Na1.85Mg1.85In1.15(PO4)3 and Ag1.69Mg1.69In1.31(PO4)3 with alluaudite-type structures.

Single crystals of two new phosphates, sodium magnesium indium(III) tris-(orthophosphate) and silver magnesium indium(III) tris-(orthophosphate), were obtained from solid-state reactions. The two phosphates are isotypic and exhibit alluaudite-type structures. They are characterized by a cationic disorder of the Mg and In sites and a partial occupation of the Na and Ag sites, respectively. The structure of both phosphates is made up of chains of edge-sharing [(Mg,In)O6] octa-hedra extending parallel to [10]. Adjacent chains are linked by PO4 tetra-hedra to form a three-dimensional framework delimiting two types of channels parallel to [001] in which the monovalent cations are situated. The coordination numbers of the Na+ cations are 6 and 8, and for both Ag+ cations 6. The corresponding coordination spheres are considerably distorted.

Chemical context

The crystal structure of the mineral alluaudite was determined by Moore (1971 ▸). Since then, many new members of this structure type, including phosphates, arsenates, molybdates, sulfates and, more recently, vanadates have been synthesized and structurally characterized. The growing inter­est in these kinds of materials is related to their inter­esting physical properties, in particular in electrochemistry and battery research. For example, the phosphate Na2Ni2Fe(PO4)3 (Essehli et al., 2015 ▸) is a promising cathode in sodium batteries since its electrochemical behaviour is comparable to that of LiFePO4. In this context, alluaudite-type phosphates such as Na1.67Zn1.67Fe1.33(PO4)3 (Khmiyas et al., 2015 ▸), Ag1.655Co1.647Fe1.352(PO4)3 (Bouraima et al., 2017 ▸) and the vanadate (Na0.7)(Na0.70, Mn0.30) (Fe3+, Fe2+)2Fe2+(VO4)3 (Benhsina et al., 2016 ▸) have been investigated by our group.

In the present work, the synthesis and structure determination of two new magnesium-based alluaudite-type phosphates with composition Na1.85Mg1.85In1.15(PO4)3 (I) and Ag1.69Mg1.69In1.31(PO4)3 (II) are reported.

Structural commentary

In the crystal structures of the two isotypic phosphates (I) and (II), site Na1 (Ag1) shows full occupancy and is located on an inversion centre (Wyckoff position 4b), and one mixed-occupied (Mg/In)2 site [occupancy ratio Mg:In = 0.51:0.49 for (I) and 0.314:0.686 for (II)], the second partially occupied Na2 (Ag2) site [occupancy 0.848 (9) for (I) and 0.6988 for (II)] and the P1 site are located on twofold rotation axes (4e) of space group type C2/c. There is another mixed-occupancy (Mg,In)1 site in a general position (8f) with occupancy ratios Mg:In = 0.68:0.32 for (I) and 0.687 (2):0.314 (2) for (II). This kind of cationic disorder is a characteristic feature of alluaudite-type structures. The principal building units in the crystal structures of (I) and (II) are [(Mg/In)1O6] and [(Mg,In)2O6] octa­hedra and two PO4 tetra­hedra (Figs. 1 ▸ and 2 ▸). Two [(Mg/In)1O6] octa­hedra are linked together by a common edge into an [(Mg/In)1)2O10] dimer. These dimers are connected through edge-sharing with [(Mg/In)2O6] octa­hedra into undulating chains extending parallel to [10] (Fig. 3 ▸). Adjacent chains are linked together by P1O4 and P2O4 tetra­hedra into (010) sheets, as shown in Fig. 4 ▸. Neighbouring sheets are finally fused into a three-dimensional framework structure by P1O4 tetra­hedra. This framework delimits two types of hexa­gonal channels oriented parallel to [001], in which the Na+ (for (I) or Ag+ (for (II) cations are located (Fig. 5 ▸). The Na—O distances fall in the range 2.307 (2)–2.960 (2) Å with coordination numbers of six for Na1 and eight for Na2, while those for Ag—O vary between 2.345 (2) and 2.963 (2) Å, with coordination numbers of six for both Ag+ cations.

