A novel zirconium polyoxometalate compound: (NH₄)₉[Zr₂(μ-OH)(H₂O)₂(AsOH)₂(AsW₇O₂₈)(AsW₁₀O₃₆)]·26H₂O

The crystal structure of the title compound, nona­ammonium (arsenic decatungstido)(arsenic heptatungstido)­di­aqua-μ-hydroxo-(hydroxy­arsenido)­di­zir­conium hexa­cosa­hydrate, which was ob­tained from the reaction of [NaAs₄W₄₀O₁₄₀]²⁷⁻ with Zr^IV, has been determined. The anionic complex consists of two hydroxyl-bridged seven-coordinate capped trigonal-prismatic zirconium ions, which are bonded to an [AsW₁₀O₃₆]⁹⁻ anion and to an [AsW₇O₂₈]¹¹⁻ anion that has two {AsOH}²⁺ capping units. The asymmetric unit contains half of the complex, with one crystallographically independent Zr atom. Crystallographic m symmetry imposed by the monoclinic C2/m space group gives rise to the asymmetric unit comprising half of the complex with one crystallographically independent Zr atom.

S1. Comment

Polyoxometalates have been extensively studied because of their useful properties in fields as diverse as catalysis and medicine (Pope, 1983; Baker & Glick, 1998). Recently, there has been much interest in the use of polyoxometalates as potential sequestration/separation agents in nuclear waste remediation, with most attention focused on coordination to the f-elements (Williams et al., 2000; Kamoshida et al., 1998; Bion et al., 1999; Gaunt et al., 2002). Relatively little attention has been given to aspects of this chemistry with zirconium, which is another important element in some nuclear waste processes (Doucet et al., 2002). In addition, Zr^IV can be used as a non-radioactive analogue for actinide ions, including Pu^IV. During our studies to increase the understanding of the interaction of Zr^IV with heteropolyanions, we obtained the title compound, (I).

The crystal structure of (I) has one symmetrically unique Zr atom, with the whole complex anion grown from the asymmetric unit by the operation (x, −y, z) (Figs. 1 and 2). The reacting [NaAs₄W₄₀O₁₄₀]²⁷⁻ anion, itself composed of four linked [AsW₉O₃₃]⁹⁻ anions, has fragmented and the two units that coordinate to the Zr⁴⁺ ions are formally [AsW₁₀O₃₆]⁹⁻ and [AsW₇O₂₈]¹¹⁻. The Zr⁴⁺ ion is seven-coordinate, with an arrangement of O-donor ligands that conforms to capped trigonal-prismatic geometry. Five O atoms from the polyxometalate fragments are bonded to Zr, with distances ranging from 2.093 (7) Å for Zr—O7 to 2.136 (6) Å for Zr1—O4. The Zr atoms are linked by a bridging hydroxyl group, with a Zr—O1 distance of 2.151 (2) Å. The coordination sphere of Zr is completed by an O atom from a water molecule in the capping position of the trigonal prism, with a Zr—O2 distance of 2.326 (6) Å. A bond-valence sum (BVS; reference?) of 1.095 was calculated for O1, which bridges the two Zr atoms, indicating an attached H atom, and it was assigned as an OH⁻ group. By comparison, a BVS of 0.341 was calculated for water atom O2. Upon coordination of Zr, the remaining unsaturated O atoms of [AsW₇O₂₈]¹¹⁻ are bonded to capping {AsOH}²⁺ groups. The assignment of the H atom was made based on the similarity of the As—O terminal bond length As3—O22 [1.769 (8) Å] to As3—O12 [1.771 (7) Å], for which O12 is a µ₂-O atom, and on the similarity in bond length to those in a previously reported polyoxometalate compound containing assigned {AsOH}²⁺ groups (Müller et al., 1996). The [AsW₁₀O₃₆]⁹⁻ unit has the unusual structural feature, for a heteropolytungstate, of a five-coordinate W5 atom, with distorted square-pyramidal geometry. This coordination probably arises because the lone pair of electrons on the As^III atom occupy the space where an O atom would need to be in order for W5 to achieve an octahedral geometry.

