Synthesis, crystal structure and charge-distribution validation of a new alluaudite-type phosphate, Na2.22Mn0.87In1.68(PO4)3

Badri, A.; Alvarez-Serrano, I.; Luisa López, M.; Ben Amara, M.

doi:10.1107/S2056989020010191

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Volume 76| Part 8| August 2020| Pages 1369-1372

https://doi.org/10.1107/S2056989020010191

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Synthesis, crystal structure and charge-distribution validation of a new alluaudite-type phosphate, Na_2.22Mn_0.87In_1.68(PO₄)₃

Abdessalem Badri,^a ^* Inmaculada Alvarez-Serrano,^b María Luisa López ^b and Mongi Ben Amara ^a

^aLaboratory of Interfacial and Advanced Materials, Faculty of Sciences (FSM), University of Monastir, Monastir 5000, Tunisia, and ^bDepartamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain
^*Correspondence e-mail: badri_abdessalem@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 25 May 2020; accepted 23 July 2020; online 31 July 2020)

Na_2.22Mn_0.87In_1.68(PO₄₎₃, sodium manganese indium tris(phosphate) (2.22/0.87/1.68), was obtained in the form of single crystals by a flux method and was structurally characterized by single-crystal X-ray diffraction. The compound belongs to the alluaudite structure type (space group C2/c) with general formula X(2)X(1)M(1)M(2)₂(PO₄)₃. The X(2) and X(1) sites are partially occupied by sodium [occupancy 0.7676 (17) and 1/2] while the M(1) and M(2) sites are fully occupied within a mixed distribution of sodium/manganese(II) and manganese(II)/indium, respectively. The three-dimensional anionic framework is built up on the basis of M(2)₂O₁₀ dimers that share opposite edges with M(1)O₆ octahedra, thus forming infinite chains extending parallel to [10 $[\overline{1}]$ ]. The linkage between these chains is ensured by PO₄ tetrahedra through common vertices. The three-dimensional network thus constructed delimits two types of hexagonal channels, resulting from the catenation of M(2)₂O₁₀ dimers, M(1)O₆ octahedra and PO₄ tetrahedra through edge- and corner-sharing. The channels are occupied by Na⁺ cations with coordination numbers of seven and eight.

Keywords: crystal structure; indium phosphate; alluaudite structure type; disorder.

CCDC reference: 2018562

1. Chemical context

The general structural formula of alluaudite-type phosphates is [A(2)A(2)][A(1)A(1)'A(1)''₂]M(1)M(2)₂(PO₄)₃ (Hatert et al., 2000 ); in the majority of natural alluaudites, the large crystallographic A sites are occupied by Na⁺, Ca²⁺ or Mn²⁺, and the distorted-octahedrally surrounded M sites are occupied by Mn²⁺, Fe²⁺, Fe³⁺, Al³⁺ or Mg²⁺ (Moore & Ito, 1979 ). Alluaudite-type phosphates are frequently used for practical applications such as corrosion inhibition, passivation of metal surfaces, or catalysis (Korzenski et al., 1998 ; Kacimi et al., 2005 ). Furthermore, as a result of the presence of channels, alluaudite-type compounds exhibit electronic and/or ionic conductivity properties (Warner et al., 1994 ; Durio et al., 2002 ). The possibility of inserting variable amounts of lithium into the channels of the alluaudite structure also makes the (Na_1–xLi_x)MnFe³⁺₂(PO₄)₃ and (Na_1–xLi_x)_1.5Mn_1.5Fe³⁺_1.5(PO₄)₃ compounds of value as potential battery materials (Hatert et al., 2004 ; Trad et al., 2018 ). A number of indium-bearing alluaudite-like compounds have also been synthesized, i.e. NaCdIn₂(PO₄)₃ (Antenucci et al., 1993 ), Na₃In₂(PO₄)₃ (Lii & Ye, 1997 ), and NaMn(Fe_1–xIn_x)₂(PO₄)₃ (Hatert et al., 2003 ). In this paper, we report the structural study of a new alluaudite-type phosphate, Na_2.22Mn_0.87In_1.68(PO₄)₃, which was obtained during our investigation of the Na₃PO₄–Mn₃(PO₄)₂–InPO₄ quasi system.

