Sodium penta­potassium penta­nickel tetra­(diphosphate), NaK₅Ni₅(P₂O₇)₄

The structure of the title compound, NaK₅Ni₅(P₂O₇)₄, is characterized by the presence of two crystallographically independent P₂O₇ groups with different conformations. The conformation of the first P₂O₇ group is eclipsed, whereas that of the second is staggered. All atoms are in general positions except for two nickel and one potassium ions which lie on symmetry centers. Moreover, the structure exhibits disorder of the cationic sites with one general position fully occupied equally by Na⁺ and Ni²⁺ cations. This mixed site is surrounded by five O atoms forming a square-based pyramid. The crystal structure consists of edge-sharing [NiO₆] octa­hedra forming infinite zigzag chains [Ni₃O₁₄] running parallel to [100]. Adjacent chains are connected through apices to P₂O₇ groups and to another [NiO₆] or to a [KO₆] octa­hedron. The resulting three-dimensional framework presents inter­secting tunnels running along the [010] and [001] directions in which the seven- and nine-coordinated potassium cations are located. The crystal structure of this new phosphate represents a new structural type.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](P-O) = 0.002 Å
• Disorder in main residue
• R factor = 0.027
• wR factor = 0.071
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    O     Ueq(max)/Ueq(min) ...        4.3 Ratio
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O5

Alert level C
PLAT213_ALERT_2_C Atom O5              has ADP max/min Ratio .....        3.3 prola
PLAT213_ALERT_2_C Atom O6              has ADP max/min Ratio .....        3.4 prola
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         P2
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    M1     O3
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    M1     O7
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    M1     O5
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    M1     O8
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    M1     O9
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    O3     M1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    O7     M1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    O8     M1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........         M1
                    O9     M1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O3     M1     O7
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O3     M1     O5
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O7     M1     O5
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O3     M1     O8
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O7     M1     O8
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O5     M1     O8
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O3     M1     O9
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O7     M1     O9
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O5     M1     O9
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........         M1
                    O8     M1     O9
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT975_ALERT_2_C Positive Residual Density at 0.47A from O5     .       0.82 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 0.61A from O9     .       0.41 eA-3

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni4    --  O5      ..       49.3 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni4    --  O8_f    ..        6.2 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni4    --  O9_f    ..       14.6 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni4    --  O7_i    ..       20.6 su
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................          3 Perc.
PLAT793_ALERT_4_G The Model has Chirality at P1      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at P2      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at P4      (Verify) ....          S

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
  25 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

  19 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

The most studied condensed phosphates are the diphosphates formerly called pyrophosphates. Most of these phosphates are polymorphic. The stability of each allotropic variety depends on several factors such as size and the electron affinity of the ions and synthesis conditions, in particular temperature and pressure. Thus in the case of Ni₂P₂O₇, we note the existence of four allotropic varieties: the form α-Ni₂P₂O₇ stable at room temperature and the γ-Ni₂P₂O₇ determined by Lukaszewicz (1967), the high temperature form β-Ni₂P₂O₇ obtained by Pietraszko & Lukaszewicz (1968) at 853 K and the δ-Ni₂P₂O₇ discovered by Masse et al. (1979). The addition of an alkali cation like Na or K in this system leads to new compounds with different structures. Indeed we find K₂NiP₂O₇ investigated by El Maadi et al. (1995), Na_7.39Ni_4.24(P₂O₇)₄ by Erragh et al. 2000) and three compounds with mixed anions: K₂Ni₄(PO₄)₂(P₂O₇); Na₄Ni₃(PO₄)₂(P₂O₇) and Na₄Ni₅(PO₄)₂(P₂O₇)₂ respectively, developed by Palkina & Maksimova (1980); Nagornyi et al. (1996) and Sanz et al. (1999) but to our knowledge no pyrophosphate with a mixture of two alkaline and nickel. The present work describes the synthesis method and the crystal structure of NaK₅Ni₅(P₂O₇)₄ diphosphate from the X-ray diffraction data on single-crystal.

