metal-organic compounds
trans-Tetracarbonylbis(triphenylphosphane-κP)molybdenum(0)
aDepartment of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA
*Correspondence e-mail: npm@uic.edu
The well known title compound, trans-[Mo(C18H15P)2(CO)4], has not been studied previously by X-ray crystallography, unlike its cis isomer. The complex possesses crystallographically imposed inversion symmetry, with the Mo atom residing on an inversion centre (1a Wyckoff position). The two triphenylphosphane groups are arranged in a staggered orientation. Each of the phenyl groups exhibits significantly different Mo—P—C—C torsion angles ranging from 2.6 (2) to 179.4 (1)°, most likely due to steric interactions based upon their positions relative to the carbonyl ligands.
CCDC reference: 980083
Related literature
For the synthesis of the title compound and a structural study of its cis isomer, see: Cotton et al. (1982). For ligand dissociation and thermal reactivity of similar compounds, see: Darensbourg & Kump (1978). For an IR analysis of metal carbonyls, see: Haas & Sheline (1967). For kinetic investigations of metal–phosphanes, see: Darensbourg & Bischoff (1993).
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
CCDC reference: 980083
10.1107/S1600536814000300/pj2007sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814000300/pj2007Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814000300/pj2007Isup3.cml
We initiated this study as part of an undergraduate teaching lab using the Bruker SMART X2S bench-top diffractometer. Students use FT—IR spectroscopy to propose whether unknown samples are either the cis- or trans-isomer, and then use crystallography to test their hypotheses. To our surprise, the trans-isomer had not been reported in the CSD. In our hands, dissolving the trans-isomer in dichloromethane causes reversion to the cis-isomer. Crystallization from chloroform, on the other hand, provides the trans arrangement cleanly.
The 0 1 0 and 0 0 1 reflections were omitted from final refinements because of the suspicion that they were affected by the beamstop. Hydrogen atoms were placed at calculated positions 0.93 angstroms from the phenyl carbons and refined using the standard riding model with Uiso(H) set to 1.2 times Ueq(C).
For the synthesis of the title compound and a structural study of its cis isomer, see: Cotton et al. (1982). For ligand dissociation and thermal reactivity of similar compounds, see: Darensbourg & Kump (1978). For an IR analysis of metal carbonyls, see: Haas & Sheline (1967). For kinetic investigations of metal–phosphanes, see: Darensbourg & Bischoff (1993).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Mo(C18H15P)2(CO)4] | Z = 1 |
Mr = 732.52 | F(000) = 374 |
Triclinic, P1 | Dx = 1.403 Mg m−3 |
