π-Complexes of Copper(I) Ionic Salts: Synthesis and Crystal Structure of (4-Allylthiosemicarbazide)(sulfamato)copper(I) and Bis(4-allylthiosemicarbazide)(sulfato-O)dicopper(I)

Abstract

Single crystals of [Cu(ATSC)]NH 2 SO 3 (1) (ATSC ±4-allylthiosemicarbazide) were obtained by electrochemical synthesis using alternating current. Compound (1) crystallizes in P2 1 2 1 2 1 sp. gr., a = 6.8284(2), b = 9.3054(3), c = 16.1576(11) A Ê , Z = 4. ATSC moiety acts as tetradentate ligand, chelating two symmetrically related copper atoms. The Cu atom possesses trigonal pyramidal coordination, formed by two sulphur atoms (one of them at the apical position), nitrogen atom and C=C bond. Sulfamate anion is associated via hydrogen bonds. By slow hydrolysis of 1 crystals of [Cu 2 (ATSC) 2 ]SO 4 (2) were obtained: P 1 sp. gr., a = 9.526(2), b = 12.687(2), c = 14.7340(10) A Ê , a = 95.119(10), b = 89.903(12), c = 109.113(14)°, Z = 4. The asymmetric unit of 2 contains two formula units, which are related by pseudosymmetry via a glide plane a. One half of four ATSC molecules act as in 1, the rest as tridentate ligands, which coordinate the two copper atoms in apical positions with sulfate anions. This Cu±S coordination was to date unknown. The structure of the ATSC ligands contributes to the unexpected competitiveness of C=bond in the coordination sphere of Cu I inspite of strong donor atoms. Die p-Komplexe von Kupfer(I)-ionischen Salzen: Die Darstellung und die Kristallstrukturen von (4-Allylthiosemicarbazid)(sulfamato)kupfer(I) und Bis(4-allylthiosemicarbazid)(sulfato-O)dikupfer(I) Inhaltsu È bersicht. Einkristalle von [Cu(ATSC)]NH 2 SO 3 (1) (ATSC±4-allylthiosemicarbazid) wurden durch die elektrochemische Synthese unter Anwendung von Wechselstrom erhalten. Die Verbindung kristallisiert in der Raumgruppe P2 1 2 1 2 1 : a = 6.8284(2), b = 9.3054(3), c = 16.1576(11) A Ê , Z = 4. Die ATSC-Einheit wirkt als vierza È hniger Ligand, die mit den zwei symmetrisch verbundenen Kupferatomen verbru È ckt ist. Das Kupferatom hat trigonal-pyramidale Umgebung mit zwei Schwefelatomen (eines axial), ein Stickstoffatom und eine C=C-Bindung. Das Sulfamatanion ist u È ber Wasserstoffbru È ckenbindungen assoziiert. Durch langsame Hydrolyse der Verbindung 1 wurden Einkristallen von [Cu 2 (ATSC) 2 ]SO 4 (2) gewonnen: Raumgruppe P 1, a = 9.526(2), b = 12.687(2), c = 14.7340(10) A Ê , a = 95.119(10), b = 89.903 (12), c = 109.113(14)°, Z = 4. Die asymmetrische Einheit der Elementarzelle von 2 entha È lt zwei mit der Pseudosymmetrie u È ber die Gleitspiegelebene a verbundene Formeleinheiten. Die Ha È lfte der vier ATSC-Moleku È le wirkt wie in 1, der andere Teil als dreiza È hniger Ligand, der die zwei Kupferatome in den Axialpositionen mit den Sulfatanionen koordiniert. Die Struktur der ATSC-Liganden tra È gt zu der unerwarteten Konkurrenzfa È higkeit der C=C-Bindung in der Koordinationsspha È re des Cu I trotz starker Donoratome bei. Die stereochemische Besonderheit dieser Cu±S-Koordination war bisher nicht bekannt.

Crystal structure of bis[μ-N-(η2-prop-2-en-1-yl)piperidine-1-carbothioamide-κ2 S:S]bis[(thiocyanato-κN)copper(I)]

“…A survey for a Cu complex containing the 1-allylthiourea fragment as a S-coordination ligand reveals 53 examples, which includes six examples of 2 --coordination of an allyl group to Cu. All of these six examples are Cu I complexes, which comprise four coordination polymers of 4allyl-semicarbazide as ligands (Mel'nyk et al, 2001(Mel'nyk et al, , 2011Olijnik et al, 2011), one coordination polymer of 1,3-diallylthiourea as ligand (BOGNUH; Vakulka et al, 2007), and one discrete centrosymmetric dimer of 1-allylthiourea as ligand (RENNON; Filinchuk et al, 1996).…”

Sulfamic Acid and Its N- and O-Substituted Derivatives

“…Structures have also been reported for the double salts MLi(NH 2 SO 3 ) 2 , where M = K, Rb, and Cs, 22 CsNHSO 3 H•NH 2 SO 3 H, 23 and (NH 4 ) 2 SO 4 •NH 2 SO 3 H. 24 Structures of Me 2 NCHN + HSO 3 − generated from reaction of DMF and the putative N-sulfonylamine, NHSO 2 (see section 2.13), has been reported 25 and of the 1:1 complex between benzo-18-crown-6 and sulfamic acid. 26 Structures of the copper π-complexes [Cu(NH 2 SO 3 ) 2 ]• (C 3 H 8 N)(H 2 O) 27 and [(CH 2 CHCH 2 ) 2 N−CHO](Cu-(NH 2 SO 3 ) 2 (H 2 O) 28 and the 4-allylthiosemicarbazide complex [Cu(CH 2 CHCH 2 NHNHCSNH 2 )]NH 2 SO 3 29 have been determined. A crystal structure has been reported for p-nitrobenzoxasulfamate monohydrate 1, and differential thermal analysis (DTA) and thermal gravimetric (TG) studies are also given, 30 and an X-ray structure of the first metal complex of 1, namely, triaquabis(p-nitrobenzoxasulfamato)copper(II) monohydrate, has been determined by the same group.…”

“…143,144 The interdiffusion coefficients of aqueous nickel sulfamate solutions have been studied 1 4 5 , 1 4 6 The pentamminecobalt(III) complexes, [(NH 3 ) 5 CoNHSO 3 ]ClO 4 and [(NH 3 ) 5 CoNH 2 SO 3 ](ClO 4 ) 2 , have been investigated. 147 Three papers from the same Ukranian group on copper(I) sulfamate π complexes report on the synthesis and crystal 29 and two copper(I) complexes with N-allyl derivatives of piperazinium sulfamate. 148 A study of the synthesis of stannous sulfamate has been published.…”

“…Two different preparations of nickel sulfamate have been reported. , The interdiffusion coefficients of aqueous nickel sulfamate solutions have been studied , The pentamminecobalt(III) complexes, [(NH 3 ) 5 CoNHSO 3 ]ClO 4 and [(NH 3 ) 5 CoNH 2 SO 3 ](ClO 4 ) 2 , have been investigated . Three papers from the same Ukranian group on copper(I) sulfamate π complexes report on the synthesis and crystal structures of [((CH 2 CHCH 2 ) 2 NCHO)Cu(NH 2 SO 3 )(H 2 O), Cu(4-allylthiosemicarbazide)]NH 2 SO 3 , and two copper(I) complexes with N -allyl derivatives of piperazinium sulfamate…”

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

“…The study of the π complex formation of copper(I) with various heteroatomic ligands shows that the type of the anion of the Cu(I) salt exerts a substantial effect on the efficiency of the formed Cu(I)-(C=C) bond [13][14][15].…”