Anhydrous Mercurous Chlorate,Hg2(ClO3)2

Colourless single crystals of the anhydrous mercurous chlorate were grown from a solution of mercuric oxide (HgO) in chloric acid (HClO₃) in the presence of elemental mercury. The crystal structure (monoclinic, P2₁/n, Z = 4, a = 816.59(12), b = 641.02(5), c = 1290.3(2) pm, β = 97.506(12)°, R(all) = 0.0317) contains trans‐O₂ClO‐Hg‐Hg‐OClO₂ molecules with a Hg‐Hg distance of 251.03(4) pm, Hg‐O (bond) distances of 218 and 224 pm and Hg‐Hg‐O angles of 177 and 165°, respectively.     

Darstellung und Kristallstruktur des Quecksilber(II)-thiodiphosphats Hg2P2S7

Preparation and Crystal Structure of Mercury (II) Thiodiphosphate Hg₂P₂S₇ Hg₂P₂S₇ crystallizes monoclinic with a = 10.887(8); b = 5.827(3); c = 8.132(6) Å und β = 103.83(6)° in space group C2.The crystal structure was determined from four-circle diffractometer data by means of the heavy atom method and refined by least squares to R = 0.094 for 1119 intensities. The structure contains P₂S₇ group which are arranged in layer parallel to the (001) plane and connected by Hg atoms to form a three-dimensional network. The Hg atoms are surrounded by four S atoms in a deformed tetrahedral arrangement (means distance Hg? S: 2.591 Å). The P₂S₇ group are composed of two PS₄ tetrahedra sharing one corner (mean distance P? S: 2.048 Å; ? P? S? P: 108.6°). According to the structural data Hg₂P₂S₇ may be interpreted as mercury(II) thiodiphosphate. The bond distance and the structural relationships between Hg₂P₂S₇ and Ag₄P₂S₇ are discussed. Hg₂P₂S₇ represents a new defect tetrahedral structural type.     

The Crystal and Molecular Structure of Mercury Fulminate (Knallquecksilber)

A short survey on the fascinating history of mercury fulminate is given. The crystal structure of Hg(CNO)₂ has been determined using single crystal X‐ray diffraction. Mercury fulminate crystallizes in an orthorhombic cell, space group Cmce with a = 5.3549(2), b = 10.4585(5), c = 7.5579(4) Å and Z = 4. The distances and angles in the O‐N≡C‐Hg‐C≡N‐O molecule are Hg‐C 2.029(6) Å, C≡N 1.143(8) Å, N‐O 1.248(6) Å and C‐Hg‐C 180.0(1)°, Hg‐C≡N 169.1(5)°, C≡N‐O 179.7(6)°. Each mercury atom is surrounded by two oxygen atoms from neighbouring Hg(CNO)₂ molecules with a nonbonding distance of Hg···O 2.833(4) Å. The Hg‐C bond lengths in the linear Hg(CNO)₂ molecules are shorter than those in the tetrahedral complex [Hg(CNO)₄]^2?. This refers to a large contribution of the 6s orbital in the Hg‐C bonds of Hg(CNO)₂. The results of the X‐ray powder investigation on Hg(CNO)₂ are also reported.     

Strong Attraction of Caffeine to the Mercurous Dumbbell in the Salt [Hg2(Caf)2](ClO4)2(H2O)2

Colourless single crystals of the caffeine adduct of mercurous perchlorate dihydrate, [Hg₂(Caf)₂](ClO₄)₂(H₂O)₂, were grown from aqueous solutions of mercurous perchlorate and caffeine by isothermal evaporation at ambient temperature. The crystal structure (monoclinic, P2₁/n, Z = 4, a = 1628.0(2), b = 780.4(1), c = 2229.6(3) pm, β = 99.84(1)°, R₁(all data) = 0.0894) contains [trans‐Caf‐Hg‐Hg‐Caf]²⁺ cations with a Hg‐Hg distance of 250.88(6) pm, Hg‐N (bond) distances of 214.4(6) and 215.1(6) pm and Hg‐Hg‐N angles of 176.9(2) and 165.1(2)°, respectively. These cations are attached via weak Hg‐O contacts to dimers which are further arranged to leave large channels into which one crystal water molecule is included. The second water molecule and the two perchlorate anions are weakly attracted to one Hg atom.     

