Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW₁₂O₄₀]⁴⁻: a synthetic, structural and computational investigation

As an extension of our continued inter­est in the preparation of inorganic–organic hybrids, we report the successful hydro­thermal synthesis of sodium tris­[tri­aqua­(μ-1,10-phenanthroline-2,9-di­carboxyl­ato)dysprosium(III)] silico­dodeca­tungstate dodeca­hydrate, {[DyNa(C₁₄H₆N₂O₄)₃(H₂O)₉(SiW₁₂O₄₀)]·12H₂O}_n or Na[Dy(PDA)(H₂O)₃]₃[SiW₁₂O₄₀]·12H₂O (1), and sodium aqua tris­[tetra­aqua­(μ-4-hydroxypyridine-2,6-di­carboxyl­ato)praseodymium(III)] silico­do­deca­tungstate dodeca­hydrate, {[NaPr(C₇H₃NO₅)₃(H₂O)₁₃(SiW₁₂O₄₀)]·12H₂O}_n or Na(H₂O)[Pr(pydc-OH)(H₂O)₄]₃[SiW₁₂O₄₀]·12H₂O (2) (in which H₂PDA is 1,10-phenanthroline-2,9-di­carb­oxy­lic acid and H₂pydc-OH is 4-hy­droxy­pyri­dine-2,6-di­carb­oxy­lic acid or chelidamic acid). Both compounds have been characterized using elemental analysis, IR spectroscopy and X-ray diffraction methods. Structural characterization by single-crystal X-ray diffraction reveals that these compounds consist of [SiW₁₂O₄₀]⁴⁻ Keggin-type polyoxometalates (POMs), where a single {W₃O₁₃} triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of inter­molecular inter­actions, such as hydrogen bonds and anion–π inter­actions, resulting in three-dimensional supra­molecular architectures. Density functional theory (DFT) studies were conducted to support these inter­molecular inter­actions in both 1 and 2, and have been rationalized using mol­ecular electrostatic potential (MEP) surface calculations.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015) for d23_4; APEX3 (Bruker, 2016) for jtm570b_4_a. Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for d23_4; SAINT (Bruker, 2016) for jtm570b_4_a. Data reduction: CrysAlis PRO (Rigaku OD, 2015) for d23_4; SAINT (Bruker, 2016) and CELL_NOW (Sheldrick, 2008) for jtm570b_4_a. Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for d23_4; SHELXT (Sheldrick, 2015a) for jtm570b_4_a. Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) for d23_4; SHELXL2018 (Sheldrick, 2015b) for jtm570b_4_a. Molecular graphics: OLEX2 (Dolomanov et al., 2009) for d23_4; DIAMOND (Brandenburg & Putz, 2012) for jtm570b_4_a. Software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) for d23_4; SHELXTL (Bruker, 2016) for jtm570b_4_a.

Sodium tris[triaqua(µ-1,10-phenanthroline-2,9-dicarboxylato)dysprosium(III)] silicododecatungstate dodecahydrate (d23_4)

Crystal data

[DyNa(C14H6N2O4)3(H2O)9(SiW12O40)]·12H2O	Dx = 3.353 Mg m^−3
Mr = 4527.40	Cu Kα radiation, λ = 1.54184 Å
Trigonal, R3	Cell parameters from 11603 reflections
a = 20.3334 (3) Å	θ = 4.3–76.8°
c = 18.7836 (3) Å	µ = 41.93 mm^−1
V = 6725.60 (19) Å^3	T = 130 K
Z = 3	Block, yellow
F(000) = 6033	0.07 × 0.05 × 0.03 mm

Data collection

SuperNova, Dual, Cu at zero, Atlas diffractometer	5475 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	5450 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 10.2273 pixels mm^-1	θmax = 77.1°, θmin = 3.4°
ω scans	h = −25→25
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2015)	k = −25→22
Tmin = 0.097, Tmax = 0.369	l = −17→23
16672 measured reflections

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0696P)^2 + 182.8632P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.036	(Δ/σ)max = 0.001
wR(F^2) = 0.098	Δρmax = 1.53 e Å^−3
S = 1.02	Δρmin = −1.89 e Å^−3
5475 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
426 parameters	Extinction coefficient: 0.000018 (3)
1 restraint	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower
Primary atom site location: dual	Absolute structure parameter: 0.013 (7)
Hydrogen site location: inferred from neighbouring sites

