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The crystal and molecular structure of a grayanotoxin VII is presented. The crystal is monoclinic, space group P21, with a = 7.647(1) Å, b = 11.7591(7) Å, c = 10.0873(6) Å, β = 91.143(8)°, V = 906.9(1) Å3, Z = 2. The structure was solved by direct methods and refined by full-matrix least-squares methods to a final R = 0.057 for 1494 independent reflections. The molecule has a tetracyclic structure consisting of two five-membered, one six-membered, and one seven-membered rings.