Synthesis and Structure of (NH4)2[(AuI4)(MI4)] (M = Ga,In)

The compounds (NH₄)₂[(AuI₄)(MI₄)] (M = Ga, In) were obtained in sealed glass ampoules by reaction of I₂, NH₄I, Au and Ga or In as air‐sensitive black crystals. Both compounds crystallize in the orthorhombic space group Pnma (No. 62) and are isotypic: (NH₄)₂[(AuI₄)(GaI₄)], a = 12.619(2), b = 20.625(5) and c = 7.693(2) Å; (NH₄)₂[(AuI₄)(InI₄)], a = 12.587(2), b = 20.606(5) and c = 7.696(2) Å. The structures can be described as constituted of NH₄⁺ cations and anionic zig zag chains of alternating tetrahedral MI₄^– (M = In, Ga) and square planar AuI₄^– units running along [010]. Within the chains, the MI₄^– ions form weak interactions with two of their I atoms to the AuI₄^– ions resulting in strongly elongated AuI₆ octahedra.     

Cerium(III) Complexes with Lacunary Polyoxotungstates. Synthesis and Structural Characterization of a Novel Heteropolyoxotungstate Based on α-[SbW9O33]9− Units

Several cerium(III) complexes with lacunary polyoxotungstates -B-XW₉O^9– ₃₃ (X=As^III, Sb^III) and W₅O^6– ₁₈, have been synthesized and characterized by single-crystal X-ray analysis, elemental analysis and IR spectroscopy. The X-ray analysis of Na₂₅[Ce(H₂O)₅As₄W₄₀O₁₄₀]63H₂O (1) reveals the framework of the well-known [As₄W₄₀O₁₄₀]^28– anion with a {Ce(H₂O)₅}³⁺ unit in the central site S1. The anion in (NH₄)₁₉[(SbW₉O₃₃)₄{WO₂(H₂O)}₂Ce₃(H₂O)₈(Sb₄O₄)]48H₂O (2) consists of a tetrahedral assembly of four -B-Sb^IIIW₉O^9– ₃₃ units connected by two additional six-coordinate tungsten atoms, three nine-coordinate monocapped square-antiprismatic cerium atoms and a Sb₄O₄ cluster. The Ce^III center in the [Ce(W₅O₁₈)₂]^9– anion in Na₉[Ce(W₅O₁₈)]NaCl30H₂O (3) displays the square-antiprismatic environment observed in all complexes of the type [Ln(W₅O₁₈)₂] ^n–.     

Complexation and the laser luminescence studies of Eu(III), Am(III), and Cm(III) with EDTA,CDTA, and PDTA and their ternary complexation with dicarboxylates

Spectroscopy has been used to determine the number of coordinated water molecules bound to Eu(III) and Cm(III) in a series of binary complexes of polyaminocarboxylate and their ternary complexes with dicarboxylates as well as with similar ligands with additional O-, N-, and S-donors. Complexes of Eu(III) and Cm(III) with polyaminocarboxylate alone contain ca. 2.5–3.0 waters of hydration. Increasing the steric requirement of a polyaminocarboxylate by increasing the number of groups in the ligand backbone does not appreciably change the hydration of these cations. The stability constants of the binary and ternary complexes of Cm(III), Am(III), and Eu(III) with these ligands were measured by solvent extraction in a solution of 0.1 M (NaClO₄). The size, basicity, specific M³⁺-second ligand interactions, and steric requirement of the ligands are the factors which affect the ternary complexation. Knowledge of the chemical species formed by actinide cations with organic ligands (carboxylates and aminocarboxylates), which are present in all nuclear waste, is important to understand the behavior of waste forms and the migration behavior of actinides in the environment.     

