Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801017056/bt6084sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801017056/bt6084Isup2.hkl |
CCDC reference: 176019
2,2'-Methylenebis(4-nitrophenol) (10.0 g, 34.4 mmol) in tetrahydrofuran (THF, 100 ml) was added slowly over a period of 30 min to a solution of NaH (1.65 g, 6.88 mmol) in THF (50 ml) with stirring at 298 K, with argon being passed over the reaction mixture. The solvent was removed under reduced pressure and the residue was dried. The sodium phenoxide (1.00 g, 2.99 mmol) were dissolved in benzene (50 ml). To this mixture, N3P3Ph2Cl4 (1.08 g, 2.99 mmol) in benzene (100 ml) at 253 K was added slowly and the resulting solution allowed to come to ambient temperature with constant stirring. After the mixture had been vigorously stirred and boiled under reflux for 36 h, the precipitated salt (NaCl) was filtered off and the solvent removed in vacuo. The cis-ansa product was separated by column chromatography. The crude product was crystallized from CH3CN [yield 0.92 g, 47%; m.p. 407 K (decomposed)].
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).
Fig. 1. An ORTEPII (Johnson, 1976) drawing of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. |
C25H18Cl2N5O6P3 | Z = 2 |
Mr = 648.25 | F(000) = 660 |
Triclinic, P1 | Dx = 1.583 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9482 (10) Å | Cell parameters from 25 reflections |
b = 11.2184 (10) Å | θ = 10–11° |
c = 12.8536 (10) Å | µ = 0.47 mm−1 |
α = 97.702 (7)° | T = 293 K |
β = 105.515 (7)° | Rod-shaped, colorless |
γ = 94.503 (7)° | 0.30 × 0.15 × 0.15 mm |
V = 1359.9 (2) Å3 |
Enraf-Nonius CAD-4 diffractometer | 4666 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 26.3°, θmin = 2.1° |
non–profiled ω scans | h = −12→11 |
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983) | k = −13→13 |
Tmin = 0.873, Tmax = 0.933 | l = 0→16 |
5465 measured reflections | 3 standard reflections every 120 min |
5465 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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.258 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.22 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
5465 reflections | (Δ/σ)max < 0.001 |
378 parameters | Δρmax = 1.28 e Å−3 |
0 restraints | Δρmin = −1.28 e Å−3 |
C25H18Cl2N5O6P3 | γ = 94.503 (7)° |
Mr = 648.25 | V = 1359.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.9482 (10) Å | Mo Kα radiation |
b = 11.2184 (10) Å | µ = 0.47 mm−1 |
c = 12.8536 (10) Å | T = 293 K |
α = 97.702 (7)° | 0.30 × 0.15 × 0.15 mm |
β = 105.515 (7)° |
Enraf-Nonius CAD-4 diffractometer | 4666 reflections with I > 2σ(I) |
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983) | Rint = 0.000 |
Tmin = 0.873, Tmax = 0.933 | 3 standard reflections every 120 min |
5465 measured reflections | intensity decay: 3% |
