The iron phosphate NaBaFe₂(PO₄)₃

Abstract

A new iron phosphate, sodium barium diiron tris­(phosphate), NaBaFe₂(PO₄)₃, has been synthesized by the flux method and shown to exhibit the well known langbeinite type structure. The Na, Ba and Fe atoms all lie on threefold axes, while the P and O atoms occupy general positions, one of the O atoms being disordered over two positions, with site occupancy factors of ca 0.7 and 0.3. The [Fe₂(PO₄)₃]_∞ framework consists of FeO₆ octa­hedra sharing all their corners with the PO₄ tetra­hedra. The Na⁺ and Ba²⁺ cations are almost equally distributed over two distinct cavities, in which they occupy slightly different positions.

Related literature

For related literature, see: Baur (1974 ▶); Moffat (1978 ▶); Padhi et al. (1997 ▶); Shannon (1976 ▶). For the structure of langbeinite, see Zemann & Zemann (1957 ▶); Battle et al. (1986 ▶, 1988 ▶).

Experimental

Crystal data

• NaBaFe₂(PO₄)₃

• M _r = 556.94

• Cubic,

• a = 9.796 (1) Å

• V = 940.1 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 7.82 mm⁻¹

• T = 293 (2) K

• 0.1 × 0.1 × 0.1 mm

Data collection

• Enraf–Nonius CAD4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.35, T _max = 0.46

• 2114 measured reflections

• 657 independent reflections

• 644 reflections with I > 2σ(I)

• R _int = 0.082

• 2 standard reflections frequency: 120 min intensity decay: 1%

Refinement

• R[F ² > 2σ(F ²)] = 0.025

• wR(F ²) = 0.059

• S = 0.92

• 657 reflections

• 70 parameters

• 4 restraints

• Δρ_max = 0.57 e Å⁻³

• Δρ_min = −0.49 e Å⁻³

• Absolute structure: Flack (1983 ▶), 123 Friedel pairs

• Flack parameter: −0.03 (3)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond angles (°).

O4Bi—Fe2—O1ii	89.8 (8)
O3—P—O4A	115.1 (3)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Iron phosphates are of increasing interst because of their potential applications in various fields ranging from catalysis (Moffat, 1978) to ionic conductivity (Padhi et al., 1997). Moreover, these materials are very attractive in terms of basic reasearch because they exhibit a rich structural chemistry owing to the possible (+2/+3) mixed valence of iron and its tendency to exhibit various coordination polyhedra.

The title cmpound, sodium barium diiron phosphate NaBaFe₂(PO₄)₃ was isolated during a systematic investigation of the Na₂O–MO–Fe₂O₃–P₂O₅ systems where M is a divalent cation. Its structure (Fig. 1) exhibits a three-dimensional [Fe₂(PO₄)₃]_∞ framework built up from corner-sharing FeO₆ octahedra and PO₄ tetrahedra. Each octahedron is linked to six adjacent tetrahedra and reciprocally each tetrahedron is connected to four neighboring octahedra. This framework delimits two sorts of large cavities, statistically occupied by the Na⁺ and Ba²⁺ cations.

The two symmetry distinct FeO₆ octahedra contained in this structure are somewhat distorted as indicated by the Fe—O distances ranging from 1.963 (5) to 1.991 (4) Å. The average <Fe—O> distances of 1.986 Å for Fe(1) and 1.973 Å for Fe(2) are slightly lower than the value 2.03 Å predicted by Shannon for octahedral Fe³⁺ ions (Shannon, 1976).

The PO₄ tetrahedron is strongly distorted with P—O distances scattering from 1.47 (2) to 1.547 (7) Å. Corresponding average value of 1.511 Å agrees with those frequently observed in anhydrous monophosphates (Baur, 1974).

