Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010101441X/av1085sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010101441X/av1085Isup2.hkl |
CCDC reference: 174850
In this study, compound (I) was prepared from the reaction of morpholine (5.23 g, 6.00 mmol) and 2-trans-6-N4P4Cl6(NnPr)2 (2.04 g, 4.00 mmol) in acetonitrile (150 ml). Triethylamine (6.07 g, 6.00 mmol) was added to this mixture at 253 K, which was then worked up according to the literature method of Contractor et al. (1987). The compound was crystallized from acetonitrile [m.p. 483 K (decomposition); yield: 2.37 g (73%)].
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C30H64N12O6P4 | Z = 1 |
Mr = 812.81 | F(000) = 436 |
Triclinic, P1 | Dx = 1.361 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.502 (8) Å | Cell parameters from 25 reflections |
b = 10.939 (14) Å | θ = 10–11° |
c = 11.814 (7) Å | µ = 0.25 mm−1 |
α = 66.39 (9)° | T = 293 K |
β = 81.63 (7)° | Rod, colorless |
γ = 81.74 (10)° | 0.30 × 0.25 × 0.20 mm |
V = 991.7 (17) Å3 |
Enraf-Nonius TurboCAD-4 diffractometer | 2115 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 26.3°, θmin = 3.7° |
non–profiled ω scans | h = 0→10 |
Absorption correction: part of the refinement model (ΔF) (SHELX97; Sheldrick, 1998) | k = −13→13 |
Tmin = 0.928, Tmax = 0.952 | l = −14→14 |
4298 measured reflections | 3 standard reflections every 120 min |
4016 independent reflections | intensity decay: 3% |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | w = 1/[σ2(Fo2) + (0.1149P)2] where P = (Fo2 + 2Fc2)/3 |
3578 reflections | (Δ/σ)max < 0.001 |
239 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C30H64N12O6P4 | γ = 81.74 (10)° |
Mr = 812.81 | V = 991.7 (17) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.502 (8) Å | Mo Kα radiation |
b = 10.939 (14) Å | µ = 0.25 mm−1 |
c = 11.814 (7) Å | T = 293 K |
α = 66.39 (9)° | 0.30 × 0.25 × 0.20 mm |
β = 81.63 (7)° |
Enraf-Nonius TurboCAD-4 diffractometer | 2115 reflections with I > 2σ(I) |
Absorption correction: part of the refinement model (ΔF) (SHELX97; Sheldrick, 1998) | Rint = 0.053 |
Tmin = 0.928, Tmax = 0.952 | 3 standard reflections every 120 min |
4298 measured reflections | intensity decay: 3% |
4016 independent reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.183 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | Δρmax = 0.43 e Å−3 |
3578 reflections | Δρmin = −0.33 e Å−3 |
239 parameters |
Experimental. Sheldrick, G·M. (anon) SHELX97 Release 97–2 (1998) I/sigma threshold for reflections = 5.000 Delta(U)/lambda**2 = 0.000 Highest even order spherical harmonic = 6 Highest odd order spherical harmonic = 3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.40556 (11) | 0.44102 (8) | 0.38496 (7) | 0.0238 (3) | |
P2 | 0.48323 (12) | 0.69968 (8) | 0.37486 (8) | 0.0256 (3) | |
N1 | 0.3773 (4) | 0.5904 (3) | 0.3770 (3) | 0.0313 (7) | |
N4 | 0.2504 (4) | 0.4118 (3) | 0.3301 (3) | 0.0290 (7) | |
N5 | 0.5560 (4) | 0.4302 (3) | 0.2841 (3) | 0.0321 (7) | |
N2 | 0.6107 (4) | 0.7407 (3) | 0.2450 (3) | 0.0342 (8) | |
O3 | −0.0534 (4) | 0.4548 (3) | 0.2349 (3) | 0.0503 (8) | |
N3 | 0.3489 (4) | 0.8299 (3) | 0.3675 (3) | 0.0333 (7) | |
O2 | 0.1327 (4) | 1.0603 (3) | 0.3446 (3) | 0.0614 (10) | |
C13 | 0.6157 (5) | 0.3065 (4) | 0.2668 (3) | 0.0357 (9) | |
H13A | 0.5320 | 0.2463 | 0.2956 | 0.043* | |
H13B | 0.7043 | 0.2631 | 0.3165 | 0.043* | |
C12 | 0.2249 (5) | 0.4983 (4) | 0.2011 (3) | 0.0412 (10) | |
H12A | 0.3220 | 0.4944 | 0.1477 | 0.049* | |
H12B | 0.1987 | 0.5904 | 0.1935 | 0.049* | |
C9 | 0.0971 (5) | 0.4093 (4) | 0.4076 (3) | 0.0366 (9) | |
H9B | 0.0652 | 0.4977 | 0.4087 | 0.044* | |
H9A | 0.1107 | 0.3470 | 0.4921 | 0.044* | |
O1 | 0.7976 (5) | 0.8563 (4) | 0.0142 (3) | 0.0688 (11) | |
C10 | −0.0309 (5) | 0.3684 (5) | 0.3597 (4) | 0.0441 (10) | |
H10A | −0.0027 | 0.2774 | 0.3645 | 0.053* | |
H10B | −0.1302 | 0.3697 | 0.4115 | 0.053* | |
C5 | 0.2158 (6) | 0.8655 (4) | 0.2944 (4) | 0.0472 (11) | |
H5B | 0.1788 | 0.7847 | 0.2965 | 0.057* | |
H5A | 0.2501 | 0.9194 | 0.2088 | 0.057* | |
C8 | 0.4000 (6) | 0.9488 (4) | 0.3747 (4) | 0.0462 (11) | |
H8B | 0.4435 | 1.0071 | 0.2932 | 0.055* | |
H8A | 0.4829 | 0.9221 | 0.4306 | 0.055* | |
C11 | 0.0899 (6) | 0.4531 (6) | 0.1606 (4) | 0.0583 (13) | |
H11A | 0.0741 | 0.5113 | 0.0753 | 0.070* | |
H11B | 0.1198 | 0.3628 | 0.1638 | 0.070* | |
C1 | 0.7418 (6) | 0.8181 (5) | 0.2315 (4) | 0.0494 (11) | |
H1A | 0.7904 | 0.7839 | 0.3090 | 0.059* | |
H1B | 0.7008 | 0.9106 | 0.2142 | 0.059* | |
C7 | 0.2571 (6) | 1.0239 (4) | 0.4217 (5) | 0.0548 (13) | |
H7A | 0.2188 | 0.9674 | 0.5054 | 0.066* | |
H7B | 0.2905 | 1.1038 | 0.4243 | 0.066* | |
C6 | 0.0792 (6) | 0.9435 (5) | 0.3426 (5) | 0.0585 (13) | |
H6B | −0.0070 | 0.9694 | 0.2896 | 0.070* | |
H6A | 0.0386 | 0.8872 | 0.4257 | 0.070* | |
C14 | 0.6705 (6) | 0.3318 (4) | 0.1323 (4) | 0.0479 (11) | |
H14B | 0.5781 | 0.3599 | 0.0853 | 0.057* | |
H14A | 0.7389 | 0.4046 | 0.0992 | 0.057* | |
C4 | 0.5434 (6) | 0.7826 (5) | 0.1261 (3) | 0.0478 (11) | |
H4B | 0.4919 | 0.8732 | 0.1034 | 0.057* | |
H4A | 0.4634 | 0.7239 | 0.1342 | 0.057* | |
C2 | 0.8684 (7) | 0.8129 (6) | 0.1277 (5) | 0.0671 (15) | |
H2A | 0.9507 | 0.8701 | 0.1183 | 0.081* | |
H2B | 0.9180 | 0.7219 | 0.1486 | 0.081* | |
C15 | 0.7601 (8) | 0.2104 (5) | 0.1146 (5) | 0.0702 (17) | |
H15B | 0.7933 | 0.2325 | 0.0280 | 0.105* | |
H15C | 0.6919 | 0.1390 | 0.1443 | 0.105* | |
H15A | 0.8524 | 0.1825 | 0.1603 | 0.105* | |
C3 | 0.6730 (8) | 0.7775 (6) | 0.0267 (5) | 0.0719 (16) | |
H3A | 0.7168 | 0.6852 | 0.0462 | 0.086* | |
H3B | 0.6272 | 0.8089 | −0.0519 | 0.086* | |
N6 | 0.4104 (4) | 0.3255 (3) | 0.5177 (2) | 0.0305 (7) | |
H5 | 0.622 (5) | 0.496 (4) | 0.244 (4) | 0.033 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0310 (5) | 0.0207 (4) | 0.0183 (4) | 0.0031 (3) | −0.0116 (4) | −0.0051 (3) |
P2 | 0.0360 (6) | 0.0184 (4) | 0.0195 (4) | 0.0064 (4) | −0.0130 (4) | −0.0039 (3) |
N1 | 0.0395 (18) | 0.0265 (15) | 0.0266 (15) | 0.0112 (13) | −0.0190 (13) | −0.0083 (12) |
N4 | 0.0366 (18) | 0.0304 (15) | 0.0210 (14) | 0.0062 (13) | −0.0165 (13) | −0.0095 (12) |
N5 | 0.0312 (17) | 0.0308 (16) | 0.0357 (17) | −0.0029 (14) | −0.0030 (14) | −0.0146 (14) |
N2 | 0.051 (2) | 0.0298 (15) | 0.0211 (15) | −0.0004 (14) | −0.0133 (14) | −0.0065 (12) |
O3 | 0.0447 (19) | 0.0589 (19) | 0.0458 (17) | −0.0020 (15) | −0.0244 (15) | −0.0130 (15) |
N3 | 0.0415 (19) | 0.0197 (14) | 0.0370 (17) | 0.0127 (13) | −0.0196 (15) | −0.0092 (12) |
O2 | 0.070 (2) | 0.0356 (16) | 0.078 (2) | 0.0272 (16) | −0.030 (2) | −0.0241 (16) |
C13 | 0.037 (2) | 0.0310 (19) | 0.033 (2) | 0.0019 (16) | 0.0006 (17) | −0.0093 (16) |
C12 | 0.038 (2) | 0.055 (2) | 0.0248 (19) | 0.0040 (19) | −0.0189 (17) | −0.0069 (17) |
C9 | 0.030 (2) | 0.050 (2) | 0.0296 (19) | 0.0021 (18) | −0.0075 (16) | −0.0157 (17) |
O1 | 0.086 (3) | 0.075 (2) | 0.0300 (16) | −0.013 (2) | 0.0038 (18) | −0.0052 (16) |
C10 | 0.038 (2) | 0.051 (2) | 0.038 (2) | −0.0036 (19) | −0.0082 (19) | −0.0110 (19) |
C5 | 0.052 (3) | 0.035 (2) | 0.059 (3) | 0.011 (2) | −0.027 (2) | −0.020 (2) |
C8 | 0.050 (3) | 0.030 (2) | 0.061 (3) | 0.0053 (19) | −0.018 (2) | −0.020 (2) |
C11 | 0.055 (3) | 0.087 (4) | 0.039 (2) | 0.000 (3) | −0.030 (2) | −0.025 (2) |
C1 | 0.059 (3) | 0.050 (3) | 0.035 (2) | −0.010 (2) | −0.002 (2) | −0.0111 (19) |
C7 | 0.064 (3) | 0.036 (2) | 0.074 (3) | 0.015 (2) | −0.024 (3) | −0.032 (2) |
C6 | 0.047 (3) | 0.043 (2) | 0.081 (3) | 0.015 (2) | −0.021 (3) | −0.022 (2) |
C14 | 0.070 (3) | 0.040 (2) | 0.032 (2) | 0.006 (2) | −0.008 (2) | −0.0165 (18) |
C4 | 0.059 (3) | 0.051 (2) | 0.0233 (19) | −0.003 (2) | −0.013 (2) | −0.0017 (17) |
C2 | 0.070 (4) | 0.072 (3) | 0.039 (3) | −0.012 (3) | 0.014 (3) | −0.004 (2) |
C15 | 0.099 (4) | 0.050 (3) | 0.053 (3) | 0.009 (3) | 0.016 (3) | −0.024 (2) |
C3 | 0.101 (5) | 0.082 (4) | 0.030 (2) | −0.013 (4) | −0.004 (3) | −0.018 (2) |
N6 | 0.049 (2) | 0.0246 (14) | 0.0154 (14) | 0.0020 (13) | −0.0185 (13) | −0.0016 (11) |
P1—N6 | 1.573 (3) | C10—H10A | 0.97 |
P1—N1 | 1.584 (4) | C10—H10B | 0.97 |
P1—N5 | 1.642 (4) | C5—C6 | 1.521 (6) |
P1—N4 | 1.672 (3) | C5—H5B | 0.97 |
P2—N6i | 1.578 (3) | C5—H5A | 0.97 |
P2—N1 | 1.587 (4) | C8—C7 | 1.531 (6) |
P2—N3 | 1.675 (4) | C8—H8B | 0.97 |
P2—N2 | 1.684 (4) | C8—H8A | 0.97 |
N4—C12 | 1.466 (4) | C11—H11A | 0.97 |
N4—C9 | 1.477 (5) | C11—H11B | 0.97 |
N5—C13 | 1.458 (5) | C1—C2 | 1.524 (7) |
N5—H5 | 0.91 (4) | C1—H1A | 0.97 |
N2—C1 | 1.448 (6) | C1—H1B | 0.97 |
N2—C4 | 1.467 (5) | C7—H7A | 0.97 |
O3—C11 | 1.397 (6) | C7—H7B | 0.97 |
O3—C10 | 1.420 (5) | C6—H6B | 0.97 |
N3—C5 | 1.437 (5) | C6—H6A | 0.97 |
N3—C8 | 1.466 (5) | C14—C15 | 1.508 (6) |
O2—C7 | 1.406 (6) | C14—H14B | 0.97 |
O2—C6 | 1.426 (6) | C14—H14A | 0.97 |
C13—C14 | 1.513 (5) | C4—C3 | 1.502 (7) |
C13—H13A | 0.97 | C4—H4B | 0.97 |
C13—H13B | 0.97 | C4—H4A | 0.97 |
C12—C11 | 1.517 (6) | C2—H2A | 0.97 |
C12—H12A | 0.97 | C2—H2B | 0.97 |
C12—H12B | 0.97 | C15—H15B | 0.96 |
C9—C10 | 1.493 (6) | C15—H15C | 0.96 |
C9—H9B | 0.97 | C15—H15A | 0.96 |
C9—H9A | 0.97 | C3—H3A | 0.97 |
O1—C3 | 1.416 (7) | C3—H3B | 0.97 |
O1—C2 | 1.425 (6) | N6—P2i | 1.578 (3) |
N6—P1—N1 | 117.50 (17) | C7—C8—H8B | 109.8 |
N6—P1—N5 | 114.88 (19) | N3—C8—H8A | 109.8 |
N1—P1—N5 | 108.8 (2) | C7—C8—H8A | 109.8 |
N6—P1—N4 | 103.34 (19) | H8B—C8—H8A | 108.2 |
