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4, 899-911 (1966)
Synopsis
The crystal structure of the 01 polymorph of nylon 4 has been determined from the
x-ray diffraction patterns of uniaxially oriented monofilaments. In general t,he crystal
structure of o nylon 4 is similar to that of a nylon 6. The unit cell is monoclinic with the
following dimensions: a = 9.29 f 0.05 A,, b = 12.24 f 0.05 A., c = 7.97 =t0.05 A.,
and p = 114.5 -I 1.0". There are eight monomeric units in the unit cell. The theoreti-
cal 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/,,of the b axis, thus leading to a staggered arrangement
of sheets. The sheets are held in place by van der Waals forces.
Introduction
Nylon 4, [-N H (CH,)&O- ],?: obtained by polymerizing 2-pyrrolidone
(I),1
CH2-CH2
I 1
CHrC=O
h6 I
possesses many of the properties characteristic of the polyamides. The
polymer is thermoplastic with a melting point of about 265°C. It may be
combined with suitable fillers or extenders and other conventional con-
stituents such as plasticizers, pigments, and dyes. The polymer can be
shaped, spread as a film or surface coating, used as an impregnant, and
* Paper presented a t the First Middle Atlantic Regional Meeting of the American
Chemical Society, Philadelphia] February 4, 1966.
t T o whom the inquiries should be addressed.
899
900 R. J. FREDERlCKS, T. 11. DOY NE, 1L S. SlMAGUE
4, 8, 16, 32, and 64 hr. Because many of the spots on the films resulted
from more than one reflecting plane, the intensities were proportioned
among the contributing planes on the basis of the magnitude of the cal-
culated structure factors for the model used. Lorentz and polarization
corrections were made in the usual manner. Spot shape corrections were
made after Franklin and Gosling.6 An isotropic temperature correction
was applied during the refining phase of the structure determination.
The value of the Debye-Waller factor B was determined by trial. The
scattering factors were calculated using the method of Vrtnd et al.' Cal-
culations required during the course of the study were performed on a
GE-225 digital computer at Lehigh University and an IBM-1620 digital
computer at Villanova University.
The infrared spectra were obtained by using the KBr pellet technique.
Results
I n general, the crystal structure of the alpha polymorph of nylon 4 is
quite similar to the a-polymorph of nylon 6 studied by Holmes et a1.*
Figure 1 is the x-ray diffraction fiber pattern of the a polymorph of
nylon 4.
The identity period ( b axis) along the fiber axis was determined from
measurements made of the t coordinate of the fifth layer line on a Bernal
chart. The b axis was found to be 12.24 f 0.05 A., in close agreement with
the expected value of 12.28 A. for extended planar zigzag chains of this
type:9 The dimensionsof the basal plane were determined from a zero layer
line reciprocal lattice net by using the trial-and-error procedures described
by Bunn'O and were as follows: a = 9.29 f 0.05 A., c = 7.97 f 0.05 A.,
and P=114.5 f 1.0". Reciprocal lattice nets for the higher layer lines
showed that the b axis was normal to the basal plane. Thus, the unit cell
and the symmetry, discussed below, were characteristic of the monoclinic
crystal system. The unit cell dimerisions were verified by calculating the
interplanar spacings for the determined unit cell and comparing these values
to the experimentally determined data. The agreement was quite good.
Fig. 1. X-ray diffraction fiber pattern of the a polymorph of nylon 4. Normal beam
method, cylindrical cassette, camera diamet,er of 5.73 em., CUKOC x-radiation, uniaxially
oriented monofilament.
903 R. J. FREDERICKS, T. H. DOYNE, R. S. SPRAGUE
TABLE I
Observed and Calculated Structure Factors and the Resulting Residual Factor for
LY Nylon 4
10
"i
604
206
116.7
67.6
100.2
117.8
16.5
50.2
021 I 4a.v
13
121 67.7 9.9 57.8
14 :iq
321
30.8 38.9 8.1
15
(continued)
The theoretical density for a nylon 4 with eight monomeric units in the
unit cell was 1.37 g./cc., and the observed density by physical flotation in a
carbon tetrachloride-toluene system was 1.254 i 0.003 g./cc. at 26.2"C.
