12-Membered borophosphate rings in KNi₅[P₆B₆O₂₃(OH)₁₃]

The title compound, potassium penta­nickel hexa­boro­phos­phate trideca­hydroxide, was synthesized under hydro­thermal conditions from the NiCl₂-K₃PO₄-B₂O₃-K₂CO₃-H₂O system. The crystal structure was determined using single-crystal X-ray diffraction at 100 K. The KNi₅[P₆B₆O₂₃(OH)₁₃] phase is cubic. For the three crystallographically distinct Ni centers, two occupy sites with 3 symmetry, while the third Ni and the K atom are located on sites. The structure is built from alternating borate and phosphate tetra­hedra forming 12-membered puckered rings with K⁺ ions at the centers. These rings are arranged as in cubic dense sphere packing. A novel feature of the new crystal structure is the presence of linear trimers of face-sharing [NiO₆] octa­hedra occupying the octa­hedral inter­stices of this sphere packing, and of single [NiO₆] octa­hedra in the tetra­hedral inter­stices. All oxygen corners of the Ni octa­hedra are linked to phosphate or borate tetra­hedra of the 12-membered rings to form a mixed anionic framework.

S1. Comment

Since the first report on the synthesis and characterization of a borophosphate in 1994 (Kniep et al., 1994), the borophosphate family has grown quickly. Presently, it incorporates a large number of compounds having various structures ranging from densely packed to microporous (Ewald et al., 2007). There are many borophosphate complexes with diverse transition metal ions. These occupy a niche within this group because of their promising properties, in particular as good candidates for generating novel magnetic materials (Maspoch et al., 2007). Compared with the tetrahedral or tetrahedral/triangular oxo-complexes in borophosphates, transition metal ions show higher flexibility in coordination geometry and a stronger tendency for forming edge- (or even face-) sharing linkages of metal–oxygen polyhedra, providing different ways of magnetic exchange. For example, antiferromagnetic properties were found for (NH₄)₄[Mn₉B₂(OH)₂(HPO₄)₄(PO₄)₆] with a mixed anionic framework built from PO₄ and BO₄ tetrahedra, and Mn five-vertex polyhedra and octahedra (Yang et al., 2006). The compound NH₄[FeBP₂O₈(OH)] exhibits one-dimensional channels and antiferromagnetic ordering at 17 K (Huang et al., 2001). So-called mixed anionic frameworks constructed from polyhedra that differ both in chemistry and geometry are often present in natural minerals and in many synthetic compounds. Some of them combine the usual properties of microporous materials with novel ones such as magnetic, optical and ion-conductive solids, and may be promising candidates for contribution to developments in many technologies (Cheetham et al., 1999; Davis, 2002; Yakubovich, 2008). Only two natural phases built from borate and phosphate oxo-complexes are known: these are the minerals seamanite Mn₃(OH)₂[B(OH)₄][PO₄] and lüneburgite Mg₃(H₂O)₆[BPO₄(OH)₃]₂. Both structures contain B atoms in a tetrahedral coordination. The first one formally should not be considered as borophosphate because there are no shared oxygen vertices between [B(OH)₄] and [PO₄] tetrahedra in its crystal structure; thus, it is classified as borate–phosphate (Yakubovich, Steele, Mochenova et al., 2009; Ewald et al., 2007). Dimers of B and P tetrahedra sharing a common vertex constitute the anionic part of the lüneburgite crystal structure. Our resarch is aimed at the synthesis and structural characterization of novel anionic borophosphate/transition metal systems containing alkali counter-cations. Here we describe a new compound based on a mixed anionic framework formed from [PO₄], [BO₄] and [NiO₆].

The asymmetric unit of the cubic structure, space groupPa3 (Fig. 1), consists of one unique tetrahedral P site, one unique tetrahedral B site (both on the general position 24d), three octahedral Ni sites (Ni1 and Ni2 on 8c with site symmetry 3, Ni3 on 4a,3), one K site (4b,3), and six O atoms on general positions. The phosphate polyhedron is strongly distorted: the P—O distances vary from 1.510 (2) to 1.565 (2) Å. As expected, the longer bonds are to O1 and O3 linked further to B; the short ones to O2 and O4 are linked further to Ni. The borate tetrahedron [BO₂(OH)₂] is more regular, with two B—OH bond lengths of 1.457 (4) and 1.471 (4) Å, and two equal B—O distances of 1.479 (4) Å. Similarly, the similarity of bond distances between O2— and OH— may be explained by the further bridging to P and Ni, respectively.

While Ni2 has nearly regular octahedral coordination (Table 1), Ni1 and Ni3 show strong angular distortions due to the formation of a linear trimer Ni1– Ni3–Ni1(-x, -y, -z) composed of face-sharing octahedra with 3 symmetry (Fig. 1). The angles O2(-y, -z, -x)—Ni3—O2(-x, -y, -z), including O2 atoms of the shared face, are only 79.6 (1)°, while those between O2 atoms of the opposite faces are 100.4 (1)°. Even the outer Ni1 octahedra are rather deformed, with small angles toward the common face and angles >90° for the outer O5—Ni1—O5(z, x, y) angles. The K⁺ ion in 3 position has six O atoms at distances of 2.792 (2) Å and six at 2.841 (2) Å (Table 1). Almost all the O atoms except O1 are involved in a system of O–H···O hydrogen bonds, providing additional cross-linking in the structure. With O···O distances between 2.846 (3) and 3.193 (3) Å they are medium to weak. The O5 and O6 hydrogen-bond donors participate in the formation of the coordination sphere around the B atoms typical for borate and borophosphate structures.

An essential building unit of the crystal structure is a 12-membered ring of alternating [BO₂(OH)₂] and [PO₄] tetrahedra sharing oxygen vertices. These rings with 3 (C₃) symmetry (Fig. 2) are aligned with their threefold axes along the four diagonals of the cubic unit cell. Their centers are occupied by the K⁺ ions and form a cubic, face-centered arrangement (Fig. 3). The octahedral interstices of this f.c.c. packing are occupied by the face-sharing linear trimers of [NiO₆] octahedra (Ni1–Ni3–Ni1) inclined in varying directions about the diagonals (Figs. 1 and 4) and connected over a borate and a phosphate tetrahedron to each of its six neighbor rings. The Ni2 atoms, also in octahedral coordination, occupy all tetrahedral interstices of this f.c.c. sphere packing but avoid contact with the inclined trimers, in varying off-center positions. All oxygen corners of the Ni octahedra are linked to phosphate or borate tetrahedra of the 12-membered rings. Two Ni2 octahedra close the 12-membered ring to form a cage by bridging the three [PO₄] tetrahedra on top and bottom (with regard of the threefold axis) over octahedral faces (O4) (Fig. 5). The free opposite faces of these Ni2 octahedra (O6) make the connection to three equatorial [BO₄] groups of three neighboring rings. Vice versa, the six [BO₄] tetrahedra in the equatorial plane of the 12-ring are linked to Ni2 octahedra of six neighboring rings by sharing common vertices. The linear trimeric [Ni₃O₁₂] unit built from octahedra sharing faces (Fig. 4) show very short Ni–Ni distances of 2.800 (1) Å. Thus, interesting magnetic properties may be expected. Possible magnetic superexchange through Ni—O—Ni pathways with an angle close to 90° may lead to ferromagnetic interactions within the trimer. Analogous trimeric units with even shorter Ni–Ni distances of 2.727 (1) Å were observed in Cs₄Ni₃O₁₀ for which spontaneous magnetization was observed between 9.5 and 21 K (Schmidt et al., 1992). It is worth mentioning that antiferromagnetic behavior has been found for several Ni phosphates with microporous crystal structures (Sanz et al., 1999; Daidouh et al., 1999; Liu et al., 2004; Guillou et al., 1999, 2001).

