1-Chloro-1,3,3,5,5-penta­phenoxy­cyclo­triphosphazene: a precursor of functionalized cyclo­phosphazene derivatives

The crystal structure of the title compound, C₃₀H₂₅ClN₃O₅P₃, shows that the direct bonding between P and Cl does not modify the structural parameters in the vicinity of this P atom. It also confirms the structural difference between the two P atoms which are each bonded to two phenoxy groups, observed in the ³¹P NMR spectrum. The crystal packing consists principally of complex stacking interactions.

S1. Comment

The title compound, (I), also known as monochloropentaphenoxycyclotriphosphazene, has already been used to synthesize polymer precursors (Dez & De Jaeger, 1996). More recently, it has been used to synthesize a wide range of cyclotriphosphazene derivatives, such as cyclotriphosphazene hydrazides (Chandrasekhar et al., 2003), cyclotriphosphazene with N,N,N',N'-tetramethylguanidine groups (Bloy & Diefenbach, 2000), and cyclotriphosphazene with 2-, 3- and 4-pyridylmethoxy groups (Diefenbach et al., 1999). Its synthesis and NMR data have been described elsewhere (Reuben, 1987; Selvaraj et al., 1991). To date, however, structural data for (I) are not available in the Cambridge Structural Database (CSD, Version 5.24; Allen, 2002). We thus present here the results of the first X-ray crystal structure analysis of (I). \sch

Fig. 1 shows a view of the asymmetric unit of (I), which consists of one molecule. The phosphazene ring is planar, with the maximum deviation from the mean least-squares plane being 0.093 (1) Å for atom P3. A small asymmetry within the bond angles of the phospazene ring is noted (Table 1), as was also observed in the related cyclic (p-halogenophenoxy)phosphazene structures (Allcock et al., 1994). The mean values of the N—P—N and P—N—P angles are 117.87 and 121.54°, respectively. The P—O, P—N, P—Cl and O—C bond lengths are in agreement with the values observed in analogous structures deposited in the CSD (Table 3). It is interesting to note that the occurrence of a Cl atom directly attached to a P atom does not modify the structural parameters in the vicinity of this atom, P1.

The phenyl units lie on both sides of the phospazene ring, three on one side and two on the other, close to which lies the Cl atom. The disposition of the three phenyl side groups on the side opposite to the Cl is such that the plane of phenoxy group C (C521—C526) attached to atom O52 (on P5) is approximately perpendicular to the phosphazene ring, with a dihedral angle of 78.59 (9)°. Phenoxy ring B (C321—C326)attached to atom O32 (on P3) is more tilted towards the phosphazene ring, with a dihedral angle of about 69.52 (9)°, and the third ring (A, C111—C116) attached to atom O11 (on P1) is nearly parallel to the phosphazene ring, with a dihedral angle of 21.6 (2)°. Furthermore, owing to optimization of C—H···π stacking interactions, these three phenyl rings are oriented so that they are approximately mutually perpendicular. Phenyl ring A is oriented perpendicular to phenyl ring B, with a dihedral angle of about 89.6 (1)°, and the distance between atom C116 and the centroid of ring B, CgB, is about 3.71 Å (Table 4). Phenyl ring B is perpendicular to ring C, with a dihedral angle of 82.4 (1)°, and the distance between atom C326 and the centroid of ring C, CgC, is about 4.18 Å (Table 4).

On the same side as the Cl atom, phenyl ring E (C311–316) attached to atom O31 is perpendicular to the phosphazene ring, with a dihedral angle of 85.8 (1)°, whereas phenyl ring D (C511—C516) attached to atom O51 is more tilted towards the phosphazene ring, with a dihedral angle of 45.62 (6)°. The dihedral angle between rings E and D [52.8 (1)°] indicates that these two rings are not in an optimal perpendicular stacking interaction. However, atom C512 is situated at a distance of 3.99 Å from the centroid of ring E, CgE (Table 4).

Surprisingly, the ³¹P NMR spectrum of (I) shows a doublet of a doublet at 22.33 p.p.m. (J_PNP = 81 and 84 Hz), attributed to atoms P3 and P5, and a doublet at 7.03 p.p.m. (J_PNP = 83 Hz), attributed to P1, instead of the expected triplet (P3 and P5) and doublet (P1). These results indicate that P3 and P5 are not strictly equivalent. A significant difference between these two P atoms is observed in the crystal structure and concerns the position of the phenoxy groups. This difference could explain the non-equivalence observed for P3 and P5 in the NMR spectrum.