Since less dense disordered matter is always present in synthetic polymers,
the experimental density is usually 5-10% less than the theoretical density.
Thus, the experimentally measured density is a further verification of the
unit cell dimensions. Attempts were made to induce higher orientation in
the polymer as an aid in determining the unit cell dimensions. Uniaxially
oriented monofilaments were placed in a Loomis 20-ton press with the fiber
axis parallel in some instances and normal in others to the ram axis of the
CRYSTALLOGRAPIIIC STUDIES OF NYLON 4. I 903
TABLE I (continued)
-
16 325)
225 \
104.4 33.0 71.4
622
17 130 12.3 46.5 34.2
18
131 24.5 63.3 38.5
230)
19
36.7 65.9 29.2
20 333
431
232) 61.3 89.1 27.8
21 241
- 49.1 25.1 24.0
341
22 251
115.8 144.6 28.8
23 20.1
149.6 129.5
351
24 353,
"3}
451 193.0 213.0 20.0
351)
25 351 1 130.3 87.8 42.5
451)
26 651
press. A pressure of 19 tons was applied and held for 1 min. Other mono-
filaments were flattened between rollers at room temperature and at
100°C. The higher orientation achieved was at the expense of crystallite
size and perfection and thus ruled out these specimens for x-ray studies.
The space group was determined from a consideration of the systematic
exhctions. An examination of the observed reflections (Table I) reveals
the following. (a) There are no systematic absences for reflections of the
904 R. J. FREDERICKS, T. H. DOYNE, R. S. SPRAGUE
type hkl. The lattice is therefore primitive. (b) Only reflections of the
type OkO fork even are observed. This indicates a twofold screw axis along
the fiber axis. (c) For the zero layer line (reflections of the type h01), only
reflections for h and 1 even were observed. This indicates the presence of a
glide plane.
Upon consulting a list of the 230 space groups," the possibilities are:
P21 (primitive, twofold screw axis), P&/m (primitive, twofold screw axis
perpendicular to a mirror plane of symmetry), P g l / c (primitive, twofold
screw axis perpendicular to a glide plane which is parallel to the c-axis).
Consider the geometry of the structural repeating unit, I1 :
H
I
CH2 CHz N CHI
/ \ / \c/\ / \ /\N
CHz CHz CHI
I1 I
0 H
I1
Repeat Distance = 12.24 f 0.05 A.
From the positions of the carbonyl oxygens, dictated by the three CH2
groups, a twofold screw axis with a translation of one-half the repeat dis-
tance is to be expected. The form of the chain also rules out mirror planes
TABLE I1
Atomic Coordinates for (X Nylon 4
Atom x Y z Atom x Y z
CHz 0.044 O.OO0 0.007 CH2 0.460 0.000 0.007
CHz 0.040 0.102 0.007 CHI 0.544 0.102 0.007
CHz 0.044 0.204 0.007 CH2 0.460 0.204 0.007
C 0.040 0.307 0.007 N 0.537 0.307 0.006
0 0.160 0.307 0.027 C 0,460 0.399 0.007
N 0.037 0.399 0.006 0 0.340 0.399 0.027
CHz 0.044 0.500 0.007 CHz 0.460 0.500 0.007
CHz 0.040 0.602 0.007 CH2 0.544 0.602 0.007
CHz 0.044 0.704 0.007 CH2 0.460 0.704 0.007
C 0.040 0.807 0.007 N 0.537 0.807 0.006
0 0.160 0.807 0.027 C 0.460 0.899 0.007
N 0.037 0.899 0.006 0 0.340 0.899 0.027
CH2 0.044 0.300 0.507 CHz 0.460 0.300 0.507
CHz 0.040 0.402 0.493 CHz 0.544 0.402 0.493
CHz 0.044 0.504 0.507 CH2 0.460 0.504 0.507
C 0.040 0.607 0.493 N 0.537 0.607 0.494
0 0.160 0.607 0.473 C 0.460 0.699 0.507
N 0.037 0.699 0.506 0 0.340 0.699 0.527
CHz 0.044 0.800 0.507 CHz 0.460 0.800 0.507
CHI 0.040 0.902 0.493 CHz 0.544 0.902 0.493
CHz 0.044 0.004 0.507 CHz 0.460 0.004 0.507
C 0.040 0.107 0.493 N 0.537 0.107 0.494
0 0.160 0.107 0.473 C 0.460 0.199 0.507
N 0.037 0.199 0.506 0 0.340 0.199 0.527
CRYSTALLOGRAPHIC STUDIES OF NYLON 4. I 905
perpendicular to the fiber axis. Thus, the possible space groups are
P2* and P21/c. From the systematic extinctions, one would expect the
space group P21/c to be the correct one. However, the three-dimensional
atomic parameters, as eventually determined (Table 11) show that the
space group is the lower symmetry P2*. One can explain this apparent
discrepancy when one considers only the xz parameters, which are what one
0- .- HN \
!3
/ = O
-0 =c
\ \
-o= c
0 - -HN
i' i
/"=O
c=o
Fig. 2. Parallel and antiparallel arrangement of the chains in a nylon 4 and the re-
sultant hydrogen bonding: ( a ) antiparallel placement of the chains permitting the
complete formation of hydrogen bonds; ( b ) parallel placement of the chains and the
resulting incomplete hydrogen bonding.
