metal-organic compounds
Tetracarbonyl[4,4-dimethyl-2-(pyridin-2-yl)-2-oxazoline-κ2N,N′]molybdenum(0)
aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
*Correspondence e-mail: matthias.beller@catalysis.de
In the title compound, [Mo(C10H12N2O)(CO)4], the molybdenum(0) center is surrounded by a bidentate diimine [4,4-dimethyl-2-(pyridin-2-yl)-2-oxazoline] and four carbonyl ligands in a distorted octahedral coordination geometry. The diimine ligand coordinates via the two nitrogen atoms.
Keywords: crystal structure; bidentate; diimine; molybdenum.
CCDC reference: 1899206
Structure description
A diimine and four carbonyl ligands are coordinated to a molybdenum(0) atom which shows a distorted octahedral coordination geometry (Fig. 1). The largest deviations from 90° are observed for N2—Mo1—N1 72.27 (3)° and C11—Mo1—N2 99.97 (4)°. The diimine ligand coordinates via the two nitrogen atoms to the metal center. The two carbonyl ligands coordinated perpendicular to the diimine ligand are slightly bent [Mo1—C12—O3 173.7 (1), Mo1—C14—O5 173.5 (1)°]. This deviation was expected as it has already been observed for similar tetra-carbonyl molybdenum(0) complexes containing 2-(pyridin-2-yl)benzoxazole (Datta et al., 2011) or 2,6-bis[(4S)-isopropyloxazolin-2-yl]pyridine acting as bidentate ligands (Heard et al., 1998).
In the crystal, molecules of the title compound are linked by weak intermolecular C—H⋯O interactions (Table 1).
Synthesis and crystallization
A mixture of Mo(CO)6 (0.10 g, 0.38 mmol) and an equimolar amount of the diimine ligand (0.67 g, 0.38 mmol) in dry toluene was refluxed under argon atmosphere and light exclusion overnight resulting in a deep-red solution. The solvent was removed in vacuo and the red residue was washed three times with n-pentane and diethyl ether. Recrystallization from CH2Cl2/n-pentane 2:1 gave deep-red crystals suitable for X-ray analysis. Yield 0.112 (76%). 1H NMR (300 MHz, CD2Cl2, p.p.m.) δ = 9.05 (d, J = 5.3 Hz, 1H), 7.95 (td, J = 7.7 Hz, 1.6 Hz, 1H), 7.87–7.83 (m, 1H), 7.50 (ddd, J = 7.3 Hz, 5.8 Hz, 1.5 Hz, 1H), 4.52 (s, 2H), 1.56 (s, 6H); 13C NMR (75 MHz, CDCl3, p.p.m.) δ = 256.8 (CO), 223.2 (CO), 203.7 (CO), 154.0 (C6Py), 137.6 (C4Py), 127.1 (C5Py), 124.6 (C3Py), 81.8 (C4Pyrox), 68.5 (C5Pyrox), 27.8 (CH3), signals for the quaternary carbon atoms C2Py and C2Pyrox were not detectable as it was also observed for a highly related manganese complex with the same diimine ligand (Steinlechner et al., 2019); IR: ν~(CO)/cm−1 = 2010, 1891, 1851, 1810; HR–MS (ESI): calcd. mass C13H12BrMoN2O4: 357.98511; found: 357.98100; elemental analysis: (calculated) C:43.77, H: 3.15, N:7.29; (found) C: 43.77, H: 3.07, N: 7.43.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1899206