In the crystal packing of (I), phenyl rings from neighbouring molecules complete the intramolecular stacking interactions between the phenoxy units on both sides of the phosphazene ring (Fig. 2). C—H···π interactions are observed between rings E and B and between rings E and D. These phenyl rings make dihedral angles of 58.5 (1) and 70.9 (1)°, respectively. For the former interaction, atom C325 is at a distance of 3.90 Å from CgE, and for the latter, atom C314 is at a distance of 3.85 Å from the centroid of ring D, CgD (Table 4). At the same time, a C—H group from a symmetry-related molecule is situated close to each N atom of the phosphazene ring, at distances ranging from 3.35 to 3.67 Å (Table 2). According to the geometric parameters, the C523—H523···N6 interaction is weak, and it may be difficult to assert the occurrence of a real C—H···N interaction.

S2. Experimental

Hexachlorocyclotriphosphazene (1 g, 1 equivalent) in solution in anhydrous tetrahydrofuran (THF) under nitrogen was stirred with NaH (60% dispersion in mineral oil, 0.63 g, 5.5 equivalents) at 268 K. A solution of phenol (1.49 g, 5.5 equivalents) in THF was added dropwise to maintain the temperature at around 268 K. The mixture was then stirred at room temperature for 24 h. The THF was evaporated and the residue was dissolved in dichloromethane, washed with water and dried over anhydrous sodium sulfate. After removal of the dichloromethane under reduced pressure, the yield reached 86% for (I), and the ³¹P NMR spectrum indicated the presence of hexaphenoxycyclotriphophazene as a side product. The title compound was crystallized in a desiccator by slow diffusion of pentane in a concentrated solution of (I) in THF. The ³¹P NMR spectrum was recorded using a Bruker DRX400 and samples were dissolved in CDCl₃ to a concentration of 10% w/v.

S3. Refinement

H atoms were treated as riding, with C—H distances in the range 0.93–0.96 Å and with U_iso(H) = 1.2U_eq(C). Please check added text.

Computing details

Data collection: CAD-4-PC (Enraf-Nonius, 1996); cell refinement: CAD-4-PC; data reduction: JANA98 (Petříček & Dušek, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.
	Fig. 2. A general view of the crystal packing of (I), projected along the a axis.

1-Chloro-1,3,3,5,5-pentaphenoxycyclotriphosphazene

Crystal data

C30H25ClN3O5P3	Dx = 1.381 Mg m^−3
Mr = 635.89	Melting point: 341 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 9.8044 (7) Å	θ = 18–21°
b = 21.3628 (13) Å	µ = 0.33 mm^−1
c = 29.2053 (15) Å	T = 293 K
V = 6117.0 (7) Å^3	Prism, colourless
Z = 8	0.52 × 0.52 × 0.41 mm
F(000) = 2624

Data collection

Enraf-Nonius CAD-4 diffractometer	4539 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.077
Graphite monochromator	θmax = 30.0°, θmin = 2.0°
θ/2θ scans	h = −13→13
Absorption correction: gaussian (JANA98; Petříček & Dušek, 1998)	k = 0→30
Tmin = 0.663, Tmax = 0.706	l = 0→41
17273 measured reflections	3 standard reflections every 60 min
8884 independent reflections	intensity decay: 7.2%

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0617P)^2 + 1.4945P] where P = (Fo^2 + 2Fc^2)/3
8884 reflections	(Δ/σ)max = 0.007
379 parameters	Δρmax = 0.37 e Å^−3
75 restraints	Δρmin = −0.27 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
Cl1	0.14178 (8)	0.42264 (4)	0.18690 (3)	0.0911 (3)
P1	0.33128 (7)	0.39001 (3)	0.17675 (2)	0.05526 (17)
N2	0.3771 (2)	0.41044 (9)	0.12739 (7)	0.0535 (5)
P3	0.43492 (6)	0.36068 (3)	0.09240 (2)	0.04921 (15)
N4	0.41402 (19)	0.28946 (9)	0.10387 (7)	0.0520 (5)
P5	0.37186 (7)	0.26686 (3)	0.15326 (2)	0.05604 (17)
N6	0.3342 (3)	0.31899 (10)	0.18929 (8)	0.0723 (6)
O11	0.4135 (2)	0.42418 (8)	0.21549 (6)	0.0711 (5)
C111	0.4274 (3)	0.48991 (12)	0.21911 (10)	0.0655 (7)
C112	0.3664 (4)	0.51895 (17)	0.25477 (14)	0.1099 (13)
H112	0.3116	0.4966	0.2750	0.132*
C113	0.3870 (5)	0.5825 (2)	0.26053 (18)	0.1373 (19)
H113	0.3456	0.6030	0.2849	0.165*
C114	0.4660 (4)	0.61510 (18)	0.23141 (17)	0.1131 (14)
H114	0.4787	0.6579	0.2356	0.136*
C115	0.5270 (4)	0.58536 (17)	0.19595 (15)	0.1032 (12)
H115	0.5811	0.6079	0.1756	0.124*
C116	0.5093 (3)	0.52167 (15)	0.18978 (12)	0.0844 (9)
H116	0.5529	0.5010	0.1659	0.101*
O31	0.38080 (18)	0.37489 (8)	0.04240 (6)	0.0619 (4)
C311	0.2503 (3)	0.35718 (12)	0.02770 (9)	0.0596 (6)
C312	0.1392 (4)	0.3898 (2)	0.03981 (14)	0.1034 (12)
H312	0.1455	0.4226	0.0606	0.124*
C313	0.0157 (4)	0.3738 (3)	0.02075 (19)	0.1421 (19)
H313	−0.0619	0.3969	0.0278	0.171*
C314	0.0062 (5)	0.3238 (3)	−0.00853 (18)	0.1304 (18)
H314	−0.0778	0.3123	−0.0207	0.156*
C315	0.1184 (6)	0.29193 (19)	−0.01949 (14)	0.1132 (15)
H315	0.1122	0.2580	−0.0394	0.136*
C316	0.2412 (4)	0.30833 (14)	−0.00198 (11)	0.0830 (9)
H316	0.3191	0.2862	−0.0102	0.100*
O32	0.59324 (17)	0.37116 (8)	0.08417 (7)	0.0664 (5)
C321	0.6600 (2)	0.42861 (11)	0.08640 (9)	0.0537 (6)
C322	0.6157 (4)	0.48016 (14)	0.06423 (12)	0.0877 (10)
H322	0.5344	0.4785	0.0479	0.105*
C326	0.7772 (3)	0.43023 (15)	0.11125 (14)	0.0926 (10)
H326	0.8079	0.3950	0.1269	0.111*
C324	0.8052 (5)	0.53627 (18)	0.08800 (19)	0.1169 (15)
H324	0.8574	0.5726	0.0869	0.140*
C323	0.6871 (4)	0.53384 (17)	0.06539 (16)	0.1087 (13)
