KNi_0.93Fe^II_0.07Fe^III(PO₄)₂: a new type of structure for a compound of composition M^IM^IIM^III(PO₄)₂

The solid solution KNi_0.93Fe^II_0.07Fe^III(PO₄)₂ {potassium [nickel(II)/iron(II)] iron(III) bis­(orthophosphate)} has been prepared by the flux method. The compound shows a new type of structure for a phosphate with the general composition M^IM^IIM^III(PO₄)₂. The framework is formed by [(Ni/Fe)O₆] polyhedra [Fe site occupancy = 0.069 (14)] linked via shared oxygen vertices forming a cis-like parallel chain stretching along a and [FeO₅] polyhedra (located on alternate sides of the chains) connected via two types of PO₄ groups into a three-dimensional structure. The K atoms are disordered between two sites, denoted K1A and K1B, with occupancies of 0.930 (9) and 0.070 (9), respectively, and reside inside channels along the a axis. Calculations of the Voronoi-Dirichlet polyhedra of the K atoms give a coordination scheme for K1A of [9 + 3] and for K1B of [10 + 2]. The most remarkable feature of the structure is the splitting of the K-atom site and the population of the K1A and K1B positions due to substitution of Ni by Fe in the (Ni/Fe) position.

S1. Introduction

The properties and structure of complex phosphates have been extensively studied in order to search and create new ferroelectric, nonlinear–optical, luminescent, ionic-conductor, catalytic and other materials (Wang et al., 2000; Roth et al., 2001; Henry et al., 2000). Phosphates of the general formula M^IM^IIFe^III(PO₄)₂ have been discussed in detail using the examples of the isotypic members KFe^IIFe^III(PO₄)₂ (Yakubovich et al., 1986), KCu^IIFe^III(PO₄)₂ (Badri et al., 2011), RbCu^IIFe^III(PO₄)₂ (Badri et al., 2013), KMgFe^III(PO₄)₂ (Badri et al., 2009) and the solid solution KMg_0.09Fe^II_0.91Fe^III(PO₄)₂ (Yatskin et al., 2012), which exhibits an original structure. We report here the structure of the solid solution of KNi_0.93Fe^II_0.07Fe^III(PO₄)₂, (I), which represents a new type of three-dimensional-framework for compounds of the type M^IM^IIM^III(PO₄)₂.

S2. Experimental

S2.1. Synthesis and crystallization

Crystals of a solid solution of (I) were obtained from a high-temperature solution in the pseudo-system K₂O–P₂O₅–MoO₃–Fe₂O₃–NiO. A mixture of KPO₃ (10.62 g), H₃PO₄ (2.94 g), Fe₂O₃ (2.88 g), NiO (2.67 g) and K₂Mo₂O₇ (3.40 g) (molar ratio K/P/Fe/Ni/Mo equal to 1:1.1:0.3:0.3:0.15) was placed in a platinum crucible and heated to 1273 K. The melt obtained was kept at this temperature for 2 h and then cooled to 873 K at a rate of 25 K h^-1. Light-yellow prismatic crystals of (I) were separated from the flux by decantation at the final crystallization temperature and were washed from the remaining flux with a hot water. The chemical composition of single crystals was verified using EDX analysis. Analysis found: K 11.42, Fe 17.46, Ni 15.97, P 17.76 at%, while KNi_0.93Fe^II_0.07Fe^III(PO₄)₂ requires K 11.39, Fe 17.40, Ni 15.90, P 18.04 at%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The structure was solved by direct methods and the positions of Fe1, Ni1, K1 and P were determined. The positions of O atoms were found as peaks with high electron density on difference Fourier maps. Anisotropic approach of displacement parameters was applied on the next stage. After all these manipulations the resulting electron density and convergence factors were found to be very high. As the electron densities of Fe and Ni positions are similar (very close atomic mass and atomic numbers) and their typical oxygen environment can be the same we supposed partial substitution of Fe by Ni and Ni by Fe. To check this idea we constrained the coordinates of Ni1—Fe1 and Ni2—Fe2 and their ADP equal for corresponding positions. The corresponding occupancies of Fe and Ni were refined using free variables. As the value for Ni2 was found negligible, we removed this position and corresponding variable from the following refinement. The occupancy factor of Fe2 was fixed at 1. Than after refinement the values of convergence factors significantly decreased comparing with the starting values, but remaining electron density was still high. At a distance approximately 0.741 Å from K1 site was found a peak with positive electron density 1.37 e Å^-3. It was suggested as K1B site, while K1 was renamed as K1A. Thus we got splitting of the K site. The ADP of these positions was constrained as equal. The occupancies of K1A and K1B were refined using free variables. As a result we got the reported convergence factors and residual electron density.

