The structures of three related keto diester and diester ylides, namely diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate, C
27H
27O
5P, (I), diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate acetic acid monosolvate, C
27H
27O
5P·C
2H
4O
2, (II), and diethyl 2-(triphenylphosphoranylidene)succinate, C
26H
27O
4P, (III), are presented. The
syn-keto
anti-ester conformations in the crystalline keto diesters are governed by electronic delocalization between the P—C and ylidic bonds and an acyl group, and by intra- and intermolecular interactions. There are also intramolecular attractive and repulsive interactions of different types (C—H
O and C—H
π) controlling the molecular conformations. The mono-ylidic diester (III) has an
anti-ester conformation, while those for (I) and (II) are related to pyrolytic formation of acetylene derivatives. The terminal nonylidic ester group in (I) was disordered over two sets of almost equally populated positions.
Supporting information
CCDC references: 842153; 842154; 842155
Diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate, (I) (m.p. 379 K, yield
68%), was prepared by reaction of carbethoxy methylene triphenylphosphorane,
Ph3P═CH—CO2Et, with ethyl malonyl chloride in dry benzene at room
temperature. Recrystallization of (I) from ethyl acetate–hexane (1:1
v/v) and then from acetic acid gave the solvate (II) (m.p. 433 K, yield 72%). Diethyl 2-(triphenylphosphoranylidene)succinate, (III) [m.p.
370 K, recrystallized from ethyl acetate–hexane (1:1 v/v),
yield 71%], was synthesized by transylidation of Ph3P═CH—CO2Et with
ethyl 2-bromoacetate in dry ethyl acetate at 313 K for 4 h. Elemental analyses
using a Fison EA 1108 analyser agreed with the determined structures of ylides
(I)–(III).
All H atoms were located from difference Fourier maps but were given different
treatment. H atoms bonded to C atoms were re-positioned at their geometrically
expected locations and allowed to ride, with C—H = 0.95–0.99 Å. The
acetic acid H atom bonded to O in (II) was refined with a restrained O—H
distance of 0.85 (2) Å. In all cases, Uiso(H) = 1.2 or
1.5Ueq(host). The terminal nonylidic ester group in (I) appeared
disordered in two almost equally populated moieties. They were refined with
soft similarity restraints on both interatomic distances and displacement
factors; refinement of the occupancy factors converged to 0.547 (3)/0.453 (3).
For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
(I) diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate
top
Crystal data top
C27H27O5P | Z = 2 |
Mr = 462.46 | F(000) = 488 |
Triclinic, P1 | Dx = 1.324 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0348 (10) Å | Cell parameters from 999 reflections |
b = 10.3770 (11) Å | θ = 4.7–50.4° |
c = 13.8951 (15) Å | µ = 0.16 mm−1 |
α = 95.994 (2)° | T = 150 K |
β = 108.342 (2)° | Block, colourless |
γ = 107.304 (2)° | 0.46 × 0.26 × 0.19 mm |
V = 1152.0 (2) Å3 | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 4935 independent reflections |
Radiation source: fine-focus sealed tube | 4077 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 27.8°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −11→11 |
Tmin = 0.95, Tmax = 0.97 | k = −13→13 |
9669 measured reflections | l = −17→17 |
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) = 0.143 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0842P)2 + 0.1991P] where P = (Fo2 + 2Fc2)/3 |
4935 reflections | (Δ/σ)max < 0.001 |
344 parameters | Δρmax = 1.05 e Å−3 |
122 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C27H27O5P | γ = 107.304 (2)° |
Mr = 462.46 | V = 1152.0 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.0348 (10) Å | Mo Kα radiation |
b = 10.3770 (11) Å | µ = 0.16 mm−1 |
c = 13.8951 (15) Å | T = 150 K |
α = 95.994 (2)° | 0.46 × 0.26 × 0.19 mm |
β = 108.342 (2)° | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 4935 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 4077 reflections with I > 2σ(I) |
Tmin = 0.95, Tmax = 0.97 | Rint = 0.021 |
9669 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 122 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.05 e Å−3 |
4935 reflections | Δρmin = −0.36 e Å−3 |
344 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
P1 | 0.43699 (5) | 0.76211 (5) | 0.22355 (3) | 0.01890 (15) | |
O1 | 0.60655 (18) | 0.57204 (15) | 0.28402 (12) | 0.0319 (3) | |
O2 | 0.85107 (17) | 0.68184 (15) | 0.26865 (12) | 0.0357 (4) | |
O4 | 0.69330 (17) | 1.02793 (14) | 0.26856 (11) | 0.0287 (3) | |
O5' | 1.0387 (4) | 1.1795 (3) | 0.2456 (3) | 0.0466 (9) | 0.522 (3) |
O6' | 1.0466 (4) | 1.2061 (3) | 0.4096 (2) | 0.0448 (9) | 0.522 (3) |
C7' | 1.0133 (6) | 1.1269 (4) | 0.3171 (3) | 0.0363 (10) | 0.522 (3) |
C8' | 1.0897 (7) | 1.3581 (5) | 0.4079 (5) | 0.0487 (13) | 0.522 (3) |
H8'A | 1.0234 | 1.3682 | 0.3392 | 0.058* | 0.522 (3) |
H8'B | 1.0598 | 1.4044 | 0.4611 | 0.058* | 0.522 (3) |
C9' | 1.2716 (5) | 1.4276 (4) | 0.4286 (4) | 0.0344 (10) | 0.522 (3) |
H9'A | 1.2941 | 1.5251 | 0.4253 | 0.052* | 0.522 (3) |
H9'B | 1.3018 | 1.3818 | 0.3762 | 0.052* | 0.522 (3) |
H9'C | 1.3375 | 1.4212 | 0.4978 | 0.052* | 0.522 (3) |
O5" | 1.0525 (4) | 1.1333 (3) | 0.4583 (2) | 0.0329 (8) | 0.478 (3) |
O6" | 1.0821 (6) | 1.2074 (4) | 0.3177 (3) | 0.0615 (11) | 0.478 (3) |
C7" | 1.0264 (6) | 1.1140 (4) | 0.3679 (3) | 0.0361 (10) | 0.478 (3) |
C8" | 1.1871 (8) | 1.3464 (6) | 0.3887 (5) | 0.0636 (15) | 0.478 (3) |
H8"A | 1.2501 | 1.3374 | 0.4586 | 0.076* | 0.478 (3) |
H8"B | 1.2658 | 1.4017 | 0.3598 | 0.076* | 0.478 (3) |
C9" | 1.0600 (8) | 1.4085 (7) | 0.3918 (6) | 0.0616 (18) | 0.478 (3) |
H9"A | 1.1148 | 1.5007 | 0.4378 | 0.092* | 0.478 (3) |
H9"B | 0.9814 | 1.3497 | 0.4180 | 0.092* | 0.478 (3) |
H9"C | 0.9998 | 1.4162 | 0.3217 | 0.092* | 0.478 (3) |
C1 | 0.6476 (2) | 0.79089 (19) | 0.24580 (14) | 0.0218 (4) | |
C2 | 0.7146 (2) | 0.6812 (2) | 0.26606 (15) | 0.0251 (4) | |
C3 | 0.7510 (2) | 0.9334 (2) | 0.26930 (14) | 0.0224 (4) | |
C4 | 0.6562 (3) | 0.4530 (2) | 0.30115 (19) | 0.0406 (6) | |
H4E | 0.5919 | 0.3989 | 0.3386 | 0.049* | |
H4D | 0.7756 | 0.4854 | 0.3458 | 0.049* | |
C5 | 0.6289 (4) | 0.3610 (3) | 0.2018 (2) | 0.0512 (7) | |
H5F | 0.6644 | 0.2826 | 0.2175 | 0.077* | |
H5E | 0.6940 | 0.4135 | 0.1651 | 0.077* | |
H5D | 0.5105 | 0.3267 | 0.1580 | 0.077* | |
C10 | 0.9394 (2) | 0.9750 (2) | 0.30138 (18) | 0.0354 (5) | |
H10A | 0.9768 | 0.9078 | 0.3390 | 0.042* | |
H10B | 0.9684 | 0.9720 | 0.2384 | 0.042* | |
C1A | 0.4024 (2) | 0.78679 (18) | 0.34417 (14) | 0.0208 (4) | |
C2A | 0.2471 (2) | 0.7800 (2) | 0.34900 (15) | 0.0258 (4) | |
H2A | 0.1544 | 0.7627 | 0.2869 | 0.031* | |
C3A | 0.2296 (3) | 0.7985 (2) | 0.44427 (16) | 0.0298 (5) | |
H3A | 0.1244 | 0.7934 | 0.4472 | 0.036* | |
C4A | 0.3638 (3) | 0.8243 (2) | 0.53527 (16) | 0.0305 (5) | |
H4A | 0.3509 | 0.8372 | 0.6005 | 0.037* | |
C5A | 0.5168 (3) | 0.8312 (2) | 0.53116 (15) | 0.0293 (5) | |
H5A | 0.6089 | 0.8487 | 0.5937 | 0.035* | |
C6A | 0.5371 (2) | 0.81274 (19) | 0.43596 (15) | 0.0246 (4) | |
H6A | 0.6426 | 0.8179 | 0.4337 | 0.030* | |
C1B | 0.3596 (2) | 0.87422 (18) | 0.14484 (14) | 0.0210 (4) | |
