Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020419/na6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020419/na6032Isup2.hkl |
CCDC reference: 155904
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.005 Å
- H-atom completeness 99%
- Disorder in solvent or counterion
- R factor = 0.058
- wR factor = 0.168
- Data-to-parameter ratio = 13.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent disorder ....................... 12.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C42.5 H36 O2 P2 Atom count from the _atom_site data: C42.5 H35.5 O2 P2 CELLZ_01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C42.50 H36 O2 P2 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 85.00 85.00 0.00 H 72.00 71.00 1.00 O 4.00 4.00 0.00 P 4.00 4.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was obtained as a by-product in the attempted synthesis of (xantphos)nickel dicyanide. Colorless crystals were obtained by recrystallization from toluene of a solution containing styrene and cyclooctadiene.
Aromatic H atoms were constrained and allowed to ride on their C atoms with Uiso(H) = 1.2Ueq(C). The methyl H atoms were constrained to an ideal geometry with Uiso(H) = 1.5Ueq(C), and allowed to rotate freely about the C—C bonds. The toluene solvent was located near an inversion centre, so the methyl group was disordered over two sites, and refined with a site-occupancy factor of 50%. The H atom, at the same position as the disordered methyl group, was not refined.
Data collection: Locally modified CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: PLATON (Spek, 2000).
Fig. 1. PLATON/ORTEP representation (Spek, 2000) of (I) with displacement ellipsoids at 50% probability level. H atoms have been omitted for clarity. |
C39H32O2P2·0.5C7H8 | Z = 2 |
Mr = 640.15 | F(000) = 673 |
Triclinic, P1 | Dx = 1.288 Mg m−3 |
a = 10.7700 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.1547 (11) Å | Cell parameters from 25 reflections |
c = 15.941 (3) Å | θ = 9.9–13.9° |
α = 91.088 (11)° | µ = 0.17 mm−1 |
β = 102.471 (11)° | T = 150 K |
γ = 116.993 (7)° | Wedge, colorless |
V = 1651.1 (4) Å3 | 0.40 × 0.28 × 0.18 mm |
Nonius CAD4 diffractometer | Rint = 0.053 |
Radiation source: rotating anode | θmax = 25.1°, θmin = 1.3° |
Graphite monochromator | h = −12→11 |
ω scans | k = 0→13 |
6185 measured reflections | l = −18→18 |
5855 independent reflections | 3 standard reflections every 60 min |
4099 reflections with I > 2σ(I)' | intensity decay: <1% |
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) = 0.168 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0952P)2 + 0.4293P] where P = (Fo2 + 2Fc2)/3 |
5855 reflections | (Δ/σ)max < 0.001 |
427 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
C39H32O2P2·0.5C7H8 | γ = 116.993 (7)° |
Mr = 640.15 | V = 1651.1 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.7700 (11) Å | Mo Kα radiation |
b = 11.1547 (11) Å | µ = 0.17 mm−1 |
