Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027121/bt6724sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027121/bt6724Isup2.hkl |
CCDC reference: 287463
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.005 Å
- R factor = 0.037
- wR factor = 0.079
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 34 Perc. PLAT230_ALERT_2_B Hirshfeld Test Diff for C3 - C6 .. 8.94 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C15 - C16 .. 7.82 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C21 - C22 .. 7.28 su PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C3
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for C11 - C12 .. 6.91 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C31 PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
0 ALERT level A = In general: serious problem 5 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
At 273 K, n-butyllithium (16 ml of 2.5 M in hexanes, 39 mmol) was added dropwise to a stirred solution of 10-(tertbutyldimethylsilyl)phenoxazine (4.84 g, 16.3 mmol) and TMEDA [Please give name in full] (5.9 ml, 39 mmol) in diethyl ether (250 ml). The reaction mixture was slowly warmed to room temperature and stirred for 16 h. The maize-yellow suspension was then cooled to 273 K and a solution of chlorodiphenylphosphine (7.0 ml, 39 mmol) in hexanes (25 ml) was added dropwise. The reaction mixture decolourized and a light-brown precipitate was formed. After stirring for 16 h at room temperature, the reaction mixture was hydrolyzed with brine (50 ml). The water layer was removed and the organic layer was dried over MgSO4. The solvent was removed and the residue purified by chromatography (cyclohexane), followed by crystallization from dichloromethane–ethanol (Ratio?). Yield 7.91 g (73%) of colourless crystals of (I), m.p. 432–433 K. Spectroscopic analysis: 1H NMR (500 MHz, C6D6, δ, p.p.m.): 0.26 (s, 6H), 0.90 (s, 9H), 6.63 (d, 2H, J = 7.7 Hz), 6.71 (t, 2H, J = 7.7 Hz), 6.89 (d, 2H, J = 7.7 Hz), 7.1 (bs, 12H), 7.5 (bs, 8H); 13C NMR (125 MHz, C6D6, δ, p.p.m.): 0.9 (CH3), 21.7 (C), 28.7 (CH3), 124.3 (CH), 125.0 (CH), 128.2 (C), 128.3 (C), 128.4 (C), 129.4(CH), 129.8 (m, CH), 136.8 (m, CH), 138.4 (C), 139.0 (m, C); 31P NMR (81 MHz, CDCl3, δ, p.p.m.): −16.6; MS (FAB+ LR): m/z (%) = 666 (M)+, (20); exact mass (FAB+ HR): 665.2425 (M)+, calculated for C42H41ONSiP2: 665.2433.
H atoms were placed in calculated positions, with C—H = 0.93–0.96 Å, and were refined as riding, with Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C) for others; the methyl groups were allowed to rotate but not to tip.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97, PARST95 (Nardelli, 1995) and PLATON (Spek, 2003).
Fig. 1. The molecular structure of the title compound, showing the labelling of all non-H atoms. H atoms have been omitted for clarity. Displacement ellipsoids are shown at the 30% probability level. |
C42H41NOP2Si | F(000) = 1408 |
