Tetra­pyridinium α-dodeca­molybdosilicate hemihydrate

The title compound, (C₅H₆N)₄[SiMo₁₂O₄₀]·0.5H₂O, was synthesized by a hydro­thermal method. The compound consists of a Keggin anion, [SiMo₁₂O₄₀]⁴⁻, disordered about a crystallographic centre of inversion, pyridinium cations, and a water mol­ecule lying on a mirror plane. The [SiMo₁₂O₄₀]⁴⁻ anions and water mol­ecules lie in layers, and the pyridinium cations lie between these layers, forming N—H...O and C—H...O contacts to the O atoms of [SiMo₁₂O₄₀]⁴⁻.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.014 Å
• Disorder in main residue
• R factor = 0.054
• wR factor = 0.150
• Data-to-parameter ratio = 10.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        O1W
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.98
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.76 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Mo1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Mo5
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O12
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O13
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O14
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O18
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O19
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O20
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mo3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mo7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        O21
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        O22
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for         N1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         C5
PLAT301_ALERT_3_C Main Residue  Disorder .........................      24.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................       4.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         14
PLAT432_ALERT_2_C Short Inter X...Y Contact  O5     ..  C8      ..       2.99 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O5     ..  C8      ..       2.99 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O9'    ..  C5      ..       2.93 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O11'   ..  C2      ..       2.96 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  29 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  17 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Tetrapyridinium α-dodecamolybdosilicate hemihydrate

Crystal data

(C5H6N)4[SiMo12O40]·0.5H2O	F(000) = 4060
Mr = 2148.81	Dx = 2.920 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 125 reflections
a = 16.670 (3) Å	θ = 2.0–16.1°
b = 20.950 (4) Å	µ = 3.11 mm^−1