S3. Results and discussion

The structure of (I) is built up from [(Ni/Fe)1O₆] and [Fe2O₅] polyhedra inter­linked via two types of PO₄ groups (Fig. 1). The Ni-atom positions [Ni is partially substituted by Fe with an occupancy of 0.069 (14)] have a significantly distorted o­cta­hedral environment, with (Ni/Fe)1—O distances in the range 2.0140 (14)–2.1975 (14) Å (Table 1). The [Fe2O₅] polyhedra show an almost regular trigonal bipyramidal shape. The Fe-atom site is located close to the centre of the O2—O4—O7 triangle, where three Fe—O bonds are spread over the range 1.8920 (13)–1.9273 (14) Å. The distances between axial O atoms and atom Fe2 are 1.9292 (14) and 2.0166 (13) Å for Fe2—O5 and Fe2—O1, respectively, and the O1—Fe2—O5 angle is 173.02 (6)°. One of the O atoms (O4) is shared by the [(Ni/Fe)1O₆] and [Fe2O₅] polyhedra; the (Ni/Fe)1—Fe2 distance is 3.6581 (12) Å and the (Ni/Fe)1—O4—Fe2 angle is 127.39 (7)° (Fig. 2a). The inter­atomic distances and angles (Table 2) show that the [P1O₄] and [P2O₄] tetra­hedra are almost regular, with classical P—O bond lengths ranging from 1.5211 (14) to 1.5675 (14) Å (Corbridge, 1980).

The [(Ni/Fe)1O₆] polyhedra are linked via common O-atom vertices, forming a cis-like parallel zigzag chain stretching along the a direction and the [Fe2O₅] polyhedra alternate with different sides of such chains (Fig. 2b). In each chain, the [P1O₄] tetra­hedron has a common edge with [(Ni/Fe)1O₆] polyhedra (Fig. 2a) and provides a monodentate type of coordination to two Fe2 and one (Ni/Fe)1 atom, while the fourth corner assembles with [Fe2O₅] polyhedra in a parallel chain. The second [P2O₄] tetra­hedron coordinates in a monodentate manner to two (Ni/Fe)1 and one Fe2 atom in the same chain, and to one Fe2 atom of the next chain. As a result of these linkages, a three-dimensional framework of the general composition [Ni_0.93Fe^II_0.07Fe^III(PO₄)₂]^- is formed. The projection of the structure of (I) on the bc plane (Fig. 2c) shows tunnels running along a, where the K⁺ cations are located.

The K atoms are disordered between two sites, K1A and K1B, in which the occupancies are 0.930 (9) and 0.070 (9), respectively. For the determination of the coordination numbers (CN) of K1A and K1B, Voronoi–Dirichlet polyhedra (VDP) were constructed using the DIRICHLET program included in the TOPOS package (Blatov et al., 1995). Details connected with this procedure are given as Supplementary information. Analysis of the solid angle (Ω) distribution revealed 12 K—O contacts for K1A and K1B [cut-off distance of 4.1 Å, neglecting those corresponding to Ω < 1.5% (Blatov et al., 1998)]. The coordination scheme for K1A and K1B is described as [9+3] [nine refers to the `ion–covalent' bonds in the range 2.7506 (17)–3.289 (2) Å, which have Ω > 5.0%, and three refers to the distances ranging from 3.4429 (18) to 3.752 (3) Å corresponding to 1.5% < Ω < 5.0%] and [10+2] [i.e. ten K—O contacts in the range 2.689 (11)–3.36 (2) Å, corresponding to Ω > 5.0%, and two bonds of 3.569 (2) (Ω = 3.23%) and 3.622 (14) Å (Ω = 3.05%) Å) (Table 2)].

The K1B sites are located around the K1A···K1A axis (running along a), with the shortest distances being between sites K1A···K1B, K1A···K1Aⁱ and K1B···K1Aⁱ of 0.44 (2), 4.74 (2) and 5.102 (3) Å, respectively. The splitting of site K1 and the filling of positions K1A and K1B implemented due to substitution of Ni with Fe in the position (Ni/Fe)1 (the occupancies of sites K1B and Fe1 are 0.07). Thus, when a K1A position moves to a K1B position there is a change in the K—O distances and the Δd of values ΔΩ (Table 2); only the K1–O7ⁱ/O6/O8ⁱⁱ distances remain virtually unchanged (Δd = 0.03–0.06 Å, ΔΩ = 0.11–0.69%), K1—O7^iv is significantly weakened (Δd = 0.39 Å, ΔΩ = 2.3%) and K1—O6^vi decreases (Δd = 0.39 Å, ΔΩ = 2.69%). [please check rewording carefully]

As a result, the K atom is moved to the O3^v–O6^vi–O8ⁱⁱ face of the [FeO₆] polyhedron, as shown in Fig. 3.

Another inter­esting fact should be noted also. In the formation of (I), a partial transition of Fe^III to Fe^II was observed, as in case of the solid solution KMg_0.09Fe^II_0.91Fe^III(PO₄)₂ (Yatskin et al., 2012).

For (I) and phosphates of the general formula M^IM^IIFe^III(PO₄)₂, the framework of the structures is built from the elements [MO₅], [MO₆] and [PO₄], but the method of their joining is different (Figs. 2a and 4a).

In the structures of compounds of type M^IM^IIFe^III(PO₄)₂ [M^I = K, Rb; M^II = Fe, Mg, (Fe/Mg), Cu], two [M^IIO₅] trigonal bipyramids are linked via an edge, resulting in a fragment of composition [M^II₂O₈]. For example, in KMg_0.09Fe^II_0.91Fe^III(PO₄)₂, [Fe₂O₈] units are connected by [(Fe/Mg)O₆] polyhedra into a two-dimensional-lattice (Figs. 4a and 4b), which additionally are linked by PO₄ tetra­hedra to form a three-dimensional-framework. The K atoms are located in hexagonal channels along [101] (Fig. 4c). Besides, the substitution of Fe by Mg in the case of KMg_0.09Fe^II_0.91Fe^III(PO₄)₂ does not caused splitting of the potassium site. In the case of (I), the [MO₅] and [MO₆] polyhedra are formed by di- and threevalent metals, respectively. These polyhedra are inter­linked by a common edge and a corner giving an infinite chain along a; these chains are connected by PO₄ tetra­hedra into a three-dimensional-framework. It should be noted that such a condensation of [MO₅] and [MO₆] polyhedra had not been found for compounds of the M^IM^IIFe^III(PO₄)₂ type. Accordingly, the key role in the formation of [M^IIM^III(PO₄)₂]^- anionic lattices is played by the nature of the polyvalent pair M^II + M^III. It is noteworthy that this factor does not exclude the possibility of the existence of polymorphs for compounds of the type M^IM^IIM^III(PO₄)₂.

