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The crystal structures of four alkyl 3-oxo-2-(tri­phenyl­phospho­ranyl­idene)­butyrates, where the alkyl group is methyl (C23H21O3P·0.5C6H6), (II), ethyl (C24H23O3P), (III), isopropyl (C25H25O3P), (IV), or tert-butyl (C26H27O3P), (V), show all of them to have the same conformation. They present a tetrahedral P atom and an sp2 yl­idic C atom, with the carbonyl groups adopting anti conformations with respect to the keto groups located close to the P atom. P-C-C-O torsion angles, bond lengths and angles indicate an effective electronic delocalization toward the keto groups. In each case, one H atom of the alkoxy group is close to one of the phenyl rings. These preferred conformations are evaluated as the result of attractive and repulsive intramolecular interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100016012/bk1566sup1.cif
Contains datablocks global, II, III, IV, V

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016012/bk1566IIsup2.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016012/bk1566IIIsup3.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016012/bk1566IVsup4.hkl
Contains datablock IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016012/bk1566Vsup5.hkl
Contains datablock V

CCDC references: 159993; 159994; 159995; 159996

Comment top

Crystalline (3-carboethoxy-3-triphenylphosphoranylidene-2-oxopropanyl)- triphenylphosphonium bromide, (I), has the conformation shown in the scheme below and its 1H NMR spectrum shows that, in solution, the ethoxylic methyl-H atoms are diamagnetically shielded by a phenyl ring (Barahona et al., 1998). Similar shielding has been observed with other nonionic ylides, indicating that the preferred conformation of (I) is not dictated by the ionic phosphonium residue (Bachrach & Nitsche, 1994; Bacaloglu et al., 1995; Abell et al., 1982; Abell & Massy-Westropp, 1982b). We have therefore examined the crystal structures of four nonionic ylides with different alkoxy groups, with R = CH3, (II), CH2CH3, (III), CH(CH3)2, (IV), and C(CH3)3, (V). One of these compounds, (III), has already been described by Abell et al. (1989) and is almost isostructural with (IV). \sch

The molecular structures of compounds (II)-(V) are shown in Figs. 1 to 4 and selected dimensions are given in Tables 1 to 8. Ylides (I) to (V) have a nearly tetrahedral P atom with helicoidally arranged phenyl rings. The PhA phenyl rings bisect the planes formed by the ylidic C atoms and the carbonyl groups, while the PhC phenyl rings present their faces to the alkoxy groups.

The Ph—P=C and Ph—P—Ph angles, which are close to 109°, indicate a slightly distorted tetrahedral environment around the P centres, arguing against dsp3-P hybridization. The major deviations from normal values are observed for the C1C—P1—C1B angles in the ethyl [101.2 (1)°], i-propyl [101.0 (2)°] and tert-butyl [100.2 (1)°] derivatives, probably as a result of a steric compression between the PhC rings and the alkoxy groups, which pushes PhC toward PhB. The sums of the angles about the ylidic C atom are in all cases consistent with a near-trigonal planar geometry and sp2 hybridization.

The P—C1 bond lengths, which are in the range 1.740 (2)–1.757 (3) Å, are in between the commonly accepted values for a single bond (~1.80–1.83 Å) and a double bond (~1.63–1.73 Å) as a consequence of electronic delocalization, which also shortens the C1—C2 and C1—C5 bonds. Consistent with this, the keto bond C2=O4 is longer than in simple ketones. However, in the ester residue, C5=O7 is slightly shorter and C5—O6 is slightly longer than in simple ketones and esters.

The P—C—C—O dihedral angles are close to zero for the keto group and near to 180 Å for the ester carbonyl O atom, showing a better delocalization toward the keto group. The carbonyl groups adopt the anti conformation to reduce dipole-dipole repulsions and the O4 atoms of the keto groups are within 2.7–2.8 Å of the P atom, i.e. within the sum of the van der Waals radii, due to favourable interactions. As a result, the P1—C1—C2 angles are lower than the normal value of 120°. Electronic delocalization has also been seen in crystalline 6-ethoxycarbonyl-6-triphenylphosphoranylidene-5-oxohexanoic acid and 5-ethoxycarbonyl-5-triphenylphosphoranyliden-4-oxopentanoic acid (Abell et al., 1988, 1991), although intramolecular hydrogen bonding could affect the conformations of these compounds.

The P1—O6 distances of ca 3 Å are consistent with a favourable interaction which could stabilize a preferred conformation. The crystal structures of (III), (IV) and (V) show a shorter than normal C8—C9 bond for the alkoxy groups [1.486 (11)–1.500 (3) Å, rather than ~1.53 Å ref?]. Again, a steric compression caused by neighbouring PhC groups could be important (Seidl et al., 1998). This question will be discussed elsewhere.

Related literature top

For related literature, see: Abell & Massy-Westropp (1982); Abell et al. (1988, 1989, 1991); Abell, Doyle & Massy-Westropp (1982); Bacaloglu et al. (1995); Bachrach & Nitsche (1994); Barahona et al. (1998); Cristau & Plúnat (1994); Seidl et al. (1998).

Experimental top

The stabilized ylides were prepared via a classical two-step method involving ester ylid C-acylation with acyl halides in order to form a phosphonium salt as the intermediate, followed by an acid-base reaction (transylidation) with a second equivalent of the ester ylid (Cristau et al., 1994). Thus, compounds (II)-(V) were obtained by the reaction of acetyl chloride with the corresponding carboalkoxymethylenetriphenylphosphorane. The general procedure used for the synthesis of each of the ylides was as follows: a solution of acyl chloride (20 mmol) in dry benzene (5 ml) was slowly added to carboalkoxymethylenetriphenylphosphorane (40 mmol) in dry benzene (100 ml) under a dry atmosphere. The stirred solution was kept at room temperature for 30 min and a white solid was separated. After filtration of the carboalkoxymethyltriphenylphosphonium chloride, the solvent was evaporated to give an oil, which was recrystallized from ethyl acetate. Yields were 70–90%.

Refinement top

Compound (IV) was the most difficult to obtain in a crystalline form suitable for X-ray diffraction, for even the best of the many samples scrutinized had less than 50% of the whole data set with I > 2σ. The systematic extinctions initially suggested the centrosymmetric space group Pbca, but it was impossible to solve the structure in that group. A solution with two molecules in the asymmetric unit came out easily, however, when the space group was changed to P212121. Even though the original model seemed to suggest only a slight symmetry link between the two independent moieties, further refinement tended to confirm the existence of a real centre. The change to Pbca substantially reduced the number of parameters, but did not worsen the agreement factors, the overall geometry or the temperature factors. Some problems were also found in structure (III), which displayed a splitting of the non-aromatic ligand into two almost equally populated halves (Fig. 2). Because of the uneven quality of the diffraction data, and in order to systematize the refinement procedures used, the phenyl rings were refined under the assumption of a flat geometry and equal bond lengths. The only solvated structure was that of (II), with half a benzene molecule per formula unit. H atoms were included at idealized positions (C—H 0.96 Å) and refined using a riding model for both coordinates and displacement parameters. The terminal methyl groups were, in addition, allowed to rotate as fixed bodies around the corresponding O—C or C—C axis.

Computing details top

For all compounds, data collection: P3/PC (Siemens, 1993); cell refinement: P3/PC; data reduction: XDISK in SHELXTL/PC (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC; software used to prepare material for publication: CIFTAB (Sheldrick, 1993), PARST (Nardelli, 1983) and the Cambridge Structural Database (Allen & Kennard, 1993).

