The title compound, C
15H
16Cl
4N
5O
2P
3, is a cyclophosphazenic lariat (PNP-pivot) ether with a spiro-cyclic 12-membered macrocyclic ligand containing two ether O and two N atoms; the phosphazene ring is nearly planar. In the macrocyclic ring, there is a four-center (trifurcate) N—H
O/N—H
N hydrogen bond. The relative inner-hole size of the macrocycle is estimated as approximately 0.95 Å.
Supporting information
CCDC reference: 243590
A solution of N3P3Cl6 (2.5 g, 7.18 mmol) in acetonitrile (100 ml) was added dropwise to a mixture of propylene glycol bis(2-aminophenyl ether) (1.85 g, 7.20 mmol) and NEt3 (3.63 g, 35.9 mmol) in acetonitrile (50 ml) at 263 K for over 1 h. After the mixture had been allowed to come to an ambient temperature, it was continued to be stirred for 26 h with argon being passed over the reaction mixture. The precipitated amine hydrochloride was filtered off and the solvent was evaporated in reduced pressure. The residue was dissolved in benzene (20 ml) and subjected to column chromatography (silica gel 40 g; eluant benzene) and crystallized from benzene–dichloromethane (2:1) (m.p. 467 K; yield 2.53 g, 66%).
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).
4,4,6,6-Tetrachlorocyclo-2,2-(propylenedioxydi-
o-phenylenediimino)- 2
λ5,4
λ5,6
λ5-triazatriphosphorine
top
Crystal data top
C15H16Cl4N5O2P3 | F(000) = 1080 |
Mr = 533.04 | Dx = 1.618 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 7.7094 (6) Å | θ = 10–15° |
b = 22.404 (2) Å | µ = 0.78 mm−1 |
c = 12.6960 (14) Å | T = 293 K |
β = 93.751 (7)° | Block, colourless |
V = 2188.2 (4) Å3 | 0.40 × 0.25 × 0.25 mm |
Z = 4 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | Rint = 0.022 |
Radiation source: fine-focus sealed tube | θmax = 26.3°, θmin = 2.4° |
Graphite monochromator | h = 0→9 |
non–profiled ω scans | k = −27→0 |
4703 measured reflections | l = −15→15 |
4385 independent reflections | 3 standard reflections every 120 min |
3132 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement top
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0525P)2 + 1.1216P] where P = (Fo2 + 2Fc2)/3 |
4385 reflections | (Δ/σ)max < 0.001 |
322 parameters | Δρmax = 0.39 e Å−3 |
1 restraint | Δρmin = −0.38 e Å−3 |
Crystal data top
C15H16Cl4N5O2P3 | V = 2188.2 (4) Å3 |
Mr = 533.04 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.7094 (6) Å | µ = 0.78 mm−1 |
b = 22.404 (2) Å | T = 293 K |
c = 12.6960 (14) Å | 0.40 × 0.25 × 0.25 mm |
β = 93.751 (7)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | Rint = 0.022 |