Mr = 665.79 | Dx = 1.191 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2yn | Cell parameters from 32114 reflections |
a = 18.8748 (18) Å | θ = 3.2–25.0° |
b = 10.8973 (10) Å | µ = 0.18 mm−1 |
c = 19.1042 (15) Å | T = 291 K |
β = 109.139 (5)° | Block, light yellow |
V = 3712.2 (6) Å3 | 0.20 × 0.10 × 0.08 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 2229 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 25.0°, θmin = 3.2° |
Detector resolution: 19 vertical, 18 horizontal pixels mm-1 | h = −22→22 |
ω scans | k = −12→12 |
32114 measured reflections | l = −22→21 |
6468 independent reflections |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 0.99 | w = [exp{4.2(sinθ/λ)2}]/[σ2(Fo2)] where P = 0.333Fo2 + 0.667Fc2 |
6468 reflections | (Δ/σ)max < 0.001 |
429 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C42H41NOP2Si | V = 3712.2 (6) Å3 |
Mr = 665.79 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 18.8748 (18) Å | µ = 0.18 mm−1 |
b = 10.8973 (10) Å | T = 291 K |
c = 19.1042 (15) Å | 0.20 × 0.10 × 0.08 mm |
β = 109.139 (5)° |
Nonius KappaCCD area-detector diffractometer | 2229 reflections with I > 2σ(I) |
32114 measured reflections | Rint = 0.041 |
6468 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.15 e Å−3 |
6468 reflections | Δρmin = −0.18 e Å−3 |
429 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 | ||
P1 | 0.22098 (5) | 0.52970 (8) | 0.04010 (5) | 0.0790 (3) | |
P2 | 0.39917 (5) | 0.74126 (8) | 0.02815 (5) | 0.0782 (3) | |
Si | 0.09955 (5) | 0.93450 (8) | −0.22507 (5) | 0.0861 (3) | |
O | 0.23899 (11) | 0.73431 (17) | −0.05367 (10) | 0.0728 (5) | |
N | 0.15712 (15) | 0.8019 (2) | −0.19669 (12) | 0.0734 (7) | |
C1 | −0.00025 (17) | 0.8857 (3) | −0.26512 (18) | 0.1211 (13) | |
H1A | −0.0061 | 0.8342 | −0.3074 | 0.182* | |
H1B | −0.0316 | 0.9568 | −0.2800 | 0.182* | |
H1C | −0.0145 | 0.8409 | −0.2286 | 0.182* | |
C2 | 0.1240 (2) | 1.0205 (3) | −0.29780 (17) | 0.1259 (13) | |
H2A | 0.1741 | 1.0518 | −0.2776 | 0.189* | |
H2B | 0.0896 | 1.0875 | −0.3149 | 0.189* | |
H2C | 0.1208 | 0.9667 | −0.3385 | 0.189* | |
C3 | 0.10914 (19) | 1.0389 (3) | −0.14562 (18) | 0.0855 (10) | |
C4 | 0.0563 (2) | 1.1502 (3) | −0.1719 (2) | 0.1463 (16) | |
H4A | 0.0054 | 1.1220 | −0.1922 | 0.219* | |
H4B | 0.0697 | 1.1943 | −0.2092 | 0.219* | |
H4C | 0.0608 | 1.2034 | −0.1306 | 0.219* | |
C5 | 0.1884 (2) | 1.0894 (3) | −0.1120 (2) | 0.1487 (17) | |
H5A | 0.1894 | 1.1484 | −0.0744 | 0.223* | |
H5B | 0.2034 | 1.1282 | −0.1500 | 0.223* | |
H5C | 0.2222 | 1.0235 | −0.0905 | 0.223* | |
C6 | 0.0875 (2) | 0.9749 (3) | −0.08525 (18) | 0.1187 (12) | |
H6A | 0.1231 | 0.9112 | −0.0637 | 0.178* | |
H6B | 0.0384 | 0.9397 | −0.1060 | 0.178* | |
H6C | 0.0873 | 1.0333 | −0.0477 | 0.178* | |
C11 | 0.16019 (16) | 0.5645 (3) | −0.05439 (15) | 0.0653 (8) | |
C12 | 0.09783 (18) | 0.4940 (3) | −0.09427 (19) | 0.0769 (9) | |
H12 | 0.0838 | 0.4273 | −0.0714 | 0.092* | |
C13 | 0.05708 (17) | 0.5215 (3) | −0.16640 (19) | 0.0806 (9) | |
