Über Münzmetall‐Quecksilber‐Chalkogenidhalogenide. II Hydrothermalsynthese,Kristallstruktur und Phasenumwandlung von CuHgSCl und CuHgSBr

On Coinage Metal Mercury Chalcogenide Halides II: Hydrothermal Synthesis, Crystal Structure, and Solid State Phase Transition of CuHgSCl and CuHgSBr The hydrothermal reaction of CuCl and CuBr with HgS in concentrated aqueous HX (X = Cl, Br) as solvent at 670 K in sealed glass ampoules yields yellow‐orange crystals of CuHgSCl and CuHgSBr. Both compounds crystallize isotypically (orthorhombic, Pbam, a = 984.01(8), b = 1775.1(2), c = 409.59(3) pm for CuHgSCl and a = 1003.7(4), b = 1833.6(5), c = 412.4(2) pm for CuHgSBr, Z = 8). The structures consist of plane folded HgS chains connected by pairs of distorted CuS₂X₂ tetrahedra sharing the X—X‐edge (X = Cl, Br) in which the copper atoms occupy off‐centered positions. The large displacement factors of the Cu atoms represent thermal vibrations as shown by additional X‐ray investigations at different temperatures. The single‐crystal structure determination shows that the earlier structure model, based on powder diffraction data, is incorrect. The structure type of CuHgSCl und CuHgSBr shows distinct similarities to the structure type of the already known compounds CuHgSeBr, AgHgSBr and AgHgSI (MHgYX). At 323 K CuHgSBr undergoes a second order phase transition into a higher symmetric structure of the MHgYX type (orthorhombic, Pmam, a = 1009.2(3), b = 918.40(4), c = 413.81(2) pm) with halved b‐axis.     

Über Münzmetall‐Quecksilber‐Chalkogenidhalogenide. V1) Solvothermalsynthese und Kristallstruktur der Hochtemperatur‐Modifikation von AgHgSI

On Coinage Metal Mercury Chalcogenide Halides. V. Solvothermal Synthesis and Crystal Structure of the High Temperature Modification of AgHgSI The solvothermal reaction of AgI and α‐HgS in diluted HI as solvent yields yellow crystals of α‐AgHgSI. The compound crystallizes in space group type P2₁2₁2₁ with a = 707.47(1), b = 773.18(2), c = 847.53(2) pm and Z = 4. The structure consists of a distorted hexagonal close packed array of sulphur and iodine, in which one fourth of the tetrahedral voids is occupied by silver and a half of the octahedral voids is occupied by mercury. The distortion of the hexagonal structure is caused by the steric demand of the lone pairs of sulphur and iodine. This could be shown by the calculation of the electron localisation function (ELF). The here described modification of AgHgSI can be obtained at 273 °C from the earlier published β‐AgHgSI and is therefore called α‐AgHgSI.     

Hydrothermalsynthese und Kristallstruktur der Münzmetall‐Quecksilber‐Chalkogenidhalogenide CuHgSeBr,AgHgSBr und AgHgSI

Hydrothermal Synthesis and Crystal Structure of the Coinage Metal Mercury Chalcogenide Halides CuHgSeBr, AgHgSBr, and AgHgSI The hydrothermal reaction of CuBr and HgSe in concentrated aqueous HBr as solvent at 285 °C yields red crystals of CuHgSeBr, the hydrothermal reaction of AgX (X = Br, I) and HgS in half‐concentrated aqueous HX (X = Br, I) as solvent at 300/400 °C yields yellow crystals of AgHgSBr and AgHgSI. The compounds crystallize isotypically (orthorhombic, Pmma, a = 1020.1(3) pm, b = 431.2(1) pm, c = 925.6(3) pm for CuHgSeBr, a = 964.8(8) pm, b = 466.1(4) pm, c = 942.6(6) pm for AgHgSBr und a = 1015.9(2) pm, b = 464.77(5) pm, c = 984.9(2) pm for AgHgSI, Z = 4). The structures consist of plane folded Hg–Y chains connected by pairs of distorted Y₂X₂ terahedra sharing the X–X‐edge (M = Cu, Ag; X = Br, I; Y = S, Se). Atoms of the monovalent metals M have a strongly distorted tetrahedral coordination of two halogen and two chalcogen atoms. The new structure type shows distinct differences in the arrangement of the Hg–Y chains in comparision to the already known CuHgSeCl, but represents the superposition structure of the order‐disorder phase γ‐Hg₃S₂Cl₂.     

