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Unusual 4‐arsonoanilinium cationic species in the hydrochloride salt of (4‐aminophenyl)arsonic acid and formed in the reaction of the acid with copper(II) sulfate, copper(II) chloride and cadmium chloride
Author(s) -
Smith Graham,
Wermuth Urs D.
Publication year - 2017
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s205322961700314x
Subject(s) - chemistry , chloride , copper , protonation , sulfate , cationic polymerization , hydrogen bond , copper chloride , inorganic chemistry , coordination polymer , medicinal chemistry , hydrochloride , crystal structure , crystallography , molecule , polymer chemistry , ion , organic chemistry
Structures having the unusual protonated 4‐arsonoanilinium species, namely in the hydrochloride salt, C 6 H 9 AsNO 3 + ·Cl − , (I), and the complex salts formed from the reaction of (4‐aminophenyl)arsonic acid ( p ‐arsanilic acid) with copper(II) sulfate, i.e. hexaaquacopper(II) bis(4‐arsonoanilinium) disulfate dihydrate, (C 6 H 9 AsNO 3 ) 2 [Cu(H 2 O) 6 ](SO 4 ) 2 ·2H 2 O, (II), with copper(II) chloride, i.e. poly[bis(4‐arsonoanilinium) [tetra‐μ‐chlorido‐cuprate(II)]], {(C 6 H 9 AsNO 3 ) 2 [CuCl 4 ]} n , (III), and with cadmium chloride, i.e. poly[bis(4‐arsonoanilinium) [tetra‐μ‐chlorido‐cadmate(II)]], {(C 6 H 9 AsNO 3 ) 2 [CdCl 4 ]} n , (IV), have been determined. In (II), the two 4‐arsonoanilinium cations are accompanied by [Cu(H 2 O) 6 ] 2+ cations with sulfate anions. In the isotypic complex salts (III) and (IV), they act as counter‐cations to the {[CuCl 4 ] 2− } n or {[CdCl 4 ] 2− } n anionic polymer sheets, respectively. In (II), the [Cu(H 2 O) 6 ] 2+ ion sits on a crystallographic centre of symmetry and displays a slightly distorted octahedral coordination geometry. The asymmetric unit for (II) contains, in addition to half the [Cu(H 2 O) 6 ] 2+ ion, one 4‐arsonoanilinium cation, a sulfate dianion and a solvent water molecule. Extensive O—H…O and N—H…O hydrogen bonds link all the species, giving an overall three‐dimensional structure. In (III), four of the chloride ligands are related by inversion [Cu—Cl = 2.2826 (8) and 2.2990 (9) Å], with the other two sites of the tetragonally distorted octahedral CuCl 6 unit occupied by symmetry‐generated Cl‐atom donors [Cu—Cl = 2.9833 (9) Å], forming a two‐dimensional coordination polymer network substructure lying parallel to (001). In the crystal, the polymer layers are linked across [001] by a number of bridging hydrogen bonds involving N—H…Cl interactions from head‐to‐head‐linked As—O—H…O 4‐arsonoanilinium cations. A three‐dimensional network structure is formed. Cd II compound (IV) is isotypic with Cu II complex (III), but with the central CdCl 6 complex repeat unit having a more regular M —Cl bond‐length range [2.5232 (12)–2.6931 (10) Å] compared to that in (III). This series of compounds represents the first reported crystal structures having the protonated 4‐arsonoanilinium species.