Figure 1

The principal building units in the structure of Na1.85Mg1.85In1.15(PO4)3, (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + , y + , −z + ; (ii) −x + , −y + , −z + 1; (iii) −x + 1, −y + 1, −z; (iv) −x + , −y + , −z; (v) −x + 1, y, −z + ; (vi) x − , −y + , z − ; (vii) x, −y + 1, z + ; (viii) x, −y + 1, z − ; (ix) −x + 2, y, −z + ; (x) −x + 2, −y + 1, −z + 1; (xi) x + , −y + , z + ; (xii) −x + , −y + , −z + 1.]

Figure 2

The principal building units in the structure of Ag1.69Mg1.69In1.31(PO4)3, (II). Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes are as in Fig. 1 ▸.

Figure 3

Edge-sharing [(Mg/In)2O6] octa­hedra and [(Mg/In)1)2O10] dimers forming an infinite chain extending parallel to [00]. Data taken from (I).

Figure 4

[(Mg/In)O6] octa­hedra and PO4 tetra­hedra forming a sheet extending parallel to (010). Data taken from (I).

Figure 5

Polyhedral representation of the crystal structure of (I) showing Na+ cations situated in the two types of channels parallel to [001].

Database Survey

The presence of disordered alkali metal or other cations in the channels of alluaudite-type structures is a concomitant feature of the cationic disorder at the octa­hedral sites, as observed for example in Cu1.35Fe3(PO4)3 (Warner et al., 1993 ▸), (Na0.38,Ca0.31)MgFe2(PO4)3 (Zid et al., 2005 ▸), K0.53Mn2.37Fe1.24(PO4)3 (Hidouri & Ben Amara, 2011 ▸), NaFe3.67(PO4)3 (Korzenski et al., 1998 ▸), Na1.25Mg1.10Fe1.90(PO4)3 (Hidouri et al., 2008 ▸), Na1.50Mn2.48Al0.85(PO4)3 (Hatert, 2006 ▸), Na1.79Mg1.79Fe1.21(PO4)3 (Hidouri et al., 2003 ▸), Na1.67Zn1.67Fe1.33(PO4)3 (Khmiyas et al., 2015 ▸) or Ag1.655Co1.647Fe1.352(PO4)3 (Bouraima et al., 2017 ▸).

Synthesis and crystallization

Single crystals of (I) and (II) were grown by solid-state reactions. The starting mixtures comprising of Mg(NO3)2·6H2O (Sigma–Aldrich, 97%), InI3 (Ventron, 99%), NH4H2PO4 (Alfa Aesar, 98%), ANO3 (A = Na or Ag) (NaNO3: Acros Organics, 99%; AgNO3: Sigma–Aldrich, 99%) were weighted in molar ratios A:Zn:In:P = 2:2:1:3 and placed in a platinum cruicible. After inter­mediate grinding and temperature treatments at 573, 673, 773 and 873 K in a platinum crucible, both mixtures were heated at 1373 K above the melting temperatures. The cruicibles were then cooled slowly to 1093 K at a rate of 5 K h−1, followed by cooling to room temperature after switching off the furnace. Transparent, colourless crystals with a blocky form were isolated from the two final products. The bulk products were not checked for phase purity.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1 ▸. In the initial stages of the refinements the occupancies of the disordered sodium (Na2) or silver (Ag2) sites were refined freely and the mixed-occupancy (Mg/In) sites were refined under consideration of full occupancy for each of these sites. The obtained occupancy rates of Mg:In were rounded and subsequently fixed for charge-neutrality of the compounds. The maximum and minimum electron densities are located 0.55 Å from Mg2 and 0.38 Å from P1 for (I) and 0.78 and 0.59 Å, respectively, from Ag2 for (II).

