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The title compound, Ph2P(O)CH(Ph)CH2COOEt or C23H23O3P, (I), assembles into columns extending down the a axis, via C—H...O hydrogen bonds. Compound (I) was isolated as a by-product in studies related to the development of a novel cyclization reaction [Evans et al. (2002). Tetrahedron Lett. 43, 299–301] and was synthesized independently to confirm its structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014642/ya6130sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014642/ya6130Isup2.hkl
Contains datablock I

CCDC reference: 197467

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

NO COMMENT

Experimental top

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).

Refinement top

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?]

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The C—H···O hydrogen-bonded column extending down the a axis. H atoms not involved in C—H···O bonds have been omitted.
Ethyl 3-(diphenylphosphinoyl)-3-phenylpropionate top
Crystal data top
C23H23O3PF(000) = 800
Mr = 378.38Dx = 1.275 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3383 reflections
a = 5.788 (5) Åθ = 3.1–25.0°
b = 17.499 (5) ŵ = 0.16 mm1
c = 19.463 (5) ÅT = 120 K
V = 1971.3 (19) Å3Rod, colourless
Z = 40.15 × 0.04 × 0.03 mm
Data collection top
Bruker–Nonius Kappa CCD area-detector
diffractometer
2169 reflections with I > 2σ(I)
Radiation source: Bruker–Nonius FR591 rotating anodeRint = 0.096
Graphite monochromatorθmax = 25.0°, θmin = 3.1°
Detector resolution: 9.091 pixels mm1 pixels mm-1h = 66
ϕ and ω scans to fill the asymmetric unitk = 1920
10345 measured reflectionsl = 2223
3383 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 0.98Δρmax = 0.16 e Å3
3383 reflectionsΔρmin = 0.22 e Å3
246 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0034 (9)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.66 (17)
Crystal data top
C23H23O3PV = 1971.3 (19) Å3
Mr = 378.38Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.788 (5) ŵ = 0.16 mm1
b = 17.499 (5) ÅT = 120 K
c = 19.463 (5) Å0.15 × 0.04 × 0.03 mm
Data collection top
Bruker–Nonius Kappa CCD area-detector
diffractometer
2169 reflections with I > 2σ(I)
10345 measured reflectionsRint = 0.096
3383 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.110Δρmax = 0.16 e Å3
S = 0.98Δρmin = 0.22 e Å3
3383 reflectionsAbsolute structure: Flack (1983)
246 parametersAbsolute structure parameter: 0.66 (17)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.9902 (2)0.11836 (6)0.21625 (5)0.0347 (3)
O11.2440 (4)0.11104 (16)0.20773 (13)0.0391 (7)
O20.5024 (6)0.03389 (15)0.09192 (14)0.0497 (8)
O30.7370 (6)0.13387 (17)0.10814 (17)0.0577 (9)
C10.8976 (7)0.2168 (2)0.2158 (2)0.0346 (10)
C20.6833 (8)0.2403 (2)0.2406 (2)0.0430 (12)
H20.57510.20350.25640.052*
C30.6279 (8)0.3172 (2)0.2421 (2)0.0443 (12)
H30.48210.33300.25950.053*
C40.7824 (7)0.3709 (2)0.2187 (2)0.0437 (11)
H40.74410.42370.22070.052*
C50.9934 (9)0.3484 (2)0.1922 (2)0.0447 (11)
H51.09870.38530.17480.054*
C61.0499 (7)0.2710 (2)0.1913 (2)0.0416 (11)
H61.19530.25530.17350.050*
C70.8936 (7)0.0793 (2)0.2975 (2)0.0348 (10)
C81.0583 (7)0.0783 (2)0.3501 (2)0.0381 (11)
