Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

The reaction of dibenzenediselenide, (SePh)₂, with mercury in refluxing xylene gives bis(benzeneselenolato)mercury(II), [Hg(SePh)₂], in a good yield. (ⁿBu₄N)[Hg(SePh)₃] is obtained by the reaction of [Hg(SePh)₂] with a solution of [SePh]^– and (ⁿBu₄N)Br in ethanol. The solid state structures of both compounds have been determined by X-ray diffraction. The mercury atom in [Hg(SePh)₂] (space group C2, a = 7.428(2), b = 5.670(1), c = 14.796(4) Å, β = 103.60(1)°) is linearly co-ordinated by two selenium atoms (Hg–Se = 2.471(2) Å, Se–Hg–Se = 178.0(3)°). Additional weak interactions between the metal and selenium atoms of neighbouring molecules (Hg…Se = 3.4–3.6 Å) associate the [Hg(SePh)₂] units to layers. The crystal structure of (ⁿBu₄N)[Hg(SePh)₃] (space group P2₁/c, a = 9.741(1), b = 17.334(1), c = 21.785(1) Å, β = 95.27(5)°) consists of discrete complex anions and (ⁿBu₄N)⁺ counter ions. The coordination geometry of mercury is distorted trigonal-planar with Hg–Se distances ranging between 2.5 and 2.6 Å.     

Synthese und Strukturen der selenolatoverbrückten Quecksilbercluster [Hg6(SePh)12(PtBu3)2] und (HPtBu3)2[Hg6(SePh)14]

Synthesis and Structures of the Selenolato-Bridged Mercury Clusters [Hg₆(SePh)₁₂(P t Bu₃)₂] and (HP t Bu₃)₂[Hg₆(SePh)₁₄] The reaction of HgCl₂ with PtBu₃ and PhSeSiMe₃ yields [Hg₆(SePh)₁₂(PtBu₃)₂] ( 1 ) and (HPtBu₃)₂[Hg₆(SePh)₁₄] ( 2 ). X-ray structural analysis of the compounds shows them to have similar Hg–Se cages with distorted tetrahedral coordination around mercury. The cages are built up from edge- and vertex-sharing distorted tetrahedra.     

[Hg8(μ‐n‐C3H7Te)12(μ‐Br)Br3] — Synthesis and Structure

The novel mercury‐tellurium cluster [Hg₈(μ‐n‐C₃H₇Te)₁₂(μ₂‐Br)Br₃] is formed during the reaction of HgBr₂ and (n‐C₃H₇Te)₂Hg in DMSO. Its crystal structure has been elucidated showing [Hg₈(μ‐n‐C₃H₇Te)₁₂(μ₂‐Br)]³⁺ units with a bromine‐centered distorted Hg₈ cube. The mercury atoms are bridged by n‐C₃H₇Te^— ligands and the resulting clusters are linked to a three‐dimensional network by bromine atoms. The close packing of the cluster is mainly determined by the flexible n‐propyl residues of the telluride building blocks.     

Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4) und [Cu3(SeMes)3(dppm)] (5)

Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] (1), [Cu(dppp)₂][Cu₂₅Se₄(SePh)₁₈(dppp)₂] (2), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] (3), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] (4), and [Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph₂P–(CH₂)_n–PPh₂, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph₂P–C≡C–PPh₂: dppa) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] ( 1 ), [Cu(dppp)₂] · [Cu₂₅Se₄(SePh)₁₈(dppp)₂] ( 2 ), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] ( 3 ), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] ( 4 ) and [Cu₃(SeMes)₃(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.     

