A lanthanum(III) complex with a lacunary polyoxotungstate: Na2(NH4)7[La(W5O18)2]·16H2O

Almeida Paz, F.A.; Balula, M.S.S.; Cavaleiro, A.M.V.; Klinowski, J.; Nogueira, H.I.S.

doi:10.1107/S1600536805003557

inorganic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages i28-i31

https://doi.org/10.1107/S1600536805003557

A lanthanum(III) complex with a lacunary polyoxotungstate: Na₂(NH₄)₇[La(W₅O₁₈)₂]·16H₂O

Filipe A. Almeida Paz,^a ^* Maria Salete S. Balula,^a Ana M. V. Cavaleiro,^a Jacek Klinowski ^b and Helena I. S. Nogueira ^a

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, and ^bDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England
^*Correspondence e-mail: fpaz@dq.ua.pt

(Received 12 January 2005; accepted 1 February 2005; online 12 February 2005)

The crystal structure of a lanthanum polyoxotungstate complex, viz. heptaammonium disodium decatungstolanthanate hexadecahydrate, Na₂(NH₄)₇[La<(W₅O₁₈)₂]·16H₂O, has been determined by single-crystal X-ray diffraction at 100 (2) K in the space group C2/c. The [La(W₅O₁₈)₂]⁹⁻ polyoxoanion has the central La³⁺ cation located on a twofold rotation axis. The close packing of the polyoxoanion-supported lanthanum(III) complexes with Na⁺ and NH₄⁺ cations leads to the formation of several intersecting undulating channels, where the water molecules of crystallization are located and involved in strong hydrogen bonds.

Comment

Polyoxometalates (POMs) are a unique type of compound showing remarkable structural diversity and potentially interesting applications in catalysis, non-linear optical and magnetic materials, liquid crystals and biomedical materials (Pope & Müller, 1994 , 2001 ; Müller et al., 1998 , and references therein; Pope, 1983 ). In the course of our research on the synthesis and structural characterization of novel functional materials containing POMs (Almeida Paz et al., 2004 ; Sousa, Paz, Cavaleiro et al., 2004 ; Sousa, Paz, Soares-Santos et al., 2004 ), we came across the title compound, (I).

A search in the literature and in the Inorganic Crystal Structure Database (Belsky et al., 2002 ) shows that the [La(W₅O₁₈)₂]⁹⁻ polyoxoanion shares striking similarities with all complexes of the [Ln(W₅O₁₈)₂]ⁿ⁻ type, where Ln = Ce⁴⁺ (Peacock & Weakley, 1971 ; Iball et al., 1974 ), Ce³⁺ (Xue et al., 2002 ), Pr³⁺, Nd³⁺ (Ozeki & Yamase, 1994a ), Sm³⁺ (Ozeki & Yamase, 1993 , 1994a,b ), Eu³⁺ (Sugeta & Yamase, 1993 ; Yamase et al., 1993 ), Gd³⁺ (Yamase & Ozeki, 1993 ; Ozeki & Yamase, 1994a; Yamase et al., 1994 ), Tb³⁺ (Ozeki & Yamase, 1994a; Ozeki et al., 1992 ), Dy³⁺ (Ozeki & Yamase, 1994a) and also with the actinide cation Th⁴⁺ (Griffith et al., 2000 ). Surprisingly, the structure containing La³⁺ cations has not been reported to date. We describe here the synthesis and crystal structure of Na₂(NH₄)₇[La(W₅O₁₈)₂]·16H₂O, determined in the space group C2/c at the low temperature of 100 (2) K; this is also the first report of a complex of the [Ln(W₅O₁₈)₂]ⁿ⁻ type crystallizing with NH₄⁺ cations.

The [La(W₅O₁₈)₂]⁹⁻ polyoxoanion has crystallographic C₂ symmetry about an axis passing through the central La³⁺ cation and perpendicular to the vector containing the W1, La1 and W1ⁱ centres [Fig. 1; symmetry code: (i) 2 − x, y, $[3\over 2]$ − z]. The two [W₅O₁₈]⁶⁻ anionic fragments are linked together via a central La³⁺ cation positioned in the lacuna of each anion (Fig. 1). This centre exhibits typical square antiprismatic coordination geometry, with La—O distances in the range 2.497 (6)–2.562 (6) Å (Table 1 and Fig. 1). The degree of staggering between the upper and lower square faces of the antiprism is only ca 0.6° from ideal.

For the [W₅O₁₈]⁶⁻ moieties, the five crystallographically unique W centres exhibit distorted {WO₆} octahedral environments, in which the central W atom is displaced in the direction of the axial oxo ligand (average distance of displacement = 0.402 Å): W—O distances and O—W—O angles are in the ranges 1.724 (6)–2.324 (6) Å and 74.5 (2)–179.0 (3)° [74.5 (2)–104.3 (3)° and 153.2 (2)–179.0 (3)° for cis and trans], respectively. The W—O distances can be divided into several groups according to the different types of O atoms (Table 3): O_I represent long bonds of the W—O1—W type (where O1 is the core O atom; see Fig. 1) found in the range 2.304 (6)–2.324 (6) Å; O_II represent those connected to the W centres which are involved in edge-sharing of adjacent octahedra [1.890 (6)–2.031 (6) Å]; O_III represent the lanthanum-bound O atoms (O15, O16, O17 and O18), and O_IV the terminal O atoms (O2, O8, O10, O12 and O14; see Fig. 1 and Table 3). As found in related compounds, pairs of short and long W—O_II bonds are observed (Table 3). This results from small displacements of the W centres, and also from the structural evidence that W1 is the statistically farthest W centre from any other: the W⋯W distances for the W2⋯W3⋯W4⋯W5 central square of [W₅O₁₈]⁶⁻ are in the range 3.264 (6)–3.291 (6) Å, while W1⋯W2—W5 distances are in the range 3.331 (6)–3.342 (6) Å. It is interesting to note that the O1 core atom lies only 0.099 (6) Å out of the plane of the equatorially bonded W2—W5 centres and in the direction of W1; the non-bonded La1⋯O1 distance is 3.271 (6) Å.

