Tetra­kis(μ2-di­phenyl­phosphinato-κ2O,O′)tetra-μ3-oxido-tetra­oxidohexa­molybdenum(V)

Mota Merelo de Aguiar, S.R.; Stöger, B.; Weil, M.; Kirchner, K.

doi:10.1107/S2414314616000365

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 1| January 2016| x160036

doi:10.1107/S2414314616000365

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Tetrakis(μ₂-diphenylphosphinato-κ²O,O′)tetra-μ₃-oxido-tetraoxidohexamolybdenum(V)

Sara Raquel Mota Merelo de Aguiar,^a Berthold Stöger,^b Matthias Weil ^b ^* and Karl Kirchner ^a

^aInstitute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163, A-1060 Vienna, Austria, and ^bInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria
^*Correspondence e-mail: Matthias.Weil@tuwien.ac.at

Edited by J. Simpson, University of Otago, New Zealand (Received 5 January 2016; accepted 7 January 2016; online 16 January 2016)

The molecule of the title compound, [Mo₄(μ₂-C₁₂H₁₀OP₂)₄(μ₃-O)₄O₄], exhibits point group symmetry 2 with the twofold rotation axis passing through two opposite P atoms. Each Mo^V atom is bridged by three O atoms resulting in an Mo₄O₄ heterocubane core. In the crystal, weak C—H⋯O interactions may help to consolidate packing of the molecules.

Keywords: crystal structure; heterocubane; molybdenum; Mo₄O₄ core.

CCDC reference: 1446068

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Chemical scheme

Structure description

The title compound had formed accidentally due to the presence of oxygen in a solution originally intended to crystallize the PNP pincer compound [Mo(PNP^Me—Ph)(CO)₂F₂] [(PNP^Me—Ph) = N,N′-bis(diphenylphosphino)-N,N′-methyl-2,6-diaminopyridine; de Aguiar et al., 2014 ]. A chloroform disolvate of the title compound was reported by Schirmer et al. (1989 ). The molecule of the title compound [MoO(μ₃-O)(μ₂-C₁₂H₁₀PO₂)]₄, exhibits point group symmetry 2 with the twofold rotation axis passing through two opposite P atoms (Fig. 1). Each molybdenum atom is bridged by three oxygen atoms resulting in a Mo₄O₄ heterocubane core. The distorted octahedral coordination spheres of the two unique molybdenum atoms [bond lengths range from 1.6686 (19) to 2.3982 (19) Å] are completed by a double-bonded terminal oxygen atom and two oxygen atoms of two diphenylphosphinate anions, each bridging two opposite molybdenum atoms in the heterocube. The short Mo⋯Mo distance of 2.6395 (3) Å indicates Mo^V⋯Mo^V interactions and causes a distortion of the Mo₄O₄ heterocubane core with O—Mo—O angles ranging from 77.94 (7) to 89.87 (7)° and Mo—O—Mo angles from 84.60 (7) to 102.02 (7) °. For characteristic bond lengths and angles of {Mo₄O₄(μ₃-O₄}⁴⁺ heterocubane cores, see: Modec et al. (2003 ). In the crystal, weak C—H⋯O interactions, Table 1, may help to consolidate packing of the molecules, Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O3ⁱ	0.93	2.52	3.188 (4)	129
C21—H21⋯O4ⁱⁱ	0.93	2.57	3.420 (5)	152
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level; H atoms are shown as spheres of arbitrary radius. Non-labelled atoms are generated by the symmetry code −x + 2, y, −z + $[{1\over 2}]$ .

Figure 2
The packing of the molecules in the crystal structure of the title compound in a view approximately along [001].

Synthesis and crystallization

The original intention was to crystallize the compound [Mo(PNP^Me—Ph)(CO)₂F₂] (de Aguiar et al., 2014). One equivalent of 1-fluoro-2,4,6-trimethylpyridinium tetrafluoridoborate was added to a solution of [Mo(PNP^Me—Ph)(CO)₃] in 10 ml CH₂Cl₂ and stirred for three days. After filtration, the solution was layered with pentane and left to stand for several days. Instead of the desired compound [Mo(PNP^Me—Ph)(CO)₂F₂], the title compound crystallized in form of dark-red blocks, apparently caused by the presence of larger amounts of oxygen in the reaction vessel.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Mo₄(C₁₂H₁₀O₂P)₄O₈]
M_r	1380.44
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	100
a, b, c (Å)	16.1061 (19), 19.891 (2), 15.254 (3)
V (Å³)	4887.0 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.21
Crystal size (mm)	0.61 × 0.49 × 0.30