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.     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [O3SS(NPPh3)2] · CH3CN, [SO(NPPh3)2] und [SCl(NPMe3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Syntheses and Crystal Structures of [O₃SS(NPPh₃)₂] · CH₃CN, [SO(NPPh₃)₂], and [SCl(NPMe₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SO₂ and SOCl₂, respectively, and by the reaction of Me₃SiNPMe₃ with S₂Cl₂. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [O₃SS((NPPh₃)₂)] · CH₃CN : Space group Pca2₁, Z = 4, structure solution with 4016 observed unique reflections, R = 0.050. Lattice dimensions at ?60°C: a = 1865.1, b = 1168.4, c = 1569.0 pm. The compound has a zwitterionic structure with a S? S bond length of 218.2 pm and bond lengths S? N of 161.2 and P? N of 160.1 pm. [SO(NPPh₃)₂] : Space group P2₁/c, Z = 4, structure solution with 2854 observed unique reflections, R = 0.113. Lattice dimensions at ?50°C: a = 1173.1, b = 1585.6, c = 1619.2 pm, b? = 98.13°. The compound forms monomeric molecules, in which the positions of S and N atoms are disordered in two positions. The bond lengths are S? N 166 pm and P? N 163 pm in average. [SCl(NPMe₃)₂]Cl : Space group P1 , Z = 2, structure solution with 2416 observed unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 613.2, b = 1030.3, c = 1111.4 pm, α = 88.48°, b? = 88.01°, γ = 83.10°. The compound forms ions [SCl(NPMe₃)₂]⁺ and Cl^?. In the cation the sulfur atom is ?-tetrahedrally coordinated with a long S? Cl distance of 246.9 pm and bond lengths S? N of 155.3 pm and P? N of 164.3 pm in average.     

Übergangsmetallphosphidokomplexe. VIII. Strukturuntersuchungen an Übergangsmetallphosphor-Vier- und Sechsringkomplexen. Die Strukturen von [(CO)4MnPH2]2, [(CO)4MnPH2]3 und [cpNiPH2]3

Transition Metal Phosphido Complexes. VIII. X-Ray Diffraction Studies of Transition Metal Phosphorus Four- and Six-Membered Ring Complexes. Structures of [(CO)₄MnPH₂]₂, [(CO)₄MnPH₂]₃, and [cpNiPH₂]₃ [(CO)₄MnPH₂]₂ 1 crystallizes triclinic in the space group P1 with a = 680.4 pm, b = 706.4 pm, c = 919.1 pm, α 110.5°, β = 91.92°, γ 115.65°, and Z = 1 formula unit. The molecule exhibits a centrosymmetrical structure. The bond angles within the planar four-membered (Mn? P)₂-ring are 76.1° at the Mn atoms and 103.9° at the P atoms, respectively. The average Mn? P bond distance is found to be 235.1 pm. [(CO)₄MnPH₂]₃ 2 crystallizes monoclinic in the space group P2/n with a = 905.2 pm, b = 974.8 pm, c = 1264.2 pm, β = 109.1°, and Z = 2 formula units. The framework of the six-membered (Mn? P)₃-ring can be described as having a twist boat conformation. The average endocyclic bond angles are with 89.1° at the Mn atoms and 130.1° at the P atoms, respectively, largely widened compared to 1 . The average Mn? P bond distance, which is found to be 238.5 pm, is also slightly increased compared to 1 . [cpNiPH₂]₃ 3 crystallizes rhombohedral in the space group R3. The cell constants (hexagonal setting) are a = b = 1686.1 pm, c = 561.1 pm and Z = 3 formula units. The six-membered (Ni? P)₃-ring exhibits a chair conformation. The endocyclic bond angles are with 92.3° at the Ni atoms and 124.3° at the P atoms, respectively, comparable with those of the six-membered ring compound 2 . The Ni? P bond distance is found to be 215.2 pm. The eyclopentadienyl ligands are disordered and have been refined as rigid groups.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXXV. Das dimere Thallium(I)-tri-tert-butoxysilanthiolat

Contributions to the Chemistry of Silicon-Sulfur Compounds. XXXV. The Dimeric Thallium(I)-tri-tert-butoxysilanethiolate Thallium(I)-tri-tert-butoxysilanethiolate is formed as a dimer by reaction of tri-tert-butoxysilanethiol with TlNO₃. The compound crystallizes as colourless triclinic plates. F.I. mass spectra show only the mass of the dimeric species (m/e = 968), in the E.I. mass spectra, however, also the peak for the monomeric unit (m/e = 484) is observed. The molecule is of 1 /C_i symmetry. The central four-membered ring is plane, the bond distances and angles therein are d (Tl? S) = 289 pm and S/Tl/S = 91.5°. The Tl atoms are additionally coordinated by an oxygen atom of the tri-tert-butoxysilyl group (d(Tl? O) = 280 pm). The mean bond angle at the threebonded sulfur atom was found to be 90° (d(S? Si) = 207.8 pm). Related details of the structure are discussed (space group P1 ; a = 927.5 pm, b = 1395.1 pm, c = 882.1 pm; α = 108.43°, β = 116.77°, γ = 90.98°; Z = 2; R = 0.032; 2887 reflections hkl).     