c = 13.996 (3) Å	T = 293 K
V = 4887.8 (17) Å^3	Block, yellow
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4413 independent reflections
Radiation source: sealed tube	3984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→16
Tmin = 0.479, Tmax = 0.537	k = −24→22
23971 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.150	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.075P)^2 + 61.8506P] where P = (Fo^2 + 2Fc^2)/3
4413 reflections	(Δ/σ)max = 0.001
442 parameters	Δρmax = 1.82 e Å^−3
37 restraints	Δρmin = −1.57 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Si1	0.65576 (13)	0.7500	0.05699 (15)	0.0309 (5)
Mo1	0.86526 (5)	0.7500	0.07992 (7)	0.0592 (3)
Mo2	0.75323 (4)	0.87468 (3)	0.18139 (4)	0.04501 (15)
Mo3	0.65768 (4)	0.7500	0.30798 (5)	0.03410 (17)
Mo4	0.54075 (4)	0.86378 (3)	0.18357 (4)	0.04322 (15)
Mo5	0.44536 (5)	0.7500	0.03670 (8)	0.0651 (3)
Mo6	0.55792 (4)	0.87368 (3)	−0.06761 (4)	0.05128 (17)
Mo7	0.65440 (5)	0.7500	−0.19601 (5)	0.03587 (18)
Mo8	0.76982 (4)	0.86373 (3)	−0.06931 (4)	0.04964 (16)
O1	0.9653 (4)	0.7500	0.0754 (5)	0.0531 (19)
O2	0.8009 (3)	0.9304 (2)	0.2431 (4)	0.0623 (15)
O3	0.6531 (4)	0.7500	0.4264 (5)	0.058 (2)
O4	0.4921 (3)	0.9209 (2)	0.2404 (5)	0.0755 (17)
O5	0.3449 (4)	0.7500	0.0339 (6)	0.055 (2)
O6	0.5119 (3)	0.9296 (3)	−0.1302 (4)	0.0684 (16)
O7	0.6586 (5)	0.7345 (4)	−0.3143 (5)	0.048 (4)	0.50
O8	0.8206 (3)	0.9211 (3)	−0.1250 (4)	0.0644 (15)
O9	0.8301 (5)	0.7981 (4)	−0.0275 (6)	0.039 (2)	0.50
O10	0.8233 (4)	0.8016 (4)	0.1578 (6)	0.0331 (19)	0.50
O11	0.7504 (5)	0.8883 (4)	0.0560 (5)	0.037 (2)	0.50
O9'	0.8652 (4)	0.8242 (4)	−0.0271 (6)	0.038 (2)	0.50
O10'	0.8593 (5)	0.8272 (4)	0.1641 (6)	0.037 (2)	0.50
O11'	0.7835 (6)	0.9162 (4)	0.0620 (6)	0.040 (2)	0.50
O12	0.7300 (3)	0.8143 (2)	0.2853 (4)	0.0664 (15)
O13	0.6489 (3)	0.9024 (3)	0.1893 (4)	0.0691 (16)
O14	0.5720 (3)	0.8114 (3)	0.2817 (4)	0.0674 (15)
O15	0.4796 (5)	0.7972 (4)	0.1393 (6)	0.040 (2)	0.50
O16	0.5596 (5)	0.8874 (4)	0.0528 (6)	0.037 (2)	0.50
O17	0.4861 (5)	0.7991 (4)	−0.0454 (6)	0.037 (2)	0.50
O15'	0.4451 (5)	0.8244 (4)	0.1421 (6)	0.038 (2)	0.50
O16'	0.5299 (5)	0.9173 (4)	0.0583 (6)	0.040 (2)	0.50
O17'	0.4533 (5)	0.8297 (4)	−0.0477 (6)	0.039 (2)	0.50
O18	0.5818 (3)	0.8131 (3)	−0.1724 (5)	0.0684 (16)
O19	0.6621 (3)	0.9013 (3)	−0.0758 (5)	0.0774 (17)
O20	0.7409 (3)	0.8111 (3)	−0.1695 (5)	0.0677 (15)
O21	0.7353 (4)	0.7988 (4)	0.0609 (5)	0.0295 (18)	0.50
O22	0.5758 (4)	0.7993 (4)	0.0552 (5)	0.0298 (18)	0.50
O23	0.6584 (4)	0.7902 (4)	−0.0372 (5)	0.0316 (19)	0.50
O24	0.6531 (4)	0.7915 (3)	0.1511 (5)	0.0277 (18)	0.50
N1	0.5544 (6)	0.8864 (5)	0.4799 (6)	0.108 (3)
H1A	0.5478	0.8627	0.4304	0.130*
C1	0.5889 (6)	0.9428 (6)	0.4715 (8)	0.094 (3)