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.45, 0.66
No. of measured, independent and observed [I > 2σ(I)] reflections	255304, 8962, 7558
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.090, 1.27
No. of reflections	8962
No. of parameters	326
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + 23.6442P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.92, −1.05
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SUPERFLIP (Palatinus & Chapuis, 2007 ), SHELXL2014 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008 ), Mercury (Macrae et al., 2006 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1446068

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616000365/sj4007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616000365/sj4007Isup2.hkl

checkCIF report

Synthesis and crystallization top

The original intention was to crystallize the compound [Mo(PNP^Me—Ph)(CO)₂F₂] (de Aguiar et al., 2014). One equivalent of 1-fluoro-2,4,6-trimethylpyridinium tetrafluoridoborate was added to a solution of [Mo(PNP^Me—Ph)(CO)₃] in 10 ml CH₂Cl₂ and stirred for three days. After filtration, the solution was layered with pentane and left to stand for several days. Instead of the desired compound [Mo(PNP^Me—Ph)(CO)₂F₂], the title compound crystallized in form of dark red blocks, apparently caused by the presence of larger amounts of oxygen in the reaction vessel.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Experimental top

Structure description top

The title compound had formed accidentally due to the presence of oxygen in a solution originally intended to crystallize the PNP pincer compound [Mo(PNP^Me—Ph)(CO)₂F₂] [(PNP^Me—Ph) = N,N'-bis(diphenylphosphino)-N,N'-methyl-2,6-diaminopyridine (de Aguiar et al., 2014). A chloroform disolvate of the title compound was reported by Schirmer et al. (1989). The molecule of the title compound, Fig. 1 [MoO(µ₃-O)(µ₂-C₁₂H₁₀PO₂)]₄, exhibits point group symmetry 2 with the twofold rotation axis passing through two opposite P atoms. Each molybdenum atom is bridged by three oxygen atoms resulting in a Mo₄O₄ heterocubane core. The distorted octahedral coordination spheres of the two unique molybdenum atoms [bond lengths range from 1.6686 (19) to 2.3982 (19) Å] are completed by a double-bonded terminal oxygen atom and two oxygen atoms of two diphenylphosphinate anions, each bridging two opposite molybdenum atoms in the heterocube. The short Mo···Mo distance of 2.6395 (3) Å indicates Mo^V···Mo^V interactions and causes a distortion of the Mo₄O₄ heterocubane core with O—Mo—O angles ranging from 77.94 (7) to 89.87 (7)° and Mo—O—Mo angles from 84.60 (7) to 102.02 (7) °. For characteristic bond lengths and angles of {Mo₄O₄(µ₃-O₄}⁴⁺ heterocubane cores, see: Modec et al. (2003). In the crystal, weak C—H···O interactions, Table 1, may help to consolidate packing of the molecules, Fig. 2.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level; H atoms are shown as spheres of arbitrary radius. Non-labelled atoms are generated by the symmetry code −x + 2, y, −z + 1/2.
	Fig. 2. The packing of the molecules in the crystal structure of the title compound in a view approximately along [001].

Tetrakis(µ₂-diphenylphosphinato-κ²O,O')tetra-µ₃-oxido-tetraoxidohexamolybdenum(V) top

Crystal data top

[Mo₄(C₁₂H₁₀O₂P)₄O₈]	D_x = 1.876 Mg m⁻³
M_r = 1380.44	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 9220 reflections
a = 16.1061 (19) Å	θ = 2.4–30.0°
b = 19.891 (2) Å	µ = 1.21 mm⁻¹
c = 15.254 (3) Å	T = 100 K
V = 4887.0 (11) Å³	Block, dark red
Z = 4	0.61 × 0.49 × 0.30 mm
F(000) = 2736

Data collection top

Bruker Kappa APEXII CCD diffractometer	7558 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω– and φ–scans	θ_max = 32.7°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −24→24
T_min = 0.45, T_max = 0.66	k = −30→30
255304 measured reflections	l = −23→23
8962 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + 23.6442P] where P = (F_o² + 2F_c²)/3
S = 1.27	(Δ/σ)_max = 0.001
8962 reflections	Δρ_max = 0.92 e Å⁻³
326 parameters	Δρ_min = −1.05 e Å⁻³

