research communications
3Dy2(NO3)9 and quantitative comparison to isotypic compounds
of AgaTechnical University of Munich, School of Natural Sciences, Department of Chemistry, Lichtenbergstrasse 4, 85747 Garching, Germany
*Correspondence e-mail: wilhelm.klein@tum.de
Single crystals of Ag3Dy2(NO3)9 (trisilver didysprosium nonanitrate) were obtained from a mixture of AgNO3 and Dy(NO3)3·5 H2O. The new compound crystallizes in P4132 (No. 213) with a = 13.2004 (4) Å, V = 2300.2 (2) Å3, Z = 4. The Ag and Dy cations are coordinated by five and six bidentate nitrate anions, respectively. Ag3Dy2(NO3)9 is isostructural to several compounds that include alkali metals or ammonium and lanthanide cations, but silver and dysprosium are included for the first time and feature the smallest ion radii observed for this structure type to date. Crystal structures of isotypic compounds are compared.
Keywords: crystal structure; dysprosium; silver; nitrate.
CCDC reference: 2266445
1. Chemical context
Double nitrates of alkali metals and lanthanides of the composition A3Ln2(NO3)9 have been found to crystallize in the chiral space groups P4132 and P4332 (Wickleder, 2002). After the first finding of K3Pr2(NO3)9 by Carnall et al. (1973), this structure type has been observed in several compounds, to date with K (Carnall et al., 1973; Vigdorchik et al., 1992; Guillou et al., 1995; Gobichon et al., 1999), Rb (Vigdorchik et al., 1990; Manek & Meyer, 1993a; Guillou et al., 1996), and NH4 (Manek & Meyer, 1992) as 'A′ cations for the lighter lanthanides La–Sm, and also detached examples with Na at the 'A′ site (Stockhause & Meyer, 1997; Luo & Corruccini, 2004) and Eu (Manek & Meyer, 1992), Gd (Manek & Meyer, 1992; Luo & Corruccini, 2004), and even Bi (Goaz et al., 2012) at the lanthanide site have been reported. The compounds are typically synthesized by dissolving the lanthanide oxides or nitrates in melts of the respective alkali metal or ammonium nitrates under anhydrous atmosphere, while lanthanum and cerium compounds have been crystallized from solutions in H2O or HNO3 (Guillou et al., 1995, 1996; Gobichon et al., 1999). For the heavier lanthanides, usually another structure type with a slightly different composition, namely in an A/Ln ratio of 2:1 instead of 3:2, is observed under similar reaction conditions (Manek & Meyer, 1992, 1993a), and also for lithium, e.g. after the use of LiNO3 as a starting material, compounds with 2:1 ratio seem to be favoured (Manek & Meyer, 1993b).
In this work a new member of this group of compounds, Ag3Dy2(NO3)9, is presented, the first one containing Ag and Dy, which has been found to crystallize in the above-mentioned structure type.
2. Structural commentary
Similar to many related compounds, the title compound was obtained from a melt of nitrates, in this case silver nitrate and dysprosium nitrate pentahydrate. However, while for synthesis of related compounds, oxides are often used as lanthanide sources and the respective alkali metal nitrate or a eutectic combination of nitrates act as solvent as well as nitrate donor, in the present experimental setting the nitrates can be deployed in stoichiometric amounts. The crystals, which were found to be suitable for i.e. a slight excess of AgNO3, as described in the experimental section. The surplus Ag is present as remaining AgNO3 as well as elemental silver after partial thermal or light-induced decomposition. So far, no hint of another compound with a 2:1 composition of metals in the Ag/Dy system, as could be expected for smaller lanthanides similar to the alkali metal or ammonium systems (Manek & Meyer, 1992, 1993a), has been observed.
