Bis(4,4'-bipyridinium) dodeca-tungsto-silicate 4,4'-bipyridine hexa-hydrate.

The title compound, (C(10)H(10)N(2))(2)[SiW(12)O(40)]·C(10)H(8)N(2)·6H(2)O or (4,4'-bipyH(2))(2)[SiW(12)O(40)].(4,4'-bipy)·6H(2)O (4,4'-bipy is 4,4'-bipyridine), was prepared under hydro-thermal conditions. The asymmetric unit contains a discrete Keggin-type [SiW(12)O(40)](4-) anion (located on a twofold axis), one 4,4'-bipy (located on a twofold axis), two (4,4'-bipyH(2))(2+) cations and six uncoordinated water mol-ecules. The polyoxoanion is constructed from a central SiO(4) tetra-hedron which shares its O atoms with four trinuclear W(3)O(13) groups, each of which is made up of three edge-sharing WO(6) octa-hedra. The water mol-ecules and [SiW(12)O(40)](4-) anions are linked through hydrogen bonds.

Related literature

For related literature, see: Hill (1998 ▶); Kurth et al. (2001 ▶); Misono (1987 ▶); Pope (1983 ▶). H4SiW12O40.nH2O was prepared according to literature procedures (Rocchiccioli-Deltcheff et al., 1983 ▶).

Experimental

Crystal data

(C10H10N2)2[SiW12O40]·C10H8N2·6H2O

M = 3454.85

Monoclinic,

a = 15.491 (5) Å

b = 18.096 (5) Å

c = 20.921 (5) Å

β = 100.834 (5)°

V = 5760 (3) Å3

Z = 4

Mo Kα radiation

μ = 23.99 mm−1

T = 293 (2) K

0.15 × 0.12 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.041, T max = 0.095