c = 15.941 (3) Å | T = 150 K |
α = 91.088 (11)° | 0.40 × 0.28 × 0.18 mm |
β = 102.471 (11)° |
Nonius CAD4 diffractometer | Rint = 0.053 |
6185 measured reflections | 3 standard reflections every 60 min |
5855 independent reflections | intensity decay: <1% |
4099 reflections with I > 2σ(I)' |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.51 e Å−3 |
5855 reflections | Δρmin = −0.46 e Å−3 |
427 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 | Occ. (<1) | |
P1 | 0.20793 (9) | 0.94189 (8) | 0.29904 (5) | 0.0212 (2) | |
P2 | 0.30943 (9) | 0.70846 (9) | 0.09805 (5) | 0.0236 (2) | |
O1 | 0.4584 (2) | 0.8873 (2) | 0.26752 (14) | 0.0228 (5) | |
O2 | 0.1413 (2) | 1.0221 (2) | 0.32667 (15) | 0.0280 (5) | |
C1 | 0.5061 (3) | 0.9973 (3) | 0.3310 (2) | 0.0200 (7) | |
C2 | 0.3998 (3) | 1.0270 (3) | 0.3475 (2) | 0.0202 (7) | |
C3 | 0.4443 (4) | 1.1379 (3) | 0.4095 (2) | 0.0267 (7) | |
H3 | 0.3745 | 1.1607 | 0.4218 | 0.032* | |
C4 | 0.5864 (4) | 1.2151 (3) | 0.4531 (2) | 0.0315 (8) | |
H4 | 0.6149 | 1.2913 | 0.4943 | 0.038* | |
C5 | 0.6874 (4) | 1.1800 (3) | 0.4361 (2) | 0.0258 (7) | |
H5 | 0.7852 | 1.2316 | 0.4675 | 0.031* | |
C6 | 0.6498 (3) | 1.0712 (3) | 0.3742 (2) | 0.0222 (7) | |
C7 | 0.5597 (3) | 0.8773 (3) | 0.2304 (2) | 0.0209 (7) | |
C8 | 0.5045 (3) | 0.7940 (3) | 0.1504 (2) | 0.0213 (7) | |
C9 | 0.6025 (3) | 0.7806 (3) | 0.1116 (2) | 0.0249 (7) | |
H9 | 0.5685 | 0.7245 | 0.0577 | 0.030* | |
C10 | 0.7480 (4) | 0.8478 (3) | 0.1505 (2) | 0.0284 (8) | |
H10 | 0.8136 | 0.8388 | 0.1227 | 0.034* | |
C11 | 0.7993 (3) | 0.9284 (3) | 0.2298 (2) | 0.0246 (7) | |
H11 | 0.8998 | 0.9730 | 0.2563 | 0.030* | |
C12 | 0.7058 (3) | 0.9452 (3) | 0.2715 (2) | 0.0202 (7) | |
C13 | 0.1818 (3) | 0.9226 (3) | 0.1839 (2) | 0.0229 (7) | |
C14 | 0.2784 (4) | 1.0227 (3) | 0.1462 (2) | 0.0299 (8) | |
H14 | 0.3655 | 1.0931 | 0.1818 | 0.036* | |
C15 | 0.2483 (4) | 1.0203 (4) | 0.0572 (2) | 0.0350 (9) | |
H15 | 0.3143 | 1.0894 | 0.0318 | 0.042* | |
C16 | 0.1231 (4) | 0.9180 (4) | 0.0053 (2) | 0.0337 (8) | |
H16 | 0.1027 | 0.9168 | −0.0558 | 0.040* | |
C17 | 0.0266 (4) | 0.8166 (4) | 0.0419 (2) | 0.0308 (8) | |
H17 | −0.0601 | 0.7462 | 0.0060 | 0.037* | |
C18 | 0.0571 (3) | 0.8184 (3) | 0.1308 (2) | 0.0255 (7) | |
H18 | −0.0078 | 0.7477 | 0.1558 | 0.031* | |
C19 | 0.1290 (3) | 0.7746 (3) | 0.3319 (2) | 0.0236 (7) | |
C20 | 0.1798 (4) | 0.6817 (3) | 0.3275 (2) | 0.0283 (8) | |
H20 | 0.2609 | 0.7036 | 0.3046 | 0.034* | |
C21 | 0.1139 (4) | 0.5572 (3) | 0.3560 (2) | 0.0353 (9) | |
H21 | 0.1507 | 0.4946 | 0.3539 | 0.042* | |
C22 | −0.0056 (4) | 0.5239 (4) | 0.3876 (2) | 0.0384 (9) | |
H22 | −0.0513 | 0.4382 | 0.4070 | 0.046* | |
C23 | −0.0586 (4) | 0.6143 (4) | 0.3910 (2) | 0.0422 (10) | |
H23 | −0.1409 | 0.5907 | 0.4129 | 0.051* | |
C24 | 0.0068 (4) | 0.7398 (4) | 0.3629 (2) | 0.0336 (8) | |
H24 | −0.0312 | 0.8016 | 0.3647 | 0.040* | |
C25 | 0.3134 (3) | 0.6801 (3) | −0.0154 (2) | 0.0235 (7) | |
