The Journal of Chemical Physics
Supplementary Information for
Manuscript A13.11.0288
TETRAZOLE ACETIC ACID:
TAUTOMERS, CONFORMERS AND ISOMERIZATION
C. Araujo-Andrade,a,b I. Revab,* and R. Faustob
a
Unidad Académica de Física de la Universidad Autónoma de Zacatecas, Zacatecas, Mexico
b Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal
Contents
Figure S1
Region of the NH stretching vibrations of the experimental spectra of
5-methyl-tetrazole monomers isolated in an N2 and in an Ar matrix.
Figure S2
MP2/6-311++G(d,p) optimized geometries and selected dihedral angles
for the conformers of the two tautomeric forms (1H- and 2H-) of TAA
Selected regions of the experimental IR spectra of TAA isolated in an N 2
matrix, recorded at 13 K before and after of annealing up to 24 K
Figure S3
2
3
5
Table S1
Internal coordinates used in the normal mode analysis of 1ccc and 1cct
conformers of 1H-TAA
6
Table S2
Internal coordinates used in the normal mode analysis of 2pcc and 2pct
conformers of 2H-TAA
7
Table S3
B3LYP/6–311++G(d,p) calculated wavenumbers, absolute intensities and
potential energy distributions for conformer 1ccc of 1H-TAA
8
Table S4
B3LYP/6–311++G(d,p) calculated wavenumbers, absolute intensities and
potential energy distributions for conformer 1cct of 1H-TAA
9
Table S5
B3LYP/6–311++G(d,p) calculated wavenumbers, absolute intensities and
potential energy distributions for conformer 2pcc of 2H-TAA
10
Table S6
B3LYP/6–311++G(d,p) calculated wavenumbers, absolute intensities and
potential energy distributions for conformer 2pct of 2H-TAA
11
Table S7
Cartesian coordinates of the B3LYP/6-311++G(d,p) optimized geometries
of conformers of 1H- and 2H- tautomers of TAA
12
Table S8
Cartesian coordinates of the MP2/6-311++G(d,p) optimized geometries
of conformers of 1H- and 2H- tautomers of TAA
14
Table S9
Cartesian coordinates of the QCISD/6-311++G(d,p) optimized geometries
of conformers of 1H- and 2H- tautomers of TAA
16
Absorbance
5-MeT : N2 matrix @15K
0.9
3455
0.6
2H
0.3
1H
0.0
3500
3480
3460
3440
3420
5-MeT : Ar matrix @15K
3471
Absorbance
0.9
2H
0.6
0.3
1H
0.0
3500
3480
3460
3440
3420
Wavenumber / cm 1
Figure S1.
Region of the NH stretching vibrations of the experimental spectra of 5-methyl-tetrazole
(5-MeT) monomers isolated in an N2 matrix (top) and in an Ar matrix (bottom) at 15 K.
1H and 2H indicate the bands associated with absorptions of two 5-MeT tautomers, differing
by the position of the annular proton. The peak positions (in cm−1) of the dominating
2H tautomer are indicated in the figure.
2
Figure S2.
MP2/6-311++G(d,p) optimized geometries and selected dihedral angles for the conformers
of the two tautomeric forms (1H- and 2H-) of TAA. The optimized Cartesian coordinates of
these forms, calculated at the B3LYP, MP2, and QCISD levels of theory with the
6-311++G(d,p) basis set are listed in Tables S7, S8, S9 of the Supplementary material.
1ccc
1cct
N1C5CC:
31.0°
C5CC=O: −27.0°
O=COH:
−1.3
N1C5CC:
33.6°
C5CC=O: −30.5°
O=COH:
176.6°
1ctc
1ttt
N1C5CC: 49.4°
C5CC=O: 128.1°
O=COH:
−0.1°
N1C5CC: 131.5°
C5CC=O: −146.0°
O=COH:
174.1°
3
Figure S2. (Continued)
2pcc
N1C5CC:
C5CC=O:
O=COH:
2pct
85.4°
−3.4°
0.0°
N1C5CC:
85.1°
C5CC=O:
−5.4°
O=COH:
178.4°
2ptt
2pt'c
N1C5CC: 127.6°
C5CC=O: −142.7°
O=COH:
174.9°
N1C5CC: 106.0°
C5CC=O: 145.4°
O=COH:
−0.8°
2ptc
2pt't
N1C5CC:
67.7°
C5CC=O: −145.3°
O=COH:
−0.1°
N1C5CC:
57.9°
C5CC=O: 140.9°
O=COH: −176.0°
4
0.30
13 K (Dep.)
13 K (Ann.)
0.25
13 K (Dep.)
13 K (Ann.)
0.25
0.20
0.15
Absorbance
Absorbance
0.20
*
0.10
0.05
0.10
0.05
0.00
3460
3450
3440
0.00
1800
3430
Wavenumber / cm
0.7
0.15
1
1785
1770
Wavenumber / cm
0.12
13 K (Dep.)
13 K (Ann.)
1
1755
13 K (Dep.)
13 K (Ann.)
0.6
0.10
Absorbance
Absorbance
0.5
0.4
0.3
0.08
0.06
0.2
*
0.04
0.1
0.0
1160
0.02
1150
1140
Wavenumber / cm
1
1055
1130
1050
1045
Wavenumber / cm
1040
1
Figure S3.
Selected regions of the experimental IR spectra of TAA isolated in an N2 matrix, recorded at
13 K before and after of the annealing procedure up to 24 K. The blue line represents the
TAA spectrum of the deposited (Dep.) matrix shortly after deposition, before annealing; the
red line that obtained after annealing (Ann.) and cooling back to 13 K. Asterisks indicate the
bands associated with absorptions of the 5-methyl-tetrazole decomposition product.
5
TABLE S1.
