Synthesis and crystal structure of bis-(μ-2-methyl-benzene-thiol-ato-κ2S:S)bis-[meth-yl(2-methyl-benzene-thiol-ato-κS)indium(III)].

The dinuclear title compound, [In2(CH3)2(C7H7S)4] or [Me(2-MeC6H4S)In-μ-(2-MeC6H4S)2InMe(2-MeC6H4S)], was prepared from the 1:2 reaction of Me3In and 2-MeC6H4SH in toluene. Its crystal structure exhibits a four-membered In2S2 ring core via bridging (2-MeC6H4S) groups. The dimeric units are further associated into a one-dimensional polymeric structure extending parallel to the a axis via inter-molecular In⋯S contacts. The In atoms are then in distorted trigonal-bipyramidal CS4 bonding environments.

Chemical context

Methyl­indium di­thiol­ates [MeIn(S2 R)] have been shown to be useful compounds for the ring-opening polymerization (ROP) of cyclic esters to produce biodegradable polymers (Allan et al., 2013 ▸; Briand et al., 2016 ▸). These compounds are prepared from the stoichiometric reaction of InMe3 with polydentate amino/oxo-di­thiols. However, the 1:2 reaction of triorganyl­indium (R 3In) with simple mono­thiols (R′SH) often results in isolation of the diorganylindium thiol­ate R 2In(SR′) (Hoffmann, 1988 ▸; Nomura et al., 1989 ▸). The favourable formation of the organylindium di­thiol­ate RIn(SR′)2 was reported to be determined by the steric bulk of the thiol­ate ligand and the R-In group, and the acidity of the thiol reactant. The 1:2 reaction of nBu3In or iBu3In and PhSH afforded the di­thiol­ate RIn(SPh)2 (R = nBu, iBu) as solids, although the compounds were poorly soluble in organic solvents, precluding crystallization. All compounds in these studies were primarily characterized by NMR. The only structurally characterized example of such a compound is [(Me3Si)3C](PhS)In-μ-(PhS)2In[C(Me3Si)3](SPh), which is prepared from the redox reaction of the indium(I) compound [(Me3Si)3CIn]4 and the di­sulfide (SPh)2 (Peppe et al., 2009 ▸). The 1:2 reaction of Me3In and 2-MeC6H4SH in toluene affords [Me(2-MeC6H4S)In-μ-(2-MeC6H4S)2InMe(2-MeC6H4S)], (I), in high yield. The modest steric bulk afforded by the 2-MeC6H4 group moderates inter­molecular bonding and increases solubility in organic solvents without preventing formation of the RIn(SR′)2 species. The observation of only one signal for the MeIn and 2-MeC6H4S groups in the 1H NMR study suggests that the compound dissociates into MeIn(2-MeC6H4S)2 monomers in tetrahydrofuran solution.

Structural commentary

The asymmetric unit comprises the dinuclear compound, [Me(2-MeC6H4S)In-μ-(2-MeC6H4S)2InMe(2-MeC6H4S)], (I) (Fig. 1 ▸). The two unique indium atoms are each bonded to a methyl carbon atom, and one terminal and one bridging (2-MeC6H4S) group, generating a nearly square-planar four-membered In2S2 ring core [S2—In1—S3 = 88.28 (6), In1—S2—In2 = 91.86 (6), S2—In2—S3 = 87.02 (6), In1—S3—In2 = 92.58 (7)°]. The In atoms are in distorted trigonal–pyramidal CS3 bonding environments [C1—In1—S1 = 127.3 (2), C1—In1—S2 = 113.1 (3), S1—In1—S2 = 114.66 (7), C1—In1—S3 = 105.7 (2), S1—In1—S3 = 96.94 (6), S2—In1—S3 = 88.28 (6), C2—In2—S3 = 118.2 (3), C2—In2—S4 = 124.1 (3), S3—In2—S4 = 115.00 (7), C2—In2—S2 = 102.4 (2), S2—In2—S3 = 87.02 (6), S2—In2—S4 = 95.87 (6)°]. Bond lengths and angles are similar at each indium atom.

Figure 1

The asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.

Supra­molecular features

The dimeric structures are further associated into one-dimensional polymers extending parallel to the a axis via inter­molecular In⋯S contacts [In1⋯S4(x − 1, y, z) = 3.091 (2), In2⋯S1(x + 1, y, z) = 2.920 (2) Å] (sum of metallic/van der Waals radii = 3.52 Å; Bondi, 1964 ▸) (Fig. 2 ▸). Such contacts are common for indium and other heavy main group metal chalcogenolates due to their large metal radii and potential for high coordination numbers (Briand et al., 2010 ▸, 2011 ▸, 2012 ▸; Appleton et al., 2011 ▸). This leads to the formation of insoluble materials for iBuIn(SPh)2 (Nomura et al., 1989 ▸). The steric bulk provided by the Me group of the (2-MeC6H4S) ligand is sufficient to moderate inter­molecular contacts and afford solubility in organic solvents (e.g. toluene and tetra­hydro­furan).

Figure 2

Part of the crystal structure of (I), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) −1 + x, y, z; (ii) 1 + x, y, z.]

Database survey

The dinuclear structure of (I) is similar to that of [Me(MeO2CCH2CH2S)In-μ-(MeO2CCH2CH2S)2InMe(MeO2CCH2CH2S)] (Allan et al., 2013 ▸). However, the ester carbonyl oxygen atoms of the terminal MeO2CCH2CH2S groups occupy the coordination site trans to the axial bridging thiol­ate sulfur atom. This precludes inter­molecular In⋯S bonding and yields discrete dimeric units. The structure of (I) is also similar to that of the structure of dimeric [(Me3Si)3C](PhS)In-μ-(PhS)2In[C(Me3Si)3](SPh) (Peppe et al., 2009 ▸). However, the steric bulk of the (Me3Si)3C precludes further inter­molecular In⋯S bonding and the indium atoms are restricted to a four-coordinate distorted tetra­hedral bonding environment. Other reported methyl­indium di­thiol­ates employ polydentate di­thiol­ate ligands, some of which possess dimeric and trimeric structures (Briand et al., 2016 ▸).

Synthesis and crystallization

2-Methyl­benzene­thiol (0.300 g, 2.42 mmol) in toluene (2 ml) was added dropwise to a stirred solution of InMe3 (0.193 g, 1.21 mmol) in toluene (5 ml). The solution was stirred for 18 h and concentrated in vacuo to 4 ml. After sitting at 296 K for 1 d, the solution was filtered to yield colourless, needle-like crystals of (I). Yield: 0.317 g (0.421 mmol, 70%). Analysis calculated for C30H34S4In2: C, 47.88; H, 4.55; N, 0.00. Found: C, 46.88; H, 4.55; N, <0.3. M.p 421–422 K.

FT—IR (cm−1): 672 s, 705 s, 741 s, 800 w, 846 w, 861 w, 939 w, 978 w, 1041 m, 1055 m, 1280 w, 1378 w, 1451 m, 1464 m, 1585 w, 2913 w, 3056 w. FT–Raman (cm−1): 121 vs, 158 s, 244 w, 322 m, 443 w, 508 s, 552 w, 675 w, 800 m, 1043 s, 1128 w, 1148 w, 1204 m, 1465 w, 1565 w, 1586 m, 2916 w, 3047 m. 1H NMR (200 MHz, n class="Chemical">thf-d 8, p.p.m.): δ = 0.23 [s, 3H, MeIn], 2.60 [s, 6H, (S-2-MeC6H4)], 7.06–7.11 [m, 4H, (S-2-MeC6 H 4)] 7.23–7.28 [m, 2H, (S-2-MeC6 H 4)], 7.62–7.66 [m, 2H, (S-2-MeC6 H 4)]. 13C{1H} NMR (101 MHz, thf-d 8, p.p.m.): δ = −5.1 (MeIn), 21.7 (S-2-MeC6H4), 124.1, 125.2, 129.4, 134.6, 138.4, 139.7 (S-2-MeC 6H4)].

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1 ▸. H atoms were included in calculated positions and refined using a riding model.