Übergangsmetallphosphidokomplexe. XVI. Die Strukturen von zwei offenkettigen,PH2-verbrückten Zweikernkomplexen cp(CO)2Fe(μ-PH2)MLn (MLn = Fe(CO)4, MnMecp(CO)2)

Transition Metal Phosphido Complexes. XVI. Structures of two Open-Chain, PH₂-Bridged Bimetallic Complexes cp(CO)₂Fe(μ-PH₂)ML_n (ML_n = Fe(CO)₄, MnMecp(CO)₂) cp(CO)₂Fe(μ-PH₂)Fe(CO)₄ 1 crystallizes monoclinic in the space group P2₁/c with a = 733.6 pm, b = 1089.8 pm, c = 1761.6 pm, β = 99.65°, and Z = 4 formula units. The bond distances of the bridging phosphorus atom to the two iron units Fe(1)(CO)₄ and cp(CO)₂Fe(2) differ with 229.0 pm (P? Fe(1)) and 226.5 pm (P? Fe(2)), respectively, only slightly. The angle Fe(1)? P? Fe(2) is with 124.8° surprisingly large for four-coordinate phosphorus. The coordination at Fe(1) is trigonal bipyramidal with axial phosphorus. The ligand sphere at Fe(2) corresponds to the so-called “piano stool” arrangement. cp(CO)₂Fe(μ-PH₂)MnMecp(CO)₂ 2 crystallizes monoclinic in the space group P2₁ with a = 750.1 pm, b = 2234.5 pm, c = 974.1 pm, β = 106.23°, and Z = 4 formula units. The P? Fe bond distance is found to be 230.0 pm, the P? Mn bond distance 224.3 pm. The angle Fe? P? Mn is with 126.8° even somewhat larger than the corresponding angle in 1 . Including the bridging PH₂-group both transition metals of 2 achieve a kind of “piano stool” arrangement for their ligand sphere.     

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°).     

Synthese und Struktur von Lithium-tris(trimethylsilyl)silanid · 1,5 DME

Synthesis and Structure of Lithium Tris(trimethylsilyl)silanide · 1,5 DME Lithium tris(trimethylsilyl)silanide · 1,5 DME 2a synthesized from tetrakis(trimethylsilyl)silane 1 [6] and methyllithium in 1,2-dimethoxyethane , crystallizes in the monoclinic space group P2₁/c with following dimensions of the unit cell determined at a temperature of measurement of ?120 ± 2°C: a = 1 072.9(3); b = 1 408.3(4); c = 1 775.1(5) pm; β = 107.74(2)°; 4 formula units (Z = 2). An X-ray structure determination (R_w = 0.040) shows the compound to be built up from two [lithium tris(trimethylsilyl)silanide] moieties which are connected via a bridging DME molecule. Two remaining sites of each four-coordinate lithium atom are occupied by a chelating DME ligand. The Li? Si distance of 263 pm is considerably longer than the sum of covalent radii; further characteristic mean bond lengths and angles are: Si? Si 234, Li? O 200, O? C 144, O?O (biß) 264 pm; Si? Si? Si 104°, Li? Si? Si 107° to 126°; O? Li? O (inside the chelate ring) 83°. Unfortunately, di(tert-butyl)bis(trimethylsilyl)silane 17 prepared from di(tert-butyl)dichlorsilane 15 , chlorotrimethylsilane and lithium, does not react with alkyllithium compounds to give the analogous silanide.     

Kristallstrukturen der Monofluorosulfite MSO2F (M = K,Rb)

Crystal Structures of Monofluorosulfites MSO₂F (M = K, Rb) Single crystals of potassium and rubidium fluorosulfite were obtained for the first time by reacting the alkali metal fluorides with sulfur dioxide in acetonitrile at 75 °C. According to the results of X‐ray structure determinations they are isotypic (monoclinic, P2₁/m, Z = 2, KSO₂F: a = 696.2(2), b = 566.3(2), c = 465.8(1) pm, β = 107.73(2)°, RbSO₂F: a = 717.2(1), b = 586.7(1), c = 484.0(1) pm, β = 107.14(1)°) and structurally analogous to potassium chlorate. In contrast to potassium fluoroselenite in which the complex anions are polymerized to linear chains by unsymmetric fluorine bridges, the fluorosulfite anion is isolated. The S–F‐distance of 159.1(2) pm (KSO₂F) corresponds to a S–F single bond, the S–O‐distance of 152.6(2) pm indicates a bond order of 1.5.     