2. Structural commentary

The principal building units (Fig. 1) of the three-dimensional framework structure of Na_2.22Mn_0.87In_1.68(PO₄)₃ are mixed-occupancy (Mn, Na) [= M(1); site symmetry 2] and (Mn1, In) [= M(2)] sites with distorted octahedral environments and two phosphate tetrahedra (P1 and P2); the two sites associated with Na⁺ cations (Na1; Na2 with site symmetry 2) are partially occupied and are situated in the resulting voids. By edge-sharing, the (Mn,In)O₆ octahedra form (Mn,In)₂O₁₀ dimers, which are linked by highly distorted (Mn,Na)O₆ octahedra into infinite zigzag chains along [10 $[\overline{1}]$ ] (Fig. 2). The connection of these chains through vertices belonging to P1O₄ and P2O₄ tetrahedra gives layers perpendicular to [010] (Fig. 3), which, in turn, are linked into the three-dimensional framework by sharing corners with phosphate tetrahedra. This framework accommodates two types of channels extending parallel to [001] in which the Na⁺ cations are located (Fig. 4).

Figure 1
The principal building units of the alluaudite-type phosphate Na_2.22Mn_0.87In_1.68(PO₄)₃ with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x, y, z − 1; (ii) x + 1, y, z + 1; (iii) x + 1, y, z + $[{3\over 2}]$ ; (iv) x, y, z − $[{3\over 2}]$ ; (v) x, y, z − $[{1\over 2}]$ ; (vi) x, y, z + $[{3\over 2}]$ ; (vii) x, y, z + 2; (viii) x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , z + $[{3\over 2}]$ ; (ix) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z; (x) x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (xi) x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z + 1; (xii) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (xiii) x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z + 2; (xiv) x + 1, y, z.]

Figure 2
Infinite zigzag chain extending parallel to [10 $[\overline{1}]$ ], built of edge-sharing M(2)₂O₁₀ and M(1)O₆ units.

Figure 3
The connection of individual chains via PO₄ tetrahedra to give sheets perpendicular to [010]_.

Figure 4
Projection of the Na_2.22Mn_0.87In_1.68(PO₄)₃ structure along the [001] direction showing channels occupied by the Na⁺ cations.

The mean <M1—O> distance of 2.329 Å is between those of 2.23 and 2.42 Å predicted by the sums of the ionic radii (Shannon, 1976 ) for Mn²⁺ and Na⁺ cations in an octahedral environment. The mean <M2—O> distance of 2.150 Å is between the mean distance of 2.142 Å observed for In³⁺ in an octahedral environment in NaCuIn(PO₄)₂ (Benhsina et al., 2020 ) and 2.238 Å for Mn²⁺ in the same coordination in K_0.53Mn_2.37Fe_1.24(PO₄)₃ (Hidouri & Ben Amara, 2011 ). The PO₄ tetrahedra show a slight distortion, as indicated by the range of P—O bond lengths [1.538 (2)–1.550 (2) Å for P1O₄ and 1.520 (3)–1.566 (2) Å for P2O₄], with mean bond lengths of <P1—O> = 1.544 (2) Å and <P2—O> = 1.546 (2) Å, consistent with 1.537 Å as calculated by Baur (1974 ) for the orthophosphate group. The coordination spheres of the two crystallographically distinct Na sites (Fig. 1) in the channels were defined under the assumption of a maximum Na—O distance L_max = 3.13 Å, suggested by Donnay & Allmann (1970 ). The environment around Na1 consists of seven O atoms with distances varying from 2.35 (3) to 2.99 (3) Å, and Na2 is bound to eight O atoms with distances in the range 2.510 (3)–2.928 (6) Å.

The refined structure model is confirmed by (i) the bond-valence method (Brown & Altermatt, 1985 ; Brown, 2002 ) and (ii) the charge-distribution (Chardi) method (Nespolo, 2015 , 2016 ). The Chardi method is a development of Pauling's concept of bond strength (Pauling, 1929 ). Instead of the empirical parameters used in the bond-valence approach, it exploits the experimental bond lengths deduced from the structural study to compute a non-integer coordination number (effective coordination number = ECoN) around a PC atom (atom placed at the center of a polyhedron, q > 0), which is coordinated by V atoms (atoms located at the vertices; q < 0); q is the formal oxidation number. ECoN takes into account not only the number of V atoms around a given PC atom, but also their weight in terms of relative distances. Calculated charges Q(i) and valences V(i) are in good agreement with the formal oxidation number (q) multiplied by occupancy rates. The dispersion factor MAPD, $[MAPD= {{100}\over{N}}\sum _{i=1}^{N}\left\vert {{q_{i}}-Q_{i}\over{q_{i}}}\right\vert]$ , which measures the mean absolute percentage deviation, is 1% for the calculated cationic charges. The variation of the ECoN value with respect to the traditional coordination number indicates the degree of distortion. The results of the two validation models are compiled in Table 1.