were obtained from a 2:1 mixture of Ag and Dy nitrates,Ag3Dy2(NO3)9 (Fig. 1) crystallizes in P4132 with most atoms at general positions except for Ag, N1 and O1 at 12d and Dy at 8c Wyckoff positions. The comprises one Ag, one Dy, two N, and five O atoms. The Dy atom, being located on a threefold axis, is coordinated by six bidentate nitrate anions with Dy—O distances of 2.557 (11)–2.732 (11) Å (see Fig. 2a), the surrounding oxygen atoms form a distorted icosahedron (Fig. 2b). The polyhedra are connected to neighbouring icosahedra via common vertices, and inside this polyhedron the Dy atom is slightly off-centre, shown by formation of the shortest Dy—O distances to O3 and O4 as part of the same NO3− anion (the lower one in Fig. 2b), most probably driven by repulsion of next-neighbour Dy atoms. The silver atom is also coordinated by five nitrate ions in exclusively bidentate manner (Fig. 3). The Ag—O distances span quite a large range, so besides eight distances between 2.741 (11) and 3.004 (11) Å two relatively short distances of 2.383 (15) Å are found. These short bonds include oxygen atoms in almost opposite positions, which form an O—Ag—O angle of 154.7 (6)°, indicating the preferred formation of AgO2 dumbbells even in an environment of quite rigid complex anions, for instance observed in Ag4SiO4 (Klein & Jansen, 2008), in contrast to a more spherical `alkali metal-like' coordination as in Ag3SbO4 (distorted rock salt structure; Klein & Jansen, 2010). Consequently, the Ag atom has its largest axis of the displacement ellipsoid perpendicular to the AgO2 dumbbell direction (see Fig. 3), which also represents the largest extension of an anisotropic parameter of all atoms in this structure (see supporting information, U22). The two independent nitrate ions are perfectly planar, with O—N—O angle sums of 360.00 and 359.79° around N1 and N2, respectively. Both the nitrate ions are situated between three bidentately coordinated metal atoms forming almost planar AgDy2(NO3) and Ag2Dy(NO3) units, respectively, as illustrated in Fig. 4. The longest N—O distances and the smallest O—N—O angles are found in the direction of coordinated Dy atoms, and in addition the Ag atom coordination, including a short Ag—O distance shows an O—N—O angle slightly below the mean value.
The appearance of this structure type for the combination Ag–Dy is somewhat remarkable. While silver as an atypical single-charged cation deforms its direct environment slightly to achieve a more convenient coordinative situation as explained above, dysprosium represents the heaviest lanthanide and, thus, the one with the smallest ionic radius observed in this structure type so far (Shannon, 1976), and a twelve-coordinate site seems to be unusual for this small lanthanide. This view is supported by the finding that compounds that include smaller lanthanide cations avoid to adopt this structure type in favour of another structure with a smaller and even a slightly different composition (A/Ln = 2:1; Manek & Meyer, 1992, 1993a). Additionally, this might be confirmed by the `underbonding' of the Dy cation, as the bond-valence sums (Brown & Altermatt, 1985) are calculated to be 2.51 valence units for the threefold positively charged ion, according to the parameters of Brese & O'Keeffe (1991).
The compstru (de la Flor et al., 2016), available at the Bilbao Crystallographic Server (Aroyo et al., 2006). With Ag3Dy2(NO3)9 as the reference structure, Table 1 lists the absolute distances between paired atoms as well as the arithmetic mean of the distance (dav) between paired atoms, the degree of lattice deviation (S) and the measure of similarity (Δ). Generally, the low values for S and Δ indicate a close relationship between all phases, including the trend to increasing numbers at larger differences of lattice parameters from Na to Rb compounds. The differences of dav, S, and Δ are of course determined in a higher degree by the more differing radii of the (more frequent) alkali metal cations than by those of the more similar lanthanide ions. Significantly, in all cases the largest displacements between atom pairs are observed for O5, i.e. the closest Ag-coordinating O atom, confirming the special bonding situation for Ag including the above-mentioned AgO2 dumbbells. Consequently, the whole NO3 anion, of which O5 is a part, is shifted slightly more than the atoms of the other anion. The Ag atom is also affected, as indicated by higher Ag—A displacements than those of the lanthanide cation pairs, while the coordination of the Ln cations remains similar (distortedly icosahedral, slightly off-centered), just accompanied by decreasing Ln—O distances with decreasing cation radii. An exception represents the, so far, only known Na structure, where the similarity as well as the relative displacements are about one order lower than for all other examples, indicating that the packing is distorted to a similar degree by the small Na cation as in the title compound by the Ag cation. However, the closest Ag—O distance is shorter than all Na—O distances in the related Na3Nd2(NO3)9.