would expect for a glide plane along the c axis. Consequently, the h0Z re-
flections would be expected to show the systematic extinctions for this
symmetry element. A similar situation was observed in nylon 6.*
When one is studying the crystal structure of synthetic polymers, the
most practical procedure to follow is trial and error. Since single crystals
large enough to place in an x-ray apparatus are rarely available and since a
heavy atom is not usually present in the structure, direct methods for
solving the phase problem and refining the structure are not practical.
The initial model of a nylon 4 was arrived at by considering infrared
spectral data, the usual bond lengths and bond angles for substances
906 R. .T. FREDERICKS, T. H. DOYNE, R. S. SPRAGUE
Fig. 3. Electron density contour map for the basal plane projection of 01 nylon 4. One
quarter of the basal plane is shown.
Fig. 4. One of the hydrogen-bonded sheets which forms half the unit cell in the 01 poly-
morph of nylon 4.
similar to nylon 4,9 the use of Dreiding stereomodels, the unit cell di-
mensions and the symmetry of the space group.
It is well known that the positions of the NH stretching band and the
amide I band are influenced by hydrogen bond formation.12,l a I n nylon 4
the amide stretching band occurs near 3390 cm.-', compared to 3240 cm.-'
in the monomer while the amide I band attributed to carbonyl absorption
CRYSTALLOGRAPHIC STUDIES OF NYLON 4. I 907
occurs at 1640 cm.-' in the polymer and 1680 cm.-l in the monomer.
Shifts of this type from the monomer to the polymer indicate hydrogen
bond formation in the latter. Infrared spectra of cast and extruded films,
fibers, and powders exhibited similar NH and amide I bands.
The identity period along the fiber axis indicated an extended planar zig-
zag conformation. Dreiding stereomodels of the nylon 4 chains showed
that the possibility of hydrogen bonding was enhanced when every second
molecule in a given plane of molecules was inverted by 180'. This is re-
ferred to as an antiparallel arrangement (see Fig. 2 ) and is similar to the
situation found in nylon 6.s The density of a nylon 4 was consistent with
the presence of eight monomeric units or four structural repeating units in
the unit cell. Since it appeared that a twofold screw axis passed through
the chain, it was reasonable to place the four structural repeating units at
the positions of the twofold screw axes in the space group. Structure
factors were then calculated for the h01 reflections and found to be in ap-
proximate agreement with the observed values. Electron density calcula-
tions were performed for the basal plane projection. The resulting electron
density contour map for one quarter of the basal plane, (Fig. 3) shows the
structural repeating units to be identical in projection. The electron
density contours are elliptical with the major axis of the ellipse parallel to
the a axis of the unit cell. Thus the plane of the extended planar zigzag
structural repeats was coincident, or nearly so, with the a axis of the basal
plane.
Since the four structural repeating units were located at the posit,ionsof
the twofold screw axes, the first half of each unit is related by symmetry
to the second half. The basal Dlane projection showed the plane of the
908 R. J. FREDERICKS. T. 1%.DOYNE, R. S. SPRAGUE
3/10 b-axis
4
Fig. 6. Displacement of the nylon 4 sheets by 8/10 of the b axis.
