Tris(piperazinediium) phosphatododeca­molybo(V,VI)phosphate

Lu, Y.; Xu, J.; Yu, H.

doi:10.1107/S1600536810002473

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m263-m264

doi:10.1107/S1600536810002473

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Tris(piperazinediium) phosphatododecamolybo(V,VI)phosphate

Yu-kun Lu,^a,^b Ji-qing Xu ^b ^* and Hai-hui Yu ^c

^aCollege of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao Shandong 266555, People's Republic of China, ^bCollege of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, People's Republic of China, and ^cCollege of Chemical Engineering, Northeast Dianli University, Jilin 132012, People's Republic of China
^*Correspondence e-mail: luyukun1983@sina.com

(Received 29 December 2009; accepted 20 January 2010; online 6 February 2010)

The title compound, (C₄H₁₂N₂)₃[PMo₁₂O₄₀] or (H₂pip)₃[PMo₁₂O₄₀] (pip is piperazine), was prepared under hydrothermal conditions. The asymmetric unit contains one-sixth of a mixed-valent Mo(V,VI) pseudo-Keggin-type [PMo₁₂O₄₀]⁶⁻ anion and half a piperazinediium cation, (H₂pip)²⁺. The discrete Keggin-type [PMo₁₂O₄₀]^6-anion has $[\overline{3}]$ site symmetry and the three (H₂pip)²⁺ cations each have $[\overline{1}]$ site symmetry at the centres of the molecules. The central P atom is on special position $[\overline{3}]$ , which is a roto-inversion position and generates the disorder of the PO₄ tetrahedron. Furthermore, six doubly bridging oxide groups are also disordered with an occupancy factor of 0.5 for each O atom. The anions and cations are linked by an extensive network of intermolecular N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For polyoxometalate chemistry, see: Pope & Müller (1991 ); Hill (1998 ); Kurth et al. (2001 ). For related structures, see: Han et al. (2005 ); Li et al. (2007 ); Yuan et al. (2008 ). For general background to bond-valence calculations, see: Brown & Altermatt (1985 ).

Experimental

Crystal data

(C₄H₁₂N₂)₃[PMo₁₂O₄₀]
M_r = 2086.72
Trigonal, $[R \overline 3c ]$
a = 17.890 (3) Å
c = 23.600 (6) Å
V = 6541 (2) Å³
Z = 6
Mo Kα radiation
μ = 3.49 mm⁻¹
T = 296 K
0.20 × 0.16 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.517, T_max = 0.682
11291 measured reflections
1413 independent reflections
1363 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.053
S = 1.14
1413 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O6	0.90	2.22	2.812 (4)	123
N1—H1D⋯O50	0.90	2.43	2.926 (6)	115
N1—H1C⋯O4ⁱ	0.90	2.20	3.041 (7)	155
N1—H1C⋯O40ⁱ	0.90	2.16	3.047 (7)	168
N1—H1C⋯O30ⁱⁱ	0.90	2.52	3.091 (6)	122
N1—H1D⋯O5	0.90	2.19	2.852 (6)	130
N1—H1D⋯O1ⁱⁱⁱ	0.90	2.14	2.900 (4)	142
C1—H1A⋯O6	0.97	2.58	3.101 (5)	114
C1—H1B⋯O4^iv	0.97	2.58	3.347 (7)	137
C2—H2A⋯O2^iv	0.97	2.43	3.291 (4)	148
C2—H2B⋯O3ⁱⁱ	0.97	2.43	3.156 (6)	132
C2—H2B⋯O2^v	0.97	2.42	3.068 (4)	124
Symmetry codes: (i) -x+y, -x, z; (ii) y, -x+y, -z; (iii) $[x+{\script{1\over 3}}, x-y+{\script{2\over 3}}, z+{\script{1\over 6}}]$ ; (iv) $[x-y+{\script{2\over 3}}, x+{\script{1\over 3}}, -z+{\script{1\over 3}}]$ ; (v) $[-y+{\script{2\over 3}}, -x+{\script{1\over 3}}, z-{\script{1\over 6}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002473/si2235sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810002473/si2235Isup2.hkl

checkCIF report

Comment top

Polyoxometalates (POMs) comprise a rich and diverse family of metal oxygen clusters made up of early transition metals (primarily including W, Mo and V) with unique redox, acidic, magnetic and catalytic properties (Pope & Müller, 1991; Hill, 1998). The Keggin-type structure was of epoch-making significance in the history of POMs chemistry (Kurth, 2001). The Keggin-type polyanions, [PMo₁₂O₄₀]^3-, have been indicated as excellent building blocks to construct novel compounds (Li et al., 2007; Yuan et al., 2008).

The structure of the title compound consists of a discrete polyoxoanion [PMo₁₂O₄₀]^6- and three diprotonated piperazine molecules. The heteropolyoxoanion [PMo₁₂O₄₀]^6- has a roto-inversion symmetry with the P1 atom located on the 3 centre. The pseudo-Keggin unit [PMo₁₂O₄₀]^6- may be viewed as a shell of {Mo₁₂O₃₆} encapsulating a disordered {PO₄} moiety, present at its center and responsible for the local tetrahedral geometry. The central P atom is surrounded by a cube of eight oxygen (six O7 and two O8) atoms with each of them half occupied due to the inversion symmetry at P1, and each oxygen of the {PO₄} group covalently bonded to three different molybdenum centers of the shell (Fig. 1). All Mo centers possess similar distorted octahedral geometry MoO₆ defined by one terminal oxygen atom, four doubly bridging oxo-groups and one central oxygen atom. Six doubly bridging oxo-groups (O3, O30, O4, O40, O5 and O50) are disordered with occupancy factor 0.5.

Extensive hydrogen bonding interactions help to stabilize the structure (Table 1). Each (H₂pip)²⁺cation donates eight N—H···O hydrogen bonds to eight bridging oxygen atoms from two [PMo₁₂O₄₀]^6- anions and two ones to two terminal oxygen atoms from the other two [PMo₁₂O₄₀]^6-anions. Each [PMo₁₂O₄₀]^6- anion joins twelve (H₂pip)²⁺cations to generate a three-dimensional supramolecular network structure (Fig.2).

Result of bond valence sum (Brown & Altermatt, 1985) calculation for Mo centers gives the average value 5.71 (5.52 for Mo1 and 5.89 for Mo2) in good agreement with the expected value of 5.75, which reveals that there exist three Mo^V and nine Mo^VI atoms in the Keggin-type compound. The three classes of Mo—O average distances are 1.663, 1.925 and 2.482 Å, being obviously larger than the corresponding distances in [PMo₁₂O₄₀]^5- (1.638, 1.891 and 2.443 Å) (Han et al., 2005).

Related literature top

For polyoxometalate chemistry, see: Pope & Müller (1991); Hill (1998); Kurth et al. (2001). For related structures, see: Han et al. (2005); Li et al. (2007); Yuan et al. (2008). For general background to bond-valence calculations, see: Brown & Altermatt (1985).

Experimental top

A mixture of KH₂PO₄.2H₂O(0.70 g, 5 mmol), MoO₃.2H₂O (0.45 g, 2.5 mmol), pip (0.43 g, 5 mmol), H₃BO₃(0.31 g, 5 mmol) and 18 ml water was stirred for 2 h in air; it was adjusted to pH = 1 with HCl solution (18 wt %) and was heated in a 25 ml stainless steel reactor with a Teflon-liner at 180°C for 5 days, and then cooled to room temperature. Black polyhedron crystals were isolated with 71% yield (based on Mo). Elemental analysis for 1: Anal. Calcd: C, 6.91; H, 1.74; N, 4.03; found: C, 6.96; H, 1.67; N, 4.11.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: RAPID-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecule of (I) with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted. [Symmetry codes: (i) -x, -y, -z; (ii)x-y, x, -z; (iii) -x + y, -x, z; (iv) -y, x-y, z; (v) y, -x + y, -z; (vi) -x + 2/3,-y + 1/3, -z + 1/3]
	Fig. 2. Ball-stick representation of the three-dimensional supramolecular network structure of (I).