The anion charge is balanced by the presence of one Na⁺ and three and a half crystallographically unique NH₄⁺ cations, Na₂(NH₄)₇[La(W₅O₁₈)₂]. Interestingly, the Na⁺ cations in the crystal structure form {Na₂(H₂O)₁₀}²⁺ moieties, exhibiting a highly distorted octahedral coordination environment in which the average Na⋯O_water contact distance is 2.372 Å (Table 2 and Fig. 2) and the Na1⋯Na1ⁱⁱ distance is 3.411 (7) Å [symmetry code: (ii) $[{1 \over 2}]$ − x, $[{1 \over 2}]$ − y, 1 − z].

The polyoxoanion-supported lanthanum(III) complex anions, [La(W₅O₁₈)₂]⁹⁻, pack closely in the ab plane in a typical brick-wall-like fashion, leading to several types of intersecting channels which accommodate the cations (Na⁺ and NH₄⁺) and the water molecules of crystallization (Figs. 3 and 4). These are, in turn, involved in an extensive hydrogen-bonded network composed of strong heteronuclear N⁺—H⋯O and homonuclear O—H⋯O interactions (not shown).

Figure 1
Mixed ellipsoid and polyhedral representation of the polyoxoanion-supported lanthanum(III) complex anion, [La(W₅O₁₈)₂]⁹⁻, showing the labelling scheme for selected atoms and emphasizing the square antiprismatic coordination environment for the central La³⁺ cation. Atoms belonging to the asymmetric unit are represented with ellipsoids drawn at the 50% probability level. [Symmetry code: (i) 2 − x, y, $[3\over2]$ − z.]

Figure 2
Schematic representation of the cationic {Na₂(H₂O)₁₀}²⁺ moieties. The Na1⋯Na1ⁱ distance is 3.411 (7) Å [symmetry code: (i) $[{1 \over 2}]$ − x, $[{1 \over 2}]$ − y, 1 − z].

Figure 3
Polyhedral representation of the crystal packing of Na₂(NH₄)₇[La(W₅O₁₈)₂]·16H₂O, viewed along the a direction.

Figure 4
Polyhedral representation of the crystal packing of Na₂(NH₄)₇[La(W₅O₁₈)₂]·16H₂O, viewed towards the ( $[\overline 8]$ ,11,1) plane.

Experimental

All chemicals were purchased from Aldrich and used without further purification. Na₂WO₄·2H₂O (9.90 g, 30 mmol) and H₃BO₃ (0.15 g, 2.43 mmol) were dissolved in hot distilled water (ca 21 ml, 363–373 K), and the final pH was adjusted to 7.1 using a 6 M aqueous solution in HCl. After 10 min, a solution of La(NO₃)₃ (3.24 mmol) in 1 M CH₃COOH (ca 5.4 ml) was added dropwise, and the resulting mixture was stirred thoroughly at 363 K for 30 min. The temperature was then slowly dropped to 343 K, after which an aqueous solution of NH₄Cl (12 g, 224 mmol) was added dropwise. The resulting solution was allowed to stand at ambient temperature for 24 h and then filtered. The collected solid was recrystallized from warm distilled water, giving good quality white crystals suitable for X-ray diffraction. Selected FT–IR data (cm⁻¹): ν(N⁺—H, from NH₄⁺) = 1401 (s), ν_as(W—O_IV, terminal W—O stretch) = 931 (s), ν_as(W—O_II—W, edge-shared W—O—W stretching mode) = 840 (s) and 789 (s).

Crystal data

Na₂(NH₄)₇[La(W₅O₁₈)₂]·16H₂O
M_r = 3013.94
Monoclinic, C2/c
a = 11.784 (2) Å
b = 14.838 (3) Å
c = 29.143 (6) Å
β = 93.26 (3)°
V = 5087.4 (18) Å³
Z = 4
D_x = 3.935 Mg m⁻³
Mo Kα radiation
Cell parameters from 1014 reflections
θ = 2.7–28.7°
μ = 23.47 mm⁻¹
T = 100 (2) K
Plate, white
0.35 × 0.21 × 0.06 mm

Data collection

Bruker SMART CCD1000 diffractometer
Thin-slice ω and φ scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.045, T_max = 0.333
21 307 measured reflections
5183 independent reflections
4577 reflections with I > 2σ(I)
R_int = 0.069
θ_max = 26.4°
h = −14 → 14
k = −18 → 18
l = −36 → 36

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.081
S = 1.08
5183 reflections
326 parameters
H-atom parameters not defined
w = 1/[σ²(F_o²) + (0.0169P)² + 65.9468P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 1.66 e Å⁻³
Δρ_min = −2.16 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

