Crystal structure of barium dinickel(II) iron(III) tris­[orthophosphate(V)], BaNi2Fe(PO4)3

Ouaatta, S.; Bouraima, A.; Benhsina, E.; Khmiyas, J.; Assani, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S2056989023000336

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ISSN: 2056-9890

Volume 79| Part 2| February 2023| Pages 95-98

https://doi.org/10.1107/S2056989023000336

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Crystal structure of barium dinickel(II) iron(III) tris[orthophosphate(V)], BaNi₂Fe(PO₄)₃

Said Ouaatta,^a ^* Adam Bouraima,^a,^b Elhassan Benhsina,^a Jamal Khmiyas,^a Abderrazzak Assani,^a Mohamed Saadi ^a and Lahcen El Ammari ^a

^aLaboratoire de Chimie Appliquée des Matériaux, Centre des Sciences des Matériaux, Faculty of Science, Mohammed V University in Rabat, Avenue Ibn Batouta, BP 1014, Rabat, Morocco, and ^bLaboratoire de Chimie des Matériaux Inorganiques, Faculté des Sciences, Département de Chimie, Université des Sciences et Techniques de Masuku, BP 943, Franceville, Gabon
^*Correspondence e-mail: saidouaatta87@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 29 November 2022; accepted 12 January 2023; online 17 January 2023)

This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.

The orthophosphate BaNi₂Fe(PO₄)₃ has been synthesized by a solid-state reaction route and characterized by single-crystal X-ray diffraction and energy-dispersive X-ray spectroscopy. The crystal structure comprises (100) sheets made up of [Ni₂O₁₀] dimers that are linked to two PO₄ tetrahedra via common edges and vertices and of linear infinite [010] chains of corner-sharing [FeO₆] octahedra and [PO₄] tetrahedra. The linkage of the sheets and chains into a framework is accomplished through common vertices of PO₄ tetrahedra and [FeO₆] octahedra. The framework is perforated by channels in which positionally disordered Ba²⁺ cations are located.

Keywords: crystal structure; orthophosphates; solid-state reactions; α-CrPO₄-type structure BaNi₂Fe(PO₄)₃.

CCDC reference: 2172184

1. Chemical context

Phosphate-based materials have been studied extensively in the past. Among them are orthophosphates, which have gained great interest in recent years owing to their structural richness (Maeda, 2004 ) and their promising applications, for example in electrochemical catalysis (Dwibedi et al., 2020 ; Cheng et al., 2021 ; Rekha et al., 2021 ; Anahmadi et al., 2022 ). Furthermore, orthophosphates doped with rare-earth cations have shown excellent optical properties (Ci et al., 2014 ; Li et al., 2021 ; Indumathi et al., 2022 ), along with a wide range of applications for use in luminescence emission displays (Li et al., 2008 ; Wan et al., 2010 ; Yang et al., 2019 ; Santos et al., 2022 ).

In this context, our research interest is connected with tris-orthophosphate-based materials with general formula (A₂/B)M₂M′(PO₄)₃, where A can be an alkali, B an alkaline earth and M and M′ transition metal cations. The crystal structures of these orthophosphates adopt the α-CrPO₄ type of structure, consisting of a three-dimensional framework made up of [MO₆] and [M′O₆] octahedra sharing corners and/or edges with PO₄ tetrahedra. This framework is permeated by channels in which the A or B cations are located.

We report herein on the synthesis and structural characterization of barium dinickel(II) iron(III) tris-orthophosphate, BaNi₂Fe(PO₄)₃.

