A uranyl sulfate cluster in Na₁₀[(UO₂)(SO₄)₄](SO₄)₂·3H₂O

Decasodium uranyl hexa­sulfate trihydrate, Na₁₀[(UO₂)(SO₄)₄](SO₄)₂·3H₂O, contains an unusual uranyl sulfate cluster with the composition [(UO₂)(SO₄)₄]^6-. The cluster is composed of a uranyl pentagonal bipyramid and four sulfate tetrahedra. Three sulfate tetrahedra are linked to the uranyl pentagonal bipyramid by the sharing of vertices, and the other shares an equatorial edge of the uranyl pentagonal bipyramid. The uranyl sulfate clusters occur in layers parallel to (010). The structure also contains two isolated symmetrically distinct sulfate tetrahedra, which also occur in layers parallel to (010). The uranyl sulfate clusters and isolated sulfate tetrahedra are linked through bonds to Na⁺ cations, and by hydrogen bonding involving the water molecules.

S1. Comment

Uranyl sulfates constitute an important group of minerals that are fairly widespread, although they are not abundant. Owing to the presence of uranium and sulfate in some ground waters, uranyl sulfate minerals may be important for determining the mobility of uranium in natural systems. We have undertaken a systematic study of the structures of natural and synthetic uranyl sulfates, and have grown crystals of the title new Na uranyl sulfate, (I), that contains the second known example of an unusual uranyl sulfate cluster. \sch

The structure of (I) contains one symmetrically distinct U⁶⁺ cation that is strongly bonded to two O atoms, forming an approximately linear (UO₂)²⁺ uranyl ion (designated Ur) with a U—O_Ur bond length of 1.777 Å. The uranyl ion is coordinated by five O atoms, located at the equatorial vertices of a pentagonal bipyramid that is capped by the O_Ur atoms. The mean U—O_eq (eq is equatorial) bond length of 2.363 Å is in excellent agreement with the average bond length of 2.37 (9) Å for uranyl polyhedra from numerous well refined structures (Burns et al., 1997).

There are six unique S⁶⁺ cations in the structure of (I), each of which is tetrahedrally coordinated by O atoms, with S—O bond lengths ranging from 1.455 to 1.477 Å Please clarify - values in CIF in range 1.436 (4)–1.524 (3) Å. The structure contains ten symmetrically distinct Na⁺ cations that are coordinated by from five to eight ligands, with mean bond lengths ranging from 2.356 to 2.617 Å.

The sums of the bond valences incident upon each site in the structure of (I) were calculated using the parameters for ^[7]U⁶⁺—O given by Burns et al. (1997), and for S⁶⁺—O and Na—O from Brese & O'Keeffe (1991). The sum at the U⁶⁺ site is 6.09, consistent with the assignment of all U as U⁶⁺. The sums at the S⁶⁺ and Na sites range from 5.97 to 6.32 and 0.90 to 1.19, respectively. Excluding the contributions of the H atoms, the sums at the O-atom positions range from 1.85 to 2.19 for atoms O1 to O26, and from 0.28 to 0.41 for atoms O27, O28 and O29, which correspond to H₂O groups.

The projection of the structure of (I) along [100] shows that it contains finite clusters of uranyl and sulfate polyhedra, as well as isolated sulfate tetrahedra (Fig. 1). The uranyl sulfate cluster is shown in Fig. 2 and involves the UrO₅ pentagonal bipyramid, which is linked to four sulfate tetrahedra, three by the sharing of equatorial vertices of the bipyramid, and one by the sharing of an equatorial edge with the S1 tetrahedron. The sharing of a tetrahedral edge with the bipyramid results in a relatively short U1—S1 distance of 3.092 (1) Å. This is only the second occurrence of this uranyl sulfate cluster; the first was recently reported in the structure of Na₆(UO₂)(SO₄)₄(H₂O)₂ (Hayden & Burns, 2001). It is only the third example of an inorganic uranyl compound that involves the sharing of the edge of a uranyl polyhedron with a tetrahedron that contains a hexavalent cation; the other example is the structure of K₄[(UO₂)(SO₄)₃] (Mikhailov et al., 1977).

The uranyl sulfate clusters in (I) are aligned parallel to (010), and occur in layers that are also parallel to (010) (Fig. 1). The orientation of each uranyl sulfate cluster within the layer is identical. The structure also contains two sulfate tetrahedra (S4 and S5) that are not components of the uranyl sulfate cluster. These tetrahedra occur in layers parallel to (010), between the layers of uranyl sulfate clusters. The uranyl sulfate clusters, as well as the S4 and S5 tetrahedra, are connected only through bonds to the Na⁺ cations, and by hydrogen bonding to the three symmetrically distinct H₂O groups that are bonded to Na⁺ cations.