Related literature

For related literature, see: Badri et al. (2009, 2011, 2013); Blatov et al. (1998); Henry et al. (2000); Roth et al. (2001); Wang et al. (2000); Yakubovich et al. (1986); Yatskin et al. (2012).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and enCIFer (Allen et al., 2004).

Figures

Fig. 1. A connected set of numbered atoms, showing displacement ellipsoids at the 50% probability level. M1 is Ni or Fe. [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z; (iii) -x+1, -y+1, -z+2; (iv) x, -y+1/2, z+1/2; (v) -x, -y+1, -z+2.]

Fig. 2. (a) The asssemblage of PO₄ tetrahedra and M1FeO₁₀ (M1 is Ni or Fe) units in (I), (b) the formation of a zigzag chain from M1O₆ (M1 is Ni or Fe) and FeO₅ polyhedra and (c) a projection of the structure of (I) on the bc plane (K atoms are shown as grey circles).

Fig. 3. The O-atom coordination around the K atoms in (a) position K1A and (b) position K1B for (I). [Symmetry codes: (i) x-1, y, z; (ii) -x, y-1/2, -z+3/2; (iii) x, -y+1/2, z+1/2; (iv) x-1, -y+1/2, z+1/2; (v) -x+1, y-1/2, -z+3/2; (vi) x, -y+1/2, z-1/2; (vi) x+1, y, z.]

Fig. 4. (a)/(b) The elementary fragment and (c) the two-dimensional-lattice in a projection along [101] (K atoms are shown as grey circles) for KMg_0.09Fe^II_0.91Fe^III(PO₄)₂ (Yatskin et al., 2012).

Potassium [nickel(II)/iron(II)] iron(III) bis(orthophosphate)

Crystal data

KNi0.93Fe1.07(PO4)2	F(000) = 667.4
Mr = 343.39	Dx = 3.464 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11250 reflections
a = 5.102 (1) Å	θ = 3.6–33°
b = 14.464 (3) Å	µ = 6.15 mm^−1
c = 9.2260 (18) Å	T = 293 K
β = 104.74 (3)°	Needle, yellow
V = 658.4 (2) Å^3	0.15 × 0.02 × 0.02 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur-3 diffractometer	2480 independent reflections
Radiation source: fine-focus sealed tube	2158 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 33°, θmin = 3.6°
Absorption correction: multi-scan (Blessing, 1995)	h = −7→7
Tmin = 0.879, Tmax = 0.914	k = −22→22
11250 measured reflections	l = −14→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	w = 1/[σ^2(Fo^2) + (0.0237P)^2 + 0.2992P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.052	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.57 e Å^−3
2480 reflections	Δρmin = −0.68 e Å^−3
124 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.0037 (5)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
K1A	0.1860 (4)	0.17581 (5)	0.81425 (17)	0.0211 (3)	0.930 (9)
K1B	0.246 (4)	0.1800 (8)	0.7879 (19)	0.0211 (3)	0.070 (9)
Fe1	0.24264 (5)	0.454843 (16)	0.96107 (2)	0.00757 (7)	0.069 (14)
Ni1	0.24264 (5)	0.454843 (16)	0.96107 (2)	0.00757 (7)	0.931 (14)
Fe2	0.77277 (5)	0.371170 (17)	0.61772 (3)	0.00758 (7)
P1	0.30800 (9)	0.49372 (3)	0.67867 (5)	0.00715 (9)
P2	0.74384 (9)	0.32811 (3)	0.96343 (5)	0.00705 (9)
O1	0.2259 (3)	0.58160 (9)	0.58775 (15)	0.0130 (3)
O2	0.4142 (3)	0.42097 (9)	0.58654 (14)	0.0113 (2)
O3	0.5067 (3)	0.51309 (9)	0.82954 (14)	0.0117 (2)
O4	0.0560 (3)	0.45257 (9)	0.72405 (14)	0.0109 (2)
O5	0.7650 (3)	0.31122 (9)	0.80337 (14)	0.0138 (3)
O6	0.4499 (3)	0.33556 (9)	0.97039 (16)	0.0131 (3)
O7	0.8819 (3)	0.25595 (9)	0.55545 (14)	0.0113 (2)
O8	0.0833 (2)	0.58636 (9)	0.96854 (14)	0.0084 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1A	0.0206 (5)	0.0201 (2)	0.0184 (3)	−0.0004 (2)	−0.0026 (3)	0.0028 (2)
K1B	0.0206 (5)	0.0201 (2)	0.0184 (3)	−0.0004 (2)	−0.0026 (3)	0.0028 (2)
Fe1	0.00739 (11)	0.00809 (12)	0.00739 (11)	−0.00049 (8)	0.00216 (7)	−0.00034 (7)
Ni1	0.00739 (11)	0.00809 (12)	0.00739 (11)	−0.00049 (8)	0.00216 (7)	−0.00034 (7)
Fe2	0.00866 (12)	0.00716 (12)	0.00668 (12)	0.00024 (9)	0.00149 (8)	−0.00032 (8)
P1	0.00745 (19)	0.0080 (2)	0.00599 (19)	0.00017 (15)	0.00174 (14)	0.00040 (14)
P2	0.00848 (19)	0.00597 (19)	0.00695 (18)	−0.00036 (15)	0.00242 (14)	0.00020 (14)
O1	0.0176 (6)	0.0121 (6)	0.0105 (6)	0.0039 (5)	0.0056 (5)	0.0040 (5)
O2	0.0108 (6)	0.0135 (6)	0.0098 (6)	0.0019 (5)	0.0032 (5)	−0.0029 (5)
O3	0.0106 (6)	0.0152 (6)	0.0079 (6)	−0.0016 (5)	−0.0003 (4)	−0.0016 (5)
O4	0.0089 (6)	0.0154 (6)	0.0088 (6)	−0.0042 (5)	0.0032 (4)	−0.0016 (4)
O5	0.0209 (7)	0.0129 (6)	0.0085 (6)	0.0000 (5)	0.0053 (5)	0.0007 (5)
O6	0.0095 (6)	0.0100 (6)	0.0207 (7)	−0.0002 (5)	0.0053 (5)	−0.0012 (5)
O7	0.0162 (6)	0.0070 (6)	0.0101 (6)	0.0000 (5)	0.0021 (5)	−0.0026 (4)
O8	0.0079 (5)	0.0071 (6)	0.0106 (6)	−0.0009 (4)	0.0031 (4)	−0.0007 (4)

