Journal of Molecular Structure
Elsevier Publishing Company, Amsterdam.
Printed in the Netherlands
101
MICROWAVE SPECTRA OF DEUTERATED GLYCOLALDEHYDES
K.-M. MARSTOKK
Department
AND HARALD
of Chemistry,
University
MØLLENDAL
of Oslo, Blindern,
Oslo 3 (Norway)
(Received January 21st, 1970)
ABSTRACT
The microwave spectra of CHzOD-CHO, CHzOH-CDO, CHDOH-CHO,
and CHDOH-CDO have been measured and a partial substitution structure of
glycolaldehyde has been ca1culated.
The rotational constants of the parent and the deuterated speeies were
found to be insufficient to yield a complete structure of the molecule.
INTRODUCTION
The microwave spectrum of glycolaldehyde was reported in a previous
paperl. Several conformers are theoretically possible for this molecule, but only
one speeies having the carbonyl and the hydroxyl groups Gisto one another was
identified. A search for other conformers was made, but none could be found.
Moreover, the great majority of the stronger lines of the spectrum was assigned
to cis-glycolaldehyde by applying Watson's first order centrifugal distortion
formulaz, and the possibility that conformers other than the cis exist at appreciable
concentrations at room temperature was considered unlikely.
In the present paper the microwave spectra of four deuterated speeies of
glycolaldehyde are presente d and the substitution coordinates 3 of the hydrogen
atoms have been calculated.
EXPERIMENT
AL
CHzOD-CHO was prepared by dissolving glycolaldehyde (purum from
Fluka A.G.) in DzO together with a drop of formic acid as catalyst. DzO and the
acid were then distilled off at reduced pressure. By repeating this proeess several
times CHzOD-CHO of about 50 % purity was obtained as determined from the
microwave and mass spectra.
J. Mol. Structure, 7 (1971) 101-109
102
K.-M. MARSTOKK,
H. MØLLENDAL
To produce a mixture of deuterated species of glycolaldehyde, anhydrous
dihydroxyfumaric acid (from Fluka A.G.) was dissolved in about 60 % D1O.The
water was removed by drying over CaCI1. The partly deuterated dihydroxyfumaric
acid was then decarboxylated in dry pyridine as described by Powers et a1.4. The
yields of CHDOH-CHO, CH1OH-CDO, and CHDOH-CDO were roughly 30 %,
15 %, and 15 %, respectively, as estimated from the microwave spectrum. Lines
belonging to CH1OH-CHO and CH1OD-CHO were also fouod in this spectrum
in addition to weak lines presurnably belonging to other dideuterated glycolaldehydes than CHDOH-CDO.
The spectra were measured at room temperature in a conventional Stark
effect spectrometer employing 50 kHz Stark modulation and phase-sensitive
detection. Frequency measurements were carried out with a frequency standard
having a stability of 0.05 p.p.m. and a calibrated communications receiver.
Calibration was perforrned against lines of known frequencies and standard
frequency broadcasts. The 12.3-26 GHz spectral region was examined.
MICROW AVE SPECTRA
The low J transitions of CH1OD-CHO, CH1OH-CDO, CHDOH-CHO,
and CHDOH-CDO were found very close to the predicted anes. Most of these
lines were confirmed by their qualitative Stark effects and rigid rotor fit.