Beiträge zur Chemie der Silicium-Schwefelverbindungen. XXXVIII. Hexa-(tri-t-butoxy)disiloxan und Hexa-(tri-t-butoxy)disilthian

Contributions to the Chemistry of Silicon Sulfur Compounds. XXXVIII. Hexa(tri-t-butoxy)disiloxane and Hexa(tri-t-butoxy)disilthiane Hexa(tri-t-butoxy)disiloxane 1 and Hexa(tri-t-butoxy)disilthiane 2 were prepared by reaction of R₃SiONa with R₃SiCl and R₃SiSNa with R₃SiCl (R = tri-t-butoxy), respectively. The mass spectra show characteristic series of fragments. A large ²⁹Si n.m.r. chemical shift of about —103.55 ppm is observed with 1 , whereas the value of 2 is —75.99 ppm. The crystal structure analysis of 1 result first in a colinear molecule (Si? ;O? ;Si = 180°) with 1 symmetry and relative short mean bond lengths of about d(Si? ;O) = 155.6 pm, but with large and strong anisotropic ellipsoids. Their quantitative rigid body analyses yield decisive corrections, namely a bent molecule with an Si? ;O? ;Si angle of 144.0° and d?_corr = 163.5 pm. Molecule 2 is also bent as expected (Si? ;S? ;Si = 110.5°, d?(Si? ;S) = 211.9 pm and after rigid body correction 108.0° and d_corr = 215.2 pm, respectively). The results of our investigations will be discussed corresponding to the energy differences of the varying configurations at the bridging atoms.     

Die Kristallstruktur des tBu2P?PP(Br)tBu2

The Crystal Structure of tBu₂P? P?P(Br)tBu₂ tBu₂P? P?P(Br)tBu₂ 1 crystallizes in the monoclinic space group P2₁/c with a = 2 888.9(3), b = 972.16(10), c = 1 534.04(14) pm, β = 105.129(8)° and 8 formula units in the unit cell. The two independent P₃-units in 1 form angles of 105.77° or 105.98°, resp. One P? P distance (220,4 pm) corresponds to a single bond, the other one (207.9 pm) to a double bond.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXXIII. Die Struktur des Bis(triphenylsilyl)sulfids

Contributions to the Chemistry of Silicon Sulphur Compounds. XXXIII. Structure of Bis (triphenylsilyl)sulphide The condensation of triphenylsilanethiol yielded bis(triphenylsilyl)sulphide ( 1 ). The compound is remarkable resistent to hydrolysis. 1 crystallizes monoclinically [P2₁/n (No. 14): a = 1707.8 pm; b = 1454.6 pm; c = 1225.0 pm; β = 97.27°; Z = 4; 4470 h k l; R = 0.053]. The molecule is bent with a bond angle Si? S? Si = 112.0°. The mean bond distances Si? S and Si? C are 215.2 pm and 187.4 pm, respectively. Some structural details are discussed.     

Synthese von Nitrenkomplexen mit N-Trimethylsilylanilin. II. Charakterisierung und Kristallstruktur der Rhenium(V)-phenylnitren-Komplexe mer-[Re(NPh)Cl3(NH2Ph)(Ph3P)] und trans-[Re(NPh)(OMe)Cl2(Ph3P)2]

Synthesis of Phenylnitrene Complexes with N-Trimethylsilylaniline. II. Characterization and Crystal Structure of the Rhenium(V) Complexes mer-[Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] and trans-[Re(NPh)(OMe)Cl₂(Ph₃P)₂] Reaction of [ReOCl₃(Ph₃P)₂] with N-trimethylsilylaniline yields mer-[Re(NPh)Cl₃(Ph₃P)₂], which reacts under air with excess of N-trimethylsilylaniline to form [Re(NPh)Cl₃ · (NH₂Ph)(Ph₃P)]. Crystallization from CH₂Cl₂/MeOH affords [Re(NPh)(OMe)Cl₂(Ph₃P)₂] as an additional product. [Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] crystallizes in the monoclinic space group P2₁/n with a = 1 192.3(3); b = 1 918.9(3); c = 1 266.3(3) pm; β = 101.71(1)°; Z = 4. The rhenium atom has a distorted octahedral environment with the Cl atoms in meridional positions. The phenyl nitrene ligand is coordinated with an almost linear arrangement Re? N1? C40 = 166.8(6)° and with a bond distance Re?N = 170.5(6) pm. [Re(NPh)(OMe)Cl₂(Ph₃P)₂] · 1/2CH₂Cl₂ crystallizes in the triclinic space group P1 : a = 1 103.1(4); b = 1 227.9(4); c = 1 711.3(5) pm; α = 70.48(3)°; β = 72.71(3)°; γ = 80.03(3)°; Z = 2. The rhenium atom exhibits a distorted octahedral coordination with the Cl atoms and the phosphine ligands in trans positions. As a consequence of the competition of the nitrene ligand and the trans-coordinated methoxy group the Re?;N bond length is slightly lengthened to 173.2(7) pm, while the Re? O bond length of 193.4(6) pm is short. The bond angles Re? N? C70 and Re? O? C80 are 173.3(7)° and 139.1(7)°, respectively.     