Geometric parameters (Å, º)

K1A—O7^i	2.7506 (17)	Fe2—K1A^x	3.7109 (10)
K1A—O1^ii	2.838 (3)	Fe2—K1B^x	3.743 (12)
K1A—O2^iii	2.8526 (18)	Fe2—K1A^xii	3.968 (3)
K1A—O6	2.8706 (16)	P1—O1	1.5218 (14)
K1A—O5^i	2.889 (2)	P1—O3	1.5248 (14)
K1A—O8^ii	2.9230 (17)	P1—O2	1.5354 (14)
K1A—O7^iv	3.177 (3)	P1—O4	1.5675 (14)
K1A—O1^v	3.209 (2)	P1—K1B^xiii	3.490 (15)
K1A—O3^v	3.289 (2)	P1—K1A^xiv	3.657 (2)
K1A—P2^vi	3.4425 (15)	P1—K1A^xiii	3.6771 (16)
K1A—P2	3.5853 (16)	P2—O6	1.5211 (14)
K1A—Fe2^iii	3.6052 (15)	P2—O5	1.5275 (14)
K1B—O7^i	2.689 (11)	P2—O7^iii	1.5461 (14)
K1B—O6	2.844 (12)	P2—O8^ix	1.5557 (13)
K1B—O8^ii	2.869 (11)	P2—K1B^xv	3.411 (11)
K1B—O1^v	3.005 (15)	P2—K1A^xv	3.4425 (15)
K1B—O2^iii	3.042 (16)	P2—K1A^x	3.663 (2)
K1B—O3^v	3.049 (17)	O1—Fe2^xi	2.0166 (13)
K1B—O5^i	3.134 (18)	O1—K1A^xiv	2.838 (3)
K1B—O5	3.23 (2)	O1—K1B^xiii	3.005 (15)
K1B—O1^ii	3.25 (2)	O1—K1A^xiii	3.209 (2)
K1B—O6^vii	3.36 (2)	O1—K1B^xiv	3.25 (3)
K1B—P2	3.402 (14)	O2—K1A^vii	2.8526 (18)
K1B—P2^vi	3.411 (11)	O2—K1B^vii	3.042 (16)
Fe1—O6	2.0140 (14)	O3—Ni1^ix	2.0797 (14)
Fe1—O8^viii	2.0230 (13)	O3—Fe1^ix	2.0797 (14)
Fe1—O8	2.0766 (13)	O3—K1B^xiii	3.049 (17)
Fe1—O3^ix	2.0797 (14)	O3—K1A^xiii	3.289 (2)
Fe1—O4	2.1518 (14)	O4—Fe2^i	1.9273 (14)
Fe1—O3	2.1975 (14)	O5—K1A^x	2.889 (2)
Fe1—P1	2.7673 (7)	O5—K1B^x	3.134 (19)
Fe1—Ni1^ix	2.8563 (7)	O6—K1B^iii	3.36 (2)
Fe1—Fe1^ix	2.8563 (7)	O7—P2^vii	1.5461 (14)
Fe1—K1B^iii	3.588 (17)	O7—K1B^x	2.689 (11)
Fe1—K1A^iii	3.8408 (18)	O7—K1A^x	2.7506 (17)
Fe2—O7	1.8920 (13)	O7—K1A^xii	3.177 (3)
Fe2—O2	1.9186 (14)	O8—P2^ix	1.5557 (13)
Fe2—O4^x	1.9273 (14)	O8—Ni1^viii	2.0230 (13)
Fe2—O5	1.9292 (14)	O8—Fe1^viii	2.0230 (13)
Fe2—O1^xi	2.0166 (13)	O8—K1B^xiv	2.869 (11)
Fe2—K1B^vii	3.587 (11)	O8—K1A^xiv	2.9230 (17)
Fe2—K1A^vii	3.6052 (15)
O7^i—K1A—O1^ii	100.32 (7)	O7—Fe2—O5	87.01 (6)
O7^i—K1A—O2^iii	170.02 (10)	O2—Fe2—O5	93.87 (6)
O1^ii—K1A—O2^iii	69.71 (6)	O4^x—Fe2—O5	90.27 (6)
O7^i—K1A—O6	100.68 (5)	O7—Fe2—O1^xi	86.64 (6)
O1^ii—K1A—O6	121.15 (8)	O2—Fe2—O1^xi	87.89 (6)
O2^iii—K1A—O6	85.34 (5)	O4^x—Fe2—O1^xi	95.17 (6)
O7^i—K1A—O5^i	55.54 (4)	O5—Fe2—O1^xi	173.02 (6)
O1^ii—K1A—O5^i	74.49 (7)	O7—Fe2—K1B^vii	77.0 (3)
O2^iii—K1A—O5^i	119.76 (9)	O2—Fe2—K1B^vii	58.0 (4)
O6—K1A—O5^i	73.83 (5)	O4^x—Fe2—K1B^vii	149.4 (2)
