TBE CRYSTAL STRUCTURE
A4
of
DIGLYOINE HYDROBROMIDE
by
(XA)
ELSA PAULINE BARNE
A.B., Syracuse University
(1944)
SUBMITTED IN PARTIAL FULFIi 1JMENT OF THE
REQlImRkENTS FOR THE DEGREE OF
MASTER OF SGIENCE
at the
MASSACHUSETTS INSTITUTE OF TECHNOLOGY
(1947)
Signature of author..............0........
...............
096
Department of Geo 6gy, May 23, 1947
Certified
Thesis Supervisor
*.hairman,000
Dpte
o
te
on........
Gradu*teSuen*000
Chairman, Department Committee on Graduate Students
The Crystal Struoture
of
Diglycine Hydrobromide
28 771G
Table of Contents
Page
Introduction
Literature and History of The Problem
Material
Figure I. Typical Habit of Crystals
Exrperimental Method of Investigation
The Unit Cell
The Space Group
Figure 2 Perspective View of Space Group
Figure 3 Derivation of Equi-points
Determination of Parameters
First Patterson Projection (xy0)
Table I De Jong I and F values
Figure 4 Patterson Projection txyo)
Preliminary Electron Density (xyo)
Sample Structure Factor Calculations
Figure 5 Electron Density (xy0)
Second Approximation
Patterson Synthesis
Second Electron Density
Preliminary Comparison of Intensities
Figure 6 Patterson Projection *xyD)
Figure 7 Patterson Projection (oyz)
Figure 8 Patterson Projection (xoz)
Figure 9 Complete Patterson Projections
Electron Density Maps (xoz) and (oyz)
Figure Ia Electron Density (xyo)
Figure 10 Electron Density (oyz).
Figure II Electron Density (xoz)
Figure 12 Complete Electron Density Maps
Atomic Positions
Second Intensity Comparison
Final Electron Density
Figure 13 Final Electron Density Map (xyo)
Table 2 Comparison of Observed and Calculated
Intensities Under Three Conditions
Structure
Discussion
Figure 14 Projection of Determined Structure
Acknowledgment
I
2
2
3
3
4
5
6
7
7
8
II
12
13
14
15
23
23
23
24
25
26
27
28
29
30
31
32
33
33
34
35
36
43
43
44
45
1
Introduction
Due to the possibilities of the use of diglycine compounds
in glycine separations and identifications and their usefullness
as therapeutic agents it would seem desirable to obtain information on the structure of one such compound. By X-ray analysis
the arrangement of the atoms in the crystal unit may be determined
and the properties of the crystal may ble accounted for in terms
of this arrangement. A crystal such as diglycine hydrobromide
affords an excellent example of the use of a heavy atom in deft
termining the phase constants which cannot be ascertained from
experimental observations.
Briefly the steps in the structure determination consisted
of the following:
I.
Determination of the unit cell and space group.
2. Determination of the atomic positions.
Literature and Hiat&ry of the Problem
As far as is known no previous work has been done on the
crystal structure of diglycine hydrobromide. The method of
preparation of diglycine hydrobromide, diglycine hydrochloride
(I) Refers to two glycine molecules, not glycylglycine.
2
and diglyoine hydrbodide has been reported by Walter S. Frost.
Previous to this diglycine hydrochloride was reported by K. Kraut3
and F. Hartmann.
Material
Orystals and powder of diglycine hydrobromide (. H,,
Br Nx 0,
)
were presented by Dr. W. S. Frost of the Burnham Soluble Iodine 0,
Auburndale, Mass. The material had been made by evaporation of
water solutions of glyoine and monoglycine hydrobromide and glyoine
and hydrobromic acid in theoretical quantities. Suitable crystals
for x-ra4 work could no.t be found in this material so that crysta3s
were grown by evaporation of a water solution of the diglyoine
hydrobromide powder. The crystals are stable in the dry condition,
very soluble in water yielding free hydrobromic acid on dissolving in water and are insoluble in alcohol and ether. The
average melting point in I63 - 165.
The orthorhombic crystals are elongated parallel to the c axis
and are almost equidimensional in cross section. The typical habit
of the crystals is shown in Figure I.
(2) Walter S. Frost. Bis (Amino-Aoid) Derivatives. I. Diglycine
Halogen Addition Products. J.A.O.S. 64 (1942) 1286.