Internal coordinates used in the normal mode analysis of 1ccc and 1cct conformers of 1H-TAA. a
H
11
O
H 10
O
7
9
8
6
H
12
H
13
N
5
1
N
4
Definition
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21
S22
S23
S24
S25
S26
S27
S28
S29
S30
S31
S32
S33
N2
N
3
Symbol
r1,2
r3,4
r2,3
r4,5 + r5,1
r4,5  r5,1
r1,10
r5,6
r6,7
r6,12 + r6,13
r6,12  r6,13
r7,8
r7,9
r9,11
12,13,6 – 12,7,6 – 12,5,6 – 13,7,6 – 13,5,6 – 5,7,6
5,7,6 – 12,7,6 – 13,7,6 – 12,5,6 – 13,5,6
12,7,6 + 13,7,6 – 12,5,6 – 13,5,6
12,7,6 – 13,7,6 – 12,5,6 + 13,5,6
12,7,6 – 13,7,6 + 12,5,6 – 13,5,6
7,11,9
9,6,7 – 9,8,7 – 6,8,7
9,8,7 – 6,8,7
1,3,2 + a (5,2,1 + 4,2,3) + b (1,4,5 + 3,5,4)
(ab) (4,2,3 – 5,2,1) + a3,5,4 –1,4,5)
10,2,1 – 10,5,1
6,4,5 – 6,1,5
6,7,9,11
5,6,7,8 + 5,6,7,9
4,5,6,7 + 1,5,6,7
2,3,4,5 + a (1,2,3,4 + 3,4,5,1) + b (4,5,1,2 + 5,1,2,3)
(ab) (3,4,5,1  1,2,3,4) + (1a) (4,5,1,2 – 5,1,2,3)
6,1,5,4
10,2,1,5
8,6,7,9
 N1N2
 N3N4
 N2N3
s CN
as CN
 NH
 C5C6
 C6C7
s CH2
as CH2
 C=O
 C−O
 OH
CH2
CCC
wagCH2
twCH2
rockCH2
OH
CCO
C=O
ring 1
ring 2
NH
C5C6
 OH
 C6C7
 C5C6
 ring 1
 ring 2
C5C6
NH
C=O
Abbreviations:  stretching, δ in-plane bending, rock  rocking, wag  wagging, tw  twisting, outof-plane bending,  torsion; s, symmetric; as, antisymmetric. Constant values: a=cos 144°; b=cos 72°.
ri,j is the distance between atoms Ai and Aj; βi,j,k is the angle between vectors AkAi and AkAj;
τi,j,k,l is the dihedral angle between the plane defined by Ai, Aj, Ak and the plane defined by Aj, Ak, Al atoms;
γi,j,k,l is the angle between the vector AkAi and the plane defined by atoms Aj, Ak, Al.
a
6
TABLE S2.
Internal coordinates used in the normal mode analysis of 2pcc and 2pct conformers of 2H-TAA. a
H
11
O
7
9
O
8
6
H
12
N
5
4
N
H
1
13
N
3
N
2
Definition
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21
S22
S23
S24
S25
S26
S27
S28
S29
S30
S31
S32
S33
H
10
Symbol
r1,2 + r3,4
r1,2  r3,4
r2,3
r4,5
r5,1
r2,10
r5,6
r6,7
r6,12 + r6,13
r6,12  r6,13
r7,8
r7,9
r9,11
12,13,6 – 12,7,6 – 12,5,6 – 13,7,6 – 13,5,6 – 5,7,6
5,7,6 – 12,7,6 – 13,7,6 – 12,5,6 – 13,5,6
12,7,6 + 13,7,6 – 12,5,6 – 13,5,6
12,7,6 – 13,7,6 – 12,5,6 + 13,5,6
12,7,6 – 13,7,6 + 12,5,6 – 13,5,6
7,11,9
9,6,7 – 9,8,7 – 6,8,7
9,8,7 – 6,8,7
1,3,2 + a (5,2,1 + 4,2,3) + b (1,4,5 + 3,5,4)
(ab) (4,2,3 – 5,2,1) + a3,5,4 –1,4,5)
10,1,2 – 10,3,2
6,4,5 – 6,1,5
6,7,9,11
5,6,7,8 + 5,6,7,9
4,5,6,7 + 1,5,6,7
2,3,4,5 + a (1,2,3,4 + 3,4,5,1) + b (4,5,1,2 + 5,1,2,3)
(ab) (3,4,5,1  1,2,3,4) + (1a) (4,5,1,2 – 5,1,2,3)
6,1,5,4
10,1,2,3
8,6,7,9
s NN
as NN
 N2N3
 C−N
 C=N
 NH
 C5C6
 C6C7
s CH2
as CH2
 C=O
 C−O
 OH
CH2
CCC
wagCH2
twCH2
rockCH2
OH
CCO
C=O
ring 1
ring 2
NH
C5C6
 OH
 C6C7
 C5C6
 ring 1
 ring 2
C5C6
NH
C=O
Abbreviations:  stretching, δ in-plane bending, rock  rocking, wag  wagging, tw  twisting, outof-plane bending,  torsion; s, symmetric; as, antisymmetric. Constant values: a=cos 144°; b=cos 72°.
ri,j is the distance between atoms Ai and Aj; βi,j,k is the angle between vectors AkAi and AkAj;
τi,j,k,l is the dihedral angle between the plane defined by Ai, Aj, Ak and the plane defined by Aj, Ak, Al atoms;
γi,j,k,l is the angle between the vector AkAi and the plane defined by atoms Aj, Ak, Al.
a
7
TABLE S3.
B3LYP/6–311++G(d,p) calculated wavenumbers (ν̃ / cm−1), absolute intensities (Ath / km mol−1) and
potential energy distributions (PED, %) for conformer 1ccc of 1H-TAA.
