Search

A series of coordination polymers (CPs), some of them featuring an unusual architecture, have been constructed by treatment of RSCH2C≡CCH2SR (R = C6H11L1, t-Bu L2) with CuX (X = Cl, Br, I) and CuX2. The outcome of the reaction of L1 with CuI depends on the metal-to-ligand ratio. Treatment of CuI with L1 in a 2 : 1 ratio affords the luminescent 2D CP [Cu4I4(μ-L1)2]n (CP1), whose grid-shaped network is built upon Cu4(μ3-I)4 cubane-like clusters as secondary building units (SBUs), interconnected via bridging L1 ligands. The use of a 1 : 1 ratio gives a material, whose particularity is the coexistence of two topological isomers within the unit cell. The first one, [{Cu(μ2-I)2Cu}(μ-L1)2]n (CP2), consists of 1D ribbons. The second isomer having a 0D topology, [{Cu(μ2-I)2Cu}(μ-L1)2] D1, is built upon discrete molecular complexes, whose dinuclear [Cu(μ2-I)2Cu] rhomboid-shaped core is spanned by two bridging L1 ligands. Mixing CuBr with L1 in MeCN solution leads to an isostructural material incorporating both 0D [{Cu(μ2-Br)2Cu}(μ-L1)2] complex D2 along with the 1D isomer [{Cu(μ2-Br)2Cu}(μ-L1)2]n (CP3). However, only the 1D CP [{Cu(μ2-Cl)2Cu}(μ-L1)2]n (CP4) results from complexation of L1 with CuCl. A stoichiometry-dependence is also noticed upon treatment of CuI with L2. Conducting the reaction in a 2 : 1 ratio yields the luminescent 2D CP [Cu4I4(μ-L2)2]n (CP5), whereas mixing equimolar amounts of the reactants produces 2D CP [{Cu(μ2-I)2Cu}(μ-L2)2]n (CP6). Structurally similar 2D CPs [{Cu(μ2-X)2Cu}(μ-L2)2]n (CP8 and CP9) result from complexation of L2 on CuBr or CuCl, respectively. Treatment of L2 with an excess of CuBr or CuBr2 in refluxing acetonitrile led to the transfer of Br to the acetylenic triple bond, generating an olefinic halogenated dithioether ligand Bu L3 that coordinates to CuBr to generate a 1D network [{Cu(μ2-Br)2Cu}(CH3CN)(μ-L3)]n (CP9). Using different conditions (propionitrile at 293 K), the reaction of L2 and excess CuBr led to the formation of a 2D network [{Cu(μ2-Br)2Cu}(μ-L2)(μ-L3)]n (CP10) incorporating both L2 and L3 in an alternating manner as assembling ligands. An isostructural chloro-analogue 2D [{Cu(μ2-Cl)2Cu}(μ-L2)(μ-L4)]n (CP11) was obtained using CuCl or CuCl2. The crystallographic work is completed by thermal analyses and investigation of the luminescence properties of CP1 and CP5 at 77 and 298 K. [ABSTRACT FROM AUTHOR]

With the aim to elaborate novel and inexpensive sulphur-rich materials featuring unusual network architectures, the coordination chemistry of the tetradentate thiaheterocycle 1,2-di(1,3-dithian-2-yl)ethane L1 ligand toward CuX and HgX2 salts was investigated. When L1 is reacted with CuI in a 1 : 1 ratio, a two-dimensional CP [{Cu(μ2-I)2Cu}(μ2-L1)]n (CP1) is formed, in which two out of four S atoms of L1 remain non-coordinated. Upon treatment of L1 with CuI in a 1 : 2 ratio, [{Cu(μ2-I)2Cu}(μ4-L1)]n (CP2) is obtained, in which each S atom of L1 coordinates to one copper centre forming a 2D layer. Raising the ligand-to-CuI ratio to 1 : 4 affords the 2D material [{Cu(μ4-I)(μ2-I)Cu}2(μ4-L1)]n (CP3), in which [Cu(μ4-I)(μ2-I)Cu]n ribbons are interconnected through μ4-bridging L1 ligands. Upon the reaction of L1 with CuBr in a 1 : 2 ratio, a 2D CP [{Cu(μ2-Br)}2(μ2-L1)(μ4-L1)0.5]n (CP4) is formed at room temperature and a 2D CP [{Cu(μ2-Br)}2(μ4-L1)]n (CP5) is obtained in refluxing propionitrile. In CP4 and CP5 Cu atoms are bridged by a single μ2-Br ligand giving rise to [Cu(μ2-Br)Cu]n ribbons but CP4 differs from CP5 from the metal to ligand ratio and the presence of non-coordinated S atoms. Employing a 1 : 3 ratio, a 1D ribbon [{Cu(μ2-Br)}3(MeCN)(μ4-L1)]n (CP6) is generated, that contains both tetrahedral and trigonal copper atoms. CP6 also presents two different L1 ligands that differ by the coordination mode of the sulphur atoms (S acting as 2 or as 4 electron-donor). With CuCl, a 2D network [{Cu(μ2-Cl)2Cu}(μ4-L1)]n (CP7) is generated. L1 coordinates also on HgX2 salts to yield CPs whose architecture depends on the ligand-to-metal ratio. The meander-shaped 1D CP [(HgI2)(μ2-L1)]n (CP8) and the linear 1D ribbons of CP9 and CP12 [(HgX2)(μ2-L1)]n (X = Br, Cl) result from treatment with L1 in a 1 : 1 ratio. In the case of HgBr2, using a 2 : 1 metal-to-ligand ratio, 1D polymeric [{BrHg(μ2-Br)2HgBr}(μ2-L1)] (CP10) is produced. HgI2 and HgBr2 have also been reacted with 2-methyl-1,3-dithiane L2 yielding the molecular complexes [{IHg(μ2-I)2HgI}(κ1-L2)2] (D1) and [HgBr2(κ1-L2)2] (M1). Two heterometallic 1D materials [{IHg(μ2-I)2HgI(μ2-I)2{Cu(RCN)2}2(μ2-L1)]n (CP13) and (CP14) result from the treatment of CP1 with HgI2 in MeCN or EtCN. Performing the reaction of CP1 with HgBr2 in acetonitrile produces the zwitterionic 2D material [Cu(MeCN)}(HgIBr2)(μ2-L1)1.5]n (CP15). [ABSTRACT FROM AUTHOR]

We herein present two polymeric solid state structures of pmdta-stabilized methyllithium with co-existing dimeric and tetrameric units, exhibiting partial incorporation of nearly omnipresent LiCl selectively in the dimeric entities. An unexpected interconnecting contact from these positions to a neighboring tetrameric unit is observed. [ABSTRACT FROM AUTHOR]

The title compound, C22H22O2S2, 1, represents an example of an ortho-vanillinbased functionalized dithioether, which could be useful as a potential chelating ligand or bridging ligand for coordination chemistry. This dithioacetal 1 crystallizes in the orthorhombic space group Pbca. The phenyl rings of the benzyl groups and that of the vanillin unit form dihedral angles of 35.38 (6) and 79.77 (6)°, respectively. The crystal structure, recorded at 100 K, displays both weak intramolecular O--H…O and intermolecular O--H…S hydrogen bonding. [ABSTRACT FROM AUTHOR]

The polymeric title compound, [Cu2(C2H3N)2(C3H6S2)2](PF6)2, represents an example of a one-dimensional coordination polymer resulting from the reaction of [Cu(MeCN)4][PF6] with 1,3-dithiolane. The cationic one-dimensional ribbon consists of two copper(I) centers each ligated by one acetonitrile molecule and interconnected through two bridging 1,3-dithiolane ligands. One S-donor site of each ligand is κ¹-bound to Cu, whereas the second S atom acts as a four-electron donor, bridging two Cu atoms in a κ4-bonding mode. The positive charge of each copper cation is compensated for by a hexafluoridophosphate counter-ion. In the crystal, the polymer chains are linked by a series of C--H ⋯F hydrogen bonds, forming a supramolecular framework. [ABSTRACT FROM AUTHOR]

Weighting both the basicity and nucleophilicity of an organolithium compound is crucial for an effective use of these reagents in syntheses. To achieve this, an aggregate of optimal size and reactivity has to be formed by adding suitable donating agents. Against usual expectations, this is not inevitably the smallest possible aggregate. In this work, we show that the monomeric complex of (trimethylsilyl)methyllithium stabilized by the bidentate ligand (R,R)-TMCDA shows no significant reactivity. In contrast, two dimeric aggregates stabilized by monodentate quinuclidine were obtained, exhibiting enhanced reactivity compared to the parent compound and to the monomeric complex. [ABSTRACT FROM AUTHOR]

The first synthetic access to stable and acyclic 1,3‐butadienes with two electron‐withdrawing carbonyl groups and their potential to deliver new molecular scaffolds through intriguing endo‐selective Diels–Alder cycloadditions are presented. The bicyclic scaffolds produced through the cycloaddition chemistry of electron‐deficient dienes afforded potent Hedgehog signaling pathway inhibitors. Uniquely deficient! A facile synthetic access to stable, electron‐deficient and acyclic 1,3‐butadienes bearing two orthogonal electron‐withdrawing groups is presented. This method opens the door to many molecular frameworks, including new Hedgehog pathway inhibitors. [ABSTRACT FROM AUTHOR]

Transition metal catalysts can mediate a plethora of skeleton rearrangements of a range of substrates to construct complex small molecules. Yet, their potential to transform common substrates into distinct molecular scaffolds has not been fully explored to deliver biologically relevant small molecules. Gold(I)‐catalyzed transformations of enynes are amongst the most intriguing rearrangements and provide opportunities to access a range of diverse scaffolds efficiently. In ligand‐directed divergent synthesis (LDS), variation of ligands in metal complexes determines the fate of substrates during their transformation into distinct scaffolds. For instance, variation of ligands for the gold(I) catalysts helps to transform oxindole derived 1,6‐enynes into several distinct molecular frameworks. In this report, we present how ligand variation in gold(I) catalysts, nucleophile‐additives and alkyl and alkynyl substitutions on the 1,6‐enynes as well as replacement of the oxindole ring with a different privileged ring‐system (PRS) influence the LDS approach to access a wider chemical space. Based on the experimental results, we propose several mechanistic pathways in gold(I)‐catalyzed cycloisomerizations and cascade reactions of 1,6‐enyne substrates leading to structurally distinct chemotypes. A ligand‐directed divergent scaffold synthesis was explored by varying the ligands for the gold(I) catalysts and the nucleophiles in the cycloisomerization reactions of oxindole based 1,6‐enynes. The strategy afforded several distinct and structurally complex molecular scaffolds. [ABSTRACT FROM AUTHOR]

Guided by the principle of biology-oriented synthesis, a collection of compounds with decahydro-4,8-epoxyazulene scaffold occurring in bioactive natural products was synthesized by the rhodium(II)- catalyzed 1,3-dipolar cycloaddition reaction of pentafulvenes and carbonyl ylides. The products can be obtained in moderate to high yields, with moderate enantioselectivity and excellent diastereoselectivity and regioselectivity. [ABSTRACT FROM AUTHOR]

