Bis(2,4-dioxo­pentan-3-ido-κ2O,O′)dioxidomolyb­denum(VI): a redetermination

Johnston, D.H.; King, C.; Seitz, A.; Sethi, M.

doi:10.1107/S2414314621007781

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 8| August 2021| x210778

https://doi.org/10.1107/S2414314621007781

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Bis(2,4-dioxopentan-3-ido-κ²O,O′)dioxidomolybdenum(VI): a redetermination

Dean H. Johnston,^a ^* Calvin King,^a Aileen Seitz ^a and Mia Sethi ^a

^aDepartment of Chemistry, Otterbein University, Westerville, OH 43081, USA
^*Correspondence e-mail: djohnston@otterbein.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 July 2021; accepted 29 July 2021; online 6 August 2021)

The title compound, [Mo(C₅H₇O₂)₂O₂] or cis-[MoO₂(acac)₂] (acac is acetylacetonate), contains a molybdenum(VI) atom coordinated by two acetylacetonate ligands and two doubly bonded oxido ligands in a distorted octahedral shape. The molecule is chiral and the asymmetric unit contains two independent molecules (one Δ, one Λ). Extensive C—H⋯O contacts are present throughout the structure. Data were collected at 100 K, providing higher precision of unit-cell parameters and atomic positions than previous determinations [Kamenar et al. (1973 ). Cryst. Struct. Commun. 2, 41–44.; Krasochka et al. (1975). Zh. Strukt. Khim. 16, 696–698].

Keywords: crystal structure; molybdenum; oxo; acetylacetonate; acac.

CCDC reference: 2100177

Structure description

The title compound is a versatile starting material for the preparation of cis-dioxidomolybdenum complexes, including complexes containing organodinitrogen ligands (Bustos et al., 1994 ) and molybdenyl adducts of platinum μ-S dimers (Henderson et al., 2011 ). MoO₂(acac)₂ has also been used to prepare dioxidomolybdenum(VI) complexes with O,N,N′ chelating ligands (Ceylan et al., 2015 ) and an amine bis(phenolate) ligand (Bowen & Wile, 2021 ). Many of these complexes have been prepared and studied for their catalytic activities, including complexes with acylpyrazolonate ligands that catalyze the deoxygenation of epoxides (Hills et al., 2013 ; Begines et al., 2018 ) and dioxidomolybdenum(VI) complexes with salicylamide ligands for the epoxidation of olefins (Annese et al., 2019 ). Molybdenum(VI) dioxido complexes with acetylacetonato ligands have also been investigated for their catalytic properties in the dehydrogenation of alcohols (Korstanje et al., 2013 ). These complexes are of particular interest due to their close structural similarities to the active sites of several molybdoenyzmes such as sulfite oxidase, xanthine oxidase, and DMSO reductase (Sousa & Fernandes, 2015 ).

Two previous structural determinations of cis-dioxidobis(acetylacetonato)molybdenum(VI) were published in the mid-1970s (Kamenar et al., 1973; Krasochka et al., 1975) based on photographic methods and room-temperature data collections. Additionally, Craven et al. (1971 ) cite an unpublished diffraction study that also confirms the cis coordination and includes additional structural information consistent with the current study. None of the previously published structure solutions attempted to locate the positions of any of the hydrogen atoms. Several closely related structures have been determined, including cis-dioxido-molybdenum complexes with 1,3-diphenylpropanedianoto ligands (Kojić-Prodić et al., 1974 ; Korstanje et al., 2013) and tert-butylacetylacetonato ligands (Nass et al., 2001 ). The structure of the product from the reaction of cis-[MoO₂(acac)₂] with the strong Lewis acid B(C₆F₅)₃ (Galsworthy et al., 1997 ) displays a nearly linear Mo=O—B arrangement [171.2 (1)°] and lengthening of the donating Mo=O bond by about 0.1 Å.

