-phases. One possible pathway is along the …Ag3B–Ag3A–Ag1B–Ag1–Ag1A–Ag1A–Ag1–Ag1B–Ag3A–Ag3–Ag1B… atoms, with distances of 1.30 (3)–1.19 (7)–0.61 (7)–0.70 (3)–1.71 (5)–0.70 (3)–0.61 (7)– 1.19 (7)–1.30 (3)–2.27 (2) Å, respectively (cf Fig. S3 in the supporting information), which all together represent small jump distances. The atoms involved here form a crimpled two-dimensional (2D) layer, as is evident when viewing along [100] in Fig. 10[link](a). The interconnection of these layers is facilitated via Ag1—Ag2A—Ag1, with a shortest distance of 3.126 (4) Å, whereas the regular Ag1 and Ag2 sites are separated from each other by as much as 3.581 (1) Å. Thus, these are discrete layers despite the 3D linking of Ag+. However, the 2+1D (two- plus one-dimensional) character of the Ag+ network and the closing of the bottleneck suggest a low ionic conduction in the low-tem­per­ature α-phase of ASP.

[Figure 10]
Figure 10
Pathways of the shortest Ag+⋯Ag+ interatomic distances in the low-tem­per­ature C2/c α-phase of Ag3Sc2(PO4)3. Note, only the Ag+ ions are shown for clarity (Ag1 positions in blue, Ag2 in green and Ag3 in turquoise). (a) A section of a single layer with x ∼ 0.25. (b) The 2+1-dimensional network viewed along [001].

Inspection of the BVEL maps of the 100 K data reveals that the minimum energy in the structure (−0.4195 eV) is located at the special position [1 \over 4], [1 \over 4], [1 \over 2]. This position is unoccupied, but 1.44 Å from this position is the regular Ag1 position, with a large site occupation. The Ag1A position is offset a further 0.83 Å. A second minimum is located at the 4e position, which is coincident with the Ag2 position. Generally, the positions for Ag+ lie within the calculated energy minimum diffusion pathways, with an activation energy limit of 0.45 eV, as depicted in Fig. 11[link].

[Figure 11]
Figure 11
(a) The Ag3Sc2(PO4)3 structure in the C2/c phase at 100 K, with anisotropic atomic displacement ellipsoids at the 95% probability level com­pared with (b) the calculated bond-valence electron landscape map [at the 0.02 (dark blue), 0.20 (green) and 0.45 eV (yellow) level above minimum]. Note that only the experimentally obtained Ag+ positions are shown on the calculated BVEL map.

The s.o.f. values change with increasing tem­per­ature. The changes below 150 K are minor, with the Ag1 site losing some occupation, as do the Ag1A and Ag3 sites, and to the same extent. The s.o.f. values for the Ag2 sites remain unchanged. Things change more significantly, however, on approaching the phase-transition tem­per­ature. At 160 K, the Ag1 site occupation takes a distinct drop, whereas the Ag3 site(s) become(s) highly populated (see Table S2 in the supporting information). This can be interpreted to be due to disorder of the Ag+ on different sites prior to phase transition.

3.4. Evolution of lattice parameters with tem­per­ature

The a and b unit-cell parameters are similar within the monoclinic phases and, thus, can be com­pared directly [Figs. 12[link](a) and 12[link](b)]. It is evident that upon phase transition, the a-lattice parameter in the β-phase increases dramatically almost linearly by about 0.04 Å. The unit-cell parameters in the α phase at 160 K better fit the trend of the β-phase; however, there is good evidence from data indexing that the c-lattice parameter is indeed 9.1328 (14) Å, instead of ∼22.57 Å, which would be indicative of the β-phase. The b-lattice parameters behave in a similar way. They increase in a slightly nonlinear way with an increase in tem­per­ature, and there is a change in slope of the data array at the αβ phase transition. The unit cells for the α- and β-phases have been subsequently transformed to the equivalent rhombohedral cells using the relationships given in the text above in order to directly com­pare the evolution of all lattice parameters as the tem­per­ature changes [Figs. 12[link](c) and 12[link](d)]. It is evident that arhomb does not increase as tem­per­ature increases, but rather decreases. In contrast, the c-lattice parameter increases linearly and perfectly fits the trend for thermal expansion of the c-lattice parameter in the β-phase.

[Figure 12]
Figure 12
Evolution of the unit-cell parameters of Ag3Sc2(PO4)3 with changes in tem­per­ature.

4. Conclusion

NaSICON-structured materials belong to the most promising group of solid electrolytes for Li-ion batteries and `beyond Li-ion battery' concepts (e.g. Na and K) due to their superior ionic conductivities. Despite it being well known for decades, the exact phase behaviour is poorly understood. One of the reasons for this is the absence of suitable single crystals that could enable an in-depth investigation of the structure, site preference and phase behaviour as a function of tem­per­ature. Moreover, the low scattering contrast of Na and, in particular, Li makes their analysis particularly difficult.

In this study, we grew NSP single crystals by the flux method and subsequently chemically exchanged Na+ by Ag+ in order to take advantage of the higher scattering contrast of Ag+. This Na+–Ag+ exchange is fast and associated with an increase of lattice parameters and unit-cell volume. The main focus of this study was the full structural characterization of Ag3Sc2(PO4)3 throughout the proposed phase-transition sequence and to evaluate its tem­per­ature dependence.

We found that the NaSICON-type com­pound shows two phase transitions from a low-tem­per­ature monoclinic α-phase to a monoclinic β-phase at about 170 K and to a rhombohedral γ-phase at about 280 K. The framework of [Sc2(PO4)3]3− is rigid and does not change significantly with tem­per­ature and change of symmetry. Major differences are found in the distribution of Ag+, especially during the transition from the β-phase to the γ-phase, suggesting that this transition is actually an order–disorder transition. Furthermore, the transition from the α- to the β-phase is associated with major changes in Ag+-site occupation. Distinct reorientations within the interconnections of polyhedra also occur. Therefore, the main driving force of this transition may also be due to an order–disorder of Ag+, which induces some displacive structural adjustments. Although there is highly anisotropic atomic displacement and splitting of the Ag positions in places, the experimentally refined total amount of Ag+ at different tem­per­atures and in the various structural states is in the range 3.02–3.05 apfu. It is acknowledged that the small observed scatter might be a real effect and could reflect a very small deficit in the phospho­rous content.

