research communications
of a methyl benzoate quadruple-bonded dimolybdenum complex
aDepartment of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 02138, USA
*Correspondence e-mail: dkiper@fas.harvard.edu
Quadruple-bond dimolybdenum complexes provide invaluable insight into the two-electron bond, with structural chemistry providing a foundation for examination of bond properties. The synthesis and solid-state structure of the quadruple-bonded dimolybdenum(II) complex tetrakis(μ-4-methylbenzoato-κ2O:O′)bis[(tetrahydrofuran-κO)molybdenum(II)] tetrahydrofuran disolvate, [Mo2(C8H7O2)4(C4H8O)2]·2C4H8O, are presented. This complex crystallizes in a triclinic cell with low-symmetry P. The dimolybdenum paddlewheel structure comprises four methylbenzoate ligands and two axial THF ligands. The dimolybdenum bond distance of 2.1012 (4) Å is exemplary of this class of compounds.
Keywords: crystal structure; quadruple bond; molybdenum; delta bond.
CCDC reference: 2242699
1. Chemical context
The two-electron bond (Lewis, 1916) is the most basic element in the field of chemistry. Quadruple-bond complexes have been central in experimentally defining the two-electron bond within a unified context of the valence (Heitler & London, 1927) and molecular orbital (Pauling, 1928; Lennard-Jones, 1929; Mulliken, 1932; James & Coolidge, 1933; Coulson & Fischer, 1949) bonding models. The importance of quadruple-bond complexes in elucidating the two-electron bond arises from the four states that originate from the two-orbital 1φφ, 3φφ*, 1φφ*, and 1φ*φ*, where φ and φ* represent bonding and antibonding orbitals, respectively. In experimental systems with σ and π bonding frameworks, the excited states are not all accessible because of the dissociation or rotation arising from population of σ and π antibonding orbitals. Quadruple-bonded metal–metal complexes, whose metal–metal linkages are characterized by a σ2π4δ2 ground state, are able to overcome this limitation. Pioneered by a σ2π4 framework and locked from rotation by diametrically opposed bulky ligands or bidentate ligands, all four states defining the δ2 two-electron bond (1δδ, 3δδ*, 1δδ*, and 1δ*δ*) may experimentally be verified for dimolybdenum quadruple-bond complexes (Engebretson et al., 1994, 1999; Cotton & Nocera, 2000; Boettcher et al., 2022).
In the preliminary investigation of Mo2(O2CCH3)4, Lawton & Mason (1965) determined the dimolybdenum bond distance to be 2.11 Å, which was later adjusted by Cotton & Norman (1971) to 2.0934 Å. As a result of the weak overlap of the dxy orbitals constituting a δ bond, one-electron oxidation or reduction of a dimolybdenum core does little to perturb the dimolybdenum bond distance, allowing for the spectroelectrochemical determination of the degree of overlap between these orbitals (Boettcher et al., 2022).
How the properties of the equatorial ligands affect the dimolybdenum bond distance has been a central question in the structural chemistry of quadruple-bond complexes (Han, 2011). Cotton proposed that either electron-withdrawing or electron-donating substituents in the of the dimolybdenum core will modulate the bonding within the quadruple-bond framework (Cotton et al., 1978). A comparative analysis of electron-donating, -neutral and -withdrawing ligands drives to the heart of this issue. Previous studies have examined the electron-neutral Mo2(p-O2CC6H5)4 (Cotton et al., 1978) and electron-withdrawing Mo2(p-O2CC6H4CF3)4 (Aigeldinger et al., 2022) groups on the paddlewheel motif to understand the electronic effect of homologous R groups on Mo—Mo bond distances. With this motivation, we have utilized a dimolybdenum core with 4-methylbenzoate and tetrahydrofuran (THF) ligands to extend the electronic effect of varying substituents. Here we present the and synthesis of tetrakis(μ-4-methylbenzoato-κ2O:O')-bis(tetrahydrofuran) dimolybdenum(II) solvate [Mo2(p-O2CC6H4CH3)4·2(C4H8O)]·C4H8O. The presence of an electron-donating methyl group on the bridging benzoate ligands results in a minor elongation of the dimolybdenum bond with respect to the parent benzoate compound and compression in comparison to a benzoate complex with an electron-withdrawing trifluoromethyl group.
2. Structural commentary
The molecular structure of the dimolybdenum complex, [Mo2(p-O2CC6H4CH3)4·2(C4H8O)] is presented in Fig. 1 as ascertained using single-crystal X-ray diffraction. The contains half of the molecule (Fig. 1), which upon inversion about the quadruple bond, yields the complete molecular structure. Pertinent bond metrics for [Mo2(p-O2CC6H4CH3)4·2(C4H8O)]·2C4H8O were collected and compiled in Table 1. Complete tables of the structural metrics of the title compound are listed in the supporting information. The dimolybdenum bond distance is 2.1012 (4) Å, which is consistent with the previously reported Mo—Mo quadruple-bond distances of 2.06–2.17 Å (Cotton et al., 2002). Noting that the dimolybdenum bond distance of the unsubstituted phenyl analogue, Mo2(O2CC6H5)4, is 2.096 (1) Å (Cotton et al., 1978), the addition of the methyl group at the 4-position of the benzoate results in an increase of the dimolybdenum bond distance by 0.0053 (1) Å.
The electron-donating nature of the methyl-substituted benzoates is illuminated by comparing the pKa values of carboxylate ligands [pKa = 4.37 for p-O2CC6H4CH3, pKa = 4.19 for O2CC6H5 (Hollingsworth et al., 2002); pKa = 3.77 for p-O2CC6H4CF3 (Rumble, 2021)]. A comparative analysis of the dimolybdenum bond lengths of [Mo2(p-O2CC6H4CH3)4·(C4H8O)] and [Mo2(p-O2CC6H4CF3)·(C4H8O)] demonstrates that the addition of an electron-donating equatorial ligand does not lead to a distinguishable variation; the d(Mo—Mo) for [Mo2(p-O2CC6H4CF3)·(C4H8O)] is 2.1098 (7) Å (Aigeldinger et al., 2022) and in this study d(Mo—Mo) for [Mo2(p-O2CC6H4CH3)·(C4H8O)] is 2.1012 (4) Å. Therefore, the addition of a ligand with electron-donating or withdrawing properties does not perturb the dimolybdenum quadruple-bond length. These observations support the findings of Han (2011) and Aigeldinger (Aigeldinger et al., 2022), concluding that while holding the axial ligand (THF) constant, placing a series of R groups on the carboxylate negligibly perturbs the Mo—Mo bond distance.
3. Supramolecular features
Molecular packing arrangements are shown in Fig. 2. The structure was solved in the triclinic P. Unbound THF molecules are ordered in between p-O2CC6H4CH3 ligands of adjacent molecules, along the b-axis, with the oxygen atom facing away from the metal center and toward the methyl groups.
The O2 oxygen atoms of the unbound THF solvent molecules are located at distances of 4.178 (3) and 6.530 (4) Å from the C13 atoms of the p-O2CC6H4CH3 ligands of adjacent molecules.
4. Database survey
A search in the Cambridge Structural Database (WebCSD, accessed November 2022; Groom et al., 2016) for the CSD search fragment C32H28Mo2O8 for Mo2(p-O2CC6H4CH3)4 yielded no hits. The CSD search fragment C40H44Mo2O10 for [Mo2(p-O2CC6H4CH3)4·(C4H8O)] also yielded no hits. The CSD reference code for Mo2(O2CCH3)4 (Cotton et al., 1974) is MOLACE01 and for Mo2(O2CC6H5)4 (Cotton et al., 1978) is MOBZOA.
5. Synthesis and crystallization
Fig. 3 shows the overall synthetic reaction scheme. Molybdenum hexacarbonyl [Mo(CO)6], p-toluic acid, anhydrous THF, and 1,2-dichlorobenzene were purchased from Sigma-Aldrich. Mo(CO)6 and p-toluic acid were combined in an oven-dried flask with anhydrous THF and anhydrous 1,2-dichlorobenzene. The reaction was heated under reflux for 48 h at 413 K under a dry N2 atmosphere (Pence et al., 1999). The reaction mixture was cooled, dried, and washed with anhydrous dichloromethane and pentane.
The crystallization was prepared in a
The crude product was dissolved in anhydrous THF, filtered, and recrystallized by vapor diffusion of pentane using a 6 by 50 mm borosilicate glass crystallization tube housed within a 20 mL glass vial. The assembly was allowed to stand at 238 K for 14 days. Orange block-shaped crystals were observed and harvested for X-ray diffraction analysis.6. Refinement
Table 2 contains crystal data, data collection, and structure details. A single orange block (0.220 mm × 0.180 mm × 0.140 mm) was chosen for single-crystal X-ray diffraction using a Bruker D8 goniometer equipped with an Photon100 CMOS detector. Data were collected as a series of φ and/or ω scans. Data integration down to 0.84 Å resolution was carried out using SAINT V8.37A with reflection spot size optimization. Absorption corrections were made with the program SADABS2016/2 (Krause et al., 2015). Space-group assignments were determined by examination of E-statistics, and successive of the structures. The structure was solved by the intrinsic phasing method and refined by least-squares methods also using SHELXT2014/5 and SHELXL2014/7 with the OLEX2 (Dolomanov et al., 2009) interface. The program PLATON (Spek, 2020) was employed to confirm the absence of higher symmetry space groups. All non-H atoms, including the disorder fragment, were located in difference-Fourier maps, and then refined anisotropically. Outlier reflections were omitted from when appropriate. Hydrogen atoms on C atoms were placed at idealized positions and refined using a riding model. The isotropic displacement parameters of all hydrogen atoms were fixed to 1.2 times the atoms they are linked to (1.5 times for methyl groups). Crystallographic details, including the software employed, have been delineated within the crystallographic information (*.cif).
|
Supporting information
CCDC reference: 2242699
https://doi.org/10.1107/S2056989023001457/ex2066sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023001457/ex2066Isup4.hkl
Cell
SAINT 8.37A (Bruker, 2015); data reduction: SAINT 8.37A (Bruker, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Mo2(C8H7O2)4(C4H8O)2]·2C4H8O | Z = 1 |
Mr = 1020.84 | F(000) = 528 |
Triclinic, P1 | Dx = 1.537 Mg m−3 |
a = 9.3923 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.6505 (8) Å | Cell parameters from 9495 reflections |
c = 12.2955 (9) Å | θ = 2.4–27.2° |
α = 78.001 (2)° | µ = 0.63 mm−1 |
β = 74.374 (2)° | T = 100 K |
γ = 69.853 (2)° | Block, orange |
V = 1102.96 (14) Å3 | 0.22 × 0.18 × 0.14 mm |
Bruker D8 goniometer with Photon 100 CMOS detector diffractometer | 3693 reflections with I > 2σ(I) |
Radiation source: IµS microfocus tube | Rint = 0.027 |
ω and phi scans | θmax = 25.1°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.731, Tmax = 0.767 | k = −12→12 |
22892 measured reflections | l = −14→14 |
3909 independent reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0302P)2 + 1.5476P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.002 |
3909 reflections | Δρmax = 0.90 e Å−3 |
282 parameters | Δρmin = −0.65 e Å−3 |
0 restraints |
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. |
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 > 2sigma(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. All non-H atoms were located in difference-Fourier maps, and then refined anisotropically. |
x | y | z | Uiso*/Ueq | ||
Mo1 | 0.39274 (2) | 0.06805 (2) | 0.53300 (2) | 0.01099 (8) | |
O1 | 0.46193 (18) | 0.23761 (15) | 0.44960 (13) | 0.0131 (3) | |
O2 | 0.68863 (17) | 0.09443 (15) | 0.37715 (13) | 0.0127 (3) | |
O3 | 0.46834 (18) | 0.07766 (15) | 0.67574 (13) | 0.0132 (3) | |
O4 | 0.69515 (18) | −0.07015 (15) | 0.60914 (13) | 0.0129 (3) | |
C1 | 0.5992 (3) | 0.2138 (2) | 0.38833 (19) | 0.0134 (5) | |
C2 | 0.6581 (3) | 0.3276 (2) | 0.33066 (19) | 0.0130 (5) | |
C3 | 0.5784 (3) | 0.4587 (2) | 0.35819 (19) | 0.0149 (5) | |
H3 | 0.4818 | 0.4759 | 0.4117 | 0.018* | |
C4 | 0.6392 (3) | 0.5629 (2) | 0.3081 (2) | 0.0170 (5) | |
H4 | 0.5854 | 0.6506 | 0.3294 | 0.020* | |
C5 | 0.7784 (3) | 0.5418 (2) | 0.2267 (2) | 0.0164 (5) | |
C6 | 0.8555 (3) | 0.4114 (2) | 0.1982 (2) | 0.0167 (5) | |
H6 | 0.9496 | 0.3951 | 0.1421 | 0.020* | |
C7 | 0.7978 (3) | 0.3058 (2) | 0.24985 (19) | 0.0152 (5) | |
H7 | 0.8535 | 0.2175 | 0.2303 | 0.018* | |
C8 | 0.8424 (3) | 0.6562 (2) | 0.1713 (2) | 0.0211 (5) | |
H8A | 0.7822 | 0.7132 | 0.1154 | 0.032* | |
H8B | 0.9513 | 0.6202 | 0.1329 | 0.032* | |
H8C | 0.8357 | 0.7098 | 0.2294 | 0.032* | |
C9 | 0.6052 (3) | 0.0033 (2) | 0.68511 (19) | 0.0134 (5) | |
C10 | 0.6588 (3) | 0.0043 (2) | 0.78726 (19) | 0.0135 (5) | |
C11 | 0.5778 (3) | 0.1055 (2) | 0.8573 (2) | 0.0187 (5) | |
H11 | 0.4876 | 0.1734 | 0.8393 | 0.022* | |
C12 | 0.6274 (3) | 0.1077 (2) | 0.9520 (2) | 0.0201 (5) | |
H12 | 0.5719 | 0.1784 | 0.9976 | 0.024* | |
C13 | 0.7570 (3) | 0.0086 (2) | 0.9827 (2) | 0.0170 (5) | |
C14 | 0.8374 (3) | −0.0929 (2) | 0.9130 (2) | 0.0160 (5) | |
H14 | 0.9261 | −0.1620 | 0.9323 | 0.019* | |
C15 | 0.7901 (3) | −0.0945 (2) | 0.81614 (19) | 0.0154 (5) | |
H15 | 0.8475 | −0.1635 | 0.7690 | 0.018* | |
C16 | 0.8066 (3) | 0.0121 (3) | 1.0881 (2) | 0.0225 (5) | |
H16A | 0.7314 | −0.0101 | 1.1555 | 0.034* | |
H16B | 0.8114 | 0.1025 | 1.0882 | 0.034* | |
H16C | 0.9093 | −0.0538 | 1.0892 | 0.034* | |
O1S | 0.10283 (19) | 0.19386 (16) | 0.61146 (14) | 0.0175 (4) | |
C1S | −0.0151 (3) | 0.1276 (3) | 0.6333 (2) | 0.0256 (6) | |
H1SA | −0.0575 | 0.1121 | 0.7161 | 0.031* | |
H1SB | 0.0293 | 0.0395 | 0.6034 | 0.031* | |
C2S | −0.1417 (3) | 0.2203 (3) | 0.5732 (2) | 0.0280 (6) | |
H2SA | −0.1805 | 0.1685 | 0.5360 | 0.034* | |
H2SB | −0.2297 | 0.2731 | 0.6273 | 0.034* | |
C3S | −0.0621 (3) | 0.3109 (3) | 0.4864 (3) | 0.0319 (7) | |
H3SA | −0.0080 | 0.2693 | 0.4155 | 0.038* | |
H3SB | −0.1370 | 0.3997 | 0.4679 | 0.038* | |
C4S | 0.0514 (3) | 0.3239 (2) | 0.5461 (2) | 0.0207 (5) | |
H4SA | 0.1401 | 0.3459 | 0.4902 | 0.025* | |
H4SB | 0.0005 | 0.3954 | 0.5966 | 0.025* | |
O2S | 0.2645 (3) | 0.5866 (2) | 0.05605 (18) | 0.0418 (5) | |
C5S | 0.2502 (4) | 0.5990 (3) | 0.1730 (3) | 0.0358 (7) | |
H5SA | 0.1489 | 0.6638 | 0.2027 | 0.043* | |
H5SB | 0.3343 | 0.6304 | 0.1809 | 0.043* | |
C6S | 0.2628 (3) | 0.4590 (3) | 0.2366 (2) | 0.0319 (6) | |
H6SA | 0.3031 | 0.4452 | 0.3061 | 0.038* | |
H6SB | 0.1613 | 0.4413 | 0.2575 | 0.038* | |
C7S | 0.3761 (4) | 0.3726 (3) | 0.1498 (3) | 0.0346 (7) | |
H7SA | 0.3680 | 0.2800 | 0.1655 | 0.042* | |
H7SB | 0.4842 | 0.3684 | 0.1463 | 0.042* | |
C8S | 0.3238 (4) | 0.4464 (3) | 0.0429 (3) | 0.0358 (7) | |
H8SA | 0.4121 | 0.4303 | −0.0236 | 0.043* | |
H8SB | 0.2420 | 0.4152 | 0.0310 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.01006 (11) | 0.01080 (11) | 0.01143 (11) | −0.00298 (7) | −0.00185 (7) | −0.00096 (7) |
O1 | 0.0120 (8) | 0.0122 (8) | 0.0138 (8) | −0.0031 (6) | −0.0019 (6) | −0.0013 (6) |
O2 | 0.0110 (8) | 0.0115 (8) | 0.0140 (8) | −0.0029 (6) | −0.0010 (6) | −0.0016 (6) |
O3 | 0.0117 (8) | 0.0131 (8) | 0.0141 (8) | −0.0027 (6) | −0.0024 (6) | −0.0022 (6) |
O4 | 0.0117 (8) | 0.0137 (8) | 0.0127 (8) | −0.0035 (6) | −0.0016 (6) | −0.0025 (6) |
C1 | 0.0132 (12) | 0.0167 (12) | 0.0114 (11) | −0.0046 (9) | −0.0043 (9) | −0.0018 (9) |
C2 | 0.0130 (11) | 0.0145 (11) | 0.0120 (11) | −0.0043 (9) | −0.0045 (9) | 0.0001 (9) |
C3 | 0.0124 (11) | 0.0167 (12) | 0.0142 (11) | −0.0036 (9) | −0.0022 (9) | −0.0012 (9) |
C4 | 0.0190 (12) | 0.0113 (11) | 0.0201 (12) | −0.0019 (9) | −0.0071 (10) | −0.0013 (9) |
C5 | 0.0169 (12) | 0.0169 (12) | 0.0164 (12) | −0.0061 (10) | −0.0075 (10) | 0.0027 (9) |
C6 | 0.0147 (12) | 0.0184 (12) | 0.0162 (12) | −0.0061 (10) | −0.0019 (9) | −0.0011 (9) |
C7 | 0.0155 (12) | 0.0136 (11) | 0.0158 (12) | −0.0029 (9) | −0.0034 (9) | −0.0028 (9) |
C8 | 0.0208 (13) | 0.0165 (12) | 0.0249 (13) | −0.0073 (10) | −0.0036 (10) | 0.0010 (10) |
C9 | 0.0138 (12) | 0.0102 (11) | 0.0155 (12) | −0.0053 (9) | −0.0022 (9) | 0.0015 (9) |
C10 | 0.0131 (11) | 0.0142 (11) | 0.0136 (11) | −0.0072 (9) | −0.0018 (9) | 0.0009 (9) |
C11 | 0.0187 (12) | 0.0156 (12) | 0.0200 (13) | −0.0032 (10) | −0.0041 (10) | −0.0022 (10) |
C12 | 0.0233 (13) | 0.0172 (12) | 0.0190 (12) | −0.0050 (10) | −0.0012 (10) | −0.0073 (10) |
C13 | 0.0187 (12) | 0.0210 (12) | 0.0146 (12) | −0.0130 (10) | −0.0012 (9) | −0.0003 (9) |
C14 | 0.0124 (11) | 0.0194 (12) | 0.0159 (12) | −0.0068 (10) | −0.0028 (9) | 0.0014 (9) |
C15 | 0.0143 (12) | 0.0160 (12) | 0.0150 (12) | −0.0056 (9) | 0.0001 (9) | −0.0030 (9) |
C16 | 0.0254 (14) | 0.0297 (14) | 0.0159 (12) | −0.0129 (11) | −0.0040 (10) | −0.0031 (10) |
O1S | 0.0154 (8) | 0.0144 (8) | 0.0207 (9) | −0.0039 (7) | −0.0050 (7) | 0.0020 (7) |
C1S | 0.0168 (13) | 0.0222 (13) | 0.0380 (16) | −0.0108 (11) | −0.0065 (11) | 0.0047 (11) |
C2S | 0.0230 (14) | 0.0279 (15) | 0.0367 (16) | −0.0105 (12) | −0.0138 (12) | 0.0023 (12) |
C3S | 0.0328 (16) | 0.0319 (16) | 0.0329 (16) | −0.0119 (13) | −0.0164 (13) | 0.0076 (12) |
C4S | 0.0186 (13) | 0.0149 (12) | 0.0242 (13) | −0.0051 (10) | −0.0027 (10) | 0.0041 (10) |
O2S | 0.0511 (14) | 0.0390 (12) | 0.0312 (11) | −0.0086 (11) | −0.0081 (10) | −0.0058 (9) |
C5S | 0.0371 (17) | 0.0394 (17) | 0.0315 (16) | −0.0117 (14) | −0.0052 (13) | −0.0086 (13) |
C6S | 0.0288 (15) | 0.0413 (17) | 0.0281 (15) | −0.0157 (13) | −0.0076 (12) | 0.0005 (13) |
C7S | 0.0352 (17) | 0.0314 (16) | 0.0390 (17) | −0.0140 (13) | −0.0055 (13) | −0.0046 (13) |
C8S | 0.0331 (16) | 0.0350 (17) | 0.0391 (17) | −0.0134 (13) | −0.0022 (13) | −0.0065 (13) |
Mo1—O3 | 2.0955 (15) | C13—C14 | 1.396 (3) |
Mo1—O1 | 2.1011 (15) | C13—C16 | 1.501 (3) |
Mo1—Mo1i | 2.1012 (4) | C14—C15 | 1.384 (3) |
Mo1—O2i | 2.1119 (15) | C14—H14 | 0.9500 |
Mo1—O4i | 2.1177 (15) | C15—H15 | 0.9500 |
Mo1—O1S | 2.5980 (16) | C16—H16A | 0.9800 |
O1—C1 | 1.275 (3) | C16—H16B | 0.9800 |
O2—C1 | 1.271 (3) | C16—H16C | 0.9800 |
O2—Mo1i | 2.1119 (15) | O1S—C4S | 1.443 (3) |
O3—C9 | 1.278 (3) | O1S—C1S | 1.449 (3) |
O4—C9 | 1.274 (3) | C1S—C2S | 1.515 (4) |
O4—Mo1i | 2.1177 (15) | C1S—H1SA | 0.9900 |
C1—C2 | 1.473 (3) | C1S—H1SB | 0.9900 |
C2—C7 | 1.396 (3) | C2S—C3S | 1.506 (4) |
C2—C3 | 1.402 (3) | C2S—H2SA | 0.9900 |
C3—C4 | 1.378 (3) | C2S—H2SB | 0.9900 |
C3—H3 | 0.9500 | C3S—C4S | 1.503 (4) |
C4—C5 | 1.395 (3) | C3S—H3SA | 0.9900 |
C4—H4 | 0.9500 | C3S—H3SB | 0.9900 |
C5—C6 | 1.397 (3) | C4S—H4SA | 0.9900 |
C5—C8 | 1.499 (3) | C4S—H4SB | 0.9900 |
C6—C7 | 1.378 (3) | O2S—C8S | 1.430 (4) |
C6—H6 | 0.9500 | O2S—C5S | 1.438 (4) |
C7—H7 | 0.9500 | C5S—C6S | 1.514 (4) |
C8—H8A | 0.9800 | C5S—H5SA | 0.9900 |
C8—H8B | 0.9800 | C5S—H5SB | 0.9900 |
C8—H8C | 0.9800 | C6S—C7S | 1.497 (4) |
C9—C10 | 1.477 (3) | C6S—H6SA | 0.9900 |
C10—C15 | 1.393 (3) | C6S—H6SB | 0.9900 |
C10—C11 | 1.397 (3) | C7S—C8S | 1.497 (4) |
C11—C12 | 1.373 (4) | C7S—H7SA | 0.9900 |
C11—H11 | 0.9500 | C7S—H7SB | 0.9900 |
C12—C13 | 1.392 (4) | C8S—H8SA | 0.9900 |
C12—H12 | 0.9500 | C8S—H8SB | 0.9900 |
O3—Mo1—O1 | 89.23 (6) | C13—C14—H14 | 119.5 |
O3—Mo1—Mo1i | 92.27 (4) | C14—C15—C10 | 120.5 (2) |
O1—Mo1—Mo1i | 93.14 (4) | C14—C15—H15 | 119.8 |
O3—Mo1—O2i | 89.85 (6) | C10—C15—H15 | 119.8 |
O1—Mo1—O2i | 176.49 (6) | C13—C16—H16A | 109.5 |
Mo1i—Mo1—O2i | 90.28 (4) | C13—C16—H16B | 109.5 |
O3—Mo1—O4i | 176.30 (6) | H16A—C16—H16B | 109.5 |
O1—Mo1—O4i | 89.37 (6) | C13—C16—H16C | 109.5 |
Mo1i—Mo1—O4i | 91.23 (4) | H16A—C16—H16C | 109.5 |
O2i—Mo1—O4i | 91.34 (6) | H16B—C16—H16C | 109.5 |
O3—Mo1—O1S | 94.89 (6) | C4S—O1S—C1S | 108.66 (18) |
O1—Mo1—O1S | 97.74 (6) | C4S—O1S—Mo1 | 111.78 (13) |
Mo1i—Mo1—O1S | 167.04 (4) | C1S—O1S—Mo1 | 120.84 (14) |
O2i—Mo1—O1S | 78.97 (5) | O1S—C1S—C2S | 106.7 (2) |
O4i—Mo1—O1S | 81.90 (6) | O1S—C1S—H1SA | 110.4 |
C1—O1—Mo1 | 116.16 (14) | C2S—C1S—H1SA | 110.4 |
C1—O2—Mo1i | 118.39 (14) | O1S—C1S—H1SB | 110.4 |
C9—O3—Mo1 | 117.32 (14) | C2S—C1S—H1SB | 110.4 |
C9—O4—Mo1i | 117.29 (14) | H1SA—C1S—H1SB | 108.6 |
O2—C1—O1 | 122.0 (2) | C3S—C2S—C1S | 103.6 (2) |
O2—C1—C2 | 118.7 (2) | C3S—C2S—H2SA | 111.0 |
O1—C1—C2 | 119.3 (2) | C1S—C2S—H2SA | 111.0 |
C7—C2—C3 | 118.6 (2) | C3S—C2S—H2SB | 111.0 |
C7—C2—C1 | 120.3 (2) | C1S—C2S—H2SB | 111.0 |
C3—C2—C1 | 121.0 (2) | H2SA—C2S—H2SB | 109.0 |
C4—C3—C2 | 120.4 (2) | C4S—C3S—C2S | 102.6 (2) |
C4—C3—H3 | 119.8 | C4S—C3S—H3SA | 111.2 |
C2—C3—H3 | 119.8 | C2S—C3S—H3SA | 111.2 |
C3—C4—C5 | 121.3 (2) | C4S—C3S—H3SB | 111.2 |
C3—C4—H4 | 119.4 | C2S—C3S—H3SB | 111.2 |
C5—C4—H4 | 119.4 | H3SA—C3S—H3SB | 109.2 |
C4—C5—C6 | 117.9 (2) | O1S—C4S—C3S | 105.1 (2) |
C4—C5—C8 | 120.9 (2) | O1S—C4S—H4SA | 110.7 |
C6—C5—C8 | 121.2 (2) | C3S—C4S—H4SA | 110.7 |
C7—C6—C5 | 121.3 (2) | O1S—C4S—H4SB | 110.7 |
C7—C6—H6 | 119.3 | C3S—C4S—H4SB | 110.7 |
C5—C6—H6 | 119.3 | H4SA—C4S—H4SB | 108.8 |
C6—C7—C2 | 120.4 (2) | C8S—O2S—C5S | 108.1 (2) |
C6—C7—H7 | 119.8 | O2S—C5S—C6S | 105.4 (2) |
C2—C7—H7 | 119.8 | O2S—C5S—H5SA | 110.7 |
C5—C8—H8A | 109.5 | C6S—C5S—H5SA | 110.7 |
C5—C8—H8B | 109.5 | O2S—C5S—H5SB | 110.7 |
H8A—C8—H8B | 109.5 | C6S—C5S—H5SB | 110.7 |
C5—C8—H8C | 109.5 | H5SA—C5S—H5SB | 108.8 |
H8A—C8—H8C | 109.5 | C7S—C6S—C5S | 101.5 (2) |
H8B—C8—H8C | 109.5 | C7S—C6S—H6SA | 111.5 |
O4—C9—O3 | 121.8 (2) | C5S—C6S—H6SA | 111.5 |
O4—C9—C10 | 119.8 (2) | C7S—C6S—H6SB | 111.5 |
O3—C9—C10 | 118.3 (2) | C5S—C6S—H6SB | 111.5 |
C15—C10—C11 | 118.5 (2) | H6SA—C6S—H6SB | 109.3 |
C15—C10—C9 | 121.3 (2) | C6S—C7S—C8S | 101.3 (2) |
C11—C10—C9 | 120.1 (2) | C6S—C7S—H7SA | 111.5 |
C12—C11—C10 | 120.5 (2) | C8S—C7S—H7SA | 111.5 |
C12—C11—H11 | 119.7 | C6S—C7S—H7SB | 111.5 |
C10—C11—H11 | 119.7 | C8S—C7S—H7SB | 111.5 |
C11—C12—C13 | 121.5 (2) | H7SA—C7S—H7SB | 109.3 |
C11—C12—H12 | 119.2 | O2S—C8S—C7S | 107.0 (2) |
C13—C12—H12 | 119.2 | O2S—C8S—H8SA | 110.3 |
C12—C13—C14 | 117.9 (2) | C7S—C8S—H8SA | 110.3 |
C12—C13—C16 | 120.3 (2) | O2S—C8S—H8SB | 110.3 |
C14—C13—C16 | 121.8 (2) | C7S—C8S—H8SB | 110.3 |
C15—C14—C13 | 121.0 (2) | H8SA—C8S—H8SB | 108.6 |
C15—C14—H14 | 119.5 | ||
Mo1i—O2—C1—O1 | −1.7 (3) | O4—C9—C10—C11 | 165.2 (2) |
Mo1i—O2—C1—C2 | 176.87 (14) | O3—C9—C10—C11 | −14.6 (3) |
Mo1—O1—C1—O2 | 0.8 (3) | C15—C10—C11—C12 | 0.4 (4) |
Mo1—O1—C1—C2 | −177.72 (15) | C9—C10—C11—C12 | −179.6 (2) |
O2—C1—C2—C7 | 11.2 (3) | C10—C11—C12—C13 | −1.3 (4) |
O1—C1—C2—C7 | −170.2 (2) | C11—C12—C13—C14 | 0.9 (4) |
O2—C1—C2—C3 | −166.7 (2) | C11—C12—C13—C16 | −178.8 (2) |
O1—C1—C2—C3 | 11.9 (3) | C12—C13—C14—C15 | 0.3 (3) |
C7—C2—C3—C4 | −1.5 (3) | C16—C13—C14—C15 | −180.0 (2) |
C1—C2—C3—C4 | 176.4 (2) | C13—C14—C15—C10 | −1.2 (3) |
C2—C3—C4—C5 | 1.9 (4) | C11—C10—C15—C14 | 0.8 (3) |
C3—C4—C5—C6 | −0.7 (3) | C9—C10—C15—C14 | −179.2 (2) |
C3—C4—C5—C8 | 179.0 (2) | C4S—O1S—C1S—C2S | 2.6 (3) |
C4—C5—C6—C7 | −1.0 (3) | Mo1—O1S—C1S—C2S | −128.57 (18) |
C8—C5—C6—C7 | 179.3 (2) | O1S—C1S—C2S—C3S | 19.8 (3) |
C5—C6—C7—C2 | 1.5 (4) | C1S—C2S—C3S—C4S | −33.5 (3) |
C3—C2—C7—C6 | −0.2 (3) | C1S—O1S—C4S—C3S | −24.1 (3) |
C1—C2—C7—C6 | −178.1 (2) | Mo1—O1S—C4S—C3S | 111.77 (19) |
Mo1i—O4—C9—O3 | −1.3 (3) | C2S—C3S—C4S—O1S | 35.7 (3) |
Mo1i—O4—C9—C10 | 178.91 (15) | C8S—O2S—C5S—C6S | −14.8 (3) |
Mo1—O3—C9—O4 | 2.6 (3) | O2S—C5S—C6S—C7S | 34.5 (3) |
Mo1—O3—C9—C10 | −177.62 (14) | C5S—C6S—C7S—C8S | −39.8 (3) |
O4—C9—C10—C15 | −14.9 (3) | C5S—O2S—C8S—C7S | −11.0 (3) |
O3—C9—C10—C15 | 165.3 (2) | C6S—C7S—C8S—O2S | 32.4 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
Funding information
We thank Daniel G. Nocera for helpful discussions and contributions to the preparation of the manuscript. DKD acknowledges Harvard University, Department of Chemistry and Chemical Biology. BMC acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant DGE–2140743 and the Herchel Smith Graduate Fellowship Program at Harvard University.
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