Bis[2,2′-(phenyl­phosphinediyl)­dibenzene­thiol­ato-κ³S,P,S′]germanium(IV)

Two tridentate phosphinethiol­ate ligands, [PhP(C₆H₄S-2)₂]²⁻, coordinate to the Ge^IV centre in a facial manner yielding the title compound, [Ge(C₁₈H₁₃PS₂)₂], which exhibits a pseudo-twofold symmetry with the two P-atom donors in a cis configuration. The Ge centre has a distorted octahedral environment. Two phenyl rings, one from each of the phosphinethiol­ate ligands, are parallel to one another, indicating π–π interactions. The molecules are linked by weak C—H...π and C—H...S interactions.

S1. Comment

Thiolates and phosphines are common ligands in coordination chemistry. Bidentate ligands using a combination of both donor sites have attracted much attention in recent decades (Stephan, 1984; Dilworth et al., 1992). Metal complexes bearing polydentate ligands with both donor sites {e.g. [PhP(C₆H₄S-2)₂]⁻²} are used in frontier research areas, such as biomimetic (Nguyen et al., 1996), metal–organic chemical vapour deposition (Pérez-Lourido et al., 1999) and catalytic (Clark et al., 2000) studies. In the course of studying the different ³¹P NMR behaviour of metal complexes with phosphinothiolate, we found that metal complexes containing the heavier congener of group 14 (i.e. Ge, Sn or Pb) have seldom been studied. Only one relevant structure with Sn, {PhP[C₆H₃(S-2)(SiMe₃-3)]₂}₂Sn₂ (Froelich et al., 1996), has been reported to date. We report here the first crystal structure of a Ge complex obtained by the reaction of a phosphinothiolate ligand and germanium chloride in tetrahydrofuran. n-BuLi was used to remove H atoms from the proligands (phenylphosphinothiol), yielding the tridentate ligand [PhP(C₆H₄S-2)₂]⁻² (L), which coordinates to the Ge centre to give the title complex, GeL₂, (I).

Complex (I) contains a Ge centre with two [PhP(C₆H₄S-2)₂]⁻² ligands (Fig. 1). Each tridentate ligand uses one P and two S donor sites to coordinate to the Ge centre in a facial manner. Molecular models strongly suggest that the ligand favours facial over meridional coordination in an octahedral complex, mainly due to the pyramidal coordination of P (Dilworth et al., 1996). The octahedron formed by the two ligands around the Ge centre is slightly distorted, due to the bite angles of the ligands (ca 81–85°) and the steric repulsion between the phosphine groups, which leads to a P1—Ge—P2 angle of 100.34 (3)°.

Complex (I) exhibits a pseudo-twofold symmetry on the P1/P2/S1/S3 plane through the Ge centre. In a rare Re^IV analogue, ReL₂ (Dilworth et al., 1996), the pseudo-twofold symmetry becomes crystallographically real. The overall geometry of these two complexes is strikingly similar, except that the P1—Re—P2 angle of 108.8 (1)° is somewhat larger than the P1—Ge—P2 angle.

The Ge—P bond lengths [2.413 (1) and 2.417 (1) Å] in (I) are almost identical to those observed in Ge[Me₃SiC(PMe₂)₂]₂Cl₂ (2.410–2.413 Å; Karsch et al., 1996), the only reported six-coordinated Ge complex available containing Ge—P bonds. Most of the Ge—S distances in (I) are around 2.4 Å (Table 1). These values are comparable with those cited for the six-coordinated complex [(L¹Fe)₂Ge][BPh₄] [2.422, 2.433 and 2.438 Å; L¹ is 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane; Glaser et al., 1999]. The reported Ge—S bond lengths in Ge complexes involving the mercaptophenyl group range from 2.195 Å in tris(benzene-1,2-dithiolato-S,S')germanium(IV) (Pfeiffer et al., 1989) to 2.477 Å in (L²)₂Ge [L² is 2,2'-thiotris(4,6-di-tert-butylphenolate); Pastor et al., 1997]. Of all the Ge—S distances in (I), only the Ge—S1 distance of 2.343 (1) Å is significantly shorter than the others (Table 1).