The sensitivity of the phase behaviour on the ordering of these ions suggests that small com­positional changes can have a great impact on the phase behaviour and, therefore, also on the ionic conductivity of NaSICON-structured materials.

Supporting information


Computing details top

For all structures, data collection: Bruker APEX2 (Bruker, 2012); cell refinement: Bruker APEX2 (Bruker, 2012); data reduction: Bruker APEX2 (Bruker, 2012); program(s) used to solve structure: SHELXL2014/7 (Sheldrick, 2014); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: ORTEP for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

(100K) top
Crystal data top
O12P3Sc2Ag3.06F(000) = 1307
Mr = 704.90Dx = 4.475 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5927 reflections
a = 15.467 (3) Åθ = 2.8–30.1°
b = 8.9627 (14) ŵ = 7.38 mm1
c = 9.1186 (15) ÅT = 100 K
β = 124.1439 (15)°Box-shaped, pale yellow
V = 1046.2 (3) Å30.14 × 0.14 × 0.09 mm
Z = 4
Data collection top
SMART APEX
diffractometer
1355 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
rotation, ω–scans at 4 different φ positionsθmax = 30.1°, θmin = 2.8°
Absorption correction: multi-scan
multiscan correction with APEX2 software (Bruker 2012)
h = 1920
Tmin = 0.38, Tmax = 0.52k = 1212
5927 measured reflectionsl = 1212
1407 independent reflections
Refinement top
Refinement on F20 constraints
Least-squares matrix: full w = 1/[σ2(Fo2) + 43.1488P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.035(Δ/σ)max < 0.001
wR(F2) = 0.087Δρmax = 1.16 e Å3
S = 1.22Δρmin = 1.19 e Å3
1407 reflectionsExtinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
140 parametersExtinction coefficient: 0.00248 (18)
12 restraints
Special details top

