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The structure of the metastable form I polymorph of the macrolide anti­biotic clarithromycin, C38H69NO13, was determined by a powder diffraction method using synchrotron radiation. The space group of form I is P21212. The initial model was determined by a mol­ecular replacement method using the structure of clarithromycin form 0 as a search model, and the final structure was obtained through Rietveld refinements. In the form I crystal structure, the clarithromycin mol­ecules are aligned parallel along the a axis in a head-to-tail manner with inter­molecular hydrogen bonds between the hy­droxy O atoms. The dimethyl­amine groups of the clari­thro­mycin mol­ecule inter­digitate between neighbouring head-to-tail clarithromycin alignments. The novel crystal packing found in form I provides a mechanism that describes the transformation of form 0 to form I.
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