S2. Experimental

Na₂₇[NaAs₄W₄₀O₁₄₀].60H₂O (2.00 g, 0.17 mmol; Klemperer, 1990) and Na₂WO₄·2H₂O (0.224 g, 0.68 mmol) were successively suspended in H₂O (100 ml). ZrCl₄ (0.158 g, 0.68 mmol) was added to the suspension, and it was heated at reflux for 1 h to yield a colourless solution. NH₄Cl (11 g, 20.56 mmol) was dissolved in the hot solution, which was allowed to cool to room temperature and was then filtered under gravity and stored at 276 K. After three months, a few colourless prismatic crystals (<0.1 g) of (I) had grown from the solution. The crystal chosen for structural determination had a size of 0.31 × 0.08 × 0.03 mm. FT–IR (ATR): 945 (W═O), 878 (W—O—W), 1618 (H—O—H), 1417 cm⁻¹ (N—H).

S3. Refinement

All Zr, W, As and O atoms of the anionic complex were refined with anisotropic displacement parameters. All solvent water O atoms and ammonium N atoms were refined isotropically. Data did not allow direct discrimination between O and N atoms, so in the later stages of refinement, the water O atoms with the highest displacement parameters were assigned as N atoms to account for the NH₄⁺ cations, which balance the charge. The positions of the H atoms were not determined. The locations of the highest peak and deepest hole in the final residual electron-density map were 0.79 and 0.62 Å, respectively, from W1.

[Please check carefully the number of atoms included in the _chemical_formula_sum 'As4 H50 N11 O94 W17 Zr2', as this does not match the total of 'As4 H97 N9 O96 W17 Zr2' in the title formula; is the title formula representation correct? PLATON is happy that the non-H atoms in the sum formula match the atom list, but please check that the H atoms are correct as the molecular weight may need to be altered.]

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XSHELL in SHELXTL (Bruker, 2001); software used to prepare material for publication: XP in SHELXTL and DIAMOND (Crystal Impact, 1998).

Figures

	Fig. 1. A view of the anion of (I). Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Polyhedral representation of the anion of (I).

(I)

Crystal data

(NH4)9[Zr2(OH)(H2O)2(AsOH)2(AsW7O28)(AsW10O36)]·26H2O	F(000) = 9552
Mr = 5349.42	Dx = 3.883 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 32.200 (4) Å	Cell parameters from 5091 reflections
b = 15.993 (2) Å	θ = 2.3–28.3°
c = 18.415 (2) Å	µ = 23.05 mm^−1
β = 105.228 (2)°	T = 100 K
V = 9150 (2) Å^3	Prismatic, colourless
Z = 4	0.31 × 0.08 × 0.03 mm

Data collection

Bruker SMART Platform CCD diffractometer	10914 independent reflections
Radiation source: fine-focus sealed tube	8830 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −42→41
Tmin = 0.437, Tmax = 1	k = −20→20
39187 measured reflections	l = −24→24

