suppmat1827. 36KB Jun 05 2011 09:30:45 PM
SUPPLEMENTARY MATERIAL
(Tables 6-8, 10, 12, 14, 19, 20, 24, 25, 28, 29)
MOLECULAR MECHANICS STUDIES (MM4) OF SULFIDES AND MERCAPTANS
Norman L. Allinger and Yi Fan
Contribution from the Computational Center for Molecular Structure and Design
Department of Chemistry, University of Georgia, Athens, GA 30602-2556
S-1
Table 6.
Comparison of Calculated and Experimental Geometries
of 1-Propanethiol
Bond Length ( Å ) and Bond Angles ( )
(ag, C1)
MM3(rg)
MM4(rg)
MW(rs)30
S-H
S-C
C-C(Me)
C-C(Methylene)
1.343
1.834
1.537
1.534
1.333
1.824
1.536
1.535
1.336
1.814
1.536
1.528
CSH
97.0
96.6
96.0
CCC
CCS
112.2
111.8
111.9
113.3
111.7
113.6
CCSH
CCCS
62.2
179.3
64.2
178.2
61.7
180.0
Parameter
Moments of Inertia
rg(MM3)
rz(MM4)
MW30
Ia
21.8179/3.22%
21.0458/-0.44%
21.1388
Ib
216.0568/0.26%
215.9561/0.23%
215.4577
Ic
225.6166/0.45%
225.1830/0.27%
224.5783
(aa, Cs)
Parameter
MM3
MM4
MW(rs)30
S-H
S-C
C-C(Me)
C-C(Methylene)
1.343
1.833
1.534
1.536
1.333
1.826
1.535
1.537
1.336
1.820
1.536
1.529
CSH
CCC
CCS
96.7
112.3
111.2
96.8
112.3
108.6
96.2
111.7
108.6
CCSH
CCCS
180.0
180.0
180.0
180.0
180.0
180.0
S-2
(Table 6 continued)
Moments of Inertia
rg(MM3)
rz(MM4)
MW30
Ia
21.1514/-1.89%
21.0812/-0.53%
21.1940
Ib
216.8275/2.69%
211.8501/0.33%
211.1483
Ic
228.2759/0.71%
223.6903/0.46%
222.6702
S-3
Table 7.
Comparison of Calculated and Experimental Geometries
of 2-Propanethiola
Bond Length ( Å ) and Bond Angles ( )
Parameter
MM3
MM4
MW(rz)31
S-H
S-C
C-C
1.343
1.841
1.537
1.333
1.827
1.535
1.345
1.849
1.520
CSH
CCC
CCS
97.4
110.7
110.2
96.4
110.9
111.1
96.5
113.6
111.2
CCSH
61.2
62.0
61.0
Moments of Inertia(Cs)
Ia
Ib
Ic
rg(MM3)
rz(MM4)
MW31
64.9556/1.45%
115.0802/0.51%
159.9976/-0.02%
64.2363/0.29%
114.2347/-0.13%
159.2697/-0.65%
64.0515
114.3780
160.3185
Moments of Inertia(C1)
Ia
Ib
Ic
rg(MM3)
rz(MM4)
MW31
64.5926/0.72%
114.6337/2.63%
162.0758/1.64%
64.3422/0.33%
111.7507/0.05%
158.8753/-0.36%
64.1331
111.6954
159.4571
_____________________________
aThe conformations of this molecule are shown in Fig. 7.
S-4
Table 8.
Comparison of Calculated and Experimental Geometries
of Diisopropyl Sulfide (I, C2)
Bond Length ( Å ) and Bond Angles ( )
Parameter
MM3
MM4
MOCED(rg)a
S-C
C1-C4
C1-C5
C-H
1.832
1.538
1.537
1.114
1.830
1.538
1.535
1.112
1.829(3)
1.528(2)
1.532(2)
1.118(3)
CSC
C4C1S2
100.9
110.5
102.0
112.5
102.9(17)
112.0(7)
C5C1S2
CCC
109.0
110.1
106.0
110.2
106.5(7)
110.5(9)
CSCH
42.0
53.0
59(7)
___________________________________
a This structure was investigated by
the molecular orbital constrained electron
diffraction (MOCED) method. See Ref. 32.
S-5
Table 10.
Comparison of Calculated and Experimental Geometries
of Thiacyclopentane(C2)
Bond Length ( Å ) and Bond Angles ( )
MM3(rg)
MM4(rg)
MM4(re)
MP2/6-31G**
ED(rg)36
C-S
1.537
1.840
1.537
1.838
1.530
1.830
1.526
1.830
1.536(2)
1.839(2)
CSC
SCC
CCC
93.3
106.6
105.5
93.4
106.9
105.9
/
/
/
93.7
106.3
106.0
93.4(5)
106.1(4)
105.0(5)
C5S1C2C3
S1C2C3C4
C2C3C4C5
-14.2
39.0
-50.4
-13.8
37.8
-48.9
/
/
/
-14.0
38.3
-49.8
-14.8(5)
40.5(12)
-52.5(16)
Parameter
C-Cave
S-6
Table 12.