The Na⁺ and Ba²⁺ cations are statistically distributed over two distinct cavities in which they occupy slightly different positions and have partial occupancies of 0.47, 0.53, 0.53 and 0.47 for Na(1), Ba(1), Na(2) and Ba(2), respectively. The environments of these cations (Fig. 2) were determined assuming all cation-oxygen distances are shorter than the shortest to next cationic site. Each of the Na(1), Ba(1) and Ba(2) environments consists of nine O atoms with cation-oxygen distances in the ranges 2.76 (2)–3.04 (2) Å, 2.753 (7)–2.950 (6) Å and 2.722 (5)–3.047 (7) Å for Na(1), Ba(1) and Ba(2), respectively. The Na(2) environment consists of six O atoms with Na—O distances varying from 2.604 (8) and 3.004 (6) Å.

The as-described structure is closely related to the langbeinite-like phosphates KBaM₂(PO₄)₃ (M = Fe, Cr) (Battle et al., 1986, 1988). However, it differs by the fact that the atom O4, which occupies a single site in the potassium phosphates, is, in the title compound, statistically occupying two distinct positions, O4A and O4B which exhibit partial occupancies of 0.7 and 0.3, respectively. These different values can be explained by the fact that the O4A site is occupied if it is bonded to Na(1), Ba(1) or Ba(2) whereas the O4B site is occupied if it is bonded to Na(1) or Ba(1).

Experimental

Single crystals of the title compund were grown in a flux of sodium dimolybdate Na₂Mo₂O₇ with an atomic ratio P:Mo = 6:1. A starting mixture of 1.071 g of Na₂CO₃, 1.993 g of BaCO₃, 8.162 g of Fe(NO₃)₃.9H₂O, 4.002 g of (NH₄)₂HPO₄ and 1.454 g of MoO₃ was dissolved in nitric acid and the obtained solution was evaporated to dryness. The dry residue was transferred into a platinum crucible and then heated up 600°C to decompose H₂O and NH₃. In a second step, the sample was melted for 1 h at 900°C and then cooled down to room temperature with a 10° h^-1 rate. The final product, obtained after washing with warm water to dissolve the flux is essentially composed of pink and prismatic shaped crystals. Their qualitative elemental analysis using electron microprobe analysis indicated the presence of Na, Ba, Fe and P and no impurity elements have been detected.

Refinement

The Ba and Fe atoms were located by direct methods and the remaining atoms were found by successive difference Fourier maps. All atomic positions were refined anisotropically.

Figures

Fig. 1.

A projection of the structure along the [111] direction.

Fig. 2.

The environments of the Na and Ba sites showing the anisotropic atomic displacements at the 50% level.

Crystal data

NaBaFe2(PO4)3	Z = 4
Mr = 556.94	F000 = 1040
Cubic, P213	Dx = 3.935 Mg m−3
Hall symbol: P 2ac 2ab 3	Mo Kα radiation λ = 0.71073 Å
a = 9.796 (1) Å	Cell parameters from 25 reflections
b = 9.796 (1) Å	θ = 9.0–13.0º
c = 9.796 (1) Å	µ = 7.82 mm−1
α = 90º	T = 293 (2) K
β = 90º	Prism, pink
γ = 90º	0.1 × 0.1 × 0.1 mm
V = 940.1 (3) Å3

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.082
Radiation source: fine-focus sealed tube	θmax = 29.9º
Monochromator: graphite	θmin = 2.9º
T = 293(2) K	h = −1→13
ω/2θ scans	k = −1→13
Absorption correction: ψ scan(North et al., 1968)	l = −1→13
Tmin = 0.35, Tmax = 0.46	2 standard reflections
2114 measured reflections	every 120 min
657 independent reflections	intensity decay: 1%
644 reflections with I > 2σ(I)

