Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, with nominal formula Cu2ScZr(PO4)3, has a beige coloration and displays fast Cu+ cation conduction at elevated temperatures. It adopts a NASICON-type structure in the space group R\overline{3}c. The examined crystal was an obverse-reverse twin with approximately equal twin components. The [ScIIIZrIV(PO4)3]2- framework is composed of corner-sharing Sc/ZrO6 octa­hedra and PO4 tetra­hedra. The Sc and Zr atoms are disordered on one atomic site on a crystallographic threefold axis. The P atom of the phosphate group lies on a crystallographic twofold axis. Nonframework Cu+ cations occupy three positions. Two of the Cu+ positions generate an approximately circular distribution around a site of \overline{3} symmetry, referred to as the M1 site in the NASICON-type structure. The other Cu+ position is situated close to the twofold symmetric M2 site, displaced into a position with a distorted square-based pyramidal coordination geometry. The structure has been determined at 100, 200 and 300 K. Changes in the refined site-occupancy factors of the Cu+ positions suggest increased mobility of Cu+ around the circular orbit close to the M1 site at room temperature, but no movement into or out of the M2 site. Free refinement of the Cu site-occupancy factors suggests that the formula of the crystal is Cu1.92(1)ScZr(PO4)3, which is consistent with the low-level presence of Cu2+ exclusively in the M2 site.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113000553/ku3084sup1.cif
Contains datablocks global, I_100K, I_200K, I_300K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113000553/ku3084I_100Ksup2.hkl
Contains datablock I_100K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113000553/ku3084I_200Ksup3.hkl
Contains datablock I_200K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113000553/ku3084I_300Ksup4.hkl
Contains datablock I_300K

Comment top

In 1976, Hong (1976) and Goodenough et al. (1976) discovered fast sodium cation transport in the solid-solution series Na1+xZr2(SiO4)x(PO4)3-x (0 x 3), which became known by the acronym NASICON (Na+ superionic conductor). This material attracted a great deal of interest at that time for use as a solid electrolyte in rechargeable sodium batteries for vehicle propulsion. Subsequently, many other NASICON-type compounds have been discovered. For example, Yao & Fray (1983) substituted Cu+ for Na+ in the phosphate end-member, NaZr2(PO4)3, which resulted in the fast Cu+ cation conductor CuZr2(PO3)3 (CUSICON). This material has been used as a high-temperature solid electrolyte in electrochemical sensors designed for the metallurgical industry. Several other copper(I) phosphate analogues have been reported, including CuTi2(PO4)3 (Mbandza et al., 1985), CuxNb1-xTi1+x(PO4)3 (0 x 1) (El Jazouli et al., 1985), Cu1+xCrxTi2-x(PO4)3 (0 x 1) (El Jazouli et al., 1985), CuTiZr(PO4)3 (Berry et al., 1992; Warner et al., 1992), Cu2CrZr(PO4)3 (Boireau et al., 1992), Cu2ScZr(PO4)3 (Warner et al., 1992), CuSn2(PO4)3 (Serghini et al., 1995) and CuHf2(PO4)3 (Ahmamouch et al., 1997). Technologically more desirable copper(I)-rich compounds that promise enhanced ionic conductivity, such as Cu3Sc2(PO4)3, have not yet been prepared. And since there are no known crystalline copper(I) silicates of any kind, it would appear that the existence of a siliceous copper(I)-rich analogue of NASICON, namely Cu1+xZr2(SiO4)x(PO4)3-x (0 < x 3), is improbable. Further details of CUSICON-type compounds are described in the monograph by Warner (2011).

Na4Zr2(SiO4)3 is considered as the prototype NASICON structure. The Na+ cations are accommodated within two distinct crystallographic sites, designated M1 and M2, as described by the formula (M1)1(M2)3[Zr2(SiO4)3]. The Cu+ cation has a strong preference for the less numerous M1 site, and it occupies this site solely in both CuZr2(PO4)3 (Bussereau et al., 1992) and CuTi2(PO4)3 (McCarron et al., 1987). An interesting feature of these copper analogues is that the Cu+ cations are distributed over six off-centred equivalent positions around the M1 site, which gives rise to a `daisy-like' feature. Furthermore, as a consequence of the large size of the M1 site, it is possible, at least in CuZr2(PO4)3, to have two Cu+ cations within the same M1 site. Fargin et al. (1992, 1994) used extended X-ray absorption fine structure (EXAFS) to show that about 20% of the M1 sites are occupied by Cu+—Cu+ pairs, about 60% are singly occupied by Cu+ cations and the remaining 20% are empty. The EXAFS results indicate Cu+—Cu+ pairs separated by a remarkably short distance of 2.40 Å, which is shorter than the Cu—Cu interatomic distance of 2.56 Å in face-centred cubic (fcc) copper metal. The presence of Cu+—Cu+ pairs is considered to be the source of the intense green luminescence (540 nm emission) of CuZr2(PO4)3 under short-wavelength ultraviolet light at room temperature (Maihold & Wulff, 1987; Le Polles et al., 1988). By comparison, Cu+—Cu+ pairs do not exist in CuTi2(PO4)3 on account of the smaller M1 site in this material (Fargin et al., 1994), which may explain why that phase is non-luminescent.

The Cu+ cations in both CuZr2(PO4)3 and CuTi2(PO4)3 have a high mobility above 600 K (Warner et al., 1992), and the conduction pathway necessitates their movement through the infinite sequence M1–M2–M1–M2–··· in three dimensions. This would imply at least a transient occupancy of the M2 site at high temperature. The crystal structure of Cu2CrZr(PO4)3, solved using powder neutron diffraction data (Boireau et al., 1993), indicates that the M2 site is partially occupied by Cu+ cations at room temperature in this more Cu(I)-rich compound, CuI(M1)1.5CuI(M2)0.5[CrZr(SiO4)3]. Furthermore, the high occupancy factor of 1.5 for the M1 site is consistent with the existence of Cu+—Cu+ pairs, as discussed above.