5465 independent reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.258 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.22 | Δρmax = 1.28 e Å−3 |
5465 reflections | Δρmin = −1.28 e Å−3 |
378 parameters |
Experimental. The dihedral angles between the phenyl ring planes [A(C1—C6), B(C8—C13), C(C14—C19), D(C20—C25)] are A/B = 86.6 (1), A/C = 42.1 (1), A/D = 87.7 (1), B/C = 69.0 (1), B/D = 12.1 (1) and C/D =80.2 (1)°. |
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 | ||
Cl1 | −0.00104 (9) | −0.06640 (7) | 0.20570 (8) | 0.0416 (3) | |
Cl2 | 0.10545 (10) | 0.22777 (10) | 0.59595 (7) | 0.0502 (3) | |
P1 | 0.33519 (7) | 0.23358 (7) | 0.35573 (6) | 0.0280 (3) | |
P2 | 0.11364 (8) | 0.26001 (8) | 0.44888 (6) | 0.0310 (3) | |
P3 | 0.07091 (7) | 0.10904 (7) | 0.25471 (6) | 0.0277 (3) | |
O1 | −0.0084 (2) | 0.1688 (2) | 0.15326 (19) | 0.0324 (5) | |
O6 | 0.0324 (2) | 0.3780 (2) | 0.44544 (18) | 0.0356 (5) | |
N1 | 0.2701 (3) | 0.2927 (3) | 0.4495 (2) | 0.0351 (6) | |
N2 | 0.0210 (3) | 0.1519 (3) | 0.3594 (2) | 0.0328 (6) | |
N3 | 0.2316 (3) | 0.1299 (3) | 0.2633 (2) | 0.0319 (6) | |
N4 | −0.5676 (3) | 0.1429 (4) | −0.0954 (3) | 0.0553 (9) | |
O2 | −0.6381 (3) | 0.2160 (4) | −0.0684 (4) | 0.0881 (13) | |
O3 | −0.6110 (4) | 0.0623 (5) | −0.1717 (4) | 0.1136 (19) | |
N5 | 0.0581 (4) | 0.6352 (3) | 0.1066 (3) | 0.0534 (9) | |
O4 | −0.0478 (4) | 0.6306 (4) | 0.0303 (3) | 0.0798 (11) | |
O5 | 0.1709 (4) | 0.6903 (4) | 0.1127 (4) | 0.0822 (12) | |
C1 | −0.1530 (3) | 0.1569 (3) | 0.0995 (3) | 0.0300 (7) | |
C2 | −0.2397 (3) | 0.2341 (3) | 0.1380 (3) | 0.0315 (7) | |
C3 | −0.3779 (3) | 0.2261 (3) | 0.0707 (3) | 0.0373 (7) | |
H3 | −0.4401 | 0.2756 | 0.0915 | 0.045* | |
C4 | −0.4217 (3) | 0.1458 (3) | −0.0253 (3) | 0.0381 (8) | |
C5 | −0.3364 (4) | 0.0674 (3) | −0.0610 (3) | 0.0411 (8) | |
H5 | −0.3697 | 0.0121 | −0.1254 | 0.049* | |
C6 | −0.1988 (3) | 0.0755 (3) | 0.0042 (3) | 0.0369 (7) | |
H6 | −0.1374 | 0.0253 | −0.0169 | 0.044* | |
C7 | −0.1968 (3) | 0.3207 (3) | 0.2451 (3) | 0.0343 (7) | |
C8 | −0.0712 (3) | 0.4141 (3) | 0.2616 (3) | 0.0319 (7) | |
C9 | −0.0640 (4) | 0.4816 (3) | 0.1789 (3) | 0.0390 (8) | |
H9 | −0.1348 | 0.4684 | 0.1131 | 0.047* | |
C10 | 0.0494 (4) | 0.5680 (3) | 0.1963 (3) | 0.0399 (8) | |
C11 | 0.1549 (4) | 0.5952 (3) | 0.2931 (3) | 0.0419 (8) | |
H11 | 0.2293 | 0.6549 | 0.3022 | 0.050* | |
C12 | 0.1472 (4) | 0.5314 (3) | 0.3761 (3) | 0.0410 (8) | |
H12 | 0.2161 | 0.5482 | 0.4430 | 0.049* | |
C13 | 0.0352 (3) | 0.4416 (3) | 0.3588 (3) | 0.0318 (7) | |
C14 | 0.4929 (3) | 0.1756 (3) | 0.4228 (3) | 0.0317 (7) | |
C15 | 0.5250 (4) | 0.1669 (3) | 0.5331 (3) | 0.0378 (7) | |
H15 | 0.4657 | 0.1936 | 0.5739 | 0.045* | |
C16 | 0.6454 (4) | 0.1184 (4) | 0.5826 (3) | 0.0494 (10) | |
H16 | 0.6665 | 0.1115 | 0.6564 | 0.059* | |
C17 | 0.7342 (4) | 0.0801 (3) | 0.5211 (4) | 0.0453 (9) | |
H17 | 0.8164 | 0.0497 | 0.5546 | 0.054* | |
C18 | 0.7021 (4) | 0.0866 (4) | 0.4113 (4) | 0.0501 (10) | |
