Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003614/bm1444sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003614/bm1444Isup2.hkl |
CCDC reference: 166961
The title complex was obtained in small yield as a by-product of the reaction between cis-[Mo(CO)4(HNC5H10)2] and two equivalents of PPh2(C6H4F-4) in dichloromethane. Crystals were obtained by cooling the reaction mixture to 273 K and were separated manually from those of cis-[Mo(CO)4{PPh2(C6H4F-4)}2].
Analysis of the difference map and the displacement parameters of the (4-fluorophenyl)diphenylphosphine ligand revealed that the benzene ring with the para-fluoro substituent has two different orientations relative to the piperidine ligand. This has been modelled as a disorder of the F atom over the two rings, with an occupancy factor of 58.8 (7)% for the major component. Refinement of the Flack (1983) parameter showed the crystal to be racemically twinned, with 27 (3)% occupying the minor configuration within the crystal. [Please supply number of Friedel pairs used.] H atoms were added at idealized positions 0.93 Å from phenyl C atoms, 0.97 Å from methylene C atoms and 0.91 Å from N21; they were then refined using a riding model, with Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids. The minor disorder component is not shown for clarity. |
[Mo(C18H14F)(C5H11N)(CO)4] | F(000) = 1168 |
Mr = 573.39 | Dx = 1.454 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 13.601 (3) Å | Cell parameters from 6006 reflections |
b = 10.981 (3) Å | θ = 2–24° |
c = 17.973 (4) Å | µ = 0.60 mm−1 |
β = 102.598 (6)° | T = 301 K |
V = 2619.9 (11) Å3 | Block, pale yellow |
Z = 4 | 0.32 × 0.19 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 4597 independent reflections |
Radiation source: fine-focus sealed tube | 4121 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −16→16 |
Tmin = 0.831, Tmax = 0.899 | k = −12→13 |
12823 measured reflections | l = −21→21 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0352P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.004 |
4597 reflections | Δρmax = 0.33 e Å−3 |
327 parameters | Δρmin = −0.21 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.27 (3) |
[Mo(C18H14F)(C5H11N)(CO)4] | V = 2619.9 (11) Å3 |
Mr = 573.39 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 13.601 (3) Å | µ = 0.60 mm−1 |
b = 10.981 (3) Å | T = 301 K |
c = 17.973 (4) Å | 0.32 × 0.19 × 0.18 mm |
β = 102.598 (6)° |
Bruker SMART CCD area-detector diffractometer | 4597 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 4121 reflections with I > 2σ(I) |