Figures top
[Figure 1] Fig. 1. The molecular structure of (II) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The molecular structure of (III) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity.
[Figure 3] Fig. 3. The molecular structure of (IV) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity.
[Figure 4] Fig. 4. The molecular structure of (V) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity.
(II) Methyl 3-oxo-2-(triphenylphosphoranylidene)butyrate top
Crystal data top
C23H21O3P·0.5C6H6F(000) = 876
Mr = 415.42Dx = 1.254 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.698 (5) ÅCell parameters from 25 reflections
b = 8.939 (4) Åθ = 7.5–12.5°
c = 23.026 (11) ŵ = 0.15 mm1
β = 91.66 (4)°T = 293 K
V = 2200.9 (17) Å3Prism, colourless
Z = 40.24 × 0.18 × 0.15 mm
Data collection top
Siemens R3m
diffractometer
Rint = 0.055
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 1.8°
Graphite monochromatorh = 1212
ω/2θ scansk = 010
4102 measured reflectionsl = 027
3892 independent reflections2 standard reflections every 98 reflections
2766 reflections with I > 2σ(I) intensity decay: <2%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.042P)2 + 0.721P]
where P = (Fo2 + 2Fc2)/3
3892 reflections(Δ/σ)max < 0.01
274 parametersΔρmax = 0.17 e Å3
33 restraintsΔρmin = 0.19 e Å3
Crystal data top
C23H21O3P·0.5C6H6V = 2200.9 (17) Å3
Mr = 415.42Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.698 (5) ŵ = 0.15 mm1
b = 8.939 (4) ÅT = 293 K
c = 23.026 (11) Å0.24 × 0.18 × 0.15 mm
β = 91.66 (4)°
Data collection top
Siemens R3m
diffractometer
Rint = 0.055
4102 measured reflections2 standard reflections every 98 reflections
3892 independent reflections intensity decay: <2%
2766 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.04333 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 1.06Δρmax = 0.17 e Å3
3892 reflectionsΔρmin = 0.19 e Å3
274 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.47999 (5)0.23447 (6)0.15600 (2)0.03199 (14)
C10.61435 (18)0.3450 (2)0.15928 (8)0.0343 (5)
C20.69652 (19)0.3280 (2)0.10973 (9)0.0367 (5)
C30.8276 (2)0.3908 (3)0.10922 (11)0.0538 (6)
H3A0.87010.36480.07330.081*
H3B0.87220.34970.14110.081*
H3C0.82400.49770.11290.081*
O40.66075 (13)0.26152 (17)0.06583 (6)0.0454 (4)
C50.6364 (2)0.4504 (2)0.20517 (9)0.0412 (5)
O60.53002 (15)0.49146 (19)0.23377 (7)0.0633 (5)
O70.73623 (15)0.5048 (2)0.21710 (7)0.0642 (5)
C80.5427 (3)0.5902 (4)0.28240 (13)0.0853 (10)
H1A0.46120.61660.29780.128*
H1B0.58620.67910.27000.128*
H1C0.58900.54100.31190.128*
C1A0.52418 (18)0.0479 (2)0.13205 (8)0.0346 (5)
C2A0.4714 (2)0.0195 (2)0.08432 (9)0.0454 (6)
H2A0.40950.02990.06420.054*
C3A0.5109 (2)0.1602 (3)0.06659 (11)0.0576 (7)
H3A10.47560.20520.03450.069*
C4A0.6019 (2)0.2334 (3)0.09615 (12)0.0624 (7)
H4A0.62820.32780.08410.075*
C5A0.6545 (2)0.1678 (3)0.14364 (11)0.0574 (7)
H5A0.71560.21840.16380.069*
C6A0.6167 (2)0.0262 (2)0.16144 (10)0.0453 (6)
H6A0.65350.01880.19310.054*
C1B0.40190 (18)0.2192 (2)0.22699 (8)0.0353 (5)
C2B0.4518 (2)0.1342 (3)0.27075 (9)0.0536 (6)
H2B0.52510.08050.26370.064*
C3B0.3932 (3)0.1287 (3)0.32486 (10)0.0672 (8)
H3B10.42740.07100.35400.081*
C4B0.2849 (2)0.2071 (3)0.33624 (10)0.0618 (7)
H4B0.24570.20240.37280.074*
C5B0.2353 (2)0.2918 (3)0.29335 (10)0.0660 (8)
H5B0.16220.34560.30090.079*
C6B0.2928 (2)0.2987 (3)0.23879 (10)0.0539 (6)
H6B0.25810.35690.20990.065*
C1C0.36249 (18)0.3000 (2)0.10758 (8)0.0340 (5)
C2C0.3850 (2)0.4251 (2)0.07360 (9)0.0405 (5)
H2C0.46110.47500.07550.049*
C3C0.2940 (2)0.4764 (3)0.03669 (9)0.0525 (6)
H3C10.30920.56030.01370.063*
C4C0.1813 (2)0.4030 (3)0.03419 (10)0.0550 (7)
H4C0.12040.43770.00950.066*
C5C0.1581 (2)0.2785 (3)0.06796 (10)0.0541 (6)
H5C0.08180.22930.06610.065*
C6C0.24802 (15)0.2270 (2)0.10444 (8)0.0463 (6)
H6C0.23220.14280.12720.056*
C1D0.11023 (15)0.0110 (2)0.03265 (8)0.0837 (10)
H1D0.18430.01780.05470.100*
C2D0.0163 (2)0.0831 (3)0.04912 (13)0.0816 (9)
H2D0.02690.13990.08270.098*
C3D0.0931 (3)0.0949 (3)0.01678 (10)0.0794 (9)
H3D0.15560.15970.02840.095*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0317 (3)0.0328 (3)0.0315 (3)0.0010 (2)0.0015 (2)0.0020 (2)
C10.0341 (11)0.0340 (11)0.0349 (11)0.0010 (9)0.0040 (9)0.0008 (9)
C20.0357 (12)0.0329 (11)0.0417 (12)0.0023 (9)0.0047 (9)0.0075 (10)
C30.0380 (13)0.0584 (16)0.0647 (16)0.0048 (12)0.0040 (11)0.0010 (13)
O40.0509 (9)0.0482 (9)0.0371 (8)0.0057 (8)0.0023 (7)0.0000 (7)
C50.0435 (13)0.0402 (13)0.0402 (12)0.0019 (11)0.0082 (10)0.0041 (10)
O60.0555 (10)0.0630 (11)0.0708 (11)0.0068 (9)0.0083 (9)0.0308 (10)
O70.0500 (10)0.0793 (12)0.0640 (11)0.0142 (9)0.0156 (8)0.0202 (10)
C80.102 (2)0.084 (2)0.0690 (19)0.0016 (19)0.0057 (17)0.0400 (17)
C1A0.0372 (11)0.0328 (11)0.0335 (11)0.0032 (9)0.0021 (9)0.0007 (9)
C2A0.0479 (14)0.0415 (13)0.0468 (13)0.0034 (11)0.0024 (11)0.0012 (11)
C3A0.0686 (17)0.0445 (14)0.0594 (16)0.0092 (13)0.0003 (13)0.0127 (13)
C4A0.0729 (18)0.0335 (13)0.0798 (19)0.0002 (13)0.0116 (15)0.0113 (14)
C5A0.0596 (16)0.0424 (14)0.0700 (17)0.0130 (12)0.0013 (13)0.0080 (13)
C6A0.0498 (14)0.0425 (13)0.0435 (13)0.0072 (11)0.0019 (11)0.0018 (11)
C1B0.0371 (11)0.0356 (11)0.0330 (10)0.0034 (9)0.0013 (9)0.0015 (9)
C2B0.0608 (16)0.0596 (15)0.0400 (13)0.0173 (13)0.0076 (11)0.0098 (12)
C3B0.090 (2)0.0712 (19)0.0398 (14)0.0169 (16)0.0086 (14)0.0181 (13)
C4B0.0699 (18)0.0722 (18)0.0424 (14)0.0045 (15)0.0154 (13)0.0018 (13)
C5B0.0567 (16)0.089 (2)0.0519 (15)0.0184 (15)0.0121 (12)0.0053 (15)
C6B0.0512 (15)0.0681 (17)0.0421 (13)0.0140 (13)0.0029 (11)0.0019 (12)
C1C0.0334 (11)0.0350 (11)0.0337 (11)0.0018 (9)0.0024 (8)0.0007 (9)
C2C0.0415 (12)0.0407 (12)0.0396 (12)0.0006 (10)0.0059 (10)0.0004 (10)
C3C0.0669 (17)0.0520 (15)0.0389 (13)0.0122 (13)0.0082 (11)0.0078 (11)
C4C0.0513 (15)0.0705 (17)0.0443 (14)0.0182 (13)0.0187 (12)0.0043 (13)
