Dilithium disodium nickel(II) cyclo­hexa­phosphate dodeca­hydrate, Li2Na2NiP6O18·12H2O

Abid, S.; Al-Deyab, S.S.; Rzaigui, M.

doi:10.1107/S1600536812029960

inorganic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages i62-i63

https://doi.org/10.1107/S1600536812029960

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Dilithium disodium nickel(II) cyclohexaphosphate dodecahydrate, Li₂Na₂NiP₆O₁₈·12H₂O

Sonia Abid,^a ^* Salem S. Al-Deyab ^b and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bPetrochemical Research Chair, College of Science, King Saud University, Riyadh, Saudi Arabia
^*Correspondence e-mail: sonia.abid@fsb.rnu.tn

(Received 14 June 2012; accepted 1 July 2012; online 7 July 2012)

The crystal structure of Li₂Na₂NiP₆O₁₈·12H₂O is characterized by the presence of six-membered P₆O₁₈⁶⁻ phosphate ring anions (internal symmetry -1) having a chair conformation and three different cations, viz. Li⁺, Na⁺ and Ni²⁺, to counterbalance the anionic charge. All atoms are in general positions except for nickel, which lies on a special position with site symmetry 2. Lithium has a tetrahedral environment (LiO₄), and sodium and nickel have octahedral environments [NaO₆ and Ni(H₂O)₆, respectively]. The P₆O₁₈ rings are linked via corner sharing by NaO₆ octahedra and LiO₄ tetrahedra to form a three-dimensional framework presenting tunnels running along [010] in which the six-coordinated Ni²⁺ cations are located. The structure is stabilized by a network of O—H⋯O hydrogen bonds.

Related literature

For the crystal chemistry of cyclic phosphates, see: Averbuch-Pouchot & Durif (1996 ). For related structures containing cyclohexaphosphate rings, see: Abid et al. (2011 ); Amri et al. (2009 ); Marouani et al. (2010 ). For hydrogen bonding, see: Blessing (1986 ). For the synthesis, see: Schülke & Kayser (1985 ).

Experimental

Crystal data

Li₂Na₂NiP₆O₁₈·12H₂O
M_r = 808.58
Monoclinic, C 2/c
a = 17.728 (9) Å
b = 10.213 (2) Å
c = 14.801 (7) Å
β = 112.04 (4)°
V = 2484.0 (18) Å³
Z = 4
Ag Kα radiation
λ = 0.56085 Å
μ = 0.69 mm⁻¹
T = 298 K
0.40 × 0.35 × 0.30 mm

Data collection

Nonius MACH-3 diffractometer
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ) T_min = 0.769, T_max = 0.819
7168 measured reflections
6076 independent reflections
4296 reflections with I > 2σ(I)
R_int = 0.035
2 standard reflections every 120 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.102
S = 1.07
6076 reflections
186 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Selected bond lengths (Å)

Na1—O1ⁱ	2.4205 (19)
Na1—O5ⁱⁱ	2.384 (2)
Na1—O7ⁱⁱⁱ	2.3737 (19)
Na1—O10ⁱⁱⁱ	2.556 (2)
Na1—O11	2.546 (2)
Na1—O12	2.323 (2)
Li—O2ⁱ	1.927 (4)
Li—O8	1.930 (5)
Li—O10	1.964 (5)
Li—O11	1.972 (5)
Ni1—O13	2.0469 (16)
Ni1—O15	2.0572 (15)
Ni1—O14	2.0693 (18)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H110⋯O15ⁱⁱⁱ	0.85	1.96	2.795 (3)	165
O10—H210⋯O4^iv	0.87	2.03	2.851 (3)	159
O11—H111⋯O14ⁱⁱⁱ	0.82	2.01	2.811 (3)	164
O11—H211⋯O2	0.86	2.25	3.031 (3)	150
O12—H112⋯O12^v	0.86	2.44	3.058 (4)	130
O12—H212⋯O3^vi	0.86	2.48	3.304 (3)	161
O12—H212⋯O4^vi	0.86	2.52	3.166 (3)	133
O15—H115⋯O4^vii	0.88	1.87	2.741 (3)	171
O15—H215⋯O5ⁱ	0.83	1.85	2.673 (3)	174
O14—H114⋯O8	0.85	1.94	2.758 (3)	163
O14—H214⋯O7^viii	0.86	1.78	2.643 (3)	174
O13—H113⋯O2ⁱ	0.83	1.97	2.789 (3)	167
O13—H213⋯O1ⁱⁱ	0.84	1.84	2.677 (3)	174
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+1, z+{\script{1\over 2}}]$ ; (v) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (vii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (viii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812029960/ff2073sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029960/ff2073Isup2.hkl