has been quantitatively compared to isotypic structures by applying the program3. Database survey
Several anhydrous rare-earth double nitrates of the composition A3Ln2(NO3)9 have been investigated, mainly including larger lanthanide elements and alkali metals of medium size or ammonium cations, as listed in the Chemical context. Obviously, all of them seem to crystallize in the above-mentioned structure type, however, for some of them only the cubic lattice parameter is given. To date, detailed structural data are available for K3La2(NO3)9 (Gobichon et al., 1999), K3Ce2(NO3)9 (Guillou et al., 1995), Rb3Ce2(NO3)9 (Guillou et al., 1996), K3Pr2(NO3)9 (Carnall et al., 1973), Rb3Pr2(NO3)9 (Manek & Meyer, 1993a), (NH4)3Pr2(NO3)9 (Manek & Meyer, 1992), Na3Nd2(NO3)9 (Stockhause & Meyer, 1997), K3Nd2(NO3)9 (Vigdorchik et al., 1992), Rb3Nd2(NO3)9 (Vigdorchik et al., 1990), and K3Bi2(NO3)9 (Goaz et al., 2012).
4. Synthesis and crystallization
An alumina crucible was charged with 359 mg AgNO3 (2.1 mmol; Merck; p.A.) and 495 mg Dy(NO3)3·5H2O (1.1 mmol; Alfa Aesar; 99.99%). The mixture was melted together at 573 K for 72 h in an Ar atmosphere, and was cooled down to 453 K at a rate of 0.1 K min−1. Within an amorphous yellow–grey matrix, pale-yellow plates were found that were hygroscopic. EDX measurements on several crystals confirm the presence of Ag and Dy as the only elements heavier than oxygen. For the X-ray data collection, crystals were immersed into perfluoroalkyl ether, which covers and acts as glue on a glass tip during the data collection at low temperatures.
5. Refinement
Crystal data, data collection and structure . The structure was refined as an inversion twin.
details are summarized in Table 2
|
Supporting information
CCDC reference: 2266445
https://doi.org/10.1107/S2056989023004747/pk2686sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004747/pk2686Isup2.hkl
Data collection: X-AREA (Stoe & Cie, 2015); cell
X-AREA (Stoe & Cie, 2015); data reduction: X-AREA (Stoe & Cie, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND 3.2k (Brandenburg & Putz (2018); software used to prepare material for publication: SHELX (Sheldrick, 2008) and publCIF (Westrip, 2010).Ag3Dy2(NO3)9 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 1206.70 | Cell parameters from 63387 reflections |