The partial three-dimensional plot in Fig.1 illustrates the connection ion-oxygen polyhedra in the crystal structure of the title compound. Among the 25 atoms include in the asymmetric unit of this structure, only three atoms (Ni1, Ni3 and K1) are in a special positions (1 symmetry). Furthermore, the structure is characterized by a cationic disorder in one general position fully occupied equally by Na1 and Ni4 atoms. This mixed site that will be noted M1 is surrounded by five oxygen atoms forming a square based pyramid. The conformations of the two crystallographically independent groups (P₂O₇) P1—O4—P2 and P3—O14—P4 are eclipsed and staggered, respectively as indicated by the torsion angles O1–P1–P2–O5 = 3.5 (2) ° and O8–P3–P4–O12 = -24.6 (2) °. The distances P1–P2 = 2.902 Å, P3–P4 = 3.015 Å and angles P1–O4–P2 = 127.65 (11)°, P3—O14—P4 = 135.07 (13)° are within the limits generally observed in condensed phosphate crystal chemistry. All three nickel atoms Ni1, Ni2 and Ni3 are surrounded by a roughly octahedral arrangement of six oxygen atoms except that in the mixed site (M1O₅). The potassium atoms K1, K2 and K3 are coordinated to six, seven and nine oxygen atoms, respectively.

The structure of NaK₅Ni₅(P₂O₇)₄ consists of edge-sharing [Ni1O₆] and [Ni2O₆] octahedra forming an infinite zigzag chains [Ni₃O₁₄] running parallel to [100], as shown in Fig. 2. Adjacent chains are connected by P₂O₇ groups, M1O₅ square-pyramid and [Ni3O₆] or [K1O₆] octahedra via vertices in the way to build three-dimensional network.

The resulting 3-D framework presents intersecting tunnels running along the [010] and [001] directions, where the K2 and K3 potassium cations are located (Fig.2). Probably, the structure of this phosphate represents a new structural type.

Related literature

For the crystal structure of nickel diphosphate, see: Lukaszewicz (1967); Pietraszko & Lukaszewicz (1968); Masse et al. (1979). For the structures of sodium and potassium nickel diphosphate, see: El Maadi et al. (1995); Erragh et al. (2000). For phosphates with mixed anions, see: Palkina & Maksimova (1980); Nagornyi et al. (1996); Sanz et al. (1999). For bond-valence analysis, see: Brown & Altermatt (1985).

S2. Experimental

NaK₅Ni₅(P₂O₇)₄ is obtained during the preparation of a mixture of triphosphate. Indeed, the powder of "NaK₂NiP₃O₁₀" synthesized by wet process is introduced into a platinum crucible, and then gradually heated to a temperature above its melting point (1073 K) for 2 h, followed by slow cooling of the order of 10 °K per hour up to 673 °K. Then the furnace is shuts down and the cooling is continued until room temperature. Small colourless single crystals were isolated from the mixture of phases. The study of crystal structure by X-ray diffraction leads to the formula of the new phosphate: NaK₅Ni₅(P₂O₇)₄.

S3. Refinement

The atomic displacement factors of O5 and O6 atoms are very large compared to other oxygen atoms because the O5 is linked to Ni4 and Na1 occupying the disordered site and O6 is related to K2 and K3 that are in the tunnels. This explains the large displacement of these atoms. The highest peak and the deepest hole in the final Fourier map are at 0.76 Å and 0.49 Å, respectively, from Na1 and K2. The refinement of the occupancy rates of the mixed site of Na1 and Ni4 led to 0.5 for Na and 0.5 for Ni. These values are in good agreement with the charge balance and the bond valence analysis which gives occupation numbers of 0.60 for Ni and 0.40 for Na (Brown & Altermatt, 1985). The not significant bonds and angles were removed from the CIF file.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

Fig. 1. Plot of NaK5Ni5(P2O7)4 crystal structure showing polyhedra linkage. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes:(i) -x, -y, -z; (ii) -x + 1, -y, -z; (iii) -x + 1, -y + 1, -z; (iv) x + 1, y + 1, z; (v) x, y + 1, z; (vi) -x + 1, -y + 1, -z + 1; (vii) -x, -y, -z + 1; (viii) -x + 1, -y, -z + 1; (ix) x + 1, y, z; (x) x - 1, y, z; (xi) x - 1, y - 1, z; (xii) x, y - 1, z.

Fig. 2. Projection views of the NaK5Ni5(P2O7)4 framework structure showing tunnels running along b and c directions where K2 and K3 atoms are located respectively.

Sodium pentapotassium pentanickel tetra(diphosphate)

Crystal data

NaK5Ni5(P2O7)4	Z = 1
Mr = 1207.80	F(000) = 590
Triclinic, P1	Dx = 3.288 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.188 (4) Å	Cell parameters from 3608 reflections
b = 9.282 (5) Å	θ = 2.6–30.2°
c = 10.026 (5) Å	µ = 5.31 mm^−1
α = 109.31 (2)°	T = 296 K
β = 90.019 (12)°	Block, colourless
γ = 104.066 (13)°	0.20 × 0.14 × 0.11 mm
V = 610.0 (5) Å^3

Data collection

Bruker APEXII CCD detector diffractometer	3608 independent reflections
Radiation source: fine-focus sealed tube	3195 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω and ϕ scans	θmax = 30.2°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	h = −10→10
Tmin = 0.511, Tmax = 0.638	k = −13→13
13411 measured reflections	l = −14→14

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)] = 0.027	w = 1/[σ^2(Fo^2) + (0.034P)^2 + 1.127P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.071	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.91 e Å^−3
3608 reflections	Δρmin = −0.91 e Å^−3
218 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0078 (9)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
Ni1	0.0000	0.0000	0.0000	0.00836 (10)
Ni2	0.36001 (4)	−0.04138 (3)	−0.12590 (3)	0.01024 (8)
Ni3	0.5000	0.5000	0.0000	0.02272 (13)
Ni4	0.42559 (7)	0.37578 (6)	0.68239 (5)	0.01395 (11)	0.50
Na1	0.42559 (7)	0.37578 (6)	0.68239 (5)	0.01395 (11)	0.50
K1	0.5000	0.0000	0.5000	0.02299 (18)
K2	0.05087 (10)	0.19327 (8)	0.42045 (7)	0.02536 (14)
K3	0.00287 (10)	0.45372 (7)	0.18072 (8)	0.02541 (14)
P1	0.36193 (8)	0.26003 (7)	0.17071 (6)	0.00759 (12)
P2	0.65917 (10)	0.34427 (8)	0.39912 (7)	0.01475 (14)
P3	−0.14668 (8)	−0.18481 (7)	0.22059 (6)	0.00879 (12)
P4	0.25079 (8)	−0.18870 (7)	0.12603 (7)	0.00936 (12)
O1	0.1486 (2)	0.1946 (2)	0.16422 (19)	0.0129 (3)
O2	0.4605 (2)	0.1478 (2)	0.06750 (18)	0.0110 (3)
O3	0.4162 (3)	0.4235 (2)	0.15797 (19)	0.0134 (3)
O4	0.4368 (2)	0.2883 (2)	0.33014 (19)	0.0118 (3)
O5	0.6436 (5)	0.3267 (3)	0.5429 (3)	0.0456 (8)
O6	0.7578 (3)	0.2302 (3)	0.3004 (3)	0.0410 (7)
O7	0.7412 (3)	0.5116 (2)	0.4030 (2)	0.0239 (4)