O7^i—K1A—O8^ii	51.58 (4)	O5—Fe2—K1B^vii	118.7 (3)
O1^ii—K1A—O8^ii	81.60 (5)	O1^xi—Fe2—K1B^vii	56.9 (3)
O2^iii—K1A—O8^ii	124.24 (5)	O7—Fe2—K1A^vii	81.29 (5)
O6—K1A—O8^ii	149.11 (8)	O2—Fe2—K1A^vii	51.87 (6)
O5^i—K1A—O8^ii	95.32 (5)	O4^x—Fe2—K1A^vii	151.31 (4)
O7^i—K1A—O7^iv	102.06 (6)	O5—Fe2—K1A^vii	113.84 (6)
O1^ii—K1A—O7^iv	52.62 (6)	O1^xi—Fe2—K1A^vii	62.27 (6)
O2^iii—K1A—O7^iv	72.43 (6)	K1B^vii—Fe2—K1A^vii	7.0 (4)
O6—K1A—O7^iv	69.43 (5)	O7—Fe2—K1A^x	45.83 (5)
O5^i—K1A—O7^iv	47.35 (5)	O2—Fe2—K1A^x	139.52 (6)
O8^ii—K1A—O7^iv	124.08 (8)	O4^x—Fe2—K1A^x	87.56 (5)
O7^i—K1A—O1^v	134.74 (10)	O5—Fe2—K1A^x	50.31 (6)
O1^ii—K1A—O1^v	114.92 (6)	O1^xi—Fe2—K1A^x	125.44 (6)
O2^iii—K1A—O1^v	53.18 (4)	K1B^vii—Fe2—K1A^x	117.9 (2)
O6—K1A—O1^v	85.11 (5)	K1A^vii—Fe2—K1A^x	119.482 (19)
O5^i—K1A—O1^v	158.60 (4)	O7—Fe2—K1B^x	43.0 (2)
O8^ii—K1A—O1^v	104.89 (6)	O2—Fe2—K1B^x	146.0 (4)
O7^iv—K1A—O1^v	121.53 (5)	O4^x—Fe2—K1B^x	85.3 (2)
O7^i—K1A—O3^v	99.96 (6)	O5—Fe2—K1B^x	56.8 (4)
O1^ii—K1A—O3^v	104.63 (5)	O1^xi—Fe2—K1B^x	119.2 (4)
O2^iii—K1A—O3^v	82.78 (4)	K1B^vii—Fe2—K1B^x	117.9 (2)
O6—K1A—O3^v	124.57 (8)	K1A^vii—Fe2—K1B^x	120.40 (18)
O5^i—K1A—O3^v	153.84 (5)	K1A^x—Fe2—K1B^x	6.8 (4)
O8^ii—K1A—O3^v	59.16 (4)	O7—Fe2—K1A^xii	52.04 (4)
O7^iv—K1A—O3^v	150.80 (6)	O2—Fe2—K1A^xii	128.03 (5)
O1^v—K1A—O3^v	45.74 (4)	O4^x—Fe2—K1A^xii	89.98 (4)
O7^i—K1A—P2^vi	25.97 (3)	O5—Fe2—K1A^xii	133.16 (5)
O1^ii—K1A—P2^vi	86.02 (5)	O1^xi—Fe2—K1A^xii	42.72 (4)
O2^iii—K1A—P2^vi	147.44 (5)	K1B^vii—Fe2—K1A^xii	77.5 (4)
O6—K1A—P2^vi	126.62 (5)	K1A^vii—Fe2—K1A^xii	84.55 (4)
O5^i—K1A—P2^vi	71.04 (4)	K1A^x—Fe2—K1A^xii	82.91 (4)
O8^ii—K1A—P2^vi	26.73 (3)	K1B^x—Fe2—K1A^xii	76.6 (4)
O7^iv—K1A—P2^vi	110.11 (6)	O1—P1—O3	112.05 (8)
O1^v—K1A—P2^vi	126.86 (7)	O1—P1—O2	110.71 (8)
O3^v—K1A—P2^vi	82.80 (4)	O3—P1—O2	112.64 (8)
O7^i—K1A—P2	106.95 (6)	O1—P1—O4	109.56 (8)
O1^ii—K1A—P2	138.80 (6)	O3—P1—O4	103.05 (8)
O2^iii—K1A—P2	81.79 (4)	O2—P1—O4	108.46 (8)
O6—K1A—P2	24.16 (3)	O1—P1—Fe1	127.33 (6)
O5^i—K1A—P2	96.16 (4)	O3—P1—Fe1	52.36 (5)
O8^ii—K1A—P2	139.60 (9)	O2—P1—Fe1	121.74 (6)
O7^iv—K1A—P2	91.24 (4)	O4—P1—Fe1	50.78 (5)
O1^v—K1A—P2	63.81 (4)	O1—P1—K1B^xiii	59.0 (2)
O3^v—K1A—P2	100.43 (6)	O3—P1—K1B^xiii	60.7 (2)
P2^vi—K1A—P2	129.59 (6)	O2—P1—K1B^xiii	105.3 (4)