4703 measured reflections | 3 standard reflections every 120 min |
4385 independent reflections | intensity decay: 1% |
3132 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.39 e Å−3 |
4385 reflections | Δρmin = −0.38 e Å−3 |
322 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 1.22064 (8) | 0.05702 (3) | 0.76557 (6) | 0.03818 (19) | |
P2 | 0.90504 (8) | 0.00286 (3) | 0.77674 (6) | 0.03835 (19) | |
P3 | 0.92797 (9) | 0.12615 (3) | 0.79513 (6) | 0.03654 (18) | |
Cl1 | 1.35067 (12) | 0.05820 (4) | 0.63470 (8) | 0.0651 (3) | |
Cl2 | 1.41572 (11) | 0.04741 (5) | 0.87429 (8) | 0.0705 (3) | |
Cl3 | 0.78221 (12) | −0.04062 (4) | 0.65661 (9) | 0.0746 (3) | |
Cl4 | 0.84543 (12) | −0.04991 (4) | 0.89612 (9) | 0.0760 (3) | |
N1 | 1.1070 (3) | −0.00186 (10) | 0.7639 (2) | 0.0472 (6) | |
N2 | 0.8198 (3) | 0.06498 (10) | 0.7892 (2) | 0.0392 (5) | |
N3 | 1.1315 (3) | 0.11874 (10) | 0.7792 (2) | 0.0462 (6) | |
N4 | 0.8343 (3) | 0.17250 (11) | 0.7095 (2) | 0.0446 (6) | |
C5 | 0.7644 (4) | 0.15883 (12) | 0.6073 (2) | 0.0421 (7) | |
C6 | 0.8301 (5) | 0.11318 (14) | 0.5468 (3) | 0.0517 (8) | |
C7 | 0.7545 (6) | 0.10102 (18) | 0.4484 (3) | 0.0651 (10) | |
C8 | 0.6165 (6) | 0.1342 (2) | 0.4074 (3) | 0.0720 (11) | |
C9 | 0.5538 (5) | 0.18070 (19) | 0.4651 (3) | 0.0637 (10) | |
C10 | 0.6270 (4) | 0.19272 (13) | 0.5640 (3) | 0.0469 (7) | |
O11 | 0.5681 (3) | 0.24012 (9) | 0.62163 (18) | 0.0545 (6) | |
C12 | 0.4333 (4) | 0.22285 (19) | 0.6886 (3) | 0.0609 (9) | |
C13 | 0.3995 (6) | 0.2723 (2) | 0.7626 (4) | 0.0768 (12) | |
C14 | 0.5588 (6) | 0.29562 (17) | 0.8240 (4) | 0.0699 (11) | |
O15 | 0.6811 (3) | 0.24993 (9) | 0.86013 (18) | 0.0541 (6) | |
C16 | 0.6387 (4) | 0.21161 (13) | 0.9391 (3) | 0.0468 (7) | |
C17 | 0.4926 (5) | 0.21737 (17) | 0.9961 (3) | 0.0612 (9) | |
C18 | 0.4619 (5) | 0.17661 (18) | 1.0734 (3) | 0.0654 (10) | |
C19 | 0.5723 (5) | 0.12967 (18) | 1.0948 (3) | 0.0580 (9) | |
C20 | 0.7198 (4) | 0.12407 (14) | 1.0389 (2) | 0.0494 (7) | |
C21 | 0.7550 (3) | 0.16484 (13) | 0.9620 (2) | 0.0413 (7) | |
N22 | 0.9128 (3) | 0.16033 (11) | 0.9079 (2) | 0.0443 (6) | |
H4 | 0.802 (4) | 0.2011 (14) | 0.738 (3) | 0.050 (10)* | |
H20 | 0.7957 | 0.0924 | 1.0534 | 0.059* | |
H22 | 1.007 (3) | 0.1691 (17) | 0.945 (3) | 0.090 (14)* | |
H61 | 0.928 (4) | 0.0898 (12) | 0.576 (2) | 0.037 (7)* | |
H71 | 0.795 (5) | 0.0725 (16) | 0.411 (3) | 0.065 (11)* | |
H81 | 0.572 (5) | 0.1277 (17) | 0.336 (3) | 0.085 (13)* | |
H91 | 0.457 (5) | 0.2029 (17) | 0.442 (3) | 0.085 (13)* | |
H121 | 0.472 (4) | 0.1869 (14) | 0.726 (3) | 0.053 (9)* | |