15853 measured reflections

5652 independent reflections

5214 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.101

S = 1.10

5652 reflections

455 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 3.60 e Å−3

Δρmin = −3.50 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027566/rk2097sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027566/rk2097Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C10H10N2)2[SiW12O40]·C10H8N2·6H2O	F(000) = 6128
Mr = 3454.85	Dx = 3.984 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 5214 reflections
a = 15.491 (5) Å	θ = 1.8–26.0°
b = 18.096 (5) Å	µ = 23.99 mm−1
c = 20.921 (5) Å	T = 293 K
β = 100.834 (5)°	Block, black
V = 5760 (3) Å3	0.15 × 0.12 × 0.10 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	5652 independent reflections
Radiation source: Rotor target	5214 reflections with I > 2σ(I)
graphite	Rint = 0.042
Detector resolution: 10.0 pixels mm-1	θmax = 26.0°, θmin = 1.8°
ω scans	h = −19→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→22
Tmin = 0.041, Tmax = 0.095	l = −23→25
15853 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.049P)2 + 129.9363P] where P = (Fo2 + 2Fc2)/3
5652 reflections	(Δ/σ)max = 0.002
455 parameters	Δρmax = 3.60 e Å−3
8 restraints	Δρmin = −3.50 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 largeas those based on F, and R–factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Si1	1.0000	0.14417 (15)	0.7500	0.0055 (5)
W1	0.98109 (2)	0.004870 (18)	0.865205 (16)	0.01358 (10)
W2	0.81326 (2)	0.150489 (19)	0.823667 (17)	0.01562 (10)
W3	0.83728 (2)	0.008359 (18)	0.701365 (16)	0.01280 (10)
W4	0.86857 (2)	0.136541 (19)	0.593364 (17)	0.01711 (10)
W5	0.83464 (2)	0.280029 (18)	0.712749 (16)	0.01327 (10)
W6	1.03445 (2)	0.282564 (18)	0.639007 (16)	0.01417 (10)
C1	0.7254 (7)	0.6611 (5)	0.4178 (5)	0.0264 (14)
H1	0.7714	0.6664	0.3953	0.032*
C2	0.6599 (7)	0.7125 (5)	0.4101 (5)	0.0254 (13)
H2	0.6598	0.7520	0.3816	0.031*
C3	0.5934 (6)	0.7045 (5)	0.4454 (5)	0.0210 (13)
C4	0.5952 (7)	0.6445 (5)	0.4877 (5)	0.0223 (13)
H4	0.5515	0.6386	0.5123	0.027*
C5	0.6624 (7)	0.5948 (5)	0.4922 (5)	0.0266 (13)
H5	0.6649	0.5544	0.5200	0.032*
C6	0.5183 (6)	0.7587 (5)	0.4376 (5)	0.0210 (13)
C7	0.4350 (6)	0.7337 (5)	0.4437 (5)	0.0219 (13)
H7	0.4262	0.6843	0.4530	0.026*