La1—O15	2.497 (6)
La1—O18	2.511 (6)
La1—O16	2.530 (6)
La1—O17	2.562 (6)

O15—La1—O15ⁱ	151.4 (3)
O15—La1—O18	72.7 (2)
O15—La1—O18ⁱ	133.7 (2)
O18—La1—O18ⁱ	74.3 (3)
O15—La1—O16ⁱ	84.66 (19)
O18—La1—O16ⁱ	151.71 (19)
O15—La1—O16	72.61 (19)
O15ⁱ—La1—O16	84.7 (2)
O18—La1—O16	112.58 (19)
O16ⁱ—La1—O16	75.0 (3)
O15—La1—O17	112.8 (2)
O15ⁱ—La1—O17	74.8 (2)
O18—La1—O17	70.99 (19)
O18ⁱ—La1—O17	85.41 (19)
O16ⁱ—La1—O17	135.25 (19)
O16—La1—O17	72.16 (19)
O15—La1—O17ⁱ	74.8 (2)
O17—La1—O17ⁱ	150.5 (3)
Symmetry code: (i) $[2-x,y,{\script{3\over 2}}-z]$ .

Table 2
Contact distances (Å)

Na1⋯O1W	2.346 (8)
Na1⋯O2W	2.402 (7)
Na1⋯O3W	2.321 (7)
Na1⋯O4W	2.328 (7)
Na1⋯O5W	2.379 (8)
Na1ⁱⁱ⋯O5W	2.456 (7)
Symmetry code: (ii) $[{\script{1\over 2}}-x,{\script{1\over 2}}-y,1-z]$ .

Table 3
W—O bond-distance categories (Å) for the [W₅O₁₈]⁶⁻ anionic fragment present in (I)

Category	Range	Average	Range
W—O_I	2.304 (6)–2.324 (6)	2.314	0.020
W—O_II (short)	1.890 (6)–1.963 (6)	1.927	0.073
W—O_II (long)	2.022 (6)–2.031 (6)	2.027	0.009
W—O_III	1.776 (6)–1.790 (6)	1.783	0.014
W—O_IV	1.726 (6)–1.734 (6)	1.730	0.008

The distinction between water molecules and NH₄⁺ cations proved to be very difficult. In order to balance the anion charge, three and a half NH₄⁺ cations have been selected, taking into consideration FT–IR data and geometrical aspects, such as charge proximity and the number of neighbours with which hydrogen bonding might occur. Since the number of possible hydrogen bonds in which the water molecules and NH₄⁺ cations could be involved is quite large, no attempt was made either to find or to place geometrically the H atoms in these groups. The highest peak in the final difference Fourier map was located 1.25 Å from O4 and the deepest hole 0.94 Å from W1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve and refine structure: SHELXTL (Bruker, 2001); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805003557/kp6036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805003557/kp6036Isup2.hkl

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SMART; data reduction: SAINT (Bruker 2001); program(s) used to solve structure: SHELXTL (Bruker 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL.

Heptaammonium disodium decatungstolanthanate hexadecahydrate top

Crystal data top

Na₂(NH₄)₇[La(W₅O₁₈)₂]_.16H₂O	F(000) = 5376
M_r = 3013.94	D_x = 3.935 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1014 reflections
a = 11.784 (2) Å	θ = 2.7–28.7°
b = 14.838 (3) Å	µ = 23.47 mm⁻¹
c = 29.143 (6) Å	T = 100 K
β = 93.26 (3)°	Plate, white
V = 5087.4 (18) Å³	0.35 × 0.21 × 0.06 mm
Z = 4

Data collection top

Bruker SMART CCD-1000 diffractometer	5183 independent reflections
Radiation source: fine-focus sealed tube	4577 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
Thin–slice ω and φ scans	θ_max = 26.4°, θ_min = 3.6°
Absorption correction: numerical (SADABS; Sheldrick, 1997)	h = −14→14
T_min = 0.045, T_max = 0.333	k = −18→18
21307 measured reflections	l = −36→36

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)] = 0.031	H-atom parameters not defined
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0169P)² + 65.9468P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
5183 reflections	Δρ_max = 1.66 e Å⁻³
326 parameters	Δρ_min = −2.16 e Å⁻³
0 restraints

Special details top

Experimental. (See detailed section in the paper)