(3) K.Kzaut and F. Hartmann. Ann 133 (1865) 101.
3
Experimental Method of Investigation
The colorless crystals of diglycine hydrobromide were investigated by means of the Do Jong, Weissenberg, precession and
rotation x-ray methods. X-ray work with the De Jong method was
done by M. J. Buerger. For the determination of parameters the
Weissenberg method was used for the hko and hol reflections
using OuX
radiation. The precession method was used for the
okl reflections using MoK, radiation. The Dawtoniethod was used
to determine the intensities.
The Unit Cell
A o-axis rotation photograph gave o a 5.40 A. Measurements
from a c-axis Weissenberg photograph gave a = 8.21 A
b
and
18.42 A.
The number of molecules per cell is 4 and may be calculated
as,
Z
Volume (density)
Formula weight ( 1.66 x 10'"
(5.40)(I8.42)(8.2I)
231.02
x IO~'
( I.66 x I0~"
(1.941)
)
= 4.12
(4) Dawton, Rl.H.V.N.
Crystal Reflections.
The Integration of Large Numbers of X-ray
Proo. Phys. Soc. 50 (1938) 9I9-$25.
(4) Klein, G.E. The Crystal Structure of Nepheline. Thetis M.I.T. (1947)
4
The Space Group
The space grpup P-2, 2,.,
using the Weissenberg
was determined by M.J. Buerger
photographs. Characteristic absences
noted indicating this space group are;
hoo
where h odd
oko
where k odd
ol
where 1 odd
F
'Reflection
Uondition for
non-extinction
h= 2n
hoo
Interpretation of
0II screw axis,
component
k
oko
.Symbol of
Extinction
E0I
2n
symmetry elenet
2,
/h
screw axis,
2,
component 1/
ool
1
2n
0OI screw axis,
component '-
2,
Only general positions occur in this space group. The equi-points
with the conventional origin'of this space group are:
x7z; '2-x, -. , '+Z;
2+x,
}2-Y,
Z; x, -i+y, i-Z.
(5) M.J.Buerger. X-Ray Orystallography, John Wiley and Sons Inc.
(1942) 83.
(6) Internationale Tabellen zur bestimmung Kristallstrukturen. I
(Gebruder borntraeger berlin (1935).
-
s
st1
2 .2
s
6
4
F
I
~-I-------
-
.1
-1---------------
-
I
I
I
0
I
I
~\
f
'4
f
I
I
4+
i;
1
.
4+
4+
WI
I!
If
I.
~
0
If
It
x1y3yx4yv iA-rn ~
F,
4
\Jr
c-
7
However, for this work the origin was taken on a two fold
screw axis because for the prism zone reflections the B terms
of the structure factor vanish. In general simplification of
the structure results if the origin of the coordinates to
which the positions of the atoms are referred is taken as a
symmetry center of the space group. With this origin the
equi-points are
xqy, z;
iit
i-y, ';
}-x,
i+y, i-Z; x,
j, 9
z
The space group symmetry elements are shown in Figure 2. Figure 3
indicates the derivation of the equi-points of the general position
as used in this work.
Determination of Parameters
First Patterson Projection (xyo).
Initially F values from a De Jong photograph taken by
Me.J
Buerger were used to obtain a Patterson projection (xyo). The
F values were obtained directly as the intensities which are
usually obtained experimentally were corrected for by means of a
mechanical cam. The
2 atterson
and Tinell method was used for all t'
the Patterson projections for this crystal. The IFI
values for
the various hko reflections used in this summation are given in
Table I.
(7) R, L. Patterson and G. Tunell. A Method For The Summation of The
Fourier Series Used in The X-ray Analysis of Orystal Structure. Amer.
Mineral. 27 (1942) 655-679.
8
Table I.
De Jong IFI
Refleotion
020
040
Observed
F 2.*
.2
060
1.2
.2
080
4.0
and F values.
