Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010101770X/na1540sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010101770X/na1540Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010101770X/na1540IIsup3.hkl |
CCDC references: 180173; 180174
A solution of 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene (7.24 g, 0.0168 mol) in a 200 ml mixture of Et2O and n-hexane (3:5) was added dropwise to a stirred solution of triethylamine (5.10 g, 0.05049 mol) in 200 ml of the same solvent mixture and then spermidine (2.39 g, 0.0168 mol) in 50 ml of the same solvent mixture was added. The reaction mixture was stirred under an atmosphere of argon at room temperature for 22 d. Triethylamine hydrochloride was filtered off and the solvent removed under reduced pressure at 303 K. Two compounds were detected [RF = 0.9 (product 1) and 0.36 (product 2)] by thin-layer chromatography using dichloromethane–ethyl acetate (3:1) as the mobile phase. These were separated by column chromatography on silica gel using dichloromethane–ethyl acetate (1:1) as eluent. The isomeric mixture of the singly bridged compound (product 1) was obtained as a colourless solid (m.p. 331–341 K, 2.5 g, yield 13.23%) and the fused tricyclic derivative (product 2), the title compound, was initially crystallized from dichloromethane–n-hexane (1:1) (m.p. 449 K, 0.8 g, yield 10%) to give structure (I) and then from DCM–ethyl acetate–n-hexane (1:1:1) to give structure (II). Found (product 2): C 48.8, H 5.10, N 18.00%; M+ 467.1. C19H26ClN6P3 requires: C 48.89, H 5.61, N 18.00%; M 466.8.
For both structures, the amino H atoms were found experimentally from a difference map and freely refined, whilst the remaining H atoms were located in idealized positions (C—H = 0.95 and 0.99 Å) with their displacement parameters riding on those of the parent atom. The ansa-bridged ring in molecules (Ia) and (Ib) exhibit positional disorder about atoms C17 and C36 (50 and 75% site occupation, respectively). Both components were constrained to idealized methylene bond lengths with isotropic displacement parameters.
For both compounds, cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990).
C19H26ClN6P3 | Z = 2 |
Mr = 466.82 | F(000) = 1464 |
Triclinic, P1 | Dx = 1.418 Mg m−3 |
a = 10.083 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.770 (3) Å | Cell parameters from 21067 reflections |
c = 25.816 (5) Å | θ = 2.9–27.5° |
α = 95.64 (3)° | µ = 0.41 mm−1 |
β = 96.98 (3)° | T = 120 K |
γ = 92.07 (3)° | Rod, colourless |
V = 3279.5 (11) Å3 | 0.18 × 0.08 × 0.05 mm |
Nonius KappaCCD area-detector diffractometer | 8616 reflections with I > 2σ(I) |
ϕ and ω scans | Rint = 0.071 |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | θmax = 27.5°, θmin = 2.9° |
Tmin = 0.929, Tmax = 0.980 | h = −13→13 |
42350 measured reflections | k = −16→16 |
14040 independent reflections | l = −33→33 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0724P)2 + 0.3311P] where P = (Fo2 + 2Fc2)/3 |
14040 reflections | (Δ/σ)max = 0.081 |
807 parameters | Δρmax = 1.28 e Å−3 |
12 restraints | Δρmin = −1.25 e Å−3 |
C19H26ClN6P3 | γ = 92.07 (3)° |
Mr = 466.82 | V = 3279.5 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.083 (2) Å | Mo Kα radiation |
b = 12.770 (3) Å | µ = 0.41 mm−1 |
c = 25.816 (5) Å | T = 120 K |
α = 95.64 (3)° | 0.18 × 0.08 × 0.05 mm |
β = 96.98 (3)° |
Nonius KappaCCD area-detector diffractometer | 14040 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 8616 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.980 | Rint = 0.071 |
42350 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 12 restraints |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 1.28 e Å−3 |
14040 reflections | Δρmin = −1.25 e Å−3 |
807 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 1.3424 (3) | 0.6147 (2) | 0.90941 (11) | 0.0396 (8) | |
C2 | 1.3999 (3) | 0.6441 (3) | 0.86725 (12) | 0.0548 (10) | |
H2 | 1.3681 | 0.7020 | 0.8497 | 0.066* | |
C3 | 1.5081 (3) | 0.5865 (3) | 0.85005 (14) | 0.0761 (13) | |
H3 | 1.5495 | 0.6062 | 0.8211 | 0.091* | |
C4 | 1.5520 (3) | 0.5023 (3) | 0.87571 (16) | 0.0748 (13) | |
H4 | 1.6236 | 0.4640 | 0.8639 | 0.090* | |
C5 | 1.4949 (3) | 0.4723 (3) | 0.91780 (17) | 0.0723 (13) | |
H5 | 1.5265 | 0.4143 | 0.9353 | 0.087* | |
C6 | 1.3909 (3) | 0.5282 (2) | 0.93407 (15) | 0.0564 (10) | |
H6 | 1.3504 | 0.5074 | 0.9631 | 0.068* | |
C7 | 1.2830 (3) | 0.76093 (19) | 0.99355 (10) | 0.0296 (7) | |
C8 | 1.3830 (3) | 0.8367 (2) | 0.99093 (11) | 0.0437 (8) | |
H8 | 1.4108 | 0.8483 | 0.9580 | 0.052* | |
C9 | 1.4429 (3) | 0.8959 (2) | 1.03636 (12) | 0.0506 (9) | |
H9 | 1.5112 | 0.9480 | 1.0344 | 0.061* | |
C10 | 1.4031 (3) | 0.8791 (2) | 1.08420 (12) | 0.0460 (9) | |
H10 | 1.4447 | 0.9190 | 1.1153 | 0.055* | |
C11 | 1.3041 (3) | 0.8054 (2) | 1.08693 (12) | 0.0496 (9) | |
H11 | 1.2767 | 0.7940 | 1.1199 | 0.059* | |
C12 | 1.2431 (3) | 0.7467 (2) | 1.04169 (11) | 0.0439 (8) | |
H12 | 1.1731 | 0.6961 | 1.0439 | 0.053* | |
C13 | 0.8806 (3) | 0.7606 (2) | 0.76703 (11) | 0.0388 (8) | |
H13A | 0.8123 | 0.7040 | 0.7692 | 0.047* | |
H13B | 0.8975 | 0.7594 | 0.7300 | 0.047* | |
C14 | 0.8289 (3) | 0.8662 (2) | 0.78491 (12) | 0.0455 (9) | |
H14A | 0.7503 | 0.8811 | 0.7603 | 0.055* | |
H14B | 0.8991 | 0.9222 | 0.7845 | 0.055* | |
C15 | 0.7896 (3) | 0.8672 (2) | 0.83981 (12) | 0.0462 (9) | |
H15A | 0.7619 | 0.9385 | 0.8512 | 0.055* | |
H15B | 0.7117 | 0.8173 | 0.8390 | 0.055* | |
C16 | 0.86495 (8) | 0.85055 (14) | 0.93217 (6) | 0.0599 (10) | |
H16A | 0.8902 | 0.9259 | 0.9430 | 0.072* | |
H16B | 0.9363 | 0.8120 | 0.9508 | 0.072* | |
C17 | 0.74701 (15) | 0.83228 (7) | 0.96402 (8) | 0.0220 (8) | 0.237 (5) |
H17A | 0.6647 | 0.8562 | 0.9446 | 0.026* | 0.237 (5) |
H17B | 0.7646 | 0.8771 | 0.9979 | 0.026* | 0.237 (5) |
C17' | 0.73092 (13) | 0.78585 (11) | 0.92995 (5) | 0.112 (2) | 0.763 (5) |
H17C | 0.6575 | 0.8353 | 0.9294 | 0.134* | 0.763 (5) |
H17D | 0.7167 | 0.7394 | 0.8965 | 0.134* | 0.763 (5) |
C18 | 0.7202 (3) | 0.71702 (9) | 0.97548 (7) | 0.115 (2) | |
H18A | 0.6588 | 0.7193 | 1.0027 | 0.138* | |
H18B | 0.6702 | 0.6796 | 0.9432 | 0.138* | |
C19 | 0.8269 (3) | 0.6520 (2) | 0.99208 (12) | 0.0455 (8) | |
H19A | 0.8121 | 0.6310 | 1.0269 | 0.055* | |
H19B | 0.9111 | 0.6962 | 0.9971 | 0.055* | |
N1 | 1.1418 (2) | 0.76046 (16) | 0.89453 (8) | 0.0317 (6) | |
N2 | 0.9215 (2) | 0.62939 (15) | 0.87237 (8) | 0.0283 (5) | |
N3 | 1.1067 (2) | 0.59708 (16) | 0.95304 (8) | 0.0330 (6) | |
N4 | 1.0061 (2) | 0.74142 (16) | 0.80033 (8) | 0.0306 (6) | |
N5 | 0.8988 (2) | 0.83828 (16) | 0.87846 (9) | 0.0348 (6) | |
N6 | 0.8481 (2) | 0.55598 (16) | 0.95856 (8) | 0.0312 (6) | |
P1 | 1.20643 (7) | 0.68303 (5) | 0.93471 (3) | 0.02953 (18) | |
P2 | 0.99490 (7) | 0.73846 (5) | 0.86324 (3) | 0.02848 (17) | |
P3 | 0.96450 (7) | 0.56492 (5) | 0.91961 (3) | 0.02814 (17) | |
Cl1 | 0.96498 (7) | 0.41079 (5) | 0.88954 (3) | 0.03920 (19) | |
C20 | 0.3384 (2) | 0.63716 (17) | 0.35175 (9) | 0.0214 (6) | |
C21 | 0.2720 (2) | 0.54289 (18) | 0.35884 (10) | 0.0275 (7) | |
H21 | 0.2895 | 0.5129 | 0.3911 | 0.033* | |
C22 | 0.1800 (3) | 0.49276 (19) | 0.31860 (11) | 0.0313 (7) | |
H22 | 0.1344 | 0.4291 | 0.3239 | 0.038* | |
C23 | 0.1541 (3) | 0.5337 (2) | 0.27148 (11) | 0.0357 (8) | |
H23 | 0.0929 | 0.4980 | 0.2440 | 0.043* | |
C24 | 0.2192 (3) | 0.6287 (2) | 0.26451 (11) | 0.0383 (8) | |
H24 | 0.2015 | 0.6584 | 0.2322 | 0.046* | |
C25 | 0.3094 (3) | 0.6799 (2) | 0.30451 (10) | 0.0321 (7) | |
H25 | 0.3521 | 0.7451 | 0.2996 | 0.039* | |
C26 | 0.4031 (2) | 0.82634 (17) | 0.42496 (9) | 0.0186 (6) | |