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + 5.7579P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.025	(Δ/σ)max = 0.002
wR(F2) = 0.059	Δρmax = 0.57 e Å−3
S = 0.92	Δρmin = −0.49 e Å−3
657 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
70 parameters	Extinction coefficient: 0.0145 (15)
4 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.03 (3)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Na1	0.9427 (12)	0.9427 (12)	0.9427 (12)	0.0144 (3)	0.4738 (16)
Ba1	0.92953 (9)	0.92953 (9)	0.92953 (9)	0.0144 (3)	0.5262 (16)
Na2	0.6862 (8)	0.6862 (8)	0.6862 (8)	0.0232 (4)	0.5262 (16)
Ba2	0.70555 (8)	0.70555 (8)	0.70555 (8)	0.0232 (4)	0.4738 (16)
Fe1	0.35313 (6)	0.85313 (6)	0.64687 (6)	0.0104 (2)
Fe2	0.91362 (6)	0.08638 (6)	0.58638 (6)	0.0101 (2)
P	0.03742 (10)	0.77099 (11)	0.62578 (10)	0.0068 (2)
O1	0.9926 (5)	0.9134 (4)	0.6562 (7)	0.0461 (14)
O2	0.9463 (5)	0.6999 (6)	0.5243 (5)	0.0440 (13)
O3	0.1846 (4)	0.7653 (6)	0.5752 (5)	0.0368 (12)
O4A	0.0112 (7)	0.6985 (10)	0.7629 (8)	0.0389 (18)	0.701 (4)
O4B	0.0527 (17)	0.672 (2)	0.738 (2)	0.0389 (18)	0.299 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.0144 (3)	0.0144 (3)	0.0144 (3)	−0.0019 (3)	−0.0019 (3)	−0.0019 (3)
Ba1	0.0144 (3)	0.0144 (3)	0.0144 (3)	−0.0019 (3)	−0.0019 (3)	−0.0019 (3)
Na2	0.0232 (4)	0.0232 (4)	0.0232 (4)	0.0016 (3)	0.0016 (3)	0.0016 (3)
Ba2	0.0232 (4)	0.0232 (4)	0.0232 (4)	0.0016 (3)	0.0016 (3)	0.0016 (3)
Fe1	0.0104 (2)	0.0104 (2)	0.0104 (2)	0.0001 (2)	−0.0001 (2)	−0.0001 (2)
Fe2	0.0101 (2)	0.0101 (2)	0.0101 (2)	0.0024 (2)	0.0024 (2)	−0.0024 (2)
P	0.0066 (4)	0.0073 (4)	0.0064 (4)	−0.0005 (3)	−0.0028 (3)	0.0010 (3)
O1	0.045 (3)	0.0170 (19)	0.076 (4)	0.0191 (19)	−0.015 (3)	−0.015 (2)
O2	0.029 (2)	0.061 (3)	0.042 (3)	0.003 (2)	−0.025 (2)	−0.031 (2)
O3	0.0120 (16)	0.063 (3)	0.035 (2)	−0.0091 (18)	0.0085 (16)	−0.023 (2)
O4A	0.020 (4)	0.066 (5)	0.031 (3)	0.020 (3)	0.015 (3)	0.040 (3)
O4B	0.020 (4)	0.066 (5)	0.031 (3)	0.020 (3)	0.015 (3)	0.040 (3)

Geometric parameters (Å, °)

