Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101019151/da1202sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101019151/da1202Isup2.hkl |
CCDC reference: 182022
Compound (I) was prepared from the reaction of 2-trans-6-bis(pyropylamino)cyclotetraphosphazatetraene (2.16 g, 4.00 mmol), pyrrolidine (4.27 g, 60.0 mmol) and triethylamine (6.07 g, 60.0 mmol) in chloroform (200 ml). The mixture was stirred at 258 K for 2 h and then immediately refluxed for 12 h. The solvent was evaporated and benzene (150 ml) with triethylamine (10.1 g, 100 mmol) was added to the residue. The resulting mixture was refluxed for 3 h and then filtered to remove triethylamine hydrochloride. The solvent was removed by rotary evaporation and the residue chromatographed on silica gel. Compound (I) was purified by fractional crystallization in light petroleum (m.p. 430 K; yield 2.27 g, 83%).
The structure was solved by direct methods. The positions of atoms H13 and H13' were obtained from the difference syntheses and refined isotropically, while the remaining H atoms were positioned geometrically at distances of 0.96 and 0.97 Å for CH3 and CH2 bonds, respectively, and allowed to ride on the attached atom. The N13—H13 and N13'-H13' bond lengths are 0.81 (4) and 0.68 (4) Å, respectively. The N13'-H13' bond distance is smaller than the conventional N—H value but was not further restrained. For eight of the pyrrolidino groups, the C atoms in the 3- and 4-positions were disordered. The occupancies of each disordered group were allowed to refine while applying a restraint that the geometries be similar.
Data collection: MolEN (Fair, 1990); cell refinement: MolEN; data reduction: MolEN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: MolEN.
C26H55N11P4 | F(000) = 2784 |
Mr = 645.69 | Dx = 1.219 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.405 (11) Å | Cell parameters from 25 reflections |
b = 21.545 (5) Å | θ = 10–18° |
c = 28.893 (16) Å | µ = 0.25 mm−1 |
β = 97.73 (6)° | T = 293 K |
V = 7035 (8) Å3 | Rod, colourless |
Z = 8 | 0.30 × 0.20 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.056 |
Radiation source: fine-focus sealed tube | θmax = 26.3°, θmin = 2.3° |
Graphite monochromator | h = −14→14 |
ω/2θ scans | k = −26→2 |
14219 measured reflections | l = −21→36 |
13799 independent reflections | 3 standard reflections every 120 min |
7479 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.055P)2] where P = (Fo2 + 2Fc2)/3 |
13799 reflections | (Δ/σ)max = 0.004 |
803 parameters | Δρmax = 0.40 e Å−3 |
783 restraints | Δρmin = −0.36 e Å−3 |
C26H55N11P4 | V = 7035 (8) Å3 |
Mr = 645.69 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.405 (11) Å | µ = 0.25 mm−1 |
b = 21.545 (5) Å | T = 293 K |
c = 28.893 (16) Å | 0.30 × 0.20 × 0.15 mm |
β = 97.73 (6)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.056 |
14219 measured reflections | 3 standard reflections every 120 min |
13799 independent reflections | intensity decay: 1% |
7479 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.051 | 783 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.40 e Å−3 |
13799 reflections | Δρmin = −0.36 e Å−3 |
803 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) | |
N1 | 0.34480 (17) | 0.69852 (9) | 0.77243 (7) | 0.0460 (5) | |
P2 | 0.46948 (6) | 0.73132 (3) | 0.77090 (2) | 0.04268 (17) | |
N3 | 0.49642 (18) | 0.79747 (9) | 0.79428 (7) | 0.0462 (5) | |
P4 | 0.45722 (6) | 0.85951 (3) | 0.76682 (2) | 0.04607 (18) | |
N5 | 0.38771 (19) | 0.85162 (10) | 0.71588 (7) | 0.0545 (6) | |
P6 | 0.37071 (6) | 0.78798 (3) | 0.68834 (2) | 0.04692 (18) | |
N7 | 0.24979 (17) | 0.74987 (10) | 0.69000 (7) | 0.0492 (5) | |
P8 | 0.22970 (6) | 0.71821 (3) | 0.73847 (2) | 0.04611 (18) | |
N9 | 0.48496 (17) | 0.74131 (9) | 0.71314 (7) | 0.0454 (5) | |
N10 | 0.56986 (19) | 0.68315 (10) | 0.79493 (8) | 0.0541 (6) | |
C1A | 0.5518 (3) | 0.61740 (14) | 0.80311 (13) | 0.0835 (10) | 0.207 (17) |
H1AA | 0.5077 | 0.5975 | 0.7761 | 0.100* | 0.207 (17) |
H1AB | 0.5115 | 0.6107 | 0.8302 | 0.100* | 0.207 (17) |
C2A | 0.6769 (16) | 0.5951 (15) | 0.8114 (16) | 0.110 (3) | 0.207 (17) |
H2AA | 0.7026 | 0.5835 | 0.7819 | 0.132* | 0.207 (17) |
H2AB | 0.6822 | 0.5588 | 0.8314 | 0.132* | 0.207 (17) |
C3A | 0.756 (4) | 0.6455 (11) | 0.834 (2) | 0.095 (2) | 0.207 (17) |
H3AA | 0.7606 | 0.6444 | 0.8680 | 0.114* | 0.207 (17) |
H3AB | 0.8352 | 0.6430 | 0.8255 | 0.114* | 0.207 (17) |
C4A | 0.6908 (3) | 0.70195 (15) | 0.81377 (11) | 0.0749 (9) | 0.207 (17) |
H4AA | 0.6886 | 0.7334 | 0.8377 | 0.090* | 0.207 (17) |
H4AB | 0.7307 | 0.7192 | 0.7891 | 0.090* | 0.207 (17) |
C1B | 0.5518 (3) | 0.61740 (14) | 0.80311 (13) | 0.0835 (10) | 0.793 (17) |
H1BA | 0.5476 | 0.5943 | 0.7741 | 0.100* | 0.793 (17) |
H1BB | 0.4791 | 0.6109 | 0.8164 | 0.100* | 0.793 (17) |
C2B | 0.6551 (7) | 0.5974 (3) | 0.8362 (4) | 0.110 (3) | 0.793 (17) |
H2BA | 0.6752 | 0.5544 | 0.8309 | 0.132* | 0.793 (17) |
H2BB | 0.6401 | 0.6020 | 0.8683 | 0.132* | 0.793 (17) |
C3B | 0.7519 (11) | 0.6406 (4) | 0.8254 (5) | 0.095 (2) | 0.793 (17) |
H3BA | 0.7883 | 0.6254 | 0.7992 | 0.114* | 0.793 (17) |
H3BB | 0.8124 | 0.6448 | 0.8522 | 0.114* | 0.793 (17) |
C4B | 0.6908 (3) | 0.70195 (15) | 0.81377 (11) | 0.0749 (9) | 0.793 (17) |
H4BA | 0.6912 | 0.7275 | 0.8414 | 0.090* | 0.793 (17) |
H4BB | 0.7282 | 0.7246 | 0.7907 | 0.090* | 0.793 (17) |
N11 | 0.37450 (19) | 0.90347 (10) | 0.79559 (8) | 0.0591 (6) | |
C5A | 0.2665 (3) | 0.93496 (18) | 0.77607 (12) | 0.0900 (11) | 0.825 (17) |
H5AA | 0.2022 | 0.9057 | 0.7681 | 0.108* | 0.825 (17) |
H5AB | 0.2780 | 0.9586 | 0.7485 | 0.108* | 0.825 (17) |
C6A | 0.2428 (10) | 0.9775 (5) | 0.8160 (2) | 0.142 (3) | 0.825 (17) |