Approximate description a
ν̃ b
Ath
PED c
 OH
 NH
as CH2
s CH2
 C=O
s CN,  C5C6, NH
as CN (+), CH2 (−), wagCH2
CH2 (+), as CN (+), wagCH2
wagCH2, as CN,  C−O, C=O,  C6C7
NH (+),  N2N3 (−)
OH, wagCH2
 N2N3 (+), NH (+)
twCH2
 C−O, OH
ring 2,  N3N4, s CN
ring 1,  N1N2
 N1N2, NH
 N3N4, ring 2, ring 1, as CN
rockCH2, C=O
 C6C7,  C−O
 C5C6, ring 2, CCC, CCO
NH,  ring 2,  ring 1
 ring 1
 OH (+), C=O, NH (+)
 ring 2,  OH (+), NH (−), C=O
C=O,  OH
C=O,  OH, rockCH2
CCO,  C5C6,  C6C7
C5C6, CCO, C=O, CCC
C5C6,  ring 2
CCC, C5C6
 C6C7,  C5C6
 C5C6,  C6C7
3549
3419
2926
2880
1761
1544
1428
1403
1370
1325
1261
1228
1199
1133
1077
1061
1027
984
942
878
762
742
708
648
626
623
495
369
324
246
170
66
29
98.1
155.2
0.7
3.3
280.7
68.0
3.7
47.4
46.3
19.1
0.9
29.5
2.9
342.1
0.5
20.0
65.5
4.5
9.4
3.2
3.9
60.5
17.3
17.5
94.2
74.1
18.0
2.5
5.1
0.2
8.5
5.6
9.5
S13 (100)
S6 (99)
S10 (78) + S9 (22)
S9 (78) + S10 (22)
S11(84)
S4 (47) + S7 (24) + S24 (16)
S5 (32) + S14 (39) + S16 (13)
S14 (56) + S5 (15) + S16 (12)
S16 (11) + S5 (23) + S12 (13) + S21 (11) + S8 (10)
S24 (21) + S3 (37)
S19 (38) + S16 (35)
S3 (44) + S24 (28)
S17 (88)
S12 (48) + S19 (26)
S23 (27) + S2 (27) + S4 (20)
S22 (66) + S1 (11)
S1 (68) + S24 (21)
S2 (53) + S23 (22) + S22 (12) + S5 (11)
S18 (64) + S33 (26)
S8 (55) + S12 (12)
S7 (18) + S23 (19) + S15 (17) + S20 (14)
S32 (48) + S30 (37) + S29 (14)
S29 (78)
S26 (31) + S33 (23) + S32 (23)
S30 (26) + S26 (23) + S32 (20) + S21 (10)
S21 (47) + S26 (13)
S33 (39) + S26 (33) + S18 (19)
S20 (36) + S7 (23) + S8 (14)
S25 (39) + S20 (25) + S21 (15) + S15 (10)
S31 (73) + S30 (12)
S15 (48) + S25 (34)
S27 (49) + S28 (48)
S28 (59) + S27 (46)
, bond stretching; , bending; tw, twisting; wag, wagging; , out-of-plane; rock, rocking; , torsion; s, symmetric;
as, antisymmetric. The combinations [(+), (+)] and [(+), (−)] denote in-phase and in-opposite-phase couplings between
coordinates of different types.
b Calculated wavenumbers were scaled by 0.978 (below 2500 cm−1) and by 0.946 (above 2500 cm−1).
c See Table S1 for definition of coordinates; PED values lower than 10% are not included.
a
8
TABLE S4.
B3LYP/6–311++G(d,p) calculated wavenumbers (ν̃ / cm−1), absolute intensities (Ath / km mol−1) and
potential energy distributions (PED, %) for conformer 1cct of 1H-TAA.
Approximate description a
ν̃ b
Ath
PED c
 OH
 NH
as CH2
s CH2
 C=O
s CN,  C5C6, NH
as CN (+), CH2 (−), wagCH2
CH2 (+), as CN (+)
wagCH2,  N2N3, NH,  C5C6
NH (+),  N2N3 (−),wagCH2
OH, wagCH2
 N2N3 (+), NH (+), twCH2
twCH2
 C−O, OH
ring 2,  N3N4, s CN
ring 1,  N1N2
 N1N2, NH
 N3N4, ring 2, ring 1, as CN
rockCH2, C=O
 C6C7,  C−O
 C5C6, ring 2, CCC, CCO
NH (+),  ring 2,  ring 1 (−)
 ring 1 (+), NH (+)
3600
3414
2912
2860
1792
1541
1433
1404
1349
1312
1246
1230
1202
1119
1077
1061
1028
983
939
872
770
742
708
648
641
551
444
366
326
254
168
70
39
70.5
156.5
1.7
5.7
234.4
57.9
1.2
35.8
51.1
93.4
309.6
101.8
2.7
35.3
0.7
19.0
50.3
6.8
6.4
12.0
0.9
56.4
10.4
10.6
30.9
8.1
103.3
3.6
1.4
1.5
21.9
17.9
10.6
S13 (100)
S6 (99)
S10 (79) + S9 (21)
S9 (79) + S10 (21)
S11(86)
S4 (47) + S7 (23) + S24 (17)
S5 (31) + S14 (43) + S16 (11)
S14 (55) + S5 (28)
S16 (20) + S3 (19) + S24 (11) + S7 (11)
S24 (14) + S3 (27) + S16 (18)
S19 (53) + S16 (19)
S3 (41) + S24 (24) + S17 (10)
S17 (77)
S12 (43) + S19 (28)
S23 (28) + S2 (25) + S4 (21)
S22 (67) + S1 (10)
S1 (68) + S24 (21)
S2 (54) + S23 (21) + S22 (12) + S5 (11)
S18 (64) + S33 (26)
S8 (54) + S12 (14)
S7 (18) + S23 (20) + S15 (16) + S20 (13)
S32 (47) + S30 (36) + S29 (17)
S29 (76) + S32 (12)
S21 (50)
S30 (32) + S32 (39) + S31 (10)
S33 (47) + S18 (19) + S26 (17)
S26 (84)
S20 (40) + S7 (22) + S8 (14)
S25 (40) + S20 (20) + S21 (15) + S15 (12)
S31 (67) + S30 (12)
S15 (47) + S25 (31)
S28 (68) + S27 (32)
S27(63) + S28 (38)
C=O
 ring 2, NH, C5C6
C=O, rockCH2,  OH
 OH
CCO,  C5C6,  C6C7
C5C6, CCO, C=O, CCC
C5C6,  ring 2
CCC, C5C6
 C5C6,  C6C7
 C6C7,  C5C6
, bond stretching; , bending; tw, twisting; wag, wagging; , out-of-plane; rock, rocking; , torsion; s, symmetric;
as, antisymmetric. The combinations [(+), (+)] and [(+), (−)] denote in-phase and in-opposite-phase couplings between
coordinates of different types.
