Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112002934/gg3269sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112002934/gg3269Isup2.hkl |
CCDC reference: 873888
Chemicals and solvents were purchased from commercial sources and used as received. 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin (TPPF20) was prepared according to a published procedure (Tomé et al., 2005). To a solution of TPPF20 (25 mg, 25.7 µmol) in dry toluene (2.5 ml; Riedel-de Haën, 99,7%), triethyl phosphite was added in excess (1.0 ml, 5.8 mmol; Sigma–Aldrich, 98%) and the mixture was stirred at reflux for 48 h under a nitrogen atmosphere. Toluene and the excess of triethyl phosphite were distilled off under reduced pressure. The crude mixture was purified by column chromatography using dichloromethane as eluent. Compound (I) was recrystallized from a mixture of dichloromethane and methanol [Solvent ratio?] at ambient temperature (yield 22%). Spectroscopic analysis: 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 8.93 (d, J = 3.3 Hz, 8H, β-H), 4.66–4.44 (m, 4H, CH2), 1.59 (t, J = 7.0 Hz, 6H, CH3), -2.92 (s, 2H, NH); 19F NMR (282 MHz, CDCl3, δ, p.p.m.): -155.26 (dd, J = 23.7 and 13.6 Hz, 2F, 5-Ar-o-F), -158.79 to -159.02 (m, 2F, 5-Ar-m-F), -160.02 (dd, J = 24.3 and 7.4 Hz, 6F, 10,15,20-Ar-o-F), -174.70 (t, J = 20.9 Hz, 3F, 10,15,20-Ar-p-F), -184.63 to -184.96 (m, 6F, 10,15,20-Ar-m-F); 31P NMR (121 MHz, CDCl3, δ, p.p.m.): 5.80 (s, R–PO3Et2).
H atoms bound to C and N atoms were placed at their idealized positions and included in the final structural model in the riding-motion approximation, with C—H = 0.95 (aromatic), 0.99 (methylene) or 0.98 Å (methyl) and N—H = 0.88 Å. The isotropic displacement parameters for these atoms were fixed at 1.5Ueq(C) for methyl H atoms and 1.2Ueq(parent) otherwise.
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C48H20F19N4O3P | F(000) = 2184 |
Mr = 1092.65 | Dx = 1.599 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5493 reflections |
a = 15.530 (2) Å | θ = 2.2–24.6° |
b = 11.2539 (17) Å | µ = 0.19 mm−1 |
c = 26.375 (3) Å | T = 150 K |
β = 100.024 (9)° | Block, red |
V = 4539.3 (11) Å3 | 0.08 × 0.05 × 0.03 mm |
Z = 4 |
Bruker APEXII X8 Kappa CCD area-detector diffractometer | 8275 independent reflections |
Radiation source: fine-focus sealed tube | 3504 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.115 |
ω and ϕ scans | θmax = 25.4°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −15→18 |
Tmin = 0.985, Tmax = 0.994 | k = −12→13 |
32626 measured reflections | l = −30→31 |
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)] = 0.084 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.271 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.1428P)2] where P = (Fo2 + 2Fc2)/3 |
8275 reflections | (Δ/σ)max < 0.001 |
678 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C48H20F19N4O3P | V = 4539.3 (11) Å3 |
Mr = 1092.65 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.530 (2) Å | µ = 0.19 mm−1 |
b = 11.2539 (17) Å | T = 150 K |
c = 26.375 (3) Å | 0.08 × 0.05 × 0.03 mm |
β = 100.024 (9)° |
Bruker APEXII X8 Kappa CCD area-detector diffractometer | 8275 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 3504 reflections with I > 2σ(I) |
Tmin = 0.985, Tmax = 0.994 | Rint = 0.115 |
32626 measured reflections |
R[F2 > 2σ(F2)] = 0.084 | 0 restraints |
wR(F2) = 0.271 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.42 e Å−3 |
8275 reflections | Δρmin = −0.34 e Å−3 |
678 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 | 0.16439 (12) | −0.33648 (17) | 0.46670 (6) | 0.0652 (6) | |
O1 | 0.1598 (3) | −0.2804 (4) | 0.41705 (15) | 0.0719 (13) | |
O2 | 0.0863 (3) | −0.4204 (4) | 0.47212 (15) | 0.0707 (13) | |
O3 | 0.2468 (3) | −0.4131 (4) | 0.48763 (17) | 0.0868 (16) | |
F1 | 0.1924 (2) | 0.0838 (3) | 0.54643 (12) | 0.0649 (10) | |
F2 | 0.1613 (2) | −0.0599 (3) | 0.46667 (11) | 0.0669 (10) | |
F3 | 0.1806 (3) | −0.3904 (3) | 0.57991 (13) | 0.0807 (12) | |