C5C0.0375 (13)0.0680 (17)0.0574 (15)0.0016 (12)0.0121 (11)0.0094 (14)
C6C0.0402 (13)0.0499 (14)0.0491 (13)0.0042 (11)0.0046 (10)0.0044 (11)
C1D0.069 (2)0.082 (2)0.099 (3)0.0062 (18)0.0163 (18)0.032 (2)
C2D0.109 (3)0.065 (2)0.070 (2)0.0011 (19)0.0006 (19)0.0028 (16)
C3D0.080 (2)0.0649 (19)0.095 (2)0.0129 (17)0.0229 (18)0.0174 (18)
Geometric parameters (Å, º) top
P1—C11.747 (2)C1B—C2B1.382 (3)
P1—C1C1.802 (2)C1B—C6B1.386 (3)
P1—C1A1.815 (2)C2B—C3B1.379 (3)
P1—C1B1.819 (2)C3B—C4B1.372 (3)
C1—C21.428 (3)C4B—C5B1.364 (3)
C1—C51.441 (3)C5B—C6B1.384 (3)
C2—O41.243 (2)C1C—C2C1.382 (3)
C2—C31.510 (3)C1C—C6C1.391 (3)
C5—O71.212 (2)C2C—C3C1.389 (3)
C5—O61.349 (3)C3C—C4C1.375 (3)
O6—C81.435 (3)C4C—C5C1.376 (3)
C1A—C6A1.384 (3)C5C—C6C1.374 (3)
C1A—C2A1.388 (3)C1D—C3Di1.3706 (16)
C2A—C3A1.385 (3)C1D—C2D1.3726 (15)
C3A—C4A1.369 (3)C2D—C3D1.3726 (16)
C4A—C5A1.376 (3)C3D—C1Di1.3706 (16)
C5A—C6A1.387 (3)
P1···O42.806 (2)P1···O62.971 (2)
C1—P1—C1C115.61 (10)C4A—C5A—C6A120.1 (2)
C1—P1—C1A108.97 (10)C1A—C6A—C5A119.9 (2)
C1C—P1—C1A106.92 (9)C2B—C1B—C6B118.67 (19)
C1—P1—C1B111.13 (10)C2B—C1B—P1121.30 (16)
C1C—P1—C1B105.66 (10)C6B—C1B—P1119.98 (16)
C1A—P1—C1B108.24 (9)C3B—C2B—C1B120.2 (2)
C2—C1—C5123.05 (19)C4B—C3B—C2B120.9 (2)
C2—C1—P1113.18 (15)C5B—C4B—C3B119.3 (2)
C5—C1—P1123.63 (16)C4B—C5B—C6B120.7 (2)
O4—C2—C1120.25 (19)C5B—C6B—C1B120.3 (2)
O4—C2—C3118.62 (19)C2C—C1C—C6C119.30 (18)
C1—C2—C3121.1 (2)C2C—C1C—P1120.01 (15)
O7—C5—O6121.1 (2)C6C—C1C—P1120.69 (15)
O7—C5—C1126.3 (2)C1C—C2C—C3C120.0 (2)
O6—C5—C1112.48 (18)C4C—C3C—C2C120.0 (2)
C5—O6—C8116.80 (19)C5C—C4C—C3C120.4 (2)
C6A—C1A—C2A119.5 (2)C4C—C5C—C6C119.9 (2)
C6A—C1A—P1118.38 (16)C5C—C6C—C1C120.48 (19)
C2A—C1A—P1122.09 (16)C3Di—C1D—C2D118.90 (18)
C3A—C2A—C1A120.0 (2)C3D—C2D—C1D121.1 (2)
C4A—C3A—C2A120.2 (2)C1Di—C3D—C2D120.0 (2)
C3A—C4A—C5A120.3 (2)
C1C—P1—C1—C275.63 (17)C1—P1—C1B—C2B72.2 (2)
C1A—P1—C1—C244.78 (17)C1C—P1—C1B—C2B161.65 (18)
C1B—P1—C1—C2163.96 (14)C1A—P1—C1B—C2B47.4 (2)
C1C—P1—C1—C5100.25 (18)C1—P1—C1B—C6B105.10 (19)
C1A—P1—C1—C5139.35 (17)C1C—P1—C1B—C6B21.0 (2)
C1B—P1—C1—C520.2 (2)C1A—P1—C1B—C6B135.28 (18)
C5—C1—C2—O4163.95 (19)C6B—C1B—C2B—C3B0.3 (4)
P1—C1—C2—O412.0 (3)P1—C1B—C2B—C3B177.7 (2)
C5—C1—C2—C315.7 (3)C1B—C2B—C3B—C4B0.0 (4)
P1—C1—C2—C3168.43 (16)C2B—C3B—C4B—C5B0.3 (4)
C2—C1—C5—O722.1 (3)C3B—C4B—C5B—C6B0.3 (4)
P1—C1—C5—O7162.47 (19)C4B—C5B—C6B—C1B0.0 (4)
C2—C1—C5—O6154.90 (19)C2B—C1B—C6B—C5B0.3 (4)
P1—C1—C5—O620.6 (3)P1—C1B—C6B—C5B177.7 (2)
O7—C5—O6—C86.1 (3)C1—P1—C1C—C2C3.7 (2)
C1—C5—O6—C8176.7 (2)C1A—P1—C1C—C2C117.79 (17)
C1—P1—C1A—C6A52.57 (19)C1B—P1—C1C—C2C127.05 (17)
C1C—P1—C1A—C6A178.19 (16)C1—P1—C1C—C6C175.47 (15)
C1B—P1—C1A—C6A68.40 (18)C1A—P1—C1C—C6C63.01 (18)
C1—P1—C1A—C2A125.12 (17)C1B—P1—C1C—C6C52.14 (18)
C1C—P1—C1A—C2A0.50 (19)C6C—C1C—C2C—C3C0.2 (3)
C1B—P1—C1A—C2A113.92 (18)P1—C1C—C2C—C3C179.42 (16)
C6A—C1A—C2A—C3A0.3 (3)C1C—C2C—C3C—C4C0.3 (3)
P1—C1A—C2A—C3A178.00 (17)C2C—C3C—C4C—C5C0.2 (4)
C1A—C2A—C3A—C4A0.1 (3)C3C—C4C—C5C—C6C0.0 (4)
C2A—C3A—C4A—C5A0.1 (4)C4C—C5C—C6C—C1C0.1 (3)
C3A—C4A—C5A—C6A0.8 (4)C2C—C1C—C6C—C5C0.0 (3)
C2A—C1A—C6A—C5A1.0 (3)P1—C1C—C6C—C5C179.22 (16)
P1—C1A—C6A—C5A178.77 (17)C3Di—C1D—C2D—C3D0.4 (4)
C4A—C5A—C6A—C1A1.2 (3)C1D—C2D—C3D—C1Di0.5 (4)
Symmetry code: (i) x, y, z.
(III) Ethyl 3-oxo-2-(triphenylphosphoranylidene)butyrate top
Crystal data top
C24H23O3PF(000) = 1648
Mr = 390.39Dx = 1.221 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 14.815 (4) Åθ = 7.5–12.5°
b = 16.226 (5) ŵ = 0.15 mm1
c = 17.670 (5) ÅT = 293 K
V = 4248 (2) Å3Prism, colourless
Z = 80.27 × 0.20 × 0.16 mm
Data collection top
Siemens R3m
diffractometer
Rint = 0.058
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.2°
Graphite monochromatorh = 017
ω/2θ scansk = 019
3911 measured reflectionsl = 020
3737 independent reflections2 standard reflections every 98 reflections
1966 reflections with I > 2σ(I) intensity decay: <2%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.133P)2]
where P = (Fo2 + 2Fc2)/3
3737 reflections(Δ/σ)max < 0.01
284 parametersΔρmax = 0.22 e Å3
33 restraintsΔρmin = 0.18 e Å3
Crystal data top
C24H23O3PV = 4248 (2) Å3
Mr = 390.39Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.815 (4) ŵ = 0.15 mm1
b = 16.226 (5) ÅT = 293 K
c = 17.670 (5) Å0.27 × 0.20 × 0.16 mm
Data collection top
Siemens R3m
diffractometer
Rint = 0.058
3911 measured reflections2 standard reflections every 98 reflections
3737 independent reflections intensity decay: <2%
1966 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.05833 restraints
wR(F2) = 0.124H-atom parameters constrained
S = 0.99Δρmax = 0.22 e Å3
3737 reflectionsΔρmin = 0.18 e Å3
284 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
P10.24167 (5)0.31573 (5)0.16808 (4)0.0385 (2)
C10.3047 (2)0.40322 (18)0.14272 (18)0.0401 (8)
C20.3338 (2)0.3965 (2)0.0655 (2)0.0501 (9)
C30.3882 (3)0.4628 (2)0.0269 (2)0.0801 (13)
H3A0.40650.44390.02220.120*
H3B0.44080.47500.05670.120*
H3C0.35210.51160.02180.120*
O40.31063 (15)0.33503 (15)0.02781 (12)0.0607 (7)
C50.3321 (3)0.4692 (2)0.1925 (2)0.0585 (10)
O70.38327 (19)0.52421 (16)0.17867 (17)0.0872 (9)
O6'0.3186 (16)0.4501 (15)0.2666 (5)0.082 (5)0.43 (3)
C8'0.336 (2)0.522 (2)0.3136 (18)0.141 (14)0.43 (3)
H8'10.32220.57170.28510.169*0.43 (3)
H8'20.39910.52370.32750.169*0.43 (3)
C9'0.279 (3)0.520 (4)0.384 (2)0.22 (2)0.43 (3)
H9'10.30340.55840.42000.326*0.43 (3)
H9'20.28000.46570.40470.326*0.43 (3)
H9'30.21850.53550.37150.326*0.43 (3)
O6''0.2771 (12)0.4741 (8)0.2534 (7)0.075 (3)0.57 (3)
C8''0.289 (2)0.5389 (11)0.3105 (12)0.116 (9)0.57 (3)
H8''10.23110.56490.32130.139*0.57 (3)
H8''20.33010.58060.29220.139*0.57 (3)
C9''0.3255 (18)0.499 (2)0.3805 (16)0.151 (9)0.57 (3)
H9''10.28090.46280.40150.227*0.57 (3)