The reaction of benzyl lithiums is an important aspect in organic and organometallic synthesis. Reported herein are detailed insights into the reactivity of benzyl lithiums as regulated by intermediate structures. By discussing the carbometalation of allylamines and the reaction of the formed benzyl-lithium compounds with electrophiles, the influence of the metal as well as the solvent on the electronic structure of the intermediate is described. This molecular structure strongly influences the reactivity of these intermediates. By choosing the appropriate reaction conditions, the regioselectivity of reactions with electrophiles can be regulated. With trimethylchlorosilane in n-pentane a selective reaction at the para-position takes place. In contrast, selective reaction at the benzylic position, with trimethylchlorostannane in tetrahydrofuran (THF) as a solvent, is accomplished. [ABSTRACT FROM AUTHOR]

Abstract Phytochemical studies of the seeds of the Cameroonian medicinal plant, Salacia staudtiana , resulted in the isolation and identification of five new cardenolides (1 – 5) as well as a new dihydro-β-agarofuran (9), along with eight known compounds. The structures of all compounds were elucidated by 1D/2D NMR, ESI-HRMS data and comparison with literature data. The relative configurations of the new compounds were defined by X-ray crystallography analysis, NOESY correlations and coupling constants. We evaluated their antibacterial efficacy against two commonly dispersed environmental strains of Escherichia coli and Bacillus subtilis , and two pathogenic strains of Staphylococcus aureus and Pseudomonas aeruginosa , compared to the standard antibiotics, streptomycin and gentamicin. Moreover, we assessed the antibacterial activity of the crude extract of the seeds in parallel to evaluate the plausible synergistic effects of the compounds in chemical defense of the seeds during germination and plant reproduction. The isolated compounds showed moderate antibacterial activities against the tested organisms. Compounds 1 and 3 and the crude extract exhibited distinct antibacterial activities against B. subtilis and S. aureus. The isolated compounds showed weak DPPH radical scavenging properties compared to the reference standard (Trolox). Our study lends evidence to the antibacterial chemical defense of S. staudtiana seeds by seed-borne compounds. Graphical abstract Unlabelled Image [ABSTRACT FROM AUTHOR]

Seven new cardenolides, staudtianoside A−F ( 1−6 ) and staudtianogenin A ( 8 ), were isolated along with six known compounds from the stem bark of the Cameroonian medicinal plant Salacia staudtiana Loes. ex Fritsch. The structures were elucidated by means of ESI-HRMS and NMR spectroscopic methods and by comparison with literature data. The relative configurations of the new compounds were determined by X-ray diffraction analysis, NOESY correlation and coupling constants. We evaluated the antibacterial efficacy of the isolated compounds against two commonly dispersed environmental strains of Escherichia coli and Bacillus subtilis , as well as against two human pathogenic clinical strains of Staphylococcus aureus and Pseudomonas aeruginosa . Compounds 1 , 2 and 8 exhibited marked antibacterial potencies against the clinically relevant P. aeruginosa that were comparable to the standard antibiotics. Compound 2 was also active against S. aureus and E. coli . Further, compounds 5 and 8 demonstrated efficacy against E. coli as well as B. subtilis . The structure-activity relationship of the tested compounds is discussed. [ABSTRACT FROM AUTHOR]