Table 1

Experimental details

	(I)	(II)
Crystal data
Chemical formula	Na1.85Mg1.85In1.15(PO4)3	Ag1.69Mg1.69In1.31(PO4)3
M r	504.46	658.40
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	296	296
a, b, c (Å)	11.9796 (13), 12.6935 (13), 6.5239 (7)	12.0273 (3), 12.8120 (3), 6.5061 (2)
β (°)	114.555 (3)	114.519 (1)
V (Å3)	902.33 (17)	912.14 (4)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	3.82	7.59
Crystal size (mm)	0.31 × 0.24 × 0.20	0.30 × 0.27 × 0.23
Data collection
Diffractometer	Bruker X8 APEXII	Bruker X8 APEXII
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.596, 0.748	0.404, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	21364, 2076, 2012	13615, 1827, 1818
R int	0.026	0.027
(sin θ/λ)max (Å−1)	0.819	0.781
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.024, 0.058, 1.29	0.022, 0.053, 1.25
No. of reflections	2076	1827
No. of parameters	97	97
Δρmax, Δρmin (e Å−3)	0.64, −0.88	2.32, −1.36

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SHELXS2016 (Sheldrick, 2015a ▸), SHELXL2016 (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), DIAMOND (Brandenburg, 2006 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018011799/wm5457sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018011799/wm5457Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989018011799/wm5457IIsup3.hkl

CCDC references: 1862981, 1862980

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

Na1.85Mg1.85In1.15(PO4)3	F(000) = 960
Mr = 504.46	Dx = 3.713 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9796 (13) Å	Cell parameters from 2076 reflections
b = 12.6935 (13) Å	θ = 2.5–35.6°
c = 6.5239 (7) Å	µ = 3.82 mm−1
β = 114.555 (3)°	T = 296 K
V = 902.33 (17) Å3	Block, colourless
Z = 4	0.31 × 0.24 × 0.20 mm

Bruker X8 APEXII diffractometer	2076 independent reflections
Radiation source: fine-focus sealed tube	2012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 35.6°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −19→19
Tmin = 0.596, Tmax = 0.748	k = −20→20
21364 measured reflections	l = −10→4

Refinement on F2	97 parameters
Least-squares matrix: full	0 restraints
R[F2 > 2σ(F2)] = 0.024	w = 1/[σ2(Fo2) + (0.0082P)2 + 5.6344P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.058	(Δ/σ)max = 0.001
S = 1.29	Δρmax = 0.64 e Å−3
2076 reflections	Δρmin = −0.88 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mg1	0.71903 (3)	0.84384 (2)	0.13247 (5)	0.00578 (6)	0.68
In1	0.71903 (3)	0.84384 (2)	0.13247 (5)	0.00578 (6)	0.32
In2	0.500000	0.73266 (2)	0.250000	0.00619 (6)	0.51
Mg2	0.500000	0.73266 (2)	0.250000	0.00619 (6)	0.49
P1	0.76657 (4)	0.60997 (4)	0.37446 (8)	0.00665 (8)
P2	0.500000	0.29168 (6)	0.250000	0.00702 (11)
Na1	0.500000	0.500000	0.000000	0.0261 (4)
Na2	1.000000	0.4813 (2)	0.750000	0.0369 (8)	0.848 (9)
O1	0.77790 (14)	0.67695 (12)	0.1877 (2)	0.0092 (2)
O2	0.83997 (14)	0.66480 (12)	0.6061 (2)	0.0096 (2)
O3	0.82556 (15)	0.50207 (12)	0.3858 (3)	0.0126 (3)
O4	0.62982 (14)	0.60255 (13)	0.3291 (3)	0.0128 (3)
O5	0.59943 (14)	0.36515 (12)	0.2450 (3)	0.0124 (3)
O6	0.45840 (13)	0.22035 (12)	0.0372 (2)	0.0099 (2)