This present article reports our findings regarding the Cu+ cation occupancy of the M1 and M2 sites in the NASICON-type copper scandium zirconium phosphate, Cu2ScZr(PO4)3. The structure has been determined at 100, 200 and 300 K. The unit-cell volumes demonstrate that there is no significant thermal expansion over this temperature range, which is a characteristic feature of NASICON-type phosphates (Anantharamulu et al., 2011). The [ScIIIZrIV(PO4)3]2- framework is essentially identical to that in all published NASICON-type structures, comprising corner-sharing Sc/ZrO6 octahedra and PO4 tetrahedra (Fig. 1). The Sc and Zr atoms assume a statistical distribution on a single atomic site within the framework. Atom Sc1/Zr1 lies on a three-fold rotation axis and displays two unique Sc/Zr—O bond distances of 2.041 (2) and 2.112 (2) Å at 300 K. Atom P1 lies on a two-fold rotation axis and displays two unique P—O bond distances of 1.520 (2) and 1.547 (2) Å at 300 K. The Sc/Zr—O and P—O bonds do not change significantly over the measured temperature range. The Sc/Zr—O distances are marginally larger than those reported for the X-ray investigation of CuZr2(PO4)3 at 298 K [2.004 (5) and 2.082 (5) Å; Bussereau et al., 1992], but the fact that the difference is small must reflect the closely comparable ionic radii for ScIII and ZrIV in octahedral coordination.

Bearing in mind that Cu2ScZr(PO4)3 exhibits enhanced ionic conductivity compared with CuZr2(PO4)3 (Warner et al., 1992), the main point of interest in the structure is the location of the non-framework Cu+ cations. The NASICON-type structure contains two distinct non-framework sites that are occupied by Na+ in the prototype compound Na4Zr2(SiO4)3 (Kohler et al., 1983). The M1 site has 3 symmetry, surrounded by six O atoms in a trigonal-antiprismatic geometry, and the M2 site has 2 symmetry, surrounded by an irregular arrangement of eight O atoms. In the asymmetric unit as reported here (Table 1), the M1 site closest to the Cu+ positions is at (1/3,2/3,1/6) and the M2 site closest to the Cu+ positions has approximate coordinates (0,1/3,1/12). Three Cu+ positions are apparent for Cu2ScZr(PO4)3: atom Cu1 lies ca 1.30 Å from the M1 site, and six equivalent positions are generated by the 3 symmetry of the M1 site (Fig. 1); atom Cu2 lies ca 1.37 Å from the M2 site, and two equivalent positions are generated by the 2 symmetry of the M2 site (Fig. 2); and atom Cu3 lies close to Cu1 and ca 1.28 Å from the M1 site, and six equivalent positions are generated by the 3 symmetry of the M1 site (Fig. 1). Positions Cu1 and Cu3 together make an essentially circular distribution around the M1 site (Fig. 1), while position Cu2 and its symmetry equivalent have distinct locations either side of the M2 site (Fig. 2). The Cu1 position is identical to that reported by Bussereau et al. (1992) in CuZr2(PO4)3, and the Cu2/Cu3 positions are identical to those reported by Boireau et al. (1993) in Cu2CrZr(PO4)3.

The coordination geometries of atoms Cu1–Cu3 are listed in Table 2 and illustrated in Fig. 3. Atom Cu1 makes two short Cu—O bonds in an approximately linear arrangement [O2—Cu1—O2i = 172.1 (7)° at 300 K], with four longer Cu—O contacts. Atom Cu2 makes three short Cu—O bonds in a planar arrangement, with two longer Cu—O contacts that define a distorted square-pyramidal geometry, with atom O2 in the apical position (τ = 0.35; Addison et al., 1984). Atom Cu3 makes three short Cu—O bonds in an approximate plane, with a fourth longer contact that defines a highly distorted triangular-based pyramid. The position of atom Cu2 relative to the M2 site is shown in Fig. 2. The Cu+ cation is displaced from the eightfold coordination environment of the M2 site into two symmetry-equivalent distorted square-pyramidal sites. The Cu2···Cu2iv [symmetry code: (iv) x - y + 1/3, -y + 2/3, -z + 1/6] distance across the M2 site is 2.52 (2) Å at 300 K, and does not change significantly down to 100 K.

The site-occupancy factors were considered in several ways. Refinement of the Sc1 and Zr1 site occupancies (constrained to sum to unity) always produced values that did not differ significantly from a 1:1 statistical ratio. These values were therefore constrained to 0.5 (relative to full occupancy for the three-fold symmetric site). For the Cu positions, the site occupancies were initially tightly restrained to sum to 1/3, consistent with charge balance for Cu+ within the formula Cu2ScZr(PO4)3. The refined values are shown in Table 3. Subsequently, the restraint was removed and the occupancies of all Cu sites were refined freely. For atoms Cu1 and Cu3, the resulting occupancies did not differ significantly from those obtained with the restraint in place. For atom Cu2, however, the differences are just about significant, and there is a consistent decrease for all three measured data sets. This may be indicative of low-level Cu2+ residing exclusively in the M2 site, as has been observed previously for CuZr2(PO4)3. Although stoichiometric CuZr2(PO4)3 is colourless, it is more commonly prepared with various shades of pale green, which indicates the presence of Cu2+. An electron paramagnetic resonance study has shown explicitly that Cu1-δZr2(PO4)3 contains Cu2+ cations (Christensen & Warner, 2006), present at a dilute concentration (δ < 1/2). Structural data for the fully oxidized compound, Cu0.5Zr2(PO4)3, are not available for comparison, but in the high-temperature (rhombohedral) green compound, Cu0.5Ti2(PO4)3, the Cu2+ cations occupy solely the M2 site (Olazcuaga et al., 1995). The freely refined Cu occupancies (Table 3) sum to 0.32 (to 2 d.p.) in each case, so the crystal appears to have a composition that is best described as Cu1.92 (1)ScZr(PO4)3. The implied low-level Cu2+ cations are present exclusively at the M2 site.