checkCIF report

Comment top

Cyclophosphohates, corresponding to the anionic formula [P_nO_3n]^n-, constitute the second important family of condensed phosphates after the polyphosphates. The identified cyclic anions, built by n corner-sharing PO₄ tetrahedra, correspond to n = 3, 4, 5, 6, 8, 9, 10 and 12. The phosphoric ring anion corresponding to n = 6, called cyclohexaphosphate, has been associated to numerous organic and/or inorganic cations (Averbuch-Pouchot & Durif, 1996). But its association to three mixed cations is still very limited. In this work, we report the preparation and the structural investigation of a novel dilithium disodium nickel cyclohexaphosphate dodecahydrate, Li₂Na₂NiP₆O₁₈.12H₂O (I). To our knowledge, there is no cyclohexaphosphate with a mixture of two alkalines and bivalent cations. The partial three-dimensional plot in Fig.1 illustrates the connection ion-oxygen polyhedra and the phosphoric ring in the crystal structure of the title compound. Among the 21 atoms included in the asymmetric unit of this structure, only the Ni atom is in a special position ((Wyckoff position 4 e, site symmetry 2)). The Li, Na and Ni atoms are coordinated to four, for the first one, and to six, for the last two, oxygen atoms. The NaO₆ and P₆O₁₈ entities are linked in an alternating manner to generate a two-dimensional open framework, forming so layers parallel to the (a,b) plane (Fig. 2). Adjacent layers are connected by the LiO₄ tetrahedra to generate a three dimensional structure exhibiting channels running along the b axis (Fig. 3). Inside these channels, the Ni²⁺ cation is coordinated by six water molecules. The [Ni(H₂O)₆]²⁺ octahedron is almost regular with Ni–O distances ranging from 2.0462 (16) to 2.0691 (18) Å. The smallest distance between two octahedral centers is 9.069 Å. The cyclic anion (P₆O₁₈)^6- has a chair conformation with geometrical characteristics that show no significant difference deviation from those observed in other cyclohexaphosphates having the same internal symmetry -1 (Abid et al. 2011,Amri et al.2009; Marouani et al.2010). In addition to its interactions with the metallic cations, the phosphoric anion establish with the water molecules an important hydrogen-bonding scheme. The examination of this latter shows the existence of strong hydrogen bonds with distances O···O ranging from 2.643 (3) to 2.677 (3) Å and other weaker ones, with O···O distances falling from 2.741 (3) to 3.304 (3) Å (Blessing, 1986).

Related literature top

For the crystal chemistry of cyclic phosphates, see: Averbuch-Pouchot & Durif (1996). For related structures containing cyclohexaphosphate rings, see: Abid et al. (2011); Amri et al. (2009); Marouani et al. (2010). For hydrogen bonding, see: Blessing (1986). For the synthesis, see: Schülke & Kayser (1985).

Experimental top

Li₂Na₂NiP₆O₁₈.12H₂O was prepared by mixing Li₆P₆O₁₈.6H₂O (0.5 g, 5 mmol), NiCl₂.6H₂O (0.71 g, 3 mmol), and NaNO₃ (0.03 g, 0.4 mmol) in 50 ml of distillated water and stirring for 30 min at temperature room. The obtained solution was allowed to stand in air until formation of good greenish single crystals of the title compound. Its chemical formula was determined by X-ray diffraction. The used Li₆P₆O₁₈.6H₂O was prepared according to the procedure of Schülke and Kayser (Schülke & Kayser, 1985)

