Crystal structure of undeca-potassium bis-[α-hemi-penta-hydrogen hexa-molybdoplatinate(IV)] dodeca-hydrate.

The title compound, K11[α-Pt(μ3-OH)2(μ3-OH0.5)Mo6(μ3-O)3(μ2-O)6O12]2·12H2O (simplified chemical formula K11[H2.5PtMo6O24]2·12H2O), containing the well-known Anderson-type heteropolyoxomolybdate anion, was obtained by hydro-thermal reaction at pH = ca 6.0. The complete polyanion dimer has 2/m symmetry. The locations of the H atoms with respect to protonated O atoms were obtained from difference Fourier maps, and confirmed by the inter-polyanion hydrogen bonds, bond-length elongation and bond-valence sums (BVSs). The title heteropolyanion has two types of protonated O atoms viz. μ3-OH, {Mo2-O(H)-Pt} and μ3-OH0.5 (disordered H atom). The [H2.5α-PtMo6O24](5.5-) polyanion forms a dimer, [(H2.5α-PtMo6O24)2](11-), held together by two pairs of μ3-O-H⋯μ1-O and of one disordered μ3-O⋯H⋯μ3-O hydrogen bonds. Three K(+) ions are located on special positions (two on twofold rotation axes, one on a mirror plane), and two K(+) ions are located on general positions with a reduced occupancy of 0.5. The remaining K(+) ion has a reduced occupancy of 0.25 for charge balance and reasonable displacement parameters. As a result, the numbers of K(+) and H(+) ions in the title compound are 5.5 and 2.5, respectively.

Chemical context

The α (planar structure) -β (bent structure) -α geometrical isomerization, according to stepwise protonation in the [PtMo6O24]8− polyoxometalate (POM) species, viz. ([H3.5 α-PtMo6O24]4.5− (Lee & Sasaki, 1998 ▸), [H4 β-PtMo6O24]4− (Lee & Sasaki, 1998 ▸; Joo et al., 1994 ▸) and [H4.5 α-PtMo6O24]3.5− (Lee & Sasaki, 1998 ▸; Lee et al., 2010 ▸; Joo et al., 2015 ▸), is an unprecedented phenomenon in the Anderson-type heteropolyanion (Anderson, 1937 ▸) as well as in the chemistry of POMs. However, in addition, differently protonated polyanion species have been reported, viz. [H2PtMo6O24]6− (Lee & Joo, 2000 ▸, 2004b ▸), and [H6PtMo6O24]2− (Lee & Joo, 2006a ▸,b ▸, 2010 ▸). Less protonated than the title polyanion, the species [H2PtMo6O24]6− was obtained in more acidic conditions (at pH 2.0 and 3.2). These polyanions are formed into dimers and polymers (in [H6PtMo6O24]2− polyanions) by inter­polyanion hydrogen bonds. Recently, a hydrogen-bonded hexa­molybdoplatinate(IV) tetra­mer, [(PtMo6O24)4H23]9−, and the trimers, [(PtMo6O24)3H16]8− and [(PtMo6O24)3H14]10− have been reported as the tetra-n-butyl­ammonium and tetra-n-butyl­ammonium/tri­ethyl­ammonium salts, respectively (Day et al., 2009 ▸). The same type of protonated species in a tungsten system, [H2.5PtW6O24]5.5−, has been reported by our group (Lee & Joo, 2004a ▸). We report herein the crystal structure of the title compound containing a new protonated species in the hexa­molybdoplatinate(IV) system by hemi­penta H+, [H2.5PtMo6O24]5.5−.

Structural commentary

Fig. 1 ▸ shows the building units of the title compound. The complete polyanion has point group symmetry m whereas the dimer (held together by hydrogen bonds) has 2/m symmetry. The O atoms of the heteropolyanion have been designated as OT (terminal Mo=O atom), OB (bridging μ 2-OB atom; Mo—O—Mo) and OC (centered μ 3-O atom; Mo2-–OC-–Pt). The protonated O atoms in the polyanion were confirmed by bond-valence sums (BVS; Brown & Altermatt, 1985 ▸; Brese & O’Keeffe, 1991 ▸), charge balance, bond-length elongation (Table 1 ▸) and the inter­polyanion hydrogen bonds (Fig. 2 ▸ and Table 2 ▸).

Figure 1

The mol­ecular structure of the [H2.5PtMo6O24]5.5− anion and surrounding K+ cations and water molecules. Displacement ellipsoids are drawn at the 30% probability level. The H atoms of the polyanion are presented as small spheres of arbitrary radius and the H atoms of water mol­ecules are omitted for clarity. [Symmetry code: (i) −x + 1, y, z.]

