Tautomerism in Drugs with Benzimidazole Carbamate Moiety: an Electronic Structure Analysis

Supplementary Information

Tautomerism in drugs with Benzimidazole Carbamate Moiety: An Electronic Structure Analysis

Yoganjaneyulu Kasetti and Prasad V. Bharatam*

Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research (NIPER),

Sector-67, S. A. S. Nagar - 160 062, Punjab, India.

Table of Contents

Table S1. Absolute Energies (a.u, ZPE corrected values, which have been scaled by a factor of 0.9153,

0.9806, and 0.9661 for HF, B3LYP, and MP2 levels respectively) of various conformers of model

carbendazim (CM)...... S3

Table S2. Absolute Energies (a.u, ZPE corrected values, which have been scaled by a factor of 0.9806 for B3LYP

levels respectively) of various conformers of model carbendazim (CM) in different solvation models.

Solvent level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method..S3

Table S3. Absolute Energies (a.u, ZPE and Gibbs free energy corrected values, which have been scaled by a factor of 0.9806 for B3LYPlevels respectively) of CM-1 and CM-2 conformers of benzimidazole carbamte based drugs in gas phase and solvation phase. Solvent level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method.a,b….. ……………………………………………………..S4

Table S4. Absolute Energies (a.u, ZPE and Gibbs free energy corrected values, which have been scaled by a factor of 0.9806 for B3LYPlevels respectively) of CM-1 and CM-2 conformers of carbamte guanidine (CG), carbamate imidazole (CI), carbendazime(CM) and Aminoimidazole (AI) in gas phase and solvation phase. Solvent level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method.a,b…………………………………………………………………………………………………..S4

Table S5.Absolute Energies (a.u, ZPE corrected values, which have been scaled by a factor of 0.9806 for B3LYP

levels respectively) of dimeric CMs (D1 – D12) and their stabilization energies obtained using

B3LYP/6-31+G (d) method, all relative energies are corrected for zero-point vibrational energy.Solvent

level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method....... S5

Table S6. Second order perturbation analysis on NBO basis....... S6

Table S7. Cartesian coordinates of conformers of model CM moiety used in this article are obtained using

B3LYP/6-31+G (d) method in gas phase....... S7

Table S8. Cartesian coordinates of conformers of model CM moiety used in this article are obtained using

B3LYP/6-31+G (d) method in aqueous phase. Solvent level calculations (using RMIN=0.5,

OFAC=0.8) have been performed using IEFPCM method....... S16

Table S9. Cartesian coordinates of dimeric CMs (D1 – D12) used in this article areobtained usingB3LYP/6-

31+G (d) method in gas phase....... S24

Table S10. NICSvalue calculated at 1Å (from the plane of molecule) using GIAO/B3LYP/6-31+G(d) method...S42

Figure S1. Optimized 3D geometries of NSC135301CN-1 to CN-3. The H-bond lengths obtained using

B3LYP/6-31+G(d) method in gas phase………………………………………………………………S43

Table S11.Relative energies (in kcal/mol) of various tautomers of model N-substituted benzimidazole carbamate moiety NSC135301 (CN)…………………………………………………………..…………….……S44

Table S12.Relative energies (in kcal/mol) of various tautomers of model benzimidazole carbamate moiety (CM).a,b,c………………………………………………………………………………………………..S44

Table S1.Absolute Energies (a.u, ZPE and Gibbs free energy corrected values, which have been scaled by a factor of 0.9153,0.9806, and 0.9661 for HF, B3LYP, and MP2levels respectively) of various conformers ofmodel carbendazim (CM).a,b

Conformer / HF / B3LYP / MP2
CM-1 / -658.87303889 / -662.83054080 / -660.93442665
CM-2 / -658.87831679 / -662.83448077 / -660.94312968
CM-3 / -658.87222798 / -662.82893640 / -660.93808222
CM-4 / -658.86857676 / -662.82692567 / -660.93104885
CM-5 / -658.86300622 / -662.82251325 / -660.92673875
CM-6 / -658.86318573 / -662.82213944 / -660.92981503
CM-7 / -658.85088621 / -662.81508041 / -660.92133171
CM-8 / -658.85434803 / -662.81668316 / -660.92404877
CM-9 / -658.83643738 / -662.79842156 / -660.90692581

a basis set used for all optimizations is 6-31+G(d).

ball relative energies are corrected for zero-point vibrational energy and Gibbs free energy.

Table S2. Absolute Energies (a.u, ZPEand Gibbs free energy corrected values, which have been scaled by a factor of 0.9806 for B3LYPlevels respectively) of various conformers of model carbendazim (CM) in different solvation models.Solvent level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method.a,b

Conformer / Gas Phase / Water / Methanol
CM-1 / -662.83054080 / -662.86344244 / -662.85894186
CM-2 / -662.83448077 / -662.86335668 / -662.85880783
CM-3 / -662.82893640 / -662.85629680 / -662.85520044
CM-4 / -662.82692567 / -662.85804843 / -662.85678736
CM-5 / -662.82251325 / -662.86014077 / -662.85490601
CM-6 / -662.82213944 / -- / -662.84781324
CM-7 / -662.81508041 / -662.83879205 / -662.83793813
CM-8 / -662.81668316 / -662.83953051 / -662.83840324
CM-9 / -662.79842156 / -662.82521026 / -662.82422429

a basis set used for all optimizations is 6-31+G(d).

ball relative energies are corrected for zero-point vibrational energy and Gibbs free energy.

Table S3. Absolute Energies (a.u, ZPE and Gibbs free energy corrected values, which have been scaled by a factor of 0.9806 for B3LYPlevels respectively) of CM-1 and CM-2 conformers of benzimidazole carbamte based drugs in gas phase and solvation phase. Solvent level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method.a,b

Drugs / Gas / Water
CM-1 / CM-2 / CM-1 / CM-2
Albendazole / -1178.8036168 / -1178.8068210 / -1178.8353391 / -1178.8341041
Mebendazole / -1007.0579819 / -1007.0628706 / -1007.0986904 / -1007.0994060
Fenbendazole / -1291.9261978 / -1291.9300582 / -1291.9625588 / -1291.9619205
Ciclobendazole / -892.7381794 / -892.7430571 / -892.7756607 / -892.7754007
Flubendazole / -1106.3174778 / -1106.3227687 / -1106.3589198 / -1106.3595673
Oxibendazole / -855.8223479 / -855.8253355 / -855.8540317 / -1695.0757990
Ricobendazole / -1253.9785282 / -1253.9801740 / -1254.0193375 / -1254.0160062
Oxifenbendazole / -1367.0958627 / -1367.1018610 / -1367.1393993 / -1367.1430786

a basis set used for all optimizations is 6-31+G(d).

ball relative energies are corrected for zero-point vibrational energy and Gibbs free energy.

