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

Moutataouia, M.; Lamire, M.; Saadi, M.; El Ammari, L.

doi:10.1107/S160053681202017X

inorganic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page i43

doi:10.1107/S160053681202017X

Open

access

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

Meryem Moutataouia,^a Mohammed Lamire,^a ^* Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Physico-Chimie des Matériaux Inorganiques, Faculté des Sciences Aïn Chock, Casablanca, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Batouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: m_lamire@yahoo.fr

(Received 21 April 2012; accepted 4 May 2012; online 12 May 2012)

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.

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 ).

Experimental

Crystal data

NaK₅Ni₅(P₂O₇)₄
M_r = 1207.80
Triclinic, $[P \overline 1]$
a = 7.188 (4) Å
b = 9.282 (5) Å
c = 10.026 (5) Å
α = 109.31 (2)°
β = 90.019 (12)°
γ = 104.066 (13)°
V = 610.0 (5) Å³
Z = 1
Mo Kα radiation
μ = 5.31 mm⁻¹
T = 296 K
0.20 × 0.14 × 0.11 mm

Data collection

Bruker APEXII CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ) T_min = 0.511, T_max = 0.638
13411 measured reflections
3608 independent reflections
3195 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.071
S = 1.03
3608 reflections
218 parameters
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.91 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681202017X/br2200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202017X/br2200Isup2.hkl

checkCIF report

Comment top

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 top

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).

Experimental top

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.

Computing details top

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 top

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) top

Crystal data top

NaK₅Ni₅(P₂O₇)₄	Z = 1
M_r = 1207.80	F(000) = 590
Triclinic, P1	D_x = 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) Å³

Data collection top

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

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.034P)² + 1.127P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.071	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.91 e Å⁻³
3608 reflections	Δρ_min = −0.91 e Å⁻³
218 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0078 (9)

Crystal data top

NaK₅Ni₅(P₂O₇)₄	γ = 104.066 (13)°
M_r = 1207.80	V = 610.0 (5) Å³
Triclinic, P1	Z = 1
a = 7.188 (4) Å	Mo Kα radiation
b = 9.282 (5) Å	µ = 5.31 mm⁻¹
c = 10.026 (5) Å	T = 296 K
α = 109.31 (2)°	0.20 × 0.14 × 0.11 mm
β = 90.019 (12)°

Data collection top

Bruker APEXII CCD detector diffractometer	3608 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	3195 reflections with I > 2σ(I)
T_min = 0.511, T_max = 0.638	R_int = 0.033
13411 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	218 parameters
wR(F²) = 0.071	0 restraints
S = 1.03	Δρ_max = 0.91 e Å⁻³
3608 reflections	Δρ_min = −0.91 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Ni1—O10ⁱ	2.0403 (19)	K3—O6^x	2.953 (3)
Ni1—O10	2.0403 (19)	K3—O12ⁱ	2.971 (3)
Ni1—O11	2.0487 (18)	K3—O3	3.053 (3)
Ni1—O11ⁱ	2.0487 (18)	K3—O8^v	3.066 (2)
Ni1—O1	2.052 (2)	K3—O14^v	3.098 (3)
Ni1—O1ⁱ	2.052 (2)	P1—O1	1.4986 (19)
Ni1—Ni2	2.9329 (14)	P1—O2	1.5178 (18)
Ni2—O2ⁱⁱ	1.9963 (19)	P1—O3	1.5200 (19)
Ni2—O10ⁱ	2.0171 (19)	P1—O4	1.602 (2)
Ni2—O6ⁱⁱ	2.024 (2)	P2—O5	1.505 (3)
Ni2—O13ⁱⁱ	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—Ni2ⁱⁱ	2.9960 (14)	P3—O8	1.514 (2)
Ni3—O3	1.9781 (19)	P3—O9	1.515 (2)
Ni3—O3ⁱⁱⁱ	1.9781 (19)	P3—O10	1.5178 (18)
Ni3—O8ⁱ	2.070 (2)	P3—O14	1.609 (2)
Ni3—O8^iv	2.070 (2)	P4—O12	1.500 (2)
Ni3—O12ⁱⁱ	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—Ni2ⁱⁱ	1.9963 (19)
M1—O5	2.132 (4)	O3—M1^vi	2.079 (2)
M1—O8^vii	2.208 (2)	O6—Ni2ⁱⁱ	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—Ni2ⁱ	2.0171 (19)
K2—O10	3.011 (2)	O11—K3ⁱ	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—K3ⁱ	2.971 (2)
K3—O11ⁱ	2.865 (2)	O13—Ni2ⁱⁱ	2.0595 (19)
K3—O7^x	2.915 (3)	O14—K3^xii	3.098 (3)