Tmin = 0.831, Tmax = 0.899 | Rint = 0.048 |
12823 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.068 | Δρmax = 0.33 e Å−3 |
S = 1.00 | Δρmin = −0.21 e Å−3 |
4597 reflections | Absolute structure: Flack (1983) |
327 parameters | Absolute structure parameter: 0.27 (3) |
1 restraint |
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 | Occ. (<1) | |
Mo1 | 0.482828 (19) | 0.18247 (3) | 0.220565 (14) | 0.04238 (9) | |
P1 | 0.36045 (7) | 0.26762 (8) | 0.29794 (5) | 0.0446 (2) | |
C11A | 0.2316 (3) | 0.2621 (3) | 0.2411 (2) | 0.0487 (9) | |
C12A | 0.1603 (2) | 0.1838 (6) | 0.25977 (19) | 0.0601 (8) | |
H12A | 0.1747 | 0.1429 | 0.3062 | 0.072* | |
C13A | 0.0679 (3) | 0.1659 (7) | 0.2099 (3) | 0.0784 (15) | |
H13A | 0.0207 | 0.1131 | 0.2227 | 0.094* | |
C14A | 0.0467 (4) | 0.2262 (5) | 0.1420 (3) | 0.0781 (15) | 0.412 (7) |
F14A | −0.0423 (5) | 0.2111 (8) | 0.0934 (5) | 0.117 (4) | 0.412 (7) |
C14D | 0.0467 (4) | 0.2262 (5) | 0.1420 (3) | 0.0781 (15) | 0.588 (7) |
H14D | −0.0149 | 0.2129 | 0.1086 | 0.094* | 0.588 (7) |
C15A | 0.1125 (4) | 0.3041 (5) | 0.1222 (3) | 0.0714 (12) | |
H15A | 0.0955 | 0.3462 | 0.0763 | 0.086* | |
C16A | 0.2049 (3) | 0.3217 (4) | 0.1699 (2) | 0.0596 (10) | |
H16A | 0.2510 | 0.3740 | 0.1551 | 0.072* | |
C11B | 0.3872 (3) | 0.4276 (3) | 0.3255 (2) | 0.0483 (9) | |
C12B | 0.4774 (3) | 0.4489 (4) | 0.3787 (2) | 0.0633 (11) | |
H12B | 0.5187 | 0.3838 | 0.3984 | 0.076* | |
C13B | 0.5055 (4) | 0.5663 (5) | 0.4021 (3) | 0.0782 (15) | |
H13B | 0.5661 | 0.5801 | 0.4367 | 0.094* | |
C14B | 0.4440 (5) | 0.6623 (5) | 0.3743 (3) | 0.0847 (16) | 0.412 (7) |
H14B | 0.4621 | 0.7410 | 0.3911 | 0.102* | 0.412 (7) |
C14E | 0.4440 (5) | 0.6623 (5) | 0.3743 (3) | 0.0847 (16) | 0.588 (7) |
F14E | 0.4692 (5) | 0.7723 (5) | 0.4014 (4) | 0.118 (3) | 0.588 (7) |
C15B | 0.3572 (4) | 0.6430 (4) | 0.3225 (3) | 0.0801 (15) | |
H15B | 0.3165 | 0.7089 | 0.3033 | 0.096* | |
C16B | 0.3280 (3) | 0.5266 (4) | 0.2976 (2) | 0.0602 (11) | |
H16B | 0.2681 | 0.5150 | 0.2618 | 0.072* | |
C11C | 0.3441 (3) | 0.2047 (4) | 0.38868 (19) | 0.0501 (10) | |
C12C | 0.2965 (4) | 0.2711 (4) | 0.4358 (2) | 0.0726 (12) | |
H12C | 0.2761 | 0.3506 | 0.4227 | 0.087* | |
C13C | 0.2787 (5) | 0.2203 (5) | 0.5026 (3) | 0.0829 (17) | |
H13C | 0.2459 | 0.2654 | 0.5337 | 0.100* | |
C14C | 0.3093 (4) | 0.1055 (6) | 0.5221 (3) | 0.0836 (17) | |
H14C | 0.2976 | 0.0724 | 0.5670 | 0.100* | |
C15C | 0.3568 (4) | 0.0374 (5) | 0.4774 (3) | 0.0949 (17) | |