2. Structural commentary

The title compound is related to the strontium and calcium homologs MNi₂Fe(PO₄)₃ (M = Sr, Ca; Ouaatta et al., 2015 , 2017 ), all adopting the α-CrPO₄ structure type (Attfield et al., 1986 ). The asymmetric unit of BaNi₂Fe(PO₄)₃ is comprised of ten sites, eight of which are on special positions, except the O3 and O4 sites on a general position (Wyckoff position 16 j). Ba1 (site occupation 0.9868) exhibits site symmetry mm2 (4 e), Ba2 (site occupation 0.0132) 2/m (4 a), Fe1 2/m (4 b), Ni1 2 (8 g), P1 mm2 (4 e), P2 2 (8 g), while O1 and O2 occupy sites with m (8 h) and m (8 i) symmetry, respectively. The framework structure of BaNi₂Fe(PO₄)₃ is composed of extended (100) sheets and linear infinite chains extending parallel to [010] (Fig. 1). The (100) sheets are made up from edge-sharing [Ni₂O₁₀] dimers linked to two P2O₄ tetrahedra via common edges to form an [Ni₂P2₂O₁₄] unit that is linked to four neighboring units (Fig. 2). Between these sheets appear the linear infinite chains resulting from the alternating linkage of P1O₄ tetrahedra and [FeO₆] octahedra, which are surrounded by a zigzag arrangement of Ba²⁺ cations (Fig. 3). The sheets and chains are linked through common vertices of PO₄ tetrahedra and [FeO₆] octahedra into a framework, which delimits two types of channels parallel to [100] and [010] in which the disordered Ba²⁺ cations are located (Figs. 4, 5).

Figure 1
The principal building units in the crystal structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + 1, −y + $[{1\over 2}]$ , z − 1; (ii) x, y, z − 1; (iii) −x + 1, −y + $[{1\over 2}]$ , z; (iv) −x + $[{3\over 2}]$ , −y + 1, z − $[{1\over 2}]$ ; (v) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vi) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vii) x − $[{1\over 2}]$ , −y + 1, z − $[{1\over 2}]$ ; (viii) −x + 2, −y + 1, −z + 2; (ix) −x + 2, y, z; (x) x, −y + 1, −z + 2; (xi) −x + $[{3\over 2}]$ , −y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (xii) −x + $[{3\over 2}]$ , y, −z + $[{3\over 2}]$ ; (xiii) x, −y + 1, −z + 1; (xiv) −x + 2, −y + 1, −z + 1; (xv) x + $[{1\over 2}]$ , y, −z + $[{3\over 2}]$ ].

Figure 2
Projection of a (100) sheet along [100] showing the [Ni₂P(2)₂O₁₄] unit.

Figure 3
A chain formed by sharing corners of [FeO₆] octahedra and P1O₄ tetrahedra, alternating with a zigzag arrangement of barium cations (Ba1) along [010].

Figure 4
Polyhedral representation of the crystal structure of BaNi₂Fe(PO₄)₃ showing Ba1 in the channels running along the [100] direction and a row of underoccupied Ba2 along [001].

Figure 5
Polyhedral representation of the crystal structure of BaNi₂Fe(PO₄)₃ showing Ba1 and Ba2 in the channels.

To confirm the structure model of BaNi₂Fe(PO₄)₃, the bond-valence method (Brown, 1977 ; 1978 ; Brown & Altermatt, 1985 ) and charge distribution (CHARDI) concept (Hoppe et al., 1989 ) were employed by making use of the programs EXPO2014 (Altomare et al., 2013 ) and CHARDI2015 (Nespolo & Guillot, 2016 ), respectively. Table 1 compiles all cationic valences V(i) computed with the bond-valence method and their related charges Q(i) obtained with the CHARDI concept. The resulting Q(i) and V(i) values are all close to the corresponding charges q(i)×sof(i) [q(i) are formal oxidation numbers weighted by the site occupation factors sof(i)]. In summary, the expected oxidation states of Ba²⁺, Ni²⁺, Fe³⁺ and P⁵⁺ are predicted through the charge distribution. The internal criterion q(i)/Q(i) is very near to 1 for all ionic species and the mean absolute percentage deviation (MAPD), which gives a measure for the agreement between the q(i) and Q(i) charges, is just 1.3%, thus confirming the validity of the structure model (Eon & Nespolo, 2015 ). The global instability index (GII; Salinas-Sanchez et al., 1992 ) of 0.13 is a further confirmation of the structure model.

Table 1
Bond valence and CHARDI analyses for the cations in the title compound

q(i) = formal oxidation number; sof(i) = site occupancy; CN(i) = classical coordination number; Q(i) = calculated charge; V(i) = calculated valence; ECoN(i) = effective coordination number.