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0359P)^2 + 201.8467P] where P = (Fo^2 + 2Fc^2)/3
10914 reflections	(Δ/σ)max = 0.002
525 parameters	Δρmax = 3.36 e Å^−3
0 restraints	Δρmin = −1.95 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
As1	0.11162 (4)	0.0000	0.32177 (7)	0.0077 (2)
As2	0.25942 (4)	0.0000	0.16804 (7)	0.0092 (3)
As3	0.21886 (3)	0.16991 (6)	0.00408 (6)	0.0159 (2)
N1	0.5531 (12)	0.136 (2)	0.137 (2)	0.096 (11)*	0.50
N2	0.5605 (15)	0.0000	0.241 (3)	0.198 (18)*
N3	0.4782 (7)	0.1535 (13)	0.2932 (11)	0.109 (6)*
N4	0.5048 (12)	0.147 (2)	0.451 (2)	0.100 (12)*	0.50
N5	0.4573 (13)	0.0000	0.993 (2)	0.168 (15)*
N6	0.1133 (15)	0.5000	0.470 (3)	0.202 (19)*
N7	0.1509 (7)	0.4160 (14)	0.1328 (12)	0.120 (7)*
O1	0.2259 (3)	0.0000	0.3336 (5)	0.0103 (18)
O2	0.2250 (2)	0.2556 (4)	0.3843 (4)	0.0171 (15)
O3	0.1947 (2)	0.1031 (4)	0.4181 (4)	0.0120 (13)
O4	0.1498 (2)	0.1864 (4)	0.3020 (4)	0.0131 (14)
O5	0.2783 (2)	0.1358 (4)	0.3695 (4)	0.0108 (13)
O6	0.2273 (2)	0.2218 (4)	0.2438 (4)	0.0123 (13)
O7	0.1772 (2)	0.0814 (4)	0.2135 (4)	0.0129 (14)
O8	0.3260 (3)	0.0000	0.0108 (5)	0.016 (2)
O9	0.3369 (2)	0.1720 (4)	0.0006 (4)	0.0200 (16)
O10	0.3755 (2)	0.0831 (4)	0.1288 (4)	0.0162 (15)
O11	0.4346 (3)	0.0000	0.2439 (6)	0.020 (2)
O12	0.2598 (2)	0.0940 (4)	0.0117 (4)	0.0165 (15)
O13	0.3095 (3)	0.0000	0.1391 (5)	0.0123 (19)
O14	0.3051 (2)	0.1779 (4)	0.1273 (4)	0.0136 (14)
O15	0.3625 (2)	0.0824 (4)	0.2674 (4)	0.0120 (13)
O16	0.2207 (2)	0.1771 (4)	0.1017 (4)	0.0146 (14)
O17	0.2729 (2)	0.0858 (4)	0.2305 (4)	0.0120 (13)
O18	0.2673 (2)	0.3228 (4)	0.1625 (4)	0.0174 (15)
O19	0.3269 (3)	0.0000	0.3562 (5)	0.0111 (19)
O20	0.3144 (2)	0.2178 (4)	0.2727 (4)	0.0111 (13)
O21	0.3651 (2)	0.1536 (4)	0.4058 (4)	0.0152 (14)
O22	0.1735 (3)	0.1031 (5)	−0.0219 (4)	0.0292 (18)
O23	0.1459 (3)	0.0000	0.0745 (5)	0.016 (2)
O24	0.0937 (2)	0.0795 (4)	0.1605 (4)	0.0131 (14)
O25	0.0247 (3)	0.0000	0.1679 (5)	0.015 (2)
O26	0.0146 (2)	0.1527 (4)	0.0899 (4)	0.0197 (15)
O27	−0.0013 (2)	0.1334 (4)	0.2315 (4)	0.0126 (13)
O28	0.0748 (2)	0.0845 (4)	0.3021 (4)	0.0119 (13)
O29	0.1224 (3)	0.0000	0.4209 (5)	0.0089 (18)
O30	0.0681 (2)	0.2174 (4)	0.2214 (4)	0.0132 (14)
O31	0.1890 (3)	0.0000	0.5333 (5)	0.0105 (18)
O32	0.1950 (2)	0.1730 (4)	0.5566 (4)	0.0177 (15)
O34	0.1087 (2)	0.3269 (4)	0.3370 (4)	0.0215 (16)
O35	0.1244 (2)	0.1819 (4)	0.4264 (4)	0.0129 (14)
O36	−0.0010 (3)	0.0000	0.3168 (5)	0.0109 (19)
O37	−0.0349 (2)	0.1552 (4)	0.3544 (4)	0.0162 (15)
O38	0.0432 (2)	0.0809 (4)	0.4349 (4)	0.0134 (14)
O39	0.0515 (3)	0.0000	0.5738 (6)	0.018 (2)
