A Microwave and Quantum Chemical Study of
Propargyl Thiocyanate (HCCCH2SCN)
Harald Møllendal,*,ϯ Alexey Konovalov,ϯ and Jean-Claude Guillemin‡,§
Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry,
University of Oslo, P. O. Box 1033 Blindern, NO-0315 Oslo, Norway, École Nationale
Supérieure de Chimie de Rennes, CNRS, UMR 6226, Avenue du Général Leclerc, CS 50837,
35708 Rennes Cedex 7, France and Université européenne de Bretagne.
Supporting Information
*To whom correspondence should be addressed. Tel: +47 2285 5674; Fax: +47 2285 5441; Email: harald.mollendal@kjemi.uio.no
ϯUniversity
‡École
§
of Oslo
Nationale Supérieure de Chimie de Rennes
Université européenne de Bretagne
1
Synthesis of Propargyl Thiocyanate
+ KSCN
Br
(acetonitrile)
SCN
Scheme S1
The synthesis of the propargyl thiocyanate has already been reported.1,2
In a 250 mL two-necked flask equipped with a stirring bar and a nitrogen inlet were introduced
propargyl bromide (15.0 g, 0.1 mol 80 % in toluene), 70 mL of dry acetonitrile and potassium
thiocyanate (10.3 g, 0.105 mol). The mixture was stirred for 3 h under reflux. At the end, after
cooling at room temperature and then filtration, a clear yellowish brown solution was obtained.
The solvent was removed in vacuo and propargyl thiocyanate was purified by distillation. bp:
23°C (0.1 mbar), Yield: 8.5 g, 88 mmol, 88 %. 1H NMR (CDCl3, 400 MHz):  2.55 (t, 1H, 4JHH
= 2.6 Hz, CH); 3.71 (d, 2H, 4JHH = 2.6 Hz, CH2); 13C NMR (CDCl3, 100 MHz):  22.9 (d, 1JCH =
151.1 Hz, CH2); 75.8 (t, 1JCH = 255.3 Hz, CH), 76.2 (d, 2JCH = 51.4 Hz, HCC-); 111.2 (s, CN).
2
TABLE 1S: B3LYP/6-311++(3df,3pd) Fundamental Vibrational Frequencies (cm−1)of
the ap conformer H-CC-CH2SCN
Harmonic
Anharmonic
1(1)
2(1)
3(1)
4(1)
5(1)
6(1)
7(1)
8(1)
9(1)
10(1)
11(1)
12(1)
13(1)
14(1)
15(1)
16(1)
17(1)
18(1)
19(1)
20(1)
21(1)
3466.869
3121.893
3069.808
2255.976
2224.149
1469.797
1257.468
1172.860
973.996
895.245
724.441
706.545
686.910
677.033
448.188
427.457
414.004
331.095
186.164
105.554
48.421
3349.298
2971.865
2976.415
2226.465
2181.489
1450.079
1238.088
1150.099
962.554
882.869
707.939
701.751
672.945
672.587
442.318
423.305
409.028
337.260
187.028
106.703
55.605
TABLE 2S: B3LYP/6-311++(3df,3pd) Vibration-Rotation
ap conformer H-CC-CH2SCN
Q( 1)
Q( 2)
Q( 3)
Q( 4)
Q( 5)
Q( 6)
Q( 7)
Q( 8)
Q( 9)
Q(10)
Q(11)
Q(12)
Q(13)
Q(14)
Q(15)
Q(16)
Q(17)
Q(18)
Q(19)
Q(20)
Q(21)
a
3.85197
-11.06873
-1.31903
4.96346
6.89129
12.38390
0.21309
-15.24834
-42.79488
18.63767
59.57009
-789.31476
93.63535
820.22119
-624.25522
-127.28279
551.48093
96.75231
-7.01380
-432.95610
418.77921
b
0.97246
-0.12350
-0.05861
2.74269
2.54747
0.15664
0.28810
0.15806
2.19786
1.41435
0.87039
-1.06957
1.22311
0.96146
0.03762
1.75407
0.75797
-0.32485
-2.55821
-1.88485
0.03198
-Constants (MHz)of the
c
0.85264
-0.22270
-0.20440
2.35972
2.20707
-0.33095
1.10408
-0.64278
1.47921
1.54475
0.98650
-0.10640
2.65703
0.08209
0.81396
2.03897
-0.85746
-0.76090
-1.33636
-0.15187
-2.84192
3
TABLE 3S: B3LYP/6-311++(3df,3pd) Fundamental Vibrational Frequencies (cm−1)of
the sc conformer H-CC-CH2SCN
1(1)
2(1)
3(1)
4(1)
5(1)
6(1)
7(1)
8(1)
9(1)
10(1)
11(1)
12(1)
13(1)
14(1)
15(1)
16(1)
17(1)
18(1)
19(1)
20(1)
21(1)
Harmonic
Anharmonic
3467.187
3110.810
3059.979
2259.822
2223.794
1454.431
1263.925
1200.155
971.204
896.050
698.653
695.653
678.160
653.170
491.428
420.149
408.601
327.256
189.830
146.053
49.955
3356.662
2958.080
2946.505
2228.986
2179.503
1427.579
1237.496
1173.502
956.675
883.259
687.525
701.914
684.026
639.951
487.686
419.182
408.664
335.221
195.348
