4-Phenyl-14,18-dithia-4-phosphatricyclo­[18.4.0.0^7,12]tetra­cosa-2,5-dien-4-one benzene hemisolvate

The asymmetric unit of the title compound, C₂₇H₂₇OPS₂·0.5C₆H₆, is composed of a heterocyclic molecule and one half-benzene ring, the solvent molecule being located on a centre of inversion. The 16-membered ring has an irregular −ap, −ap, +sp, +ac, −sc, +ap, −ap, −sc, +ap, −ap, +sc, +sp, −ap, +ap, +sp, −ac conformation. The phospho­rus tetra­hedron exhibits its usual deformation, with C—P—C angles smaller than the usual tetra­hedral value of 109.5° and O—P—C angles greater than this value. In the structure, there is a stacking inter­action between the P-bonded benzene rings. Furthermore, there is a weak inter­molecular C—H...O hydrogen bond. In this way, a hydrogen-bonded chain is created along the crystallographic a axis.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.062
• wR factor = 0.182
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT331_ALERT_2_A Small Average Phenyl C-C Dist.   C51    -C53_a         1.33 Ang.

Author Response: Small average benzene C-C distance is caused by disorder. For details see comment.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.60 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C26
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C22
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist.   C22    -C27           1.37 Ang.

Author Response: Small average benzene C-C distance is caused by disorder. For details see comment.

PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The design of cation-binding compounds for biological, environmental or recycling purposes is of crucial importance (Bashall et al., 1994). The development of new technologies, based on binding of cations, is restrained by the properties of the ligands used. Thus, compounds like crown ethers (Pedersen, 1967), podands or cryptands (Lehn, 1978; Mathieu et al., 1978), were recently widely studied (Hancock et al., 1996; Lukes et al., 2001). The main disadvantage of podands is their low selectivity (Pujo-Bouteille et al., 1998). Crown ethers and cryptands selectively and specifically bind different cations. For example, [2.2.2]-cryptand (trade name Kryptofix) selectively binds K⁺ cations, when [2.2.1]-cryptand selectively binds Na⁺ cations and PNP-5-ethers bind only alkaline metals without preferring any of them (Kruszynski & Wieczorek, 2004). There is a great need of agents, which interact with specific cations. Increasing selectivity can be imposed by the introduction of geometric restraints. Complexation depends not only on an appropriate topography, but also on neutralizing the charge of the ion or on possessing electron lone pairs·Thus, introducing —P═O or —P═S groups should affect the selectivity of the compound (Kruszynski & Wieczorek, 2004). We have designed and synthesized a compound containing a 16-membered heteroatom ring, with geometrical restraints induced by double bonds, and three structural units capable of binding cations; the π-electron clouds of aromatic rings and the electron lone pairs of S and O atoms.

A perspective view of the title compound, (I), together with the atom-numbering scheme is shown in Fig. 1. The asymmetric unit is composed of a tricyclic molecule and half a benzene ring located on a centre of inversion. The solvent benzene molecule shows signs of disorder, which is demonstrated by relatively large displacement ellipsoids. This is the first structure of a 16-membered heteroatom ring containing one P and two S atoms in positions 1, 7 and 11. The 16-membered ring has irregular -ap, -ap, +sp, +ac, -sc, +ap, -ap, -sc, +ap, -ap, +sc, +sp, -ap, +ap, +sp, -ac conformation (beginning with P1—C1—C2—C3 and following with C1—C2—C3—C8). The tetrahedrally coordinated P atom exhibits its usual deformation, with C—P—C and angles smaller than 109.5° and O—P—C angles greater than 109.5° (Table 1). The macrocyclic benzene rings are inclined by 88.28 (10)° with respect to each other, and make angles of 77.85 (13) and 84.21 (10)° with the fused benzene ring. In the structure, a stacking interaction can be found between the fused benzene rings [second ring generated by (−x + 1, −y + 1, −z + 2); the distance between ring centroids is 4.229 (6) Å, the perpendicular distance between the rings is 3.682 (6) Å, and the angle between the vector linking the ring centroids and normal to one of planes is 29.4 (4)°]. In addition, there is one intermolecular C—H···O contact (Table 2 and Fig. 2), which according to Desiraju & Steiner (1999) can be classified as a weak hydrogen bond. In this way, a hydrogen-bonded chain is created along the crystallographic a axis. There are no further unusual intermolecular short contact in the structure.

