Sn Cl Research Articles

Dichloridodiphenylbis(thiourea-κS)tin(IV)

The title compound, [Sn(C6H5)2Cl2(CH4N2S)2], has been obtained from the reaction between Sn(C6H5)2Cl2 and SC(NH2)2. The asymmetric unit consists of one half of the mol­ecular unit, the remainder generated by a twofold rotation axis located along the Cl—Sn—Cl bonds. The SnIV atom is coordinated by two phenyl groups, two Cl atoms and two thio­urea ligands in an all trans octa­hedral C2Cl2S2 environment. Individual mol­ecules are connected through N—H⋯Cl hydrogen bonds, leading to a three-dimensional network structure. Intra­molecular N—H⋯Cl hydrogen bonds are also present.

Unusual Reactivity of a C,N-Chelated Stannylene with Siloxanes and Silanols

The reactivity of stannylene (LCN)2Sn (1), where LCN is the 2-(N,N-dimethylaminomethyl)phenyl substituent, toward (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), silicon grease, and triphenylsilanol was explored. The reaction of 1 with one equivalent of TEMPO and silicon grease yielded cyclo-[(LCN)2SnOSn(LCN)2OSiMe2O] (6a), whereas the addition of two equivalents of TEMPO afforded cyclo-[(LCN)(LCN—O)SnOSiMe2OSiMe2O] (6b), in which the amine nitrogen atom of one of the LCN ligands is oxidized to N-oxide. The reaction of 1 with one equivalent of TEMPO and subsequent addition of triphenylsilanol gave (LCN)2Sn(OSiPh3)2 (5), which further reacted with air in a chloroform solution to provide [(LCN)(LCN═O)Sn(OSiPh3)Cl] (7), containing one of the chelating LCN ligands in the corresponding N-oxide form. In contrast, the direct reactions of 1 with one or two equivalents of triphenylsilanol gave rise to the adduct [Sn(OSiPh3)2]·C6H5CH2NMe2 (8a) and the salt [C6H5CH2N(H)Me2]+[Sn(OSiPh3)3]− (8b), respectively. All co...

Activation of E–Cl bonds (E = C, Si, Ge and Sn) by a C,N-chelated stannylene

The reactivity of (L(CN))(2)Sn (1) (where L(CN) is 2-(N,N-dimethylaminomethyl)phenyl-) towards various substrates containing E–Cl bond(s) has been studied (E = C, Si, Ge and Sn). Alkyl chlorides like chloroform or dichloromethane reacts with 1 to form (L(CN))(2)SnCl(2) and unidentified by-products in poor yields. The reaction of benzoyl chloride with 1 at low temperature yielded a thermally unstable product (L(CN))(2)Sn(Cl)C(O)Ph (2) which was isolated and characterized by both multinuclear NMR spectroscopy and X-ray diffraction techniques. The vicinity of the central tin atom in 2 reveals trigonal bipyramidal geometry. Attempts to oxidize 2 by dioxygen to give the corresponding organotin(IV) benzoate failed. On the other hand, the reaction of the in situ prepared (L(CN))(2)Sn=O (synthesized by the reaction of 1 with dioxygen) with PhCOCl resulted in the formation of the desired organotin(IV) benzoate (L(CN))(2)Sn(Cl)C(=O)OPh (3). The reaction of 1 with Ph3GeCl yielded triphenylgermyl-substituted diorganotin(IV) chloride (L(CN))(2)Sn(Cl)GePh(3) (4) which subsequently gave mixed diorganotin(IV) chloride-oxide [(L(CN))(2)SnCl](2)O (5) upon loss of the GePh(3) moiety in the air. When the same reaction was carried out in benzene instead of chloroform a unique [Ph(3)Ge](4)[Sn(6)O(8)] cluster (6) was obtained. Similarly, the reaction of 1 with Ph3SiCl provided triphenylsilyl-substituted diorganotin(IV) chloride (L(CN))(2)Sn(Cl)SiPh(3) (7) which was then oxidized to (L(CN))(2)Sn(Cl)OSiPh(3) (8). The unprecedented reaction of 1 with (n-Bu)(3)SnCl provided the distannane (L(CN))(2)Sn(Cl)SnBu(3) (9) which could be oxidized by dioxygen to a distannoxane (L(CN))(2)Sn(Cl)OSnBu(3) (10). In addition, the solid-state structures of 3, 5, 6 and 8 were determined by the X-ray diffraction techniques.