H81.20870.09800.34190.046*
C91.0034 (8)0.0486 (2)0.41433 (19)0.0379 (10)
H91.11510.04890.45010.045*
C100.7873 (8)0.0188 (2)0.4259 (2)0.0384 (11)
H100.74970.00190.46960.046*
C110.6234 (8)0.0189 (2)0.3736 (2)0.0388 (11)
H110.47480.00240.38160.047*
C120.6754 (7)0.0497 (2)0.3098 (2)0.0360 (10)
H120.56160.05050.27460.043*
C130.8206 (7)0.0706 (2)0.1506 (2)0.0352 (11)
H130.65380.08010.16090.042*
C140.8719 (7)0.1046 (2)0.0802 (2)0.0340 (10)
C150.7096 (8)0.1499 (2)0.0480 (2)0.0355 (10)
H150.56730.16050.07040.043*
C160.7517 (7)0.1801 (2)0.0166 (2)0.0371 (10)
H160.63750.21050.03850.045*
C170.9584 (8)0.1662 (2)0.0490 (2)0.0362 (11)
H170.98720.18690.09330.043*
C181.1245 (7)0.1220 (2)0.0169 (2)0.0385 (10)
H181.26800.11270.03900.046*
C191.0815 (7)0.0912 (2)0.0480 (2)0.0364 (11)
H191.19590.06100.07010.044*
C200.8608 (8)0.0166 (2)0.1527 (2)0.0419 (11)
H20A1.01400.02830.13270.050*
H20B0.86130.03400.20110.050*
C210.6773 (9)0.0592 (2)0.1136 (2)0.0416 (11)
C220.5660 (11)0.1819 (3)0.0744 (3)0.074 (2)
H22A0.55570.16890.02500.089*
H22B0.41210.17440.09550.089*
C230.6421 (13)0.2623 (3)0.0830 (3)0.089 (2)
H23A0.79580.26880.06270.134*
H23B0.53230.29650.06000.134*
H23C0.64840.27480.13210.134*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0310 (5)0.0408 (6)0.0322 (5)0.0013 (6)0.0004 (5)0.0009 (5)
O10.0277 (14)0.0511 (17)0.0384 (16)0.0006 (14)0.0004 (13)0.0026 (15)
O20.047 (2)0.0437 (17)0.058 (2)0.0001 (19)0.0141 (18)0.0018 (14)
O30.073 (3)0.039 (2)0.061 (2)0.0075 (17)0.0155 (18)0.0071 (16)
C10.038 (2)0.042 (2)0.024 (2)0.0093 (19)0.003 (2)0.004 (2)
C20.041 (3)0.037 (3)0.051 (3)0.004 (2)0.001 (2)0.003 (2)
C30.033 (3)0.047 (3)0.053 (3)0.003 (2)0.001 (2)0.006 (2)
C40.046 (3)0.037 (3)0.048 (3)0.003 (2)0.014 (2)0.000 (2)
C50.049 (3)0.045 (3)0.040 (2)0.013 (3)0.004 (3)0.0042 (19)
C60.039 (3)0.045 (3)0.041 (3)0.006 (2)0.0006 (19)0.001 (2)
C70.033 (2)0.033 (2)0.039 (3)0.0001 (18)0.003 (2)0.0009 (19)
C80.030 (3)0.042 (3)0.043 (3)0.0022 (18)0.0017 (19)0.001 (2)
C90.039 (2)0.040 (2)0.035 (2)0.002 (3)0.007 (2)0.0043 (19)
C100.044 (3)0.038 (3)0.033 (2)0.006 (2)0.005 (2)0.002 (2)
C110.031 (2)0.038 (2)0.047 (3)0.000 (2)0.001 (2)0.004 (2)
C120.037 (3)0.036 (2)0.034 (2)0.0002 (19)0.0014 (18)0.004 (2)
C130.032 (3)0.043 (3)0.031 (2)0.002 (2)0.0002 (18)0.000 (2)
C140.037 (2)0.033 (2)0.032 (2)0.005 (2)0.0019 (19)0.0053 (19)
C150.034 (3)0.034 (2)0.038 (3)0.0028 (19)0.003 (2)0.001 (2)
C160.033 (3)0.038 (2)0.040 (3)0.000 (2)0.003 (2)0.000 (2)
C170.047 (3)0.035 (2)0.026 (2)0.006 (2)0.003 (2)0.0023 (19)
C180.033 (2)0.041 (2)0.041 (3)0.004 (2)0.003 (2)0.003 (2)
C190.030 (2)0.040 (3)0.039 (3)0.0011 (18)0.0025 (19)0.008 (2)
C200.045 (3)0.044 (3)0.037 (2)0.005 (2)0.002 (2)0.003 (2)
C210.051 (3)0.037 (3)0.036 (3)0.001 (2)0.003 (2)0.000 (2)
C220.111 (6)0.037 (3)0.073 (4)0.011 (3)0.021 (4)0.007 (3)
C230.139 (6)0.045 (3)0.084 (4)0.000 (4)0.009 (4)0.006 (3)
Geometric parameters (Å, º) top
P1—O11.484 (3)C11—C121.387 (5)
P1—C11.805 (4)C11—H110.9500
P1—C71.811 (4)C12—H120.9500
P1—C131.815 (4)C13—C141.523 (5)
O2—C211.183 (5)C13—C201.544 (6)
O3—C211.356 (5)C13—H131.0000
O3—C221.456 (6)C14—C151.379 (6)
C1—C61.379 (5)C14—C191.385 (6)
C1—C21.393 (6)C15—C161.386 (6)