C2B | 0.2996 (2) | 0.9705 (2) | 0.18141 (15) | 0.0264 (4) | |
H2B | 0.3034 | 0.9827 | 0.2510 | 0.032* | |
C3B | 0.2342 (3) | 1.0488 (2) | 0.11635 (17) | 0.0321 (5) | |
H3B | 0.1926 | 1.1139 | 0.1414 | 0.038* | |
C4B | 0.2294 (3) | 1.0323 (2) | 0.01516 (17) | 0.0320 (5) | |
H4B | 0.1842 | 1.0859 | −0.0292 | 0.038* | |
C5B | 0.2903 (3) | 0.9380 (2) | −0.02145 (16) | 0.0293 (4) | |
H5B | 0.2876 | 0.9270 | −0.0908 | 0.035* | |
C6B | 0.3554 (2) | 0.8594 (2) | 0.04331 (15) | 0.0254 (4) | |
H6B | 0.3975 | 0.7949 | 0.0180 | 0.030* | |
C1C | 0.3063 (2) | 0.59012 (18) | 0.14644 (14) | 0.0212 (4) | |
C2C | 0.1670 (2) | 0.5135 (2) | 0.16481 (16) | 0.0283 (4) | |
H2C | 0.1447 | 0.5476 | 0.2229 | 0.034* | |
C3C | 0.0602 (3) | 0.3873 (2) | 0.09867 (17) | 0.0336 (5) | |
H3C | −0.0347 | 0.3357 | 0.1119 | 0.040* | |
C4C | 0.0905 (3) | 0.3366 (2) | 0.01446 (17) | 0.0328 (5) | |
H4C | 0.0159 | 0.2508 | −0.0310 | 0.039* | |
C5C | 0.2301 (3) | 0.4107 (2) | −0.00427 (16) | 0.0318 (5) | |
H5C | 0.2517 | 0.3753 | −0.0623 | 0.038* | |
C6C | 0.3384 (3) | 0.5365 (2) | 0.06153 (16) | 0.0281 (4) | |
H6C | 0.4346 | 0.5864 | 0.0489 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0163 (2) | 0.0197 (3) | 0.0190 (3) | 0.00511 (18) | 0.00554 (19) | 0.00358 (18) |
O1 | 0.0287 (8) | 0.0301 (8) | 0.0425 (9) | 0.0144 (6) | 0.0137 (7) | 0.0171 (7) |
O2 | 0.0211 (7) | 0.0341 (8) | 0.0492 (9) | 0.0114 (6) | 0.0097 (7) | 0.0026 (7) |
O4 | 0.0250 (7) | 0.0245 (7) | 0.0318 (8) | 0.0064 (6) | 0.0075 (6) | 0.0015 (6) |
O5' | 0.055 (2) | 0.0402 (18) | 0.0358 (19) | 0.0016 (15) | 0.0196 (16) | 0.0086 (15) |
O6' | 0.0425 (15) | 0.0391 (16) | 0.0403 (16) | −0.0021 (13) | 0.0180 (13) | −0.0029 (14) |
C7' | 0.0273 (17) | 0.0380 (19) | 0.0356 (19) | −0.0018 (15) | 0.0166 (17) | −0.0020 (18) |
C8' | 0.032 (2) | 0.029 (2) | 0.078 (3) | 0.0099 (19) | 0.016 (2) | −0.008 (2) |
C9' | 0.0219 (19) | 0.0130 (18) | 0.053 (3) | −0.0001 (15) | 0.0014 (18) | −0.0012 (17) |
O5" | 0.0279 (16) | 0.0422 (19) | 0.0237 (16) | 0.0065 (13) | 0.0063 (12) | 0.0135 (14) |
O6" | 0.072 (2) | 0.0453 (19) | 0.0356 (18) | −0.0183 (17) | 0.0159 (16) | 0.0058 (16) |
C7" | 0.0305 (18) | 0.040 (2) | 0.031 (2) | −0.0012 (16) | 0.0156 (18) | 0.0046 (19) |
C8" | 0.054 (3) | 0.047 (3) | 0.073 (3) | 0.007 (2) | 0.014 (2) | 0.005 (2) |
C9" | 0.050 (4) | 0.046 (4) | 0.077 (4) | 0.009 (3) | 0.014 (3) | 0.012 (3) |
C1 | 0.0169 (9) | 0.0248 (10) | 0.0226 (9) | 0.0057 (7) | 0.0073 (7) | 0.0044 (7) |
C2 | 0.0207 (9) | 0.0270 (10) | 0.0231 (9) | 0.0074 (8) | 0.0044 (8) | 0.0013 (8) |
C3 | 0.0196 (9) | 0.0264 (10) | 0.0186 (9) | 0.0052 (8) | 0.0068 (7) | 0.0034 (7) |
C4 | 0.0446 (13) | 0.0358 (12) | 0.0508 (14) | 0.0229 (11) | 0.0171 (11) | 0.0232 (11) |
C5 | 0.0581 (17) | 0.0308 (13) | 0.0567 (17) | 0.0169 (12) | 0.0097 (13) | 0.0081 (11) |
C10 | 0.0208 (10) | 0.0339 (11) | 0.0463 (13) | 0.0040 (8) | 0.0105 (9) | 0.0096 (10) |
C1A | 0.0227 (9) | 0.0179 (9) | 0.0217 (9) | 0.0065 (7) | 0.0087 (7) | 0.0042 (7) |
C2A | 0.0226 (10) | 0.0266 (10) | 0.0285 (10) | 0.0087 (8) | 0.0093 (8) | 0.0074 (8) |
C3A | 0.0328 (11) | 0.0293 (11) | 0.0374 (11) | 0.0151 (9) | 0.0209 (9) | 0.0114 (9) |
C4A | 0.0460 (13) | 0.0265 (10) | 0.0272 (10) | 0.0164 (9) | 0.0194 (9) | 0.0088 (8) |
C5A | 0.0373 (12) | 0.0269 (11) | 0.0215 (10) | 0.0129 (9) | 0.0067 (9) | 0.0035 (8) |
C6A | 0.0259 (10) | 0.0223 (9) | 0.0238 (9) | 0.0082 (8) | 0.0075 (8) | 0.0033 (8) |
C1B | 0.0150 (8) | 0.0190 (9) | 0.0240 (9) | 0.0023 (7) | 0.0042 (7) | 0.0038 (7) |
C2B | 0.0270 (10) | 0.0238 (10) | 0.0266 (10) | 0.0079 (8) | 0.0088 (8) | 0.0039 (8) |
C3B | 0.0312 (11) | 0.0281 (11) | 0.0400 (12) | 0.0147 (9) | 0.0125 (9) | 0.0090 (9) |
C4B | 0.0288 (11) | 0.0289 (11) | 0.0370 (12) | 0.0111 (9) | 0.0071 (9) | 0.0141 (9) |
C5B | 0.0287 (10) | 0.0298 (11) | 0.0262 (10) | 0.0065 (8) | 0.0081 (8) | 0.0105 (8) |
C6B | 0.0243 (10) | 0.0253 (10) | 0.0263 (10) | 0.0077 (8) | 0.0094 (8) | 0.0066 (8) |
C1C | 0.0197 (9) | 0.0189 (9) | 0.0222 (9) | 0.0065 (7) | 0.0042 (7) | 0.0054 (7) |
C2C | 0.0268 (10) | 0.0263 (10) | 0.0280 (10) | 0.0046 (8) | 0.0102 (9) | 0.0042 (8) |
C3C | 0.0262 (10) | 0.0260 (11) | 0.0407 (12) | 0.0009 (8) | 0.0098 (9) | 0.0060 (9) |
C4C | 0.0297 (11) | 0.0207 (10) | 0.0360 (12) | 0.0058 (8) | 0.0010 (9) | 0.0005 (8) |
C5C | 0.0347 (11) | 0.0278 (11) | 0.0290 (11) | 0.0117 (9) | 0.0078 (9) | −0.0004 (9) |
C6C | 0.0265 (10) | 0.0267 (10) | 0.0300 (10) | 0.0078 (8) | 0.0108 (8) | 0.0036 (8) |
Geometric parameters (Å, º) top
P1—C1 | 1.7546 (18) | C5—H5D | 0.9800 |
P1—C1A | 1.8055 (19) | C10—H10A | 0.9900 |
P1—C1C | 1.8106 (19) | C10—H10B | 0.9900 |
P1—C1B | 1.8183 (19) | C1A—C6A | 1.391 (3) |
O1—C2 | 1.361 (2) | C1A—C2A | 1.407 (3) |
O1—C4 | 1.452 (2) | C2A—C3A | 1.382 (3) |
O2—C2 | 1.220 (2) | C2A—H2A | 0.9500 |
O4—C3 | 1.240 (2) | C3A—C4A | 1.383 (3) |
O5'—C7' | 1.233 (4) | C3A—H3A | 0.9500 |
O6'—C7' | 1.344 (4) | C4A—C5A | 1.383 (3) |
O6'—C8' | 1.512 (6) | C4A—H4A | 0.9500 |
C7'—C10 | 1.479 (4) | C5A—C6A | 1.393 (3) |
C8'—C9' | 1.503 (6) | C5A—H5A | 0.9500 |
C8'—H8'A | 0.9900 | C6A—H6A | 0.9500 |
C8'—H8'B | 0.9900 | C1B—C6B | 1.390 (3) |
C9'—H9'A | 0.9800 | C1B—C2B | 1.393 (3) |
C9'—H9'B | 0.9800 | C2B—C3B | 1.389 (3) |
C9'—H9'C | 0.9800 | C2B—H2B | 0.9500 |
O5"—C7" | 1.186 (4) | C3B—C4B | 1.384 (3) |
O6"—C7" | 1.323 (5) | C3B—H3B | 0.9500 |
O6"—C8" | 1.501 (6) | C4B—C5B | 1.384 (3) |
C7"—C10 | 1.463 (4) | C4B—H4B | 0.9500 |
C8"—C9" | 1.484 (7) | C5B—C6B | 1.388 (3) |
C8"—H8"A | 0.9900 | C5B—H5B | 0.9500 |
C8"—H8"B | 0.9900 | C6B—H6B | 0.9500 |
C9"—H9"A | 0.9800 | C1C—C2C | 1.389 (3) |
C9"—H9"B | 0.9800 | C1C—C6C | 1.400 (3) |
C9"—H9"C | 0.9800 | C2C—C3C | 1.389 (3) |
C1—C3 | 1.432 (3) | C2C—H2C | 0.9500 |
C1—C2 | 1.453 (3) | C3C—C4C | 1.371 (3) |
C3—C10 | 1.525 (3) | C3C—H3C | 0.9500 |
C4—C5 | 1.499 (4) | C4C—C5C | 1.387 (3) |
C4—H4E | 0.9900 | C4C—H4C | 0.9500 |
C4—H4D | 0.9900 | C5C—C6C | 1.387 (3) |
C5—H5F | 0.9800 | C5C—H5C | 0.9500 |
C5—H5E | 0.9800 | C6C—H6C | 0.9500 |
| | | |
C1—P1—C1A | 111.30 (9) | C7"—C10—H10A | 109.3 |
C1—P1—C1C | 111.19 (9) | C7'—C10—H10A | 132.2 |
C1A—P1—C1C | 109.69 (8) | C3—C10—H10A | 109.3 |
C1—P1—C1B | 112.06 (9) | C7"—C10—H10B | 109.3 |
C1A—P1—C1B | 108.99 (9) | C7'—C10—H10B | 84.9 |
C1C—P1—C1B | 103.30 (8) | C3—C10—H10B | 109.3 |
C2—O1—C4 | 117.47 (16) | H10A—C10—H10B | 107.9 |
C7'—O6'—C8' | 112.7 (4) | C6A—C1A—C2A | 119.28 (17) |
O5'—C7'—O6' | 120.9 (3) | C6A—C1A—P1 | 117.54 (14) |
O5'—C7'—C10 | 120.5 (3) | C2A—C1A—P1 | 123.18 (14) |
O6'—C7'—C10 | 118.6 (3) | C3A—C2A—C1A | 119.93 (18) |
C9'—C8'—O6' | 111.9 (4) | C3A—C2A—H2A | 120.0 |
C9'—C8'—H8'A | 109.2 | C1A—C2A—H2A | 120.0 |
O6'—C8'—H8'A | 109.2 | C2A—C3A—C4A | 120.57 (19) |
C9'—C8'—H8'B | 109.2 | C2A—C3A—H3A | 119.7 |
O6'—C8'—H8'B | 109.2 | C4A—C3A—H3A | 119.7 |
H8'A—C8'—H8'B | 107.9 | C5A—C4A—C3A | 119.83 (18) |
C8'—C9'—H9'A | 109.5 | C5A—C4A—H4A | 120.1 |
C8'—C9'—H9'B | 109.5 | C3A—C4A—H4A | 120.1 |
H9'A—C9'—H9'B | 109.5 | C4A—C5A—C6A | 120.49 (19) |
C8'—C9'—H9'C | 109.5 | C4A—C5A—H5A | 119.8 |
H9'A—C9'—H9'C | 109.5 | C6A—C5A—H5A | 119.8 |
H9'B—C9'—H9'C | 109.5 | C1A—C6A—C5A | 119.89 (18) |
