The isopropyl and tert-butyl diesters of triphenylphosphonium ylides,
(Ia), (Ib), (IIa) and (IIb), were synthesized by transylidation (Cristau &
Plénat, 1994). The general procedure was as follows. A solution of
methyl or
ethyl chloroformate (20 mmol) in dry benzene (8 ml) was added slowly to
isopropyl or tert-butyl 2-triphenylphosphoranylidene acetate
(Ph3P═CH—CO2R, R = iPr or tBu; 40 mmol) in dry
benzene (100 ml) under a dry atmosphere. The resulting solution was stirred
for 4 h at room temperature and a white solid separated. The carboalkoxy
methyltriphenylphosphonium chloride (Ph3P+—CH2—CO2R Cl-;
R = iPr or tBu) was removed by filtration and the solvent was
evaporated, giving a solid or an oil. Recrystallization from ethyl acetate
gave the title novel diester ylides, (Ia), (Ib), (IIa) or (IIb) (yields
65–80%).
For methyl isopropyl 2-triphenylphosphoranylidene malonate, (Ia): yield 82%;
m.p. 393 K; analysis calculated for C25H25O4P: C 71.42, H 5.99%; found:
C 71.70, H 6.22%.
For ethyl isopropyl 2-triphenylphosphoranylidene malonate, (Ib): yield 78%;
m.p. 397 K; analysis calculated for C26H27O4P: C 71.88, H 6.26%; found:
C 72.15, H 6.35%.
For methyl tert-butyl 2-triphenylphosphoranylidene malonate, (IIa):
yield 70%; m.p. 460 K; analysis calculated for C26H27O4P: C 71.88, H
6.26%; found: C 72.12, H 6.30%.
For ethyl tert-butyl 2-triphenylphosphoranylidene malonate, (IIb): yield
65%; m.p. 412 K; analysis calculated for C27H29O4P: C 72.31, H 6.52%;
found: C 72.45, H 6.80%.
1H NMR spectra in solution were monitored on a Bruker DRX 300 spectrometer
referenced to trimethyl siloxane. IR spectra were obtained with a KBr
disk on a Bruker IFS 56 FT spectrometer. Elemental analyses were carried out
with a Fison EA 1108 analyser. Spectroscopic data are available in the
archived CIF.
H atoms were placed in idealized positions and allowed to ride on their parent
atoms, with C—H = 0.93 (aromatic), 0.97 (CH2) or 0.96 Å (CH3), and
with Uiso(H) = 1.2Ueq(C) for aromatic H and CH2, or
1.5Ueq(C) for CH3.
Some terminal groups were disordered over two different orientations and
accordingly were refined with a metrically restrained split model; these were
the OMe group in (Ia) and the OEt groups in (Ib and IIb). The refinements
converged to final occupancies of 0.66/0.34 (2), 0.616/384 (4) and
0.747 (4)/0.253 (4), using two, seven and three restraints, respectively.
For all compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2001); data reduction: SAINT-NT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008) and PLATON (Spek, 2003).
(Ia) methyl isopropyl 2-(triphenylphosphoranyliden)malonate
top
Crystal data top
C25H25O4P | Z = 2 |
Mr = 420.42 | F(000) = 444 |
Triclinic, P1 | Dx = 1.277 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8033 (6) Å | Cell parameters from 1718 reflections |
b = 10.4492 (7) Å | θ = 2.5–21.9° |
c = 11.2169 (7) Å | µ = 0.15 mm−1 |
α = 100.573 (2)° | T = 273 K |
β = 94.878 (2)° | Block, colourless |
γ = 102.446 (3)° | 0.20 × 0.17 × 0.14 mm |
V = 1093.64 (12) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3133 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 27.8°, θmin = 1.9° |
ϕ and ω scans | h = −12→12 |
9176 measured reflections | k = −13→13 |
4675 independent reflections | l = −14→14 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0646P)2] where P = (Fo2 + 2Fc2)/3 |
4675 reflections | (Δ/σ)max < 0.001 |
282 parameters | Δρmax = 0.27 e Å−3 |
2 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C25H25O4P | γ = 102.446 (3)° |
Mr = 420.42 | V = 1093.64 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.8033 (6) Å | Mo Kα radiation |
b = 10.4492 (7) Å | µ = 0.15 mm−1 |
c = 11.2169 (7) Å | T = 273 K |
α = 100.573 (2)° | 0.20 × 0.17 × 0.14 mm |
β = 94.878 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3133 reflections with I > 2σ(I) |
9176 measured reflections | Rint = 0.025 |
4675 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 2 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.27 e Å−3 |
4675 reflections | Δρmin = −0.17 e Å−3 |
282 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 | Occ. (<1) |
P1 | 0.15100 (5) | 0.32873 (5) | 0.22639 (5) | 0.04233 (17) | |
O1 | 0.37276 (15) | 0.23368 (13) | 0.12939 (14) | 0.0538 (4) | |
O2 | 0.36216 (19) | 0.04992 (16) | 0.20754 (18) | 0.0788 (6) | |
O3 | 0.2072 (16) | 0.0425 (8) | 0.3867 (10) | 0.0620 (16) | 0.66 (2) |
C7 | 0.1996 (15) | 0.0002 (13) | 0.5010 (12) | 0.067 (2) | 0.66 (2) |
H7A | 0.2688 | −0.0506 | 0.5119 | 0.101* | 0.66 (2) |
H7B | 0.1074 | −0.0545 | 0.5011 | 0.101* | 0.66 (2) |
H7C | 0.2175 | 0.0774 | 0.5666 | 0.101* | 0.66 (2) |
O3' | 0.221 (3) | 0.0571 (15) | 0.4171 (15) | 0.0620 (16) | 0.34 (2) |
C7' | 0.189 (3) | 0.022 (3) | 0.5312 (17) | 0.067 (2) | 0.34 (2) |
H7'A | 0.1025 | 0.0448 | 0.5505 | 0.101* | 0.34 (2) |
H7'B | 0.2640 | 0.0703 | 0.5947 | 0.101* | 0.34 (2) |
H7'C | 0.1793 | −0.0725 | 0.5246 | 0.101* | 0.34 (2) |
O4 | 0.14402 (17) | 0.23495 (16) | 0.46638 (14) | 0.0638 (4) | |
C1 | 0.2189 (2) | 0.20166 (19) | 0.27093 (19) | 0.0444 (5) | |
C2 | 0.3203 (2) | 0.1497 (2) | 0.2025 (2) | 0.0510 (5) | |
C3 | 0.1872 (2) | 0.1672 (2) | 0.3853 (2) | 0.0490 (5) | |
C4 | 0.4666 (2) | 0.1924 (2) | 0.0455 (2) | 0.0575 (6) | |
H4 | 0.5222 | 0.1391 | 0.0827 | 0.069* | |
C5 | 0.3833 (3) | 0.1088 (3) | −0.0698 (3) | 0.0808 (8) | |
H5A | 0.3202 | 0.0327 | −0.0520 | 0.121* | |
H5B | 0.4458 | 0.0787 | −0.1241 | 0.121* | |
H5C | 0.3299 | 0.1608 | −0.1078 | 0.121* | |
C6 | 0.5634 (3) | 0.3176 (3) | 0.0289 (3) | 0.0889 (9) | |
H6A | 0.5101 | 0.3695 | −0.0096 | 0.133* | |
H6B | 0.6325 | 0.2948 | −0.0216 | 0.133* | |
H6C | 0.6098 | 0.3691 | 0.1073 | 0.133* | |
C11 | 0.2649 (2) | 0.49492 (19) | 0.27479 (18) | 0.0438 (5) | |
C12 | 0.3953 (2) | 0.5102 (2) | 0.3400 (2) | 0.0540 (6) | |
H12 | 0.4224 | 0.4358 | 0.3598 | 0.065* | |
C13 | 0.4854 (3) | 0.6352 (3) | 0.3759 (2) | 0.0692 (7) | |
H13 | 0.5739 | 0.6448 | 0.4184 | 0.083* | |
C14 | 0.4447 (3) | 0.7456 (2) | 0.3490 (3) | 0.0728 (7) | |
H14 | 0.5053 | 0.8299 | 0.3745 | 0.087* | |
C15 | 0.3155 (3) | 0.7322 (2) | 0.2850 (2) | 0.0666 (7) | |
H15 | 0.2883 | 0.8074 | 0.2677 | 0.080* | |
C16 | 0.2259 (2) | 0.6077 (2) | 0.2464 (2) | 0.0534 (6) | |
H16 | 0.1391 | 0.5985 | 0.2012 | 0.064* | |
C21 | −0.0163 (2) | 0.3286 (2) | 0.28335 (18) | 0.0449 (5) | |
C22 | −0.0486 (2) | 0.4440 (2) | 0.3444 (2) | 0.0534 (6) | |
H22 | 0.0186 | 0.5248 | 0.3597 | 0.064* | |
C23 | −0.1797 (3) | 0.4405 (3) | 0.3830 (2) | 0.0640 (7) | |
H23 | −0.1998 | 0.5183 | 0.4247 | 0.077* | |
C24 | −0.2795 (3) | 0.3221 (3) | 0.3595 (2) | 0.0654 (7) | |
H24 | −0.3682 | 0.3202 | 0.3837 | 0.079* | |
C25 | −0.2496 (2) | 0.2072 (3) | 0.3011 (2) | 0.0623 (6) | |
H25 | −0.3178 | 0.1271 | 0.2862 | 0.075* | |
C26 | −0.1183 (2) | 0.2088 (2) | 0.2637 (2) | 0.0552 (6) | |
H26 | −0.0983 | 0.1295 | 0.2252 | 0.066* | |
C31 | 0.1138 (2) | 0.29891 (19) | 0.06101 (18) | 0.0436 (5) | |
C32 | 0.0160 (2) | 0.1853 (2) | −0.0032 (2) | 0.0598 (6) | |
H32 | −0.0332 | 0.1261 | 0.0395 | 0.072* | |
C33 | −0.0098 (3) | 0.1588 (3) | −0.1287 (2) | 0.0678 (7) | |
H33 | −0.0768 | 0.0827 | −0.1698 | 0.081* | |
C34 | 0.0622 (3) | 0.2432 (3) | −0.1932 (2) | 0.0646 (7) | |
H34 | 0.0456 | 0.2244 | −0.2782 | 0.078* | |
C35 | 0.1591 (3) | 0.3557 (2) | −0.1321 (2) | 0.0668 (7) | |
H35 | 0.2080 | 0.4140 | −0.1757 | 0.080* | |
C36 | 0.1851 (2) | 0.3833 (2) | −0.0061 (2) | 0.0574 (6) | |
H36 | 0.2517 | 0.4601 | 0.0342 | 0.069* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0441 (3) | 0.0381 (3) | 0.0480 (3) | 0.0128 (2) | 0.0062 (2) | 0.0135 (2) |
O1 | 0.0579 (9) | 0.0459 (8) | 0.0698 (10) | 0.0214 (7) | 0.0239 (8) | 0.0250 (7) |
O2 | 0.0845 (12) | 0.0628 (11) | 0.1221 (16) | 0.0449 (10) | 0.0522 (11) | 0.0531 (10) |
O3 | 0.104 (3) | 0.0550 (18) | 0.039 (4) | 0.032 (2) | 0.013 (4) | 0.023 (2) |
C7 | 0.093 (3) | 0.076 (5) | 0.050 (5) | 0.034 (2) | 0.023 (3) | 0.033 (4) |
O3' | 0.104 (3) | 0.0550 (18) | 0.039 (4) | 0.032 (2) | 0.013 (4) | 0.023 (2) |
C7' | 0.093 (3) | 0.076 (5) | 0.050 (5) | 0.034 (2) | 0.023 (3) | 0.033 (4) |
O4 | 0.0813 (12) | 0.0655 (10) | 0.0530 (10) | 0.0303 (9) | 0.0134 (9) | 0.0160 (8) |
C1 | 0.0481 (12) | 0.0404 (11) | 0.0501 (12) | 0.0149 (9) | 0.0078 (10) | 0.0166 (9) |
C2 | 0.0488 (13) | 0.0414 (12) | 0.0683 (15) | 0.0123 (10) | 0.0114 (11) | 0.0221 (11) |
C3 | 0.0470 (12) | 0.0441 (12) | 0.0568 (14) | 0.0109 (10) | 0.0004 (11) | 0.0153 (11) |
C4 | 0.0513 (13) | 0.0590 (14) | 0.0721 (16) | 0.0213 (11) | 0.0205 (12) | 0.0232 (12) |
C5 | 0.0772 (19) | 0.0745 (18) | 0.090 (2) | 0.0271 (15) | 0.0163 (16) | 0.0020 (15) |
C6 | 0.086 (2) | 0.0833 (19) | 0.097 (2) | 0.0016 (16) | 0.0353 (17) | 0.0286 (16) |
C11 | 0.0461 (12) | 0.0401 (11) | 0.0463 (12) | 0.0105 (9) | 0.0065 (9) | 0.0110 (9) |
C12 | 0.0523 (14) | 0.0525 (13) | 0.0574 (14) | 0.0134 (11) | 0.0049 (11) | 0.0118 (11) |
C13 | 0.0506 (14) | 0.0719 (17) | 0.0754 (18) | 0.0023 (13) | −0.0004 (12) | 0.0092 (14) |
C14 | 0.0714 (18) | 0.0505 (15) | 0.0839 (19) | −0.0067 (13) | 0.0086 (15) | 0.0072 (13) |
C15 | 0.0790 (18) | 0.0455 (14) | 0.0791 (18) | 0.0142 (13) | 0.0183 (15) | 0.0190 (12) |
C16 | 0.0564 (13) | 0.0433 (12) | 0.0636 (15) | 0.0148 (10) | 0.0083 (11) | 0.0154 (10) |
C21 | 0.0460 (12) | 0.0499 (12) | 0.0441 (12) | 0.0179 (10) | 0.0052 (9) | 0.0160 (9) |
C22 | 0.0606 (14) | 0.0533 (13) | 0.0520 (13) | 0.0210 (11) | 0.0102 (11) | 0.0153 (10) |
C23 | 0.0693 (17) | 0.0766 (18) | 0.0588 (15) | 0.0367 (14) | 0.0185 (13) | 0.0187 (13) |
C24 | 0.0543 (15) | 0.095 (2) | 0.0581 (15) | 0.0318 (15) | 0.0145 (12) | 0.0247 (14) |
C25 | 0.0503 (14) | 0.0775 (17) | 0.0588 (15) | 0.0070 (12) | 0.0074 (11) | 0.0225 (13) |
C26 | 0.0522 (13) | 0.0576 (14) | 0.0563 (14) | 0.0128 (11) | 0.0103 (11) | 0.0120 (11) |
C31 | 0.0460 (12) | 0.0405 (11) | 0.0478 (12) | 0.0155 (9) | 0.0044 (9) | 0.0121 (9) |
C32 | 0.0647 (15) | 0.0536 (14) | 0.0567 (15) | 0.0040 (12) | 0.0069 (12) | 0.0126 (11) |
C33 | 0.0681 (16) | 0.0639 (16) | 0.0602 (16) | 0.0062 (13) | −0.0029 (13) | 0.0008 (13) |
C34 | 0.0762 (17) | 0.0722 (17) | 0.0501 (14) | 0.0322 (14) | −0.0015 (13) | 0.0114 (13) |
C35 | 0.0835 (18) | 0.0638 (16) | 0.0570 (15) | 0.0135 (14) | 0.0086 (13) | 0.0268 (13) |
C36 | 0.0656 (15) | 0.0509 (13) | 0.0546 (14) | 0.0081 (11) | 0.0023 (11) | 0.0171 (11) |
Geometric parameters (Å, º) top
P1—C1 | 1.7388 (19) | C12—C13 | 1.377 (3) |
P1—C11 | 1.809 (2) | C12—H12 | 0.9300 |
P1—C21 | 1.810 (2) | C13—C14 | 1.374 (3) |
P1—C31 | 1.815 (2) | C13—H13 | 0.9300 |
O1—C2 | 1.360 (2) | C14—C15 | 1.368 (4) |
O1—C4 | 1.445 (3) | C14—H14 | 0.9300 |
O2—C2 | 1.208 (2) | C15—C16 | 1.374 (3) |
O3—C3 | 1.362 (4) | C15—H15 | 0.9300 |
O3—C7 | 1.434 (5) | C16—H16 | 0.9300 |
C7—H7A | 0.9600 | C21—C22 | 1.386 (3) |
C7—H7B | 0.9600 | C21—C26 | 1.392 (3) |
C7—H7C | 0.9600 | C22—C23 | 1.385 (3) |
O3'—C3 | 1.361 (7) | C22—H22 | 0.9300 |
O3'—C7' | 1.435 (8) | C23—C24 | 1.368 (3) |
C7'—H7'A | 0.9600 | C23—H23 | 0.9300 |
C7'—H7'B | 0.9600 | C24—C25 | 1.361 (3) |
C7'—H7'C | 0.9600 | C24—H24 | 0.9300 |
O4—C3 | 1.211 (2) | C25—C26 | 1.385 (3) |
C1—C3 | 1.436 (3) | C25—H25 | 0.9300 |
C1—C2 | 1.443 (3) | C26—H26 | 0.9300 |
C4—C5 | 1.483 (3) | C31—C36 | 1.378 (3) |
C4—C6 | 1.494 (3) | C31—C32 | 1.388 (3) |
C4—H4 | 0.9800 | C32—C33 | 1.374 (3) |
C5—H5A | 0.9600 | C32—H32 | 0.9300 |
C5—H5B | 0.9600 | C33—C34 | 1.361 (3) |
C5—H5C | 0.9600 | C33—H33 | 0.9300 |
C6—H6A | 0.9600 | C34—C35 | 1.366 (3) |
C6—H6B | 0.9600 | C34—H34 | 0.9300 |
C6—H6C | 0.9600 | C35—C36 | 1.379 (3) |
C11—C12 | 1.380 (3) | C35—H35 | 0.9300 |
C11—C16 | 1.395 (3) | C36—H36 | 0.9300 |
| | | |
C1—P1—C11 | 114.92 (9) | C11—C12—H12 | 119.9 |
C1—P1—C21 | 109.49 (9) | C14—C13—C12 | 120.1 (2) |
C11—P1—C21 | 108.93 (9) | C14—C13—H13 | 120.0 |
C1—P1—C31 | 110.74 (9) | C12—C13—H13 | 120.0 |
C11—P1—C31 | 106.43 (9) | C15—C14—C13 | 120.4 (2) |
C21—P1—C31 | 105.91 (9) | C15—C14—H14 | 119.8 |
C2—O1—C4 | 118.34 (16) | C13—C14—H14 | 119.8 |
C3—O3—C7 | 116.3 (7) | C14—C15—C16 | 120.0 (2) |
C3—O3'—C7' | 120.6 (18) | C14—C15—H15 | 120.0 |
O3'—C7'—H7'A | 109.5 | C16—C15—H15 | 120.0 |
O3'—C7'—H7'B | 109.5 | C15—C16—C11 | 120.2 (2) |
H7'A—C7'—H7'B | 109.5 | C15—C16—H16 | 119.9 |
O3'—C7'—H7'C | 109.5 | C11—C16—H16 | 119.9 |
H7'A—C7'—H7'C | 109.5 | C22—C21—C26 | 118.1 (2) |
H7'B—C7'—H7'C | 109.5 | C22—C21—P1 | 122.64 (17) |
C3—C1—C2 | 122.36 (18) | C26—C21—P1 | 119.22 (16) |
C3—C1—P1 | 117.71 (15) | C23—C22—C21 | 120.9 (2) |
C2—C1—P1 | 119.26 (15) | C23—C22—H22 | 119.5 |
O2—C2—O1 | 121.2 (2) | C21—C22—H22 | 119.5 |
O2—C2—C1 | 128.4 (2) | C24—C23—C22 | 119.8 (2) |
O1—C2—C1 | 110.30 (17) | C24—C23—H23 | 120.1 |
O4—C3—O3' | 113.3 (8) | C22—C23—H23 | 120.1 |
O4—C3—O3 | 124.7 (5) | C25—C24—C23 | 120.4 (2) |
O4—C3—C1 | 126.00 (19) | C25—C24—H24 | 119.8 |
O3'—C3—C1 | 120.3 (9) | C23—C24—H24 | 119.8 |
O3—C3—C1 | 109.2 (5) | C24—C25—C26 | 120.5 (2) |
O1—C4—C5 | 109.69 (18) | C24—C25—H25 | 119.8 |
O1—C4—C6 | 106.54 (19) | C26—C25—H25 | 119.8 |
C5—C4—C6 | 113.9 (2) | C25—C26—C21 | 120.3 (2) |
O1—C4—H4 | 108.9 | C25—C26—H26 | 119.9 |
C5—C4—H4 | 108.9 | C21—C26—H26 | 119.9 |
C6—C4—H4 | 108.9 | C36—C31—C32 | 117.4 (2) |
C4—C5—H5A | 109.5 | C36—C31—P1 | 122.03 (16) |
C4—C5—H5B | 109.5 | C32—C31—P1 | 120.52 (16) |
H5A—C5—H5B | 109.5 | C33—C32—C31 | 121.3 (2) |
C4—C5—H5C | 109.5 | C33—C32—H32 | 119.4 |
H5A—C5—H5C | 109.5 | C31—C32—H32 | 119.4 |
H5B—C5—H5C | 109.5 | C34—C33—C32 | 120.4 (2) |
C4—C6—H6A | 109.5 | C34—C33—H33 | 119.8 |
C4—C6—H6B | 109.5 | C32—C33—H33 | 119.8 |
H6A—C6—H6B | 109.5 | C33—C34—C35 | 119.4 (2) |
C4—C6—H6C | 109.5 | C33—C34—H34 | 120.3 |
H6A—C6—H6C | 109.5 | C35—C34—H34 | 120.3 |
H6B—C6—H6C | 109.5 | C34—C35—C36 | 120.5 (2) |
C12—C11—C16 | 119.1 (2) | C34—C35—H35 | 119.7 |
C12—C11—P1 | 118.92 (16) | C36—C35—H35 | 119.7 |
C16—C11—P1 | 121.99 (16) | C31—C36—C35 | 121.0 (2) |
C13—C12—C11 | 120.2 (2) | C31—C36—H36 | 119.5 |
C13—C12—H12 | 119.9 | C35—C36—H36 | 119.5 |
| | | |
C11—P1—C1—C3 | 91.24 (18) | C11—C12—C13—C14 | 1.3 (4) |
C21—P1—C1—C3 | −31.72 (19) | C12—C13—C14—C15 | −0.9 (4) |
C31—P1—C1—C3 | −148.13 (16) | C13—C14—C15—C16 | −0.5 (4) |
C11—P1—C1—C2 | −79.61 (19) | C14—C15—C16—C11 | 1.6 (4) |
C21—P1—C1—C2 | 157.44 (16) | C12—C11—C16—C15 | −1.2 (3) |
C31—P1—C1—C2 | 41.02 (19) | P1—C11—C16—C15 | 179.91 (17) |
C4—O1—C2—O2 | 8.0 (3) | C1—P1—C21—C22 | 131.52 (18) |
C4—O1—C2—C1 | −174.49 (17) | C11—P1—C21—C22 | 5.1 (2) |
C3—C1—C2—O2 | 22.0 (4) | C31—P1—C21—C22 | −109.04 (18) |
P1—C1—C2—O2 | −167.6 (2) | C1—P1—C21—C26 | −49.68 (19) |
C3—C1—C2—O1 | −155.35 (19) | C11—P1—C21—C26 | −176.12 (16) |
P1—C1—C2—O1 | 15.0 (2) | C31—P1—C21—C26 | 69.76 (18) |
C7'—O3'—C3—O4 | 7 (3) | C26—C21—C22—C23 | −1.0 (3) |
C7'—O3'—C3—O3 | −136 (10) | P1—C21—C22—C23 | 177.79 (16) |
C7'—O3'—C3—C1 | −180 (2) | C21—C22—C23—C24 | −0.7 (3) |
C7—O3—C3—O4 | −11.2 (16) | C22—C23—C24—C25 | 1.6 (4) |
C7—O3—C3—O3' | 30 (7) | C23—C24—C25—C26 | −0.6 (4) |
C7—O3—C3—C1 | 171.4 (10) | C24—C25—C26—C21 | −1.2 (3) |
C2—C1—C3—O4 | 153.5 (2) | C22—C21—C26—C25 | 2.0 (3) |
P1—C1—C3—O4 | −17.0 (3) | P1—C21—C26—C25 | −176.85 (16) |
C2—C1—C3—O3' | −18.5 (15) | C1—P1—C31—C36 | −115.23 (18) |
P1—C1—C3—O3' | 171.0 (15) | C11—P1—C31—C36 | 10.3 (2) |
C2—C1—C3—O3 | −29.1 (8) | C21—P1—C31—C36 | 126.16 (18) |
P1—C1—C3—O3 | 160.3 (7) | C1—P1—C31—C32 | 61.69 (19) |
C2—O1—C4—C5 | 85.8 (2) | C11—P1—C31—C32 | −172.75 (17) |
C2—O1—C4—C6 | −150.5 (2) | C21—P1—C31—C32 | −56.92 (19) |
C1—P1—C11—C12 | 1.1 (2) | C36—C31—C32—C33 | −0.6 (3) |
C21—P1—C11—C12 | 124.33 (17) | P1—C31—C32—C33 | −177.64 (18) |
C31—P1—C11—C12 | −121.88 (17) | C31—C32—C33—C34 | 0.9 (4) |
C1—P1—C11—C16 | 179.97 (17) | C32—C33—C34—C35 | −0.9 (4) |
C21—P1—C11—C16 | −56.78 (19) | C33—C34—C35—C36 | 0.6 (4) |
C31—P1—C11—C16 | 57.00 (19) | C32—C31—C36—C35 | 0.3 (3) |
C16—C11—C12—C13 | −0.2 (3) | P1—C31—C36—C35 | 177.29 (17) |
P1—C11—C12—C13 | 178.70 (17) | C34—C35—C36—C31 | −0.3 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | | | 2.799 (2) | |
P1···O4 | | | 3.030 (2) | |
C5—H5C···Cg3 | 0.96 | 2.89 | 3.657 (3) | 138 |
C23—H23···O4i | 0.93 | 2.56 | 3.430 (3) | 156 |
Symmetry code: (i) −x, −y+1, −z+1. |
(Ib) ethyl isopropyl 2-(triphenylphosphoranyliden)malonate
top
Crystal data top
C26H27O4P | F(000) = 920 |
Mr = 434.45 | Dx = 1.245 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1773 reflections |
a = 12.5175 (16) Å | θ = 2.4–18.8° |
b = 9.1555 (12) Å | µ = 0.15 mm−1 |
c = 20.351 (3) Å | T = 140 K |
β = 96.342 (2)° | Block, colourless |
V = 2318.0 (5) Å3 | 0.18 × 0.16 × 0.16 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2713 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 28.1°, θmin = 2.0° |
ϕ and ω scans | h = −16→16 |
19001 measured reflections | k = −12→11 |
5252 independent reflections | l = −26→26 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0649P)2] where P = (Fo2 + 2Fc2)/3 |
5252 reflections | (Δ/σ)max < 0.001 |
300 parameters | Δρmax = 0.33 e Å−3 |
7 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C26H27O4P | V = 2318.0 (5) Å3 |
Mr = 434.45 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.5175 (16) Å | µ = 0.15 mm−1 |
b = 9.1555 (12) Å | T = 140 K |
c = 20.351 (3) Å | 0.18 × 0.16 × 0.16 mm |
β = 96.342 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2713 reflections with I > 2σ(I) |
19001 measured reflections | Rint = 0.053 |
5252 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 7 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 0.86 | Δρmax = 0.33 e Å−3 |
5252 reflections | Δρmin = −0.27 e Å−3 |
