research communications
of a 1:1 adduct of triphenyltin chloride with 3-cyclohexhyl-2-phenyl-1,3-thiazolidin-4-one
aThe Pennsylvania State University, Department of Biochemistry and Molecular Biology, University Park, PA 16802, USA, bPennsylvania State University, Brandywine Campus, Department of Chemistry, Brandywine, PA 19063, USA, and cThe Pennsylvania State University, Department of Chemistry, Abington College, Abington, PA 19001, USA
*Correspondence e-mail: kcc10@psu.edu
In the centrosymmetric (racemic) title compound, chlorido(3-cyclohexhyl-2-phenyl-1,3-thiazolidin-4-one-κO)triphenyltin(IV), [Sn(C6H5)3Cl(C15H19NOS)], the tin(IV) atom exhibits a trigonal–bipyramidal coordination geometry with the three phenyl groups in equatorial positions and the chloride anion and ligand oxygen atom present at axial sites [O—Sn—Cl = 175.07 (14)°]. The thiazolidinone ring of the ligand adopts an with the S atom as the flap. The dihedral angles between the heterocycle ring plane (all atoms) are 44.3 (9)° with respect to the pendant C-phenyl plane and 34.3 (11)° to the N-cyclohexyl ring (all atoms). The C-phenyl and N-cyclohexyl ring are close to orthogonal to each other, with a dihedral angle of 81.1 (4)° between them. In the crystal, molecules are linked by weak C—H⋯Cl hydrogen bonds to generate [001] chains.
CCDC reference: 1894217
1. Chemical context
Substituted 1,3-thiazolidin-4-ones themselves as well as ligands attached to various metals exhibit a wide range of biological activity (Jain et al., 2012; Kozlowski et al. 2002). The ligand of the title compound, (N)-3-xyclohexyl-2-phenyl-1,3-thiazolidine-4-one, is easily prepared from N-cyclcohexylidene aniline and thioglycolic acid utilizing a method originally proposed by Surrey (1947). The of (N)-3-cyclohexyl-2-phenyl-1,3-thiazolidine-4-one has previously been reported (Cannon et al. 2013), as have a number of other 2,3-disubstituted-thiazolidin-4-one structures (Yennawar et al., 2017; Vigorita et al., 1979). Furthermore, the X-ray of 2,3-diphenyl-1,3-thiazolidin-4-one as a 1:1 adduct with triphenyltin chloride has been described (Smith et al. 1995), and along with related complexes has biological activity against Cerotysistis Ulmi, the fungus that causes Dutch Elm Disease (Beraldo & de Lima, 2008).
Herein, we report the synthesis and N)-3-cyclohexhyl-2-phenyl-1,3-thiazolidin-4-one.
of the 1:1 adduct of triphenyltin chloride with (2. Structural commentary
The title compound (Fig. 1) shows a five-coordinate geometry around the tin atom (Table 1) with three phenyl groups placed equatorially, and a chloride ligand and an O-bonded thiazolidinone ligand at the axial sites. The Cl—Sn—O(ligand) principal axis is almost 5° off its ideal linear geometry with a bond angle of 175.07 (14)°. The (N)-3-cyclohexhyl-2-phenyl-1,3-thiazolidin-4-one ligand contains a chiral center at the 2-carbon atom (C21): in the arbitrarily chosen this atom has an R configuration, but crystal symmetry generates a racemic mixture.
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The most closely related structure previously reported is that of 2,3-diphenyl-1,3-thiazolidin-4-one as a 1:1 adduct with triphenyltin chloride (Smith et al., 1995). Since this molecule had a less bulky phenyl group at N3 (N1 in our numbering scheme) than the more bulky cyclohexyl group, the principal angle is almost exactly linear at 179.2°. Previously, using Mössbauer effect spectroscopy, the 2,3-diphenyl-1,3-thiazolidin-4-one as a 1:1 adduct with triphenyltin chloride gave an r value (the ratio of quadrupole splitting to isomer shift) of 2.41, indicative of the tin with a greater than four. Although Mössbauer spectroscopy was not used in our study, we see the same coordination properties with the title molecule in the X-ray structure. The Sn—O bond length was found to be 2.500 Å for the tin–diphenylthiazolidinone adduct, using Mössbauer techniques as well as the X-ray data, whereas, the X-ray data for the title compound yields an Sn—O bond length of 2.488 (4) Å. These values are almost the same and show no difference in having the presence of phenyl and a cyclohexyl group at C2 and N3 (C21 and N1 in our numbering scheme) versus a phenyl group at each location.
3. Supramolecular features
The surface of the title compound is primarily hydrophobic due to four aromatic and one aliphatic ring resulting in intermolecular van der Waals interactions (Fig. 2) between the various aromatic rings. A sole weak hydrogen bond between the chiral carbon atom (C21) with a chloride ion of the neighboring molecule related by translation symmetry in the c-axis direction [H⋯Cl = 2.76 Å, C⋯Cl = 3.569 (9) Å, C—H⋯Cl = 140°] helps to consolidate the packing.
4. Database survey
There is only one closely related structure previously reported and that is 2,3-diphenyl-1,3-thiazolidin-4-one as a 1:1 adduct with triphenyltin chloride (Smith et al., 1995).
5. Synthesis and crystallization
The synthesis of (N)-3-cyclohexyl-2-phenyl-1,3-thiazolidine-4-one has been previously reported (Cannon et al., 2013).
