Table S1: Optimized parameters for HOCl, HOBr and HOI halogen bond donors at MP2/aug-cc-pVTZ(-PP)theoretical level (Distance are in Å and angles in degrees).
Parameters / HOCl / HOBr / HOIO2-X1 / 1.698 / 1.822 / 1.988
H3-O2 / 0.969 / 0.969 / 0.969
H3-O2-X1 / 102.5 / 102.9 / 104.2
Table S2: Optimized parameters for HNHCl, HNHBr and HNHI halogen bond donors at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / HNHCl / HNHBr / HNHIN2-X1 / 1.746 / 1.882 / 2.060
H3-N2 / 1.017 / 1.017 / 1.018
H4-N2 / 1.017 / 1.017 / 1.018
H3-N2-X1 / 103.9 / 103.7 / 104.1
H4-N2-X1 / 103.9 / 103.7 / 104.1
H4-N2-X1-H3 / -110.3 / -109.8 / -109.9
Table S3: Optimized parameters for CH2O···HOCl, CH2O···HOBr and CH2O···HOI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / CH2O···HOCl / CH2O···HOBr / CH2O···HOIC2-O1 / 1.218 / 1.218 / 1.218
H3-C2 / 1.097 / 1.097 / 1.097
H4-C2 / 1.096 / 1.096 / 1.097
H5-O1 / 1.805 / 1.817 / 1.837
O6-H5 / 0.981 / 0.981 / 0.980
X7-O6 / 1.692 / 1.815 / 1.978
H3-C2-O1 / 120.7 / 120.7 / 120.8
H4-C2-O1 / 121.4 / 121.3 / 121.3
H5-O1-C2 / 120.3 / 121.1 / 122.4
O6-H5-O1 / 172.4 / 172.4 / 173.0
X7-O6-H5 / 101.6 / 101.8 / 102.8
H4-C2-O1-H3 / 180.0 / -180.0 / -180.0
H5-O1-C2-H4 / 0.9 / -0.5 / -0.1
O6-H5-O1-C2 / 8.0 / 0.2 / 0.1
X7-O6-H5-O1 / -11.7 / -0.8 / -2.0
Table S4: Optimized parameters for CH3CHO···HOCl, CH3CHO···HOBr and CH3CHO···HOI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / CH3CHO···HOCl / CH3CHO···HOBr / CH3CHO···HOIC2-O1 / 1.222 / 1.222 / 1.222
C3-C2 / 1.491 / 1.490 / 1.491
H4-C2 / 1.101 / 1.102 / 1.101
H5-C3 / 1.086 / 1.086 / 1.086
H6-C3 / 1.091 / 1.091 / 1.091
H7-C3 / 1.091 / 1.091 / 1.091
H8-O1 / 1.765 / 1.766 / 1.797
O9-H8 / 0.984 / 0.986 / 0.983
X10-O9 / 1.691 / 1.816 / 1.977
C3-C2-O1 / 123.6 / 123.8 / 123.7
H4-C2-O1 / 119.6 / 119.5 / 119.4
H5-C3-C2 / 110.9 / 110.9 / 110.9
H6-C3-C2 / 109.0 / 109.0 / 109.1
H7-C3-C2 / 109.1 / 109.1 / 109.0
H8-O1-C2 / 119.4 / 107.5 / 121.9
O9-H8-O1 / 174.0 / 166.4 / 174.1
X10-O9-H8 / 101.6 / 102.1 / 102.8
H4-C2-O1-C3 / -180.0 / 179.9 / -180.0
H5-C3-C2-O1 / -0.04 / -0.2 / 0.1
H6-C3-C2-O1 / 121.8 / 121.6 / 122.0
H7-C3-C2-O1 / -121.9 / -122.0 / -121.6
H8-O1-C2-H4 / 0.7 / 0.9 / -1.7
O9-H8-O1-C2 / -1.8 / 1.9 / -13.2
X10-O9-H8-O1 / -14.9 / 63.5 / 20.2