Table 1

Selected geometric parameters (, )

Pt1O1C	2.003(5)	Mo1O2C	2.110(4)
Pt1O2C	1.981(3)	Mo2O2C	2.141(3)
Pt1O3C	2.000(3)	Mo2O3C	2.307(4)
Pt1O4C	2.001(5)	Mo3O3C	2.316(4)
Mo1O1C	2.277(3)	Mo3O4C	2.140(3)
Pt1O1CMo1	98.38(17)	Pt1O3CMo2	99.35(15)
Mo1O1CMo1i	92.86(18)	Pt1O3CMo3	99.91(14)
Pt1O2CMo1	104.91(15)	Mo2O3CMo3	92.10(13)
Pt1O2CMo2	105.82(15)	Pt1O4CMo3	106.09(17)
Mo1O2CMo2	99.12(14)	Mo3O4CMo3i	97.5(2)

Symmetry code: (i) .

Figure 2

Polyhedral view of the heteropolyanion in the title compound with O—H⋯O contacts of the inter­anion hydrogen bonds shown as red dashed lines. [Symmetry codes: (i) x, − y + 1, − z + 1; (ii) − x + 1, y, z; (iii) − x + 1, − y + 1, − z + 1.]

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1CH1O1C ii	0.99(3)	1.62(6)	2.595(10)	165(17)
O3CH3O9T iii	0.97(3)	1.64(3)	2.605(5)	171(5)
O3WH3BO4W i	0.85(3)	2.07(14)	2.697(15)	130(15)
O4WH4AO9T iii	0.85(3)	2.06(7)	2.826(11)	150(12)
O4WH4BO3W i	0.85(3)	1.89(5)	2.697(15)	159(5)

Symmetry codes: (i) ; (ii) ; (iii) .

Confirmation of the protonated O atoms was strongly supported by the BVS analysis. The calculated BVSs for expected protonation atoms O1C and O3C are 1.46 and 1.39 valence units (v.u.), respectively, if the valence of the O—H bond is not included. Since the BVS value around the O atom should be 2.0 v.u., the missing valences of O1C and O3C are 0.54 and 0.61 v.u., respectively, which corresponds to the valence of the O—H bonds. The BVS value for the unproton­ated O2C, O4C, O5B–O8B atoms are 1.87, 1.78, 1.88, 1.60, 1.88 and 1.76 v.u., respectively. The value of O6B is relatively small but it is not protonated. As a result, the protonated O atoms are O1C and O3C.

The positions of atoms H1 and H3 on the protonated atoms O1C and O3C, respectively, were obtained from difference Fourier maps. The heteropolyanion forms a 2/m symmetric dimer {[H2.5PtMo6O24]2}11−, held together by each of the four μ 3(Mo2Pt)-O3C-–H3⋯μ 1(Mo)-O9T and one disordered μ 3(Mo2Pt)-O1C⋯H1⋯μ 3-O1C hydrogen bonds (Table 2 ▸ and Fig. 2 ▸).

While the structure of the dimeric polyanions is clear, the disorder among the potassium atoms and water mol­ecules makes it difficult to be as certain of the chemical structure in the regions in between. The K1–K3 ions were located in special positions, one on a mirror plane and two on twofold rotation axes. The calculated BVSs for the K1–K3 ions are 1.00, 0.90 and 1.00 v.u. (K+⋯O distance 〈 3.00 Å), respectively. Reasonable displacement parameters of K4 and K5 atoms were obtained by reducing the site occupancies to 0.5, and the BVSs for K4 and K5 ions are 1.04 and 0.91 v.u., respectively. The occupancy of K6 was further reduced to 0.25 for charge balance and reasonable displacement parameters. The calculated BVSs was 0.54 v.u. For the same reason, the occupancies of water mol­ecules O2W–O6W were reduced to 0.5. The K+ ions are variously coordinated by O atoms as [K1(OT)6]+, [K2(OT)4(OW)2]+, [K3(OC)2(OB)(OT)2(OW)2]+, [K4(OT)(OW)6]+, [K5(OT)2(OW)3]+ and [K6(OT)(OW)]+.

Supra­molecular features

The polyanion dimers are three-dimensionally linked only via K⋯OB, C and T inter­actions. Water mol­ecules O1W, O2W and O5W do not contribute to the hydrogen bonds.