t5 F
2
12
2
F
51%%w
14
34
14
-4
40
II
-34
@100
0120
0140
I.I'
8.4
5.4
84
-92
54
-74
IO
120
7.6
76
130
140
150
160
170
180
190
1100
III0
1120
1130
1140
1150
200
210
220
230
240
250
260
270
280
290
2100
21I0
0.0
0
.5
5
1.2
5.I
12
6.6
4.0
8.5
1.2
10.6
51
66
0
85
2.0
12
106
20
7.8
.5
78
5
0.0
0
41
4.1
.4
1.2
5.7
5.7
I.I
1.8
1.8
15.8
2.9
7.5
8.5
4
12
57
57
II
Is
18
158
29
75
85
16
2120
2130
1.6
.I
3.9
2140
5.3
53
2150
I.I
II
11.7
I17
4
53
13
32
320
330
5.3
340
350
1.3
3.2
.4
I
39
87
0
22
-35
71
-8I
0
-92
-35
-103
-32
-88
-22
0
-64
-20
-35
-75
-75
-33
-42
-42
-I26
54
-87
92
-28
I0
-62
73
33
-108
20
-73
36
-57
9
Table I (ont.-)
De Jong 1'1k and
Reflection
360
370
380
390
3100
3110
F values.
F
Observed
F
.a
.9
.4
.3
4.2
8
9
4
3
28
-30
20
42
71
65
84
3
280
167
17
3120
3130
7.1
.3
28.0
400
.2
410
3.9
.5
.3
.4
2
39
5
3
4
8.0
80
89
.9
131*00
9
-30
144
20
420
430
440
150
460
470
480
490
9.7
4100
0,
4110
4120
13,6
.8
510
5.7
.7
520
530
540
550
560
570
580
590
5100
5110
600
610
620
630
640
650
.4
11.8
2.9
.4
9.9
0
5.0
I.1
130
4
97
17
-14
62
-22
17
-20
98
0
0
136
117
8
28
57
7
75
20 V&
118
29
84lb?
4
99
0
50
II
54
99
0
71
-33
47
2.2
4.9
22
49
5.4
.4
6.0
0
4.5
0
54
74
4
60
0
45
-20
0
28
-7 I
660
.8
0
8
670
5.I
5I
-70
77
0
67
-
0
10
The prism zones of this space group project as the plane
group 0" which is shown in figure 3. Pertinent data for the
interpretation of the Patterson projection of this plane group
follows.
No. Equi-pts
Group
Coordinates of
egni-points
Fourier Series *F' Series Data
Data
Group
C',
The 2atterson projection depends on F
and not on
Wt.
Rep.
~
Ptst
2_X_1
F . Thus it is
independent of the phase constants. The distance from the origin to a
peak corresponds to an interatomic distance in the crystals. The
Patterson projection (xyo)
of one fourth of the cell (the motif) of
diglycine hydrobromide obtained is given in Figure 4. In view of the
high atomic weight of bromine in the molecule undoubtedly the intense
peaks
1127, 1260 and 543 represent the br-Br interatomic distances.
These points occur at the points Ex },}
,
2y 1; and 2-x, 2y, re-
spectively. With information from the above table the x and y parameters
of the heavy bromine atom were determined as shown in the following
table
table.
(8) A.' L. Patterson. Tabulated Data For The Seventeen Plane Groups.
Zeits,.Krist. vol. 90 (1935) 5I7-542.
7
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QI
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GE'
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Peak
2x+2
2y4j
2
x
2y
x
y
543
1127
-__
1260
3 1f.
Okz
-.
2
reliminary Electron Density
(xyo)
in view of the high atomic scattering power (f)
of bromine
compared with that of the other atoms oxygen, nitrogen and carbon
in the molecule it was assumed that the heavy bromine determined
the phases. Since in projection the crystal is centrosymmetriaal
the phases will be either o or T i.e. t or -.
For the space group
,,
D. , choosing the origin at a
symmetry center the components of the structure factor for an
atom in the general position are as follows:
A
4kcos2Tt(hxtky+lz)+ cos21(h[ +x]+k[I-yi-lz) +
cos2lT(h [ -x1+ k( +y] +1[
I'))
B = 4fsin2(hxtky +1z) + sin2T(h[
sin24(h [-
+ k1i+y1l 1-z)
+ cog2i4(-hx-ky t1I[Jt ')
-+x'+k -y'l-lz) +
+ sin2Tf(-hx-ky + 1[ +z)
kor the various reflections these may be reduced to;
Refl.
hko
hko
okl
okl
hol
hol
A
h+k = 2n
4cos2nhxcos27rky
4cos2'kxcos2rky
k41 - 2n
4cos2irkycos2-iiz
4cos2kycos2flz
htl -2n
4cos2rhxcos2Tilz
4cos2Trhxcos2mlz
,
A
h+k = 2n+I
-4sin2-,hxsin2rky
4sin2lhxsin'wky
k+l -2n+1
-4sin2wkysin2rlz
4sin2TRkysin2-r1z
h+1=2n+I
-4sin2-ihxsin2rl z
4sin2rhxsin21z
l
B
0
0
0
0
0
0
.