Crystal data top

[Mo₄(C₁₂H₁₀O₂P)₄O₈]	V = 4887.0 (11) Å³
M_r = 1380.44	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 16.1061 (19) Å	µ = 1.21 mm⁻¹
b = 19.891 (2) Å	T = 100 K
c = 15.254 (3) Å	0.61 × 0.49 × 0.30 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	8962 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	7558 reflections with I > 2σ(I)
T_min = 0.45, T_max = 0.66	R_int = 0.061
255304 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.27	w = 1/[σ²(F_o²) + 23.6442P] where P = (F_o² + 2F_c²)/3
8962 reflections	Δρ_max = 0.92 e Å⁻³
326 parameters	Δρ_min = −1.05 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mo1	0.94264 (2)	0.30980 (2)	0.15695 (2)	0.00840 (5)
Mo2	1.05855 (2)	0.21599 (2)	0.15724 (2)	0.00870 (5)
P1	0.76853 (4)	0.26945 (3)	0.25500 (4)	0.01124 (11)
P2	1.0000	0.45135 (4)	0.2500	0.01029 (15)
P3	1.0000	0.07459 (5)	0.2500	0.01125 (15)
O1	1.06085 (11)	0.31230 (9)	0.18613 (12)	0.0102 (3)
O2	0.93968 (11)	0.21393 (9)	0.18558 (12)	0.0095 (3)
O3	0.93008 (12)	0.31794 (10)	0.04868 (12)	0.0133 (3)
O4	1.07105 (12)	0.20672 (10)	0.04932 (12)	0.0142 (3)
O5	1.18201 (11)	0.21577 (10)	0.19500 (13)	0.0121 (3)
O6	0.81967 (11)	0.31237 (10)	0.19196 (12)	0.0120 (3)
O7	0.94434 (12)	0.41077 (9)	0.18832 (12)	0.0114 (3)
O8	1.05526 (12)	0.11516 (9)	0.18828 (13)	0.0133 (3)
C1	0.69240 (16)	0.22699 (13)	0.19004 (18)	0.0136 (4)
C2	0.72255 (18)	0.17894 (16)	0.1312 (2)	0.0199 (5)
H2	0.7791	0.1696	0.1289	0.024*
C3	0.6680 (2)	0.14529 (17)	0.0762 (2)	0.0226 (6)
H3	0.6880	0.1134	0.0369	0.027*
C4	0.58371 (19)	0.15910 (17)	0.0796 (2)	0.0218 (6)
H4	0.5471	0.1361	0.0433	0.026*
C5	0.5542 (2)	0.20701 (18)	0.1370 (2)	0.0260 (6)
H5	0.4976	0.2162	0.1389	0.031*
C6	0.60803 (18)	0.24191 (17)	0.1924 (2)	0.0212 (5)
H6	0.5878	0.2747	0.2303	0.025*
C7	0.71892 (16)	0.32266 (13)	0.33376 (17)	0.0128 (4)
C8	0.66756 (17)	0.29415 (14)	0.39712 (19)	0.0166 (5)
H8	0.6589	0.2479	0.3977	0.020*
C9	0.62922 (19)	0.33445 (16)	0.4595 (2)	0.0208 (5)
H9	0.5942	0.3153	0.5010	0.025*
C10	0.64329 (19)	0.40329 (16)	0.4597 (2)	0.0207 (5)
H10	0.6179	0.4303	0.5017	0.025*
C11	0.6953 (2)	0.43199 (15)	0.3972 (2)	0.0215 (5)
H11	0.7045	0.4782	0.3975	0.026*
C12	0.73355 (18)	0.39208 (14)	0.3343 (2)	0.0175 (5)
H12	0.7686	0.4113	0.2928	0.021*
C13	1.06447 (16)	0.50353 (13)	0.18254 (17)	0.0130 (4)
C14	1.1143 (2)	0.55275 (15)	0.2199 (2)	0.0220 (6)
H14	1.1133	0.5597	0.2802	0.026*
C15	1.1655 (2)	0.59151 (16)	0.1671 (2)	0.0254 (6)
H15	1.1998	0.6238	0.1922	0.031*
C16	1.1659 (2)	0.58250 (16)	0.0774 (2)	0.0226 (6)
H16	1.1989	0.6098	0.0422	0.027*
C17	1.1175 (2)	0.53317 (18)	0.0397 (2)	0.0245 (6)
H17	1.1187	0.5265	−0.0206	0.029*
C18	1.0667 (2)	0.49336 (16)	0.09217 (19)	0.0210 (5)
H18	1.0342	0.4599	0.0669	0.025*
C19	1.06746 (18)	0.02056 (14)	0.31128 (19)	0.0167 (5)
C20	1.0336 (2)	−0.0317 (2)	0.3592 (3)	0.0397 (10)
H20	0.9762	−0.0371	0.3614	0.048*
C21	1.0845 (3)	−0.0761 (2)	0.4042 (4)	0.0500 (13)
H21	1.0613	−0.1109	0.4366	0.060*
C22	1.1683 (3)	−0.0686 (2)	0.4008 (3)	0.0392 (10)