Table S5: Optimized parameters for (CH3O)CHO···HOCl, (CH3O)CHO···HOBr and (CH3O)CHO···HOI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / (CH3O)CHO···HOCl / (CH3O)CHO···HOBr / (CH3O)CHO···HOIC2-O1 / 1.217 / 1.216 / 1.216
H3-C2 / 1.091 / 1.091 / 1.091
O4-C2 / 1.326 / 1.326 / 1.327
C5-O4 / 1.444 / 1.443 / 1.443
H6-C5 / 1.086 / 1.086 / 1.086
H7-C5 / 1.086 / 1.086 / 1.086
H8-C5 / 1.083 / 1.083 / 1.083
H9-O1 / 1.771 / 1.781 / 1.804
O10-H9 / 0.983 / 0.983 / 0.982
X11-O10 / 1.691 / 1.814 / 1.977
H3-C2-O1 / 124.4 / 124.3 / 124.3
O4-C2-O1 / 124.8 / 124.9 / 124.9
C5-O4-C2 / 114.6 / 114.5 / 114.5
H6-C5-O4 / 109.9 / 109.9 / 109.9
H7-C5-O4 / 109.9 / 109.9 / 109.9
H8-C5-O4 / 105.2 / 105.2 / 105.2
H9-O1-C2 / 119.8 / 120.4 / 121.7
O10-H9-O1 / 172.8 / 172.9 / 173.2
X11-O10-H9 / 101.5 / 101.7 / 102.8
O4-C2-O1-H3 / -180.0 / 180.0 / -180.0
C5-O4-C2-O1 / -0.02 / 0.03 / -0.01
H6-C5-O4-C2 / -60.1 / -60.8 / -60.2
H7-C5-O4-C2 / 60.6 / 59.9 / 60.5
H8-C5-O4-C2 / -179.8 / 179.5 / -179.9
H9-O1-C2-H3 / -0.04 / -0.05 / 0.001
O10-H9-O1-C2 / -0.2 / -0.3 / 0.8
X11-O10-H9-O1 / 0.2 / 0.3 / -0.8
Table S6: Optimized parameters for NH2CHO···HOCl, NH2CHO···HOBr and NH2CHO···HOI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / NH2CHO···HOCl / NH2CHO···HOBr / NH2CHO···HOIC2-O1 / 1.227 / 1.227 / 1.227
H3-C2 / 1.095 / 1.095 / 1.096
N4-C2 / 1.346 / 1.346 / 1.346
H5-N4 / 1.006 / 1.006 / 1.006
H6-N4 / 1.003 / 1.003 / 1.003
H7-O1 / 1.719 / 1.729 / 1.749
O8-H7 / 0.988 / 0.988 / 0.987
X9-O8 / 169.0 / 1.813 / 1.974
H3-C2-O1 / 122.3 / 1221.1 / 122.1
N4-C2-O1 / 123.7 / 123.7 / 123.8
H5-N4-C2 / 119.4 / 119.4 / 119.4
H6-N4-C2 / 120.9 / 120.9 / 120.9
H7-O1-C2 / 119.0 / 119.4 / 121.5
O8-H7-O1 / 174.6 / 174.8 / 174.6
X9-O8-H7 / 101.6 / 101.8 / 102.8
N4-C2-O1-H3 / -180.0 / -180.0 / -180.0
H5-N4-C2-O1 / -0.006 / -0.004 / -0.02
H6-N4-C2-O1 / -180.0 / -180.0 / -180.0
H7-O1-C2-H3 / 0.1 / 0.1 / 0.1
O8-H7-O1-C2 / 0.3 / 0.5 / 0.9
X9-O8-H7-O1 / -0.3 / -0.7 / -1.2
Table S7: Optimized parameters for CH2O···HNHCl, CH2O···HNHBr and CH2O···HNHI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / CH2O···HNHCl / CH2O···HNHBr / CH2O···HNHIC2-O1 / 1.217 / 1.217 / 1.217
H3-C2 / 1.098 / 1.098 / 1.098
H4-C2 / 1.098 / 1.098 / 1. 099
H5-O1 / 2.071 / 2.073 / 2.084
N6-H5 / 1.022 / 1.022 / 1.023