C7"—O6"—C8" | 112.4 (4) | C1A—C6A—H6A | 120.1 |
O5"—C7"—O6" | 125.9 (4) | C5A—C6A—H6A | 120.1 |
O5"—C7"—C10 | 121.2 (4) | C6B—C1B—C2B | 119.15 (17) |
O6"—C7"—C10 | 112.6 (3) | C6B—C1B—P1 | 118.37 (14) |
C9"—C8"—O6" | 102.1 (5) | C2B—C1B—P1 | 122.44 (15) |
C9"—C8"—H8"A | 111.4 | C3B—C2B—C1B | 120.13 (19) |
O6"—C8"—H8"A | 111.4 | C3B—C2B—H2B | 119.9 |
C9"—C8"—H8"B | 111.4 | C1B—C2B—H2B | 119.9 |
O6"—C8"—H8"B | 111.4 | C4B—C3B—C2B | 120.2 (2) |
H8"A—C8"—H8"B | 109.2 | C4B—C3B—H3B | 119.9 |
C8"—C9"—H9"A | 109.5 | C2B—C3B—H3B | 119.9 |
C8"—C9"—H9"B | 109.5 | C5B—C4B—C3B | 120.02 (19) |
H9"A—C9"—H9"B | 109.5 | C5B—C4B—H4B | 120.0 |
C8"—C9"—H9"C | 109.5 | C3B—C4B—H4B | 120.0 |
H9"A—C9"—H9"C | 109.5 | C4B—C5B—C6B | 119.89 (19) |
H9"B—C9"—H9"C | 109.5 | C4B—C5B—H5B | 120.1 |
C3—C1—C2 | 122.75 (16) | C6B—C5B—H5B | 120.1 |
C3—C1—P1 | 114.85 (14) | C5B—C6B—C1B | 120.59 (19) |
C2—C1—P1 | 120.38 (14) | C5B—C6B—H6B | 119.7 |
O2—C2—O1 | 121.46 (18) | C1B—C6B—H6B | 119.7 |
O2—C2—C1 | 126.42 (18) | C2C—C1C—C6C | 118.79 (17) |
O1—C2—C1 | 112.12 (16) | C2C—C1C—P1 | 121.46 (15) |
O4—C3—C1 | 122.02 (17) | C6C—C1C—P1 | 119.58 (14) |
O4—C3—C10 | 117.17 (17) | C3C—C2C—C1C | 120.3 (2) |
C1—C3—C10 | 120.75 (17) | C3C—C2C—H2C | 119.8 |
O1—C4—C5 | 112.60 (19) | C1C—C2C—H2C | 119.8 |
O1—C4—H4E | 109.1 | C4C—C3C—C2C | 120.6 (2) |
C5—C4—H4E | 109.1 | C4C—C3C—H3C | 119.7 |
O1—C4—H4D | 109.1 | C2C—C3C—H3C | 119.7 |
C5—C4—H4D | 109.1 | C3C—C4C—C5C | 119.85 (19) |
H4E—C4—H4D | 107.8 | C3C—C4C—H4C | 120.1 |
C4—C5—H5F | 109.5 | C5C—C4C—H4C | 120.1 |
C4—C5—H5E | 109.5 | C4C—C5C—C6C | 120.1 (2) |
H5F—C5—H5E | 109.5 | C4C—C5C—H5C | 119.9 |
C4—C5—H5D | 109.5 | C6C—C5C—H5C | 119.9 |
H5F—C5—H5D | 109.5 | C5C—C6C—C1C | 120.27 (19) |
H5E—C5—H5D | 109.5 | C5C—C6C—H6C | 119.9 |
C7"—C10—C3 | 111.8 (3) | C1C—C6C—H6C | 119.9 |
C7'—C10—C3 | 109.1 (2) | | |
| | | |
C8'—O6'—C7'—O5' | 8.9 (6) | C1C—P1—C1A—C2A | −61.19 (17) |
C8'—O6'—C7'—C10 | −168.8 (4) | C1B—P1—C1A—C2A | 51.25 (18) |
C7'—O6'—C8'—C9' | −86.3 (6) | C6A—C1A—C2A—C3A | −0.2 (3) |
C8"—O6"—C7"—O5" | 0.4 (8) | P1—C1A—C2A—C3A | 179.29 (15) |
C8"—O6"—C7"—C10 | −173.8 (4) | C1A—C2A—C3A—C4A | 0.3 (3) |
C7"—O6"—C8"—C9" | −86.1 (6) | C2A—C3A—C4A—C5A | −0.2 (3) |
C1A—P1—C1—C3 | −80.33 (15) | C3A—C4A—C5A—C6A | 0.2 (3) |
C1C—P1—C1—C3 | 157.05 (14) | C2A—C1A—C6A—C5A | 0.2 (3) |
C1B—P1—C1—C3 | 42.00 (16) | P1—C1A—C6A—C5A | −179.37 (14) |
C1A—P1—C1—C2 | 83.96 (17) | C4A—C5A—C6A—C1A | −0.2 (3) |
C1C—P1—C1—C2 | −38.66 (18) | C1—P1—C1B—C6B | 64.08 (16) |
C1B—P1—C1—C2 | −153.71 (15) | C1A—P1—C1B—C6B | −172.28 (14) |
C4—O1—C2—O2 | −3.1 (3) | C1C—P1—C1B—C6B | −55.69 (16) |
C4—O1—C2—C1 | 177.55 (17) | C1—P1—C1B—C2B | −118.12 (16) |
C3—C1—C2—O2 | −27.6 (3) | C1A—P1—C1B—C2B | 5.52 (18) |
P1—C1—C2—O2 | 169.36 (16) | C1C—P1—C1B—C2B | 122.11 (16) |
C3—C1—C2—O1 | 151.68 (17) | C6B—C1B—C2B—C3B | 1.0 (3) |
P1—C1—C2—O1 | −11.3 (2) | P1—C1B—C2B—C3B | −176.77 (15) |
C2—C1—C3—O4 | −167.36 (18) | C1B—C2B—C3B—C4B | −0.5 (3) |
P1—C1—C3—O4 | −3.5 (2) | C2B—C3B—C4B—C5B | −0.2 (3) |
C2—C1—C3—C10 | 9.8 (3) | C3B—C4B—C5B—C6B | 0.3 (3) |
P1—C1—C3—C10 | 173.65 (15) | C4B—C5B—C6B—C1B | 0.2 (3) |
C2—O1—C4—C5 | −80.1 (3) | C2B—C1B—C6B—C5B | −0.9 (3) |
O5"—C7"—C10—C7' | 171.7 (11) | P1—C1B—C6B—C5B | 177.00 (15) |
O6"—C7"—C10—C7' | −13.8 (5) | C1—P1—C1C—C2C | 142.81 (16) |
O5"—C7"—C10—C3 | 81.8 (5) | C1A—P1—C1C—C2C | 19.27 (18) |
O6"—C7"—C10—C3 | −103.7 (5) | C1B—P1—C1C—C2C | −96.82 (17) |
O5'—C7'—C10—C7" | 166.1 (10) | C1—P1—C1C—C6C | −41.96 (17) |
O6'—C7'—C10—C7" | −16.2 (5) | C1A—P1—C1C—C6C | −165.50 (15) |
O5'—C7'—C10—C3 | −93.2 (5) | C1B—P1—C1C—C6C | 78.40 (16) |
O6'—C7'—C10—C3 | 84.5 (4) | C6C—C1C—C2C—C3C | −1.2 (3) |
O4—C3—C10—C7" | 25.1 (3) | P1—C1C—C2C—C3C | 174.02 (16) |
C1—C3—C10—C7" | −152.2 (2) | C1C—C2C—C3C—C4C | 0.0 (3) |
O4—C3—C10—C7' | −4.8 (3) | C2C—C3C—C4C—C5C | 0.9 (3) |
C1—C3—C10—C7' | 178.0 (2) | C3C—C4C—C5C—C6C | −0.5 (3) |
C1—P1—C1A—C6A | −5.13 (17) | C4C—C5C—C6C—C1C | −0.8 (3) |
C1C—P1—C1A—C6A | 118.35 (15) | C2C—C1C—C6C—C5C | 1.6 (3) |
C1B—P1—C1A—C6A | −129.22 (14) | P1—C1C—C6C—C5C | −173.71 (15) |
C1—P1—C1A—C2A | 175.33 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O2 | 0.99 | 2.23 | 2.853 (3) | 120 |
C2A—H2A···O2i | 0.95 | 2.54 | 3.189 (3) | 126 |
C3B—H3B···O5′i | 0.95 | 2.48 | 3.327 (5) | 150 |
C4A—H4A···O4ii | 0.95 | 2.38 | 3.245 (3) | 151 |
C9′—H9′A···Cg1iii | 0.98 | 2.74 | 3.712 (4) | 172 |
C4C—H4C···Cg2iv | 0.95 | 2.79 | 3.604 (2) | 144 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+1; (iii) x+1, y+1, z; (iv) −x, −y+1, −z. |
(II) diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate acetic acid monosolvate
top
Crystal data top
C27H27O5P·C2H4O2 | Z = 2 |
Mr = 522.51 | F(000) = 552 |
Triclinic, P1 | Dx = 1.294 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.957 (4) Å | Cell parameters from 999 reflections |
b = 10.589 (4) Å | θ = 4.8–50.9° |
c = 14.928 (6) Å | µ = 0.15 mm−1 |
α = 78.191 (6)° | T = 150 K |
β = 71.505 (6)° | Block, yellow |
γ = 64.285 (6)° | 0.46 × 0.38 × 0.32 mm |
V = 1340.7 (9) Å3 | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 5728 independent reflections |
Radiation source: fine-focus sealed tube | 4037 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.112 |
ϕ and ω scans | θmax = 28.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −13→12 |
Tmin = 0.93, Tmax = 0.95 | k = −13→13 |
11211 measured 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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0898P)2] where P = (Fo2 + 2Fc2)/3 |
5728 reflections | (Δ/σ)max = 0.002 |
341 parameters | Δρmax = 0.49 e Å−3 |
1 restraint | Δρmin = −0.36 e Å−3 |
Crystal data top
C27H27O5P·C2H4O2 | γ = 64.285 (6)° |
Mr = 522.51 | V = 1340.7 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.957 (4) Å | Mo Kα radiation |
b = 10.589 (4) Å | µ = 0.15 mm−1 |
c = 14.928 (6) Å | T = 150 K |
α = 78.191 (6)° | 0.46 × 0.38 × 0.32 mm |
β = 71.505 (6)° | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 5728 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 4037 reflections with I > 2σ(I) |
Tmin = 0.93, Tmax = 0.95 | Rint = 0.112 |
11211 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 1 restraint |
wR(F2) = 0.171 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.49 e Å−3 |
5728 reflections | Δρmin = −0.36 e Å−3 |
341 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.20921 (6) | 0.45376 (5) | 0.21302 (3) | 0.03343 (17) | |
O1 | 0.43004 (17) | 0.16911 (15) | 0.17944 (11) | 0.0476 (4) | |
O2 | 0.64867 (18) | 0.1986 (2) | 0.14911 (15) | 0.0729 (6) | |
O4 | 0.36228 (17) | 0.57094 (17) | 0.28961 (12) | 0.0537 (4) | |
O5 | 0.5715 (2) | 0.2387 (3) | 0.37845 (15) | 0.0920 (8) | |
O6 | 0.81302 (16) | 0.21769 (16) | 0.31395 (11) | 0.0509 (4) | |
C1 | 0.4074 (2) | 0.3871 (2) | 0.20554 (14) | 0.0367 (5) | |
C2 | 0.5089 (2) | 0.2468 (2) | 0.17496 (15) | 0.0425 (5) | |
C3 | 0.4558 (2) | 0.4612 (2) | 0.24915 (15) | 0.0411 (5) | |
C4 | 0.5150 (3) | 0.0350 (3) | 0.13786 (19) | 0.0579 (6) | |
H4E | 0.5878 | −0.0311 | 0.1751 | 0.070* | |
H4D | 0.5749 | 0.0476 | 0.0721 | 0.070* | |
C5 | 0.4032 (3) | −0.0211 (3) | 0.1382 (2) | 0.0718 (8) | |