F4 | 0.2058 (3) | −0.2426 (3) | 0.65892 (12) | 0.0731 (11) | |
F5 | 0.0266 (2) | 0.5186 (3) | 0.66925 (13) | 0.0673 (10) | |
F6 | −0.1342 (3) | 0.6132 (4) | 0.64182 (15) | 0.0882 (12) | |
F7 | −0.2752 (2) | 0.5047 (4) | 0.66976 (14) | 0.0885 (13) | |
F8 | −0.2534 (2) | 0.3073 (4) | 0.72954 (14) | 0.0816 (12) | |
F9 | −0.0921 (2) | 0.2125 (3) | 0.75712 (13) | 0.0701 (10) | |
F10 | 0.3384 (3) | 0.6298 (3) | 0.84165 (14) | 0.0870 (12) | |
F11 | 0.3764 (3) | 0.7932 (4) | 0.91557 (16) | 0.0953 (13) | |
F12 | 0.3993 (3) | 0.7278 (4) | 1.01585 (15) | 0.0971 (14) | |
F13 | 0.3848 (3) | 0.4970 (4) | 1.04133 (13) | 0.0877 (13) | |
F14 | 0.3393 (3) | 0.3333 (4) | 0.96711 (12) | 0.0749 (11) | |
F15 | 0.6237 (3) | 0.1375 (4) | 0.75765 (16) | 0.0873 (12) | |
F16 | 0.7822 (3) | 0.0394 (4) | 0.7903 (2) | 0.1208 (18) | |
F17 | 0.8006 (3) | −0.1359 (5) | 0.8611 (2) | 0.132 (2) | |
F18 | 0.6577 (4) | −0.2269 (6) | 0.8920 (3) | 0.171 (3) | |
F19 | 0.4985 (3) | −0.1341 (5) | 0.8574 (2) | 0.145 (2) | |
N1 | 0.1609 (3) | 0.1585 (4) | 0.70239 (15) | 0.0414 (11) | |
N2 | 0.1990 (3) | 0.3254 (4) | 0.78848 (15) | 0.0444 (11) | |
H2 | 0.2278 | 0.2685 | 0.7758 | 0.053* | |
N3 | 0.3714 (3) | 0.2208 (4) | 0.81267 (16) | 0.0464 (12) | |
N4 | 0.3350 (3) | 0.0582 (4) | 0.72488 (16) | 0.0460 (12) | |
H4 | 0.3053 | 0.1129 | 0.7384 | 0.055* | |
C1 | −0.0037 (4) | −0.3951 (7) | 0.4477 (3) | 0.074 (2) | |
H1A | −0.0372 | −0.4704 | 0.4437 | 0.089* | |
H1B | −0.0035 | −0.3626 | 0.4129 | 0.089* | |
C2 | −0.0486 (5) | −0.3094 (7) | 0.4773 (3) | 0.095 (2) | |
H2A | −0.0465 | −0.3390 | 0.5124 | 0.142* | |
H2B | −0.1097 | −0.3007 | 0.4605 | 0.142* | |
H2C | −0.0193 | −0.2321 | 0.4784 | 0.142* | |
C3 | 0.2754 (5) | −0.5152 (7) | 0.4624 (3) | 0.090 (2) | |
H3A | 0.2741 | −0.4977 | 0.4255 | 0.108* | |
H3B | 0.2359 | −0.5832 | 0.4650 | 0.108* | |
C4 | 0.3669 (6) | −0.5454 (8) | 0.4880 (4) | 0.114 (3) | |
H4A | 0.4035 | −0.4741 | 0.4900 | 0.171* | |
H4B | 0.3908 | −0.6065 | 0.4679 | 0.171* | |
H4C | 0.3661 | −0.5755 | 0.5228 | 0.171* | |
C5 | 0.0818 (4) | 0.2156 (5) | 0.69625 (19) | 0.0442 (14) | |
C6 | 0.0604 (3) | 0.3071 (5) | 0.72770 (19) | 0.0424 (14) | |
C7 | 0.1153 (4) | 0.3562 (5) | 0.76999 (19) | 0.0449 (14) | |
C8 | 0.0934 (4) | 0.4527 (6) | 0.8017 (2) | 0.0560 (16) | |
H8 | 0.0389 | 0.4929 | 0.7978 | 0.067* | |
C9 | 0.1640 (4) | 0.4752 (6) | 0.8375 (2) | 0.0560 (16) | |
H9 | 0.1681 | 0.5340 | 0.8637 | 0.067* | |
C10 | 0.2323 (4) | 0.3948 (5) | 0.8295 (2) | 0.0509 (15) | |
C11 | 0.3161 (4) | 0.3847 (5) | 0.85936 (19) | 0.0482 (15) | |
C12 | 0.3793 (4) | 0.3005 (5) | 0.8522 (2) | 0.0453 (14) | |
C13 | 0.4612 (4) | 0.2863 (6) | 0.8868 (2) | 0.0531 (16) | |
H13 | 0.4822 | 0.3323 | 0.9166 | 0.064* | |
C14 | 0.5024 (4) | 0.1945 (5) | 0.8682 (2) | 0.0528 (16) | |
H14 | 0.5576 | 0.1622 | 0.8829 | 0.063* | |
C15 | 0.4466 (4) | 0.1550 (5) | 0.8221 (2) | 0.0455 (14) | |
C16 | 0.4693 (4) | 0.0632 (5) | 0.7899 (2) | 0.0471 (14) | |
C17 | 0.4182 (4) | 0.0218 (5) | 0.7452 (2) | 0.0492 (15) | |
C18 | 0.4415 (4) | −0.0647 (6) | 0.7108 (2) | 0.0592 (17) | |
H18 | 0.4958 | −0.1056 | 0.7147 | 0.071* | |
C19 | 0.3746 (4) | −0.0793 (6) | 0.6718 (2) | 0.0593 (16) | |
H19 | 0.3734 | −0.1312 | 0.6433 | 0.071* | |
C20 | 0.3050 (4) | −0.0027 (5) | 0.6808 (2) | 0.0479 (14) | |
C21 | 0.2211 (4) | 0.0068 (5) | 0.65156 (19) | 0.0485 (15) | |
C22 | 0.1532 (4) | 0.0812 (5) | 0.66182 (19) | 0.0439 (14) | |
C23 | 0.0671 (4) | 0.0888 (5) | 0.6306 (2) | 0.0486 (15) | |
H23 | 0.0461 | 0.0439 | 0.6005 | 0.058* | |
C24 | 0.0226 (4) | 0.1707 (5) | 0.6520 (2) | 0.0461 (14) | |
H24 | −0.0362 | 0.1947 | 0.6405 | 0.055* | |
C25 | 0.2015 (4) | −0.0746 (5) | 0.6055 (2) | 0.0483 (14) | |
C26 | 0.1893 (4) | −0.0347 (5) | 0.5558 (2) | 0.0503 (15) | |
C27 | 0.1738 (4) | −0.1092 (6) | 0.5137 (2) | 0.0514 (15) | |
C28 | 0.1727 (4) | −0.2326 (6) | 0.5202 (2) | 0.0543 (16) | |
C29 | 0.1841 (4) | −0.2716 (6) | 0.5702 (2) | 0.0582 (16) | |