H18 | 0.7615 | 0.0592 | 0.3708 | 0.060* | |
C19 | 0.5815 (3) | 0.1338 (3) | 0.3607 (3) | 0.0400 (8) | |
H19 | 0.5593 | 0.1378 | 0.2864 | 0.048* | |
C20 | 0.3899 (3) | 0.3516 (3) | 0.2879 (3) | 0.0316 (7) | |
C21 | 0.4966 (4) | 0.4433 (3) | 0.3478 (3) | 0.0399 (8) | |
H21 | 0.5401 | 0.4423 | 0.4213 | 0.048* | |
C22 | 0.5367 (5) | 0.5352 (4) | 0.2969 (4) | 0.0545 (10) | |
H22 | 0.6064 | 0.5973 | 0.3365 | 0.065* | |
C23 | 0.4730 (5) | 0.5349 (4) | 0.1867 (4) | 0.0562 (11) | |
H23 | 0.5015 | 0.5961 | 0.1523 | 0.067* | |
C24 | 0.3696 (5) | 0.4462 (4) | 0.1290 (4) | 0.0538 (10) | |
H24 | 0.3269 | 0.4473 | 0.0554 | 0.065* | |
C25 | 0.3266 (4) | 0.3539 (3) | 0.1784 (3) | 0.0391 (8) | |
H25 | 0.2554 | 0.2934 | 0.1382 | 0.047* | |
H71 | −0.271 (4) | 0.377 (3) | 0.254 (3) | 0.034 (9)* | |
H72 | −0.168 (4) | 0.285 (4) | 0.314 (4) | 0.043 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0380 (5) | 0.0385 (5) | 0.0493 (5) | 0.0022 (3) | 0.0121 (4) | 0.0128 (4) |
Cl2 | 0.0474 (6) | 0.0793 (7) | 0.0343 (5) | 0.0136 (5) | 0.0197 (4) | 0.0255 (4) |
P1 | 0.0174 (4) | 0.0401 (5) | 0.0296 (5) | 0.0073 (3) | 0.0081 (3) | 0.0118 (3) |
P2 | 0.0236 (4) | 0.0473 (5) | 0.0283 (5) | 0.0106 (3) | 0.0122 (3) | 0.0136 (4) |
P3 | 0.0176 (4) | 0.0377 (5) | 0.0319 (5) | 0.0076 (3) | 0.0091 (3) | 0.0128 (3) |
O1 | 0.0183 (10) | 0.0473 (13) | 0.0361 (12) | 0.0091 (9) | 0.0086 (9) | 0.0178 (10) |
O6 | 0.0309 (12) | 0.0531 (14) | 0.0310 (12) | 0.0170 (10) | 0.0160 (9) | 0.0137 (10) |
N1 | 0.0236 (13) | 0.0504 (17) | 0.0335 (14) | 0.0090 (11) | 0.0100 (10) | 0.0076 (12) |
N2 | 0.0199 (12) | 0.0483 (16) | 0.0363 (14) | 0.0079 (10) | 0.0135 (10) | 0.0138 (12) |
N3 | 0.0156 (12) | 0.0504 (16) | 0.0334 (14) | 0.0098 (10) | 0.0099 (10) | 0.0099 (12) |
N4 | 0.0278 (16) | 0.075 (2) | 0.054 (2) | 0.0099 (15) | −0.0024 (14) | 0.0068 (18) |
O2 | 0.0342 (16) | 0.103 (3) | 0.104 (3) | 0.0299 (18) | −0.0129 (17) | −0.010 (2) |
O3 | 0.050 (2) | 0.168 (4) | 0.083 (3) | 0.034 (2) | −0.022 (2) | −0.045 (3) |
N5 | 0.066 (2) | 0.0454 (19) | 0.057 (2) | 0.0124 (16) | 0.0205 (18) | 0.0252 (15) |
O4 | 0.082 (2) | 0.092 (3) | 0.067 (2) | 0.010 (2) | 0.0061 (19) | 0.051 (2) |
O5 | 0.080 (2) | 0.077 (2) | 0.101 (3) | −0.0044 (19) | 0.032 (2) | 0.051 (2) |
C1 | 0.0203 (14) | 0.0390 (16) | 0.0347 (16) | 0.0051 (11) | 0.0088 (12) | 0.0168 (13) |
C2 | 0.0212 (14) | 0.0398 (17) | 0.0374 (17) | 0.0067 (12) | 0.0087 (12) | 0.0166 (13) |
C3 | 0.0203 (14) | 0.0472 (19) | 0.0483 (19) | 0.0099 (12) | 0.0101 (13) | 0.0170 (15) |
C4 | 0.0207 (15) | 0.050 (2) | 0.0429 (19) | 0.0054 (13) | 0.0025 (13) | 0.0171 (15) |
C5 | 0.0325 (17) | 0.051 (2) | 0.0379 (18) | 0.0035 (14) | 0.0066 (14) | 0.0081 (15) |
C6 | 0.0276 (16) | 0.050 (2) | 0.0370 (17) | 0.0118 (13) | 0.0104 (13) | 0.0123 (14) |
C7 | 0.0241 (15) | 0.0477 (19) | 0.0368 (18) | 0.0117 (13) | 0.0134 (13) | 0.0127 (14) |
C8 | 0.0272 (15) | 0.0380 (17) | 0.0349 (16) | 0.0115 (12) | 0.0120 (12) | 0.0107 (13) |