H13 | 0.0167 | 0.4722 | −0.1920 | 0.097* | |
C14 | 0.07552 (18) | 0.6219 (3) | −0.20154 (16) | 0.0759 (9) | |
H14 | 0.0475 | 0.6396 | −0.2504 | 0.091* | |
C15 | 0.13545 (18) | 0.6958 (3) | −0.16409 (18) | 0.0686 (8) | |
C16 | 0.17685 (18) | 0.6632 (3) | −0.09248 (19) | 0.0670 (8) | |
C21 | 0.17432 (18) | 0.3967 (3) | 0.06417 (15) | 0.0718 (9) | |
C22 | 0.20826 (17) | 0.2839 (3) | 0.06824 (15) | 0.0781 (9) | |
H22 | 0.2531 | 0.2789 | 0.0580 | 0.094* | |
C23 | 0.1788 (2) | 0.1783 (3) | 0.08682 (18) | 0.0895 (10) | |
H23 | 0.2028 | 0.1033 | 0.0884 | 0.107* | |
C24 | 0.1128 (2) | 0.1860 (3) | 0.10315 (18) | 0.0983 (11) | |
H24 | 0.0919 | 0.1157 | 0.1159 | 0.118* | |
C25 | 0.07842 (19) | 0.2967 (4) | 0.10051 (19) | 0.0990 (11) | |
H25 | 0.0340 | 0.3013 | 0.1116 | 0.119* | |
C26 | 0.10822 (19) | 0.4010 (3) | 0.08185 (18) | 0.0915 (10) | |
H26 | 0.0842 | 0.4758 | 0.0809 | 0.110* | |
C31 | 0.1943 (2) | 0.6486 (3) | 0.09347 (19) | 0.0756 (9) | |
C32 | 0.1369 (2) | 0.7304 (3) | 0.06577 (19) | 0.0992 (11) | |
H32 | 0.1083 | 0.7255 | 0.0159 | 0.119* | |
C33 | 0.1198 (3) | 0.8195 (4) | 0.1085 (3) | 0.1285 (16) | |
H33 | 0.0805 | 0.8737 | 0.0875 | 0.154* | |
C34 | 0.1601 (3) | 0.8282 (4) | 0.1812 (3) | 0.1363 (18) | |
H34 | 0.1488 | 0.8885 | 0.2103 | 0.164* | |
C35 | 0.2171 (3) | 0.7485 (5) | 0.2115 (2) | 0.1246 (16) | |
H35 | 0.2446 | 0.7540 | 0.2617 | 0.150* | |
C36 | 0.2345 (2) | 0.6585 (4) | 0.1681 (2) | 0.1059 (12) | |
H36 | 0.2737 | 0.6044 | 0.1896 | 0.127* | |
C41 | 0.35536 (18) | 0.7928 (2) | −0.06731 (16) | 0.0690 (8) | |
C42 | 0.39207 (18) | 0.8436 (3) | −0.11312 (19) | 0.0795 (9) | |
H42 | 0.4436 | 0.8562 | −0.0943 | 0.095* | |
C43 | 0.3539 (2) | 0.8756 (3) | −0.18563 (19) | 0.0851 (10) | |
H43 | 0.3800 | 0.9087 | −0.2149 | 0.102* | |
C44 | 0.2777 (2) | 0.8586 (3) | −0.21488 (17) | 0.0811 (9) | |
H44 | 0.2529 | 0.8767 | −0.2645 | 0.097* | |
C45 | 0.23726 (19) | 0.8148 (3) | −0.17097 (18) | 0.0705 (9) | |
C46 | 0.27755 (19) | 0.7808 (3) | −0.09856 (17) | 0.0676 (8) | |
C51 | 0.39031 (16) | 0.8775 (3) | 0.07991 (17) | 0.0723 (9) | |
C52 | 0.40297 (18) | 0.9960 (4) | 0.06191 (18) | 0.0929 (10) | |
H52 | 0.4152 | 1.0099 | 0.0192 | 0.111* | |
C53 | 0.3981 (2) | 1.0952 (3) | 0.1055 (3) | 0.1059 (12) | |
H53 | 0.4078 | 1.1740 | 0.0924 | 0.127* | |
C54 | 0.3789 (2) | 1.0769 (4) | 0.1675 (2) | 0.1044 (12) | |
H54 | 0.3753 | 1.1431 | 0.1968 | 0.125* | |
C55 | 0.36526 (19) | 0.9610 (5) | 0.1862 (2) | 0.1046 (12) | |
H55 | 0.3522 | 0.9481 | 0.2285 | 0.126* | |
C56 | 0.37075 (16) | 0.8619 (4) | 0.1426 (2) | 0.0873 (10) | |
H56 | 0.3610 | 0.7833 | 0.1561 | 0.105* | |
C61 | 0.49927 (17) | 0.7405 (3) | 0.03746 (17) | 0.0705 (8) | |
C62 | 0.5531 (2) | 0.8103 (3) | 0.08804 (17) | 0.0753 (9) | |
H62 | 0.5385 | 0.8717 | 0.1142 | 0.090* | |
C63 | 0.6286 (2) | 0.7904 (3) | 0.10043 (19) | 0.0893 (10) | |
H63 | 0.6642 | 0.8372 | 0.1355 | 0.107* | |
C64 | 0.6517 (2) | 0.7016 (3) | 0.0611 (2) | 0.0900 (10) | |
H64 | 0.7025 | 0.6886 | 0.0694 | 0.108* | |
C65 | 0.5990 (2) | 0.6327 (3) | 0.0096 (2) | 0.0914 (10) | |
H65 | 0.6139 | 0.5730 | −0.0175 | 0.110* | |
C66 | 0.5239 (2) | 0.6523 (3) | −0.00184 (17) | 0.0834 (10) | |
H66 | 0.4886 | 0.6050 | −0.0369 | 0.100* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0682 (6) | 0.0870 (6) | 0.0849 (6) | −0.0005 (5) | 0.0292 (5) | 0.0145 (5) |
P2 | 0.0736 (6) | 0.0800 (6) | 0.0802 (6) | −0.0107 (5) | 0.0241 (5) | 0.0105 (5) |
Si | 0.0979 (8) | 0.0771 (6) | 0.0799 (7) | 0.0011 (6) | 0.0245 (6) | −0.0018 (5) |
O | 0.0713 (14) | 0.0893 (14) | 0.0589 (13) | −0.0156 (12) | 0.0229 (12) | 0.0043 (11) |
N | 0.077 (2) | 0.0775 (17) | 0.0626 (17) | −0.0054 (15) | 0.0185 (15) | 0.0091 (13) |
C1 | 0.097 (3) | 0.102 (3) | 0.126 (3) | 0.006 (2) | −0.014 (2) | −0.024 (2) |
C2 | 0.197 (4) | 0.094 (3) | 0.096 (3) | 0.035 (3) | 0.060 (3) | 0.027 (2) |
C3 | 0.088 (3) | 0.089 (2) | 0.088 (2) | −0.017 (2) | 0.039 (2) | −0.007 (2) |
C4 | 0.184 (5) | 0.090 (3) | 0.179 (4) | 0.022 (3) | 0.080 (3) | −0.015 (3) |
C5 | 0.123 (3) | 0.171 (4) | 0.170 (4) | −0.071 (3) | 0.073 (3) | −0.093 (3) |
C6 | 0.140 (3) | 0.119 (3) | 0.110 (3) | −0.026 (3) | 0.058 (3) | −0.028 (2) |
C11 | 0.063 (2) | 0.064 (2) | 0.071 (2) | −0.0031 (17) | 0.0248 (18) | −0.0030 (18) |
C12 | 0.085 (3) | 0.069 (2) | 0.082 (2) | 0.001 (2) | 0.034 (2) | 0.0017 (19) |
C13 | 0.077 (2) | 0.074 (2) | 0.087 (3) | −0.0118 (19) | 0.022 (2) | −0.009 (2) |
C14 | 0.076 (2) | 0.082 (2) | 0.065 (2) | 0.001 (2) | 0.0173 (19) | −0.008 (2) |
C15 | 0.076 (2) | 0.071 (2) | 0.055 (2) | −0.0052 (19) | 0.0166 (19) | −0.0001 (18) |
C16 | 0.063 (2) | 0.068 (2) | 0.074 (2) | −0.0094 (18) | 0.028 (2) | −0.0084 (19) |
C21 | 0.070 (2) | 0.070 (2) | 0.080 (2) | 0.0089 (18) | 0.0302 (19) | 0.0058 (17) |
C22 | 0.074 (2) | 0.088 (2) | 0.075 (2) | 0.002 (2) | 0.0283 (18) | 0.0013 (19) |
C23 | 0.101 (3) | 0.072 (3) | 0.098 (3) | 0.006 (2) | 0.035 (2) | 0.002 (2) |
C24 | 0.110 (3) | 0.077 (3) | 0.118 (3) | −0.022 (2) | 0.050 (3) | −0.005 (2) |
C25 | 0.092 (3) | 0.082 (3) | 0.145 (3) | −0.009 (2) | 0.069 (2) | −0.002 (2) |
C26 | 0.086 (3) | 0.074 (2) | 0.129 (3) | 0.003 (2) | 0.055 (2) | 0.004 (2) |
C31 | 0.077 (2) | 0.080 (2) | 0.068 (3) | −0.014 (2) | 0.021 (2) | 0.005 (2) |
C32 | 0.129 (3) | 0.097 (3) | 0.079 (3) | 0.010 (3) | 0.044 (2) | −0.008 (2) |
C33 | 0.183 (5) | 0.114 (3) | 0.101 (3) | 0.025 (3) | 0.064 (4) | −0.004 (3) |
C34 | 0.200 (6) | 0.116 (4) | 0.118 (5) | −0.031 (4) | 0.087 (4) | −0.026 (3) |
C35 | 0.145 (5) | 0.163 (5) | 0.069 (3) | −0.053 (4) | 0.039 (3) | −0.012 (3) |
C36 | 0.105 (3) | 0.137 (4) | 0.076 (3) | −0.024 (3) | 0.030 (3) | 0.003 (3) |
C41 | 0.072 (2) | 0.071 (2) | 0.067 (2) | −0.0087 (17) | 0.0268 (19) | 0.0057 (16) |
C42 | 0.079 (2) | 0.079 (2) | 0.082 (3) | −0.0115 (18) | 0.029 (2) | 0.0071 (19) |
C43 | 0.097 (3) | 0.085 (2) | 0.082 (3) | −0.014 (2) | 0.041 (2) | 0.015 (2) |
C44 | 0.092 (3) | 0.090 (2) | 0.062 (2) | −0.010 (2) | 0.027 (2) | 0.0069 (18) |
