Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014642/ya6130sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014642/ya6130Isup2.hkl |
CCDC reference: 197467
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.006 Å
- R factor = 0.055
- wR factor = 0.110
- Data-to-parameter ratio = 13.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
STRVAL_01 From the CIF: _refine_ls_abs_structure_Flack 0.660 From the CIF: _refine_ls_abs_structure_Flack_su 0.170 Alert C Flack test results are ambiguous. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 3383 Count of symmetry unique reflns 2021 Completeness (_total/calc) 167.39% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1362 Fraction of Friedel pairs measured 0.674 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared in 70% yield by the reaction of ethyl propiolate with triphenylphosphine under reflux in a THF–water mixture; this is similar in nature to the method reported previously by Richards & Tebby (1971).
Despite the measurement of 67% of Friedel equivalents and the presence of phosphorus in the crystal structure the refined value of the Flack (1983) parameter did not allow the determination of the absolute configuration of the title compound in the crystal. [Were the Friedel equivalents merged?]
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski &Minor, 1997); data reduction: DENZO, COLLECT and maXus (Mackay et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1998).
C23H23O3P | F(000) = 800 |
Mr = 378.38 | Dx = 1.275 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3383 reflections |
a = 5.788 (5) Å | θ = 3.1–25.0° |
b = 17.499 (5) Å | µ = 0.16 mm−1 |
c = 19.463 (5) Å | T = 120 K |
V = 1971.3 (19) Å3 | Rod, colourless |
Z = 4 | 0.15 × 0.04 × 0.03 mm |
Bruker–Nonius Kappa CCD area-detector diffractometer | 2169 reflections with I > 2σ(I) |
Radiation source: Bruker–Nonius FR591 rotating anode | Rint = 0.096 |
Graphite monochromator | θmax = 25.0°, θmin = 3.1° |
Detector resolution: 9.091 pixels mm1 pixels mm-1 | h = −6→6 |
ϕ and ω scans to fill the asymmetric unit | k = −19→20 |
10345 measured reflections | l = −22→23 |
3383 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.055 | w = 1/[σ2(Fo2) + (0.0301P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.110 | (Δ/σ)max < 0.001 |
S = 0.98 | Δρmax = 0.16 e Å−3 |
3383 reflections | Δρmin = −0.22 e Å−3 |
246 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0034 (9) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.66 (17) |