Structural and Coordinative Variability in Zinc(II), Cadmium(II), and Mercury(II) Complexes of 2‐Pyridineformamide 3‐Hexamethyleneiminylthiosemicarbazone

Sodium in dry methanol reduces 2‐cyanopyridine in the presence of 3‐hexamethyleneiminylthiosemicarbazide and produces 2‐pyridineformamide 3‐hexamethyleneiminylthiosemicarbazone, HAmhexim ( 1 ). Complexes with zinc(II ), cadmium(II ) and mercury(II ) have been prepared and characterized by spectroscopic techniques. In addition, the crystal structures of HAmhexim ( 1 ), [Zn(Amhexim)(OAc)]₂μ·μDMSO ( 2 ), [Cd(HAmhexim)Cl₂]μ·μDMSO ( 7 ), [Cd(Amhexim)₂] ( 8 ), [Cd(HAmhexim)Br₂]μ·μDMSO ( 9 ), [Cd(HAmhexim)I₂]μ·μEtOH ( 10 ), [Hg(HAmhexim)Cl₂]μ·μDMSO ( 11 ), [Hg(Amhexim)Br]₂ ( 13 ), [Hg₃(HAmhexim)(Amhexim)Br₅]μ·μH₂O ( 14 ) and [Hg(Amhexim)I]₂ ( 15 ) have been determined. Coordination of the anionic and neutral thiosemicarbazone ligand occurs through the pyridine nitrogen atom, imine nitrogen atom, and thiolato or thione sulfur atom. In [Zn(Amhexim)(OAc)]₂ one of the bridging acetato ligands has monodentate coordination and the other bridges in a bidentate manner. [Cd(Amhexim)₂] is a 6‐coordinate species while the other cadmium complexes are 5‐coordinate. In [Hg(Amhexim)Br]₂ and [Hg(Amhexim)I]₂ the thiolato sulfur atoms act as bridges between the Hg atoms to form dimeric compounds and [Hg₃(HAmhexim)(Amhexim)Br₅]μ·μH₂O is a trinuclear complex with three different centers — two metallic centers have a 5‐coordination and the another one has 4‐coordination. In addition, [Hg(HAmhexim)Cl₂]μ·μDMSO and [Hg₃(HAmhexim)(Amhexim)Br₅]μ·μH₂O shown a supramolecular one‐dimensional hydrogen‐bonded self‐assembling.     

Synthesen und Charakterisierungen der ersten Tris‐ und Tetrakis(trifluormethyl)palladate(II) und ‐platinate(II), [M(CF3)3(PPh3)]— und [M(CF3)4]2— (M = Pd,Pt)

Syntheses and Characterizations of the First Tris and Tetrakis(trifluoromethyl) Palladates(II) and Platinates(II), [M(CF₃)₃(PPh₃)]^— and [M(CF₃)₄]^2— (M = Pd, Pt) Tris(trifluoromethyl)(triphenylphosphino)palladate(II) and platinate(II), [M(CF₃)₃PPh₃]^—, and the tetrakis(trifluoromethyl)metallates, [M(CF₃)₄]^2— (M = Pd, Pt), are prepared from the reactions of [MCl₂(PPh₃)₂] and Me₃SiCF₃ / [Me₄N]F or [I(CF₃)₂]^— salts in good yields. [Me₄N][M(CF₃)₃(PPh₃)] crystallize isotypically in the orthorhombic space group Pnma (no. 62) with Z = 4. The NMR spectra of the new compounds are described.     

Synthesis and Characterization of [Hg(sulfamethoxazolato)2]·2DMSO and[Cu2(μ‐CH3CO2)4(sulfamethoxazole)2]

[Hg(sulfamethoxazolato)₂]·2DMSO ( 1 ) and [Cu₂(CH₃COO)₄(sulfa‐methoxazole)₂] ( 2 ) can be obtained by the reaction of sulfamethoxazole with mercury acetate or copper acetate in methanol. The structures of the two complexes were characterized by single crystal X—ray diffractometry. Compound 1 consists of sulfamethoxazolato ligands bridging the metal ions building an unidimensional chain. Two solvent dimethylsulfoxide molecules are involved via N‐H···O hydrogen bridges. The mercury atom shows a linear primary coordination arrangement formed by two trans deprotonated sulfonamidic nitrogen atoms. The overall coordination around the metal atom may be regarded as a strongly distorted octahedron when the interactions of mercury with four sulfonamidic oxygen atoms [bond distances of 2.761(4) Å—2.971(4) Å] are also considered to build an equatorial plane and the N1 and N1′ atoms [bond distance of 2.037(5) Å] occupy the apical positions. Compound 2 is a dinuclear complex in which the copper ions are bridged by four syn‐syn acetate ligands which are related by a symmetry centre located in the centre of the complex. Each copper atom presents a nearly octahedral coordination where the equatorial plane is formed by four oxygen atoms and an isoxazolic nitrogen atom and the second copper atom occupy the apical positions.     

