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The reactions of equimolar amounts of tetraorganylphosphonium chloride with 2,5-dichlorobenzenesulfonic, 2,4-dinitrobenzenesulfonic, and 2-carboxybenzenesulfonic acids in water afford organyltriphenylphosphonium organosulfonates [Ph3PR][OSO2R'] (R = Ph, R' = C6H3Cl2-2,5 (I); R = C6H11-cyclo, R' = C6H3Cl2-2,5 (II); R = CH2OMe, R' = C6H3(NO2)2-2,4 (III); R = CH2OMe, R' = C6H4(COOH-2) (IV)). According to the X-ray diffraction (XRD) data (CIF files ССDС nos. 2142598 (I), 2144330 (II), 2144708 (III), and 2145604 (IV)), the complexes are ionic. The phosphorus atoms in the cations of complexes I‒IV are characterized by the tetrahedral coordination, and the organosulfonate anions have the usual geometry with the tetrahedral sulfur atom. The Р−С bond lengths are 1.7665(18)−1.836(2) Å, and the СРС bond angles vary in a range of 103.81(6)°−113.43(7)°. The structural organization in the crystals of complexes I−IV is formed by numerous weak hydrogen bonds between the cations and anions, such as S=O···H−CAr, N=O···H−CAr, C=O···H−CAr, etc. The arenesulfonate anions in complex I are structured into dimers by molecules of water of crystallization. [ABSTRACT FROM AUTHOR]

Ionic organyl-triphenylphosphonium 2,4-dinitrobenzenesulfonates [Ph3PR][OSO2C6H3(NO2)2-2,4], R = CH2OMe (1), CH2CN (2), CH2CH = CHCH2PPh3 (3) are prepared by the reaction of organyl-triphenylphosphonium halides with 2,4-dinitrobenzenesulfonic acid in water and are structurally characterized. According to the XRD data, the phosphorus atoms in cations 1-3 have a distorted tetrahedral coordination, the sulfonate anions have a usual geometry with a sulfur atom in a tetrahedral environment. The lengths of P–C bonds vary within 1.742(2)-1.872(2) Å; the CPC bond angles fall within 104.92(6)-113.43(11)°. In the arenesulfonate anions of the complexes, the S–C distances are close to each other (1.743(2)-1.806(3) Å), all the S–O bonds are almost equal (1.4324(15)-1.477(2) Å). The [Ph3PCH2CH=CHCH2PPh3]+ cations of complex 3 contain second-order rotation-reflection axes passing through the centers of the C=C double bonds (point group C2h). The structures of 1, 3 contain short CAr⋯H(Ph) contacts (CH⋯π interactions) (2.829 Å (1), 2.769 Å (3)). The structures of 1-3 are mainly determined by weak intermolecular O⋯H contacts 2.30-2.61 Å (1), 2.23-2.68 Å (2), 2.35-2.69 Å (3). [ABSTRACT FROM AUTHOR]