Kristallstrukturen „supramolekularer”︁ (Benzo‐18‐krone‐6)kaliumtetrathiocyanatometallate: Ein dimerer Komplex {[K(Benzo‐18‐krone‐6)]2[Hg(SCN)4]}2 und zwei isomere Komplexe [K(Benzo‐18‐krone‐6)][Cd(SCN)3] mit kettenförmigen Trithiocyanatocadmat‐Anionen

Crystal Structures of „Supramolecular”︁ Benzo‐18‐crown‐6 Potassium Tetrathiocyanato Metallates: A Dimeric Complex {[K(Benzo‐18‐crown‐6)]₂[Hg(SCN)₄]}₂ and Two Isomeric Complexes [K(Benzo‐18‐crown‐6)][Cd(SCN)₃] Containing Trithiocyanato Cadmate Anions with Chain Structures By reaction of potassium thiocyanatomercurate(II) complexes with benzo‐18‐crown‐6 (2,3‐benzo‐1,4,7,10,13,16‐hexaoxacyclooctadec‐2‐ene) crystals of {[K(benzo‐18‐crown‐6)]₂[Hg(SCN₄)]}₂ ( 1 ) were obtained. 1 crystallizes monoclinic, space group P2₁/n (non‐standard setting of P2₁/c), a = 1737.35(2), b = 1377.16(2), c = 1984.12(3) pm, β = 100.637(1)°, Z = 2. With potassium tetrathiocyanatocadmate(II) two modifications of a complex [K(benzo‐18‐crown‐6)][Cd(SCN)₃] ( 2 , 3 ), of different symmetry were formed. 2 crystallizes monoclinic, P2₁/c, a = 1158,31(3), b = 1096,55(2), c = 2028,46(2) pm, β = 99,5261(2)°, Z = 4, 3  orthorhombic, P2₁cn, a = 1105,95(3), b = 1413,07(4), c = 1617,10(5) pm, Z = 4. 1 has a dimeric structure, built up from a dication K₂(benzo‐18‐crown‐6)₂]²⁺ and two [K(benzo‐18‐crown‐6)]⁺ cations, which are bridged by two [Hg(SCN)₄]^2– anions. In 2 and 3 triply bridged infinite [{Cd(SCN)₃^–}_n] zigzag chains, stretching along screw axes, are to be found as anions. In 2 these chains exist in two conformations related by inversion symmetry, whereas in 3 only one form can be found. [K(benzo‐18‐crown‐6)]⁺ cations are linked to the anion chains via K · · · S interactions of different lengths.     

Synthese und Kristallstrukturen von (3‐Methylpyridinium)3[DyCl6] und (3‐Methylpyridinium)2[DyCl5(Ethanol)]

Preparation and Structure of (3‐Methylpyridinium)₃[DyCl₆] and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] The complex chlorides (3‐Methylpyridinium)₃[DyCl₆] ( 1 ) and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] ( 2 ) have been prepared for the first time. The crystal structures have been determined from single crystal X‐ray diffraction data. 1 crystallizes in the trigonal space group R3c (Z = 36) with a = 2953.3(3) pm, b = 2953.3(3) pm and c = 3252.5(4) pm, compound 2 crystallizes in the triclinic space group P1 (Z = 2) with a = 704.03(8) pm, b = 808.10(8) pm, c = 1937.0(2) pm, α = 77.94(1)°, β = 87.54(1)° and γ = 83.26(1)°. The structures contain isolated octahedral building units [DyCl₆]^3– and [DyCl₅(Ethanol)]^2–, respectively.     

Synthese und Kristallstrukturen von (2‐Methylpyridinium)3[TbCl6] und (2‐Methylpyridinium)2[TbCl5(1‐Butanol)]

Preparation and Structure of (2‐Methylpyridinium)₃[TbCl₆] and (2‐Methylpyridinium)₂[TbCl₅(1‐Butanol)] The complex chlorides (2‐Methylpyridinium)₃[TbCl₆] (1) and (2‐Methylpyridinium)₂[TbCl₅(1‐Butanol)] (2) have been prepared for the first time. The crystal structures have been determinated from single crystal X‐ray diffraction data. 1 crystallizes in the monoclinic space group C2/c (Z = 8) with a = 3241,2(5) pm, b = 897,41(9) pm, c = 1774,2(2) pm and β = 97,83(2)°, 2 in the monoclinic space group P2₁/n (Z = 4) with a = 1372,96(16) pm, b = 997,57(9) pm, c = 1820,5(2) pm and β = 108,75(1)°. The structures contain isolated octahedral building units [TbCl₆]^3– and [TbCl₅(1‐Butanol)]^2–, respectively.     

