[(CH3)2NH2]4[H4PMo12O40]Cl2·4H2O

Wu, C.-D.; Lu, C.-Z.; Lin, X.; Yang, W.-B.; Zhuang, H.-H.; Huang, J.-S.

doi:10.1107/S1600536801010467

[(CH₃)₂NH₂]₄[H₄PMo₁₂O₄₀]Cl₂·4H₂O

C.-D. Wu, C.-Z. Lu, X. Lin, W.-B. Yang, H.-H. Zhuang and J.-S. Huang

The hydrothermal reaction of an aqueous solution of sodium molybdate, hypophosphorous acid, hydrochloric acid and N,N-dimethylformamide (DMF) gave rise to tetradimethylammonium tetrahydroxydotriacontaoxo(tetraoxophosphato)dodecamolybdate dihydrochloride tetrahydrate. The polyanion has a β-Keggin structure, with P—O distances ranging from 1.535 (5) to 1.552 (5) Å and Mo—O distances from 1.664 (4) to 2.509 (4) Å.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010467/cf6065sup1.cif Contains datablocks I, new
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010467/cf6065Isup2.hkl Contains datablock I

CCDC reference: 172189

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (N-C) = 0.013 Å
H-atom completeness 55%
R factor = 0.034
wR factor = 0.090
Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and the formula from the _atom_site* data.
          Atom count from _chemical_formula_sum:C8 H44 Cl2 Mo12 N4 O44 P1
          Atom count from the _atom_site data:  C8 H24 Cl2 Mo12 N4 O44 P1

ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.845
          Tmax scaled      0.539 Tmin scaled      0.260

CELLZ_01
         From the CIF: _cell_formula_units_Z    4
         From the CIF: _chemical_formula_sum  C8 H44 Cl2 Mo12 N4 O44 P
         TEST: Compare cell contents of formula and atom_site data

         atom    Z*formula  cif sites diff
         C         32.00     32.00    0.00
         H        176.00     96.00   80.00
         Cl         8.00      8.00    0.00
         Mo        48.00     48.00    0.00
         N         16.00     16.00    0.00
         O        176.00    176.00    0.00
         P          4.00      4.00    0.00
          Difference between formula and atom_site contents detected.
          WARNING: H atoms missing from atom site list. Is this intentional?

Comment top

The structure of the [PMo₁₂O₄₀]^3- heteropolyanion was first reported by Strandberg (1975) and then by D'amour & Allmann (1976). Fruchart and Souchay had shown that reduction of the Keggin-structure anion α-[PMo₁₂O₄₀]^3- in aqueous acidic solutions leaded to a stable heteropoly blue isomeric β-anion (1968). However, the conclusion had not been structurally proved until 1985 (Barrows et al., 1985). The title compound, (I), is a pseudo-Keggin (Keggin, 1934) heteropoly compound, of which four Mo atoms are reduced (confirmed by cerimetric titration) and four bridging O atoms are protonated. The Mo—O distances range from 2.090 (4) to 2.115 (3) Å (cf. 1.92 Å for oxidized structures) and Mo—O—Mo angles from 115.7 (2) to 147.8 (2)° (cf. 92° for the oxidized structures) (Barrows et al., 1985).

As shown in Fig. 1, the [PMo₁₂O₄₀]^2- polyanion consists of one {PO₄} tetrahedron and 12 {MoO₆} octahedra. The central almost regular {PO₄} is a tetrahedron with P—O distances ranging from 1.535 (5) to 1.552 (5) Å and O—P—O angles ranging from 109.1 (2) to 110.0 (3)°. The coordination environment for each Mo atom is a distorted octahedron, with Mo—O distances ranging from 1.664 (4) to 2.509 (4) Å and angles involving the neighboring O atoms from 71.2 (1) to 105.6 (2)°. The {PO₄} tetrahedeon and 12 {MoO₆} octahedra are linked together through µ₄-O atoms. All O atoms of the anion can be divided into three groups: terminal O atoms, µ₂-O atoms and µ₄-O atoms. The distances between terminal O atoms and Mo atoms range from 1.664 (4) to 1.678 (4) Å, while that of µ₂-O atoms and µ₄-O atoms range from 1.865 (4) to 2.115 (3) Å and from 2.406 (3) to 2.509 (4) Å, respectively.

