Intermolecular Hg Research Articles

A Computational Chemistry Investigation of the Influence of Steric Bulk of Dithiocarbamato-Bound Organic Substituents upon Spodium Bonding in Three Homoleptic Mercury(II) Bis(N,N-dialkyldithiocarbamato) Compounds for Alkyl = Ethyl, Isobutyl, and Cyclohexyl

Three homoleptic Hg(S2CNR2)2, for R = ethyl (1), isobutyl (2), and cyclohexyl (3), compounds apparently exhibit a steric-dependent supramolecular association in their crystals. The small group in 1 allows for dimer formation via covalent Hg–S interactions through an eight-membered {–HgSCS}2 ring as the dithiocarbamato ligands bridge centrosymmetrically related Hg atoms; intradimer Hg···S interactions are noted. By contrast, centrosymmetrically related molecules in 2 are aligned to enable intermolecular Hg···S interactions, but the separations greatly exceed the van der Waals radii. The large group in 3 precludes both dimerization and intermolecular Hg···S interactions. Computational chemistry indicates that the potential region at the Hg atom is highly dependent on the coordination geometry about the Hg atom. Intramolecular (1) and intermolecular (2) spodium bonding (SpB) is demonstrated. Even at separations approaching 0.4 Å beyond the sum of the assumed van der Waals radii, the energy of the stabilization afforded by the structure directs SpB in 2 amounts to approximately 2.5 kcal/mol. A natural bond orbital (NBO) analysis points to the importance of the LP(S) → σ*(Hg–S) charge transfer and to the dominance of the dispersion forces and electron correlation to the SpB in 2.

The Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d10∙∙∙d10Interactions between Closed Shell (Ag+Hg2+) Metal Ions.

Here, a new tellurium and mercury containing mercuraazametallamacrocycle has been prepared via (2+2) condensation of bis(o-aminophenyl)telluride and bis(o-formylphenyl)mercury(II). The isolated bright yellow solid of mercuraazametallamacrocycle has adopted unsymmetrical figure-of-eight conformation in the crystal structure. To study the metallophilic interactions between closed shell metal ions, the macrocyclic ligand has been treated with two equiv of AgOTf (OTf = trifluoromethansulfonate) and AgBF4, which afforded greenish-yellow bimetallic silver complexes. The isolated silver complexes displayed intramolecular Hg···Ag, Te···Ag interactions as well as intermolecular Hg···Hg interactions and formed an extended 1D molecular chain by directing six atoms to interact as TeII···AgI···HgII···HgII···AgI···TeII in a non linear fashion. The Hg···Ag, Te···Ag interactions have also been studied in solution by 199Hg, 125Te NMR spectroscopy, absorption, and emission spectroscopy. In DFT calculations, the Atom in Molecule (AIM) analysis, non-covalent interactions (NCI), natural bonding orbital (NBO) analysis strongly supported for experimental evidences and revealed that the intermolecular Hg···Hg interaction is stronger than the intramolecular Hg···Ag interactions.

Metallophilic Mercuraazamacrocycles Derived from Bis{6‐formyl‐(2,3,4‐trimethoxy)phenyl}mercury: Reactivity with d10and d8Metal Ions