Table 1
CHARDI and BVS analysis of cations in Na_2.22Mn_0.87In_1.68(PO₄)₃

M1 = Mn/Na, M2 = Mn/In, q = formal oxidation number, sof(i) = site-occupation factor, Q(i) = calculated charges, CN = coordination number, ECoN = number of effective coordination, d_ar = arithmetic average distance to oxygen atoms and d_med = weighted average distance to oxygen atoms.

Cation	q.sof(i)	Q(i)	V(i).sof(i)	CN(i)	ECoN(i)	d_average	d_med
Na1	0.50	0.50	0.542	7	5.56	2.550	2.428
Na2	0.77	0.75	0.716	8	6.70	2.738	2.653
M1	1.54	1.56	1.421	6	6.00	2.329	2.330
M2	2.84	2.84	2.696	6	5.87	2.150	2.141
P1	5.00	4.92	4.873	4	4.00	1.544	1.544
P2	5.00	5.05	4.844	4	3.98	1.546	1.545

3. Synthesis and crystallization

Commercially available NaNO₃, Mn(NO₃)₂·6H₂O, In₂O₃, MoO₃ and (NH₄)₂HPO₄ were mixed in stoichiometric ratios of 2:1:1:1:2 and dissolved in aqueous nitric acid. The resulting solution was then evaporated by heating at 353 K. The obtained dry residue was ground in an agate mortar, and then heated increasingly in an open platinum crucible up to 873 K. The sample was then reground and mixed with sodium dimolybdate Na₂Mo₂O₇ in the molar ratio P:Mo = 2:1. The mixture was heated for 1 h at 1243 K to give a melt that was subsequently cooled down to room temperature at a rate of 10 K h⁻¹. Brown hexagonally shaped crystals were obtained by washing the final product with hot water in order to dissolve the flux.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The bond lengths involving M1—O and M2—O are those between the mean Na—O and Mn—O and the mean In—O and Mn—O bond lengths, respectively. We used EADP, EXYZ and SUMP constraints within SHELXL2018/3 (Sheldrick, 2015 ) for the mixed-occupied M1 [refined ratio Mn:Na = 0.5438 (14):0.4562 (14)] and M2 [refined ratio In:Mn = 0.8443 (5):0.1557 (5)] sites. Na2 shows an occupancy of 0.7676 (17), and free refinement of the occupancy of Na1 resulted in a value very close to 0.5. For the final refinement, this value was fixed at 0.5, and all other occupancies were refined to ensure electrical neutrality of the compound. The remaining maximum and minimum electron densities are located 0.74 Å from P2 and 1.07 Å from O24, respectively.

Table 2
Experimental details

Crystal data
Chemical formula	Na_2.22Mn_0.87In_1.68(PO₄)₃
M_r	575.82
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.412 (2), 12.855 (2), 6.599 (1)
β (°)	114.727 (2)
V (Å³)	956.4 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.81
Crystal size (mm)	0.29 × 0.17 × 0.11

Data collection
Diffractometer	Nonius Kappa CCD
Absorption correction	Part of the refinement model (ΔF) (Parkin et al., 1995 )
T_min, T_max	0.178, 0.222
No. of measured, independent and observed [I > 2σ(I)] reflections	1183, 1183, 1172
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.054, 1.31
No. of reflections	1183
No. of parameters	102
No. of restraints	3
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.83
Computer programs: KappaCCD Server Software (Nonius, 1997 ), HKL SCALEPACK and DENZO (Otwinovski & Minor, 1997 ), SIR92 (Altomare et al., 1993 ), SHELXL2018/3 (Sheldrick, 2015), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and DIAMOND (Brandenburg, 1999 ).