Condensation reactions assisted by acidic hydrogen bonded hydroxyl groups in solid tin(ii)hydroxychloride

Tin(II)hydroxychloride is reported as a heterogeneous Brønsted acid catalyst. Sn(OH)Cl was synthesized by a precipitation method and characterized by XRD, FT-IR, 1H MAS NMR, SEM, TG-DTA and N2 sorption. The acidity measurements of tin(II)hydroxychloride by FT-IR pyridine adsorption and 1H MAS NMR showed the presence of Brønsted acidity. The Brønsted acidity can be attributed to strong hydrogen bonding between the –OH and Cl groups. Sn(OH)Cl showed high activity for important condensation reactions such as the Prins condensation, Claisen–Schmidt condensation and ketalization. The catalytic activity of Sn(OH)Cl was compared with that of SnO, SnO2 and Sn2(OH)2O. The catalyst was recycled three times with a negligible decrease in activity.

Synthesis and molecular structure of mixed-metal stannylene derivatives of cyclopentadienyl(nitrosyl)(carbonyl) manganese

The metathesis of CpMn(CO)(NO)SnCl3 (I) and anionic carbonyls (ML−) Mn(CO)5−,Co(CO)4−,Cp′Mo(CO)3−,Cp′W(CO)3−,Cp″Mo(CO)3− provided trinuclear mixed-metal complexes of general formula CpMn(CO)(NO)SnCl2ML (VIII–XII; Cp = C5H5, Cp′ = C5H4CH3, Cp″ = C5H3(C4H9)2). Along with XII, the product of transmetallation Cp″Mo(CO)3SnCl3 (XIII) was separated. Interaction of I with Fe2(CO)82− gave the mixed-metal cluster Cp(CO)(NO)Mn–SnCl2–Fe(CO)4–SnCl2–MnCp(CO)(NO) (XIV) which contain the pentanuclear metal-chain. As determined by the single crystal XRD analysis, the Mn–Sn distance in CpMn(CO)(NO)Sn fragment is 0.2 Å shorter than the expected value based on the Mn/Sn sum of covalent radii (SCR). From the other hand, the shortening of Sn–ML distances is in an accord with the donor ability of an ML fragment in the row Co(CO)4 ∼ Mn(CO)5 < Fe(CO)4 < CpMn(CO)(NO < Cp′Mo(CO)3 < Cp′W(CO)3 < Cp″Mo(CO)3 owing to the additive back donation of the transition metal d-LEP to Sn vacant orbitals. The absence of substantial elongation of the Sn–Cl distances may result from the π-back donation of transition metal d-orbitals to tin d-orbitals.

Cephalosporin Tin(II) Complexes: Synthesis, Characterization, and Antibacterial Activity

The synthesis and spectral characterization of mononuclear cephalosporin tin(II) complexes of general formula [Sn(L)Cl] (L = monoanion of cephalothin HL1, cephradine HL2, cefotaxime HL3, cefazolin HL4, and ceftriaxone HL5), are reported. They were characterized by physicochemical and spectroscopic methods. The spectra indicated that the antibiotics act as multidentate ligand toward metal ions, via the amide and lactam carbonyl and carboxylate and N-azomoieties. The complexes are nontoxic, insoluble in water, and common organic solvents and probably have polymeric structures. The ligands and their tin complexes have been screened for their antibacterial activities and found to be quite active in this respect. Coordination of cephalothin and cephradine to tin(II) ion showed an enhancement of the antibacterial activity.