Synthesis and crystallization

Crystals of the title compound were prepared by the reaction of K2MoO4·2H2O and K2Pt(OH)6 at pH = ca 6.0. as described in a previous report (Joo et al., 1994 ▸).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. Atoms H1 and H3 in the polyanion were located in difference Fourier maps and refined with U iso(H) = 1.5U eq(O), and a distance restraint of O—H = 1.00 (3) Å using the DFIX command in SHELXL2014/7 (Sheldrick, 2015 ▸). The occupancy of atom H1 was reduced to 0.5 because of disorder. Reasonable displacement parameters for atoms K4–K6 and water mol­ecules O2W–O5W were obtained by reducing their site occupancies to 0.5 because of disorder. The occupancy of K6 was further reduced to 0.25 for charge balance and reasonable displacement parameters. All H atoms of water mol­ecules O1W–O4W were found in difference Fourier maps and refined with distance and angle restraints of O—H = 0.85 (3) Å and HA—OW—HB = 1.35 (3) Å, respectively, using the command DFIX, and were included in the refinement with U iso(H) = 1.5U eq(O). The H atoms on O5W were positioned geometrically and refined using a riding model (HFIX 23), with OW—H = 0.97 Å and U iso(H) = 1.5U eq(O).

Table 3

Experimental details

Crystal data
Chemical formula	K11[H2.5PtMo6O24]212H2O
M r	1480.40
Crystal system, space group	Orthorhombic, C m c e
Temperature (K)	173
a, b, c ()	16.8552(4), 22.7112(7), 15.5503(4)
V (3)	5952.7(3)
Z	8
Radiation type	Mo K
(mm1)	8.00
Crystal size (mm)	0.25 0.15 0.14
Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 ▸)
T min, T max	0.424, 0.746
No. of measured, independent and observed [I > 2(I)] reflections	16741, 3826, 3257
R int	0.044
(sin /)max (1)	0.667
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.031, 0.076, 1.06
No. of reflections	3826
No. of parameters	264
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
max, min (e 3)	1.50, 1.32

Computer programs: APEX2 and SAINT (Bruker, 2009 ▸), SHELXS2014 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg, 1998 ▸).

The reflections (0,2,0) and (3,1,2) were omitted in the final refinement as they were obscured by the beamstop. The highest peak in the difference map is 0.86 Å from Pt1 and the deepest hole is 0.88 Å from Pt1.

Crystal structure: contains datablock(s) New_Global_Publ_Block, I. DOI: 10.1107/S2056989015014188/br2251sup1.cif

CCDC reference: 1415450

Additional supporting information: crystallographic information; 3D view; checkCIF report

K11[H2.5PtMo6O24]2·12H2O	Dx = 3.304 Mg m−3
Mr = 1480.40	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmce	Cell parameters from 3642 reflections
a = 16.8552 (4) Å	θ = 2.4–28.2°
b = 22.7112 (7) Å	µ = 8.00 mm−1
c = 15.5503 (4) Å	T = 173 K
V = 5952.7 (3) Å3	Block, pale yellow
Z = 8	0.25 × 0.15 × 0.14 mm
F(000) = 5512

Bruker SMART APEXII CCD diffractometer	3826 independent reflections
Radiation source: rotating anode	3257 reflections with I > 2σ(I)
Detector resolution: 10.0 pixels mm-1	Rint = 0.044
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −22→22
Tmin = 0.424, Tmax = 0.746	k = −30→17
16741 measured reflections	l = −16→20