A (2+2) Dipodal condensation of bis{6‐formyl‐(2,3,4‐trimethoxy)phenyl}mercury (14) with various 1,2‐disubstitued diamines e.g., ethylenediamine,trans‐1,2‐diaminocyclohexane ando‐phenylenediamine led to the formation of 22‐membered mercuraazametallamacrocycles, [Hg‐{1‐C6H‐2,3,4‐(OCH3)3‐6‐(CHN)}2‐CH2–CH2]2(15), [Hg‐{1‐C6H‐2,3,4‐(OCH3)3‐6‐(CHN)}2‐C6H10]2(16) and [Hg‐{1‐C6H‐2,3,4‐(OCH3)3‐6‐(CHN)}2‐C6H4]2(17) respectively. The acceptor abilities and reactivities of the macrocycles are compared with the corresponding 22‐membered mercuraazametallamacrocycles obtained from the condensation of bis(formylphenyl)mercury (12) with the diamines. Also attempts have been made to prepare macrocycles with functionalized aryldiamines. Orange colored CuIcomplexes,24([15·Cu]ClO4) and26([16·Cu]ClO4), were obtained upon the treatment of [Cu(CH3CN)4ClO4] with macrocycles15and16, respectively. Similarly, brown colored AgIcomplexes,25([15·Ag]ClO4), and27([16·Ag]ClO4) were isolated by reacting macrocycles15and16with AgClO4. The reaction of macrocycle15with equimolar Pt(COD)Cl2afforded cyclometalated platinum(II) complex, Pt‐{1‐C6H‐2,3,4‐(OCH3)3‐6‐(CHN‐CH2)}2(28). Bis(2‐amino‐5‐methylphenyl)mercury (23), shows a very strong intermolecular Hg···Hg interaction. Density functional theory calculations and atoms in molecules analysis revealed the presence of metallophilic d10···d10interactions as well as d10···d8interactions in the synthesized compounds.

Synthesis, spectral, crystal structures, Hirshfeld surface analysis and DFT studies on phenylmercury(II) dithiocarbamate complexes and their utility for the preparation of mercury sulfide nanoparticles

Three new phenylmercury(II) dithiocarbamate complexes incorporating the furyl moiety, namely (N,N-difurfuryldithiocarbamato-S,S′)phenylmercury(II) (1), (N-furfuryl-N-(4-chlorobenzyl)dithiocarbamato-S,S′)phenylmercury(II) (2), and (N-furfuryl-N-(2-phenylethyl)dithiocarbamato-S,S′)phenylmercury(II) (3) have been prepared and characterized by elemental analysis, IR, 1H, and 13C NMR spectroscopy and X-ray crystallography. The crystal structures of 1, 2 and 3 show a linear mercury(II) core at the centre of the molecules. Weak intermolecular Hg⋯S interactions in 2 and 3 lead to the formation of linear chain and head to tail dimers, respectively. The Hirshfeld surface analysis and the associated 2D fingerprint plots of 1–3 have been also studied to evaluate intermolecular interactions. Theoretical calculations of isolated molecules of 1–3 have been performed using DFT method at B3LYP-LANL2DZ basis set. The geometrical parameters of 1–3 are in a good agreement with those obtained from the XRD experiment. The energy gap between EHOMO and ELUMO have been calculated. The molecular electrostatic potential (MEP) analysis support the substantial contribution of the resonance structure R1R2N+ = CS22− to the description of their structures. Complex 1 has been utilized as single source precursor to afford mercury sulfide nanoparticles via solvothermal decomposition in ethylenediammine. The as-prepared HgS nanoparticles were characterized using powder X-ray diffraction (PXRD), Transmission electron microscopy (TEM), Energy dispersive X-ray spectra (EDS) and Diffuse reflectance spectra(DRS). The band gap energy calculated from DRS spectrum shows evidence of quantum confinement.

(Benzylthiolato-κS)phenylmercury(II)

The title complex, [Hg(C6H5)(C7H7S)], was synthesized from benzyl 4-methylpiperidine-1-carbodithioate. In the complex, the HgIIcation binds to a C atom of a phenyl ring and the S atom of a benzylthiolate ligand in a linear coordination geometry. The molecule is bent at the methylene C atom and the S atom, resulting in asynconformation with respect to the benzyl and phenyl rings. The dihedral angle between the phenyl and benzyl rings is 64.6 (2)°. The crystal structure is stabilized by intermolecular Hg...S [3.290 (3) Å] contacts and C—H...π interactions, generating a three-dimensional network.