H1B	0.6049	0.9580	0.4121	0.112*
C2	0.6001 (7)	0.9776 (5)	0.5498 (9)	0.108 (4)
H2B	0.6276	1.0161	0.5449	0.129*
C3	0.5737 (7)	0.9593 (5)	0.6343 (7)	0.097 (3)
H3A	0.5807	0.9852	0.6876	0.116*
C4	0.5365 (6)	0.9026 (6)	0.6421 (6)	0.094 (4)
H4A	0.5160	0.8892	0.7006	0.112*
C5	0.5296 (4)	0.8662 (5)	0.5658 (7)	0.084 (3)
H5A	0.5071	0.8258	0.5716	0.101*
N2	0.8483 (4)	0.9738 (3)	0.5573 (5)	0.066 (2)
H2A	0.8753	1.0088	0.5580	0.079*
C6	0.8327 (5)	0.9439 (4)	0.4728 (5)	0.062 (2)
H6A	0.8517	0.9613	0.4160	0.075*
C7	0.7905 (5)	0.8897 (4)	0.4708 (5)	0.059 (2)
H7A	0.7792	0.8700	0.4128	0.070*
C8	0.7641 (6)	0.8636 (4)	0.5530 (6)	0.068 (3)
H8A	0.7348	0.8258	0.5518	0.082*
C9	0.7803 (5)	0.8924 (4)	0.6373 (5)	0.062 (2)
H9A	0.7632	0.8737	0.6940	0.074*
C10	0.8213 (5)	0.9486 (4)	0.6401 (5)	0.063 (2)
H10A	0.8305	0.9692	0.6979	0.076*
O1W	0.4402 (13)	0.7500	0.7020 (16)	0.109 (5)	0.50
H1WA	0.4278	0.7171	0.7343	0.130*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0264 (10)	0.0386 (12)	0.0279 (11)	0.000	−0.0010 (8)	0.000
Mo1	0.0267 (4)	0.0999 (8)	0.0510 (5)	0.000	−0.0027 (4)	0.000
Mo2	0.0542 (3)	0.0466 (3)	0.0341 (3)	−0.0043 (3)	−0.0041 (2)	−0.0099 (2)
Mo3	0.0413 (4)	0.0375 (4)	0.0235 (3)	0.000	0.0014 (3)	0.000
Mo4	0.0472 (3)	0.0466 (3)	0.0358 (3)	0.0045 (3)	0.0068 (2)	−0.0090 (2)
Mo5	0.0270 (4)	0.1036 (8)	0.0647 (6)	0.000	−0.0019 (4)	0.000
Mo6	0.0530 (3)	0.0535 (3)	0.0473 (3)	−0.0019 (3)	−0.0137 (3)	0.0195 (3)
Mo7	0.0461 (4)	0.0372 (4)	0.0243 (3)	0.000	−0.0006 (3)	0.000
Mo8	0.0503 (3)	0.0557 (3)	0.0429 (3)	−0.0005 (3)	0.0105 (3)	0.0191 (3)
O1	0.035 (3)	0.063 (4)	0.062 (4)	0.000	−0.003 (3)	0.000
O2	0.067 (3)	0.054 (3)	0.066 (3)	−0.019 (3)	−0.022 (3)	0.006 (3)
O3	0.045 (4)	0.101 (6)	0.029 (3)	0.000	0.001 (3)	0.000
O4	0.081 (3)	0.049 (3)	0.096 (4)	0.024 (3)	0.045 (3)	0.017 (3)
O5	0.033 (3)	0.053 (4)	0.081 (5)	0.000	0.001 (3)	0.000
O6	0.087 (3)	0.069 (3)	0.049 (3)	0.037 (3)	−0.017 (3)	−0.009 (3)
O7	0.057 (4)	0.066 (11)	0.021 (3)	0.005 (4)	0.000 (3)	0.001 (4)
O8	0.076 (3)	0.065 (3)	0.052 (3)	−0.035 (3)	0.017 (3)	−0.004 (3)
O9	0.032 (4)	0.050 (5)	0.034 (4)	−0.006 (4)	0.003 (3)	0.007 (4)
O10	0.026 (4)	0.037 (4)	0.037 (4)	−0.003 (3)	−0.002 (3)	0.006 (4)
O11	0.039 (4)	0.039 (4)	0.033 (4)	−0.004 (4)	0.006 (3)	−0.003 (4)
O9'	0.035 (4)	0.051 (5)	0.030 (4)	−0.002 (4)	0.009 (4)	0.002 (4)
O10'	0.034 (4)	0.036 (4)	0.040 (4)	0.002 (4)	−0.001 (4)	0.001 (4)
O11'	0.046 (5)	0.038 (5)	0.035 (4)	−0.005 (4)	0.001 (4)	−0.005 (4)
O12	0.039 (2)	0.062 (3)	0.098 (3)	−0.002 (2)	−0.004 (2)	0.040 (3)
O13	0.040 (2)	0.063 (3)	0.105 (4)	−0.006 (2)	−0.007 (3)	0.049 (3)
O14	0.040 (2)	0.062 (3)	0.100 (3)	−0.004 (2)	−0.007 (2)	0.040 (3)