Na1—O1i	2.864 (12)	Ba2—O3xiii	2.772 (5)
Na1—O1	2.864 (12)	Ba2—O3xiv	2.772 (5)
Na1—O1ii	2.864 (12)	Ba2—O2ii	2.952 (5)
Na1—O4Biii	2.86 (3)	Ba2—O2	2.952 (5)
Na1—O4Biv	2.86 (3)	Ba2—O2i	2.952 (5)
Na1—O4Bv	2.86 (3)	Ba2—O4Avi	3.047 (7)
Na1—O4Avi	3.045 (17)	Ba2—O4Avii	3.047 (7)
Na1—O4Avii	3.045 (17)	Ba2—O4Aviii	3.047 (7)
Na1—O4Aviii	3.045 (17)	Fe1—O2ii	1.979 (4)
Na1—O2ix	2.763 (17)	Fe1—O2xv	1.979 (4)
Na1—O2x	2.763 (17)	Fe1—O2xvi	1.979 (4)
Na1—O2xi	2.763 (17)	Fe1—O3xiii	1.990 (4)
Ba1—O1i	2.753 (7)	Fe1—O3	1.990 (4)
Ba1—O1	2.753 (7)	Fe1—O3xvii	1.990 (4)
Ba1—O1ii	2.753 (7)	Fe1—Ba1xviii	3.6878 (19)
Ba1—O4Biii	2.89 (3)	Fe1—Ba2iv	3.7867 (6)
Ba1—O4Biv	2.89 (3)	Fe1—Ba2xv	3.7867 (6)
Ba1—O4Bv	2.89 (3)	Fe2—O4Bxix	1.946 (18)
Ba1—O4Avi	2.902 (10)	Fe2—O4Bii	1.946 (18)
Ba1—O4Avii	2.902 (10)	Fe2—O4Bxii	1.946 (18)
Ba1—O4Aviii	2.902 (10)	Fe2—O1xx	1.984 (5)
Ba1—O2ix	2.950 (6)	Fe2—O1xxi	1.984 (5)
Ba1—O2x	2.950 (6)	Fe2—O1xxii	1.984 (5)
Ba1—O2xi	2.950 (6)	Fe2—O4Axix	1.982 (7)
Na2—O3xii	2.604 (8)	Fe2—O4Aii	1.982 (7)
Na2—O3xiii	2.604 (8)	Fe2—O4Axii	1.982 (7)
Na2—O3xiv	2.604 (8)	P—O4B	1.470 (18)
Na2—O2	3.004 (6)	P—O1xxiii	1.493 (4)
Na2—O2i	3.004 (6)	P—O2xxiii	1.506 (4)
Na2—O2ii	3.004 (6)	P—O3	1.526 (4)
Ba2—O3xii	2.772 (5)	P—O4A	1.541 (7)
O1i—Na1—O1	94.9 (5)	O2ix—Ba1—O2xi	55.17 (13)
O1i—Na1—O1ii	94.9 (5)	O2x—Ba1—O2xi	55.17 (13)
O1—Na1—O1ii	94.9 (5)	O3xii—Na2—O3xiii	100.1 (3)
O1i—Na1—O4Biii	58.0 (4)	O3xii—Na2—O3xiv	100.1 (3)
O1—Na1—O4Biii	79.6 (4)	O3xiii—Na2—O3xiv	100.1 (3)
O1ii—Na1—O4Biii	151.3 (7)	O3xii—Na2—O2	83.46 (16)
O1i—Na1—O4Biv	151.3 (7)	O3xiii—Na2—O2	158.5 (4)
O1—Na1—O4Biv	58.0 (4)	O3xiv—Na2—O2	58.53 (12)
O1ii—Na1—O4Biv	79.6 (4)	O3xii—Na2—O2i	58.53 (12)
O4Biii—Na1—O4Biv	118.89 (19)	O3xiii—Na2—O2i	83.46 (16)
O1i—Na1—O4Bv	79.6 (4)	O3xiv—Na2—O2i	158.5 (4)
O1—Na1—O4Bv	151.3 (7)	O2—Na2—O2i	115.68 (18)