Synthese und Kristallstruktur von 2‐Azido‐4,6‐dichloro‐s‐triazin

Synthesis and Crystal Structure of 2‐Azido‐4,6‐dichloro‐s‐triazine Single crystals of 2‐azido‐4,6‐dichloro‐s‐triazine were obtained from a reaction between cyanuric chloride and sodium azide. The structure of this compound was determined by single crystal X‐ray diffraction. 2‐Azido‐4,6‐dichloro‐s‐triazine crystallizes in the orthorhombic space group Pbca (no. 61), Z = 8, a = 746.48(8) pm, b = 952.6(1) pm, c = 2001.6(2) pm. The crystal structure contains (C₃N₃)(N₃)Cl₂ molecules being arranged in a tape‐like fashion, with tapes running along a‐axis direction. The tapes are combined with each other by interlocking azide‐ligands including an angle of approximately 90°. This arrangement leads to the formation of corrugated layers in the crystal structure.     

Phase Transition of a Dicyanamide with Rutile‐like Structure: Syntheses and Crystal Structures of α‐ and β‐Cd[N(CN)2]2

Cadmium dicyanamide Cd[N(CN)₂]₂ was synthesized through aqueous ion exchange at room temperature. A reversible phase transition was detected by in situ X‐ray powder diffractometry above 55 °C. The crystal structures of both phases were determined by X‐ray powder diffraction (β‐Cd[N(CN)₂]₂: T = 22 °C, a = 621.60(3), b = 748.76(4), c = 770.21(5) pm, β = 91.784(3)°, P2₁/n (no. 14), Z = 2, wR_p = 0.063, R_p = 0.050, R_F = 0.059; α‐Cd[N(CN)₂]₂: T = 150 °C, a = 624.62(5), b = 752.92(6), c = 768.30(7) pm, Pnnm (no. 58), Z = 2, wR_p = 0.083, R_p = 0.064, R_F = 0.087). Both polymorphs consist of Cd²⁺ and bent planar [N(CN)₂]^— ions. α‐Cd[N(CN)₂]₂ crystallizes analogously to rutile and is isotypic with M^II[N(CN)₂]₂(M = Mg, Cr, Mn, Co, Ni, Cu). The monoclinic low‐temperature polymorph β‐Cd[N(CN)₂]₂ is closely related to that of the orthorhombic high‐temperature polymorph α‐Cd[N(CN)₂]₂ by a translationengleiche transition of index 2.     

γ‐HIO3 – a Metastable,Centrosymmetric Polymorph of Iodic Acid

From solutions of chromium(III) perchlorate and periodic acid, single crystals of γ‐HIO₃ were obtained and characterized by single‐crystal X‐ray diffraction, Raman spectroscopy and thermal analysis. The compound crystallizes in the orthorhombic crystal system, space group Pbca (a = 563.92, b = 611.10, c = 1507.16 pm). The structure is built up by dimers (HIO₃)₂, which are formed by hydrogen bonds. The crystals are metastable and transform into the stable modification, α‐HIO₃, within a couple of weeks.     

Oxovanadium(IV,V) Complexes with 2‐Acetylpyridine‐2‐furanoylhydrazone (Hapf) as Ligand. X‐Ray Crystal Structures of [VO2(apf)] and [V2O2(μ‐O)2(apf)2]