O7^i—K1A—Fe2^iii	157.97 (9)	O4—P1—K1B^xiii	146.2 (4)
O1^ii—K1A—Fe2^iii	101.41 (5)	Fe1—P1—K1B^xiii	107.8 (3)
O2^iii—K1A—Fe2^iii	31.94 (3)	O1—P1—K1A^xiv	46.69 (6)
O6—K1A—Fe2^iii	64.61 (3)	O3—P1—K1A^xiv	98.76 (6)
O5^i—K1A—Fe2^iii	128.15 (5)	O2—P1—K1A^xiv	147.69 (6)
O8^ii—K1A—Fe2^iii	135.93 (5)	O4—P1—K1A^xiv	69.68 (6)
O7^iv—K1A—Fe2^iii	88.38 (4)	Fe1—P1—K1A^xiv	83.15 (4)
O1^v—K1A—Fe2^iii	33.80 (3)	K1B^xiii—P1—K1A^xiv	83.1 (3)
O3^v—K1A—Fe2^iii	77.96 (4)	O1—P1—K1A^xiii	60.34 (6)
P2^vi—K1A—Fe2^iii	160.56 (6)	O3—P1—K1A^xiii	63.36 (6)
P2—K1A—Fe2^iii	52.87 (2)	O2—P1—K1A^xiii	98.95 (7)
O7^i—K1B—O6	102.9 (4)	O4—P1—K1A^xiii	152.53 (7)
O7^i—K1B—O8^ii	52.7 (2)	Fe1—P1—K1A^xiii	112.40 (4)
O6—K1B—O8^ii	155.6 (4)	K1B^xiii—P1—K1A^xiii	6.4 (4)
O7^i—K1B—O1^v	150.3 (10)	K1A^xiv—P1—K1A^xiii	88.15 (3)
O6—K1B—O1^v	89.5 (4)	O6—P2—O5	111.42 (9)
O8^ii—K1B—O1^v	111.8 (5)	O6—P2—O7^iii	110.40 (8)
O7^i—K1B—O2^iii	153.8 (10)	O5—P2—O7^iii	105.71 (8)
O6—K1B—O2^iii	82.4 (4)	O6—P2—O8^ix	112.97 (7)
O8^ii—K1B—O2^iii	119.4 (5)	O5—P2—O8^ix	110.18 (8)
O1^v—K1B—O2^iii	53.70 (19)	O7^iii—P2—O8^ix	105.76 (8)
O7^i—K1B—O3^v	107.7 (5)	O6—P2—K1B	55.9 (4)
O6—K1B—O3^v	135.6 (7)	O5—P2—K1B	70.6 (4)
O8^ii—K1B—O3^v	62.7 (3)	O7^iii—P2—K1B	86.9 (2)
O1^v—K1B—O3^v	49.3 (3)	O8^ix—P2—K1B	166.1 (2)
O2^iii—K1B—O3^v	84.0 (3)	O6—P2—K1B^xv	119.6 (4)
O7^i—K1B—O5^i	53.1 (3)	O5—P2—K1B^xv	128.4 (5)
O6—K1B—O5^i	70.5 (3)	O7^iii—P2—K1B^xv	49.9 (2)
O8^ii—K1B—O5^i	91.3 (4)	O8^ix—P2—K1B^xv	56.7 (2)
O1^v—K1B—O5^i	155.0 (6)	K1B—P2—K1B^xv	134.4 (3)
O2^iii—K1B—O5^i	107.1 (7)	O6—P2—K1A^xv	112.25 (8)
O3^v—K1B—O5^i	153.6 (4)	O5—P2—K1A^xv	135.70 (8)
O7^i—K1B—O5	100.8 (6)	O7^iii—P2—K1A^xv	51.17 (5)
O6—K1B—O5	48.5 (3)	O8^ix—P2—K1A^xv	57.68 (5)
O8^ii—K1B—O5	127.9 (8)	K1B—P2—K1A^xv	131.9 (3)
O1^v—K1B—O5	67.4 (4)	K1B^xv—P2—K1A^xv	7.3 (4)
O2^iii—K1B—O5	101.7 (3)	O6—P2—K1A	50.57 (6)
O3^v—K1B—O5	94.1 (7)	O5—P2—K1A	77.01 (7)
O5^i—K1B—O5	106.5 (3)	O7^iii—P2—K1A	86.20 (6)
O7^i—K1B—O1^ii	92.1 (6)	O8^ix—P2—K1A	163.05 (6)
O6—K1B—O1^ii	109.3 (7)	K1B—P2—K1A	6.6 (4)
O8^ii—K1B—O1^ii	75.7 (4)	K1B^xv—P2—K1A	131.4 (3)
O1^v—K1B—O1^ii	109.3 (5)	K1A^xv—P2—K1A	128.10 (5)
O2^iii—K1B—O1^ii	62.2 (4)	O6—P2—K1A^x	140.05 (6)
O3^v—K1B—O1^ii	100.9 (4)	O5—P2—K1A^x	48.60 (6)
O5^i—K1B—O1^ii	65.8 (5)	O7^iii—P2—K1A^x	59.70 (6)