Measurement and analysis of the pure rotational spectra of tin monochloride, SnCl, using laser ablation equipped chirped pulse and cavity Fourier transform microwave spectroscopy

The pure rotational spectrum of tin monochloride, SnCl, has been measured and analyzed using chirped pulse and cavity Fourier transform microwave spectrometers equipped with a laser ablation source. SnCl, in its X2Π12 electronic state, has been measured in the 8–17GHz region. Rotational constants, centrifugal distortion constants, Λ-doubling constants, magnetic hyperfine constants, and nuclear electric quadrupole coupling constants for multiple isotopologues have been determined and are reported. The bond length, nuclear magnetic and quadrupole constants have been analyzed and compared against the family of tetral halides. Analysis of the bond length and hyperfine interactions point to a Sn–Cl single bond which is largely ionic in nature.

Dichloridobis(pyridine-2-thiolato-κ2N,S)tin(IV): a new polymorph

The title compound, [SnCl2(C5H4NS)2], is the product of reaction of 2,2′-dipyridyl disulfide with tin tetra­chloride. The SnIV atom adopts a distorted octa­hedral geometry, with the two bidentate pyridine-2-thiol­ate ligands forming two planar four-membered chelate rings. The two Sn—Cl, two Sn—N and two Sn—S bonds are in cis, cis and trans configurations, respectively. The crystal grown from acetonitrile represents a new monoclinic polymorph in space group C2/c with the mol­ecule having twofold rotational symmetry, the SnIV atom lying on the twofold axis. The mol­ecular structure of the monoclinic polymorph is very close to that of the triclinic polymorph studied previously in space group P-1, the mol­ecule occupying a general position [Masaki & Matsunami (1976 ▶). Bull. Chem. Soc. Jpn, 49, 3274–3279; Masaki et al. (1978 ▶). Bull. Chem. Soc. Jpn, 51, 3298–3301]. Apparently, the formation of the two polymorphs is determined by the different systems of inter­molecular inter­actions. In the crystal of the monoclinic polymorph, mol­ecules are bound into ribbons along the c axis by C—H⋯Cl hydrogen bonds, whereas in the crystal of the triclinic polymorph, mol­ecules form chains along the a axis by attractive S⋯S inter­actions. The crystal studied was a pseudo-merohedral twin; the refined BASF value is 0.221 (1).

The inorganic speciation of tin(II) in aqueous solution

This paper reports new voltammetric measurements on the interactions between tin(II) and the most important natural inorganic ligands, OH−, Cl−, F−, CO32-, SO42- and PO43-. For a better understanding of tin(II) speciation, an analysis is also given of prior data on the same systems from the literature. The formation constants were determined at t=25°C in different ionic media and at different ionic strengths, specifically the following: Sn(OH)q (0.1⩽I/molL−1⩽1.0 in NaNO3), SnClr and Sn(OH)Cl (0.1⩽I/molL−1⩽2.3 in Na(NO3, Cl)), Sn(SO4)r (0.1⩽I/molL−1⩽1.6 in Na(NO3, SO4)), SnHqCO3 and SnHqPO4 (0.15⩽I/molL−1⩽1.0 in NaNO3), where the subscripts r and q represent the stoichiometric coefficients. Concerning the SnFr species, reliable literature values were considered (0.15⩽I/molL−1⩽1.0 in NaClO4). Fifteen voltammetric measurements were performed in synthetic seawater; the total seawater binding ability was evaluated by a model in which synthetic seawater is expressed as a single salt, BA. The formation of species between tin(II) and the anion of the marine salt (A) was also proposed, and the corresponding stability constants at different salinities (5⩽S⩽50) were reported. In addition, studies on the solubility of Sn(OH)2(s) were carried out using voltammetry and light scattering measurements. The “extra-stability” of the mixed species with respect to the parent species was evaluated, in particular for Sn(OH)Cl and the corresponding species involving the anion of the marine salt (A). The dependence of the formation constants on ionic strength was analysed using extended Debye-Hückel and Specific ion Interaction Theory (SIT) type equations. Tin(II) speciation was also evaluated in different natural fluid conditions, where, in all cases, carbonate complexation was predominant, hampering the formation of hydrolytic species throughout the investigated pH range. Moreover, some formation enthalpy changes were calculated for the Sn(OH)+, Sn(OH)2(aq), Sn(OH)2(s), Sn(OH)3-, Sn2(OH)22+, Sn3(OH)42+, Sn(OH)Cl, SnCl+, SnCl2 and SnCl3- species on the basis of the available literature stability constant values at different temperatures and using the empirical relationships reported in the literature. The ΔH values at t=25°C were positive in all cases except for the Sn(OH)2(s) and Sn(OH)3- species, indicating an increase in the stability constant values with increasing temperature.This work represents an advance in the knowledge, understanding and modelling of the inorganic speciation of tin(II) in natural fluids, particularly for solutions containing chloride, fluoride, sulphate, carbonate and phosphate anions.