Tris(piperazinediium) phosphatododecamolybdo(V,VI)phosphate top

Crystal data top

(C₄H₁₂N₂)₃[PMo₁₂O₄₀]	D_x = 3.178 Mg m⁻³
M_r = 2086.72	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 7741 reflections
a = 17.890 (3) Å	θ = 2.3–25.9°
c = 23.600 (6) Å	µ = 3.49 mm⁻¹
V = 6541 (2) Å³	T = 296 K
Z = 6	Polyhedron, black
F(000) = 5934	0.20 × 0.16 × 0.11 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1413 independent reflections
Radiation source: fine-focus sealed tube	1363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 10 pixels mm^-1	θ_max = 25.9°, θ_min = 2.2°
ω scans	h = −21→20
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −21→21
T_min = 0.517, T_max = 0.682	l = −25→28
11291 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.020	H-atom parameters constrained
wR(F²) = 0.053	w = 1/[σ²(F_o²) + (0.0243P)² + 29.698P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max < 0.001
1413 reflections	Δρ_max = 0.66 e Å⁻³
142 parameters	Δρ_min = −0.61 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000246 (16)

Crystal data top

(C₄H₁₂N₂)₃[PMo₁₂O₄₀]	Z = 6
M_r = 2086.72	Mo Kα radiation
Trigonal, R3c	µ = 3.49 mm⁻¹
a = 17.890 (3) Å	T = 296 K
c = 23.600 (6) Å	0.20 × 0.16 × 0.11 mm
V = 6541 (2) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	1413 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1363 reflections with I > 2σ(I)
T_min = 0.517, T_max = 0.682	R_int = 0.056
11291 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.053	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0243P)² + 29.698P] where P = (F_o² + 2F_c²)/3
1413 reflections	Δρ_max = 0.66 e Å⁻³
142 parameters	Δρ_min = −0.61 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O40	−0.0237 (5)	0.1531 (4)	0.0737 (3)	0.0207 (13)	0.50
O30	0.0735 (4)	0.2139 (4)	−0.0190 (2)	0.0197 (11)	0.50
O50	0.1366 (4)	0.1818 (4)	0.0714 (2)	0.0194 (11)	0.50
C1	0.2710 (2)	0.1678 (2)	0.20485 (14)	0.0309 (8)
H1A	0.2122	0.1414	0.2187	0.037*
H1B	0.3058	0.2205	0.2261	0.037*
C2	0.3615 (2)	0.2263 (2)	0.11974 (13)	0.0268 (7)
H2A	0.3992	0.2809	0.1383	0.032*
H2B	0.3605	0.2373	0.0796	0.032*
Mo1	−0.038697 (18)	0.177638 (17)	0.000676 (10)	0.02000 (11)
Mo2	0.046862 (16)	0.131369 (17)	0.123257 (11)	0.01944 (11)
N1	0.27315 (17)	0.18861 (18)	0.14324 (12)	0.0247 (6)
H1C	0.2375	0.1402	0.1241	0.030*
H1D	0.2541	0.2262	0.1386	0.030*
O1	−0.05695 (18)	0.26048 (17)	0.00042 (11)	0.0377 (6)
O2	0.06793 (17)	0.1903 (2)	0.18145 (11)	0.0451 (7)
O3	0.0872 (4)	0.2510 (4)	−0.0075 (2)	0.0184 (11)	0.50
O4	−0.0138 (4)	0.1855 (4)	0.0855 (3)	0.0191 (13)	0.50
O5	0.1516 (4)	0.2187 (4)	0.0842 (2)	0.0187 (11)	0.50
O6	0.09680 (17)	0.06339 (16)	0.14146 (18)	0.0583 (10)
O7	0.0325 (2)	0.0921 (2)	0.02241 (16)	0.0151 (8)	0.50
O8	0.0000	0.0000	0.0639 (3)	0.0148 (13)	0.50
P1	0.0000	0.0000	0.0000	0.0119 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O40	0.027 (3)	0.026 (4)	0.017 (3)	0.019 (3)	−0.001 (2)	−0.003 (2)
O30	0.019 (3)	0.020 (3)	0.020 (3)	0.010 (3)	0.000 (2)	0.000 (2)
O50	0.019 (3)	0.021 (3)	0.018 (3)	0.010 (3)	0.000 (2)	−0.002 (2)
C1	0.0290 (18)	0.045 (2)	0.0244 (16)	0.0228 (16)	0.0041 (13)	0.0029 (14)
C2	0.0221 (16)	0.0303 (17)	0.0239 (16)	0.0099 (14)	−0.0001 (12)	0.0070 (13)
Mo1	0.02413 (17)	0.01744 (16)	0.02263 (17)	0.01355 (12)	0.00507 (10)	0.00335 (9)
Mo2	0.01881 (16)	0.02439 (17)	0.01642 (16)	0.01178 (12)	−0.00270 (9)	−0.00659 (10)
N1	0.0208 (13)	0.0267 (14)	0.0283 (14)	0.0131 (11)	−0.0023 (11)	0.0028 (11)
O1	0.0555 (17)	0.0341 (14)	0.0390 (14)	0.0340 (13)	0.0132 (12)	0.0100 (11)
O2	0.0340 (15)	0.0623 (19)	0.0436 (16)	0.0276 (14)	−0.0132 (12)	−0.0350 (14)
O3	0.020 (3)	0.014 (3)	0.022 (3)	0.009 (3)	−0.001 (2)	0.001 (2)
O4	0.023 (3)	0.020 (3)	0.021 (3)	0.015 (3)	0.000 (2)	−0.005 (2)
O5	0.021 (3)	0.019 (3)	0.018 (3)	0.011 (3)	−0.001 (2)	−0.003 (2)
O6	0.0199 (13)	0.0171 (13)	0.137 (3)	0.0088 (10)	0.0052 (16)	0.0017 (15)
O7	0.0169 (19)	0.016 (2)	0.0123 (18)	0.0078 (16)	0.0009 (15)	0.0017 (14)
O8	0.015 (2)	0.015 (2)	0.015 (3)	0.0074 (10)	0.000	0.000
P1	0.0117 (5)	0.0117 (5)	0.0124 (8)	0.0058 (2)	0.000	0.000

