Crystal structure and Hirshfeld surface analysis of the elusive tri­chloro­bis­(diethyl ether)oxo­molybdenum(V)

Shaw, T.E.; LeMagueres, P.; Sattelberger, A.P.; Jurca, T.

doi:10.1107/S2053229620011626

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 76| Part 10| October 2020| Pages 947-951

https://doi.org/10.1107/S2053229620011626

Crystal structure and Hirshfeld surface analysis of the elusive trichlorobis(diethyl ether)oxomolybdenum(V)

Thomas E. Shaw,^a,^b Pierre LeMagueres,^c Alfred P. Sattelberger ^a ^* and Titel Jurca ^a,^b ^*

^aDepartment of Chemistry, University of Central Florida, Orlando, FL 32816, USA, ^bRenewable Energy and Chemical Transformations Cluster, University of Central Florida, Orlando, FL 32816, USA, and ^cRigaku Americas Corporation, The Woodlands, TX 77381, USA
^*Correspondence e-mail: al.sattelberger@knights.ucf.edu, titel.jurca@ucf.edu

Edited by A. Lemmerer, University of the Witwatersrand, South Africa (Received 21 July 2020; accepted 25 August 2020; online 19 September 2020)

First reported in 1930, MoCl₃O(Et₂O)₂ is a by-product of the reductive synthesis of MoCl₄(OEt₂)₂ from MoCl₅. We report herein the X-ray crystal structure and Hirshfeld surface characteristics of mer-MoCl₃O(Et₂O)₂, or [MoCl₃O(C₄H₁₀O)₂]. The compound crystallizes in the orthorhombic space group P2₁2₁2₁. The molybdenyl (Mo=O) bond length is 1.694 (3) Å and the cis- and trans-Mo—O distances are 2.157 (3) and 2.304 (3) Å, respectively. Intermolecular Mo=O⋯H bonding is present in the lattice, with the shortest distance being 2.572 Å.

Keywords: molybdenum(V) oxohalide; crystal structure; Hirshfeld surface analysis.

CCDC reference: 2013034

1. Introduction

The red–orange diethyl ether adduct of molybdenum(IV) chloride, MoCl₄(OEt₂)₂ (1), is a useful synthon for mid-valent molybdenum chemistry (Kuiper et al., 2008a ,b ). It can be prepared anaerobically by reducing a suspension of molybdenum pentachloride, MoCl₅, in diethyl ether with any one of the following reductants: norbornene (Castellani & Gallazzi, 1985 ), allyltrimethylsilane (Persson & Andersson, 1993 ), or elemental tin (Stoffelbach et al., 2001 ). 1 is sparingly soluble in ether and easily isolated by filtration. The crystalline solid slowly loses ether on standing at room temperature and more rapidly under vacuum. Each of the published preparations provide 1 in ≥80% yield. Two of the reported syntheses (Castellani & Gallazzi, 1985; Stoffelbach et al., 2001) note that if either the diethyl ether is not sufficiently dry and/or the MoCl₅ is contaminated with oxyhalides, the green molybdenum(V) oxo–chloro compound MoCl₃O(OEt₂)₂ (2) forms as a by-product. The latter compound was first reported in 1930 (Wardlaw & Webb, 1930 ). The solid-state structure of 2 (Scheme 1) has never been reported and is the subject of the present work.

2. Experimental

2.1. Synthesis and crystallization

Compound 1 was prepared essentially as described by Persson & Andersson (1993), by adding excess C₃H₅SiMe₃ dropwise to a stirred diethyl ether suspension of MoCl₅ inside an mBraun inert atmosphere glove-box (water and O₂ levels of ≤1 ppm). For practical reasons, the reaction was carried out at approximately −30 °C rather than at the reported −78 °C. The red–orange solid product, which formed immediately at low temperature upon addition of the silane, was stirred for 2 h at room temperature and then filtered off and washed with fresh diethyl ether collected on an mBraun solvent purification system. The red–orange filtrate was concentrated to ca 15 ml, placed in a scintillation vial, and stored in the −35 °C freezer of the glove-box. After several days, a well-formed dark-green crystal of 2 was observed at the bottom of the vial. A crystal of 2 with dimensions 0.16 × 0.21 × 0.60 mm was removed from the mother liquor, coated with Paratone oil, removed from the glove-box, quickly secured to a MiteGen micromount, and mounted on the diffractometer under a cryostream (100 K) to prevent the loss of diethyl ether. Notably, 2 rapidly degrades in Paratone under ambient conditions (Fig. S1 in the supporting information).

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were attached via the riding model at calculated positions.

Table 1
Experimental details

Crystal data
Chemical formula	[MoCl₃O(C₄H₁₀O)₂]
M_r	366.53
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	8.6186 (7), 12.250 (1), 13.5681 (11)
V (Å³)	1432.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.46
Crystal size (mm)	0.6 × 0.21 × 0.16

Data collection
Diffractometer	Rigaku XtaLAB Mini II
Absorption correction	Gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2020 $[Rigaku Oxford Diffraction (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.614, 0.831
No. of measured, independent and observed [I > 2σ(I)] reflections	7488, 3179, 2959
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.069, 1.01
No. of reflections	3179
No. of parameters	153
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.87
Absolute structure	Flack x determined using 1123 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.01 (5)
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2020 $[Rigaku Oxford Diffraction (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

3. Results and discussion

MoCl₃O(Et₂O)₂ (2) crystallized in the enantiomorphic space group P2₁2₁2₁ with a single molecule in the asymmetric unit. The structure and atom-labeling scheme are shown in Fig. 1(a). A partially occupied unit cell, with hydrogen bonding represented by dashed lines, is shown in Fig. 1(b). Expanded packing diagrams of eight unit cells (2 × 2 × 2) are displayed in the supporting information (Fig. S2); beyond the description of hydrogen-bonding interactions provided (vide infra), there are no remarkable features requiring further discussion. The isolated MoCl₃O(Et₂O)₂ complex exists in a distorted octahedral geometry, with the chloro ligands adopting a meridional configuration. This is consistent with predicted structures and analogous oxomolybdenum complexes with solvent ligands coordinated through the O heteroatoms (Castellani & Gallazzi, 1985; Stoffelbach et al., 2001; Vitzthumecker et al., 2017 ; Marchetti et al., 2013 ). Selected bond lengths are shown in Table 2, showcasing the metal-to-ligand bond lengths and angles.

Table 2
Selected geometric parameters (Å, °)

Mo1—Cl1	2.3469 (13)	Mo1—O3	2.304 (3)
Mo1—Cl3	2.3530 (13)	O2—C1	1.468 (6)
Mo1—Cl2	2.3159 (13)	O2—C3	1.463 (6)
Mo1—O1	1.694 (3)	O3—C5	1.455 (5)
Mo1—O2	2.157 (3)	O3—C7	1.463 (5)

O1—Mo1—O3	173.06 (14)	O1—Mo1—O2	93.09 (14)
O2—Mo1—Cl2	168.30 (9)	O3—Mo1—Cl2	88.37 (9)
Cl1—Mo1—Cl3	165.00 (5)	O3—Mo1—Cl1	82.92 (8)
O1—Mo1—Cl2	98.48 (12)	O3—Mo1—Cl3	82.19 (8)
O1—Mo1—Cl1	98.02 (11)	O2—Mo1—O3	80.10 (11)
O1—Mo1—Cl3	96.55 (11)

Figure 1
(a) The asymmetric unit of 2, showing the labeling scheme for the complex. Displacement ellipsoids are drawn at the 50% probability level. (b) The partially filled P2₁2₁2₁ unit cell of 2, showing the inter- and intramolecular hydrogen-bonding interactions.

As expected, the O atom of the diethyl ether ligand that is trans to the molybdenum–oxo bond is elongated [2.304 (3) Å] compared to the O atom trans to a meridional chloro ligand [2.157 (3) Å]. In fact, the molybdenum–oxo bond length, as well as the lengths of the meridional chloro ligands, are similar to analogous complexes (Table 3) (Marchetti et al., 2013; Vitzthumecker et al., 2017; Di Nicola et al., 2015 ). The slight differences in the bond lengths of the meridional chloro ligands can be explained by the donating nature of the coordinating solvents. The only complex with longer Mo—O(solvent) bonds is MoCl₃O(H₃COCH₂CH₂OCH₂Cl), which is likely a result of the chloro functioning as a weak electron-withdrawing group. The lability of the diethyl ether ligands and the relatively short lifetime of the isolated MoCl₃O(Et₂O)₂ complex under ambient conditions can thus be explained by the elongated Mo—O(solvent) bonds (Fig. S1 in the supporting information).

Table 3
Comparative Mo—L and Mo—X bond lengths of MoCl₃O(Et₂O)₂ (2) and analogous complexes

The ligand represented by `thf' is tetrahydrofuran.

MoCl₃O(Et₂O)₂	MoCl₃O(thf)₂	MoCl₃O(MeOH)₂	MoCl₃O[MeO(CH₂)₂OCH₂Cl]
	(Marchetti et al., 2013)	(Vitzthumecker et al., 2017)	(Di Nicola et al., 2015)
Mo1—Cl1 2.3469 (13)	Mo—Cl2 2.3513 (9)	Mo1—Cl2 2.3642 (8)	Mo1—Cl5 2.3542 (8)
Mo1—Cl3 2.3530 (13)	Mo—Cl1 2.3646 (8)	Mo1—Cl1 2.3434 (7)	Mo1—Cl4 2.3453 (7)
Mo1—Cl2 2.3159 (13)	Mo—Cl3 2.3191 (9)	Mo1—Cl3 2.3741 (9)	Mo1—Cl2 2.3216 (7)
Mo1—O2 2.157 (3)	Mo—O2(thf) 2.146 (2)	Mo—O2 2.099 (2)	Mo1—O2 2.161 (2)
Mo1—O3 2.304 (3)	Mo—O3(thf) 2.277 (2)	Mo—O3 2.266 (2)	Mo1—O3 2.420 (2)
Mo1—O1 1.694 (3)	Mo—O1(oxo) 1.682 (2)	Mo1—O1 1.655 (2)	Mo1—O1 1.666 (2)

There are instances of intermolecular hydrogen bonding that occur between the molybdenum–oxo linkage and neighboring diethyl ether ligands. Specifically, Mo1=O1⋯H1Bⁱ—C1ⁱ and Mo1=O1⋯H5Bⁱⁱ—C5ⁱⁱ [symmetry codes: (i) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (ii) −x + $[{1\over 2}]$ , −y + 1, z + $[{1\over 2}]$ ], with bond lengths of 2.683 and 2.572 Å, respectively (Fig. 1b). These two bonding interactions explain the extended Mo1=O1 bond distance [1.694 (3) Å] compared to analogous oxomolybdenum complexes (Table 3). An intramolecular close contact is also present between two meridional chloro ligands and neighboring diethyl ether H atoms, viz. Cl1⋯H1A—C1, Cl3⋯H4B—C4, and Cl3⋯H8B—C8, with bond lengths of 2.697, 2.949, and 2.946 Å, respectively. Atom Cl3 also experiences an intermolecular contact through Cl3⋯H5Aⁱⁱ—C5ⁱⁱ and Cl3⋯H2Aⁱⁱ—C2ⁱⁱ, with bond lengths of 2.926 and 2.927 Å, respectively. These close contacts are a direct cause of the extended Mo—Cl bond lengths of Mo1—Cl1 and Mo1—Cl3 (Table 2). A basal plane was generated through the meridional plane of the complex with the equation −0.272x + 0.709y − 0.650z − 0.536 = 0 (Fig. S3 in the supporting information). The distance of the molybdenum centre from the centroid of the basal plane is 0.264 Å and the fractional coordinates from the atom projection to the plane are (0.134701, 0.460936, 0.478813). This centre–centroid distance is shorter than that reported for the MoCl₃O(MeOH)₂ and MoCl₃O[MeO(CH₂)₂OCH₂Cl] adducts, which display respective distances of 0.322 and 0.378 Å, but is similar to that of MoCl₃O(PMe₃)(O=PMe₃), which has a distance of 0.256 Å (Marchetti et al., 2013; Limberg et al., 1996 ).

The d_norm Hirshfeld surface (−0.0313 to 1.2958 Å) was generated using CrystalExplorer17 (Turner et al., 2017 ) and can be seen in Fig. 2. There are four red portions of the surface, generated by interactions that are shorter than van der Waals radii, all of which are the result of Mo=O⋯H—C interactions between the CH₂ hydrogens of the coordinated diethyl ether and the Mo=O oxygen. Two of these interactions are the result of exterior diethyl ether hydrogens near the interior Mo=O bond, while the other two are caused by two exterior Mo=O bonds interacting with interior diethyl ether ligands. The Hirshfeld surface with neighboring atoms and molecules is elaborated in Fig. S4 (see supporting information). The spatial configuration of neighboring molecules is a direct result of these close contact interactions, causing the coordinated diethyl ethers to lie in proximity to one another. Because of this, the majority of the Hirshfeld surface is the result of H⋯H interactions between interior and exterior diethyl ethers, which account for 49.9% of the surface (Fig. 3b). The points of intimate contact between the diethyl ether H atoms and the molybdenum–oxo bonds account for a total of 10.9% of the surface (Figs. 3d and 3e). Intriguingly, contact between the meridional chloro ligands and diethyl ether H atoms account for 37.4% of the Hirshfeld surface, but do not account for any of the close contact points of the surface. The remaining percentages of the Hirshfeld surface can be seen in the remainder of Fig. 3. As expected, no portions of the surface are caused by interactions, both interior and exterior, from Mo or C atoms.

Figure 2
d_norm Hirshfeld surface of MoCl₃O(Et₂O)₂ from various viewpoints highlighting the areas of intimate contact.

Figure 3
Two-dimensional (2D) fingerprint plots identifying the percent composition of the Hirshfeld surface from the various noncovalent interactions, with the accompanying percent contribution to the Hirshfeld surface: (a) the complete fingerprint plot accounting for all interactions, (b) interactions between interior and exterior H atoms, (c) interactions between interior Cl and exterior H atoms, (d) interactions between interior H and exterior Cl atoms, (e) interactions between interior O and exterior H atoms, (f) interactions between interior H and exterior O atoms, (g) interactions between interior Cl and exterior O atoms, and (h) interactions between interior O and exterior Cl atoms.

4. Conclusion

The crystal structure and Hirshfeld surface character of mer-MoCl₃O(Et₂O)₂, along with fingerprint-plot analysis, have been reported. The chloro ligands adopt a meridional configuration, with one diethyl ether ligand coordinated trans to a chloro ligand and one trans to the molybdenum–oxo bond. The molybdenum–diethyl ether bond trans to the molybdenum–oxo bond is noticeably longer than seen in analogous complexes, consistent with the lability of the coordinated diethyl ether. Intermolecular hydrogen bonds occur between the molybdenum–oxo bond and the CH₂ diethyl ether groups of neighboring complexes. Unresolved is the source of the molybdenyl O atom in 2. All reagents were of high purity and the liquid starting materials were thoroughly dried and deoxygenated. The yield of 2 described above was estimated to be <5%. When a second reaction was carried out with identical quantities of the same reagents, but closer to room temperature, the filtrate was green and the yield of 2 increased significantly (>10%). We surmise from this result that diethyl ether is at least a contributing source of the molybdenyl O atom in 2. Further work would be needed to identify the organic side products and develop a mechanistic picture of exactly how the oxygen transfer occurs. With a confirmed structure, the door is open for implementation of mer-MoCl₃O(Et₂O)₂ (2) as a potential oxomolybdenum(V) synthon.

Supporting information

CCDC reference: 2013034

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2053229620011626/ef3009sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2053229620011626/ef3009Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229620011626/ef3009sup3.pdf

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2020); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2020); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2020); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Trichloridobis(diethyl ether)oxidomolybdenum(V) top

Crystal data top

[MoCl₃O(C₄H₁₀O)₂]	D_x = 1.700 Mg m⁻³
M_r = 366.53	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3727 reflections
a = 8.6186 (7) Å	θ = 2.2–30.5°
b = 12.250 (1) Å	µ = 1.46 mm⁻¹
c = 13.5681 (11) Å	T = 100 K
V = 1432.5 (2) Å³	Block, green
Z = 4	0.6 × 0.21 × 0.16 mm
F(000) = 740

Data collection top

Rigaku XtaLAB Mini II diffractometer	R_int = 0.042
Absorption correction: gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2020)	θ_max = 27.5°, θ_min = 2.2°
T_min = 0.614, T_max = 0.831	h = −11→10
7488 measured reflections	k = −15→15
3179 independent reflections	l = −17→16
2959 reflections with I > 2σ(I)

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0278P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.033	(Δ/σ)_max < 0.001
wR(F²) = 0.069	Δρ_max = 0.53 e Å⁻³
S = 1.01	Δρ_min = −0.87 e Å⁻³
3179 reflections	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
153 parameters	Extinction coefficient: 0.0042 (6)
0 restraints	Absolute structure: Flack x determined using 1123 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Hydrogen site location: mixed	Absolute structure parameter: 0.01 (5)

Special details top

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

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

	x	y	z	U_iso*/U_eq
Mo1	0.14299 (5)	0.44571 (3)	0.49142 (3)	0.01453 (13)
Cl3	0.28566 (14)	0.58992 (10)	0.56149 (9)	0.0189 (3)
Cl1	−0.00756 (16)	0.33468 (10)	0.38785 (9)	0.0220 (3)
Cl2	−0.07724 (14)	0.49900 (10)	0.57657 (9)	0.0209 (3)
O2	0.3298 (4)	0.4174 (3)	0.3888 (2)	0.0174 (8)
O3	0.0863 (4)	0.5768 (2)	0.3751 (2)	0.0144 (7)
O1	0.2054 (4)	0.3474 (3)	0.5698 (2)	0.0168 (8)
C5	0.0851 (6)	0.5576 (4)	0.2693 (3)	0.0182 (11)
H5A	0.135 (6)	0.491 (4)	0.258 (4)	0.022*
H5B	0.160 (6)	0.612 (4)	0.235 (4)	0.022*
C6	−0.0733 (6)	0.5618 (4)	0.2246 (4)	0.0236 (12)
H6A	−0.066049	0.547134	0.153769	0.035*
H6B	−0.118133	0.634422	0.235048	0.035*
H6C	−0.139516	0.506695	0.255753	0.035*
C7	0.0422 (6)	0.6881 (4)	0.4026 (4)	0.0190 (12)
H7A	0.027585	0.691699	0.474858	0.023*
H7B	−0.058213	0.706262	0.371106	0.023*
C3	0.4417 (6)	0.4994 (4)	0.3559 (4)	0.0224 (12)
H3A	0.396033	0.572873	0.364903	0.027*
H3B	0.461479	0.489161	0.284577	0.027*
C1	0.3840 (7)	0.3043 (5)	0.3786 (4)	0.0229 (13)
H1A	0.289 (6)	0.265 (4)	0.396 (4)	0.027*
H1B	0.467 (6)	0.293 (4)	0.421 (4)	0.027*
C8	0.1614 (7)	0.7714 (4)	0.3723 (4)	0.0286 (13)
H8A	0.174268	0.769715	0.300548	0.043*
H8B	0.260723	0.754567	0.404031	0.043*
H8C	0.126930	0.844267	0.392619	0.043*
C2	0.4275 (8)	0.2761 (4)	0.2751 (4)	0.0314 (14)
H2A	0.340121	0.291847	0.231139	0.047*
H2B	0.453518	0.198366	0.271139	0.047*
H2C	0.517573	0.319693	0.255101	0.047*
C4	0.5935 (6)	0.4942 (5)	0.4102 (4)	0.0346 (15)
H4A	0.647842	0.426657	0.392671	0.052*
H4B	0.573964	0.495383	0.481324	0.052*
H4C	0.657549	0.557115	0.391958	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01522 (19)	0.0139 (2)	0.0144 (2)	−0.00072 (17)	0.00121 (18)	−0.00088 (18)
Cl3	0.0200 (6)	0.0202 (6)	0.0165 (6)	−0.0034 (5)	−0.0024 (5)	−0.0025 (5)
Cl1	0.0286 (7)	0.0161 (6)	0.0213 (7)	−0.0050 (6)	−0.0044 (6)	−0.0019 (6)
Cl2	0.0174 (6)	0.0251 (7)	0.0202 (7)	0.0015 (6)	0.0047 (6)	−0.0008 (6)
O2	0.0203 (18)	0.0119 (17)	0.0200 (18)	0.0030 (14)	0.0045 (15)	0.0044 (14)
O3	0.0205 (17)	0.0124 (18)	0.0103 (16)	0.0035 (14)	−0.0016 (14)	−0.0012 (14)
O1	0.0164 (17)	0.0174 (18)	0.0166 (18)	0.0003 (15)	0.0010 (15)	−0.0014 (16)
C5	0.025 (3)	0.021 (3)	0.009 (2)	0.002 (3)	0.002 (2)	−0.002 (2)
C6	0.029 (3)	0.023 (3)	0.019 (3)	0.000 (3)	−0.007 (2)	−0.001 (3)
C7	0.024 (3)	0.008 (2)	0.024 (3)	0.004 (2)	−0.001 (2)	−0.001 (2)
C3	0.022 (3)	0.023 (3)	0.022 (3)	−0.004 (2)	0.007 (2)	0.003 (2)
C1	0.031 (3)	0.018 (3)	0.020 (3)	0.012 (2)	0.002 (3)	0.002 (2)
C8	0.041 (3)	0.014 (3)	0.031 (3)	−0.001 (3)	−0.003 (3)	0.000 (2)
C2	0.051 (4)	0.021 (3)	0.022 (3)	0.011 (3)	0.007 (3)	−0.003 (3)
C4	0.019 (3)	0.050 (4)	0.035 (3)	−0.001 (3)	0.005 (3)	−0.001 (3)

Geometric parameters (Å, º) top

Mo1—Cl1	2.3469 (13)	C7—H7B	0.9900
Mo1—Cl3	2.3530 (13)	C7—C8	1.506 (7)
Mo1—Cl2	2.3159 (13)	C3—H3A	0.9900
Mo1—O1	1.694 (3)	C3—H3B	0.9900
Mo1—O2	2.157 (3)	C3—C4	1.502 (7)
Mo1—O3	2.304 (3)	C1—H1A	0.97 (5)
O2—C1	1.468 (6)	C1—H1B	0.93 (5)
O2—C3	1.463 (6)	C1—C2	1.493 (7)
O3—C5	1.455 (5)	C8—H8A	0.9800
O3—C7	1.463 (5)	C8—H8B	0.9800
C5—H5A	0.93 (5)	C8—H8C	0.9800
C5—H5B	1.04 (5)	C2—H2A	0.9800
C5—C6	1.494 (7)	C2—H2B	0.9800
C6—H6A	0.9800	C2—H2C	0.9800
C6—H6B	0.9800	C4—H4A	0.9800
C6—H6C	0.9800	C4—H4B	0.9800
C7—H7A	0.9900	C4—H4C	0.9800

O1—Mo1—O3	173.06 (14)	O3—C7—C8	112.6 (4)
O2—Mo1—Cl2	168.30 (9)	H7A—C7—H7B	107.8
Cl1—Mo1—Cl3	165.00 (5)	C8—C7—H7A	109.1
O1—Mo1—Cl2	98.48 (12)	C8—C7—H7B	109.1
O1—Mo1—Cl1	98.02 (11)	O2—C3—H3A	108.9
O1—Mo1—Cl3	96.55 (11)	O2—C3—H3B	108.9
O1—Mo1—O2	93.09 (14)	O2—C3—C4	113.3 (4)
O3—Mo1—Cl2	88.37 (9)	H3A—C3—H3B	107.7
O3—Mo1—Cl1	82.92 (8)	C4—C3—H3A	108.9
O3—Mo1—Cl3	82.19 (8)	C4—C3—H3B	108.9
O2—Mo1—O3	80.10 (11)	O2—C1—H1A	100 (3)
Cl2—Mo1—Cl3	90.87 (5)	O2—C1—H1B	109 (3)
Cl2—Mo1—Cl1	90.51 (5)	O2—C1—C2	112.7 (4)
O2—Mo1—Cl3	89.52 (9)	H1A—C1—H1B	115 (4)
O2—Mo1—Cl1	86.14 (10)	C2—C1—H1A	109 (3)
C3—O2—Mo1	125.4 (3)	C2—C1—H1B	110 (3)
C3—O2—C1	114.2 (4)	C7—C8—H8A	109.5
C1—O2—Mo1	116.8 (3)	C7—C8—H8B	109.5
C5—O3—Mo1	124.4 (3)	C7—C8—H8C	109.5
C5—O3—C7	113.6 (4)	H8A—C8—H8B	109.5
C7—O3—Mo1	122.0 (3)	H8A—C8—H8C	109.5
O3—C5—H5A	107 (3)	H8B—C8—H8C	109.5
O3—C5—H5B	110 (3)	C1—C2—H2A	109.5
O3—C5—C6	113.7 (4)	C1—C2—H2B	109.5
H5A—C5—H5B	101 (4)	C1—C2—H2C	109.5
C6—C5—H5A	113 (3)	H2A—C2—H2B	109.5
C6—C5—H5B	111 (3)	H2A—C2—H2C	109.5
C5—C6—H6A	109.5	H2B—C2—H2C	109.5
C5—C6—H6B	109.5	C3—C4—H4A	109.5
C5—C6—H6C	109.5	C3—C4—H4B	109.5
H6A—C6—H6B	109.5	C3—C4—H4C	109.5
H6A—C6—H6C	109.5	H4A—C4—H4B	109.5
H6B—C6—H6C	109.5	H4A—C4—H4C	109.5
O3—C7—H7A	109.1	H4B—C4—H4C	109.5
O3—C7—H7B	109.1

Mo1—O2—C3—C4	98.5 (5)	C5—O3—C7—C8	−68.7 (5)
Mo1—O2—C1—C2	143.0 (4)	C7—O3—C5—C6	−67.0 (5)
Mo1—O3—C5—C6	110.8 (4)	C3—O2—C1—C2	−57.5 (6)
Mo1—O3—C7—C8	113.4 (4)	C1—O2—C3—C4	−58.9 (6)

Comparative Mo—L and Mo—X bond lengths of MoCl₃O(Et₂O)₂ (2) and analogous complexes (Marchetti et al., 2013; Vitzthumecker et al., 2017; Di Nicola et al., 2015) top

MoCl₃O(Et₂O)₂	MoCl₃O(thf)₂	MoCl₃O(MeOH)₂	MoCl₃O(MeO(CH₂)₂OCH₂Cl)
Mo1—Cl1 2.353 (1)	Mo—Cl2 2.3513 (9)	Mo1—Cl2 2.3642 (8)	Mo1—Cl5 2.3542 (8)
Mo1—Cl3 2.347 (1)	Mo—Cl1 2.3646 (8)	Mo1—Cl1 2.3434 (7)	Mo1—Cl4 2.3453 (7)
Mo1—Cl2 2.316 (1)	Mo—Cl3 2.3191 (9)	Mo1—Cl3 2.3741 (9)	Mo1—Cl2 2.3216 (7)
Mo1—O2 2.158 (3)	Mo—O2(thf) 2.146 (2)	Mo—O2 2.099 (2)	Mo1—O2 2.161 (2)
Mo1—O3 2.305 (3)	Mo—O3(thf) 2.277 (2)	Mo—O3 2.266 (2)	Mo1—O3 2.420 (2)
Mo1—O1 1.694 (3)	Mo—O1(oxide) 1.682 (2)	Mo1—O1 1.655 (2)	Mo1—O1 1.666 (2)

Acknowledgements

This work was supported by start-up funding from the Department of Chemistry, College of Science, and the Faculty Cluster Initiative at the University of Central Florida.

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