The title compound presents the second example of a borophosphate with a zwölfer single ring according to the nomenclature introduced by Ewald et al. (2007). We obtained the first compound with a similar structure also under hydrothermal conditions: Na_0.45K(Mg_0.6Ni_0.2Al_0.2)Ni₂{(Ni_0.5Al_0.3Mg_0.2)₂ [B₆P₆O₂₄(OH)₁₂]}, (II) (Yakubovich, Steele, Mochenova et al., 2009). The same anionic sublattice formed from O atoms characterizes both crystal structures. Both have K atoms encapsulated in borophosphate rings built from 12 tetrahedra. In (II), two of the three symmetrically independent Ni²⁺ octahedra are `diluted' by Mg<sup>2+</sup> and Al<sup>3+</sup> cations and differ slightly in size from the `pure` polyhedra discussed here. The main difference between the crystal structures of (I) and (II) is the distribution of other cations in their micropores. In (II) (Yakubovich, Steele, Mochenova et al., 2009) Na atoms are statistically distributed in the centers of octahedra with C₃ symmetry [Na—O distances are 2.203 (9) and 2.261 (9) Å] which are empty in the present structure, (I). On the contrary, in the crystal structure of the pure Ni–borophosphate additional H atoms occupy 1/6 positions of general type near O2, forming disordered hydroxyl groups.

The new compound KNi₅[P₆B₆O₂₃(OH)₁₃], (I), is topologically related to the cyclophosphates Cs₃V₃(PO₃)₁₂ (Lavrov et al., 1981), (III), and NaM(PO₃)₃ (M = Zn or Mg) (Abrahams et al., 2000), (IV), as parent structures. The anionic sublattices of all three structures based on six symmetrically independent O atoms are very similar. In our case (I), the 12-membered cyclophosphate ring with two independent P sites transforms to the borophosphate architecture by ordered occupation by B and P. The rings are all filled by 12-coordinate alkali cations (site 4b). The single octahedral site of Ni2 in (I) corresponds to that of V2 in (III) and Zn2 in (IV). The peculiar trimeric octahedral face-sharing [Ni₃O₁₂] unit in (I) is replaced in (III) by a Cs–V–Cs unit, and in (IV) by a Zn–Na–Zn group. Of course, the geometric and bonding properties of these groups are rather different in all three cases and therefore, despite the same space-group type and the close topological relationship, the structures are not isotypic. This is especially true for the Zn compound (IV), as here an additional octahedral site is occupied by Na3.

It is interesting that another sodium zincophosphate Na[Zn(PO₄)](H₂O), a zeolite-type material `CZP' (Harrison et al., 1996) is considered as an archetype for some borophosphates, namely for A<sup>+</sup>M<sup>2+</sup>(H<sub>2</sub>O)<sub>2</sub>(BP<sub>2</sub>O<sub>8</sub>)(H<sub>2</sub>O), A<sup>2+</sup><sub>0.5</sub>M<sup>2+</sup>(H<sub>2</sub>O)<sub>2</sub>(BP<sub>2</sub>O<sub>8</sub>)(H<sub>2</sub>O), and M<sup>3+</sup>(H<sub>2</sub>O)<sub>2</sub>(BP<sub>2</sub>O<sub>8</sub>)(H<sub>2</sub>O), where A = Na, K, Ca, and M = Zn, Co, Ni, Fe, Mn, Cd, Sc, In (Boy et al., 2001a,b; Boy, Stowasser et al., 2001; Shi, Shan, Dai et al., 2003; Shi, Shan, He et al., 2003; Menezes et al., 2007; Yakubovich, Steele & Dimitrova, 2009; Yilmaz et al., 2000; Ge et al., 2003; Ewald et al., 2004, 2006). The `CZP' crystal structure is based on an anionic framework formed from [ZnO₄] and [PO₄] tetrahedra sharing vertices. In borophosphates the [BO₄] tetrahedron plays the role of one independent [ZnO₄] polyhedron, while the second [ZnO₄] tetrahedron transforms in an [M(H₂O)₂O₄] octahedron. According to Boy, Stowasser et al. (2001) at 453 K water molecules that coordinate Zn atoms in NaZn(H₂O)₂(BP₂O₈)(H₂O) are lost from the crystal structure. This leads to a transformation of Zn octahedra into tetrahedra, and the mixed anionic framework {ZnBP₂O₈} in the borophosphate becomes topologically identical to that {Zn₂P₂O₈} in Na[Zn(PO₄)](H₂O) (Figs. 6, 7). The above examples demonstrate a tendency of subsistence of phosphate archetypes for borophosphate compounds. To our knowledge, no cases of opposite processes have been cited in the literature up to now.