Comparison of Calculated and Experimental Geometries
of Thiane (Cs)
Bond Length ( Å ) and Bond Angles ( )
Parameter
MM3
MM4
MW39
ED40
C-C
C-S
C-H
1.536
1.813
1.114
1.531
1.814
1.113
1.533
1.832
1.095
1.528(3)
1.811(4)
1.114(2)
CSC
C2C3C4
C3C4C5
97.5
112.7
112.6
97.4
112.7
112.9
99.2
107.9
109.2
97.6(8)
112.3(4)
113.6(8)
HCH
CCS
106.4
111.3
106.4
112.8
108.5
114.1
105.9(9)
112.7(2)
Moments of Inertia
rg(MM3)
rz(MM4)
MW39
Ia
127.673/0.87%
125.9488/-0.50%
126.575
Ib
168.229/1.08%
168.9888/0.51%
168.134
Ic
263.601/-0.13%
264.3356/0.15%
263.949
S-7
Table 14.
Dipole Moments(Debye)
Compound
MM3
MM4
Exp.
Ref.
Methanethiol
Ethanethiol(gauche)
Ethanethiol(trans)
Dimethyl Sulfide
Methylethylsulfide(trans)
1-Propanethiol(aa)
1-Propanethiol(ag)
2-Propanethiol(trans)
2-Propanethiol(gauche)
1-butanethiol
2-butanethiol
1.410
1.410
1.410
1.570
1.549
1.413
1.410
1.404
1.409
1.413
1.408
1.552
1.561
1.557
1.559
1.560
1.558
1.561
1.564
1.564
1.558
1.566
1.532
1.61±0.05
1.560±0.032
1.50±0.01
1.554±0.004
1.598±0.054
1.683±0.010
1.61±0.02
1.53±0.02
1.55a
1.50a
21
41
42
26
43
30
30
31
31
44
44
___________________________
a
These dipole moments are obtained in benzene, all other dipole moments are from gas phase.
S-8
Table 19.
MP2/6-31G*
2994
2985
2979
2977
2941
2895
2893
2890
1488
1478
1478
1469
1453
1398
1367
1297
1248
1076
1048
989
975
965
781
739
687
341
249
197
167
74
RMS
AVG.
Vibrational Spectrum of trans-Methyl Ethyl Sulfide(Cs) (cm-1)
MM3
2987
2967
2987
2966
2932
2885
2880
2870
1467
1457
1488
1442
1431
1354
1417
1376
1278
1032
1011
978
1011
1024
841
704
666
332
265
231
201
86
32
2
MM4
2998
2972
2997
2971
2945
2900
2895
2879
1473
1461
1448
1413
1397
1412
1295
1348
1250
1053
1081
965
965
983
800
724
668
341
254
228
190
84
7
-6
Diff.(MM4 - ab initio)
4
-13
18
-6
4
5
2
-11
-15
-17
-30
-56
-56
14
-72
51
2
-23
33
-24
-10
18
19
-15
-19
0
5
31
23
10
S-9
Assignment
Asy. CH3 str.
Asy. CH3(CH2) str.
Asy. CH3 str.
Asy. CH3(CH2) str.
Asy. CH2 str.
Sym. CH3(CH2) str.
Sym. CH3 str.
Sym. CH2 str.
Asy. CH3(CH2), CH2 def.
Asy. CH3(CH2) def.
CH2 def.
CH2 def.
Asy. CH3 def.
Sym. CH3(CH2) def.
Sym. CH3 def.
CH2 wagging
CH2 twist
CH3(CH2),CH3 rock
CH2 rock
CC str.
CH3 rock
CH3(CH2),CH3 rock
CH3(CH2),CH2 rock
CS str.
CS str.
CCS bending
CH3 torsion
CSC bending
CH3 torsion
CSCC torsion
Table 20.
Vibrational Spectrum of Thiacyclopentane(C2) (cm-1)
MP2/6-31G**a
MM3
MM4
Diff.(MM4 - ab initio)
2965
2964
2944
2937
2898
2898
2883
2882
1484
1472
1461
1458
1336
1313
1294
1265
1220
1200
1134
1059
1037
1031
960
885
882
878
820
690
686
502
461
287
108
2944
2944
2937
2936
2892
2889
2881
2873
1446
1444
1443
1433
1393
1365
1335
1291
1221
1218
1163
1142
1022
1016
972
830
906
875
814
671
627
503
413
318
120
2964
2964
2939
2937
2909
2908
2888
2878
1506
1499
1469
1448
1420
1374
1278
1272
1209
1200
1151
1125
1060
1001
993
904
888
825
771
703
669
531
455
282
114
-1
0
-5
0
11
10
5
4
22
27
8
-10
84
61
-16
27
-11
0
17
66
23
-30
33
19
6
-53
-49
13
-17
29
-6
-5
6
RMS
27
29
AVG.