References
1. W. 0. Ney, W. R. Nummy, and C. E. Barnes, U.S. Pat. 2,638,463 (May 12, 1953).
2. K. Dachs and E. Schwartz, Ange-w. Chem. Intern. Ed., 1,430 (1962).
3. Y. Kinoshita, Makromol. Chem., 3 3 , l (1959).
4. D. C. Vogelsong, J . Polymer Sci. A , 1,1055 (1963).
5. R. J. Fredericks, T. H. Doyne, and R. S. Sprague, J . Polymer Sci. A-2, 4, 913
(1966).
6. R. E. Franklin and R. G. Gosling, Acta Cryst., 6,678 (1953).
7. V. Vand, P. F. Eiland, and R. Pepinsky, Acta Cryst., 10,303 (1957).
8. D. R. Holmes, C. W. Bunn, and D. J. Smith, J . Polymer Sci., 17, 159 (1955).
9. L. Pauling and R. B. Corey, Proc. Roy. Soc. (London),B141,lO (1953).
10. C. W. Bunn, Chemical Crystallography, Oxford Univ. Press, 1961.
11. N. F. M. Henry and K. Lonsdale, International Tables for X-ray Crystallogruphy,
Vol. I, Kynoch Press, Birmingham, England, 1952.
12. A. Miyake, J . Polymer Sci., 44, 223 (1960).
13. L. J. Bellamy, The Infra-red Spectra of Complex Molecules, Wiley, New York,
1960.
14. G. C. Pimentel and A. L. McClellan, The Hydrogen Bond, Freeman, San Francisco,
1960.
15. C. A. Coulson, Valence, Oxford Univ. Press, 1952.
Resume
La structure cristalline du polymorphe LY du nylon 4 a 6th d6termin6e a u depart de
diagrammes de diffraction aux rayons-X de monofilaments orient& dans un axe. En
general la structure cristalline du nylon LY 4 est semblable ii celle du n$on 6. La
(Y
groupe spatial est P d . Les chaines de nylon 4 sont du type zig-zag planaire Btendu avec
un plan du zig-zag approximativement parallele B l'axe a de la cellule unitaire. Le long
de l'axe a, toute l'autre chaine est renvers6e; un arrangement antiparalkle des chaines
permet une liaison hydrogene complete et la formation de feuilles de chaines de nylon 4.
Le long de l'axe c de la cellule unitaire la seconde feuille est dkplac6e de 3/10 de l'axe b,
ceci amenant B un arrangement alterne des feuilles. Les feuilles sont tenues en place
par des forces de van der Waals.
Zusammenfassung
Die Kristallstruktur der a-Form von Nylon 4 wurde aus Rijntgendiagrammen voii
uniaxial orientierten Monofilamenten bestimmt. I m allgemeinen ist die Kristallstruk-
tur von a-Nylon 4 derjenigen von a-Nylon 6 ahnlich. Die Elementarzell~ist monoklin
und besitzt folgende Dimensionen: a = 9,29 f 0,05 A, b = 12,24 f 0,05 A, c = 7,97 f
0,05 A, und 6 = 114,5 f 1,O". In der Elementarzelle befinden sich acht Monomerein-
heiten. Die theoretische Dichte betragt 1,37 g/cm3 und die beobachtete 1,25 g/cm3.
Die Raumgruppe ist P21. Die Ketten von Nylon 4 sind vom gestreckten ebenen Zick-
zack-Typ mit der Zickzackebene abgenahert parallel zur a-Ache der Elementarzelle.
Langs der a-Ache besteht eine Inversion jeder zweiten Kette-eine antiparallele
Kettenanordnung-, was eine vollstandige Ausbildung von Wasserstoffbindungen
sowie die Bildung von Schichten aus Nylon 4-Ketten erlaubt. Langs der c-Ache der
Elementarzelle ist die zweite Schichte um 3/,0 der b-Achse verschoben, was zu einer
Anordnung mit versetzten Schichten fiihrt. Die Festlegung der Schichten geschieht
durch van der Waals-KrSifte.
Received February 24, 1966
Revised April 23, 1966
Prod. No. 8AF