H22	1.2023	−0.0988	0.4303	0.047*
C23	1.2032 (2)	−0.0169 (2)	0.3543 (3)	0.0347 (9)
H23	1.2605	−0.0117	0.3534	0.042*
C24	1.1529 (2)	0.02794 (18)	0.3083 (2)	0.0240 (6)
H24	1.1766	0.0626	0.2759	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.00826 (8)	0.00886 (8)	0.00810 (8)	−0.00049 (6)	−0.00012 (6)	0.00068 (6)
Mo2	0.00835 (8)	0.00926 (9)	0.00849 (8)	−0.00033 (6)	0.00031 (6)	−0.00117 (6)
P1	0.0070 (2)	0.0143 (3)	0.0124 (3)	−0.0001 (2)	0.0006 (2)	0.0027 (2)
P2	0.0124 (4)	0.0087 (3)	0.0099 (4)	0.000	0.0000 (3)	0.000
P3	0.0108 (4)	0.0090 (3)	0.0140 (4)	0.000	−0.0004 (3)	0.000
O1	0.0085 (7)	0.0114 (7)	0.0107 (7)	−0.0012 (6)	0.0007 (6)	−0.0018 (6)
O2	0.0082 (7)	0.0090 (7)	0.0113 (7)	−0.0008 (6)	0.0015 (6)	0.0006 (6)
O3	0.0136 (8)	0.0160 (8)	0.0102 (8)	−0.0018 (7)	0.0002 (6)	0.0013 (6)
O4	0.0156 (8)	0.0163 (8)	0.0106 (8)	−0.0012 (7)	0.0007 (6)	−0.0023 (7)
O5	0.0086 (7)	0.0138 (8)	0.0140 (8)	0.0000 (6)	0.0006 (6)	−0.0045 (6)
O6	0.0082 (7)	0.0150 (8)	0.0128 (8)	0.0016 (6)	0.0006 (6)	0.0036 (6)
O7	0.0134 (8)	0.0093 (7)	0.0116 (7)	−0.0009 (6)	−0.0026 (6)	0.0012 (6)
O8	0.0144 (8)	0.0104 (8)	0.0151 (8)	0.0001 (6)	0.0030 (7)	−0.0005 (6)
C1	0.0104 (10)	0.0141 (10)	0.0161 (11)	−0.0001 (8)	−0.0012 (8)	0.0021 (9)
C2	0.0151 (11)	0.0237 (13)	0.0209 (13)	0.0016 (10)	0.0005 (10)	−0.0026 (11)
C3	0.0228 (14)	0.0254 (14)	0.0196 (13)	0.0006 (11)	−0.0033 (11)	−0.0058 (11)
C4	0.0189 (13)	0.0261 (14)	0.0204 (13)	−0.0030 (11)	−0.0072 (10)	−0.0008 (11)
C5	0.0151 (12)	0.0329 (16)	0.0300 (16)	0.0029 (12)	−0.0070 (11)	−0.0062 (13)
C6	0.0126 (11)	0.0276 (14)	0.0233 (13)	0.0030 (10)	−0.0019 (10)	−0.0052 (11)
C7	0.0112 (10)	0.0141 (10)	0.0130 (10)	0.0000 (8)	0.0007 (8)	0.0006 (8)
C8	0.0159 (11)	0.0167 (11)	0.0174 (11)	−0.0026 (9)	0.0039 (9)	0.0014 (9)
C9	0.0192 (12)	0.0248 (14)	0.0182 (12)	−0.0009 (11)	0.0053 (10)	0.0011 (11)
C10	0.0186 (12)	0.0250 (14)	0.0184 (12)	0.0014 (11)	0.0017 (10)	−0.0048 (11)
C11	0.0226 (13)	0.0171 (12)	0.0247 (14)	−0.0005 (10)	0.0015 (11)	−0.0031 (11)
C12	0.0160 (11)	0.0153 (11)	0.0212 (12)	−0.0007 (9)	0.0028 (10)	0.0019 (10)
C13	0.0143 (10)	0.0099 (9)	0.0149 (10)	0.0003 (8)	0.0018 (8)	−0.0014 (8)
C14	0.0251 (14)	0.0185 (12)	0.0223 (13)	−0.0083 (11)	0.0022 (11)	−0.0047 (10)
C15	0.0308 (16)	0.0184 (13)	0.0271 (15)	−0.0106 (12)	0.0056 (12)	−0.0028 (11)
C16	0.0207 (13)	0.0182 (12)	0.0289 (15)	0.0008 (10)	0.0083 (11)	0.0060 (11)
C17	0.0263 (15)	0.0329 (16)	0.0144 (12)	−0.0008 (12)	0.0057 (11)	0.0023 (11)
C18	0.0246 (13)	0.0247 (14)	0.0138 (11)	−0.0064 (11)	0.0036 (10)	−0.0017 (10)
C19	0.0164 (11)	0.0139 (11)	0.0197 (12)	0.0007 (9)	−0.0033 (9)	0.0027 (9)
C20	0.0243 (16)	0.039 (2)	0.055 (3)	−0.0017 (15)	−0.0042 (16)	0.0294 (19)
C21	0.048 (3)	0.040 (2)	0.062 (3)	0.0002 (19)	−0.014 (2)	0.032 (2)
C22	0.044 (2)	0.0339 (19)	0.039 (2)	0.0173 (17)	−0.0218 (18)	0.0018 (16)
C23	0.0236 (15)	0.050 (2)	0.0302 (17)	0.0138 (15)	−0.0116 (13)	−0.0103 (16)
C24	0.0177 (13)	0.0319 (16)	0.0226 (14)	0.0053 (11)	−0.0051 (11)	−0.0037 (12)