Related literature

For related literature, see: Abrahams et al. (2000); Boy et al. (2001a, 2001b, 2001c); Davis (2002); Ewald et al. (2004, 2006, 2007); Guillou et al. (2001); Huang et al. (2001); Kniep et al. (1994); Maspoch et al. (2007); Yakubovich (2008); Yang et al. (2006).

S2. Experimental

The title compound was synthesized under mild hydrothermal conditions. The starting materials – fine chemicals of NiCl₂, K₃PO₄, B₂O₃, and K₂CO₃ – were mixed in distilled water (weight ratio 4:2:8:1:45) and placed in a PTFE-lined stainless steel autoclave. The pH of the initial solution was 5–6. The experiment was performed at a temperature of 553 K and a pressure of 7 x 10³ kPa over a period of 20 d. Light green crystals of an octahedral shape up to 0.3 mm were filtered off, washed with water and dried in air. The presence of Ni, K, P, O and B in the samples was confirmed by qualitative X-ray spectral analysis (Jeol JSM-6480LV, EDSINCA-Wave 500).

S3. Refinement

The positions of two independent H atoms at O5 and O6 were obtained by difference Fourier techniques and were refined with isotropic displacement parameters. The O—H bond lengths were constrained to 0.85 Å. As in this stage the formula remained unbalanced, namely {KNi₅P₆B₆O₂₄(OH₁₂}^- (Z = 4), the coordinates of one more proton per formula had to be localized. The only reasonable position for an additional H atom was found at O2 which had a low bond valence sum and enough space for OH^-. Thus it could bear 1/6 disordered H in a 24d position. A structure model including a calculated position for this H3 atom gave a small lowering of R values and reasonable geometric parameters for a hydrogen bond toward O6.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures

	Fig. 1. The main structural elements of the title compound. Displacement ellipsoids are drawn at the 90% probability level. Dashed H3 disordered with 1/6 occupation. Symmetry transformations: a -y, -z, -x; b –z, -x, -y; c –x, -y, -z; d y, z, x; e z, x, y; f -1/2 + z, x, 0.5 - y; g -1/2 + x, y,0.5 - z; h 0.5 - z, -x, 1/2 + y; i –y, -1/2 + z, 0.5 - x; k 1/2 + x, y, 0.5 - z.
	Fig. 2. The 12-membered puckered ring of alternating [PO4] and [BO4] tetrahedra centered by K shown (a) along the threefold axis along [111] and (b) appr. from [011].
	Fig. 3. Cubic close packed (f.c.c.) arrangement of the borophosphate rings in four orientations. Only the B and P atoms and their direct connections are shown.
	Fig. 4. Linear trimer of the [NiO6] octahedra with symmetry and its connection to the fragments of six neighboring borophosphate rings.
	Fig. 5. Linkage of the Ni2 octahedra to the borophosphate rings. For clarity, the O ligands at Ni are cut off.
	Fig. 6. The Na[Zn(PO4)](H2O) (CZP) crystal structure in an [001] projection.
	Fig. 7. The A^+M^2+(H2O)2(BP2O8)(H2O) crystal structure transformed to the CZP type shown for the Na, Mn variety.