Cation	q(i)	sof(i)	CN(i)	ECoN(i)	V(i)	Q(i)	q(i)/Q(i)
Ba1	1.98	0.99	8	7.99	2.37	1.98	1.00
Ba2	0.02	0.01	8	5.43	0.02	0.99
Ni	2.00	1.00	6	5.97	2.00	1.98	1.01
Fe	3.00	1.00	4	5.96	3.01	2.99	1.00
P1	5.00	1.00	4	3.99	4.95	4.83	1.04
P2	5.00	1.00	4	3.96	4.85	5.11	0.98

3. Database survey

It is reasonable to compare the crystal structure of the title compound with that of α-CrPO₄ (Glaum et al., 1986 ). Both phosphates crystallize in the orthorhombic system in space group type Imma. Their unit-cell parameters are nearly the same despite the differences between their chemical formulae. In the structure of α-CrPO₄, the Cr³⁺ and P⁵⁺ cations occupy four special positions that are part of a framework is comprised of [CrO₆] octahedra and [PO₄] tetrahedra. The resultant framework is permeated by vacant channels along [100] and [010]. The formula of α-CrPO₄ can be written as X1X2Cr1Cr2₂(PO₄)₃, where X1, X2 represent the empty channel sites. Accordingly, the substitution of Cr1 or Cr2 by a divalent cation requires charge compensation by cations located in the channels to result in AA'MM'₂(PO₄)₃ compounds such as BaNi₂Fe(PO₄)₃, or MNi₂Fe(PO₄)₃ (M = Sr, Ca; Ouaatta et al., 2015, 2017). The difference between BaNi₂Fe(PO₄)₃ and the closely related MNi₂Fe(PO₄)₃ structures pertains to the M site, which is split into two sites for the title compound and fully occupied for M = Ca, Sr.

4. Synthesis and crystallization

BaNi₂Fe(PO₄)₃ was prepared from a mixture of Ba(NO₃)₂ (Merck, 98.5%), Ni(NO₃)₂·6H₂O (Riedel-de-Haén, 97%), Fe(NO₃)₃·9H₂O (Panreac, 98%) and H₃PO₄ (85%_wt) in the molar ratio of Ba:Ni:Fe:P = 1:2:1:3. The precursors were suspended in 50 ml of distilled water and stirred without warming for 24 h before heating to dryness at 373 K. The obtained dry residue was ground in an agate mortar until homogeneous, subsequently heated in a platinum crucible up to 673 K to remove volatile decomposition products, and then melted at 1433 K. After being kept at this temperature for one h, the melt was cooled down slowly at a rate of 5 K h⁻¹ to 1233 K and then to room temperature. Single crystals with a brown color and different forms were obtained after leaching with distilled water.

Chemical analysis of the title phosphate was performed with an energy-dispersive X-ray spectroscopy (EDS) microprobe mounted on a JEOL JSM-IT100 in TouchScope^TM scanning electron microscope. The EDS spectrum is depicted in Fig. 6 and confirms the presence of only barium, nickel, iron, phosphorus and oxygen in approximately the correct ratios, as shown in Table 2.

Table 2
Atom percentages in BaNi₂Fe(PO₄)₃ as determined by EDS

Element	Atomic percentage	Sigma
O	56.74	0.13
P	19.60	0.16
Fe	5.63	0.17
Ni	12.25	0.27
Ba	5.78	0.30
Total	100.00

Figure 6
SEM micrograph and results of an EDS measurement of the title compound.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. After assignment of the atomic sites according to the related MNi₂Fe(PO₄)₃ structures (M = Sr, Ca; Ouaatta et al., 2015, 2017), a difference-Fourier map revealed a maximum electron density of 3.61 Å⁻³ that was finally modeled as a considerably underoccupied Ba site (Ba2). For the final model, the sum of site-occupation factors for the Ba1 and Ba2 sites were constrained to be 1. The highest remaining maximum and minimum electronic densities are 0.59 Å and 0.47 Å from Ba1 and Ni1, respectively.