H9''20.34050.54090.41680.227*0.57 (3)
H9''30.37870.46820.36790.227*0.57 (3)
C1A0.3113 (2)0.22495 (19)0.16040 (18)0.0455 (8)
C2A0.2844 (3)0.1552 (2)0.1214 (2)0.0730 (12)
H2AA0.22910.15470.09650.088*
C3A0.3394 (3)0.0863 (3)0.1193 (3)0.0973 (17)
H3AA0.32080.03960.09300.117*
C4A0.4213 (3)0.0865 (3)0.1557 (3)0.0910 (16)
H4AA0.45730.03950.15530.109*
C5A0.4498 (3)0.1560 (3)0.1928 (3)0.0980 (16)
H5AA0.50570.15680.21670.118*
C6A0.3948 (2)0.2252 (2)0.1943 (2)0.0796 (13)
H6AA0.41480.27260.21870.095*
C1B0.1984 (2)0.31892 (19)0.26423 (15)0.0389 (7)
C2B0.2353 (3)0.2738 (2)0.32263 (19)0.0619 (10)
H2BA0.28550.24080.31390.074*
C3B0.1977 (3)0.2777 (3)0.3947 (2)0.0848 (14)
H3BA0.22290.24750.43410.102*
C4B0.1234 (3)0.3261 (3)0.4077 (2)0.0849 (14)
H4BA0.09800.32830.45580.102*
C5B0.0866 (3)0.3713 (3)0.3496 (2)0.0850 (14)
H5BA0.03680.40470.35870.102*
C6B0.1229 (2)0.3674 (2)0.2780 (2)0.0630 (11)
H6BA0.09680.39730.23880.076*
C1C0.13793 (19)0.3022 (2)0.11422 (18)0.0442 (8)
C2C0.0811 (2)0.2367 (2)0.13070 (19)0.0563 (10)
H2CA0.09860.19690.16560.068*
C3C0.0020 (3)0.2308 (3)0.0949 (2)0.0794 (14)
H3CA0.04020.18710.10620.095*
C4C0.0285 (3)0.2890 (3)0.0429 (3)0.0837 (14)
H4CA0.08370.28410.01840.100*
C5C0.0273 (2)0.3545 (3)0.0273 (2)0.0754 (12)
H5CA0.00900.39470.00690.091*
C6C0.1108 (2)0.3612 (2)0.06236 (18)0.0520 (9)
H6CA0.14860.40530.05100.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0394 (4)0.0370 (4)0.0392 (4)0.0038 (4)0.0003 (4)0.0011 (4)
C10.0360 (18)0.0341 (18)0.050 (2)0.0072 (16)0.0027 (15)0.0060 (15)
C20.038 (2)0.057 (2)0.055 (2)0.0084 (19)0.0046 (18)0.017 (2)
C30.075 (3)0.086 (3)0.078 (3)0.009 (2)0.015 (2)0.035 (2)
O40.0630 (16)0.0670 (18)0.0521 (15)0.0027 (14)0.0113 (13)0.0051 (14)
C50.055 (2)0.054 (2)0.066 (3)0.011 (2)0.006 (2)0.001 (2)
O70.088 (2)0.0572 (16)0.116 (2)0.0350 (16)0.0004 (19)0.0050 (18)
O6'0.085 (10)0.100 (11)0.061 (6)0.043 (8)0.005 (5)0.009 (5)
C8'0.16 (3)0.18 (3)0.085 (16)0.09 (2)0.000 (16)0.049 (16)
C9'0.29 (5)0.23 (4)0.13 (3)0.10 (4)0.12 (3)0.08 (3)
O6''0.105 (8)0.060 (5)0.061 (4)0.030 (5)0.007 (5)0.019 (3)
C8''0.16 (2)0.085 (8)0.099 (12)0.047 (10)0.007 (14)0.018 (7)
C9''0.150 (17)0.191 (19)0.11 (2)0.061 (16)0.007 (14)0.061 (14)
C1A0.0430 (19)0.039 (2)0.054 (2)0.0021 (16)0.0083 (18)0.0024 (18)
C2A0.064 (3)0.044 (2)0.112 (3)0.009 (2)0.017 (2)0.019 (2)
C3A0.075 (3)0.045 (3)0.172 (5)0.008 (3)0.040 (3)0.019 (3)
C4A0.076 (3)0.059 (3)0.137 (5)0.026 (3)0.031 (3)0.009 (3)
C5A0.070 (3)0.111 (4)0.112 (4)0.036 (3)0.014 (3)0.026 (3)
C6A0.057 (3)0.077 (3)0.106 (3)0.020 (2)0.015 (2)0.032 (3)
C1B0.0451 (19)0.0360 (18)0.0357 (18)0.0084 (17)0.0018 (15)0.0015 (16)
C2B0.079 (3)0.058 (2)0.049 (2)0.009 (2)0.001 (2)0.0098 (19)
C3B0.127 (4)0.077 (3)0.050 (3)0.008 (3)0.006 (3)0.011 (2)
C4B0.100 (4)0.102 (4)0.053 (3)0.030 (3)0.032 (3)0.010 (3)
C5B0.067 (3)0.122 (4)0.066 (3)0.006 (3)0.015 (2)0.023 (3)
C6B0.059 (2)0.081 (3)0.050 (2)0.006 (2)0.0002 (19)0.010 (2)
C1C0.0361 (18)0.050 (2)0.046 (2)0.0064 (17)0.0042 (15)0.0038 (17)
C2C0.054 (2)0.058 (2)0.056 (2)0.013 (2)0.0046 (19)0.0004 (19)
C3C0.053 (2)0.107 (4)0.079 (3)0.026 (3)0.008 (2)0.024 (3)
C4C0.057 (3)0.120 (4)0.075 (3)0.005 (3)0.016 (2)0.029 (3)
C5C0.062 (3)0.087 (3)0.078 (3)0.005 (3)0.028 (2)0.004 (3)
C6C0.051 (2)0.057 (2)0.048 (2)0.0046 (19)0.0098 (18)0.0029 (19)
Geometric parameters (Å, º) top
P1—C11.757 (3)C2A—C3A1.384 (5)
P1—C1A1.804 (3)C3A—C4A1.374 (5)
P1—C1B1.817 (3)C4A—C5A1.371 (5)
P1—C1C1.821 (3)C5A—C6A1.388 (5)
C1—C21.434 (4)C1B—C2B1.378 (4)
C1—C51.444 (4)C1B—C6B1.389 (4)
C2—O41.248 (4)C2B—C3B1.392 (4)
C2—C31.507 (4)C3B—C4B1.370 (5)
C5—O71.197 (4)C4B—C5B1.375 (5)
C5—O6''1.352 (7)C5B—C6B1.376 (4)
C5—O6'1.360 (8)C1C—C2C1.386 (4)
O6'—C8'1.457 (9)C1C—C6C1.385 (4)
C8'—C9'1.494 (10)C2C—C3C1.387 (4)
O6''—C8''1.466 (8)C3C—C4C1.375 (5)
C8''—C9''1.497 (10)C4C—C5C1.374 (5)
C1A—C6A1.374 (4)C5C—C6C1.388 (4)
C1A—C2A1.383 (4)
P1···O42.699 (4)P1···O6''3.026 (7)
P1···O6'3.014 (8)
C1—P1—C1A109.67 (14)C6A—C1A—P1118.6 (3)
C1—P1—C1B113.78 (14)C2A—C1A—P1122.7 (3)
C1A—P1—C1B107.20 (15)C3A—C2A—C1A120.3 (4)
C1—P1—C1C114.37 (15)C4A—C3A—C2A120.4 (4)
C1A—P1—C1C110.18 (15)C5A—C4A—C3A119.8 (4)
C1B—P1—C1C101.19 (14)C4A—C5A—C6A119.6 (4)
C2—C1—C5123.5 (3)C1A—C6A—C5A121.1 (4)
C2—C1—P1109.9 (2)C2B—C1B—C6B119.3 (3)
C5—C1—P1126.4 (3)C2B—C1B—P1123.0 (3)
O4—C2—C1119.1 (3)C6B—C1B—P1117.7 (2)
O4—C2—C3118.4 (3)C1B—C2B—C3B120.1 (4)
C1—C2—C3122.5 (4)C4B—C3B—C2B120.0 (4)
O7—C5—O6''120.0 (6)C3B—C4B—C5B119.9 (4)
O7—C5—O6'117.3 (7)C4B—C5B—C6B120.5 (4)
O6''—C5—O6'32.7 (6)C5B—C6B—C1B120.1 (4)
O7—C5—C1127.4 (4)C2C—C1C—C6C119.5 (3)
O6''—C5—C1111.1 (6)C2C—C1C—P1119.7 (3)
O6'—C5—C1112.1 (8)C6C—C1C—P1120.5 (2)
C5—O6'—C8'109.9 (18)C1C—C2C—C3C119.7 (3)
O6'—C8'—C9'111 (3)C4C—C3C—C2C120.7 (4)
C5—O6''—C8''121.3 (11)C5C—C4C—C3C119.5 (4)
O6''—C8''—C9''107.6 (16)C4C—C5C—C6C120.5 (4)
C6A—C1A—C2A118.6 (3)C1C—C6C—C5C119.9 (3)
C1A—P1—C1—C261.7 (3)C2A—C3A—C4A—C5A1.8 (7)
C1B—P1—C1—C2178.3 (2)C3A—C4A—C5A—C6A1.2 (7)
C1C—P1—C1—C262.7 (3)C2A—C1A—C6A—C5A2.9 (6)
C1A—P1—C1—C5112.6 (3)P1—C1A—C6A—C5A177.5 (3)
C1B—P1—C1—C57.4 (3)C4A—C5A—C6A—C1A1.1 (7)
C1C—P1—C1—C5123.0 (3)C1—P1—C1B—C2B104.3 (3)
C5—C1—C2—O4176.2 (3)C1A—P1—C1B—C2B17.2 (3)
P1—C1—C2—O41.7 (4)C1C—P1—C1B—C2B132.6 (3)
C5—C1—C2—C36.4 (5)C1—P1—C1B—C6B77.7 (3)
P1—C1—C2—C3179.1 (3)C1A—P1—C1B—C6B160.9 (3)
C2—C1—C5—O72.8 (6)C1C—P1—C1B—C6B45.4 (3)
P1—C1—C5—O7170.7 (3)C6B—C1B—C2B—C3B0.6 (5)
C2—C1—C5—O6''162.9 (10)P1—C1B—C2B—C3B178.6 (3)
P1—C1—C5—O6''23.6 (11)C1B—C2B—C3B—C4B0.3 (6)
C2—C1—C5—O6'161.9 (14)C2B—C3B—C4B—C5B0.5 (6)
P1—C1—C5—O6'11.7 (14)C3B—C4B—C5B—C6B1.0 (7)
O7—C5—O6'—C8'26 (2)C4B—C5B—C6B—C1B1.3 (6)
O6''—C5—O6'—C8'77 (3)C2B—C1B—C6B—C5B1.1 (5)
C1—C5—O6'—C8'172.4 (14)P1—C1B—C6B—C5B179.2 (3)
C5—O6'—C8'—C9'150 (5)C1—P1—C1C—C2C178.0 (2)
O7—C5—O6''—C8''10 (2)C1A—P1—C1C—C2C57.9 (3)