I13
hko
:LI
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.
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-
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A sample calculation of the determination of the phases
is given below.
Reflection
Parameters
x
Y
6tructure Factor
ces2irhx
/m
Phase
cos21gy
220
.178
.034
-. 618
.910
130
.178
.034
.437
.802
4-
With the phase constants determined in the abive manner
and using the F values of Table I as obtained from the De Jong
photograpj an electron density p (xyo) was made. The electron
density map
(xyo) of
of the cell, the motif, is given in
Figure 5. With 4 molecules per cell the position of 4 carbons,
I bromine, 2 nitrogens and 4 oxygens (i.e. II positions) should
appear in the electron density map of L of the cell. In the
electron density map obtained the bromine appeared where it was
put in
the structure.
However,many more than 10 other peaks are
seen to occur indicating quite some error.
Second ApproximationDue to the error just indicated it was necessary to obtain
more x-ray data. This was done by means of the Weissenberg
method for the hko and hol reflections using CuKa. radiation and
the precession method for okl reflections usigg MoK.radiation.
The intensities were determined by the Dawton method and corrections
to obtain
IF( are given below. Since intensities are obtained
experimentally and
F's or their squares are used as coefficients
of a Fourier series for electron density maps and Patterson projections
it
is necessary to compute F's. As -1 is a function of sin 5-
16
(7 C
),
sin
must be calculated for all reflections. This
was done by means of the formula
sint
(ah
2
+ o*'-'l'
(- ba
=
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(cjTF
CI.
C
020
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II
(9) M.J. Buerger and G.B. Klein. Correction of X-ray Diffraction
Intensities for Lorentz and Polarization Factors. J. App. Phys.
Vol. 16 No. 7 July 1945 408-4I8.
17
Refleotion
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1.2672
520
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1.2890
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1.3755
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930
940
950
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9
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okl Reflections
Reflection
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020
040
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1.0030
1.0119
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060
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1.0270
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Reflection
sins
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0120
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7
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I
I
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0
2
0
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3
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5
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17
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sin -
c--3kkQ
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0462
0106
0126
0146
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$10) M.J. Buerger. The Photography og The Reciprocal Lattice. ASxED
Monograph No.I
23
Patterson SynthesisPatterson projections were obtained using the new above
The three projections r(xyo), e (oyz),
ande(xoz)
cell are given in Figures
The Br-Br vectors ar
eemoi-d
6, 7 and8.
(Fl
,
for 4 of the
the
(xyo) projection are the same as obtained in the initial
Patterson using De Jong values although the rest of the plot is
different. The complete Pattersons for all three projections are
given in Figure 9. The originsof the three projections are seen
displaced as in each case the origin is on the symmetry element,
the two fold screw axis, and the relation to one another may be
seen from the space group representation of Figure 2.
Second Electron DensityUsing the new
density Q (xyo)
F values for hko reflections, a second electron
was prepared. This second electron density resulted
in the correct number of atomic position peaks. The first electron
density e (xyo) seemt4to be much in error due to an insufficient number
of terms having been used in the series. In the second electron
density etxyo)
I37 terms were used, whereas in the first
75 terms were used.
5v -
to
one only
,.
Preliminary Uomparison of IntemsitiesA preliminary check of intensities for hko reflections was made
using the atomic positions as indicated in the second electron density
e (xyo)
(f)
and assuming an average value of the atomic scattering factor
for the nitrogen, oxygen and carbon as it
was impossible to de-
termine which of these positions represented whiuh atoms. A sample
calculation of intensity follows.
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Parametbks
x
y
mf
Structuie Factor/m
cos21hx '3 cos2Tky
+
150
Br
I
3
4
5
*178
.093
.108
.417
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7
8
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41.51
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-.861
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.588
-.982
-. 982
-.867
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7.75
4074
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5.25
5.19
3.97
6.34
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6.34
--. 861
5.25
I.II
044
-.509
.588
=+ 33.80
The atomic scattering factorf, is determined for each atom for
each refledtion as a function of sine. * The rough comparison of
observed and calculated intensities is given in Table 2.