O15	0.036 (4)	0.037 (4)	0.049 (5)	0.014 (4)	0.008 (4)	0.000 (4)
O16	0.041 (4)	0.035 (4)	0.035 (4)	0.003 (4)	0.003 (4)	−0.005 (4)
O17	0.036 (4)	0.034 (4)	0.042 (4)	0.001 (4)	−0.004 (4)	−0.008 (4)
O15'	0.040 (4)	0.042 (5)	0.032 (4)	−0.005 (4)	0.004 (4)	0.003 (4)
O16'	0.039 (4)	0.042 (5)	0.037 (4)	0.009 (4)	−0.004 (4)	0.004 (4)
O17'	0.041 (4)	0.033 (4)	0.043 (5)	−0.004 (4)	−0.009 (4)	0.003 (4)
O18	0.044 (2)	0.049 (3)	0.112 (4)	−0.004 (2)	−0.001 (3)	−0.012 (3)
O19	0.047 (3)	0.058 (3)	0.127 (4)	0.003 (2)	−0.005 (3)	−0.032 (3)
O20	0.043 (2)	0.048 (3)	0.112 (4)	0.000 (2)	−0.006 (3)	−0.015 (3)
O21	0.029 (4)	0.039 (4)	0.020 (3)	0.002 (3)	−0.003 (3)	−0.006 (3)
O22	0.031 (4)	0.039 (4)	0.020 (3)	−0.003 (3)	−0.003 (3)	0.003 (3)
O23	0.028 (4)	0.046 (5)	0.021 (3)	−0.001 (3)	0.000 (3)	−0.003 (3)
O24	0.029 (3)	0.028 (4)	0.026 (4)	0.000 (3)	0.003 (3)	−0.002 (3)
N1	0.121 (7)	0.126 (7)	0.078 (5)	0.021 (6)	−0.022 (5)	−0.046 (5)
C1	0.079 (6)	0.118 (8)	0.084 (6)	−0.013 (6)	0.003 (5)	0.040 (6)
C2	0.088 (6)	0.060 (6)	0.175 (12)	−0.004 (5)	−0.052 (7)	0.011 (7)
C3	0.123 (8)	0.091 (6)	0.076 (6)	0.021 (6)	−0.021 (6)	−0.045 (5)
C4	0.079 (6)	0.156 (10)	0.045 (4)	−0.015 (7)	−0.002 (4)	0.025 (6)
C5	0.101 (7)	0.069 (6)	0.082 (6)	−0.025 (5)	−0.026 (5)	0.002 (5)
N2	0.083 (5)	0.048 (4)	0.067 (4)	−0.002 (3)	−0.008 (3)	0.009 (3)
C6	0.081 (5)	0.064 (5)	0.042 (4)	0.013 (4)	0.009 (4)	0.013 (4)
C7	0.083 (5)	0.053 (4)	0.040 (4)	0.009 (4)	−0.006 (4)	−0.008 (3)
C8	0.074 (5)	0.061 (5)	0.069 (5)	0.000 (4)	0.003 (4)	0.001 (4)
C9	0.082 (5)	0.057 (4)	0.046 (4)	0.002 (4)	0.018 (4)	0.008 (3)
C10	0.083 (5)	0.067 (5)	0.040 (4)	0.001 (4)	0.001 (4)	−0.006 (4)
O1W	0.099 (8)	0.117 (9)	0.109 (8)	0.000	−0.028 (7)	0.000

Geometric parameters (Å, º)

Si1—O23^i	1.566 (8)	Mo6—O6	1.652 (5)
Si1—O23	1.566 (8)	Mo6—O16	1.710 (8)
Si1—O24	1.578 (7)	Mo6—O19	1.834 (5)
Si1—O24^i	1.578 (7)	Mo6—O18	1.980 (6)
Si1—O21	1.675 (8)	Mo6—O17'	1.991 (9)
Si1—O21^i	1.675 (8)	Mo6—O17	1.992 (8)
Si1—O22^i	1.686 (8)	Mo6—O16'	2.039 (9)
Si1—O22	1.686 (8)	Mo6—O22	2.339 (7)
Mo1—O1	1.669 (6)	Mo6—O23	2.458 (8)
Mo1—O10	1.687 (8)	Mo7—O7^i	1.688 (7)
Mo1—O10^i	1.687 (8)	Mo7—O7	1.688 (7)
Mo1—O9^i	1.903 (9)	Mo7—O18^i	1.822 (5)
Mo1—O9	1.903 (9)	Mo7—O18	1.822 (5)
Mo1—O10'	2.003 (9)	Mo7—O20	1.964 (5)
Mo1—O10'^i	2.003 (9)	Mo7—O20^i	1.964 (5)
Mo1—O9'^i	2.159 (9)	Mo7—O23	2.378 (7)
Mo1—O9'	2.159 (9)	Mo7—O23^i	2.378 (7)
Mo1—O21^i	2.411 (7)	Mo8—O8	1.665 (5)
Mo1—O21	2.411 (7)	Mo8—O9	1.800 (9)
Mo2—O2	1.656 (5)	Mo8—O20	1.848 (6)
Mo2—O11	1.779 (8)	Mo8—O11	1.856 (8)
Mo2—O13	1.836 (5)	Mo8—O9'	1.888 (7)
Mo2—O11'	1.950 (8)	Mo8—O19	1.962 (5)
Mo2—O10	1.954 (8)	Mo8—O11'	2.154 (8)
Mo2—O12	1.966 (5)	Mo8—O21	2.346 (7)
Mo2—O10'	2.043 (8)	Mo8—O23	2.454 (8)
