Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N₃P₃Cl_{(6 − n)}(NHBu^t)_n derivatives

A series of compounds of the N₃P₃Cl_{(6 − n)}(NHBu^t)_n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N₃P₃Cl₅(NHBu^t) and N₃P₃Cl₂(NHBu^t)₄ have been determined at 120 K, and those of N₃P₃Cl₆ and N₃P₃Cl₄(NHBu^t)₂ have been redetermined at 120 K. These are compared with the known structure of N₃P₃(NHBu^t)₆ studied at 150 K. Trends in molecular parameters [phosphazene ring, P—Cl and P—N(HBu^t) distances, PCl₂ angles, and endo- and exocyclic phosphazene ring parameters] across the series are observed. Hydrogen-bonding motifs are identified, characterized and compared. Both the molecular and the hydrogen-bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBu^t) group.

1. Introduction

During extensive investigations of the replacement patterns of chloride substituents in N₃P₃Cl₆ by amines (Shaw, 1976; Krishnamurthy et al., 1976) the following conclusions were reached:

(i) Primary amines, H₂NR, show a greater degree of variation in substitution patterns than secondary amines, HNR₂.

(ii) Most secondary amines follow a predominantly non-geminal path, in which a PCl₂ group is attacked in preference to a PCl(NR₂) group.

(iii) At disubstitution, N₃P₃Cl₄(NHR)₂, both geminal and non-geminal replacements occur, depending on the R group. For R = Et only non-geminal cis and trans derivatives were observed, for R = Prⁱ all three isomers, geminal and non-geminal, were obtained, whilst for R = Bu^t only the geminal derivative was isolated. Thus, under comparable conditions, the increasing steric bulk of the R group causes a change from non-geminal to geminal substitution.

(iv) At tetra-substitution, N₃P₃Cl₂(NHR)₄, a geminal pattern prevails.

Thus, when a cyclotriphosphazene compound containing PCl₂ groups is allowed to react with tertiary butylamine, H₂NBu^t, geminal P(NHBu^t)₂ groups are formed with very few exceptions (Das et al., 1965; Begley et al., 1979; Krishnamurthy et al., 1980, Coles et al., 2001), and so tertiary butylamine is the preferred reagent to introduce geminal P(NHR)₂ groupings into a cyclotriphosphazene derivative. The different substitution patterns have been explained by nucleophilic attack at different reaction sites, viz. at phosphorus or at the H atom of the PCl(NHR) grouping, giving rise to a proton abstraction/chloride ion elimination mechanism, which has been discussed elsewhere (Das et al., 1965; Ganapathiappan & Krishnamurthy, 1987). If the P atom becomes more susceptible to nucleophilic attack, which occurs in N₄P₄Cl₈ (Krishnamurthy et al., 1977, 1978), the balance is tipped towards non-geminal replacements giving rise to PCl(NHBu^t) groups. H₂NBu^t is the most sterically hindered of the primary amines discussed, which is also borne out by the fact that under many reaction conditions only tetra-substitution, N₃P₃Cl₂(NHBu^t)₄, is usually achieved (Das et al., 1965), although the fully substituted derivative, N₃P₃(NHBu^t)₆, can be obtained under very drastic conditions (Das et al., 1965; Bickley et al., 2003). Whilst many other phosphazene derivatives containing P—Cl and P—NHR groupings are rather unstable, this does not seem to apply to tertiary butylamino derivatives. Following previous work (Beşli, Coles, Davies, Hursthouse, Kiliç, Mayer & Shaw, 2002; Beşli, Coles, Davies, Hursthouse, Kiliç, Mayer, Shaw & Yenilmez, 2002; Coles, Davies, Eaton, Hursthouse et al., 2004) the crystal structures of a series of tertiary butylamino derivatives of cyclophosphazene have been determined, and their molecular parameters and hydrogen-bonding motifs are discussed in the light of the chemical and physical properties of the compounds.

2. Experimental

2.1. Preparation of compounds

Hexachlorocyclotriphosphazene (1) (15 g, 43.16 mmol) and tert-butylamine (12.6 g, 173 mmol) were dissolved in dichloromethane (200 ml) under argon pressure in a 250 ml three-necked round-bottomed flask. The reaction mixture was stirred and refluxed in an oil-bath for 6 d. tert-Butylamine hydrochloride was filtered off and the solvent was removed at 303 K. Two compounds were detected by thin-layer chromatography [R_f = 0.6 (2) and 0.3 (3), N₃P₃Cl₄(NHBu^t)₂], using dichloromethane–n-hexane (1:2) as the mobile phase. The crude product was subjected to column chromatography on silica gel using dichloromethane–n-hexane (1:2) as the eluant. 1-tert-Butylamino-1,3,3,5,5-pentachlorocyclotriphosphazatriene (2) was separated and recrystallized from n-hexane. Found: C 12.56, H 2.74, N 14.66%; (M+H)⁺, 384 C₄H₁₀Cl₅N₄P₃; requires: C 12.50, H 2.62, N 14.58%; M 383.34. M.p. 319 K [literature 262–263 K (Das et al., 1965); 383 K (Begley et al., 1979)]. Yield 2 g, 21%. 1,1-Bis(tert-butylamino)-3,3,5,5-tetrachloro­cyclo­tri­phos­phazene (3) was separated and recrystallized from n-hexane–dichloromethane (1:1). Found: C 22.74, H 4.68, N 16.15%; (M+H)⁺, 421 C₈H₂₀Cl₄N₅P₃; requires: C 22.82, H 4.79, N 16.63%; M 421. M.p. 393–395 K [literature 393–395 K (Das et al., 1965); 394 K (Begley et al., 1979)]. Yield 4.35 g, 24%.

Details of the preparation of N₃P₃Cl₂(NHBu^t)₄ (4) have been reported elsewhere (Das et al., 1965), with m.p. = 429 K from light petroleum.

2.2. X-ray crystallography

Data were collected at low temperature on an Nonius KappaCCD area-detector diffractometer located at the window of a Nonius FR591 rotating-anode X-ray generator, equipped with a molybdenum target (λ_Mo Kα = 0.71073 Å). Structures were solved and refined using the SHELX97 (Sheldrick, 1997) suite of programs. Data were corrected for absorption effects by means of comparison of equivalent reflections using the program SORTAV (Blessing, 1997). Non-H atoms were refined anisotropically, whilst H atoms were located from a difference map and freely refined isotropically for all N-bound H atoms, whereas all methyl H atoms were located in idealized positions according to a riding model, with their displacement parameters based on the values of their parent atoms. Compound (3) exhibited some rotational disorder in one Bu^t group. It also crystallized in a chiral space group with a Flack (1983) parameter that refined to a value of 0.08 (8), and hence it can be assumed that the correct absolute structure has been determined. Pertinent data collection and refinement parameters are collated in Table 1.¹

Table 1
Data collection and refinement parameters for structures (1)–(4)

	(1)	(2)	(3)	(4)
Crystal data
Chemical formula	Cl6N3P3	C4H10Cl5N4P3	C8H20Cl4N5P3	C16H40Cl2N7P3
Mr	347.64	384.32	421.00	494.36
Cell setting, space group	Orthorhombic, Pnma	Monoclinic, P21/c	Orthorhombic, Pna21	Monoclinic, P21/n
Temperature (K)	120 (2)	120 (2)	120 (2)	120 (2)
a, b, c (Å)	13.8572 (8), 12.8086 (11), 6.0801 (5)	13.8045 (14), 10.7964 (16), 20.7719 (12)	20.3441 (7), 11.9481 (4), 15.9661 (7)	12.5207 (2), 16.1282 (2), 13.1311 (2)
β (°)	90	104.132 (7)	90	95.9030 (10)
V (Å^3)	1079.17 (14)	3002.1 (6)	3880.9 (3)	2637.59 (7)
Z	4	8	8	4
Dx Mg m^−3)	2.140	1.701	1.441	1.245
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	1403	6816	29 220	16 145
θ range (°)	2.9–27.5	2.9–27.5	2.9–27.5	2.9–27.5
μ (mm^−1)	1.99	1.27	0.85	0.45
Crystal form, colour	Plate, colourless	Cut plate, colourless	Plate, colourless	Block, colourless
Crystal size (mm)	0.50 × 0.40 × 0.10	0.18 × 0.10 × 0.02	0.16 × 0.14 × 0.06	0.40 × 0.25 × 0.25
Data collection
Diffractometer	Bruker–Nonius KappaCCD area detector	Bruker–Nonius 95 mm CCD camera on κ goniostat	Bruker–Nonius KappaCCD area detector	Bruker–Nonius KappaCCD area detector
Data collection method	φ and ω scans	φ and ω scans	φ and ω scans	φ and ω scans
Absorption correction	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)
Tmin	0.437	0.804	0.875	0.842
Tmax	0.826	0.975	0.951	0.897
No. of measured, independent and observed reflections	7733, 1283, 1194	40 456, 6867, 5549	29 635, 8587, 5744	29 576, 5994, 5106
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.022	0.044	0.078	0.057
θmax (°)	27.5	27.5	27.5	27.5
Range of h, k, l	−16 → h → 18	−17 → h → 17	−26 → h → 24	−16 → h → 16
	−14 → k → 16	−14 → k → 14	−13 → k → 15	−20 → k → 20
	−7 → l → 7	−26 → l → 26	−20 → l → 20	−17 → l → 17
Refinement
Refinement on	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.028, 0.074, 1.26	0.034, 0.086, 1.07	0.053, 0.107, 1.02	0.038, 0.100, 1.04
No. of reflections	1283	6867	8587	5994
No. of parameters	62	370	414	270
H-atom treatment	No H atoms present	Difmap	Mixture of independent and constrained refinement	Mixture of independent and constrained refinement
Weighting scheme	w = 1/[σ^2(Fo^2) + (0.0403P)^2 + 0.3798P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 1.5716P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0134P)^2 + 2.2238P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 1.1457P], where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	0.005	0.001	0.011	0.030
Δρmax, Δρmin (e Å^−3)	0.67, −0.68	0.49, −0.50	0.44, −0.43	0.27, −0.33
Extinction method	SHELXL	SHELXL	SHELXL	SHELXL
Extinction coefficient	0.0213 (18)	0.0021 (2)	0.0041 (3)	0.0099 (11)
Flack parameter	–	–	Flack (1983)	–
Computer programs used: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL (Sheldrick, 1997), PLATON (Spek, 1998).

3. Discussion

3.1. Molecular structures

Changes in molecular parameters of cyclophosphazene derivatives have been investigated as a function of substituents at fixed positions (Coles, Davies, Hursthouse et al., 2004); the overall architecture of these molecules remained the same, and so the designation of bond length and bond angle parameters was unambiguous for such a series of compounds. The molecules in the present study have different degrees of substitution of Cl atoms by NHBu^t residues, and this situation requires some modifications in the designation of their molecular parameters, as summarized in Fig. 1. The endocyclic bond angle α is defined as N—P(X)₂—N, the endocyclic bond angle β as (Y)₂P—N—P(X)₂ or (XY)P—N—P(X)₂, the endocyclic bond angle γ as N—P(XY)—N or N—P(Y)₂—N and the endocyclic bond angle δ as (X)₂P—N—P(X)₂ or (Y)₂P—N—P(Y)₂, where X = Cl and Y = NHBu^t. Analogous descriptions apply to definitions of the endocyclic bond lengths a, b, c etc., as summarized in Fig. 1. Selected molecular parameters for all the crystal structures used in this comparison are given in Table 2.

Table 2
Selected molecular parameters for structures (1)–(5)

	(1)	(2)	(3)	(4)	(5)
a	1.577 (3)	1.594 (2)	1.619 (1)	1.623 (2)	1.578 (4)
b	–	1.567 (2)	1.556 (1)	1.560 (2)	–
Δ(P–N) = a − b	–	0.027 (2)	0.063 (1)	0.063 (2)	–
c	–	1.575 (2)	1.577 (1)	1.598 (2)	–
d	1.986 (3)	1.991 (1)	2.003 (2)	2.034 (1)	–
d′	–	2.017 (1)	–	–	–
e	–	–	1.616 (1)	1.644 (2)	1.638 (4)
e′	–	1.600 (2)	–	–	–
α	118.5 (2)	119.2 (1)	119.9 (3)	121.3 (1)	–
β	121.1 (2)	121.6 (1)	123.5 (2)	121.9 (1)	121.9 (2)
γ	–	116.9 (1)	112.3 (2)	114.4 (1)	115.9 (2)
δ	–	120.6 (1)	118.4 (2)	126.7 (1)	–
θ	101.9 (1)	101.2 (1)	99.3 (1)	98.0 (1)	–
ω	–	–	104.8 (2)	102.5 (1)	101.7 (2)
λ	–	107.4 (1)	–	–	–
ΣN	–	358.3 (1)	358.8 (2)	353.7 (1)	355.1 (2)

Figure 1 Designation of molecular parameter descriptors for (1)–(5).