Potassium pentanickel hexaborophosphate tridecahydroxide

Crystal data

KNi5[P6B6O23(OH)13]	Dx = 3.188 Mg m^−3
Mr = 2344.67	Mo Kα radiation, λ = 0.71073 Å
Cubic, Pa3	Cell parameters from 1017 reflections
Hall symbol: -P 2ac 2ab 3	θ = 2.6–20.7°
a = 13.467 (2) Å	µ = 4.52 mm^−1
V = 2442.3 (6) Å^3	T = 100 K
Z = 2	Octahedron, light green
F(000) = 2320	0.1 × 0.1 × 0.1 mm

Data collection

CCD area detector diffractometer	1012 independent reflections
Radiation source: sealed tube	821 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.6°
ϕ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	k = −17→17
Tmin = 0.637, Tmax = 0.643	l = −17→17
27118 measured reflections

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)] = 0.032	Hydrogen site location: difference Fourier map
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0217P)^2 + 0.P] where P = (Fo^2 + 2Fc^2)/3
1012 reflections	(Δ/σ)max < 0.001
89 parameters	Δρmax = 0.45 e Å^−3
2 restraints	Δρmin = −0.58 e Å^−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.

Refinement. Refinement ofF² against ALL reflections. The weightedR-factor wR and goodness of fitS are based onF², conventional R-factorsR are based onF, withF set to zero for negativeF². The threshold expression ofF²> σ(F²) is used only for calculatingR-factors(gt)etc. and is not relevant to the choice of reflections for refinement. R-factors based onF² are statistically about twice as large as those based onF, andR- 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)
K1	0.0000	0.0000	0.5000	0.0089 (4)
B1	−0.2254 (3)	−0.0250 (3)	0.3044 (3)	0.0077 (8)
Ni1	0.12004 (3)	0.12004 (3)	0.12004 (3)	0.00669 (18)
Ni2	0.15090 (3)	−0.15090 (3)	0.34910 (3)	0.00843 (19)
Ni3	0.0000	0.0000	0.0000	0.0075 (2)
P1	−0.02930 (7)	−0.00705 (7)	0.25147 (6)	0.0075 (2)
O3	−0.14022 (16)	−0.03100 (17)	0.23535 (17)	0.0094 (5)
O2	0.01861 (16)	0.00812 (17)	0.15127 (16)	0.0087 (5)
H3	0.0606	−0.0388	0.1560	0.010*	0.16667
O4	0.01509 (17)	−0.08936 (16)	0.31354 (16)	0.0087 (5)
O5	0.22086 (17)	0.06718 (18)	0.21905 (17)	0.0102 (5)
H1	0.199 (3)	0.060 (3)	0.2779 (10)	0.012*
O1	−0.01956 (17)	0.09216 (16)	0.31125 (16)	0.0092 (5)
O6	0.21310 (17)	−0.11212 (17)	0.21395 (17)	0.0098 (5)
H2	0.178 (2)	−0.131 (3)	0.1648 (17)	0.012*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0089 (4)	0.0089 (4)	0.0089 (4)	−0.0004 (4)	−0.0004 (4)	0.0004 (4)
B1	0.010 (2)	0.009 (2)	0.0040 (18)	−0.0013 (16)	0.0024 (15)	−0.0020 (15)
Ni1	0.00669 (18)	0.00669 (18)	0.00669 (18)	−0.00002 (17)	−0.00002 (17)	−0.00002 (17)
Ni2	0.00843 (19)	0.00843 (19)	0.00843 (19)	−0.00001 (18)	−0.00001 (18)	0.00001 (18)
Ni3	0.0075 (2)	0.0075 (2)	0.0075 (2)	−0.0001 (2)	−0.0001 (2)	−0.0001 (2)
P1	0.0078 (4)	0.0077 (4)	0.0069 (4)	−0.0003 (3)	0.0012 (3)	−0.0006 (4)
O3	0.0070 (12)	0.0135 (13)	0.0078 (12)	0.0003 (10)	0.0011 (10)	−0.0024 (10)
O2	0.0086 (13)	0.0094 (12)	0.0082 (12)	−0.0005 (10)	0.0010 (10)	−0.0005 (10)
O4	0.0091 (13)	0.0095 (12)	0.0075 (12)	0.0013 (10)	−0.0021 (10)	0.0005 (10)
O5	0.0112 (13)	0.0126 (13)	0.0067 (12)	0.0029 (10)	0.0011 (10)	0.0010 (10)
O1	0.0121 (13)	0.0077 (12)	0.0078 (12)	0.0006 (10)	−0.0008 (10)	0.0008 (10)
O6	0.0106 (13)	0.0103 (13)	0.0086 (13)	−0.0023 (10)	−0.0018 (10)	−0.0001 (10)