C9 | 0.0359 (18) | 0.0425 (18) | 0.0402 (18) | 0.0125 (14) | 0.0079 (14) | 0.0137 (14) |
C10 | 0.0444 (19) | 0.0359 (18) | 0.048 (2) | 0.0136 (14) | 0.0210 (16) | 0.0158 (14) |
C11 | 0.0377 (19) | 0.0354 (18) | 0.052 (2) | −0.0006 (14) | 0.0134 (16) | 0.0064 (15) |
C12 | 0.0346 (17) | 0.0435 (19) | 0.0425 (19) | 0.0092 (14) | 0.0065 (14) | 0.0047 (14) |
C13 | 0.0315 (15) | 0.0351 (16) | 0.0334 (16) | 0.0109 (12) | 0.0136 (13) | 0.0083 (12) |
C14 | 0.0198 (14) | 0.0377 (17) | 0.0392 (17) | 0.0036 (11) | 0.0072 (12) | 0.0148 (13) |
C15 | 0.0357 (17) | 0.0390 (18) | 0.0381 (18) | 0.0046 (13) | 0.0071 (14) | 0.0110 (14) |
C16 | 0.047 (2) | 0.049 (2) | 0.045 (2) | 0.0021 (16) | −0.0072 (16) | 0.0242 (17) |
C17 | 0.0273 (17) | 0.0420 (19) | 0.062 (2) | 0.0040 (14) | −0.0019 (15) | 0.0218 (17) |
C18 | 0.0225 (16) | 0.060 (2) | 0.077 (3) | 0.0148 (15) | 0.0177 (17) | 0.031 (2) |
C19 | 0.0223 (15) | 0.056 (2) | 0.048 (2) | 0.0100 (13) | 0.0115 (14) | 0.0241 (16) |
C20 | 0.0232 (14) | 0.0381 (17) | 0.0380 (17) | 0.0078 (12) | 0.0122 (12) | 0.0116 (13) |
C21 | 0.0309 (17) | 0.045 (2) | 0.0435 (19) | 0.0038 (14) | 0.0098 (14) | 0.0086 (15) |
C22 | 0.046 (2) | 0.048 (2) | 0.075 (3) | 0.0006 (17) | 0.024 (2) | 0.016 (2) |
C23 | 0.054 (2) | 0.052 (2) | 0.075 (3) | 0.0086 (18) | 0.028 (2) | 0.033 (2) |
C24 | 0.060 (3) | 0.063 (3) | 0.049 (2) | 0.018 (2) | 0.0189 (19) | 0.034 (2) |
C25 | 0.0363 (18) | 0.0472 (19) | 0.0364 (17) | 0.0080 (14) | 0.0097 (14) | 0.0148 (14) |
Cl1—P3 | 1.9970 (12) | C7—H72 | 1.00 (4) |
Cl2—P2 | 1.9930 (12) | C8—C13 | 1.384 (5) |
P1—N1 | 1.607 (3) | C8—C9 | 1.399 (5) |
P1—N3 | 1.617 (3) | C9—C10 | 1.377 (5) |
P1—C14 | 1.792 (3) | C9—H9 | 0.9300 |
P1—C20 | 1.806 (3) | C10—C11 | 1.375 (5) |
P2—N1 | 1.568 (3) | C11—C12 | 1.377 (5) |
P2—N2 | 1.589 (3) | C11—H11 | 0.9300 |
P2—O6 | 1.604 (2) | C12—C13 | 1.392 (5) |
P3—N3 | 1.569 (2) | C12—H12 | 0.9300 |
P3—N2 | 1.585 (3) | C14—C15 | 1.386 (5) |
P3—O1 | 1.594 (2) | C14—C19 | 1.405 (5) |
O1—C1 | 1.407 (4) | C15—C16 | 1.387 (5) |
O6—C13 | 1.405 (4) | C15—H15 | 0.9300 |
N4—O2 | 1.195 (5) | C16—C17 | 1.391 (6) |
N4—O3 | 1.201 (5) | C16—H16 | 0.9300 |
N4—C4 | 1.485 (4) | C17—C18 | 1.374 (6) |
N5—O5 | 1.217 (5) | C17—H17 | 0.9300 |
N5—O4 | 1.225 (5) | C18—C19 | 1.384 (5) |
N5—C10 | 1.476 (5) | C18—H18 | 0.9300 |
C1—C6 | 1.370 (5) | C19—H19 | 0.9300 |
C1—C2 | 1.404 (4) | C20—C25 | 1.384 (5) |
C2—C3 | 1.403 (4) | C20—C21 | 1.398 (5) |
C2—C7 | 1.512 (5) | C21—C22 | 1.381 (5) |
C3—C4 | 1.371 (5) | C21—H21 | 0.9300 |
C3—H3 | 0.9300 | C22—C23 | 1.388 (7) |
C4—C5 | 1.385 (5) | C22—H22 | 0.9300 |
C5—C6 | 1.390 (5) | C23—C24 | 1.354 (7) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—H6 | 0.9300 | C24—C25 | 1.382 (5) |
C7—C8 | 1.516 (5) | C24—H24 | 0.9300 |
C7—H71 | 1.02 (4) | C25—H25 | 0.9300 |
N1—P1—N3 | 115.58 (14) | C13—C8—C7 | 122.6 (3) |