H122 | 0.331 (5) | 0.2115 (14) | 0.648 (3) | 0.060 (10)* | |
H131 | 0.362 (5) | 0.3072 (18) | 0.727 (3) | 0.081 (12)* | |
H132 | 0.318 (5) | 0.2572 (18) | 0.808 (3) | 0.086 (14)* | |
H141 | 0.626 (6) | 0.3185 (19) | 0.787 (4) | 0.094 (16)* | |
H142 | 0.529 (4) | 0.3181 (16) | 0.879 (3) | 0.062 (10)* | |
H171 | 0.416 (5) | 0.2469 (16) | 0.981 (3) | 0.068 (11)* | |
H181 | 0.368 (5) | 0.1812 (15) | 1.109 (3) | 0.064 (11)* | |
H191 | 0.558 (4) | 0.1007 (14) | 1.142 (3) | 0.051 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0225 (3) | 0.0401 (4) | 0.0525 (4) | −0.0013 (3) | 0.0066 (3) | −0.0053 (3) |
P2 | 0.0253 (3) | 0.0323 (4) | 0.0573 (5) | −0.0025 (3) | 0.0018 (3) | 0.0008 (3) |
P3 | 0.0267 (3) | 0.0317 (4) | 0.0515 (4) | 0.0013 (3) | 0.0049 (3) | −0.0046 (3) |
Cl1 | 0.0646 (5) | 0.0675 (6) | 0.0667 (6) | −0.0075 (4) | 0.0310 (4) | −0.0106 (4) |
Cl2 | 0.0361 (4) | 0.0971 (7) | 0.0763 (6) | 0.0036 (4) | −0.0117 (4) | −0.0065 (5) |
Cl3 | 0.0650 (6) | 0.0542 (5) | 0.1010 (8) | −0.0042 (4) | −0.0226 (5) | −0.0271 (5) |
Cl4 | 0.0539 (5) | 0.0719 (6) | 0.1039 (8) | −0.0001 (4) | 0.0179 (5) | 0.0415 (5) |
N1 | 0.0294 (12) | 0.0340 (12) | 0.0790 (19) | 0.0023 (10) | 0.0104 (12) | −0.0027 (12) |
N2 | 0.0235 (11) | 0.0357 (12) | 0.0587 (15) | −0.0005 (9) | 0.0051 (10) | −0.0038 (11) |
N3 | 0.0268 (12) | 0.0377 (13) | 0.0748 (17) | −0.0044 (10) | 0.0096 (11) | −0.0084 (12) |
N4 | 0.0491 (15) | 0.0342 (13) | 0.0509 (16) | 0.0080 (11) | 0.0064 (12) | −0.0063 (12) |
C5 | 0.0465 (16) | 0.0327 (14) | 0.0481 (17) | −0.0061 (12) | 0.0094 (13) | 0.0027 (13) |
C6 | 0.065 (2) | 0.0429 (17) | 0.0489 (19) | 0.0010 (15) | 0.0138 (16) | −0.0020 (14) |
C7 | 0.088 (3) | 0.054 (2) | 0.054 (2) | −0.016 (2) | 0.020 (2) | −0.0082 (18) |
C8 | 0.083 (3) | 0.086 (3) | 0.047 (2) | −0.028 (2) | 0.002 (2) | 0.002 (2) |
C9 | 0.055 (2) | 0.076 (3) | 0.059 (2) | −0.0085 (19) | −0.0014 (18) | 0.015 (2) |
C10 | 0.0443 (17) | 0.0429 (16) | 0.0540 (19) | −0.0066 (13) | 0.0074 (14) | 0.0110 (14) |
O11 | 0.0509 (13) | 0.0450 (12) | 0.0687 (15) | 0.0074 (10) | 0.0126 (11) | 0.0114 (11) |
C12 | 0.0382 (18) | 0.075 (3) | 0.070 (2) | 0.0063 (17) | 0.0065 (17) | 0.013 (2) |
C13 | 0.067 (3) | 0.078 (3) | 0.086 (3) | 0.041 (2) | 0.013 (2) | 0.017 (2) |
C14 | 0.083 (3) | 0.0396 (19) | 0.089 (3) | 0.0228 (19) | 0.023 (2) | −0.002 (2) |
O15 | 0.0527 (13) | 0.0392 (11) | 0.0710 (15) | 0.0105 (10) | 0.0093 (11) | −0.0046 (11) |
C16 | 0.0448 (17) | 0.0438 (16) | 0.0518 (18) | 0.0013 (13) | 0.0028 (14) | −0.0157 (14) |
