L. C A V A L C A , P.

D O M I A N O ,

G. F A V A G A S P A R R I A N D P. B O L D R I N I

CRUICKSHANK, D. W. J. (1949). Acta Cryst. 2, 65.

CRUICKSHANK, D. W. J. (1950). Acta Cryst. 3, 72.
CRUICKSHANK, D. W. J. (1956). Acta Cryst. 9, 747.
KUNCHUR, N. R. & TRUXER, M. R. (1958a). J. Chem. Soc.
p.2551.
KUNCHUR, N. R. & TRUTER, M. R. (1958b). J. Chem. Soc.
p. 3478.
International Tables for X-ray Crystallography (1962). Voi.
III, pp. 202, 211. Birmingham: Kynoch Press.
NARDELLI, M., CAVALCA, L. & FAVA, G. (1957). Gazz.
chim. Ital. 87, 1232.

885

NARDELLI, M. & CHIERICI, I. (1958). Ric. Sci. 28, 1016.

NARDELLI, M., FAVAGASPARRI, G. BOLDRINI,P. (1965).
Acta Cryst. 18, 618.
NARDELLI, M., FAVAGASPARRI,G., GIRALDIBATTISTINI,G.
& DOMIANO, P. (1966). Acta Cryst. 20, 349.
NARDELLI,M., MUSATTI,A., DOMIANO,P. & ANDREETTI,G.
(1964). Ric. Sci. 34, II-A, 711.
NARDELLI, M., MUSATTI,A., DOMIANO,P. & ANDREETTI,G.
(1965). Ric. Sci., 35, II-A, 469, 477, 807.
PHILLIPS, D. C. (1956). Acta Cryst. 9, 819.
ROLLETr, J. S. & SPARKS,R. A. (1960). Acta Cryst. 13, 273.

Acta Cryst. (1967). 22, 885

The Crystal Structure of p-Aminobenzoie Acid*

BY T. F. LAIt AND RICHARD E. MARSH

Gates and Crellin Laboratories of Chemistry, California Institute o f Technology, Pasadena, California, U.S.A.
(Received 2 November 1966)
The crystal structure of a monoclinic modification of p-aminobenzoic acid has been determined from
three-dimensional X-ray diffraction data. The unit-cell dimensions are: a=18-551, b=3-860, c=
18-642 A, ,8= 93.56; the space group is P2~/n. There are 8 molecules in the unit cell, and hence two in
the asymmetric unit. The structure was refined by least-squares methods to an R index, for 1916 observed reflections, of 0.073 and a goodness of fit of 1.29; the resulting standard deviations in the bond
distances are 0.006/~. The dimensions of the two structurally distinct molecules are closely similar,
and suggest a small amount of quinoid character. The amino and carboxyl groups are displaced slightly
from the planes of the benzene rings, and the nitrogen atoms are non-planar. Pairs of molecules are
linked together, to form dimers, through two O - H ' . . O hydrogen bonds arranged about a center of
symmetry; an additional N-H.--O hydrogen bond is formed by one of the two kinds of molecule.
Twinning and disorder are common for these crystals. In the disordered structure, which is based on an
orthorhombic unit cell half as large as the monoclinic cell, the hydrogen-bonded dimers apparently
remain intact but the arrangement of N-H..-O bonds becomes random.

Introduction
Preliminary X-ray diffraction photographs of crystals
of p-aminobenzoic acid, NH/C6H4CO2H, indicated an
interesting combination of twinning and disorder. Although the crystals are monoclinic, the a and e axes
are very nearly equal in length, leading to an approximately orthogonal cell bounded by (101), (10i), and
(010). Zero-level Weissenberg photographs about b
show almost exact mm symmetry, a reflection hOl having essentially the same intensity (and spacing) as the
corresponding reflection lOh. In addition, twinning
about (101) or (10i) is common, as evidenced by increased symmetry of upper-level photographs and by
a slight splitting of the high-angle reflections. Finally,
extensive streaking along alternate reciprocal lattice
rows of upper-level Weissenberg photographs about b
* Contribution No. 3444 from the Gates and Crellin
Laboratories of Chemistry. This investigation was supported
in part by Research Grant HE-02143 from the National Heart
Institute, Public Health Service, to the California Institute of
Technology.
!" Present address: Department of Chemistry, University
of Hong Kong, Hong Kong.

indicates severe disorder for many crystals; in the limiting case, when these lattice rows become continua, the
intensities of the remaining spots show orthorhombic
symmetry corresponding to the space group Pnma and
a unit cell half as large as the monoclinic cell. In view
of these interesting observations and because of the
importance ofp-aminobenzoic acid in certain biological
processes, we have undertaken the present investigation.
During the course of this investigation, the work of
Killean, Tollin, Watson & Young (1965; hereafter,
KTWY) was reported. They have apparently observed
the same sort of twinning and disorder; and after suitable transformation of axes, the two-dimensional
structure they report is in satisfactory agreement with
our results.

Experimental
Our crystals ofp-aminobenzoic acid were obtained by
evaporation of aqueous ethanol and methanol solutions. They grow in the form of long, fibrous needles
similar to modification I found by KTWY; we have
not obtained the other forms reported by them, nor
that reported by Prasad, Kapadia & Thakar (1937)

886

THE

CRYSTAL

STRUCTURE

and, more recently, by All6aume, Salas-Ciminago &

Decap (1966). Since the crystals shatter when cut with
a razor blade, all photcgraphs were taken with crystals
mounted along the needle (b) axis.
A large number of crystals were examined. Most of
them were badly twinned (as evidenced by the additional symmetry of upper-layer Weissenberg photographs); often the disorder streaks (see Introduction)
were absent on fresh crystals but grew increasingly
severe as the crystal aged. Eventually, a crystal about
0"2 mm in diameter was found which showed no significant amount of twinning or disorder; it was used to
collect all the data.
Values of the cell dimensions a, c, and fl were obtained from a least-squares fit to measurements made
on a zero-level Weissenberg photograph prepared in
a special camera, of nominal radius 10 cm, which holds
the film in the asymmetric position; the value of b was
obtained from Okl and hkO precession photographs
calibrated with the known values of c* and a*. The
space group P21/n was indicated by the absence of
reflections kO! with ( h + l ) odd and 0k0 with k odd.
The density was measured by flotation. Crystallographic data are given in Table 1.
Table 1. Crystal data
p - A m i n o b e n z o i c acid
C7HvNO2