O10ⁱ—Ni1—O10	180.00 (14)	O9^vii—K2—O4	89.43 (7)
O10ⁱ—Ni1—O11	89.76 (7)	O1—K2—O4	51.46 (5)
O10—Ni1—O11	90.24 (7)	O7^vi—K2—O4	67.65 (6)
O10ⁱ—Ni1—O11ⁱ	90.24 (7)	O6^x—K2—O10	60.85 (7)
O10—Ni1—O11ⁱ	89.76 (7)	O9^vii—K2—O10	124.00 (7)
O11—Ni1—O11ⁱ	180.00 (7)	O1—K2—O10	58.11 (6)
O10ⁱ—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)
O11ⁱ—Ni1—O1	84.06 (8)	O9^vii—K2—O9	81.83 (7)
O10ⁱ—Ni1—O1ⁱ	85.36 (8)	O1—K2—O9	105.24 (6)
O10—Ni1—O1ⁱ	94.64 (8)	O7^vi—K2—O9	151.80 (7)
O11—Ni1—O1ⁱ	84.06 (8)	O4—K2—O9	129.11 (6)
O11ⁱ—Ni1—O1ⁱ	95.94 (8)	O10—K2—O9	49.03 (5)
O1—Ni1—O1ⁱ	180.00 (15)	O12^v—K3—O1	106.14 (7)
O2ⁱⁱ—Ni2—O10ⁱ	169.20 (7)	O12^v—K3—O11ⁱ	117.27 (7)
O2ⁱⁱ—Ni2—O6ⁱⁱ	93.83 (9)	O1—K3—O11ⁱ	57.90 (6)
O10ⁱ—Ni2—O6ⁱⁱ	89.84 (9)	O12^v—K3—O7^x	134.29 (7)
O2ⁱⁱ—Ni2—O13ⁱⁱ	89.76 (8)	O1—K3—O7^x	112.03 (6)
O10ⁱ—Ni2—O13ⁱⁱ	99.83 (8)	O11ⁱ—K3—O7^x	104.10 (6)
O6ⁱⁱ—Ni2—O13ⁱⁱ	97.60 (11)	O12^v—K3—O6^x	172.29 (6)
O2ⁱⁱ—Ni2—O2	86.65 (8)	O1—K3—O6^x	66.64 (6)
O10ⁱ—Ni2—O2	88.70 (8)	O11ⁱ—K3—O6^x	61.89 (7)
O6ⁱⁱ—Ni2—O2	174.32 (10)	O7^x—K3—O6^x	50.52 (6)
O13ⁱⁱ—Ni2—O2	88.07 (8)	O12^v—K3—O12ⁱ	91.74 (7)
O2ⁱⁱ—Ni2—O11	82.20 (7)	O1—K3—O12ⁱ	106.98 (6)
O10ⁱ—Ni2—O11	87.57 (7)	O11ⁱ—K3—O12ⁱ	51.26 (5)
O6ⁱⁱ—Ni2—O11	91.53 (11)	O7^x—K3—O12ⁱ	100.05 (8)
O13ⁱⁱ—Ni2—O11	168.23 (7)	O6^x—K3—O12ⁱ	93.03 (7)
O2—Ni2—O11	82.93 (8)	O12^v—K3—O3	58.80 (6)
O3—Ni3—O3ⁱⁱⁱ	180.00 (9)	O1—K3—O3	50.60 (5)
O3—Ni3—O8ⁱ	93.37 (8)	O11ⁱ—K3—O3	96.32 (6)
O3ⁱⁱⁱ—Ni3—O8ⁱ	86.63 (8)	O7^x—K3—O3	137.10 (7)
O3—Ni3—O8^iv	86.63 (8)	O6^x—K3—O3	113.49 (6)
O3ⁱⁱⁱ—Ni3—O8^iv	93.37 (8)	O12ⁱ—K3—O3	121.90 (6)
O8ⁱ—Ni3—O8^iv	180.00 (17)	O12^v—K3—O8^v	83.94 (7)
O3—Ni3—O12ⁱⁱ	97.37 (7)	O1—K3—O8^v	161.23 (6)
O3ⁱⁱⁱ—Ni3—O12ⁱⁱ	82.63 (7)	O11ⁱ—K3—O8^v	103.49 (6)
O8ⁱ—Ni3—O12ⁱⁱ	100.17 (8)	O7^x—K3—O8^v	67.60 (7)
O8^iv—Ni3—O12ⁱⁱ	79.83 (8)	O6^x—K3—O8^v	103.75 (7)
O3—Ni3—O12^v	82.63 (7)	O12ⁱ—K3—O8^v	56.06 (6)
O3ⁱⁱⁱ—Ni3—O12^v	97.37 (7)	O3—K3—O8^v	142.67 (6)
O8ⁱ—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)
O12ⁱⁱ—Ni3—O12^v	180.0	O11ⁱ—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)	O12ⁱ—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.

Experimental details

Crystal data
Chemical formula	NaK₅Ni₅(P₂O₇)₄
M_r	1207.80
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.188 (4), 9.282 (5), 10.026 (5)
α, β, γ (°)	109.31 (2), 90.019 (12), 104.066 (13)
V (Å³)	610.0 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	5.31
Crystal size (mm)	0.20 × 0.14 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1999)
T_min, T_max	0.511, 0.638
No. of measured, independent and observed [I > 2σ(I)] reflections	13411, 3608, 3195
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.707

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.071, 1.03
No. of reflections	3608
No. of parameters	218
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.91

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
El Maadi, A., Boukhari, A. & Holt, E. M. (1995). J. Chem. Crystallogr. 25, 531–536. CAS Google Scholar
Erragh, F., Boukhari, A., Abraham, F. & Elouadi, B. (2000). J. Solid State Chem. 152, 323–331. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Lukaszewicz, K. (1967). Bull. Acad. Pol. Sci. Ser. Sci. Chim. 15, 47–51. CAS Google Scholar
Masse, R., Guitel, J. C. & Durif, A. (1979). Mater. Res. Bull. 14, 337–341. CrossRef CAS Web of Science Google Scholar
Nagornyi, P. G., Kapshuk, A. A., Sobolev, A. N. & Golego, N. V. (1996). Kristallografiya, 41, 835–838. CAS Google Scholar
Palkina, K. K. & Maksimova, S. I. (1980). Dokl. Akad. Nauk SSSR, 250, 1130–1134. CAS Google Scholar
Pietraszko, A. & Lukaszewicz, K. (1968). Bull. Acad. Pol. Sci. Ser. Sci. Chim. 16, 183–187. CAS Google Scholar
Sanz, F., Parada, C., Rojo, J. M. & Ruiz-Valero, C. (1999). Chem. Mater. 11, 2673–2679. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1999). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar