jcc1544_supp.doc 363KB Jun 05 2011 09:30:49 PM

Supplementary Materials.
Table I. a) Internuclear Distances (Å) and b) Angles (degrees) for the optimized
structures of the three energetically most stable N(1)-H/N(5)-H (K15), N(2)H/N(5)-H (K25) and cis-enolic/N(1)-H (cE1) neutral allopurinol tautomers.
Table II. Corrected Wave Number ( , cm-1), Intensity (I, KM/mol) and
Vibrational Normal Modes Assignment for each absorption corresponding to the
theoretical IR vibrational spectra of a) N(1)-H/N(5)-H (K15), and b) N(2)-H/N(5)H (K25) and cis-enolic/N(1)-H (cE1) neutral allopurinol tautomers. * means out
of the molecular plane vibrational modes at this wave number; * means  and 
combined vibrational modes.
Figure 1. Total Electronic Charge Density contour maps (0.1-0.3 e/Å3 range,
changes in 0.05 units) at the optimized molecular plane for the three
energetically most stable N(1)-H/N(5)-H (K15), N(2)-H/N(5)-H (K25) and cisenolic/N(1)-H (cE1) allopurinol tautomers.
Figure 2. 3-D Molecular Electrostatic Potential isosurfaces (-30 kcal/mol) for
the N(1)-H/N(5)-H (K15), N(2)-H/N(5)-H (K25) and

cis-enolic/N(1)-H (cE1)

neutral allopurinol tautomers.
Figure 3. 3D-HOMOs (upper series) and LUMOs (lower series) Wave Functions
(0.025 level) for the N(1)-H/N(5)-H (K15), N(2)-H/N(5)-H (K25) and (c) cisenolic/N(1)-H (cE1) neutral allopurinol tautomers.

1

Group
N1-N2
N2-C3
C3-C9
C9-C4
C4-N5
N5-C6
C6-N7
N7-C8
C8-C9
N1-C8
C4-O
N5-H
O-H
C6-H
C3-H
N1-H
N2-H

K15
1.372
1.343
1.425
1.450
1.443
1.376
1.316
1.373
1.416
1.366
1.235
1.025
-1.097
1.091
1.021
--

K25
1.365

1.364
1.398
1.454
1.427
1.388
1.307
1.384
1.439
1.353
1.237
1.024
-1.097
1.090
-1.021

cE1
1.374
1.338
1.432
1.415

1.340
1.363
1.341
1.353
1.426
1.369
1.356
-0.988
1.097
1.091
1.020
--

Table Ia.

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Group
N1-N2-C3
N2-C3-C9

C3-C9-C8
C9-C8-N1
C8-N1-N2
C8-C9-C4
C9-C4-N5
C4-N5-C6
N5-C6-N7
C6-N7-C8
N7-C8-C9
N1-C8-N7
C3-C9-C4
N5-C4-O
C9-C4-O
C4-N5-H
C4-O-H
C6-N5-H
N5-C6-H
N7-C6-H
N2-C3-H
C9-C3-H

C8-N1-H
C3-N2-H
N2-N1-H
N1-N2-H

K15
105.16
111.30
104.93
105.78
112.82
119.02
109.65
125.91
124.96
112.11
128.35
125.87
136.05
120.16

130.19
114.64
-119.45
115.92
119.12
119.78
128.92
127.43
-119.75
--

K25
115.38
104.91
105.13
111.69
102.88
120.94
109.48
125.43

125.83
113.36
124.95
123.35
133.92
121.13
129.39
115.12
-119.45
114.97
119.20
122.78
132.30
-126.81
-117.81

cE1
105.81
110.98
104.99

105.53
112.68
114.09
121.31
117.68
128.29
111.93
126.71
127.77
140.92
118.28
120.41
-105.22
-115.32
116.39
119.60
129.43
127.65
-119.66
--

Table Ib.