Extraction chromatographic study of aluminium(III) and mutual separation of aluminium(III), gallium(III), indium(III) and thallium(III) with N-n-octylaniline

A selective method has been developed for extraction chromatographic studies of aluminium(III) and its separation from several metal ions with a chromatographic column containing N-n-octylaniline (liquid anion exchanger) coated on silanized silica gel as a stationary phase. The aluminium(III) was quantitatively extracted with the 0.065 mol/L N-n-octylaninine from 0.013 to 0.05 mol/L sodium succinate at a flow rate of 1.0 mL/min. The extracted metal ion has been recovered by eluting with 25.0 mL of 0.05 mol/L hydrochloric acid and estimated spectrophotometrically with aurintricarboxylic acid. The effects of the acid concentration, the reagent concentration, the flow rate and the eluting agents have been investigated. The log-log plots of distribution coefficient (KdAl(III)) versus N-n-octylaniline concentrationin 0.005 and 0.007 mol/L sodium succinate gave theslopes 0.5 and 0.7 respectively and showed theprobable composition of theextracted species was 1:1 (metal to amine ratio) and the nature of extracted species is [RR''NH2+ Al succinate2-] org. .The extraction of aluminium(III) was carried out in the presence of various ions to ascertain the tolerance limit of individual ions. Aluminium(III) has been separated from multicomponent mixtures, pharmaceutical samples and synthetic mixtures corresponding to alloys. A scheme for mutual separation of aluminium(III), indium(III), gallium(III) and thallium(III) has been developed by using suitable masking agents. The method is fast, accurate and precise.     

New complexes of lanthanide Ln(III), (Ln = La, Sm, Gd, Er) with Schiff bases derived from 2-furaldehyde and phenylenediamines

Some new Schiff bases derivates from 2-furaldehyde and phenylenediamines (L^1-3) and their complexes with lanthanum (La), samarium (Sm), gadolinium (Gd) and erbium (Er) have been synthesized. These complexes with general formula [Ln(L^1-3)₂(NO₃)₂]NO₃·nH₂O (Ln = La, Sm, Gd, Er) were characterized by elemental analysis, UV-Vis, FT-IR and fluorescence spectroscopy, molar conductivity and thermal analysis. The metallic ions were found to be eight coordinated. The emission spectra of these complexes indicate the typical luminescence characteristics of the Sm(III), La(III), Er(III) and Gd(III) ions.     

1,3-Dimethyl-2-phenyl-1,3-diazaphospholidine-2-oxide as ligand for the preparation of luminescent lanthanide complexes

Abstract

Europium(III) coordination compounds having general formula [Eu(β-dike)₃L₂] (β-dike?=?dibenzoylmethanate, tenoyltrifluoroacetonate; L?=?1,3-dimethyl-2-phenyl-1,3-diazaphospholidine-2-oxide) were isolated and characterized. The complexes exhibited bright red emission associated to the ⁵D₀→⁷F_J transitions of the metal center upon excitation with near-UV light, with intrinsic quantum yields around 51% and 65%, respectively, for the dibenzoylmethanate and tenoyltrifluoroacetonate derivatives. More information about the behavior of 1,3-dimethyl-2-phenyl-1,3-diazaphospholidine-2-oxide as an antenna-ligand towards trivalent lanthanide ions was obtained by its coordination to [Ln(NO₃)₃] (Ln?=?Eu, Gd, Tb) metal fragments.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

Die Chlorooxoarsenate(III) (PPh4)2[As4O2Cl10] · 2 CH3CN und (PPh4)2[As2OCl6] · 3 CH3CN

The Chlorooxoarsenates(III) (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN and (PPh₄)₂[As₂OCl₆] · 3 CH₃CN (PPh₄)₂[As₂Cl₈] can be prepared from As₂O₃, SOCl₂ and PPh₄Cl in acetonitrile. Its oxidation with chlorine yields PPh₄[AsCl₆]. This was also obtained directly from arsenic, chlorine and PPh₄Cl, (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN being a side product; the latter was obtained with high yield from AsCl₃, As₂O₃ and PPh₄Cl in acetonitrile. By addition of PPh₄Cl it was converted to (PPh₄)₂[As₂OCl₆] · 3 CH₃CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As₄O₂Cl₁₀]^2– ion can be regarded as a centrosymmetric association product of two Cl₂AsOAsCl₂ molecules and two Cl^– ions, each Cl^– ion being coordinated with all four As atoms. In the [As₂OCl₆]^2– ion the As atoms are linked via the O atom and two Cl atoms.     

