[(Di-o-tolyl­phosphino)meth­yl]diphenyl­phosphine sulfide

Pitroda, P.P.; Badgett, A.H.; Dickey, G.A.; Gray, D.L.; Shelby, Q.D.

doi:10.1107/S1600536809034059

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2307

doi:10.1107/S1600536809034059

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[(Di-o-tolylphosphino)methyl]diphenylphosphine sulfide

Priyanka P. Pitroda,^a Ansonia H. Badgett,^a Geralyn A. Dickey,^a Danielle L. Gray ^b and Quinetta D. Shelby ^a ^*

^aDePaul University, Department of Chemistry, 1110 West Belden Avenue, Chicago, Illinois 60614, USA, and ^bUniversity of Illinois, School of Chemical Sciences, Box 59-1, 505 South Mathews Avenue, Urbana, Illinois 61801, USA
^*Correspondence e-mail: qshelby@depaul.edu

(Received 24 August 2009; accepted 25 August 2009; online 5 September 2009)

In the title compound, C₂₇H₂₆P₂S, the P—C—P angle is 114.33 (13)°. The bond distances are longer and the bond angles are smaller at the P atom bonded to the o-tolyl groups owing to the presence of a lone pair of electrons. One phenyl ring is disordered over three sites [occupancies 0.317 (8), 0.250 (8), and 0.433 (6)] and the other phenyl ring is disordered over two sites [occupancies 0.871 (6) and 0.129 (6)].

Related literature

For the synthesis of unsymmetrical (phosphinomethyl)phosphine monosulfides, see: Grim & Mitchell (1977 ); Grim et al. (1980 ). For the structures of related disulfides, see: Carmalt et al. (1996 ); Jones et al. (2002 ).

Experimental

Crystal data

C₂₇H₂₆P₂S
M_r = 444.48
Monoclinic, P 2₁ /c
a = 20.0639 (15) Å
b = 7.2739 (5) Å
c = 16.4160 (11) Å
β = 92.519 (4)°
V = 2393.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 193 K
0.35 × 0.33 × 0.19 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.935, T_max = 0.974
40516 measured reflections
4447 independent reflections
3092 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.112
S = 1.01
4447 reflections
439 parameters
713 restraints
H-atom parameters not refined
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2005 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and CrystalMaker (CrystalMaker, 1994 ); software used to prepare material for publication: XCIF (Bruker, 2005).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034059/ng2633sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034059/ng2633Isup2.hkl

checkCIF report

Comment top

Unsymmetrical (phosphinomethyl)phosphine monosulfides have been examined as ligands and have been used as precursors to their corresponding mixed bisphosphine ligands (Grim & Mitchell, 1977; Grim et al., 1980). We are interested in the steric properties of mixed aryl-aryl bisphosphine sulfides and their derivatives. The title compound, (di-o-tolylphosphino)methyldiphenylphosphine sulfide (C₂₇H₂₆P₂S), has not previously been reported, and its structure is shown in Fig. 1. The phenyl ring C1 to C6 is disordered over three sites and the phenyl ring C7 to C12 is disordered over two sites. The compound has a P1═S1 bond length of 1.950 (1) Å, which is similar to the P═S bond distances found in (bisphosphino)methane disulfides (Jones et al., 2002; Camalt et al., 1996). The P1—C(methylene) bond distance of 1.812 (3) Å is slightly shorter than the P2—C(methylene) bond distance of 1.852 (3) Å, where P1 is the diphenylphosphino P atom bonded to sulfur and P2 is the (di-o-tolyl)phosphino P atom. The P—C—P bond angle of 114.33 (13)° is larger than the expected value of 109.5° for a tetrahedral C atom. The C—P1—C bond angles range from 104.5 (4) to 106.15 (13)°. However, the C—P2—C bond angles of 100.23 (10) to 100.94 (11)° are significantly smaller. The longer bond distances and smaller bond angles at P2 are due to its lone pair of electrons.

Related literature top

For the synthesis of unsymmetrical (phosphinomethyl)phosphine monosulfides, see: Grim & Mitchell (1977); Grim et al. (1980). For the structures of related disulfides, see: Carmalt et al. (1996); Jones et al. (2002).