Table S4. Absolute Energies (a.u, ZPE and Gibbs free energy corrected values, which have been scaled by a factor of 0.9806 for B3LYPlevels respectively) of CM-1 and CM-2 conformers of carbamte guanidine (CG), carbamate imidazole (CI), carbendazime(CM) and Aminoimidazole (AI) in gas phase and solvation phase. Solvent level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method.a,b

Molecule / Gas / Water
CM-1 / CM-2 / CM-1 / CM-2
Carbamate guanidine / -433.08047176 / -433.07061416 / -433.11674127 / -433.10308568
Carbamate imidazole / -509.25795482 / -509.26569678 / -509.28824174 / -509.28890475
Carbendazime / -662.83054080 / -662.83448077 / -662.86344244 / -662.86335668
Amino imidazole / -281.42807928 / -281.44225836 / -281.46077677 / -281.47188019

a basis set used for all optimizations is 6-31+G(d).

ball relative energies are corrected for zero-point vibrational energy and Gibbs free energy.

Table S5. Absolute Energies (a.u, ZPE corrected values, which have been scaled by a factor of 0.9806 for B3LYP

levels respectively) of dimeric SLUs (D1 – D12) and their stabilization energies obtained using

B3LYP/6-31+G (d) method, all relative energies are corrected for zero-point vibrational energySolvent

level calculations (using RMIN=0.5,OFAC=0.8) have been performed using IEFPCM method.

Dimer / Molecular unit / Gas phase / Water / Methanol
D1 / CM-1 / -1325.67226276 / -1325.69846911 / -1325.69692488
D2 / CM-2 / -1325.67249302 / -1325.69718641 / -1325.69591286
D3 / CM-5 / -1325.66131763 / -1325.69137243 / -1325.68941720
D4 / CM-3 / -1325.66101058 / -1325.69020470 / -1325.68846612
D5 / CM-2 / -1325.66010434 / -1325.68847526 / -1325.68659718
D6 / CM-4 / -1325.65472429 / -- / -1325.68407664
D7 / CM-3 / -1325.65314956 / -- / -1325.62892861
D8 / CM-6 / -1325.63752433 / -1325.67400032 / -1325.67213002
D9 / CM-7 / -1325.63439511 / -1325.65496022 / -1325.65388097

a basis set used for all optimizations is 6-31+G(d).

ball relative energies are corrected for zero-point vibrational energy and Gibbs free energy.

Table S6. Second order perturbation analysis on NBO basis.

Structure / Donor NBO (i) / Acceptor NBO (j) / E(2) / E(i)-E(j) / F(i, j)
kcal/mol / a. u. / a. u.
nN5 / π * (O1-C2) / 66.50 / 0.26 / 0.119
CM-1 / nN5 / π * (N7-C6) / 43.07 / 0.29 / 0.102
nN7 / σ* (C6-N10) / 10.71 / 0.81 / 0.084
nN10 / π* (N7-C6) / 55.51 / 0.27 / 0.110
nN10 / π* (C9-C16) / 37.02 / 0.30 / 0.095
n2O1 / σ* (C2-O3) / 31.44 / 0.63 / 0.127
n2O1 / π* (N5-C2) / 23.12 / 0.71 / 0.117
n2O3 / π* (O1-C2) / 10.40 / 1.15 / 0.098
n2O3 / π* (O1-C2) / 47.80 / 0.32 / 0.116
CM-2 / nN5 / π * (O1-C2) / 14.08 / 0.90 / 0.103
nN5 / σ * (N10-C6) / 18.84 / 0.77 / 0.109
nN7 / π * (N5-C6) / 55.00 / 0.27 / 0.113
nN7 / π * (C8-C13) / 37.91 / 0.29 / 0.096
nN10 / π* (N5-C6) / 62.87 / 0.26 / 0.118
nN10 / π* (C9-C16) / 39.47 / 0.29 / 0.096
n2O1 / σ* (C2-O3) / 30.06 / 0.64 / 0.125
n2O1 / σ* (N5-C2) / 18.67 / 0.74 / 0.107
n2O3 / π* (O1-C2) / 9.37 / 1.11 / 0.091
n2O3 / π* (O1-C2) / 48.43 / 0.31 / 0.114

Table S7.Cartesian coordinates of conformers of model SU moiety used in this article areobtained using

B3LYP/6-31+G(d,p) methodin gas phase.

CM-1

O -2.43242000 1.22035700 -0.00001400

O -3.83539900 -0.55498500 0.00019000

N -1.64320500 -0.98635900 0.00014500

N 0.15867300 0.66190100 -0.00006000

N 0.66349300 -1.47470000 0.00009900

C 3.87035300 1.13031400 -0.00023800

C 2.53820800 1.56235600 -0.00022400

H 2.28754100 2.61899000 -0.00030200

C 1.54829300 0.58471700 -0.00010500

C 1.87469500 -0.78765800 -0.00000400

C 3.19719000 -1.21887800 -0.00001800

H 3.44957100 -2.27540900 0.00006000

C 4.19378100 -0.23470800 -0.00013800

C -0.39250300 -0.59433800 0.00006500

C -2.59888500 -0.00855200 0.00009700

C -4.92832400 0.37268400 0.00015100

H -4.89912500 1.00663500 0.89130200

H -5.82758800 -0.24529700 0.00024700

H -4.89920200 1.00646900 -0.89112000

H 4.66687200 1.86878400 -0.00033000

H -0.46220200 1.46756200 -0.00010600

H 0.52026200 -2.47443500 0.00018900

H 5.23684900 -0.53779400 -0.00015200

CM-2

O 2.47206600 1.27197400 0.00021700

O 3.82175900 -0.56600100 -0.00013400

N 1.61436000 -0.86484800 -0.00015800

N -0.22695900 0.70684900 0.00013800

N -0.66498900 -1.50704500 -0.00027100

C -3.94494700 1.05602700 0.00021800

C -2.63607300 1.54349400 0.00030200

H -2.43083500 2.61071400 0.00049800

C -1.61325000 0.59553800 0.00012300

C -1.86394200 -0.79952300 -0.00013400

C -3.18272800 -1.26879000 -0.00021500

H -3.38610900 -2.33583500 -0.00041200

C -4.21263600 -0.32790000 -0.00003600

C 0.25523800 -0.57440400 -0.00010000

C 2.62709200 0.05873300 -0.00000500

C 4.97583100 0.29727000 0.00000800

H 4.97880900 0.92690900 -0.89326900

H 5.83222300 -0.37706700 -0.00013400

H 4.97884000 0.92657200 0.89352200

H -4.77316000 1.75973900 0.00035100

H 0.36192600 1.53109700 0.00029900

H 1.84872100 -1.85044400 -0.00034200

H -5.24541300 -0.66683900 -0.00009400

CM-3

O 3.91406000 -1.03820000 -0.00002600

O 2.64652200 0.85381900 0.00011300

N 1.63742800 -1.18089800 -0.00032800

N -0.06478700 0.56972200 -0.00038900

N -0.68241000 -1.59715200 0.00009500

C -3.74234900 1.22294700 -0.00001200

C -2.39766000 1.60182100 -0.00026200

H -2.10707300 2.64909100 -0.00048900

C -1.45650100 0.57328600 -0.00020600

C -1.81911900 -0.79589400 0.00009100

C -3.17163700 -1.15598700 0.00033500

H -3.46131700 -2.20269800 0.00056200

C -4.12143100 -0.13424400 0.00028200

C 0.31628200 -0.74735100 -0.00018800

C 2.82786300 -0.49233300 -0.00007200

C 3.86336200 1.63203100 0.00044500

H 4.45162400 1.41043700 0.89348300

H 3.53598100 2.67194800 0.00060500

H 4.45188800 1.41079200 -0.89250800

H -4.51018800 1.99181100 -0.00004600

H 0.57126300 1.35364900 -0.00057400

H 1.73688400 -2.18939200 -0.00032900

H -5.17818800 -0.38795300 0.00047000

CM-4

O -2.26701300 1.75271700 0.00000000

O -3.94521400 0.30782300 0.00000000

N -1.80878400 -0.54160700 0.00000000

N 0.19763600 0.84190600 0.00000000

N 0.41516300 -1.34181900 0.00000000

C 3.93765300 0.81662400 0.00000000

C 2.67488900 1.42109700 0.00000000

H 2.56546600 2.50142900 0.00000000

C 1.56465100 0.58217500 0.00000000

C 1.70759300 -0.82081800 0.00000000

C 2.96133000 -1.42369300 0.00000000

H 3.07231800 -2.50427400 0.00000000

C 4.07852100 -0.57949100 0.00000000

C -0.51221900 -0.32804600 0.00000000

C -2.61803100 0.56853300 0.00000000

C -4.40600500 -1.05017500 0.00000000

H -4.06151900 -1.58093700 -0.89206600

H -5.49549700 -0.97774600 0.00000000

H -4.06151900 -1.58093600 0.89206600

H 4.82479000 1.44332100 0.00000000

H -0.32069100 1.71953300 0.00000000

H 0.14339400 -2.31430200 0.00000000

H 5.07267900 -1.01698800 0.00000000

CM-5

O -3.92882600 -1.00478500 -0.00030400

O -2.61829500 0.84526100 0.00019200

N -1.65545100 -1.27365100 -0.00027200

N 0.01127200 0.53890300 0.00005200

N 0.66750500 -1.55309700 -0.00027300

C 3.68156800 1.27086800 0.00026800

C 2.32136000 1.60683000 0.00028400

H 1.99752600 2.64360000 0.00044300

C 1.40423600 0.56118200 0.00009100

C 1.82604900 -0.78408900 -0.00011700

C 3.17596600 -1.11984100 -0.00013300

H 3.50256400 -2.15577800 -0.00029200

C 4.10057700 -0.06738000 0.00006300

C -0.45764900 -0.75665700 -0.00016400

C -2.80601500 -0.53636100 -0.00014800