300 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 | Occ. (<1) |
P1 | 0.73850 (5) | 0.02844 (7) | 0.17875 (3) | 0.0439 (2) | |
O1 | 0.62126 (16) | 0.2614 (2) | 0.10059 (10) | 0.0973 (8) | |
O2 | 0.73010 (15) | 0.2958 (2) | 0.02568 (9) | 0.0903 (7) | |
O3 | 0.9224 (3) | 0.1642 (6) | 0.0498 (2) | 0.0647 (15) | 0.616 (4) |
O3' | 0.9339 (5) | 0.2182 (8) | 0.0701 (4) | 0.070 (3) | 0.384 (4) |
O4 | 0.95195 (13) | 0.04885 (19) | 0.14924 (9) | 0.0686 (5) | |
C1 | 0.77891 (17) | 0.1334 (2) | 0.11455 (10) | 0.0456 (6) | |
C2 | 0.71144 (19) | 0.2344 (3) | 0.07458 (12) | 0.0510 (6) | |
C3 | 0.8908 (2) | 0.1173 (3) | 0.10908 (13) | 0.0595 (7) | |
C4 | 0.5427 (2) | 0.3578 (4) | 0.06629 (17) | 0.0883 (10) | |
H4 | 0.5727 | 0.4019 | 0.0285 | 0.106* | |
C5 | 0.4466 (3) | 0.2731 (4) | 0.04265 (18) | 0.1286 (14) | |
H5A | 0.4660 | 0.1958 | 0.0144 | 0.193* | |
H5B | 0.3950 | 0.3358 | 0.0184 | 0.193* | |
H5C | 0.4159 | 0.2321 | 0.0797 | 0.193* | |
C6 | 0.5222 (3) | 0.4721 (4) | 0.11353 (19) | 0.1204 (13) | |
H6A | 0.5880 | 0.5221 | 0.1279 | 0.181* | |
H6B | 0.4940 | 0.4289 | 0.1510 | 0.181* | |
H6C | 0.4710 | 0.5405 | 0.0927 | 0.181* | |
C7 | 1.0358 (3) | 0.1456 (6) | 0.0431 (3) | 0.0897 (17) | 0.616 (4) |
H7A | 1.0459 | 0.1293 | −0.0029 | 0.108* | 0.616 (4) |
H7B | 1.0637 | 0.0615 | 0.0685 | 0.108* | 0.616 (4) |
C7' | 1.0485 (5) | 0.2473 (9) | 0.0793 (5) | 0.0897 (17) | 0.384 (4) |
H7'A | 1.0751 | 0.2396 | 0.1258 | 0.108* | 0.384 (4) |
H7'B | 1.0626 | 0.3455 | 0.0645 | 0.108* | 0.384 (4) |
C8 | 1.0953 (6) | 0.2825 (8) | 0.0683 (4) | 0.185 (4) | 0.616 (4) |
H8A | 1.0629 | 0.3663 | 0.0457 | 0.278* | 0.616 (4) |
H8B | 1.1692 | 0.2756 | 0.0601 | 0.278* | 0.616 (4) |
H8C | 1.0914 | 0.2923 | 0.1149 | 0.278* | 0.616 (4) |
C8' | 1.1053 (8) | 0.1363 (14) | 0.0393 (6) | 0.185 (4) | 0.384 (4) |
H8'A | 1.0862 | 0.1536 | −0.0070 | 0.278* | 0.384 (4) |
H8'B | 1.0837 | 0.0394 | 0.0502 | 0.278* | 0.384 (4) |
H8'C | 1.1817 | 0.1460 | 0.0496 | 0.278* | 0.384 (4) |
C11 | 0.78585 (17) | −0.1571 (2) | 0.17111 (12) | 0.0472 (6) | |
C12 | 0.82857 (19) | −0.2374 (3) | 0.22506 (12) | 0.0571 (7) | |
H12 | 0.8358 | −0.1957 | 0.2670 | 0.069* | |
C13 | 0.8607 (2) | −0.3802 (3) | 0.21667 (16) | 0.0739 (8) | |
H13 | 0.8901 | −0.4339 | 0.2531 | 0.089* | |
C14 | 0.8498 (2) | −0.4429 (3) | 0.15545 (18) | 0.0774 (9) | |
H14 | 0.8701 | −0.5396 | 0.1503 | 0.093* | |
C15 | 0.8090 (2) | −0.3634 (3) | 0.10210 (15) | 0.0775 (8) | |
H15 | 0.8021 | −0.4059 | 0.0603 | 0.093* | |
C16 | 0.7780 (2) | −0.2208 (3) | 0.10917 (13) | 0.0622 (7) | |
H16 | 0.7515 | −0.1669 | 0.0722 | 0.075* | |
C21 | 0.78327 (17) | 0.0933 (2) | 0.26071 (11) | 0.0447 (6) | |
C22 | 0.74220 (18) | 0.0353 (3) | 0.31610 (11) | 0.0544 (6) | |
H22 | 0.6935 | −0.0416 | 0.3109 | 0.065* | |
C23 | 0.7725 (2) | 0.0898 (3) | 0.37771 (12) | 0.0631 (7) | |
H23 | 0.7435 | 0.0505 | 0.4140 | 0.076* | |
C24 | 0.8454 (2) | 0.2020 (3) | 0.38665 (13) | 0.0670 (8) | |
H24 | 0.8656 | 0.2390 | 0.4287 | 0.080* | |
C25 | 0.8880 (2) | 0.2588 (3) | 0.33310 (14) | 0.0661 (7) | |
H25 | 0.9383 | 0.3337 | 0.3389 | 0.079* | |
C26 | 0.85643 (19) | 0.2052 (3) | 0.27018 (12) | 0.0560 (7) | |
H26 | 0.8851 | 0.2455 | 0.2340 | 0.067* | |
C31 | 0.59357 (18) | 0.0143 (3) | 0.17709 (11) | 0.0483 (6) | |
C32 | 0.5370 (2) | −0.0903 (3) | 0.13930 (14) | 0.0718 (8) | |
H32 | 0.5733 | −0.1551 | 0.1144 | 0.086* | |
C33 | 0.4269 (2) | −0.1000 (4) | 0.13799 (18) | 0.0948 (11) | |
H33 | 0.3892 | −0.1696 | 0.1114 | 0.114* | |
C34 | 0.3730 (2) | −0.0081 (4) | 0.17536 (19) | 0.0952 (11) | |
H34 | 0.2988 | −0.0163 | 0.1750 | 0.114* | |
C35 | 0.4283 (2) | 0.0969 (4) | 0.21374 (15) | 0.0805 (9) | |
H35 | 0.3919 | 0.1598 | 0.2394 | 0.097* | |
C36 | 0.5376 (2) | 0.1081 (3) | 0.21376 (12) | 0.0627 (7) | |
H36 | 0.5747 | 0.1804 | 0.2390 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0432 (4) | 0.0451 (4) | 0.0433 (4) | 0.0004 (3) | 0.0037 (3) | 0.0017 (3) |
O1 | 0.0757 (13) | 0.1258 (17) | 0.0976 (15) | 0.0543 (13) | 0.0420 (12) | 0.0682 (13) |
O2 | 0.0849 (14) | 0.1184 (17) | 0.0729 (13) | 0.0319 (12) | 0.0317 (11) | 0.0499 (13) |
O3 | 0.046 (2) | 0.087 (4) | 0.064 (3) | 0.003 (2) | 0.0169 (18) | 0.019 (3) |
O3' | 0.060 (4) | 0.083 (5) | 0.068 (5) | −0.025 (3) | 0.017 (3) | 0.003 (4) |
O4 | 0.0474 (11) | 0.0798 (13) | 0.0781 (13) | 0.0087 (9) | 0.0050 (9) | 0.0189 (11) |
C1 | 0.0432 (14) | 0.0486 (14) | 0.0455 (14) | 0.0017 (11) | 0.0062 (11) | 0.0044 (11) |
C2 | 0.0501 (15) | 0.0578 (16) | 0.0455 (15) | 0.0045 (12) | 0.0074 (12) | 0.0042 (13) |
C3 | 0.0533 (17) | 0.0624 (17) | 0.0637 (18) | 0.0032 (14) | 0.0110 (14) | 0.0111 (14) |
C4 | 0.073 (2) | 0.106 (3) | 0.089 (2) | 0.039 (2) | 0.0226 (18) | 0.049 (2) |
C5 | 0.127 (3) | 0.132 (3) | 0.114 (3) | 0.014 (3) | −0.042 (3) | 0.027 (3) |
C6 | 0.105 (3) | 0.114 (3) | 0.143 (3) | 0.038 (2) | 0.017 (3) | 0.019 (3) |
C7 | 0.065 (3) | 0.115 (5) | 0.096 (4) | −0.009 (3) | 0.037 (3) | 0.019 (3) |
C7' | 0.065 (3) | 0.115 (5) | 0.096 (4) | −0.009 (3) | 0.037 (3) | 0.019 (3) |
C8 | 0.108 (5) | 0.275 (11) | 0.185 (7) | −0.092 (6) | 0.070 (5) | −0.089 (7) |
C8' | 0.108 (5) | 0.275 (11) | 0.185 (7) | −0.092 (6) | 0.070 (5) | −0.089 (7) |
C11 | 0.0423 (13) | 0.0456 (14) | 0.0534 (15) | −0.0011 (11) | 0.0035 (11) | 0.0028 (12) |
C12 | 0.0542 (16) | 0.0559 (17) | 0.0607 (17) | 0.0005 (13) | 0.0035 (13) | 0.0091 (13) |
C13 | 0.0708 (19) | 0.0570 (18) | 0.091 (2) | 0.0082 (15) | −0.0022 (17) | 0.0204 (17) |
C14 | 0.074 (2) | 0.0485 (18) | 0.110 (3) | 0.0069 (14) | 0.0072 (19) | −0.0025 (19) |
C15 | 0.087 (2) | 0.064 (2) | 0.080 (2) | 0.0066 (17) | 0.0030 (17) | −0.0158 (17) |
C16 | 0.0716 (18) | 0.0575 (17) | 0.0557 (17) | 0.0105 (14) | −0.0008 (13) | −0.0047 (13) |
C21 | 0.0407 (13) | 0.0452 (13) | 0.0477 (14) | 0.0006 (11) | 0.0032 (11) | −0.0013 (11) |
C22 | 0.0525 (15) | 0.0623 (16) | 0.0481 (15) | −0.0106 (13) | 0.0047 (12) | −0.0009 (13) |
C23 | 0.0606 (17) | 0.083 (2) | 0.0454 (16) | 0.0006 (15) | 0.0063 (13) | 0.0012 (14) |
C24 | 0.0610 (18) | 0.083 (2) | 0.0545 (17) | 0.0064 (15) | −0.0067 (14) | −0.0168 (15) |
C25 | 0.0597 (17) | 0.0647 (18) | 0.0721 (19) | −0.0076 (14) | −0.0006 (15) | −0.0161 (15) |
C26 | 0.0563 (16) | 0.0552 (16) | 0.0566 (16) | −0.0027 (13) | 0.0075 (13) | −0.0004 (13) |
C31 | 0.0432 (13) | 0.0504 (14) | 0.0513 (14) | −0.0013 (12) | 0.0056 (11) | 0.0065 (12) |
C32 | 0.0519 (17) | 0.0607 (17) | 0.102 (2) | −0.0052 (14) | 0.0039 (15) | −0.0089 (16) |
C33 | 0.057 (2) | 0.077 (2) | 0.147 (3) | −0.0189 (17) | −0.005 (2) | −0.006 (2) |
C34 | 0.0464 (18) | 0.111 (3) | 0.129 (3) | −0.0029 (19) | 0.015 (2) | 0.030 (2) |
C35 | 0.0547 (19) | 0.109 (3) | 0.080 (2) | 0.0156 (18) | 0.0176 (16) | 0.0113 (19) |
C36 | 0.0502 (16) | 0.0799 (19) | 0.0577 (17) | 0.0052 (14) | 0.0045 (13) | −0.0009 (15) |
Geometric parameters (Å, º) top
P1—C1 | 1.741 (2) | C8'—H8'C | 0.9600 |
P1—C21 | 1.801 (2) | C11—C12 | 1.379 (3) |
P1—C11 | 1.811 (2) | C11—C16 | 1.382 (3) |
P1—C31 | 1.815 (2) | C12—C13 | 1.384 (3) |
O1—C2 | 1.322 (3) | C12—H12 | 0.9300 |
O1—C4 | 1.442 (3) | C13—C14 | 1.365 (4) |
O2—C2 | 1.188 (3) | C13—H13 | 0.9300 |
O3—C3 | 1.379 (4) | C14—C15 | 1.359 (4) |
O3—C7 | 1.451 (3) | C14—H14 | 0.9300 |
O3'—C3 | 1.367 (7) | C15—C16 | 1.375 (3) |
O3'—C7' | 1.451 (3) | C15—H15 | 0.9300 |
O4—C3 | 1.228 (3) | C16—H16 | 0.9300 |
C1—C3 | 1.425 (3) | C21—C26 | 1.373 (3) |
C1—C2 | 1.441 (3) | C21—C22 | 1.395 (3) |
C4—C6 | 1.463 (4) | C22—C23 | 1.364 (3) |
C4—C5 | 1.467 (4) | C22—H22 | 0.9300 |
C4—H4 | 0.9800 | C23—C24 | 1.373 (3) |
C5—H5A | 0.9600 | C23—H23 | 0.9300 |
C5—H5B | 0.9600 | C24—C25 | 1.368 (3) |
C5—H5C | 0.9600 | C24—H24 | 0.9300 |
C6—H6A | 0.9600 | C25—C26 | 1.387 (3) |
C6—H6B | 0.9600 | C25—H25 | 0.9300 |
C6—H6C | 0.9600 | C26—H26 | 0.9300 |
C7—C8 | 1.518 (3) | C31—C32 | 1.375 (3) |
C7—H7A | 0.9700 | C31—C36 | 1.378 (3) |
C7—H7B | 0.9700 | C32—C33 | 1.379 (4) |
C7'—C8' | 1.526 (3) | C32—H32 | 0.9300 |
C7'—H7'A | 0.9700 | C33—C34 | 1.362 (4) |
C7'—H7'B | 0.9700 | C33—H33 | 0.9300 |
C8—H8A | 0.9600 | C34—C35 | 1.377 (4) |
C8—H8B | 0.9600 | C34—H34 | 0.9300 |
C8—H8C | 0.9600 | C35—C36 | 1.372 (3) |
C8'—H8'A | 0.9600 | C35—H35 | 0.9300 |
C8'—H8'B | 0.9600 | C36—H36 | 0.9300 |
| | | |
C1—P1—C21 | 115.24 (11) | H8'B—C8'—H8'C | 109.5 |
C1—P1—C11 | 109.17 (11) | C12—C11—C16 | 118.9 (2) |
C21—P1—C11 | 108.51 (11) | C12—C11—P1 | 122.24 (19) |
C1—P1—C31 | 113.44 (10) | C16—C11—P1 | 118.85 (18) |
C21—P1—C31 | 104.40 (11) | C11—C12—C13 | 119.9 (2) |
C11—P1—C31 | 105.51 (11) | C11—C12—H12 | 120.1 |
C2—O1—C4 | 119.2 (2) | C13—C12—H12 | 120.1 |
C3—O3—C7 | 115.1 (4) | C14—C13—C12 | 120.6 (3) |
C3—O3'—C7' | 119.8 (7) | C14—C13—H13 | 119.7 |
C3—C1—C2 | 122.8 (2) | C12—C13—H13 | 119.7 |
C3—C1—P1 | 111.77 (17) | C15—C14—C13 | 119.7 (3) |
C2—C1—P1 | 125.22 (17) | C15—C14—H14 | 120.2 |
O2—C2—O1 | 120.1 (2) | C13—C14—H14 | 120.2 |
O2—C2—C1 | 128.2 (2) | C14—C15—C16 | 120.7 (3) |
O1—C2—C1 | 111.5 (2) | C14—C15—H15 | 119.6 |
O4—C3—O3' | 118.4 (4) | C16—C15—H15 | 119.6 |
O4—C3—O3 | 121.5 (3) | C15—C16—C11 | 120.2 (3) |
O4—C3—C1 | 123.1 (2) | C15—C16—H16 | 119.9 |
O3'—C3—C1 | 115.4 (4) | C11—C16—H16 | 119.9 |
O3—C3—C1 | 114.6 (3) | C26—C21—C22 | 118.1 (2) |
O1—C4—C6 | 106.2 (3) | C26—C21—P1 | 120.69 (18) |
O1—C4—C5 | 109.0 (3) | C22—C21—P1 | 121.22 (18) |
C6—C4—C5 | 113.3 (3) | C23—C22—C21 | 120.9 (2) |
O1—C4—H4 | 109.4 | C23—C22—H22 | 119.5 |
C6—C4—H4 | 109.4 | C21—C22—H22 | 119.5 |
C5—C4—H4 | 109.4 | C22—C23—C24 | 120.6 (2) |
C4—C5—H5A | 109.5 | C22—C23—H23 | 119.7 |
C4—C5—H5B | 109.5 | C24—C23—H23 | 119.7 |
H5A—C5—H5B | 109.5 | C25—C24—C23 | 119.4 (2) |
C4—C5—H5C | 109.5 | C25—C24—H24 | 120.3 |
H5A—C5—H5C | 109.5 | C23—C24—H24 | 120.3 |
H5B—C5—H5C | 109.5 | C24—C25—C26 | 120.3 (2) |
C4—C6—H6A | 109.5 | C24—C25—H25 | 119.8 |
C4—C6—H6B | 109.5 | C26—C25—H25 | 119.8 |
H6A—C6—H6B | 109.5 | C21—C26—C25 | 120.7 (2) |
C4—C6—H6C | 109.5 | C21—C26—H26 | 119.7 |
H6A—C6—H6C | 109.5 | C25—C26—H26 | 119.7 |
H6B—C6—H6C | 109.5 | C32—C31—C36 | 118.4 (2) |
O3—C7—C8 | 108.7 (4) | C32—C31—P1 | 120.77 (19) |
O3—C7—H7A | 110.0 | C36—C31—P1 | 120.80 (19) |
C8—C7—H7A | 110.0 | C31—C32—C33 | 120.5 (3) |
O3—C7—H7B | 110.0 | C31—C32—H32 | 119.8 |
C8—C7—H7B | 110.0 | C33—C32—H32 | 119.8 |
H7A—C7—H7B | 108.3 | C34—C33—C32 | 120.4 (3) |
O3'—C7'—C8' | 108.7 (6) | C34—C33—H33 | 119.8 |
O3'—C7'—H7'A | 109.9 | C32—C33—H33 | 119.8 |
C8'—C7'—H7'A | 109.9 | C33—C34—C35 | 119.9 (3) |
O3'—C7'—H7'B | 109.9 | C33—C34—H34 | 120.0 |
C8'—C7'—H7'B | 109.9 | C35—C34—H34 | 120.0 |
H7'A—C7'—H7'B | 108.3 | C36—C35—C34 | 119.5 (3) |
C7'—C8'—H8'A | 109.5 | C36—C35—H35 | 120.3 |
C7'—C8'—H8'B | 109.5 | C34—C35—H35 | 120.3 |
H8'A—C8'—H8'B | 109.5 | C35—C36—C31 | 121.3 (3) |
C7'—C8'—H8'C | 109.5 | C35—C36—H36 | 119.4 |
H8'A—C8'—H8'C | 109.5 | C31—C36—H36 | 119.4 |
| | | |
C21—P1—C1—C3 | 72.0 (2) | P1—C11—C12—C13 | 178.16 (19) |
C11—P1—C1—C3 | −50.4 (2) | C11—C12—C13—C14 | −0.5 (4) |
C31—P1—C1—C3 | −167.72 (17) | C12—C13—C14—C15 | 1.4 (4) |
C21—P1—C1—C2 | −103.2 (2) | C13—C14—C15—C16 | −0.5 (4) |
C11—P1—C1—C2 | 134.5 (2) | C14—C15—C16—C11 | −1.3 (4) |
C31—P1—C1—C2 | 17.1 (2) | C12—C11—C16—C15 | 2.1 (4) |
C4—O1—C2—O2 | 4.5 (4) | P1—C11—C16—C15 | −177.3 (2) |
C4—O1—C2—C1 | −178.6 (2) | C1—P1—C21—C26 | −8.9 (2) |
C3—C1—C2—O2 | 15.0 (4) | C11—P1—C21—C26 | 113.87 (19) |
P1—C1—C2—O2 | −170.4 (2) | C31—P1—C21—C26 | −133.97 (19) |
C3—C1—C2—O1 | −161.6 (2) | C1—P1—C21—C22 | 168.92 (18) |
P1—C1—C2—O1 | 13.0 (3) | C11—P1—C21—C22 | −68.4 (2) |
C7'—O3'—C3—O4 | −3.2 (8) | C31—P1—C21—C22 | 43.8 (2) |
C7'—O3'—C3—O3 | −107.7 (12) | C26—C21—C22—C23 | 1.1 (3) |
C7'—O3'—C3—C1 | 157.5 (5) | P1—C21—C22—C23 | −176.75 (18) |
C7—O3—C3—O4 | −8.6 (6) | C21—C22—C23—C24 | −0.9 (4) |
C7—O3—C3—O3' | 82.9 (10) | C22—C23—C24—C25 | −0.2 (4) |
C7—O3—C3—C1 | −178.8 (3) | C23—C24—C25—C26 | 1.1 (4) |
C2—C1—C3—O4 | 168.6 (2) | C22—C21—C26—C25 | −0.2 (3) |
P1—C1—C3—O4 | −6.7 (3) | P1—C21—C26—C25 | 177.64 (18) |
C2—C1—C3—O3' | 8.9 (5) | C24—C25—C26—C21 | −0.9 (4) |
P1—C1—C3—O3' | −166.4 (4) | C1—P1—C31—C32 | 85.3 (2) |
C2—C1—C3—O3 | −21.4 (4) | C21—P1—C31—C32 | −148.4 (2) |
P1—C1—C3—O3 | 163.3 (3) | C11—P1—C31—C32 | −34.1 (2) |
C2—O1—C4—C6 | −125.0 (3) | C1—P1—C31—C36 | −94.8 (2) |
C2—O1—C4—C5 | 112.5 (3) | C21—P1—C31—C36 | 31.5 (2) |
C3—O3—C7—C8 | −90.3 (6) | C11—P1—C31—C36 | 145.8 (2) |
C3—O3'—C7'—C8' | 85.6 (10) | C36—C31—C32—C33 | 0.4 (4) |
C1—P1—C11—C12 | 138.36 (19) | P1—C31—C32—C33 | −179.7 (2) |
C21—P1—C11—C12 | 12.0 (2) | C31—C32—C33—C34 | −1.6 (5) |
C31—P1—C11—C12 | −99.4 (2) | C32—C33—C34—C35 | 1.2 (5) |
C1—P1—C11—C16 | −42.3 (2) | C33—C34—C35—C36 | 0.2 (5) |
C21—P1—C11—C16 | −168.59 (19) | C34—C35—C36—C31 | −1.3 (4) |
C31—P1—C11—C16 | 80.0 (2) | C32—C31—C36—C35 | 1.0 (4) |
C16—C11—C12—C13 | −1.2 (4) | P1—C31—C36—C35 | −178.9 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | | | 2.953 (2) | |
P1···O4 | | | 2.809 (2) | |
C5—H5C···Cg3 | 0.96 | 2.93 | 3.663 (4) | 134 |
C25—H25···O4i | 0.93 | 2.40 | 3.323 (3) | 172 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
(IIa) methyl
tert-butyl 2-(triphenylphosphoranyliden)malonate
top
Crystal data top
C26H27O4P | F(000) = 920 |
Mr = 434.45 | Dx = 1.201 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7347 reflections |
a = 9.8140 (7) Å | θ = 2.4–27.5° |
b = 15.889 (2) Å | µ = 0.14 mm−1 |
c = 15.404 (2) Å | T = 140 K |
β = 90.413 (2)° | Block, colourless |
V = 2402.0 (5) Å3 | 0.16 × 0.16 × 0.16 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4501 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 27.8°, θmin = 1.8° |
ϕ and ω scans | h = −11→12 |
19840 measured reflections | k = −20→20 |
5292 independent reflections | l = −20→20 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0764P)2 + 0.8536P] where P = (Fo2 + 2Fc2)/3 |
5292 reflections | (Δ/σ)max = 0.008 |
284 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
Crystal data top
C26H27O4P | V = 2402.0 (5) Å3 |
Mr = 434.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8140 (7) Å | µ = 0.14 mm−1 |
b = 15.889 (2) Å | T = 140 K |
c = 15.404 (2) Å | 0.16 × 0.16 × 0.16 mm |
β = 90.413 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4501 reflections with I > 2σ(I) |
19840 measured reflections | Rint = 0.021 |
5292 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.60 e Å−3 |
5292 reflections | Δρmin = −0.45 e Å−3 |
284 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 | 0.14127 (4) | 0.18082 (3) | 0.47388 (3) | 0.03449 (14) | |
O1 | −0.03175 (14) | 0.28668 (8) | 0.56513 (8) | 0.0484 (3) | |
O2 | −0.04149 (14) | 0.22305 (9) | 0.69524 (8) | 0.0525 (3) | |
O3 | 0.11969 (15) | 0.08631 (9) | 0.70944 (8) | 0.0583 (4) | |
O4 | 0.2686 (2) | 0.06909 (18) | 0.60761 (12) | 0.1345 (12) | |
C1 | 0.09323 (16) | 0.16494 (10) | 0.58150 (10) | 0.0365 (3) | |
C2 | 0.00120 (17) | 0.22425 (10) | 0.62166 (10) | 0.0392 (4) | |
C3 | 0.16718 (18) | 0.10306 (12) | 0.63060 (11) | 0.0464 (4) | |
C4 | −0.1236 (3) | 0.35562 (14) | 0.58826 (14) | 0.0665 (6) | |
C5 | −0.1376 (4) | 0.40236 (18) | 0.50279 (19) | 0.0982 (10) | |
H5A | −0.0491 | 0.4191 | 0.4831 | 0.147* | |
H5B | −0.1933 | 0.4514 | 0.5109 | 0.147* | |
H5C | −0.1795 | 0.3662 | 0.4604 | 0.147* | |
C6 | −0.0546 (5) | 0.40994 (18) | 0.6566 (2) | 0.1148 (13) | |
H6A | −0.0497 | 0.3796 | 0.7104 | 0.172* | |
H6B | −0.1063 | 0.4606 | 0.6646 | 0.172* | |
H6C | 0.0357 | 0.4240 | 0.6380 | 0.172* | |
C7 | −0.2604 (3) | 0.3214 (2) | 0.6159 (2) | 0.1119 (13) | |
H7A | −0.2498 | 0.2907 | 0.6692 | 0.168* | |
H7B | −0.2955 | 0.2846 | 0.5717 | 0.168* | |
H7C | −0.3226 | 0.3672 | 0.6245 | 0.168* | |
C8 | 0.1943 (3) | 0.02723 (16) | 0.76090 (15) | 0.0767 (7) | |
H8A | 0.1602 | 0.0277 | 0.8192 | 0.115* | |
H8B | 0.2890 | 0.0423 | 0.7615 | 0.115* | |
H8C | 0.1839 | −0.0281 | 0.7367 | 0.115* | |
C11 | 0.26076 (17) | 0.26686 (10) | 0.46337 (11) | 0.0387 (4) | |
C12 | 0.3300 (2) | 0.28250 (12) | 0.38661 (11) | 0.0477 (4) | |
H12A | 0.3128 | 0.2493 | 0.3380 | 0.057* | |
C13 | 0.4241 (2) | 0.34692 (14) | 0.38185 (14) | 0.0588 (5) | |
H13 | 0.4692 | 0.3575 | 0.3301 | 0.071* | |
C14 | 0.4506 (3) | 0.39522 (15) | 0.45370 (16) | 0.0708 (7) | |
H14 | 0.5143 | 0.4384 | 0.4506 | 0.085* | |
C15 | 0.3836 (3) | 0.38024 (15) | 0.53036 (15) | 0.0707 (7) | |
H15 | 0.4021 | 0.4134 | 0.5788 | 0.085* | |
C16 | 0.2890 (2) | 0.31607 (12) | 0.53573 (12) | 0.0512 (5) | |
H16 | 0.2444 | 0.3059 | 0.5877 | 0.061* | |
C21 | 0.22434 (17) | 0.09091 (10) | 0.42527 (10) | 0.0387 (4) | |
C22 | 0.1478 (2) | 0.03033 (12) | 0.38286 (13) | 0.0517 (4) | |
H22 | 0.0537 | 0.0360 | 0.3789 | 0.062* | |
C23 | 0.2116 (3) | −0.03907 (13) | 0.34610 (16) | 0.0658 (6) | |
H23 | 0.1600 | −0.0800 | 0.3178 | 0.079* | |
C24 | 0.3503 (3) | −0.04726 (14) | 0.35148 (16) | 0.0666 (6) | |
H24 | 0.3925 | −0.0938 | 0.3268 | 0.080* | |
C25 | 0.4274 (2) | 0.01279 (14) | 0.39303 (14) | 0.0602 (5) | |
H25 | 0.5216 | 0.0069 | 0.3962 | 0.072* | |
C26 | 0.36547 (19) | 0.08184 (13) | 0.43009 (13) | 0.0500 (4) | |
H26 | 0.4179 | 0.1224 | 0.4583 | 0.060* | |
C31 | −0.00707 (18) | 0.20010 (11) | 0.40597 (11) | 0.0418 (4) | |
C32 | −0.1290 (2) | 0.16113 (13) | 0.42658 (14) | 0.0539 (5) | |
H32 | −0.1345 | 0.1261 | 0.4748 | 0.065* | |
C33 | −0.2431 (2) | 0.17488 (16) | 0.37440 (17) | 0.0695 (6) | |
H33 | −0.3251 | 0.1489 | 0.3882 | 0.083* | |
C34 | −0.2367 (3) | 0.22568 (18) | 0.30367 (17) | 0.0772 (7) | |
H34 | −0.3143 | 0.2351 | 0.2700 | 0.093* | |
C35 | −0.1165 (3) | 0.26294 (19) | 0.28190 (16) | 0.0804 (8) | |
H35 | −0.1117 | 0.2965 | 0.2326 | 0.096* | |
C36 | −0.0010 (2) | 0.25077 (15) | 0.33332 (14) | 0.0625 (5) | |