Experimental top

The title compound was prepared from a procedure adapted from that described by Grim et al. (1980) for the synthesis of unsymmetric (phosphinomethyl)phosphine sulfides. Under an N₂ atmosphere, Ph₂PSCH₂Li was formed from the addition of MeLi (8.84 ml of a 1.6 M solution in Et₂O, 14.1 mmol) over 1 h to a suspension of Ph₃PS (4.16 g, 14.1 mmol) in THF (16 ml) and Et₂O (12 ml). After stirring an additional hour, the Ph₂PSCH₂Li solution was added to a suspension of (o-tolyl)₂PCl (3.51 g, 14.1 mmol) in Et₂O (16 ml) over 3 h. The mixture was stirred overnight. Solvents were removed under vacuum, and the residue was dissolved in CH₂Cl₂ (24 ml), washed with H₂O (3 × 25 ml), and dried over MgSO₄. Solvent was removed, and the resulting oil was dissolved in absolute EtOH (50 ml) to give colorless clusters of the title compound (2.69 g, 43%). Mp: 128.4–129.0 °C. Anal. Calcd for C₂₇H₂₆P₂S: C, 72.96; H, 5.90; P, 13.94; S, 7.21. Found: C, 72.65; H, 5.94; P, 14.70; S, 7.28. ¹H NMR (CDCl₃): δ 2.30 (s, CH₃), 3.34 (d, 12.5 Hz, CH₂), 7.05–7.88 (m, C₆H₅ and C₆H₄CH₃). ¹³C{¹H} NMR (CDCl₃): δ 21.3 (d, ³J_CP = 22 Hz, CH₃), 33.1 (dd, ¹J_CP = 54 Hz, ¹J_CP = 32 Hz, CH₂), 126.0 (s, C₆H₄CH₃), 128.4 (d, J = 12 Hz, m-C₆H₅), 128.8 (s, C₆H₄CH₃), 130.2 (d, J = 5 Hz, C₆H₄CH₃), 131.2–131.7 (o-,p-C₆H₅ and C₆H₄CH₃), 132.3 (d, ¹J_CP = 82 Hz, i–PC₆H₅), 136.2 (dd, ¹J_CP = 15,8 Hz, i–PC₆H₄CH₃), 142.3 (d, ²J_CP = 29 Hz, i–CCH₃). ³¹P {¹H} NMR (CDCl₃): δ -48.5 (d, ²J_PP = 74 Hz, P(C₆H₄CH₃)₂), 40.2 (d, ²J_PP = 74 Hz, PS(C₆H₅)₂). IR (nujol mull between KBr plates, cm^-1): C—H (3074, 3050), CC (1593, 1470, 1436), PS (745).

Single crystals suitable for X-ray diffraction were grown from slow diffusion of pentane into a concentrated EtOH solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (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) and CrystalMaker (CrystalMaker, 1994); software used to prepare material for publication: XCIF (Bruker, 2005).

Figures top

Fig. 1. Molecular structure of the title compound showing disorder of the phenyl ring C1 to C6 over three sites and the phenyl ring C7 to C12 over two sites with 35% probability ellipsoids for non-H atoms and circles of arbitrary size for H atoms.

[(Di-o-tolylphosphino)methyl]diphenylphosphine sulfide top

Crystal data top

C₂₇H₂₆P₂S	F(000) = 936
M_r = 444.48	D_x = 1.233 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5909 reflections
a = 20.0639 (15) Å	θ = 2.7–24.2°
b = 7.2739 (5) Å	µ = 0.28 mm⁻¹
c = 16.4160 (11) Å	T = 193 K
β = 92.519 (4)°	Prism, colourless
V = 2393.5 (3) Å³	0.35 × 0.33 × 0.19 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	4447 independent reflections
Radiation source: fine-focus sealed tube	3092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
profile data from ϕ and ω scans	θ_max = 25.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −24→24
T_min = 0.935, T_max = 0.974	k = −8→8
40516 measured reflections	l = −19→19

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters not refined
S = 1.01	w = 1/[σ²(F_o²) + (0.0481P)² + 1.3507P] where P = (F_o² + 2F_c²)/3
4447 reflections	(Δ/σ)_max = 0.001
439 parameters	Δρ_max = 0.36 e Å⁻³
713 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₇H₂₆P₂S	V = 2393.5 (3) Å³
M_r = 444.48	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 20.0639 (15) Å	µ = 0.28 mm⁻¹
b = 7.2739 (5) Å	T = 193 K
c = 16.4160 (11) Å	0.35 × 0.33 × 0.19 mm
β = 92.519 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	4447 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3092 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.974	R_int = 0.063
40516 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	713 restraints
wR(F²) = 0.112	H-atom parameters not refined
S = 1.01	Δρ_max = 0.36 e Å⁻³
4447 reflections	Δρ_min = −0.22 e Å⁻³
439 parameters

Special details top

Experimental. One distinct cell was identified using APEX2 (Bruker, 2004). Six frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2005) then corrected for absorption by integration using SHELXTL/XPREP V2005/2 (Bruker, 2005) before using SADABS (Bruker, 2005) to sort, merge, and scale the combined data. No decay correction was applied.