F.W. 137.14
F(000) = 576

Monoclinic; space group P21/n

a = 18-551 _+0"002/~,
b = 3"860_+0"010
c = 18"642 _+0"003
f l = 9 3 . 5 6 +_0.02
V= 1332/~3
Z=8

Dm= 1"360 g.cm-3

Dx = 1.367 g.cm-3

Our photographs seem to correspond with those

described by KTWY. As reported by them, the hO!
photograph has almost exact mm symmetry and the
apparent cell dimensions are approximately 12.7 and
13.6 ./~; however, rather than doubling both axes, we
have been able to index the upper-level photographs
by choosing a new set of a and c axes rotated by
approximately 45 from the a and b directions of
KTWY. With this transformation of axes, our values
of the cell dimensions are in excellent agreement with
those reported by KTWY, their values of a and b corresponding, on the basis of our cell, to a = c = 18"63 A,
fl=93.6 .
Intensities were estimated visually from multiplefilm equi-inclination Weissenberg photographs (Cu Ka)
of layers 0 to 3 about b. A standard deviation was
assigned to each observation according to the expression given by Sharma & McConnell (1965), and was
used in obtaining film and pack factors for each set
of photographs and an average intensity (and its
standard deviation) for each reflection. These and all
subsequent calculations were carried out on an IBM

OF

p-AMINOBENZOIC

ACID

7094 computer under the C R Y R M system (Duchamp,

1964).
The intensities were corrected for Lp factors but not
for absorption (/zR 2 0" 1). Data from the different levels
were scaled together by preparing, for each level, an
equi-inclination Weissenberg photograph and a zerolevel anti-equi-inclination photograph, both photographs covering the same oscillation range, being carefully timed, and recorded on different portions of the
same film (Brown & Marsh, 1963). The resulting list
of data comprised 2509 independent reflections, of
which 573 were too weak to be observed above background and 15 were cut off by the beam-stop.
Determination and refinement of the structure

Approximate scale and temperature factors were obtained by Wilson's method, and unsharpened Patterson
projections onto (010) were calculated. The sharpened
map gave clear evidence as to the orientations of the
benzene rings and also indicated the probable positions
of the atoms adjacent to the rings; packing and hydrogen-bonding considerations led to a trial set of x and z
coordinates for the twenty heavy atoms (two molecules) in the asymmetric unit. After five cycles of
least-squares refinement, including individual isotropic
temperature parameters, the R index for the hOl reflections was 0.113. Approximate y coordinates were
deduced assuming planar molecules, and three leastsquares cycles based on the entire set of three-dimensional data led to an R index of 0.125.
During these preliminary refinement cycles, the
weighting function was that suggested by Hughes
(1941 )" since the quantity minimized was X w(FZo- F 2~2
this function represents a compromise between unit
weights and those appropriate if the only errors were
due to observational uncertainties (in which case I/w =
1/a(F2o)~_l/FZo). We have found such a compromise
scheme useful in early refinement stages.
For the final refinement stages, weights Vw were
taken equal to the reciprocals of the standard deviations of the individual values of F2o as derived during
the data reduction process (see Experimental); five
strong reflections apparently suffering from extinction
were given zero weight. Atomic form factors were
taken from International Tables .for X-ray Crystallography (1962). The full matrix of normal equations
was collected until it became too large (over 207 parameters) to fit into core memory.
After two least-squares cycles including anisotropic
temperature factors, a three-dimensional difference
synthesis was calculated; this map gave clear indication
of the approximate positions of all the hydrogen atoms.
Their coordinates were further adjusted through two
least-squares cycles in which the remaining parameters
were held fixed. For the final four cycles, the complete
list of 237 parameters was adjusted: coordinates of all
34 atoms, anisotropic temperature parameters for the
20 heavy atoms, isotropic temperature factors for the

T. F. L A I

AND

RICHARD

E. M A R S H

887

Table 2. The heavy-atom parameters and their standard deviations (in parentheses)
All values have been multiplied by 104. The anisotropic temperature factor is expressed in the form
exp [-- (bl lh 2 + b22k 2 + b3312+ blzhk + bj 3hl+ b23kl)].

N
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
O(1)
0(2)

x
Molecule A
3461 (1)
1542 (i)
2214 (2)
2842 (2)
2829 (2)
2160 (2)
1531 (2)
0879 (2)
0866 (1)
0276 (1)

bll

b22

b33

bl 2

bl 3

5079 (8)
2733 (7)
1898 (8)
2738 (8)
4379 (8)
5258 (8)
4422 (8)
1681 (8)
0089 (6)
2586 (6)

- 1666 (2)
-0711 (1)
-0372 (2)
-0675 (2)
- 1343 (2)
- 1686 (2)
- 1374 (2)
-0394 (2)
0180 (1)
-0754 (1)

28 (1)
26 (1)
28 (1)
27 (!)
27 (I)
32 (1)
28 (1)
28 (1)
29 (I)
23 (l)

1388 (34)
649 (24)
846 (27)
832 (28)
821 (27)
756 (27)
722 (26)
708 (24)
1083 (23)
1192 (22)

42 (I)
25 (1)
28 (1)
31 (1)
31 (1)
31 (1)
29 (1)
24 (1)
28 (1)
35 (1)

- 3 7 (9)
- 6 (7)
- 4 (8)
4 (8)
- 2 8 (8)
0 (8)
16 (8)
8 (7)
- 2 2 (6)
- 2 (6)

10 (2)
- 2 (1)
- 3 (1)
- 5 (2)
9 (2)
5 (2)
1 (1)
0 (1)
- 1 (1)
- 1 (1)

49 (10)
- 1 2 (7)
- 1 1 (8)
- 2 3 (8)
- 5 6 (8)
21 (8)
- 4 (7)
- 7 (7)
57 (6)
115 (6)

N
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
O(I)
0(2)

