Crystal structure of zwitterionic 2-[bis-(2-meth-oxy-phen-yl)phosphanium-yl]-4-methyl-benzene-sulfonate monohydrate di-chloro-methane monosolvate.

In the title compound, C21H21O5PS·H2O·CH2Cl2, the phospho-nium-sulfonate zwitterion has the acidic H atom located on the P atom rather than the sulfonate group. The S-O bond lengths [1.4453 (15)-1.4521 (14) Å] are essentially equal. In the crystal, the water mol-ecules bridge two zwitterions via Owater-H⋯Osulfonate hydrogen bonds into a centrosymmetric dimer. The dimers are further linked by weak CAr-yl-H⋯Osulfonate hydrogen bonds into chains extending along [100]. The PH(+) group is not involved in inter-molecular inter-actions.

Chemical context

Phosphane ligands (Allen, 2014 ▸) are ubiquitous in coordination and organometallic chemistry and have been used to synthesize a wide variety of metal complexes and catalysts (Hartwig, 2010 ▸). Incorporation of additional potential donor groups within the phosphane structure provides added versatility to such ligands. For example, ortho-phosphanyl-benzene­sulfonate (PO) ligands, such as 2-[bis­(2-meth­oxy­phen­yl)phosphanyl]benzene­sulfonate, bind to PdII in a κ2 P,O mode to form (PO)PdR species that are active for the polymerization of ethyl­ene (Cai et al., 2012 ▸; Contrella & Jordan, 2014 ▸; Zhou et al., 2014 ▸), copolymerization of ethyl­ene and polar monomers (Drent et al., 2002 Nakamura et al., 2013 ▸), non-alternating copolymerization of ethyl­ene and CO (Drent et al., 2002b ▸), and alternating copolymerization of CO with polar monomers (Nakamura et al., 2011 ▸, 2012 ▸). Phosphanyl-arene­sulfonate ligands derived from para-toluene­sulfonic acid are useful because the extra methyl group provides a convenient NMR handle for characterizing complexes and monitoring reactions.

The zwitterion 2-[bis­(2-meth­oxy­phen­yl)phosphanium­yl]-4-methyl­benzene­sulfonate (1, Scheme 1) was synthesized by sequential reaction of PCl3 with dili­thia­ted p-tol­uene­sulfonate and 1-li­thio-2-meth­oxy­benzene, followed by acidification of HCl (Scheme 2) (Vela et al., 2007 ▸). Here we report the crystal structure of 1·H2O·CH2Cl2, (I).

Structural commentary

Compound 1 crystallizes as the phospho­nium–sulfonate zwitterion in which the acidic H atom is located on the P atom rather than the sulfonate group (Fig. 1 ▸). The S—O bond distances fall within the narrow range of 1.4453 (15) to 1.4521 (14) Å, and the P—C distances lie within the range of 1.7794 (18) to 1.7984 (18) Å. The P—H atom was located in a difference Fourier map and refined without additional restraints. The P—H bond length is 1.22 (2) Å. Compound 1 adopts an exo 3 conformation, i.e. the ortho meth­oxy and sulfonate groups point toward the PH+ group (Feng et al., 2014 ▸). Tris(ortho-substituted ar­yl)phosphanes normally exhibit exo 3 conformations (Howell et al., 1999 ▸) because the ortho substituents cause less steric congestion when they point toward the P lone pair (exo) rather than toward the other aryl rings (endo). Addition of an H+ at phospho­rous should not add significant steric congestion and therefore it is not surprising that 1 also adopts the exo 3 conformation. The Ometh­oxy⋯P distances, 2.7691 (14) and 2.7940 (14) Å, are shorter than the sum of the O and P van der Waals radii (3.35 Å). The O3⋯H1(P1) distance is 2.44 (2) Å.

Figure 1

The mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The dashed line denotes a hydrogen bond.