C8	0.3650 (7)	0.7838 (5)	0.4357 (5)	0.0228 (14)
H8	0.3090	0.7681	0.4396	0.027*
C9	0.4582 (6)	0.8799 (5)	0.4160 (5)	0.0240 (14)
H9	0.4648	0.9297	0.4069	0.029*
C10	0.5303 (7)	0.8325 (5)	0.4228 (5)	0.0227 (13)
H10	0.5850	0.8498	0.4175	0.027*
C11	0.5736 (6)	−0.0110 (5)	0.7442 (4)	0.0195 (13)
H11	0.6235	−0.0379	0.7401	0.023*
C12	0.5755 (6)	0.0660 (5)	0.7443 (4)	0.0174 (12)
H12	0.6269	0.0908	0.7406	0.021*
C13	0.5000	0.1061 (7)	0.7500	0.0159 (14)
C14	0.5000	0.1881 (6)	0.7500	0.0146 (14)
C15	0.5682 (6)	0.2278 (5)	0.7320 (4)	0.0174 (12)
H15	0.6147	0.2029	0.7193	0.021*
C16	0.5676 (6)	0.3045 (5)	0.7328 (4)	0.0206 (13)
H16	0.6141	0.3307	0.7214	0.025*
N1	0.7246 (6)	0.6045 (5)	0.4565 (4)	0.0265 (13)
H1N	0.770 (5)	0.584 (6)	0.461 (6)	0.040*
N2	0.3794 (6)	0.8539 (4)	0.4226 (4)	0.0252 (14)
H2N	0.334 (5)	0.875 (6)	0.419 (6)	0.038*
N3	0.5000	−0.0457 (6)	0.7500	0.0192 (16)
N4	0.5000	0.3407 (6)	0.7500	0.0192 (16)
O1	0.9447 (4)	−0.0617 (3)	0.9112 (3)	0.0163 (12)
O2	1.0599 (4)	0.0597 (3)	0.9308 (3)	0.0120 (10)
O3	1.0822 (4)	−0.0439 (3)	0.8440 (3)	0.0122 (10)
O5	0.8959 (4)	0.0815 (3)	0.8665 (3)	0.0116 (9)
O6	0.8667 (4)	0.2281 (3)	0.8797 (3)	0.0134 (9)
O7	0.7236 (4)	0.1323 (3)	0.8568 (3)	0.0165 (11)
O8	0.7635 (4)	0.2270 (3)	0.7623 (3)	0.0146 (8)
O9	0.7957 (4)	0.0824 (3)	0.7520 (3)	0.0141 (8)
O10	0.9299 (4)	0.1957 (3)	0.7773 (3)	0.0104 (8)
O11	0.9167 (4)	−0.0197 (3)	0.7808 (3)	0.0135 (9)
O12	0.7571 (4)	−0.0570 (3)	0.6969 (3)	0.0198 (12)
O13	0.9484 (4)	0.0926 (3)	0.6913 (3)	0.0096 (8)
O14	0.7932 (4)	0.0625 (3)	0.6220 (3)	0.0135 (9)
O15	0.8026 (4)	0.1562 (3)	0.5197 (3)	0.0184 (12)
O16	0.9609 (4)	0.2067 (3)	0.5959 (3)	0.0136 (9)
O17	0.8220 (4)	0.2048 (3)	0.6488 (3)	0.0146 (9)
O18	0.7599 (4)	0.3442 (3)	0.6770 (3)	0.0198 (12)
O19	1.1124 (4)	0.3313 (3)	0.7084 (3)	0.0136 (10)
O20	1.0266 (5)	0.3501 (3)	0.5807 (3)	0.0214 (13)
O21	0.9400 (4)	0.3087 (3)	0.6807 (3)	0.0159 (9)
O1W	0.9247 (5)	0.4797 (4)	0.5870 (4)	0.0332 (12)
H1A	0.890 (7)	0.469 (7)	0.615 (4)	0.050*
H1B	0.920 (8)	0.457 (6)	0.553 (4)	0.050*
O2W	0.8790 (5)	0.5277 (4)	0.4605 (4)	0.0319 (13)
H2A	0.932 (7)	0.547 (6)	0.463 (5)	0.048*
H2B	0.859 (7)	0.506 (6)	0.427 (4)	0.048*
O3W	0.7508 (5)	0.4587 (4)	0.5805 (4)	0.0380 (13)
H3A	0.780 (8)	0.416 (4)	0.594 (5)	0.057*
H3B	0.763 (9)	0.487 (5)	0.618 (4)	0.057*

