Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803002137/ob6212sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803002137/ob6212Isup2.hkl |
CCDC reference: 204724
The title phosphonium salt, (I), was obtained when the product of the reaction between stannic iodide and the phosphonium ylide, (benzoylmethylene)triphenylphosphorane was crystallized in dry methanol.
All the H atoms were located from difference Fourier maps and their positional and Uiso parameters were refined. The C—H bond distances range from 0.91 (3) to 0.98 (2) Å.
Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.
C26H22OP+·I− | Dx = 1.482 Mg m−3 |
Mr = 508.31 | Melting point: decomposes above 473 K K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 10.870 (2) Å | Cell parameters from 805 reflections |
b = 18.932 (2) Å | θ = 10.2–23.6° |
c = 22.135 (3) Å | µ = 1.49 mm−1 |
V = 4555.2 (11) Å3 | T = 120 K |
Z = 8 | Block, light yellow |
F(000) = 2032 | 0.46 × 0.32 × 0.28 mm |
Bruker SMART 1K CCD diffractometer | 5663 independent reflections |
Radiation source: fine-focus sealed tube | 4873 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 28.3°, θmin = 2.2° |
Absorption correction: integration (XPREP in SHELXTL; Bruker, 1998) | h = −13→14 |
Tmin = 0.555, Tmax = 0.684 | k = −25→24 |
29262 measured reflections | l = −29→23 |
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)] = 0.026 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.057 | All H-atom parameters refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0193P)2 + 4.7P] where P = (Fo2 + 2Fc2)/3 |
5663 reflections | (Δ/σ)max = 0.002 |
350 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.74 e Å−3 |
C26H22OP+·I− | V = 4555.2 (11) Å3 |
Mr = 508.31 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.870 (2) Å | µ = 1.49 mm−1 |
b = 18.932 (2) Å | T = 120 K |
c = 22.135 (3) Å | 0.46 × 0.32 × 0.28 mm |
Bruker SMART 1K CCD diffractometer | 5663 independent reflections |
Absorption correction: integration (XPREP in SHELXTL; Bruker, 1998) | 4873 reflections with I > 2σ(I) |
Tmin = 0.555, Tmax = 0.684 | Rint = 0.030 |
29262 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.057 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.62 e Å−3 |
5663 reflections | Δρmin = −0.74 e Å−3 |
350 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.340625 (13) | 0.346975 (7) | 0.393471 (6) | 0.02309 (5) | |