	U11	U22	U33	U12	U13	U23
Mg1	0.00607 (11)	0.00594 (11)	0.00620 (11)	−0.00056 (8)	0.00342 (8)	−0.00092 (8)
In1	0.00607 (11)	0.00594 (11)	0.00620 (11)	−0.00056 (8)	0.00342 (8)	−0.00092 (8)
In2	0.00700 (12)	0.00580 (11)	0.00657 (11)	0.000	0.00360 (9)	0.000
Mg2	0.00700 (12)	0.00580 (11)	0.00657 (11)	0.000	0.00360 (9)	0.000
P1	0.00876 (19)	0.00636 (18)	0.00521 (17)	−0.00120 (14)	0.00328 (15)	−0.00039 (14)
P2	0.0072 (3)	0.0077 (3)	0.0054 (2)	0.000	0.0018 (2)	0.000
Na1	0.0375 (9)	0.0121 (6)	0.0156 (6)	0.0017 (6)	−0.0020 (6)	0.0029 (5)
Na2	0.0228 (11)	0.0569 (17)	0.0235 (11)	0.000	0.0020 (8)	0.000
O1	0.0121 (6)	0.0098 (6)	0.0062 (5)	−0.0004 (5)	0.0044 (5)	0.0014 (4)
O2	0.0136 (6)	0.0099 (6)	0.0053 (5)	−0.0027 (5)	0.0039 (5)	−0.0017 (4)
O3	0.0189 (7)	0.0062 (5)	0.0135 (6)	0.0003 (5)	0.0077 (5)	−0.0009 (5)
O4	0.0109 (6)	0.0136 (6)	0.0156 (7)	−0.0035 (5)	0.0072 (5)	−0.0016 (5)
O5	0.0090 (6)	0.0111 (6)	0.0155 (7)	−0.0012 (5)	0.0036 (5)	0.0053 (5)
O6	0.0083 (5)	0.0131 (6)	0.0076 (5)	0.0007 (5)	0.0026 (4)	−0.0026 (5)