150.371
59.812
TABLE 4S: B3LYP/6-311++(3df,3pd) Vibration-Rotation
sc conformer H-CC-CH2SCN
Q( 1)
Q( 2)
Q( 3)
Q( 4)
Q( 5)
Q( 6)
Q( 7)
Q( 8)
Q( 9)
Q(10)
Q(11)
Q(12)
Q(13)
Q(14)
Q(15)
Q(16)
Q(17)
Q(18)
Q(19)
Q(20)
Q(21)
a
-1.52932
7.60114
3.60062
7.55063
3.69001
-11.75861
6.39145
11.90416
-5.77097
2.74017
-2.78774
-59.42550
58.18733
8.16997
-21.04165
-21.11744
7.95384
0.24415
-19.48122
5.23168
-26.00426
b
3.61100
-4.23088
-1.57720
5.03310
5.29875
5.02402
0.47306
-5.32026
6.33629
2.39948
2.22295
-13.28047
19.05297
4.65550
5.63360
-10.91854
16.03433
-0.29914
-1.72656
0.12461
-8.85996
-Constants (MHz)of the
c
1.50740
-0.57716
0.22065
3.44950
2.94643
1.20738
-0.35909
-2.21323
1.80359
2.35848
1.35545
-2.51210
3.39822
2.90470
2.86143
1.40514
0.48624
-0.51175
-1.11265
-0.07186
-0.94671
4
Comments for the Spectra Tables:
Hamiltonian: Watson’s A-reduction Ir representation3
Transition labels: J’’ K-1’’ K+1’’ J’ K-1’ J K+1’
obs. – calc.: the observed – the calculated residuals
weight: the estimated uncertainties of the observed frequencies. Each transition is weighted
according to the inverse square of its estimated uncertainty
t: Student’s t-test4
distortion correction: centrifugal distortion correction
total: correction from quartic and sextic (if included) centrifugal distortion constants
higher: contribution from sextic centrifugal distortion constants
fixed: contribution from fixed quartic and/or fixed sextic centrifugal distortion constants. The
values of fixed constants are also displayed
rms deviation: root-mean-square deviation. Defined dimensionless in a weighted least-squares
fit4
: Ray’s asymmetry parameter defined by  = (2B – A – C)/(A – C)
Pseudo-inertial defect: defined by  = Ic – Ia – Ib
Uncertainties: The uncertainties represent one standard deviation
Significant digits: the number of significant digits of each fitted constant is listed on the
diagonal of the correlation matrix
Units: the observed frequencies, the residuals, the distortion corrections, and the rotational
constants are in MHz, the quartic centrifugal distortion constants are in kHz, the sextic
centrifugal distortion constants (if applied) are in Hz, and the principal axis inertial constants and
the inertial defect are in u Å2
5
Table 5S: Microwave Spectrum of the Ground Vibrational State of the ap
Conformer of H-CC-CH2SCN
Total number of transitions: 233
Transition
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
11
11
11
11
11
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
13
13
13
13
13
14
14
14
14
5
5
6
6
7
7
2
5
5
6
6
7
7
8
8
2
3
3
4
4
1
2
3
4
4
6
6
7
7
1
4
4
5
5
6
6
7
7
8
8
9
9
1
2
3
5
5
4
4
3
3
2
9
6
5
5
4
4
3
3
2
10
9
8
8
7
12
11
9
9
8
7
6
6
5
13
10
9
9
8
8
7
7
6
6
5
5
4
14
13
12
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
12
12
12
12
12
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
15
15
15
15
5
5
6
6
7
7
2
5
5
6
6
7
7
8
8
2
3
3
4
4
1
2
3
4
4
6
6
7
7
1
4
4
5
5
6
6
7
7
8
8
9
9
1
2
3
5
obs. frequency
6
5
5
4
4
3
10
7
6
6
5
5
4
4
3
11
10
9
9
8
13
12
10
10
9
8
7
7
6
14
11
10
10
9
9
8
8
7
7
6
6
5
15
14
13
11
26526.140
26526.140
26526.140
26526.140
26526.140
26526.140
29143.850
29178.990
29178.990
29178.990
29178.990
29178.990
29178.990
29178.990
29178.990
31787.210
31847.050
31853.090
31838.130
31838.130
33674.240
34429.420
34513.400
34493.370
34493.370
34485.670
34485.670
34485.670
34485.670
36254.140
37149.970
37149.970
37142.700
37142.700
37139.070
37139.070
37139.070
37139.070
37139.070
37139.070
37139.070
37139.070
38831.840
39707.960
39820.980
39797.660
obs.- weight
calc.