Selective fluorometric detection of pyrophosphate by 3-hydroxyflavone-diphenyltin(iv) complex in aqueous micellar medium

3-Hydroxyflavonate-diphenyltin(IV) chloride (Ph(2)Sn(Ofl)Cl) was prepared and characterized structurally by single crystal X-ray diffraction. The compound possesses high fluorescence (λ(max) 464 nm with excitation at 400 nm) in neutral aqueous solutions containing 5 mM cetyltrimethylammonium chloride and does not lose the flavonol ligand even at high dilution. The fluorescence is selectively quenched by pyrophosphate (PPi) (linear range 0-5 μM, detection limit 0.1 μM). Determination of 1 μM PPi tolerates the presence of 100-fold excess of AMP, ADP, inorganic phosphate and acetate, and 10-fold excess of ATP. From concentration profiles of the quenching effect it is concluded that quenching occurs due to formation of the complex (Ph(2)Sn(Ofl))(3)PPi, which is transformed at higher PPi concentrations to a simple 1 : 1 complex Ph(2)Sn(Ofl)(PPi). No flavonol ligand exchange with PPi is observed. A series of related organotin(IV) complexes were prepared in situ by reacting 3-hydroxyflavone with Me(2)SnCl(2), PhSnCl(3) and n-BuSnCl(3). The derivatives of Me(2)SnCl(2) and PhSnCl(3) behave similarly to Ph(2)Sn(Ofl)Cl but with lower sensitivity to PPi. However, the n-butyltin(IV) derivative tentatively of the composition n-BuSn(Ofl)(2) undergoes fluorescence enhancement rather than quenching in the presence of PPi in the μM concentration range. The results of this study demonstrate that the use of metal flavonol complexes as optical sensors for anions is a promising approach.

Reactivity of lithium n-butyl amidinates towards group 14 metal(ii) chlorides providing series of hetero- and homoleptic tetrylenes

The new class of homo- and heteroleptic n-butyl-N,N'-disubstituted amidinato group 14 metal(II) complexes were prepared by salt elimination from starting lithium amidinates and metal(II) chlorides both in stoichiometric ratio 2:1 and 1:1, respectively. The target amidinates contain less bulky isopropyl or cyclohexyl as well as a sterically demanding aromatic substituent. Desired 1:1 Pb(II) complexes are not accessible by the described procedure. Ligand transfer from Pb to Sn is taking place if homoleptic Pb(II) compounds are reacted with SnCl(2). Prepared tetrylenes were characterized by (1)H, (13)C, (119)Sn and (207)Pb NMR spectroscopy in C(6)D(6) or THF-d(8). X-Ray diffraction studies of one heteroleptic Ge(II) monomeric where the coordination polyhedron of the three coordinated germanium atoms is a trigonal pyramid, two different dimeric structures of heteroleptic Sn(II) complexes, one amidine hydroiodide byproduct and the oxidation product of the heteroleptic chloro Sn(II) amidinate as a tetranuclear species with two Sn(IV) and two Sn(II) atoms in central Sn(2)O(2) planar ring were performed on appropriate single crystals. The dimer of one of the heteroleptic stannylenes reveals a new type of monomeric units connection, weak Sn-Cl contact and an interaction of the tin atom with delocalized N-C(C)-N system of the amidinato ligand of the second molecule.