O6'—C5—O6''—C8''84 (3)C1B—P1—C1C—C2C55.3 (3)
C1—C5—O6''—C8''177.1 (13)C1—P1—C1C—C6C4.6 (3)
C5—O6''—C8''—C9''108 (3)C1A—P1—C1C—C6C128.7 (3)
C1—P1—C1A—C6A50.0 (3)C1B—P1—C1C—C6C118.1 (3)
C1B—P1—C1A—C6A74.0 (3)C6C—C1C—C2C—C3C0.3 (5)
C1C—P1—C1A—C6A176.7 (3)P1—C1C—C2C—C3C173.7 (3)
C1—P1—C1A—C2A129.6 (3)C1C—C2C—C3C—C4C0.4 (5)
C1B—P1—C1A—C2A106.4 (3)C2C—C3C—C4C—C5C1.3 (6)
C1C—P1—C1A—C2A2.9 (3)C3C—C4C—C5C—C6C1.6 (6)
C6A—C1A—C2A—C3A2.4 (5)C2C—C1C—C6C—C5C0.0 (5)
P1—C1A—C2A—C3A178.0 (3)P1—C1C—C6C—C5C173.4 (3)
C1A—C2A—C3A—C4A0.1 (6)C4C—C5C—C6C—C1C0.9 (6)
(IV) i-Propyl 3-oxo-2-(triphenylphosphoranylidene)butyrate top
Crystal data top
C25H25O3PF(000) = 1712
Mr = 404.42Dx = 1.238 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 14.932 (7) Åθ = 7.5–12.5°
b = 16.343 (6) ŵ = 0.15 mm1
c = 17.780 (7) ÅT = 293 K
V = 4339 (3) Å3Prism, colourless
Z = 80.22 × 0.19 × 0.16 mm
Data collection top
Siemens R3m
diffractometer
Rint = 0.096
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.2°
Graphite monochromatorh = 017
ω/2θ scansk = 019
4441 measured reflectionsl = 021
3824 independent reflections2 standard reflections every 98 reflections
1801 reflections with I > 2σ(I) intensity decay: <2%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.089Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.034P)2 + 5.363]
where P = (Fo2 + 2Fc2)/3
3824 reflections(Δ/σ)max < 0.01
266 parametersΔρmax = 0.20 e Å3
27 restraintsΔρmin = 0.21 e Å3
Crystal data top
C25H25O3PV = 4339 (3) Å3
Mr = 404.42Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.932 (7) ŵ = 0.15 mm1
b = 16.343 (6) ÅT = 293 K
c = 17.780 (7) Å0.22 × 0.19 × 0.16 mm
Data collection top
Siemens R3m
diffractometer
Rint = 0.096
4441 measured reflections2 standard reflections every 98 reflections
3824 independent reflections intensity decay: <2%
1801 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.08927 restraints
wR(F2) = 0.160H-atom parameters constrained
S = 1.03Δρmax = 0.20 e Å3
3824 reflectionsΔρmin = 0.21 e Å3
266 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.24246 (9)0.81464 (8)0.33182 (7)0.0393 (3)
C10.3038 (3)0.9024 (3)0.3555 (3)0.0366 (12)
C20.3371 (3)0.8993 (3)0.4316 (3)0.0454 (14)
C30.3935 (4)0.9649 (3)0.4644 (3)0.0713 (18)
H3A0.40940.95070.51510.107*
H3B0.44700.97100.43490.107*
H3C0.36081.01550.46440.107*
O40.3171 (2)0.8374 (2)0.46870 (19)0.0499 (10)
C50.3299 (4)0.9647 (4)0.3036 (3)0.0584 (17)
O60.2863 (4)0.9633 (3)0.2377 (3)0.1111 (19)
O70.3773 (3)1.0242 (3)0.3153 (2)0.0858 (15)
C80.3073 (8)1.0227 (6)0.1809 (5)0.123 (4)
H8A0.35611.05820.19800.148*
C90.3462 (5)0.9777 (6)0.1160 (5)0.139 (4)
H9A0.40370.95610.12980.208*
H9B0.30710.93360.10210.208*
H9C0.35291.01430.07420.208*
C100.2208 (8)1.0575 (5)0.1580 (5)0.155 (4)
H10D0.20091.09580.19540.232*
H10E0.22751.08520.11070.232*
H10F0.17761.01450.15290.232*
C1A0.3131 (3)0.7264 (3)0.3413 (2)0.0319 (11)
C2A0.2847 (4)0.6564 (3)0.3786 (3)0.0580 (16)
H2A0.22880.65560.40160.070*
C3A0.3392 (4)0.5872 (3)0.3821 (3)0.0663 (18)
H3A10.31990.54040.40700.080*
C4A0.4227 (4)0.5892 (4)0.3477 (4)0.079 (2)
H4A0.45920.54310.34910.095*
C5A0.4523 (4)0.6590 (4)0.3115 (4)0.084 (2)
H5A0.50900.66050.28990.101*
C6A0.3963 (4)0.7272 (4)0.3075 (3)0.0675 (18)
H6A0.41530.77370.28190.081*
C1B0.1996 (3)0.8152 (3)0.2374 (2)0.0381 (12)
C2B0.2417 (4)0.7738 (3)0.1792 (3)0.0684 (17)
H2B0.29360.74400.18860.082*
C3B0.2063 (5)0.7767 (4)0.1066 (4)0.084 (2)
H3B10.23530.74940.06770.101*
C4B0.1291 (5)0.8193 (4)0.0923 (4)0.086 (2)
H4B0.10550.82090.04400.103*
C5B0.0871 (5)0.8597 (5)0.1503 (4)0.092 (2)
H5B0.03450.88840.14070.111*
C6B0.1214 (4)0.8586 (4)0.2222 (3)0.0681 (18)
H6B0.09240.88670.26060.082*
C1C0.1401 (3)0.7997 (3)0.3854 (3)0.0373 (12)
C2C0.0848 (3)0.7339 (3)0.3695 (3)0.0535 (15)
H2C0.10170.69520.33390.064*
C3C0.0036 (4)0.7262 (4)0.4074 (3)0.0640 (18)
H3C10.03400.68220.39720.077*
C4C0.0210 (4)0.7842 (4)0.4604 (4)0.078 (2)
H4C0.07460.77810.48640.093*
C5C0.0334 (4)0.8517 (4)0.4752 (3)0.0733 (19)
H5C0.01560.89150.50950.088*
C6C0.1152 (3)0.8582 (3)0.4375 (3)0.0546 (15)
H6C0.15300.90210.44750.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0412 (8)0.0444 (7)0.0324 (6)0.0043 (8)0.0017 (7)0.0001 (7)
C10.040 (3)0.036 (3)0.033 (3)0.004 (3)0.001 (2)0.006 (2)
C20.043 (4)0.056 (3)0.037 (3)0.013 (3)0.009 (3)0.012 (3)
C30.070 (5)0.068 (4)0.075 (4)0.006 (4)0.010 (4)0.015 (4)
O40.041 (2)0.061 (2)0.047 (2)0.003 (2)0.0148 (18)0.0129 (19)
C50.069 (4)0.053 (4)0.053 (4)0.017 (3)0.022 (3)0.010 (3)
O60.149 (5)0.096 (4)0.088 (4)0.067 (3)0.038 (3)0.042 (3)
O70.099 (4)0.070 (3)0.089 (3)0.029 (3)0.021 (3)0.015 (3)
C80.182 (11)0.114 (8)0.074 (6)0.071 (8)0.041 (7)0.014 (6)
C90.114 (8)0.171 (9)0.131 (8)0.043 (7)0.006 (7)0.040 (7)
C100.247 (14)0.119 (7)0.099 (7)0.014 (9)0.022 (8)0.017 (6)
C1A0.038 (3)0.027 (3)0.031 (3)0.001 (2)0.004 (2)0.006 (2)
C2A0.063 (4)0.046 (3)0.065 (4)0.008 (3)0.002 (3)0.005 (3)
C3A0.060 (5)0.053 (4)0.086 (5)0.011 (4)0.022 (4)0.002 (3)
C4A0.077 (5)0.063 (5)0.097 (6)0.002 (4)0.018 (5)0.001 (4)
C5A0.069 (5)0.091 (5)0.093 (6)0.011 (5)0.009 (4)0.007 (4)
C6A0.071 (4)0.066 (4)0.066 (4)0.001 (4)0.004 (4)0.004 (3)
C1B0.046 (3)0.030 (3)0.039 (3)0.013 (3)0.008 (3)0.006 (3)
C2B0.078 (4)0.067 (4)0.060 (4)0.001 (4)0.009 (4)0.004 (3)
C3B0.087 (6)0.092 (6)0.073 (5)0.009 (4)0.006 (4)0.008 (4)
C4B0.088 (6)0.100 (6)0.070 (5)0.022 (5)0.012 (5)0.006 (5)
C5B0.075 (5)0.112 (6)0.089 (6)0.015 (5)0.007 (5)0.024 (5)
C6B0.077 (5)0.074 (4)0.054 (4)0.002 (4)0.002 (4)0.010 (3)
C1C0.045 (3)0.032 (3)0.035 (3)0.001 (3)0.003 (2)0.002 (2)
C2C0.053 (4)0.063 (4)0.045 (3)0.009 (3)0.001 (3)0.003 (3)
C3C0.054 (4)0.069 (5)0.069 (4)0.019 (3)0.001 (3)0.000 (4)
C4C0.068 (5)0.091 (5)0.074 (5)0.001 (4)0.002 (4)0.007 (4)
C5C0.049 (4)0.092 (5)0.079 (5)0.005 (4)0.016 (4)0.002 (4)
C6C0.040 (3)0.066 (4)0.058 (4)0.003 (3)0.001 (3)0.003 (3)
