A New Chair‐shaped Conformation Containing HgHgOHgHgO: Synthesis and Structure of Hg4(L2)2(NO3)4 (L2 = morpholin‐4‐ylpyridin‐2‐ylmethyleneamine)

. The complex Hg₄(L²)₂(NO₃)₄ ( 1 ) (L² = morpholin‐4‐ylpyridin‐2‐ylmethyleneamine) has been synthesized and characterized by CHN analysis, IR, and UV/Vis spectroscopy. The crystal structure of 1 was determined using single‐crystal X‐ray diffraction. The crystal structure of 1 contains four mercury atoms, four nitrate anions (two terminal and two bridge ones) and two L² ligand molecules. A chair shape, six‐membered ring is formed with the sequence OHgHgOHgHg built from Hg–Hg dumbbells and oxygen atoms from the nitrate co‐ligands. In the crystal structure, the asymmetric unit of the compound is built up by one‐half of the molecule. It contains the Hg₂²⁺ moiety with a mercury–mercury bonded core, in which one diimine ligand is coordinated to one of the mercury atoms. The nitrate anions act as anisobidentate and bidentate ligands.     

Pseudohalogeno‐Metallverbindungen. LXXVI Molekülstruktur von Tetrafulminatomercurat(II), [Hg(CNO)4]2–

Pseudohalogeno Metal Compounds. LXXVI Molecular Structure of Tetrafulminatomercurate, [Hg(CNO)₄]^2– Crystals of [AsPh₄]₂[Hg(CNO)₄] contain [AsPh₄]⁺ cations and [Hg(CNO)₄]^2– anions. The tetrafulminatomercurate ion forms a slightly distorted tetrahedron with linear fulminate ligands. In the crystal the [Hg(CNO)₄]^2– anions are separated by the AsPh₄⁺ cations which explains the thermal stability of this compound.     

Structural and Solution Studies of two Mercury(II) Complexes with [1,3‐Bis(2‐ethoxy)benzene]triazene

The reaction of [1,3‐bis(2‐ethoxy)benzene]triazene, [ HL ], with Hg(SCN)₂ and Hg(CH₃COO)₂, resulted in the formation of the complexes [Hg L (SCN)] ( 1 ) and [Hg L ₂] · CH₃OH ( 2 ). They were characterized by means of X‐ray crystallography, CHN analysis, FT‐IR, ¹H NMR, and ¹³C NMR spectroscopy. The structure of compound 1 consists of two independent complexes in which the Hg^II atoms are stacked along the crystallographic a axis to form infinite chains. Each Hg^II atom is chelated by one L ligand and one SCN ligand, whereas in compound 2 , the Hg^II atom is surrounded by two L ligands. In addition, 1D chains formed by metal–π interactions are connected to each other by C–H ··· π stacking interactions in the structure of 1 , which results in a 2D architecture. An interesting feature of compound 2 is the presence of C–H ··· π edge‐to‐face interactions.     

3‐Methylamido‐3′,4′‐ethyl­enedithiotetra­thia­fulvalene­(+) potassium tetra­isothio­cyanato­mercury(II)

In the title compound, (C₁₀H₉NOS₆)K[Hg(SCN)₄] or (EDT–TTF–CONHMe)K[Hg(SCN)₄)], fully oxidized organic (EDT–TTF–CONHMe)^+· radical cations form quasi‐one‐dimensional stacks running along the monoclinic 2₁ axis and alternating along the crystallographic [101] direction with inorganic anion stacks made from mixed K⁺–[Hg(SCN)₄]²⁻ ribbons. For each anion, three essentially collinear SCN ligands inter­act with the K⁺ ions via short N⋯K contacts, while the terminal N atom of the fourth SCN group is engaged in a number of hydrogen‐bond contacts with the –CH, –NH and –CH₂ hydrogen‐bond donors of the amide function. Radical cations are dimerized along the stacks and the crystal conductivity is activated.     