The two phenyl rings, one from each of the two phosphinothiolate ligands, are parallel to each other, with a separation (ring centroid to phenyl plane) of 3.5 (1) Å. This usually indicates the existence of a π–π interaction. Although similar distances between phenyl–phenyl planes are found in the ReL₂ analogue [3.1 (1) and 3.5 (1) Å for two independent molecules], the phenyl pairs are positioned differently in these two complexes. In ReL₂, the two phenyl rings are twisted away from each other, while those in (I) are arranged almost face to face (Fig. 1). Compared with the ReL₂ analogue, the smaller P—M—P angle (ca 8° smaller) in (I), together with the larger S—M—S angle (ca 10° larger) across it, provides evidence for a stronger π–π interaction in (I). These angular differences are consistent with the twist of the coordination planes around the metal centre. In (I), the twist between the P2/Ge1/S3 and P1/Ge1/S1 planes is 6.2 (1)°, while the twist between similar planes in ReL₂ is 17.1 (1)°. The smaller twist in (I) brings the two phenyl rings closer and hence produces a smaller P—M—P angle.

The molecules of (I) pack with weak C—H···π and C—H···S hydrogen-bond interactions (Table 2). The C—H···S interatomic distances and angles are comparable with those found in the report on Zn₂(µ-C₆H₄S₂)₂(C₁₀H₈N₂)₂ [H···S = 2.84 Å, C···S = 3.637 (2) Å and C—H···S = 143°], where a possible C—H···S hydrogen bond is proposed (Hatch et al., 2003).

S2. Experimental

The title complex was obtained in a two-step reaction. First, the phosphinothiolate ligand was generated by mixing a tetrahydrofuran (thf) solution of the proligand PhP(C₆H₄SH-2)₂ with n-BuLi in a 1:2 molar ratio at 273 K. An equimolar quantity (with respect to the ligand) of GeCl₄ was added to this solution and stirred for 4 h. The yellow precipitate extracted using CH₂Cl₂ gave suitable crystals of (I) on re-crystallization in thf. The melting point was determined to be 542 (1) K. The ¹H NMR spectrum gave a multiplet around 6.85–7.16 p.p.m. and ³¹P NMR a singlet at −17.82 p.p.m.

S3. Refinement

All H atoms were placed in calculated positions with C—H distances of 0.93 Å. They were included using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular packing of (I), showing the intermolecular C—H···S and most of the C—H···π interactions (Table 2). [Symmetry codes: (2) 1 − x, 1/2 + y, 1/2 − z; (3) −x, −y, 1 − z; (3a) 1 − x, 1 − y, 1 − z; (4) x, 1/2 − y, 1/2 + z.]

Bis[2,2'-(phenylphosphinediyl)dibenzenethiolato-κ³S,P,S']germanium(IV)

Crystal data

[Ge(C18H13PS2)2]	F(000) = 1472
Mr = 721.34	Dx = 1.478 Mg m^−3
Monoclinic, P21/c	Melting point: 269(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71069 Å
a = 11.537 (4) Å	Cell parameters from 20 reflections
b = 16.729 (3) Å	θ = 4.9–7.4°
c = 16.882 (4) Å	µ = 1.33 mm^−1
β = 95.96 (2)°	T = 298 K
V = 3240.7 (14) Å^3	Prism, yellow
Z = 4	0.55 × 0.35 × 0.25 mm

Data collection

Rigaku AFC-7S diffractometer	Rint = 0.026
ω/2θ scans	θmax = 26°, θmin = 2.2°
Absorption correction: ψ scan (North et al., 1968)	h = 0→14
Tmin = 0.635, Tmax = 0.720	k = 0→20
6696 measured reflections	l = −20→20
6369 independent reflections	3 standard reflections every 150 reflections
3913 reflections with I > 2σ(I)	intensity decay: −0.4%

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0243P)^2 + 0.899P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.033	(Δ/σ)max = 0.001
wR(F^2) = 0.094	Δρmax = 0.34 e Å^−3
S = 1.01	Δρmin = −0.30 e Å^−3
6369 reflections	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
389 parameters	Extinction coefficient: 0.00152 (17)
0 restraints