Electron Density maps Q(xoz) and Q (oyz)Electron density maps t(xoz)
andc (oyz) using the same pro.
ceedure as was used for Q (xyo) were prepared and are given in
Figure 10 and Figure II.
The three complete electron density iaps
all drawn to the same origin are given in figure 12.
(II) M.J. Buerger and G.E. Klein. Correction of Diffraction
Amplitudes for Lorentz and Polarization Factors. J. App. Phys. Vol. 17
No. 4 April 1946
285-306.
(12) Internationale Tabellen zur bestimmung Kristallstrukturen. I.
(Gebruder -Borntraeger, Berlin (1935).
(IW) M.Je Buerger. Numerical Structure Factor Tables.
America Special Paper 33.
Geol. Soc.
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33
Atomic Positions-
By comparing the three electron density maps and assuming
the diglycine structure to be made up of glyoine molecules of
known structure
which of the peaks represented the oxygenpwhich
$he nitrogens and which the carbons were decided upon. The atomic
positions so obtained are:
Atomic positions as determined from
the electron density maps
B
00
N
0
0
0
0
N
0
0
Y
.178 .035
.089
.106
.268
.470
.196
.423
.380
.430
.430
.112
.333
.065
.283
*172
.145
.193
.475 .213
.423 .283
y
.215
.370
.180
z
*167
.333
.120
.I180 .I58
*363 .183
.417 .542
.484
.422
.443
.037
.037
.017
*127
.342
.350
.350
x
z
.072 .083
.161
.I44
.083
.370
.482 .092
.220 .433
*054 .092
.173 .233
.315 .123
.lo5 .408
.225 .100
.173 .400
Atomic positions referred
to the same origin
y
Br
0
G
N
0
0
.178
.035
.089
.106
.268
.470
.380
.196
.430
.430
.112
.333
0
.423
.283
0
.065
.172
N
.145
0
.475
.193
.213
0
.423
.283
z
.833
*833
.I20
.I158
.317
.842
.517
.373
.I58
.650
.350
Second Intensity ComparisonIntensity calculations were made using the parameters as determined from the electron density maps. A comparison of the
observed and calculated intensities using a specific atomic scattering factor, f,
for each of the atoms for each reflection is given in
Table 2.
(14) G. Albrecht and R. Corey.
J. A. 0. S. 61,
5
(1939).
Final Slectron Density I(xyo)-.
Only foar sign changes were found from those determined by Br
alone. The changes were for N320, 0 22 0, 6I0Aand
An electron density map
vno reflections.
(xyo) made with tthese 4 sign changes
showed a slight shift of parameters as indicated in Figure I3.
The new set of parameters from the final electron density
(xyo)
are:
Br
0
0
N
0
0
0
0
N
0
0
x
.178
.095
*104
.278
.462
.200
.450
.072
.149
.472
.418
y
.035
.380
.428
.430
.110
.338
.267
.170
.194
.213
.263
The agreement between observed and calculated intensities is
somewhat improved with these new parameters as is shown for a few
reflections in Table 2.
I/
zo
'(-.
'tf/7
UI2 ?
12-S
I I
167
757
1.5s
10
314
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36
Table 2
Comparison of Observed and Calculated Intensities Under Three Conditions
Condition I.
Rough comparison using an average scattering factor f,
for oxygen, nitrogen and carbon in intensity calculations.
for oxygen, nitrogen
Condition 2
Intensity comparison using correct f
and carbon as well as for bromine.
Condition 3
Intensity comparison using final x and y atomic positions
and condition 2.