3

I

Assignment

3561.74

98.76

I

Assignment

 N(1)-H

923.16

40.07

61.51

 N(5)-H

886.79*

7.16

3206.65
3133.62

0.78
7.94

 C(3)-H
 C(6)-H

873.86
834.42*

13.84
19.60

1747.00

597.0
6

751.77*

15.99

1589.29

125.6
1

703.10*

54.46

1546.98

70.13

678.85

9.49

1502.57

10.84

653.19*

3.46

N(5)-H vib.
Ring vib.

1425.52

12.44

628.35*

48.02

N(5)-H vib.
Ring vib.
 C=O

1398.13

3.56

585.73

9.62

Ring vib.

1387.24

24.31

 C=O
Ring vib.
N(5)-H vib.
Ring vib.
C(6)-H vib.
 C=O
Ring vib.
N(1)-H vib.
 C=O
Ring vib.
C(3)-H vib.
N(5)-H vib.
 C=O
Ring vib.
N-H vib.
C(3)-H vib.
 C=O
Ring vib.
N(5)-H vib.
 C=O
Ring vib.
N(5)-H vib.

Ring vib.
C(3)-H vib.
C(6)-H vib.
Pyrimidinic
ring vib.
Ring vib.
C(3)-H vib.
Ring vib.
C(3)-H vib.
Ring vib.
C=O vib.
N(5)-H vib.
Ring vib.
 C=O
Ring vib.

3497.38

532.34*

70.51

1352.55

6.08

517.08

3.78

1286.12

2.68

491.27

1.44

Pyrimidinic
ring vib.

1209.03

34.64

476.05*

15.99

N(1)-H vib.
Ring vib.

1190.30

14.00

300.53

2.04

Ring vib.

1104.93

6.54

251.00*

1.01

Ring vib.

1071.07

25.61

1024.74

34.14

Ring vib.
C(6)-H vib.
 C=O
Ring vib.
N(1)-H vib.
C=O vib.
Ring vib.
C(3)-H vib.
 C=O
Ring vib.
C(3)-H vib.
 C=O
Ring vib.
N(5)-H vib.
 C=O
Ring vib.
 C=O
Ring vib.

N(1)-H vib.
N(5)-H vib.
Ring vib.
Ring vib.





188.59*
147.68*

4.02
5.13

Ring vib.
Ring vib.

Table IIa.
4

K25

cE1

I

Assignment

3562.08

124.21

 N(2)-H

3501.56

56.40

3216.28
3124.77
1735.96

1.41
12.78
558.78

1609.11

144.59

1556.49

18.62

1470.16

43.07

1449.14

6.95

1399.41

24.94

1381.96

6.04

1354.89

11.54



I

Assignment

3571.37

65.77

 N(5)-H

3568.59

115.59

 C(3)-H
C(6)-H vib.
Ring vib.
N(5)-H vib.
C=O vib.
 C(6)-H
Ring vib.
C-H/N-Hvib.
 C=O
Ring vib.
 C(6)-H
 N(5)-H
 C=O
Ring vib.
 C(6)-H
 N(5)-H
 C=O
 N(2)-H
C(3)-H vib.
Ring vib.
N(2)-H vib.
 C(6)-H
C(3)-H vib.
 C=O
Ring vib.
N(5)-H vib.
 C=O

3204.47
3133.37
1628.95

1.05
18.44
162.28

 OH
 N(1)-H
 N(1)-H
 OH
 C(3)-H
 C(6)-H
Ring vib.
* COH
 N(1)-H

1575.11

227.17

1475.93

67.59

1451.56

82.54

 rings
C(3)-H vib.
 C-O
C(6)-H/
N(1)-H vib.

