Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023422/xu2254sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023422/xu2254Isup2.hkl |
CCDC reference: 610991
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.005 Å
- R factor = 0.050
- wR factor = 0.098
- Data-to-parameter ratio = 15.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 49 Perc. PLAT230_ALERT_2_C Hirshfeld Test Diff for P1 - O1 .. 5.78 su PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 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 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general background, see: Brunner & Limmer (1991). For synthesis, see: Niu et al. (2007).
A mixture of diphenylphosphine oxide (5 mmol), 1-ethynyl-1-cyclohexanol (7.5 mmol), CuI (0.5 mmol), ethylenediamine (EDA)(0.75 mmol) in 10 ml DMSO under N2 atmosphere was heated at 333 K for 18 h. The resulting solution was cooled to room temperature, and then 10 ml chloroform and 10 ml brine were added to the solution. The organic layer was washed with brine (10 ml) and dried with anhydrous Na2SO4. After filtration, the filtrate was concentrated in vacuo to give a pale yellow semisolid. The crude product was then purified by silica gel column chromatography, EtOAc-hexane (1:1) as the eluent. The single crystals of (I) were obtained from the EtOAc-hexane solution (Niu et al., 2007).
H atoms were placed in calculated positions with C—H = 0.93 (aromatic), 0.97 Å (methylene) and O—H = 0.82 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C,O).
Alkenylphosphine oxides are useful compounds in numerous synthetic transformations. For example, heteroatom nucleophiles of primary ls@zapatalite:/e/xu2254$ and secondary amines readily add to the olefinic bond in alkenylphosphine oxide to give useful bifunctional adducts, which allow further synthetic elaboration (Brunner & Limmer, 1991).
The molecular structure of (I) is shown in Fig. 1. The molecule displays an E-configuration about C═C bond. Two phenyl rings are nearly perpendicular to each other with a dihedral angle of 80.09 (8)°.
Intermolecular O–H···O hydrogen bonding (Table 1) is observed in the crystal structure of (I). The crystal structure is further stabilized by π-π stacking between C1-benzene and C1i-benzene [symmetry code: (i) 1 - x, 1 - y, 1 - z], inter-planar separation being 3.4928 (3)Å (Fig. 2).
For general background, see: Brunner & Limmer (1991). For synthesis, see: Niu et al. (2007).
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: XSCANS; 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), with 50% probability displacement ellipsoids. | |
Fig. 2. The packing of (I), showing the hydrogen bonding (dashed lines). |
C20H23O2P | F(000) = 696 |
Mr = 326.35 | Dx = 1.229 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 6.0174 (15) Å | θ = 4.8–11.1° |
b = 10.452 (2) Å | µ = 0.16 mm−1 |
c = 28.043 (5) Å | T = 295 K |
β = 90.81 (2)° | Prism, colorless |
V = 1763.6 (6) Å3 | 0.4 × 0.3 × 0.2 mm |
Z = 4 |
Bruker P4 diffractometer | Rint = 0.055 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 2.0° |
Graphite monochromator | h = −1→7 |
ω scans | k = −12→1 |
4757 measured reflections | l = −33→33 |
3293 independent reflections | 3 standard reflections every 97 reflections |
1621 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.001P)2] where P = (Fo2 + 2Fc2)/3 |
3293 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C20H23O2P | V = 1763.6 (6) Å3 |
Mr = 326.35 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.0174 (15) Å | µ = 0.16 mm−1 |
b = 10.452 (2) Å | T = 295 K |
c = 28.043 (5) Å | 0.4 × 0.3 × 0.2 mm |
β = 90.81 (2)° |
Bruker P4 diffractometer | Rint = 0.055 |
4757 measured reflections | 3 standard reflections every 97 reflections |
3293 independent reflections | intensity decay: none |
1621 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.25 e Å−3 |
3293 reflections | Δρmin = −0.35 e Å−3 |
209 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 | 0.40018 (14) | 0.51414 (7) | 0.63461 (3) | 0.0457 (2) | |
O1 | 0.6039 (3) | 0.58117 (18) | 0.65258 (6) | 0.0524 (5) | |
O2 | −0.1924 (3) | 0.77017 (19) | 0.59673 (7) | 0.0590 (6) | |
H2B | −0.2480 | 0.7239 | 0.6170 | 0.071* | |
C1 | 0.4511 (5) | 0.4185 (3) | 0.58228 (9) | 0.0427 (7) | |
C2 | 0.2967 (5) | 0.3344 (3) | 0.56462 (10) | 0.0621 (9) | |
H2A | 0.1644 | 0.3223 | 0.5807 | 0.075* | |
C3 | 0.3346 (6) | 0.2672 (3) | 0.52318 (11) | 0.0724 (11) | |
H3A | 0.2274 | 0.2113 | 0.5112 | 0.087* | |
C4 | 0.5315 (6) | 0.2833 (3) | 0.49970 (11) | 0.0646 (9) | |
H4A | 0.5571 | 0.2378 | 0.4718 | 0.077* | |
C5 | 0.6881 (5) | 0.3646 (3) | 0.51669 (11) | 0.0644 (9) | |
H5A | 0.8218 | 0.3744 | 0.5008 | 0.077* | |
C6 | 0.6478 (5) | 0.4333 (3) | 0.55804 (10) | 0.0568 (9) | |
H6A | 0.7547 | 0.4901 | 0.5696 | 0.068* | |
C7 | 0.2825 (5) | 0.4049 (3) | 0.67727 (9) | 0.0443 (7) | |
C8 | 0.4023 (5) | 0.2988 (3) | 0.69112 (11) | 0.0659 (10) | |
H8A | 0.5410 | 0.2837 | 0.6780 | 0.079* | |
C9 | 0.3183 (7) | 0.2141 (4) | 0.72434 (12) | 0.0816 (11) | |
H9A | 0.4011 | 0.1430 | 0.7336 | 0.098* | |
C10 | 0.1129 (7) | 0.2351 (4) | 0.74366 (11) | 0.0773 (12) | |
H10A | 0.0563 | 0.1782 | 0.7659 | 0.093* | |
C11 | −0.0072 (6) | 0.3394 (4) | 0.73009 (11) | 0.0725 (10) | |
H11A | −0.1455 | 0.3540 | 0.7434 | 0.087* | |
C12 | 0.0741 (5) | 0.4246 (3) | 0.69656 (10) | 0.0585 (9) | |
H12A | −0.0110 | 0.4946 | 0.6871 | 0.070* | |
C13 | 0.1806 (5) | 0.6189 (3) | 0.61876 (9) | 0.0468 (8) | |
H13A | 0.0558 | 0.5841 | 0.6038 | 0.056* | |
C14 | 0.1824 (5) | 0.7429 (3) | 0.62682 (10) | 0.0469 (8) | |
H14A | 0.3121 | 0.7773 | 0.6399 | 0.056* | |
C15 | −0.0060 (5) | 0.8346 (3) | 0.61683 (10) | 0.0452 (7) | |
C16 | 0.0617 (5) | 0.9337 (3) | 0.57950 (10) | 0.0585 (9) | |
H16A | 0.1980 | 0.9755 | 0.5899 | 0.070* | |
H16B | 0.0900 | 0.8909 | 0.5495 | 0.070* | |
C17 | −0.1181 (5) | 1.0336 (3) | 0.57195 (11) | 0.0700 (10) | |
H17A | −0.0682 | 1.0962 | 0.5489 | 0.084* | |
H17B | −0.2506 | 0.9928 | 0.5590 | 0.084* | |
C18 | −0.1741 (6) | 1.1005 (3) | 0.61773 (12) | 0.0817 (11) | |
H18A | −0.2938 | 1.1609 | 0.6119 | 0.098* | |
H18B | −0.0456 | 1.1480 | 0.6292 | 0.098* | |
C19 | −0.2443 (5) | 1.0046 (3) | 0.65560 (11) | 0.0751 (10) | |
H19A | −0.3834 | 0.9649 | 0.6459 | 0.090* | |
H19B | −0.2683 | 1.0491 | 0.6855 | 0.090* | |
C20 | −0.0674 (5) | 0.9015 (3) | 0.66299 (10) | 0.0588 (9) | |
H20A | 0.0649 | 0.9403 | 0.6769 | 0.071* | |