Special details

Experimental. The scan width was (1.31 + 0.35tanθ)° with an ω scan speed of 16° per minute (up to 4 scans to achieve I/σ(I) > 15). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.4976 (3)	0.1715 (2)	0.15359 (18)	0.0426 (8)
C2	0.5242 (3)	0.2473 (2)	0.1273 (2)	0.0547 (9)
H2	0.5083	0.292	0.1571	0.066*
C3	0.5742 (3)	0.2564 (3)	0.0569 (2)	0.0671 (11)
H3	0.5932	0.3071	0.0397	0.08*
C4	0.5956 (3)	0.1903 (3)	0.0123 (2)	0.0698 (12)
H4	0.6294	0.1966	−0.0349	0.084*
C5	0.5676 (3)	0.1150 (3)	0.0366 (2)	0.0594 (10)
H5	0.5806	0.0711	0.0049	0.071*
C6	0.5198 (3)	0.1038 (2)	0.1085 (2)	0.0482 (9)
C7	0.5446 (3)	0.12284 (19)	0.31860 (18)	0.0405 (7)
C8	0.6420 (3)	0.1717 (2)	0.3370 (2)	0.0528 (9)
H8	0.6467	0.2207	0.3116	0.063*
C9	0.7313 (3)	0.1477 (3)	0.3927 (3)	0.0727 (12)
H9	0.7966	0.1799	0.4045	0.087*
C10	0.7222 (4)	0.0755 (3)	0.4304 (3)	0.0888 (15)
H10	0.7814	0.0596	0.4687	0.107*
C11	0.6283 (4)	0.0266 (3)	0.4129 (3)	0.0730 (12)
H11	0.6251	−0.0221	0.4391	0.088*
C12	0.5370 (3)	0.0487 (2)	0.3562 (2)	0.0464 (8)
C13	0.3606 (3)	0.24116 (18)	0.27134 (19)	0.0390 (7)
C14	0.2812 (3)	0.2785 (2)	0.2152 (2)	0.0591 (10)
H14	0.2674	0.2579	0.1639	0.071*
C15	0.2238 (4)	0.3458 (3)	0.2363 (3)	0.0806 (14)
H15	0.1712	0.371	0.199	0.097*
C16	0.2430 (4)	0.3758 (2)	0.3113 (3)	0.0812 (14)
H16	0.204	0.4218	0.3245	0.097*
C17	0.3193 (4)	0.3392 (2)	0.3676 (3)	0.0665 (11)
H17	0.3311	0.3597	0.419	0.08*
C18	0.3784 (3)	0.2719 (2)	0.3474 (2)	0.0474 (8)
H18	0.4306	0.247	0.3853	0.057*
C19	0.1245 (3)	−0.04691 (19)	0.3094 (2)	0.0426 (8)
C20	0.1721 (3)	−0.1125 (2)	0.2713 (2)	0.0501 (9)
C21	0.1582 (3)	−0.1887 (2)	0.3030 (3)	0.0646 (11)
H21	0.19	−0.2327	0.2796	0.077*
C22	0.0989 (4)	−0.1991 (2)	0.3677 (3)	0.0733 (13)
H22	0.0883	−0.2505	0.3865	0.088*
C23	0.0540 (4)	−0.1347 (3)	0.4060 (3)	0.0697 (12)
H23	0.0158	−0.1428	0.4512	0.084*
C24	0.0662 (3)	−0.0584 (2)	0.3766 (2)	0.0532 (9)
H24	0.0356	−0.0149	0.4017	0.064*
C25	0.0452 (3)	0.06936 (18)	0.18684 (19)	0.0409 (8)
C26	−0.0738 (3)	0.06807 (19)	0.1970 (2)	0.0487 (9)
H26	−0.0977	0.0605	0.2474	0.058*
C27	−0.1550 (3)	0.0781 (2)	0.1321 (2)	0.0583 (10)