0.148
0.147
0.825
0.825
0.659
0.659
0.188
-0.649
-0.649
0.475
0.475
0.515
0.515
-0.099
-0.099
0.046
0.188
0.028
0.117
0.048
0.263
0.293
-0.260
-0.279
-0.401
0.163
0.163
0.814
0.814
0.196
0.103
-0.104
0.218
0.216
-0.263
-0.263
0.804
0.804
0.674
0.674
-0.245
-0.245
-0.059
0.016
-0.271
0.172
0.40
0.40
0.75
0.75
0.75
0.75
0.25
0.40
0.40
0.40
0.40
0.40
0.40
0.40
0.40
0.15
0.15
0.20
0.15
0.15
0.30
0.20
0.20
0.20
0.20
0.75
0.75
0.75
0.75
0.30
0.25
0.25
0.25
0.25
0.75
0.75
1.0
1.0
1.0
1.0
1.0
1.0
0.15
0.10
0.50
0.10
t
0.3
0.3
1.0
1.0
0.8
0.8
0.7
-1.5
-1.5
1.1
1.1
1.2
1.2
-0.2
-0.2
0.3
1.1
0.1
0.7
0.3
0.8
1.3
-1.2
-1.3
-1.8
0.2
0.2
1.0
1.0
0.6
0.4
-0.4
0.8
0.8
-0.3
-0.3
0.7
0.7
0.6
0.6
-0.2
-0.2
-0.6
0.1
-0.5
1.6
distortion corrections
total
fixed
1.505
1.505
2.465
2.465
3.599
3.599
-0.503
1.499
1.499
2.555
2.555
3.803
3.803
5.242
5.242
-0.730
-0.233
-0.236
0.503
0.503
-1.141
-1.003
-0.481
0.323
0.323
2.596
2.596
4.072
4.072
-1.439
0.090
0.090
1.194
1.194
2.540
2.540
4.129
4.129
5.962
5.962
8.038
8.038
-1.782
-1.703
-1.125
0.983
-2.3E-3
-2.3E-3
-6.7E-4
-6.7E-4
1.1E-3
1.1E-3
5.0E-3
-4.1E-3
-4.1E-3
-2.1E-3
-2.1E-3
-1.1E-4
-1.1E-4
2.1E-3
2.1E-3
8.3E-3
-0.013
-0.016
-9.5E-3
-9.6E-3
0.214
0.013
-0.023
-0.014
-0.014
-6.7E-3
-6.7E-3
-3.9E-3
-3.9E-3
0.272
-0.019
-0.019
-0.014
-0.014
-1.0E-2
-1.0E-2
-6.6E-3
-6.6E-3
-3.4E-3
-3.4E-3
-6.7E-5
-6.7E-5
0.340
0.029
-0.033
-0.019
6
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
5
6
6
7
7
8
8
9
9
2
2
3
3
5
5
7
7
9
9
2
2
3
3
5
5
6
6
7
7
8
8
9
9
10
10
2
3
3
5
5
6
6
7
7
8
8
9
9
10
10
2
3
3
4
4
9
9
8
8
7
7
6
6
5
14
13
13
12
11
10
9
8
7
6
15
14
14
13
12
11
11
10
10
9
9
8
8
7
7
6
16
15
14
13
12
12
11
11
10
10
9
9
8
8
7
17
16
15
15
14
15
15
15
15
15
15
15
15
15
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
19
19
19
19
19
5
6
6
7
7
8
8
9
9
2
2
3
3
5
5
7
7
9
9
2
2
3
3
5
5
6
6
7
7
8
8
9
9
10
10
2
3
3
5
5
6
6
7
7
8
8
9
9
10
10
2
3
3
4
4
10
10
9
9
8
8
7
7
6
15
14
14
13
12
11
10
9
8
7
16
15
15
14
13
12
12
11
11
10
10
9
9
8
8
7
17
16
15
14
13
13
12
12
11
11
10
10
9
9
8
18
17
16
16
15
39797.660
39792.410
39792.410
39792.410
39792.410
39792.410
39792.410
39792.410
39792.410
42344.570
42821.700
42480.560
42506.770
42452.790
42452.790
42446.200
42446.200
42446.200
42446.200
44979.040
45541.970
45140.180
45175.540
45108.830
45108.830
45102.440
45102.440
45099.420
45099.420
45099.420
45099.420
45099.420
45099.420
45099.420
45099.420
47611.420
47800.560
47847.710
47765.100
47765.100
47757.020
47757.020
47753.080
47753.080
47753.080
47753.080
47753.080
47753.080
47753.080
47753.080
50241.730
50461.020
50522.920
50441.190
50442.750
0.169
-0.991
-0.991
0.572
0.572
0.702
0.702
-0.099
-0.099
0.014
0.040
0.029
-0.090
-0.112
-0.117
0.617
0.617
0.417
0.417
-0.104
-0.149
-0.104
-0.367
0.080
0.070
0.102
0.102
-0.093
-0.093
0.729
0.729
0.279
0.279
-1.066
-1.066
-0.175
0.131
-0.041
0.039
0.023
-0.220
-0.220
-0.559
-0.559
0.701
0.701
0.490
0.490
-0.745
-0.745
-0.067
0.156
0.216
0.178
-0.070
0.10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.10
0.15