Although the room-temperature molecular structure of N₃P₃Cl₆ (1) had been reported (Bullen, 1971), a low-temperature structure (depicted in Fig. 2) was determined for the purposes of accurate comparison in this study.

Figure 2 The molecular structure and numbering scheme of (1).

The structures of the two chemically equivalent molecules in the asymmetric unit of N₃P₃Cl₅(NHBu^t) (2) are shown in Fig. 3, and a number of structural differences from (1) are observed. There is a significant decrease in γ, with a corresponding increase in β, and smaller changes are observed in α and δ. There is a marked increase in bond length a and a marked decrease in b, whereas c is largely unaffected. The non-geminal P—Cl bond, d′, is longer than the corresponding bond lengths, d, of the PCl₂ group. The opposite behaviour is observed for the exocyclic P—N bond length e′, which is substantially shorter than those in geminal groups, e. Both effects have been observed in similar structures (Ahmed & Pollard, 1972; Ahmed & Gabe, 1975; Ahmed & Fortier, 1980; Alkubaisi et al., 1988; Beşli, Coles, Davies, Hursthouse, Kilic, Mayer, Shaw & Yenilmez, 2002; Coles, Davies, Eaton et al., 2004; Beşli, Coles, Davies, Hursthouse et al., 2004; Beşli, Coles, Davies, Eaton et al., 2004). The sum of the bond angles around the exocyclic N atom [358.3 (1)°] shows that it has trigonal planar character.

Figure 3 The molecular structure and numbering scheme of (2).

Although the crystal structure of N₃P₃Cl₄(NHBu^t)₂ (3) had been previously determined (Begley et al., 1979), the study was performed at room temperature and the data were of insufficient quality to determine H-atom positions. As (3) is a typical example of a geminally disubstituted derivative of the type, N₃P₃Cl₄R₂, where R is a strongly electron-releasing substituent, an accurate structure (shown in Fig. 4) was determined at low temperature, so that the molecular parameters could be included in this work. The structure exhibits two chemically equivalent molecules in the asymmetric unit. The bond lengths a of 1.619 (1) Å are relatively long, whereas those for b of 1.556 (1) Å are relatively short, giving a Δ(P—N) (= a − b) value of 0.063 (1) Å, one of the largest observed from a survey of the Cambridge Structural Database (CSD; Allen, 2002). Concomitantly, there is a very small bond angle α of 112.3 (2)° and a very large β angle of 123.5 (2)°. The exocyclic P—N bond length, e, of 1.616 (1) Å is quite short for this type of bond, indicating extensive back-donation of the lone-pair of electrons on the N atom towards the P atom. This bond shortening might have been even greater were it not for the conformation of the NHBu^t substituents, one of which is in almost a complete Type II conformation, while the other is between Type I and III [an explanation of these conformational types is given by Fincham et al. (1986)]. The back-donation is also demonstrated by the sum of the bond angles around the exocyclic N atoms of 358.8 (2)°, showing their trigonal planar character. Increases in P—Cl bond lengths, d, and a decrease in bond angle Cl—P—Cl, ω, are also noted.

Figure 4 The molecular structure and numbering scheme of (3).

The crystal structure of N₃P₃Cl₂(NHBu^t)₄ (4) is presented in Fig. 5. The effect on molecular parameters resulting from the large electron-releasing capacity of the NHBu^t substituents is also demonstrated in this compound, as the changes in some parameters are further enhanced compared with the disubstituted compound (3). The bond angle α of 114.4 (1)° bears this out, as do the respective bond lengths a and b of 1.623 (2) and 1.560 (2) Å, giving a Δ(P—N) value of 0.063 (2) Å. The averaged sum of bond angles around the exocyclic N atoms of 353.7 (1)° is the lowest in this series of compounds and indicates the greatest deviation from a trigonal planar structure.

Figure 5 The molecular structure and numbering scheme of (4).

The low-temperature structure of N₃P₃(NHBu^t)₆ (5) has been reported previously (Bickley et al., 2003) with the CSD refcode GUZVIG, and is used for comparison in this study. As expected for such a symmetrically substituted derivative, there are no statistically significant variations in the endocyclic P—N bond lengths. The averaged sum of the bond angles around the exocyclic N atoms of 355.1 (2)° is also somewhat lower than those for (2) and (3).

A measure of the conformational orientation of the NHBu^t groups relative to each other is given by the torsion angle to both adjacent ring N atoms. A measure of the close-packed nature of the NHBu^t groups is given by the non-bonded separation of the central C atoms between adjacent moieties (Table 3). It can be seen from Table 3 that there is a general decrease in this C⋯C distance for a corresponding increase in the number of NHBu^t groups situated about the N₃P₃ core. This trend is indicative of the fact that these groups are more tightly clustered around the core and hence impede any interactions with it, owing to an increase in steric hindrance. Another indication of the close-packed nature of the NHBu^t groups is the dihedral angle between the plane of the N₃P₃ ring and the orientation of the NHBu^t group with respect to the P—N bond (Table 3). With an increasing number of NHBu^t groups there is, on average, a corresponding increase in the torsion angle, indicating that this group must increasingly twist away from its sterically unhindered optimal position.

Table 3
Geometric parameters for NH—Bu^t groups

Compound		Torsion angles of NHBu^t substituents to both adjacent ring N atoms		C⋯C separations between central atoms on adjacent NHBu^t groups
(2)	Molecule A	31.9 (5)	162.5 (4)
	Molecule B	−41.1 (5)	−171.5 (5)
(3)	Molecule A	41.2 (5)	−82.1 (5)	4.72
		49.0 (5)	172.5 (5)
	Molecule B	−37.8 (5)	86.8 (5)	4.68
		−51.3 (6)	−174.4 (5)
(4)	Molecule A	−43.07 (16)	84.84 (16)	4.74
		−42.2 (2)	85.23 (19)	4.75
		−37.63 (17)	−162.53 (15)
		−32.4 (2)	−158.29 (17)
(5)	Molecule A	−63.84	79.70	4.579
		−61.85	−83.88	4.605
		−51.52	83.18	4.548
		59.28	170.73
		45.75	171.70
		−45.32	−173.10
	Molecule B	59.80	79.12	4.575
		−63.30	−81.27	4.569
		−60.85	84.54	4.554
		−49.67	169.13
		48.31	172.77
		−45.01	173.10

3.2. Hydrogen bonding

The hydrogen bonding in the crystal structure of (2) is depicted in Fig. 6, which shows the formation of discreet head-to-tail dimers containing an eight-membered ring as a result of donation from the Bu^tN—H group to the ring N atom of another molecule. The conformation of this ring is approximately saddle-shaped, with slightly different distances between donor and acceptor atoms, of 3.079 (4) and 3.095 (4) Å, respectively.

Figure 6 The hydrogen-bonded structure formed by (2).

The hydrogen bonding in the crystal structure of (3) is presented in Fig. 7 and leads to the formation of a similar structural arrangement to (2), where the intermolecular hydrogen bonds form an eight-membered ring of complementary dimers. The corresponding donor–acceptor separation distances of (3) are 3.123 (3) and 3.167 (4) Å, respectively, making them somewhat longer than those in (2).

Figure 7 The hydrogen-bonded structure formed by (3).

The hydrogen bonding exhibited by (4) forms a similar dimer motif (Fig. 8), although the conformation of the eight-membered ring differs in that it is a boat form with the P atoms at the apices and the central six atoms coplanar. The symmetric N⋯N distances, with a value of 3.392 (4) Å, are even longer than in (3), indicating weaker hydrogen bonding, which presumably arises from an increase in steric hindrance in the hydrogen-bonding region.

Figure 8 The hydrogen-bonded structure formed by (4).

Bickley et al. (2003) reported no hydrogen bonding in the crystal structure of N₃P₃(NHBu^t)₆ (5). As the shortest N⋯N separation in the structure is 4.950 (5) Å there is certainly no sign of a hydrogen bond from any Bu^tN—H group to a ring N atom. There may be a very weak intramolecular interaction from one NHBu^t group to another NHBu^t group in a cis non-geminal position, because there are two of these interactions having separations of 3.751 (5) and 3.766 (5) Å in chemically identical environments in the two molecules composing the asymmetric unit.

3.3. Structure–property relationships

The molecular parameters of (2)–(5) are discussed in terms of the basicity of each molecule. The NHBu^t substituent is one of the most base-strengthening primary amino residues so far investigated, with a substituent constant α_R value of 5.9 (Feakins et al., 1969). The basicities of the more basic compounds N₃P₃(NHBu^t)₆ and N₃P₃Cl₂(NHBu^t)₄ have been measured in nitrobenzene solution with values of 8.0 and 4.35, respectively (Feakins et al., 1964). In fact, the basicity of 8.0 for (4) would be ∼ 9.9, if allowance were made for the saturation effect (Feakins et al., 1969). The basicity values of the remaining derivatives have been obtained by summation of known substituent basicity constants (Σα_R) according to the previously described (Beşli, Coles, Davies, Hursthouse, Kilic, Mayer & Shaw, 2002), viz. −20.3, −14 and −8 for (1), (2) and (3), respectively. These Σα_R values span a range of 30 pK_a units.

3.3.1. Molecular structures

Although the preparation of (2) has been published on two occasions, different physical properties were reported; the first report (Das et al., 1965) gave a melting point of 262–263 K and later a ³¹P NMR spectrum with absorptions at 16.0 and −5.3 p.p.m. (Keat et al., 1976). The sample of (2) prepared for this study has a melting point of 319 K and a ³¹P NMR spectrum with absorptions at 21.1 and 13.45 p.p.m. The fact that the structure is confirmed by X-ray crystallography (Fig. 3) indicates that the former report must have been incorrectly assigned to a different product. The second report (Begley et al., 1979) gave a melting point of 383 K for (2), which may indicate a different polymorph, and investigations into this result are underway.

The electron-donating power of the NHBu^t group is demonstrated by the Δ(P—N) values of (2), (3) and (4), which are 0.027 (2), 0.063 (1) and 0.063 (2) Å, respectively (Table 2). As indicated by the results above, a simple additive behaviour is not expected for endocyclic parameters. For (2), in particular, some of the electron density appears to be diverted into lengthening the P(NHBu^t)—Cl bond, which at 2.017 (1) Å is considerably longer than the other P—Cl bonds in this compound. There are substantial changes in some bond angles, but again these are non-uniform, e.g. reduction in α.

In contrast to the non-uniform changes in endocyclic parameters, the exocyclic values follow uniform and consistent trends. The effect of the electron-releasing capacity of the substituents on the average values of the P—Cl bonds and the Cl—P—Cl bond angles in the remaining PCl₂ groups are compared with the sum of the substituent basicity constants (∑α_R) in Table 4, where the structures of some related PPh₂ derivatives have been included, viz. N₃P₃Cl₄Ph₂ (6) (Mani et al., 1965) and N₃P₃Cl₂Ph₄ (7) (Mani et al., 1966). In this series of compounds there is a good correlation between the increase in P—Cl bond length and the increase in ∑α_R, as shown graphically in Fig. 9(a). Although the changes are small for the disubstituted compounds in this sequence, they are in keeping with the electron-supplying properties discussed above. For the tetrasubstituted compounds the effects on the P—Cl bond lengths are rather larger, as expected, because the effects of four donor groups are spread over only two P—Cl bonds, whereas the effects of two donors are spread over four P—Cl bonds for the disubstituted derivatives. A similar explanation can account for the concomitant decrease in Cl—P—Cl bond angles with ∑α_R (shown graphically in Fig. 9a), which is expected from a lengthening of the P—Cl bonds.

Table 4
Sum of substituent basicity constants (∑α_R), geometric parameters and averaged ³⁵Cl NQR frequencies of the PCl₂ group of (1)–(4), (6) and (7)

Compounds N₃P₃Cl₄Ph₂ (6) and N₃P₃Cl₂Ph₄ (7) are included for comparison purposes.

