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
CCDC references: 159993; 159994; 159995; 159996
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%.
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.
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).
(II) Methyl 3-oxo-2-(triphenylphosphoranylidene)butyrate
top
Crystal data top
C23H21O3P·0.5C6H6 | F(000) = 876 |
Mr = 415.42 | Dx = 1.254 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.698 (5) Å | Cell parameters from 25 reflections |
b = 8.939 (4) Å | θ = 7.5–12.5° |
c = 23.026 (11) Å | µ = 0.15 mm−1 |
β = 91.66 (4)° | T = 293 K |
V = 2200.9 (17) Å3 | Prism, colourless |
Z = 4 | 0.24 × 0.18 × 0.15 mm |
Data collection top
Siemens R3m diffractometer | Rint = 0.055 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = −12→12 |
ω/2θ scans | k = 0→10 |
4102 measured reflections | l = 0→27 |
3892 independent reflections | 2 standard reflections every 98 reflections |
2766 reflections with I > 2σ(I) | intensity decay: <2% |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-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 parameters | Δρmax = 0.17 e Å−3 |
33 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C23H21O3P·0.5C6H6 | V = 2200.9 (17) Å3 |
Mr = 415.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.698 (5) Å | µ = 0.15 mm−1 |
b = 8.939 (4) Å | T = 293 K |
c = 23.026 (11) Å | 0.24 × 0.18 × 0.15 mm |
β = 91.66 (4)° | |
Data collection top
Siemens R3m diffractometer | Rint = 0.055 |
4102 measured reflections | 2 standard reflections every 98 reflections |
3892 independent reflections | intensity decay: <2% |
2766 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 33 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.17 e Å−3 |
3892 reflections | Δρmin = −0.19 e Å−3 |
274 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | −0.47999 (5) | −0.23447 (6) | 0.15600 (2) | 0.03199 (14) | |
C1 | −0.61435 (18) | −0.3450 (2) | 0.15928 (8) | 0.0343 (5) | |
C2 | −0.69652 (19) | −0.3280 (2) | 0.10973 (9) | 0.0367 (5) | |
C3 | −0.8276 (2) | −0.3908 (3) | 0.10922 (11) | 0.0538 (6) | |
H3A | −0.8701 | −0.3648 | 0.0733 | 0.081* | |
H3B | −0.8722 | −0.3497 | 0.1411 | 0.081* | |
H3C | −0.8240 | −0.4977 | 0.1129 | 0.081* | |
O4 | −0.66075 (13) | −0.26152 (17) | 0.06583 (6) | 0.0454 (4) | |
C5 | −0.6364 (2) | −0.4504 (2) | 0.20517 (9) | 0.0412 (5) | |
O6 | −0.53002 (15) | −0.49146 (19) | 0.23377 (7) | 0.0633 (5) | |
O7 | −0.73623 (15) | −0.5048 (2) | 0.21710 (7) | 0.0642 (5) | |
C8 | −0.5427 (3) | −0.5902 (4) | 0.28240 (13) | 0.0853 (10) | |
H1A | −0.4612 | −0.6166 | 0.2978 | 0.128* | |
H1B | −0.5862 | −0.6791 | 0.2700 | 0.128* | |
H1C | −0.5890 | −0.5410 | 0.3119 | 0.128* | |
C1A | −0.52418 (18) | −0.0479 (2) | 0.13205 (8) | 0.0346 (5) | |
C2A | −0.4714 (2) | 0.0195 (2) | 0.08432 (9) | 0.0454 (6) | |
H2A | −0.4095 | −0.0299 | 0.0642 | 0.054* | |
C3A | −0.5109 (2) | 0.1602 (3) | 0.06659 (11) | 0.0576 (7) | |
H3A1 | −0.4756 | 0.2052 | 0.0345 | 0.069* | |
C4A | −0.6019 (2) | 0.2334 (3) | 0.09615 (12) | 0.0624 (7) | |
H4A | −0.6282 | 0.3278 | 0.0841 | 0.075* | |
C5A | −0.6545 (2) | 0.1678 (3) | 0.14364 (11) | 0.0574 (7) | |
H5A | −0.7156 | 0.2184 | 0.1638 | 0.069* | |
C6A | −0.6167 (2) | 0.0262 (2) | 0.16144 (10) | 0.0453 (6) | |
H6A | −0.6535 | −0.0188 | 0.1931 | 0.054* | |
C1B | −0.40190 (18) | −0.2192 (2) | 0.22699 (8) | 0.0353 (5) | |
C2B | −0.4518 (2) | −0.1342 (3) | 0.27075 (9) | 0.0536 (6) | |
H2B | −0.5251 | −0.0805 | 0.2637 | 0.064* | |
C3B | −0.3932 (3) | −0.1287 (3) | 0.32486 (10) | 0.0672 (8) | |
H3B1 | −0.4274 | −0.0710 | 0.3540 | 0.081* | |
C4B | −0.2849 (2) | −0.2071 (3) | 0.33624 (10) | 0.0618 (7) | |
H4B | −0.2457 | −0.2024 | 0.3728 | 0.074* | |
C5B | −0.2353 (2) | −0.2918 (3) | 0.29335 (10) | 0.0660 (8) | |
H5B | −0.1622 | −0.3456 | 0.3009 | 0.079* | |
C6B | −0.2928 (2) | −0.2987 (3) | 0.23879 (10) | 0.0539 (6) | |
H6B | −0.2581 | −0.3569 | 0.2099 | 0.065* | |
C1C | −0.36249 (18) | −0.3000 (2) | 0.10758 (8) | 0.0340 (5) | |
C2C | −0.3850 (2) | −0.4251 (2) | 0.07360 (9) | 0.0405 (5) | |
H2C | −0.4611 | −0.4750 | 0.0755 | 0.049* | |
C3C | −0.2940 (2) | −0.4764 (3) | 0.03669 (9) | 0.0525 (6) | |
H3C1 | −0.3092 | −0.5603 | 0.0137 | 0.063* | |
C4C | −0.1813 (2) | −0.4030 (3) | 0.03419 (10) | 0.0550 (7) | |
H4C | −0.1204 | −0.4377 | 0.0095 | 0.066* | |
C5C | −0.1581 (2) | −0.2785 (3) | 0.06796 (10) | 0.0541 (6) | |
H5C | −0.0818 | −0.2293 | 0.0661 | 0.065* | |
C6C | −0.24802 (15) | −0.2270 (2) | 0.10444 (8) | 0.0463 (6) | |
H6C | −0.2322 | −0.1428 | 0.1272 | 0.056* | |
C1D | −0.11023 (15) | 0.0110 (2) | −0.03265 (8) | 0.0837 (10) | |
H1D | −0.1843 | 0.0178 | −0.0547 | 0.100* | |
C2D | −0.0163 (2) | −0.0831 (3) | −0.04912 (13) | 0.0816 (9) | |
H2D | −0.0269 | −0.1399 | −0.0827 | 0.098* | |
C3D | 0.0931 (3) | −0.0949 (3) | −0.01678 (10) | 0.0794 (9) | |
H3D | 0.1556 | −0.1597 | −0.0284 | 0.095* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0317 (3) | 0.0328 (3) | 0.0315 (3) | −0.0010 (2) | 0.0015 (2) | −0.0020 (2) |
C1 | 0.0341 (11) | 0.0340 (11) | 0.0349 (11) | −0.0010 (9) | 0.0040 (9) | −0.0008 (9) |
C2 | 0.0357 (12) | 0.0329 (11) | 0.0417 (12) | 0.0023 (9) | 0.0047 (9) | −0.0075 (10) |
C3 | 0.0380 (13) | 0.0584 (16) | 0.0647 (16) | −0.0048 (12) | −0.0040 (11) | −0.0010 (13) |
O4 | 0.0509 (9) | 0.0482 (9) | 0.0371 (8) | −0.0057 (8) | −0.0023 (7) | 0.0000 (7) |
C5 | 0.0435 (13) | 0.0402 (13) | 0.0402 (12) | −0.0019 (11) | 0.0082 (10) | −0.0041 (10) |
O6 | 0.0555 (10) | 0.0630 (11) | 0.0708 (11) | −0.0068 (9) | −0.0083 (9) | 0.0308 (10) |
O7 | 0.0500 (10) | 0.0793 (12) | 0.0640 (11) | −0.0142 (9) | 0.0156 (8) | 0.0202 (10) |
C8 | 0.102 (2) | 0.084 (2) | 0.0690 (19) | 0.0016 (19) | −0.0057 (17) | 0.0400 (17) |
C1A | 0.0372 (11) | 0.0328 (11) | 0.0335 (11) | −0.0032 (9) | −0.0021 (9) | −0.0007 (9) |
C2A | 0.0479 (14) | 0.0415 (13) | 0.0468 (13) | −0.0034 (11) | 0.0024 (11) | 0.0012 (11) |
C3A | 0.0686 (17) | 0.0445 (14) | 0.0594 (16) | −0.0092 (13) | −0.0003 (13) | 0.0127 (13) |
C4A | 0.0729 (18) | 0.0335 (13) | 0.0798 (19) | 0.0002 (13) | −0.0116 (15) | 0.0113 (14) |
C5A | 0.0596 (16) | 0.0424 (14) | 0.0700 (17) | 0.0130 (12) | −0.0013 (13) | −0.0080 (13) |
C6A | 0.0498 (14) | 0.0425 (13) | 0.0435 (13) | 0.0072 (11) | 0.0019 (11) | −0.0018 (11) |
C1B | 0.0371 (11) | 0.0356 (11) | 0.0330 (10) | −0.0034 (9) | −0.0013 (9) | −0.0015 (9) |
C2B | 0.0608 (16) | 0.0596 (15) | 0.0400 (13) | 0.0173 (13) | −0.0076 (11) | −0.0098 (12) |
C3B | 0.090 (2) | 0.0712 (19) | 0.0398 (14) | 0.0169 (16) | −0.0086 (14) | −0.0181 (13) |
C4B | 0.0699 (18) | 0.0722 (18) | 0.0424 (14) | −0.0045 (15) | −0.0154 (13) | −0.0018 (13) |
C5B | 0.0567 (16) | 0.089 (2) | 0.0519 (15) | 0.0184 (15) | −0.0121 (12) | 0.0053 (15) |
C6B | 0.0512 (15) | 0.0681 (17) | 0.0421 (13) | 0.0140 (13) | −0.0029 (11) | −0.0019 (12) |
C1C | 0.0334 (11) | 0.0350 (11) | 0.0337 (11) | 0.0018 (9) | 0.0024 (8) | 0.0007 (9) |
C2C | 0.0415 (12) | 0.0407 (12) | 0.0396 (12) | −0.0006 (10) | 0.0059 (10) | 0.0004 (10) |
C3C | 0.0669 (17) | 0.0520 (15) | 0.0389 (13) | 0.0122 (13) | 0.0082 (11) | −0.0078 (11) |
C4C | 0.0513 (15) | 0.0705 (17) | 0.0443 (14) | 0.0182 (13) | 0.0187 (12) | 0.0043 (13) |
C5C | 0.0375 (13) | 0.0680 (17) | 0.0574 (15) | −0.0016 (12) | 0.0121 (11) | 0.0094 (14) |
C6C | 0.0402 (13) | 0.0499 (14) | 0.0491 (13) | −0.0042 (11) | 0.0046 (10) | −0.0044 (11) |
C1D | 0.069 (2) | 0.082 (2) | 0.099 (3) | −0.0062 (18) | −0.0163 (18) | 0.032 (2) |
C2D | 0.109 (3) | 0.065 (2) | 0.070 (2) | −0.0011 (19) | 0.0006 (19) | 0.0028 (16) |
C3D | 0.080 (2) | 0.0649 (19) | 0.095 (2) | 0.0129 (17) | 0.0229 (18) | 0.0174 (18) |
Geometric parameters (Å, º) top
P1—C1 | 1.747 (2) | C1B—C2B | 1.382 (3) |
P1—C1C | 1.802 (2) | C1B—C6B | 1.386 (3) |
P1—C1A | 1.815 (2) | C2B—C3B | 1.379 (3) |
P1—C1B | 1.819 (2) | C3B—C4B | 1.372 (3) |
C1—C2 | 1.428 (3) | C4B—C5B | 1.364 (3) |
C1—C5 | 1.441 (3) | C5B—C6B | 1.384 (3) |
C2—O4 | 1.243 (2) | C1C—C2C | 1.382 (3) |
C2—C3 | 1.510 (3) | C1C—C6C | 1.391 (3) |
C5—O7 | 1.212 (2) | C2C—C3C | 1.389 (3) |
C5—O6 | 1.349 (3) | C3C—C4C | 1.375 (3) |
O6—C8 | 1.435 (3) | C4C—C5C | 1.376 (3) |
C1A—C6A | 1.384 (3) | C5C—C6C | 1.374 (3) |
C1A—C2A | 1.388 (3) | C1D—C3Di | 1.3706 (16) |
C2A—C3A | 1.385 (3) | C1D—C2D | 1.3726 (15) |
C3A—C4A | 1.369 (3) | C2D—C3D | 1.3726 (16) |
C4A—C5A | 1.376 (3) | C3D—C1Di | 1.3706 (16) |
C5A—C6A | 1.387 (3) | | |
| | | |
P1···O4 | 2.806 (2) | P1···O6 | 2.971 (2) |
| | | |
C1—P1—C1C | 115.61 (10) | C4A—C5A—C6A | 120.1 (2) |
C1—P1—C1A | 108.97 (10) | C1A—C6A—C5A | 119.9 (2) |
C1C—P1—C1A | 106.92 (9) | C2B—C1B—C6B | 118.67 (19) |
C1—P1—C1B | 111.13 (10) | C2B—C1B—P1 | 121.30 (16) |
C1C—P1—C1B | 105.66 (10) | C6B—C1B—P1 | 119.98 (16) |
C1A—P1—C1B | 108.24 (9) | C3B—C2B—C1B | 120.2 (2) |
C2—C1—C5 | 123.05 (19) | C4B—C3B—C2B | 120.9 (2) |
C2—C1—P1 | 113.18 (15) | C5B—C4B—C3B | 119.3 (2) |
C5—C1—P1 | 123.63 (16) | C4B—C5B—C6B | 120.7 (2) |
O4—C2—C1 | 120.25 (19) | C5B—C6B—C1B | 120.3 (2) |
O4—C2—C3 | 118.62 (19) | C2C—C1C—C6C | 119.30 (18) |
C1—C2—C3 | 121.1 (2) | C2C—C1C—P1 | 120.01 (15) |
O7—C5—O6 | 121.1 (2) | C6C—C1C—P1 | 120.69 (15) |
O7—C5—C1 | 126.3 (2) | C1C—C2C—C3C | 120.0 (2) |
O6—C5—C1 | 112.48 (18) | C4C—C3C—C2C | 120.0 (2) |
C5—O6—C8 | 116.80 (19) | C5C—C4C—C3C | 120.4 (2) |
C6A—C1A—C2A | 119.5 (2) | C4C—C5C—C6C | 119.9 (2) |
C6A—C1A—P1 | 118.38 (16) | C5C—C6C—C1C | 120.48 (19) |
C2A—C1A—P1 | 122.09 (16) | C3Di—C1D—C2D | 118.90 (18) |
C3A—C2A—C1A | 120.0 (2) | C3D—C2D—C1D | 121.1 (2) |
C4A—C3A—C2A | 120.2 (2) | C1Di—C3D—C2D | 120.0 (2) |
C3A—C4A—C5A | 120.3 (2) | | |
| | | |
C1C—P1—C1—C2 | −75.63 (17) | C1—P1—C1B—C2B | −72.2 (2) |
C1A—P1—C1—C2 | 44.78 (17) | C1C—P1—C1B—C2B | 161.65 (18) |
C1B—P1—C1—C2 | 163.96 (14) | C1A—P1—C1B—C2B | 47.4 (2) |
C1C—P1—C1—C5 | 100.25 (18) | C1—P1—C1B—C6B | 105.10 (19) |
C1A—P1—C1—C5 | −139.35 (17) | C1C—P1—C1B—C6B | −21.0 (2) |
C1B—P1—C1—C5 | −20.2 (2) | C1A—P1—C1B—C6B | −135.28 (18) |
C5—C1—C2—O4 | −163.95 (19) | C6B—C1B—C2B—C3B | 0.3 (4) |
P1—C1—C2—O4 | 12.0 (3) | P1—C1B—C2B—C3B | 177.7 (2) |
C5—C1—C2—C3 | 15.7 (3) | C1B—C2B—C3B—C4B | 0.0 (4) |
P1—C1—C2—C3 | −168.43 (16) | C2B—C3B—C4B—C5B | −0.3 (4) |
C2—C1—C5—O7 | −22.1 (3) | C3B—C4B—C5B—C6B | 0.3 (4) |
P1—C1—C5—O7 | 162.47 (19) | C4B—C5B—C6B—C1B | 0.0 (4) |
C2—C1—C5—O6 | 154.90 (19) | C2B—C1B—C6B—C5B | −0.3 (4) |
P1—C1—C5—O6 | −20.6 (3) | P1—C1B—C6B—C5B | −177.7 (2) |
O7—C5—O6—C8 | −6.1 (3) | C1—P1—C1C—C2C | 3.7 (2) |
C1—C5—O6—C8 | 176.7 (2) | C1A—P1—C1C—C2C | −117.79 (17) |
C1—P1—C1A—C6A | 52.57 (19) | C1B—P1—C1C—C2C | 127.05 (17) |
C1C—P1—C1A—C6A | 178.19 (16) | C1—P1—C1C—C6C | −175.47 (15) |
C1B—P1—C1A—C6A | −68.40 (18) | C1A—P1—C1C—C6C | 63.01 (18) |
C1—P1—C1A—C2A | −125.12 (17) | C1B—P1—C1C—C6C | −52.14 (18) |
C1C—P1—C1A—C2A | 0.50 (19) | C6C—C1C—C2C—C3C | −0.2 (3) |
C1B—P1—C1A—C2A | 113.92 (18) | P1—C1C—C2C—C3C | −179.42 (16) |
C6A—C1A—C2A—C3A | 0.3 (3) | C1C—C2C—C3C—C4C | 0.3 (3) |
P1—C1A—C2A—C3A | 178.00 (17) | C2C—C3C—C4C—C5C | −0.2 (4) |
C1A—C2A—C3A—C4A | 0.1 (3) | C3C—C4C—C5C—C6C | 0.0 (4) |
C2A—C3A—C4A—C5A | 0.1 (4) | C4C—C5C—C6C—C1C | 0.1 (3) |
C3A—C4A—C5A—C6A | −0.8 (4) | C2C—C1C—C6C—C5C | 0.0 (3) |
C2A—C1A—C6A—C5A | −1.0 (3) | P1—C1C—C6C—C5C | 179.22 (16) |
P1—C1A—C6A—C5A | −178.77 (17) | C3Di—C1D—C2D—C3D | 0.4 (4) |
C4A—C5A—C6A—C1A | 1.2 (3) | C1D—C2D—C3D—C1Di | −0.5 (4) |
Symmetry code: (i) −x, −y, −z. |
(III) Ethyl 3-oxo-2-(triphenylphosphoranylidene)butyrate
top
Crystal data top
C24H23O3P | F(000) = 1648 |
Mr = 390.39 | Dx = 1.221 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 14.815 (4) Å | θ = 7.5–12.5° |
b = 16.226 (5) Å | µ = 0.15 mm−1 |
c = 17.670 (5) Å | T = 293 K |
V = 4248 (2) Å3 | Prism, colourless |
Z = 8 | 0.27 × 0.20 × 0.16 mm |
Data collection top
Siemens R3m diffractometer | Rint = 0.058 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = 0→17 |
ω/2θ scans | k = 0→19 |
3911 measured reflections | l = 0→20 |