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. Structure was phased by direct methods (Sheldrick, 2008). Systematic conditions suggested the unambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F². The highest peaks in the final difference Fourier map were in the vicinity of atoms P1, P2, and C20; the final map had no other significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude or resolution.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.18814 (4)	−0.05273 (10)	0.82663 (4)	0.0549 (2)
P1	0.17515 (4)	0.14683 (10)	0.90362 (4)	0.0423 (2)
P2	0.32375 (3)	0.25293 (8)	0.91684 (4)	0.03177 (17)
C1	0.0953 (4)	0.2626 (17)	0.8887 (9)	0.0559 (19)	0.317 (8)
C2	0.0797 (6)	0.4395 (18)	0.9115 (9)	0.071 (2)	0.317 (8)
H2A	0.1137	0.5115	0.9380	0.085*	0.317 (8)
C3	0.0176 (6)	0.5177 (16)	0.8982 (8)	0.078 (2)	0.317 (8)
H3A	0.0086	0.6398	0.9151	0.093*	0.317 (8)
C4	−0.0306 (6)	0.412 (2)	0.8595 (9)	0.087 (2)	0.317 (8)
H4A	−0.0738	0.4624	0.8487	0.104*	0.317 (8)
C5	−0.0178 (5)	0.235 (2)	0.8360 (10)	0.080 (2)	0.317 (8)
H5A	−0.0521	0.1646	0.8095	0.096*	0.317 (8)
C6	0.0448 (5)	0.1597 (17)	0.8507 (10)	0.067 (2)	0.317 (8)
H6A	0.0532	0.0367	0.8347	0.081*	0.317 (8)
C1B	0.0989 (6)	0.276 (2)	0.8738 (11)	0.061 (2)	0.250 (8)
C2B	0.0880 (7)	0.453 (2)	0.9018 (12)	0.068 (2)	0.250 (8)
H2BA	0.1211	0.5052	0.9379	0.082*	0.250 (8)
C3B	0.0327 (7)	0.558 (2)	0.8813 (10)	0.080 (2)	0.250 (8)
H3BA	0.0289	0.6783	0.9032	0.096*	0.250 (8)
C4B	−0.0169 (7)	0.490 (2)	0.8293 (10)	0.083 (2)	0.250 (8)
H4BA	−0.0552	0.5615	0.8147	0.100*	0.250 (8)
C5B	−0.0092 (6)	0.316 (2)	0.7994 (10)	0.086 (2)	0.250 (8)
H5BA	−0.0427	0.2648	0.7636	0.104*	0.250 (8)
C6B	0.0469 (6)	0.216 (2)	0.8210 (10)	0.071 (2)	0.250 (8)
H6BA	0.0506	0.0964	0.7984	0.085*	0.250 (8)
C1C	0.0946 (3)	0.2509 (10)	0.8906 (4)	0.0525 (16)	0.433 (6)
C2C	0.0866 (4)	0.4292 (11)	0.8658 (5)	0.0660 (17)	0.433 (6)
H2CA	0.1242	0.5051	0.8574	0.079*	0.433 (6)
C3C	0.0224 (4)	0.4969 (13)	0.8530 (5)	0.0841 (19)	0.433 (6)
H3CA	0.0154	0.6204	0.8359	0.101*	0.433 (6)
C4C	−0.0306 (4)	0.3838 (12)	0.8654 (5)	0.0897 (19)	0.433 (6)
H4CA	−0.0744	0.4310	0.8559	0.108*	0.433 (6)
C5C	−0.0232 (3)	0.2051 (12)	0.8908 (6)	0.083 (2)	0.433 (6)
H5CA	−0.0610	0.1300	0.8995	0.100*	0.433 (6)
C6C	0.0405 (3)	0.1378 (11)	0.9032 (5)	0.0685 (19)	0.433 (6)
H6CA	0.0474	0.0143	0.9204	0.082*	0.433 (6)
C7	0.17930 (17)	0.0688 (5)	1.00919 (18)	0.0414 (9)	0.871 (6)
C8	0.19203 (18)	−0.1139 (4)	1.0286 (2)	0.0522 (10)	0.871 (6)
H8A	0.1983	−0.2005	0.9863	0.063*	0.871 (6)
C9	0.1956 (2)	−0.1711 (5)	1.1092 (2)	0.0640 (12)	0.871 (6)
H9A	0.2044	−0.2964	1.1220	0.077*	0.871 (6)
C10	0.1867 (2)	−0.0475 (5)	1.1703 (2)	0.0607 (11)	0.871 (6)
H10A	0.1892	−0.0869	1.2255	0.073*	0.871 (6)
C11	0.1740 (2)	0.1334 (6)	1.1521 (2)	0.0565 (11)	0.871 (6)
