cis-ansa-2,4-Di­chloro-2,4-[2,2′-methyl­enebis(4-nitro­phenoxy)]-6,6-di­phenylcyclo-2λ⁵,4λ⁵,6λ⁵-triphosph­aza­triene

The title compound, C₂₅H₁₈Cl₂N₅O₆P₃, consists of a non-planar trimeric phosphazene ring, one bulky 2,2′-methyl­enebis(4-nitro­phenoxy) side group, two cis-Cl atoms and two geminal phenyl groups. The P—Cl bond lengths are 1.9930 (12) and 1.9970 (12) Å, while the P—N and P—O distances are 1.568 (3)–1.617 (3) and 1.594 (2)–1.604 (2) Å. The core bond angles Cl—P—N, Cl—P—O, P—N—P, N—P—N and N—P—O are 106.9 (1)–110.2 (1), 97.9 (1)–102.5 (1), 118.8 (2)—123.1 (2), 115.6 (1)-118.7 (2) and 106.4 (1)–111.2 (1)°, respectively. In the 2,2′-methyl­enebis(4-nitro­phenoxy) side group, the phenyl rings are almost perpendicular to each other.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.067
• wR factor = 0.258
• Data-to-parameter ratio = 14.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



DIFMN_02  Alert C The minimum difference density is < -0.1*ZMAX*0.75
          _refine_diff_density_min given =     -1.280
          Test value =     -1.275

DIFMN_03  Alert C The minimum difference density is < -0.1*ZMAX*0.75
          The relevant atom site should be identified.

DIFMX_01  Alert C The maximum difference density is > 0.1*ZMAX*0.75
          _refine_diff_density_max given =      1.280
          Test value =      1.275

DIFMX_02  Alert C The minimum difference density is > 0.1*ZMAX*0.75
          The relevant atom site should be identified.

RFACR_01  Alert C The value of the weighted R factor is > 0.25
          Weighted R factor given   0.258


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 5 Alert Level C = Please check

---

S1. Comment

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.

S2. Experimental

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)].

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 ORTEPII (Johnson, 1976) drawing of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.

(I)

Crystal data

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) Å^3

Data collection

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

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.258	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
5465 reflections	(Δ/σ)max < 0.001
378 parameters	Δρmax = 1.28 e Å^−3
0 restraints	Δρmin = −1.28 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

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

Geometric parameters (Å, º)

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)