TABLE
1
THE MICROWAVESPECTRUM,OF CH2OD-CHO
Transition
Observed
JK-1Kl
--+ Jk' -lK' 1
frequency
(MHz)
00. o
10.1
20.2
21.2
30,3
32,2
40,4
53,3
53,3
63.3
74.3
73.4
84.4
84.5
95.4
95.5
105.5
--+ 11. 1
--+ 11. o
--+ 21.1
--+ 30.3
--+ 31.2
--+ 41,3
--+ 41,3
--+ 44, o
--+ 62,4
--+ 72.6
--+ 65,2
--+ 82.7
--+ 75.3
--+ 75.2
--+ 86,3
--+ 86.2
--+ 96.4
22373.78
12607.77
14390.33
23956.65
17357.03
17740.04
21785.78
24943.86
16949.93
15805.32
25141.45
23212,09
13084.87
13357:32
25538,26
25565.10
13522.66
J. Mol. Structure,
7 (1971)
101-109
Calculated
*
frequency
(MHz)
22373.783
12607.851
14390.266
23956.740
17357.065
17740,101
21785.736
24943.817
16950.024
15805,256
25141.398
23212.189
13084.750
13357.204
25538.184
25565.007
13522.673
Centrifugal
dist. correction
(MHz)
0.016
0.022
0.083
-0.534
-0.012
-1.996
-0.570
- 2.454
-7.48:;
-5.170
-1.857
-5.794
4.903
4.448
0.642
0.573
11.267
MICROW
TABLE
A VE SPECTRA
OF DEUTERA
TED
103
GL YCOLALDEHYDES
1 (continued)
Transition
Observed
Calculated
JK-lKj
frequency*
(MHz)
frequency
(MHz)
Centrifugal
dist. correction
(MHz)
13602.16
22643.78
25873.93
25896.85
25904.40
13883.18
13905.39
23100.46
24179.82
14219.70
14225.69
22966.62
23296.42
14550.52
14551.92
22636.93
22732.20
22253.92
22280.34
15218.50
15218.50
21859.31
21866.39
15560.60
15560.60
15910.25
15910.25
21062.43
16268.45
16268.45
20656.74
20656.74
16636.39
16636.39
20243.71
20243.71
17015.23
17015.23
19821.09
19821.09
17405.95
17405.95
19387.30
19387.30
17809.42
17809.42
18226.76
18226.76
13602.136
22643.743
25873.973
25896.888
25904.352
13883.165
13905.289
23100.463
24179.872
14219.630
14225.597
22966.634
23296.485
14550.451
14552.024
22636.954
22732.208
22253.865
22280.313
15218.473
15218.576
21859.326
21866.459
15560.588
15560.614
15910.141
15910.147
21062.549
16268.353
16268.355
20656.698
20656.823
16636.345
16636.346
20243.752
20243.783
17015.172
17015.172
19821.197
19821.205
17405.846
17405.844
19387.307
19387.310
17809.342
17809.343
18226.719
18226.719
11.009
-33.255
-43.160
6.066
6.031
21.510
21.386
- 56.466
-62.422
36.501
36.448
-85.733
-88.675
57.095
57.074
-121.877
-123.157
- 165.994
-166.504
118.533
118.530
-219.162
-219.352
161.107
161.106
212.741
212.740
- 356.556
274.303
274.302
-442.552
-442,559
346.661
346.661
- 541.300
-541.302
430.686
430.686
-653.650
-653.651
527.247
527.246
- 780.468
-780.468
637.208
637.209
761.539
761.539
--+ J.
1\ K'1
105,6
--+ 96,3
105.5
--+ 114. 8
105.6
--+ 114. 7
116.5
--+107.4
116.6
--+ 107.3
126.6
--+117.5
126.7
--+ 117.4
126.6
--+ 135.9
126.7
--+ 135.8
147.7
--+ 138.6
147.8
--+138.5
147.7
--+ 156.10
147.8
--+ 156.9
168.8
--+ 159.7
168.9
--+159.6
168.8
--+ 177.11
168.9
--+177.10
189.9
--+198.12
189.10
--+ 198.11
2010.10 --+ 1911.9
2010.11 --+ 1911.8
2010. 1O --+ 21 9. 13
2010. 11 --+ 219. 12
2211.11 --+ 2112. 10
2211.12 --+ 2112.9
2412,12 --+ 2313.11
2412.13 --+ 2313.10
2412.13 --+ 2511, 14
2613.13 --+ 2514. 12
2613.14 --+ 2514 11
2613.13 --+ 2712. 16
2613.14 --+ 2712. 15
2814.14 --+ 2715. 13
2814.15 - 2715.12
2814,14 --+ 2913. 17
2814,15 --+ 2913. 16
3015.15 --+ 2916. 14
3015,16 --+ 2916.13
3015,15 --+ 3114. 18
3015,16 --+ 3114. 17
3216.16 --+ 3117, 15
3216,17 --+ 3117.14
3216.16 --+ 3315.19
3216,17 --+ 3315. 18
3417.17 --+ 3318.16
3417.18 --+ 3318, 15
3618.18 --+ 3519.17
3618.19 --+ 3519.16
-* ::1:0.05 MHz.