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	Occ. (<1)
W4	0.44911 (3)	0.69357 (3)	0.56892 (4)	0.01497 (17)
W1	0.41288 (4)	0.77239 (4)	0.87226 (4)	0.01785 (18)
W2	0.52603 (4)	0.80714 (4)	0.70932 (4)	0.01734 (18)
W3	0.48229 (4)	0.62447 (4)	0.71593 (4)	0.02049 (19)
Dy1	0.51195 (5)	0.65952 (5)	0.37516 (5)	0.0164 (2)
Si1	0.3333	0.6667	0.7162 (4)	0.0118 (11)
Na1	0.3333	0.6667	0.2727 (9)	0.043 (3)
O3	0.4885 (6)	0.7885 (6)	0.8053 (6)	0.017 (2)
O8	0.5293 (6)	0.7869 (5)	0.6112 (6)	0.0158 (19)
O12	0.4913 (6)	0.6406 (6)	0.6149 (6)	0.016 (2)
O11	0.4427 (5)	0.6170 (6)	0.8083 (6)	0.017 (2)
O6	0.6133 (6)	0.8872 (6)	0.7191 (7)	0.021 (2)
O7	0.5555 (5)	0.7296 (6)	0.7265 (6)	0.017 (2)
O2	0.4173 (6)	0.6883 (6)	0.9140 (6)	0.017 (2)
O1	0.4622 (7)	0.8404 (7)	0.9358 (6)	0.024 (2)
O15	0.2638 (6)	0.4988 (7)	0.3514 (7)	0.024 (2)
O10	0.5381 (6)	0.5854 (6)	0.7255 (6)	0.020 (2)
C10	0.5397 (10)	0.5640 (10)	0.5073 (9)	0.024 (3)
O13	0.4852 (6)	0.7001 (6)	0.4845 (6)	0.018 (2)
O17	0.6409 (6)	0.7464 (6)	0.3883 (8)	0.030 (3)
O20	0.5127 (8)	0.6757 (8)	0.2497 (7)	0.033 (3)
C9	0.5742 (12)	0.5423 (11)	0.5605 (11)	0.031 (4)
O21	0.3066 (8)	0.5641 (8)	0.1948 (9)	0.038 (3)
O16	0.3803 (6)	0.5977 (7)	0.3480 (7)	0.022 (2)
N1	0.4311 (7)	0.5416 (7)	0.4422 (7)	0.017 (2)
O9	0.4179 (5)	0.6902 (5)	0.6868 (5)	0.0102 (17)
C1	0.3314 (8)	0.5341 (8)	0.3712 (8)	0.017 (3)
C4	0.3389 (10)	0.4085 (9)	0.5160 (10)	0.026 (3)
H4	0.3069	0.3627	0.5409	0.031*
C6	0.4613 (9)	0.5179 (8)	0.4940 (9)	0.018 (3)
C2	0.3576 (8)	0.5003 (9)	0.4272 (9)	0.019 (3)
C8	0.5273 (12)	0.4744 (12)	0.5997 (11)	0.033 (4)
H8	0.5501	0.4596	0.6357	0.040*
O18	0.7546 (9)	0.7895 (10)	0.4416 (16)	0.081 (8)
C12	0.6903 (10)	0.6552 (12)	0.5338 (11)	0.034 (4)
H12	0.7430	0.6887	0.5413	0.041*
C13	0.6505 (9)	0.6725 (9)	0.4802 (11)	0.027 (4)
C3	0.3093 (10)	0.4326 (10)	0.4634 (11)	0.029 (4)
H3	0.2570	0.4039	0.4516	0.035*
N2	0.5771 (7)	0.6266 (7)	0.4684 (8)	0.020 (3)
C5	0.4156 (11)	0.4509 (10)	0.5333 (12)	0.030 (4)
C11	0.6533 (12)	0.5922 (13)	0.5729 (11)	0.036 (5)
H11	0.6792	0.5807	0.6085	0.043*
C7	0.4529 (13)	0.4307 (11)	0.5880 (11)	0.035 (4)
H7	0.4241	0.3862	0.6157	0.041*
C14	0.6855 (10)	0.7409 (10)	0.4339 (14)	0.038 (5)
O4	0.3333	0.6667	0.8022 (9)	0.011 (3)
O14	0.3542 (5)	0.6058 (6)	0.5595 (6)	0.017 (2)
O5	0.4639 (6)	0.8485 (6)	0.6953 (6)	0.016 (2)
O19	0.5444 (8)	0.5750 (7)	0.3202 (8)	0.033 (3)
O25	0.9043 (12)	0.8861 (17)	0.3944 (13)	0.097 (10)
O23	0.440 (2)	0.5157 (19)	0.207 (2)	0.135 (15)
O26	0.7339 (19)	0.992 (3)	0.622 (2)	0.066 (11)	0.5
O28	0.525 (2)	1.000 (2)	0.950 (2)	0.058 (9)*	0.5
O27	0.578 (2)	1.010 (2)	0.775 (2)	0.061 (9)*	0.5
O22	0.3333	0.6667	0.126 (3)	0.050 (13)*	0.5
O24	0.362 (3)	0.473 (3)	0.083 (2)	0.087 (16)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W4	0.0123 (3)	0.0143 (3)	0.0178 (4)	0.0062 (2)	0.0011 (2)	−0.0014 (2)
W1	0.0173 (3)	0.0159 (3)	0.0187 (4)	0.0071 (2)	−0.0012 (2)	−0.0036 (2)
W2	0.0118 (3)	0.0150 (3)	0.0229 (4)	0.0049 (2)	−0.0009 (2)	−0.0024 (2)
W3	0.0175 (3)	0.0197 (3)	0.0263 (4)	0.0108 (3)	−0.0022 (3)	−0.0013 (3)
Dy1	0.0146 (4)	0.0155 (4)	0.0208 (5)	0.0089 (3)	0.0030 (3)	0.0004 (3)
Si1	0.0097 (15)	0.0097 (15)	0.016 (3)	0.0048 (8)	0.000	0.000
Na1	0.040 (5)	0.040 (5)	0.050 (9)	0.020 (2)	0.000	0.000
O3	0.017 (5)	0.019 (5)	0.014 (5)	0.008 (4)	−0.002 (4)	0.001 (4)
O8	0.016 (5)	0.010 (4)	0.019 (5)	0.005 (4)	−0.001 (4)	0.002 (4)
O12	0.016 (5)	0.018 (5)	0.019 (6)	0.012 (4)	−0.005 (4)	−0.005 (4)
O11	0.011 (4)	0.018 (5)	0.016 (5)	0.004 (4)	0.001 (4)	0.003 (4)
O6	0.009 (4)	0.019 (5)	0.032 (6)	0.005 (4)	0.002 (4)	−0.001 (4)
O7	0.011 (4)	0.013 (5)	0.020 (5)	0.001 (4)	−0.002 (4)	−0.001 (4)
O2	0.015 (4)	0.017 (5)	0.019 (6)	0.008 (4)	0.002 (4)	0.003 (4)
O1	0.029 (6)	0.025 (6)	0.017 (6)	0.013 (5)	0.000 (4)	−0.003 (4)
O15	0.014 (5)	0.031 (6)	0.027 (6)	0.011 (4)	−0.001 (4)	−0.008 (5)
O10	0.017 (5)	0.025 (5)	0.019 (5)	0.012 (4)	−0.001 (4)	−0.003 (4)
C10	0.028 (8)	0.033 (8)	0.018 (8)	0.021 (7)	−0.006 (6)	−0.013 (6)
O13	0.015 (5)	0.019 (5)	0.019 (6)	0.008 (4)	−0.003 (4)	−0.003 (4)
O17	0.015 (5)	0.020 (6)	0.051 (8)	0.005 (4)	0.005 (5)	0.002 (5)
O20	0.042 (7)	0.048 (8)	0.021 (7)	0.031 (7)	0.005 (5)	0.004 (5)
C9	0.044 (11)	0.032 (9)	0.026 (9)	0.026 (8)	0.002 (8)	0.001 (7)
O21	0.034 (7)	0.035 (7)	0.046 (9)	0.017 (6)	0.010 (6)	0.004 (6)
O16	0.013 (5)	0.027 (6)	0.026 (6)	0.010 (4)	−0.005 (4)	−0.002 (5)
N1	0.020 (6)	0.016 (5)	0.019 (6)	0.013 (5)	0.001 (5)	−0.007 (5)
O9	0.012 (4)	0.007 (4)	0.011 (5)	0.004 (3)	−0.003 (3)	−0.002 (3)
C1	0.020 (7)	0.021 (7)	0.013 (7)	0.014 (6)	−0.002 (5)	−0.003 (5)
C4	0.027 (8)	0.015 (7)	0.030 (9)	0.007 (6)	0.008 (7)	0.007 (6)
C6	0.021 (7)	0.019 (7)	0.019 (8)	0.014 (6)	0.003 (6)	−0.005 (5)
C2	0.018 (7)	0.022 (7)	0.017 (8)	0.010 (6)	0.008 (5)	−0.003 (6)
C8	0.048 (11)	0.046 (11)	0.027 (9)	0.040 (10)	0.006 (8)	0.014 (8)
O18	0.018 (7)	0.035 (9)	0.17 (3)	−0.001 (6)	−0.006 (10)	0.017 (12)
C12	0.023 (8)	0.044 (11)	0.033 (11)	0.015 (8)	−0.017 (7)	−0.013 (8)
C13	0.015 (7)	0.018 (7)	0.045 (11)	0.006 (6)	−0.007 (7)	−0.010 (7)
C3	0.028 (8)	0.020 (7)	0.039 (11)	0.011 (7)	0.001 (7)	0.000 (7)
N2	0.019 (6)	0.024 (6)	0.025 (7)	0.016 (5)	0.001 (5)	−0.006 (5)
C5	0.033 (9)	0.019 (7)	0.044 (11)	0.017 (7)	0.004 (8)	0.000 (7)
C11	0.038 (10)	0.053 (12)	0.032 (10)	0.033 (9)	−0.016 (8)	−0.017 (9)
C7	0.054 (12)	0.026 (8)	0.028 (10)	0.024 (9)	0.000 (8)	0.005 (7)
C14	0.019 (8)	0.018 (8)	0.076 (16)	0.009 (7)	−0.011 (8)	−0.008 (8)
O4	0.011 (4)	0.011 (4)	0.011 (8)	0.005 (2)	0.000	0.000
O14	0.013 (4)	0.016 (5)	0.021 (6)	0.007 (4)	−0.005 (4)	−0.003 (4)
O5	0.017 (5)	0.015 (5)	0.016 (5)	0.009 (4)	0.003 (4)	−0.003 (4)
O19	0.053 (8)	0.025 (6)	0.036 (8)	0.030 (6)	0.018 (6)	0.010 (5)
O25	0.045 (11)	0.14 (2)	0.048 (14)	0.000 (12)	−0.003 (9)	0.015 (13)
O23	0.18 (4)	0.11 (2)	0.16 (4)	0.11 (3)	−0.08 (3)	−0.07 (2)
O26	0.030 (16)	0.09 (3)	0.06 (2)	0.016 (17)	−0.015 (15)	−0.02 (2)
O24	0.11 (4)	0.11 (4)	0.04 (2)	0.06 (3)	0.00 (2)	0.04 (2)

Geometric parameters (Å, º)