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

Refinement. Refined as a 2-component perfect inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sc10.10203 (8)0.25195 (11)0.05474 (13)0.0050 (2)
P10.35876 (11)0.38433 (16)0.26564 (18)0.0052 (3)
P200.4592 (2)0.250.0046 (4)
O10.1466 (3)0.0559 (5)0.2158 (5)0.0080 (8)
O20.4383 (3)0.0532 (5)0.0841 (5)0.0104 (8)
O30.2570 (3)0.3149 (5)0.2230 (5)0.0088 (8)
O40.3766 (3)0.3584 (5)0.1176 (5)0.0110 (8)
O50.0517 (3)0.1805 (5)0.5612 (5)0.0090 (8)
O60.0781 (3)0.3570 (5)0.2413 (5)0.0073 (8)
Ag10.30043 (6)0.14045 (8)0.45602 (12)0.0124 (3)0.811 (5)
Ag1A0.2700 (15)0.165 (2)0.4865 (16)0.083 (7)0.105 (6)
Ag1B0.314 (3)0.121 (5)0.407 (7)0.020 (12)*0.015 (4)
Ag200.10026 (7)0.250.0123 (2)0.992 (4)
Ag2A0.039 (4)0.097 (5)0.121 (8)0.025 (11)0.012 (2)
Ag3A0.3343 (10)0.0728 (16)0.308 (3)0.039 (4)0.047 (3)
Ag3B0.2899 (11)0.0455 (17)0.141 (3)0.036 (4)0.044 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sc10.0045 (4)0.0046 (5)0.0052 (4)0.0003 (3)0.0024 (3)0.0004 (3)
P10.0038 (6)0.0051 (6)0.0053 (5)0.0001 (5)0.0017 (4)0.0007 (4)
P20.0053 (8)0.0032 (8)0.0059 (8)00.0035 (6)0
O10.0076 (18)0.0060 (18)0.0067 (16)0.0005 (14)0.0017 (14)0.0002 (14)
O20.0122 (19)0.0092 (19)0.0076 (17)0.0025 (16)0.0042 (15)0.0039 (14)
O30.0057 (18)0.0081 (19)0.0108 (18)0.0024 (14)0.0035 (14)0.0001 (14)
O40.0131 (19)0.011 (2)0.0098 (17)0.0004 (16)0.0072 (15)0.0006 (15)
O50.0079 (18)0.0086 (19)0.0067 (16)0.0044 (15)0.0017 (14)0.0016 (14)
O60.0044 (16)0.0092 (19)0.0069 (16)0.0007 (14)0.0023 (14)0.0010 (14)
Ag10.0083 (3)0.0112 (3)0.0063 (3)0.0019 (2)0.0028 (2)0.0028 (2)
Ag1A0.065 (10)0.102 (10)0.026 (5)0.018 (8)0.008 (5)0.005 (5)
Ag20.0174 (3)0.0055 (3)0.0245 (4)00.0182 (3)0
Ag2A0.014 (14)0.018 (15)0.042 (17)0.008 (12)0.014 (12)0.005 (13)
Ag3A0.013 (4)0.027 (6)0.081 (7)0.004 (4)0.030 (4)0.021 (5)
Ag3B0.016 (5)0.026 (6)0.079 (7)0.009 (4)0.034 (4)0.019 (5)
Geometric parameters (Å, º) top
Sc1—O4i2.035 (5)Ag1A—Ag2Aii3.19 (5)
Sc1—O2i2.038 (4)Ag1A—Ag2Avii3.28 (5)
Sc1—O32.071 (4)Ag1A—Ag3Avi3.30 (2)
Sc1—O5ii2.089 (4)Ag1B—Ag3A1.19 (7)
Sc1—O12.141 (4)Ag1B—Ag3A1.19 (7)
Sc1—O62.150 (4)Ag1B—O2vi2.29 (4)
P1—O5iii1.514 (4)Ag1B—Ag3B2.34 (7)
P1—O31.527 (4)Ag1B—Ag1Aiii2.77 (7)
P1—O41.539 (5)Ag1B—Ag3Bvi2.79 (6)
P1—O1iv1.554 (4)Ag1B—Ag2Avii3.23 (6)
P2—O2iv1.513 (4)Ag2—Ag2Aii0.98 (6)
P2—O2v1.513 (4)Ag2—Ag2A0.98 (6)
P2—O6ii1.554 (4)Ag2—O1ii2.488 (4)
P2—O61.554 (4)Ag2—O5ii2.581 (4)
Ag1—Ag1B0.61 (7)Ag2A—O5ii1.73 (6)
Ag1—Ag1A0.70 (3)Ag2A—Ag2Aii1.95 (12)
Ag1—Ag3A1.800 (19)Ag2A—O4viii2.50 (5)
Ag1—Ag1Aiii2.27 (3)Ag2A—Ag1ix3.13 (4)
Ag1—O6iii2.308 (4)Ag2A—Ag1Aii3.19 (5)
Ag1—Ag3Bvi2.440 (19)Ag2A—Ag1Bix3.23 (6)
Ag1—O2vi2.476 (5)Ag2A—Ag1Aix3.28 (5)
Ag1—Ag1iii2.887 (2)Ag3A—Ag3B1.30 (3)
Ag1—Ag3B2.91 (2)Ag3A—O2vi2.375 (17)
Ag1A—Ag1B1.30 (7)Ag3A—O6x2.544 (17)
Ag1A—Ag1Aiii1.71 (5)Ag3A—Ag1Axi3.30 (2)
Ag1A—Ag1iii2.27 (3)Ag3B—Ag1Axi2.27 (2)
Ag1A—Ag3Bvi2.27 (2)Ag3B—O6x2.390 (14)
Ag1A—O6iii2.274 (12)Ag3B—Ag1xi2.440 (19)
Ag1A—Ag3A2.47 (3)Ag3B—O4i2.473 (16)
Ag1A—Ag1Biii2.77 (7)Ag3B—Ag1Bxi2.79 (6)
O4i—Sc1—O2i93.57 (18)O1—Sc1—O687.06 (16)
O4i—Sc1—O394.73 (18)O5iii—P1—O3108.5 (2)
O2i—Sc1—O392.89 (17)O5iii—P1—O4110.3 (3)
O4i—Sc1—O5ii95.31 (18)O3—P1—O4112.5 (2)
O2i—Sc1—O5ii94.81 (18)O5iii—P1—O1iv109.8 (2)
O3—Sc1—O5ii166.93 (17)O3—P1—O1iv108.7 (2)
O4i—Sc1—O190.10 (17)O4—P1—O1iv106.9 (2)
O2i—Sc1—O1176.11 (17)O2iv—P2—O2v112.3 (4)
O3—Sc1—O185.54 (16)O2iv—P2—O6ii110.5 (2)
O5ii—Sc1—O186.10 (17)O2v—P2—O6ii107.9 (2)
O4i—Sc1—O6176.90 (18)O2iv—P2—O6107.9 (2)
O2i—Sc1—O689.29 (17)O2v—P2—O6110.5 (2)
O3—Sc1—O686.32 (17)O6ii—P2—O6107.7 (3)
O5ii—Sc1—O683.24 (17)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x, y, z+1/2; (iii) x+1/2, y+1/2, z+1; (iv) x+1/2, y+1/2, z+1/2; (v) x1/2, y+1/2, z; (vi) x, y, z+1/2; (vii) x+1/2, y+1/2, z+1/2; (viii) x1/2, y1/2, z; (ix) x1/2, y+1/2, z1/2; (x) x+1/2, y1/2, z+1/2; (xi) x, y, z1/2.
(200K) top
Crystal data top
O12Ag3.03P3Sc2F(000) = 3907.3
Mr = 701.67Dx = 4.447 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 50538 reflections
a = 15.5374 (2) Åθ = 1.8–33.1°
b = 8.9703 (1) ŵ = 7.15 mm1
c = 22.5718 (3) ÅT = 200 K
β = 89.9984 (4)°Box-shaped, pale yellow
V = 3145.95 (7) Å30.14 × 0.14 × 0.09 mm
Z = 12
Data collection top
SMART APEX
diffractometer
2271 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
rotation, ω–scans at 4 different φ positionsθmax = 33.1°, θmin = 1.8°
Absorption correction: multi-scan
multiscan correction with APEX2 software (Bruker 2012)
h = 2323
Tmin = 0.51, Tmax = 0.65k = 1313
50538 measured reflectionsl = 3434
6307 independent reflections
Refinement top
Refinement on F20 constraints
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0362P)2 + 12.7531P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.032(Δ/σ)max < 0.001
wR(F2) = 0.107Δρmax = 1.08 e Å3
S = 1.04Δρmin = 0.92 e Å3
6307 reflectionsExtinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
380 parametersExtinction coefficient: 0.00029 (3)
42 restraints
Special details top