The title compound contains two chlorine anions in its crystal structure. As shown in Fig. 2, the (CH₃)₂NH₂⁺ and Cl^- ions and water molecules are filled inside the unit cell. Finally, it should also be pointed out, as no (CH₃)₂NH₂⁺ ion was added to the reaction, the cation might derive from DMF, however, the mechanism is still to be further studied.

Experimental top

The title compound was prepared by hydrothermal synthesis from a mixture of Na₂MoO₄·2H₂O (1.21 g, 5 mmol), DMF (0.5 ml), 35% HCl (2.5 ml), 35% H₃PO₂ (0.2 ml) in H₂O (8 ml), heated at 433 K for one day and cooled. After filtration, the filtrate was allowed to stand in air for about one week, whereupon blue crystals suitable for X-ray diffraction study were obtained. Elemental analysis, calculated: Mo 53.46, P 1.44, Cl 3.29, C 4.46, N 2.60, H 2.06%; found: Mo 53.39, P 1.39, Cl 3.30, C 4.41, N 2.54, H 2.02%.

Computing details top

Data collection: SMART (Siemens, 1994); cell refinement: SMART and SAINT (Siemens, 1996); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL.

Figures top

	Fig. 1. The structure of the [(H₄PMo₁₂O₄₀)]^2- anion. [Author: the hpg file for this figure did not convert well with regard to the atom labels. Please forward a postscript file with the proof corrections]
	Fig. 2. Packing diagram viewed down the a axis.

tetradimethylammonium hexahydroxytriacontaoxo- (tetraoxophosphato)dodecamolybdate dichloride top

Crystal data top

(C₂H₆NH₂)₄[H₄PMo₁₂O₄₀]Cl₂·4H₂O	D_x = 2.801 Mg m⁻³
M_r = 2153.62	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 5625 reflections
a = 14.9803 (7) Å	θ = 1.6–25.0°
b = 15.0682 (8) Å	µ = 3.09 mm⁻¹
c = 22.6217 (12) Å	T = 293 K
V = 5106.3 (5) Å³	Prism, blue
Z = 4	0.45 × 0.25 × 0.20 mm
F(000) = 4100

Data collection top

SMART CCD diffractometer	4616 independent reflections
Radiation source: fine-focus sealed tube	3868 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −16→17
T_min = 0.308, T_max = 0.638	k = −17→17
16093 measured reflections	l = −16→26

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0451P)² + 4.5711P] where P = (F_o² + 2F_c²)/3
4616 reflections	(Δ/σ)_max = 0.001
346 parameters	Δρ_max = 0.77 e Å⁻³
0 restraints	Δρ_min = −1.45 e Å⁻³

Crystal data top

(C₂H₆NH₂)₄[H₄PMo₁₂O₄₀]Cl₂·4H₂O	V = 5106.3 (5) Å³
M_r = 2153.62	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 14.9803 (7) Å	µ = 3.09 mm⁻¹
b = 15.0682 (8) Å	T = 293 K
c = 22.6217 (12) Å	0.45 × 0.25 × 0.20 mm

Data collection top

SMART CCD diffractometer	4616 independent reflections
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	3868 reflections with I > 2σ(I)
T_min = 0.308, T_max = 0.638	R_int = 0.045
16093 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.77 e Å⁻³
4616 reflections	Δρ_min = −1.45 e Å⁻³
346 parameters

