Tetrapotassium disodium decavanadate(V) decahydrate

The title compound, K₄Na₂[V₁₀O₂₈]·10H₂O, is isostructural with the known disodium tetra­ammonium salt of the centrosymmetric [V₁₀O₁₈]^6- anion.

S1. Comment

In the course of our work with Schiff base vanadium complexes, several polyoxovanadates formed, particularly crystalline decavanadates (Cavaco et al., 1995; Costa Pessoa et al., 1998, 1999). In the present case, we isolated the title compound, (I), while attempting to obtain N-salicylidenetyrosinate (sal–Tyr) oxovanadium complexes. The hydrolysis of vanadium(V) is very complex, but by combination of potentiometric and ⁵¹V NMR spectroscopy, its speciation was determined in the whole pH range (Pettersson et al., 1983). In the slightly acid pH range (3.0–5.5), yellow–orange decavanadates [H_nV₁₀O₂₈]^(6-n)- form. The hydrolysis of vanadium(IV) is also quite complex. On increasing the pH starting in the acid range, V^IVO²⁺ hydroxide precipitates in the pH range 4–8 (Boas & Costa Pessoa, 1987). In the present case, the pH is ~5, but the sal–Tyr ligand coordinates to V^IVO²⁺ and hinders the precipitation of the hydroxide. The VO(sal–Tyr) complex is soluble, it does not precipitate and the formation of a compound of V^V may then be explained by the slow oxidation of V^IVO²⁺ by atmospheric oxygen. Decavanadates being the dominant V^V species at pH ~5 therefore form slowly as crystalline compounds. This explains why several decavanadate salts have been obtained by our group under relatively similar conditions. In particular, this compound is isostructural with the disodium tetraammonium salt (Cavaco et al., 1995), with the replacement of NH₄⁺ by K⁺ ions. Valence bond calculations show that all V—O and V═O bond distances are consistent with the non-protonation of the decavanadate ion, thus confirming the assumed overall charge of -6.

S2. Experimental

Tyrosine was dissolved in 15 ml of an aqueous solution containing sodium acetate (2 mmol) and potassium hydroxide (2 mmol), and salicylaldehyde (4 mmol) dissolved in 18 ml of ethanol was added. 14 ml of an aqueous solution of VOSO₄ (4 mmol) were added slowly, followed by 1 ml of pyridine. The mixture was kept in a beaker covered with Parafilm at 277–279 K and after five weeks red–brown crystals of the title compound were separated.

S3. Refinement

K– and Na-atom sites were assigned on the basis of the observed electron density. H atoms of water molecules were refined with their 1–2 and 1–3 distances restrained to 0.9 (2) and 1.45 (4) Å, respectively. Crystallographic software was used through the OSCAIL interface of McArdle (1995).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: SDP (Nonius, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick & Schneider, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick & Schneider, 1997).

(I)

Crystal data

K4Na2[V10O28]·10H2O	Z = 1
Mr = 1339.94	F(000) = 652
Triclinic, P1	Dx = 2.678 Mg m^−3
a = 8.5893 (6) Å	Mo Kα radiation, λ = 0.71069 Å
b = 10.3543 (6) Å	Cell parameters from 25 reflections
c = 10.9893 (6) Å	θ = 14.0–15.9°
α = 69.194 (5)°	µ = 3.33 mm^−1
β = 87.122 (5)°	T = 293 K
γ = 66.172 (5)°	Prism, dark orange
V = 830.75 (9) Å^3	0.40 × 0.35 × 0.30 mm

Data collection

Nonius CAD-4 diffractometer	4320 reflections with I > 2σ(I)
Radiation source: Nonius FR-591 rotating anode generator	Rint = 0.033
Graphite monochromator	θmax = 30.0°, θmin = 2.0°
ω–2θ scans	h = −12→0
Absorption correction: ψ scan (North et al., 1968)	k = −14→13
Tmin = 0.252, Tmax = 0.368	l = −15→15
5134 measured reflections	3 standard reflections every 60 min
4832 independent reflections	intensity decay: 0.9%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	All H-atom parameters refined
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.032P)^2 + 1.1139P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.010
4832 reflections	Δρmax = 1.06 e Å^−3
284 parameters	Δρmin = −1.28 e Å^−3
15 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (4)