C17 | 0.052 (2) | 0.062 (2) | 0.071 (2) | 0.0158 (18) | 0.0131 (17) | −0.0132 (19) |
C18 | 0.056 (2) | 0.082 (3) | 0.061 (2) | 0.001 (2) | 0.0200 (18) | −0.022 (2) |
C19 | 0.062 (2) | 0.071 (2) | 0.0417 (18) | −0.0061 (19) | 0.0061 (16) | −0.0050 (18) |
C20 | 0.0486 (18) | 0.0562 (19) | 0.0423 (17) | 0.0031 (14) | −0.0051 (14) | −0.0092 (14) |
C21 | 0.0342 (14) | 0.0456 (16) | 0.0437 (16) | 0.0008 (12) | −0.0007 (12) | −0.0166 (13) |
N22 | 0.0320 (12) | 0.0494 (14) | 0.0508 (15) | 0.0015 (11) | −0.0018 (11) | −0.0110 (12) |
Geometric parameters (Å, º) top
P3—N2 | 1.603 (2) | C21—C16 | 1.398 (4) |
P3—N3 | 1.604 (2) | C10—C9 | 1.370 (5) |
P3—N22 | 1.635 (3) | C16—C17 | 1.384 (5) |
P3—N4 | 1.636 (3) | C18—C19 | 1.369 (5) |
P1—N3 | 1.559 (2) | C18—C17 | 1.373 (6) |
P1—N1 | 1.583 (2) | C18—H181 | 0.88 (4) |
P1—Cl2 | 1.9853 (11) | C19—H191 | 0.90 (3) |
P1—Cl1 | 1.9961 (11) | C6—C7 | 1.372 (5) |
P2—N2 | 1.552 (2) | C6—H61 | 0.97 (3) |
P2—N1 | 1.579 (2) | C12—C13 | 1.486 (6) |
P2—Cl3 | 1.9957 (11) | C12—H121 | 0.97 (3) |
P2—Cl4 | 1.9993 (12) | C12—H122 | 0.95 (3) |
O15—C16 | 1.375 (4) | C9—C8 | 1.379 (6) |
O15—C14 | 1.446 (4) | C9—H91 | 0.93 (4) |
O11—C10 | 1.383 (4) | C17—H171 | 0.90 (4) |
O11—C12 | 1.438 (4) | C8—C7 | 1.372 (6) |
N22—C21 | 1.439 (4) | C8—H81 | 0.95 (4) |
N22—H22 | 0.863 (19) | C7—H71 | 0.87 (4) |
C5—C10 | 1.387 (4) | C13—C14 | 1.504 (6) |
C5—C6 | 1.393 (4) | C13—H131 | 0.94 (4) |
C5—N4 | 1.407 (4) | C13—H132 | 0.95 (4) |
C20—C21 | 1.377 (4) | C14—H142 | 0.90 (4) |
C20—C19 | 1.385 (5) | C14—H141 | 0.88 (5) |
C20—H20 | 0.9300 | N4—H4 | 0.79 (3) |
| | | |
N2—P3—N3 | 114.57 (12) | C19—C18—H181 | 121 (2) |
N2—P3—N22 | 112.02 (13) | C17—C18—H181 | 118 (2) |
N3—P3—N22 | 106.58 (13) | C18—C19—C20 | 119.2 (4) |
N2—P3—N4 | 107.80 (13) | C18—C19—H191 | 126 (2) |
N3—P3—N4 | 112.01 (14) | C20—C19—H191 | 115 (2) |
N22—P3—N4 | 103.33 (13) | C7—C6—C5 | 120.0 (4) |
N3—P1—N1 | 119.53 (12) | C7—C6—H61 | 120.7 (17) |
N3—P1—Cl2 | 109.77 (11) | C5—C6—H61 | 119.4 (17) |
N1—P1—Cl2 | 108.21 (10) | O11—C12—C13 | 109.7 (3) |
N3—P1—Cl1 | 109.27 (11) | O11—C12—H121 | 107.4 (18) |
N1—P1—Cl1 | 107.91 (10) | C13—C12—H121 | 111.8 (19) |
Cl2—P1—Cl1 | 100.45 (5) | O11—C12—H122 | 111 (2) |
N2—P2—N1 | 119.83 (12) | C13—C12—H122 | 112 (2) |
N2—P2—Cl3 | 109.43 (10) | H121—C12—H122 | 105 (3) |
N1—P2—Cl3 | 108.06 (11) | C10—C9—C8 | 119.8 (4) |
N2—P2—Cl4 | 109.47 (10) | C10—C9—H91 | 117 (3) |
N1—P2—Cl4 | 108.40 (10) | C8—C9—H91 | 123 (3) |
Cl3—P2—Cl4 | 99.77 (6) | C18—C17—C16 | 119.8 (3) |
P2—N2—P3 | 123.30 (13) | C18—C17—H171 | 120 (2) |