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
La1	1.0000	0.09129 (4)	0.7500	0.01326 (15)
W1	0.83850 (3)	0.08924 (2)	0.566443 (12)	0.01359 (9)
W2	0.73229 (3)	0.13421 (2)	0.667717 (12)	0.01323 (9)
W3	0.96366 (3)	0.23890 (2)	0.638543 (12)	0.01351 (9)
W4	1.08600 (3)	0.04483 (2)	0.622843 (12)	0.01412 (9)
W5	0.85720 (3)	−0.05948 (2)	0.652336 (12)	0.01338 (9)
O1	0.9070 (5)	0.0899 (4)	0.6421 (2)	0.0151 (13)
O2	0.7856 (5)	0.0904 (4)	0.5097 (2)	0.0203 (14)
O3	0.7072 (5)	0.1246 (4)	0.5987 (2)	0.0140 (12)
O4	0.8925 (5)	0.2099 (4)	0.57513 (19)	0.0147 (12)
O5	0.8069 (5)	−0.0304 (4)	0.5862 (2)	0.0179 (13)
O6	0.9913 (5)	0.0531 (4)	0.5620 (2)	0.0166 (13)
O7	0.7168 (5)	0.0047 (4)	0.6651 (2)	0.0154 (12)
O8	0.5963 (5)	0.1687 (4)	0.6779 (2)	0.0178 (13)
O9	0.8039 (5)	0.2481 (4)	0.6531 (2)	0.0169 (13)
O10	0.9999 (5)	0.3494 (4)	0.6269 (2)	0.0211 (14)
O11	1.0941 (5)	0.1747 (4)	0.6174 (2)	0.0180 (13)
O12	1.2100 (5)	0.0079 (4)	0.5996 (2)	0.0251 (15)
O13	1.0057 (5)	−0.0692 (4)	0.6278 (2)	0.0127 (12)
O14	0.8107 (6)	−0.1701 (4)	0.6510 (2)	0.0207 (14)
O15	0.8013 (5)	0.1329 (4)	0.7240 (2)	0.0161 (13)
O16	1.0112 (5)	0.2266 (4)	0.6976 (2)	0.0155 (12)
O17	1.1215 (5)	0.0473 (4)	0.6834 (2)	0.0159 (13)
O18	0.9127 (5)	−0.0436 (4)	0.7097 (2)	0.0155 (12)
Na1	0.1204 (3)	0.2857 (2)	0.47812 (12)	0.0186 (7)
N1	0.0000	0.7900 (7)	0.7500	0.032 (3)
N2	0.1042 (7)	0.3948 (5)	0.7263 (3)	0.0261 (19)
N3	0.8511 (6)	0.1850 (5)	0.4290 (2)	0.0167 (15)
N4	0.9494 (7)	0.5085 (5)	0.4338 (3)	0.0235 (17)
O1W	0.0583 (6)	0.2921 (5)	0.4003 (2)	0.0260 (15)
O2W	−0.0695 (6)	0.3137 (4)	0.5005 (2)	0.0222 (14)
O3W	0.1434 (6)	0.4411 (4)	0.4788 (3)	0.0309 (17)
O4W	0.0678 (6)	0.1349 (4)	0.4829 (2)	0.0255 (15)
O5W	0.2105 (5)	0.2822 (4)	0.5533 (2)	0.0220 (14)
O6W	0.3948 (7)	0.0042 (6)	0.6641 (3)	0.053 (2)
O7W	0.7070 (7)	0.3741 (6)	0.7112 (3)	0.047 (2)
O8W	0.6629 (7)	0.1685 (6)	0.7958 (3)	0.047 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0161 (3)	0.0145 (3)	0.0090 (3)	0.000	−0.0008 (3)	0.000
W1	0.01746 (18)	0.01594 (17)	0.00727 (18)	0.00045 (13)	−0.00023 (14)	0.00015 (12)
W2	0.01532 (17)	0.01612 (18)	0.00823 (18)	0.00101 (13)	0.00057 (13)	−0.00002 (12)
W3	0.01793 (18)	0.01355 (17)	0.00901 (18)	−0.00041 (13)	0.00038 (14)	0.00072 (12)
W4	0.01569 (18)	0.01644 (18)	0.01024 (19)	0.00115 (13)	0.00088 (14)	−0.00047 (12)
W5	0.01770 (18)	0.01348 (17)	0.00886 (18)	−0.00063 (12)	−0.00014 (14)	0.00007 (12)
O1	0.021 (3)	0.013 (3)	0.011 (3)	−0.003 (2)	0.004 (3)	0.002 (2)
O2	0.026 (3)	0.023 (3)	0.012 (3)	−0.001 (3)	0.001 (3)	0.003 (2)
O3	0.012 (3)	0.017 (3)	0.012 (3)	0.001 (2)	0.002 (2)	0.000 (2)
O4	0.022 (3)	0.019 (3)	0.003 (3)	0.000 (2)	−0.001 (2)	0.004 (2)
O5	0.022 (3)	0.020 (3)	0.012 (3)	0.000 (3)	0.000 (3)	0.001 (2)
O6	0.020 (3)	0.020 (3)	0.009 (3)	0.003 (2)	0.001 (3)	0.001 (2)
O7	0.019 (3)	0.020 (3)	0.007 (3)	0.004 (2)	0.000 (2)	0.003 (2)
O8	0.018 (3)	0.025 (3)	0.010 (3)	0.004 (3)	−0.005 (2)	0.000 (2)
O9	0.017 (3)	0.016 (3)	0.018 (4)	0.005 (2)	0.003 (3)	0.001 (2)
O10	0.022 (3)	0.015 (3)	0.026 (4)	−0.005 (3)	0.000 (3)	0.004 (3)
O11	0.016 (3)	0.017 (3)	0.022 (4)	−0.002 (2)	0.003 (3)	0.002 (2)
O12	0.022 (3)	0.026 (3)	0.027 (4)	0.002 (3)	0.006 (3)	−0.006 (3)
O13	0.016 (3)	0.013 (3)	0.010 (3)	0.000 (2)	−0.001 (2)	0.000 (2)
O14	0.028 (3)	0.018 (3)	0.015 (3)	−0.003 (3)	0.000 (3)	0.002 (2)
O15	0.015 (3)	0.019 (3)	0.014 (3)	0.000 (2)	0.001 (2)	−0.002 (2)
O16	0.021 (3)	0.022 (3)	0.003 (3)	−0.002 (2)	0.001 (2)	0.001 (2)
O17	0.018 (3)	0.017 (3)	0.014 (3)	0.002 (2)	0.003 (3)	0.001 (2)
O18	0.022 (3)	0.015 (3)	0.009 (3)	−0.003 (2)	0.001 (3)	−0.001 (2)
Na1	0.0227 (18)	0.0187 (17)	0.0145 (19)	0.0011 (14)	0.0011 (15)	−0.0017 (13)
N1	0.075 (10)	0.004 (5)	0.015 (6)	0.000	−0.004 (6)	0.000
N2	0.030 (4)	0.022 (4)	0.028 (5)	−0.011 (3)	0.013 (4)	−0.004 (3)
N3	0.021 (4)	0.022 (4)	0.008 (4)	0.002 (3)	0.002 (3)	0.001 (3)
N4	0.026 (4)	0.024 (4)	0.020 (5)	−0.003 (3)	−0.002 (3)	0.008 (3)
O1W	0.028 (4)	0.033 (4)	0.017 (4)	0.004 (3)	−0.003 (3)	0.003 (3)
O2W	0.028 (3)	0.027 (3)	0.013 (3)	0.007 (3)	0.005 (3)	0.006 (3)
O3W	0.034 (4)	0.020 (3)	0.037 (5)	−0.003 (3)	−0.007 (3)	0.004 (3)
O4W	0.037 (4)	0.020 (3)	0.020 (4)	−0.007 (3)	0.005 (3)	−0.001 (3)
O5W	0.024 (3)	0.030 (4)	0.013 (3)	0.003 (3)	0.004 (3)	0.003 (3)
O6W	0.046 (5)	0.059 (6)	0.052 (6)	0.017 (4)	−0.013 (4)	−0.022 (5)
O7W	0.053 (5)	0.046 (5)	0.041 (6)	0.004 (4)	0.009 (4)	−0.007 (4)
O8W	0.050 (5)	0.042 (5)	0.050 (6)	−0.005 (4)	0.014 (4)	−0.009 (4)