C2—C31.383 (6)C15—H150.9500
C2—H20.9500C16—C171.374 (6)
C3—C41.376 (6)C16—H160.9500
C3—H30.9500C17—C181.383 (6)
C4—C51.383 (6)C17—H170.9500
C4—H40.9500C18—C191.396 (6)
C5—C61.394 (6)C18—H180.9500
C5—H50.9500C19—H190.9500
C6—H60.9500C20—C211.504 (6)
C7—C121.386 (6)C20—H20A0.9900
C7—C81.399 (5)C20—H20B0.9900
C8—C91.391 (5)C22—C231.484 (7)
C8—H80.9500C22—H22A0.9900
C9—C101.374 (6)C22—H22B0.9900
C9—H90.9500C23—H23A0.9800
C10—C111.391 (6)C23—H23B0.9800
C10—H100.9500C23—H23C0.9800
O1—P1—C1112.06 (17)C14—C13—P1110.4 (3)
O1—P1—C7111.75 (17)C20—C13—P1110.8 (3)
C1—P1—C7105.87 (18)C14—C13—H13107.7
O1—P1—C13114.64 (18)C20—C13—H13107.7
C1—P1—C13105.97 (18)P1—C13—H13107.7
C7—P1—C13105.92 (19)C15—C14—C19119.3 (4)
C21—O3—C22114.8 (4)C15—C14—C13120.0 (4)
C6—C1—C2119.1 (4)C19—C14—C13120.7 (4)
C6—C1—P1117.9 (3)C14—C15—C16120.7 (4)
C2—C1—P1123.0 (3)C14—C15—H15119.6
C3—C2—C1120.0 (4)C16—C15—H15119.6
C3—C2—H2120.0C17—C16—C15120.1 (4)
C1—C2—H2120.0C17—C16—H16119.9
C4—C3—C2120.5 (4)C15—C16—H16119.9
C4—C3—H3119.8C16—C17—C18119.8 (4)
C2—C3—H3119.8C16—C17—H17120.1
C3—C4—C5120.2 (4)C18—C17—H17120.1
C3—C4—H4119.9C17—C18—C19120.0 (4)
C5—C4—H4119.9C17—C18—H18120.0
C4—C5—C6119.3 (4)C19—C18—H18120.0
C4—C5—H5120.4C14—C19—C18120.0 (4)
C6—C5—H5120.4C14—C19—H19120.0
C1—C6—C5120.9 (4)C18—C19—H19120.0
C1—C6—H6119.6C21—C20—C13111.7 (4)
C5—C6—H6119.6C21—C20—H20A109.3
C12—C7—C8119.3 (4)C13—C20—H20A109.3
C12—C7—P1125.0 (3)C21—C20—H20B109.3
C8—C7—P1115.7 (3)C13—C20—H20B109.3
C9—C8—C7120.5 (4)H20A—C20—H20B107.9
C9—C8—H8119.8O2—C21—O3123.4 (4)
C7—C8—H8119.8O2—C21—C20126.8 (4)
C10—C9—C8119.8 (4)O3—C21—C20109.7 (4)
C10—C9—H9120.1O3—C22—C23107.1 (5)
C8—C9—H9120.1O3—C22—H22A110.3
C9—C10—C11120.1 (4)C23—C22—H22A110.3
C9—C10—H10120.0O3—C22—H22B110.3
C11—C10—H10120.0C23—C22—H22B110.3
C12—C11—C10120.5 (4)H22A—C22—H22B108.5
C12—C11—H11119.7C22—C23—H23A109.5
C10—C11—H11119.8C22—C23—H23B109.5
C7—C12—C11119.9 (4)H23A—C23—H23B109.5
C7—C12—H12120.1C22—C23—H23C109.5
C11—C12—H12120.1H23A—C23—H23C109.5
C14—C13—C20112.4 (3)H23B—C23—H23C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O1i1.002.603.588 (5)171
C12—H12···O1i0.952.493.366 (5)154
C2—H2···O1i0.952.683.463 (5)140
C19—H19···O2ii0.952.473.385 (6)163
Symmetry codes: (i) x1, y, z; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC23H23O3P
Mr378.38
Crystal system, space groupOrthorhombic, P212121
Temperature (K)120
a, b, c (Å)5.788 (5), 17.499 (5), 19.463 (5)
V3)1971.3 (19)
Z4
Radiation typeMo Kα
µ (mm1)0.16
Crystal size (mm)0.15 × 0.04 × 0.03
Data collection
DiffractometerBruker–Nonius Kappa CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10345, 3383, 2169
Rint0.096
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.110, 0.98
No. of reflections3383
No. of parameters246
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.22
Absolute structureFlack (1983)
Absolute structure parameter0.66 (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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O1i1.002.603.588 (5)171
C12—H12···O1i0.952.493.366 (5)154
C2—H2···O1i0.952.683.463 (5)140
C19—H19···O2ii0.952.473.385 (6)163
Symmetry codes: (i) x1, y, z; (ii) x+1, y, z.
 

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