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
Mo1	0.52413 (3)	−0.12694 (3)	0.41208 (2)	0.02241 (14)
Mo2	0.90300 (3)	−0.12836 (3)	0.45329 (2)	0.02278 (14)
Mo3	0.72576 (3)	−0.12815 (3)	0.34095 (2)	0.02241 (14)
Mo4	0.49640 (4)	−0.2500	0.55895 (3)	0.02137 (17)
Mo5	0.67296 (3)	−0.13119 (3)	0.61515 (2)	0.01957 (13)
Mo6	0.87958 (4)	−0.2500	0.58057 (3)	0.02083 (16)
Mo7	0.69432 (3)	−0.00835 (3)	0.47544 (2)	0.02279 (13)
Cl1	1.04719 (18)	−0.2500	0.30235 (11)	0.0518 (6)
Cl2	0.68407 (15)	0.2500	0.26296 (10)	0.0415 (6)
P1	0.70035 (11)	−0.2500	0.47753 (8)	0.0149 (4)
O1	0.9514 (3)	−0.2500	0.6371 (2)	0.0323 (14)
O2	0.5758 (2)	−0.0218 (3)	0.44803 (16)	0.0256 (8)
O3	0.6771 (2)	−0.0641 (3)	0.67374 (16)	0.0307 (9)
O4	0.7034 (3)	0.1001 (3)	0.48767 (18)	0.0333 (10)
O5	0.8021 (3)	−0.2500	0.4856 (2)	0.0209 (11)
O6	0.6727 (2)	−0.1660 (2)	0.44290 (15)	0.0203 (8)
O7	0.9573 (3)	−0.2500	0.4264 (2)	0.0235 (12)
O8	0.6694 (2)	−0.0533 (3)	0.55117 (16)	0.0255 (9)
O9	0.9346 (2)	−0.1613 (3)	0.53001 (15)	0.0243 (9)
O10	0.6548 (3)	−0.2500	0.5391 (2)	0.0187 (11)
O11	0.5476 (2)	−0.1603 (3)	0.60879 (15)	0.0224 (8)
O12	0.7923 (2)	−0.1618 (3)	0.60303 (16)	0.0234 (8)
O13	0.8357 (2)	−0.1380 (3)	0.37983 (16)	0.0247 (9)
O14	0.8142 (2)	−0.0489 (3)	0.47890 (16)	0.0258 (9)
O15	0.6001 (2)	−0.1139 (3)	0.34373 (16)	0.0248 (9)
O16	0.3909 (3)	−0.2500	0.5835 (2)	0.0280 (13)
O17	0.5123 (3)	−0.2500	0.3971 (2)	0.0238 (12)
O18	0.7188 (3)	−0.2500	0.3262 (2)	0.0261 (12)
O19	0.4928 (2)	−0.1605 (3)	0.49627 (16)	0.0302 (9)
O20	0.4279 (3)	−0.0872 (3)	0.38600 (18)	0.0346 (10)
O21	0.6718 (3)	−0.2500	0.6649 (2)	0.0221 (12)
O22	0.9877 (3)	−0.0626 (3)	0.43334 (17)	0.0360 (11)
O23	0.7495 (3)	−0.0881 (3)	0.27354 (17)	0.0343 (10)
O24	0.7223 (2)	−0.0052 (3)	0.38493 (15)	0.0254 (9)
O101	0.5965 (3)	0.0864 (3)	0.32466 (17)	0.0330 (10)
O102	0.6143 (9)	0.2500	0.7104 (5)	0.125 (4)
O103	0.4613 (5)	0.2500	0.2462 (3)	0.088 (3)
N1	0.5509 (3)	−0.0347 (4)	0.2284 (2)	0.0383 (13)
N2	0.3499 (6)	0.2500	0.1476 (4)	0.057 (2)
N3	0.7597 (10)	0.2500	0.6511 (7)	0.129 (6)
C1	0.4530 (4)	−0.0237 (6)	0.2277 (3)	0.058 (2)
H1A	0.4267	−0.0619	0.2569	0.087*
H1B	0.4304	−0.0391	0.1893	0.087*
H1C	0.4382	0.0369	0.2364	0.087*
C2	0.5965 (5)	0.0230 (6)	0.1847 (3)	0.063 (2)
H2A	0.6598	0.0135	0.1869	0.095*
H2B	0.5836	0.0841	0.1934	0.095*
H2C	0.5757	0.0090	0.1457	0.095*
C3	0.3517 (7)	0.1708 (8)	0.1111 (6)	0.116 (4)
H3A	0.3503	0.1191	0.1359	0.174*
H3B	0.4054	0.1704	0.0879	0.174*
H3C	0.3008	0.1706	0.0853	0.174*
C4	0.7657 (10)	0.1759 (17)	0.6131 (8)	0.289 (17)
H4A	0.7593	0.1224	0.6357	0.434*
H4B	0.8228	0.1760	0.5937	0.434*
H4C	0.7192	0.1790	0.5840	0.434*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0196 (2)	0.0251 (3)	0.0226 (3)	0.0038 (2)	−0.00269 (18)	−0.0011 (2)
Mo2	0.0187 (2)	0.0298 (3)	0.0199 (3)	−0.0037 (2)	0.00098 (18)	0.0018 (2)