C -3.82676200 1.62480500 0.00033200

H -4.42166900 1.40766900 -0.89055100

H -3.50313400 2.66780100 0.00060300

H -4.42174700 1.40723100 0.89105600

H 4.42330300 2.06431900 0.00041700

H -0.63528600 1.31650300 0.00018000

H 0.59370900 -2.56047700 -0.00042300

H 5.16245000 -0.29589600 0.00005600

CM-6

O 2.31047300 1.76532000 -0.00000700

O 3.96570800 0.27746200 -0.00014800

N 1.76182500 -0.45606400 0.00004500

N -0.26613000 0.87968000 0.00004900

N -0.41891400 -1.37134500 -0.00000200

C -3.99780800 0.75308400 -0.00000500

C -2.76195500 1.40308000 0.00002500

H -2.69361100 2.48761700 0.00004800

C -1.62670800 0.59260400 0.00002400

C -1.69864400 -0.82288600 -0.00000700

C -2.94702600 -1.45639000 -0.00003500

H -3.01357900 -2.54060300 -0.00005700

C -4.08768500 -0.65388100 -0.00003400

C 0.37379900 -0.32769300 0.00003300

C 2.65221700 0.59575100 -0.00003200

C 4.42041900 -1.08174400 0.00007100

H 4.09154200 -1.61071900 0.90271500

H 5.50908100 -1.02025500 0.00007800

H 4.09157000 -1.61099500 -0.90242100

H -4.90875800 1.34574700 -0.00000500

H 0.21776100 1.77018000 0.00006700

H 2.06857700 -1.41972000 -0.00000900

H -5.06914600 -1.12095700 -0.00005500

CM-7

O 2.37882900 1.18512100 -0.00002700

O 3.81862900 -0.53949800 0.00002100

N 1.62648400 -1.04228900 -0.00001200

N -0.11019400 0.64785200 -0.00004300

N -0.70077000 -1.51156900 -0.00008400

C -3.80875700 1.19109900 0.00002900

C -2.46659600 1.57394700 -0.00000600

H -2.17571200 2.62042100 -0.00002600

C -1.49633800 0.56650800 -0.00001100

C -1.89010700 -0.79531400 0.00000400

C -3.22873800 -1.18466000 0.00002000

H -3.52100600 -2.23136400 0.00001600

C -4.18491400 -0.16593000 0.00004400

C 0.33334600 -0.61016500 -0.00004200

C 2.55299700 -0.12801200 -0.00000700

C 4.86298100 0.45123900 0.00005300

H 4.80192800 1.07713400 -0.89404400

H 5.78922300 -0.12355500 0.00010100

H 4.80185100 1.07715900 0.89412800

H -4.58132800 1.95530500 0.00004000

H -0.57377900 -2.51374300 0.00026000

H -5.23939400 -0.42795400 0.00006800

H 1.36667600 1.35138100 -0.00003000

CM-8

O 2.24932700 1.73953900 -0.00022100

O 3.90661600 0.31871800 -0.00014900

N 1.78897700 -0.56876300 -0.00000900

N -0.17473800 0.85248300 -0.00006900

N -0.44871000 -1.36995500 0.00013000

C -3.91198900 0.85732600 0.00005100

C -2.63909000 1.42887000 -0.00004000

H -2.50066600 2.50610100 -0.00013600

C -1.53443400 0.57061000 -0.00000200

C -1.72929800 -0.83330600 0.00012500

C -2.99820100 -1.41139100 0.00021600

H -3.13764600 -2.48918200 0.00031300

C -4.08996800 -0.53995500 0.00017700

C 0.44273700 -0.32586700 0.00001200

C 2.58557800 0.46379900 -0.00012200

H -4.78634300 1.50262400 0.00002500

H -0.18065200 -2.34371600 0.00020700

H -5.09621400 -0.94990900 0.00024500

H 1.23684600 1.78130600 -0.00019400

C 4.43118600 -1.01993200 -0.00004900

H 4.10249400 -1.55796500 -0.89283100

H 5.51425600 -0.89477400 -0.00008900

H 4.10254000 -1.55781300 0.89284100

CM-9

O 3.93587100 0.20031100 0.00041400

O 2.33773600 1.73825200 0.00056600

N 1.75770200 -0.53463000 0.00005700

N -0.26988700 0.85674400 -0.00008200

N -0.44363100 -1.38854500 -0.00009800

C -3.99783600 0.76589500 -0.00035200

C -2.75798700 1.40652100 -0.00025800

H -2.68429500 2.49107600 -0.00025000

C -1.62613600 0.58799600 -0.00017700

C -1.70837700 -0.82817700 -0.00018800

C -2.96465500 -1.45099500 -0.00028600

H -3.03740800 -2.53477500 -0.00029700

C -4.09886200 -0.64179900 -0.00036700

C 0.38864700 -0.36772900 -0.00003000

C 2.60917000 0.40565000 0.00032700

H -4.90473100 1.36496900 -0.00041700

H -5.08425500 -1.10049200 -0.00044400

H 0.18140400 1.75990400 0.00001200

H 3.17835800 2.22979900 0.00076300

C 4.38187600 -1.17275200 0.00019800

H 4.01364500 -1.68433400 0.89213800

H 4.01383000 -1.68399200 -0.89201500

H 5.47027300 -1.11331100 0.00032200

Table S8.Cartesian coordinates of conformers of model CM moiety used in this article are obtained using

B3LYP/6-31+G(d) method in aqueous phase. Solvent level calculations (using RMIN=0.5,

OFAC=0.8) have been performed using IEFPCM method.