Structural properties and antibacterial potency of new supramolecular organotin(IV) dithiocarboxylates

A series of new organotin(IV) derivatives; Me 3SnL ( 1), Bu 3SnL ( 2), Ph 3SnL ( 3), Me 2SnClL ( 4), Bu 2SnClL ( 5), Ph 2SnClL ( 6), Et 2SnClL ( 7) and Et 2SnL 2 ( 8) where L = N-(2,3-dimethylphenyl)piperazine-1-carbodithioate have been synthesized and characterized by various analytical techniques. Among these techniques, 1H and 13C NMR were carried out to asses solution structures whereas the solid state structures were confirmed by FT-IR and X-ray single crystal analysis ( 3, 5 and 8). Crystal structure of complex ( 3) and ( 5) showed distorted trigonal bipyramidal geometry and square pyramidal geometry, respectively. The inclination of the structure 5 towards square-pyramidal may be due to the presence of the Sn–Cl⋯HN-piperazine hydrogen bonds between the adjacent molecules. A supramolecular structure is shown by compound ( 8), with central tin atom exists in a distorted octahedral geometry. The antibacterial results indicated the profound activity of the compounds against various strains of bacteria. In addition to this, the triorganotin(IV) derivatives were found more active than diorganotin(IV) compounds.

Diorganotin(IV) complexes of N-mono-, di- and tri-chloroacetyl, N′, N″-bis(isopropyl) phosphoric triamide

Three new carbacylamidophosphates with formula CH n Cl 3− n C(O)NHP(O)(NHCH(CH 3) 2) 2 ( n = 2 ( 1); n = 1 ( 2); n = 0 ( 3)) and their organotin compounds with formula (1)SnCl 2Me 2(μ- 1)SnCl 2Me 2 ( 4), SnCl 2Me 2( 2) 2·C 6H 5CH 3 ( 5) and [SnCl 2Me 2( 3)] n ( 6) were synthesized and characterized by elemental, IR and NMR spectra analyses. The spectroscopic properties of complexes were compared with those corresponding ligands. The crystal structures of complexes were determined by X-ray crystallography, which reveals that complex 4 is binuclear structure with two non-equivalent Sn atoms. One adopts a distorted trans(C,C) cis(O P,O P) cis(Cl,Cl) octahedral configuration, while the other adopts a distorted trigonal bipyramidal geometry composed of two methyl groups, two chlorine atoms and carbonyl group. Molecule 5 is centrosymmetric with two O P, disordered chlorine and methyl groups in trans positions. Toluene molecules are located in the interlayer spaces of 5. In compound 6, bonding via both PO and CO functionalities forms 1D infinite chain structures along b axis. The Sn–O P bond length in 6 is significantly longer than the same distance in 4 and 5, while the O P and Sn–Cl bonds are shorter. The bond lengths in these complexes were compared with those of N-benzoyl carbacylamidophosphates.

Chloridodiphen-yl{[1-(1,3-thia-zol-2-yl-κN)ethyl-idene]-4-phenyl-thio-semicarbazidato-κN,S}tin(IV) methanol monosolvate.