C30 | 0.1964 (4) | −0.1962 (5) | 0.6119 (2) | 0.0516 (15) | |
C31 | −0.0288 (4) | 0.3623 (5) | 0.71366 (19) | 0.0439 (14) | |
C32 | −0.0416 (4) | 0.4645 (5) | 0.6848 (2) | 0.0509 (15) | |
C33 | −0.1236 (5) | 0.5140 (6) | 0.6701 (2) | 0.0599 (17) | |
C34 | −0.1937 (4) | 0.4599 (7) | 0.6847 (2) | 0.0618 (18) | |
C35 | −0.1836 (4) | 0.3604 (6) | 0.7142 (2) | 0.0565 (17) | |
C36 | −0.1015 (4) | 0.3105 (6) | 0.7285 (2) | 0.0520 (16) | |
C37 | 0.3387 (4) | 0.4742 (6) | 0.9018 (2) | 0.0532 (16) | |
C38 | 0.3487 (4) | 0.5943 (6) | 0.8903 (2) | 0.0636 (18) | |
C39 | 0.3683 (5) | 0.6778 (6) | 0.9283 (3) | 0.0703 (19) | |
C40 | 0.3803 (4) | 0.6445 (7) | 0.9787 (3) | 0.0676 (19) | |
C41 | 0.3728 (4) | 0.5294 (7) | 0.9919 (2) | 0.0656 (19) | |
C42 | 0.3503 (4) | 0.4462 (6) | 0.9528 (2) | 0.0577 (16) | |
C43 | 0.5571 (4) | 0.0040 (6) | 0.8070 (2) | 0.0517 (15) | |
C44 | 0.6306 (4) | 0.0473 (7) | 0.7901 (3) | 0.0611 (17) | |
C45 | 0.7121 (5) | −0.0020 (8) | 0.8070 (3) | 0.078 (2) | |
C46 | 0.7202 (6) | −0.0920 (10) | 0.8415 (4) | 0.087 (3) | |
C47 | 0.6500 (7) | −0.1388 (8) | 0.8575 (3) | 0.096 (3) | |
C48 | 0.5673 (5) | −0.0895 (7) | 0.8406 (3) | 0.084 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0666 (12) | 0.0658 (13) | 0.0601 (11) | 0.0103 (10) | 0.0028 (8) | −0.0159 (9) |
O1 | 0.070 (3) | 0.088 (4) | 0.056 (2) | −0.001 (2) | 0.009 (2) | −0.015 (2) |
O2 | 0.073 (3) | 0.065 (3) | 0.070 (3) | −0.003 (3) | 0.001 (2) | −0.007 (2) |
O3 | 0.080 (3) | 0.087 (4) | 0.086 (3) | 0.030 (3) | −0.006 (3) | −0.039 (3) |
F1 | 0.090 (3) | 0.052 (2) | 0.0554 (19) | 0.0117 (19) | 0.0192 (17) | 0.0056 (17) |
F2 | 0.088 (3) | 0.068 (2) | 0.0454 (18) | 0.0150 (19) | 0.0137 (17) | 0.0033 (18) |
F3 | 0.120 (3) | 0.046 (2) | 0.068 (2) | 0.004 (2) | −0.005 (2) | −0.0005 (18) |
F4 | 0.117 (3) | 0.050 (2) | 0.0492 (19) | 0.001 (2) | 0.0055 (19) | 0.0046 (17) |
F5 | 0.068 (2) | 0.052 (2) | 0.081 (2) | −0.0046 (18) | 0.0117 (19) | 0.0102 (18) |
F6 | 0.106 (3) | 0.066 (3) | 0.091 (3) | 0.030 (2) | 0.011 (2) | 0.015 (2) |
F7 | 0.066 (3) | 0.117 (4) | 0.083 (2) | 0.042 (2) | 0.013 (2) | −0.005 (2) |
F8 | 0.061 (2) | 0.103 (3) | 0.085 (2) | −0.002 (2) | 0.025 (2) | −0.004 (2) |
F9 | 0.068 (2) | 0.067 (3) | 0.081 (2) | 0.0026 (19) | 0.0283 (18) | 0.019 (2) |
F10 | 0.137 (4) | 0.059 (3) | 0.065 (2) | −0.008 (2) | 0.019 (2) | 0.002 (2) |
F11 | 0.124 (4) | 0.057 (3) | 0.106 (3) | −0.011 (2) | 0.023 (3) | −0.013 (2) |
F12 | 0.117 (3) | 0.083 (3) | 0.078 (2) | 0.016 (3) | −0.018 (2) | −0.037 (2) |
F13 | 0.109 (3) | 0.095 (3) | 0.053 (2) | 0.032 (3) | −0.0021 (19) | −0.009 (2) |
F14 | 0.105 (3) | 0.063 (3) | 0.057 (2) | 0.010 (2) | 0.0155 (19) | 0.0069 (19) |
F15 | 0.082 (3) | 0.083 (3) | 0.106 (3) | −0.011 (2) | 0.044 (2) | 0.011 (3) |
F16 | 0.052 (3) | 0.124 (4) | 0.193 (5) | −0.016 (3) | 0.041 (3) | −0.076 (4) |
F17 | 0.079 (3) | 0.140 (5) | 0.157 (4) | 0.062 (3) | −0.031 (3) | −0.077 (4) |
F18 | 0.180 (6) | 0.163 (6) | 0.178 (5) | 0.103 (5) | 0.054 (4) | 0.082 (5) |
F19 | 0.111 (4) | 0.125 (4) | 0.219 (6) | 0.043 (3) | 0.084 (4) | 0.108 (4) |
N1 | 0.046 (3) | 0.036 (3) | 0.044 (2) | 0.001 (2) | 0.012 (2) | −0.001 (2) |
N2 | 0.049 (3) | 0.044 (3) | 0.040 (2) | 0.006 (2) | 0.007 (2) | −0.008 (2) |
N3 | 0.042 (3) | 0.043 (3) | 0.054 (3) | 0.000 (2) | 0.010 (2) | 0.001 (2) |
N4 | 0.048 (3) | 0.041 (3) | 0.051 (3) | 0.001 (2) | 0.013 (2) | −0.008 (2) |
C1 | 0.068 (5) | 0.085 (6) | 0.067 (4) | −0.009 (4) | 0.009 (4) | 0.006 (4) |
C2 | 0.099 (6) | 0.077 (6) | 0.108 (6) | 0.006 (5) | 0.018 (5) | 0.013 (5) |
C3 | 0.088 (6) | 0.067 (5) | 0.113 (6) | 0.002 (4) | 0.008 (5) | −0.030 (5) |
C4 | 0.102 (7) | 0.068 (6) | 0.168 (8) | 0.032 (5) | 0.015 (6) | −0.008 (6) |
C5 | 0.050 (4) | 0.046 (4) | 0.039 (3) | −0.006 (3) | 0.014 (3) | 0.001 (3) |
C6 | 0.047 (3) | 0.043 (4) | 0.039 (3) | 0.000 (3) | 0.013 (2) | 0.003 (3) |
C7 | 0.053 (4) | 0.041 (4) | 0.042 (3) | 0.005 (3) | 0.010 (3) | 0.001 (3) |
C8 | 0.064 (4) | 0.058 (4) | 0.046 (3) | 0.013 (3) | 0.012 (3) | −0.008 (3) |