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

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sc10.50010 (7)0.50012 (11)0.14829 (4)0.0068 (2)
Sc20.16665 (7)0.50004 (11)0.01837 (4)0.0066 (2)
Sc30.33339 (7)0.00017 (11)0.18514 (4)0.0067 (2)
P10.47918 (9)0.14549 (15)0.08337 (7)0.0079 (3)
P20.64584 (9)0.35413 (15)0.25015 (7)0.0084 (3)
P30.68724 (9)0.64565 (15)0.08316 (7)0.0084 (3)
P40.50.7916 (2)0.250.0079 (4)
P50.33333 (10)0.70845 (14)0.08326 (6)0.0080 (3)
O10.4883 (3)0.3159 (4)0.08891 (17)0.0132 (9)
O20.4250 (3)0.1146 (4)0.02788 (18)0.0209 (11)
O30.5695 (2)0.0755 (4)0.07750 (16)0.0125 (8)
O40.4365 (3)0.0808 (5)0.13861 (18)0.0194 (10)
O50.5915 (3)0.3854 (4)0.19487 (18)0.0205 (11)
O60.6551 (3)0.1837 (4)0.25570 (17)0.0125 (9)
O70.7354 (2)0.4248 (4)0.24389 (16)0.0127 (8)
O80.6035 (3)0.4196 (4)0.30531 (18)0.0196 (10)
O90.5975 (2)0.5752 (4)0.08933 (16)0.0140 (9)
O100.7297 (3)0.5803 (5)0.02801 (18)0.0195 (9)
O110.7417 (3)0.6148 (4)0.13859 (18)0.0203 (10)
O120.6779 (3)0.8161 (4)0.07766 (17)0.0112 (9)
O130.5109 (3)0.6949 (4)0.19513 (18)0.0192 (10)
O140.5805 (2)0.8920 (4)0.25575 (16)0.0124 (9)
O150.4133 (2)0.6090 (4)0.08927 (16)0.0124 (9)
O160.3449 (3)0.8052 (4)0.0283 (2)0.0211 (11)
O170.3223 (3)0.8051 (4)0.13828 (19)0.0196 (10)
O180.2531 (2)0.6091 (4)0.07772 (16)0.0112 (9)
Ag1A0.3268 (4)0.3601 (7)0.0994 (6)0.0365 (15)0.301 (15)
Ag1B0.3373 (3)0.3576 (5)0.0726 (6)0.0425 (17)0.385 (15)
Ag2A0.5141 (3)0.8265 (4)0.0943 (6)0.0377 (15)0.374 (15)
Ag2B0.5105 (3)0.8112 (8)0.0677 (6)0.0342 (15)0.285 (15)
Ag3A0.65575 (19)0.3122 (3)0.1006 (3)0.0353 (14)0.220 (4)
Ag3B0.65310.3260.07430.0463 (9)0.446 (4)
Ag40.5040 (6)0.14149 (14)0.2378 (2)0.0411 (18)0.3213 (15)
Ag5A0.6812 (3)0.6727 (4)0.2635 (6)0.0332 (14)0.332 (15)
Ag5B0.6775 (3)0.6858 (6)0.2363 (6)0.0363 (15)0.346 (15)
Ag6A0.6407 (6)0.0407 (11)0.16664 (12)0.107 (3)0.393 (12)
Ag6B0.7000 (7)1.0032 (12)0.16681 (13)0.119 (3)0.369 (13)
Ag6C0.6536 (9)0.9433 (15)0.1664 (2)0.103 (4)0.267 (13)
Ag7A0.5345 (7)0.4392 (11)0.0026 (3)0.034 (2)0.142 (7)
Ag7B0.4905 (6)0.4301 (14)0.0013 (2)0.056 (2)0.199 (8)
Ag7C0.4600 (9)0.4833 (13)0.0005 (3)0.055 (2)0.171 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sc10.0076 (6)0.0077 (5)0.0050 (4)0.0003 (4)0.0004 (4)0.0002 (4)
Sc20.0067 (5)0.0067 (5)0.0064 (4)0.0001 (4)0.0006 (4)0.0006 (4)
Sc30.0072 (5)0.0069 (5)0.0059 (4)0.0001 (4)0.0009 (4)0.0006 (4)
P10.0055 (6)0.0078 (6)0.0103 (6)0.0017 (5)0.0008 (6)0.0042 (5)
P20.0057 (7)0.0064 (6)0.0129 (7)0.0008 (5)0.0005 (6)0.0034 (5)
P30.0064 (7)0.0079 (6)0.0109 (6)0.0015 (5)0.0002 (6)0.0033 (5)
P40.0061 (9)0.0066 (9)0.0109 (9)00.0051 (8)0
P50.0070 (6)0.0066 (6)0.0104 (6)0.0004 (6)0.0052 (6)0.0000 (6)
O10.018 (2)0.0088 (18)0.0130 (19)0.0012 (16)0.0003 (17)0.0020 (15)
O20.016 (2)0.022 (2)0.025 (2)0.0026 (18)0.009 (2)0.0094 (18)
O30.0076 (18)0.0178 (19)0.0121 (18)0.0010 (17)0.0018 (15)0.0007 (17)
O40.016 (2)0.020 (2)0.023 (2)0.0015 (19)0.0094 (18)0.0018 (19)
O50.015 (2)0.018 (2)0.028 (2)0.0025 (17)0.012 (2)0.0079 (18)
O60.015 (2)0.0052 (17)0.018 (2)0.0037 (15)0.0006 (18)0.0024 (16)
O70.0090 (18)0.0161 (19)0.0131 (18)0.0029 (17)0.0027 (16)0.0015 (17)
O80.018 (2)0.016 (2)0.025 (2)0.0011 (18)0.0071 (19)0.0042 (19)
O90.0095 (19)0.0171 (19)0.0154 (19)0.0044 (17)0.0007 (16)0.0056 (17)
O100.017 (2)0.018 (2)0.024 (2)0.0064 (18)0.0102 (18)0.0021 (19)
O110.015 (2)0.023 (2)0.023 (2)0.0011 (18)0.0100 (19)0.0103 (18)
O120.017 (2)0.0050 (17)0.0114 (18)0.0007 (15)0.0022 (17)0.0027 (15)