	U11	U22	U33	U12	U13	U23
Si1	0.0050 (12)	0.0012 (11)	0.0111 (12)	0.000	0.0033 (10)	0.000
W1	0.0161 (2)	0.00723 (17)	0.01860 (19)	0.00094 (13)	0.00648 (14)	0.00361 (12)
W2	0.0143 (2)	0.01192 (18)	0.02205 (19)	0.00164 (13)	0.00714 (14)	−0.00002 (13)
W3	0.0121 (2)	0.00709 (17)	0.01982 (18)	−0.00403 (12)	0.00457 (13)	−0.00200 (12)
W4	0.0176 (2)	0.01453 (19)	0.01848 (19)	0.00010 (14)	0.00146 (14)	0.00044 (13)
W5	0.0137 (2)	0.00674 (17)	0.01943 (18)	0.00445 (12)	0.00332 (13)	0.00175 (12)
W6	0.0179 (2)	0.00714 (17)	0.01819 (18)	−0.00104 (13)	0.00512 (14)	0.00300 (12)
C1	0.022 (3)	0.022 (3)	0.037 (3)	0.000 (2)	0.010 (2)	−0.002 (2)
C2	0.023 (3)	0.019 (2)	0.035 (3)	0.001 (2)	0.008 (2)	0.000 (2)
C3	0.018 (3)	0.017 (2)	0.029 (3)	0.000 (2)	0.007 (2)	−0.002 (2)
C4	0.019 (2)	0.018 (2)	0.031 (2)	0.001 (2)	0.007 (2)	−0.001 (2)
C5	0.023 (3)	0.022 (3)	0.034 (3)	0.001 (2)	0.005 (2)	0.001 (2)
C6	0.020 (3)	0.015 (2)	0.028 (3)	0.002 (2)	0.005 (2)	0.000 (2)
C7	0.020 (3)	0.017 (2)	0.030 (3)	0.003 (2)	0.006 (2)	0.000 (2)
C8	0.019 (3)	0.019 (3)	0.032 (3)	0.003 (3)	0.009 (3)	0.002 (3)
C9	0.023 (3)	0.016 (3)	0.033 (3)	0.002 (3)	0.006 (3)	−0.002 (3)
C10	0.021 (3)	0.016 (2)	0.031 (3)	0.000 (2)	0.007 (2)	0.000 (2)
C11	0.018 (2)	0.012 (2)	0.029 (2)	0.001 (2)	0.003 (2)	−0.002 (2)
C12	0.016 (2)	0.011 (2)	0.025 (2)	0.000 (2)	0.003 (2)	0.000 (2)
C13	0.015 (3)	0.010 (3)	0.022 (3)	0.000	0.002 (2)	0.000
C14	0.014 (3)	0.009 (3)	0.021 (3)	0.000	0.004 (2)	0.000
C15	0.016 (2)	0.011 (2)	0.025 (2)	0.000 (2)	0.004 (2)	0.000 (2)
C16	0.020 (3)	0.014 (2)	0.028 (3)	−0.002 (2)	0.004 (2)	0.002 (2)
N1	0.020 (3)	0.021 (2)	0.038 (3)	0.004 (2)	0.005 (2)	−0.004 (2)
N2	0.023 (3)	0.019 (3)	0.034 (3)	0.006 (2)	0.008 (2)	0.001 (2)
N3	0.018 (3)	0.011 (3)	0.029 (3)	0.000	0.004 (3)	0.000
N4	0.019 (3)	0.013 (3)	0.025 (3)	0.000	0.002 (3)	0.000
O1	0.018 (3)	0.010 (3)	0.023 (3)	0.001 (2)	0.007 (2)	0.007 (2)
O2	0.011 (2)	0.0089 (19)	0.016 (2)	0.0007 (18)	0.0036 (17)	0.0043 (17)
O3	0.013 (2)	0.005 (2)	0.019 (2)	0.0014 (18)	0.0047 (18)	0.0035 (18)
O5	0.0132 (18)	0.0082 (17)	0.0149 (17)	−0.0005 (16)	0.0060 (15)	0.0017 (15)
O6	0.0144 (19)	0.0075 (18)	0.0190 (18)	0.0021 (16)	0.0049 (17)	−0.0011 (16)
O7	0.015 (3)	0.014 (2)	0.021 (2)	0.003 (2)	0.006 (2)	0.000 (2)
O8	0.0131 (17)	0.0107 (16)	0.0201 (16)	0.0028 (15)	0.0037 (15)	0.0016 (15)
O9	0.0138 (16)	0.0097 (15)	0.0194 (15)	0.0000 (14)	0.0050 (14)	−0.0002 (14)
O10	0.0116 (17)	0.0047 (16)	0.0155 (16)	0.0012 (15)	0.0039 (15)	0.0004 (14)
O11	0.0158 (18)	0.0084 (17)	0.0171 (18)	−0.0005 (16)	0.0049 (16)	0.0026 (16)
O12	0.016 (3)	0.014 (3)	0.030 (3)	−0.004 (2)	0.007 (2)	−0.002 (2)
O13	0.0106 (16)	0.0052 (16)	0.0142 (16)	0.0010 (15)	0.0054 (14)	−0.0004 (14)
O14	0.0119 (18)	0.0090 (17)	0.0194 (17)	−0.0019 (16)	0.0025 (16)	−0.0018 (16)
O15	0.019 (3)	0.016 (3)	0.019 (3)	0.002 (2)	0.002 (2)	0.004 (2)
O16	0.0141 (19)	0.0090 (18)	0.0189 (18)	0.0006 (17)	0.0061 (16)	0.0016 (16)
O17	0.0140 (17)	0.0103 (16)	0.0193 (16)	0.0017 (15)	0.0023 (15)	0.0004 (15)
O18	0.022 (3)	0.016 (2)	0.023 (3)	0.009 (2)	0.007 (2)	0.007 (2)
O19	0.015 (2)	0.005 (2)	0.021 (2)	−0.0026 (18)	0.0053 (18)	0.0020 (18)
O20	0.025 (3)	0.015 (3)	0.026 (3)	0.000 (2)	0.008 (2)	0.012 (2)
O21	0.0165 (18)	0.0096 (17)	0.0224 (18)	0.0011 (16)	0.0053 (16)	0.0014 (16)
O1W	0.029 (2)	0.026 (2)	0.044 (2)	−0.001 (2)	0.006 (2)	0.005 (2)
O2W	0.025 (3)	0.026 (3)	0.045 (3)	0.001 (2)	0.008 (2)	−0.003 (2)
O3W	0.032 (3)	0.033 (2)	0.048 (3)	0.001 (2)	0.005 (2)	0.007 (2)