Supporting information

CCDC reference: 2018562

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989020010191/wm5566sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020010191/wm5566Isup2.hkl

CHARDI and BVS analysis of cation polyhedra in Na2.22Mn0.87In1.68(PO4)3. DOI: https://doi.org/10.1107/S2056989020010191/wm5566sup3.docx

checkCIF report

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinovski & Minor, 1997); data reduction: HKL DENZO (Otwinovski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Sodium manganese indium tris(phosphate) (2.22/0.87/1.68) top

Crystal data top

Na_2.22Mn_0.87In_1.68(PO₄)₃	F(000) = 1100
M_r = 575.82	D_x = 4.115 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.412 (2) Å	θ = 3.2–28.9°
b = 12.855 (2) Å	µ = 5.81 mm⁻¹
c = 6.599 (1) Å	T = 293 K
β = 114.727 (2)°	Prism, brown
V = 956.4 (3) Å³	0.29 × 0.17 × 0.11 mm
Z = 4

Data collection top

Nonius Kappa CCD diffractometer	1172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
non–profiled ω/2τ scans	θ_max = 28.9°, θ_min = 2.4°
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995)	h = −16→14
T_min = 0.178, T_max = 0.222	k = 0→16
1183 measured reflections	l = 0→8
1183 independent reflections

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.021	w = 1/[σ²(F_o²) + (0.0135P)² + 7.1094P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.054	(Δ/σ)_max = 0.023
S = 1.31	Δρ_max = 0.73 e Å⁻³
1183 reflections	Δρ_min = −0.83 e Å⁻³
102 parameters

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)
Na1	0.492 (3)	0.003 (3)	0.013 (5)	0.017 (2)	0.5
Na2	0	−0.0079 (4)	0.75	0.0586 (13)	0.7676 (17)
Mn	0.5	0.22924 (8)	0.25	0.0128 (2)	0.5438 (14)
Na	0.5	0.22924 (8)	0.25	0.0128 (2)	0.4562 (14)
In	0.22327 (2)	0.15486 (2)	0.64458 (4)	0.00781 (9)	0.8443 (5)
Mn1	0.22327 (2)	0.15486 (2)	0.64458 (4)	0.00781 (9)	0.1557 (5)
P1	0.5	0.21702 (9)	0.75	0.0075 (2)
O11	0.5471 (2)	0.2867 (2)	0.9611 (4)	0.0138 (5)
O12	0.4072 (2)	0.14288 (19)	0.7683 (4)	0.0140 (5)
P2	0.23767 (7)	0.10662 (6)	1.13105 (13)	0.00841 (17)
O21	0.1736 (3)	0.0029 (2)	1.1238 (4)	0.0172 (5)
O22	0.2293 (2)	0.17542 (19)	1.3198 (4)	0.0112 (5)
O23	0.1663 (2)	0.16388 (19)	0.9065 (4)	0.0139 (5)
O24	0.3668 (2)	0.0921 (2)	1.1731 (5)	0.0206 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.023 (7)	0.013 (3)	0.012 (5)	0.004 (4)	0.005 (3)	−0.002 (3)
Na2	0.027 (2)	0.073 (3)	0.055 (3)	0	−0.0025 (19)	0
Mn	0.0146 (5)	0.0121 (5)	0.0141 (5)	0	0.0083 (4)	0
Na	0.0146 (5)	0.0121 (5)	0.0141 (5)	0	0.0083 (4)	0
In	0.00802 (13)	0.00782 (13)	0.00813 (14)	0.00050 (8)	0.00390 (10)	0.00093 (8)
Mn1	0.00802 (13)	0.00782 (13)	0.00813 (14)	0.00050 (8)	0.00390 (10)	0.00093 (8)
P1	0.0062 (5)	0.0092 (5)	0.0055 (5)	0	0.0008 (4)	0
O11	0.0097 (11)	0.0174 (12)	0.0121 (11)	0.0005 (9)	0.0024 (9)	−0.0062 (9)
O12	0.0083 (11)	0.0139 (12)	0.0184 (13)	−0.0007 (9)	0.0042 (10)	0.0045 (9)
P2	0.0131 (4)	0.0069 (4)	0.0063 (4)	0.0012 (3)	0.0051 (3)	0.0005 (3)
O21	0.0287 (14)	0.0080 (11)	0.0163 (13)	0.0006 (10)	0.0108 (11)	0.0008 (9)
O22	0.0154 (12)	0.0105 (11)	0.0081 (11)	−0.0003 (9)	0.0053 (9)	−0.0005 (9)
O23	0.0232 (13)	0.0120 (12)	0.0079 (11)	0.0027 (9)	0.0079 (10)	0.0021 (9)
O24	0.0201 (14)	0.0249 (14)	0.0206 (14)	0.0084 (11)	0.0124 (11)	0.0071 (11)