C45 | 0.077 (3) | 0.075 (2) | 0.061 (2) | −0.0063 (19) | 0.024 (2) | 0.0015 (17) |
C46 | 0.073 (2) | 0.075 (2) | 0.060 (2) | −0.0093 (18) | 0.028 (2) | 0.0063 (17) |
C51 | 0.062 (2) | 0.085 (3) | 0.068 (2) | −0.0054 (17) | 0.0201 (18) | 0.0173 (18) |
C52 | 0.115 (3) | 0.085 (3) | 0.092 (3) | 0.001 (2) | 0.051 (2) | 0.010 (2) |
C53 | 0.112 (3) | 0.089 (3) | 0.127 (3) | 0.004 (2) | 0.052 (3) | 0.013 (3) |
C54 | 0.089 (3) | 0.115 (4) | 0.115 (4) | 0.023 (2) | 0.041 (2) | 0.002 (3) |
C55 | 0.097 (3) | 0.136 (4) | 0.093 (3) | 0.012 (3) | 0.048 (2) | 0.013 (3) |
C56 | 0.071 (2) | 0.103 (3) | 0.092 (3) | −0.0025 (19) | 0.033 (2) | 0.013 (2) |
C61 | 0.074 (2) | 0.066 (2) | 0.070 (2) | −0.008 (2) | 0.0223 (19) | 0.0048 (18) |
C62 | 0.075 (3) | 0.075 (2) | 0.082 (3) | −0.010 (2) | 0.033 (2) | −0.0021 (18) |
C63 | 0.076 (3) | 0.100 (3) | 0.088 (3) | −0.014 (2) | 0.022 (2) | 0.004 (2) |
C64 | 0.070 (3) | 0.100 (3) | 0.105 (3) | −0.005 (2) | 0.036 (2) | 0.009 (2) |
C65 | 0.089 (3) | 0.088 (3) | 0.104 (3) | 0.001 (2) | 0.040 (3) | 0.004 (2) |
C66 | 0.088 (3) | 0.074 (2) | 0.087 (3) | −0.011 (2) | 0.027 (2) | −0.004 (2) |
P1—C31 | 1.819 (3) | C24—C25 | 1.363 (4) |
P1—C21 | 1.831 (3) | C24—H24 | 0.9300 |
P1—C11 | 1.833 (3) | C25—C26 | 1.366 (4) |
P2—C51 | 1.822 (3) | C25—H25 | 0.9300 |
P2—C41 | 1.826 (3) | C26—H26 | 0.9300 |
P2—C61 | 1.839 (3) | C31—C32 | 1.369 (4) |
P1—P2 | 4.1453 (12) | C31—C36 | 1.382 (4) |
Si—N | 1.783 (2) | C32—C33 | 1.373 (4) |
Si—C2 | 1.855 (3) | C32—H32 | 0.9300 |
Si—C3 | 1.858 (3) | C33—C34 | 1.349 (5) |
Si—C1 | 1.863 (3) | C33—H33 | 0.9300 |
O—C46 | 1.390 (3) | C34—C35 | 1.355 (5) |
O—C16 | 1.399 (3) | C34—H34 | 0.9300 |
N—C15 | 1.435 (3) | C35—C36 | 1.392 (5) |
N—C45 | 1.436 (3) | C35—H35 | 0.9300 |
C1—H1A | 0.9600 | C36—H36 | 0.9300 |
C1—H1B | 0.9600 | C41—C42 | 1.396 (4) |
C1—H1C | 0.9600 | C41—C46 | 1.398 (3) |
C2—H2A | 0.9600 | C42—C43 | 1.380 (4) |
C2—H2B | 0.9600 | C42—H42 | 0.9300 |
C2—H2C | 0.9600 | C43—C44 | 1.375 (4) |
C3—C6 | 1.514 (4) | C43—H43 | 0.9300 |
C3—C5 | 1.524 (4) | C44—C45 | 1.390 (4) |
C3—C4 | 1.546 (4) | C44—H44 | 0.9300 |
C4—H4A | 0.9600 | C45—C46 | 1.393 (4) |
C4—H4B | 0.9600 | C51—C56 | 1.374 (4) |
C4—H4C | 0.9600 | C51—C52 | 1.377 (4) |
C5—H5A | 0.9600 | C52—C53 | 1.385 (4) |
C5—H5B | 0.9600 | C52—H52 | 0.9300 |
C5—H5C | 0.9600 | C53—C54 | 1.362 (4) |
C6—H6A | 0.9600 | C53—H53 | 0.9300 |
C6—H6B | 0.9600 | C54—C55 | 1.360 (4) |
C6—H6C | 0.9600 | C54—H54 | 0.9300 |
C11—C16 | 1.391 (3) | C55—C56 | 1.390 (4) |
C11—C12 | 1.403 (3) | C55—H55 | 0.9300 |
C12—C13 | 1.373 (3) | C56—H56 | 0.9300 |
C12—H12 | 0.9300 | C61—C62 | 1.379 (3) |
C13—C14 | 1.387 (4) | C61—C66 | 1.390 (4) |
C13—H13 | 0.9300 | C62—C63 | 1.383 (4) |
C14—C15 | 1.381 (3) | C62—H62 | 0.9300 |
C14—H14 | 0.9300 | C63—C64 | 1.381 (4) |
C15—C16 | 1.381 (4) | C63—H63 | 0.9300 |
C21—C22 | 1.376 (3) | C64—C65 | 1.370 (4) |
C21—C26 | 1.396 (4) | C64—H64 | 0.9300 |
C22—C23 | 1.374 (4) | C65—C66 | 1.378 (4) |
C22—H22 | 0.9300 | C65—H65 | 0.9300 |