O130.018 (2)0.018 (2)0.021 (2)0.0006 (18)0.0049 (19)0.0102 (18)
O140.012 (2)0.0125 (19)0.0127 (19)0.0056 (15)0.0035 (17)0.0013 (15)
O150.0083 (19)0.0132 (19)0.0158 (19)0.0042 (15)0.0026 (17)0.0040 (16)
O160.021 (2)0.0122 (19)0.030 (2)0.0009 (17)0.008 (2)0.0125 (18)
O170.018 (2)0.014 (2)0.027 (2)0.0032 (17)0.007 (2)0.0122 (18)
O180.0098 (19)0.015 (2)0.0089 (17)0.0035 (16)0.0014 (16)0.0002 (15)
Ag1A0.0219 (15)0.0134 (12)0.074 (4)0.0051 (10)0.029 (2)0.008 (2)
Ag1B0.0164 (12)0.0097 (8)0.102 (4)0.0046 (7)0.034 (2)0.0088 (18)
Ag2A0.0121 (9)0.0101 (9)0.091 (4)0.0028 (6)0.0162 (18)0.0230 (16)
Ag2B0.0085 (10)0.0241 (15)0.070 (4)0.0020 (10)0.0069 (19)0.029 (2)
Ag3A0.0083 (14)0.0229 (16)0.075 (4)0.0012 (11)0.0067 (13)0.0323 (15)
Ag3B0.0140 (8)0.0156 (8)0.109 (2)0.0055 (6)0.0217 (10)0.0310 (10)
Ag40.0206 (16)0.0093 (6)0.093 (5)0.0053 (11)0.038 (3)0.0079 (10)
Ag5A0.0134 (11)0.0112 (9)0.075 (4)0.0046 (7)0.0192 (18)0.0197 (16)
Ag5B0.0096 (9)0.0198 (12)0.080 (4)0.0007 (8)0.0089 (17)0.0297 (18)
Ag6A0.154 (6)0.157 (5)0.0100 (9)0.055 (3)0.0344 (17)0.0198 (16)
Ag6B0.109 (5)0.237 (7)0.0111 (11)0.020 (4)0.0193 (16)0.035 (2)
Ag6C0.163 (9)0.125 (6)0.0203 (18)0.076 (5)0.041 (3)0.029 (2)
Ag7A0.051 (4)0.041 (4)0.011 (2)0.004 (3)0.009 (2)0.003 (2)
Ag7B0.045 (4)0.112 (5)0.0105 (15)0.025 (4)0.007 (2)0.019 (2)
Ag7C0.089 (5)0.060 (5)0.0144 (19)0.036 (4)0.028 (2)0.010 (3)
Geometric parameters (Å, º) top
Sc1—O52.045 (4)Ag3A—Ag7A3.120 (12)
Sc1—O132.049 (4)Ag3A—Ag6Bvii3.223 (10)
Sc1—O8i2.052 (4)Ag3A—O18x2.424 (5)
Sc1—O92.124 (4)Ag3B—O18x2.492 (4)
Sc1—O152.133 (3)Ag3B—O16iv2.598 (5)
Sc1—O12.136 (4)Ag3B—Ag7A2.654 (11)
Sc2—O2ii2.044 (3)Ag3B—Ag7Civ2.977 (10)
Sc2—O16iii2.047 (4)Ag3B—Ag7B3.189 (8)
Sc2—O10iv2.051 (4)Ag4—Ag4i0.564 (13)
Sc2—O3v2.126 (4)Ag4—O6i2.506 (10)
Sc2—O12vi2.132 (3)Ag4—O14vii2.566 (6)
Sc2—O182.135 (3)Ag4—O14viii2.599 (6)
Sc3—O11vi2.047 (4)Ag4—Ag6A2.812 (11)
Sc3—O42.048 (4)Ag4—Ag6Ai3.244 (11)
Sc3—O17vii2.052 (4)Ag5A—Ag5B0.628 (4)
Sc3—O14viii2.124 (3)Ag5A—O17i2.516 (12)
Sc3—O6i2.127 (4)Ag5A—O6xi2.581 (6)
Sc3—O7vi2.129 (4)Ag5A—Ag6Bxii2.862 (14)
P1—O41.527 (5)Ag5A—Ag6C3.299 (16)
P1—O21.534 (4)Ag5B—O7xi2.574 (6)
P1—O11.540 (4)Ag5B—Ag6C2.822 (17)
P1—O31.543 (4)Ag5B—Ag6B3.270 (14)
P2—O81.525 (4)Ag5B—Ag6Bxii3.329 (14)
P2—O51.533 (4)Ag6A—Ag6Cvii0.897 (9)
P2—O71.536 (4)Ag6A—Ag6Bvii0.981 (7)
P2—O61.541 (4)Ag6A—O14vii2.588 (8)
P3—O101.526 (4)Ag6A—Ag2Avii3.198 (13)
P3—O111.536 (4)Ag6A—Ag4i3.244 (11)
P3—O91.538 (4)Ag6B—Ag6C0.899 (7)
P3—O121.541 (3)Ag6B—Ag6Aix0.981 (6)
P4—O13i1.522 (4)Ag6B—O7xi2.359 (6)
P4—O131.522 (4)Ag6B—O18xiii2.372 (7)
P4—O14i1.547 (4)Ag6B—Ag1Axiii2.801 (15)
P4—O141.547 (4)Ag6B—Ag5Axi2.862 (14)
P5—O171.524 (4)Ag6B—Ag3Aix3.224 (10)
P5—O161.525 (4)Ag6B—Ag1Bxiii3.284 (14)
P5—O151.535 (4)Ag6B—Ag5Bxi3.329 (14)
P5—O181.537 (4)Ag6C—Ag6Aix0.897 (9)
Ag1A—Ag1B0.628 (6)Ag6C—Ag1Axiii3.175 (17)
Ag1A—Ag6Bvi2.800 (15)Ag6C—Ag4ix3.341 (16)
Ag1A—Ag6Cvi3.175 (17)Ag7A—Ag7B0.695 (9)
Ag1A—Ag7C3.239 (17)Ag7A—Ag7Civ0.704 (9)
Ag1A—O12vi2.398 (6)Ag7A—Ag7C1.225 (17)
Ag1A—O8i2.465 (11)Ag7A—Ag7Biv1.235 (16)
Ag1B—Ag7C2.748 (18)Ag7A—Ag7Aiv1.53 (2)
Ag1B—Ag7B2.977 (14)Ag7A—O15iv2.268 (7)
Ag1B—Ag7Aiv3.189 (14)Ag7A—Ag2Biv2.837 (15)
Ag1B—Ag6Bvi3.284 (14)Ag7A—Ag1Biv3.189 (14)
Ag1B—O12vi2.507 (7)Ag7B—Ag7C0.674 (9)
Ag1B—O10iv2.559 (12)Ag7B—Ag7Civ1.093 (14)
Ag2A—Ag2B0.620 (5)Ag7B—Ag7Aiv1.235 (16)
Ag2A—Ag6C2.906 (14)Ag7B—Ag7Biv1.29 (2)
Ag2A—Ag7Biv3.116 (15)Ag7B—O9iv2.412 (7)