C27 | 0.3411 (2) | 0.83565 (19) | 0.47068 (9) | 0.0249 (6) | |
H27 | 0.3232 | 0.7747 | 0.4875 | 0.030* | |
C28 | 0.3056 (2) | 0.93363 (19) | 0.49158 (10) | 0.0291 (7) | |
H28 | 0.2630 | 0.9393 | 0.5225 | 0.035* | |
C29 | 0.3319 (2) | 1.02262 (19) | 0.46767 (10) | 0.0294 (7) | |
H29 | 0.3090 | 1.0896 | 0.4824 | 0.035* | |
C30 | 0.3918 (3) | 1.01403 (19) | 0.42211 (11) | 0.0313 (7) | |
H30 | 0.4083 | 1.0751 | 0.4052 | 0.038* | |
C31 | 0.4277 (2) | 0.91697 (18) | 0.40117 (10) | 0.0270 (6) | |
H31 | 0.4698 | 0.9121 | 0.3701 | 0.032* | |
C32 | 0.9282 (2) | 0.8979 (2) | 0.42656 (10) | 0.0322 (7) | |
H32A | 0.9584 | 0.8772 | 0.4619 | 0.039* | |
H32B | 0.9450 | 0.9750 | 0.4275 | 0.039* | |
C33 | 1.0076 (3) | 0.8416 (2) | 0.38679 (11) | 0.0366 (8) | |
H33A | 0.9774 | 0.8627 | 0.3515 | 0.044* | |
H33B | 1.1035 | 0.8636 | 0.3957 | 0.044* | |
C34 | 0.9914 (3) | 0.7229 (2) | 0.38533 (11) | 0.0362 (7) | |
H34A | 1.0397 | 0.6898 | 0.3573 | 0.043* | |
H34B | 1.0324 | 0.7011 | 0.4192 | 0.043* | |
C35 | 0.83072 (18) | 0.57042 (18) | 0.35966 (6) | 0.0413 (7)* | |
H35A | 0.8536 | 0.5598 | 0.3233 | 0.050* | |
H35B | 0.7334 | 0.5538 | 0.3573 | 0.050* | |
C36 | 0.8965 (3) | 0.4874 (3) | 0.38765 (13) | 0.0336 (9)* | 0.766 (4) |
H36A | 0.8686 | 0.4183 | 0.3676 | 0.040* | 0.766 (4) |
H36B | 0.9944 | 0.4976 | 0.3879 | 0.040* | 0.766 (4) |
C36' | 0.9129 (4) | 0.5507 (5) | 0.41458 (10) | 0.035 (3)* | 0.234 (4) |
H36C | 1.0031 | 0.5298 | 0.4075 | 0.042* | 0.234 (4) |
H36D | 0.9249 | 0.6193 | 0.4365 | 0.042* | 0.234 (4) |
C37 | 0.8680 (3) | 0.4834 (3) | 0.44247 (13) | 0.0536 (8)* | |
H37A | 0.8951 | 0.5527 | 0.4623 | 0.064* | |
H37B | 0.9247 | 0.4304 | 0.4585 | 0.064* | |
C38 | 0.7215 (2) | 0.45638 (19) | 0.44933 (10) | 0.0298 (7) | |
H38A | 0.6621 | 0.4699 | 0.4175 | 0.036* | |
H38B | 0.7103 | 0.3808 | 0.4543 | 0.036* | |
N7 | 0.59369 (18) | 0.72563 (14) | 0.37250 (7) | 0.0194 (5) | |
N8 | 0.73921 (19) | 0.71003 (14) | 0.46598 (7) | 0.0203 (5) | |
N9 | 0.48550 (19) | 0.62735 (14) | 0.44824 (7) | 0.0202 (5) | |
N10 | 0.78406 (17) | 0.87171 (10) | 0.41318 (5) | 0.0237 (5) | |
N11 | 0.84986 (19) | 0.68468 (15) | 0.37572 (8) | 0.0252 (5) | |
N12 | 0.6847 (2) | 0.52100 (15) | 0.49506 (8) | 0.0261 (5) | |
P4 | 0.46370 (6) | 0.70183 (4) | 0.40109 (2) | 0.01903 (15) | |
P5 | 0.73643 (6) | 0.74502 (5) | 0.40754 (2) | 0.02041 (15) | |
P6 | 0.62769 (6) | 0.63663 (5) | 0.48377 (2) | 0.02108 (15) | |
Cl2 | 0.59698 (6) | 0.69072 (5) | 0.55835 (2) | 0.02968 (16) | |
C39 | 0.1471 (2) | −0.12569 (18) | 0.66002 (10) | 0.0260 (6) | |
C40 | 0.0129 (3) | −0.1088 (2) | 0.66526 (11) | 0.0394 (8) | |
H40 | −0.0115 | −0.0757 | 0.6971 | 0.047* | |
C41 | −0.0842 (3) | −0.1412 (3) | 0.62327 (12) | 0.0507 (9) | |
H41 | −0.1756 | −0.1312 | 0.6270 | 0.061* | |
C42 | −0.0510 (3) | −0.1877 (2) | 0.57633 (11) | 0.0438 (8) | |
H42 | −0.1187 | −0.2103 | 0.5482 | 0.053* | |
C43 | 0.0821 (3) | −0.2009 (2) | 0.57088 (11) | 0.0384 (8) | |
H43 | 0.1061 | −0.2317 | 0.5385 | 0.046* | |
C44 | 0.1801 (3) | −0.1699 (2) | 0.61193 (10) | 0.0317 (7) | |
H44 | 0.2714 | −0.1786 | 0.6075 | 0.038* | |
C45 | 0.3659 (2) | −0.21159 (19) | 0.71504 (10) | 0.0266 (7) | |
C46 | 0.3083 (3) | −0.3023 (2) | 0.73031 (11) | 0.0381 (8) | |
H46 | 0.2234 | −0.3004 | 0.7426 | 0.046* | |
C47 | 0.3746 (3) | −0.3957 (2) | 0.72758 (13) | 0.0509 (9) | |
H47 | 0.3362 | −0.4575 | 0.7385 | 0.061* | |
C48 | 0.4979 (3) | −0.3978 (2) | 0.70865 (12) | 0.0487 (9) | |
H48 | 0.5432 | −0.4617 | 0.7065 | 0.058* | |
C49 | 0.5541 (3) | −0.3103 (2) | 0.69337 (11) | 0.0386 (8) | |
H49 | 0.6384 | −0.3129 | 0.6805 | 0.046* | |
C50 | 0.4887 (3) | −0.2168 (2) | 0.69652 (10) | 0.0333 (7) | |
H50 | 0.5288 | −0.1554 | 0.6858 | 0.040* | |
C51 | 0.2031 (3) | 0.0428 (2) | 0.91327 (11) | 0.0425 (8) | |
H51A | 0.2675 | 0.1042 | 0.9215 | 0.051* | |
H51B | 0.2069 | 0.0034 | 0.9446 | 0.051* | |
C52 | 0.0639 (3) | 0.0804 (2) | 0.90072 (11) | 0.0458 (9) | |
H52A | 0.0001 | 0.0188 | 0.8913 | 0.055* | |
H52B | 0.0378 | 0.1212 | 0.9322 | 0.055* | |
C53 | 0.0556 (3) | 0.1480 (2) | 0.85625 (11) | 0.0428 (8) | |
H53A | −0.0396 | 0.1602 | 0.8453 | 0.051* | |
H53B | 0.1014 | 0.2173 | 0.8690 | 0.051* | |
C54 | 0.0937 (3) | 0.16376 (19) | 0.76459 (10) | 0.0315 (7) | |
H54A | −0.0030 | 0.1587 | 0.7514 | 0.038* | |
H54B | 0.1413 | 0.1296 | 0.7366 | 0.038* | |
C55 | 0.1397 (3) | 0.2811 (2) | 0.77375 (11) | 0.0361 (7) | |
H55A | 0.1332 | 0.3093 | 0.7392 | 0.043* | |
H55B | 0.0757 | 0.3186 | 0.7942 | 0.043* | |
C56 | 0.2800 (3) | 0.3086 (2) | 0.80177 (11) | 0.0353 (7) | |
H56A | 0.2818 | 0.3811 | 0.8195 | 0.042* | |
H56B | 0.2985 | 0.2605 | 0.8293 | 0.042* | |
C57 | 0.3922 (3) | 0.30256 (19) | 0.76739 (11) | 0.0338 (7) | |
H57A | 0.3883 | 0.3632 | 0.7462 | 0.041* | |
H57B | 0.4790 | 0.3091 | 0.7903 | 0.041* | |
N13 | 0.1992 (2) | −0.07999 (15) | 0.76704 (8) | 0.0267 (5) | |
N14 | 0.3746 (2) | 0.07920 (14) | 0.80620 (8) | 0.0257 (5) | |
N15 | 0.3685 (2) | 0.00306 (15) | 0.70382 (8) | 0.0285 (6) | |
N16 | 0.2407 (2) | −0.02515 (16) | 0.86913 (8) | 0.0332 (6) | |
N17 | 0.1146 (2) | 0.10323 (16) | 0.81053 (8) | 0.0296 (6) | |
N18 | 0.3875 (2) | 0.20524 (15) | 0.73198 (8) | 0.0256 (5) | |
P7 | 0.27298 (6) | −0.09339 (5) | 0.71551 (2) | 0.02276 (16) | |
P8 | 0.23538 (7) | 0.01850 (5) | 0.81155 (3) | 0.02572 (17) | |
P9 | 0.41908 (7) | 0.09054 (5) | 0.75073 (3) | 0.02404 (16) | |
Cl3 | 0.62644 (6) | 0.08788 (5) | 0.76304 (3) | 0.03483 (17) | |
H4N | 1.067 (2) | 0.7835 (19) | 0.7946 (10) | 0.036 (8)* | |
H6N | 0.849 (3) | 0.499 (2) | 0.9769 (11) | 0.053 (9)* | |
H10N | 0.7485 (5) | 0.9093 (3) | 0.38460 (12) | 0.018* | |
H12N | 0.645 (3) | 0.498 (2) | 0.5130 (11) | 0.042 (9)* | |
H16N | 0.209 (2) | −0.0844 (18) | 0.8667 (9) | 0.024 (7)* | |
H18N | 0.404 (2) | 0.2118 (18) | 0.7047 (9) | 0.023 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0267 (14) | 0.0500 (17) | 0.0363 (17) | 0.0033 (13) | −0.0038 (13) | −0.0143 (14) |
C2 | 0.0345 (16) | 0.088 (2) | 0.0379 (18) | 0.0005 (17) | 0.0046 (15) | −0.0098 (17) |
C3 | 0.0407 (19) | 0.130 (3) | 0.049 (2) | −0.002 (2) | 0.0063 (17) | −0.030 (2) |
C4 | 0.0378 (19) | 0.092 (3) | 0.080 (3) | 0.0161 (19) | −0.0093 (19) | −0.048 (2) |
C5 | 0.043 (2) | 0.071 (2) | 0.094 (3) | 0.0173 (18) | −0.008 (2) | −0.024 (2) |
C6 | 0.0367 (17) | 0.0513 (19) | 0.075 (2) | 0.0089 (16) | −0.0022 (17) | −0.0131 (18) |
C7 | 0.0313 (14) | 0.0284 (13) | 0.0291 (14) | 0.0037 (12) | 0.0017 (12) | 0.0046 (11) |
C8 | 0.0457 (17) | 0.0519 (17) | 0.0310 (16) | −0.0099 (15) | −0.0010 (14) | 0.0036 (14) |
C9 | 0.0503 (18) | 0.0532 (18) | 0.0428 (19) | −0.0163 (16) | −0.0036 (16) | −0.0039 (15) |
C10 | 0.0484 (18) | 0.0512 (18) | 0.0333 (17) | 0.0017 (15) | −0.0048 (15) | −0.0090 (14) |
C11 | 0.0580 (19) | 0.0622 (19) | 0.0279 (16) | −0.0028 (17) | 0.0062 (15) | 0.0027 (15) |
C12 | 0.0507 (18) | 0.0473 (17) | 0.0318 (16) | −0.0062 (15) | 0.0041 (14) | −0.0011 (14) |
C13 | 0.0464 (17) | 0.0337 (14) | 0.0330 (16) | 0.0046 (13) | −0.0111 (14) | 0.0053 (12) |
C14 | 0.0484 (18) | 0.0389 (15) | 0.0448 (18) | 0.0160 (14) | −0.0135 (15) | 0.0014 (14) |
C15 | 0.0395 (17) | 0.0330 (14) | 0.065 (2) | 0.0150 (13) | −0.0010 (16) | 0.0054 (15) |
C16 | 0.077 (2) | 0.0565 (19) | 0.055 (2) | 0.0282 (18) | 0.0288 (18) | 0.0170 (16) |
C17 | 0.0226 (10) | 0.0220 (10) | 0.0214 (11) | 0.0013 (7) | 0.0030 (7) | 0.0020 (7) |
C17' | 0.039 (2) | 0.244 (7) | 0.073 (3) | 0.060 (3) | 0.034 (2) | 0.069 (4) |
C18 | 0.036 (2) | 0.051 (2) | 0.253 (7) | 0.0062 (18) | 0.006 (3) | 0.002 (3) |
C19 | 0.0503 (17) | 0.0328 (15) | 0.0554 (19) | −0.0014 (14) | 0.0250 (15) | −0.0064 (14) |