Molecule B
3304 (1)
-5445 (7)
4286 (1)
-2821 (7)
4624 (2)
-2073 (8)
4309 (2)
-2967 (8)
3642 (2)
-4648 (8)
3300 (2)
-5452 (8)
3622 (2)
-4530 (8)
4615 (2)
- 1727 (8)
5213 (1)
-0236 (6)
4248 (1)
-2343 (6)

3401 (1)
1519 (2)
2194 (2)
2817 (2)
2783 (2)
2111 (2)
1489 (2)
0862 (2)
0883 (1)
0262 (1)

38 (I)
26 (1)
29 (1)
29 (1)
28 (1)
28 (1)
28 (1)
25 (1)
29 (1)
36 (I)

1154 (28)
594 (23)
708 (25)
716 (25)
748 (25)
762 (25)
708 (25)
706 (24)
1198 (24)
1218 (23)

27 (1)
28 (1)
30 (1)
29 (1)
27 (1)
29 (1)
27 (1)
29 (i)
30 (1)
25 (1)

- 5 7 (8)
27 (7)
- 8 (8)
- 2 (8)
37 (8)
- 3 3 (8)
16 (8)
21 (7)
- 6 1 (7)
-81 (7)

3 (1)
- 1 (1)
- 4 (2)
- 5 (2)
2 (1)
0 (2)
- 3 (1)
1 (1)
4 (1)
- 5 (1)

36 (8)
- 8 (7)
- 1 (8)
- 5 (8)
7 (7)
- 7 (8)
- 1 9 (7)
- 13 (8)
12 (6)
21 (6)

14 h y d r o g e n a t o m s , a n d a scale factor. The p a r a m e t e r s

o f the h y d r o g e n a t o m s were kept in one m a t r i x a n d
the h e a v y - a t o m p a r a m e t e r s and the scale factor in a
second matrix.
D u r i n g the last cycle, no h e a v y - a t o m p a r a m e t e r
shifted by as m u c h as o n e - t h i r d of its s t a n d a r d deviation, n o r a n y h y d r o g e n - a t o m p a r a m e t e r by 0.5 e.s.d.
T h e final R index for 1916 observed reflections o f n o n zero weight is 0.073 a n d the g o o d n e s s o f fit, (Z w(F2oF 2 ) / m - s ) ~, is 1.29.
T h e h e a v y - a t o m p a r a m e t e r s and their s t a n d a r d dev i a t i o n s are given in T a b l e 2; those of the h y d r o g e n
atoms, in T a b l e 3. T h e s t a n d a r d deviations were calculated f r o m the d i a g o n a l elements of the least-squares
T a b l e 3. The parameters, and their standard deviations,

of the hydrogen atoms

Values for the coordinates have been multiplied by 103. The
temperature factors are in the form exp ( - B sin2 0/)~2).

x(a.T)
Molecule A
H(1)
- 0 0 9 (2)
H(2)
224 (2)
H(3)
330 (2)
H(4)
390 (2)
H(5)
346 (2)
H(6)
215 (2)
H(7)
106 (1)
Molecule
H(I)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7)

B
450(2)
508 (2)
457 (2)
359 (2)
301 (2)
282 (1)
337 (I)

y(a,,)

z(az)

B (as)

135
065
238
484
678
666
490

(10)
(8)
(8)
(9)
(10)
(9)
(7)

-053 (2)
011 (2)
- 0 4 4 (2)
- 139 (2)
- 199 (2)
- 217 (2)
- 163 (1)

5.1 (0.9)
2.7 (0.7)
3.2 (0.7)
4-6 (0.8)
6.9 (1.0)
5"2 (0"9)
2'2 (0"7)

-I11
-067
-250
-517
-711
-671
-506

(11)
(8)
(8)
(9)
(11)
(7)
(7)

-013 (2)
220 (2)
330 (2)
383 (2)
341 (2)
206 (1)
100 (2)

7-7(1.1)
3.1 (0.7)
3.8 (0.8)
4.2 (0.8)
6-3 (1.0)
2.2 (0.6)
2.9 (0.7)

b23

inverse matrices; since two separate matrices were collected, the e.s.d.'s m a y be slightly low.
T h e observed a n d calculated structure factors are
listed in Table 4. The electron density projected o n t o
(010), calculated at the c o n c l u s i o n o f the refinement,
is s h o w n in Fig. 1; the c o r r e s p o n d i n g difference map,
for which the c o n t r i b u t i o n s o f the h y d r o g e n a t o m s were
o m i t t e d from the Fc's, is s h o w n in Fig.2.

Discussion

The molecular structure

In each of the two structurally distinct molecules in the
a s y m m e t r i c unit (A a n d B), the a t o m s o f the six-membered benzene ring are c o p l a n a r within 0.01 A ; however,
the substituent a m i n o a n d c a r b o x y l g r o u p s are displaced
significantly f r o m the plane. The e q u a t i o n s o f the
best planes o f the two rings, a n d the deviations o f the
various a t o m s f r o m these planes, are given in T a b l e 5.
In b o t h molecules a t o m s C(7) a n d N are displaced
f r o m the planes o f the ring a t o m s by a b o u t the same
a m o u n t s , 0-06-0-07 A, and in the same directions.
A t o m s C(1), C(7), O(1), a n d 0 ( 2 ) of the c a r b o x y l
groups are themselves c o p l a n a r , but these planes are
bent out o f the planes of the benzene rings a n d also
r o t a t e d slightly - by a b o u t 1.5 for molecule A and
2.5 for B - a b o u t the C(1)-C(7) bonds.
T h e i n t r a m o l e c u l a r b o n d distances a n d angles are
s h o w n in Fig. 3. T h e e s t i m a t e d s t a n d a r d deviations in
distances involving the heavier a t o m s are a b o u t 0.006 A,
and a b o u t 0.4 in the angles; for b o n d s i n v o l v i n g
h y d r o g e n atoms, the uncertainties are a p p r o x i m a t e l y
ten times larger. In light o f the scatter a m o n g chemically e q u i v a l e n t distances, these s t a n d a r d deviations seem
quite reasonable.

888

THE

CRYSTAL

STRUCTURE

each group
refinement.

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++

+t
++

i,,
-++

:+ :++ ;:! +i+ :H +:

+l

i+ !+ :J
:~ :If

~,io
-v,

-Lo

LSl
i,,
is,+
iio
,,o

I+
-i.,
-i.
-io
-.