https://doi.org/10.1107/S2414314619002839/im4003sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619002839/im4003Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).[Mo(C10H12N2O)(CO)4] | F(000) = 768 |
Mr = 384.20 | Dx = 1.698 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8166 (3) Å | Cell parameters from 9837 reflections |
b = 12.2837 (5) Å | θ = 2.2–30.6° |
c = 14.0636 (6) Å | µ = 0.90 mm−1 |
β = 99.3347 (11)° | T = 150 K |
V = 1502.93 (10) Å3 | Prism, red |
Z = 4 | 0.50 × 0.49 × 0.36 mm |
Bruker APEXII CCD diffractometer | 3993 independent reflections |
Radiation source: fine-focus sealed tube | 3889 reflections with I > 2σ(I) |
Detector resolution: 8.3333 pixels mm-1 | Rint = 0.017 |
φ and ω scans | θmax = 29.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −11→12 |
Tmin = 0.69, Tmax = 0.74 | k = −16→16 |
29586 measured reflections | l = −19→19 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.016 | H-atom parameters constrained |
wR(F2) = 0.043 | w = 1/[σ2(Fo2) + (0.0202P)2 + 0.6769P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.004 |
3993 reflections | Δρmax = 0.41 e Å−3 |
201 parameters | Δρmin = −0.44 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.80476 (13) | 0.45885 (9) | 0.99223 (8) | 0.0202 (2) | |
H1 | 0.8765 | 0.4015 | 1.0089 | 0.024* | |
C2 | 0.81678 (13) | 0.55152 (10) | 1.04953 (8) | 0.0228 (2) | |
H2 | 0.8953 | 0.5569 | 1.1042 | 0.027* | |
C3 | 0.71361 (14) | 0.63589 (10) | 1.02638 (9) | 0.0248 (2) | |
H3 | 0.7219 | 0.7008 | 1.0636 | 0.030* | |
C4 | 0.59747 (13) | 0.62380 (9) | 0.94757 (9) | 0.0222 (2) | |
H4 | 0.5233 | 0.6795 | 0.9305 | 0.027* | |
C5 | 0.59241 (12) | 0.52863 (9) | 0.89456 (8) | 0.01714 (19) | |
C6 | 0.47421 (12) | 0.50561 (9) | 0.81159 (8) | 0.01724 (19) | |
C7 | 0.26379 (14) | 0.53003 (10) | 0.70282 (9) | 0.0248 (2) | |
H7A | 0.2551 | 0.5782 | 0.6458 | 0.030* | |
H7B | 0.1597 | 0.5170 | 0.7183 | 0.030* | |
C8 | 0.34159 (12) | 0.42100 (9) | 0.68335 (8) | 0.0191 (2) | |
C9 | 0.23763 (15) | 0.32331 (11) | 0.68853 (10) | 0.0273 (2) | |
H9A | 0.2944 | 0.2563 | 0.6801 | 0.041* | |
H9B | 0.1481 | 0.3286 | 0.6374 | 0.041* | |