W4—O8	1.949 (10)	Na1—O21^ii	2.378 (18)
W4—O12	1.888 (10)	Na1—O21^i	2.378 (18)
W4—O13	1.725 (11)	Na1—O21	2.378 (18)
W4—O9	2.296 (10)	Na1—O16^i	2.494 (15)
W4—O14^i	1.940 (10)	Na1—O16	2.494 (15)
W4—O14	1.870 (10)	Na1—O16^ii	2.494 (15)
W1—O3	1.884 (11)	Na1—O22	2.76 (7)
W1—O11^i	1.909 (10)	O11—W1^ii	1.909 (10)
W1—O2^i	1.952 (10)	O2—W1^ii	1.952 (10)
W1—O2	1.924 (10)	O15—Dy1^ii	2.306 (10)
W1—O1	1.719 (11)	O15—C1	1.247 (19)
W1—O4	2.343 (10)	C10—C9	1.41 (3)
W2—O3	1.921 (11)	C10—C6	1.41 (2)
W2—O8	1.896 (11)	C10—N2	1.33 (2)
W2—O6	1.716 (10)	O17—C14	1.29 (2)
W2—O7	1.974 (11)	C9—C8	1.43 (3)
W2—O9	2.332 (9)	C9—C11	1.43 (3)
W2—O5	1.853 (10)	O16—C1	1.25 (2)
W3—O12	1.919 (11)	N1—C6	1.36 (2)
W3—O11	1.886 (11)	N1—C2	1.33 (2)
W3—O7	1.908 (10)	C1—C2	1.49 (2)
W3—O10	1.689 (11)	C4—C3	1.37 (3)
W3—O9	2.356 (9)	C4—C5	1.39 (3)
W3—O5^ii	1.938 (10)	C6—C5	1.41 (2)
Dy1—O15^i	2.306 (10)	C2—C3	1.40 (2)
Dy1—O13	2.375 (11)	C8—C7	1.34 (3)
Dy1—O17	2.329 (11)	O18—C14	1.26 (2)
Dy1—O20	2.379 (13)	C12—C13	1.44 (3)
Dy1—O16	2.374 (11)	C12—C11	1.34 (3)
Dy1—N1	2.469 (13)	C13—N2	1.32 (2)
Dy1—N2	2.482 (14)	C13—C14	1.48 (3)
Dy1—O19	2.364 (12)	C5—C7	1.45 (3)
Si1—O9	1.633 (10)	O4—W1^i	2.343 (10)
Si1—O9^ii	1.633 (10)	O4—W1^ii	2.343 (10)
Si1—O9^i	1.633 (10)	O14—W4^ii	1.940 (10)
Si1—O4	1.615 (19)	O5—W3^i	1.938 (10)
O8—W4—O9	73.7 (4)	O9^i—Si1—O9	109.2 (4)
O12—W4—O8	88.4 (4)	O9^ii—Si1—O9	109.2 (4)
O12—W4—O9	74.9 (4)	O4—Si1—O9^ii	109.8 (4)
O12—W4—O14^i	157.7 (5)	O4—Si1—O9	109.8 (4)
O13—W4—O8	100.6 (5)	O4—Si1—O9^i	109.8 (4)
O13—W4—O12	99.6 (5)	O21^ii—Na1—O21^i	86.1 (7)
O13—W4—O9	172.0 (4)	O21^ii—Na1—O21	86.1 (7)
O13—W4—O14^i	102.6 (5)	O21^i—Na1—O21	86.1 (7)
O13—W4—O14	100.6 (5)	O21—Na1—O16^ii	104.8 (4)
O14—W4—O8	158.4 (5)	O21—Na1—O16^i	162.2 (4)
O14^i—W4—O8	85.4 (4)	O21—Na1—O16	80.8 (5)
O14—W4—O12	92.6 (5)	O21^i—Na1—O16^ii	162.2 (4)
O14^i—W4—O9	82.8 (4)	O21^i—Na1—O16	104.8 (4)
O14—W4—O9	85.7 (4)	O21^i—Na1—O16^i	80.8 (5)
O14—W4—O14^i	85.6 (6)	O21^ii—Na1—O16	162.2 (4)
O3—W1—O11^i	86.9 (5)	O21^ii—Na1—O16^i	104.8 (4)
O3—W1—O2^i	158.6 (4)	O21^ii—Na1—O16^ii	80.8 (5)
O3—W1—O2	91.7 (4)	O21—Na1—O22	52.0 (5)
O3—W1—O4	85.1 (4)	O21^i—Na1—O22	52.0 (5)
O11^i—W1—O2^i	86.9 (4)	O21^ii—Na1—O22	52.0 (5)
O11^i—W1—O2	158.5 (5)	O16^i—Na1—O16	91.0 (6)
O11^i—W1—O4	84.1 (4)	O16^ii—Na1—O16	91.0 (6)
O2—W1—O2^i	86.7 (6)	O16^ii—Na1—O16^i	91.0 (6)
O2—W1—O4	74.4 (4)	O16^ii—Na1—O22	124.5 (4)
O2^i—W1—O4	73.9 (4)	O16^i—Na1—O22	124.5 (4)
O1—W1—O3	103.1 (5)	O16—Na1—O22	124.5 (4)
O1—W1—O11^i	101.7 (5)	W1—O3—W2	150.5 (6)
O1—W1—O2	99.5 (5)	W2—O8—W4	120.3 (5)
O1—W1—O2^i	98.2 (5)	W4—O12—W3	121.2 (5)
O1—W1—O4	170.1 (5)	W3—O11—W1^ii	151.5 (6)
O3—W2—O7	86.4 (5)	W3—O7—W2	120.0 (5)
O3—W2—O9	83.7 (4)	W1—O2—W1^ii	120.1 (6)
O8—W2—O3	157.4 (4)	C1—O15—Dy1^ii	141.1 (10)
O8—W2—O7	85.9 (4)	C6—C10—C9	119.4 (17)
O8—W2—O9	73.8 (4)	N2—C10—C9	123.5 (16)
O6—W2—O3	101.9 (5)	N2—C10—C6	117.1 (15)
O6—W2—O8	100.3 (5)	W4—O13—Dy1	158.6 (6)
O6—W2—O7	99.0 (5)	C14—O17—Dy1	125.2 (11)
O6—W2—O9	170.9 (4)	C10—C9—C8	118.1 (18)
O6—W2—O5	101.6 (5)	C10—C9—C11	116.9 (18)
O7—W2—O9	73.9 (4)	C11—C9—C8	125.0 (19)
O5—W2—O3	86.0 (5)	Dy1—O16—Na1	118.1 (5)
O5—W2—O8	93.8 (4)	C1—O16—Dy1	125.2 (10)
O5—W2—O7	159.1 (4)	C1—O16—Na1	116.6 (9)
O5—W2—O9	85.9 (4)	C6—N1—Dy1	120.7 (10)
O12—W3—O9	72.9 (4)	C2—N1—Dy1	119.8 (11)
O12—W3—O5^ii	85.8 (5)	C2—N1—C6	119.5 (13)
O11—W3—O12	157.5 (4)	W4—O9—W2	92.2 (3)
O11—W3—O7	93.3 (5)	W4—O9—W3	91.0 (3)
O11—W3—O9	85.6 (4)	W2—O9—W3	91.6 (3)
O11—W3—O5^ii	84.9 (4)	Si1—O9—W4	124.8 (6)
O7—W3—O12	87.5 (5)	Si1—O9—W2	123.7 (5)
O7—W3—O9	74.5 (4)	Si1—O9—W3	123.9 (5)
O7—W3—O5^ii	157.4 (4)	O15—C1—O16	124.7 (14)
O10—W3—O12	99.0 (5)	O15—C1—C2	119.4 (14)
O10—W3—O11	103.0 (5)	O16—C1—C2	116.0 (13)
O10—W3—O7	100.6 (5)	C3—C4—C5	120.2 (16)
O10—W3—O9	170.5 (5)	C10—C6—C5	121.8 (16)
O10—W3—O5^ii	101.7 (5)	N1—C6—C10	116.8 (15)
O5^ii—W3—O9	82.9 (4)	N1—C6—C5	121.3 (15)
O15^i—Dy1—O13	72.5 (4)	N1—C2—C1	114.1 (14)
O15^i—Dy1—O17	84.8 (4)	N1—C2—C3	122.0 (16)
O15^i—Dy1—O20	71.1 (5)	C3—C2—C1	123.9 (15)
O15^i—Dy1—O16	81.1 (4)	C7—C8—C9	123.0 (17)
O15^i—Dy1—N1	132.5 (4)	C11—C12—C13	120.2 (16)
O15^i—Dy1—N2	134.4 (4)	C12—C13—C14	124.9 (15)
O15^i—Dy1—O19	141.5 (4)	N2—C13—C12	121.1 (17)
O13—Dy1—O20	142.7 (4)	N2—C13—C14	114.0 (16)
O13—Dy1—N1	74.9 (4)	C4—C3—C2	119.0 (16)
O13—Dy1—N2	74.3 (4)	C10—N2—Dy1	121.3 (10)
O17—Dy1—O13	90.6 (4)	C13—N2—Dy1	119.5 (12)
O17—Dy1—O20	94.2 (5)	C13—N2—C10	119.2 (15)
O17—Dy1—O16	165.4 (4)	C4—C5—C6	117.9 (17)
O17—Dy1—N1	129.3 (5)	C4—C5—C7	124.8 (17)
O17—Dy1—N2	65.1 (5)	C6—C5—C7	117.3 (17)
O17—Dy1—O19	88.9 (5)	C12—C11—C9	119.1 (18)
O20—Dy1—N1	126.5 (5)	C8—C7—C5	120.3 (18)
O20—Dy1—N2	140.3 (4)	O17—C14—C13	116.1 (15)
O16—Dy1—O13	88.6 (4)	O18—C14—O17	124 (2)
O16—Dy1—O20	77.8 (4)	O18—C14—C13	120 (2)
O16—Dy1—N1	64.4 (4)	W1^i—O4—W1^ii	91.6 (5)
O16—Dy1—N2	128.4 (4)	W1—O4—W1^ii	91.6 (5)
N1—Dy1—N2	64.1 (4)	W1^i—O4—W1	91.6 (5)
O19—Dy1—O13	145.6 (4)	Si1—O4—W1^i	124.2 (3)
O19—Dy1—O20	71.5 (5)	Si1—O4—W1	124.2 (3)
O19—Dy1—O16	99.9 (5)	Si1—O4—W1^ii	124.2 (3)
O19—Dy1—N1	79.0 (4)	W4—O14—W4^ii	151.9 (6)
O19—Dy1—N2	74.4 (5)	W2—O5—W3^i	153.0 (6)
O9^i—Si1—O9^ii	109.2 (4)
Dy1^ii—O15—C1—O16	−87 (2)	O9^ii—Si1—O9—W2	177.8 (4)
Dy1^ii—O15—C1—C2	92.5 (19)	O9^i—Si1—O9—W2	58.5 (10)
Dy1—O17—C14—O18	−178 (2)	O9^i—Si1—O9—W3	177.8 (4)
Dy1—O17—C14—C13	1 (2)	O9^ii—Si1—O9—W3	−62.9 (10)
Dy1—O16—C1—O15	−172.7 (11)	O9—Si1—O4—W1^i	178.1 (3)
Dy1—O16—C1—C2	8.1 (18)	O9^i—Si1—O4—W1	−61.9 (3)
Dy1—N1—C6—C10	0.5 (17)	O9^ii—Si1—O4—W1	178.1 (3)
Dy1—N1—C6—C5	179.4 (12)	O9—Si1—O4—W1	58.1 (3)
Dy1—N1—C2—C1	−2.9 (16)	O9^i—Si1—O4—W1^ii	178.1 (3)
Dy1—N1—C2—C3	179.6 (12)	O9^ii—Si1—O4—W1^ii	58.1 (3)
Na1—O16—C1—O15	11 (2)	O9—Si1—O4—W1^ii	−61.9 (3)
Na1—O16—C1—C2	−168.5 (10)	O9^ii—Si1—O4—W1^i	−61.9 (3)
O3—W2—O8—W4	3.7 (15)	O9^i—Si1—O4—W1^i	58.1 (3)
O3—W2—O5—W3^i	−27.3 (13)	C1—C2—C3—C4	−177.1 (15)
O8—W4—O12—W3	72.3 (6)	C4—C5—C7—C8	178.6 (19)
O8—W4—O13—Dy1	145.2 (15)	C6—C10—C9—C8	−1 (2)
O8—W4—O14—W4^ii	39 (2)	C6—C10—C9—C11	−178.3 (16)
O8—W2—O5—W3^i	130.1 (13)	C6—C10—N2—Dy1	−1.1 (19)
O12—W4—O13—Dy1	55.1 (16)	C6—C10—N2—C13	178.4 (14)
O12—W4—O14—W4^ii	131.1 (14)	C6—N1—C2—C1	178.0 (12)
O12—W3—O11—W1^ii	40 (2)	C6—N1—C2—C3	0 (2)
O11^i—W1—O3—W2	−24.7 (12)	C6—C5—C7—C8	0 (3)
O6—W2—O8—W4	172.6 (6)	C2—N1—C6—C10	179.7 (13)
O6—W2—O5—W3^i	−128.6 (13)	C2—N1—C6—C5	−1 (2)
O7—W2—O8—W4	74.2 (6)	C8—C9—C11—C12	−178 (2)
O7—W2—O5—W3^i	42 (2)	C12—C13—N2—Dy1	−179.8 (13)
O7—W3—O11—W1^ii	130.9 (13)	C12—C13—N2—C10	1 (2)
O2—W1—O3—W2	133.9 (13)	C12—C13—C14—O17	179.3 (18)
O2^i—W1—O3—W2	49 (2)	C12—C13—C14—O18	−2 (3)
O1—W1—O3—W2	−125.9 (13)	C13—C12—C11—C9	0 (3)
O15—C1—C2—N1	177.7 (13)	C3—C4—C5—C6	−1 (3)
O15—C1—C2—C3	−5 (2)	C3—C4—C5—C7	−180.0 (18)
O10—W3—O11—W1^ii	−127.4 (13)	N2—C10—C9—C8	178.6 (16)
C10—C9—C8—C7	0 (3)	N2—C10—C9—C11	1 (3)
C10—C9—C11—C12	−1 (3)	N2—C10—C6—N1	0 (2)
C10—C6—C5—C4	−179.3 (15)	N2—C10—C6—C5	−178.5 (15)
C10—C6—C5—C7	0 (2)	N2—C13—C14—O17	−1 (3)
O13—W4—O12—W3	172.8 (6)	N2—C13—C14—O18	178 (2)
O13—W4—O14—W4^ii	−128.6 (14)	C5—C4—C3—C2	0 (3)
C9—C10—C6—N1	179.9 (14)	C11—C9—C8—C7	177.5 (19)
C9—C10—C6—C5	1 (2)	C11—C12—C13—N2	0 (3)
C9—C10—N2—Dy1	179.4 (12)	C11—C12—C13—C14	179.6 (19)
C9—C10—N2—C13	−1 (2)	C14—C13—N2—Dy1	0 (2)
C9—C8—C7—C5	0 (3)	C14—C13—N2—C10	−179.3 (15)
O16—C1—C2—N1	−3.0 (19)	O4—W1—O3—W2	59.7 (12)
O16—C1—C2—C3	174.5 (15)	O4—Si1—O9—W4	176.8 (4)
N1—C6—C5—C4	2 (2)	O4—Si1—O9—W2	−61.9 (6)
N1—C6—C5—C7	−179.3 (15)	O4—Si1—O9—W3	57.4 (6)
N1—C2—C3—C4	0 (3)	O14—W4—O12—W3	−86.1 (7)
O9—W4—O12—W3	−1.3 (5)	O14^i—W4—O12—W3	−1.2 (15)
O9—W4—O14—W4^ii	56.5 (13)	O14^i—W4—O13—Dy1	−127.2 (15)
O9—W2—O8—W4	−0.3 (5)	O14—W4—O13—Dy1	−39.4 (16)
O9—W2—O5—W3^i	56.7 (13)	O14^i—W4—O14—W4^ii	−26.6 (16)
O9—W3—O11—W1^ii	56.8 (13)	O5—W2—O8—W4	−84.9 (6)
O9^i—Si1—O9—W4	−62.8 (6)	O5^ii—W3—O11—W1^ii	−26.5 (13)
O9^ii—Si1—O9—W4	56.4 (7)