Mo3	0.0238 (3)	0.0269 (3)	0.0165 (2)	0.0001 (2)	0.00005 (18)	0.00272 (19)
Mo4	0.0159 (3)	0.0302 (4)	0.0179 (3)	0.000	0.0019 (3)	0.000
Mo5	0.0194 (2)	0.0227 (3)	0.0166 (2)	−0.00018 (19)	0.00151 (17)	−0.00262 (19)
Mo6	0.0153 (3)	0.0304 (4)	0.0167 (3)	0.000	−0.0014 (2)	0.000
Mo7	0.0271 (3)	0.0201 (3)	0.0212 (2)	−0.0003 (2)	0.00027 (19)	0.00061 (19)
Cl1	0.0616 (15)	0.0495 (16)	0.0445 (14)	0.000	0.0158 (12)	0.000
Cl2	0.0421 (12)	0.0495 (15)	0.0330 (12)	0.000	0.0087 (9)	0.000
P1	0.0138 (8)	0.0185 (11)	0.0123 (8)	0.000	0.0004 (7)	0.000
O1	0.024 (3)	0.048 (4)	0.025 (3)	0.000	−0.005 (2)	0.000
O2	0.027 (2)	0.025 (2)	0.024 (2)	0.0048 (18)	−0.0001 (16)	−0.0019 (17)
O3	0.033 (2)	0.037 (3)	0.021 (2)	−0.0010 (19)	0.0025 (16)	−0.0068 (18)
O4	0.042 (2)	0.021 (2)	0.036 (2)	−0.0032 (19)	0.0026 (19)	0.0005 (19)
O5	0.017 (2)	0.028 (3)	0.018 (3)	0.000	−0.003 (2)	0.000
O6	0.0202 (18)	0.023 (2)	0.0177 (18)	−0.0002 (16)	0.0007 (14)	0.0022 (16)
O7	0.018 (2)	0.027 (3)	0.026 (3)	0.000	0.003 (2)	0.000
O8	0.028 (2)	0.028 (2)	0.0205 (19)	0.0004 (17)	0.0018 (15)	−0.0019 (17)
O9	0.0159 (18)	0.036 (2)	0.0214 (19)	−0.0019 (17)	−0.0001 (15)	0.0005 (17)
O10	0.016 (2)	0.027 (3)	0.014 (2)	0.000	0.0027 (19)	0.000
O11	0.0197 (18)	0.028 (2)	0.0199 (18)	0.0002 (17)	0.0034 (15)	−0.0015 (16)
O12	0.0211 (18)	0.028 (2)	0.0209 (19)	−0.0026 (17)	0.0000 (15)	−0.0024 (16)
O13	0.025 (2)	0.029 (2)	0.0197 (19)	0.0014 (17)	0.0016 (15)	0.0024 (16)
O14	0.0273 (19)	0.027 (2)	0.0234 (19)	0.0010 (18)	−0.0021 (15)	−0.0018 (17)
O15	0.026 (2)	0.029 (2)	0.0192 (19)	0.0009 (17)	−0.0026 (15)	0.0010 (17)
O16	0.020 (3)	0.040 (4)	0.023 (3)	0.000	0.004 (2)	0.000
O17	0.023 (3)	0.030 (3)	0.019 (3)	0.000	−0.001 (2)	0.000
O18	0.025 (3)	0.033 (3)	0.020 (3)	0.000	0.000 (2)	0.000
O19	0.0226 (19)	0.048 (3)	0.0198 (19)	0.0021 (19)	0.0006 (15)	0.0070 (19)
O20	0.028 (2)	0.040 (3)	0.036 (2)	0.010 (2)	−0.0051 (18)	−0.001 (2)
O21	0.024 (3)	0.028 (3)	0.014 (2)	0.000	0.003 (2)	0.000
O22	0.029 (2)	0.047 (3)	0.032 (2)	−0.014 (2)	0.0030 (17)	0.005 (2)
O23	0.037 (2)	0.043 (3)	0.023 (2)	0.000 (2)	0.0030 (17)	0.0086 (19)
O24	0.0295 (19)	0.027 (2)	0.0201 (19)	−0.0007 (18)	0.0024 (16)	0.0009 (16)
O101	0.039 (2)	0.029 (2)	0.031 (2)	0.004 (2)	−0.0027 (18)	0.0005 (19)
O102	0.172 (12)	0.121 (10)	0.082 (8)	0.000	−0.028 (7)	0.000
O103	0.045 (4)	0.184 (11)	0.035 (4)	0.000	0.011 (3)	0.000
N1	0.037 (3)	0.043 (4)	0.035 (3)	−0.003 (3)	−0.004 (2)	0.003 (2)
N2	0.044 (5)	0.071 (7)	0.057 (6)	0.000	−0.006 (4)	0.000
N3	0.120 (12)	0.173 (17)	0.094 (11)	0.000	−0.028 (9)	0.000
C1	0.040 (4)	0.078 (6)	0.056 (5)	0.002 (4)	0.004 (3)	−0.020 (4)
C2	0.069 (5)	0.086 (6)	0.034 (4)	−0.030 (5)	0.001 (3)	0.016 (4)
C3	0.082 (7)	0.121 (10)	0.145 (11)	−0.051 (8)	−0.019 (7)	−0.032 (9)
C4	0.116 (12)	0.51 (4)	0.24 (2)	−0.127 (18)	0.045 (13)	−0.24 (2)