The structure of (I) is classed with those uranyl compounds containing isolated clusters of polyhedra of high bond valence, owing to the presence of the uranyl sulfate clusters, as well as the isolated sulfate tetrahedra (Burns et al., 1996). This structural class is relatively rare in uranyl compounds, which tend to be dominated by sheets of uranyl polyhedra and other polyhedra of high bond valence.

Although the sharing of an equatorial edge of a uranyl polyhedron with a sulfate tetrahedron is rare in uranyl compounds, it is possibly rather common in solutions containing uranyl and sulfate. Using a combination of EXAFS and NMR spectroscopy, Moll et al. (2000) characterized the structures of uranyl sulfate complexes in acidic solutions. They found several complexes that involve the sharing of edges between uranyl pentagonal bipyramids and sulfate tetrahedra, as indicated by U—S distances in the range 3.10–3.14 Å, which are in excellent agreement with the value of 3.092 (1) Å found in (I).

The Flack parameter (Flack, 1983) of 0.439 (2) indicated that racemic twinning may be present. The final cycles of the refinement included racemic twinning, which reduced R₁ from 0.041 to 0.019.

S2. Experimental

A uranyl sulfate solution was prepared by dissolving UO₃ (5.78 g; Alfa Aesar) in a solution containing ultrapure water (40 ml) and concentrated sulfuric acid (5.2 ml). A small quantity (5 ml) of the solution was placed in a test tube and the pH adjusted to 4.0 using sodium hydroxide. The resulting solution was placed in a Fisher Scientific Isotemp oven at 343 K until evaporation was complete. Amongst the products, acicular light-yellow crystals of (I) up to 0.5 mm in length were recovered.

S3. Refinement

As is typical for compounds containing U, it was not possible to locate the positions of the H atoms in the difference Fourier maps, thus their positions were excluded from the refinement.

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-NT (Bruker, 1998); data reduction: SAINT-NT; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A polyhedral representation of the structure of (I) projected along [100]. Uranyl pentagonal bipyramids and sulfate tetrahedra are shown shaded with crosses and parallel lines, respectively. The positions of Na^+ cations and H2O groups are shown as solid and open circles, respectively.
	Fig. 2. The uranyl sulfate cluster in the structure of (I). Displacement ellipsoids are drawn at the ??% probability level. Please provide missing information.

(I)

Crystal data

Na10[(UO2)(SO4)4](SO4)2·3H2O	F(000) = 2144
Mr = 1130.34	Dx = 2.928 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9368 reflections
a = 9.3072 (5) Å	θ = 4.6–68.9°
b = 28.7064 (14) Å	µ = 7.11 mm^−1
c = 9.6152 (3) Å	T = 293 K
β = 93.401 (1)°	Irregular fragment, yellow
V = 2564.4 (2) Å^3	0.24 × 0.14 × 0.12 × 0.08 (radius) mm
Z = 4

Data collection

Bruker Apex CCD area-detector diffractometer	10066 reflections with I > 2σ(I)
ω scans	θmax = 34.5°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→14
Tmin = 0.260, Tmax = 0.426	k = −45→44
25908 measured reflections	l = −15→15
10449 independent reflections

