Crystal structures of allyltriphenyl-phosphonium halogenocuprates(I)

Alternating-current electrochemical synthesis is used to obtain for the first time halogenocuprates of an allyl derivative of phosphonium of the composition (CH₂=CHCH₂(C₆H₅)₃P)CuX₂ (X = Br (I), Cl (II)). Compound I crystallizes in the space group P2₁, a = 9.6341(3) Å, b = 12.4167(4) Å, c = 9.9618(4) Å, β = 117.484(5)°, Z = 2. Compound II crystallizes in the space group P2₁/n, a = 9.9725(5) Å, b = 15.4586(8) Å, c = 13.7557(5) Å, β = 90.429(4)°, Z = 4. In the structures of I and II quasilinear CuX ₂ ^? anions are held by C-H…X hydrogen bonds inside a framework formed by the stacking of phenyl groups from CH₂=CHCH₂(C₆P₅)₃P⁺ cations. Allyl groups are not involved in coordination with copper(I) atoms.     

Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))]

Reactions of a solution of AgNO₃ in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO₃ to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag₂(C₄H₈N₂(C₃H₅)₂(H⁺)₂)(H₂O)₂(NO₃)₂](NO₃)₂ (I) and [Ag(C₆H₄N₃(OC₃H₅)(NO₃))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P2₁/c; for I: a = 7.053(3)Å, b = 9.389(3)Å, c = 15.488(4)Å, β = 91.60°, V = 1025.3(6)ų, Z = 4; for II: a = 10.650(4)Å, b = 15.062(5)Å, c = 7.412(4)Å, β = 104.20(3)°, V = 1152.6(8)ų, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO₃ 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO ₃ ^? bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.     

Zwitterionic [(H3NCH2C≡CC≡CCH2NH3)]Cu2Cl4 π-Complex: Template Synthesis and Crystal Structure

Crystals of the [(H₃NCH₂CCCCCH₂NH₃)]Cu₂Cl₄ -complex, formed in the oxidative dimerization of propargylammonium cations, were obtained by ac electrochemical synthesis from CuCl₂ · 2H₂O and propargylammonium chloride ([CCCH₂NH₃]Cl) and studied by X-ray diffraction analysis (DARCh automated diffractometer, MoK radiation, /2 scan mode; 2275 reflections with F 4(F), R = 0.048). Crystals are monoclinic: space group B2/b, a = 19.591(6) Å, b = 7.299(3) Å, c = 8.636(3) Å, = 106.83(3)°, Z = 4. The structure consists of individual [(H₃NCH₂CCCCCH₂NH₃)]Cu₂Cl₄ moietes united through the elongated Cu···Cl contacts (2.827(5) Å) into chains oriented along the [010] direction. The bond of the centrosymmetric propargylammonium dimer is -coordintated by copper(I) atom and is elongated to 1.227(6) Å.     

Copper(I) Acetylenide π-Complexes. Synthesis and Structure of Cluster Compound HAmp[Cu9Cl8(C≡CCH2OH)2] (HAmp is 4-Aminopyridinium Cation)

Crystals of the HAmp[Cu₉Cl₈(CCCH₂OH)₂] cluster compound (HAmp is the 4-aminopyridinium cation (NH₂–C₅H₄NH)⁺) were obtained through ac electrochemical synthesis and their structure was determined using X-ray diffraction analysis (DARCh autodiffractometer, /2 scan mode, 3435 independent reflections with F 4(F), R = 0.047). The crystals are triclinic: space group P , a = 12.547(5) Å, b = 12.502(4) Å, c = 8.201(2) Å, = 75.93(2)°, = 82.21(3)°, = 76.05(3)°, V = 1207(2) ų, Z = 2. Two crystallographically independent moieties ^–(CCCH₂OH) were detected in the complex structure. Each moiety acts as a double bridging ,-ligand and binds four or five Cu(I) atoms, thus forming the [Cu₄(CCCH₂OH)] and [Cu₈(CCCH₂OH)₂] clusters. The shortest Cu···Cu distance is equal to 2.337(4) Å.     

Zwitterionic copper(I) π-complexes with monosubstituted alkynes. Synthesis and X-ray diffraction study of a π-complex of copper(I) chloride with 4-ethynyl-4-hydroxy-2,2,6,6-tetramethylpiperidinium chloride

The first mononuclear π-complex of copper(I) chloride with monosubstituted alkyne of the formula [(C₉H₁₆NH₂(OH)C≡CH)CuCl₂] was obtained in the system CuCl-HCl-H₂O-(C₉H₁₆NH₂(OH)C≡CH)Cl (C₉H₁₆NH ₂ ⁺ (OH)C≡CH is the 4-ethynyl-4-hydroxy-2,2,6,6-tetramethylpiperidinium cation) and studied by single-crystal X-ray and X-ray powder diffraction. The crystals are monoclinic: a = 16.868(8) Å, b = 13.177(8) Å, c = 13.32(1) Å, γ = 103.50(4)°, space group P2₁/b, Z = 8. The structure of the complex contains two crystallographically independent zwitterionic entities of the formula [(C₉H₁₆NH₂(OH)C≡CH)CuCl₂], which result from π-coordination of the potential π-bidentate bond C≡C of the organic cation to one Cu(I) atom of the inorganic anion CuCl ₂ ^? . The distances Cu-m (m is the midpoint of the C≡C bond) are 1.91(2) Å. Along with weak intermolecular hydrogen bonds ≡CH...Cl and intramolecular contacts OH...Cl, the structure is stabilized by a directed ionic interaction through strong NH...Cl bonds.