H6AA | 0.2724 | 1.0189 | 0.8113 | 0.170* | 0.825 (17) |
H6AB | 0.1585 | 0.9802 | 0.8175 | 0.170* | 0.825 (17) |
C7A | 0.3051 (7) | 0.9504 (5) | 0.8604 (2) | 0.104 (3) | 0.825 (17) |
H7AA | 0.3267 | 0.9823 | 0.8837 | 0.125* | 0.825 (17) |
H7AB | 0.2569 | 0.9193 | 0.8731 | 0.125* | 0.825 (17) |
C8A | 0.4122 (3) | 0.92202 (16) | 0.84414 (11) | 0.0783 (10) | 0.825 (17) |
H8AA | 0.4763 | 0.9519 | 0.8459 | 0.094* | 0.825 (17) |
H8AB | 0.4387 | 0.8863 | 0.8631 | 0.094* | 0.825 (17) |
C5B | 0.2665 (3) | 0.93496 (18) | 0.77607 (12) | 0.0900 (11) | 0.175 (17) |
H5BA | 0.2109 | 0.9071 | 0.7583 | 0.108* | 0.175 (17) |
H5BB | 0.2820 | 0.9702 | 0.7569 | 0.108* | 0.175 (17) |
C6B | 0.226 (4) | 0.955 (2) | 0.8212 (11) | 0.142 (3) | 0.175 (17) |
H6BA | 0.1658 | 0.9868 | 0.8162 | 0.170* | 0.175 (17) |
H6BB | 0.1947 | 0.9197 | 0.8370 | 0.170* | 0.175 (17) |
C7B | 0.338 (3) | 0.9786 (15) | 0.8478 (15) | 0.104 (3) | 0.175 (17) |
H7BA | 0.3683 | 1.0144 | 0.8328 | 0.125* | 0.175 (17) |
H7BB | 0.3294 | 0.9885 | 0.8799 | 0.125* | 0.175 (17) |
C8B | 0.4122 (3) | 0.92202 (16) | 0.84414 (11) | 0.0783 (10) | 0.175 (17) |
H8BA | 0.4960 | 0.9317 | 0.8495 | 0.094* | 0.175 (17) |
H8BB | 0.3949 | 0.8901 | 0.8659 | 0.094* | 0.175 (17) |
N12 | 0.5785 (2) | 0.90199 (10) | 0.76797 (8) | 0.0614 (6) | |
C9A | 0.6850 (3) | 0.87427 (17) | 0.75484 (13) | 0.0853 (10) | 0.202 (16) |
H9AA | 0.6694 | 0.8330 | 0.7420 | 0.102* | 0.202 (16) |
H9AB | 0.7468 | 0.8718 | 0.7814 | 0.102* | 0.202 (16) |
C10A | 0.719 (4) | 0.9188 (16) | 0.7180 (12) | 0.144 (4) | 0.202 (16) |
H10A | 0.8016 | 0.9156 | 0.7140 | 0.173* | 0.202 (16) |
H10B | 0.6694 | 0.9140 | 0.6882 | 0.173* | 0.202 (16) |
C11A | 0.692 (2) | 0.978 (2) | 0.743 (2) | 0.190 (5) | 0.202 (16) |
H11A | 0.7419 | 0.9821 | 0.7727 | 0.228* | 0.202 (16) |
H11B | 0.6990 | 1.0142 | 0.7240 | 0.228* | 0.202 (16) |
C12A | 0.5671 (3) | 0.96528 (16) | 0.74929 (14) | 0.0962 (12) | 0.202 (16) |
H12A | 0.5391 | 0.9939 | 0.7713 | 0.115* | 0.202 (16) |
H12B | 0.5150 | 0.9669 | 0.7199 | 0.115* | 0.202 (16) |
C9B | 0.6850 (3) | 0.87427 (17) | 0.75484 (13) | 0.0853 (10) | 0.798 (16) |
H9BA | 0.6668 | 0.8484 | 0.7273 | 0.102* | 0.798 (16) |
H9BB | 0.7249 | 0.8493 | 0.7801 | 0.102* | 0.798 (16) |
C10B | 0.7600 (7) | 0.9292 (4) | 0.7449 (5) | 0.144 (4) | 0.798 (16) |
H10C | 0.8137 | 0.9185 | 0.7228 | 0.173* | 0.798 (16) |
H10D | 0.8053 | 0.9449 | 0.7733 | 0.173* | 0.798 (16) |
C11B | 0.6674 (7) | 0.9762 (6) | 0.7240 (5) | 0.190 (5) | 0.798 (16) |
H11C | 0.6967 | 1.0183 | 0.7289 | 0.228* | 0.798 (16) |
H11D | 0.6458 | 0.9692 | 0.6908 | 0.228* | 0.798 (16) |
C12B | 0.5671 (3) | 0.96528 (16) | 0.74929 (14) | 0.0962 (12) | 0.798 (16) |
H12C | 0.4935 | 0.9697 | 0.7284 | 0.115* | 0.798 (16) |
H12D | 0.5674 | 0.9950 | 0.7745 | 0.115* | 0.798 (16) |
N13 | 0.3827 (2) | 0.79886 (13) | 0.63406 (8) | 0.0620 (7) | |
H13 | 0.339 (2) | 0.7788 (11) | 0.6153 (9) | 0.045 (8)* | |
N14 | 0.1404 (2) | 0.65953 (11) | 0.72376 (7) | 0.0608 (6) | |
C13A | 0.1425 (3) | 0.62096 (17) | 0.68396 (12) | 0.0908 (11) | 0.37 (3) |
H13A | 0.2112 | 0.5940 | 0.6880 | 0.109* | 0.37 (3) |
H13B | 0.1442 | 0.6458 | 0.6560 | 0.109* | 0.37 (3) |
C14A | 0.030 (3) | 0.5835 (19) | 0.6807 (13) | 0.108 (5) | 0.37 (3) |
H14A | −0.0396 | 0.6076 | 0.6685 | 0.130* | 0.37 (3) |
H14B | 0.0332 | 0.5459 | 0.6624 | 0.130* | 0.37 (3) |
C15A | 0.034 (3) | 0.5703 (14) | 0.7316 (12) | 0.101 (4) | 0.37 (3) |
H15A | 0.0816 | 0.5334 | 0.7396 | 0.121* | 0.37 (3) |
H15B | −0.0448 | 0.5628 | 0.7391 | 0.121* | 0.37 (3) |
C16A | 0.0879 (3) | 0.62429 (17) | 0.75916 (11) | 0.0870 (11) | 0.37 (3) |
H16A | 0.0282 | 0.6484 | 0.7720 | 0.104* | 0.37 (3) |
H16B | 0.1476 | 0.6110 | 0.7843 | 0.104* | 0.37 (3) |
C13B | 0.1425 (3) | 0.62096 (17) | 0.68396 (12) | 0.0908 (11) | 0.63 (3) |
H13C | 0.2209 | 0.6038 | 0.6833 | 0.109* | 0.63 (3) |
H13D | 0.1199 | 0.6443 | 0.6554 | 0.109* | 0.63 (3) |
C14B | 0.0545 (13) | 0.5700 (8) | 0.6888 (8) | 0.108 (5) | 0.63 (3) |
H14C | −0.0096 | 0.5719 | 0.6631 | 0.130* | 0.63 (3) |
H14D | 0.0926 | 0.5299 | 0.6881 | 0.130* | 0.63 (3) |
C15B | 0.0073 (17) | 0.5782 (9) | 0.7338 (7) | 0.101 (4) | 0.63 (3) |
H15C | −0.0733 | 0.5937 | 0.7288 | 0.121* | 0.63 (3) |
H15D | 0.0090 | 0.5394 | 0.7509 | 0.121* | 0.63 (3) |
C16B | 0.0879 (3) | 0.62429 (17) | 0.75916 (11) | 0.0870 (11) | 0.63 (3) |
H16C | 0.0445 | 0.6517 | 0.7773 | 0.104* | 0.63 (3) |
H16D | 0.1491 | 0.6036 | 0.7802 | 0.104* | 0.63 (3) |
N15 | 0.15265 (19) | 0.76191 (11) | 0.76978 (7) | 0.0595 (6) | |
C17A | 0.0354 (3) | 0.7854 (2) | 0.75284 (12) | 0.0947 (12) | 0.509 (12) |
H17A | −0.0075 | 0.7573 | 0.7304 | 0.114* | 0.509 (12) |
H17B | 0.0390 | 0.8261 | 0.7388 | 0.114* | 0.509 (12) |
C18A | −0.0197 (12) | 0.7881 (8) | 0.7980 (4) | 0.098 (3) | 0.509 (12) |
H18A | −0.0854 | 0.8170 | 0.7953 | 0.118* | 0.509 (12) |
H18B | −0.0475 | 0.7475 | 0.8061 | 0.118* | 0.509 (12) |
C19A | 0.0802 (13) | 0.8100 (12) | 0.8336 (7) | 0.104 (3) | 0.509 (12) |
H19A | 0.0921 | 0.8544 | 0.8315 | 0.125* | 0.509 (12) |
H19B | 0.0666 | 0.7995 | 0.8651 | 0.125* | 0.509 (12) |
C20A | 0.1821 (3) | 0.77473 (15) | 0.81960 (9) | 0.0643 (8) | 0.509 (12) |
H20A | 0.2541 | 0.7991 | 0.8254 | 0.077* | 0.509 (12) |
H20B | 0.1936 | 0.7363 | 0.8371 | 0.077* | 0.509 (12) |
C17B | 0.0354 (3) | 0.7854 (2) | 0.75284 (12) | 0.0947 (12) | 0.491 (12) |
H17C | −0.0192 | 0.7513 | 0.7449 | 0.114* | 0.491 (12) |
H17D | 0.0376 | 0.8107 | 0.7252 | 0.114* | 0.491 (12) |
C18B | −0.0026 (13) | 0.8233 (7) | 0.7915 (5) | 0.098 (3) | 0.491 (12) |
H18C | −0.0863 | 0.8178 | 0.7933 | 0.118* | 0.491 (12) |
H18D | 0.0129 | 0.8671 | 0.7871 | 0.118* | 0.491 (12) |
