Tris(4-formyl­phen­yl)phosphane oxide tetra­hydro­furan hemisolvate

Kakoullis Jr, J.; Fronczek, F.R.; Maverick, A.W.

doi:10.1107/S1600536813020059

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1362-o1363

doi:10.1107/S1600536813020059

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Tris(4-formylphenyl)phosphane oxide tetrahydrofuran hemisolvate

James Kakoullis Jr,^a ‡ Frank R. Fronczek ^a ^* and Andrew W. Maverick ^a

^aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 25 June 2013; accepted 19 July 2013; online 31 July 2013)

The title compound, C₂₁H₁₅O₄P·0.5C₄H₈O, contains an ordered phosphane oxide in a general position and a tetrahydrofuran solvent molecule disordered about a twofold axis. All three aldehyde substituents are nearly coplanar with their attached benzene rings, with C—C—C—O torsion angles in the range 1.64 (17)–4.24 (19)°. All three have different conformations with respect to the P=O group, one syn, one anti, and one gauche. Two of the aldehyde substituents form intermolecular C—H⋯O contacts.

Related literature

For synthetic procedures, see: Bartlett et al. (1978 ); Chalier et al. (1996 ); Kumagai & Itsuno (2001 ). For use as a precursor in supramolecular chemistry, see: Kakoullis (2007 ); Pariya et al. (2008 ). For weak hydrogen bonds, see: Desiraju & Steiner (1999 ). For related structures, see: Daly (1964 ); Etter & Baures (1988 ); Siegler et al. (2007 ); Spek (1987 ); Brock et al. (1985 ); Lenstra (2007 ); Thierbach et al. (1980 ); Baures & Silverton (1990 ); Baures (1991 ).

Experimental

Crystal data

C₂₁H₁₅O₄P·0.5C₄H₈O
M_r = 398.35
Monoclinic, C 2/c
a = 21.371 (3) Å
b = 13.474 (2) Å
c = 13.436 (2) Å
β = 99.018 (9)°
V = 3821.1 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 110 K
0.45 × 0.43 × 0.38 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.926, T_max = 0.937
36155 measured reflections
7598 independent reflections
5928 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.116
S = 1.03
7598 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O3ⁱ	0.95	2.56	3.4303 (16)	152
C14—H14⋯O1ⁱⁱ	0.95	2.50	3.1575 (14)	127
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813020059/fj2638sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813020059/fj2638Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813020059/fj2638Isup3.cml

checkCIF report

Comment top

Triphenylphosphane oxide (TPPO) has been extensively structurally studied, as a result of the high basicity of its O atom, which makes it an excellent hydrogen-bond acceptor. Its utility as a crystallization aid for molecules having hydrogen-bond donors was reported by Etter & Baures (1988), which has led to its use in forming molecular cocrystals (Siegler et al., 2007). Also, it has four known polymorphs (Spek, 1987; Brock et al., 1985; Lenstra, 2007) and several known solvates (Thierbach et al., 1980; Baures & Silverton, 1990; Baures, 1991).

Tris(4-formylphenyl)phosphane was first reported by Bartlett et al. (1978), but was also synthesized later by other groups (Chalier et al., 1996). Our interest in the phosphane and the corresponding phosphane oxide (I) stems from their use as precursors to multifunctional ligands for supramolecular chemistry (Kakoullis, 2007; Pariya et al., 2008;). The structure of (I) is illustrated in Fig. 1, showing only one orientation of the THF solvent molecule, which is disordered about a twofold axis. Atom C2S lies 0.51 Å from that axis, and the nearest distance between partially populated sites is 1.00 Å (C2S···C3S at 1 - x, y, 3/2 - z), so the resolution of the data (0.64 Å) allowed individual refinement of the partially populated positions without constraint. The three aldehyde substituents are nearly coplanar with the phenyl groups to which they are attached, with maximum torsion angle magnitude 4.24 (19) ° for C17—C18—C21—O4. The three 4-formylphenyl groups all have different conformations with respect to the phosphane oxide bond. Aldehyde C7═O2 is syn to P1═O1, with O1—P1···C7—O2 torsion angle -11.6 (1)°, while the corresponding torsion angles are 78.8 (1)° for O3 and -172.6 (1)° for O4. Intermolecular interactions include C—H···O contacts (Desiraju & Steiner, 1999) for two of the three aldehydes as donors. These are C7—H···O3(1/2 + x, 1/2 + y, z) with C···O distance 3.4303 (16) Å and 152° angle about H, and the shorter but less linear contact C14—H···O1(1/2 - x, 1/2 - y, 1 - z), 3.1575 (14) Å and 127°.