C9 | 0.069 (4) | 0.053 (4) | 0.045 (3) | 0.011 (3) | 0.008 (3) | −0.013 (3) |
C10 | 0.068 (4) | 0.046 (4) | 0.041 (3) | 0.002 (3) | 0.016 (3) | 0.001 (3) |
C11 | 0.061 (4) | 0.041 (4) | 0.042 (3) | 0.004 (3) | 0.006 (3) | −0.004 (3) |
C12 | 0.047 (4) | 0.046 (4) | 0.045 (3) | −0.008 (3) | 0.012 (3) | 0.002 (3) |
C13 | 0.054 (4) | 0.058 (4) | 0.048 (3) | −0.006 (3) | 0.012 (3) | −0.005 (3) |
C14 | 0.045 (4) | 0.055 (4) | 0.060 (4) | −0.003 (3) | 0.014 (3) | 0.008 (3) |
C15 | 0.043 (3) | 0.047 (4) | 0.050 (3) | −0.009 (3) | 0.017 (3) | 0.007 (3) |
C16 | 0.047 (4) | 0.041 (4) | 0.057 (3) | −0.010 (3) | 0.018 (3) | 0.004 (3) |
C17 | 0.051 (4) | 0.046 (4) | 0.053 (3) | 0.001 (3) | 0.016 (3) | −0.004 (3) |
C18 | 0.060 (4) | 0.056 (4) | 0.062 (4) | 0.012 (3) | 0.012 (3) | −0.006 (3) |
C19 | 0.066 (4) | 0.055 (4) | 0.059 (4) | 0.010 (3) | 0.015 (3) | −0.011 (3) |
C20 | 0.052 (4) | 0.045 (4) | 0.049 (3) | 0.003 (3) | 0.014 (3) | −0.002 (3) |
C21 | 0.068 (4) | 0.039 (4) | 0.041 (3) | −0.001 (3) | 0.015 (3) | −0.005 (3) |
C22 | 0.056 (4) | 0.033 (3) | 0.046 (3) | −0.001 (3) | 0.016 (3) | 0.002 (3) |
C23 | 0.063 (4) | 0.046 (4) | 0.039 (3) | −0.002 (3) | 0.014 (3) | −0.004 (3) |
C24 | 0.047 (3) | 0.043 (4) | 0.050 (3) | −0.004 (3) | 0.012 (3) | 0.000 (3) |
C25 | 0.060 (4) | 0.042 (4) | 0.043 (3) | 0.015 (3) | 0.011 (3) | 0.001 (3) |
C26 | 0.059 (4) | 0.032 (4) | 0.060 (4) | 0.011 (3) | 0.011 (3) | 0.009 (3) |
C27 | 0.055 (4) | 0.057 (4) | 0.042 (3) | 0.012 (3) | 0.008 (3) | 0.001 (3) |
C28 | 0.049 (4) | 0.055 (5) | 0.058 (4) | 0.009 (3) | 0.008 (3) | 0.001 (3) |
C29 | 0.073 (4) | 0.040 (4) | 0.059 (4) | 0.007 (3) | 0.002 (3) | 0.001 (3) |
C30 | 0.069 (4) | 0.045 (4) | 0.038 (3) | 0.009 (3) | 0.004 (3) | 0.001 (3) |
C31 | 0.046 (4) | 0.042 (4) | 0.042 (3) | 0.002 (3) | 0.006 (3) | −0.007 (3) |
C32 | 0.053 (4) | 0.047 (4) | 0.054 (3) | −0.003 (3) | 0.013 (3) | −0.008 (3) |
C33 | 0.080 (5) | 0.050 (4) | 0.049 (3) | 0.014 (4) | 0.010 (3) | 0.001 (3) |
C34 | 0.062 (5) | 0.068 (5) | 0.056 (4) | 0.021 (4) | 0.013 (3) | −0.007 (4) |
C35 | 0.048 (4) | 0.067 (5) | 0.059 (4) | −0.002 (3) | 0.023 (3) | −0.015 (4) |
C36 | 0.051 (4) | 0.059 (5) | 0.047 (3) | 0.006 (3) | 0.011 (3) | −0.004 (3) |
C37 | 0.055 (4) | 0.056 (4) | 0.049 (3) | 0.007 (3) | 0.010 (3) | −0.004 (3) |
C38 | 0.078 (5) | 0.058 (5) | 0.054 (4) | −0.004 (4) | 0.009 (3) | 0.002 (4) |
C39 | 0.084 (5) | 0.049 (5) | 0.076 (5) | −0.004 (4) | 0.009 (4) | −0.005 (4) |
C40 | 0.071 (5) | 0.062 (5) | 0.064 (4) | 0.009 (4) | −0.006 (3) | −0.021 (4) |
C41 | 0.071 (5) | 0.075 (6) | 0.045 (4) | 0.015 (4) | −0.005 (3) | −0.007 (4) |
C42 | 0.061 (4) | 0.053 (5) | 0.057 (4) | 0.011 (3) | 0.007 (3) | 0.001 (4) |
C43 | 0.042 (4) | 0.049 (4) | 0.065 (4) | 0.000 (3) | 0.013 (3) | −0.005 (3) |
C44 | 0.049 (4) | 0.067 (5) | 0.068 (4) | −0.005 (4) | 0.012 (3) | −0.022 (4) |
C45 | 0.051 (5) | 0.083 (6) | 0.104 (6) | −0.009 (5) | 0.023 (4) | −0.045 (5) |
C46 | 0.066 (6) | 0.092 (7) | 0.097 (6) | 0.032 (5) | 0.001 (5) | −0.048 (5) |
C47 | 0.105 (7) | 0.089 (7) | 0.095 (6) | 0.042 (6) | 0.018 (5) | 0.024 (5) |
C48 | 0.067 (5) | 0.088 (6) | 0.107 (6) | 0.019 (4) | 0.037 (4) | 0.029 (5) |
P1—O1 | 1.444 (5) | C8—C9 | 1.341 (8) |
P1—O3 | 1.562 (5) | C8—H8 | 0.9500 |
P1—O2 | 1.564 (5) | C9—C10 | 1.437 (8) |
P1—C28 | 1.821 (6) | C9—H9 | 0.9500 |
O2—C1 | 1.461 (7) | C10—C11 | 1.404 (8) |
O3—C3 | 1.436 (8) | C11—C12 | 1.399 (8) |
F1—C26 | 1.359 (6) | C11—C37 | 1.502 (8) |
F2—C27 | 1.342 (6) | C12—C13 | 1.440 (8) |
F3—C29 | 1.365 (7) | C13—C14 | 1.351 (8) |
F4—C30 | 1.329 (6) | C13—H13 | 0.9500 |
F5—C32 | 1.346 (7) | C14—C15 | 1.436 (8) |
F6—C33 | 1.337 (7) | C14—H14 | 0.9500 |
F7—C34 | 1.356 (7) | C15—C16 | 1.419 (8) |
F8—C35 | 1.360 (7) | C16—C17 | 1.382 (8) |
F9—C36 | 1.330 (7) | C16—C43 | 1.513 (8) |
F10—C38 | 1.327 (7) | C17—C18 | 1.421 (8) |
F11—C39 | 1.353 (8) | C18—C19 | 1.338 (8) |
F12—C40 | 1.351 (7) | C18—H18 | 0.9500 |
