suppmat1451.doc 153KB Jun 05 2011 09:30:52 PM
03/24/01
Supplementary Material for:
Molecular Mechanics (MM4) Calculations on Carbonyl Compounds
Part III: Cycloketones (n = 4 - 11)
Charles H. Langley, Jenn-Huei Lii, and Norman L. Allinger*
Computational Center for Molecular Structure and Design
Department of Chemistry, Chemistry Annex
The University of Georgia
Athens, GA 30602-2526
* author to whom correspondence should be addressed
office: (706) 542-2043
FAX: (706) 542-2673
S-1
Supplementary Material
Figs. 4, 8 and 9.
Tables XI, XIV, XVI, XIX and XX.
S-2
O
˚
˚
˚
˚
CH3
H3 C
C
CH3
Fig. 4
S-3
O
[333]
O
1
2
O
[12222]
O
O
3
O
O
4
5
6
O
O
[12213]
7
O
8
9
10
O
[234]
O
11
O
O
12
13
[135]
14
15
Fig. 8
O
S-4
O
O
[1414]
O
1-crown
2-crown
3-crown
O
O
[2323]
O
1-keto
2-keto
Fig. 9
3-keto
S-5
Table XI. tert-Butyl Rotation Barriers in Axial t-Butylcyclohexanone (kcal/mol)
B3LYP/6-31G*
MM3
MM4
(t-butyl orientation: )
(t-butyl orientation: )
(t-butyl orientation: )
0.13 (0˚)
0.11 (0˚)
0.05 (0˚)
0.00 (14˚)
0.00 (13˚)
0.00 (11˚)
4.66 (180˚)
5.60 (180˚)
6.06 (180˚)
S-6
Table XIV. Exp. and Calculated Structures† of Cycloheptanone
Parameter
ED
(ref. 41)
MM3
(rg)
MM4
(rg)
rC=O
1.219 (12)
1.211
1.213
rC'-Cavc (type 1-3)
1.517*
1.521
1.522
rC-Cavc (type 1-1)
1.536 (3)
1.537
1.539
rC-Havc
1.124 (7)
1.113
1.113
117.8
118.4
114.2
114.0
105.9
106.5
CC'C (type 1-3-1)
CCCavc
HCH
117.3 (18)
115.5 (5)
103.2 (26)
†Boltzmann averages based on MM3 and MM4 relative energies.
*Assumed by author.
S-7
9
3
4
5
8
7
2
1
6
O
1
1
O
6
2
2
5
7
4
3
9
8
cyclononanone dimer
Table XVI. X-Ray† and Calculated‡ Structures of Cyclononanone Dimer
Bond Lengths
X-ray
MM3 MM4 Bond Angles
X-ray
(Å)
(Ref. 46)
(deg)
(r)
(r)
1
2
C1=O
1.20
1.25
1.209
1.207
C1-C2
1.38
1.55
1.518
2-3
1.63
1.59
3-4
1.51
4-5
MM3
(g)
MM4
(g)
1
2
9-1-2
124
121
117.0
117.1
1.522
1-2-3
116
106
114.5
113.4
1.539
1.542
2-3-4
111
121
115.4
114.5
1.68
1.533
1.534
3-4-5
118
116
118.0
117.5
1.60
1.34
1.537
1.535
4-5-6
117
114
117.0
116.9
5-6
1.54
1.65
1.535
1.534
5-6-7
125
113
118.7
119.2
6-7
1.43
1.49
1.536
1.535
6-7-8
119
119
116.2
116.1
7-8
1.51
1.61
1.542
1.543
7-8-9
122
114
115.1
115.0
8-9
1.53
1.58
1.547
1.547
8-9-1
112
112
113.6
111.4
9-1
C1(1)...C1(2)
1.55
1.45
1.523
1.519
C9-C1=O
121
120
121.4
121.4
3.68
3.566
3.346
C2-C1=O
114
115
121.5
121.4
X-ray
MM3
(g)
MM4
(g)
Dihedrals
(deg)
MM3
(g)
MM4
(g)
Dihedrals
(deg)
1
2
1-2-3-4
81
-62
68.3
72.0
2-3-4-5
-66
43
-60.3
3-4-5-6
-61
92
4-5-6-7
65
5-6-7-8
49
X-ray
1
2
6-7-8-9
-96
98
-98.7
-98.9
-60.3
7-8-9-1
79
-76
81.1
83.7
-72.1
-72.8
8-9-1-2
-105
125
-113.7
-115.7
-71
68.3
67.4
9-1-2-3
48
-65
58.5
56.0
-63
56.1
55.7
† Crystal observed at 1550 reflections at R-value of 11.6%. Space Group P2 /c, monoclinic.