The 1:1 adduct with triphenyltin chloride was prepared by dissolving 0.0023 mol of N-3-cyclohexhyl-2-phenyl-1,3-thiazolidin-4-one in 15 ml of acetone and adding this solution dropwise to a 15 mL solution of triphenyltin chloride (0.0023 mol) in a 50 ml round-bottom flask while stirring at room temperature for 3 h. Stirring was then stopped and the solution was allowed to stand for an additional 10 h. A precipitate was apparent, which was filtered and the filtrate was reduced under vacuum on a rotary evaporator, dried under vacuum to give an oily residue, which formed crystals when heated in ligroin. Recrystallization from ligroin solution yielded 0.0022 mol (97% yield) of the title 1:1 complex in the form of colorless blocks: m.p. 372–375 K (no literature reports).
Triphenyltinchloride-3-cyclohexyl-2-phenyl-1,3-thiazolidin-4-one: Yield (97%); m.p. 372–375 K, cm−1 1658.6 (C=O); 1H NMR (CDCl3): 7.78–7.27 (20 H, m, aromatics), 5.66 (1H, d, J = 1.9 Hz, C2), 3.89 (1H, dd, J = 1.9 Hz and J = 15.6 Hz, C5), 3.85–3.78 (1H, m, NCH), 3.58 (1H, d, J = 15.6 Hz, C5), 1.79–0.91 (10H, m, cyclohexyls); 13C NMR: 171.77 (C4), 142.98, 137.78, 136.34 (t, 25.3 Hz), 130.62, 129.32 (t, J = 32.2 Hz), 129.07, 128.88, 128.52, 126.38, 62.83 (C2), 56.30, 33.23 (C5), 31.03, 30.12, 26.10, 25.42. C33H34OClSnNS.
6. Refinement
In spite of our search for a better crystal we had to work with one that was not optimal, as is evident from the high value of Rint = 0.0721. Upon we observed positional disorder in almost a fourth of the structure (nine out of thirty-eight non-H atoms). As a result, some parameters such as the ADP max/min ratio (8.2) for one of the atoms are slightly above optimal values but the atomic connectivity is clearly established. Crystal data, data collection and structure details are summarized in Table 2. The H atoms were placed geometrically and allowed to ride on their parent C atoms during with C—H distances of 0.93 Å (aromatic) and 0.97 Å (methylene), with Uiso(H) = 1.2Ueq (aromatic or methylene C) or 1.5Ueq(methyl C).
Supporting information
CCDC reference: 1894217
https://doi.org/10.1107/S2056989019001592/hb7780sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019001592/hb7780Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019001592/hb7780Isup3.mol
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[Sn(C6H5)3Cl(C15H19NOS)] | F(000) = 1320 |
Mr = 646.81 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.360 (5) Å | Cell parameters from 4375 reflections |
b = 18.879 (6) Å | θ = 2.3–26.4° |
c = 10.992 (3) Å | µ = 1.00 mm−1 |
β = 102.524 (5)° | T = 218 K |
V = 3111.8 (17) Å3 | Block, colorless |
Z = 4 | 0.15 × 0.11 × 0.10 mm |
Bruker CCD area detector diffractometer | 7791 independent reflections |
Radiation source: fine-focus sealed tube | 5009 reflections with I > 2σ(I) |
Parallel-graphite monochromator | Rint = 0.072 |
phi and ω scans | θmax = 28.6°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS, Bruker, 2001) | h = −16→20 |
Tmin = 0.865, Tmax = 0.907 | k = −25→25 |
24296 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.083 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.221 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0926P)2 + 6.5369P] where P = (Fo2 + 2Fc2)/3 |