H27	−0.2341	0.079	0.1387	0.07*
C28	−0.1187 (3)	0.0869 (2)	0.0571 (2)	0.0552 (10)
H28	−0.174	0.0923	0.0133	0.066*
C29	−0.0031 (3)	0.08777 (19)	0.0464 (2)	0.0471 (8)
H29	0.0194	0.0935	−0.0046	0.057*
C30	0.0827 (3)	0.08004 (18)	0.11180 (18)	0.0388 (7)
C31	0.1394 (3)	0.12209 (18)	0.34870 (19)	0.0390 (7)
C32	0.0676 (3)	0.1879 (2)	0.3389 (2)	0.0524 (9)
H32	0.0218	0.1957	0.2909	0.063*
C33	0.0633 (4)	0.2424 (2)	0.4002 (2)	0.0628 (10)
H33	0.0137	0.2863	0.3938	0.075*
C34	0.1329 (4)	0.2316 (2)	0.4708 (2)	0.0658 (11)
H34	0.1298	0.2681	0.5121	0.079*
C35	0.2063 (4)	0.1674 (2)	0.4803 (2)	0.0626 (10)
H35	0.2542	0.161	0.5277	0.075*
C36	0.2098 (3)	0.1124 (2)	0.4203 (2)	0.0514 (9)
H36	0.2593	0.0686	0.4274	0.062*
P1	0.43131 (7)	0.15171 (5)	0.24313 (5)	0.03569 (19)
P2	0.15233 (7)	0.05018 (5)	0.27032 (5)	0.03649 (19)
S1	0.49654 (8)	0.00613 (6)	0.14389 (6)	0.0552 (2)
S2	0.42126 (8)	−0.01910 (5)	0.33668 (6)	0.0518 (2)
S3	0.24374 (9)	−0.10036 (5)	0.18502 (6)	0.0567 (3)
S4	0.22994 (7)	0.08414 (6)	0.09253 (5)	0.0472 (2)
Ge1	0.33115 (3)	0.027470 (19)	0.21073 (2)	0.03788 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0351 (17)	0.056 (2)	0.0356 (17)	−0.0016 (16)	−0.0008 (14)	−0.0006 (16)
C2	0.050 (2)	0.066 (2)	0.047 (2)	−0.0068 (19)	0.0044 (17)	0.0065 (18)
C3	0.057 (2)	0.086 (3)	0.058 (2)	−0.008 (2)	0.008 (2)	0.023 (2)
C4	0.051 (2)	0.117 (4)	0.043 (2)	0.001 (3)	0.0080 (19)	0.015 (2)
C5	0.0352 (19)	0.095 (3)	0.047 (2)	0.008 (2)	−0.0009 (16)	−0.010 (2)
C6	0.0333 (17)	0.069 (2)	0.0407 (19)	0.0013 (16)	−0.0023 (15)	−0.0017 (17)
C7	0.0341 (16)	0.0444 (18)	0.0412 (18)	0.0057 (15)	−0.0051 (14)	−0.0035 (15)
C8	0.042 (2)	0.065 (2)	0.050 (2)	−0.0051 (18)	−0.0022 (16)	−0.0056 (18)
C9	0.047 (2)	0.091 (3)	0.075 (3)	−0.009 (2)	−0.018 (2)	−0.008 (3)
C10	0.065 (3)	0.103 (4)	0.088 (3)	0.009 (3)	−0.041 (3)	0.008 (3)
C11	0.063 (3)	0.069 (3)	0.079 (3)	0.010 (2)	−0.030 (2)	0.014 (2)
C12	0.0410 (19)	0.049 (2)	0.0474 (19)	0.0082 (16)	−0.0061 (15)	0.0009 (16)
C13	0.0398 (17)	0.0294 (16)	0.0479 (19)	−0.0019 (14)	0.0049 (15)	0.0021 (14)
C14	0.061 (2)	0.048 (2)	0.065 (2)	0.0096 (19)	−0.008 (2)	0.0097 (18)