Synthesis and Structural Characterization of [Cu20Se4(μ3‐SePh)12(PPh3)6] and [Ag(SePh)]∞

Reaction of lithium phenylselenothiolate, generated in situ from the reductive cleavage of PhSe‐SiMe₃ with alkyl lithium reagents and insertion of elemental sulfur, with triphenylphosphine solubilized CuCl affords the molecular cluster complex [Cu₂₀Se₄ (μ₃‐SePh)₁₂(PPh₃)₆] ( 1 ). The analogous reaction with AgCl yields the extended structure [Ag(SePh)]_∞ ( 2 ) in which an infinite layer of Ag^I atoms is capped on either side by μ₄‐SePh ligands. 1: space group P¯1, a = 17.9510(6), b = 18.1712(7), c = 31.4311(11) Å, a = 78.098(2), β = 82.905(2), γ = 70.012(2)°. 2: space group C2/c, a = 5.8762(6), b = 7.2989(7), c = 29.124(2) Å, β = 95.790(3)°.     

Chemical Conversion of Hg‐Clusters: Synthesis and Crystal Structure of $ {\rm [(DMSO)_2 Co(NC \overline{S)_4(Hg}-TePh)_2]_{\rm n} }$, the First Compound Containing a Polymeric Hg—Te Chain

The six‐membered ring Hg₃Te₃ of [Hg₃Cl₃(μ‐TePh)₃]·2 DMSO {(Ph = C₆H₅; DMSO = (CH₃)₂SO} was opened by redissolution with DMSO, reacting with Co[Hg(SCN)₄] and affording polymeric . The monoclinic novel compound belong to the space group P2₁/n and assembles in a bidimensional lattice tetrahedral Hg^II(SCN)₂Te₂‐ and octahedral Co^II(NCS)₄(DMSO)₂‐chains linked trough SCN bridges along the crystallographic axis b and diagonally to the ac axes. The structure of [(DMSO)₂Co(NCS)₄(Hg—TePh)₂]_n is limited by the DMSO ligands in the axial positions of the Co‐octahedrons.     

Strukturen von neuen Bis(pentafluorophenyl)halogenomercuraten [{Hg(C6F5)2}3(μ‐X)]— (X = Cl,Br, I)

Structures of New Bis(pentafluorophenyl)halogeno Mercurates [{Hg(C₆F₅)₂}₃(μ‐X)]^— (X = Cl, Br, I) From the reactions of [PNP]Cl or [PPh₄]Y (Y = Br, I) with Hg(C₆F₅)₂ crystals of the composition [Cat][{Hg(C₆F₅)₂}₃X] (Cat = PNP, X = Cl ( 1 ); Cat = PPh₄, X = Br ( 2 ), I ( 3 )) are formed. 1 crystallizes in the triclinic space group P1¯, 2 and 3 crystallize isotypically in the monoclinic space group C2/c. In the crystals the halide anions are surrounded by three Hg(C₆F₅)₂ molecules. The reaction of [PPh₄]Br with Hg(C₆F₅)₂ under slightly changed conditions gives the compound [PPh₄]₂[{Hg(C₆F₅)₂}₃(μ‐Br)][{Hg(C₆F₅)₂}₂(μ‐Br)] ( 4 ).     