The first X-ray crystal structure of a mercury(II) complex with an SP(N)3-based ligand: Synthesis and crystal structure of SP(NC5H10)3 and [Hg{SP(NC5H10)3}Cl2]2

The synthesis, spectral characteristics (IR and NMR), elemental analysis and X-ray crystal structure of phosphorothioic triamide SP(NC₅H₁₀)₃ (1) and its dinuclear mercury(II) complex [Hg₂(μ-Cl)₂(Cl)₂{SP(NC₅H₁₀)₃}₂] (2) were investigated. A survey using the Cambridge Structural Database (CSD, version 5.38, May 2017) shows structures of coordination compounds of Au, Ag, Cd, Cu, Li, Mo, Ni, Pd, Te, Ti, Zn, and Zr with sulfur-donor SP(N)₃-based ligands; the complex 2 is the first example of a mercury complex with the SP(N)₃-based ligand studied by X-ray crystallography. Valence bond calculation was performed for the Hg–S bond in 2 and compared with the Hg–O bond in the only structure with a Cl₂Hg–OP(N)₃ structural motive in the CSD. The calculation confirms a more covalent nature of the Hg–S bond with respect to the Hg–O bond made by the EP(N)₃-based ligands (E?=?S, O). The supramolecular structures based on C–H···S?=?P contacts in 1 and C–H···S═P and C–H···Cl–Hg assemblies in 2 are discussed.     

Synthesis,Structure, and Solution Study of a Mercury(II) Complex with the Ligand [1‐(2‐Methoxyphenyl)‐3‐(4‐chlorophenyl)]triazene

The title ligand, [1‐(2‐methoxyphenyl)‐3‐(4‐chlorophenyl)]triazene, H L ( 1 ), was prepared. In a reaction with Hg(NO₃)₂ it forms the complex [Hg(C₂₆H₂₂Cl₂N₆O₂)], [Hg L ₂] ( 2 ). Both compounds were characterized by means of X‐ray crystallography, CHN analysis, FT‐IR, ¹H NMR, and ¹³C NMR spectroscopy. In the structure of compound 1 , two independent fragments are present in the unit cell. They exhibit trans arrangement about the –N=N– double bond. The dihedral angles between two benzene rings in both fragments are 4.36 and 18.79 Å, respectively. Non‐classic C–H ··· N hydrogen bonding and C–H ··· π interactions form a layer structure along the crystallographic ab plane [110]. In compound 2 , the Hg^II atom is hexacoordinated by two tridentate [1‐(2‐methoxyphenyl)‐3‐(4‐chlorophenyl)]triazenide ligands through a N₂O₂ set. In addition, in the structure of 2 , monomeric complexes are connected to each other by C–H ··· π stacking interactions, resulting in a 2D architecture. These C–H ··· π edge‐to‐face interactions are present with H ··· π distances of 3.156 and 3.027 Å. The results of studies of the stoichiometry and formation of complex 2 in methanol solution were found to support its solid state stoichiometry.     

Variability in the Coordination Modes of 2‐Pyridineformamide Thiosemicarbazone (HAm4DH) in some Zinc(II), Cadmium(II), and Mercury(II) Complexes

The reduction of 2‐cyanopyridine by sodium in dry methanol in the presence of thiosemicarbazide produces 2‐pyridineformamide thiosemicarbazone, HAm4DH. The reactions of the potentially tridentate ligand HAm4DH with salts of Zn, Cd, and Hg gave a variety of metal‐ligand complexes. The complexes were characterized by mass spectrometry as well as IR and multinuclear NMR (¹H, ¹³C, ¹³C CP/MAS, ¹¹³Cd, ¹⁹⁹Hg) spectroscopy. The crystal structures of [Zn(Am4DH)(OAc)]₂·H₂O, [Hg(HAm4DH)₂Br₂]·C₂H₅OH and [Hg(μ‐S‐Am4DH)Br] were obtained. Coordination of anionic Am4DH^? occurs through the pyridyl nitrogen, imine nitrogen and thiolato sulfur atoms, while the neutral ligands in [Hg(HAm4DH)₂Br₂] coordinate as monodentate ligands through their thione sulfur atoms. One of the acetate ligands in [Zn(Am4DH)(OAc)]₂·H₂O is bridging monodentate and the other bridging bidentate. [Hg(μ‐S‐Am4DH)Br] features five‐coordinate mercury centers with bridging thiolato sulfur atoms. The intermolecular arrangement is dictated by hydrogen bonding from the amino groups and by π‐π stacking of the pyridine rings.     