CM-1

O 2.46449900 1.23730000 0.00023000

O 3.83746700 -0.57824800 -0.00172200

N 1.64711700 -0.96805400 -0.00166300

N -0.17768400 0.68155800 -0.00173900

N -0.65698400 -1.45079300 -0.00010300

C -3.87963600 1.11215900 0.00052300

C -2.55946900 1.56473200 -0.00054000

H -2.31555100 2.62824100 -0.00134000

C -1.56219700 0.58813700 -0.00073300

C -1.86963200 -0.78269600 0.00026600

C -3.18930000 -1.23865500 0.00137800

H -3.42439700 -2.30400900 0.00217700

C -4.18848600 -0.26448400 0.00148900

C 0.37532100 -0.56400400 -0.00121000

C 2.60035600 -0.00160600 -0.00104300

C 4.94465200 0.34731700 0.00338000

H 4.91888500 0.97698000 -0.88738900

H 5.83363100 -0.28136700 0.00309500

H 4.91531100 0.97116700 0.89813000

H -4.69137500 1.84021200 0.00062300

H 0.38103400 1.54295500 -0.00213900

H -0.51641700 -2.47550000 -0.00009800

H -5.23364500 -0.57545800 0.00234200

CM-2

O -2.50144500 1.28400800 -0.00497400

O -3.82272500 -0.57294800 0.00169300

N -1.61406600 -0.84276500 0.00038400

N 0.24260200 0.72194800 0.00172700

N 0.65944800 -1.49317400 -0.00062300

C 3.96249700 1.04165300 0.00070500

C 2.65527200 1.53824900 0.00153800

H 2.45159400 2.60839300 0.00262100

C 1.62639600 0.59550400 0.00102400

C 1.86748700 -0.79998700 -0.00021000

C 3.18375100 -1.28115500 -0.00105900

H 3.38591500 -2.35187300 -0.00219400

C 4.22146700 -0.34562700 -0.00063200

C -0.26202200 -0.54761900 0.00014200

C -2.63858100 0.06559800 -0.00133800

C -4.99803900 0.26714800 0.00153900

H -5.01419700 0.89451900 0.89625800

H -5.83908600 -0.42616600 0.00372300

H -5.01632400 0.89151400 -0.89522600

H 4.79743700 1.74127200 0.00110900

H -0.30012200 1.58744200 -0.00116900

H -1.85122100 -1.84529000 0.00182600

H 5.25410900 -0.69294000 -0.00137300

CM-3

O 3.91662900 -1.03562700 0.00026400

O 2.63614400 0.84414000 0.00015400

N 1.64190400 -1.19137200 -0.00042700

N -0.05777900 0.55656700 -0.00044400

N -0.68318000 -1.60595900 -0.00001600

C -3.72998000 1.23212000 0.00006300

C -2.38148400 1.60255600 -0.00024800

H -2.07747300 2.64870900 -0.00047900

C -1.44743300 0.56612500 -0.00024800

C -1.81924700 -0.80022600 0.00003800

C -3.17518300 -1.15400200 0.00036100

H -3.47808300 -2.20064500 0.00061700

C -4.11927100 -0.12414000 0.00037800

C 0.32600900 -0.75502300 -0.00029000

C 2.82115500 -0.48914500 -0.00000200

C 3.83420800 1.65679500 0.00035200

H 4.42387300 1.45284300 0.89684800

H 3.47524300 2.68586800 -0.00013800

H 4.42455900 1.45222300 -0.89555300

H -4.49450900 2.00801800 0.00007600

H 0.57276600 1.34701800 -0.00078000

H 1.75239400 -2.21532300 -0.00078400

H -5.18022000 -0.37182200 0.00064100

CM-4

O -2.30729100 1.76700900 0.00161600

O -3.95525300 0.29317600 -0.00090200

N -1.80925900 -0.52080900 0.00011100

N 0.21188200 0.85472500 -0.00058700

N 0.41265200 -1.32761300 0.00043600

C 3.94982100 0.80466800 -0.00035400

C 2.69378600 1.42270900 -0.00060400

H 2.59047900 2.50690200 -0.00102500

C 1.57863000 0.58753400 -0.00037400

C 1.70679100 -0.81555000 0.00014900

C 2.95596700 -1.43348600 0.00038100

H 3.05159300 -2.51834000 0.00081300

C 4.07813600 -0.59689300 0.00013200

C -0.49539300 -0.31171500 0.00008500

C -2.62172800 0.56054700 0.00037700

C -4.41382700 -1.07183900 -0.00052100

H -4.06490700 -1.59743500 -0.89326400

H -5.50340400 -1.00458000 -0.00137600

H -4.06626500 -1.59639500 0.89336600

H 4.84586600 1.42375300 -0.00054900

H -0.27112900 1.74784400 0.00013800

H 0.14617400 -2.32067200 0.00051600

H 5.07193000 -1.04253000 0.00033400

CM-5

O -3.93162100 -0.98319600 -0.20942900

O -2.59924400 0.81541000 0.18309100

N -1.66634300 -1.28233400 -0.06169600

N 0.01124800 0.53608900 -0.12575200

N 0.65617300 -1.53982900 0.08220500

C 3.66573100 1.26510900 -0.06125600

C 2.31357200 1.60779200 -0.12449800

H 1.98673600 2.64394800 -0.22465200

C 1.39853700 0.55503500 -0.08550400

C 1.81217500 -0.77964700 0.05971100

C 3.16296200 -1.12629400 0.11597000

H 3.48145700 -2.16474800 0.21798600

C 4.08182100 -0.07605300 0.06917800

C -0.44640300 -0.74623100 -0.02893600

C -2.79089800 -0.52396800 -0.05038000

C -3.79463300 1.62698800 0.17829800

H -4.30346000 1.54235900 -0.78271000

H -3.44249900 2.64441900 0.34223400

H -4.46401900 1.31699300 0.98207700

H 4.41655000 2.05522200 -0.09346900

H -0.59550300 1.35962000 -0.21174200

H 0.59496300 -2.56867300 0.16804500

H 5.14797300 -0.30072400 0.11413900

CM-7

O -2.37235200 1.18659600 -0.00047100

O -3.81779700 -0.53616400 -0.00039700

N -1.62932300 -1.04344100 -0.00059000

N 0.10832600 0.64412100 -0.00050000

N 0.70442300 -1.51581900 -0.00011700

C 3.80835700 1.19518100 0.00018700

C 2.46494200 1.57938300 -0.00021500

H 2.17547100 2.62969600 -0.00051400

C 1.49614800 0.56804300 -0.00022200

C 1.88869500 -0.79429000 0.00006500

C 3.22888900 -1.18497000 0.00057000

H 3.51656600 -2.23565600 0.00089000

C 4.18467900 -0.16458000 0.00061400

C -0.32706600 -0.62036100 -0.00046500

C -2.55323600 -0.12261300 -0.00046200

C -4.87446800 0.45224500 0.00143200

H -4.81289900 1.07316600 0.89848300

H -5.79619100 -0.12943900 0.00208000

H -4.81491900 1.07435900 -0.89493000

H 4.58294100 1.96122300 0.00018300

H 0.59822300 -2.53765100 -0.00050400

H 5.24208500 -0.42635200 0.00098300

H -1.35570100 1.34495000 -0.00030700

CM-8

O -2.23692400 1.73613300 -0.00107000

O -3.90471700 0.32810200 -0.00022600

N -1.78902900 -0.57492800 -0.00078700

N 0.17343400 0.84920200 0.00008800

N 0.45272000 -1.37459800 -0.00131200

C 3.91352300 0.86053000 0.00136100

C 2.63981600 1.43401100 0.00126900

H 2.50431600 2.51503900 0.00196600

C 1.53539000 0.57234500 0.00032200

C 1.72840200 -0.83232600 -0.00046600

C 2.99866800 -1.41211000 -0.00052000

H 3.13225000 -2.49323800 -0.00120600

C 4.09067200 -0.53960900 0.00045500

C -0.43740200 -0.33833200 -0.00070700

C -2.58174800 0.45606000 -0.00072200

H 4.79039200 1.50702100 0.00215400

H 0.19869900 -2.37011500 -0.00065800

H 5.09966600 -0.95012200 0.00053000

H -1.21933500 1.76686600 -0.00072100

C -4.45715800 -1.00639500 0.00167300

H -4.13837300 -1.54429300 0.89771900

H -5.53747000 -0.86067100 0.00113900

H -4.13788000 -1.54714700 -0.89247500

CM-9

O 3.92930000 0.20984000 -0.00002500

O 2.30689500 1.71808300 -0.00056700

N 1.75959000 -0.54673500 0.00017800

N -0.26876300 0.85107300 0.00067400

N -0.44231500 -1.39036600 -0.00056500

C -3.99770100 0.76900600 0.00003300

C -2.75390800 1.40584000 0.00052900

H -2.67037000 2.49208700 0.00103600

C -1.62544200 0.58183200 0.00022600

C -1.71255300 -0.83308700 -0.00039500

C -2.97076600 -1.45458800 -0.00086400

H -3.05419900 -2.54111600 -0.00114000

C -4.10396200 -0.63945600 -0.00070600

C 0.39540200 -0.36042300 0.00012200

C 2.61338600 0.40925000 0.00003500

H -4.90443400 1.37285700 0.00042300

H -5.09291100 -1.09661300 -0.00054700

H 0.17719600 1.75876900 0.00098000

H 3.12114300 2.25687300 -0.00063300

C 4.41542000 -1.15469200 0.00087900

H 4.06568600 -1.67100200 0.89701800

H 4.06576400 -1.67218200 -0.89454400

H 5.50373300 -1.06294700 0.00098800

Table S9. Cartesian coordinates of of dimeric CMs (D1 – D12) used in this article are obtained using B3LYP/6-

31+G (d) method in gas phase.