Geometric parameters (Å, º) top

O40—O4	0.586 (5)	Mo2—O6	1.884 (3)
O40—Mo1	1.830 (7)	Mo2—O6^iv	1.921 (3)
O40—Mo2	1.898 (7)	Mo2—O5	1.968 (6)
O30—O3	0.641 (5)	Mo2—O4	1.991 (7)
O30—Mo1	1.833 (6)	Mo2—O7	2.458 (4)
O30—Mo1ⁱ	1.892 (6)	Mo2—O8	2.494 (4)
O50—O5	0.650 (5)	N1—H1C	0.9000
O50—Mo1ⁱ	1.833 (5)	N1—H1D	0.9000
O50—Mo2	1.855 (6)	O3—Mo1ⁱ	2.007 (6)
C1—N1	1.497 (4)	O5—Mo1ⁱ	2.061 (5)
C1—C2ⁱⁱ	1.504 (5)	O6—Mo2^v	1.921 (3)
C1—H1A	0.9700	O7—P1	1.541 (4)
C1—H1B	0.9700	O7—O8	1.747 (5)
C2—N1	1.481 (4)	O7—O7ⁱⁱⁱ	1.793 (5)
C2—C1ⁱⁱ	1.504 (5)	O7—O7ⁱ	1.793 (5)
C2—H2A	0.9700	O7—Mo1ⁱ	2.492 (4)
C2—H2B	0.9700	O8—P1	1.508 (7)
Mo1—O1	1.669 (2)	O8—O7^v	1.747 (5)
Mo1—O50ⁱⁱⁱ	1.833 (5)	O8—O7^iv	1.747 (5)
Mo1—O30ⁱⁱⁱ	1.892 (6)	O8—Mo2^v	2.494 (4)
Mo1—O3	1.970 (6)	O8—Mo2^iv	2.494 (4)
Mo1—O3ⁱⁱⁱ	2.007 (6)	P1—O8^vi	1.508 (7)
Mo1—O4	2.039 (7)	P1—O7ⁱ	1.541 (4)
Mo1—O5ⁱⁱⁱ	2.061 (5)	P1—O7^vi	1.541 (4)
Mo1—O7	2.485 (4)	P1—O7^v	1.541 (4)
Mo1—O7ⁱⁱⁱ	2.492 (4)	P1—O7ⁱⁱⁱ	1.541 (4)
Mo2—O2	1.656 (2)	P1—O7^iv	1.541 (4)

O4—O40—Mo1	102.6 (13)	O6—Mo2—O7	92.98 (15)
O4—O40—Mo2	90.4 (13)	O40—Mo2—O7	58.4 (2)
Mo1—O40—Mo2	145.2 (4)	O6^iv—Mo2—O7	92.46 (15)
O3—O30—Mo1	92.6 (9)	O5—Mo2—O7	72.26 (18)
O3—O30—Mo1ⁱ	90.9 (9)	O4—Mo2—O7	72.59 (19)
Mo1—O30—Mo1ⁱ	147.3 (3)	O2—Mo2—O8	158.13 (17)
O5—O50—Mo1ⁱ	101.3 (9)	O50—Mo2—O8	83.6 (2)
O5—O50—Mo2	90.2 (9)	O6—Mo2—O8	64.16 (14)
Mo1ⁱ—O50—Mo2	151.6 (3)	O40—Mo2—O8	84.4 (2)
N1—C1—C2ⁱⁱ	110.1 (3)	O6^iv—Mo2—O8	63.75 (14)
N1—C1—H1A	109.6	O5—Mo2—O8	102.89 (18)
C2ⁱⁱ—C1—H1A	109.6	O4—Mo2—O8	101.46 (19)
N1—C1—H1B	109.6	O7—Mo2—O8	41.32 (15)
C2ⁱⁱ—C1—H1B	109.6	C2—N1—C1	111.5 (2)
H1A—C1—H1B	108.1	C2—N1—H1C	109.3
N1—C2—C1ⁱⁱ	110.2 (3)	C1—N1—H1C	109.3
N1—C2—H2A	109.6	C2—N1—H1D	109.3
C1ⁱⁱ—C2—H2A	109.6	C1—N1—H1D	109.3
N1—C2—H2B	109.6	H1C—N1—H1D	108.0
C1ⁱⁱ—C2—H2B	109.6	O30—O3—Mo1	68.4 (9)
H2A—C2—H2B	108.1	O30—O3—Mo1ⁱ	70.5 (9)
O1—Mo1—O40	109.5 (2)	Mo1—O3—Mo1ⁱ	128.0 (3)
O1—Mo1—O50ⁱⁱⁱ	110.5 (2)	O40—O4—Mo2	72.5 (12)
O40—Mo1—O50ⁱⁱⁱ	139.9 (3)	O40—O4—Mo1	61.1 (12)
O1—Mo1—O30	110.5 (2)	Mo2—O4—Mo1	124.0 (3)
O40—Mo1—O30	93.3 (3)	O50—O5—Mo2	70.5 (8)
O50ⁱⁱⁱ—Mo1—O30	75.3 (3)	O50—O5—Mo1ⁱ	60.7 (8)
O1—Mo1—O30ⁱⁱⁱ	110.9 (2)	Mo2—O5—Mo1ⁱ	125.0 (3)
O40—Mo1—O30ⁱⁱⁱ	74.5 (3)	Mo2—O6—Mo2^v	139.8 (2)
O50ⁱⁱⁱ—Mo1—O30ⁱⁱⁱ	88.9 (2)	P1—O7—O8	54.2 (2)
O30—Mo1—O30ⁱⁱⁱ	138.6 (4)	P1—O7—O7ⁱⁱⁱ	54.43 (7)
O1—Mo1—O3	94.28 (19)	O8—O7—O7ⁱⁱⁱ	89.79 (17)
O40—Mo1—O3	89.8 (3)	P1—O7—O7ⁱ	54.43 (7)
O50ⁱⁱⁱ—Mo1—O3	89.9 (2)	O8—O7—O7ⁱ	89.79 (17)
O30—Mo1—O3	18.98 (15)	O7ⁱⁱⁱ—O7—O7ⁱ	88.7 (3)
O30ⁱⁱⁱ—Mo1—O3	153.5 (3)	P1—O7—Mo2	124.6 (2)
O1—Mo1—O3ⁱⁱⁱ	94.68 (19)	O8—O7—Mo2	70.4 (2)
O40—Mo1—O3ⁱⁱⁱ	88.2 (3)	O7ⁱⁱⁱ—O7—Mo2	132.5 (2)
O50ⁱⁱⁱ—Mo1—O3ⁱⁱⁱ	86.0 (2)	O7ⁱ—O7—Mo2	132.1 (2)
O30—Mo1—O3ⁱⁱⁱ	152.5 (3)	P1—O7—Mo1	123.5 (2)
O30ⁱⁱⁱ—Mo1—O3ⁱⁱⁱ	18.62 (15)	O8—O7—Mo1	131.7 (2)
O3—Mo1—O3ⁱⁱⁱ	171.0 (3)	O7ⁱⁱⁱ—O7—Mo1	69.08 (18)
O1—Mo1—O4	94.32 (19)	O7ⁱ—O7—Mo1	130.5 (3)
O40—Mo1—O4	16.3 (2)	Mo2—O7—Mo1	92.09 (13)
O50ⁱⁱⁱ—Mo1—O4	154.9 (2)	P1—O7—Mo1ⁱ	123.1 (2)
O30—Mo1—O4	93.5 (3)	O8—O7—Mo1ⁱ	132.1 (2)
O30ⁱⁱⁱ—Mo1—O4	85.0 (3)	O7ⁱⁱⁱ—O7—Mo1ⁱ	129.8 (3)
O3—Mo1—O4	85.0 (3)	O7ⁱ—O7—Mo1ⁱ	68.69 (18)
O3ⁱⁱⁱ—Mo1—O4	95.3 (3)	Mo2—O7—Mo1ⁱ	92.48 (13)
O1—Mo1—O5ⁱⁱⁱ	93.53 (18)	Mo1—O7—Mo1ⁱ	91.83 (12)
O40—Mo1—O5ⁱⁱⁱ	155.4 (2)	P1—O8—O7^v	55.9 (2)
O50ⁱⁱⁱ—Mo1—O5ⁱⁱⁱ	18.00 (17)	P1—O8—O7^iv	55.9 (2)
O30—Mo1—O5ⁱⁱⁱ	86.4 (2)	O7^v—O8—O7^iv	91.7 (3)
O30ⁱⁱⁱ—Mo1—O5ⁱⁱⁱ	89.6 (2)	P1—O8—O7	55.9 (2)
O3—Mo1—O5ⁱⁱⁱ	97.2 (2)	O7^v—O8—O7	91.7 (3)
O3ⁱⁱⁱ—Mo1—O5ⁱⁱⁱ	81.2 (2)	O7^iv—O8—O7	91.7 (3)
O4—Mo1—O5ⁱⁱⁱ	171.7 (2)	P1—O8—Mo2	124.17 (12)
O1—Mo1—O7	159.29 (14)	O7^v—O8—Mo2	130.90 (13)
O40—Mo1—O7	58.4 (2)	O7^iv—O8—Mo2	131.30 (13)
O50ⁱⁱⁱ—Mo1—O7	83.9 (2)	O7—O8—Mo2	68.26 (14)
O30—Mo1—O7	57.5 (2)	P1—O8—Mo2^v	124.17 (12)
O30ⁱⁱⁱ—Mo1—O7	83.3 (2)	O7^v—O8—Mo2^v	68.26 (14)
O3—Mo1—O7	70.30 (18)	O7^iv—O8—Mo2^v	130.90 (13)
O3ⁱⁱⁱ—Mo1—O7	101.25 (18)	O7—O8—Mo2^v	131.30 (13)
O4—Mo1—O7	71.25 (19)	Mo2—O8—Mo2^v	91.53 (17)
O5ⁱⁱⁱ—Mo1—O7	101.87 (18)	P1—O8—Mo2^iv	124.17 (12)
O1—Mo1—O7ⁱⁱⁱ	158.48 (13)	O7^v—O8—Mo2^iv	131.30 (13)
O40—Mo1—O7ⁱⁱⁱ	85.4 (2)	O7^iv—O8—Mo2^iv	68.26 (14)
O50ⁱⁱⁱ—Mo1—O7ⁱⁱⁱ	55.5 (2)	O7—O8—Mo2^iv	130.90 (13)
O30—Mo1—O7ⁱⁱⁱ	83.1 (2)	Mo2—O8—Mo2^iv	91.53 (17)
O30ⁱⁱⁱ—Mo1—O7ⁱⁱⁱ	56.9 (2)	Mo2^v—O8—Mo2^iv	91.53 (17)
O3—Mo1—O7ⁱⁱⁱ	101.45 (18)	O8^vi—P1—O8	180.0
O3ⁱⁱⁱ—Mo1—O7ⁱⁱⁱ	69.63 (18)	O8^vi—P1—O7ⁱ	69.92 (14)
O4—Mo1—O7ⁱⁱⁱ	101.55 (19)	O8—P1—O7ⁱ	110.08 (14)
O5ⁱⁱⁱ—Mo1—O7ⁱⁱⁱ	70.14 (18)	O8^vi—P1—O7^vi	69.92 (14)
O7—Mo1—O7ⁱⁱⁱ	42.23 (15)	O8—P1—O7^vi	110.08 (14)
O2—Mo2—O50	111.8 (2)	O7ⁱ—P1—O7^vi	108.86 (14)
O2—Mo2—O6	101.02 (16)	O8^vi—P1—O7	110.08 (14)
O50—Mo2—O6	83.7 (2)	O8—P1—O7	69.92 (14)
O2—Mo2—O40	110.1 (2)	O7ⁱ—P1—O7	71.14 (14)
O50—Mo2—O40	89.8 (3)	O7^vi—P1—O7	180.0 (4)
O6—Mo2—O40	148.3 (2)	O8^vi—P1—O7^v	110.08 (14)
O2—Mo2—O6^iv	101.43 (16)	O8—P1—O7^v	69.92 (14)
O50—Mo2—O6^iv	146.7 (2)	O7ⁱ—P1—O7^v	71.14 (14)
O6—Mo2—O6^iv	87.82 (16)	O7^vi—P1—O7^v	71.14 (14)
O40—Mo2—O6^iv	80.8 (2)	O7—P1—O7^v	108.86 (14)
O2—Mo2—O5	93.44 (19)	O8^vi—P1—O7ⁱⁱⁱ	69.92 (14)
O50—Mo2—O5	19.28 (15)	O8—P1—O7ⁱⁱⁱ	110.08 (14)
O6—Mo2—O5	92.81 (19)	O7ⁱ—P1—O7ⁱⁱⁱ	108.86 (14)
O40—Mo2—O5	90.9 (3)	O7^vi—P1—O7ⁱⁱⁱ	108.86 (14)
O6^iv—Mo2—O5	164.7 (2)	O7—P1—O7ⁱⁱⁱ	71.14 (14)
O2—Mo2—O4	93.90 (19)	O7^v—P1—O7ⁱⁱⁱ	180.0 (3)
O50—Mo2—O4	91.0 (3)	O8^vi—P1—O7^iv	110.08 (14)
O6—Mo2—O4	165.1 (2)	O8—P1—O7^iv	69.92 (14)
O40—Mo2—O4	17.11 (16)	O7ⁱ—P1—O7^iv	180.0 (3)
O6^iv—Mo2—O4	89.0 (2)	O7^vi—P1—O7^iv	71.14 (14)
O5—Mo2—O4	86.5 (3)	O7—P1—O7^iv	108.86 (14)
O2—Mo2—O7	160.55 (15)	O7^v—P1—O7^iv	108.86 (14)
O50—Mo2—O7	56.0 (2)	O7ⁱⁱⁱ—P1—O7^iv	71.14 (14)