Geometric parameters (Å, º) top

Na1—O12ⁱ	2.35 (3)	Mn—O23^xi	2.330 (3)
Na1—O12ⁱⁱ	2.38 (3)	Mn—O11ⁱⁱⁱ	2.335 (3)
Na1—O24ⁱⁱⁱ	2.38 (3)	Mn—O11ⁱ	2.335 (3)
Na1—O24^iv	2.45 (3)	In—O12	2.084 (2)
Na1—O24ⁱ	2.489 (18)	In—O21^v	2.107 (3)
Na1—O24ⁱⁱ	2.811 (17)	In—O23	2.127 (3)
Na1—O12^v	2.99 (3)	In—O11^xii	2.144 (2)
Na2—O21	2.510 (3)	In—O22ⁱ	2.192 (2)
Na2—O21^vi	2.510 (3)	In—O22^xiii	2.246 (2)
Na2—O21^v	2.616 (3)	P1—O12	1.538 (2)
Na2—O21^vii	2.616 (3)	P1—O12ⁱⁱⁱ	1.538 (2)
Na2—O23^vi	2.901 (5)	P1—O11ⁱⁱⁱ	1.550 (2)
Na2—O23	2.901 (5)	P1—O11	1.550 (2)
Na2—O11^viii	2.928 (6)	P2—O24	1.520 (3)
Na2—O11^ix	2.928 (6)	P2—O21	1.543 (3)
Mn—O24ⁱ	2.323 (3)	P2—O23	1.557 (3)
Mn—O24ⁱⁱⁱ	2.323 (3)	P2—O22	1.566 (2)
Mn—O23^x	2.330 (3)