-3
8
S-10
Assignment
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
CH2 bending
CH2 bending
CH2 bending
CH2 bending
CH2 wagging
CH2 wagging
CH2 wagging
CH2 wagging
CH2 twist
CH2 twist
CH2 twist
CH2 twist
CH2 twist
CC str.
CC str.
ring def. (CCC)
ring def. (CSC, CC)
CH2 rock
CH2 rock
ring def. (CCC, CS)
ring def. (CCC, CS)
ring def. (CCC)
ring def. (CCS, CSC)
torsion
torsion
____________________________
aThe wavenumbers for C-H stretching are scaled down to 92% of original values,
while the others are scaled down to 95%.
S-11
Table 24.
anti-gauche
0.0
Relative Stability of Methyl Ethyl Sulfide Conformers
Method
Ref.
IR
E
54
IR(Liquid)
E
55
IR
H
53
0.03±0.05
Raman
H
56
0.25±0.15
ED
Nt/(Nt+Ng)
37
0.05±0.01
IR
H
52
-8.37
CNDO/2
E
57
-1.21
4-31G
E
58
0.04
MP2/3-21G**
E
59
-0.13
MM3
E
11
0.00
MP2/6-31G*
E
this work
0.12
MM4
G
this work
-0.07
MM4
∆E
this work
-0.27
MM4
∆Η
this work
0.14±0.05
0.0
S-12
Table 25.
Input for the Heat Calculations of Sulfides and Mercaptans
WT Hf(0)
ENTHALPY
10
10
10
10
7
9
10
9
8
7
8
8
7
9
8
8
8
7
5
6
9
9
7
-5.47
-11.07
-8.96
-16.23
-14.24
-19.96
-18.21
-21.63
-45.15
-8.15
-15.18
-22.97
-24.43
-28.99
-23.26
-26.20
-30.38
-28.01
-35.37
-33.91
-11.42
-16.34
-2.32
30.31
49.78
48.95
68.71
68.71
88.46
68.56
88.14
169.59
78.67
95.69
114.87
106.55
107.40
88.54
87.29
107.70
107.86
127.10
127.32
102.11
97.56
51.62
COMPOUND
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
3-THIAPENTANE
2-PROPANETHIOL
3-ME-2THIABUTANE
DI-T-BUTYLSULFID
THIACYCLOPENTANE
THIACYCLOHEXANE
CYCLOHEXANETHIOL
2-THIAHEXANE
3,3DIME-2THIABUT
2ME1PROPANETHIOL
2ME2PROPANETHIOL
2ME2BUTANETHIOL
SUMH Hatom
-317.18
-617.93
-634.36
-918.58
-935.11
-1235.86
-918.68
-1235.86
-2438.86
-1108.94
-1409.12
-1693.25
-1536.41
-1536.61
-1220.59
-1219.43
-1520.08
-1536.61
-1837.35
-1837.35
-1393.07
-1409.69
-512.11
C-S
1
1
2
1
2
2
1
2
2
2
2
1
2
2
1
1
1
445.71
721.59
721.59
997.47
997.47
1273.35
997.47
1273.35
2376.87
1169.17
1445.05
1720.93
1549.23
1549.23
1273.35
1273.35
1549.23
1549.23
1825.11
1825.11
1445.05
1445.05
787.24
S-H
1
1
0
1
0
0
1
0
0
0
0
1
0
0
1
1
1
S-13
POP TORS COMPOUND
0.00
0.10
0.00
0.31
0.11
0.29
0.10
0.15
0.00
0.00
0.00
0.16
0.51
0.04
0.16
0.00
0.12
0.21
0.16
0.40
0.14
0.16
0.19
SEC
0
0
0
0
0
0
1
1
0
0
0
1
0
0
0
0
0
-0.57
0.00
0.00
0.57
0.57
1.14
0.00
0.57
1.14
0.57
0.00
0.00
1.71
0.57
0.57
0.00
0.57
1.14
1.14
1.14
0.57
0.57
0.57
TER
0
0
0
0
0
0
0
0
2
0
0
0
0
1
0
1
1
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
3-THIAPENTANE
2-PROPANETHIOL
3-ME-2THIABUTANE
DI-T-BUTYLSULFIDE
THIACYCLOPENTANE
THIACYCLOHEXANE
CYCLOHEXANETHIOL
2-THIAHEXANE
3,3DIME-2THIABUTA
2ME1PROPANETHIOL
2ME2PROPANETHIOL
2ME2BUTANETHIOL
2ME3THIAPENTANE
2,2DIME3THIAPENTA
2,4DIME3THIAPENTA
CYCLOPENTANETHIOL
2-METHIACYCLOPENT
ETHANE12DITHIOL
S-Me
1
0
2
0
1
0
0
1
0
0
0
0
1
1
0
0
0
SCCS
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2ME3THIAPENTANE
2,2DIME3THIAPENT
2,4DIME3THIAPENT
CYCLOPENTANETHIOL
2-METHIACYCLOPEN
ETHANE12DITHIOL
2
2
2
1
2
2
0
0
0
1
0
2
S-14
1
0
2
1
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
Table 28.