C15	0.074 (3)	0.052 (3)	0.112 (4)	0.025 (2)	−0.006 (3)	0.015 (3)
C16	0.074 (3)	0.039 (2)	0.132 (4)	0.008 (2)	0.020 (3)	−0.011 (3)
C17	0.059 (3)	0.049 (2)	0.094 (3)	−0.008 (2)	0.018 (2)	−0.026 (2)
C18	0.0438 (19)	0.0427 (19)	0.055 (2)	−0.0061 (16)	0.0027 (16)	−0.0073 (16)
C19	0.0392 (18)	0.0356 (17)	0.0502 (19)	−0.0024 (14)	−0.0093 (15)	0.0059 (15)
C20	0.048 (2)	0.0367 (18)	0.062 (2)	−0.0068 (16)	−0.0113 (17)	0.0018 (16)
C21	0.061 (2)	0.037 (2)	0.093 (3)	−0.0054 (18)	−0.005 (2)	0.010 (2)
C22	0.074 (3)	0.041 (2)	0.103 (4)	−0.012 (2)	−0.001 (3)	0.028 (2)
C23	0.063 (3)	0.075 (3)	0.071 (3)	−0.017 (2)	0.003 (2)	0.029 (2)
C24	0.049 (2)	0.051 (2)	0.058 (2)	−0.0093 (17)	−0.0029 (18)	0.0105 (18)
C25	0.0365 (17)	0.0315 (16)	0.052 (2)	0.0002 (14)	−0.0091 (15)	0.0043 (15)
C26	0.0412 (19)	0.0394 (19)	0.064 (2)	−0.0050 (15)	−0.0035 (17)	0.0062 (17)
C27	0.0355 (19)	0.051 (2)	0.085 (3)	−0.0047 (16)	−0.0126 (19)	0.008 (2)
C28	0.048 (2)	0.044 (2)	0.067 (3)	−0.0001 (17)	−0.0242 (19)	0.0004 (18)
C29	0.057 (2)	0.0330 (17)	0.047 (2)	0.0002 (16)	−0.0137 (16)	0.0000 (15)
C30	0.0416 (18)	0.0303 (16)	0.0420 (18)	−0.0001 (14)	−0.0077 (14)	0.0001 (14)
C31	0.0403 (17)	0.0333 (16)	0.0434 (18)	−0.0040 (14)	0.0047 (15)	0.0011 (14)
C32	0.052 (2)	0.045 (2)	0.059 (2)	−0.0008 (17)	0.0002 (18)	−0.0012 (17)
C33	0.071 (3)	0.043 (2)	0.075 (3)	0.0051 (19)	0.010 (2)	−0.0104 (19)
C34	0.082 (3)	0.053 (2)	0.065 (3)	−0.010 (2)	0.020 (2)	−0.020 (2)
C35	0.076 (3)	0.066 (3)	0.045 (2)	−0.006 (2)	0.005 (2)	−0.0064 (19)
C36	0.058 (2)	0.050 (2)	0.046 (2)	0.0038 (17)	0.0031 (17)	0.0009 (16)
P1	0.0341 (4)	0.0353 (4)	0.0364 (4)	0.0017 (3)	−0.0028 (3)	−0.0002 (3)
P2	0.0357 (4)	0.0320 (4)	0.0403 (4)	0.0004 (3)	−0.0030 (3)	0.0024 (3)
S1	0.0487 (5)	0.0551 (5)	0.0619 (6)	0.0137 (4)	0.0056 (4)	−0.0140 (5)
S2	0.0536 (5)	0.0415 (5)	0.0567 (5)	0.0031 (4)	−0.0116 (4)	0.0109 (4)
S3	0.0694 (6)	0.0358 (5)	0.0637 (6)	−0.0030 (4)	0.0014 (5)	−0.0115 (4)
S4	0.0444 (5)	0.0557 (5)	0.0399 (4)	0.0007 (4)	−0.0036 (4)	0.0044 (4)
Ge1	0.03819 (19)	0.03251 (18)	0.04136 (19)	0.00401 (15)	−0.00347 (14)	−0.00254 (14)

Geometric parameters (Å, º)

C1—C2	1.388 (5)	C20—C21	1.398 (5)
C1—C6	1.404 (5)	C20—S3	1.759 (4)
C1—P1	1.794 (3)	C21—C22	1.358 (6)
C2—C3	1.382 (5)	C21—H21	0.93
C2—H2	0.93	C22—C23	1.385 (6)
C3—C4	1.375 (6)	C22—H22	0.93
C3—H3	0.93	C23—C24	1.383 (5)
C4—C5	1.373 (6)	C23—H23	0.93
C4—H4	0.93	C24—H24	0.93
C5—C6	1.396 (5)	C25—C30	1.392 (4)
C5—H5	0.93	C25—C26	1.402 (5)
C6—S1	1.770 (4)	C25—P2	1.804 (3)
C7—C8	1.398 (5)	C26—C27	1.376 (5)
C7—C12	1.401 (5)	C26—H26	0.93
C7—P1	1.794 (3)	C27—C28	1.382 (5)
C8—C9	1.380 (5)	C27—H27	0.93
C8—H8	0.93	C28—C29	1.365 (5)
C9—C10	1.374 (6)	C28—H28	0.93
C9—H9	0.93	C29—C30	1.410 (4)
C10—C11	1.364 (6)	C29—H29	0.93
C10—H10	0.93	C30—S4	1.764 (3)
C11—C12	1.397 (5)	C31—C32	1.378 (5)
C11—H11	0.93	C31—C36	1.393 (4)
C12—S2	1.756 (4)	C31—P2	1.806 (3)
C13—C18	1.378 (4)	C32—C33	1.384 (5)
C13—C14	1.395 (4)	C32—H32	0.93
C13—P1	1.792 (3)	C33—C34	1.377 (6)
C14—C15	1.372 (5)	C33—H33	0.93
C14—H14	0.93	C34—C35	1.367 (5)
C15—C16	1.358 (6)	C34—H34	0.93
C15—H15	0.93	C35—C36	1.373 (5)
C16—C17	1.371 (6)	C35—H35	0.93
C16—H16	0.93	C36—H36	0.93
C17—C18	1.378 (5)	P1—Ge1	2.4131 (10)
C17—H17	0.93	P2—Ge1	2.4173 (12)
C18—H18	0.93	S1—Ge1	2.3429 (12)
C19—C24	1.390 (5)	S2—Ge1	2.3979 (11)
C19—C20	1.412 (5)	S3—Ge1	2.3848 (10)
C19—P2	1.795 (3)	S4—Ge1	2.4000 (10)
C2—C1—C6	120.3 (3)	C23—C24—H24	120.1
C2—C1—P1	124.5 (3)	C19—C24—H24	120.1
C6—C1—P1	115.2 (3)	C30—C25—C26	121.0 (3)
C3—C2—C1	120.1 (4)	C30—C25—P2	118.8 (2)
C3—C2—H2	119.9	C26—C25—P2	120.1 (3)
C1—C2—H2	119.9	C27—C26—C25	119.7 (4)
C4—C3—C2	119.7 (4)	C27—C26—H26	120.1
C4—C3—H3	120.1	C25—C26—H26	120.1
C2—C3—H3	120.1	C26—C27—C28	119.7 (3)
C5—C4—C3	120.9 (4)	C26—C27—H27	120.1
C5—C4—H4	119.6	C28—C27—H27	120.1
C3—C4—H4	119.6	C29—C28—C27	121.1 (3)
C4—C5—C6	120.6 (4)	C29—C28—H28	119.5
C4—C5—H5	119.7	C27—C28—H28	119.5
C6—C5—H5	119.7	C28—C29—C30	120.8 (3)
C5—C6—C1	118.3 (3)	C28—C29—H29	119.6
C5—C6—S1	120.4 (3)	C30—C29—H29	119.6
C1—C6—S1	121.3 (3)	C25—C30—C29	117.7 (3)
C8—C7—C12	120.2 (3)	C25—C30—S4	124.7 (2)
C8—C7—P1	120.7 (3)	C29—C30—S4	117.6 (3)
C12—C7—P1	119.0 (2)	C32—C31—C36	119.0 (3)
C9—C8—C7	120.5 (4)	C32—C31—P2	122.6 (3)
C9—C8—H8	119.7	C36—C31—P2	118.3 (3)
C7—C8—H8	119.7	C31—C32—C33	120.3 (3)
C10—C9—C8	118.9 (4)	C31—C32—H32	119.8
C10—C9—H9	120.6	C33—C32—H32	119.8
C8—C9—H9	120.6	C34—C33—C32	119.8 (4)
C11—C10—C9	121.6 (4)	C34—C33—H33	120.1
C11—C10—H10	119.2	C32—C33—H33	120.1
C9—C10—H10	119.2	C35—C34—C33	120.2 (4)
C10—C11—C12	121.0 (4)	C35—C34—H34	119.9
C10—C11—H11	119.5	C33—C34—H34	119.9
C12—C11—H11	119.5	C34—C35—C36	120.3 (4)
C11—C12—C7	117.8 (3)	C34—C35—H35	119.8
C11—C12—S2	117.6 (3)	C36—C35—H35	119.8
C7—C12—S2	124.7 (2)	C35—C36—C31	120.3 (3)
C18—C13—C14	119.3 (3)	C35—C36—H36	119.9
C18—C13—P1	122.1 (2)	C31—C36—H36	119.9
C14—C13—P1	118.5 (3)	C13—P1—C1	108.37 (16)
C15—C14—C13	119.4 (4)	C13—P1—C7	110.74 (15)
C15—C14—H14	120.3	C1—P1—C7	107.77 (15)
C13—C14—H14	120.3	C13—P1—Ge1	123.99 (11)
C16—C15—C14	120.7 (4)	C1—P1—Ge1	101.77 (11)
C16—C15—H15	119.7	C7—P1—Ge1	103.04 (11)
C14—C15—H15	119.7	C19—P2—C25	108.31 (14)
C15—C16—C17	120.8 (4)	C19—P2—C31	107.55 (15)
C15—C16—H16	119.6	C25—P2—C31	110.62 (15)
C17—C16—H16	119.6	C19—P2—Ge1	101.78 (12)
C16—C17—C18	119.5 (4)	C25—P2—Ge1	104.34 (12)
C16—C17—H17	120.2	C31—P2—Ge1	123.26 (11)
C18—C17—H17	120.2	C6—S1—Ge1	100.47 (12)
C13—C18—C17	120.3 (4)	C12—S2—Ge1	101.99 (12)
C13—C18—H18	119.8	C20—S3—Ge1	100.30 (11)
C17—C18—H18	119.8	C30—S4—Ge1	103.05 (11)
C24—C19—C20	120.6 (3)	S1—Ge1—S3	97.23 (4)
C24—C19—P2	123.1 (3)	S1—Ge1—S2	94.46 (4)
C20—C19—P2	116.2 (3)	S3—Ge1—S2	90.35 (4)
C21—C20—C19	117.9 (4)	S1—Ge1—S4	90.57 (4)
C21—C20—S3	120.3 (3)	S3—Ge1—S4	92.46 (4)
C19—C20—S3	121.8 (3)	S2—Ge1—S4	173.88 (4)
C22—C21—C20	120.8 (4)	S1—Ge1—P1	81.12 (3)
C22—C21—H21	119.6	S3—Ge1—P1	175.61 (3)
C20—C21—H21	119.6	S2—Ge1—P1	85.73 (3)
C21—C22—C23	121.3 (4)	S4—Ge1—P1	91.62 (3)
C21—C22—H22	119.3	S1—Ge1—P2	175.83 (3)
C23—C22—H22	119.3	S3—Ge1—P2	81.59 (3)
C24—C23—C22	119.6 (4)	S2—Ge1—P2	89.55 (4)
C24—C23—H23	120.2	S4—Ge1—P2	85.50 (4)
C22—C23—H23	120.2	P1—Ge1—P2	100.34 (3)
C23—C24—C19	119.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···S1^i	0.93	2.88	3.671 (3)	143
C34—H34···S4^ii	0.93	2.99	3.808 (3)	147
C22—H22···Cg1^iii	0.93	2.92	3.798 (4)	157
C27—H27···Cg2^iv	0.93	3.12	3.861 (4)	138
C15—H15···Cg3^v	0.93	3.27	3.987 (5)	136
C3—H3···Cg4^vi	0.93	3.28	4.032 (5)	139

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