O8	−0.2634 (3)	−0.3502 (2)	0.1363 (2)	0.0172 (4)
O9	−0.2049 (3)	−0.1394 (2)	0.3710 (2)	0.0174 (4)
O10	−0.1531 (2)	−0.0619 (2)	0.15276 (19)	0.0120 (3)
O11	0.1762 (2)	−0.1410 (2)	0.00776 (19)	0.0107 (3)
O12	0.2715 (3)	−0.3547 (2)	0.0742 (2)	0.0167 (4)
O13	0.4217 (3)	−0.0687 (2)	0.21951 (19)	0.0143 (3)
O14	0.0753 (3)	−0.1883 (2)	0.2327 (2)	0.0164 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.00652 (18)	0.00716 (18)	0.0118 (2)	0.00142 (14)	0.00205 (15)	0.00396 (15)
Ni2	0.00772 (14)	0.00786 (14)	0.01396 (16)	0.00273 (11)	0.00143 (11)	0.00166 (11)
Ni3	0.0308 (3)	0.0183 (2)	0.0120 (2)	−0.0114 (2)	−0.0028 (2)	0.00858 (19)
Ni4	0.0144 (2)	0.0095 (2)	0.0161 (2)	−0.00049 (17)	−0.00043 (18)	0.00461 (18)
Na1	0.0144 (2)	0.0095 (2)	0.0161 (2)	−0.00049 (17)	−0.00043 (18)	0.00461 (18)
K1	0.0363 (5)	0.0181 (4)	0.0159 (4)	0.0108 (3)	0.0048 (3)	0.0049 (3)
K2	0.0255 (3)	0.0285 (3)	0.0226 (3)	0.0048 (3)	−0.0035 (2)	0.0110 (3)
K3	0.0256 (3)	0.0181 (3)	0.0365 (4)	0.0065 (2)	0.0080 (3)	0.0139 (3)
P1	0.0070 (2)	0.0060 (2)	0.0097 (3)	0.00174 (19)	0.0021 (2)	0.0025 (2)
P2	0.0162 (3)	0.0093 (3)	0.0164 (3)	0.0049 (2)	−0.0048 (2)	0.0001 (2)
P3	0.0081 (3)	0.0080 (3)	0.0102 (3)	0.0015 (2)	0.0023 (2)	0.0034 (2)
P4	0.0078 (3)	0.0087 (3)	0.0124 (3)	0.0021 (2)	0.0017 (2)	0.0047 (2)
O1	0.0082 (8)	0.0119 (8)	0.0164 (8)	0.0017 (6)	0.0021 (6)	0.0025 (7)
O2	0.0098 (8)	0.0098 (7)	0.0116 (8)	0.0037 (6)	0.0029 (6)	0.0004 (6)
O3	0.0178 (9)	0.0092 (8)	0.0141 (8)	0.0024 (7)	0.0027 (7)	0.0058 (7)
O4	0.0097 (8)	0.0142 (8)	0.0111 (8)	0.0020 (6)	0.0019 (6)	0.0049 (7)
O5	0.088 (2)	0.0238 (12)	0.0236 (12)	0.0141 (13)	−0.0258 (13)	0.0071 (10)
O6	0.0198 (11)	0.0277 (12)	0.0533 (16)	0.0167 (10)	−0.0176 (11)	−0.0223 (11)
O7	0.0176 (9)	0.0138 (9)	0.0312 (11)	−0.0018 (7)	0.0042 (8)	−0.0001 (8)
O8	0.0208 (9)	0.0105 (8)	0.0165 (9)	0.0004 (7)	−0.0026 (7)	0.0024 (7)
O9	0.0195 (9)	0.0202 (9)	0.0126 (8)	0.0070 (7)	0.0047 (7)	0.0043 (7)
O10	0.0106 (8)	0.0115 (8)	0.0174 (8)	0.0050 (6)	0.0044 (6)	0.0081 (7)
O11	0.0085 (7)	0.0118 (8)	0.0140 (8)	0.0033 (6)	0.0013 (6)	0.0066 (6)
O12	0.0211 (9)	0.0093 (8)	0.0218 (9)	0.0061 (7)	0.0042 (7)	0.0065 (7)
O13	0.0108 (8)	0.0177 (9)	0.0135 (8)	0.0005 (7)	0.0001 (6)	0.0062 (7)
O14	0.0102 (8)	0.0264 (10)	0.0195 (9)	0.0071 (7)	0.0051 (7)	0.0150 (8)