Mg1—O5i	1.9992 (16)	P2—O6v	1.5558 (15)
Mg1—O3i	2.0690 (16)	P2—O6	1.5558 (15)
Mg1—O2ii	2.1030 (15)	Na1—O5iii	2.3068 (15)
Mg1—O6iii	2.1099 (15)	Na1—O5	2.3068 (15)
Mg1—O1iv	2.1207 (14)	Na1—O4	2.4387 (16)
Mg1—O1	2.2144 (15)	Na1—O4iii	2.4388 (16)
In2—O4v	2.1783 (17)	Na1—O4viii	2.6072 (15)
In2—O4	2.1784 (17)	Na1—O4v	2.6072 (15)
In2—O2ii	2.1807 (15)	Na1—O5viii	2.9603 (17)
In2—O2vi	2.1807 (15)	Na1—O5v	2.9603 (17)
In2—O6vii	2.2115 (15)	Na2—O3	2.4401 (17)
In2—O6iii	2.2115 (15)	Na2—O3ix	2.4401 (17)
P1—O3	1.5287 (16)	Na2—O3x	2.5955 (17)
P1—O1	1.5373 (15)	Na2—O3vii	2.5955 (17)
P1—O4	1.5419 (16)	Na2—O6xi	2.856 (3)
P1—O2	1.5609 (15)	Na2—O6xii	2.856 (3)
P2—O5	1.5238 (16)	Na2—O2	2.913 (3)
P2—O5v	1.5238 (16)	Na2—O2ix	2.913 (3)
O5i—Mg1—O3i	95.94 (6)	O5—Na1—O4viii	72.41 (6)
O5i—Mg1—O2ii	111.05 (6)	O4—Na1—O4viii	111.56 (7)
O3i—Mg1—O2ii	86.09 (6)	O4iii—Na1—O4viii	68.44 (7)
O5i—Mg1—O6iii	162.43 (6)	O5iii—Na1—O4v	72.41 (6)
O3i—Mg1—O6iii	99.50 (6)	O5—Na1—O4v	107.59 (6)
O2ii—Mg1—O6iii	78.50 (6)	O4—Na1—O4v	68.44 (7)
O5i—Mg1—O1iv	87.10 (6)	O4iii—Na1—O4v	111.56 (7)
O3i—Mg1—O1iv	100.00 (6)	O4viii—Na1—O4v	180.0
O2ii—Mg1—O1iv	160.31 (6)	O5iii—Na1—O5viii	52.70 (6)
O6iii—Mg1—O1iv	82.03 (6)	O5—Na1—O5viii	127.30 (6)
O5i—Mg1—O1	81.05 (6)	O4—Na1—O5viii	85.86 (5)
O3i—Mg1—O1	174.39 (6)	O4iii—Na1—O5viii	94.14 (5)
O2ii—Mg1—O1	90.57 (6)	O4viii—Na1—O5viii	66.27 (5)
O6iii—Mg1—O1	84.22 (6)	O4v—Na1—O5viii	113.73 (5)
O1iv—Mg1—O1	84.63 (6)	O5iii—Na1—O5v	127.30 (6)
O4v—In2—O4	81.40 (8)	O5—Na1—O5v	52.70 (6)
O4v—In2—O2ii	165.44 (6)	O4—Na1—O5v	94.14 (5)
O4—In2—O2ii	86.40 (6)	O4iii—Na1—O5v	85.86 (5)
O4v—In2—O2vi	86.40 (6)	O4viii—Na1—O5v	113.73 (5)
O4—In2—O2vi	165.44 (6)	O4v—Na1—O5v	66.27 (5)
O2ii—In2—O2vi	106.70 (8)	O5viii—Na1—O5v	180.0
O4v—In2—O6vii	90.87 (6)	O3—Na2—O3ix	167.61 (15)
O4—In2—O6vii	113.19 (6)	O3—Na2—O3x	98.29 (5)
O2ii—In2—O6vii	86.65 (5)	O3ix—Na2—O3x	80.70 (5)
O2vi—In2—O6vii	74.72 (5)	O3—Na2—O3vii	80.70 (5)
O4v—In2—O6iii	113.19 (6)	O3ix—Na2—O3vii	98.29 (5)
O4—In2—O6iii	90.87 (6)	O3x—Na2—O3vii	170.69 (14)
O2ii—In2—O6iii	74.72 (5)	O3—Na2—O6xi	73.60 (6)
O2vi—In2—O6iii	86.65 (5)	O3ix—Na2—O6xi	118.42 (10)
O6vii—In2—O6iii	148.70 (8)	O3x—Na2—O6xi	84.80 (7)
O3—P1—O1	110.04 (9)	O3vii—Na2—O6xi	103.66 (8)
O3—P1—O4	112.79 (9)	O3—Na2—O6xii	118.42 (10)
O1—P1—O4	108.57 (9)	O3ix—Na2—O6xii	73.60 (6)
O3—P1—O2	106.82 (9)	O3x—Na2—O6xii	103.66 (8)
O1—P1—O2	108.72 (8)	O3vii—Na2—O6xii	84.80 (7)
O4—P1—O2	109.83 (9)	O6xi—Na2—O6xii	52.60 (8)
O5—P2—O5v	104.53 (13)	O3—Na2—O2	54.35 (6)
O5—P2—O6v	114.33 (8)	O3ix—Na2—O2	114.22 (10)
O5v—P2—O6v	107.48 (9)	O3x—Na2—O2	109.91 (9)
O5—P2—O6	107.48 (9)	O3vii—Na2—O2	61.95 (6)
O5v—P2—O6	114.33 (8)	O6xi—Na2—O2	126.98 (4)
O6v—P2—O6	108.82 (12)	O6xii—Na2—O2	146.30 (5)
O5iii—Na1—O5	180.0	O3—Na2—O2ix	114.22 (10)
O5iii—Na1—O4	99.83 (6)	O3ix—Na2—O2ix	54.35 (6)
O5—Na1—O4	80.17 (6)	O3x—Na2—O2ix	61.95 (6)
O5iii—Na1—O4iii	80.17 (6)	O3vii—Na2—O2ix	109.91 (9)
O5—Na1—O4iii	99.83 (6)	O6xi—Na2—O2ix	146.30 (5)
O4—Na1—O4iii	180.0	O6xii—Na2—O2ix	126.98 (4)
O5iii—Na1—O4viii	107.59 (6)	O2—Na2—O2ix	73.83 (9)