H11A	0.1677	0.2189	1.1949	0.068*	0.871 (6)
C12	0.1704 (2)	0.1923 (5)	1.0719 (2)	0.0462 (9)	0.871 (6)
H12A	0.1618	0.3180	1.0598	0.055*	0.871 (6)
C7B	0.1592 (12)	0.102 (3)	1.0092 (7)	0.046 (3)	0.129 (6)
C8B	0.1518 (12)	−0.082 (3)	1.0271 (10)	0.052 (3)	0.129 (6)
H8BA	0.1495	−0.1707	0.9848	0.062*	0.129 (6)
C9B	0.1479 (13)	−0.135 (3)	1.1080 (10)	0.061 (2)	0.129 (6)
H9BA	0.1429	−0.2607	1.1214	0.073*	0.129 (6)
C10B	0.1512 (12)	−0.005 (3)	1.1684 (10)	0.060 (3)	0.129 (6)
H10B	0.1484	−0.0429	1.2236	0.072*	0.129 (6)
C11B	0.1585 (15)	0.177 (3)	1.1507 (12)	0.053 (3)	0.129 (6)
H11B	0.1606	0.2653	1.1934	0.064*	0.129 (6)
C12B	0.1626 (16)	0.232 (3)	1.0703 (13)	0.048 (3)	0.129 (6)
H12B	0.1678	0.3587	1.0575	0.058*	0.129 (6)
C13	0.23640 (12)	0.3288 (3)	0.89744 (14)	0.0368 (6)
H13A	0.2261	0.4254	0.9375	0.044*
H13B	0.2322	0.3845	0.8424	0.044*
C14	0.33277 (12)	0.2801 (3)	1.02845 (13)	0.0319 (5)
C15	0.35109 (13)	0.1284 (3)	1.07706 (14)	0.0355 (6)
C16	0.35666 (13)	0.1529 (4)	1.16115 (15)	0.0436 (7)
H16A	0.3688	0.0513	1.1950	0.052*
C17	0.34508 (15)	0.3198 (4)	1.19610 (15)	0.0480 (7)
H17A	0.3490	0.3328	1.2537	0.058*
C18	0.32772 (15)	0.4695 (4)	1.14798 (15)	0.0506 (8)
H18A	0.3196	0.5856	1.1721	0.061*
C19	0.32229 (13)	0.4484 (3)	1.06448 (14)	0.0399 (6)
H19A	0.3111	0.5516	1.0312	0.048*
C20	0.36521 (17)	−0.0566 (4)	1.04103 (17)	0.0573 (8)
H20A	0.3286	−0.0909	1.0025	0.086*
H20B	0.3692	−0.1484	1.0847	0.086*
H20C	0.4070	−0.0512	1.0124	0.086*
C21	0.36910 (13)	0.4573 (3)	0.88391 (13)	0.0349 (6)
C22	0.43854 (14)	0.4437 (4)	0.88096 (16)	0.0482 (7)
C23	0.47409 (17)	0.5932 (5)	0.8522 (2)	0.0655 (9)
H23A	0.5212	0.5849	0.8500	0.079*
C24	0.4426 (2)	0.7518 (4)	0.82709 (18)	0.0670 (10)
H24A	0.4678	0.8514	0.8070	0.080*
C25	0.37510 (19)	0.7663 (4)	0.83110 (15)	0.0559 (8)
H25A	0.3531	0.8768	0.8148	0.067*
C26	0.33887 (15)	0.6207 (3)	0.85878 (14)	0.0415 (6)
H26A	0.2918	0.6320	0.8608	0.050*
C27	0.47553 (16)	0.2744 (5)	0.9088 (2)	0.0741 (10)
H27A	0.4531	0.1654	0.8856	0.111*
H27B	0.4763	0.2674	0.9684	0.111*
H27C	0.5214	0.2797	0.8906	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0666 (5)	0.0505 (4)	0.0476 (4)	−0.0067 (4)	0.0020 (4)	−0.0170 (3)
P1	0.0467 (4)	0.0439 (4)	0.0360 (4)	−0.0044 (3)	0.0011 (3)	−0.0062 (3)
P2	0.0453 (4)	0.0260 (3)	0.0240 (3)	0.0012 (3)	0.0009 (3)	−0.0007 (2)
C1	0.040 (3)	0.071 (3)	0.056 (4)	0.000 (3)	0.001 (3)	−0.010 (3)
C2	0.052 (3)	0.075 (3)	0.084 (4)	0.007 (3)	−0.012 (4)	−0.009 (4)
C3	0.053 (4)	0.086 (4)	0.094 (4)	0.011 (3)	−0.004 (4)	−0.003 (4)
C4	0.051 (3)	0.099 (4)	0.110 (4)	0.014 (3)	−0.007 (4)	−0.001 (4)
C5	0.046 (3)	0.097 (4)	0.097 (5)	−0.001 (4)	−0.007 (4)	−0.008 (4)
C6	0.046 (3)	0.081 (4)	0.075 (5)	−0.003 (3)	−0.003 (4)	−0.011 (4)