O4—O40—Mo1—O1	−21.8 (14)	O1—Mo1—O7—O8	111.4 (4)
Mo2—O40—Mo1—O1	−131.3 (6)	O40—Mo1—O7—O8	52.7 (4)
O4—O40—Mo1—O50ⁱⁱⁱ	162.3 (11)	O50ⁱⁱⁱ—Mo1—O7—O8	−112.8 (4)
Mo2—O40—Mo1—O50ⁱⁱⁱ	52.7 (9)	O30—Mo1—O7—O8	170.8 (4)
O4—O40—Mo1—O30	91.4 (13)	O30ⁱⁱⁱ—Mo1—O7—O8	−23.2 (4)
Mo2—O40—Mo1—O30	−18.2 (7)	O3—Mo1—O7—O8	155.1 (4)
O4—O40—Mo1—O30ⁱⁱⁱ	−128.9 (14)	O3ⁱⁱⁱ—Mo1—O7—O8	−28.1 (4)
Mo2—O40—Mo1—O30ⁱⁱⁱ	121.6 (7)	O4—Mo1—O7—O8	63.7 (4)
O4—O40—Mo1—O3	72.7 (13)	O5ⁱⁱⁱ—Mo1—O7—O8	−111.4 (4)
Mo2—O40—Mo1—O3	−36.8 (6)	O7ⁱⁱⁱ—Mo1—O7—O8	−69.8 (3)
O4—O40—Mo1—O3ⁱⁱⁱ	−116.1 (13)	O1—Mo1—O7—O7ⁱⁱⁱ	−178.8 (3)
Mo2—O40—Mo1—O3ⁱⁱⁱ	134.4 (6)	O40—Mo1—O7—O7ⁱⁱⁱ	122.4 (3)
Mo2—O40—Mo1—O4	−109.5 (17)	O50ⁱⁱⁱ—Mo1—O7—O7ⁱⁱⁱ	−43.0 (3)
O4—O40—Mo1—O5ⁱⁱⁱ	179.8 (10)	O30—Mo1—O7—O7ⁱⁱⁱ	−119.4 (3)
Mo2—O40—Mo1—O5ⁱⁱⁱ	70.3 (10)	O30ⁱⁱⁱ—Mo1—O7—O7ⁱⁱⁱ	46.5 (3)
O4—O40—Mo1—O7	139.5 (14)	O3—Mo1—O7—O7ⁱⁱⁱ	−135.1 (3)
Mo2—O40—Mo1—O7	30.0 (5)	O3ⁱⁱⁱ—Mo1—O7—O7ⁱⁱⁱ	41.6 (3)
O4—O40—Mo1—O7ⁱⁱⁱ	174.2 (13)	O4—Mo1—O7—O7ⁱⁱⁱ	133.5 (3)
Mo2—O40—Mo1—O7ⁱⁱⁱ	64.7 (6)	O5ⁱⁱⁱ—Mo1—O7—O7ⁱⁱⁱ	−41.6 (3)
O3—O30—Mo1—O1	32.5 (10)	O1—Mo1—O7—O7ⁱ	−109.7 (4)
Mo1ⁱ—O30—Mo1—O1	128.2 (6)	O40—Mo1—O7—O7ⁱ	−168.5 (4)
O3—O30—Mo1—O40	−79.8 (9)	O50ⁱⁱⁱ—Mo1—O7—O7ⁱ	26.0 (3)
Mo1ⁱ—O30—Mo1—O40	16.0 (7)	O30—Mo1—O7—O7ⁱ	−50.4 (3)
O3—O30—Mo1—O50ⁱⁱⁱ	139.3 (10)	O30ⁱⁱⁱ—Mo1—O7—O7ⁱ	115.6 (3)
Mo1ⁱ—O30—Mo1—O50ⁱⁱⁱ	−125.0 (7)	O3—Mo1—O7—O7ⁱ	−66.0 (3)
O3—O30—Mo1—O30ⁱⁱⁱ	−149.9 (9)	O3ⁱⁱⁱ—Mo1—O7—O7ⁱ	110.7 (3)
Mo1ⁱ—O30—Mo1—O30ⁱⁱⁱ	−54.2 (6)	O4—Mo1—O7—O7ⁱ	−157.4 (3)
Mo1ⁱ—O30—Mo1—O3	95.7 (11)	O5ⁱⁱⁱ—Mo1—O7—O7ⁱ	27.5 (3)
O3—O30—Mo1—O3ⁱⁱⁱ	−172.2 (5)	O7ⁱⁱⁱ—Mo1—O7—O7ⁱ	69.1 (4)
Mo1ⁱ—O30—Mo1—O3ⁱⁱⁱ	−76.5 (8)	O1—Mo1—O7—Mo2	46.0 (4)
O3—O30—Mo1—O4	−63.5 (9)	O40—Mo1—O7—Mo2	−12.7 (3)
Mo1ⁱ—O30—Mo1—O4	32.3 (7)	O50ⁱⁱⁱ—Mo1—O7—Mo2	−178.2 (2)
O3—O30—Mo1—O5ⁱⁱⁱ	124.9 (9)	O30—Mo1—O7—Mo2	105.4 (2)
Mo1ⁱ—O30—Mo1—O5ⁱⁱⁱ	−139.4 (6)	O30ⁱⁱⁱ—Mo1—O7—Mo2	−88.63 (19)
O3—O30—Mo1—O7	−128.6 (10)	O3—Mo1—O7—Mo2	89.7 (2)
Mo1ⁱ—O30—Mo1—O7	−32.8 (5)	O3ⁱⁱⁱ—Mo1—O7—Mo2	−93.52 (19)
O3—O30—Mo1—O7ⁱⁱⁱ	−164.7 (9)	O4—Mo1—O7—Mo2	−1.6 (2)
Mo1ⁱ—O30—Mo1—O7ⁱⁱⁱ	−69.0 (6)	O5ⁱⁱⁱ—Mo1—O7—Mo2	−176.75 (17)
O5—O50—Mo2—O2	−18.4 (9)	O7ⁱⁱⁱ—Mo1—O7—Mo2	−135.2 (2)
Mo1ⁱ—O50—Mo2—O2	−133.3 (7)	O1—Mo1—O7—Mo1ⁱ	−46.5 (4)
O5—O50—Mo2—O6	−117.7 (9)	O40—Mo1—O7—Mo1ⁱ	−105.3 (3)
Mo1ⁱ—O50—Mo2—O6	127.3 (7)	O50ⁱⁱⁱ—Mo1—O7—Mo1ⁱ	89.3 (2)
O5—O50—Mo2—O40	93.3 (9)	O30—Mo1—O7—Mo1ⁱ	12.9 (2)
Mo1ⁱ—O50—Mo2—O40	−21.6 (7)	O30ⁱⁱⁱ—Mo1—O7—Mo1ⁱ	178.8 (2)
O5—O50—Mo2—O6^iv	166.0 (7)	O3—Mo1—O7—Mo1ⁱ	−2.81 (18)
Mo1ⁱ—O50—Mo2—O6^iv	51.1 (9)	O3ⁱⁱⁱ—Mo1—O7—Mo1ⁱ	173.92 (18)
Mo1ⁱ—O50—Mo2—O5	−114.9 (13)	O4—Mo1—O7—Mo1ⁱ	−94.2 (2)
O5—O50—Mo2—O4	76.3 (9)	O5ⁱⁱⁱ—Mo1—O7—Mo1ⁱ	90.70 (19)
Mo1ⁱ—O50—Mo2—O4	−38.7 (7)	O7ⁱⁱⁱ—Mo1—O7—Mo1ⁱ	132.3 (3)
O5—O50—Mo2—O7	144.4 (9)	O7ⁱⁱⁱ—O7—O8—P1	44.36 (15)
Mo1ⁱ—O50—Mo2—O7	29.4 (6)	O7ⁱ—O7—O8—P1	−44.36 (15)
O5—O50—Mo2—O8	177.7 (9)	Mo2—O7—O8—P1	−179.77 (14)
Mo1ⁱ—O50—Mo2—O8	62.7 (7)	Mo1—O7—O8—P1	105.6 (3)