1421.48

26.69

Ring vib.
N(1)-H/
C(6)-H vib.
C-O/COH

1369.24

95.70

Ring vib.
N(5)-H vib.
 C(6)-H
 C=O
 rings
 C(6)-H
N(2)-H/
C(3)-H vib.
 C=O

1352.85

55.14

1325.35

31.65

Ring vib.
C(6)-H vib.
N(1)-H vib.
C-O/COH
Ring vib.
C(6)-H vib.
N(1)-H vib.
C-O/COH
Ring vib.
* COH



Ring vib.
 C-O
N(1)-H vib.
Ring vib.
C(6)-H vib.
C-O/COH

Table IIb.

5

1310.29

K25
2.95

Ring vib.
N(2)H/
C(3)-H vib.
 C(6)-H
 C=O
Ring vib.
C(3)-H vib.
 C(6)-H
 C=O
Ring vib.
N(2)-H vib.
 C=O
C(6)-H vib.
Ring vib.
N(5)-H vib.
Ring vib.
 C(6)-H
C=O vib.
Ring vib.
 C(6)-H
N(2)-H vib.
 C=O
 C(3)-H
Ring vib.

1310.66

cE1
35.21

1225.31

29.86

1270.10

13.34

Ring vib.
N(1)-H vib.
* COH

1147.90

96.48

1197.17

14.52

1144.26

6.68

1077.26

139.93

Ring vib.
C(3)-H vib.
C-O/COH
 N(1)-H
Ring vib.
* COH
Ring vib.
* COH

1088.82

8.99

1053.99

49.29

1035.82

9.48

1058.66

11.57

Ring vib.
* COH
 C(3)-H

924.72

1.92

929.98*

8.08

9.52

C(6)-H vib.
Ring vib.

921.32

57.80

876.44

0.87

869.48

28.46

780.53*

0.12

Ring vib.
 C(6)-H
 C=O
C(3)-H vib.
Ring vib.

C(6)-H vib.
Pyrimidinic
ring vib.
Ring vib.
C(3)-H vib.
 C-O
Ring vib.
 C-O

888.42*

821.98*

18.14

737.27*

29.42

773.77*

25.34

703.63*

26.18

700.98

3.23

690.19

2.53

C(3)-H vib.
Ring vib.
N(5)-H vib.
Ring vib.
Ring vib.

671.80*

25.32

Ring vib.
C(6)-H vib.
* COH
N(1)-H vib.

C(3)-H vib.
Pyrazolic
ring vib.
C(3)-H vib.
Ring vib.
Ring vib.
C-O/COH
Ring vib.
 N(1)-H
* COH

Table IIb (continuation).

6

647.68*

K25
87.37

619.70*

10.01

584.75

8.11

545.26*

39.22

525.29*

27.93

521.58

3.66

497.59

2.36

307.79

11.16

261.79*

cE1
N(2)-H vib.
N(5)-H vib.
Ring vib.
N(5)-H vib.
N(2)-H vib.
Ring vib.
Ring vib.
 C(6)-H
N(5)-H vib.
C=O vib.
N(2)-H vib.
Ring vib.

652.06*

5.75

N(1)-H vib.
Ring vib.
 OH
Ring vib.
C-O/COH

594.20

0.50

565.52*

130.95

OH vib.
 N(1)-H
Ring vib.

552.60*

8.35

N(5)-H vib.
N(2)-H vib.
Ring vib.
Ring vib.
 C(6)-H
 C=O
Pyrimidinic
ring vib.
 C(6)-H
Ring vib.
C=O vib.

513.85

0.88

508.45

4.05

462.99*

37.55

Ring vib.
N(1)-H vib.
OH vib.
Pyrimidinic
ring vib.
 C-O
Pyrimidinic
ring vib.
 C-O
N(1)-H vib.
Ring vib.

287.50

6.09

9.29

Ring vib.

284.57*

2.27

189.16*

4.60

Ring vib.

196.91*

2.80

146.94*

16.15

C=O vib.
Ring vib.

159.34*

0.00

Pyrimidinic
ring vib.
C-O/OH
Ring vib.
N(1)-H vib.
Ring vib.
C(3)-H vib.
Ring vib.

Table IIb (continuation).

7

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