H36 | 0.0805 | 0.2769 | 0.3187 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0317 (2) | 0.0407 (2) | 0.0311 (2) | −0.00082 (15) | 0.00176 (16) | 0.00031 (15) |
O1 | 0.0604 (8) | 0.0452 (7) | 0.0397 (6) | 0.0135 (6) | 0.0059 (6) | 0.0031 (5) |
O2 | 0.0598 (8) | 0.0608 (8) | 0.0369 (6) | 0.0137 (6) | 0.0121 (6) | 0.0032 (6) |
O3 | 0.0698 (9) | 0.0637 (8) | 0.0416 (7) | 0.0220 (7) | 0.0111 (6) | 0.0158 (6) |
O4 | 0.1237 (17) | 0.218 (3) | 0.0619 (11) | 0.1255 (19) | 0.0422 (11) | 0.0563 (14) |
C1 | 0.0329 (8) | 0.0443 (8) | 0.0324 (8) | −0.0009 (6) | 0.0025 (6) | 0.0019 (6) |
C2 | 0.0375 (8) | 0.0437 (9) | 0.0365 (8) | −0.0004 (7) | 0.0010 (7) | 0.0003 (7) |
C3 | 0.0423 (9) | 0.0602 (11) | 0.0367 (9) | 0.0093 (8) | 0.0055 (7) | 0.0048 (8) |
C4 | 0.0855 (16) | 0.0594 (12) | 0.0547 (12) | 0.0324 (12) | 0.0033 (11) | 0.0003 (10) |
C5 | 0.148 (3) | 0.0711 (16) | 0.0752 (17) | 0.0497 (18) | −0.0028 (17) | 0.0162 (13) |
C6 | 0.189 (4) | 0.0683 (17) | 0.087 (2) | 0.038 (2) | −0.022 (2) | −0.0282 (15) |
C7 | 0.0759 (19) | 0.144 (3) | 0.116 (3) | 0.055 (2) | 0.0222 (18) | 0.028 (2) |
C8 | 0.107 (2) | 0.0749 (15) | 0.0482 (12) | 0.0345 (14) | 0.0042 (12) | 0.0197 (11) |
C11 | 0.0375 (8) | 0.0423 (8) | 0.0362 (8) | −0.0050 (6) | 0.0034 (6) | −0.0004 (6) |
C12 | 0.0543 (11) | 0.0522 (10) | 0.0367 (9) | −0.0108 (8) | 0.0093 (8) | −0.0066 (7) |
C13 | 0.0675 (13) | 0.0599 (11) | 0.0492 (11) | −0.0187 (10) | 0.0215 (10) | −0.0041 (9) |
C14 | 0.0799 (16) | 0.0644 (13) | 0.0686 (14) | −0.0346 (12) | 0.0257 (12) | −0.0163 (11) |
C15 | 0.0813 (16) | 0.0729 (14) | 0.0583 (13) | −0.0342 (12) | 0.0195 (11) | −0.0266 (11) |
C16 | 0.0537 (11) | 0.0596 (11) | 0.0405 (9) | −0.0142 (9) | 0.0119 (8) | −0.0097 (8) |
C21 | 0.0391 (8) | 0.0423 (8) | 0.0349 (8) | 0.0013 (7) | 0.0058 (6) | 0.0005 (6) |
C22 | 0.0480 (10) | 0.0488 (10) | 0.0584 (11) | −0.0050 (8) | 0.0063 (9) | −0.0071 (8) |
C23 | 0.0749 (15) | 0.0492 (11) | 0.0736 (15) | −0.0066 (10) | 0.0117 (12) | −0.0171 (10) |
C24 | 0.0785 (16) | 0.0508 (11) | 0.0707 (14) | 0.0140 (10) | 0.0229 (12) | −0.0059 (10) |
C25 | 0.0510 (11) | 0.0665 (13) | 0.0631 (13) | 0.0156 (10) | 0.0121 (9) | 0.0021 (10) |
C26 | 0.0411 (10) | 0.0579 (11) | 0.0510 (10) | 0.0033 (8) | 0.0044 (8) | −0.0041 (8) |
C31 | 0.0384 (9) | 0.0502 (9) | 0.0368 (8) | 0.0050 (7) | −0.0040 (7) | −0.0031 (7) |
C32 | 0.0430 (10) | 0.0631 (11) | 0.0556 (11) | −0.0014 (9) | −0.0047 (8) | −0.0016 (9) |
C33 | 0.0419 (11) | 0.0859 (16) | 0.0804 (16) | −0.0019 (10) | −0.0139 (11) | −0.0127 (13) |
C34 | 0.0609 (15) | 0.1006 (19) | 0.0696 (15) | 0.0190 (13) | −0.0283 (12) | −0.0068 (14) |
C35 | 0.0766 (17) | 0.107 (2) | 0.0575 (14) | 0.0124 (15) | −0.0199 (12) | 0.0199 (13) |
C36 | 0.0559 (12) | 0.0820 (15) | 0.0494 (11) | 0.0028 (10) | −0.0049 (9) | 0.0153 (10) |
Geometric parameters (Å, º) top
P1—C1 | 1.7451 (16) | C12—H12A | 0.9300 |
P1—C11 | 1.8092 (17) | C13—C14 | 1.370 (3) |
P1—C21 | 1.8097 (17) | C13—H13 | 0.9300 |
P1—C31 | 1.8126 (17) | C14—C15 | 1.376 (3) |
O1—C2 | 1.357 (2) | C14—H14 | 0.9300 |
O1—C4 | 1.464 (2) | C15—C16 | 1.382 (3) |
O2—C2 | 1.211 (2) | C15—H15 | 0.9300 |
O3—C3 | 1.331 (2) | C16—H16 | 0.9300 |
O3—C8 | 1.427 (2) | C21—C22 | 1.382 (2) |
O4—C3 | 1.188 (2) | C21—C26 | 1.394 (2) |
C1—C3 | 1.434 (2) | C22—C23 | 1.390 (3) |
C1—C2 | 1.447 (2) | C22—H22 | 0.9300 |
C4—C7 | 1.512 (4) | C23—C24 | 1.369 (3) |
C4—C6 | 1.516 (4) | C23—H23 | 0.9300 |
C4—C5 | 1.517 (3) | C24—C25 | 1.373 (3) |
C5—H5A | 0.9600 | C24—H24 | 0.9300 |
C5—H5B | 0.9600 | C25—C26 | 1.380 (3) |
C5—H5C | 0.9600 | C25—H25 | 0.9300 |
C6—H6A | 0.9600 | C26—H26 | 0.9300 |
C6—H6B | 0.9600 | C31—C36 | 1.380 (3) |
C6—H6C | 0.9600 | C31—C32 | 1.386 (3) |
C7—H7A | 0.9600 | C32—C33 | 1.391 (3) |
C7—H7B | 0.9600 | C32—H32 | 0.9300 |
C7—H7C | 0.9600 | C33—C34 | 1.358 (4) |
C8—H8A | 0.9600 | C33—H33 | 0.9300 |
C8—H8B | 0.9600 | C34—C35 | 1.364 (4) |
C8—H8C | 0.9600 | C34—H34 | 0.9300 |
C11—C16 | 1.388 (2) | C35—C36 | 1.392 (3) |
C11—C12 | 1.390 (2) | C35—H35 | 0.9300 |
C12—C13 | 1.381 (3) | C36—H36 | 0.9300 |
| | | |
C1—P1—C11 | 111.96 (8) | C13—C12—H12A | 119.7 |
C1—P1—C21 | 113.86 (8) | C11—C12—H12A | 119.7 |
C11—P1—C21 | 105.38 (8) | C14—C13—C12 | 119.70 (18) |
C1—P1—C31 | 110.57 (8) | C14—C13—H13 | 120.1 |
C11—P1—C31 | 109.82 (8) | C12—C13—H13 | 120.1 |
C21—P1—C31 | 104.89 (8) | C13—C14—C15 | 120.47 (19) |
C2—O1—C4 | 122.33 (14) | C13—C14—H14 | 119.8 |
C3—O3—C8 | 117.18 (16) | C15—C14—H14 | 119.8 |
C3—C1—C2 | 122.41 (15) | C14—C15—C16 | 120.27 (19) |
C3—C1—P1 | 117.44 (12) | C14—C15—H15 | 119.9 |
C2—C1—P1 | 119.05 (12) | C16—C15—H15 | 119.9 |
O2—C2—O1 | 121.96 (15) | C15—C16—C11 | 119.88 (17) |
O2—C2—C1 | 127.64 (15) | C15—C16—H16 | 120.1 |
O1—C2—C1 | 110.37 (14) | C11—C16—H16 | 120.1 |
O4—C3—O3 | 118.73 (17) | C22—C21—C26 | 119.29 (16) |
O4—C3—C1 | 125.16 (17) | C22—C21—P1 | 120.04 (14) |
O3—C3—C1 | 116.04 (15) | C26—C21—P1 | 120.66 (14) |
O1—C4—C7 | 110.4 (2) | C21—C22—C23 | 120.03 (19) |
O1—C4—C6 | 108.8 (2) | C21—C22—H22 | 120.0 |
C7—C4—C6 | 113.7 (3) | C23—C22—H22 | 120.0 |
O1—C4—C5 | 101.97 (18) | C24—C23—C22 | 120.1 (2) |
C7—C4—C5 | 110.2 (2) | C24—C23—H23 | 120.0 |
C6—C4—C5 | 111.2 (2) | C22—C23—H23 | 120.0 |
C4—C5—H5A | 109.5 | C23—C24—C25 | 120.43 (19) |
C4—C5—H5B | 109.5 | C23—C24—H24 | 119.8 |
H5A—C5—H5B | 109.5 | C25—C24—H24 | 119.8 |
C4—C5—H5C | 109.5 | C24—C25—C26 | 120.1 (2) |
H5A—C5—H5C | 109.5 | C24—C25—H25 | 119.9 |
H5B—C5—H5C | 109.5 | C26—C25—H25 | 119.9 |
C4—C6—H6A | 109.5 | C25—C26—C21 | 120.04 (19) |
C4—C6—H6B | 109.5 | C25—C26—H26 | 120.0 |
H6A—C6—H6B | 109.5 | C21—C26—H26 | 120.0 |
C4—C6—H6C | 109.5 | C36—C31—C32 | 119.25 (18) |
H6A—C6—H6C | 109.5 | C36—C31—P1 | 121.82 (15) |
H6B—C6—H6C | 109.5 | C32—C31—P1 | 118.91 (14) |
C4—C7—H7A | 109.5 | C31—C32—C33 | 119.4 (2) |
C4—C7—H7B | 109.5 | C31—C32—H32 | 120.3 |
H7A—C7—H7B | 109.5 | C33—C32—H32 | 120.3 |
C4—C7—H7C | 109.5 | C34—C33—C32 | 121.0 (2) |
H7A—C7—H7C | 109.5 | C34—C33—H33 | 119.5 |
H7B—C7—H7C | 109.5 | C32—C33—H33 | 119.5 |
O3—C8—H8A | 109.5 | C33—C34—C35 | 120.1 (2) |
O3—C8—H8B | 109.5 | C33—C34—H34 | 120.0 |
H8A—C8—H8B | 109.5 | C35—C34—H34 | 120.0 |
O3—C8—H8C | 109.5 | C34—C35—C36 | 120.1 (2) |
H8A—C8—H8C | 109.5 | C34—C35—H35 | 119.9 |
H8B—C8—H8C | 109.5 | C36—C35—H35 | 119.9 |
C16—C11—C12 | 119.09 (16) | C31—C36—C35 | 120.2 (2) |
C16—C11—P1 | 118.67 (13) | C31—C36—H36 | 119.9 |
C12—C11—P1 | 122.16 (13) | C35—C36—H36 | 119.9 |
C13—C12—C11 | 120.58 (17) | | |
| | | |
C11—P1—C1—C3 | −94.67 (15) | C14—C15—C16—C11 | −0.4 (4) |
C21—P1—C1—C3 | 24.74 (16) | C12—C11—C16—C15 | 0.8 (3) |
C31—P1—C1—C3 | 142.52 (14) | P1—C11—C16—C15 | 177.62 (19) |
C11—P1—C1—C2 | 73.63 (15) | C1—P1—C21—C22 | 89.73 (16) |
C21—P1—C1—C2 | −166.96 (13) | C11—P1—C21—C22 | −147.19 (15) |
C31—P1—C1—C2 | −49.18 (15) | C31—P1—C21—C22 | −31.27 (17) |
C4—O1—C2—O2 | −1.5 (3) | C1—P1—C21—C26 | −90.24 (16) |
C4—O1—C2—C1 | 179.97 (17) | C11—P1—C21—C26 | 32.84 (16) |
C3—C1—C2—O2 | −11.8 (3) | C31—P1—C21—C26 | 148.75 (15) |
P1—C1—C2—O2 | −179.49 (15) | C26—C21—C22—C23 | 0.5 (3) |
C3—C1—C2—O1 | 166.58 (16) | P1—C21—C22—C23 | −179.50 (16) |
P1—C1—C2—O1 | −1.12 (19) | C21—C22—C23—C24 | −0.3 (3) |
C8—O3—C3—O4 | −0.7 (3) | C22—C23—C24—C25 | 0.0 (4) |
C8—O3—C3—C1 | −177.8 (2) | C23—C24—C25—C26 | 0.3 (4) |
C2—C1—C3—O4 | −158.2 (3) | C24—C25—C26—C21 | −0.1 (3) |
P1—C1—C3—O4 | 9.6 (3) | C22—C21—C26—C25 | −0.2 (3) |
C2—C1—C3—O3 | 18.6 (3) | P1—C21—C26—C25 | 179.73 (15) |
P1—C1—C3—O3 | −173.51 (14) | C1—P1—C31—C36 | 149.13 (17) |
C2—O1—C4—C7 | −57.8 (3) | C11—P1—C31—C36 | 25.08 (19) |
C2—O1—C4—C6 | 67.6 (3) | C21—P1—C31—C36 | −87.72 (18) |
C2—O1—C4—C5 | −174.9 (2) | C1—P1—C31—C32 | −32.46 (18) |
C1—P1—C11—C16 | −7.33 (18) | C11—P1—C31—C32 | −156.51 (15) |
C21—P1—C11—C16 | −131.61 (15) | C21—P1—C31—C32 | 90.70 (16) |
C31—P1—C11—C16 | 115.91 (16) | C36—C31—C32—C33 | −0.9 (3) |
C1—P1—C11—C12 | 169.37 (15) | P1—C31—C32—C33 | −179.39 (16) |
C21—P1—C11—C12 | 45.09 (17) | C31—C32—C33—C34 | 0.1 (3) |
C31—P1—C11—C12 | −67.39 (17) | C32—C33—C34—C35 | 1.2 (4) |
C16—C11—C12—C13 | −1.0 (3) | C33—C34—C35—C36 | −1.7 (4) |
P1—C11—C12—C13 | −177.70 (17) | C32—C31—C36—C35 | 0.5 (3) |
C11—C12—C13—C14 | 0.8 (4) | P1—C31—C36—C35 | 178.9 (2) |
C12—C13—C14—C15 | −0.3 (4) | C34—C35—C36—C31 | 0.8 (4) |
C13—C14—C15—C16 | 0.2 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | | | 2.729 (2) | |
P1···O4 | | | 2.986 (2) | |
C5—H5C···Cg3 | 0.96 | 2.99 | 3.788 (3) | 141 |
C23—H23···O2i | 0.93 | 2.56 | 3.424 (2) | 154 |
C25—H25···O4ii | 0.93 | 2.39 | 3.255 (3) | 155 |
C34—H34···O2iii | 0.93 | 2.59 | 3.511 (3) | 171 |
C13—H13···O3iv | 0.93 | 2.54 | 3.455 (3) | 166 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1/2. |
(IIb) ethyl
tert-butyl 2-(triphenylphosphoranyliden)malonate