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
V1	0.81086 (4)	0.99951 (4)	0.52006 (3)	0.01349 (7)
V2	1.12315 (4)	0.71476 (4)	0.49940 (3)	0.01603 (8)
V3	0.97440 (5)	0.70792 (4)	0.76604 (3)	0.01836 (8)
V4	0.97047 (4)	1.00558 (4)	0.25469 (3)	0.01601 (8)
V5	1.32986 (4)	0.71094 (4)	0.72355 (4)	0.01809 (8)
O2	1.1596 (2)	0.61295 (18)	0.41017 (16)	0.0236 (3)
O3	0.8942 (2)	0.6027 (2)	0.86523 (17)	0.0292 (4)
O4	1.0054 (2)	0.90210 (18)	0.16651 (15)	0.0231 (3)
O5	1.5240 (2)	0.61032 (19)	0.79070 (17)	0.0271 (3)
O6	0.93052 (17)	1.12532 (15)	0.39354 (13)	0.0140 (3)
O7	0.89665 (17)	0.88038 (15)	0.41290 (14)	0.0148 (3)
O8	0.81796 (17)	1.11693 (15)	0.61964 (14)	0.0146 (3)
O13	0.76500 (18)	0.86770 (16)	0.64264 (14)	0.0176 (3)
O15	0.62465 (18)	1.12507 (17)	0.42806 (15)	0.0180 (3)
O23	1.01890 (19)	0.62951 (16)	0.63169 (15)	0.0192 (3)
O25	1.32989 (18)	0.63232 (16)	0.59548 (15)	0.0189 (3)
O34	1.05651 (19)	1.14232 (17)	0.16503 (14)	0.0191 (3)
O35	1.20537 (19)	0.61595 (17)	0.82557 (15)	0.0203 (3)
O45	0.74827 (18)	1.13821 (16)	0.20181 (14)	0.0185 (3)
K1	1.31538 (7)	0.28838 (6)	0.50606 (6)	0.03117 (12)
K2	1.76536 (12)	0.31748 (9)	0.92721 (7)	0.0624 (3)
Na1	0.57073 (12)	0.83232 (11)	0.13120 (9)	0.0267 (2)
O1W	1.2960 (2)	1.0124 (2)	0.01396 (18)	0.0302 (4)
O2W	0.4705 (2)	1.0180 (2)	0.7446 (2)	0.0368 (4)
O3W	1.1602 (3)	0.3170 (2)	0.7440 (2)	0.0429 (5)
O4W	1.4305 (3)	0.3230 (2)	0.9773 (2)	0.0427 (5)
O5W	0.5293 (3)	1.3148 (2)	0.7010 (3)	0.0511 (6)
H11W	1.229 (4)	1.053 (4)	0.064 (3)	0.047 (10)*
H12W	1.230 (4)	1.012 (5)	−0.042 (3)	0.067 (13)*
H21W	0.564 (3)	0.965 (3)	0.719 (3)	0.039 (9)*
H22W	0.406 (4)	0.968 (4)	0.753 (4)	0.047 (10)*
H31W	1.103 (4)	0.416 (2)	0.718 (4)	0.058 (11)*
H32W	1.089 (4)	0.276 (4)	0.749 (4)	0.067 (13)*
H41W	1.347 (4)	0.414 (3)	0.939 (4)	0.066 (13)*
H42W	1.415 (6)	0.289 (5)	1.059 (2)	0.081 (15)*
H51W	0.615 (3)	1.265 (3)	0.667 (3)	0.049 (10)*
H52W	0.494 (4)	1.413 (2)	0.660 (3)	0.054 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.01202 (14)	0.01221 (14)	0.01500 (15)	−0.00463 (11)	0.00070 (11)	−0.00394 (11)
V2	0.01828 (16)	0.01105 (14)	0.01692 (16)	−0.00441 (12)	0.00011 (12)	−0.00478 (12)
V3	0.01893 (16)	0.01500 (15)	0.01711 (16)	−0.00706 (13)	0.00116 (12)	−0.00126 (12)
V4	0.01863 (16)	0.01432 (15)	0.01333 (15)	−0.00507 (12)	−0.00040 (12)	−0.00486 (12)
V5	0.01524 (15)	0.01448 (15)	0.01869 (16)	−0.00318 (12)	−0.00345 (12)	−0.00231 (12)
O2	0.0261 (8)	0.0181 (7)	0.0278 (8)	−0.0067 (6)	0.0014 (6)	−0.0123 (6)
O3	0.0318 (9)	0.0267 (8)	0.0257 (8)	−0.0158 (7)	0.0056 (7)	−0.0019 (7)
O4	0.0277 (8)	0.0241 (8)	0.0201 (7)	−0.0099 (6)	0.0023 (6)	−0.0117 (6)
O5	0.0204 (7)	0.0228 (8)	0.0298 (9)	−0.0028 (6)	−0.0067 (6)	−0.0064 (7)
O6	0.0133 (6)	0.0118 (6)	0.0145 (6)	−0.0036 (5)	0.0003 (5)	−0.0036 (5)
O7	0.0144 (6)	0.0130 (6)	0.0168 (6)	−0.0054 (5)	0.0005 (5)	−0.0053 (5)
O8	0.0141 (6)	0.0130 (6)	0.0152 (6)	−0.0040 (5)	0.0011 (5)	−0.0054 (5)
O13	0.0166 (6)	0.0164 (6)	0.0183 (7)	−0.0074 (5)	0.0019 (5)	−0.0040 (5)
O15	0.0141 (6)	0.0178 (7)	0.0197 (7)	−0.0052 (5)	−0.0003 (5)	−0.0054 (5)
O23	0.0215 (7)	0.0132 (6)	0.0212 (7)	−0.0073 (5)	0.0004 (5)	−0.0040 (5)
O25	0.0169 (6)	0.0130 (6)	0.0219 (7)	−0.0020 (5)	−0.0010 (5)	−0.0054 (5)
O34	0.0216 (7)	0.0183 (7)	0.0152 (6)	−0.0077 (6)	0.0024 (5)	−0.0043 (5)
O35	0.0211 (7)	0.0151 (6)	0.0179 (7)	−0.0055 (6)	−0.0021 (5)	−0.0003 (5)
O45	0.0181 (7)	0.0175 (7)	0.0168 (7)	−0.0054 (5)	−0.0030 (5)	−0.0045 (5)
K1	0.0296 (3)	0.0270 (2)	0.0378 (3)	−0.0107 (2)	0.0032 (2)	−0.0141 (2)
K2	0.0668 (5)	0.0434 (4)	0.0374 (4)	0.0147 (3)	−0.0052 (3)	−0.0130 (3)
Na1	0.0298 (5)	0.0238 (4)	0.0265 (5)	−0.0123 (4)	0.0018 (4)	−0.0075 (4)
O1W	0.0250 (8)	0.0381 (10)	0.0239 (8)	−0.0100 (7)	0.0032 (7)	−0.0110 (7)
O2W	0.0299 (9)	0.0437 (11)	0.0559 (13)	−0.0211 (9)	0.0183 (9)	−0.0347 (10)
O3W	0.0377 (11)	0.0196 (8)	0.0636 (14)	−0.0086 (8)	−0.0177 (10)	−0.0072 (9)
O4W	0.0594 (14)	0.0279 (10)	0.0266 (10)	−0.0045 (9)	−0.0088 (9)	−0.0082 (8)
O5W	0.0537 (13)	0.0235 (9)	0.0639 (15)	−0.0127 (9)	0.0389 (12)	−0.0106 (10)