Table 1

Experimental details

Crystal data
Chemical formula	[In2(CH3)2(C7H7S)4]
M r	752.45
Crystal system, space group	Monoclinic, P21
Temperature (K)	173
a, b, c (Å)	7.4441 (15), 14.625 (3), 14.074 (3)
β (°)	99.693 (3)
V (Å3)	1510.4 (5)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.82
Crystal size (mm)	0.45 × 0.08 × 0.03
Data collection
Diffractometer	Bruker SMART1000/P4
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a ▸)
T min, T max	0.495, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	10442, 5591, 4742
R int	0.041
(sin θ/λ)max (Å−1)	0.650
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.034, 0.074, 1.04
No. of reflections	5591
No. of parameters	332
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.49, −1.01
Absolute structure	Flack (1983 ▸), 2079 Friedel pairs
Absolute structure parameter	0.41 (3)

Computer programs: SMART (Bruker, 1999 ▸), SAINT (Bruker, 2006 ▸), SHELXS97 and SHELXTL (Sheldrick, 2008b ▸), SHELXL2013 (Sheldrick, 2015 ▸) and DIAMOND (Brandenburg, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017003498/lh5837sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017003498/lh5837Isup2.hkl

CCDC reference: 1535922

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

[In2(CH3)2(C7H7S)4]	F(000) = 752
Mr = 752.45	Dx = 1.655 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.4441 (15) Å	Cell parameters from 5877 reflections
b = 14.625 (3) Å	θ = 2.8–27.8°
c = 14.074 (3) Å	µ = 1.82 mm−1
β = 99.693 (3)°	T = 173 K
V = 1510.4 (5) Å3	Rod, colourless
Z = 2	0.45 × 0.08 × 0.03 mm

Bruker SMART1000/P4 diffractometer	5591 independent reflections
Radiation source: fine-focus sealed tube, K760	4742 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.495, Tmax = 0.956	k = −18→19
10442 measured reflections	l = −18→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0276P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
5591 reflections	Δρmax = 0.49 e Å−3
332 parameters	Δρmin = −1.01 e Å−3
1 restraint	Absolute structure: Flack (1983), 2079 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.41 (3)

Experimental. Crystal decay was monitored by repeating the initial 50 frames at the end of the data collection and analyzing duplicate reflections.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin

	x	y	z	Uiso*/Ueq
In1	0.60776 (7)	0.80291 (3)	0.26699 (4)	0.02518 (14)
In2	1.05764 (7)	0.69727 (3)	0.23677 (4)	0.02406 (14)
S1	0.4196 (2)	0.70588 (16)	0.35474 (14)	0.0268 (4)
S2	0.7227 (3)	0.72420 (11)	0.12869 (14)	0.0218 (4)
S3	0.9290 (3)	0.76607 (13)	0.37732 (15)	0.0232 (4)
S4	1.2193 (2)	0.80568 (17)	0.14747 (13)	0.0268 (4)
C1	0.5973 (11)	0.9472 (6)	0.2527 (7)	0.036 (2)
H1A	0.6958	0.9746	0.2988	0.054*
H1B	0.4796	0.9694	0.2656	0.054*
H1C	0.6115	0.9641	0.1870	0.054*
C2	1.0874 (11)	0.5515 (5)	0.2317 (7)	0.034 (2)
H2A	1.2104	0.5364	0.2206	0.051*
H2B	0.9975	0.5265	0.1792	0.051*
H2C	1.0678	0.5249	0.2931	0.051*
C3	0.4643 (10)	0.7328 (5)	0.4795 (6)	0.0235 (17)
C4	0.4170 (10)	0.6667 (5)	0.5433 (6)	0.0269 (18)
C5	0.4608 (11)	0.6852 (6)	0.6420 (6)	0.0346 (19)
H5	0.4308	0.6413	0.6865	0.042*
C6	0.5449 (11)	0.7639 (6)	0.6763 (6)	0.035 (2)
H6	0.5751	0.7736	0.7439	0.042*
C7	0.5863 (11)	0.8296 (5)	0.6137 (6)	0.034 (2)
H7	0.6436	0.8850	0.6376	0.040*
C8	0.5435 (10)	0.8145 (6)	0.5147 (5)	0.0297 (18)
H8	0.5687	0.8604	0.4711	0.036*
C9	0.3221 (13)	0.5794 (6)	0.5076 (6)	0.041 (2)
H9A	0.2848	0.5467	0.5618	0.061*
H9B	0.4054	0.5410	0.4780	0.061*
H9C	0.2143	0.5937	0.4597	0.061*
C10	0.6499 (9)	0.6072 (5)	0.1171 (5)	0.0196 (16)
C11	0.6429 (10)	0.5650 (5)	0.0265 (6)	0.0254 (17)
C12	0.6019 (10)	0.4720 (5)	0.0215 (6)	0.0307 (19)
H12	0.5984	0.4414	−0.0383	0.037*
C13	0.5667 (11)	0.4229 (5)	0.0989 (6)	0.035 (2)
H13	0.5361	0.3599	0.0918	0.042*
C14	0.5755 (11)	0.4651 (5)	0.1872 (6)	0.0305 (19)
H14	0.5540	0.4311	0.2417	0.037*
C15	0.6163 (11)	0.5583 (5)	0.1957 (6)	0.0285 (18)
H15	0.6208	0.5881	0.2560	0.034*
C16	0.6849 (12)	0.6168 (6)	−0.0591 (6)	0.037 (2)
H16A	0.8122	0.6372	−0.0464	0.056*
H16B	0.6045	0.6701	−0.0708	0.056*
H16C	0.6656	0.5770	−0.1159	0.056*
C17	1.0334 (10)	0.8758 (5)	0.4071 (6)	0.0281 (18)
C18	1.0799 (11)	0.8983 (6)	0.5038 (7)	0.038 (2)
C19	1.1513 (12)	0.9872 (7)	0.5242 (8)	0.050 (3)
H19	1.1826	1.0054	0.5897	0.060*
C20	1.1768 (12)	1.0467 (7)	0.4554 (9)	0.058 (3)
H20	1.2259	1.1055	0.4727	0.070*
C21	1.1315 (12)	1.0226 (6)	0.3587 (8)	0.049 (3)
H21	1.1498	1.0646	0.3097	0.059*
C22	1.0589 (11)	0.9361 (5)	0.3345 (7)	0.037 (2)
H22	1.0272	0.9187	0.2688	0.044*
C23	1.0596 (12)	0.8356 (7)	0.5848 (6)	0.045 (2)
H23A	1.1387	0.7822	0.5831	0.068*
H23B	0.9325	0.8154	0.5782	0.068*
H23C	1.0941	0.8677	0.6462	0.068*
C24	1.1434 (10)	0.7751 (5)	0.0239 (6)	0.0267 (18)
C25	1.0177 (10)	0.8323 (5)	−0.0341 (5)	0.0276 (18)
C26	0.9738 (11)	0.8081 (7)	−0.1314 (6)	0.042 (2)
H26	0.8901	0.8452	−0.1730	0.050*
C27	1.0464 (13)	0.7330 (6)	−0.1693 (6)	0.045 (2)
H27	1.0144	0.7192	−0.2360	0.054*
C28	1.1654 (12)	0.6781 (6)	−0.1103 (7)	0.044 (2)
H28	1.2144	0.6253	−0.1359	0.053*
C29	1.2146 (10)	0.6990 (6)	−0.0141 (6)	0.0334 (17)
H29	1.2980	0.6608	0.0263	0.040*
C30	0.9353 (11)	0.9151 (6)	0.0057 (7)	0.040 (2)
H30A	1.0317	0.9593	0.0289	0.060*
H30B	0.8745	0.8965	0.0593	0.060*
H30C	0.8462	0.9432	−0.0451	0.060*