Ag2A—Ag6Aix3.198 (13)Ag7B—O15iv2.511 (9)
Ag2A—O3ix2.424 (5)Ag7B—Ag2Biv2.632 (17)
Ag2B—Ag7Biv2.632 (17)Ag7B—Ag2Aiv3.116 (15)
Ag2B—Ag7Aiv2.837 (15)Ag7C—Ag7Aiv0.704 (9)
Ag2B—Ag7Civ3.091 (16)Ag7C—Ag7Biv1.093 (14)
Ag2B—Ag6C3.364 (15)Ag7C—Ag7Civ1.28 (3)
Ag2B—O2iv2.469 (12)Ag7C—O9iv2.276 (7)
Ag2B—O3ix2.552 (9)Ag7C—Ag3Biv2.977 (10)
Ag3A—Ag3B0.607 (6)Ag7C—Ag2Biv3.091 (16)
Ag3A—Ag6A2.865 (10)
O5—Sc1—O1396.14 (16)O17vii—Sc3—O6i172.14 (16)
O5—Sc1—O8i96.05 (17)O14viii—Sc3—O6i84.62 (14)
O13—Sc1—O8i95.81 (18)O11vi—Sc3—O7vi88.97 (17)
O5—Sc1—O989.26 (17)O4—Sc3—O7vi172.32 (15)
O13—Sc1—O989.69 (18)O17vii—Sc3—O7vi89.44 (18)
O8i—Sc1—O9171.90 (15)O14viii—Sc3—O7vi85.07 (15)
O5—Sc1—O15172.29 (18)O6i—Sc3—O7vi85.12 (15)
O13—Sc1—O1589.05 (15)O4—P1—O2111.1 (2)
O8i—Sc1—O1589.07 (15)O4—P1—O1110.5 (2)
O9—Sc1—O1585.06 (15)O2—P1—O1107.2 (2)
O5—Sc1—O189.59 (15)O4—P1—O3108.1 (2)
O13—Sc1—O1172.16 (16)O2—P1—O3110.8 (2)
O8i—Sc1—O188.88 (17)O1—P1—O3109.1 (2)
O9—Sc1—O185.03 (16)O8—P2—O5110.9 (2)
O15—Sc1—O184.73 (14)O8—P2—O7107.9 (2)
O2ii—Sc2—O16iii96.07 (16)O5—P2—O7110.4 (2)
O2ii—Sc2—O10iv96.28 (18)O8—P2—O6110.8 (2)
O16iii—Sc2—O10iv96.09 (19)O5—P2—O6107.4 (2)
O2ii—Sc2—O3v89.20 (16)O7—P2—O6109.4 (2)
O16iii—Sc2—O3v89.37 (18)O10—P3—O11110.9 (2)
O10iv—Sc2—O3v171.80 (15)O10—P3—O9108.0 (2)
O2ii—Sc2—O12vi89.34 (16)O11—P3—O9110.6 (2)
O16iii—Sc2—O12vi172.05 (17)O10—P3—O12110.9 (2)
O10iv—Sc2—O12vi89.08 (17)O11—P3—O12107.2 (2)
O3v—Sc2—O12vi84.87 (16)O9—P3—O12109.3 (2)
O2ii—Sc2—O18171.84 (18)O13i—P4—O13110.5 (3)
O16iii—Sc2—O1889.24 (15)O13i—P4—O14i108.1 (2)
O10iv—Sc2—O1889.28 (16)O13—P4—O14i110.7 (2)
O3v—Sc2—O1884.66 (14)O13i—P4—O14110.7 (2)
O12vi—Sc2—O1884.77 (14)O13—P4—O14108.1 (2)
O11vi—Sc3—O495.95 (17)O14i—P4—O14108.8 (3)
O11vi—Sc3—O17vii96.06 (16)O17—P5—O16110.6 (2)
O4—Sc3—O17vii95.87 (19)O17—P5—O15110.4 (2)
O11vi—Sc3—O14viii171.97 (18)O16—P5—O15107.9 (3)
O4—Sc3—O14viii89.45 (16)O17—P5—O18107.8 (2)
O17vii—Sc3—O14viii89.27 (15)O16—P5—O18111.0 (2)
O11vi—Sc3—O6i89.53 (15)O15—P5—O18109.0 (2)
O4—Sc3—O6i89.02 (16)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+1/2, y+1/2, z; (iii) x+1/2, y+3/2, z; (iv) x+1, y+1, z; (v) x1/2, y+1/2, z; (vi) x1/2, y1/2, z; (vii) x, y1, z; (viii) x+1, y1, z+1/2; (ix) x, y+1, z; (x) x+1/2, y1/2, z; (xi) x+3/2, y+1/2, z+1/2; (xii) x+3/2, y1/2, z+1/2; (xiii) x+1/2, y+1/2, z.
(300K) top
Crystal data top
O12P3Sc2Ag3.05Dx = 4.44 Mg m3
Mr = 703.49Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c:HCell parameters from 7548 reflections
Hall symbol: -R 3 2"cθ = 2.7–29.9°
a = 8.9756 (4) ŵ = 7.31 mm1
c = 22.6248 (10) ÅT = 295 K
V = 1578.49 (16) Å3Box-shaped, pale yellow
Z = 60.14 × 0.14 × 0.09 mm
F(000) = 1957
Data collection top
SMART APEX
diffractometer
472 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
rotation, ω–scans at 4 different φ positionsθmax = 29.9°, θmin = 2.7°
Absorption correction: multi-scan
multiscan correction with APEX2 software (Bruker 2012)
h = 1212
Tmin = 0.38, Tmax = 0.52k = 1212
7548 measured reflectionsl = 3030
496 independent reflections
Refinement top
Refinement on F20 constraints
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0213P)2 + 4.9245P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.018(Δ/σ)max = 0.001
wR(F2) = 0.044Δρmax = 0.39 e Å3
S = 1.11Δρmin = 0.36 e Å3
496 reflectionsExtinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
60 parametersExtinction coefficient: 0.00216 (14)
0 restraints
Special details top