The preparation of oxovanadium(IV, V) coordination compounds with 2‐acetylpyridine‐2‐furanoylhydrazone (Hapf) is described. [VO(apf)(acac)] was prepared from oxovanadium(IV) diacetylacetonate [VO(acac)₂] by reaction with Hapf in methanol or dichloromethane. The complex is paramagnetic and its EPR spectrum is consistent with an octahedral coordination for the vanadium(IV) atom. Voltammetry studies of [VO(apf)(acac)] indicate an irreversible oxidation, in agreement with the chemical behavior of the compound in solution. The vanadium(IV) complex undergoes slow oxidation in alcoholic solution, losing the acetylacetonate ligand to form [VO₂(apf)] and [V₂O₂(μ‐O)₂(apf)₂]. The crystal structures of these last compounds were determined by X‐ray diffraction methods. [V₂O₂(μ‐O)₂(apf)₂] crystallizes monoclinic [P2₁/c, Z = 2, a = 817.400(10), b = 1650.90(3), c = 984.70(2) pm, β = 112.7190(10)°]. The crystal structure consists of dimeric units, in which two μ‐oxo ligands subtend asymmetric bridges between the vanadium atoms in a very distorted octahedral coordination. In the crystal of [VO₂(apf)], orthorhombic [Pnma, Z = 4, a = 1630.000(10), b = 675.10(4), c = 1136.40(2) pm], the vanadium(V) atom is pentacoordinated.     

Synthese und Kristallstruktur der Rhenium(VII)‐Nitridchloride ReNCl4 und ReNCl4·H2O

Syntheses and Crystal Structures of the Rhenium(VII) Nitride Chlorides ReNCl₄ and ReNCl₄·H₂O Rhenium(VII) nitride chloride, ReNCl₄ ( 1 ) is obtained in form of brown needles with metallic luster by the reaction of ReCl₅ with Cl₃VNCl at 140 °C under vacuum in a sealed glass ampoule. It crystallizes in the tetragonal space group I4 with the lattice parameters a = 826.7(4), c = 405.1(2) pm, and Z = 2. The square pyramidal molecules are connected by asymmetric nitrido bridges to form chains along the crystallographic c axis. The shorter Re‐N distance of 163.0(5) pm corresponds to a triple bond, while the pronounced longer distance of 242.0(5) pm can be interpreted with a weak donor bond. The reaction of ReCl₅ with VN at 170 °C under vacuum in a sealed glass ampoule yields red needles of ReNCl₄·H₂O ( 2 ). It crystallizes in the orthorhombic space group Pnma with a = 1075.4(2), b = 1108.5(2), c = 547.7(5) pm and Z = 4. The Re atoms exhibit a distorted octahedral coordination with the aqua ligand in trans position to the nitrido ligand. The Re‐N triple bond has a bond distance of 166.1(11) pm. The complexes are connected by hydrogen bridges O‐H···N to form chains.     

Pb2(OH)2[p‐O2C‐C6H4‐CO2]: Synthese und Kristallstruktur

Pb₂(OH)₂[p‐O₂C‐C₆H₄‐CO₂]: Synthesis and Crystal Structure Single crystals of Pb₂(OH)₂[p‐O₂C‐C₆H₄‐CO₂] ( 1 ) were obtained by hydrothermal reaction of terephthalic acid and PbCO₃ at 180 °C (10 days). 1 crystallizes in the monoclinic space group P2₁/c with Z = 2 (a = 1115.6(2) pm, b = 380.10(4) pm, c = 1141.3(2) pm, β = 93.39(1)°, V = 0.4831(1) nm³). The crystal structure is characterized by ladder‐type Pb(OH)_3/3 double chains, which are connected to a three‐dimensional framework by terephthalate dianions.     

M(benzo‐18‐crown‐6)I4 (M = Cd,Hg): Tetraiodide,Iodide–Iodine Adduct,or an Inclusion Compound of Iodine in MI2@(benzo‐18‐crown‐6)?

M(benzo‐18‐crown‐6)I₄ (M = Cd, Hg) are obtained as red columnar crystals from the reactions of benzo‐18‐crown‐6 (b18c6), cadmium and mercury iodide, respectively, and iodine in molar ratios of 1:1:2 in acetonitrile. They both crystallize with the orthorhombic crystal system, P2₁2₁2₁, a = 833.7(1), b = 1610.9(1), c = 1846.8(1) pm, V = 2480.3(1) 10⁶·pm³, Z = 4, for M = Cd and a = 823.4(1), b = 1616.5(1), c = 1866.1(1) pm, V = 2483.8(2) 10⁶·pm³ for M = Hg. The crystal structures consist of [M(b18c6)]I₂ molecules which are connected to a slightly lengthened iodine molecule via a secondary contact, according to the formulation I₂@[MI₂@(b18c6)].     