The title compound, [Sn(C6H5)2(C12H11N4S2)Cl]·CH4O, is formed during the reaction between 2-acetyl­thia­zole 4-phenyl­thio­semicarbazone (Hacthptsc) and diphenyl­tin(IV) dichloride in methanol. In the crystal structure, the Sn atom exhibits an octa­hedral geometry with the [N2S] anionic tridentate thio­semicarbazone ligand having chloride trans to the central N and the two phenyl groups trans to each other. The Sn—Cl distance is 2.5929 (6), Sn—S is 2.4896 (6) and Sn—N to the central N is 2.3220 (16) Å. The MeOH mol­ecules link the Sn complexes into one-dimensional chains via N—H⋯O and O—H⋯Cl hydrogen bonds.

(2-Amidoethyl)trichlorotin(IV)complexes with amido ligands and chloride ion: supramolecular arrays from H-bonds involving the amido and chloride ions

AbstractComplexes, (H2NCOCH2CH2-C,O)(L)SnCl3(2:L= XCH2CH2CONH2; X = H or Cl), rather than (H2NCOCH2CH2-C,O)SnCl3, have been isolated from reaction mixtures containing hydrochloric acid, tin and acrylamide in Et2O solution. Ligand exchange reactions occur between (2: L= EtCONH2) and HCONMe2or HCONHBu. The anionic complex, [pyridinium][(H2NCOCH2CH2-C,O)SnCl4],3, was isolated from a reaction mixture composed of pyridine and2. In both complex types,2and3, tin is hexacoordinate, in which the octahedral geometries are somewhat distorted due to variations in the Sn—Cl bond lengths, exemplifying thetranseffect, and the small bite angles of the chelating (2-amidoethyl-C,O) ligand. The supramolecular structures are dominated by intermolecular hydrogen-bonds with the NH2groups as the donor species. A feature of each crystal structure is a double chain in which the NH2group of the (2-amidoethyl-C,O) ligand acts as donor for N—H···X (X = Cl or O) intermolecular hydrogen-bonds.

Syntheses of Group 4 ansa‐Trovacene Complexes and Conversion of [1]Silatrovacenophanes into Paramagnetic Metallopolymers by Ring‐Opening Polymerization

An improved protocol for the selective dilithiation of [V(η(5)-C(5)H(5))(η(7)-C(7)H(7))] has been developed, which afforded [V(η(5)-C(5)H(4)Li)(η(7)-C(7)H(6)Li)]·PMDTA (5; PMDTA=N,N,N',N'',N''-pentamethyldiethylenetriamine) in almost quantitative yield (98%). In the solid state, the species features a dimeric structure with two terminal and two bridging lithium atoms, with the latter connecting both sandwich subunits. Reaction with suitable Group 4 dihalide compounds enabled the isolation of highly strained silicon- and germanium-bridged [1]trovacenophanes 6 and 7. Similarly, reaction of 5 with Cl(2)Sn(2)tBu(4) afforded the rather unstrained complex [V(η(5)-C(5)H(4))(η(7)-C(7)H(6))Sn(2)tBu(4)] (8), which together with 7 represent the first trovacenophanes to incorporate heavier analogues of silicon in the ansa-bridge. Ring-opening polymerization reactions of [V(η(5)-C(5)H(4))(η(7)-C(7)H(6))SiRR'] (2a: R=R'=Me; 6: R=Me, R'=iPr) were performed by heating in a solution of toluene in the presence of the Karstedt catalyst, which resulted in the formation of the corresponding soluble poly(trovacenylsilanes) in yields of 41 and 33%, respectively. As estimated by gel permeation chromatography (GPC), the macromolecules possess molecular weights of M(n)=10,010 and 5580 g mol(-1) with polydispersity indices of 2.31 and 1.64 for 9 and 10, respectively. ESR spectroscopic studies on 9 and 10 revealed only a single broad resonance in each case without any identifiable (51)V hyperfine coupling.

Tetrachloridobis(dibenzyl sulfoxide-κO)tin(IV)

The six-coordinate SnIV atom in the title compound, [SnCl4(C14H14OS)2], exists in a cis-SnCl4O2 octa­hedral geometry. Of the four Cl atoms, two are close to adjacent S atoms [Cl⋯S = 3.320 (1) and 3.376 (1) Å]; the Sn—Cl bonds involving these two Cl atoms are longer than the other two Sn—Cl bonds.