N1—P1—N4 | 107.90 (18) | O3—C11—C12 | 112.6 (3) |
N5—P1—N4 | 103.09 (17) | O3—C11—H11A | 109.1 |
N6i—P2—N1 | 122.53 (17) | C12—C11—H11A | 109.1 |
N6i—P2—N3 | 107.50 (17) | O3—C11—H11B | 109.1 |
N1—P2—N3 | 103.06 (19) | C12—C11—H11B | 109.1 |
N6i—P2—N2 | 104.83 (18) | H11A—C11—H11B | 107.8 |
N1—P2—N2 | 108.59 (17) | N2—C1—C2 | 112.1 (4) |
N3—P2—N2 | 110.07 (18) | N2—C1—H1A | 109.2 |
P1—N1—P2 | 136.9 (2) | C2—C1—H1A | 109.2 |
C12—N4—C9 | 108.6 (3) | N2—C1—H1B | 109.2 |
C12—N4—P1 | 115.8 (3) | C2—C1—H1B | 109.2 |
C9—N4—P1 | 114.8 (2) | H1A—C1—H1B | 107.9 |
C13—N5—P1 | 123.6 (3) | O2—C7—C8 | 111.1 (4) |
C13—N5—H5 | 113 (2) | O2—C7—H7A | 109.4 |
P1—N5—H5 | 123 (2) | C8—C7—H7A | 109.4 |
C1—N2—C4 | 110.4 (3) | O2—C7—H7B | 109.4 |
C1—N2—P2 | 119.8 (3) | C8—C7—H7B | 109.4 |
C4—N2—P2 | 117.6 (3) | H7A—C7—H7B | 108.0 |
C11—O3—C10 | 109.1 (3) | O2—C6—C5 | 110.3 (4) |
C5—N3—C8 | 110.9 (3) | O2—C6—H6B | 109.6 |
C5—N3—P2 | 122.1 (3) | C5—C6—H6B | 109.6 |
C8—N3—P2 | 119.5 (3) | O2—C6—H6A | 109.6 |
C7—O2—C6 | 110.1 (3) | C5—C6—H6A | 109.6 |
N5—C13—C14 | 111.9 (3) | H6B—C6—H6A | 108.1 |
N5—C13—H13A | 109.2 | C15—C14—C13 | 113.0 (4) |
C14—C13—H13A | 109.2 | C15—C14—H14B | 109.0 |
N5—C13—H13B | 109.2 | C13—C14—H14B | 109.0 |
C14—C13—H13B | 109.2 | C15—C14—H14A | 109.0 |
H13A—C13—H13B | 107.9 | C13—C14—H14A | 109.0 |
N4—C12—C11 | 110.0 (4) | H14B—C14—H14A | 107.8 |
N4—C12—H12A | 109.7 | N2—C4—C3 | 110.1 (4) |
C11—C12—H12A | 109.7 | N2—C4—H4B | 109.6 |
N4—C12—H12B | 109.7 | C3—C4—H4B | 109.6 |
C11—C12—H12B | 109.7 | N2—C4—H4A | 109.6 |
H12A—C12—H12B | 108.2 | C3—C4—H4A | 109.6 |
N4—C9—C10 | 111.4 (3) | H4B—C4—H4A | 108.1 |
N4—C9—H9B | 109.3 | O1—C2—C1 | 110.0 (5) |
C10—C9—H9B | 109.3 | O1—C2—H2A | 109.7 |
N4—C9—H9A | 109.3 | C1—C2—H2A | 109.7 |
C10—C9—H9A | 109.3 | O1—C2—H2B | 109.7 |
H9B—C9—H9A | 108.0 | C1—C2—H2B | 109.7 |
C3—O1—C2 | 110.8 (4) | H2A—C2—H2B | 108.2 |
O3—C10—C9 | 111.7 (4) | C14—C15—H15B | 109.5 |
O3—C10—H10A | 109.3 | C14—C15—H15C | 109.5 |
C9—C10—H10A | 109.3 | H15B—C15—H15C | 109.5 |
O3—C10—H10B | 109.3 | C14—C15—H15A | 109.5 |
C9—C10—H10B | 109.3 | H15B—C15—H15A | 109.5 |
H10A—C10—H10B | 107.9 | H15C—C15—H15A | 109.5 |
N3—C5—C6 | 111.4 (4) | O1—C3—C4 | 112.5 (4) |
N3—C5—H5B | 109.4 | O1—C3—H3A | 109.1 |
C6—C5—H5B | 109.4 | C4—C3—H3A | 109.1 |
N3—C5—H5A | 109.4 | O1—C3—H3B | 109.1 |
C6—C5—H5A | 109.4 | C4—C3—H3B | 109.1 |