With the aim to elaborate novel and inexpensive sulphur-rich materials featuring unusual network architectures, the coordination chemistry of the tetradentate thiaheterocycle 1,2-di(1,3-dithian-2-yl)ethane L1 ligand toward CuX and HgX 2 salts was investigated. When L1 is reacted with CuI in a 1 : 1 ratio, a two-dimensional CP [{Cu(μ 2 -I) 2 Cu}(μ 2 -L1)] n (CP1) is formed, in which two out of four S atoms of L1 remain non-coordinated. Upon treatment of L1 with CuI in a 1 : 2 ratio, [{Cu(μ 2 -I) 2 Cu}(μ 4 -L1)] n (CP2) is obtained, in which each S atom of L1 coordinates to one copper centre forming a 2D layer. Raising the ligand-to-CuI ratio to 1 : 4 affords the 2D material [{Cu(μ 4 -I)(μ 2 -I)Cu} 2 (μ 4 -L1)] n (CP3), in which [Cu(μ 4 -I)(μ 2 -I)Cu] n ribbons are interconnected through μ 4 -bridging L1 ligands. Upon the reaction of L1 with CuBr in a 1 : 2 ratio, a 2D CP [{Cu(μ 2 -Br)} 2 (μ 2 -L1)(μ 4 -L1) 0.5 ] n (CP4) is formed at room temperature and a 2D CP [{Cu(μ 2 -Br)} 2 (μ 4 -L1)] n (CP5) is obtained in refluxing propionitrile. In CP4 and CP5 Cu atoms are bridged by a single μ 2 -Br ligand giving rise to [Cu(μ 2 -Br)Cu] n ribbons but CP4 differs from CP5 from the metal to ligand ratio and the presence of non-coordinated S atoms. Employing a 1 : 3 ratio, a 1D ribbon [{Cu(μ 2 -Br)} 3 (MeCN)(μ 4 -L1)] n (CP6) is generated, that contains both tetrahedral and trigonal copper atoms. CP6 also presents two different L1 ligands that differ by the coordination mode of the sulphur atoms (S acting as 2 or as 4 electron-donor). With CuCl, a 2D network [{Cu(μ 2 -Cl) 2 Cu}(μ 4 -L1)] n (CP7) is generated. L1 coordinates also on HgX 2 salts to yield CPs whose architecture depends on the ligand-to-metal ratio. The meander-shaped 1D CP [(HgI 2 )(μ 2 -L1)] n (CP8) and the linear 1D ribbons of CP9 and CP12 [(HgX 2 )(μ 2 -L1)] n (X = Br, Cl) result from treatment with L1 in a 1 : 1 ratio. In the case of HgBr 2 , using a 2 : 1 metal-to-ligand ratio, 1D polymeric [{BrHg(μ 2 -Br) 2 HgBr}(μ 2 -L1)] (CP10) is produced. HgI 2 and HgBr 2 have also been reacted with 2-methyl-1,3-dithiane L2 yielding the molecular complexes [{IHg(μ 2 -I) 2 HgI}(κ 1 -L2) 2 ] (D1) and [HgBr 2 (κ 1 -L2) 2 ] (M1). Two heterometallic 1D materials [{IHg(μ 2 -I) 2 HgI(μ 2 -I) 2 {Cu(RCN) 2 } 2 (μ 2 -L1)] n (CP13) and (CP14) result from the treatment of CP1 with HgI 2 in MeCN or EtCN. Performing the reaction of CP1 with HgBr 2 in acetonitrile produces the zwitterionic 2D material [Cu(MeCN)}(HgIBr 2 )(μ 2 -L1) 1.5 ] n (CP15).

The presence of metal centers with often highly conserved coordination environments is crucial for roughly half of all proteins, having structural, regulatory, or enzymatic function. To understand and mimic the function of metallo-enzymes, bioinorganic chemists pursue the challenge of synthesizing model compounds with well-defined, often heteroleptic metal sites. Recently, we reported the design of tailored homoleptic coordination environments for various transition metal cations based on unimolecular DNA G-quadruplex structures, templating the regioselective positioning of imidazole ligandosides L I . Here, we expand this modular system to more complex, heteroleptic coordination environments by combining L I with a new benzoate ligandoside L B within the same oligonucleotide. The modifications still allow the correct folding of parallel tetramolecular and antiparallel unimolecular G-quadruplexes. Interestingly, the incorporation of L B results in strong destabilization expressed in lower thermal denaturation temperatures T m . While no transition metal cations could be bound by G-quadruplexes containing only L B , heteroleptic derivatives containing both L I and L B were found to complex Cu II , Ni II , and Zn II . Especially in case of Cu II we found strong stabilizations of up to Δ T m = +34°C. The here shown system represents an important step toward the design of more complex coordination environments inside DNA scaffolds, promising to culminate in the preparation of functional metallo-DNAzymes., (Copyright © 2020 Punt, Stratmann, Sevim, Knauer, Strohmann and Clever.)