D1

O -3.67720500 -0.00781700 -2.05662600

O -3.69802200 -0.00624700 0.20943600

N -1.70399500 -0.00383800 -0.79633000

N -1.27802300 -0.00441000 -3.19702400

N 0.43255200 -0.00115200 -1.81362700

C -0.92597700 -0.00323200 -1.87564200

C -0.13374500 -0.00310500 -3.99042900

C 0.05009300 -0.00348300 -5.37058200

C 1.36861300 -0.00177600 -5.83848500

C 2.45866300 0.00024400 -4.95156600

C 2.27258400 0.00065600 -3.56555000

C 0.95936200 -0.00106000 -3.10071700

C -3.05265600 -0.00601900 -0.98893200

C -5.13171500 -0.00865100 0.14066600

H -2.26114700 -0.00599100 -3.45527700

H 0.95871800 -0.00060600 -0.91636000

H 1.55075600 -0.00201700 -6.90941600

H 3.46923600 0.00153500 -5.35048800

H 3.10653200 0.00224700 -2.87156900

H -5.49549800 0.88195600 -0.37927900

H -5.49256000 -0.90112500 -0.37812100

H -5.47013000 -0.00853900 1.17821400

O 3.67720500 0.00781700 2.05662600

O 3.69802200 0.00624700 -0.20943600

N 1.70399500 0.00383800 0.79633000

N 1.27802300 0.00441000 3.19702400

N -0.43255200 0.00115200 1.81362700

C 0.92597700 0.00323200 1.87564200

C 0.13374500 0.00310500 3.99042900

C -0.05009300 0.00348300 5.37058200

C -1.36861300 0.00177600 5.83848500

C -2.45866300 -0.00024400 4.95156600

C -2.27258400 -0.00065600 3.56555000

C -0.95936200 0.00106000 3.10071700

C 3.05265600 0.00601900 0.98893200

C 5.13171500 0.00865100 -0.14066600

H 2.26114700 0.00599100 3.45527700

H -0.95871800 0.00060600 0.91636000

H -1.55075600 0.00201700 6.90941600

H -3.46923600 -0.00153500 5.35048800

H -3.10653200 -0.00224700 2.87156900

H 5.49549800 -0.88195600 0.37927900

H 5.49256000 0.90112500 0.37812100

H 5.47013000 0.00853900 -1.17821400

H -0.79292100 -0.00503900 -6.05535600

H 0.79292100 0.00503900 6.05535600

D2

O -3.66475400 -0.35010700 -2.17180600

O -3.76079900 -0.10818500 0.08719500

N -1.75364100 -0.15112000 -0.89036800

N -1.17653300 -0.38701500 -3.22494800

N 0.47692300 -0.17570200 -1.71636200

C -0.82813500 -0.23491800 -1.91175700

C 0.00544300 -0.43072100 -3.95309000

C 0.26847100 -0.56891100 -5.31533200

C 1.61091300 -0.57011900 -5.70091200

C 2.64446700 -0.43773500 -4.75289700

C 2.37219400 -0.30015500 -3.39127000

C 1.03216700 -0.29661200 -2.98855700

C -3.10691600 -0.21505700 -1.08753800

C -5.19722400 -0.16125400 0.00314300

H -2.14070200 -0.44790600 -3.53357100

H 1.86127100 -0.67537400 -6.75303600

H 3.67704100 -0.44318300 -5.09235500

H 3.16474200 -0.19788600 -2.65698700

H -5.57414100 0.66179100 -0.60917600

H -5.51969900 -1.11393200 -0.42434200

H -5.54473000 -0.06478800 1.03204700

O 3.66475400 0.35010700 2.17180600

O 3.76079900 0.10818500 -0.08719500

N 1.75364100 0.15112000 0.89036800

N 1.17653300 0.38701500 3.22494800

N -0.47692300 0.17570200 1.71636200

C 0.82813500 0.23491800 1.91175700

C -0.00544300 0.43072100 3.95309000

C -0.26847100 0.56891100 5.31533200

C -1.61091300 0.57011900 5.70091200

C -2.64446700 0.43773500 4.75289700

C -2.37219400 0.30015500 3.39127000

C -1.03216700 0.29661200 2.98855700

C 3.10691600 0.21505700 1.08753800

C 5.19722400 0.16125400 -0.00314300

H 2.14070200 0.44790600 3.53357100

H -1.86127100 0.67537400 6.75303600

H -3.67704100 0.44318300 5.09235500

H -3.16474200 0.19788600 2.65698700

H 5.57414100 -0.66179100 0.60917600

H 5.51969900 1.11393200 0.42434200

H 5.54473000 0.06478800 -1.03204700

H -0.52961500 -0.67105000 -6.04556100

H 0.52961500 0.67105000 6.04556100

H 1.37089300 0.03296600 -0.07147600

H -1.37089300 -0.03296600 0.07147600

D3

O -3.56866900 0.00279600 -1.02300700

O -3.98814800 0.00759300 1.20679600

N -1.80421500 0.00301800 0.42003200

N -1.90756500 0.00747500 2.87724500

N 0.04198600 0.00317700 1.86658400

C -1.30042300 0.00454000 1.64693700

C -0.94255400 0.00797000 3.88518900

C -1.03569700 0.01051300 5.27417700

C 0.16594100 0.01019600 5.99179600

C 1.40956100 0.00744400 5.33675700

C 1.50281100 0.00489700 3.94140200

C 0.30441500 0.00521000 3.23054900

C -3.12975300 0.00431800 0.11988600

C -5.39045600 0.00903700 0.88491000

H -2.91463600 0.00896900 2.96500100

H 0.73469500 0.00096300 1.09015700

H 0.13363500 0.01211600 7.07772300

H 2.32141000 0.00728500 5.92743100

H 2.45517600 0.00275900 3.41996200

H -5.64839900 0.89964900 0.30639700

H -5.65106800 -0.88312500 0.30999000

H -5.90985200 0.01174200 1.84515200

O 3.56866900 -0.00279600 1.02300700

O 3.98814800 -0.00759300 -1.20679600

N 1.80421500 -0.00301800 -0.42003200

N 1.90756500 -0.00747500 -2.87724500

N -0.04198600 -0.00317700 -1.86658400

C 1.30042300 -0.00454000 -1.64693700

C 0.94255400 -0.00797000 -3.88518900

C 1.03569700 -0.01051300 -5.27417700

C -0.16594100 -0.01019600 -5.99179600

C -1.40956100 -0.00744400 -5.33675700

C -1.50281100 -0.00489700 -3.94140200

C -0.30441500 -0.00521000 -3.23054900

C 3.12975300 -0.00431800 -0.11988600

C 5.39045600 -0.00903700 -0.88491000

H 2.91463600 -0.00896900 -2.96500100

H -0.73469500 -0.00096300 -1.09015700

H -0.13363500 -0.01211600 -7.07772300

H -2.32141000 -0.00728500 -5.92743100

H -2.45517600 -0.00275900 -3.41996200

H 5.64839900 -0.89964900 -0.30639700

H 5.65106800 0.88312500 -0.30999000

H 5.90985200 -0.01174200 -1.84515200

H -1.99635400 0.01265900 5.78139300

H 1.99635400 -0.01265900 -5.78139300

D4

O -3.72235400 0.00031400 -0.93725100

O -4.04324900 -0.00273100 1.31316000

N -1.92392300 -0.00107500 0.46949200

N -1.87354900 -0.00416600 2.90971000

N 0.05414800 -0.00226000 1.76187400

C -1.26383100 -0.00247400 1.68346300

C -0.86363300 -0.00513100 3.86706200

C -0.88540100 -0.00687800 5.26096000

C 0.35300200 -0.00738100 5.90788000

C 1.55975900 -0.00618000 5.18059600

C 1.57353000 -0.00443400 3.78516500

C 0.33951500 -0.00390900 3.12484400

C -3.26626400 -0.00105400 0.19167800

C -5.46506600 -0.00278400 1.06917200