Mercurous Dimethylglyoximato Nitrate,Hg2(Dmg)2(NO3)2

Colourless needles of mercurous dimethylglyoximato nitrate, Hg₂(Dmg)₂(NO₃)₂, grow from a diluted nitric acid solution of mercurous nitrate and dimethylglyoxime. The crystal structure (triclinic, P1¯, a = 728.50(13), b = 1066.8(2), c = 1167.9(2) pm, α = 93.78(2)°, β = 94.16(2)°, γ = 98.61(2)°, R_all = 0, 0726) contains the cations [Hg₂(Dmg)₂]²⁺ and “non‐coordinating” (NO₃)^— anions. In the cation, two neutral dimethylglyoxime molecules coordinate bidentately with Hg—N distances in the narrow range of 236 to 239 pm to the mercurous ion, Hg₂²⁺, which exhibits a Hg—Hg bond distance of 252.23(8) pm).     

Molekül‐ und Kristallstruktur von Quecksilber(II)‐α‐Amino‐γ‐methylmercapto‐butyrat,Hg(Met)2

Molecular and Crystal Structure of Mercuric α‐Amino‐γ‐methyl‐mercapto‐butyrate, Hg(Met)₂ The mercuric salt of deprotonated methionine, Hg(Met)₂, was obtained as colourless needles from aqueous solutions of methionine and HgCl₂ or HgO, respectively. The crystal structure (monoclinic, P2₁, Z = 2, a = 984, 2(2), 507, 96(6), c = 1574, 2(3) pm, β = 93, 05(2)°; R_all = 0, 055) exhibits formula‐like molecules with strong Hg—N coordination at a distance of 216 pm; one oxygen atom adds to a chelate like N—Hg—O coordination. Stacking of these molecules adds two oxygen atoms of different methionate anions to an effective 2+2+2 ?octahedral”? coordination around the mercuric ion. Thereby a layer structure parallel (001) is formed with the methyl‐mercapto function on top and bottom of these layers.     

The Monohydrate of Basic Mercuric Nitrate, [Hg(OH)](NO3)(H2O)

Colourless single crystals of [Hg(OH)](NO₃)(H₂O) were obtained by slow evaporation of an aqueous solution of Hg(NO₃)₂ and Bi(NO₃)₃. The crystal structure (orthorhombic, Pbca, Z = 8, a = 943.2(2), b = 697.6(1), c = 1349.0(2) pm, R₁(all) = 0.0780) contains [Hg(OH)] = …OH–Hg–OH–Hg… zig zag chains (O–Hg–O angle: 168°, Hg–O–Hg angle: 112°, Hg–OH distance: 212 pm) to which one water molecule is attached loosely. The [Hg(OH)](H₂O) chains are connected via bis‐monodentate‐bridging nitrate ions to corrugated layers that are stacked in the [001] direction. Hg²⁺ has an effective 2+2+2(+1) coordination.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXX. Die Struktur des Tetra-t-butoxy-1,3,2,4-dithiadisiletans

Contributions to the Chemistry of Silicon-Sulfur Compounds. XXX. Structure of Tetra-t-butoxy-1,3,2,4-dithiadisiletane Alcoholysis of silicon disulfide by t-butanol yielded the title compound. [(t-BuO)₂SiS]₂ crystallizes orthorhombically in the space group Pbca (no. 61) with a = 1708.4(5), b = 1560.8(3), c = 907.1(3) pm and Z = 4 molecules per unit cell. The molecule has the crystallographic 1 –C_i point symmetry and consequently the Si₂S₂ four-membered ring is rigid plane. The bond distances of this ring are Si? S = 214.2 and 213.1 pm and the bond angles S? Si? S = 97.8° and Si? S? Si = 82.2°. Related details of the structure are discussed.