Geometric parameters (Å, º) top
P1—C11.753 (5)C3A—C4A1.389 (6)
P1—C1A1.795 (4)C4A—C5A1.383 (6)
P1—C1B1.796 (5)C5A—C6A1.394 (6)
P1—C1C1.818 (5)C1B—C2B1.386 (6)
C1—C51.429 (7)C1B—C6B1.393 (6)
C1—C21.443 (6)C2B—C3B1.396 (6)
C2—O41.244 (6)C3B—C4B1.370 (7)
C2—C31.483 (7)C4B—C5B1.376 (6)
C5—O71.221 (6)C5B—C6B1.379 (6)
C5—O61.341 (6)C1C—C2C1.385 (5)
O6—C81.436 (8)C1C—C6C1.383 (5)
C8—C101.469 (11)C2C—C3C1.392 (6)
C8—C91.486 (11)C3C—C4C1.386 (6)
C1A—C6A1.380 (6)C4C—C5C1.395 (6)
C1A—C2A1.389 (5)C5C—C6C1.397 (6)
C2A—C3A1.394 (6)
P1···O42.703 (16)P1···O63.023 (16)
C1—P1—C1A109.1 (2)C1A—C2A—C3A120.7 (5)
C1—P1—C1B114.0 (2)C4A—C3A—C2A119.0 (6)
C1A—P1—C1B107.5 (2)C5A—C4A—C3A120.7 (6)
C1—P1—C1C115.1 (2)C4A—C5A—C6A119.5 (6)
C1A—P1—C1C109.7 (2)C1A—C6A—C5A120.6 (6)
C1B—P1—C1C101.0 (2)C2B—C1B—C6B118.9 (5)
C5—C1—C2122.5 (5)C2B—C1B—P1122.3 (4)
C5—C1—P1124.8 (4)C6B—C1B—P1118.8 (4)
C2—C1—P1112.2 (4)C1B—C2B—C3B120.2 (6)
O4—C2—C1116.3 (5)C4B—C3B—C2B120.4 (6)
O4—C2—C3121.1 (5)C3B—C4B—C5B119.3 (7)
C1—C2—C3122.6 (5)C4B—C5B—C6B121.2 (7)
O7—C5—O6116.4 (6)C5B—C6B—C1B119.9 (6)
O7—C5—C1128.0 (5)C2C—C1C—C6C120.9 (5)
O6—C5—C1114.9 (5)C2C—C1C—P1120.0 (4)
C5—O6—C8119.8 (5)C6C—C1C—P1119.0 (4)
O6—C8—C10105.4 (9)C1C—C2C—C3C119.4 (5)
O6—C8—C9107.3 (8)C4C—C3C—C2C119.8 (6)
C10—C8—C9108.7 (8)C3C—C4C—C5C121.0 (6)
C6A—C1A—C2A119.4 (5)C4C—C5C—C6C118.6 (6)
C6A—C1A—P1118.7 (4)C1C—C6C—C5C120.2 (5)
C2A—C1A—P1121.8 (4)
C1A—P1—C1—C5111.7 (5)P1—C1A—C6A—C5A178.0 (4)
C1B—P1—C1—C58.5 (5)C4A—C5A—C6A—C1A1.9 (9)
C1C—P1—C1—C5124.6 (5)C1—P1—C1B—C2B99.3 (5)
C1A—P1—C1—C259.7 (4)C1A—P1—C1B—C2B21.8 (5)
C1B—P1—C1—C2179.8 (3)C1C—P1—C1B—C2B136.7 (4)
C1C—P1—C1—C264.1 (4)C1—P1—C1B—C6B80.8 (4)
C5—C1—C2—O4172.5 (5)C1A—P1—C1B—C6B158.1 (4)
P1—C1—C2—O40.9 (6)C1C—P1—C1B—C6B43.2 (4)
C5—C1—C2—C36.4 (8)C6B—C1B—C2B—C3B0.7 (8)
P1—C1—C2—C3177.9 (4)P1—C1B—C2B—C3B179.4 (4)
C2—C1—C5—O74.2 (9)C1B—C2B—C3B—C4B1.0 (10)
P1—C1—C5—O7174.7 (5)C2B—C3B—C4B—C5B0.4 (11)
C2—C1—C5—O6173.8 (5)C3B—C4B—C5B—C6B0.4 (11)
P1—C1—C5—O615.7 (8)C4B—C5B—C6B—C1B0.6 (10)
O7—C5—O6—C89.5 (11)C2B—C1B—C6B—C5B0.1 (8)
C1—C5—O6—C8179.6 (7)P1—C1B—C6B—C5B179.8 (5)
C5—O6—C8—C10129.3 (8)C1—P1—C1C—C2C177.7 (4)
C5—O6—C8—C9115.0 (8)C1A—P1—C1C—C2C58.8 (4)
C1—P1—C1A—C6A50.1 (4)C1B—P1—C1C—C2C54.4 (4)
C1B—P1—C1A—C6A74.1 (4)C1—P1—C1C—C6C2.9 (5)
C1C—P1—C1A—C6A176.9 (4)C1A—P1—C1C—C6C126.4 (4)
C1—P1—C1A—C2A132.8 (4)C1B—P1—C1C—C6C120.4 (4)
C1B—P1—C1A—C2A103.1 (4)C6C—C1C—C2C—C3C0.9 (8)
C1C—P1—C1A—C2A5.9 (4)P1—C1C—C2C—C3C175.6 (4)
C6A—C1A—C2A—C3A0.3 (6)C1C—C2C—C3C—C4C0.1 (8)
P1—C1A—C2A—C3A176.9 (4)C2C—C3C—C4C—C5C1.6 (9)
C1A—C2A—C3A—C4A0.2 (7)C3C—C4C—C5C—C6C2.3 (9)
C2A—C3A—C4A—C5A0.9 (9)C2C—C1C—C6C—C5C0.1 (8)
C3A—C4A—C5A—C6A1.9 (10)P1—C1C—C6C—C5C174.9 (4)
C2A—C1A—C6A—C5A0.8 (8)C4C—C5C—C6C—C1C1.5 (9)
(V) tert-Butyl 3-oxo-2-(triphenylphosphoranylidene)butyrate top
Crystal data top
C26H27O3PF(000) = 888
Mr = 418.45Dx = 1.241 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.668 (6) ÅCell parameters from 25 reflections
b = 13.975 (8) Åθ = 7.5–12.5°
c = 16.625 (11) ŵ = 0.15 mm1
β = 94.69 (5)°T = 293 K
V = 2239 (2) Å3Prism, colourless
Z = 40.30 × 0.20 × 0.18 mm
Data collection top
Siemens R3m
diffractometer
Rint = 0.054
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 1.9°
Graphite monochromatorh = 1111
ω/2θ scansk = 016
4193 measured reflectionsl = 019
3945 independent reflections2 standard reflections every 98 reflections
3025 reflections with I > 2σ(I) intensity decay: <2%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.077P)2 + 0.987P]
where P = (Fo2 + 2Fc2)/3
3945 reflections(Δ/σ)max < 0.01
276 parametersΔρmax = 0.18 e Å3
27 restraintsΔρmin = 0.21 e Å3
Crystal data top
C26H27O3PV = 2239 (2) Å3
Mr = 418.45Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.668 (6) ŵ = 0.15 mm1
b = 13.975 (8) ÅT = 293 K
c = 16.625 (11) Å0.30 × 0.20 × 0.18 mm
β = 94.69 (5)°
Data collection top
Siemens R3m
diffractometer
Rint = 0.054
4193 measured reflections2 standard reflections every 98 reflections
3945 independent reflections intensity decay: <2%
3025 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.04027 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 1.01Δρmax = 0.18 e Å3
3945 reflectionsΔρmin = 0.21 e Å3
276 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.18890 (5)0.29959 (3)0.22089 (3)0.03110 (13)
C10.12454 (18)0.19803 (12)0.17013 (10)0.0345 (4)
C20.00061 (19)0.16606 (14)0.20169 (11)0.0400 (4)
C30.0759 (2)0.07768 (16)0.17056 (14)0.0618 (6)
H3A0.17380.09030.16410.093*
H3B0.04400.06010.11940.093*
H3C0.05810.02630.20830.093*
O40.04949 (14)0.21336 (10)0.25602 (8)0.0509 (4)
C50.1774 (2)0.15793 (13)0.09832 (11)0.0389 (4)
O60.24531 (13)0.22371 (8)0.05717 (7)0.0396 (3)
O70.1600 (2)0.07672 (10)0.07506 (10)0.0700 (5)
C80.3159 (2)0.19793 (16)0.01497 (11)0.0481 (5)
C90.4259 (3)0.1244 (2)0.00615 (17)0.0950 (10)
H9A0.47760.14210.05570.142*
H9B0.38320.06310.01260.142*
H9C0.48740.12080.03630.142*
C100.2093 (3)0.1672 (2)0.08248 (13)0.0746 (8)
H10A0.17120.10620.06940.112*
H10B0.13630.21380.08850.112*
H10C0.25320.16210.13200.112*
C110.3796 (3)0.29185 (19)0.03685 (13)0.0720 (8)
H11A0.44880.31030.00500.108*
H11B0.42180.28500.08680.108*
H11C0.30880.34010.04260.108*
C1A0.07392 (18)0.40116 (12)0.20733 (10)0.0354 (4)
C2A0.0222 (2)0.44906 (15)0.27118 (12)0.0488 (5)
H2A0.04600.42870.32380.059*
C3A0.0641 (2)0.52658 (15)0.25745 (14)0.0579 (6)
H3A10.09800.55840.30090.069*
C4A0.1008 (2)0.55750 (15)0.18025 (15)0.0567 (6)
H4A0.15870.61020.17140.068*
C5A0.0512 (2)0.50982 (15)0.11592 (14)0.0557 (6)
H5A0.07590.53030.06350.067*
C6A0.0352 (2)0.43152 (14)0.12929 (12)0.0470 (5)
H6A0.06760.39910.08570.056*
C1B0.35675 (18)0.33577 (13)0.19026 (10)0.0367 (4)
C2B0.3808 (2)0.42288 (14)0.15553 (13)0.0530 (6)
H2B0.30790.46530.14350.064*