Complexation studies of Cm(III), Am(III), and Eu(III) with linear and cyclic carboxylates and polyaminocarboxylates

Solvent extraction and potentiometric titration methods have been used to measure the stability constants of Cm(III), Am(III), and Eu(III) with both linear and cyclic carboxylates and polyaminocarboxylates in an ionic strength of 0.1?mol?L^?1 (NaClO₄). Luminescence lifetime measurements of Cm(III) and Eu(III) were used to study the change in hydration upon complexation over a range of concentrations and pH values. Aromatic carboxylates, phthalate (1,2 benzene dicarboxylates, PHA), trimesate (1,3,5 benzene tricarboxylates, TSA), pyromellitate (1,2,4,5 tetracarboxylates, PMA), hemimellitate (1,2,3 benzene tricarboxylates, HMA), and trimellitate (1,2,4 benzene tricarboxylates, TMA) form only 1?:?1 complexes, while both 1?:?1 and 1?:?2 complexes were observed with PHA. Their complexation strength follows the order: PHA～TSA>TMA>PMA>HMA. Carboxylate ligands with adjacent carboxylate groups are bidentate and replace two water molecules upon complexation, while TSA displaces 1.5 water molecules of hydration upon complexation. Only 1?:?1 complexes were observed with the macrocyclic dicarboxylates 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N′-diacetate (K21DA) and 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N′-diacetate (K22DA); both 1?:?1 and 1?:?2 complexes were observed with methyleneiminodiacetate (MIDA), hydroxyethyleneiminodiacetate (HIDA), benzene-1,2-bis oxyacetate (BDODA), and ethylenediaminediacetate (EDDA), while three complexes (1?:?1, 1?:?2, and 1?:?3) were observed with pyridine 2,6 dicarboxylates (DPA) and chelidamate (CA). The complexes of M-MIDA are tridentate, while that of M-HIDA is tetradentate in both 1?:?1 and 1?:?2 complexes. The M-BDODA and M-EDDA complexes are tetradentate in the 1?:?1 and bidentate in the 1?:?2 complexes. The complexes of M-K22DA are octadentate with one water molecule of hydration, while that of K21DA is heptadentate with two water molecules of hydration. Simple polyaminocarboxylate 1,2 diaminopropanetetraacetate (PDTA) and ethylenediamine N,N′-diacetic-N,N′-dipropionate (ENDADP) like ethylenediaminetetraacetate (EDTA) form only 1?:?1 complexes and their complexes are hexadentate. Polyaminocarboxylates with additional functional groups in the ligand backbone, e.g., ethylenebis(oxyethylenenitrilo) tetraacetate (EGTA), and 1,6 diaminohexanetetraacetate (HDTA) or with additional number of groups in the carboxylate arms diethylenetriamine pentaacetato-monoamide (DTPA-MA), diethylenetriamine pentaacetato-bis-methoxyethylamide (DTPA-BMEA), and diethylenetriamine pentaacetato-bis glucosaamide (DTPA-BGAM) are octadentate with one water molecule of hydration, except N-methyl MS-325 which is heptadentate with two water molecules of hydration and HDTA which is probably dimeric with three water molecules of hydration. Macrocyclic tetraaminocarboxylate, 1,4,7,10-tetraazacyclododecanetetraacetate (DOTA) forms only 1?:?1 complex which is octadentate with one water molecule of hydration. The functionalization of these carboxylates and polycarboxylates affect the complexation ability toward metal cations. The results, in conjunction with previous results on the Eu(III) complexes, provide insight into the relation between ligand steric requirement and the hydration state of the Cm(III) and Eu(III) complexes in solution. The data are discussed in terms of ionic radii of the metal cations, cavity size, basicity, and ligand steric effects upon complexation.     

The Affinity of Gallium(III) and Indium(III) for Nitrogen Donor Ligands

Abstract

Dedicated to Professor Arthur Martell on the occasion of his seventy fifth birthday.