O1ii—Na1—O4Bv	58.0 (4)	O3xii—Na2—O2ii	158.5 (4)
O4Biii—Na1—O4Bv	118.89 (19)	O3xiii—Na2—O2ii	58.53 (12)
O4Biv—Na1—O4Bv	118.89 (19)	O3xiv—Na2—O2ii	83.46 (16)
O1i—Na1—O4Avi	46.9 (2)	O2—Na2—O2ii	115.68 (18)
O1—Na1—O4Avi	107.0 (6)	O2i—Na2—O2ii	115.68 (18)
O1ii—Na1—O4Avi	49.5 (3)	O3xii—Ba2—O3xiii	92.09 (15)
O1i—Na1—O4Avii	49.5 (3)	O3xii—Ba2—O3xiv	92.09 (15)
O1—Na1—O4Avii	46.9 (2)	O3xiii—Ba2—O3xiv	92.09 (15)
O1ii—Na1—O4Avii	107.0 (6)	O3xii—Ba2—O2ii	148.54 (14)
O1i—Na1—O4Aviii	107.0 (6)	O3xiii—Ba2—O2ii	57.63 (12)
O1—Na1—O4Aviii	49.5 (3)	O3xiv—Ba2—O2ii	81.64 (14)
O1ii—Na1—O4Aviii	46.9 (2)	O3xii—Ba2—O2	81.64 (14)
O4Avi—Na1—O4Aviii	81.1 (5)	O3xiii—Ba2—O2	148.54 (14)
O4Avii—Na1—O4Aviii	81.1 (5)	O3xiv—Ba2—O2	57.63 (12)
O1i—Na1—O2ix	97.97 (19)	O2ii—Ba2—O2	118.95 (3)
O1—Na1—O2ix	104.0 (2)	O3xii—Ba2—O2i	57.63 (12)
O1ii—Na1—O2ix	156.0 (6)	O3xiii—Ba2—O2i	81.64 (14)
O4Biv—Na1—O2ix	97.9 (6)	O3xiv—Ba2—O2i	148.54 (14)
O4Bv—Na1—O2ix	104.6 (6)	O2ii—Ba2—O2i	118.95 (3)
O4Avi—Na1—O2ix	134.2 (2)	O2—Ba2—O2i	118.95 (3)
O4Avii—Na1—O2ix	96.81 (16)	O3xii—Ba2—O4Avi	104.95 (16)
O4Aviii—Na1—O2ix	144.2 (3)	O3xiii—Ba2—O4Avi	83.7 (2)
O1i—Na1—O2x	156.0 (6)	O3xiv—Ba2—O4Avi	162.54 (16)
O1—Na1—O2x	97.97 (19)	O2ii—Ba2—O4Avi	81.80 (17)
O1ii—Na1—O2x	104.0 (2)	O2—Ba2—O4Avi	127.8 (2)
O4Biii—Na1—O2x	104.6 (6)	O2i—Ba2—O4Avi	47.59 (16)
O4Biv—Na1—O2x	49.4 (4)	O3xii—Ba2—O4Avii	83.7 (2)
O4Bv—Na1—O2x	97.9 (6)	O3xiii—Ba2—O4Avii	162.54 (16)
O4Avi—Na1—O2x	144.2 (3)	O3xiv—Ba2—O4Avii	104.95 (16)
O4Avii—Na1—O2x	134.2 (2)	O2ii—Ba2—O4Avii	127.8 (2)
O4Aviii—Na1—O2x	96.81 (16)	O2—Ba2—O4Avii	47.59 (16)
O2ix—Na1—O2x	59.2 (4)	O2i—Ba2—O4Avii	81.80 (17)
O1i—Na1—O2xi	104.0 (2)	O4Avi—Ba2—O4Avii	81.1 (3)
O1—Na1—O2xi	156.0 (6)	O3xii—Ba2—O4Aviii	162.54 (17)
O1ii—Na1—O2xi	97.97 (19)	O3xiii—Ba2—O4Aviii	104.95 (16)