O5—K1B—O1^ii	156.2 (6)	O8^ix—P2—K1A^x	106.85 (6)
O7^i—K1B—O6^vii	68.6 (4)	K1B—P2—K1A^x	84.2 (3)
O6—K1B—O6^vii	114.9 (7)	K1B^xv—P2—K1A^x	85.0 (4)
O8^ii—K1B—O6^vii	59.7 (4)	K1A^xv—P2—K1A^x	91.41 (4)
O1^v—K1B—O6^vii	81.6 (6)	K1A—P2—K1A^x	89.48 (3)
O2^iii—K1B—O6^vii	132.8 (5)	P1—O1—Fe2^xi	137.28 (9)
O3^v—K1B—O6^vii	52.3 (4)	P1—O1—K1A^xiv	110.35 (7)
O5^i—K1B—O6^vii	120.0 (4)	Fe2^xi—O1—K1A^xiv	108.47 (6)
O5—K1B—O6^vii	69.2 (5)	P1—O1—K1B^xiii	95.2 (2)
O1^ii—K1B—O6^vii	134.5 (4)	Fe2^xi—O1—K1B^xiii	88.9 (4)
O7^i—K1B—P2	113.8 (5)	K1A^xiv—O1—K1B^xiii	108.4 (4)
O6—K1B—P2	26.30 (14)	P1—O1—K1A^xiii	95.33 (6)
O8^ii—K1B—P2	154.1 (9)	Fe2^xi—O1—K1A^xiii	83.94 (6)
O1^v—K1B—P2	68.2 (3)	K1A^xiv—O1—K1A^xiii	114.92 (6)
O2^iii—K1B—P2	82.3 (3)	K1B^xiii—O1—K1A^xiii	7.2 (4)
O3^v—K1B—P2	109.9 (6)	P1—O1—K1B^xiv	107.2 (3)
O5^i—K1B—P2	95.5 (3)	Fe2^xi—O1—K1B^xiv	111.3 (2)
O5—K1B—P2	26.47 (13)	K1A^xiv—O1—K1B^xiv	3.1 (2)
O1^ii—K1B—P2	129.7 (6)	K1B^xiii—O1—K1B^xiv	109.3 (5)
O6^vii—K1B—P2	95.6 (6)	K1A^xiii—O1—K1B^xiv	116.0 (2)
O7^i—K1B—P2^vi	26.09 (11)	P1—O2—Fe2	129.17 (8)
O6—K1B—P2^vi	128.8 (4)	P1—O2—K1A^vii	134.54 (8)
O8^ii—K1B—P2^vi	26.96 (10)	Fe2—O2—K1A^vii	96.18 (7)
O1^v—K1B—P2^vi	136.0 (6)	P1—O2—K1B^vii	140.6 (4)
O2^iii—K1B—P2^vi	139.0 (7)	Fe2—O2—K1B^vii	89.7 (4)
O3^v—K1B—P2^vi	87.0 (3)	K1A^vii—O2—K1B^vii	7.7 (4)
O5^i—K1B—P2^vi	68.8 (3)	P1—O3—Ni1^ix	176.08 (9)
O5—K1B—P2^vi	118.9 (6)	P1—O3—Fe1^ix	176.08 (9)
O1^ii—K1B—P2^vi	80.6 (4)	Ni1^ix—O3—Fe1^ix	0.000 (8)
O6^vii—K1B—P2^vi	64.0 (3)	P1—O3—Fe1	94.31 (7)
P2—K1B—P2^vi	137.9 (5)	Ni1^ix—O3—Fe1	83.74 (5)
O6—Fe1—O8^viii	101.51 (5)	Fe1^ix—O3—Fe1	83.74 (5)
O6—Fe1—O8	171.50 (5)	P1—O3—K1B^xiii	93.5 (2)
O8^viii—Fe1—O8	84.17 (5)	Ni1^ix—O3—K1B^xiii	86.6 (2)
O6—Fe1—O3^ix	87.67 (6)	Fe1^ix—O3—K1B^xiii	86.6 (2)
O8^viii—Fe1—O3^ix	97.41 (6)	Fe1—O3—K1B^xiii	150.2 (4)
O8—Fe1—O3^ix	85.31 (5)	P1—O3—K1A^xiii	92.16 (6)
O6—Fe1—O4	97.02 (6)	Ni1^ix—O3—K1A^xiii	88.36 (5)
O8^viii—Fe1—O4	97.72 (5)	Fe1^ix—O3—K1A^xiii	88.36 (5)
O8—Fe1—O4	88.39 (5)	Fe1—O3—K1A^xiii	156.82 (7)
O3^ix—Fe1—O4	162.92 (5)	K1B^xiii—O3—K1A^xiii	6.7 (4)
O6—Fe1—O3	87.88 (5)	P1—O4—Fe2^i	130.97 (8)
O8^viii—Fe1—O3	163.69 (5)	P1—O4—Fe1	94.85 (7)
O8—Fe1—O3	88.12 (5)	Fe2^i—O4—Fe1	127.39 (7)
O3^ix—Fe1—O3	96.26 (5)	P2—O5—Fe2	144.00 (9)
O4—Fe1—O3	67.64 (5)	P2—O5—K1A^x	108.04 (8)