Strainless Heats of Formation of Sulfides and Mercaptans
WT Hf(0)a
ENTHALPY
10
10
10
10
7
10
8
8
-4.63
-11.16
-9.02
-17.00
-15.26
-18.75
-26.62
-11.84
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
COMPOUND
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
2-PROPANETHIOL
2ME2PROPANETHIOL
25DITHIAHEXANE
SUMH Hatom
POP TORS COMPOUND
-295.31 445.71 0.00
-576.84 721.59 0.00
-590.63 721.59 0.00
-858.57 997.47 0.00
-872.16 997.47 0.00
-858.38 997.47 0.00
-1139.91 1273.35 0.00
-1069.22 1339.00 0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
C-S
1
1
2
1
2
1
1
4
TER
0
0
0
0
0
0
1
0
S-H
1
1
0
1
0
1
1
0
SEC
0
0
0
0
0
1
0
0
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
2-PROPANETHIOL
2ME2PROPANETHIOL
25DITHIAHEXANE
S-Me
1
0
2
0
1
0
0
2
SCCS
0
0
0
0
0
0
0
1
Best Values:
C-S = -70.7021
S-H = -85.1621
S-ME = 0.7528
SCCS = -0.3171
SEC = -1.9757
WT
Hfb
Hf(0)a
Hf-Hf(0)
10
10
10
10
10
10
10
10
-4.71
-11.11
-8.94
-16.96
-15.34
-18.75
-26.62
-11.84
-4.63
-11.16
-9.02
-17.00
-15.26
-18.75
-26.62
-11.84
–0.08
0.05
0.08
0.04
–0.08
0.00
0.00
0
COMPOUND
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
2-PROPANETHIOL
2ME2PROPANETHIOL
25DITHIAHEXANE
The standard deviation = 0.05, based on 8 equations.
The weighted standard deviation = 0.05 based on 8 equations.
S-15
TER = -4.1957
________________________
aMM4
calculated heats of formation.
heats of formation.
bCalculated strainless
S-16
Table 29.
Strain Energies of Sulfides and Mercaptans
Inherent Strain
Total Strain Energy POP TORS COMPOUND
0.09
–0.04
–0.08
–0.04
0.08
0.23
-0.01
–0.49
0.06
–0.08
0.84
0.76
1.66
0.09
0.00
0.10
0.00
0.31
0.11
0.29
0.10
-0.57
0.00
0.00
0.57
0.57
1.14
0.00
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
3-THIAPENTANE
2-PROPANETHIOL
0.76
6.42
0.76
–0.67
0.32
0.06
1.30
1.03
0.00
1.48
0.88
1.39
1.60
6.01
0.91
0.33
0.00
1.49
7.56
1.33
–0.67
0.48
2.28
1.91
1.76
0.00
2.19
2.23
2.70
3.15
6.72
1.64
1.09
1.34
0.15
0.00
0.00
0.00
0.16
0.51
0.04
0.16
0.00
0.12
0.21
0.16
0.40
0.14
0.16
0.19
0.20
0.57
1.14
0.57
0.00
0.00
1.71
0.57
0.57
0.00
0.57
1.14
1.14
1.14
0.57
0.57
0.57
1.14
3-ME-2THIABUTANE
DI-T-BUTYLSULFIDE
THIACYCLOPENTANE
THIACYCLOHEXANE
CYCLOHEXANETHIOL
2-THIAHEXANE
3,3DIME-2THIABUTA
2ME1PROPANETHIOL
2ME2PROPANETHIOL
2ME2BUTANETHIOL
2ME3THIAPENTANE
2,2DIME3THIAPENTA
2,4DIME3THIAPENTA
CYCLOPENTANETHIOL
2-METHIACYCLOPENT
ETHANE12DITHIOL
25DITHIAHEXANE
S-17
(Tables 6-8, 10, 12, 14, 19, 20, 24, 25, 28, 29)
MOLECULAR MECHANICS STUDIES (MM4) OF SULFIDES AND MERCAPTANS
Norman L. Allinger and Yi Fan
Contribution from the Computational Center for Molecular Structure and Design
Department of Chemistry, University of Georgia, Athens, GA 30602-2556
S-1
Table 6.