F13—C41 | 1.335 (7) | C19—C20 | 1.434 (8) |
F14—C42 | 1.345 (7) | C19—H19 | 0.9500 |
F15—C44 | 1.320 (8) | C20—C21 | 1.398 (8) |
F16—C45 | 1.328 (9) | C21—C22 | 1.409 (8) |
F17—C46 | 1.358 (8) | C21—C25 | 1.510 (8) |
F18—C47 | 1.336 (10) | C22—C23 | 1.446 (7) |
F19—C48 | 1.324 (8) | C23—C24 | 1.335 (7) |
N1—C22 | 1.368 (6) | C23—H23 | 0.9500 |
N1—C5 | 1.371 (7) | C24—H24 | 0.9500 |
N2—C7 | 1.352 (7) | C25—C26 | 1.367 (7) |
N2—C10 | 1.362 (7) | C25—C30 | 1.384 (8) |
N2—H2 | 0.8800 | C26—C27 | 1.378 (8) |
N3—C12 | 1.365 (7) | C27—C28 | 1.399 (8) |
N3—C15 | 1.369 (7) | C28—C29 | 1.371 (8) |
N4—C20 | 1.361 (7) | C29—C30 | 1.376 (8) |
N4—C17 | 1.374 (7) | C31—C32 | 1.375 (8) |
N4—H4 | 0.8800 | C31—C36 | 1.386 (8) |
C1—C2 | 1.488 (10) | C32—C33 | 1.381 (8) |
C1—H1A | 0.9900 | C33—C34 | 1.360 (9) |
C1—H1B | 0.9900 | C34—C35 | 1.356 (9) |
C2—H2A | 0.9800 | C35—C36 | 1.385 (8) |
C2—H2B | 0.9800 | C37—C42 | 1.361 (8) |
C2—H2C | 0.9800 | C37—C38 | 1.400 (9) |
C3—C4 | 1.503 (10) | C38—C39 | 1.370 (9) |
C3—H3A | 0.9900 | C39—C40 | 1.360 (9) |
C3—H3B | 0.9900 | C40—C41 | 1.353 (10) |
C4—H4A | 0.9800 | C41—C42 | 1.392 (9) |
C4—H4B | 0.9800 | C43—C48 | 1.368 (9) |
C4—H4C | 0.9800 | C43—C44 | 1.385 (9) |
C5—C6 | 1.398 (7) | C44—C45 | 1.384 (10) |
C5—C24 | 1.446 (7) | C45—C46 | 1.353 (12) |
C6—C7 | 1.395 (7) | C46—C47 | 1.344 (12) |
C6—C31 | 1.504 (7) | C47—C48 | 1.399 (11) |
C7—C8 | 1.446 (8) | ||
O1—P1—O3 | 118.0 (3) | N4—C20—C19 | 106.8 (5) |
O1—P1—O2 | 115.5 (2) | C21—C20—C19 | 127.7 (5) |
O3—P1—O2 | 103.6 (3) | C20—C21—C22 | 126.6 (5) |
O1—P1—C28 | 114.1 (3) | C20—C21—C25 | 115.8 (5) |
O3—P1—C28 | 97.9 (2) | C22—C21—C25 | 117.6 (5) |
O2—P1—C28 | 105.6 (3) | N1—C22—C21 | 124.2 (5) |
C1—O2—P1 | 122.7 (4) | N1—C22—C23 | 110.8 (5) |
C3—O3—P1 | 125.3 (4) | C21—C22—C23 | 125.1 (5) |
C22—N1—C5 | 104.5 (4) | C24—C23—C22 | 107.2 (5) |
C7—N2—C10 | 110.4 (5) | C24—C23—H23 | 126.4 |
C7—N2—H2 | 124.8 | C22—C23—H23 | 126.4 |
C10—N2—H2 | 124.8 | C23—C24—C5 | 106.2 (5) |
C12—N3—C15 | 104.9 (4) | C23—C24—H24 | 126.9 |
C20—N4—C17 | 110.0 (5) | C5—C24—H24 | 126.9 |
C20—N4—H4 | 125.0 | C26—C25—C30 | 116.2 (5) |
C17—N4—H4 | 125.0 | C26—C25—C21 | 123.2 (6) |
O2—C1—C2 | 113.3 (6) | C30—C25—C21 | 120.6 (5) |
O2—C1—H1A | 108.9 | F1—C26—C25 | 119.5 (5) |
C2—C1—H1A | 108.9 | F1—C26—C27 | 117.3 (5) |
O2—C1—H1B | 108.9 | C25—C26—C27 | 123.2 (6) |
C2—C1—H1B | 108.9 | F2—C27—C26 | 118.0 (6) |
H1A—C1—H1B | 107.7 | F2—C27—C28 | 121.4 (5) |
C1—C2—H2A | 109.5 | C26—C27—C28 | 120.6 (5) |
C1—C2—H2B | 109.5 | C29—C28—C27 | 115.7 (6) |
H2A—C2—H2B | 109.5 | C29—C28—P1 | 121.3 (5) |
C1—C2—H2C | 109.5 | C27—C28—P1 | 122.8 (4) |
H2A—C2—H2C | 109.5 | F3—C29—C28 | 119.5 (6) |
H2B—C2—H2C | 109.5 | F3—C29—C30 | 117.3 (5) |
O3—C3—C4 | 108.5 (6) | C28—C29—C30 | 123.2 (6) |
O3—C3—H3A | 110.0 | F4—C30—C29 | 118.8 (5) |
C4—C3—H3A | 110.0 | F4—C30—C25 | 120.2 (5) |
O3—C3—H3B | 110.0 | C29—C30—C25 | 121.0 (5) |
C4—C3—H3B | 110.0 | C32—C31—C36 | 117.5 (5) |
H3A—C3—H3B | 108.4 | C32—C31—C6 | 121.3 (5) |
C3—C4—H4A | 109.5 | C36—C31—C6 | 121.2 (5) |
C3—C4—H4B | 109.5 | F5—C32—C31 | 120.1 (5) |
H4A—C4—H4B | 109.5 | F5—C32—C33 | 117.9 (6) |
C3—C4—H4C | 109.5 | C31—C32—C33 | 122.0 (6) |
H4A—C4—H4C | 109.5 | F6—C33—C34 | 120.3 (6) |
H4B—C4—H4C | 109.5 | F6—C33—C32 | 120.8 (6) |
N1—C5—C6 | 125.2 (5) | C34—C33—C32 | 119.0 (6) |
N1—C5—C24 | 111.3 (5) | F7—C34—C35 | 118.8 (6) |
C6—C5—C24 | 123.5 (5) | F7—C34—C33 | 120.3 (7) |
C7—C6—C5 | 126.2 (5) | C35—C34—C33 | 120.9 (6) |
C7—C6—C31 | 116.2 (5) | C34—C35—F8 | 121.0 (6) |
C5—C6—C31 | 117.5 (5) | C34—C35—C36 | 120.0 (6) |
N2—C7—C6 | 127.0 (5) | F8—C35—C36 | 118.9 (6) |
N2—C7—C8 | 107.0 (5) | F9—C36—C35 | 119.8 (6) |
C6—C7—C8 | 126.0 (5) | F9—C36—C31 | 119.6 (5) |
C9—C8—C7 | 107.7 (5) | C35—C36—C31 | 120.6 (6) |
C9—C8—H8 | 126.2 | C42—C37—C38 | 115.9 (6) |
C7—C8—H8 | 126.2 | C42—C37—C11 | 123.7 (6) |
C8—C9—C10 | 108.2 (5) | C38—C37—C11 | 120.4 (5) |
C8—C9—H9 | 125.9 | F10—C38—C39 | 118.4 (6) |