Cubic, P4132 | θ = 2.2–30.7° |
a = 13.2004 (4) Å | µ = 9.07 mm−1 |
V = 2300.2 (2) Å3 | T = 223 K |
Z = 4 | Plate, yellow |
F(000) = 2208 | 0.4 × 0.3 × 0.1 mm |
Dx = 3.485 Mg m−3 |
Stoe StadiVari diffractometer | 763 independent reflections |
Radiation source: Genix 3D HF Mo | 715 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.159 |
Detector resolution: 5.81 pixels mm-1 | θmax = 26.0°, θmin = 2.2° |
ω scans | h = −16→16 |
Absorption correction: empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015) | k = −16→16 |
Tmin = 0.001, Tmax = 0.215 | l = −16→16 |
37326 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.0538P)2 + 51.0589P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.122 | (Δ/σ)max < 0.001 |
S = 1.18 | Δρmax = 2.01 e Å−3 |
763 reflections | Δρmin = −1.07 e Å−3 |
65 parameters | Absolute structure: Refined as an inversion twin |
0 restraints | Absolute structure parameter: 0.18 (6) |
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. |
x | y | z | Uiso*/Ueq | ||
Ag | 0.42059 (11) | 0.1250 | 0.17059 (11) | 0.0411 (6) | |
Dy | 0.03885 (6) | 0.03885 (6) | 0.03885 (6) | 0.0233 (4) | |
N1 | 0.2541 (9) | 0.1250 | 0.0041 (9) | 0.014 (4) | |
O1 | 0.1852 (8) | 0.1250 | −0.0648 (8) | 0.021 (3) | |
O2 | 0.2346 (8) | 0.0854 (8) | 0.0870 (8) | 0.022 (2) | |
N2 | 0.3881 (11) | 0.3676 (11) | 0.1011 (10) | 0.023 (3) | |
O3 | 0.4747 (8) | 0.3304 (9) | 0.0888 (9) | 0.025 (2) | |
O4 | 0.3674 (8) | 0.4493 (8) | 0.0530 (9) | 0.024 (2) | |
O5 | 0.3217 (10) | 0.3253 (11) | 0.1508 (9) | 0.035 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag | 0.0260 (7) | 0.0713 (17) | 0.0260 (7) | −0.0052 (7) | −0.0006 (8) | 0.0052 (7) |
Dy | 0.0233 (4) | 0.0233 (4) | 0.0233 (4) | 0.0002 (3) | 0.0002 (3) | 0.0002 (3) |
N1 | 0.015 (5) | 0.011 (8) | 0.015 (5) | 0.000 (4) | −0.001 (7) | 0.000 (4) |
O1 | 0.022 (5) | 0.017 (7) | 0.022 (5) | −0.005 (4) | −0.003 (6) | 0.005 (4) |
O2 | 0.026 (6) | 0.022 (5) | 0.018 (5) | 0.001 (4) | 0.000 (5) | 0.007 (4) |
N2 | 0.019 (7) | 0.031 (8) | 0.018 (7) | −0.006 (6) | 0.001 (5) | −0.004 (6) |
O3 | 0.015 (5) | 0.030 (6) | 0.029 (6) | 0.005 (5) | 0.005 (5) | 0.008 (5) |