top
Crystal data top
C27H29O4P | Z = 2 |
Mr = 448.47 | F(000) = 476 |
Triclinic, P1 | Dx = 1.231 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9616 (7) Å | Cell parameters from 2361 reflections |
b = 10.3589 (8) Å | θ = 2.3–23.8° |
c = 14.5644 (11) Å | µ = 0.14 mm−1 |
α = 97.388 (2)° | T = 140 K |
β = 107.705 (3)° | Block, colourless |
γ = 105.338 (2)° | 0.20 × 0.18 × 0.14 mm |
V = 1209.55 (16) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3919 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 27.9°, θmin = 2.1° |
ϕ and ω scans | h = −11→11 |
10154 measured reflections | k = −13→13 |
5183 independent reflections | l = −18→18 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.070P)2 + 0.1417P] where P = (Fo2 + 2Fc2)/3 |
5183 reflections | (Δ/σ)max = 0.018 |
299 parameters | Δρmax = 0.36 e Å−3 |
3 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C27H29O4P | γ = 105.338 (2)° |
Mr = 448.47 | V = 1209.55 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9616 (7) Å | Mo Kα radiation |
b = 10.3589 (8) Å | µ = 0.14 mm−1 |
c = 14.5644 (11) Å | T = 140 K |
α = 97.388 (2)° | 0.20 × 0.18 × 0.14 mm |
β = 107.705 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3919 reflections with I > 2σ(I) |
10154 measured reflections | Rint = 0.019 |
5183 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 3 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.36 e Å−3 |
5183 reflections | Δρmin = −0.16 e Å−3 |
299 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 | Occ. (<1) |
P1 | 0.42921 (4) | 0.76990 (4) | 0.21270 (3) | 0.03683 (9) | |
O1 | 0.61257 (12) | 0.58687 (10) | 0.27373 (8) | 0.0503 (3) | |
O2 | 0.84030 (12) | 0.68548 (12) | 0.24039 (9) | 0.0627 (3) | |
O3 | 0.89536 (17) | 0.95837 (9) | 0.25831 (11) | 0.0572 (4) | 0.747 (4) |
C8 | 0.9971 (3) | 1.10238 (17) | 0.29425 (10) | 0.0817 (7) | 0.747 (4) |
H8A | 1.0887 | 1.1173 | 0.2703 | 0.098* | 0.747 (4) |
H8B | 0.9315 | 1.1587 | 0.2671 | 0.098* | 0.747 (4) |
C9 | 1.0620 (4) | 1.1465 (4) | 0.40136 (14) | 0.0982 (11) | 0.747 (4) |
H9A | 1.1305 | 1.2410 | 0.4207 | 0.147* | 0.747 (4) |
H9B | 1.1265 | 1.0908 | 0.4289 | 0.147* | 0.747 (4) |
H9C | 0.9720 | 1.1367 | 0.4254 | 0.147* | 0.747 (4) |
O3' | 0.8921 (5) | 0.97469 (16) | 0.2822 (3) | 0.0572 (4) | 0.253 (4) |
C8' | 1.0056 (6) | 1.1099 (3) | 0.2922 (3) | 0.0817 (7) | 0.253 (4) |
H8'A | 1.1063 | 1.1042 | 0.2825 | 0.098* | 0.253 (4) |
H8'B | 0.9546 | 1.1598 | 0.2469 | 0.098* | 0.253 (4) |
C9' | 1.0355 (14) | 1.1705 (14) | 0.3943 (4) | 0.0982 (11) | 0.253 (4) |
H9'A | 1.1079 | 1.2637 | 0.4118 | 0.147* | 0.253 (4) |
H9'B | 1.0860 | 1.1186 | 0.4368 | 0.147* | 0.253 (4) |
H9'C | 0.9324 | 1.1695 | 0.4017 | 0.147* | 0.253 (4) |
O4 | 0.67961 (12) | 1.03388 (11) | 0.26410 (8) | 0.0535 (3) | |
C1 | 0.63747 (16) | 0.79704 (14) | 0.23226 (10) | 0.0389 (3) | |
C2 | 0.71058 (17) | 0.68898 (15) | 0.24759 (11) | 0.0437 (4) | |
C3 | 0.73341 (17) | 0.93876 (16) | 0.25398 (11) | 0.0434 (4) | |
C4 | 0.6506 (2) | 0.45896 (17) | 0.28767 (14) | 0.0604 (5) | |
C5 | 0.5013 (3) | 0.3781 (2) | 0.30767 (18) | 0.0906 (7) | |
H5A | 0.4969 | 0.4265 | 0.3671 | 0.136* | |
H5B | 0.5095 | 0.2894 | 0.3156 | 0.136* | |
H5C | 0.4027 | 0.3670 | 0.2531 | 0.136* | |
C6 | 0.6591 (3) | 0.3845 (2) | 0.19436 (17) | 0.0876 (7) | |
H6A | 0.7545 | 0.4366 | 0.1825 | 0.131* | |
H6B | 0.5610 | 0.3740 | 0.1395 | 0.131* | |
H6C | 0.6671 | 0.2955 | 0.2016 | 0.131* | |
C7 | 0.8083 (3) | 0.4914 (2) | 0.37591 (19) | 0.1079 (9) | |
H7A | 0.7975 | 0.5395 | 0.4332 | 0.162* | |
H7B | 0.8995 | 0.5478 | 0.3624 | 0.162* | |
H7C | 0.8280 | 0.4074 | 0.3880 | 0.162* | |
C11 | 0.38572 (16) | 0.79984 (15) | 0.32493 (10) | 0.0408 (4) | |
C12 | 0.23174 (17) | 0.80506 (16) | 0.32664 (12) | 0.0484 (4) | |
H12 | 0.1475 | 0.7972 | 0.2679 | 0.058* | |
C13 | 0.2051 (2) | 0.82173 (17) | 0.41457 (12) | 0.0557 (4) | |
H13 | 0.1027 | 0.8250 | 0.4152 | 0.067* | |
C14 | 0.3288 (2) | 0.83371 (18) | 0.50179 (13) | 0.0601 (5) | |
H14 | 0.3101 | 0.8453 | 0.5613 | 0.072* | |
C15 | 0.4802 (2) | 0.82852 (19) | 0.50116 (12) | 0.0600 (5) | |
H15 | 0.5637 | 0.8365 | 0.5603 | 0.072* | |
C16 | 0.50869 (18) | 0.81148 (16) | 0.41330 (11) | 0.0479 (4) | |
H16 | 0.6113 | 0.8078 | 0.4134 | 0.058* | |
C21 | 0.35241 (16) | 0.87693 (14) | 0.13323 (10) | 0.0387 (3) | |
C22 | 0.35132 (18) | 0.85366 (16) | 0.03733 (11) | 0.0482 (4) | |
H22 | 0.3908 | 0.7853 | 0.0161 | 0.058* | |
C23 | 0.2925 (2) | 0.93023 (17) | −0.02746 (12) | 0.0541 (4) | |
H23 | 0.2928 | 0.9135 | −0.0917 | 0.065* | |
C24 | 0.2337 (2) | 1.03107 (17) | 0.00327 (13) | 0.0584 (5) | |
H24 | 0.1929 | 1.0823 | −0.0403 | 0.070* | |
C25 | 0.2354 (2) | 1.05596 (18) | 0.09807 (14) | 0.0659 (5) | |
H25 | 0.1954 | 1.1243 | 0.1187 | 0.079* | |
C26 | 0.2958 (2) | 0.98094 (17) | 0.16349 (12) | 0.0549 (4) | |
H26 | 0.2984 | 1.0003 | 0.2282 | 0.066* | |
C31 | 0.30318 (16) | 0.59683 (14) | 0.14338 (11) | 0.0408 (4) | |
C32 | 0.16589 (19) | 0.52632 (17) | 0.16322 (13) | 0.0542 (4) | |
H32 | 0.1432 | 0.5649 | 0.2166 | 0.065* | |
C33 | 0.0628 (2) | 0.39923 (18) | 0.10418 (15) | 0.0628 (5) | |
H33 | −0.0288 | 0.3526 | 0.1182 | 0.075* | |
C34 | 0.0946 (2) | 0.34161 (17) | 0.02529 (14) | 0.0603 (5) | |
H34 | 0.0238 | 0.2567 | −0.0149 | 0.072* | |
C35 | 0.2306 (2) | 0.40903 (17) | 0.00554 (13) | 0.0578 (5) | |
H35 | 0.2525 | 0.3693 | −0.0478 | 0.069* | |
C36 | 0.33556 (19) | 0.53558 (16) | 0.06426 (11) | 0.0491 (4) | |
H36 | 0.4285 | 0.5801 | 0.0508 | 0.059* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.03210 (16) | 0.03876 (18) | 0.03629 (18) | 0.00930 (14) | 0.00937 (14) | 0.00832 (14) |
O1 | 0.0479 (5) | 0.0490 (5) | 0.0612 (6) | 0.0198 (4) | 0.0214 (5) | 0.0227 (5) |
O2 | 0.0406 (5) | 0.0616 (7) | 0.0897 (8) | 0.0200 (5) | 0.0248 (5) | 0.0179 (6) |
O3 | 0.0395 (5) | 0.0494 (7) | 0.0758 (9) | 0.0041 (5) | 0.0276 (6) | −0.0050 (6) |
C8 | 0.0526 (10) | 0.0702 (13) | 0.1054 (16) | −0.0009 (10) | 0.0298 (10) | 0.0010 (11) |
C9 | 0.0669 (16) | 0.102 (2) | 0.1039 (19) | 0.0286 (15) | 0.0094 (14) | −0.0035 (16) |
O3' | 0.0395 (5) | 0.0494 (7) | 0.0758 (9) | 0.0041 (5) | 0.0276 (6) | −0.0050 (6) |
C8' | 0.0526 (10) | 0.0702 (13) | 0.1054 (16) | −0.0009 (10) | 0.0298 (10) | 0.0010 (11) |
C9' | 0.0669 (16) | 0.102 (2) | 0.1039 (19) | 0.0286 (15) | 0.0094 (14) | −0.0035 (16) |
O4 | 0.0471 (5) | 0.0440 (6) | 0.0600 (7) | 0.0109 (5) | 0.0110 (5) | 0.0072 (5) |
C1 | 0.0329 (6) | 0.0424 (7) | 0.0394 (7) | 0.0101 (6) | 0.0116 (5) | 0.0103 (6) |
C2 | 0.0338 (7) | 0.0491 (8) | 0.0424 (8) | 0.0101 (6) | 0.0097 (6) | 0.0070 (6) |
C3 | 0.0370 (7) | 0.0475 (8) | 0.0402 (8) | 0.0081 (6) | 0.0112 (6) | 0.0089 (6) |
C4 | 0.0587 (9) | 0.0517 (9) | 0.0688 (11) | 0.0229 (7) | 0.0108 (8) | 0.0250 (8) |
C5 | 0.0988 (14) | 0.0734 (12) | 0.1100 (16) | 0.0247 (11) | 0.0420 (12) | 0.0494 (11) |
C6 | 0.1047 (14) | 0.0654 (12) | 0.1031 (16) | 0.0413 (11) | 0.0407 (12) | 0.0157 (11) |
C7 | 0.0982 (16) | 0.0875 (14) | 0.1065 (18) | 0.0310 (13) | −0.0155 (14) | 0.0405 (13) |
C11 | 0.0376 (7) | 0.0405 (7) | 0.0401 (7) | 0.0080 (6) | 0.0124 (6) | 0.0079 (6) |
C12 | 0.0400 (7) | 0.0541 (9) | 0.0475 (8) | 0.0128 (7) | 0.0144 (6) | 0.0073 (7) |
C13 | 0.0502 (8) | 0.0595 (10) | 0.0609 (9) | 0.0147 (7) | 0.0283 (7) | 0.0102 (8) |
C14 | 0.0696 (9) | 0.0676 (11) | 0.0509 (9) | 0.0199 (8) | 0.0329 (8) | 0.0158 (8) |
C15 | 0.0606 (9) | 0.0758 (11) | 0.0419 (8) | 0.0204 (8) | 0.0150 (7) | 0.0188 (8) |
C16 | 0.0432 (7) | 0.0581 (9) | 0.0423 (8) | 0.0162 (7) | 0.0138 (6) | 0.0137 (7) |
C21 | 0.0306 (6) | 0.0374 (7) | 0.0412 (7) | 0.0066 (5) | 0.0071 (5) | 0.0081 (6) |
C22 | 0.0521 (8) | 0.0468 (8) | 0.0477 (8) | 0.0169 (7) | 0.0184 (7) | 0.0132 (6) |
C23 | 0.0605 (9) | 0.0559 (9) | 0.0459 (8) | 0.0176 (7) | 0.0161 (7) | 0.0198 (7) |
C24 | 0.0581 (9) | 0.0533 (9) | 0.0616 (10) | 0.0205 (7) | 0.0111 (8) | 0.0242 (7) |
C25 | 0.0835 (11) | 0.0590 (9) | 0.0676 (11) | 0.0420 (8) | 0.0254 (9) | 0.0195 (8) |
C26 | 0.0674 (9) | 0.0540 (9) | 0.0492 (9) | 0.0301 (7) | 0.0196 (7) | 0.0120 (7) |
C31 | 0.0358 (6) | 0.0400 (7) | 0.0426 (7) | 0.0123 (6) | 0.0076 (6) | 0.0112 (6) |
C32 | 0.0445 (8) | 0.0483 (9) | 0.0643 (10) | 0.0079 (7) | 0.0201 (7) | 0.0070 (7) |
C33 | 0.0455 (8) | 0.0467 (9) | 0.0871 (13) | 0.0041 (7) | 0.0226 (8) | 0.0084 (9) |
C34 | 0.0491 (9) | 0.0414 (9) | 0.0692 (11) | 0.0098 (7) | 0.0002 (8) | 0.0018 (8) |
C35 | 0.0642 (10) | 0.0468 (9) | 0.0529 (9) | 0.0174 (8) | 0.0122 (8) | 0.0004 (7) |
C36 | 0.0492 (8) | 0.0458 (8) | 0.0475 (8) | 0.0109 (7) | 0.0156 (7) | 0.0078 (7) |
Geometric parameters (Å, º) top
P1—C1 | 1.7383 (14) | C7—H7B | 0.9600 |
P1—C11 | 1.8004 (15) | C7—H7C | 0.9600 |
P1—C31 | 1.8107 (14) | C11—C16 | 1.383 (2) |
P1—C21 | 1.8142 (15) | C11—C12 | 1.403 (2) |
O1—C2 | 1.3603 (18) | C12—C13 | 1.370 (2) |
