4,6-Bis(diphenyl­phosphan­yl)-2,8-di­methyl­phenoxathiin dichloro­methane monosolvate

Marimuthu, T.; Friedrich, H.B.; Bala, M.D.

doi:10.1107/S1600536812009920

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1040

doi:10.1107/S1600536812009920

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4,6-Bis(diphenylphosphanyl)-2,8-dimethylphenoxathiin dichloromethane monosolvate

Thashree Marimuthu,^a Holger B. Friedrich ^a and Muhammad D. Bala ^a ^*

^aSchool of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
^*Correspondence e-mail: bala@ukzn.ac.za

(Received 22 February 2012; accepted 6 March 2012; online 10 March 2012)

The title compound, C₃₈H₃₀OP₂S·CH₂Cl₂, belongs to the xanthene family of ligands containing S- and O-donor atoms in the central heterocylic ring. Positions 2 and 8 on the xanthene backbone are functionalized with methyl groups to allow for the selective functionalization of the backbone at positions 4 and 6 with diphenylphosphanyl units. The title compound shows a significant `roof-like' bending along the axis of planarity involving the O- and S-donor atoms and the benzene rings, resulting in a dihedral angle between the mean planes of the benzene rings of 32.88 (13)°.

Related literature

For a closely related compound, see: Goertz et al. (1998 ). For complexation to metal centre and catalysis, see: Kranenburg et al. (1995 ). For related P-donor ligands, see: Marimuthu et al. (2008 ). For a related structure, see: Hillebrand et al. (1995 ).

Experimental

Crystal data

C₃₈H₃₀OP₂S·CH₂Cl₂
M_r = 681.55
Monoclinic, P 2₁ /n
a = 9.3605 (7) Å
b = 20.6796 (15) Å
c = 18.1360 (15) Å
β = 104.955 (1)°
V = 3391.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 173 K
0.47 × 0.36 × 0.28 mm

Data collection

Bruker APEXII CCD diffractometer
46059 measured reflections
8183 independent reflections
6527 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.07
8183 reflections
408 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009920/fj2525sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009920/fj2525Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009920/fj2525Isup3.cml

checkCIF report

Comment top

The title compound, 4,6-bis(diphenylphosphanyl)-2,8-dimethylphenoxathiin (I) (Fig. 1), has been reported as a ligand on rhodium for hydroformylation of olefins and on nickel for hydrocyanation of styrene (Kranenburg et al., 1995). Compound (I) consists of two very nearly regular planar hexagonal carbocyclic rings joined to a non-planar heterocyclic ring. The planes of the aromatic rings of the xanthene backbone bisect at an angle of 147.12° with the S atom lying out of the ring planes.

A comparison of (I) with the closely related structure reported by Goertz et al. (1998) shows that sixantphos can adopt two different conformations in the solid state with different crystallographic parameters and cell contents. The conformational differences were due to the presence of an incorporated solvent molecule in (I) and the significant roof-like bending of the backbone framework along the axis of planarity involving the O and S heterocyclic atoms and the aromatic rings. The dihedral angle of 32.88° between the least-squares planes of the aromatic rings of (I) is significant when compared to the essentially co-planar aromatic rings in the phenoxazine backbone of the Goertz et al. (1998) compound. The title compound crystallizes in the P2₁/n space group, while the previously reported structure was in the P2₁/c space group. A similar difference in conformation was reported by (Hillebrand et al., 1995) for two separate crystals of xantphos. The bond lengths for (I) are in good agreement with those in the reported structure, but the internal bond angles of the heterocyclic ring are slightly shorter in (I). This is consistent with a bent geometry of the heterocyle in (I) [C11—S1—C5] 98.28 (7) and [C12—O1—C6] 117.5 (1)° compared to 101.4 (1) and 124.4 (2)° for similar bond angles in the previously reported crystal structure.

Upon complexation to a metal centre the backbone of sixantphos tends to bend to accommodate the extra steric congestion around the metal centre (Goertz et al., 1998). Therefore when compound (I) is used as a ligand, the backbone needs little tilting in order to coordinate to a metal centre. The bond angles at the P atoms range from 100.04 (6) to 102.95 (7)° which are similar to those found for a realated P donor ligand [99.93 (10) to 103.02 (10)°] (Marimuthu et al., 2008).

Related literature top

For a closely related compound, see: Goertz et al. (1998). For complexation to metal centre and catalysis, see: Kranenburg et al. (1995). For related P-donor ligands, see: Marimuthu et al. (2008). For a related structure, see: Hillebrand et al. (1995).

Experimental top

A solution of 2,8-dimethylphenoxathiin (1.5 g, 6.6 mmol) and TMEDA (2.5 ml, 16.8 mmol) in 45 ml of dry degassed Et₂O was cooled to 0 °C. To the chilled solution, nBuLi (10.3 ml, 16.8 mmol) was added dropwise. The reaction mixture was allowed to warm to room temperature and left to stir for 16 h. The resulting dark orange reaction mixture was cooled to 0 °C and PPh₂Cl (3.1 ml, 16.8 mmol) in hexane (6 ml) added dropwise. The reaction mixture slowly decolourized and a fine precipitate formed. The reaction was allowed to stir for a further 16 h. Thereafter, the reaction was slowly hydroylsed with 40 ml of 10% HCl/brine mixture (1/1). The organic layer was removed, and the aqueous layer extracted with dichloromethane. The combined fractions were dried over MgSO₄, filtered, and the volume reduced to give a yellow oil. The crude product was washed with hexane (3 x 20 ml), the oil dissolved in dichloromethane, and an equal volume of ethanol added slowly. The solution was left to recrystalize at room temperature and the crystals filtered and dried under vacuum. Recrystallization from dichloromethane/ethanol (1:1) afforded colourless crystals of (I) suitable for X-ray analysis. [yield: 2.2 g, 62%; m.p. 457 K]. Spectroscopic analysis: ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 7.29 – 7.12 (m, 20H), 6.86 (apparent d, J = 1.0 Hz, 2H), 6.22 (bs, 2H), 2.05 (s, 6H); ¹³C NMR (101 MHz, CDCl₃, δ, p.p.m.): 152.2(t, J(P,C) = 24.4 Hz, CO), 137.2 (t, J(P,C) = 13.1 Hz phenyl C-ipso, PC), 133.9 (t, J (P,C) =21 Hz, CH phenyl), 133.5 (C), 132.7 (CH), 128.2 (CH phenyl), 128.1 (t, J(P,C) = 3.5 Hz, CH phenyl), 127.6 (CH) 127.3 (dd, J(P,C) = 12.6, 11 Hz, CHCHC–P), 119.5 (CS), 20.6 (CH₃); ³¹P NMR (243 MHz, CDCl₃ δ, p.p.m.): -17.9; IR (neat, ν_max, cm-1): 3050 (w), 2961 (w), 2921 (w), 1556 (m), 1476 (m), 1432 (m), 1402 (s), 1238 (m), 1221 (m) 1199 (m), 742 (s), 692 (s); HR—MS (ESI) (m/z): 597.1559 [M + H]⁺ calcd. for C₃₈H₃₁OP₂S, 597.1565.

Structure description top

For a closely related compound, see: Goertz et al. (1998). For complexation to metal centre and catalysis, see: Kranenburg et al. (1995). For related P-donor ligands, see: Marimuthu et al. (2008). For a related structure, see: Hillebrand et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP diagram of compound (I). Thermal ellipsoids are represented at the 50% probability level

4,6-Bis(diphenylphosphanyl)-2,8-dimethylphenoxathiin dichloromethane monosolvate top

Crystal data top

C₃₈H₃₀OP₂S·CH₂Cl₂	F(000) = 1416
M_r = 681.55	D_x = 1.335 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9922 reflections
a = 9.3605 (7) Å	θ = 2.3–28.3°
b = 20.6796 (15) Å	µ = 0.38 mm⁻¹
c = 18.1360 (15) Å	T = 173 K
β = 104.955 (1)°	Prism, colourless
V = 3391.7 (5) Å³	0.47 × 0.36 × 0.28 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	6527 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
Graphite monochromator	θ_max = 28.0°, θ_min = 1.5°
φ and ω scans	h = −12→12
46059 measured reflections	k = −27→27
8183 independent reflections	l = −15→23

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0535P)² + 0.4429P] where P = (F_o² + 2F_c²)/3
8183 reflections	(Δ/σ)_max = 0.001
408 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₃₈H₃₀OP₂S·CH₂Cl₂	V = 3391.7 (5) Å³
M_r = 681.55	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.3605 (7) Å	µ = 0.38 mm⁻¹
b = 20.6796 (15) Å	T = 173 K
c = 18.1360 (15) Å	0.47 × 0.36 × 0.28 mm
β = 104.955 (1)°