S2. Experimental

The title compound was synthesized according to the method of Pietrusiewicz (2000). Elemental analysis for C, H, O, P, S (calculated/found): 71.83/71.91, 6.03/5.99, 3.19/3.14, 6.17/6.01, 12.78/12.66%. IR (KBr, cm⁻¹): 3120 (s, νC—H, ar), 3055 (m, νC—H, CH), 2910 (s, νC—H, CH₂), 2870 (s, νC—H, CH₂), 1670 (m, νCδb C), 1600 (s, νCδdb C), 1525 (s, νCδdb C), 1455 (v, νC—H, CH₂), 1263 (m, νPδb O), 705 (m, νC(—S). FABs–MS [M+H]⁺: 79, 463.

S3. Refinement

H atoms were placed in calculated positions and refined as riding on their parent atoms [aromatic C—H = 0.93 Å, CH₂ C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Version 1.4; Bruno et al., 2002) and ORTEP-3 (Windows Version 1.062; Farrugia 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Part of the molecular packing of the title compound, showing intermolecular hydrogen bonds creating a chain along the crystallographic a axis. Hydrogen bonds are indicated by dashed lines.

4-Phenyl-14,18-dithia-4-phosphatricyclo[18.4.0.0^7,12]tetracosa-2,5- dien-4-one benzene solvate