N1—P1—C14 | 107.18 (15) | C9—C8—C7 | 119.9 (3) |
N3—P1—C14 | 110.77 (14) | C10—C9—C8 | 119.1 (3) |
N1—P1—C20 | 109.11 (15) | C10—C9—H9 | 120.5 |
N3—P1—C20 | 107.95 (15) | C8—C9—H9 | 120.5 |
C14—P1—C20 | 105.82 (14) | C11—C10—C9 | 123.4 (3) |
N1—P2—N2 | 118.13 (15) | C11—C10—N5 | 118.2 (3) |
N1—P2—O6 | 110.74 (15) | C9—C10—N5 | 118.4 (4) |
N2—P2—O6 | 109.57 (13) | C10—C11—C12 | 118.1 (3) |
N1—P2—Cl2 | 110.16 (12) | C10—C11—H11 | 121.0 |
N2—P2—Cl2 | 108.42 (11) | C12—C11—H11 | 121.0 |
O6—P2—Cl2 | 97.92 (9) | C11—C12—C13 | 119.2 (3) |
N3—P3—N2 | 118.71 (15) | C11—C12—H12 | 120.4 |
N3—P3—O1 | 106.37 (13) | C13—C12—H12 | 120.4 |
N2—P3—O1 | 111.16 (13) | C8—C13—C12 | 122.8 (3) |
N3—P3—Cl1 | 110.07 (11) | C8—C13—O6 | 119.9 (3) |
N2—P3—Cl1 | 106.87 (11) | C12—C13—O6 | 117.3 (3) |
O1—P3—Cl1 | 102.49 (10) | C15—C14—C19 | 119.9 (3) |
C1—O1—P3 | 128.84 (19) | C15—C14—P1 | 121.0 (3) |
C13—O6—P2 | 115.58 (19) | C19—C14—P1 | 119.0 (3) |
P2—N1—P1 | 123.14 (19) | C14—C15—C16 | 120.1 (4) |
P3—N2—P2 | 118.80 (16) | C14—C15—H15 | 119.9 |
P3—N3—P1 | 120.64 (17) | C16—C15—H15 | 119.9 |
O2—N4—O3 | 123.7 (4) | C15—C16—C17 | 119.4 (4) |
O2—N4—C4 | 118.2 (4) | C15—C16—H16 | 120.3 |
O3—N4—C4 | 118.0 (4) | C17—C16—H16 | 120.3 |
O5—N5—O4 | 124.1 (4) | C18—C17—C16 | 120.8 (3) |
O5—N5—C10 | 117.7 (4) | C18—C17—H17 | 119.6 |
O4—N5—C10 | 118.2 (4) | C16—C17—H17 | 119.6 |
C6—C1—C2 | 123.2 (3) | C17—C18—C19 | 120.2 (4) |
C6—C1—O1 | 116.3 (3) | C17—C18—H18 | 119.9 |
C2—C1—O1 | 120.2 (3) | C19—C18—H18 | 119.9 |
C3—C2—C1 | 115.8 (3) | C18—C19—C14 | 119.4 (4) |
C3—C2—C7 | 118.8 (3) | C18—C19—H19 | 120.3 |
C1—C2—C7 | 125.4 (3) | C14—C19—H19 | 120.3 |
C4—C3—C2 | 120.4 (3) | C25—C20—C21 | 119.6 (3) |
C4—C3—H3 | 119.8 | C25—C20—P1 | 121.2 (3) |
C2—C3—H3 | 119.8 | C21—C20—P1 | 119.2 (3) |
C3—C4—C5 | 123.4 (3) | C22—C21—C20 | 119.5 (4) |
C3—C4—N4 | 118.5 (3) | C22—C21—H21 | 120.3 |
C5—C4—N4 | 118.2 (3) | C20—C21—H21 | 120.3 |
C4—C5—C6 | 116.8 (3) | C21—C22—C23 | 119.9 (4) |
C4—C5—H5 | 121.6 | C21—C22—H22 | 120.0 |
C6—C5—H5 | 121.6 | C23—C22—H22 | 120.0 |
C1—C6—C5 | 120.4 (3) | C24—C23—C22 | 120.4 (4) |
C1—C6—H6 | 119.8 | C24—C23—H23 | 119.8 |
C5—C6—H6 | 119.8 | C22—C23—H23 | 119.8 |
C2—C7—C8 | 116.0 (3) | C23—C24—C25 | 120.7 (4) |
C2—C7—H71 | 113 (2) | C23—C24—H24 | 119.6 |
C8—C7—H71 | 100 (2) | C25—C24—H24 | 119.6 |
C2—C7—H72 | 118 (2) | C24—C25—C20 | 119.9 (3) |
C8—C7—H72 | 101 (2) | C24—C25—H25 | 120.1 |
H71—C7—H72 | 107 (3) | C20—C25—H25 | 120.1 |
C13—C8—C9 | 117.3 (3) | ||
N3—P3—O1—C1 | 167.7 (3) | C13—C8—C9—C10 | 2.3 (5) |
N2—P3—O1—C1 | −61.7 (3) | C7—C8—C9—C10 | 178.5 (3) |
Cl1—P3—O1—C1 | 52.2 (3) | C8—C9—C10—C11 | −2.5 (6) |
N1—P2—O6—C13 | 55.1 (3) | C8—C9—C10—N5 | 177.7 (3) |
N2—P2—O6—C13 | −76.9 (3) | O5—N5—C10—C11 | 16.4 (6) |
Cl2—P2—O6—C13 | 170.3 (2) | O4—N5—C10—C11 | −164.6 (4) |
N2—P2—N1—P1 | 7.7 (3) | O5—N5—C10—C9 | −163.8 (4) |
O6—P2—N1—P1 | −119.7 (2) | O4—N5—C10—C9 | 15.2 (6) |