Data collection top

Bruker APEXII CCD diffractometer	6527 reflections with I > 2σ(I)
46059 measured reflections	R_int = 0.039
8183 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.07	Δρ_max = 0.46 e Å⁻³
8183 reflections	Δρ_min = −0.51 e Å⁻³
408 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
C1	0.67489 (15)	−0.01794 (7)	0.12353 (8)	0.0246 (3)
C2	0.61337 (16)	−0.07280 (7)	0.08142 (8)	0.0275 (3)
H2	0.6780	−0.1031	0.0675	0.033*
C3	0.46158 (16)	−0.08469 (7)	0.05916 (8)	0.0282 (3)
C4	0.36781 (16)	−0.04140 (7)	0.08135 (8)	0.0274 (3)
H4	0.2641	−0.0486	0.0671	0.033*
C5	0.42542 (15)	0.01272 (7)	0.12445 (8)	0.0245 (3)
C6	0.57712 (15)	0.02502 (7)	0.14406 (8)	0.0234 (3)
C7	0.63835 (15)	0.19416 (7)	0.18215 (8)	0.0240 (3)
C8	0.55781 (16)	0.25217 (7)	0.17171 (8)	0.0272 (3)
H8	0.6101	0.2920	0.1770	0.033*
C9	0.40319 (16)	0.25350 (7)	0.15383 (9)	0.0295 (3)
C10	0.32755 (16)	0.19526 (7)	0.14747 (9)	0.0302 (3)
H10	0.2225	0.1952	0.1351	0.036*
C11	0.40387 (16)	0.13687 (7)	0.15907 (8)	0.0260 (3)
C12	0.55822 (15)	0.13654 (7)	0.17502 (7)	0.0233 (3)
C13	0.39974 (19)	−0.14374 (8)	0.01255 (10)	0.0377 (4)
H13A	0.3703	−0.1759	0.0455	0.057*
H13B	0.4754	−0.1623	−0.0097	0.057*
H13C	0.3134	−0.1313	−0.0284	0.057*
C14	0.31804 (19)	0.31613 (8)	0.14184 (11)	0.0410 (4)
H14A	0.2463	0.3155	0.0918	0.062*
H14B	0.3867	0.3523	0.1441	0.062*
H14C	0.2657	0.3213	0.1818	0.062*
C21	0.93204 (15)	−0.01030 (7)	0.25149 (8)	0.0249 (3)
C22	0.83985 (17)	−0.03259 (8)	0.29494 (9)	0.0319 (3)
H22	0.7394	−0.0424	0.2710	0.038*
C23	0.89407 (18)	−0.04055 (9)	0.37329 (9)	0.0376 (4)
H23	0.8297	−0.0556	0.4024	0.045*
C24	1.04062 (18)	−0.02698 (8)	0.40987 (9)	0.0353 (4)
H24	1.0763	−0.0326	0.4635	0.042*
C25	1.13368 (18)	−0.00517 (8)	0.36723 (10)	0.0362 (4)
H25	1.2345	0.0038	0.3913	0.043*
C26	1.07971 (17)	0.00357 (8)	0.28947 (9)	0.0328 (3)
H26	1.1442	0.0194	0.2609	0.039*
C31	0.94616 (16)	−0.07369 (7)	0.11622 (9)	0.0270 (3)
C32	0.9978 (2)	−0.12632 (8)	0.16371 (10)	0.0425 (4)
H32	0.9980	−0.1242	0.2161	0.051*
C33	1.0489 (2)	−0.18156 (9)	0.13569 (12)	0.0523 (5)
H33	1.0840	−0.2169	0.1688	0.063*
C34	1.0487 (2)	−0.18526 (9)	0.05995 (11)	0.0451 (4)
H34	1.0836	−0.2232	0.0408	0.054*
C35	0.99786 (18)	−0.13374 (8)	0.01163 (9)	0.0372 (4)
H35	0.9971	−0.1365	−0.0408	0.045*
C36	0.94815 (16)	−0.07838 (8)	0.03957 (9)	0.0308 (3)
H36	0.9148	−0.0429	0.0062	0.037*