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)] = 0.031	Hydrogen site location: difference Fourier map
wR(F2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0297P)2 + 46.2991P] where P = (Fo2 + 2Fc2)/3
3826 reflections	(Δ/σ)max = 0.001
264 parameters	Δρmax = 1.50 e Å−3
14 restraints	Δρmin = −1.32 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.5000	0.37721 (2)	0.50594 (2)	0.00882 (8)
Mo1	0.40210 (3)	0.43798 (2)	0.34971 (3)	0.01424 (11)
Mo2	0.30535 (3)	0.36824 (2)	0.49776 (3)	0.01495 (11)
Mo3	0.40452 (2)	0.29903 (2)	0.65278 (3)	0.01481 (11)
O1C	0.5000	0.4557 (2)	0.4473 (3)	0.0123 (10)
H1	0.5000	0.485 (6)	0.495 (8)	0.018*	0.5
O2C	0.41239 (19)	0.36081 (16)	0.4244 (2)	0.0125 (7)
O3C	0.41006 (19)	0.39059 (16)	0.5875 (2)	0.0131 (7)
H3	0.402 (3)	0.4250 (19)	0.623 (3)	0.020*
O4C	0.5000	0.2979 (2)	0.5621 (3)	0.0131 (10)
O5B	0.5000	0.4138 (2)	0.2959 (3)	0.0160 (11)
O6B	0.3265 (2)	0.44740 (18)	0.4460 (2)	0.0208 (8)
O7B	0.3379 (2)	0.29588 (17)	0.5512 (2)	0.0176 (8)
O8B	0.5000	0.3212 (2)	0.7162 (3)	0.0158 (11)
O9T	0.4015 (2)	0.51246 (17)	0.3235 (3)	0.0187 (8)
O10T	0.3402 (2)	0.40612 (17)	0.2754 (2)	0.0196 (8)
O11T	0.2431 (2)	0.3418 (2)	0.4200 (3)	0.0266 (9)
O12T	0.2448 (2)	0.3962 (2)	0.5763 (3)	0.0273 (10)
O13T	0.3397 (2)	0.33250 (19)	0.7226 (3)	0.0237 (9)
O14T	0.4017 (2)	0.22555 (18)	0.6778 (3)	0.0228 (9)
K1	0.2500	0.30728 (8)	0.2500	0.0221 (4)
K2	0.2500	0.43286 (8)	0.7500	0.0267 (4)
K3	0.5000	0.28050 (8)	0.33118 (12)	0.0254 (4)
K4	0.09783 (17)	0.43827 (17)	0.5206 (2)	0.0371 (7)	0.5
K5	0.09202 (17)	0.3486 (2)	0.4765 (2)	0.0595 (12)	0.5
K6	0.1660 (5)	0.2717 (3)	0.6235 (4)	0.0478 (19)	0.25
O1W	0.1839 (3)	0.4814 (2)	0.3701 (4)	0.0412 (13)
H1A	0.159 (4)	0.451 (2)	0.346 (5)	0.062*
H1B	0.219 (4)	0.465 (3)	0.402 (4)	0.062*
O2W	0.0345 (5)	0.3851 (4)	0.3785 (6)	0.033 (2)	0.5
H2A	0.066 (6)	0.355 (3)	0.371 (10)	0.049*	0.5
H2B	0.065 (6)	0.414 (4)	0.363 (10)	0.049*	0.5
O3W	0.4326 (6)	0.4488 (5)	0.9311 (7)	0.041 (3)	0.5
H3A	0.466 (7)	0.470 (6)	0.958 (7)	0.062*	0.5
H3B	0.446 (9)	0.452 (7)	0.878 (3)	0.062*	0.5
O4W	0.4571 (6)	0.4175 (4)	0.8141 (6)	0.038 (2)	0.5
H4A	0.448 (8)	0.448 (4)	0.785 (8)	0.057*	0.5
H4B	0.5000	0.424 (5)	0.842 (4)	0.057*