The complexes of In(III) and Ga(III) with a variety of nitrogen donor ligands were studied in aqueous solution by glass electrode potentiometry at 25°C in 0.1 M NaNO₃. The ligands were 2-aminomethylpyri-dine (AMPY), ethylenediamine (EN), N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (THPED), and N,N-bis(2-hydroxyethyl)glycine (BICIN). A variety of mixed ligand complexes of the MLOH type were detected with many of the above ligands as L. The logK₁ values obtained were with Ga(III) 8.40 (AMPY), 7.94 (THPED) 12.72 (EN), and In(III) 7.6 (AMPY), 8.20 (THPED), and 7.06 (BICIN). These formation constants are discussed in relation to previous predictions that In(III) and Ga(III) would have a substantial chemistry with nitrogen donor ligands. Of particular interest is the Ga(III) system with EN, where a very stable Ga(EN)³⁺ complex is formed, but no higher complexes except for hydrolyzed species such as Ga(EN)OH²⁺ and Ga(EN)(OH)₂ ⁺.     

Osmium (VIII)-mediated oxidation of arsenic (III)/antimony (III) by 1-equivalent oxidants

Os(VIII) catalysis of oxidation of As(III)/Sb(III) by 1-equivalent oxidants like Ce(IV) and Mn(III) in acid medium is studied. A multistep mechanism involving the intervention of the intermediate oxidation states of osmium is found to apply. Specific rates of different steps in the mechanism are estimated and used to calculate reaction rates which are in reasonable agreement with those of experiment.     

Iridium(III) and rhodium(III) cyclometalated complexes containing sulfur and selenium donor ligands

Treatment of [M(Buppy)₂Cl]₂ (M=Ir (1), Rh (2); BuppyH=2-(4^′-tert-butylphenyl)pyridine) with Na(Et₂NCS₂), K[S₂P(OMe)₂], and K[N(Ph₂PS)₂]₂ afforded monomeric [Ir(Buppy)₂(S^∧S)] (S^∧S=Et₂NCS₂ (3), S₂P(OMe)₂ (4), N(PPh₂S)₂ (5)) and [Rh(Buppy)₂(S^∧S)] (S^∧S=Et₂NCS₂ (6), S₂P(OMe)₂ (7), N(PPh₂S)₂ (8)), respectively. Reaction of 1 with Na[N(PPh₂Se)₂] gave [Ir(Buppy)₂{N(PPh₂Se)₂}] (9). The crystal structures of 3, 4, 7, and 8 have been determined. Treatment of 1 or 2 with AgOTf (OTf=triflate) followed by reaction with KSCN gave dinuclear [{M(Buppy)₂}₂(μ-SCN)₂] (M=Ir (10), Rh (11)), in which the SCN⁻ ligands bind to the two metal centers in a μ-S,N fashion. Interaction of 1 and 2 with [Et₄N]₂[WQ₄] gave trinuclear heterometallic complexes [{Ir(Buppy)₂}₂(μ-WQ₄)] (Q=S (12), Se (13)) and [{Rh(Buppy)₂}₂{(μ-WQ)₄}] (Q=S (14), Se (15)), respectively. Hydrolysis of 12 led to formation of [{Ir(Buppy)₂}₂{W(O)(μ-S)₂(μ₃-S)}] (16) that has been characterized by X-ray diffraction.     

Neue Synthesewege für Thiohalogeno- und Cyclothioarsenate(III). Kristallstrukturen von PPh4[As2SBr6] · CH3CN und PPh4[SAsS5]

Novel Routes to the Synthesis of Thiohalogeno- and Cyclothioarsenates(III). Crystal Structures of PPh₄[As₂SBr₆] · CH₃CN and PPh₄[SAsS₅] By reactions of (PPh₄)₂[As₂Cl₈] and (PPh₄)₂[As₂Br₈] with Na₂S₄ in acetonitrile (PPh₄)₂[As₂SCl₆] · CH₃CN and (PPh₄)₂[As₂SBr₆] · CH₃CN were obtained, respectively. Using K₂S₅, PPh₄[As₂SCl₅] and PPh₄[SAsS₅] were the products. The latter can also be obtained from PPh₄[As₂SCl₅] and Na₂S₄, while PPh₄[As₃S₃Br₄] is formed from PPh₄[As₂SBr₅] with K₂S₅. Two X-ray crystal structure determinations were performed. PPh₄[As₂SBr₆] · CH₃CN: triclinic, P1 , Z = 2, a = 1200.4(7), b = 1507.3(6), c = 1594.4(8) pm, α = 81.59(2), β = 78.22(3), γ = 80.58(2)°, R = 0.096 for 2298 observed reflexions. The structure contains [As₂SBr₆]^2? -ions in which the two Sb atoms are joined via one S and two Br atoms. PPh₄[SAsS₅]: triclinic, P1 , Z = 2, a = 1133.9(4), b = 1142.5(4), c = 1186.9(5) pm, α = 102.77(4), β = 107.74(3), γ = 106.65(3)°, R = 0.043 für 2677 reflexions. In the [SAsS₅]^? -ion an AsS₅ ring in the chair conformation is present.     