H5F | 0.4582 | −0.1119 | 0.1104 | 0.108* | |
H5E | 0.3320 | 0.0448 | 0.1010 | 0.108* | |
H5D | 0.3448 | −0.0336 | 0.2036 | 0.108* | |
C7 | 0.6621 (2) | 0.2789 (3) | 0.32173 (16) | 0.0479 (6) | |
C8 | 0.8633 (3) | 0.1030 (3) | 0.38472 (18) | 0.0558 (6) | |
H8A | 0.8251 | 0.0304 | 0.3859 | 0.067* | |
H8B | 0.8228 | 0.1386 | 0.4484 | 0.067* | |
C9 | 1.0367 (3) | 0.0422 (3) | 0.3572 (2) | 0.0682 (8) | |
H9A | 1.0752 | −0.0351 | 0.4036 | 0.102* | |
H9B | 1.0729 | 0.1154 | 0.3559 | 0.102* | |
H9C | 1.0752 | 0.0068 | 0.2943 | 0.102* | |
C10 | 0.6225 (2) | 0.4054 (2) | 0.25232 (17) | 0.0465 (5) | |
H10A | 0.6908 | 0.3798 | 0.1884 | 0.056* | |
H10B | 0.6411 | 0.4801 | 0.2704 | 0.056* | |
C1A | 0.1010 (2) | 0.4085 (2) | 0.32761 (14) | 0.0357 (4) | |
C2A | −0.0596 (2) | 0.4510 (2) | 0.35274 (16) | 0.0445 (5) | |
H2A | −0.1165 | 0.5033 | 0.3074 | 0.053* | |
C3A | −0.1353 (3) | 0.4174 (3) | 0.44278 (18) | 0.0559 (6) | |
H3A | −0.2443 | 0.4472 | 0.4596 | 0.067* | |
C4A | −0.0533 (3) | 0.3406 (3) | 0.50856 (18) | 0.0589 (7) | |
H4A | −0.1060 | 0.3186 | 0.5709 | 0.071* | |
C5A | 0.1047 (3) | 0.2957 (3) | 0.48420 (16) | 0.0549 (6) | |
H5A | 0.1608 | 0.2406 | 0.5294 | 0.066* | |
C6A | 0.1827 (3) | 0.3301 (2) | 0.39452 (14) | 0.0429 (5) | |
H6A | 0.2916 | 0.3003 | 0.3786 | 0.051* | |
C1B | 0.1800 (2) | 0.3891 (2) | 0.12034 (14) | 0.0393 (5) | |
C2B | 0.2702 (3) | 0.3967 (2) | 0.02825 (16) | 0.0541 (6) | |
H2B | 0.3470 | 0.4331 | 0.0153 | 0.065* | |
C3B | 0.2479 (4) | 0.3512 (3) | −0.04472 (18) | 0.0690 (8) | |
H3B | 0.3108 | 0.3548 | −0.1073 | 0.083* | |
C4B | 0.1351 (4) | 0.3010 (3) | −0.0266 (2) | 0.0703 (8) | |
H4B | 0.1192 | 0.2712 | −0.0768 | 0.084* | |
C5B | 0.0450 (3) | 0.2938 (3) | 0.0642 (2) | 0.0660 (8) | |
H5B | −0.0333 | 0.2594 | 0.0763 | 0.079* | |
C6B | 0.0676 (3) | 0.3363 (2) | 0.13812 (18) | 0.0491 (6) | |
H6B | 0.0063 | 0.3293 | 0.2008 | 0.059* | |
C1C | 0.1317 (2) | 0.6433 (2) | 0.18739 (14) | 0.0362 (4) | |
C2C | −0.0116 (2) | 0.7311 (2) | 0.23842 (16) | 0.0440 (5) | |
H2C | −0.0665 | 0.6940 | 0.2937 | 0.053* | |
C3C | −0.0748 (3) | 0.8728 (2) | 0.20915 (18) | 0.0536 (6) | |
H3C | −0.1737 | 0.9319 | 0.2437 | 0.064* | |
C4C | 0.0049 (3) | 0.9278 (3) | 0.1306 (2) | 0.0601 (7) | |
H4C | −0.0384 | 1.0249 | 0.1108 | 0.072* | |
C5C | 0.1466 (3) | 0.8428 (3) | 0.08074 (19) | 0.0646 (7) | |
H5C | 0.2018 | 0.8815 | 0.0265 | 0.078* | |
C6C | 0.2113 (3) | 0.7005 (2) | 0.10812 (18) | 0.0537 (6) | |
H6C | 0.3100 | 0.6424 | 0.0727 | 0.064* | |
C1D | 0.5082 (3) | 0.7776 (3) | 0.35152 (18) | 0.0568 (6) | |
C2D | 0.4898 (4) | 0.8994 (3) | 0.3972 (2) | 0.0818 (9) | |
H2DC | 0.5888 | 0.9085 | 0.3802 | 0.123* | |
H2DB | 0.4557 | 0.8836 | 0.4662 | 0.123* | |
H2DA | 0.4127 | 0.9857 | 0.3753 | 0.123* | |
O2D | 0.3820 (2) | 0.7546 (2) | 0.37491 (15) | 0.0728 (6) | |
H2D | 0.396 (4) | 0.676 (2) | 0.358 (3) | 0.110 (13)* | |
O1D | 0.6243 (2) | 0.7102 (2) | 0.29592 (18) | 0.0879 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0351 (3) | 0.0375 (3) | 0.0302 (3) | −0.0155 (2) | −0.0107 (2) | −0.0020 (2) |
O1 | 0.0455 (8) | 0.0399 (9) | 0.0529 (9) | −0.0124 (7) | −0.0115 (7) | −0.0071 (7) |
O2 | 0.0395 (9) | 0.0735 (13) | 0.0953 (15) | −0.0109 (9) | −0.0048 (9) | −0.0318 (11) |
O4 | 0.0447 (9) | 0.0592 (10) | 0.0635 (11) | −0.0164 (8) | −0.0204 (8) | −0.0171 (8) |
O5 | 0.0576 (11) | 0.1364 (19) | 0.0747 (14) | −0.0509 (12) | −0.0278 (10) | 0.0524 (13) |
O6 | 0.0444 (8) | 0.0560 (10) | 0.0565 (10) | −0.0227 (7) | −0.0233 (7) | 0.0096 (7) |
C1 | 0.0345 (10) | 0.0429 (12) | 0.0324 (10) | −0.0157 (9) | −0.0095 (8) | −0.0005 (8) |
C2 | 0.0376 (11) | 0.0477 (13) | 0.0370 (11) | −0.0123 (10) | −0.0098 (9) | −0.0029 (9) |
C3 | 0.0377 (11) | 0.0489 (13) | 0.0383 (11) | −0.0195 (10) | −0.0128 (9) | 0.0031 (9) |
C4 | 0.0571 (15) | 0.0471 (14) | 0.0615 (16) | −0.0117 (11) | −0.0119 (12) | −0.0134 (11) |
C5 | 0.0774 (18) | 0.0539 (16) | 0.085 (2) | −0.0198 (14) | −0.0257 (16) | −0.0158 (14) |
C7 | 0.0412 (12) | 0.0649 (15) | 0.0432 (13) | −0.0243 (11) | −0.0183 (10) | 0.0033 (11) |
C8 | 0.0652 (15) | 0.0547 (15) | 0.0535 (14) | −0.0240 (12) | −0.0306 (12) | 0.0084 (11) |
C9 | 0.0597 (16) | 0.0637 (17) | 0.0782 (19) | −0.0121 (13) | −0.0360 (14) | 0.0013 (14) |
C10 | 0.0416 (11) | 0.0531 (14) | 0.0509 (13) | −0.0237 (10) | −0.0172 (10) | 0.0029 (10) |
C1A | 0.0387 (10) | 0.0392 (11) | 0.0328 (10) | −0.0192 (9) | −0.0069 (8) | −0.0056 (8) |
C2A | 0.0435 (12) | 0.0489 (13) | 0.0461 (13) | −0.0218 (10) | −0.0109 (10) | −0.0074 (10) |
C3A | 0.0517 (14) | 0.0654 (16) | 0.0543 (15) | −0.0350 (12) | 0.0062 (12) | −0.0174 (12) |
C4A | 0.0758 (17) | 0.0684 (17) | 0.0374 (13) | −0.0445 (14) | 0.0033 (12) | −0.0065 (11) |
C5A | 0.0729 (16) | 0.0603 (15) | 0.0367 (12) | −0.0343 (13) | −0.0147 (12) | 0.0040 (10) |
C6A | 0.0492 (12) | 0.0479 (12) | 0.0344 (11) | −0.0229 (10) | −0.0111 (9) | −0.0007 (9) |
C1B | 0.0445 (11) | 0.0363 (11) | 0.0374 (11) | −0.0105 (9) | −0.0185 (9) | −0.0038 (8) |
C2B | 0.0755 (16) | 0.0543 (14) | 0.0351 (12) | −0.0287 (12) | −0.0152 (11) | −0.0009 (10) |
C3B | 0.109 (2) | 0.0559 (16) | 0.0373 (14) | −0.0219 (16) | −0.0283 (14) | −0.0030 (11) |
C4B | 0.100 (2) | 0.0523 (16) | 0.0684 (19) | −0.0126 (15) | −0.0548 (18) | −0.0130 (13) |
C5B | 0.0699 (17) | 0.0557 (16) | 0.089 (2) | −0.0174 (13) | −0.0432 (16) | −0.0203 (14) |
C6B | 0.0502 (13) | 0.0485 (13) | 0.0569 (14) | −0.0196 (11) | −0.0208 (11) | −0.0105 (11) |
C1C | 0.0400 (11) | 0.0402 (11) | 0.0351 (11) | −0.0180 (9) | −0.0165 (9) | −0.0013 (8) |
C2C | 0.0504 (13) | 0.0416 (12) | 0.0406 (12) | −0.0170 (10) | −0.0128 (10) | −0.0060 (9) |
C3C | 0.0562 (14) | 0.0418 (13) | 0.0596 (15) | −0.0115 (11) | −0.0191 (12) | −0.0089 (11) |
C4C | 0.0785 (18) | 0.0374 (13) | 0.0700 (17) | −0.0219 (13) | −0.0341 (15) | 0.0050 (12) |
C5C | 0.0849 (19) | 0.0540 (16) | 0.0590 (16) | −0.0398 (15) | −0.0169 (14) | 0.0123 (12) |
C6C | 0.0515 (13) | 0.0498 (14) | 0.0538 (14) | −0.0238 (11) | −0.0016 (11) | −0.0020 (11) |
C1D | 0.0566 (15) | 0.0656 (17) | 0.0525 (15) | −0.0298 (13) | −0.0170 (13) | 0.0040 (12) |
C2D | 0.110 (2) | 0.099 (2) | 0.0642 (19) | −0.069 (2) | −0.0172 (17) | −0.0072 (16) |
O2D | 0.0613 (11) | 0.0912 (16) | 0.0785 (14) | −0.0412 (11) | −0.0045 (10) | −0.0288 (12) |
O1D | 0.0545 (11) | 0.0822 (15) | 0.1196 (19) | −0.0270 (10) | −0.0053 (12) | −0.0202 (13) |
Geometric parameters (Å, º) top
P1—C1 | 1.758 (2) | C4A—C5A | 1.376 (3) |
P1—C1A | 1.806 (2) | C4A—H4A | 0.9500 |
P1—C1B | 1.812 (2) | C5A—C6A | 1.383 (3) |
P1—C1C | 1.817 (2) | C5A—H5A | 0.9500 |
O1—C2 | 1.343 (3) | C6A—H6A | 0.9500 |
O1—C4 | 1.450 (3) | C1B—C6B | 1.389 (3) |
O2—C2 | 1.212 (2) | C1B—C2B | 1.392 (3) |
O4—C3 | 1.255 (2) | C2B—C3B | 1.389 (4) |
O5—C7 | 1.188 (3) | C2B—H2B | 0.9500 |
O6—C7 | 1.329 (2) | C3B—C4B | 1.372 (4) |
O6—C8 | 1.457 (3) | C3B—H3B | 0.9500 |
C1—C3 | 1.417 (3) | C4B—C5B | 1.376 (4) |
C1—C2 | 1.455 (3) | C4B—H4B | 0.9500 |
C3—C10 | 1.514 (3) | C5B—C6B | 1.386 (3) |
C4—C5 | 1.470 (4) | C5B—H5B | 0.9500 |
C4—H4E | 0.9900 | C6B—H6B | 0.9500 |
C4—H4D | 0.9900 | C1C—C6C | 1.387 (3) |
C5—H5F | 0.9800 | C1C—C2C | 1.389 (3) |
C5—H5E | 0.9800 | C2C—C3C | 1.388 (3) |
