Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046600/fl2164sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046600/fl2164Isup2.hkl |
CCDC reference: 672836
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.030
- wR factor = 0.084
- Data-to-parameter ratio = 19.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for P1 - C1 .. 9.96 su
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.708 0.930 Tmin(prime) and Tmax expected: 0.853 0.930 RR(prime) = 0.831 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.83 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for P1 - C3 .. 5.54 su
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a solution of trimethylsilylacetylene (5 mmol, 0.71 ml) in anhydrous pentane (5 ml) and anhydrous ether (5 ml), was added n-BuLi (1.6 M) solution in hexane (6 mmol, 3.8 ml) in a dropwise manner at 195 K (-78 °C). The reaction solution was stirred continuously for 1 h. Then bis(2,2,2-trifluoroethyl)phosphorochloridate was added dropwise at the same temperature and the mixture was stirred for an additional hour. The reaction solution was stirred overnight at ambient temperature and was then quenched with a saturated aqueous solution of ammonium chloride. The organic layer was separated and washed with water. The aqueous layers were washed with ether, and the organic fractions were combined, washed with saturated NaCl solution and dried over MgSO4. The oxide was purified by column chromatography (hexane/ethyl acetate, 1/1) and crystals of sufficient quality for single-crystal diffraction analysis were obtained from ethyl acetate by slow evaporation. 1H NMR (400 MHz, CDCl3) δ 3.30 (d, 3H, J = 12.45 Hz), 13C NMR (100 MHz) δ 92.12 (d, 3 C, J = 45.45 Hz), 77.35 (d, 3 C, J = 233.88 Hz), 31P NMR (162 MHz) δ -55.3..
Treatment of hydrogen atoms: All hydrogen atoms were added in calculated positions with a C—H bond distance of 0.95 Å and were refined with Uiso(H) = 1.2Ueq(C).
The e.s.d. values of the cell parameters are taken from the software recognizing that the values are unreasonably small (Herbstein, 2000).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).
C6H3OP | Dx = 1.294 Mg m−3 |
Mr = 122.05 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 7248 reflections |
a = 6.8646 (9) Å | θ = 3.0–30.6° |
b = 9.7823 (13) Å | µ = 0.33 mm−1 |
c = 9.3277 (12) Å | T = 100 K |
V = 626.37 (14) Å3 | Block, colorless |
Z = 4 | 0.48 × 0.23 × 0.22 mm |
F(000) = 248 |
Bruker SMART APEX CCD diffractometer | 821 independent reflections |
Radiation source: fine-focus sealed tube | 796 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 28.3°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | h = −9→9 |
Tmin = 0.708, Tmax = 0.930 | k = −13→13 |
7459 measured reflections | l = −12→12 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.049P)2 + 0.2795P] where P = (Fo2 + 2Fc2)/3 |
821 reflections | (Δ/σ)max = 0.001 |
43 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C6H3OP | V = 626.37 (14) Å3 |
Mr = 122.05 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 6.8646 (9) Å | µ = 0.33 mm−1 |
b = 9.7823 (13) Å | T = 100 K |
c = 9.3277 (12) Å | 0.48 × 0.23 × 0.22 mm |
Bruker SMART APEX CCD diffractometer | 821 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | 796 reflections with I > 2σ(I) |
Tmin = 0.708, Tmax = 0.930 | Rint = 0.018 |
7459 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.45 e Å−3 |
821 reflections | Δρmin = −0.33 e Å−3 |
43 parameters |
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 | ||
P1 | 0.42049 (6) | 0.7500 | 0.53431 (4) | 0.01596 (17) | |
O1 | 0.29767 (18) | 0.7500 | 0.40356 (13) | 0.0205 (3) | |
C1 | 0.37974 (17) | 0.60900 (12) | 0.64477 (12) | 0.0199 (2) | |
C4 | 0.8405 (3) | 0.7500 | 0.47595 (18) | 0.0235 (4) | |
H4 | 0.9760 | 0.7500 | 0.4552 | 0.028* | |
C3 | 0.6715 (3) | 0.7500 | 0.50180 (18) | 0.0191 (3) | |
C2 | 0.33869 (17) | 0.51443 (13) | 0.71937 (12) | 0.0230 (3) | |
H2 | 0.3060 | 0.4390 | 0.7788 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0142 (2) | 0.0159 (2) | 0.0178 (2) | 0.000 | −0.00015 (13) | 0.000 |
O1 | 0.0186 (6) | 0.0219 (6) | 0.0209 (6) | 0.000 | −0.0035 (4) | 0.000 |
C1 | 0.0181 (5) | 0.0199 (5) | 0.0217 (5) | 0.0000 (4) | 0.0004 (4) | −0.0012 (4) |