Geometric parameters (Å, º)

V1—O15	1.6790 (14)	O6—V5^i	2.2819 (14)
V1—O13	1.7052 (15)	O6—V3^i	2.3597 (14)
V1—O7	1.9135 (14)	O7—K1^ii	2.9097 (15)
V1—O8	1.9213 (14)	O8—V4^i	1.9909 (14)
V1—O6	2.0828 (14)	O8—V2^i	2.0076 (14)
V1—O6^i	2.1276 (13)	O13—K1^ii	2.9411 (16)
V1—V5^i	3.0515 (5)	O15—V5^i	2.0670 (15)
V1—V3	3.0907 (5)	O15—K1^iii	2.7968 (15)
V1—K1^ii	3.6599 (7)	O23—K1^ii	2.9679 (16)
V1—K1^iii	4.0665 (7)	O34—V3^i	1.8789 (15)
V2—O2	1.6147 (16)	O34—K2^v	3.1619 (17)
V2—O23	1.8140 (16)	O35—K2^iv	3.0754 (18)
V2—O25	1.8221 (15)	O45—V5^i	1.8897 (15)
V2—O7	1.9903 (14)	O45—K2^v	2.9614 (17)
V2—O8^i	2.0076 (14)	K1—O15^viii	2.7968 (15)
V2—O6^i	2.2475 (14)	K1—O7^ii	2.9097 (15)
V2—V4	3.0708 (5)	K1—O3W	2.930 (3)
V2—V5	3.0878 (5)	K1—O2W^viii	2.934 (2)
V2—K1^ii	3.7836 (7)	K1—O13^ii	2.9411 (16)
V2—K1	4.0143 (7)	K1—O23^ii	2.9679 (16)
V3—O3	1.5925 (17)	K1—O5W^viii	3.043 (3)
V3—O35	1.8525 (15)	K1—V1^ii	3.6599 (7)
V3—O23	1.8787 (16)	K1—Na1^ii	3.7780 (12)
V3—O34^i	1.8789 (15)	K1—V2^ii	3.7836 (7)
V3—O13	2.0144 (15)	K1—V5^vi	3.8581 (7)
V3—O6^i	2.3597 (14)	K2—O4^vi	2.8197 (17)
V3—V5	3.0764 (5)	K2—O4W	2.883 (3)
V3—V4^i	3.1177 (5)	K2—O45^ix	2.9614 (17)
V3—K1^ii	3.9658 (7)	K2—O35^iv	3.0754 (18)
V3—K2^iv	4.0101 (10)	K2—O34^ix	3.1619 (17)
V4—O4	1.6204 (15)	K2—O5W^viii	3.300 (3)
V4—O45	1.8146 (15)	K2—O3^x	3.398 (2)
V4—O34	1.8174 (15)	K2—V4^ix	3.7773 (9)
V4—O8^i	1.9909 (14)	K2—V5^iv	3.8160 (9)
V4—O7	2.0143 (14)	K2—Na1^ii	3.9576 (15)
V4—O6	2.2206 (14)	K2—V3^iv	4.0101 (10)
V4—V5^i	3.1058 (5)	Na1—O5W^xi	2.315 (2)
V4—V3^i	3.1177 (5)	Na1—O4W^ii	2.320 (2)
V4—K2^v	3.7773 (9)	Na1—O2W^xi	2.324 (2)
V5—O5	1.6077 (16)	Na1—O3W^ii	2.353 (2)
V5—O35	1.8203 (16)	Na1—O1W^vii	2.398 (2)
V5—O25	1.8593 (15)	Na1—O1W^xii	2.434 (2)
V5—O45^i	1.8897 (15)	Na1—Na1^xiii	3.4175 (19)
V5—O15^i	2.0670 (15)	Na1—K1^ii	3.7780 (12)
V5—O6^i	2.2819 (14)	Na1—K2^ii	3.9576 (15)
V5—V1^i	3.0515 (5)	O1W—Na1^x	2.398 (2)
V5—V4^i	3.1058 (5)	O1W—Na1^xii	2.434 (2)
V5—K2^iv	3.8160 (9)	O2W—Na1^xi	2.324 (2)
V5—K1^vi	3.8581 (7)	O2W—K1^iii	2.934 (2)
O2—K1	2.8613 (17)	O3W—Na1^ii	2.353 (2)
O3—K2^vii	3.398 (2)	O4W—Na1^ii	2.320 (2)
O4—K2^vi	2.8197 (17)	O5W—Na1^xi	2.315 (2)
O5—K2	2.7827 (17)	O5W—K1^iii	3.043 (3)
O6—V1^i	2.1276 (13)	O5W—K2^iii	3.300 (3)
O6—V2^i	2.2475 (14)
O15—V1—O13	106.38 (7)	O15^i—V5—K2^iv	131.13 (5)