O4 | 0.022 (6) | 0.017 (5) | 0.033 (7) | 0.001 (5) | −0.001 (5) | 0.000 (5) |
O5 | 0.036 (7) | 0.043 (8) | 0.027 (6) | −0.014 (6) | 0.008 (6) | 0.007 (6) |
Ag—O5i | 2.383 (15) | Dy—O1i | 2.626 (2) |
Ag—O5ii | 2.383 (15) | Dy—O1vii | 2.626 (2) |
Ag—O2iii | 2.741 (11) | Dy—O1 | 2.626 (2) |
Ag—O2 | 2.741 (11) | Dy—O2 | 2.732 (11) |
Ag—O4ii | 2.793 (11) | Dy—O2vii | 2.732 (11) |
Ag—O4i | 2.793 (11) | Dy—O2i | 2.732 (11) |
Ag—O5iii | 2.960 (15) | N1—O2 | 1.240 (14) |
Ag—O5 | 2.960 (15) | N1—O2iii | 1.240 (14) |
Ag—N2ii | 2.972 (14) | N1—O1 | 1.29 (2) |
Ag—N2i | 2.972 (14) | O1—Dyviii | 2.626 (2) |
Ag—O3 | 3.004 (11) | N2—O5 | 1.230 (17) |
Ag—O3iii | 3.004 (11) | N2—O3 | 1.255 (18) |
Dy—O3iv | 2.557 (11) | N2—O4 | 1.281 (18) |
Dy—O3v | 2.557 (11) | N2—Agvii | 2.972 (14) |
Dy—O3vi | 2.557 (11) | O3—Dyix | 2.557 (11) |
Dy—O4vi | 2.572 (11) | O4—Dyix | 2.572 (11) |
Dy—O4iv | 2.572 (11) | O4—Agvii | 2.793 (11) |
Dy—O4v | 2.572 (11) | O5—Agvii | 2.383 (15) |
O5i—Ag—O5ii | 154.7 (6) | O3vi—Dy—O4v | 118.6 (3) |
O5i—Ag—O2iii | 120.7 (4) | O4vi—Dy—O4v | 70.6 (4) |
O5ii—Ag—O2iii | 83.8 (4) | O4iv—Dy—O4v | 70.6 (4) |
O5i—Ag—O2 | 83.8 (4) | O3iv—Dy—O1i | 66.9 (4) |
O5ii—Ag—O2 | 120.7 (4) | O3v—Dy—O1i | 67.4 (3) |
O2iii—Ag—O2 | 46.8 (4) | O3vi—Dy—O1i | 168.5 (4) |
O5i—Ag—O4ii | 109.2 (4) | O4vi—Dy—O1i | 139.4 (2) |
O5ii—Ag—O4ii | 48.8 (3) | O4iv—Dy—O1i | 112.0 (4) |
O2iii—Ag—O4ii | 115.5 (3) | O4v—Dy—O1i | 72.6 (3) |
O2—Ag—O4ii | 162.3 (3) | O3iv—Dy—O1vii | 168.5 (4) |
O5i—Ag—O4i | 48.8 (3) | O3v—Dy—O1vii | 66.9 (4) |
O5ii—Ag—O4i | 109.2 (4) | O3vi—Dy—O1vii | 67.4 (3) |
O2iii—Ag—O4i | 162.3 (3) | O4vi—Dy—O1vii | 72.6 (3) |
O2—Ag—O4i | 115.5 (3) | O4iv—Dy—O1vii | 139.4 (2) |
O4ii—Ag—O4i | 82.1 (5) | O4v—Dy—O1vii | 112.0 (4) |
O5i—Ag—O5iii | 116.8 (5) | O1i—Dy—O1vii | 106.9 (3) |
O5ii—Ag—O5iii | 73.3 (5) | O3iv—Dy—O1 | 67.4 (3) |
O2iii—Ag—O5iii | 74.9 (3) | O3v—Dy—O1 | 168.5 (4) |
O2—Ag—O5iii | 64.8 (3) | O3vi—Dy—O1 | 66.9 (4) |
O4ii—Ag—O5iii | 116.5 (3) | O4vi—Dy—O1 | 112.0 (4) |
O4i—Ag—O5iii | 96.8 (3) | O4iv—Dy—O1 | 72.6 (3) |
O5i—Ag—O5 | 73.3 (5) | O4v—Dy—O1 | 139.4 (2) |
O5ii—Ag—O5 | 116.8 (5) | O1i—Dy—O1 | 106.9 (3) |
O2iii—Ag—O5 | 64.8 (3) | O1vii—Dy—O1 | 106.9 (3) |
O2—Ag—O5 | 74.9 (3) | O3iv—Dy—O2 | 65.6 (4) |
O4ii—Ag—O5 | 96.8 (3) | O3v—Dy—O2 | 122.7 (4) |