N1 | 0.0310 (12) | 0.0356 (11) | 0.0282 (12) | −0.0046 (10) | 0.0012 (10) | 0.0072 (10) |
N2 | 0.0280 (11) | 0.0281 (11) | 0.0289 (12) | 0.0017 (9) | 0.0026 (10) | 0.0038 (9) |
N3 | 0.0346 (12) | 0.0316 (11) | 0.0327 (12) | 0.0045 (10) | −0.0008 (10) | 0.0086 (10) |
N4 | 0.0335 (12) | 0.0304 (11) | 0.0283 (12) | 0.0043 (10) | 0.0023 (10) | 0.0052 (10) |
N5 | 0.0404 (13) | 0.0294 (11) | 0.0349 (13) | 0.0086 (10) | 0.0060 (11) | 0.0003 (10) |
N6 | 0.0359 (12) | 0.0290 (11) | 0.0294 (12) | 0.0009 (10) | 0.0074 (10) | 0.0029 (10) |
P1 | 0.0281 (4) | 0.0337 (4) | 0.0263 (4) | 0.0029 (3) | 0.0009 (3) | 0.0032 (3) |
P2 | 0.0283 (4) | 0.0287 (3) | 0.0281 (4) | 0.0032 (3) | 0.0013 (3) | 0.0036 (3) |
P3 | 0.0296 (4) | 0.0277 (3) | 0.0272 (4) | 0.0042 (3) | 0.0033 (3) | 0.0026 (3) |
Cl1 | 0.0555 (4) | 0.0263 (3) | 0.0369 (4) | 0.0042 (3) | 0.0117 (3) | 0.0005 (3) |
C20 | 0.0177 (11) | 0.0229 (12) | 0.0221 (13) | 0.0068 (10) | 0.0005 (10) | −0.0042 (10) |
C21 | 0.0296 (13) | 0.0248 (12) | 0.0274 (14) | 0.0044 (11) | 0.0030 (11) | −0.0006 (11) |
C22 | 0.0315 (14) | 0.0202 (12) | 0.0395 (16) | 0.0023 (11) | 0.0006 (13) | −0.0065 (12) |
C23 | 0.0271 (14) | 0.0397 (15) | 0.0355 (16) | 0.0066 (12) | −0.0051 (13) | −0.0108 (13) |
C24 | 0.0330 (15) | 0.0512 (16) | 0.0304 (15) | 0.0044 (14) | −0.0023 (13) | 0.0097 (13) |
C25 | 0.0284 (14) | 0.0353 (14) | 0.0313 (15) | −0.0050 (12) | −0.0004 (12) | 0.0040 (12) |
C26 | 0.0161 (11) | 0.0194 (11) | 0.0194 (12) | 0.0037 (10) | −0.0002 (10) | −0.0012 (10) |
C27 | 0.0252 (13) | 0.0258 (12) | 0.0242 (13) | 0.0015 (11) | 0.0048 (11) | 0.0030 (10) |
C28 | 0.0300 (14) | 0.0355 (14) | 0.0217 (13) | 0.0080 (12) | 0.0052 (11) | −0.0026 (11) |
C29 | 0.0273 (13) | 0.0243 (12) | 0.0344 (15) | 0.0071 (11) | 0.0015 (12) | −0.0075 (11) |
C30 | 0.0336 (14) | 0.0216 (12) | 0.0395 (16) | 0.0043 (12) | 0.0061 (13) | 0.0045 (11) |
C31 | 0.0292 (13) | 0.0258 (12) | 0.0274 (14) | 0.0077 (11) | 0.0070 (11) | 0.0023 (11) |
C32 | 0.0273 (13) | 0.0382 (14) | 0.0290 (15) | −0.0093 (12) | −0.0024 (12) | 0.0035 (12) |
C33 | 0.0195 (13) | 0.0610 (18) | 0.0278 (15) | −0.0037 (13) | 0.0010 (12) | 0.0024 (13) |
C34 | 0.0240 (13) | 0.0514 (17) | 0.0332 (16) | 0.0121 (13) | 0.0033 (12) | 0.0011 (13) |
C38 | 0.0329 (14) | 0.0238 (12) | 0.0355 (15) | 0.0042 (11) | 0.0098 (12) | 0.0098 (11) |
N7 | 0.0180 (9) | 0.0202 (9) | 0.0203 (10) | 0.0052 (8) | 0.0035 (8) | 0.0003 (8) |
N8 | 0.0219 (10) | 0.0198 (9) | 0.0179 (10) | 0.0009 (8) | −0.0005 (8) | −0.0007 (8) |
N9 | 0.0210 (10) | 0.0182 (9) | 0.0214 (10) | 0.0014 (8) | 0.0022 (8) | 0.0028 (8) |
N10 | 0.0231 (10) | 0.0221 (10) | 0.0260 (11) | 0.0008 (9) | 0.0033 (9) | 0.0033 (9) |
N11 | 0.0210 (10) | 0.0285 (11) | 0.0264 (11) | 0.0074 (9) | 0.0043 (9) | 0.0010 (9) |
N12 | 0.0290 (11) | 0.0227 (10) | 0.0265 (11) | −0.0005 (9) | 0.0004 (10) | 0.0061 (9) |
P4 | 0.0189 (3) | 0.0178 (3) | 0.0203 (3) | 0.0031 (3) | 0.0025 (3) | 0.0007 (2) |
P5 | 0.0198 (3) | 0.0222 (3) | 0.0192 (3) | 0.0035 (3) | 0.0024 (3) | 0.0013 (3) |
P6 | 0.0250 (3) | 0.0179 (3) | 0.0196 (3) | 0.0005 (3) | 0.0003 (3) | 0.0015 (2) |
Cl2 | 0.0392 (3) | 0.0290 (3) | 0.0205 (3) | −0.0045 (3) | 0.0055 (3) | 0.0011 (3) |
C39 | 0.0275 (13) | 0.0255 (12) | 0.0243 (13) | 0.0025 (11) | −0.0015 (11) | 0.0036 (11) |
C40 | 0.0329 (15) | 0.0549 (17) | 0.0317 (15) | 0.0071 (14) | 0.0037 (13) | 0.0097 (13) |
C41 | 0.0287 (15) | 0.086 (2) | 0.0382 (17) | −0.0025 (16) | −0.0023 (14) | 0.0210 (16) |
C42 | 0.0412 (17) | 0.0600 (18) | 0.0265 (15) | −0.0114 (15) | −0.0106 (13) | 0.0088 (14) |
C43 | 0.0459 (17) | 0.0446 (16) | 0.0220 (14) | 0.0013 (14) | −0.0024 (13) | −0.0019 (12) |
C44 | 0.0302 (14) | 0.0362 (14) | 0.0279 (15) | 0.0062 (12) | 0.0023 (12) | −0.0014 (12) |
C45 | 0.0294 (13) | 0.0280 (13) | 0.0209 (13) | 0.0071 (11) | −0.0009 (11) | −0.0025 (11) |
C46 | 0.0450 (16) | 0.0283 (14) | 0.0427 (17) | 0.0100 (13) | 0.0113 (14) | 0.0017 (12) |
C47 | 0.072 (2) | 0.0278 (14) | 0.058 (2) | 0.0134 (15) | 0.0222 (17) | 0.0096 (14) |
C48 | 0.0621 (19) | 0.0434 (16) | 0.0424 (18) | 0.0300 (15) | 0.0098 (16) | 0.0001 (14) |
C49 | 0.0407 (16) | 0.0453 (16) | 0.0304 (15) | 0.0169 (14) | 0.0039 (13) | 0.0019 (13) |
C50 | 0.0332 (15) | 0.0395 (15) | 0.0258 (14) | 0.0026 (13) | −0.0014 (12) | 0.0023 (12) |
C51 | 0.067 (2) | 0.0334 (15) | 0.0276 (15) | −0.0011 (15) | 0.0143 (14) | −0.0026 (12) |
C52 | 0.0596 (19) | 0.0429 (16) | 0.0355 (17) | 0.0012 (15) | 0.0199 (15) | −0.0102 (14) |
C53 | 0.0496 (17) | 0.0421 (16) | 0.0402 (17) | 0.0157 (14) | 0.0195 (14) | 0.0006 (13) |
C54 | 0.0334 (14) | 0.0327 (14) | 0.0281 (15) | 0.0142 (12) | 0.0023 (12) | −0.0012 (12) |
C55 | 0.0418 (16) | 0.0306 (14) | 0.0385 (16) | 0.0126 (13) | 0.0098 (13) | 0.0064 (12) |
C56 | 0.0465 (16) | 0.0224 (13) | 0.0355 (16) | 0.0048 (13) | 0.0032 (14) | −0.0040 (12) |
C57 | 0.0418 (15) | 0.0230 (13) | 0.0363 (16) | 0.0012 (12) | 0.0073 (13) | −0.0012 (12) |
N13 | 0.0297 (11) | 0.0241 (10) | 0.0259 (11) | −0.0021 (9) | 0.0034 (9) | 0.0015 (9) |
N14 | 0.0340 (11) | 0.0200 (10) | 0.0228 (11) | 0.0006 (9) | 0.0018 (9) | 0.0035 (8) |
N15 | 0.0368 (12) | 0.0236 (10) | 0.0247 (11) | −0.0036 (10) | 0.0073 (10) | −0.0014 (9) |
N16 | 0.0526 (14) | 0.0227 (11) | 0.0252 (12) | −0.0026 (11) | 0.0092 (11) | 0.0021 (9) |
N17 | 0.0353 (12) | 0.0297 (11) | 0.0239 (11) | 0.0085 (10) | 0.0055 (10) | −0.0011 (9) |
N18 | 0.0331 (12) | 0.0225 (10) | 0.0221 (11) | 0.0041 (9) | 0.0042 (10) | 0.0043 (9) |
P7 | 0.0271 (3) | 0.0197 (3) | 0.0205 (3) | 0.0019 (3) | 0.0015 (3) | −0.0013 (3) |
P8 | 0.0321 (4) | 0.0235 (3) | 0.0210 (3) | 0.0010 (3) | 0.0039 (3) | −0.0005 (3) |
P9 | 0.0268 (3) | 0.0222 (3) | 0.0224 (3) | 0.0027 (3) | 0.0001 (3) | 0.0015 (3) |
Cl3 | 0.0284 (3) | 0.0375 (3) | 0.0393 (4) | 0.0055 (3) | 0.0007 (3) | 0.0109 (3) |
C1—C2 | 1.371 (4) | C33—H33B | 0.9900 |
C1—C6 | 1.402 (4) | C34—N11 | 1.475 (3) |
C1—P1 | 1.806 (3) | C34—H34A | 0.9900 |
C2—C3 | 1.428 (5) | C34—H34B | 0.9900 |
C2—H2 | 0.9500 | C35—N11 | 1.476 (3) |
C3—C4 | 1.376 (6) | C35—C36 | 1.474 (4) |
C3—H3 | 0.9500 | C35—C36' | 1.6000 (11) |
C4—C5 | 1.369 (6) | C35—H35A | 0.9900 |
C4—H4 | 0.9500 | C35—H35B | 0.9900 |
C5—C6 | 1.373 (5) | C36—C37 | 1.483 (5) |
C5—H5 | 0.9500 | C36—H36A | 0.9900 |
C6—H6 | 0.9500 | C36—H36B | 0.9900 |
C7—C12 | 1.379 (4) | C36'—C37 | 1.279 (6) |
C7—C8 | 1.384 (4) | C36'—H36C | 0.9900 |
C7—P1 | 1.804 (3) | C36'—H36D | 0.9900 |
C8—C9 | 1.390 (4) | C37—C38 | 1.540 (4) |
C8—H8 | 0.9500 | C37—H37A | 0.9900 |
C9—C10 | 1.378 (4) | C37—H37B | 0.9900 |
C9—H9 | 0.9500 | C38—N12 | 1.466 (3) |
C10—C11 | 1.360 (4) | C38—H38A | 0.9900 |
C10—H10 | 0.9500 | C38—H38B | 0.9900 |
C11—C12 | 1.387 (4) | N7—P5 | 1.601 (2) |
C11—H11 | 0.9500 | N7—P4 | 1.614 (2) |
C12—H12 | 0.9500 | N8—P6 | 1.577 (2) |
C13—N4 | 1.483 (3) | N8—P5 | 1.612 (2) |
C13—C14 | 1.513 (4) | N9—P6 | 1.599 (2) |
C13—H13A | 0.9900 | N9—P4 | 1.616 (2) |
C13—H13B | 0.9900 | N10—P5 | 1.6582 (15) |
C14—C15 | 1.516 (4) | N10—H10N | 0.9597 (10) |
C14—H14A | 0.9900 | N11—P5 | 1.657 (2) |
C14—H14B | 0.9900 | N12—P6 | 1.643 (2) |
C15—N5 | 1.476 (4) | N12—H12N | 0.73 (3) |
C15—H15A | 0.9900 | P6—Cl2 | 2.0440 (10) |
C15—H15B | 0.9900 | C39—C44 | 1.395 (4) |
C16—N5 | 1.463 (3) | C39—C40 | 1.399 (4) |
C16—C17 | 1.5492 (10) | C39—P7 | 1.799 (2) |
C16—C17' | 1.5503 (10) | C40—C41 | 1.389 (4) |
C16—H16A | 0.9900 | C40—H40 | 0.9500 |
C16—H16B | 0.9900 | C41—C42 | 1.380 (4) |
C17—C18 | 1.5501 (10) | C41—H41 | 0.9500 |
C17—H17A | 0.9900 | C42—C43 | 1.380 (4) |
C17—H17B | 0.9900 | C42—H42 | 0.9500 |
C17'—C18 | 1.5467 (10) | C43—C44 | 1.376 (4) |
