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

Ould Saleck, A.; Assani, A.; Saadi, M.; Mercier, C.; Follet, C.; El Ammari, L.

doi:10.1107/S2056989018011799

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ISSN: 2056-9890

Volume 74| Part 9| September 2018| Pages 1358-1361

https://doi.org/10.1107/S2056989018011799

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Na_1.85Mg_1.85In_1.15(PO₄)₃ and Ag_1.69Mg_1.69In_1.31(PO₄)₃ with alluaudite-type structures

Ahmed Ould Saleck,^a ^* Abderrazzak Assani,^a Mohamed Saadi,^a Cyrille Mercier,^b Claudine Follet ^b and Lahcen El Ammari ^a

^aLaboratoire de Chimie Appliquée des Matériaux, Centre Sciences des Matériaux, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Batouta, BP 1014, Rabat, Morocco, and ^bUniversité de Valenciennes, EA 2443 – LMCPA – Laboratoire des Matériaux Céramiques et Procédés Associés, F-59313 Valenciennes, France
^*Correspondence e-mail: a_ouldsaleck@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 July 2018; accepted 20 August 2018; online 24 August 2018)

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] octahedra extending parallel to [10 $[\overline{1}]$ ]. Adjacent chains are linked by PO₄ tetrahedra 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.

Keywords: crystal structure; mixed-metal phosphate; solid-state reaction; disorder; alluaudite.

CCDC references: 1862981; 1862980

1. 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 Na_1.67Zn_1.67Fe_1.33(PO₄)₃ (Khmiyas et al., 2015 ), Ag_1.655Co_1.647Fe_1.352(PO₄)₃ (Bouraima et al., 2017 ) and the vanadate (Na_0.7)(Na_0.70, Mn_0.30) (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 Na_1.85Mg_1.85In_1.15(PO₄)₃ (I) and Ag_1.69Mg_1.69In_1.31(PO₄)₃ (II) are reported.

2. 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 $[\overline{1}]$ ] (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 Na_1.85Mg_1.85In_1.15(PO₄)₃, (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (iii) −x + 1, −y + 1, −z; (iv) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z; (v) −x + 1, y, −z + $[{1\over 2}]$ ; (vi) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (vii) x, −y + 1, z + $[{1\over 2}]$ ; (viii) x, −y + 1, z − $[{1\over 2}]$ ; (ix) −x + 2, y, −z + $[{3\over 2}]$ ; (x) −x + 2, −y + 1, −z + 1; (xi) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (xii) −x + $[{3\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1.]

Figure 2
The principal building units in the structure of Ag_1.69Mg_1.69In_1.31(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 $[\overline{1}]$ ]. 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].

3. 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 Cu_1.35Fe₃(PO₄)₃ (Warner et al., 1993 ), (Na_0.38,Ca_0.31)MgFe₂(PO₄)₃ (Zid et al., 2005 ), K_0.53Mn_2.37Fe_1.24(PO₄)₃ (Hidouri & Ben Amara, 2011 ), NaFe_3.67(PO₄)₃ (Korzenski et al., 1998 ), Na_1.25Mg_1.10Fe_1.90(PO₄)₃ (Hidouri et al., 2008 ), Na_1.50Mn_2.48Al_0.85(PO₄)₃ (Hatert, 2006 ), Na_1.79Mg_1.79Fe_1.21(PO₄)₃ (Hidouri et al., 2003 ), Na_1.67Zn_1.67Fe_1.33(PO₄)₃ (Khmiyas et al., 2015) or Ag_1.655Co_1.647Fe_1.352(PO₄)₃ (Bouraima et al., 2017).

4. 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.