b Calculated wavenumbers were scaled by 0.978 (below 2500 cm−1) and by 0.946 (above 2500 cm−1).
c See Table S1 for definition of coordinates; PED values lower than 10% are not included.
a
9
TABLE S5.
B3LYP/6–311++G(d,p) calculated wavenumbers (ν̃ / cm−1), absolute intensities (Ath / km mol−1) and
potential energy distributions (PED, %) for conformer 2pcc of 2H-TAA.
Approximate description a
ν̃ b
Ath
PED c
 OH
 NH
as CH2
s CH2
 C=O
 C=N,  C5C6, NH
NH (+),  C5C6, as NN,  C−N (−)
CH2
wagCH2 (+),  C6C7, OH (−)
 C−N (+), twCH2, NH (+)
OH (+), wagCH2 (+)
s NN
twCH2 (+), as NN (−)
as NN (+), ring 1, twCH2 (+),  C=N
 C−O, OH, wagCH2
 N2N3, ring 1
ring 2,  C=N
ring 1,  C−N, as NN
rockCH2, C=O
 C6C7
 C5C6, ring 2, CCC,  C−O,  ring 2
 ring 1
 ring 2,  C5C6
 OH,  ring 2
C=O
NH
C=O,  OH, rockCH2
CCO,  C5C6,  C6C7
C5C6, rockCH2
C5C6, CCO, C=O, CCC,  ring 2
CCC, C5C6
 C5C6,  C6C7
 C6C7,  C5C6
3556
3437
2942
2902
1787
1517
1457
1410
1353
1334
1266
1243
1177
1167
1117
1091
1045
1016
917
862
824
723
709
635
607
588
502
368
317
311
102
50
39
80.4
125.3
0.0
3.5
296.6
27.4
7.9
22.9
65.8
17.2
1.7
5.5
25.1
8.9
331.5
11.8
11.7
16.8
1.4
6.2
27.5
24.1
26.4
106.6
57.5
44.9
21.9
5.4
8.2
1.0
2.8
2.8
0.8
S13 (100)
S6 (99)
S10 (99)
S9 (99)
S11(86)
S5 (47) + S7 (21) + S24 (11)
S24 (39) + S7 (15) + S2 (12) + S4 (10)
S14 (89)
S16 (34) + S8 (10) + S19 (10)
S4 (26) + S17 (15) + S24 (15)
S19 (43) + S16 (31)
S1 (83)
S17 (50) + S2 (24)
S2 (34) + S22 (26) + S17 (15) + S5 (13)
S12 (52) + S19 (24) + S16 (10)
S3 (72) + S22 (22)
S23 (47) + S5 (18)
S22 (36) + S4 (27) + S2 (12)
S18 (54) + S33 (24)
S8 (54)
S7 (14) + S23 (16) + S15 (15) + S12 (10) + S30 (10)
S29 (76)
S30 (61) + S7 (10)
S26 (56) + S33 (32)
S21 (59)
S32 (85)
S33 (37) + S26 (44) + S18 (13)
S20 (42) + S7 (20) + S8 (12)
S25 (78) + S18 (15)
S31 (31) + S20 (24) + S21 (13) + S15 (13) + S30 (10)
S15 (46) + S31 (44)
S28 (87) + S27 (13)
S27 (85) + S28 (14)
, bond stretching; , bending; tw, twisting; wag, wagging; , out-of-plane; rock, rocking; , torsion; s, symmetric;
as, antisymmetric. The combinations [(+), (+)] and [(+), (−)] denote in-phase and in-opposite-phase couplings between
coordinates of different types.
b Calculated wavenumbers were scaled by 0.978 (below 2500 cm−1) and by 0.946 (above 2500 cm−1).
c See Table S2 for definition of coordinates; PED values lower than 10% are not included.
a
10
TABLE S6.
B3LYP/6–311++G(d,p) calculated wavenumbers (ν̃ / cm−1), absolute intensities (Ath / km mol−1) and
potential energy distributions (PED, %) for conformer 2pct of 2H-TAA.