C4 | 0.0196 (9) | 0.0248 (9) | 0.0261 (9) | 0.000 | 0.0001 (6) | 0.000 |
C3 | 0.0190 (8) | 0.0182 (7) | 0.0200 (7) | 0.000 | 0.0007 (6) | 0.000 |
C2 | 0.0227 (6) | 0.0222 (6) | 0.0242 (6) | −0.0002 (4) | 0.0022 (4) | −0.0001 (5) |
P1—O1 | 1.4826 (12) | C1—C2 | 1.1914 (17) |
P1—C1 | 1.7443 (12) | C4—C3 | 1.185 (3) |
P1—C1i | 1.7443 (12) | C4—H4 | 0.9500 |
P1—C3 | 1.7495 (18) | C2—H2 | 0.9500 |
O1—P1—C1 | 113.25 (5) | C1i—P1—C3 | 105.09 (5) |
O1—P1—C1i | 113.25 (5) | C2—C1—P1 | 175.54 (11) |
C1—P1—C1i | 104.52 (8) | C3—C4—H4 | 180.0 |
O1—P1—C3 | 114.67 (8) | C4—C3—P1 | 178.24 (17) |
C1—P1—C3 | 105.09 (5) | C1—C2—H2 | 180.0 |
Symmetry code: (i) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O1ii | 0.95 | 2.26 | 3.210 (2) | 179 |
C2—H2···O1iii | 0.95 | 2.30 | 3.2433 (14) | 174 |
Symmetry codes: (ii) x+1, y, z; (iii) −x+1/2, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H3OP |
Mr | 122.05 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 100 |
a, b, c (Å) | 6.8646 (9), 9.7823 (13), 9.3277 (12) |
V (Å3) | 626.37 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.48 × 0.23 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-Plus; Bruker, 2003) |
Tmin, Tmax | 0.708, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7459, 821, 796 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.084, 1.12 |
No. of reflections | 821 |
No. of parameters | 43 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.33 |
Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Bruker, 2003).
P1—C1i | 1.7443 (12) | ||
O1—P1—C1i | 113.25 (5) | C1—P1—C1i | 104.52 (8) |
Symmetry code: (i) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O1ii | 0.95 | 2.26 | 3.210 (2) | 179.4 |
C2—H2···O1iii | 0.95 | 2.30 | 3.2433 (14) | 173.7 |
Symmetry codes: (ii) x+1, y, z; (iii) −x+1/2, −y+1, z+1/2. |
As an aspect of our research into the Diels-Alder chemistry of electron poor alkynyl phosphonates we attempted the synthesis of bis(2,2,2-trifluoroethyl)(trimethylsilyl)ethynyl phosphonate by reacting lithium trimethylsilyl acetylide with bis(2,2,2-trifluoroethyl)phosphorochloridate as shown in Figure 1. Displacement of not only the chlorine but also of the two –OCH2CF3 groups resulted, after aqueous workup and loss of the trimethylsilyl group, in the unplanned formation of triethynylphosphine oxide in 25% yield. While the triethynylphosphine oxide is mentioned in some spectroscopic publications (Yang et al., 1992; Rosenberg & Drenth, 1972) no synthesis is reported in the scientific literature.
In the solid state the title compound is found to be located on a crystallographic mirror plane with the P=O as well as one of the acetylene units bisected by this plane (Figure 2). The phosphorus center exhibits pseudo-tetrahedral geometry with three acetetylene substituents and the double bonded oxygen atom. The bond distances and angles are unexceptional.
Crystal packing is dominated by hydrogen bonds between the acetylenic H atoms and the P=O oxygen with all three acetylene units forming relatively strong C—H···O hydrogen bonds. Two of the three hydrogen bonds towards each oxygen atom are symmetry related by the crystallographic mirror plane and are coplanar with each other and the P=O unit. The third C—H···O hydrogen bond is at an angle of 67.49 (7) ° to this plane (as given by the angles between the lines defined by P1—O1 and O1—C4iii (symmetry code iv = x - 1, y, z). (Figure 3)
The Cambridge crystallographic database does not have any other entries for hydrogen bonds between acetylene and O=P units, but the parameters observed here are in good agreement with those listed for hydrogen bonds towards other O=X units such as ketones or aldehydes (Cambridge Structural Database, V5.28; Allen 2002). The H···P=O angles of the title compound are 133.70° for H2v···O1—P1 and 112.35° for H4iv···O1—P1, respectively (symmetry code v = 1/2 - x, 1 - y, 1 - z).
The three dimensional crystal structure thus formed by the hydrogen bonding interactions actually consists of two interpenetrating networks that are each heavily interconnected via H-bonding, but that are not connected via such interactions with each other (Figures 4 and 5).