H9C | 0.2033 | 0.3220 | 0.7514 | 0.041* | |
C10 | 0.40366 (16) | 0.42340 (11) | 0.58851 (9) | 0.0282 (2) | |
H10A | 0.4746 | 0.4848 | 0.5886 | 0.042* | |
H10B | 0.3181 | 0.4317 | 0.5350 | 0.042* | |
H10C | 0.4582 | 0.3553 | 0.5808 | 0.042* | |
C11 | 0.61991 (14) | 0.18720 (10) | 0.71624 (9) | 0.0228 (2) | |
C12 | 0.57667 (13) | 0.20789 (9) | 0.89897 (8) | 0.0206 (2) | |
C13 | 0.87057 (14) | 0.23449 (10) | 0.85597 (9) | 0.0234 (2) | |
C14 | 0.78619 (15) | 0.38044 (11) | 0.70982 (10) | 0.0288 (3) | |
Mo1 | 0.67341 (2) | 0.30510 (2) | 0.80894 (2) | 0.01647 (4) | |
N1 | 0.69605 (10) | 0.44698 (7) | 0.91437 (7) | 0.01694 (17) | |
N2 | 0.47339 (10) | 0.41686 (7) | 0.76431 (7) | 0.01688 (17) | |
O1 | 0.36316 (10) | 0.57885 (7) | 0.78477 (6) | 0.02363 (17) | |
O2 | 0.58250 (12) | 0.11532 (8) | 0.66411 (7) | 0.0349 (2) | |
O3 | 0.52810 (11) | 0.14502 (8) | 0.94630 (7) | 0.03051 (19) | |
O4 | 0.99039 (12) | 0.19647 (8) | 0.88247 (8) | 0.0361 (2) | |
O5 | 0.85256 (15) | 0.41239 (12) | 0.65282 (10) | 0.0525 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0178 (5) | 0.0222 (5) | 0.0203 (5) | 0.0002 (4) | 0.0024 (4) | −0.0003 (4) |
C2 | 0.0204 (5) | 0.0283 (6) | 0.0193 (5) | −0.0023 (4) | 0.0016 (4) | −0.0047 (4) |
C3 | 0.0249 (5) | 0.0240 (5) | 0.0253 (6) | −0.0021 (4) | 0.0038 (4) | −0.0094 (4) |
C4 | 0.0218 (5) | 0.0193 (5) | 0.0257 (5) | 0.0014 (4) | 0.0038 (4) | −0.0049 (4) |
C5 | 0.0160 (4) | 0.0168 (5) | 0.0188 (5) | −0.0004 (4) | 0.0032 (4) | −0.0013 (4) |
C6 | 0.0160 (4) | 0.0162 (5) | 0.0195 (5) | 0.0011 (4) | 0.0030 (4) | 0.0008 (4) |
C7 | 0.0201 (5) | 0.0238 (5) | 0.0277 (6) | 0.0024 (4) | −0.0041 (4) | −0.0006 (4) |
C8 | 0.0188 (5) | 0.0186 (5) | 0.0186 (5) | −0.0018 (4) | −0.0007 (4) | 0.0009 (4) |
C9 | 0.0239 (6) | 0.0263 (6) | 0.0299 (6) | −0.0083 (5) | −0.0015 (5) | 0.0019 (5) |
C10 | 0.0324 (6) | 0.0332 (6) | 0.0187 (5) | −0.0029 (5) | 0.0031 (5) | 0.0012 (5) |
C11 | 0.0219 (5) | 0.0238 (5) | 0.0229 (5) | 0.0034 (4) | 0.0039 (4) | −0.0025 (4) |
C12 | 0.0191 (5) | 0.0209 (5) | 0.0206 (5) | 0.0018 (4) | −0.0002 (4) | −0.0049 (4) |
C13 | 0.0237 (5) | 0.0202 (5) | 0.0268 (6) | 0.0023 (4) | 0.0053 (4) | −0.0028 (4) |
C14 | 0.0244 (6) | 0.0292 (6) | 0.0338 (6) | 0.0018 (5) | 0.0074 (5) | 0.0004 (5) |
Mo1 | 0.01612 (5) | 0.01496 (5) | 0.01826 (5) | 0.00169 (3) | 0.00256 (3) | −0.00258 (3) |
N1 | 0.0160 (4) | 0.0164 (4) | 0.0186 (4) | −0.0001 (3) | 0.0034 (3) | −0.0015 (3) |