Structure description top

For the crystal chemistry of cyclic phosphates, see: Averbuch-Pouchot & Durif (1996). For related structures containing cyclohexaphosphate rings, see: Abid et al. (2011); Amri et al. (2009); Marouani et al. (2010). For hydrogen bonding, see: Blessing (1986). For the synthesis, see: Schülke & Kayser (1985).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. ORTEP-3 (Farrugia, 1997) view of (I) with atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. [Symmetry codes: (i) 0.5-x, 1.5-y, -z; (ii) 0.5-x, -0.5+y, 0.5-z; (iii) 1-x, y, 0.5-z; (iv) 0.5-x, 0.5+y, 0.5-z; (v) 0.5+x, 1.5-y, 0.5+z]
	Fig. 2. View of [Na₂(P₆O₁₈)]_n^4n- developed along the c axis.
	Fig. 3. Projection of the structure of Li₂Na₂NiP₆O₁₈.12H₂O along the b axis

Dilithium disodium nickel(II) cyclohexaphosphate dodecahydrate top

Crystal data top

Li₂Na₂NiP₆O₁₈·12H₂O	F(000) = 1640
M_r = 808.58	D_x = 2.162 Mg m⁻³
Monoclinic, C2/c	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 17.728 (9) Å	θ = 8.3–10.8°
b = 10.213 (2) Å	µ = 0.69 mm⁻¹
c = 14.801 (7) Å	T = 298 K
β = 112.04 (4)°	Prism, green
V = 2484.0 (18) Å³	0.40 × 0.35 × 0.30 mm
Z = 4

Data collection top

Nonius MACH-3 diffractometer	4296 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 28.0°, θ_min = 2.3°
non–profiled ω scans	h = −29→27
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −1→17
T_min = 0.769, T_max = 0.819	l = −1→24
7168 measured reflections	2 standard reflections every 120 min
6076 independent reflections	intensity decay: 2%

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0389P)² + 4.028P] where P = (F_o² + 2F_c²)/3
6076 reflections	(Δ/σ)_max = 0.003
186 parameters	Δρ_max = 0.80 e Å⁻³
2 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

Li₂Na₂NiP₆O₁₈·12H₂O	V = 2484.0 (18) Å³
M_r = 808.58	Z = 4
Monoclinic, C2/c	Ag Kα radiation, λ = 0.56085 Å
a = 17.728 (9) Å	µ = 0.69 mm⁻¹
b = 10.213 (2) Å	T = 298 K
c = 14.801 (7) Å	0.40 × 0.35 × 0.30 mm
β = 112.04 (4)°