Geometric parameters (Å, º) top

La1—O15	2.497 (6)	W3—O10	1.732 (6)
La1—O15ⁱ	2.497 (6)	W3—O16	1.789 (6)
La1—O18	2.511 (6)	W3—O11	1.939 (6)
La1—O18ⁱ	2.511 (6)	W3—O9	1.958 (6)
La1—O16ⁱ	2.530 (6)	W3—O4	2.031 (6)
La1—O16	2.530 (6)	W3—O1	2.314 (5)
La1—O17	2.562 (6)	W4—O12	1.734 (6)
La1—O17ⁱ	2.562 (6)	W4—O17	1.790 (6)
W1—O2	1.734 (7)	W4—O11	1.936 (6)
W1—O6	1.890 (6)	W4—O13	1.948 (6)
W1—O5	1.910 (6)	W4—O6	2.043 (6)
W1—O4	1.913 (6)	W4—O1	2.312 (6)
W1—O3	1.928 (6)	W5—O14	1.731 (6)
W1—O1	2.304 (6)	W5—O18	1.776 (6)
W2—O8	1.724 (6)	W5—O13	1.933 (6)
W2—O15	1.789 (6)	W5—O7	1.963 (6)
W2—O7	1.931 (6)	W5—O5	2.031 (6)
W2—O9	1.947 (6)	W5—O1	2.316 (5)
W2—O3	2.022 (6)	Na1—Na1ⁱⁱ	3.411 (7)
W2—O1	2.324 (6)

Na1···O1W	2.346 (8)	Na1···O4W	2.328 (7)
Na1···O2W	2.402 (7)	Na1···O5W	2.379 (8)
Na1···O3W	2.321 (7)	Na1ⁱⁱ···O5W	2.456 (7)

