suppmat1064.doc 139KB Jun 05 2011 09:30:47 PM

SUPPLEMENTARY MATERIAL: TABLES  III Ð X
An Ab Initio Molecular Orbital Study of the Energies and Conformers of 3,4­Dihydro­1,2­
dithiin, 3,6­Dihydro­1,2­dithiin, 4H­1,3­Dithiin, and 2,3­Dihydro­1,4­dithiin

Fillmore Freeman, 



*,  

 

Choonsun Lee, Henry N.  Po,

 

and  Warren J.  Hehre

,

Department of Chemistry, University of California, Irvine, CA 92697­2025

 Department of Chemistry, California State University, Long Beach, CA 90840



Wavefunction, Inc., 18401 Von Karman Avenue, Suite 370, Irvine, CA 92612

1

Table III. 6­31G* Optimized Geometries for the  Conformers of 3,4­Dihydro­1,2­dithiin (1,9)
 
H

3

H

S1
S2

H

H
1

C1, half­chair (1) 

Bond length ()
­S1­S2­
­S2­C3­
­C3­C4­
­C4­C5=
­C5=C6­
=C6­S1­
=C5­H
=C6­H
­C3­Hax
­C3­Heq
­C4­Hax
­C4­Heq

Bond angle (o)
­S1­S2­C3­
­S2­C3­C4­
­C3­C4­C5=
­C4­C5=C6­
­C5=C6­S1­
=C6­S1­S2­
Torsion angle (o) 
Hax­C3­C4­Hax
Heq­C3­C4­Heq
S1­C6=C5­C4­
=C6­S1­S2­C3­
­C3­C4­C5=C6­
S2­C3­C4­ Hax
S2­C3­C4­ Heq
Twist angle (o)
Dipole moment (debye)

2.062
1.819

1.527
1.509
1.320
1.770
1.078
1.075
1.082
1.083
1.087
1.088
98.0
111.9
115.7
128.4
127.4
100.8
166.5
68.9
0.2
48.7

12.0
71.7
173.0
25.8
2.9

2

C1, boat  (9)
2.078
1.834
1.542
1.508
1.321
1.773
1.076
1.074
1.082
1.082
1.085

1.084
102.4
114.6
114.6
121.6
119.6
99.0

2.1
49.8
60.9

3.05

Table IV.  6­31G* Optimized Geometries  for the conformers of  3,6­Dihydro­1,2­dithiin (2, 10)
H

S2
3

H
S1

H

H
2

C2, half­chair (2)

Cs, boat (10)

2.056
1.815
1.508
1.321
1.508
1.815
1.078
1.084

2.099
1.838
1.502
1.320
1.502
1.838
1.075
1.082

Bond length ()
­S1­S2­
­S2­C3­
­C3­C4=
­C4=C5­
=C5­C6­
­C6­S1­
=C­H
­C3­Hax
­C3­Heq

1.085

Bond angle (o)
­S1­S2­C3­
­S2­C3­C4­
­C3­C4=C5­
­C4=C5­C6­
=C5­C6­S1­
­C6­S1­S2­
Torsion angle (o)
­C6­S1­S2­C3­
­C3­C4=C5­C6­
­S1­C6­ C5=C4­
­S1­S2­C3­C4­
Twist angle (o)
Dipole moment (debye)

3

98.5
114.4
128.1
128.1
114.4
98.5

102.0
112.8
120.9
120.9
112.8
102.0

61.9
1.0
20.5
51.2
35.5
2.7

0
0

0
3.4

Table V.  6­31G* Optimized Geometries  for the Conformers of   4H­1,3­dithiins (3,11)
H

H

2

H
S3

H

S1
3

C1, half­chair (3)

C1, boat (11)

Bond length ()
­S1­C2­
­C2­S3­
­S3­C4­
­C4­C5=
­C5=C6­
=C6­S1­
=C5­H
=C6­H
­C2­Hax

1.809
1.806
1.814
1.506
1.321
1.762
1.078
1.075
1.081

1.819
1.823
1.832
1.502
1.320
1.772
1.076
1.074
1.082

­C2­Heq

1.081

1.081

­C4­Hax

1.086

1.079

­C4­Heq

1.084

1.081

Bond angle (o)
­S1­C2­S3­
­C2­S3­C4­
­S3­C4­C5=
­C4­C5=C6­
­C5=C6­S1­
=C6­S1­C2­
Torsion angle (o)
­S1­C2­S3­C4­
­C2­S3­C4­C5=
­S3­C4C5=C6­
­C4­C5=C6­S1­
­C5=C6­S1­C2­
=C6­S1­C2­S3
Twist angle (o)
Dipole moment (debye)