C41	0.89248 (15)	0.27288 (7)	0.18795 (8)	0.0268 (3)
C42	0.86834 (18)	0.29087 (8)	0.11127 (9)	0.0360 (4)
H42	0.8192	0.2619	0.0723	0.043*
C43	0.91518 (19)	0.35028 (9)	0.09168 (11)	0.0425 (4)
H43	0.8969	0.3622	0.0395	0.051*
C44	0.98901 (19)	0.39268 (8)	0.14815 (11)	0.0428 (4)
H44	1.0223	0.4333	0.1346	0.051*
C45	1.0138 (2)	0.37585 (8)	0.22366 (11)	0.0429 (4)
H45	1.0639	0.4050	0.2622	0.051*
C46	0.96594 (18)	0.31636 (8)	0.24391 (10)	0.0343 (3)
H46	0.9834	0.3052	0.2963	0.041*
C51	0.88289 (17)	0.19002 (7)	0.31191 (9)	0.0297 (3)
C52	0.7990 (2)	0.22244 (9)	0.35306 (10)	0.0415 (4)
H52	0.7145	0.2464	0.3270	0.050*
C53	0.8384 (2)	0.21988 (11)	0.43235 (11)	0.0525 (5)
H53	0.7803	0.2421	0.4601	0.063*
C54	0.9611 (3)	0.18540 (10)	0.47112 (11)	0.0568 (6)
H54	0.9873	0.1839	0.5253	0.068*
C55	1.0442 (3)	0.15360 (10)	0.43126 (12)	0.0649 (6)
H55	1.1289	0.1299	0.4577	0.078*
C56	1.0059 (2)	0.15565 (9)	0.35211 (11)	0.0495 (5)
H56	1.0647	0.1332	0.3250	0.059*
O1	0.63781 (10)	0.07871 (4)	0.18809 (6)	0.0254 (2)
P1	0.87456 (4)	0.001195 (17)	0.14751 (2)	0.02475 (9)
P2	0.84253 (4)	0.189890 (18)	0.20739 (2)	0.02557 (9)
S1	0.30570 (4)	0.064058 (19)	0.15779 (2)	0.03050 (10)
C57	0.5549 (3)	0.08998 (11)	0.36408 (12)	0.0588 (5)
H57A	0.5305	0.0567	0.3235	0.071*
H57B	0.6410	0.1149	0.3574	0.071*
Cl1	0.40384 (9)	0.14207 (3)	0.35502 (3)	0.07616 (19)
Cl2	0.60096 (7)	0.05229 (3)	0.45321 (3)	0.06801 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0241 (7)	0.0248 (7)	0.0251 (7)	−0.0002 (5)	0.0067 (5)	0.0043 (5)
C2	0.0296 (7)	0.0257 (7)	0.0280 (7)	−0.0009 (6)	0.0091 (6)	0.0003 (6)
C3	0.0308 (7)	0.0282 (7)	0.0247 (7)	−0.0043 (6)	0.0057 (6)	0.0014 (6)
C4	0.0249 (7)	0.0309 (7)	0.0253 (7)	−0.0040 (6)	0.0047 (6)	0.0032 (6)
C5	0.0248 (7)	0.0258 (7)	0.0227 (7)	0.0007 (5)	0.0059 (5)	0.0038 (5)
C6	0.0251 (7)	0.0229 (7)	0.0214 (6)	−0.0011 (5)	0.0045 (5)	0.0027 (5)
C7	0.0238 (7)	0.0282 (7)	0.0198 (6)	0.0004 (6)	0.0052 (5)	−0.0020 (5)
C8	0.0293 (7)	0.0249 (7)	0.0272 (7)	0.0013 (6)	0.0068 (6)	−0.0024 (6)
C9	0.0291 (7)	0.0298 (7)	0.0293 (8)	0.0061 (6)	0.0070 (6)	−0.0013 (6)
C10	0.0233 (7)	0.0352 (8)	0.0322 (8)	0.0030 (6)	0.0075 (6)	−0.0019 (6)
C11	0.0244 (7)	0.0295 (7)	0.0246 (7)	−0.0011 (6)	0.0074 (6)	−0.0007 (6)
C12	0.0246 (7)	0.0260 (7)	0.0191 (6)	0.0031 (5)	0.0051 (5)	0.0008 (5)
C13	0.0369 (9)	0.0360 (9)	0.0406 (9)	−0.0076 (7)	0.0107 (7)	−0.0098 (7)