H5B—C5—H5A | 108.0 | H3A—C3—H3B | 107.8 |
N3—C8—C7 | 109.5 (4) | P1—N6—P2i | 130.4 (2) |
N3—C8—H8B | 109.8 | ||
N6—P1—N1—P2 | 84.7 (3) | C9—N4—C12—C11 | −53.9 (4) |
N5—P1—N1—P2 | −48.0 (3) | P1—N4—C12—C11 | 175.2 (3) |
N4—P1—N1—P2 | −159.1 (3) | C12—N4—C9—C10 | 54.7 (4) |
N6i—P2—N1—P1 | −58.0 (3) | P1—N4—C9—C10 | −173.9 (3) |
N3—P2—N1—P1 | −179.0 (3) | C11—O3—C10—C9 | 58.8 (5) |
N2—P2—N1—P1 | 64.3 (3) | N4—C9—C10—O3 | −57.7 (4) |
N6—P1—N4—C12 | −174.8 (3) | C8—N3—C5—C6 | −54.5 (5) |
N1—P1—N4—C12 | 60.1 (3) | P2—N3—C5—C6 | 156.1 (3) |
N5—P1—N4—C12 | −54.8 (3) | C5—N3—C8—C7 | 54.0 (5) |
N6—P1—N4—C9 | 57.4 (3) | P2—N3—C8—C7 | −155.7 (3) |
N1—P1—N4—C9 | −67.7 (3) | C10—O3—C11—C12 | −59.4 (5) |
N5—P1—N4—C9 | 177.3 (3) | N4—C12—C11—O3 | 58.6 (5) |
N6—P1—N5—C13 | 45.6 (4) | C4—N2—C1—C2 | −54.1 (5) |
N1—P1—N5—C13 | 179.6 (3) | P2—N2—C1—C2 | 164.3 (3) |
N4—P1—N5—C13 | −66.1 (3) | C6—O2—C7—C8 | 60.7 (5) |
N6i—P2—N2—C1 | −35.4 (3) | N3—C8—C7—O2 | −57.6 (5) |
N1—P2—N2—C1 | −167.9 (3) | C7—O2—C6—C5 | −59.6 (5) |
N3—P2—N2—C1 | 80.0 (3) | N3—C5—C6—O2 | 56.9 (5) |
N6i—P2—N2—C4 | −174.3 (3) | N5—C13—C14—C15 | 169.5 (4) |
N1—P2—N2—C4 | 53.1 (3) | C1—N2—C4—C3 | 53.3 (5) |
N3—P2—N2—C4 | −59.0 (3) | P2—N2—C4—C3 | −164.1 (3) |
N6i—P2—N3—C5 | −169.1 (3) | C3—O1—C2—C1 | −57.2 (6) |
N1—P2—N3—C5 | −38.4 (4) | N2—C1—C2—O1 | 55.9 (5) |
N2—P2—N3—C5 | 77.3 (4) | C2—O1—C3—C4 | 59.0 (6) |
N6i—P2—N3—C8 | 44.1 (3) | N2—C4—C3—O1 | −56.5 (6) |
N1—P2—N3—C8 | 174.7 (3) | N1—P1—N6—P2i | −55.0 (3) |
N2—P2—N3—C8 | −69.6 (3) | N5—P1—N6—P2i | 74.8 (3) |
P1—N5—C13—C14 | 144.0 (3) | N4—P1—N6—P2i | −173.7 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C30H64N12O6P4 |
Mr | 812.81 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.502 (8), 10.939 (14), 11.814 (7) |
α, β, γ (°) | 66.39 (9), 81.63 (7), 81.74 (10) |
V (Å3) | 991.7 (17) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Enraf-Nonius TurboCAD-4 diffractometer |
Absorption correction | Part of the refinement model (ΔF) (SHELX97; Sheldrick, 1998) |
Tmin, Tmax | 0.928, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4298, 4016, 2115 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.183, 0.89 |
No. of reflections | 3578 |
No. of parameters | 239 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.33 |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