O15—La1—O15ⁱ	151.4 (3)	O12—W4—O11	103.6 (3)
O15—La1—O18	72.7 (2)	O17—W4—O11	92.8 (3)
O15—La1—O18ⁱ	133.7 (2)	O12—W4—O13	100.3 (3)
O15ⁱ—La1—O18ⁱ	72.71 (19)	O17—W4—O13	91.9 (3)
O18—La1—O18ⁱ	74.3 (3)	O11—W4—O13	153.8 (2)
O15—La1—O16ⁱ	84.66 (19)	O12—W4—O6	96.4 (3)
O15ⁱ—La1—O16ⁱ	72.61 (19)	O17—W4—O6	159.9 (3)
O18—La1—O16ⁱ	151.71 (19)	O11—W4—O6	84.1 (3)
O18ⁱ—La1—O16ⁱ	112.58 (19)	O13—W4—O6	82.7 (2)
O15—La1—O16	72.61 (19)	O12—W4—O1	170.7 (3)
O15ⁱ—La1—O16	84.7 (2)	O17—W4—O1	85.4 (2)
O18—La1—O16	112.58 (19)	O11—W4—O1	77.4 (2)
O18ⁱ—La1—O16	151.71 (19)	O13—W4—O1	77.2 (2)
O16ⁱ—La1—O16	75.0 (3)	O6—W4—O1	74.5 (2)
O15—La1—O17	112.8 (2)	O14—W5—O18	104.3 (3)
O15ⁱ—La1—O17	74.8 (2)	O14—W5—O13	102.3 (3)
O18—La1—O17	70.99 (19)	O18—W5—O13	93.8 (3)
O18ⁱ—La1—O17	85.41 (19)	O14—W5—O7	101.3 (3)
O16ⁱ—La1—O17	135.25 (19)	O18—W5—O7	91.5 (3)
O16—La1—O17	72.16 (19)	O13—W5—O7	153.7 (2)
O15—La1—O17ⁱ	74.8 (2)	O14—W5—O5	96.0 (3)
O15ⁱ—La1—O17ⁱ	112.8 (2)	O18—W5—O5	159.6 (3)
O18—La1—O17ⁱ	85.41 (19)	O13—W5—O5	83.5 (2)
O18ⁱ—La1—O17ⁱ	70.99 (19)	O7—W5—O5	82.7 (2)
O16ⁱ—La1—O17ⁱ	72.16 (19)	O14—W5—O1	170.8 (3)
O16—La1—O17ⁱ	135.25 (19)	O18—W5—O1	84.9 (2)
O17—La1—O17ⁱ	150.5 (3)	O13—W5—O1	77.4 (2)
O2—W1—O6	103.3 (3)	O7—W5—O1	77.4 (2)
O2—W1—O5	103.3 (3)	O5—W5—O1	74.8 (2)
O6—W1—O5	87.7 (3)	W1—O1—W4	92.4 (2)
O2—W1—O4	102.5 (3)	W1—O1—W3	92.7 (2)
O6—W1—O4	87.9 (3)	W4—O1—W3	89.7 (2)
O5—W1—O4	154.1 (3)	W1—O1—W5	92.4 (2)
O2—W1—O3	102.0 (3)	W4—O1—W5	89.8 (2)
O6—W1—O3	154.7 (3)	W3—O1—W5	174.9 (3)
O5—W1—O3	86.0 (3)	W1—O1—W2	92.3 (2)
O4—W1—O3	87.2 (2)	W4—O1—W2	175.3 (3)
O2—W1—O1	179.0 (3)	W3—O1—W2	90.4 (2)
O6—W1—O1	77.5 (2)	W5—O1—W2	89.66 (19)
O5—W1—O1	77.2 (2)	W1—O3—W2	115.3 (3)
O4—W1—O1	76.9 (2)	W1—O4—W3	115.8 (3)
O3—W1—O1	77.3 (2)	W1—O5—W5	115.6 (3)
O8—W2—O15	102.9 (3)	W1—O6—W4	115.7 (3)
O8—W2—O7	102.4 (3)	W2—O7—W5	114.3 (3)
O15—W2—O7	93.6 (3)	W2—O9—W3	114.9 (3)
O8—W2—O9	101.5 (3)	W4—O11—W3	114.8 (3)
O15—W2—O9	91.7 (3)	W5—O13—W4	114.6 (3)
O7—W2—O9	153.7 (2)	W2—O15—La1	130.6 (3)
O8—W2—O3	96.2 (3)	W3—O16—La1	129.6 (3)
O15—W2—O3	160.9 (2)	W4—O17—La1	130.0 (3)
O7—W2—O3	83.3 (2)	W5—O18—La1	131.7 (3)
O9—W2—O3	83.3 (3)	O3W—Na1—O4W	170.1 (3)
O8—W2—O1	171.2 (3)	O3W—Na1—O1W	89.9 (3)
O15—W2—O1	85.8 (2)	O4W—Na1—O1W	91.6 (3)
O7—W2—O1	77.8 (2)	O3W—Na1—O5W	88.2 (3)
O9—W2—O1	76.9 (2)	O4W—Na1—O5W	91.7 (3)
O3—W2—O1	75.1 (2)	O1W—Na1—O5W	171.7 (3)
O10—W3—O16	102.5 (3)	O3W—Na1—O2W	86.3 (3)
O10—W3—O11	101.2 (3)	O4W—Na1—O2W	83.9 (3)
O16—W3—O11	92.5 (3)	O1W—Na1—O2W	90.6 (3)
O10—W3—O9	103.1 (3)	O5W—Na1—O2W	97.3 (3)
O16—W3—O9	93.0 (3)	O3W—Na1—O5Wⁱⁱ	108.3 (3)
O11—W3—O9	153.2 (2)	O4W—Na1—O5Wⁱⁱ	81.5 (3)
O10—W3—O4	96.7 (3)	O1W—Na1—O5Wⁱⁱ	82.6 (2)
O16—W3—O4	160.8 (3)	O5W—Na1—O5Wⁱⁱ	90.3 (2)
O11—W3—O4	84.3 (3)	O2W—Na1—O5Wⁱⁱ	163.8 (3)
O9—W3—O4	81.9 (3)	O3W—Na1—Na1ⁱⁱ	101.7 (2)
O10—W3—O1	171.2 (3)	O4W—Na1—Na1ⁱⁱ	85.1 (2)
O16—W3—O1	86.3 (2)	O1W—Na1—Na1ⁱⁱ	126.7 (2)
O11—W3—O1	77.3 (2)	O5W—Na1—Na1ⁱⁱ	46.06 (17)
O9—W3—O1	76.9 (2)	O2W—Na1—Na1ⁱⁱ	141.3 (2)
O4—W3—O1	74.5 (2)	O5Wⁱⁱ—Na1—Na1ⁱⁱ	44.23 (17)
O12—W4—O17	103.6 (3)	Na1—O5W—Na1ⁱⁱ	89.7 (2)