H -2.87443100 -0.00460300 3.04358900

H 0.38386000 -0.00871800 6.99415600

H 2.50255900 -0.00662200 5.72131200

H 2.49946800 -0.00349500 3.21775800

H -5.75286100 0.89046600 0.51025700

H -5.75240300 -0.89476600 0.50799800

H -5.92465000 -0.00415400 2.05822700

O 3.72235400 -0.00031400 0.93725100

O 4.04324900 0.00273100 -1.31316000

N 1.92392300 0.00107500 -0.46949200

N 1.87354900 0.00416600 -2.90971000

N -0.05414800 0.00226000 -1.76187400

C 1.26383100 0.00247400 -1.68346300

C 0.86363300 0.00513100 -3.86706200

C 0.88540100 0.00687800 -5.26096000

C -0.35300200 0.00738100 -5.90788000

C -1.55975900 0.00618000 -5.18059600

C -1.57353000 0.00443400 -3.78516500

C -0.33951500 0.00390900 -3.12484400

C 3.26626400 0.00105400 -0.19167800

C 5.46506600 0.00278400 -1.06917200

H 2.87443100 0.00460300 -3.04358900

H -0.38386000 0.00871800 -6.99415600

H -2.50255900 0.00662200 -5.72131200

H -2.49946800 0.00349500 -3.21775800

H 5.75286100 -0.89046600 -0.51025700

H 5.75240300 0.89476600 -0.50799800

H 5.92465000 0.00415400 -2.05822700

H -1.81600000 -0.00780600 5.82235100

H 1.81600000 0.00780600 -5.82235100

H 1.29763900 -0.00016600 0.36345400

H -1.29763900 0.00016600 -0.36345400

D5

O -1.54726900 -0.38863400 -3.12458600

O -1.57002800 -0.14421700 -0.85709000

N 0.39930300 -0.20057000 -1.90596700

N 0.97413700 -0.43294900 -4.24697800

N 2.62232800 -0.22420000 -2.72083700

C 1.32793500 -0.28388200 -2.93381600

C 2.16337200 -0.47383800 -4.96676600

C 2.43882300 -0.60716300 -6.32718200

C 3.78488000 -0.60538800 -6.69951300

C 4.81067700 -0.47512800 -5.74205300

C 4.52532700 -0.34260400 -4.38304600

C 3.18192700 -0.34156200 -3.99039900

C -0.95908600 -0.25677400 -2.06203700

C -3.02077900 -0.18749500 -0.86628300

H 0.01523400 -0.49367200 -4.56836700

H 4.04498800 -0.70662100 -7.74965200

H 5.84606100 -0.47824800 -6.07230900

H 5.31538800 -0.24204200 -3.64438800

H -3.40946300 0.63698800 -1.46775900

H -3.35777200 -1.14086300 -1.27875400

H -3.30657400 -0.08426400 0.18073700

O 1.54726900 0.38863400 3.12458600

O 1.57002800 0.14421700 0.85709000

N -0.39930300 0.20057000 1.90596700

N -0.97413700 0.43294900 4.24697800

N -2.62232800 0.22420000 2.72083700

C -1.32793500 0.28388200 2.93381600

C -2.16337200 0.47383800 4.96676600

C -2.43882300 0.60716300 6.32718200

C -3.78488000 0.60538800 6.69951300

C -4.81067700 0.47512800 5.74205300

C -4.52532700 0.34260400 4.38304600

C -3.18192700 0.34156200 3.99039900

C 0.95908600 0.25677400 2.06203700

C 3.02077900 0.18749500 0.86628300

H -0.01523400 0.49367200 4.56836700

H -4.04498800 0.70662100 7.74965200

H -5.84606100 0.47824800 6.07230900

H -5.31538800 0.24204200 3.64438800

H 3.40946300 -0.63698800 1.46775900

H 3.35777200 1.14086300 1.27875400

H 3.30657400 0.08426400 -0.18073700

H 1.64852500 -0.70761800 -7.06613900

H -1.64852500 0.70761800 7.06613900

H -0.78988800 0.08594000 0.97122300

H 0.78988800 -0.08594000 -0.97122300

D6

O -0.23326600 -1.55007900 -0.00081900

O -0.40659300 -3.75483800 -0.00051100

N 1.70291100 -2.85191800 0.00001500

N 2.26060100 -0.46017200 -0.00024900

N 3.87043100 -1.94803900 0.00051200

C 2.50501900 -1.79940600 0.00006800

C 3.46029700 0.24755800 -0.00002500

C 3.72584700 1.61493200 -0.00020100

C 5.07114200 1.99813000 0.00012300

C 6.10705800 1.04868700 0.00060900

C 5.83675200 -0.32445300 0.00079000

C 4.49751400 -0.70468300 0.00046500

C 0.36271300 -2.63430900 -0.00044800

C 0.22110100 -5.04419900 -0.00012000

H 1.32633500 -0.04767500 -0.00064800

H 4.30479400 -2.85942200 0.00081700

H 5.31923700 3.05588300 -0.00000300

H 7.14035900 1.38434100 0.00084900

H 6.63825000 -1.05781000 0.00116600

H 0.84012800 -5.17779000 -0.89171100

H 0.83955800 -5.17752800 0.89190700

H -0.60286800 -5.76103800 -0.00027800

O 0.23326600 1.55007900 -0.00089000

O 0.40659300 3.75483800 -0.00052100

N -1.70291200 2.85191800 0.00000500

N -2.26060100 0.46017200 -0.00026700

N -3.87043100 1.94803900 0.00051400

C -2.50501900 1.79940600 0.00005700

C -3.46029700 -0.24755800 -0.00003700

C -3.72584700 -1.61493200 -0.00021600

C -5.07114200 -1.99813000 0.00011800

C -6.10705800 -1.04868700 0.00061800

C -5.83675200 0.32445300 0.00080400

C -4.49751400 0.70468300 0.00046800

C -0.36271300 2.63430900 -0.00047900

C -0.22110100 5.04419900 -0.00008700

H -1.32633500 0.04767500 -0.00069800

H -4.30479400 2.85942200 0.00083800

H -5.31923700 -3.05588300 -0.00000900

H -7.14035800 -1.38434100 0.00086700

H -6.63825000 1.05781000 0.00119100

H -0.83954600 5.17750400 0.89195200

H -0.84014000 5.17781400 -0.89166600

H 0.60286900 5.76103700 -0.00023600

H 2.91544900 2.33648700 -0.00056800

H -2.91544900 -2.33648700 -0.00059000

D7

O 0.05426600 -1.68215000 0.00015700

O 2.08159100 -2.69248100 0.00029900

N 1.95637000 -0.41884600 0.00004600

N 4.29312600 -1.13376300 0.00019800

N 3.79470400 1.06321500 -0.00035500

C 3.32282900 -0.16083600 -0.00004400

C 5.51459000 -0.47037200 0.00002700

C 6.83452500 -0.92010500 0.00013300

C 7.83198900 0.05800700 -0.00011700

C 7.51279400 1.43078900 -0.00046000

C 6.18885700 1.87021500 -0.00056500

C 5.17491800 0.90483900 -0.00031800

C 1.27704000 -1.60169300 0.00016700

C 1.39636300 -3.96515200 0.00043700

H 4.11337300 -2.12687000 0.00049000

H 8.87482800 -0.24766700 -0.00004500

H 8.31801100 2.16077300 -0.00064700

H 5.93960000 2.92734300 -0.00083100

H 0.77460800 -4.05817400 0.89318000

H 0.77458900 -4.05835600 -0.89227300

H 2.18986900 -4.71286600 0.00050500

O -0.05425900 1.68222600 0.00027600

O -2.08157000 2.69258100 0.00033500

N -1.95639900 0.41893400 0.00002100

N -4.29319500 1.13376700 0.00009400

N -3.79467700 -1.06318800 -0.00028100

C -3.32285100 0.16088400 -0.00005800

C -5.51463000 0.47032100 -0.00003400

C -6.83458400 0.91999700 0.00002600

