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The title compound was obtained as an unexpected by-product in the attempted biaryl coupling of phenyl 1-methoxy-2-naphthoate with 2-methoxy-1-naphthyl magnesium bromide. From ether/petroleum ether it crystallizes from the purified reaction mixture as colorless plates of the space group  P 2 1 / a ;  a  = 1258.7(5) pm,  b  = 1791.1(8) pm,  c  = 583.8(2) pm, and  β  = 93.68(3)°. The most characteristic feature of the structure is an intramolecular hydrogen bond quasi forming a fourth 6-membered nearly planar ring system.

Crystal structure of phenyl 1-hydroxy-2-naphthoate, an unexpected product from an attempted aryl aryl coupling reaction 1