Geometric parameters (Å, º) top

Mo1—O20	1.668 (4)	Mo5—O10	2.497 (3)
Mo1—O17	1.893 (1)	Mo6—O1	1.672 (5)
Mo1—O15	1.930 (4)	Mo6—O12ⁱ	1.933 (4)
Mo1—O2	1.941 (4)	Mo6—O12	1.933 (4)
Mo1—O19	2.026 (4)	Mo6—O9	1.943 (4)
Mo1—O6	2.406 (3)	Mo6—O9ⁱ	1.943 (4)
Mo2—O22	1.672 (4)	Mo6—O5	2.442 (5)
Mo2—O9	1.866 (4)	Mo7—O4	1.663 (4)
Mo2—O14	1.881 (4)	Mo7—O8	1.879 (4)
Mo2—O13	1.949 (4)	Mo7—O2	1.892 (4)
Mo2—O7	2.096 (2)	Mo7—O14	1.899 (4)
Mo2—O5	2.486 (3)	Mo7—O24	2.090 (3)
Mo3—O23	1.678 (4)	Mo7—O6	2.508 (4)
Mo3—O18	1.869 (1)	P1—O5	1.535 (5)
Mo3—O13	1.873 (4)	P1—O6	1.545 (4)
Mo3—O15	1.896 (4)	P1—O6ⁱ	1.545 (4)
Mo3—O24	2.104 (4)	P1—O10	1.552 (5)
Mo3—O6	2.505 (3)	O5—Mo2ⁱ	2.486 (3)
Mo4—O16	1.676 (5)	O7—Mo2ⁱ	2.096 (2)
Mo4—O11	1.921 (4)	O10—Mo5ⁱ	2.497 (3)
Mo4—O11ⁱ	1.921 (4)	O17—Mo1ⁱ	1.8933 (11)
Mo4—O19ⁱ	1.958 (4)	O18—Mo3ⁱ	1.8690 (11)
Mo4—O19	1.958 (4)	O21—Mo5ⁱ	2.115 (3)
Mo4—O10	2.415 (5)	N1—C1	1.477 (8)
Mo5—O3	1.669 (4)	N1—C2	1.482 (8)
Mo5—O8	1.865 (4)	N2—C3	1.452 (12)
Mo5—O12	1.866 (3)	N2—C3ⁱⁱ	1.452 (12)
Mo5—O11	1.933 (3)	N3—C4	1.413 (18)
Mo5—O21	2.115 (3)	N3—C4ⁱⁱ	1.413 (18)