5. 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	Na_1.85Mg_1.85In_1.15(PO₄)₃	Ag_1.69Mg_1.69In_1.31(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[F² > 2σ(F²)], wR(F²), S	0.024, 0.058, 1.29	0.022, 0.053, 1.25
No. of reflections	2076	1827
No. of parameters	97	97
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC references: 1862981; 1862980

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989018011799/wm5457sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018011799/wm5457Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989018011799/wm5457IIsup3.hkl

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Sodium magnesium indium(III) tris(orthophosphate) (I) top

Crystal data top

Na_1.85Mg_1.85In_1.15(PO₄)₃	F(000) = 960
M_r = 504.46	D_x = 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

Data collection top

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

Refinement top

Refinement on F²	97 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.024	w = 1/[σ²(F_o²) + (0.0082P)² + 5.6344P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.058	(Δ/σ)_max = 0.001
S = 1.29	Δρ_max = 0.64 e Å⁻³
2076 reflections	Δρ_min = −0.88 e Å⁻³

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Mg1—O5ⁱ	1.9992 (16)	P2—O6^v	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—O1^iv	2.1207 (14)	Na1—O4	2.4387 (16)
Mg1—O1	2.2144 (15)	Na1—O4ⁱⁱⁱ	2.4388 (16)
In2—O4^v	2.1783 (17)	Na1—O4^viii	2.6072 (15)
In2—O4	2.1784 (17)	Na1—O4^v	2.6072 (15)
In2—O2ⁱⁱ	2.1807 (15)	Na1—O5^viii	2.9603 (17)
In2—O2^vi	2.1807 (15)	Na1—O5^v	2.9603 (17)
In2—O6^vii	2.2115 (15)	Na2—O3	2.4401 (17)
In2—O6ⁱⁱⁱ	2.2115 (15)	Na2—O3^ix	2.4401 (17)
P1—O3	1.5287 (16)	Na2—O3^x	2.5955 (17)
P1—O1	1.5373 (15)	Na2—O3^vii	2.5955 (17)
P1—O4	1.5419 (16)	Na2—O6^xi	2.856 (3)
P1—O2	1.5609 (15)	Na2—O6^xii	2.856 (3)
P2—O5	1.5238 (16)	Na2—O2	2.913 (3)
P2—O5^v	1.5238 (16)	Na2—O2^ix	2.913 (3)