Table 3
Experimental details

Crystal data
Chemical formula	BaNi₂Fe(PO₄)₃
M_r	595.52
Crystal system, space group	Orthorhombic, Imma
Temperature (K)	296
a, b, c (Å)	10.4711 (2), 13.2007 (3), 6.6132 (1)
V (Å³)	914.12 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	10.46
Crystal size (mm)	0.32 × 0.25 × 0.19

Data collection
Diffractometer	Bruker X8 APEX Diffractometer
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.624, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	18099, 1460, 1440
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.893

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.036, 1.21
No. of reflections	1460
No. of parameters	58
Δρ_max, Δρ_min (e Å⁻³)	1.33, −0.78
Computer programs: APEX3 (Bruker, 2016 ), SAINT (Bruker, 2016), SAINT (Bruker, 2016), SHELXT2014/4 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ), publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2172184

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023000336/wm5667sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023000336/wm5667Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Barium dinickel(II) iron(III) tris[orthophosphate(V)] top

Crystal data top

BaNi₂Fe(PO₄)₃	D_x = 4.327 Mg m⁻³
M_r = 595.52	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Imma	Cell parameters from 1460 reflections
a = 10.4711 (2) Å	θ = 3.1–39.4°
b = 13.2007 (3) Å	µ = 10.46 mm⁻¹
c = 6.6132 (1) Å	T = 296 K
V = 914.12 (3) Å³	Block, colourless
Z = 4	0.32 × 0.25 × 0.19 mm
F(000) = 1116

Data collection top

Bruker X8 APEX Diffractometer	1460 independent reflections
Radiation source: fine-focus sealed tube	1440 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 39.4°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −18→13
T_min = 0.624, T_max = 0.748	k = −23→23
18099 measured reflections	l = −11→11

Refinement top

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)] = 0.015	w = 1/[σ²(F_o²) + (0.0147P)² + 1.8221P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.036	(Δ/σ)_max = 0.001
S = 1.21	Δρ_max = 1.33 e Å⁻³
1460 reflections	Δρ_min = −0.78 e Å⁻³
58 parameters	Extinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00403 (16)

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)
Ba1	0.500000	0.250000	0.39902 (2)	0.00770 (4)	0.9868
Ba2	1.000000	0.500000	1.000000	0.020 (2)	0.0132
Ni1	0.750000	0.36701 (2)	0.750000	0.00501 (4)
Fe1	1.000000	0.500000	0.500000	0.00337 (5)
P1	0.500000	0.250000	0.90454 (8)	0.00317 (8)
P2	0.750000	0.57020 (3)	0.750000	0.00365 (6)
O1	0.500000	0.34524 (8)	1.03493 (17)	0.00581 (16)
O2	0.61939 (10)	0.250000	0.76536 (17)	0.00534 (15)
O3	0.78276 (8)	0.63385 (6)	0.93423 (13)	0.00771 (12)
O4	0.86254 (7)	0.49395 (6)	0.70839 (12)	0.00574 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.00681 (5)	0.01253 (6)	0.00377 (5)	0.000	0.000	0.000
Ba2	0.014 (5)	0.041 (8)	0.006 (4)	0.000	0.000	0.000 (4)
Ni1	0.00498 (7)	0.00383 (7)	0.00621 (8)	0.000	0.00057 (5)	0.000
Fe1	0.00303 (10)	0.00352 (10)	0.00355 (10)	0.000	0.000	0.00008 (8)
P1	0.00348 (18)	0.00281 (17)	0.00322 (18)	0.000	0.000	0.000
P2	0.00380 (13)	0.00392 (13)	0.00324 (12)	0.000	0.00055 (10)	0.000
O1	0.0078 (4)	0.0033 (3)	0.0063 (4)	0.000	0.000	−0.0014 (3)
O2	0.0042 (4)	0.0063 (4)	0.0055 (4)	0.000	0.0016 (3)	0.000
O3	0.0096 (3)	0.0080 (3)	0.0055 (3)	−0.0024 (2)	0.0007 (2)	−0.0023 (2)
O4	0.0045 (3)	0.0058 (3)	0.0070 (3)	0.0009 (2)	0.0016 (2)	0.0006 (2)