:',+'
I,114, +.]
.~I
IIC

~iiil+:i
:,+ ;ll
......

,;i
H

io

-,

-~;

i !i ':i

-v,

it,,,

~+, :~+,,
.2o,

)6

:11 :L*
:l: "

-<

~l

:; ':+,

:+' ,;: ;1
o' to': ',+

-;

",,

.+.,'*
:I l

:11

+,

-,

.;,,

-i

;1
-+.

:',~ 2,
It

;l

1+

~+

.,,

-..o

+,~

-+

-i.

+
+,

-~,
-z~

z,

"~"

:i

:: '::

-1

"i'ii !!
l:

),

,s

-;'

!! :: i

:,!+

'

i i]

i i[i :i

.+,
; V
.......

i ,l

-,

t,
i,

1,
-+,6

l: 7;

-+L

l.

,.

,,

:+,;

',: :;:

4:

! ,i! ,i~

-I
4'
-6

Ill
*,,
6~

,,i ii ::ii
',1 " ,
17

-iz

.1.,

s~.

-,,
-l,,

:I~":+'~' '

-i
-i)

),
-.-,,

:;

1)

....

:1-1'

),

-,o

:~
g-i+
-+
-.

-+.

~,

ii :i!-~!!
o

~os

io,

i!-ii

-lo

-~

-+1

-,

-+ t,
i

l +. I;

:;

).

17

++ ++ +

-is

~,

ii ;!!-~!!
-*

,~

-~.

,:
II

;~' 1
-')

H ++
" "

-,"

2,

-1~

-,,

-,

:i I+' . . . . . . . . .
:f ,3~ ,;4
:t :+ :):
....
,*::
? '~: 'H
;) fl:s , 2?- s s
: :: .:t

....

,,

z**

: ,l:

..

21+,

;,,o

iio :~i,o :::

i! ,!! ;?! i~ .ii ::
-::
lo

-PII

i+

Z7

-~I

los

-~:
-?,

,,; -~ .,~
',~ ;P

.1~

s,

-.

:0

-::

!i -i! -~
ii
i.

-~,

io

-;'o

-z
7'

-i,
II

-,z
-ll
-l+
-+
-.
.,
-6
.+,

-i)
II
)s
.;'+
)
_.,~
+,,
~+

-~
.,
.:

-p+
.,,,+
_,,0
~c

;,

so

;'0

+,

,+
_.,.,
. . ,

-,0
.+

i+
+,

.p,
+,
-+,+
-:<

-ll

,'I
.~+'

-,:

,-+, ;+

:,+ .: ::
so

-,
-s
-+,

~o
.
.l

-+a
..

:I

;;

'~

-is

I.

is

....

-io

-i+

-,,

!:!i _i!i !!-ii -i!

,,i-!i :! !~ ]! !i
i~!+ .:~ -:2 :!
.
i;,

',
-io

-~,
so
-+,,

,,l
,+
,l

;'
-,

t+ ii

++:t+

++ +3 ++

"......'

:: ::-:!
: :", '!~
i11 "
~ i! .d

+!i !+ !+
!! :!i '!
]!-!+ i!
......

+;'
-is

-,'
-,

-,
-t

-L.
+.

:II

I~

-+? .,,",+'

-,
-.,o

+!+++++++++
':,o

.1+

;~
l:

~',
;I
11

ioo

,H

:I "
o' "4 ....
: ,L'
: IT

:.'I
-"

..

;,

:i ii :i
!!-ii
l:

t:

i~

-,~

-i,
-lz

-i,

I;4'

-,

.,

i++

.11

i~

+:+o; ::+':
: ':.: "-':',

.......

!+ -++

,o +,; -II

:'

:If ::
-'-,~ I~

b'

....
:',;

~:
+- .
so

:l.+

:; _.:
....
:I

:X

; ,+~ ....

:~ -+'l

-+':

*
s

-'

-+,
-s

s
++i

-[

.+

+,

+,

::

I'

-;:

~+
++
+,

++,
-~,
++

-+

'
io

.~s

'~
+e
60

: Ill-If
ix
l,
,++

.,

3;
-~}

!! !~ " -~:"::' i::

+- +

-i !+ H,
.+

'+ :l
' t;

_~

.+

-I
o
i

II
;'+

st

,l

:; 1, !+1 :I
:+' 2:
'
o' '1 . . . . . . . .

,.

-t!
+,
,u
,
.
-..i
+<

-,,
:~,i

+,~

-,,,
-i
-,
.+,
-s
-+
-+

,:

-+~
..

i,

-:: :',' I :
-~I :1 I"

-s

~,+
-;,4
zl
-;,,
- ++
_,.+
-;'+
+,

-..

-l.
sT

+i+ +! .... t+ ++ ++

:',:

.,
-..,+

.,
-,
0
+
z
,+
+

,t

'I

-s
-z

-,,

*-i!
-~

::

tf

-,,

!-i! i

+++ ++ +i+++ ;:
-|

;t

-+

':

i.',

-lOS
,*
-++

.++
I

.i

-,, ".,o' ".

:t~ :++' !'.
:'i
:'d
~+,
.
-~i
-~,

:~

? 71 :ll
-~.
II

,o

.~.,

,! 'i! ;!:
-+".

:, ,:+, -,.,

I l~
; 2:

,+'
t:

.,

+.: :'J ,': ,+,i

%+ ,~ -,:',

))

-)

....

.,

:~+
++ :+
:' ,;~

-s)

+s

:l; 11
:If t +.

:i

i il] i' +++i+ ++++++

+:ii-i]:
,i ;ii-~il ++!+ ii il ++ +' !i :i! #, 11 :!i .;:
:t'

.is

::

"

-lo

,, It
,'I " "l+

...+

.....

-+,

11
"

~!i
!i #
-:o I; :l:

-~s
s~

-,,

II

i .i! :~ ?~ !i :::

"'+

-~

1~

~
l,

.
.

+o

i)

I~ :~
~! ,ii
::: :: :: :: ?;i
1i !i~ '.',i ii !! :::
ii ii ?~! !!~ :~i ~!! .H

-,,

,,-l;
L++

',!II ]i!
-?
.l; _;,o

:,,:-+,

a ~i] ........