0.10
0.10
0.10
0.10
1.0
1.0
1.0
1.0
0.15
0.20
0.10
0.30
0.10
0.10
0.15
0.15
0.50
0.50
1.0
1.0
1.0
1.0
1.0
1.0
0.20
0.15
0.15
0.10
0.10
0.20
0.20
0.75
0.75
1.0
1.0
1.0
1.0
1.0
1.0
0.15
0.20
0.25
0.25
0.25
1.6
-0.9
-0.9
0.5
0.5
0.6
0.6
-0.1
-0.1
0.1
0.2
0.3
-0.8
-1.0
-1.1
0.6
0.6
0.4
0.4
-0.6
-0.7
-1.0
-1.1
0.7
0.6
0.6
0.6
-0.2
-0.2
0.7
0.7
0.3
0.3
-1.0
-1.0
-0.8
0.8
-0.2
0.4
0.2
-1.0
-1.0
-0.7
-0.7
0.6
0.6
0.4
0.4
-0.7
-0.7
-0.4
0.7
0.8
0.6
-0.3
0.983
2.426
2.426
4.129
4.129
6.093
6.093
8.318
8.318
-2.137
-2.481
-1.541
-1.568
0.710
0.710
4.067
4.067
8.537
8.537
-2.629
-3.083
-2.024
-2.064
0.371
0.371
2.009
2.009
3.941
3.941
6.168
6.168
8.690
8.690
11.509
11.509
-3.185
-2.577
-2.637
-0.038
-0.038
1.698
1.698
3.744
3.744
6.103
6.103
8.775
8.775
11.760
11.760
-3.807
-3.204
-3.293
-2.034
-2.037
-0.019
-0.014
-0.014
-0.010
-0.010
-6.4E-3
-6.4E-3
-2.6E-3
-2.6E-3
0.042
-0.246
-0.043
-0.064
-0.025
-0.025
-0.014
-0.014
-5.8E-3
-5.8E-3
0.058
-0.322
-0.055
-0.086
-0.033
-0.033
-0.025
-0.025
-0.020
-0.020
-0.014
-0.014
-9.7E-3
-9.7E-3
-4.9E-3
-4.9E-3
0.079
-0.068
-0.116
-0.042
-0.042
-0.033
-0.033
-0.026
-0.026
-0.020
-0.020
-0.014
-0.014
-9.0E-3
-9.0E-3
0.105
-0.084
-0.153
-0.072
-0.075
7
18
18
18
18
18
18
18
18
18
18
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
5
5
6
6
8
8
9
9
10
10
2
2
3
4
4
5
5
6
6
8
8
9
9
10
10
2
2
4
4
5
5
6
6
8
8
10
10
4
4
5
5
6
6
7
7
8
8
10
10
2
4
5
5
8
8
14
13
13
12
11
10
10
9
9
8
18
17
16
16
15
15
14
14
13
12
11
11
10
10
9
19
18
17
16
16
15
15
14
13
12
11
10
18
17
17
16
16
15
15
14
14
13
12
11
21
19
18
17
15
14
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
5
5
6
6
8
8
9
9
10
10
2
2
3
4
4
5
5
6
6
8
8
9
9
10
10
2
2
4
4
5
5
6
6
8
8
10
10
4
4
5
5
6
6
7
7
8
8
10
10
2
4
5
5
8
8
15
14
14
13
12
11
11
10
10
9
19
18
17
17
16
16
15
15
14
13
12
12
11
11
10
20
19
18
17
17
16
16
15
14
13
12
11
19
18
18
17
17
16
16
15
15
14
13
12
22
20
19
18
16
15
50421.970
50421.970
50412.220
50412.220
50406.670
50406.670
50406.670
50406.670
50406.670
50406.670
52870.290
53729.450
53201.250
53101.220
53104.290
53079.420
53079.420
53068.270
53068.270
53060.410
53060.410
53060.410
53060.410
53060.410
53060.410
55494.850
56463.370
55762.700
55766.340
55736.960
55736.960
55724.270
55724.270
55714.440
55714.440
55714.440
55714.440
58424.550
58430.220
58395.320
58395.320
58380.020
58380.020
58372.200
58372.200
58368.100
58368.100
58368.100
58368.100
60737.610
61087.730
61054.700
61054.700
61022.700
61022.700
0.110
0.083
-0.235
-0.235
0.462
0.462
0.536
0.536
-0.557
-0.557
0.648
0.552
0.154
-0.254
0.222
0.245
0.202
0.270
0.270
0.225
0.225
0.631
0.631
-0.286
-0.286
-0.179
-0.105
-0.036
-0.051
-0.073
-0.140
0.378
0.377
0.121
0.121
0.205
0.205
-0.263
0.342
-0.139
-0.242
-0.129
-0.130
-0.139
-0.139
-0.517
-0.517
0.252
0.252
-0.434
0.017
0.220
0.066
-0.387
-0.387
0.10
0.10
0.10
0.10
1.0
1.0
1.0
1.0
1.0
1.0
0.10
0.15
0.10
0.15
0.20
0.10
0.10
0.15
0.15
0.50
0.50
1.0
1.0
1.0
1.0
0.10
0.10
0.10
0.20
0.10
0.10
0.25
0.25
0.20
0.30
0.30
0.30
0.15
0.25
0.10
0.10
0.10
0.10
0.10
0.10