Comparison of Calculated and Experimental Geometries
of 1-Propanethiol
Bond Length ( Å ) and Bond Angles ( )
(ag, C1)
MM3(rg)
MM4(rg)
MW(rs)30
S-H
S-C
C-C(Me)
C-C(Methylene)
1.343
1.834
1.537
1.534
1.333
1.824
1.536
1.535
1.336
1.814
1.536
1.528
CSH
97.0
96.6
96.0
CCC
CCS
112.2
111.8
111.9
113.3
111.7
113.6
CCSH
CCCS
62.2
179.3
64.2
178.2
61.7
180.0
Parameter
Moments of Inertia
rg(MM3)
rz(MM4)
MW30
Ia
21.8179/3.22%
21.0458/-0.44%
21.1388
Ib
216.0568/0.26%
215.9561/0.23%
215.4577
Ic
225.6166/0.45%
225.1830/0.27%
224.5783
(aa, Cs)
Parameter
MM3
MM4
MW(rs)30
S-H
S-C
C-C(Me)
C-C(Methylene)
1.343
1.833
1.534
1.536
1.333
1.826
1.535
1.537
1.336
1.820
1.536
1.529
CSH
CCC
CCS
96.7
112.3
111.2
96.8
112.3
108.6
96.2
111.7
108.6
CCSH
CCCS
180.0
180.0
180.0
180.0
180.0
180.0
S-2
(Table 6 continued)
Moments of Inertia
rg(MM3)
rz(MM4)
MW30
Ia
21.1514/-1.89%
21.0812/-0.53%
21.1940
Ib
216.8275/2.69%
211.8501/0.33%
211.1483
Ic
228.2759/0.71%
223.6903/0.46%
222.6702
S-3
Table 7.
Comparison of Calculated and Experimental Geometries
of 2-Propanethiola
Bond Length ( Å ) and Bond Angles ( )
Parameter
MM3
MM4
MW(rz)31
S-H
S-C
C-C
1.343
1.841
1.537
1.333
1.827
1.535
1.345
1.849
1.520
CSH
CCC
CCS
97.4
110.7
110.2
96.4
110.9
111.1
96.5
113.6
111.2
CCSH
61.2
62.0
61.0
Moments of Inertia(Cs)
Ia
Ib
Ic
rg(MM3)
rz(MM4)
MW31
64.9556/1.45%
115.0802/0.51%
159.9976/-0.02%
64.2363/0.29%
114.2347/-0.13%
159.2697/-0.65%
64.0515
114.3780
160.3185
Moments of Inertia(C1)
Ia
Ib
Ic
rg(MM3)
rz(MM4)
MW31
64.5926/0.72%
114.6337/2.63%
162.0758/1.64%
64.3422/0.33%
111.7507/0.05%
158.8753/-0.36%
64.1331
111.6954
159.4571
_____________________________
aThe conformations of this molecule are shown in Fig. 7.
S-4
Table 8.
Comparison of Calculated and Experimental Geometries
of Diisopropyl Sulfide (I, C2)
Bond Length ( Å ) and Bond Angles ( )
Parameter
MM3
MM4
MOCED(rg)a
S-C
C1-C4
C1-C5
C-H
1.832
1.538
1.537
1.114
1.830
1.538
1.535
1.112
1.829(3)
1.528(2)
1.532(2)
1.118(3)
CSC
C4C1S2
100.9
110.5
102.0
112.5
102.9(17)
112.0(7)
C5C1S2
CCC
109.0
110.1
106.0
110.2
106.5(7)
110.5(9)
CSCH
42.0
53.0
59(7)
___________________________________
a This structure was investigated by
the molecular orbital constrained electron
diffraction (MOCED) method. See Ref. 32.
S-5
Table 10.
Comparison of Calculated and Experimental Geometries
of Thiacyclopentane(C2)
Bond Length ( Å ) and Bond Angles ( )
MM3(rg)
MM4(rg)
MM4(re)
MP2/6-31G**
ED(rg)36
C-S
1.537
1.840
1.537
1.838
1.530
1.830
1.526
1.830
1.536(2)
1.839(2)
CSC
SCC
CCC
93.3
106.6
105.5
93.4
106.9
105.9
/
/
/
93.7
106.3
106.0
93.4(5)
106.1(4)
105.0(5)
C5S1C2C3
S1C2C3C4
C2C3C4C5
-14.2
39.0
-50.4
-13.8
37.8
-48.9
/
/
/
-14.0
38.3
-49.8
-14.8(5)
40.5(12)
-52.5(16)
Parameter
C-Cave
S-6
Table 12.