The polymeric title compound, [Cu 2 (C 2 H 3 N) 2 (C 3 H 6 S 2 ) 2 ](PF 6 ) 2 , represents an example of a one-dimensional coordination polymer resulting from the reaction of [Cu(MeCN) 4 ][PF 6 ] with 1,3-di-thiol-ane. The cationic one-dimensional ribbon consists of two copper(I) centers each ligated by one aceto-nitrile mol-ecule and inter-connected through two bridging 1,3-di-thiol-ane ligands. One S-donor site of each ligand is κ 1 -bound to Cu, whereas the second S atom acts as a four-electron donor, bridging two Cu atoms in a κ 4 -bonding mode. The positive charge of each copper cation is compensated for by a hexa-fluorido-phosphate counter-ion. In the crystal, the polymer chains are linked by a series of C-H⋯F hydrogen bonds, forming a supra-molecular framework., (© Knauer et al. 2020.)

The parent compound 1,3-dithiane (L1) was reacted with CuI providing the 1D coordination polymer [{Cu(μ 2 -I) 2 Cu}(μ 2 -L1) 2 ] n (CP1), an isostructural compound [{Cu(μ 2 -Br) 2 Cu}(μ 2 -L1) 2 ] n (CP2) was isolated upon treatment of CuBr with L1. In contrast, treatment of L1 with CuCl results in the formation of 2D polymeric [{Cu(μ 2 -Cl) 2 Cu}(μ 2 -L1)] n (CP3), in which each sulfur atom acts as a 4-electron donor. The 1D compounds [{Cu(μ 2 -X) 2 Cu}(μ 2 -L2) 2 ] n (CP7, X = Br, and CP8, X = Cl) resulting from treatment of 2-methyl-1,3 dithiane (L2) with CuBr and CuCl are isostructural with their CuI homologue [{Cu(μ 2 -I) 2 Cu}(μ 2 -L2) 2 ] n (CP5), reported previously. Using CuCN, a 2D CP of composition [{Cu(μ 2 -CN) 2 Cu}(μ 2 -L2) 2 ] n (CP9) has been isolated. Complexation of 2-isobutyl-1,3-dithiane (L3) on CuI generates a 2D material [{Cu 3 (μ 3 -I)(μ 2 -I) 2 (μ 2 -L3) 2 }] n (CP10), incorporating the usual trinuclear μ 3 -I-capped Cu clusters as SBUs, whereas 2D-polymeric compounds [{Cu(μ 2 -Br) 2 Cu}(μ 2 -L3) 2 ] n (CP11) and [{Cu(μ 2 -Cl) 2 Cu}(μ 2 -L3) 2 ] n (CP12) were obtained with CuBr and CuCl. Treatment of 2-Me 3 Si-1,3-dithiane (L4) with CuX yields the series [{Cu 2 (μ 4 -X)(μ 2 -X)}(μ 2 -L4)] n (CP13-CP15). With 2-phenyl-1,3-dithiane (L5), the outcome of the reaction with CuI depends on the reaction conditions. Reaction with CuI in MeCN provides a 1D ribbon [{Cu(μ 2 -I) 2 Cu}(MeCN) 2 (μ 2 -L5) 2 ] n (CP16), whereas treatment of CuI with L5 in hot EtCN yields 2D-polymeric[{Cu 3 (μ 3 -I)(μ 2 -I) 2 (μ 2 -L5) 2 }] n (CP17). A reversible phase transition from triclinic P1̅ to monoclinic P2 1 / m is observed when recording the structure of CP16 at five different temperatures in the 100-300 K range. Ligand L6 containing a ferrocenyl function at the 2-position was also probed as organometallic dithioether ligand. Reaction of L6 with 1 equiv of CuI produces the 0D dinuclear complex [{Cu(μ 2 -I) 2 Cu}(η 1 -L6) 2 (MeCN) 2 ] (D1), whereas treatment with 2 equiv of CuI affords the novel 1D CP [{Cu(μ 3 -I) 2 Cu}(μ-L6)] n (CP18), in which both S atoms of one L6 molecule span two copper centers of the infinite (CuI) n ribbon. Some selected results of thermal analyses and luminescence measurements are also presented.