-16

,,

,tl

-{

i+

....

+)

11

I '+, t:
: ,o+.
+ -,It
',1 ++o
+ "

,,~

2 ,g,+
o

if! -[i -!
.

-I,

++++ 11 i?!i :i!i

::!i
ii !+;~
:l I -It

ii

~:,

-,1

l: :I:

il-il i::

-,

-,

-.,o

]!~ -!i -!:

-ii

..... .,:i +i!.,.ii, ":++ ++ +++i+

,<

?ii ~ii ':

-i~

i!! i! :o i! :ii
!~! i! !~:!! :i
,, ,~,+ J ;

',t, L+ 2+'

~'i~

.o

.i,

....
II

:;1

:;: -,L +

+)

-.o

:::: +::
l

-~oo
16
,~4

i~[ ]!
,

";
-~1

-i,

.,~
s

lot
-;'~
zl

.l
o
,

t:
~o

l+O
-.,

' !+ ++

~1 :+4
+~ -;++

i! _H :!! i+ ++ :i+
H ii i~ :3......
.y
~;
Fi s

,-+
,oi

:f-:;
-.

-)

:~ ii ii

":

l+' ll
:l ;k'

;' ,

tt

.....
1
,,

s.~

" ;~

+s

,.,

',: ~: -;:
;" :::
:

i +ii11 :i :ii ill i! -il ::

-lob

*z

" :: -:I
" 'I' "l:

-,i

i! ~ii-iii
ioo

i:

;o'

,! '-ii :ii i:!i :!: :": !! ii

++++++++++ ++ H ++i
)o
)+
)

_..+

)*,
o

:h Ill

' ::~+ I::

-~.,

II

~Is

-~

-~
-~
-.

.,,

s,6

" :l;

,z,

+ i!i :i!! i! !i
.,.

s~

-i~,

.,

2 d', 41',

z.,

-,
-i
o

-v,
-I)
-14

i ii :ii

:',~ !!-!i _[i

,~6

~o

0 I

-i.
-i+
-i

-~,,
-~++
-.s

i :t;

I 1 -I'+

i! '!i .ii~

-~

-,o
-.

+,
/I
llt
,,i

~+,o
-,q$

~,

+'

i!!';ii 'ii

i)
,II

,i :!i :]~
io

:l::

io+
,6.'

:t; '+'t+.o %', ,

++

io

-,

-,~1

,+ I:' :I::

-,~+
-z(
.

,S6

ii!

'6

: ~ !!
:: :: !i

i]ii;ii
I: :L'

"'"

;:I

I ;',: -,7

:i,'

~;'

-,(
-,u
-hi,

,
-P+
~ ,,

-I+
-i)
-is

i! !ii :!ii

-,o

*m

-,

-+

-io

-,,~

.,,,
s

io
~.,
i

;;t

-:+

i
,
)

with an asterisk
were omitted
from the leasthave been omitted
from the refinement
unless
o f Fo.

: ,:o* l?;

..... tt

:I: -I:

-+
o

i:}i-:il

!!i ,!! .2

?i ili ,+! i~ !? '; :~' !i-!~

-I,

,i

-',~

:I'll

-io
.+
-I

,"

ACID

~ ~i~ .,~
++i+ :++ ,iiiii " ii -,'i !i i+i :+;! : t+ ': lo' ,+; ;++ il ii ii
:I ,~o ,+I
",++:;I
,+ ,: :+ ..... +:+! 1 i! -~:
++ -++'o i~ :ii-qi !i :!i]i! !~ i?--:!

-i,

sl

l~ tt

::1

211

?i *ii ":

!;i!";!!
~i ill i]i

-+,J

l: ,~1 4+',+
',1
':I-_'IgII
II -;'4

io
II

:P 2 ' -;:+

s,,

:~
-,)

L,

.it~

,,

',I :~:

.,I

~ii !i .-!i

o' I',' :+",'

~'ii '?!
io

;'o

ii !~i '-!i

,1o

.+,
-,;'

-H

*,! :i! ;i!

H *i! ]i~
i,

':~

H ;t+ '++

-,

++
-1,

-i+o

-,o
-i,

...o+,
.
IIi
-,
+,<,
o
z,l

)..,+

f:++ -,,,:

-+, ;;+.. ,L'++

+is

I+'
"4
,,
,os

,o)

I ,:+' -,',I

! :iF:H~ i! :i! !!~ !! ~? 5

ii

-i

-,,~
i.+

-It

v,

:,.
,,~+

),o
++.

+
-~

:t:- , , ,I,'-,;'
)s
-,s
io~.

:i :~i

!1i ;+i _,:i

-7

.,o

-, %, -,::

:~ +:I

;+2

....
I

the values
o f h , lOFo, a n d 1 0 F ~ . R e f l e c t i o n s
indicated
sign preceding
Fo s i g n i f i e s ' l e s s t h a n " t h e s e r e f l e c t i o n s
the value of Fe exceeds
the threshold
value

are given
A minus

p-AMINOBENZOIC

4. Observed and calculated structure factors

Table
Within
squares

OF

-is
i.
1.

i
z
+

+,
+o

.+,
-,,

s,
-+

}
t ;'o

?ii]i' ":i+ ....

-~

;: ++ ++++ +!
11
;o
......

:t
~ -I,+

"1

......