H323	0.6543	0.5692	0.0505	0.130*
C325	0.8503 (4)	0.4866 (2)	0.11258 (19)	0.1208 (16)
H325	0.9291	0.4899	0.1302	0.145*
O51	0.24651 (18)	0.22109 (8)	0.15158 (7)	0.0674 (5)
C511	0.2378 (2)	0.17115 (11)	0.12018 (10)	0.0592 (6)
C512	0.1730 (3)	0.18113 (14)	0.07923 (12)	0.0760 (8)
H512	0.1398	0.2206	0.0716	0.091*
C513	0.1581 (4)	0.13160 (19)	0.04967 (14)	0.0942 (10)
H513	0.1136	0.1375	0.0219	0.113*
C514	0.2079 (4)	0.07369 (18)	0.06050 (16)	0.1018 (12)
H514	0.1994	0.0407	0.0399	0.122*
C515	0.2706 (4)	0.06451 (14)	0.10190 (15)	0.0976 (12)
H515	0.3020	0.0248	0.1097	0.117*
C516	0.2873 (3)	0.11354 (13)	0.13210 (12)	0.0781 (8)
H516	0.3314	0.1076	0.1600	0.094*
O52	0.4855 (2)	0.22160 (8)	0.17332 (7)	0.0695 (5)
C521	0.6234 (3)	0.23736 (12)	0.17021 (9)	0.0623 (6)
C522	0.6829 (3)	0.27531 (16)	0.20214 (11)	0.0844 (9)
H522	0.6319	0.2915	0.2262	0.101*
C523	0.8203 (4)	0.2892 (2)	0.19810 (13)	0.1006 (11)
H523	0.8609	0.3163	0.2190	0.121*
C524	0.8957 (4)	0.2641 (2)	0.16436 (14)	0.0976 (11)
H524	0.9883	0.2731	0.1622	0.117*
C525	0.8352 (4)	0.22543 (19)	0.13326 (15)	0.1097 (13)
H525	0.8866	0.2083	0.1096	0.132*
C526	0.6986 (3)	0.21157 (15)	0.13661 (12)	0.0873 (10)
H526	0.6583	0.1844	0.1157	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0693 (5)	0.1003 (6)	0.1035 (7)	0.0130 (4)	0.0235 (4)	−0.0095 (5)
P1	0.0648 (4)	0.0511 (3)	0.0498 (3)	0.0059 (3)	0.0038 (3)	−0.0042 (3)
N2	0.0615 (11)	0.0468 (10)	0.0524 (12)	0.0047 (9)	0.0005 (9)	0.0004 (8)
P3	0.0481 (3)	0.0509 (3)	0.0486 (3)	−0.0030 (3)	0.0023 (3)	−0.0021 (3)
N4	0.0541 (11)	0.0488 (10)	0.0531 (12)	0.0000 (8)	0.0033 (9)	−0.0054 (8)
P5	0.0650 (4)	0.0469 (3)	0.0562 (4)	0.0011 (3)	0.0058 (3)	0.0015 (3)
N6	0.1119 (19)	0.0545 (12)	0.0504 (13)	0.0018 (12)	0.0145 (13)	0.0016 (10)
O11	0.0957 (14)	0.0608 (11)	0.0569 (11)	0.0068 (9)	−0.0136 (10)	−0.0069 (8)
C111	0.0780 (17)	0.0616 (15)	0.0570 (16)	0.0033 (13)	−0.0080 (14)	−0.0151 (12)
C112	0.139 (3)	0.094 (2)	0.096 (3)	−0.025 (2)	0.042 (2)	−0.040 (2)
C113	0.155 (4)	0.102 (3)	0.155 (4)	−0.025 (3)	0.055 (4)	−0.075 (3)
C114	0.118 (3)	0.077 (2)	0.145 (4)	−0.014 (2)	−0.006 (3)	−0.038 (2)
C115	0.114 (3)	0.091 (3)	0.105 (3)	−0.034 (2)	0.001 (2)	−0.010 (2)
C116	0.091 (2)	0.080 (2)	0.082 (2)	−0.0077 (17)	0.0084 (18)	−0.0214 (16)
O31	0.0669 (11)	0.0685 (11)	0.0504 (10)	−0.0149 (8)	−0.0013 (8)	0.0068 (8)
C311	0.0693 (16)	0.0594 (14)	0.0502 (13)	−0.0104 (12)	−0.0084 (13)	0.0043 (12)
C312	0.079 (2)	0.130 (3)	0.102 (3)	0.012 (2)	−0.016 (2)	−0.033 (2)
C313	0.071 (2)	0.215 (6)	0.141 (4)	0.013 (3)	−0.021 (3)	−0.018 (4)
C314	0.105 (3)	0.163 (5)	0.122 (4)	−0.052 (3)	−0.058 (3)	0.022 (3)
C315	0.155 (4)	0.090 (3)	0.095 (3)	−0.045 (3)	−0.054 (3)	0.005 (2)
C316	0.112 (3)	0.0653 (18)	0.072 (2)	−0.0072 (17)	−0.0192 (19)	−0.0057 (15)
O32	0.0513 (9)	0.0601 (10)	0.0879 (14)	−0.0070 (8)	0.0105 (9)	−0.0096 (9)
C321	0.0472 (12)	0.0554 (13)	0.0585 (15)	−0.0049 (10)	0.0080 (11)	0.0007 (11)
C322	0.094 (2)	0.081 (2)	0.088 (2)	−0.0048 (17)	0.0011 (19)	0.0280 (18)
C326	0.075 (2)	0.077 (2)	0.125 (3)	0.0002 (16)	−0.025 (2)	0.005 (2)
C324	0.100 (3)	0.074 (2)	0.178 (5)	−0.023 (2)	0.027 (3)	−0.007 (3)
C323	0.107 (3)	0.082 (2)	0.137 (4)	−0.008 (2)	0.019 (3)	0.034 (2)
C325	0.069 (2)	0.108 (3)	0.185 (5)	−0.022 (2)	−0.039 (3)	−0.010 (3)
O51	0.0675 (11)	0.0589 (10)	0.0759 (13)	−0.0059 (8)	0.0179 (10)	−0.0014 (9)
C511	0.0477 (13)	0.0528 (14)	0.0769 (18)	−0.0098 (10)	0.0146 (13)	0.0021 (12)
C512	0.0588 (16)	0.0712 (18)	0.098 (2)	−0.0062 (13)	−0.0001 (16)	0.0073 (17)
C513	0.085 (2)	0.107 (3)	0.091 (3)	−0.021 (2)	−0.0138 (19)	−0.008 (2)
C514	0.101 (3)	0.081 (2)	0.123 (3)	−0.026 (2)	−0.002 (2)	−0.024 (2)
C515	0.106 (3)	0.0510 (17)	0.136 (4)	−0.0067 (16)	0.005 (3)	−0.0052 (19)
C516	0.0836 (19)	0.0622 (16)	0.088 (2)	−0.0064 (15)	−0.0017 (17)	0.0077 (16)
O52	0.0762 (12)	0.0526 (10)	0.0798 (14)	0.0011 (8)	−0.0101 (10)	0.0119 (9)
C521	0.0734 (16)	0.0524 (13)	0.0612 (16)	0.0098 (12)	−0.0112 (13)	0.0080 (12)
C522	0.085 (2)	0.107 (3)	0.0608 (19)	−0.0034 (18)	0.0003 (16)	−0.0139 (16)
C523	0.097 (3)	0.126 (3)	0.079 (3)	−0.014 (2)	−0.021 (2)	−0.012 (2)
C524	0.068 (2)	0.127 (3)	0.098 (3)	0.020 (2)	−0.0100 (19)	0.007 (2)
C525	0.087 (3)	0.128 (3)	0.114 (3)	0.036 (2)	0.005 (2)	−0.032 (3)
C526	0.085 (2)	0.083 (2)	0.093 (2)	0.0225 (17)	−0.0099 (19)	−0.0278 (18)

Geometric parameters (Å, º)

Cl1—P1	2.0064 (10)	O32—C321	1.392 (3)
P1—N6	1.561 (2)	C321—C322	1.349 (4)
P1—O11	1.5693 (19)	C321—C326	1.360 (4)
P1—N2	1.572 (2)	C322—C323	1.344 (4)
N2—P3	1.580 (2)	C322—H322	0.9300
P3—N4	1.571 (2)	C326—C325	1.402 (4)
P3—O31	1.5830 (18)	C326—H326	0.9300
P3—O32	1.5866 (17)	C324—C323	1.334 (5)
N4—P5	1.576 (2)	C324—C325	1.355 (5)
P5—O51	1.5711 (19)	C324—H324	0.9300
P5—N6	1.576 (2)	C323—H323	0.9300
P5—O52	1.5871 (19)	C325—H325	0.9300
O11—C111	1.415 (3)	O51—C511	1.410 (3)
C111—C112	1.352 (4)	C511—C516	1.368 (4)
C111—C116	1.356 (4)	C511—C512	1.371 (4)
C112—C113	1.383 (5)	C512—C513	1.373 (4)
C112—H112	0.9300	C512—H512	0.9300
C113—C114	1.345 (6)	C513—C514	1.367 (5)
C113—H113	0.9300	C513—H513	0.9300
C114—C115	1.354 (5)	C514—C515	1.370 (5)
C114—H114	0.9300	C514—H514	0.9300
C115—C116	1.383 (4)	C515—C516	1.379 (4)
C115—H115	0.9300	C515—H515	0.9300
C116—H116	0.9300	C516—H516	0.9300
O31—C311	1.402 (3)	O52—C521	1.396 (3)
C311—C312	1.341 (4)	C521—C526	1.346 (4)
C311—C316	1.360 (4)	C521—C522	1.367 (4)
C312—C313	1.376 (5)	C522—C523	1.384 (5)
C312—H312	0.9300	C522—H522	0.9300
C313—C314	1.370 (6)	C523—C524	1.343 (5)
C313—H313	0.9300	C523—H523	0.9300
C314—C315	1.333 (6)	C524—C525	1.364 (5)
C314—H314	0.9300	C524—H524	0.9300
C315—C316	1.354 (5)	C525—C526	1.375 (5)
C315—H315	0.9300	C525—H525	0.9300
C316—H316	0.9300	C526—H526	0.9300
N6—P1—O11	105.88 (12)	C311—C316—H316	120.1
N6—P1—N2	118.69 (11)	C321—O32—P3	125.24 (15)
O11—P1—N2	112.66 (11)	C322—C321—C326	120.5 (3)
N6—P1—Cl1	108.66 (11)	C322—C321—O32	123.1 (2)
O11—P1—Cl1	101.97 (9)	C326—C321—O32	116.4 (2)
N2—P1—Cl1	107.68 (9)	C323—C322—C321	121.1 (3)
P1—N2—P3	120.59 (12)	C323—C322—H322	119.4
N4—P3—N2	117.82 (11)	C321—C322—H322	119.4
N4—P3—O31	109.80 (10)	C321—C326—C325	118.0 (3)
N2—P3—O31	110.32 (10)	C321—C326—H326	121.0
N4—P3—O32	107.25 (10)	C325—C326—H326	121.0
N2—P3—O32	110.74 (11)	C323—C324—C325	121.0 (3)
O31—P3—O32	99.27 (10)	C323—C324—H324	119.5
P3—N4—P5	121.74 (12)	C325—C324—H324	119.5
O51—P5—N4	111.55 (11)	C324—C323—C322	119.9 (4)
O51—P5—N6	106.09 (12)	C324—C323—H323	120.1
N4—P5—N6	117.12 (11)	C322—C323—H323	120.1
O51—P5—O52	100.45 (10)	C324—C325—C326	119.4 (4)
N4—P5—O52	109.91 (11)	C324—C325—H325	120.3
N6—P5—O52	110.39 (13)	C326—C325—H325	120.3
P1—N6—P5	122.30 (14)	C511—O51—P5	122.59 (15)
C111—O11—P1	124.42 (16)	C516—C511—C512	121.8 (3)
C112—C111—C116	121.3 (3)	C516—C511—O51	119.6 (3)
C112—C111—O11	118.1 (3)	C512—C511—O51	118.6 (2)
C116—C111—O11	120.4 (2)	C511—C512—C513	118.5 (3)
C111—C112—C113	118.7 (4)	C511—C512—H512	120.7
C111—C112—H112	120.7	C513—C512—H512	120.7
C113—C112—H112	120.7	C514—C513—C512	120.9 (4)
C114—C113—C112	121.0 (4)	C514—C513—H513	119.5
C114—C113—H113	119.5	C512—C513—H513	119.5
C112—C113—H113	119.5	C513—C514—C515	119.6 (3)
C113—C114—C115	119.7 (4)	C513—C514—H514	120.2
C113—C114—H114	120.2	C515—C514—H514	120.2
C115—C114—H114	120.2	C514—C515—C516	120.6 (3)
C114—C115—C116	120.4 (4)	C514—C515—H515	119.7
C114—C115—H115	119.8	C516—C515—H515	119.7
C116—C115—H115	119.8	C511—C516—C515	118.6 (3)
C111—C116—C115	119.0 (3)	C511—C516—H516	120.7
C111—C116—H116	120.5	C515—C516—H516	120.7
C115—C116—H116	120.5	C521—O52—P5	120.57 (16)
C311—O31—P3	122.46 (15)	C526—C521—C522	120.4 (3)
C312—C311—C316	120.9 (3)	C526—C521—O52	118.7 (3)
C312—C311—O31	121.3 (3)	C522—C521—O52	120.8 (3)
C316—C311—O31	117.5 (3)	C521—C522—C523	119.0 (3)
C311—C312—C313	118.6 (4)	C521—C522—H522	120.5
C311—C312—H312	120.7	C523—C522—H522	120.5
C313—C312—H312	120.7	C524—C523—C522	120.8 (4)
C314—C313—C312	120.4 (4)	C524—C523—H523	119.6
C314—C313—H313	119.8	C522—C523—H523	119.6
C312—C313—H313	119.8	C523—C524—C525	119.4 (4)
C315—C314—C313	119.5 (4)	C523—C524—H524	120.3
C315—C314—H314	120.2	C525—C524—H524	120.3
C313—C314—H314	120.2	C524—C525—C526	120.4 (4)
C314—C315—C316	120.7 (4)	C524—C525—H525	119.8
C314—C315—H315	119.7	C526—C525—H525	119.8
C316—C315—H315	119.7	C521—C526—C525	119.8 (3)
C315—C316—C311	119.8 (4)	C521—C526—H526	120.1
C315—C316—H316	120.1	C525—C526—H526	120.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C523—H523···N6^i	0.93	2.69	3.352 (4)	129
C315—H315···N4^ii	0.93	2.89	3.621 (4)	136
C515—H515···N2^iii	0.93	3.05	3.672 (4)	126

Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x−1/2, −y+1/2, −z; (iii) −x+1/2, y−1/2, z.