Zinkselenid- und Zinktelluridcluster mit Phenylselenolat- und Phenyltellurolatliganden. Die Kristallstrukturen von [NEt4]2[Zn4Cl4(SePh)6], [NEt4]2[Zn8Cl4Se(SePh)12], [Zn8Se(SePh)14(PnPr3)2], [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr,Ph) und [Zn10Te4(TePh)12(PR3)2] (R = nPr,Ph)

Zincselenide- and Zinctellurideclusters with Phenylselenolate- and Phenyltellurolateligands. The Crystal Structures of [NEt₄]₂[Zn₄Cl₄(SePh)₆], [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂], [Zn₈Se(SePh)₁₄(PⁿPr₃)₂], [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr, Ph), and [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr, Ph) In the prescence of NEt₄Cl ZnCl₂ reacts with PhSeSiMe₃ or a mixture of PhSeSiMe₃/Se(SiMe₃)₂ to form the ionic complexes [NEt₄]₂[Zn₄Cl₄(SePh)₆] 1 or [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂] 2 respectively. The use of PⁿPr₃ instead of the quarternary ammonia salt leads in toluene to the formation of crystalline [Zn₈Se(SePh)₁₄(PⁿPr₃)₂] 3 . Reactions of ZnCl₂ with PhTeSiMe₃ and tertiary phosphines result in acetone in crystallisation of the ionic clusters [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr 4 , Ph 5 ) and in THF of the uncharged [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr 6 , Ph 7 ). The structures of 1–7 were obtained by X-ray single crystal structure. ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1212,4(2) pm, b = 3726,1(8) pm, c = 1379,4(3) pm β = 99,83(3)°; 2 space group P2₁/c (Nr. 14), Z = 4, a = 3848,6(8) pm, b = 1784,9(4) pm, c = 3432,0(7) pm, β = 97,78(3)°; 3 : space group Pnn2 (No. 34), Z = 2, a = 2027,8(4) pm, b = 2162,3(4) pm, c = 1668,5(3) pm; 4 : space group P2₁/c (No. 14), Z = 4, a = 1899,8(4) pm, b = 2227,0(5) pm, c = 2939,0(6) pm, β = 101,35(3)°; 5 : space group space group P2₁/n (No. 14), Z = 4, a = 2231,0(5) pm, b = 1919,9(4) pm, c = 3139,5(6) pm, β = 109,97(4)°; 6 : space group I4₁/a (No. 88), Z = 4, a = b = 2566,0(4) pm, c = 2130,1(4) pm; 7 : space group P1¯ (No. 2), Z = 2, a = 2068,4(4) pm, b = 2187,8(4) pm, c = 2351,5(5) pm, α = 70,36°, β = 84,62°, γ( = 63,63°)     

Poly[[[tri(urea‐κO)manganese(II)]‐μ‐thiocyanato‐κ2N:S‐mercury(II)]‐tri‐μ‐tetrathiocyanato]

The title complex, [MnHg(SCN)₄(CH₄N₂O)₃]_n, consists of slightly distorted octahedral MnN₃O₃ and tetrahedral HgS₄ units. The Mn^II atom is coordinated by the O atoms of three urea mol­ecules and by the N atoms of three SCN^? ions; Hg^II is coordinated by four S atoms from SCN^? ions. Each pair of Mn^II and Hg^II atoms is connected by an –SCN– bridge, forming infinite two‐dimensional –Mn—NCS—Hg– networks.     

Poly[bis(N‐methylformamide)tetra‐μ‐thiocyanato‐manganese(II)mercury(II)]

The title complex, [MnHg(NCS)₄(C₂H₅NO)₂]_n, consists of slightly distorted MnN₄O₂ octa­hedra and HgS₄ tetra­hedra. Each Mn^II cation is bound to four N atoms of the NCS groups and two O atoms of the N‐methyl­formamide (NMF) ligands in a cis configuration. Each Hg^II cation is coordinated to four S atoms of NCS groups. Each pair of Mn^II and Hg^II cations is connected by an –NCS– bridge, forming an infinite three‐dimensional –Mn—NCS—Hg– network.     