Data collection top

Nonius MACH-3 diffractometer	4296 reflections with I > 2σ(I)
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	R_int = 0.035
T_min = 0.769, T_max = 0.819	2 standard reflections every 120 min
7168 measured reflections	intensity decay: 2%
6076 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	2 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.07	Δρ_max = 0.80 e Å⁻³
6076 reflections	Δρ_min = −0.60 e Å⁻³
186 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Na1	0.38942 (6)	0.74638 (9)	0.40089 (7)	0.02302 (18)
Li	0.2602 (3)	0.4883 (4)	0.2527 (3)	0.0258 (8)
O8	0.28521 (9)	0.47433 (15)	0.13696 (11)	0.0182 (3)
O9	0.16879 (9)	0.61570 (15)	0.04655 (11)	0.0209 (3)
O10	0.14882 (10)	0.42811 (17)	0.22717 (13)	0.0249 (3)
H110	0.1134	0.4875	0.2021	0.030*
H210	0.1389	0.4015	0.2772	0.030*
O11	0.25138 (10)	0.67633 (16)	0.27740 (13)	0.0260 (3)
H111	0.2134	0.6824	0.2962	0.031*
H211	0.2414	0.7291	0.2287	0.031*
O12	0.42660 (15)	0.6531 (2)	0.28051 (17)	0.0437 (5)
H112	0.4775	0.6725	0.3012	0.052*
H212	0.4065	0.6762	0.2205	0.052*
P1	0.15702 (3)	0.94221 (5)	0.03614 (4)	0.01251 (9)
P3	0.21812 (3)	0.48781 (5)	0.04013 (4)	0.01248 (9)
P2	0.09260 (3)	0.68397 (5)	−0.03712 (4)	0.01298 (9)
O4	0.07807 (9)	0.62089 (15)	−0.13208 (11)	0.0196 (3)
O2	0.16821 (9)	0.89346 (15)	0.13535 (10)	0.0177 (3)
O7	0.16162 (10)	0.37702 (15)	0.00214 (12)	0.0216 (3)
O5	0.02574 (9)	0.69398 (17)	−0.00121 (12)	0.0227 (3)
O6	0.24650 (8)	0.97174 (17)	0.04034 (11)	0.0208 (3)
O1	0.10493 (10)	1.05743 (15)	−0.00194 (12)	0.0243 (3)
O3	0.12913 (10)	0.82657 (15)	−0.04140 (11)	0.0216 (3)
Ni1	0.5000	0.24488 (3)	0.2500	0.01249 (7)
O15	0.48362 (9)	0.09969 (14)	0.33724 (11)	0.0172 (3)
H115	0.5184	0.0349	0.3502	0.021*
H215	0.4838	0.1271	0.3902	0.021*
O14	0.37693 (8)	0.24893 (14)	0.16516 (11)	0.0172 (3)
H114	0.3569	0.3256	0.1540	0.021*
H214	0.3616	0.2121	0.1087	0.021*
O13	0.47785 (9)	0.38693 (15)	0.33445 (11)	0.0197 (3)
H113	0.4355	0.3760	0.3454	0.024*
H213	0.5162	0.4089	0.3860	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0231 (4)	0.0223 (4)	0.0243 (4)	−0.0004 (3)	0.0097 (3)	−0.0018 (4)
Li	0.0293 (19)	0.029 (2)	0.0183 (18)	0.0059 (17)	0.0085 (15)	0.0022 (16)
O8	0.0169 (6)	0.0231 (7)	0.0128 (6)	0.0045 (5)	0.0036 (5)	0.0027 (5)
O9	0.0216 (6)	0.0225 (7)	0.0143 (6)	0.0095 (5)	0.0019 (5)	−0.0022 (6)
O10	0.0241 (7)	0.0267 (8)	0.0248 (8)	0.0044 (6)	0.0104 (6)	0.0044 (7)
O11	0.0289 (8)	0.0247 (7)	0.0284 (9)	−0.0001 (6)	0.0155 (7)	0.0001 (7)
O12	0.0520 (13)	0.0494 (12)	0.0371 (11)	0.0085 (10)	0.0251 (10)	0.0033 (10)
P1	0.01273 (18)	0.01321 (18)	0.0114 (2)	−0.00086 (15)	0.00431 (15)	0.00013 (16)
P3	0.01266 (18)	0.01344 (19)	0.0114 (2)	−0.00034 (15)	0.00457 (15)	0.00006 (16)
P2	0.01426 (19)	0.01291 (18)	0.0112 (2)	−0.00007 (15)	0.00409 (16)	−0.00088 (16)
O4	0.0237 (7)	0.0195 (6)	0.0145 (6)	−0.0021 (5)	0.0059 (5)	−0.0057 (5)
O2	0.0196 (6)	0.0219 (6)	0.0131 (6)	−0.0040 (5)	0.0078 (5)	0.0001 (5)
O7	0.0271 (7)	0.0190 (6)	0.0192 (7)	−0.0097 (6)	0.0094 (6)	−0.0030 (6)
O5	0.0182 (6)	0.0324 (8)	0.0196 (7)	0.0028 (6)	0.0096 (6)	0.0047 (6)
O6	0.0143 (5)	0.0354 (8)	0.0134 (6)	−0.0041 (6)	0.0061 (5)	0.0029 (6)
O1	0.0257 (7)	0.0206 (7)	0.0226 (8)	0.0085 (6)	0.0045 (6)	0.0000 (6)
O3	0.0344 (8)	0.0162 (6)	0.0148 (6)	−0.0090 (6)	0.0100 (6)	−0.0035 (5)
Ni1	0.01256 (13)	0.01290 (14)	0.01169 (14)	0.000	0.00419 (11)	0.000
O15	0.0206 (6)	0.0162 (6)	0.0149 (6)	0.0014 (5)	0.0069 (5)	0.0012 (5)
O14	0.0160 (5)	0.0176 (6)	0.0159 (6)	0.0017 (5)	0.0035 (5)	−0.0010 (5)
O13	0.0193 (6)	0.0220 (7)	0.0186 (7)	−0.0005 (5)	0.0080 (5)	−0.0051 (6)