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

Sodium aqua tris[tetraaqua(µ-4-hydroxypyridine-2,6-dicarboxylato)praseodymium(III)] silicododecatungstate dodecahydrate (jtm570b_4_a)

Crystal data

[NaPr(C7H3NO5)3(H2O)13(SiW12O40)]·12H2O	Dx = 3.601 Mg m^−3
Mr = 4307.67	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 9882 reflections
a = 18.119 (3) Å	θ = 2.3–29.1°
c = 21.078 (3) Å	µ = 19.14 mm^−1
V = 5993 (2) Å^3	T = 100 K
Z = 3	Column, light yellow
F(000) = 5790	0.24 × 0.13 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer	7142 independent reflections
Radiation source: fine-focus sealed tube	6106 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
Detector resolution: 8.3333 pixels mm^-1	θmax = 29.2°, θmin = 1.6°
φ and ω scans	h = −24→24
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −24→24
Tmin = 0.09, Tmax = 0.22	l = −28→28
74256 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0314P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
7142 reflections	Δρmax = 1.97 e Å^−3
385 parameters	Δρmin = −2.07 e Å^−3
241 restraints	Absolute structure: Flack x determined using 2688 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (7)

Special details

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = -30.00 and 210.00°. The scan time was 10 sec/frame. Analysis of 1347 reflections having I/σ(I) > 12 and chosen from the full data set with CELL_NOW (Sheldrick, 2008) showed the crystal to belong to the trigonal system and to have a very minor twin component. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW.