Si1—O10	1.614 (6)	C3—C4	1.397 (13)
Si1—O10i	1.614 (6)	C3—C6	1.507 (13)
Si1—O13	1.627 (5)	C4—C5	1.366 (13)
Si1—O13i	1.627 (5)	C4—H4	0.9300
W1—O1	1.703 (6)	C5—N1	1.337 (14)
W1—O11	1.911 (5)	C5—H5	0.9300
W1—O5	1.918 (6)	C6—C10	1.391 (13)
W1—O3	1.921 (6)	C6—C7	1.395 (14)
W1—O2	1.931 (6)	C7—C8	1.400 (13)
W1—O13i	2.366 (5)	C7—H7	0.9300
W2—O7	1.697 (6)	C8—N2	1.325 (12)
W2—O5	1.889 (5)	C8—H8	0.9300
W2—O6	1.915 (6)	C9—N2	1.340 (13)
W2—O9	1.921 (6)	C9—C10	1.394 (14)
W2—O8	1.945 (6)	C9—H9	0.9300
W2—O10	2.353 (6)	C10—H10	0.9300
W3—O12	1.706 (6)	C11—N3	1.327 (11)
W3—O9	1.894 (6)	C11—C12	1.395 (12)
W3—O14	1.939 (6)	C11—H11	0.9300
W3—O11	1.940 (5)	C12—C13	1.400 (11)
W3—O3i	1.948 (6)	C12—H12	0.9300
W3—O13	2.338 (5)	C13—C12ii	1.400 (11)
W4—O15	1.719 (6)	C13—C14	1.483 (17)
W4—O2i	1.904 (6)	C14—C15ii	1.388 (11)
W4—O16	1.907 (6)	C14—C15	1.388 (11)
W4—O17	1.924 (6)	C15—C16	1.387 (12)
W4—O14	1.943 (6)	C15—H15	0.9300
W4—O13	2.325 (5)	C16—N4	1.341 (11)
W5—O18	1.709 (6)	C16—H16	0.9300
W5—O17	1.894 (6)	N1—H1N	0.79 (6)
W5—O8	1.909 (6)	N2—H2N	0.79 (6)
W5—O19i	1.935 (6)	N3—C11ii	1.327 (11)
W5—O21	1.948 (6)	N4—C16ii	1.341 (11)
W5—O10	2.363 (5)	O2—W4i	1.904 (6)
W6—O20	1.715 (6)	O3—W3i	1.948 (6)
W6—O21	1.898 (6)	O6—W6i	1.923 (6)
W6—O16	1.900 (6)	O10—W6i	2.341 (5)
W6—O19	1.919 (6)	O13—W1i	2.366 (5)
W6—O6i	1.923 (6)	O19—W5i	1.935 (6)
W6—O10i	2.341 (5)	O1W—H1A	0.89 (6)
C1—N1	1.306 (13)	O1W—H1B	0.81 (6)
C1—C2	1.364 (14)	O2W—H2A	0.88 (9)
C1—H1	0.9300	O2W—H2B	0.80 (6)
C2—C3	1.383 (14)	O3W—H3A	0.92 (6)
C2—H2	0.9300	O3W—H3B	0.93 (6)
O10—Si1—O10i	109.4 (4)	O19—W6—O6i	88.7 (2)
O10—Si1—O13	109.3 (3)	O20—W6—O10i	170.4 (3)
O10i—Si1—O13	109.4 (3)	O21—W6—O10i	85.3 (2)
O10—Si1—O13i	109.4 (3)	O16—W6—O10i	84.6 (2)
O10i—Si1—O13i	109.3 (3)	O19—W6—O10i	73.5 (2)
O13—Si1—O13i	110.0 (4)	O6i—W6—O10i	74.0 (2)
O1—W1—O11	100.7 (3)	N1—C1—C2	120.9 (10)
O1—W1—O5	101.7 (3)	N1—C1—H1	119.5
O11—W1—O5	86.6 (2)	C2—C1—H1	119.5