Synthesis and X‐ray Structural Characterization of the Polymeric Cluster Compound [Hg3(O2SePh)(SePh)5]n

Two synthetic routes to prepare [Hg₃(O₂SePh)(SePh)₅]_n and its structural characterization are presented in this paper. This compound results either from the partial oxidation of mercury phenylselenolate clusters or from a mixture of its components with defined stoichiometry. This compound was observed in almost all of our reactions as a by‐product, during the development of the synthesis of new mercury selenolate clusters. It was now characterized by single‐crystal X‐ray diffractometry, elemental analysis, and infrared spectroscopy.     

Präparation,Kristallstruktur und thermisches Verhalten der Quecksilber(I)phosphate α-(Hg2)3(PO4)2, β-(Hg2)3(PO4)2 und (Hg2)2P2O7

Contributions on Crystal Structures and Thermal Behaviour of Anhydrous Phosphates. XXIII. Preparation, Crystal Structure, and Thermal Behaviour of the Mercury(I) Phosphates α-(Hg₂)₃(PO₄)₂, β-(Hg₂)₃(PO₄)₂, and (Hg₂)₂P₂O₇ Light-yellow single crystals of (Hg₂)₂P₂O₇ have been obtained via chemical vapour transport in a temperature gradient (500 °C → 450 °C, 23 d) using Hg₂Cl₂ as transport agent. Characteristic feature of the crystal structure (P2/n, Z = 2, a = 9,186(1), b = 4,902(1), c = 9,484(1) Å, β = 98,82(2)°, 1228 independent of 5004 reflections, R(F) = 0,066 for 61 variables, 7 atoms in the asymmetric unit) are Hg₂²⁺-units with d(Hg1–Hg1) = 2,508 Å and d(Hg2–Hg2) = 2,519 Å. The dumbbells Hg₂²⁺ are coordinated by oxygen, thus forming polyhedra [(Hg1₂)O₄] and [(Hg2₂)O₆]. These polyhedra share some oxygen atoms. In addition they are linked by the diphosphate anion P₂O₇^4– (ecliptic conformation; ∠(P,O,P) = 129°) to built up the 3-dimensional structure. Under hydrothermal conditions (T = 400 °C) orange single crystals of the mercury(I) orthophosphates α-(Hg₂)₃(PO₄)₂ and β-(Hg₂)₃(PO₄)₂ have been obtained from (Hg₂)₂P₂O₇ and H₃PO₄ (c = 1%). The crystal structures of both modifications have been refined from X-ray single crystal data [α-form (β-form): P2₁/c (P2₁/n), Z = 2 (2), a = 8,576(3) (7,869(3)), b = 4,956(1) (8,059(3)), c = 15,436(3) (9,217(4)) Å, β = 128,16(3) (108,76(4))°, 1218 (1602) independent reflections of 4339 (6358) reflections, R(F) = 0,039 (0,048) for 74 (74) variables, 8 (8) atoms in the asymmetric unit]. In the structure of α-(Hg₂)₃(PO₄)₂ three crystallographically independent mercury atoms, located in two independent dumbbells, are coordinated by three oxygen atoms each. Thus, [(Hg₂)O₆] dimers with a strongly distorted tetrahedral coordination of all mercury atoms are formed. Such dimers are present besides [(Hg₂)O₅]-polyhedra in the less dense crystal structure of β-(Hg₂)₃(PO₄)₂ (d(Hg–Hg) = 2,518 Å). The mercury(I) phosphates are thermally labile and disproportionate between 200 °C (β-(Hg₂)₃(PO₄)₂) and 480 °C (α-(Hg₂)₃(PO₄)₂) to elemental mercury and the corresponding mercury(II) phosphate.     