O6—W1—O1—W4	0.1 (2)	O4—W1—O6—W4	76.9 (3)
O5—W1—O1—W4	90.6 (2)	O3—W1—O6—W4	−1.9 (8)
O4—W1—O1—W4	−90.6 (2)	O1—W1—O6—W4	−0.1 (3)
O3—W1—O1—W4	179.3 (2)	O12—W4—O6—W1	178.5 (3)
O6—W1—O1—W3	90.0 (2)	O17—W4—O6—W1	3.7 (9)
O5—W1—O1—W3	−179.6 (3)	O11—W4—O6—W1	−78.4 (3)
O4—W1—O1—W3	−0.8 (2)	O13—W4—O6—W1	78.9 (3)
O3—W1—O1—W3	−90.8 (2)	O1—W4—O6—W1	0.1 (3)
O6—W1—O1—W5	−89.7 (2)	O8—W2—O7—W5	178.7 (3)
O5—W1—O1—W5	0.7 (2)	O15—W2—O7—W5	−77.2 (3)
O4—W1—O1—W5	179.5 (3)	O9—W2—O7—W5	24.0 (7)
O3—W1—O1—W5	89.5 (2)	O3—W2—O7—W5	83.8 (3)
O6—W1—O1—W2	−179.5 (2)	O1—W2—O7—W5	7.7 (3)
O5—W1—O1—W2	−89.0 (2)	O14—W5—O7—W2	−178.4 (3)
O4—W1—O1—W2	89.8 (2)	O18—W5—O7—W2	76.7 (3)
O3—W1—O1—W2	−0.3 (2)	O13—W5—O7—W2	−25.0 (7)
O17—W4—O1—W1	−178.9 (2)	O5—W5—O7—W2	−83.7 (3)
O11—W4—O1—W1	87.1 (2)	O1—W5—O7—W2	−7.8 (3)
O13—W4—O1—W1	−85.9 (2)	O8—W2—O9—W3	−179.7 (3)
O6—W4—O1—W1	−0.1 (2)	O15—W2—O9—W3	76.8 (4)
O17—W4—O1—W3	88.4 (2)	O7—W2—O9—W3	−24.9 (8)
O11—W4—O1—W3	−5.6 (2)	O3—W2—O9—W3	−84.7 (3)
O13—W4—O1—W3	−178.7 (3)	O1—W2—O9—W3	−8.5 (3)
O6—W4—O1—W3	−92.8 (2)	O10—W3—O9—W2	179.5 (3)
O17—W4—O1—W5	−86.5 (2)	O16—W3—O9—W2	−76.9 (4)
O11—W4—O1—W5	179.5 (3)	O11—W3—O9—W2	24.6 (8)
O13—W4—O1—W5	6.5 (2)	O4—W3—O9—W2	84.4 (3)
O6—W4—O1—W5	92.3 (2)	O1—W3—O9—W2	8.6 (3)
O16—W3—O1—W1	179.8 (2)	O12—W4—O11—W3	177.9 (3)
O11—W3—O1—W1	−86.8 (2)	O17—W4—O11—W3	−77.3 (4)
O9—W3—O1—W1	85.9 (2)	O13—W4—O11—W3	22.8 (8)
O4—W3—O1—W1	0.7 (2)	O6—W4—O11—W3	82.7 (3)
O16—W3—O1—W4	−87.9 (2)	O1—W4—O11—W3	7.3 (3)
O11—W3—O1—W4	5.6 (2)	O10—W3—O11—W4	−178.4 (3)
O9—W3—O1—W4	178.2 (3)	O16—W3—O11—W4	78.3 (4)
O4—W3—O1—W4	93.1 (2)	O9—W3—O11—W4	−23.4 (8)
O16—W3—O1—W2	87.4 (2)	O4—W3—O11—W4	−82.7 (3)
O11—W3—O1—W2	−179.1 (3)	O1—W3—O11—W4	−7.3 (3)
O9—W3—O1—W2	−6.5 (2)	O14—W5—O13—W4	179.0 (3)
O4—W3—O1—W2	−91.6 (2)	O18—W5—O13—W4	−75.5 (3)
O18—W5—O1—W1	−179.2 (3)	O7—W5—O13—W4	25.7 (7)
O13—W5—O1—W1	85.9 (2)	O5—W5—O13—W4	84.3 (3)
O7—W5—O1—W1	−86.4 (2)	O1—W5—O13—W4	8.5 (3)
O5—W5—O1—W1	−0.7 (2)	O12—W4—O13—W5	−179.4 (3)
O18—W5—O1—W4	88.5 (2)	O17—W4—O13—W5	76.4 (3)
O13—W5—O1—W4	−6.5 (2)	O11—W4—O13—W5	−23.9 (8)
O7—W5—O1—W4	−178.8 (3)	O6—W4—O13—W5	−84.2 (3)
O5—W5—O1—W4	−93.0 (2)	O1—W4—O13—W5	−8.5 (3)
O18—W5—O1—W2	−86.9 (2)	O8—W2—O15—La1	179.2 (4)
O13—W5—O1—W2	178.2 (3)	O7—W2—O15—La1	75.5 (4)
O7—W5—O1—W2	5.9 (2)	O9—W2—O15—La1	−78.7 (4)
O5—W5—O1—W2	91.6 (2)	O3—W2—O15—La1	−4.2 (10)
O15—W2—O1—W1	−179.0 (2)	O1—W2—O15—La1	−2.0 (3)
O7—W2—O1—W1	86.4 (2)	O15ⁱ—La1—O15—W2	101.7 (4)
O9—W2—O1—W1	−86.2 (2)	O18—La1—O15—W2	−58.4 (4)
O3—W2—O1—W1	0.3 (2)	O18ⁱ—La1—O15—W2	−104.9 (4)
O15—W2—O1—W3	−86.2 (2)	O16ⁱ—La1—O15—W2	138.8 (4)
O7—W2—O1—W3	179.2 (3)	O16—La1—O15—W2	62.8 (4)