Cl2—P2—N1—P1 | 133.03 (18) | C9—C10—C11—C12 | 0.8 (6) |
N3—P1—N1—P2 | −4.0 (3) | N5—C10—C11—C12 | −179.3 (3) |
C14—P1—N1—P2 | −128.1 (2) | C10—C11—C12—C13 | 0.9 (5) |
C20—P1—N1—P2 | 117.8 (2) | C9—C8—C13—C12 | −0.6 (5) |
N3—P3—N2—P2 | 26.2 (3) | C7—C8—C13—C12 | −176.7 (3) |
O1—P3—N2—P2 | −97.58 (19) | C9—C8—C13—O6 | 179.0 (3) |
Cl1—P3—N2—P2 | 151.34 (15) | C7—C8—C13—O6 | 2.9 (5) |
N1—P2—N2—P3 | −18.6 (3) | C11—C12—C13—C8 | −1.0 (5) |
O6—P2—N2—P3 | 109.47 (18) | C11—C12—C13—O6 | 179.4 (3) |
Cl2—P2—N2—P3 | −144.72 (15) | P2—O6—C13—C8 | 91.7 (3) |
N2—P3—N3—P1 | −22.9 (3) | P2—O6—C13—C12 | −88.7 (3) |
O1—P3—N3—P1 | 103.29 (19) | N1—P1—C14—C15 | 11.4 (3) |
Cl1—P3—N3—P1 | −146.39 (15) | N3—P1—C14—C15 | −115.5 (3) |
N1—P1—N3—P3 | 11.5 (3) | C20—P1—C14—C15 | 127.8 (3) |
C14—P1—N3—P3 | 133.65 (18) | N1—P1—C14—C19 | −171.3 (3) |
C20—P1—N3—P3 | −110.93 (19) | N3—P1—C14—C19 | 61.8 (3) |
P3—O1—C1—C6 | −98.9 (3) | C20—P1—C14—C19 | −55.0 (3) |
P3—O1—C1—C2 | 87.0 (3) | C19—C14—C15—C16 | 0.8 (5) |
C6—C1—C2—C3 | −1.9 (5) | P1—C14—C15—C16 | 178.0 (3) |
O1—C1—C2—C3 | 171.7 (3) | C14—C15—C16—C17 | 0.8 (6) |
C6—C1—C2—C7 | 176.6 (3) | C15—C16—C17—C18 | −1.9 (6) |
O1—C1—C2—C7 | −9.8 (5) | C16—C17—C18—C19 | 1.3 (6) |
C1—C2—C3—C4 | 0.7 (5) | C17—C18—C19—C14 | 0.4 (6) |
C7—C2—C3—C4 | −177.9 (3) | C15—C14—C19—C18 | −1.4 (5) |
C2—C3—C4—C5 | 1.3 (5) | P1—C14—C19—C18 | −178.7 (3) |
C2—C3—C4—N4 | −178.3 (3) | N1—P1—C20—C25 | −115.7 (3) |
O2—N4—C4—C3 | 4.5 (6) | N3—P1—C20—C25 | 10.6 (3) |
O3—N4—C4—C3 | −170.5 (5) | C14—P1—C20—C25 | 129.2 (3) |
O2—N4—C4—C5 | −175.1 (4) | N1—P1—C20—C21 | 63.2 (3) |
O3—N4—C4—C5 | 9.9 (7) | N3—P1—C20—C21 | −170.5 (3) |
C3—C4—C5—C6 | −2.0 (6) | C14—P1—C20—C21 | −51.8 (3) |
N4—C4—C5—C6 | 177.6 (3) | C25—C20—C21—C22 | 0.4 (5) |
C2—C1—C6—C5 | 1.2 (5) | P1—C20—C21—C22 | −178.6 (3) |
O1—C1—C6—C5 | −172.7 (3) | C20—C21—C22—C23 | −1.1 (6) |
C4—C5—C6—C1 | 0.8 (5) | C21—C22—C23—C24 | 1.3 (7) |
C3—C2—C7—C8 | −123.8 (3) | C22—C23—C24—C25 | −0.6 (7) |
C1—C2—C7—C8 | 57.7 (4) | C23—C24—C25—C20 | −0.1 (6) |
C2—C7—C8—C13 | −135.8 (3) | C21—C20—C25—C24 | 0.3 (5) |
C2—C7—C8—C9 | 48.2 (4) | P1—C20—C25—C24 | 179.2 (3) |
Experimental details
Crystal data | |
Chemical formula | C25H18Cl2N5O6P3 |
Mr | 648.25 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.9482 (10), 11.2184 (10), 12.8536 (10) |
α, β, γ (°) | 97.702 (7), 105.515 (7), 94.503 (7) |
V (Å3) | 1359.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.47 |
Crystal size (mm) | 0.30 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Part of the refinement model (ΔF) (Walker & Stuart, 1983) |
Tmin, Tmax | 0.873, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5465, 5465, 4666 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.258, 1.22 |
No. of reflections | 5465 |
No. of parameters | 378 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.28, −1.28 |
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).