P1 | 0.37220 (5) | 0.11545 (3) | 0.32890 (2) | 0.01544 (10) | |
O1 | 0.20335 (14) | 0.17728 (8) | 0.23889 (7) | 0.0244 (3) | |
C1 | 0.39361 (19) | 0.19780 (10) | 0.28896 (9) | 0.0170 (4) | |
H1 | 0.478 (2) | 0.1994 (11) | 0.2761 (10) | 0.019 (6)* | |
H2 | 0.383 (2) | 0.2342 (14) | 0.3157 (12) | 0.034 (7)* | |
C2 | 0.30185 (18) | 0.20869 (10) | 0.23813 (9) | 0.0177 (4) | |
C3 | 0.33438 (19) | 0.25922 (10) | 0.18899 (9) | 0.0197 (4) | |
C4 | 0.2558 (2) | 0.26312 (12) | 0.13911 (10) | 0.0258 (5) | |
H4 | 0.186 (2) | 0.2312 (14) | 0.1372 (12) | 0.034 (7)* | |
C5 | 0.2815 (2) | 0.30947 (14) | 0.09199 (11) | 0.0325 (5) | |
H5 | 0.228 (3) | 0.3097 (15) | 0.0574 (13) | 0.045 (8)* | |
C6 | 0.3850 (3) | 0.35259 (13) | 0.09479 (12) | 0.0347 (6) | |
H6 | 0.405 (3) | 0.3839 (15) | 0.0630 (13) | 0.041 (8)* | |
C7 | 0.4641 (2) | 0.34901 (13) | 0.14419 (11) | 0.0313 (5) | |
H7 | 0.534 (2) | 0.3784 (13) | 0.1459 (11) | 0.028 (6)* | |
C8 | 0.4391 (2) | 0.30237 (11) | 0.19148 (10) | 0.0241 (4) | |
H8 | 0.492 (2) | 0.3014 (13) | 0.2254 (12) | 0.030 (7)* | |
C11 | 0.50269 (18) | 0.10598 (10) | 0.37836 (9) | 0.0177 (4) | |
C12 | 0.5937 (2) | 0.05561 (12) | 0.36804 (10) | 0.0256 (5) | |
H12 | 0.587 (2) | 0.0254 (14) | 0.3328 (12) | 0.038 (7)* | |
C13 | 0.6922 (2) | 0.04983 (15) | 0.40828 (11) | 0.0346 (6) | |
H13 | 0.753 (3) | 0.0162 (14) | 0.4016 (12) | 0.039 (8)* | |
C14 | 0.6987 (2) | 0.09405 (13) | 0.45788 (11) | 0.0285 (5) | |
H14 | 0.760 (3) | 0.0901 (14) | 0.4868 (12) | 0.038 (7)* | |
C15 | 0.6084 (2) | 0.14484 (12) | 0.46803 (10) | 0.0251 (4) | |
H15 | 0.613 (2) | 0.1744 (13) | 0.5013 (11) | 0.026 (6)* | |
C16 | 0.5098 (2) | 0.15087 (11) | 0.42866 (9) | 0.0221 (4) | |
H16 | 0.449 (2) | 0.1855 (13) | 0.4347 (11) | 0.029 (7)* | |
C21 | 0.23968 (18) | 0.11510 (10) | 0.37758 (9) | 0.0173 (4) | |
C22 | 0.15386 (19) | 0.17010 (11) | 0.37802 (10) | 0.0215 (4) | |
H22 | 0.161 (2) | 0.2094 (13) | 0.3497 (11) | 0.025 (6)* | |
C23 | 0.0595 (2) | 0.17014 (12) | 0.42064 (11) | 0.0262 (5) | |
H23 | 0.005 (2) | 0.2089 (13) | 0.4204 (11) | 0.029 (7)* | |
C24 | 0.0512 (2) | 0.11619 (13) | 0.46268 (10) | 0.0277 (5) | |
H24 | −0.009 (2) | 0.1188 (13) | 0.4916 (12) | 0.032 (7)* | |
C25 | 0.1358 (2) | 0.06123 (13) | 0.46219 (10) | 0.0277 (5) | |
H25 | 0.129 (2) | 0.0259 (13) | 0.4901 (12) | 0.029 (7)* | |
C26 | 0.2311 (2) | 0.06032 (11) | 0.42026 (10) | 0.0232 (4) | |
H26 | 0.290 (2) | 0.0229 (12) | 0.4199 (10) | 0.018 (6)* | |
C31 | 0.37251 (18) | 0.04508 (10) | 0.27484 (9) | 0.0174 (4) | |
C32 | 0.2969 (2) | −0.01413 (11) | 0.28208 (10) | 0.0232 (4) | |
H32 | 0.243 (2) | −0.0173 (12) | 0.3164 (11) | 0.023 (6)* | |
C33 | 0.3046 (2) | −0.06942 (12) | 0.24049 (11) | 0.0301 (5) | |
H33 | 0.256 (2) | −0.1086 (13) | 0.2457 (12) | 0.032 (7)* | |
C34 | 0.3869 (2) | −0.06619 (12) | 0.19311 (11) | 0.0275 (5) | |
H34 | 0.394 (2) | −0.1038 (13) | 0.1675 (11) | 0.028 (7)* | |
C35 | 0.4615 (2) | −0.00716 (12) | 0.18558 (10) | 0.0269 (5) | |
H35 | 0.520 (3) | −0.0065 (14) | 0.1517 (12) | 0.037 (7)* | |
C36 | 0.4551 (2) | 0.04867 (12) | 0.22622 (10) | 0.0240 (4) | |
H36 | 0.506 (2) | 0.0881 (13) | 0.2208 (12) | 0.034 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.02751 (8) | 0.02053 (7) | 0.02123 (7) | −0.00078 (5) | 0.00089 (5) | −0.00326 (5) |
P1 | 0.0140 (2) | 0.0163 (2) | 0.0160 (2) | −0.00006 (18) | 0.00037 (18) | −0.00063 (18) |
O1 | 0.0183 (7) | 0.0290 (8) | 0.0261 (8) | −0.0041 (6) | −0.0024 (6) | 0.0027 (6) |
C1 | 0.0169 (10) | 0.0165 (9) | 0.0178 (9) | −0.0009 (7) | −0.0006 (7) | 0.0001 (7) |
C2 | 0.0168 (9) | 0.0176 (9) | 0.0186 (10) | 0.0012 (7) | 0.0009 (7) | −0.0028 (7) |
C3 | 0.0201 (10) | 0.0194 (9) | 0.0196 (10) | 0.0036 (8) | 0.0028 (8) | −0.0005 (7) |
C4 | 0.0240 (11) | 0.0295 (12) | 0.0240 (11) | 0.0030 (9) | −0.0017 (9) | 0.0017 (9) |
C5 | 0.0359 (14) | 0.0373 (13) | 0.0243 (12) | 0.0095 (11) | −0.0013 (10) | 0.0048 (10) |
C6 | 0.0392 (14) | 0.0336 (13) | 0.0312 (13) | 0.0102 (11) | 0.0125 (10) | 0.0116 (10) |
C7 | 0.0296 (12) | 0.0295 (12) | 0.0348 (13) | −0.0007 (10) | 0.0088 (10) | 0.0080 (10) |
C8 | 0.0233 (11) | 0.0227 (10) | 0.0262 (11) | −0.0001 (8) | 0.0019 (9) | 0.0017 (8) |
C11 | 0.0151 (9) | 0.0225 (9) | 0.0155 (9) | −0.0006 (7) | −0.0006 (7) | 0.0021 (7) |
C12 | 0.0240 (11) | 0.0294 (11) | 0.0235 (11) | 0.0074 (9) | −0.0018 (9) | −0.0062 (9) |
C13 | 0.0248 (12) | 0.0458 (15) | 0.0333 (13) | 0.0165 (11) | −0.0057 (10) | −0.0089 (11) |
C14 | 0.0213 (11) | 0.0394 (13) | 0.0248 (11) | 0.0034 (9) | −0.0074 (9) | −0.0018 (10) |
C15 | 0.0246 (11) | 0.0309 (11) | 0.0199 (10) | −0.0009 (9) | −0.0021 (8) | −0.0034 (9) |
C16 | 0.0206 (10) | 0.0246 (10) | 0.0212 (10) | 0.0024 (9) | −0.0009 (8) | −0.0026 (8) |
C21 | 0.0161 (9) | 0.0198 (9) | 0.0162 (9) | 0.0003 (7) | 0.0016 (7) | −0.0027 (7) |
C22 | 0.0210 (10) | 0.0200 (9) | 0.0233 (10) | 0.0012 (8) | 0.0001 (8) | −0.0004 (8) |