O40	0.0444 (2)	0.2149 (4)	0.3494 (4)	0.0145 (14)
O41	0.1190 (2)	0.0837 (4)	0.5392 (4)	0.0131 (14)
O1S	0.9572 (6)	0.0000	0.0119 (11)	0.087 (6)*
O2S	0.9309 (4)	0.0000	0.1672 (7)	0.033 (3)*
O3S	0.9028 (3)	0.1525 (6)	0.1128 (5)	0.043 (2)*
O4S	0.9314 (4)	0.2206 (7)	0.9985 (6)	0.058 (3)*
O5S	0.4352 (3)	0.2578 (7)	0.4752 (6)	0.052 (3)*
O6S	0.4032 (3)	0.2426 (6)	0.2334 (5)	0.044 (2)*
O7S	0.4462 (4)	0.1290 (7)	0.0805 (7)	0.065 (3)*
O8S	0.2027 (4)	0.3947 (8)	0.2780 (7)	0.072 (3)*
O9S	0.1359 (3)	0.1388 (5)	0.6860 (4)	0.0288 (18)*
O10S	0.1391 (3)	0.2381 (5)	0.1286 (5)	0.036 (2)*
O11S	0.2306 (5)	0.0000	0.8691 (8)	0.048 (4)*
O12S	0.1434 (4)	0.0000	0.7799 (7)	0.043 (3)*
O13S	0.3160 (2)	0.1530 (5)	0.5312 (4)	0.0258 (17)*
O14S	0.2725 (4)	0.0000	0.4967 (7)	0.032 (3)*
O15S	0.1445 (8)	0.5000	0.3388 (14)	0.117 (8)*
O16S	0.2259 (5)	0.0000	0.6932 (9)	0.057 (4)*
O17S	0.5223 (6)	0.1347 (12)	0.1843 (11)	0.043 (5)*	0.50
W1	0.321038 (13)	0.10475 (2)	0.06040 (2)	0.01323 (9)
W2	0.379104 (17)	0.0000	0.21031 (3)	0.01162 (11)
W3	0.265639 (12)	0.21944 (2)	0.18656 (2)	0.01066 (8)
W4	0.324427 (12)	0.11620 (2)	0.33244 (2)	0.01023 (8)
W5	0.141090 (17)	0.0000	0.16639 (3)	0.01075 (11)
W6	0.041151 (12)	0.11540 (2)	0.17691 (2)	0.01162 (8)
W7	0.101637 (12)	0.22102 (2)	0.32628 (2)	0.01119 (8)
W8	0.165378 (12)	0.10633 (2)	0.48902 (2)	0.01024 (8)
W9	0.076287 (17)	0.0000	0.50341 (3)	0.00978 (11)
W10	0.011628 (12)	0.11589 (2)	0.33834 (2)	0.01043 (8)
Zr1	0.21186 (3)	0.13110 (5)	0.31672 (5)	0.01027 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.0056 (6)	0.0063 (6)	0.0118 (6)	0.000	0.0033 (5)	0.000
As2	0.0093 (6)	0.0062 (6)	0.0130 (6)	0.000	0.0046 (5)	0.000
As3	0.0141 (5)	0.0162 (5)	0.0183 (5)	0.0007 (4)	0.0059 (4)	0.0019 (4)
O1	0.011 (5)	0.003 (4)	0.015 (5)	0.000	0.002 (4)	0.000
O2	0.019 (4)	0.012 (3)	0.023 (4)	−0.005 (3)	0.011 (3)	−0.012 (3)
O3	0.010 (3)	0.009 (3)	0.018 (3)	0.000 (3)	0.006 (3)	0.005 (3)
O4	0.009 (3)	0.009 (3)	0.022 (4)	−0.002 (3)	0.006 (3)	0.002 (3)
O5	0.011 (3)	0.009 (3)	0.013 (3)	0.002 (3)	0.005 (3)	−0.002 (2)
O6	0.008 (3)	0.012 (3)	0.016 (3)	0.001 (3)	0.002 (3)	0.001 (3)
O7	0.015 (3)	0.010 (3)	0.016 (3)	−0.001 (3)	0.007 (3)	−0.001 (3)
O8	0.017 (5)	0.017 (5)	0.015 (5)	0.000	0.006 (4)	0.000
O9	0.022 (4)	0.016 (4)	0.028 (4)	0.001 (3)	0.016 (3)	0.006 (3)
O10	0.019 (4)	0.011 (3)	0.023 (4)	−0.003 (3)	0.013 (3)	−0.003 (3)
O11	0.012 (5)	0.016 (5)	0.034 (6)	0.000	0.009 (5)	0.000
O12	0.014 (4)	0.016 (3)	0.019 (4)	0.001 (3)	0.003 (3)	−0.002 (3)
O13	0.011 (5)	0.008 (4)	0.020 (5)	0.000	0.007 (4)	0.000
