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
O
C CH3
H3C
CH3
˚ ˚ ˚ ˚
O
O O
O
O O
1-crown 2-crown 3-crown
1-keto 2-keto 3-keto
[1414]
[2323]
Table XI.
tert
-Butyl Rotation Barriers in Axial
t
-Butylcyclohexanone (kcal/mol)
B3LYP/6-31G* (t-butyl orientation: )
MM3 (t-butyl orientation: )
MM4 (t-butyl orientation: )
0.13 (0˚) 0.11 (0˚) 0.05 (0˚)
0.00 (14˚) 0.00 (13˚) 0.00 (11˚)
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
CC'C (type 1-3-1) 117.3 (18) 117.8 118.4
CCCavc 115.5 (5) 114.2 114.0
HCH 103.2 (26) 105.9 106.5
Table XVI. X-Ray† and Calculated‡ Structures of Cyclononanone Dimer
2-3 1.63 1.59 1.539 1.542 2-3-4 111 121 115.4 114.5
3-4 1.51 1.68 1.533 1.534 3-4-5 118 116 118.0 117.5
4-5 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 1.55 1.45 1.523 1.519 C9-C1=O 121 120 121.4 121.4
3-4-5-6 -61 92 -72.1 -72.8 8-9-1-2 -105 125 -113.7 -115.7
4-5-6-7 65 -71 68.3 67.4 9-1-2-3 48 -65 58.5 56.0
5-6-7-8 49 -63 56.1 55.7
1
cyclodecanone (3-keto)
Table XIX.
X-Ray† and Calculated Structures of Cyclodecanone
Bond LengthsX-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.
Bond Lengths
(Å) (Ref. 60)X-ray MM3(r)
MM4 (r)
Bond Angles
(deg) 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