Syntheses,Characterization and X‐Ray Structures of the first Copper(I) and Silver(I) Complexes with ATT (ATT = 6‐Aza‐2‐thiothymine)

The reaction of copper(I) chloride with 6‐aza‐2‐thiothymine (ATT, 1 ) and triphenylphosphane in methanol/chloroform gives [(ATT)CuCl(PPh₃)] ( 2 ) as a neutral complex. [(ATT)Ag(NO₃)(PPh₃)₂]·MeOH ( 3 ) can be obtained by the reaction of 1 with silver(I) nitrate and triphenylphosphane in methanol/chloroform in excellent yields and the single crystals of 3 can be obtained from acetonitril solution. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at —80 °C: space group I2/a with a = 1859.3(1), b = 1143.2(1), c = 2208.2(1) pm, β = 104.84(1)°, Z = 8, R₁ = 0.0355 and for 3 at —80 °C: space group P2₁/c with a = 1344.1(1), b = 1553.6(1), c = 1977, 3(3) pm, β = 105.26(1)°, Z = 4, R₁ = 0.0436.     

Pb(18‐crown‐6)Cl2 and Hg(18‐crown‐6)I2: Molecular Dihalides Trapped in a Crown Ether

Pb(18‐crown‐6)Cl₂ and Hg(18‐crown‐6)I₂ are obtained as transparent colourless crystals of needle and hexagonal shape, respectively, by isothermal evaporation of their dichloromethane solutions. Pb(18‐crown‐6)Cl₂ crystallizes with the trigonal crystal system [ , no. 148, a = b = 1176.3(2), c = 1191.8(3) pm, V = 1428.2(5) 10⁶·pm³, Z = 3] whereas Hg(18‐crown‐6)I₂ crystallizes with the orthorhombic crystal system (Pnma, no. 62, a = 1613.9(2) pm, b = 2822.2(5) pm, c = 841.3(1) pm, V = 3832(1)10⁶·pm³, Z = 8). Both compounds are characterized by linear MX₂ (HgI₂ or PbCl₂) molecular units which are encrypted by the crown ether. In both cases, the divalent metal ion resides in the middle of the crown ether resulting in a hexagonal bipyramidal coordination environment for the metal cations. The molecular symmetry comes close to D_3d. Hg(18‐crown‐6)I₂ and Pb(18‐crown‐6)Cl₂ differ in the way the single MX₂@18‐crown‐6 units are packed. Whereas the Hg(18‐crown‐6)I₂ molecules are arranged in a (distorted) cubic closest packing, the Pb(18‐crown‐6)Cl₂ molecules adopt a hexagonal closest packing.     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][NdCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][NdCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][NdCl₄(H₂O)₂] was prepared for the first time and the crystal structure was determined by X‐ray methods from single crystals. The compound crystallizes in the orthorhombic space group Cmca (Z = 8) with a = 1793.5(2) pm, b = 936.6(2) pm and c = 1232.8(2) pm. The anionic part of the structure is built up by chains of edge connected [NdCl_4/2Cl₂(H₂O)₂]^– trigondodecahedra. In order to study the interactions between the neodymium cation and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Komplexe einwertiger Dibenzo‐18‐Krone‐6‐Kationen mit Triiodid als Anionen

Complexes of Monovalent Dibenzo‐18‐crown‐6 Cations with Triiodide as Anions The new polyiodides [NH₄(db18c6)]₂(I₃)₂ ( 1 ), [NH₄(db18c6)](db18c6)I₃ ( 2 ), [Na_1/2(db18c6)H₂O]₂I₃ ( 3 ), [Rb(db18c6)]I₃ ( 4 ), [Rb(db18c6)]₂(I₃)₂ ( 5 ), [Cs(db18c6)]I₃ ( 6 ), and [Cs₂(db18c6)₃][Cs(db18c6)_3/2](I₃)₃ ( 7 ) were obtained from reactions of dibenzo‐18‐crown‐6 (db18c6) and iodine with NH₄I, NaI, RbI, and CsI. Their crystal structures were determined by single‐crystal X‐ray diffraction. ( 1 ) M = NH₄, ( 5 ) M = Rb: monoclinic, P2₁/n, a = 1409,67(8), b = 2211,63(14), c = 1627,16(10) pm, β = 101,030(5)°, Z = 4 (crystal data for M = NH₄); ( 2 ): monoclinic, Pn, a = 1345,26(14), b = 773,82(4), c = 2095,10(20) pm, β = 94,439(8)°, Z = 2; ( 3 ): orthorhombic, Pnaa, a = 931,59(13), b = 2213,3(5), c = 2223,9(4) pm, Z = 4; ( 4 ): monoclinic, P2₁/n, a = 999,50(6), b = 1711,33(10), c = 1517,45(9) pm, β = 99,021(5)°, Z = 4; ( 6 ): triclinic, , a = 705,16(9), b = 1137,93(14), c = 1678,90(20) pm, α = 73,719(10), β = 79,782(10), γ = 83,669(10)°, Z = 2; ( 7 ): triclinic, , a = 1519,25(6), b = 1702,49(7), c = 2136,41(9) pm, α = 102,641(3), β = 101,989(3), γ = 91,911(3)°, Z = 2. 1 : 1 cations centered by M, [M(db18c6)]⁺, are found in the structures of ( 1 – 6 ). In contrast, the triple decker cation found in ( 7 ) is less common. The crystal structures are completed by mostly asymmetrically linear I₃^? anions.     

