The crystal structure of the α polymorph of nylon 4 has been determined from the x‐ray diffraction patterns of uniaxially oriented monofilaments. In general the crystal structure of α nylon 4 is similar to that of α nylon 6. The unit cell is monoclinic with the following dimensions: a = 9.29 ± 0.05 A., b = 12.24 ± 0.05 A., c = 7.97 ± 0.05 A., and β = 114.5 ± 1.0°. There are eight monomeric units in the unit cell. The theoretical density is 1.37 g./cc. and the observed density 1.25 g./cc. The space group is P21. The nylon 4 chains are of the extended planar zigzag type, with the plane of the zigzag approximately parallel to the a axis of the unit cell. Along the a axis, every other chain is inverted—an antiparallel arrangement of chains—thus permitting complete hydrogen bonding and the formation of sheets of nylon 4 chains. Along the c axis of the unit cell, the second sheet is displaced by3/10 of the b axis, thus leading to a staggered arrangement of sheets. The sheets are held in place by van der Waals forces.

The salts of L-aspartic acid with divalent zinc, cobalt and nickel crystallize as tri-hydrates, and are isomorphous. Unit-cell dimensions are:

The x-ray structure analysis of a single crystal of the fi-form of 2-11-bromoundecanoyl-1, l'dicaprin has revealed an arrangement of carbon atom chains within a molecular layer that is identical to that found in the fi-form monoacid triglycerides. However the packing of the molecular layers within the crystal lattice is substantially different because of the unequal fatty acid chain-lengths in the symmetrical diacid triglyceride of this investigation.Insufficient diffraction data owing to difficulty in preparing crystals of adequate size prohibits computation of precise interatomic distances and angles for this triglyceride.

In addition to the α polymorph, two crystalline forms of nylon 4, the β and δ polymorphs, have been observed and studied. The β polymorph of nylon 4, which has not been found in a pure condition, appears to be similar to the β polymorph of nylon 6. The extended planar zigzag conformation of chains, found in the α polymorph, is present also in the β polymorph. Three models have been proposed to explain the observed data. In model 1, the staggered shear of van der Waals bonded sheets found in the α polymorph is abandoned; in model 2, the sheets are displaced by 1/2 the b axis, and in model 3 the chains are arranged in a parallel array. The β polymorph is converted to the α form in air upon heating for 11 min. at 227°C. and upon immersion in water for 2 hr. Models 1 and 2 would be converted to the α polymorph by a slippage of the van der Waals bonded sheets while the conversion from model 3 would involve a rupture of hydrogen bonds, a rotation of the chains through 90°, and the reformation of hydrogen bonds. The δ polymorph is formed by rapidly quenching extruded nylon 4 against chilled rolls. It is a metastable form which has only been observed in an unoriented condition. Upon orientation it is completely converted to the α polymorph. In addition to this, its conversion to the α form occurs under conditions similar to the β–α transition. The observed diffraction pattern can be indexed on the basis of a hexagonal packing of chains. High‐temperature x‐ray diffraction studies of the α polymorph suggest that the δ form, or a structure similar to it, is the high‐temperature form of nylon 4.

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