C17'—H17C | 0.9900 | C43—H43 | 0.9500 |
C17'—H17D | 0.9900 | C44—H44 | 0.9500 |
C18—C19 | 1.433 (4) | C45—C50 | 1.382 (4) |
C18—H18A | 0.9900 | C45—C46 | 1.390 (4) |
C18—H18B | 0.9900 | C45—P7 | 1.805 (3) |
C19—N6 | 1.467 (3) | C46—C47 | 1.388 (4) |
C19—H19A | 0.9900 | C46—H46 | 0.9500 |
C19—H19B | 0.9900 | C47—C48 | 1.390 (4) |
N1—P2 | 1.600 (2) | C47—H47 | 0.9500 |
N1—P1 | 1.601 (2) | C48—C49 | 1.349 (4) |
N2—P3 | 1.565 (2) | C48—H48 | 0.9500 |
N2—P2 | 1.605 (2) | C49—C50 | 1.385 (4) |
N3—P3 | 1.599 (2) | C49—H49 | 0.9500 |
N3—P1 | 1.606 (2) | C50—H50 | 0.9500 |
N4—P2 | 1.646 (2) | C51—N16 | 1.459 (3) |
N4—H4N | 0.84 (2) | C51—C52 | 1.509 (4) |
N5—P2 | 1.674 (2) | C51—H51A | 0.9900 |
N6—P3 | 1.644 (2) | C51—H51B | 0.9900 |
N6—H6N | 0.91 (3) | C52—C53 | 1.499 (4) |
P3—Cl1 | 2.0439 (11) | C52—H52A | 0.9900 |
C20—C25 | 1.388 (4) | C52—H52B | 0.9900 |
C20—C21 | 1.395 (3) | C53—N17 | 1.462 (3) |
C20—P4 | 1.797 (2) | C53—H53A | 0.9900 |
C21—C22 | 1.393 (3) | C53—H53B | 0.9900 |
C21—H21 | 0.9500 | C54—N17 | 1.476 (3) |
C22—C23 | 1.371 (4) | C54—C55 | 1.540 (3) |
C22—H22 | 0.9500 | C54—H54A | 0.9900 |
C23—C24 | 1.396 (4) | C54—H54B | 0.9900 |
C23—H23 | 0.9500 | C55—C56 | 1.521 (4) |
C24—C25 | 1.385 (4) | C55—H55A | 0.9900 |
C24—H24 | 0.9500 | C55—H55B | 0.9900 |
C25—H25 | 0.9500 | C56—C57 | 1.521 (4) |
C26—C31 | 1.391 (3) | C56—H56A | 0.9900 |
C26—C27 | 1.398 (3) | C56—H56B | 0.9900 |
C26—P4 | 1.803 (2) | C57—N18 | 1.464 (3) |
C27—C28 | 1.390 (3) | C57—H57A | 0.9900 |
C27—H27 | 0.9500 | C57—H57B | 0.9900 |
C28—C29 | 1.378 (4) | N13—P7 | 1.599 (2) |
C28—H28 | 0.9500 | N13—P8 | 1.617 (2) |
C29—C30 | 1.383 (4) | N14—P9 | 1.570 (2) |
C29—H29 | 0.9500 | N14—P8 | 1.606 (2) |
C30—C31 | 1.381 (3) | N15—P9 | 1.587 (2) |
C30—H30 | 0.9500 | N15—P7 | 1.611 (2) |
C31—H31 | 0.9500 | N16—P8 | 1.634 (2) |
C32—N10 | 1.471 (3) | N16—H16N | 0.80 (2) |
C32—C33 | 1.519 (4) | N17—P8 | 1.657 (2) |
C32—H32A | 0.9900 | N18—P9 | 1.618 (2) |
C32—H32B | 0.9900 | N18—H18N | 0.76 (2) |
C33—C34 | 1.514 (4) | P9—Cl3 | 2.0783 (10) |
C33—H33A | 0.9900 | ||
C2—C1—C6 | 118.9 (3) | N11—C35—C36 | 125.34 (18) |
C2—C1—P1 | 122.6 (2) | N11—C35—C36' | 88.3 (3) |
C6—C1—P1 | 118.4 (2) | C36—C35—C36' | 38.0 (3) |
C1—C2—C3 | 119.1 (3) | N11—C35—H35A | 106.1 |
C1—C2—H2 | 120.4 | C36—C35—H35A | 105.9 |
C3—C2—H2 | 120.4 | C36'—C35—H35A | 131.4 |
C4—C3—C2 | 119.6 (4) | N11—C35—H35B | 106.1 |
C4—C3—H3 | 120.2 | C36—C35—H35B | 105.9 |
C2—C3—H3 | 120.2 | C36'—C35—H35B | 114.0 |
C5—C4—C3 | 121.6 (4) | H35A—C35—H35B | 106.3 |
C5—C4—H4 | 119.2 | C37—C36—C35 | 115.4 (3) |
C3—C4—H4 | 119.2 | C37—C36—H36A | 108.4 |
C4—C5—C6 | 118.4 (4) | C35—C36—H36A | 108.6 |
C4—C5—H5 | 120.8 | C37—C36—H36B | 108.4 |
C6—C5—H5 | 120.8 | C35—C36—H36B | 108.3 |
C5—C6—C1 | 122.4 (4) | H36A—C36—H36B | 107.5 |
C5—C6—H6 | 118.8 | C37—C36'—C35 | 120.1 (4) |
C1—C6—H6 | 118.8 | C37—C36'—H36C | 107.6 |
C12—C7—C8 | 118.9 (2) | C35—C36'—H36C | 107.6 |
C12—C7—P1 | 120.9 (2) | C37—C36'—H36D | 106.9 |
C8—C7—P1 | 120.2 (2) | C35—C36'—H36D | 106.9 |
C7—C8—C9 | 120.2 (3) | H36C—C36'—H36D | 107.0 |
C7—C8—H8 | 119.9 | C36'—C37—C36 | 42.0 (3) |
C9—C8—H8 | 119.9 | C36'—C37—C38 | 128.2 (3) |
C10—C9—C8 | 120.0 (3) | C36—C37—C38 | 115.8 (3) |
C10—C9—H9 | 120.0 | C36'—C37—H37A | 66.4 |
C8—C9—H9 | 120.0 | C36—C37—H37A | 108.4 |
C11—C10—C9 | 120.0 (3) | C38—C37—H37A | 108.3 |
C11—C10—H10 | 120.0 | C36'—C37—H37B | 122.6 |
C9—C10—H10 | 120.0 | C36—C37—H37B | 108.3 |
C10—C11—C12 | 120.3 (3) | C38—C37—H37B | 108.3 |
C10—C11—H11 | 119.9 | H37A—C37—H37B | 107.4 |
C12—C11—H11 | 119.9 | N12—C38—C37 | 109.6 (2) |
C7—C12—C11 | 120.7 (3) | N12—C38—H38A | 109.8 |
C7—C12—H12 | 119.7 | C37—C38—H38A | 109.8 |
C11—C12—H12 | 119.7 | N12—C38—H38B | 109.7 |
N4—C13—C14 | 110.3 (2) | C37—C38—H38B | 109.7 |
N4—C13—H13A | 109.6 | H38A—C38—H38B | 108.2 |
C14—C13—H13A | 109.6 | P5—N7—P4 | 118.73 (12) |
N4—C13—H13B | 109.6 | P6—N8—P5 | 124.13 (12) |
C14—C13—H13B | 109.6 | P6—N9—P4 | 117.73 (12) |
H13A—C13—H13B | 108.1 | C32—N10—P5 | 116.62 (14) |
C13—C14—C15 | 111.0 (2) | C32—N10—H10N | 110.0 (4) |
C13—C14—H14A | 109.4 | P5—N10—H10N | 114.8 (3) |
C15—C14—H14A | 109.4 | C34—N11—C35 | 113.81 (18) |
C13—C14—H14B | 109.4 | C34—N11—P5 | 120.43 (17) |
C15—C14—H14B | 109.4 | C35—N11—P5 | 119.07 (14) |
H14A—C14—H14B | 108.0 | C38—N12—P6 | 115.73 (17) |
N5—C15—C14 | 113.1 (2) | C38—N12—H12N | 120 (2) |
N5—C15—H15A | 109.0 | P6—N12—H12N | 109 (2) |
C14—C15—H15A | 109.0 | N7—P4—N9 | 115.81 (10) |
N5—C15—H15B | 109.0 | N7—P4—C20 | 106.98 (11) |
C14—C15—H15B | 109.0 | N9—P4—C20 | 107.62 (11) |
H15A—C15—H15B | 107.8 | N7—P4—C26 | 107.96 (10) |
N5—C16—C17 | 141.22 (14) | N9—P4—C26 | 109.84 (11) |
N5—C16—C17' | 105.04 (13) | C20—P4—C26 | 108.38 (11) |
C17—C16—C17' | 37.78 (9) | N7—P5—N8 | 114.07 (11) |
N5—C16—H16A | 101.7 | N7—P5—N10 | 110.02 (10) |
C17—C16—H16A | 101.7 | N8—P5—N10 | 107.55 (9) |
C17'—C16—H16A | 131.9 | N7—P5—N11 | 108.66 (10) |
N5—C16—H16B | 101.7 | N8—P5—N11 | 111.35 (11) |
C17—C16—H16B | 101.7 | N10—P5—N11 | 104.78 (10) |
C17'—C16—H16B | 108.0 | N8—P6—N9 | 116.46 (10) |
H16A—C16—H16B | 104.7 | N8—P6—N12 | 111.08 (11) |
C16—C17—C18 | 115.60 (15) | N9—P6—N12 | 112.50 (10) |
C16—C17—H17A | 108.4 | N8—P6—Cl2 | 108.62 (8) |
C18—C17—H17A | 108.4 | N9—P6—Cl2 | 107.51 (8) |
C16—C17—H17B | 108.4 | N12—P6—Cl2 | 99.10 (9) |
C18—C17—H17B | 108.4 | C44—C39—C40 | 119.0 (2) |
H17A—C17—H17B | 107.4 | C44—C39—P7 | 121.3 (2) |
C18—C17'—C16 | 115.73 (15) | C40—C39—P7 | 119.7 (2) |
C18—C17'—H17C | 108.4 | C41—C40—C39 | 119.0 (3) |
C16—C17'—H17C | 108.3 | C41—C40—H40 | 120.5 |
C18—C17'—H17D | 108.3 | C39—C40—H40 | 120.5 |
C16—C17'—H17D | 108.3 | C42—C41—C40 | 121.5 (3) |
H17C—C17'—H17D | 107.4 | C42—C41—H41 | 119.2 |
C19—C18—C17' | 120.8 (2) | C40—C41—H41 | 119.2 |
C19—C18—C17 | 121.8 (2) | C41—C42—C43 | 119.1 (3) |
C17'—C18—C17 | 37.81 (10) | C41—C42—H42 | 120.4 |
C19—C18—H18A | 106.9 | C43—C42—H42 | 120.4 |
C17'—C18—H18A | 130.9 | C44—C43—C42 | 120.5 (3) |
C17—C18—H18A | 106.9 | C44—C43—H43 | 119.7 |
C19—C18—H18B | 106.9 | C42—C43—H43 | 119.7 |
C17'—C18—H18B | 71.8 | C43—C44—C39 | 120.7 (3) |
C17—C18—H18B | 106.9 | C43—C44—H44 | 119.6 |
H18A—C18—H18B | 106.7 | C39—C44—H44 | 119.6 |
C18—C19—N6 | 118.8 (2) | C50—C45—C46 | 118.8 (2) |
C18—C19—H19A | 107.6 | C50—C45—P7 | 122.0 (2) |
N6—C19—H19A | 107.6 | C46—C45—P7 | 119.1 (2) |
C18—C19—H19B | 107.6 | C45—C46—C47 | 120.2 (3) |
N6—C19—H19B | 107.6 | C45—C46—H46 | 119.9 |
H19A—C19—H19B | 107.0 | C47—C46—H46 | 119.9 |
P2—N1—P1 | 122.35 (13) | C48—C47—C46 | 119.3 (3) |
P3—N2—P2 | 123.78 (13) | C48—C47—H47 | 120.3 |
P3—N3—P1 | 120.82 (14) | C46—C47—H47 | 120.3 |
C13—N4—P2 | 115.92 (18) | C49—C48—C47 | 121.0 (3) |
C13—N4—H4N | 109.2 (18) | C49—C48—H48 | 119.5 |
P2—N4—H4N | 112.9 (18) | C47—C48—H48 | 119.5 |
C16—N5—C15 | 112.6 (2) | C48—C49—C50 | 119.8 (3) |
C16—N5—P2 | 116.59 (15) | C48—C49—H49 | 120.1 |
C15—N5—P2 | 120.52 (18) | C50—C49—H49 | 120.1 |
C19—N6—P3 | 116.33 (18) | C45—C50—C49 | 120.9 (3) |
C19—N6—H6N | 110.9 (18) | C45—C50—H50 | 119.5 |
P3—N6—H6N | 116.5 (18) | C49—C50—H50 | 119.5 |
N1—P1—N3 | 116.79 (12) | N16—C51—C52 | 110.9 (2) |
N1—P1—C7 | 108.74 (12) | N16—C51—H51A | 109.5 |
N3—P1—C7 | 106.52 (12) | C52—C51—H51A | 109.5 |
N1—P1—C1 | 111.37 (13) | N16—C51—H51B | 109.5 |
N3—P1—C1 | 108.00 (13) | C52—C51—H51B | 109.5 |
C7—P1—C1 | 104.65 (13) | H51A—C51—H51B | 108.1 |
N1—P2—N2 | 114.90 (11) | C53—C52—C51 | 111.6 (2) |
N1—P2—N4 | 108.00 (12) | C53—C52—H52A | 109.3 |
N2—P2—N4 | 109.58 (11) | C51—C52—H52A | 109.3 |
N1—P2—N5 | 109.79 (12) | C53—C52—H52B | 109.3 |
N2—P2—N5 | 109.40 (12) | C51—C52—H52B | 109.3 |