Geometric parameters (Å, º)

Ni1—O10^i	2.0403 (19)	K3—O6^x	2.953 (3)
Ni1—O10	2.0403 (19)	K3—O12^i	2.971 (3)
Ni1—O11	2.0487 (18)	K3—O3	3.053 (3)
Ni1—O11^i	2.0487 (18)	K3—O8^v	3.066 (2)
Ni1—O1	2.052 (2)	K3—O14^v	3.098 (3)
Ni1—O1^i	2.052 (2)	P1—O1	1.4986 (19)
Ni1—Ni2	2.9329 (14)	P1—O2	1.5178 (18)
Ni2—O2^ii	1.9963 (19)	P1—O3	1.5200 (19)
Ni2—O10^i	2.0171 (19)	P1—O4	1.602 (2)
Ni2—O6^ii	2.024 (2)	P2—O5	1.505 (3)
Ni2—O13^ii	2.0595 (19)	P2—O6	1.509 (2)
Ni2—O2	2.120 (2)	P2—O7	1.509 (2)
Ni2—O11	2.1504 (18)	P2—O4	1.631 (2)
Ni2—Ni2^ii	2.9960 (14)	P3—O8	1.514 (2)
Ni3—O3	1.9781 (19)	P3—O9	1.515 (2)
Ni3—O3^iii	1.9781 (19)	P3—O10	1.5178 (18)
Ni3—O8^i	2.070 (2)	P3—O14	1.609 (2)
Ni3—O8^iv	2.070 (2)	P4—O12	1.500 (2)
Ni3—O12^ii	2.342 (2)	P4—O13	1.508 (2)
Ni3—O12^v	2.342 (2)	P4—O11	1.5333 (19)
M1—O3^vi	2.079 (2)	P4—O14	1.654 (2)
M1—O7^vi	2.112 (2)	O2—Ni2^ii	1.9963 (19)
M1—O5	2.132 (4)	O3—M1^vi	2.079 (2)
M1—O8^vii	2.208 (2)	O6—Ni2^ii	2.024 (2)
M1—O9^vii	2.269 (2)	O6—K2^ix	2.574 (3)
K1—O13^viii	2.696 (2)	O6—K3^ix	2.953 (3)
K1—O13	2.696 (2)	O7—M1^vi	2.112 (2)
K1—O5^viii	2.839 (3)	O7—K2^vi	2.770 (2)
K1—O5	2.839 (3)	O7—K3^ix	2.915 (2)
K1—O9^ix	2.842 (2)	O8—Ni3^xi	2.070 (2)
K1—O9^vii	2.842 (2)	O8—M1^vii	2.208 (2)
K2—O6^x	2.574 (3)	O8—K3^xii	3.066 (2)
K2—O9^vii	2.609 (2)	O9—M1^vii	2.269 (2)
K2—O1	2.667 (2)	O9—K2^vii	2.609 (2)
K2—O7^vi	2.770 (2)	O9—K1^x	2.842 (2)
K2—O4	2.938 (2)	O10—Ni2^i	2.0171 (19)
K2—O10	3.011 (2)	O11—K3^i	2.865 (2)
K2—O9	3.064 (3)	O12—Ni3^xii	2.342 (2)
K3—O12^v	2.760 (2)	O12—K3^xii	2.760 (2)
K3—O1	2.805 (2)	O12—K3^i	2.971 (2)
K3—O11^i	2.865 (2)	O13—Ni2^ii	2.0595 (19)
K3—O7^x	2.915 (3)	O14—K3^xii	3.098 (3)
O10^i—Ni1—O10	180.00 (14)	O9^vii—K2—O4	89.43 (7)
O10^i—Ni1—O11	89.76 (7)	O1—K2—O4	51.46 (5)
O10—Ni1—O11	90.24 (7)	O7^vi—K2—O4	67.65 (6)