Ag1.69Mg1.69In1.31(PO4)3	F(000) = 1219
Mr = 658.40	Dx = 4.794 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.0273 (3) Å	Cell parameters from 1827 reflections
b = 12.8120 (3) Å	θ = 2.5–33.7°
c = 6.5061 (2) Å	µ = 7.59 mm−1
β = 114.519 (1)°	T = 296 K
V = 912.14 (4) Å3	Block, colourless
Z = 4	0.30 × 0.27 × 0.23 mm

Bruker X8 APEXII diffractometer	1827 independent reflections
Radiation source: fine-focus sealed tube	1818 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 33.7°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −18→18
Tmin = 0.404, Tmax = 0.748	k = −20→20
13615 measured reflections	l = −10→7

Refinement on F2	0 restraints
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0071P)2 + 8.2996P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.022	(Δ/σ)max = 0.001
wR(F2) = 0.053	Δρmax = 2.32 e Å−3
S = 1.25	Δρmin = −1.36 e Å−3
1827 reflections	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
97 parameters	Extinction coefficient: 0.00143 (15)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
In1	0.71633 (3)	0.84600 (3)	0.12503 (6)	0.0061 (2)	0.314 (2)
Mg1	0.71633 (3)	0.84600 (3)	0.12503 (6)	0.0061 (2)	0.687 (2)
Mg2	0.500000	0.73554 (2)	0.250000	0.00583 (9)	0.314 (2)
In2	0.500000	0.73554 (2)	0.250000	0.00583 (9)	0.686 (2)
Ag1	0.500000	0.500000	0.000000	0.02109 (10)
Ag2	1.000000	0.48627 (5)	0.750000	0.03258 (15)	0.6988
P1	0.76583 (5)	0.61258 (4)	0.37509 (9)	0.00362 (10)
P2	0.500000	0.29241 (6)	0.250000	0.00404 (13)
O1	0.77898 (15)	0.67881 (13)	0.1901 (3)	0.0064 (3)
O2	0.84069 (15)	0.66448 (13)	0.6096 (3)	0.0065 (3)
O3	0.81775 (16)	0.50301 (13)	0.3825 (3)	0.0096 (3)
O4	0.62999 (15)	0.60993 (13)	0.3340 (3)	0.0080 (3)
O5	0.60107 (15)	0.36446 (13)	0.2501 (3)	0.0094 (3)
O6	0.45894 (15)	0.22207 (13)	0.0360 (3)	0.0062 (3)