Refinement

Refinement on F^2	H-atom parameters not refined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0282P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.019	(Δ/σ)max = 0.002
wR(F^2) = 0.052	Δρmax = 0.93 e Å^−3
S = 1.05	Δρmin = −1.24 e Å^−3
10449 reflections	Absolute structure: Flack (1983), with 5006 Friedel pairs
416 parameters	Absolute structure parameter: 0.439 (2)
2 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
U1	0.117953 (17)	0.172515 (3)	0.696301 (17)	0.01439 (2)
S1	−0.11623 (9)	0.15912 (3)	0.45796 (9)	0.01543 (14)
S2	0.38717 (9)	0.16209 (3)	0.96581 (9)	0.01610 (14)
S3	−0.03532 (8)	0.16488 (3)	1.04377 (8)	0.01603 (12)
S4	0.21865 (9)	0.03151 (3)	0.29219 (8)	0.01878 (13)
S5	0.78445 (8)	0.03411 (3)	−0.13011 (8)	0.01805 (12)
S6	0.46938 (8)	0.16342 (3)	0.54651 (8)	0.01602 (12)
Na1	0.1251 (4)	0.32337 (4)	0.7061 (4)	0.0241 (4)
Na2	0.4833 (2)	0.24722 (7)	0.78712 (19)	0.0359 (4)
Na3	−0.2622 (2)	0.24994 (7)	0.5766 (2)	0.0316 (4)
Na4	0.22358 (19)	0.13916 (6)	0.28164 (18)	0.0317 (4)
Na5	0.11915 (19)	0.06453 (6)	−0.04699 (17)	0.0318 (3)
Na6	−0.0031 (2)	0.04078 (6)	0.57542 (17)	0.0321 (3)
Na7	−0.4227 (2)	0.06777 (6)	0.40864 (17)	0.0366 (4)
Na8	−0.11440 (18)	0.06521 (6)	0.21720 (16)	0.0321 (3)
Na9	0.42990 (18)	0.06284 (6)	0.76510 (17)	0.0318 (3)
Na10	−0.28505 (18)	0.13828 (7)	0.79182 (18)	0.0332 (3)
O1	0.0897 (3)	0.23354 (9)	0.6812 (3)	0.0277 (6)
O2	0.1440 (3)	0.11117 (8)	0.7059 (3)	0.0256 (6)
O3	0.3210 (3)	0.17916 (12)	0.5761 (4)	0.0438 (8)
O4	−0.0161 (4)	0.16558 (12)	0.8905 (3)	0.0406 (8)
O5	0.2865 (3)	0.19232 (9)	0.8734 (3)	0.0266 (5)
O6	−0.1311 (2)	0.16340 (9)	0.6120 (2)	0.0212 (4)
O7	0.0430 (2)	0.16202 (9)	0.4464 (2)	0.0225 (4)
O8	−0.1746 (3)	0.11500 (10)	0.4081 (3)	0.0318 (6)
O9	−0.1861 (3)	0.19877 (9)	0.3862 (3)	0.0259 (5)
O10	0.5324 (3)	0.17253 (10)	0.9270 (3)	0.0317 (6)
O11	0.3492 (3)	0.11331 (9)	0.9449 (3)	0.0284 (6)
O12	0.3688 (3)	0.17704 (9)	0.1093 (3)	0.0260 (5)
O13	−0.1880 (4)	0.16677 (17)	1.0577 (5)	0.0627 (13)
O14	0.0401 (4)	0.20344 (12)	1.1102 (4)	0.0487 (9)
O15	0.0234 (5)	0.12141 (12)	1.0994 (4)	0.0551 (11)
O16	0.1067 (3)	0.05279 (12)	0.3716 (3)	0.0376 (7)
O17	0.1563 (4)	0.01848 (11)	0.1546 (3)	0.0434 (8)
O18	0.3357 (3)	0.06549 (10)	0.2789 (3)	0.0360 (6)
O19	0.2770 (3)	−0.01061 (9)	0.3630 (3)	0.0282 (5)
O20	0.8779 (4)	0.05647 (11)	−0.2272 (3)	0.0459 (8)
O21	0.8645 (4)	0.02722 (13)	0.0040 (3)	0.0461 (8)
O22	0.7325 (3)	−0.01091 (9)	−0.1844 (3)	0.0348 (6)
O23	0.6603 (3)	0.06492 (10)	−0.1104 (3)	0.0325 (6)
O24	0.5685 (3)	0.19579 (10)	0.6154 (3)	0.0327 (6)
O25	0.4786 (5)	0.16355 (14)	0.3965 (3)	0.0489 (9)
O26	0.4939 (4)	0.11701 (11)	0.6039 (4)	0.0438 (8)
O27	0.0926 (3)	0.40772 (9)	0.6603 (3)	0.0282 (5)
O28	−0.2477 (4)	0.24963 (11)	0.8406 (4)	0.0447 (8)
O29	0.4996 (4)	−0.01434 (10)	0.0809 (3)	0.0366 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.01240 (3)	0.01648 (4)	0.01410 (3)	−0.00035 (5)	−0.00071 (2)	0.00157 (5)
S1	0.0134 (3)	0.0187 (3)	0.0140 (3)	0.0002 (3)	−0.0006 (2)	−0.0021 (3)
S2	0.0144 (3)	0.0180 (3)	0.0155 (3)	0.0007 (3)	−0.0023 (3)	−0.0006 (3)
S3	0.0149 (3)	0.0187 (3)	0.0147 (3)	−0.0014 (2)	0.0030 (2)	−0.0012 (2)