Related literature top

For synthetic procedures, see: Bartlett et al. (1978); Chalier et al. (1996); Kumagai & Itsuno (2001). For use as a precursor in supramolecular chemistry, see: Kakoullis (2007); Pariya et al. (2008). For weak hydrogen bonds, see: Desiraju & Steiner (1999). For related structures, see: Daly (1964); Etter & Baures (1988); Siegler et al. (2007); Spek (1987); Brock et al. (1985); Lenstra (2007); Thierbach et al. (1980); Baures & Silverton (1990); Baures (1991).

Experimental top

To prepare (I), the precursor tris(4-formylphenyl)phosphane was first prepared following and combining elements of the procedures for the synthesis of tris(4-formylphenyl)phosphane (Bartlett et al., 1978) and bis(4-formylphenyl)dimethylsilane (Kumagai & Itsuno, 2001). A sample of 4-bromobenzaldehyde dimethyl acetal (5 ml, 29.9 mmol) was combined with 40 ml dry THF in an inert atmosphere in a round-bottom flask. The solution was brought to -78 °C under streaming N₂, and n-butyllithium/hexanes 1.6 M (19.8 ml, 31.7 mmol) was added over approximately 1 h while stirring. The solution initially turned from colorless to light yellow, then to milky white. After 2 h, at -78 °C, PCl₃ (0.80 ml, 9.17 mmol) was added over a period of 15 minutes. When the PCl₃ was added, the solution turned orange-red. The solution was kept at -78 °C for another 1 h. Then the solution was allowed to come to room temperature over 1 h. The solvent was evaporated, leaving the crude acetal, which was dissolved in a mixture of dichloromethane and water. The solution was then washed: first with concentrated NaHCO₃ and then with brine. The organic phase was dried over Na₂SO₄. The organic phase was then evaporated, leaving a residue (5.24 g). The crude material was dissolved in 50 ml THF and 50 ml 2 M HCl. The solution was stirred under reflux conditions for 1 h under a stream of N₂. To the solution, 50 ml of water and 50 ml of ethyl acetate were added. The organic phase was then washed, first with concentrated NaHCO₃ and then with brine, dried over Na₂SO₄ and evaporated, leaving a residue (3.97 g). This residue, which is crude tris(4-formylphenyl)phosphane and tris(4-formylphenyl)phosphane oxide (I), was dissolved in 25% CHCl₃/ 75% ethyl acetate and applied to a silica gel column with 25% CHCl₃/ 75% ethyl acetate as the mobile phase. The column was run as a flash column. This process yielded pure tris(4-formylphenyl)phosphane, 1.51 g, 44% yield. Continuing to run the flash column produced pure tris(4-formylphenyl)phosphane oxide (I),1.92 g, 56% yield. Crystals of (I) were prepared by evaporation of a solution in THF over one week.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Numbering scheme and ellipsoids at the 50% level. H atoms are represented with arbitrary radius. Only one orientation of the disordered solvent molecule is shown.