0.30
0.30
0.75
0.75
0.20
0.15
0.15
0.15
0.30
0.30
1.0
0.8
-2.2
-2.2
0.4
0.4
0.5
0.5
-0.5
-0.5
6.3
3.6
1.4
-1.5
1.0
2.3
1.9
1.6
1.6
0.4
0.4
0.6
0.6
-0.3
-0.3
-1.8
-1.2
-0.3
-0.2
-0.7
-1.3
1.4
1.4
0.6
0.4
0.6
0.6
-1.6
1.2
-1.3
-2.2
-1.2
-1.2
-1.3
-1.3
-1.6
-1.6
0.3
0.3
-2.0
0.1
1.3
0.4
-1.2
-1.2
-0.522
-0.522
1.313
1.313
5.965
5.965
8.786
8.786
11.937
11.937
-4.497
-5.412
-4.037
-2.681
-2.686
-1.084
-1.085
0.850
0.850
5.749
5.749
8.719
8.719
12.036
12.036
-5.259
-6.377
-3.412
-3.420
-1.731
-1.731
0.304
0.304
5.451
5.451
12.054
12.054
-4.233
-4.245
-2.465
-2.465
-0.329
-0.329
2.180
2.180
5.067
5.067
11.987
11.987
-7.007
-5.146
-3.291
-3.291
4.593
4.593
-0.053
-0.053
-0.042
-0.042
-0.026
-0.026
-0.020
-0.020
-0.014
-0.014
0.138
-0.637
-0.200
-0.091
-0.094
-0.067
-0.067
-0.052
-0.052
-0.034
-0.034
-0.027
-0.027
-0.020
-0.020
0.178
-0.771
-0.112
-0.118
-0.083
-0.083
-0.065
-0.065
-0.043
-0.043
-0.027
-0.027
-0.138
-0.147
-0.102
-0.102
-0.079
-0.079
-0.064
-0.064
-0.053
-0.053
-0.035
-0.035
0.285
-0.168
-0.124
-0.124
-0.064
-0.064
8
23 3 21 24 3 22
23 4 19 24 4 20
23 5 19 24 5 20
23 5 18 24 5 19
23 6 18 24 6 19
23 6 17 24 6 18
23 7 17 24 7 18
23 7 16 24 7 17
24 3 22 25 3 23
24 3 21 25 3 22
24 4 21 25 4 22
24 4 20 25 4 21
24 5 20 25 5 21
24 5 19 25 5 20
24 6 19 25 6 20
24 6 18 25 6 19
24 8 17 25 8 18
24 8 16 25 8 17
24 9 16 25 9 17
24 9 15 25 9 16
24 10 15 25 10 16
24 10 14 25 10 15
25 3 22 26 3 23
25 6 20 26 6 21
25 6 19 26 6 20
25 7 19 26 7 20
25 7 18 26 7 19
25 8 18 26 8 19
25 8 17 26 8 18
25 9 17 26 9 18
25 9 16 26 9 17
26 3 24 27 3 25
26 3 23 27 3 24
26 6 21 27 6 22
26 6 20 27 6 21
26 7 20 27 7 21
26 7 19 27 7 20
26 8 19 27 8 20
26 8 18 27 8 19
26 9 18 27 9 19
26 9 17 27 9 18
27 6 22 28 6 23
27 6 21 28 6 22
27 7 21 28 7 22
27 7 20 28 7 21
27 8 20 28 8 21
27 8 19 28 8 20
27 9 19 28 9 20
27 9 18 28 9 19
28 3 26 29 3 27
28 3 25 29 3 26
28 4 24 29 4 25
28 6 23 29 6 24
28 6 22 29 6 23
28 7 22 29 7 23
63762.920
63760.670
63714.290
63714.290
63693.840
63693.840
63683.070
63683.070
66422.200
66656.030
66416.090
66428.370
66374.660
66374.660
66351.180
66351.180
66332.620
66332.620
66329.810
66329.810
66329.810
66329.810
69362.620
69009.380
69009.380
68994.770
68994.770
68987.550
68987.550
68984.000
68984.000
71738.600
72074.770
71667.470
71667.470
71651.780
71651.780
71643.090
71643.090
71638.150
71638.150
74326.200
74326.200
74308.000
74308.000
74298.310
74298.310
74293.520
74293.520
77050.680
77515.340
77116.600
76985.870
76985.870
76965.470
-0.068
-0.075
0.168
-0.059
0.012
0.009
-0.097
-0.097
-0.155
-0.595
0.109
0.018
0.250
-0.079
-0.105
-0.110
0.045
0.045
0.112
0.112
0.650
0.650
-0.113
0.203
0.195
-0.334
-0.334
-0.058
-0.058
-0.058
-0.058
-0.081
0.301
-0.052
-0.064
0.263
0.263
0.246
0.246
-0.404
-0.404
-0.137
-0.155
-0.242
-0.242
0.019
0.019
0.327
0.327
0.097
-0.029
0.112
0.229
0.202
0.180
0.10
0.10
0.20
0.20
0.10
0.10
0.10
0.10
0.25
0.30
0.20
0.15
0.40
0.40
0.10
0.10
0.15
0.15
0.75
0.75
1.0
1.0
0.20
0.15
0.15
0.20
0.20
0.40
0.40
0.50
0.50
0.15
0.20
0.10
0.10
0.20