1
Unit cell: a = 7.588(2) Å, b = 13.214(3) Å, c = 25.148(6) Å and = 96.26(2)˚
‡ MM3 and MM4 dihedrals are given for only one calculated enantiomer, the other enantiomer has the
same dihedrals but with opposite signs.
S-8
cyclodecanone (3-keto
)
8
9
7
O
10
1
5
2
4
3
6
Table XIX. X-Ray† and Calculated Structures of Cyclodecanone
Bond Lengths
(Å)
X-ray
(Ref. 59)
MM3
(r)
MM4
(r)
Bond Angles
(deg)
X-ray
MM3
MM4
C1=O
1.220(1)
1.209
1.207
C10-C1=O
120.6(1)
121.6
121.4
C1-C2
1.520(2)
1.523
1.525
C2-C1=O
120.2(1)
120.9
120.9
2-3
1.539(2)
1.543
1.545
10-1-2
119.1(1)
117.2
117.6
3-4
1.533(2)
1.538
1.537
1-2-3
118.7(1)
116.3
115.6
4-5
1.532(2)
1.536
1.531
2-3-4
115.2(1)
116.4
115.4
5-6
1.536(2)
1.540
1.536
3-4-5
114.9(1)
116.1
115.2
6-7
1.537(2)
1.536
1.534
4-5-6
114.2(1)
114.1
114.0
7-8
1.537(2)
1.540
1.538
5-6-7
114.7(1)
114.4
114.2
8-9
1.536(2)
1.538
1.538
6-7-8
117.4(1)
117.0
117.1
9-10
1.537(2)
1.538
1.534
7-8-9
117.9(1)
117.8
117.7
10-1
1.515(2)
1.524
1.521
8-9-10
117.0(1)
118.2
117.1
9-10-1
114.9(1)
114.7
113.7
Dihedrals
(deg)
X-ray
MM3
MM4
Dihedrals
(deg)
X-ray
MM3
MM4
1-2-3-4
-70.2(1)
-66.6
-68.7
6-7-8-9
66.1(2)
64.2
64.8
2-3-4-5
59.6(1)
61.5
61.3
7-8-9-10
-64.6(1)
-68.0
-66.1
3-4-5-6
65.2(1)
61.0
63.7
8-9-10-1
-56.0(1)
-48.2
-52.4
4-5-6-7
-158.6(1)
-157.4
-158.3
9-10-1-2
152.3(1)
154.0
156.0
5-6-7-8
51.4(2)
56.1
53.8
10-1-2-3
-49.1(2)
-58.3
-54.5
†The crystal structure was determined from 1392 reflections at an R-value of 3.4%.
The C–C X-ray bond lengths have a correction of +0.002 Å for thermal motions.
Space group P21/c, monoclinic. Unit cell dimensions: a = 7.023(2), b = 5.418(2), c = 23.456 (4) Å
and = 95.16(2) deg.