O4i—Ag—O5 | 116.5 (3) | O3vi—Dy—O2 | 108.3 (3) |
O5iii—Ag—O5 | 136.1 (5) | O4vi—Dy—O2 | 158.2 (3) |
O5i—Ag—N2ii | 133.8 (4) | O4iv—Dy—O2 | 104.7 (3) |
O5ii—Ag—N2ii | 23.4 (4) | O4v—Dy—O2 | 129.0 (4) |
O2iii—Ag—N2ii | 99.1 (3) | O1i—Dy—O2 | 62.4 (2) |
O2—Ag—N2ii | 142.2 (4) | O1vii—Dy—O2 | 103.1 (4) |
O4ii—Ag—N2ii | 25.4 (3) | O1—Dy—O2 | 47.8 (4) |
O4i—Ag—N2ii | 97.1 (3) | O3iv—Dy—O2vii | 122.7 (4) |
O5iii—Ag—N2ii | 94.4 (4) | O3v—Dy—O2vii | 108.3 (3) |
O5—Ag—N2ii | 108.1 (3) | O3vi—Dy—O2vii | 65.6 (4) |
O5i—Ag—N2i | 23.4 (4) | O4vi—Dy—O2vii | 104.7 (3) |
O5ii—Ag—N2i | 133.8 (4) | O4iv—Dy—O2vii | 129.0 (4) |
O2iii—Ag—N2i | 142.2 (4) | O4v—Dy—O2vii | 158.2 (3) |
O2—Ag—N2i | 99.1 (3) | O1i—Dy—O2vii | 103.1 (4) |
O4ii—Ag—N2i | 97.1 (3) | O1vii—Dy—O2vii | 47.8 (4) |
O4i—Ag—N2i | 25.4 (3) | O1—Dy—O2vii | 62.4 (2) |
O5iii—Ag—N2i | 108.1 (3) | O2—Dy—O2vii | 60.9 (4) |
O5—Ag—N2i | 94.4 (4) | O3iv—Dy—O2i | 108.3 (3) |
N2ii—Ag—N2i | 117.8 (5) | O3v—Dy—O2i | 65.6 (4) |
O5i—Ag—O3 | 107.3 (4) | O3vi—Dy—O2i | 122.7 (4) |
O5ii—Ag—O3 | 75.0 (4) | O4vi—Dy—O2i | 129.0 (4) |
O2iii—Ag—O3 | 66.5 (3) | O4iv—Dy—O2i | 158.2 (3) |
O2—Ag—O3 | 103.9 (3) | O4v—Dy—O2i | 104.7 (3) |
O4ii—Ag—O3 | 61.3 (3) | O1i—Dy—O2i | 47.8 (4) |
O4i—Ag—O3 | 127.5 (3) | O1vii—Dy—O2i | 62.4 (2) |
O5iii—Ag—O3 | 132.0 (3) | O1—Dy—O2i | 103.1 (4) |
O5—Ag—O3 | 42.9 (3) | O2—Dy—O2i | 60.9 (4) |
N2ii—Ag—O3 | 65.8 (3) | O2vii—Dy—O2i | 60.9 (4) |
N2i—Ag—O3 | 119.9 (4) | O2—N1—O2iii | 122.9 (18) |
O5i—Ag—O3iii | 75.0 (4) | O2—N1—O1 | 118.5 (9) |
O5ii—Ag—O3iii | 107.3 (4) | O2iii—N1—O1 | 118.5 (9) |
O2iii—Ag—O3iii | 103.9 (3) | N1—O1—Dy | 98.7 (3) |
O2—Ag—O3iii | 66.5 (3) | N1—O1—Dyviii | 98.7 (3) |
O4ii—Ag—O3iii | 127.5 (3) | Dy—O1—Dyviii | 162.6 (6) |
O4i—Ag—O3iii | 61.3 (3) | N1—O2—Dy | 94.9 (9) |
O5iii—Ag—O3iii | 42.9 (3) | N1—O2—Ag | 95.1 (9) |
O5—Ag—O3iii | 132.0 (3) | Dy—O2—Ag | 169.6 (5) |
N2ii—Ag—O3iii | 119.9 (4) | O5—N2—O3 | 122.7 (15) |
N2i—Ag—O3iii | 65.8 (3) | O5—N2—O4 | 119.7 (14) |
O3—Ag—O3iii | 170.1 (5) | O3—N2—O4 | 117.4 (13) |
O3iv—Dy—O3v | 116.77 (16) | O5—N2—Agvii | 50.3 (9) |
O3iv—Dy—O3vi | 116.77 (16) | O3—N2—Agvii | 170.4 (11) |
O3v—Dy—O3vi | 116.77 (16) | O4—N2—Agvii | 69.4 (8) |
O3iv—Dy—O4vi | 118.6 (3) | N2—O3—Dyix | 97.0 (9) |