C5—H5D | 0.9800 | C2C—H2C | 0.9500 |
C7—C10 | 1.502 (3) | C3C—C4C | 1.370 (4) |
C8—C9 | 1.503 (3) | C3C—H3C | 0.9500 |
C8—H8A | 0.9900 | C4C—C5C | 1.364 (3) |
C8—H8B | 0.9900 | C4C—H4C | 0.9500 |
C9—H9A | 0.9800 | C5C—C6C | 1.387 (3) |
C9—H9B | 0.9800 | C5C—H5C | 0.9500 |
C9—H9C | 0.9800 | C6C—H6C | 0.9500 |
C10—H10A | 0.9900 | C1D—O1D | 1.205 (3) |
C10—H10B | 0.9900 | C1D—O2D | 1.309 (3) |
C1A—C6A | 1.393 (3) | C1D—C2D | 1.496 (4) |
C1A—C2A | 1.401 (3) | C2D—H2DC | 0.9800 |
C2A—C3A | 1.377 (3) | C2D—H2DB | 0.9800 |
C2A—H2A | 0.9500 | C2D—H2DA | 0.9800 |
C3A—C4A | 1.378 (4) | O2D—H2D | 0.859 (10) |
C3A—H3A | 0.9500 | | |
| | | |
C1—P1—C1A | 111.97 (10) | C2A—C3A—H3A | 119.9 |
C1—P1—C1B | 109.70 (9) | C4A—C3A—H3A | 119.9 |
C1A—P1—C1B | 110.24 (10) | C5A—C4A—C3A | 120.1 (2) |
C1—P1—C1C | 111.04 (9) | C5A—C4A—H4A | 119.9 |
C1A—P1—C1C | 109.79 (9) | C3A—C4A—H4A | 119.9 |
C1B—P1—C1C | 103.79 (9) | C4A—C5A—C6A | 120.6 (2) |
C2—O1—C4 | 117.60 (17) | C4A—C5A—H5A | 119.7 |
C7—O6—C8 | 116.27 (18) | C6A—C5A—H5A | 119.7 |
C3—C1—C2 | 121.40 (18) | C5A—C6A—C1A | 119.8 (2) |
C3—C1—P1 | 116.91 (15) | C5A—C6A—H6A | 120.1 |
C2—C1—P1 | 120.31 (15) | C1A—C6A—H6A | 120.1 |
O2—C2—O1 | 121.0 (2) | C6B—C1B—C2B | 119.3 (2) |
O2—C2—C1 | 126.9 (2) | C6B—C1B—P1 | 121.96 (16) |
O1—C2—C1 | 112.09 (17) | C2B—C1B—P1 | 118.67 (17) |
O4—C3—C1 | 121.68 (18) | C3B—C2B—C1B | 120.0 (3) |
O4—C3—C10 | 117.81 (19) | C3B—C2B—H2B | 120.0 |
C1—C3—C10 | 120.45 (19) | C1B—C2B—H2B | 120.0 |
O1—C4—C5 | 108.07 (19) | C4B—C3B—C2B | 120.2 (3) |
O1—C4—H4E | 110.1 | C4B—C3B—H3B | 119.9 |
C5—C4—H4E | 110.1 | C2B—C3B—H3B | 119.9 |
O1—C4—H4D | 110.1 | C3B—C4B—C5B | 120.1 (2) |
C5—C4—H4D | 110.1 | C3B—C4B—H4B | 119.9 |
H4E—C4—H4D | 108.4 | C5B—C4B—H4B | 119.9 |
C4—C5—H5F | 109.5 | C4B—C5B—C6B | 120.5 (3) |
C4—C5—H5E | 109.5 | C4B—C5B—H5B | 119.8 |
H5F—C5—H5E | 109.5 | C6B—C5B—H5B | 119.8 |
C4—C5—H5D | 109.5 | C5B—C6B—C1B | 119.9 (2) |
H5F—C5—H5D | 109.5 | C5B—C6B—H6B | 120.1 |
H5E—C5—H5D | 109.5 | C1B—C6B—H6B | 120.1 |
O5—C7—O6 | 123.3 (2) | C6C—C1C—C2C | 118.8 (2) |
O5—C7—C10 | 125.3 (2) | C6C—C1C—P1 | 118.53 (16) |
O6—C7—C10 | 111.42 (19) | C2C—C1C—P1 | 122.33 (16) |
O6—C8—C9 | 107.0 (2) | C3C—C2C—C1C | 120.4 (2) |
O6—C8—H8A | 110.3 | C3C—C2C—H2C | 119.8 |
C9—C8—H8A | 110.3 | C1C—C2C—H2C | 119.8 |
O6—C8—H8B | 110.3 | C4C—C3C—C2C | 120.2 (2) |
C9—C8—H8B | 110.3 | C4C—C3C—H3C | 119.9 |
H8A—C8—H8B | 108.6 | C2C—C3C—H3C | 119.9 |
C8—C9—H9A | 109.5 | C5C—C4C—C3C | 119.9 (2) |
C8—C9—H9B | 109.5 | C5C—C4C—H4C | 120.1 |
H9A—C9—H9B | 109.5 | C3C—C4C—H4C | 120.1 |
C8—C9—H9C | 109.5 | C4C—C5C—C6C | 120.9 (2) |
H9A—C9—H9C | 109.5 | C4C—C5C—H5C | 119.5 |
H9B—C9—H9C | 109.5 | C6C—C5C—H5C | 119.5 |
C7—C10—C3 | 111.72 (18) | C1C—C6C—C5C | 119.8 (2) |
C7—C10—H10A | 109.3 | C1C—C6C—H6C | 120.1 |
C3—C10—H10A | 109.3 | C5C—C6C—H6C | 120.1 |
C7—C10—H10B | 109.3 | O1D—C1D—O2D | 122.7 (3) |
C3—C10—H10B | 109.3 | O1D—C1D—C2D | 124.3 (3) |
H10A—C10—H10B | 107.9 | O2D—C1D—C2D | 112.9 (2) |
C6A—C1A—C2A | 119.03 (19) | C1D—C2D—H2DC | 109.5 |
C6A—C1A—P1 | 117.46 (15) | C1D—C2D—H2DB | 109.5 |
C2A—C1A—P1 | 123.49 (16) | H2DC—C2D—H2DB | 109.5 |
C3A—C2A—C1A | 120.3 (2) | C1D—C2D—H2DA | 109.5 |
C3A—C2A—H2A | 119.8 | H2DC—C2D—H2DA | 109.5 |
C1A—C2A—H2A | 119.8 | H2DB—C2D—H2DA | 109.5 |
C2A—C3A—C4A | 120.1 (2) | C1D—O2D—H2D | 113 (2) |
| | | |
C1A—P1—C1—C3 | −78.19 (18) | C2A—C3A—C4A—C5A | −0.8 (4) |
C1B—P1—C1—C3 | 159.07 (16) | C3A—C4A—C5A—C6A | 1.7 (4) |
C1C—P1—C1—C3 | 44.92 (18) | C4A—C5A—C6A—C1A | −1.3 (4) |
C1A—P1—C1—C2 | 88.59 (18) | C2A—C1A—C6A—C5A | −0.1 (3) |
C1B—P1—C1—C2 | −34.15 (19) | P1—C1A—C6A—C5A | 178.33 (17) |
C1C—P1—C1—C2 | −148.30 (16) | C1—P1—C1B—C6B | 134.37 (18) |
C4—O1—C2—O2 | −10.0 (3) | C1A—P1—C1B—C6B | 10.6 (2) |
C4—O1—C2—C1 | 171.04 (19) | C1C—P1—C1B—C6B | −106.92 (19) |
C3—C1—C2—O2 | −29.3 (3) | C1—P1—C1B—C2B | −47.6 (2) |
P1—C1—C2—O2 | 164.5 (2) | C1A—P1—C1B—C2B | −171.33 (16) |
C3—C1—C2—O1 | 149.61 (19) | C1C—P1—C1B—C2B | 71.14 (18) |
P1—C1—C2—O1 | −16.6 (2) | C6B—C1B—C2B—C3B | −0.3 (3) |
C2—C1—C3—O4 | −168.0 (2) | P1—C1B—C2B—C3B | −178.42 (18) |
P1—C1—C3—O4 | −1.4 (3) | C1B—C2B—C3B—C4B | 1.2 (4) |
C2—C1—C3—C10 | 8.9 (3) | C2B—C3B—C4B—C5B | −0.9 (4) |
P1—C1—C3—C10 | 175.57 (15) | C3B—C4B—C5B—C6B | −0.3 (4) |
C2—O1—C4—C5 | −171.7 (2) | C4B—C5B—C6B—C1B | 1.2 (4) |
C8—O6—C7—O5 | −4.9 (4) | C2B—C1B—C6B—C5B | −0.9 (3) |
C8—O6—C7—C10 | 173.45 (19) | P1—C1B—C6B—C5B | 177.16 (17) |
C7—O6—C8—C9 | 175.1 (2) | C1—P1—C1C—C6C | 47.4 (2) |
O5—C7—C10—C3 | −11.2 (4) | C1A—P1—C1C—C6C | 171.81 (17) |
O6—C7—C10—C3 | 170.46 (18) | C1B—P1—C1C—C6C | −70.35 (19) |
O4—C3—C10—C7 | 104.3 (2) | C1—P1—C1C—C2C | −139.24 (17) |
C1—C3—C10—C7 | −72.8 (3) | C1A—P1—C1C—C2C | −14.9 (2) |
C1—P1—C1A—C6A | 0.4 (2) | C1B—P1—C1C—C2C | 102.96 (18) |
C1B—P1—C1A—C6A | 122.82 (16) | C6C—C1C—C2C—C3C | 1.4 (3) |
C1C—P1—C1A—C6A | −123.43 (16) | P1—C1C—C2C—C3C | −171.88 (17) |
C1—P1—C1A—C2A | 178.72 (17) | C1C—C2C—C3C—C4C | −1.2 (3) |
C1B—P1—C1A—C2A | −58.8 (2) | C2C—C3C—C4C—C5C | 0.3 (4) |
C1C—P1—C1A—C2A | 54.91 (19) | C3C—C4C—C5C—C6C | 0.4 (4) |
C6A—C1A—C2A—C3A | 1.0 (3) | C2C—C1C—C6C—C5C | −0.7 (3) |
P1—C1A—C2A—C3A | −177.32 (17) | P1—C1C—C6C—C5C | 172.85 (19) |
C1A—C2A—C3A—C4A | −0.5 (3) | C4C—C5C—C6C—C1C | −0.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6A—H6A···O5 | 0.95 | 2.57 | 3.498 (4) | 165 |
C5—H5E···Cg2 | 0.98 | 2.97 | 3.820 (3) | 146 |
O2D—H2D···O4 | 0.86 (1) | 1.85 (2) | 2.636 (3) | 152 (4) |
C10—H10B···O1D | 0.99 | 2.47 | 3.430 (3) | 163 |
C2A—H2A···O1Di | 0.95 | 2.59 | 3.377 (3) | 140 |
C2D—H2DB···O5ii | 0.98 | 2.41 | 3.345 (4) | 160 |
C4B—H4B···Cg3iii | 0.95 | 2.85 | 3.711 (4) | 152 |
C9—H9B···Cg1iv | 0.98 | 2.86 | 3.744 (4) | 150 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) x+1, y, z. |
(III) diethyl 2-(triphenylphosphoranylidene)succinate
top
Crystal data top
C26H27O4P | F(000) = 1840 |
Mr = 434.45 | Dx = 1.231 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 982 reflections |
a = 8.7357 (10) Å | θ = 4.2–50.1° |
b = 16.8280 (18) Å | µ = 0.15 mm−1 |
c = 31.896 (4) Å | T = 150 K |
V = 4688.9 (9) Å3 | Plate, colourless |
Z = 8 | 0.57 × 0.47 × 0.06 mm |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 5370 independent reflections |
Radiation source: fine-focus sealed tube | 3279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.086 |
ϕ and ω scans | θmax = 27.9°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −11→11 |
Tmin = 0.92, Tmax = 0.99 | k = −21→21 |
36723 measured reflections | l = −41→39 |
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) = 0.139 | H-atom parameters constrained |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0767P)2] where P = (Fo2 + 2Fc2)/3 |
5370 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C26H27O4P | V = 4688.9 (9) Å3 |
Mr = 434.45 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.7357 (10) Å | µ = 0.15 mm−1 |
b = 16.8280 (18) Å | T = 150 K |
c = 31.896 (4) Å | 0.57 × 0.47 × 0.06 mm |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 5370 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 3279 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 0.99 | Rint = 0.086 |