C26 | 0.3458 (4) | 0.7916 (4) | −0.0607 (2) | 0.0325 (8) | |
H26 | 0.3677 | 0.8767 | −0.0318 | 0.039* | |
C27 | 0.3466 (4) | 0.7801 (4) | −0.1466 (3) | 0.0420 (10) | |
H27 | 0.3711 | 0.8579 | −0.1760 | 0.050* | |
C28 | 0.3123 (4) | 0.6576 (4) | −0.1906 (2) | 0.0445 (10) | |
H28 | 0.3112 | 0.6501 | −0.2502 | 0.053* | |
C29 | 0.2795 (5) | 0.5460 (4) | −0.1471 (3) | 0.0498 (11) | |
H29 | 0.2571 | 0.4611 | −0.1766 | 0.060* | |
C30 | 0.2789 (4) | 0.5569 (4) | −0.0599 (2) | 0.0379 (9) | |
H30 | 0.2545 | 0.4790 | −0.0307 | 0.045* | |
C31 | 0.2556 (4) | 0.5393 (3) | 0.1322 (2) | 0.0269 (8) | |
C32 | 0.3418 (5) | 0.4774 (4) | 0.1485 (3) | 0.0473 (11) | |
H32 | 0.4360 | 0.5216 | 0.1397 | 0.057* | |
C33 | 0.2937 (5) | 0.3521 (4) | 0.1773 (3) | 0.0566 (12) | |
H33 | 0.3560 | 0.3122 | 0.1894 | 0.068* | |
C34 | 0.1571 (5) | 0.2844 (4) | 0.1887 (2) | 0.0475 (11) | |
H34 | 0.1244 | 0.1980 | 0.2084 | 0.057* | |
C35 | 0.0690 (5) | 0.3426 (4) | 0.1713 (2) | 0.0449 (11) | |
H35 | −0.0260 | 0.2962 | 0.1787 | 0.054* | |
C36 | 0.1165 (4) | 0.4691 (4) | 0.1428 (2) | 0.0368 (9) | |
H36 | 0.0534 | 0.5081 | 0.1305 | 0.044* | |
C43 | 0.9075 (4) | 1.1511 (4) | 0.3689 (3) | 0.0451 (11) | |
H43A | 0.9766 | 1.1201 | 0.3612 | 0.068* | |
H43B | 0.9406 | 1.2033 | 0.4266 | 0.068* | |
H43C | 0.8996 | 1.2087 | 0.3246 | 0.068* | |
C44 | 0.7747 (5) | 0.9380 (4) | 0.4297 (2) | 0.0411 (10) | |
H44A | 0.8470 | 0.9107 | 0.4228 | 0.062* | |
H44B | 0.6817 | 0.8569 | 0.4229 | 0.062* | |
H44C | 0.8046 | 0.9887 | 0.4875 | 0.062* | |
C45 | 0.7605 (3) | 1.0285 (3) | 0.3603 (2) | 0.0235 (7) | |
C46 | 0.4044 (5) | 0.4421 (4) | 0.4208 (3) | 0.0476 (11) | |
H46 | 0.3367 | 0.4020 | 0.3663 | 0.057* | |
C47 | 0.3631 (5) | 0.3993 (4) | 0.4959 (3) | 0.0476 (11) | |
H47 | 0.2686 | 0.3288 | 0.4918 | 0.057* | |
C48 | 0.5430 (5) | 0.5428 (4) | 0.4235 (3) | 0.0461 (10) | |
C49 | 0.5890 (10) | 0.5856 (8) | 0.3400 (6) | 0.050 (2) | 0.50 |
H49A | 0.6910 | 0.6533 | 0.3544 | 0.075* | 0.50 |
H49B | 0.5309 | 0.6249 | 0.3083 | 0.075* | 0.50 |
H49C | 0.5746 | 0.5061 | 0.3038 | 0.075* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0211 (4) | 0.0230 (4) | 0.0223 (4) | 0.0118 (4) | 0.0073 (3) | 0.0009 (3) |
P2 | 0.0225 (5) | 0.0237 (4) | 0.0243 (5) | 0.0105 (4) | 0.0062 (4) | −0.0010 (3) |
O1 | 0.0190 (11) | 0.0203 (11) | 0.0270 (12) | 0.0065 (9) | 0.0086 (9) | −0.0054 (9) |
O2 | 0.0279 (13) | 0.0322 (13) | 0.0292 (13) | 0.0187 (11) | 0.0074 (10) | −0.0024 (10) |
C1 | 0.0247 (17) | 0.0153 (15) | 0.0196 (16) | 0.0081 (13) | 0.0077 (13) | 0.0028 (12) |
C2 | 0.0214 (16) | 0.0188 (15) | 0.0201 (16) | 0.0087 (13) | 0.0063 (13) | 0.0011 (13) |
C3 | 0.0273 (18) | 0.0277 (18) | 0.0265 (18) | 0.0142 (15) | 0.0071 (15) | −0.0020 (14) |
C4 | 0.034 (2) | 0.0241 (18) | 0.033 (2) | 0.0122 (16) | 0.0054 (16) | −0.0096 (15) |
C5 | 0.0232 (17) | 0.0241 (17) | 0.0222 (17) | 0.0064 (14) | 0.0018 (14) | −0.0019 (14) |
