The peptide N-Boc-L-Pro-dehydro-Leu-OCH3 was synthesized by coupling dehydroleucine methyl ester with Boc-Pro-OH. It was crystallized from its solution in a methanol-water mixture at 4°C and the crystals belong to the orthorhfmbic space group P2,2,2, with a = 10.239( 1) A, b = 19.276(4) A, c = 20.319(3) A, V = 401q1) A3, and Z = 8. The structure was solved by direct methods using MULTAN 80. The structure was refined to an R value of 0.095 for 1871 observed reflections. There are two crystallographically independent molecules in the unit cell. The molecular dimensions of the two molecules are very similar. The backbone conformation angles of these molecules are as follows: B' = -176(1)', u , -, = -2(2)O, +, = -72(1)O, +, = 141(1)', w1 = = 148(1)O, w,, = 167(1)O, c p, , = -67(1)', +12 = 175(1)O, and el, = 172(1)O, respectively. Other torsion angles such as % = 8 6 ( 1 ) ' , x2 = -5(2)", +; , = 131(1)', and x12 = -16(2)O are interesting to define the backbone conformation together with the dehydro-Leu side chain as a conformation similar to that of the 8-bend type 11. The central amide bond of Pro-dehydro-Leu segment is deviated from the planarity. The Boc group adopts a trans-& conformation. The side-chain torsion angles xl, x2, x3, x4, and Bo for Pro-residue in the two molecules are 11(2)", -11(2)', 6(2)O, 2(1)O, -9(1)O and -18(1)', 31(1)O, -31(1)', 21(1)O, andl(1)' respectively. The side chain of the Pro residue of molecule A is in the flattened CY-end0 conformation while the pyrrolidine ring in molecule B adopts the well-known CT-ex0 conformation. The side-chain torsion angles x, x2,', and x2,2 in the leucyl residues of molecules A and B are -5(2)", -111(2)O, 126(2)O and -16(2)O, -110(2)O, and 133(2)', respectively. The molecular packing is stabilized by intermolecular hydrogen bonds and van der Waals interactions. 169(1)O, = -9qi)o, #2 = -179(1)0, e, = 179(1)', e: = 174(1)O, = -3(1)0, = -~(i)o, *Supplementary material: The listing of observed and calculated structure factors for the peptide N-Boc-L-Pro-dehydro-Leu-OCH3 and other tables are available on microfiche. Please