O9—W2—O1—W3	6.5 (2)	O17—La1—O15—W2	1.5 (4)
O3—W2—O1—W3	93.0 (2)	O17ⁱ—La1—O15—W2	−148.3 (4)
O15—W2—O1—W5	88.6 (2)	O10—W3—O16—La1	179.7 (4)
O7—W2—O1—W5	−6.0 (2)	O11—W3—O16—La1	−78.3 (4)
O9—W2—O1—W5	−178.6 (3)	O9—W3—O16—La1	75.5 (4)
O3—W2—O1—W5	−92.1 (2)	O4—W3—O16—La1	1.7 (10)
O2—W1—O3—W2	−179.0 (3)	O1—W3—O16—La1	−1.1 (4)
O6—W1—O3—W2	2.1 (7)	O15ⁱ—La1—O16—W3	137.3 (4)
O5—W1—O3—W2	78.2 (3)	O15—La1—O16—W3	−60.3 (4)
O4—W1—O3—W2	−76.9 (3)	O18—La1—O16—W3	1.8 (4)
O1—W1—O3—W2	0.4 (3)	O18ⁱ—La1—O16—W3	100.7 (5)
O8—W2—O3—W1	178.6 (3)	O16ⁱ—La1—O16—W3	−149.3 (5)
O15—W2—O3—W1	1.9 (9)	O17—La1—O16—W3	61.5 (4)
O7—W2—O3—W1	−79.5 (3)	O17ⁱ—La1—O16—W3	−105.4 (4)
O9—W2—O3—W1	77.8 (3)	O12—W4—O17—La1	−179.8 (4)
O1—W2—O3—W1	−0.4 (3)	O11—W4—O17—La1	75.5 (4)
O2—W1—O4—W3	−179.8 (3)	O13—W4—O17—La1	−78.7 (4)
O6—W1—O4—W3	−76.7 (3)	O6—W4—O17—La1	−5.1 (10)
O5—W1—O4—W3	3.7 (8)	O1—W4—O17—La1	−1.7 (3)
O3—W1—O4—W3	78.6 (3)	O15ⁱ—La1—O17—W4	−149.2 (4)
O1—W1—O4—W3	1.0 (3)	O15—La1—O17—W4	1.6 (4)
O10—W3—O4—W1	178.1 (3)	O18—La1—O17—W4	62.5 (4)
O16—W3—O4—W1	−3.9 (9)	O18ⁱ—La1—O17—W4	137.5 (4)
O11—W3—O4—W1	77.4 (3)	O16ⁱ—La1—O17—W4	−104.7 (4)
O9—W3—O4—W1	−79.5 (3)	O16—La1—O17—W4	−60.0 (4)
O1—W3—O4—W1	−1.0 (3)	O17ⁱ—La1—O17—W4	101.2 (4)
O2—W1—O5—W5	179.9 (3)	O14—W5—O18—La1	−179.2 (4)
O6—W1—O5—W5	76.8 (3)	O13—W5—O18—La1	77.1 (4)
O4—W1—O5—W5	−3.6 (8)	O7—W5—O18—La1	−77.2 (4)
O3—W1—O5—W5	−78.7 (3)	O5—W5—O18—La1	−4.2 (10)
O1—W1—O5—W5	−0.9 (3)	O1—W5—O18—La1	0.1 (4)
O14—W5—O5—W1	−179.5 (3)	O15ⁱ—La1—O18—W5	−105.9 (4)
O18—W5—O5—W1	5.3 (9)	O15—La1—O18—W5	61.1 (4)
O13—W5—O5—W1	−77.8 (3)	O18ⁱ—La1—O18—W5	−151.9 (5)
O7—W5—O5—W1	79.8 (3)	O16ⁱ—La1—O18—W5	99.5 (5)
O1—W5—O5—W1	0.9 (3)	O16—La1—O18—W5	−1.0 (5)
O2—W1—O6—W4	179.2 (3)	O17—La1—O18—W5	−61.4 (4)
O5—W1—O6—W4	−77.6 (3)	O17ⁱ—La1—O18—W5	136.6 (4)

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

W—O bond distance categories (Å) for the [W₅O₁₈]^6- anionic fragment present in (I) {[···] average; (···) difference} top

Categories		average	difference
W—O_I	2.304 (6)–2.324 (6)	[2.314]	(0.020)
W—O_II (short)	1.890 (6)–1.963 (6)	[1.927]	(0.073)
W—O_II (long)	2.022 (6)–2.031 (6)	[2.027]	(0.009)
W—O_III	1.776 (6)–1.790 (6)	[1.783]	(0.014)
W—O_IV	1.726 (6)–1.734 (6)	[1.730]	(0.008)

Acknowledgements

We are grateful to the Fundação para a Ciência e Tecnologia (FCT, Portugal) for their general financial support under the POCTI programme (supported by FEDER).

References

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Volume 61| Part 3| March 2005| Pages i28-i31

https://doi.org/10.1107/S1600536805003557

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