H15C | 0.3769 | −0.0418 | 0.4915 | 0.114* | |
C16C | 0.3752 (4) | 0.0878 (5) | 0.4098 (3) | 0.0744 (13) | |
H16C | 0.4085 | 0.0421 | 0.3793 | 0.089* | |
C1 | 0.5372 (3) | 0.0343 (4) | 0.2864 (2) | 0.0529 (10) | |
O1 | 0.5756 (3) | −0.0456 (3) | 0.32094 (18) | 0.0788 (9) | |
C2 | 0.5693 (3) | 0.1307 (3) | 0.1515 (2) | 0.0535 (9) | |
O2 | 0.6223 (3) | 0.1050 (3) | 0.11212 (19) | 0.0812 (9) | |
C3 | 0.5951 (3) | 0.2785 (4) | 0.2782 (2) | 0.0515 (9) | |
O3 | 0.6625 (2) | 0.3375 (3) | 0.30974 (17) | 0.0731 (8) | |
C4 | 0.4545 (3) | 0.3324 (4) | 0.1538 (2) | 0.0569 (10) | |
O4 | 0.4483 (3) | 0.4191 (3) | 0.11827 (19) | 0.0900 (11) | |
N21 | 0.3457 (2) | 0.0726 (3) | 0.15121 (16) | 0.0487 (7) | |
H21 | 0.2903 | 0.1147 | 0.1571 | 0.058* | |
C22 | 0.3322 (4) | −0.0510 (4) | 0.1790 (2) | 0.0746 (13) | |
H22A | 0.3323 | −0.0471 | 0.2329 | 0.089* | |
H22B | 0.3889 | −0.1010 | 0.1731 | 0.089* | |
C23 | 0.2359 (4) | −0.1108 (5) | 0.1375 (3) | 0.0928 (17) | |
H23A | 0.2335 | −0.1935 | 0.1560 | 0.111* | |
H23B | 0.1789 | −0.0669 | 0.1486 | 0.111* | |
C24 | 0.2270 (4) | −0.1135 (5) | 0.0523 (2) | 0.0797 (14) | |
H24A | 0.2774 | −0.1679 | 0.0401 | 0.096* | |
H24B | 0.1610 | −0.1435 | 0.0273 | 0.096* | |
C25 | 0.2419 (4) | 0.0114 (5) | 0.0248 (2) | 0.0840 (15) | |
H25A | 0.1854 | 0.0621 | 0.0301 | 0.101* | |
H25B | 0.2433 | 0.0080 | −0.0289 | 0.101* | |
C26 | 0.3388 (4) | 0.0686 (4) | 0.0686 (2) | 0.0771 (14) | |
H26A | 0.3954 | 0.0226 | 0.0586 | 0.093* | |
H26B | 0.3436 | 0.1509 | 0.0501 | 0.093* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.04345 (15) | 0.04365 (14) | 0.04083 (14) | −0.00124 (19) | 0.01087 (10) | −0.00172 (17) |
P1 | 0.0468 (5) | 0.0471 (5) | 0.0405 (5) | 0.0025 (4) | 0.0110 (4) | 0.0015 (4) |
C11A | 0.042 (2) | 0.052 (2) | 0.051 (2) | 0.0035 (18) | 0.0098 (17) | −0.0059 (17) |
C12A | 0.055 (2) | 0.070 (2) | 0.0581 (19) | −0.004 (4) | 0.0183 (16) | −0.005 (3) |
C13A | 0.051 (2) | 0.098 (4) | 0.090 (3) | −0.014 (3) | 0.024 (2) | −0.020 (3) |
C14A | 0.055 (3) | 0.094 (4) | 0.080 (3) | 0.009 (2) | 0.000 (2) | −0.018 (3) |
F14A | 0.067 (4) | 0.126 (9) | 0.134 (6) | 0.007 (5) | −0.026 (4) | −0.024 (5) |
C14D | 0.055 (3) | 0.094 (4) | 0.080 (3) | 0.009 (2) | 0.000 (2) | −0.018 (3) |
C15A | 0.065 (3) | 0.076 (3) | 0.064 (3) | 0.011 (2) | −0.007 (2) | −0.001 (2) |
C16A | 0.053 (2) | 0.065 (3) | 0.061 (3) | 0.003 (2) | 0.011 (2) | 0.011 (2) |
C11B | 0.051 (2) | 0.052 (2) | 0.047 (2) | 0.0038 (18) | 0.0200 (18) | −0.0025 (17) |
C12B | 0.070 (3) | 0.066 (3) | 0.054 (2) | −0.002 (2) | 0.015 (2) | −0.010 (2) |