O4Biii—Na1—O2xi	97.9 (6)	O3xiv—Ba2—O4Aviii	83.7 (2)
O4Biv—Na1—O2xi	104.6 (6)	O2ii—Ba2—O4Aviii	47.59 (16)
O4Avi—Na1—O2xi	96.81 (16)	O2—Ba2—O4Aviii	81.80 (17)
O4Avii—Na1—O2xi	144.2 (3)	O2i—Ba2—O4Aviii	127.8 (2)
O4Aviii—Na1—O2xi	134.2 (2)	O4Avi—Ba2—O4Aviii	81.1 (3)
O2ix—Na1—O2xi	59.2 (4)	O4Avii—Ba2—O4Aviii	81.1 (3)
O2x—Na1—O2xi	59.2 (4)	O2ii—Fe1—O2xv	87.3 (2)
O1i—Ba1—O1	100.10 (14)	O2ii—Fe1—O2xvi	87.3 (2)
O1i—Ba1—O1ii	100.10 (14)	O2xv—Fe1—O2xvi	87.3 (2)
O1—Ba1—O1ii	100.10 (14)	O2ii—Fe1—O3xiii	88.26 (18)
O1i—Ba1—O4Biii	58.8 (4)	O2xv—Fe1—O3xiii	89.2 (2)
O1—Ba1—O4Biii	80.9 (4)	O2xvi—Fe1—O3xiii	174.5 (2)
O1ii—Ba1—O4Biii	158.5 (4)	O2ii—Fe1—O3	174.5 (2)
O1i—Ba1—O4Biv	158.5 (4)	O2xv—Fe1—O3	88.26 (18)
O1—Ba1—O4Biv	58.8 (4)	O2xvi—Fe1—O3	89.2 (2)
O1ii—Ba1—O4Biv	80.9 (4)	O3xiii—Fe1—O3	95.0 (2)
O4Biii—Ba1—O4Biv	116.8 (2)	O2ii—Fe1—O3xvii	89.2 (2)
O1i—Ba1—O4Bv	80.9 (4)	O2xv—Fe1—O3xvii	174.5 (2)
O1—Ba1—O4Bv	158.5 (4)	O2xvi—Fe1—O3xvii	88.26 (18)
O1ii—Ba1—O4Bv	58.8 (4)	O3xiii—Fe1—O3xvii	95.0 (2)
O4Biii—Ba1—O4Bv	116.8 (2)	O3—Fe1—O3xvii	95.0 (2)
O4Biv—Ba1—O4Bv	116.8 (2)	O4Bxix—Fe2—O4Bii	80.8 (9)
O1i—Ba1—O4Avi	49.19 (16)	O4Bxix—Fe2—O4Bxii	80.8 (9)
O1—Ba1—O4Avi	114.25 (19)	O4Bii—Fe2—O4Bxii	80.8 (9)
O1ii—Ba1—O4Avi	51.94 (17)	O4Bxix—Fe2—O1xx	169.5 (6)
O1i—Ba1—O4Avii	51.94 (17)	O4Bii—Fe2—O1xx	89.8 (8)
O1—Ba1—O4Avii	49.19 (16)	O4Bxii—Fe2—O1xx	93.0 (5)
O1ii—Ba1—O4Avii	114.25 (19)	O4Bxix—Fe2—O1xxi	93.0 (5)
O1i—Ba1—O4Aviii	114.25 (19)	O4Bii—Fe2—O1xxi	169.5 (6)
O1—Ba1—O4Aviii	51.94 (17)	O4Bxii—Fe2—O1xxi	89.8 (8)
O1ii—Ba1—O4Aviii	49.19 (16)	O1xx—Fe2—O1xxi	95.5 (3)
O4Avi—Ba1—O4Aviii	86.1 (2)	O4Bxix—Fe2—O1xxii	89.8 (8)
O4Avii—Ba1—O4Aviii	86.1 (2)	O4Bii—Fe2—O1xxii	93.0 (5)
O1i—Ba1—O2ix	96.20 (14)	O4Bxii—Fe2—O1xxii	169.5 (6)
O1—Ba1—O2ix	102.04 (15)	O1xx—Fe2—O1xxii	95.5 (3)
O1ii—Ba1—O2ix	149.64 (14)	O1xxi—Fe2—O1xxii	95.5 (3)