36723 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 0.91 | Δρmax = 0.44 e Å−3 |
5370 reflections | Δρmin = −0.22 e Å−3 |
280 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 | 0.38078 (5) | 0.69916 (3) | 0.386546 (14) | 0.03634 (15) | |
C1 | 0.4447 (2) | 0.79581 (10) | 0.38635 (5) | 0.0408 (4) | |
C2 | 0.3418 (2) | 0.85878 (11) | 0.39276 (6) | 0.0448 (5) | |
C4 | 0.0842 (3) | 0.89068 (13) | 0.41259 (7) | 0.0634 (6) | |
H4E | −0.0206 | 0.8718 | 0.4062 | 0.076* | |
H4D | 0.0996 | 0.9419 | 0.3979 | 0.076* | |
C5 | 0.0989 (3) | 0.90361 (17) | 0.45882 (8) | 0.0937 (9) | |
H5F | 0.0228 | 0.9427 | 0.4680 | 0.141* | |
H5D | 0.2019 | 0.9233 | 0.4652 | 0.141* | |
H5E | 0.0817 | 0.8533 | 0.4735 | 0.141* | |
C7 | 0.6443 (2) | 0.84084 (12) | 0.33282 (6) | 0.0486 (5) | |
C8 | 0.8441 (3) | 0.88952 (18) | 0.28885 (7) | 0.0786 (8) | |
H8A | 0.7728 | 0.9290 | 0.2767 | 0.094* | |
H8B | 0.8510 | 0.8437 | 0.2695 | 0.094* | |
C9 | 0.9968 (3) | 0.92536 (15) | 0.29493 (7) | 0.0758 (7) | |
H9A | 1.0368 | 0.9435 | 0.2679 | 0.114* | |
H9B | 1.0665 | 0.8857 | 0.3068 | 0.114* | |
H9C | 0.9886 | 0.9707 | 0.3141 | 0.114* | |
C10 | 0.6092 (2) | 0.81764 (11) | 0.37734 (6) | 0.0442 (5) | |
H10A | 0.6381 | 0.8624 | 0.3959 | 0.053* | |
H10B | 0.6747 | 0.7718 | 0.3849 | 0.053* | |
O1 | 0.19299 (15) | 0.83379 (8) | 0.39720 (4) | 0.0532 (4) | |
O2 | 0.37471 (17) | 0.92975 (8) | 0.39475 (5) | 0.0646 (4) | |
O5 | 0.55822 (19) | 0.84003 (12) | 0.30378 (5) | 0.0841 (5) | |
O6 | 0.78997 (16) | 0.86372 (9) | 0.32963 (4) | 0.0647 (4) | |
C1A | 0.2689 (2) | 0.66724 (11) | 0.34156 (5) | 0.0394 (4) | |
C2A | 0.2356 (2) | 0.58718 (11) | 0.33495 (6) | 0.0494 (5) | |
H2A | 0.2702 | 0.5487 | 0.3545 | 0.059* | |
C3A | 0.1535 (3) | 0.56328 (13) | 0.30046 (6) | 0.0583 (6) | |
H3A | 0.1305 | 0.5086 | 0.2964 | 0.070* | |
C4A | 0.1043 (3) | 0.61895 (15) | 0.27166 (7) | 0.0674 (6) | |
H4A | 0.0469 | 0.6027 | 0.2479 | 0.081* | |
C5A | 0.1384 (3) | 0.69795 (14) | 0.27739 (7) | 0.0716 (7) | |
H5A | 0.1049 | 0.7361 | 0.2575 | 0.086* | |
C6A | 0.2215 (3) | 0.72220 (12) | 0.31208 (6) | 0.0578 (6) | |
H6A | 0.2460 | 0.7768 | 0.3156 | 0.069* | |
C1B | 0.5467 (2) | 0.63510 (10) | 0.38504 (6) | 0.0426 (4) | |
C2B | 0.5955 (2) | 0.59260 (13) | 0.41934 (7) | 0.0619 (6) | |
H2B | 0.5397 | 0.5945 | 0.4449 | 0.074* | |
C3B | 0.7286 (3) | 0.54631 (14) | 0.41617 (10) | 0.0831 (8) | |
H3B | 0.7617 | 0.5160 | 0.4396 | 0.100* | |
C4B | 0.8107 (3) | 0.54424 (14) | 0.38006 (11) | 0.0811 (8) | |
H4B | 0.9014 | 0.5132 | 0.3785 | 0.097* | |
C5B | 0.7631 (3) | 0.58684 (15) | 0.34599 (9) | 0.0778 (7) | |
H5B | 0.8214 | 0.5859 | 0.3209 | 0.093* | |
C6B | 0.6299 (2) | 0.63142 (13) | 0.34803 (7) | 0.0604 (6) | |
H6B | 0.5954 | 0.6596 | 0.3240 | 0.072* | |
C1C | 0.2735 (2) | 0.67433 (10) | 0.43362 (5) | 0.0394 (4) | |
C2C | 0.3098 (3) | 0.71111 (13) | 0.47069 (6) | 0.0642 (6) | |
H2C | 0.3878 | 0.7504 | 0.4709 | 0.077* | |
C3C | 0.2359 (3) | 0.69245 (14) | 0.50755 (6) | 0.0712 (7) | |
H3C | 0.2633 | 0.7188 | 0.5328 | 0.085* | |
C4C | 0.1240 (3) | 0.63659 (14) | 0.50794 (7) | 0.0648 (6) | |
H4C | 0.0707 | 0.6245 | 0.5331 | 0.078* | |
C5C | 0.0896 (3) | 0.59846 (19) | 0.47187 (8) | 0.1050 (11) | |
H5C | 0.0147 | 0.5575 | 0.4721 | 0.126* | |
C6C | 0.1614 (3) | 0.61794 (17) | 0.43466 (7) | 0.0891 (9) | |
H6C | 0.1324 | 0.5917 | 0.4095 | 0.107* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0408 (3) | 0.0337 (3) | 0.0345 (3) | 0.00096 (19) | 0.0005 (2) | 0.00099 (19) |
C1 | 0.0459 (11) | 0.0364 (10) | 0.0403 (10) | −0.0044 (8) | 0.0022 (8) | 0.0005 (8) |
C2 | 0.0538 (12) | 0.0372 (11) | 0.0435 (11) | −0.0022 (9) | 0.0049 (9) | 0.0022 (8) |
C4 | 0.0618 (14) | 0.0590 (14) | 0.0693 (16) | 0.0173 (11) | 0.0116 (11) | 0.0064 (11) |
C5 | 0.106 (2) | 0.099 (2) | 0.0760 (19) | 0.0275 (17) | 0.0241 (16) | 0.0050 (16) |
C7 | 0.0478 (12) | 0.0536 (12) | 0.0443 (12) | −0.0071 (10) | 0.0023 (9) | −0.0036 (9) |
C8 | 0.0692 (16) | 0.117 (2) | 0.0492 (14) | −0.0274 (15) | 0.0122 (11) | 0.0072 (13) |
C9 | 0.0647 (15) | 0.0887 (18) | 0.0740 (16) | −0.0083 (13) | 0.0185 (13) | 0.0083 (13) |
C10 | 0.0466 (11) | 0.0446 (11) | 0.0414 (11) | −0.0069 (8) | −0.0013 (8) | 0.0009 (8) |
O1 | 0.0500 (9) | 0.0410 (7) | 0.0686 (9) | 0.0048 (6) | 0.0064 (7) | 0.0010 (6) |
O2 | 0.0739 (10) | 0.0348 (8) | 0.0852 (11) | −0.0045 (7) | 0.0134 (8) | 0.0009 (7) |
O5 | 0.0636 (10) | 0.1417 (16) | 0.0470 (10) | −0.0314 (10) | −0.0066 (8) | 0.0100 (9) |
O6 | 0.0520 (9) | 0.0923 (12) | 0.0498 (9) | −0.0176 (8) | 0.0037 (7) | 0.0092 (7) |
C1A | 0.0422 (10) | 0.0413 (10) | 0.0348 (9) | 0.0018 (8) | 0.0034 (8) | −0.0001 (8) |
C2A | 0.0576 (13) | 0.0438 (11) | 0.0468 (12) | 0.0031 (9) | −0.0026 (10) | −0.0016 (9) |
C3A | 0.0684 (14) | 0.0571 (13) | 0.0494 (13) | −0.0089 (11) | −0.0018 (11) | −0.0120 (10) |
C4A | 0.0744 (16) | 0.0852 (18) | 0.0425 (13) | −0.0115 (13) | −0.0093 (11) | −0.0095 (12) |
C5A | 0.0924 (19) | 0.0718 (16) | 0.0506 (14) | −0.0038 (14) | −0.0229 (12) | 0.0129 (11) |
C6A | 0.0743 (15) | 0.0493 (12) | 0.0497 (12) | −0.0027 (11) | −0.0124 (11) | 0.0078 (10) |
C1B | 0.0422 (11) | 0.0351 (10) | 0.0504 (12) | 0.0002 (8) | −0.0029 (9) | −0.0025 (8) |
C2B | 0.0581 (14) | 0.0591 (14) | 0.0684 (15) | 0.0070 (11) | −0.0075 (11) | 0.0140 (11) |
C3B | 0.0650 (16) | 0.0691 (17) | 0.115 (2) | 0.0115 (14) | −0.0223 (16) | 0.0248 (15) |
C4B | 0.0471 (14) | 0.0573 (15) | 0.139 (3) | 0.0140 (12) | −0.0045 (16) | −0.0110 (16) |
C5B | 0.0564 (15) | 0.0755 (17) | 0.102 (2) | 0.0116 (13) | 0.0140 (14) | −0.0210 (15) |
C6B | 0.0549 (13) | 0.0640 (14) | 0.0622 (14) | 0.0127 (11) | 0.0063 (11) | −0.0058 (11) |
C1C | 0.0455 (11) | 0.0373 (10) | 0.0354 (10) | 0.0011 (8) | 0.0007 (8) | 0.0022 (8) |
C2C | 0.0829 (16) | 0.0674 (14) | 0.0424 (12) | −0.0246 (12) | 0.0022 (11) | −0.0024 (10) |
C3C | 0.101 (2) | 0.0781 (16) | 0.0347 (11) | −0.0097 (15) | 0.0030 (12) | −0.0056 (10) |
C4C | 0.0672 (15) | 0.0833 (17) | 0.0439 (13) | 0.0016 (13) | 0.0147 (11) | 0.0108 (11) |
C5C | 0.111 (2) | 0.146 (3) | 0.0577 (17) | −0.077 (2) | 0.0224 (15) | −0.0071 (17) |
C6C | 0.103 (2) | 0.120 (2) | 0.0444 (14) | −0.0636 (18) | 0.0150 (13) | −0.0151 (13) |
Geometric parameters (Å, º) top
P1—C1 | 1.7196 (18) | C2A—H2A | 0.9500 |
P1—C1B | 1.8073 (19) | C3A—C4A | 1.380 (3) |
P1—C1A | 1.8172 (18) | C3A—H3A | 0.9500 |
P1—C1C | 1.8186 (18) | C4A—C5A | 1.375 (3) |
C1—C2 | 1.404 (3) | C4A—H4A | 0.9500 |
C1—C10 | 1.511 (3) | C5A—C6A | 1.385 (3) |
C2—O2 | 1.230 (2) | C5A—H5A | 0.9500 |
C2—O1 | 1.374 (2) | C6A—H6A | 0.9500 |
C4—O1 | 1.435 (2) | C1B—C2B | 1.375 (3) |
C4—C5 | 1.496 (3) | C1B—C6B | 1.388 (3) |
C4—H4E | 0.9900 | C2B—C3B | 1.404 (3) |
C4—H4D | 0.9900 | C2B—H2B | 0.9500 |
C5—H5F | 0.9800 | C3B—C4B | 1.357 (4) |
C5—H5D | 0.9800 | C3B—H3B | 0.9500 |
C5—H5E | 0.9800 | C4B—C5B | 1.367 (4) |
C7—O5 | 1.193 (2) | C4B—H4B | 0.9500 |
C7—O6 | 1.334 (2) | C5B—C6B | 1.386 (3) |
C7—C10 | 1.504 (3) | C5B—H5B | 0.9500 |
C8—O6 | 1.451 (2) | C6B—H6B | 0.9500 |
C8—C9 | 1.477 (3) | C1C—C6C | 1.364 (3) |
C8—H8A | 0.9900 | C1C—C2C | 1.372 (3) |
C8—H8B | 0.9900 | C2C—C3C | 1.378 (3) |
C9—H9A | 0.9800 | C2C—H2C | 0.9500 |