DFT calculations

The relative stability of the observed exo 3 conformation versus alternative exo 2 and exo 1 conformations was investigated by DFT calculations using the hybrid exchange-correlation functional PBE0 (Perdew et al., 1996 ▸, 1997 ▸) and the 6-311G(d,p) basis set for all atoms. The optimized structure is the exo 3 conformer, in which the meth­oxy and sulfonate groups point toward the PH+ group. Geometry optimizations were also carried out on two conformers in which the SO3 group was kept exo but one (exo 2) or two (exo 1) meth­oxy groups were rotated away from the PH+ group. The exo 2 and exo 1 conformers were calculated to be 1.2 and 2.5 kcal mol−1 less stable than the exo 3 isomer, respectively. The HOMO of the exo 3 conformer is comprised of p orbitals of the sulfonate O atoms, while the LUMO is delocalized over the phenyl rings and P—Caromatic bonds (Fig. 2 ▸).

Figure 2

HOMO (−0.2289 Hartrees, left) and LUMO (−0.0483 Hartrees, right) orbitals of 1.

Supra­molecular features

Two O atoms of the SO3 − group are hydrogen bonded with the co-crystallized water mol­ecule, forming inversion dimers (Fig. 3 ▸). The Owater—H⋯Osulfonate contacts are 1.96 (3) and 1.98 (3) Å (Table 1 ▸). These dimers are further linked by CAryl—H⋯Osulfonate hydrogen bonds into infinite chains running along the [100] direction (Fig. 4 ▸). A similar CAr–SO3 −⋯H2O⋯CAr–SO3 −⋯H2O⋯ hydrogen-bonding motif was observed in [Na(18-crown-6)(H2O)][2-{(o-CF3-Ph)2P}-4-Me-benzene­sulfonate] (Feng et al., 2014 ▸).

Figure 3

Dimer formation through Owater—H⋯Osulfonate hydrogen bonds (dashed lines).

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H1O⋯O1	0.91 (3)	1.96 (3)	2.862 (2)	170 (3)
O6—H2O⋯O2i	0.92 (3)	1.98 (3)	2.877 (2)	164 (3)
C19—H19⋯O3ii	0.95	2.47	3.180 (2)	132

Symmetry codes: (i) ; (ii) .

Figure 4

A fragment of the crystal packing of the title compound with inter­molecular hydrogen bonds shown as dashed light-blue lines. Color scheme: C grey, H white, O red, P orange, S yellow.

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.36, last update May 2015; Groom & Allen, 2014 ▸) revealed structural reports for two analogues of 1 that contain 4-chloro-substituted meth­oxy­phenyl (CSD refcode ODUNOS; Wucher et al., 2013 ▸) or 2,6-di­meth­oxy­phenyl substituents at phospho­rous (CSD refcode: LEXLEG; Liu et al., 2007 ▸). These compounds also crystallized as zwitterions in which the acidic proton is located on the P atom and feature close Ometh­oxy⋯P contacts (2.764 to 2.927 Å). The structure of the tri­ethyl­ammonium salt of 2-[bis­(2-meth­oxy­phen­yl)phos­phanyl]benzene­sulfonate has also been reported (CSD refcode HAGKEH; Bettucci et al., 2008 ▸). In this case, the acidic H atom is located at tri­ethyl­amine rather than on the P atom and the Ometh­oxy⋯P distances are 2.877 and 2.903 Å.

Synthesis and crystallization

Compound 1 was synthesized by a modification of a previously reported procedure (Vela et al., 2007 ▸) comprising sequential reaction of PCl3 with dili­thia­ted p-toluene­sulfonate and 1-li­thio-2-meth­oxy­benzene, followed by acidification of HCl, to afford 1 in 70–75% yield on a 3–4 g scale (Scheme 2). The product was purified by recrystallization (CH2Cl2/Et2O, volume ratio 1/3, layering at 273K). Crystals of 1·H2O·CH2Cl2 (I) suitable for the X-ray diffraction analysis were obtained by layering Et2O on a CH2Cl2 solution of 1 at 277 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding-model approximation, with U iso(H) set to 1.2–1.5U eq(C). The P- and O-bound H atoms were located in a difference Fourier map and refined isotropically.

