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The heteroaryl substituents of this ligand provide both hard and soft donor sites. Surprisingly, the phosphorus atom in <jats:bold>2<\/jats:bold> is divalent and the hydrogen atom is directly bonded to one ring nitrogen atom and hydrogen bonded to the second. Compound <jats:bold>2<\/jats:bold> decomposes in any common solvent other than diethyl ether and a new preparation to improve the yields of <jats:bold>2<\/jats:bold> is presented. A coordination polymer, [{Cs(bth)<jats:sub>2<\/jats:sub>P}<jats:sub>8<\/jats:sub>] (<jats:bold>3<\/jats:bold>) (bth=benzothiazol\u20102\u2010yl), was obtained when the <jats:italic>sec<\/jats:italic>\u2010phosphane <jats:bold>2<\/jats:bold> was allowed to react with elemental caesium in a 1:1 ratio in diethyl ether at \u221278\u2009\u00b0C. In <jats:bold>3<\/jats:bold> each anion is coordinated to four caesium cations and vice versa. The central phosphorus atom is coordinated to two metal atoms above and below the mean plane of the anion in positions in which the two lone pairs of a four\u2010electron donor are anticipated. Two additional cations \u03bc\u2010bridge both ring nitrogen atoms. 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