O4—O40—Mo2—O2	19.0 (13)	Mo1ⁱ—O7—O8—P1	−104.8 (3)
Mo1—O40—Mo2—O2	132.1 (6)	P1—O7—O8—O7^v	45.85 (16)
O4—O40—Mo2—O50	−94.2 (12)	O7ⁱⁱⁱ—O7—O8—O7^v	90.21 (18)
Mo1—O40—Mo2—O50	18.9 (6)	O7ⁱ—O7—O8—O7^v	1.5 (3)
O4—O40—Mo2—O6	−171.7 (10)	Mo2—O7—O8—O7^v	−133.9 (2)
Mo1—O40—Mo2—O6	−58.6 (9)	Mo1—O7—O8—O7^v	151.4 (2)
O4—O40—Mo2—O6^iv	117.9 (13)	Mo1ⁱ—O7—O8—O7^v	−59.0 (5)
Mo1—O40—Mo2—O6^iv	−129.0 (6)	P1—O7—O8—O7^iv	−45.85 (16)
O4—O40—Mo2—O5	−75.0 (12)	O7ⁱⁱⁱ—O7—O8—O7^iv	−1.5 (3)
Mo1—O40—Mo2—O5	38.1 (6)	O7ⁱ—O7—O8—O7^iv	−90.21 (18)
Mo1—O40—Mo2—O4	113.1 (16)	Mo2—O7—O8—O7^iv	134.4 (2)
O4—O40—Mo2—O7	−143.5 (13)	Mo1—O7—O8—O7^iv	59.7 (5)
Mo1—O40—Mo2—O7	−30.3 (5)	Mo1ⁱ—O7—O8—O7^iv	−150.7 (2)
O4—O40—Mo2—O8	−177.8 (13)	P1—O7—O8—Mo2	179.77 (14)
Mo1—O40—Mo2—O8	−64.7 (6)	O7ⁱⁱⁱ—O7—O8—Mo2	−135.9 (2)
C1ⁱⁱ—C2—N1—C1	57.4 (4)	O7ⁱ—O7—O8—Mo2	135.4 (2)
C2ⁱⁱ—C1—N1—C2	−57.3 (4)	Mo1—O7—O8—Mo2	−74.6 (3)
Mo1ⁱ—O30—O3—Mo1	−147.5 (4)	Mo1ⁱ—O7—O8—Mo2	75.0 (3)
Mo1—O30—O3—Mo1ⁱ	147.5 (4)	P1—O7—O8—Mo2^v	108.0 (3)
O1—Mo1—O3—O30	−149.7 (9)	O7ⁱⁱⁱ—O7—O8—Mo2^v	152.3 (3)
O40—Mo1—O3—O30	100.7 (9)	O7ⁱ—O7—O8—Mo2^v	63.6 (4)
O50ⁱⁱⁱ—Mo1—O3—O30	−39.1 (9)	Mo2—O7—O8—Mo2^v	−71.8 (3)
O30ⁱⁱⁱ—Mo1—O3—O30	48.1 (14)	Mo1—O7—O8—Mo2^v	−146.5 (2)
O3ⁱⁱⁱ—Mo1—O3—O30	23.6 (10)	Mo1ⁱ—O7—O8—Mo2^v	3.1 (6)
O4—Mo1—O3—O30	116.3 (9)	P1—O7—O8—Mo2^iv	−108.1 (3)
O5ⁱⁱⁱ—Mo1—O3—O30	−55.6 (9)	O7ⁱⁱⁱ—O7—O8—Mo2^iv	−63.8 (4)
O7—Mo1—O3—O30	44.5 (9)	O7ⁱ—O7—O8—Mo2^iv	−152.5 (3)
O7ⁱⁱⁱ—Mo1—O3—O30	15.5 (9)	Mo2—O7—O8—Mo2^iv	72.1 (3)
O1—Mo1—O3—Mo1ⁱ	170.2 (3)	Mo1—O7—O8—Mo2^iv	−2.5 (6)
O40—Mo1—O3—Mo1ⁱ	60.7 (4)	Mo1ⁱ—O7—O8—Mo2^iv	147.1 (2)
O50ⁱⁱⁱ—Mo1—O3—Mo1ⁱ	−79.2 (4)	O2—Mo2—O8—P1	−179.9 (2)
O30—Mo1—O3—Mo1ⁱ	−40.0 (7)	O50—Mo2—O8—P1	−43.38 (17)
O30ⁱⁱⁱ—Mo1—O3—Mo1ⁱ	8.1 (9)	O6—Mo2—O8—P1	−129.43 (12)
O3ⁱⁱⁱ—Mo1—O3—Mo1ⁱ	−16.5 (4)	O40—Mo2—O8—P1	47.0 (2)
O4—Mo1—O3—Mo1ⁱ	76.3 (4)	O6^iv—Mo2—O8—P1	129.51 (12)
O5ⁱⁱⁱ—Mo1—O3—Mo1ⁱ	−95.6 (4)	O5—Mo2—O8—P1	−42.59 (17)
O7—Mo1—O3—Mo1ⁱ	4.4 (3)	O4—Mo2—O8—P1	46.4 (2)
O7ⁱⁱⁱ—Mo1—O3—Mo1ⁱ	−24.5 (4)	O7—Mo2—O8—P1	0.23 (14)
Mo1—O40—O4—Mo2	−147.5 (7)	O2—Mo2—O8—O7^v	−107.8 (4)
Mo2—O40—O4—Mo1	147.5 (7)	O50—Mo2—O8—O7^v	28.7 (4)
O2—Mo2—O4—O40	−162.2 (12)	O6—Mo2—O8—O7^v	−57.4 (3)
O50—Mo2—O4—O40	85.9 (13)	O40—Mo2—O8—O7^v	119.1 (4)
O6—Mo2—O4—O40	17 (2)	O6^iv—Mo2—O8—O7^v	−158.4 (4)
O6^iv—Mo2—O4—O40	−60.8 (12)	O5—Mo2—O8—O7^v	29.5 (4)
O5—Mo2—O4—O40	104.6 (13)	O4—Mo2—O8—O7^v	118.4 (4)
O7—Mo2—O4—O40	32.1 (12)	O7—Mo2—O8—O7^v	72.3 (4)
O8—Mo2—O4—O40	2.2 (13)	O2—Mo2—O8—O7^iv	107.9 (4)
O2—Mo2—O4—Mo1	163.3 (4)	O50—Mo2—O8—O7^iv	−115.6 (4)
O50—Mo2—O4—Mo1	51.3 (4)	O6—Mo2—O8—O7^iv	158.3 (4)
O6—Mo2—O4—Mo1	−17.6 (11)	O40—Mo2—O8—O7^iv	−25.2 (4)
O40—Mo2—O4—Mo1	−34.6 (10)	O6^iv—Mo2—O8—O7^iv	57.3 (3)
O6^iv—Mo2—O4—Mo1	−95.3 (4)	O5—Mo2—O8—O7^iv	−114.8 (4)
O5—Mo2—O4—Mo1	70.1 (4)	O4—Mo2—O8—O7^iv	−25.9 (4)
O7—Mo2—O4—Mo1	−2.5 (3)	O7—Mo2—O8—O7^iv	−72.0 (4)
O8—Mo2—O4—Mo1	−32.4 (4)	O2—Mo2—O8—O7	179.9 (3)