C23H23O3P | V = 1971.3 (19) Å3 |
Mr = 378.38 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.788 (5) Å | µ = 0.16 mm−1 |
b = 17.499 (5) Å | T = 120 K |
c = 19.463 (5) Å | 0.15 × 0.04 × 0.03 mm |
Bruker–Nonius Kappa CCD area-detector diffractometer | 2169 reflections with I > 2σ(I) |
10345 measured reflections | Rint = 0.096 |
3383 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.110 | Δρmax = 0.16 e Å−3 |
S = 0.98 | Δρmin = −0.22 e Å−3 |
3383 reflections | Absolute structure: Flack (1983) |
246 parameters | Absolute structure parameter: 0.66 (17) |
0 restraints |
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 | 0.9902 (2) | 0.11836 (6) | 0.21625 (5) | 0.0347 (3) | |
O1 | 1.2440 (4) | 0.11104 (16) | 0.20773 (13) | 0.0391 (7) | |
O2 | 0.5024 (6) | −0.03389 (15) | 0.09192 (14) | 0.0497 (8) | |
O3 | 0.7370 (6) | −0.13387 (17) | 0.10814 (17) | 0.0577 (9) | |
C1 | 0.8976 (7) | 0.2168 (2) | 0.2158 (2) | 0.0346 (10) | |
C2 | 0.6833 (8) | 0.2403 (2) | 0.2406 (2) | 0.0430 (12) | |
H2 | 0.5751 | 0.2035 | 0.2564 | 0.052* | |
C3 | 0.6279 (8) | 0.3172 (2) | 0.2421 (2) | 0.0443 (12) | |
H3 | 0.4821 | 0.3330 | 0.2595 | 0.053* | |
C4 | 0.7824 (7) | 0.3709 (2) | 0.2187 (2) | 0.0437 (11) | |
H4 | 0.7441 | 0.4237 | 0.2207 | 0.052* | |
C5 | 0.9934 (9) | 0.3484 (2) | 0.1922 (2) | 0.0447 (11) | |
H5 | 1.0987 | 0.3853 | 0.1748 | 0.054* | |
C6 | 1.0499 (7) | 0.2710 (2) | 0.1913 (2) | 0.0416 (11) | |
H6 | 1.1953 | 0.2553 | 0.1735 | 0.050* | |
C7 | 0.8936 (7) | 0.0793 (2) | 0.2975 (2) | 0.0348 (10) | |
C8 | 1.0583 (7) | 0.0783 (2) | 0.3501 (2) | 0.0381 (11) | |
H8 | 1.2087 | 0.0980 | 0.3419 | 0.046* | |
C9 | 1.0034 (8) | 0.0486 (2) | 0.41433 (19) | 0.0379 (10) | |
H9 | 1.1151 | 0.0489 | 0.4501 | 0.045* | |
C10 | 0.7873 (8) | 0.0188 (2) | 0.4259 (2) | 0.0384 (11) | |
H10 | 0.7497 | −0.0019 | 0.4696 | 0.046* | |
C11 | 0.6234 (8) | 0.0189 (2) | 0.3736 (2) | 0.0388 (11) | |
H11 | 0.4748 | −0.0024 | 0.3816 | 0.047* | |
C12 | 0.6754 (7) | 0.0497 (2) | 0.3098 (2) | 0.0360 (10) | |
H12 | 0.5616 | 0.0505 | 0.2746 | 0.043* | |
C13 | 0.8206 (7) | 0.0706 (2) | 0.1506 (2) | 0.0352 (11) | |
H13 | 0.6538 | 0.0801 | 0.1609 | 0.042* | |
C14 | 0.8719 (7) | 0.1046 (2) | 0.0802 (2) | 0.0340 (10) | |
C15 | 0.7096 (8) | 0.1499 (2) | 0.0480 (2) | 0.0355 (10) | |
H15 | 0.5673 | 0.1605 | 0.0704 | 0.043* | |
C16 | 0.7517 (7) | 0.1801 (2) | −0.0166 (2) | 0.0371 (10) | |
H16 | 0.6375 | 0.2105 | −0.0385 | 0.045* | |
C17 | 0.9584 (8) | 0.1662 (2) | −0.0490 (2) | 0.0362 (11) | |
