Synthesis and crystal structure of bis­(μ-2-methyl­benzene­thiol­ato-κ2S:S)bis­[meth­yl(2-methyl­benzene­thiol­ato-κS)indium(III)]

Briand, G.G.; Decken, A.; Dickie, C.M.; MacNeil, G.

doi:10.1107/S2056989017003498

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Volume 73| Part 4| April 2017| Pages 481-483

https://doi.org/10.1107/S2056989017003498

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Synthesis and crystal structure of bis(μ-2-methylbenzenethiolato-κ²S:S)bis[methyl(2-methylbenzenethiolato-κS)indium(III)]

Glen G. Briand,^a ^* Andreas Decken,^b Courtney M. Dickie ^a and Gregory MacNeil ^a

^aDepartment of Chemistry and Biochemistry, Mount Allison University, 63C York Street, Sackville, NB, E4L 1G8, Canada, and ^bDepartment of Chemistry, University of New Brunswick, Fredericton, NB, E3B 5A3, Canada
^*Correspondence e-mail: gbriand@mta.ca

Edited by A. J. Lough, University of Toronto, Canada (Received 17 February 2017; accepted 3 March 2017; online 10 March 2017)

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 intermolecular In⋯S contacts. The In atoms are then in distorted trigonal–bipyramidal CS₄ bonding environments.

Keywords: crystal structure; indium; thiolate; dinuclear; coordination polymer.

CCDC reference: 1535922

1. Chemical context

Methylindium dithiolates [MeIn(S₂R)] 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 (R₃In) with simple monothiols (R′SH) often results in isolation of the diorganylindium thiolate R₂In(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.

2. 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.

3. 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.]

4. 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).

5. 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, thf-d₈, p.p.m.): δ = 0.23 [s, 3H, MeIn], 2.60 [s, 6H, (S-2-MeC₆H₄)], 7.06–7.11 [m, 4H, (S-2-MeC₆H₄)] 7.23–7.28 [m, 2H, (S-2-MeC₆H₄)], 7.62–7.66 [m, 2H, (S-2-MeC₆H₄)]. ¹³C{¹H} NMR (101 MHz, thf-d₈, 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-MeC₆H₄)].

6. 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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC reference: 1535922

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017003498/lh5837sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017003498/lh5837Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Bis(µ-2-methylbenzenethiolato-κ²S:S)bis[methyl(2-methylbenzenethiolato-κS)indium(III)] top

Crystal data top

[In₂(CH₃)₂(C₇H₇S)₄]	F(000) = 752
M_r = 752.45	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0276P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
5591 reflections	Δρ_max = 0.49 e Å⁻³
332 parameters	Δρ_min = −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)

Special details top

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

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Funding information

Funding for this research was provided by: Natural Sciences and Engineering Research Council of Canada; Canada Foundation for Innovation; New Brunswick Innovation Foundation; Mount Allison University.

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