Approximate description a
ν̃ b
Ath
PED c
 OH
 NH
as CH2
s CH2
 C=O
 C=N,  C5C6 (−), NH (+)
NH (−),  C5C6 (+), as NN,  C−N
CH2
3601
3436
2923
2881
1820
1517
1458
1413
1346
1318
1246
1244
1180
1169
1100
1091
1045
1016
920
854
821
726
713
624
591
559
422
366
319
313
102
53
41
53.3
128.9
0.4
9.1
250.6
24.1
5.3
15.9
33.5
76.1
222.7
182.7
20.8
9.6
50.9
12.7
13.1
16.5
0.5
7.6
25.0
13.7
24.5
20.6
46.8
1.2
114.6
3.2
5.2
6.8
7.2
7.2
1.6
S13 (100)
S6 (99)
S10 (100)
S9 (100)
S11(88)
S5 (48) + S7 (20) + S24 (12)
S24 (36) + S7 (15) + S2 (11) + S4 (10)
S14 (84)
S4 (17) + S24 (23) + S17 (18)
S16 (57) + S4 (11)
S1 (49) + S19 (30)
S19 (36) + S1 (38)
S17 (54) + S2 (2)
S2 (40) + S22 (27) + S5 (13)
S12 (50) + S19 (22)
S3 (71) + S22 (21)
S23 (47) + S5 (18)
S22 (37) + S4 (27) + S2 (18)
S18 (56) + S33 (26)
S8 (50) + S15 (12)
S7 (16) + S23 (17) + S12 (14) + S15 (12)
S29 (72)
S30 (63)
S21 (60)
S32 (85)
S33 (66) + S18 (18)
S26 (94)
S20 (42) + S7 (20) + S8 (12)
S25 (77) + S18 (16)
S31 (32) + S20 (22) + S21 (13) + S30 (10)
S15 (46) + S31 (44)
S28 (100)
S27 (97)
 C−N, NH, twCH2
wagCH2,  C−N
s NN (+), OH (−)
OH (+), s NN (+)
twCH2, as NN
as NN, ring 1,  C=N
 C−O, OH
 N2N3, ring 1
ring 2,  C=N
ring 1,  C−N, as NN
rockCH2, C=O
 C6C7, CCC
 C5C6, ring 2,  C−O,CCC
 ring 1
 ring 2
C=O
NH
C=O, rockCH2
 OH
CCO,  C5C6,  C6C7
C5C6, rockCH2
C5C6, CCO, C=O,  ring 2
CCC, C5C6
 C5C6
 C6C7
, bond stretching; , bending; tw, twisting; wag, wagging; , out-of-plane; rock, rocking; , torsion; s, symmetric;
as, antisymmetric. The combinations [(+), (+)] and [(+), (−)] denote in-phase and in-opposite-phase couplings between
coordinates of different types.
b Calculated wavenumbers were scaled by 0.978 (below 2500 cm−1) and by 0.946 (above 2500 cm−1).
c See Table S2 for definition of coordinates; PED values lower than 10% are not included.
a
11
TABLE S7.
Cartesian coordinates for the geometries of conformers of 1H- and 2H- tautomers of TAA
optimized at the B3LYP/6-311++G(d,p) level.
1ccc
N
N
N
N
C
C
C
O
O
H
H
H
H
1.02407700
2.36891300
2.76456400
1.71037400
0.63239100
-0.76401500
-1.85308300
-1.69594500
-3.06228500
0.44731800
-3.72739200
-0.91174800
-0.90959900
0.87083100
0.91611700
-0.30781700
-1.16684000
-0.41648600
-0.93885900
0.10148500
1.29968300
-0.47898400
1.70125500
0.22446300
-1.71484500
-1.43933500
1cct
0.07323400
-0.01779200
-0.09062900
-0.05636000
0.04342100
0.13303800
-0.00279200
-0.01179300
-0.09249600
0.11013200
-0.15257900
-0.62170300
1.09729000
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.04027500
-2.37906200
-2.74318800
-1.67226500
-0.61950400
0.78173600
1.86202400
1.66944000
3.10882900
-0.48181600
3.11852200
0.92207600
0.91305300
1ctc
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.02884200
-2.34066200
-2.68532400
-1.62930800
-0.60203800
0.76716400
1.93183100
2.91999200
1.75700400
-0.50318600
2.54527000
0.88829800
0.86085400
0.88698300
0.90089700
-0.33090700
-1.16407900
-0.39101500
-0.87995200
-0.09120600
-0.56803900
1.25277700
1.74009700
1.69201900
-0.87568000
-1.91156200
0.87018500
0.88635900
-0.34453700
-1.18059300
-0.40712700
-0.89904600
0.14652000
1.33264500
-0.33788900
1.71226400
-1.30322700
-1.26213400
-1.76693100
0.11425500
-0.04547600
-0.15601000
-0.08228900
0.08234300
0.24409700
-0.00780300
-0.01074100
-0.18472600
0.17286500
-0.19693000
1.27055000
-0.40791900
1ttt
0.16069700
-0.15734900
-0.30303200
-0.09721500
0.18815100
0.53512200
-0.03390400
-0.51609300
0.11262800
0.28478500
-0.24296100
1.62602900
0.20195100
N
N
N
N
C
C
C
O
O
H
H
H
H
12
-1.70304500
-2.73245900
-2.23017100
-0.89003300
-0.56862500
0.79896200
1.98761300
3.06405400
1.77972900
-1.86618400
0.83059200
0.93722100
0.93035500
-1.04681500
-0.16931600
0.99585600
0.90977400
-0.36633600
-0.92821400
-0.00746200
-0.49357800
1.30961800
-2.03645400
1.53120200
-1.18710600
-1.85038000
-0.11661500
-0.21042800
-0.02686300
0.19290500
0.13330800
0.32499200
-0.03861400
-0.25360600
-0.04507500
-0.23386000
0.09299700
1.38141300
-0.24221500
TABLE S7. (Continued)
2pct
2pcc
N
N
N
N
C
C
C
O
O
H
H
H
H
1.29650000
2.43839200