Comparison of Calculated and Experimental Geometries
of Thiane (Cs)
Bond Length ( Å ) and Bond Angles ( )
Parameter
MM3
MM4
MW39
ED40
C-C
C-S
C-H
1.536
1.813
1.114
1.531
1.814
1.113
1.533
1.832
1.095
1.528(3)
1.811(4)
1.114(2)
CSC
C2C3C4
C3C4C5
97.5
112.7
112.6
97.4
112.7
112.9
99.2
107.9
109.2
97.6(8)
112.3(4)
113.6(8)
HCH
CCS
106.4
111.3
106.4
112.8
108.5
114.1
105.9(9)
112.7(2)
Moments of Inertia
rg(MM3)
rz(MM4)
MW39
Ia
127.673/0.87%
125.9488/-0.50%
126.575
Ib
168.229/1.08%
168.9888/0.51%
168.134
Ic
263.601/-0.13%
264.3356/0.15%
263.949
S-7
Table 14.
Dipole Moments(Debye)
Compound
MM3
MM4
Exp.
Ref.
Methanethiol
Ethanethiol(gauche)
Ethanethiol(trans)
Dimethyl Sulfide
Methylethylsulfide(trans)
1-Propanethiol(aa)
1-Propanethiol(ag)
2-Propanethiol(trans)
2-Propanethiol(gauche)
1-butanethiol
2-butanethiol
1.410
1.410
1.410
1.570
1.549
1.413
1.410
1.404
1.409
1.413
1.408
1.552
1.561
1.557
1.559
1.560
1.558
1.561
1.564
1.564
1.558
1.566
1.532
1.61±0.05
1.560±0.032
1.50±0.01
1.554±0.004
1.598±0.054
1.683±0.010
1.61±0.02
1.53±0.02
1.55a
1.50a
21
41
42
26
43
30
30
31
31
44
44
___________________________
a
These dipole moments are obtained in benzene, all other dipole moments are from gas phase.
S-8
Table 19.
MP2/6-31G*
2994
2985
2979
2977
2941
2895
2893
2890
1488
1478
1478
1469
1453
1398
1367
1297
1248
1076
1048
989
975
965
781
739
687
341
249
197
167
74
RMS
AVG.
Vibrational Spectrum of trans-Methyl Ethyl Sulfide(Cs) (cm-1)
MM3
2987
2967
2987
2966
2932
2885
2880
2870
1467
1457
1488
1442
1431
1354
1417
1376
1278
1032
1011
978
1011
1024
841
704
666
332
265
231
201
86
32
2
MM4
2998
2972
2997
2971
2945
2900
2895
2879
1473
1461
1448
1413
1397
1412
1295
1348
1250
1053
1081
965
965
983
800
724
668
341
254
228
190
84
7
-6
Diff.(MM4 - ab initio)
4
-13
18
-6
4
5
2
-11
-15
-17
-30
-56
-56
14
-72
51
2
-23
33
-24
-10
18
19
-15
-19
0
5
31
23
10
S-9
Assignment
Asy. CH3 str.
Asy. CH3(CH2) str.
Asy. CH3 str.
Asy. CH3(CH2) str.
Asy. CH2 str.
Sym. CH3(CH2) str.
Sym. CH3 str.
Sym. CH2 str.
Asy. CH3(CH2), CH2 def.
Asy. CH3(CH2) def.
CH2 def.
CH2 def.
Asy. CH3 def.
Sym. CH3(CH2) def.
Sym. CH3 def.
CH2 wagging
CH2 twist
CH3(CH2),CH3 rock
CH2 rock
CC str.
CH3 rock
CH3(CH2),CH3 rock
CH3(CH2),CH2 rock
CS str.
CS str.
CCS bending
CH3 torsion
CSC bending
CH3 torsion
CSCC torsion
Table 20.
Vibrational Spectrum of Thiacyclopentane(C2) (cm-1)
MP2/6-31G**a
MM3
MM4
Diff.(MM4 - ab initio)
2965
2964
2944
2937
2898
2898
2883
2882
1484
1472
1461
1458
1336
1313
1294
1265
1220
1200
1134
1059
1037
1031
960
885
882
878
820
690
686
502
461
287
108
2944
2944
2937
2936
2892
2889
2881
2873
1446
1444
1443
1433
1393
1365
1335
1291
1221
1218
1163
1142
1022
1016
972
830
906
875
814
671
627
503
413
318
120
2964
2964
2939
2937
2909
2908
2888
2878
1506
1499
1469
1448
1420
1374
1278
1272
1209
1200
1151
1125
1060
1001
993
904
888
825
771
703
669
531
455
282
114
-1
0
-5
0
11
10
5
4
22
27
8
-10
84
61
-16
27
-11
0
17
66
23
-30
33
19
6
-53
-49
13
-17
29
-6
-5
6
RMS
27
29
AVG.