C6 | 0.0250 (17) | 0.0226 (17) | 0.0205 (16) | 0.0110 (14) | 0.0088 (13) | 0.0054 (13) |
C7 | 0.0233 (17) | 0.0186 (15) | 0.0255 (17) | 0.0110 (14) | 0.0124 (14) | 0.0063 (13) |
C8 | 0.0204 (16) | 0.0209 (16) | 0.0239 (17) | 0.0107 (14) | 0.0053 (13) | 0.0048 (13) |
C9 | 0.0275 (18) | 0.0288 (18) | 0.0215 (17) | 0.0155 (15) | 0.0074 (14) | −0.0008 (14) |
C10 | 0.0284 (18) | 0.0355 (19) | 0.0307 (19) | 0.0194 (16) | 0.0152 (15) | 0.0067 (15) |
C11 | 0.0215 (17) | 0.0286 (18) | 0.0255 (18) | 0.0127 (15) | 0.0070 (14) | 0.0064 (14) |
C12 | 0.0228 (17) | 0.0175 (15) | 0.0219 (16) | 0.0096 (13) | 0.0084 (13) | 0.0047 (13) |
C13 | 0.0245 (17) | 0.0243 (17) | 0.0262 (17) | 0.0149 (14) | 0.0106 (14) | 0.0023 (14) |
C14 | 0.0314 (19) | 0.0242 (18) | 0.0306 (19) | 0.0097 (15) | 0.0087 (15) | 0.0016 (15) |
C15 | 0.040 (2) | 0.0292 (19) | 0.033 (2) | 0.0116 (17) | 0.0139 (17) | 0.0097 (16) |
C16 | 0.042 (2) | 0.035 (2) | 0.0240 (18) | 0.0185 (18) | 0.0092 (16) | 0.0028 (15) |
C17 | 0.0282 (19) | 0.036 (2) | 0.0266 (19) | 0.0149 (16) | 0.0060 (15) | −0.0007 (15) |
C18 | 0.0216 (17) | 0.0294 (18) | 0.0272 (18) | 0.0122 (15) | 0.0086 (14) | 0.0019 (14) |
C19 | 0.0247 (17) | 0.0269 (17) | 0.0164 (16) | 0.0112 (14) | 0.0022 (13) | −0.0001 (13) |
C20 | 0.0310 (19) | 0.0258 (18) | 0.0273 (18) | 0.0114 (15) | 0.0101 (15) | 0.0020 (14) |
C21 | 0.047 (2) | 0.0246 (18) | 0.032 (2) | 0.0140 (17) | 0.0107 (17) | 0.0043 (15) |
C22 | 0.048 (2) | 0.0232 (18) | 0.0280 (19) | 0.0030 (17) | 0.0105 (17) | 0.0010 (15) |
C23 | 0.034 (2) | 0.042 (2) | 0.040 (2) | 0.0051 (18) | 0.0197 (18) | 0.0017 (18) |
C24 | 0.031 (2) | 0.032 (2) | 0.035 (2) | 0.0109 (16) | 0.0132 (16) | −0.0028 (16) |
C25 | 0.0185 (16) | 0.0279 (18) | 0.0217 (17) | 0.0104 (14) | 0.0018 (13) | −0.0003 (14) |
C26 | 0.036 (2) | 0.0316 (19) | 0.036 (2) | 0.0198 (17) | 0.0100 (17) | 0.0068 (16) |
C27 | 0.038 (2) | 0.050 (2) | 0.041 (2) | 0.021 (2) | 0.0131 (18) | 0.020 (2) |
C28 | 0.037 (2) | 0.061 (3) | 0.024 (2) | 0.013 (2) | 0.0093 (17) | 0.0047 (19) |
C29 | 0.056 (3) | 0.042 (2) | 0.036 (2) | 0.008 (2) | 0.017 (2) | −0.0120 (19) |
C30 | 0.046 (2) | 0.0247 (19) | 0.032 (2) | 0.0054 (17) | 0.0158 (18) | −0.0021 (15) |
C31 | 0.0288 (18) | 0.0269 (18) | 0.0214 (17) | 0.0107 (15) | 0.0050 (14) | −0.0002 (14) |
C32 | 0.042 (2) | 0.031 (2) | 0.073 (3) | 0.0167 (19) | 0.022 (2) | 0.023 (2) |
C33 | 0.053 (3) | 0.034 (2) | 0.078 (3) | 0.019 (2) | 0.010 (2) | 0.020 (2) |
C34 | 0.061 (3) | 0.030 (2) | 0.031 (2) | 0.006 (2) | 0.007 (2) | 0.0081 (17) |
C35 | 0.047 (2) | 0.034 (2) | 0.032 (2) | −0.0021 (19) | 0.0176 (19) | −0.0023 (17) |
C36 | 0.036 (2) | 0.031 (2) | 0.035 (2) | 0.0069 (17) | 0.0147 (17) | −0.0052 (16) |
C43 | 0.0217 (19) | 0.043 (2) | 0.054 (3) | 0.0007 (17) | 0.0130 (18) | −0.0219 (19) |
C44 | 0.058 (3) | 0.059 (3) | 0.0228 (19) | 0.043 (2) | 0.0051 (18) | 0.0027 (18) |
C45 | 0.0184 (16) | 0.0251 (17) | 0.0233 (17) | 0.0082 (14) | 0.0033 (13) | −0.0023 (13) |