Geometric parameters (Å, º) top

Ba1—O1ⁱ	2.7163 (11)	Ni1—O4	2.0670 (8)
Ba1—O1ⁱⁱ	2.7163 (11)	Ni1—O4^xii	2.0670 (8)
Ba1—O2ⁱⁱⁱ	2.7262 (11)	Ni1—O3^x	2.1163 (8)
Ba1—O2	2.7262 (11)	Ni1—O3^iv	2.1163 (8)
Ba1—O3^iv	2.7530 (8)	Fe1—O4	1.9944 (8)
Ba1—O3^v	2.7530 (8)	Fe1—O4^ix	1.9944 (8)
Ba1—O3^vi	2.7530 (8)	Fe1—O4^xiii	1.9944 (8)
Ba1—O3^vii	2.7530 (8)	Fe1—O4^xiv	1.9944 (8)
Ba2—O4	2.4077 (8)	Fe1—O1^iv	2.0559 (11)
Ba2—O4^viii	2.4078 (8)	Fe1—O1^xv	2.0559 (11)
Ba2—O4^ix	2.4078 (8)	P1—O1	1.5246 (11)
Ba2—O4^x	2.4078 (8)	P1—O1ⁱⁱⁱ	1.5246 (11)
Ba2—O3^ix	2.9129 (9)	P1—O2	1.5524 (11)
Ba2—O3^x	2.9129 (9)	P1—O2ⁱⁱⁱ	1.5524 (11)
Ba2—O3^viii	2.9129 (9)	P2—O3	1.5192 (8)
Ba2—O3	2.9129 (9)	P2—O3^xii	1.5193 (8)
Ni1—O2^xi	2.0655 (7)	P2—O4^xii	1.5739 (8)
Ni1—O2	2.0655 (7)	P2—O4	1.5739 (8)

O1ⁱ—Ba1—O1ⁱⁱ	55.14 (4)	O4^viii—Ba2—O3	124.49 (2)
O1ⁱ—Ba1—O2ⁱⁱⁱ	141.97 (2)	O4^ix—Ba2—O3	111.55 (2)
O1ⁱⁱ—Ba1—O2ⁱⁱⁱ	141.97 (2)	O4^x—Ba2—O3	68.45 (2)
O1ⁱ—Ba1—O2	141.97 (2)	O3^ix—Ba2—O3	102.68 (3)
O1ⁱⁱ—Ba1—O2	141.97 (2)	O3^x—Ba2—O3	77.32 (3)
O2ⁱⁱⁱ—Ba1—O2	54.59 (5)	O3^viii—Ba2—O3	180.0
O1ⁱ—Ba1—O3^iv	109.44 (2)	O2^xi—Ni1—O2	83.20 (5)
O1ⁱⁱ—Ba1—O3^iv	79.47 (2)	O2^xi—Ni1—O4	102.84 (3)
O2ⁱⁱⁱ—Ba1—O3^iv	107.68 (3)	O2—Ni1—O4	172.00 (3)
O2—Ba1—O3^iv	63.00 (2)	O2^xi—Ni1—O4^xii	172.00 (4)
O1ⁱ—Ba1—O3^v	79.47 (2)	O2—Ni1—O4^xii	102.84 (3)
O1ⁱⁱ—Ba1—O3^v	109.44 (2)	O4—Ni1—O4^xii	71.66 (4)
O2ⁱⁱⁱ—Ba1—O3^v	63.00 (2)	O2^xi—Ni1—O3^x	86.40 (4)
O2—Ba1—O3^v	107.68 (3)	O2—Ni1—O3^x	93.14 (4)
O3^iv—Ba1—O3^v	170.30 (4)	O4—Ni1—O3^x	92.48 (3)
O1ⁱ—Ba1—O3^vi	79.47 (2)	O4^xii—Ni1—O3^x	88.02 (3)
O1ⁱⁱ—Ba1—O3^vi	109.44 (2)	O2^xi—Ni1—O3^iv	93.14 (4)
O2ⁱⁱⁱ—Ba1—O3^vi	107.68 (3)	O2—Ni1—O3^iv	86.40 (4)
O2—Ba1—O3^vi	63.00 (2)	O4—Ni1—O3^iv	88.02 (3)
O3^iv—Ba1—O3^vi	67.69 (4)	O4^xii—Ni1—O3^iv	92.48 (3)
O3^v—Ba1—O3^vi	111.43 (4)	O3^x—Ni1—O3^iv	179.39 (5)
O1ⁱ—Ba1—O3^vii	109.44 (2)	O2^xi—Ni1—P2	138.40 (2)
O1ⁱⁱ—Ba1—O3^vii	79.47 (2)	O2—Ni1—P2	138.40 (2)
O2ⁱⁱⁱ—Ba1—O3^vii	63.00 (2)	O4—Fe1—O4^ix	92.40 (5)
O2—Ba1—O3^vii	107.68 (3)	O4—Fe1—O4^xiii	87.60 (5)
O3^iv—Ba1—O3^vii	111.43 (4)	O4^ix—Fe1—O4^xiii	180.0
O3^v—Ba1—O3^vii	67.69 (4)	O4—Fe1—O4^xiv	180.0