-3
8
S-10
Assignment
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
C-H str.
CH2 bending
CH2 bending
CH2 bending
CH2 bending
CH2 wagging
CH2 wagging
CH2 wagging
CH2 wagging
CH2 twist
CH2 twist
CH2 twist
CH2 twist
CH2 twist
CC str.
CC str.
ring def. (CCC)
ring def. (CSC, CC)
CH2 rock
CH2 rock
ring def. (CCC, CS)
ring def. (CCC, CS)
ring def. (CCC)
ring def. (CCS, CSC)
torsion
torsion
____________________________
aThe wavenumbers for C-H stretching are scaled down to 92% of original values,
while the others are scaled down to 95%.
S-11
Table 24.
anti-gauche
0.0
Relative Stability of Methyl Ethyl Sulfide Conformers
Method
Ref.
IR
E
54
IR(Liquid)
E
55
IR
H
53
0.03±0.05
Raman
H
56
0.25±0.15
ED
Nt/(Nt+Ng)
37
0.05±0.01
IR
H
52
-8.37
CNDO/2
E
57
-1.21
4-31G
E
58
0.04
MP2/3-21G**
E
59
-0.13
MM3
E
11
0.00
MP2/6-31G*
E
this work
0.12
MM4
G
this work
-0.07
MM4
∆E
this work
-0.27
MM4
∆Η
this work
0.14±0.05
0.0
S-12
Table 25.
Input for the Heat Calculations of Sulfides and Mercaptans
WT Hf(0)
ENTHALPY
10
10
10
10
7
9
10
9
8
7
8
8
7
9
8
8
8
7
5
6
9
9
7
-5.47
-11.07
-8.96
-16.23
-14.24
-19.96
-18.21
-21.63
-45.15
-8.15
-15.18
-22.97
-24.43
-28.99
-23.26
-26.20
-30.38
-28.01
-35.37
-33.91
-11.42
-16.34
-2.32
30.31
49.78
48.95
68.71
68.71
88.46
68.56
88.14
169.59
78.67
95.69
114.87
106.55
107.40
88.54
87.29
107.70
107.86
127.10
127.32
102.11
97.56
51.62
COMPOUND
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
3-THIAPENTANE
2-PROPANETHIOL
3-ME-2THIABUTANE
DI-T-BUTYLSULFID
THIACYCLOPENTANE
THIACYCLOHEXANE
CYCLOHEXANETHIOL
2-THIAHEXANE
3,3DIME-2THIABUT
2ME1PROPANETHIOL
2ME2PROPANETHIOL
2ME2BUTANETHIOL
SUMH Hatom
-317.18
-617.93
-634.36
-918.58
-935.11
-1235.86
-918.68
-1235.86
-2438.86
-1108.94
-1409.12
-1693.25
-1536.41
-1536.61
-1220.59
-1219.43
-1520.08
-1536.61
-1837.35
-1837.35
-1393.07
-1409.69
-512.11
C-S
1
1
2
1
2
2
1
2
2
2
2
1
2
2
1
1
1
445.71
721.59
721.59
997.47
997.47
1273.35
997.47
1273.35
2376.87
1169.17
1445.05
1720.93
1549.23
1549.23
1273.35
1273.35
1549.23
1549.23
1825.11
1825.11
1445.05
1445.05
787.24
S-H
1
1
0
1
0
0
1
0
0
0
0
1
0
0
1
1
1
S-13
POP TORS COMPOUND
0.00
0.10
0.00
0.31
0.11
0.29
0.10
0.15
0.00
0.00
0.00
0.16
0.51
0.04
0.16
0.00
0.12
0.21
0.16
0.40
0.14
0.16
0.19
SEC
0
0
0
0
0
0
1
1
0
0
0
1
0
0
0
0
0
-0.57
0.00
0.00
0.57
0.57
1.14
0.00
0.57
1.14
0.57
0.00
0.00
1.71
0.57
0.57
0.00
0.57
1.14
1.14
1.14
0.57
0.57
0.57
TER
0
0
0
0
0
0
0
0
2
0
0
0
0
1
0
1
1
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
3-THIAPENTANE
2-PROPANETHIOL
3-ME-2THIABUTANE
DI-T-BUTYLSULFIDE
THIACYCLOPENTANE
THIACYCLOHEXANE
CYCLOHEXANETHIOL
2-THIAHEXANE
3,3DIME-2THIABUTA
2ME1PROPANETHIOL
2ME2PROPANETHIOL
2ME2BUTANETHIOL
2ME3THIAPENTANE
2,2DIME3THIAPENTA
2,4DIME3THIAPENTA
CYCLOPENTANETHIOL
2-METHIACYCLOPENT
ETHANE12DITHIOL
S-Me
1
0
2
0
1
0
0
1
0
0
0
0
1
1
0
0
0
SCCS
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2ME3THIAPENTANE
2,2DIME3THIAPENT
2,4DIME3THIAPENT
CYCLOPENTANETHIOL
2-METHIACYCLOPEN
ETHANE12DITHIOL
2
2
2
1
2
2
0
0
0
1
0
2
S-14
1
0
2
1
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
Table 28.