O12ⁱ—Na1—O12ⁱⁱ	172.0 (8)	O21^vii—Na2—O11^ix	84.12 (12)
O12ⁱ—Na1—O24ⁱⁱⁱ	100.6 (13)	O23^vi—Na2—O11^ix	145.72 (9)
O12ⁱⁱ—Na1—O24ⁱⁱⁱ	80.8 (10)	O23—Na2—O11^ix	123.11 (7)
Na1^xiv—Na1—O24^iv	73 (10)	O11^viii—Na2—O11^ix	51.21 (13)
O12ⁱ—Na1—O24^iv	79.9 (10)	O24ⁱ—Mn—O24ⁱⁱⁱ	81.29 (13)
O12ⁱⁱ—Na1—O24^iv	97.6 (12)	O24ⁱ—Mn—O23^x	164.09 (10)
O24ⁱⁱⁱ—Na1—O24^iv	172.4 (9)	O24ⁱⁱⁱ—Mn—O23^x	86.16 (9)
O12ⁱ—Na1—O24ⁱ	76.2 (8)	O24ⁱ—Mn—O23^xi	86.16 (9)
O12ⁱⁱ—Na1—O24ⁱ	111.7 (10)	O24ⁱⁱⁱ—Mn—O23^xi	164.09 (10)
O24ⁱⁱⁱ—Na1—O24ⁱ	76.9 (7)	O23^x—Mn—O23^xi	107.74 (13)
O24^iv—Na1—O24ⁱ	110.6 (11)	O24ⁱ—Mn—O11ⁱⁱⁱ	91.16 (9)
O12ⁱ—Na1—O24ⁱⁱ	102.3 (8)	O24ⁱⁱⁱ—Mn—O11ⁱⁱⁱ	117.37 (9)
O12ⁱⁱ—Na1—O24ⁱⁱ	69.7 (6)	O23^x—Mn—O11ⁱⁱⁱ	85.95 (9)
O24ⁱⁱⁱ—Na1—O24ⁱⁱ	102.7 (9)	O23^xi—Mn—O11ⁱⁱⁱ	72.40 (9)
O24^iv—Na1—O24ⁱⁱ	69.8 (6)	O24ⁱ—Mn—O11ⁱ	117.37 (9)
O24ⁱ—Na1—O24ⁱⁱ	178.4 (15)	O24ⁱⁱⁱ—Mn—O11ⁱ	91.16 (9)
O12ⁱ—Na1—O12^v	135.0 (10)	O23^x—Mn—O11ⁱ	72.40 (9)
O12ⁱⁱ—Na1—O12^v	51.9 (6)	O23^xi—Mn—O11ⁱ	85.95 (9)
O24ⁱⁱⁱ—Na1—O12^v	96.7 (9)	O11ⁱⁱⁱ—Mn—O11ⁱ	143.12 (14)
O24^iv—Na1—O12^v	88.1 (10)	O12—In—O21^v	101.37 (10)
O24ⁱ—Na1—O12^v	67.8 (5)	O12—In—O23	111.59 (10)
O24ⁱⁱ—Na1—O12^v	113.8 (11)	O21^v—In—O23	85.28 (10)
O21—Na2—O21^vi	173.7 (3)	O12—In—O11^xii	159.80 (10)
O21—Na2—O21^v	80.14 (8)	O21^v—In—O11^xii	95.68 (10)
O21^vi—Na2—O21^v	99.71 (8)	O23—In—O11^xii	80.34 (10)
O21—Na2—O21^vii	99.71 (8)	O12—In—O22ⁱ	84.96 (10)
O21^vi—Na2—O21^vii	80.14 (8)	O21^v—In—O22ⁱ	100.43 (10)
O21^v—Na2—O21^vii	177.2 (3)	O23—In—O22ⁱ	161.27 (10)
O21—Na2—O23^vi	119.88 (19)	O11^xii—In—O22ⁱ	81.35 (9)
O21^vi—Na2—O23^vi	54.39 (10)	O12—In—O22^xiii	80.47 (9)
O21^v—Na2—O23^vi	115.22 (16)	O21^v—In—O22^xiii	176.57 (10)
O21^vii—Na2—O23^vi	62.40 (10)	O23—In—O22^xiii	91.36 (9)
O21—Na2—O23	54.39 (10)	O11^xii—In—O22^xiii	83.08 (9)
O21^vi—Na2—O23	119.88 (19)	O22ⁱ—In—O22^xiii	82.57 (9)
O21^v—Na2—O23	62.40 (10)	O12—P1—O12ⁱⁱⁱ	103.4 (2)
O21^vii—Na2—O23	115.22 (16)	O12—P1—O11ⁱⁱⁱ	114.56 (13)
O23^vi—Na2—O23	80.89 (17)	O12ⁱⁱⁱ—P1—O11ⁱⁱⁱ	107.48 (14)
O21—Na2—O11^viii	115.83 (18)	O12—P1—O11	107.48 (14)
O21^vi—Na2—O11^viii	70.36 (11)	O12ⁱⁱⁱ—P1—O11	114.56 (13)
O21^v—Na2—O11^viii	84.12 (12)	O11ⁱⁱⁱ—P1—O11	109.4 (2)
O21^vii—Na2—O11^viii	98.43 (14)	O24—P2—O21	112.98 (16)
O23^vi—Na2—O11^viii	123.11 (7)	O24—P2—O23	111.62 (15)
O23—Na2—O11^viii	145.71 (9)	O21—P2—O23	107.34 (15)
O21—Na2—O11^ix	70.36 (11)	O24—P2—O22	109.88 (15)
O21^vi—Na2—O11^ix	115.83 (18)	O21—P2—O22	107.94 (14)
O21^v—Na2—O11^ix	98.43 (14)	O23—P2—O22	106.81 (14)

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

CHARDI and BVS analysis of cations in Na_2.22Mn_0.87In_1.68(PO₄)₃ top

Cation	q.sof(i)	Q(i)	V(i).sof(i)	CN(i)	ECoN(i)	d_average	d_med
Na1	0.50	0.50	0.542	7	5.56	2.550	2.428
Na2	0.77	0.75	0.716	8	6.70	2.738	2.653
M1	1.54	1.56	1.421	6	6.00	2.329	2.330
M2	2.84	2.84	2.696	6	5.87	2.150	2.141
P1	5.00	4.92	4.873	4	4.00	1.544	1.544
P2	5.00	5.05	4.844	4	3.98	1.546	1.545

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