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

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sc1000.14842 (2)0.00827 (15)
P10.29136 (6)00.250.00926 (16)
O10.18295 (17)0.97638 (18)0.19508 (6)0.0219 (3)
O20.19558 (15)0.17300 (15)0.08945 (5)0.0154 (3)
Ag110.017 (2)0.0807 (6)0.00192 (12)0.0774 (17)0.1688 (7)
Ag210.021 (3)0.221 (3)0.0255 (11)0.039 (8)*0.0085 (10)
Ag220.0155 (6)0.3117 (11)0.0625 (5)0.0418 (17)0.140 (9)
Ag20.0256 (4)0.33330.08330.056 (3)0.381 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sc10.00878 (18)0.00878 (18)0.0073 (2)0.00439 (9)00
P10.0073 (2)0.0095 (3)0.0117 (3)0.00473 (13)0.00210 (9)0.00421 (18)
O10.0185 (6)0.0236 (7)0.0244 (6)0.0111 (5)0.0089 (5)0.0025 (5)
O20.0114 (5)0.0135 (5)0.0158 (5)0.0022 (5)0.0032 (4)0.0029 (4)
Ag110.0746 (19)0.126 (2)0.0142 (5)0.037 (5)0.0002 (18)0.0271 (13)
Ag220.0142 (10)0.024 (2)0.076 (3)0.0017 (9)0.0007 (11)0.034 (2)
Ag20.0109 (7)0.0152 (12)0.143 (8)0.0076 (6)0.0143 (17)0.029 (3)
Geometric parameters (Å, º) top
Sc1—O1i2.0504 (12)Ag11—Ag211.35 (3)
Sc1—O1ii2.0504 (12)Ag11—Ag21x1.71 (3)
Sc1—O1iii2.0505 (12)Ag11—Ag21xi1.85 (3)
Sc1—O2iv2.1324 (11)Ag11—Ag21iv2.31 (3)
Sc1—O2v2.1324 (11)Ag11—Ag21v2.41 (3)
Sc1—O22.1324 (11)Ag21—Ag221.18 (3)
P1—O1iii1.5261 (12)Ag21—Ag21.64 (3)
P1—O1vi1.5262 (12)Ag21—Ag11xi1.71 (3)
P1—O2vii1.5398 (11)Ag21—Ag11x1.85 (3)
P1—O2viii1.5398 (11)Ag21—Ag22xiii2.11 (3)
O1—Ag21ix2.22 (2)Ag21—Ag21xi2.22 (4)
O1—Ag22ix2.420 (8)Ag21—Ag21x2.22 (4)
O2—Ag21iv2.28 (2)Ag21—Ag11v2.31 (3)
O2—Ag11x2.299 (3)Ag22—Ag20.501 (12)
O2—Ag212.33 (2)Ag22—Ag22xiii1.00 (2)
O2—Ag22iv2.362 (7)Ag22—Ag21xiii2.11 (3)
O2—Ag112.419 (9)Ag22—O2v2.362 (7)
O2—Ag2iv2.4504 (14)Ag22—O1xiv2.420 (8)
O2—Ag11iv2.491 (11)Ag22—Ag11xi2.784 (18)
O2—Ag222.559 (6)Ag22—Ag11x2.952 (18)
O2—Ag22.572 (3)Ag22—Ag21xi3.08 (3)
Ag11—Ag11xi0.668 (3)Ag2—Ag22xiii0.501 (12)
Ag11—Ag11iv1.147 (4)Ag2—Ag21xiii1.64 (3)
Ag11—Ag11xii1.327 (5)Ag2—Ag11xiii2.892 (5)
O1i—Sc1—O1ii95.87 (5)O1ii—Sc1—O2172.26 (5)
O1i—Sc1—O1iii95.87 (5)O1iii—Sc1—O289.27 (5)
O1ii—Sc1—O1iii95.87 (5)O2iv—Sc1—O284.99 (5)
O1i—Sc1—O2iv172.26 (5)O2v—Sc1—O284.99 (5)
O1ii—Sc1—O2iv89.27 (5)O1iii—P1—O1vi110.77 (11)
O1iii—Sc1—O2iv89.34 (5)O1iii—P1—O2vii110.73 (7)
O1i—Sc1—O2v89.27 (5)O1vi—P1—O2vii107.78 (7)
O1ii—Sc1—O2v89.34 (5)O1iii—P1—O2viii107.78 (7)
O1iii—Sc1—O2v172.26 (5)O1vi—P1—O2viii110.73 (7)
O2iv—Sc1—O2v84.99 (5)O2vii—P1—O2viii109.05 (10)
O1i—Sc1—O289.34 (5)
Symmetry codes: (i) y+1, xy+1, z; (ii) x+y1, x, z; (iii) x, y1, z; (iv) x+y, x, z; (v) y, xy, z; (vi) xy+1, y+1, z+1/2; (vii) x+2/3, y+1/3, z+1/3; (viii) x+y+1/3, y1/3, z+1/6; (ix) x+1/3, x+y+2/3, z+1/6; (x) y, x+y, z; (xi) xy, x, z; (xii) x, y, z; (xiii) xy+1/3, y+2/3, z+1/6; (xiv) x+1/3, x+y1/3, z+1/6.
(520K) top
Crystal data top
O12P3Sc2Ag3.02Dx = 4.404 Mg m3
Mr = 700.59Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c:HCell parameters from 4628 reflections
Hall symbol: -R 3 2"cθ = 2.7–38.4°
a = 8.9671 (8) ŵ = 7.24 mm1
c = 22.7622 (19) ÅT = 520 K
V = 1585.1 (3) Å3Box-shaped, pale yellow
Z = 60.12 × 0.12 × 0.08 mm
F(000) = 1949.6
Data collection top
SMART APEX
diffractometer
700 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
rotation, ω–scans at different φ positionsθmax = 38.4°, θmin = 2.7°
Absorption correction: multi-scan
multiscan correction with APEX2 software (Bruker 2012)
h = 1215
Tmin = 0.417, Tmax = 0.581k = 158
4628 measured reflectionsl = 3930
924 independent reflections
Refinement top
Refinement on F20 constraints
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0271P)2 + 2.9952P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.033(Δ/σ)max < 0.001
wR(F2) = 0.071Δρmax = 0.78 e Å3
S = 1.07Δρmin = 0.64 e Å3
924 reflectionsExtinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
60 parametersExtinction coefficient: 0.00173 (18)
0 restraints
Special details top