C23 | 0.0186 (11) | 0.0299 (12) | 0.0300 (12) | 0.0051 (9) | 0.0031 (9) | −0.0048 (9) |
C24 | 0.0178 (11) | 0.0410 (13) | 0.0243 (11) | −0.0037 (9) | 0.0057 (9) | −0.0045 (10) |
C25 | 0.0271 (12) | 0.0348 (12) | 0.0213 (11) | −0.0028 (9) | 0.0046 (9) | 0.0049 (9) |
C26 | 0.0217 (11) | 0.0243 (11) | 0.0235 (11) | 0.0018 (9) | 0.0020 (8) | 0.0020 (8) |
C31 | 0.0173 (9) | 0.0174 (9) | 0.0174 (9) | 0.0010 (7) | −0.0018 (7) | −0.0025 (7) |
C32 | 0.0226 (10) | 0.0223 (10) | 0.0247 (11) | −0.0027 (8) | 0.0031 (8) | −0.0007 (8) |
C33 | 0.0288 (12) | 0.0234 (11) | 0.0380 (14) | −0.0079 (9) | −0.0008 (10) | −0.0067 (10) |
C34 | 0.0270 (12) | 0.0264 (11) | 0.0292 (12) | 0.0028 (9) | −0.0052 (9) | −0.0106 (9) |
C35 | 0.0240 (11) | 0.0334 (12) | 0.0231 (11) | 0.0021 (9) | 0.0033 (9) | −0.0069 (9) |
C36 | 0.0239 (11) | 0.0252 (11) | 0.0230 (11) | −0.0041 (9) | 0.0037 (8) | −0.0023 (8) |
P1—C31 | 1.791 (2) | C14—H14 | 0.93 (3) |
P1—C21 | 1.799 (2) | C15—C16 | 1.386 (3) |
P1—C11 | 1.801 (2) | C15—H15 | 0.93 (3) |
P1—C1 | 1.807 (2) | C16—H16 | 0.94 (3) |
O1—C2 | 1.225 (2) | C21—C22 | 1.398 (3) |
C1—C2 | 1.518 (3) | C21—C26 | 1.406 (3) |
C1—H1 | 0.96 (2) | C22—C23 | 1.393 (3) |
C1—H2 | 0.92 (3) | C22—H22 | 0.98 (2) |
C2—C3 | 1.491 (3) | C23—C24 | 1.385 (3) |
C3—C4 | 1.398 (3) | C23—H23 | 0.94 (3) |
C3—C8 | 1.402 (3) | C24—C25 | 1.389 (3) |
C4—C5 | 1.391 (3) | C24—H24 | 0.92 (3) |
C4—H4 | 0.97 (3) | C25—C26 | 1.391 (3) |
C5—C6 | 1.392 (4) | C25—H25 | 0.91 (3) |
C5—H5 | 0.96 (3) | C26—H26 | 0.95 (2) |
C6—C7 | 1.393 (4) | C31—C32 | 1.399 (3) |
C6—H6 | 0.95 (3) | C31—C36 | 1.403 (3) |
C7—C8 | 1.396 (3) | C32—C33 | 1.396 (3) |
C7—H7 | 0.94 (3) | C32—H32 | 0.96 (2) |
C8—H8 | 0.95 (3) | C33—C34 | 1.380 (3) |
C11—C12 | 1.393 (3) | C33—H33 | 0.92 (3) |
C11—C16 | 1.403 (3) | C34—C35 | 1.391 (3) |
C12—C13 | 1.397 (3) | C34—H34 | 0.91 (3) |
C12—H12 | 0.97 (3) | C35—C36 | 1.390 (3) |
C13—C14 | 1.383 (3) | C35—H35 | 0.98 (3) |
C13—H13 | 0.93 (3) | C36—H36 | 0.94 (3) |
C14—C15 | 1.393 (3) | ||
C31—P1—C21 | 113.51 (9) | C15—C14—H14 | 116.8 (17) |
C31—P1—C11 | 109.32 (9) | C16—C15—C14 | 120.1 (2) |
C21—P1—C11 | 105.44 (9) | C16—C15—H15 | 119.6 (16) |
C31—P1—C1 | 108.33 (9) | C14—C15—H15 | 120.3 (16) |
C21—P1—C1 | 113.53 (9) | C15—C16—C11 | 119.4 (2) |
C11—P1—C1 | 106.37 (9) | C15—C16—H16 | 120.7 (16) |
C2—C1—P1 | 113.28 (14) | C11—C16—H16 | 119.9 (16) |