P1—N6 | 1.573 (3) | P2—N6i | 1.578 (3) |
P1—N1 | 1.584 (4) | P2—N1 | 1.587 (4) |
P1—N5 | 1.642 (4) | P2—N3 | 1.675 (4) |
P1—N4 | 1.672 (3) | P2—N2 | 1.684 (4) |
N6—P1—N1 | 117.50 (17) | N6i—P2—N3 | 107.50 (17) |
N6—P1—N5 | 114.88 (19) | N1—P2—N3 | 103.06 (19) |
N1—P1—N5 | 108.8 (2) | N6i—P2—N2 | 104.83 (18) |
N6—P1—N4 | 103.34 (19) | N1—P2—N2 | 108.59 (17) |
N1—P1—N4 | 107.90 (18) | N3—P2—N2 | 110.07 (18) |
N5—P1—N4 | 103.09 (17) | P1—N1—P2 | 136.9 (2) |
N6i—P2—N1 | 122.53 (17) | P1—N6—P2i | 130.4 (2) |
N6—P1—N1—P2 | 84.7 (3) | N2—P2—N1—P1 | 64.3 (3) |
N5—P1—N1—P2 | −48.0 (3) | N1—P1—N6—P2i | −55.0 (3) |
N4—P1—N1—P2 | −159.1 (3) | N5—P1—N6—P2i | 74.8 (3) |
N6i—P2—N1—P1 | −58.0 (3) | N4—P1—N6—P2i | −173.7 (2) |
N3—P2—N1—P1 | −179.0 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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Cyclophosphazenes have attracted much interest as a result of their potential use in the sythesis of new small-molecule organocyclophosphazenes (Allcock et al., 1992) and high polymeric phosphazenes with inorganic backbones, which have many different uses (Allcock et al., 1987; Hökelek et al., 1996), and aryloxy side groups, which may be useful as high refractive index glasses (Olshavsky & Allcock, 1995), ferroelectric and non-linear optical polymers (Allcock et al., 1991), liquid crystalline materials (Allcock & Kim, 1991) and biomedical materials (Cohen et al., 1990).
On the other hand, some of the aminophosphazenes are thought to be useful as cancer chemotherapeutic agents (Chernov et al., 1959; van der Huizen, 1984). A relationship has been determined between the structures of the cyclophosphazenes and cytostatic activity (van der Huizen, 1984), and for effective tumuor-growth inhibition, electron-donating groups (e.g. aziridine, pyrrolidine, morpholine, primary and secondary amines) in the P–N ring skeletons seem to be essential.
The crystal structures of some N4P4Cl8 derivatives, such as [N4P4(NMe2)8], (II) (Bullen, 1962), β-trans-N4P4(NHMe)4Ph4, (III) (Bullen & Mallinson, 1972), [N4P4Cl4(NEt2)4], (IV) (Hökelek & Kılıç, 1990), [N4P4Cl7(OC6H2-2,6-tBu2-4-Me)], (V) (Hökelek et al., 1996), [N4P4(NC4H8O)6(NHCH2CH3), (VI) (Hökelek, Kılıç & Kılıç, 1998), and [N4P4(NC5H10)6(NHEt)2], (VII) (Hökelek et al., 1999), have been determined.