Tris(4-formylphenyl)phosphane oxide tetrahydrofuran hemisolvate top

Crystal data top

C₂₁H₁₅O₄P·0.5C₄H₈O	F(000) = 1664
M_r = 398.35	D_x = 1.385 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7492 reflections
a = 21.371 (3) Å	θ = 2.5–33.7°
b = 13.474 (2) Å	µ = 0.17 mm⁻¹
c = 13.436 (2) Å	T = 110 K
β = 99.018 (9)°	Fragment, yellow
V = 3821.1 (10) Å³	0.45 × 0.43 × 0.38 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	7598 independent reflections
Radiation source: fine-focus sealed tube	5928 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω and ϕ scans	θ_max = 33.7°, θ_min = 3.0°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −33→33
T_min = 0.926, T_max = 0.937	k = −19→21
36155 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0523P)² + 2.5619P] where P = (F_o² + 2F_c²)/3
7598 reflections	(Δ/σ)_max = 0.001
280 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₂₁H₁₅O₄P·0.5C₄H₈O	V = 3821.1 (10) Å³
M_r = 398.35	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.371 (3) Å	µ = 0.17 mm⁻¹
b = 13.474 (2) Å	T = 110 K
c = 13.436 (2) Å	0.45 × 0.43 × 0.38 mm
β = 99.018 (9)°