T. F. LAI A N D

RICHARD

Table 5. The best planes of the benzene rings, atoms

C(1)-C(6), and the deviations of the individual atoms

from these planes

Molecule A

Molecule B
q~ =

0.4645

qz = --0"8855

q3 =
D=

889

bonds, the nitrogen atoms are significantly non-planar;

the positions of the hydrogen atoms H(4) and H(5)
correspond to a configuration about midway between
tetrahedral and planar.
The only significant differences between corresponding distances in the two molecules involve the C-O
bonds, the C(7)-O(1) distance being shorter and the
C(7)-O(2) distance longer in molecule A. Apparently
there is less contribution of the structure

The direction cosines q are relative to a, b, a n d c*, respectively;

D is the origin-to-plane distance.
ql = - 0 - 0 0 9 4
q2 =
0"8878
q3 =
0"4599
D=
0"287/~,

E. M A R S H

0"0031
4"570]k

(D

Deviation
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
N
C(7)
O(1)
0(2)
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7)

- 0.001
- 0.004
0.009
- 0.009
0.005
0.001
-0.061
- 0.073
-0.118
-- 0"065
--0"29
--0-01
0.08
0.09
0"23
0.05
-0-05

- 0.004
0.003
0-002
- 0"005
0"003
0.001
-0.057
- 0.058
-0.046
- 0.137
-0.22
-0.08
0.05
0.07
0-25
0.02
-0.01

/
--C

in molecule A. As a concomitance, the O(2)-H. O(1)

hydrogen bonds between pairs of A molecules are
weaker, and longer, than those between pairs of B molecules (see later discussion).
The C-H, N - H , and O - H distances are typical for
X-ray diffraction investigations, being somewhat shorter than the standard values for internuclear separations.
Some interesting comparisons can be made with the
molecular dimensions of 2-amino-3-methylbenzoic acid
(Brown & Marsh, 1963). In general, the C-C distances
in that molecule suggest very nearly the same amount
of o-quinone contribution as ofp-quinone contribution
in the present compound; however, the C(1)-C(2) and
C(3)-C(2) distances (C(2) is the atom bonded to the
o-amino group) are slightly longer, perhaps as a result
of overcrowding, and the C(2)-N distance is a bit
shorter - 1.367 ~ , com 9ared with an average value of

t t~ttkk.J))llIJI I

' 'f ((((((~)'~'~]~,, I

/--.

, 0(6),

,,.t,~.,))/
C(4)/
I

,"

,L, YI1((0))
~ ~ II(IG))D)III
\

"--" " ~ ' ? ~

, ~\ Icteo)lJI
~
X ~
i

.) ~

t...
/-x ! C((~OJ)/cc~

((~_~)..w(~));I /

/lllff~'~\\', \

/lllltttUJJJJllt "

f ~ ~ J J

Jl/..~,~\

rc~II,.._"S-3((f(~-h']~11)/
r --~ ttkkk~)))//
>>.~(c_., \ , ~

t\~JJll

",I((()))C7 . (0)) ---. /

,,. ~'

L_ I

~k ~

!)~<,.<,

~--

) fflh"3))l-((ft"')llll',~uJl

0(5),~~

\e
O

The distances indicate a small but significant contribution of the quinoid structure. The average value
of the central bond distances C(2)-C(3) and C(5)-C(6)
is 1.375/~, compared with an average value of 1.399 ,~
for the remaining ring C-C distances; the C(1)-C(7)
and C(4)-N bonds are about 0.06 A shorter than normal single bonds. Despite the shortening of the C - N

-t

OH

,, )

(-"\x
0(5))__.C(4)
},-'"--\
~,N

',m.//~,'k',,
,/fft(C'D))l

'-'

.//,~,\'-,

' ~ - - - " Illffm"~X~ X

ffl(((((~'~'t

~\k\k\~A

Fig. 1. The electron density projected on to (010). C o n t o u r s are at intervals of 1 e . ~ -2, beginning with the I e . ~ -2 c o n t o u r which

is dashed.

890

THE

CRYSTAL

STRUCTURE

OF

H(I)(~ 0

p-AMINOBENZOIC

z..........
.

ACID

H ( 6 ~ 2 )

~ -6"

-/~2~H(2) ~H'~'

Fig. 2. A composite representation of the final three-dimensional difference map in which the hydrogen contributions were
omitted from the Fc's. Contours are at intervals of 0.1 e.,~,-a beginning with 0.1 e.,~-3.

1.8 o

0"99
120

20.2

20"I

121"I

114'

248
Fig. 3. Bond distances and angles.

@00

T. F. LAI A N D R I C H A R D
1.380 A in the present case. The additional doublebond character in the C - N bond is reflected in a more
nearly planar nitrogen atom in 2-amino-3-methylbenzoic acid.
The dimensions of the carboxyl group and the O. O
hydrogen-bond distance in 2-amino-3-methylbenzoic
acid agree within experimental error with the values
we find for molecule A.
The structure viewed down the b axis is shown in
Fig.4. As is typical of carboxylic acids, pairs of molecules of each type (A and B) form dimers linked together by two hydrogen bonds across a center of symmetry (rather than along a 21 axis, as was indicated
by KTWY). The two O - H . . . O distances are significantly different: 2-64 ,~ for pairs of A molecules and
2"61 A for B. The O - H . . . O angles are 167 and 166 ,
respectively.
The more interesting hydrogen bonds - more interesting in that they appear to be the focal points of the
twinning and the disorder - are the N - H - - . O bonds
linking molecules of type A to those of type B. The
nitrogen atom of molecule B forms a single, relatively
strong (2.985 A) N - H ( 4 ) . . . O(1) bond to molecule A;
this bond is approximately linear, the N - H . . . O angle

"~,

//...0 m

"'-

~\.,

"g
~,

,,,, . . 3 C ~ c ~ r ) ~ .

~$~)

~ '~ : : ~ . ' - ~ ~ e ' z ~ , , , ,

-.-.~o~:~->>~,,-,.~.o~,
Tr

"'"

c~

.~3

.... ,

It

..

ca

891

being about 174. On the other hand, H(4) of molecule

A points approximately midway between two O(1)
atoms of B molecules lying one on top of the other
along b. If these N . . . O interactions can be called
hydrogen bonds at all ('bifurcated', presumably), they
are extremely weak, for the N . . . O distances are 3.35
and 3.42A, the N - H . . . O angles 142 and 137 , and
the H . . . O distances over 2.5/~; it is probably more
resonable to categorize them as van der Waals interactions.
The question immediately arises as to why the two
types of molecules have different environments, at first
thought, it would seem a simple matter to arrange them
so as to be structurally equivalent, each forming a
single, strong N - H . . . O hydrogen bond to a neighbor.
Indeed, there is a nearly exact twofold screw operation,
along the direction [101], relating molecules A and B
(Fig.4), and another screw operation relating pairs of
molecules along the direction [10T]. However, incorporation of these operations in a lattice so as to form a
four-molecule orthorhombic cell, as is necessary to
make the molecules equivalent, leads to one of the two
space groups P2~2~21 or P2~221, thus requiring that
the two molecules within a dimer be related by either
a 21 or a 2 axis rather than by a center. Quite obviously
there is no satisfactory arrangement of equivalent mol-

The hydrogen bonding

E. M A R S H

"~

"-

, t% .d
~,4_4~4

'IT

-'%

'~ . d : g . - ~ ~"

%-~v~._~e~,_~-

.~.,m,~-..