Table 2

Experimental details

Crystal data
Chemical formula	C21H21O5PS·CH2Cl2·H2O
M r	519.35
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	100
a, b, c (Å)	9.6437 (6), 15.9441 (11), 15.9641 (11)
β (°)	105.051 (2)
V (Å3)	2370.4 (3)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.47
Crystal size (mm)	0.32 × 0.18 × 0.12
Data collection
Diffractometer	Bruker D8 Venture PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.693, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	53574, 4888, 4349
R int	0.030
(sin θ/λ)max (Å−1)	0.627
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.106, 1.05
No. of reflections	4888
No. of parameters	304
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.48, −0.66

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), OLEX2 (Dolomanov et al., 2009 ▸), Mercury (Macrae et al., 2008 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016000669/cv5502sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016000669/cv5502Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989016000669/cv5502Isup3.cml

CCDC reference: 1447138

Additional supporting information: crystallographic information; 3D view; checkCIF report

C21H21O5PS·CH2Cl2·H2O	F(000) = 1080
Mr = 519.35	Dx = 1.455 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.6437 (6) Å	Cell parameters from 9610 reflections
b = 15.9441 (11) Å	θ = 2.2–26.4°
c = 15.9641 (11) Å	µ = 0.47 mm−1
β = 105.051 (2)°	T = 100 K
V = 2370.4 (3) Å3	Block, colorless
Z = 4	0.32 × 0.18 × 0.12 mm

Bruker D8 Venture PHOTON 100 CMOS diffractometer	4888 independent reflections
Radiation source: INCOATEC ImuS micro-focus source	4349 reflections with I > 2σ(I)
Mirrors monochromator	Rint = 0.030
Detector resolution: 10.4167 pixels mm-1	θmax = 26.5°, θmin = 2.2°
ω and phi scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −19→19
Tmin = 0.693, Tmax = 0.745	l = −20→19
53574 measured reflections

Refinement on F2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038	Hydrogen site location: mixed
wR(F2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0536P)2 + 2.7024P] where P = (Fo2 + 2Fc2)/3
4888 reflections	(Δ/σ)max = 0.001
304 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.66 e Å−3

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.