Synthesis,IR Spectra,Thermal Analysis and Crystal Structures of Bis(saccharinato)mercury(II) Complexes with 2–Aminomethylpyridine and 2–Aminoethylpyridine

Two bis(saccharinato) (sac) complexes of mercury(II) with 2–aminomethylpyridine (ampy) and 2–aminoethylpyridine (aepy) were synthesized and characterized by means of elemental analysis, FT–IR spectroscopy and thermal analysis and single crystal X–ray diffraction. trans–[Hg(sac)₂(ampy)₂] ( 1 ) crystallizes in the monoclinic space group P2₁/c [a = 10.8274(4), b = 16.4903(6), c = 7.7889(3) Å; β = 99.500(1)°] and [Hg(sac)₂(aepy)] ( 2 ) also crystallizes monoclinic in space group P2₁/n [a = 9.0423(4), b = 14.0594(6), c = 18.0146(8) Å; ß = 98.806(1)°]. Both 1 and 2 consist of neutral monomeric units. The mercury(II) ion in 1 lies on an inversion centre and exhibit distorted octahedral coordination by two sac anions and two ampy ligands, whereas the mercury(II) ion in 2 is tetrahedrally coordinated by an aepy and two sac ligands. The sac ligands in both complexes are N–coordinated, while the ampy and aepy ligands act as a bidentate ligand forming two symmetrically chelate rings around the mercury(II) ion.     

Bis{[μ‐N,N′‐bis­(salicyl­idene)‐1,4‐butane­di­amine‐N,N′,O,O′‐copper(II)]‐μ‐chloro‐chloromercury(II)}

A new tetranuclear Cu^II–Hg^II–Hg^II–Cu^II complex, [Cu₂Hg₂Cl₄(C₁₈H₁₈N₂O₂)₂], has been prepared by means of a copper complex found in the literature. The molecular structure of this complex was determined by X‐ray diffraction and the Cu–Hg–Hg–Cu chain was seen to be non‐linear. The change in magnetic susceptibility with temperature was recorded for this complex and observed to abide by the Curie–Weiss law. The coordination around the Hg^II ions is square pyramidal. The Cu?Hg bridging distance is 3.5269 (7) Å.     

(Nitrato‐κO)bis(pyridine‐2‐carboxamide‐κ2N1,O)mercury(II) nitrate

In the title compound, [Hg(NO₃)(C₆H₆N₂O)₂]NO₃, the Hg^II atom is five‐coordinate. The distorted square‐pyramidal mercury(II) coordination environment is achieved by two N,O‐bidentate picolinamide ligands, with one O‐monodentate nitrate ion in the apical position. A seven‐coordinate extended coordination environment is completed by two additional weak Hg...O interactions, one from the coordinated nitrate ion and one from the other nitrate ion, to give seven‐coordination. The molecules are linked into a two‐dimensional network by N—H...O hydrogen bonds.     

Crystallographic report: Bis(N,N‐dibenzyldithiocarbamato)mercury(II)

The monomeric structure of Hg[S₂CN(CH₂Ph)₂]₂, in which the mercury atom lies on a two fold axis that relates the unsymmetrically chelating dithiocarbamate ligands, features a severely distorted tetrahedral geometry. Copyright © 2004 John Wiley & Sons, Ltd.     

Mono‐ and Dimethyl‐1,2,4‐Triazolate as Ligands for the Mercuric Ion in the Cationic Three‐dimensional Coordination Polymer of [Hg2(Mmt)(Dmt)2](NO3)(H2O)

Colourless crystals of [Hg₂(Mmt)(Dmt)₂](NO₃)(H₂O) were obtained from a reaction of mercuric nitrate with monomethyl‐ and dimethyl‐1,2,4‐triazolate (Mmt^? and Dmt^?, respectively). In the crystal structure (monoclinic, C2/c (no. 15), a = 2579.4(4), b = 1231.1(2), c = 1634.8(2) pm, β = 128.32(1)°, V = 4073.3(11)·10⁶·pm³, Z = 8, R₁ [I₀ > 2σ(I₀)]: 0.0355), half of the mercuric ions are essentially two‐coordinate (Hg–N: 210‐215 pm), the other half are tetrahedrally surrounded by N‐donor atoms (Hg–N: 221, 225 pm) of the Mmt^? and Dmt^? anions. These three‐N ligands construct a three‐dimensional framework.     

(1,3‐Dimethylimidazolidine‐2‐selone‐κSe)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) bis(perchlorate) and bis(2,2′‐bipyridyl‐κ2N,N′)(imidazolidine‐2‐thione‐κS)copper(II) bis(perchlorate)