7791 reflections | (Δ/σ)max < 0.001 |
365 parameters | Δρmax = 2.50 e Å−3 |
133 restraints | Δρmin = −1.16 e Å−3 |
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. 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.5942 (3) | 0.0290 (3) | 0.2921 (4) | 0.0467 (14) | |
C2 | 0.5376 (4) | 0.0374 (4) | 0.1758 (4) | 0.092 (3) | |
H2 | 0.5556 | 0.0224 | 0.1045 | 0.111* | |
C3 | 0.4542 (4) | 0.0681 (4) | 0.1662 (5) | 0.116 (4) | |
H3 | 0.4163 | 0.0738 | 0.0884 | 0.139* | |
C4 | 0.4274 (3) | 0.0905 (4) | 0.2728 (7) | 0.089 (3) | |
H4 | 0.3715 | 0.1111 | 0.2664 | 0.106* | |
C5 | 0.4839 (4) | 0.0821 (4) | 0.3891 (5) | 0.097 (3) | |
H5 | 0.4660 | 0.0971 | 0.4604 | 0.116* | |
C6 | 0.5674 (4) | 0.0513 (3) | 0.3987 (4) | 0.077 (2) | |
H6 | 0.6052 | 0.0457 | 0.4765 | 0.092* | |
C7 | 0.7266 (4) | −0.1279 (2) | 0.2527 (5) | 0.0585 (17) | |
C12 | 0.6759 (5) | −0.1492 (3) | 0.1380 (5) | 0.108 (4) | |
H12 | 0.6395 | −0.1167 | 0.0872 | 0.130* | |
C11 | 0.6795 (5) | −0.2190 (4) | 0.0993 (6) | 0.132 (4) | |
H11 | 0.6455 | −0.2333 | 0.0225 | 0.158* | |
C10 | 0.7338 (6) | −0.2676 (2) | 0.1753 (8) | 0.126 (4) | |
H10 | 0.7362 | −0.3143 | 0.1494 | 0.151* | |
C9 | 0.7845 (5) | −0.2463 (3) | 0.2900 (8) | 0.123 (4) | |
H9 | 0.8209 | −0.2788 | 0.3409 | 0.148* | |
C8 | 0.7809 (4) | −0.1765 (3) | 0.3287 (5) | 0.085 (3) | |
H8 | 0.8148 | −0.1622 | 0.4055 | 0.102* | |
C13 | 0.8355 (3) | 0.0451 (2) | 0.3297 (6) | 0.0504 (14) | |
C18 | 0.8226 (3) | 0.1176 (3) | 0.3135 (7) | 0.104 (4) | |
H18 | 0.7653 | 0.1364 | 0.2996 | 0.125* | |
C17 | 0.8953 (5) | 0.1621 (2) | 0.3179 (9) | 0.141 (6) | |
H17 | 0.8867 | 0.2107 | 0.3071 | 0.169* | |
C16 | 0.9809 (4) | 0.1341 (3) | 0.3387 (8) | 0.115 (4) | |
H16 | 1.0296 | 0.1639 | 0.3417 | 0.138* | |
C15 | 0.9938 (3) | 0.0615 (4) | 0.3550 (7) | 0.092 (3) | |
H15 | 1.0511 | 0.0428 | 0.3688 | 0.111* | |
C14 | 0.9211 (3) | 0.0170 (2) | 0.3505 (6) | 0.075 (2) | |
H14 | 0.9298 | −0.0315 | 0.3614 | 0.090* | |
C19 | 0.7557 (6) | 0.0101 (4) | 0.0116 (7) | 0.0592 (19) | |
C20B | 0.839 (2) | −0.0392 (13) | 0.0291 (17) | 0.068 (6) | 0.66 (6) |
H20A | 0.8263 | −0.0855 | 0.0595 | 0.081* | 0.66 (6) |
H20B | 0.8894 | −0.0187 | 0.0872 | 0.081* | 0.66 (6) |
C21B | 0.810 (2) | 0.0427 (14) | −0.166 (3) | 0.064 (5) | 0.66 (6) |
H21B | 0.7775 | 0.0400 | −0.2531 | 0.077* | 0.66 (6) |
C22A | 0.864 (3) | 0.0842 (15) | −0.190 (4) | 0.065 (9) | 0.34 (6) |
C23A | 0.872 (4) | 0.1077 (19) | −0.307 (4) | 0.098 (15) | 0.34 (6) |
H23A | 0.8325 | 0.0919 | −0.3783 | 0.117* | 0.34 (6) |
C24A | 0.940 (5) | 0.155 (2) | −0.317 (5) | 0.12 (2) | 0.34 (6) |
H24A | 0.9452 | 0.1706 | −0.3956 | 0.147* | 0.34 (6) |
C25A | 0.999 (4) | 0.179 (2) | −0.211 (6) | 0.13 (2) | 0.34 (6) |
H25A | 1.0439 | 0.2101 | −0.2180 | 0.161* | 0.34 (6) |
C26A | 0.990 (2) | 0.155 (2) | −0.094 (6) | 0.125 (15) | 0.34 (6) |
H26A | 1.0300 | 0.1709 | −0.0232 | 0.150* | 0.34 (6) |
C27A | 0.923 (3) | 0.1079 (19) | −0.084 (4) | 0.080 (9) | 0.34 (6) |
H27A | 0.9174 | 0.0922 | −0.0058 | 0.096* | 0.34 (6) |
C20A | 0.811 (3) | −0.051 (3) | 0.003 (4) | 0.056 (8) | 0.34 (6) |
H20C | 0.7807 | −0.0935 | 0.0184 | 0.067* | 0.34 (6) |