C10—C9—H9 | 125.9 | F10—C38—C37 | 120.1 (6) |
N2—C10—C11 | 125.9 (5) | C39—C38—C37 | 121.5 (6) |
N2—C10—C9 | 106.8 (5) | F11—C39—C40 | 120.3 (6) |
C11—C10—C9 | 127.2 (5) | F11—C39—C38 | 119.7 (6) |
C12—C11—C10 | 125.6 (5) | C40—C39—C38 | 120.0 (7) |
C12—C11—C37 | 118.4 (5) | F12—C40—C41 | 119.6 (6) |
C10—C11—C37 | 115.9 (5) | F12—C40—C39 | 119.5 (7) |
N3—C12—C11 | 125.1 (5) | C41—C40—C39 | 120.8 (6) |
N3—C12—C13 | 111.3 (5) | F13—C41—C40 | 120.7 (6) |
C11—C12—C13 | 123.6 (5) | F13—C41—C42 | 121.0 (7) |
C14—C13—C12 | 106.1 (5) | C40—C41—C42 | 118.3 (6) |
C14—C13—H13 | 126.9 | F14—C42—C37 | 119.7 (6) |
C12—C13—H13 | 126.9 | F14—C42—C41 | 117.0 (6) |
C13—C14—C15 | 106.9 (5) | C37—C42—C41 | 123.3 (7) |
C13—C14—H14 | 126.6 | C48—C43—C44 | 118.1 (6) |
C15—C14—H14 | 126.6 | C48—C43—C16 | 121.9 (6) |
N3—C15—C16 | 125.4 (5) | C44—C43—C16 | 119.9 (6) |
N3—C15—C14 | 110.8 (5) | F15—C44—C45 | 118.9 (7) |
C16—C15—C14 | 123.7 (5) | F15—C44—C43 | 120.1 (6) |
C17—C16—C15 | 126.1 (5) | C45—C44—C43 | 121.0 (8) |
C17—C16—C43 | 117.4 (5) | F16—C45—C46 | 120.0 (9) |
C15—C16—C43 | 116.5 (5) | F16—C45—C44 | 120.7 (9) |
N4—C17—C16 | 126.5 (5) | C46—C45—C44 | 119.3 (8) |
N4—C17—C18 | 106.3 (5) | C47—C46—C45 | 121.3 (8) |
C16—C17—C18 | 127.2 (6) | C47—C46—F17 | 118.7 (10) |
C19—C18—C17 | 109.0 (5) | C45—C46—F17 | 120.0 (10) |
C19—C18—H18 | 125.5 | F18—C47—C46 | 121.5 (9) |
C17—C18—H18 | 125.5 | F18—C47—C48 | 118.7 (9) |
C18—C19—C20 | 107.8 (5) | C46—C47—C48 | 119.7 (8) |
C18—C19—H19 | 126.1 | F19—C48—C43 | 119.9 (6) |
C20—C19—H19 | 126.1 | F19—C48—C47 | 119.5 (8) |
N4—C20—C21 | 125.5 (5) | C43—C48—C47 | 120.5 (7) |
O1—P1—O2—C1 | −36.7 (5) | O2—P1—C28—C27 | −127.4 (5) |
O3—P1—O2—C1 | −167.3 (4) | C27—C28—C29—F3 | 177.6 (5) |
C28—P1—O2—C1 | 90.4 (5) | P1—C28—C29—F3 | −6.5 (8) |
O1—P1—O3—C3 | −59.0 (7) | C27—C28—C29—C30 | −0.3 (9) |
O2—P1—O3—C3 | 70.1 (6) | P1—C28—C29—C30 | 175.6 (5) |
C28—P1—O3—C3 | 178.3 (6) | F3—C29—C30—F4 | 1.2 (9) |
P1—O2—C1—C2 | −81.5 (7) | C28—C29—C30—F4 | 179.1 (5) |
P1—O3—C3—C4 | 166.7 (6) | F3—C29—C30—C25 | 179.4 (5) |
C22—N1—C5—C6 | −177.1 (5) | C28—C29—C30—C25 | −2.7 (10) |
C22—N1—C5—C24 | 1.9 (6) | C26—C25—C30—F4 | −178.6 (5) |
N1—C5—C6—C7 | 0.6 (9) | C21—C25—C30—F4 | 2.3 (9) |
C24—C5—C6—C7 | −178.2 (5) | C26—C25—C30—C29 | 3.2 (9) |
N1—C5—C6—C31 | 177.7 (5) | C21—C25—C30—C29 | −175.9 (6) |
C24—C5—C6—C31 | −1.1 (8) | C7—C6—C31—C32 | 81.8 (6) |
C10—N2—C7—C6 | 178.6 (5) | C5—C6—C31—C32 | −95.6 (6) |
C10—N2—C7—C8 | 0.0 (6) | C7—C6—C31—C36 | −99.5 (6) |
C5—C6—C7—N2 | 0.1 (9) | C5—C6—C31—C36 | 83.1 (6) |
C31—C6—C7—N2 | −177.0 (5) | C36—C31—C32—F5 | −179.9 (5) |
C5—C6—C7—C8 | 178.5 (5) | C6—C31—C32—F5 | −1.3 (7) |
C31—C6—C7—C8 | 1.3 (8) | C36—C31—C32—C33 | −0.9 (8) |
N2—C7—C8—C9 | −0.2 (7) | C6—C31—C32—C33 | 177.8 (5) |
C6—C7—C8—C9 | −178.8 (5) | F5—C32—C33—F6 | −0.6 (8) |
C7—C8—C9—C10 | 0.4 (7) | C31—C32—C33—F6 | −179.7 (5) |
C7—N2—C10—C11 | 177.5 (5) | F5—C32—C33—C34 | 179.0 (5) |
C7—N2—C10—C9 | 0.3 (6) | C31—C32—C33—C34 | −0.1 (9) |
C8—C9—C10—N2 | −0.4 (7) | F6—C33—C34—F7 | 1.3 (9) |
C8—C9—C10—C11 | −177.6 (6) | C32—C33—C34—F7 | −178.3 (5) |
N2—C10—C11—C12 | −0.7 (9) | F6—C33—C34—C35 | −178.8 (5) |
C9—C10—C11—C12 | 175.9 (6) | C32—C33—C34—C35 | 1.6 (9) |
N2—C10—C11—C37 | 178.3 (5) | F7—C34—C35—F8 | −1.3 (8) |
C9—C10—C11—C37 | −5.0 (8) | C33—C34—C35—F8 | 178.8 (5) |
C15—N3—C12—C11 | −178.3 (5) | F7—C34—C35—C36 | 177.8 (5) |
C15—N3—C12—C13 | 0.9 (6) | C33—C34—C35—C36 | −2.1 (9) |
C10—C11—C12—N3 | 5.2 (9) | C34—C35—C36—F9 | −179.5 (5) |
C37—C11—C12—N3 | −173.8 (5) | F8—C35—C36—F9 | −0.5 (8) |
C10—C11—C12—C13 | −173.9 (5) | C34—C35—C36—C31 | 1.1 (8) |
C37—C11—C12—C13 | 7.1 (8) | F8—C35—C36—C31 | −179.8 (5) |
N3—C12—C13—C14 | −1.5 (6) | C32—C31—C36—F9 | −179.0 (5) |
C11—C12—C13—C14 | 177.8 (5) | C6—C31—C36—F9 | 2.3 (8) |
C12—C13—C14—C15 | 1.3 (6) | C32—C31—C36—C35 | 0.4 (8) |
C12—N3—C15—C16 | −177.6 (5) | C6—C31—C36—C35 | −178.3 (5) |
C12—N3—C15—C14 | −0.1 (6) | C12—C11—C37—C42 | −68.9 (8) |