SYNTHESIS AND CHARACTERIZATION OF THE FORMAL Ni(III) AND Cu(III) COORDINATION COMPLEXES OF THE NEW 1,2-DITHIOLENE, 1,4-BUTANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE

Abstract

The new 1,2-dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate, has been isolated. In addition, new monoanionic bis-complexes with nickel and copper have been prepared and isolated. The formal Ni(III) complex crystallizes in the orthorombic space group, P_bca, with a = 9.762(9), b = 12.53(2), and c = 23.166(3) Å, with 4 molecules in the unit cell. The structure was refined to an R = 9.01% (R_w = 8.95%). The formal Cu(III) complex crystallizes in the monoclinic space group, C_2/c, with a = 25.567(6), b = 8.011(3), c = 14.504(3) Å, and β = 106.17(2)° with 4 molecules in the unit cell. The structure refined to R = 4.2% with R _w = 4.3%. Comparisons to similar 1,2-dithiolenes suggest this ligand produces only modest structural and electronic differences when compared to the 1,3-propanediyldithioethylene-1,2-dithiolate complexes. The oxidation (to a neutral complex) and reduction (to a dianion) for the Ni(III) and Cu(III) complexes show large differences from those of maleonitriledithiolate. Other physical data are presented as well.     

Ein- und zweikernige Fluorokomplexe des Titan(III), Chrom(III) und Eisen(III) Darstellung und Struktur von (NMe4)(Ti(H2O)4F2)TiF6 · H2O, (NMe4)3Cr2F9 und (NMe4)3Fe2F9

Mono- and Dinuclear Fluoro Complexes of Titanium (III), Chromium (III), and Iron(III). Syntheses and Structures of (NMe₄) (Ti(H₂O)₄F₂)TiF₆ · H₂O, (NMe₄)₃Cr₂F₉, and (NMe₄)₃Fe₂F₉ The title compounds have been prepared by reaction of MCl₃ (M = Ti, Cr, Fe) with NMe₄F in dimethylformamide. (NMe₄)₃Cr₂F₉ and (NMe₄)₃Fe₂F₉ contain the face-sharing biocathedral M₂F₉^3? unit. The M…M distances are 277.1(1) and 289.8(3) pm in (NMe₄)₃Cr₂F₉ and (NMe₄)Fe₂F₉, respectively. (NMe₄)(Ti(H₂O)₄F₂)TiF₆ · H₂O contains trans-Ti^III(H₂O)₄F₂⁺ cations and Ti^IVF₆^2? anions. Crystal data: (NMe₄)₃Cr₂F₉: hexagonal, space group P6₃/m, a = 804.1(3), c = 1857.5(4) pm, Z = 2, 529 reflections, R = 0.049; (NMe₄)₃Fe₂F₉: hexagonal, space group P6₃/m, a = 804.7(5), c = 1 861.6(5) pm, Z = 2, 635 reflections, R = 0,046; (NMe₄)(Ti(H₂O)₄F₂)TiF₆ · H₂O: orthorhombic, space group Pbca, a = 776.9(2), b = 1 616.3(3), c = 2 428.6(7) pm, Z = 8, 2 784 reflections, R = 0,056.     

