π-Complexes of copper(I) halides with 3-(allylamino)-(C3H5NHC2H4CN, Apn) and 3-(diallylamino)-((C3H5)2NC2H4CN, Dapn)-propanenitrile. syntheses and crystal structures of compounds [CuCl(Apn)], [(H+Apn)Cu2Cl3], [(H+Dapn)CuCl2], and [(H+Dapn)CuBr2]

3-(diallylamino)propanenitrile ((C3H5)2NC2H4CN, L) π-complexes with copper(I) ionic salts. Syntheses and crystal structures of compounds [Cu(H+L)ClO4]ClO4 · H2O, [Cu(H+L)BF4]BF4 · H2O, and [Cu(H+L)(H2O)]SiF6 · H2O

“…One more O (I) or F (II) atom of another independent (I) or (II) anion is significantly remote from the copper(I) atom by 2.899(7) Å (for complex I) or 2.950(7) Å (in structure II). In the structures of com pounds I and II, the both Cu(I)-middle of C=C bond distances differ slightly: 1.994(6), 2.012(6) Å (І) and 1.997 (6) There are two substantial distinctions in the organi zation of the coordination environment of the metal atom in the recently studied cuprohalide complexes with the considered ligand Cu(H + L)X 2 , X = Cl, Br (IV) [16] and that in complexes I-III. (1) Unlike halide complexes IV, where one of the C=C bonds of H + L is coordinated by the metal atom, the both olefin bonds are coordinated by the chelating mode to Cu(I) in considered compounds I-III.…”

“…We have recently synthesized and structurally stud ied the first π complexes of copper(I) halides with N mono and N diallyl derivatives of aminopro panenitriles [16]. In this work, we present the results of the syntheses and X ray single crystal study of the π complexes of Cu(I) ionic salts with 3 (dially lamino)propanenitrile (L) of the composition 3 (Diallylamino)propanenitrile was synthesized by the heating with a reflux condenser of acrylonitrile (Merck) (7 mL, 0.11 mol) and dial lylamine (Aldrich) (16 mL, 0.13 mol) in a water bath at 50-60°С for 8 h followed by keeping the reaction mixture at ambient temperature for 48 h [17].…”

Synthesis and Structure of [Cu(Hapn)]NO3]NO3, [Cu(Hapn)(H2O)2]SiF6, [Cu(Hapn)(H2O)BF4]BF4∙H2O and [Cu(Hapn)(NH2SO3)2] π-complexes (apn = 3-(prop-2-en-1-ylamino)propanenitrile)

“…For comparison, the analogous angle between planes passing through two neighbouring inorganic units [CuCl] 2 in the halide complex is 65°. 16 The metal atom possesses a tetrahedral surrounding consisting of the middle (further m) of double C(5)=C(6)-bond, N (C≡N-group) and 2 oxygen atoms from two NO 3 - Table 2). The angle formed by three Cu atoms in the chain [Cu(Hapn) 2+ ] n equals to 152°.…”

“…It has been noticed that atoms of Cl or Br compete for space in coordination polyhedron with allyl groups and cyano group in the halide complexes of Cu(I) with diallylaminopropanenitrile (the tertiary amine N-atom is protonated). 16,17 Still one of the two olefin bonds and halide atoms have a priority, and CN-group (as well as the second C=C-bond) does not coordinate to the metal ion.…”

“…Depending on the status (cation or molecular) of 3-(prop-2-en-1-ylamino)propanenitrile the number of active groups for coordination changes, which, in turn, influences the composition of coordination polyhedron of the Cu ion (other ligand moieties, such as sol-vent molecules or anions, occupy usually the apical position of the coordination polyhedron) and complexity of the arisen inorganic component in a compound: from (CuCl) 2 to (Cu 2 Cl 3 ) n n-. 16 Thus, being in molecular state, apn is coordinated to Cu with allyl-and amino-group and Cl -in the following sequence (C=C ≥ NH >…), whereas C≡N-group is not coordinated. Cationic form of apn provides these groups the same chance to be coordinated with the metal atom: C=C ≥ C≡N > Hal.…”