In the first title salt, [Cu(C₁₂H₈N₂)₂(C₅H₁₀N₂Se)](ClO₄)₂, the Cu^II centre occupies a distorted trigonal–bipyramidal environment defined by four N donors from two 1,10‐phenanthroline (phen) ligands and by the Se donor of a 1,3‐dimethylimidazolidine‐2‐selone ligand, with the equatorial plane defined by the Se and by two N donors from different phen ligands and the axial sites occupied by the two remaining N donors, one from each phen ligand. The Cu—N distances span the range 1.980 (10)–2.114 (11) Å and the Cu—Se distance is 2.491 (3) Å. Intermolecular π–π contacts between imidazolidine rings and the central rings of phen ligands generate chains of cations. In the second salt, [Cu(C₁₀H₈N₂)₂(C₃H₆N₂S)](ClO₄)₂, the Cu^II centre occupies a similar distorted trigonal–bipyramidal environment comprising four N donors from two 2,2′‐bipyridyl (bipy) ligands and an S donor from an imidazolidine‐2‐thione ligand. The equatorial plane is defined by the S donor and two N donors from different bipy ligands. The Cu—N distances span the range 1.984 (6)–2.069 (7) Å and the Cu—S distance is 2.366 (3) Å. Intermolecular π–π contacts between imidazolidine and pyridyl rings form chains of cations. A major difference between the two structures is due to the presence in the second complex of two N—H...O hydrogen bonds linking the imidazolidine N—H hydrogen‐bond donors to perchlorate O‐atom acceptors.     

Darstellung von Organylquecksilber(II)‐di(methansulfonyl)amiden und Kristallstruktur von Ph–Hg–N(SO2Me)2

Polysulfonylamines. CXXIV. Preparation of Organylmercury(II) Di(methanesulfonyl)amides and Crystal Structure of Ph–Hg–N(SO₂Me)₂ Four N,N‐disulfonylated organylmercury(II) amides R–Hg–N(SO₂Me)₂, where R is Me, ⁱPr, Me₃SiCH₂ or Ph, were obtained on treating the appropriate chlorides RHgCl with AgN(SO₂Me)₂, and characterized by ¹H and ¹³C NMR spectra. In the crystal structure of the phenyl compound (orthorhombic, space group Pbca, Z = 8, X‐ray diffraction at –95 °C), the molecule exhibits a covalent and significantly bent C–Hg–N grouping [bond angle 172.7(3)°; Hg–C 204.0(8), Hg–N 209.1(7) pm]. One sulfonyl oxygen atom forms a short intramolecular Hg…O contact [296.1(5) pm] and simultaneously catenates glide‐plane related molecules via a second Hg…O interaction 297.6(5) pm], thus conferring upon Hg^II the effective coordination number 4 and a geometrically irregular coordination polyhedron (bond angles from 173 to 54°).     

A photochromic dinuclear compound: aquatetrakis(μ‐2,3‐diphenylprop‐2‐enoato)bis(2,3‐diphenylprop‐2‐enoato)ethanolbis(1,10‐phenanthroline)dilanthanum(III)

The title dinuclear complex, (aqua‐1κO)tetrakis(μ‐2,3‐diphenylprop‐2‐enoato‐1:2κ²O:O′)bis(2,3‐diphenylprop‐2‐enoato)‐1κO;2κO‐(ethanol‐2κO)bis(1,10‐phenanthroline)‐1κ²N,N′;2κ²N,N′‐dilanthanum(III), [La₂(C₁₅H₁₁O₂)₆(C₁₂H₈N₂)₂(C₂H₅OH)(H₂O)], contains two similar La^III centres with distorted [LaO₆N₂] bicapped triganol–prismatic coordination polyhedra formed by six phenylcinnamate (PCA⁻ or 2,3‐diphenylprop‐2‐enoate) ligands, two 1,10‐phenanthroline (phen) ligands, a coordinating ethanol molecule and a coordinating water molecule. The two metal centres are bridged by four μ‐PCA⁻ ligands, with the remaining two PCA⁻ ligands coordinated in a monodentate fashion. The noncoordinated carboxylate O atoms on the terminal PCA⁻ ligands form O—H...O hydrogen bonds with the coordinated solvent molecules. Each La centre is also coordinated by a bidentate phen ligand. The PCA⁻ ligands all adopt syn–syn orientations, with the two phenyl rings presenting dihedral angles of about 70°. The compound displays photochromic behaviour both in solution and in the solid state.     

Bis(N,N′‐dimethylimidazol‐2‐yl­idene)mercury chlorotriiodo­mercury dimethyl sulfoxide solvate

The double mercury salt [Hg(C₅H₈N₂)₂][HgClI₃]·C₂H₆OS was prepared and its structure characterized. The [Hg(C₅H₈N₂)₂]²⁺ cation lies about an inversion centre and the [HgClI₃]^2? anion lies on a mirror plane. Cations and anions are linked to form a one‐dimensional polymer by weak Hg?Cl interactions [Hg?Cl 3.3744 (3) Å]. The mercury–carbene bond distance [2.076 (7) Å] is typical of a dicationic mercury–carbene species.     

