Home Crystal structure of dichlorido-bis(dimethyl sulphoxide-κO)-bis(4-methylbenzyl-κC1)tin(IV), C20H30Cl2O2S2Sn
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Crystal structure of dichlorido-bis(dimethyl sulphoxide-κO)-bis(4-methylbenzyl-κC1)tin(IV), C20H30Cl2O2S2Sn

  • Kong Mun Lo , See Mun Lee and Edward R.T. Tiekink ORCID logo EMAIL logo
Published/Copyright: July 11, 2020

Abstract

C20H30Cl2O2S2Sn, monoclinic, P21/n (no. 14), a = 8.2430(1) Å, b = 13.7471(1) Å, c = 11.1619(2) Å, β = 110.864(2)°, V = 1181.90(3) Å3, Z = 2, Rgt(F) = 0.0164, wRref(F2) = 0.0445, T = 100(2) K.

CCDC no.: 2012228

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Colourless prism
Size:0.12 × 0.11 × 0.05 mm
Wavelength:Cu Kα radiation (1.54184 Å)
μ:12.4 mm−1
Diffractometer, scan mode:XtaLAB Synergy, ω
θmax, completeness:67.1°, >99%
N(hkl)measured, N(hkl)unique, Rint:14266, 2105, 0.020
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2051
N(param)refined:127
Programs:CrysAlisPRO [1], SHELX [2], [3], WinGX/ORTEP [4]
Table 2:

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

AtomxyzUiso*/Ueq
Sn0.50.50.50.01157(7)
Cl10.32862(6)0.49166(2)0.25754(4)0.01891(10)
S10.61206(5)0.73651(3)0.57748(3)0.01483(10)
O10.56601(14)0.65583(7)0.47547(10)0.0163(2)
C10.7390(2)0.47050(12)0.46739(15)0.0164(3)
H1A0.7395410.5088390.3924590.020*
H1B0.8378030.4929770.5428680.020*
C20.76585(19)0.36606(11)0.44419(15)0.0143(3)
C30.72325(19)0.32899(11)0.31983(15)0.0150(3)
H30.6853810.3721340.2487330.018*
C40.7355(2)0.23017(11)0.29892(15)0.0158(3)
H40.7064280.2067860.2137320.019*
C50.78993(19)0.16469(11)0.40094(16)0.0166(3)
C60.8378(2)0.20182(11)0.52483(16)0.0183(3)
H60.8789690.1588430.5959500.022*
C70.8263(2)0.30068(12)0.54596(15)0.0174(3)
H70.8602640.3242210.6314070.021*
C80.7966(2)0.05704(12)0.37749(18)0.0245(4)
H8A0.8890910.0435890.3438380.037*
H8B0.6849840.0357520.3151520.037*
H8C0.8201000.0217860.4582390.037*
C90.8428(2)0.73326(12)0.64729(17)0.0237(4)
H9A0.8795130.6716900.6932320.035*
H9B0.8836400.7875950.7073820.035*
H9C0.8922290.7386970.5796630.035*
C100.5912(2)0.84531(11)0.48602(16)0.0215(3)
H10A0.6578950.8389380.4292170.032*
H10B0.6356110.9004850.5440790.032*
H10C0.4685940.8562480.4345410.032*

Source of material

Di(4-methylbenzyl)tin dichloride was synthesized by the direct reaction of 4-methylbenzyl chloride (Merck) and metallic tin powder (Merck) in toluene according to a literature procedure [5]. Di(4-methylbenzyl)tin dichloride (0.40 g, 1.0 mmol) and dimethyl sulphoxide (Merck, 0.14 mL, 2.0 mmol) were heated in 95% ethanol (20 mL) and stirred for 2 h. After filtration, the filtrate was evaporated slowly until colourless crystals formed. Yield: 0.30 g (54%). M.pt (Mel-temp II digital melting point apparatus): >573 K (dec.). IR (Bruker Vertex 70v FTIR Spectrophotometer; cm−1): 903 (m) ν(S—O), 298 (s) ν(Sn—Cl). NMR (Bruker Ascend 400 MHz NMR spectrometer, chemical shifts relative to Me4Si, DMSO-d6 solution, p.p.m. at 50°): δ 2.25 (s, 3H, CH3), 2.28 (s, 2H, CH2), 2.37 (s, 3H, SCH3), 2.50 (s, 3H, SCH3), 7.00–7.24 (m, 4H, Ph-H). 13C{1H} NMR (as for 1H NMR): δ 21.2 (CH3), 40.8, 42.6 (SCH3), 63.2 (CH2), 127.0, 128.5, 130.0, 134.0 (Ph—C).

Experimental details

The C-bound H atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). Owing to poor agreement, one reflection, i.e. (−3 2 8), was removed from the final cycles of refinement.

Comment

The crystal and molecular structures of the title compound, (4-MeC6H4CH2)2SnCl2(DMSO)2 (I), were determined in connection with on-going studies into the structural chemistry of diorganotin dihalide adducts of diorgano sulphoxides, which can adopt five- and six-coordinate geometries depending on the number of coordinated diorgano sulphoxide molecules [6], [7], [8]. The molecular structure of (I) is shown in the figure (70% displacement ellipsoids; unlabelled atoms are related by the symmetry operation 1 − x, 1 − y, 1 − z) and has the Sn atom located on a centre of inversion.