O10^i—Ni1—O11^i	90.24 (7)	O6^x—K2—O10	60.85 (7)
O10—Ni1—O11^i	89.76 (7)	O9^vii—K2—O10	124.00 (7)
O11—Ni1—O11^i	180.00 (7)	O1—K2—O10	58.11 (6)
O10^i—Ni1—O1	94.64 (8)	O7^vi—K2—O10	158.76 (6)
O10—Ni1—O1	85.36 (8)	O4—K2—O10	101.33 (6)
O11—Ni1—O1	95.94 (8)	O6^x—K2—O9	84.11 (8)
O11^i—Ni1—O1	84.06 (8)	O9^vii—K2—O9	81.83 (7)
O10^i—Ni1—O1^i	85.36 (8)	O1—K2—O9	105.24 (6)
O10—Ni1—O1^i	94.64 (8)	O7^vi—K2—O9	151.80 (7)
O11—Ni1—O1^i	84.06 (8)	O4—K2—O9	129.11 (6)
O11^i—Ni1—O1^i	95.94 (8)	O10—K2—O9	49.03 (5)
O1—Ni1—O1^i	180.00 (15)	O12^v—K3—O1	106.14 (7)
O2^ii—Ni2—O10^i	169.20 (7)	O12^v—K3—O11^i	117.27 (7)
O2^ii—Ni2—O6^ii	93.83 (9)	O1—K3—O11^i	57.90 (6)
O10^i—Ni2—O6^ii	89.84 (9)	O12^v—K3—O7^x	134.29 (7)
O2^ii—Ni2—O13^ii	89.76 (8)	O1—K3—O7^x	112.03 (6)
O10^i—Ni2—O13^ii	99.83 (8)	O11^i—K3—O7^x	104.10 (6)
O6^ii—Ni2—O13^ii	97.60 (11)	O12^v—K3—O6^x	172.29 (6)
O2^ii—Ni2—O2	86.65 (8)	O1—K3—O6^x	66.64 (6)
O10^i—Ni2—O2	88.70 (8)	O11^i—K3—O6^x	61.89 (7)
O6^ii—Ni2—O2	174.32 (10)	O7^x—K3—O6^x	50.52 (6)
O13^ii—Ni2—O2	88.07 (8)	O12^v—K3—O12^i	91.74 (7)
O2^ii—Ni2—O11	82.20 (7)	O1—K3—O12^i	106.98 (6)
O10^i—Ni2—O11	87.57 (7)	O11^i—K3—O12^i	51.26 (5)
O6^ii—Ni2—O11	91.53 (11)	O7^x—K3—O12^i	100.05 (8)
O13^ii—Ni2—O11	168.23 (7)	O6^x—K3—O12^i	93.03 (7)
O2—Ni2—O11	82.93 (8)	O12^v—K3—O3	58.80 (6)
O3—Ni3—O3^iii	180.00 (9)	O1—K3—O3	50.60 (5)
O3—Ni3—O8^i	93.37 (8)	O11^i—K3—O3	96.32 (6)
O3^iii—Ni3—O8^i	86.63 (8)	O7^x—K3—O3	137.10 (7)
O3—Ni3—O8^iv	86.63 (8)	O6^x—K3—O3	113.49 (6)
O3^iii—Ni3—O8^iv	93.37 (8)	O12^i—K3—O3	121.90 (6)
O8^i—Ni3—O8^iv	180.00 (17)	O12^v—K3—O8^v	83.94 (7)
O3—Ni3—O12^ii	97.37 (7)	O1—K3—O8^v	161.23 (6)
O3^iii—Ni3—O12^ii	82.63 (7)	O11^i—K3—O8^v	103.49 (6)
O8^i—Ni3—O12^ii	100.17 (8)	O7^x—K3—O8^v	67.60 (7)
O8^iv—Ni3—O12^ii	79.83 (8)	O6^x—K3—O8^v	103.75 (7)
O3—Ni3—O12^v	82.63 (7)	O12^i—K3—O8^v	56.06 (6)