Atoms Cu1 and Cu3 show a change in occupancy with temperature, whereby atom Cu3 becomes progressively occupied at the expense of Cu1 as the temperature is increased. The occupancy of both the Cu1 and Cu3 positions indicates an essentially circular distribution of Cu+ around the M1 site, with a radius in the approximate range 1.27–1.30 Å [given by the distance between the Cu1/Cu3 positions and the M1 site at (1/3,2/3,1/6)]. This is consistent with a Cu+—Cu+ distance of 2.54–2.60 Å, which is comparable with that in fcc copper metal. As observed by Boireau et al. (1993) for Cu2CrZr(PO4)3, the total occupation factor of ca 1.5 around the M1 site suggests that there must be Cu+—Cu+ pairs in some of these sites. However, the fact that the Cu+—Cu+ distance is significantly longer than that reported for CuZr2(PO4)3 (2.40 Å; Fargin et al., 1992, 1994) may account for why Cu2ScZr(PO4)3 does not luminesce under ultraviolet light. The apparent migration of Cu+ from the Cu1 to the Cu3 position as the temperature increases suggests that Cu+ becomes more mobile around this circular orbit at room temperature compared with 100 K. For Cu+ cations to migrate further through the structure, they must move from this orbit into the Cu2 position and subsequently pass to the symmetry-equivalent Cu2 position on the other side of the M2 site (Fig. 4). The fact that the site occupancy of Cu2 does not change between 100 and 300 K suggests that the activation barrier for these steps is not overcome at 300 K.

Related literature top

For related literature, see: Addison et al. (1984); Ahmamouch et al. (1997); Anantharamulu et al. (2011); Berry et al. (1992); Boireau et al. (1992, 1993); Bruker (2010); Bussereau et al. (1992); Christensen & Warner (2006); El Jazouli, Serghini, Brochu, Dance & Le Flem (1985); Fargin et al. (1992, 1994); Goodenough et al. (1976); Herbst-Irmer & Sheldrick (2002); Hong (1976); Kohler et al. (1983); Le Polles, Parent, Olazcuaga, Le Flem & Hagenmuller (1988); Maihold & Wulff (1987); Mbandza et al. (1985); McCarron et al. (1987); Olazcuaga et al. (1995); Serghini et al. (1995); Sheldrick (2008); Spek (2003); Warner (2011); Warner et al. (1992); Yao & Fray (1983).

Experimental top

A sample (0.02 mol) of Cu2ScZr(PO4)3 was prepared by the following method. The starting materials comprised copper(II) oxide (99.99%), scandium oxide (99.99%), zirconium oxide (99.9975%) and ammonium dihydrogenphosphate (99.999%), all supplied by Aldrich Chemie GmbH. Stoichiometric amounts of these reagents were weighed and then ground intimately to a fine powder with a planetary monomill (Frisch Pulverisette) using a zirconia bowl and balls for 1 h. Cyclohexane (AnalaR grade) was used as the liquid medium. The reaction mixture was placed in an alumina crucible and heated to 673 K under air, and maintained overnight at 673 K before cooling to room temperature. The calcined product was ground (dry) with an agate pestle and mortar to a fine powder then placed in an alumina boat, which was inserted inside a horizontal tube furnace with facilities for a controlled atmosphere. The material was heated to 1573 K under a flowing Ar atmosphere with trace levels of O2 [p(O2) \sim 1 Pa] for 12 h then cooled to room temperature. All heating and cooling rates were 180 K h-1.

The product material appeared to be homogenous and had a beige coloration. Phase purity was confirmed with a Philips PW1710 powder diffractometer using Cu Kα radiation. All of the X-ray reflections corresponded to a NASICON-type phase. The reflection positions were remarkably close to those for the pure zirconium analogue, CuZr2(PO4)3 (PDF 81–526; Bussereau et al., 1992), as indicated by the closely comparable lattice parameters (Table 4). This material was the source of the crystal used for the structural analysis, whereby all three data sets were collected from the same crystal. It was also the source for the sintered polycrystalline monolith used for the ionic conductivity measurements reported elsewhere (Warner et al., 1992).

Refinement top

The analysed crystal was an obverse–reverse twin (Herbst-Irmer & Sheldrick, 2002) with approximately equal twin components. For the data integrated using the specified unit cell, the systematic absences were not consistent with either the obverse or reverse setting. Since the structure was known to adopt space group R3c, the obverse R setting was selected, and reflections violating the systematic absence conditions (i.e. those from the reverse component) were discarded. The systematic absence conditions for the c-glide were then clear, and space group R3c could be selected. The data were merged in XPREP (Bruker, 2010) and the resulting data set was used to solve and partially refine the structure. The twin law corresponding to the obverse–reverse twinning [0 -1 0 / -1 0 0 / 0 0 -1] could then be identified using the TwinRotMat procedure in PLATON (Spek, 2003), and a SHELXL97 (Sheldrick, 2008) HKLF-5 file could be conveniently written out from that program. The final refined scale factor for the twinning was consistent within the standard uncertainty for all three data sets: 0.528 (3) (100 K), 0.524 (3) (200 K) and 0.528 (3) (300 K).

Atoms Sc1 and Zr1 were constrained to have identical coordinates and atomic displacement parameters. The atom site lies on a three-fold axis. The site-occupancy factors were constrained to be 0.5 (relative to full occupancy for the site), as described in the Comment. The positions of atoms Cu1, Cu2 and Cu3 were clearly identifiable in the Fourier map. Their site-occupancy factors were treated as described in the Comment. In the 300 K data set, it was necessary to restrain the anisotropic displacement parameters of the Cu atoms to approximate isotropic behaviour (ISOR restraint in SHELXL97, with an s.u. of 0.01 Å2). For consistency, this restraint was ultimately applied to all of the data sets. The refined site occupancies for Cu1, Cu2 and Cu3 in each case sum to 0.32 (to 2 d.p.), giving 1.92 Cu atoms per unit cell.