O1—W1—O3	100.2 (3)	C1—C2—C3	118.5 (10)
O11—W1—O3	89.2 (2)	C1—C2—H2	120.8
O5—W1—O3	158.2 (2)	C3—C2—H2	120.8
O1—W1—O2	101.2 (3)	C2—C3—C4	119.5 (9)
O11—W1—O2	158.0 (2)	C2—C3—C6	120.7 (9)
O5—W1—O2	87.9 (2)	C4—C3—C6	119.8 (9)
O3—W1—O2	88.0 (2)	C5—C4—C3	118.6 (10)
O1—W1—O13i	172.0 (2)	C5—C4—H4	120.7
O11—W1—O13i	84.5 (2)	C3—C4—H4	120.7
O5—W1—O13i	84.6 (2)	N1—C5—C4	119.7 (9)
O3—W1—O13i	73.7 (2)	N1—C5—H5	120.2
O2—W1—O13i	73.8 (2)	C4—C5—H5	120.2
O7—W2—O5	102.2 (3)	C10—C6—C7	119.7 (9)
O7—W2—O6	100.6 (3)	C10—C6—C3	121.1 (9)
O5—W2—O6	91.0 (2)	C7—C6—C3	119.2 (8)
O7—W2—O9	100.8 (3)	C6—C7—C8	119.3 (9)
O5—W2—O9	86.0 (2)	C6—C7—H7	120.4
O6—W2—O9	158.5 (3)	C8—C7—H7	120.4
O7—W2—O8	98.9 (3)	N2—C8—C7	119.2 (9)
O5—W2—O8	158.8 (3)	N2—C8—H8	120.4
O6—W2—O8	87.4 (2)	C7—C8—H8	120.4
O9—W2—O8	87.8 (2)	N2—C9—C10	120.0 (9)
O7—W2—O10	170.8 (2)	N2—C9—H9	120.0
O5—W2—O10	85.5 (2)	C10—C9—H9	120.0
O6—W2—O10	73.8 (2)	C6—C10—C9	118.4 (9)
O9—W2—O10	84.7 (2)	C6—C10—H10	120.8
O8—W2—O10	73.8 (2)	C9—C10—H10	120.8
O12—W3—O9	101.6 (3)	N3—C11—C12	119.3 (9)
O12—W3—O14	99.7 (3)	N3—C11—H11	120.3
O9—W3—O14	91.1 (2)	C12—C11—H11	120.3
O12—W3—O11	101.7 (3)	C11—C12—C13	120.1 (9)
O9—W3—O11	86.2 (2)	C11—C12—H12	119.9
O14—W3—O11	158.5 (2)	C13—C12—H12	119.9
O12—W3—O3i	99.4 (3)	C12ii—C13—C12	117.5 (11)
O9—W3—O3i	158.7 (2)	C12ii—C13—C14	121.2 (6)
O14—W3—O3i	89.0 (2)	C12—C13—C14	121.2 (6)
O11—W3—O3i	85.9 (2)	C15ii—C14—C15	117.5 (11)
O12—W3—O13	171.3 (2)	C15ii—C14—C13	121.2 (6)
O9—W3—O13	85.6 (2)	C15—C14—C13	121.2 (5)
O14—W3—O13	74.9 (2)	C16—C15—C14	120.5 (9)
O11—W3—O13	83.6 (2)	C16—C15—H15	119.7
O3i—W3—O13	73.9 (2)	C14—C15—H15	119.7
O15—W4—O2i	101.0 (3)	N4—C16—C15	120.0 (9)
O15—W4—O16	101.7 (3)	N4—C16—H16	120.0
O2i—W4—O16	91.3 (2)	C15—C16—H16	120.0
O15—W4—O17	100.4 (3)	C1—N1—C5	122.8 (9)
O2i—W4—O17	158.6 (2)	C1—N1—H1N	109 (9)
O16—W4—O17	85.4 (3)	C5—N1—H1N	127 (9)
O15—W4—O14	97.4 (3)	C8—N2—C9	123.4 (9)