C3B0.5149 (3)0.44709 (18)0.13853 (16)0.0732 (8)
H3B10.53170.50590.11510.088*
C4B0.6225 (3)0.3846 (2)0.15619 (16)0.0738 (8)
H4B0.71170.40120.14420.089*
C5B0.5997 (2)0.2981 (2)0.19135 (15)0.0684 (7)
H5B0.67320.25630.20370.082*
C6B0.4667 (2)0.27323 (17)0.20840 (13)0.0548 (6)
H6B0.45080.21440.23210.066*
C1C0.23235 (18)0.27963 (12)0.32746 (10)0.0343 (4)
C2C0.2898 (2)0.35439 (14)0.37385 (11)0.0447 (5)
H2C0.29890.41440.35070.054*
C3C0.3337 (2)0.34044 (16)0.45419 (12)0.0542 (5)
H3C10.37080.39120.48510.065*
C4C0.3223 (2)0.25140 (18)0.48849 (13)0.0586 (6)
H4C0.35180.24180.54250.070*
C5C0.2669 (2)0.17649 (16)0.44229 (13)0.0573 (6)
H5C0.25980.11630.46540.069*
C6C0.2219 (2)0.19025 (13)0.36192 (11)0.0442 (5)
H6C0.18470.13940.33120.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0352 (2)0.0294 (2)0.0298 (2)0.00098 (19)0.00963 (18)0.00049 (19)
C10.0409 (10)0.0316 (9)0.0318 (9)0.0032 (8)0.0086 (7)0.0004 (7)
C20.0409 (10)0.0458 (11)0.0334 (10)0.0055 (9)0.0036 (8)0.0077 (8)
C30.0633 (14)0.0641 (15)0.0589 (14)0.0286 (12)0.0100 (11)0.0041 (12)
O40.0472 (8)0.0645 (9)0.0438 (8)0.0032 (7)0.0195 (6)0.0010 (7)
C50.0508 (11)0.0306 (10)0.0364 (10)0.0010 (8)0.0112 (8)0.0025 (8)
O60.0515 (8)0.0371 (7)0.0326 (6)0.0052 (6)0.0181 (6)0.0040 (5)
O70.1192 (14)0.0322 (8)0.0636 (10)0.0131 (8)0.0388 (10)0.0106 (7)
C80.0527 (12)0.0647 (13)0.0292 (9)0.0022 (11)0.0174 (8)0.0092 (9)
C90.089 (2)0.123 (3)0.0776 (19)0.0474 (19)0.0360 (16)0.0048 (18)
C100.0835 (18)0.100 (2)0.0415 (13)0.0231 (16)0.0143 (12)0.0191 (13)
C110.0781 (17)0.0963 (19)0.0456 (13)0.0302 (15)0.0297 (12)0.0018 (13)
C1A0.0360 (10)0.0316 (9)0.0391 (10)0.0007 (8)0.0074 (8)0.0017 (8)
C2A0.0512 (12)0.0561 (13)0.0404 (11)0.0137 (10)0.0109 (9)0.0007 (9)
C3A0.0552 (13)0.0555 (14)0.0633 (14)0.0159 (11)0.0071 (11)0.0114 (11)
C4A0.0491 (12)0.0398 (12)0.0802 (16)0.0079 (10)0.0001 (11)0.0010 (11)
C5A0.0583 (14)0.0504 (13)0.0572 (13)0.0019 (11)0.0023 (11)0.0173 (10)
C6A0.0537 (12)0.0464 (12)0.0417 (11)0.0036 (10)0.0085 (9)0.0038 (9)
C1B0.0380 (10)0.0392 (10)0.0342 (9)0.0063 (8)0.0107 (8)0.0066 (8)
C2B0.0582 (13)0.0379 (11)0.0659 (14)0.0130 (10)0.0229 (11)0.0053 (10)
C3B0.0764 (17)0.0544 (14)0.0942 (19)0.0308 (14)0.0398 (15)0.0150 (13)
C4B0.0511 (14)0.094 (2)0.0804 (18)0.0323 (15)0.0295 (13)0.0366 (16)
C5B0.0393 (12)0.096 (2)0.0720 (16)0.0007 (13)0.0149 (11)0.0114 (15)
C6B0.0428 (12)0.0632 (14)0.0599 (13)0.0048 (10)0.0134 (10)0.0077 (11)
C1C0.0351 (9)0.0370 (10)0.0316 (9)0.0040 (8)0.0066 (7)0.0004 (7)
C2C0.0519 (12)0.0441 (11)0.0381 (11)0.0037 (9)0.0046 (9)0.0016 (9)
C3C0.0615 (14)0.0616 (14)0.0384 (11)0.0011 (11)0.0022 (10)0.0072 (10)
C4C0.0666 (15)0.0726 (15)0.0357 (10)0.0089 (13)0.0013 (10)0.0008 (11)
C5C0.0728 (15)0.0507 (13)0.0483 (13)0.0077 (11)0.0036 (11)0.0155 (10)
C6C0.0558 (12)0.0377 (10)0.0386 (10)0.0011 (9)0.0017 (9)0.0025 (8)
Geometric parameters (Å, º) top
P1—C11.7400 (19)C2A—C3A1.375 (3)
P1—C1A1.8058 (19)C3A—C4A1.373 (3)
P1—C1C1.809 (2)C4A—C5A1.379 (3)
P1—C1B1.812 (2)C5A—C6A1.384 (3)
C1—C21.429 (3)C1B—C2B1.375 (3)
C1—C51.449 (3)C1B—C6B1.390 (3)
C2—O41.243 (2)C2B—C3B1.391 (3)
C2—C31.504 (3)C3B—C4B1.371 (4)
C5—O71.206 (2)C4B—C5B1.369 (3)
C5—O61.348 (2)C5B—C6B1.383 (3)
O6—C81.472 (2)C1C—C6C1.381 (2)
C8—C91.500 (3)C1C—C2C1.388 (3)
C8—C111.507 (3)C2C—C3C1.382 (3)
C8—C101.522 (3)C3C—C4C1.377 (3)
C1A—C2A1.383 (3)C4C—C5C1.380 (3)
C1A—C6A1.387 (3)C5C—C6C1.384 (3)
P1···O42.707 (2)P1···O63.012 (2)
C1—P1—C1A112.87 (10)C2A—C1A—P1122.84 (15)
C1—P1—C1C113.23 (9)C6A—C1A—P1118.25 (14)
C1A—P1—C1C109.56 (8)C3A—C2A—C1A120.4 (2)
C1—P1—C1B112.60 (9)C4A—C3A—C2A120.7 (2)
C1A—P1—C1B107.57 (9)C3A—C4A—C5A119.6 (2)
C1C—P1—C1B100.18 (9)C4A—C5A—C6A120.1 (2)
C2—C1—C5123.22 (16)C5A—C6A—C1A120.34 (19)
C2—C1—P1110.90 (13)C2B—C1B—C6B119.69 (19)
C5—C1—P1125.35 (13)C2B—C1B—P1123.42 (15)
O4—C2—C1118.95 (18)C6B—C1B—P1116.75 (15)
O4—C2—C3118.97 (17)C1B—C2B—C3B119.5 (2)
C1—C2—C3122.07 (17)C4B—C3B—C2B120.3 (2)
O7—C5—O6122.67 (17)C5B—C4B—C3B120.5 (2)
O7—C5—C1125.34 (17)C4B—C5B—C6B119.6 (2)
O6—C5—C1111.94 (15)C5B—C6B—C1B120.3 (2)
C5—O6—C8121.60 (15)C6C—C1C—C2C119.33 (17)
O6—C8—C9110.13 (17)C6C—C1C—P1121.78 (13)
O6—C8—C11102.09 (16)C2C—C1C—P1118.60 (14)
C9—C8—C11110.9 (2)C3C—C2C—C1C120.55 (19)
O6—C8—C10109.79 (17)C4C—C3C—C2C120.0 (2)
C9—C8—C10113.8 (2)C3C—C4C—C5C119.69 (19)
C11—C8—C10109.47 (19)C4C—C5C—C6C120.6 (2)
C2A—C1A—C6A118.91 (18)C1C—C6C—C5C119.86 (18)
C1A—P1—C1—C263.94 (15)C2A—C1A—C6A—C5A1.4 (3)
C1C—P1—C1—C261.26 (15)P1—C1A—C6A—C5A179.13 (15)
C1B—P1—C1—C2174.03 (13)C1—P1—C1B—C2B118.93 (17)
C1A—P1—C1—C5107.93 (17)C1A—P1—C1B—C2B6.06 (19)
C1C—P1—C1—C5126.87 (16)C1C—P1—C1B—C2B120.49 (17)
C1B—P1—C1—C514.10 (19)C1—P1—C1B—C6B65.36 (18)
C5—C1—C2—O4169.35 (17)C1A—P1—C1B—C6B169.66 (15)
P1—C1—C2—O42.7 (2)C1C—P1—C1B—C6B55.23 (17)
C5—C1—C2—C39.9 (3)C6B—C1B—C2B—C3B0.4 (3)
P1—C1—C2—C3178.02 (15)P1—C1B—C2B—C3B175.98 (17)
C2—C1—C5—O729.6 (3)C1B—C2B—C3B—C4B0.0 (3)
P1—C1—C5—O7159.49 (18)C2B—C3B—C4B—C5B0.6 (4)
C2—C1—C5—O6147.80 (17)C3B—C4B—C5B—C6B0.7 (4)
P1—C1—C5—O623.1 (2)C4B—C5B—C6B—C1B0.2 (4)
O7—C5—O6—C86.6 (3)C2B—C1B—C6B—C5B0.3 (3)
C1—C5—O6—C8175.92 (16)P1—C1B—C6B—C5B176.17 (18)
C5—O6—C8—C959.9 (3)C1—P1—C1C—C6C3.62 (18)
C5—O6—C8—C11177.79 (18)C1A—P1—C1C—C6C130.58 (16)
C5—O6—C8—C1066.2 (2)C1B—P1—C1C—C6C116.51 (16)
C1—P1—C1A—C2A122.77 (17)C1—P1—C1C—C2C177.51 (14)
C1C—P1—C1A—C2A4.40 (19)C1A—P1—C1C—C2C55.52 (16)
C1B—P1—C1A—C2A112.41 (17)C1B—P1—C1C—C2C57.39 (15)
C1—P1—C1A—C6A56.63 (17)C6C—C1C—C2C—C3C1.4 (3)
C1C—P1—C1A—C6A176.20 (14)P1—C1C—C2C—C3C175.40 (16)
C1B—P1—C1A—C6A68.19 (17)C1C—C2C—C3C—C4C1.0 (3)
C6A—C1A—C2A—C3A1.2 (3)C2C—C3C—C4C—C5C0.1 (3)
P1—C1A—C2A—C3A179.43 (16)C3C—C4C—C5C—C6C0.4 (3)
C1A—C2A—C3A—C4A0.2 (3)C2C—C1C—C6C—C5C0.9 (3)
C2A—C3A—C4A—C5A0.4 (3)P1—C1C—C6C—C5C174.71 (16)
C3A—C4A—C5A—C6A0.2 (3)C4C—C5C—C6C—C1C0.0 (3)
C4A—C5A—C6A—C1A0.8 (3)