O20—Mo1—O17	101.9 (2)	O11—Mo5—O10	71.37 (15)
O20—Mo1—O15	100.92 (18)	O21—Mo5—O10	76.04 (13)
O17—Mo1—O15	90.69 (19)	O1—Mo6—O12ⁱ	103.56 (17)
O20—Mo1—O2	101.53 (19)	O1—Mo6—O12	103.56 (17)
O17—Mo1—O2	155.69 (18)	O12ⁱ—Mo6—O12	86.9 (2)
O15—Mo1—O2	90.99 (16)	O1—Mo6—O9	100.23 (17)
O20—Mo1—O19	102.83 (18)	O12ⁱ—Mo6—O9	156.20 (15)
O17—Mo1—O19	84.4 (2)	O12—Mo6—O9	88.20 (16)
O15—Mo1—O19	156.25 (15)	O1—Mo6—O9ⁱ	100.23 (17)
O2—Mo1—O19	84.37 (17)	O12ⁱ—Mo6—O9ⁱ	88.20 (16)
O20—Mo1—O6	171.74 (18)	O12—Mo6—O9ⁱ	156.20 (15)
O17—Mo1—O6	84.18 (17)	O9—Mo6—O9ⁱ	87.0 (2)
O15—Mo1—O6	73.24 (13)	O1—Mo6—O5	168.3 (2)
O2—Mo1—O6	73.12 (14)	O12ⁱ—Mo6—O5	84.80 (13)
O19—Mo1—O6	83.14 (13)	O12—Mo6—O5	84.80 (13)
O22—Mo2—O9	102.48 (17)	O9—Mo6—O5	71.57 (13)
O22—Mo2—O14	104.03 (19)	O9ⁱ—Mo6—O5	71.57 (13)
O9—Mo2—O14	93.56 (16)	O4—Mo7—O8	102.62 (18)
O22—Mo2—O13	101.92 (17)	O4—Mo7—O2	103.71 (19)
O9—Mo2—O13	154.74 (16)	O8—Mo7—O2	94.24 (16)
O14—Mo2—O13	86.79 (16)	O4—Mo7—O14	103.38 (19)
O22—Mo2—O7	98.34 (19)	O8—Mo7—O14	91.97 (16)
O9—Mo2—O7	86.51 (18)	O2—Mo7—O14	150.11 (16)
O14—Mo2—O7	157.05 (17)	O4—Mo7—O24	97.12 (18)
O13—Mo2—O7	83.61 (18)	O8—Mo7—O24	160.20 (16)
O22—Mo2—O5	167.92 (17)	O2—Mo7—O24	82.50 (14)
O9—Mo2—O5	71.62 (16)	O14—Mo7—O24	81.85 (15)
O14—Mo2—O5	87.07 (15)	O4—Mo7—O6	171.97 (16)
O13—Mo2—O5	83.19 (16)	O8—Mo7—O6	84.31 (14)
O7—Mo2—O5	71.15 (14)	O2—Mo7—O6	71.41 (14)
O23—Mo3—O18	101.7 (2)	O14—Mo7—O6	80.19 (14)
O23—Mo3—O13	105.60 (18)	O24—Mo7—O6	76.12 (13)
O18—Mo3—O13	93.16 (19)	O5—P1—O6	109.1 (2)
O23—Mo3—O15	101.52 (18)	O5—P1—O6ⁱ	109.07 (17)
O18—Mo3—O15	93.57 (19)	O6—P1—O6ⁱ	110.0 (3)
O13—Mo3—O15	150.05 (16)	O5—P1—O10	109.2 (3)