C23—C24 | 1.382 (4) | C66—H66 | 0.9300 |
C23—H23 | 0.9300 | ||
C31—P1—C21 | 100.32 (14) | C25—C24—H24 | 120.0 |
C31—P1—C11 | 101.88 (15) | C23—C24—H24 | 120.0 |
C21—P1—C11 | 102.34 (14) | C24—C25—C26 | 120.9 (3) |
C51—P2—C41 | 101.49 (14) | C24—C25—H25 | 119.5 |
C51—P2—C61 | 103.04 (15) | C26—C25—H25 | 119.5 |
C41—P2—C61 | 102.27 (15) | C25—C26—C21 | 120.8 (3) |
N—Si—C2 | 111.17 (14) | C25—C26—H26 | 119.6 |
N—Si—C3 | 111.19 (14) | C21—C26—H26 | 119.6 |
C2—Si—C3 | 108.74 (15) | C32—C31—C36 | 116.4 (3) |
N—Si—C1 | 109.08 (13) | C32—C31—P1 | 125.2 (3) |
C2—Si—C1 | 107.61 (16) | C36—C31—P1 | 118.3 (3) |
C3—Si—C1 | 108.96 (15) | C31—C32—C33 | 122.8 (4) |
C46—O—C16 | 113.1 (2) | C31—C32—H32 | 118.6 |
C15—N—C45 | 110.4 (2) | C33—C32—H32 | 118.6 |
C15—N—Si | 123.6 (2) | C34—C33—C32 | 119.9 (4) |
C45—N—Si | 119.6 (2) | C34—C33—H33 | 120.1 |
Si—C1—H1A | 109.5 | C32—C33—H33 | 120.1 |
Si—C1—H1B | 109.5 | C33—C34—C35 | 119.7 (5) |
H1A—C1—H1B | 109.5 | C33—C34—H34 | 120.1 |
Si—C1—H1C | 109.5 | C35—C34—H34 | 120.1 |
H1A—C1—H1C | 109.5 | C34—C35—C36 | 120.4 (5) |
H1B—C1—H1C | 109.5 | C34—C35—H35 | 119.8 |
Si—C2—H2A | 109.5 | C36—C35—H35 | 119.8 |
Si—C2—H2B | 109.5 | C31—C36—C35 | 120.8 (4) |
H2A—C2—H2B | 109.5 | C31—C36—H36 | 119.6 |
Si—C2—H2C | 109.5 | C35—C36—H36 | 119.6 |
H2A—C2—H2C | 109.5 | C42—C41—C46 | 115.9 (3) |
H2B—C2—H2C | 109.5 | C42—C41—P2 | 126.3 (3) |
C6—C3—C5 | 108.6 (3) | C46—C41—P2 | 117.8 (2) |
C6—C3—C4 | 107.6 (3) | C43—C42—C41 | 121.8 (3) |
C5—C3—C4 | 107.0 (3) | C43—C42—H42 | 119.1 |
C6—C3—Si | 111.2 (2) | C41—C42—H42 | 119.1 |
C5—C3—Si | 112.6 (2) | C44—C43—C42 | 120.4 (3) |
C4—C3—Si | 109.6 (2) | C44—C43—H43 | 119.8 |
C3—C4—H4A | 109.5 | C42—C43—H43 | 119.8 |
C3—C4—H4B | 109.5 | C43—C44—C45 | 120.6 (3) |
H4A—C4—H4B | 109.5 | C43—C44—H44 | 119.7 |
C3—C4—H4C | 109.5 | C45—C44—H44 | 119.7 |
H4A—C4—H4C | 109.5 | C44—C45—C46 | 117.5 (3) |
H4B—C4—H4C | 109.5 | C44—C45—N | 123.5 (3) |
C3—C5—H5A | 109.5 | C46—C45—N | 119.0 (3) |
C3—C5—H5B | 109.5 | O—C46—C45 | 119.0 (3) |
H5A—C5—H5B | 109.5 | O—C46—C41 | 117.4 (3) |
C3—C5—H5C | 109.5 | C45—C46—C41 | 123.7 (3) |
H5A—C5—H5C | 109.5 | C56—C51—C52 | 116.9 (3) |
H5B—C5—H5C | 109.5 | C56—C51—P2 | 118.1 (3) |
C3—C6—H6A | 109.5 | C52—C51—P2 | 125.1 (3) |
C3—C6—H6B | 109.5 | C51—C52—C53 | 122.0 (3) |
H6A—C6—H6B | 109.5 | C51—C52—H52 | 119.0 |
C3—C6—H6C | 109.5 | C53—C52—H52 | 119.0 |
H6A—C6—H6C | 109.5 | C54—C53—C52 | 119.8 (4) |
H6B—C6—H6C | 109.5 | C54—C53—H53 | 120.1 |
C16—C11—C12 | 115.6 (3) | C52—C53—H53 | 120.1 |
C16—C11—P1 | 120.0 (2) | C55—C54—C53 | 119.5 (4) |
C12—C11—P1 | 124.4 (3) | C55—C54—H54 | 120.3 |
C13—C12—C11 | 121.3 (3) | C53—C54—H54 | 120.3 |
C13—C12—H12 | 119.3 | C54—C55—C56 | 120.4 (4) |
C11—C12—H12 | 119.3 | C54—C55—H55 | 119.8 |
C12—C13—C14 | 120.7 (3) | C56—C55—H55 | 119.8 |
C12—C13—H13 | 119.6 | C51—C56—C55 | 121.4 (3) |
C14—C13—H13 | 119.6 | C51—C56—H56 | 119.3 |
C15—C14—C13 | 120.1 (3) | C55—C56—H56 | 119.3 |
C15—C14—H14 | 119.9 | C62—C61—C66 | 117.4 (3) |