O5ⁱ—Mg1—O3ⁱ	95.94 (6)	O5—Na1—O4^viii	72.41 (6)
O5ⁱ—Mg1—O2ⁱⁱ	111.05 (6)	O4—Na1—O4^viii	111.56 (7)
O3ⁱ—Mg1—O2ⁱⁱ	86.09 (6)	O4ⁱⁱⁱ—Na1—O4^viii	68.44 (7)
O5ⁱ—Mg1—O6ⁱⁱⁱ	162.43 (6)	O5ⁱⁱⁱ—Na1—O4^v	72.41 (6)
O3ⁱ—Mg1—O6ⁱⁱⁱ	99.50 (6)	O5—Na1—O4^v	107.59 (6)
O2ⁱⁱ—Mg1—O6ⁱⁱⁱ	78.50 (6)	O4—Na1—O4^v	68.44 (7)
O5ⁱ—Mg1—O1^iv	87.10 (6)	O4ⁱⁱⁱ—Na1—O4^v	111.56 (7)
O3ⁱ—Mg1—O1^iv	100.00 (6)	O4^viii—Na1—O4^v	180.0
O2ⁱⁱ—Mg1—O1^iv	160.31 (6)	O5ⁱⁱⁱ—Na1—O5^viii	52.70 (6)
O6ⁱⁱⁱ—Mg1—O1^iv	82.03 (6)	O5—Na1—O5^viii	127.30 (6)
O5ⁱ—Mg1—O1	81.05 (6)	O4—Na1—O5^viii	85.86 (5)
O3ⁱ—Mg1—O1	174.39 (6)	O4ⁱⁱⁱ—Na1—O5^viii	94.14 (5)
O2ⁱⁱ—Mg1—O1	90.57 (6)	O4^viii—Na1—O5^viii	66.27 (5)
O6ⁱⁱⁱ—Mg1—O1	84.22 (6)	O4^v—Na1—O5^viii	113.73 (5)
O1^iv—Mg1—O1	84.63 (6)	O5ⁱⁱⁱ—Na1—O5^v	127.30 (6)
O4^v—In2—O4	81.40 (8)	O5—Na1—O5^v	52.70 (6)
O4^v—In2—O2ⁱⁱ	165.44 (6)	O4—Na1—O5^v	94.14 (5)
O4—In2—O2ⁱⁱ	86.40 (6)	O4ⁱⁱⁱ—Na1—O5^v	85.86 (5)
O4^v—In2—O2^vi	86.40 (6)	O4^viii—Na1—O5^v	113.73 (5)
O4—In2—O2^vi	165.44 (6)	O4^v—Na1—O5^v	66.27 (5)
O2ⁱⁱ—In2—O2^vi	106.70 (8)	O5^viii—Na1—O5^v	180.0
O4^v—In2—O6^vii	90.87 (6)	O3—Na2—O3^ix	167.61 (15)
O4—In2—O6^vii	113.19 (6)	O3—Na2—O3^x	98.29 (5)
O2ⁱⁱ—In2—O6^vii	86.65 (5)	O3^ix—Na2—O3^x	80.70 (5)
O2^vi—In2—O6^vii	74.72 (5)	O3—Na2—O3^vii	80.70 (5)
O4^v—In2—O6ⁱⁱⁱ	113.19 (6)	O3^ix—Na2—O3^vii	98.29 (5)
O4—In2—O6ⁱⁱⁱ	90.87 (6)	O3^x—Na2—O3^vii	170.69 (14)
O2ⁱⁱ—In2—O6ⁱⁱⁱ	74.72 (5)	O3—Na2—O6^xi	73.60 (6)
O2^vi—In2—O6ⁱⁱⁱ	86.65 (5)	O3^ix—Na2—O6^xi	118.42 (10)
O6^vii—In2—O6ⁱⁱⁱ	148.70 (8)	O3^x—Na2—O6^xi	84.80 (7)
O3—P1—O1	110.04 (9)	O3^vii—Na2—O6^xi	103.66 (8)
O3—P1—O4	112.79 (9)	O3—Na2—O6^xii	118.42 (10)
O1—P1—O4	108.57 (9)	O3^ix—Na2—O6^xii	73.60 (6)
O3—P1—O2	106.82 (9)	O3^x—Na2—O6^xii	103.66 (8)
O1—P1—O2	108.72 (8)	O3^vii—Na2—O6^xii	84.80 (7)
O4—P1—O2	109.83 (9)	O6^xi—Na2—O6^xii	52.60 (8)
O5—P2—O5^v	104.53 (13)	O3—Na2—O2	54.35 (6)
O5—P2—O6^v	114.33 (8)	O3^ix—Na2—O2	114.22 (10)
O5^v—P2—O6^v	107.48 (9)	O3^x—Na2—O2	109.91 (9)
O5—P2—O6	107.48 (9)	O3^vii—Na2—O2	61.95 (6)
O5^v—P2—O6	114.33 (8)	O6^xi—Na2—O2	126.98 (4)
O6^v—P2—O6	108.82 (12)	O6^xii—Na2—O2	146.30 (5)
O5ⁱⁱⁱ—Na1—O5	180.0	O3—Na2—O2^ix	114.22 (10)
O5ⁱⁱⁱ—Na1—O4	99.83 (6)	O3^ix—Na2—O2^ix	54.35 (6)
O5—Na1—O4	80.17 (6)	O3^x—Na2—O2^ix	61.95 (6)
O5ⁱⁱⁱ—Na1—O4ⁱⁱⁱ	80.17 (6)	O3^vii—Na2—O2^ix	109.91 (9)
O5—Na1—O4ⁱⁱⁱ	99.83 (6)	O6^xi—Na2—O2^ix	146.30 (5)
O4—Na1—O4ⁱⁱⁱ	180.0	O6^xii—Na2—O2^ix	126.98 (4)
O5ⁱⁱⁱ—Na1—O4^viii	107.59 (6)	O2—Na2—O2^ix	73.83 (9)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, −y+3/2, −z+1; (iii) −x+1, −y+1, −z; (iv) −x+3/2, −y+3/2, −z; (v) −x+1, y, −z+1/2; (vi) x−1/2, −y+3/2, z−1/2; (vii) x, −y+1, z+1/2; (viii) x, −y+1, z−1/2; (ix) −x+2, y, −z+3/2; (x) −x+2, −y+1, −z+1; (xi) x+1/2, −y+1/2, z+1/2; (xii) −x+3/2, −y+1/2, −z+1.