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. Hatoms attached to carbon were placed in calculated positions (C—H = 0.95 Å) while those attached to oxygen were placed in positions that would generate the most favorable hydrogen bonding interactions with O—H = 0.87 Å. All were included as riding contributions with displacement parameters 1.2 - 1.5 times those of the attached atoms. An attempt to refine the model with the full twinned data led to some atoms becoming NPD and since the twin component was minor, it was not included in the final refinement.

the crystal used was mounted on a nylon loop with a drop of heavy oil and mounted in a cold nitrogen stream on a Bruker Smart APEX CCD diffractometer. A full sphere of data was collected from which it was determined that the crystal consisted of two components (CELL-NOW). The raw data were converted to F² values using the multi-component version of SAINT under the control of the 2-component orientation file generated by CELL-NOW. Correction for absorption and merging of equivalent reflections for the 2-component reflection file was carried out with TWINABS which also extracted a single-component reflection file from the full data set for structure solution. The structure was solved by direct methods and refined by full-matrix, least squares.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Na1	0.333333	0.666667	0.2314 (5)	0.038 (3)
W1	0.25977 (4)	0.53062 (4)	0.48154 (2)	0.00999 (12)
W2	0.13249 (4)	0.48260 (4)	0.60810 (2)	0.01449 (13)
W3	0.15307 (4)	0.69539 (4)	0.61336 (2)	0.01467 (14)
W4	0.21000 (4)	0.61161 (4)	0.75405 (3)	0.01871 (15)
Pr1	0.16948 (6)	0.42412 (6)	0.29909 (4)	0.0231 (2)
Si1	0.333333	0.666667	0.6130 (3)	0.0060 (10)
O1	0.3227 (7)	0.4982 (7)	0.2939 (5)	0.025 (2)
O2	0.4232 (7)	0.6357 (7)	0.2907 (5)	0.031 (3)
O3	0.6776 (7)	0.7460 (7)	0.3773 (5)	0.024 (2)
O4	0.7212 (8)	0.6804 (8)	0.4459 (5)	0.039 (3)
O5	0.4381 (9)	0.4029 (8)	0.4840 (6)	0.042 (3)
H5	0.389837	0.364795	0.471572	0.063*
O6	0.2088 (10)	0.4350 (9)	0.1846 (6)	0.056 (4)
H6A	0.263966	0.464596	0.181036	0.085*
H6B	0.186077	0.460446	0.164136	0.085*
O7	0.0718 (9)	0.4521 (9)	0.2250 (6)	0.053 (4)
H7A	0.019239	0.421080	0.237491	0.079*
H7B	0.076639	0.438468	0.186281	0.079*
O8	0.0681 (7)	0.2813 (7)	0.2456 (5)	0.032 (3)
H8A	0.097665	0.261656	0.226972	0.047*
H8B	0.037425	0.289026	0.217472	0.047*
O9	0.2233 (7)	0.3224 (7)	0.3174 (5)	0.037 (3)
H9A	0.183122	0.275868	0.334543	0.056*
H9B	0.267011	0.345728	0.342743	0.056*
O10	0.2354 (6)	0.4843 (6)	0.4074 (4)	0.015 (2)
O11	0.0276 (7)	0.4063 (7)	0.6181 (5)	0.022 (2)
O12	0.1309 (7)	0.5762 (7)	0.8086 (5)	0.025 (2)
O13	0.0551 (7)	0.6863 (7)	0.6217 (5)	0.024 (2)
O14	0.3762 (5)	0.6132 (5)	0.4720 (4)	0.0095 (18)
O15	0.2857 (6)	0.4523 (6)	0.5222 (4)	0.015 (2)
O16	0.1485 (6)	0.4700 (6)	0.5200 (4)	0.016 (2)
O17	0.1244 (6)	0.5798 (6)	0.5935 (4)	0.016 (2)
O18	0.1632 (6)	0.5225 (6)	0.6932 (4)	0.019 (2)
O19	0.1760 (6)	0.6706 (6)	0.6954 (4)	0.018 (2)
O20	0.2894 (6)	0.7213 (6)	0.7886 (5)	0.022 (2)
O21	0.2267 (6)	0.8131 (6)	0.6237 (4)	0.015 (2)
O22	0.2918 (5)	0.7230 (5)	0.5879 (4)	0.0076 (17)
O23	0.333333	0.666667	0.6905 (7)	0.011 (3)
N1	0.5262 (8)	0.6094 (7)	0.3649 (6)	0.020 (3)
C1	0.3930 (11)	0.5599 (11)	0.3123 (8)	0.029 (4)
C2	0.4468 (10)	0.5463 (10)	0.3609 (7)	0.021 (3)
C3	0.4127 (11)	0.4739 (10)	0.3990 (7)	0.028 (4)
H3	0.355016	0.429804	0.395111	0.033*
C4	0.4670 (11)	0.4694 (11)	0.4427 (8)	0.027 (4)
C5	0.5495 (10)	0.5347 (10)	0.4472 (7)	0.021 (3)
H5A	0.586555	0.531993	0.477771	0.026*
C6	0.5795 (10)	0.6054 (10)	0.4071 (7)	0.017 (3)
C7	0.6672 (9)	0.6826 (9)	0.4105 (7)	0.018 (3)
O24	0.8781 (10)	0.7242 (11)	0.3652 (7)	0.076 (5)
H24A	0.832420	0.675348	0.358365	0.114*
H24B	0.908181	0.718589	0.394985	0.114*
O25	0.9855 (12)	0.7199 (12)	0.4581 (8)	0.078 (5)
O26	0.419 (3)	0.796 (3)	0.162 (3)	0.089 (17)	0.333
H26A	0.407985	0.833191	0.180072	0.133*	0.3333
H26B	0.398461	0.801453	0.126332	0.133*	0.3333
O27	0.8519 (17)	0.8712 (16)	0.3783 (11)	0.047 (7)	0.5
H27A	0.894064	0.862536	0.386301	0.071*	0.5
H27B	0.845674	0.872527	0.337500	0.071*	0.5
O28	0.1006 (19)	0.5532 (18)	0.1200 (14)	0.062 (8)	0.5
H28A	0.106582	0.552073	0.160863	0.093*	0.5
H28B	0.057832	0.560834	0.111714	0.093*	0.5
O29	0.539 (2)	0.4313 (19)	0.5778 (13)	0.030 (5)	0.3822
H29A	0.575381	0.471452	0.602593	0.045*	0.3822
H29B	0.489431	0.427642	0.581411	0.045*	0.3822
O29A	0.843 (2)	1.032 (2)	0.2569 (17)	0.030 (5)	0.3047
H29C	0.820662	1.043854	0.224200	0.045*	0.3047
H29D	0.842092	1.061804	0.289391	0.045*	0.3047
O29B	0.860 (2)	0.949 (2)	0.2776 (17)	0.030 (5)	0.3134
H29E	0.865937	0.999268	0.275746	0.045*	0.3134
H29F	0.858118	0.929738	0.239316	0.045*	0.3134