Geometric parameters (Å, º)

K1—O4^i	2.792 (2)	Ni2—O4^iii	2.064 (2)
K1—O4	2.792 (2)	Ni2—O4	2.064 (2)
K1—O4^ii	2.792 (2)	Ni2—O4^iv	2.064 (2)
K1—O4^iii	2.792 (2)	Ni2—O6^iii	2.071 (2)
K1—O4^iv	2.792 (2)	Ni2—O6^iv	2.071 (2)
K1—O4^v	2.792 (2)	Ni2—O6	2.071 (2)
K1—O1^iii	2.841 (2)	Ni3—O2^viii	2.055 (2)
K1—O1^i	2.841 (2)	Ni3—O2^vii	2.055 (2)
K1—O1^v	2.841 (2)	Ni3—O2^ix	2.055 (2)
K1—O1	2.841 (2)	Ni3—O2^x	2.055 (2)
K1—O1^iv	2.841 (2)	Ni3—O2	2.055 (2)
K1—O1^ii	2.841 (2)	Ni3—O2^xi	2.055 (2)
B1—O6^vi	1.457 (4)	Ni3—Ni1^xi	2.8000 (9)
B1—O5^vi	1.471 (4)	P1—O2	1.510 (2)
B1—O3	1.479 (4)	P1—O4	1.512 (2)
B1—O1^v	1.480 (4)	P1—O3	1.543 (2)
Ni1—O5^vii	2.032 (2)	P1—O1	1.565 (2)
Ni1—O5^viii	2.032 (2)	O2—H3	0.8500
Ni1—O5	2.032 (2)	O5—B1^xii	1.471 (4)
Ni1—O2	2.077 (2)	O5—H1	0.851 (19)
Ni1—O2^viii	2.077 (2)	O1—B1^i	1.480 (4)
Ni1—O2^vii	2.077 (2)	O6—B1^xii	1.457 (4)
Ni1—Ni3	2.8000 (9)	O6—H2	0.85 (3)
O4^i—K1—O4	118.98 (7)	O2^viii—Ni1—O2^vii	78.63 (9)
O4^i—K1—O4^ii	61.02 (7)	O5^vii—Ni1—Ni3	124.22 (7)
O4—K1—O4^ii	180.00 (4)	O5^viii—Ni1—Ni3	124.22 (7)
O4^i—K1—O4^iii	118.98 (7)	O5—Ni1—Ni3	124.22 (7)
O4—K1—O4^iii	61.02 (7)	O2—Ni1—Ni3	47.02 (6)
O4^ii—K1—O4^iii	118.98 (7)	O2^viii—Ni1—Ni3	47.02 (6)
O4^i—K1—O4^iv	180.0	O2^vii—Ni1—Ni3	47.02 (6)
O4—K1—O4^iv	61.02 (7)	O4^iii—Ni2—O4	86.73 (9)
O4^ii—K1—O4^iv	118.98 (7)	O4^iii—Ni2—O4^iv	86.73 (9)
O4^iii—K1—O4^iv	61.02 (7)	O4—Ni2—O4^iv	86.73 (9)
O4^i—K1—O4^v	61.02 (7)	O4^iii—Ni2—O6^iii	93.06 (9)
O4—K1—O4^v	118.98 (7)	O4—Ni2—O6^iii	178.76 (9)
O4^ii—K1—O4^v	61.02 (7)	O4^iv—Ni2—O6^iii	92.04 (9)
O4^iii—K1—O4^v	180.0	O4^iii—Ni2—O6^iv	178.76 (9)
O4^iv—K1—O4^v	118.98 (7)	O4—Ni2—O6^iv	92.04 (9)
O4^i—K1—O1^iii	105.69 (7)	O4^iv—Ni2—O6^iv	93.06 (9)