The Sn atom is hexa-coordinated within an all-trans C2Cl2O2 donor set defined by the methylene-C1 [2.1652(15) Å], DMSO-O1 [2.2508(10) Å] and chlorido-Cl1 [2.5709(4) Å] atoms. The phenyl ring of the benzyl residue is folded to be disposed over the DMSO molecule. The arrangement enables the formation of an intramolecular S(lone-pair)⋯π(phenyl) contact with the S1⋯Cg(C2–C7) separation = 3.23 Å; see [9] for a recent discussion on S(lone-pair)⋯π(arene) interactions. It is noted that the resonances ascribed to DMSO-methyl substituents are distinct in both the 1H and 13C{1H} NMR spectra suggesting the S(lone-pair)⋯π(phenyl) contact persists in DMSO-d6 solution.

There are three structures in the literature of general formula R2SnCl2(DMSO)2. While the 4-FC6H4CH2 derivative [6] has an all-trans conformation as found in (I), the R = Me [10] and R = Ph [11] species have the chloride atoms cis and the Sn-bound organo-substituents, trans. The structural diversity broadens when the nature of the R groups in the sulphoxide molecule are changed, e.g. five-coordinate geometries are found in each of (2-ClC6H4CH2)2SnCl2[(PhCH2)2S=O] [7] and (4-BrC6H4CH2)2SnBr2[(PhCH2)2S=O] [8].

In the crystal of (I), directional methyl-C—H⋯Cl [C10—H10b⋯Cl1i: H10b⋯Cl1i = 2.78 Å, C10⋯Cl1i = 3.7166(17) Å with angle at H10b = 161° for symmetry operation (i) 1/2 + x, 3/2 − y, 1/2 + z] and C—H⋯π(phenyl) interactions [C9—H9c⋯Cg(C2–C7)ii: H9c⋯Cg(C2–C7)ii = 2.71 Å with angle at H9c = 134° for (ii) 2 − x, 1 − y, 1 − z] assemble molecules into a three-dimensional architecture.

The molecular packing was further analysed by calculating the Hirshfeld surface and the full- and delineated two-dimensional fingerprint plots, employing Crystal Explorer 17 [12] and standard protocols [13]. The analysis shows all surface contacts involve H with by far the greatest contribution of 67.8% being from H⋯H contacts. The next most important contributions are from Cl⋯H/H⋯Cl and C⋯H/H⋯C contacts, making percentage contributions of 14.9 and 11.5%, respectively. Smaller contributions are made by O⋯H/H⋯O [3.8%] and S⋯H/H⋯S [2.1%] contacts.

Acknowledgements

Sunway University Sdn Bhd is thanked for financial support of this work through Grant No. STR-RCTR-RCCM-001-2019.

References

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Received: 2020-06-10
Accepted: 2020-06-25
Published Online: 2020-07-11
Published in Print: 2020-08-26

©2020 Kong Mun Lo et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  67. Crystal structure of 3,3′-(1,2-phenylenebis(methylene))bis(1-methyl-1H-imidazol-3-ium) bis(hexafluoridophosphate), C16H20F12N4P2
  68. Crystal structure of catena-poly[diaqua-(μ2-tartrato-κ4O,O′:O′′,O′′′)zinc(II)], C4H8O8Zn
  69. The crystal structure of (6aR,6bS,8aS,8bR,9S,11aS,12aS,12bS)-10-(4-acetoxy-3-methylbutyl)-6a,8a,9-trimethyl-3,4,5,6,6a,6b,7,8,8a,8b,9,10,11a,12,12a,12b-hexadecahydro-1H-naphtho[2′,1′:4,5]indeno[2,1-b]furan-4-yl acetate, C31H48O5
  70. Crystal structure of 4,4′-(oxybis(methylene))bis(bromobenzene), C14H12Br2O
  71. Crystal structure of (N,N-dimethylsulphoxide)-[N-(3-ethoxy-2-(oxide)benzylidene)-3-methoxybenzenecarbohydrazonato-κ3N,O,O′]-dioxo-molybdenum(VI), C19H22MoN2O7S
  72. Crystal structure of dichlorido-bis(dimethyl sulphoxide-κO)-bis(4-methylbenzyl-κC1)tin(IV), C20H30Cl2O2S2Sn
  73. Crystal structure of (E)-2-amino-N′-(2-hydroxy-4-(2-(piperidin-1-yl)ethoxy)benzylidene)benzohydrazide monohydrate, C21H26N4O3 ⋅ H2O
  74. Crystal structure of chloridotris(4-chlorophenyl)(dimethyl sulfoxide-κO)tin(IV), C20H18Cl4OSSn
  75. Crystal structure of catena{di-aqua-sodium-[N-(hydroxyethyl), N-isopropyl-dithiocarbamato]}n, [C6H16NNaO2S2]n
  76. Crystal structure of 2,2,4,4,6,6-hexakis(4-chlorophenyl)-1,3,5,2,4,6-trithiatristanninane, C36H24Cl6S3Sn3
  77. Crystal structure of 6-methoxy-3-(5-(3-methoxyphenyl)-1,3,4-oxadiazol-2-yl)-4H-chromen-4-one-methanol (1/1), C20H18N2O6
  78. Crystal structure of hexanedihydrazide, C6H14N4O2
  79. Crystal structure of tert-butyl 2-(hydroxymethyl)-5-{4-[(methoxycarbonyl)amino]phenyl}-2,5-dihydro-1H-pyrrole-1-carboxylate, C18H24N2O5
  80. Crystal structure of [(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-κS]-(triphenylphosphine-κP)-gold(I), C28H26AuN2O3PS
  81. Crystal structure of [O-ethyl N-(4-nitrophenyl)thiocarbamato-κS](tri-4-tolylphosphine-κP)gold(I) tetrahydrofuran solvate, C30H30AuN2O3PS, C4H8O
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