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

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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)-N(2)-H/N(5)-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/Å

3

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

cis-enolic/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.

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Group

K15

K25

cE1

N1-N2

1.372

1.365

1.374

N2-C3

1.343

1.364

1.338

C3-C9

1.425

1.398

1.432

C9-C4

1.450

1.454

1.415

C4-N5

1.443

1.427

1.340

N5-C6

1.376

1.388

1.363

C6-N7

1.316

1.307

1.341

N7-C8

1.373

1.384

1.353

C8-C9

1.416

1.439

1.426

N1-C8

1.366

1.353

1.369

C4-O

1.235

1.237

1.356

N5-H

1.025

1.024

--O-H

--

0.988

C6-H

1.097

C3-H

1.091

1.090

1.091

N1-H

1.021

--

1.020

N2-H

--

1.021

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Group

K15

K25

cE1

N1-N2-C3

105.16

115.38

105.81

N2-C3-C9

111.30

104.91

110.98

C3-C9-C8

104.93

105.13

104.99

C9-C8-N1

105.78

111.69

105.53

C8-N1-N2

112.82

102.88

112.68

C8-C9-C4

119.02

120.94

114.09

C9-C4-N5

109.65

109.48

121.31

C4-N5-C6

125.91

125.43

117.68

N5-C6-N7

124.96

125.83

128.29

C6-N7-C8

112.11

113.36

111.93

N7-C8-C9

128.35

124.95

126.71

N1-C8-N7

125.87

123.35

127.77

C3-C9-C4

136.05

133.92

140.92

N5-C4-O

120.16

121.13

118.28

C9-C4-O

130.19

129.39

120.41

C4-N5-H

114.64

115.12

--C4-O-H

--

105.22

C6-N5-H

119.45

--N5-C6-H

115.92

114.97

115.32

N7-C6-H

119.12

119.20

116.39

N2-C3-H

119.78

122.78

119.60

C9-C3-H

128.92

132.30

129.43

C8-N1-H

127.43

--

127.65

C3-N2-H

--

126.81

N2-N1-H

119.75

--

119.66

N1-N2-H

--

117.81

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

I Assignment



I Assignment

3561.74 98.76 _ N(1)-H 923.16 40.07 Ring vib.

C(3)-H vib.

3497.38 61.51 _ N(5)-H 886.79* 7.16 C(6)-H vib.

Pyrimidinic ring vib.

3206.65 0.78 _ C(3)-H 873.86 13.84 Ring vib.

3133.62 7.94 _ C(6)-H 834.42* 19.60 C(3)-H vib.

Ring vib.

1747.00 597.0

6 Ring vib. C=O N(5)-H vib.

751.77* 15.99 C(3)-H vib.

Ring vib. C=O vib.

1589.29 125.6

1 C(6)-H vib.Ring vib.

 C=O

703.10* 54.46 N(5)-H vib.

Ring vib.

 C=O

1546.98 70.13 Ring vib.

N(1)-H vib.

 C=O

678.85 9.49 Ring vib.

1502.57 10.84 Ring vib.

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

 C=O

653.19* 3.46 N(5)-H vib.

Ring vib.

1425.52 12.44 Ring vib.

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

 C=O

628.35* 48.02 N(5)-H vib.

Ring vib.

 C=O

1398.13 3.56 Ring vib.

N(5)-H vib.

 C=O

585.73 9.62 Ring vib.

1387.24 24.31 Ring vib.

N(5)-H vib. 532.34* 70.51 N(1)-H vib.N(5)-H vib. Ring vib.

1352.55 6.08 Ring vib.

C(6)-H vib.

 C=O

517.08 3.78 Ring vib.

1286.12 2.68 Ring vib.

N(1)-H vib. C=O vib.

491.27 1.44 Pyrimidinic

ring vib.

1209.03 34.64 Ring vib.

C(3)-H vib.

 C=O

476.05* 15.99 N(1)-H vib.

Ring vib.

1190.30 14.00 Ring vib.

C(3)-H vib.

 C=O

300.53 2.04 Ring vib.

1104.93 6.54 Ring vib.

N(5)-H vib.

 C=O

251.00* 1.01 Ring vib.

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K25 cE1



I Assignment



I Assignment

3562.08 124.21 _ N(2)-H 3571.37 65.77 _ OH

 N(1)-H

3501.56 56.40 _ N(5)-H 3568.59 115.59 _ N(1)-H

 OH

3216.28 1.41 _ C(3)-H 3204.47 1.05 _ C(3)-H

3124.77 12.78 C(6)-H vib. 3133.37 18.44 _ C(6)-H

1735.96 558.78 Ring vib.

N(5)-H vib. C=O vib.