"

"gk

,' ! ,..
"1.. ~

'-

~
""

......

"" "
Fig.4. The structure viewed along the b axis.

'--'i
i

,,

892

THE

CRYSTAL

STRUCTURE

ecules w h i c h m a i n t a i n s the sanctity o f the h y d r o g e n b o n d e d dimers.

T h e d i s o r d e r e d o r t h o r h o m b i c structure (see Introduction) a p p a r e n t l y is a c h i e v e d by i n t r o d u c i n g a rand o m n e s s as to w h e t h e r m o l e c u l e A or m o l e c u l e B f o r m s
the s t r o n g N - H . . . O
h y d r o g e n b o n d . This has the
effect o f i n t r o d u c i n g a m i r r o r p l a n e p e r p e n d i c u l a r to
t h e b axis - t h a t is, in the p l a n e o f Fig. 4. Thus, if m o l ecule B (Fig. 4) a n d its c e n t r o s y m m e t r i c a l l y related m a t e
are reflected t h r o u g h a m i r r o r p l a n e at y = , they are
in p o s i t i o n to accept s t r o n g (2.98 .A) h y d r o g e n b o n d s
f r o m m o l e c u l e A a n d f r o m a n o t h e r m o l e c u l e - also
t y p e A - t o w a r d the l o w e r l e f t - h a n d c o r n e r o f F i g . 4 ;
h o w e v e r , they w o u l d n o l o n g e r be able to f o r m h y d r o gen b o n d s with the m o l e c u l e s in the center o f the cell.
A r a n d o m d i s t r i b u t i o n o f the t w o a r r a n g e m e n t s , tog e t h e r w i t h a very small a d j u s t m e n t o f the a t o m i c coo r d i n a t e s , leads to an o r t h o r h o m b i c u n i t cell, space
g r o u p Pnma, h a l f as large as the m o n o c l i n i c cell a n d
w i t h its a a n d c axes directed a l o n g the [10T] a n d [101]
d i r e c t i o n s o f t h e m o n o c l i n i c cell. T h e f o u r m o l e c u l e s
in t h e o r t h o r h o m b i c cell w o u l d o c c u p y e i g h t f o l d general positions, each site b e i n g o c c u p i e d h a l f the time.
This a r r a n g e m e n t seems to explain satisfactorily the app e a r a n c e o f the upper-level p h o t o g r a p h s .
T w i n n i n g is a c o m m o n p h e n o m e o n w h e n t h e r e is a
simple metric r e l a t i o n s h i p b e t w e e n cell d i m e n s i o n s . In
the p r e s e n t case it is d o u b t l e s s d u e to the near equality
o f t h e a a n d c axes, which, in turn, reflects the p s e u d o o r t h o r h o m b i c s y m m e t r y a n d the structural similarities
b e t w e e n the t w o types o f molecules.

OF p-AMINOBENZOIC
Table 6
Axis i
Molecule A
C(4)
1
2
3

T a b l e 6. Description of thermal ellipsoids

qtl, qi2, qi3 are the direction cosines of the principal axes
relative to the unit cell axes.
Axis i
Molecule A
N
1
2
3

C(1)

C(2)

C(3)

1
2
3
1
2
3
1
2
3

Bi
(A2)

qtl

q~2

q~3

8"51
5-78
3"64

-0"099
0"234
-0"967

0-965
-0"213
-0.151

0"248
0"932
0"265

3"96
3"89
3"21

- 0"493
- 0-640
0"589

- 0-630
0"730
0"265

0"629
0.279
0"726

5-06
4"32
3"47

- 0"004
- 0"716
0"698

- 0.991
0"097
0"093

0.135
0"734
0"665

5"16
4"46
3"40

- 0"260
- 0"547
0"796

- 0"848
0-524
0"082

0.477
0"686
0"550

(cont.)

B~
(/~2)

q~l

qt2

q~3

5.59
3"78
3"55

0.246
0"328
-0"912

-0.785
0"620
0"011

0-552
0"691
0"466

C(5)

i
2
3

4"71
4.40
4"03

0"093
0.970
- 0"225

0"824
- 0"201
- 0"530

0"552
0.076
0"830

C(6)

l
2
3

4"44
4.02
3"73

- 0"445
-0-275
0"853

- 0"854
0"417
- 0"311

0"297
0.882
0"366

C(7)

1
2
3

4"29
3"89
3"21

-0-379
-0"876
0-299

-0"909
0.413
0"060

0.199
0-303
0"932

O(1)

1
2
3

6"76
4.04
3"52

-0"157
- 0-890
0-429

0"946
- 0.260
-0"193

0"292
0.430
0"854

0(2)

1
2
3

8"00
4"06
3"14

-0-061
- 0"305
0"950

0"881
- 0.465
- 0.092

0"473
0"849
0"237

7"29
4"86
3"68

--0"369
0"925
- 0"092

0.920
0"348
- 0" 182

0-159
0"094
0.983

Molecule B
N
1
2
3
C(1)

1
2
3

4.26
3"65
3.15

- 0.602
0"363
0"712

- 0.433
0"601
-0"672

0.707
0"689
0-160

C(2)

1
2
3

4"68
4.22
3"54

-0-678
0"007
0"735

0'146
- 0"979
0"144

0"761
0.204
0"615

C(3)

1
2
3

4"67
4"27
3"43

-0"691
-0.111
0"714

-0"083
0"994
0"074

0"759
0"016
0"651

C(4)

1
2
3

4"75
3"82
3"45

- 0"491
-0"452
0"745

- 0"871
0.229
- 0.436

0"004
0"889
0"459

C(5)

1
2
3

4"78
4"11
3"52

-0.465
-0"383
0"798

0"885
-0-223
0.409

0.050
0.918
0"393

C(6)