Computing details top

For all compounds, data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT and XPREP (Bruker, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Two perpendicular views of Cu2ScZr(PO4)3, showing the approximately circular distribution of Cu+ cations (white spheres) around the M1 site at (1/3,2/3,1/6) at 300 K. Displacement ellipsoids are shown at the 50% probability level for Sc/Zr, P and O atoms.
[Figure 2] Fig. 2. Two perpendicular views of the Cu2 positions (white spheres) around the M2 site at 300 K. Displacement ellipsoids are shown at the 50% probability level for Sc/Zr, P and O atoms. Dashed black lines indicate the Cu—O bonds listed in Table 1, where the symmetry codes are defined.
[Figure 3] Fig. 3. The coordination geometries of Cu1, Cu2 and Cu3. Displacement ellipsoids are shown at the 50% probability level. The Cu—O bonds are listed in Table 1, where the symmetry codes are defined.
[Figure 4] Fig. 4. A projection along the c axis, showing all Cu+ sites as white spheres. The M2 sites link between the circular orbits formed around the M1 sites.
(I_100K) Copper scandium zirconium phosphate top
Crystal data top
Cu1.92O12P3ScZrDx = 3.552 Mg m3
Mr = 543.09Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3cCell parameters from 8756 reflections
Hall symbol: -R 3 2"cθ = 3.2–28.1°
a = 8.9266 (4) ŵ = 6.14 mm1
c = 22.0738 (14) ÅT = 100 K
V = 1523.28 (14) Å3Block, beige
Z = 60.08 × 0.04 × 0.04 mm
F(000) = 1546
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
422 independent reflections
Radiation source: fine-focus sealed tube408 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ω and ϕ scansθmax = 28.3°, θmin = 4.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = 110
Tmin = 0.570, Tmax = 0.787k = 011
36910 measured reflectionsl = 2728
Refinement top
Refinement on F218 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.021Secondary atom site location: difference Fourier map
wR(F2) = 0.051 w = 1/[σ2(Fo2) + (0.0001P)2 + 12.5114P]
where P = (Fo2 + 2Fc2)/3
S = 1.30(Δ/σ)max < 0.001
422 reflectionsΔρmax = 0.36 e Å3
58 parametersΔρmin = 0.70 e Å3
Crystal data top
Cu1.92O12P3ScZrZ = 6
Mr = 543.09Mo Kα radiation
Trigonal, R3cµ = 6.14 mm1
a = 8.9266 (4) ÅT = 100 K
c = 22.0738 (14) Å0.08 × 0.04 × 0.04 mm
V = 1523.28 (14) Å3
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
422 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
408 reflections with I > 2σ(I)
Tmin = 0.570, Tmax = 0.787Rint = 0.036
36910 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02118 restraints
wR(F2) = 0.051 w = 1/[σ2(Fo2) + (0.0001P)2 + 12.5114P]
where P = (Fo2 + 2Fc2)/3
S = 1.30Δρmax = 0.36 e Å3
422 reflectionsΔρmin = 0.70 e Å3
58 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.1658 (5)0.5695 (14)0.1679 (2)0.0143 (18)0.225 (10)
Cu20.1073 (8)0.4206 (8)0.1309 (3)0.011 (2)0.065 (2)
Cu30.179 (3)0.633 (9)0.1762 (16)0.010 (9)0.029 (10)
Zr10.00000.00000.14246 (3)0.00489 (16)0.50
Sc10.00000.00000.14246 (3)0.00489 (16)0.50
P10.00000.28683 (10)0.25000.0061 (2)
O10.0062 (4)0.1943 (3)0.19311 (10)0.0165 (5)
O20.1616 (3)0.4696 (2)0.24977 (11)0.0134 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0153 (15)0.016 (3)0.0077 (13)0.0052 (16)0.0010 (10)0.0061 (15)
Cu20.015 (3)0.009 (3)0.012 (3)0.008 (3)0.003 (2)0.002 (2)
Cu30.012 (10)0.011 (15)0.006 (9)0.004 (9)0.005 (6)0.000 (7)
Zr10.00485 (19)0.00485 (19)0.0050 (2)0.00243 (9)0.0000.000
Sc10.00485 (19)0.00485 (19)0.0050 (2)0.00243 (9)0.0000.000
P10.0067 (4)0.0051 (3)0.0070 (4)0.0033 (2)0.0012 (4)0.0006 (2)
O10.0155 (11)0.0176 (13)0.0170 (10)0.0086 (11)0.0027 (11)0.0106 (10)
O20.0118 (10)0.0067 (9)0.0162 (9)0.0005 (8)0.0022 (10)0.0010 (9)
Geometric parameters (Å, º) top
Zr1—O12.041 (2)Cu1—O12.965 (10)
Zr1—O1i2.041 (2)Cu1—O2vi3.236 (4)
Zr1—O1ii2.041 (2)Cu2—O2vii2.128 (6)
Zr1—O2iii2.113 (2)Cu2—O12.227 (6)
Zr1—O2iv2.113 (2)Cu2—O2ix2.253 (6)
Zr1—O2v2.113 (2)Cu2—O22.665 (6)
P1—O11.519 (2)Cu2—O1vii2.769 (7)