Geometric parameters (Å, º) top

Mo1—O3	1.6717 (19)	C5—C6	1.396 (4)
Mo1—O1	1.9559 (18)	C5—H5	0.9300
Mo1—O2	1.9569 (18)	C6—H6	0.9300
Mo1—O6	2.0519 (18)	C7—C8	1.393 (4)
Mo1—O7	2.0648 (18)	C7—C12	1.401 (4)
Mo1—O1ⁱ	2.3950 (19)	C8—C9	1.389 (4)
Mo1—Mo2	2.6395 (3)	C8—H8	0.9300
Mo2—O4	1.6686 (19)	C9—C10	1.388 (4)
Mo2—O2	1.9632 (18)	C9—H9	0.9300
Mo2—O1	1.9661 (18)	C10—C11	1.392 (4)
Mo2—O8	2.0615 (19)	C10—H10	0.9300
Mo2—O5	2.0701 (19)	C11—C12	1.390 (4)
Mo2—O2ⁱ	2.3982 (19)	C11—H11	0.9300
P1—O6	1.527 (2)	C12—H12	0.9300
P1—O5ⁱ	1.5351 (19)	C13—C14	1.389 (4)
P1—C1	1.789 (3)	C13—C18	1.394 (4)
P1—C7	1.789 (3)	C14—C15	1.388 (4)
P2—O7	1.5298 (19)	C14—H14	0.9300
P2—O7ⁱ	1.5298 (19)	C15—C16	1.379 (5)
P2—C13ⁱ	1.793 (3)	C15—H15	0.9300
P2—C13	1.793 (3)	C16—C17	1.379 (5)
P3—O8ⁱ	1.526 (2)	C16—H16	0.9300
P3—O8	1.526 (2)	C17—C18	1.391 (4)
P3—C19	1.791 (3)	C17—H17	0.9300
P3—C19ⁱ	1.791 (3)	C18—H18	0.9300
O1—Mo1ⁱ	2.3950 (19)	C19—C20	1.383 (5)
O2—Mo2ⁱ	2.3982 (19)	C19—C24	1.385 (4)
O5—P1ⁱ	1.5351 (19)	C20—C21	1.386 (5)
C1—C6	1.391 (4)	C20—H20	0.9300
C1—C2	1.398 (4)	C21—C22	1.360 (7)
C2—C3	1.387 (4)	C21—H21	0.9300
C2—H2	0.9300	C22—C23	1.369 (7)
C3—C4	1.386 (4)	C22—H22	0.9300
C3—H3	0.9300	C23—C24	1.393 (5)
C4—C5	1.379 (5)	C23—H23	0.9300
C4—H4	0.9300	C24—H24	0.9300