O4—K1—O1^iii	111.58 (6)	O6^iii—Ni2—O6^iv	88.17 (10)
O4^ii—K1—O1^iii	68.42 (6)	O4^iii—Ni2—O6	92.04 (9)
O4^iii—K1—O1^iii	52.43 (6)	O4—Ni2—O6	93.06 (9)
O4^iv—K1—O1^iii	74.31 (7)	O4^iv—Ni2—O6	178.76 (9)
O4^v—K1—O1^iii	127.57 (6)	O6^iii—Ni2—O6	88.17 (10)
O4^i—K1—O1^i	52.43 (6)	O6^iv—Ni2—O6	88.17 (10)
O4—K1—O1^i	105.69 (7)	O4^iii—Ni2—K1	52.46 (6)
O4^ii—K1—O1^i	74.31 (7)	O4—Ni2—K1	52.46 (6)
O4^iii—K1—O1^i	68.42 (6)	O4^iv—Ni2—K1	52.46 (6)
O4^iv—K1—O1^i	127.57 (6)	O6^iii—Ni2—K1	126.55 (7)
O4^v—K1—O1^i	111.58 (6)	O6^iv—Ni2—K1	126.55 (7)
O1^iii—K1—O1^i	64.32 (3)	O6—Ni2—K1	126.55 (7)
O4^i—K1—O1^v	74.31 (7)	O2^viii—Ni3—O2^vii	79.63 (10)
O4—K1—O1^v	68.42 (6)	O2^viii—Ni3—O2^ix	180.0
O4^ii—K1—O1^v	111.58 (6)	O2^vii—Ni3—O2^ix	100.37 (10)
O4^iii—K1—O1^v	127.57 (6)	O2^viii—Ni3—O2^x	100.37 (10)
O4^iv—K1—O1^v	105.69 (7)	O2^vii—Ni3—O2^x	180.00 (13)
O4^v—K1—O1^v	52.43 (6)	O2^ix—Ni3—O2^x	79.63 (10)
O1^iii—K1—O1^v	180.0	O2^viii—Ni3—O2	79.63 (10)
O1^i—K1—O1^v	115.68 (3)	O2^vii—Ni3—O2	79.63 (10)
O4^i—K1—O1	68.42 (6)	O2^ix—Ni3—O2	100.37 (10)
O4—K1—O1	52.43 (6)	O2^x—Ni3—O2	100.37 (10)
O4^ii—K1—O1	127.57 (6)	O2^viii—Ni3—O2^xi	100.37 (10)
O4^iii—K1—O1	74.31 (7)	O2^vii—Ni3—O2^xi	100.37 (10)
O4^iv—K1—O1	111.58 (6)	O2^ix—Ni3—O2^xi	79.63 (10)
O4^v—K1—O1	105.69 (7)	O2^x—Ni3—O2^xi	79.63 (10)
O1^iii—K1—O1	115.68 (3)	O2—Ni3—O2^xi	180.000 (16)
O1^i—K1—O1	64.32 (3)	O2^viii—Ni3—Ni1	47.68 (6)
O1^v—K1—O1	64.32 (3)	O2^vii—Ni3—Ni1	47.68 (6)
O4^i—K1—O1^iv	127.57 (6)	O2^ix—Ni3—Ni1	132.32 (6)
O4—K1—O1^iv	74.31 (7)	O2^x—Ni3—Ni1	132.32 (6)
O4^ii—K1—O1^iv	105.69 (7)	O2—Ni3—Ni1	47.68 (6)
O4^iii—K1—O1^iv	111.58 (6)	O2^xi—Ni3—Ni1	132.32 (6)
O4^iv—K1—O1^iv	52.43 (6)	O2^viii—Ni3—Ni1^xi	132.32 (6)