0.20
0.30
0.30
0.40
0.40
0.10
0.10
0.20
0.20
0.15
0.15
0.40
0.40
0.20
0.10
0.20
0.30
0.30
0.20
-0.6
-0.7
0.8
-0.3
0.1
0.1
-0.9
-0.9
-0.6
-1.8
0.5
0.1
0.6
-0.2
-1.0
-1.0
0.3
0.3
0.1
0.1
0.6
0.6
-0.5
1.2
1.2
-1.5
-1.5
-0.1
-0.1
-0.1
-0.1
-0.5
1.4
-0.5
-0.6
1.2
1.2
0.7
0.7
-0.9
-0.9
-1.3
-1.5
-1.1
-1.1
0.1
0.1
0.7
0.7
0.5
-0.4
0.5
0.7
0.6
0.8
-7.594
-6.185
-4.214
-4.215
-1.874
-1.874
0.870
0.870
-8.748
-9.321
-7.272
-7.311
-5.238
-5.239
-2.794
-2.794
3.357
3.357
7.076
7.076
11.228
11.228
-10.742
-3.818
-3.818
-0.837
-0.837
2.587
2.587
6.457
6.457
-11.357
-12.302
-4.952
-4.952
-1.850
-1.850
1.709
1.709
5.730
5.730
-6.198
-6.199
-2.975
-2.975
0.719
0.719
4.892
4.892
-14.387
-15.869
-12.988
-7.563
-7.563
-4.217
-0.187
-0.222
-0.149
-0.150
-0.116
-0.116
-0.094
-0.094
-0.211
-0.659
-0.241
-0.270
-0.179
-0.180
-0.138
-0.138
-0.093
-0.093
-0.079
-0.079
-0.066
-0.066
-0.814
-0.164
-0.164
-0.133
-0.133
-0.111
-0.111
-0.094
-0.094
-0.257
-0.998
-0.194
-0.194
-0.157
-0.157
-0.131
-0.131
-0.111
-0.111
-0.227
-0.227
-0.183
-0.183
-0.153
-0.153
-0.131
-0.131
-0.296
-1.462
-0.566
-0.265
-0.265
-0.214
9
28
28
28
28
28
28
28
28
28
29
29
29
29
29
29
29
29
29
29
29
29
29
7
8
8
9
9
10
10
11
11
3
4
4
6
6
7
7
8
8
9
9
10
10
21
21
20
20
19
19
18
18
17
27
26
25
24
23
23
22
22
21
21
20
20
19
29
29
29
29
29
29
29
29
29
30
30
30
30
30
30
30
30
30
30
30
30
30
7
8
8
9
9
10
10
11
11
3
4
4
6
6
7
7
8
8
9
9
10
10
22
22
21
21
20
20
19
19
18
28
27
26
25
24
24
23
23
22
22
21
21
20
rms deviation:
76965.470
76954.220
76954.220
76947.840
76947.840
76945.810
76945.810
76945.810
76945.810
79704.550
79750.250
79794.030
79645.470
79645.470
79623.030
79623.030
79610.050
79610.050
79603.150
79603.150
79599.700
79599.700
0.179
0.263
0.263
-0.140
-0.140
0.328
0.328
0.397
0.397
0.134
0.092
0.244
0.019
-0.020
0.356
0.355
0.201
0.201
0.229
0.229
-0.106
-0.106
0.20
0.30
0.30
0.20
0.20
0.40
0.40
0.40
0.40
0.25
0.20
0.25
0.20
0.20
0.20
0.20
0.20
0.20
0.25
0.25
0.40
0.40
0.8
0.8
0.8
-0.7
-0.7
0.8
0.8
0.9
0.9
0.5
0.4
0.9
0.1
-0.1
1.6
1.6
0.9
0.9
0.9
0.9
-0.2
-0.2
-4.217
-0.386
-0.386
3.939
3.939
8.763
8.763
14.089
14.089
-16.067
-14.535
-14.732
-9.051
-9.051
-5.580
-5.580
-1.612
-1.612
2.867
2.867
7.860
7.860
-0.214
-0.179
-0.179
-0.152
-0.152
-0.132
-0.132
-0.114
-0.114
-0.310
-0.528
-0.675
-0.308
-0.308
-0.248
-0.248
-0.207
-0.207
-0.177
-0.177
-0.153
-0.153
1.0994
Rotational constants (MHz) and kappa:
14134.0
1382.5018
+3.9
0.0079
1269.3008
0.0079
-0.982401
0.000003
Inertial constants and defect (uÅ**2):
35.7562
365.55400
+0.0099
0.0021
398.15550
0.0025
-3.15
0.01
-0.0227
fixed
-0.00105
fixed
Quartic distortion constants:
0.16763
-4.356
+0.00087
0.017
197
fixed
Significant Digits and Correlation Matrix:
6
0.932
8
-0.929
-0.976
8
-0.126
0.077
0.082
5
0.162
0.046
-0.017
-0.514
4
10
Table 6S: Microwave Spectrum of the First Excited State of the C-S torsion of
the ap Conformer of H-CC-CH2SCN
Total number of transitions:
Transition
9
9
10
10
11
11
12
12
12
12
13
13
13
13
13
14
14
14
14
15
15
15
16
16
16
16
16
17
17
17
18