4

114.5
98.2
115.2
128.3
129.0
101.0

116.0
101.7
114.3
122.0
120.9
98.3

64.8
49.7
21.8
0.9
11.2
47.1
33.2
1.9

17.0
39.7
57.5
4.4
50.2
55.7
1.49

Table VI.  6­31G* Optimized  Geometries  for the Conformers of 2,3­Dihydro­1,4­dithiin (4, 12)
H
3

S1
H

2

H

C2, half­chair  (4)
Bond length ()
­S1­C2­
­C2­C3­
­C5=C6­
=C6­S1­
=C­H
­C­Hax
­C­Heq
Bond angle (o)
­S1­C2­C3­
­C5=C6­S1­
=C6­S1­C2­
Torsion angle (o)
H­C=C­H
Hax­C2­C3­Hax
Heq­C2­C3­Heq
­S1­C2­C3­S4­
­S4­C5=C6­S1­
­C5=C6­S1­C2­
=C6­S1­C2­C3­
Twist angle (o)
Dipole moment (debye)

1.813
1.527
1.321
1.763
1.075
1.081
1.083
113.2
128.7
101.5

H
S4

4

Cs, boat (12)
1.826
1.542
1.322
1.763
1.075
1.081

117.5
122.8
101.0

1.5
176.8
55.3
70.3
1.3
12.7
47.8
33.0
0.8

5

0
0
46.8
43.7
0
2.1

 Table VII.  Frequency Calculations (6­31G*) for 3,4­dihydro­1,2­dithiins (1)
H
3

H

S1
S2

H

H
1

half chair
normal
vibrational 
modes 
frequency,
­1

Planar
normal
Vibrational 
modes 
Frequency,

 cm
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A

145.77
263.40
339.77
424.28
467.50
565.19
703.34
730.70
769.38
811.04
931.41
985.19
1084.88
1110.29
1129.01
1291.21
1323.21
1373.18
1454.63
1504.46
1533.57
1610.00
1624.44
1853.49
3197.02
3228.60
3250.76
3304.90
3338.65
3377.98

 cm
A"
A"
A'
A"
A'
A'
A'
A"
A'
A"
A'
A'
A"
A"
A'
A"
A'
A"
A'
A'
A'
A'
A'
A'
A'
A"
A'
A"
A'
A'
6

­1

­259.78
­135.34
349.37
420.50
454.67
540.89
710.14
726.56
756.16
872.05
891.08
949.11
1078.76
1107.72
1173.23
1345.20
1352.34
1412.42
1448.57
1510.32
1533.18
1623.93
1656.19
1882.00
3204.10
3230.39
3268.09
3318.11
3337.57
3375.78

boat
normal
vibrational 
modes 
frequency,
.cm
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A

­1

115.59
227.19
352.48
392.78
525.80
546.88
660.93
718.54
797.20
814.93
941.50
989.18
1079.13
1107.06
1124.77
1271.84
1307.51
1364.30
1450.22
1469.02
1517.09
1630.26
1639.70
1825.37
3221.85
3247.45
3265.92
3301.68
3357.57
3396.16

Table VIII.  Frequency Calculations (6­31G*) for 3,6­dihydro­1,2­dithiins (2)

 

half chair
normal
vibrational 
modes 
frequency,
­1

planar
normal
vibrational 
modes 
frequency,

 cm
B
A
B
A
A
A
B
B
A
B
A
A
B
B
A
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A

156.16
223.08
335.75
391.67
486.77
567.57
704.46
712.35
762.41
902.53
963.62
994.81
1025.98
1090.23
1122.11
1310.09
1317.73
1341.14
1442.52
1458.83
1545.99
1603.63
1604.16
1894.24
3230.02
3230.05
3273.88
3274.37
3327.12
3351.61

 cm
A2
B1
B2
A2
A1
A1
B2
B1
A1
B2
A2
A1
B1
B2
A2
A2
B1
A1
B2
A1
B2
B2
A1
A1
A1
B2
B1
A2
B2
A1

7

­1

­216.17
­130.26
347.18
393.38
438.10
530.32
698.54
708.66
750.94
908.10
979.02
983.34
1026.87
1123.05
1136.01
1316.71
1328.22
1355.38
1455.11
1476.60
1555.09
1624.11
1624.41
1926.27
3232.65
3232.70
3275.40
3277.26
3323.11
3347.59

boat
normal
vibrational 
modes 
frequency,
 cm
A"
A'
A"
A'
A"
A'
A"
A'
A"
A'
A'
A'
A"
A"
A"
A'
A"
A'
A"
A'
A"
A"
A'
A'
A"
A'
A"
A'
A"
A'