The asymmetric unit of the title compound contains two crystallographically independent cis-[MoO₂(acac)₂] molecules, one each of the Δ and Λ forms (Fig. 1). The molecular structure adopts a distorted octahedral arrangement around the Mo^VI atoms, with oxido ligands in a cis arrangement and oxido-molybdenum-oxido angles of 105.40 (4) and 105.59 (5)°. As observed previously (Krasochka, 1973 ; Kojić-Prodić et al., 1974), the Mo—O bond distances trans to the molybdenum-oxygen double bonds are significantly lengthened [avg = 2.185 (5) Å] relative to the other molybdenum–oxygen distances [avg = 1.999 (11) Å] (see Table 1 for selected bond distances and angles). The four molybdenum oxygen distances for the doubly-bonded oxido ligands average 1.7012 (16) Å, in agreement with the average distance found for over 140 similar cis-dioxido molybdenum complexes in the Cambridge Structural Database (Groom et al., 2016 ). These metrics are also in agreement with relatively narrow distribution of molybdenum–oxygen distances observed by Mayer (1988 ) for cis-dioxido complexes.

Table 1
Selected geometric parameters (Å, °)

Mo1—O1	1.7029 (9)	Mo2—O7	1.6996 (9)
Mo1—O2	1.7001 (9)	Mo2—O8	1.7021 (9)
Mo1—O3	2.1825 (8)	Mo2—O9	2.1808 (8)
Mo1—O4	2.1921 (8)	Mo2—O10	2.1848 (9)
Mo1—O5	2.0060 (8)	Mo2—O11	1.9898 (8)
Mo1—O6	1.9897 (8)	Mo2—O12	2.0106 (8)

O2—Mo1—O1	105.40 (4)	O7—Mo2—O8	105.59 (5)

Figure 1
Displacement ellipsoid (50% probability) diagram of the two independent molecules with the numbering scheme for the non-hydrogen atoms.

All of the hydrogen-bonding contacts are weak C—H⋯O interactions with D⋯A distances between 3.3 and 3.5 Å (see Table 2 and Fig. 2). There are contacts between C—H atoms and all four of the oxido ligands, including two contacts to O1 and three contacts to O8. Additional C—H contacts are made to most of the acetylacetonate oxygen atoms as well.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O8ⁱ	0.93 (1)	2.62 (2)	3.4834 (16)	155 (2)
C5—H5B⋯O10ⁱⁱ	0.98 (1)	2.50 (1)	3.4652 (15)	170 (2)
C6—H6A⋯O8	0.97 (1)	2.51 (2)	3.3894 (15)	151 (2)
C8—H8⋯O7ⁱⁱⁱ	0.91 (1)	2.79 (2)	3.4071 (14)	126 (1)
C10—H10A⋯O6^iv	0.95 (1)	2.68 (2)	3.3334 (15)	127 (1)
C10—H10C⋯O1^v	0.97 (1)	2.50 (2)	3.3126 (15)	141 (2)
C11—H11B⋯O3ⁱ	0.99 (1)	2.48 (1)	3.4415 (14)	163 (2)
C15—H15A⋯O1ⁱⁱ	0.93 (1)	2.55 (2)	3.4592 (15)	167 (2)
C15—H15C⋯O4	0.96 (1)	2.53 (2)	3.4018 (15)	152 (2)
C16—H16A⋯O11^vi	0.94 (1)	2.66 (2)	3.3127 (15)	128 (2)
C16—H16B⋯O8^vii	0.96 (2)	2.52 (2)	3.3971 (17)	153 (2)
C18—H18⋯O2^viii	0.92 (1)	2.82 (2)	3.4646 (15)	128 (1)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) x+1, y, z; (vi) ; (vii) ; (viii) .

Figure 2
Packing diagram (viewed along a), showing extensive weak C—H⋯O contacts (red dotted lines) throughout the crystal structure.

Synthesis and crystallization

The title compound was prepared using the Inorganic Syntheses procedure (Chakravorti & Bandyopadhyay, 1992 ) with some modifications adapted from Arnáiz (1995 ). A sample of 3.0 grams of ammonium para-molybdate was dissolved in 6.0 ml of 24%_wt aqueous ammonia. A syringe was used to add 7.0 ml of 2,4-pentanedione with stirring. Concentrated nitric acid (5.0 ml) was added and the solution was stirred for 30 min. The product precipitated as a pale-yellow solid and was isolated by filtration and washed with deionized water (2 × 10 ml), followed by ethanol (1 × 10 ml), and diethyl ether (1 × 10 ml). Over multiple preparations the yield averaged around 90%. Characterization by ¹H NMR and FTIR agrees with previously reported values (Chakravorti & Bandyopadhyay, 1992; Arnáiz, 1995).

Three different crystallization methods were utilized: slow evaporation from a concentrated solution in 2,4-pentanedione, vapor diffusion (dichloromethane/diethyl ether), and layering (dichloromethane/diethyl ether) in a standard 5 mm NMR tube. All three methods produced crystals, but the highest quality crystals and those used in this study were produced from solvent layering.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[Mo(C₅H₇O₂)₂O₂]
M_r	326.15
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.0111 (3), 12.4143 (4), 12.6847 (4)
α, β, γ (°)	75.649 (1), 89.272 (1), 87.072 (1)
V (Å³)	1220.56 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.09
Crystal size (mm)	0.28 × 0.22 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.676, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	82074, 11855, 10556
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.835

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.04
No. of reflections	11855
No. of parameters	391
No. of restraints	28
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	1.19, −1.11
Computer programs: APEX3 (Bruker, 2020 ), SAINT (Bruker, 2020), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), CrystalMaker (Palmer, 2019 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2100177

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314621007781/wm4150sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621007781/wm4150Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621007781/wm4150Isup3.mol

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2020); cell refinement: SAINT (Bruker, 2020); data reduction: SAINT (Bruker, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: CrystalMaker (Palmer, 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Bis(2,4-dioxopentan-3-ido-κ²O,O')dioxidomolybdenum(VI) top

Crystal data top

[Mo(C₅H₇O₂)₂O₂]	Z = 4
M_r = 326.15	F(000) = 656
Triclinic, P1	D_x = 1.775 Mg m⁻³
a = 8.0111 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4143 (4) Å	Cell parameters from 9760 reflections
c = 12.6847 (4) Å	θ = 3.0–36.3°
α = 75.649 (1)°	µ = 1.09 mm⁻¹
β = 89.272 (1)°	T = 100 K
γ = 87.072 (1)°	Block, yellow
V = 1220.56 (7) Å³	0.28 × 0.22 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	10556 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.035
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 36.4°, θ_min = 1.7°
T_min = 0.676, T_max = 0.747	h = −13→13
82074 measured reflections	k = −20→20
11855 independent reflections	l = −21→21

Refinement top

Refinement on F²	28 restraints
Least-squares matrix: full	0 constraints
R[F² > 2σ(F²)] = 0.023	Only H-atom coordinates refined
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0307P)² + 0.524P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.003
11855 reflections	Δρ_max = 1.19 e Å⁻³
391 parameters	Δρ_min = −1.11 e Å⁻³

Special details top

Refinement. All H atoms were located in a difference-Fourier map. Hydrogen atom positions were refined with C—H distances restrained to 0.98 (2) Å (CH₃) or 0.95 (2) Å (ring C) and with U_iso(H) = 1.5U_eq(C) (methyl) or U_iso(H) = 1.2U_eq(C) (ring).

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

	x	y	z	U_iso*/U_eq
Mo1	0.19729 (2)	0.76693 (2)	0.56793 (2)	0.01071 (2)
O1	0.01992 (11)	0.69604 (7)	0.57195 (8)	0.01646 (15)
O2	0.14825 (12)	0.86914 (7)	0.63247 (7)	0.01718 (15)
O3	0.45296 (11)	0.82176 (7)	0.55088 (7)	0.01484 (14)
O4	0.32120 (11)	0.65709 (7)	0.47653 (7)	0.01407 (14)
O5	0.30012 (10)	0.65609 (7)	0.69609 (7)	0.01323 (13)
O6	0.17058 (11)	0.86448 (7)	0.41831 (7)	0.01522 (14)
C1	0.37036 (18)	0.55651 (10)	0.34261 (11)	0.0194 (2)
H1A	0.408 (2)	0.5708 (16)	0.2707 (13)	0.029*
H1B	0.457 (2)	0.5162 (15)	0.3884 (16)	0.029*
H1C	0.286 (2)	0.5032 (14)	0.3486 (16)	0.029*
C2	0.30151 (14)	0.65672 (9)	0.37795 (9)	0.01315 (17)
C3	0.21648 (16)	0.74411 (10)	0.30091 (9)	0.01650 (19)
H3	0.205 (2)	0.7355 (14)	0.2306 (12)	0.020*
C4	0.16005 (14)	0.84288 (9)	0.32317 (9)	0.01329 (17)
C5	0.08566 (17)	0.93714 (10)	0.23647 (10)	0.0183 (2)
H5A	0.170 (2)	0.9885 (14)	0.2000 (15)	0.028*
H5B	0.033 (2)	0.9095 (15)	0.1802 (14)	0.028*
H5C	0.002 (2)	0.9801 (15)	0.2663 (16)	0.028*
C6	0.42700 (16)	0.58188 (10)	0.86696 (9)	0.0170 (2)
H6A	0.416 (2)	0.5069 (12)	0.8582 (16)	0.026*
H6B	0.333 (2)	0.5953 (15)	0.9090 (15)	0.026*
H6C	0.5274 (19)	0.5743 (15)	0.9049 (15)	0.026*
C7	0.42379 (14)	0.66499 (9)	0.75910 (8)	0.01228 (16)
C8	0.54477 (15)	0.74177 (10)	0.73039 (9)	0.01541 (18)
H8	0.6317 (19)	0.7423 (14)	0.7754 (13)	0.018*
C9	0.56069 (13)	0.81282 (9)	0.62473 (9)	0.01234 (17)
C10	0.71393 (15)	0.87800 (10)	0.59652 (11)	0.0180 (2)
H10A	0.689 (2)	0.9523 (12)	0.5569 (15)	0.027*
H10B	0.776 (2)	0.8840 (15)	0.6561 (13)	0.027*
H10C	0.788 (2)	0.8426 (15)	0.5532 (15)	0.027*
Mo2	0.31234 (2)	0.23314 (2)	0.94971 (2)	0.01062 (2)
O7	0.35933 (12)	0.13590 (7)	1.06697 (7)	0.01702 (15)
O8	0.49058 (11)	0.30206 (7)	0.91316 (8)	0.01682 (15)
O9	0.18784 (11)	0.33673 (7)	0.80520 (7)	0.01435 (14)
O10	0.05669 (11)	0.17773 (7)	0.96628 (7)	0.01557 (15)
O11	0.33915 (11)	0.12896 (7)	0.85341 (7)	0.01430 (14)
O12	0.20855 (11)	0.34966 (7)	1.01892 (7)	0.01405 (14)
C11	0.42605 (16)	0.05038 (9)	0.70948 (10)	0.01590 (19)
H11A	0.506 (2)	0.0052 (14)	0.7626 (15)	0.024*
H11B	0.481 (2)	0.0759 (15)	0.6381 (12)	0.024*
H11C	0.338 (2)	0.0040 (14)	0.6990 (15)	0.024*
C12	0.35213 (13)	0.14698 (9)	0.74799 (9)	0.01179 (16)
C13	0.29618 (16)	0.24372 (9)	0.67571 (9)	0.01583 (19)
H13	0.312 (2)	0.2494 (14)	0.6000 (11)	0.019*
C14	0.20743 (13)	0.33250 (9)	0.70739 (9)	0.01210 (16)
C15	0.13314 (16)	0.42696 (10)	0.62128 (10)	0.01670 (19)
H15A	0.095 (2)	0.4053 (15)	0.5610 (13)	0.025*
H15B	0.043 (2)	0.4672 (15)	0.6472 (16)	0.025*
H15C	0.219 (2)	0.4773 (14)	0.5942 (15)	0.025*
C16	−0.20236 (16)	0.12360 (11)	1.04748 (12)	0.0219 (2)
H16A	−0.178 (2)	0.0492 (13)	1.0454 (17)	0.033*
H16B	−0.280 (2)	0.1597 (16)	0.9911 (15)	0.033*
H16C	−0.265 (2)	0.1222 (16)	1.1124 (14)	0.033*
C17	−0.04876 (14)	0.18876 (9)	1.03822 (9)	0.01463 (18)
C18	−0.03130 (16)	0.26312 (11)	1.10536 (10)	0.0182 (2)
H18	−0.116 (2)	0.2651 (15)	1.1543 (14)	0.022*
C19	0.08525 (14)	0.34274 (9)	1.08878 (9)	0.01445 (18)
C20	0.07649 (18)	0.43275 (12)	1.14881 (11)	0.0220 (2)
H20A	0.087 (3)	0.5039 (13)	1.1019 (16)	0.033*
H20B	−0.027 (2)	0.4408 (16)	1.1843 (16)	0.033*
H20C	0.163 (2)	0.4253 (17)	1.1994 (15)	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01212 (4)	0.01239 (4)	0.00833 (4)	−0.00019 (3)	−0.00151 (3)	−0.00391 (3)
O1	0.0145 (3)	0.0165 (4)	0.0190 (4)	−0.0011 (3)	−0.0029 (3)	−0.0055 (3)
O2	0.0220 (4)	0.0167 (4)	0.0150 (4)	−0.0011 (3)	0.0008 (3)	−0.0078 (3)
O3	0.0153 (3)	0.0185 (4)	0.0102 (3)	−0.0043 (3)	−0.0011 (3)	−0.0016 (3)
O4	0.0174 (4)	0.0143 (3)	0.0106 (3)	0.0010 (3)	−0.0004 (3)	−0.0037 (3)
O5	0.0147 (3)	0.0152 (3)	0.0094 (3)	−0.0023 (3)	−0.0017 (3)	−0.0018 (3)
O6	0.0229 (4)	0.0129 (3)	0.0099 (3)	0.0008 (3)	−0.0041 (3)	−0.0031 (3)
C1	0.0265 (6)	0.0172 (5)	0.0161 (5)	0.0006 (4)	0.0036 (4)	−0.0079 (4)
C2	0.0152 (4)	0.0140 (4)	0.0111 (4)	−0.0026 (3)	0.0016 (3)	−0.0043 (3)
C3	0.0244 (5)	0.0163 (5)	0.0096 (4)	−0.0001 (4)	−0.0026 (4)	−0.0048 (3)
C4	0.0157 (4)	0.0138 (4)	0.0102 (4)	−0.0028 (3)	−0.0027 (3)	−0.0020 (3)
C5	0.0240 (5)	0.0165 (5)	0.0127 (4)	−0.0004 (4)	−0.0066 (4)	0.0000 (4)
C6	0.0228 (5)	0.0171 (5)	0.0096 (4)	0.0007 (4)	−0.0027 (4)	−0.0004 (3)
C7	0.0156 (4)	0.0126 (4)	0.0090 (4)	0.0017 (3)	−0.0015 (3)	−0.0037 (3)
C8	0.0176 (5)	0.0159 (4)	0.0126 (4)	−0.0016 (4)	−0.0050 (4)	−0.0029 (3)
C9	0.0133 (4)	0.0114 (4)	0.0134 (4)	0.0000 (3)	−0.0004 (3)	−0.0051 (3)
C10	0.0146 (5)	0.0172 (5)	0.0234 (6)	−0.0040 (4)	0.0003 (4)	−0.0070 (4)
Mo2	0.01235 (4)	0.01240 (4)	0.00711 (4)	0.00003 (3)	0.00073 (3)	−0.00262 (3)
O7	0.0226 (4)	0.0168 (4)	0.0105 (3)	−0.0003 (3)	−0.0010 (3)	−0.0013 (3)
O8	0.0153 (4)	0.0165 (4)	0.0181 (4)	−0.0016 (3)	0.0027 (3)	−0.0033 (3)
O9	0.0188 (4)	0.0146 (3)	0.0095 (3)	0.0024 (3)	−0.0003 (3)	−0.0034 (3)
O10	0.0151 (3)	0.0185 (4)	0.0147 (4)	−0.0040 (3)	0.0028 (3)	−0.0066 (3)
O11	0.0214 (4)	0.0131 (3)	0.0083 (3)	0.0013 (3)	0.0016 (3)	−0.0029 (2)
O12	0.0161 (3)	0.0159 (3)	0.0115 (3)	−0.0007 (3)	0.0016 (3)	−0.0062 (3)
C11	0.0213 (5)	0.0137 (4)	0.0135 (4)	0.0010 (4)	0.0031 (4)	−0.0052 (3)
C12	0.0132 (4)	0.0124 (4)	0.0102 (4)	−0.0018 (3)	0.0025 (3)	−0.0037 (3)
C13	0.0244 (5)	0.0145 (4)	0.0085 (4)	0.0012 (4)	0.0011 (4)	−0.0031 (3)
C14	0.0146 (4)	0.0116 (4)	0.0100 (4)	−0.0021 (3)	−0.0006 (3)	−0.0020 (3)
C15	0.0233 (5)	0.0129 (4)	0.0127 (4)	−0.0002 (4)	−0.0046 (4)	−0.0009 (3)
C16	0.0159 (5)	0.0220 (5)	0.0248 (6)	−0.0044 (4)	0.0025 (4)	0.0002 (4)
C17	0.0139 (4)	0.0151 (4)	0.0127 (4)	0.0001 (3)	0.0004 (3)	0.0007 (3)
C18	0.0185 (5)	0.0222 (5)	0.0141 (5)	0.0002 (4)	0.0065 (4)	−0.0054 (4)
C19	0.0173 (4)	0.0173 (4)	0.0091 (4)	0.0039 (4)	−0.0006 (3)	−0.0050 (3)
C20	0.0263 (6)	0.0251 (6)	0.0181 (5)	0.0048 (5)	−0.0002 (4)	−0.0135 (5)

Geometric parameters (Å, º) top

Mo1—O1	1.7029 (9)	Mo2—O7	1.6996 (9)
Mo1—O2	1.7001 (9)	Mo2—O8	1.7021 (9)
Mo1—O3	2.1825 (8)	Mo2—O9	2.1808 (8)
Mo1—O4	2.1921 (8)	Mo2—O10	2.1848 (9)
Mo1—O5	2.0060 (8)	Mo2—O11	1.9898 (8)
Mo1—O6	1.9897 (8)	Mo2—O12	2.0106 (8)
O3—C9	1.2624 (13)	O9—C14	1.2623 (13)
O4—C2	1.2635 (13)	O10—C17	1.2632 (14)
O5—C7	1.3067 (13)	O11—C12	1.3036 (13)
O6—C4	1.3041 (13)	O12—C19	1.3104 (14)
C1—H1A	0.933 (14)	C11—H11A	0.984 (14)
C1—H1B	0.947 (15)	C11—H11B	0.988 (14)
C1—H1C	0.957 (14)	C11—H11C	0.962 (14)
C1—C2	1.5010 (16)	C11—C12	1.4961 (15)
C2—C3	1.4183 (16)	C12—C13	1.3761 (16)
C3—H3	0.931 (14)	C13—H13	0.953 (14)
C3—C4	1.3782 (16)	C13—C14	1.4191 (16)
C4—C5	1.4971 (16)	C14—C15	1.4942 (16)
C5—H5A	0.983 (14)	C15—H15A	0.932 (14)
C5—H5B	0.975 (14)	C15—H15B	0.961 (14)
C5—H5C	0.968 (15)	C15—H15C	0.957 (14)
C6—H6A	0.973 (14)	C16—H16A	0.941 (14)
C6—H6B	0.946 (14)	C16—H16B	0.961 (15)
C6—H6C	0.931 (14)	C16—H16C	0.955 (15)
C6—C7	1.4952 (16)	C16—C17	1.4944 (17)
C7—C8	1.3762 (16)	C17—C18	1.4152 (17)
C8—H8	0.907 (14)	C18—H18	0.917 (14)
C8—C9	1.4184 (16)	C18—C19	1.3709 (17)
C9—C10	1.4955 (16)	C19—C20	1.4986 (17)
C10—H10A	0.948 (14)	C20—H20A	0.942 (15)
C10—H10B	0.931 (14)	C20—H20B	0.950 (15)
C10—H10C	0.965 (14)	C20—H20C	0.935 (15)

O1—Mo1—O3	165.66 (4)	O7—Mo2—O8	105.59 (5)
O1—Mo1—O4	89.35 (4)	O7—Mo2—O9	164.58 (4)
O1—Mo1—O5	93.60 (4)	O7—Mo2—O10	87.98 (4)
O1—Mo1—O6	98.03 (4)	O7—Mo2—O11	95.53 (4)
O2—Mo1—O1	105.40 (4)	O7—Mo2—O12	96.98 (4)
O2—Mo1—O3	88.56 (4)	O8—Mo2—O9	89.81 (4)
O2—Mo1—O4	165.18 (4)	O8—Mo2—O10	166.15 (4)
O2—Mo1—O5	97.16 (4)	O8—Mo2—O11	97.67 (4)
O2—Mo1—O6	95.35 (4)	O8—Mo2—O12	94.14 (4)
O3—Mo1—O4	76.80 (3)	O9—Mo2—O10	76.68 (3)
O5—Mo1—O3	81.17 (3)	O11—Mo2—O9	81.38 (3)
O5—Mo1—O4	82.99 (3)	O11—Mo2—O10	83.47 (3)
O6—Mo1—O3	83.63 (3)	O11—Mo2—O12	159.82 (4)
O6—Mo1—O4	80.95 (3)	O12—Mo2—O9	82.36 (3)
O6—Mo1—O5	160.01 (4)	O12—Mo2—O10	81.22 (3)
C9—O3—Mo1	127.94 (7)	C14—O9—Mo2	128.23 (7)
C2—O4—Mo1	128.41 (7)	C17—O10—Mo2	127.20 (8)
C7—O5—Mo1	130.40 (7)	C12—O11—Mo2	131.47 (7)
C4—O6—Mo1	132.43 (7)	C19—O12—Mo2	129.74 (7)
H1A—C1—H1B	108.5 (17)	H11A—C11—H11B	109.9 (16)
H1A—C1—H1C	105.8 (17)	H11A—C11—H11C	108.6 (15)
H1B—C1—H1C	103.1 (16)	H11B—C11—H11C	106.5 (15)
C2—C1—H1A	115.0 (12)	C12—C11—H11A	111.4 (11)
C2—C1—H1B	113.3 (13)	C12—C11—H11B	110.9 (10)
C2—C1—H1C	110.2 (12)	C12—C11—H11C	109.4 (11)
O4—C2—C1	117.22 (10)	O11—C12—C11	114.43 (9)
O4—C2—C3	123.67 (10)	O11—C12—C13	124.15 (10)
C3—C2—C1	119.10 (10)	C13—C12—C11	121.35 (10)
C2—C3—H3	117.7 (11)	C12—C13—H13	118.0 (10)
C4—C3—C2	123.42 (10)	C12—C13—C14	123.58 (10)
C4—C3—H3	118.8 (11)	C14—C13—H13	118.3 (10)
O6—C4—C3	124.17 (10)	O9—C14—C13	123.53 (10)
O6—C4—C5	114.20 (10)	O9—C14—C15	117.53 (10)
C3—C4—C5	121.60 (10)	C13—C14—C15	118.93 (10)
C4—C5—H5A	112.3 (11)	C14—C15—H15A	113.4 (12)
C4—C5—H5B	110.8 (11)	C14—C15—H15B	113.3 (12)
C4—C5—H5C	111.2 (12)	C14—C15—H15C	108.1 (11)
H5A—C5—H5B	106.9 (16)	H15A—C15—H15B	107.6 (16)
H5A—C5—H5C	107.7 (16)	H15A—C15—H15C	105.6 (16)
H5B—C5—H5C	107.8 (16)	H15B—C15—H15C	108.5 (15)
H6A—C6—H6B	105.2 (16)	H16A—C16—H16B	110.9 (18)
H6A—C6—H6C	101.7 (16)	H16A—C16—H16C	107.2 (17)
H6B—C6—H6C	112.9 (17)	H16B—C16—H16C	102.8 (17)
C7—C6—H6A	110.9 (12)	C17—C16—H16A	112.3 (12)
C7—C6—H6B	110.0 (12)	C17—C16—H16B	109.7 (12)
C7—C6—H6C	115.2 (12)	C17—C16—H16C	113.5 (12)
O5—C7—C6	114.28 (10)	O10—C17—C16	117.36 (11)
O5—C7—C8	124.26 (10)	O10—C17—C18	123.12 (11)
C8—C7—C6	121.45 (10)	C18—C17—C16	119.44 (11)
C7—C8—H8	121.1 (11)	C17—C18—H18	115.8 (12)
C7—C8—C9	123.91 (10)	C19—C18—C17	124.01 (10)
C9—C8—H8	114.2 (11)	C19—C18—H18	119.2 (11)
O3—C9—C8	123.05 (10)	O12—C19—C18	124.32 (10)
O3—C9—C10	117.50 (10)	O12—C19—C20	114.39 (11)
C8—C9—C10	119.42 (10)	C18—C19—C20	121.27 (11)
C9—C10—H10A	112.2 (12)	C19—C20—H20A	112.1 (13)
C9—C10—H10B	114.7 (12)	C19—C20—H20B	114.9 (12)
C9—C10—H10C	109.6 (11)	C19—C20—H20C	112.8 (13)
H10A—C10—H10B	105.2 (16)	H20A—C20—H20B	102.8 (17)
H10A—C10—H10C	108.5 (16)	H20A—C20—H20C	104.7 (18)
H10B—C10—H10C	106.2 (16)	H20B—C20—H20C	108.6 (18)

Mo1—O3—C9—C8	14.91 (16)	Mo2—O9—C14—C13	11.74 (16)
Mo1—O3—C9—C10	−167.23 (8)	Mo2—O9—C14—C15	−167.95 (8)
Mo1—O4—C2—C1	−165.78 (8)	Mo2—O10—C17—C16	−167.33 (8)
Mo1—O4—C2—C3	13.14 (16)	Mo2—O10—C17—C18	15.86 (16)
Mo1—O5—C7—C6	159.72 (8)	Mo2—O11—C12—C11	160.69 (8)
Mo1—O5—C7—C8	−21.55 (16)	Mo2—O11—C12—C13	−22.43 (17)
Mo1—O6—C4—C3	−21.18 (18)	Mo2—O12—C19—C18	−20.31 (17)
Mo1—O6—C4—C5	160.91 (8)	Mo2—O12—C19—C20	161.61 (8)
O4—C2—C3—C4	6.18 (19)	O10—C17—C18—C19	10.74 (19)
O5—C7—C8—C9	−7.08 (18)	O11—C12—C13—C14	−4.41 (19)
C1—C2—C3—C4	−174.93 (11)	C11—C12—C13—C14	172.26 (11)
C2—C3—C4—O6	−3.75 (19)	C12—C13—C14—O9	8.31 (19)
C2—C3—C4—C5	174.01 (11)	C12—C13—C14—C15	−172.00 (11)
C6—C7—C8—C9	171.56 (11)	C16—C17—C18—C19	−166.01 (12)
C7—C8—C9—O3	9.00 (18)	C17—C18—C19—O12	−10.0 (2)
C7—C8—C9—C10	−168.82 (11)	C17—C18—C19—C20	167.99 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O8ⁱ	0.93 (1)	2.62 (2)	3.4834 (16)	155 (2)
C5—H5B···O10ⁱⁱ	0.98 (1)	2.50 (1)	3.4652 (15)	170 (2)
C6—H6A···O8	0.97 (1)	2.51 (2)	3.3894 (15)	151 (2)
C8—H8···O7ⁱⁱⁱ	0.91 (1)	2.79 (2)	3.4071 (14)	126 (1)
C10—H10A···O6^iv	0.95 (1)	2.68 (2)	3.3334 (15)	127 (1)
C10—H10C···O1^v	0.97 (1)	2.50 (2)	3.3126 (15)	141 (2)
C11—H11B···O3ⁱ	0.99 (1)	2.48 (1)	3.4415 (14)	163 (2)
C15—H15A···O1ⁱⁱ	0.93 (1)	2.55 (2)	3.4592 (15)	167 (2)
C15—H15C···O4	0.96 (1)	2.53 (2)	3.4018 (15)	152 (2)
C16—H16A···O11^vi	0.94 (1)	2.66 (2)	3.3127 (15)	128 (2)
C16—H16B···O8^vii	0.96 (2)	2.52 (2)	3.3971 (17)	153 (2)
C18—H18···O2^viii	0.92 (1)	2.82 (2)	3.4646 (15)	128 (1)

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

Funding information

Funding for this research was provided by: National Science Foundation, Directorate for Education and Human Resources (grant No. 0942850 to Dean Johnston); Otterbein University Student Research Fund (grant to Calvin King, Aileen Seitz, Mia Sethi).

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