S-9
7
6
5
4
8
3
9
2
10
11
1
cycloundecanone
[335]
O
Table XX. X-Ray† and Calculated Structures of Cycloundecanone
Bond Lengths
X-ray
MM3
MM4
Bond Angles
(Å)
(Ref. 60)
(deg)
(r)
(r)
X-ray
MM3
MM4
C1=O
1.213(3)
1.209
1.207
C11-C1=O
120.4(2)
122.0
122.5
C1-C2
1.518(3)
1.528
1.522
C2-C1=O
120.1(2)
121.3
121.6
2-3
1.540(3)
1.550
1.546
1-2-3
113.9(2)
113.1
112.1
3-4
1.524(3)
1.537
1.537
2-3-4
114.6(2)
114.8
114.4
4-5
1.528(3)
1.536
1.533
3-4-5
116.0(2)
115.8
115.4
5-6
1.525(3)
1.536
1.534
4-5-6
115.6(2)
114.3
114.4
6-7
1.539(3)
1.540
1.538
5-6-7
114.0(2)
113.7
113.6
7-8
1.542(3)
1.539
1.536
6-7-8
114.2(2)
114.8
114.3
8-9
1.539(3)
1.547
1.541
7-8-9
113.8(2)
113.8
113.4
9-10
1.530(3)
1.536
1.532
8-9-10
115.4(2)
114.5
114.3
10-11
1.530(3)
1.537
1.534
9-10-11
113.8(2)
115.2
114.2
11-1
1.516(3)
1.523
1.524
10-11-1
114.6(2)
114.1
113.7
11-1-2
119.5(2)
116.7
115.9
Dihedrals
(deg)
X-ray
MM3
MM4
Dihedrals
(deg)
X-ray
MM3
MM4
1-2-3-4
-95.1(3)
-97.9
-97.8
7-8-9-10
-139.8(2)
-140.1
-140.1
2-3-4-5
55.7(3)
55.3
57.0
8-9-10-11
61.4(3)
63.6
62.4
3-4-5-6
64.6(3)
64.2
62.4
9-10-11-1
59.6(3)
55.5
57.2
4-5-6-7
-173.7(2)
-172.5
-172.7
10-11-1-2
-159.6(2)
-157.1
-159.9
5-6-7-8
63.6(3)
63.5
63.2
11-1-2-3
127.2(2)
130.2
129.5
6-7-8-9
64. 0(3)
65.0
66.0
†Structure determined from 1416 reflections at an R-value of 4.8%. Space Group: P2 /c, monoclinic.
1
Unit cell: a = 7.305(2) , b = 5.600(2) , c = 24.566(7) Å , = 91.29(2)˚.
The C–C X-ray bond lengths have a correction of +0.002 Å for thermal motions.
Supplementary Material for:
Molecular Mechanics (MM4) Calculations on Carbonyl Compounds
Part III: Cycloketones (n = 4 - 11)
Charles H. Langley, Jenn-Huei Lii, and Norman L. Allinger*
Computational Center for Molecular Structure and Design
Department of Chemistry, Chemistry Annex
The University of Georgia
Athens, GA 30602-2526
* author to whom correspondence should be addressed
office: (706) 542-2043
FAX: (706) 542-2673
S-1
Supplementary Material
Figs. 4, 8 and 9.
Tables XI, XIV, XVI, XIX and XX.
S-2
O
˚
˚
˚
˚
CH3
H3 C
C
CH3
Fig. 4
S-3
O
[333]
O
1
2
O
[12222]
O
O
3
O
O
4
5
6
O
O
[12213]
7
O
8
9
10
O
[234]
O
11
O
O
12
13
[135]
14
15
Fig. 8
O
S-4
O
O
[1414]
O
1-crown
2-crown
3-crown
O
O
[2323]
O
1-keto
2-keto
Fig. 9
3-keto
S-5
Table XI. tert-Butyl Rotation Barriers in Axial t-Butylcyclohexanone (kcal/mol)
B3LYP/6-31G*
MM3
MM4
(t-butyl orientation: )
(t-butyl orientation: )
(t-butyl orientation: )
0.13 (0˚)
0.11 (0˚)
0.05 (0˚)
0.00 (14˚)
0.00 (13˚)
0.00 (11˚)
4.66 (180˚)
5.60 (180˚)
6.06 (180˚)
S-6
Table XIV. Exp. and Calculated Structures† of Cycloheptanone
Parameter
ED
(ref. 41)
MM3
(rg)
MM4
(rg)
rC=O
1.219 (12)
1.211
1.213
rC'-Cavc (type 1-3)
1.517*
1.521
1.522
rC-Cavc (type 1-1)
1.536 (3)
1.537
1.539
rC-Havc
1.124 (7)
1.113
1.113
117.8
118.4
114.2
114.0
105.9
106.5
CC'C (type 1-3-1)
CCCavc
HCH
117.3 (18)
115.5 (5)
103.2 (26)
†Boltzmann averages based on MM3 and MM4 relative energies.