C14	0.0365 (9)	0.0333 (9)	0.0520 (11)	0.0091 (7)	0.0092 (8)	−0.0033 (7)
C21	0.0251 (7)	0.0226 (7)	0.0275 (7)	−0.0001 (5)	0.0077 (6)	0.0006 (5)
C22	0.0248 (7)	0.0389 (8)	0.0326 (8)	−0.0013 (6)	0.0083 (6)	0.0037 (7)
C23	0.0347 (8)	0.0482 (10)	0.0329 (8)	0.0002 (7)	0.0143 (7)	0.0074 (7)
C24	0.0381 (8)	0.0388 (9)	0.0275 (8)	0.0037 (7)	0.0056 (7)	0.0012 (7)
C25	0.0290 (8)	0.0400 (9)	0.0366 (9)	−0.0044 (7)	0.0028 (7)	−0.0006 (7)
C26	0.0278 (7)	0.0366 (8)	0.0344 (8)	−0.0057 (6)	0.0090 (6)	0.0021 (7)
C31	0.0239 (7)	0.0295 (7)	0.0295 (7)	−0.0012 (6)	0.0100 (6)	0.0010 (6)
C32	0.0623 (12)	0.0354 (9)	0.0346 (9)	0.0130 (8)	0.0213 (8)	0.0060 (7)
C33	0.0747 (14)	0.0362 (10)	0.0512 (11)	0.0197 (9)	0.0256 (10)	0.0075 (8)
C34	0.0497 (11)	0.0378 (9)	0.0529 (11)	0.0042 (8)	0.0222 (9)	−0.0104 (8)
C35	0.0331 (8)	0.0480 (10)	0.0332 (8)	−0.0062 (7)	0.0133 (7)	−0.0104 (7)
C36	0.0262 (7)	0.0366 (8)	0.0295 (8)	−0.0028 (6)	0.0070 (6)	0.0014 (6)
C41	0.0230 (7)	0.0286 (7)	0.0307 (8)	0.0013 (6)	0.0103 (6)	−0.0018 (6)
C42	0.0326 (8)	0.0440 (9)	0.0329 (8)	−0.0032 (7)	0.0109 (7)	0.0005 (7)
C43	0.0360 (9)	0.0503 (10)	0.0437 (10)	0.0030 (8)	0.0146 (8)	0.0166 (8)
C44	0.0377 (9)	0.0320 (8)	0.0648 (12)	0.0037 (7)	0.0244 (9)	0.0092 (8)
C45	0.0466 (10)	0.0309 (8)	0.0563 (11)	−0.0075 (7)	0.0224 (9)	−0.0110 (8)
C46	0.0391 (9)	0.0325 (8)	0.0340 (8)	−0.0034 (7)	0.0141 (7)	−0.0045 (6)
C51	0.0310 (7)	0.0262 (7)	0.0288 (7)	−0.0041 (6)	0.0022 (6)	0.0022 (6)
C52	0.0394 (9)	0.0540 (11)	0.0308 (8)	−0.0005 (8)	0.0084 (7)	0.0023 (8)
C53	0.0611 (12)	0.0645 (13)	0.0334 (10)	−0.0123 (10)	0.0150 (9)	−0.0037 (9)
C54	0.0847 (16)	0.0486 (11)	0.0274 (9)	−0.0151 (11)	−0.0030 (9)	0.0046 (8)
C55	0.0803 (16)	0.0536 (12)	0.0421 (11)	0.0176 (11)	−0.0182 (11)	0.0022 (10)
C56	0.0538 (11)	0.0435 (10)	0.0405 (10)	0.0141 (9)	−0.0069 (8)	−0.0034 (8)
O1	0.0243 (5)	0.0226 (5)	0.0271 (5)	0.0010 (4)	0.0027 (4)	−0.0005 (4)
P1	0.02381 (18)	0.02421 (18)	0.02701 (19)	−0.00075 (14)	0.00797 (14)	0.00316 (14)
P2	0.02309 (18)	0.02554 (19)	0.02756 (19)	0.00042 (14)	0.00558 (14)	−0.00296 (14)
S1	0.02473 (18)	0.0316 (2)	0.0379 (2)	−0.00240 (14)	0.01310 (15)	−0.00110 (16)
C57	0.0696 (14)	0.0653 (13)	0.0483 (12)	−0.0136 (11)	0.0277 (11)	0.0025 (10)
Cl1	0.1172 (6)	0.0525 (3)	0.0529 (3)	0.0151 (3)	0.0113 (3)	0.0040 (2)
Cl2	0.0751 (4)	0.0842 (4)	0.0416 (3)	0.0195 (3)	0.0094 (3)	0.0037 (3)

Geometric parameters (Å, º) top

C1—C6	1.393 (2)	C26—H26	0.9500
C1—C2	1.405 (2)	C31—C32	1.395 (2)
C1—P1	1.8492 (14)	C31—C36	1.399 (2)
C2—C3	1.395 (2)	C31—P1	1.8345 (15)
C2—H2	0.9500	C32—C33	1.384 (2)
C3—C4	1.384 (2)	C32—H32	0.9500
C3—C13	1.513 (2)	C33—C34	1.375 (3)
C4—C5	1.392 (2)	C33—H33	0.9500
C4—H4	0.9500	C34—C35	1.384 (3)
C5—C6	1.3953 (19)	C34—H34	0.9500
C5—S1	1.7601 (14)	C35—C36	1.380 (2)
C6—O1	1.3996 (16)	C35—H35	0.9500
C7—C12	1.3961 (19)	C36—H36	0.9500
C7—C8	1.4035 (19)	C41—C46	1.397 (2)
C7—P2	1.8489 (14)	C41—C42	1.400 (2)
C8—C9	1.399 (2)	C41—P2	1.8367 (15)
C8—H8	0.9500	C42—C43	1.381 (2)
C9—C10	1.387 (2)	C42—H42	0.9500
C9—C14	1.507 (2)	C43—C44	1.389 (3)
C10—C11	1.391 (2)	C43—H43	0.9500
C10—H10	0.9500	C44—C45	1.373 (3)
C11—C12	1.3983 (19)	C44—H44	0.9500
C11—S1	1.7610 (15)	C45—C46	1.391 (2)
C12—O1	1.3966 (16)	C45—H45	0.9500
C13—H13A	0.9800	C46—H46	0.9500
C13—H13B	0.9800	C51—C52	1.387 (2)
C13—H13C	0.9800	C51—C56	1.389 (2)
C14—H14A	0.9800	C51—P2	1.8349 (16)
C14—H14B	0.9800	C52—C53	1.390 (2)
C14—H14C	0.9800	C52—H52	0.9500
C21—C22	1.389 (2)	C53—C54	1.380 (3)
C21—C26	1.406 (2)	C53—H53	0.9500
C21—P1	1.8381 (15)	C54—C55	1.360 (3)
C22—C23	1.390 (2)	C54—H54	0.9500
C22—H22	0.9500	C55—C56	1.387 (3)
C23—C24	1.390 (2)	C55—H55	0.9500
C23—H23	0.9500	C56—H56	0.9500
C24—C25	1.381 (2)	C57—Cl2	1.745 (2)
C24—H24	0.9500	C57—Cl1	1.751 (2)
C25—C26	1.382 (2)	C57—H57A	0.9900
C25—H25	0.9500	C57—H57B	0.9900

C6—C1—C2	117.04 (13)	C32—C31—P1	124.33 (12)
C6—C1—P1	119.63 (11)	C36—C31—P1	117.76 (11)
C2—C1—P1	123.24 (11)	C33—C32—C31	120.99 (16)
C3—C2—C1	122.92 (13)	C33—C32—H32	119.5
C3—C2—H2	118.5	C31—C32—H32	119.5
C1—C2—H2	118.5	C34—C33—C32	120.07 (17)
C4—C3—C2	118.47 (13)	C34—C33—H33	120.0
C4—C3—C13	120.31 (14)	C32—C33—H33	120.0
C2—C3—C13	121.22 (14)	C33—C34—C35	120.08 (16)
C3—C4—C5	120.04 (13)	C33—C34—H34	120.0
C3—C4—H4	120.0	C35—C34—H34	120.0
C5—C4—H4	120.0	C36—C35—C34	119.97 (15)
C4—C5—C6	120.73 (13)	C36—C35—H35	120.0
C4—C5—S1	119.29 (11)	C34—C35—H35	120.0
C6—C5—S1	119.92 (11)	C35—C36—C31	120.98 (15)
C1—C6—C5	120.74 (13)	C35—C36—H36	119.5
C1—C6—O1	117.41 (12)	C31—C36—H36	119.5
C5—C6—O1	121.77 (12)	C46—C41—C42	118.26 (14)
C12—C7—C8	117.39 (13)	C46—C41—P2	124.34 (12)
C12—C7—P2	118.59 (10)	C42—C41—P2	117.07 (12)
C8—C7—P2	124.00 (11)	C43—C42—C41	120.73 (16)
C9—C8—C7	122.37 (14)	C43—C42—H42	119.6
C9—C8—H8	118.8	C41—C42—H42	119.6
C7—C8—H8	118.8	C42—C43—C44	120.15 (16)
C10—C9—C8	118.53 (13)	C42—C43—H43	119.9
C10—C9—C14	119.65 (14)	C44—C43—H43	119.9
C8—C9—C14	121.81 (14)	C45—C44—C43	119.93 (16)
C9—C10—C11	120.66 (13)	C45—C44—H44	120.0
C9—C10—H10	119.7	C43—C44—H44	120.0
C11—C10—H10	119.7	C44—C45—C46	120.29 (16)
C10—C11—C12	119.89 (13)	C44—C45—H45	119.9
C10—C11—S1	119.63 (11)	C46—C45—H45	119.9
C12—C11—S1	120.42 (11)	C45—C46—C41	120.62 (16)
C7—C12—O1	117.70 (12)	C45—C46—H46	119.7
C7—C12—C11	121.12 (13)	C41—C46—H46	119.7
O1—C12—C11	121.11 (12)	C52—C51—C56	118.19 (16)
C3—C13—H13A	109.5	C52—C51—P2	124.20 (12)
C3—C13—H13B	109.5	C56—C51—P2	117.61 (13)
H13A—C13—H13B	109.5	C51—C52—C53	120.12 (18)
C3—C13—H13C	109.5	C51—C52—H52	119.9
H13A—C13—H13C	109.5	C53—C52—H52	119.9
H13B—C13—H13C	109.5	C54—C53—C52	120.7 (2)
C9—C14—H14A	109.5	C54—C53—H53	119.7
C9—C14—H14B	109.5	C52—C53—H53	119.7
H14A—C14—H14B	109.5	C55—C54—C53	119.59 (18)
C9—C14—H14C	109.5	C55—C54—H54	120.2
H14A—C14—H14C	109.5	C53—C54—H54	120.2
H14B—C14—H14C	109.5	C54—C55—C56	120.28 (19)
C22—C21—C26	117.78 (14)	C54—C55—H55	119.9
C22—C21—P1	124.39 (11)	C56—C55—H55	119.9
C26—C21—P1	117.83 (11)	C55—C56—C51	121.12 (19)
C21—C22—C23	120.19 (14)	C55—C56—H56	119.4
C21—C22—H22	119.9	C51—C56—H56	119.4
C23—C22—H22	119.9	C12—O1—C6	117.53 (10)
C24—C23—C22	121.29 (15)	C31—P1—C21	100.06 (7)
C24—C23—H23	119.4	C31—P1—C1	100.04 (6)
C22—C23—H23	119.4	C21—P1—C1	102.95 (6)
C25—C24—C23	119.08 (15)	C51—P2—C41	101.66 (7)
C25—C24—H24	120.5	C51—P2—C7	100.36 (7)
C23—C24—H24	120.5	C41—P2—C7	101.89 (6)
C24—C25—C26	119.79 (15)	C5—S1—C11	98.28 (7)
C24—C25—H25	120.1	Cl2—C57—Cl1	111.22 (11)
C26—C25—H25	120.1	Cl2—C57—H57A	109.4
C25—C26—C21	121.85 (14)	Cl1—C57—H57A	109.4
C25—C26—H26	119.1	Cl2—C57—H57B	109.4
C21—C26—H26	119.1	Cl1—C57—H57B	109.4
C32—C31—C36	117.91 (14)	H57A—C57—H57B	108.0

C6—C1—C2—C3	1.0 (2)	C46—C41—C42—C43	−0.4 (2)
P1—C1—C2—C3	−175.58 (11)	P2—C41—C42—C43	−174.05 (13)
C1—C2—C3—C4	−1.8 (2)	C41—C42—C43—C44	0.9 (2)
C1—C2—C3—C13	178.82 (14)	C42—C43—C44—C45	−0.8 (3)
C2—C3—C4—C5	0.4 (2)	C43—C44—C45—C46	0.3 (3)
C13—C3—C4—C5	179.78 (14)	C44—C45—C46—C41	0.2 (3)
C3—C4—C5—C6	1.7 (2)	C42—C41—C46—C45	−0.1 (2)
C3—C4—C5—S1	−175.53 (11)	P2—C41—C46—C45	173.01 (13)
C2—C1—C6—C5	1.2 (2)	C56—C51—C52—C53	−0.2 (3)
P1—C1—C6—C5	177.91 (10)	P2—C51—C52—C53	−179.86 (14)
C2—C1—C6—O1	178.01 (12)	C51—C52—C53—C54	0.2 (3)
P1—C1—C6—O1	−5.27 (17)	C52—C53—C54—C55	0.0 (3)
C4—C5—C6—C1	−2.6 (2)	C53—C54—C55—C56	−0.1 (3)
S1—C5—C6—C1	174.68 (11)	C54—C55—C56—C51	0.1 (3)
C4—C5—C6—O1	−179.26 (12)	C52—C51—C56—C55	0.0 (3)
S1—C5—C6—O1	−2.00 (18)	P2—C51—C56—C55	179.73 (17)
C12—C7—C8—C9	−0.8 (2)	C7—C12—O1—C6	−145.15 (12)
P2—C7—C8—C9	−178.94 (11)	C11—C12—O1—C6	37.94 (17)
C7—C8—C9—C10	1.0 (2)	C1—C6—O1—C12	145.19 (12)
C7—C8—C9—C14	−179.24 (14)	C5—C6—O1—C12	−38.02 (17)
C8—C9—C10—C11	0.4 (2)	C32—C31—P1—C21	11.81 (16)
C14—C9—C10—C11	−179.35 (14)	C36—C31—P1—C21	−168.59 (11)
C9—C10—C11—C12	−2.0 (2)	C32—C31—P1—C1	−93.41 (15)
C9—C10—C11—S1	175.18 (12)	C36—C31—P1—C1	86.19 (12)
C8—C7—C12—O1	−177.71 (12)	C22—C21—P1—C31	−98.97 (13)
P2—C7—C12—O1	0.51 (17)	C26—C21—P1—C31	80.13 (12)
C8—C7—C12—C11	−0.8 (2)	C22—C21—P1—C1	3.88 (14)
P2—C7—C12—C11	177.42 (10)	C26—C21—P1—C1	−177.02 (12)
C10—C11—C12—C7	2.2 (2)	C6—C1—P1—C31	174.71 (11)
S1—C11—C12—C7	−174.93 (10)	C2—C1—P1—C31	−8.79 (13)
C10—C11—C12—O1	178.99 (13)	C6—C1—P1—C21	71.84 (12)
S1—C11—C12—O1	1.87 (18)	C2—C1—P1—C21	−111.66 (12)
C26—C21—C22—C23	0.0 (2)	C52—C51—P2—C41	71.69 (15)
P1—C21—C22—C23	179.12 (12)	C56—C51—P2—C41	−107.97 (14)
C21—C22—C23—C24	−0.4 (3)	C52—C51—P2—C7	−32.88 (15)
C22—C23—C24—C25	0.0 (3)	C56—C51—P2—C7	147.46 (13)
C23—C24—C25—C26	0.8 (2)	C46—C41—P2—C51	9.70 (14)
C24—C25—C26—C21	−1.2 (2)	C42—C41—P2—C51	−177.11 (12)
C22—C21—C26—C25	0.8 (2)	C46—C41—P2—C7	113.06 (13)
P1—C21—C26—C25	−178.36 (12)	C42—C41—P2—C7	−73.75 (12)
C36—C31—C32—C33	−0.3 (3)	C12—C7—P2—C51	−88.24 (12)
P1—C31—C32—C33	179.32 (15)	C8—C7—P2—C51	89.85 (13)
C31—C32—C33—C34	−0.2 (3)	C12—C7—P2—C41	167.38 (11)
C32—C33—C34—C35	0.1 (3)	C8—C7—P2—C41	−14.54 (13)
C33—C34—C35—C36	0.5 (3)	C4—C5—S1—C11	−150.31 (12)
C34—C35—C36—C31	−1.0 (2)	C6—C5—S1—C11	32.39 (12)
C32—C31—C36—C35	0.9 (2)	C10—C11—S1—C5	150.43 (12)
P1—C31—C36—C35	−178.76 (12)	C12—C11—S1—C5	−32.45 (13)

Experimental details

Crystal data
Chemical formula	C₃₈H₃₀OP₂S·CH₂Cl₂
M_r	681.55
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	9.3605 (7), 20.6796 (15), 18.1360 (15)
β (°)	104.955 (1)
V (Å³)	3391.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.47 × 0.36 × 0.28

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	46059, 8183, 6527
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.07
No. of reflections	8183
No. of parameters	408
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.51

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We thank Dr Manuel Fernandes for the data collection and SASOL, THRIP and the University of KwaZulu-Natal for financial support.

References

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Hillebrand, S., Bruckmann, J., Kruger, C. & Haenel, M. W. (1995). Tetrahedron Lett. 36, 75–78. CSD CrossRef CAS Web of Science Google Scholar
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Marimuthu, T., Bala, M. D. & Friedrich, H. B. (2008). Acta Cryst. E64, o711. Web of Science CSD CrossRef IUCr Journals Google Scholar
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