O5W	0.0461 (6)	0.2998 (5)	0.5369 (7)	0.051 (3)	0.5
H5A	0.0637	0.2610	0.5192	0.077*	0.5
H5B	0.0637	0.3054	0.5958	0.077*	0.5

	U11	U22	U33	U12	U13	U23
Pt1	0.00455 (12)	0.00998 (13)	0.01192 (13)	0.000	0.000	−0.00001 (10)
Mo1	0.0159 (2)	0.0116 (2)	0.0152 (2)	0.00145 (17)	−0.00367 (16)	0.00085 (17)
Mo2	0.0058 (2)	0.0224 (3)	0.0166 (2)	−0.00089 (16)	0.00046 (15)	0.00087 (18)
Mo3	0.0083 (2)	0.0173 (2)	0.0188 (2)	−0.00036 (17)	0.00244 (16)	0.00565 (18)
O1C	0.013 (2)	0.011 (2)	0.014 (2)	0.000	0.000	0.0032 (19)
O2C	0.0108 (17)	0.0133 (18)	0.0134 (17)	−0.0018 (14)	−0.0018 (13)	−0.0013 (14)
O3C	0.0082 (16)	0.0160 (19)	0.0151 (17)	0.0009 (14)	0.0038 (13)	−0.0016 (14)
O4C	0.012 (2)	0.010 (2)	0.017 (3)	0.000	0.000	0.003 (2)
O5B	0.014 (2)	0.017 (3)	0.018 (3)	0.000	0.000	−0.005 (2)
O6B	0.0136 (18)	0.029 (2)	0.0201 (19)	0.0078 (17)	0.0040 (15)	0.0056 (17)
O7B	0.0113 (18)	0.021 (2)	0.0211 (19)	−0.0064 (15)	−0.0024 (14)	0.0052 (16)
O8B	0.012 (2)	0.018 (3)	0.017 (3)	0.000	0.000	0.001 (2)
O9T	0.020 (2)	0.0154 (19)	0.021 (2)	−0.0003 (15)	−0.0019 (16)	0.0000 (15)
O10T	0.0150 (19)	0.022 (2)	0.0214 (19)	−0.0014 (16)	−0.0032 (15)	−0.0007 (16)
O11T	0.0155 (19)	0.045 (3)	0.020 (2)	−0.0050 (19)	−0.0028 (15)	0.0079 (19)
O12T	0.0132 (19)	0.046 (3)	0.023 (2)	0.0072 (18)	0.0036 (16)	0.006 (2)
O13T	0.0104 (18)	0.037 (3)	0.024 (2)	0.0049 (17)	0.0041 (15)	0.0083 (18)
O14T	0.0162 (19)	0.025 (2)	0.028 (2)	−0.0049 (16)	−0.0038 (16)	0.0080 (18)
K1	0.0160 (8)	0.0282 (10)	0.0223 (9)	0.000	0.0027 (6)	0.000
K2	0.0275 (10)	0.0299 (10)	0.0227 (9)	0.000	0.0033 (7)	0.000
K3	0.0253 (9)	0.0248 (10)	0.0262 (9)	0.000	0.000	−0.0107 (7)
K4	0.0198 (14)	0.061 (2)	0.0307 (16)	0.0001 (13)	−0.0029 (12)	−0.0010 (15)
K5	0.0178 (15)	0.118 (4)	0.0425 (19)	0.0099 (18)	0.0007 (13)	−0.013 (2)
K6	0.091 (5)	0.019 (3)	0.034 (3)	−0.010 (3)	0.037 (3)	−0.007 (2)
O1W	0.038 (3)	0.039 (3)	0.047 (3)	0.016 (2)	−0.017 (2)	−0.010 (2)
O2W	0.039 (5)	0.037 (5)	0.022 (4)	0.006 (4)	0.007 (4)	0.000 (4)
O3W	0.024 (5)	0.067 (8)	0.032 (6)	0.010 (5)	−0.009 (5)	−0.005 (5)
O4W	0.052 (6)	0.027 (5)	0.035 (5)	0.004 (5)	−0.002 (4)	0.001 (4)
O5W	0.059 (7)	0.049 (7)	0.045 (6)	0.016 (6)	−0.003 (5)	−0.021 (5)

