research communications
Synthesis and μ-2-methylbenzenethiolato-κ2S:S)bis[methyl(2-methylbenzenethiolato-κS)indium(III)]
of bis(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
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 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 (ROP) of cyclic 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 6H4S)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.
comprises the dinuclear compound, [Me(2-MeC3. 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).
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 . H atoms were included in calculated positions and refined using a riding model.
details are summarized in Table 1Supporting information
CCDC reference: 1535922
https://doi.org/10.1107/S2056989017003498/lh5837sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017003498/lh5837Isup2.hkl
Data collection: SMART (Bruker, 1999); cell
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).[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 |
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 Canadahttps://doi.org/10.13039/501100000038; Canada Foundation for Innovationhttps://doi.org/10.13039/501100000196; New Brunswick Innovation Foundationhttps://doi.org/10.13039/501100000240; Mount Allison Universityhttps://doi.org/10.13039/501100004633.
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