18
18
18
19
19
20
20
20
20
21
21
21
21
21
5
5
5
5
5
5
4
4
5
5
3
4
4
5
5
2
3
4
4
2
4
4
2
5
5
6
6
2
5
5
2
3
5
5
5
5
3
4
5
5
4
5
5
6
6
5
4
6
5
7
6
9
8
8
7
10
10
9
9
8
13
12
11
10
14
12
11
15
12
11
11
10
16
13
12
17
16
14
13
15
14
18
17
16
15
18
17
16
16
15
10
10
11
11
12
12
13
13
13
13
14
14
14
14
14
15
15
15
15
16
16
16
17
17
17
17
17
18
18
18
19
19
19
19
20
20
21
21
21
21
22
22
22
22
22
5
5
5
5
5
5
4
4
5
5
3
4
4
5
5
2
3
4
4
2
4
4
2
5
5
6
6
2
5
5
2
3
5
5
5
5
3
4
5
5
4
5
5
6
6
96
obs. frequency
6
5
7
6
8
7
10
9
9
8
11
11
10
10
9
14
13
12
11
15
13
12
16
13
12
12
11
17
14
13
18
17
15
14
16
15
19
18
17
16
19
18
17
17
16
26567.500
26567.500
29224.810
29224.810
31882.430
31882.430
34546.820
34546.820
34540.730
34540.730
37233.530
37207.520
37207.520
37198.950
37198.950
39769.200
39881.960
39868.010
39868.010
42410.200
42529.570
42529.570
45048.790
45178.010
45178.010
45171.620
45171.620
47685.340
47838.580
47838.580
50319.440
50537.530
50499.370
50499.370
53160.570
53160.570
55866.850
55847.700
55822.400
55822.400
58514.540
58484.800
58484.800
58469.920
58469.920
obs.- weight
calc.
0.636
0.636
0.223
0.223
-0.176
-0.176
0.093
-0.032
-0.218
-0.218
0.328
0.513
0.300
-0.689
-0.691
-0.140
-0.323
0.105
-0.244
0.151
0.112
-0.440
0.055
-0.071
-0.082
-0.062
-0.062
0.053
0.139
0.122
-0.151
-0.245
0.087
0.058
-0.067
-0.112
-0.006
-0.431
-0.127
-0.197
0.331
-0.179
-0.287
0.220
0.218
0.50
0.50
0.50
0.50
0.50
0.50
0.25
0.25
0.50
0.50
0.30
0.15
0.15
0.50
0.50
0.15
0.10
0.10
0.10
0.15
0.25
0.25
0.15
0.15
0.15
0.25
0.25
0.15
0.20
0.20
0.15
0.20
0.15
0.15
0.20
0.20
0.50
0.50
0.25
0.25
0.30
0.15
0.15
0.15
0.15
t
0.8
0.8
0.3
0.3
-0.2
-0.2
0.2
-0.1
-0.3
-0.3
0.7
2.2
1.3
-0.9
-0.9
-0.6
-2.2
0.7
-1.7
0.7
0.3
-1.1
0.3
-0.3
-0.4
-0.2
-0.2
0.3
0.4
0.4
-0.9
-0.8
0.4
0.2
-0.2
-0.4
-0.0
-0.5
-0.3
-0.5
0.7
-0.8
-1.2
0.9
0.9
distortion corrections
total
fixed
1.464
1.464
1.445
1.445
1.379
1.379
0.239
0.239
1.261
1.261
-0.885
-0.015
-0.015
1.087
1.087
-1.828
-1.252
-0.330
-0.330
-2.288
-0.710
-0.711
-2.810
0.183
0.183
1.818
1.818
-3.400
-0.260
-0.260
-4.059
-3.460
-0.782
-0.782
-1.388
-1.388
-5.044
-3.760
-2.081
-2.081
-4.632
-2.867
-2.867
-0.735
-0.735
-2.4E-3
-2.4E-3
-4.2E-3
-4.2E-3
-6.7E-3
-6.7E-3
-0.014
-0.014
-9.9E-3
-9.9E-3
-0.034
-0.019
-0.020
-0.014
-0.014
0.029
-0.034
-0.026
-0.026
0.042
-0.035
-0.035
0.058
-0.034
-0.034
-0.026
-0.026
0.079
-0.043
-0.043
0.106
-0.085
-0.055
-0.055
-0.068
-0.068
-0.123
-0.115
-0.085
-0.085
-0.141
-0.104
-0.104
-0.081
-0.081
11
21
21
22
22
22
22
22
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
25
26
26
27
27
27
27
27
27
27
28
28
29
29
29
29
29
29
29
8
8
3
5
5
6
6
3
4
5
5
6
6
7
7
4
4
5
5
6
6
7
7
7
7
5
5
6
6
7
7
7
7
6
6
3
7
7
7
7
8
8
6
6
5
6
6
7
7
8
8
14
13
19
18
17
17
16
20
20
19
18
18
17
17
16
21
20
20
19
19
18
18
18
17
17
21
20
20
19
19
19
18
18
21
20
24
21
21
20
20
20
19
23
22
25
24
23
23
22
22
21
22
22
23
23
23
23
23
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
27
27
28
28
28
28
28
28
28
29
29
30
30
30
30
30
30
30
8
8
3
5
5
6
6
3
4
5
5
6
6