H20D | 0.8661 | −0.0471 | 0.0667 | 0.067* | 0.34 (6) |
C21A | 0.798 (4) | 0.029 (3) | −0.184 (6) | 0.060 (7) | 0.34 (6) |
H21A | 0.7564 | 0.0262 | −0.2650 | 0.071* | 0.34 (6) |
C22B | 0.8812 (14) | 0.0986 (13) | −0.158 (2) | 0.076 (5) | 0.66 (6) |
C23B | 0.9134 (19) | 0.1135 (13) | −0.264 (3) | 0.103 (7) | 0.66 (6) |
H23B | 0.8852 | 0.0945 | −0.3402 | 0.124* | 0.66 (6) |
C24B | 0.988 (2) | 0.1569 (12) | −0.255 (4) | 0.132 (11) | 0.66 (6) |
H24B | 1.0091 | 0.1669 | −0.3264 | 0.158* | 0.66 (6) |
C25B | 1.0296 (15) | 0.1853 (13) | −0.141 (4) | 0.150 (13) | 0.66 (6) |
H25B | 1.0792 | 0.2143 | −0.1357 | 0.180* | 0.66 (6) |
C26B | 0.9975 (14) | 0.1704 (14) | −0.035 (3) | 0.128 (9) | 0.66 (6) |
H26B | 1.0256 | 0.1894 | 0.0414 | 0.154* | 0.66 (6) |
C27B | 0.9233 (15) | 0.1271 (14) | −0.043 (2) | 0.094 (6) | 0.66 (6) |
H27B | 0.9018 | 0.1171 | 0.0276 | 0.113* | 0.66 (6) |
C28 | 0.6744 (6) | 0.1067 (4) | −0.1129 (7) | 0.0641 (19) | |
H28 | 0.6264 | 0.0907 | −0.0735 | 0.077* | |
C29 | 0.7082 (7) | 0.1766 (5) | −0.0520 (10) | 0.093 (3) | |
H29A | 0.7557 | 0.1948 | −0.0888 | 0.111* | |
H29B | 0.7319 | 0.1695 | 0.0364 | 0.111* | |
C30 | 0.6307 (9) | 0.2297 (6) | −0.0715 (11) | 0.120 (4) | |
H30A | 0.5858 | 0.2131 | −0.0284 | 0.144* | |
H30B | 0.6524 | 0.2751 | −0.0363 | 0.144* | |
C31 | 0.5898 (10) | 0.2386 (6) | −0.2066 (12) | 0.123 (4) | |
H31A | 0.5402 | 0.2713 | −0.2162 | 0.148* | |
H31B | 0.6336 | 0.2587 | −0.2485 | 0.148* | |
C32 | 0.5578 (9) | 0.1698 (7) | −0.2659 (12) | 0.122 (4) | |
H32A | 0.5334 | 0.1770 | −0.3541 | 0.146* | |
H32B | 0.5106 | 0.1514 | −0.2287 | 0.146* | |
C33 | 0.6344 (7) | 0.1158 (5) | −0.2490 (8) | 0.086 (3) | |
H33A | 0.6120 | 0.0707 | −0.2849 | 0.103* | |
H33B | 0.6796 | 0.1323 | −0.2917 | 0.103* | |
Cl1 | 0.74786 (14) | −0.04867 (12) | 0.53404 (17) | 0.0666 (5) | |
N1 | 0.7461 (5) | 0.0513 (3) | −0.0871 (5) | 0.0578 (15) | |
O1 | 0.7073 (4) | 0.0135 (3) | 0.0899 (4) | 0.0620 (13) | |
S1A | 0.837 (2) | −0.0549 (18) | −0.145 (3) | 0.067 (5) | 0.34 (6) |
S1B | 0.861 (2) | −0.0454 (11) | −0.121 (2) | 0.083 (4) | 0.66 (6) |
Sn1 | 0.72177 (3) | −0.02084 (2) | 0.31194 (4) | 0.04302 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.037 (3) | 0.044 (3) | 0.059 (4) | −0.008 (2) | 0.010 (3) | −0.002 (3) |
C2 | 0.056 (5) | 0.162 (10) | 0.056 (4) | 0.029 (6) | 0.006 (4) | −0.001 (5) |
C3 | 0.060 (6) | 0.167 (12) | 0.107 (7) | 0.032 (7) | −0.010 (5) | −0.004 (8) |
C4 | 0.045 (5) | 0.077 (6) | 0.144 (8) | 0.018 (4) | 0.022 (4) | −0.005 (6) |
C5 | 0.081 (7) | 0.103 (8) | 0.116 (7) | 0.023 (6) | 0.042 (5) | −0.008 (6) |
C6 | 0.071 (5) | 0.099 (6) | 0.064 (5) | 0.027 (5) | 0.020 (4) | −0.009 (5) |
C7 | 0.062 (5) | 0.050 (3) | 0.072 (4) | 0.005 (3) | 0.035 (4) | 0.006 (3) |
C12 | 0.162 (11) | 0.066 (5) | 0.090 (7) | −0.007 (6) | 0.011 (6) | −0.019 (5) |
C11 | 0.195 (14) | 0.075 (6) | 0.141 (10) | −0.037 (7) | 0.068 (8) | −0.042 (6) |
C10 | 0.154 (12) | 0.054 (5) | 0.206 (12) | −0.025 (5) | 0.116 (9) | −0.031 (6) |
C9 | 0.132 (11) | 0.057 (5) | 0.201 (12) | 0.025 (6) | 0.080 (8) | 0.022 (6) |
C8 | 0.090 (7) | 0.057 (4) | 0.113 (7) | 0.020 (4) | 0.034 (5) | 0.014 (4) |