Silver magnesium indium(III) tris(orthophosphate) (II) top

Crystal data top

Ag_1.69Mg_1.69In_1.31(PO₄)₃	F(000) = 1219
M_r = 658.40	D_x = 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

Data collection top

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

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0071P)² + 8.2996P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.022	(Δ/σ)_max = 0.001
wR(F²) = 0.053	Δρ_max = 2.32 e Å⁻³
S = 1.25	Δρ_min = −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)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

In1—O5ⁱ	2.0146 (17)	Ag1—O5^viii	2.9625 (19)
In1—O3ⁱ	2.0495 (17)	Ag1—O5^v	2.9625 (19)
In1—O1ⁱⁱ	2.0985 (16)	Ag2—O3	2.4934 (19)
In1—O2ⁱⁱⁱ	2.1098 (17)	Ag2—O3^ix	2.4934 (19)
In1—O6^iv	2.1140 (16)	Ag2—O3^x	2.6713 (18)
In1—O1	2.2518 (17)	Ag2—O3^vii	2.6713 (18)
Mg2—O4	2.1502 (17)	Ag2—O2^ix	2.8751 (18)
Mg2—O4^v	2.1503 (17)	Ag2—O2	2.8751 (18)
Mg2—O2ⁱⁱⁱ	2.1665 (16)	Ag2—O6^xi	2.9558 (18)
Mg2—O2^vi	2.1665 (16)	Ag2—O6^xii	2.9558 (18)
Mg2—O6^vii	2.1827 (16)	P1—O3	1.5290 (17)
Mg2—O6^iv	2.1827 (16)	P1—O1	1.5335 (17)
Ag1—O5	2.3450 (17)	P1—O4	1.5425 (17)
Ag1—O5^iv	2.3451 (17)	P1—O2	1.5624 (17)
Ag1—O4^iv	2.5162 (17)	P2—O5^v	1.5261 (17)
Ag1—O4	2.5162 (17)	P2—O5	1.5261 (17)
Ag1—O4^viii	2.6449 (17)	P2—O6	1.5569 (17)
Ag1—O4^v	2.6449 (17)	P2—O6^v	1.5569 (17)