J. Mol. Structure, 7 (1971) 101-109
104
K.-M. MARSTOKK,
H. MøLLENDAL
T ABLE 2
THE MICROWAVE
SPECTRUM
OF CH2OH-CDO
Transition
Observed
JK-1Kl
--->-J"'-lK'l
frequency*
(MHz)
frequency
(MHz)
--->-
1,.,
1,. o
--->-2,.,
21930.30
21930.295
-0.039
--->-
12372.23
14118.04
12372.270
14118.113
-0.028
-0.073
--->- 30.3
23422.23
17023.56
17281.05
21360.55
15324.26
22578.16
20070.51
25046.76
23333.30
15130.65
15513.56
15513.56
20851.08
15900.93
15900.93
16293.57
16293.57
19963.58
16692.88
16692.88
19519.01
17099.79
17099.79
19069.93
19069.93
17514.81
17514.81
18613.64
18613.64
17939.09
17939.09
18149.13
18149.13
18373.16
18373.16
23422.295
17023.644
17281.028
21360.502
15324.184
22578.165
20070.491
25046.795
23333.284
15130.499
15513.529
15513.630
20851.101
15900.827
15900.853
16293.614
16293.621
19963.689
16692.922
16692.924
19519.167
17099.682
17099.682
19069.928
19069.956
17514.763
17514.763
18613.673
18613.680
17938.990
17938.990
18149.183
18149.183
18373.160
18373.160
00. o
10.1
20.2
2'.2
30.3
32.2
40.4
63.3
73.4
84.4
105.6
126.7
189.9
20,0.,0
20,0.11
20,0.11
2211.11
2211.12
24,2.,2
2413.13
2412.13
2613.13
2613. 14
2613.13
28,4.,4
2814.15
--->- 3'.2
--->- 4'.3
--->- 4'.3
2814.14
--->-2913.17
--->- 72.6
--->- 82.7
--->- 93.7
--->-114.7
--->-135.8
--->-17,0.8
--->-1911.9
--->-1911.8
--->-219. 12
--->-21,2. 10
--->-21,2.9
--->-2313. 11
--->-23,3.,0
--->-2511.14
--->-25,4. 12
--->-2514. 11
--->-27,2. 16
--->-27,5.,3
--->-27,5.,2
2814. 15 --->-2913. 16
3015.15 --->-29,6. 14
3015.16 --->-29,6.13
3015.15 --->-31,4. 18
3015.16 --->-31,4.,7
32,6.,6
--->-31,7.,5
32,6.,7--->-31,7.,4
32,6.,6
--->-3315.19
32,6.,7
--->-3315.18
34,7. 17 --->-33 18. 16
34,7.,8
--->-3318.15
* ::J::0.1OMHz.
J. Mol. Structure, 7 (1971) 101-109
Calculated
Centrifugal
dist. correction
(MHz)
-0.639
-0.327
-1.950
-1.090
-4.688
-5.706
-14.229
-37.032
-53.156
63.253
89.642
89.640
-182.899
122.420
122.420
162.273
162.273
-295.211
209.886
209.886
-365.362
265.947
265.947
-445.754
-445.758
331.141
331.141
-537.065
-537.066
406.155
406.155
-639.676
-639.676
491.677
491.677
MICROW
TABLE
A VE SPECTRA
OF DEUTERATED
105
GLYCOLALDEHYDES
3
THE MICROWAVESPECTRUM OF CHDOH-CHO
Transition
Observed
JK-IKI
--+ J", -lK' 1
frequency*
(MHz)
00.0
20.2
21.2
30.3
32.2
40.4
53.3
63.3
74.4
84.4
95.4
95.5
105.5
1I6.5
1I6.6
126.6
137.6
137.7
158.8
158.7
158.8
179.8
179.9
1910. 9
191;).10
1910.9
1910.10
2111.10
21".11
21",10
2312."