C9—H9B | 0.9800 | C3C—C4C | 1.356 (3) |
C9—H9C | 0.9800 | C3C—H3C | 0.9500 |
C10—H10A | 0.9900 | C4C—C5C | 1.351 (3) |
C10—H10B | 0.9900 | C4C—H4C | 0.9500 |
C1A—C6A | 1.383 (3) | C5C—C6C | 1.382 (3) |
C1A—C2A | 1.394 (3) | C5C—H5C | 0.9500 |
C2A—C3A | 1.374 (3) | C6C—H6C | 0.9500 |
| | | |
C1—P1—C1B | 107.68 (9) | C3A—C2A—H2A | 119.6 |
C1—P1—C1A | 116.83 (8) | C1A—C2A—H2A | 119.6 |
C1B—P1—C1A | 103.53 (8) | C2A—C3A—C4A | 119.8 (2) |
C1—P1—C1C | 112.80 (8) | C2A—C3A—H3A | 120.1 |
C1B—P1—C1C | 107.35 (8) | C4A—C3A—H3A | 120.1 |
C1A—P1—C1C | 107.88 (9) | C5A—C4A—C3A | 120.0 (2) |
C2—C1—C10 | 116.92 (16) | C5A—C4A—H4A | 120.0 |
C2—C1—P1 | 120.37 (15) | C3A—C4A—H4A | 120.0 |
C10—C1—P1 | 122.64 (14) | C4A—C5A—C6A | 120.3 (2) |
O2—C2—O1 | 120.86 (17) | C4A—C5A—H5A | 119.8 |
O2—C2—C1 | 126.21 (19) | C6A—C5A—H5A | 119.8 |
O1—C2—C1 | 112.93 (16) | C1A—C6A—C5A | 120.2 (2) |
O1—C4—C5 | 112.15 (18) | C1A—C6A—H6A | 119.9 |
O1—C4—H4E | 109.2 | C5A—C6A—H6A | 119.9 |
C5—C4—H4E | 109.2 | C2B—C1B—C6B | 119.45 (19) |
O1—C4—H4D | 109.2 | C2B—C1B—P1 | 122.52 (16) |
C5—C4—H4D | 109.2 | C6B—C1B—P1 | 117.98 (15) |
H4E—C4—H4D | 107.9 | C1B—C2B—C3B | 119.2 (2) |
C4—C5—H5F | 109.5 | C1B—C2B—H2B | 120.4 |
C4—C5—H5D | 109.5 | C3B—C2B—H2B | 120.4 |
H5F—C5—H5D | 109.5 | C4B—C3B—C2B | 120.9 (2) |
C4—C5—H5E | 109.5 | C4B—C3B—H3B | 119.6 |
H5F—C5—H5E | 109.5 | C2B—C3B—H3B | 119.6 |
H5D—C5—H5E | 109.5 | C3B—C4B—C5B | 120.0 (2) |
O5—C7—O6 | 123.05 (19) | C3B—C4B—H4B | 120.0 |
O5—C7—C10 | 126.98 (19) | C5B—C4B—H4B | 120.0 |
O6—C7—C10 | 109.97 (17) | C4B—C5B—C6B | 120.1 (2) |
O6—C8—C9 | 107.42 (19) | C4B—C5B—H5B | 119.9 |
O6—C8—H8A | 110.2 | C6B—C5B—H5B | 119.9 |
C9—C8—H8A | 110.2 | C5B—C6B—C1B | 120.2 (2) |
O6—C8—H8B | 110.2 | C5B—C6B—H6B | 119.9 |
C9—C8—H8B | 110.2 | C1B—C6B—H6B | 119.9 |
H8A—C8—H8B | 108.5 | C6C—C1C—C2C | 117.32 (18) |
C8—C9—H9A | 109.5 | C6C—C1C—P1 | 123.35 (14) |
C8—C9—H9B | 109.5 | C2C—C1C—P1 | 119.27 (15) |
H9A—C9—H9B | 109.5 | C1C—C2C—C3C | 121.6 (2) |
C8—C9—H9C | 109.5 | C1C—C2C—H2C | 119.2 |
H9A—C9—H9C | 109.5 | C3C—C2C—H2C | 119.2 |
H9B—C9—H9C | 109.5 | C4C—C3C—C2C | 120.2 (2) |
C7—C10—C1 | 115.89 (16) | C4C—C3C—H3C | 119.9 |
C7—C10—H10A | 108.3 | C2C—C3C—H3C | 119.9 |
C1—C10—H10A | 108.3 | C5C—C4C—C3C | 118.8 (2) |
C7—C10—H10B | 108.3 | C5C—C4C—H4C | 120.6 |
C1—C10—H10B | 108.3 | C3C—C4C—H4C | 120.6 |
H10A—C10—H10B | 107.4 | C4C—C5C—C6C | 121.2 (2) |
C2—O1—C4 | 117.24 (16) | C4C—C5C—H5C | 119.4 |
C7—O6—C8 | 117.79 (16) | C6C—C5C—H5C | 119.4 |
C6A—C1A—C2A | 118.75 (18) | C1C—C6C—C5C | 120.8 (2) |
C6A—C1A—P1 | 120.03 (15) | C1C—C6C—H6C | 119.6 |
C2A—C1A—P1 | 121.15 (13) | C5C—C6C—H6C | 119.6 |
C3A—C2A—C1A | 120.87 (18) | | |
| | | |
C1B—P1—C1—C2 | −171.83 (14) | C2A—C1A—C6A—C5A | 2.0 (3) |
C1A—P1—C1—C2 | 72.30 (16) | P1—C1A—C6A—C5A | 178.93 (18) |
C1C—P1—C1—C2 | −53.57 (17) | C4A—C5A—C6A—C1A | −0.9 (4) |
C1B—P1—C1—C10 | 11.26 (17) | C1—P1—C1B—C2B | 106.72 (17) |
C1A—P1—C1—C10 | −104.62 (15) | C1A—P1—C1B—C2B | −128.96 (17) |
C1C—P1—C1—C10 | 129.52 (14) | C1C—P1—C1B—C2B | −15.00 (19) |
C10—C1—C2—O2 | −5.6 (3) | C1—P1—C1B—C6B | −71.05 (17) |
P1—C1—C2—O2 | 177.28 (16) | C1A—P1—C1B—C6B | 53.28 (17) |
C10—C1—C2—O1 | 174.82 (15) | C1C—P1—C1B—C6B | 167.24 (15) |
P1—C1—C2—O1 | −2.3 (2) | C6B—C1B—C2B—C3B | 0.0 (3) |
O5—C7—C10—C1 | −4.0 (3) | P1—C1B—C2B—C3B | −177.73 (17) |
O6—C7—C10—C1 | 175.86 (16) | C1B—C2B—C3B—C4B | 1.2 (4) |
C2—C1—C10—C7 | −81.0 (2) | C2B—C3B—C4B—C5B | −0.8 (4) |
P1—C1—C10—C7 | 96.03 (19) | C3B—C4B—C5B—C6B | −0.8 (4) |
O2—C2—O1—C4 | −12.4 (3) | C4B—C5B—C6B—C1B | 2.0 (4) |
C1—C2—O1—C4 | 167.14 (16) | C2B—C1B—C6B—C5B | −1.6 (3) |
C5—C4—O1—C2 | −76.2 (2) | P1—C1B—C6B—C5B | 176.23 (17) |
O5—C7—O6—C8 | 0.7 (3) | C1—P1—C1C—C6C | 151.7 (2) |
C10—C7—O6—C8 | −179.09 (18) | C1B—P1—C1C—C6C | −89.8 (2) |
C9—C8—O6—C7 | 169.7 (2) | C1A—P1—C1C—C6C | 21.2 (2) |
C1—P1—C1A—C6A | −8.67 (19) | C1—P1—C1C—C2C | −31.1 (2) |
C1B—P1—C1A—C6A | −126.82 (17) | C1B—P1—C1C—C2C | 87.31 (18) |
C1C—P1—C1A—C6A | 119.61 (16) | C1A—P1—C1C—C2C | −161.69 (16) |
C1—P1—C1A—C2A | 168.22 (15) | C6C—C1C—C2C—C3C | −0.3 (4) |
C1B—P1—C1A—C2A | 50.07 (17) | P1—C1C—C2C—C3C | −177.67 (18) |
C1C—P1—C1A—C2A | −63.50 (17) | C1C—C2C—C3C—C4C | −0.1 (4) |
C6A—C1A—C2A—C3A | −1.8 (3) | C2C—C3C—C4C—C5C | 1.7 (4) |
P1—C1A—C2A—C3A | −178.78 (16) | C3C—C4C—C5C—C6C | −2.9 (5) |
C1A—C2A—C3A—C4A | 0.7 (3) | C2C—C1C—C6C—C5C | −0.8 (4) |
C2A—C3A—C4A—C5A | 0.4 (4) | P1—C1C—C6C—C5C | 176.4 (2) |
C3A—C4A—C5A—C6A | −0.3 (4) | C4C—C5C—C6C—C1C | 2.5 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4B—H4B···O2i | 0.95 | 2.46 | 3.389 (3) | 165 |
Symmetry code: (i) −x+3/2, y−1/2, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C27H27O5P | C27H27O5P·C2H4O2 | C26H27O4P |
Mr | 462.46 | 522.51 | 434.45 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Orthorhombic, Pbca |
Temperature (K) | 150 | 150 | 150 |
a, b, c (Å) | 9.0348 (10), 10.3770 (11), 13.8951 (15) | 9.957 (4), 10.589 (4), 14.928 (6) | 8.7357 (10), 16.8280 (18), 31.896 (4) |
α, β, γ (°) | 95.994 (2), 108.342 (2), 107.304 (2) | 78.191 (6), 71.505 (6), 64.285 (6) | 90, 90, 90 |
V (Å3) | 1152.0 (2) | 1340.7 (9) | 4688.9 (9) |
Z | 2 | 2 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.16 | 0.15 | 0.15 |
Crystal size (mm) | 0.46 × 0.26 × 0.19 | 0.46 × 0.38 × 0.32 | 0.57 × 0.47 × 0.06 |
|
Data collection |
Diffractometer | Bruker SMART? CCD area-detector diffractometer | Bruker SMART? CCD area-detector diffractometer | Bruker SMART? CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) | Multi-scan (SADABS; Sheldrick, 2001) | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.95, 0.97 | 0.93, 0.95 | 0.92, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9669, 4935, 4077 | 11211, 5728, 4037 | 36723, 5370, 3279 |
Rint | 0.021 | 0.112 | 0.086 |
(sin θ/λ)max (Å−1) | 0.657 | 0.660 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.143, 1.09 | 0.058, 0.171, 0.93 | 0.052, 0.139, 0.91 |
No. of reflections | 4935 | 5728 | 5370 |
No. of parameters | 344 | 341 | 280 |
No. of restraints | 122 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.05, −0.36 | 0.49, −0.36 | 0.44, −0.22 |
Selected bond lengths (Å) for (I) topP1—C1 | 1.7546 (18) | O1—C4 | 1.452 (2) |
P1—C1A | 1.8055 (19) | O2—C2 | 1.220 (2) |
P1—C1C | 1.8106 (19) | O4—C3 | 1.240 (2) |
P1—C1B | 1.8183 (19) | C1—C3 | 1.432 (3) |
O1—C2 | 1.361 (2) | C1—C2 | 1.453 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O2 | 0.99 | 2.23 | 2.853 (3) | 120 |
C2A—H2A···O2i | 0.95 | 2.54 | 3.189 (3) | 126 |
C3B—H3B···O5'i | 0.95 | 2.48 | 3.327 (5) | 150 |
C4A—H4A···O4ii | 0.95 | 2.38 | 3.245 (3) | 151 |
C9'—H9'A···Cg1iii | 0.98 | 2.74 | 3.712 (4) | 172 |
C4C—H4C···Cg2iv | 0.95 | 2.79 | 3.604 (2) | 144 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+1; (iii) x+1, y+1, z; (iv) −x, −y+1, −z. |
π–π contacts (Å, °) for (I) topGroup_1/Group_2 | CCD (Å) | PCD (Å) |
Cg1···Cg1ii | 3.8512 (12) | 3.5410 (8) |
Cg3···Cg3iv | 3.9326 (12) | 3.6424 (8) |
Symmetry codes: (ii) -x + 1, -y + 2, -z + 1; (iv) -x, -y + 1, -z;
Cg1 is the centroid of the C1A–C6A ring, Cg2 that of the C1B–C6B ring and Cg3
that of the C1C–C6C ring.