Di-μ-chlorido-bis[chloridobis(dimethyl sulfoxide-κO)tin(II)

The structure of the title compound, [Sn2Cl4(C2H6OS)4], contains dimers formed through weak Sn⋯Cl [3.691 (2) Å] inter­actions, resulting in a planar Sn2Cl2 core with an inversion center at the centre of the four-membered ring. The SnII atoms are penta­coordinated and have a distorted octa­hedral Ψ-SnCl3O2 coordination geometry. The O atoms from the dimethyl sulfoxide mol­ecules occupy trans positions, while the Cl atoms exhibit a meridional arrangement.

Interaction of ethyltrichlorostannane withN,N‐dimethylamides ofO‐ trimethylsilyl‐α‐hydroxyacids

AbstractReactions of ethyltrichlorostannane withN,N‐dimethylamides of 2‐(trimethylsilyl)glycolic (2a), 2(S)‐lactic [(S)‐2b] and mandelic (2c) acids led to the first representatives of tin(IV)O,O‐monochelates containing the five‐membered SnOCC(O) monoanionic chelate cycles as a result of the substitution of one halogen atom. According to the X‐ray data, in the case of the derivatives of glycolic and mandelic acids, the isolated complexes have dimeric structures {EtCl2Sn[OCH(R)C(O)NMe2]}2[R = H (3a), Ph (3c)] with the bridge oxygen atoms and hexacoordinated tin atoms. By contrast, in the case of the derivative of lactic acid (S)‐2b, the product of the reaction is the cationic–anionic complex 2EtCl2Sn[OCH(Me)C(O)NMe2]·HCl (4), which is the adduct of two molecules of the respective monomeric complex with HCl. In addition,N,N‐dimethylamide ofO‐triethylstannylglycolic acid (5) with tetracoordinated tin is described. To analyze the stability of complex 4, the experimental charge density study and the quantum chemical calculations [PBE0/6‐311G(d,p)] were carried out. Topological analysis of the experimental and calculated electron density distribution functions allowed us to conclude that the strong OH···O bond with pronounced covalent contribution stabilizes the dimeric structure of 4 to a greater extent than the bridged SnCl bonds. Copyright © 2010 John Wiley &amp; Sons, Ltd.

Room‐Temperature Synthesis of the Highly Polar Cluster Compound Sn[SnCl][W3Cl13

AbstractA new synthetic strategy is employed to synthesize a tungsten trinuclear cluster compound with an ionic liquid (IL) as the reaction medium. Dark brown block‐shaped crystals of Sn[SnCl][W3Cl13] were obtained at room temperature by reacting tin and WCl6 in Lewis acidic ionic liquid [BMIM]Cl/AlCl3 ([BMIM]+ = 1‐butyl‐3‐methylimidazolium). Compound Sn[SnCl][W3Cl13] crystallizes in the polar hexagonal space group P63 with cell parameters a = 959.8(1) and c = 1190.3(2) pm. The crystallographic point group of the [W3(μ3‐Cl)(μ‐Cl)3Cl9]3– cluster anions is C3, but C3v pseudosymmetry is observed within twice the standard deviation of the bond lengths. The W–W bond length is 272.18(6) pm. The tin(II) cations, which are in trigonal pyramidal and in distorted trigonal‐antiprismatic coordination spheres that comprise chloride ions, connect the clusters into layers that are stacked according to the 63 screw axis. One of the chloride ions is bound only to a single tin cation resulting in a [SnIICl]+ group with a Sn–Cl bond length of 236.1(5) pm. The pronounced polarity of the crystal structure means that its diffraction pattern exhibits huge deviations from Friedel's law. Most remarkable is that the intensity (Fc2) of reflection 004 is 175 % of the intensity of the 00$\bar {4}$ reflection.