Pt1—O1C	2.003 (5)	O13T—K2	2.768 (4)
Pt1—O2C	1.981 (3)	O14T—K1ii	2.890 (4)
Pt1—O3C	2.000 (3)	O14T—K3iii	2.907 (4)
Pt1—O4C	2.001 (5)	O14T—K5ii	2.934 (6)
Mo1—O1C	2.277 (3)	K1—O10Tvi	2.740 (4)
Mo1—O2C	2.110 (4)	K1—O11Tvi	2.760 (4)
Mo2—O2C	2.141 (3)	K1—O14Tii	2.890 (4)
Mo2—O3C	2.307 (4)	K1—O14Tvii	2.890 (4)
Mo3—O3C	2.316 (4)	K2—O13Tv	2.768 (4)
Mo3—O4C	2.140 (3)	K2—O12Tv	2.828 (4)
Pt1—O2Ci	1.981 (3)	K2—O1Wviii	2.919 (6)
Pt1—O3Ci	2.000 (3)	K2—O1Wix	2.919 (6)
Pt1—K3	3.4943 (18)	K2—O9Tviii	3.060 (4)
Mo1—O10T	1.717 (4)	K2—O9Tix	3.060 (4)
Mo1—O9T	1.740 (4)	K3—O2Ci	2.759 (4)
Mo1—O5B	1.930 (3)	K3—O5Wx	2.852 (12)
Mo1—O6B	1.978 (4)	K3—O5Wii	2.852 (12)
Mo1—K3	3.9494 (17)	K3—O14Tvii	2.907 (4)
Mo2—O11T	1.709 (4)	K3—O14Txi	2.907 (4)
Mo2—O12T	1.714 (4)	K3—O8Bxi	2.921 (5)
Mo2—O7B	1.921 (4)	K4—O3Wv	0.940 (11)
Mo2—O6B	2.002 (4)	K4—O2W	2.735 (10)
Mo3—O14T	1.714 (4)	K4—O4Wv	2.773 (11)
Mo3—O13T	1.717 (4)	K4—O1Wix	2.884 (6)
Mo3—O7B	1.939 (4)	K4—O3Wxii	2.894 (10)
Mo3—O8B	1.953 (3)	K4—O1W	2.923 (7)
Mo3—Mo3i	3.2187 (8)	K4—O3Wiv	2.963 (12)
O1C—Mo1i	2.278 (3)	K4—O5W	3.274 (12)
O1C—H1	0.99 (3)	K5—O5W	1.647 (13)
O2C—K3	2.759 (4)	K5—O2W	1.987 (10)
O2C—K6ii	3.370 (7)	K5—O3Wv	2.723 (13)
O3C—H3	0.97 (3)	K5—O5Wxiii	2.744 (11)
O4C—Mo3i	2.140 (3)	K5—O2Wxiii	2.750 (9)
O5B—Mo1i	1.930 (3)	K5—O14Tii	2.934 (6)
O5B—K3	3.077 (6)	K6—O5W	2.512 (14)
O7B—K6ii	3.121 (7)	K6—O13Tv	2.765 (7)
O7B—K6	3.155 (8)	K6—O11Tii	3.074 (8)
O8B—Mo3i	1.953 (3)	K6—O7Bii	3.121 (7)
O8B—K3iii	2.921 (5)	K6—O2Cii	3.370 (7)
O9T—K2iv	3.060 (4)	O1W—H1A	0.88 (3)
O10T—K1	2.740 (4)	O1W—H1B	0.86 (3)
O11T—K5	2.698 (5)	O2W—H2A	0.86 (3)
O11T—K1	2.760 (4)	O2W—H2B	0.87 (3)
O11T—K6ii	3.074 (8)	O3W—H3A	0.86 (3)
O12T—K4	2.792 (5)	O3W—H3B	0.85 (3)
O12T—K2	2.828 (4)	O4W—H4A	0.85 (3)
O12T—K5	3.195 (6)	O4W—H4B	0.85 (3)
O12T—K6	3.210 (7)	O5W—H5A	0.9700
O13T—K6v	2.765 (7)	O5W—H5B	0.9700
Pt1—O1C—Mo1	98.38 (17)	O2C—K3—O5Wx	101.0 (2)
Mo1—O1C—Mo1i	92.86 (18)	O2Ci—K3—O5Wx	84.2 (2)
Pt1—O2C—Mo1	104.91 (15)	O2C—K3—O5Wii	84.2 (2)
Pt1—O2C—Mo2	105.82 (15)	O2Ci—K3—O5Wii	101.0 (2)
Mo1—O2C—Mo2	99.12 (14)	O5Wx—K3—O5Wii	31.6 (4)
Pt1—O3C—Mo2	99.35 (15)	O2C—K3—O14Tvii	99.06 (11)
Pt1—O3C—Mo3	99.91 (14)	O2Ci—K3—O14Tvii	140.13 (13)
Mo2—O3C—Mo3	92.10 (13)	O5Wx—K3—O14Tvii	135.6 (2)
Pt1—O4C—Mo3	106.09 (17)	O5Wii—K3—O14Tvii	113.9 (2)
Mo3—O4C—Mo3i	97.5 (2)	O2C—K3—O14Txi	140.14 (13)
O2Ci—Pt1—O2C	96.4 (2)	O2Ci—K3—O14Txi	99.06 (11)
O2Ci—Pt1—O3C	177.79 (14)	O5Wx—K3—O14Txi	113.9 (2)
O2C—Pt1—O3C	82.50 (15)	O5Wii—K3—O14Txi	135.6 (2)
O2Ci—Pt1—O3Ci	82.50 (15)	O14Tvii—K3—O14Txi	69.49 (16)
O2C—Pt1—O3Ci	177.79 (14)	O2C—K3—O8Bxi	147.63 (7)
O3C—Pt1—O3Ci	98.6 (2)	O2Ci—K3—O8Bxi	147.63 (7)
O2Ci—Pt1—O4C	96.31 (14)	O5Wx—K3—O8Bxi	86.3 (2)