O14	0.011 (3)	0.010 (3)	0.022 (4)	−0.004 (3)	0.008 (3)	−0.001 (3)
O15	0.009 (3)	0.009 (3)	0.021 (4)	−0.004 (3)	0.009 (3)	−0.002 (3)
O16	0.016 (4)	0.015 (3)	0.016 (3)	0.000 (3)	0.009 (3)	0.003 (3)
O17	0.014 (3)	0.008 (3)	0.015 (3)	0.000 (3)	0.006 (3)	−0.002 (3)
O18	0.020 (4)	0.008 (3)	0.029 (4)	−0.001 (3)	0.015 (3)	0.003 (3)
O19	0.007 (4)	0.015 (5)	0.012 (5)	0.000	0.003 (4)	0.000
O20	0.012 (3)	0.003 (3)	0.020 (3)	−0.002 (2)	0.007 (3)	−0.001 (2)
O21	0.009 (3)	0.017 (3)	0.019 (4)	−0.001 (3)	0.003 (3)	−0.003 (3)
O22	0.025 (4)	0.036 (5)	0.029 (4)	−0.008 (4)	0.011 (4)	−0.002 (4)
O23	0.012 (5)	0.019 (5)	0.019 (5)	0.000	0.007 (4)	0.000
O24	0.009 (3)	0.011 (3)	0.019 (4)	−0.002 (3)	0.003 (3)	−0.004 (3)
O25	0.008 (5)	0.019 (5)	0.018 (5)	0.000	0.005 (4)	0.000
O26	0.014 (4)	0.020 (4)	0.023 (4)	0.003 (3)	0.003 (3)	0.003 (3)
O27	0.009 (3)	0.011 (3)	0.018 (3)	−0.002 (3)	0.004 (3)	0.000 (3)
O28	0.006 (3)	0.005 (3)	0.026 (4)	0.002 (2)	0.006 (3)	0.001 (3)
O29	0.010 (5)	0.010 (4)	0.008 (4)	0.000	0.004 (4)	0.000
O30	0.011 (3)	0.008 (3)	0.022 (4)	0.002 (3)	0.007 (3)	0.008 (3)
O31	0.004 (4)	0.013 (5)	0.014 (5)	0.000	0.000 (4)	0.000
O32	0.011 (3)	0.022 (4)	0.020 (4)	−0.003 (3)	0.003 (3)	−0.007 (3)
O34	0.014 (4)	0.010 (3)	0.043 (5)	0.000 (3)	0.010 (3)	0.002 (3)
O35	0.012 (3)	0.009 (3)	0.020 (4)	0.003 (3)	0.008 (3)	0.002 (3)
O36	0.005 (4)	0.011 (4)	0.019 (5)	0.000	0.008 (4)	0.000
O37	0.012 (3)	0.007 (3)	0.030 (4)	0.003 (3)	0.006 (3)	0.003 (3)
O38	0.011 (3)	0.015 (3)	0.013 (3)	0.001 (3)	0.000 (3)	−0.001 (3)
O39	0.013 (5)	0.023 (5)	0.023 (5)	0.000	0.014 (4)	0.000
O40	0.009 (3)	0.012 (3)	0.023 (4)	0.001 (3)	0.005 (3)	0.001 (3)
O41	0.008 (3)	0.015 (3)	0.017 (3)	0.001 (3)	0.005 (3)	−0.002 (3)
W1	0.0137 (2)	0.01087 (18)	0.0180 (2)	0.00032 (15)	0.00926 (16)	0.00254 (15)
W2	0.0086 (3)	0.0092 (2)	0.0191 (3)	0.000	0.0074 (2)	0.000
W3	0.01027 (19)	0.00604 (17)	0.01749 (19)	−0.00063 (13)	0.00686 (15)	0.00138 (14)
W4	0.00735 (18)	0.00818 (17)	0.01611 (19)	−0.00149 (13)	0.00478 (14)	−0.00191 (14)
W5	0.0075 (3)	0.0113 (2)	0.0143 (3)	0.000	0.0043 (2)	0.000
W6	0.00733 (18)	0.01180 (18)	0.01585 (19)	0.00229 (14)	0.00324 (14)	0.00292 (14)
W7	0.00740 (18)	0.00674 (17)	0.0206 (2)	0.00004 (13)	0.00579 (15)	0.00048 (14)
W8	0.00645 (18)	0.01066 (17)	0.01456 (19)	−0.00184 (14)	0.00447 (14)	−0.00288 (14)
W9	0.0061 (2)	0.0106 (2)	0.0143 (3)	0.000	0.0056 (2)	0.000
W10	0.00557 (17)	0.00871 (17)	0.01802 (19)	0.00153 (13)	0.00491 (14)	0.00081 (14)
Zr1	0.0074 (4)	0.0084 (4)	0.0163 (5)	−0.0008 (3)	0.0053 (3)	−0.0005 (3)