	U11	U22	U33	U12	U13	U23
In1	0.0262 (3)	0.0223 (2)	0.0294 (3)	−0.0009 (2)	0.0116 (2)	−0.0015 (3)
In2	0.0220 (3)	0.0244 (3)	0.0273 (3)	−0.0018 (2)	0.0085 (2)	−0.0032 (2)
S1	0.0209 (9)	0.0376 (11)	0.0221 (10)	−0.0070 (10)	0.0047 (8)	−0.0036 (10)
S2	0.0205 (10)	0.0232 (9)	0.0225 (10)	−0.0030 (7)	0.0057 (8)	−0.0025 (8)
S3	0.0218 (10)	0.0283 (9)	0.0203 (10)	−0.0009 (8)	0.0062 (9)	−0.0015 (8)
S4	0.0204 (9)	0.0356 (10)	0.0244 (10)	−0.0058 (11)	0.0039 (8)	0.0023 (11)
C1	0.033 (5)	0.031 (5)	0.042 (5)	−0.004 (4)	0.003 (4)	−0.006 (4)
C2	0.027 (5)	0.021 (4)	0.053 (6)	0.006 (3)	0.005 (4)	−0.004 (4)
C3	0.016 (4)	0.026 (3)	0.029 (4)	0.007 (3)	0.006 (3)	0.000 (3)
C4	0.021 (4)	0.033 (4)	0.027 (4)	0.005 (3)	0.004 (3)	0.002 (3)
C5	0.044 (5)	0.033 (4)	0.027 (4)	0.005 (4)	0.008 (4)	0.005 (4)
C6	0.035 (5)	0.044 (4)	0.025 (5)	0.001 (4)	0.005 (4)	−0.002 (4)
C7	0.033 (5)	0.032 (4)	0.037 (5)	−0.008 (4)	0.008 (4)	−0.014 (4)
C8	0.027 (4)	0.032 (4)	0.032 (4)	0.001 (4)	0.010 (3)	−0.002 (4)
C9	0.059 (6)	0.039 (5)	0.022 (5)	−0.011 (4)	0.004 (4)	0.002 (4)
C10	0.010 (4)	0.024 (4)	0.025 (4)	0.002 (3)	0.005 (3)	−0.002 (3)
C11	0.017 (4)	0.031 (4)	0.030 (4)	0.006 (3)	0.009 (3)	−0.003 (3)
C12	0.027 (4)	0.029 (4)	0.036 (5)	0.003 (4)	0.002 (4)	−0.012 (4)
C13	0.032 (5)	0.021 (4)	0.052 (6)	−0.009 (4)	0.008 (4)	0.000 (4)
C14	0.029 (5)	0.026 (4)	0.040 (5)	0.000 (3)	0.016 (4)	0.001 (4)
C15	0.031 (5)	0.030 (4)	0.025 (4)	−0.004 (4)	0.009 (4)	0.001 (3)
C16	0.040 (5)	0.041 (5)	0.032 (5)	−0.001 (4)	0.010 (4)	0.000 (4)
C17	0.018 (4)	0.029 (4)	0.038 (5)	−0.002 (3)	0.007 (4)	−0.008 (4)
C18	0.013 (4)	0.046 (5)	0.054 (6)	0.008 (4)	0.007 (4)	−0.022 (5)
C19	0.026 (5)	0.066 (7)	0.058 (7)	−0.005 (5)	0.005 (5)	−0.037 (6)
C20	0.026 (5)	0.054 (6)	0.096 (10)	−0.011 (5)	0.015 (6)	−0.036 (7)
C21	0.036 (5)	0.035 (5)	0.081 (8)	−0.008 (4)	0.021 (5)	−0.012 (5)
C22	0.034 (5)	0.029 (4)	0.052 (6)	−0.007 (4)	0.023 (4)	−0.009 (4)
C23	0.037 (5)	0.071 (6)	0.027 (5)	0.012 (5)	0.003 (4)	−0.007 (4)
C24	0.023 (4)	0.035 (4)	0.024 (4)	−0.007 (3)	0.011 (3)	0.003 (3)
C25	0.024 (4)	0.033 (4)	0.025 (4)	−0.010 (3)	0.002 (3)	0.005 (3)
C26	0.039 (5)	0.049 (5)	0.034 (5)	−0.013 (5)	−0.006 (4)	0.015 (5)
C27	0.053 (6)	0.061 (6)	0.020 (5)	−0.028 (5)	0.004 (4)	−0.002 (4)
C28	0.048 (6)	0.044 (6)	0.043 (6)	−0.011 (5)	0.017 (5)	−0.017 (4)
C29	0.022 (4)	0.042 (4)	0.038 (5)	−0.003 (4)	0.009 (3)	0.000 (5)
C30	0.027 (5)	0.035 (4)	0.055 (6)	0.004 (4)	−0.002 (4)	0.015 (4)