Mo2—O21	2.336 (7)	O7—O7^i	0.649 (19)
Mo2—O24	2.450 (7)	O23—O23^i	1.686 (17)
Mo3—O3	1.659 (6)	O24—O24^i	1.738 (14)
Mo3—O12	1.835 (5)	N1—C1	1.319 (15)
Mo3—O12^i	1.835 (5)	N1—C5	1.339 (13)
Mo3—O14^i	1.957 (5)	N1—H1A	0.8600
Mo3—O14	1.957 (5)	C1—C2	1.329 (16)
Mo3—O24^i	2.363 (7)	C1—H1B	0.9300
Mo3—O24	2.363 (7)	C2—C3	1.318 (16)
Mo4—O4	1.650 (5)	C2—H2B	0.9300
Mo4—O14	1.834 (5)	C3—C4	1.345 (16)
Mo4—O15	1.835 (9)	C3—H3A	0.9300
Mo4—O15'	1.886 (9)	C4—C5	1.317 (14)
Mo4—O16	1.921 (8)	C4—H4A	0.9300
Mo4—O13	1.978 (5)	C5—H5A	0.9300
Mo4—O16'	2.089 (8)	N2—C10	1.351 (10)
Mo4—O22	2.323 (7)	N2—C6	1.365 (10)
Mo4—O24	2.452 (7)	N2—H2A	0.8600
Mo5—O5	1.675 (6)	C6—C7	1.337 (12)
Mo5—O17^i	1.686 (8)	C6—H6A	0.9300
Mo5—O17	1.686 (8)	C7—C8	1.348 (11)
Mo5—O15	1.835 (9)	C7—H7A	0.9300
Mo5—O15^i	1.835 (9)	C8—C9	1.353 (11)
Mo5—O17'^i	2.050 (9)	C8—H8A	0.9300
Mo5—O17'	2.050 (9)	C9—C10	1.361 (12)
Mo5—O15'	2.147 (9)	C9—H9A	0.9300
Mo5—O15'^i	2.147 (9)	C10—H10A	0.9300
Mo5—O22	2.421 (7)	O1W—H1WA	0.8500
Mo5—O22^i	2.421 (7)
O23^i—Si1—O23	65.2 (6)	O17'^i—Mo5—O15'^i	78.7 (3)
O23^i—Si1—O24	179.2 (4)	O17'—Mo5—O15'^i	171.1 (3)
O23—Si1—O24	114.0 (4)	O15'—Mo5—O15'^i	93.2 (5)
O23^i—Si1—O24^i	114.0 (4)	O5—Mo5—O22	154.21 (19)
O23—Si1—O24^i	179.2 (4)	O17^i—Mo5—O22	88.3 (3)
O24—Si1—O24^i	66.8 (5)	O17—Mo5—O22	56.7 (3)
O23^i—Si1—O21	109.5 (4)	O15—Mo5—O22	53.6 (3)
O23—Si1—O21	71.1 (4)	O15^i—Mo5—O22	82.4 (3)
O24—Si1—O21	70.0 (3)	O17'^i—Mo5—O22	110.5 (3)
O24^i—Si1—O21	109.3 (4)	O17'—Mo5—O22	69.9 (3)
O23^i—Si1—O21^i	71.1 (4)	O15'—Mo5—O22	67.6 (3)
O23—Si1—O21^i	109.5 (4)	O15'^i—Mo5—O22	103.8 (3)
O24—Si1—O21^i	109.3 (4)	O5—Mo5—O22^i	154.21 (19)
O24^i—Si1—O21^i	70.0 (3)	O17^i—Mo5—O22^i	56.7 (3)
O21—Si1—O21^i	75.2 (5)	O17—Mo5—O22^i	88.3 (3)
O23^i—Si1—O22^i	71.3 (4)	O15—Mo5—O22^i	82.4 (3)
O23—Si1—O22^i	109.8 (4)	O15^i—Mo5—O22^i	53.6 (3)
O24—Si1—O22^i	109.1 (4)	O17'^i—Mo5—O22^i	69.9 (3)
O24^i—Si1—O22^i	69.7 (3)	O17'—Mo5—O22^i	110.5 (3)
O21—Si1—O22^i	179.0 (4)	O15'—Mo5—O22^i	103.8 (3)
O21^i—Si1—O22^i	104.6 (4)	O15'^i—Mo5—O22^i	67.6 (3)
O23^i—Si1—O22	109.8 (4)	O22—Mo5—O22^i	50.5 (4)
O23—Si1—O22	71.3 (4)	O6—Mo6—O16	114.3 (3)
O24—Si1—O22	69.7 (3)	O6—Mo6—O19	100.6 (3)
O24^i—Si1—O22	109.1 (4)	O16—Mo6—O19	89.6 (4)
O21—Si1—O22	104.6 (4)	O6—Mo6—O18	98.9 (2)
O21^i—Si1—O22	179.0 (4)	O16—Mo6—O18	146.5 (3)
O22^i—Si1—O22	75.5 (5)	O19—Mo6—O18	88.0 (2)
O1—Mo1—O10	116.0 (3)	O6—Mo6—O17'	89.7 (3)
O1—Mo1—O10^i	116.0 (3)	O16—Mo6—O17'	87.4 (4)
O10—Mo1—O10^i	79.8 (5)	O19—Mo6—O17'	169.6 (3)
O1—Mo1—O9^i	106.1 (3)	O18—Mo6—O17'	89.0 (3)
O10—Mo1—O9^i	136.3 (4)	O6—Mo6—O17	111.1 (3)
O10^i—Mo1—O9^i	92.5 (4)	O16—Mo6—O17	89.3 (4)
O1—Mo1—O9	106.1 (3)	O19—Mo6—O17	145.7 (3)
O10—Mo1—O9	92.5 (4)	O18—Mo6—O17	74.5 (3)
O10^i—Mo1—O9	136.3 (4)	O17'—Mo6—O17	24.5 (3)