Geometric parameters (Å, º)

As1—O29	1.767 (8)	O19—W4	1.906 (2)
As1—O28^i	1.770 (6)	O20—W3	1.917 (7)
As1—O28	1.770 (6)	O20—W4	1.940 (6)
As2—O17	1.770 (6)	O21—W4	1.723 (7)
As2—O17^i	1.770 (6)	O23—W5	1.738 (9)
As2—O13	1.826 (9)	O24—W6	1.884 (6)
As3—O22	1.770 (8)	O24—W5	1.968 (6)
As3—O12	1.772 (7)	O25—W6	1.916 (2)
As3—O16	1.787 (6)	O25—W6^i	1.916 (2)
N1—O17S	1.48 (4)	O26—W6	1.713 (7)
N4—N4^ii	1.90 (7)	O27—W6	1.919 (6)
O1—Zr1^i	2.150 (2)	O27—W10	1.922 (6)
O1—Zr1	2.150 (2)	O28—W6	2.329 (7)
O2—Zr1	2.327 (6)	O28—W7	2.347 (6)
O3—W8	1.801 (6)	O28—W10	2.357 (6)
O3—Zr1	2.130 (6)	O29—W8	2.338 (6)
O4—W7	1.811 (6)	O29—W8^i	2.338 (6)
O4—Zr1	2.136 (6)	O29—W9	2.388 (8)
O5—W4	1.816 (6)	O30—W6	1.928 (6)
O5—Zr1	2.107 (6)	O30—W7	1.949 (7)
O6—W3	1.823 (6)	O31—W8^i	1.952 (4)
O6—Zr1	2.123 (6)	O31—W8	1.952 (4)
O7—W5	1.807 (6)	O32—W8	1.724 (7)
O7—Zr1	2.093 (7)	O34—W7	1.714 (7)
O8—W1	1.934 (5)	O35—W7	1.902 (7)
O8—W1^i	1.934 (5)	O35—W8	1.932 (6)
O9—W1	1.711 (7)	O36—W10	1.916 (2)
O10—W1	1.902 (7)	O36—W10^i	1.916 (2)
O10—W2	1.984 (7)	O37—W10	1.719 (6)
O11—W2	1.729 (10)	O38—W10	1.885 (6)
O12—W1	1.946 (7)	O38—W9	1.924 (6)
O13—W2	2.281 (9)	O39—W9	1.690 (9)
O13—W1^i	2.308 (6)	O40—W10	1.884 (6)
O13—W1	2.308 (6)	O40—W7	2.000 (6)
O14—W1	1.865 (6)	O41—W9	1.907 (6)
O14—W3	1.995 (6)	O41—W8	1.986 (6)
O15—W2	1.849 (6)	W2—O15^i	1.849 (6)
O15—W4	2.001 (6)	W2—O10^i	1.984 (7)
O16—W3	1.952 (7)	W5—O7^i	1.807 (6)
O17—W4	2.209 (7)	W5—O24^i	1.968 (6)
O17—W3	2.276 (6)	W9—O41^i	1.907 (6)
O18—W3	1.716 (6)	W9—O38^i	1.924 (6)
O19—W4^i	1.906 (2)
O29—As1—O28^i	98.7 (3)	O5—W4—O17	81.5 (3)
O29—As1—O28	98.7 (3)	O19—W4—O17	87.5 (3)
O28^i—As1—O28	99.5 (4)	O20—W4—O17	74.1 (2)
O17—As2—O17^i	101.7 (4)	O15—W4—O17	82.7 (2)
O17—As2—O13	96.0 (3)	O23—W5—O7	104.9 (3)
O17^i—As2—O13	96.0 (3)	O23—W5—O7^i	104.9 (3)
O22—As3—O12	98.7 (3)	O7—W5—O7^i	92.1 (4)
O22—As3—O16	96.7 (3)	O23—W5—O24^i	102.2 (3)
O12—As3—O16	97.9 (3)	O7—W5—O24^i	152.1 (3)
Zr1^i—O1—Zr1	154.4 (5)	O7^i—W5—O24^i	87.3 (3)
W8—O3—Zr1	159.3 (4)	O23—W5—O24	102.2 (3)
W7—O4—Zr1	158.2 (4)	O7—W5—O24	87.3 (3)