C46 | 0.066 (3) | 0.049 (3) | 0.036 (2) | 0.041 (2) | 0.000 (2) | −0.0012 (19) |
C47 | 0.057 (3) | 0.041 (2) | 0.052 (3) | 0.030 (2) | 0.009 (2) | 0.003 (2) |
C48 | 0.063 (3) | 0.041 (2) | 0.049 (3) | 0.037 (2) | 0.013 (2) | 0.007 (2) |
C49 | 0.055 (5) | 0.036 (5) | 0.054 (5) | 0.019 (4) | 0.008 (4) | 0.002 (4) |
P1—O2 | 1.488 (2) | C22—C23 | 1.371 (6) |
P1—C2 | 1.809 (3) | C22—H22 | 0.9500 |
P1—C13 | 1.790 (3) | C23—C24 | 1.386 (5) |
P1—C19 | 1.808 (3) | C23—H23 | 0.9500 |
P2—C8 | 1.848 (3) | C24—H24 | 0.9500 |
P2—C25 | 1.844 (3) | C25—C30 | 1.383 (5) |
P2—C31 | 1.837 (3) | C25—C26 | 1.392 (5) |
O1—C7 | 1.392 (4) | C26—C27 | 1.376 (5) |
O1—C1 | 1.396 (4) | C26—H26 | 0.9500 |
C1—C6 | 1.382 (4) | C27—C28 | 1.373 (6) |
C1—C2 | 1.400 (4) | C27—H27 | 0.9500 |
C2—C3 | 1.396 (4) | C28—C29 | 1.377 (6) |
C3—C4 | 1.374 (5) | C28—H28 | 0.9500 |
C3—H3 | 0.9500 | C29—C30 | 1.395 (5) |
C4—C5 | 1.386 (5) | C29—H29 | 0.9500 |
C4—H4 | 0.9500 | C30—H30 | 0.9500 |
C5—C6 | 1.395 (4) | C31—C32 | 1.375 (5) |
C5—H5 | 0.9500 | C31—C36 | 1.392 (5) |
C6—C45 | 1.524 (4) | C32—C33 | 1.380 (5) |
C7—C12 | 1.390 (4) | C32—H32 | 0.9500 |
C7—C8 | 1.403 (4) | C33—C34 | 1.371 (6) |
C8—C9 | 1.393 (4) | C33—H33 | 0.9500 |
C9—C10 | 1.378 (5) | C34—C35 | 1.360 (6) |
C9—H9 | 0.9500 | C34—H34 | 0.9500 |
C10—C11 | 1.384 (5) | C35—C36 | 1.388 (5) |
C10—H10 | 0.9500 | C35—H35 | 0.9500 |
C11—C12 | 1.395 (4) | C36—H36 | 0.9500 |
C11—H11 | 0.9500 | C43—C45 | 1.526 (5) |
C12—C45 | 1.519 (4) | C43—H43A | 0.9800 |
C13—C18 | 1.387 (5) | C43—H43B | 0.9800 |
C13—C14 | 1.389 (4) | C43—H43C | 0.9800 |
C14—C15 | 1.383 (5) | C44—C45 | 1.542 (5) |
C14—H14 | 0.9500 | C44—H44A | 0.9800 |
C15—C16 | 1.374 (5) | C44—H44B | 0.9800 |
C15—H15 | 0.9500 | C44—H44C | 0.9800 |
C16—C17 | 1.385 (5) | C46—C47 | 1.384 (6) |
C16—H16 | 0.9500 | C46—C48 | 1.393 (6) |
C17—C18 | 1.382 (5) | C46—H46 | 0.9500 |
C17—H17 | 0.9500 | C47—C48i | 1.380 (6) |
C18—H18 | 0.9500 | C47—H47 | 0.9500 |
C19—C20 | 1.382 (5) | C48—C47i | 1.380 (6) |
C19—C24 | 1.397 (5) | C48—C49 | 1.530 (9) |
C20—C21 | 1.381 (5) | C49—H49A | 0.9800 |
C20—H20 | 0.9500 | C49—H49B | 0.9800 |
C21—C22 | 1.379 (5) | C49—H49C | 0.9800 |
C21—H21 | 0.9500 | ||
O2—P1—C2 | 110.04 (14) | C22—C23—C24 | 120.7 (4) |
O2—P1—C13 | 111.59 (14) | C22—C23—H23 | 119.6 |
O2—P1—C19 | 110.03 (14) | C24—C23—H23 | 119.6 |
C13—P1—C2 | 107.61 (14) | C23—C24—C19 | 119.4 (3) |
C19—P1—C2 | 109.31 (15) | C23—C24—H24 | 120.3 |
C13—P1—C19 | 108.21 (15) | C19—C24—H24 | 120.3 |
C25—P2—C8 | 99.94 (14) | C30—C25—C26 | 118.1 (3) |
C31—P2—C8 | 100.80 (15) | C30—C25—P2 | 125.6 (3) |
C31—P2—C25 | 102.83 (15) | C26—C25—P2 | 116.2 (3) |
C7—O1—C1 | 118.0 (2) | C27—C26—C25 | 120.9 (3) |
C6—C1—O1 | 121.3 (3) | C27—C26—H26 | 119.6 |
C6—C1—C2 | 122.8 (3) | C25—C26—H26 | 119.6 |
O1—C1—C2 | 115.9 (3) | C28—C27—C26 | 120.9 (4) |
C3—C2—C1 | 117.4 (3) | C28—C27—H27 | 119.6 |
C1—C2—P1 | 129.2 (2) | C26—C27—H27 | 119.6 |