In1—C1	2.119 (9)	C12—C13	1.366 (12)
In1—S1	2.466 (2)	C12—H12	0.9500
In1—S2	2.531 (2)	C13—C14	1.379 (11)
In1—S3	2.678 (2)	C13—H13	0.9500
In1—S4i	3.0910 (19)	C14—C15	1.398 (10)
In2—C2	2.146 (8)	C14—H14	0.9500
In2—S4	2.460 (2)	C15—H15	0.9500
In2—S3	2.546 (2)	C16—H16A	0.9800
In2—S2	2.722 (2)	C16—H16B	0.9800
In2—S1ii	2.9201 (19)	C16—H16C	0.9800
S1—C3	1.776 (8)	C17—C22	1.386 (12)
S1—In2i	2.9201 (19)	C17—C18	1.386 (12)
S2—C10	1.794 (7)	C18—C19	1.415 (12)
S3—C17	1.802 (8)	C18—C23	1.491 (13)
S4—C24	1.792 (8)	C19—C20	1.339 (15)
C1—H1A	0.9800	C19—H19	0.9500
C1—H1B	0.9800	C20—C21	1.391 (14)
C1—H1C	0.9800	C20—H20	0.9500
C2—H2A	0.9800	C21—C22	1.395 (11)
C2—H2B	0.9800	C21—H21	0.9500
C2—H2C	0.9800	C22—H22	0.9500
C3—C8	1.386 (10)	C23—H23A	0.9800
C3—C4	1.404 (10)	C23—H23B	0.9800
C4—C5	1.398 (11)	C23—H23C	0.9800
C4—C9	1.504 (11)	C24—C29	1.379 (11)
C5—C6	1.361 (11)	C24—C25	1.409 (10)
C5—H5	0.9500	C25—C26	1.399 (11)
C6—C7	1.373 (11)	C25—C30	1.508 (11)
C6—H6	0.9500	C26—C27	1.371 (13)
C7—C8	1.393 (11)	C26—H26	0.9500
C7—H7	0.9500	C27—C28	1.368 (13)
C8—H8	0.9500	C27—H27	0.9500
C9—H9A	0.9800	C28—C29	1.376 (11)
C9—H9B	0.9800	C28—H28	0.9500
C9—H9C	0.9800	C29—H29	0.9500
C10—C15	1.374 (10)	C30—H30A	0.9800
C10—C11	1.409 (10)	C30—H30B	0.9800
C11—C12	1.393 (10)	C30—H30C	0.9800
C11—C16	1.500 (11)
C1—In1—S1	127.3 (2)	C12—C11—C10	116.6 (7)
C1—In1—S2	113.1 (3)	C12—C11—C16	121.7 (8)
S1—In1—S2	114.66 (7)	C10—C11—C16	121.6 (7)
C1—In1—S3	105.7 (2)	C13—C12—C11	122.9 (8)
S1—In1—S3	96.94 (6)	C13—C12—H12	118.6
S2—In1—S3	88.28 (6)	C11—C12—H12	118.6
C1—In1—S4i	85.4 (2)	C12—C13—C14	119.8 (7)
S1—In1—S4i	73.86 (6)	C12—C13—H13	120.1
S2—In1—S4i	89.64 (6)	C14—C13—H13	120.1
S3—In1—S4i	168.67 (6)	C13—C14—C15	119.3 (8)
C2—In2—S4	124.1 (3)	C13—C14—H14	120.4
C2—In2—S3	118.2 (3)	C15—C14—H14	120.4
S4—In2—S3	115.00 (7)	C10—C15—C14	120.4 (8)
C2—In2—S2	102.4 (2)	C10—C15—H15	119.8
S4—In2—S2	95.87 (6)	C14—C15—H15	119.8
S3—In2—S2	87.02 (6)	C11—C16—H16A	109.5
C2—In2—S1ii	88.3 (2)	C11—C16—H16B	109.5