W4—O5—Zr1	130.7 (3)	O7^i—W5—O24	152.1 (3)
W3—O6—Zr1	131.2 (3)	O24^i—W5—O24	80.5 (4)
W5—O7—Zr1	146.3 (4)	O26—W6—O24	101.8 (3)
W1—O8—W1^i	120.0 (5)	O26—W6—O25	101.3 (4)
W1—O10—W2	119.0 (3)	O24—W6—O25	86.1 (3)
As3—O12—W1	128.2 (4)	O26—W6—O27	100.8 (3)
As2—O13—W2	129.9 (5)	O24—W6—O27	157.3 (3)
As2—O13—W1^i	118.9 (3)	O25—W6—O27	88.3 (3)
W2—O13—W1^i	93.7 (3)	O26—W6—O30	99.3 (3)
As2—O13—W1	118.9 (3)	O24—W6—O30	90.2 (3)
W2—O13—W1	93.7 (3)	O25—W6—O30	159.4 (3)
W1^i—O13—W1	93.1 (3)	O27—W6—O30	87.3 (3)
W1—O14—W3	153.5 (4)	O26—W6—O28	171.2 (3)
W2—O15—W4	147.8 (3)	O24—W6—O28	83.7 (2)
As3—O16—W3	130.5 (4)	O25—W6—O28	85.8 (3)
As2—O17—W4	136.4 (3)	O27—W6—O28	74.0 (2)
As2—O17—W3	120.8 (3)	O30—W6—O28	73.6 (2)
W4—O17—W3	94.6 (2)	O34—W7—O4	103.5 (3)
W4^i—O19—W4	154.3 (5)	O34—W7—O35	102.0 (3)
W3—O20—W4	117.3 (3)	O4—W7—O35	90.1 (3)
W6—O24—W5	154.7 (4)	O34—W7—O30	99.5 (3)
W6—O25—W6^i	148.9 (5)	O4—W7—O30	91.9 (3)
W6—O27—W10	121.5 (3)	O35—W7—O30	157.3 (3)
As1—O28—W6	118.5 (3)	O34—W7—O40	97.2 (3)
As1—O28—W7	118.6 (3)	O4—W7—O40	159.2 (3)
W6—O28—W7	92.4 (2)	O35—W7—O40	85.4 (3)
As1—O28—W10	133.3 (3)	O30—W7—O40	84.7 (3)
W6—O28—W10	91.3 (2)	O34—W7—O28	166.6 (3)
W7—O28—W10	92.9 (2)	O4—W7—O28	88.0 (2)
As1—O29—W8	118.9 (3)	O35—W7—O28	84.6 (3)
As1—O29—W8^i	118.9 (3)	O30—W7—O28	72.8 (2)
W8—O29—W8^i	93.3 (3)	O40—W7—O28	71.4 (2)
As1—O29—W9	132.1 (5)	O32—W8—O3	104.2 (3)
W8—O29—W9	92.2 (2)	O32—W8—O35	101.9 (3)
W8^i—O29—W9	92.2 (2)	O3—W8—O35	89.5 (3)
W6—O30—W7	121.1 (3)	O32—W8—O31	99.0 (3)
W8^i—O31—W8	121.2 (4)	O3—W8—O31	93.3 (3)
W7—O35—W8	144.4 (4)	O35—W8—O31	157.6 (3)
W10—O36—W10^i	150.6 (5)	O32—W8—O41	96.8 (3)
W10—O38—W9	152.5 (4)	O3—W8—O41	159.0 (3)
W10—O40—W7	122.7 (3)	O35—W8—O41	85.0 (3)
W9—O41—W8	121.9 (3)	O31—W8—O41	84.5 (3)
O9—W1—O14	102.2 (3)	O32—W8—O29	167.0 (3)
O9—W1—O10	99.3 (3)	O3—W8—O29	86.5 (3)
O14—W1—O10	92.4 (3)	O35—W8—O29	85.4 (2)
O9—W1—O8	99.5 (3)	O31—W8—O29	72.6 (3)
O14—W1—O8	157.8 (3)	O41—W8—O29	72.9 (3)
O10—W1—O8	88.8 (3)	O39—W9—O41	100.2 (3)
O9—W1—O12	101.4 (3)	O39—W9—O41^i	100.2 (3)
O14—W1—O12	86.5 (3)	O41—W9—O41^i	89.1 (4)