X7-N6 / 1.747 / 1.881 / 2.058
H8-N6 / 1.016 / 1.017 / 1.018
H3-C2-O1 / 121.1 / 121.1 / 121.1
H4-C2-O1 / 121.4 / 121.4 / 121.3
H5-O1-C2 / 100.6 / 99.8 / 99.5
N6-H5-O1 / 145.6 / 144.3 / 143.9
X7-N6-H5 / 103.4 / 103.2 / 103.5
H8-N6-X7 / 103.9 / 103.8 / 104.2
H4-C2-O1-H3 / 180.0 / 180.0 / 180.0
H5-O1-C2-H4 / -3.3 / -2.9 / -0.5
N6-H5-O1-C2 / -5.6 / -4.2 / -5.5
X7-N6-H5-O1 / 289.3 / 285.9 / 284.9
H8-N6-X7-H5 / 111.2 / 110.8 / 110.8
Table S8: Optimized parameters for CH3CHO···HNHCl, CH3CHO···HNHBr and CH3CHO···HNHI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / CH3CHO···HNHCl / CH3CHO···HNHBr / CH3CHO···HNHIC2-O1 / 1.220 / 1.220 / 1.220
C3-C2 / 1.494 / 1.493 / 1.493
H4-C2 / 1.103 / 1.103 / 1.103
H5-C3 / 1.086 / 1.086 / 1.086
H6-C3 / 1.091 / 1.091 / 1.091
H7-C3 / 1.091 / 1.091 / 1.091
H8-O1 / 2.023 / 2.024 / 2.042
N9-H8 / 1.023 / 1.024 / 1.024
X10-N9 / 1.747 / 1.881 / 2.057
H11-N9 / 1.016 / 1.017 / 1.018
C3-C2-O1 / 124. 0 / 124.0 / 124.1
H4-C2-O1 / 119.7 / 119.6 / 119.6
H5-C3-C2 / 110.8 / 110.9 / 110.9
H6-C3-C2 / 109.0 / 109.0 / 108.9
H7-C3-C2 / 109.2 / 109.2 / 109.2
H8-O1-C2 / 101.1 / 100.1 / 99.2
N9-H8-O1 / 150.0 / 148.8 / 147.6
X10-N9-H8 / 103.4 / 103.1 / 103.4
H11-N9-X10 / 103.8 / 103.7 / 104.1
H4-C2-O1-C3 / 179.9 / 179.8 / 179.7
H5-C3-C2-O1 / 0.1 / -0.1 / -0.8
H6-C3-C2-O1 / 121.8 / 121.6 / 120.8
H7-C3-C2-O1 / 238.2 / 238.0 / 237.2
H8-O1-C2-H4 / 7.4 / 7.6 / 8.6
N9-H8-O1-C2 / 7.4 / 8.3 / 8.5
X10-N9-H8-O1 / 74.4 / 76.1 / 77.9
H11-N9-X10-H8 / 248.9 / 249.3 / 249.3
Table S9: Optimized parameters for (CH3O)CHO···HNHCl, (CH3O)CHO···HNHBr and (CH3O)CHO···HNHI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / (CH3O)CHO···HNHCl / (CH3O)CHO···HNHBr / (CH3O)CHO···HNHIC2-O1 / 1.214 / 1.214 / 1.214
H3-C2 / 1.092 / 1.092 / 1.092
O4-C2 / 1.332 / 1.332 / 1.332
C5-O4 / 1.441 / 1.441 / 1.441
H6-C5 / 1.087 / 1.087 / 1.087
H7-C5 / 1 .087 / 1.087 / 1.087
H8-C5 / 1.083 / 1.083 / 1.083
H9-O1 / 2.029 / 2.027 / 2.037
N10-H9 / 1.022 / 1.023 / 1.023
X11-N10 / 1.749 / 1.882 / 2.057
H12-N10 / 1.017 / 1.017 / 1.018
H3-C2-O1 / 124.6 / 124.4 / 124.4
O4-C2-O1 / 125.1 / 125.1 / 125.1
C5-O4-C2 / 114.3 / 114 .3 / 114.3
H6-C5-O4 / 110.0 / 110.0 / 110.0
H7-C5-O4 / 110. / 110.0 / 110 .0
H8-C5-O4 / 105.3 / 105.3 / 105.3