O3^iii—Ni3—O12^v	97.37 (7)	O3—K3—O8^v	142.67 (6)
O8^i—Ni3—O12^v	79.83 (8)	O12^v—K3—O14^v	50.49 (6)
O8^iv—Ni3—O12^v	100.17 (8)	O1—K3—O14^v	149.36 (6)
O12^ii—Ni3—O12^v	180.0	O11^i—K3—O14^v	145.51 (6)
O3^vi—M1—O7^vi	97.28 (9)	O7^x—K3—O14^v	84.43 (6)
O3^vi—M1—O5	100.21 (10)	O6^x—K3—O14^v	134.95 (6)
O7^vi—M1—O5	107.23 (9)	O12^i—K3—O14^v	94.58 (6)
O3^vi—M1—O8^vii	80.71 (8)	O3—K3—O14^v	99.55 (5)
O7^vi—M1—O8^vii	100.81 (9)	O8^v—K3—O14^v	48.38 (6)
O5—M1—O8^vii	151.53 (8)	O1—P1—O2	113.34 (11)
O3^vi—M1—O9^vii	146.47 (7)	O1—P1—O3	112.74 (10)
O7^vi—M1—O9^vii	97.27 (9)	O2—P1—O3	111.86 (11)
O5—M1—O9^vii	104.03 (9)	O1—P1—O4	104.08 (10)
O8^vii—M1—O9^vii	66.96 (7)	O2—P1—O4	109.57 (10)
O13^viii—K1—O13	180.0	O3—P1—O4	104.53 (10)
O13^viii—K1—O5^viii	91.78 (7)	O5—P2—O6	112.93 (17)
O13—K1—O5^viii	88.22 (7)	O5—P2—O7	114.35 (14)
O13^viii—K1—O5	88.22 (7)	O6—P2—O7	112.17 (15)
O13—K1—O5	91.78 (7)	O5—P2—O4	104.13 (15)
O5^viii—K1—O5	180.00 (14)	O6—P2—O4	104.89 (12)
O13^viii—K1—O9^ix	104.71 (6)	O7—P2—O4	107.41 (11)
O13—K1—O9^ix	75.29 (6)	O8—P3—O9	109.31 (12)
O5^viii—K1—O9^ix	75.29 (9)	O8—P3—O10	114.40 (11)
O5—K1—O9^ix	104.71 (9)	O9—P3—O10	112.48 (11)
O13^viii—K1—O9^vii	75.29 (6)	O8—P3—O14	107.93 (11)
O13—K1—O9^vii	104.71 (6)	O9—P3—O14	105.88 (11)
O5^viii—K1—O9^vii	104.71 (9)	O10—P3—O14	106.35 (10)
O5—K1—O9^vii	75.29 (9)	O12—P4—O13	114.34 (12)
O9^ix—K1—O9^vii	180.0	O12—P4—O11	112.79 (11)
O6^x—K2—O9^vii	149.78 (9)	O13—P4—O11	114.65 (11)
O6^x—K2—O1	74.28 (9)	O12—P4—O14	105.83 (11)
O9^vii—K2—O1	135.37 (7)	O13—P4—O14	103.88 (11)
O6^x—K2—O7^vi	107.73 (8)	O11—P4—O14	103.90 (10)
O9^vii—K2—O7^vi	75.36 (8)	P1—O4—P2	127.65 (11)
O1—K2—O7^vi	102.63 (7)	P3—O14—P4	135.07 (13)
O6^x—K2—O4	119.96 (9)
O1—P1—P2—O5	3.52 (17)	O8—P3—P4—O12	−24.60 (12)

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