C13 | 0.042 (3) | 0.056 (3) | 0.056 (4) | 0.005 (3) | 0.016 (3) | 0.004 (3) |
C18 | 0.061 (5) | 0.052 (4) | 0.199 (12) | −0.002 (4) | 0.028 (7) | 0.006 (6) |
C17 | 0.083 (7) | 0.074 (6) | 0.257 (17) | −0.023 (5) | 0.016 (9) | 0.024 (9) |
C16 | 0.071 (5) | 0.104 (6) | 0.173 (12) | −0.034 (5) | 0.034 (7) | 0.011 (8) |
C15 | 0.054 (5) | 0.115 (7) | 0.117 (8) | −0.004 (5) | 0.037 (5) | 0.009 (7) |
C14 | 0.051 (4) | 0.078 (5) | 0.098 (7) | 0.005 (4) | 0.019 (4) | 0.002 (5) |
C19 | 0.086 (6) | 0.055 (4) | 0.042 (3) | 0.008 (3) | 0.025 (3) | 0.006 (3) |
C20B | 0.112 (15) | 0.075 (9) | 0.016 (6) | 0.041 (10) | 0.015 (8) | −0.020 (5) |
C21B | 0.114 (12) | 0.046 (9) | 0.041 (8) | 0.014 (7) | 0.038 (8) | −0.006 (6) |
C22A | 0.09 (2) | 0.037 (10) | 0.082 (18) | 0.008 (12) | 0.054 (16) | −0.017 (11) |
C23A | 0.16 (4) | 0.048 (16) | 0.12 (2) | −0.01 (2) | 0.10 (2) | −0.001 (17) |
C24A | 0.14 (5) | 0.06 (2) | 0.21 (4) | 0.00 (3) | 0.13 (4) | 0.02 (3) |
C25A | 0.12 (3) | 0.043 (19) | 0.28 (5) | 0.00 (2) | 0.13 (4) | −0.04 (3) |
C26A | 0.05 (2) | 0.09 (3) | 0.23 (4) | 0.015 (14) | 0.02 (2) | −0.01 (3) |
C27A | 0.053 (16) | 0.050 (17) | 0.14 (2) | 0.033 (12) | 0.017 (17) | −0.008 (19) |
C20A | 0.060 (18) | 0.080 (17) | 0.021 (13) | 0.016 (13) | −0.003 (12) | 0.016 (13) |
C21A | 0.10 (2) | 0.042 (15) | 0.050 (17) | 0.004 (10) | 0.037 (15) | 0.011 (14) |
C22B | 0.079 (11) | 0.069 (9) | 0.093 (12) | 0.024 (9) | 0.047 (9) | 0.015 (9) |
C23B | 0.112 (17) | 0.082 (14) | 0.142 (15) | 0.032 (10) | 0.087 (14) | 0.025 (12) |
C24B | 0.11 (2) | 0.066 (14) | 0.25 (3) | 0.041 (13) | 0.12 (2) | 0.047 (17) |
C25B | 0.081 (15) | 0.085 (19) | 0.29 (4) | 0.027 (10) | 0.057 (18) | 0.05 (2) |
C26B | 0.071 (12) | 0.079 (14) | 0.22 (2) | 0.021 (9) | 0.012 (14) | 0.015 (15) |
C27B | 0.076 (11) | 0.070 (14) | 0.136 (14) | 0.018 (9) | 0.021 (10) | −0.015 (11) |
C28 | 0.084 (6) | 0.060 (4) | 0.052 (4) | 0.015 (4) | 0.023 (4) | 0.005 (3) |
C29 | 0.099 (7) | 0.072 (5) | 0.099 (7) | 0.022 (5) | 0.006 (5) | −0.027 (5) |
C30 | 0.157 (11) | 0.084 (7) | 0.116 (7) | 0.055 (7) | 0.021 (7) | −0.013 (6) |
C31 | 0.145 (11) | 0.097 (7) | 0.126 (8) | 0.057 (7) | 0.024 (7) | 0.017 (7) |
C32 | 0.116 (10) | 0.124 (8) | 0.108 (8) | 0.039 (7) | −0.013 (7) | 0.014 (6) |
C33 | 0.106 (8) | 0.078 (6) | 0.065 (5) | 0.011 (5) | 0.002 (5) | 0.003 (4) |
Cl1 | 0.0649 (12) | 0.0897 (14) | 0.0434 (9) | −0.0031 (10) | 0.0077 (8) | 0.0144 (9) |
N1 | 0.080 (4) | 0.056 (3) | 0.044 (3) | 0.015 (3) | 0.026 (3) | 0.005 (2) |
O1 | 0.082 (4) | 0.074 (3) | 0.034 (2) | 0.011 (3) | 0.020 (2) | 0.006 (2) |
S1A | 0.097 (12) | 0.051 (7) | 0.057 (9) | 0.020 (6) | 0.030 (7) | 0.003 (6) |
S1B | 0.137 (12) | 0.062 (5) | 0.064 (6) | 0.028 (6) | 0.050 (7) | 0.001 (4) |
Sn1 | 0.0411 (3) | 0.0463 (3) | 0.0426 (3) | 0.0028 (2) | 0.01113 (18) | 0.00347 (19) |
Sn1—C1 | 2.141 (4) | C21B—S1B | 1.86 (4) |
Sn1—C7 | 2.130 (4) | C22A—C23A | 1.3900 |
Sn1—C13 | 2.119 (4) | C22A—C27A | 1.3900 |
Sn1—Cl1 | 2.4439 (19) | C22A—C21A | 1.47 (4) |
Sn1—O1 | 2.488 (4) | C23A—H23A | 0.9300 |
C1—C2 | 1.3900 | C23A—C24A | 1.3900 |
C1—C6 | 1.3900 | C24A—H24A | 0.9300 |
C2—H2 | 0.9300 | C24A—C25A | 1.3900 |
C2—C3 | 1.3900 | C25A—H25A | 0.9300 |
C3—H3 | 0.9300 | C25A—C26A | 1.3900 |