2312.12
2312.12
2513.12
2513.13
2513.12
2513.13
2714.13
2714.14
2714.13
2714.14
2915.14
2915.15
2915.14
2915.15
3116,15
3116. 16
--+ 11.1
--+ 21.1
--+ 30.3
--+ 31.2
--+ 41.3
--+ 41.3
--+ 62.4
--+ 72.6
--+ 83.5
--+ 93.7
--+ 104.7
--+ 104.6
--+ 114. 6
--+ 125,8
--+ 125.7
--+ 135.9
--+ 146.9
--+ 146.8
--+ 149.5
--+ 167.10
--+ 167.9
--+188.11
--+ 188.10
--+ 1811.8
--+ 18".7
--+ 209. 12
--+ 209."
--+ 2012. 9
--+ 2012.8
--+ 2210. 13
--+ 2213. 10
--+ 2213. 9
--+ 2411. 13
--+ 2414. "
--+ 2414.10
--+ 2612. 15
--+ 2612.14
--+ 2615.12
--+ 2615. 11
--+ 2813.16
--+ 2813. 15
--+ 2816.13
--+ 2816.12
--+ 3014. 17
--+ 3014. 16
--+ 3017.14
--+ 3017. 13
21831.85
13841.87
23855.90
16665.54
18056.67
20878.11
17752.80
17143.00
15560.15
22303.04
12796.99
14251.39
24612.95
13375.20
13827.60
25530.97
13662.22
13793.52
21812.81
13859.48
13895.96
14032.44
14042.16
21443.90
21443.90
14198.38
14200.95
21261.83
21261.83
14360.47
21083.74
21083.74
14518.12
20910.80
20910.80
14669.49
14669.49
20743.56
20743.56
14814.00
14814.00
20583.50
20583.50
14949.80
14949.80
20431.46
20431.46
Calculated
frequency
(MHz)
21831.777
13841.945
23856.052
16665.51I
18056.799
20878.057
17752.843
17143.045
15560.213
22303.046
12796.961
14251.379
24612.945
13375.168
13827.616
25530.866
13662.272
13793.454
21812.919
13859.501
13895.841
14032.337
14042.085
21443.750
21443.780
14198.283
14200.836
21261.928
21261.935
14360.378
21083.828
21083.830
14518.105
20910.682
20910.682
14669.584
14669.626
20743.585
20743.585
14813.957
14813.967
20583.540
20583.540
14949.851
14949.853
20431.481
20431.481
Centrifugal
dist. correction
(MHz)
-0.038
-0.088
-0.616
-0.394
- 2.032
-1.296
-6.959
-4.091
-13.866
-13.840
-18.766
-22.532
-28.931
-32.717
-34.813
-48.812
-51.040
- 52.024
19.881
- 74.467
- 74.879
-103.803
-103.962
53.924
53.923
-139.827
-139.884
79.130
79.129
-183.278
110.724
110.724
-234.880
149.404
149.404
-295.318
-295.321
195.869
195.869
-365.315
-365.315
250.816
250.816
-445.560
-445.560
314.944
314.944
J. Mol. Structure. 7 (1971) 101-109
106
K.-M.
MARSTOKK,
H. M0LLENDAL
TABLE 3 (continued)
---~---
Transition
J K- l K l
--+
31,6.,5
31,6.,6
33,7.,6
33,7.,7
33,7.,6
33 17. 17
35,8.,7
35 18. 18
--+ 32,5.,8
--+ 3215. 17
--+ 32,8. 15
--+ 32,8. 14
--+ 34,6.,9
--+ 34'6 18
--+ 34,9.,6
--+ 34,9. 15
J", -
l K' l
Calculated
Observed
frequency*
frequency
(MHz)
(MHz)
--------------------_.._.-
Centrifugal
dist. correction
(MHz)
15076.25
15076.25
20288.28
20288.28
15192.32
15192.32
20154.75
20154.75
-536.755
-536.755
388.955
388.955
-639.242
-639.242
473.536
473.536
15076.188
15076.189
20288.297
20288.297
15192.347
15192.347
20154.826
20154.826
* :::!:0.07 MHz.