N4—P2—N5 | 104.68 (11) | H52A—C52—H52B | 108.0 |
N2—P3—N3 | 116.99 (12) | N17—C53—C52 | 114.2 (2) |
N2—P3—N6 | 112.73 (12) | N17—C53—H53A | 108.7 |
N3—P3—N6 | 110.54 (12) | C52—C53—H53A | 108.7 |
N2—P3—Cl1 | 106.73 (9) | N17—C53—H53B | 108.7 |
N3—P3—Cl1 | 108.48 (9) | C52—C53—H53B | 108.7 |
N6—P3—Cl1 | 99.77 (8) | H53A—C53—H53B | 107.6 |
C25—C20—C21 | 118.8 (2) | N17—C54—C55 | 116.3 (2) |
C25—C20—P4 | 119.40 (18) | N17—C54—H54A | 108.2 |
C21—C20—P4 | 121.79 (19) | C55—C54—H54A | 108.2 |
C20—C21—C22 | 119.9 (2) | N17—C54—H54B | 108.2 |
C20—C21—H21 | 120.0 | C55—C54—H54B | 108.2 |
C22—C21—H21 | 120.0 | H54A—C54—H54B | 107.4 |
C23—C22—C21 | 121.2 (2) | C56—C55—C54 | 117.3 (2) |
C23—C22—H22 | 119.4 | C56—C55—H55A | 108.0 |
C21—C22—H22 | 119.4 | C54—C55—H55A | 108.0 |
C22—C23—C24 | 118.9 (2) | C56—C55—H55B | 108.0 |
C22—C23—H23 | 120.5 | C54—C55—H55B | 108.0 |
C24—C23—H23 | 120.5 | H55A—C55—H55B | 107.2 |
C25—C24—C23 | 120.3 (3) | C57—C56—C55 | 115.9 (2) |
C25—C24—H24 | 119.9 | C57—C56—H56A | 108.3 |
C23—C24—H24 | 119.9 | C55—C56—H56A | 108.3 |
C24—C25—C20 | 120.8 (2) | C57—C56—H56B | 108.3 |
C24—C25—H25 | 119.6 | C55—C56—H56B | 108.3 |
C20—C25—H25 | 119.6 | H56A—C56—H56B | 107.4 |
C31—C26—C27 | 118.5 (2) | N18—C57—C56 | 114.1 (2) |
C31—C26—P4 | 120.77 (18) | N18—C57—H57A | 108.7 |
C27—C26—P4 | 120.51 (18) | C56—C57—H57A | 108.7 |
C28—C27—C26 | 120.3 (2) | N18—C57—H57B | 108.7 |
C28—C27—H27 | 119.9 | C56—C57—H57B | 108.7 |
C26—C27—H27 | 119.9 | H57A—C57—H57B | 107.6 |
C29—C28—C27 | 120.4 (2) | P7—N13—P8 | 121.84 (13) |
C29—C28—H28 | 119.8 | P9—N14—P8 | 120.57 (13) |
C27—C28—H28 | 119.8 | P9—N15—P7 | 118.08 (13) |
C28—C29—C30 | 119.8 (2) | C51—N16—P8 | 119.61 (18) |
C28—C29—H29 | 120.1 | C51—N16—H16N | 113.8 (17) |
C30—C29—H29 | 120.1 | P8—N16—H16N | 111.0 (17) |
C31—C30—C29 | 120.2 (2) | C53—N17—C54 | 114.3 (2) |
C31—C30—H30 | 119.9 | C53—N17—P8 | 125.57 (18) |
C29—C30—H30 | 119.9 | C54—N17—P8 | 117.22 (17) |
C30—C31—C26 | 120.9 (2) | C57—N18—P9 | 124.45 (18) |
C30—C31—H31 | 119.5 | C57—N18—H18N | 115.4 (18) |
C26—C31—H31 | 119.6 | P9—N18—H18N | 113.6 (18) |
N10—C32—C33 | 111.05 (19) | N13—P7—N15 | 118.26 (11) |
N10—C32—H32A | 109.5 | N13—P7—C39 | 107.85 (12) |
C33—C32—H32A | 109.4 | N15—P7—C39 | 109.02 (11) |
N10—C32—H32B | 109.4 | N13—P7—C45 | 109.70 (12) |
C33—C32—H32B | 109.4 | N15—P7—C45 | 109.07 (12) |
H32A—C32—H32B | 108.0 | C39—P7—C45 | 101.65 (11) |
C34—C33—C32 | 112.1 (2) | N14—P8—N13 | 112.50 (11) |
C34—C33—H33A | 109.2 | N14—P8—N16 | 110.26 (12) |
C32—C33—H33A | 109.2 | N13—P8—N16 | 108.47 (11) |
C34—C33—H33B | 109.2 | N14—P8—N17 | 109.46 (11) |
C32—C33—H33B | 109.2 | N13—P8—N17 | 111.44 (11) |
H33A—C33—H33B | 107.9 | N16—P8—N17 | 104.40 (12) |
N11—C34—C33 | 112.4 (2) | N14—P9—N15 | 118.85 (11) |
N11—C34—H34A | 109.1 | N14—P9—N18 | 111.35 (11) |
C33—C34—H34A | 109.1 | N15—P9—N18 | 108.84 (11) |
N11—C34—H34B | 109.1 | N14—P9—Cl3 | 104.28 (9) |
C33—C34—H34B | 109.1 | N15—P9—Cl3 | 107.12 (9) |
H34A—C34—H34B | 107.9 | N18—P9—Cl3 | 105.40 (9) |
C6—C1—C2—C3 | −0.6 (4) | C37—C38—N12—P6 | 87.8 (2) |
P1—C1—C2—C3 | 179.3 (2) | P5—N7—P4—N9 | −38.94 (16) |
C1—C2—C3—C4 | 0.5 (5) | P5—N7—P4—C20 | −158.89 (12) |
C2—C3—C4—C5 | −0.4 (5) | P5—N7—P4—C26 | 84.64 (14) |
C3—C4—C5—C6 | 0.4 (5) | P6—N9—P4—N7 | 34.09 (16) |
C4—C5—C6—C1 | −0.5 (5) | P6—N9—P4—C20 | 153.69 (13) |
C2—C1—C6—C5 | 0.6 (5) | P6—N9—P4—C26 | −88.51 (15) |
P1—C1—C6—C5 | −179.3 (3) | C25—C20—P4—N7 | −48.9 (2) |
C12—C7—C8—C9 | 0.9 (4) | C21—C20—P4—N7 | 128.9 (2) |
P1—C7—C8—C9 | −179.3 (2) | C25—C20—P4—N9 | −174.0 (2) |
C7—C8—C9—C10 | 0.2 (5) | C21—C20—P4—N9 | 3.8 (2) |
C8—C9—C10—C11 | −0.8 (5) | C25—C20—P4—C26 | 67.2 (2) |
C9—C10—C11—C12 | 0.2 (5) | C21—C20—P4—C26 | −114.9 (2) |
C8—C7—C12—C11 | −1.5 (4) | C31—C26—P4—N7 | 26.0 (2) |
P1—C7—C12—C11 | 178.7 (2) | C27—C26—P4—N7 | −148.09 (18) |
C10—C11—C12—C7 | 1.0 (5) | C31—C26—P4—N9 | 153.11 (18) |
N4—C13—C14—C15 | −64.6 (3) | C27—C26—P4—N9 | −21.0 (2) |
C13—C14—C15—N5 | 55.1 (3) | C31—C26—P4—C20 | −89.6 (2) |
N5—C16—C17—C18 | 78.5 (3) | C27—C26—P4—C20 | 96.4 (2) |
C17'—C16—C17—C18 | 56.87 (14) | P4—N7—P5—N8 | 14.50 (16) |
N5—C16—C17'—C18 | 136.68 (16) | P4—N7—P5—N10 | −106.44 (13) |
C17—C16—C17'—C18 | −57.17 (14) | P4—N7—P5—N11 | 139.37 (12) |
C16—C17'—C18—C19 | −46.4 (2) | P6—N8—P5—N7 | 15.59 (18) |
C16—C17'—C18—C17 | 57.05 (14) | P6—N8—P5—N10 | 137.90 (13) |
C16—C17—C18—C19 | 43.6 (3) | P6—N8—P5—N11 | −107.84 (15) |
C16—C17—C18—C17' | −57.01 (14) | C32—N10—P5—N7 | −158.18 (15) |
C17'—C18—C19—N6 | −73.1 (3) | C32—N10—P5—N8 | 77.03 (17) |
C17—C18—C19—N6 | −117.7 (2) | C32—N10—P5—N11 | −41.54 (17) |
C14—C13—N4—P2 | 60.5 (3) | C34—N11—P5—N7 | 153.58 (18) |
C17—C16—N5—C15 | 40.3 (3) | C35—N11—P5—N7 | −56.87 (18) |
C17'—C16—N5—C15 | 53.9 (2) | C34—N11—P5—N8 | −80.0 (2) |
C17—C16—N5—P2 | −105.2 (2) | C35—N11—P5—N8 | 69.59 (17) |
C17'—C16—N5—P2 | −91.62 (16) | C34—N11—P5—N10 | 36.0 (2) |
C14—C15—N5—C16 | 173.8 (2) | C35—N11—P5—N10 | −174.44 (14) |
C14—C15—N5—P2 | −42.3 (3) | P5—N8—P6—N9 | −20.01 (18) |
C18—C19—N6—P3 | 97.7 (3) | P5—N8—P6—N12 | 110.52 (15) |
P2—N1—P1—N3 | −14.1 (2) | P5—N8—P6—Cl2 | −141.50 (12) |
P2—N1—P1—C7 | −134.63 (16) | P4—N9—P6—N8 | −5.86 (17) |
P2—N1—P1—C1 | 110.57 (17) | P4—N9—P6—N12 | −135.73 (13) |
P3—N3—P1—N1 | 19.6 (2) | P4—N9—P6—Cl2 | 116.21 (11) |
P3—N3—P1—C7 | 141.23 (15) | C38—N12—P6—N8 | −65.00 (19) |
P3—N3—P1—C1 | −106.83 (17) | C38—N12—P6—N9 | 67.57 (19) |
C12—C7—P1—N1 | 121.0 (2) | C38—N12—P6—Cl2 | −179.10 (15) |
C8—C7—P1—N1 | −58.7 (3) | C44—C39—C40—C41 | 3.1 (4) |
C12—C7—P1—N3 | −5.6 (3) | P7—C39—C40—C41 | −175.3 (2) |
C8—C7—P1—N3 | 174.7 (2) | C39—C40—C41—C42 | −1.3 (5) |
C12—C7—P1—C1 | −119.9 (2) | C40—C41—C42—C43 | −0.9 (5) |
C8—C7—P1—C1 | 60.4 (3) | C41—C42—C43—C44 | 1.1 (4) |
C2—C1—P1—N1 | 13.5 (3) | C42—C43—C44—C39 | 0.8 (4) |
C6—C1—P1—N1 | −166.6 (2) | C40—C39—C44—C43 | −2.9 (4) |
C2—C1—P1—N3 | 143.0 (2) | P7—C39—C44—C43 | 175.5 (2) |
C6—C1—P1—N3 | −37.1 (3) | C50—C45—C46—C47 | 0.9 (4) |
C2—C1—P1—C7 | −103.8 (2) | P7—C45—C46—C47 | 176.5 (2) |
C6—C1—P1—C7 | 76.1 (2) | C45—C46—C47—C48 | −1.0 (4) |
P1—N1—P2—N2 | −3.8 (2) | C46—C47—C48—C49 | 0.5 (5) |
P1—N1—P2—N4 | −126.44 (15) | C47—C48—C49—C50 | 0.1 (4) |
P1—N1—P2—N5 | 119.98 (16) | C46—C45—C50—C49 | −0.3 (4) |
P3—N2—P2—N1 | 18.3 (2) | P7—C45—C50—C49 | −175.8 (2) |
P3—N2—P2—N4 | 140.11 (15) | C48—C49—C50—C45 | −0.2 (4) |
P3—N2—P2—N5 | −105.66 (17) | N16—C51—C52—C53 | −63.8 (3) |
C13—N4—P2—N1 | −159.13 (17) | C51—C52—C53—N17 | 48.4 (3) |
C13—N4—P2—N2 | 75.04 (19) | N17—C54—C55—C56 | 49.1 (3) |
C13—N4—P2—N5 | −42.2 (2) | C54—C55—C56—C57 | 84.5 (3) |
C16—N5—P2—N1 | −67.88 (18) | C55—C56—C57—N18 | −48.3 (3) |
C15—N5—P2—N1 | 149.5 (2) | C52—C51—N16—P8 | 56.0 (3) |
C16—N5—P2—N2 | 59.07 (18) | C52—C53—N17—C54 | 173.6 (2) |
C15—N5—P2—N2 | −83.6 (2) | C52—C53—N17—P8 | −26.2 (3) |
C16—N5—P2—N4 | 176.42 (14) | C55—C54—N17—C53 | 54.9 (3) |
C15—N5—P2—N4 | 33.8 (2) | C55—C54—N17—P8 | −107.0 (2) |
P2—N2—P3—N3 | −13.4 (2) | C56—C57—N18—P9 | −70.5 (3) |
P2—N2—P3—N6 | 116.45 (16) | P8—N13—P7—N15 | −9.7 (2) |
P2—N2—P3—Cl1 | −135.01 (13) | P8—N13—P7—C39 | −133.83 (15) |
P1—N3—P3—N2 | −6.5 (2) | P8—N13—P7—C45 | 116.25 (15) |
P1—N3—P3—N6 | −137.34 (15) | P9—N15—P7—N13 | 17.93 (19) |
P1—N3—P3—Cl1 | 114.21 (14) | P9—N15—P7—C39 | 141.53 (14) |
C19—N6—P3—N2 | −72.9 (2) | P9—N15—P7—C45 | −108.28 (15) |
C19—N6—P3—N3 | 60.1 (2) | C44—C39—P7—N13 | −162.3 (2) |
C19—N6—P3—Cl1 | 174.17 (18) | C40—C39—P7—N13 | 16.0 (2) |
C25—C20—C21—C22 | 0.9 (4) | C44—C39—P7—N15 | 68.1 (2) |
P4—C20—C21—C22 | −176.97 (19) | C40—C39—P7—N15 | −113.5 (2) |