O2i—W4—O14	89.5 (2)	C8—N2—H2N	108 (9)
O16—W4—O14	160.3 (2)	C9—N2—H2N	129 (9)
O17—W4—O14	86.7 (2)	C11ii—N3—C11	123.6 (11)
O15—W4—O13	171.5 (2)	C16ii—N4—C16	121.4 (11)
O2i—W4—O13	75.2 (2)	W4i—O2—W1	120.5 (3)
O16—W4—O13	86.1 (2)	W1—O3—W3i	121.0 (3)
O17—W4—O13	83.5 (2)	W2—O5—W1	151.4 (3)
O14—W4—O13	75.1 (2)	W2—O6—W6i	121.3 (3)
O18—W5—O17	102.0 (3)	W5—O8—W2	121.2 (3)
O18—W5—O8	99.6 (3)	W3—O9—W2	151.4 (3)
O17—W5—O8	91.6 (3)	Si1—O10—W6i	125.0 (3)
O18—W5—O19i	101.0 (3)	Si1—O10—W2	124.4 (3)
O17—W5—O19i	156.7 (2)	W6i—O10—W2	90.93 (19)
O8—W5—O19i	88.5 (3)	Si1—O10—W5	124.1 (3)
O18—W5—O21	102.2 (3)	W6i—O10—W5	91.59 (19)
O17—W5—O21	86.0 (3)	W2—O10—W5	90.8 (2)
O8—W5—O21	158.1 (2)	W1—O11—W3	150.2 (3)
O19i—W5—O21	85.3 (2)	Si1—O13—W4	125.0 (3)
O18—W5—O10	171.0 (3)	Si1—O13—W3	124.9 (3)
O17—W5—O10	84.8 (2)	W4—O13—W3	91.37 (19)
O8—W5—O10	74.2 (2)	Si1—O13—W1i	123.6 (3)
O19i—W5—O10	72.7 (2)	W4—O13—W1i	90.46 (18)
O21—W5—O10	84.0 (2)	W3—O13—W1i	91.39 (18)
O20—W6—O21	101.0 (3)	W3—O14—W4	118.5 (3)
O20—W6—O16	102.7 (3)	W6—O16—W4	150.9 (3)
O21—W6—O16	87.3 (3)	W5—O17—W4	152.4 (3)
O20—W6—O19	99.3 (3)	W6—O19—W5i	122.0 (3)
O21—W6—O19	88.2 (3)	W6—O21—W5	149.3 (3)
O16—W6—O19	158.0 (2)	H1A—O1W—H1B	119 (9)
O20—W6—O6i	99.9 (3)	H2A—O2W—H2B	117 (10)
O21—W6—O6i	159.0 (2)	H3A—O3W—H3B	102 (6)
O16—W6—O6i	87.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O3W	0.89 (10)	2.15 (11)	2.699 (11)	119 (7)
O1W—H1B···O2W	0.81 (9)	2.31 (9)	2.749 (12)	115 (10)
O1W—H1B···O20	0.81 (9)	2.54 (11)	2.844 (10)	104 (8)
N1—H1N···O2W	0.78 (9)	1.97 (9)	2.754 (12)	172 (14)
O3W—H3A···O18	0.91 (9)	2.24 (10)	2.878 (10)	127 (9)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O3W	0.89 (10)	2.15 (11)	2.699 (11)	119 (7)
O1W—H1B⋯O2W	0.81 (9)	2.31 (9)	2.749 (12)	115 (10)
O1W—H1B⋯O20	0.81 (9)	2.54 (11)	2.844 (10)	104 (8)
N1—H1N⋯O2W	0.78 (9)	1.97 (9)	2.754 (12)	172 (14)
O3W—H3A⋯O18	0.91 (9)	2.24 (10)	2.878 (10)	127 (9)