Crystal data

C27H27OPS2·0.5C6H6	Z = 2
Mr = 501.67	F(000) = 530
Triclinic, P1	Dx = 1.243 Mg m^−3
a = 5.492 (1) Å	Cu Kα radiation, λ = 1.54178 Å
b = 14.098 (1) Å	Cell parameters from 25 reflections
c = 18.056 (1) Å	θ = 5.0–25.0°
α = 101.92 (1)°	µ = 2.51 mm^−1
β = 91.52 (1)°	T = 291 K
γ = 100.83 (1)°	Prism, colourless
V = 1340.4 (3) Å^3	0.35 × 0.33 × 0.31 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	5155 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
Graphite monochromator	θmax = 75.0°, θmin = 2.5°
ω–2θ scans	h = 0→6
Absorption correction: numerical (X-RED32; Stoe & Cie, 1999)	k = −17→17
Tmin = 0.473, Tmax = 0.507	l = −22→22
6116 measured reflections	3 standard reflections every 60 min
5512 independent reflections	intensity decay: 11.3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: mixed
wR(F^2) = 0.182	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.1002P)^2 + 0.714P] where P = (Fo^2 + 2Fc^2)/3
5512 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.44869 (9)	0.25594 (4)	0.83092 (3)	0.04345 (18)
S1	0.31456 (17)	0.33957 (6)	0.50919 (4)	0.0727 (2)
S2	−0.16347 (15)	0.04734 (5)	0.58578 (4)	0.0663 (2)
O1	0.7059 (3)	0.26417 (15)	0.80580 (12)	0.0623 (5)
C1	0.2688 (4)	0.32519 (17)	0.78772 (12)	0.0438 (5)
H1	0.1014	0.3215	0.8031	0.053*
C2	0.3731 (4)	0.38156 (17)	0.74235 (12)	0.0459 (5)
H2	0.5433	0.3846	0.7296	0.055*
C3	0.2556 (4)	0.45207 (17)	0.71133 (13)	0.0459 (5)
C4	0.0814 (5)	0.49724 (19)	0.75230 (14)	0.0530 (5)
H4	0.0351	0.4795	0.7975	0.064*
C5	−0.0240 (6)	0.5673 (2)	0.72771 (17)	0.0625 (6)
H5	−0.1406	0.5962	0.7559	0.075*
C6	0.0447 (6)	0.5945 (2)	0.66077 (18)	0.0682 (7)
H6	−0.0219	0.6432	0.6444	0.082*
C7	0.2107 (6)	0.5496 (2)	0.61873 (16)	0.0646 (7)
H7	0.2523	0.5672	0.5731	0.078*
C8	0.3200 (5)	0.47791 (19)	0.64224 (14)	0.0524 (5)
C9	0.4848 (5)	0.4263 (2)	0.59060 (15)	0.0612 (6)
H9A	0.5760	0.3912	0.6188	0.073*
H9B	0.6047	0.4753	0.5730	0.073*
C10	0.1007 (6)	0.2622 (3)	0.55788 (18)	0.0751 (8)
H10A	0.1917	0.2228	0.5820	0.090*
H10B	0.0285	0.3041	0.5973	0.090*
C11	−0.1018 (7)	0.1955 (3)	0.5048 (2)	0.0793 (9)
H11A	−0.0307	0.1498	0.4680	0.095*
H11B	−0.1839	0.2345	0.4776	0.095*
C12	−0.2915 (6)	0.1375 (3)	0.5465 (2)	0.0818 (9)
H12A	−0.4338	0.1037	0.5118	0.098*
H12B	−0.3485	0.1829	0.5872	0.098*
C13	−0.3635 (5)	0.0334 (2)	0.66203 (16)	0.0637 (7)
H13A	−0.3577	0.0971	0.6957	0.076*
H13B	−0.5337	0.0071	0.6418	0.076*
C14	−0.2756 (5)	−0.0360 (2)	0.70469 (16)	0.0601 (6)
C15	−0.4017 (7)	−0.1339 (3)	0.6910 (2)	0.0816 (10)
H15	−0.5429	−0.1541	0.6577	0.098*
C16	−0.3202 (9)	−0.2017 (3)	0.7263 (3)	0.0979 (13)
H16	−0.4071	−0.2668	0.7170	0.118*
C17	−0.1119 (9)	−0.1728 (3)	0.7748 (3)	0.0964 (12)
H17	−0.0565	−0.2187	0.7979	0.116*
C18	0.0172 (7)	−0.0763 (2)	0.7898 (2)	0.0762 (8)
H18	0.1583	−0.0576	0.8231	0.091*
C19	−0.0623 (5)	−0.00640 (19)	0.75526 (15)	0.0573 (6)
C20	0.0754 (5)	0.09650 (18)	0.77219 (14)	0.0513 (5)
H20	−0.0068	0.1452	0.7467	0.062*
C21	0.2804 (5)	0.13211 (18)	0.81524 (15)	0.0525 (5)
H21	0.3534	0.0977	0.8460	0.063*
C22	0.4458 (4)	0.30653 (18)	0.93115 (14)	0.0511 (5)
C23	0.2419 (6)	0.2866 (3)	0.97138 (18)	0.0800 (9)