O2C—Pt1—O4C	96.31 (14)	O5Wii—K3—O8Bxi	86.3 (2)
O3C—Pt1—O4C	81.95 (14)	O14Tvii—K3—O8Bxi	57.34 (11)
O3Ci—Pt1—O4C	81.94 (14)	O14Txi—K3—O8Bxi	57.34 (11)
O2Ci—Pt1—O1C	82.88 (14)	O2C—K3—O5B	56.17 (11)
O2C—Pt1—O1C	82.88 (14)	O2Ci—K3—O5B	56.16 (11)
O3C—Pt1—O1C	98.84 (14)	O5Wx—K3—O5B	139.2 (2)
O3Ci—Pt1—O1C	98.84 (14)	O5Wii—K3—O5B	139.2 (2)
O4C—Pt1—O1C	178.8 (2)	O14Tvii—K3—O5B	84.27 (12)
O10T—Mo1—O9T	104.34 (18)	O14Txi—K3—O5B	84.27 (12)
O10T—Mo1—O5B	96.18 (18)	O8Bxi—K3—O5B	131.98 (15)
O9T—Mo1—O5B	100.4 (2)	O3Wv—K4—O2W	123.0 (7)
O10T—Mo1—O6B	99.42 (17)	O3Wv—K4—O4Wv	28.4 (7)
O9T—Mo1—O6B	93.92 (17)	O2W—K4—O4Wv	122.9 (3)
O5B—Mo1—O6B	155.52 (18)	O3Wv—K4—O12T	108.9 (6)
O10T—Mo1—O2C	94.06 (16)	O2W—K4—O12T	116.4 (2)
O9T—Mo1—O2C	159.58 (16)	O4Wv—K4—O12T	87.2 (2)
O5B—Mo1—O2C	86.13 (18)	O3Wv—K4—O1Wix	69.1 (7)
O6B—Mo1—O2C	74.10 (15)	O2W—K4—O1Wix	162.1 (3)
O10T—Mo1—O1C	164.43 (18)	O4Wv—K4—O1Wix	74.3 (3)
O9T—Mo1—O1C	89.35 (18)	O12T—K4—O1Wix	65.64 (16)
O5B—Mo1—O1C	73.73 (16)	O3Wv—K4—O3Wxii	41.1 (6)
O6B—Mo1—O1C	86.76 (15)	O2W—K4—O3Wxii	82.6 (3)
O2C—Mo1—O1C	73.78 (15)	O4Wv—K4—O3Wxii	56.8 (3)
O11T—Mo2—O12T	105.6 (2)	O12T—K4—O3Wxii	143.3 (2)
O11T—Mo2—O7B	100.41 (18)	O1Wix—K4—O3Wxii	106.2 (3)
O12T—Mo2—O7B	100.32 (18)	O3Wv—K4—O1W	145.6 (8)
O11T—Mo2—O6B	98.06 (18)	O2W—K4—O1W	72.2 (2)
O12T—Mo2—O6B	93.40 (19)	O4Wv—K4—O1W	164.8 (3)
O7B—Mo2—O6B	153.03 (15)	O12T—K4—O1W	85.57 (15)
O11T—Mo2—O2C	96.48 (16)	O1Wix—K4—O1W	90.59 (19)
O12T—Mo2—O2C	155.60 (17)	O3Wxii—K4—O1W	131.1 (3)
O7B—Mo2—O2C	85.55 (15)	O3Wv—K4—O3Wiv	93.5 (8)
O6B—Mo2—O2C	72.94 (14)	O2W—K4—O3Wiv	86.3 (3)
O11T—Mo2—O3C	167.10 (17)	O4Wv—K4—O3Wiv	121.7 (3)
O12T—Mo2—O3C	86.74 (16)	O12T—K4—O3Wiv	126.5 (2)
O7B—Mo2—O3C	73.03 (14)	O1Wix—K4—O3Wiv	79.4 (3)
O6B—Mo2—O3C	84.81 (14)	O3Wxii—K4—O3Wiv	83.3 (3)
O2C—Mo2—O3C	72.23 (13)	O1W—K4—O3Wiv	54.5 (2)
O14T—Mo3—O13T	105.6 (2)	O3Wv—K4—O5W	92.1 (8)
O14T—Mo3—O7B	97.66 (17)	O2W—K4—O5W	62.3 (3)
O13T—Mo3—O7B	99.35 (17)	O4Wv—K4—O5W	71.1 (3)
O14T—Mo3—O8B	99.1 (2)	O12T—K4—O5W	83.3 (2)
O13T—Mo3—O8B	95.24 (18)	O1Wix—K4—O5W	134.1 (2)
O7B—Mo3—O8B	153.87 (17)	O3Wxii—K4—O5W	78.6 (3)
O14T—Mo3—O4C	99.17 (19)	O1W—K4—O5W	121.1 (2)
O13T—Mo3—O4C	154.17 (19)	O3Wiv—K4—O5W	145.3 (3)
O7B—Mo3—O4C	84.17 (15)	O5W—K5—O11T	126.2 (4)
O8B—Mo3—O4C	73.51 (16)	O2W—K5—O11T	103.6 (3)
O14T—Mo3—O3C	167.13 (17)	O5W—K5—O3Wv	100.9 (4)
O13T—Mo3—O3C	84.56 (16)	O2W—K5—O3Wv	89.0 (4)
O7B—Mo3—O3C	72.52 (14)	O11T—K5—O3Wv	111.3 (3)
O8B—Mo3—O3C	87.51 (17)	O5W—K5—O5Wxiii	30.0 (4)
O4C—Mo3—O3C	72.02 (15)	O2W—K5—O5Wxiii	91.0 (4)
Pt1—O1C—Mo1i	98.38 (17)	O11T—K5—O5Wxiii	152.7 (3)
Mo1—O5B—Mo1i	117.5 (3)	O3Wv—K5—O5Wxiii	91.6 (3)
Mo1—O6B—Mo2	108.78 (18)	O5W—K5—O2Wxiii	98.9 (4)