S4	0.0214 (3)	0.0161 (3)	0.0192 (3)	−0.0001 (3)	0.0035 (2)	0.0013 (2)
S5	0.0199 (3)	0.0155 (3)	0.0191 (3)	0.0000 (2)	0.0034 (2)	−0.0011 (2)
S6	0.0147 (3)	0.0184 (3)	0.0152 (3)	−0.0020 (2)	0.0024 (2)	0.0001 (2)
Na1	0.0189 (8)	0.0289 (6)	0.0246 (10)	0.0034 (7)	0.0020 (6)	0.0014 (7)
Na2	0.0443 (10)	0.0276 (9)	0.0381 (9)	0.0029 (8)	0.0221 (7)	0.0028 (7)
Na3	0.0316 (8)	0.0215 (8)	0.0435 (9)	−0.0035 (6)	0.0166 (7)	−0.0025 (7)
Na4	0.0304 (8)	0.0322 (9)	0.0329 (8)	0.0042 (7)	0.0047 (6)	−0.0003 (7)
Na5	0.0373 (8)	0.0286 (8)	0.0307 (7)	0.0025 (6)	0.0102 (6)	0.0006 (6)
Na6	0.0404 (8)	0.0294 (8)	0.0275 (7)	−0.0010 (7)	0.0105 (6)	0.0000 (6)
Na7	0.0439 (9)	0.0339 (9)	0.0328 (8)	0.0072 (7)	0.0106 (7)	−0.0009 (7)
Na8	0.0416 (9)	0.0309 (8)	0.0244 (7)	−0.0062 (6)	0.0071 (6)	−0.0026 (6)
Na9	0.0379 (8)	0.0279 (7)	0.0305 (7)	−0.0092 (6)	0.0094 (6)	−0.0014 (6)
Na10	0.0253 (7)	0.0400 (10)	0.0347 (8)	0.0013 (7)	0.0055 (6)	0.0093 (8)
O1	0.0289 (17)	0.0199 (10)	0.0338 (15)	0.0041 (9)	−0.0027 (12)	0.0025 (10)
O2	0.0303 (17)	0.0186 (9)	0.0268 (12)	0.0011 (9)	−0.0080 (12)	0.0012 (10)
O3	0.0129 (11)	0.061 (2)	0.058 (2)	0.0067 (12)	0.0109 (12)	0.0228 (16)
O4	0.0430 (18)	0.065 (2)	0.0141 (11)	−0.0114 (15)	0.0065 (11)	0.0007 (11)
O5	0.0279 (12)	0.0216 (11)	0.0282 (11)	0.0026 (9)	−0.0152 (9)	0.0013 (9)
O6	0.0148 (9)	0.0350 (12)	0.0139 (9)	−0.0013 (8)	0.0018 (7)	0.0000 (8)
O7	0.0141 (9)	0.0350 (12)	0.0186 (10)	0.0011 (8)	0.0030 (8)	−0.0044 (9)
O8	0.0314 (14)	0.0268 (13)	0.0374 (15)	−0.0090 (11)	0.0047 (12)	−0.0150 (11)
O9	0.0248 (11)	0.0296 (12)	0.0230 (11)	0.0047 (10)	−0.0019 (9)	0.0060 (9)
O10	0.0182 (11)	0.0410 (16)	0.0365 (15)	−0.0026 (9)	0.0061 (10)	0.0041 (11)
O11	0.0361 (15)	0.0156 (11)	0.0327 (14)	0.0006 (10)	−0.0050 (11)	−0.0025 (9)
O12	0.0322 (13)	0.0285 (12)	0.0173 (10)	0.0023 (9)	0.0015 (9)	−0.0030 (8)
O13	0.0170 (14)	0.124 (4)	0.048 (2)	0.0050 (16)	0.0079 (14)	−0.010 (2)
O14	0.062 (2)	0.0415 (18)	0.0446 (17)	−0.0315 (16)	0.0200 (16)	−0.0234 (14)
O15	0.095 (3)	0.0233 (16)	0.047 (2)	0.0139 (18)	0.0009 (19)	0.0100 (14)
O16	0.0369 (15)	0.0412 (17)	0.0364 (15)	0.0176 (13)	0.0157 (12)	0.0060 (12)
O17	0.067 (2)	0.0360 (15)	0.0256 (12)	−0.0082 (15)	−0.0131 (13)	−0.0001 (11)
O18	0.0328 (14)	0.0247 (13)	0.0505 (17)	−0.0100 (11)	0.0026 (12)	0.0077 (12)
O19	0.0340 (13)	0.0185 (11)	0.0327 (12)	0.0060 (10)	0.0064 (10)	0.0066 (10)
O20	0.061 (2)	0.0335 (15)	0.0463 (17)	−0.0173 (14)	0.0322 (16)	−0.0043 (13)
O21	0.055 (2)	0.051 (2)	0.0305 (14)	0.0244 (16)	−0.0142 (13)	−0.0086 (13)
O22	0.0422 (16)	0.0174 (12)	0.0462 (16)	−0.0088 (11)	0.0136 (13)	−0.0100 (11)
O23	0.0315 (13)	0.0301 (14)	0.0357 (14)	0.0117 (11)	0.0011 (11)	−0.0060 (11)
O24	0.0282 (13)	0.0338 (15)	0.0361 (14)	−0.0134 (11)	0.0032 (11)	−0.0101 (11)
O25	0.054 (2)	0.077 (3)	0.0164 (12)	−0.0252 (19)	0.0072 (13)	−0.0010 (13)
O26	0.061 (2)	0.0192 (14)	0.0521 (19)	0.0046 (14)	0.0127 (16)	0.0080 (13)
O27	0.0293 (13)	0.0275 (12)	0.0273 (12)	−0.0021 (10)	−0.0021 (9)	−0.0035 (9)
O28	0.0523 (18)	0.0341 (16)	0.0447 (17)	0.0046 (13)	−0.0214 (14)	−0.0079 (12)
O29	0.0484 (17)	0.0231 (14)	0.0391 (15)	−0.0034 (13)	0.0099 (12)	0.0009 (12)