O10—W1—O12	159.1 (3)	O39—W9—O38^i	102.2 (3)
O8—W1—O12	84.6 (3)	O41—W9—O38^i	157.5 (3)
O9—W1—O13	170.1 (3)	O41^i—W9—O38^i	88.8 (3)
O14—W1—O13	85.6 (3)	O39—W9—O38	102.2 (3)
O10—W1—O13	74.0 (3)	O41—W9—O38	88.8 (3)
O8—W1—O13	73.4 (3)	O41^i—W9—O38	157.5 (3)
O12—W1—O13	85.1 (3)	O38^i—W9—O38	84.6 (4)
O11—W2—O15	102.8 (3)	O39—W9—O29	170.2 (4)
O11—W2—O15^i	102.8 (3)	O41—W9—O29	73.0 (2)
O15—W2—O15^i	90.9 (4)	O41^i—W9—O29	73.0 (2)
O11—W2—O10^i	96.9 (3)	O38^i—W9—O29	85.0 (2)
O15—W2—O10^i	159.7 (3)	O38—W9—O29	85.0 (2)
O15^i—W2—O10^i	89.1 (3)	O37—W10—O40	99.4 (3)
O11—W2—O10	96.9 (3)	O37—W10—O38	102.9 (3)
O15—W2—O10	89.1 (3)	O40—W10—O38	90.0 (3)
O15^i—W2—O10	159.7 (3)	O37—W10—O36	104.0 (3)
O10^i—W2—O10	84.1 (4)	O40—W10—O36	156.5 (3)
O11—W2—O13	166.5 (4)	O38—W10—O36	86.6 (3)
O15—W2—O13	86.6 (3)	O37—W10—O27	99.2 (3)
O15^i—W2—O13	86.6 (3)	O40—W10—O27	87.3 (3)
O10^i—W2—O13	73.2 (3)	O38—W10—O27	157.9 (3)
O10—W2—O13	73.2 (3)	O36—W10—O27	87.3 (3)
O18—W3—O6	101.6 (3)	O37—W10—O28	169.3 (3)
O18—W3—O20	98.8 (3)	O40—W10—O28	73.1 (2)
O6—W3—O20	93.1 (3)	O38—W10—O28	85.0 (3)
O18—W3—O16	101.2 (3)	O36—W10—O28	83.5 (3)
O6—W3—O16	89.8 (3)	O27—W10—O28	73.3 (2)
O20—W3—O16	158.8 (3)	O7—Zr1—O5	131.9 (2)
O18—W3—O14	96.5 (3)	O7—Zr1—O6	80.9 (2)
O6—W3—O14	161.7 (3)	O5—Zr1—O6	83.7 (2)
O20—W3—O14	87.0 (3)	O7—Zr1—O3	121.1 (2)
O16—W3—O14	83.8 (3)	O5—Zr1—O3	94.0 (2)
O18—W3—O17	171.7 (3)	O6—Zr1—O3	148.9 (2)
O6—W3—O17	80.5 (3)	O7—Zr1—O4	77.5 (3)
O20—W3—O17	73.0 (2)	O5—Zr1—O4	147.9 (2)
O16—W3—O17	86.8 (3)	O6—Zr1—O4	90.1 (2)
O14—W3—O17	82.0 (2)	O3—Zr1—O4	75.5 (2)
O21—W4—O5	100.0 (3)	O7—Zr1—O1	78.6 (3)
O21—W4—O19	100.4 (3)	O5—Zr1—O1	79.5 (3)
O5—W4—O19	94.1 (3)	O6—Zr1—O1	133.0 (3)
O21—W4—O20	97.6 (3)	O3—Zr1—O1	76.2 (3)
O5—W4—O20	92.2 (3)	O4—Zr1—O1	125.2 (3)
O19—W4—O20	159.6 (3)	O7—Zr1—O2	142.1 (3)
O21—W4—O15	95.9 (3)	O5—Zr1—O2	72.7 (2)
O5—W4—O15	164.0 (3)	O6—Zr1—O2	73.4 (2)
O19—W4—O15	83.0 (3)	O3—Zr1—O2	76.3 (2)
O20—W4—O15	85.6 (3)	O4—Zr1—O2	75.3 (2)
O21—W4—O17	171.7 (3)	O1—Zr1—O2	139.1 (3)

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