C1B	0.043 (3)	0.075 (4)	0.064 (4)	−0.001 (3)	0.001 (3)	−0.013 (4)
C2B	0.050 (3)	0.075 (4)	0.078 (4)	0.009 (3)	−0.010 (4)	−0.008 (4)
C3B	0.053 (4)	0.089 (4)	0.096 (5)	0.009 (4)	−0.013 (4)	−0.006 (4)
C4B	0.049 (4)	0.095 (4)	0.105 (5)	0.007 (4)	−0.011 (4)	0.001 (4)
C5B	0.056 (4)	0.101 (5)	0.101 (5)	0.010 (4)	−0.012 (4)	−0.007 (4)
C6B	0.048 (4)	0.086 (4)	0.077 (5)	0.001 (3)	−0.003 (4)	−0.016 (4)
C1C	0.040 (3)	0.068 (3)	0.050 (3)	0.001 (3)	0.001 (3)	−0.010 (3)
C2C	0.048 (3)	0.080 (3)	0.071 (4)	0.014 (3)	0.000 (3)	0.000 (3)
C3C	0.059 (3)	0.090 (4)	0.102 (4)	0.014 (3)	−0.014 (4)	−0.001 (3)
C4C	0.051 (3)	0.102 (4)	0.115 (4)	0.019 (3)	−0.006 (3)	0.001 (4)
C5C	0.043 (3)	0.096 (4)	0.109 (5)	0.003 (3)	−0.007 (4)	0.001 (4)
C6C	0.045 (3)	0.078 (3)	0.082 (4)	0.002 (3)	−0.007 (3)	−0.003 (3)
C7	0.039 (2)	0.0454 (18)	0.0400 (16)	−0.0063 (15)	0.0060 (14)	−0.0034 (14)
C8	0.061 (3)	0.0448 (17)	0.0503 (19)	−0.0038 (17)	0.0025 (18)	−0.0024 (15)
C9	0.077 (3)	0.054 (2)	0.060 (2)	−0.009 (2)	0.000 (2)	0.0094 (17)
C10	0.065 (3)	0.068 (2)	0.0488 (19)	−0.013 (2)	0.0013 (18)	0.0137 (17)
C11	0.064 (3)	0.065 (2)	0.0410 (18)	−0.0041 (19)	0.0078 (17)	−0.0046 (17)
C12	0.053 (2)	0.0448 (19)	0.0410 (17)	0.0009 (17)	0.0072 (15)	0.0000 (15)
C7B	0.051 (6)	0.046 (5)	0.042 (5)	−0.005 (5)	0.008 (5)	−0.005 (4)
C8B	0.057 (6)	0.051 (5)	0.047 (4)	−0.003 (5)	0.007 (5)	−0.002 (5)
C9B	0.070 (5)	0.059 (4)	0.055 (4)	−0.008 (5)	0.005 (5)	0.007 (4)
C10B	0.068 (6)	0.065 (5)	0.048 (5)	−0.002 (5)	0.009 (5)	0.003 (4)
C11B	0.059 (6)	0.058 (5)	0.044 (5)	0.001 (5)	0.009 (5)	−0.003 (5)
C12B	0.052 (5)	0.051 (5)	0.041 (4)	0.000 (5)	0.009 (5)	−0.006 (4)
C13	0.0462 (16)	0.0366 (13)	0.0273 (13)	0.0028 (12)	−0.0012 (11)	−0.0007 (11)
C14	0.0413 (14)	0.0286 (12)	0.0258 (12)	−0.0027 (10)	0.0009 (11)	0.0035 (10)
C15	0.0463 (15)	0.0312 (12)	0.0290 (13)	−0.0029 (11)	0.0011 (11)	0.0056 (10)
C16	0.0578 (18)	0.0384 (14)	0.0341 (15)	−0.0083 (13)	−0.0032 (12)	0.0119 (12)
C17	0.075 (2)	0.0459 (16)	0.0225 (13)	−0.0131 (14)	0.0001 (13)	0.0025 (12)
C18	0.088 (2)	0.0335 (14)	0.0309 (15)	−0.0065 (14)	0.0042 (14)	−0.0035 (11)
C19	0.0645 (18)	0.0290 (12)	0.0261 (13)	−0.0012 (12)	0.0006 (12)	0.0000 (10)
C20	0.090 (2)	0.0353 (14)	0.0467 (17)	0.0146 (15)	0.0050 (16)	0.0089 (13)
C21	0.0525 (17)	0.0326 (13)	0.0197 (12)	−0.0025 (12)	0.0021 (11)	−0.0010 (10)
C22	0.0532 (19)	0.0486 (16)	0.0430 (16)	−0.0055 (14)	0.0026 (13)	0.0022 (13)
C23	0.065 (2)	0.066 (2)	0.067 (2)	−0.0211 (17)	0.0168 (17)	−0.0008 (17)
C24	0.105 (3)	0.0478 (18)	0.0497 (19)	−0.0274 (19)	0.0251 (19)	−0.0001 (15)
C25	0.103 (3)	0.0338 (15)	0.0310 (15)	−0.0033 (16)	0.0081 (16)	0.0023 (12)
C26	0.0657 (18)	0.0327 (13)	0.0261 (13)	0.0003 (12)	0.0022 (12)	0.0004 (10)
C27	0.0474 (19)	0.075 (2)	0.100 (3)	0.0043 (17)	0.0044 (18)	0.018 (2)

Geometric parameters (Å, º) top

S1—P1	1.950 (1)	C9—H9A	0.9500
P1—C1C	1.790 (5)	C10—C11	1.371 (4)
P1—C7B	1.806 (9)	C10—H10A	0.9500
P1—C13	1.812 (3)	C11—C12	1.385 (4)
P1—C1	1.816 (6)	C11—H11A	0.9500
P1—C7	1.822 (3)	C12—H12A	0.9500
P1—C1B	1.843 (7)	C7B—C12B	1.378 (8)
P2—C21	1.837 (2)	C7B—C8B	1.380 (8)
P2—C14	1.844 (2)	C8B—C9B	1.389 (8)
P2—C13	1.852 (3)	C8B—H8BA	0.9500
C1—C2	1.380 (7)	C9B—C10B	1.365 (8)
C1—C6	1.387 (7)	C9B—H9BA	0.9500
C2—C3	1.379 (7)	C10B—C11B	1.367 (8)
C2—H2A	0.9500	C10B—H10B	0.9500
C3—C4	1.369 (7)	C11B—C12B	1.386 (8)
C3—H3A	0.9500	C11B—H11B	0.9500
C4—C5	1.369 (7)	C12B—H12B	0.9500
C4—H4A	0.9500	C13—H13A	0.9900
C5—C6	1.383 (8)	C13—H13B	0.9900
C5—H5A	0.9500	C14—C19	1.380 (3)
C6—H6A	0.9500	C14—C15	1.401 (3)
C1B—C2B	1.386 (7)	C15—C16	1.391 (3)
C1B—C6B	1.397 (7)	C15—C20	1.502 (3)
C2B—C3B	1.377 (8)	C16—C17	1.367 (4)
C2B—H2BA	0.9500	C16—H16A	0.9500
C3B—C4B	1.375 (8)	C17—C18	1.381 (4)
C3B—H3BA	0.9500	C17—H17A	0.9500
C4B—C5B	1.367 (8)	C18—C19	1.379 (3)
C4B—H4BA	0.9500	C18—H18A	0.9500
C5B—C6B	1.376 (8)	C19—H19A	0.9500
C5B—H5BA	0.9500	C20—H20A	0.9800
C6B—H6BA	0.9500	C20—H20B	0.9800
C1C—C2C	1.367 (6)	C20—H20C	0.9800
C1C—C6C	1.384 (6)	C21—C26	1.388 (3)
C2C—C3C	1.385 (7)	C21—C22	1.400 (4)
C2C—H2CA	0.9500	C22—C23	1.394 (4)
C3C—C4C	1.367 (7)	C22—C27	1.499 (4)
C3C—H3CA	0.9500	C23—C24	1.370 (5)
C4C—C5C	1.371 (7)	C23—H23A	0.9500
C4C—H4CA	0.9500	C24—C25	1.363 (4)
C5C—C6C	1.376 (7)	C24—H24A	0.9500
C5C—H5CA	0.9500	C25—C26	1.373 (4)
C6C—H6CA	0.9500	C25—H25A	0.9500
C7—C12	1.383 (4)	C26—H26A	0.9500
C7—C8	1.387 (4)	C27—H27A	0.9800
C8—C9	1.386 (4)	C27—H27B	0.9800
C8—H8A	0.9500	C27—H27C	0.9800
C9—C10	1.364 (4)

C1C—P1—C7B	89.6 (8)	C8—C9—H9A	120.0
C1C—P1—C13	107.2 (3)	C9—C10—C11	120.1 (3)
C7B—P1—C13	109.5 (8)	C9—C10—H10A	119.9
C7B—P1—C1	91.1 (9)	C11—C10—H10A	119.9
C13—P1—C1	104.5 (4)	C10—C11—C12	120.4 (3)
C1C—P1—C7	104.4 (2)	C10—C11—H11A	119.8
C13—P1—C7	106.15 (13)	C12—C11—H11A	119.8
C1—P1—C7	106.0 (5)	C7—C12—C11	120.3 (3)
C7B—P1—C1B	99.6 (10)	C7—C12—H12A	119.9
C13—P1—C1B	99.7 (6)	C11—C12—H12A	119.9
C7—P1—C1B	114.5 (6)	C12B—C7B—C8B	120.8 (10)
C1C—P1—S1	112.6 (2)	C12B—C7B—P1	124.8 (14)
C7B—P1—S1	121.6 (7)	C8B—C7B—P1	113.8 (12)
C13—P1—S1	113.40 (9)	C7B—C8B—C9B	118.9 (10)
C1—P1—S1	113.6 (4)	C7B—C8B—H8BA	120.5
C7—P1—S1	112.50 (12)	C9B—C8B—H8BA	120.5
C1B—P1—S1	109.9 (6)	C10B—C9B—C8B	120.1 (11)
C21—P2—C14	100.23 (10)	C10B—C9B—H9BA	120.0
C21—P2—C13	100.70 (11)	C8B—C9B—H9BA	120.0
C14—P2—C13	100.94 (11)	C9B—C10B—C11B	121.1 (12)
C2—C1—C6	117.0 (7)	C9B—C10B—H10B	119.5
C2—C1—P1	127.3 (8)	C11B—C10B—H10B	119.5
C6—C1—P1	115.7 (8)	C10B—C11B—C12B	119.7 (11)
C3—C2—C1	123.8 (8)	C10B—C11B—H11B	120.2
C3—C2—H2A	118.1	C12B—C11B—H11B	120.2
C1—C2—H2A	118.1	C7B—C12B—C11B	119.4 (11)
C4—C3—C2	117.2 (8)	C7B—C12B—H12B	120.3
C4—C3—H3A	121.4	C11B—C12B—H12B	120.3
C2—C3—H3A	121.4	P1—C13—P2	114.33 (13)
C5—C4—C3	121.3 (9)	P1—C13—H13A	108.7
C5—C4—H4A	119.3	P2—C13—H13A	108.7
C3—C4—H4A	119.3	P1—C13—H13B	108.7
C4—C5—C6	120.3 (8)	P2—C13—H13B	108.7
C4—C5—H5A	119.8	H13A—C13—H13B	107.6
C6—C5—H5A	119.8	C19—C14—C15	119.7 (2)
C5—C6—C1	120.3 (8)	C19—C14—P2	120.73 (18)
C5—C6—H6A	119.9	C15—C14—P2	119.56 (18)
C1—C6—H6A	119.9	C16—C15—C14	118.2 (2)
C2B—C1B—C6B	111.8 (7)	C16—C15—C20	119.8 (2)
C2B—C1B—P1	121.8 (10)	C14—C15—C20	122.0 (2)
C6B—C1B—P1	126.4 (10)	C17—C16—C15	121.5 (2)
C3B—C2B—C1B	124.9 (9)	C17—C16—H16A	119.3
C3B—C2B—H2BA	117.6	C15—C16—H16A	119.3
C1B—C2B—H2BA	117.6	C16—C17—C18	120.2 (2)
C4B—C3B—C2B	120.4 (9)	C16—C17—H17A	119.9
C4B—C3B—H3BA	119.8	C18—C17—H17A	119.9
C2B—C3B—H3BA	119.8	C19—C18—C17	119.2 (2)
C5B—C4B—C3B	117.7 (9)	C19—C18—H18A	120.4
C5B—C4B—H4BA	121.1	C17—C18—H18A	120.4
C3B—C4B—H4BA	121.1	C18—C19—C14	121.2 (2)
C4B—C5B—C6B	120.1 (9)	C18—C19—H19A	119.4
C4B—C5B—H5BA	119.9	C14—C19—H19A	119.4
C6B—C5B—H5BA	119.9	C15—C20—H20A	109.5
C5B—C6B—C1B	125.1 (9)	C15—C20—H20B	109.5
C5B—C6B—H6BA	117.5	H20A—C20—H20B	109.5
C1B—C6B—H6BA	117.5	C15—C20—H20C	109.5
C2C—C1C—C6C	121.7 (6)	H20A—C20—H20C	109.5
C2C—C1C—P1	122.0 (6)	H20B—C20—H20C	109.5
C6C—C1C—P1	116.2 (5)	C26—C21—C22	118.2 (2)
C1C—C2C—C3C	118.6 (6)	C26—C21—P2	124.4 (2)
C1C—C2C—H2CA	120.7	C22—C21—P2	117.34 (19)
C3C—C2C—H2CA	120.7	C23—C22—C21	118.8 (3)
C4C—C3C—C2C	119.2 (7)	C23—C22—C27	119.4 (3)
C4C—C3C—H3CA	120.4	C21—C22—C27	121.9 (2)
C2C—C3C—H3CA	120.4	C24—C23—C22	121.5 (3)
C3C—C4C—C5C	122.7 (7)	C24—C23—H23A	119.2
C3C—C4C—H4CA	118.6	C22—C23—H23A	119.2
C5C—C4C—H4CA	118.6	C25—C24—C23	119.7 (3)
C4C—C5C—C6C	118.0 (7)	C25—C24—H24A	120.1
C4C—C5C—H5CA	121.0	C23—C24—H24A	120.1
C6C—C5C—H5CA	121.0	C24—C25—C26	119.9 (3)
C5C—C6C—C1C	119.7 (6)	C24—C25—H25A	120.1
C5C—C6C—H6CA	120.1	C26—C25—H25A	120.1
C1C—C6C—H6CA	120.1	C25—C26—C21	121.8 (3)
C12—C7—C8	118.7 (3)	C25—C26—H26A	119.1
C12—C7—P1	120.2 (3)	C21—C26—H26A	119.1
C8—C7—P1	121.2 (2)	C22—C27—H27A	109.5
C9—C8—C7	120.5 (3)	C22—C27—H27B	109.5
C9—C8—H8A	119.7	H27A—C27—H27B	109.5
C7—C8—H8A	119.7	C22—C27—H27C	109.5
C10—C9—C8	120.1 (3)	H27A—C27—H27C	109.5
C10—C9—H9A	120.0	H27B—C27—H27C	109.5

C1C—P1—C1—C2	135 (12)	C1—P1—C7—C8	126.1 (5)
C7B—P1—C1—C2	78.6 (10)	C1B—P1—C7—C8	127.8 (6)
C13—P1—C1—C2	−31.9 (8)	S1—P1—C7—C8	1.4 (2)
C7—P1—C1—C2	80.0 (8)	C12—C7—C8—C9	0.1 (2)
C1B—P1—C1—C2	−89 (6)	P1—C7—C8—C9	179.4 (2)
S1—P1—C1—C2	−156.0 (6)	C7—C8—C9—C10	0.0 (2)
C1C—P1—C1—C6	−44 (11)	C8—C9—C10—C11	0.0 (4)
C7B—P1—C1—C6	−100.8 (11)	C9—C10—C11—C12	−0.2 (5)
C13—P1—C1—C6	148.7 (7)	C8—C7—C12—C11	−0.2 (4)
C7—P1—C1—C6	−99.4 (8)	P1—C7—C12—C11	−179.5 (3)
C1B—P1—C1—C6	91 (6)	C10—C11—C12—C7	0.2 (5)
S1—P1—C1—C6	24.6 (9)	C1C—P1—C7B—C12B	−77.1 (12)
C6—C1—C2—C3	−0.4 (3)	C13—P1—C7B—C12B	31.0 (13)
P1—C1—C2—C3	−179.9 (11)	C1—P1—C7B—C12B	−74.8 (13)
C1—C2—C3—C4	−0.4 (3)	C7—P1—C7B—C12B	110 (3)
C2—C3—C4—C5	0.8 (7)	C1B—P1—C7B—C12B	−73.0 (13)
C3—C4—C5—C6	−0.3 (9)	S1—P1—C7B—C12B	166.4 (11)
C4—C5—C6—C1	−0.6 (9)	C1C—P1—C7B—C8B	111.5 (13)
C2—C1—C6—C5	0.9 (6)	C13—P1—C7B—C8B	−140.4 (12)
P1—C1—C6—C5	−179.6 (9)	C1—P1—C7B—C8B	113.8 (14)
C1C—P1—C1B—C2B	93 (3)	C7—P1—C7B—C8B	−61 (3)
C7B—P1—C1B—C2B	70.6 (11)	C1B—P1—C7B—C8B	115.6 (14)
C13—P1—C1B—C2B	−41.3 (8)	S1—P1—C7B—C8B	−5.0 (17)
C1—P1—C1B—C2B	83 (6)	C12B—C7B—C8B—C9B	0.1 (3)
C7—P1—C1B—C2B	71.6 (8)	P1—C7B—C8B—C9B	171.9 (15)
S1—P1—C1B—C2B	−160.7 (6)	C7B—C8B—C9B—C10B	0.0 (3)
C1C—P1—C1B—C6B	−88 (3)	C8B—C9B—C10B—C11B	0.0 (7)
C7B—P1—C1B—C6B	−110.7 (14)	C9B—C10B—C11B—C12B	−0.1 (9)
C13—P1—C1B—C6B	137.4 (11)	C8B—C7B—C12B—C11B	−0.2 (7)
C1—P1—C1B—C6B	−99 (6)	P1—C7B—C12B—C11B	−171.0 (17)
C7—P1—C1B—C6B	−109.7 (11)	C10B—C11B—C12B—C7B	0.2 (9)
S1—P1—C1B—C6B	18.0 (14)	C1C—P1—C13—P2	175.8 (2)
C6B—C1B—C2B—C3B	0.3 (3)	C7B—P1—C13—P2	80.0 (8)
P1—C1B—C2B—C3B	179.2 (13)	C1—P1—C13—P2	176.5 (5)
C1B—C2B—C3B—C4B	0.0 (3)	C7—P1—C13—P2	64.67 (17)
C2B—C3B—C4B—C5B	0.1 (7)	C1B—P1—C13—P2	−176.1 (6)
C3B—C4B—C5B—C6B	−0.4 (9)	S1—P1—C13—P2	−59.34 (14)
C4B—C5B—C6B—C1B	0.8 (10)	C21—P2—C13—P1	168.44 (12)
C2B—C1B—C6B—C5B	−0.7 (7)	C14—P2—C13—P1	−88.82 (14)
P1—C1B—C6B—C5B	−179.5 (14)	C21—P2—C14—C19	45.2 (2)
C7B—P1—C1C—C2C	121.0 (9)	C13—P2—C14—C19	−57.9 (2)
C13—P1—C1C—C2C	10.7 (5)	C21—P2—C14—C15	−134.2 (2)
C1—P1—C1C—C2C	−3 (12)	C13—P2—C14—C15	122.7 (2)
C7—P1—C1C—C2C	123.0 (5)	C19—C14—C15—C16	1.4 (4)
C1B—P1—C1C—C2C	−37 (3)	P2—C14—C15—C16	−179.21 (19)
S1—P1—C1C—C2C	−114.7 (4)	C19—C14—C15—C20	−178.1 (3)
C7B—P1—C1C—C6C	−62.1 (9)	P2—C14—C15—C20	1.3 (4)
C13—P1—C1C—C6C	−172.5 (4)	C14—C15—C16—C17	−0.4 (4)
C1—P1—C1C—C6C	174 (12)	C20—C15—C16—C17	179.1 (3)
C7—P1—C1C—C6C	−60.1 (5)	C15—C16—C17—C18	−0.3 (4)
C1B—P1—C1C—C6C	140 (3)	C16—C17—C18—C19	0.0 (4)
S1—P1—C1C—C6C	62.2 (5)	C17—C18—C19—C14	1.1 (4)
C6C—C1C—C2C—C3C	0.0 (3)	C15—C14—C19—C18	−1.8 (4)
P1—C1C—C2C—C3C	176.6 (5)	P2—C14—C19—C18	178.8 (2)
C1C—C2C—C3C—C4C	−0.2 (3)	C14—P2—C21—C26	−98.9 (2)
C2C—C3C—C4C—C5C	0.6 (6)	C13—P2—C21—C26	4.4 (2)
C3C—C4C—C5C—C6C	−0.8 (8)	C14—P2—C21—C22	83.8 (2)
C4C—C5C—C6C—C1C	0.5 (8)	C13—P2—C21—C22	−172.85 (19)
C2C—C1C—C6C—C5C	−0.1 (6)	C26—C21—C22—C23	−0.7 (4)
P1—C1C—C6C—C5C	−177.0 (5)	P2—C21—C22—C23	176.7 (2)
C1C—P1—C7—C12	−56.9 (3)	C26—C21—C22—C27	178.5 (3)
C7B—P1—C7—C12	−49 (3)	P2—C21—C22—C27	−4.1 (4)
C13—P1—C7—C12	56.2 (3)	C21—C22—C23—C24	0.0 (5)
C1—P1—C7—C12	−54.6 (5)	C27—C22—C23—C24	−179.1 (3)
C1B—P1—C7—C12	−52.8 (7)	C22—C23—C24—C25	0.9 (5)
S1—P1—C7—C12	−179.3 (2)	C23—C24—C25—C26	−1.2 (4)
C1C—P1—C7—C8	123.7 (3)	C24—C25—C26—C21	0.6 (4)
C7B—P1—C7—C8	132 (3)	C22—C21—C26—C25	0.4 (4)
C13—P1—C7—C8	−123.2 (2)	P2—C21—C26—C25	−176.84 (19)

Experimental details

Crystal data
Chemical formula	C₂₇H₂₆P₂S
M_r	444.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	193
a, b, c (Å)	20.0639 (15), 7.2739 (5), 16.4160 (11)
β (°)	92.519 (4)
V (Å³)	2393.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.35 × 0.33 × 0.19

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.935, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	40516, 4447, 3092
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.607

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.112, 1.01
No. of reflections	4447
No. of parameters	439
No. of restraints	713
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.22

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and CrystalMaker (CrystalMaker, 1994), XCIF (Bruker, 2005).

Acknowledgements

We thank the National Science Foundation (grant CHE-0548107) for support of this work. AHB thanks the NSF LSAMP Program (grant HRD-0413000) for research support. The Materials Chemistry Laboratory at the University of Illinois was supported in part by grants from the NSF (CHE 95–03145 and CHE 03–43032).

References

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