Dilithium disodium nickel(II) cyclo-hexa-phosphate dodeca-hydrate, Li(2)Na(2)NiP(6)O(18)·12H(2)O.

The crystal structure of Li(2)Na(2)NiP(6)O(18)·12H(2)O is characterized by the presence of six-membered P(6)O(18) (6-) phosphate ring anions (inter-nal symmetry -1) having a chair conformation and three different cations, viz. Li(+), Na(+) and Ni(2+), 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 tetra-hedral environment (LiO(4)), and sodium and nickel have octa-hedral environments [NaO(6) and Ni(H(2)O)(6), respectively]. The P(6)O(18) rings are linked via corner sharing by NaO(6) octa-hedra and LiO(4) tetra-hedra to form a three-dimensional framework presenting tunnels running along [010] in which the six-coordinated Ni(2+) 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 = 808.58

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.102

S = 1.07

6076 reflections

186 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.80 e Å−3

Δρmin = −0.61 e Å−3

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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812029960/ff2073sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029960/ff2073Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Li2Na2NiP6O18·12H2O	F(000) = 1640
Mr = 808.58	Dx = 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

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

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(Fo2) + (0.0389P)2 + 4.028P] where P = (Fo2 + 2Fc2)/3
6076 reflections	(Δ/σ)max = 0.003
186 parameters	Δρmax = 0.80 e Å−3
2 restraints	Δρmin = −0.61 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

Na1—O1i	2.4205 (19)	P3—O7	1.4754 (16)
Na1—O5ii	2.384 (2)	P3—O6iv	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—Na1v	2.384 (2)
Li—O10	1.964 (5)	O6—P3iv	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—O13vi	2.0469 (16)
O9—P2	1.6088 (17)	Ni1—O15vi	2.0572 (15)
P1—O1	1.4712 (16)	Ni1—O15	2.0572 (15)
P1—O2	1.4917 (17)	Ni1—O14vi	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—O6iv	108.36 (9)
O12—Na1—O1i	100.91 (8)	O8—P3—O6iv	110.34 (9)
O7iii—Na1—O1i	90.64 (7)	O9—P3—O6iv	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—Na1v	124.59 (10)
O11—Na1—O10iii	75.86 (7)	P1—O6—P3iv	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—O13vi	89.73 (9)
O2i—Li—O11	113.7 (2)	O13—Ni1—O15vi	177.22 (6)
O8—Li—O11	107.3 (2)	O13vi—Ni1—O15vi	91.32 (7)
O10—Li—O11	101.3 (2)	O13—Ni1—O15	91.32 (7)
P3—O8—Li	118.83 (15)	O13vi—Ni1—O15	177.22 (6)
P3—O9—P2	129.04 (10)	O15vi—Ni1—O15	87.76 (9)
Li—O10—Na1i	109.74 (15)	O13—Ni1—O14vi	90.89 (7)
Li—O11—Na1	106.55 (15)	O13vi—Ni1—O14vi	87.49 (7)
O1—P1—O2	118.46 (10)	O15vi—Ni1—O14vi	91.73 (6)
O1—P1—O3	109.69 (10)	O15—Ni1—O14vi	89.92 (6)
O2—P1—O3	110.66 (9)	O13—Ni1—O14	87.49 (7)
O1—P1—O6	109.65 (10)	O13vi—Ni1—O14	90.89 (7)
O2—P1—O6	105.21 (9)	O15vi—Ni1—O14	89.92 (6)
O3—P1—O6	101.78 (9)	O15—Ni1—O14	91.73 (6)
O7—P3—O8	118.66 (10)	O14vi—Ni1—O14	177.71 (8)

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···O4vii	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···O12vi	0.86	2.44	3.058 (4)	130
O12—H212···O3iv	0.86	2.48	3.304 (3)	161
O12—H212···O4iv	0.86	2.52	3.166 (3)	133
O15—H115···O4viii	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···O7ix	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

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) ; (ii) ; (iii) .

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⋯O4iv	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⋯O12v	0.86	2.44	3.058 (4)	130
O12—H212⋯O3vi	0.86	2.48	3.304 (3)	161
O12—H212⋯O4vi	0.86	2.52	3.166 (3)	133
O15—H115⋯O4vii	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⋯O7viii	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) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .