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First reported in 1930, MoCl
3O(Et
2O)
2 is a by-product of the reductive synthesis of MoCl
4(OEt
2)
2 from MoCl
5. We report herein the X-ray crystal structure and Hirshfeld surface characteristics of
mer-MoCl
3O(Et
2O)
2, or [MoCl
3O(C
4H
10O)
2]. The compound crystallizes in the orthorhombic space group
P2
12
12
1. 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.
Supporting information
CCDC reference: 2013034
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] | Dx = 1.700 Mg m−3 |
Mr = 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 | Rint = 0.042 |
Absorption correction: gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2020) | θmax = 27.5°, θmin = 2.2° |
Tmin = 0.614, Tmax = 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(Fo2) + (0.0278P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.033 | (Δ/σ)max < 0.001 |
wR(F2) = 0.069 | Δρmax = 0.53 e Å−3 |
S = 1.01 | Δρmin = −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 | Uiso*/Ueq | |
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) topMoCl3O(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) |
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