N2 | 0.0157 (4) | 0.0169 (4) | 0.0175 (4) | 0.0000 (3) | 0.0011 (3) | −0.0004 (3) |
O1 | 0.0221 (4) | 0.0188 (4) | 0.0278 (4) | 0.0061 (3) | −0.0028 (3) | −0.0021 (3) |
O2 | 0.0370 (5) | 0.0319 (5) | 0.0348 (5) | 0.0000 (4) | 0.0031 (4) | −0.0164 (4) |
O3 | 0.0329 (5) | 0.0296 (5) | 0.0291 (5) | −0.0049 (4) | 0.0050 (4) | 0.0036 (4) |
O4 | 0.0253 (5) | 0.0372 (6) | 0.0451 (6) | 0.0118 (4) | 0.0038 (4) | 0.0035 (4) |
O5 | 0.0479 (7) | 0.0630 (8) | 0.0537 (7) | −0.0011 (6) | 0.0295 (6) | 0.0126 (6) |
C1—N1 | 1.3411 (14) | C8—C9 | 1.5190 (16) |
C1—C2 | 1.3888 (16) | C8—C10 | 1.5219 (16) |
C1—H1 | 0.9500 | C9—H9A | 0.9800 |
C2—C3 | 1.3825 (17) | C9—H9B | 0.9800 |
C2—H2 | 0.9500 | C9—H9C | 0.9800 |
C3—C4 | 1.3895 (16) | C10—H10A | 0.9800 |
C3—H3 | 0.9500 | C10—H10B | 0.9800 |
C4—C5 | 1.3833 (15) | C10—H10C | 0.9800 |
C4—H4 | 0.9500 | C11—O2 | 1.1608 (15) |
C5—N1 | 1.3550 (14) | C11—Mo1 | 1.9545 (12) |
C5—C6 | 1.4605 (15) | C12—O3 | 1.1469 (15) |
C6—N2 | 1.2764 (14) | C12—Mo1 | 2.0265 (12) |
C6—O1 | 1.3381 (13) | C13—O4 | 1.1598 (16) |
C7—O1 | 1.4587 (14) | C13—Mo1 | 1.9592 (12) |
C7—C8 | 1.5492 (16) | C14—O5 | 1.1363 (18) |
C7—H7A | 0.9900 | C14—Mo1 | 2.0587 (13) |
C7—H7B | 0.9900 | Mo1—N2 | 2.2427 (9) |
C8—N2 | 1.4899 (13) | Mo1—N1 | 2.2758 (9) |
N1—C1—C2 | 122.69 (11) | H9A—C9—H9C | 109.5 |
N1—C1—H1 | 118.7 | H9B—C9—H9C | 109.5 |
C2—C1—H1 | 118.7 | C8—C10—H10A | 109.5 |
C3—C2—C1 | 119.50 (11) | C8—C10—H10B | 109.5 |
C3—C2—H2 | 120.2 | H10A—C10—H10B | 109.5 |
C1—C2—H2 | 120.2 | C8—C10—H10C | 109.5 |
C2—C3—C4 | 118.64 (11) | H10A—C10—H10C | 109.5 |
C2—C3—H3 | 120.7 | H10B—C10—H10C | 109.5 |
C4—C3—H3 | 120.7 | O2—C11—Mo1 | 176.39 (11) |
C5—C4—C3 | 118.38 (11) | O3—C12—Mo1 | 173.73 (10) |
C5—C4—H4 | 120.8 | O4—C13—Mo1 | 177.11 (11) |
C3—C4—H4 | 120.8 | O5—C14—Mo1 | 173.48 (13) |
N1—C5—C4 | 123.57 (10) | C11—Mo1—C13 | 90.12 (5) |
N1—C5—C6 | 113.01 (9) | C11—Mo1—C12 | 84.24 (5) |
C4—C5—C6 | 123.41 (10) | C13—Mo1—C12 | 88.20 (5) |
N2—C6—O1 | 119.03 (10) | C11—Mo1—C14 | 88.40 (5) |
N2—C6—C5 | 121.64 (10) | C13—Mo1—C14 | 85.87 (5) |
O1—C6—C5 | 119.32 (9) | C12—Mo1—C14 | 170.54 (5) |
O1—C7—C8 | 105.58 (9) | C11—Mo1—N2 | 99.97 (4) |
O1—C7—H7A | 110.6 | C13—Mo1—N2 | 168.48 (4) |
C8—C7—H7A | 110.6 | C12—Mo1—N2 | 98.28 (4) |
O1—C7—H7B | 110.6 | C14—Mo1—N2 | 88.83 (4) |
C8—C7—H7B | 110.6 | C11—Mo1—N1 | 171.17 (4) |
H7A—C7—H7B | 108.8 | C13—Mo1—N1 | 98.04 (4) |
N2—C8—C9 | 109.77 (9) | C12—Mo1—N1 | 92.61 (4) |