Synthesis, Structural Characterization and Supramolecularity of (O-methyl dithiocarbonato)(N,N-dimethylaminophenyl) mercury(II)

A new mercury(II) complex [Me2NC6H4HgS(S)COMe] (1) was synthesized and characterized by elemental anaylsis, FT-IR, and 1H and 13C NMR spectroscopy. The structure of complex (1) has been confirmed by X-ray diffraction and proved to have a linear coordination geometry around the metal ion with Hg(S2COMe) being in S,S conformation. Intramolecular Hg···S secondary bond resulting in chelation [3.113 (1) Å], while intermolecular Hg···S interactions in the 3.265–3.740 Å range were also observed to form zig-zag supramolecular tapes. In addition, these supramolecular arrays are moreover connected by C-H···S, C-H···O, and C-H···π intermolecular interactions, consolidating a 3D network.

Synthesis and structural characterization of monomeric mercury(II) selenolate complexes derived from 2-phenylbenzamide ligands.

Monomeric Hg(II) selenolate complexes derived from 2-phenylbenzamide ligands were prepared by oxidative addition of diselenides [{C6H4(CONR2)Se}2, R = Me, Et, iPr] to elemental Hg and reductive cleavage of the Se–N bond of isoselenazolone derivatives [(NO2)C6H3(CONSe)R, (R = allyl, nbutyl)] followed by the treatment with HgCl2. The complexes have been characterized by multinuclear NMR (1H, 13C and 77Se) spectroscopy and mass spectrometry which suggest the monomeric form of these in solution. The molecular structures of diselenides [C6H4(CONR2)Se]2 and mercury selenolates [Hg{(NO2)C6H3(CONH-C3H5) Se}2], [Hg{C6H4(CONiPr2)Se}2] and [Hg{C6H4(CONMe2)Se}2] were established by a single crystal X-ray diffraction study. Diselenides show strong intramolecular non-bonded Se⋯O interactions, which are influenced by the nature of C(O)NR̲2 and decrease with the sterically bulky alkyl substituent (Se⋯O =2.823 Å for R = di-Me, 2.760 Å for R = allyl, and 3.157 Å for R = di-iPr). Mercury complexes derived from less bulky 2-phenyl-N,N-dialkylbenzamide ligands associated with poor or no intramolecular nonbonded Hg⋯O interactions (4.91 Å for R = di-Me, 4.199 Å for R = allyl) and instead strong intermolecular Hg⋯O [2.792(3) and 2.820(4) Å] for di-Me and allyl and Hg⋯Se [3.3212(5) and 3.4076(8) Å] interactions were observed which lead to a dimeric form in the crystals. On the other hand, the mercury complex derived from the sterically bulky diisopropyl amide ligand shows a strong intramolecular non-bonded Hg⋯O (2.860 Å) interaction, adopts linear geometry and exists as a monomer. Thermogravimetric analysis (TGA) of the mercury selenolate complexes revealed two-step decomposition which leads to the formation of HgSe. The mercury selenolate complex 3c derived from the sterically bulky 2-phenyl-N,Ndiisopropylbenzamide ligand decomposed to give HgSe in the range of 220-300 °C.

Crystal structures of three mercury(II) complexes [HgCl2 L] where L is a bidentate chiral imine ligand.

The crystal structures of three complexes [HgCl2 L] were determined, namely, (S)-(+)-di-chlorido-[1-phenyl-N-(pyridin-2-yl-methyl-idene)ethyl-amine-κ(2) N,N']mercury(II), [HgCl2(C14H14N2)], (S)-(+)-di-chlorido-[1-(4-methyl-phen-yl)-N-(pyridin-2-yl-methyl-idene)ethyl-amine-κ(2) N,N']mercury(II), [HgCl2(C15H16N2)], and (1S,2S,3S,5R)-(+)-di-chlorido-[N-(pyridin-2-yl-methyl-idene)isopino-camph-eyl-amine-κ(2) N,N']mercury(II), [HgCl2(C16H22N2)]. The complexes consist of a bidentate chiral imine ligand coordinating to HgCl2 and crystallize with four independent mol-ecules in the first complex and two independent mol-ecules in the other two. The coordination geometry of mercury is tetra-hedral, with strong distortion towards a disphenoidal geometry, as a consequence of the imine bite angle being close to 70°. The Cl-Hg-Cl angles span a large range, 116.0 (2)-138.3 (3)°, which is related to the aggregation state in the crystals. For small Cl-Hg-Cl angles, complexes have a tendency to form dimers, via inter-molecular Hg⋯Cl contacts. These contacts become less significant in the third complex, which features the largest intra-molecular Cl-Hg-Cl angles.