Geometric parameters (Å, º)

U1—O1	1.776 (2)	Na3—O28	2.534 (4)
U1—O2	1.779 (2)	Na3—O5^v	2.622 (3)
U1—O3	2.281 (3)	Na3—O6	2.780 (3)
U1—O4	2.315 (3)	Na4—O18	2.359 (3)
U1—O5	2.317 (2)	Na4—O12	2.454 (3)
U1—O6	2.424 (2)	Na4—O7	2.466 (3)
U1—O7	2.480 (2)	Na4—O15^viii	2.533 (5)
U1—S1	3.0915 (9)	Na4—O25	2.652 (4)
S1—O8	1.448 (3)	Na4—O16	2.862 (4)
S1—O9	1.463 (3)	Na4—O14^viii	2.950 (5)
S1—O7	1.495 (2)	Na5—O19^ix	2.336 (3)
S1—O6	1.501 (2)	Na5—O17	2.354 (3)
S2—O10	1.455 (3)	Na5—O15^viii	2.364 (4)
S2—O11	1.455 (3)	Na5—O11^viii	2.563 (3)
S2—O12^i	1.464 (3)	Na5—O21^vii	2.672 (5)
S2—O5	1.524 (3)	Na5—O2^viii	2.749 (4)
S3—O13	1.436 (4)	Na5—O20^vii	2.763 (4)
S3—O14	1.440 (3)	Na6—O16	2.290 (3)
S3—O15	1.451 (3)	Na6—O20^x	2.298 (3)
S3—O4	1.495 (3)	Na6—O17^xi	2.353 (4)
S4—O16	1.461 (3)	Na6—O21^xii	2.387 (4)
S4—O17	1.462 (3)	Na6—O2	2.707 (3)
S4—O18	1.473 (3)	Na7—O22^xii	2.388 (3)
S4—O19	1.475 (3)	Na7—O29^xii	2.400 (4)
S5—O20	1.462 (3)	Na7—O27^v	2.502 (3)
S5—O21	1.464 (3)	Na7—O18^vii	2.507 (3)
S5—O22	1.465 (3)	Na7—O26^vii	2.510 (4)
S5—O23	1.476 (3)	Na7—O8	2.678 (3)
S6—O24	1.443 (3)	Na7—O25^vii	2.899 (5)
S6—O25	1.450 (3)	Na8—O21^vii	2.320 (3)
S6—O26	1.455 (3)	Na8—O22^xii	2.349 (3)
S6—O3	1.496 (3)	Na8—O15^viii	2.388 (5)
Na1—O13^ii	2.331 (5)	Na8—O8	2.418 (3)
Na1—O25^iii	2.377 (5)	Na8—O16	2.491 (4)
Na1—O9^iv	2.476 (4)	Na8—O27^v	2.858 (3)
Na1—O27	2.477 (3)	Na8—O17	2.948 (4)
Na1—O12^iii	2.508 (5)	Na9—O26	2.299 (4)
Na1—O1	2.609 (3)	Na9—O19^xi	2.306 (3)
Na1—O10^v	2.772 (5)	Na9—O29^xi	2.373 (3)
Na2—O14^ii	2.299 (4)	Na9—O23^i	2.394 (3)
Na2—O24	2.385 (3)	Na9—O11	2.410 (3)
Na2—O9^iv	2.444 (3)	Na10—O23^x	2.374 (3)
Na2—O28^vi	2.526 (4)	Na10—O10^vii	2.409 (3)
Na2—O10	2.558 (3)	Na10—O6	2.420 (3)
Na2—O5	2.590 (3)	Na10—O24^vii	2.680 (4)
Na3—O24^vii	2.260 (3)	Na10—O26^vii	2.726 (4)
Na3—O14^v	2.313 (4)	Na10—O4	2.738 (4)
Na3—O12^iii	2.436 (3)	Na10—O13	2.783 (5)
Na3—O9	2.483 (3)	Na10—O20^x	2.807 (4)
O1—U1—O2	178.20 (14)	O12—Na4—O25	69.46 (10)
O1—U1—O3	89.96 (14)	O7—Na4—O25	106.81 (11)
O2—U1—O3	89.70 (14)	O15^viii—Na4—O25	160.88 (14)
O1—U1—O4	93.80 (14)	O18—Na4—O16	53.33 (9)
O2—U1—O4	87.21 (14)	O12—Na4—O16	145.32 (11)