C -7.83200600 -0.05815800 -0.00015700

C -7.51274900 -1.43092700 -0.00039200

C -6.18879300 -1.87029400 -0.00045200

C -5.17489700 -0.90487300 -0.00027200

C -1.27704500 1.60177800 0.00020200

C -1.39631700 3.96523800 0.00052400

H -4.11350700 2.12688600 0.00028800

H -8.87485700 0.24747000 -0.00011700

H -8.31793500 -2.16094600 -0.00052800

H -5.93948900 -2.92741100 -0.00063400

H -0.77452200 4.05845600 -0.89217000

H -0.77458200 4.05822300 0.89328400

H -2.18981000 4.71296600 0.00059400

H 7.08292900 -1.97827500 0.00039700

H -7.08303500 1.97815600 0.00020600

H -1.35404800 -0.41336300 -0.00009300

H 1.35402800 0.41345900 -0.00008000

D8

O 0.13846000 -1.54725600 -0.00007500

O 0.27759500 -3.76678000 0.00016900

N -1.80520800 -2.74413700 0.00016900

N -2.39692800 -0.37197500 0.00003200

N -4.01755600 -1.94448800 -0.00002900

C -2.72872400 -1.69427800 0.00004700

C -3.60317000 0.31838000 -0.00006000

C -3.90135300 1.68179000 -0.00012200

C -5.25419100 2.02495300 -0.00021500

C -6.26494100 1.04058400 -0.00024800

C -5.95677800 -0.31918800 -0.00018900

C -4.60453900 -0.68375100 -0.00009500

C -0.44170900 -2.62076800 0.00007200

C -0.34749000 -5.05754300 0.00034100

H -1.46151900 0.02793900 0.00004900

H -5.53523100 3.07497600 -0.00026500

H -7.30638500 1.35201800 -0.00032300

H -6.73283300 -1.07924100 -0.00021800

H -0.95221600 -5.20454400 0.90290000

H -0.95227500 -5.20475200 -0.90214600

H 0.47377300 -5.77455600 0.00039400

O -0.13846100 1.54725900 -0.00001300

O -0.27759300 3.76678300 0.00019200

N 1.80521000 2.74413800 0.00016700

N 2.39692700 0.37197500 0.00004800

N 4.01755700 1.94448700 -0.00003200

C 2.72872400 1.69427800 0.00005200

C 3.60316800 -0.31838100 -0.00005100

C 3.90135000 -1.68179100 -0.00010600

C 5.25418800 -2.02495500 -0.00020900

C 6.26493900 -1.04058700 -0.00025500

C 5.95677700 0.31918500 -0.00020200

C 4.60453800 0.68374900 -0.00009800

C 0.44171000 2.62077000 0.00010900

C 0.34749400 5.05754500 0.00030800

H 1.46151800 -0.02793700 0.00008700

H 5.53522700 -3.07497900 -0.00025600

H 7.30638300 -1.35202200 -0.00033700

H 6.73283300 1.07923800 -0.00024000

H 0.95227000 5.20471900 -0.90219000

H 0.95223000 5.20458000 0.90285600

H -0.47376800 5.77455900 0.00034400

H -3.11758500 2.43314400 -0.00009900

H 3.11758100 -2.43314500 -0.00007400

H -2.25658300 -3.64917300 0.00019200

H 2.25658500 3.64917400 0.00017800

D9

O 1.56068400 -3.94751800 0.00008200

O -0.67918200 -3.73383500 0.00034100

N 0.53374600 -1.84009000 0.00017900

N 2.94853700 -1.86563700 -0.00008200

N 1.90091200 0.11809300 0.00006700

C 1.76954700 -1.23828500 0.00005500

C 3.90861300 -0.86319200 -0.00016800

C 5.30565600 -0.93574000 -0.00032100

C 6.02014800 0.26251500 -0.00037600

C 5.36329100 1.50957500 -0.00028000

C 3.97012100 1.59808400 -0.00012800

C 3.25960200 0.39691500 -0.00007300

C 0.51788400 -3.14583100 0.00019800

C -0.72943700 -5.17457400 0.00036400

H 1.11567900 0.78520200 0.00019100

H 7.10661700 0.23554000 -0.00049400

H 5.95383500 2.42193000 -0.00032700

H 3.45866600 2.55600700 -0.00005500

H -0.24659000 -5.57584700 -0.89405200

H -0.24635300 -5.57582600 0.89466200

H -1.79254600 -5.41531000 0.00050800

O -1.56078500 3.94755200 0.00010100

O 0.67909000 3.73396400 0.00032000

N -0.53376000 1.84017000 0.00018100

N -2.94855600 1.86562000 -0.00007200

N -1.90084800 -0.11806500 0.00005900

C -1.76954000 1.23831800 0.00005700

C -3.90859100 0.86313400 -0.00016100

C -5.30563600 0.93561900 -0.00031000

C -6.02007400 -0.26266800 -0.00037500

C -5.36316200 -1.50969900 -0.00029500

C -3.96998800 -1.59814700 -0.00014700

C -3.25952500 -0.39694500 -0.00008000

C -0.51795100 3.14590800 0.00019600

C 0.72928200 5.17470500 0.00034600

H -1.11558800 -0.78514400 0.00014800

H -7.10654500 -0.23574100 -0.00049000

H -5.95366600 -2.42208000 -0.00035100

H -3.45848600 -2.55604500 -0.00008600

H 0.24620300 5.57593400 0.89465700

H 0.24639400 5.57596000 -0.89405600

H 1.79238000 5.41548800 0.00046300

H 5.81100800 -1.89729400 -0.00039500

H -5.81103300 1.89715000 -0.00037400

H 2.40657100 -3.33085300 -0.00003300

H -2.40664800 3.33085200 0.00000400

S1 | Page

Table S10. NICSvalue calculated at 1Å (from the plane of molecule) using GIAO/B3LYP/6-31+G(d) method.

In the five membered imidazole ring system of carbamate imidazole and carbendazim

Molecule / NICS
(/ppm)
CM-1 / CM-2
Carbamate imidazole / 6.413 / 9.195
Carbendazim / 5.789 / 8.037

Figure S1. Optimized 3D geometries of NSC135301 CN-1 to CN-4. The H-bond lengths obtained using B3LYP/6-31+G(d) method.

CN-1 / CN-2 / CN-3
CN-4

Table S11.Relative energies (in kcal/mol) of various tautomers of model N-substituted benzimidazole carbamate moiety NSC135301 (CN).a,b,c

Conformer / Gas phase / Water phase
CN-1 / 0.00 / 0.00
CN-2 / 9.48 / 4.94
CN-3 / 4.86 / 3.55
CN-4 / 4.98 / 4.51

a Basis set used for all optimizations is 6-31+G(d).

bAll relative energies are corrected for zero-point vibrational energy and thermal correction to Gibbs free energy.

c Implicit solvent analysis using IEFPCM level using B3LYP/6-31+G(d) method.

Table S12.Relative energies (in kcal/mol) of various tautomers of model benzimidazole carbamate moiety (CM).a,b,c

Geometry optimization was performed using M06-2X/6-31+G(d) method. Results suggested that in water phase both the conformers CM-1 and CM-2 are having the possibility to exist in the equilibrium with respect to monomeric studies.

Conformer / Gas phase / Water phase
CM-1 / 2.76 / 0.97
CM-2 / 0.00 / 0.00
CM-3 / 3.23 / 1.93

a Basis set used for all optimizations is 6-31+G(d).

bAll relative energies are corrected for zero-point vibrational energy and thermal correction to Gibbs free energy.

c Implicit solvent analysis using IEFPCM level using M06-2X/6-31+G(d) method.

S1 | Page