C19B | 0.0708 (14) | 0.7990 (12) | 0.8345 (7) | 0.104 (3) | 0.491 (12) |
H19C | 0.0882 | 0.8318 | 0.8573 | 0.125* | 0.491 (12) |
H19D | 0.0291 | 0.7661 | 0.8483 | 0.125* | 0.491 (12) |
C20B | 0.1821 (3) | 0.77473 (15) | 0.81960 (9) | 0.0643 (8) | 0.491 (12) |
H20C | 0.2448 | 0.8053 | 0.8250 | 0.077* | 0.491 (12) |
H20D | 0.2074 | 0.7372 | 0.8366 | 0.077* | 0.491 (12) |
C21 | 0.5032 (3) | 0.68387 (14) | 0.68630 (10) | 0.0651 (8) | |
H21A | 0.4743 | 0.6487 | 0.7024 | 0.078* | |
H21B | 0.4559 | 0.6868 | 0.6559 | 0.078* | |
C22 | 0.6262 (4) | 0.6719 (3) | 0.6796 (2) | 0.158 (2) | |
H22A | 0.6669 | 0.6586 | 0.7097 | 0.190* | |
H22B | 0.6250 | 0.6364 | 0.6589 | 0.190* | |
C23 | 0.6976 (5) | 0.7164 (3) | 0.6626 (2) | 0.186 (3) | |
H23A | 0.7745 | 0.6990 | 0.6609 | 0.278* | |
H23B | 0.7051 | 0.7515 | 0.6832 | 0.278* | |
H23C | 0.6627 | 0.7292 | 0.6321 | 0.278* | |
C24 | 0.4600 (3) | 0.84573 (17) | 0.61711 (11) | 0.0813 (10) | |
H24A | 0.5143 | 0.8608 | 0.6435 | 0.098* | |
H24B | 0.5069 | 0.8259 | 0.5957 | 0.098* | |
C25 | 0.4006 (4) | 0.8977 (2) | 0.59405 (17) | 0.1232 (16) | |
H25A | 0.3581 | 0.9198 | 0.6159 | 0.148* | |
H25B | 0.3432 | 0.8831 | 0.5686 | 0.148* | |
C26 | 0.4864 (5) | 0.9422 (2) | 0.57486 (19) | 0.163 (2) | |
H26A | 0.4432 | 0.9765 | 0.5597 | 0.245* | |
H26B | 0.5275 | 0.9207 | 0.5527 | 0.245* | |
H26C | 0.5426 | 0.9573 | 0.6001 | 0.245* | |
N1' | 0.01902 (18) | 0.73300 (9) | 0.93977 (7) | 0.0473 (5) | |
P2' | 0.03272 (6) | 0.79705 (3) | 0.96671 (2) | 0.03945 (16) | |
N3' | 0.15650 (17) | 0.83197 (10) | 0.97359 (7) | 0.0474 (5) | |
P4' | 0.26129 (6) | 0.81276 (3) | 1.01283 (2) | 0.04435 (17) | |
N5' | 0.22810 (17) | 0.76900 (10) | 1.05396 (7) | 0.0458 (5) | |
P6' | 0.10374 (6) | 0.73303 (3) | 1.04896 (2) | 0.04014 (16) | |
N7' | 0.09068 (18) | 0.67086 (9) | 1.01919 (6) | 0.0460 (5) | |
P8' | 0.04384 (6) | 0.66789 (3) | 0.96510 (2) | 0.04333 (17) | |
N9' | −0.00204 (16) | 0.78167 (9) | 1.02180 (6) | 0.0400 (5) | |
N10' | −0.06239 (18) | 0.84547 (9) | 0.93969 (7) | 0.0476 (5) | |
C27 | −0.1737 (2) | 0.82553 (13) | 0.91193 (10) | 0.0594 (7) | |
H27A | −0.2234 | 0.8037 | 0.9313 | 0.071* | |
H27B | −0.1583 | 0.7985 | 0.8866 | 0.071* | |
C28 | −0.2315 (3) | 0.88441 (17) | 0.89340 (13) | 0.0906 (11) | |
H28A | −0.2758 | 0.8781 | 0.8627 | 0.109* | |
H28B | −0.2845 | 0.9003 | 0.9142 | 0.109* | |
C29 | −0.1307 (3) | 0.92750 (17) | 0.89111 (13) | 0.0949 (12) | |
H29A | −0.1562 | 0.9704 | 0.8922 | 0.114* | |
H29B | −0.0957 | 0.9210 | 0.8627 | 0.114* | |
C30 | −0.0443 (3) | 0.91176 (13) | 0.93338 (11) | 0.0724 (9) | |
H30A | 0.0363 | 0.9203 | 0.9280 | 0.087* | |
H30B | −0.0611 | 0.9351 | 0.9604 | 0.087* | |
N11' | 0.36406 (18) | 0.78368 (11) | 0.98481 (7) | 0.0565 (6) | |
C31A | 0.3589 (3) | 0.77980 (17) | 0.93453 (10) | 0.0800 (10) | 0.427 (12) |
H31A | 0.3309 | 0.8184 | 0.9197 | 0.096* | 0.427 (12) |
H31B | 0.3073 | 0.7463 | 0.9220 | 0.096* | 0.427 (12) |
C32A | 0.4855 (13) | 0.7672 (14) | 0.9274 (8) | 0.123 (3) | 0.427 (12) |
H32A | 0.4885 | 0.7407 | 0.9004 | 0.147* | 0.427 (12) |
H32B | 0.5266 | 0.8056 | 0.9228 | 0.147* | 0.427 (12) |
C33A | 0.5400 (14) | 0.7354 (8) | 0.9711 (5) | 0.098 (3) | 0.427 (12) |
H33A | 0.5233 | 0.6912 | 0.9700 | 0.117* | 0.427 (12) |
H33B | 0.6250 | 0.7416 | 0.9764 | 0.117* | 0.427 (12) |
C34A | 0.4813 (3) | 0.76650 (19) | 1.00769 (12) | 0.0882 (11) | 0.427 (12) |
H34A | 0.4754 | 0.7385 | 1.0336 | 0.106* | 0.427 (12) |
H34B | 0.5254 | 0.8030 | 1.0194 | 0.106* | 0.427 (12) |
C31B | 0.3589 (3) | 0.77980 (17) | 0.93453 (10) | 0.0800 (10) | 0.573 (12) |
H31C | 0.3470 | 0.8205 | 0.9203 | 0.096* | 0.573 (12) |
H31D | 0.2952 | 0.7527 | 0.9213 | 0.096* | 0.573 (12) |
C32B | 0.4781 (9) | 0.7534 (10) | 0.9270 (6) | 0.123 (3) | 0.573 (12) |
H32C | 0.4750 | 0.7085 | 0.9245 | 0.147* | 0.573 (12) |
H32D | 0.5042 | 0.7704 | 0.8990 | 0.147* | 0.573 (12) |
C33B | 0.5583 (9) | 0.7733 (7) | 0.9698 (4) | 0.098 (3) | 0.573 (12) |
H33C | 0.5837 | 0.8160 | 0.9671 | 0.117* | 0.573 (12) |
H33D | 0.6274 | 0.7468 | 0.9754 | 0.117* | 0.573 (12) |
C34B | 0.4813 (3) | 0.76650 (19) | 1.00769 (12) | 0.0882 (11) | 0.573 (12) |
H34C | 0.4822 | 0.7241 | 1.0190 | 0.106* | 0.573 (12) |
H34D | 0.5070 | 0.7940 | 1.0337 | 0.106* | 0.573 (12) |
N12' | 0.3279 (2) | 0.87301 (11) | 1.03988 (7) | 0.0607 (6) | |
C35 | 0.3787 (3) | 0.92183 (16) | 1.01382 (12) | 0.0916 (11) | |
H35A | 0.3221 | 0.9357 | 0.9878 | 0.110* | |
H35B | 0.4492 | 0.9071 | 1.0019 | 0.110* | |
C36 | 0.4085 (5) | 0.97335 (19) | 1.04831 (15) | 0.1216 (15) | |
H36A | 0.4913 | 0.9846 | 1.0498 | 0.146* | |
H36B | 0.3607 | 1.0097 | 1.0391 | 0.146* | |
C37 | 0.3834 (3) | 0.95028 (16) | 1.09453 (13) | 0.0853 (10) | |
H37A | 0.3518 | 0.9831 | 1.1122 | 0.102* | |
H37B | 0.4545 | 0.9339 | 1.1126 | 0.102* | |
C38 | 0.2934 (3) | 0.89998 (15) | 1.08238 (10) | 0.0711 (9) | |
H38A | 0.2968 | 0.8693 | 1.1071 | 0.085* | |
H38B | 0.2140 | 0.9170 | 1.0767 | 0.085* | |
N13' | 0.0751 (2) | 0.72003 (12) | 1.10119 (9) | 0.0528 (7) | |
H13' | 0.114 (2) | 0.7277 (12) | 1.1205 (9) | 0.043 (9)* | |
N14' | 0.1396 (2) | 0.62516 (10) | 0.94170 (7) | 0.0575 (6) | |
C39A | 0.2613 (3) | 0.61582 (16) | 0.96217 (11) | 0.0769 (9) | 0.674 (16) |
H39A | 0.2650 | 0.5964 | 0.9926 | 0.092* | 0.674 (16) |
H39B | 0.3032 | 0.6551 | 0.9656 | 0.092* | 0.674 (16) |
C40A | 0.3142 (10) | 0.5738 (6) | 0.9286 (3) | 0.109 (3) | 0.674 (16) |
H40A | 0.3001 | 0.5305 | 0.9349 | 0.131* | 0.674 (16) |
H40B | 0.3986 | 0.5807 | 0.9298 | 0.131* | 0.674 (16) |
C41A | 0.2470 (9) | 0.5938 (7) | 0.8812 (3) | 0.110 (4) | 0.674 (16) |
H41A | 0.2858 | 0.6289 | 0.8686 | 0.132* | 0.674 (16) |
H41B | 0.2428 | 0.5599 | 0.8589 | 0.132* | 0.674 (16) |