*Assumed by author.
S-7
9
3
4
5
8
7
2
1
6
O
1
1
O
6
2
2
5
7
4
3
9
8
cyclononanone dimer
Table XVI. X-Ray† and Calculated‡ Structures of Cyclononanone Dimer
Bond Lengths
X-ray
MM3 MM4 Bond Angles
X-ray
(Å)
(Ref. 46)
(deg)
(r)
(r)
1
2
C1=O
1.20
1.25
1.209
1.207
C1-C2
1.38
1.55
1.518
2-3
1.63
1.59
3-4
1.51
4-5
MM3
(g)
MM4
(g)
1
2
9-1-2
124
121
117.0
117.1
1.522
1-2-3
116
106
114.5
113.4
1.539
1.542
2-3-4
111
121
115.4
114.5
1.68
1.533
1.534
3-4-5
118
116
118.0
117.5
1.60
1.34
1.537
1.535
4-5-6
117
114
117.0
116.9
5-6
1.54
1.65
1.535
1.534
5-6-7
125
113
118.7
119.2
6-7
1.43
1.49
1.536
1.535
6-7-8
119
119
116.2
116.1
7-8
1.51
1.61
1.542
1.543
7-8-9
122
114
115.1
115.0
8-9
1.53
1.58
1.547
1.547
8-9-1
112
112
113.6
111.4
9-1
C1(1)...C1(2)
1.55
1.45
1.523
1.519
C9-C1=O
121
120
121.4
121.4
3.68
3.566
3.346
C2-C1=O
114
115
121.5
121.4
X-ray
MM3
(g)
MM4
(g)
Dihedrals
(deg)
MM3
(g)
MM4
(g)
Dihedrals
(deg)
1
2
1-2-3-4
81
-62
68.3
72.0
2-3-4-5
-66
43
-60.3
3-4-5-6
-61
92
4-5-6-7
65
5-6-7-8
49
X-ray
1
2
6-7-8-9
-96
98
-98.7
-98.9
-60.3
7-8-9-1
79
-76
81.1
83.7
-72.1
-72.8
8-9-1-2
-105
125
-113.7
-115.7
-71
68.3
67.4
9-1-2-3
48
-65
58.5
56.0
-63
56.1
55.7
† Crystal observed at 1550 reflections at R-value of 11.6%. Space Group P2 /c, monoclinic.
1
Unit cell: a = 7.588(2) Å, b = 13.214(3) Å, c = 25.148(6) Å and = 96.26(2)˚
‡ MM3 and MM4 dihedrals are given for only one calculated enantiomer, the other enantiomer has the
same dihedrals but with opposite signs.
S-8
cyclodecanone (3-keto
)
8
9
7
O
10
1
5
2
4
3
6
Table XIX. X-Ray† and Calculated Structures of Cyclodecanone
Bond Lengths
(Å)
X-ray
(Ref. 59)
MM3
(r)
MM4
(r)
Bond Angles
(deg)
X-ray
MM3
MM4
C1=O
1.220(1)
1.209
1.207
C10-C1=O
120.6(1)
121.6
121.4
C1-C2
1.520(2)
1.523
1.525
C2-C1=O
120.2(1)
120.9
120.9
2-3
1.539(2)
1.543
1.545
10-1-2
119.1(1)
117.2
117.6
3-4
1.533(2)
1.538
1.537
1-2-3
118.7(1)
116.3
115.6
4-5
1.532(2)
1.536
1.531
2-3-4
115.2(1)
116.4
115.4
5-6
1.536(2)
1.540
1.536
3-4-5
114.9(1)
116.1
115.2
6-7
1.537(2)
1.536
1.534
4-5-6
114.2(1)
114.1
114.0
7-8
1.537(2)
1.540
1.538
5-6-7
114.7(1)
114.4
114.2
8-9
1.536(2)
1.538
1.538
6-7-8
117.4(1)
117.0
117.1
9-10
1.537(2)
1.538
1.534
7-8-9
117.9(1)
117.8
117.7
10-1
1.515(2)
1.524
1.521
8-9-10
117.0(1)
118.2
117.1
9-10-1
114.9(1)
114.7
113.7
Dihedrals
(deg)
X-ray
MM3
MM4
Dihedrals
(deg)
X-ray
MM3
MM4
1-2-3-4
-70.2(1)
-66.6
-68.7
6-7-8-9
66.1(2)
64.2
64.8
2-3-4-5
59.6(1)
61.5
61.3
7-8-9-10
-64.6(1)
-68.0
-66.1
3-4-5-6
65.2(1)
61.0
63.7
8-9-10-1
-56.0(1)
-48.2
-52.4
4-5-6-7
-158.6(1)
-157.4
-158.3
9-10-1-2
152.3(1)
154.0
156.0
5-6-7-8
51.4(2)
56.1
53.8
10-1-2-3
-49.1(2)
-58.3
-54.5
†The crystal structure was determined from 1392 reflections at an R-value of 3.4%.