2.46872800
1.29727100
0.59144300
-0.81135000
-1.84173900
-1.61704800
-3.09174500
3.22731100
-3.71343700
-0.99015100
-0.98973300
0.34287900
0.47809000
-0.12142600
-0.67899400
-0.38650700
-0.82739400
0.17533200
1.25961300
-0.32023300
0.99309500
0.35026000
-1.77806700
-0.99275700
N
N
N
N
C
C
C
O
O
H
H
H
H
1.05400900
0.39472400
-0.78644000
-0.92562100
0.19797200
0.42807400
-0.06583200
-0.53097500
0.09739200
0.76049100
-0.22410500
-0.07920500
1.49350700
1.28819500
2.43246700
2.46181700
1.28679800
0.58112000
-0.82819100
-1.84676800
-1.57546500
-3.14200600
3.22300600
-3.20587400
-0.99812500
-1.00113600
-1.39659100
-2.46022800
-2.32495900
-1.12161400
-0.56407200
0.81809700
1.94179200
3.05352300
1.57017400
-3.31077800
2.34319700
0.99238300
0.93447300
-0.00816500
0.31990400
0.12308700
-0.35441700
-0.42677900
-0.92255100
0.02224200
-0.33898300
1.31960000
0.68365100
1.84973000
-1.86120100
-1.11745200
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.10181400
-0.38049600
0.92294100
1.08202900
-0.15605700
-0.41224600
-0.01102100
0.27225600
-0.05038700
-0.78742900
0.19701300
0.11480200
-1.48200500
-1.59854600
-2.56496400
-2.19561500
-0.92596400
-0.56860100
0.81334400
1.97348700
3.03078700
1.77517700
-3.51305500
0.84972700
0.95727800
0.94459000
-1.39659300
-2.46022700
-2.32495600
-1.12161200
-0.56407200
0.81809800
1.94179200
3.05351900
1.57017400
-3.31077700
2.34319100
0.99237800
0.93447800
-0.00802100
0.31995500
0.12296900
-0.35455900
-0.42676100
-0.92250400
0.02224600
-0.33901400
1.31960400
0.68375800
1.84971100
-1.86121400
-1.11727600
-1.16177600
-0.25538200
0.98448700
0.90482000
-0.40328300
-0.89596800
-0.01778300
-0.50629600
1.30884900
-0.49059400
1.54379100
-0.98551100
-1.89095000
-0.17105600
-0.27067700
-0.01284300
0.28333600
0.18306400
0.45353100
-0.05206800
-0.34147100
-0.09194000
-0.53290600
0.12218300
1.53723900
0.03228900
2pt't
2pt'c
N
N
N
N
C
C
C
O
O
H
H
H
H
1.03315600
0.37065800
-0.77360500
-0.88402000
0.21787000
0.46249800
-0.09004300
-0.56662900
0.01550600
0.70675600
0.40058300
-0.00159300
1.53796300
2ptt
2ptc
N
N
N
N
C
C
C
O
O
H
H
H
H
0.39433500
0.48269600
-0.18461100
-0.74109600
-0.37758400
-0.78786000
0.21636000
1.27721900
-0.18423500
1.01540100
-1.06683600
-1.76395400
-0.89324500
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.10181400
-0.38045300
0.92295900
1.08198300
-0.15611400
-0.41236000
-0.01101800
0.27222800
-0.05024100
-0.78733500
0.19722400
0.11458300
-1.48214200
13
-0.94429800
-2.23020100
-2.64853600
-1.60637500
-0.56972500
0.81459500
1.98451600
3.04622500
1.79209700
-2.84055600
0.87020800
0.96067200
0.93265700
0.88388300
0.81411600
-0.40571800
-1.18263500
-0.38670700
-0.87900600
-0.01028700
-0.49908100
1.32070700
1.61997500
1.55878600
-0.99525800
-1.86804200
0.29332000
-0.02967700
-0.31576500
-0.18880800
0.18333200
0.44488700
-0.04746000
-0.31471100
-0.10661500
-0.05574200
0.09736600
1.52569700
0.00524400
TABLE S8.
Cartesian coordinates for the geometries of conformers of 1H- and 2H- tautomers of TAA
optimized at the MP2/6-311++G(d,p) level.
1ccc
N
N
N
N
C
C
C
O
O
H
H
H
H
1.03913700
2.35626900
2.72720100
1.66765300
0.61369400
-0.77198400
-1.83839700
-1.68842700
-3.00554000
0.48279100
-3.65104500
-0.92370500
-0.90800600
0.86847000
0.91381600
-0.33856800
-1.17770300
-0.41094500
-0.89860000
0.10372800
1.30821200
-0.50612400
1.70907900
0.19526700
-1.83869600
-1.10954600
1cct
0.18317200
-0.06641800
-0.24857600
-0.13415300
0.12677100
0.38050200
0.00004200
-0.01861600
-0.27111200
0.28765900
-0.44816500
-0.15297200
1.44923800
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.05140700
-2.36476500
-2.70769300
-1.63387400
-0.60128100
0.78876200
1.84765400
1.66284000
3.05564800
-0.51124400
3.01296500
0.92668300
0.91704200
1ctc
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.02495800
-2.31224200
-2.65045100
-1.60000100
-0.58302800
0.77615400
1.90534500
2.83364500
1.75906700
-0.50611500
2.52037600
0.90023700
0.86654000
0.89224800
0.90849700
-0.35572400
-1.17354300
-0.38275300
-0.83996700
-0.09809500
-0.59852100
1.25089300
