organic compounds Acta Crystallographica Section E
Experimental
Structure Reports Online
Crystal data
ISSN 1600-5368
Tris[3,5-bis(trifluoromethyl)phenyl]phosphine oxide Omar bin Shawkataly,a*‡ Mohd. Aslam A. Pankhi,a Mohamed Ismail Mohamed-Ibrahim,a M. Razak Hamdana and Hoong-Kun Funb a
Chemical Sciences Programme, School of Distance Education, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bX-Ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia Correspondence e-mail:
[email protected] Received 2 March 2009; accepted 9 April 2009
˚; Key indicators: single-crystal X-ray study; T = 294 K; mean (C–C) = 0.003 A disorder in main residue; R factor = 0.041; wR factor = 0.113; data-to-parameter ratio = 8.0.
= 106.562 (10) ˚3 V = 1327.7 (3) A Z=2 Mo K radiation = 0.25 mm1 T = 294 K 0.48 0.38 0.22 mm
C24H9F18OP Mr = 686.28 Triclinic, P1 ˚ a = 10.7937 (2) A ˚ b = 11.8786 (10) A ˚ c = 12.5066 (10) A = 111.065 (10) = 103.645 (10)
Data collection Bruker SMART APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2005) Tmin = 0.890, Tmax = 0.947
7134 measured reflections 4535 independent reflections 3611 reflections with I > 2(I) Rint = 0.021
Refinement R[F 2 > 2(F 2)] = 0.041 wR(F 2) = 0.113 S = 1.02 4535 reflections 565 parameters
168 restraints H-atom parameters constrained ˚ 3 max = 0.20 e A ˚ 3 min = 0.27 e A
Table 1 ˚ , ). Hydrogen-bond geometry (A
In the title compound, C24H9F18OP, an intramolecular C— H O short contact generates a five-membered ring, producing an S(5) ring motif. The dihedral angles between the benzene rings are 57.68 (10), 77.80 (11) and 79.48 (10) . Each of the six trifluoromethyl substituents shows rotational disorder over two positions with refined site-occupany ratios of 0.64 (3)/0.36 (3), 0.649 (14)/0.351 (14), 0.52 (2)/0.48 (2), 0.545 (16)/0.455 (16), 0.774 (9)/0.226 (9) and 0.63 (5)/0.37 (5). The crystal structure is stabilized by intermolecular C—H O and C—H F interactions.
Related literature For C—F bond lengths, see: Allen et al. (1987). For the stereochemistry of triphenylphosphine oxide complexes and for P—C bond distances, see: Bandoli et al. (1970); Ruban & Zabel (1976); Baures & Silverton (1990); Lynch et al. (1992); Shawkataly et al. (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995).
D—H A
D—H
H A
D A
D—H A
C18—H18A O1 C10—H10A O1i C20—H20A F10Aii
0.93 0.93 0.93
2.58 2.38 2.50
2.992 (3) 3.203 (3) 3.418 (12)
108 147 167
Symmetry codes: (i) x þ 1; y þ 1; z; (ii) x þ 1; y þ 1; z þ 1.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
The authors thank the Malaysian Government and Universiti Sains Malaysia for research grant 1001/PJJAUH/ 811115. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2588).
References
‡ On secondment to: Multimedia University, Melaka Campus, Jalan Ayer Keroh Lama, 75450 Melaka, Malaysia.
o1080
Shawkataly et al.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. Bandoli, G., Bortolozo, G., Clemente, D. A., Coratto, U. & Panottoni, C. (1970). J. Chem. Soc. A, pp. 2278–2280. Baures, P. W. & Silverton, J. V. (1990). Acta Cryst. C46, 715–717. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Lynch, D. E., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1992). Aust. J. Chem., 45, 835–844. Ruban, G. & Zabel, V. (1976). Cryst. Struct. Commun. 5, 671–677. Shawkataly, O. B., Ramalingam, K., Selvakumar, S., Fun, H.-K. & Razak, I. A. (1997). Acta Cryst. C53, 1451–1452. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Spek, A. L. (2009). Acta Cryst. D65, 148–155.