O15—V1—O7	98.08 (7)	O6^i—V5—K2^iv	102.16 (4)
O13—V1—O7	96.15 (7)	V1^i—V5—K2^iv	125.554 (17)
O15—V1—O8	97.10 (7)	V3—V5—K2^iv	70.220 (19)
O13—V1—O8	97.06 (7)	V2—V5—K2^iv	131.09 (2)
O7—V1—O8	156.18 (6)	V4^i—V5—K2^iv	65.206 (15)
O15—V1—O6	88.31 (6)	O5—V5—K1^vi	63.46 (7)
O13—V1—O6	165.31 (6)	O35—V5—K1^vi	150.57 (5)
O7—V1—O6	81.12 (6)	O25—V5—K1^vi	64.79 (5)
O8—V1—O6	81.09 (6)	O45^i—V5—K1^vi	117.53 (5)
O15—V1—O6^i	166.79 (7)	O15^i—V5—K1^vi	44.71 (4)
O13—V1—O6^i	86.81 (6)	O6^i—V5—K1^vi	109.31 (4)
O7—V1—O6^i	80.82 (6)	V1^i—V5—K1^vi	71.015 (14)
O8—V1—O6^i	80.21 (6)	V3—V5—K1^vi	147.784 (16)
O6—V1—O6^i	78.51 (6)	V2—V5—K1^vi	86.845 (14)
O15—V1—V5^i	39.93 (5)	V4^i—V5—K1^vi	126.360 (16)
O13—V1—V5^i	146.31 (5)	K2^iv—V5—K1^vi	141.86 (2)
O7—V1—V5^i	90.49 (4)	V2—O2—K1	125.15 (8)
O8—V1—V5^i	89.44 (4)	V3—O3—K2^vii	147.01 (10)
O6—V1—V5^i	48.38 (4)	V4—O4—K2^vi	150.08 (9)
O6^i—V1—V5^i	126.88 (4)	V5—O5—K2	144.90 (10)
O15—V1—V3	143.51 (5)	V1—O6—V1^i	101.49 (6)
O13—V1—V3	37.14 (5)	V1—O6—V4	94.07 (5)
O7—V1—V3	89.30 (4)	V1^i—O6—V4	93.00 (5)
O8—V1—V3	89.34 (4)	V1—O6—V2^i	93.82 (5)
O6—V1—V3	128.18 (4)	V1^i—O6—V2^i	92.31 (5)
O6^i—V1—V3	49.67 (4)	V4—O6—V2^i	169.43 (7)
V5^i—V1—V3	176.520 (15)	V1—O6—V5^i	88.59 (5)
O15—V1—K1^ii	85.13 (5)	V1^i—O6—V5^i	169.87 (7)
O13—V1—K1^ii	52.19 (5)	V4—O6—V5^i	87.22 (5)
O7—V1—K1^ii	52.17 (4)	V2^i—O6—V5^i	85.95 (5)
O8—V1—K1^ii	147.85 (5)	V1—O6—V3^i	171.60 (7)
O6—V1—K1^ii	131.06 (4)	V1^i—O6—V3^i	86.90 (5)
O6^i—V1—K1^ii	104.08 (4)	V4—O6—V3^i	85.74 (5)
V5^i—V1—K1^ii	111.119 (15)	V2^i—O6—V3^i	85.43 (5)
V3—V1—K1^ii	71.389 (14)	V5^i—O6—V3^i	83.01 (5)
O15—V1—K1^iii	32.37 (5)	V1—O7—V2	107.90 (7)
O13—V1—K1^iii	86.04 (5)	V1—O7—V4	106.63 (6)
O7—V1—K1^iii	125.97 (4)	V2—O7—V4	100.13 (6)
O8—V1—K1^iii	74.76 (4)	V1—O7—K1^ii	96.53 (5)
O6—V1—K1^iii	107.31 (4)	V2—O7—K1^ii	99.38 (5)
O6^i—V1—K1^iii	152.87 (4)	V4—O7—K1^ii	143.20 (6)
V5^i—V1—K1^iii	63.785 (14)	V1—O8—V4^i	107.47 (6)
V3—V1—K1^iii	118.970 (15)	V1—O8—V2^i	107.28 (7)
K1^ii—V1—K1^iii	91.982 (14)	V4^i—O8—V2^i	100.34 (6)
O2—V2—O23	103.34 (8)	V1—O13—V3	112.12 (7)
O2—V2—O25	102.01 (8)	V1—O13—K1^ii	100.55 (6)
O23—V2—O25	95.48 (7)	V3—O13—K1^ii	104.76 (6)
O2—V2—O7	100.76 (7)	V1—O15—V5^i	108.65 (7)
O23—V2—O7	89.93 (6)	V1—O15—K1^iii	128.88 (8)
O25—V2—O7	154.66 (6)	V5^i—O15—K1^iii	103.96 (6)
O2—V2—O8^i	99.83 (7)	V2—O23—V3	115.68 (8)