C16—O15—C14 | 119.5 (3) | C16—C17—H171 | 120 (2) |
C10—O11—C12 | 112.4 (2) | C7—C8—C9 | 119.9 (4) |
C21—N22—P3 | 124.20 (19) | C7—C8—H81 | 120 (2) |
C21—N22—H22 | 116 (3) | C9—C8—H81 | 120 (2) |
P3—N22—H22 | 118 (3) | C6—C7—C8 | 120.7 (4) |
C10—C5—C6 | 118.7 (3) | C6—C7—H71 | 120 (3) |
C10—C5—N4 | 118.9 (3) | C8—C7—H71 | 119 (3) |
C6—C5—N4 | 122.5 (3) | C12—C13—C14 | 114.6 (3) |
P1—N3—P3 | 123.22 (14) | C12—C13—H131 | 112 (2) |
P2—N1—P1 | 119.43 (14) | C14—C13—H131 | 100 (2) |
C21—C20—C19 | 120.7 (3) | C12—C13—H132 | 106 (3) |
C21—C20—H20 | 119.7 | C14—C13—H132 | 111 (3) |
C19—C20—H20 | 119.7 | H131—C13—H132 | 113 (3) |
C20—C21—C16 | 119.4 (3) | O15—C14—C13 | 114.3 (3) |
C20—C21—N22 | 120.3 (3) | O15—C14—H142 | 110 (2) |
C16—C21—N22 | 120.3 (3) | C13—C14—H142 | 111 (2) |
C9—C10—O11 | 120.4 (3) | O15—C14—H141 | 100 (3) |
C9—C10—C5 | 120.9 (3) | C13—C14—H141 | 115 (3) |
O11—C10—C5 | 118.7 (3) | H142—C14—H141 | 106 (3) |
O15—C16—C17 | 124.3 (3) | C5—N4—P3 | 126.9 (2) |
O15—C16—C21 | 116.1 (3) | C5—N4—H4 | 119 (2) |
C17—C16—C21 | 119.6 (3) | P3—N4—H4 | 111 (2) |
C19—C18—C17 | 121.3 (3) | | |
| | | |
N1—P2—N2—P3 | −2.9 (3) | C6—C5—C10—O11 | −176.4 (3) |
Cl3—P2—N2—P3 | −128.42 (16) | N4—C5—C10—O11 | 2.4 (4) |
Cl4—P2—N2—P3 | 123.19 (16) | C14—O15—C16—C17 | −7.5 (5) |
N3—P3—N2—P2 | 4.0 (3) | C14—O15—C16—C21 | 173.5 (3) |
N22—P3—N2—P2 | −117.57 (18) | C20—C21—C16—O15 | −178.9 (3) |
N4—P3—N2—P2 | 129.41 (18) | N22—C21—C16—O15 | 2.9 (4) |
N2—P3—N22—C21 | −40.7 (3) | C20—C21—C16—C17 | 2.0 (4) |
N3—P3—N22—C21 | −166.7 (2) | N22—C21—C16—C17 | −176.2 (3) |
N4—P3—N22—C21 | 75.1 (3) | C17—C18—C19—C20 | 1.5 (6) |
N1—P1—N3—P3 | 1.7 (3) | C21—C20—C19—C18 | −0.5 (5) |
Cl2—P1—N3—P3 | −124.09 (18) | C10—C5—C6—C7 | −2.5 (5) |
Cl1—P1—N3—P3 | 126.65 (17) | N4—C5—C6—C7 | 178.7 (3) |
N2—P3—N3—P1 | −3.4 (3) | C10—O11—C12—C13 | 169.3 (3) |
N22—P3—N3—P1 | 121.1 (2) | O11—C10—C9—C8 | 178.4 (3) |
N4—P3—N3—P1 | −126.6 (2) | C5—C10—C9—C8 | 0.3 (5) |
N2—P2—N1—P1 | 0.9 (3) | C19—C18—C17—C16 | −0.7 (6) |
Cl3—P2—N1—P1 | 127.07 (16) | O15—C16—C17—C18 | 180.0 (3) |
Cl4—P2—N1—P1 | −125.68 (16) | C21—C16—C17—C18 | −1.1 (5) |
N3—P1—N1—P2 | −0.3 (3) | C10—C9—C8—C7 | −1.5 (6) |
Cl2—P1—N1—P2 | 126.22 (16) | C5—C6—C7—C8 | 1.3 (5) |
Cl1—P1—N1—P2 | −125.91 (16) | C9—C8—C7—C6 | 0.7 (6) |
C19—C20—C21—C16 | −1.3 (4) | O11—C12—C13—C14 | −52.3 (5) |
C19—C20—C21—N22 | 177.0 (3) | C16—O15—C14—C13 | −70.4 (5) |
P3—N22—C21—C20 | 94.5 (3) | C12—C13—C14—O15 | −39.9 (6) |
P3—N22—C21—C16 | −87.3 (3) | C10—C5—N4—P3 | 151.0 (2) |