O1—Mo1—O4—O40	159.5 (13)	O50—Mo2—O8—O7	−43.6 (2)
O50ⁱⁱⁱ—Mo1—O4—O40	−27.6 (17)	O6—Mo2—O8—O7	−129.66 (18)
O30—Mo1—O4—O40	−89.6 (13)	O40—Mo2—O8—O7	46.8 (2)
O30ⁱⁱⁱ—Mo1—O4—O40	48.9 (13)	O6^iv—Mo2—O8—O7	129.28 (18)
O3—Mo1—O4—O40	−106.6 (13)	O5—Mo2—O8—O7	−42.8 (2)
O3ⁱⁱⁱ—Mo1—O4—O40	64.4 (13)	O4—Mo2—O8—O7	46.1 (2)
O5ⁱⁱⁱ—Mo1—O4—O40	−1 (3)	O2—Mo2—O8—Mo2^v	−45.7 (3)
O7—Mo1—O4—O40	−35.7 (13)	O50—Mo2—O8—Mo2^v	90.84 (19)
O7ⁱⁱⁱ—Mo1—O4—O40	−5.9 (13)	O6—Mo2—O8—Mo2^v	4.78 (12)
O1—Mo1—O4—Mo2	−162.3 (4)	O40—Mo2—O8—Mo2^v	−178.8 (2)
O40—Mo1—O4—Mo2	38.2 (11)	O6^iv—Mo2—O8—Mo2^v	−96.28 (18)
O50ⁱⁱⁱ—Mo1—O4—Mo2	10.6 (9)	O5—Mo2—O8—Mo2^v	91.6 (2)
O30—Mo1—O4—Mo2	−51.4 (4)	O4—Mo2—O8—Mo2^v	−179.4 (2)
O30ⁱⁱⁱ—Mo1—O4—Mo2	87.0 (4)	O7—Mo2—O8—Mo2^v	134.44 (16)
O3—Mo1—O4—Mo2	−68.4 (4)	O2—Mo2—O8—Mo2^iv	45.9 (3)
O3ⁱⁱⁱ—Mo1—O4—Mo2	102.5 (4)	O50—Mo2—O8—Mo2^iv	−177.6 (2)
O5ⁱⁱⁱ—Mo1—O4—Mo2	37.6 (19)	O6—Mo2—O8—Mo2^iv	96.35 (18)
O7—Mo1—O4—Mo2	2.5 (3)	O40—Mo2—O8—Mo2^iv	−87.2 (2)
O7ⁱⁱⁱ—Mo1—O4—Mo2	32.3 (4)	O6^iv—Mo2—O8—Mo2^iv	−4.70 (12)
Mo1ⁱ—O50—O5—Mo2	153.9 (5)	O5—Mo2—O8—Mo2^iv	−176.80 (18)
Mo2—O50—O5—Mo1ⁱ	−153.9 (5)	O4—Mo2—O8—Mo2^iv	−87.8 (2)
O2—Mo2—O5—O50	163.0 (9)	O7—Mo2—O8—Mo2^iv	−133.99 (16)
O6—Mo2—O5—O50	61.8 (9)	O7^v—O8—P1—O8^vi	0 (100)
O40—Mo2—O5—O50	−86.8 (9)	O7^iv—O8—P1—O8^vi	0 (23)
O6^iv—Mo2—O5—O50	−30.3 (14)	O7—O8—P1—O8^vi	0 (100)
O4—Mo2—O5—O50	−103.3 (9)	Mo2—O8—P1—O8^vi	0 (100)
O7—Mo2—O5—O50	−30.5 (8)	Mo2^v—O8—P1—O8^vi	0 (100)
O8—Mo2—O5—O50	−2.4 (9)	Mo2^iv—O8—P1—O8^vi	0 (23)
O2—Mo2—O5—Mo1ⁱ	−169.1 (3)	O7^v—O8—P1—O7ⁱ	−60.0
O50—Mo2—O5—Mo1ⁱ	27.9 (7)	O7^iv—O8—P1—O7ⁱ	180.0
O6—Mo2—O5—Mo1ⁱ	89.7 (3)	O7—O8—P1—O7ⁱ	60.0
O40—Mo2—O5—Mo1ⁱ	−58.9 (4)	Mo2—O8—P1—O7ⁱ	59.75 (15)
O6^iv—Mo2—O5—Mo1ⁱ	−2.4 (9)	Mo2^v—O8—P1—O7ⁱ	−60.25 (15)
O4—Mo2—O5—Mo1ⁱ	−75.4 (3)	Mo2^iv—O8—P1—O7ⁱ	179.75 (15)
O7—Mo2—O5—Mo1ⁱ	−2.6 (3)	O7^v—O8—P1—O7^vi	60.0
O8—Mo2—O5—Mo1ⁱ	25.5 (3)	O7^iv—O8—P1—O7^vi	−60.0
O2—Mo2—O6—Mo2^v	153.3 (3)	O7—O8—P1—O7^vi	180.0
O50—Mo2—O6—Mo2^v	−95.6 (4)	Mo2—O8—P1—O7^vi	179.75 (15)
O40—Mo2—O6—Mo2^v	−16.4 (6)	Mo2^v—O8—P1—O7^vi	59.75 (15)
O6^iv—Mo2—O6—Mo2^v	52.1 (4)	Mo2^iv—O8—P1—O7^vi	−60.25 (15)
O5—Mo2—O6—Mo2^v	−112.6 (3)	O7^v—O8—P1—O7	−120.0
O4—Mo2—O6—Mo2^v	−25.8 (10)	O7^iv—O8—P1—O7	120.0
O7—Mo2—O6—Mo2^v	−40.2 (3)	Mo2—O8—P1—O7	−0.25 (15)
O8—Mo2—O6—Mo2^v	−9.7 (3)	Mo2^v—O8—P1—O7	−120.25 (15)
O2—Mo2—O7—P1	179.9 (3)	Mo2^iv—O8—P1—O7	119.75 (15)
O50—Mo2—O7—P1	124.1 (3)	O7^iv—O8—P1—O7^v	−120.0
O6—Mo2—O7—P1	43.7 (3)	O7—O8—P1—O7^v	120.0
O40—Mo2—O7—P1	−121.9 (4)	Mo2—O8—P1—O7^v	119.75 (15)
O6^iv—Mo2—O7—P1	−44.2 (3)	Mo2^v—O8—P1—O7^v	−0.25 (15)
O5—Mo2—O7—P1	135.7 (3)	Mo2^iv—O8—P1—O7^v	−120.25 (15)
O4—Mo2—O7—P1	−132.4 (3)	O7^v—O8—P1—O7ⁱⁱⁱ	180.0
O8—Mo2—O7—P1	−0.22 (13)	O7^iv—O8—P1—O7ⁱⁱⁱ	60.0
O2—Mo2—O7—O8	−179.9 (3)	O7—O8—P1—O7ⁱⁱⁱ	−60.0
O50—Mo2—O7—O8	124.3 (3)	Mo2—O8—P1—O7ⁱⁱⁱ	−60.25 (15)
O6—Mo2—O7—O8	43.93 (13)	Mo2^v—O8—P1—O7ⁱⁱⁱ	179.75 (15)
O40—Mo2—O7—O8	−121.6 (3)	Mo2^iv—O8—P1—O7ⁱⁱⁱ	59.75 (15)