O3—Mo1—O1	109.88 (9)	C6—C1—P1	123.7 (2)
O3—Mo1—O2	108.17 (9)	C2—C1—P1	116.1 (2)
O1—Mo1—O2	89.87 (7)	C3—C2—C1	119.9 (3)
O3—Mo1—O6	97.93 (9)	C3—C2—H2	120.1
O1—Mo1—O6	151.61 (7)	C1—C2—H2	120.1
O2—Mo1—O6	86.71 (7)	C4—C3—C2	120.1 (3)
O3—Mo1—O7	97.84 (8)	C4—C3—H3	119.9
O1—Mo1—O7	84.81 (7)	C2—C3—H3	119.9
O2—Mo1—O7	153.70 (7)	C5—C4—C3	119.9 (3)
O6—Mo1—O7	85.89 (8)	C5—C4—H4	120.0
O3—Mo1—O1ⁱ	169.29 (8)	C3—C4—H4	120.0
O1—Mo1—O1ⁱ	78.16 (7)	C4—C5—C6	120.9 (3)
O2—Mo1—O1ⁱ	78.27 (7)	C4—C5—H5	119.6
O6—Mo1—O1ⁱ	73.54 (7)	C6—C5—H5	119.6
O7—Mo1—O1ⁱ	75.43 (7)	C1—C6—C5	119.0 (3)
O3—Mo1—Mo2	98.95 (7)	C1—C6—H6	120.5
O1—Mo1—Mo2	47.86 (5)	C5—C6—H6	120.5
O2—Mo1—Mo2	47.78 (5)	C8—C7—C12	119.8 (3)
O6—Mo1—Mo2	134.41 (5)	C8—C7—P1	119.4 (2)
O7—Mo1—Mo2	132.67 (5)	C12—C7—P1	120.8 (2)
O1ⁱ—Mo1—Mo2	91.70 (4)	C9—C8—C7	120.3 (3)
O4—Mo2—O2	109.42 (9)	C9—C8—H8	119.9
O4—Mo2—O1	109.06 (9)	C7—C8—H8	119.9
O2—Mo2—O1	89.39 (7)	C10—C9—C8	119.9 (3)
O4—Mo2—O8	97.02 (9)	C10—C9—H9	120.1
O2—Mo2—O8	84.49 (7)	C8—C9—H9	120.1
O1—Mo2—O8	153.77 (8)	C9—C10—C11	120.1 (3)
O4—Mo2—O5	99.12 (9)	C9—C10—H10	120.0
O2—Mo2—O5	151.09 (7)	C11—C10—H10	120.0
O1—Mo2—O5	85.51 (7)	C12—C11—C10	120.4 (3)
O8—Mo2—O5	87.63 (8)	C12—C11—H11	119.8
O4—Mo2—O2ⁱ	169.42 (8)	C10—C11—H11	119.8
O2—Mo2—O2ⁱ	77.94 (7)	C11—C12—C7	119.5 (3)
O1—Mo2—O2ⁱ	78.02 (7)	C11—C12—H12	120.2
O8—Mo2—O2ⁱ	75.76 (7)	C7—C12—H12	120.2
O5—Mo2—O2ⁱ	73.16 (7)	C14—C13—C18	119.6 (3)
O4—Mo2—Mo1	99.31 (7)	C14—C13—P2	120.5 (2)
O2—Mo2—Mo1	47.57 (5)	C18—C13—P2	119.9 (2)
O1—Mo2—Mo1	47.54 (5)	C15—C14—C13	119.8 (3)
O8—Mo2—Mo1	132.06 (5)	C15—C14—H14	120.1
O5—Mo2—Mo1	132.95 (5)	C13—C14—H14	120.1
O2ⁱ—Mo2—Mo1	91.27 (4)	C16—C15—C14	120.4 (3)
O6—P1—O5ⁱ	114.95 (10)	C16—C15—H15	119.8
O6—P1—C1	106.55 (12)	C14—C15—H15	119.8
O5ⁱ—P1—C1	107.61 (12)	C17—C16—C15	120.2 (3)
O6—P1—C7	109.45 (12)	C17—C16—H16	119.9
O5ⁱ—P1—C7	108.04 (12)	C15—C16—H16	119.9
C1—P1—C7	110.19 (12)	C16—C17—C18	119.8 (3)
O7—P2—O7ⁱ	116.31 (15)	C16—C17—H17	120.1
O7—P2—C13ⁱ	108.61 (11)	C18—C17—H17	120.1
O7ⁱ—P2—C13ⁱ	106.97 (11)	C17—C18—C13	120.1 (3)
O7—P2—C13	106.97 (11)	C17—C18—H18	119.9
O7ⁱ—P2—C13	108.61 (11)	C13—C18—H18	119.9
C13ⁱ—P2—C13	109.25 (17)	C20—C19—C24	119.3 (3)
O8ⁱ—P3—O8	116.17 (15)	C20—C19—P3	119.2 (2)
O8ⁱ—P3—C19	110.42 (12)	C24—C19—P3	121.5 (2)
O8—P3—C19	106.58 (12)	C19—C20—C21	120.4 (4)
O8ⁱ—P3—C19ⁱ	106.58 (12)	C19—C20—H20	119.8
O8—P3—C19ⁱ	110.42 (12)	C21—C20—H20	119.8
C19—P3—C19ⁱ	106.27 (19)	C22—C21—C20	119.9 (4)
Mo1—O1—Mo2	84.60 (7)	C22—C21—H21	120.0
Mo1—O1—Mo1ⁱ	101.77 (7)	C20—C21—H21	120.0
Mo2—O1—Mo1ⁱ	101.73 (8)	C21—C22—C23	120.6 (3)
Mo1—O2—Mo2	84.65 (7)	C21—C22—H22	119.7
Mo1—O2—Mo2ⁱ	101.90 (7)	C23—C22—H22	119.7
Mo2—O2—Mo2ⁱ	102.02 (7)	C22—C23—C24	120.2 (4)
P1ⁱ—O5—Mo2	129.43 (11)	C22—C23—H23	119.9
P1—O6—Mo1	132.12 (11)	C24—C23—H23	119.9
P2—O7—Mo1	131.57 (11)	C19—C24—C23	119.5 (3)
P3—O8—Mo2	132.15 (12)	C19—C24—H24	120.2
C6—C1—C2	120.1 (3)	C23—C24—H24	120.2