O23—V2—O8^i	154.90 (6)	V2—O23—K1^ii	101.88 (6)
O25—V2—O8^i	88.97 (6)	V3—O23—K1^ii	107.70 (6)
O7—V2—O8^i	76.29 (6)	V2—O25—V5	114.02 (8)
O2—V2—O6^i	174.71 (7)	V4—O34—V3^i	115.01 (8)
O23—V2—O6^i	81.16 (6)	V4—O34—K2^v	94.83 (6)
O25—V2—O6^i	80.13 (6)	V3^i—O34—K2^v	102.40 (6)
O7—V2—O6^i	76.27 (5)	V5—O35—V3	113.77 (8)
O8^i—V2—O6^i	75.28 (5)	V5—O35—K2^iv	99.20 (7)
O2—V2—V4	90.33 (6)	V3—O35—K2^iv	106.26 (7)
O23—V2—V4	130.15 (5)	V4—O45—V5^i	113.94 (7)
O25—V2—V4	128.60 (5)	V4—O45—K2^v	101.84 (6)
O7—V2—V4	40.22 (4)	V5^i—O45—K2^v	101.45 (6)
O8^i—V2—V4	39.63 (4)	O15^viii—K1—O2	122.38 (5)
O6^i—V2—V4	84.59 (4)	O15^viii—K1—O7^ii	112.26 (4)
O2—V2—V5	135.16 (6)	O2—K1—O7^ii	119.89 (5)
O23—V2—V5	83.51 (5)	O15^viii—K1—O3W	140.35 (5)
O25—V2—V5	33.37 (5)	O2—K1—O3W	83.44 (5)
O7—V2—V5	123.74 (4)	O7^ii—K1—O3W	68.43 (5)
O8^i—V2—V5	86.87 (4)	O15^viii—K1—O2W^viii	78.18 (5)
O6^i—V2—V5	47.49 (3)	O2—K1—O2W^viii	142.96 (5)
V4—V2—V5	119.160 (15)	O7^ii—K1—O2W^viii	67.79 (5)
O2—V2—K1^ii	83.13 (6)	O3W—K1—O2W^viii	65.29 (5)
O23—V2—K1^ii	50.14 (5)	O15^viii—K1—O13^ii	73.60 (4)
O25—V2—K1^ii	145.01 (5)	O2—K1—O13^ii	118.76 (5)
O7—V2—K1^ii	49.35 (4)	O7^ii—K1—O13^ii	54.87 (4)
O8^i—V2—K1^ii	124.65 (4)	O3W—K1—O13^ii	123.04 (5)
O6^i—V2—K1^ii	97.92 (4)	O2W^viii—K1—O13^ii	95.64 (5)
V4—V2—K1^ii	85.470 (15)	O15^viii—K1—O23^ii	121.37 (5)
V5—V2—K1^ii	128.645 (16)	O2—K1—O23^ii	75.93 (5)
O2—V2—K1	35.65 (6)	O7^ii—K1—O23^ii	54.49 (4)
O23—V2—K1	79.34 (5)	O3W—K1—O23^ii	92.15 (5)
O25—V2—K1	78.51 (5)	O2W^viii—K1—O23^ii	122.28 (5)
O7—V2—K1	126.83 (4)	O13^ii—K1—O23^ii	51.92 (4)
O8^i—V2—K1	125.71 (4)	O15^viii—K1—O5W^viii	86.93 (5)
O6^i—V2—K1	149.38 (4)	O2—K1—O5W^viii	84.96 (5)
V4—V2—K1	125.974 (15)	O7^ii—K1—O5W^viii	122.61 (5)
V5—V2—K1	106.688 (15)	O3W—K1—O5W^viii	64.17 (6)
K1^ii—V2—K1	87.394 (14)	O2W^viii—K1—O5W^viii	64.26 (5)
O3—V3—O35	104.92 (8)	O13^ii—K1—O5W^viii	154.86 (5)
O3—V3—O23	101.60 (8)	O23^ii—K1—O5W^viii	151.29 (5)
O35—V3—O23	90.92 (7)	O15^viii—K1—V1^ii	84.19 (3)
O3—V3—O34^i	104.09 (8)	O2—K1—V1^ii	134.01 (4)
O35—V3—O34^i	89.87 (7)	O7^ii—K1—V1^ii	31.29 (3)
O23—V3—O34^i	153.16 (7)	O3W—K1—V1^ii	98.76 (4)
O3—V3—O13	100.72 (8)	O2W^viii—K1—V1^ii	73.12 (4)
O35—V3—O13	154.35 (7)	O13^ii—K1—V1^ii	27.26 (3)
O23—V3—O13	83.21 (6)	O23^ii—K1—V1^ii	58.11 (3)
O34^i—V3—O13	84.55 (6)	O5W^viii—K1—V1^ii	137.38 (4)