	x	y	z	Uiso*/Ueq
P1	0.63863 (5)	0.30456 (3)	0.33309 (3)	0.01288 (12)
H1P	0.592 (2)	0.2397 (14)	0.2950 (14)	0.018 (5)*
S1	0.43769 (5)	0.17697 (3)	0.41453 (3)	0.01702 (12)
O1	0.50338 (15)	0.10620 (9)	0.38266 (10)	0.0261 (3)
O2	0.34252 (15)	0.15453 (10)	0.46751 (10)	0.0269 (3)
O3	0.37411 (14)	0.23600 (9)	0.34604 (9)	0.0210 (3)
O4	0.86431 (15)	0.19197 (8)	0.35798 (9)	0.0210 (3)
O5	0.51406 (15)	0.34403 (9)	0.15930 (8)	0.0206 (3)
C1	0.77958 (19)	0.33171 (11)	0.50245 (12)	0.0155 (4)
H1	0.8372	0.3678	0.4781	0.019*
C2	0.66711 (19)	0.28789 (11)	0.44773 (11)	0.0139 (3)
C3	0.58188 (19)	0.23434 (11)	0.48294 (12)	0.0155 (4)
C4	0.6117 (2)	0.22566 (12)	0.57215 (12)	0.0188 (4)
H4	0.5552	0.1890	0.5966	0.023*
C5	0.7235 (2)	0.27025 (12)	0.62605 (12)	0.0187 (4)
H5	0.7417	0.2642	0.6871	0.022*
C6	0.8093 (2)	0.32358 (12)	0.59237 (12)	0.0170 (4)
C7	0.9324 (2)	0.37081 (13)	0.65044 (13)	0.0227 (4)
H7A	0.9220	0.3708	0.7099	0.034*
H7B	0.9323	0.4287	0.6299	0.034*
H7C	1.0231	0.3437	0.6493	0.034*
C8	0.51505 (19)	0.38810 (11)	0.29746 (12)	0.0159 (4)
C9	0.4711 (2)	0.44064 (12)	0.35526 (13)	0.0202 (4)
H9	0.5089	0.4336	0.4160	0.024*
C10	0.3720 (2)	0.50321 (13)	0.32356 (14)	0.0239 (4)
H10	0.3426	0.5402	0.3624	0.029*
C11	0.3158 (2)	0.51167 (13)	0.23483 (15)	0.0246 (4)
H11	0.2461	0.5540	0.2136	0.030*
C12	0.3583 (2)	0.46027 (12)	0.17634 (13)	0.0209 (4)
H12	0.3185	0.4670	0.1157	0.025*
C13	0.46023 (19)	0.39848 (12)	0.20784 (12)	0.0173 (4)
C14	0.4860 (2)	0.36077 (14)	0.06819 (13)	0.0261 (4)
H14A	0.3827	0.3561	0.0413	0.039*
H14B	0.5378	0.3201	0.0416	0.039*
H14C	0.5184	0.4176	0.0595	0.039*
C15	0.80656 (19)	0.32846 (12)	0.31142 (11)	0.0152 (4)
C16	0.8366 (2)	0.40458 (12)	0.27736 (12)	0.0192 (4)
H16	0.7672	0.4482	0.2665	0.023*
C17	0.9686 (2)	0.41647 (13)	0.25930 (13)	0.0224 (4)
H17	0.9894	0.4678	0.2349	0.027*
C18	1.0697 (2)	0.35248 (13)	0.27735 (13)	0.0226 (4)
H18	1.1612	0.3615	0.2670	0.027*
C19	1.0407 (2)	0.27600 (13)	0.30998 (13)	0.0208 (4)
H19	1.1106	0.2326	0.3208	0.025*
C20	0.9083 (2)	0.26368 (12)	0.32663 (12)	0.0173 (4)
C21	0.9467 (2)	0.11736 (13)	0.35617 (14)	0.0258 (4)
H21A	0.9509	0.1062	0.2965	0.039*
H21B	0.9012	0.0699	0.3775	0.039*
H21C	1.0442	0.1251	0.3932	0.039*
C22	0.2653 (5)	0.3457 (2)	0.5203 (2)	0.0676 (11)
H22A	0.2056	0.3047	0.4801	0.081*
H22B	0.3569	0.3518	0.5038	0.081*
Cl1	0.30192 (7)	0.30568 (5)	0.62409 (4)	0.04587 (19)
Cl2	0.17791 (9)	0.44136 (4)	0.50619 (5)	0.0517 (2)
O6	0.73753 (17)	−0.00322 (11)	0.45863 (11)	0.0308 (4)
H1O	0.656 (4)	0.027 (2)	0.436 (2)	0.049 (8)*
H2O	0.701 (3)	−0.053 (2)	0.4720 (19)	0.043 (8)*

	U11	U22	U33	U12	U13	U23
P1	0.0121 (2)	0.0138 (2)	0.0124 (2)	0.00178 (16)	0.00263 (17)	0.00083 (16)
S1	0.0143 (2)	0.0180 (2)	0.0173 (2)	−0.00200 (17)	0.00148 (17)	0.00157 (17)
O1	0.0245 (7)	0.0214 (7)	0.0283 (8)	0.0011 (6)	−0.0007 (6)	−0.0049 (6)
O2	0.0227 (7)	0.0324 (8)	0.0255 (8)	−0.0092 (6)	0.0062 (6)	0.0041 (6)
O3	0.0141 (6)	0.0255 (7)	0.0207 (7)	−0.0009 (5)	−0.0003 (5)	0.0048 (6)
O4	0.0217 (7)	0.0174 (7)	0.0268 (7)	0.0068 (5)	0.0115 (6)	0.0045 (5)
O5	0.0244 (7)	0.0213 (7)	0.0148 (7)	0.0010 (6)	0.0027 (5)	0.0006 (5)
C1	0.0151 (8)	0.0143 (8)	0.0173 (9)	0.0025 (7)	0.0044 (7)	−0.0010 (7)
C2	0.0147 (8)	0.0138 (8)	0.0134 (8)	0.0043 (7)	0.0043 (7)	0.0012 (7)
C3	0.0137 (8)	0.0159 (9)	0.0162 (9)	0.0026 (7)	0.0025 (7)	0.0006 (7)
C4	0.0182 (9)	0.0209 (9)	0.0179 (9)	0.0014 (7)	0.0058 (7)	0.0035 (7)
C5	0.0213 (9)	0.0210 (9)	0.0139 (9)	0.0045 (7)	0.0047 (7)	0.0015 (7)
C6	0.0160 (9)	0.0168 (9)	0.0173 (9)	0.0047 (7)	0.0026 (7)	−0.0020 (7)
C7	0.0234 (10)	0.0239 (10)	0.0186 (9)	−0.0010 (8)	0.0017 (8)	−0.0030 (8)
C8	0.0123 (8)	0.0153 (9)	0.0198 (9)	0.0020 (7)	0.0038 (7)	0.0036 (7)
C9	0.0198 (9)	0.0202 (10)	0.0211 (9)	0.0029 (7)	0.0063 (8)	0.0025 (7)
C10	0.0229 (10)	0.0199 (10)	0.0323 (11)	0.0051 (8)	0.0131 (9)	0.0028 (8)
C11	0.0159 (9)	0.0206 (10)	0.0381 (12)	0.0039 (7)	0.0080 (8)	0.0117 (9)
C12	0.0162 (9)	0.0209 (9)	0.0229 (10)	−0.0024 (7)	0.0002 (7)	0.0093 (8)
C13	0.0133 (8)	0.0172 (9)	0.0211 (9)	−0.0029 (7)	0.0039 (7)	0.0027 (7)
C14	0.0339 (11)	0.0273 (11)	0.0166 (9)	−0.0028 (9)	0.0055 (8)	0.0023 (8)
C15	0.0136 (8)	0.0191 (9)	0.0131 (8)	−0.0004 (7)	0.0037 (7)	−0.0023 (7)
C16	0.0199 (9)	0.0189 (9)	0.0183 (9)	−0.0006 (7)	0.0040 (7)	−0.0011 (7)
C17	0.0247 (10)	0.0223 (10)	0.0213 (10)	−0.0082 (8)	0.0077 (8)	−0.0020 (8)
C18	0.0170 (9)	0.0303 (11)	0.0221 (10)	−0.0056 (8)	0.0083 (8)	−0.0079 (8)
C19	0.0158 (9)	0.0272 (10)	0.0196 (9)	0.0025 (8)	0.0049 (7)	−0.0045 (8)
C20	0.0183 (9)	0.0196 (9)	0.0140 (8)	−0.0001 (7)	0.0042 (7)	−0.0015 (7)
C21	0.0311 (11)	0.0198 (10)	0.0289 (11)	0.0109 (8)	0.0117 (9)	0.0024 (8)
C22	0.126 (3)	0.0495 (18)	0.0368 (15)	0.043 (2)	0.0374 (19)	0.0161 (13)
Cl1	0.0453 (4)	0.0621 (4)	0.0305 (3)	0.0225 (3)	0.0103 (3)	0.0118 (3)
Cl2	0.0798 (5)	0.0347 (3)	0.0452 (4)	0.0190 (3)	0.0245 (4)	0.0098 (3)
O6	0.0241 (8)	0.0272 (8)	0.0389 (9)	−0.0020 (7)	0.0040 (7)	0.0056 (7)

P1—C8	1.7794 (18)	C10—C11	1.386 (3)
P1—C15	1.7828 (18)	C10—H10	0.9500
P1—C2	1.7984 (18)	C11—C12	1.382 (3)
P1—H1P	1.22 (2)	C11—H11	0.9500
S1—O2	1.4453 (15)	C12—C13	1.390 (3)
S1—O1	1.4495 (15)	C12—H12	0.9500
S1—O3	1.4521 (14)	C14—H14A	0.9800
S1—C3	1.7816 (19)	C14—H14B	0.9800
O4—C20	1.359 (2)	C14—H14C	0.9800
O4—C21	1.435 (2)	C15—C16	1.391 (3)
O5—C13	1.354 (2)	C15—C20	1.402 (3)
O5—C14	1.434 (2)	C16—C17	1.389 (3)
C1—C2	1.391 (3)	C16—H16	0.9500
C1—C6	1.395 (3)	C17—C18	1.389 (3)
C1—H1	0.9500	C17—H17	0.9500
C2—C3	1.400 (3)	C18—C19	1.383 (3)
C3—C4	1.385 (3)	C18—H18	0.9500
C4—C5	1.388 (3)	C19—C20	1.384 (3)
C4—H4	0.9500	C19—H19	0.9500
C5—C6	1.388 (3)	C21—H21A	0.9800
C5—H5	0.9500	C21—H21B	0.9800
C6—C7	1.505 (3)	C21—H21C	0.9800
C7—H7A	0.9800	C22—Cl1	1.725 (3)
C7—H7B	0.9800	C22—Cl2	1.728 (3)
C7—H7C	0.9800	C22—H22A	0.9900
C8—C9	1.391 (3)	C22—H22B	0.9900
C8—C13	1.400 (3)	O6—H1O	0.91 (3)
C9—C10	1.384 (3)	O6—H2O	0.92 (3)
C9—H9	0.9500
C8—P1—C15	110.16 (9)	C12—C11—C10	121.81 (18)
C8—P1—C2	110.40 (8)	C12—C11—H11	119.1
C15—P1—C2	108.82 (8)	C10—C11—H11	119.1
C8—P1—H1P	110.0 (10)	C11—C12—C13	118.80 (18)
C15—P1—H1P	108.8 (10)	C11—C12—H12	120.6
C2—P1—H1P	108.6 (10)	C13—C12—H12	120.6
O2—S1—O1	114.48 (9)	O5—C13—C12	125.99 (18)
O2—S1—O3	113.14 (9)	O5—C13—C8	114.20 (16)
O1—S1—O3	112.20 (9)	C12—C13—C8	119.81 (18)
O2—S1—C3	106.35 (9)	O5—C14—H14A	109.5
O1—S1—C3	105.80 (8)	O5—C14—H14B	109.5
O3—S1—C3	103.80 (8)	H14A—C14—H14B	109.5
C20—O4—C21	117.55 (15)	O5—C14—H14C	109.5
C13—O5—C14	117.51 (15)	H14A—C14—H14C	109.5
C2—C1—C6	121.17 (17)	H14B—C14—H14C	109.5
C2—C1—H1	119.4	C16—C15—C20	120.20 (17)
C6—C1—H1	119.4	C16—C15—P1	123.67 (14)
C1—C2—C3	119.83 (17)	C20—C15—P1	116.05 (14)
C1—C2—P1	116.93 (14)	C17—C16—C15	119.71 (18)
C3—C2—P1	123.24 (14)	C17—C16—H16	120.1
C4—C3—C2	119.16 (17)	C15—C16—H16	120.1
C4—C3—S1	119.96 (14)	C16—C17—C18	119.23 (19)
C2—C3—S1	120.87 (14)	C16—C17—H17	120.4
C3—C4—C5	120.43 (18)	C18—C17—H17	120.4
C3—C4—H4	119.8	C19—C18—C17	121.78 (18)
C5—C4—H4	119.8	C19—C18—H18	119.1
C6—C5—C4	121.25 (17)	C17—C18—H18	119.1
C6—C5—H5	119.4	C18—C19—C20	118.94 (18)
C4—C5—H5	119.4	C18—C19—H19	120.5
C5—C6—C1	118.16 (17)	C20—C19—H19	120.5
C5—C6—C7	121.47 (17)	O4—C20—C19	125.57 (18)
C1—C6—C7	120.37 (17)	O4—C20—C15	114.34 (16)
C6—C7—H7A	109.5	C19—C20—C15	120.09 (18)
C6—C7—H7B	109.5	O4—C21—H21A	109.5
H7A—C7—H7B	109.5	O4—C21—H21B	109.5
C6—C7—H7C	109.5	H21A—C21—H21B	109.5
H7A—C7—H7C	109.5	O4—C21—H21C	109.5
H7B—C7—H7C	109.5	H21A—C21—H21C	109.5
C9—C8—C13	120.48 (17)	H21B—C21—H21C	109.5
C9—C8—P1	122.19 (15)	Cl1—C22—Cl2	115.01 (17)
C13—C8—P1	117.32 (14)	Cl1—C22—H22A	108.5
C10—C9—C8	119.47 (19)	Cl2—C22—H22A	108.5
C10—C9—H9	120.3	Cl1—C22—H22B	108.5
C8—C9—H9	120.3	Cl2—C22—H22B	108.5
C9—C10—C11	119.59 (19)	H22A—C22—H22B	107.5
C9—C10—H10	120.2	H1O—O6—H2O	102 (3)
C11—C10—H10	120.2
C6—C1—C2—C3	−0.2 (3)	C8—C9—C10—C11	1.2 (3)
C6—C1—C2—P1	179.37 (14)	C9—C10—C11—C12	−1.4 (3)
C8—P1—C2—C1	−91.04 (15)	C10—C11—C12—C13	0.0 (3)
C15—P1—C2—C1	29.98 (16)	C14—O5—C13—C12	12.9 (3)
C8—P1—C2—C3	88.50 (16)	C14—O5—C13—C8	−167.84 (16)
C15—P1—C2—C3	−150.48 (15)	C11—C12—C13—O5	−179.18 (17)
C1—C2—C3—C4	−0.3 (3)	C11—C12—C13—C8	1.6 (3)
P1—C2—C3—C4	−179.79 (14)	C9—C8—C13—O5	178.92 (16)
C1—C2—C3—S1	−179.67 (13)	P1—C8—C13—O5	−2.3 (2)
P1—C2—C3—S1	0.8 (2)	C9—C8—C13—C12	−1.7 (3)
O2—S1—C3—C4	21.46 (18)	P1—C8—C13—C12	177.04 (14)
O1—S1—C3—C4	−100.67 (16)	C8—P1—C15—C16	4.33 (19)
O3—S1—C3—C4	141.04 (15)	C2—P1—C15—C16	−116.84 (16)
O2—S1—C3—C2	−159.14 (15)	C8—P1—C15—C20	−172.54 (14)
O1—S1—C3—C2	78.73 (16)	C2—P1—C15—C20	66.29 (16)
O3—S1—C3—C2	−39.55 (17)	C20—C15—C16—C17	−0.7 (3)
C2—C3—C4—C5	0.8 (3)	P1—C15—C16—C17	−177.42 (15)
S1—C3—C4—C5	−179.82 (14)	C15—C16—C17—C18	−1.3 (3)
C3—C4—C5—C6	−0.8 (3)	C16—C17—C18—C19	2.3 (3)
C4—C5—C6—C1	0.4 (3)	C17—C18—C19—C20	−1.3 (3)
C4—C5—C6—C7	−178.82 (18)	C21—O4—C20—C19	−14.4 (3)
C2—C1—C6—C5	0.1 (3)	C21—O4—C20—C15	165.79 (17)
C2—C1—C6—C7	179.34 (17)	C18—C19—C20—O4	179.46 (18)
C15—P1—C8—C9	−109.47 (16)	C18—C19—C20—C15	−0.8 (3)
C2—P1—C8—C9	10.75 (19)	C16—C15—C20—O4	−178.46 (16)
C15—P1—C8—C13	71.78 (16)	P1—C15—C20—O4	−1.5 (2)
C2—P1—C8—C13	−168.00 (14)	C16—C15—C20—C19	1.7 (3)
C13—C8—C9—C10	0.3 (3)	P1—C15—C20—C19	178.73 (14)
P1—C8—C9—C10	−178.39 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H1O···O1	0.91 (3)	1.96 (3)	2.862 (2)	170 (3)
O6—H2O···O2i	0.92 (3)	1.98 (3)	2.877 (2)	164 (3)
C19—H19···O3ii	0.95	2.47	3.180 (2)	132