N2—C8—C10 | 108.88 (9) | C14—Mo1—N1 | 95.51 (5) |
C9—C8—C10 | 111.28 (10) | N2—Mo1—N1 | 72.27 (3) |
N2—C8—C7 | 101.97 (9) | C1—N1—C5 | 117.14 (9) |
C9—C8—C7 | 112.74 (10) | C1—N1—Mo1 | 126.21 (7) |
C10—C8—C7 | 111.75 (10) | C5—N1—Mo1 | 116.61 (7) |
C8—C9—H9A | 109.5 | C6—N2—C8 | 107.86 (9) |
C8—C9—H9B | 109.5 | C6—N2—Mo1 | 116.06 (7) |
H9A—C9—H9B | 109.5 | C8—N2—Mo1 | 135.66 (7) |
C8—C9—H9C | 109.5 | C6—O1—C7 | 105.34 (9) |
N1—C1—C2—C3 | −0.11 (18) | C4—C5—N1—Mo1 | −175.19 (9) |
C1—C2—C3—C4 | 1.91 (18) | C6—C5—N1—Mo1 | 5.07 (11) |
C2—C3—C4—C5 | −1.37 (18) | O1—C6—N2—C8 | 2.20 (13) |
C3—C4—C5—N1 | −1.03 (17) | C5—C6—N2—C8 | −178.33 (9) |
C3—C4—C5—C6 | 178.69 (11) | O1—C6—N2—Mo1 | 175.93 (8) |
N1—C5—C6—N2 | −0.35 (15) | C5—C6—N2—Mo1 | −4.60 (13) |
C4—C5—C6—N2 | 179.90 (11) | C9—C8—N2—C6 | −123.82 (11) |
N1—C5—C6—O1 | 179.12 (9) | C10—C8—N2—C6 | 114.14 (11) |
C4—C5—C6—O1 | −0.63 (16) | C7—C8—N2—C6 | −4.08 (11) |
O1—C7—C8—N2 | 4.53 (11) | C9—C8—N2—Mo1 | 64.25 (13) |
O1—C7—C8—C9 | 122.16 (10) | C10—C8—N2—Mo1 | −57.79 (13) |
O1—C7—C8—C10 | −111.62 (11) | C7—C8—N2—Mo1 | −176.01 (8) |
C2—C1—N1—C5 | −2.20 (16) | N2—C6—O1—C7 | 0.96 (14) |
C2—C1—N1—Mo1 | 175.57 (8) | C5—C6—O1—C7 | −178.52 (10) |
C4—C5—N1—C1 | 2.79 (16) | C8—C7—O1—C6 | −3.51 (12) |
C6—C5—N1—C1 | −176.95 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O2i | 0.95 | 2.61 | 3.2786 (15) | 128 |
C10—H10A···O4ii | 0.98 | 2.64 | 3.4880 (17) | 145 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3/2, y+1/2, −z+3/2. |
Funding information
CS acknowledges financial support from EU fund H2020-MSCA-ITN-2015 in Horizon 2020 as part of the NoNoMeCat (grant agreement No. 675020). The publication of this article was funded by the Open Access Fund of the Leibniz Association.
References
Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2014). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Datta, P., Sardar, D., Mukhopadhyay, A. P., López-Torres, E., Pastor, C. J. & Sinha, C. (2011). J. Organomet. Chem. 696, 488–495. CrossRef Google Scholar
Heard, P. J. & Tocher, D. A. (1998). J. Chem. Soc. Dalton Trans. pp. 2169–2176. Web of Science 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
Steinlechner, C., Roesel, A. F., Oberem, E., Päpcke, A., Rockstroh, N., Gloaguen, F., Lochbrunner, S., Ludwig, R., Spannenberg, A., Junge, H., Francke, R. & Beller, M. (2019). ACS Catal. pp. 2091–2100. CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.