7
7
4
4
5
5
6
6
7
7
7
7
5
5
6
6
7
7
7
7
6
6
3
7
7
7
7
8
8
6
6
5
6
6
7
7
8
8
rms deviation:
15
14
20
19
18
18
17
21
21
20
19
19
18
18
17
22
21
21
20
20
19
19
19
18
18
22
21
21
20
20
20
19
19
22
21
25
22
22
21
21
21
20
24
23
26
25
24
24
23
23
22
58458.120
58458.120
61354.520
61148.300
61148.300
61130.570
61130.570
64054.270
63848.790
63811.770
63811.770
63791.230
63791.230
63780.740
63780.740
66517.090
66530.480
66476.030
66476.030
66453.160
66453.160
66440.560
66440.560
66440.560
66440.560
69141.190
69141.190
69114.880
69114.880
69100.800
69100.800
69100.800
69100.800
71776.770
71776.770
74907.350
74421.900
74421.900
74421.900
74421.900
74411.660
74411.660
77103.030
77103.030
79807.960
79767.030
79767.030
79744.470
79744.470
79731.440
79731.440
-0.071
-0.071
-0.160
0.279
0.118
0.205
0.203
-0.169
-0.007
0.094
-0.143
-0.194
-0.197
-0.044
-0.044
-0.210
0.446
0.060
-0.284
0.266
0.261
-0.064
-0.064
-0.064
-0.064
0.262
-0.228
0.088
0.079
0.054
0.054
0.054
0.054
-0.367
-0.380
0.248
0.016
0.016
0.016
0.016
-0.292
-0.292
-0.204
-0.233
0.125
0.008
-0.034
0.182
0.181
-0.047
-0.047
0.15
0.15
0.20
0.10
0.10
0.15
0.15
0.20
0.20
0.10
0.10
0.10
0.10
0.15
0.15
0.15
0.25
0.25
0.25
0.10
0.10
0.15
0.15
0.15
0.15
0.40
0.40
0.10
0.10
0.15
0.15
0.15
0.15
0.20
0.20
0.25
0.20
0.25
0.20
0.25
0.30
0.30
0.15
0.15
0.30
0.10
0.10
0.15
0.15
0.10
0.10
-0.4
-0.4
-0.6
1.8
0.8
0.9
0.9
-0.7
-0.0
0.6
-0.9
-1.3
-1.3
-0.2
-0.2
-0.9
1.1
0.2
-0.7
1.7
1.7
-0.3
-0.3
-0.3
-0.3
0.4
-0.4
0.6
0.5
0.2
0.2
0.2
0.2
-1.2
-1.2
2.1
0.1
0.0
0.1
0.0
-0.6
-0.6
-0.9
-1.0
0.3
0.1
-0.3
0.8
0.8
-0.4
-0.4
4.653
4.653
-7.327
-3.750
-3.750
-1.516
-1.516
-8.557
-6.676
-4.734
-4.735
-2.398
-2.398
0.342
0.342
-7.858
-7.898
-5.826
-5.827
-3.385
-3.385
-0.527
-0.527
-0.527
-0.527
-7.029
-7.031
-4.482
-4.482
-1.505
-1.505
-1.505
-1.505
-5.694
-5.694
-14.850
-3.807
-3.807
-3.807
-3.807
-0.119
-0.119
-8.482
-8.482
-13.054
-10.066
-10.067
-6.601
-6.601
-2.638
-2.638
-0.054
-0.054
-0.428
-0.126
-0.127
-0.098
-0.098
-0.539
-0.206
-0.152
-0.153
-0.118
-0.118
-0.096
-0.096
-0.246
-0.275
-0.182
-0.183
-0.141
-0.141
-0.115
-0.115
-0.115
-0.115
-0.217
-0.219
-0.167
-0.167
-0.136
-0.136
-0.136
-0.136
-0.198
-0.198
-1.236
-0.187
-0.187
-0.187
-0.187
-0.157
-0.157
-0.271
-0.271
-0.413
-0.315
-0.315
-0.253
-0.253
-0.211
-0.211
1.1989
12
Rotational constants (MHz) and kappa:
13715
1383.5566
+fixed
0.0095
1272.3385
0.0098
-0.982123
0.000003
Inertial constants and defect (uÅ**2):
36.849
365.27533
+fixed
0.0025
397.20489
0.0030
-4.919
0.005
-0.0227
fixed
-0.00105
fixed
Quartic distortion constants:
0.17681
-4.348
+0.0015
0.038
197
fixed
Significant Digits and Correlation Matrix:
8
-0.957
8
0.491
-0.315
5
-0.338
0.373
-0.685
4
References
(1)
(2)
(3)
Yura, Y. Chem. Pharm. Bull. 1962, 10, 1094.
Midtgaard, T.; Gundersen, G.; Nielsen, C. J. J. Mol. Struct. 1988, 176, 159.
Watson, J. K. G. Vibrational Spectra and Structure; Elsevier: Amsterdam, 1977;
Vol. 6.
(4)
York, 1964.
Hamilton, W. C. Statistics in Physical Science; The Ronald Press Company: New
13