O6—Fe1—P1	91.52 (4)	Fe2—O5—K1A^x	98.77 (7)
O8^viii—Fe1—P1	131.91 (4)	P2—O5—K1B^x	112.9 (3)
O8—Fe1—P1	89.26 (4)	Fe2—O5—K1B^x	92.2 (4)
O3^ix—Fe1—P1	129.51 (4)	K1A^x—O5—K1B^x	7.0 (4)
O4—Fe1—P1	34.36 (4)	P2—O5—K1B	83.0 (4)
O3—Fe1—P1	33.33 (4)	Fe2—O5—K1B	115.3 (3)
O6—Fe1—Ni1^ix	86.67 (4)	K1A^x—O5—K1B	101.4 (2)
O8^viii—Fe1—Ni1^ix	146.34 (4)	K1B^x—O5—K1B	106.5 (3)
O8—Fe1—Ni1^ix	85.14 (4)	P2—O6—Fe1	124.85 (8)
O3^ix—Fe1—Ni1^ix	49.89 (4)	P2—O6—K1B	97.8 (5)
O4—Fe1—Ni1^ix	113.79 (4)	Fe1—O6—K1B	122.9 (3)
O3—Fe1—Ni1^ix	46.37 (4)	P2—O6—K1A	105.27 (8)
P1—Fe1—Ni1^ix	79.66 (3)	Fe1—O6—K1A	119.60 (7)
O6—Fe1—Fe1^ix	86.67 (4)	K1B—O6—K1A	8.8 (5)
O8^viii—Fe1—Fe1^ix	146.34 (4)	P2—O6—K1B^iii	124.1 (3)
O8—Fe1—Fe1^ix	85.14 (4)	Fe1—O6—K1B^iii	79.5 (2)
O3^ix—Fe1—Fe1^ix	49.89 (4)	K1B—O6—K1B^iii	108.4 (5)
O4—Fe1—Fe1^ix	113.79 (4)	K1A—O6—K1B^iii	100.0 (2)
O3—Fe1—Fe1^ix	46.37 (4)	P2^vii—O7—Fe2	136.99 (9)
P1—Fe1—Fe1^ix	79.66 (3)	P2^vii—O7—K1B^x	104.0 (3)
Ni1^ix—Fe1—Fe1^ix	0.000 (14)	Fe2—O7—K1B^x	108.3 (3)
O6—Fe1—K1B^iii	66.9 (4)	P2^vii—O7—K1A^x	102.87 (7)
O8^viii—Fe1—K1B^iii	53.0 (3)	Fe2—O7—K1A^x	104.61 (6)
O8—Fe1—K1B^iii	112.8 (3)	K1B^x—O7—K1A^x	9.2 (5)
O3^ix—Fe1—K1B^iii	58.02 (18)	P2^vii—O7—K1A^xii	95.45 (6)
O4—Fe1—K1B^iii	138.77 (19)	Fe2—O7—K1A^xii	99.95 (6)
O3—Fe1—K1B^iii	143.2 (3)	K1B^x—O7—K1A^xii	108.9 (6)
P1—Fe1—K1B^iii	157.8 (3)	K1A^x—O7—K1A^xii	118.09 (9)
Ni1^ix—Fe1—K1B^iii	103.3 (2)	P2^ix—O8—Ni1^viii	122.18 (7)
Fe1^ix—Fe1—K1B^iii	103.3 (2)	P2^ix—O8—Fe1^viii	122.18 (7)
O6—Fe1—K1A^iii	72.20 (5)	Ni1^viii—O8—Fe1^viii	0.000 (14)
O8^viii—Fe1—K1A^iii	48.48 (5)	P2^ix—O8—Fe1	123.74 (7)
O8—Fe1—K1A^iii	107.93 (5)	Ni1^viii—O8—Fe1	95.83 (5)
O3^ix—Fe1—K1A^iii	58.87 (4)	Fe1^viii—O8—Fe1	95.83 (5)
O4—Fe1—K1A^iii	138.18 (4)	P2^ix—O8—K1B^xiv	96.3 (2)
O3—Fe1—K1A^iii	147.80 (5)	Ni1^viii—O8—K1B^xiv	92.7 (5)
P1—Fe1—K1A^iii	162.15 (3)	Fe1^viii—O8—K1B^xiv	92.7 (5)
Ni1^ix—Fe1—K1A^iii	105.94 (3)	Fe1—O8—K1B^xiv	123.8 (4)
Fe1^ix—Fe1—K1A^iii	105.94 (3)	P2^ix—O8—K1A^xiv	95.59 (6)
K1B^iii—Fe1—K1A^iii	5.6 (3)	Ni1^viii—O8—K1A^xiv	100.30 (7)
O7—Fe2—O2	128.91 (6)	Fe1^viii—O8—K1A^xiv	100.30 (7)
O7—Fe2—O4^x	116.89 (6)	Fe1—O8—K1A^xiv	118.35 (6)
O2—Fe2—O4^x	114.18 (6)	K1B^xiv—O8—K1A^xiv	8.7 (5)

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