O1—C4 | 1.476 (2) | C12—H12 | 0.9300 |
O2—C2 | 1.2080 (18) | C13—C14 | 1.374 (2) |
O3—C3 | 1.392 (2) | C13—H13 | 0.9300 |
O3—C8 | 1.4560 (17) | C14—C15 | 1.374 (2) |
C8—C9 | 1.451 (2) | C14—H14 | 0.9300 |
C8—H8A | 0.9700 | C15—C16 | 1.378 (2) |
C8—H8B | 0.9700 | C15—H15 | 0.9300 |
C9—H9A | 0.9600 | C16—H16 | 0.9300 |
C9—H9B | 0.9600 | C21—C22 | 1.383 (2) |
C9—H9C | 0.9600 | C21—C26 | 1.384 (2) |
O3'—C3 | 1.287 (4) | C22—C23 | 1.381 (2) |
O3'—C8' | 1.4560 (19) | C22—H22 | 0.9300 |
C8'—C9' | 1.451 (2) | C23—C24 | 1.373 (2) |
C8'—H8'A | 0.9700 | C23—H23 | 0.9300 |
C8'—H8'B | 0.9700 | C24—C25 | 1.366 (3) |
C9'—H9'A | 0.9600 | C24—H24 | 0.9300 |
C9'—H9'B | 0.9600 | C25—C26 | 1.380 (2) |
C9'—H9'C | 0.9600 | C25—H25 | 0.9300 |
O4—C3 | 1.2174 (19) | C26—H26 | 0.9300 |
C1—C3 | 1.429 (2) | C31—C32 | 1.388 (2) |
C1—C2 | 1.448 (2) | C31—C36 | 1.388 (2) |
C4—C6 | 1.507 (3) | C32—C33 | 1.381 (2) |
C4—C5 | 1.511 (3) | C32—H32 | 0.9300 |
C4—C7 | 1.515 (3) | C33—C34 | 1.368 (3) |
C5—H5A | 0.9600 | C33—H33 | 0.9300 |
C5—H5B | 0.9600 | C34—C35 | 1.368 (2) |
C5—H5C | 0.9600 | C34—H34 | 0.9300 |
C6—H6A | 0.9600 | C35—C36 | 1.380 (2) |
C6—H6B | 0.9600 | C35—H35 | 0.9300 |
C6—H6C | 0.9600 | C36—H36 | 0.9300 |
C7—H7A | 0.9600 | | |
| | | |
C1—P1—C11 | 113.80 (6) | H6B—C6—H6C | 109.5 |
C1—P1—C31 | 111.58 (7) | C4—C7—H7A | 109.5 |
C11—P1—C31 | 107.85 (7) | C4—C7—H7B | 109.5 |
C1—P1—C21 | 110.05 (7) | H7A—C7—H7B | 109.5 |
C11—P1—C21 | 109.51 (7) | C4—C7—H7C | 109.5 |
C31—P1—C21 | 103.53 (6) | H7A—C7—H7C | 109.5 |
C2—O1—C4 | 122.35 (13) | H7B—C7—H7C | 109.5 |
C3—O3—C8 | 112.12 (16) | C16—C11—C12 | 118.70 (14) |
C9—C8—O3 | 113.2 (2) | C16—C11—P1 | 117.81 (12) |
C9—C8—H8A | 108.9 | C12—C11—P1 | 123.41 (11) |
O3—C8—H8A | 108.9 | C13—C12—C11 | 120.20 (14) |
C9—C8—H8B | 108.9 | C13—C12—H12 | 119.9 |
O3—C8—H8B | 108.9 | C11—C12—H12 | 119.9 |
H8A—C8—H8B | 107.7 | C12—C13—C14 | 120.39 (16) |
C8—C9—H9A | 109.5 | C12—C13—H13 | 119.8 |
C8—C9—H9B | 109.5 | C14—C13—H13 | 119.8 |
H9A—C9—H9B | 109.5 | C13—C14—C15 | 120.02 (16) |
C8—C9—H9C | 109.5 | C13—C14—H14 | 120.0 |
H9A—C9—H9C | 109.5 | C15—C14—H14 | 120.0 |
H9B—C9—H9C | 109.5 | C14—C15—C16 | 120.26 (15) |
C3—O3'—C8' | 127.1 (3) | C14—C15—H15 | 119.9 |
C9'—C8'—O3' | 99.5 (6) | C16—C15—H15 | 119.9 |
C9'—C8'—H8'A | 111.9 | C15—C16—C11 | 120.44 (15) |
O3'—C8'—H8'A | 111.9 | C15—C16—H16 | 119.8 |
C9'—C8'—H8'B | 111.8 | C11—C16—H16 | 119.8 |
O3'—C8'—H8'B | 111.9 | C22—C21—C26 | 118.28 (14) |
H8'A—C8'—H8'B | 109.6 | C22—C21—P1 | 118.11 (12) |
C8'—C9'—H9'A | 109.5 | C26—C21—P1 | 123.61 (12) |
C8'—C9'—H9'B | 109.5 | C23—C22—C21 | 121.10 (16) |
H9'A—C9'—H9'B | 109.5 | C23—C22—H22 | 119.4 |
C8'—C9'—H9'C | 109.5 | C21—C22—H22 | 119.5 |
H9'A—C9'—H9'C | 109.5 | C24—C23—C22 | 119.78 (16) |
H9'B—C9'—H9'C | 109.5 | C24—C23—H23 | 120.1 |
C3—C1—C2 | 123.02 (12) | C22—C23—H23 | 120.1 |
C3—C1—P1 | 113.73 (11) | C25—C24—C23 | 119.73 (16) |
C2—C1—P1 | 121.77 (10) | C25—C24—H24 | 120.1 |
O2—C2—O1 | 122.42 (15) | C23—C24—H24 | 120.1 |
O2—C2—C1 | 127.20 (15) | C24—C25—C26 | 120.77 (17) |
O1—C2—C1 | 110.38 (12) | C24—C25—H25 | 119.6 |
O4—C3—O3' | 114.29 (16) | C26—C25—H25 | 119.6 |
O4—C3—O3 | 122.50 (13) | C25—C26—C21 | 120.31 (16) |
O4—C3—C1 | 124.35 (13) | C25—C26—H26 | 119.8 |
O3'—C3—C1 | 120.22 (15) | C21—C26—H26 | 119.8 |
O3—C3—C1 | 113.09 (13) | C32—C31—C36 | 118.47 (13) |
O1—C4—C6 | 110.87 (15) | C32—C31—P1 | 121.13 (12) |
O1—C4—C5 | 101.49 (15) | C36—C31—P1 | 120.25 (11) |
C6—C4—C5 | 110.16 (16) | C33—C32—C31 | 120.42 (17) |
O1—C4—C7 | 109.66 (14) | C33—C32—H32 | 119.8 |
C6—C4—C7 | 112.54 (19) | C31—C32—H32 | 119.8 |
C5—C4—C7 | 111.59 (18) | C34—C33—C32 | 120.36 (16) |
C4—C5—H5A | 109.5 | C34—C33—H33 | 119.8 |
C4—C5—H5B | 109.5 | C32—C33—H33 | 119.8 |
H5A—C5—H5B | 109.5 | C33—C34—C35 | 119.91 (15) |
C4—C5—H5C | 109.5 | C33—C34—H34 | 120.0 |
H5A—C5—H5C | 109.5 | C35—C34—H34 | 120.0 |
H5B—C5—H5C | 109.5 | C34—C35—C36 | 120.46 (17) |
C4—C6—H6A | 109.5 | C34—C35—H35 | 119.8 |
C4—C6—H6B | 109.5 | C36—C35—H35 | 119.8 |
H6A—C6—H6B | 109.5 | C35—C36—C31 | 120.36 (15) |
C4—C6—H6C | 109.5 | C35—C36—H36 | 119.8 |
H6A—C6—H6C | 109.5 | C31—C36—H36 | 119.8 |
| | | |
C3—O3—C8—C9 | 82.8 (3) | P1—C11—C12—C13 | 176.87 (12) |
C3—O3'—C8'—C9' | 89.8 (7) | C11—C12—C13—C14 | 0.1 (2) |
C11—P1—C1—C3 | −78.64 (12) | C12—C13—C14—C15 | −0.2 (3) |
C31—P1—C1—C3 | 159.04 (11) | C13—C14—C15—C16 | 0.1 (3) |
C21—P1—C1—C3 | 44.70 (13) | C14—C15—C16—C11 | 0.2 (3) |
C11—P1—C1—C2 | 87.90 (13) | C12—C11—C16—C15 | −0.3 (2) |
C31—P1—C1—C2 | −34.42 (14) | P1—C11—C16—C15 | −177.20 (13) |
C21—P1—C1—C2 | −148.77 (12) | C1—P1—C21—C22 | 63.88 (12) |
C4—O1—C2—O2 | −4.9 (2) | C11—P1—C21—C22 | −170.31 (10) |
C4—O1—C2—C1 | 175.87 (12) | C31—P1—C21—C22 | −55.49 (12) |
C3—C1—C2—O2 | −32.2 (2) | C1—P1—C21—C26 | −115.75 (13) |
P1—C1—C2—O2 | 162.53 (13) | C11—P1—C21—C26 | 10.05 (14) |
C3—C1—C2—O1 | 146.98 (14) | C31—P1—C21—C26 | 124.87 (13) |
P1—C1—C2—O1 | −18.30 (17) | C26—C21—C22—C23 | −1.2 (2) |
C8'—O3'—C3—O4 | −22.0 (5) | P1—C21—C22—C23 | 179.17 (11) |
C8'—O3'—C3—O3 | 103.0 (5) | C21—C22—C23—C24 | −0.1 (2) |
C8'—O3'—C3—C1 | 169.7 (3) | C22—C23—C24—C25 | 0.7 (2) |
C8—O3—C3—O4 | 10.9 (2) | C23—C24—C25—C26 | 0.1 (3) |
C8—O3—C3—O3' | −51.4 (2) | C24—C25—C26—C21 | −1.4 (3) |
C8—O3—C3—C1 | −171.79 (13) | C22—C21—C26—C25 | 1.9 (2) |
C2—C1—C3—O4 | −162.15 (15) | P1—C21—C26—C25 | −178.43 (13) |
P1—C1—C3—O4 | 4.2 (2) | C1—P1—C31—C32 | 143.80 (13) |
C2—C1—C3—O3' | 4.9 (3) | C11—P1—C31—C32 | 18.12 (15) |
P1—C1—C3—O3' | 171.3 (2) | C21—P1—C31—C32 | −97.89 (14) |
C2—C1—C3—O3 | 20.5 (2) | C1—P1—C31—C36 | −40.81 (14) |
P1—C1—C3—O3 | −173.11 (11) | C11—P1—C31—C36 | −166.49 (12) |
C2—O1—C4—C6 | −58.90 (18) | C21—P1—C31—C36 | 77.51 (13) |
C2—O1—C4—C5 | −175.89 (14) | C36—C31—C32—C33 | −1.1 (2) |
C2—O1—C4—C7 | 66.0 (2) | P1—C31—C32—C33 | 174.34 (14) |
C1—P1—C11—C16 | −13.50 (15) | C31—C32—C33—C34 | −0.2 (3) |
C31—P1—C11—C16 | 110.86 (12) | C32—C33—C34—C35 | 1.0 (3) |
C21—P1—C11—C16 | −137.12 (12) | C33—C34—C35—C36 | −0.5 (3) |
C1—P1—C11—C12 | 169.76 (12) | C34—C35—C36—C31 | −0.8 (3) |
C31—P1—C11—C12 | −65.88 (14) | C32—C31—C36—C35 | 1.6 (2) |
C21—P1—C11—C12 | 46.14 (14) | P1—C31—C36—C35 | −173.87 (13) |
C16—C11—C12—C13 | 0.2 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | | | 2.877 (2) | |
P1···O4 | | | 2.877 (2) | |
C5—H5C···Cg3 | 0.96 | 3.07 | 3.944 (2) | 152 |
C34—H34···Cg2i | 0.93 | 2.90 | 3.712 (2) | 146 |
C12—H12···O2ii | 0.93 | 2.57 | 3.168 (2) | 123 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1, y, z. |
Experimental details
| (Ia) | (Ib) | (IIa) | (IIb) |
Crystal data |
Chemical formula | C25H25O4P | C26H27O4P | C26H27O4P | C27H29O4P |
Mr | 420.42 | 434.45 | 434.45 | 448.47 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 273 | 140 | 140 | 140 |
a, b, c (Å) | 9.8033 (6), 10.4492 (7), 11.2169 (7) | 12.5175 (16), 9.1555 (12), 20.351 (3) | 9.8140 (7), 15.889 (2), 15.404 (2) | 8.9616 (7), 10.3589 (8), 14.5644 (11) |
α, β, γ (°) | 100.573 (2), 94.878 (2), 102.446 (3) | 90, 96.342 (2), 90 | 90, 90.413 (2), 90 | 97.388 (2), 107.705 (3), 105.338 (2) |
V (Å3) | 1093.64 (12) | 2318.0 (5) | 2402.0 (5) | 1209.55 (16) |
Z | 2 | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.15 | 0.15 | 0.14 | 0.14 |
Crystal size (mm) | 0.20 × 0.17 × 0.14 | 0.18 × 0.16 × 0.16 | 0.16 × 0.16 × 0.16 | 0.20 × 0.18 × 0.14 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9176, 4675, 3133 | 19001, 5252, 2713 | 19840, 5292, 4501 | 10154, 5183, 3919 |
Rint | 0.025 | 0.053 | 0.021 | 0.019 |
(sin θ/λ)max (Å−1) | 0.655 | 0.662 | 0.657 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.134, 1.01 | 0.057, 0.140, 0.86 | 0.052, 0.144, 1.04 | 0.050, 0.136, 1.03 |
No. of reflections | 4675 | 5252 | 5292 | 5183 |
No. of parameters | 282 | 300 | 284 | 299 |
No. of restraints | 2 | 7 | 0 | 3 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.17 | 0.33, −0.27 | 0.60, −0.45 | 0.36, −0.16 |
Selected bond lengths (Å) for (Ia) topP1—C1 | 1.7388 (19) | C1—C3 | 1.436 (3) |
O2—C2 | 1.208 (2) | C1—C2 | 1.443 (3) |
O4—C3 | 1.211 (2) | | |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | . | . | 2.799 (2) | . |
P1···O4 | . | . | 3.030 (2) | . |
C5—H5C···Cg3 | 0.96 | 2.89 | 3.657 (3) | 138 |
C23—H23···O4i | 0.93 | 2.56 | 3.430 (3) | 156 |
Symmetry code: (i) −x, −y+1, −z+1. |
Selected bond lengths (Å) for (Ib) topP1—C1 | 1.741 (2) | C1—C3 | 1.425 (3) |
O2—C2 | 1.188 (3) | C1—C2 | 1.441 (3) |
O4—C3 | 1.228 (3) | | |
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | . | . | 2.953 (2) | . |
P1···O4 | . | . | 2.809 (2) | . |
C5—H5C···Cg3 | 0.96 | 2.93 | 3.663 (4) | 134 |
C25—H25···O4i | 0.93 | 2.40 | 3.323 (3) | 172.3 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
Selected bond lengths (Å) for (IIa) topP1—C1 | 1.7451 (16) | C1—C3 | 1.434 (2) |