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.051 (5)	0.051 (5)	0.013 (6)	0.025 (2)	0.000	0.000
W1	0.0121 (3)	0.0115 (3)	0.0055 (2)	0.0051 (2)	−0.0007 (2)	−0.0016 (2)
W2	0.0142 (3)	0.0158 (3)	0.0107 (3)	0.0054 (3)	0.0044 (2)	0.0018 (2)
W3	0.0154 (3)	0.0195 (3)	0.0107 (3)	0.0099 (3)	0.0037 (2)	0.0002 (2)
W4	0.0241 (3)	0.0247 (3)	0.0068 (3)	0.0118 (3)	0.0057 (2)	0.0023 (2)
Pr1	0.0280 (5)	0.0301 (5)	0.0095 (4)	0.0132 (4)	−0.0055 (3)	−0.0069 (3)
Si1	0.0078 (15)	0.0078 (15)	0.002 (2)	0.0039 (7)	0.000	0.000
O1	0.024 (5)	0.026 (5)	0.024 (5)	0.011 (4)	0.004 (4)	−0.005 (4)
O2	0.033 (5)	0.029 (5)	0.026 (5)	0.012 (4)	0.001 (4)	0.001 (4)
O3	0.025 (5)	0.025 (5)	0.025 (5)	0.015 (4)	−0.001 (4)	−0.003 (4)
O4	0.037 (6)	0.039 (7)	0.029 (6)	0.010 (5)	−0.014 (5)	0.004 (5)
O5	0.056 (8)	0.037 (7)	0.032 (6)	0.023 (6)	0.016 (6)	0.009 (5)
O6	0.061 (8)	0.073 (9)	0.030 (7)	0.030 (7)	0.003 (6)	−0.003 (6)
O7	0.052 (8)	0.060 (8)	0.019 (6)	0.007 (6)	−0.020 (5)	0.007 (5)
O8	0.024 (5)	0.035 (6)	0.035 (6)	0.015 (5)	−0.007 (5)	−0.020 (5)
O9	0.024 (6)	0.031 (6)	0.049 (7)	0.008 (5)	0.002 (5)	−0.008 (5)
O10	0.012 (4)	0.016 (4)	0.010 (4)	0.003 (3)	0.001 (3)	−0.004 (3)
O11	0.022 (5)	0.024 (5)	0.019 (5)	0.011 (5)	0.003 (4)	0.001 (4)
O12	0.032 (6)	0.031 (6)	0.014 (5)	0.017 (5)	0.005 (4)	0.007 (4)
O13	0.023 (5)	0.029 (6)	0.019 (5)	0.012 (5)	0.003 (4)	0.002 (4)
O14	0.014 (4)	0.011 (4)	0.002 (4)	0.006 (3)	−0.001 (3)	−0.001 (3)
O15	0.016 (4)	0.014 (4)	0.012 (4)	0.006 (3)	0.002 (3)	−0.001 (3)
O16	0.021 (4)	0.016 (4)	0.011 (4)	0.010 (4)	−0.001 (3)	−0.001 (3)
O17	0.012 (4)	0.022 (4)	0.012 (4)	0.008 (4)	0.001 (3)	−0.002 (3)
O18	0.020 (4)	0.023 (5)	0.012 (4)	0.009 (4)	0.003 (4)	0.001 (4)
O19	0.022 (4)	0.019 (4)	0.013 (4)	0.009 (4)	0.005 (4)	−0.003 (3)
O20	0.025 (5)	0.026 (5)	0.015 (4)	0.014 (4)	−0.001 (4)	−0.003 (4)
O21	0.021 (4)	0.018 (4)	0.010 (4)	0.013 (4)	0.000 (3)	−0.001 (3)
O22	0.008 (2)	0.008 (2)	0.007 (2)	0.0039 (15)	−0.0016 (13)	0.0004 (13)
O23	0.013 (4)	0.013 (4)	0.005 (5)	0.0067 (18)	0.000	0.000
N1	0.028 (5)	0.016 (5)	0.018 (5)	0.013 (4)	−0.003 (4)	−0.006 (4)
C1	0.030 (6)	0.030 (6)	0.028 (6)	0.016 (5)	0.005 (5)	−0.008 (5)
C2	0.025 (6)	0.022 (6)	0.018 (6)	0.013 (5)	−0.001 (5)	−0.004 (5)
C3	0.027 (6)	0.029 (6)	0.026 (6)	0.013 (5)	0.011 (5)	−0.001 (5)
C4	0.030 (6)	0.028 (6)	0.023 (6)	0.015 (5)	0.014 (5)	−0.007 (5)
C5	0.022 (6)	0.026 (6)	0.017 (6)	0.012 (5)	−0.003 (5)	−0.004 (5)
C6	0.021 (6)	0.021 (6)	0.010 (5)	0.012 (5)	0.001 (4)	−0.006 (4)
C7	0.021 (6)	0.021 (6)	0.015 (5)	0.012 (5)	0.002 (4)	−0.004 (4)
O24	0.054 (9)	0.103 (11)	0.058 (9)	0.030 (8)	−0.006 (7)	−0.004 (8)
O25	0.098 (10)	0.076 (10)	0.069 (9)	0.050 (8)	−0.012 (8)	−0.011 (8)
O26	0.09 (2)	0.10 (2)	0.08 (2)	0.047 (15)	−0.009 (13)	0.017 (13)
O27	0.062 (12)	0.048 (12)	0.028 (11)	0.025 (10)	0.001 (9)	0.002 (9)
O28	0.073 (14)	0.051 (12)	0.058 (13)	0.028 (10)	−0.019 (11)	0.013 (10)
O29	0.036 (8)	0.026 (7)	0.028 (7)	0.016 (6)	−0.003 (6)	0.000 (6)
O29A	0.036 (8)	0.026 (7)	0.028 (7)	0.016 (6)	−0.003 (6)	0.000 (6)
O29B	0.036 (8)	0.026 (7)	0.028 (7)	0.016 (6)	−0.003 (6)	0.000 (6)

Geometric parameters (Å, º)