	U11	U22	U33	U12	U13	U23
In1	0.00587 (16)	0.00690 (16)	0.00638 (17)	−0.00070 (10)	0.00336 (11)	−0.00109 (10)
Mg1	0.00587 (16)	0.00690 (16)	0.00638 (17)	−0.00070 (10)	0.00336 (11)	−0.00109 (10)
Mg2	0.00560 (13)	0.00642 (13)	0.00604 (13)	0.000	0.00297 (9)	0.000
In2	0.00560 (13)	0.00642 (13)	0.00604 (13)	0.000	0.00297 (9)	0.000
Ag1	0.03303 (18)	0.00978 (13)	0.01314 (14)	0.00397 (10)	0.00229 (11)	0.00201 (9)
Ag2	0.0127 (2)	0.0291 (3)	0.0406 (3)	0.000	−0.00429 (19)	0.000
P1	0.0037 (2)	0.0038 (2)	0.0036 (2)	−0.00040 (15)	0.00170 (17)	−0.00038 (15)
P2	0.0035 (3)	0.0051 (3)	0.0031 (3)	0.000	0.0010 (2)	0.000
O1	0.0069 (6)	0.0084 (6)	0.0043 (6)	−0.0004 (5)	0.0027 (5)	0.0011 (5)
O2	0.0084 (6)	0.0072 (6)	0.0034 (6)	−0.0025 (5)	0.0020 (5)	−0.0018 (5)
O3	0.0106 (7)	0.0043 (6)	0.0142 (8)	0.0006 (5)	0.0055 (6)	−0.0022 (5)
O4	0.0052 (6)	0.0078 (6)	0.0120 (7)	0.0002 (5)	0.0045 (6)	0.0009 (5)
O5	0.0055 (6)	0.0091 (7)	0.0129 (8)	−0.0018 (5)	0.0032 (6)	0.0031 (6)
O6	0.0052 (6)	0.0091 (6)	0.0043 (6)	−0.0006 (5)	0.0019 (5)	−0.0014 (5)