O3—U1—O4	156.68 (12)	O7—Na4—O16	75.57 (10)
O1—U1—O5	84.75 (10)	O15^viii—Na4—O16	75.97 (11)
O2—U1—O5	96.92 (10)	O25—Na4—O16	116.72 (12)
O3—U1—O5	78.87 (13)	O18—Na4—O14^viii	142.76 (12)
O4—U1—O5	78.58 (11)	O12—Na4—O14^viii	70.69 (10)
O1—U1—O6	86.86 (10)	O7—Na4—O14^viii	78.39 (10)
O2—U1—O6	92.01 (10)	O15^viii—Na4—O14^viii	50.32 (10)
O3—U1—O6	130.10 (11)	O25—Na4—O14^viii	122.80 (12)
O4—U1—O6	73.14 (10)	O16—Na4—O14^viii	119.54 (10)
O5—U1—O6	149.84 (9)	O19^ix—Na5—O17	82.43 (12)
O1—U1—O7	90.52 (11)	O19^ix—Na5—O15^viii	161.09 (16)
O2—U1—O7	87.69 (11)	O17—Na5—O15^viii	86.56 (13)
O3—U1—O7	73.32 (11)	O19^ix—Na5—O11^viii	78.81 (10)
O4—U1—O7	129.56 (10)	O17—Na5—O11^viii	104.46 (12)
O5—U1—O7	151.79 (9)	O15^viii—Na5—O11^viii	89.20 (15)
O6—U1—O7	56.95 (7)	O19^ix—Na5—O21^vii	112.74 (12)
O8—S1—O9	112.13 (18)	O17—Na5—O21^vii	73.28 (12)
O8—S1—O7	112.20 (16)	O15^viii—Na5—O21^vii	78.33 (15)
O9—S1—O7	109.66 (15)	O11^viii—Na5—O21^vii	167.39 (12)
O8—S1—O6	110.08 (16)	O19^ix—Na5—O2^viii	85.15 (10)
O9—S1—O6	109.73 (15)	O17—Na5—O2^viii	165.73 (13)
O7—S1—O6	102.62 (13)	O15^viii—Na5—O2^viii	103.42 (12)
O8—S1—U1	126.01 (14)	O11^viii—Na5—O2^viii	66.07 (9)
O9—S1—U1	121.80 (12)	O21^vii—Na5—O2^viii	118.35 (11)
O7—S1—U1	52.38 (9)	O19^ix—Na5—O20^vii	102.57 (11)
O6—S1—U1	50.25 (9)	O17—Na5—O20^vii	122.91 (12)
O10—S2—O11	112.61 (17)	O15^viii—Na5—O20^vii	96.32 (15)
O10—S2—O12^i	110.09 (18)	O11^viii—Na5—O20^vii	132.51 (11)
O11—S2—O12^i	111.79 (16)	O21^vii—Na5—O20^vii	52.07 (9)
O10—S2—O5	106.38 (17)	O2^viii—Na5—O20^vii	66.77 (9)
O11—S2—O5	109.36 (15)	O16—Na6—O20^x	159.86 (14)
O12^i—S2—O5	106.28 (16)	O16—Na6—O17^xi	94.65 (12)
O13—S3—O14	112.9 (2)	O20^x—Na6—O17^xi	101.54 (14)
O13—S3—O15	110.6 (3)	O16—Na6—O21^xii	97.24 (14)
O14—S3—O15	109.6 (3)	O20^x—Na6—O21^xii	97.58 (14)
O13—S3—O4	105.6 (2)	O17^xi—Na6—O21^xii	78.85 (13)
O14—S3—O4	110.06 (19)	O16—Na6—O2	92.60 (13)
O15—S3—O4	108.1 (2)	O20^x—Na6—O2	74.10 (12)
O16—S4—O17	108.8 (2)	O17^xi—Na6—O2	95.63 (11)
O16—S4—O18	108.8 (2)	O21^xii—Na6—O2	169.05 (12)
O17—S4—O18	110.30 (19)	O22^xii—Na7—O29^xii	92.03 (11)
O16—S4—O19	110.86 (16)	O22^xii—Na7—O27^v	76.41 (11)