CRYSTAL STRUCTURE OF THE ISOMORPHOUS COMPLEXES TETRAAQUABIS(2,6-DIHYDROXY-BENZOATO-O)(2,6-DIHYDROXY-BENZOATO-O,O)TERBIUM(III) AND HOLMIUM(III) DIHYDRATE

Abstract

The structures of isomorphic Tb(III) and Ho(III) complexes with 2,6-dihydroxybenzoic acid of formula [Tb(C₇H₅O₄] 2H₂O and [Ho(C₇H₅O₄)₃ 4H₂O] 2H₂O has been determined by X-ray diffraction and refined to a residual R = 0.030 for 5376 observed reflections and R = 0.0284 for 5660 observed reflections, for Tb(III) and Ho(III) complexes, respectively. Crystals are triclinic, space group P1 with a= 10.748(2), b=11.309(2), c = 12.452(2)Å, α = 82.28(3), ? = 73.05(5), γ = 68.27(3)° for Tb(III) and a= 10.731(2), b=11.269(2), c = 12.436(2)Å, α = 82.25(3), β = 72.92(3), γ = 68.46(3)° for Ho(III).

In the structure of these monomelic complexes the metal ions are coordinated by oxygen atoms of one bidentate chelating and two monodentate carboxylate groups and four molecules of water. Tb-O distances are in the range 2.323(3)-2.506(3) Å and Ho-0 2.297(3)-2.486(3) Å. The crystal structure, consisting of discrete units of neutral complexes with two molecules of water of crystallization is stabilized by intra-and intermolecular hydrogen bonds.     

Spectrophotometry Determination of Arsenic(III) and Antimony(III) by Means of Isonicotinoylhydrazones of 4-Dimethylaminobezaldehyde (4-Dbih) and 2-Hydroxynaphthaldehyde (2-Hnih)

Abstract

4-DBIH and 2-HNIH react with As(III) and Sb(III) respectively, in CH₃COOH medium to form colored complexes stable in presence of EDTA. As(III) and Sb(III) do not react with 2-HNIH and 4-DBIH respectively, and the Sb(III)-2-HNIH complex is extractable into isoamyl alcohol. These behaviours were used for the spectrophotometry determination of As (III) and Sb(III) in presence of several cations.     

Synthese,Kristallstrukturen und Magnetismus von (Hg6As4)[MoCl6]Cl, (Hg6As4)[TiCl6]Cl und (Hg6As4)[TiBr6]Br

Polycationic Hg–As Frameworks with Trapped Anions. II Synthesis, Crystal Structure, and Magnetism of (Hg₆As₄)[MoCl₆]Cl, (Hg₆As₄)[TiCl₆]Cl, and (Hg₆As₄)[TiBr₆]Br (Hg₆As₄)[MoCl₆]Cl is obtained by reaction of Hg₂Cl₂, Hg, As, and MoCl₄ in closed, evacuated glass ampoules in a temperature gradient 450 → 400 °C in form of dark red cubelike crystals. (Hg₆As₄)[TiCl₆]Cl and (Hg₆As₄)[TiBr₆]Br are also formed in closed, evacuated ampoules from Hg₂X₂ (X = Cl, Br), Hg, As, and Ti metal at 275 °C and 245 °C in form of dark green and black crystals, respectively. All three compounds are air and light sensitive. They crystallize isotypically (cubic, Pa 3, a = 1207.8(4) pm for (Hg₆As₄)[MoCl₆]Cl, a = 1209.4(3) pm for (Hg₆As₄)[TiCl₆]Cl, a = 1230.9(3) pm for (Hg₆As₄)[TiBr₆]Br, Z = 4). The structures consist of a three‐dimensionally connected Hg–As framework which is made up of As₂ groups (As–As distance averaged 242 pm) each connected via six Hg atoms to six neighbouring As₂ groups. There are two cavities of different size in the polycationic framework. The bigger cavity is filled with [MoCl₆]^3–, [TiCl₆]^3–, and [TiBr₆]^3– ions of nearly ideal octahedral shape, the smaller cavity with discrete halide ions. The magnetic properties of the two Ti containing compounds are in accordance with a d¹ paramagnetism. The temperature dependence and the magnitude of the magnetic moment can be interpreted with consideration of the spin‐orbit coupling. The so far known representatives of this structure type can be characterised by the ionic formula (Hg₆Y₄)⁴⁺[MX₆]^3–X^– (Y = As, Sb; M = Sb³⁺, Bi³⁺, Mo³⁺, Ti³⁺; X = Cl, Br).