Mo2—O7B—Mo3	119.1 (2)	O2W—K5—O2Wxiii	21.7 (3)
Mo3i—O8B—Mo3	111.0 (2)	O11T—K5—O2Wxiii	124.7 (3)
O10T—K1—O10Tvi	69.96 (16)	O3Wv—K5—O2Wxiii	85.5 (3)
O10T—K1—O11Tvi	83.21 (13)	O5Wxiii—K5—O2Wxiii	69.7 (3)
O10Tvi—K1—O11Tvi	69.68 (12)	O5W—K5—O14Tii	95.6 (4)
O10T—K1—O11T	69.68 (12)	O2W—K5—O14Tii	68.3 (3)
O10Tvi—K1—O11T	83.21 (13)	O11T—K5—O14Tii	70.56 (14)
O11Tvi—K1—O11T	147.0 (2)	O3Wv—K5—O14Tii	156.5 (3)
O10T—K1—O14Tii	130.28 (12)	O5Wxiii—K5—O14Tii	94.5 (3)
O10Tvi—K1—O14Tii	77.07 (11)	O2Wxiii—K5—O14Tii	75.4 (2)
O11Tvi—K1—O14Tii	118.84 (11)	O5W—K5—K5xiii	62.0 (4)
O11T—K1—O14Tii	70.39 (12)	O2W—K5—K5xiii	60.8 (3)
O10T—K1—O14Tvii	77.07 (11)	O5W—K5—O12T	109.2 (4)
O10Tvi—K1—O14Tvii	130.28 (12)	O2W—K5—O12T	128.6 (4)
O11Tvi—K1—O14Tvii	70.39 (12)	O11T—K5—O12T	54.31 (13)
O11T—K1—O14Tvii	118.84 (11)	O3Wv—K5—O12T	65.4 (2)
O14Tii—K1—O14Tvii	150.10 (18)	O5Wxiii—K5—O12T	130.8 (3)
O13T—K2—O13Tv	69.14 (16)	O2Wxiii—K5—O12T	142.4 (3)
O13T—K2—O12T	68.14 (12)	O14Tii—K5—O12T	124.24 (14)
O13Tv—K2—O12T	83.57 (13)	O5W—K6—O13Tv	108.0 (3)
O13T—K2—O12Tv	83.57 (13)	O5W—K6—O11Tii	119.7 (3)
O13Tv—K2—O12Tv	68.14 (12)	O13Tv—K6—O11Tii	128.8 (3)
O12T—K2—O12Tv	145.8 (2)	O5W—K6—O7Bii	69.0 (3)
O13T—K2—O1Wviii	116.05 (13)	O13Tv—K6—O7Bii	176.7 (3)
O13Tv—K2—O1Wviii	131.23 (13)	O11Tii—K6—O7Bii	53.59 (14)
O12T—K2—O1Wviii	145.01 (14)	O5W—K6—O7B	120.2 (3)
O12Tv—K2—O1Wviii	64.73 (13)	O13Tv—K6—O7B	104.7 (3)
O13T—K2—O1Wix	131.23 (13)	O11Tii—K6—O7B	67.06 (18)
O13Tv—K2—O1Wix	116.05 (13)	O7Bii—K6—O7B	78.15 (17)
O12T—K2—O1Wix	64.73 (13)	O5W—K6—O12T	89.2 (3)
O12Tv—K2—O1Wix	145.01 (14)	O13Tv—K6—O12T	76.85 (18)
O1Wviii—K2—O1Wix	96.3 (2)	O11Tii—K6—O12T	118.9 (2)
O13T—K2—O9Tviii	147.91 (12)	O7Bii—K6—O12T	104.03 (19)
O13Tv—K2—O9Tviii	79.69 (11)	O7B—K6—O12T	52.07 (14)
O12T—K2—O9Tviii	116.73 (11)	O5W—K6—O2Cii	78.0 (3)
O12Tv—K2—O9Tviii	77.81 (11)	O13Tv—K6—O2Cii	128.6 (2)
O1Wviii—K2—O9Tviii	79.00 (12)	O11Tii—K6—O2Cii	52.97 (13)
O1Wix—K2—O9Tviii	69.48 (13)	O7Bii—K6—O2Cii	50.21 (13)
O13T—K2—O9Tix	79.69 (11)	O7B—K6—O2Cii	115.9 (2)
O13Tv—K2—O9Tix	147.92 (12)	O12T—K6—O2Cii	153.9 (2)
O12T—K2—O9Tix	77.81 (11)	H1A—O1W—H1B	103 (4)
O12Tv—K2—O9Tix	116.74 (11)	H2A—O2W—H2B	101 (5)
O1Wviii—K2—O9Tix	69.48 (13)	H3A—O3W—H3B	105 (5)
O1Wix—K2—O9Tix	79.00 (12)	H4A—O4W—H4B	107 (5)
O9Tviii—K2—O9Tix	132.12 (16)	H5A—O5W—H5B	107.1
O2C—K3—O2Ci	64.72 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1C—H1···O1Cxiv	0.99 (3)	1.62 (6)	2.595 (10)	165 (17)
O3C—H3···O9Tix	0.97 (3)	1.64 (3)	2.605 (5)	171 (5)
O3W—H3B···O4Wi	0.85 (3)	2.07 (14)	2.697 (15)	130 (15)
O4W—H4A···O9Tix	0.85 (3)	2.06 (7)	2.826 (11)	150 (12)
O4W—H4B···O3Wi	0.85 (3)	1.89 (5)	2.697 (15)	159 (5)