Reflection
Observed I Observed Y401
k~o
220
NO
150
230
160
270
040
020
180
330
140
II00
210
080
130
0120
410
530
470
450
II
510
290
3130
2100
44.I
37.9
29.6
26.I
25.7
20.9
15.6
I5.0
14.4
I0.0
9.34
6.6
6.2
5.8
5.75
5.6
5.2
4.9
4.7
4.4
4.2
4.1
Calo.VI/ 4
Condition
Cale. I/ 4
Condition
Cal. 4/4
Condition
I
2
3
41
36
42
37
29
32
31
42
39
34
32
32
40
34.9
33.8
29
25
30
24
24
20
19
16
16
I5
15
23.3
23.3
22
27* I
20.9
2I.0I
16.6
14.7
20.1
9.6
20.6
31
33
29
29
25
21
25
22
25
19
12
17
I7
14
18*7
20
18
20
14
13
13
15.8
19
20.1
II
13
1908
II
14
15
14
I4.9
3.4
12
3.0
II
17
12.9
16.3
2.9
II
I4.7
31
25
21
24
22
23
17.5
I2
13
18*7
18
18
19
17
19
12
15
14.6
14.6
I7
IS
17.8
14.3
37
Refleotion
250
350
240
560
490
1120
260
280
4110
200
600
340
620
3110
0140
8140
2230
190
0160
1200
760
3100
5200
6140
3170
540
720
1050
1070
740
580
640
4210
060
670
7400
1180
910
III0
5110
4190
6120
2140
Observed I
2.7
2.7
2.2
1.9
1.9
1.7
1.6
1.6
1.6
1.3
1.2
1.2
1.2
I.I
.93
.92
.92
.90
.85
.81
.79
.76
.75
.74
.73
.71
.66
.65
.65
.64
.64
.64
.58
.55
.55
.53
.51
.50
.49
.49
.49
.48
.47
Observed V4-0I
8alo. \FI/4
Condition
I
I0
I0
9
9
9
8
8
8
8
7
7
7
7
7
6
6
6
6
6
6
6
6
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
4
4
4
4
4
4
13.8
13.5
12.4
13.4
13.7
13.4
7.6
9.6
12.8
12*5
7*98
7.8
13.2
I3.5
II.*8
Galo. \i/4 0 alo0.NX/4
Condit ion Condition
3
2
12
10.6
12.0
14.8
13
13
I0
I0
I3
I0
I0
II
14
9.5
14*9
IS.0
15
12.4
10.6
14
I0.5
I0
6
7
13
13
II
12
II
17
17.97
1106
19
8.2
9.8
15*9
11.3
12.5
8
12.5
15
13
II
13
14
I0.05
I0
6*96
12
I0
12
8.36
7.88
3.6
8.7
7
8
14
6
9
12
9.7
10
5.0
II
6
7
I0
9
I0
13
38
Reflection
Observed I Observed
I40ICalo.[Fi/4
Condition
I
Calo.JIf/4
Condition
2
6180
800
6160
2210
3150
2130
780
5190
1150
.45
.45
.45
.44
.43
.41
.40
.39
.38
12
13
II
II
9
8
7
12
7
320
4170
420
0100
1220
.36
.36
.36
.33
.32
3
12
3
5
8.5
870
370
360
2180
5I00
.30
.30
.29
.29
.28
8
6
7
9
4.5
0200
.28
820
400
440
5130
2110
980
8120
2190
7120
170
9110
.26
.25
*25
.24
.24
.21
.23
.22
.21
.21
.20
6
4.5
5
9
4.5
13.9
10
7.9
5
5
II
850
.20
3
690
590
6100
4120
6170
.19
.19
8
7
.18
6
.18
.18
3
6
8100
840
.16
.16
7
7
430
940
460
520
2160
6190
.I6
.15
.14
.14
.14
.13
5
II
3.5
5
5
8.6
930
.13
6
1170
960
1160
.13
.12
.11
6
5
5
10
Calo.\I/4
Condition
3
39
Refleotion
Observed I
Observed \(II
Cale. fV/4
Condition
I
alo.{ i/4
Condition
2
k C)
2150
990
4160
5150
860
660
0180
0220
1190
610
480
950
6130
1130
I010
8110
890
7140
4I00
3120
390
380
2120
4140
4200
550
570
5120
5140
6110
6150
I000
.II
.I0
*I0Q
.I0I
.10
.10
.I0
.I0
.08
.08
.06
.06
.05
.05
.05
.02
.01
.0I
0
0
0
0
0
0
0
0
0
0
0
0
0
0
6.5
6.8
5
5
6
6
2
4
3.6
2
7
6
4
5
4
2
Gale. \Ii/4
Gondition
3
Comparison of Observed and Calculated Intensities under Condition(2)
Reflection
Cale. fi/4
Cale. I/Io'
Observed I
OK
061
041
41
34
27
032
031
33
I7.4
15.4
002
31
27
012
28
12.5
5.7
5.2
7.0
071
19
0120
18
053
21
040
073
033
17
I7
II.6
4.6
6.4
4.6
12.4
12
7
7
4.7
4.6
3.3
3.4
3.2
2.7
2.4
2.4
051
0101
II
15
1.9
3.6
022
12
2.3
2.3
093
092
0140
080
014
14
13
3.1
2.7
12
2.3
2.2
2.1
2.0
14
3.1
2.7
034
15
3.6
004
0160
0152
18.7
5.6
1.9
1.9
081
006
0122
0146
0200
A620
0181
0221
0112
'II
II
II
20
I0
12
8
1.9
6.4
1.6
2.3
1.9
1.85
1.7
1.4
1.3
1.20
.97
995
.8
.8
I.0
.8
I0
I0
1.6
1.6
12
8
5
4
5
7
2.3
.4
.25
.7
.7
.7
.76
.7
.67
.4
.6
.8
10
1.6
091
0213
7
II
0180
0132
0193
0134
3
.8
1.9
.14
.8
.6
.65
.55
.5
.5
.5
.5
.5
.5
.4
0201
0191
060
-
20
18.5
28
17.4
OI3
0142
045
065
0211
075
0105
085
0192
0162
084
7
8
9
I5
4
9
9
5
7
5
5
1.0
I.o
1.3
3.6
.25
1.3
1.3
.4
.8
.4
.4
.4
.4
.00
.25
.2
.2
Reflection
calo.