O17—S4—O19	108.86 (18)	O29^xii—Na7—O27^v	151.02 (13)
O18—S4—O19	109.21 (16)	O22^xii—Na7—O18^vii	109.89 (13)
O20—S5—O21	109.3 (2)	O29^xii—Na7—O18^vii	91.61 (12)
O20—S5—O22	110.87 (18)	O27^v—Na7—O18^vii	68.43 (10)
O21—S5—O22	109.6 (2)	O22^xii—Na7—O26^vii	152.38 (15)
O20—S5—O23	108.6 (2)	O29^xii—Na7—O26^vii	74.00 (11)
O21—S5—O23	109.23 (18)	O27^v—Na7—O26^vii	126.39 (12)
O22—S5—O23	109.25 (18)	O18^vii—Na7—O26^vii	94.50 (13)
O24—S6—O25	112.42 (19)	O22^xii—Na7—O8	78.75 (11)
O24—S6—O26	109.5 (2)	O29^xii—Na7—O8	128.33 (13)
O25—S6—O26	111.3 (2)	O27^v—Na7—O8	76.01 (10)
O24—S6—O3	106.9 (2)	O18^vii—Na7—O8	139.51 (12)
O25—S6—O3	107.3 (2)	O26^vii—Na7—O8	91.23 (12)
O26—S6—O3	109.3 (2)	O22^xii—Na7—O25^vii	146.16 (12)
O13^ii—Na1—O25^iii	159.25 (19)	O29^xii—Na7—O25^vii	121.72 (12)
O13^ii—Na1—O9^iv	86.26 (18)	O27^v—Na7—O25^vii	74.38 (10)
O25^iii—Na1—O9^iv	85.27 (16)	O18^vii—Na7—O25^vii	74.45 (11)
O13^ii—Na1—O27	81.97 (17)	O26^vii—Na7—O25^vii	52.01 (10)
O25^iii—Na1—O27	85.00 (15)	O8—Na7—O25^vii	77.95 (11)
O9^iv—Na1—O27	116.71 (15)	O21^vii—Na8—O22^xii	91.29 (15)
O13^ii—Na1—O12^iii	120.06 (19)	O21^vii—Na8—O15^viii	85.30 (16)
O25^iii—Na1—O12^iii	73.17 (16)	O22^xii—Na8—O15^viii	174.39 (16)
O9^iv—Na1—O12^iii	151.43 (17)	O21^vii—Na8—O8	159.61 (14)
O27—Na1—O12^iii	80.50 (12)	O22^xii—Na8—O8	85.01 (11)
O13^ii—Na1—O1	99.13 (18)	O15^viii—Na8—O8	96.65 (13)
O25^iii—Na1—O1	98.72 (17)	O21^vii—Na8—O16	118.87 (13)
O9^iv—Na1—O1	83.74 (10)	O22^xii—Na8—O16	99.48 (12)
O27—Na1—O1	159.51 (19)	O15^viii—Na8—O16	86.07 (14)
O12^iii—Na1—O1	81.33 (12)	O8—Na8—O16	81.53 (11)
O13^ii—Na1—O10^v	66.61 (16)	O21^vii—Na8—O27^v	85.92 (11)
O25^iii—Na1—O10^v	125.40 (18)	O22^xii—Na8—O27^v	70.28 (10)
O9^iv—Na1—O10^v	148.78 (18)	O15^viii—Na8—O27^v	104.99 (13)
O27—Na1—O10^v	76.03 (11)	O8—Na8—O27^v	73.93 (10)
O12^iii—Na1—O10^v	53.59 (11)	O16—Na8—O27^v	153.98 (10)
O1—Na1—O10^v	85.59 (13)	O21^vii—Na8—O17	68.53 (11)
O14^ii—Na2—O24	76.63 (13)	O22^xii—Na8—O17	109.07 (11)
O14^ii—Na2—O9^iv	94.55 (13)	O15^viii—Na8—O17	73.80 (13)
O24—Na2—O9^iv	155.63 (14)	O8—Na8—O17	131.55 (11)
O14^ii—Na2—O28^vi	82.26 (15)	O16—Na8—O17	50.99 (9)