Data collection top

Nonius KappaCCD diffractometer	7598 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	5928 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.937	R_int = 0.023
36155 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.03	Δρ_max = 0.40 e Å⁻³
7598 reflections	Δρ_min = −0.39 e Å⁻³
280 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
P1	0.328736 (12)	0.285691 (19)	0.269566 (19)	0.01652 (7)
O1	0.27730 (4)	0.35710 (6)	0.23209 (6)	0.02304 (16)
O2	0.58557 (5)	0.58191 (7)	0.41717 (7)	0.0341 (2)
O3	0.21889 (4)	−0.06198 (6)	0.57196 (7)	0.02736 (18)
O4	0.42853 (5)	−0.02731 (8)	−0.07657 (8)	0.0385 (2)
C1	0.40140 (5)	0.34656 (8)	0.32453 (7)	0.01777 (18)
C2	0.40518 (5)	0.44958 (8)	0.31497 (8)	0.02015 (19)
H2	0.3691	0.4861	0.2848	0.024*
C3	0.46164 (5)	0.49869 (8)	0.34949 (8)	0.0224 (2)
H3	0.4643	0.5687	0.3425	0.027*
C4	0.51435 (5)	0.44465 (8)	0.39446 (8)	0.02102 (19)
C5	0.51021 (5)	0.34239 (9)	0.40684 (8)	0.0227 (2)
H5	0.5459	0.3063	0.4393	0.027*
C6	0.45398 (5)	0.29303 (8)	0.37179 (8)	0.0217 (2)
H6	0.4512	0.2232	0.3798	0.026*
C7	0.57583 (6)	0.49462 (10)	0.42927 (9)	0.0268 (2)
H7	0.6096	0.4556	0.4632	0.032*
C8	0.30889 (5)	0.20142 (7)	0.36429 (7)	0.01710 (17)
C9	0.26866 (5)	0.12078 (8)	0.33428 (8)	0.01918 (19)
H9	0.2543	0.1092	0.2647	0.023*
C10	0.24976 (5)	0.05794 (8)	0.40579 (8)	0.01975 (19)
H10	0.2230	0.0029	0.3855	0.024*
C11	0.27051 (5)	0.07641 (8)	0.50828 (8)	0.01879 (18)
C12	0.30915 (5)	0.15758 (8)	0.53806 (8)	0.0211 (2)
H12	0.3223	0.1703	0.6078	0.025*
C13	0.32874 (5)	0.22025 (8)	0.46671 (8)	0.01944 (18)
H13	0.3554	0.2753	0.4873	0.023*
C14	0.25276 (5)	0.01018 (8)	0.58758 (8)	0.0222 (2)
H14	0.2692	0.0255	0.6557	0.027*
C15	0.35007 (5)	0.21019 (7)	0.16835 (7)	0.01758 (18)
C16	0.39073 (5)	0.12789 (8)	0.18493 (8)	0.0216 (2)
H16	0.4074	0.1081	0.2517	0.026*
C17	0.40635 (6)	0.07555 (9)	0.10328 (9)	0.0244 (2)
H17	0.4348	0.0211	0.1141	0.029*
C18	0.38019 (5)	0.10291 (9)	0.00515 (8)	0.0234 (2)
C19	0.34019 (5)	0.18443 (9)	−0.01138 (8)	0.0236 (2)
H19	0.3228	0.2031	−0.0782	0.028*
C20	0.32550 (5)	0.23890 (8)	0.07013 (8)	0.02047 (19)
H20	0.2988	0.2955	0.0588	0.025*
C21	0.39321 (6)	0.04313 (10)	−0.08199 (9)	0.0303 (3)
H21	0.3722	0.0616	−0.1469	0.036*
O1S	0.45041 (11)	0.23429 (19)	0.84831 (19)	0.0494 (6)	0.50
C1S	0.51269 (14)	0.1940 (3)	0.8648 (3)	0.0386 (6)	0.50
H11S	0.5170	0.1448	0.9202	0.058*	0.50
H12S	0.5443	0.2473	0.8831	0.058*	0.50
C2S	0.5231 (3)	0.1445 (4)	0.7670 (3)	0.0762 (15)	0.50
H21S	0.5678	0.1498	0.7565	0.114*	0.50
H22S	0.5104	0.0738	0.7652	0.114*	0.50
C3S	0.4797 (3)	0.2050 (3)	0.6906 (4)	0.0720 (16)	0.50
H31S	0.5012	0.2656	0.6715	0.108*	0.50
H32S	0.4648	0.1657	0.6292	0.108*	0.50
C4S	0.4278 (2)	0.2296 (4)	0.7434 (3)	0.0701 (14)	0.50
H41S	0.4094	0.2944	0.7196	0.105*	0.50
H42S	0.3943	0.1786	0.7298	0.105*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.01646 (12)	0.01632 (11)	0.01603 (11)	0.00020 (9)	0.00027 (8)	−0.00027 (9)
O1	0.0221 (4)	0.0220 (4)	0.0238 (4)	0.0043 (3)	−0.0003 (3)	0.0014 (3)
O2	0.0340 (5)	0.0338 (5)	0.0348 (5)	−0.0149 (4)	0.0062 (4)	−0.0057 (4)
O3	0.0300 (4)	0.0246 (4)	0.0285 (4)	−0.0029 (3)	0.0075 (3)	0.0020 (3)
O4	0.0330 (5)	0.0477 (6)	0.0363 (5)	−0.0048 (4)	0.0103 (4)	−0.0206 (4)
C1	0.0174 (4)	0.0189 (4)	0.0169 (4)	−0.0015 (3)	0.0024 (3)	−0.0020 (3)
C2	0.0220 (5)	0.0203 (4)	0.0182 (4)	−0.0007 (4)	0.0032 (3)	0.0007 (4)
C3	0.0260 (5)	0.0209 (5)	0.0209 (4)	−0.0049 (4)	0.0050 (4)	−0.0006 (4)
C4	0.0196 (5)	0.0259 (5)	0.0183 (4)	−0.0045 (4)	0.0052 (3)	−0.0043 (4)
C5	0.0176 (5)	0.0259 (5)	0.0244 (5)	0.0008 (4)	0.0021 (4)	−0.0037 (4)
C6	0.0201 (5)	0.0197 (5)	0.0249 (5)	0.0004 (4)	0.0015 (4)	−0.0024 (4)
C7	0.0223 (5)	0.0335 (6)	0.0253 (5)	−0.0075 (4)	0.0059 (4)	−0.0076 (5)
C8	0.0164 (4)	0.0176 (4)	0.0172 (4)	0.0005 (3)	0.0021 (3)	−0.0003 (3)
C9	0.0196 (5)	0.0209 (4)	0.0166 (4)	−0.0014 (4)	0.0014 (3)	−0.0033 (3)
C10	0.0193 (4)	0.0190 (4)	0.0210 (4)	−0.0022 (4)	0.0035 (3)	−0.0027 (4)
C11	0.0202 (4)	0.0177 (4)	0.0190 (4)	0.0018 (3)	0.0049 (3)	−0.0010 (3)
C12	0.0251 (5)	0.0215 (5)	0.0162 (4)	−0.0001 (4)	0.0017 (4)	−0.0019 (3)
C13	0.0208 (5)	0.0186 (4)	0.0182 (4)	−0.0019 (4)	0.0008 (3)	−0.0025 (3)
C14	0.0263 (5)	0.0210 (5)	0.0206 (5)	0.0026 (4)	0.0076 (4)	−0.0006 (4)
C15	0.0177 (4)	0.0187 (4)	0.0159 (4)	−0.0024 (3)	0.0012 (3)	−0.0008 (3)
C16	0.0242 (5)	0.0221 (5)	0.0180 (4)	0.0012 (4)	0.0012 (4)	−0.0007 (4)
C17	0.0242 (5)	0.0250 (5)	0.0239 (5)	0.0005 (4)	0.0037 (4)	−0.0053 (4)
C18	0.0229 (5)	0.0287 (5)	0.0192 (4)	−0.0076 (4)	0.0053 (4)	−0.0064 (4)
C19	0.0231 (5)	0.0311 (5)	0.0160 (4)	−0.0066 (4)	0.0009 (4)	−0.0004 (4)
C20	0.0197 (4)	0.0230 (5)	0.0177 (4)	−0.0028 (4)	−0.0001 (3)	0.0013 (4)
C21	0.0289 (6)	0.0398 (7)	0.0235 (5)	−0.0105 (5)	0.0086 (4)	−0.0111 (5)
O1S	0.0330 (11)	0.0568 (14)	0.0539 (14)	−0.0007 (10)	−0.0072 (10)	0.0064 (11)
C1S	0.0297 (13)	0.0431 (17)	0.0399 (16)	−0.0004 (11)	−0.0043 (12)	−0.0067 (14)
C2S	0.107 (5)	0.078 (3)	0.039 (2)	0.021 (3)	0.001 (2)	−0.008 (2)
C3S	0.128 (5)	0.0307 (17)	0.046 (2)	−0.003 (2)	−0.022 (3)	0.0030 (17)
C4S	0.070 (3)	0.078 (3)	0.050 (2)	−0.030 (2)	−0.0275 (19)	0.036 (2)

