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Polymorphism in diphenyl ether has been identified during in situ crystallization via single-crystal X-ray diffraction. Only weak inter- and intramolecular C−H···π interactions control the packing of the molecules in both crystal forms monoclinic centrosymmetric (P2₁/n) in form I and orthorhombic noncentrosymmetric (P2₁2₁2₁) in form II.