In1—O5i	2.0146 (17)	Ag1—O5viii	2.9625 (19)
In1—O3i	2.0495 (17)	Ag1—O5v	2.9625 (19)
In1—O1ii	2.0985 (16)	Ag2—O3	2.4934 (19)
In1—O2iii	2.1098 (17)	Ag2—O3ix	2.4934 (19)
In1—O6iv	2.1140 (16)	Ag2—O3x	2.6713 (18)
In1—O1	2.2518 (17)	Ag2—O3vii	2.6713 (18)
Mg2—O4	2.1502 (17)	Ag2—O2ix	2.8751 (18)
Mg2—O4v	2.1503 (17)	Ag2—O2	2.8751 (18)
Mg2—O2iii	2.1665 (16)	Ag2—O6xi	2.9558 (18)
Mg2—O2vi	2.1665 (16)	Ag2—O6xii	2.9558 (18)
Mg2—O6vii	2.1827 (16)	P1—O3	1.5290 (17)
Mg2—O6iv	2.1827 (16)	P1—O1	1.5335 (17)
Ag1—O5	2.3450 (17)	P1—O4	1.5425 (17)
Ag1—O5iv	2.3451 (17)	P1—O2	1.5624 (17)
Ag1—O4iv	2.5162 (17)	P2—O5v	1.5261 (17)
Ag1—O4	2.5162 (17)	P2—O5	1.5261 (17)
Ag1—O4viii	2.6449 (17)	P2—O6	1.5569 (17)
Ag1—O4v	2.6449 (17)	P2—O6v	1.5569 (17)
O5i—In1—O3i	93.91 (7)	O4viii—Ag1—O5viii	68.99 (5)
O5i—In1—O1ii	86.84 (7)	O4v—Ag1—O5viii	111.01 (5)
O3i—In1—O1ii	102.20 (7)	O5—Ag1—O5v	52.97 (7)
O5i—In1—O2iii	110.35 (7)	O5iv—Ag1—O5v	127.03 (7)
O3i—In1—O2iii	87.27 (7)	O4iv—Ag1—O5v	84.06 (5)
O1ii—In1—O2iii	159.96 (6)	O4—Ag1—O5v	95.94 (5)
O5i—In1—O6iv	160.79 (7)	O4viii—Ag1—O5v	111.01 (5)
O3i—In1—O6iv	104.16 (7)	O4v—Ag1—O5v	68.99 (5)
O1ii—In1—O6iv	83.05 (6)	O5viii—Ag1—O5v	180.0
O2iii—In1—O6iv	77.49 (6)	O3—Ag2—O3ix	170.14 (8)
O5i—In1—O1	79.17 (7)	O3—Ag2—O3x	101.46 (5)
O3i—In1—O1	170.47 (7)	O3ix—Ag2—O3x	78.02 (5)
O1ii—In1—O1	84.09 (6)	O3—Ag2—O3vii	78.02 (5)
O2iii—In1—O1	89.01 (6)	O3ix—Ag2—O3vii	101.46 (5)
O6iv—In1—O1	83.56 (6)	O3x—Ag2—O3vii	174.11 (7)
O4—Mg2—O4v	83.10 (9)	O3—Ag2—O2ix	116.17 (5)
O4—Mg2—O2iii	85.00 (6)	O3ix—Ag2—O2ix	54.71 (5)
O4v—Mg2—O2iii	166.46 (6)	O3x—Ag2—O2ix	62.21 (5)
O4—Mg2—O2vi	166.46 (6)	O3vii—Ag2—O2ix	112.62 (5)
O4v—Mg2—O2vi	84.99 (6)	O3—Ag2—O2	54.71 (5)
O2iii—Mg2—O2vi	107.51 (9)	O3ix—Ag2—O2	116.17 (5)
O4—Mg2—O6vii	111.55 (6)	O3x—Ag2—O2	112.62 (5)
O4v—Mg2—O6vii	90.29 (6)	O3vii—Ag2—O2	62.21 (5)
O2iii—Mg2—O6vii	88.11 (6)	O2ix—Ag2—O2	74.85 (7)
O2vi—Mg2—O6vii	74.86 (6)	O3—Ag2—O6xi	73.59 (5)
O4—Mg2—O6iv	90.29 (6)	O3ix—Ag2—O6xi	115.97 (5)
O4v—Mg2—O6iv	111.55 (6)	O3x—Ag2—O6xi	83.88 (5)
O2iii—Mg2—O6iv	74.86 (6)	O3vii—Ag2—O6xi	101.50 (5)
O2vi—Mg2—O6iv	88.11 (6)	O2ix—Ag2—O6xi	145.67 (5)
O6vii—Mg2—O6iv	151.18 (9)	O2—Ag2—O6xi	127.48 (4)
O4—Mg2—O5iv	83.64 (6)	O3—Ag2—O6xii	115.97 (5)
O5—Ag1—O5iv	180.0	O3ix—Ag2—O6xii	73.59 (5)
O5—Ag1—O4iv	98.18 (6)	O3x—Ag2—O6xii	101.50 (5)
O5iv—Ag1—O4iv	81.82 (6)	O3vii—Ag2—O6xii	83.88 (5)
O5—Ag1—O4	81.82 (6)	O2ix—Ag2—O6xii	127.48 (4)
O5iv—Ag1—O4	98.17 (6)	O2—Ag2—O6xii	145.67 (5)
O4iv—Ag1—O4	180.0	O6xi—Ag2—O6xii	50.87 (6)
O5—Ag1—O4viii	70.42 (6)	O3—P1—O1	111.04 (10)
O5iv—Ag1—O4viii	109.58 (6)	O3—P1—O4	112.00 (10)
O4iv—Ag1—O4viii	67.05 (7)	O1—P1—O4	108.85 (9)
O4—Ag1—O4viii	112.95 (7)	O3—P1—O2	107.32 (10)
O5—Ag1—O4v	109.58 (6)	O1—P1—O2	109.01 (9)
O5iv—Ag1—O4v	70.42 (6)	O4—P1—O2	108.55 (10)
O4iv—Ag1—O4v	112.95 (7)	O5v—P2—O5	105.56 (14)
O4—Ag1—O4v	67.05 (7)	O5v—P2—O6	113.12 (9)
O4viii—Ag1—O4v	180.00 (5)	O5—P2—O6	107.91 (9)
O5—Ag1—O5viii	127.03 (7)	O5v—P2—O6v	107.91 (9)
O5iv—Ag1—O5viii	52.97 (7)	O5—P2—O6v	113.12 (9)
O4iv—Ag1—O5viii	95.94 (5)	O6—P2—O6v	109.26 (13)
O4—Ag1—O5viii	84.06 (5)