C3—C2—P1 | 113.4 (2) | C27—C28—C29 | 119.2 (4) |
C4—C3—C2 | 121.7 (3) | C27—C28—H28 | 120.4 |
C4—C3—H3 | 119.2 | C29—C28—H28 | 120.4 |
C2—C3—H3 | 119.2 | C28—C29—C30 | 120.3 (4) |
C3—C4—C5 | 119.0 (3) | C28—C29—H29 | 119.9 |
C3—C4—H4 | 120.5 | C30—C29—H29 | 119.9 |
C5—C4—H4 | 120.5 | C25—C30—C29 | 120.7 (4) |
C4—C5—C6 | 122.0 (3) | C25—C30—H30 | 119.6 |
C4—C5—H5 | 119.0 | C29—C30—H30 | 119.6 |
C6—C5—H5 | 119.0 | C32—C31—C36 | 117.7 (3) |
C1—C6—C5 | 117.2 (3) | C32—C31—P2 | 125.3 (3) |
C1—C6—C45 | 121.3 (3) | C36—C31—P2 | 117.0 (3) |
C5—C6—C45 | 121.3 (3) | C31—C32—C33 | 121.1 (4) |
C12—C7—O1 | 121.3 (3) | C31—C32—H32 | 119.4 |
C12—C7—C8 | 122.9 (3) | C33—C32—H32 | 119.4 |
O1—C7—C8 | 115.8 (3) | C34—C33—C32 | 120.7 (4) |
C9—C8—C7 | 117.5 (3) | C34—C33—H33 | 119.6 |
C7—C8—P2 | 120.9 (2) | C32—C33—H33 | 119.6 |
C9—C8—P2 | 121.6 (2) | C35—C34—C33 | 119.1 (4) |
C10—C9—C8 | 120.9 (3) | C35—C34—H34 | 120.5 |
C10—C9—H9 | 119.6 | C33—C34—H34 | 120.5 |
C8—C9—H9 | 119.6 | C34—C35—C36 | 120.7 (4) |
C9—C10—C11 | 120.4 (3) | C34—C35—H35 | 119.6 |
C9—C10—H10 | 119.8 | C36—C35—H35 | 119.6 |
C11—C10—H10 | 119.8 | C35—C36—C31 | 120.6 (4) |
C10—C11—C12 | 121.0 (3) | C35—C36—H36 | 119.7 |
C10—C11—H11 | 119.5 | C31—C36—H36 | 119.7 |
C12—C11—H11 | 119.5 | C45—C43—H43A | 109.5 |
C7—C12—C11 | 117.4 (3) | C45—C43—H43B | 109.5 |
C7—C12—C45 | 121.2 (3) | H43A—C43—H43B | 109.5 |
C11—C12—C45 | 121.3 (3) | C45—C43—H43C | 109.5 |
C18—C13—C14 | 119.1 (3) | H43A—C43—H43C | 109.5 |
C18—C13—P1 | 120.9 (2) | H43B—C43—H43C | 109.5 |
C14—C13—P1 | 119.5 (3) | C45—C44—H44A | 109.5 |
C15—C14—C13 | 120.3 (3) | C45—C44—H44B | 109.5 |
C15—C14—H14 | 119.9 | H44A—C44—H44B | 109.5 |
C13—C14—H14 | 119.9 | C45—C44—H44C | 109.5 |
C16—C15—C14 | 120.1 (3) | H44A—C44—H44C | 109.5 |
C16—C15—H15 | 119.9 | H44B—C44—H44C | 109.5 |
C14—C15—H15 | 119.9 | C12—C45—C6 | 108.9 (3) |
C15—C16—C17 | 120.3 (3) | C12—C45—C43 | 110.9 (3) |
C15—C16—H16 | 119.9 | C6—C45—C43 | 111.6 (3) |
C17—C16—H16 | 119.9 | C12—C45—C44 | 108.5 (3) |
C18—C17—C16 | 119.6 (3) | C6—C45—C44 | 108.0 (3) |
C18—C17—H17 | 120.2 | C43—C45—C44 | 109.0 (3) |
C16—C17—H17 | 120.2 | C47—C46—C48 | 121.4 (4) |
C17—C18—C13 | 120.6 (3) | C47—C46—H46 | 119.3 |
C17—C18—H18 | 119.7 | C48—C46—H46 | 119.3 |
C13—C18—H18 | 119.7 | C48i—C47—C46 | 121.1 (4) |
C20—C19—C24 | 119.3 (3) | C48i—C47—H47 | 119.4 |
C20—C19—P1 | 124.9 (3) | C46—C47—H47 | 119.4 |
C24—C19—P1 | 115.8 (3) | C47i—C48—C46 | 117.4 (4) |
C21—C20—C19 | 120.6 (3) | C47i—C48—C49 | 121.6 (5) |
C21—C20—H20 | 119.7 | C46—C48—C49 | 120.9 (5) |
C19—C20—H20 | 119.7 | C48—C49—H49A | 109.5 |
C22—C21—C20 | 119.9 (4) | C48—C49—H49B | 109.5 |
C22—C21—H21 | 120.1 | H49A—C49—H49B | 109.5 |
C20—C21—H21 | 120.1 | C48—C49—H49C | 109.5 |
C23—C22—C21 | 120.1 (3) | H49A—C49—H49C | 109.5 |
C23—C22—H22 | 120.0 | H49B—C49—H49C | 109.5 |
C21—C22—H22 | 120.0 | ||
C7—O1—C1—C6 | −18.6 (4) | P1—C13—C18—C17 | 169.4 (3) |
C7—O1—C1—C2 | 161.4 (3) | O2—P1—C19—C20 | −170.4 (3) |