H23	0.0980	0.2446	0.9471	0.096*
C24	0.2487 (9)	0.3284 (4)	1.0477 (2)	0.1027 (14)
H24	0.1103	0.3132	1.0748	0.123*
C25	0.4538 (9)	0.3911 (4)	1.0835 (2)	0.0980 (12)
H25	0.4583	0.4175	1.1352	0.118*
C26	0.6530 (9)	0.4153 (4)	1.0439 (2)	0.1137 (16)
H26	0.7911	0.4613	1.0678	0.136*
C27	0.6518 (7)	0.3719 (3)	0.96815 (19)	0.0845 (10)
H27	0.7919	0.3871	0.9417	0.101*
C51	0.3077 (13)	−0.0315 (7)	0.0375 (5)	0.165 (3)
H51	0.1691	−0.0524	0.0628	0.198*
C52	0.4245 (16)	0.0639 (7)	0.0547 (5)	0.163 (3)
H52	0.3736	0.1074	0.0945	0.196*
C53	0.6097 (13)	0.0964 (5)	0.0159 (4)	0.134 (2)
H53	0.6819	0.1633	0.0255	0.161*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0339 (3)	0.0507 (3)	0.0467 (3)	0.0099 (2)	0.0023 (2)	0.0113 (2)
S1	0.0887 (5)	0.0739 (5)	0.0517 (4)	0.0072 (4)	0.0087 (3)	0.0125 (3)
S2	0.0751 (5)	0.0611 (4)	0.0607 (4)	0.0161 (3)	0.0099 (3)	0.0055 (3)
O1	0.0374 (8)	0.0754 (12)	0.0769 (12)	0.0154 (8)	0.0110 (8)	0.0180 (10)
C1	0.0367 (10)	0.0502 (11)	0.0437 (11)	0.0069 (8)	0.0026 (8)	0.0103 (9)
C2	0.0410 (10)	0.0541 (12)	0.0412 (11)	0.0055 (9)	0.0010 (8)	0.0109 (9)
C3	0.0457 (11)	0.0486 (11)	0.0410 (11)	0.0037 (9)	−0.0007 (9)	0.0096 (9)
C4	0.0603 (14)	0.0540 (13)	0.0440 (11)	0.0100 (10)	0.0020 (10)	0.0104 (10)
C5	0.0698 (16)	0.0580 (15)	0.0618 (15)	0.0208 (12)	0.0036 (13)	0.0104 (12)
C6	0.0826 (19)	0.0575 (15)	0.0691 (17)	0.0185 (14)	−0.0032 (15)	0.0212 (13)
C7	0.0765 (18)	0.0636 (16)	0.0564 (15)	0.0060 (13)	0.0026 (13)	0.0262 (12)
C8	0.0538 (13)	0.0557 (13)	0.0465 (12)	0.0024 (10)	0.0019 (10)	0.0163 (10)
C9	0.0597 (15)	0.0748 (17)	0.0494 (13)	0.0047 (12)	0.0103 (11)	0.0208 (12)
C10	0.0774 (19)	0.081 (2)	0.0598 (16)	0.0001 (16)	−0.0011 (14)	0.0135 (15)
C11	0.092 (2)	0.0709 (19)	0.0695 (19)	0.0107 (16)	−0.0167 (16)	0.0112 (15)
C12	0.0722 (19)	0.0709 (19)	0.095 (2)	0.0053 (15)	−0.0214 (17)	0.0133 (17)
C13	0.0515 (14)	0.0707 (17)	0.0602 (15)	0.0099 (12)	0.0007 (11)	−0.0032 (13)
C14	0.0597 (14)	0.0566 (14)	0.0543 (14)	0.0041 (11)	0.0102 (11)	−0.0038 (11)
C15	0.080 (2)	0.0671 (19)	0.079 (2)	−0.0086 (16)	0.0057 (16)	−0.0068 (16)
C16	0.122 (3)	0.0500 (17)	0.105 (3)	−0.0095 (19)	0.012 (2)	0.0039 (18)
C17	0.127 (3)	0.0487 (16)	0.110 (3)	0.0094 (19)	0.006 (3)	0.0173 (18)
C18	0.093 (2)	0.0507 (15)	0.083 (2)	0.0100 (14)	−0.0018 (17)	0.0143 (14)
C19	0.0637 (15)	0.0469 (12)	0.0571 (14)	0.0083 (11)	0.0084 (11)	0.0034 (10)
C20	0.0543 (13)	0.0455 (12)	0.0525 (13)	0.0104 (10)	0.0021 (10)	0.0066 (10)
C21	0.0524 (13)	0.0510 (12)	0.0569 (13)	0.0152 (10)	0.0023 (10)	0.0132 (10)
C22	0.0489 (12)	0.0553 (13)	0.0499 (12)	0.0108 (10)	−0.0048 (9)	0.0139 (10)
C23	0.0719 (19)	0.099 (2)	0.0549 (16)	−0.0058 (17)	0.0080 (14)	0.0048 (16)
C24	0.109 (3)	0.127 (3)	0.0589 (19)	0.000 (3)	0.0236 (19)	0.008 (2)
C25	0.111 (3)	0.119 (3)	0.0495 (17)	0.012 (2)	−0.0090 (18)	−0.0037 (18)
C26	0.109 (3)	0.133 (4)	0.067 (2)	−0.020 (3)	−0.016 (2)	−0.008 (2)
C27	0.073 (2)	0.100 (3)	0.0627 (18)	−0.0123 (18)	−0.0077 (15)	0.0039 (17)
C51	0.131 (5)	0.164 (7)	0.214 (8)	0.029 (5)	0.080 (5)	0.066 (6)
C52	0.168 (6)	0.160 (7)	0.172 (7)	0.064 (5)	0.077 (6)	0.023 (5)
C53	0.129 (5)	0.112 (4)	0.165 (6)	0.024 (4)	−0.002 (4)	0.042 (4)

Geometric parameters (Å, º)

P1—O1	1.4859 (17)	C13—H13A	0.9700
P1—C21	1.777 (3)	C13—H13B	0.9700
P1—C1	1.781 (2)	C14—C15	1.392 (4)
P1—C22	1.805 (3)	C14—C19	1.408 (4)
S1—C9	1.813 (3)	C15—C16	1.384 (6)
S1—C10	1.819 (3)	C15—H15	0.9300
S2—C13	1.803 (3)	C16—C17	1.366 (6)
S2—C12	1.814 (4)	C16—H16	0.9300
C1—C2	1.324 (3)	C17—C18	1.379 (5)
C1—H1	0.9628	C17—H17	0.9300
C2—C3	1.473 (3)	C18—C19	1.397 (4)
C2—H2	0.9637	C18—H18	0.9300
C3—C4	1.393 (3)	C19—C20	1.470 (3)
C3—C8	1.406 (3)	C20—C21	1.305 (4)
C4—C5	1.374 (4)	C20—H20	1.0596
C4—H4	0.9300	C21—H21	0.9360
C5—C6	1.383 (4)	C22—C23	1.367 (4)
C5—H5	0.9300	C22—C27	1.375 (4)
C6—C7	1.365 (4)	C23—C24	1.379 (5)
C6—H6	0.9300	C23—H23	0.9300
C7—C8	1.398 (4)	C24—C25	1.349 (6)
C7—H7	0.9300	C24—H24	0.9300
C8—C9	1.493 (4)	C25—C26	1.351 (6)
C9—H9A	0.9700	C25—H25	0.9300
C9—H9B	0.9700	C26—C27	1.377 (5)
C10—C11	1.490 (4)	C26—H26	0.9300
C10—H10A	0.9700	C27—H27	0.9300
C10—H10B	0.9700	C51—C53^i	1.337 (10)
C11—C12	1.516 (5)	C51—C52	1.345 (10)
C11—H11A	0.9700	C51—H51	0.9300
C11—H11B	0.9700	C52—C53	1.315 (9)
C12—H12A	0.9700	C52—H52	0.9300
C12—H12B	0.9700	C53—C51^i	1.337 (10)
C13—C14	1.502 (4)	C53—H53	0.9300
O1—P1—C21	113.51 (12)	C14—C13—H13A	110.0
O1—P1—C1	113.10 (11)	S2—C13—H13A	110.0
C21—P1—C1	107.95 (11)	C14—C13—H13B	110.0
O1—P1—C22	111.75 (12)	S2—C13—H13B	110.0
C21—P1—C22	106.03 (12)	H13A—C13—H13B	108.4
C1—P1—C22	103.80 (11)	C15—C14—C19	119.0 (3)
C9—S1—C10	99.52 (13)	C15—C14—C13	118.9 (3)
C13—S2—C12	100.59 (17)	C19—C14—C13	122.0 (2)
C2—C1—P1	119.89 (17)	C16—C15—C14	120.9 (3)
C2—C1—H1	125.0	C16—C15—H15	119.5
P1—C1—H1	114.9	C14—C15—H15	119.5
C1—C2—C3	125.2 (2)	C17—C16—C15	119.9 (3)
C1—C2—H2	122.3	C17—C16—H16	120.1
C3—C2—H2	112.3	C15—C16—H16	120.1
C4—C3—C8	118.6 (2)	C16—C17—C18	120.7 (4)
C4—C3—C2	119.6 (2)	C16—C17—H17	119.6
C8—C3—C2	121.8 (2)	C18—C17—H17	119.6
C5—C4—C3	121.8 (2)	C17—C18—C19	120.5 (3)
C5—C4—H4	119.1	C17—C18—H18	119.8
C3—C4—H4	119.1	C19—C18—H18	119.8
C4—C5—C6	119.5 (3)	C18—C19—C14	119.0 (3)
C4—C5—H5	120.2	C18—C19—C20	120.1 (3)
C6—C5—H5	120.2	C14—C19—C20	120.9 (2)
C7—C6—C5	119.8 (3)	C21—C20—C19	126.8 (2)
C7—C6—H6	120.1	C21—C20—H20	118.7
C5—C6—H6	120.1	C19—C20—H20	114.5
C6—C7—C8	121.9 (3)	C20—C21—P1	125.4 (2)
C6—C7—H7	119.1	C20—C21—H21	124.9
C8—C7—H7	119.1	P1—C21—H21	109.5
C7—C8—C3	118.4 (2)	C23—C22—C27	118.2 (3)
C7—C8—C9	118.9 (2)	C23—C22—P1	122.7 (2)
C3—C8—C9	122.5 (2)	C27—C22—P1	119.0 (2)
C8—C9—S1	112.82 (19)	C22—C23—C24	120.3 (3)
C8—C9—H9A	109.0	C22—C23—H23	119.8
S1—C9—H9A	109.0	C24—C23—H23	119.8
C8—C9—H9B	109.0	C25—C24—C23	120.7 (4)
S1—C9—H9B	109.0	C25—C24—H24	119.6
H9A—C9—H9B	107.8	C23—C24—H24	119.6
C11—C10—S1	111.8 (2)	C24—C25—C26	119.8 (3)
C11—C10—H10A	109.3	C24—C25—H25	120.1
S1—C10—H10A	109.3	C26—C25—H25	120.1
C11—C10—H10B	109.3	C25—C26—C27	120.1 (4)
S1—C10—H10B	109.3	C25—C26—H26	119.9
H10A—C10—H10B	107.9	C27—C26—H26	119.9
C10—C11—C12	111.6 (3)	C22—C27—C26	120.7 (4)
C10—C11—H11A	109.3	C22—C27—H27	119.6
C12—C11—H11A	109.3	C26—C27—H27	119.6
C10—C11—H11B	109.3	C53^i—C51—C52	120.2 (6)
C12—C11—H11B	109.3	C53^i—C51—H51	119.9
H11A—C11—H11B	108.0	C52—C51—H51	119.9
C11—C12—S2	111.8 (3)	C53—C52—C51	120.9 (7)
C11—C12—H12A	109.3	C53—C52—H52	119.6
S2—C12—H12A	109.3	C51—C52—H52	119.6
C11—C12—H12B	109.3	C52—C53—C51^i	118.8 (7)
S2—C12—H12B	109.3	C52—C53—H53	120.6
H12A—C12—H12B	107.9	C51^i—C53—H53	120.6
C14—C13—S2	108.35 (19)
P1—C1—C2—C3	−171.50 (17)	C11—C12—S2—C13	155.6 (2)
C1—C2—C3—C8	−152.8 (2)	C12—S2—C13—C14	−177.01 (19)
C2—C3—C8—C9	8.4 (4)	S2—C13—C14—C19	75.7 (3)
C3—C8—C9—S1	103.1 (3)	C13—C14—C19—C20	3.9 (4)
C8—C9—S1—C10	−56.4 (2)	C14—C19—C20—C21	−176.9 (3)
C9—S1—C10—C11	168.0 (3)	C19—C20—C21—P1	177.0 (2)
S1—C10—C11—C12	−175.2 (3)	C20—C21—P1—C1	7.2 (3)
C10—C11—C12—S2	−68.6 (4)	C21—P1—C1—C2	−130.6 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1^ii	0.96	2.18	3.094 (3)	159

Symmetry code: (ii) x−1, y, z.