C12—O11—C10—C9 | 91.9 (4) | C6—C5—N4—P3 | −30.2 (4) |
C12—O11—C10—C5 | −89.9 (3) | N2—P3—N4—C5 | −40.4 (3) |
C6—C5—C10—C9 | 1.8 (4) | N3—P3—N4—C5 | 86.5 (3) |
N4—C5—C10—C9 | −179.4 (3) | N22—P3—N4—C5 | −159.1 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O15 | 0.78 (3) | 2.16 (3) | 2.891 (3) | 156 (3) |
N4—H4···O11 | 0.78 (3) | 2.42 (3) | 2.730 (3) | 105 (3) |
N4—H4···N22 | 0.78 (3) | 2.44 (4) | 2.566 (4) | 90 (4) |
Experimental details
Crystal data |
Chemical formula | C15H16Cl4N5O2P3 |
Mr | 533.04 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.7094 (6), 22.404 (2), 12.6960 (14) |
β (°) | 93.751 (7) |
V (Å3) | 2188.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.40 × 0.25 × 0.25 |
|
Data collection |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4703, 4385, 3132 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.624 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.110, 1.02 |
No. of reflections | 4385 |
No. of parameters | 322 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.38 |
Selected geometric parameters (Å, º) topP3—N2 | 1.603 (2) | P1—N3 | 1.559 (2) |
P3—N3 | 1.604 (2) | P1—N1 | 1.583 (2) |
P3—N22 | 1.635 (3) | P2—N2 | 1.552 (2) |
P3—N4 | 1.636 (3) | P2—N1 | 1.579 (2) |
| | | |
N2—P3—N3 | 114.57 (12) | N3—P1—N1 | 119.53 (12) |
N2—P3—N22 | 112.02 (13) | N2—P2—N1 | 119.83 (12) |
N3—P3—N22 | 106.58 (13) | P2—N2—P3 | 123.30 (13) |
N2—P3—N4 | 107.80 (13) | P1—N3—P3 | 123.22 (14) |
N3—P3—N4 | 112.01 (14) | P2—N1—P1 | 119.43 (14) |
N22—P3—N4 | 103.33 (13) | | |
| | | |
N4—P3—N22—C21 | 75.1 (3) | C10—O11—C12—C13 | 169.3 (3) |
P3—N22—C21—C16 | −87.3 (3) | O11—C12—C13—C14 | −52.3 (5) |
C12—O11—C10—C5 | −89.9 (3) | C16—O15—C14—C13 | −70.4 (5) |
N4—C5—C10—O11 | 2.4 (4) | C12—C13—C14—O15 | −39.9 (6) |
C14—O15—C16—C21 | 173.5 (3) | C10—C5—N4—P3 | 151.0 (2) |
N22—C21—C16—O15 | 2.9 (4) | N22—P3—N4—C5 | −159.1 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O15 | 0.78 (3) | 2.16 (3) | 2.891 (3) | 156 (3) |
N4—H4···O11 | 0.78 (3) | 2.42 (3) | 2.730 (3) | 105 (3) |
N4—H4···N22 | 0.78 (3) | 2.44 (4) | 2.566 (4) | 90 (4) |
N3P3Cl6 is a standard compound for trimeric phosphazene derivatives. It has potential use in the preparation of new small organocyclophosphazenes and high polymeric phosphazene derivatives with inorganic backbones and various side groups (Allcock et al., 1992; Olshavsky & Allcock, 1995; Hökelek et al., 1996).