Poly[[bis(dimethyl sulfoxide‐κO)tris(thiocyanato‐κN)­manganese(II)]‐μ‐thio­cyanato‐κ2N:S‐mercury(II)]

In the title complex, [MnHg(SCN)₄(C₂H₆SO)₂]_n, each Hg atom is tetrahedrally coordinated to four S atoms of the SCN ions, while each Mn atom is octahedrally coordinated to four N atoms of the SCN ions and two O atoms of the di­methyl sulfoxide mol­ecules which occupy the trans positions. Each pair of Hg and Mn atoms is bridged by one SCN ion. Two Mn atoms, two Hg atoms and four SCN ions make a 16‐membered ring which organises into a two‐dimensional network. The di­methyl sulfoxide ligands are extended perpendicular to the plane on both sides.     

Mercuric Bis(N‐imino‐methyl‐formamidate), Hg(Imf)2

Single crystals of mercuric bis(N‐imino‐methyl‐formamidate), Hg(Imf)₂, were obtained from aqueous solutions of 1,2,4‐triazole and Hg(NO₃)₂·2H₂O. The crystal structure [monoclinic, P2₁/c (no. 14), a = 499.6(2), b = 1051.2(4), c = 711.1(3) pm, β = 117.55(1)°, Z = 2, R₁ for 890 reflections with I₀>2σ(I₀): 0.0369] contains linear centrosymmetric Hg(Imf)₂ molecules with Hg–N distances of only 203.5(7) pm. Two plus two intra‐ and intermolecular nitrogen atoms add to an effective coordination number of 6.     

trans‐Bis(benzoato‐O)tetrakis(methanol‐O)iron(II): ligand bulk is not structure‐determining

The title compound, [Fe(C₇H₅O₂)₂(CH₄O)₄], is a centrosymmetric six‐coordinate Fe^II complex coordinated by two axial monodentate benzoate ligands and four methanol ligands in the equatorial plane [Fe—O_benzoate 2.0935 (7) Å, and Fe—O_methanol 2.1310 (7) and 2.1290 (7) Å]. The benzoate ligands adopt monodentate ligation, rather than a bridged polymeric structure, because of strong intra‐ and intermolecular hydrogen bonds to the methanol ligands. This structure is nearly identical to that obtained with a much bulkier carboxyl­ate ligand [Chavez, Que & Tolman (2001). Chem. Commun. pp. 111–112].     

Complexation of methylparathion and bis(2‐hydroxyethyl)sulfide by the tridentate lewis acid [(o‐C6F4Hg)3]

The interaction of trimeric perflu‐ oro‐ortho‐phenylene mercury ( 1 ) with bis(2‐hydroxy‐ ethyl)sulfide (S((CH₂)₂OH)₂) in dichloromethane and methylparathion (SP(OMe)₂(p‐C₆H₄NO₂)) in 1,2‐dichloroethane leads to the crystallization of [ 1 ⋅ (S((CH₂)₂OH)₂)] and [ 1 ⋅ (μ₃‐SP(OMe)₂(p‐C₆H₄‐ NO₂))₂], respectively. These two adducts have been characterized by elemental analysis and single crystal X‐ray diffraction. The structure of [ 1 ⋅ S((CH₂)₂OH)₂] shows that the bis(2‐hydroxyethyl)sulfide molecule interacts with the mercury centers of 1 by formation of a Hg–S interaction of 3.138(4) Å. Association of the two components is further strengthened by the coordination of one of the oxygen atoms of the bis(2‐hydroxyethyl)sulfide molecule. This oxygen atom interacts simultaneously with three mercury centers of 1 with Hg–O distances ranging from 2.889(8) to 3.142(9) Å. In the lattice, molecules of [ 1 ⋅ (S((CH₂)₂OH)₂)] associate with compact cofacial dimers with Hg–Hg metallophilic contacts of 3.794 Å and 4.076 Å. The structure of [ 1 ⋅ (μ₃‐SP(OMe)₂(p‐C₆H₄NO₂))₂] is that of a 2:1 complex in which two molecules of methylparathion are triply coordinated via their sulfur atom to the mercury centers of 1 on either side of the molecular plane. The Hg–S contacts fall within the range of 3.278 and 3.651 Å. © 2005 Wiley Periodicals, Inc. 16:292–297, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20125