On the Use of Mercury Bis(Phenylselenolate) for the Synthesis of Polymeric Clusters: Synthesis and X-ray Structural Characterization of [Hg5Cl3(PhSe)7] n , [Hg7Cl3(PhSe)11] n and [Hg7Br3(PhSe)11] n

(PhSe)₂Hg reacts in DMF with HgX₂ (X = Cl, Br) in the presence of bis(pyrimidin-2-thio)methane/triphenylphosphine/4,4′-bipyridine, to give the polymeric cages [Hg₅Cl₃(PhSe)₇] _n (1), [Hg₇Cl₃(PhSe)₁₁] _n (2) and [Hg₇Br₃(PhSe)₁₁] _n (3). In compound 1 the polymeric chains along the a axis are linked through H···Cl interactions in the c axis, assembling a two-dimensional lattice in the ac plane. The analogue compounds 2 and 3 attain bulky single clusters with the general formula Hg₁₄X₆(SePh)₂₂ (X = Cl, Br), accomplished by the symmetrical combination of two asymmetric units [Hg₇X₃(PhSe)₁₁]. While the polymerization of the single units of 2 along the c axis occurs through 4 selenium atoms, the polymerization of 3 arises through 6 bonds involving Hg and Se atoms. Although 2 and 3 seem to be resultant from the random assembly of asymmetrical rings, both cluster compounds present symmetry centers.     

Polysulfonylamine. XXXVII. Darstellung von Quecksilberdimesylamiden. Kristall- und Molekülstrukturen von Hg[N(SO2CH3)2]2, Hg[{N(SO2CH3)2}2(DMSO)2] und Hg[{N(SO2CH3)2}2(HMPA)]

Polysulfonyl Amines. XXXVII. Preparation of Mercury Dimesylamides. Crystal and Molecular Structures of Hg[N(SO₂CH₃)₂]₂, Hg[{N(SO₂CH₃)₂}₂(DMSO)₂], and Hg[{N(SO₂CH₃)₂}₂(HMPA)] Hg[N(SO₂CH₃)₂]₂ ( 1 ) and Hg₂[N(SO₂CH₃)₂]₂ ( 2 a ) are formed as colourless, sparingly soluble precipitates when solutions of Hg(NO₃)₂ or Hg₂(NO₃)₂ in dilute nitric acid are added to an aqueous HN(SO₂CH₃)₂ solution. By a similar reaction, Hg₂[N(SO₂C₆H₄ ? Cl? 4)₂]₂ is obtained. 1 forms isolable complexes of composition Hg[N(SO₂CH₃)₂]₂ · 2 L with L = dimethyl sulfoxide (complex 3 a ), acetonitrile, dimethyl formamide, pyridine or 1,10-phenanthroline and a (1/1) complex Hg[N(SO₂CH₃)₂]₂ · HMPA ( 4 ) with hexamethyl phosphoramide. Attempted complexation of 2 a with some of these ligands induced formation of Hg⁰ and the corresponding Hg^II complexes. Crystallographic data (at -95°C) are for 1: space group 14₁/a, a = 990.7(2), c = 2897.7(8) pm, V = 2.844 nm³, Z = 8, D_x = 2.545Mgm^?3; for 4a: space group P1 , a = 767.8(2), b = 859.2(2), c = 925.2(2)pm α = 68.44(2), β = 86.68(2), γ = 76.24(2)°, V = 0.551nm³, Z = 1, D_x = 2.113 Mgm^?3; for 4: space group P2₁/c, a = 1041.3(3), b = 1545.4(3), c = 1542.5(3) pm, β = 100.30(2)°, V = 2.474nm³, Z = 4, D_x = 1.944Mgm³. The three compounds form molecular crystals. The molecular structures contain a linear or approximately linear, covalent NHgN moiety; the Hg? N distances and N? Hg? N angles are 206.7(4) pm and 176.3(2)° for 1, 207.2(2) pm and 180.0° for 3a, 205.7(4)/206.7(4) pm and 170.5(1)° for 4. In the complexes 3a and 4, the 0-ligands are bonded to the Hg atoms perpendicularly to the N? Hg? N axes, leading in 3a to a square-planar trans-(N₂O₂) coordination with Hg? 0 261.2(2) pm and N? Hg? O 92.3(1)/87.7(1)°, in 4 to a slightly distorted T-shaped (N₂O) geometry with Hg? 0 246.2(4)pm and N? Hg? 0 96.7(1)/92.0(1)°. In all three structures, the primary coordination is extended to a severely distorted (N₂O₄) hexacoordination by the appropriate number of secondary, inter- and/or intramolecular Hg…?0 inter-actions (0 atoms from sulfonyl groups, Hg…?O distances in the range 280—300pm). The intramolecular Hg…?O interactions give rise to nearly planar four-membered [HgNSO] rings. The molecule of 1 has a two-fold axis through the bisector of the N? Hg? N angle, the molecule of 3a an inversion center at the Hg atom. The molecule of 4 has no symmetry.     