C13B | 0.078 (4) | 0.084 (4) | 0.071 (3) | −0.013 (3) | 0.014 (3) | −0.024 (3) |
C14B | 0.101 (4) | 0.064 (4) | 0.103 (4) | −0.019 (3) | 0.052 (3) | −0.026 (3) |
C14E | 0.101 (4) | 0.064 (4) | 0.103 (4) | −0.019 (3) | 0.052 (3) | −0.026 (3) |
F14E | 0.146 (6) | 0.065 (3) | 0.156 (6) | −0.030 (4) | 0.059 (5) | −0.031 (4) |
C15B | 0.082 (3) | 0.059 (3) | 0.106 (4) | 0.008 (2) | 0.035 (3) | 0.003 (2) |
C16B | 0.055 (3) | 0.053 (2) | 0.075 (3) | 0.004 (2) | 0.019 (2) | 0.002 (2) |
C11C | 0.051 (2) | 0.058 (3) | 0.0420 (17) | 0.0004 (19) | 0.0117 (15) | 0.0019 (18) |
C12C | 0.104 (4) | 0.066 (3) | 0.054 (2) | 0.013 (3) | 0.030 (2) | 0.007 (2) |
C13C | 0.109 (4) | 0.095 (4) | 0.052 (3) | 0.001 (3) | 0.035 (3) | 0.001 (3) |
C14C | 0.081 (4) | 0.117 (5) | 0.058 (3) | −0.003 (3) | 0.028 (3) | 0.027 (3) |
C15C | 0.096 (4) | 0.096 (4) | 0.100 (4) | 0.019 (3) | 0.037 (3) | 0.048 (3) |
C16C | 0.082 (3) | 0.075 (3) | 0.074 (3) | 0.019 (3) | 0.036 (3) | 0.022 (2) |
C1 | 0.055 (3) | 0.055 (2) | 0.051 (2) | −0.002 (2) | 0.018 (2) | −0.006 (2) |
O1 | 0.094 (2) | 0.0621 (19) | 0.077 (2) | 0.0230 (19) | 0.0100 (18) | 0.0133 (17) |
C2 | 0.061 (2) | 0.047 (2) | 0.055 (2) | −0.0079 (17) | 0.018 (2) | −0.0071 (17) |
O2 | 0.093 (2) | 0.0738 (19) | 0.093 (2) | −0.0014 (18) | 0.056 (2) | −0.0147 (18) |
C3 | 0.055 (3) | 0.057 (2) | 0.044 (2) | −0.002 (2) | 0.0127 (18) | 0.0017 (18) |
O3 | 0.0556 (18) | 0.084 (2) | 0.074 (2) | −0.0145 (17) | 0.0021 (15) | −0.0158 (17) |
C4 | 0.051 (2) | 0.063 (3) | 0.054 (2) | −0.008 (2) | 0.0045 (19) | 0.001 (2) |
O4 | 0.094 (2) | 0.074 (2) | 0.090 (2) | −0.0173 (19) | −0.0064 (19) | 0.036 (2) |
N21 | 0.0497 (19) | 0.0497 (18) | 0.0477 (17) | −0.0021 (14) | 0.0126 (14) | −0.0047 (14) |
C22 | 0.093 (3) | 0.072 (3) | 0.054 (2) | −0.030 (3) | 0.006 (2) | 0.008 (2) |
C23 | 0.108 (4) | 0.097 (4) | 0.065 (3) | −0.060 (3) | 0.001 (3) | 0.007 (3) |
C24 | 0.090 (3) | 0.077 (3) | 0.070 (3) | −0.026 (3) | 0.014 (3) | −0.024 (3) |
C25 | 0.095 (4) | 0.100 (4) | 0.050 (3) | −0.033 (3) | 0.002 (2) | −0.005 (2) |
C26 | 0.099 (4) | 0.079 (3) | 0.048 (2) | −0.039 (3) | 0.005 (2) | 0.001 (2) |
Mo1—C1 | 2.053 (5) | N21—C22 | 1.472 (5) |
Mo1—C2 | 1.971 (4) | C22—C23 | 1.509 (6) |
Mo1—C3 | 1.956 (4) | C23—C24 | 1.508 (6) |
Mo1—C4 | 2.024 (4) | C24—C25 | 1.487 (7) |
Mo1—N21 | 2.339 (3) | C25—C26 | 1.516 (6) |
Mo1—P1 | 2.5670 (10) | N21—H21 | 0.91 |
P1—C11A | 1.827 (4) | C12A—H12A | 0.93 |
P1—C11B | 1.840 (4) | C12B—H12B | 0.93 |
P1—C11C | 1.829 (4) | C12C—H12C | 0.93 |