C42A | 0.1240 (3) | 0.61166 (16) | 0.89130 (10) | 0.0843 (11) | 0.674 (16) |
H42A | 0.0951 | 0.6479 | 0.8734 | 0.101* | 0.674 (16) |
H42B | 0.0687 | 0.5778 | 0.8839 | 0.101* | 0.674 (16) |
C39B | 0.2613 (3) | 0.61582 (16) | 0.96217 (11) | 0.0769 (9) | 0.326 (16) |
H39C | 0.2685 | 0.5818 | 0.9844 | 0.092* | 0.326 (16) |
H39D | 0.2947 | 0.6531 | 0.9774 | 0.092* | 0.326 (16) |
C40B | 0.319 (2) | 0.6003 (10) | 0.9193 (6) | 0.109 (3) | 0.326 (16) |
H40C | 0.3429 | 0.6377 | 0.9044 | 0.131* | 0.326 (16) |
H40D | 0.3879 | 0.5741 | 0.9273 | 0.131* | 0.326 (16) |
C41B | 0.2234 (17) | 0.5664 (10) | 0.8879 (10) | 0.110 (4) | 0.326 (16) |
H41C | 0.2418 | 0.5625 | 0.8562 | 0.132* | 0.326 (16) |
H41D | 0.2071 | 0.5258 | 0.9000 | 0.132* | 0.326 (16) |
C42B | 0.1240 (3) | 0.61166 (16) | 0.89130 (10) | 0.0843 (11) | 0.326 (16) |
H42C | 0.1326 | 0.6488 | 0.8731 | 0.101* | 0.326 (16) |
H42D | 0.0475 | 0.5930 | 0.8811 | 0.101* | 0.326 (16) |
N15' | −0.0785 (2) | 0.62664 (10) | 0.95272 (8) | 0.0564 (6) | |
C43A | −0.0746 (4) | 0.56145 (16) | 0.96743 (14) | 0.0973 (12) | 0.290 (13) |
H43A | 0.0008 | 0.5512 | 0.9855 | 0.117* | 0.290 (13) |
H43B | −0.0889 | 0.5337 | 0.9408 | 0.117* | 0.290 (13) |
C44A | −0.1734 (19) | 0.5588 (10) | 0.9968 (10) | 0.148 (4) | 0.290 (13) |
H44A | −0.1434 | 0.5686 | 1.0290 | 0.178* | 0.290 (13) |
H44B | −0.2065 | 0.5173 | 0.9959 | 0.178* | 0.290 (13) |
C45A | −0.268 (2) | 0.6047 (15) | 0.978 (2) | 0.154 (2) | 0.290 (13) |
H45A | −0.3121 | 0.6191 | 1.0027 | 0.184* | 0.290 (13) |
H45B | −0.3215 | 0.5878 | 0.9527 | 0.184* | 0.290 (13) |
C46A | −0.1903 (3) | 0.65497 (16) | 0.96260 (11) | 0.0781 (9) | 0.290 (13) |
H46A | −0.2302 | 0.6748 | 0.9347 | 0.094* | 0.290 (13) |
H46B | −0.1743 | 0.6862 | 0.9868 | 0.094* | 0.290 (13) |
C43B | −0.0746 (4) | 0.56145 (16) | 0.96743 (14) | 0.0973 (12) | 0.710 (13) |
H43C | −0.0348 | 0.5574 | 0.9991 | 0.117* | 0.710 (13) |
H43D | −0.0329 | 0.5365 | 0.9469 | 0.117* | 0.710 (13) |
C44B | −0.1993 (7) | 0.5416 (4) | 0.9645 (5) | 0.148 (4) | 0.710 (13) |
H44C | −0.2084 | 0.5081 | 0.9862 | 0.178* | 0.710 (13) |
H44D | −0.2304 | 0.5286 | 0.9331 | 0.178* | 0.710 (13) |
C45B | −0.2584 (11) | 0.6001 (6) | 0.9781 (9) | 0.154 (2) | 0.710 (13) |
H45C | −0.2584 | 0.6013 | 1.0117 | 0.184* | 0.710 (13) |
H45D | −0.3398 | 0.6014 | 0.9631 | 0.184* | 0.710 (13) |
C46B | −0.1903 (3) | 0.65497 (16) | 0.96260 (11) | 0.0781 (9) | 0.710 (13) |
H46C | −0.2324 | 0.6742 | 0.9349 | 0.094* | 0.710 (13) |
H46D | −0.1761 | 0.6858 | 0.9872 | 0.094* | 0.710 (13) |
C47 | −0.0327 (2) | 0.83818 (12) | 1.04840 (9) | 0.0521 (7) | |
H47A | 0.0009 | 0.8341 | 1.0809 | 0.063* | |
H47B | 0.0016 | 0.8747 | 1.0359 | 0.063* | |
C48 | −0.1641 (3) | 0.84632 (17) | 1.04517 (12) | 0.0828 (10) | |
H48A | −0.1973 | 0.8109 | 1.0595 | 0.099* | |
H48B | −0.1978 | 0.8472 | 1.0125 | 0.099* | |
C49 | −0.1988 (4) | 0.9046 (2) | 1.06846 (15) | 0.1306 (17) | |
H49A | −0.2835 | 0.9074 | 1.0653 | 0.196* | |
H49B | −0.1678 | 0.9399 | 1.0540 | 0.196* | |
H49C | −0.1673 | 0.9036 | 1.1010 | 0.196* | |
C50 | −0.0032 (3) | 0.67237 (17) | 1.11358 (10) | 0.0812 (10) | |
H50A | −0.0609 | 0.6630 | 1.0867 | 0.097* | |
H50B | −0.0456 | 0.6878 | 1.1382 | 0.097* | |
C51 | 0.0622 (5) | 0.6123 (2) | 1.13033 (19) | 0.150 (2) | |
H51A | 0.0998 | 0.5961 | 1.1047 | 0.180* | |
H51B | 0.1247 | 0.6231 | 1.1552 | 0.180* | |
C52 | −0.0063 (8) | 0.5631 (3) | 1.1470 (2) | 0.248 (4) | |
H52A | 0.0443 | 0.5285 | 1.1564 | 0.372* | |
H52B | −0.0670 | 0.5504 | 1.1226 | 0.372* | |
H52C | −0.0421 | 0.5776 | 1.1733 | 0.372* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0378 (12) | 0.0547 (13) | 0.0446 (12) | −0.0050 (10) | 0.0020 (10) | 0.0022 (10) |
P2 | 0.0359 (4) | 0.0454 (4) | 0.0456 (4) | −0.0001 (3) | 0.0015 (3) | −0.0021 (3) |
N3 | 0.0448 (12) | 0.0454 (12) | 0.0456 (12) | 0.0029 (10) | −0.0039 (10) | −0.0026 (10) |
P4 | 0.0431 (4) | 0.0459 (4) | 0.0472 (4) | −0.0010 (3) | −0.0013 (3) | −0.0031 (3) |
N5 | 0.0550 (14) | 0.0540 (14) | 0.0506 (13) | 0.0023 (11) | −0.0075 (11) | 0.0002 (11) |
P6 | 0.0414 (4) | 0.0618 (5) | 0.0371 (4) | −0.0090 (3) | 0.0033 (3) | −0.0010 (3) |
N7 | 0.0359 (12) | 0.0726 (15) | 0.0375 (12) | −0.0104 (10) | −0.0006 (9) | −0.0002 (10) |
P8 | 0.0362 (4) | 0.0649 (5) | 0.0369 (4) | −0.0087 (3) | 0.0036 (3) | −0.0028 (3) |
N9 | 0.0372 (12) | 0.0547 (13) | 0.0448 (12) | −0.0048 (10) | 0.0078 (9) | −0.0057 (10) |
N10 | 0.0430 (13) | 0.0491 (14) | 0.0670 (15) | 0.0050 (11) | −0.0045 (11) | 0.0010 (11) |
C1A | 0.084 (3) | 0.0474 (19) | 0.114 (3) | 0.0087 (17) | −0.008 (2) | 0.0153 (18) |
C2A | 0.109 (4) | 0.084 (3) | 0.130 (7) | 0.020 (3) | −0.012 (4) | 0.029 (5) |
C3A | 0.063 (2) | 0.109 (3) | 0.107 (6) | 0.024 (3) | −0.012 (3) | 0.014 (3) |
C4A | 0.0434 (18) | 0.084 (2) | 0.091 (2) | 0.0079 (16) | −0.0138 (16) | −0.0026 (18) |
C1B | 0.084 (3) | 0.0474 (19) | 0.114 (3) | 0.0087 (17) | −0.008 (2) | 0.0153 (18) |
C2B | 0.109 (4) | 0.084 (3) | 0.130 (7) | 0.020 (3) | −0.012 (4) | 0.029 (5) |
C3B | 0.063 (2) | 0.109 (3) | 0.107 (6) | 0.024 (3) | −0.012 (3) | 0.014 (3) |
C4B | 0.0434 (18) | 0.084 (2) | 0.091 (2) | 0.0079 (16) | −0.0138 (16) | −0.0026 (18) |
N11 | 0.0549 (15) | 0.0599 (15) | 0.0591 (15) | 0.0124 (12) | −0.0048 (12) | −0.0119 (11) |
C5A | 0.076 (2) | 0.103 (3) | 0.088 (2) | 0.041 (2) | −0.002 (2) | −0.002 (2) |
C6A | 0.153 (6) | 0.124 (8) | 0.147 (5) | 0.086 (6) | 0.010 (4) | −0.031 (4) |
C7A | 0.099 (4) | 0.117 (6) | 0.093 (4) | 0.039 (4) | −0.002 (3) | −0.036 (4) |
C8A | 0.079 (2) | 0.082 (2) | 0.071 (2) | 0.0130 (19) | 0.0004 (18) | −0.0280 (18) |
C5B | 0.076 (2) | 0.103 (3) | 0.088 (2) | 0.041 (2) | −0.002 (2) | −0.002 (2) |