Na1—O2^i	2.333 (13)	Si1—O22	1.629 (9)
Na1—O2^ii	2.333 (13)	Si1—O22^i	1.629 (9)
Na1—O2	2.333 (13)	Si1—O22^ii	1.629 (9)
Na1—O26	2.53 (5)	Si1—O23	1.633 (16)
Na1—O26^ii	2.53 (5)	O1—C1	1.264 (19)
Na1—O26^i	2.53 (5)	O2—C1	1.282 (19)
Na1—Pr1^i	4.137 (4)	O3—C7	1.276 (17)
Na1—Pr1	4.137 (4)	O4—C7	1.247 (18)
Na1—Pr1^ii	4.137 (4)	O5—C4	1.36 (2)
W1—O10	1.724 (9)	O5—H5	0.8399
W1—O14	1.890 (9)	O6—H6A	0.8699
W1—O15	1.906 (9)	O6—H6B	0.8701
W1—O16	1.927 (10)	O7—H7A	0.8699
W1—O14^ii	1.938 (8)	O7—H7B	0.8701
W1—O22^i	2.320 (8)	O8—H8A	0.8701
W2—O11	1.714 (10)	O8—H8B	0.8701
W2—O17	1.864 (10)	O9—H9A	0.8700
W2—O18	1.911 (9)	O9—H9B	0.8701
W2—O16	1.911 (9)	N1—C2	1.318 (18)
W2—O21^i	1.969 (9)	N1—C6	1.340 (19)
W2—O22^i	2.321 (8)	C1—C2	1.52 (2)
W3—O13	1.708 (11)	C2—C3	1.39 (2)
W3—O21	1.879 (9)	C3—C4	1.38 (2)
W3—O19	1.884 (10)	C3—H3	0.9500
W3—O17	1.936 (10)	C4—C5	1.37 (2)
W3—O15^ii	1.945 (9)	C5—C6	1.40 (2)
W3—O22	2.367 (9)	C5—H5A	0.9500
W4—O12	1.693 (10)	C6—C7	1.51 (2)
W4—O18	1.897 (10)	O24—H24A	0.8700
W4—O20^i	1.919 (10)	O24—H24B	0.8700
W4—O20	1.922 (10)	O26—H26A	0.8692
W4—O19	1.926 (10)	O26—H26B	0.8697
W4—O23	2.357 (8)	O27—H27A	0.8700
Pr1—O1	2.407 (11)	O27—H27B	0.8700
Pr1—O3^ii	2.468 (10)	O28—H28A	0.8699
Pr1—O2^ii	2.477 (11)	O28—H28B	0.8702
Pr1—O6	2.496 (13)	O29—H29A	0.8701
Pr1—O9	2.509 (12)	O29—H29B	0.8698
Pr1—O10	2.554 (9)	O29A—H29C	0.8702
Pr1—N1^ii	2.567 (12)	O29A—H29D	0.8699
Pr1—O8	2.567 (11)	O29B—H29E	0.8698
Pr1—O7	2.593 (12)	O29B—H29F	0.8701
O2^i—Na1—O2^ii	94.0 (5)	O9—Pr1—O10	84.6 (3)
O2^i—Na1—O2	94.0 (5)	O1—Pr1—N1^ii	124.3 (4)
O2^ii—Na1—O2	94.0 (5)	O3^ii—Pr1—N1^ii	63.0 (4)
O2^i—Na1—O26	71.8 (14)	O2^ii—Pr1—N1^ii	63.5 (4)
O2^ii—Na1—O26	151.8 (13)	O6—Pr1—N1^ii	134.0 (4)
O2—Na1—O26	110.8 (12)	O9—Pr1—N1^ii	134.7 (4)
O2^i—Na1—O26^ii	151.8 (13)	O10—Pr1—N1^ii	66.7 (3)
O2^ii—Na1—O26^ii	110.8 (12)	O1—Pr1—O8	125.9 (3)
O2—Na1—O26^ii	71.8 (14)	O3^ii—Pr1—O8	69.6 (4)
O26—Na1—O26^ii	90.2 (18)	O2^ii—Pr1—O8	139.6 (4)
O2^i—Na1—O26^i	110.8 (12)	O6—Pr1—O8	71.8 (4)
O2^ii—Na1—O26^i	71.8 (14)	O9—Pr1—O8	70.8 (4)
O2—Na1—O26^i	151.8 (13)	O10—Pr1—O8	140.3 (3)
O26—Na1—O26^i	90.2 (18)	N1^ii—Pr1—O8	109.7 (4)
O26^ii—Na1—O26^i	90.2 (18)	O1—Pr1—O7	125.0 (4)
O2^i—Na1—Pr1^i	77.1 (3)	O3^ii—Pr1—O7	102.9 (4)
O2^ii—Na1—Pr1^i	121.4 (4)	O2^ii—Pr1—O7	66.6 (4)
O2—Na1—Pr1^i	31.7 (3)	O6—Pr1—O7	66.3 (5)
O26—Na1—Pr1^i	80.0 (12)	O9—Pr1—O7	142.2 (4)
O26^ii—Na1—Pr1^i	78.6 (14)	O10—Pr1—O7	132.4 (4)
O26^i—Na1—Pr1^i	165.0 (13)	N1^ii—Pr1—O7	70.2 (4)
O2^i—Na1—Pr1	121.4 (4)	O8—Pr1—O7	73.6 (4)
O2^ii—Na1—Pr1	31.7 (3)	O1—Pr1—Na1	51.4 (3)
O2—Na1—Pr1	77.1 (3)	O3^ii—Pr1—Na1	153.4 (3)
O26—Na1—Pr1	165.0 (13)	O2^ii—Pr1—Na1	29.7 (3)
O26^ii—Na1—Pr1	80.0 (12)	O6—Pr1—Na1	63.7 (4)
O26^i—Na1—Pr1	78.6 (14)	O9—Pr1—Na1	119.8 (3)
Pr1^i—Na1—Pr1	108.75 (14)	O10—Pr1—Na1	85.4 (3)
O2^i—Na1—Pr1^ii	31.7 (3)	N1^ii—Pr1—Na1	93.1 (3)
O2^ii—Na1—Pr1^ii	77.1 (3)	O8—Pr1—Na1	133.7 (3)
O2—Na1—Pr1^ii	121.4 (4)	O7—Pr1—Na1	77.4 (3)
O26—Na1—Pr1^ii	78.6 (14)	O22—Si1—O22^i	110.0 (4)
O26^ii—Na1—Pr1^ii	165.0 (13)	O22—Si1—O22^ii	110.0 (4)
O26^i—Na1—Pr1^ii	80.0 (12)	O22^i—Si1—O22^ii	110.0 (4)
Pr1^i—Na1—Pr1^ii	108.75 (14)	O22—Si1—O23	108.9 (4)
Pr1—Na1—Pr1^ii	108.75 (14)	O22^i—Si1—O23	108.9 (4)
O10—W1—O14	101.6 (4)	O22^ii—Si1—O23	108.9 (4)
O10—W1—O15	98.3 (4)	C1—O1—Pr1	148.2 (10)
O14—W1—O15	92.6 (4)	C1—O2—Na1	118.2 (10)
O10—W1—O16	99.4 (4)	C1—O2—Pr1^i	122.8 (10)
O14—W1—O16	158.7 (4)	Na1—O2—Pr1^i	118.7 (5)
O15—W1—O16	87.9 (4)	C7—O3—Pr1^i	126.1 (9)
O10—W1—O14^ii	102.5 (4)	C4—O5—H5	108.1
O14—W1—O14^ii	86.4 (5)	Pr1—O6—H6A	109.1
O15—W1—O14^ii	159.0 (4)	Pr1—O6—H6B	109.3
O16—W1—O14^ii	85.6 (4)	H6A—O6—H6B	109.5
O10—W1—O22^i	169.9 (4)	Pr1—O7—H7A	109.0
O14—W1—O22^i	86.3 (3)	Pr1—O7—H7B	109.5
O15—W1—O22^i	75.0 (3)	H7A—O7—H7B	109.5
O16—W1—O22^i	73.2 (3)	Pr1—O8—H8A	109.5
O14^ii—W1—O22^i	84.0 (3)	Pr1—O8—H8B	109.2
O11—W2—O17	101.7 (4)	H8A—O8—H8B	109.5
O11—W2—O18	100.7 (5)	Pr1—O9—H9A	109.4
O17—W2—O18	86.8 (4)	Pr1—O9—H9B	109.3
O11—W2—O16	101.3 (5)	H9A—O9—H9B	109.5
O17—W2—O16	92.3 (4)	W1—O10—Pr1	165.8 (5)
O18—W2—O16	157.7 (4)	W1—O14—W1^i	150.4 (5)
O11—W2—O21^i	99.9 (4)	W1—O15—W3^i	120.7 (5)
O17—W2—O21^i	158.2 (4)	W2—O16—W1	121.2 (5)
O18—W2—O21^i	86.6 (4)	W2—O17—W3	151.8 (5)
O16—W2—O21^i	86.1 (4)	W4—O18—W2	151.4 (6)
O11—W2—O22^i	171.1 (4)	W3—O19—W4	153.0 (5)
O17—W2—O22^i	85.9 (4)	W4^ii—O20—W4	121.9 (5)
O18—W2—O22^i	84.3 (4)	W3—O21—W2^ii	122.2 (5)
O16—W2—O22^i	73.4 (4)	Si1—O22—W1^ii	123.8 (5)
O21^i—W2—O22^i	72.8 (3)	Si1—O22—W2^ii	123.7 (4)
O13—W3—O21	102.2 (5)	W1^ii—O22—W2^ii	92.2 (3)
O13—W3—O19	103.0 (4)	Si1—O22—W3	124.6 (5)
O21—W3—O19	92.8 (4)	W1^ii—O22—W3	91.1 (3)
O13—W3—O17	102.4 (4)	W2^ii—O22—W3	91.9 (3)
O21—W3—O17	155.2 (4)	Si1—O23—W4	124.7 (3)
O19—W3—O17	85.0 (4)	Si1—O23—W4^ii	124.7 (3)