C6—C1—C2—C3 | 1.1 (5) | C13—P1—C19—C20 | 67.5 (3) |
O1—C1—C2—C3 | −178.8 (3) | C2—P1—C19—C20 | −49.4 (3) |
C6—C1—C2—P1 | −179.3 (2) | O2—P1—C19—C24 | 10.3 (3) |
O1—C1—C2—P1 | 0.7 (4) | C13—P1—C19—C24 | −111.8 (3) |
O2—P1—C2—C3 | 8.5 (3) | C2—P1—C19—C24 | 131.3 (3) |
C13—P1—C2—C3 | 130.3 (2) | C24—C19—C20—C21 | −2.2 (5) |
C19—P1—C2—C3 | −112.4 (2) | P1—C19—C20—C21 | 178.6 (3) |
O2—P1—C2—C1 | −171.1 (3) | C19—C20—C21—C22 | 1.3 (5) |
C13—P1—C2—C1 | −49.3 (3) | C20—C21—C22—C23 | −0.3 (6) |
C19—P1—C2—C1 | 68.0 (3) | C21—C22—C23—C24 | 0.0 (6) |
C1—C2—C3—C4 | −0.3 (5) | C22—C23—C24—C19 | −0.8 (6) |
P1—C2—C3—C4 | −179.9 (3) | C20—C19—C24—C23 | 1.9 (5) |
C2—C3—C4—C5 | −1.2 (5) | P1—C19—C24—C23 | −178.8 (3) |
C3—C4—C5—C6 | 1.9 (5) | C31—P2—C25—C30 | 1.5 (3) |
O1—C1—C6—C5 | 179.5 (3) | C8—P2—C25—C30 | 105.1 (3) |
C2—C1—C6—C5 | −0.4 (5) | C31—P2—C25—C26 | 177.4 (3) |
O1—C1—C6—C45 | −5.5 (4) | C8—P2—C25—C26 | −79.0 (3) |
C2—C1—C6—C45 | 174.6 (3) | C30—C25—C26—C27 | −1.4 (5) |
C4—C5—C6—C1 | −1.1 (5) | P2—C25—C26—C27 | −177.7 (3) |
C4—C5—C6—C45 | −176.1 (3) | C25—C26—C27—C28 | 1.5 (6) |
C1—O1—C7—C12 | 20.0 (4) | C26—C27—C28—C29 | −1.2 (6) |
C1—O1—C7—C8 | −160.5 (3) | C27—C28—C29—C30 | 1.0 (6) |
C12—C7—C8—C9 | −0.1 (5) | C26—C25—C30—C29 | 1.2 (6) |
O1—C7—C8—C9 | −179.5 (3) | P2—C25—C30—C29 | 177.1 (3) |
C12—C7—C8—P2 | −178.9 (2) | C28—C29—C30—C25 | −1.1 (6) |
O1—C7—C8—P2 | 1.6 (4) | C25—P2—C31—C32 | 72.7 (4) |
C31—P2—C8—C9 | 83.9 (3) | C8—P2—C31—C32 | −30.2 (4) |
C25—P2—C8—C9 | −21.3 (3) | C25—P2—C31—C36 | −107.7 (3) |
C31—P2—C8—C7 | −97.3 (3) | C8—P2—C31—C36 | 149.4 (3) |
C25—P2—C8—C7 | 157.5 (3) | C36—C31—C32—C33 | −2.2 (6) |
C7—C8—C9—C10 | −0.5 (5) | P2—C31—C32—C33 | 177.3 (3) |
P2—C8—C9—C10 | 178.3 (2) | C31—C32—C33—C34 | 1.5 (7) |
C8—C9—C10—C11 | 1.0 (5) | C32—C33—C34—C35 | −0.2 (7) |
C9—C10—C11—C12 | −1.0 (5) | C33—C34—C35—C36 | −0.3 (6) |
O1—C7—C12—C11 | 179.5 (3) | C34—C35—C36—C31 | −0.5 (6) |
C8—C7—C12—C11 | 0.1 (4) | C32—C31—C36—C35 | 1.8 (5) |
O1—C7—C12—C45 | 2.6 (4) | P2—C31—C36—C35 | −177.8 (3) |
C8—C7—C12—C45 | −176.8 (3) | C7—C12—C45—C6 | −23.6 (4) |
C10—C11—C12—C7 | 0.4 (5) | C11—C12—C45—C6 | 159.7 (3) |
C10—C11—C12—C45 | 177.3 (3) | C7—C12—C45—C43 | −146.6 (3) |
O2—P1—C13—C18 | −85.5 (3) | C11—C12—C45—C43 | 36.6 (4) |
C19—P1—C13—C18 | 35.7 (3) | C7—C12—C45—C44 | 93.7 (3) |
C2—P1—C13—C18 | 153.7 (3) | C11—C12—C45—C44 | −83.1 (4) |
O2—P1—C13—C14 | 86.1 (3) | C1—C6—C45—C12 | 25.0 (4) |
C19—P1—C13—C14 | −152.7 (3) | C5—C6—C45—C12 | −160.2 (3) |
C2—P1—C13—C14 | −34.7 (3) | C1—C6—C45—C43 | 147.7 (3) |
C18—C13—C14—C15 | 1.9 (5) | C5—C6—C45—C43 | −37.6 (4) |
P1—C13—C14—C15 | −170.0 (3) | C1—C6—C45—C44 | −92.6 (4) |
C13—C14—C15—C16 | −0.6 (6) | C5—C6—C45—C44 | 82.2 (4) |
C14—C15—C16—C17 | −0.2 (6) | C48—C46—C47—C48i | 1.6 (7) |
C15—C16—C17—C18 | −0.3 (5) | C47—C46—C48—C47i | −1.6 (6) |
C16—C17—C18—C13 | 1.6 (5) | C47—C46—C48—C49 | 177.7 (5) |