a = 9.3443 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.2267 (15) Å | Cell parameters from 6345 reflections |
c = 10.7258 (16) Å | θ = 2.2–25.1° |
α = 64.794 (4)° | µ = 0.51 mm−1 |
β = 69.417 (4)° | T = 300 K |
γ = 83.699 (4)° | Block, yellow |
V = 867.2 (2) Å3 | 0.62 × 0.45 × 0.33 mm |
Bruker SMART X2S benchtop diffractometer | 2907 independent reflections |
Radiation source: XOS X-beam microfocus source | 2770 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.020 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 24.7°, θmin = 2.3° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | k = −12→12 |
Tmin = 0.70, Tmax = 0.85 | l = −12→12 |
7865 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0238P)2 + 0.3878P] where P = (Fo2 + 2Fc2)/3 |
2907 reflections | (Δ/σ)max = 0.001 |
214 parameters | Δρmax = 0.25 e Å−3 |
61 restraints | Δρmin = −0.28 e Å−3 |
[Mo(C18H15P)2(CO)4] | γ = 83.699 (4)° |
Mr = 732.52 | V = 867.2 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.3443 (13) Å | Mo Kα radiation |
b = 10.2267 (15) Å | µ = 0.51 mm−1 |
c = 10.7258 (16) Å | T = 300 K |
α = 64.794 (4)° | 0.62 × 0.45 × 0.33 mm |
β = 69.417 (4)° |
Bruker SMART X2S benchtop diffractometer | 2907 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 2770 reflections with I > 2σ(I) |
Tmin = 0.70, Tmax = 0.85 | Rint = 0.020 |
7865 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 61 restraints |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.25 e Å−3 |
2907 reflections | Δρmin = −0.28 e Å−3 |
214 parameters |
Experimental. For synthesis of the compound, see Cotton (1982). Yellow crystals of the title compound suitable for X-ray diffraction were obtained by layering methanol above a chloroform solution of the title compound and allowing the layers to mix gradually. This crystallization method was performed on the bench with reagent grade solvents and without use of an inert atmosphere. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
Mo1 | 0 | 0 | 1.0 | 0.02814 (8) | |
P1 | 0.21394 (5) | 0.16894 (5) | 0.79865 (5) | 0.02888 (12) | |
O1 | 0.0078 (2) | 0.1374 (2) | 1.21320 (19) | 0.0659 (5) | |
O2 | 0.2517 (2) | −0.22032 (19) | 1.0879 (2) | 0.0677 (5) | |
C1 | 0.0065 (2) | 0.0886 (2) | 1.1355 (2) | 0.0396 (4) | |
C2 | 0.1594 (2) | −0.1425 (2) | 1.0585 (2) | 0.0400 (4) | |
C5 | 0.2591 (2) | 0.3109 (2) | 0.8425 (2) | 0.0360 (4) | |
C6 | 0.3274 (3) | 0.2769 (3) | 0.9478 (2) | 0.0516 (5) | |
H6 | 0.3582 | 0.1834 | 0.99 | 0.062* | |
C7 | 0.3502 (3) | 0.3800 (3) | 0.9906 (3) | 0.0643 (7) | |
H7 | 0.3976 | 0.3557 | 1.0602 | 0.077* | |
C8 | 0.3043 (4) | 0.5164 (3) | 0.9327 (3) | 0.0750 (8) | |
H8 | 0.3201 | 0.5855 | 0.9619 | 0.09* | |
C9 | 0.2344 (4) | 0.5514 (3) | 0.8306 (4) | 0.0842 (9) | |
H9 | 0.2014 | 0.6445 | 0.7915 | 0.101* | |