1.75059400
1.66305000
-0.70760500
-1.90046700
0.87093200
0.88643300
-0.37455400
-1.19121600
-0.39967300
-0.85954600
0.14569900
1.33916900
-0.36591100
1.72281900
-1.32899200
-1.00559600
-1.83434400
0.18422600
-0.08888600
-0.26551800
-0.12450300
0.14737400
0.42692900
-0.00926300
-0.01815000
-0.32551700
0.28667300
-0.31889500
1.50653900
-0.05245500
1ttt
0.18254300
-0.19595900
-0.35544800
-0.09587600
0.23317600
0.64760100
-0.03594800
-0.61781800
0.12244500
0.31869800
-0.31371400
1.72942700
0.41278000
N
N
N
N
C
C
C
O
O
H
H
H
H
14
-1.60984500
-2.66212700
-2.24196700
-0.94532800
-0.55150600
0.81489600
1.94928900
2.97316200
1.76158100
-1.69786100
0.84174200
0.96438500
0.95259900
-1.05722500
-0.24114200
0.96447100
0.92288600
-0.34372000
-0.83667500
-0.01112200
-0.53922900
1.31399300
-2.04822800
1.53785500
-0.78908900
-1.87247100
-0.18374900
-0.37302500
-0.06010500
0.33463500
0.25145100
0.57620500
-0.05951700
-0.41641800
-0.12208500
-0.37115300
0.12302400
1.66149300
0.26152900
TABLE S8. (Continued)
2pct
2pcc
N
N
N
N
C
C
C
O
O
H
H
H
H
1.25722600
2.39025600
2.45951100
1.28601300
0.57618500
-0.82515900
-1.81114100
-1.52855000
-3.08061600
3.16504700
-3.65800300
-1.01211000
-1.01195100
0.41816900
0.53043800
-0.16251600
-0.77454400
-0.41448500
-0.83857300
0.17206800
1.22307000
-0.26742600
1.09642200
0.41692100
-1.80633300
-0.94704900
N
N
N
N
C
C
C
O
O
H
H
H
H
1.03688000
0.36613900
-0.77384200
-0.86706700
0.22630800
0.47632800
-0.07989700
-0.60287500
0.09747400
0.69208300
-0.27191200
0.00292800
1.54891500
1.25236200
2.38717300
2.45125600
1.27232400
0.56560600
-0.84194800
-1.81512500
-1.48761900
-3.12666200
3.16531800
-3.19908500
-1.02129800
-1.02369700
1.04534400
2.24455100
2.52386000
1.42804800
0.54959500
-0.82706000
-1.91247700
-2.98922800
-1.54062100
2.91836100
-2.29409900
-0.92526500
-1.01317000
-0.58724700
-0.71152300
0.13866400
0.87618600
0.42775100
0.96773900
-0.00872100
-0.10836200
-0.73416500
-1.39940200
-1.30423200
1.85846500
1.25221900
N
N
N
N
C
C
C
O
O
H
H
H
H
-0.95099800
-0.41045000
0.58136200
0.71072900
-0.21513000
-0.39211900
0.01869100
-0.52088400
1.09874800
-0.72668100
1.31309800
0.23683300
-1.42932200
-1.53146900
-2.50967700
-2.21870400
-0.95581500
-0.55143500
0.82456500
1.94676400
2.96191200
1.76670700
-3.42806300
0.86249200
0.97061400
0.95629200
1.39296000
2.42705300
2.28448700
1.06959700
0.54658300
-0.82936000
-1.90911700
-2.99157200
-1.52406300
3.27900500
-2.26926800
-1.01802800
-0.93394800
0.60184600
0.47593900
-0.41778000
-0.92005000
-0.29662600
-0.54903700
0.02910900
-0.47401900
1.21080900
1.01336300
1.51803900
-1.61973800
-0.08634700
-1.17637300
-0.29994400
0.96342600
0.91420100
-0.37350100
-0.82079100
-0.02134200
-0.54973900
1.31060600
-0.56184200
1.54379000
-0.71367500
-1.87058000
-0.1999060
-0.3545860
-0.04137100
0.36188000
0.25759800
0.61331100
-0.06281400
-0.44239400
-0.14441200
-0.6959210
0.13354100
1.69505000
0.35108500
2pt't
2pt'c
N
N
N
N
C
C
C
O
O
H
H
H
H
1.02936200
0.35780700
-0.76683100
-0.84873200
0.23483400
0.48588800
-0.09993900
-0.60236500
0.00299900
0.67017500
0.40716000
0.02820500
1.56344800
2ptt
2ptc
N
N
N
N
C
C
C
O
O
H
H
H
H
0.43202700
0.51856600
-0.19926600
-0.80235700
-0.41031200
-0.81057500
0.21489100
1.25566200
-0.13187600
1.08785900
-1.00392800
-1.78943000
-0.89161100
N
N
N
N
C
C
C
O
O
H
H
H
H
0.92244100
0.10847500
-0.87448300
-0.69883300
0.38243200
0.89221400
-0.00360900
-0.18952300
-0.53997100
0.21887200
-1.07752200
0.98619800
1.87897700
15
-1.00507300
-2.23238200
-2.56861900
-1.48664700
-0.55104300
0.83117400
1.94582300
2.95675700
1.76325400
-2.88362100
0.87262900
0.97901600
0.96520500
0.89438700
0.77009400
-0.46074200
-1.19765600
-0.37037900
-0.77654300
-0.00923600
-0.54418200
1.32389200
1.54553500
1.56526500
-0.61713200
-1.83699200
0.40949500
-0.06255300
-0.45489200
-0.24030600
0.27891900
0.66053400
-0.05981100
-0.43681700
-0.19001100
-0.11691900
0.10867800
1.73546000
0.44735500
TABLE S9.
Cartesian coordinates for the geometries of conformers of 1H- and 2H- tautomers of TAA
optimized at the QCISD/6-311++G(d,p).
