Tetra­carbon­yl[4,4-dimethyl-2-(pyridin-2-yl)-2-oxazoline-κ2N,N′]molybdenum(0)

Steinlechner, C.; Spannenberg, A.; Junge, H.; Beller, M.

doi:10.1107/S2414314619002839

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 2| February 2019| x190283

https://doi.org/10.1107/S2414314619002839

Open

access

Tetracarbonyl[4,4-dimethyl-2-(pyridin-2-yl)-2-oxazoline-κ²N,N′]molybdenum(0)

Christoph Steinlechner,^a Anke Spannenberg,^a Henrik Junge ^a and Matthias Beller ^a ^*

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
^*Correspondence e-mail: matthias.beller@catalysis.de

Edited by W. Imhof, University Koblenz-Landau, Germany (Received 29 January 2019; accepted 25 February 2019; online 28 February 2019)

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 ).

Figure 1
Molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids correspond to 30% probability.

In the crystal, molecules of the title compound are linked by weak intermolecular C—H⋯O interactions (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 crystal structure 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 (C_6Py), 137.6 (C_4Py), 127.1 (C_5Py), 124.6 (C_3Py), 81.8 (C_4Pyrox), 68.5 (C_5Pyrox), 27.8 (CH₃), signals for the quaternary carbon atoms C_2Py and C_2Pyrox 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Mo(C₁₀H₁₂N2O)(CO)₄]
M_r	384.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	8.8166 (3), 12.2837 (5), 14.0636 (6)
β (°)	99.3347 (11)
V (Å³)	1502.93 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.90
Crystal size (mm)	0.50 × 0.49 × 0.36

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.69, 0.74
No. of measured, independent and observed [I > 2σ(I)] reflections	29586, 3993, 3889
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.043, 1.10
No. of reflections	3993
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.44
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), XP in SHELXTL and SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1899206

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619002839/im4003sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619002839/im4003Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: 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).

Tetracarbonyl[4,4-dimethyl-2-(pyridin-2-yl)-2-oxazoline-κ²N,N']molybdenum(0) top

Crystal data top

[Mo(C₁₀H₁₂N2O)(CO)₄]	F(000) = 768
M_r = 384.20	D_x = 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

Data collection top

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	R_int = 0.017
φ and ω scans	θ_max = 29.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −11→12
T_min = 0.69, T_max = 0.74	k = −16→16
29586 measured reflections	l = −19→19

Refinement top

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(F_o²) + (0.0202P)² + 0.6769P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.004
3993 reflections	Δρ_max = 0.41 e Å⁻³
201 parameters	Δρ_min = −0.44 e Å⁻³

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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.