4,4,6,6-Tetra­chloro-2,2-(propyl­ene­dioxy­di-o-phenyl­enedi­imino)-2λ⁵,4λ⁵,6λ⁵-cyclotriphosphazene

The title compound, C₁₅H₁₆Cl₄N₅O₂P₃, 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.

S1. Comment

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(OC₆H₂-2,6^tBu2–4-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 Q_T = 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.

S2. Experimental

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%).

Computing details

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).

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. The broken lines show hydrogen bonds.
	Fig. 2. Packing diagram of (I).

4,4,6,6-Tetrachlorocyclo-2,2-(propylenedioxydi-o-phenylenediimino)- 2λ⁵,4λ⁵,6λ⁵-triazatriphosphorine

Crystal data

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) Å^3	0.40 × 0.25 × 0.25 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0525P)^2 + 1.1216P] where P = (Fo^2 + 2Fc^2)/3
4385 reflections	(Δ/σ)max < 0.001
322 parameters	Δρmax = 0.39 e Å^−3
1 restraint	Δρmin = −0.38 e Å^−3

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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)