C11A—C12A | 1.391 (6) | C13A—H13A | 0.93 |
C11A—C16A | 1.411 (5) | C13B—H13B | 0.93 |
C12A—C13A | 1.390 (5) | C13C—H13C | 0.93 |
C13A—C14A | 1.362 (8) | C14C—H14C | 0.93 |
C14A—F14A | 1.339 (8) | C14E—H14B | 0.93 |
C14A—C15A | 1.341 (7) | C15A—H15A | 0.93 |
C15A—C16A | 1.373 (6) | C15B—H15B | 0.93 |
C11B—C16B | 1.381 (5) | C15C—H15C | 0.93 |
C11B—C12B | 1.401 (5) | C16A—H16A | 0.93 |
C12B—C13B | 1.384 (7) | C16B—H16B | 0.93 |
C13B—C14B | 1.371 (8) | C16C—H16C | 0.93 |
C14B—C15B | 1.351 (7) | C22—H22A | 0.97 |
C15B—C16B | 1.384 (6) | C22—H22B | 0.97 |
C11C—C16C | 1.380 (6) | C23—H23A | 0.97 |
C11C—C12C | 1.380 (5) | C23—H23B | 0.97 |
C12C—C13C | 1.392 (6) | C24—H24A | 0.97 |
C13C—C14C | 1.349 (7) | C24—H24B | 0.97 |
C14C—C15C | 1.360 (8) | C25—H25A | 0.97 |
C15C—C16C | 1.407 (6) | C25—H25B | 0.97 |
C1—O1 | 1.134 (5) | C26—H26A | 0.97 |
C2—O2 | 1.150 (4) | C26—H26B | 0.97 |
C3—O3 | 1.164 (4) | C14A—H14D | 0.93 |
C4—O4 | 1.140 (5) | C14B—H14B | 0.93 |
N21—C26 | 1.467 (5) | ||
C1—Mo1—C2 | 86.87 (15) | C25—C24—C23 | 109.4 (4) |
C1—Mo1—C3 | 88.88 (17) | C24—C25—C26 | 112.0 (4) |
C1—Mo1—C4 | 169.94 (17) | N21—C26—C25 | 113.3 (4) |
C1—Mo1—N21 | 92.50 (13) | C26—N21—H21 | 105.4 |
C1—Mo1—P1 | 99.85 (10) | C22—N21—H21 | 105.1 |
C2—Mo1—C3 | 89.15 (16) | Mo1—N21—H21 | 105.0 |
C2—Mo1—C4 | 85.63 (16) | C13A—C12A—H12A | 119.4 |
C2—Mo1—N21 | 91.80 (13) | C11A—C12A—H12A | 119.9 |
C2—Mo1—P1 | 173.15 (12) | C13B—C12B—H12B | 119.6 |
C3—Mo1—C4 | 84.32 (16) | C11B—C12B—H12B | 120.0 |
C3—Mo1—N21 | 178.36 (15) | C11C—C12C—H12C | 119.9 |
C3—Mo1—P1 | 92.29 (12) | C13C—C12C—H12C | 119.8 |
C4—Mo1—N21 | 94.42 (13) | C12A—C13A—H13A | 120.5 |
C4—Mo1—P1 | 87.85 (12) | C12B—C13B—H13B | 120.2 |
N21—Mo1—P1 | 86.60 (8) | C14C—C13C—H13C | 120.0 |
C11A—P1—C11C | 101.42 (17) | C12C—C13C—H13C | 120.0 |
C11A—P1—C11B | 106.96 (17) | C13C—C14C—H14C | 119.4 |
C11C—P1—C11B | 100.14 (17) | C15C—C14C—H14C | 119.5 |
C11A—P1—Mo1 | 109.93 (11) | C15B—C14E—H14B | 119.0 |
C11C—P1—Mo1 | 124.41 (13) | C16A—C15A—H15A | 119.9 |
C11B—P1—Mo1 | 112.32 (11) | C16B—C15B—H15B | 119.6 |
C12A—C11A—C16A | 116.8 (3) | C14C—C15C—H15C | 120.0 |
C12A—C11A—P1 | 121.3 (3) | C16C—C15C—H15C | 120.5 |
C16A—C11A—P1 | 121.1 (3) | C15A—C16A—H16A | 119.5 |
C13A—C12A—C11A | 120.7 (5) | C11A—C16A—H16A | 119.5 |
C14A—C13A—C12A | 119.6 (5) | C11B—C16B—H16B | 119.9 |
F14A—C14A—C15A | 117.7 (6) | C15B—C16B—H16B | 119.7 |
F14A—C14A—C13A | 120.6 (6) | C11C—C16C—H16C | 119.7 |
C15A—C14A—C13A | 121.7 (4) | C15C—C16C—H16C | 119.8 |
C14A—C15A—C16A | 119.8 (5) | N21—C22—H22A | 109.2 |