H17 | 0.9872 | 0.1869 | −0.0933 | 0.043* | |
C18 | 1.1245 (7) | 0.1220 (2) | −0.0169 (2) | 0.0385 (10) | |
H18 | 1.2680 | 0.1127 | −0.0390 | 0.046* | |
C19 | 1.0815 (7) | 0.0912 (2) | 0.0480 (2) | 0.0364 (11) | |
H19 | 1.1959 | 0.0610 | 0.0701 | 0.044* | |
C20 | 0.8608 (8) | −0.0166 (2) | 0.1527 (2) | 0.0419 (11) | |
H20A | 1.0140 | −0.0283 | 0.1327 | 0.050* | |
H20B | 0.8613 | −0.0340 | 0.2011 | 0.050* | |
C21 | 0.6773 (9) | −0.0592 (2) | 0.1136 (2) | 0.0416 (11) | |
C22 | 0.5660 (11) | −0.1819 (3) | 0.0744 (3) | 0.074 (2) | |
H22A | 0.5557 | −0.1689 | 0.0250 | 0.089* | |
H22B | 0.4121 | −0.1744 | 0.0955 | 0.089* | |
C23 | 0.6421 (13) | −0.2623 (3) | 0.0830 (3) | 0.089 (2) | |
H23A | 0.7958 | −0.2688 | 0.0627 | 0.134* | |
H23B | 0.5323 | −0.2965 | 0.0600 | 0.134* | |
H23C | 0.6484 | −0.2748 | 0.1321 | 0.134* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0310 (5) | 0.0408 (6) | 0.0322 (5) | −0.0013 (6) | 0.0004 (5) | 0.0009 (5) |
O1 | 0.0277 (14) | 0.0511 (17) | 0.0384 (16) | 0.0006 (14) | 0.0004 (13) | 0.0026 (15) |
O2 | 0.047 (2) | 0.0437 (17) | 0.058 (2) | 0.0001 (19) | −0.0141 (18) | −0.0018 (14) |
O3 | 0.073 (3) | 0.039 (2) | 0.061 (2) | 0.0075 (17) | −0.0155 (18) | −0.0071 (16) |
C1 | 0.038 (2) | 0.042 (2) | 0.024 (2) | −0.0093 (19) | −0.003 (2) | 0.004 (2) |
C2 | 0.041 (3) | 0.037 (3) | 0.051 (3) | −0.004 (2) | −0.001 (2) | 0.003 (2) |
C3 | 0.033 (3) | 0.047 (3) | 0.053 (3) | 0.003 (2) | 0.001 (2) | −0.006 (2) |
C4 | 0.046 (3) | 0.037 (3) | 0.048 (3) | 0.003 (2) | −0.014 (2) | 0.000 (2) |
C5 | 0.049 (3) | 0.045 (3) | 0.040 (2) | −0.013 (3) | −0.004 (3) | 0.0042 (19) |
C6 | 0.039 (3) | 0.045 (3) | 0.041 (3) | −0.006 (2) | 0.0006 (19) | 0.001 (2) |
C7 | 0.033 (2) | 0.033 (2) | 0.039 (3) | −0.0001 (18) | 0.003 (2) | 0.0009 (19) |
C8 | 0.030 (3) | 0.042 (3) | 0.043 (3) | −0.0022 (18) | −0.0017 (19) | −0.001 (2) |
C9 | 0.039 (2) | 0.040 (2) | 0.035 (2) | −0.002 (3) | −0.007 (2) | 0.0043 (19) |
C10 | 0.044 (3) | 0.038 (3) | 0.033 (2) | 0.006 (2) | 0.005 (2) | 0.002 (2) |
C11 | 0.031 (2) | 0.038 (2) | 0.047 (3) | 0.000 (2) | −0.001 (2) | 0.004 (2) |
C12 | 0.037 (3) | 0.036 (2) | 0.034 (2) | 0.0002 (19) | −0.0014 (18) | 0.004 (2) |
C13 | 0.032 (3) | 0.043 (3) | 0.031 (2) | 0.002 (2) | −0.0002 (18) | 0.000 (2) |
C14 | 0.037 (2) | 0.033 (2) | 0.032 (2) | −0.005 (2) | −0.0019 (19) | −0.0053 (19) |
C15 | 0.034 (3) | 0.034 (2) | 0.038 (3) | 0.0028 (19) | −0.003 (2) | −0.001 (2) |
C16 | 0.033 (3) | 0.038 (2) | 0.040 (3) | 0.000 (2) | −0.003 (2) | 0.000 (2) |