C13—C14—C15—N3 | −0.8 (6) | C10—C11—C37—C42 | 112.0 (6) |
C13—C14—C15—C16 | 176.8 (5) | C12—C11—C37—C38 | 111.4 (6) |
N3—C15—C16—C17 | −2.8 (9) | C10—C11—C37—C38 | −67.7 (7) |
C14—C15—C16—C17 | 180.0 (5) | C42—C37—C38—F10 | −179.8 (6) |
N3—C15—C16—C43 | 178.4 (5) | C11—C37—C38—F10 | −0.1 (9) |
C14—C15—C16—C43 | 1.2 (8) | C42—C37—C38—C39 | −0.5 (9) |
C20—N4—C17—C16 | −179.6 (5) | C11—C37—C38—C39 | 179.3 (6) |
C20—N4—C17—C18 | 1.5 (6) | F10—C38—C39—F11 | 0.1 (10) |
C15—C16—C17—N4 | −2.9 (9) | C37—C38—C39—F11 | −179.2 (6) |
C43—C16—C17—N4 | 175.8 (5) | F10—C38—C39—C40 | −179.3 (6) |
C15—C16—C17—C18 | 175.8 (6) | C37—C38—C39—C40 | 1.4 (11) |
C43—C16—C17—C18 | −5.4 (9) | F11—C39—C40—F12 | 0.8 (10) |
N4—C17—C18—C19 | −0.3 (7) | C38—C39—C40—F12 | −179.8 (6) |
C16—C17—C18—C19 | −179.3 (6) | F11—C39—C40—C41 | −179.7 (6) |
C17—C18—C19—C20 | −0.9 (7) | C38—C39—C40—C41 | −0.3 (11) |
C17—N4—C20—C21 | 176.2 (5) | F12—C40—C41—F13 | −0.7 (10) |
C17—N4—C20—C19 | −2.0 (6) | C39—C40—C41—F13 | 179.8 (6) |
C18—C19—C20—N4 | 1.8 (7) | F12—C40—C41—C42 | 177.9 (6) |
C18—C19—C20—C21 | −176.3 (6) | C39—C40—C41—C42 | −1.6 (10) |
N4—C20—C21—C22 | 0.8 (9) | C38—C37—C42—F14 | 178.1 (5) |
C19—C20—C21—C22 | 178.6 (6) | C11—C37—C42—F14 | −1.7 (9) |
N4—C20—C21—C25 | −177.0 (5) | C38—C37—C42—C41 | −1.5 (9) |
C19—C20—C21—C25 | 0.8 (9) | C11—C37—C42—C41 | 178.8 (6) |
C5—N1—C22—C21 | 177.4 (5) | F13—C41—C42—F14 | 1.6 (9) |
C5—N1—C22—C23 | −1.3 (6) | C40—C41—C42—F14 | −177.0 (6) |
C20—C21—C22—N1 | 1.5 (9) | F13—C41—C42—C37 | −178.9 (6) |
C25—C21—C22—N1 | 179.3 (5) | C40—C41—C42—C37 | 2.5 (10) |
C20—C21—C22—C23 | 179.9 (5) | C17—C16—C43—C48 | −92.7 (7) |
C25—C21—C22—C23 | −2.3 (8) | C15—C16—C43—C48 | 86.2 (8) |
N1—C22—C23—C24 | 0.2 (6) | C17—C16—C43—C44 | 89.7 (7) |
C21—C22—C23—C24 | −178.4 (5) | C15—C16—C43—C44 | −91.4 (6) |
C22—C23—C24—C5 | 0.9 (6) | C48—C43—C44—F15 | −179.9 (6) |
N1—C5—C24—C23 | −1.8 (6) | C16—C43—C44—F15 | −2.3 (9) |
C6—C5—C24—C23 | 177.2 (5) | C48—C43—C44—C45 | −0.6 (9) |
C20—C21—C25—C26 | −111.5 (6) | C16—C43—C44—C45 | 177.1 (6) |
C22—C21—C25—C26 | 70.4 (7) | F15—C44—C45—F16 | −1.0 (9) |
C20—C21—C25—C30 | 67.5 (7) | C43—C44—C45—F16 | 179.6 (6) |
C22—C21—C25—C30 | −110.6 (6) | F15—C44—C45—C46 | 177.9 (6) |
C30—C25—C26—F1 | 179.3 (5) | C43—C44—C45—C46 | −1.5 (10) |
C21—C25—C26—F1 | −1.7 (9) | F16—C45—C46—C47 | −177.4 (7) |
C30—C25—C26—C27 | −0.8 (9) | C44—C45—C46—C47 | 3.7 (11) |
C21—C25—C26—C27 | 178.2 (5) | F16—C45—C46—F17 | 3.4 (10) |
F1—C26—C27—F2 | −1.2 (8) | C44—C45—C46—F17 | −175.5 (6) |
C25—C26—C27—F2 | 178.9 (5) | C45—C46—C47—F18 | −179.4 (7) |
F1—C26—C27—C28 | 177.8 (5) | F17—C46—C47—F18 | −0.2 (12) |
C25—C26—C27—C28 | −2.1 (9) | C45—C46—C47—C48 | −3.7 (13) |
F2—C27—C28—C29 | −178.4 (5) | F17—C46—C47—C48 | 175.5 (7) |
C26—C27—C28—C29 | 2.6 (9) | C44—C43—C48—F19 | −179.4 (7) |
F2—C27—C28—P1 | 5.8 (8) | C16—C43—C48—F19 | 2.9 (11) |
C26—C27—C28—P1 | −173.2 (4) | C44—C43—C48—C47 | 0.6 (11) |
O1—P1—C28—C29 | −175.2 (5) | C16—C43—C48—C47 | −177.1 (7) |
O3—P1—C28—C29 | −49.6 (6) | F18—C47—C48—F19 | −2.7 (13) |
O2—P1—C28—C29 | 57.0 (6) | C46—C47—C48—F19 | −178.5 (8) |
O1—P1—C28—C27 | 0.5 (6) | F18—C47—C48—C43 | 177.3 (8) |
O3—P1—C28—C27 | 126.0 (5) | C46—C47—C48—C43 | 1.5 (13) |
Experimental details
Crystal data | |
Chemical formula | C48H20F19N4O3P |
Mr | 1092.65 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 15.530 (2), 11.2539 (17), 26.375 (3) |
β (°) | 100.024 (9) |
V (Å3) | 4539.3 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.08 × 0.05 × 0.03 |
Data collection | |
Diffractometer | Bruker APEXII X8 Kappa CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.985, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32626, 8275, 3504 |
Rint | 0.115 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.084, 0.271, 0.99 |
No. of reflections | 8275 |
No. of parameters | 678 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.34 |
Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).