C20—C21—C22—C23 | 0.8 (4) | C44—C39—P7—C45 | −47.0 (2) |
C21—C22—C23—C24 | −1.6 (4) | C40—C39—P7—C45 | 131.4 (2) |
C22—C23—C24—C25 | 0.7 (4) | C50—C45—P7—N13 | −143.0 (2) |
C23—C24—C25—C20 | 1.0 (4) | C46—C45—P7—N13 | 41.5 (2) |
C21—C20—C25—C24 | −1.8 (4) | C50—C45—P7—N15 | −12.0 (2) |
P4—C20—C25—C24 | 176.1 (2) | C46—C45—P7—N15 | 172.5 (2) |
C31—C26—C27—C28 | −0.1 (3) | C50—C45—P7—C39 | 103.0 (2) |
P4—C26—C27—C28 | 174.07 (18) | C46—C45—P7—C39 | −72.4 (2) |
C26—C27—C28—C29 | −0.4 (4) | P9—N14—P8—N13 | 35.02 (18) |
C27—C28—C29—C30 | 1.2 (4) | P9—N14—P8—N16 | 156.24 (13) |
C28—C29—C30—C31 | −1.3 (4) | P9—N14—P8—N17 | −89.45 (16) |
C29—C30—C31—C26 | 0.8 (4) | P7—N13—P8—N14 | −15.73 (19) |
C27—C26—C31—C30 | 0.0 (4) | P7—N13—P8—N16 | −137.98 (15) |
P4—C26—C31—C30 | −174.24 (19) | P7—N13—P8—N17 | 107.64 (15) |
N10—C32—C33—C34 | −61.8 (3) | C51—N16—P8—N14 | 87.8 (2) |
C32—C33—C34—N11 | 55.0 (3) | C51—N16—P8—N13 | −148.6 (2) |
N11—C35—C36—C37 | 60.4 (4) | C51—N16—P8—N17 | −29.7 (2) |
C36'—C35—C36—C37 | 45.4 (3) | C53—N17—P8—N14 | −103.0 (2) |
N11—C35—C36'—C37 | 132.6 (5) | C54—N17—P8—N14 | 56.6 (2) |
C36—C35—C36'—C37 | −59.6 (5) | C53—N17—P8—N13 | 131.9 (2) |
C35—C36'—C37—C36 | 52.1 (4) | C54—N17—P8—N13 | −68.46 (19) |
C35—C36'—C37—C38 | −35.3 (7) | C53—N17—P8—N16 | 15.0 (2) |
C35—C36—C37—C36' | −55.1 (3) | C54—N17—P8—N16 | 174.66 (17) |
C35—C36—C37—C38 | 64.2 (4) | P8—N14—P9—N15 | −28.21 (19) |
C36'—C37—C38—N12 | −92.4 (5) | P8—N14—P9—N18 | 99.46 (15) |
C36—C37—C38—N12 | −140.4 (3) | P8—N14—P9—Cl3 | −147.36 (12) |
C33—C32—N10—P5 | 56.9 (2) | P7—N15—P9—N14 | 0.2 (2) |
C33—C34—N11—C35 | 164.10 (19) | P7—N15—P9—N18 | −128.61 (14) |
C33—C34—N11—P5 | −44.9 (3) | P7—N15—P9—Cl3 | 117.89 (13) |
C36—C35—N11—C34 | 51.8 (3) | C57—N18—P9—N14 | 33.0 (2) |
C36'—C35—N11—C34 | 60.9 (2) | C57—N18—P9—N15 | 165.9 (2) |
C36—C35—N11—P5 | −99.7 (3) | C57—N18—P9—Cl3 | −79.5 (2) |
C36'—C35—N11—P5 | −90.5 (2) |
C19H26ClN6P3 | F(000) = 1952 |
Mr = 466.82 | Dx = 1.391 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.163 (3) Å | Cell parameters from 10998 reflections |
b = 16.298 (3) Å | θ = 2.9–27.5° |
c = 17.401 (4) Å | µ = 0.41 mm−1 |
β = 103.36 (3)° | T = 120 K |
V = 4459.7 (15) Å3 | Plate, colourless |
Z = 8 | 0.2 × 0.1 × 0.01 mm |
Nonius KappaCCD area-detector diffractometer | 3119 reflections with I > 2σ(I) |
ϕ and ω scans | Rint = 0.125 |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | θmax = 27.5°, θmin = 3.1° |
Tmin = 0.923, Tmax = 0.998 | h = −20→20 |
20266 measured reflections | k = −21→21 |
5053 independent reflections | l = −22→22 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.0486P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.125 | (Δ/σ)max = 0.004 |
S = 0.99 | Δρmax = 0.36 e Å−3 |
5053 reflections | Δρmin = −0.46 e Å−3 |
271 parameters |
C19H26ClN6P3 | V = 4459.7 (15) Å3 |
Mr = 466.82 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.163 (3) Å | µ = 0.41 mm−1 |
b = 16.298 (3) Å | T = 120 K |
c = 17.401 (4) Å | 0.2 × 0.1 × 0.01 mm |
β = 103.36 (3)° |
Nonius KappaCCD area-detector diffractometer | 5053 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 3119 reflections with I > 2σ(I) |
Tmin = 0.923, Tmax = 0.998 | Rint = 0.125 |
20266 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.36 e Å−3 |
5053 reflections | Δρmin = −0.46 e Å−3 |
271 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. |
x | y | z | Uiso*/Ueq | ||
H6N | 0.1965 (18) | 0.1702 (17) | 0.4645 (17) | 0.008 (8)* | |
H4N | 0.4170 (18) | 0.1591 (17) | 0.1983 (17) | 0.008 (8)* | |
C1 | 0.42780 (18) | 0.36418 (18) | 0.36553 (18) | 0.0241 (7) | |
C2 | 0.4102 (2) | 0.3729 (2) | 0.2845 (2) | 0.0327 (8) | |
H2 | 0.4079 | 0.3257 | 0.2521 | 0.039* | |
C3 | 0.3961 (2) | 0.4495 (2) | 0.2499 (2) | 0.0411 (9) | |
H3 | 0.385 | 0.4549 | 0.1941 | 0.049* | |
C4 | 0.3982 (2) | 0.5185 (2) | 0.2970 (2) | 0.0431 (10) | |
H4 | 0.3876 | 0.5712 | 0.2735 | 0.052* | |
C5 | 0.4156 (2) | 0.5105 (2) | 0.3781 (2) | 0.0434 (10) | |
H5 | 0.4177 | 0.5578 | 0.4103 | 0.052* | |
C6 | 0.4300 (2) | 0.43410 (19) | 0.4123 (2) | 0.0351 (9) | |
H6 | 0.4415 | 0.4289 | 0.4682 | 0.042* | |
C7 | 0.52253 (19) | 0.26647 (17) | 0.49500 (18) | 0.0223 (7) | |
C8 | 0.6045 (2) | 0.28115 (19) | 0.4867 (2) | 0.0302 (8) | |
H8 | 0.6147 | 0.289 | 0.4356 | 0.036* | |
C9 | 0.6720 (2) | 0.2844 (2) | 0.5533 (2) | 0.0347 (8) | |
H9 | 0.7281 | 0.2949 | 0.5475 | 0.042* | |
C10 | 0.6572 (2) | 0.27223 (19) | 0.6274 (2) | 0.0310 (8) | |
H10 | 0.703 | 0.2744 | 0.6727 | 0.037* | |
C11 | 0.5764 (2) | 0.25714 (19) | 0.63570 (19) | 0.0314 (8) | |
H11 | 0.5668 | 0.2484 | 0.6869 | 0.038* | |
C12 | 0.5082 (2) | 0.25444 (18) | 0.57012 (18) | 0.0283 (8) | |
H12 | 0.4523 | 0.2445 | 0.5765 | 0.034* | |
C13 | 0.3362 (2) | 0.07773 (18) | 0.15500 (18) | 0.0264 (7) | |
H13A | 0.3386 | 0.0889 | 0.0996 | 0.032* | |
H13B | 0.2756 | 0.0727 | 0.1569 | 0.032* | |
C14 | 0.3814 (2) | −0.00197 (18) | 0.18165 (17) | 0.0256 (7) | |
H14A | 0.4421 | 0.0033 | 0.1802 | 0.031* | |
H14B | 0.3562 | −0.0462 | 0.1446 | 0.031* | |
C15 | 0.3753 (2) | −0.02545 (18) | 0.26466 (18) | 0.0260 (7) | |
H15A | 0.3152 | −0.0372 | 0.2647 | 0.031* | |
H15B | 0.4086 | −0.0761 | 0.2808 | 0.031* | |
C16 | 0.42570 (19) | 0.01382 (19) | 0.40587 (17) | 0.0250 (7) | |
H16A | 0.4359 | 0.0636 | 0.4393 | 0.03* | |
H16B | 0.4794 | −0.0179 | 0.4167 | 0.03* | |
C17 | 0.3585 (2) | −0.03777 (19) | 0.43218 (19) | 0.0287 (8) | |
H17A | 0.3809 | −0.0531 | 0.4882 | 0.034* | |
H17B | 0.3507 | −0.0892 | 0.401 | 0.034* | |
C18 | 0.2711 (2) | 0.00195 (18) | 0.42457 (18) | 0.0265 (7) | |
H18A | 0.2312 | −0.0404 | 0.435 | 0.032* | |
H18B | 0.2501 | 0.0207 | 0.3694 | 0.032* | |
C19 | 0.2693 (2) | 0.07484 (18) | 0.47973 (17) | 0.0253 (7) | |
H19A | 0.2442 | 0.0569 | 0.5238 | 0.03* | |
H19B | 0.3283 | 0.0929 | 0.5026 | 0.03* | |
N1 | 0.45432 (15) | 0.19633 (14) | 0.34809 (14) | 0.0214 (6) | |
N2 | 0.28675 (15) | 0.15504 (14) | 0.31403 (13) | 0.0195 (6) | |
N3 | 0.34976 (15) | 0.24846 (15) | 0.44175 (14) | 0.0229 (6) | |
N4 | 0.37503 (18) | 0.14686 (16) | 0.20538 (15) | 0.0217 (6) | |
N5 | 0.40726 (15) | 0.04013 (14) | 0.32244 (14) | 0.0211 (6) | |
N6 | 0.21975 (17) | 0.14502 (16) | 0.43906 (16) | 0.0227 (6) | |
P1 | 0.43457 (5) | 0.26312 (5) | 0.40941 (5) | 0.0204 (2) | |
P2 | 0.38028 (5) | 0.13773 (5) | 0.30062 (4) | 0.0191 (2) | |
P3 | 0.26993 (5) | 0.20260 (5) | 0.38743 (4) | 0.0199 (2) | |
Cl1 | 0.17833 (5) | 0.28921 (5) | 0.34667 (4) | 0.0273 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0189 (15) | 0.0237 (16) | 0.0280 (18) | 0.0001 (13) | 0.0022 (13) | −0.0012 (14) |
C2 | 0.0348 (19) | 0.0330 (19) | 0.0285 (19) | 0.0027 (16) | 0.0038 (15) | 0.0012 (15) |
C3 | 0.044 (2) | 0.044 (2) | 0.031 (2) | 0.0074 (18) | 0.0014 (17) | 0.0121 (17) |
C4 | 0.040 (2) | 0.032 (2) | 0.053 (3) | 0.0053 (17) | 0.0007 (19) | 0.0094 (18) |
C5 | 0.054 (2) | 0.0233 (18) | 0.049 (3) | 0.0015 (17) | 0.004 (2) | −0.0014 (17) |
C6 | 0.044 (2) | 0.0298 (18) | 0.030 (2) | 0.0008 (16) | 0.0059 (17) | −0.0045 (15) |
C7 | 0.0236 (16) | 0.0221 (15) | 0.0193 (17) | −0.0011 (13) | 0.0012 (13) | −0.0036 (13) |
C8 | 0.0275 (18) | 0.0403 (19) | 0.0237 (18) | −0.0035 (15) | 0.0080 (14) | −0.0079 (15) |
C9 | 0.0233 (17) | 0.043 (2) | 0.035 (2) | −0.0051 (16) | 0.0011 (15) | −0.0125 (16) |
C10 | 0.0282 (19) | 0.0309 (18) | 0.0277 (19) | 0.0038 (15) | −0.0063 (15) | −0.0068 (14) |
C11 | 0.038 (2) | 0.0321 (18) | 0.0196 (17) | −0.0018 (16) | −0.0017 (15) | 0.0023 (14) |
C12 | 0.0274 (18) | 0.0302 (18) | 0.0261 (19) | 0.0008 (15) | 0.0040 (15) | −0.0001 (14) |
C13 | 0.0296 (18) | 0.0312 (17) | 0.0174 (17) | −0.0030 (15) | 0.0036 (14) | −0.0018 (14) |