The C–C X-ray bond lengths have a correction of +0.002 Å for thermal motions.
Space group P21/c, monoclinic. Unit cell dimensions: a = 7.023(2), b = 5.418(2), c = 23.456 (4) Å
and = 95.16(2) deg.
S-9
7
6
5
4
8
3
9
2
10
11
1
cycloundecanone
[335]
O
Table XX. X-Ray† and Calculated Structures of Cycloundecanone
Bond Lengths
X-ray
MM3
MM4
Bond Angles
(Å)
(Ref. 60)
(deg)
(r)
(r)
X-ray
MM3
MM4
C1=O
1.213(3)
1.209
1.207
C11-C1=O
120.4(2)
122.0
122.5
C1-C2
1.518(3)
1.528
1.522
C2-C1=O
120.1(2)
121.3
121.6
2-3
1.540(3)
1.550
1.546
1-2-3
113.9(2)
113.1
112.1
3-4
1.524(3)
1.537
1.537
2-3-4
114.6(2)
114.8
114.4
4-5
1.528(3)
1.536
1.533
3-4-5
116.0(2)
115.8
115.4
5-6
1.525(3)
1.536
1.534
4-5-6
115.6(2)
114.3
114.4
6-7
1.539(3)
1.540
1.538
5-6-7
114.0(2)
113.7
113.6
7-8
1.542(3)
1.539
1.536
6-7-8
114.2(2)
114.8
114.3
8-9
1.539(3)
1.547
1.541
7-8-9
113.8(2)
113.8
113.4
9-10
1.530(3)
1.536
1.532
8-9-10
115.4(2)
114.5
114.3
10-11
1.530(3)
1.537
1.534
9-10-11
113.8(2)
115.2
114.2
11-1
1.516(3)
1.523
1.524
10-11-1
114.6(2)
114.1
113.7
11-1-2
119.5(2)
116.7
115.9
Dihedrals
(deg)
X-ray
MM3
MM4
Dihedrals
(deg)
X-ray
MM3
MM4
1-2-3-4
-95.1(3)
-97.9
-97.8
7-8-9-10
-139.8(2)
-140.1
-140.1
2-3-4-5
55.7(3)
55.3
57.0
8-9-10-11
61.4(3)
63.6
62.4
3-4-5-6
64.6(3)
64.2
62.4
9-10-11-1
59.6(3)
55.5
57.2
4-5-6-7
-173.7(2)
-172.5
-172.7
10-11-1-2
-159.6(2)
-157.1
-159.9
5-6-7-8
63.6(3)
63.5
63.2
11-1-2-3
127.2(2)
130.2
129.5
6-7-8-9
64. 0(3)
65.0
66.0
†Structure determined from 1416 reflections at an R-value of 4.8%. Space Group: P2 /c, monoclinic.
1
Unit cell: a = 7.305(2) , b = 5.600(2) , c = 24.566(7) Å , = 91.29(2)˚.
The C–C X-ray bond lengths have a correction of +0.002 Å for thermal motions.