P1—O1vi1.519 (2)Cu2—O2v2.910 (6)
P1—O21.546 (2)Cu2—O2iv3.313 (7)
P1—O2vi1.5458 (19)Cu2—O2vi3.362 (6)
Cu1—O22.007 (4)Cu3—O2vii2.09 (3)
Cu1—O2vii2.029 (4)Cu3—O22.13 (4)
Cu1—O1vii2.607 (4)Cu3—O2viii2.28 (6)
Cu1—O2viii2.755 (11)Cu3—O1vii2.62 (3)
Cu1—O2ix2.833 (8)Cu3—O2ix3.20 (5)
O2—Cu1—O2vii171.9 (4)O1vii—Cu2—O2vi58.28 (12)
O2—Cu1—O1vii110.62 (14)O2v—Cu2—O2vi118.92 (19)
O2vii—Cu1—O1vii63.07 (11)O2iv—Cu2—O2vi83.49 (15)
O2—Cu1—O2viii72.2 (3)O2vii—Cu3—O2145 (4)
O2vii—Cu1—O2viii113.8 (4)O2vii—Cu3—O2viii134 (3)
O1vii—Cu1—O2viii106.6 (3)O2—Cu3—O2viii81.0 (12)
O2—Cu1—O2ix111.4 (3)O2vii—Cu3—O1vii62.1 (8)
O2vii—Cu1—O2ix70.2 (2)O2—Cu3—O1vii106.0 (14)
O1vii—Cu1—O2ix120.9 (3)O2viii—Cu3—O1vii122 (2)
O2viii—Cu1—O2ix124.51 (16)O2vii—Cu3—O2ix61.6 (13)
O2—Cu1—O155.8 (2)O2—Cu3—O2ix96 (2)
O2vii—Cu1—O1117.6 (4)O2viii—Cu3—O2ix128.0 (9)
O1vii—Cu1—O189.2 (2)O1vii—Cu3—O2ix108.5 (18)
O2viii—Cu1—O1127.82 (12)O1—Zr1—O1i92.84 (9)
O2ix—Cu1—O182.1 (3)O1—Zr1—O1ii92.84 (9)
O2—Cu1—O2vi50.55 (12)O1i—Zr1—O1ii92.84 (9)
O2vii—Cu1—O2vi122.01 (16)O1—Zr1—O2iii173.40 (9)
O1vii—Cu1—O2vi61.37 (9)O1i—Zr1—O2iii93.68 (9)
O2viii—Cu1—O2vi96.72 (17)O1ii—Zr1—O2iii87.80 (9)
O2ix—Cu1—O2vi129.5 (4)O1—Zr1—O2v93.68 (9)
O1—Cu1—O2vi47.86 (11)O1i—Zr1—O2v87.80 (9)
O2vii—Cu2—O1161.6 (3)O1ii—Zr1—O2v173.40 (9)
O2vii—Cu2—O2ix81.8 (2)O2iii—Zr1—O2v85.60 (9)
O1—Cu2—O2ix116.4 (3)O1—Zr1—O2iv87.80 (9)
O2vii—Cu2—O2113.8 (3)O1i—Zr1—O2iv173.40 (9)
O1—Cu2—O259.95 (15)O1ii—Zr1—O2iv93.68 (9)
O2ix—Cu2—O2109.6 (3)O2iii—Zr1—O2iv85.60 (9)
O2vii—Cu2—O1vii58.97 (16)O2v—Zr1—O2iv85.60 (9)
O1—Cu2—O1vii102.8 (2)O1—P1—O1vi111.59 (18)
O2ix—Cu2—O1vii140.8 (3)O1—P1—O2107.62 (14)
O2—Cu2—O1vii88.97 (19)O1vi—P1—O2111.05 (14)
O2vii—Cu2—O2vi113.5 (2)O1—P1—O2vi111.06 (13)
O1—Cu2—O2vi48.73 (13)O1vi—P1—O2vi107.62 (14)
O2ix—Cu2—O2vi155.3 (3)O2—P1—O2vi107.87 (17)
O2—Cu2—O2vi47.26 (11)
Symmetry codes: (i) x+y, x, z; (ii) y, xy, z; (iii) x+y1/3, y2/3, z1/6; (iv) x1/3, xy+1/3, z1/6; (v) y+2/3, x+1/3, z1/6; (vi) x, x+y, z+1/2; (vii) y1/3, x+y+1/3, z+1/3; (viii) x+y, x+1, z; (ix) xy+2/3, x+1/3, z+1/3.
(I_200K) Copper scandium zirconium phosphate top
Crystal data top
Cu1.92O12P3ScZrDx = 3.543 Mg m3
Mr = 543.09Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3cCell parameters from 2369 reflections
Hall symbol: -R 3 2"cθ = 3.2–28.1°
a = 8.9344 (5) ŵ = 6.13 mm1
c = 22.0918 (16) ÅT = 200 K
V = 1527.19 (16) Å3Block, beige
Z = 60.08 × 0.04 × 0.04 mm
F(000) = 1546
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
422 independent reflections
Radiation source: fine-focus sealed tube387 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω and ϕ scansθmax = 28.2°, θmin = 4.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = 109
Tmin = 0.545, Tmax = 0.787k = 1111
15401 measured reflectionsl = 028
Refinement top
Refinement on F218 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.027Secondary atom site location: difference Fourier map
wR(F2) = 0.057 w = 1/[σ2(Fo2) + (0.0042P)2 + 15.7557P]
where P = (Fo2 + 2Fc2)/3
S = 1.19(Δ/σ)max < 0.001
422 reflectionsΔρmax = 0.49 e Å3
58 parametersΔρmin = 0.51 e Å3
Crystal data top
Cu1.92O12P3ScZrZ = 6
Mr = 543.09Mo Kα radiation
Trigonal, R3cµ = 6.13 mm1
a = 8.9344 (5) ÅT = 200 K
c = 22.0918 (16) Å0.08 × 0.04 × 0.04 mm
V = 1527.19 (16) Å3
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
422 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
387 reflections with I > 2σ(I)
Tmin = 0.545, Tmax = 0.787Rint = 0.043
15401 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02718 restraints
wR(F2) = 0.057 w = 1/[σ2(Fo2) + (0.0042P)2 + 15.7557P]
where P = (Fo2 + 2Fc2)/3
S = 1.19Δρmax = 0.49 e Å3
422 reflectionsΔρmin = 0.51 e Å3
58 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.1660 (6)0.570 (2)0.1679 (3)0.023 (3)0.210 (13)
Cu20.1070 (11)0.4216 (11)0.1311 (3)0.017 (3)0.064 (3)
Cu30.179 (3)0.639 (7)0.1768 (13)0.014 (8)0.044 (13)
Zr10.00000.00000.14248 (3)0.00594 (18)0.50
Sc10.00000.00000.14248 (3)0.00594 (18)0.50
P10.00000.28708 (12)0.25000.0072 (3)