O13—W3—O15^ii	98.8 (4)	W4—O23—W4^ii	90.9 (4)
O21—W3—O15^ii	87.6 (4)	Si1—O23—W4^i	124.7 (3)
O19—W3—O15^ii	157.6 (4)	W4—O23—W4^i	90.9 (4)
O17—W3—O15^ii	85.3 (4)	W4^ii—O23—W4^i	90.9 (4)
O13—W3—O22	170.7 (4)	C2—N1—C6	119.9 (13)
O21—W3—O22	73.2 (3)	C2—N1—Pr1^i	120.3 (10)
O19—W3—O22	85.5 (4)	C6—N1—Pr1^i	119.6 (10)
O17—W3—O22	82.0 (3)	O1—C1—O2	122.7 (15)
O15^ii—W3—O22	73.2 (3)	O1—C1—C2	120.6 (15)
O12—W4—O18	101.7 (5)	O2—C1—C2	116.7 (15)
O12—W4—O20^i	100.7 (5)	N1—C2—C3	123.9 (14)
O18—W4—O20^i	90.7 (4)	N1—C2—C1	114.5 (14)
O12—W4—O20	100.9 (5)	C3—C2—C1	121.6 (14)
O18—W4—O20	157.2 (4)	C4—C3—C2	116.6 (15)
O20^i—W4—O20	88.7 (6)	C4—C3—H3	121.7
O12—W4—O19	101.6 (4)	C2—C3—H3	121.7
O18—W4—O19	84.7 (4)	O5—C4—C5	119.5 (15)
O20^i—W4—O19	157.7 (4)	O5—C4—C3	120.5 (16)
O20—W4—O19	87.2 (4)	C5—C4—C3	119.8 (15)
O12—W4—O23	171.9 (5)	C4—C5—C6	120.5 (14)
O18—W4—O23	84.4 (4)	C4—C5—H5A	119.8
O20^i—W4—O23	73.6 (4)	C6—C5—H5A	119.8
O20—W4—O23	73.6 (4)	N1—C6—C5	119.3 (14)
O19—W4—O23	84.2 (4)	N1—C6—C7	115.9 (13)
O1—Pr1—O3^ii	131.7 (4)	C5—C6—C7	124.7 (13)
O1—Pr1—O2^ii	75.1 (4)	O4—C7—O3	126.4 (14)
O3^ii—Pr1—O2^ii	125.7 (4)	O4—C7—C6	118.6 (13)
O1—Pr1—O6	73.0 (4)	O3—C7—C6	115.0 (13)
O3^ii—Pr1—O6	141.3 (4)	H24A—O24—H24B	109.5
O2^ii—Pr1—O6	85.6 (4)	Na1—O26—H26A	101.6
O1—Pr1—O9	69.7 (4)	Na1—O26—H26B	120.6
O3^ii—Pr1—O9	76.4 (4)	H26A—O26—H26B	91.2
O2^ii—Pr1—O9	144.2 (4)	H27A—O27—H27B	109.5
O6—Pr1—O9	90.4 (4)	H28A—O28—H28B	109.5
O1—Pr1—O10	68.9 (3)	H29A—O29—H29B	109.5
O3^ii—Pr1—O10	74.7 (3)	H29C—O29A—H29D	109.5
O2^ii—Pr1—O10	76.6 (3)	H29E—O29B—H29F	109.5
O6—Pr1—O10	140.9 (4)
O14—W1—O10—Pr1	−127 (2)	O22^i—Si1—O23—W4	−58.5 (3)
O15—W1—O10—Pr1	138 (2)	O22^ii—Si1—O23—W4	−178.5 (3)
O16—W1—O10—Pr1	49 (2)	O22—Si1—O23—W4^ii	−58.5 (3)
O14^ii—W1—O10—Pr1	−39 (2)	O22^i—Si1—O23—W4^ii	−178.5 (3)
O22^i—W1—O10—Pr1	91 (3)	O22^ii—Si1—O23—W4^ii	61.5 (3)
O10—W1—O14—W1^i	131.2 (10)	O22—Si1—O23—W4^i	−178.5 (3)
O15—W1—O14—W1^i	−129.8 (10)	O22^i—Si1—O23—W4^i	61.5 (3)
O16—W1—O14—W1^i	−39.1 (17)	O22^ii—Si1—O23—W4^i	−58.5 (3)
O14^ii—W1—O14—W1^i	29.2 (11)	Pr1—O1—C1—O2	−78 (3)
O22^i—W1—O14—W1^i	−55.0 (10)	Pr1—O1—C1—C2	103 (2)
O11—W2—O17—W3	123.6 (11)	Na1—O2—C1—O1	13 (2)
O18—W2—O17—W3	23.4 (11)	Pr1^i—O2—C1—O1	−160.3 (11)
O16—W2—O17—W3	−134.3 (11)	Na1—O2—C1—C2	−168.4 (10)
O21^i—W2—O17—W3	−49.0 (18)	Pr1^i—O2—C1—C2	18.4 (18)
O22^i—W2—O17—W3	−61.1 (11)	C6—N1—C2—C3	1 (2)
O12—W4—O18—W2	127.5 (12)	Pr1^i—N1—C2—C3	−174.0 (11)
O20^i—W4—O18—W2	−131.4 (12)	C6—N1—C2—C1	178.7 (12)
O20—W4—O18—W2	−42.9 (19)	Pr1^i—N1—C2—C1	3.9 (16)
O19—W4—O18—W2	26.7 (12)	O1—C1—C2—N1	164.6 (13)
O23—W4—O18—W2	−57.9 (11)	O2—C1—C2—N1	−14.1 (19)
O13—W3—O19—W4	130.1 (13)	O1—C1—C2—C3	−17 (2)
O21—W3—O19—W4	−126.7 (13)	O2—C1—C2—C3	163.8 (14)
O17—W3—O19—W4	28.6 (12)	N1—C2—C3—C4	−1 (2)
O15^ii—W3—O19—W4	−36 (2)	C1—C2—C3—C4	−178.3 (13)
O22—W3—O19—W4	−53.8 (12)	C2—C3—C4—O5	176.9 (13)
O13—W3—O21—W2^ii	−171.8 (5)	C2—C3—C4—C5	1 (2)
O19—W3—O21—W2^ii	84.3 (6)	O5—C4—C5—C6	−177.3 (14)
O17—W3—O21—W2^ii	0.2 (13)	C3—C4—C5—C6	−1 (2)
O15^ii—W3—O21—W2^ii	−73.3 (5)	C2—N1—C6—C5	−1 (2)
O22—W3—O21—W2^ii	−0.1 (4)	Pr1^i—N1—C6—C5	173.7 (10)
O22^i—Si1—O22—W1^ii	−58.1 (6)	C2—N1—C6—C7	−176.7 (12)
O22^ii—Si1—O22—W1^ii	63.2 (6)	Pr1^i—N1—C6—C7	−1.9 (15)
O23—Si1—O22—W1^ii	−177.4 (3)	C4—C5—C6—N1	1 (2)
O22^i—Si1—O22—W2^ii	−178.2 (3)	C4—C5—C6—C7	176.4 (13)
O22^ii—Si1—O22—W2^ii	−56.9 (9)	Pr1^i—O3—C7—O4	173.4 (11)
O23—Si1—O22—W2^ii	62.4 (5)	Pr1^i—O3—C7—C6	−9.0 (16)
O22^i—Si1—O22—W3	61.3 (9)	N1—C6—C7—O4	−175.5 (13)
O22^ii—Si1—O22—W3	−177.5 (4)	C5—C6—C7—O4	9 (2)
O23—Si1—O22—W3	−58.1 (5)	N1—C6—C7—O3	6.6 (17)
O22—Si1—O23—W4	61.5 (3)	C5—C6—C7—O3	−168.6 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O26^ii	0.87	2.12	2.91 (6)	151
O7—H7A···O11^iii	0.87	2.36	3.084 (17)	141
O7—H7A···O21^iv	0.87	2.29	2.988 (18)	138
O7—H7B···O4^v	0.87	2.16	2.956 (19)	152
O8—H8A···O12^vi	0.87	2.17	2.929 (15)	146
O8—H8B···O4^v	0.87	2.40	3.103 (17)	138
O9—H9A···O29B^ii	0.87	2.50	3.09 (4)	123
C5—H5A···O29	0.95	2.64	3.28 (3)	126
O24—H24A···O11^vii	0.87	2.48	3.109 (19)	130
O26—H26A···O7^ii	0.87	2.23	3.10 (6)	180
O26—H26B···O27^viii	0.87	1.97	2.84 (6)	179
O27—H27A···O24	0.87	2.42	2.94 (3)	120
O27—H27B···O29B	0.87	1.79	2.51 (4)	138
O28—H28A···O7	0.87	2.09	2.75 (3)	132
O29—H29A···O11^i	0.87	2.59	3.18 (3)	127
O29A—H29C···O5^ix	0.87	1.96	2.83 (4)	180
O29A—H29D···O24^x	0.87	1.91	2.78 (4)	175
O29B—H29F···O12^xi	0.87	2.27	3.03 (4)	146

Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z; (iii) −y+1/3, x−y+2/3, z−1/3; (iv) −x+y−2/3, −x+2/3, z−1/3; (v) x−2/3, y−1/3, z−1/3; (vi) −x+y−1/3, −x+1/3, z−2/3; (vii) −x+y+1/3, −x+2/3, z−1/3; (viii) −x+y+1/3, −x+5/3, z−1/3; (ix) x+1/3, y+2/3, z−1/3; (x) −x+y+1, −x+2, z; (xi) x+2/3, y+1/3, z−2/3.