H9-O1-C2 / 116.5 / 117.3 / 119.9
N10-H9-O1 / 162.8 / 163.7 / 164.3
X11-N10-H9 / 102.9 / 102.6 / 102.8
H12-N10-H9 / 106.1 / 105.8 / 105.6
O4-C2-O1-H3 / 180.0 / 180.2 / 180.0
C5-O4-C2-O1 / -0.1 / -0.1 / -0.1
H6-C5-O4-C2 / -60.1 / -60.2 / -60.1
H7-C5-O4-C2 / 60.5 / 60.5 / 60.6
H8-C5-O4-C2 / 180.2 / 180.1 / 180.2
H9-O1-C2-H3 / -5.0 / -5.4 / -5.7
N10-H9-O1-C2 / -4.1 / -9.0 / -13.8
X11-N10-H9-O1 / 21.3 / 23.0 / 25.9
H12-N10-H9-X11 / 108.4 / 108.0 / 108.5
Table S10: Optimized parameters for NH2CHO···HNHCl, NH2CHO···HNHBr and NH2CHO···HNHI complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / NH2CHO···HNHCl / NH2CHO···HNHBr / NH2CHO···HNHIC2-O1 / 1.224 / 1.224 / 1.224
H3-C2 / 1.098 / 1.098 / 1.098
N4-C2 / 1.350 / 1.350 / 1.350
H5-N4 / 1.006 / 1.006 / 1.006
H6-N4 / 1.003 / 1.003 / 1.003
H7-O1 / 1.968 / 1.9704 / 1.982
N8-H7 / 1.025 / 1.026 / 1.026
X9-N8 / 1.748 / 1.881 / 2.056
H10-N8 / 1.016 / 1.017 / 1.018
H3-C2-O1 / 122.3 / 122.3 / 122.2
N4-C2-O1 / 124.2 / 124.2 / 124.3
H5-N4-C2 / 119.4 / 119.4 / 119.4
H6-N4-C2 / 120.8 / 120.8 / 120.8
H7-O1-C2 / 100.4 / 99.3 / 98.7
N8-H7-O1 / 153.6 / 151.8 / 150.5
X9-N8-H7 / 103.4 / 103.1 / 103.3
H10-N8-H7 / 106.6 / 106.4 / 1 06.2
N4-C2-O1-H3 / 179.8 / 179.7 / 179.7
H5-N4-C2-O1 / 1.669 / 1.847 / 2.300
H6-N4-C2-O1 / 178.0 / 177.8 / 177.2
H7-O1-C2-H3 / 5.5 / 5.2 / 5.7
N8-H7-O1-C2 / 2.9 / 1.2 / 5.1
X9-N8-H7-O1 / 68.5 / 73.5 / 72.2
H10-N8-H7-X9 / 109.0 / 108.7 / 109.3
Table S11: Optimized parameters for CH2O···ClOH, CH2O···BrOH and CH2O···IOH complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / CH2O···ClOH / CH2O···BrOH / CH2O···IOHC2-O1 / 1.215 / 1.216 / 1.218
H3-C2 / 1.099 / 1.097 / 1.096
H4-C2 / 1.099 / 1.099 / 1.098
X5-O1 / 2.705 / 2.651 / 2.700
O6-X5 / 1.706 / 1.836 / 2.001
H7-O6 / 0.968 / 0.968 / 0.967
H3-C2-O1 / 121.4 / 121.1 / 120.9
H4-C2-O1 / 121.4 / 121.3 / 121.2
X5-O1-C2 / 104.0 / 107.7 / 110.9
O6-X5-O1 / 170.5 / 172.1 / 173.0
H7-O6-X5 / 102.4 / 102.9 / 104.6
H4-C2-O1-H3 / 180.0 / 180.0 / 180.0
X5-O1-C2-H4 / 0.1 / 0.04 / -0.03
O6-X5-O1-C2 / 0.1 / 0.2 / -0.4
H7-O6-X5-O1 / 179.5 / 180.1 / 178.9
Table S12: Optimized parameters for CH3CHO···ClOH, CH3CHO···BrOH and CH3CHO···IOH complexes at MP2/aug-cc-pVTZ(-PP)theoretical level (Distance are in Å and angles in degrees).