A structure analysis of the title compound, (I), was undertaken to determine the influences of the relatively hindered side groups, and also of the steric and electronic factors, on the macrocyclic tetraphosphazene ring. The title compound is illustrated in Fig. 1. The structure consists of a centrosymmetric non-planar cyclic tetrameric phosphazene ring in a chair conformation, with two n-propylamino (in 2,6-trans positions) and six bulky morpholino side groups. The four P atoms are coplanar and the four N atoms are displaced above (+) and below (-) their plane by equal amounts [N1 - 0.513 (4) Å and N6 - 0.317 (4) Å]. The conformation of the macrocyclic phosphazene ring is indicated by the torsion angles of the ring bonds in which the symmetry operation reverses the sign of a torsion angle (Fig. 2).
As can be seen from the distribution of the endocyclic torsion angles, it appears that in the central ring there are two local pseudo-mirrors, one running along the midpoints of the N6—P2' and N6'—P2 bonds, the other along the midpoints of the P1—N1 and P1'—N1' bonds. The P—N—P bond angles are 130.4 (2) and 136.9 (2)° (average 133.7°). The P—N—P bond angles are in the ranges 135.1 (4)–139.2 (4), 133.6 (2)–139.3 (2), 127.3 (2)–134.4 (2) and 130.0 (1)–130.1 (1)° in compounds (IV), (V), (VI) and (VII), respectively. It was reported that such large angles appear to be characteristic of molecules containing chlorine or fluorine (George et al., 1972). Although, the title compound contains neither chlorine nor fluorine, large P—N—P angles appear to be due to the different substituents on the P atoms; the endocyclic N—P—N angles vary in the range 117.5 (2)–122.5 (2)° [average 120.0°].
In trimeric phosphazenes, it has been observed that endocyclic (N—P—N) angles about P decrease, while exocyclic (R—P—R') angles increase (Kılıç et al., 1996; Hökelek et al., 1996, 1998, 1999). The title compound and other tetrameric phosphazenes containing bulky phenoxy groups (Allcock et al., 1995) are different. The exocyclic N2—P2—N3 angle [110.1 (2)°] is highly affected, while the endocyclic N1—P2—N6' angle [122.6 (2)°] is less affected, by the existence of the two repelling morpholino groups bonded to the P2 atom, compared with the parent compound N4P4Cl8 (Cl—P—Cl 103.1° and N—P—N 120.5°; Wagner & Vos, 1968). On the other hand, the exocyclic N4—P1—N5 angle [103.1 (2)°] remains unchanged, while the endocyclic N1—P1—N6 angle [117.5 (2)°] decreases as a result of the morpholino and n-propylamino groups bonded to the P1 atom. These interactions show that steric factors are more dominant than electronic factors, with respect to the ring skeleton. The P1—N1—P2 angle is 136.9 (2)°, but the P1—N6—P2' angle [130.4 (2)°] is narrowed compared with the corresponding angles in N4P4Cl8 (133.6 and 137.6°; Wagner & Vos, 1968).
In tetrameric phosphazenes, the P—N bond lengths have been correlated with the electronegativities of the substituents (Bullen & Tucker, 1972). In the present structure, the bulky morpholino and n-propylamino groups are electron donating. In the chair-shaped cyclic tetrameric phosphazene ring, the P—N bond distances vary from 1.573 (3) to 1.587 (4) Å. The average ring P—N bond length is 1.580 Å. In related compounds, the mean bond lengths are 1.561 Å in (IV), 1.558 Å in (V), 1.583 Å in (VI) and 1.585 Å in (VII). The P—N bond lengths are considerably shorter than the P—N single-bond length of 1.683 (5) Å (Allen et al., 1987). The short bonds in the ring have an appreciable double-bond character; this is generally observed for phosphanitrilic molecules (Wagner & Vos, 1968).
The mean exocyclic bond length (1.668 Å) is nearly the same as that in (II) (1.679 Å). It has been generally observed that the exocyclic P—N bonds are longer than the endocyclic P—N bonds in the ring (Ahmed & Pollard, 1972).