Notes: CCD is the centroid-to-centroid distance and PCD is the (mean)
centroid to opposite plane distance. The rings are parallel by symmetry.
For details, see Janiak (2000). |
Selected bond lengths (Å) for (II) topP1—C1 | 1.758 (2) | O1—C4 | 1.450 (3) |
P1—C1A | 1.806 (2) | O2—C2 | 1.212 (2) |
P1—C1B | 1.812 (2) | O4—C3 | 1.255 (2) |
P1—C1C | 1.817 (2) | C1—C3 | 1.417 (3) |
O1—C2 | 1.343 (3) | C1—C2 | 1.455 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6A—H6A···O5 | 0.95 | 2.57 | 3.498 (4) | 165 |
C5—H5E···Cg2 | 0.98 | 2.97 | 3.820 (3) | 146 |
O2D—H2D···O4 | 0.859 (10) | 1.85 (2) | 2.636 (3) | 152 (4) |
C10—H10B···O1D | 0.99 | 2.47 | 3.430 (3) | 163 |
C2A—H2A···O1Di | 0.95 | 2.59 | 3.377 (3) | 140 |
C2D—H2DB···O5ii | 0.98 | 2.41 | 3.345 (4) | 160 |
C4B—H4B···Cg3iii | 0.95 | 2.85 | 3.711 (4) | 152 |
C9—H9B···Cg1iv | 0.98 | 2.86 | 3.744 (4) | 150 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) x+1, y, z. |
π–π contacts (Å) for (II) topGroup_1/Group_2 | CCD (Å) | PCD (Å) |
Cg1···Cg1v | 3.762 (2) | 3.520 (2) |
Cg2···Cg2iii | 3.814 (2) | 3.630 (2) |
Symmetry codes: (v) -x, -y + 1, -z + 1; (iii) -x, -y + 1, -z.
Cg1 is the centroid of the C1A–C6A ring, Cg2 that of the C1B–C6B ring and Cg3
that of the C1C–C6C ring.
Notes: CCD is the centroid-to-centroid distance and PCD is the (mean)
centroid to opposite plane distance. The rings are parallel by symmetry.
For details, see Janiak (2000). |
Selected bond lengths (Å) for (III) topP1—C1 | 1.7196 (18) | C1—C10 | 1.511 (3) |
P1—C1B | 1.8073 (19) | C2—O2 | 1.230 (2) |
P1—C1A | 1.8172 (18) | C2—O1 | 1.374 (2) |
P1—C1C | 1.8186 (18) | C4—O1 | 1.435 (2) |
C1—C2 | 1.404 (3) | | |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4B—H4B···O2i | 0.95 | 2.46 | 3.389 (3) | 165 |
Symmetry code: (i) −x+3/2, y−1/2, z. |
The conformations of triphenylphosphonium ylides with a single keto or ester group conjugated with the ylidic double bond are best established by X-ray crystallography, provided that suitable crystals can be isolated, or else inferred from NMR or IR spectroscopy (Bachrach & Nitsche, 1994). The ylidic residue is typically close to planar, with electronic delocalization involving the P atom, the ylidic C atom and the associated acyl group. The conformations are designated as syn or anti, depending on the orientation of the acyl group, either towards or away from the P atom (Aitken et al., 2000) [part (a) of second scheme]. However, these classical representations of structures with a C═P double bond are inadequate in that they neglect electronic delocalizations. The existence of zwitterionic structures with extensive delocalization [part (b) of second scheme] provides due evidence of this fact (Bachrach, 1992). In addition, conformations with two acyl groups could be syn–syn, syn–anti or anti–anti (Aitken et al. 2000) [part (c) of second scheme].
Only syn–anti and anti–anti conformers of aliphatic diacyl derivatives have been observed to date and the latter only with a few diesters (Castañeda et al., 2001, 2005). The situation is more complicated with different acyl groups, but generally in aliphatic keto esters the ester acyl group is anti and the keto acyl group syn (Castañeda et al., 2001, 2003). In mixed aliphatic diesters, the smaller ester group is usually syn and the large group anti with respect to P (Castañeda et al., 2009a,b). These generalizations do not apply when aryl groups are present in the ylidic residue, where electronic delocalization and steric effects have to be considered, nor to some diylides with bulky structures (Aitken et al., 2000).
The present work involves three triphenyl phosphonium ylides: two keto diesters, diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate, C27H27O5P, (I), and diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate acetic acid solvate, C29H31O7P, (II), and one diester, diethyl 2-(triphenylphosphoranylidene)succinate, C26H27O4P, (III), with one ylidic and one nonylidic ester group. These ylides were prepared in order to examine whether nonylidic external carboxylic ester groups affect the conformations of the ylidic moieties in the crystal structures.
Figs. 1(a), 2(a) and 3(a) show the corresponding molecular views and the atomic labelling schemes used for (I), (II) and (III), respectively. These three ylides share common features, in particular a slightly distorted tetrahedral arragement around the P atom, with the phenyl groups in a propeller-like disposition, as observed for stabilized keto ester ylides (Castañeda et al., 2001). The sums of the angles about the ylidic atom C1 are very near the ideal 360°, consistent with sp2 hybridization [357.99 (42)° in (I), 358.62 (48)° in (II) and 359.93 (45)° in (III)] in a near trigonal-planar geometry.
The P—C1 bond lengths [mean = 1.74 (2) Å] lie between accepted values for single and double bonds (1.80–1.83 Å and 1.66 Å, respectively; Howells et al., 1973) due to electronic delocalization which shortens C1—C2 (in all three structures) and C1—C3 [in (I) and (II)]. The ylidic keto carbonyl bonds are longer than the typical value of 1.21 Å [C3—O4 = 1.239 (2)–1.254 (2) Å] for keto-ester, diester and diketo ylides (Castañeda et al., 2001, 2005).
In the crystalline stabilized ylides (I)–(II), the keto O atom and the ylidic alkoxy groups are oriented towards P with syn-keto and anti-ester conformations, respectively. (Figs. 1–2). A syn-keto conformation is also established by pyrolysis of diketo or keto ester-ylides, i.e. (I), where syn-keto conformations are required to form keto or ester acetylenes, respectively (Gough & Trippett, 1962; Chopard et al. 1965).
Coplanarity between the ylidic keto carbonyl and ester carbonyl units in (I) and (II) is indicated by their torsion angles. The P—C—C—O torsion angles are close to -2.5° for the keto group and near to 167° for the ester carbonyl, showing stronger delocalization of the keto group. The keto and ester carbonyl groups in (I) and (II) have opposite orientations, which reduces dipole–dipole repulsions, and the keto O atoms are within 2.88–2.91 Å of P, i.e. within the sum of the van der Waals radii (Standard reference?), and favourable interactions should stabilize the conformer. The ester groups in (I)–(III) have the typical Z conformation (Eliel & Wilen, 1994) and are approximately in the ylidic plane.
The keto diester ylide solvate, (II), was prepared because acetic acid can promote the formation of good single crystals (Abel et al. 1989) and new intermolecular interactions could modify the syn-keto anti-ester conformation of ylide (I). However, (II) is a 1:1 ylide solvate with intermolecular hydrogen-bond interactions and syn-keto anti-ester conformations as in (I).
The anti-ester conformations in crystalline ylides (I)–(III) (Figs. 1–3) do not depend on the presence of a syn-keto group and could be favoured by alkoxy O···P interactions, an attractive C—H···π effect (Nishio et al. 1995) or the absence of nonbonded steric repulsion between alkoxy ylidic and nonylidic ester groups. In the crystal structure and in solution (1H NMR), the structures present one alkoxy group syn to P directed towards the face of a phenyl group which is approximately orthogonal to the ylidic C—P bond with a modestly stabilizing C—H···π interaction (Nishio et al. 1995; Nishio & Hirota, 1989). The crystalline structure of the mono ylidic diester, (III), determined by X-ray crystallography showed an anti-ester conformation with a contact distance of 2.8177 (15) Å between atoms P1 and O1.
The nonbonding interactions in (I), (II) and (III) are quite different in all three structures. Compound (III) presents only one close P···O contact [P1..O1 = 2.818 (2) Å] and one moderate C—H···O intermolecular bond (Table 6), the remaining interactions being mostly van der Waals. Compounds (I) and (II), instead, display a large number of stabilizing nonbonding contacts of diverse nature and strength. There are two short intramolecular P···O in each [P1···O1 = 2.877 (2) Å and P1···O4 = 2.879 (2) Å in (I); P1···O1 = 2.888 (2) Å and P1···O4 = 2.915 (2) Å in (II)], many conventional and non-conventional hydrogen bonds and C—H···π contacts (both intra- and intermolecular) (Tables 2 and 4) and some π···π stacking interactions between aromatic rings (Tables 7 and 8). All these contacts are presented schematically in Figs. 1(b), 2(b) and 3(b), and their inspection confirms a final three-dimensional packing structure for (I) and (II), but a much simpler one-dimensional (chain-like) structure for (III).