Crystal structure of Ag₃Dy₂(NO₃)₉ and qu­anti­tative comparison to isotypic compounds

The crystal structure of the title compound and its particular relation to isotypic compounds is considered.

Abstract

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 space group P4₁32 (No. 213) with a = 13.2004 (4) Å, V = 2300.2 (2) ų, 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.

1. Chemical context

Double nitrates of alkali metals and lanthanides of the composition A ₃ Ln ₂(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 structure determination were obtained from a 2:1 mixture of Ag and Dy nitrates, 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.

Ag₃Dy₂(NO₃)₉ (Fig. 1 ▸) crystallizes in space group P4₁32 with most atoms at general positions except for Ag, N1 and O1 at 12d and Dy at 8c Wyckoff positions. The asymmetric unit 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. 2 ▸ a), the surrounding oxygen atoms form a distorted icosa­hedron (Fig. 2 ▸ b). 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. 2 ▸ b), 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, U ₂₂). 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.

Figure 1.

Unit cell of Ag₃Dy₂(NO₃)₉, view along the c axis, atomic displacement ellipsoids are drawn with a probability of 60%.

Figure 2.

Twelvefold coordination of the Dy³⁺ ion by six bidentate nitrate ions in Ag₃Dy₂(NO₃)₉: (a) view along the threefold symmetry axis; (b) distorted icosa­hedron around Dy. Atoms are drawn at the 60% probability level. [Symmetry codes: (i) z +  , −y +  , x −  ; (iv) x −  , z +  , −y +  ; (v) −y +  , x −  , z +  ; (vi) −y +  , −z, x −  ; (vii) x −  ; −y +  , −z; (viii) −z, x −  , −y +  .]

Figure 3.

Coordination of the Ag⁺ cation by five bidentate nitrate anions. The shorter Ag—O bonds, which define the AgO₂ dumbbell, are emphasized, displacement ellipsoids are drawn at the 60% probability level. [Symmetry codes: (ii) y, z, x; (iii) x +  , −z +  , y −  .]

Figure 4.

Planar surrounding of the two independent nitrate anions: NO₃(1) (upper) coordinating two Dy and one Ag, view perpendicular to the twofold symmetry axis through Ag, N1, and O1; NO₃(2) (lower) coordinating one Dy and two Ag, the short Ag—O5 bond is drawn thicker than other Ag—O bonds. All atoms are shown at the 60% probability level. [Symmetry codes: (i) z +  , −y +  , x −  ; (iv) x −  , z +  , −y +  ; (ix) y +  , −x +  , z −  ; (x) x +  , −y +  , −z.]

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 coordination number 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 crystal structure has been qu­anti­tatively compared to isotypic structures by applying the program 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 (d _av) 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 d _av, 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.

Table 1. Structure comparison of Ag₃Dy₂(NO₃)₉ with Na₃Nd₂(NO₃)₉ ^a , K₃Ce₂(NO₃)₉ ^b , K₃Pr₂(NO₃)₉ ^c,g , Rb₃Ce₂(NO₃)₉ ^d , Rb₃Pr₂(NO₃)₉ ^e,g , and Rb₃Nd₂(NO₃)₉ ^f,g , by using the program Compstru (de la Flor et al., 2016 ▸).

Cubic lattice parameters (Å), absolute atomic displacements (Å), arithmetic mean displacements (d _av; 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.

3. Database survey

Several anhydrous rare-earth double nitrates of the composition A ₃ Ln ₂(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 refinement details are summarized in Table 2 ▸. The structure was refined as an inversion twin.

Table 2. Experimental details.

Crystal data
Chemical formula	Ag3Dy2(NO3)9
M r	1206.70
Crystal system, space group	Cubic, P4132
Temperature (K)	223
a (Å)	13.2004 (4)
V (Å3)	2300.2 (2)
Z	4
Radiation type	Mo Kα
μ (mm−1)	9.07
Crystal size (mm)	0.4 × 0.3 × 0.1
Data collection
Diffractometer	Stoe StadiVari
Absorption correction	Empirical (using intensity measurements) (X-AREA; Stoe & Cie, 2015 ▸)
T min, T max	0.001, 0.215
No. of measured, independent and observed [I > 2σ(I)] reflections	37326, 763, 715
R int	0.159
(sin θ/λ)max (Å−1)	0.617
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.045, 0.122, 1.18
No. of reflections	763
Δρmax, Δρmin (e Å−3)	2.01, −1.07
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.18 (6)

Computer programs: X-AREA (Stoe & Cie, 2015 ▸), SHELXS97and SHELX (Sheldrick, 2008 ▸), SHELXL2014/7 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg & Putz (2018 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

CCDC reference: 2266445

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

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

Data collection

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

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)

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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.