O4Biii—Ba1—O2ix	47.5 (4)	O1xx—Fe2—O4Axix	168.6 (3)
O4Biv—Ba1—O2ix	93.1 (4)	O1xxi—Fe2—O4Axix	77.4 (3)
O4Bv—Ba1—O2ix	99.2 (4)	O1xxii—Fe2—O4Axix	94.1 (3)
O4Avi—Ba1—O2ix	132.27 (18)	O4Bxix—Fe2—O4Aii	78.2 (6)
O4Avii—Ba1—O2ix	95.97 (17)	O4Bii—Fe2—O4Aii	15.9 (5)
O4Aviii—Ba1—O2ix	141.66 (18)	O4Bxii—Fe2—O4Aii	95.9 (8)
O1i—Ba1—O2x	149.64 (14)	O1xx—Fe2—O4Aii	94.1 (3)
O1—Ba1—O2x	96.20 (14)	O1xxi—Fe2—O4Aii	168.6 (3)
O1ii—Ba1—O2x	102.04 (15)	O1xxii—Fe2—O4Aii	77.4 (3)
O4Biii—Ba1—O2x	99.2 (4)	O4Axix—Fe2—O4Aii	94.0 (3)
O4Biv—Ba1—O2x	47.5 (4)	O1xx—Fe2—O4Axii	77.4 (3)
O4Bv—Ba1—O2x	93.1 (4)	O1xxi—Fe2—O4Axii	94.1 (3)
O4Avi—Ba1—O2x	141.66 (18)	O1xxii—Fe2—O4Axii	168.6 (3)
O4Avii—Ba1—O2x	132.27 (18)	O4Axix—Fe2—O4Axii	94.0 (3)
O4Aviii—Ba1—O2x	95.97 (17)	O4Aii—Fe2—O4Axii	94.0 (3)
O2ix—Ba1—O2x	55.17 (13)	O4B—P—O1xxiii	119.9 (10)
O1i—Ba1—O2xi	102.04 (15)	O4B—P—O2xxiii	104.3 (11)
O1—Ba1—O2xi	149.64 (14)	O1xxiii—P—O2xxiii	112.9 (3)
O1ii—Ba1—O2xi	96.20 (14)	O4B—P—O3	97.0 (6)
O4Biii—Ba1—O2xi	93.1 (4)	O1xxiii—P—O3	112.2 (3)
O4Biv—Ba1—O2xi	99.2 (4)	O2xxiii—P—O3	109.2 (3)
O4Bv—Ba1—O2xi	47.5 (4)	O4B—P—O4A	20.6 (6)
O4Avi—Ba1—O2xi	95.97 (16)	O1xxiii—P—O4A	102.0 (4)
O4Avii—Ba1—O2xi	141.66 (18)	O2xxiii—P—O4A	105.3 (4)
O4Aviii—Ba1—O2xi	132.27 (18)	O3—P—O4A	115.1 (3)

Symmetry codes: (i) y, z, x; (ii) z, x, y; (iii) y+1/2, −z+3/2, −x+1; (iv) −x+1, y+1/2, −z+3/2; (v) −z+3/2, −x+1, y+1/2; (vi) y, z, x+1; (vii) x+1, y, z; (viii) z, x+1, y; (ix) y+1/2, −z+3/2, −x+2; (x) −x+2, y+1/2, −z+3/2; (xi) −z+3/2, −x+2, y+1/2; (xii) −y+3/2, −z+1, x+1/2; (xiii) −z+1, x+1/2, −y+3/2; (xiv) x+1/2, −y+3/2, −z+1; (xv) x−1/2, −y+3/2, −z+1; (xvi) −y+1, z+1/2, −x+3/2; (xvii) y−1/2, −z+3/2, −x+1; (xviii) −x+3/2, −y+2, z−1/2; (xix) −x+1, y−1/2, −z+3/2; (xx) −z+3/2, −x+1, y−1/2; (xxi) −y+2, z−1/2, −x+3/2; (xxii) x, y−1, z; (xxiii) x−1, y, z.