O10.0064 (4)0.1945 (4)0.19295 (11)0.0184 (6)
O20.1615 (3)0.4697 (3)0.24963 (13)0.0148 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.023 (2)0.029 (6)0.0112 (19)0.008 (3)0.0026 (15)0.011 (3)
Cu20.020 (5)0.014 (5)0.018 (4)0.008 (4)0.009 (3)0.007 (3)
Cu30.015 (10)0.016 (14)0.010 (7)0.007 (8)0.007 (5)0.001 (7)
Zr10.0063 (2)0.0063 (2)0.0053 (3)0.00313 (11)0.0000.000
Sc10.0063 (2)0.0063 (2)0.0053 (3)0.00313 (11)0.0000.000
P10.0084 (5)0.0065 (4)0.0074 (5)0.0042 (3)0.0019 (5)0.0009 (3)
O10.0183 (13)0.0190 (15)0.0188 (12)0.0100 (13)0.0037 (13)0.0115 (11)
O20.0136 (12)0.0078 (11)0.0170 (10)0.0008 (10)0.0027 (12)0.0012 (11)
Geometric parameters (Å, º) top
Cu1—O22.005 (5)Cu3—O2i2.09 (3)
Cu1—O2i2.028 (5)Cu3—O22.16 (4)
Cu1—O1i2.607 (6)Cu3—O2ii2.25 (5)
Cu1—O2ii2.756 (16)Cu3—O1i2.62 (2)
Cu1—O2iii2.830 (13)Cu3—O1ii3.15 (6)
Cu1—O12.965 (15)Zr1—O12.042 (2)
Cu1—O2iv3.240 (5)Zr1—O1vii2.042 (2)
Cu2—O2i2.124 (8)Zr1—O1viii2.042 (2)
Cu2—O12.229 (7)Zr1—O2ix2.117 (2)
Cu2—O2iii2.258 (8)Zr1—O2v2.117 (2)
Cu2—O22.660 (8)Zr1—O2vi2.117 (2)
Cu2—O1i2.761 (9)P1—O11.524 (2)
Cu2—O2v2.923 (9)P1—O1iv1.524 (2)
Cu2—O2vi3.325 (9)P1—O21.546 (2)
Cu2—O2iv3.361 (8)P1—O2iv1.546 (2)
O2—Cu1—O2i171.9 (5)O1—Cu2—O2iv48.89 (16)
O2—Cu1—O1i110.5 (2)O2iii—Cu2—O2iv155.1 (4)
O2i—Cu1—O1i63.09 (16)O2—Cu2—O2iv47.30 (14)
O2—Cu1—O2ii72.3 (4)O1i—Cu2—O2iv58.38 (16)
O2i—Cu1—O2ii113.6 (6)O2v—Cu2—O2iv118.8 (2)
O1i—Cu1—O2ii106.6 (5)O2vi—Cu2—O2iv83.57 (18)
O2—Cu1—O2iii111.5 (6)O2i—Cu3—O2142 (3)
O2i—Cu1—O2iii70.3 (3)O2i—Cu3—O2ii136 (3)
O1i—Cu1—O2iii121.0 (4)O2—Cu3—O2ii81.4 (10)
O2ii—Cu1—O2iii124.5 (2)O2i—Cu3—O1i62.2 (7)
O2—Cu1—O155.8 (3)O2—Cu3—O1i105.3 (14)
O2i—Cu1—O1117.7 (6)O2ii—Cu3—O1i124.1 (17)
O1i—Cu1—O189.1 (3)O2i—Cu3—O1ii90.7 (16)
O2ii—Cu1—O1127.93 (15)O2—Cu3—O1ii125.1 (16)
O2iii—Cu1—O182.0 (5)O2ii—Cu3—O1ii51.3 (12)
O2—Cu1—O2iv50.46 (14)O1i—Cu3—O1ii85.0 (11)
O2i—Cu1—O2iv122.0 (2)O1—Zr1—O1vii93.01 (10)
O1i—Cu1—O2iv61.33 (11)O1—Zr1—O1viii93.01 (10)
O2ii—Cu1—O2iv96.7 (3)O1vii—Zr1—O1viii93.01 (10)
O2iii—Cu1—O2iv129.5 (6)O1—Zr1—O2ix173.29 (11)
O1—Cu1—O2iv47.93 (14)O1vii—Zr1—O2ix93.59 (11)
O2i—Cu2—O1162.1 (4)O1viii—Zr1—O2ix87.82 (11)
O2i—Cu2—O2iii81.9 (3)O1—Zr1—O2v93.59 (11)
O1—Cu2—O2iii116.0 (4)O1vii—Zr1—O2v87.82 (11)
O2i—Cu2—O2114.0 (4)O1viii—Zr1—O2v173.29 (11)
O1—Cu2—O260.07 (19)O2ix—Zr1—O2v85.48 (11)
O2iii—Cu2—O2109.5 (4)O1—Zr1—O2vi87.82 (10)
O2i—Cu2—O1i59.2 (2)O1vii—Zr1—O2vi173.29 (11)
O1—Cu2—O1i103.0 (3)O1viii—Zr1—O2vi93.59 (11)
O2iii—Cu2—O1i141.0 (3)O2ix—Zr1—O2vi85.48 (11)
O2—Cu2—O1i89.1 (2)O2v—Zr1—O2vi85.48 (11)
O2i—Cu2—O2vi120.6 (3)O1—P1—O1iv111.7 (2)
O1—Cu2—O2vi58.7 (2)O1—P1—O2107.46 (16)
O2iii—Cu2—O2vi105.5 (3)O1iv—P1—O2111.16 (15)
O2—Cu2—O2vi117.8 (2)O1—P1—O2iv111.16 (15)
O1i—Cu2—O2vi94.3 (3)O1iv—P1—O2iv107.46 (16)
O2v—Cu2—O2vi54.29 (17)O2—P1—O2iv107.8 (2)
O2i—Cu2—O2iv113.9 (3)
Symmetry codes: (i) y1/3, x+y+1/3, z+1/3; (ii) x+y, x+1, z; (iii) xy+2/3, x+1/3, z+1/3; (iv) x, x+y, z+1/2; (v) y+2/3, x+1/3, z1/6; (vi) x1/3, xy+1/3, z1/6; (vii) x+y, x, z; (viii) y, xy, z; (ix) x+y1/3, y2/3, z1/6.
(I_300K) Copper scandium zirconium phosphate top
Crystal data top
Cu1.92O12P3ScZrDx = 3.557 Mg m3
Mr = 543.09Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3cCell parameters from 4179 reflections
Hall symbol: -R 3 2"cθ = 3.2–28.1°
a = 8.9206 (7) ŵ = 6.15 mm1
c = 22.071 (2) ÅT = 300 K
V = 1521.0 (2) Å3Block, beige
Z = 60.08 × 0.04 × 0.04 mm
F(000) = 1546
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
421 independent reflections
Radiation source: fine-focus sealed tube398 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω and ϕ scansθmax = 28.2°, θmin = 4.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = 109
Tmin = 0.552, Tmax = 0.786k = 1111
16030 measured reflectionsl = 028
Refinement top
Refinement on F218 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.023Secondary atom site location: difference Fourier map
wR(F2) = 0.058 w = 1/[σ2(Fo2) + (0.P)2 + 12.6264P]
where P = (Fo2 + 2Fc2)/3
S = 1.29(Δ/σ)max < 0.001