doi:10.1107/S1600536809013488
Acta Cryst. (2009). E65, o1080
supplementary materials
supplementary materials Acta Cryst. (2009). E65, o1080
[ doi:10.1107/S1600536809013488 ]
Tris[3,5-bis(trifluoromethyl)phenyl]phosphine oxide O. bin Shawkataly, M. A. A. Pankhi, M. I. Mohamed-Ibrahim, M. R. Hamdan and H.-K. Fun Comment There has been considerable research on the stereochemistry of triphenyl phosphine oxide complexes (Bandoli et al., 1970; Ruban & Zabel, 1976; Spek, 1987; Baures & Silverton, 1990; Shawkataly et al., 1997) involving different space groups. A search of the Cambridge Structural Database (Version 5.29; Allen, 2007) revealed only 9 reported structures of the parent triphenylphosphine complexes as opposed to complexes of triphenylphosphine oxides. Our interest in complexes of triphenylphosphine led us to determine the X-ray crystal structure of the title compound, Fig. 1, in order to elucidate its conformation. The bond lengths and angles of the title compound, Fig. 1, are within normal ranges (Allen et al., 1987). An intramolecular C—H···O hydrogen bond generates a five-membered ring, producing a S(5) ring motif (Bernstein et al., 1995). The P atom binds to three C atoms and one O atom in a nearly ideal tetrahedral geometry with the average O—P—C bond angle 112.84°. In the title compound, the P═O distance of 1.475 (3)Å, is less than the value reported for triphenylphospine oxide [1.487 (2)Å (Baures & Silverton, 1990)]. The average P—C bond distance is 1.813Å which is slightly longer than the distance observed in triphenylphosphine oxides previously studied; 1.799 (3)Å in OPPh3 (Baures & Silverton, 1990) and 1.76 (1)Å in its adduct with tricarboxylic acid (Lynch et al., 1992). This slight lengthening is probably due to the presence of electron withdrawing -CF3 groups bonded to the phenyl rings. The trifluoromethyl substituents show rotational disorder over two positions with a refined site-occupany ratio of 0.64 (3)/0.36 (3), 0.649 (14)/0.351 (14), 0.52 (2)/0.48 (2), 0.545 (16)/0.455 (16), 0.774 (9)/0.226 (9), and 0.63 (5)/0.37 (5) and average C—F distance of 1.300Å. This value is slightly shorter than that of the normal -CF3 bond distance (Allen et al., 1987). The mean C—P—C bond angle is 105.90°, while the O—P—C bond angles show a slight variation: 113.01 (10), 114.31 (9) and 111.18 (10)° for O—P—C9, O—P—C1, and O—P—C17 respectively. The dihedral angles between the phenyl rings and the planes containing O, P and the corresponding ipso-C atoms are 79.52 (13), 29.14 (13), 10.70 (13)°, respectively. These are close to the values for the unsubstituted analogue [77.2 (1), 36.3 (1) and 11.9 (1)°]. The crystal structure is stabilized by intermolecular C—H···O and C—H···F interactions (Table 1). Experimental The title compound was supplied by Strem Chemicals. Single crystals of (I) were obtained by slow evaporation of an ethanol solution. Refinement All of the hydrogen atoms were positioned geometrically and refined with a riding approximation model with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C). The trifluoromethyl substituents show rotational disorder over two positions with a refined site-occupany ratios of 0.64 (3)/0.36 (3) for F1, F2, F3, 0.649 (14)/0.351 (14) for F4, F5, F6, 0.52 (2)/0.48 (2) for F7, F8, F9, 0.545 (16)/0.455 (16) for F10, F11, F12, 0.774 (9)/0.226 (9) for F13, F14, F15 and 0.63 (5)/0.37 (5) for F16, F17, F18
sup-1
supplementary materials respectively. Rigid-bond restraints were applied for the fluorine groups in order to improve the high displacement ellipsoids of the groups but this was not particularly succesful, except that the refinement convergence was more stable.