The interplay of thiophilic and hydrogen bonding interactions in the supramolecular architecture of phenylmercury 4-hydroxypiperidine dithiocarbamate

A new phenylmercury(II) dithiocarbamate complex [PhHg(S2CN(CH2)4CH(OH)], (1) has been synthesized and characterized by elemental analyses, IR, 1H and 13C NMR spectroscopy and X-ray crystallography. The crystal structure of 1 shows a linear arrangement at the Hg(II) centre of the molecule through bonding of the sulphur atom of the dithiocarbamate ligand and the carbon atom of the aromatic ring. Weak intermolecular thiophilic Hg···S interactions lead to a “head-to-tail” dimer and the presence of a hydroxyl group at the periphery of piperidine moiety generates a 1D-chain network through intermolecular O···H interactions. The nature of weak intra- and intermolecular Hg···S, H···S and intermolecular O···H interactions have been assessed with the help of ab initio calculations and atoms-in-molecules (AIM) approach.

Phenylmercury(II) methylferrocenyldithiocarbamate-functionalized dye-sensitized solar cells with hydroxy as an anchoring group

A new heterobimetallic phenylmercury(II) dithiocarbamate complex having the ferrocenyl moiety (C5H5)Fe(C5H4) (Fc), PhHgS2CN(CH2Fc)CH2CH2OH, (1) has been prepared and characterized by elemental analyses, UV–vis, IR, 1H and 13C NMR spectroscopies and X-ray crystallography. The crystal structure of 1 showed a linear core at the Hg(II) centre of the molecule bounded by the sulfur atom of the dithiocarbamate ligand and carbon atom of the aromatic ring. Weak intermolecular Hg···S interactions lead to “head to tail” dimer in this compound and presence of hydroxyl group generates one-dimensional chain network. This ferrocenyl-based organomercury(II) dithiocarbamate complex compound comprising of a –OH moiety showed improved light-harvesting properties as a photosensitizer in dye-sensitized solar cells (DSSCs). The short-circuit current and open-circuit potential obtained with this compound were 6.95 mA/cm2 and −0.645 V, respectively, resulting in the enhanced overall conversion efficiency of 3.2 %.

Effect of pyridyl substituents leading to the formation of green luminescent mercury(ii) coordination polymers, zinc(ii) dimers and a monomer

Pyridine-2, -3 and -4 functionalized dithiocarbamate ligands yielded the coordination polymers with mercury, namely [{Hg(L)2}n] (L = L1, C5H4NCH2NCS2CH2C7H5O2 (1); L2, C5H4NCH2NCS2CH3 (2); L3, C5H4NCH2NCS2CH2C4H3O (3); and L4, C5H4NCH2NCS2CH2CH2C6H5 (4)), [PhHg(L3)] (5), and mononuclear [Hg(L5)2], L5 = C5H4NCH2NCS2CH2C6H5 (6). Unexpectedly, the pyridine-2-functionalized ligand, L6, C5H4NCH2NCS2CH2C6H5 gave a cyclized product, benzyl-2H-imidazo[1,5-a]pyridine-3-thione (7), C14H13N2S, instead of a mercury complex. Complexes with zinc were also characterized, namely dinuclear [Zn2(L5)4] (8) and [Zn2(L7)4], L7 = CH3CH2O2C5H9NCS2 (9) and a mononuclear complex [Zn(L8)2], L8 = C4H3NCH3CH2NCS2CH2C6H5 (10). These ten compounds have been characterized by microanalysis and X-ray crystallography. Complexes (1, 2) and 3 are 1-D and 2-D coordination polymers in which the ligands are uniquely bonded in the bridging-chelating mode in a μ2, κ3-N, S, S fashion establishing square pyramidal five-coordinate and octahedral six-coordinate geometries about the Hg atom respectively. The structure of 4 is also a 1-D coordination polymer formed via bridging sulphur bonds with a five-coordinate distorted geometry about the mercury atom. 6 is a mononuclear mercury(II) complex forming an interesting polymeric 1-D architecture through intermolecular Hg⋯S interactions. 8 is the first example of a homoleptic dinuclear zinc(II) dithiocarbamate complex bridged through ligand L5 in a μ2, κ3-N, S(11), S(13) bridging-chelating manner. L7 and L8 form a typical S, S-bridged dimer 9 and a mononuclear complex 10. The nature of the Hg–N and Zn–N bonds in the coordination polymers 1, 2 and 3 and in the dinuclear 8 has been assessed by DFT calculations. Complexes 1–9 are luminescent in both solution and solid phases; especially, significant red shifted green emission in the solid phase for the coordination polymers 1, 2 and 3 shows good structure–property correlations.

Synthesis, structures, and spectroscopic properties of Hg(II) complexes of bidentate NN and tridentate NNO Schiff-base ligands

Reactions of HgX2 (X = Cl, N3, NO3) with (E)-2-methoxy-N-(pyridin-2-ylmethylene)aniline (L1) and (E)-4-methoxy-N-(pyridin-2-ylmethylene)aniline (L2) in ethanol gave two monomers, [HgL1(Cl)2] (1) and [HgL2(NO3)2(DMSO)] (5), and three coordination polymers, {[HgL1(N3)2]2·Hg(N3)2}n (2), [HgL2(Cl)2]n (3), and [HgL2(NO3)2]n·nCH3CN (4). Compounds 1–5 were characterized by elemental analysis, IR, NMR spectroscopy, and single-crystal X-ray diffraction. The common feature of monomeric 1 and 5 is the presence of intra- and intermolecular Hg–O bonds. In the absence of these, polymeric structures arise as a result of azide, chloride, and nitrate bridging in 2, 3, and 4, respectively. Fluorescent properties of 1–5 were also investigated.

1-(Bromomercurio)ferrocene

The asymmetric unit of the title compound, [Fe(C5H5)(C5H4BrHg)], contains two independent mol­ecules, A and B, in which the Hg—C bond lengths are 2.045 (6) and 2.046 (6) Å, the Hg—Br bond lengths are 2.4511 (9) and 2.4562 (7) Å, and the C—Hg—Br angles are 176.42 (17) and 177.32 (17)°. The two cyclo­penta­dienyl rings of mol­ecule A are eclipsed, while those of mol­ecule B are almost staggered. The HgBr groups are connected by inter­molecular Hg⋯Br contacts of 3.3142 (9)–3.4895 (11) Å, forming layers parallel to (001). These layers contain both four-membered (HgBr)2 and eight-membered (HgBr)4 rings. Ferrocene–ferrocene C—H⋯π contacts connect the mol­ecular layers along the c-axis direction.

Syntheses, structures, and properties of two luminous mercury(II) halide compounds containing a tetradentate N-donor Schiff base

A 1D coordination polymer [Hg2(L)Br4]n (1) and one dinuclear compound [Hg2(L)I4] (2) [L=N,N′-(bis(pyridin-2-yl)benzylidene)ethane-1,2-diamine] are isolated using a 2:1M ratio of HgBr2/HgI2 and Schiff base (L) in methanol–acetonitrile solution mixture and X-ray crystallographically characterized. Structural analyses show that in 1 1D chain is formed through binucleating bis(bidentate) bridging behavior of L and asymmetric Hg-(μ-Br)2-Hg bridges in an alternate fashion; one terminal bromide unit completes the distorted square pyramidal geometry around each mercury(II). In 2, two mercury(II) centers are connected by bis(bidentate) bridging behavior of L and two iodides bound to each metal(II) center remain as terminal resulting in a discrete dinuclear entity with distorted tetrahedral geometry. Weak intermolecular Hg⋯I and I⋯I interactions in 2 promote dimensionality. In DMF solutions, 1 and 2 display intraligand 1(π–π∗) fluorescence.

The interplay of secondary Hg⋯S, Hg⋯N and Hg⋯π bonding interactions in supramolecular structures of phenylmercury(ii) dithiocarbamates

Three new phenylmercury(II) and one mercury(II) dithiocarbamate complexes viz.PhHg S2CN(PyCH2)Bz (1), PhHg S2CN(PyCH2)CH3 (2), PhHg S2CN(Bz)CH3 (3), and [Hg (NCS2(PyCH2)Bz)2] (4) (Py = pyridine; Bz = benzyl) have been synthesized and characterized by elemental analyses, IR, electronic absorption, 1H and 13C NMR spectroscopy. The crystal structures of 1, 2 and 3 showed a linear S–Hg–C core at the centre of the molecule, in which the metal atom is bound to the sulfur atom of the dithiocarbamate ligand and a carbon atom of the aromatic ring. In contrast the crystal structure of 4 showed a linear S–Hg–S core at the Hg(II) centre of the molecule. Weak intermolecular Hg⋯N (Py) interactions link molecules into a linear chain in the case of 1, whereas chains of dimers are formed in 2 through intermolecular Hg⋯N (Py) and Hg⋯S interactions. 3 forms a conventional face-to-edge dimeric structure through intermolecular Hg⋯S secondary bonding and 4 forms a linear chain of dimers through face-to-face Hg⋯S secondary bonding. In order to elucidate the nature of these secondary bonding interactions and the electronic absorption spectra of the complexes, ab initio quantum chemical calculations at the MP2 level and density functional theory calculations were carried out for 1–3. Complexes 1 and 2 exhibited photoluminescent properties in the solid state as well as in the solution phase. Studies indicate that Hg⋯S interactions decrease and Hg⋯N interactions increase the chances of photoluminescence in the solid phase

Syntheses, crystal, photoluminescence and electrochemical investigation of some new phenylmercury(ii) dithiocarbamate complexes involving ferrocene

A series of new heterobimetallic phenylmercury(II) dithiocarbamate complexes incorporating the ferrocenyl moiety (C(5)H(5))Fe(C(5)H(4)) (Fc), namely PhHgS(2)CN(CH(2)Fc)CH(2)C(6)H(5), (1), PhHgS(2)CN(CH(2)Fc)CH(CH(3))(2), (2), PhHgS(2)CN(CH(2)Fc)(CH(2))(3)CH(3), (3) and [PhHgS(2)CN(CH(2)Fc)](2)(CH(2)C(6)H(4)CH(2)), (4) have been prepared and characterized by elemental analysis, UV-Vis, IR, (1)H and (13)C NMR spectroscopies. The crystal structures of 1, 2 and 4 showed a linear core at the Hg(II) centre of the molecule, bound by the sulfur atom of the dithiocarbamate ligand and carbon atom of the aromatic ring. Weak intermolecular Hg...S interactions form "head-to-tail" dimers in the cases of 1 and 2. 4 forms a similar dimeric structure, forming two pairs of Hg...S interactions to generate a tetrametallic unit. The observed quasi-reversible cyclic voltammograms of the complexes have been corroborated by calculating gross electron population at each atom for the neutral as well its oxidized species obtained at the density functional level (DFT) of theory, which suggests an electron withdrawing effect from the organomercury(ii)-dithiocarbamate group. The electronic absorption bands of all the four complexes were assigned with the help of time dependent density functional theory (TD-DFT) calculations. Upon excitation at approximately 440 nm 1, 3 and 4 exhibited a medium strong photoluminescence emission at approximately 500 nm as a consequence of MLCT intraligand charge transfer. 1, when excited at 256 nm exhibits photoluminescence emission at 398 nm.

Formation of Extended 1D and 2D Coordination Polymers in Tetrathioether Complexes of Mercury(II) and Copper(I): Crystal Structures of [{{Ge(CH2SPh)4}HgBr2}n] and [{{Ge(CH2SPh)4}(Cu2l2}}n

AbstractA one‐dimensional (1D) coordination polymer of stoichiometry [{{Ge(CH2SPh)4}HgBr2}n] (2b) has been prepared by treatment of HgBr2 with the functionalized germane Ge(CH2SPh)4 (1b), which is acting as a tetradentate thioether ligands. The extended structure results from weak intermolecular Hg–S interactions linking the monomeric {Ge(CH2SPh)4}HgBr2 units, as established using single‐crystal X‐ray diffraction. The effective coordination around the mercury atoms is best described as distorted octahedral. Upon reaction of CuI with 1b in a 2:1 metal‐to‐ligand ratio, the novel metal‐organic polymer [{{Ge(CH2SPh)4}(Cu2I2)}n] (3), which incorporates rhombic dinuclear Cu(μ‐I)2Cu units within its 2D sheet‐like network, was obtained. The luminescence properties of 1b and 3 have been investigated both in solution and in the solid state. Upon treatment of 1b with [{Re(μ‐Br)(CO)3(THF)}2] the mononuclear compound fac‐[ReBr(CO)3{Ge(CH2SPh)4}] (4) is formed. In this chelate complex, two CH2SPh arms are ligated on ReI, the remaining two CH2SPh arms are dangling.

Synthesis, crystal structures and luminescent properties of phenylmercury(II) complexes with thiohydrazone ligands having weak Hg····π and Hg····Hg interactions

The Reaction of phenylmercury(II) acetate with salicylaldehyde morpholine N-thiohydrazone (H 2smth) and 2-hydroxyacetophenone morpholine N-thiohydrazone (H 2apmth) in dry ethanol under gentle refluxing condition form light yellow complexes [PhHg(Hsmth)] ( 1) and [PhHg(Hapmth)] ( 2) involving formation of Hg-S bond from the thiol form of the ligands after deprotonation of the SH proton. The structures of the complexes as determined by X-ray crystallography shows that the complex ( 1) has a distorted T-shaped geometry while the complex ( 2) adopts familiar linear coordination geometry. Complex ( 2) has two independent molecules comprising the asymmetric unit. Both the complexes form two-dimensional supramolecular assemblies due to a combination of weak intermolecular Hg····π and Hg····Hg interactions. The Hg····π and Hg····Hg distances are 3.937 and 4.0216(10) Å, respectively, possibly indicating weak mercuriophilic interactions. The luminescent properties of the complexes in solution and in the solid state at room temperature are also described.

Complexation of 1,4-Bis(phenylthio)butane on Mercury(II) Salts: Formation of Extended 2D Coordination Polymers

Two novel two-dimensional (2D) coordination polymers of stoichiometry [{PhS(CH2)4SPh}Hg2X4]n (X = Cl, 2a; X = Br, 2b) have been prepared by treatment of HgX2 with PhS(CH2)4SPh 1, acting as bridging dithioether ligand. The extended 2D structures result from bridging coordination of 1 between two mercury atoms and intermolecular Hg–X interactions, thus linking the HgX2 units in two dimensions. As established for 2a,b by single-crystal X-ray diffraction, the coordination around the Hg centers in both isomorphous compounds (monoclinic, space group P21/c) is distorted tetrahedral, with quite short Hg-thioether bonds of 2.4780(19) (2a) and 2.499(3) A (2b), respectively.

Formation of extended 1D coordination polymers in tetrathioether complexes of mercury(II): Effect of the organic substituents on the crystal structures of {Si(CH 2SR) 4}HgBr 2 (R = Me, Ph)

Two novel one-dimensional (1D) coordination polymers of stoichiometry [{Si(CH 2SR) 4}HgBr 2] n (R = Me, 2a; R = Ph, 2b) have been prepared by treatment of HgBr 2 with the functionalized silanes Si(CH 2SR) 4 (R = Me, 1a; R = Ph, 1b) acting as tetradentate thioether ligands. The extended structures result from intermolecular Hg–S interactions linking the monomeric {Si(CH 2SR) 4}HgBr 2 units, as established for 2a, b using single-crystal X-ray diffraction. The effective coordination around the Hg atoms in both compounds is best described as distorted octahedral.