C15A—C16A—C11A | 121.3 (4) | C23—C22—H22A | 109.0 |
C16B—C11B—C12B | 118.1 (4) | N21—C22—H22B | 108.8 |
C16B—C11B—P1 | 126.0 (3) | C23—C22—H22B | 109.1 |
C12B—C11B—P1 | 115.8 (3) | H22A—C22—H22B | 107.8 |
C13B—C12B—C11B | 120.4 (5) | C22—C23—H23A | 108.9 |
C14B—C13B—C12B | 120.0 (5) | C24—C23—H23A | 109.2 |
C15B—C14B—C13B | 120.2 (5) | C22—C23—H23B | 109.4 |
C14B—C15B—C16B | 121.0 (5) | C24—C23—H23B | 109.3 |
C11B—C16B—C15B | 120.4 (4) | H23A—C23—H23B | 107.9 |
C16C—C11C—C12C | 118.7 (4) | C25—C24—H24A | 109.6 |
C16C—C11C—P1 | 120.5 (3) | C23—C24—H24A | 109.9 |
C12C—C11C—P1 | 120.8 (3) | C25—C24—H24B | 110.0 |
C11C—C12C—C13C | 120.7 (4) | C23—C24—H24B | 109.5 |
C14C—C13C—C12C | 119.8 (5) | H24A—C24—H24B | 108.3 |
C13C—C14C—C15C | 121.3 (5) | C24—C25—H25A | 108.9 |
C14C—C15C—C16C | 119.4 (5) | C26—C25—H25A | 109.3 |
C11C—C16C—C15C | 120.1 (5) | C24—C25—H25B | 109.3 |
O1—C1—Mo1 | 173.6 (4) | C26—C25—H25B | 109.1 |
O2—C2—Mo1 | 177.0 (3) | H25A—C25—H25B | 107.9 |
O3—C3—Mo1 | 177.2 (3) | N21—C26—H26A | 109.2 |
O4—C4—Mo1 | 173.4 (4) | C25—C26—H26A | 109.0 |
C26—N21—C22 | 109.2 (3) | N21—C26—H26B | 108.7 |
C26—N21—Mo1 | 115.0 (2) | C25—C26—H26B | 108.8 |
C22—N21—Mo1 | 116.0 (2) | H26A—C26—H26B | 107.8 |
N21—C22—C23 | 113.1 (4) | C15B—C14B—H14B | 119.9 |
C24—C23—C22 | 112.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···C11a | 0.91 | 2.46 | 3.231 (4) | 142 |
N21—H21···C16a | 0.91 | 2.59 | 3.398 (5) | 148 |
C14C—H14C···O1i | 0.93 | 2.68 | 3.352 (6) | 130 |
C13C—H13C···O3i | 0.93 | 2.93 | 3.535 (6) | 124 |
C23—H23A···O2ii | 0.97 | 2.70 | 3.467 (6) | 137 |
C24—H24B···O4iii | 0.97 | 2.80 | 3.468 (6) | 127 |
C24—H24A···F14Aiv | 0.97 | 2.77 | 3.618 (9) | 146 |
Symmetry codes: (i) −x+1, y, −z+1; (ii) x−1/2, y−1/2, z; (iii) −x+1/2, y−1/2, −z; (iv) x+1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Mo(C18H14F)(C5H11N)(CO)4] |
Mr | 573.39 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 301 |
a, b, c (Å) | 13.601 (3), 10.981 (3), 17.973 (4) |
β (°) | 102.598 (6) |
V (Å3) | 2619.9 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.32 × 0.19 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.831, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12823, 4597, 4121 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.068, 1.00 |
No. of reflections | 4597 |
No. of parameters | 327 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.21 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.27 (3) |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXTL (Sheldrick, 1997), SHELXTL.