­1

31.34
228.09
318.12
401.28
494.04
535.60
667.59
677.45
792.19
849.95
972.74
1012.37
1043.66
1099.90
1118.14
1269.47
1329.09
1351.67
1405.30
1408.36
1534.35
1621.35
1636.81
1871.18
3249.18
3251.72
3303.10
3305.71
3360.99
3384.39

Table IX.  Frequency Calculations (6­31G*) for 4H­1,3­dithiins (3)
 

half chair
normal
vibrational 
modes 
frequency,
­1

planar
normal
modes 

 cm
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A

121.12
231.44
364.07
378.54
464.36
666.03
732.36
749.22
779.83
845.42
859.41
932.43
1030.17
1055.73
1099.03
1270.80
1331.00
1341.90
1384.24
1459.41
1514.18
1594.75
1615.78
1855.31
3220.16
3264.69
3272.82
3329.07
3336.49
3379.77

vibrational 
frequency,
cm

A"
A"
A'
A'
A"
A'
A"
A'
A'
A'
A'
A"
A"
A'
A"
A"
A"
A'
A'
A'
A'
A'
A'
A'
A'
A"
A'
A"
A'
A'

­1

­210.74
­112.25
381.56
397.23
426.33
628.56
739.28
748.41
767.00
874.53
908.79
931.39
1007.30
1073.27
1102.59
1274.97
1329.81
1339.34
1405.65
1479.13
1518.52
1631.34
1638.95
1885.72
3230.10
3269.21
3277.97
3333.92
3337.70
3375.39

8

boat
normal
vibrational 
modes 
frequency,
 cm
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A

­1

103.00
198.40
359.87
370.71
494.66
637.93
704.39
742.58
801.06
839.65
885.37
941.81
1018.56
1066.93
1099.62
1263.47
1295.39
1343.00
1378.12
1432.11
1496.94
1614.03
1627.33
1832.27
3252.81
3273.34
3307.66
3333.68
3357.67
3395.80

Table X.  Frequency Calculations (6­31G*) for 2,3­Dihydro­1,4­dithiins (4)
 

half chair
normal
vibrational 
modes 
frequency,
­1

planar
normal
modes 

 cm
B
A
A
B
A
B
A
B
A
B
B
B
A
A
A
B
A
A
B
A
B
B
A
A
B
A
A
B
B
A

85.85
277.38
347.44
440.66
474.03
674.86
694.33
738.09
746.43
773.00
897.04
999.11
1030.43
1073.35
1093.13
1266.65
1305.92
1348.58
1433.15
1474.28
1493.57
1616.99
1623.46
1811.1
3246.79
3255.59
3301.48
3313.42
3367.59
3389.58

vibrational 
frequency,
 cm

A2
B1
A1
A2
B2
A1
B2
B1
A1
B1
B2
B2
A2
A2
A1
A1
B1
A2
A1
B2
B2
B2
A1
A1
B2
A1
A2
B1
B2
A1

9

­1

­280.16
­124.92
349.88
456.45
469.35
647.21
714.72
745.44
748.34
829.46
853.06
913.04
1031.13
1079.40
1125.23
1323.78
1335.94
1398.98
1447.70
1449.02
1503.40
1633.48
1662.37
1839.88
3254.02
3272.75
3297.96
3323.13
3369.21
3390.91

boat
normal
vibrational 
modes 
frequency,
 cm
A"
A'
A'
A"
A"
A"
A'
A'
A'
A"
A'
A"
A"
A"
A'
A'
A'
A"
A'
A"
A"
A"
A'
A'
A"
A'
A"
A'
A"
A'

­1

­147.05
166.40
343.00
417.23
514.61
654.01
683.45
763.77
793.34
831.27
841.01
906.14
1064.42
1079.58
1094.78
1284.10
1317.83
1390.75
1421.01
1439.05
1481.92
1617.35
1643.49
1785.35
3246.47
3262.94
3291.11
3317.35
3371.17
3394.76