O23—Mo3—O24	96.79 (19)	O6—P1—O10	109.7 (2)
O18—Mo3—O24	161.48 (18)	O6ⁱ—P1—O10	109.73 (17)
O13—Mo3—O24	82.49 (15)	Mo7—O2—Mo1	126.8 (2)
O15—Mo3—O24	81.93 (15)	P1—O5—Mo6	125.3 (3)
O23—Mo3—O6	170.30 (17)	P1—O5—Mo2ⁱ	124.66 (14)
O18—Mo3—O6	85.56 (18)	Mo6—O5—Mo2ⁱ	88.26 (13)
O13—Mo3—O6	80.13 (13)	P1—O5—Mo2	124.66 (14)
O15—Mo3—O6	71.36 (13)	Mo6—O5—Mo2	88.3 (1)
O24—Mo3—O6	75.96 (13)	Mo2ⁱ—O5—Mo2	95.0 (2)
O16—Mo4—O11	100.50 (16)	P1—O6—Mo1	126.6 (2)
O16—Mo4—O11ⁱ	100.50 (16)	P1—O6—Mo3	124.6 (2)
O11—Mo4—O11ⁱ	89.5 (2)	Mo1—O6—Mo3	88.3 (1)
O16—Mo4—O19ⁱ	102.38 (17)	P1—O6—Mo7	126.33 (19)
O11—Mo4—O19ⁱ	157.10 (15)	Mo1—O6—Mo7	88.4 (1)
O11ⁱ—Mo4—O19ⁱ	87.19 (17)	Mo3—O6—Mo7	90.8 (1)
O16—Mo4—O19	102.38 (17)	Mo2ⁱ—O7—Mo2	122.0 (2)
O11—Mo4—O19	87.19 (17)	Mo5—O8—Mo7	158.2 (2)
O11ⁱ—Mo4—O19	157.10 (15)	Mo2—O9—Mo6	128.5 (2)
O19ⁱ—Mo4—O19	87.1 (3)	P1—O10—Mo4	126.8 (3)
O16—Mo4—O10	171.3 (2)	P1—O10—Mo5ⁱ	124.79 (14)
O11—Mo4—O10	73.51 (12)	Mo4—O10—Mo5ⁱ	88.8 (1)
O11ⁱ—Mo4—O10	73.51 (12)	P1—O10—Mo5	124.79 (14)
O19ⁱ—Mo4—O10	83.83 (13)	Mo4—O10—Mo5	88.8 (1)
O19—Mo4—O10	83.83 (13)	Mo5ⁱ—O10—Mo5	91.6 (2)
O3—Mo5—O8	103.64 (19)	Mo4—O11—Mo5	126.3 (2)
O3—Mo5—O12	103.36 (17)	Mo5—O12—Mo6	149.0 (2)
O8—Mo5—O12	93.95 (16)	Mo3—O13—Mo2	148.2 (2)
O3—Mo5—O11	103.45 (17)	Mo2—O14—Mo7	149.4 (2)
O8—Mo5—O11	93.29 (16)	Mo3—O15—Mo1	126.9 (2)
O12—Mo5—O11	149.68 (16)	Mo1—O17—Mo1ⁱ	156.7 (3)
O3—Mo5—O21	95.20 (18)	Mo3—O18—Mo3ⁱ	158.5 (3)
O8—Mo5—O21	161.10 (16)	Mo4—O19—Mo1	147.8 (2)
O12—Mo5—O21	82.94 (17)	Mo5ⁱ—O21—Mo5	115.7 (2)
O11—Mo5—O21	80.77 (17)	Mo7—O24—Mo3	116.6 (2)
O3—Mo5—O10	170.30 (16)	C1—N1—C2	112.7 (6)
O8—Mo5—O10	85.06 (14)	C3—N2—C3ⁱⁱ	110.6 (13)
O12—Mo5—O10	79.98 (16)	C4—N3—C4ⁱⁱ	104 (2)