\I/4
Calo.
I/IO
Observed I
Q.)k .
.8
0,II4
OIZ6
064
0172
0113
046
0174
095
0131
7
9
094
5
7
9
1.3
4
4
0124
0154
0106
024
3
4
2
6
7
5
3
.2
.14
.25
.2
.2
.I3
.16
.I13
.57
.8
.13
.4
.I
.14
.4
.8
.25
.06
.03
.03
.03
.08
.25
0
1.3
.I
42
Comparison of Observed and Calculated Intensities Under Condition (2)
Reflection
201
002
I0I
203
102
302
301
403
501
202
502
Observed I
ObservedYl
28.97
13.15
6.11
6038
5.38
3063
2.47
38
32
22
4.29
2.07
2.93
1.71
12
I0
2052
1.59
1.76
1.71
I.33
1.31
1.58
I.54
40067
1.24
1.17
1.02
.98
7.4
16
7.0
6.1
13
.91
.84
.73'
504
401
206
.28
901
.20
204
.18
.15
404
205
405
505
605
803
601
402
702
.025
0
0
0
1905
12*4
7.8
.71
.53
.53
.43
.33
.33
.31
.14
.13
.I0
.I0
.09
.05
.05
.04
.03
13.5
8
7.5
705
400
104
802
602
503
29
25
1.26
.83
902
36
31
13
1.36
1.05
.97
i90
15
Calo. fI
9.5
8
304
600
004
701
006
200
800
105
Observed 6tIF
.95
.73
.66
5.9
5.7
5.5
5.0
4.4
4.4
3.9
.57
.57
.56
.53
3.4
3.4
.44
.43
.39
.37
.36
.32
.32
.30
.22
.22
.20
2.7
2.5
.17
.16
3.3
3.2
2.3
2.3
2.2
I.9
1.9
1.8
1.3
1.3
1.2
1.15
.95
8.3
10
1805
13
23
21
I0
13
7
9
9
6
6
9
3
4
4
5
7
.22
2
7
5
8
6
8.5
Structure
Unit cells
a
b
8.2I A
18.42 A
o
5.40 A
Space group:
Atomic positions:
y
I
z
Br
.178
.935
*833
0
G
N
0
0
.095
.I04
.278
.462
.200
.380
.428
.430
.110
.338
.833
*120
.158
.317
*842
.450
.517
.373
.158
.650
*350
o
o
.072
N
0
.149
.472
.267
.170
.I94
.213
0
.418
*283
Discussion
The above structure can only be regarded as an approximate
structure. The atomic positions are in some error due principally
to the overlapping of the atoms in projection. The atoms could not
be further resolved as only zero level photographs were taken so
that only projections of the cell could be obtained. No account has
been taken so far of the position of the hydrogen atoms in the
structure or of their contribution to calculated intensities. A
projection of the determined structure on xyo is given in Figure 18.
Here the shape of the glycine molecule may easily be seen.
Ok
Ce
rL
rf %rrL-ANV Ol
45
Aoknowledgment
The writer is indebted to Prof.I. J. Buerger for the
suggestion of diglycine bydrobromide for orystal struoture
determination. Suggestions during the work and reading of
the manuscript were most helpful.