1ccc
N
N
N
N
C
C
C
O
O
H
H
H
H
1.04248500
2.37500700
2.73612700
1.66375600
0.62057300
-0.77037300
-1.84428300
-1.69643500
-3.02245100
0.49374300
-3.67857000
-0.91872200
-0.90248600
0.87113300
0.89932000
-0.33022700
-1.17805200
-0.40757000
-0.90165700
0.10252700
1.31284500
-0.50397900
1.71228200
0.19100400
-1.82523900
-1.14399100
1cct
0.17740500
-0.05972400
-0.23334500
-0.13070500
0.11671600
0.35577600
-0.00137000
-0.02307000
-0.24787900
0.26957000
-0.41774100
-0.20166300
1.41527000
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.05540100
-2.38374500
-2.71735900
-1.62980900
-0.60814900
0.78722000
1.85320400
1.66882700
3.07330000
-0.52257200
3.06240700
0.91922300
0.91447900
1ctc
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.02017000
-2.32609400
-2.66656500
-1.60743000
-0.59213400
0.77192000
1.91016000
2.85146900
1.77495900
-0.50115300
2.53959700
0.88933600
0.86292300
0.89381300
0.90117700
-0.33783000
-1.17190200
-0.38447200
-0.85430000
-0.09734000
-0.59460000
1.25165500
1.74865500
1.67467200
-0.75503500
-1.90486100
0.87302400
0.87132700
-0.36652200
-1.19137300
-0.39673300
-0.86318900
0.14462700
1.34370000
-0.36199300
1.72507900
-1.32807000
-1.04267100
-1.82141200
0.17937300
-0.08105900
-0.25084600
-0.12280500
0.13610100
0.40213100
-0.00945800
-0.02196400
-0.30183400
0.26915900
-0.29494000
1.47455700
-0.10367000
1ttt
0.16384700
-0.19556400
-0.33494500
-0.08399800
0.21859100
0.62008500
-0.03369400
-0.60989900
0.14245100
0.28411300
-0.27990100
1.70369100
0.35640900
N
N
N
N
C
C
C
O
O
H
H
H
H
16
-1.63508700
-2.69246800
-2.25931600
-0.93464900
-0.56148600
0.80741700
1.96191800
2.99842200
1.79912800
-1.73754100
0.88179000
0.94161500
0.93728600
-1.05821900
-0.21943700
0.96420700
0.92577100
-0.33828700
-0.85438500
-0.01499500
-0.54666600
1.31871300
-2.04620700
1.57715000
-0.87891900
-1.86866100
-0.16343800
-0.32784700
-0.05808800
0.29062600
0.21448900
0.52056200
-0.05192800
-0.38580100
-0.09287200
-0.33301300
0.12147400
1.60621600
0.14719600
TABLE S9. (Continued)
2pct
2pcc
N
N
N
N
C
C
C
O
O
H
H
H
H
1.29325200
2.42958700
2.44817500
1.27248900
0.58378600
-0.81981700
-1.82553400
-1.56791100
-3.09029700
3.21917700
-3.69003700
-1.00075600
-0.99784200
0.16666500
0.41362600
0.00805200
-0.53480100
-0.42694500
-0.89643700
0.18114800
1.32450900
-0.30555300
0.87008400
0.42031500
-1.76486700
-1.19856400
N
N
N
N
C
C
C
O
O
H
H
H
H
1.10622100
0.45480200
-0.80723300
-1.02072400
0.15057100
0.32045900
-0.03901100
-0.35319700
0.04573200
0.88374200
-0.18691200
-0.31479700
1.35412100
1.28090200
2.42260200
2.44549800
1.26688400
0.57332500
-0.83676600
-1.83010800
-1.52647500
-3.13878600
3.21195200
-3.21994300
-1.00859800
-1.01123800
-1.13314000
-2.31559700
-2.48425100
-1.36507000
-0.55508100
0.83136300
1.92886500
3.06740400
1.51398000
-3.03476400
2.28230500
0.94728900
1.00962500
-0.44192800
0.09822000
0.40968700
0.07065600
-0.44259800
-0.93347500
0.02688900
-0.31430200
1.31626400
0.25129500
1.85474000
-1.10667500
-1.87640700
N
N
N
N
C
C
C
O
O
H
H
H
H
-1.03714700
-0.74342000
0.53390800
1.13065000
0.16168100
0.41719500
-0.00563600
-0.25732600
-0.03114900
-1.43292800
-0.27791000
1.48927000
-0.09802300
-1.53133000
-2.52574000
-2.22331400
-0.96870400
-0.55982300
0.82088300
1.95099100
2.97192900
1.79119700
-3.44205000
0.89779900
0.95729700
0.95325500
1.41177800
2.45692700
2.28462700
1.07230800
0.55598500
-0.82402100
-1.91906100
-3.02351600
-1.54369500
3.31570700
-2.30096400
-1.00119300
-0.93275400
0.05177900
0.33843200
0.06796500
-0.42358600
-0.42447300
-0.89629200
0.02419400
-0.34935000
1.32679500
0.72694700
1.84298100
-1.88026000
-0.97192800
-1.17214500
-0.29325900
0.95526800
0.91914000
-0.37742600
-0.82326500
-0.02386500
-0.55889300
1.31557300
-0.55507200
1.58719300
-0.73411700
-1.86713900
-0.19771700
-0.34563800
-0.03646400
0.34997500
0.24252500
0.60164500
-0.05791200
-0.43068200
-0.14148400
-0.67621100
0.13258900
1.68399200
0.32832100
2pt't
2pt'c
N
N
N
N
C
C
C
O
O
H
H
H
H
1.07872400
0.41042700
-0.79479400
-0.95068900
0.19434800
0.40425000
-0.07242100
-0.47218700
-0.00163700
0.78621700
0.31788100
-0.14265000
1.46641400
2ptt
2ptc
N
N
N
N
C
C
C
O
O
H
H
H
H
0.28729900
0.44696100
-0.10492300
-0.66079900
-0.40877000
-0.83907500
0.22047700
1.31822700
-0.15586700
0.94868900
-1.06400300
-1.76961900
-1.02949000
N
N
N
N
C
C
C
O
O
H
H
H
H
1.10296600
0.32561600
-0.96096100
-1.05922400
0.20317700
0.52137100
0.01336000
-0.32664800
0.02972700
0.68237700
-0.28818400
0.08958900
1.60536800
17
-0.99332000
-2.24804800
-2.59190600
-1.52553300
-0.55963900
0.82385100
1.95769200
2.98054400
1.80021000
-2.88966500
0.91132800
0.96706000
0.94548000
0.89445700
0.77811200
-0.44856800
-1.19227800
-0.35949600
-0.79826400
-0.01411000
-0.55182500
1.32741400
1.55471900
1.60253200
-0.70844100
-1.84436800
0.37521800
-0.06033500
-0.41671500
-0.22638000
0.25418400
0.61406300
-0.05456600
-0.41458600
-0.16362200
-0.10950400
0.11155800
1.69529400
0.34371400