T ABLE 4
THE MICROWAVE
SPECTRUM OF CHDOH-CDO
Transition
Observed
Calculated
JK-1Kl
--+ J", - lK' 1
frequency*
(MHz)
frequency
(MHz)
00. o
20.2
2'.2
30.3
32.2
40.4
--+1,.,
--+2,.,
--+ 30.3
20526.47
12945.27
23761.46
15874.46
19681.09
20266.31
25882.23
20526.51
12945.29
23762.22
15874.58
19682.48
20266.93
25882.21
5,.4
--+
3'.2
--+4'.3
--+4'.3
--+52.3
* :::!:0.12 MHz.
The higher J transitions of the three monodeuterated glycolaldehydes were
readily assigned using a procedure very similar to the one reported for the main
species1. The lines were fitted to Watson's first order centrifugal distortion formula
w = Wo-dJJ2(J+l)2-dJKJ(J+l)<P/)
-dK<Pz4)-dwJWoJ(J
+ l )-dWKWO<pz2)
(l)
using the computer program MB07 described in ref. 1. The spectra are shown in
Tables 1-3 and the results cf the least squares fitting are given in Table 5.
For CHDOH-CDO a centrifugal distortion analysis was not carried art,
and the rotational constants given in Table 5 are estimated from low J transitions.
The spectrum ofthis speeies is shown in Table 4.
J. Mol. Structure, 7 (1971) 101-109
~
....
(")
::o
O
~
>
<:
T ABLE 5
MOLECULAR
CONSTANTS FOR ISOTOPIC GLYCOLALDEHYDES
-----CHDOH-CDO
--7
Speeies
CH2OH-CHO*
CH2OD-CHO
CH2OH-CDO
CHDOH-CHO
Number of lines
a(MHz)**
49
0.089
---------
65
0.071
38
0.068
55
0.077
A
(MHz)
18446.410:1: 0.026
17490.806:1:0.015
17151.310:1:0.033
16987.977 :1:0.031
B
(MHz)
6526.042:1: 0.008
6499.754:1:0.006
6362.975 :1:0.021
6385.521 :1:0.007
6233.30:1:0.10
C
(MHz)
4969.274:1:0.012
4882.969 :1:0.008
4779.018 :1:0.010
4843.832:1:0.017
4663.73::1:0.10
lA
(am u A2)
27.40539 :1:0.00004
28.90267 :1:0.00002
29.47477 :1:0.00006
29.75816:1:0.00005
31.8690
:1:0.0003
IB
(amu A2)
77 .46364 :1:0.00009
77. 77694 :1:0.00007
79.44884:1:0.00021
79.16832 :1:0.00009
81.1017
:1:0.0013
le
(amu A2)
101.73136 :1:0.00025
103.52943 :1:0.00017
105.78136 :1:0.00022
104.36592 :1:0.00037
108.3963
:1:0.0023
dJ
(kHz)
-27.14:1:0.54
-23.83:1:0.61
dJK
(kHz)
- 73.22 :1:0.72
-65.04:1:0.48
~
dK
(kHz)
~
:-
dWJ X 106
dWK;< 106
V)
IA+IB-Ie
(amu A2)
~
s:::
~
s:::
... * Taken from ref. I.
88.3:1: 1.4
5.648 :1:0.096
-3.40:1:0.12
3.13767 :1:0.00027
."
-23.4:1:
1.8
-54.79:1:0.66
- 29.9:1: 1.3
- 58.35 :1:0.80
84.2:1: 1.1
61.4:1: 1.3
73.4:1: 1.7
4.87 :1:0.13
5.28:1:0.43
6.38 :1:0.28
-4.137:1:0.094
3.15018 :1:0.00019
--"---
-2.32:1:0.11
3.14225:1:0.00031
-3.54:1:0.17
15862.78:1:
0.15
t1'1
on
"el
t1'1
(")
...,
::o
>
O
"1
tj
t1'1
c::
...,
t1'1
::o
>
...,
t1'1
tj
O
t""
><
(")
O
t""
>
t""
tj
t1'1
::c
K'
tj
t1'1
on
-viCalcY/Njt
-.I ** a = [1:(V1ObS.
-::::
\J:)
-.I
Conversion factor 505531 MHz amu A2.
The uncertainties are standard deviations.
o
.!..
o
\J:)
......
o
-.]
