Supramolecular interactions in 2,6-diamino-4-chloropyrimidin-1-ium 5-chlorosalicylate and bis(2,6-diamino-4-chloropyrimidin-1-ium) naphthalene-1,5-disulfonate

Abstract

The crystals of two new salts, 2,6-diamino-4-chloropyrimidin-1-ium 5-chlorosalicylate, C 4 H 6 ClN 4 + ÁC 7 H 4 ClO 3 À , (I), and bis(2,6-diamino-4-chloropyrimidin-1-ium) naphthalene-1,5-di-sulfonate, 2C 4 H 6 ClN 4 + ÁC 10 H 6 O 6 S 2 2À , (II), have been synthesized and characterized by single-crystal X-ray diffraction. In both compounds, the N atom of the pyrimidine group in between the amino substituents is protonated and the pyrimidinium cation forms a pair of N-HÁ Á ÁO hydrogen bonds with the carboxylate/sulfonate ion, leading to a robust R 2 2 (8) motif (supramolecular heterosynthon). In compound (I), a selfcomplementary base pairing involving the other pyrimidinium ring nitrogen atom and one of the amino groups via a pair of N-HÁ Á ÁN hydrogen bonds [R 2 2 (8) homosynthon] is also present. In compound (II), the crystallographic inversion centre coincides with the inversion centre of the naphthalene-1,5-disulfonate ion and all the sulfonate O atoms are hydrogen-bond acceptors, generating fused-ring motifs and a quadruple DDAA array. A halogen-bond (ClÁ Á ÁCl) interaction is present in (I) with a distance and angle of 3.3505 (12) Å and 151. 37 (10) , respectively. In addition, a C-ClÁ Á Á interaction and ainteraction in (I) and a -interaction in (II) further stabilize these crystal structures.

Insights on structure and interactions of 2-amino-4-methoxy-6-methylpyrimidinium salts with 4-aminosalicylate and 5-chlorosalicylate: a combined experimental and theoretical charge–density analysis

“…2). The hydroxy group of 5-chlorosalicylic acid is deprotonated and the proton transferred to the N atom of 2-aminopyrimidine (Ebenezer & Muthiah, 2012;Kantouch et al, 2013;Jeevaraj et al, 2018;Darious & Muthiah, 2018). In the cation, one of the pyrimidine N atoms (N1) is protonated and this is confirmed from the increase of the bond angle at N1 [C2-N1-C1 = 121.7 ( 2) ].…”

“…5-Chlorosalicylic acid (5ClSA) and has found many applications in medical and pharmaceutical research and industry, particularly in the treatment of acne, psoriasis, calluses, corns, keratosis pilaris and warts (Ray et al, 2012). 5-Chlorosalicylic acid is presently finding use in the cosmetics industry (Swinton Darious et al, 2018). The salts 2-amino-4-methoxy-6-methyl- Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS (Sheldrick, 2008), SHELXT2014 (Sheldrick, 2015a), OLEX2 (Dolomanov et al, 2009), PLATON (Spek, 2020), Mercury (Macrae et al, 2020), ORTEP-3 for Windows (Farrugia, 2012), SHELXL2014 (Sheldrick, 2015b) and WinGX (Farrugia, 2012).…”

2-Amino-4-(4-methoxyphenyl)-6-(4-methylphenyl)pyrimidin-1-ium chloride

“…As a continuation of our research program to expand the use of novel synthetic chalcones (Lee et al 2016), the title aminopyrimidine compound was synthesized from chalcone and its crystal structure was determined. Other examples of aminopyrimidinium salt structures have been published recently (Swinton Darious et al, 2018;Jeevaraj et al, 2016).…”

Insights into the interactions between salt molecules: A combined experimental and computational study

“…5-Chlorosalicylic acid (5ClSA) is a potential candidate have found enormous application in medical and pharmaceutical research and industry, particularly in the treatment of acene, psoriasis, calluses, corns, keratosis pilaris and warts [22]. 5-Chlorosalicylic acid is presently nding burgeoning use in cosmetic industry [23]. The title salts, namely, 2-amino 4-methoxy 6-methyl pyrimidinium 4-amino salicylate (2A4M6MP-4AMSA) (I), and 2-amino 4-methoxy 6-methyl pyrimidinium 5-chloro salicylate (2A4M6MP-5ClSA) (II), have been investigated in order to study the hydrogen bonding patterns and supramolecular architectures in the crystalline state.…”

“…[18,23,49,55]. In the cation, one of the pyrimidine nitrogen atoms (N1) is protonated and this is con rmed from the increase of bond angle at N1 [C2-N1-C1: 121.7 (2)°], and this angle is comparable with the unprotonated atom N2 [C4-N2-C1: 116.17(19)°] and this also further con rmed from the corresponding reported bond angle of neutral 2-amino-4-methoxy-6-methylpyrimidine[17, 18], which is signi cantly high [116.0(18)°].…”