C17 | 0.047 (3) | 0.035 (2) | 0.026 (2) | −0.006 (2) | −0.003 (2) | 0.0023 (19) |
C18 | 0.033 (2) | 0.041 (2) | 0.041 (3) | −0.004 (2) | 0.003 (2) | −0.003 (2) |
C19 | 0.030 (2) | 0.040 (3) | 0.039 (3) | −0.0011 (18) | −0.0025 (19) | −0.008 (2) |
C20 | 0.045 (3) | 0.044 (3) | 0.037 (2) | 0.005 (2) | −0.002 (2) | 0.003 (2) |
C21 | 0.051 (3) | 0.037 (3) | 0.036 (3) | 0.001 (2) | 0.003 (2) | 0.000 (2) |
C22 | 0.111 (6) | 0.037 (3) | 0.073 (4) | −0.011 (3) | −0.021 (4) | −0.007 (3) |
C23 | 0.139 (6) | 0.045 (3) | 0.084 (4) | 0.000 (4) | 0.009 (4) | −0.006 (3) |
P1—O1 | 1.484 (3) | C11—C12 | 1.387 (5) |
P1—C1 | 1.805 (4) | C11—H11 | 0.9500 |
P1—C7 | 1.811 (4) | C12—H12 | 0.9500 |
P1—C13 | 1.815 (4) | C13—C14 | 1.523 (5) |
O2—C21 | 1.183 (5) | C13—C20 | 1.544 (6) |
O3—C21 | 1.356 (5) | C13—H13 | 1.0000 |
O3—C22 | 1.456 (6) | C14—C15 | 1.379 (6) |
C1—C6 | 1.379 (5) | C14—C19 | 1.385 (6) |
C1—C2 | 1.393 (6) | C15—C16 | 1.386 (6) |
C2—C3 | 1.383 (6) | C15—H15 | 0.9500 |
C2—H2 | 0.9500 | C16—C17 | 1.374 (6) |
C3—C4 | 1.376 (6) | C16—H16 | 0.9500 |
C3—H3 | 0.9500 | C17—C18 | 1.383 (6) |
C4—C5 | 1.383 (6) | C17—H17 | 0.9500 |
C4—H4 | 0.9500 | C18—C19 | 1.396 (6) |
C5—C6 | 1.394 (6) | C18—H18 | 0.9500 |
C5—H5 | 0.9500 | C19—H19 | 0.9500 |
C6—H6 | 0.9500 | C20—C21 | 1.504 (6) |
C7—C12 | 1.386 (6) | C20—H20A | 0.9900 |
C7—C8 | 1.399 (5) | C20—H20B | 0.9900 |
C8—C9 | 1.391 (5) | C22—C23 | 1.484 (7) |
C8—H8 | 0.9500 | C22—H22A | 0.9900 |
C9—C10 | 1.374 (6) | C22—H22B | 0.9900 |
C9—H9 | 0.9500 | C23—H23A | 0.9800 |
C10—C11 | 1.391 (6) | C23—H23B | 0.9800 |
C10—H10 | 0.9500 | C23—H23C | 0.9800 |
O1—P1—C1 | 112.06 (17) | C14—C13—P1 | 110.4 (3) |
O1—P1—C7 | 111.75 (17) | C20—C13—P1 | 110.8 (3) |
C1—P1—C7 | 105.87 (18) | C14—C13—H13 | 107.7 |
O1—P1—C13 | 114.64 (18) | C20—C13—H13 | 107.7 |
C1—P1—C13 | 105.97 (18) | P1—C13—H13 | 107.7 |
C7—P1—C13 | 105.92 (19) | C15—C14—C19 | 119.3 (4) |
C21—O3—C22 | 114.8 (4) | C15—C14—C13 | 120.0 (4) |
C6—C1—C2 | 119.1 (4) | C19—C14—C13 | 120.7 (4) |
C6—C1—P1 | 117.9 (3) | C14—C15—C16 | 120.7 (4) |
C2—C1—P1 | 123.0 (3) | C14—C15—H15 | 119.6 |
C3—C2—C1 | 120.0 (4) | C16—C15—H15 | 119.6 |
C3—C2—H2 | 120.0 | C17—C16—C15 | 120.1 (4) |
C1—C2—H2 | 120.0 | C17—C16—H16 | 119.9 |
C4—C3—C2 | 120.5 (4) | C15—C16—H16 | 119.9 |
C4—C3—H3 | 119.8 | C16—C17—C18 | 119.8 (4) |
C2—C3—H3 | 119.8 | C16—C17—H17 | 120.1 |
C3—C4—C5 | 120.2 (4) | C18—C17—H17 | 120.1 |
C3—C4—H4 | 119.9 | C17—C18—C19 | 120.0 (4) |
C5—C4—H4 | 119.9 | C17—C18—H18 | 120.0 |