O6^iv—Mo2—O7—O8	−44.02 (13)	O7^v—O8—P1—O7^iv	120.0
O5—Mo2—O7—O8	135.9 (2)	O7—O8—P1—O7^iv	−120.0
O4—Mo2—O7—O8	−132.2 (2)	Mo2—O8—P1—O7^iv	−120.25 (15)
O2—Mo2—O7—O7ⁱⁱⁱ	−109.2 (3)	Mo2^v—O8—P1—O7^iv	119.75 (15)
O50—Mo2—O7—O7ⁱⁱⁱ	−165.0 (4)	Mo2^iv—O8—P1—O7^iv	−0.25 (15)
O6—Mo2—O7—O7ⁱⁱⁱ	114.6 (2)	O8—O7—P1—O8^vi	180.0
O40—Mo2—O7—O7ⁱⁱⁱ	−50.9 (3)	O7ⁱⁱⁱ—O7—P1—O8^vi	59.27 (17)
O6^iv—Mo2—O7—O7ⁱⁱⁱ	26.7 (2)	O7ⁱ—O7—P1—O8^vi	−59.27 (17)
O5—Mo2—O7—O7ⁱⁱⁱ	−153.4 (3)	Mo2—O7—P1—O8^vi	−179.74 (15)
O4—Mo2—O7—O7ⁱⁱⁱ	−61.5 (3)	Mo1—O7—P1—O8^vi	59.6 (2)
O8—Mo2—O7—O7ⁱⁱⁱ	70.69 (16)	Mo1ⁱ—O7—P1—O8^vi	−58.9 (2)
O2—Mo2—O7—O7ⁱ	109.2 (3)	O7ⁱⁱⁱ—O7—P1—O8	−120.73 (17)
O50—Mo2—O7—O7ⁱ	53.3 (3)	O7ⁱ—O7—P1—O8	120.73 (17)
O6—Mo2—O7—O7ⁱ	−27.0 (2)	Mo2—O7—P1—O8	0.26 (15)
O40—Mo2—O7—O7ⁱ	167.4 (4)	Mo1—O7—P1—O8	−120.4 (2)
O6^iv—Mo2—O7—O7ⁱ	−115.0 (2)	Mo1ⁱ—O7—P1—O8	121.1 (2)
O5—Mo2—O7—O7ⁱ	65.0 (3)	O8—O7—P1—O7ⁱ	−120.73 (17)
O4—Mo2—O7—O7ⁱ	156.8 (3)	O7ⁱⁱⁱ—O7—P1—O7ⁱ	118.5 (3)
O8—Mo2—O7—O7ⁱ	−70.97 (16)	Mo2—O7—P1—O7ⁱ	−120.5 (2)
O2—Mo2—O7—Mo1	−46.0 (4)	Mo1—O7—P1—O7ⁱ	118.9 (4)
O50—Mo2—O7—Mo1	−101.8 (2)	Mo1ⁱ—O7—P1—O7ⁱ	0.36 (16)
O6—Mo2—O7—Mo1	177.83 (12)	O8—O7—P1—O7^vi	60.87 (7)
O40—Mo2—O7—Mo1	12.3 (2)	O7ⁱⁱⁱ—O7—P1—O7^vi	−59.9 (2)
O6^iv—Mo2—O7—Mo1	89.88 (12)	O7ⁱ—O7—P1—O7^vi	−178.39 (15)
O5—Mo2—O7—Mo1	−90.2 (2)	Mo2—O7—P1—O7^vi	61.1 (2)
O4—Mo2—O7—Mo1	1.7 (2)	Mo1—O7—P1—O7^vi	−59.5 (2)
O8—Mo2—O7—Mo1	133.89 (18)	Mo1ⁱ—O7—P1—O7^vi	−178.03 (18)
O2—Mo2—O7—Mo1ⁱ	46.0 (4)	O8—O7—P1—O7^v	−59.27 (17)
O50—Mo2—O7—Mo1ⁱ	−9.9 (2)	O7ⁱⁱⁱ—O7—P1—O7^v	180.0
O6—Mo2—O7—Mo1ⁱ	−90.25 (12)	O7ⁱ—O7—P1—O7^v	61.5 (3)
O40—Mo2—O7—Mo1ⁱ	104.2 (3)	Mo2—O7—P1—O7^v	−59.0 (2)
O6^iv—Mo2—O7—Mo1ⁱ	−178.20 (12)	Mo1—O7—P1—O7^v	−179.64 (15)
O5—Mo2—O7—Mo1ⁱ	1.74 (18)	Mo1ⁱ—O7—P1—O7^v	61.8 (4)
O4—Mo2—O7—Mo1ⁱ	93.6 (2)	O8—O7—P1—O7ⁱⁱⁱ	120.73 (17)
O8—Mo2—O7—Mo1ⁱ	−134.18 (18)	O7ⁱ—O7—P1—O7ⁱⁱⁱ	−118.5 (3)
O1—Mo1—O7—P1	−179.1 (2)	Mo2—O7—P1—O7ⁱⁱⁱ	121.0 (2)
O40—Mo1—O7—P1	122.1 (4)	Mo1—O7—P1—O7ⁱⁱⁱ	0.36 (15)
O50ⁱⁱⁱ—Mo1—O7—P1	−43.3 (3)	Mo1ⁱ—O7—P1—O7ⁱⁱⁱ	−118.2 (4)
O30—Mo1—O7—P1	−119.7 (3)	O8—O7—P1—O7^iv	59.27 (17)
O30ⁱⁱⁱ—Mo1—O7—P1	46.2 (3)	O7ⁱⁱⁱ—O7—P1—O7^iv	−61.5 (3)
O3—Mo1—O7—P1	−135.4 (3)	O7ⁱ—O7—P1—O7^iv	180.0
O3ⁱⁱⁱ—Mo1—O7—P1	41.3 (3)	Mo2—O7—P1—O7^iv	59.5 (2)
O4—Mo1—O7—P1	133.2 (3)	Mo1—O7—P1—O7^iv	−61.1 (4)
O5ⁱⁱⁱ—Mo1—O7—P1	−41.9 (3)	Mo1ⁱ—O7—P1—O7^iv	−179.64 (16)
O7ⁱⁱⁱ—Mo1—O7—P1	−0.32 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O6	0.90	2.22	2.812 (4)	123
N1—H1D···O50	0.90	2.43	2.926 (6)	115
N1—H1C···O4^v	0.90	2.20	3.041 (7)	155
N1—H1C···O40^v	0.90	2.16	3.047 (7)	168
N1—H1C···O30ⁱ	0.90	2.52	3.091 (6)	122
N1—H1D···O5	0.90	2.19	2.852 (6)	130
N1—H1D···O1^vii	0.90	2.14	2.900 (4)	142
C1—H1A···O6	0.97	2.58	3.101 (5)	114
C1—H1B···O4^viii	0.97	2.58	3.347 (7)	137
C2—H2A···O2^viii	0.97	2.43	3.291 (4)	148
C2—H2B···O3ⁱ	0.97	2.43	3.156 (6)	132
C2—H2B···O2^ix	0.97	2.42	3.068 (4)	124