Dinuclear Manganese(II) Complexes with Bridging Selenidodiarsenate Anions [As2Se4]4−, [As2Se5]4− and [As2Se6]2−

Solvothermal reaction of [MnCl₂(amine)] (amine = terpy and tren) with elemental As and Se at a 1:1:2 molar ratio in H₂O/tren (10:1) affords the dimanganese(II) complexes [{Mn(terpy)}₂(μ‐As₂Se₄)] ( 1 ) and [{Mn(tren)}₂(μ‐As₂Se₅)] ( 2 ) respectively. The tetradentate [As₂Se₄]^4? bridging ligands in 1 contain a central As–As bond and exhibit approximately C_2h symmetry. Pairs of gauche sited Se atoms participate in five‐membered As₂Se₂Mn chelate rings. In contrast, two AsSe₃ pyramids share a common corner in the [As₂Se₅]^4? ligands of 2 and each coordinates an [Mn(tren)]²⁺ fragment through a single terminal Se atom. Such dinuclear complexes are linked into tetranuclear moieties through weak Se···Mn interactions of length 3.026(3) Å involving one of these terminal Se atoms. At a 1:3:6 molar ratio, solvothermal reaction of [MnCl₂(tren)] with As and Se leads to formation of a second dinuclear complex [{Mn(tren)}₂(μ‐As₂Se₆)₂] ( 3 ), which contains two bridging bidentate [As₂Se₆]^2? ligands. These are cyclic with an As₂Se₄ ring and can be regarded as being derived from [As₂Se₅]^4? anions by formation of two Se‐Se bonds to an additional Se atom.     

A New Chain Polymer via Thermolysis: [Hg(μ‐Br)2(3,5‐Br2py)]∞

The new ligand‐deficient chain polymer [Hg(μ‐Br)₂(3,5‐Br₂py)]_∞ has been obtained in form of single crystals by thermolysis of the ligand‐rich [Hg(μ‐Br)₂(3,5‐Br₂py)₂]_∞ at 180 °C at ambient pressure. From this reaction, high quality crystals of the product are directly accessible. The title compound features Hg^II cations in a distorted square‐pyramidal coordination; their metal centers aggregate via edge‐sharing with asymmetric halide bridges to chains in which all apical N donor ligands are oriented to the same side of the [Hg(μ‐Br)₂]_∞ backbone. The new polymer cannot be prepared by stoichiometric reaction in solution.     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von Quecksilber(II)‐bis(tetracyanoborat) Hg[B(CN)4]2 und Diquecksilber(I)‐bis(tetracyanoborat) Hg2[B(CN)4]2

Preparation, Spectroscopic Characterization and Crystal Structures of Mercury(II)‐bis(tetracyanoborate) Hg[B(CN)₄]₂ and Dimercury(I)‐bis(tetracyanoborate) Hg₂[B(CN)₄]₂ Hg[B(CN)₄]₂ ( 1 ) is synthesised by the reaction between Hg(NO₃)₂ and K[B(CN)₄]₂. In a comproportionation reaction of 1 with elemental mercury the corresponding mercury(I) salt Hg₂[B(CN)₄]₂ ( 2 ) is obtained. The compounds were characterised by vibrational‐ and NMR‐spectroscopy, and their crystal structures were determined. Hg[B(CN)₄]₂ crystallizes in the trigonal system in the space group P3¯m1 with a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)ų, and one formula unit per unit cell. For Hg₂[B(CN)₄]₂ an orthorhombic unit cell with a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)Å, and Z = 4 is observed.