Mo1—C1 | 2.053 (5) | P1—C11B | 1.840 (4) |
Mo1—C2 | 1.971 (4) | P1—C11C | 1.829 (4) |
Mo1—C3 | 1.956 (4) | C14A—F14A | 1.339 (8) |
Mo1—C4 | 2.024 (4) | C1—O1 | 1.134 (5) |
Mo1—N21 | 2.339 (3) | C2—O2 | 1.150 (4) |
Mo1—P1 | 2.5670 (10) | C3—O3 | 1.164 (4) |
P1—C11A | 1.827 (4) | C4—O4 | 1.140 (5) |
C1—Mo1—C2 | 86.87 (15) | C2—Mo1—P1 | 173.15 (12) |
C1—Mo1—C3 | 88.88 (17) | C3—Mo1—C4 | 84.32 (16) |
C1—Mo1—C4 | 169.94 (17) | C3—Mo1—N21 | 178.36 (15) |
C1—Mo1—N21 | 92.50 (13) | C3—Mo1—P1 | 92.29 (12) |
C1—Mo1—P1 | 99.85 (10) | C4—Mo1—N21 | 94.42 (13) |
C2—Mo1—C3 | 89.15 (16) | C4—Mo1—P1 | 87.85 (12) |
C2—Mo1—C4 | 85.63 (16) | N21—Mo1—P1 | 86.60 (8) |
C2—Mo1—N21 | 91.80 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···C11a | 0.91 | 2.46 | 3.231 (4) | 142 |
N21—H21···C16a | 0.91 | 2.59 | 3.398 (5) | 148 |
C14C—H14C···O1i | 0.93 | 2.68 | 3.352 (6) | 130 |
C13C—H13C···O3i | 0.93 | 2.93 | 3.535 (6) | 124 |
C23—H23A···O2ii | 0.97 | 2.70 | 3.467 (6) | 137 |
C24—H24B···O4iii | 0.97 | 2.80 | 3.468 (6) | 127 |
C24—H24A···F14Aiv | 0.97 | 2.77 | 3.618 (9) | 146 |
Symmetry codes: (i) −x+1, y, −z+1; (ii) x−1/2, y−1/2, z; (iii) −x+1/2, y−1/2, −z; (iv) x+1/2, y−1/2, z. |
The molybdenum(0) complex cis-[Mo(CO)4(HNC5H10)2] is a convenient precursor for a range of cis-[Mo(CO)4L2] (L = phosphine, phosphite etc) complexes. Structural studies on a wide range of such complexes have been reported. However, to date, the structure of only one other intermediate piperidine–phosphine complex, namely cis-[Mo((CO)4(HNC5H10)(PR3)], has been reported (Cotton et al., 1982a). A diffraction study of cis-tetracarbonyl[(4-fluorophenyl)diphenylphosphine-P](piperidine-N)- molybdenum(0), (I) (Fig. 1), reveals a similar structure to that of [Mo(CO)4(HNC5H10)(PPhMe2)] [(II); Cotton et al., 1982b], but with a significantly smaller P—Mo—N angle [86.28 (7)° for (I) versus 90.77 (7)° for (II); see Table 1]. The piperidine ligand of (I) exhibits the expected chair conformation, and the distances and angles of this ligand are similar to those found for (II).
The geometry about the P atom is distorted tetrahedral and similar to the analogous complex cis-[Mo(CO)4{P(C6H4F-4)3}2] [(III); Alyea et al., 1994]. The molecules of (I) are involved in a number of C—H···O intermolcular interactions from both the piperidine and the phenyl groups, forming a three-dimensional network (see Table 2). The ability of C—H to act as a hydrogen-bond donor to oxygen was established by Taylor & Kennard (1982). They showed that C—H···O interactions (i) are essentially electrostatic in nature, (ii) show C···O distances ranging from 3 to 4 Å and (iii) are likely to be linear. The phosphine ligands are involved in C—H···π and π–π hydrogen-bond interactions with contacts from the ring centres to H atoms of 3.5 and 3.1 Å, respectively. These C—H···π and π–π interactions combine to form chains along the c axis and these chains can be thought of as containing C—H···π/π–π dimers linked via C—H···π interactions. These C—H···π/π–π interactions between the phenyl rings of phenyl phosphines are well known and have been extensively investigated by Dance and co-workers (Dance & Scudder, 1995, 1996a,b; Lewis & Dance, 2000). The steric demands of the Mo coordination sphere promote formation of an unusual intramolecular N—H···π hydrogen bond between one of the phenyl rings and the N atom of the piperidine moeity. The fluoro substitutent of the 4-fluorophenyl ring is disorderd over two rings, with a 58% occupancy for the major position, which is involved in an intermolecular C—H···F interaction with the piperidine moeity (Table 2). A comparison of the Mo—P bond lengths for (I) and (II) (Cotton et al., 1982b), and the related complex (III) (Alyea et al., 1994), which contains parafluorophenyl groups, shows that the Mo—P bond in (I) is shorter than in (II); the values are 2.5670 (10) and 2.576 (2) Å, respectively, and are consistent with the Mo—P bond length of 2.5644 (4) Å in (III). Evidently, while the presence of an F atom in the para position of the phenyl ring has no effect upon the P—C distances and P—C—P angles, it does reduce the Mo—P distance significantly; this is consistent with the steric argument put forward by Alyea et al. (1994).