O3^vi—Ba1—O3^vii	170.30 (4)	O4^ix—Fe1—O4^xiv	87.60 (5)
O4—Ba2—O4^viii	180.0	O4^xiii—Fe1—O4^xiv	92.40 (5)
O4—Ba2—O4^ix	73.43 (4)	O4—Fe1—O1^iv	87.83 (3)
O4^viii—Ba2—O4^ix	106.57 (4)	O4^ix—Fe1—O1^iv	87.83 (3)
O4—Ba2—O4^x	106.57 (4)	O4^xiii—Fe1—O1^iv	92.17 (3)
O4^viii—Ba2—O4^x	73.43 (4)	O4^xiv—Fe1—O1^iv	92.17 (3)
O4^ix—Ba2—O4^x	180.0	O4—Fe1—O1^xv	92.17 (3)
O4—Ba2—O3^ix	111.55 (2)	O4^ix—Fe1—O1^xv	92.17 (3)
O4^viii—Ba2—O3^ix	68.45 (2)	O4^xiii—Fe1—O1^xv	87.83 (3)
O4^ix—Ba2—O3^ix	55.51 (2)	O4^xiv—Fe1—O1^xv	87.83 (3)
O4^x—Ba2—O3^ix	124.49 (2)	O1^iv—Fe1—O1^xv	180.0
O4—Ba2—O3^x	68.45 (2)	O1—P1—O1ⁱⁱⁱ	111.11 (9)
O4^viii—Ba2—O3^x	111.55 (2)	O1—P1—O2	109.59 (3)
O4^ix—Ba2—O3^x	124.49 (2)	O1ⁱⁱⁱ—P1—O2	109.59 (3)
O4^x—Ba2—O3^x	55.51 (2)	O1—P1—O2ⁱⁱⁱ	109.59 (3)
O3^ix—Ba2—O3^x	180.0	O1ⁱⁱⁱ—P1—O2ⁱⁱⁱ	109.59 (3)
O4—Ba2—O3^viii	124.49 (2)	O2—P1—O2ⁱⁱⁱ	107.28 (9)
O4^viii—Ba2—O3^viii	55.51 (2)	O3—P2—O3^xii	112.84 (7)
O4^ix—Ba2—O3^viii	68.45 (2)	O3—P2—O4^xii	112.49 (4)
O4^x—Ba2—O3^viii	111.55 (2)	O3^xii—P2—O4^xii	108.95 (5)
O3^ix—Ba2—O3^viii	77.32 (3)	O3—P2—O4	108.95 (5)
O3^x—Ba2—O3^viii	102.68 (3)	O3^xii—P2—O4	112.49 (4)
O4—Ba2—O3	55.51 (2)	O4^xii—P2—O4	100.50 (6)

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

Bond valence and CHARDI analyses for the cations in the title compound top

q(i) = formal oxidation number; sof(i) = site occupancy; CN(i) = classical coordination number; Q(i) = calculated charge; V(i) = calculated valence; ECoN(i) = effective coordination number.

Cation	q(i)	sof(i)	CN(i)	ECoN(i)	V(i)	Q(i)	q(i)/Q(i)
Ba1	1.98	0.99	8	7.99	2.37	1.98	1.00
Ba2	0.02	0.01	8	5.43	0.02	0.99
Ni	2.00	1.00	6	5.97	2.00	1.98	1.01
Fe	3.00	1.00	4	5.96	3.01	2.99	1.00
P1	5.00	1.00	4	3.99	4.95	4.83	1.04
P2	5.00	1.00	4	3.96	4.85	5.11	0.98

Atom percentages in BaNi₂Fe(PO₄)₃ as determined by EDS top

Element	Atomic percentage	Sigma
O	56.74	0.13
P	19.60	0.16
Fe	5.63	0.17
Ni	12.25	0.27
Ba	5.78	0.30
Total	100.00

Acknowledgements

The authors thank the Faculty of Science, Mohammed V University in Rabat, for the X-ray measurements.

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