S4—In2—S1ii	77.21 (6)	H16A—C16—H16B	109.5
S3—In2—S1ii	88.45 (6)	C11—C16—H16C	109.5
S2—In2—S1ii	169.21 (6)	H16A—C16—H16C	109.5
C3—S1—In1	109.9 (3)	H16B—C16—H16C	109.5
C3—S1—In2i	125.0 (3)	C22—C17—C18	122.0 (8)
In1—S1—In2i	106.71 (7)	C22—C17—S3	120.2 (6)
C10—S2—In1	111.6 (2)	C18—C17—S3	117.8 (6)
C10—S2—In2	98.4 (2)	C17—C18—C19	116.1 (9)
In1—S2—In2	91.86 (6)	C17—C18—C23	124.3 (8)
C17—S3—In2	109.2 (3)	C19—C18—C23	119.6 (8)
C17—S3—In1	105.3 (3)	C20—C19—C18	123.0 (9)
In2—S3—In1	92.58 (7)	C20—C19—H19	118.5
C24—S4—In2	103.5 (2)	C18—C19—H19	118.5
In1—C1—H1A	109.5	C19—C20—C21	120.1 (9)
In1—C1—H1B	109.5	C19—C20—H20	120.0
H1A—C1—H1B	109.5	C21—C20—H20	120.0
In1—C1—H1C	109.5	C20—C21—C22	119.2 (10)
H1A—C1—H1C	109.5	C20—C21—H21	120.4
H1B—C1—H1C	109.5	C22—C21—H21	120.4
In2—C2—H2A	109.5	C17—C22—C21	119.5 (9)
In2—C2—H2B	109.5	C17—C22—H22	120.2
H2A—C2—H2B	109.5	C21—C22—H22	120.2
In2—C2—H2C	109.5	C18—C23—H23A	109.5
H2A—C2—H2C	109.5	C18—C23—H23B	109.5
H2B—C2—H2C	109.5	H23A—C23—H23B	109.5
C8—C3—C4	120.1 (7)	C18—C23—H23C	109.5
C8—C3—S1	122.8 (6)	H23A—C23—H23C	109.5
C4—C3—S1	117.0 (6)	H23B—C23—H23C	109.5
C5—C4—C3	117.4 (7)	C29—C24—C25	121.0 (7)
C5—C4—C9	120.9 (7)	C29—C24—S4	119.9 (6)
C3—C4—C9	121.6 (7)	C25—C24—S4	119.0 (6)
C6—C5—C4	122.2 (8)	C26—C25—C24	116.1 (8)
C6—C5—H5	118.9	C26—C25—C30	121.7 (8)
C4—C5—H5	118.9	C24—C25—C30	122.2 (7)
C5—C6—C7	120.2 (8)	C27—C26—C25	122.8 (8)
C5—C6—H6	119.9	C27—C26—H26	118.6
C7—C6—H6	119.9	C25—C26—H26	118.6
C6—C7—C8	119.5 (7)	C28—C27—C26	119.4 (8)
C6—C7—H7	120.3	C28—C27—H27	120.3
C8—C7—H7	120.3	C26—C27—H27	120.3
C3—C8—C7	120.4 (7)	C27—C28—C29	120.3 (9)
C3—C8—H8	119.8	C27—C28—H28	119.8
C7—C8—H8	119.8	C29—C28—H28	119.8
C4—C9—H9A	109.5	C28—C29—C24	120.3 (8)
C4—C9—H9B	109.5	C28—C29—H29	119.8
H9A—C9—H9B	109.5	C24—C29—H29	119.8
C4—C9—H9C	109.5	C25—C30—H30A	109.5
H9A—C9—H9C	109.5	C25—C30—H30B	109.5
H9B—C9—H9C	109.5	H30A—C30—H30B	109.5
C15—C10—C11	121.1 (7)	C25—C30—H30C	109.5
C15—C10—S2	121.1 (6)	H30A—C30—H30C	109.5
C11—C10—S2	117.7 (6)	H30B—C30—H30C	109.5