O3—V3—O6^i	174.76 (8)	O15^viii—K1—Na1^ii	102.23 (4)
O35—V3—O6^i	80.19 (6)	O2—K1—Na1^ii	105.01 (4)
O23—V3—O6^i	76.91 (6)	O7^ii—K1—Na1^ii	84.83 (3)
O34^i—V3—O6^i	76.81 (6)	O3W—K1—Na1^ii	38.52 (4)
O13—V3—O6^i	74.16 (5)	O2W^viii—K1—Na1^ii	37.95 (4)
O3—V3—V5	137.67 (7)	O13^ii—K1—Na1^ii	130.67 (4)
O35—V3—V5	32.79 (5)	O23^ii—K1—Na1^ii	127.93 (4)
O23—V3—V5	82.87 (5)	O5W^viii—K1—Na1^ii	37.78 (4)
O34^i—V3—V5	83.37 (5)	V1^ii—K1—Na1^ii	104.38 (2)
O13—V3—V5	121.56 (4)	O15^viii—K1—V2^ii	132.59 (4)
O6^i—V3—V5	47.41 (3)	O2—K1—V2^ii	89.79 (4)
O3—V3—V1	131.45 (7)	O7^ii—K1—V2^ii	31.27 (3)
O35—V3—V1	123.61 (5)	O3W—K1—V2^ii	69.43 (4)
O23—V3—V1	78.29 (5)	O2W^viii—K1—V2^ii	96.79 (4)
O34^i—V3—V1	78.99 (5)	O13^ii—K1—V2^ii	59.88 (3)
O13—V3—V1	30.74 (4)	O23^ii—K1—V2^ii	27.98 (3)
O6^i—V3—V1	43.42 (3)	O5W^viii—K1—V2^ii	133.60 (4)
V5—V3—V1	90.832 (14)	V1^ii—K1—V2^ii	50.150 (11)
O3—V3—V4^i	135.96 (7)	Na1^ii—K1—V2^ii	101.17 (2)
O35—V3—V4^i	80.84 (5)	O15^viii—K1—V5^vi	31.33 (3)
O23—V3—V4^i	122.16 (5)	O2—K1—V5^vi	91.39 (4)
O34^i—V3—V4^i	31.89 (5)	O7^ii—K1—V5^vi	135.67 (3)
O13—V3—V4^i	81.29 (4)	O3W—K1—V5^vi	152.08 (4)
O6^i—V3—V4^i	45.26 (3)	O2W^viii—K1—V5^vi	106.79 (4)
V5—V3—V4^i	60.183 (12)	O13^ii—K1—V5^vi	83.43 (3)
V1—V3—V4^i	61.077 (12)	O23^ii—K1—V5^vi	113.24 (4)
O3—V3—K1^ii	84.22 (7)	O5W^viii—K1—V5^vi	88.09 (4)
O35—V3—K1^ii	136.19 (5)	V1^ii—K1—V5^vi	104.390 (16)
O23—V3—K1^ii	45.48 (5)	Na1^ii—K1—V5^vi	118.73 (2)
O34^i—V3—K1^ii	130.10 (5)	V2^ii—K1—V5^vi	138.190 (18)
O13—V3—K1^ii	45.82 (4)	O5—K2—O4^vi	130.10 (6)
O6^i—V3—K1^ii	91.27 (4)	O5—K2—O4W	72.15 (6)
V5—V3—K1^ii	122.892 (16)	O4^vi—K2—O4W	118.95 (6)
V1—V3—K1^ii	60.999 (13)	O5—K2—O45^ix	123.43 (6)
V4^i—V3—K1^ii	122.022 (15)	O4^vi—K2—O45^ix	103.65 (5)
O3—V3—K2^iv	89.01 (7)	O4W—K2—O45^ix	66.61 (5)
O35—V3—K2^iv	47.41 (5)	O5—K2—O35^iv	93.48 (5)
O23—V3—K2^iv	138.22 (5)	O4^vi—K2—O35^iv	131.48 (5)
O34^i—V3—K2^iv	50.36 (5)	O4W—K2—O35^iv	91.17 (5)
O13—V3—K2^iv	134.79 (5)	O45^ix—K2—O35^iv	51.91 (4)
O6^i—V3—K2^iv	95.43 (4)	O5—K2—O34^ix	139.60 (6)
V5—V3—K2^iv	63.568 (17)	O4^vi—K2—O34^ix	81.62 (5)
V1—V3—K2^iv	123.520 (18)	O4W—K2—O34^ix	118.17 (6)
V4^i—V3—K2^iv	62.534 (17)	O45^ix—K2—O34^ix	51.64 (4)
K1^ii—V3—K2^iv	173.05 (2)	O35^iv—K2—O34^ix	49.97 (4)
O4—V4—O45	102.88 (8)	O5—K2—O5W^viii	70.03 (5)
O4—V4—O34	102.79 (8)	O4^vi—K2—O5W^viii	75.39 (5)