421 reflectionsΔρmax = 0.46 e Å3
58 parametersΔρmin = 0.49 e Å3
Crystal data top
Cu1.92O12P3ScZrZ = 6
Mr = 543.09Mo Kα radiation
Trigonal, R3cµ = 6.15 mm1
a = 8.9206 (7) ÅT = 300 K
c = 22.071 (2) Å0.08 × 0.04 × 0.04 mm
V = 1521.0 (2) Å3
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
421 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
398 reflections with I > 2σ(I)
Tmin = 0.552, Tmax = 0.786Rint = 0.037
16030 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02318 restraints
wR(F2) = 0.058 w = 1/[σ2(Fo2) + (0.P)2 + 12.6264P]
where P = (Fo2 + 2Fc2)/3
S = 1.29Δρmax = 0.46 e Å3
421 reflectionsΔρmin = 0.49 e Å3
58 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.1651 (6)0.570 (2)0.1681 (4)0.026 (4)0.177 (12)
Cu20.1080 (13)0.4216 (12)0.1314 (4)0.027 (3)0.066 (3)
Cu30.181 (3)0.647 (6)0.1755 (7)0.029 (6)0.078 (13)
Zr10.00000.00000.14254 (3)0.00770 (18)0.50
Sc10.00000.00000.14254 (3)0.00770 (18)0.50
P10.00000.28715 (11)0.25000.0086 (2)
O10.0069 (4)0.1951 (4)0.19303 (11)0.0218 (6)
O20.1621 (3)0.4700 (3)0.24962 (13)0.0173 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.025 (3)0.028 (6)0.017 (3)0.008 (3)0.0040 (19)0.013 (3)
Cu20.035 (5)0.027 (5)0.024 (4)0.018 (4)0.012 (4)0.010 (4)
Cu30.035 (7)0.031 (12)0.019 (4)0.014 (8)0.010 (4)0.007 (5)
Zr10.0080 (2)0.0080 (2)0.0071 (3)0.00401 (11)0.0000.000
Sc10.0080 (2)0.0080 (2)0.0071 (3)0.00401 (11)0.0000.000
P10.0098 (5)0.0076 (4)0.0090 (5)0.0049 (2)0.0021 (5)0.0010 (2)
O10.0220 (13)0.0237 (15)0.0215 (12)0.0129 (13)0.0042 (13)0.0122 (11)
O20.0168 (11)0.0097 (11)0.0187 (10)0.0015 (9)0.0031 (11)0.0012 (11)
Geometric parameters (Å, º) top
Zr1—O12.041 (2)Cu1—O2viii2.742 (19)
Zr1—O1i2.041 (2)Cu1—O2ix2.838 (17)
Zr1—O1ii2.041 (2)Cu1—O12.962 (18)
Zr1—O2iii2.112 (2)Cu2—O2vii2.124 (8)
Zr1—O2iv2.112 (2)Cu2—O12.219 (8)
Zr1—O2v2.112 (2)Cu2—O2ix2.252 (9)
P1—O11.520 (2)Cu2—O22.650 (9)
P1—O1vi1.520 (2)Cu2—O1vii2.760 (10)
P1—O21.547 (2)Cu3—O2vii2.059 (15)
P1—O2vi1.547 (2)Cu3—O2viii2.22 (3)
Cu1—O22.003 (5)Cu3—O22.22 (4)
Cu1—O2vii2.024 (5)Cu3—O1vii2.606 (16)
Cu1—O1vii2.591 (8)
O2—Cu1—O2vii172.1 (7)O2ix—Cu2—O2v105.5 (3)
O2—Cu1—O1vii111.0 (3)O2—Cu2—O2v118.0 (3)
O2vii—Cu1—O1vii63.30 (19)O1vii—Cu2—O2v94.1 (3)
O2—Cu1—O2viii72.3 (5)O2iv—Cu2—O2v54.13 (18)
O2vii—Cu1—O2viii114.1 (8)O2vii—Cu2—O2vi113.8 (3)
O1vii—Cu1—O2viii107.0 (7)O1—Cu2—O2vi48.88 (17)
O2—Cu1—O2ix111.0 (7)O2ix—Cu2—O2vi155.6 (4)
O2vii—Cu1—O2ix69.9 (4)O2—Cu2—O2vi47.46 (14)
O1vii—Cu1—O2ix120.8 (5)O1vii—Cu2—O2vi58.35 (16)
O2viii—Cu1—O2ix124.3 (2)O2iv—Cu2—O2vi118.9 (3)
O2—Cu1—O155.7 (4)O2v—Cu2—O2vi83.5 (2)
O2vii—Cu1—O1117.5 (7)O2vii—Cu3—O2viii140 (2)
O1vii—Cu1—O189.2 (3)O2vii—Cu3—O2139 (2)
O2viii—Cu1—O1127.84 (18)O2viii—Cu3—O280.2 (5)
O2ix—Cu1—O181.8 (6)O2vii—Cu3—O1vii62.6 (4)
O2—Cu1—O2vi50.72 (14)O2viii—Cu3—O1vii125.3 (9)
O2vii—Cu1—O2vi122.3 (2)O2—Cu3—O1vii103.5 (14)
O1vii—Cu1—O2vi61.48 (12)O1—Zr1—O1i93.04 (10)
O2viii—Cu1—O2vi96.9 (4)O1—Zr1—O1ii93.04 (10)
O2ix—Cu1—O2vi129.3 (7)O1i—Zr1—O1ii93.04 (10)
O1—Cu1—O2vi47.96 (15)O1—Zr1—O2iii173.22 (11)
O2vii—Cu2—O1161.9 (5)O1i—Zr1—O2iii93.62 (11)
O2vii—Cu2—O2ix81.7 (3)O1ii—Zr1—O2iii87.91 (10)
O1—Cu2—O2ix116.4 (4)O1—Zr1—O2iv93.62 (11)
O2vii—Cu2—O2114.2 (4)O1i—Zr1—O2iv87.91 (10)
O1—Cu2—O260.2 (2)O1ii—Zr1—O2iv173.22 (11)
O2ix—Cu2—O2109.8 (4)O2iii—Zr1—O2iv85.33 (10)
O2vii—Cu2—O1vii59.0 (2)O1—Zr1—O2v87.91 (10)
O1—Cu2—O1vii102.9 (3)O1i—Zr1—O2v173.22 (11)
O2ix—Cu2—O1vii140.7 (3)O1ii—Zr1—O2v93.62 (11)
O2—Cu2—O1vii89.2 (3)O2iii—Zr1—O2v85.33 (10)
O2vii—Cu2—O2iv124.8 (3)O2iv—Zr1—O2v85.33 (10)
O1—Cu2—O2iv70.7 (3)O1—P1—O1vi111.8 (2)
O2ix—Cu2—O2iv56.2 (2)O1—P1—O2107.24 (16)
O2—Cu2—O2iv112.8 (3)O1vi—P1—O2111.22 (15)
O1vii—Cu2—O2iv146.8 (4)O1—P1—O2vi111.22 (15)
O2vii—Cu2—O2v120.2 (4)O1vi—P1—O2vi107.24 (16)
O1—Cu2—O2v58.8 (2)O2—P1—O2vi108.1 (2)
Symmetry codes: (i) x+y, x, z; (ii) y, xy, z; (iii) x+y1/3, y2/3, z1/6; (iv) y+2/3, x+1/3, z1/6; (v) x1/3, xy+1/3, z1/6; (vi) x, x+y, z+1/2; (vii) y1/3, x+y+1/3, z+1/3; (viii) x+y, x+1, z; (ix) xy+2/3, x+1/3, z+1/3.