O9^i—Mo1—O9	64.0 (5)	O6—Mo6—O16'	91.9 (3)
O1—Mo1—O10'	94.1 (3)	O16—Mo6—O16'	22.6 (3)
O10—Mo1—O10'	23.3 (3)	O19—Mo6—O16'	97.4 (3)
O10^i—Mo1—O10'	96.7 (4)	O18—Mo6—O16'	166.8 (3)
O9^i—Mo1—O10'	151.3 (4)	O17'—Mo6—O16'	83.5 (4)
O9—Mo1—O10'	91.2 (4)	O17—Mo6—O16'	94.6 (4)
O1—Mo1—O10'^i	94.1 (3)	O6—Mo6—O22	157.1 (3)
O10—Mo1—O10'^i	96.7 (4)	O16—Mo6—O22	52.1 (3)
O10^i—Mo1—O10'^i	23.3 (3)	O19—Mo6—O22	97.8 (3)
O9^i—Mo1—O10'^i	91.2 (4)	O18—Mo6—O22	95.2 (3)
O9—Mo1—O10'^i	151.3 (4)	O17'—Mo6—O22	72.6 (3)
O10'—Mo1—O10'^i	107.6 (5)	O17—Mo6—O22	55.9 (3)
O1—Mo1—O9'^i	88.5 (2)	O16'—Mo6—O22	72.1 (3)
O10—Mo1—O9'^i	155.5 (3)	O6—Mo6—O23	155.9 (3)
O10^i—Mo1—O9'^i	89.2 (3)	O16—Mo6—O23	86.4 (3)
O9^i—Mo1—O9'^i	21.6 (3)	O19—Mo6—O23	65.8 (3)
O9—Mo1—O9'^i	80.4 (4)	O18—Mo6—O23	62.3 (2)
O10'—Mo1—O9'^i	171.6 (3)	O17'—Mo6—O23	104.1 (3)
O10'^i—Mo1—O9'^i	80.0 (3)	O17—Mo6—O23	79.9 (3)
O1—Mo1—O9'	88.5 (2)	O16'—Mo6—O23	109.0 (3)
O10—Mo1—O9'	89.2 (3)	O22—Mo6—O23	46.5 (2)
O10^i—Mo1—O9'	155.5 (3)	O7^i—Mo7—O7	22.2 (6)
O9^i—Mo1—O9'	80.4 (4)	O7^i—Mo7—O18^i	110.2 (4)
O9—Mo1—O9'	21.6 (3)	O7—Mo7—O18^i	93.8 (4)
O10'—Mo1—O9'	80.0 (3)	O7^i—Mo7—O18	93.8 (4)
O10'^i—Mo1—O9'	171.6 (3)	O7—Mo7—O18	110.2 (4)
O9'^i—Mo1—O9'	92.1 (5)	O18^i—Mo7—O18	93.0 (3)
O1—Mo1—O21^i	153.4 (2)	O7^i—Mo7—O20	91.7 (3)
O10—Mo1—O21^i	88.3 (3)	O7—Mo7—O20	106.3 (3)
O10^i—Mo1—O21^i	55.0 (3)	O18^i—Mo7—O20	157.8 (3)
O9^i—Mo1—O21^i	53.9 (3)	O18—Mo7—O20	88.9 (2)
O9—Mo1—O21^i	82.0 (3)	O7^i—Mo7—O20^i	106.3 (3)
O10'—Mo1—O21^i	111.3 (3)	O7—Mo7—O20^i	91.7 (3)
O10'^i—Mo1—O21^i	71.2 (3)	O18^i—Mo7—O20^i	88.9 (2)
O9'^i—Mo1—O21^i	67.5 (2)	O18—Mo7—O20^i	157.8 (3)
O9'—Mo1—O21^i	103.2 (2)	O20—Mo7—O20^i	81.3 (3)
O1—Mo1—O21	153.4 (2)	O7^i—Mo7—O23	147.9 (4)
O10—Mo1—O21	55.0 (3)	O7—Mo7—O23	169.5 (4)
O10^i—Mo1—O21	88.3 (3)	O18^i—Mo7—O23	96.1 (3)
O9^i—Mo1—O21	82.0 (3)	O18—Mo7—O23	65.9 (3)
O9—Mo1—O21	53.9 (3)	O20—Mo7—O23	64.6 (3)
O10'—Mo1—O21	71.2 (3)	O20^i—Mo7—O23	91.9 (3)
O10'^i—Mo1—O21	111.3 (3)	O7^i—Mo7—O23^i	169.5 (4)
O9'^i—Mo1—O21	103.2 (2)	O7—Mo7—O23^i	147.9 (4)
O9'—Mo1—O21	67.5 (2)	O18^i—Mo7—O23^i	65.9 (3)
O21^i—Mo1—O21	50.2 (4)	O18—Mo7—O23^i	96.1 (3)
O2—Mo2—O11	114.5 (3)	O20—Mo7—O23^i	91.9 (3)
O2—Mo2—O13	101.6 (3)	O20^i—Mo7—O23^i	64.6 (3)
O11—Mo2—O13	89.0 (3)	O23—Mo7—O23^i	41.5 (4)
O2—Mo2—O11'	90.4 (3)	O8—Mo8—O9	114.8 (3)
O11—Mo2—O11'	24.5 (3)	O8—Mo8—O20	102.0 (3)
O13—Mo2—O11'	98.9 (3)	O9—Mo8—O20	86.3 (3)
O2—Mo2—O10	110.7 (3)	O8—Mo8—O11	109.3 (3)
O11—Mo2—O10	88.6 (4)	O9—Mo8—O11	90.1 (4)
O13—Mo2—O10	145.5 (3)	O20—Mo8—O11	146.8 (3)
O11'—Mo2—O10	92.9 (4)	O8—Mo8—O9'	92.0 (3)
O2—Mo2—O12	99.4 (3)	O9—Mo8—O9'	24.9 (3)
O11—Mo2—O12	145.9 (3)	O20—Mo8—O9'	101.2 (3)
O13—Mo2—O12	88.4 (2)	O11—Mo8—O9'	88.5 (4)
O11'—Mo2—O12	166.4 (3)	O8—Mo8—O19	98.9 (3)
O10—Mo2—O12	74.8 (3)	O9—Mo8—O19	146.3 (3)
O2—Mo2—O10'	89.4 (3)	O20—Mo8—O19	88.1 (2)
O11—Mo2—O10'	89.1 (4)	O11—Mo8—O19	76.9 (3)
O13—Mo2—O10'	168.6 (3)	O9'—Mo8—O19	164.0 (3)
O11'—Mo2—O10'	83.8 (4)	O8—Mo8—O11'	88.7 (3)
O10—Mo2—O10'	23.2 (3)	O9—Mo8—O11'	93.1 (4)
O12—Mo2—O10'	86.8 (3)	O20—Mo8—O11'	168.5 (3)
O2—Mo2—O21	156.6 (3)	O11—Mo8—O11'	21.7 (3)
O11—Mo2—O21	52.7 (3)	O9'—Mo8—O11'	82.4 (4)
O13—Mo2—O21	97.9 (3)	O19—Mo8—O11'	86.1 (3)
O11'—Mo2—O21	73.7 (3)	O8—Mo8—O21	155.2 (3)
O10—Mo2—O21	54.7 (3)	O9—Mo8—O21	56.1 (3)
O12—Mo2—O21	94.1 (3)	O20—Mo8—O21	100.3 (3)
O10'—Mo2—O21	72.2 (3)	O11—Mo8—O21	52.0 (3)
O2—Mo2—O24	156.8 (3)	O9'—Mo8—O21	73.1 (3)
O11—Mo2—O24	85.7 (3)	O19—Mo8—O21	92.5 (3)
O13—Mo2—O24	65.8 (2)	O11'—Mo8—O21	70.1 (3)
O11'—Mo2—O24	110.2 (3)	O8—Mo8—O23	157.5 (3)
O10—Mo2—O24	79.7 (3)	O9—Mo8—O23	83.4 (3)
O12—Mo2—O24	62.4 (2)	O20—Mo8—O23	64.3 (2)
O10'—Mo2—O24	102.8 (3)	O11—Mo8—O23	82.5 (3)
O21—Mo2—O24	45.9 (2)	O9'—Mo8—O23	107.8 (3)
O3—Mo3—O12	101.7 (2)	O19—Mo8—O23	64.4 (3)
O3—Mo3—O12^i	101.7 (2)	O11'—Mo8—O23	104.1 (3)
O12—Mo3—O12^i	94.4 (3)	O21—Mo8—O23	46.2 (2)
O3—Mo3—O14^i	98.9 (2)	O7^i—O7—Mo7	78.9 (3)
O12—Mo3—O14^i	158.3 (3)	Mo8—O9—Mo1	146.4 (5)
O12^i—Mo3—O14^i	88.0 (2)	Mo1—O10—Mo2	149.2 (5)
O3—Mo3—O14	98.9 (2)	Mo2—O11—Mo8	152.0 (5)
O12—Mo3—O14	88.0 (2)	Mo8—O9'—Mo1	122.2 (3)
O12^i—Mo3—O14	158.3 (3)	Mo1—O10'—Mo2	120.4 (4)
O14^i—Mo3—O14	82.1 (3)	Mo2—O11'—Mo8	118.4 (4)
O3—Mo3—O24^i	157.97 (18)	Mo3—O12—Mo2	136.8 (3)
O12—Mo3—O24^i	97.5 (3)	Mo2—O13—Mo4	137.0 (3)
O12^i—Mo3—O24^i	65.8 (2)	Mo4—O14—Mo3	137.8 (3)
O14^i—Mo3—O24^i	63.9 (2)	Mo4—O15—Mo5	147.8 (5)
O14—Mo3—O24^i	92.5 (2)	Mo6—O16—Mo4	153.2 (5)
O3—Mo3—O24	157.97 (18)	Mo5—O17—Mo6	145.8 (5)
O12—Mo3—O24	65.8 (2)	Mo4—O15'—Mo5	121.8 (4)
O12^i—Mo3—O24	97.5 (3)	Mo6—O16'—Mo4	117.7 (4)
O14^i—Mo3—O24	92.5 (2)	Mo6—O17'—Mo5	120.9 (4)
O14—Mo3—O24	63.9 (2)	Mo7—O18—Mo6	137.1 (3)
O24^i—Mo3—O24	43.1 (3)	Mo6—O19—Mo8	137.5 (3)
O4—Mo4—O14	102.3 (3)	Mo8—O20—Mo7	136.4 (3)
O4—Mo4—O15	116.2 (3)	Si1—O21—Mo2	122.7 (4)
O14—Mo4—O15	87.5 (3)	Si1—O21—Mo8	121.5 (4)
O4—Mo4—O15'	92.9 (3)	Mo2—O21—Mo8	97.8 (3)
O14—Mo4—O15'	102.0 (3)	Si1—O21—Mo1	117.1 (4)
O15—Mo4—O15'	25.1 (3)	Mo2—O21—Mo1	95.4 (2)
O4—Mo4—O16	110.7 (3)	Mo8—O21—Mo1	96.4 (3)
O14—Mo4—O16	145.2 (3)	Si1—O22—Mo4	122.9 (4)
O15—Mo4—O16	88.0 (4)	Si1—O22—Mo6	121.3 (4)
O15'—Mo4—O16	87.6 (4)	Mo4—O22—Mo6	98.6 (3)
O4—Mo4—O13	97.6 (3)	Si1—O22—Mo5	116.8 (4)
O14—Mo4—O13	87.5 (2)	Mo4—O22—Mo5	96.0 (3)
O15—Mo4—O13	146.2 (3)	Mo6—O22—Mo5	95.2 (3)
O15'—Mo4—O13	164.1 (3)	Si1—O23—O23^i	57.4 (3)
O16—Mo4—O13	77.5 (3)	Si1—O23—Mo7	126.5 (5)
O4—Mo4—O16'	88.4 (3)	O23^i—O23—Mo7	69.2 (2)
O14—Mo4—O16'	167.0 (3)	Si1—O23—Mo8	120.9 (4)
O15—Mo4—O16'	94.4 (4)	O23^i—O23—Mo8	128.86 (18)
O15'—Mo4—O16'	84.4 (4)	Mo7—O23—Mo8	94.2 (3)
O16—Mo4—O16'	22.6 (3)	Si1—O23—Mo6	120.6 (4)
O13—Mo4—O16'	83.9 (3)	O23^i—O23—Mo6	135.33 (18)
O4—Mo4—O22	156.7 (3)	Mo7—O23—Mo6	94.1 (3)
O14—Mo4—O22	99.2 (3)	Mo8—O23—Mo6	92.2 (3)
O15—Mo4—O22	55.7 (3)	Si1—O24—O24^i	56.6 (3)
O15'—Mo4—O22	73.8 (3)	Si1—O24—Mo3	124.9 (4)
O16—Mo4—O22	51.1 (3)	O24^i—O24—Mo3	68.43 (17)
O13—Mo4—O22	92.3 (3)	Si1—O24—Mo2	121.1 (4)
O16'—Mo4—O22	71.6 (3)	O24^i—O24—Mo2	135.35 (16)
O4—Mo4—O24	155.9 (3)	Mo3—O24—Mo2	94.5 (3)
O14—Mo4—O24	63.4 (2)	Si1—O24—Mo4	121.1 (4)
O15—Mo4—O24	83.8 (3)	O24^i—O24—Mo4	128.16 (17)
O15'—Mo4—O24	108.6 (3)	Mo3—O24—Mo4	94.5 (2)
O16—Mo4—O24	81.8 (3)	Mo2—O24—Mo4	92.8 (2)
O13—Mo4—O24	64.1 (2)	C1—N1—C5	119.8 (9)
O16'—Mo4—O24	104.0 (3)	C1—N1—H1A	120.1
O22—Mo4—O24	46.0 (2)	C5—N1—H1A	120.1
O5—Mo5—O17^i	112.8 (4)	N1—C1—C2	118.6 (10)
O5—Mo5—O17	112.8 (4)	N1—C1—H1B	120.7
O17^i—Mo5—O17	75.2 (6)	C2—C1—H1B	120.7
O5—Mo5—O15	109.2 (3)	C3—C2—C1	122.2 (11)
O17^i—Mo5—O15	137.5 (4)	C3—C2—H2B	118.9
O17—Mo5—O15	94.6 (4)	C1—C2—H2B	118.9
O5—Mo5—O15^i	109.2 (3)	C2—C3—C4	118.9 (10)
O17^i—Mo5—O15^i	94.6 (4)	C2—C3—H3A	120.5
O17—Mo5—O15^i	137.5 (4)	C4—C3—H3A	120.5
O15—Mo5—O15^i	65.3 (5)	C5—C4—C3	119.0 (9)
O5—Mo5—O17'^i	92.9 (3)	C5—C4—H4A	120.5
O17^i—Mo5—O17'^i	23.6 (3)	C3—C4—H4A	120.5
O17—Mo5—O17'^i	94.5 (4)	C4—C5—N1	121.2 (9)
O15—Mo5—O17'^i	150.5 (4)	C4—C5—H5A	119.4
O15^i—Mo5—O17'^i	89.5 (4)	N1—C5—H5A	119.4
O5—Mo5—O17'	92.9 (3)	C10—N2—C6	120.0 (7)
O17^i—Mo5—O17'	94.5 (4)	C10—N2—H2A	120.0
O17—Mo5—O17'	23.6 (3)	C6—N2—H2A	120.0
O15—Mo5—O17'	89.5 (4)	C7—C6—N2	120.6 (7)
O15^i—Mo5—O17'	150.5 (4)	C7—C6—H6A	119.7
O17'^i—Mo5—O17'	109.1 (5)	N2—C6—H6A	119.7
O5—Mo5—O15'	90.8 (3)	C6—C7—C8	119.9 (8)
O17^i—Mo5—O15'	155.9 (4)	C6—C7—H7A	120.0
O17—Mo5—O15'	91.5 (4)	C8—C7—H7A	120.0
O15—Mo5—O15'	21.7 (3)	C7—C8—C9	119.9 (8)
O15^i—Mo5—O15'	81.6 (4)	C7—C8—H8A	120.1
O17'^i—Mo5—O15'	171.1 (3)	C9—C8—H8A	120.1
O17'—Mo5—O15'	78.7 (3)	C8—C9—C10	120.8 (8)
O5—Mo5—O15'^i	90.8 (3)	C8—C9—H9A	119.6
O17^i—Mo5—O15'^i	91.5 (4)	C10—C9—H9A	119.6
O17—Mo5—O15'^i	155.9 (4)	N2—C10—C9	118.8 (7)
O15—Mo5—O15'^i	81.6 (4)	N2—C10—H10A	120.6
O15^i—Mo5—O15'^i	21.7 (3)	C9—C10—H10A	120.6

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O14	0.86	2.38	3.20 (1)	161
N2—H2A···O16^ii	0.86	2.43	3.29 (1)	174
N2—H2A···O16′^ii	0.86	2.21	3.05 (1)	166
C2—H2B···O11′^ii	0.93	2.07	2.96 (1)	160
C3—H3A···O4^iii	0.93	2.52	3.25 (1)	136
C4—H4A···O6^iv	0.93	2.52	3.26 (1)	137
C5—H5A···O9′^v	0.93	2.45	2.93 (1)	112
C7—H7A···O12	0.93	2.28	3.20 (1)	169
C8—H8A···O7^vi	0.93	2.59	3.28 (1)	131
C9—H9A···O20^iv	0.93	2.35	3.26 (1)	168

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