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱⁱ	0.93	2.52	3.188 (4)	129
C21—H21···O4ⁱⁱⁱ	0.93	2.57	3.420 (5)	152

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱ	0.93	2.52	3.188 (4)	129
C21—H21···O4ⁱⁱ	0.93	2.57	3.420 (5)	152

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

Experimental details

Crystal data
Chemical formula	[Mo₄(C₁₂H₁₀O₂P)₄O₈]
M_r	1380.44
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	100
a, b, c (Å)	16.1061 (19), 19.891 (2), 15.254 (3)
V (Å³)	4887.0 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.21
Crystal size (mm)	0.61 × 0.49 × 0.30

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.45, 0.66
No. of measured, independent and observed [I > 2σ(I)] reflections	255304, 8962, 7558
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.090, 1.27
No. of reflections	8962
No. of parameters	326
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + 23.6442P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.92, −1.05

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2014 (Sheldrick, 2015), XP in SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

Acknowledgements

Financial support by the Austrian Science Fund (FWF) (Project No. P24202-N17) is gratefully acknowledged. The X-ray centre of TU Wien is acknowledged for providing access to the single-crystal diffractometer.

References

Aguiar, S. R. M. M. de, Stöger, B., Pittenauer, E., Puchberger, M., Allmaier, G., Veiros, L. F. & Kirchner, K. (2014). J. Organomet. Chem. 760, 74–83. PubMed Google Scholar
Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Modec, B., Brenčič, J., Burkholder, E. M. & Zubieta, J. (2003). Dalton Trans. pp. 4618–4625. CSD CrossRef Google Scholar
Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790. Web of Science CrossRef CAS IUCr Journals Google Scholar
Schirmer, W., Flörke, U. & Haupt, H.-J. (1989). Z. Anorg. Allg. Chem. 574, 239–255. CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 1| Part 1| January 2016| x160036

doi:10.1107/S2414314616000365

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