Figures
Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering scheme. Open bonds link the F atoms of the minor disorder components.
Tris[3,5-bis(trifluoromethyl)phenyl]phosphine oxide Crystal data C24H9F18OP
Z=2
Mr = 686.28
F000 = 676
Triclinic, P1
Dx = 1.717 Mg m−3
Hall symbol: -P 1 a = 10.7937 (2) Å b = 11.8786 (10) Å c = 12.5066 (10) Å α = 111.065 (10)º β = 103.645 (10)º γ = 106.562 (10)º
Mo Kα radiation λ = 0.71073 Å Cell parameters from 5230 reflections θ = 1.9–28.3º µ = 0.25 mm−1 T = 294 K Block, colourless 0.48 × 0.38 × 0.22 mm
V = 1327.7 (3) Å3
Data collection Bruker SMART APEXII CCD area-detector diffractometer Radiation source: fine-focus sealed tube
4535 independent reflections
Monochromator: graphite
3611 reflections with I > 2σ(I) Rint = 0.021
T = 293 K
θmax = 25.0º
φ and ω scans
θmin = 1.9º
Absorption correction: multi-scan (SADABS; Bruker, 2005) Tmin = 0.890, Tmax = 0.947 7134 measured reflections
h = −11→12 k = −13→14 l = −14→10
Refinement Refinement on F2
sup-2
Secondary atom site location: difference Fourier map
supplementary materials Least-squares matrix: full
Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041
H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0656P)2 + 0.1383P]
wR(F2) = 0.113
where P = (Fo2 + 2Fc2)/3
S = 1.02
(Δ/σ)max = 0.001
4535 reflections
Δρmax = 0.20 e Å−3
565 parameters
Δρmin = −0.27 e Å−3
168 restraints Extinction correction: none Primary atom site location: structure-invariant direct methods
Special details 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. 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 > 2sigma(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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) P1 O1 C1 C2 H2A C3 C4 H4A C5 C6 H6A C7 C8 C9 C10 H10A C11 C12 H12A C13 C14
x
y
z
Uiso*/Ueq
0.69584 (5) 0.66832 (14) 0.56380 (18) 0.4957 (2) 0.5191 0.3928 (2) 0.3564 (2) 0.2866 0.4241 (2) 0.5283 (2) 0.5740 0.3816 (3) 0.3197 (4) 0.70486 (19) 0.5806 (2) 0.4954 0.5843 (2) 0.7100 (2) 0.7117 0.8329 (2) 0.8311 (2)
0.56123 (5) 0.62576 (14) 0.52657 (18) 0.6106 (2) 0.6809 0.5897 (2) 0.4856 (2) 0.4716 0.4021 (2) 0.42242 (19) 0.3661 0.2847 (3) 0.6811 (4) 0.40435 (18) 0.29374 (19) 0.3003 0.1740 (2) 0.1634 (2) 0.0828 0.2734 (2) 0.3936 (2)
0.16458 (4) 0.08623 (14) 0.22911 (18) 0.24927 (19) 0.2305 0.2974 (2) 0.3248 (2) 0.3562 0.3053 (2) 0.25787 (19) 0.2455 0.3293 (3) 0.3178 (3) 0.08552 (17) 0.00606 (18) −0.0021 −0.0606 (2) −0.0525 (2) −0.0982 0.02403 (19) 0.09427 (18)
0.03853 (15) 0.0516 (4) 0.0408 (4) 0.0473 (5) 0.057* 0.0532 (5) 0.0552 (5) 0.066* 0.0506 (5) 0.0460 (5) 0.055* 0.0733 (7) 0.0804 (8) 0.0404 (4) 0.0459 (5) 0.055* 0.0531 (5) 0.0574 (6) 0.069* 0.0537 (5) 0.0474 (5)
Occ. (