H20B | −0.1218 | 0.8385 | 0.6854 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0464 (4) | 0.0406 (5) | 0.0503 (4) | 0.0011 (5) | 0.0049 (3) | −0.0005 (4) |
O1 | 0.0434 (12) | 0.0539 (13) | 0.0599 (12) | −0.0062 (11) | −0.0018 (10) | −0.0015 (11) |
O2 | 0.0529 (13) | 0.0498 (14) | 0.0743 (14) | −0.0060 (12) | −0.0043 (12) | 0.0101 (11) |
C1 | 0.0474 (17) | 0.0373 (16) | 0.0435 (17) | −0.0005 (16) | 0.0052 (14) | 0.0026 (14) |
C2 | 0.063 (2) | 0.064 (2) | 0.060 (2) | −0.011 (2) | 0.0169 (18) | −0.0109 (19) |
C3 | 0.078 (3) | 0.070 (3) | 0.070 (2) | −0.017 (2) | 0.014 (2) | −0.020 (2) |
C4 | 0.082 (3) | 0.062 (2) | 0.0500 (19) | 0.010 (2) | 0.0108 (19) | −0.0059 (18) |
C5 | 0.058 (2) | 0.076 (3) | 0.060 (2) | 0.008 (2) | 0.0148 (18) | −0.001 (2) |
C6 | 0.0515 (19) | 0.061 (2) | 0.0583 (19) | −0.0027 (18) | 0.0055 (16) | −0.0047 (18) |
C7 | 0.0497 (18) | 0.0390 (18) | 0.0443 (17) | −0.0005 (16) | 0.0055 (15) | −0.0030 (14) |
C8 | 0.071 (2) | 0.063 (2) | 0.065 (2) | 0.015 (2) | 0.0119 (18) | 0.0115 (19) |
C9 | 0.106 (3) | 0.069 (2) | 0.070 (2) | 0.011 (3) | 0.010 (2) | 0.026 (2) |
C10 | 0.104 (3) | 0.076 (3) | 0.052 (2) | −0.024 (3) | 0.011 (2) | 0.014 (2) |
C11 | 0.069 (2) | 0.090 (3) | 0.059 (2) | −0.006 (2) | 0.0199 (19) | 0.004 (2) |
C12 | 0.058 (2) | 0.057 (2) | 0.0607 (19) | 0.0034 (19) | 0.0092 (17) | 0.0015 (18) |
C13 | 0.0467 (19) | 0.0422 (18) | 0.0516 (18) | −0.0031 (16) | 0.0022 (15) | 0.0002 (15) |
C14 | 0.0468 (18) | 0.0454 (18) | 0.0486 (17) | −0.0009 (16) | 0.0074 (15) | 0.0035 (16) |
C15 | 0.0461 (18) | 0.0363 (17) | 0.0531 (18) | 0.0013 (16) | 0.0029 (15) | 0.0011 (15) |
C16 | 0.067 (2) | 0.0463 (19) | 0.063 (2) | 0.0043 (18) | 0.0169 (17) | 0.0113 (17) |
C17 | 0.083 (2) | 0.056 (2) | 0.071 (2) | 0.012 (2) | 0.0157 (19) | 0.020 (2) |
C18 | 0.103 (3) | 0.046 (2) | 0.097 (3) | 0.020 (2) | 0.016 (2) | 0.008 (2) |
C19 | 0.092 (3) | 0.060 (2) | 0.074 (2) | 0.023 (2) | 0.024 (2) | 0.002 (2) |
C20 | 0.074 (2) | 0.051 (2) | 0.0520 (18) | 0.0087 (19) | 0.0087 (17) | 0.0001 (17) |
P1—O1 | 1.4933 (18) | C10—H10A | 0.9300 |
P1—C1 | 1.805 (3) | C11—C12 | 1.388 (4) |
P1—C7 | 1.806 (3) | C11—H11A | 0.9300 |
P1—C13 | 1.768 (3) | C12—H12A | 0.9300 |
O2—C15 | 1.418 (3) | C13—C14 | 1.315 (3) |
O2—H2B | 0.8200 | C13—H13A | 0.9300 |
C1—C2 | 1.367 (4) | C14—C15 | 1.508 (4) |
C1—C6 | 1.382 (3) | C14—H14A | 0.9300 |
C2—C3 | 1.379 (4) | C15—C20 | 1.521 (4) |
C2—H2A | 0.9300 | C15—C16 | 1.532 (3) |
C3—C4 | 1.374 (4) | C16—C17 | 1.516 (4) |
C3—H3A | 0.9300 | C16—H16A | 0.9700 |
C4—C5 | 1.350 (4) | C16—H16B | 0.9700 |
C4—H4A | 0.9300 | C17—C18 | 1.504 (4) |
C5—C6 | 1.388 (4) | C17—H17A | 0.9700 |
C5—H5A | 0.9300 | C17—H17B | 0.9700 |
C6—H6A | 0.9300 | C18—C19 | 1.524 (4) |
C7—C8 | 1.376 (4) | C18—H18A | 0.9700 |
C7—C12 | 1.388 (4) | C18—H18B | 0.9700 |
C8—C9 | 1.386 (4) | C19—C20 | 1.527 (4) |
C8—H8A | 0.9300 | C19—H19A | 0.9700 |
C9—C10 | 1.374 (4) | C19—H19B | 0.9700 |
C9—H9A | 0.9300 | C20—H20A | 0.9700 |
C10—C11 | 1.360 (4) | C20—H20B | 0.9700 |
O1—P1—C13 | 113.65 (13) | C14—C13—P1 | 124.2 (3) |
O1—P1—C1 | 112.72 (12) | C14—C13—H13A | 117.9 |
C13—P1—C1 | 105.86 (13) | P1—C13—H13A | 117.9 |
O1—P1—C7 | 113.62 (12) | C13—C14—C15 | 126.1 (3) |
C13—P1—C7 | 105.04 (14) | C13—C14—H14A | 116.9 |
