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Abstract: While reactions of AgC5F4N with elemental arsenic, antimony, and bismuth proceed selectively yielding E(C5F4N)3 (E=As, Sb, Bi), those with white and red phosphorus remained obscure giving product mixtures of so far unknown stoichiometry. The phosphorus compound was therefore prepared by an alternative route. P(C5F4N)3 and As(C5F4N)3 crystallize isostructurally in the monoclinic space group P21/c (no. 14) with four molecules per unit cell. π–π Offset stacking together with edge-face stacking lead to dimeric units which are connected by a second edge-face stacking of nitrogen onto the opposite side of the same tetrafluoropyridyl ring extending the structure into infinite chains. [Copyright &y& Elsevier]