Parameters / CH3CHO···ClOH / CH3CHO···BrOH / CH3CHO···IOHC2-O1 / 1.218 / 1.220 / 1.222
C3-C2 / 1.495 / 1.492 / 1.490
H4-C2 / 1.104 / 1.103 / 1.102
H5-C3 / 1.086 / 1.086 / 1.085
H6-C3 / 1.091 / 1.091 / 1.091
H7-C3 / 1.091 / 1.091 / 1.091
X8-O1 / 2.665 / 2.609 / 2.655
O9-X8 / 1.708 / 1.840 / 2.005
H10-O9 / 0.968 / 0.968 / 0.967
C3-C2-O1 / 124.2 / 124.0 / 123.7
H4-C2-O1 / 119.6 / 119.4 / 119.3
H5-C3-C2 / 110.8 / 110.8 / 110.8
H6-C3-C2 / 109.1 / 109.1 / 109.0
H7-C3-C2 / 109.1 / 109.1 / 109.0
X8-O1-C2 / 105.1 / 108.4 / 111.5
O9-X8-O1 / 171.7 / 173.0 / 173.7
H10-O9-X8 / 102.3 / 102.8 / 104.6
H4-C2-O1-C3 / 180.0 / 180.0 / 180.0
H5-C3-C2-O1 / -0.0006 / 0.01 / -0.004
H6-C3-C2-O1 / 121.7 / 121.8 / 121.8
H7-C3-C2-O1 / 238.3 / 238.2 / 238.2
X8-O1-C2-H4 / 0.1 / -0.04 / 0.04
O9-X8-O1-C2 / 0.1 / -0.2 / -0.1
H10-O9-X8-O1 / 180.0 / 180.1 / 179.9
Table S13: Optimized parameters for (CH3O)CHO···ClOH, (CH3O)CHO···BrOH and (CH3O)CHO···IOH complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / (CH3O)CHO···ClOH / (CH3O)CHO···BrOH / (CH3O)CHO···IOHC2-O1 / 1.211 / 1.214 / 1.217
O3-C2 / 1.335 / 1.330 / 1.326
C4-O3 / 1.441 / 1.442 / 1.444
H5-C2 / 1.093 / 1.092 / 1.092
H6-C4 / 1.087 / 1.087 / 1.086
H7-C4 / 1.087 / 1.087 / 1.086
H8-C4 / 1.083 / 1.083 / 1.083
X9-O1 / 2.713 / 2.651 / 2.687
O10-X9 / 1.706 / 1.837 / 2.003
H11-O10 / 0.968 / 0.968 / 0.967
O3-C2-O1 / 125.4 / 125.2 / 125.0
C4-O3-C2 / 114.2 / 114.3 / 114.4
H5-C2-O1 / 124.7 / 124.4 / 124.2
H6-C4-O3 / 110.0 / 110.0 / 109.9
H7-C4-O3 / 110.0 / 110.0 / 109.9
H8-C4-O3 / 105.4 / 105.3 / 105.2
X9-O1-C2 / 104.1 / 108.0 / 111.5
O10-X9-O1 / 172.3 / 174.0 / 175.5
H11-O10-X9 / 102.4 / 102.9 / 104.6
C4-O3-C2-O1 / 0.02 / 0.003 / -0.07
H5-C2-O1-O3 / 180.0 / 180.0 / -180.0
H6-C4-O3-C2 / -60.4 / -60.3 / -60.3
H7-C4-O3-C2 / 60.2 / 60.3 / 60.4
H8-C4-O3-C2 / 179.9 / 180.0 / -179.9
X9-O1-C2-H5 / 0.5 / 0.2 / -1.2