 C(6)-H

1628.95 162.28 Ring vib.

* COH

 N(1)-H

1609.11 144.59 Ring vib.

C-H/N-Hvib.

 C=O

1575.11 227.17 Ring vib.

 C-O N(1)-H vib.

1556.49 18.62 Ring vib.

 C(6)-H

 N(5)-H

 C=O

1475.93 67.59 Ring vib.

C(6)-H vib.

C-O/COH

1470.16 43.07 Ring vib.

 C(6)-H

 N(5)-H

 C=O

 N(2)-H C(3)-H vib.

1451.56 82.54 _ rings

C(3)-H vib.

 C-O C(6)-H/ N(1)-H vib.

1449.14 6.95 Ring vib.

N(2)-H vib.

 C(6)-H C(3)-H vib.

 C=O

1421.48 26.69 Ring vib.

N(1)-H/ C(6)-H vib.

C-O/COH

1399.41 24.94 Ring vib.

N(5)-H vib.

 C=O

1369.24 95.70 Ring vib.

C-O/COH

1381.96 6.04 Ring vib.

N(5)-H vib.  C(6)-H  C=O

1352.85 55.14 Ring vib.

C-O/COH

1354.89 11.54  rings

 C(6)-H N(2)-H/ C(3)-H vib.

 C=O

1325.35 31.65 Ring vib.

* COH

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K25 cE1

1310.29 2.95 Ring vib.

N(2)H/ C(3)-H vib.

 C(6)-H

 C=O

1310.66 35.21 Ring vib.

C(6)-H vib.

* COH N(1)-H vib.

1225.31 29.86 Ring vib.

C(3)-H vib.

 C(6)-H

 C=O

1270.10 13.34 Ring vib.

N(1)-H vib.

* COH

1147.90 96.48 Ring vib.

N(2)-H vib.

 C=O C(6)-H vib.

1197.17 14.52 Ring vib.

C(3)-H vib.

C-O/COH

 N(1)-H

1088.82 8.99 Ring vib.

N(5)-H vib. 1144.26 6.68 Ring vib._* COH

1053.99 49.29 Ring vib.

 C(6)-H C=O vib.

1077.26 139.93 Ring vib.

* COH

1035.82 9.48 Ring vib.

 C(6)-H N(2)-H vib.

 C=O

 C(3)-H

1058.66 11.57 Ring vib.

* COH

 C(3)-H

924.72 1.92 Ring vib. 929.98* 8.08 C(6)-H vib.

Pyrimidinic ring vib.

888.42* 9.52 C(6)-H vib.

Ring vib. 921.32 57.80 C(3)-H vib.Ring vib.

 C-O

876.44 0.87 Ring vib.

 C(6)-H

 C=O

869.48 28.46 Ring vib.

 C-O

780.53* 0.12 C(3)-H vib.

Ring vib. 821.98* 18.14 C(3)-H vib.Pyrazolic

ring vib.

737.27* 29.42 C(3)-H vib.

Ring vib. 773.77* 25.34 C(3)-H vib.Ring vib.

703.63* 26.18 N(5)-H vib.

Ring vib. 700.98 3.23 _C-O/Ring vib.COH

690.19 2.53 Ring vib. 671.80* 25.32 Ring vib.

 N(1)-H

* COH

[image:6.612.121.527.95.629.2]

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K25 cE1

647.68* 87.37 N(2)-H vib.

N(5)-H vib. Ring vib.

652.06* 5.75 N(1)-H vib.

Ring vib.

 OH

619.70* 10.01 N(5)-H vib.

594.20 0.50 Ring vib.

C-O/COH

584.75 8.11 Ring vib.

 C(6)-H N(5)-H vib.

C=O vib.

565.52* 130.95 OH vib.

 N(1)-H Ring vib.

545.26* 39.22 N(2)-H vib.

Ring vib. 552.60* 8.35 N(1)-H vib.Ring vib.

OH vib.

525.29* 27.93 N(5)-H vib.

ring vib.

 C-O

521.58 3.66 Ring vib.

 C(6)-H

 C=O

ring vib.

 C-O

ring vib.

 C(6)-H

462.99* 37.55 N(1)-H vib.

Ring vib.

307.79 11.16 Ring vib.

C=O vib. 287.50 6.09 Pyrimidinic ring vib.

C-O/OH

261.79* 9.29 Ring vib. 284.57* 2.27 Ring vib.

N(1)-H vib.

189.16* 4.60 Ring vib. 196.91* 2.80 Ring vib.

C(3)-H vib.

146.94* 16.15 C=O vib.

Ring vib. 159.34* 0.00 Ring vib.

[image:7.612.119.501.82.477.2]

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