O45—V4—O34	94.78 (7)	O4W—K2—O5W^viii	60.42 (6)
O4—V4—O8^i	99.48 (7)	O45^ix—K2—O5W^viii	116.16 (6)
O45—V4—O8^i	155.08 (6)	O35^iv—K2—O5W^viii	150.03 (5)
O34—V4—O8^i	90.84 (6)	O34^ix—K2—O5W^viii	150.27 (5)
O4—V4—O7	99.29 (7)	O5—K2—O3^x	63.33 (5)
O45—V4—O7	89.45 (6)	O4^vi—K2—O3^x	109.23 (6)
O34—V4—O7	155.94 (6)	O4W—K2—O3^x	128.55 (6)
O8^i—V4—O7	76.13 (6)	O45^ix—K2—O3^x	119.25 (5)
O4—V4—O6	174.08 (7)	O35^iv—K2—O3^x	68.10 (5)
O45—V4—O6	80.33 (6)	O34^ix—K2—O3^x	84.42 (5)
O34—V4—O6	81.75 (6)	O5W^viii—K2—O3^x	120.75 (5)
O8^i—V4—O6	76.49 (5)	O5—K2—V4^ix	147.76 (5)
O7—V4—O6	75.64 (5)	O4^vi—K2—V4^ix	82.13 (4)
O4—V4—V2	89.18 (6)	O4W—K2—V4^ix	92.67 (5)
O45—V4—V2	129.10 (5)	O45^ix—K2—V4^ix	28.05 (3)
O34—V4—V2	130.87 (5)	O35^iv—K2—V4^ix	57.70 (3)
O8^i—V4—V2	40.03 (4)	O34^ix—K2—V4^ix	28.65 (3)
O7—V4—V2	39.65 (4)	O5W^viii—K2—V4^ix	127.41 (5)
O6—V4—V2	84.95 (4)	O3^x—K2—V4^ix	111.41 (4)
O4—V4—V5^i	136.49 (6)	O5—K2—V5^iv	99.53 (4)
O45—V4—V5^i	33.79 (5)	O4^vi—K2—V5^iv	130.22 (4)
O34—V4—V5^i	83.45 (5)	O4W—K2—V5^iv	67.48 (4)
O8^i—V4—V5^i	123.68 (4)	O45^ix—K2—V5^iv	29.03 (3)
O7—V4—V5^i	87.11 (4)	O35^iv—K2—V5^iv	28.09 (3)
O6—V4—V5^i	47.21 (4)	O34^ix—K2—V5^iv	57.69 (3)
V2—V4—V5^i	119.319 (15)	O5W^viii—K2—V5^iv	127.63 (5)
O4—V4—V3^i	135.80 (6)	O3^x—K2—V5^iv	95.12 (4)
O45—V4—V3^i	84.29 (5)	V4^ix—K2—V5^iv	48.284 (13)
O34—V4—V3^i	33.10 (5)	O5—K2—Na1^ii	87.78 (5)
O8^i—V4—V3^i	87.34 (4)	O4^vi—K2—Na1^ii	84.38 (4)
O7—V4—V3^i	124.58 (4)	O4W—K2—Na1^ii	35.44 (5)
O6—V4—V3^i	49.00 (4)	O45^ix—K2—Na1^ii	80.42 (4)
V2—V4—V3^i	120.110 (14)	O35^iv—K2—Na1^ii	122.59 (4)
V5^i—V4—V3^i	59.248 (12)	O34^ix—K2—Na1^ii	124.13 (4)
O4—V4—K2^v	81.14 (6)	O5W^viii—K2—Na1^ii	35.77 (4)
O45—V4—K2^v	50.11 (5)	O3^x—K2—Na1^ii	150.56 (4)
O34—V4—K2^v	56.52 (5)	V4^ix—K2—Na1^ii	95.95 (3)
O8^i—V4—K2^v	146.06 (5)	V5^iv—K2—Na1^ii	95.20 (3)
O7—V4—K2^v	137.60 (4)	O5—K2—V3^iv	112.54 (4)
O6—V4—K2^v	104.64 (4)	O4^vi—K2—V3^iv	106.14 (4)
V2—V4—K2^v	169.35 (2)	O4W—K2—V3^iv	113.67 (5)
V5^i—V4—K2^v	66.510 (16)	O45^ix—K2—V3^iv	56.92 (3)
V3^i—V4—K2^v	70.383 (19)	O35^iv—K2—V3^iv	26.33 (3)
O5—V5—O35	105.10 (8)	O34^ix—K2—V3^iv	27.23 (3)
O5—V5—O25	100.58 (8)	O5W^viii—K2—V3^iv	173.05 (5)
O35—V5—O25	93.10 (7)	O3^x—K2—V3^iv	65.45 (4)
O5—V5—O45^i	102.48 (8)	V4^ix—K2—V3^iv	47.084 (12)
O35—V5—O45^i	90.89 (7)	V5^iv—K2—V3^iv	46.212 (12)