C13—C14—H14 | 119.9 | C62—C61—P2 | 124.3 (3) |
C16—C15—C14 | 117.7 (3) | C66—C61—P2 | 117.8 (3) |
C16—C15—N | 119.2 (3) | C61—C62—C63 | 121.0 (3) |
C14—C15—N | 123.1 (3) | C61—C62—H62 | 119.5 |
C15—C16—C11 | 124.4 (3) | C63—C62—H62 | 119.5 |
C15—C16—O | 119.1 (3) | C64—C63—C62 | 120.5 (3) |
C11—C16—O | 116.4 (3) | C64—C63—H63 | 119.8 |
C22—C21—C26 | 116.9 (3) | C62—C63—H63 | 119.8 |
C22—C21—P1 | 117.9 (3) | C65—C64—C63 | 119.4 (3) |
C26—C21—P1 | 125.1 (3) | C65—C64—H64 | 120.3 |
C23—C22—C21 | 122.8 (3) | C63—C64—H64 | 120.3 |
C23—C22—H22 | 118.6 | C64—C65—C66 | 119.7 (3) |
C21—C22—H22 | 118.6 | C64—C65—H65 | 120.1 |
C22—C23—C24 | 118.6 (3) | C66—C65—H65 | 120.1 |
C22—C23—H23 | 120.7 | C65—C66—C61 | 122.0 (3) |
C24—C23—H23 | 120.7 | C65—C66—H66 | 119.0 |
C25—C24—C23 | 119.9 (3) | C61—C66—H66 | 119.0 |
C2—Si—N—C15 | −155.8 (2) | P1—C31—C32—C33 | −179.2 (3) |
C3—Si—N—C15 | 82.9 (3) | C31—C32—C33—C34 | −0.5 (6) |
C1—Si—N—C15 | −37.3 (3) | C32—C33—C34—C35 | −0.3 (7) |
C2—Si—N—C45 | 55.1 (3) | C33—C34—C35—C36 | 0.5 (7) |
C3—Si—N—C45 | −66.2 (3) | C32—C31—C36—C35 | −0.7 (5) |
C1—Si—N—C45 | 173.6 (2) | P1—C31—C36—C35 | 179.4 (3) |
N—Si—C3—C6 | −59.1 (3) | C34—C35—C36—C31 | 0.0 (6) |
C2—Si—C3—C6 | 178.2 (2) | C51—P2—C41—C42 | 93.8 (3) |
C1—Si—C3—C6 | 61.2 (3) | C61—P2—C41—C42 | −12.5 (3) |
N—Si—C3—C5 | 63.0 (3) | C51—P2—C41—C46 | −86.4 (2) |
C2—Si—C3—C5 | −59.7 (3) | C61—P2—C41—C46 | 167.4 (2) |
C1—Si—C3—C5 | −176.7 (3) | C46—C41—C42—C43 | −2.3 (4) |
N—Si—C3—C4 | −177.9 (2) | P2—C41—C42—C43 | 177.6 (2) |
C2—Si—C3—C4 | 59.4 (3) | C41—C42—C43—C44 | 0.4 (5) |
C1—Si—C3—C4 | −57.7 (3) | C42—C43—C44—C45 | 3.2 (5) |
C31—P1—C11—C16 | 75.7 (2) | C43—C44—C45—C46 | −4.5 (4) |
C21—P1—C11—C16 | 179.2 (2) | C43—C44—C45—N | 176.2 (3) |
C31—P1—C11—C12 | −107.4 (3) | C15—N—C45—C44 | 144.6 (3) |
C21—P1—C11—C12 | −3.9 (3) | Si—N—C45—C44 | −62.5 (3) |
C16—C11—C12—C13 | 0.6 (4) | C15—N—C45—C46 | −34.7 (3) |
P1—C11—C12—C13 | −176.4 (2) | Si—N—C45—C46 | 118.1 (3) |
C11—C12—C13—C14 | −1.5 (4) | C16—O—C46—C45 | 35.0 (3) |
C12—C13—C14—C15 | 0.0 (5) | C16—O—C46—C41 | −146.2 (3) |
C13—C14—C15—C16 | 2.2 (4) | C44—C45—C46—O | −178.7 (3) |
C13—C14—C15—N | −179.2 (3) | N—C45—C46—O | 0.6 (4) |
C45—N—C15—C16 | 34.5 (4) | C44—C45—C46—C41 | 2.5 (4) |
Si—N—C15—C16 | −117.0 (3) | N—C45—C46—C41 | −178.1 (3) |
C45—N—C15—C14 | −144.1 (3) | C42—C41—C46—O | −177.9 (2) |
Si—N—C15—C14 | 64.4 (3) | P2—C41—C46—O | 2.2 (4) |
C14—C15—C16—C11 | −3.2 (4) | C42—C41—C46—C45 | 0.8 (4) |
N—C15—C16—C11 | 178.2 (3) | P2—C41—C46—C45 | −179.1 (2) |
C14—C15—C16—O | 178.5 (2) | C41—P2—C51—C56 | 138.9 (2) |
N—C15—C16—O | −0.2 (4) | C61—P2—C51—C56 | −115.5 (2) |
C12—C11—C16—C15 | 1.8 (4) | C41—P2—C51—C52 | −42.3 (3) |
P1—C11—C16—C15 | 178.9 (2) | C61—P2—C51—C52 | 63.3 (3) |
C12—C11—C16—O | −179.8 (2) | C56—C51—C52—C53 | 1.4 (5) |
P1—C11—C16—O | −2.7 (3) | P2—C51—C52—C53 | −177.4 (3) |
C46—O—C16—C15 | −35.4 (3) | C51—C52—C53—C54 | −1.2 (5) |