Geometric parameters (Å, º) top

P1—O1	1.4880 (8)	C12—H12	0.9500
P1—C8	1.8050 (10)	C13—H13	0.9500
P1—C1	1.8083 (11)	C14—H14	0.9500
P1—C15	1.8129 (10)	C15—C20	1.3963 (14)
O2—C7	1.2099 (16)	C15—C16	1.4050 (15)
O3—C14	1.2107 (14)	C16—C17	1.3882 (15)
O4—C21	1.2078 (17)	C16—H16	0.9500
C1—C2	1.3975 (15)	C17—C18	1.3984 (16)
C1—C6	1.4009 (15)	C17—H17	0.9500
C2—C3	1.3905 (15)	C18—C19	1.3881 (17)
C2—H2	0.9500	C18—C21	1.4830 (16)
C3—C4	1.3968 (16)	C19—C20	1.3944 (15)
C3—H3	0.9500	C19—H19	0.9500
C4—C5	1.3924 (16)	C20—H20	0.9500
C4—C7	1.4851 (15)	C21—H21	0.9500
C5—C6	1.3895 (15)	O1S—C4S	1.418 (4)
C5—H5	0.9500	O1S—C1S	1.422 (4)
C6—H6	0.9500	C1S—C2S	1.519 (5)
C7—H7	0.9500	C1S—H11S	0.9900
C8—C13	1.3981 (14)	C1S—H12S	0.9900
C8—C9	1.4049 (14)	C2S—C3S	1.510 (6)
C9—C10	1.3873 (15)	C2S—H21S	0.9900
C9—H9	0.9500	C2S—H22S	0.9900
C10—C11	1.4013 (14)	C3S—C4S	1.446 (8)
C10—H10	0.9500	C3S—H31S	0.9900
C11—C12	1.3909 (15)	C3S—H32S	0.9900
C11—C14	1.4839 (15)	C4S—H41S	0.9900
C12—C13	1.3904 (15)	C4S—H42S	0.9900

O1—P1—C8	113.74 (5)	C11—C14—H14	117.6
O1—P1—C1	112.73 (5)	C20—C15—C16	120.01 (10)
C8—P1—C1	106.20 (5)	C20—C15—P1	116.88 (8)
O1—P1—C15	111.61 (5)	C16—C15—P1	123.09 (8)
C8—P1—C15	106.89 (5)	C17—C16—C15	119.67 (10)
C1—P1—C15	105.07 (5)	C17—C16—H16	120.2
C2—C1—C6	119.95 (10)	C15—C16—H16	120.2
C2—C1—P1	118.12 (8)	C16—C17—C18	120.06 (11)
C6—C1—P1	121.87 (8)	C16—C17—H17	120.0
C3—C2—C1	120.11 (10)	C18—C17—H17	120.0
C3—C2—H2	119.9	C19—C18—C17	120.31 (10)
C1—C2—H2	119.9	C19—C18—C21	119.37 (11)
C2—C3—C4	119.68 (10)	C17—C18—C21	120.29 (11)
C2—C3—H3	120.2	C18—C19—C20	119.97 (10)
C4—C3—H3	120.2	C18—C19—H19	120.0
C5—C4—C3	120.36 (10)	C20—C19—H19	120.0
C5—C4—C7	118.73 (11)	C19—C20—C15	119.93 (10)
C3—C4—C7	120.91 (10)	C19—C20—H20	120.0
C6—C5—C4	120.07 (10)	C15—C20—H20	120.0
C6—C5—H5	120.0	O4—C21—C18	124.90 (12)
C4—C5—H5	120.0	O4—C21—H21	117.6
C5—C6—C1	119.79 (10)	C18—C21—H21	117.6
C5—C6—H6	120.1	C4S—O1S—C1S	107.6 (3)
C1—C6—H6	120.1	O1S—C1S—C2S	107.0 (3)
O2—C7—C4	124.11 (12)	O1S—C1S—H11S	110.3
O2—C7—H7	117.9	C2S—C1S—H11S	110.3
C4—C7—H7	117.9	O1S—C1S—H12S	110.3
C13—C8—C9	120.03 (9)	C2S—C1S—H12S	110.3
C13—C8—P1	120.75 (8)	H11S—C1S—H12S	108.6
C9—C8—P1	119.01 (7)	C3S—C2S—C1S	101.2 (4)
C10—C9—C8	120.31 (9)	C3S—C2S—H21S	111.5
C10—C9—H9	119.8	C1S—C2S—H21S	111.5
C8—C9—H9	119.8	C3S—C2S—H22S	111.5
C9—C10—C11	119.38 (10)	C1S—C2S—H22S	111.5
C9—C10—H10	120.3	H21S—C2S—H22S	109.4
C11—C10—H10	120.3	C4S—C3S—C2S	103.1 (4)
C12—C11—C10	120.30 (10)	C4S—C3S—H31S	111.2
C12—C11—C14	118.26 (9)	C2S—C3S—H31S	111.2
C10—C11—C14	121.44 (10)	C4S—C3S—H32S	111.2
C13—C12—C11	120.57 (9)	C2S—C3S—H32S	111.2
C13—C12—H12	119.7	H31S—C3S—H32S	109.1
C11—C12—H12	119.7	O1S—C4S—C3S	109.3 (3)
C12—C13—C8	119.39 (10)	O1S—C4S—H41S	109.8
C12—C13—H13	120.3	C3S—C4S—H41S	109.8
C8—C13—H13	120.3	O1S—C4S—H42S	109.8
O3—C14—C11	124.87 (10)	C3S—C4S—H42S	109.8
O3—C14—H14	117.6	H41S—C4S—H42S	108.3

O1—P1—C1—C2	−8.16 (10)	C14—C11—C12—C13	178.05 (10)
C8—P1—C1—C2	−133.35 (8)	C11—C12—C13—C8	0.44 (16)
C15—P1—C1—C2	113.60 (9)	C9—C8—C13—C12	1.05 (16)
O1—P1—C1—C6	174.63 (8)	P1—C8—C13—C12	175.71 (8)
C8—P1—C1—C6	49.43 (10)	C12—C11—C14—O3	179.01 (11)
C15—P1—C1—C6	−63.62 (10)	C10—C11—C14—O3	−1.64 (17)
C6—C1—C2—C3	1.99 (16)	O1—P1—C15—C20	11.07 (10)
P1—C1—C2—C3	−175.28 (8)	C8—P1—C15—C20	136.02 (8)
C1—C2—C3—C4	−0.51 (15)	C1—P1—C15—C20	−111.41 (9)
C2—C3—C4—C5	−1.42 (16)	O1—P1—C15—C16	−170.73 (9)
C2—C3—C4—C7	178.15 (10)	C8—P1—C15—C16	−45.78 (10)
C3—C4—C5—C6	1.87 (16)	C1—P1—C15—C16	66.79 (10)
C7—C4—C5—C6	−177.70 (10)	C20—C15—C16—C17	0.10 (16)
C4—C5—C6—C1	−0.39 (16)	P1—C15—C16—C17	−178.04 (8)
C2—C1—C6—C5	−1.54 (16)	C15—C16—C17—C18	−1.91 (17)
P1—C1—C6—C5	175.63 (8)	C16—C17—C18—C19	2.16 (17)
C5—C4—C7—O2	175.74 (11)	C16—C17—C18—C21	−175.80 (11)
C3—C4—C7—O2	−3.83 (17)	C17—C18—C19—C20	−0.57 (17)
O1—P1—C8—C13	−97.60 (9)	C21—C18—C19—C20	177.40 (10)
C1—P1—C8—C13	26.97 (10)	C18—C19—C20—C15	−1.24 (16)
C15—P1—C8—C13	138.76 (9)	C16—C15—C20—C19	1.48 (16)
O1—P1—C8—C9	77.11 (9)	P1—C15—C20—C19	179.73 (8)
C1—P1—C8—C9	−158.32 (8)	C19—C18—C21—O4	177.78 (12)
C15—P1—C8—C9	−46.53 (9)	C17—C18—C21—O4	−4.24 (19)
C13—C8—C9—C10	−1.68 (16)	C4S—O1S—C1S—C2S	−11.3 (4)
P1—C8—C9—C10	−176.43 (8)	O1S—C1S—C2S—C3S	28.0 (4)
C8—C9—C10—C11	0.82 (16)	C1S—C2S—C3S—C4S	−33.6 (5)
C9—C10—C11—C12	0.67 (16)	C1S—O1S—C4S—C3S	−11.4 (4)
C9—C10—C11—C14	−178.66 (10)	C2S—C3S—C4S—O1S	29.0 (5)
C10—C11—C12—C13	−1.31 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.95	2.56	3.4303 (16)	152
C14—H14···O1ⁱⁱ	0.95	2.50	3.1575 (14)	127

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.95	2.56	3.4303 (16)	152
C14—H14···O1ⁱⁱ	0.95	2.50	3.1575 (14)	127

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

Footnotes

‡Current address: Natural Science Department, Clearwater Campus, St Petersburg College, PO Box 13489, St Petersburg, FL 33733-3489, USA.

Acknowledgements

The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents. This work was supported in part by the US Department of Energy (DE—FG02–01ER15267).

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