C4—C5—C6 | 119.3 (4) | C19—C18—H18 | 120.0 |
C4—C5—H5 | 120.4 | C14—C19—C18 | 120.0 (4) |
C6—C5—H5 | 120.4 | C14—C19—H19 | 120.0 |
C1—C6—C5 | 120.9 (4) | C18—C19—H19 | 120.0 |
C1—C6—H6 | 119.6 | C21—C20—C13 | 111.7 (4) |
C5—C6—H6 | 119.6 | C21—C20—H20A | 109.3 |
C12—C7—C8 | 119.3 (4) | C13—C20—H20A | 109.3 |
C12—C7—P1 | 125.0 (3) | C21—C20—H20B | 109.3 |
C8—C7—P1 | 115.7 (3) | C13—C20—H20B | 109.3 |
C9—C8—C7 | 120.5 (4) | H20A—C20—H20B | 107.9 |
C9—C8—H8 | 119.8 | O2—C21—O3 | 123.4 (4) |
C7—C8—H8 | 119.8 | O2—C21—C20 | 126.8 (4) |
C10—C9—C8 | 119.8 (4) | O3—C21—C20 | 109.7 (4) |
C10—C9—H9 | 120.1 | O3—C22—C23 | 107.1 (5) |
C8—C9—H9 | 120.1 | O3—C22—H22A | 110.3 |
C9—C10—C11 | 120.1 (4) | C23—C22—H22A | 110.3 |
C9—C10—H10 | 120.0 | O3—C22—H22B | 110.3 |
C11—C10—H10 | 120.0 | C23—C22—H22B | 110.3 |
C12—C11—C10 | 120.5 (4) | H22A—C22—H22B | 108.5 |
C12—C11—H11 | 119.7 | C22—C23—H23A | 109.5 |
C10—C11—H11 | 119.8 | C22—C23—H23B | 109.5 |
C7—C12—C11 | 119.9 (4) | H23A—C23—H23B | 109.5 |
C7—C12—H12 | 120.1 | C22—C23—H23C | 109.5 |
C11—C12—H12 | 120.1 | H23A—C23—H23C | 109.5 |
C14—C13—C20 | 112.4 (3) | H23B—C23—H23C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O1i | 1.00 | 2.60 | 3.588 (5) | 171 |
C12—H12···O1i | 0.95 | 2.49 | 3.366 (5) | 154 |
C2—H2···O1i | 0.95 | 2.68 | 3.463 (5) | 140 |
C19—H19···O2ii | 0.95 | 2.47 | 3.385 (6) | 163 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C23H23O3P |
Mr | 378.38 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 5.788 (5), 17.499 (5), 19.463 (5) |
V (Å3) | 1971.3 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.15 × 0.04 × 0.03 |
Data collection | |
Diffractometer | Bruker–Nonius Kappa CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10345, 3383, 2169 |
Rint | 0.096 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.110, 0.98 |
No. of reflections | 3383 |
No. of parameters | 246 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.22 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.66 (17) |
Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski &Minor, 1997), DENZO, COLLECT and maXus (Mackay et al., 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1993), WinGX (Farrugia, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O1i | 1.00 | 2.60 | 3.588 (5) | 171 |
C12—H12···O1i | 0.95 | 2.49 | 3.366 (5) | 154 |
C2—H2···O1i | 0.95 | 2.68 | 3.463 (5) | 140 |
C19—H19···O2ii | 0.95 | 2.47 | 3.385 (6) | 163 |
Symmetry codes: (i) x−1, y, z; (ii) 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
NO COMMENT