The crystal structure of polycaproamide: Nylon 6

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Abstract
The crystal structure of nylon 6 (NH (CH2)5CO)p has been determined by interpretation of the x‐ray diffraction patterns given by drawn, rolled fibers. The determination was part of a program to investigate the relation between structure and physical properties, in particular melting point. Nylon 6 melts 50°C. lower than its isomer nylon 66 (NH (CH2)6NH·CO (CH2)4CO)p; it had been suggested that this was due to deficient hydrogen‐bond formation in nylon 6 crystallites. The unit cell contains eight chemical units (NH (CH2)5CO) and is monoclinic with a = 9.56 A., b = 17.24 A., c = 8.01 A., and β = 671/2°. Calculated density = 1.23. Observed density for a drawn monofilament = 1.16. The structure consists of planar chains of CH2 groups and amide groups tilted 7° from the (001) plane. Alternate chains in this plane are oppositely directed, an arrangement which allows all hydrogen bonds to be made perfectly. The hydrogen‐bonded sheets of atoms are packed in an “up‐and‐down” staggered configuration along the c‐axis. Distances between atoms in neighboring molecules are all normal van der Waals contact distances. It appears, from a general survey of polyamide melting points published elsewhere, that the determining factor is the number of CH2 groups between the amide “anchor points”—polymers with odd numbers of CH2 groups melt lower than those with even numbers. The present work shows that the odd number of CH2 groups in this polymer does not lead to deficient hydrogenbond formation, and that the lower melting point of nylon 6 as compared with nylon 66 must be ascribed to some other cause, possibly connected with the propagation of vibrations along odd‐numbered chain segments.

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