C10 | 0.2122 (3) | 0.4496 (3) | 0.7848 (3) | 0.0604 (6) | |
H10 | 0.1654 | 0.4753 | 0.7146 | 0.072* | |
C11 | 0.3989 (2) | 0.0886 (2) | 0.7434 (2) | 0.0375 (4) | |
C12 | 0.3988 (3) | −0.0338 (2) | 0.7195 (3) | 0.0527 (6) | |
H12 | 0.3059 | −0.0751 | 0.7371 | 0.063* | |
C13 | 0.5324 (3) | −0.0962 (3) | 0.6703 (3) | 0.0684 (7) | |
H13 | 0.5289 | −0.1772 | 0.6529 | 0.082* | |
C14 | 0.6677 (3) | −0.0407 (4) | 0.6475 (3) | 0.0800 (9) | |
H14 | 0.7578 | −0.0844 | 0.6167 | 0.096* | |
C15 | 0.6720 (3) | 0.0795 (4) | 0.6694 (4) | 0.0992 (12) | |
H15 | 0.7659 | 0.119 | 0.6516 | 0.119* | |
C16 | 0.5381 (3) | 0.1452 (3) | 0.7183 (4) | 0.0735 (8) | |
H16 | 0.5431 | 0.2271 | 0.7339 | 0.088* | |
C17 | 0.1953 (2) | 0.27353 (19) | 0.61689 (19) | 0.0348 (4) | |
C18 | 0.3120 (3) | 0.3699 (2) | 0.5024 (2) | 0.0542 (6) | |
H18 | 0.4008 | 0.3822 | 0.5174 | 0.065* | |
C19 | 0.2971 (3) | 0.4474 (3) | 0.3666 (3) | 0.0668 (7) | |
H19 | 0.3751 | 0.5128 | 0.2912 | 0.08* | |
C20 | 0.1676 (4) | 0.4284 (3) | 0.3421 (2) | 0.0657 (7) | |
H20 | 0.1576 | 0.4813 | 0.2506 | 0.079* | |
C21 | 0.0550 (3) | 0.3322 (3) | 0.4515 (3) | 0.0659 (7) | |
H21 | −0.0316 | 0.3174 | 0.4346 | 0.079* | |
C22 | 0.0681 (3) | 0.2555 (2) | 0.5893 (2) | 0.0485 (5) | |
H22 | −0.0109 | 0.1909 | 0.6641 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.02853 (13) | 0.02430 (12) | 0.02774 (12) | −0.00060 (8) | −0.00954 (9) | −0.00693 (9) |
P1 | 0.0288 (3) | 0.0261 (2) | 0.0290 (2) | −0.00119 (18) | −0.00896 (19) | −0.00910 (19) |
O1 | 0.0699 (12) | 0.0822 (12) | 0.0664 (11) | 0.0004 (9) | −0.0223 (9) | −0.0497 (10) |
O2 | 0.0675 (11) | 0.0606 (10) | 0.0694 (11) | 0.0316 (9) | −0.0346 (10) | −0.0197 (9) |
C1 | 0.0355 (11) | 0.0402 (11) | 0.0406 (11) | −0.0005 (8) | −0.0115 (9) | −0.0150 (9) |
C2 | 0.0432 (12) | 0.0351 (10) | 0.0358 (10) | 0.0027 (9) | −0.0130 (9) | −0.0100 (8) |
C5 | 0.0347 (10) | 0.0355 (10) | 0.0353 (10) | −0.0054 (8) | −0.0057 (8) | −0.0156 (8) |
C6 | 0.0599 (14) | 0.0485 (12) | 0.0477 (12) | −0.0108 (10) | −0.0196 (11) | −0.0170 (10) |
C7 | 0.0701 (17) | 0.0782 (18) | 0.0525 (14) | −0.0245 (14) | −0.0167 (12) | −0.0311 (13) |
C8 | 0.088 (2) | 0.0738 (19) | 0.0778 (19) | −0.0188 (15) | −0.0106 (16) | −0.0531 (16) |
C9 | 0.110 (3) | 0.0520 (16) | 0.115 (3) | 0.0194 (16) | −0.046 (2) | −0.0537 (17) |
C10 | 0.0742 (17) | 0.0479 (13) | 0.0787 (17) | 0.0172 (12) | −0.0379 (14) | −0.0379 (13) |
C11 | 0.0330 (10) | 0.0387 (10) | 0.0354 (10) | 0.0038 (8) | −0.0102 (8) | −0.0122 (8) |
C12 | 0.0471 (13) | 0.0524 (13) | 0.0599 (14) | 0.0043 (10) | −0.0101 (11) | −0.0314 (11) |
C13 | 0.0693 (18) | 0.0652 (16) | 0.0713 (17) | 0.0220 (13) | −0.0159 (14) | −0.0399 (14) |
C14 | 0.0568 (17) | 0.099 (2) | 0.087 (2) | 0.0381 (16) | −0.0221 (15) | −0.0508 (19) |