O24—Na2—O28^vi	77.98 (12)	O27^v—Na8—O17	154.46 (10)
O9^iv—Na2—O28^vi	123.88 (13)	O26—Na9—O19^xi	154.92 (15)
O14^ii—Na2—O10	149.75 (14)	O26—Na9—O29^xi	78.49 (12)
O24—Na2—O10	77.80 (12)	O19^xi—Na9—O29^xi	97.22 (12)
O9^iv—Na2—O10	115.22 (11)	O26—Na9—O23^i	93.44 (14)
O28^vi—Na2—O10	76.83 (12)	O19^xi—Na9—O23^i	111.62 (12)
O14^ii—Na2—O5	144.08 (15)	O29^xi—Na9—O23^i	96.41 (12)
O24—Na2—O5	96.64 (12)	O26—Na9—O11	100.44 (12)
O9^iv—Na2—O5	77.07 (10)	O19^xi—Na9—O11	82.65 (10)
O28^vi—Na2—O5	131.50 (12)	O29^xi—Na9—O11	177.19 (14)
O10—Na2—O5	55.19 (9)	O23^i—Na9—O11	86.23 (11)
O24^vii—Na3—O14^v	78.88 (14)	O23^x—Na10—O10^vii	88.50 (10)
O24^vii—Na3—O12^iii	156.81 (13)	O23^x—Na10—O6	134.20 (12)
O14^v—Na3—O12^iii	83.14 (14)	O10^vii—Na10—O6	136.91 (12)
O24^vii—Na3—O9	86.97 (11)	O23^x—Na10—O24^vii	133.17 (11)
O14^v—Na3—O9	135.18 (14)	O10^vii—Na10—O24^vii	75.03 (11)
O12^iii—Na3—O9	116.18 (11)	O6—Na10—O24^vii	70.41 (9)
O24^vii—Na3—O28	80.12 (12)	O23^x—Na10—O26^vii	83.84 (11)
O14^v—Na3—O28	81.83 (13)	O10^vii—Na10—O26^vii	85.42 (11)
O12^iii—Na3—O28	82.96 (11)	O6—Na10—O26^vii	92.79 (11)
O9—Na3—O28	137.39 (13)	O24^vii—Na10—O26^vii	51.91 (9)
O24^vii—Na3—O5^v	135.32 (13)	O23^x—Na10—O4	109.25 (11)
O14^v—Na3—O5^v	84.97 (12)	O10^vii—Na10—O4	110.84 (12)
O12^iii—Na3—O5^v	56.27 (9)	O6—Na10—O4	66.08 (9)
O9—Na3—O5^v	75.82 (10)	O24^vii—Na10—O4	117.58 (11)
O28—Na3—O5^v	138.35 (12)	O26^vii—Na10—O4	158.80 (12)
O24^vii—Na3—O6	70.75 (11)	O23^x—Na10—O13	87.85 (14)
O14^v—Na3—O6	147.90 (13)	O10^vii—Na10—O13	65.50 (11)
O12^iii—Na3—O6	122.70 (11)	O6—Na10—O13	113.28 (12)
O9—Na3—O6	54.49 (8)	O24^vii—Na10—O13	121.68 (13)
O28—Na3—O6	82.96 (10)	O26^vii—Na10—O13	149.96 (12)
O5^v—Na3—O6	124.20 (10)	O4—Na10—O13	50.03 (10)
O18—Na4—O12	97.36 (11)	O23^x—Na10—O20^x	54.06 (9)
O18—Na4—O7	124.36 (12)	O10^vii—Na10—O20^x	141.04 (11)
O12—Na4—O7	137.71 (12)	O6—Na10—O20^x	81.81 (10)
O18—Na4—O15^viii	96.87 (12)	O24^vii—Na10—O20^x	136.91 (12)
O12—Na4—O15^viii	91.95 (13)	O26^vii—Na10—O20^x	99.14 (12)
O7—Na4—O15^viii	89.82 (13)	O4—Na10—O20^x	77.04 (11)
O18—Na4—O25	81.71 (13)

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