Experimental details

(II)(III)(IV)(V)
Crystal data
Chemical formulaC23H21O3P·0.5C6H6C24H23O3PC25H25O3PC26H27O3P
Mr415.42390.39404.42418.45
Crystal system, space groupMonoclinic, P21/nOrthorhombic, PbcaOrthorhombic, PbcaMonoclinic, P21/n
Temperature (K)293293293293
a, b, c (Å)10.698 (5), 8.939 (4), 23.026 (11)14.815 (4), 16.226 (5), 17.670 (5)14.932 (7), 16.343 (6), 17.780 (7)9.668 (6), 13.975 (8), 16.625 (11)
α, β, γ (°)90, 91.66 (4), 9090, 90, 9090, 90, 9090, 94.69 (5), 90
V3)2200.9 (17)4248 (2)4339 (3)2239 (2)
Z4884
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.150.150.150.15
Crystal size (mm)0.24 × 0.18 × 0.150.27 × 0.20 × 0.160.22 × 0.19 × 0.160.30 × 0.20 × 0.18
Data collection
DiffractometerSiemens R3m
diffractometer
Siemens R3m
diffractometer
Siemens R3m
diffractometer
Siemens R3m
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4102, 3892, 2766 3911, 3737, 1966 4441, 3824, 1801 4193, 3945, 3025
Rint0.0550.0580.0960.054
(sin θ/λ)max1)0.5950.5950.5940.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.094, 1.06 0.058, 0.124, 0.99 0.089, 0.160, 1.03 0.040, 0.101, 1.01
No. of reflections3892373738243945
No. of parameters274284266276
No. of restraints33332727
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.190.22, 0.180.20, 0.210.18, 0.21

Computer programs: P3/PC (Siemens, 1993), P3/PC, XDISK in SHELXTL/PC (Sheldrick, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC, CIFTAB (Sheldrick, 1993), PARST (Nardelli, 1983) and the Cambridge Structural Database (Allen & Kennard, 1993).

Selected geometric parameters (Å, º) for (II) top
P1—C11.747 (2)C2—O41.243 (2)
P1—C1C1.802 (2)C2—C31.510 (3)
P1—C1A1.815 (2)C5—O71.212 (2)
P1—C1B1.819 (2)C5—O61.349 (3)
C1—C21.428 (3)O6—C81.435 (3)
C1—C51.441 (3)
P1···O42.806 (2)P1···O62.971 (2)
C1—P1—C1C115.61 (10)C1A—P1—C1B108.24 (9)
C1—P1—C1A108.97 (10)C2—C1—C5123.05 (19)
C1C—P1—C1A106.92 (9)C2—C1—P1113.18 (15)
C1—P1—C1B111.13 (10)C5—C1—P1123.63 (16)
C1C—P1—C1B105.66 (10)
P1—C1—C2—O412.0 (3)P1—C1—C5—O7162.47 (19)
Selected geometric parameters (Å, º) for (III) top
P1—C11.757 (3)C5—O71.197 (4)
P1—C1A1.804 (3)C5—O6''1.352 (7)
P1—C1B1.817 (3)C5—O6'1.360 (8)
P1—C1C1.821 (3)O6'—C8'1.457 (9)
C1—C21.434 (4)C8'—C9'1.494 (10)
C1—C51.444 (4)O6''—C8''1.466 (8)
C2—O41.248 (4)C8''—C9''1.497 (10)
C2—C31.507 (4)
P1···O42.699 (4)P1···O6''3.026 (7)
P1···O6'3.014 (8)
C1—P1—C1A109.67 (14)C1B—P1—C1C101.19 (14)
C1—P1—C1B113.78 (14)C2—C1—C5123.5 (3)
C1A—P1—C1B107.20 (15)C2—C1—P1109.9 (2)
C1—P1—C1C114.37 (15)C5—C1—P1126.4 (3)
C1A—P1—C1C110.18 (15)
P1—C1—C2—O41.7 (4)P1—C1—C5—O7170.7 (3)
Selected geometric parameters (Å, º) for (IV) top
P1—C11.753 (5)C2—C31.483 (7)
P1—C1A1.795 (4)C5—O71.221 (6)
P1—C1B1.796 (5)C5—O61.341 (6)
P1—C1C1.818 (5)O6—C81.436 (8)
C1—C51.429 (7)C8—C101.469 (11)
C1—C21.443 (6)C8—C91.486 (11)
C2—O41.244 (6)
P1···O42.703 (16)P1···O63.023 (16)
C1—P1—C1A109.1 (2)C1B—P1—C1C101.0 (2)
C1—P1—C1B114.0 (2)C5—C1—C2122.5 (5)
C1A—P1—C1B107.5 (2)C5—C1—P1124.8 (4)
C1—P1—C1C115.1 (2)C2—C1—P1112.2 (4)
C1A—P1—C1C109.7 (2)
P1—C1—C2—O40.9 (6)P1—C1—C5—O7174.7 (5)
Selected geometric parameters (Å, º) for (V) top
P1—C11.7400 (19)C2—C31.504 (3)
P1—C1A1.8058 (19)C5—O71.206 (2)
P1—C1C1.809 (2)C5—O61.348 (2)
P1—C1B1.812 (2)O6—C81.472 (2)
C1—C21.429 (3)C8—C91.500 (3)
C1—C51.449 (3)C8—C111.507 (3)
C2—O41.243 (2)C8—C101.522 (3)
P1···O42.707 (2)P1···O63.012 (2)
C1—P1—C1A112.87 (10)C1C—P1—C1B100.18 (9)
C1—P1—C1C113.23 (9)C2—C1—C5123.22 (16)
C1A—P1—C1C109.56 (8)C2—C1—P1110.90 (13)
C1—P1—C1B112.60 (9)C5—C1—P1125.35 (13)
C1A—P1—C1B107.57 (9)
P1—C1—C2—O42.7 (2)P1—C1—C5—O7159.49 (18)
 

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