Geometric parameters (Å, º) top

Na1—O1ⁱ	2.4205 (19)	P3—O7	1.4754 (16)
Na1—O5ⁱⁱ	2.384 (2)	P3—O6^iv	1.5948 (17)
Na1—O7ⁱⁱⁱ	2.3737 (19)	P2—O5	1.4735 (17)
Na1—O10ⁱⁱⁱ	2.556 (2)	P2—O4	1.4782 (17)
Na1—O11	2.546 (2)	P2—O3	1.6047 (16)
Na1—O12	2.323 (2)	O2—Liⁱⁱⁱ	1.927 (4)
Li—O2ⁱ	1.927 (4)	O7—Na1ⁱ	2.3737 (19)
Li—O8	1.930 (5)	O5—Na1^v	2.384 (2)
Li—O10	1.964 (5)	O6—P3^iv	1.5948 (17)
Li—O11	1.972 (5)	O1—Na1ⁱⁱⁱ	2.4205 (19)
O8—P3	1.4860 (17)	Ni1—O13	2.0469 (16)
O9—P3	1.5944 (16)	Ni1—O13^vi	2.0469 (16)
O9—P2	1.6088 (17)	Ni1—O15^vi	2.0572 (15)
P1—O1	1.4712 (16)	Ni1—O15	2.0572 (15)
P1—O2	1.4917 (17)	Ni1—O14^vi	2.0693 (18)
P1—O3	1.5908 (16)	Ni1—O14	2.0693 (18)
P1—O6	1.5929 (17)

O12—Na1—O7ⁱⁱⁱ	167.54 (8)	O7—P3—O9	110.00 (10)
O12—Na1—O5ⁱⁱ	93.23 (9)	O8—P3—O9	106.07 (9)
O7ⁱⁱⁱ—Na1—O5ⁱⁱ	91.05 (7)	O7—P3—O6^iv	108.36 (9)
O12—Na1—O1ⁱ	100.91 (8)	O8—P3—O6^iv	110.34 (9)
O7ⁱⁱⁱ—Na1—O1ⁱ	90.64 (7)	O9—P3—O6^iv	102.15 (9)
O5ⁱⁱ—Na1—O1ⁱ	91.76 (7)	O5—P2—O4	119.77 (10)
O12—Na1—O11	78.89 (9)	O5—P2—O3	110.02 (10)
O7ⁱⁱⁱ—Na1—O11	96.33 (7)	O4—P2—O3	106.67 (9)
O5ⁱⁱ—Na1—O11	171.92 (7)	O5—P2—O9	108.00 (10)
O1ⁱ—Na1—O11	91.45 (7)	O4—P2—O9	109.84 (9)
O12—Na1—O10ⁱⁱⁱ	78.55 (8)	O3—P2—O9	100.90 (9)
O7ⁱⁱⁱ—Na1—O10ⁱⁱⁱ	89.14 (7)	P1—O2—Liⁱⁱⁱ	118.66 (16)
O5ⁱⁱ—Na1—O10ⁱⁱⁱ	101.04 (7)	P3—O7—Na1ⁱ	123.98 (10)
O1ⁱ—Na1—O10ⁱⁱⁱ	167.20 (7)	P2—O5—Na1^v	124.59 (10)
O11—Na1—O10ⁱⁱⁱ	75.86 (7)	P1—O6—P3^iv	133.24 (10)
O2ⁱ—Li—O8	115.4 (2)	P1—O1—Na1ⁱⁱⁱ	121.77 (10)
O2ⁱ—Li—O10	107.4 (2)	P1—O3—P2	131.77 (10)
O8—Li—O10	110.8 (2)	O13—Ni1—O13^vi	89.73 (9)
O2ⁱ—Li—O11	113.7 (2)	O13—Ni1—O15^vi	177.22 (6)
O8—Li—O11	107.3 (2)	O13^vi—Ni1—O15^vi	91.32 (7)
O10—Li—O11	101.3 (2)	O13—Ni1—O15	91.32 (7)
P3—O8—Li	118.83 (15)	O13^vi—Ni1—O15	177.22 (6)
P3—O9—P2	129.04 (10)	O15^vi—Ni1—O15	87.76 (9)
Li—O10—Na1ⁱ	109.74 (15)	O13—Ni1—O14^vi	90.89 (7)
Li—O11—Na1	106.55 (15)	O13^vi—Ni1—O14^vi	87.49 (7)
O1—P1—O2	118.46 (10)	O15^vi—Ni1—O14^vi	91.73 (6)
O1—P1—O3	109.69 (10)	O15—Ni1—O14^vi	89.92 (6)
O2—P1—O3	110.66 (9)	O13—Ni1—O14	87.49 (7)
O1—P1—O6	109.65 (10)	O13^vi—Ni1—O14	90.89 (7)
O2—P1—O6	105.21 (9)	O15^vi—Ni1—O14	89.92 (6)
O3—P1—O6	101.78 (9)	O15—Ni1—O14	91.73 (6)
O7—P3—O8	118.66 (10)	O14^vi—Ni1—O14	177.71 (8)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x+1/2, −y+3/2, −z; (v) x−1/2, −y+3/2, z−1/2; (vi) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H110···O15ⁱⁱⁱ	0.85	1.96	2.795 (3)	165
O10—H210···O4^vii	0.87	2.03	2.851 (3)	159
O11—H111···O14ⁱⁱⁱ	0.82	2.01	2.811 (3)	164
O11—H211···O2	0.86	2.25	3.031 (3)	150
O12—H112···O12^vi	0.86	2.44	3.058 (4)	130
O12—H212···O3^iv	0.86	2.48	3.304 (3)	161
O12—H212···O4^iv	0.86	2.52	3.166 (3)	133
O15—H115···O4^viii	0.88	1.87	2.741 (3)	171
O15—H215···O5ⁱ	0.83	1.85	2.673 (3)	174
O14—H114···O8	0.85	1.94	2.758 (3)	163
O14—H214···O7^ix	0.86	1.78	2.643 (3)	174
O13—H113···O2ⁱ	0.83	1.97	2.789 (3)	167
O13—H213···O1ⁱⁱ	0.84	1.84	2.677 (3)	174