3737 independent reflections | 2 standard reflections every 98 reflections |
1966 reflections with I > 2σ(I) | intensity decay: <2% |
Refinement top
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-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 parameters | Δρmax = 0.22 e Å−3 |
33 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C24H23O3P | V = 4248 (2) Å3 |
Mr = 390.39 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.815 (4) Å | µ = 0.15 mm−1 |
b = 16.226 (5) Å | T = 293 K |
c = 17.670 (5) Å | 0.27 × 0.20 × 0.16 mm |
Data collection top
Siemens R3m diffractometer | Rint = 0.058 |
3911 measured reflections | 2 standard reflections every 98 reflections |
3737 independent reflections | intensity decay: <2% |
1966 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 33 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.22 e Å−3 |
3737 reflections | Δρmin = −0.18 e Å−3 |
284 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
P1 | 0.24167 (5) | 0.31573 (5) | 0.16808 (4) | 0.0385 (2) | |
C1 | 0.3047 (2) | 0.40322 (18) | 0.14272 (18) | 0.0401 (8) | |
C2 | 0.3338 (2) | 0.3965 (2) | 0.0655 (2) | 0.0501 (9) | |
C3 | 0.3882 (3) | 0.4628 (2) | 0.0269 (2) | 0.0801 (13) | |
H3A | 0.4065 | 0.4439 | −0.0222 | 0.120* | |
H3B | 0.4408 | 0.4750 | 0.0567 | 0.120* | |
H3C | 0.3521 | 0.5116 | 0.0218 | 0.120* | |
O4 | 0.31063 (15) | 0.33503 (15) | 0.02781 (12) | 0.0607 (7) | |
C5 | 0.3321 (3) | 0.4692 (2) | 0.1925 (2) | 0.0585 (10) | |
O7 | 0.38327 (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) |
H8'1 | 0.3222 | 0.5717 | 0.2851 | 0.169* | 0.43 (3) |
H8'2 | 0.3991 | 0.5237 | 0.3275 | 0.169* | 0.43 (3) |
C9' | 0.279 (3) | 0.520 (4) | 0.384 (2) | 0.22 (2) | 0.43 (3) |
H9'1 | 0.3034 | 0.5584 | 0.4200 | 0.326* | 0.43 (3) |
H9'2 | 0.2800 | 0.4657 | 0.4047 | 0.326* | 0.43 (3) |
H9'3 | 0.2185 | 0.5355 | 0.3715 | 0.326* | 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''1 | 0.2311 | 0.5649 | 0.3213 | 0.139* | 0.57 (3) |
H8''2 | 0.3301 | 0.5806 | 0.2922 | 0.139* | 0.57 (3) |
C9'' | 0.3255 (18) | 0.499 (2) | 0.3805 (16) | 0.151 (9) | 0.57 (3) |
H9''1 | 0.2809 | 0.4628 | 0.4015 | 0.227* | 0.57 (3) |
H9''2 | 0.3405 | 0.5409 | 0.4168 | 0.227* | 0.57 (3) |
H9''3 | 0.3787 | 0.4682 | 0.3679 | 0.227* | 0.57 (3) |
C1A | 0.3113 (2) | 0.22495 (19) | 0.16040 (18) | 0.0455 (8) | |
C2A | 0.2844 (3) | 0.1552 (2) | 0.1214 (2) | 0.0730 (12) | |
H2AA | 0.2291 | 0.1547 | 0.0965 | 0.088* | |
C3A | 0.3394 (3) | 0.0863 (3) | 0.1193 (3) | 0.0973 (17) | |
H3AA | 0.3208 | 0.0396 | 0.0930 | 0.117* | |
C4A | 0.4213 (3) | 0.0865 (3) | 0.1557 (3) | 0.0910 (16) | |
H4AA | 0.4573 | 0.0395 | 0.1553 | 0.109* | |
C5A | 0.4498 (3) | 0.1560 (3) | 0.1928 (3) | 0.0980 (16) | |
H5AA | 0.5057 | 0.1568 | 0.2167 | 0.118* | |
C6A | 0.3948 (2) | 0.2252 (2) | 0.1943 (2) | 0.0796 (13) | |
H6AA | 0.4148 | 0.2726 | 0.2187 | 0.095* | |
C1B | 0.1984 (2) | 0.31892 (19) | 0.26423 (15) | 0.0389 (7) | |
C2B | 0.2353 (3) | 0.2738 (2) | 0.32263 (19) | 0.0619 (10) | |
H2BA | 0.2855 | 0.2408 | 0.3139 | 0.074* | |
C3B | 0.1977 (3) | 0.2777 (3) | 0.3947 (2) | 0.0848 (14) | |
H3BA | 0.2229 | 0.2475 | 0.4341 | 0.102* | |
C4B | 0.1234 (3) | 0.3261 (3) | 0.4077 (2) | 0.0849 (14) | |
H4BA | 0.0980 | 0.3283 | 0.4558 | 0.102* | |
C5B | 0.0866 (3) | 0.3713 (3) | 0.3496 (2) | 0.0850 (14) | |
H5BA | 0.0368 | 0.4047 | 0.3587 | 0.102* | |
C6B | 0.1229 (2) | 0.3674 (2) | 0.2780 (2) | 0.0630 (11) | |
H6BA | 0.0968 | 0.3973 | 0.2388 | 0.076* | |
C1C | 0.13793 (19) | 0.3022 (2) | 0.11422 (18) | 0.0442 (8) | |
C2C | 0.0811 (2) | 0.2367 (2) | 0.13070 (19) | 0.0563 (10) | |
H2CA | 0.0986 | 0.1969 | 0.1656 | 0.068* | |
C3C | −0.0020 (3) | 0.2308 (3) | 0.0949 (2) | 0.0794 (14) | |
H3CA | −0.0402 | 0.1871 | 0.1062 | 0.095* | |
C4C | −0.0285 (3) | 0.2890 (3) | 0.0429 (3) | 0.0837 (14) | |
H4CA | −0.0837 | 0.2841 | 0.0184 | 0.100* | |
C5C | 0.0273 (2) | 0.3545 (3) | 0.0273 (2) | 0.0754 (12) | |
H5CA | 0.0090 | 0.3947 | −0.0069 | 0.091* | |
C6C | 0.1108 (2) | 0.3612 (2) | 0.06236 (18) | 0.0520 (9) | |
H6CA | 0.1486 | 0.4053 | 0.0510 | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0394 (4) | 0.0370 (4) | 0.0392 (4) | −0.0038 (4) | 0.0003 (4) | −0.0011 (4) |
C1 | 0.0360 (18) | 0.0341 (18) | 0.050 (2) | −0.0072 (16) | 0.0027 (15) | 0.0060 (15) |
C2 | 0.038 (2) | 0.057 (2) | 0.055 (2) | 0.0084 (19) | 0.0046 (18) | 0.017 (2) |
C3 | 0.075 (3) | 0.086 (3) | 0.078 (3) | −0.009 (2) | 0.015 (2) | 0.035 (2) |
O4 | 0.0630 (16) | 0.0670 (18) | 0.0521 (15) | 0.0027 (14) | 0.0113 (13) | −0.0051 (14) |
C5 | 0.055 (2) | 0.054 (2) | 0.066 (3) | −0.011 (2) | −0.006 (2) | −0.001 (2) |
O7 | 0.088 (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) |
C1A | 0.0430 (19) | 0.039 (2) | 0.054 (2) | −0.0021 (16) | 0.0083 (18) | 0.0024 (18) |
C2A | 0.064 (3) | 0.044 (2) | 0.112 (3) | −0.009 (2) | 0.017 (2) | −0.019 (2) |
C3A | 0.075 (3) | 0.045 (3) | 0.172 (5) | −0.008 (3) | 0.040 (3) | −0.019 (3) |
C4A | 0.076 (3) | 0.059 (3) | 0.137 (5) | 0.026 (3) | 0.031 (3) | 0.009 (3) |
C5A | 0.070 (3) | 0.111 (4) | 0.112 (4) | 0.036 (3) | −0.014 (3) | −0.026 (3) |
C6A | 0.057 (3) | 0.077 (3) | 0.106 (3) | 0.020 (2) | −0.015 (2) | −0.032 (3) |
C1B | 0.0451 (19) | 0.0360 (18) | 0.0357 (18) | −0.0084 (17) | 0.0018 (15) | 0.0015 (16) |
C2B | 0.079 (3) | 0.058 (2) | 0.049 (2) | 0.009 (2) | 0.001 (2) | 0.0098 (19) |
C3B | 0.127 (4) | 0.077 (3) | 0.050 (3) | −0.008 (3) | 0.006 (3) | 0.011 (2) |
C4B | 0.100 (4) | 0.102 (4) | 0.053 (3) | −0.030 (3) | 0.032 (3) | −0.010 (3) |
C5B | 0.067 (3) | 0.122 (4) | 0.066 (3) | 0.006 (3) | 0.015 (2) | −0.023 (3) |
C6B | 0.059 (2) | 0.081 (3) | 0.050 (2) | 0.006 (2) | 0.0002 (19) | −0.010 (2) |
C1C | 0.0361 (18) | 0.050 (2) | 0.046 (2) | −0.0064 (17) | 0.0042 (15) | −0.0038 (17) |
C2C | 0.054 (2) | 0.058 (2) | 0.056 (2) | −0.013 (2) | 0.0046 (19) | 0.0004 (19) |
C3C | 0.053 (2) | 0.107 (4) | 0.079 (3) | −0.026 (3) | 0.008 (2) | −0.024 (3) |
C4C | 0.057 (3) | 0.120 (4) | 0.075 (3) | −0.005 (3) | −0.016 (2) | −0.029 (3) |
C5C | 0.062 (3) | 0.087 (3) | 0.078 (3) | 0.005 (3) | −0.028 (2) | −0.004 (3) |
C6C | 0.051 (2) | 0.057 (2) | 0.048 (2) | −0.0046 (19) | −0.0098 (18) | −0.0029 (19) |
Geometric parameters (Å, º) top
P1—C1 | 1.757 (3) | C2A—C3A | 1.384 (5) |
P1—C1A | 1.804 (3) | C3A—C4A | 1.374 (5) |
P1—C1B | 1.817 (3) | C4A—C5A | 1.371 (5) |
P1—C1C | 1.821 (3) | C5A—C6A | 1.388 (5) |
C1—C2 | 1.434 (4) | C1B—C2B | 1.378 (4) |
C1—C5 | 1.444 (4) | C1B—C6B | 1.389 (4) |
C2—O4 | 1.248 (4) | C2B—C3B | 1.392 (4) |
C2—C3 | 1.507 (4) | C3B—C4B | 1.370 (5) |
C5—O7 | 1.197 (4) | C4B—C5B | 1.375 (5) |
C5—O6'' | 1.352 (7) | C5B—C6B | 1.376 (4) |
C5—O6' | 1.360 (8) | C1C—C2C | 1.386 (4) |
O6'—C8' | 1.457 (9) | C1C—C6C | 1.385 (4) |
C8'—C9' | 1.494 (10) | C2C—C3C | 1.387 (4) |
O6''—C8'' | 1.466 (8) | C3C—C4C | 1.375 (5) |
C8''—C9'' | 1.497 (10) | C4C—C5C | 1.374 (5) |
C1A—C6A | 1.374 (4) | C5C—C6C | 1.388 (4) |
C1A—C2A | 1.383 (4) | | |
| | | |
P1···O4 | 2.699 (4) | P1···O6'' | 3.026 (7) |
P1···O6' | 3.014 (8) | | |
| | | |
C1—P1—C1A | 109.67 (14) | C6A—C1A—P1 | 118.6 (3) |
C1—P1—C1B | 113.78 (14) | C2A—C1A—P1 | 122.7 (3) |
C1A—P1—C1B | 107.20 (15) | C3A—C2A—C1A | 120.3 (4) |
C1—P1—C1C | 114.37 (15) | C4A—C3A—C2A | 120.4 (4) |
C1A—P1—C1C | 110.18 (15) | C5A—C4A—C3A | 119.8 (4) |
C1B—P1—C1C | 101.19 (14) | C4A—C5A—C6A | 119.6 (4) |
C2—C1—C5 | 123.5 (3) | C1A—C6A—C5A | 121.1 (4) |
C2—C1—P1 | 109.9 (2) | C2B—C1B—C6B | 119.3 (3) |
C5—C1—P1 | 126.4 (3) | C2B—C1B—P1 | 123.0 (3) |
O4—C2—C1 | 119.1 (3) | C6B—C1B—P1 | 117.7 (2) |
O4—C2—C3 | 118.4 (3) | C1B—C2B—C3B | 120.1 (4) |
C1—C2—C3 | 122.5 (4) | C4B—C3B—C2B | 120.0 (4) |
O7—C5—O6'' | 120.0 (6) | C3B—C4B—C5B | 119.9 (4) |
O7—C5—O6' | 117.3 (7) | C4B—C5B—C6B | 120.5 (4) |
O6''—C5—O6' | 32.7 (6) | C5B—C6B—C1B | 120.1 (4) |
O7—C5—C1 | 127.4 (4) | C2C—C1C—C6C | 119.5 (3) |
O6''—C5—C1 | 111.1 (6) | C2C—C1C—P1 | 119.7 (3) |
O6'—C5—C1 | 112.1 (8) | C6C—C1C—P1 | 120.5 (2) |
C5—O6'—C8' | 109.9 (18) | C1C—C2C—C3C | 119.7 (3) |
O6'—C8'—C9' | 111 (3) | C4C—C3C—C2C | 120.7 (4) |
C5—O6''—C8'' | 121.3 (11) | C5C—C4C—C3C | 119.5 (4) |
O6''—C8''—C9'' | 107.6 (16) | C4C—C5C—C6C | 120.5 (4) |
C6A—C1A—C2A | 118.6 (3) | C1C—C6C—C5C | 119.9 (3) |
| | | |
C1A—P1—C1—C2 | 61.7 (3) | C2A—C3A—C4A—C5A | −1.8 (7) |
C1B—P1—C1—C2 | −178.3 (2) | C3A—C4A—C5A—C6A | 1.2 (7) |
C1C—P1—C1—C2 | −62.7 (3) | C2A—C1A—C6A—C5A | −2.9 (6) |
C1A—P1—C1—C5 | −112.6 (3) | P1—C1A—C6A—C5A | 177.5 (3) |
C1B—P1—C1—C5 | 7.4 (3) | C4A—C5A—C6A—C1A | 1.1 (7) |
C1C—P1—C1—C5 | 123.0 (3) | C1—P1—C1B—C2B | −104.3 (3) |
C5—C1—C2—O4 | 176.2 (3) | C1A—P1—C1B—C2B | 17.2 (3) |
P1—C1—C2—O4 | 1.7 (4) | C1C—P1—C1B—C2B | 132.6 (3) |
C5—C1—C2—C3 | −6.4 (5) | C1—P1—C1B—C6B | 77.7 (3) |
P1—C1—C2—C3 | 179.1 (3) | C1A—P1—C1B—C6B | −160.9 (3) |
C2—C1—C5—O7 | −2.8 (6) | C1C—P1—C1B—C6B | −45.4 (3) |
P1—C1—C5—O7 | 170.7 (3) | C6B—C1B—C2B—C3B | −0.6 (5) |
C2—C1—C5—O6'' | 162.9 (10) | P1—C1B—C2B—C3B | −178.6 (3) |
P1—C1—C5—O6'' | −23.6 (11) | C1B—C2B—C3B—C4B | 0.3 (6) |
C2—C1—C5—O6' | −161.9 (14) | C2B—C3B—C4B—C5B | −0.5 (6) |
P1—C1—C5—O6' | 11.7 (14) | C3B—C4B—C5B—C6B | 1.0 (7) |
O7—C5—O6'—C8' | 26 (2) | C4B—C5B—C6B—C1B | −1.3 (6) |
O6''—C5—O6'—C8' | −77 (3) | C2B—C1B—C6B—C5B | 1.1 (5) |
C1—C5—O6'—C8' | −172.4 (14) | P1—C1B—C6B—C5B | 179.2 (3) |
C5—O6'—C8'—C9' | 150 (5) | C1—P1—C1C—C2C | −178.0 (2) |
O7—C5—O6''—C8'' | −10 (2) | C1A—P1—C1C—C2C | 57.9 (3) |
O6'—C5—O6''—C8'' | 84 (3) | C1B—P1—C1C—C2C | −55.3 (3) |
C1—C5—O6''—C8'' | −177.1 (13) | C1—P1—C1C—C6C | −4.6 (3) |
C5—O6''—C8''—C9'' | −108 (3) | C1A—P1—C1C—C6C | −128.7 (3) |
C1—P1—C1A—C6A | 50.0 (3) | C1B—P1—C1C—C6C | 118.1 (3) |
C1B—P1—C1A—C6A | −74.0 (3) | C6C—C1C—C2C—C3C | 0.3 (5) |
C1C—P1—C1A—C6A | 176.7 (3) | P1—C1C—C2C—C3C | 173.7 (3) |
C1—P1—C1A—C2A | −129.6 (3) | C1C—C2C—C3C—C4C | 0.4 (5) |
C1B—P1—C1A—C2A | 106.4 (3) | C2C—C3C—C4C—C5C | −1.3 (6) |
C1C—P1—C1A—C2A | −2.9 (3) | C3C—C4C—C5C—C6C | 1.6 (6) |
C6A—C1A—C2A—C3A | 2.4 (5) | C2C—C1C—C6C—C5C | 0.0 (5) |
P1—C1A—C2A—C3A | −178.0 (3) | P1—C1C—C6C—C5C | −173.4 (3) |
C1A—C2A—C3A—C4A | −0.1 (6) | C4C—C5C—C6C—C1C | −0.9 (6) |
(IV) i-Propyl 3-oxo-2-(triphenylphosphoranylidene)butyrate
top
Crystal data top
C25H25O3P | F(000) = 1712 |
Mr = 404.42 | Dx = 1.238 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 14.932 (7) Å | θ = 7.5–12.5° |
b = 16.343 (6) Å | µ = 0.15 mm−1 |
c = 17.780 (7) Å | T = 293 K |
V = 4339 (3) Å3 | Prism, colourless |
Z = 8 | 0.22 × 0.19 × 0.16 mm |
Data collection top
Siemens R3m diffractometer | Rint = 0.096 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = 0→17 |
ω/2θ scans | k = 0→19 |
4441 measured reflections | l = 0→21 |
3824 independent reflections | 2 standard reflections every 98 reflections |
1801 reflections with I > 2σ(I) | intensity decay: <2% |
Refinement top
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)] = 0.089 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.160 | H-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 parameters | Δρmax = 0.20 e Å−3 |
27 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C25H25O3P | V = 4339 (3) Å3 |
Mr = 404.42 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.932 (7) Å | µ = 0.15 mm−1 |
b = 16.343 (6) Å | T = 293 K |
c = 17.780 (7) Å | 0.22 × 0.19 × 0.16 mm |
Data collection top
Siemens R3m diffractometer | Rint = 0.096 |
4441 measured reflections | 2 standard reflections every 98 reflections |
3824 independent reflections | intensity decay: <2% |
1801 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.089 | 27 restraints |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.20 e Å−3 |
3824 reflections | Δρmin = −0.21 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
P1 | 0.24246 (9) | 0.81464 (8) | −0.33182 (7) | 0.0393 (3) | |
C1 | 0.3038 (3) | 0.9024 (3) | −0.3555 (3) | 0.0366 (12) | |
C2 | 0.3371 (3) | 0.8993 (3) | −0.4316 (3) | 0.0454 (14) | |
C3 | 0.3935 (4) | 0.9649 (3) | −0.4644 (3) | 0.0713 (18) | |
H3A | 0.4094 | 0.9507 | −0.5151 | 0.107* | |
H3B | 0.4470 | 0.9710 | −0.4349 | 0.107* | |
H3C | 0.3608 | 1.0155 | −0.4644 | 0.107* | |
O4 | 0.3171 (2) | 0.8374 (2) | −0.46870 (19) | 0.0499 (10) | |
C5 | 0.3299 (4) | 0.9647 (4) | −0.3036 (3) | 0.0584 (17) | |
O6 | 0.2863 (4) | 0.9633 (3) | −0.2377 (3) | 0.1111 (19) | |
O7 | 0.3773 (3) | 1.0242 (3) | −0.3153 (2) | 0.0858 (15) | |
C8 | 0.3073 (8) | 1.0227 (6) | −0.1809 (5) | 0.123 (4) | |
H8A | 0.3561 | 1.0582 | −0.1980 | 0.148* | |
C9 | 0.3462 (5) | 0.9777 (6) | −0.1160 (5) | 0.139 (4) | |
H9A | 0.4037 | 0.9561 | −0.1298 | 0.208* | |
H9B | 0.3071 | 0.9336 | −0.1021 | 0.208* | |
H9C | 0.3529 | 1.0143 | −0.0742 | 0.208* | |
C10 | 0.2208 (8) | 1.0575 (5) | −0.1580 (5) | 0.155 (4) | |
H10D | 0.2009 | 1.0958 | −0.1954 | 0.232* | |
H10E | 0.2275 | 1.0852 | −0.1107 | 0.232* | |
H10F | 0.1776 | 1.0145 | −0.1529 | 0.232* | |
C1A | 0.3131 (3) | 0.7264 (3) | −0.3413 (2) | 0.0319 (11) | |
C2A | 0.2847 (4) | 0.6564 (3) | −0.3786 (3) | 0.0580 (16) | |
H2A | 0.2288 | 0.6556 | −0.4016 | 0.070* | |
C3A | 0.3392 (4) | 0.5872 (3) | −0.3821 (3) | 0.0663 (18) | |
H3A1 | 0.3199 | 0.5404 | −0.4070 | 0.080* | |
C4A | 0.4227 (4) | 0.5892 (4) | −0.3477 (4) | 0.079 (2) | |
H4A | 0.4592 | 0.5431 | −0.3491 | 0.095* | |
C5A | 0.4523 (4) | 0.6590 (4) | −0.3115 (4) | 0.084 (2) | |
H5A | 0.5090 | 0.6605 | −0.2899 | 0.101* | |
C6A | 0.3963 (4) | 0.7272 (4) | −0.3075 (3) | 0.0675 (18) | |
H6A | 0.4153 | 0.7737 | −0.2819 | 0.081* | |
C1B | 0.1996 (3) | 0.8152 (3) | −0.2374 (2) | 0.0381 (12) | |
C2B | 0.2417 (4) | 0.7738 (3) | −0.1792 (3) | 0.0684 (17) | |
H2B | 0.2936 | 0.7440 | −0.1886 | 0.082* | |
C3B | 0.2063 (5) | 0.7767 (4) | −0.1066 (4) | 0.084 (2) | |
H3B1 | 0.2353 | 0.7494 | −0.0677 | 0.101* | |
C4B | 0.1291 (5) | 0.8193 (4) | −0.0923 (4) | 0.086 (2) | |
H4B | 0.1055 | 0.8209 | −0.0440 | 0.103* | |
C5B | 0.0871 (5) | 0.8597 (5) | −0.1503 (4) | 0.092 (2) | |
H5B | 0.0345 | 0.8884 | −0.1407 | 0.111* | |
C6B | 0.1214 (4) | 0.8586 (4) | −0.2222 (3) | 0.0681 (18) | |
H6B | 0.0924 | 0.8867 | −0.2606 | 0.082* | |
C1C | 0.1401 (3) | 0.7997 (3) | −0.3854 (3) | 0.0373 (12) | |
C2C | 0.0848 (3) | 0.7339 (3) | −0.3695 (3) | 0.0535 (15) | |
H2C | 0.1017 | 0.6952 | −0.3339 | 0.064* | |
C3C | 0.0036 (4) | 0.7262 (4) | −0.4074 (3) | 0.0640 (18) | |
H3C1 | −0.0340 | 0.6822 | −0.3972 | 0.077* | |
C4C | −0.0210 (4) | 0.7842 (4) | −0.4604 (4) | 0.078 (2) | |
H4C | −0.0746 | 0.7781 | −0.4864 | 0.093* | |
C5C | 0.0334 (4) | 0.8517 (4) | −0.4752 (3) | 0.0733 (19) | |
H5C | 0.0156 | 0.8915 | −0.5095 | 0.088* | |
C6C | 0.1152 (3) | 0.8582 (3) | −0.4375 (3) | 0.0546 (15) | |
H6C | 0.1530 | 0.9021 | −0.4475 | 0.065* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0412 (8) | 0.0444 (7) | 0.0324 (6) | −0.0043 (8) | 0.0017 (7) | −0.0001 (7) |
C1 | 0.040 (3) | 0.036 (3) | 0.033 (3) | 0.004 (3) | −0.001 (2) | −0.006 (2) |
C2 | 0.043 (4) | 0.056 (3) | 0.037 (3) | 0.013 (3) | 0.009 (3) | 0.012 (3) |
C3 | 0.070 (5) | 0.068 (4) | 0.075 (4) | −0.006 (4) | 0.010 (4) | 0.015 (4) |
O4 | 0.041 (2) | 0.061 (2) | 0.047 (2) | −0.003 (2) | 0.0148 (18) | −0.0129 (19) |
C5 | 0.069 (4) | 0.053 (4) | 0.053 (4) | −0.017 (3) | 0.022 (3) | 0.010 (3) |
O6 | 0.149 (5) | 0.096 (4) | 0.088 (4) | −0.067 (3) | 0.038 (3) | −0.042 (3) |
O7 | 0.099 (4) | 0.070 (3) | 0.089 (3) | −0.029 (3) | 0.021 (3) | −0.015 (3) |
C8 | 0.182 (11) | 0.114 (8) | 0.074 (6) | −0.071 (8) | 0.041 (7) | −0.014 (6) |
C9 | 0.114 (8) | 0.171 (9) | 0.131 (8) | −0.043 (7) | −0.006 (7) | −0.040 (7) |
C10 | 0.247 (14) | 0.119 (7) | 0.099 (7) | 0.014 (9) | −0.022 (8) | −0.017 (6) |
C1A | 0.038 (3) | 0.027 (3) | 0.031 (3) | −0.001 (2) | 0.004 (2) | 0.006 (2) |
C2A | 0.063 (4) | 0.046 (3) | 0.065 (4) | 0.008 (3) | −0.002 (3) | −0.005 (3) |
C3A | 0.060 (5) | 0.053 (4) | 0.086 (5) | −0.011 (4) | 0.022 (4) | −0.002 (3) |
C4A | 0.077 (5) | 0.063 (5) | 0.097 (6) | 0.002 (4) | 0.018 (5) | −0.001 (4) |
C5A | 0.069 (5) | 0.091 (5) | 0.093 (6) | 0.011 (5) | −0.009 (4) | 0.007 (4) |
C6A | 0.071 (4) | 0.066 (4) | 0.066 (4) | −0.001 (4) | 0.004 (4) | 0.004 (3) |
C1B | 0.046 (3) | 0.030 (3) | 0.039 (3) | −0.013 (3) | 0.008 (3) | −0.006 (3) |
C2B | 0.078 (4) | 0.067 (4) | 0.060 (4) | 0.001 (4) | 0.009 (4) | −0.004 (3) |
C3B | 0.087 (6) | 0.092 (6) | 0.073 (5) | −0.009 (4) | −0.006 (4) | 0.008 (4) |
C4B | 0.088 (6) | 0.100 (6) | 0.070 (5) | −0.022 (5) | 0.012 (5) | 0.006 (5) |
C5B | 0.075 (5) | 0.112 (6) | 0.089 (6) | −0.015 (5) | 0.007 (5) | −0.024 (5) |
C6B | 0.077 (5) | 0.074 (4) | 0.054 (4) | 0.002 (4) | 0.002 (4) | −0.010 (3) |
C1C | 0.045 (3) | 0.032 (3) | 0.035 (3) | −0.001 (3) | −0.003 (2) | −0.002 (2) |
C2C | 0.053 (4) | 0.063 (4) | 0.045 (3) | −0.009 (3) | −0.001 (3) | 0.003 (3) |
C3C | 0.054 (4) | 0.069 (5) | 0.069 (4) | −0.019 (3) | 0.001 (3) | 0.000 (4) |
C4C | 0.068 (5) | 0.091 (5) | 0.074 (5) | −0.001 (4) | −0.002 (4) | −0.007 (4) |
C5C | 0.049 (4) | 0.092 (5) | 0.079 (5) | 0.005 (4) | −0.016 (4) | −0.002 (4) |
C6C | 0.040 (3) | 0.066 (4) | 0.058 (4) | 0.003 (3) | 0.001 (3) | 0.003 (3) |
Geometric parameters (Å, º) top
P1—C1 | 1.753 (5) | C3A—C4A | 1.389 (6) |
P1—C1A | 1.795 (4) | C4A—C5A | 1.383 (6) |
P1—C1B | 1.796 (5) | C5A—C6A | 1.394 (6) |
P1—C1C | 1.818 (5) | C1B—C2B | 1.386 (6) |
C1—C5 | 1.429 (7) | C1B—C6B | 1.393 (6) |
C1—C2 | 1.443 (6) | C2B—C3B | 1.396 (6) |
C2—O4 | 1.244 (6) | C3B—C4B | 1.370 (7) |
C2—C3 | 1.483 (7) | C4B—C5B | 1.376 (6) |
C5—O7 | 1.221 (6) | C5B—C6B | 1.379 (6) |
C5—O6 | 1.341 (6) | C1C—C2C | 1.385 (5) |
O6—C8 | 1.436 (8) | C1C—C6C | 1.383 (5) |
C8—C10 | 1.469 (11) | C2C—C3C | 1.392 (6) |
C8—C9 | 1.486 (11) | C3C—C4C | 1.386 (6) |
C1A—C6A | 1.380 (6) | C4C—C5C | 1.395 (6) |
C1A—C2A | 1.389 (5) | C5C—C6C | 1.397 (6) |
C2A—C3A | 1.394 (6) | | |
| | | |
P1···O4 | 2.703 (16) | P1···O6 | 3.023 (16) |
| | | |
C1—P1—C1A | 109.1 (2) | C1A—C2A—C3A | 120.7 (5) |
C1—P1—C1B | 114.0 (2) | C4A—C3A—C2A | 119.0 (6) |
C1A—P1—C1B | 107.5 (2) | C5A—C4A—C3A | 120.7 (6) |
C1—P1—C1C | 115.1 (2) | C4A—C5A—C6A | 119.5 (6) |
C1A—P1—C1C | 109.7 (2) | C1A—C6A—C5A | 120.6 (6) |