C14 | 0.0327 (18) | 0.0250 (16) | 0.0185 (17) | −0.0049 (15) | 0.0049 (14) | −0.0060 (13) |
C15 | 0.0306 (18) | 0.0249 (17) | 0.0235 (18) | −0.0016 (14) | 0.0084 (15) | −0.0012 (13) |
C16 | 0.0252 (17) | 0.0303 (17) | 0.0175 (17) | 0.0068 (14) | 0.0010 (14) | 0.0054 (13) |
C17 | 0.038 (2) | 0.0252 (16) | 0.0238 (18) | 0.0038 (15) | 0.0084 (15) | 0.0038 (14) |
C18 | 0.0306 (18) | 0.0286 (17) | 0.0207 (17) | −0.0052 (14) | 0.0065 (14) | 0.0016 (14) |
C19 | 0.0267 (17) | 0.0332 (17) | 0.0160 (17) | 0.0018 (14) | 0.0053 (14) | 0.0022 (13) |
N1 | 0.0210 (13) | 0.0262 (13) | 0.0174 (13) | 0.0000 (11) | 0.0051 (11) | −0.0049 (11) |
N2 | 0.0183 (13) | 0.0270 (13) | 0.0131 (13) | −0.0018 (11) | 0.0031 (10) | −0.0031 (10) |
N3 | 0.0225 (14) | 0.0286 (14) | 0.0170 (13) | −0.0018 (11) | 0.0036 (11) | −0.0083 (11) |
N4 | 0.0202 (15) | 0.0301 (15) | 0.0156 (14) | −0.0036 (12) | 0.0062 (12) | −0.0041 (11) |
N5 | 0.0279 (14) | 0.0212 (12) | 0.0141 (13) | −0.0013 (11) | 0.0046 (11) | −0.0014 (11) |
N6 | 0.0225 (14) | 0.0277 (15) | 0.0192 (14) | 0.0029 (12) | 0.0074 (12) | −0.0029 (12) |
P1 | 0.0201 (4) | 0.0232 (4) | 0.0173 (4) | −0.0012 (3) | 0.0032 (3) | −0.0035 (3) |
P2 | 0.0203 (4) | 0.0214 (4) | 0.0151 (4) | 0.0003 (3) | 0.0029 (3) | −0.0013 (3) |
P3 | 0.0195 (4) | 0.0239 (4) | 0.0159 (4) | 0.0004 (3) | 0.0028 (3) | −0.0012 (3) |
Cl1 | 0.0277 (4) | 0.0306 (4) | 0.0232 (4) | 0.0085 (3) | 0.0048 (3) | 0.0018 (3) |
C1—C2 | 1.380 (4) | C14—H14B | 0.99 |
C1—C6 | 1.396 (4) | C15—N5 | 1.477 (4) |
C1—P1 | 1.808 (3) | C15—H15A | 0.99 |
C2—C3 | 1.381 (5) | C15—H15B | 0.99 |
C2—H2 | 0.95 | C16—N5 | 1.477 (4) |
C3—C4 | 1.387 (5) | C16—C17 | 1.525 (4) |
C3—H3 | 0.95 | C16—H16A | 0.99 |
C4—C5 | 1.379 (5) | C16—H16B | 0.99 |
C4—H4 | 0.95 | C17—C18 | 1.532 (4) |
C5—C6 | 1.377 (5) | C17—H17A | 0.99 |
C5—H5 | 0.95 | C17—H17B | 0.99 |
C6—H6 | 0.95 | C18—C19 | 1.532 (4) |
C7—C8 | 1.386 (4) | C18—H18A | 0.99 |
C7—C12 | 1.393 (4) | C18—H18B | 0.99 |
C7—P1 | 1.807 (3) | C19—N6 | 1.479 (4) |
C8—C9 | 1.398 (4) | C19—H19A | 0.99 |
C8—H8 | 0.95 | C19—H19B | 0.99 |
C9—C10 | 1.380 (5) | N1—P2 | 1.603 (2) |
C9—H9 | 0.95 | N1—P1 | 1.607 (2) |
C10—C11 | 1.368 (5) | N2—P3 | 1.571 (2) |
C10—H10 | 0.95 | N2—P2 | 1.607 (3) |
C11—C12 | 1.392 (4) | N3—P3 | 1.598 (2) |
C11—H11 | 0.95 | N3—P1 | 1.615 (3) |
C12—H12 | 0.95 | N4—P2 | 1.646 (3) |
C13—N4 | 1.476 (4) | N4—H4N | 0.74 (3) |
C13—C14 | 1.510 (4) | N5—P2 | 1.670 (2) |
C13—H13A | 0.99 | N6—P3 | 1.638 (3) |
C13—H13B | 0.99 | N6—H6N | 0.76 (3) |
C14—C15 | 1.519 (4) | P3—Cl1 | 2.0499 (11) |
C14—H14A | 0.99 | ||
C2—C1—C6 | 118.9 (3) | N5—C16—C17 | 117.3 (2) |
C2—C1—P1 | 120.3 (2) | N5—C16—H16A | 108 |
C6—C1—P1 | 120.4 (2) | C17—C16—H16A | 108 |
C1—C2—C3 | 120.8 (3) | N5—C16—H16B | 108 |
C1—C2—H2 | 119.6 | C17—C16—H16B | 108 |
C3—C2—H2 | 119.6 | H16A—C16—H16B | 107.2 |
C2—C3—C4 | 119.7 (3) | C16—C17—C18 | 116.6 (2) |
C2—C3—H3 | 120.1 | C16—C17—H17A | 108.1 |
C4—C3—H3 | 120.1 | C18—C17—H17A | 108.1 |
C5—C4—C3 | 119.9 (3) | C16—C17—H17B | 108.1 |
C5—C4—H4 | 120 | C18—C17—H17B | 108.1 |
C3—C4—H4 | 120 | H17A—C17—H17B | 107.3 |
C6—C5—C4 | 120.2 (3) | C17—C18—C19 | 115.1 (3) |
C6—C5—H5 | 119.9 | C17—C18—H18A | 108.5 |
C4—C5—H5 | 119.9 | C19—C18—H18A | 108.5 |
C5—C6—C1 | 120.4 (3) | C17—C18—H18B | 108.5 |
C5—C6—H6 | 119.8 | C19—C18—H18B | 108.5 |
C1—C6—H6 | 119.8 | H18A—C18—H18B | 107.5 |
C8—C7—C12 | 119.5 (3) | N6—C19—C18 | 112.7 (2) |
C8—C7—P1 | 120.5 (2) | N6—C19—H19A | 109 |
C12—C7—P1 | 120.0 (2) | C18—C19—H19A | 109 |
C7—C8—C9 | 120.1 (3) | N6—C19—H19B | 109 |
C7—C8—H8 | 119.9 | C18—C19—H19B | 109 |
C9—C8—H8 | 119.9 | H19A—C19—H19B | 107.8 |
C10—C9—C8 | 119.9 (3) | P2—N1—P1 | 120.43 (16) |
C10—C9—H9 | 120.1 | P3—N2—P2 | 123.38 (14) |
C8—C9—H9 | 120.1 | P3—N3—P1 | 119.83 (15) |
C11—C10—C9 | 120.1 (3) | C13—N4—P2 | 116.4 (2) |
C11—C10—H10 | 120 | C13—N4—H4N | 113 (2) |
C9—C10—H10 | 120 | P2—N4—H4N | 111 (2) |
C10—C11—C12 | 120.9 (3) | C16—N5—C15 | 114.7 (2) |
C10—C11—H11 | 119.6 | C16—N5—P2 | 118.89 (19) |
C12—C11—H11 | 119.6 | C15—N5—P2 | 120.19 (18) |
C7—C12—C11 | 119.5 (3) | C19—N6—P3 | 115.1 (2) |
C7—C12—H12 | 120.2 | C19—N6—H6N | 115 (2) |
C11—C12—H12 | 120.2 | P3—N6—H6N | 113 (2) |
N4—C13—C14 | 111.4 (2) | N1—P1—N3 | 116.48 (13) |
N4—C13—H13A | 109.3 | N1—P1—C7 | 109.18 (13) |
C14—C13—H13A | 109.3 | N3—P1—C7 | 106.67 (14) |
N4—C13—H13B | 109.3 | N1—P1—C1 | 109.79 (14) |
C14—C13—H13B | 109.3 | N3—P1—C1 | 107.97 (14) |
H13A—C13—H13B | 108 | C7—P1—C1 | 106.26 (13) |
C13—C14—C15 | 112.0 (3) | N1—P2—N2 | 115.84 (13) |
C13—C14—H14A | 109.2 | N1—P2—N4 | 108.88 (14) |
C15—C14—H14A | 109.2 | N2—P2—N4 | 107.40 (14) |
C13—C14—H14B | 109.2 | N1—P2—N5 | 109.00 (12) |
C15—C14—H14B | 109.2 | N2—P2—N5 | 109.83 (13) |
H14A—C14—H14B | 107.9 | N4—P2—N5 | 105.37 (13) |
N5—C15—C14 | 112.1 (2) | N2—P3—N3 | 116.36 (13) |
N5—C15—H15A | 109.2 | N2—P3—N6 | 111.35 (14) |
C14—C15—H15A | 109.2 | N3—P3—N6 | 112.22 (14) |
N5—C15—H15B | 109.2 | N2—P3—Cl1 | 107.78 (9) |
C14—C15—H15B | 109.2 | N3—P3—Cl1 | 107.61 (10) |
H15A—C15—H15B | 107.9 | N6—P3—Cl1 | 100.06 (11) |
C6—C1—C2—C3 | 0.8 (5) | C8—C7—P1—N3 | −177.8 (2) |
P1—C1—C2—C3 | 173.2 (3) | C12—C7—P1—N3 | 2.0 (3) |
C1—C2—C3—C4 | −1.0 (5) | C8—C7—P1—C1 | −62.8 (3) |
C2—C3—C4—C5 | 1.0 (6) | C12—C7—P1—C1 | 117.0 (3) |
C3—C4—C5—C6 | −0.7 (6) | C2—C1—P1—N1 | 22.0 (3) |
C4—C5—C6—C1 | 0.5 (6) | C6—C1—P1—N1 | −165.7 (2) |
C2—C1—C6—C5 | −0.5 (5) | C2—C1—P1—N3 | −105.9 (3) |
P1—C1—C6—C5 | −172.9 (3) | C6—C1—P1—N3 | 66.3 (3) |
C12—C7—C8—C9 | −0.4 (5) | C2—C1—P1—C7 | 140.0 (3) |
P1—C7—C8—C9 | 179.4 (2) | C6—C1—P1—C7 | −47.8 (3) |
C7—C8—C9—C10 | 0.5 (5) | P1—N1—P2—N2 | 4.2 (2) |
C8—C9—C10—C11 | −0.1 (5) | P1—N1—P2—N4 | 125.28 (17) |
C9—C10—C11—C12 | −0.5 (5) | P1—N1—P2—N5 | −120.26 (17) |
C8—C7—C12—C11 | −0.2 (5) | P3—N2—P2—N1 | −20.5 (2) |
P1—C7—C12—C11 | 180.0 (2) | P3—N2—P2—N4 | −142.38 (17) |
C10—C11—C12—C7 | 0.6 (5) | P3—N2—P2—N5 | 103.53 (18) |
N4—C13—C14—C15 | 62.6 (3) | C13—N4—P2—N1 | 157.3 (2) |
C13—C14—C15—N5 | −55.5 (3) | C13—N4—P2—N2 | −76.6 (2) |
N5—C16—C17—C18 | −60.9 (4) | C13—N4—P2—N5 | 40.5 (3) |
C16—C17—C18—C19 | −67.4 (4) | C16—N5—P2—N1 | 57.2 (2) |
C17—C18—C19—N6 | 135.0 (3) | C15—N5—P2—N1 | −151.8 (2) |
C14—C13—N4—P2 | −56.7 (3) | C16—N5—P2—N2 | −70.7 (2) |
C17—C16—N5—C15 | −47.2 (4) | C15—N5—P2—N2 | 80.3 (3) |
C17—C16—N5—P2 | 105.3 (3) | C16—N5—P2—N4 | 174.0 (2) |
C14—C15—N5—C16 | −163.7 (3) | C15—N5—P2—N4 | −35.1 (3) |
C14—C15—N5—P2 | 44.2 (3) | P2—N2—P3—N3 | 11.0 (2) |
C18—C19—N6—P3 | −79.9 (3) | P2—N2—P3—N6 | −119.29 (18) |
P2—N1—P1—N3 | 19.6 (2) | P2—N2—P3—Cl1 | 131.90 (15) |
P2—N1—P1—C7 | 140.46 (17) | P1—N3—P3—N2 | 14.8 (2) |
P2—N1—P1—C1 | −103.43 (18) | P1—N3—P3—N6 | 144.69 (17) |
P3—N3—P1—N1 | −29.7 (2) | P1—N3—P3—Cl1 | −106.18 (15) |
P3—N3—P1—C7 | −151.91 (16) | C19—N6—P3—N2 | 67.5 (2) |
P3—N3—P1—C1 | 94.24 (19) | C19—N6—P3—N3 | −64.9 (2) |
C8—C7—P1—N1 | 55.5 (3) | C19—N6—P3—Cl1 | −178.79 (19) |
C12—C7—P1—N1 | −124.6 (2) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C19H26ClN6P3 | C19H26ClN6P3 |
Mr | 466.82 | 466.82 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 10.083 (2), 12.770 (3), 25.816 (5) | 16.163 (3), 16.298 (3), 17.401 (4) |
α, β, γ (°) | 95.64 (3), 96.98 (3), 92.07 (3) | 90, 103.36 (3), 90 |
V (Å3) | 3279.5 (11) | 4459.7 (15) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.41 | 0.41 |
Crystal size (mm) | 0.18 × 0.08 × 0.05 | 0.2 × 0.1 × 0.01 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.929, 0.980 | 0.923, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42350, 14040, 8616 | 20266, 5053, 3119 |