O3v—Dy—O4vi | 76.0 (4) | N2—O3—Ag | 95.2 (9) |
O3vi—Dy—O4vi | 50.0 (3) | Dyix—O3—Ag | 157.7 (5) |
O3iv—Dy—O4iv | 50.0 (3) | N2—O4—Dyix | 95.6 (8) |
O3v—Dy—O4iv | 118.6 (3) | N2—O4—Agvii | 85.1 (8) |
O3vi—Dy—O4iv | 76.0 (4) | Dyix—O4—Agvii | 170.9 (5) |
O4vi—Dy—O4iv | 70.6 (4) | N2—O5—Agvii | 106.3 (11) |
O3iv—Dy—O4v | 76.0 (4) | N2—O5—Ag | 98.0 (11) |
O3v—Dy—O4v | 50.0 (3) | Agvii—O5—Ag | 148.6 (5) |
Symmetry codes: (i) y, z, x; (ii) x+1/4, −z+1/4, y−1/4; (iii) z+1/4, −y+1/4, x−1/4; (iv) −y+1/2, −z, x−1/2; (v) −z, x−1/2, −y+1/2; (vi) x−1/2, −y+1/2, −z; (vii) z, x, y; (viii) y+1/4, −x+1/4, z−1/4; (ix) x+1/2, −y+1/2, −z. |
Cubic lattice parameters (Å), absolute atomic displacements (Å), arithmetic mean displacements (dav; Å), degree of lattice distortion (S), and measure of similarity (Δ)h. |
A = | Na | K | K | Rb | Rb | Rb |
Ln = | Nd | Ce | Pr | Ce | Pr | Nd |
a | 13.1279 | 13.5975 | 13.52 | 13.8411 | 13.8091 | 13.759 |
A | 0.0035 | 0.3157 | 0.3325 | 0.4725 | 0.4680 | 0.4729 |
Ln | 0.0151 | 0.2318 | 0.2440 | 0.3670 | 0.3768 | 0.3885 |
N1 | 0.0261 | 0.1605 | 0.1997 | 0.1848 | 0.2296 | 0.2352 |
O1 | 0.0187 | 0.2072 | 0.2035 | 0.2576 | 0.2912 | 0.3080 |
O2 | 0.0170 | 0.1786 | 0.1821 | 0.2763 | 0.2582 | 0.2646 |
N2 | 0.0223 | 0.3350 | 0.3555 | 0.5195 | 0.4883 | 0.4907 |
O3 | 0.0577 | 0.3059 | 0.3072 | 0.4321 | 0.4278 | 0.4502 |
O4 | 0.0346 | 0.3302 | 0.3271 | 0.4027 | 0.4815 | 0.4732 |
O5 | 0.0577 | 0.4583 | 0.4839 | 0.6160 | 0.6490 | 0.6483 |
dav | 0.0320 | 0.2966 | 0.3080 | 0.4136 | 0.4280 | 0.4338 |
S | 0.0032 | 0.0166 | 0.0135 | 0.0261 | 0.0249 | 0.0230 |
Δ | 0.003 | 0.032 | 0.033 | 0.044 | 0.046 | 0.046 |
Notes: (a) Stockhause & Meyer (1997); (b) Guillou et al. (1995); (c) Carnall et al. (1973); (d) Guillou et al. (1996); (e) Manek & Meyer (1993a); (f) Vigdorchik et al. (1990); (g) K3Pr2(NO3)9, Rb3Pr2(NO3)9, and Rb3Nd2(NO3)9 were originally described in P4332 and were transformed into P4132; (h) atom displacements are calculated by applying the lattice parameter of Ag3Dy2(NO3)9 [a = 13.2004 (4) Å] to the structure models of the listed compounds. |
Acknowledgements
Maria Müller is gratefully acknowledged for the EDX measurements.
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