O2—C2 | 1.211 (2) | C1—C2 | 1.447 (2) |
O4—C3 | 1.188 (2) | | |
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | . | . | 2.729 (2) | . |
P1···O4 | . | . | 2.986 (2) | . |
C5—H5C···Cg3 | 0.96 | 2.99 | 3.788 (3) | 141 |
C23—H23···O2i | 0.93 | 2.56 | 3.424 (2) | 154 |
C25—H25···O4ii | 0.93 | 2.39 | 3.255 (3) | 155 |
C34—H34···O2iii | 0.93 | 2.59 | 3.511 (3) | 171 |
C13—H13···O3iv | 0.93 | 2.54 | 3.455 (3) | 166 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1/2. |
Selected bond lengths (Å) for (IIb) topP1—C1 | 1.7383 (14) | C1—C3 | 1.429 (2) |
O2—C2 | 1.2080 (18) | C1—C2 | 1.448 (2) |
O4—C3 | 1.2174 (19) | | |
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···A | D—H | H···A | D···A | D—H···A |
P1···O1 | . | . | 2.877 (2) | . |
P1···O4 | . | . | 2.877 (2) | . |
C5—H5C···Cg3 | 0.96 | 3.07 | 3.944 (2) | 152 |
C34—H34···Cg2i | 0.93 | 2.90 | 3.712 (2) | 146 |
C12—H12···O2ii | 0.93 | 2.57 | 3.168 (2) | 123 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1, y, z. |
π–π contacts (Å, °) for (IIb) topGroup 1 | Group 2 | DA (°) | IPD (Å) | CCD (Å) |
Cg1 | Cg1ii | 0 | 3.386 | 3.974 (2) |
Cg3 | Cg3i | 0 | 3.663 | 3.937 (2) |
Cg1 and Cg3 are as defined in Fig. 1.
Symmetry codes: (i) -x, 1-y, -z, (ii) 1-x, 2-y, 1-z.
DA is the mean slippage angle, IPD is the mean interplanar distance and
CCD is the centre-to-centre distance (for details, see Janiak, 2000). |
The conformations of crystalline triphenylphosphonium ylides stabilized by electron-withdrawing groups such as ester, keto or cyano depend on the balance between electronic delocalization and intra- and intermolecular non-bonding interactions (Castañeda et al., 2003; Castañeda, Acuña et al., 2007). The bond between P and the ylidic C atom allows free rotation at ambient temperatures on the NMR time scale, indicating the inadequacy of a structure with a classical C═P double bond (Bachrach & Nitsche, 1994). In ylides stabilized by a single keto or ester group, there is a strong interaction between cationoid phosphorus and the syn acyl O atom (Wilson & Tebby, 1972; Zeliger et al., 1969), but syn–syn diesters have never been observed and are not shown, as in the first scheme for syn–anti and anti–anti mixtures. The crystal conformation is controlled by minor changes in the diester groups because the dimethyl ester is a 1:1 anti–anti:syn–anti mixture, in the methyl ethyl diester the acyl O atom of the methyl ester group is syn and that of the ethyl ester group is anti (Castañeda, Jullian et al., 2007), and in the diethyl ester both acyl O atoms are anti to the P atom (Castañeda et al., 2005). This limited evidence indicates that acyl groups can adopt either geometry, but the bulkier alkoxy group tends to be syn to P.
A series of diesters with methoxy, ethoxy, isopropoxy or tert-butoxy groups, methyl isopropyl-, ethyl isopropyl-, methyl tert-butyl- and ethyl tert-butyl 2-triphenylphosphoranylidene malonate diesters, Ph3P═C(CO2R)CO2R' (where R = Me or Et and R' = iPr or tBu), the title compounds (Ia)–(IIb), respectively, have been prepared and their structures analysed. Figs. 1, 3, 5 and 7 show the molecular structures of the compounds, while Figs. 2, 4, 6 and 8 present the corresponding packing views. Selected bond distances for (Ia), (Ib), (IIa) and (IIb) are given in Tables 1, 3, 5 and 7. Tables 2, 4, 6, 8 and 9 show the non-bonding interactions and short contacts relevant to the packing discussion.
In the crystals of these diesters, the bulkier alkoxy groups are oriented towards, and smaller alkoxy groups away from, the P atom. The ester groups have Z conformations, as is typical of carboxylic esters (Eliel & Wilen, 1994), and are approximately in the ylidic plane. The 1H and 13C NMR spectra of these diesters indicate that the conformations are the same in solution and the solid state, as detailed elsewhere (Reference?). The geometries of the crystalline diesters are governed by the balance between ylidic resonance and intra- and intermolecular interactions. As is generally the case, the C≐P bond lengths are in between those characteristic of single and double bonds (Howells et al., 1973) and in solution the 1H and 13C NMR signals indicate free rotation about this bond. However, in the crystal structure, the orientations of the phenyl groups are similar in the four ylides and are apparently insensitive to the bulkiness of the alkoxy ester groups.
To a first approximation, the bonds between the ylidic and acyl C atoms are in the same plane, consistent with important ylidic resonance. Some angles at these C atoms differ from the expected 120°, but the sum of the angles is approximately 360°. In earlier observations of ylidic diesters with methoxy or ethoxy substituents, we found that the bulkier alkoxy group was oriented towards the P atom (Castañeda, Jullian et al., 2007), and the present results fit this generalization. In the crystal structure, bulky alkoxy groups oriented away from the P atom would interfere both intra- and intermolecularly. Both isopropoxy and tert-butoxy groups are oriented towards the face of the phenyl group which is approximately orthogonal to the C≐P bond, as shown by the 1H NMR signals in solution (CDCl3). The bond lengths between ylidic and acyl C atoms are in between those typical of single and double bonds, as are those in the acyl groups (Howells et al., 1973).
Elsewhere, we show that computed interatomic distances and angles for isolated molecules are generally similar to those in the crystal structure (Reference?). Computations indicate that the conformations of isolated ylidic diesters have minor effects on their computed energies, indicating the role of intermolecular interactions in controlling conformation. Intramolecular interactions in the crystal structure, and probably also in solution, involve interactions between cationoid P and acyl and alkyl O atoms in the syn position, which slightly lengthens the acyl group syn to P relative to the anti acyl group, as shown by the relative lengths of O4—C3 and O2—C2. This generalization fails for the methyl tert-butyl diester, (IIa). There are also, in some diesters, intramolecular interactions between methyl H atoms and anti acyl O atoms. There are always intermolecular interactions between phenyl H atoms and the acyl O atoms of an adjacent molecule (Desiraju & Steiner, 1999). These interactions between phenyl H atoms and acyl O atoms are generally important and play key roles in determining the conformations of individual molecules and crystal structures (Castañeda, Jullian et al., 2007).
In the crystal structure of (Ib) (Fig. 4), one alkoxy group syn to P is directed towards the face of a phenyl group which is approximately orthogonal to the ylidic C—P bond. The consequent C—H—π interaction should be modestly stabilizing (Nishio et al., 1995, Nishio & Hirota, 1989) and is seen in a variety of diesters and keto esters. In the other ester residue, the syn-acyl group is oriented between two phenyl groups, and independent evidence indicates that for some diester ylides the geometries are similar for isolated molecules and in the crystal structure.
Due to the common skeleton, all four ylides exhibit analogous weak intramolecular interactions, viz. two short P···O contacts and one further C—H···π hydrogen bond between the terminal methyl H atom (C5—H5C) and the phenyl ring C31–C36 (Cg3) (entries 1–3 in Tables 2, 4, 6 and 8). There are, however, differences in the intermolecular interactions and the derived packing schemes. In (Ia) and (Ib), there is one non-conventional intermolecular C—H···O bond between the C21–C26 phenyl ring (Cg2) and atom O4, but it gives dissimilar packing schemes: in (Ia), hydrogen-bonded dimers are built up around a group of symmetry centres (Fig. 2), while for (Ib) it results in the formation of a chain around the screw axis running along the unique b axis (Fig. 4) In ylides (IIa) and (IIb), these interactions differ, viz. in (IIa), the preferred intermolecular contacts are non-conventional C—H···O bonds (Table 6,) while in (IIb) they are mainly C—H···π (Table 8) and π–π bonds (Table 9), and the crystal structures differ. In (IIa), the predominant C—H···O bonds are spread uniformly in four directions (Fig. 6), generating a homogeneously connected three-dimensional structure. In (IIb), dimeric structures are built up around a group of symmetry centres [at (0, 1/2, 0), Zone A in Fig. 8], connected into [111] chains by rather weak π–π bonds around the inversion centre at (1/2, 1, 1/2) (B in Fig. 8). Finally, weak hydrogen bonds with atom O2 as an acceptor link these chains, with their [100] translated homologues, into a two-dimensional structure parallel to the (011) plane.