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

Experimental details

Crystal data
Chemical formula	Li₂Na₂NiP₆O₁₈·12H₂O
M_r	808.58
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	17.728 (9), 10.213 (2), 14.801 (7)
β (°)	112.04 (4)
V (Å³)	2484.0 (18)
Z	4
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.69
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Nonius MACH-3
Absorption correction	Part of the refinement model (ΔF) (Walker & Stuart, 1983)
T_min, T_max	0.769, 0.819
No. of measured, independent and observed [I > 2σ(I)] reflections	7168, 6076, 4296
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.102, 1.07
No. of reflections	6076
No. of parameters	186
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.60

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Na1—O1ⁱ	2.4205 (19)	Li—O8	1.930 (5)
Na1—O5ⁱⁱ	2.384 (2)	Li—O10	1.964 (5)
Na1—O7ⁱⁱⁱ	2.3737 (19)	Li—O11	1.972 (5)
Na1—O10ⁱⁱⁱ	2.556 (2)	Ni1—O13	2.0469 (16)
Na1—O11	2.546 (2)	Ni1—O15	2.0572 (15)
Na1—O12	2.323 (2)	Ni1—O14	2.0693 (18)
Li—O2ⁱ	1.927 (4)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H110···O15ⁱⁱⁱ	0.85	1.96	2.795 (3)	165
O10—H210···O4^iv	0.87	2.03	2.851 (3)	159
O11—H111···O14ⁱⁱⁱ	0.82	2.01	2.811 (3)	164
O11—H211···O2	0.86	2.25	3.031 (3)	150
O12—H112···O12^v	0.86	2.44	3.058 (4)	130
O12—H212···O3^vi	0.86	2.48	3.304 (3)	161
O12—H212···O4^vi	0.86	2.52	3.166 (3)	133
O15—H115···O4^vii	0.88	1.87	2.741 (3)	171
O15—H215···O5ⁱ	0.83	1.85	2.673 (3)	174
O14—H114···O8	0.85	1.94	2.758 (3)	163
O14—H214···O7^viii	0.86	1.78	2.643 (3)	174
O13—H113···O2ⁱ	0.83	1.97	2.789 (3)	167
O13—H213···O1ⁱⁱ	0.84	1.84	2.677 (3)	174

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

Acknowledgements

This work was supported by the Tunisian Ministry of H. E. Sc. R. and the Deanship of Scientific Research at King Saud University (research group project No. RGP-VPP-089).

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