C6B | 0.153 (6) | 0.124 (8) | 0.147 (5) | 0.086 (6) | 0.010 (4) | −0.031 (4) |
C7B | 0.099 (4) | 0.117 (6) | 0.093 (4) | 0.039 (4) | −0.002 (3) | −0.036 (4) |
C8B | 0.079 (2) | 0.082 (2) | 0.071 (2) | 0.0130 (19) | 0.0004 (18) | −0.0280 (18) |
N12 | 0.0508 (15) | 0.0535 (15) | 0.0778 (16) | −0.0061 (12) | 0.0006 (12) | 0.0043 (12) |
C9A | 0.055 (2) | 0.096 (3) | 0.105 (3) | −0.0126 (19) | 0.0142 (19) | 0.003 (2) |
C10A | 0.086 (6) | 0.153 (6) | 0.202 (10) | −0.041 (4) | 0.049 (6) | 0.031 (6) |
C11A | 0.114 (5) | 0.179 (6) | 0.275 (13) | −0.031 (5) | 0.016 (6) | 0.144 (8) |
C12A | 0.090 (3) | 0.061 (2) | 0.135 (3) | −0.024 (2) | 0.005 (2) | 0.025 (2) |
C9B | 0.055 (2) | 0.096 (3) | 0.105 (3) | −0.0126 (19) | 0.0142 (19) | 0.003 (2) |
C10B | 0.086 (6) | 0.153 (6) | 0.202 (10) | −0.041 (4) | 0.049 (6) | 0.031 (6) |
C11B | 0.114 (5) | 0.179 (6) | 0.275 (13) | −0.031 (5) | 0.016 (6) | 0.144 (8) |
C12B | 0.090 (3) | 0.061 (2) | 0.135 (3) | −0.024 (2) | 0.005 (2) | 0.025 (2) |
N13 | 0.0595 (16) | 0.0892 (19) | 0.0368 (13) | −0.0288 (14) | 0.0045 (12) | −0.0014 (13) |
N14 | 0.0599 (15) | 0.0846 (17) | 0.0403 (12) | −0.0295 (13) | 0.0153 (11) | −0.0125 (12) |
C13A | 0.111 (3) | 0.094 (3) | 0.071 (2) | −0.034 (2) | 0.025 (2) | −0.017 (2) |
C14A | 0.142 (7) | 0.103 (8) | 0.081 (8) | −0.067 (6) | 0.018 (6) | −0.022 (6) |
C15A | 0.096 (8) | 0.106 (5) | 0.109 (3) | −0.054 (5) | 0.043 (5) | −0.017 (4) |
C16A | 0.090 (3) | 0.114 (3) | 0.0588 (19) | −0.040 (2) | 0.0198 (18) | −0.0001 (19) |
C13B | 0.111 (3) | 0.094 (3) | 0.071 (2) | −0.034 (2) | 0.025 (2) | −0.017 (2) |
C14B | 0.142 (7) | 0.103 (8) | 0.081 (8) | −0.067 (6) | 0.018 (6) | −0.022 (6) |
C15B | 0.096 (8) | 0.106 (5) | 0.109 (3) | −0.054 (5) | 0.043 (5) | −0.017 (4) |
C16B | 0.090 (3) | 0.114 (3) | 0.0588 (19) | −0.040 (2) | 0.0198 (18) | −0.0001 (19) |
N15 | 0.0458 (13) | 0.0895 (18) | 0.0416 (13) | 0.0107 (12) | −0.0002 (10) | −0.0063 (12) |
C17A | 0.059 (2) | 0.154 (4) | 0.068 (2) | 0.037 (2) | −0.0042 (18) | −0.003 (2) |
C18A | 0.060 (5) | 0.117 (9) | 0.121 (5) | 0.024 (7) | 0.025 (3) | −0.012 (7) |
C19A | 0.095 (4) | 0.158 (7) | 0.065 (3) | 0.031 (4) | 0.032 (3) | 0.000 (4) |
C20A | 0.064 (2) | 0.086 (2) | 0.0437 (16) | 0.0075 (16) | 0.0126 (14) | −0.0073 (15) |
C17B | 0.059 (2) | 0.154 (4) | 0.068 (2) | 0.037 (2) | −0.0042 (18) | −0.003 (2) |
C18B | 0.060 (5) | 0.117 (9) | 0.121 (5) | 0.024 (7) | 0.025 (3) | −0.012 (7) |
C19B | 0.095 (4) | 0.158 (7) | 0.065 (3) | 0.031 (4) | 0.032 (3) | 0.000 (4) |
C20B | 0.064 (2) | 0.086 (2) | 0.0437 (16) | 0.0075 (16) | 0.0126 (14) | −0.0073 (15) |
C21 | 0.061 (2) | 0.072 (2) | 0.0642 (18) | 0.0003 (16) | 0.0167 (15) | −0.0208 (15) |
C22 | 0.110 (4) | 0.144 (4) | 0.239 (6) | −0.015 (3) | 0.091 (4) | −0.098 (4) |
C23 | 0.117 (4) | 0.186 (6) | 0.277 (8) | −0.027 (4) | 0.108 (5) | −0.080 (5) |
C24 | 0.083 (2) | 0.106 (3) | 0.0560 (19) | −0.036 (2) | 0.0153 (17) | 0.0018 (19) |
C25 | 0.106 (3) | 0.117 (3) | 0.140 (4) | −0.019 (3) | −0.004 (3) | 0.051 (3) |
C26 | 0.146 (4) | 0.150 (4) | 0.196 (5) | −0.047 (4) | 0.030 (4) | 0.082 (4) |
N1' | 0.0573 (14) | 0.0454 (12) | 0.0396 (11) | 0.0058 (10) | 0.0078 (10) | −0.0010 (10) |
P2' | 0.0365 (4) | 0.0450 (4) | 0.0373 (3) | 0.0056 (3) | 0.0067 (3) | 0.0023 (3) |
N3' | 0.0363 (12) | 0.0565 (14) | 0.0498 (12) | −0.0023 (10) | 0.0078 (10) | 0.0072 (10) |
P4' | 0.0347 (4) | 0.0568 (4) | 0.0425 (4) | −0.0026 (3) | 0.0088 (3) | 0.0002 (3) |
N5' | 0.0322 (11) | 0.0627 (14) | 0.0420 (12) | −0.0033 (10) | 0.0031 (9) | 0.0064 (10) |
P6' | 0.0360 (4) | 0.0508 (4) | 0.0340 (3) | −0.0001 (3) | 0.0060 (3) | 0.0014 (3) |
N7' | 0.0530 (13) | 0.0466 (13) | 0.0375 (11) | 0.0039 (10) | 0.0028 (10) | 0.0010 (9) |
P8' | 0.0476 (4) | 0.0443 (4) | 0.0380 (4) | 0.0056 (3) | 0.0053 (3) | −0.0015 (3) |
N9' | 0.0341 (11) | 0.0493 (12) | 0.0374 (11) | 0.0054 (9) | 0.0083 (9) | −0.0028 (9) |
N10' | 0.0461 (13) | 0.0466 (13) | 0.0488 (12) | 0.0047 (10) | 0.0017 (10) | 0.0037 (10) |
C27 | 0.0450 (16) | 0.075 (2) | 0.0560 (17) | 0.0094 (15) | 0.0004 (14) | 0.0062 (15) |
C28 | 0.074 (3) | 0.096 (3) | 0.095 (3) | 0.026 (2) | −0.012 (2) | 0.014 (2) |
C29 | 0.091 (3) | 0.088 (3) | 0.107 (3) | 0.034 (2) | 0.018 (2) | 0.040 (2) |
C30 | 0.075 (2) | 0.0499 (19) | 0.089 (2) | 0.0102 (16) | 0.0013 (18) | 0.0085 (16) |
N11' | 0.0365 (13) | 0.0901 (17) | 0.0436 (13) | 0.0116 (11) | 0.0083 (10) | 0.0012 (11) |
C31A | 0.073 (2) | 0.120 (3) | 0.0515 (18) | 0.021 (2) | 0.0248 (16) | 0.0046 (18) |
C32A | 0.104 (4) | 0.182 (9) | 0.095 (3) | 0.046 (4) | 0.063 (3) | 0.019 (5) |
C33A | 0.048 (4) | 0.135 (10) | 0.115 (4) | 0.008 (6) | 0.030 (3) | −0.025 (7) |
C34A | 0.0425 (19) | 0.144 (3) | 0.078 (2) | 0.022 (2) | 0.0081 (17) | 0.011 (2) |
C31B | 0.073 (2) | 0.120 (3) | 0.0515 (18) | 0.021 (2) | 0.0248 (16) | 0.0046 (18) |
C32B | 0.104 (4) | 0.182 (9) | 0.095 (3) | 0.046 (4) | 0.063 (3) | 0.019 (5) |
C33B | 0.048 (4) | 0.135 (10) | 0.115 (4) | 0.008 (6) | 0.030 (3) | −0.025 (7) |
C34B | 0.0425 (19) | 0.144 (3) | 0.078 (2) | 0.022 (2) | 0.0081 (17) | 0.011 (2) |
N12' | 0.0648 (16) | 0.0673 (15) | 0.0529 (14) | −0.0220 (12) | 0.0185 (12) | −0.0076 (12) |
C35 | 0.104 (3) | 0.087 (3) | 0.088 (2) | −0.042 (2) | 0.030 (2) | −0.003 (2) |
C36 | 0.159 (4) | 0.090 (3) | 0.120 (3) | −0.057 (3) | 0.034 (3) | −0.016 (3) |
C37 | 0.079 (2) | 0.077 (2) | 0.099 (3) | −0.0183 (19) | 0.010 (2) | −0.025 (2) |
C38 | 0.074 (2) | 0.076 (2) | 0.065 (2) | −0.0106 (17) | 0.0166 (17) | −0.0184 (16) |
N13' | 0.0474 (15) | 0.0761 (18) | 0.0350 (14) | −0.0119 (13) | 0.0058 (12) | 0.0027 (12) |
N14' | 0.0638 (16) | 0.0638 (15) | 0.0441 (13) | 0.0195 (12) | 0.0041 (11) | −0.0085 (11) |