C14—C13—C18—C17 | −2.3 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C39H32O2P2·0.5C7H8 |
Mr | 640.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 10.7700 (11), 11.1547 (11), 15.941 (3) |
α, β, γ (°) | 91.088 (11), 102.471 (11), 116.993 (7) |
V (Å3) | 1651.1 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.40 × 0.28 × 0.18 |
Data collection | |
Diffractometer | Nonius CAD4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)'] reflections | 6185, 5855, 4099 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.168, 1.01 |
No. of reflections | 5855 |
No. of parameters | 427 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.46 |
Computer programs: Locally modified CAD-4 Software (Enraf-Nonius, 1989), SET4 (de Boer & Duisenberg, 1984), HELENA (Spek, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2000).
P1—O2 | 1.488 (2) | P2—C8 | 1.848 (3) |
P1—C2 | 1.809 (3) | P2—C25 | 1.844 (3) |
P1—C13 | 1.790 (3) | P2—C31 | 1.837 (3) |
P1—C19 | 1.808 (3) | ||
O2—P1—C2 | 110.04 (14) | C31—P2—C8 | 100.80 (15) |
O2—P1—C13 | 111.59 (14) | C31—P2—C25 | 102.83 (15) |
O2—P1—C19 | 110.03 (14) | C1—C2—P1 | 129.2 (2) |
C13—P1—C2 | 107.61 (14) | C3—C2—P1 | 113.4 (2) |
C19—P1—C2 | 109.31 (15) | C7—C8—P2 | 120.9 (2) |
C13—P1—C19 | 108.21 (15) | C9—C8—P2 | 121.6 (2) |
C25—P2—C8 | 99.94 (14) |
The title structure, (I), is similar to the bis(diphenylphosphino) derivative, (II) (Hillebrand et al., 1995; Kranenburg et al., 1995), and the bis(methylphenylphosphine) oxide compound (Hamada et al., 1997). The atoms in the xanthane backbone of (I) do not have the symmetry associated with (II), but are folded at a similar angle, 158.9 (1)° [cf. 156.6° in (II)], due to the steric congestion between the diphenylphosphine groups and the xanthane unit.
The geometry around each P atom is distinct due to the different oxidation states: the P—C bond distances [mean 1.802 (11) Å] around P1, formally PV, are shorter than those at P2 [PIII; mean 1.843 (6) Å]. The C—P1—C bond angles tend towards tetrahedral [average 108.4 (9)°] whilst the corresponding ones around P2 are more acute [average 101.2 (15)°].
The lone pair and oxide group on the P atoms in (I) have an in–out orientation, whereas in (II), the lone pairs point towards each other (in–in), so that only a small adjustment is required for metal chelation (Kranenburg et al., 1995). This can be correlated with the distance between the P atoms which increases from 4.045 (1) Å in (II) to 4.693 (2) Å in (I).
The asymmetry of the ligand is also shown by the C—C—P angles at the substituted C atoms of the xanthane unit, namely C2 and C8. In (I), the angle deformation is again dependent on the nature of the phosphine; thus, those around C2 are 113.4 (2) and 129.2 (2)° (for P1), whilst around C8 are 120.9 (2) and 121.6 (2)° (for P2). In the (more) symmetric ligand (II), the C—C—P angles are 118.4 (2) and 125.1 (3)°, i.e. the reverse situation is present.