Strainless Heats of Formation of Sulfides and Mercaptans
WT Hf(0)a
ENTHALPY
10
10
10
10
7
10
8
8
-4.63
-11.16
-9.02
-17.00
-15.26
-18.75
-26.62
-11.84
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
COMPOUND
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
2-PROPANETHIOL
2ME2PROPANETHIOL
25DITHIAHEXANE
SUMH Hatom
POP TORS COMPOUND
-295.31 445.71 0.00
-576.84 721.59 0.00
-590.63 721.59 0.00
-858.57 997.47 0.00
-872.16 997.47 0.00
-858.38 997.47 0.00
-1139.91 1273.35 0.00
-1069.22 1339.00 0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
C-S
1
1
2
1
2
1
1
4
TER
0
0
0
0
0
0
1
0
S-H
1
1
0
1
0
1
1
0
SEC
0
0
0
0
0
1
0
0
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
2-PROPANETHIOL
2ME2PROPANETHIOL
25DITHIAHEXANE
S-Me
1
0
2
0
1
0
0
2
SCCS
0
0
0
0
0
0
0
1
Best Values:
C-S = -70.7021
S-H = -85.1621
S-ME = 0.7528
SCCS = -0.3171
SEC = -1.9757
WT
Hfb
Hf(0)a
Hf-Hf(0)
10
10
10
10
10
10
10
10
-4.71
-11.11
-8.94
-16.96
-15.34
-18.75
-26.62
-11.84
-4.63
-11.16
-9.02
-17.00
-15.26
-18.75
-26.62
-11.84
–0.08
0.05
0.08
0.04
–0.08
0.00
0.00
0
COMPOUND
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
2-PROPANETHIOL
2ME2PROPANETHIOL
25DITHIAHEXANE
The standard deviation = 0.05, based on 8 equations.
The weighted standard deviation = 0.05 based on 8 equations.
S-15
TER = -4.1957
________________________
aMM4
calculated heats of formation.
heats of formation.
bCalculated strainless
S-16
Table 29.
Strain Energies of Sulfides and Mercaptans
Inherent Strain
Total Strain Energy POP TORS COMPOUND
0.09
–0.04
–0.08
–0.04
0.08
0.23
-0.01
–0.49
0.06
–0.08
0.84
0.76
1.66
0.09
0.00
0.10
0.00
0.31
0.11
0.29
0.10
-0.57
0.00
0.00
0.57
0.57
1.14
0.00
METHANETHIOL
ETHANETHIOL
DIMETHYLSULFIDE
1-PROPANETHIOL
2-THIABUTANE
3-THIAPENTANE
2-PROPANETHIOL
0.76
6.42
0.76
–0.67
0.32
0.06
1.30
1.03
0.00
1.48
0.88
1.39
1.60
6.01
0.91
0.33
0.00
1.49
7.56
1.33
–0.67
0.48
2.28
1.91
1.76
0.00
2.19
2.23
2.70
3.15
6.72
1.64
1.09
1.34
0.15
0.00
0.00
0.00
0.16
0.51
0.04
0.16
0.00
0.12
0.21
0.16
0.40
0.14
0.16
0.19
0.20
0.57
1.14
0.57
0.00
0.00
1.71
0.57
0.57
0.00
0.57
1.14
1.14
1.14
0.57
0.57
0.57
1.14
3-ME-2THIABUTANE
DI-T-BUTYLSULFIDE
THIACYCLOPENTANE
THIACYCLOHEXANE
CYCLOHEXANETHIOL
2-THIAHEXANE
3,3DIME-2THIABUTA
2ME1PROPANETHIOL
2ME2PROPANETHIOL
2ME2BUTANETHIOL
2ME3THIAPENTANE
2,2DIME3THIAPENTA
2,4DIME3THIAPENTA
CYCLOPENTANETHIOL
2-METHIACYCLOPENT
ETHANE12DITHIOL
25DITHIAHEXANE
S-17