Compound	Molecular formula	P—Cl (Å)	Cl—P—Cl (°)	∑αR	Averaged ^35Cl NQR frequencies (77 K) (MHz)
(1)	N3P3Cl6	1.986 (3)	101.9 (1)	0.0	28.482
(2)	N3P3Cl5(NHBu^t)	1.991 (1)	101.2 (1)	5.9	–
(6)	N3P3Cl4Ph2	1.998 (6)	100.3 (2)	8.4	27.759
(3)	N3P3Cl4(NHBu^t)2	2.003 (2)	99.3 (1)	11.8	27.481
(7)	N3P3Cl2Ph4	2.017 (4)	98.5 (2)	16.8	26.511
(4)	N3P3Cl2(NHBu^t)4	2.034 (1)	98.0 (1)	23.6	26.398

Figure 9 Correlation between (a) the sum of substituent basicity constants (∑αR) and (b) averaged ^35Cl NQR frequencies (MHz) for P—Cl bond lengths and Cl—P—Cl bond angles for data presented in Table 4.

The above linear relationships are mirrored in a number of other physical properties. In a study of the Faraday effect of some aminochlorocyclotriphosphazenes in CCl₄ solution, it was noted that in a plot of the number of amino substituents versus the molecular magnetic rotation geminal derivatives gave a good straight-line relationship, whilst non-geminal derivatives showed positive deviations (Bruniquel et al., 1973). A possible explanation of these observations is that the former only depends on electron distributions within the plane of the N₃P₃ ring, whereas in the latter there is ample evidence from crystallographic data that there is an electron transfer, which changes the parameters of substituents above and below this ring.

In this study a significant correlation has been observed between molecular parameters and ³⁵Cl NQR frequencies of PCl₂ groups of cyclophosphazene derivatives, perhaps because this technique deals with crystalline substances as does crystallography. It has been shown previously that a linear relationship exists between ³⁵Cl NQR frequencies and the P—Cl bond lengths both for Ph derivatives (Keat et al., 1972) and for NHBu^t derivatives (Sridharan et al., 1980). It is found that such a relationship holds for the compounds reported in this study and that it also extends to their Cl—P—Cl bond angles (Fig. 9b). These results are also important because the observed linear correlations between molecular parameters and a physical parameter (³⁵Cl NQR frequency) for molecules in the solid state are mirrored in the analogous dependence on a physical parameter (sum of substituent basicity constants, ∑α_R) for molecules in the solution state.

The structural data also permit some tentative conclusions to be drawn as to why there is a mono, N₃P₃Cl₅(NHBu^t), but no tris derivative, N₃P₃Cl₃(NHBu^t)₃, because the successive substitutions of the cyclophosphazene group change molecular parameters, particularly the P—Cl bond lengths. There is now a good deal of evidence for a hydrogen abstraction/chloride ion elimination mechanism leading to a trigonal planar intermediate, which then reacts rapidly with any nucleophile present (Das et al., 1965; Ganapathiappan & Krishnamurthy, 1987). The proposed mechanism for nucleophilic substitution at a phosphorus site bearing an NHBu^t group is shown in Fig. 10. When X = Cl, which is electron withdrawing, the proton abstraction by base is reversible, which was clearly shown by a D₂O shake-up in proton NMR spectroscopy to eliminate the N–H coupling in (3) and (4) (Das et al., 1965). If X = NHBu^t, which is a strongly electron-supplying group, proton abstraction is irreversible and thus prevents isolation of the tris derivative.

Figure 10 Proposed mechanism for nucleophilic substitution at a phosphorus site bearing an NHBu^t group.

3.3.2. Hydrogen-bonding trends

Compounds (2), (3) and (4) form eight-membered-ring hydrogen-bonded dimers, with the rings in a saddle shape for (2) and (3) and a boat conformation for (4). The increase in average N⋯N distances for (2) (3.087 Å), (3) (3.145 Å) and (4) (3.392 Å) are probably due to steric crowding. There are no intermolecular hydrogen bonds for (5), which is a result of the steric shielding of the potential acceptor N atoms in the cyclophosphazene core of the molecule.

The position of protonation of cyclophosphazene derivatives was originally deduced to be the ring N atoms from potentiometric studies, and this hypothesis was later proven by crystallography (Mani & Wagner, 1971; Shaw, 1976). These same N atoms are involved in the observed hydrogen-bonding patterns. However, the weakest base (2) seems to form the strongest hydrogen bonds, and the strongest base (5) does not form any intermolecular hydrogen-bonded interactions. Undoubtedly steric hindrance must be the cause, a conclusion supported by the geometric and conformational results (see above) regarding the relative conformations of the NHBu^t groups.

4. Conclusions

This is the first series of products from reaction of N₃P₃Cl₆ with a given amine (in this case a bulky primary amine, H₂NR), where all the compounds have been characterized crystallographically. The three hydrogen-bonded dimers show two types of eight-membered ring conformation; one is saddle shaped with slightly different hydrogen bridges for N₃P₃Cl₅(NHBu^t) and N₃P₃Cl₄(NHBu^t)₂, whereas for N₃P₃Cl₂(NHBu^t)₄ the two intermolecular hydrogen-bonded bridges are identical and the conformation is that of a boat. The changes in observed molecular parameters show good correlation with changes in other physical properties, such as the substituent basicity constants, the Faraday effect, some ³¹P NMR parameters and ³⁵Cl NQR frequencies. In spite of the much increased basicity of the ring N atoms, the capacity for intermolecular hydrogen-bonding decreases from the monosubstituted compound, N₃P₃Cl₅(NHBu^t), to N₃P₃Cl₂(NHBu^t)₄ and has disappeared altogether for N₃P₃(NHBu^t)₆. This behaviour is attributed to steric hindrance. The change in molecular parameters with increasing replacement of Cl atoms by NHBu^t groups gives rise to regular changes for exocyclic parameters, but is somewhat erratic for endocyclic parameters because of the different degrees and positions of substitution.

Supporting information

Computing details

Data collection: COLLECT (Hooft, 1998) for (2); DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, 1998) for (3), (4). Cell refinement: DENZO, COLLECT for (1); DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, 1998) for (2); DENZO & COLLECT for (3), (4). Data reduction: DENZO, COLLECT for (1); DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, 1998) for (2); DENZO & COLLECT for (3), (4). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (1), (3), (4). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: PLATON (Spek, 1998) for (1).

Figures

(1) Hexachlorocyclotriphosphazene

Crystal data

Cl6N3P3	Dx = 2.140 Mg m^−3
Mr = 347.64	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1403 reflections
a = 13.8572 (8) Å	θ = 2.9–27.5°
b = 12.8086 (11) Å	µ = 1.99 mm^−1
c = 6.0801 (5) Å	T = 120 K
V = 1079.17 (14) Å^3	Plate, colourless
Z = 4	0.50 × 0.40 × 0.10 mm
F(000) = 672

Data collection

Bruker-Nonius KappaCCD Area Detector diffractometer	1283 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1194 reflections with I > 2σ(I)
10cm confocal mirrors monochromator	Rint = 0.022
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −16→18
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, G.M., 2003)	k = −14→16
Tmin = 0.437, Tmax = 0.826	l = −7→7
7733 measured reflections

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)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0403P)^2 + 0.3798P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.074	(Δ/σ)max = 0.005
S = 1.26	Δρmax = 0.67 e Å^−3
1283 reflections	Δρmin = −0.69 e Å^−3
62 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0213 (18)

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
N1	0.64922 (15)	0.7500	0.5951 (4)	0.0187 (5)
N2	0.49315 (11)	0.64417 (11)	0.4448 (2)	0.0181 (3)
P1	0.59531 (3)	0.64294 (3)	0.55879 (7)	0.01317 (16)
P2	0.43947 (4)	0.7500	0.39325 (10)	0.01308 (18)
Cl1	0.58539 (3)	0.57022 (4)	0.84708 (7)	0.02287 (16)
Cl2	0.68240 (3)	0.54925 (4)	0.39215 (8)	0.02194 (16)
Cl3	0.31285 (4)	0.7500	0.54745 (11)	0.02096 (18)
Cl4	0.39841 (5)	0.7500	0.08080 (10)	0.02267 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0111 (9)	0.0146 (10)	0.0305 (12)	0.000	−0.0067 (9)	0.000
N2	0.0126 (7)	0.0139 (7)	0.0278 (8)	−0.0005 (5)	−0.0068 (6)	−0.0011 (6)
P1	0.0108 (3)	0.0123 (3)	0.0163 (3)	0.00129 (15)	−0.00187 (15)	0.00004 (16)
P2	0.0099 (3)	0.0142 (3)	0.0152 (3)	0.000	−0.0025 (2)	0.000
Cl1	0.0268 (3)	0.0243 (3)	0.0175 (2)	0.00142 (18)	0.00102 (17)	0.00455 (17)
Cl2	0.0205 (2)	0.0217 (3)	0.0236 (3)	0.00652 (17)	0.00390 (17)	−0.00308 (17)
Cl3	0.0138 (3)	0.0267 (4)	0.0223 (3)	0.000	0.0039 (2)	0.000
Cl4	0.0212 (3)	0.0320 (4)	0.0147 (3)	0.000	−0.0039 (2)	0.000

Geometric parameters (Å, º)

N1—P1	1.5771 (11)	P1—Cl1	1.9897 (6)
N1—P1^i	1.5771 (11)	P2—N2^i	1.5777 (15)
N2—P1	1.5763 (15)	P2—Cl4	1.9831 (9)
N2—P2	1.5777 (15)	P2—Cl3	1.9894 (9)
P1—Cl2	1.9806 (6)
P1—N1—P1^i	120.80 (13)	Cl2—P1—Cl1	102.07 (3)
P1—N2—P2	121.29 (9)	N2^i—P2—N2	118.46 (11)
N2—P1—N1	118.57 (9)	N2^i—P2—Cl4	109.01 (6)
N2—P1—Cl2	109.17 (6)	N2—P2—Cl4	109.01 (6)
N1—P1—Cl2	108.05 (8)	N2^i—P2—Cl3	108.79 (6)
N2—P1—Cl1	109.26 (6)	N2—P2—Cl3	108.79 (6)
N1—P1—Cl1	108.45 (9)	Cl4—P2—Cl3	101.44 (4)

Symmetry code: (i) x, −y+3/2, z.

(2) 1-tert-butylamino-1,3,3,5,5-pentachlorocyclotriphosphazatriene

Crystal data

C4H10Cl5N4P3	Dx = 1.701 Mg m^−3
Mr = 384.32	Melting point: 46°C K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.8045 (14) Å	Cell parameters from 6816 reflections
b = 10.7964 (16) Å	θ = 2.9–27.5°
c = 20.7719 (12) Å	µ = 1.27 mm^−1
β = 104.132 (7)°	T = 120 K
V = 3002.1 (6) Å^3	Cut plate, colourless
Z = 8	0.18 × 0.10 × 0.02 mm
F(000) = 1536

Data collection

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	6867 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	5549 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
Φ & ω scans	h = −17→17
Absorption correction: multi-scan SORTAV (Blessing, 1997)	k = −14→14
Tmin = 0.804, Tmax = 0.975	l = −26→26
40456 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	Difmap
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 1.5716P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
6867 reflections	Δρmax = 0.49 e Å^−3
370 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0021 (2)