Cl1—P3 | 1.9970 (12) | P2—N2 | 1.589 (3) |
Cl2—P2 | 1.9930 (12) | P2—O6 | 1.604 (2) |
P1—N1 | 1.607 (3) | P3—N3 | 1.569 (2) |
P1—N3 | 1.617 (3) | P3—N2 | 1.585 (3) |
P1—C14 | 1.792 (3) | P3—O1 | 1.594 (2) |
P1—C20 | 1.806 (3) | O1—C1 | 1.407 (4) |
P2—N1 | 1.568 (3) | O6—C13 | 1.405 (4) |
N1—P1—N3 | 115.58 (14) | N3—P3—N2 | 118.71 (15) |
N1—P1—C14 | 107.18 (15) | N3—P3—O1 | 106.37 (13) |
N3—P1—C14 | 110.77 (14) | N2—P3—O1 | 111.16 (13) |
N1—P1—C20 | 109.11 (15) | N3—P3—Cl1 | 110.07 (11) |
N3—P1—C20 | 107.95 (15) | N2—P3—Cl1 | 106.87 (11) |
C14—P1—C20 | 105.82 (14) | O1—P3—Cl1 | 102.49 (10) |
N1—P2—N2 | 118.13 (15) | C1—O1—P3 | 128.84 (19) |
N1—P2—O6 | 110.74 (15) | C13—O6—P2 | 115.58 (19) |
N2—P2—O6 | 109.57 (13) | P2—N1—P1 | 123.14 (19) |
N1—P2—Cl2 | 110.16 (12) | P3—N2—P2 | 118.80 (16) |
N2—P2—Cl2 | 108.42 (11) | P3—N3—P1 | 120.64 (17) |
O6—P2—Cl2 | 97.92 (9) |
We have previously investigated the reactions of sodium 2,2'-methylenebis-(4-nitrophenoxide) and hexachlorocyclotriphosphazatriene, N3P3Cl6. When equal amounts of the reactants were reacted, the reaction yields two different products, namely the cis-ansa and spiro-isomers (Hökelek, Akduran, Yıldız et al., 2000). The title compound, (I), is the first cis-ansa-cyclophosphazene derivative, and was obtained from the reaction of N3P3Ph2Cl4 and 2,2'-methylenebis(4-nitrophenoxide).
N3P3Cl6 is the starting material for the preparation of trimeric phosphazene. The crystal structures of N3P3Cl6 (Bullen, 1971) and a few of its derivatives with bulky phenoxy groups, such as Cl4N3P3[(OC6H3)(NO2)CH2(OC6H3)(NO2)], (II) (Hökelek, Akduran, Yıldız et al., 2000), [Cl5N3P3(OC6H2-2,6-tBu2-4-Me], (III) (Hökelek et al., 1999), [Cl5N3P3(OC6H2-2,4,6-tBu3)], (IV) (Kılıç et al., 1996), [N3P3(OC6H4OCH2Ph-4)6], (V) (Allcock et al., 1996), [Cl5N3P3—P3N3Cl4(OC6H3-2,6-tBu2)], (VI) (Hökelek et al., 1994), [N3P3Cl4(OC6H3Cl2-o)2], (VII), and [N3P3Cl4(OC6H3Me2-o)2], (VIII) (Allcock, Ngo et al., 1992), have been reported.
The study of cyclic phosphazenes has attracted great interest with respect to their synthetic, spectroscopic and unusual structural properties (Shaw, 1980; Fincham et al., 1986; Krishnamurty & Woods, 1987). The bulky phenoxy derivatives of N3P3Cl6 (tri-P) and N4P4Cl8 (tetra-P) have potential uses in the synthesis of small-molecule organocyclophosphazenes with inorganic backbones and aryloxy side groups (Olshavsky & Allcock, 1995; Hökelek & Kılıç, 1990). Structural studies of tri-P and tetra-P derivatives, e.g. [Cl5N3P3(OC6H2O-2,4,6-Me)], (IX) (Hökelek, Akduran, Begeç et al., 2000), [Cl5N3P3(OC6H2-2,6-tBu2-4-Me)], (X) (Hökelek et al., 1999), and [Cl7N4P4(OC6H2-2,6-tBu2-4-Me)], (XI) (Hökelek et al., 1996), have been the focus of interest by our group. These organocyclophosphazenes are also useful models for the related linear organopolyphosphazenes (Allcock, Dembek et al., 1992). The organic, inorganic or organometallic side groups are highly effective in determining the specific physical or chemical properties of polyphosphazenes (Allcock et al., 1996).
Aziridino, pyrrolidino, and primary and other secondary aminophosphazene derivatives are also useful as cancer chemotherapeutic agents (Chernov et al., 1959; van der Huizen, 1984). A close relationship has been observed between the structures of the cyclophosphazene derivatives and cytostatic activity (van der Huizen, 1984). The electron donating groups in the tri-P and tetra-P phosphazenes seem to be essential for effective tumour-growth inhibition.