Rint | 0.071 | 0.125 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.158, 1.06 | 0.054, 0.125, 0.99 |
No. of reflections | 14040 | 5053 |
No. of parameters | 807 | 271 |
No. of restraints | 12 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.28, −1.25 | 0.36, −0.46 |
Computer programs: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997), COLLECT and DENZO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990).
C35—C36—C37—C38 | 64.2 (4) | C54—C55—C56—C57 | 84.5 (3) |
C32—N10—P5—N7 | −158.18 (15) | C51—N16—P8—N13 | −148.6 (2) |
C35—N11—P5—N7 | −56.87 (18) | C54—N17—P8—N13 | −68.46 (19) |
C38—N12—P6—N9 | 67.57 (19) | C57—N18—P9—N15 | 165.9 (2) |
C16—C17—C18—C19 | −67.4 (4) | C16—N5—P2—N1 | 57.2 (2) |
C13—N4—P2—N1 | 157.3 (2) | C19—N6—P3—N3 | −64.9 (2) |
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As part of our investigations on the chiral properties of cyclophosphazenes and, in particular, that of configurational isomers, we have investigated the reaction of 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene with spermine and spermidine. The single-bridged derivatives arising from the reaction with spermine have been demonstrated to be a 50:50 mixture of meso and racemic forms (Coles et al., 2002). The analogous reaction with spermidine is expected to give rise to two racemates, which have been observed by 31P NMR, but, so far, have not been separated. Another product from this reaction is a fused tricyclic system (see Scheme below) based on a single trimer unit, which is the subject of the present study as it has given rise to different polymorphic forms.
Polymorphism in cyclophosphazene chemistry has hitherto been confined to tetrameric, N4P4, or higher ring systems. A review article (Shaw, 1978) mentions tetrameric and pentameric derivatives. The first and probably the best known are the K– (Hazekamp et al., 1962) and T– (Wagner & Vos, 1968) forms of N4P4Cl8 differing in the shape of the eight-membered N4P4 ring. Protonated cationic tetramer species, (N4HP4Me8)2CoCl4, display two types of eight-membered-ring conformations in the same unit cell (Trotter & Whitlow, 1970). Three different crystalline modifications of the pentameric fluoride, N5P5F10, have been reported, two of which had their structures determined (Hartsuiker & Wagner, 1974; Pauzenga-Hartsuiker, 1975). The acyclic cation (Ph3P═N-PPh3)+, often favoured to stabilize complex inorganic and organometallic anions, displays a variety of P—N—P bond angles. In one structure, both bent and linear forms have been observed in the same asymmetric unit (Wilson & Bau, 1974).
We now report the first example of polymorphism involving a trimer N3P3 structure. Unlike the other examples of polymorphism referred to above, this is not a function of the NP skeleton. The backbone of the structures presented [Figs. 1, 2, 3 and 4 for molecules (Ia), (Ib), (Ic) and (IIa) found in the structures of (I) and (II), respectively] is the cyclic N3P3 moiety of cyclotriphosphazene. The driving force behind this polymorphic behaviour is the conformation of two NH groups, which are part of a nine-membered cis-ansa moiety linked to a six-membered bis-amino ring bonded to two P atoms in the N3P3 ring. The conformation of the NH moieties is determined by the chiral nature of the P atoms to which they are bonded. An inversion of chirality about these atoms necessitates a flipping of the NH group and as a result there are differing molecular conformations in the two crystal structures presented.
As the conformational arrangements of these molecules are to be compared, their structures will be discussed simultaneously. Selected geometric parameters for the total of four molecules presented are given in Tables 1 and 2 for structures (I) and (II), respectively. The bond lengths and angles in all four molecules conform to expected values derived from structures found in the Cambridge Structural Database (Allen & Kennard, 1993; Orpen et al., 1992). The asymmetric unit of (I) comprises three independent molecules, each exhibiting different conformational forms. Molecules (Ia), (Ib) and (Ic) in (I) are depicted in Figs. 1, 2 and 3, respectively, whilst the structure of (II) [molecule (IIa)] is presented in Fig. 4.
The structures of (I) and (II) exhibit the same connectivity yet crystallize in different space groups, indicating that they are polymorphic in nature. Molecules (Ia), (Ic) and (IIa) all have the same chirality, i.e. R about atoms P2/P3, P8/P9 and P2/P3, whilst molecule (Ib) has S chirality for atoms P5 and P6. The conformations of the primary amino groups, and hence those of the ring systems of which they are components, are best described and compared using the torsion angles given in Tables 1 and 2. The conformation of molecule (Ia) may be assigned as the α form and is described by the torsion angles C13—N4—P2—N1, C16—N5—P2—N1, C16—C17—C18—C19 and C19—N6—P3—N3. Molecule (Ib) has torsion angles (C32—N10—P5—N7, C35—N11—P5—N7, C35—C36—C37—C38 and C38—N12—P6—N9) similar in magnitude but opposite in sign, indicating an inverted conformation to that of the α form, arising from the alternative chirality adopted by P5 and P6. Hence, the R/R racemate generated through the centre of symmetry in the space group would exhibit essentially the same form as that of (Ia), the α form. The β form exhibited by molecule (Ic) [characterized by torsion angles C51—N16—P8—N13, C54—N17—P8—N13, C54—C55—C56—C57 and C57—N18—P9—N15] is similar to that of the α form, apart from the conformation of the N18—P9 bond, which has a torsion angle that is greater than 100° larger in magnitude. Molecule (IIa) has the same numbering scheme as that of molecule (Ia) and is hence characterized by the same torsion angles. Comparison of these angles essentially shows it to be the α form. By puckering analysis (Cremer & Pople, 1975) the conformations of the spiro-P—N—C—C—C—N rings is shown to be that of a boat; however, in the case of molecule (Ib) the apical atoms (P5 and C33) are opposite in orientation to those of the other molecules, which is due to the inversion in chirality about P5. The conformations adopted by the nine-membered rings may be compared using the torsion angles described in Tables 1 and 2 [C16—C17—C18—C19, C35—C36—C37—C38, C54—C55—C56—C57 and C16—C17—C18—C19 for molecules (Ia), (Ib), (Ic) and (IIa) respectively]. From these values, it can be seen that (Ia) and (IIa) adopt a similar α conformation [inverted in (Ib) as a result of the chirality inversion], whereas the conformation is more distorted in (Ic), i.e. the β form.
The behaviour described above has implications on the conformation of the cyclophosphazene ring system, which one would normally expect to be planar. Puckering analysis (Cremer & Pople, 1975) shows the N3P3 ring in (Ia) to be a boat, whilst the remaining molecules exhibit a twist-boat conformation. The deviations from planarity are not great, but nevertheless significant [maximum deviations: molecule (Ia) 0.133 Å (P1); (Ib) = 0.259 Å (P4); (Ic) = 0.221 Å (N14); and (IIa) = 0.181 Å (P1)]. The smaller deviations in the α form with respect to that of the β form indicate that less strain on the system is induced by this arrangement. This is not accompanied by a decrease of the P···P non-bonded distance, as has been observed in similar, but shorter, ansa-bridged N3P3 systems (Contractor et al., 1986), because the P···P cross-ring separations are comparable to those observed in unstrained N3P3 containing structures (Contractor et al., 1986).