Brydson Rowan K H, Gray Morven L, Kennedy Alan R, O'Hara Benjamin C, Reid Michael W, Ugbolue Ifeka
Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland, United Kingdom.
Acta Crystallogr C Struct Chem. 2025 Feb 1;81(Pt 2):102-108. doi: 10.1107/S2053229625000701. Epub 2025 Jan 30.
Three alkali metal salt forms of the diuretic chlorothiazide (systematic name: 6-chloro-1,1-dioxo-2H-1,2,4-benzothiazine-7-sulfonamide, HCTZ) are described. When crystallized from aqueous solution, the Na and K salts, namely, poly[[μ-aqua-aqua(μ-6-chloro-1,1-dioxo-7-sulfamoyl-2H-1,2,4-benzothiadiazin-2-ido)sodium] hemihydrate], {[Na(CHClNOS)(HO)]·0.5HO}, and poly[[diaqua(μ-6-chloro-1,1-dioxo-7-sulfamoyl-2H-1,2,4-benzothiadiazin-2-ido)potassium] hemihydrate], {[K(CHClNOS)(HO)]·0.5HO}, are both found to have stoichiometry MCTZ·2.5HO, with CTZ deprotonated at a heterocyclic ring N atom. Both the stoichiometry and the deprotonation site are different to those described in previously published versions of these structures. The Cs salt form is found to be the monohydrate CsCTZ·HO, namely, poly[[aqua(μ-6-chloro-1,1-dioxo-7-sulfamoyl-2H-1,2,4-benzothiadiazin-2-ido)caesium], [Cs(CHClNOS)(HO)]. As with the Na and K cognates, this structure is also deprotonated at the heterocyclic ring. NaCTZ is found to be a two-dimensional coordination polymer with bridges between Na centres formed by HO and SO groups, and by links through the length of the coordinated CTZ anions. Water ligands in KCTZ and CsCTZ are terminal, rather than bridging between metal centres, but both compounds form structures where M-Cl interactions link two-dimensional motifs formed via M-O bonds (and in CsCTZ, M-N bonds) into three-dimensional coordination polymers.
本文描述了利尿药氯噻嗪（系统命名：6-氯-1,1-二氧代-2H-1,2,4-苯并噻嗪-7-磺酰胺，HCTZ）的三种碱金属盐形式。从水溶液中结晶时，钠和钾盐，即聚[[μ-水合水合（μ-6-氯-1,1-二氧代-7-氨磺酰基-2H-1,2,4-苯并噻二嗪-2-亚氨基）钠]半水合物]，{[Na(CHClNOS)(HO)]·0.5HO}，和聚[[二水合（μ-6-氯-1,1-二氧代-7-氨磺酰基-2H-1,2,4-苯并噻二嗪-2-亚氨基）钾]半水合物]，{[K(CHClNOS)(HO)]·0.5HO}，均发现其化学计量比为MCTZ·2.5HO，其中CTZ在杂环N原子处去质子化。化学计量比和去质子化位点均与这些结构先前发表版本中描述的不同。发现铯盐形式为一水合物CsCTZ·HO，即聚[[水合（μ-6-氯-1,1-二氧代-7-氨磺酰基-2H-1,2,4-苯并噻二嗪-2-亚氨基）铯]，[Cs(CHClNOS)(HO)]。与钠和钾同类物一样，该结构在杂环处也去质子化。发现NaCTZ是一种二维配位聚合物，在钠中心之间形成桥键，由HO和SO基团以及通过配位CTZ阴离子的长度形成的连接键构成。KCTZ和CsCTZ中的水配体是末端的，而非在金属中心之间桥连，但这两种化合物均形成这样的结构，其中M-Cl相互作用将通过M-O键（在CsCTZ中为M-N键）形成二维基序连接成三维配位聚合物。