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
C1	0.17129 (17)	1.3566 (2)	0.02067 (11)	0.0200 (5)
C2	0.06088 (19)	1.3307 (3)	−0.01014 (13)	0.0267 (5)
C3	0.1898 (2)	1.4958 (2)	0.02625 (14)	0.0281 (5)
C4	0.2045 (2)	1.2962 (2)	0.08855 (12)	0.0258 (5)
N1	0.19717 (16)	0.94770 (19)	−0.13223 (10)	0.0262 (5)
N2	0.19499 (15)	1.06715 (17)	−0.01843 (9)	0.0221 (4)
N3	0.29851 (14)	1.16389 (18)	−0.10223 (9)	0.0203 (4)
N4	0.23111 (15)	1.30907 (17)	−0.02485 (10)	0.0190 (4)
P1	0.27037 (4)	1.04750 (5)	−0.14864 (3)	0.01853 (13)
P2	0.16093 (4)	0.95511 (5)	−0.06614 (3)	0.01894 (13)
P3	0.26885 (4)	1.17078 (5)	−0.03256 (3)	0.01697 (13)
Cl1	0.21669 (5)	1.10893 (6)	−0.24080 (3)	0.03175 (15)
Cl2	0.39452 (5)	0.96200 (6)	−0.15753 (3)	0.02996 (15)
Cl3	0.19861 (5)	0.79780 (5)	−0.01638 (3)	0.03274 (15)
Cl4	0.01293 (4)	0.94518 (6)	−0.08895 (3)	0.03296 (15)
Cl5	0.39640 (5)	1.14713 (6)	0.03862 (3)	0.03337 (16)
H2A	0.0431 (18)	1.365 (2)	−0.0526 (13)	0.022 (6)*
H2B	0.023 (2)	1.364 (3)	0.0177 (14)	0.036 (8)*
H2C	0.046 (2)	1.242 (3)	−0.0130 (13)	0.036 (8)*
H3A	0.257 (2)	1.505 (3)	0.0443 (13)	0.027 (7)*
H3B	0.172 (2)	1.533 (2)	−0.0176 (14)	0.027 (7)*
H3C	0.151 (2)	1.530 (3)	0.0543 (14)	0.035 (8)*
H4A	0.165 (2)	1.333 (3)	0.1171 (15)	0.043 (8)*
H4B	0.276 (2)	1.310 (3)	0.1100 (13)	0.028 (7)*
H4C	0.191 (2)	1.208 (3)	0.0842 (14)	0.038 (8)*
H4N	0.2283 (18)	1.349 (2)	−0.0552 (12)	0.016 (6)*
C5	0.49140 (17)	1.1284 (2)	0.33533 (12)	0.0232 (5)
C6	0.4741 (2)	1.1961 (3)	0.26974 (15)	0.0363 (7)
C7	0.5492 (2)	1.2093 (3)	0.39132 (16)	0.0383 (7)
C8	0.5476 (2)	1.0082 (3)	0.3331 (2)	0.0404 (7)
N5	0.12289 (14)	0.9223 (2)	0.23559 (9)	0.0255 (4)
N6	0.21928 (13)	1.02251 (18)	0.35386 (9)	0.0199 (4)
N7	0.32415 (14)	0.9041 (2)	0.27736 (10)	0.0295 (5)
N8	0.39181 (15)	1.1045 (2)	0.34894 (11)	0.0264 (5)
P4	0.22630 (4)	0.88148 (6)	0.22243 (3)	0.01944 (13)
P5	0.11899 (4)	0.98830 (6)	0.30245 (3)	0.01815 (13)
P6	0.32529 (4)	0.98200 (5)	0.34220 (3)	0.01789 (13)
Cl6	0.21650 (5)	0.70290 (6)	0.19752 (3)	0.02974 (15)
Cl7	0.23985 (5)	0.95840 (6)	0.13795 (3)	0.03634 (17)
Cl8	0.03513 (5)	1.13916 (6)	0.28189 (3)	0.03327 (16)
Cl9	0.03580 (4)	0.88348 (6)	0.34766 (3)	0.02836 (14)
Cl10	0.38806 (5)	0.86825 (7)	0.41762 (3)	0.03675 (17)
H6A	0.435 (2)	1.148 (3)	0.2370 (15)	0.040 (9)*
H6B	0.537 (2)	1.217 (3)	0.2576 (14)	0.044 (8)*
H6C	0.438 (3)	1.276 (3)	0.2701 (17)	0.063 (11)*
H7A	0.615 (2)	1.231 (3)	0.3834 (15)	0.050 (9)*
H7B	0.515 (2)	1.288 (3)	0.3950 (15)	0.047 (9)*
H7C	0.562 (3)	1.160 (3)	0.4311 (18)	0.058 (10)*
H8A	0.610 (2)	1.026 (3)	0.3230 (14)	0.039 (8)*
H8B	0.515 (2)	0.955 (3)	0.2961 (15)	0.042 (9)*
H8C	0.558 (3)	0.963 (4)	0.376 (2)	0.071 (12)*
H8N	0.366 (2)	1.166 (3)	0.3608 (13)	0.026 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0267 (12)	0.0161 (12)	0.0190 (11)	0.0017 (9)	0.0092 (10)	−0.0025 (9)
C2	0.0273 (13)	0.0306 (15)	0.0251 (13)	0.0023 (11)	0.0121 (11)	0.0016 (11)
C3	0.0371 (16)	0.0185 (13)	0.0300 (14)	0.0025 (11)	0.0104 (13)	−0.0027 (10)
C4	0.0351 (15)	0.0252 (14)	0.0191 (11)	0.0033 (11)	0.0110 (11)	0.0014 (10)
N1	0.0335 (12)	0.0238 (11)	0.0245 (10)	−0.0090 (9)	0.0133 (9)	−0.0085 (8)
N2	0.0315 (11)	0.0152 (10)	0.0231 (10)	−0.0039 (8)	0.0135 (9)	−0.0009 (8)
N3	0.0232 (10)	0.0181 (10)	0.0228 (10)	−0.0026 (8)	0.0117 (8)	−0.0018 (8)
N4	0.0272 (11)	0.0132 (10)	0.0189 (10)	0.0014 (8)	0.0097 (9)	0.0029 (8)
P1	0.0213 (3)	0.0177 (3)	0.0178 (3)	0.0012 (2)	0.0071 (2)	−0.0008 (2)
P2	0.0222 (3)	0.0148 (3)	0.0204 (3)	−0.0024 (2)	0.0064 (2)	0.0002 (2)
P3	0.0197 (3)	0.0141 (3)	0.0179 (3)	−0.0009 (2)	0.0061 (2)	−0.0003 (2)
Cl1	0.0399 (4)	0.0327 (4)	0.0203 (3)	0.0059 (3)	0.0029 (3)	0.0040 (2)
Cl2	0.0280 (3)	0.0291 (3)	0.0342 (3)	0.0092 (3)	0.0104 (3)	−0.0037 (2)
Cl3	0.0450 (4)	0.0155 (3)	0.0345 (3)	0.0012 (3)	0.0035 (3)	0.0038 (2)
Cl4	0.0221 (3)	0.0410 (4)	0.0352 (3)	−0.0039 (3)	0.0059 (3)	0.0008 (3)
Cl5	0.0248 (3)	0.0396 (4)	0.0313 (3)	0.0065 (3)	−0.0016 (3)	0.0024 (3)
C5	0.0164 (11)	0.0228 (13)	0.0327 (13)	−0.0002 (9)	0.0108 (10)	−0.0009 (10)
C6	0.0265 (14)	0.0481 (19)	0.0379 (16)	0.0022 (14)	0.0150 (13)	0.0100 (14)
C7	0.0253 (14)	0.0468 (19)	0.0432 (17)	−0.0061 (13)	0.0092 (13)	−0.0141 (15)
C8	0.0273 (15)	0.0286 (16)	0.073 (2)	0.0020 (12)	0.0282 (16)	−0.0028 (16)
N5	0.0199 (10)	0.0361 (12)	0.0189 (9)	0.0058 (9)	0.0019 (8)	−0.0050 (9)
N6	0.0175 (9)	0.0237 (11)	0.0199 (9)	−0.0012 (8)	0.0073 (8)	−0.0047 (8)
N7	0.0164 (10)	0.0430 (13)	0.0296 (11)	0.0030 (9)	0.0064 (9)	−0.0163 (10)
N8	0.0198 (10)	0.0185 (11)	0.0462 (13)	−0.0002 (8)	0.0184 (10)	−0.0029 (9)
P4	0.0195 (3)	0.0222 (3)	0.0176 (3)	0.0022 (2)	0.0064 (2)	−0.0023 (2)
P5	0.0166 (3)	0.0213 (3)	0.0179 (3)	0.0020 (2)	0.0068 (2)	−0.0001 (2)
P6	0.0163 (3)	0.0197 (3)	0.0184 (3)	0.0001 (2)	0.0058 (2)	−0.0017 (2)
Cl6	0.0296 (3)	0.0221 (3)	0.0383 (3)	−0.0009 (2)	0.0096 (3)	−0.0046 (2)
Cl7	0.0490 (4)	0.0354 (4)	0.0314 (3)	0.0103 (3)	0.0228 (3)	0.0111 (3)
Cl8	0.0320 (3)	0.0288 (3)	0.0396 (3)	0.0128 (3)	0.0099 (3)	0.0048 (3)
Cl9	0.0254 (3)	0.0350 (4)	0.0254 (3)	−0.0095 (3)	0.0076 (2)	0.0017 (2)
Cl10	0.0366 (4)	0.0386 (4)	0.0366 (3)	0.0096 (3)	0.0119 (3)	0.0178 (3)

Geometric parameters (Å, º)

C1—N4	1.490 (3)	C5—N8	1.492 (3)
C1—C4	1.519 (3)	C5—C6	1.513 (4)
C1—C3	1.524 (3)	C5—C7	1.516 (4)
C1—C2	1.528 (3)	C5—C8	1.518 (4)
C2—H2A	0.93 (3)	C6—H6A	0.92 (3)
C2—H2B	0.94 (3)	C6—H6B	0.99 (3)
C2—H2C	0.98 (3)	C6—H6C	1.00 (4)
C3—H3A	0.91 (3)	C7—H7A	0.99 (3)
C3—H3B	0.97 (3)	C7—H7B	0.98 (3)
C3—H3C	0.95 (3)	C7—H7C	0.96 (4)
C4—H4A	0.99 (3)	C8—H8A	0.96 (3)
C4—H4B	0.99 (3)	C8—H8B	0.98 (3)
C4—H4C	0.97 (3)	C8—H8C	1.00 (4)
N1—P1	1.570 (2)	N5—P5	1.5733 (19)
N1—P2	1.5737 (19)	N5—P4	1.581 (2)
N2—P2	1.562 (2)	N6—P5	1.5722 (19)
N2—P3	1.5886 (19)	N6—P6	1.6014 (18)
N3—P1	1.5736 (19)	N7—P4	1.560 (2)
N3—P3	1.5991 (18)	N7—P6	1.585 (2)
N4—P3	1.6021 (19)	N8—P6	1.597 (2)
N4—H4N	0.76 (3)	N8—H8N	0.82 (3)
P1—Cl1	1.9902 (8)	P4—Cl7	1.9909 (8)
P1—Cl2	1.9946 (8)	P4—Cl6	1.9922 (9)
P2—Cl4	1.9844 (9)	P5—Cl8	1.9834 (9)
P2—Cl3	1.9901 (9)	P5—Cl9	2.0020 (8)
P3—Cl5	2.0200 (9)	P6—Cl10	2.0125 (9)
N4—C1—C4	110.64 (19)	N8—C5—C6	107.7 (2)
N4—C1—C3	106.22 (19)	N8—C5—C7	106.9 (2)
C4—C1—C3	110.2 (2)	C6—C5—C7	110.5 (2)
N4—C1—C2	108.78 (18)	N8—C5—C8	111.1 (2)
C4—C1—C2	110.8 (2)	C6—C5—C8	110.8 (2)
C3—C1—C2	110.1 (2)	C7—C5—C8	109.8 (2)
C1—C2—H2A	109.3 (15)	C5—C6—H6A	109.2 (19)
C1—C2—H2B	108.9 (17)	C5—C6—H6B	112.5 (18)
H2A—C2—H2B	112 (2)	H6A—C6—H6B	110 (2)
C1—C2—H2C	112.4 (17)	C5—C6—H6C	112 (2)
H2A—C2—H2C	109 (2)	H6A—C6—H6C	107 (3)
H2B—C2—H2C	105 (2)	H6B—C6—H6C	106 (3)
C1—C3—H3A	105.9 (17)	C5—C7—H7A	110.1 (19)
C1—C3—H3B	109.8 (16)	C5—C7—H7B	112.7 (19)
H3A—C3—H3B	110 (2)	H7A—C7—H7B	106 (3)
C1—C3—H3C	108.4 (17)	C5—C7—H7C	107 (2)
H3A—C3—H3C	111 (2)	H7A—C7—H7C	107 (3)
H3B—C3—H3C	111 (2)	H7B—C7—H7C	114 (3)
C1—C4—H4A	107.4 (17)	C5—C8—H8A	109.3 (18)
C1—C4—H4B	113.3 (15)	C5—C8—H8B	112.6 (18)
H4A—C4—H4B	108 (2)	H8A—C8—H8B	102 (2)
C1—C4—H4C	109.1 (17)	C5—C8—H8C	111 (2)
H4A—C4—H4C	109 (2)	H8A—C8—H8C	110 (3)
H4B—C4—H4C	110 (2)	H8B—C8—H8C	111 (3)
P1—N1—P2	120.85 (13)	P5—N5—P4	120.40 (12)
P2—N2—P3	122.38 (12)	P5—N6—P6	121.25 (11)
P1—N3—P3	120.80 (12)	P4—N7—P6	122.14 (12)
C1—N4—P3	128.93 (16)	C5—N8—P6	131.54 (17)
C1—N4—H4N	113.9 (19)	C5—N8—H8N	114.4 (19)
P3—N4—H4N	113.8 (19)	P6—N8—H8N	114.0 (19)
N1—P1—N3	119.38 (10)	N7—P4—N5	119.15 (10)
N1—P1—Cl1	109.22 (8)	N7—P4—Cl7	109.17 (9)
N3—P1—Cl1	107.54 (8)	N5—P4—Cl7	108.62 (8)
N1—P1—Cl2	108.39 (9)	N7—P4—Cl6	109.47 (9)
N3—P1—Cl2	109.70 (8)	N5—P4—Cl6	107.94 (9)
Cl1—P1—Cl2	101.05 (4)	Cl7—P4—Cl6	100.94 (4)
N2—P2—N1	118.84 (10)	N6—P5—N5	119.46 (10)
N2—P2—Cl4	109.04 (8)	N6—P5—Cl8	108.91 (8)
N1—P2—Cl4	108.49 (9)	N5—P5—Cl8	109.00 (8)
N2—P2—Cl3	109.35 (8)	N6—P5—Cl9	108.97 (8)
N1—P2—Cl3	108.14 (9)	N5—P5—Cl9	107.78 (9)
Cl4—P2—Cl3	101.60 (4)	Cl8—P5—Cl9	101.17 (4)
N2—P3—N3	116.88 (10)	N7—P6—N8	113.58 (12)
N2—P3—N4	113.50 (10)	N7—P6—N6	116.98 (10)
N3—P3—N4	107.17 (10)	N8—P6—N6	106.72 (11)
N2—P3—Cl5	105.06 (8)	N7—P6—Cl10	104.53 (9)
N3—P3—Cl5	106.65 (8)	N8—P6—Cl10	107.95 (9)
N4—P3—Cl5	106.93 (8)	N6—P6—Cl10	106.54 (7)

(3) 1,1-bis(tert-butylamino)-3,3,5,5-tetrachlorocyclotriphosphazene

Crystal data

C8H20Cl4N5P3	Dx = 1.441 Mg m^−3
Mr = 421.00	Melting point: 121°C K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
a = 20.3441 (7) Å	Cell parameters from 29220 reflections
b = 11.9481 (4) Å	θ = 2.9–27.5°
c = 15.9661 (7) Å	µ = 0.85 mm^−1
V = 3880.9 (3) Å^3	T = 120 K
Z = 8	Plate, colourless
F(000) = 1728	0.16 × 0.14 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer	5744 reflections with I > 2σ(I)
Radiation source: Nonius FR591 rotating anode	Rint = 0.078
Graphite monochromator	θmax = 27.5°, θmin = 2.9°
Detector resolution: 9.091 pixels mm^-1	h = −26→24
ϕ & ω scans	k = −13→15
29635 measured reflections	l = −20→20
8587 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.053	w = 1/[σ^2(Fo^2) + (0.0134P)^2 + 2.2238P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.107	(Δ/σ)max = 0.011
S = 1.02	Δρmax = 0.44 e Å^−3
8587 reflections	Δρmin = −0.43 e Å^−3
414 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
7 restraints	Extinction coefficient: 0.0041 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.08 (8)

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	Occ. (<1)
C2	−0.4512 (8)	0.743 (2)	0.4483 (12)	0.112 (8)	0.67 (3)
H2A	−0.4808	0.6937	0.4173	0.169*	0.67 (3)
H2B	−0.4319	0.7981	0.4097	0.169*	0.67 (3)
H2C	−0.4760	0.7826	0.4920	0.169*	0.67 (3)
C3	−0.369 (3)	0.590 (2)	0.5647 (14)	0.148 (18)	0.47 (4)
H3A	−0.3895	0.6142	0.6175	0.222*	0.47 (4)
H3B	−0.3213	0.5950	0.5696	0.222*	0.47 (4)
H3C	−0.3820	0.5132	0.5523	0.222*	0.47 (4)
C4	−0.358 (4)	0.783 (7)	0.506 (6)	0.18 (3)	0.34 (9)
H4A	−0.3794	0.8415	0.4718	0.263*	0.34 (9)
H4B	−0.3120	0.7770	0.4898	0.263*	0.34 (9)
H4C	−0.3615	0.8037	0.5652	0.263*	0.34 (9)
C2'	−0.4626 (11)	0.652 (4)	0.497 (3)	0.11 (2)	0.33 (3)
H2'1	−0.4822	0.6544	0.4414	0.163*	0.33 (3)
H2'2	−0.4821	0.7112	0.5321	0.163*	0.33 (3)
H2'3	−0.4709	0.5792	0.5231	0.163*	0.33 (3)
C3'	−0.430 (2)	0.5882 (18)	0.5435 (14)	0.115 (13)	0.53 (4)
H3'1	−0.4644	0.6273	0.5751	0.172*	0.53 (4)
H3'2	−0.3998	0.5517	0.5826	0.172*	0.53 (4)
H3'3	−0.4504	0.5316	0.5073	0.172*	0.53 (4)
C4'	−0.3537 (11)	0.755 (3)	0.530 (2)	0.109 (9)	0.66 (9)
H4'1	−0.3807	0.7975	0.5700	0.163*	0.66 (9)
H4'2	−0.3362	0.8057	0.4876	0.163*	0.66 (9)
H4'3	−0.3172	0.7195	0.5604	0.163*	0.66 (9)
C9	0.0429 (2)	0.3132 (4)	0.5383 (3)	0.0542 (12)
C10	0.0612 (3)	0.2948 (6)	0.6290 (3)	0.0810 (18)
H10A	0.0586	0.2148	0.6420	0.122*
H10B	0.0307	0.3362	0.6650	0.122*
H10C	0.1061	0.3215	0.6387	0.122*
C11	−0.0255 (3)	0.2668 (6)	0.5210 (4)	0.092 (2)
H11A	−0.0368	0.2792	0.4621	0.139*
H11B	−0.0576	0.3051	0.5567	0.139*
H11C	−0.0261	0.1864	0.5331	0.139*
C12	0.0465 (3)	0.4379 (5)	0.5192 (4)	0.0747 (16)
H12A	0.0338	0.4510	0.4608	0.112*
H12B	0.0915	0.4645	0.5281	0.112*
H12C	0.0165	0.4786	0.5564	0.112*
C13	0.2241 (2)	0.2599 (4)	0.3576 (4)	0.0603 (14)
C14	0.2131 (3)	0.3736 (5)	0.3901 (5)	0.092 (2)
H14A	0.1745	0.4063	0.3628	0.138*
H14B	0.2518	0.4199	0.3784	0.138*
H14C	0.2057	0.3702	0.4507	0.138*
C15	0.2367 (5)	0.2734 (7)	0.2645 (6)	0.151 (4)
H15A	0.2451	0.1999	0.2395	0.226*
H15B	0.2751	0.3218	0.2561	0.226*
H15C	0.1982	0.3074	0.2379	0.226*
C16	0.2799 (3)	0.2025 (6)	0.3986 (10)	0.200 (7)
H16A	0.2854	0.1278	0.3741	0.301*
H16B	0.2712	0.1955	0.4587	0.301*
H16C	0.3202	0.2461	0.3900	0.301*
H1	−0.388 (2)	0.573 (4)	0.397 (3)	0.046 (14)*
H11	−0.249 (2)	0.586 (4)	0.460 (3)	0.041 (15)*
H21	0.1181 (16)	0.229 (3)	0.509 (2)	0.008 (9)*
H31	0.173 (2)	0.129 (4)	0.350 (3)	0.049 (16)*
C1	−0.3933 (3)	0.6702 (5)	0.4910 (4)	0.0712 (16)
C5	−0.1693 (2)	0.6632 (4)	0.4244 (3)	0.0543 (12)
C6	−0.1428 (2)	0.6708 (6)	0.3369 (4)	0.0800 (18)
H6A	−0.1463	0.5976	0.3097	0.120*
H6B	−0.0966	0.6938	0.3388	0.120*
H6C	−0.1682	0.7261	0.3052	0.120*
C7	−0.1292 (3)	0.5754 (5)	0.4739 (4)	0.0761 (17)
H7A	−0.1463	0.5701	0.5312	0.114*
H7B	−0.0829	0.5981	0.4757	0.114*
H7C	−0.1329	0.5024	0.4464	0.114*
C8	−0.1650 (3)	0.7762 (5)	0.4685 (4)	0.0776 (18)
H8A	−0.1827	0.7695	0.5253	0.116*
H8B	−0.1905	0.8317	0.4371	0.116*
H8C	−0.1190	0.8001	0.4713	0.116*
N1	−0.30158 (17)	0.5506 (3)	0.2866 (2)	0.0435 (9)
N2	−0.3072 (3)	0.7070 (4)	0.1649 (3)	0.1009 (19)
N3	−0.29394 (19)	0.7680 (3)	0.3284 (3)	0.0515 (10)
N4	−0.36383 (19)	0.6142 (4)	0.4171 (3)	0.0534 (11)
N5	−0.23848 (19)	0.6238 (4)	0.4261 (3)	0.0454 (10)
N6	−0.03308 (19)	0.1839 (3)	0.2602 (3)	0.0641 (12)
N7	0.05133 (15)	0.0956 (3)	0.3745 (2)	0.0405 (8)
N8	0.05692 (17)	0.3148 (3)	0.3371 (2)	0.0438 (9)
N9	0.0917 (2)	0.2535 (3)	0.4862 (2)	0.0439 (9)
N10	0.16547 (17)	0.1856 (4)	0.3660 (3)	0.0478 (10)
P1	−0.29935 (5)	0.64228 (9)	0.36204 (7)	0.0412 (3)
P2	−0.30042 (7)	0.58105 (11)	0.19244 (8)	0.0559 (3)
P3	−0.30301 (9)	0.80076 (11)	0.23443 (10)	0.0724 (4)
P4	0.09009 (5)	0.21355 (8)	0.38894 (7)	0.0366 (2)
P5	−0.01174 (6)	0.08397 (10)	0.31956 (8)	0.0474 (3)
P6	0.00700 (6)	0.29605 (10)	0.26488 (8)	0.0466 (3)
Cl1	−0.36884 (8)	0.49371 (16)	0.13073 (10)	0.0968 (6)
Cl2	−0.21973 (7)	0.51581 (14)	0.13800 (10)	0.0869 (5)
Cl3	−0.38089 (11)	0.90060 (15)	0.22077 (15)	0.1250 (8)
Cl4	−0.23133 (12)	0.90792 (15)	0.20127 (14)	0.1250 (8)
Cl5	−0.09017 (6)	0.04494 (12)	0.39055 (11)	0.0761 (4)
Cl6	−0.00575 (7)	−0.05702 (13)	0.25320 (12)	0.0884 (5)
Cl7	−0.05738 (7)	0.42134 (14)	0.26403 (12)	0.0889 (5)
Cl8	0.05032 (8)	0.32122 (14)	0.15388 (9)	0.0779 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.084 (9)	0.133 (16)	0.120 (12)	0.047 (9)	0.015 (8)	−0.038 (11)
C3	0.24 (5)	0.132 (18)	0.068 (13)	0.02 (2)	0.08 (2)	0.000 (11)
C4	0.30 (7)	0.10 (3)	0.12 (4)	−0.02 (3)	0.09 (4)	−0.08 (3)
C2'	0.058 (14)	0.15 (5)	0.12 (3)	−0.016 (15)	0.037 (14)	−0.08 (3)
C3'	0.17 (3)	0.092 (13)	0.083 (14)	−0.036 (15)	0.071 (17)	−0.026 (10)
C4'	0.102 (13)	0.125 (19)	0.099 (16)	−0.040 (9)	0.034 (8)	−0.083 (14)
C9	0.059 (3)	0.063 (3)	0.042 (3)	−0.002 (2)	0.007 (2)	−0.007 (2)
C10	0.101 (4)	0.097 (5)	0.046 (3)	−0.012 (3)	0.012 (3)	−0.003 (3)
C11	0.057 (4)	0.140 (6)	0.081 (4)	−0.012 (3)	0.022 (3)	−0.047 (4)
C12	0.100 (4)	0.064 (4)	0.060 (4)	0.017 (3)	−0.005 (3)	−0.015 (3)
C13	0.043 (3)	0.046 (3)	0.092 (4)	−0.012 (2)	0.010 (3)	−0.006 (3)
C14	0.073 (4)	0.061 (4)	0.143 (6)	−0.034 (3)	0.028 (4)	−0.026 (4)
C15	0.184 (8)	0.120 (7)	0.148 (8)	−0.090 (6)	0.103 (7)	−0.044 (6)
C16	0.067 (5)	0.087 (5)	0.45 (2)	−0.025 (4)	−0.095 (8)	0.076 (9)
C1	0.062 (3)	0.072 (4)	0.080 (4)	−0.003 (3)	0.020 (3)	−0.037 (3)
C5	0.044 (3)	0.059 (3)	0.060 (3)	−0.004 (2)	−0.007 (2)	−0.011 (3)
C6	0.045 (3)	0.119 (5)	0.076 (4)	−0.002 (3)	0.007 (3)	−0.002 (4)
C7	0.061 (3)	0.075 (4)	0.092 (4)	0.002 (3)	−0.035 (3)	−0.003 (3)
C8	0.064 (4)	0.065 (4)	0.104 (5)	−0.012 (3)	−0.001 (3)	−0.025 (4)
N1	0.052 (2)	0.037 (2)	0.041 (2)	−0.0007 (16)	0.0007 (16)	−0.0093 (16)
N2	0.206 (6)	0.045 (3)	0.052 (3)	0.008 (3)	−0.016 (3)	−0.001 (2)
N3	0.065 (2)	0.0328 (19)	0.056 (3)	0.0015 (17)	−0.0126 (19)	−0.0045 (19)
N4	0.041 (2)	0.060 (3)	0.060 (3)	−0.0062 (19)	0.0079 (18)	−0.026 (2)
N5	0.046 (2)	0.045 (2)	0.045 (3)	0.0000 (18)	−0.0044 (18)	0.002 (2)
N6	0.067 (2)	0.058 (3)	0.068 (3)	−0.023 (2)	−0.035 (2)	0.019 (2)
N7	0.0369 (18)	0.0331 (18)	0.051 (2)	−0.0075 (13)	−0.0025 (16)	0.0003 (17)
N8	0.056 (2)	0.039 (2)	0.037 (2)	−0.0031 (16)	−0.0107 (17)	0.0014 (16)
N9	0.043 (2)	0.049 (2)	0.040 (2)	0.0046 (18)	−0.0097 (18)	0.0033 (18)
N10	0.039 (2)	0.038 (2)	0.066 (3)	−0.0014 (16)	0.0074 (18)	−0.009 (2)
P1	0.0432 (6)	0.0370 (6)	0.0435 (7)	0.0015 (5)	−0.0029 (5)	−0.0090 (5)
P2	0.0798 (9)	0.0458 (8)	0.0421 (8)	0.0002 (6)	−0.0045 (7)	−0.0068 (6)
P3	0.1206 (13)	0.0385 (8)	0.0581 (10)	0.0094 (7)	−0.0194 (9)	0.0017 (7)
P4	0.0390 (6)	0.0331 (5)	0.0376 (6)	−0.0020 (4)	−0.0004 (5)	−0.0003 (5)
P5	0.0443 (6)	0.0423 (7)	0.0556 (8)	−0.0092 (5)	−0.0050 (6)	−0.0005 (6)
P6	0.0510 (7)	0.0469 (7)	0.0418 (7)	−0.0012 (5)	−0.0053 (6)	0.0052 (6)
Cl1	0.0960 (11)	0.1181 (14)	0.0764 (11)	−0.0027 (9)	−0.0231 (9)	−0.0433 (10)
Cl2	0.0928 (11)	0.1003 (12)	0.0676 (10)	−0.0094 (9)	0.0356 (8)	−0.0106 (9)
Cl3	0.1551 (18)	0.0762 (11)	0.1436 (18)	0.0425 (11)	−0.0792 (15)	−0.0088 (12)
Cl4	0.184 (2)	0.0677 (12)	0.1231 (17)	−0.0158 (12)	0.0341 (15)	0.0258 (11)
Cl5	0.0451 (7)	0.0758 (9)	0.1073 (12)	−0.0139 (6)	0.0053 (7)	0.0157 (9)
Cl6	0.0932 (11)	0.0679 (10)	0.1041 (13)	−0.0155 (7)	−0.0111 (10)	−0.0372 (9)
Cl7	0.0780 (10)	0.0827 (11)	0.1061 (13)	0.0319 (8)	−0.0103 (9)	0.0138 (10)
Cl8	0.0958 (11)	0.0974 (12)	0.0405 (7)	−0.0169 (8)	0.0030 (7)	0.0059 (8)

Geometric parameters (Å, º)

C2—C1	1.617 (15)	C15—H15C	0.9800
C2—H2A	0.9800	C16—H16A	0.9800
C2—H2B	0.9800	C16—H16B	0.9800
C2—H2C	0.9800	C16—H16C	0.9800
C3—C1	1.59 (3)	C1—N4	1.482 (6)
C3—H3A	0.9800	C5—N5	1.485 (6)
C3—H3B	0.9800	C5—C6	1.499 (7)
C3—H3C	0.9800	C5—C8	1.525 (7)
C4—C1	1.55 (6)	C5—C7	1.547 (7)
C4—H4A	0.9800	C6—H6A	0.9800
C4—H4B	0.9800	C6—H6B	0.9800
C4—H4C	0.9800	C6—H6C	0.9800
C2'—C1	1.43 (2)	C7—H7A	0.9800
C2'—H2'1	0.9800	C7—H7B	0.9800
C2'—H2'2	0.9800	C7—H7C	0.9800
C2'—H2'3	0.9800	C8—H8A	0.9800
C3'—C1	1.492 (18)	C8—H8B	0.9800
C3'—H3'1	0.9800	C8—H8C	0.9800
C3'—H3'2	0.9800	N1—P2	1.547 (4)
C3'—H3'3	0.9800	N1—P1	1.628 (4)
C4'—C1	1.44 (2)	N2—P2	1.574 (5)
C4'—H4'1	0.9800	N2—P3	1.579 (5)
C4'—H4'2	0.9800	N3—P3	1.561 (4)
C4'—H4'3	0.9800	N3—P1	1.599 (4)
C9—N9	1.480 (6)	N4—P1	1.615 (4)
C9—C10	1.510 (7)	N4—H1	0.77 (4)
C9—C12	1.522 (7)	N5—P1	1.621 (4)
C9—C11	1.523 (7)	N5—H11	0.73 (4)
C10—H10A	0.9800	N6—P6	1.571 (4)
C10—H10B	0.9800	N6—P5	1.585 (4)
C10—H10C	0.9800	N7—P5	1.560 (3)
C11—H11A	0.9800	N7—P4	1.631 (3)
C11—H11B	0.9800	N8—P6	1.553 (4)
C11—H11C	0.9800	N8—P4	1.614 (3)
C12—H12A	0.9800	N9—P4	1.624 (4)
C12—H12B	0.9800	N9—H21	0.71 (3)
C12—H12C	0.9800	N10—P4	1.611 (4)
C13—C14	1.471 (7)	N10—H31	0.73 (5)
C13—C16	1.480 (9)	P2—Cl1	1.999 (2)
C13—N10	1.492 (5)	P2—Cl2	2.014 (2)
C13—C15	1.517 (10)	P3—Cl3	1.995 (2)
C14—H14A	0.9800	P3—Cl4	2.012 (3)
C14—H14B	0.9800	P5—Cl6	1.9939 (19)
C14—H14C	0.9800	P5—Cl5	2.0119 (18)
C15—H15A	0.9800	P6—Cl7	1.9892 (18)
C15—H15B	0.9800	P6—Cl8	2.0020 (19)
C1—C2—H2A	109.5	N4—C1—C3	101.2 (9)
C1—C2—H2B	109.5	C3'—C1—C3	49.1 (13)
C1—C2—H2C	109.5	C4—C1—C3	106 (5)
C1—C3—H3A	109.5	C2'—C1—C2	52.6 (18)
C1—C3—H3B	109.5	C4'—C1—C2	102.2 (19)
C1—C3—H3C	109.5	N4—C1—C2	101.7 (7)
C1—C4—H4A	109.4	C3'—C1—C2	103 (2)
C1—C4—H4B	109.5	C4—C1—C2	86 (4)
C1—C4—H4C	109.5	C3—C1—C2	149 (2)
C1—C2'—H2'1	109.5	N5—C5—C6	112.2 (4)
C1—C2'—H2'2	109.5	N5—C5—C8	109.1 (4)
H2'1—C2'—H2'2	109.5	C6—C5—C8	110.8 (5)
C1—C2'—H2'3	109.5	N5—C5—C7	106.0 (4)
H2'1—C2'—H2'3	109.5	C6—C5—C7	109.1 (5)
H2'2—C2'—H2'3	109.5	C8—C5—C7	109.5 (4)
C1—C3'—H3'1	109.5	C5—C6—H6A	109.5
C1—C3'—H3'2	109.5	C5—C6—H6B	109.5
H3'1—C3'—H3'2	109.5	H6A—C6—H6B	109.5
C1—C3'—H3'3	109.5	C5—C6—H6C	109.5
H3'1—C3'—H3'3	109.5	H6A—C6—H6C	109.5
H3'2—C3'—H3'3	109.5	H6B—C6—H6C	109.5
C1—C4'—H4'1	109.5	C5—C7—H7A	109.5
C1—C4'—H4'2	109.5	C5—C7—H7B	109.5
H4'1—C4'—H4'2	109.5	H7A—C7—H7B	109.5
C1—C4'—H4'3	109.5	C5—C7—H7C	109.5
H4'1—C4'—H4'3	109.5	H7A—C7—H7C	109.5
H4'2—C4'—H4'3	109.5	H7B—C7—H7C	109.5
N9—C9—C10	107.7 (4)	C5—C8—H8A	109.5
N9—C9—C12	109.1 (4)	C5—C8—H8B	109.5
C10—C9—C12	108.8 (5)	H8A—C8—H8B	109.5
N9—C9—C11	109.6 (4)	C5—C8—H8C	109.5
C10—C9—C11	110.2 (5)	H8A—C8—H8C	109.5
C12—C9—C11	111.3 (5)	H8B—C8—H8C	109.5
C9—C10—H10A	109.5	P2—N1—P1	124.1 (2)
C9—C10—H10B	109.5	P2—N2—P3	118.5 (3)
H10A—C10—H10B	109.5	P3—N3—P1	123.4 (2)
C9—C10—H10C	109.5	C1—N4—P1	131.9 (4)
H10A—C10—H10C	109.5	C1—N4—H1	112 (4)
H10B—C10—H10C	109.5	P1—N4—H1	115 (4)
C9—C11—H11A	109.5	C5—N5—P1	132.0 (4)
C9—C11—H11B	109.5	C5—N5—H11	119 (4)
H11A—C11—H11B	109.5	P1—N5—H11	109 (4)
C9—C11—H11C	109.5	P6—N6—P5	118.2 (2)
H11A—C11—H11C	109.5	P5—N7—P4	123.7 (2)
H11B—C11—H11C	109.5	P6—N8—P4	123.1 (2)
C9—C12—H12A	109.5	C9—N9—P4	131.8 (3)
C9—C12—H12B	109.5	C9—N9—H21	115 (3)
H12A—C12—H12B	109.5	P4—N9—H21	112 (3)
C9—C12—H12C	109.5	C13—N10—P4	131.1 (3)
H12A—C12—H12C	109.5	C13—N10—H31	110 (4)
H12B—C12—H12C	109.5	P4—N10—H31	118 (4)
C14—C13—C16	112.9 (6)	N3—P1—N4	115.7 (2)
C14—C13—N10	113.4 (4)	N3—P1—N5	106.7 (2)
C16—C13—N10	107.4 (5)	N4—P1—N5	104.4 (2)
C14—C13—C15	105.8 (6)	N3—P1—N1	112.7 (2)
C16—C13—C15	110.6 (8)	N4—P1—N1	103.9 (2)
N10—C13—C15	106.7 (5)	N5—P1—N1	113.3 (2)
C13—C14—H14A	109.5	N1—P2—N2	119.7 (2)
C13—C14—H14B	109.5	N1—P2—Cl1	110.23 (16)
H14A—C14—H14B	109.5	N2—P2—Cl1	107.5 (2)
C13—C14—H14C	109.5	N1—P2—Cl2	109.93 (16)
H14A—C14—H14C	109.5	N2—P2—Cl2	108.7 (3)
H14B—C14—H14C	109.5	Cl1—P2—Cl2	98.78 (9)
C13—C15—H15A	109.5	N3—P3—N2	120.3 (2)
C13—C15—H15B	109.5	N3—P3—Cl3	110.41 (18)
H15A—C15—H15B	109.5	N2—P3—Cl3	107.7 (2)
C13—C15—H15C	109.5	N3—P3—Cl4	109.07 (18)
H15A—C15—H15C	109.5	N2—P3—Cl4	107.8 (3)
H15B—C15—H15C	109.5	Cl3—P3—Cl4	99.57 (11)
C13—C16—H16A	109.5	N10—P4—N8	115.9 (2)
C13—C16—H16B	109.5	N10—P4—N9	105.0 (2)
H16A—C16—H16B	109.5	N8—P4—N9	106.1 (2)
C13—C16—H16C	109.5	N10—P4—N7	104.43 (19)
H16A—C16—H16C	109.5	N8—P4—N7	111.89 (18)
H16B—C16—H16C	109.5	N9—P4—N7	113.5 (2)
C2'—C1—C4'	128.8 (15)	N7—P5—N6	119.61 (18)
C2'—C1—N4	112.8 (10)	N7—P5—Cl6	108.90 (14)
C4'—C1—N4	116.0 (11)	N6—P5—Cl6	109.58 (19)
C2'—C1—C3'	51 (3)	N7—P5—Cl5	110.87 (16)
C4'—C1—C3'	120 (2)	N6—P5—Cl5	107.12 (18)
N4—C1—C3'	110.7 (8)	Cl6—P5—Cl5	98.74 (8)
C2'—C1—C4	125 (3)	N8—P6—N6	119.9 (2)
C4'—C1—C4	20 (5)	N8—P6—Cl7	109.09 (15)
N4—C1—C4	109 (3)	N6—P6—Cl7	107.47 (18)
C3'—C1—C4	136 (3)	N8—P6—Cl8	110.35 (15)
C2'—C1—C3	99 (3)	N6—P6—Cl8	108.3 (2)
C4'—C1—C3	86 (3)	Cl7—P6—Cl8	99.84 (9)
C2'—C1—N4—P1	153 (3)	P3—N2—P2—Cl2	−117.2 (4)
C4'—C1—N4—P1	−11 (2)	P1—N3—P3—N2	−9.6 (5)
C3'—C1—N4—P1	−152 (2)	P1—N3—P3—Cl3	116.7 (3)
C4—C1—N4—P1	9 (4)	P1—N3—P3—Cl4	−134.8 (2)
C3—C1—N4—P1	−102 (2)	P2—N2—P3—N3	−1.4 (6)
C2—C1—N4—P1	99.0 (11)	P2—N2—P3—Cl3	−129.0 (4)
C6—C5—N5—P1	−33.5 (7)	P2—N2—P3—Cl4	124.4 (4)
C8—C5—N5—P1	89.6 (5)	C13—N10—P4—N8	49.0 (5)
C7—C5—N5—P1	−152.5 (4)	C13—N10—P4—N9	−67.8 (5)
C10—C9—N9—P4	161.9 (4)	C13—N10—P4—N7	172.5 (5)
C12—C9—N9—P4	−80.2 (5)	P6—N8—P4—N10	104.2 (3)
C11—C9—N9—P4	42.0 (7)	P6—N8—P4—N9	−139.7 (3)
C14—C13—N10—P4	12.2 (8)	P6—N8—P4—N7	−15.3 (3)
C16—C13—N10—P4	137.5 (7)	C9—N9—P4—N10	164.5 (4)
C15—C13—N10—P4	−103.9 (6)	C9—N9—P4—N8	41.2 (5)
P3—N3—P1—N4	−108.7 (3)	C9—N9—P4—N7	−82.1 (5)
P3—N3—P1—N5	135.7 (3)	P5—N7—P4—N10	−128.2 (3)
P3—N3—P1—N1	10.7 (4)	P5—N7—P4—N8	−2.1 (3)
C1—N4—P1—N3	−51.3 (6)	P5—N7—P4—N9	118.0 (3)
C1—N4—P1—N5	65.6 (6)	P4—N7—P5—N6	12.2 (4)
C1—N4—P1—N1	−175.4 (5)	P4—N7—P5—Cl6	139.2 (2)
C5—N5—P1—N3	−37.8 (5)	P4—N7—P5—Cl5	−113.2 (2)
C5—N5—P1—N4	−160.8 (4)	P6—N6—P5—N7	−5.3 (5)
C5—N5—P1—N1	86.8 (5)	P6—N6—P5—Cl6	−132.1 (3)
P2—N1—P1—N3	−1.5 (3)	P6—N6—P5—Cl5	121.8 (3)
P2—N1—P1—N4	124.5 (3)	P4—N8—P6—N6	22.7 (4)
P2—N1—P1—N5	−122.8 (3)	P4—N8—P6—Cl7	147.1 (2)
P1—N1—P2—N2	−8.8 (4)	P4—N8—P6—Cl8	−104.2 (2)
P1—N1—P2—Cl1	−134.1 (2)	P5—N6—P6—N8	−11.3 (5)
P1—N1—P2—Cl2	118.0 (2)	P5—N6—P6—Cl7	−136.5 (3)
P3—N2—P2—N1	10.2 (6)	P5—N6—P6—Cl8	116.5 (3)
P3—N2—P2—Cl1	136.8 (4)

(4) 1,1-bis(tert-butylamino)-3-tert-butylamino,3,5,5-tetrachlorocyclotriphosphazene

Crystal data

C16H40Cl2N7P3	Dx = 1.245 Mg m^−3
Mr = 494.36	Melting point: 156°C K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.5207 (2) Å	Cell parameters from 16145 reflections
b = 16.1282 (2) Å	θ = 2.9–27.5°
c = 13.1311 (2) Å	µ = 0.45 mm^−1
β = 95.903 (1)°	T = 120 K
V = 2637.59 (7) Å^3	Block, colourless
Z = 4	0.40 × 0.25 × 0.25 mm
F(000) = 1056

Data collection

Nonius KappaCCD diffractometer	5994 independent reflections
Radiation source: Nonius FR591 rotating anode	5106 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ & ω scans	h = −16→16
Absorption correction: multi-scan SORTAV (Blessing, 1997)	k = −20→20
Tmin = 0.842, Tmax = 0.897	l = −17→17
29576 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 1.1457P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.030
5994 reflections	Δρmax = 0.27 e Å^−3
270 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0099 (11)

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
H1	0.5933 (18)	−0.0370 (13)	0.5905 (17)	0.042 (6)*
H11	0.4996 (18)	0.1429 (14)	0.6398 (17)	0.045 (6)*
H31	0.5229 (18)	0.2541 (14)	0.3219 (17)	0.042 (7)*
H21	0.6316 (19)	0.0881 (16)	0.3033 (19)	0.055 (7)*
P1	0.63377 (3)	0.08705 (2)	0.58445 (3)	0.02532 (12)
P3	0.63247 (3)	0.18505 (3)	0.40326 (3)	0.02778 (12)
P2	0.80248 (3)	0.19328 (3)	0.55589 (4)	0.03258 (13)
Cl2	0.84288 (5)	0.29406 (3)	0.64477 (4)	0.05608 (16)
Cl1	0.95356 (4)	0.15530 (4)	0.53476 (5)	0.05977 (17)
N3	0.58128 (11)	0.11988 (8)	0.47570 (10)	0.0278 (3)
N5	0.54212 (12)	0.10666 (9)	0.66307 (11)	0.0304 (3)
N4	0.64835 (12)	−0.01365 (9)	0.59446 (11)	0.0301 (3)
N1	0.75032 (11)	0.12700 (9)	0.62159 (11)	0.0325 (3)
N2	0.74589 (12)	0.22426 (9)	0.45138 (11)	0.0350 (3)
C3	0.76775 (17)	−0.04221 (12)	0.45807 (16)	0.0447 (5)
H3A	0.7933	0.0152	0.4587	0.067*
H3B	0.7042	−0.0477	0.4084	0.067*
H3C	0.8244	−0.0792	0.4388	0.067*
N6	0.64041 (14)	0.13570 (10)	0.29421 (11)	0.0364 (3)
N7	0.55544 (14)	0.26399 (10)	0.36771 (13)	0.0377 (4)
C1	0.73873 (14)	−0.06543 (11)	0.56431 (14)	0.0333 (4)
C5	0.55491 (15)	0.11040 (11)	0.77714 (13)	0.0363 (4)
C2	0.83600 (16)	−0.05749 (14)	0.64443 (18)	0.0503 (5)
H2A	0.8152	−0.0727	0.7119	0.076*
H2B	0.8619	−0.0001	0.6462	0.076*
H2C	0.8932	−0.0946	0.6265	0.076*
C4	0.69899 (17)	−0.15479 (11)	0.56321 (16)	0.0435 (5)
H4A	0.6803	−0.1698	0.6315	0.065*
H4B	0.7557	−0.1918	0.5439	0.065*
H4C	0.6354	−0.1603	0.5135	0.065*
C9	0.71139 (18)	0.15448 (13)	0.21300 (14)	0.0462 (5)
C13	0.53940 (17)	0.34388 (12)	0.41971 (17)	0.0451 (5)
C14	0.5342 (2)	0.33081 (15)	0.53378 (19)	0.0596 (6)
H14A	0.6028	0.3083	0.5646	0.089*
H14B	0.4764	0.2918	0.5442	0.089*
H14C	0.5202	0.3839	0.5661	0.089*
C7	0.6104 (2)	0.19089 (16)	0.81287 (18)	0.0641 (7)
H7A	0.5687	0.2381	0.7835	0.096*
H7B	0.6826	0.1923	0.7904	0.096*
H7C	0.6156	0.1940	0.8878	0.096*
C11	0.7121 (2)	0.24687 (15)	0.19187 (18)	0.0636 (7)
H11A	0.6387	0.2656	0.1706	0.095*
H11B	0.7578	0.2583	0.1372	0.095*
H11C	0.7402	0.2764	0.2542	0.095*
C6	0.4424 (2)	0.10919 (19)	0.81066 (19)	0.0659 (7)
H6A	0.4021	0.1574	0.7819	0.099*
H6B	0.4467	0.1112	0.8856	0.099*
H6C	0.4056	0.0582	0.7861	0.099*
C8	0.6176 (2)	0.03628 (16)	0.82168 (16)	0.0665 (7)
H8A	0.6902	0.0373	0.8000	0.100*
H8B	0.5812	−0.0149	0.7973	0.100*
H8C	0.6220	0.0384	0.8966	0.100*
C16	0.6307 (3)	0.40328 (15)	0.4028 (3)	0.0764 (8)
H16A	0.6335	0.4117	0.3292	0.115*
H16B	0.6989	0.3797	0.4329	0.115*
H16C	0.6184	0.4566	0.4355	0.115*
C15	0.4322 (2)	0.37871 (17)	0.3725 (3)	0.0849 (10)
H15A	0.4350	0.3874	0.2990	0.127*
H15B	0.4180	0.4316	0.4052	0.127*
H15C	0.3746	0.3394	0.3830	0.127*
C10	0.8250 (2)	0.1240 (2)	0.2457 (2)	0.0788 (9)
H10A	0.8236	0.0642	0.2588	0.118*
H10B	0.8537	0.1529	0.3082	0.118*
H10C	0.8708	0.1352	0.1911	0.118*
C12	0.6643 (3)	0.1099 (2)	0.11594 (18)	0.0873 (10)
H12A	0.6638	0.0500	0.1284	0.131*
H12B	0.7083	0.1219	0.0601	0.131*
H12C	0.5908	0.1292	0.0971	0.131*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0261 (2)	0.0272 (2)	0.0223 (2)	0.00094 (15)	0.00046 (15)	−0.00082 (15)
P3	0.0311 (2)	0.0283 (2)	0.0236 (2)	−0.00109 (16)	0.00111 (16)	0.00031 (16)
P2	0.0271 (2)	0.0378 (3)	0.0321 (2)	−0.00539 (17)	−0.00020 (18)	−0.00413 (18)
Cl2	0.0661 (4)	0.0490 (3)	0.0506 (3)	−0.0197 (2)	−0.0065 (3)	−0.0131 (2)
Cl1	0.0278 (2)	0.0839 (4)	0.0679 (4)	0.0016 (2)	0.0064 (2)	−0.0007 (3)
N3	0.0272 (7)	0.0316 (7)	0.0239 (7)	−0.0024 (5)	−0.0019 (5)	0.0015 (5)
N5	0.0323 (7)	0.0341 (7)	0.0250 (7)	0.0063 (6)	0.0037 (6)	0.0000 (6)
N4	0.0301 (7)	0.0276 (7)	0.0326 (7)	0.0019 (6)	0.0033 (6)	0.0001 (6)
N1	0.0290 (7)	0.0383 (8)	0.0286 (7)	−0.0027 (6)	−0.0047 (6)	−0.0004 (6)
N2	0.0340 (8)	0.0384 (8)	0.0321 (8)	−0.0085 (6)	0.0014 (6)	0.0027 (6)
C3	0.0504 (11)	0.0439 (11)	0.0419 (11)	0.0110 (9)	0.0143 (9)	−0.0009 (8)
N6	0.0513 (9)	0.0328 (8)	0.0255 (7)	−0.0035 (7)	0.0064 (7)	0.0005 (6)
N7	0.0455 (9)	0.0316 (8)	0.0337 (9)	0.0034 (7)	−0.0059 (7)	0.0000 (7)
C1	0.0341 (9)	0.0323 (9)	0.0332 (9)	0.0085 (7)	0.0015 (7)	−0.0014 (7)
C5	0.0450 (10)	0.0392 (9)	0.0254 (8)	−0.0006 (8)	0.0074 (7)	−0.0039 (7)
C2	0.0401 (10)	0.0528 (12)	0.0551 (13)	0.0142 (9)	−0.0099 (10)	−0.0050 (10)
C4	0.0521 (11)	0.0316 (9)	0.0459 (11)	0.0090 (8)	0.0010 (9)	0.0004 (8)
C9	0.0626 (13)	0.0510 (12)	0.0271 (9)	−0.0049 (10)	0.0139 (9)	0.0026 (8)
C13	0.0525 (12)	0.0300 (9)	0.0525 (12)	0.0056 (8)	0.0040 (10)	−0.0013 (8)
C14	0.0730 (16)	0.0506 (13)	0.0573 (14)	0.0064 (11)	0.0169 (12)	−0.0156 (11)
C7	0.0888 (19)	0.0628 (15)	0.0413 (12)	−0.0232 (13)	0.0095 (12)	−0.0190 (11)
C11	0.0826 (18)	0.0592 (14)	0.0522 (14)	−0.0116 (12)	0.0224 (12)	0.0149 (11)
C6	0.0584 (14)	0.0952 (19)	0.0476 (13)	−0.0038 (13)	0.0223 (11)	−0.0077 (13)
C8	0.103 (2)	0.0694 (16)	0.0267 (10)	0.0293 (14)	0.0026 (11)	0.0066 (10)
C16	0.097 (2)	0.0361 (12)	0.101 (2)	−0.0156 (12)	0.0297 (18)	−0.0048 (13)
C15	0.091 (2)	0.0548 (15)	0.102 (2)	0.0380 (14)	−0.0250 (18)	−0.0109 (15)
C10	0.0745 (18)	0.112 (2)	0.0562 (15)	0.0246 (16)	0.0362 (14)	0.0176 (15)
C12	0.134 (3)	0.099 (2)	0.0318 (12)	−0.043 (2)	0.0274 (15)	−0.0190 (13)

Geometric parameters (Å, º)

P1—N3	1.5995 (13)	C4—H4C	0.9800
P1—N1	1.6236 (14)	C9—C11	1.516 (3)
P1—N4	1.6380 (15)	C9—C10	1.525 (4)
P1—N5	1.6512 (14)	C9—C12	1.528 (3)
P3—N3	1.5956 (14)	C13—C14	1.521 (3)
P3—N2	1.6221 (15)	C13—C15	1.527 (3)
P3—N7	1.6361 (16)	C13—C16	1.525 (3)
P3—N6	1.6502 (16)	C14—H14A	0.9800
P2—N1	1.5586 (15)	C14—H14B	0.9800
P2—N2	1.5604 (15)	C14—H14C	0.9800
P2—Cl2	2.0343 (7)	C7—H7A	0.9800
P2—Cl1	2.0343 (7)	C7—H7B	0.9800
N5—C5	1.491 (2)	C7—H7C	0.9800
N5—H11	0.83 (2)	C11—H11A	0.9800
N4—C1	1.492 (2)	C11—H11B	0.9800
N4—H1	0.78 (2)	C11—H11C	0.9800
C3—C1	1.524 (3)	C6—H6A	0.9800
C3—H3A	0.9800	C6—H6B	0.9800
C3—H3B	0.9800	C6—H6C	0.9800
C3—H3C	0.9800	C8—H8A	0.9800
N6—C9	1.488 (2)	C8—H8B	0.9800
N6—H21	0.79 (2)	C8—H8C	0.9800
N7—C13	1.482 (2)	C16—H16A	0.9800
N7—H31	0.71 (2)	C16—H16B	0.9800
C1—C4	1.524 (3)	C16—H16C	0.9800
C1—C2	1.531 (3)	C15—H15A	0.9800
C5—C8	1.514 (3)	C15—H15B	0.9800
C5—C6	1.519 (3)	C15—H15C	0.9800
C5—C7	1.524 (3)	C10—H10A	0.9800
C2—H2A	0.9800	C10—H10B	0.9800
C2—H2B	0.9800	C10—H10C	0.9800
C2—H2C	0.9800	C12—H12A	0.9800
C4—H4A	0.9800	C12—H12B	0.9800
C4—H4B	0.9800	C12—H12C	0.9800
N3—P1—N1	114.26 (7)	C11—C9—C10	110.2 (2)
N3—P1—N4	115.59 (8)	N6—C9—C12	107.14 (18)
N1—P1—N4	106.27 (8)	C11—C9—C12	108.6 (2)
N3—P1—N5	104.28 (7)	C10—C9—C12	110.6 (2)
N1—P1—N5	113.40 (8)	N7—C13—C14	110.79 (16)
N4—P1—N5	102.63 (8)	N7—C13—C15	106.74 (18)
N3—P3—N2	114.45 (7)	C14—C13—C15	109.0 (2)
N3—P3—N7	114.94 (8)	N7—C13—C16	109.87 (18)
N2—P3—N7	105.93 (8)	C14—C13—C16	109.8 (2)
N3—P3—N6	105.27 (8)	C15—C13—C16	110.5 (2)
N2—P3—N6	113.43 (8)	C13—C14—H14A	109.5
N7—P3—N6	102.36 (9)	C13—C14—H14B	109.5
N1—P2—N2	121.88 (8)	H14A—C14—H14B	109.5
N1—P2—Cl2	108.91 (6)	C13—C14—H14C	109.5
N2—P2—Cl2	108.20 (6)	H14A—C14—H14C	109.5
N1—P2—Cl1	108.50 (6)	H14B—C14—H14C	109.5
N2—P2—Cl1	108.72 (6)	C5—C7—H7A	109.5
Cl2—P2—Cl1	97.99 (3)	C5—C7—H7B	109.5
P3—N3—P1	126.65 (9)	H7A—C7—H7B	109.5
C5—N5—P1	128.76 (12)	C5—C7—H7C	109.5
C5—N5—H11	109.9 (16)	H7A—C7—H7C	109.5
P1—N5—H11	111.5 (16)	H7B—C7—H7C	109.5
C1—N4—P1	127.94 (13)	C9—C11—H11A	109.5
C1—N4—H1	113.6 (16)	C9—C11—H11B	109.5
P1—N4—H1	112.4 (16)	H11A—C11—H11B	109.5
P2—N1—P1	121.38 (9)	C9—C11—H11C	109.5
P2—N2—P3	121.19 (9)	H11A—C11—H11C	109.5
C1—C3—H3A	109.5	H11B—C11—H11C	109.5
C1—C3—H3B	109.5	C5—C6—H6A	109.5
H3A—C3—H3B	109.5	C5—C6—H6B	109.5
C1—C3—H3C	109.5	H6A—C6—H6B	109.5
H3A—C3—H3C	109.5	C5—C6—H6C	109.5
H3B—C3—H3C	109.5	H6A—C6—H6C	109.5
C9—N6—P3	128.14 (14)	H6B—C6—H6C	109.5
C9—N6—H21	114.3 (18)	C5—C8—H8A	109.5
P3—N6—H21	108.4 (18)	C5—C8—H8B	109.5
C13—N7—P3	130.48 (14)	H8A—C8—H8B	109.5
C13—N7—H31	119.5 (19)	C5—C8—H8C	109.5
P3—N7—H31	109.7 (19)	H8A—C8—H8C	109.5
N4—C1—C3	111.34 (14)	H8B—C8—H8C	109.5
N4—C1—C4	106.02 (15)	C13—C16—H16A	109.5
C3—C1—C4	109.39 (16)	C13—C16—H16B	109.5
N4—C1—C2	110.01 (15)	H16A—C16—H16B	109.5
C3—C1—C2	111.16 (17)	C13—C16—H16C	109.5
C4—C1—C2	108.75 (16)	H16A—C16—H16C	109.5
N5—C5—C8	110.72 (15)	H16B—C16—H16C	109.5
N5—C5—C6	106.48 (16)	C13—C15—H15A	109.5
C8—C5—C6	109.7 (2)	C13—C15—H15B	109.5
N5—C5—C7	110.01 (16)	H15A—C15—H15B	109.5
C8—C5—C7	110.6 (2)	C13—C15—H15C	109.5
C6—C5—C7	109.21 (19)	H15A—C15—H15C	109.5
C1—C2—H2A	109.5	H15B—C15—H15C	109.5
C1—C2—H2B	109.5	C9—C10—H10A	109.5
H2A—C2—H2B	109.5	C9—C10—H10B	109.5
C1—C2—H2C	109.5	H10A—C10—H10B	109.5
H2A—C2—H2C	109.5	C9—C10—H10C	109.5
H2B—C2—H2C	109.5	H10A—C10—H10C	109.5
C1—C4—H4A	109.5	H10B—C10—H10C	109.5
C1—C4—H4B	109.5	C9—C12—H12A	109.5
H4A—C4—H4B	109.5	C9—C12—H12B	109.5
C1—C4—H4C	109.5	H12A—C12—H12B	109.5
H4A—C4—H4C	109.5	C9—C12—H12C	109.5
H4B—C4—H4C	109.5	H12A—C12—H12C	109.5
N6—C9—C11	110.26 (17)	H12B—C12—H12C	109.5
N6—C9—C10	109.96 (17)
N2—P3—N3—P1	−3.94 (14)	N3—P3—N2—P2	5.12 (14)
N7—P3—N3—P1	−126.90 (11)	N7—P3—N2—P2	132.81 (11)
N6—P3—N3—P1	121.29 (11)	N6—P3—N2—P2	−115.70 (12)
N1—P1—N3—P3	0.75 (14)	N3—P3—N6—C9	−158.29 (17)
N4—P1—N3—P3	−123.07 (11)	N2—P3—N6—C9	−32.4 (2)
N5—P1—N3—P3	125.09 (11)	N7—P3—N6—C9	81.23 (19)
N3—P1—N5—C5	−162.53 (15)	N3—P3—N7—C13	85.23 (19)
N1—P1—N5—C5	−37.63 (17)	N2—P3—N7—C13	−42.2 (2)
N4—P1—N5—C5	76.55 (16)	N6—P3—N7—C13	−161.24 (18)
N3—P1—N4—C1	84.84 (16)	P1—N4—C1—C3	−46.5 (2)
N1—P1—N4—C1	−43.07 (16)	P1—N4—C1—C4	−165.37 (13)
N5—P1—N4—C1	−162.36 (14)	P1—N4—C1—C2	77.2 (2)
N2—P2—N1—P1	−0.23 (15)	P1—N5—C5—C8	−47.0 (2)
Cl2—P2—N1—P1	126.77 (9)	P1—N5—C5—C6	−166.22 (16)
Cl1—P2—N1—P1	−127.59 (9)	P1—N5—C5—C7	75.6 (2)
N3—P1—N1—P2	1.51 (14)	P3—N6—C9—C11	−44.4 (3)
N4—P1—N1—P2	130.20 (10)	P3—N6—C9—C10	77.4 (2)
N5—P1—N1—P2	−117.82 (11)	P3—N6—C9—C12	−162.41 (19)
N1—P2—N2—P3	−3.33 (16)	P3—N7—C13—C14	−41.1 (3)
Cl2—P2—N2—P3	−130.64 (9)	P3—N7—C13—C15	−159.7 (2)
Cl1—P2—N2—P3	123.93 (10)	P3—N7—C13—C16	80.4 (2)

 

Footnotes

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: DE5025 ). Services for accessing these data are described at the back of the journal.