Symmetry codes: (i) y, −x+y, −z; (v) −x+y, −x, z; (vii) x+1/3, x−y+2/3, z+1/6; (viii) x−y+2/3, x+1/3, −z+1/3; (ix) −y+2/3, −x+1/3, z−1/6.

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)₃[PMo₁₂O₄₀]
M_r	2086.72
Crystal system, space group	Trigonal, R3c
Temperature (K)	296
a, c (Å)	17.890 (3), 23.600 (6)
V (Å³)	6541 (2)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	3.49
Crystal size (mm)	0.20 × 0.16 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.517, 0.682
No. of measured, independent and observed [I > 2σ(I)] reflections	11291, 1413, 1363
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.053, 1.14
No. of reflections	1413
No. of parameters	142
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0243P)² + 29.698P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.61

Computer programs: RAPID-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O6	0.90	2.22	2.812 (4)	122.7
N1—H1D···O50	0.90	2.43	2.926 (6)	115.1
N1—H1C···O4ⁱ	0.90	2.20	3.041 (7)	154.5
N1—H1C···O40ⁱ	0.90	2.16	3.047 (7)	167.9
N1—H1C···O30ⁱⁱ	0.90	2.52	3.091 (6)	122.2
N1—H1D···O5	0.90	2.19	2.852 (6)	130.1
N1—H1D···O1ⁱⁱⁱ	0.90	2.14	2.900 (4)	141.8
C1—H1A···O6	0.97	2.58	3.101 (5)	113.8
C1—H1B···O4^iv	0.97	2.58	3.347 (7)	136.6
C2—H2A···O2^iv	0.97	2.43	3.291 (4)	148.1
C2—H2B···O3ⁱⁱ	0.97	2.43	3.156 (6)	131.8
C2—H2B···O2^v	0.97	2.42	3.068 (4)	124.1

Symmetry codes: (i) −x+y, −x, z; (ii) y, −x+y, −z; (iii) x+1/3, x−y+2/3, z+1/6; (iv) x−y+2/3, x+1/3, −z+1/3; (v) −y+2/3, −x+1/3, z−1/6.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (20571032 and 20333070).

References

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