O3—P1—O2—C1 | −167.3 (4) | P1—O2—C1—C2 | −81.5 (7) |
C28—P1—O3—C3 | 178.3 (6) | P1—O3—C3—C4 | 166.7 (6) |
C—H···A | C—H | H···A | C···A | C—H···A |
C3—H3A···F7iii | 0.99 | 2.52 | 3.487 (9) | 167 |
C13—H13···F12iv | 0.95 | 2.42 | 3.062 (7) | 124 |
C24—H24···O1iii | 0.95 | 2.43 | 3.327 (7) | 157 |
C—F···F—C | C—F/F—C | F···F | C—F···F | F···F—C |
C35—F8···(F15—C44)v | 1.360 (7)/1.320 (8) | 2.887 (6) | 164.6 (4) | 133.9 (4) |
C39—F11···(F19—C48)vi | 1.353 (8)/1.324 (8) | 2.763 (7) | 121.6 (4) | 165.8 (4) |
C—H···Cg | C—H | H···Cg | C···Cg | C—H···Cg |
C8—H8···Cg1i | 0.95 | 2.96 | 3.842 (7) | 155 |
C18—H18···Cg2ii | 0.95 | 2.83 | 3.552 (7) | 133 |
C—F···Cg | C—F | F···Cg | C···Cg | C—F···Cg |
C33—F6···Cg3i | 1.337 (7) | 3.576 (5) | 4.454 (7) | 123.4 (3) |
C46—F17···Cg1ii | 1.358 (8) | 3.124 (6) | 4.157 (11) | 131.9 (5) |
P═O···Cg | P═O | O···Cg | P···Cg | P═O···Cg |
P1—O1···Cg4iii | 1.444 (5) | 3.372 (5) | 4.395 (3) | 127.0 (2) |
Symmetry codes: (i) -x, y+1/2, -z+3/2; (ii) -x+1, y-1/2, -z+3/2; (iii) -x, -y, -z+1; (iv) -x+1, -y+1, -z+2; (v) x-1, y, z; (vi) x, y+1, z. Cg1, Cg2, Cg3 and Cg4 are the centroids of the rings N1/C5/C22–C24, N3/C12–C15, N2/C7–C10 and C31–C36, respectively. |
New synthetic strategies and primary building blocks have been developed for the specific design of multidimensional coordination polymers which combine a myriad metallic centres with ligands having multiple binding sites. For this purpose, porphyrin macrocycles can be designed having several coordination-capable groups located at the periphery of their core, which may ultimately also allow fine tuning of the framework topology (Natarajan & Mahata, 2009; Choi et al., 2009). Compared with carboxylate-based ligands, phosphonates are less commonly used to prepare coordination polymers, due to three main factors: (i) dense layered materials are usually formed, compared with the more interesting porous frameworks which may exhibit high surface areas; (ii) the growth of single crystals with phosphonates is generally more difficult because they often precipitate rapidly as less ordered and insoluble phases; (iii) the coordination chemistry of phosphonate groups is more complex due to their various stages of deprotonation (Natarajan & Mahata, 2009; Shimizu et al., 2009). Despite all these limitations, phosphonate-based ligands are still highly attractive molecules to prepare hybrid materials with different structures and interesting properties. A search of the literature yields only a handful of phosphorylporphyrins (Atefi et al., 2006; Enakieva et al., 2009; Matano et al., 2007) which may be employed as precursor structural building blocks for multiporphyrin arrays and networks (Natarajan & Mahata, 2009; Shimizu et al., 2009). Following our research interest in the use of phosphonate-based organic ligands for the construction of coordination polymers (Cunha-Silva, Lima et al., 2009; Cunha-Silva, Ananias et al., 2009; Cunha-Silva et al., 2007; Shi et al., 2008; Silva et al., 2011), we report herein the synthesis, structural characterization and crystallographic details of an isolated intermediate molecule, namely 5-[4-(diethoxyphosphoryl)-2,3,5,6-tetrafluorophenyl]-10,15,20-tris(pentafluorophenyl)porphyrin, (I), obtained in our quest to isolate phosphonic acid-based porphyrin molecules for self-assembly with metallic centres.
The asymmetric unit of (I) comprises a single molecule of the porphyrin derivative (Fig. 1). The porphyrin central core is approximately planar, with the largest distance from one atom (C14) to the average plane being 0.174 (6) Å. The substituent benzene rings subtend angles with the porphyrin core in the range 64.3 (2)–89.6 (3)°. These values agree well with those typically observed in related materials [a search of the Cambridge Structural Database (Version 5.32; Allen, 2002) yields 66 hits, with all of the angles being in the range ca 60–90°, mean 77.5°], and allow a minimization of the steric repulsion between the F atoms and the porphyrin core. It is noteworthy that the F atoms are almost coplanar with their respective aromatic rings, with the overall deviation being less than 0.084 (5) Å (for F17).
The P═O group of the phosphoryl moiety is located in the approximate average plane of the benzene ring to which it is attached [the ring···P═O angle is about 4.0 (3)°]. This conformation of the phosphoryl group enables a significant reduction of the steric impediment associated with the presence of the two pendant and highly flexible ethyl groups (Fig. 1). The conformational arrangements of the two ethyl substituents are different. Firstly, while methylene atom C1 forms an antiperiplanar angle with its neighbouring O3—P1—C28 group, for methylene atom C3 the antiperiplanar angle is instead formed with its neighbouring O2—P1—O3 group. Secondly, the two torsion angles involving the terminal methyl groups are also not similar, being (-)-synclinal for P1—O2—C1—C2 and (+)-antiperiplanar for P1—O3—C3—C4 (Table 1).
The molecule of (I) lacks typical hydrogen-bonding donors, and therefore strong supramolecular interactions mediating the crystal packing are absent. In addition, the asymmetric nature of the molecule also seems to avoid the presence of typical π–π interactions. Thus, the crystal packing is ensured by weak interactions such as C—H···π, C—F···π, P═O···π, C—H···(O,F) and F···F contacts (Fig. 2; see Table 2 for geometric details of all these interactions). Molecules of (I) form supramolecular layers in the ab plane of the unit cell, having essentially C—H···π contacts between the cores of adjacent porphyrin rings. The bulky phosphonate groups point towards these interlayer spaces and are engaged in a number of weak C—H···O and C—H···F interactions (Fig. 2 and Table 2).
It is noteworthy that the crystal structure contains a small void volume of ca 46 Å3 (Fig. 2). Although this empty space is suitable for the inclusion of a small solvent molecule, such as water, the total electron density found within the cavity is less than four electrons and highly smeared out, thus avoiding a sensible location and refinement of additional molecular entities within the crystal structure.