The first synthetic access to stable and acyclic 1,3-butadienes with two electron-withdrawing carbonyl groups and their potential to deliver new molecular scaffolds through intriguing endo-selective Diels-Alder cycloadditions are presented. The bicyclic scaffolds produced through the cycloaddition chemistry of electron-deficient dienes afforded potent Hedgehog signaling pathway inhibitors., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A structurally unique and strongly luminescent nonporous 3D coordination polymer (CP) [Cu 8 I 8 (methyldithiane) 4 ] n , CP3, has been prepared in a quasi-anticipated manner from 2-methyl-1,3-dithiane, L1, and CuI. This CP incorporates an unprecedented Cu 8 I 8 cluster built upon two side-fused open cubanes. The crystal structure of CP3 has been determined at 100, 150, 200, 250, 300, 350, and 400 K to study the temperature dependence of the Cu···Cu distances. Two other topological 1D and 2D CPs isomers of formula [{Cu 2 I 2 }(L1) 2 ] n featuring dinuclear {Cu 2 (μ 2 -I) 2 } rhomboids were also obtained independently by control of the reaction conditions. These two CPs convert into CP3 in hot PrCN, thus indicating that this latter material is the thermodynamic product. While CP1 and CP2 are not emissive, CP3 exhibits an intense luminescence due to the incorporation of the octanuclear Cu 8 I 8 clusters as secondary building units within the network. The photophysical properties of CP3 have been investigated and rationalized by means of DFT and TDDFT computing. Furthermore, the thermal stability of these materials has been studied by ATG and DSC analyses. The Raman spectra of CP1-3 have been recorded in the solid state in the 50-500 cm -1 region.

The title compound, C17H27NO2S, exhibits a distorted geometry of the aromatic ring with elongated bonds at the ipso-C atom. The S atom deviates from the aromatic ring plane by 0.393 (4) Å. Similar to this, the adjacent isopropyl groups are bent out of the aromatic ring plane by -0.125 (4) and -0.154 (4) Å. Even the distant isopropyl group in para-position to the sulfonyl moiety shows a slight deviation from the ring plane of 0.111 (5) Å. These distortions, which are caused by the bulky substituents, can also be observed in related sulfonyl-aziridine structures.

The title compound, [Ge(CH3)3(C7H5O2)], was obtained as a by-product in the synthesis of the corresponding aldehyde. Two slightly different mol-ecules are present in the asymmetric unit. In both mol-ecules, the geometry of the aromatic ring plane is distorted by varying intensities. Additionally, the Ge atoms deviate from the mean aromatic ring planes. Whereas the distance of the Ge atom to the ring plane is only 0.101 (4) Å in the first mol-ecule, this distance is increased to 0.210 (4) Å in the second. In the crystal structure, centrosymmetric O-H⋯O hydrogen-bonded dimers are formed. The title compound is isostructural with the Si analogue [Haberecht et al. (2004 ▶). Acta Cryst. E60, o329-0330].

In the title compound, C16H20Si, a geometry different from an ideal tetra-hedron can be observed at the Si atom. The bonds from Si to the benzylic C atoms [Si-C = 1.884 (1) and 1.883 (1) Å] are slightly elongated compared to the Si-Cmeth-yl bonds [Si-C = 1.856 (1) and 1.853 (1) Å]. The Cbenz-yl-Si-Cbenz-yl bond angle [C-Si-C = 107.60 (6)°] is decreased from the ideal tetra-hedral angle by 1.9°. These distortions can be explained easily by Bent's rule. In the crystal, mol-ecules inter-act only by van der Waals forces.