C39A | 0.055 (2) | 0.091 (2) | 0.086 (2) | 0.0224 (17) | 0.0127 (18) | −0.0082 (19) |
C40A | 0.114 (4) | 0.099 (8) | 0.119 (5) | 0.064 (6) | 0.032 (4) | 0.002 (5) |
C41A | 0.134 (6) | 0.136 (10) | 0.068 (4) | 0.056 (7) | 0.041 (4) | −0.002 (5) |
C42A | 0.113 (3) | 0.090 (2) | 0.0519 (19) | 0.030 (2) | 0.0183 (18) | −0.0128 (17) |
C39B | 0.055 (2) | 0.091 (2) | 0.086 (2) | 0.0224 (17) | 0.0127 (18) | −0.0082 (19) |
C40B | 0.114 (4) | 0.099 (8) | 0.119 (5) | 0.064 (6) | 0.032 (4) | 0.002 (5) |
C41B | 0.134 (6) | 0.136 (10) | 0.068 (4) | 0.056 (7) | 0.041 (4) | −0.002 (5) |
C42B | 0.113 (3) | 0.090 (2) | 0.0519 (19) | 0.030 (2) | 0.0183 (18) | −0.0128 (17) |
N15' | 0.0551 (15) | 0.0478 (14) | 0.0641 (15) | −0.0022 (11) | 0.0001 (12) | −0.0020 (11) |
C43A | 0.098 (3) | 0.057 (2) | 0.133 (3) | −0.023 (2) | 0.002 (2) | 0.012 (2) |
C44A | 0.118 (6) | 0.085 (5) | 0.231 (12) | −0.045 (4) | −0.015 (6) | 0.045 (7) |
C45A | 0.098 (4) | 0.164 (5) | 0.206 (6) | −0.043 (4) | 0.046 (4) | 0.045 (5) |
C46A | 0.0494 (19) | 0.099 (3) | 0.085 (2) | −0.0122 (18) | 0.0063 (17) | −0.0032 (19) |
C43B | 0.098 (3) | 0.057 (2) | 0.133 (3) | −0.023 (2) | 0.002 (2) | 0.012 (2) |
C44B | 0.118 (6) | 0.085 (5) | 0.231 (12) | −0.045 (4) | −0.015 (6) | 0.045 (7) |
C45B | 0.098 (4) | 0.164 (5) | 0.206 (6) | −0.043 (4) | 0.046 (4) | 0.045 (5) |
C46B | 0.0494 (19) | 0.099 (3) | 0.085 (2) | −0.0122 (18) | 0.0063 (17) | −0.0032 (19) |
C47 | 0.0516 (17) | 0.0558 (17) | 0.0506 (16) | 0.0092 (13) | 0.0132 (13) | −0.0101 (13) |
C48 | 0.059 (2) | 0.103 (3) | 0.090 (2) | 0.0210 (19) | 0.0228 (18) | −0.023 (2) |
C49 | 0.105 (3) | 0.158 (4) | 0.130 (3) | 0.063 (3) | 0.021 (3) | −0.052 (3) |
C50 | 0.095 (3) | 0.104 (3) | 0.0487 (18) | −0.037 (2) | 0.0240 (17) | −0.0046 (18) |
C51 | 0.221 (6) | 0.089 (3) | 0.158 (4) | −0.036 (4) | 0.087 (4) | 0.007 (3) |
C52 | 0.423 (13) | 0.142 (5) | 0.209 (7) | −0.080 (7) | 0.153 (7) | 0.015 (5) |
N1—P8 | 1.587 (2) | C25—C26 | 1.526 (5) |
N1—P2 | 1.594 (2) | N1'—P2' | 1.582 (2) |
P2—N3 | 1.589 (2) | N1'—P8' | 1.590 (2) |
P2—N10 | 1.630 (2) | P2'—N3' | 1.588 (2) |
P2—N9 | 1.715 (2) | P2'—N10' | 1.627 (2) |
N3—P4 | 1.588 (2) | P2'—N9' | 1.724 (2) |
P4—N5 | 1.584 (2) | N3'—P4' | 1.588 (2) |
P4—N11 | 1.640 (2) | P4'—N5' | 1.602 (2) |
P4—N12 | 1.655 (3) | P4'—N11' | 1.636 (2) |
N5—P6 | 1.584 (2) | P4'—N12' | 1.647 (2) |
P6—N13 | 1.610 (2) | N5'—P6' | 1.606 (2) |
P6—N7 | 1.611 (2) | P6'—N7' | 1.588 (2) |
P6—N9 | 1.724 (2) | P6'—N13' | 1.611 (3) |
N7—P8 | 1.602 (2) | P6'—N9' | 1.707 (2) |
P8—N15 | 1.640 (2) | N7'—P8' | 1.583 (2) |
P8—N14 | 1.643 (2) | P8'—N14' | 1.642 (2) |
N9—C21 | 1.490 (3) | P8'—N15' | 1.652 (3) |
N10—C1A | 1.455 (4) | N9'—C47 | 1.506 (3) |
N10—C4A | 1.470 (4) | N10'—C30 | 1.458 (3) |
C1A—C2A | 1.494 (14) | N10'—C27 | 1.472 (3) |
C2A—C3A | 1.505 (15) | C27—C28 | 1.495 (4) |
C3A—C4A | 1.505 (14) | C28—C29 | 1.486 (5) |
C2B—C3B | 1.509 (11) | C29—C30 | 1.501 (4) |
N11—C5A | 1.452 (4) | N11'—C31A | 1.448 (3) |
N11—C8A | 1.466 (3) | N11'—C34A | 1.458 (4) |
C5A—C6A | 1.526 (6) | C31A—C32A | 1.511 (12) |
C6A—C7A | 1.497 (9) | C32A—C33A | 1.498 (14) |
C7A—C8A | 1.497 (6) | C33A—C34A | 1.485 (10) |
C6B—C7B | 1.496 (15) | C32B—C33B | 1.498 (13) |
N12—C9A | 1.448 (4) | N12'—C35 | 1.458 (4) |
N12—C12A | 1.466 (4) | N12'—C38 | 1.460 (4) |
C9A—C10A | 1.520 (14) | C35—C36 | 1.500 (4) |
C10A—C11A | 1.511 (15) | C36—C37 | 1.488 (5) |
C11A—C12A | 1.480 (14) | C37—C38 | 1.502 (4) |
C10B—C11B | 1.527 (10) | N13'—C50 | 1.437 (4) |
N13—C24 | 1.468 (4) | N14'—C39A | 1.448 (4) |
N14—C13A | 1.421 (4) | N14'—C42A | 1.472 (3) |
N14—C16A | 1.465 (4) | C39A—C40A | 1.511 (7) |
C13A—C14A | 1.512 (13) | C40A—C41A | 1.538 (10) |
C14A—C15A | 1.493 (14) | C41A—C42A | 1.521 (8) |
C15A—C16A | 1.493 (13) | C40B—C41B | 1.510 (14) |
C14B—C15B | 1.484 (11) | N15'—C43A | 1.466 (4) |
N15—C17A | 1.451 (4) | N15'—C46A | 1.477 (4) |
N15—C20A | 1.460 (3) | C43A—C44A | 1.501 (13) |
C17A—C18A | 1.524 (10) | C44A—C45A | 1.504 (15) |
C18A—C19A | 1.505 (14) | C45A—C46A | 1.505 (14) |
C19A—C20A | 1.489 (11) | C44B—C45B | 1.506 (14) |
C18B—C19B | 1.496 (14) | C47—C48 | 1.500 (4) |
C21—C22 | 1.464 (5) | C48—C49 | 1.502 (5) |
C22—C23 | 1.390 (7) | C50—C51 | 1.539 (6) |
C24—C25 | 1.427 (5) | C51—C52 | 1.438 (7) |
P8—N1—P2 | 122.07 (14) | P2'—N1'—P8' | 122.93 (13) |
N3—P2—N1 | 120.53 (12) | N1'—P2'—N3' | 120.14 (12) |
N3—P2—N10 | 107.78 (12) | N1'—P2'—N10' | 107.94 (11) |
N1—P2—N10 | 106.50 (12) | N3'—P2'—N10' | 106.29 (12) |
N3—P2—N9 | 105.18 (11) | N1'—P2'—N9' | 105.48 (10) |
N1—P2—N9 | 106.95 (11) | N3'—P2'—N9' | 106.64 (11) |
N10—P2—N9 | 109.64 (12) | N10'—P2'—N9' | 110.19 (11) |
P4—N3—P2 | 121.15 (13) | P4'—N3'—P2' | 122.48 (14) |
N5—P4—N3 | 116.48 (11) | N3'—P4'—N5' | 116.93 (12) |
N5—P4—N11 | 106.43 (13) | N3'—P4'—N11' | 105.48 (12) |
N3—P4—N11 | 112.06 (12) | N5'—P4'—N11' | 113.47 (12) |
N5—P4—N12 | 112.99 (13) | N3'—P4'—N12' | 112.84 (13) |
N3—P4—N12 | 106.08 (12) | N5'—P4'—N12' | 104.59 (12) |
N11—P4—N12 | 101.94 (13) | N11'—P4'—N12' | 102.79 (13) |
P6—N5—P4 | 124.88 (14) | P4'—N5'—P6' | 120.77 (13) |
N5—P6—N13 | 110.05 (14) | N7'—P6'—N5' | 118.24 (12) |
N5—P6—N7 | 118.27 (12) | N7'—P6'—N13' | 110.17 (13) |
N13—P6—N7 | 106.75 (13) | N5'—P6'—N13' | 106.70 (13) |
N5—P6—N9 | 105.16 (11) | N7'—P6'—N9' | 105.06 (11) |
N13—P6—N9 | 109.36 (13) | N5'—P6'—N9' | 107.83 (12) |
N7—P6—N9 | 107.01 (12) | N13'—P6'—N9' | 108.52 (13) |
P8—N7—P6 | 117.81 (12) | P8'—N7'—P6' | 124.29 (13) |
N1—P8—N7 | 116.79 (12) | N7'—P8'—N1' | 115.73 (11) |
N1—P8—N15 | 105.80 (12) | N7'—P8'—N14' | 105.92 (12) |
N7—P8—N15 | 112.83 (12) | N1'—P8'—N14' | 113.10 (12) |
N1—P8—N14 | 112.73 (13) | N7'—P8'—N15' | 113.47 (12) |