Compound (I) was studied to understand the influence of the highly hindered 2,2'-methylenebis(4-nitrophenoxy) side groups on the structure of the cyclic trimeric phosphazene ring (Fig. 1). The structure consists of a non-planar trimeric phosphazene ring and 2,2'-methylenebis(4-nitrophenoxy) group, together with two cis-Cl atoms and two geminal phenyl groups attached to the P2, P3 and P1 atoms, respectively. The three N atoms are displaced on opposite sides, + and -, with respect to the plane through the P atoms as follows: N1 - 0.024 (3), N2 + 0.239 (3) and N3 + 0.154 (3) Å.
In trimeric and tetrameric phosphazenes, the P—N bond lengths may be correlated with the orbital electronegativities of groups of atoms (Bullen & Tucker, 1972). In such structures, the lengths of the P—N bonds depend on the electronegativities of the substituents. In (I), the Cl atoms and 2,2'-methylenebis(4-nitrophenoxy) groups are slightly electron withdrawing, thus, the P—Cl and P—O bonds do not change considerably. In a given N3P3R6 structure, the lengths of the P—N bonds are generally equal, provided all of the substituents (R) are the same. If R is a difunctional bulky substituent (Kubono et al., 1994) or contains different substituents, the P—N bonds may show significant variations (Fincham et al., 1986; Contractor et al., 1985). When electron-donating groups are present, different P—N distances in the cyclotri(phosphazene) ring can be expected. In (I), there is a distinct difference between the electronegativities of the atoms attached to the P atoms; the P—N bond distances vary from 1.568 (3) to 1.617 (3) Å [average 1.589 (3) Å], while in a similar compound, (II), the P—N bond lengths are from 1.574 (3)–1.581 (3) Å [average 1.577 (3) Å]. In phosphazene derivatives, the P—N single and double bonds are generally in the ranges 1.63–1.69 and 1.57–1.60 Å, respectively (Allen et al., 1987). In (I), the shorter P—N bonds have appreciable double-bond character (Wagner & Vos, 1968), e.g. in related compounds, the corresponding mean bond lengths are: 1.576 (3) Å in (II), 1.573 (3) Å in (III), 1.58 (1) Å in (IV), 1.576 (5) Å in (VI), 1.572 (3) Å in [N3P3Cl4Ph(PPh2)], (XII) (Allcock et al., 1990), and 1.581 (3) Å in the starting material (N3P3Cl6; Bullen, 1971). The P—Cl and P—O bonds are almost equal, with mean values of 1.995 (1) and 1.599 (2) Å, respectively.
The P—N—P bond angles range from 118.8 (2) to 123.1 (2)° and, in addition, the N—P—N bond angles vary between 115.6 (1) and 118.7 (2)°. The endocyclic N1—P1—N3 angle [115.6 (1)°] is decreased and the N1—P2—N2 [118.1 (2)] and N2—P3—N3 [118.7 (2)°] angles are not changed significantly. On the other hand, the endocyclic P1—N1—P2 angle [123.1 (2)°] is increased and the P2—N2—P3 [118.8 (2)] and P1—N3—P3 [120.6 (2)°] angles are decreased, while the exocyclic C14—P1—C20 [105.8 (1)] and O1—P3—Cl1 [102.5 (1)°] angles are increased and the O6—P2—Cl2 angle [97.9 (1)°] is decreased with respect to the values [118.3 (2), 121.4 (3) and 101.2 (1)°, respectively] in the 3P3Cl6 starting material (Bullen, 1971). The O1—P3—N3 [106.4 (1)°] angle is smaller than the other O—P—N bond angles. These variations in the endo- and exocyclic bond angles may be due to both the electronic and/or steric interactions (Kılıç et al., 1996).
The Cl—P—N, Cl—P—O and N—P—O bond angles are in the ranges 106.9 (1)–110.2 (1) [average 108.6 (1)°], 97.9 (1)–102.5 (1) [average 100.2 (1)°] and 106.4 (1)–111.2 (1)° [average 109.5 (1)°], compared with the corresponding values in compound (II) of 108.7 (1)–109.9 (2) [average 109.2 (1)°], 99.4 (1)–103.6 (1) [average 101.5 (1)°] and 109.9 (2)–110.4 (2)° [average 110.2 (2)°].
In trimeric phosphazenes, it has been observed that endocyclic N—P—N angles about P decrease while exocyclic R—P—Cl angles increase (Contractor et al., 1985; Fincham et al., 1986; Hökelek et al., 1994; Kılıç et al., 1996), which are different from the case found in tetrameric phosphazenes containing bulky phenoxy groups (Allcock, Dembek et al., 1992; Hökelek et al., 1996; Hökelek & Kılıç, 1990). In (I), the N—P—N angles are larger and the O—P—Cl angles are smaller than the corresponding angles in N3P3Cl5(NPPh3), (XIII) [114.4 (1) and 107.2 (1)°; Fincham et al., 1986], N3P3Cl4(NPPh3)2, (XIV) [109.2 (4) and 110.9 (4)°; Fincham et al., 1986], (XII) [114.5 (2) and 106.7 (1)°] and (III) [115.1 (1) and 106.79 (9)°], which implies less electron donation to the N3P3 ring.