C3—C4 | 1.3900 | C26A—H26A | 0.9300 |
C4—H4 | 0.9300 | C26A—C27A | 1.3900 |
C4—C5 | 1.3900 | C27A—H27A | 0.9300 |
C5—H5 | 0.9300 | C20A—H20C | 0.9700 |
C5—C6 | 1.3900 | C20A—H20D | 0.9700 |
C6—H6 | 0.9300 | C20A—S1A | 1.76 (5) |
C7—C12 | 1.3900 | C21A—H21A | 0.9800 |
C7—C8 | 1.3900 | C21A—N1 | 1.52 (6) |
C12—H12 | 0.9300 | C21A—S1A | 1.71 (7) |
C12—C11 | 1.3900 | C22B—C23B | 1.3900 |
C11—H11 | 0.9300 | C22B—C27B | 1.3900 |
C11—C10 | 1.3900 | C23B—H23B | 0.9300 |
C10—H10 | 0.9300 | C23B—C24B | 1.3900 |
C10—C9 | 1.3900 | C24B—H24B | 0.9300 |
C9—H9 | 0.9300 | C24B—C25B | 1.3900 |
C9—C8 | 1.3900 | C25B—H25B | 0.9300 |
C8—H8 | 0.9300 | C25B—C26B | 1.3900 |
C13—C18 | 1.3900 | C26B—H26B | 0.9300 |
C13—C14 | 1.3900 | C26B—C27B | 1.3900 |
C18—H18 | 0.9300 | C27B—H27B | 0.9300 |
C18—C17 | 1.3900 | C28—H28 | 0.9800 |
C17—H17 | 0.9300 | C28—C29 | 1.519 (12) |
C17—C16 | 1.3900 | C28—C33 | 1.499 (11) |
C16—H16 | 0.9300 | C28—N1 | 1.501 (10) |
C16—C15 | 1.3900 | C29—H29A | 0.9700 |
C15—H15 | 0.9300 | C29—H29B | 0.9700 |
C15—C14 | 1.3900 | C29—C30 | 1.536 (13) |
C14—H14 | 0.9300 | C30—H30A | 0.9700 |
C19—C20B | 1.56 (3) | C30—H30B | 0.9700 |
C19—C20A | 1.44 (4) | C30—C31 | 1.491 (15) |
C19—N1 | 1.317 (9) | C31—H31A | 0.9700 |
C19—O1 | 1.257 (8) | C31—H31B | 0.9700 |
C20B—H20A | 0.9700 | C31—C32 | 1.488 (17) |
C20B—H20B | 0.9700 | C32—H32A | 0.9700 |
C20B—S1B | 1.76 (2) | C32—H32B | 0.9700 |
C21B—H21B | 0.9800 | C32—C33 | 1.537 (14) |
C21B—C22B | 1.50 (2) | C33—H33A | 0.9700 |
C21B—N1 | 1.46 (3) | C33—H33B | 0.9700 |
C2—C1—C6 | 120.0 | C26A—C27A—C22A | 120.0 |
C2—C1—Sn1 | 121.3 (3) | C26A—C27A—H27A | 120.0 |
C6—C1—Sn1 | 118.7 (3) | C19—C20A—H20C | 109.5 |
C1—C2—H2 | 120.0 | C19—C20A—H20D | 109.5 |
C1—C2—C3 | 120.0 | C19—C20A—S1A | 111 (2) |
C3—C2—H2 | 120.0 | H20C—C20A—H20D | 108.1 |
C2—C3—H3 | 120.0 | S1A—C20A—H20C | 109.5 |
C2—C3—C4 | 120.0 | S1A—C20A—H20D | 109.5 |
C4—C3—H3 | 120.0 | C22A—C21A—H21A | 108.1 |
C3—C4—H4 | 120.0 | C22A—C21A—N1 | 108 (4) |
C5—C4—C3 | 120.0 | C22A—C21A—S1A | 118 (4) |
C5—C4—H4 | 120.0 | N1—C21A—H21A | 108.1 |
C4—C5—H5 | 120.0 | N1—C21A—S1A | 107 (3) |
C6—C5—C4 | 120.0 | S1A—C21A—H21A | 108.1 |
C6—C5—H5 | 120.0 | C23B—C22B—C21B | 118.2 (12) |
C1—C6—H6 | 120.0 | C23B—C22B—C27B | 120.0 |
C5—C6—C1 | 120.0 | C27B—C22B—C21B | 121.1 (12) |
C5—C6—H6 | 120.0 | C22B—C23B—H23B | 120.0 |
C12—C7—C8 | 120.0 | C22B—C23B—C24B | 120.0 |
C12—C7—Sn1 | 120.1 (3) | C24B—C23B—H23B | 120.0 |
C8—C7—Sn1 | 119.9 (3) | C23B—C24B—H24B | 120.0 |
C7—C12—H12 | 120.0 | C23B—C24B—C25B | 120.0 |
C11—C12—C7 | 120.0 | C25B—C24B—H24B | 120.0 |
C11—C12—H12 | 120.0 | C24B—C25B—H25B | 120.0 |
C12—C11—H11 | 120.0 | C26B—C25B—C24B | 120.0 |
C12—C11—C10 | 120.0 | C26B—C25B—H25B | 120.0 |
C10—C11—H11 | 120.0 | C25B—C26B—H26B | 120.0 |
C11—C10—H10 | 120.0 | C25B—C26B—C27B | 120.0 |
C9—C10—C11 | 120.0 | C27B—C26B—H26B | 120.0 |
C9—C10—H10 | 120.0 | C22B—C27B—H27B | 120.0 |
C10—C9—H9 | 120.0 | C26B—C27B—C22B | 120.0 |
C10—C9—C8 | 120.0 | C26B—C27B—H27B | 120.0 |
C8—C9—H9 | 120.0 | C29—C28—H28 | 107.0 |
C7—C8—H8 | 120.0 | C33—C28—H28 | 107.0 |
C9—C8—C7 | 120.0 | C33—C28—C29 | 111.6 (7) |
C9—C8—H8 | 120.0 | C33—C28—N1 | 113.1 (6) |