C2—C1—H1 | 113.8 (14) | C22—C21—C26 | 120.05 (19) |
P1—C1—H1 | 107.1 (13) | C22—C21—P1 | 122.39 (15) |
C2—C1—H2 | 107.3 (17) | C26—C21—P1 | 117.26 (15) |
P1—C1—H2 | 108.5 (16) | C23—C22—C21 | 119.7 (2) |
H1—C1—H2 | 107 (2) | C23—C22—H22 | 119.5 (14) |
O1—C2—C3 | 121.92 (18) | C21—C22—H22 | 120.7 (14) |
O1—C2—C1 | 119.90 (18) | C24—C23—C22 | 120.2 (2) |
C3—C2—C1 | 118.17 (17) | C24—C23—H23 | 122.4 (15) |
C4—C3—C8 | 119.8 (2) | C22—C23—H23 | 117.4 (15) |
C4—C3—C2 | 117.71 (19) | C23—C24—C25 | 120.3 (2) |
C8—C3—C2 | 122.52 (19) | C23—C24—H24 | 118.4 (16) |
C5—C4—C3 | 120.2 (2) | C25—C24—H24 | 121.3 (16) |
C5—C4—H4 | 121.1 (16) | C24—C25—C26 | 120.5 (2) |
C3—C4—H4 | 118.6 (16) | C24—C25—H25 | 119.5 (16) |
C4—C5—C6 | 119.9 (2) | C26—C25—H25 | 119.9 (16) |
C4—C5—H5 | 118.4 (17) | C25—C26—C21 | 119.2 (2) |
C6—C5—H5 | 121.6 (17) | C25—C26—H26 | 121.0 (14) |
C5—C6—C7 | 120.4 (2) | C21—C26—H26 | 119.8 (14) |
C5—C6—H6 | 121.3 (18) | C32—C31—C36 | 120.17 (19) |
C7—C6—H6 | 118.3 (18) | C32—C31—P1 | 121.23 (16) |
C6—C7—C8 | 119.9 (2) | C36—C31—P1 | 118.53 (15) |
C6—C7—H7 | 120.0 (16) | C33—C32—C31 | 119.3 (2) |
C8—C7—H7 | 120.1 (16) | C33—C32—H32 | 120.7 (14) |
C7—C8—C3 | 119.8 (2) | C31—C32—H32 | 119.9 (14) |
C7—C8—H8 | 119.2 (15) | C34—C33—C32 | 120.5 (2) |
C3—C8—H8 | 120.9 (15) | C34—C33—H33 | 120.2 (17) |
C12—C11—C16 | 120.40 (19) | C32—C33—H33 | 119.3 (17) |
C12—C11—P1 | 121.86 (16) | C33—C34—C35 | 120.3 (2) |
C16—C11—P1 | 117.74 (15) | C33—C34—H34 | 119.3 (16) |
C11—C12—C13 | 119.6 (2) | C35—C34—H34 | 120.4 (16) |
C11—C12—H12 | 118.7 (16) | C36—C35—C34 | 120.3 (2) |
C13—C12—H12 | 121.8 (16) | C36—C35—H35 | 121.1 (16) |
C14—C13—C12 | 119.9 (2) | C34—C35—H35 | 118.6 (16) |
C14—C13—H13 | 120.2 (17) | C35—C36—C31 | 119.4 (2) |
C12—C13—H13 | 119.9 (17) | C35—C36—H36 | 119.5 (16) |
C13—C14—C15 | 120.7 (2) | C31—C36—H36 | 121.0 (16) |
C13—C14—H14 | 122.5 (17) | ||
C31—P1—C1—C2 | 53.60 (16) | P1—C11—C16—C15 | 179.53 (17) |
C21—P1—C1—C2 | −73.47 (16) | C31—P1—C21—C22 | −116.56 (18) |
C11—P1—C1—C2 | 171.02 (14) | C11—P1—C21—C22 | 123.80 (18) |
P1—C1—C2—O1 | 22.6 (2) | C1—P1—C21—C22 | 7.7 (2) |
P1—C1—C2—C3 | −158.66 (14) | C31—P1—C21—C26 | 69.73 (18) |
O1—C2—C3—C4 | −8.2 (3) | C11—P1—C21—C26 | −49.90 (18) |
C1—C2—C3—C4 | 173.10 (18) | C1—P1—C21—C26 | −165.96 (16) |
O1—C2—C3—C8 | 171.43 (19) | C26—C21—C22—C23 | −0.4 (3) |
C1—C2—C3—C8 | −7.3 (3) | P1—C21—C22—C23 | −173.94 (17) |