C1B—P1—C1C | 101.0 (2) | C2B—C1B—C6B | 118.9 (5) |
C5—C1—C2 | 122.5 (5) | C2B—C1B—P1 | 122.3 (4) |
C5—C1—P1 | 124.8 (4) | C6B—C1B—P1 | 118.8 (4) |
C2—C1—P1 | 112.2 (4) | C1B—C2B—C3B | 120.2 (6) |
O4—C2—C1 | 116.3 (5) | C4B—C3B—C2B | 120.4 (6) |
O4—C2—C3 | 121.1 (5) | C3B—C4B—C5B | 119.3 (7) |
C1—C2—C3 | 122.6 (5) | C4B—C5B—C6B | 121.2 (7) |
O7—C5—O6 | 116.4 (6) | C5B—C6B—C1B | 119.9 (6) |
O7—C5—C1 | 128.0 (5) | C2C—C1C—C6C | 120.9 (5) |
O6—C5—C1 | 114.9 (5) | C2C—C1C—P1 | 120.0 (4) |
C5—O6—C8 | 119.8 (5) | C6C—C1C—P1 | 119.0 (4) |
O6—C8—C10 | 105.4 (9) | C1C—C2C—C3C | 119.4 (5) |
O6—C8—C9 | 107.3 (8) | C4C—C3C—C2C | 119.8 (6) |
C10—C8—C9 | 108.7 (8) | C3C—C4C—C5C | 121.0 (6) |
C6A—C1A—C2A | 119.4 (5) | C4C—C5C—C6C | 118.6 (6) |
C6A—C1A—P1 | 118.7 (4) | C1C—C6C—C5C | 120.2 (5) |
C2A—C1A—P1 | 121.8 (4) | | |
| | | |
C1A—P1—C1—C5 | −111.7 (5) | P1—C1A—C6A—C5A | 178.0 (4) |
C1B—P1—C1—C5 | 8.5 (5) | C4A—C5A—C6A—C1A | −1.9 (9) |
C1C—P1—C1—C5 | 124.6 (5) | C1—P1—C1B—C2B | −99.3 (5) |
C1A—P1—C1—C2 | 59.7 (4) | C1A—P1—C1B—C2B | 21.8 (5) |
C1B—P1—C1—C2 | 179.8 (3) | C1C—P1—C1B—C2B | 136.7 (4) |
C1C—P1—C1—C2 | −64.1 (4) | C1—P1—C1B—C6B | 80.8 (4) |
C5—C1—C2—O4 | 172.5 (5) | C1A—P1—C1B—C6B | −158.1 (4) |
P1—C1—C2—O4 | 0.9 (6) | C1C—P1—C1B—C6B | −43.2 (4) |
C5—C1—C2—C3 | −6.4 (8) | C6B—C1B—C2B—C3B | −0.7 (8) |
P1—C1—C2—C3 | −177.9 (4) | P1—C1B—C2B—C3B | 179.4 (4) |
C2—C1—C5—O7 | 4.2 (9) | C1B—C2B—C3B—C4B | 1.0 (10) |
P1—C1—C5—O7 | 174.7 (5) | C2B—C3B—C4B—C5B | −0.4 (11) |
C2—C1—C5—O6 | 173.8 (5) | C3B—C4B—C5B—C6B | −0.4 (11) |
P1—C1—C5—O6 | −15.7 (8) | C4B—C5B—C6B—C1B | 0.6 (10) |
O7—C5—O6—C8 | −9.5 (11) | C2B—C1B—C6B—C5B | −0.1 (8) |
C1—C5—O6—C8 | 179.6 (7) | P1—C1B—C6B—C5B | 179.8 (5) |
C5—O6—C8—C10 | 129.3 (8) | C1—P1—C1C—C2C | −177.7 (4) |
C5—O6—C8—C9 | −115.0 (8) | C1A—P1—C1C—C2C | 58.8 (4) |
C1—P1—C1A—C6A | 50.1 (4) | C1B—P1—C1C—C2C | −54.4 (4) |
C1B—P1—C1A—C6A | −74.1 (4) | C1—P1—C1C—C6C | −2.9 (5) |
C1C—P1—C1A—C6A | 176.9 (4) | C1A—P1—C1C—C6C | −126.4 (4) |
C1—P1—C1A—C2A | −132.8 (4) | C1B—P1—C1C—C6C | 120.4 (4) |
C1B—P1—C1A—C2A | 103.1 (4) | C6C—C1C—C2C—C3C | 0.9 (8) |
C1C—P1—C1A—C2A | −5.9 (4) | P1—C1C—C2C—C3C | 175.6 (4) |
C6A—C1A—C2A—C3A | 0.3 (6) | C1C—C2C—C3C—C4C | −0.1 (8) |
P1—C1A—C2A—C3A | −176.9 (4) | C2C—C3C—C4C—C5C | −1.6 (9) |
C1A—C2A—C3A—C4A | −0.2 (7) | C3C—C4C—C5C—C6C | 2.3 (9) |
C2A—C3A—C4A—C5A | −0.9 (9) | C2C—C1C—C6C—C5C | −0.1 (8) |
C3A—C4A—C5A—C6A | 1.9 (10) | P1—C1C—C6C—C5C | −174.9 (4) |
C2A—C1A—C6A—C5A | 0.8 (8) | C4C—C5C—C6C—C1C | −1.5 (9) |
(V)
tert-Butyl 3-oxo-2-(triphenylphosphoranylidene)butyrate
top
Crystal data top
C26H27O3P | F(000) = 888 |
Mr = 418.45 | Dx = 1.241 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.668 (6) Å | Cell parameters from 25 reflections |
b = 13.975 (8) Å | θ = 7.5–12.5° |
c = 16.625 (11) Å | µ = 0.15 mm−1 |
β = 94.69 (5)° | T = 293 K |
V = 2239 (2) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.20 × 0.18 mm |
Data collection top
Siemens R3m diffractometer | Rint = 0.054 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.9° |
Graphite monochromator | h = −11→11 |
ω/2θ scans | k = 0→16 |
4193 measured reflections | l = 0→19 |
3945 independent reflections | 2 standard reflections every 98 reflections |
3025 reflections with I > 2σ(I) | intensity decay: <2% |
Refinement top
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-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 parameters | Δρmax = 0.18 e Å−3 |
27 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C26H27O3P | V = 2239 (2) Å3 |
Mr = 418.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.668 (6) Å | µ = 0.15 mm−1 |
b = 13.975 (8) Å | T = 293 K |
c = 16.625 (11) Å | 0.30 × 0.20 × 0.18 mm |
β = 94.69 (5)° | |
Data collection top
Siemens R3m diffractometer | Rint = 0.054 |
4193 measured reflections | 2 standard reflections every 98 reflections |
3945 independent reflections | intensity decay: <2% |
3025 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 27 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.18 e Å−3 |
3945 reflections | Δρmin = −0.21 e Å−3 |
276 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | −0.18890 (5) | −0.29959 (3) | −0.22089 (3) | 0.03110 (13) | |
C1 | −0.12454 (18) | −0.19803 (12) | −0.17013 (10) | 0.0345 (4) | |
C2 | 0.00061 (19) | −0.16606 (14) | −0.20169 (11) | 0.0400 (4) | |
C3 | 0.0759 (2) | −0.07768 (16) | −0.17056 (14) | 0.0618 (6) | |
H3A | 0.1738 | −0.0903 | −0.1641 | 0.093* | |
H3B | 0.0440 | −0.0601 | −0.1194 | 0.093* | |
H3C | 0.0581 | −0.0263 | −0.2083 | 0.093* | |
O4 | 0.04949 (14) | −0.21336 (10) | −0.25602 (8) | 0.0509 (4) | |
C5 | −0.1774 (2) | −0.15793 (13) | −0.09832 (11) | 0.0389 (4) | |
O6 | −0.24531 (13) | −0.22371 (8) | −0.05717 (7) | 0.0396 (3) | |
O7 | −0.1600 (2) | −0.07672 (10) | −0.07506 (10) | 0.0700 (5) | |
C8 | −0.3159 (2) | −0.19793 (16) | 0.01497 (11) | 0.0481 (5) | |
C9 | −0.4259 (3) | −0.1244 (2) | −0.00615 (17) | 0.0950 (10) | |
H9A | −0.4776 | −0.1421 | −0.0557 | 0.142* | |
H9B | −0.3832 | −0.0631 | −0.0126 | 0.142* | |
H9C | −0.4874 | −0.1208 | 0.0363 | 0.142* | |
C10 | −0.2093 (3) | −0.1672 (2) | 0.08248 (13) | 0.0746 (8) | |
H10A | −0.1712 | −0.1062 | 0.0694 | 0.112* | |
H10B | −0.1363 | −0.2138 | 0.0885 | 0.112* | |
H10C | −0.2532 | −0.1621 | 0.1320 | 0.112* | |
C11 | −0.3796 (3) | −0.29185 (19) | 0.03685 (13) | 0.0720 (8) | |
H11A | −0.4488 | −0.3103 | −0.0050 | 0.108* | |
H11B | −0.4218 | −0.2850 | 0.0868 | 0.108* | |
H11C | −0.3088 | −0.3401 | 0.0426 | 0.108* | |
C1A | −0.07392 (18) | −0.40116 (12) | −0.20733 (10) | 0.0354 (4) | |
C2A | −0.0222 (2) | −0.44906 (15) | −0.27118 (12) | 0.0488 (5) | |
H2A | −0.0460 | −0.4287 | −0.3238 | 0.059* | |
C3A | 0.0641 (2) | −0.52658 (15) | −0.25745 (14) | 0.0579 (6) | |
H3A1 | 0.0980 | −0.5584 | −0.3009 | 0.069* | |
C4A | 0.1008 (2) | −0.55750 (15) | −0.18025 (15) | 0.0567 (6) | |
H4A | 0.1587 | −0.6102 | −0.1714 | 0.068* | |
C5A | 0.0512 (2) | −0.50982 (15) | −0.11592 (14) | 0.0557 (6) | |