Tetra(N,N′‐tetramethylharnstoff)‐Beryllium‐Triiodid, [Be(TMH)4](I3)2

Tetra(N,N′‐tetramethylurea)‐beryllium‐triiodide, [Be(TMU)₄](I₃)₂ ( 1 ) was prepared from beryllium powder and iodine in N,N′‐tetramethylurea to give orange crystals, which were characterized by X‐ray diffraction and IR spectroscopy. Compound 1 crystallizes monoclinically in the space group C2/c with four formula units per unit cell. Lattice dimensions at 100(2) K: a = 1906.6(1), b = 1185.7(1), c = 1895.0(1) pm, β = 113.60(1) °, R₁ = 0.0291. The structure of 1 consists of distorted tetrahedral cations [Be(TMU)₄]²⁺ with Be–O bond lengths of 162.5(5) and 160.8(5) pm and triiodide ions without site symmetry.     

Synthese und Eigenschaften von Ph3Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph3SnO)4Te(OH)2] und trans‐[(Ph3SnO)2Te(OMe)4]

The reaction of Te(OH)₆ with Ph₃SnOH in ethanol leads to the formation of trans‐[(Ph₃SnO)₄Te(OH)₂] ( 1 ). Compound 1 crystallizes triclinic in the space group P\bar{1} with a = 996.6(2) pm, b = 1365.4(3) pm, c = 1368.2(3) pm and α = 71.15(2)°, β = 71.48(2)°, γ = 74.81(3)° (at 220 K). The molecular structure of 1 consists of a tellurium atom, which is coordinated nearly octahedrally by four Ph₃SnO units and two hydroxyl groups that are trans to each other. The Te–O bond lengths are in the range of 190.5(2) and 193.7(2) pm. Treatment of 1 with methanol under reflux yields trans‐[(Ph₃SnO)₂Te(OMe)₄] ( 2 ). Compound 2 crystallizes triclinic in the space group P\bar{1} with a = 1012.8(1) pm, b = 1422.4(2) pm, c = 1618.1(2) pm, and α = 100.44(1)°, β = 107.92(1)°, γ = 110.66(1)° (at 220 K). 2 forms centrosymmetric molecules in which the tellurium atom is surrounded nearly octahedrally by four methoxy groups and two trans arranged Ph₃SnO units. The Te–O bond lengths of 187.9(3)–194.5(3) pm are similar to those observed in 1 .     

Synthesis and Crystal Structure of AgCuVO4

Dark red single crystals of AgCuVO₄ were obtained from hydroxide fluxes in Ag‐containers at 430 °C. According to X‐ray diffraction data AgCuVO₄ crystallizes in the orthorhombic space group Pnma (Z = 4, a = 925.5(1) pm, b = 677.8(1) pm, c = 540.1(1) pm, wR2 = 0.0753). The Pearson code (oP28) and Wyckoff sequence (dc⁴a) indicate that AgCuVO₄ is related to the olivine‐type of structure, but the first coordination sphere of Ag^I and Cu^II differ significantly from the C.N. 6 with irregular square‐pyramidal [AgO₅] polyhedra and distorted square‐planar [CuO₄] units. These differences in crystal chemistry are discussed and MAPLE as well as ECoN values are given.