The structures of the organic, inorganic or organometallic side groups are highly effective in determining the specific physical and chemical properties of phosphazene polymers (Allcock et al., 1987, 1996). Some of the polymeric phosphazene derivatives may be useful as high refractive index glasses (Olshavsky & Allcock, 1995), ferroelectric and non-linear optical polymers (Dembek et al., 1991; Allcock et al., 1995), liquid crystalline materials (Allcock & Kim, 1991) and biomedical materials (Cohen et al., 1990).
The crystal structures of N3P3Cl6 (Bullen, 1971) and a few of its derivatives with bulky phenoxy groups have been reported.
In the literature, there are only a limited number of reports concerning the structures of the cyclophosphazenic lariat (PNP-pivot) ethers (Yıldız et al., 1999; Brandt et al., 1999, 2001; Bartsch et al., 2002).
Two kinds of compounds are expected to be formed from the reaction of N3P3Cl6 with propylene glycol bis(2-aminophenyl ether), namely spiro- and ansa-cyclophosphazenic lariat ethers. However, only the spiro-cyclic 12-membered macrocyclic ligand, (I), has been isolated, which is a new class of macrocyclic multidentate ligand where the macrocycle and the phosphazene rings are linked, forming a novel structure.
The title compound, (I), may be a potential ion-selective reagent for lithium and transition metal cations. The structure determination of (I) was carried out in order to estimate the macrocyclic ring hole size and to understand the influence of the highly hindered macrocyclic ring on the structure of the cyclic trimeric phosphazene. The macrocyclic ring (Fig. 1) comprises two ether O and two N atoms. The intramolecular P3···C13 [5.222 (3) Å], C10···C21 [5.123 (4) Å], N4···O11 [2.730 (4) Å], N4···O15 [2.891 (4) Å], N22···O11 [4.712 (4) Å] and N22···O15 [2.729 (4) Å] distances may indicate the hole size of the macrocyclic ring. When only the N and O atoms are taken into account, the mean N···O distance is 3.266 (4) Å. A least-squares plane defined by atoms N4, N22, O11 and O15 has maximum deviations on either side of the plane of 0.145 (2), −0.122(2, −0.080 (2) and 0.070 (2) Å, respectively.
The relative macrocyclic inner-hole size is estimated as approximately 0.95 Å, taking into account the best least-squares plane defined by atoms N4, N22, O11 and O15. and the trifurcate hydrogen bond in the macrocycle, using the `modified covalent radii' of Nsp2 (0.66 Å) and Osp3 (0.76 Å) atoms (Goodwin et al., 1982; Adam et al., 1983; Drummond et al., 1982). The macrocycle is contracted with a trifurcate N—H···O/N—H···N hydrogen bond, where the central part of the macrocycle is occupied by the trifurcate hydrogen bond.
The phosphazene ring is nearly planar. The P—N bonds are in the range 1.552 (2)–1.604 (2) Å. The P—N bonds have a regular variation with the distance from P3 in the ring: P3—N3 ≈ P3—N2 > P1—N3 ≈ P2—N2 < P1—N1 ≈ P2—N1. The phosphazene ring P—N bonds (Table 1) have double-bond character. On the other hand, the P—N bonds in the macrocycle are near the lower limit of the single-bond length. In phosphazene derivatives, the P—N single and double bonds are generally in the ranges 1.628–1.691 and 1.571–1.604 Å, respectively (Allen et al., 1987). The shortening in the macroring P—N bonds may probably be due to electron releasing from the N atoms of the macrocycle to the phosphazene ring.
In the phosphazene ring, for the angles nearest to the macrocycle, viz. endocyclic α(N2—P3—N3) and exocyclic α'(N4—P3—N22), α is decreased while α' is increased with increasing electron supply and repulsions of the substituents relative to the standard compound N3P3Cl6. The β(P2—N2—P3) and β(P1—N3—P3) values are seen to change considerably and seem to increase with increasing electron supply to the N3P3 ring (Kılıç et al., 1996). In (I), β(P2—N2—P3) ≈ β(P1—N3—P3) > (P1—N1—P2); the α [114.6 (1)°] angle is significantly smaller and the α' angle [103.3 (1)°] a little larger than the corresponding values [118.3 (2) and 101.2 (1)°, respectively], but the β angles [123.3 (1) and 123.2 (1)°] are larger than the reported value [121.4 (3)°] in N3P3Cl6 standard compound (Bullen, 1971).
On the other hand, the α angle [114.6 (1)°] is larger than the corresponding value [109.2 (4)°] in [N3P3Cl4(NPPh3)2] (Fincham et al., 1986), but is not significantly different from the values [114.4 (1) and 114.5 (2)°] in [N3P3Cl5(NPPh3)] (Fincham et al., 1986) and [N3P3Cl4Ph(PPh2)] (Allcock et al., 1990) and is a little smaller than the α values [115.8 (1), 115.1 (1) and 115.8 (1)°] in N3P3Cl2[(OC6H3)(NO2)CH2(OC6H3)(NO2)(Ph2)] (Hökelek et al., 2001), [N3P3Cl5(OC6H2-2,6tBu2–4-Me] (Hökelek et al., 1999) and [N3P3Cl5(OC6H2(tBu)3-2,4,6)] (Kılıç et al., 1996), respectively. In (I), the macrocycle releases electrons to the N3P3 ring as seen for one of the NPPh3 groups in [N3P3Cl4(NPPh3)2] (Fincham et al., 1986); the NPPh3 group is known to be a very strong electron-releasing group in phosphazene chemistry.
In the macrocycle, there is a four-center (trifurcate) N—H···O/N—H···N hydrogen bond (Table 2). The Cremer & Pople (1975) total puckering amplitude for the macrocycle is QT = 1.602 (4) Å and the torsion angles (Table 1) have the sequence -ap, +ap, +sp, -sc, +ap, -sc, -sc, -sc, +ap, +sp, -ac, +sc (sp denotes synperiplanar, sc synclinal and ap antiperiplanar), corresponding to the P3—N4, ···, N22—P3 bond sequence. The conformation of the macrocyclic ring is conditioned by the three hydrogen bonds (Fig. 1) and planarity of the two benzo-fused N—C—C—O systems.
As can be seen from the packing diagram (Fig. 2), the macrocyclic ligands are elongated approximately parallel to the (0 1/2 1) planes and stacked along the a axis. Dipole–dipole and van der Waals interactions are also effective in the molecular packing.