C8—C3—C4—C5 | 0.2 (3) | C21—C22—C23—C24 | 0.4 (3) |
C2—C3—C4—C5 | 179.9 (2) | C22—C23—C24—C25 | −0.8 (3) |
C3—C4—C5—C6 | −0.7 (4) | C23—C24—C25—C26 | 1.1 (4) |
C4—C5—C6—C7 | 0.8 (4) | C24—C25—C26—C21 | −1.1 (3) |
C5—C6—C7—C8 | −0.5 (4) | C22—C21—C26—C25 | 0.7 (3) |
C6—C7—C8—C3 | 0.1 (3) | P1—C21—C26—C25 | 174.60 (17) |
C4—C3—C8—C7 | 0.1 (3) | C21—P1—C31—C32 | −17.3 (2) |
C2—C3—C8—C7 | −179.6 (2) | C11—P1—C31—C32 | 100.12 (18) |
C31—P1—C11—C12 | 7.4 (2) | C1—P1—C31—C32 | −144.36 (17) |
C21—P1—C11—C12 | 129.79 (18) | C21—P1—C31—C36 | 165.93 (16) |
C1—P1—C11—C12 | −109.35 (19) | C11—P1—C31—C36 | −76.67 (18) |
C31—P1—C11—C16 | −171.95 (16) | C1—P1—C31—C36 | 38.85 (19) |
C21—P1—C11—C16 | −49.58 (18) | C36—C31—C32—C33 | 0.0 (3) |
C1—P1—C11—C16 | 71.28 (18) | P1—C31—C32—C33 | −176.74 (18) |
C16—C11—C12—C13 | 0.2 (3) | C31—C32—C33—C34 | 0.7 (4) |
P1—C11—C12—C13 | −179.13 (19) | C32—C33—C34—C35 | −1.2 (4) |
C11—C12—C13—C14 | −0.1 (4) | C33—C34—C35—C36 | 0.9 (4) |
C12—C13—C14—C15 | −0.5 (4) | C34—C35—C36—C31 | −0.2 (3) |
C13—C14—C15—C16 | 0.8 (4) | C32—C31—C36—C35 | −0.3 (3) |
C14—C15—C16—C11 | −0.7 (3) | P1—C31—C36—C35 | 176.56 (17) |
C12—C11—C16—C15 | 0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.96 (2) | 2.50 (2) | 3.445 (3) | 165.2 (18) |
C1—H2···I1 | 0.92 (3) | 2.78 (3) | 3.696 (2) | 177 (2) |
C14—H14···I1ii | 0.93 (3) | 3.03 (3) | 3.802 (2) | 141 (2) |
C24—H24···I1iii | 0.92 (3) | 3.09 (3) | 3.983 (2) | 164 (2) |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x+1/2, −y+1/2, −z+1; (iii) x−1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C26H22OP+·I− |
Mr | 508.31 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 120 |
a, b, c (Å) | 10.870 (2), 18.932 (2), 22.135 (3) |
V (Å3) | 4555.2 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.49 |
Crystal size (mm) | 0.46 × 0.32 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD diffractometer |
Absorption correction | Integration (XPREP in SHELXTL; Bruker, 1998) |
Tmin, Tmax | 0.555, 0.684 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29262, 5663, 4873 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.057, 1.05 |
No. of reflections | 5663 |
No. of parameters | 350 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.62, −0.74 |
Computer programs: SMART-NT (Bruker, 1998), SMART-NT, SAINT-NT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON97 (Spek, 1997), SHELXL97.