H5A | 0.0759 | −0.5303 | −0.0635 | 0.067* | |
C6A | −0.0352 (2) | −0.43152 (14) | −0.12929 (12) | 0.0470 (5) | |
H6A | −0.0676 | −0.3991 | −0.0857 | 0.056* | |
C1B | −0.35675 (18) | −0.33577 (13) | −0.19026 (10) | 0.0367 (4) | |
C2B | −0.3808 (2) | −0.42288 (14) | −0.15553 (13) | 0.0530 (6) | |
H2B | −0.3079 | −0.4653 | −0.1435 | 0.064* | |
C3B | −0.5149 (3) | −0.44709 (18) | −0.13853 (16) | 0.0732 (8) | |
H3B1 | −0.5317 | −0.5059 | −0.1151 | 0.088* | |
C4B | −0.6225 (3) | −0.3846 (2) | −0.15619 (16) | 0.0738 (8) | |
H4B | −0.7117 | −0.4012 | −0.1442 | 0.089* | |
C5B | −0.5997 (2) | −0.2981 (2) | −0.19135 (15) | 0.0684 (7) | |
H5B | −0.6732 | −0.2563 | −0.2037 | 0.082* | |
C6B | −0.4667 (2) | −0.27323 (17) | −0.20840 (13) | 0.0548 (6) | |
H6B | −0.4508 | −0.2144 | −0.2321 | 0.066* | |
C1C | −0.23235 (18) | −0.27963 (12) | −0.32746 (10) | 0.0343 (4) | |
C2C | −0.2898 (2) | −0.35439 (14) | −0.37385 (11) | 0.0447 (5) | |
H2C | −0.2989 | −0.4144 | −0.3507 | 0.054* | |
C3C | −0.3337 (2) | −0.34044 (16) | −0.45419 (12) | 0.0542 (5) | |
H3C1 | −0.3708 | −0.3912 | −0.4851 | 0.065* | |
C4C | −0.3223 (2) | −0.25140 (18) | −0.48849 (13) | 0.0586 (6) | |
H4C | −0.3518 | −0.2418 | −0.5425 | 0.070* | |
C5C | −0.2669 (2) | −0.17649 (16) | −0.44229 (13) | 0.0573 (6) | |
H5C | −0.2598 | −0.1163 | −0.4654 | 0.069* | |
C6C | −0.2219 (2) | −0.19025 (13) | −0.36192 (11) | 0.0442 (5) | |
H6C | −0.1847 | −0.1394 | −0.3312 | 0.053* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0352 (2) | 0.0294 (2) | 0.0298 (2) | −0.00098 (19) | 0.00963 (18) | 0.00049 (19) |
C1 | 0.0409 (10) | 0.0316 (9) | 0.0318 (9) | −0.0032 (8) | 0.0086 (7) | 0.0004 (7) |
C2 | 0.0409 (10) | 0.0458 (11) | 0.0334 (10) | −0.0055 (9) | 0.0036 (8) | 0.0077 (8) |
C3 | 0.0633 (14) | 0.0641 (15) | 0.0589 (14) | −0.0286 (12) | 0.0100 (11) | 0.0041 (12) |
O4 | 0.0472 (8) | 0.0645 (9) | 0.0438 (8) | −0.0032 (7) | 0.0195 (6) | 0.0010 (7) |
C5 | 0.0508 (11) | 0.0306 (10) | 0.0364 (10) | −0.0010 (8) | 0.0112 (8) | 0.0025 (8) |
O6 | 0.0515 (8) | 0.0371 (7) | 0.0326 (6) | −0.0052 (6) | 0.0181 (6) | −0.0040 (5) |
O7 | 0.1192 (14) | 0.0322 (8) | 0.0636 (10) | −0.0131 (8) | 0.0388 (10) | −0.0106 (7) |
C8 | 0.0527 (12) | 0.0647 (13) | 0.0292 (9) | −0.0022 (11) | 0.0174 (8) | −0.0092 (9) |
C9 | 0.089 (2) | 0.123 (3) | 0.0776 (19) | 0.0474 (19) | 0.0360 (16) | −0.0048 (18) |
C10 | 0.0835 (18) | 0.100 (2) | 0.0415 (13) | −0.0231 (16) | 0.0143 (12) | −0.0191 (13) |
C11 | 0.0781 (17) | 0.0963 (19) | 0.0456 (13) | −0.0302 (15) | 0.0297 (12) | −0.0018 (13) |
C1A | 0.0360 (10) | 0.0316 (9) | 0.0391 (10) | −0.0007 (8) | 0.0074 (8) | 0.0017 (8) |
C2A | 0.0512 (12) | 0.0561 (13) | 0.0404 (11) | 0.0137 (10) | 0.0109 (9) | −0.0007 (9) |
C3A | 0.0552 (13) | 0.0555 (14) | 0.0633 (14) | 0.0159 (11) | 0.0071 (11) | −0.0114 (11) |
C4A | 0.0491 (12) | 0.0398 (12) | 0.0802 (16) | 0.0079 (10) | −0.0001 (11) | 0.0010 (11) |
C5A | 0.0583 (14) | 0.0504 (13) | 0.0572 (13) | 0.0019 (11) | −0.0023 (11) | 0.0173 (10) |
C6A | 0.0537 (12) | 0.0464 (12) | 0.0417 (11) | 0.0036 (10) | 0.0085 (9) | 0.0038 (9) |
C1B | 0.0380 (10) | 0.0392 (10) | 0.0342 (9) | −0.0063 (8) | 0.0107 (8) | −0.0066 (8) |
C2B | 0.0582 (13) | 0.0379 (11) | 0.0659 (14) | −0.0130 (10) | 0.0229 (11) | −0.0053 (10) |
C3B | 0.0764 (17) | 0.0544 (14) | 0.0942 (19) | −0.0308 (14) | 0.0398 (15) | −0.0150 (13) |
C4B | 0.0511 (14) | 0.094 (2) | 0.0804 (18) | −0.0323 (15) | 0.0295 (13) | −0.0366 (16) |
C5B | 0.0393 (12) | 0.096 (2) | 0.0720 (16) | −0.0007 (13) | 0.0149 (11) | −0.0114 (15) |
C6B | 0.0428 (12) | 0.0632 (14) | 0.0599 (13) | 0.0048 (10) | 0.0134 (10) | 0.0077 (11) |
C1C | 0.0351 (9) | 0.0370 (10) | 0.0316 (9) | 0.0040 (8) | 0.0066 (7) | −0.0004 (7) |
C2C | 0.0519 (12) | 0.0441 (11) | 0.0381 (11) | −0.0037 (9) | 0.0046 (9) | −0.0016 (9) |
C3C | 0.0615 (14) | 0.0616 (14) | 0.0384 (11) | −0.0011 (11) | −0.0022 (10) | −0.0072 (10) |
C4C | 0.0666 (15) | 0.0726 (15) | 0.0357 (10) | 0.0089 (13) | −0.0013 (10) | 0.0008 (11) |
C5C | 0.0728 (15) | 0.0507 (13) | 0.0483 (13) | 0.0077 (11) | 0.0036 (11) | 0.0155 (10) |
C6C | 0.0558 (12) | 0.0377 (10) | 0.0386 (10) | 0.0011 (9) | 0.0017 (9) | 0.0025 (8) |
Geometric parameters (Å, º) top
P1—C1 | 1.7400 (19) | C2A—C3A | 1.375 (3) |
P1—C1A | 1.8058 (19) | C3A—C4A | 1.373 (3) |
P1—C1C | 1.809 (2) | C4A—C5A | 1.379 (3) |
P1—C1B | 1.812 (2) | C5A—C6A | 1.384 (3) |
C1—C2 | 1.429 (3) | C1B—C2B | 1.375 (3) |
C1—C5 | 1.449 (3) | C1B—C6B | 1.390 (3) |
C2—O4 | 1.243 (2) | C2B—C3B | 1.391 (3) |
C2—C3 | 1.504 (3) | C3B—C4B | 1.371 (4) |
C5—O7 | 1.206 (2) | C4B—C5B | 1.369 (3) |
C5—O6 | 1.348 (2) | C5B—C6B | 1.383 (3) |
O6—C8 | 1.472 (2) | C1C—C6C | 1.381 (2) |
C8—C9 | 1.500 (3) | C1C—C2C | 1.388 (3) |
C8—C11 | 1.507 (3) | C2C—C3C | 1.382 (3) |
C8—C10 | 1.522 (3) | C3C—C4C | 1.377 (3) |
C1A—C2A | 1.383 (3) | C4C—C5C | 1.380 (3) |
C1A—C6A | 1.387 (3) | C5C—C6C | 1.384 (3) |
| | | |
P1···O4 | 2.707 (2) | P1···O6 | 3.012 (2) |
| | | |
C1—P1—C1A | 112.87 (10) | C2A—C1A—P1 | 122.84 (15) |
C1—P1—C1C | 113.23 (9) | C6A—C1A—P1 | 118.25 (14) |
C1A—P1—C1C | 109.56 (8) | C3A—C2A—C1A | 120.4 (2) |
C1—P1—C1B | 112.60 (9) | C4A—C3A—C2A | 120.7 (2) |
C1A—P1—C1B | 107.57 (9) | C3A—C4A—C5A | 119.6 (2) |
C1C—P1—C1B | 100.18 (9) | C4A—C5A—C6A | 120.1 (2) |
C2—C1—C5 | 123.22 (16) | C5A—C6A—C1A | 120.34 (19) |
C2—C1—P1 | 110.90 (13) | C2B—C1B—C6B | 119.69 (19) |
C5—C1—P1 | 125.35 (13) | C2B—C1B—P1 | 123.42 (15) |
O4—C2—C1 | 118.95 (18) | C6B—C1B—P1 | 116.75 (15) |
O4—C2—C3 | 118.97 (17) | C1B—C2B—C3B | 119.5 (2) |
C1—C2—C3 | 122.07 (17) | C4B—C3B—C2B | 120.3 (2) |
O7—C5—O6 | 122.67 (17) | C5B—C4B—C3B | 120.5 (2) |
O7—C5—C1 | 125.34 (17) | C4B—C5B—C6B | 119.6 (2) |
O6—C5—C1 | 111.94 (15) | C5B—C6B—C1B | 120.3 (2) |
C5—O6—C8 | 121.60 (15) | C6C—C1C—C2C | 119.33 (17) |
O6—C8—C9 | 110.13 (17) | C6C—C1C—P1 | 121.78 (13) |
O6—C8—C11 | 102.09 (16) | C2C—C1C—P1 | 118.60 (14) |
C9—C8—C11 | 110.9 (2) | C3C—C2C—C1C | 120.55 (19) |