O4^v—K1—O1^iv	68.42 (6)	O2^vii—Ni3—Ni1^xi	132.32 (6)
O1^iii—K1—O1^iv	115.68 (3)	O2^ix—Ni3—Ni1^xi	47.68 (6)
O1^i—K1—O1^iv	180.0	O2^x—Ni3—Ni1^xi	47.68 (6)
O1^v—K1—O1^iv	64.32 (3)	O2—Ni3—Ni1^xi	132.32 (6)
O1—K1—O1^iv	115.68 (3)	O2^xi—Ni3—Ni1^xi	47.68 (6)
O4^i—K1—O1^ii	111.58 (6)	Ni1—Ni3—Ni1^xi	180.00 (4)
O4—K1—O1^ii	127.57 (6)	O2—P1—O4	115.12 (14)
O4^ii—K1—O1^ii	52.43 (6)	O2—P1—O3	108.44 (13)
O4^iii—K1—O1^ii	105.69 (7)	O4—P1—O3	107.89 (13)
O4^iv—K1—O1^ii	68.42 (6)	O2—P1—O1	107.96 (13)
O4^v—K1—O1^ii	74.31 (7)	O4—P1—O1	107.96 (13)
O1^iii—K1—O1^ii	64.32 (3)	O3—P1—O1	109.38 (13)
O1^i—K1—O1^ii	115.68 (3)	O2—P1—K1	146.46 (10)
O1^v—K1—O1^ii	115.68 (3)	O4—P1—K1	54.92 (9)
O1—K1—O1^ii	180.00 (8)	O3—P1—K1	105.00 (9)
O1^iv—K1—O1^ii	64.32 (3)	O1—P1—K1	57.02 (9)
O6^vi—B1—O5^vi	111.3 (3)	B1—O3—P1	130.6 (2)
O6^vi—B1—O3	106.8 (3)	P1—O2—Ni3	145.75 (15)
O5^vi—B1—O3	107.0 (3)	P1—O2—Ni1	124.07 (14)
O6^vi—B1—O1^v	112.9 (3)	Ni3—O2—Ni1	85.30 (9)
O5^vi—B1—O1^v	109.0 (3)	P1—O2—H3	96.7
O3—B1—O1^v	109.6 (3)	Ni3—O2—H3	96.7
O5^vii—Ni1—O5^viii	91.47 (10)	Ni1—O2—H3	96.7
O5^vii—Ni1—O5	91.47 (10)	P1—O4—Ni2	140.63 (15)
O5^viii—Ni1—O5	91.47 (10)	P1—O4—K1	98.78 (11)
O5^vii—Ni1—O2	170.90 (9)	Ni2—O4—K1	91.65 (8)
O5^viii—Ni1—O2	96.34 (9)	B1^xii—O5—Ni1	118.9 (2)
O5—Ni1—O2	93.00 (9)	B1^xii—O5—H1	106 (3)
O5^vii—Ni1—O2^viii	96.35 (9)	Ni1—O5—H1	115 (3)
O5^viii—Ni1—O2^viii	93.00 (9)	B1^i—O1—P1	128.9 (2)
O5—Ni1—O2^viii	170.90 (9)	B1^i—O1—K1	135.6 (2)
O2—Ni1—O2^viii	78.63 (9)	P1—O1—K1	95.46 (10)
O5^vii—Ni1—O2^vii	93.00 (9)	B1^xii—O6—Ni2	125.6 (2)
O5^viii—Ni1—O2^vii	170.90 (9)	B1^xii—O6—H2	115 (2)
O5—Ni1—O2^vii	96.35 (9)	Ni2—O6—H2	113 (2)
O2—Ni1—O2^vii	78.63 (9)

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