108
K.-M. MARSTOKK,
H. MØLLENDAL
STRUCTURE
Since the heavy atoms have not been substituted the complete rs structure
of glycolaldehyde cannot be calculated. However, the substitution coordinates of
the hydrogen atoms have been calculated from Kraitchman's equations 3,employing
CHzOH-CHO as the parent molecule. The standard deviations of these coordinates were calculated from the standard deviations of the rotational constants
using the formula for propagation of errors5 and a computer program MB13.
They do not, of course, inc1ude systematic errors. The coordinates are shown in
Table 6 and the molecule is depicted in Fig. l.
TABLE 6
SUBSTlTUTlON
COORDINATES
Principal
Atom
FOR GLYCOLALDEHYDE
axes
a
b
c
(A)
(A)
(A)
H(1)
-0.5485::1:0.0004
H(2,2')
-0.9804::1:0.0002
1.2308 ::1:0.0001
1.3857 ::1:0.0001
H(3)
-1.2811
::1:0.0001
-1.4733
::1:0.0001
0.0*
::1:0.8818::1:0.0002
0.0**
* The coordinate is 0.0 for symmetry reasons. Kraitchman's equations yield 0.0821 ::1:0.0012Å.
** The coordinate is 0.0 for symmetry reasons. Kraitchman's equations yield 0.0508 ::1:0.0031Å.
The uncertainties are standard deviations ca1culated from the standard deviations of the
rotational constants. Systematic errors are not included.
o
o
a
H(3)
Fig. 1. Projection of glycolaldehyde in the a-b plane.
Attempts were also made to calculate the ro structure of the molecule by
the least squares method usmg a computer program MB12 allowing all independent
parameters to vary, but no unique minimum was found. The same difficulty was
also experienced when the C=O distance solely or the C=O and C-H distances
simultanously were preset to constant values. However, convergence was achieved
J. Mol. Structure, 7 (1971) 101-109
MICROW
A VE SPECTRA
OF DEUTERA
TED
GL YCOLALDEHYDES
109
when the C=O and C-C distances simultaneously were kept constant in the least
squares fitting. In Table 7 we have given the structural parameters and the range
in which they vary when the C=O distance is kept constant at 1.216 Å (the ro
value found for acetaldehyde6) and the C-C distance is varying in the range
TABLE 7
MOLECULAR
STRUCTURE
c-O
C-C
C-O
O-H
C-H (CH2OH)
C-H (CHO)
L c-c~o
L O-C-C
L C-O-H
LC-C-H (CH2OH)
L H-C-H
L C-C-H (CHO)
OF GLYCOLALDEHYDE*
1.216Å (ass.)
1.501 ::1:0.005 Å (ass.)
1.401-1.406 Å
1.071-1.097 Å
1.105-1.109 Å
1.085-1.097 Å
121.8-124.2°
113.2-114.4°
100.0-101.5°
108.4-108.7°
107.1-107.4°
116.2-116.5°
* See text.
1.501:t 0.005Å (ref.6). Thesebond angles and distancesare, of course, subjectto
rather large uncertainties and must be regarded with caution. A comparison with
structural parameters of related compounds is therefore considered to be of little
value. Obviously, the present experimental data on glycolaldehyde is insufficient
to yield a complete and accurate structure for the molecule.
ACKNOWLEDGEMENT
Financial support from the Norwegian Research Council for Science and
Humanities is gratefully acknowledged.
REFERENCES
l
2
3
4
5
6
K.-M. MARSTOKK AND H. MØLLENDAL, J. Mol. Structure, 5 (1970) 205.
J. K. G. WATSON, J. Chem. Phys., 45 (1966) 1360.
J. KRAITCHMAN, Am. J. Phys., 21 (1953) 17.
H. H. POWERS, G. TABAKOGLU AND H. Z. SABLE, Biochem. Prep., 4 (1955) 56.
J. TOPPING, Errors of Observation and their Treatment,
Chapman
and Hall, London,
R. W. KILB, C. C. LIN AND E. B. WILSON, JR., J. Chem. Phys., 26 (957) 1695.
1963.
J. Mol. Structure, 7 (1971) 101-109