O6—C8—C10 | 109.79 (17) | C4C—C3C—C2C | 120.0 (2) |
C9—C8—C10 | 113.8 (2) | C3C—C4C—C5C | 119.69 (19) |
C11—C8—C10 | 109.47 (19) | C4C—C5C—C6C | 120.6 (2) |
C2A—C1A—C6A | 118.91 (18) | C1C—C6C—C5C | 119.86 (18) |
| | | |
C1A—P1—C1—C2 | 63.94 (15) | C2A—C1A—C6A—C5A | −1.4 (3) |
C1C—P1—C1—C2 | −61.26 (15) | P1—C1A—C6A—C5A | 179.13 (15) |
C1B—P1—C1—C2 | −174.03 (13) | C1—P1—C1B—C2B | −118.93 (17) |
C1A—P1—C1—C5 | −107.93 (17) | C1A—P1—C1B—C2B | 6.06 (19) |
C1C—P1—C1—C5 | 126.87 (16) | C1C—P1—C1B—C2B | 120.49 (17) |
C1B—P1—C1—C5 | 14.10 (19) | C1—P1—C1B—C6B | 65.36 (18) |
C5—C1—C2—O4 | 169.35 (17) | C1A—P1—C1B—C6B | −169.66 (15) |
P1—C1—C2—O4 | −2.7 (2) | C1C—P1—C1B—C6B | −55.23 (17) |
C5—C1—C2—C3 | −9.9 (3) | C6B—C1B—C2B—C3B | −0.4 (3) |
P1—C1—C2—C3 | 178.02 (15) | P1—C1B—C2B—C3B | −175.98 (17) |
C2—C1—C5—O7 | 29.6 (3) | C1B—C2B—C3B—C4B | 0.0 (3) |
P1—C1—C5—O7 | −159.49 (18) | C2B—C3B—C4B—C5B | 0.6 (4) |
C2—C1—C5—O6 | −147.80 (17) | C3B—C4B—C5B—C6B | −0.7 (4) |
P1—C1—C5—O6 | 23.1 (2) | C4B—C5B—C6B—C1B | 0.2 (4) |
O7—C5—O6—C8 | 6.6 (3) | C2B—C1B—C6B—C5B | 0.3 (3) |
C1—C5—O6—C8 | −175.92 (16) | P1—C1B—C6B—C5B | 176.17 (18) |
C5—O6—C8—C9 | 59.9 (3) | C1—P1—C1C—C6C | −3.62 (18) |
C5—O6—C8—C11 | 177.79 (18) | C1A—P1—C1C—C6C | −130.58 (16) |
C5—O6—C8—C10 | −66.2 (2) | C1B—P1—C1C—C6C | 116.51 (16) |
C1—P1—C1A—C2A | −122.77 (17) | C1—P1—C1C—C2C | −177.51 (14) |
C1C—P1—C1A—C2A | 4.40 (19) | C1A—P1—C1C—C2C | 55.52 (16) |
C1B—P1—C1A—C2A | 112.41 (17) | C1B—P1—C1C—C2C | −57.39 (15) |
C1—P1—C1A—C6A | 56.63 (17) | C6C—C1C—C2C—C3C | 1.4 (3) |
C1C—P1—C1A—C6A | −176.20 (14) | P1—C1C—C2C—C3C | 175.40 (16) |
C1B—P1—C1A—C6A | −68.19 (17) | C1C—C2C—C3C—C4C | −1.0 (3) |
C6A—C1A—C2A—C3A | 1.2 (3) | C2C—C3C—C4C—C5C | 0.1 (3) |
P1—C1A—C2A—C3A | −179.43 (16) | C3C—C4C—C5C—C6C | 0.4 (3) |
C1A—C2A—C3A—C4A | −0.2 (3) | C2C—C1C—C6C—C5C | −0.9 (3) |
C2A—C3A—C4A—C5A | −0.4 (3) | P1—C1C—C6C—C5C | −174.71 (16) |
C3A—C4A—C5A—C6A | 0.2 (3) | C4C—C5C—C6C—C1C | 0.0 (3) |
C4A—C5A—C6A—C1A | 0.8 (3) | | |
Experimental details
| (II) | (III) | (IV) | (V) |
Crystal data |
Chemical formula | C23H21O3P·0.5C6H6 | C24H23O3P | C25H25O3P | C26H27O3P |
Mr | 415.42 | 390.39 | 404.42 | 418.45 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca | Orthorhombic, Pbca | Monoclinic, P21/n |
Temperature (K) | 293 | 293 | 293 | 293 |
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), 90 | 90, 90, 90 | 90, 90, 90 | 90, 94.69 (5), 90 |
V (Å3) | 2200.9 (17) | 4248 (2) | 4339 (3) | 2239 (2) |
Z | 4 | 8 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.15 | 0.15 | 0.15 | 0.15 |
Crystal size (mm) | 0.24 × 0.18 × 0.15 | 0.27 × 0.20 × 0.16 | 0.22 × 0.19 × 0.16 | 0.30 × 0.20 × 0.18 |
|
Data collection |
Diffractometer | Siemens 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 |
Rint | 0.055 | 0.058 | 0.096 | 0.054 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.594 | 0.595 |
|
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 reflections | 3892 | 3737 | 3824 | 3945 |
No. of parameters | 274 | 284 | 266 | 276 |
No. of restraints | 33 | 33 | 27 | 27 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.19 | 0.22, −0.18 | 0.20, −0.21 | 0.18, −0.21 |
Selected geometric parameters (Å, º) for (II) topP1—C1 | 1.747 (2) | C2—O4 | 1.243 (2) |
P1—C1C | 1.802 (2) | C2—C3 | 1.510 (3) |
P1—C1A | 1.815 (2) | C5—O7 | 1.212 (2) |
P1—C1B | 1.819 (2) | C5—O6 | 1.349 (3) |
C1—C2 | 1.428 (3) | O6—C8 | 1.435 (3) |
C1—C5 | 1.441 (3) | | |
| | | |
P1···O4 | 2.806 (2) | P1···O6 | 2.971 (2) |
| | | |
C1—P1—C1C | 115.61 (10) | C1A—P1—C1B | 108.24 (9) |
C1—P1—C1A | 108.97 (10) | C2—C1—C5 | 123.05 (19) |
C1C—P1—C1A | 106.92 (9) | C2—C1—P1 | 113.18 (15) |
C1—P1—C1B | 111.13 (10) | C5—C1—P1 | 123.63 (16) |
C1C—P1—C1B | 105.66 (10) | | |
| | | |
P1—C1—C2—O4 | 12.0 (3) | P1—C1—C5—O7 | 162.47 (19) |
Selected geometric parameters (Å, º) for (III) topP1—C1 | 1.757 (3) | C5—O7 | 1.197 (4) |
P1—C1A | 1.804 (3) | C5—O6'' | 1.352 (7) |
P1—C1B | 1.817 (3) | C5—O6' | 1.360 (8) |
P1—C1C | 1.821 (3) | O6'—C8' | 1.457 (9) |
C1—C2 | 1.434 (4) | C8'—C9' | 1.494 (10) |
C1—C5 | 1.444 (4) | O6''—C8'' | 1.466 (8) |
C2—O4 | 1.248 (4) | C8''—C9'' | 1.497 (10) |
C2—C3 | 1.507 (4) | | |
| | | |
P1···O4 | 2.699 (4) | P1···O6'' | 3.026 (7) |
P1···O6' | 3.014 (8) | | |
| | | |
C1—P1—C1A | 109.67 (14) | C1B—P1—C1C | 101.19 (14) |
C1—P1—C1B | 113.78 (14) | C2—C1—C5 | 123.5 (3) |
C1A—P1—C1B | 107.20 (15) | C2—C1—P1 | 109.9 (2) |
C1—P1—C1C | 114.37 (15) | C5—C1—P1 | 126.4 (3) |
C1A—P1—C1C | 110.18 (15) | | |
| | | |
P1—C1—C2—O4 | 1.7 (4) | P1—C1—C5—O7 | 170.7 (3) |
Selected geometric parameters (Å, º) for (IV) topP1—C1 | 1.753 (5) | C2—C3 | 1.483 (7) |
P1—C1A | 1.795 (4) | C5—O7 | 1.221 (6) |
P1—C1B | 1.796 (5) | C5—O6 | 1.341 (6) |
P1—C1C | 1.818 (5) | O6—C8 | 1.436 (8) |
C1—C5 | 1.429 (7) | C8—C10 | 1.469 (11) |
C1—C2 | 1.443 (6) | C8—C9 | 1.486 (11) |
C2—O4 | 1.244 (6) | | |
| | | |
P1···O4 | 2.703 (16) | P1···O6 | 3.023 (16) |
| | | |
C1—P1—C1A | 109.1 (2) | C1B—P1—C1C | 101.0 (2) |
C1—P1—C1B | 114.0 (2) | C5—C1—C2 | 122.5 (5) |
C1A—P1—C1B | 107.5 (2) | C5—C1—P1 | 124.8 (4) |
C1—P1—C1C | 115.1 (2) | C2—C1—P1 | 112.2 (4) |
C1A—P1—C1C | 109.7 (2) | | |
| | | |
P1—C1—C2—O4 | 0.9 (6) | P1—C1—C5—O7 | 174.7 (5) |
Selected geometric parameters (Å, º) for (V) topP1—C1 | 1.7400 (19) | C2—C3 | 1.504 (3) |
P1—C1A | 1.8058 (19) | C5—O7 | 1.206 (2) |
P1—C1C | 1.809 (2) | C5—O6 | 1.348 (2) |
P1—C1B | 1.812 (2) | O6—C8 | 1.472 (2) |
C1—C2 | 1.429 (3) | C8—C9 | 1.500 (3) |
C1—C5 | 1.449 (3) | C8—C11 | 1.507 (3) |
C2—O4 | 1.243 (2) | C8—C10 | 1.522 (3) |
| | | |
P1···O4 | 2.707 (2) | P1···O6 | 3.012 (2) |
| | | |
C1—P1—C1A | 112.87 (10) | C1C—P1—C1B | 100.18 (9) |
C1—P1—C1C | 113.23 (9) | C2—C1—C5 | 123.22 (16) |
C1A—P1—C1C | 109.56 (8) | C2—C1—P1 | 110.90 (13) |
C1—P1—C1B | 112.60 (9) | C5—C1—P1 | 125.35 (13) |
C1A—P1—C1B | 107.57 (9) | | |
| | | |
P1—C1—C2—O4 | −2.7 (2) | P1—C1—C5—O7 | −159.49 (18) |
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.