C15 | 0.0332 (14) | 0.136 (3) | 0.151 (3) | 0.0142 (17) | −0.0281 (18) | −0.085 (3) |
C16 | 0.0379 (13) | 0.0846 (19) | 0.114 (2) | 0.0031 (12) | −0.0185 (14) | −0.0620 (19) |
C17 | 0.0421 (11) | 0.0287 (9) | 0.0281 (9) | 0.0027 (8) | −0.0091 (8) | −0.0094 (7) |
C18 | 0.0534 (14) | 0.0503 (13) | 0.0410 (12) | −0.0077 (10) | −0.0067 (10) | −0.0080 (10) |
C19 | 0.0797 (19) | 0.0506 (14) | 0.0345 (12) | −0.0025 (13) | 0.0013 (12) | −0.0006 (10) |
C20 | 0.092 (2) | 0.0577 (15) | 0.0327 (12) | 0.0155 (14) | −0.0212 (13) | −0.0079 (11) |
C21 | 0.0777 (18) | 0.0697 (16) | 0.0470 (13) | 0.0055 (14) | −0.0362 (13) | −0.0097 (12) |
C22 | 0.0520 (13) | 0.0496 (12) | 0.0361 (11) | −0.0042 (10) | −0.0186 (10) | −0.0062 (9) |
Mo1—C1 | 2.034 (2) | C11—C16 | 1.373 (3) |
Mo1—C1i | 2.034 (2) | C11—C12 | 1.380 (3) |
Mo1—C2i | 2.035 (2) | C12—C13 | 1.376 (3) |
Mo1—C2 | 2.035 (2) | C12—H12 | 0.93 |
Mo1—P1i | 2.4879 (5) | C13—C14 | 1.343 (4) |
Mo1—P1 | 2.4879 (5) | C13—H13 | 0.93 |
P1—C5 | 1.8341 (19) | C14—C15 | 1.353 (4) |
P1—C11 | 1.8430 (19) | C14—H14 | 0.93 |
P1—C17 | 1.8430 (19) | C15—C16 | 1.395 (4) |
O1—C1 | 1.143 (3) | C15—H15 | 0.93 |
O2—C2 | 1.141 (2) | C16—H16 | 0.93 |
C5—C10 | 1.376 (3) | C17—C22 | 1.370 (3) |
C5—C6 | 1.389 (3) | C17—C18 | 1.390 (3) |
C6—C7 | 1.378 (3) | C18—C19 | 1.381 (3) |
C6—H6 | 0.93 | C18—H18 | 0.93 |
C7—C8 | 1.354 (4) | C19—C20 | 1.374 (4) |
C7—H7 | 0.93 | C19—H19 | 0.93 |
C8—C9 | 1.367 (4) | C20—C21 | 1.352 (4) |
C8—H8 | 0.93 | C20—H20 | 0.93 |
C9—C10 | 1.386 (3) | C21—C22 | 1.390 (3) |
C9—H9 | 0.93 | C21—H21 | 0.93 |
C10—H10 | 0.93 | C22—H22 | 0.93 |
C1—Mo1—C1i | 180.00 (11) | C5—C10—H10 | 119.8 |
C1—Mo1—C2i | 89.09 (8) | C9—C10—H10 | 119.8 |
C1i—Mo1—C2i | 90.91 (8) | C16—C11—C12 | 117.4 (2) |
C1—Mo1—C2 | 90.91 (8) | C16—C11—P1 | 124.63 (17) |
C1i—Mo1—C2 | 89.09 (8) | C12—C11—P1 | 117.92 (16) |
C2i—Mo1—C2 | 180.0 | C13—C12—C11 | 121.8 (2) |
C1—Mo1—P1i | 89.67 (6) | C13—C12—H12 | 119.1 |
C1i—Mo1—P1i | 90.33 (6) | C11—C12—H12 | 119.1 |
C2i—Mo1—P1i | 87.97 (6) | C14—C13—C12 | 120.3 (3) |
C2—Mo1—P1i | 92.03 (6) | C14—C13—H13 | 119.9 |
C1—Mo1—P1 | 90.33 (6) | C12—C13—H13 | 119.9 |
C1i—Mo1—P1 | 89.67 (6) | C13—C14—C15 | 119.4 (3) |
C2i—Mo1—P1 | 92.04 (6) | C13—C14—H14 | 120.3 |
C2—Mo1—P1 | 87.97 (6) | C15—C14—H14 | 120.3 |
P1i—Mo1—P1 | 180.0 | C14—C15—C16 | 121.2 (3) |
C5—P1—C11 | 104.37 (9) | C14—C15—H15 | 119.4 |
C5—P1—C17 | 102.38 (9) | C16—C15—H15 | 119.4 |
C11—P1—C17 | 99.19 (9) | C11—C16—C15 | 119.8 (3) |
C5—P1—Mo1 | 112.63 (6) | C11—C16—H16 | 120.1 |
C11—P1—Mo1 | 116.61 (6) | C15—C16—H16 | 120.1 |
C17—P1—Mo1 | 119.47 (6) | C22—C17—C18 | 117.96 (19) |
O1—C1—Mo1 | 178.84 (18) | C22—C17—P1 | 121.05 (14) |
O2—C2—Mo1 | 178.21 (19) | C18—C17—P1 | 120.96 (16) |
C10—C5—C6 | 117.94 (19) | C19—C18—C17 | 120.5 (2) |