C18—C13—C14 | 120.0 | N1—C28—H28 | 107.0 |
C18—C13—Sn1 | 118.4 (3) | N1—C28—C29 | 110.8 (7) |
C14—C13—Sn1 | 121.5 (3) | C28—C29—H29A | 109.9 |
C13—C18—H18 | 120.0 | C28—C29—H29B | 109.9 |
C13—C18—C17 | 120.0 | C28—C29—C30 | 109.0 (9) |
C17—C18—H18 | 120.0 | H29A—C29—H29B | 108.3 |
C18—C17—H17 | 120.0 | C30—C29—H29A | 109.9 |
C16—C17—C18 | 120.0 | C30—C29—H29B | 109.9 |
C16—C17—H17 | 120.0 | C29—C30—H30A | 109.4 |
C17—C16—H16 | 120.0 | C29—C30—H30B | 109.4 |
C17—C16—C15 | 120.0 | H30A—C30—H30B | 108.0 |
C15—C16—H16 | 120.0 | C31—C30—C29 | 111.0 (9) |
C16—C15—H15 | 120.0 | C31—C30—H30A | 109.4 |
C14—C15—C16 | 120.0 | C31—C30—H30B | 109.4 |
C14—C15—H15 | 120.0 | C30—C31—H31A | 109.3 |
C13—C14—H14 | 120.0 | C30—C31—H31B | 109.3 |
C15—C14—C13 | 120.0 | H31A—C31—H31B | 108.0 |
C15—C14—H14 | 120.0 | C32—C31—C30 | 111.5 (10) |
C20A—C19—C20B | 19 (2) | C32—C31—H31A | 109.3 |
N1—C19—C20B | 113.4 (10) | C32—C31—H31B | 109.3 |
N1—C19—C20A | 112.3 (16) | C31—C32—H32A | 109.5 |
O1—C19—C20B | 122.6 (10) | C31—C32—H32B | 109.5 |
O1—C19—C20A | 122.1 (17) | C31—C32—C33 | 110.7 (10) |
O1—C19—N1 | 123.8 (7) | H32A—C32—H32B | 108.1 |
C19—C20B—H20A | 111.0 | C33—C32—H32A | 109.5 |
C19—C20B—H20B | 111.0 | C33—C32—H32B | 109.5 |
C19—C20B—S1B | 104.0 (13) | C28—C33—C32 | 109.5 (8) |
H20A—C20B—H20B | 109.0 | C28—C33—H33A | 109.8 |
S1B—C20B—H20A | 111.0 | C28—C33—H33B | 109.8 |
S1B—C20B—H20B | 111.0 | C32—C33—H33A | 109.8 |
C22B—C21B—H21B | 108.2 | C32—C33—H33B | 109.8 |
C22B—C21B—S1B | 111 (2) | H33A—C33—H33B | 108.2 |
N1—C21B—H21B | 108.2 | C19—N1—C21B | 117.1 (14) |
N1—C21B—C22B | 117.3 (17) | C19—N1—C21A | 115 (2) |
N1—C21B—S1B | 103.6 (16) | C19—N1—C28 | 120.9 (6) |
S1B—C21B—H21B | 108.2 | C21B—N1—C21A | 14 (3) |
C23A—C22A—C27A | 120.0 | C21B—N1—C28 | 121.9 (13) |
C23A—C22A—C21A | 118 (2) | C28—N1—C21A | 123 (2) |
C27A—C22A—C21A | 121 (2) | C19—O1—Sn1 | 135.9 (5) |
C22A—C23A—H23A | 120.0 | C21A—S1A—C20A | 93 (3) |
C24A—C23A—C22A | 120.0 | C20B—S1B—C21B | 92.3 (14) |
C24A—C23A—H23A | 120.0 | C1—Sn1—Cl1 | 98.31 (14) |
C23A—C24A—H24A | 120.0 | C1—Sn1—O1 | 84.26 (18) |
C25A—C24A—C23A | 120.0 | C7—Sn1—C1 | 118.5 (2) |
C25A—C24A—H24A | 120.0 | C7—Sn1—Cl1 | 95.29 (16) |
C24A—C25A—H25A | 120.0 | C7—Sn1—O1 | 87.11 (19) |
C24A—C25A—C26A | 120.0 | C13—Sn1—C1 | 118.0 (2) |
C26A—C25A—H25A | 120.0 | C13—Sn1—C7 | 120.2 (2) |
C25A—C26A—H26A | 120.0 | C13—Sn1—Cl1 | 94.63 (17) |
C25A—C26A—C27A | 120.0 | C13—Sn1—O1 | 80.4 (2) |
C27A—C26A—H26A | 120.0 | Cl1—Sn1—O1 | 175.07 (14) |
C22A—C27A—H27A | 120.0 | ||
C1—C2—C3—C4 | 0.0 | C23A—C24A—C25A—C26A | 0.0 |
C2—C1—C6—C5 | 0.0 | C24A—C25A—C26A—C27A | 0.0 |
C2—C1—Sn1—C7 | −61.0 (4) | C25A—C26A—C27A—C22A | 0.0 |
C2—C1—Sn1—C13 | 98.6 (4) | C27A—C22A—C23A—C24A | 0.0 |
C2—C1—Sn1—Cl1 | −161.6 (3) | C27A—C22A—C21A—N1 | 53 (5) |
C2—C1—Sn1—O1 | 22.6 (4) | C27A—C22A—C21A—S1A | −68 (5) |
C2—C3—C4—C5 | 0.0 | C20A—C19—C20B—S1B | 68 (6) |
C3—C4—C5—C6 | 0.0 | C20A—C19—N1—C21B | −18 (2) |
C4—C5—C6—C1 | 0.0 | C20A—C19—N1—C21A | −3 (3) |
C6—C1—C2—C3 | 0.0 | C20A—C19—N1—C28 | 165 (2) |
C6—C1—Sn1—C7 | 117.3 (3) | C20A—C19—O1—Sn1 | 39 (3) |
C6—C1—Sn1—C13 | −83.2 (4) | C21A—C22A—C23A—C24A | −173 (4) |
C6—C1—Sn1—Cl1 | 16.6 (3) | C21A—C22A—C27A—C26A | 173 (4) |
C6—C1—Sn1—O1 | −159.1 (4) | C22B—C21B—N1—C19 | −105 (2) |
C7—C12—C11—C10 | 0.0 | C22B—C21B—N1—C21A | 169 (17) |
C12—C7—C8—C9 | 0.0 | C22B—C21B—N1—C28 | 72 (3) |
C12—C7—Sn1—C1 | 46.3 (4) | C22B—C21B—S1B—C20B | 100.0 (17) |
C12—C7—Sn1—C13 | −112.8 (4) | C22B—C23B—C24B—C25B | 0.0 |
C12—C7—Sn1—Cl1 | 148.7 (3) | C23B—C22B—C27B—C26B | 0.0 |
C12—C7—Sn1—O1 | −35.6 (4) | C23B—C24B—C25B—C26B | 0.0 |
C12—C11—C10—C9 | 0.0 | C24B—C25B—C26B—C27B | 0.0 |
C11—C10—C9—C8 | 0.0 | C25B—C26B—C27B—C22B | 0.0 |
C10—C9—C8—C7 | 0.0 | C27B—C22B—C23B—C24B | 0.0 |
C8—C7—C12—C11 | 0.0 | C28—C29—C30—C31 | −56.4 (14) |
C8—C7—Sn1—C1 | −134.1 (4) | C29—C28—C33—C32 | −58.0 (12) |
C8—C7—Sn1—C13 | 66.9 (4) | C29—C28—N1—C19 | 90.0 (10) |
C8—C7—Sn1—Cl1 | −31.6 (4) | C29—C28—N1—C21B | −87.1 (16) |
C8—C7—Sn1—O1 | 144.1 (4) | C29—C28—N1—C21A | −103 (3) |
C13—C18—C17—C16 | 0.0 | C29—C30—C31—C32 | 57.4 (16) |
C18—C13—C14—C15 | 0.0 | C30—C31—C32—C33 | −57.3 (16) |
C18—C13—Sn1—C1 | −7.3 (4) | C31—C32—C33—C28 | 57.0 (14) |
C18—C13—Sn1—C7 | 151.8 (4) | C33—C28—C29—C30 | 57.6 (12) |
C18—C13—Sn1—Cl1 | −109.3 (4) | C33—C28—N1—C19 | −143.8 (8) |
C18—C13—Sn1—O1 | 70.9 (4) | C33—C28—N1—C21B | 39.1 (17) |
C18—C17—C16—C15 | 0.0 | C33—C28—N1—C21A | 23 (3) |
C17—C16—C15—C14 | 0.0 | N1—C19—C20B—S1B | −22.9 (17) |
C16—C15—C14—C13 | 0.0 | N1—C19—C20A—S1A | −7 (3) |
C14—C13—C18—C17 | 0.0 | N1—C19—O1—Sn1 | −157.1 (6) |
C14—C13—Sn1—C1 | 176.1 (3) | N1—C21B—C22B—C23B | −148.8 (19) |
C14—C13—Sn1—C7 | −24.8 (4) | N1—C21B—C22B—C27B | 41 (3) |
C14—C13—Sn1—Cl1 | 74.1 (4) | N1—C21B—S1B—C20B | −26.7 (18) |
C14—C13—Sn1—O1 | −105.7 (4) | N1—C21A—S1A—C20A | −13 (4) |
C19—C20B—S1B—C21B | 27.5 (17) | N1—C28—C29—C30 | −175.3 (8) |
C19—C20A—S1A—C21A | 12 (4) | N1—C28—C33—C32 | 176.3 (9) |
C19—O1—Sn1—C1 | 175.4 (7) | O1—C19—C20B—S1B | 162.3 (11) |
C19—O1—Sn1—C7 | −65.6 (7) | O1—C19—C20A—S1A | 158.2 (17) |
C19—O1—Sn1—C13 | 55.7 (7) | O1—C19—N1—C21B | 177.3 (15) |
C19—O1—Sn1—Cl1 | 53.7 (18) | O1—C19—N1—C21A | −168 (3) |
C20B—C19—C20A—S1A | −104 (8) | O1—C19—N1—C28 | 0.1 (12) |
C20B—C19—N1—C21B | 2.6 (17) | S1A—C21A—N1—C19 | 11 (4) |
C20B—C19—N1—C21A | 18 (3) | S1A—C21A—N1—C21B | 112 (17) |
C20B—C19—N1—C28 | −174.6 (13) | S1A—C21A—N1—C28 | −156 (2) |
C20B—C19—O1—Sn1 | 17.1 (17) | S1B—C21B—C22B—C23B | 92.4 (18) |
C21B—C22B—C23B—C24B | −170 (2) | S1B—C21B—C22B—C27B | −78 (2) |
C21B—C22B—C27B—C26B | 170 (2) | S1B—C21B—N1—C19 | 17.8 (19) |
C22A—C23A—C24A—C25A | 0.0 | S1B—C21B—N1—C21A | −68 (14) |
C22A—C21A—N1—C19 | −116 (3) | S1B—C21B—N1—C28 | −165.0 (11) |
C22A—C21A—N1—C21B | −15 (12) | Sn1—C1—C2—C3 | 178.2 (4) |
C22A—C21A—N1—C28 | 77 (4) | Sn1—C1—C6—C5 | −178.3 (4) |
C22A—C21A—S1A—C20A | 109 (4) | Sn1—C7—C12—C11 | 179.7 (4) |
C23A—C22A—C27A—C26A | 0.0 | Sn1—C7—C8—C9 | −179.7 (4) |
C23A—C22A—C21A—N1 | −134 (3) | Sn1—C13—C18—C17 | −176.6 (4) |
C23A—C22A—C21A—S1A | 106 (4) | Sn1—C13—C14—C15 | 176.5 (4) |
Acknowledgements
We thank Temple University, Department of Chemistry, for the use of their Bruker 500 MHz NMR spectrometer.
Funding information
Funding for this research was provided by: NSF funding (CHEM-0131112) for the X-ray diffractometer .
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