N7—P8—N14 | 104.95 (11) | N1'—P8'—N15' | 106.39 (12) |
N15—P8—N14 | 103.01 (13) | N14'—P8'—N15' | 101.43 (13) |
C21—N9—P2 | 116.24 (18) | C47—N9'—P6' | 117.38 (15) |
C21—N9—P6 | 114.78 (17) | C47—N9'—P2' | 114.44 (16) |
P2—N9—P6 | 107.86 (12) | P6'—N9'—P2' | 107.84 (11) |
C1A—N10—C4A | 110.7 (2) | C30—N10'—C27 | 110.1 (2) |
C1A—N10—P2 | 125.6 (2) | C30—N10'—P2' | 126.27 (19) |
C4A—N10—P2 | 123.55 (19) | C27—N10'—P2' | 123.03 (18) |
N10—C1A—C2A | 100.7 (13) | N10'—C27—C28 | 104.7 (2) |
C1A—C2A—C3A | 110 (3) | C29—C28—C27 | 103.9 (3) |
C4A—C3A—C2A | 100 (2) | C28—C29—C30 | 104.5 (3) |
N10—C4A—C3A | 108.2 (17) | N10'—C30—C29 | 103.6 (3) |
C5A—N11—C8A | 111.6 (2) | C31A—N11'—C34A | 110.6 (2) |
C5A—N11—P4 | 126.1 (2) | C31A—N11'—P4' | 125.68 (19) |
C8A—N11—P4 | 121.85 (19) | C34A—N11'—P4' | 123.18 (19) |
N11—C5A—C6A | 102.4 (4) | N11'—C31A—C32A | 103.7 (9) |
C7A—C6A—C5A | 107.5 (5) | C33A—C32A—C31A | 105.2 (13) |
C8A—C7A—C6A | 101.8 (7) | C34A—C33A—C32A | 102.6 (13) |
N11—C8A—C7A | 105.3 (3) | N11'—C34A—C33A | 105.4 (7) |
C9A—N12—C12A | 108.9 (3) | C35—N12'—C38 | 108.5 (2) |
C9A—N12—P4 | 119.6 (2) | C35—N12'—P4' | 120.89 (19) |
C12A—N12—P4 | 118.3 (2) | C38—N12'—P4' | 123.62 (19) |
N12—C9A—C10A | 102.9 (16) | N12'—C35—C36 | 105.1 (3) |
C11A—C10A—C9A | 96 (3) | C37—C36—C35 | 107.2 (3) |
C12A—C11A—C10A | 100 (2) | C36—C37—C38 | 103.8 (3) |
N12—C12A—C11A | 100 (2) | N12'—C38—C37 | 103.3 (3) |
C24—N13—P6 | 124.0 (2) | C50—N13'—P6' | 124.6 (2) |
C13A—N14—C16A | 108.3 (2) | C39A—N14'—C42A | 111.0 (2) |
C13A—N14—P8 | 125.6 (2) | C39A—N14'—P8' | 124.33 (19) |
C16A—N14—P8 | 121.03 (19) | C42A—N14'—P8' | 121.31 (19) |
N14—C13A—C14A | 104.9 (16) | N14'—C39A—C40A | 105.3 (5) |
C15A—C14A—C13A | 97 (2) | C39A—C40A—C41A | 102.2 (7) |
C14A—C15A—C16A | 110 (3) | C42A—C41A—C40A | 105.1 (7) |
N14—C16A—C15A | 102.0 (16) | N14'—C42A—C41A | 104.4 (5) |
C17A—N15—C20A | 110.2 (2) | C43A—N15'—C46A | 109.5 (3) |
C17A—N15—P8 | 123.5 (2) | C43A—N15'—P8' | 117.4 (2) |
C20A—N15—P8 | 125.67 (19) | C46A—N15'—P8' | 117.53 (19) |
N15—C17A—C18A | 101.1 (6) | N15'—C43A—C44A | 101.8 (9) |
C19A—C18A—C17A | 103.6 (12) | C43A—C44A—C45A | 109 (2) |
C20A—C19A—C18A | 101.6 (12) | C44A—C45A—C46A | 99.3 (16) |
N15—C20A—C19A | 106.3 (8) | N15'—C46A—C45A | 108.5 (14) |
C22—C21—N9 | 114.8 (3) | C48—C47—N9' | 111.2 (2) |
C23—C22—C21 | 122.8 (5) | C47—C48—C49 | 113.0 (3) |
C25—C24—N13 | 115.3 (3) | N13'—C50—C51 | 112.8 (3) |
C24—C25—C26 | 112.0 (4) | C52—C51—C50 | 117.6 (5) |
Experimental details
Crystal data | |
Chemical formula | C26H55N11P4 |
Mr | 645.69 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.405 (11), 21.545 (5), 28.893 (16) |
β (°) | 97.73 (6) |
V (Å3) | 7035 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14219, 13799, 7479 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.121, 1.03 |
No. of reflections | 13799 |
No. of parameters | 803 |
No. of restraints | 783 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.36 |
Computer programs: MolEN (Fair, 1990), MolEN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
N1—P8 | 1.587 (2) | N1'—P2' | 1.582 (2) |
N1—P2 | 1.594 (2) | N1'—P8' | 1.590 (2) |
P2—N3 | 1.589 (2) | P2'—N3' | 1.588 (2) |
P2—N9 | 1.715 (2) | P2'—N9' | 1.724 (2) |
N3—P4 | 1.588 (2) | N3'—P4' | 1.588 (2) |
P4—N5 | 1.584 (2) | P4'—N5' | 1.602 (2) |
N5—P6 | 1.584 (2) | N5'—P6' | 1.606 (2) |
P6—N7 | 1.611 (2) | P6'—N7' | 1.588 (2) |
P6—N9 | 1.724 (2) | P6'—N9' | 1.707 (2) |
N7—P8 | 1.602 (2) | N7'—P8' | 1.583 (2) |
P8—N1—P2 | 122.07 (14) | P2'—N1'—P8' | 122.93 (13) |
N3—P2—N1 | 120.53 (12) | N1'—P2'—N3' | 120.14 (12) |
N3—P2—N9 | 105.18 (11) | N1'—P2'—N9' | 105.48 (10) |
N1—P2—N9 | 106.95 (11) | N3'—P2'—N9' | 106.64 (11) |
P4—N3—P2 | 121.15 (13) | P4'—N3'—P2' | 122.48 (14) |
N5—P4—N3 | 116.48 (11) | N3'—P4'—N5' | 116.93 (12) |
P6—N5—P4 | 124.88 (14) | P4'—N5'—P6' | 120.77 (13) |
N5—P6—N7 | 118.27 (12) | N7'—P6'—N5' | 118.24 (12) |
N5—P6—N9 | 105.16 (11) | N7'—P6'—N9' | 105.06 (11) |
N7—P6—N9 | 107.01 (12) | N5'—P6'—N9' | 107.83 (12) |
P8—N7—P6 | 117.81 (12) | P8'—N7'—P6' | 124.29 (13) |
N1—P8—N7 | 116.79 (12) | N7'—P8'—N1' | 115.73 (11) |
P2—N9—P6 | 107.86 (12) | P6'—N9'—P2' | 107.84 (11) |
The structures of tri- and tetraphosphazene derivatives with different substituents have been the subject of much interest in our laboratory. Examples include 2,cis-4,trans-6,trans-8-tetrachloro-2,4,6,8- tetrakis(diethylamino)cyclotetra(phosphazene), (II) (Hökelek & Kılıç, 1990), 2-(2,6-di-tert-butylphenoxy)-2',4,4,4',6,6,6'-nonachloro-2,2'- bi(cyclotri-λ5-phosphazene), (III) (Hökelek et al., 1994), N3P3Cl5[OC6H2(tBu)3-2,4,6], (IV) (Kılıç et al., 1996), 2-(2,6-di-tert-butyl-4-methylphenoxy)-2,4,4,6,6,8,8-heptachlorocyclo- 2λ5,4λ5,6λ5,8λ5-tetraphosphazatetraene, (V) (Hökelek et al., 1996), trans-2,6-bis(ethylamino)-2,4,4,6,8,8-hexamorpholinocyclo- 2λ5,4λ5,6λ5,8λ5-tetraphosphazatetraene, (VI) (Hökelek et al., 1998), 2,4,4,6,6-pentachloro-2-(2,6-di-tert-butyl-4-methylphenoxy)cyclo- 2λ5,4λ5,6λ5-triphosphazatriene, (VII) (Hökelek, Kılıç, Begeç A & Kılıç, 1999), trans-2,6-bis(ethylamino)2,4,4,6,8,8-hexapiperidinocyclo- 2λ5,4λ5,6λ5,8λ5-tetraphosphazatetraene, (VIII) (Hökelek, Kılıç E. & Kılıç 1999), 2,2'-[triethyleneglycolbis(pentylether-2-amino)-2,2',4,4,4',4',6,6,6',6'- decachlorobicyclo-2λ5,2'λ5,4λ5,4'λ5,6λ5,6'λ5– triphosphazatriene, (IX) (Yıldız et al., 1999), 2,4-[2,2'-methylenebis(4-nitrophenoxy)]-2,4,6,6-tetrachlorocyclo- 2λ5,4λ5,6λ5-triphosphazatriene (ansa), (X) (Hökelek, Akduran, N., Yıldız et al., 2000) and 2,4,4,6,6-pentachloro-2-(2,4,6-trimethylphenoxy)cyclo- 2λ5,4λ5,6λ5-triphosphazatriene, (XI) (Hökelek, Akduran, N., Kılıç et al., 2000).