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

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sc1000.14848 (2)0.01194 (13)
P10.29026 (7)00.250.01233 (14)
O10.1810 (2)0.9740 (2)0.19569 (7)0.0292 (3)
O20.19695 (17)0.17375 (18)0.09026 (6)0.0219 (3)
Ag110.014 (2)0.0879 (8)0.00319 (13)0.107 (2)0.1692 (9)
Ag210.0180 (18)0.223 (2)0.0271 (7)0.028 (4)*0.0136 (12)
Ag220.0172 (6)0.3069 (10)0.0576 (4)0.057 (2)0.142 (7)
Ag20.0253 (3)0.33330.08330.069 (4)0.357 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sc10.01192 (16)0.01192 (16)0.01199 (19)0.00596 (8)00
P10.00960 (19)0.0121 (3)0.0161 (2)0.00606 (13)0.00224 (11)0.0045 (2)
O10.0259 (7)0.0332 (8)0.0318 (7)0.0172 (7)0.0122 (6)0.0016 (7)
O20.0147 (6)0.0177 (6)0.0249 (6)0.0018 (5)0.0056 (5)0.0042 (5)
Ag110.091 (3)0.178 (4)0.0262 (7)0.049 (6)0.003 (3)0.0419 (19)
Ag220.0199 (9)0.043 (3)0.091 (4)0.0032 (11)0.0007 (14)0.044 (3)
Ag20.0184 (7)0.0220 (12)0.166 (10)0.0110 (6)0.0191 (17)0.038 (3)
Geometric parameters (Å, º) top
Sc1—O1i2.0542 (14)Ag11—Ag211.310 (19)
Sc1—O1ii2.0542 (14)Ag11—Ag11xii1.475 (6)
Sc1—O1iii2.0542 (14)Ag11—Ag21x1.77 (2)
Sc1—O22.1334 (13)Ag11—Ag21xi1.87 (3)
Sc1—O2iv2.1334 (13)Ag11—Ag222.309 (12)
Sc1—O2v2.1334 (13)Ag11—Ag21iv2.40 (2)
P1—O1ii1.5215 (14)Ag21—Ag221.03 (2)
P1—O1vi1.5215 (14)Ag21—Ag21.601 (19)
P1—O2vii1.5360 (14)Ag21—Ag11xi1.77 (2)
P1—O2viii1.5361 (14)Ag21—Ag11x1.87 (3)
O1—Ag21ix2.244 (14)Ag21—Ag22xiii2.18 (2)
O1—Ag22ix2.360 (8)Ag21—Ag21x2.28 (3)
O2—Ag21iv2.269 (13)Ag21—Ag11v2.40 (2)
O2—Ag11x2.325 (3)Ag22—Ag20.623 (11)
O2—Ag212.354 (13)Ag22—Ag22xiii1.24 (2)
O2—Ag22iv2.367 (7)Ag22—Ag21xiii2.18 (2)
O2—Ag112.440 (10)Ag22—Ag11xi2.709 (17)
O2—Ag2iv2.4455 (16)Ag22—Ag11x2.828 (18)
O2—Ag11iv2.474 (11)Ag22—Ag21xi3.038 (17)
O2—Ag222.550 (6)Ag2—Ag22xiii0.623 (11)
O2—Ag22.578 (3)Ag2—Ag21xiii1.601 (19)
Ag11—Ag11xi0.748 (3)Ag2—Ag11xiii2.821 (4)
Ag11—Ag11iv1.271 (5)
O1i—Sc1—O1ii95.14 (6)O1ii—Sc1—O2v173.12 (6)
O1i—Sc1—O1iii95.14 (6)O1iii—Sc1—O2v89.24 (6)
O1ii—Sc1—O1iii95.14 (6)O2—Sc1—O2v85.47 (6)
O1i—Sc1—O289.24 (6)O2iv—Sc1—O2v85.47 (6)
O1ii—Sc1—O289.73 (6)O1ii—P1—O1vi110.83 (13)
O1iii—Sc1—O2173.12 (6)O1ii—P1—O2vii110.73 (8)
O1i—Sc1—O2iv173.12 (6)O1vi—P1—O2vii107.85 (8)
O1ii—Sc1—O2iv89.24 (6)O1ii—P1—O2viii107.86 (8)
O1iii—Sc1—O2iv89.73 (6)O1vi—P1—O2viii110.73 (8)
O2—Sc1—O2iv85.48 (6)O2vii—P1—O2viii108.84 (12)
O1i—Sc1—O2v89.73 (6)
Symmetry codes: (i) y+1, xy+1, z; (ii) x, y1, z; (iii) x+y1, x, z; (iv) x+y, x, z; (v) y, xy, z; (vi) xy+1, y+1, z+1/2; (vii) x+2/3, y+1/3, z+1/3; (viii) x+y+1/3, y1/3, z+1/6; (ix) x+1/3, x+y+2/3, z+1/6; (x) y, x+y, z; (xi) xy, x, z; (xii) x, y, z; (xiii) xy+1/3, y+2/3, z+1/6.
 

Acknowledgements

We would like to express our kind thanks to Edgar Dachs (Salzburg) for performing the low-tem­per­ature heat capacity measurements.

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