C10—C5—P1 | 121.47 (16) | C19—C18—H18 | 119.8 |
C6—C5—P1 | 120.24 (16) | C17—C18—H18 | 119.8 |
C7—C6—C5 | 120.8 (2) | C20—C19—C18 | 120.4 (2) |
C7—C6—H6 | 119.6 | C20—C19—H19 | 119.8 |
C5—C6—H6 | 119.6 | C18—C19—H19 | 119.8 |
C8—C7—C6 | 120.8 (3) | C21—C20—C19 | 119.7 (2) |
C8—C7—H7 | 119.6 | C21—C20—H20 | 120.2 |
C6—C7—H7 | 119.6 | C19—C20—H20 | 120.2 |
C7—C8—C9 | 119.3 (2) | C20—C21—C22 | 120.3 (3) |
C7—C8—H8 | 120.3 | C20—C21—H21 | 119.9 |
C9—C8—H8 | 120.3 | C22—C21—H21 | 119.9 |
C8—C9—C10 | 120.7 (3) | C17—C22—C21 | 121.2 (2) |
C8—C9—H9 | 119.6 | C17—C22—H22 | 119.4 |
C10—C9—H9 | 119.6 | C21—C22—H22 | 119.4 |
C5—C10—C9 | 120.4 (2) |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Mo(C18H15P)2(CO)4] |
Mr | 732.52 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 300 |
a, b, c (Å) | 9.3443 (13), 10.2267 (15), 10.7258 (16) |
α, β, γ (°) | 64.794 (4), 69.417 (4), 83.699 (4) |
V (Å3) | 867.2 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.51 |
Crystal size (mm) | 0.62 × 0.45 × 0.33 |
Data collection | |
Diffractometer | Bruker SMART X2S benchtop |
Absorption correction | Multi-scan (SADABS; Bruker, 2012) |
Tmin, Tmax | 0.70, 0.85 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7865, 2907, 2770 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.588 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.058, 1.11 |
No. of reflections | 2907 |
No. of parameters | 214 |
No. of restraints | 61 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.28 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).
Acknowledgements
The Department of Chemistry and the College of Liberal Arts & Sciences at UIC are acknowledged for purchasing a Bruker SMART X2S bench-top diffractometer, and for providing supplies and equipment for the inorganic teaching lab that motivated this study.
References
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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.
We initiated this study as part of an undergraduate teaching lab using the Bruker SMART X2S bench-top diffractometer. Students use FT—IR spectroscopy to propose whether unknown samples are either the cis- or trans-isomer, and then use crystallography to test their hypotheses. To our surprise, the trans-isomer had not been reported in the CSD. In our hands, dissolving the trans-isomer in dichloromethane causes reversion to the cis-isomer. Crystallization from chloroform, on the other hand, provides the trans arrangement cleanly.
The 0 1 0 and 0 0 1 reflections were omitted from final refinements because of the suspicion that they were affected by the beamstop. Hydrogen atoms were placed at calculated positions 0.93 angstroms from the phenyl carbons and refined using the standard riding model with Uiso(H) set to 1.2 times Ueq(C).