C1—P1—C7 | 105.15 (12) | C15—C14—H14A | 116.9 |
C15—O2—H2B | 109.5 | O2—C15—C14 | 111.1 (2) |
C2—C1—C6 | 118.4 (3) | O2—C15—C20 | 110.9 (2) |
C2—C1—P1 | 121.9 (2) | C14—C15—C20 | 109.0 (2) |
C6—C1—P1 | 119.6 (2) | O2—C15—C16 | 105.4 (2) |
C1—C2—C3 | 120.9 (3) | C14—C15—C16 | 110.5 (2) |
C1—C2—H2A | 119.6 | C20—C15—C16 | 109.9 (2) |
C3—C2—H2A | 119.6 | C17—C16—C15 | 111.4 (2) |
C4—C3—C2 | 119.7 (3) | C17—C16—H16A | 109.3 |
C4—C3—H3A | 120.1 | C15—C16—H16A | 109.3 |
C2—C3—H3A | 120.1 | C17—C16—H16B | 109.3 |
C5—C4—C3 | 120.7 (3) | C15—C16—H16B | 109.3 |
C5—C4—H4A | 119.7 | H16A—C16—H16B | 108.0 |
C3—C4—H4A | 119.7 | C18—C17—C16 | 111.6 (3) |
C4—C5—C6 | 119.4 (3) | C18—C17—H17A | 109.3 |
C4—C5—H5A | 120.3 | C16—C17—H17A | 109.3 |
C6—C5—H5A | 120.3 | C18—C17—H17B | 109.3 |
C1—C6—C5 | 120.9 (3) | C16—C17—H17B | 109.3 |
C1—C6—H6A | 119.5 | H17A—C17—H17B | 108.0 |
C5—C6—H6A | 119.5 | C17—C18—C19 | 110.9 (3) |
C8—C7—C12 | 118.8 (3) | C17—C18—H18A | 109.5 |
C8—C7—P1 | 119.2 (2) | C19—C18—H18A | 109.5 |
C12—C7—P1 | 122.0 (2) | C17—C18—H18B | 109.5 |
C7—C8—C9 | 120.7 (3) | C19—C18—H18B | 109.5 |
C7—C8—H8A | 119.7 | H18A—C18—H18B | 108.0 |
C9—C8—H8A | 119.7 | C18—C19—C20 | 111.0 (2) |
C10—C9—C8 | 120.1 (4) | C18—C19—H19A | 109.4 |
C10—C9—H9A | 119.9 | C20—C19—H19A | 109.4 |
C8—C9—H9A | 119.9 | C18—C19—H19B | 109.4 |
C11—C10—C9 | 119.7 (3) | C20—C19—H19B | 109.4 |
C11—C10—H10A | 120.2 | H19A—C19—H19B | 108.0 |
C9—C10—H10A | 120.2 | C15—C20—C19 | 112.7 (2) |
C10—C11—C12 | 120.9 (3) | C15—C20—H20A | 109.0 |
C10—C11—H11A | 119.6 | C19—C20—H20A | 109.0 |
C12—C11—H11A | 119.6 | C15—C20—H20B | 109.0 |
C7—C12—C11 | 119.8 (3) | C19—C20—H20B | 109.0 |
C7—C12—H12A | 120.1 | H20A—C20—H20B | 107.8 |
C11—C12—H12A | 120.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···O1i | 0.82 | 2.01 | 2.813 (3) | 166 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C20H23O2P |
Mr | 326.35 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 6.0174 (15), 10.452 (2), 28.043 (5) |
β (°) | 90.81 (2) |
V (Å3) | 1763.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4757, 3293, 1621 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.098, 1.07 |
No. of reflections | 3293 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.35 |
Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···O1i | 0.82 | 2.01 | 2.813 (3) | 166 |
Symmetry code: (i) x−1, y, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Alkenylphosphine oxides are useful compounds in numerous synthetic transformations. For example, heteroatom nucleophiles of primary ls@zapatalite:/e/xu2254$ and secondary amines readily add to the olefinic bond in alkenylphosphine oxide to give useful bifunctional adducts, which allow further synthetic elaboration (Brunner & Limmer, 1991).
The molecular structure of (I) is shown in Fig. 1. The molecule displays an E-configuration about C═C bond. Two phenyl rings are nearly perpendicular to each other with a dihedral angle of 80.09 (8)°.
Intermolecular O–H···O hydrogen bonding (Table 1) is observed in the crystal structure of (I). The crystal structure is further stabilized by π-π stacking between C1-benzene and C1i-benzene [symmetry code: (i) 1 - x, 1 - y, 1 - z], inter-planar separation being 3.4928 (3)Å (Fig. 2).