C46—O—C16—C11 | 146.1 (3) | C52—C53—C54—C55 | 0.4 (6) |
C31—P1—C21—C22 | −147.1 (2) | C53—C54—C55—C56 | 0.1 (6) |
C11—P1—C21—C22 | 108.2 (2) | C52—C51—C56—C55 | −1.0 (5) |
C31—P1—C21—C26 | 30.1 (3) | P2—C51—C56—C55 | 177.9 (2) |
C11—P1—C21—C26 | −74.6 (3) | C54—C55—C56—C51 | 0.3 (5) |
C26—C21—C22—C23 | 1.6 (5) | C51—P2—C61—C62 | 14.5 (3) |
P1—C21—C22—C23 | 179.1 (2) | C41—P2—C61—C62 | 119.6 (3) |
C21—C22—C23—C24 | −1.0 (5) | C51—P2—C61—C66 | −174.5 (2) |
C22—C23—C24—C25 | 0.1 (5) | C41—P2—C61—C66 | −69.5 (2) |
C23—C24—C25—C26 | 0.0 (5) | C66—C61—C62—C63 | −1.9 (4) |
C24—C25—C26—C21 | 0.7 (5) | P2—C61—C62—C63 | 169.2 (2) |
C22—C21—C26—C25 | −1.5 (5) | C61—C62—C63—C64 | 1.4 (5) |
P1—C21—C26—C25 | −178.7 (3) | C62—C63—C64—C65 | −0.2 (5) |
C21—P1—C31—C32 | −98.9 (3) | C63—C64—C65—C66 | −0.4 (5) |
C11—P1—C31—C32 | 6.2 (3) | C64—C65—C66—C61 | 0.0 (5) |
C21—P1—C31—C36 | 81.0 (3) | C62—C61—C66—C65 | 1.2 (4) |
C11—P1—C31—C36 | −173.9 (3) | P2—C61—C66—C65 | −170.4 (2) |
C36—C31—C32—C33 | 0.9 (5) |
Experimental details
Crystal data | |
Chemical formula | C42H41NOP2Si |
Mr | 665.79 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 291 |
a, b, c (Å) | 18.8748 (18), 10.8973 (10), 19.1042 (15) |
β (°) | 109.139 (5) |
V (Å3) | 3712.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.20 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32114, 6468, 2229 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.079, 0.99 |
No. of reflections | 6468 |
No. of parameters | 429 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.18 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1991), SHELXL97, PARST95 (Nardelli, 1995) and PLATON (Spek, 2003).
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The title compound, (I), is a diphosphine ligand used for highly regioselective hydroformylation reactions, one of the most important homogeneously catalysed industrial reactions, which produces mixtures of linear and branched aldehydes from olefins, carbon monoxide and hydrogen (Claver & van Leeuwen, 2000). In order to achieve high selectivity towards formation of one product, the appropriate ligand must be employed. van Leeuwen has pioneered the use of xanthene- and phenoxazine-based diphosphine ligands (Kranenburg et al., 1995; van der Veen et al., 1998), which give extremely regioselective rhodium catalysts that produce linear aldehydes.
As part of our investigation of structural modifications of hydroformylation catalysts, the title new ligand, (I), was prepared following a modified literature procedure (Antonio et al., 1989; Petrassi et al., 2000; van der Veen et al., 2000). According to the preliminary results, this compound was found to be superior over nixantphos as a ligand with regard to selectivity (Osiński & Eilbracht, 2005). It was believed that a crystal structure determination of this compound might allow for the determination of important ligand factors, such as the cone angle and the flexibility range of the natural bite angle.