Experimental details

(I_100K)(I_200K)(I_300K)
Crystal data
Chemical formulaCu1.92O12P3ScZrCu1.92O12P3ScZrCu1.92O12P3ScZr
Mr543.09543.09543.09
Crystal system, space groupTrigonal, R3cTrigonal, R3cTrigonal, R3c
Temperature (K)100200300
a, c (Å)8.9266 (4), 22.0738 (14)8.9344 (5), 22.0918 (16)8.9206 (7), 22.071 (2)
V3)1523.28 (14)1527.19 (16)1521.0 (2)
Z666
Radiation typeMo KαMo KαMo Kα
µ (mm1)6.146.136.15
Crystal size (mm)0.08 × 0.04 × 0.040.08 × 0.04 × 0.040.08 × 0.04 × 0.04
Data collection
DiffractometerBruker Nonius X8 APEXII CCD area-detector
diffractometer
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2010)
Multi-scan
(SADABS; Bruker, 2010)
Multi-scan
(SADABS; Bruker, 2010)
Tmin, Tmax0.570, 0.7870.545, 0.7870.552, 0.786
No. of measured, independent and
observed [I > 2σ(I)] reflections
36910, 422, 408 15401, 422, 387 16030, 421, 398
Rint0.0360.0430.037
(sin θ/λ)max1)0.6660.6660.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.051, 1.30 0.027, 0.057, 1.19 0.023, 0.058, 1.29
No. of reflections422422421
No. of parameters585858
No. of restraints181818
w = 1/[σ2(Fo2) + (0.0001P)2 + 12.5114P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0042P)2 + 15.7557P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.P)2 + 12.6264P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.36, 0.700.49, 0.510.46, 0.49

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SAINT and XPREP (Bruker, 2010), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) for (I_300K) top
Cu1—O22.003 (5)Cu2—O2iii2.252 (9)
Cu1—O2i2.024 (5)Cu2—O22.650 (9)
Cu1—O1i2.591 (8)Cu2—O1i2.760 (10)
Cu1—O2ii2.742 (19)Cu3—O2i2.059 (15)
Cu1—O2iii2.838 (17)Cu3—O2ii2.22 (3)
Cu1—O12.962 (18)Cu3—O22.22 (4)
Cu2—O2i2.124 (8)Cu3—O1i2.606 (16)
Cu2—O12.219 (8)
Symmetry codes: (i) y1/3, x+y+1/3, z+1/3; (ii) x+y, x+1, z; (iii) xy+2/3, x+1/3, z+1/3.
Fractional coordinates, site symmetry and site-occupancy factors for Cu2ScZr(PO4)3 at 300 K top
SiteSite symmetryxyzOccupancy
Zr13000.14254 (3)0.5
Sc13000.14254 (3)0.5
P1200.28715 (11)0.251.0
O110.0069 (4)0.1951 (4)0.19303 (11)1.0
O210.1621 (3)0.4700 (3)0.24962 (13)1.0
Cu1M110.1651 (5)0.570 (2)0.1681 (4)0.177 (12)
Cu2M210.1080 (13)0.4216 (12)0.1314 (4)0.066 (3)
Cu3M110.181 (3)0.647 (6)0.1755 (7)0.078 (13)
Site-occupancy factors for Cu1, Cu2 and Cu3 at 100–300 K top
Temperature (K)Cu1 (restrained)Cu1 (free)Cu2 (restrained)Cu2 (free)Cu3 (restrained)Cu3 (free)
1000.230 (4)0.225 (10)0.0732 (16)0.065 (2)0.030 (4)0.029 (10)
2000.216 (4)0.210 (13)0.073 (2)0.064 (3)0.044 (4)0.044 (13)
3000.180 (4)0.177 (12)0.074 (2)0.066 (3)0.079 (4)0.078 (13)
Hexagonal cell constants for various CUSICON compounds at room temperature top
Compounda ( Å)c (Å)V3)Reference
CuZr2(PO4)38.9012 (2)22.2021 (6)1523.6 (1)Bussereau et al. (1992)
CuTiZr(PO4)38.686 (1)21.762 (5)1421.8Warner & Skou (2011)
CuTi2(PO4)38.523 (2)21.303 (4)1340.2McCarron et al. (1987)
Cu2CrTi(PO4)38.57021.291354.2El Jazouli et al. (1985)
Cu2CrZr(PO4)38.7449 (3)21.819 (1)1445.0Boireau et al. (1992)
Cu2ScZr(PO4)38.9206 (7)22.071 (2)1521.0 (2)This work
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds