A study of the pyramidality index in tris­(2,4,6-triiso­propyl­phen­yl)phos­phonium perchlorate

The title compound, C₄₅H₇₀P⁺·ClO₄⁻ or [Tripp₃PH⁺][ClO₄⁻], was produced from the perchlorate salt of the corresponding radical cation Tripp₃P^·+ through very slow H-atom abstraction reactions in a solution of 1,2-di­meth­oxy­ethane (Tripp is 2,4,6-triiso­propyl­phen­yl). The H atom on the P atom was located in a difference map and was freely refined with an isotropic displacement consistent with full occupancy [P—H = 1.37 (3) Å]. It is the most sterically congested tri­aryl­phospho­nium salt yet to be reported and has a `propeller' arrangement of the three Tripp groups around the P atom, with the protonation site located along the mol­ecular threefold axis. There are short contacts between the flanking isopropyl methine H atoms and the P atom [P...H = 1.99 (2)–2.17 (2) Å]. The sum of the angles around the P atom [Σ(C—P—C) = 349.9 (6)°] is a convenient index of pyramidality for tricoordinate centres. This value is significantly larger than in analogous Mes₃PH⁺ salts (Mes is mesityl or 2,4,6-tri­methyl­phen­yl), for which the average of the three reported structures in the literature is Σ(C—P—C) = 345.3 (6)°. For comparison, in the ubiquitous Ph₃PH⁺ salts, this parameter has a typical average value of only 333.3 (9)°. The value of Σ(C—P—C) in the title compound is midway between that of the neutral phosphane Tripp₃P [334.4 (6)°] and the phospho­niumyl radical cation Tripp₃P^·+ [359.8 (2)°]. This geometrical feature provides additional support for the assignment as a phospho­nium salt.

S1. Introduction

There is intense current inter­est in the preparation and isolation of stable phospho­niumyl radical cations (Bullock et al., 2013; Boeré et al., 2008; Sasaki et al., 2002, 2004, 2006; Sasaki & Yoshifuji, 2007; Chalier et al., 1996). Exhaustive studies have shown that this can be achieved only when very bulky substituents are employed, and thus far all the successful examples use bulky aryl groups. The widely used 2,4,6-tri­methyl­phenyl (Mes) group has been shown to lead to persistent radical cations of the type [Mes₃P^.+] but these are still reactive species and salts have never been isolated. By increasing the steric bulk through the use of various aryl groups that have in common flanking 2,6-diiso­propyl groups, designated ^i-Pr₂Ar, a number of stable [^i-Pr₂Ar₃P^.+] radical cations have now been reported. Significantly, Pan et al. (2013) recently reported the first crystal structures in this class with a number of salts containing the 2,4,6-triiso­propyl­phenyl (Tripp) group. Three structures of the type [Tripp₃P^.+]X^- were reported with X^- = SbF₆^-, [Al{OC(CF₃)₃}₄^-] and [Al{OCMe(CF₃)₂}₄^-], as well as [MesTripp₂P^.+][Al{OC(CF₃)₃}₄^-]. Each of the [Tripp₃P^.+]X^- salts were found to have structures that are planar within experimental error, with an average of the sums of angles around P (for background on this parameter, see: Boeré & Zhang, 2005), Σ(C—P—C) = 359.8 (2)°, whilst the [MesTripp₂P^.+] cation was found to be mildly pyramidal with Σ(C—P—C) = 349.15 (6)° (Pan et al., 2013). These workers report that solutions of [Tripp₃P^.+]X^- salts retain their colour when reacted with the H-atom source ⁿBu₃SnH. We have also prepared [Tripp₃P^.+]X^- salts with a variety of anions via the corresponding silver(I) salts with the identity of the radical cations confirmed by electron paramagnetic resonance (EPR) spectroscopy (see below). Although we obtained stable solid materials with X^- = SbF₆^-, AsF₆^- and ClO₄^-, we have been unable to obtain diffracting crystals. However, solutions of [Tripp₃P^.+][ClO₄^-] slowly deposit large blocks over long storage in the dark that, while streaked with residual red colour (presumably from occluded radical cation), are predominantly colourless. The structure determination reported here demonstrates that these are the diamagnetic phospho­nium salts which are probably obtained by very slow H-atom abstraction reactions. Thus, our results do not contradict the reports that a rapid reaction with reactive H atom sources such as ⁿBu₃SnH does not occur for the [Tripp₃P^.+] radical cation, but over time, perhaps with lattice forces as a driving mechanism, the H-atom abstraction product does form even from relatively unreactive H-atom sources (other molecules of the radical cation or the 1,2-di­meth­oxy­ethane solvent). Radical attack on C—H bonds by phosponiumyl ions has recently been reported and can be made catalytic with the addition of suitable Lewis acids (Ménard et al., 2013).

S2. Experimental

S2.1. Synthesis and crystallization

A small qu­antity of tris­(2,4,6-triiso­propyl­phenyl)­phosphane (Tripp₃P), prepared according to the literature method of Sasaki et al. (2002), was placed in the wide limb [outer diameter (od) 8 mm] end of a Pyrex `T' tube, and a grain of AgClO<sub>4</sub> was added to the solid. Dried degassed 1,2-di­meth­oxy­ethane (DME; distilled under N<sub>2</sub> from molten sodium) was added by syringe (1.0 ml) and the reaction mixture was immediately connected to a vacuum line and freeze–thaw degassed three times. While still under vacuum, the opening was sealed by melting the glass. After cooling the hot glass, the reaction mixture was carefully thawed and shaken to dissolve the reagents. An immediate intense deep-red colour developed. Small qu­anti­ties of the red material were decanted into the other arm of the vessel, which consists of a 4 mm od EPR tube. Solvent was then carefully distilled into the narrow limb to ensure a dilute solution of the radical. The EPR spectrum (X-band, 9.7674 GHz) was determined (Fig. 3) at ambient temperature (ca 291 K). The spectrum displays the characteristic doublet from coupling to the single <sup>31</sup>P nucleus with a hyperfine splitting of 23.62 mT and third-order corrected g value of 2.0060. Unresolved coupling to H atoms of the 2,4,6-triiso­propyl­phenyl ring is evident from the need to include about 15% Gaussian character to the simulated line shape. The spectrum displays unsymmetrical linewidths, which fit to a `slow tumbling' equation: LW = (0.650 – 0.10m) mT (Murphy, 2009). This data may be compared to a reported a(³¹P) = 23.3 mT and (likely uncorrected) g = 2.008 for solutions made up from the corresponding SbF₆^- salt in CH₂Cl₂ solutions (Pan et al., 2013). Repeated attempts to grow crystals of such salts with a variety of anions from many different solvents were unsuccessful, but over a very long time (4–5 years) during storage of the sealed T-tube in the dark at ambient temperature, large blocks developed containing red tinted streaks, but which are nevertheless predominantly colourless. Successful solution of the single-crystal structure shows that rather than the expected radical cation salt [Tripp₃P^.+][ClO₄^-], which has a deep-red colour, the crystals are composed of colourless diamagnetic phospho­nium salt, [Tripp₃PH⁺][ClO₄^-], (I). We believe that this product results from slow H-atom abstraction, either from the reaction medium (solvent, adventitious moisture) or from other cation molecules. The other possibility, that excess silver salt has hydrolysed to HClO₄ which then protonated unreacted phosphane, cannot be ruled out entirely, but does not seem to be consistent with the timescale of the reaction that was established from monitoring the EPR spectra.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atom were treated as riding, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl, C—H = 1.00 Å and U_iso(H) = 1.2U_eq(C) for methine and C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms. The PLATON `CALC VOID' routine (Spek, 2009) was used to identify solvent-accessible voids in the unit cell.

S3. Results and discussion

We report here the structure determination of tris­(2,4,6-triiso­propyl­phenyl)­phospho­nium perchlorate, [Tripp₃PH⁺][ClO₄^-], (I) (Fig. 1). There are only a relatively small number of structures reported that contain Ar₃PH⁺ cations. A search of the Cambridge Structural Database (CSD, Version 5.34, with updates to May 2013; Allen, 2002) resulted in 45 different structures: of these 24 contain the Ph₃PH⁺ ion and another eight are closely related [such as (XC₆H₄)Ph₂PH⁺ ions]. Taking three of the more accurately determined structures containing this ion [refcodes ABERAA (Junk & Atwood, 1999), BARVUL (Boorman et al., 1981) and KAXQUW (Hagenbach & Abram, 2005)] yields an average value for Σ(C—P—C) = 333.3 (9)° (see Table 2). Obviously more sterically bulky phospho­nium salts identified from this search include four exemplars of tris­(2,4,6-tri­meth­oxy­phenyl)­phospho­nium salts [refcodes LAFGEE10, WIBJEW and WIBJIA (Dunbar & Quillevere, 1993), and TAJGAM (Dunbar & Pence, 1991)]. These structures show greater variation in pyramidality compared to Ph₃PH⁺ apparently because the substituents take differing orientations around the P atom, resulting in an average Σ(C—P—C) value of 340 (3)°, with a rather large s.u. value. The bulkiest structures reported to date contain Mes₃PH⁺ ions, for which three structures are in the CSD [refcodes LUWPOJ (Ménard & Stephan, 2010), QUHCAY (Jiang et al., 2009) and XALCUK (Schäfer et al., 2011)]. These display fairly consistent structural features with `propeller' orientations of the aryl rings, yielding an average Σ(C—P—C) value of 345.3 (6)°. The increased steric bulk of the Tripp substituent is then clearly observable by the Σ(C—P—C) value of 349.9 (6)° in (I). The pyramidality index of (I) places it firmly between the planarity observed in Tripp₃P^.+ salts, with an average Σ(C—P—C) value of 359.8 (2)° (Pan et al., 2013), and the more pyramidal neutral Tripp₃P, for which the Σ(C—P—C) value is 334.4 (6)° (refcode XUNXEJ; Sasaki et al., 2002). This distinctive structural feature provides strong support for our identification of the title cation as a phospho­nium ion.

An unusual feature of the structure, and one that is likely a direct consequence of steric crowding, is the presence of short intra­molecular distances between atom H1 on phospho­rus and the three flanking iso­propyl group methine H atoms H7, H25 and H37, ranging from 1.99 (2) to 2.17 (2) Å, and thus shorter than or equal to the sums of their van der Waals radii of 2.18 Å. Perusal of space-filling molecular models shows that atom H1 is completely buried amongst these flanking iso­propyl group atoms. Severe steric crowding is also indicated by distortions in the aryl ring. In particular, the C31-ring shows a distinct boat conformation; from the least-squares plane defined by atoms C32/C33/C35/C36 (r.m.s. deviation = 0.002 Å), the other atoms deviate by 0.058 (4) (C34) 0.064 (4) (C32) and 0.627 (5) Å (P1). By contrast, in neutral Tripp₃P, the most distorted ring has the ipso-C and P atoms 0.046 and 0.491 Å, respectively, out of plane (refcode XUNXEJ; Sasaki et al., 2002). The final feature of note in this structure is the presence of four voids in the unit cell with a volume of 30 ų each (Fig. 2). These were identified with the help of the PLATON `CALC VOID' routine (Spek, 2009), as well as with Mercury (Macrae et al., 2006). However, the voids seem to be empty of any nuclei. Most likely these cavities are merely consequences of packing such large cations with the relatively small perchlorate anions, but we cannot rule out the possibility that some contain free electrons left over from the H-atom abstraction reactions that lead to these phospho­nium salts.

Related literature

For general background, see: Bullock et al. (2013); Boeré et al. (2008); Chalier et al. (1996); Murphy (2009); Pan et al. (2013); Sasaki & Yoshifuji (2007); Sasaki et al. (2004, 2006). For synthesis details, see: Sasaki et al. (2002). For related structures, see: Boorman et al. (1981); Dunbar & Pence (1991); Dunbar & Quillevere (1993); Hagenbach & Abram (2005); Jiang et al. (2009); Junk & Atwood (1999); Ménard & Stephan (2010); Schäfer et al. (2011). For refinement details, see: Spek (2009). For geometric data, see: Boeré & Zhang (2005).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

The structure of the cation–anion pair in (I), with displacement elipsoids drawn at the 40% probability level and showing the atom-numbering scheme. H atoms on C atoms have been omitted to enhance visibility.

A packing view with the b axis vertical and the bisector of a and c perpendicular. The contact surfaces of the small void volumes in the lattice are shown in yellow (each cavity has a volume of ~30 ų). H atoms on C atoms have been omitted to enhance visibility.

(a) The X-band (9.8 GHz) EPR spectrum of a solution of [Tripp₃P^.+]ClO₄^- in 1,2-dimethoxyethane at 291 K, showing the expected doublet with a(³¹P) = 23.62 mT. (b) The simulation obtained in which the line widths fit to 0.650–0.10m mT, consistent with incomplete averaging of the g and a tensors caused by slow tumbling in solution.

Tris(2,4,6-triisopropylphenyl)phosphonium perchlorate

Crystal data

C45H70P^+·ClO4^−	Dx = 1.131 Mg m^−3
Mr = 741.43	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 9973 reflections
a = 13.6822 (14) Å	θ = 2.2–27.4°
b = 17.0621 (18) Å	µ = 0.16 mm^−1
c = 18.660 (2) Å	T = 173 K
V = 4356.1 (8) Å^3	Block, red
Z = 4	0.38 × 0.21 × 0.17 mm
F(000) = 1616

Data collection

Bruker APEXII CCD area-detector diffractometer	10021 independent reflections
Radiation source: fine-focus sealed tube, Bruker D8	7663 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 66.06 pixels mm^-1	θmax = 27.5°, θmin = 1.9°
phi and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −22→22
Tmin = 0.941, Tmax = 0.973	l = −24→24
61837 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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0506P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
10021 reflections	Δρmax = 0.35 e Å^−3
483 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.49 (7)

Special details

Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass capillary and cooled in the gas stream of the diffractometer Kryoflex device.

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. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
P1	0.71447 (5)	0.49036 (4)	0.96924 (3)	0.02084 (14)
H1	0.7281 (19)	0.4174 (15)	0.9396 (13)	0.029 (7)*
C1	0.63959 (17)	0.53394 (15)	0.90014 (12)	0.0195 (5)
C2	0.56611 (18)	0.48513 (15)	0.87098 (12)	0.0234 (5)
C3	0.50853 (19)	0.51520 (17)	0.81573 (13)	0.0288 (6)
H3	0.4585	0.4833	0.7958	0.035*
C4	0.5221 (2)	0.59044 (17)	0.78886 (13)	0.0300 (6)
C5	0.5947 (2)	0.63629 (16)	0.81843 (13)	0.0294 (6)
H5	0.6048	0.6873	0.7995	0.035*
C6	0.65371 (18)	0.61146 (15)	0.87468 (13)	0.0236 (5)
C7	0.54422 (19)	0.40214 (16)	0.89658 (14)	0.0283 (6)
H7	0.5865	0.3920	0.9393	0.034*
C8	0.4378 (2)	0.3928 (2)	0.92063 (19)	0.0512 (9)
H8A	0.4277	0.3398	0.9393	0.077*
H8B	0.3943	0.4017	0.8797	0.077*
H8C	0.4234	0.4311	0.9583	0.077*
C9	0.5711 (3)	0.34194 (19)	0.83992 (17)	0.0527 (9)
H9A	0.6397	0.3487	0.8262	0.079*
H9B	0.5294	0.3492	0.7977	0.079*
H9C	0.5615	0.2891	0.8593	0.079*
C10	0.7262 (2)	0.66905 (16)	0.90601 (14)	0.0275 (6)
H10	0.7506	0.6465	0.9521	0.033*
C11	0.6792 (2)	0.74829 (16)	0.92315 (16)	0.0374 (7)
H11A	0.6207	0.7401	0.9525	0.056*
H11B	0.6610	0.7746	0.8784	0.056*
H11C	0.7259	0.7809	0.9495	0.056*
C12	0.8143 (2)	0.68025 (19)	0.85671 (17)	0.0424 (8)
H12A	0.7923	0.7008	0.8104	0.064*
H12B	0.8470	0.6298	0.8495	0.064*
H12C	0.8601	0.7174	0.8787	0.064*
C13	0.4545 (2)	0.62553 (19)	0.73408 (15)	0.0405 (7)
H13	0.4855	0.6750	0.7166	0.049*
C14	0.3592 (3)	0.6481 (3)	0.77047 (19)	0.0691 (12)
H14A	0.3733	0.6806	0.8125	0.104*
H14B	0.3246	0.6006	0.7855	0.104*
H14C	0.3184	0.6777	0.7368	0.104*
C15	0.4353 (3)	0.5749 (2)	0.66933 (17)	0.0682 (13)
H15A	0.3998	0.5276	0.6840	0.102*
H15B	0.4976	0.5599	0.6474	0.102*
H15C	0.3960	0.6042	0.6346	0.102*
C16	0.84116 (17)	0.51992 (14)	0.97472 (13)	0.0207 (5)
C17	0.88062 (17)	0.56252 (14)	1.03215 (13)	0.0217 (5)
C18	0.98159 (18)	0.57168 (15)	1.03514 (14)	0.0258 (6)
H18	1.0092	0.5996	1.0742	0.031*
C19	1.04335 (18)	0.54141 (16)	0.98298 (14)	0.0265 (6)
C20	1.00227 (18)	0.50219 (16)	0.92537 (14)	0.0282 (6)
H20	1.0440	0.4824	0.8889	0.034*
C21	0.90236 (18)	0.49091 (16)	0.91918 (13)	0.0249 (5)
C22	0.81955 (18)	0.60123 (15)	1.08964 (13)	0.0256 (6)
H22	0.7495	0.5945	1.0758	0.031*
C23	0.8396 (2)	0.68941 (17)	1.09352 (18)	0.0423 (8)
H23A	0.8327	0.7124	1.0457	0.063*
H23B	0.9062	0.6982	1.1111	0.063*
H23C	0.7928	0.7140	1.1263	0.063*
C24	0.8328 (2)	0.5626 (2)	1.16243 (14)	0.0424 (8)
H24A	0.9015	0.5662	1.1769	0.064*
H24B	0.8135	0.5074	1.1594	0.064*
H24C	0.7919	0.5894	1.1979	0.064*
C25	0.8642 (2)	0.44669 (17)	0.85350 (15)	0.0314 (7)
H25	0.7921	0.4558	0.8503	0.038*
C26	0.9106 (2)	0.4753 (2)	0.78344 (15)	0.0468 (8)
H26A	0.9800	0.4612	0.7828	0.070*
H26B	0.9040	0.5324	0.7801	0.070*
H26C	0.8774	0.4508	0.7427	0.070*
C27	0.8810 (3)	0.35937 (19)	0.86237 (19)	0.0508 (9)
H27A	0.8545	0.3422	0.9086	0.076*
H27B	0.9512	0.3483	0.8607	0.076*
H27C	0.8480	0.3311	0.8236	0.076*
C28	1.15313 (19)	0.55200 (18)	0.98844 (15)	0.0329 (7)
H28	1.1677	0.5794	1.0346	0.039*
C29	1.1909 (2)	0.60306 (19)	0.92731 (16)	0.0414 (8)
H29A	1.1575	0.6538	0.9283	0.062*
H29B	1.1781	0.5770	0.8814	0.062*
H29C	1.2614	0.6111	0.9329	0.062*
C30	1.2057 (2)	0.4737 (2)	0.98903 (19)	0.0517 (9)
H30A	1.1978	0.4481	0.9424	0.078*
H30B	1.1779	0.4403	1.0266	0.078*
H30C	1.2754	0.4821	0.9985	0.078*
C31	0.64563 (17)	0.47203 (14)	1.05060 (12)	0.0201 (5)
C32	0.66011 (18)	0.39765 (15)	1.08289 (12)	0.0225 (5)
C33	0.58916 (19)	0.37086 (15)	1.13016 (13)	0.0256 (6)
H33	0.5978	0.3213	1.1524	0.031*
C34	0.50577 (19)	0.41436 (15)	1.14596 (13)	0.0246 (6)
C35	0.49834 (18)	0.48942 (15)	1.11824 (13)	0.0230 (5)
H35	0.4445	0.5211	1.1321	0.028*
C36	0.56674 (17)	0.52000 (15)	1.07095 (12)	0.0206 (5)
C37	0.74783 (19)	0.34504 (16)	1.06815 (14)	0.0292 (6)
H37	0.7949	0.3749	1.0375	0.035*
C38	0.8002 (2)	0.32274 (19)	1.13796 (16)	0.0445 (8)
H38A	0.7586	0.2873	1.1659	0.067*
H38B	0.8134	0.3702	1.1659	0.067*
H38C	0.8620	0.2965	1.1266	0.067*
C39	0.7175 (2)	0.27152 (16)	1.02758 (17)	0.0416 (7)
H39A	0.6848	0.2864	0.9829	0.062*
H39B	0.6726	0.2406	1.0572	0.062*
H39C	0.7756	0.2402	1.0165	0.062*
C40	0.55330 (18)	0.60468 (15)	1.04719 (12)	0.0240 (6)
H40	0.6086	0.6183	1.0144	0.029*
C41	0.5575 (2)	0.66073 (16)	1.11175 (14)	0.0298 (6)
H41A	0.5021	0.6502	1.1437	0.045*
H41B	0.5542	0.7150	1.0948	0.045*
H41C	0.6188	0.6526	1.1379	0.045*
C42	0.4580 (2)	0.61740 (17)	1.00626 (14)	0.0324 (6)
H42A	0.4025	0.6058	1.0377	0.049*
H42B	0.4561	0.5825	0.9646	0.049*
H42C	0.4542	0.6720	0.9902	0.049*
C43	0.4206 (2)	0.38079 (17)	1.18748 (15)	0.0332 (6)
H43	0.3853	0.4254	1.2106	0.040*
C44	0.4478 (2)	0.32272 (18)	1.24584 (16)	0.0399 (7)
H44A	0.4910	0.3482	1.2806	0.060*
H44B	0.4815	0.2778	1.2244	0.060*
H44C	0.3884	0.3047	1.2701	0.060*
C45	0.3518 (2)	0.3441 (2)	1.13227 (17)	0.0465 (8)
H45A	0.3874	0.3049	1.1042	0.070*
H45B	0.3269	0.3850	1.1002	0.070*
H45C	0.2970	0.3189	1.1570	0.070*
Cl1	0.78075 (7)	0.88844 (5)	0.75076 (5)	0.0552 (2)
O1	0.7831 (4)	0.96017 (17)	0.71385 (17)	0.1182 (14)
O2	0.6876 (2)	0.8538 (2)	0.74828 (17)	0.0901 (10)
O3	0.8475 (3)	0.8343 (2)	0.7175 (2)	0.1257 (14)
O4	0.8087 (2)	0.8991 (2)	0.82266 (15)	0.0973 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0185 (3)	0.0253 (3)	0.0188 (3)	−0.0014 (3)	0.0000 (3)	0.0019 (3)
C1	0.0177 (12)	0.0262 (14)	0.0145 (11)	0.0017 (10)	−0.0005 (9)	−0.0008 (10)
C2	0.0241 (13)	0.0294 (14)	0.0167 (11)	0.0011 (12)	0.0016 (10)	−0.0035 (11)
C3	0.0260 (14)	0.0398 (16)	0.0207 (12)	0.0001 (13)	−0.0050 (10)	−0.0070 (12)
C4	0.0323 (15)	0.0381 (17)	0.0196 (13)	0.0091 (13)	−0.0004 (11)	−0.0019 (12)
C5	0.0365 (16)	0.0298 (15)	0.0219 (13)	0.0042 (13)	0.0019 (12)	0.0049 (11)
C6	0.0245 (13)	0.0269 (14)	0.0194 (12)	0.0034 (11)	0.0037 (10)	0.0002 (11)
C7	0.0310 (15)	0.0282 (15)	0.0258 (13)	−0.0065 (12)	−0.0027 (11)	−0.0034 (11)
C8	0.0360 (18)	0.057 (2)	0.061 (2)	−0.0150 (17)	0.0068 (16)	0.0041 (18)
C9	0.080 (3)	0.0335 (18)	0.0446 (19)	−0.0040 (18)	0.0115 (18)	−0.0086 (15)
C10	0.0315 (15)	0.0241 (14)	0.0270 (13)	−0.0010 (12)	−0.0014 (12)	0.0046 (11)
C11	0.0480 (18)	0.0252 (15)	0.0389 (16)	−0.0005 (14)	0.0010 (14)	0.0004 (13)
C12	0.0354 (17)	0.0398 (18)	0.052 (2)	−0.0051 (14)	0.0081 (14)	0.0047 (15)
C13	0.0431 (18)	0.0502 (19)	0.0282 (15)	0.0111 (15)	−0.0090 (13)	0.0019 (14)
C14	0.063 (2)	0.098 (3)	0.047 (2)	0.051 (2)	−0.0156 (18)	−0.016 (2)
C15	0.080 (3)	0.090 (3)	0.0343 (18)	0.043 (2)	−0.0275 (18)	−0.0183 (19)
C16	0.0174 (11)	0.0218 (13)	0.0228 (12)	−0.0001 (10)	−0.0003 (10)	0.0019 (11)
C17	0.0227 (13)	0.0222 (13)	0.0201 (12)	0.0004 (10)	0.0004 (10)	0.0000 (11)
C18	0.0216 (13)	0.0325 (15)	0.0233 (12)	−0.0024 (11)	−0.0009 (11)	−0.0009 (12)
C19	0.0192 (13)	0.0321 (15)	0.0281 (14)	0.0016 (11)	0.0008 (10)	0.0022 (12)
C20	0.0233 (13)	0.0339 (16)	0.0273 (13)	0.0050 (12)	0.0048 (10)	−0.0025 (12)
C21	0.0254 (13)	0.0262 (14)	0.0230 (12)	−0.0018 (11)	0.0020 (10)	−0.0019 (11)
C22	0.0190 (12)	0.0325 (15)	0.0254 (13)	−0.0013 (11)	0.0016 (10)	−0.0082 (12)
C23	0.0353 (17)	0.0366 (18)	0.055 (2)	−0.0014 (14)	0.0025 (15)	−0.0204 (15)
C24	0.0401 (18)	0.063 (2)	0.0240 (15)	0.0047 (16)	0.0042 (13)	−0.0059 (14)
C25	0.0240 (14)	0.0371 (17)	0.0331 (15)	−0.0030 (12)	0.0032 (12)	−0.0133 (13)
C26	0.0512 (19)	0.061 (2)	0.0283 (15)	−0.0086 (17)	0.0038 (14)	−0.0092 (15)
C27	0.057 (2)	0.0396 (19)	0.056 (2)	−0.0027 (16)	0.0104 (17)	−0.0166 (17)
C28	0.0186 (13)	0.0521 (19)	0.0279 (15)	−0.0014 (13)	−0.0017 (11)	−0.0009 (13)
C29	0.0275 (16)	0.056 (2)	0.0406 (16)	−0.0087 (15)	0.0012 (13)	0.0034 (16)
C30	0.0270 (16)	0.065 (2)	0.063 (2)	0.0111 (16)	0.0034 (15)	0.0160 (18)
C31	0.0196 (12)	0.0250 (14)	0.0156 (11)	−0.0032 (11)	0.0008 (9)	0.0026 (10)
C32	0.0243 (13)	0.0240 (13)	0.0193 (12)	0.0012 (11)	−0.0014 (10)	−0.0018 (11)
C33	0.0298 (14)	0.0240 (14)	0.0231 (13)	−0.0004 (11)	0.0011 (11)	0.0056 (11)
C34	0.0290 (14)	0.0255 (14)	0.0194 (12)	−0.0034 (12)	0.0036 (10)	−0.0012 (11)
C35	0.0214 (13)	0.0251 (14)	0.0226 (12)	0.0019 (11)	0.0006 (10)	−0.0016 (11)
C36	0.0203 (12)	0.0244 (14)	0.0173 (11)	−0.0002 (11)	−0.0018 (9)	−0.0016 (10)
C37	0.0298 (15)	0.0280 (15)	0.0298 (14)	0.0059 (12)	0.0059 (11)	0.0046 (12)
C38	0.0427 (19)	0.0468 (19)	0.0439 (18)	0.0132 (16)	−0.0075 (15)	0.0040 (15)
C39	0.0512 (18)	0.0303 (16)	0.0432 (16)	0.0136 (15)	0.0068 (17)	−0.0055 (14)
C40	0.0250 (13)	0.0247 (14)	0.0221 (13)	0.0026 (11)	0.0029 (10)	0.0024 (11)
C41	0.0328 (16)	0.0253 (15)	0.0313 (14)	−0.0007 (12)	0.0029 (12)	−0.0027 (12)
C42	0.0311 (15)	0.0336 (16)	0.0325 (14)	0.0075 (13)	−0.0027 (12)	0.0017 (12)
C43	0.0329 (16)	0.0317 (16)	0.0349 (15)	−0.0021 (13)	0.0144 (12)	0.0037 (13)
C44	0.0462 (18)	0.0438 (18)	0.0296 (15)	−0.0114 (14)	0.0043 (14)	0.0090 (14)
C45	0.0308 (16)	0.061 (2)	0.0475 (19)	−0.0125 (16)	−0.0042 (14)	0.0205 (17)
Cl1	0.0641 (6)	0.0443 (5)	0.0572 (5)	−0.0157 (5)	−0.0263 (5)	0.0151 (4)
O1	0.219 (4)	0.0507 (17)	0.085 (2)	−0.015 (2)	−0.022 (3)	0.0322 (16)
O2	0.0644 (19)	0.120 (3)	0.086 (2)	−0.0278 (17)	−0.0308 (16)	−0.002 (2)
O3	0.106 (3)	0.090 (2)	0.182 (4)	0.021 (2)	0.026 (3)	−0.016 (3)
O4	0.112 (3)	0.114 (3)	0.0653 (18)	−0.060 (2)	−0.0460 (18)	0.0211 (17)

Geometric parameters (Å, º)

P1—C1	1.807 (2)	C24—H24C	0.9800
P1—C16	1.808 (2)	C25—C27	1.517 (4)
P1—C31	1.814 (2)	C25—C26	1.533 (4)
P1—H1	1.37 (3)	C25—H25	1.0000
C1—C2	1.414 (3)	C26—H26A	0.9800
C1—C6	1.419 (4)	C26—H26B	0.9800
C2—C3	1.395 (3)	C26—H26C	0.9800
C2—C7	1.524 (4)	C27—H27A	0.9800
C3—C4	1.391 (4)	C27—H27B	0.9800
C3—H3	0.9500	C27—H27C	0.9800
C4—C5	1.379 (4)	C28—C30	1.517 (4)
C4—C13	1.503 (4)	C28—C29	1.525 (4)
C5—C6	1.390 (3)	C28—H28	1.0000
C5—H5	0.9500	C29—H29A	0.9800
C6—C10	1.513 (4)	C29—H29B	0.9800
C7—C9	1.519 (4)	C29—H29C	0.9800
C7—C8	1.532 (4)	C30—H30A	0.9800
C7—H7	1.0000	C30—H30B	0.9800
C8—H8A	0.9800	C30—H30C	0.9800
C8—H8B	0.9800	C31—C36	1.407 (3)
C8—H8C	0.9800	C31—C32	1.419 (3)
C9—H9A	0.9800	C32—C33	1.389 (3)
C9—H9B	0.9800	C32—C37	1.524 (3)
C9—H9C	0.9800	C33—C34	1.393 (4)
C10—C12	1.529 (4)	C33—H33	0.9500
C10—C11	1.530 (4)	C34—C35	1.385 (4)
C10—H10	1.0000	C34—C43	1.512 (4)
C11—H11A	0.9800	C35—C36	1.388 (3)
C11—H11B	0.9800	C35—H35	0.9500
C11—H11C	0.9800	C36—C40	1.522 (4)
C12—H12A	0.9800	C37—C39	1.523 (4)
C12—H12B	0.9800	C37—C38	1.534 (4)
C12—H12C	0.9800	C37—H37	1.0000
C13—C15	1.508 (4)	C38—H38A	0.9800
C13—C14	1.519 (5)	C38—H38B	0.9800
C13—H13	1.0000	C38—H38C	0.9800
C14—H14A	0.9800	C39—H39A	0.9800
C14—H14B	0.9800	C39—H39B	0.9800
C14—H14C	0.9800	C39—H39C	0.9800
C15—H15A	0.9800	C40—C42	1.527 (4)
C15—H15B	0.9800	C40—C41	1.539 (4)
C15—H15C	0.9800	C40—H40	1.0000
C16—C17	1.403 (3)	C41—H41A	0.9800
C16—C21	1.421 (3)	C41—H41B	0.9800
C17—C18	1.391 (3)	C41—H41C	0.9800
C17—C22	1.512 (3)	C42—H42A	0.9800
C18—C19	1.389 (4)	C42—H42B	0.9800
C18—H18	0.9500	C42—H42C	0.9800
C19—C20	1.385 (4)	C43—C44	1.518 (4)
C19—C28	1.516 (4)	C43—C45	1.530 (4)
C20—C21	1.385 (4)	C43—H43	1.0000
C20—H20	0.9500	C44—H44A	0.9800
C21—C25	1.531 (3)	C44—H44B	0.9800
C22—C24	1.520 (4)	C44—H44C	0.9800
C22—C23	1.531 (4)	C45—H45A	0.9800
C22—H22	1.0000	C45—H45B	0.9800
C23—H23A	0.9800	C45—H45C	0.9800
C23—H23B	0.9800	Cl1—O1	1.405 (3)
C23—H23C	0.9800	Cl1—O2	1.406 (3)
C24—H24A	0.9800	Cl1—O4	1.407 (3)
C24—H24B	0.9800	Cl1—O3	1.439 (4)
C1—P1—C16	117.98 (11)	C27—C25—C21	110.2 (3)
C1—P1—C31	111.95 (11)	C27—C25—C26	110.1 (3)
C16—P1—C31	119.91 (11)	C21—C25—C26	112.6 (2)
C1—P1—H1	99.3 (11)	C27—C25—H25	107.9
C16—P1—H1	98.4 (11)	C21—C25—H25	107.9
C31—P1—H1	104.5 (10)	C26—C25—H25	107.9
C2—C1—C6	121.1 (2)	C25—C26—H26A	109.5
C2—C1—P1	115.81 (19)	C25—C26—H26B	109.5
C6—C1—P1	123.06 (18)	H26A—C26—H26B	109.5
C3—C2—C1	118.0 (2)	C25—C26—H26C	109.5
C3—C2—C7	117.5 (2)	H26A—C26—H26C	109.5
C1—C2—C7	124.5 (2)	H26B—C26—H26C	109.5
C4—C3—C2	122.0 (3)	C25—C27—H27A	109.5
C4—C3—H3	119.0	C25—C27—H27B	109.5
C2—C3—H3	119.0	H27A—C27—H27B	109.5
C5—C4—C3	118.4 (2)	C25—C27—H27C	109.5
C5—C4—C13	119.3 (3)	H27A—C27—H27C	109.5
C3—C4—C13	122.0 (3)	H27B—C27—H27C	109.5
C4—C5—C6	123.2 (3)	C19—C28—C30	111.4 (2)
C4—C5—H5	118.4	C19—C28—C29	110.7 (2)
C6—C5—H5	118.4	C30—C28—C29	110.4 (2)
C5—C6—C1	117.2 (2)	C19—C28—H28	108.1
C5—C6—C10	118.3 (2)	C30—C28—H28	108.1
C1—C6—C10	124.4 (2)	C29—C28—H28	108.1
C9—C7—C2	111.3 (2)	C28—C29—H29A	109.5
C9—C7—C8	111.3 (3)	C28—C29—H29B	109.5
C2—C7—C8	112.0 (2)	H29A—C29—H29B	109.5
C9—C7—H7	107.3	C28—C29—H29C	109.5
C2—C7—H7	107.3	H29A—C29—H29C	109.5
C8—C7—H7	107.3	H29B—C29—H29C	109.5
C7—C8—H8A	109.5	C28—C30—H30A	109.5
C7—C8—H8B	109.5	C28—C30—H30B	109.5
H8A—C8—H8B	109.5	H30A—C30—H30B	109.5
C7—C8—H8C	109.5	C28—C30—H30C	109.5
H8A—C8—H8C	109.5	H30A—C30—H30C	109.5
H8B—C8—H8C	109.5	H30B—C30—H30C	109.5
C7—C9—H9A	109.5	C36—C31—C32	120.9 (2)
C7—C9—H9B	109.5	C36—C31—P1	121.60 (18)
H9A—C9—H9B	109.5	C32—C31—P1	115.93 (18)
C7—C9—H9C	109.5	C33—C32—C31	117.8 (2)
H9A—C9—H9C	109.5	C33—C32—C37	118.1 (2)
H9B—C9—H9C	109.5	C31—C32—C37	124.1 (2)
C6—C10—C12	111.4 (2)	C32—C33—C34	122.1 (2)
C6—C10—C11	112.3 (2)	C32—C33—H33	118.9
C12—C10—C11	110.3 (2)	C34—C33—H33	118.9
C6—C10—H10	107.5	C35—C34—C33	118.3 (2)
C12—C10—H10	107.5	C35—C34—C43	119.0 (2)
C11—C10—H10	107.5	C33—C34—C43	122.5 (2)
C10—C11—H11A	109.5	C34—C35—C36	122.4 (2)
C10—C11—H11B	109.5	C34—C35—H35	118.8
H11A—C11—H11B	109.5	C36—C35—H35	118.8
C10—C11—H11C	109.5	C35—C36—C31	118.0 (2)
H11A—C11—H11C	109.5	C35—C36—C40	117.4 (2)
H11B—C11—H11C	109.5	C31—C36—C40	124.5 (2)
C10—C12—H12A	109.5	C39—C37—C32	111.1 (2)
C10—C12—H12B	109.5	C39—C37—C38	110.2 (2)
H12A—C12—H12B	109.5	C32—C37—C38	111.1 (2)
C10—C12—H12C	109.5	C39—C37—H37	108.1
H12A—C12—H12C	109.5	C32—C37—H37	108.1
H12B—C12—H12C	109.5	C38—C37—H37	108.1
C4—C13—C15	115.1 (3)	C37—C38—H38A	109.5
C4—C13—C14	109.0 (2)	C37—C38—H38B	109.5
C15—C13—C14	110.8 (3)	H38A—C38—H38B	109.5
C4—C13—H13	107.2	C37—C38—H38C	109.5
C15—C13—H13	107.2	H38A—C38—H38C	109.5
C14—C13—H13	107.2	H38B—C38—H38C	109.5
C13—C14—H14A	109.5	C37—C39—H39A	109.5
C13—C14—H14B	109.5	C37—C39—H39B	109.5
H14A—C14—H14B	109.5	H39A—C39—H39B	109.5
C13—C14—H14C	109.5	C37—C39—H39C	109.5
H14A—C14—H14C	109.5	H39A—C39—H39C	109.5
H14B—C14—H14C	109.5	H39B—C39—H39C	109.5
C13—C15—H15A	109.5	C36—C40—C42	112.6 (2)
C13—C15—H15B	109.5	C36—C40—C41	110.9 (2)
H15A—C15—H15B	109.5	C42—C40—C41	109.6 (2)
C13—C15—H15C	109.5	C36—C40—H40	107.9
H15A—C15—H15C	109.5	C42—C40—H40	107.9
H15B—C15—H15C	109.5	C41—C40—H40	107.9
C17—C16—C21	120.7 (2)	C40—C41—H41A	109.5
C17—C16—P1	123.83 (18)	C40—C41—H41B	109.5
C21—C16—P1	115.24 (18)	H41A—C41—H41B	109.5
C18—C17—C16	118.1 (2)	C40—C41—H41C	109.5
C18—C17—C22	118.1 (2)	H41A—C41—H41C	109.5
C16—C17—C22	123.8 (2)	H41B—C41—H41C	109.5
C19—C18—C17	122.3 (2)	C40—C42—H42A	109.5
C19—C18—H18	118.9	C40—C42—H42B	109.5
C17—C18—H18	118.9	H42A—C42—H42B	109.5
C20—C19—C18	118.5 (2)	C40—C42—H42C	109.5
C20—C19—C28	120.8 (2)	H42A—C42—H42C	109.5
C18—C19—C28	120.8 (2)	H42B—C42—H42C	109.5
C21—C20—C19	122.2 (2)	C34—C43—C44	115.2 (2)
C21—C20—H20	118.9	C34—C43—C45	106.5 (2)
C19—C20—H20	118.9	C44—C43—C45	111.5 (2)
C20—C21—C16	118.2 (2)	C34—C43—H43	107.8
C20—C21—C25	118.1 (2)	C44—C43—H43	107.8
C16—C21—C25	123.7 (2)	C45—C43—H43	107.8
C17—C22—C24	112.3 (2)	C43—C44—H44A	109.5
C17—C22—C23	111.3 (2)	C43—C44—H44B	109.5
C24—C22—C23	111.2 (2)	H44A—C44—H44B	109.5
C17—C22—H22	107.2	C43—C44—H44C	109.5
C24—C22—H22	107.2	H44A—C44—H44C	109.5
C23—C22—H22	107.2	H44B—C44—H44C	109.5
C22—C23—H23A	109.5	C43—C45—H45A	109.5
C22—C23—H23B	109.5	C43—C45—H45B	109.5
H23A—C23—H23B	109.5	H45A—C45—H45B	109.5
C22—C23—H23C	109.5	C43—C45—H45C	109.5
H23A—C23—H23C	109.5	H45A—C45—H45C	109.5
H23B—C23—H23C	109.5	H45B—C45—H45C	109.5
C22—C24—H24A	109.5	O1—Cl1—O2	111.8 (2)
C22—C24—H24B	109.5	O1—Cl1—O4	110.4 (2)
H24A—C24—H24B	109.5	O2—Cl1—O4	109.4 (2)
C22—C24—H24C	109.5	O1—Cl1—O3	109.5 (3)
H24A—C24—H24C	109.5	O2—Cl1—O3	106.9 (2)
H24B—C24—H24C	109.5	O4—Cl1—O3	108.8 (3)
C16—P1—C1—C2	146.53 (17)	C17—C16—C21—C20	3.4 (4)
C31—P1—C1—C2	−68.1 (2)	P1—C16—C21—C20	−171.3 (2)
C16—P1—C1—C6	−32.0 (2)	C17—C16—C21—C25	−177.6 (2)
C31—P1—C1—C6	113.3 (2)	P1—C16—C21—C25	7.7 (3)
C6—C1—C2—C3	0.7 (3)	C18—C17—C22—C24	−69.6 (3)
P1—C1—C2—C3	−177.85 (18)	C16—C17—C22—C24	112.4 (3)
C6—C1—C2—C7	−178.2 (2)	C18—C17—C22—C23	55.8 (3)
P1—C1—C2—C7	3.2 (3)	C16—C17—C22—C23	−122.1 (3)
C1—C2—C3—C4	0.5 (4)	C20—C21—C25—C27	77.1 (3)
C7—C2—C3—C4	179.5 (2)	C16—C21—C25—C27	−101.8 (3)
C2—C3—C4—C5	−0.3 (4)	C20—C21—C25—C26	−46.2 (4)
C2—C3—C4—C13	−174.3 (2)	C16—C21—C25—C26	134.8 (3)
C3—C4—C5—C6	−1.2 (4)	C20—C19—C28—C30	−58.8 (3)
C13—C4—C5—C6	173.0 (3)	C18—C19—C28—C30	122.0 (3)
C4—C5—C6—C1	2.4 (4)	C20—C19—C28—C29	64.4 (3)
C4—C5—C6—C10	−175.8 (2)	C18—C19—C28—C29	−114.8 (3)
C2—C1—C6—C5	−2.1 (3)	C1—P1—C31—C36	−30.9 (2)
P1—C1—C6—C5	176.36 (19)	C16—P1—C31—C36	113.7 (2)
C2—C1—C6—C10	176.0 (2)	C1—P1—C31—C32	134.71 (18)
P1—C1—C6—C10	−5.5 (3)	C16—P1—C31—C32	−80.7 (2)
C3—C2—C7—C9	69.0 (3)	C36—C31—C32—C33	5.8 (3)
C1—C2—C7—C9	−112.1 (3)	P1—C31—C32—C33	−159.94 (19)
C3—C2—C7—C8	−56.4 (3)	C36—C31—C32—C37	−175.0 (2)
C1—C2—C7—C8	122.6 (3)	P1—C31—C32—C37	19.2 (3)
C5—C6—C10—C12	−75.3 (3)	C31—C32—C33—C34	0.3 (4)
C1—C6—C10—C12	106.6 (3)	C37—C32—C33—C34	−178.9 (2)
C5—C6—C10—C11	48.9 (3)	C32—C33—C34—C35	−5.7 (4)
C1—C6—C10—C11	−129.2 (3)	C32—C33—C34—C43	169.8 (2)
C5—C4—C13—C15	135.5 (3)	C33—C34—C35—C36	5.4 (4)
C3—C4—C13—C15	−50.6 (4)	C43—C34—C35—C36	−170.3 (2)
C5—C4—C13—C14	−99.5 (3)	C34—C35—C36—C31	0.5 (4)
C3—C4—C13—C14	74.5 (4)	C34—C35—C36—C40	−177.0 (2)
C1—P1—C16—C17	113.2 (2)	C32—C31—C36—C35	−6.2 (3)
C31—P1—C16—C17	−29.3 (3)	P1—C31—C36—C35	158.77 (18)
C1—P1—C16—C21	−72.3 (2)	C32—C31—C36—C40	171.1 (2)
C31—P1—C16—C21	145.16 (19)	P1—C31—C36—C40	−24.0 (3)
C21—C16—C17—C18	−3.5 (4)	C33—C32—C37—C39	67.4 (3)
P1—C16—C17—C18	170.7 (2)	C31—C32—C37—C39	−111.7 (3)
C21—C16—C17—C22	174.4 (2)	C33—C32—C37—C38	−55.6 (3)
P1—C16—C17—C22	−11.3 (4)	C31—C32—C37—C38	125.2 (3)
C16—C17—C18—C19	1.1 (4)	C35—C36—C40—C42	−62.3 (3)
C22—C17—C18—C19	−177.0 (2)	C31—C36—C40—C42	120.5 (3)
C17—C18—C19—C20	1.3 (4)	C35—C36—C40—C41	60.9 (3)
C17—C18—C19—C28	−179.5 (3)	C31—C36—C40—C41	−116.4 (3)
C18—C19—C20—C21	−1.4 (4)	C35—C34—C43—C44	−149.6 (3)
C28—C19—C20—C21	179.4 (3)	C33—C34—C43—C44	34.9 (4)
C19—C20—C21—C16	−0.9 (4)	C35—C34—C43—C45	86.2 (3)
C19—C20—C21—C25	−179.9 (3)	C33—C34—C43—C45	−89.3 (3)