O5ⁱ—In1—O3ⁱ	93.91 (7)	O4^viii—Ag1—O5^viii	68.99 (5)
O5ⁱ—In1—O1ⁱⁱ	86.84 (7)	O4^v—Ag1—O5^viii	111.01 (5)
O3ⁱ—In1—O1ⁱⁱ	102.20 (7)	O5—Ag1—O5^v	52.97 (7)
O5ⁱ—In1—O2ⁱⁱⁱ	110.35 (7)	O5^iv—Ag1—O5^v	127.03 (7)
O3ⁱ—In1—O2ⁱⁱⁱ	87.27 (7)	O4^iv—Ag1—O5^v	84.06 (5)
O1ⁱⁱ—In1—O2ⁱⁱⁱ	159.96 (6)	O4—Ag1—O5^v	95.94 (5)
O5ⁱ—In1—O6^iv	160.79 (7)	O4^viii—Ag1—O5^v	111.01 (5)
O3ⁱ—In1—O6^iv	104.16 (7)	O4^v—Ag1—O5^v	68.99 (5)
O1ⁱⁱ—In1—O6^iv	83.05 (6)	O5^viii—Ag1—O5^v	180.0
O2ⁱⁱⁱ—In1—O6^iv	77.49 (6)	O3—Ag2—O3^ix	170.14 (8)
O5ⁱ—In1—O1	79.17 (7)	O3—Ag2—O3^x	101.46 (5)
O3ⁱ—In1—O1	170.47 (7)	O3^ix—Ag2—O3^x	78.02 (5)
O1ⁱⁱ—In1—O1	84.09 (6)	O3—Ag2—O3^vii	78.02 (5)
O2ⁱⁱⁱ—In1—O1	89.01 (6)	O3^ix—Ag2—O3^vii	101.46 (5)
O6^iv—In1—O1	83.56 (6)	O3^x—Ag2—O3^vii	174.11 (7)
O4—Mg2—O4^v	83.10 (9)	O3—Ag2—O2^ix	116.17 (5)
O4—Mg2—O2ⁱⁱⁱ	85.00 (6)	O3^ix—Ag2—O2^ix	54.71 (5)
O4^v—Mg2—O2ⁱⁱⁱ	166.46 (6)	O3^x—Ag2—O2^ix	62.21 (5)
O4—Mg2—O2^vi	166.46 (6)	O3^vii—Ag2—O2^ix	112.62 (5)
O4^v—Mg2—O2^vi	84.99 (6)	O3—Ag2—O2	54.71 (5)
O2ⁱⁱⁱ—Mg2—O2^vi	107.51 (9)	O3^ix—Ag2—O2	116.17 (5)
O4—Mg2—O6^vii	111.55 (6)	O3^x—Ag2—O2	112.62 (5)
O4^v—Mg2—O6^vii	90.29 (6)	O3^vii—Ag2—O2	62.21 (5)
O2ⁱⁱⁱ—Mg2—O6^vii	88.11 (6)	O2^ix—Ag2—O2	74.85 (7)
O2^vi—Mg2—O6^vii	74.86 (6)	O3—Ag2—O6^xi	73.59 (5)
O4—Mg2—O6^iv	90.29 (6)	O3^ix—Ag2—O6^xi	115.97 (5)
O4^v—Mg2—O6^iv	111.55 (6)	O3^x—Ag2—O6^xi	83.88 (5)
O2ⁱⁱⁱ—Mg2—O6^iv	74.86 (6)	O3^vii—Ag2—O6^xi	101.50 (5)
O2^vi—Mg2—O6^iv	88.11 (6)	O2^ix—Ag2—O6^xi	145.67 (5)
O6^vii—Mg2—O6^iv	151.18 (9)	O2—Ag2—O6^xi	127.48 (4)
O4—Mg2—O5^iv	83.64 (6)	O3—Ag2—O6^xii	115.97 (5)
O5—Ag1—O5^iv	180.0	O3^ix—Ag2—O6^xii	73.59 (5)
O5—Ag1—O4^iv	98.18 (6)	O3^x—Ag2—O6^xii	101.50 (5)
O5^iv—Ag1—O4^iv	81.82 (6)	O3^vii—Ag2—O6^xii	83.88 (5)
O5—Ag1—O4	81.82 (6)	O2^ix—Ag2—O6^xii	127.48 (4)
O5^iv—Ag1—O4	98.17 (6)	O2—Ag2—O6^xii	145.67 (5)
O4^iv—Ag1—O4	180.0	O6^xi—Ag2—O6^xii	50.87 (6)
O5—Ag1—O4^viii	70.42 (6)	O3—P1—O1	111.04 (10)
O5^iv—Ag1—O4^viii	109.58 (6)	O3—P1—O4	112.00 (10)
O4^iv—Ag1—O4^viii	67.05 (7)	O1—P1—O4	108.85 (9)
O4—Ag1—O4^viii	112.95 (7)	O3—P1—O2	107.32 (10)
O5—Ag1—O4^v	109.58 (6)	O1—P1—O2	109.01 (9)
O5^iv—Ag1—O4^v	70.42 (6)	O4—P1—O2	108.55 (10)
O4^iv—Ag1—O4^v	112.95 (7)	O5^v—P2—O5	105.56 (14)
O4—Ag1—O4^v	67.05 (7)	O5^v—P2—O6	113.12 (9)
O4^viii—Ag1—O4^v	180.00 (5)	O5—P2—O6	107.91 (9)
O5—Ag1—O5^viii	127.03 (7)	O5^v—P2—O6^v	107.91 (9)
O5^iv—Ag1—O5^viii	52.97 (7)	O5—P2—O6^v	113.12 (9)
O4^iv—Ag1—O5^viii	95.94 (5)	O6—P2—O6^v	109.26 (13)
O4—Ag1—O5^viii	84.06 (5)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, −y+3/2, −z; (iii) −x+3/2, −y+3/2, −z+1; (iv) −x+1, −y+1, −z; (v) −x+1, y, −z+1/2; (vi) x−1/2, −y+3/2, z−1/2; (vii) x, −y+1, z+1/2; (viii) x, −y+1, z−1/2; (ix) −x+2, y, −z+3/2; (x) −x+2, −y+1, −z+1; (xi) x+1/2, −y+1/2, z+1/2; (xii) −x+3/2, −y+1/2, −z+1.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray diffraction data collections and Mohammed V University in Rabat, Morocco, for financial support.

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