1
2
3

4"60
3-88
3"40

- 0"547
-0"611
0"572

- 0"690
0"716
0.105

0"507
0-375
0"776

C(7)

1
2
3

4.47
3"95
3"37

-0-355
0-044
0"934

-0"779
0"537
-0"322

0"537
0"838
0"098

O(1)

1
2
3

7"39
4-10
3"78

-0"255
0'233
- 0"938

0"966
0"013
- 0-259

0"063
0"956
0"287

0(2)

1
2
3

7"82
4"60
3"28

-0"399
-0"856
0"330

0.910
-0.414
0"027

0"138
0-363
0"921

The temperature factors

T h e m a g n i t u d e s a n d o r i e n t a t i o n s o f the v i b r a t i o n
ellipsoids d e r i v e d f r o m the a n i s o t r o p i c t e m p e r a t u r e
factors (Table 2) are given in T a b l e 6. W h i l e the principal v i b r a t i o n s o f all the a t o m s t e n d s to be d i r e c t e d
a l o n g the b axis, o n l y the n i t r o g e n a n d o x y g e n a t o m s
s h o w p r o n o u n c e d a n i s o t r o p y . F o r each o f t h e m , t h e
m a x i m u m v i b r a t i o n is a p p r o x i m a t e l y p e r p e n d i c u l a r to
t h e m o l e c u l a r plane.

ACID

C o r r e s p o n d i n g a t o m s in the t w o m o l e c u l e s h a v e
closely similar t h e r m a l m o t i o n s . T h e slightly larger

T. F. LAI A N D R I C H A R D
amplitude of the nitrogen atom in molecule A over
that in molecule B undoubtedly reflects the weaker
N . - . O interaction discussed earlier.

References
ALLI~AUME,M., SALAS-CIMINAGO,G. & DECAP, J. (1966).
C. R. Acad. Sci., Paris, C262, 416.
BROWN, G. M. & MARSH, R. E. (1963). Acta Cryst. 16, 191.
DUCHAMP, D. J. (1964). Amer. Cryst. Assoc. Meeting,
Bozeman, Montana, paper B-14, p.29.

E. M A R S H

893

HUGHES, E. W. (1941). J. Amer. Chem. Soc. 63, 1737.

International Tables for X-ray Crystallography (1962).
Vol. II, p. 202-203. Birmingham: Kynoch Press.
KILLEAN, R. C. G., TOLLIN, P., WATSON, D. G. & YOUNG,
D. W. (1965)..4cta Cryst. 19, 482.
PRASAD, M., KAPADIA, M. R. THAKAR, V. C. (1937).
J. Indian Chem. Soc. 14, 667; J. Univ. Bombay, 8, Pt. 3,
123.
SHARMA, B. D. & MCCONNELL,J. F. (1965). Acta Cryst. 19,
797.
WILSON, A. J. C. (1942). Nature, Lond. 150, 151.

Acta Cryst. (1967). 22, 893

The Conformation of Non-Aromatic Ring Compounds. XXVIII*. The Crystal Structure

of a-Chloro-6-valerolactam
BY C. ROMERS, ELISABETHW. M. RUTTEN, CATHARINAA. A. VAN DRIEL AND W. W. SANDERS

Laboratory of Organic Chemistry, University of Leiden, The Netherlands

(Received 26 April 1966 and in revised form 16 September 1966)
Crystals of ~-chloro-~-valerolactam are monoclinic with space group P2~/e and Z = 4. The lattice constants at room temperature are a=11.73, b=6-20, c=9.51 A., ,8=112-0 . The structure was solved
from a minimum function M4 which was directly computed and contoured at the machine output.
Both b- and c-axis data were refined separately with a least-squares program and the results are compared.
The molecule has a half-chair conformation with the chlorine atom in equatorial position. The peptide
linkage NH-CO has the cis configuration. Unusual bond lengths are not observed.

Introduction

Experimental

During the synthesis of ~,co-diaminohexanecarboxylic

acid, via the amination of ct-chloro-oenantholactam
(Brenner & Rickenbacker, 1958) the corresponding
compound ~-chloro-O-valerolactam

~-Chloro-8-valerolactam, CsHsNOC1, melting point

121-122C, was crystallized from toluene. The monoclinic crystals are colourless, lath-shaped, frequently
twinned and elongated along [010] with main face (100).
The needle direction [010] appears to be bent about
[001] in such a way as to give the main face (100) a
slightly curved shape. The reflexions h00, and to a less
degree reflexions hkO, but not 0k0, recorded on a zero
layer non-integrated Weissenberg photograph, are extended on one side of the film and contracted on the
other, in accordance with the focusing geometry of the
reflecting plane (100).
Very small crystals cut perpendicular to the needle
axis do not show this effect and, moreover, their reflexions at high 0 values appear to be stronger than
the corresponding ones of b-axis exposures. The diffraction photographs were taken with Cu Kct radiation
( 2 = 1.5418 A). The lattice constants at room temperature were determined from zero layer non-integrated
Weissenberg photographs about [010] and [001]. These
exposures were superposed with aluminum powder
lines (a=4.0489 A at 20C) for calibration purposes.
The diffraction data
a = 11.73 + 0.02A t = 112.0_ 0.2 Z = 4
b = 6-20+0-01A dexp= 1"38g.cm -3 F(000)=280
c = 9.51 _+0.01A dx = 1.42g.cm -3/z(CuK~) = 4 3 c m -I

CH2--NH

CH2

\
/

CH2

/\
Cl

C--O

C
H

was used as a model substance for the study of the

reactivity of the chloro-amino substitution (Henniger,
1966). The title compound contains the peptide linkage
- N H - C O - in the cis configuration. In addition, it belongs to a class of non-aromatic cyclic compounds
which are being extensively investigated in this laboratory [trans-2,5-, cis-2,3- and trans-2,3-dichloro-l,4dioxane, Altona, Knobler & Romers (1963), Altona &
Romers (1963a, b); trans-2,3-dichloro-, 2-phenyl- and
trans-2,5-dibromo-l,4-dithiane, Kalff & Romers (1965,
1966a, 1966b), cyclohexane-l,4-dione, Mossel & Romers (1964)].
* Part XXVII, Geise (1967).