Symmetry codes: (i) x, −y−1/2, z; (ii) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	(C₂H₆NH₂)₄[H₄PMo₁₂O₄₀]Cl₂·4H₂O
M_r	2153.62
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	14.9803 (7), 15.0682 (8), 22.6217 (12)
V (Å³)	5106.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.09
Crystal size (mm)	0.45 × 0.25 × 0.20

Data collection
Diffractometer	SMART CCD diffractometer
Absorption correction	Empirical (using intensity measurements) (SADABS; Sheldrick, 1996)
T_min, T_max	0.308, 0.638
No. of measured, independent and observed [I > 2σ(I)] reflections	16093, 4616, 3868
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.10
No. of reflections	4616
No. of parameters	346
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.77, −1.45

Computer programs: SMART (Siemens, 1994), SMART and SAINT (Siemens, 1996), XPREP in SHELXTL (Siemens, 1994), SHELXTL.

Selected geometric parameters (Å, º) top

Mo1—O20	1.668 (4)	Mo4—O10	2.415 (5)
Mo1—O17	1.893 (1)	Mo5—O3	1.669 (4)
Mo1—O15	1.930 (4)	Mo5—O8	1.865 (4)
Mo1—O2	1.941 (4)	Mo5—O12	1.866 (3)
Mo1—O19	2.026 (4)	Mo5—O11	1.933 (3)
Mo1—O6	2.406 (3)	Mo5—O21	2.115 (3)
Mo2—O22	1.672 (4)	Mo5—O10	2.497 (3)
Mo2—O9	1.866 (4)	Mo6—O1	1.672 (5)
Mo2—O14	1.881 (4)	Mo6—O12	1.933 (4)
Mo2—O13	1.949 (4)	Mo6—O9	1.943 (4)
Mo2—O7	2.096 (2)	Mo6—O5	2.442 (5)
Mo2—O5	2.486 (3)	Mo7—O4	1.663 (4)
Mo3—O23	1.678 (4)	Mo7—O8	1.879 (4)
Mo3—O18	1.869 (1)	Mo7—O2	1.892 (4)
Mo3—O13	1.873 (4)	Mo7—O14	1.899 (4)
Mo3—O15	1.896 (4)	Mo7—O24	2.090 (3)
Mo3—O24	2.104 (4)	Mo7—O6	2.508 (4)
Mo3—O6	2.505 (3)	P1—O5	1.535 (5)
Mo4—O16	1.676 (5)	P1—O6	1.545 (4)
Mo4—O11	1.921 (4)	P1—O10	1.552 (5)
Mo4—O19	1.958 (4)

O5—P1—O6	109.1 (2)	Mo4—O10—Mo5	88.8 (1)
O5—P1—O10	109.2 (3)	Mo5ⁱ—O10—Mo5	91.6 (2)
O6—P1—O10	109.7 (2)	Mo4—O11—Mo5	126.3 (2)
Mo7—O2—Mo1	126.8 (2)	Mo5—O12—Mo6	149.0 (2)
Mo6—O5—Mo2	88.3 (1)	Mo3—O13—Mo2	148.2 (2)
Mo2ⁱ—O5—Mo2	95.0 (2)	Mo2—O14—Mo7	149.4 (2)
Mo1—O6—Mo3	88.3 (1)	Mo3—O15—Mo1	126.9 (2)
Mo1—O6—Mo7	88.4 (1)	Mo1—O17—Mo1ⁱ	156.7 (3)
Mo3—O6—Mo7	90.8 (1)	Mo3—O18—Mo3ⁱ	158.5 (3)
Mo2ⁱ—O7—Mo2	122.0 (2)	Mo4—O19—Mo1	147.8 (2)
Mo5—O8—Mo7	158.2 (2)	Mo5ⁱ—O21—Mo5	115.7 (2)
Mo2—O9—Mo6	128.5 (2)	Mo7—O24—Mo3	116.6 (2)
Mo4—O10—Mo5ⁱ	88.8 (1)

Symmetry code: (i) x, −y−1/2, z.

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