O25—V5—O45^i	154.67 (6)	Na1^ii—K2—V3^iv	137.29 (3)
O5—V5—O15^i	97.45 (8)	O5W^xi—Na1—O4W^ii	85.01 (9)
O35—V5—O15^i	157.44 (6)	O5W^xi—Na1—O2W^xi	86.54 (9)
O25—V5—O15^i	83.43 (6)	O4W^ii—Na1—O2W^xi	169.82 (9)
O45^i—V5—O15^i	83.35 (6)	O5W^xi—Na1—O3W^ii	85.66 (10)
O5—V5—O6^i	171.89 (8)	O4W^ii—Na1—O3W^ii	99.87 (8)
O35—V5—O6^i	83.01 (6)	O2W^xi—Na1—O3W^ii	85.11 (8)
O25—V5—O6^i	78.47 (6)	O5W^xi—Na1—O1W^vii	96.50 (9)
O45^i—V5—O6^i	77.22 (6)	O4W^ii—Na1—O1W^vii	88.19 (8)
O15^i—V5—O6^i	74.45 (5)	O2W^xi—Na1—O1W^vii	87.14 (8)
O5—V5—V1^i	128.87 (7)	O3W^ii—Na1—O1W^vii	171.82 (8)
O35—V5—V1^i	126.04 (5)	O5W^xi—Na1—O1W^xii	169.80 (10)
O25—V5—V1^i	78.97 (5)	O4W^ii—Na1—O1W^xii	103.13 (8)
O45^i—V5—V1^i	78.48 (5)	O2W^xi—Na1—O1W^xii	85.91 (8)
O15^i—V5—V1^i	31.42 (4)	O3W^ii—Na1—O1W^xii	86.87 (8)
O6^i—V5—V1^i	43.03 (4)	O1W^vii—Na1—O1W^xii	89.96 (7)
O5—V5—V3	138.52 (7)	O5W^xi—Na1—Na1^xiii	141.28 (8)
O35—V5—V3	33.44 (5)	O4W^ii—Na1—Na1^xiii	98.02 (7)
O25—V5—V3	85.31 (5)	O2W^xi—Na1—Na1^xiii	85.07 (7)
O45^i—V5—V3	84.34 (5)	O3W^ii—Na1—Na1^xiii	130.97 (8)
O15^i—V5—V3	124.03 (4)	O1W^vii—Na1—Na1^xiii	45.41 (5)
O6^i—V5—V3	49.58 (4)	O1W^xii—Na1—Na1^xiii	44.56 (5)
V1^i—V5—V3	92.608 (14)	O5W^xi—Na1—K1^ii	53.62 (8)
O5—V5—V2	133.17 (7)	O4W^ii—Na1—K1^ii	126.32 (6)
O35—V5—V2	82.90 (5)	O2W^xi—Na1—K1^ii	50.93 (6)
O25—V5—V2	32.62 (4)	O3W^ii—Na1—K1^ii	50.84 (7)
O45^i—V5—V2	123.77 (5)	O1W^vii—Na1—K1^ii	124.80 (6)
O15^i—V5—V2	82.29 (4)	O1W^xii—Na1—K1^ii	116.18 (5)
O6^i—V5—V2	46.56 (3)	Na1^xiii—Na1—K1^ii	135.61 (4)
V1^i—V5—V2	62.050 (12)	O5W^xi—Na1—K2^ii	56.44 (8)
V3—V5—V2	60.950 (12)	O4W^ii—Na1—K2^ii	46.10 (7)
O5—V5—V4^i	134.74 (6)	O2W^xi—Na1—K2^ii	123.94 (6)
O35—V5—V4^i	81.62 (5)	O3W^ii—Na1—K2^ii	126.02 (6)
O25—V5—V4^i	124.04 (5)	O1W^vii—Na1—K2^ii	61.01 (5)
O45^i—V5—V4^i	32.28 (4)	O1W^xii—Na1—K2^ii	133.75 (6)
O15^i—V5—V4^i	81.95 (4)	Na1^xiii—Na1—K2^ii	98.77 (4)
O6^i—V5—V4^i	45.57 (3)	K1^ii—Na1—K2^ii	110.03 (3)
V1^i—V5—V4^i	61.541 (12)	Na1^x—O1W—Na1^xii	90.04 (7)
V3—V5—V4^i	60.568 (12)	Na1^xi—O2W—K1^iii	91.12 (7)
V2—V5—V4^i	91.833 (14)	Na1^ii—O3W—K1	90.64 (8)
O5—V5—K2^iv	83.31 (7)	Na1^ii—O4W—K2	98.46 (8)
O35—V5—K2^iv	52.71 (5)	Na1^xi—O5W—K1^iii	88.60 (9)
O25—V5—K2^iv	144.80 (5)	Na1^xi—O5W—K2^iii	87.79 (9)
O45^i—V5—K2^iv	49.52 (5)	K1^iii—O5W—K2^iii	175.68 (8)

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