P1—C1 | 1.807 (2) | C1—C2 | 1.518 (3) |
O1—C2 | 1.225 (2) | ||
C31—P1—C1 | 108.33 (9) | O1—C2—C1 | 119.90 (18) |
C2—C1—P1 | 113.28 (14) | C3—C2—C1 | 118.17 (17) |
O1—C2—C3 | 121.92 (18) | ||
P1—C1—C2—O1 | 22.6 (2) | P1—C1—C2—C3 | −158.66 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.96 (2) | 2.50 (2) | 3.445 (3) | 165.2 (18) |
C1—H2···I1 | 0.92 (3) | 2.78 (3) | 3.696 (2) | 177 (2) |
C14—H14···I1ii | 0.93 (3) | 3.03 (3) | 3.802 (2) | 141 (2) |
C24—H24···I1iii | 0.92 (3) | 3.09 (3) | 3.983 (2) | 164 (2) |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x+1/2, −y+1/2, −z+1; (iii) x−1/2, −y+1/2, −z+1. |
Phosphonium keto ylides react with metal salts to form not only ylide complexes but also phosphonium salts (Antipin et al., 1984; Baby Mariyatra et al., 2002) and phosphonium metalates (Albanese et al., 1989; Bart et al.,1982). The action of trimethyltin chloride on (benzoylmethylene)triphenylphosphorane led to the first O-coordinated ketoylide complex (Buckel et al., 1972). The reaction of SnI4 with the same ylide was performed to prepare a six-coordinate complex, containing the ylide. However, the above reaction in benzene yielded the product of composition [(C6H5)3PCH2COPh]2[SnI6], as revealed by its elemental analysis (analysis found: C 37.98, H 2.78%; calculated: C 38.01, H 2.70%). The product was recrystallized from methanol. Its 1H NMR in CDCl3 indicates that it is a phosphonium salt different from the initial phosphonium metalate. The investigation reported herein has been undertaken to assign the molecular and supramolecular structure of the title compound, (I).
The molecular structure of (I) is unexceptional and formed by the C protonation of the parent ylide. It is confirmed that compound (I) is an ion pair (Fig. 1) with a distance of 4.6231 (7) Å between the P+ and I− centers. The metrical parameters in (I) resemble those of the isomorphous nitrate salt (Pbca with Z = 8; Baby Mariyatra et al., 2002), but differ from the parent ylide (Kalyanasundari et al., 1994). The crystal structure can be best described as a zigzag chain formed by C—H···O hydrogen-bonding interactions (Table 2 and Fig. 2). The H1—C1—C2—O1 torsion angle [145.4 (14)°] indicates that atoms H1 and O1 are considerably distorted from an antiperiplanar arrangement, as expected for the formation of a zigzag chain. The I− ions are embedded in the space between the chains and contribute to the three -dimensional arrangement via three C—H···I interactions (Table 2 and Fig. 3). The C···I distances [3.696 (2), 3.802 (2) and 3.983 (2) Å] are comparable to those observed in the fulleride salt [(C6H5)4P]2(C60)I0.35 (C···I− = 3.67 Å; Penicaud et al., 1993) and those observed in (α-ferrocenylphenacyl)triphenylphosphonium iodide [C···I = 3.836 (7), 3.932 (7) and 3.995 (7) Å; Ahmed et al., 1996].
The present results indicate that the phosphonium salt is present in the C-protonated form both in solution and solid state. The ylidic C atom is involved in hydrogen-bonding interactions, as observed in many similar structures (Yufit et al., 2000; Baby Mariyatra et al., 2002). We attribute the predominance of the C-protonated form to the considerable carbanionic character of the ylidic C atom in spite of resonance stabilization.