The bicyclic P4N5 ring system, based on cyclotetraphosphazatetraene, was discovered by Sau in 1975 (Cameron et al., 1975; Sau, 1976). In subsequent years, several studies devoted to the formation of this class of compounds were published (Contractor et al., 1987; Krishnamurthy, 1989; Narayanaswamy et al., 1985; Krishnamurthy et al., 1979). These involved the reactions of 2-trans-6-bis(primary alkylamino)hexachloro derivatives, viz. dimethylamine, diethylamine, dibenzylamine, pyrrolidine, t-butylamine, piperidine and morpholine (Krishnamurthy, 1989).
Some of the aminophosphazene derivatives are thought to be useful as chemotherapeutic agents for the treatment of cancer (Chernov et al., 1959; van der Huizen, 1984). A relationship has been observed between the structures of the cyclophosphazenes and cytostatic activity (van der Huizen, 1984). For effective inhibition of tumour growth, electron-donating groups (e.g. aziridine and pyrrolidine) in the P—N ring skeletons seem to be essential.
The crystal structures of some bicyclic phosphazene derivatives, such as N4P4(NMe2)5(NHR)(NR) and N4P4(NHR)6(NR) (R is Me or Et), have been reported in the literature (Deutsch et al., 1987; Cameron & Mannan, 1977; Cameron et al., 1979; Cameron et al., 1986; Krishnamurthy et al., 1982). We have investigated the reactions of trans-2,6-bis(propylamino)-2,4,4,6,8,8-hexachlorocyclo- 2λ5,4λ5,6λ5,8λ5-tetraphosphazatetraene and pyrrolidine in CHCl3. The reaction yielded two different products, bicyclic (I) and monocyclic (XII), both fully substituted tetraphosphazene derivatives. The title compound, (I), was separated as a major product from the reaction mixture by column chromatography, and it is the first example of NnPr-bridged bicyclic phosphazenes. The main objective of this study was to determine the influences of the highly hindered bridged NnPr chain and the pyrrolidine and NHnPr side groups on the structure of the bicyclic phosphazene ring. \sch
The title compound, (I), is shown in Fig. 1. The asymmetric unit contains two molecules, almost related by a non-crystallographic inversion centre at approximately (1/4,3/4,7/8) Query last. The phosphazene consists of an eight-membered ring, (PN)4, with the second and sixth P atoms in the ring being bridged by a propylamino group. One of the bridged P atoms has a second propylamino group attached, while the other is substituted by a pyrrolidino group. The other P atoms have further pyrrolidino groups attached. The bicyclic molecule is made up of two N3P3 rings fused by a common PNP fragment. The six-membered rings are in sofa conformations (Fig. 2). Each ring is V-shaped, with each of the two halves, P2/N3/P4/N5/P6, P2/N1/P8/N7/P6, P2'/N3'/P4'/N5'/P6' and P2'/N1'/P8'/N7'/P6', being essentially planar. In the two molecules, the two halves are inclined at angles of 62.2 (2) and 62.3 (2)°. The halves make angles of 62.5 (2) and 55.4 (2), respectively, and 56.3 (2) and 61.4 (2)°, respectively, with the planes defined by the propylamino bridges, P2/N9/P6 and P2'/N9'/P6'.
The maximum separations between the two non-bridged P atoms in each molecule are P4···P8 4.013 (4) and P4'···P8' 4.108 (4) Å. All other P···P distances in the two molecules are in the ranges 2.751 (2)–2.809 (2) and 2.773 (2)–2.804 (3) Å, with means of 2.778 (2) and 2.787 (2) Å, respectively. The N atoms are displaced above (+) and below (-) the least-squares planes through the P atoms by the following distances: N1 - 0.608 (4), N3 - 0.447 (4), N5 0.446 (4), N7 0.073 (3) and N9 1.596 (4), and N1' 0.329 (3), N3' 0.525 (4), N5' -0.011 (3), N7' -0.218 (3) and N9' -1.616 (3) Å.
The conformations of the bicyclic phosphazenes resemble the `adamantane' structure. The dihedral angles of the bicyclic rings in (I) (Fig. 2) reflect the structural aspects. The sums of the bond angles around atoms N9 and N9' [338.9 (2) and 339.7 (2)°] show a changing of the hybridizations of the N atoms from trigonal planar towards pyramidal.
In the P4N4 tetraphosphazene ring systems, the endocyclic P—N and P'-N' bond distances vary from 1.584 (2) to 1.611 (2) Å [average 1.592 (2) Å] and from 1.582 (2) to 1.606 (2) Å [average 1.591 (2) Å] in the two molecules. The longest P—N bonds in the present bicyclic molecules are those involving the bridging groups. The P—N bonds of the bridging propylamine groups [N9—P2 1.715 (2) and N9—P6 1.724 (2), and N9'-P2' 1.724 (2) and N9'-P6' 1.707 (2) Å] have different values in both molecules. The corresponding values reported in the literature are 1.73 (1) and 1.76 (1) Å in N4P4(NMe2)5(NHEt)(NEt) (Cameron & Mannan, 1977), 1.709 (6) and 1.723 (6) Å in N4P4(NHMe)6(NMe) (Cameron et al., 1979) and 1.706 (4) and 1.725 (4) Å in N4P4(NMe2)5(NHMe)(NMe) (Cameron et al., 1986). The exocyclic P—N and P'-N' bond distances vary from 1.610 (2) to 1.655 (2) Å [average 1.636 (2) Å] and 1.611 (3) to 1.652 (2) Å [average 1.636 (2) Å] for the two molecules. Structure determinations carried out in our laboratory of the trimeric and tetrameric phosphazenes, compounds (II)-(XI), have shown that the P—N bond ranges are between 1.55–1.61 and 1.63–1.66 Å for endocyclic and exocyclic values, respectively.
In bicyclic phosphazenes, three types of P—N bonds are observed: the peripheral ones (1.57–1.61 Å) retain their phosphazenic character, the exocyclic P—N bonds (1.63–1.66 Å) are slightly longer and the P—N bonds at the bridgehead (1.71–1.76 Å) are close to the value associated with a P—N single bond (1.77–1.80 Å) (Krishnamurthy, 1994). In (I), the single and double bond character of the endo- and exocyclic P—N bonds cannot be easily distinguished (Table 1), since they retain their phosphazenic character in the phosphazene macrorings. On the other hand, the bridgehead P—N bonds are outside the limits of the usual P—N single bond range.
The packing of the molecules in the unit cell is due to van der Waals and dipole-dipole forces of interaction (Fig. 3). The molecules are aligned parallel to the bc plane, while, in the a direction, the molecules are packed in staggered layers.
In conclusion, the substituents bonded to P atoms play a very important role in the conformations of bicyclic phosphazene rings.