O10-X9-O1-C2 / 1.4 / 1.1 / -26.4
H11-O10-X9-O1 / -174.4 / -179.6 / 144.0
Table S14: Optimized parameters for NH2CHO···ClOH, NH2CHO···BrOH and NH2CHO···IOH complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / NH2CHO···ClOH / NH2CHO···BrOH / NH2CHO···IOHC2-O1 / 1.222 / 1.225 / 1.228
N3-C2 / 1.352 / 1.348 / 1.344
H4-C2 / 1.099 / 1.098 / 1.097
H5-N3 / 1.006 / 1.006 / 1.006
H6-N3 / 1.003 / 1.003 / 1.003
X7-O1 / 2.635 / 2.578 / 2.614
O8-X7 / 1.711 / 1.843 / 2.010
H9-O8 / 0.968 / 0.967 / 0.967
N3-C2-O1 / 124.4 / 124.2 / 123.9
H4-C2-O1 / 122.3 / 122.1 / 121.9
H5-N3-C2 / 119.4 / 119.5 / 119.5
H6-N3-C2 / 120.9 / 120.9 / 120.8
X7-O1-C2 / 103.9 / 107.3 / 110.8
O8-X7-O1 / 172.5 / 173.6 / 174.8
H9-O8-X7 / 102.3 / 102.8 / 104.6
H4-C2-O1-N3 / 180.0 / 180.0 / -180.0
H5-N3-C2-O1 / -0.06 / -0.1 / 0.2
H6-N3-C2-O1 / -179.9 / -179.9 / 179.8
X7-O1-C2-H4 / -0.1 / -0.05 / 0.8
O8-X7-O1-C2 / -0.1 / 0.09 / 16.7
H9-O8-X7-O1 / 178.9 / 178.9 / -151.8
Table S15: Optimized parameters for CH2O···ClNH2, CH2O···BrNH2 and CH2O···INH2 complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / CH2O···ClNH2 / CH2O···BrNH2 / CH2O···INH2C2-O1 / 1.214 / 1.215 / 1.216
H3-C2 / 1.100 / 1.099 / 1.098
H4-C2 / 1.099 / 1.099 / 1 .099
X5-O1 / 2.958 / 2.886 / 2.888
N6-X5 / 1.749 / 1.887 / 2.066
H7-N6 / 1.017 / 1.017 / 1.018
H8-N6 / 1.017 / 1.017 / 1.018
H3-C2-O1 / 121.5 / 121.4 / 121.2
H4-C2-O1 / 121.4 / 121.3 / 121.2
X5-O1-C2 / 96.4 / 101.3 / 106.1
N6-X5-O1 / 164.5 / 167.7 / 170.0
H7-N6-X5 / 104.0 / 103.8 / 104.5
H8-N6-H7 / 105.5 / 105.2 / 104.9
H4-C2-O1-H3 / 180.0 / 180.0 / 180.0
X5-O1-C2-H4 / -0.02 / 0.2 / -0.1
N6-X5-O1-C2 / -0.5 / 0.3 / 0.
H7-N6-X5-O1 / 235.9 / 234.4 / 234.5
H8-N6-H7-X5 / 109.1 / 108.8 / 109.7
Table S16: Optimized parameters for CH3CHO···ClNH2, CH3CHO···BrNH2 and CH3CHO···INH2 complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / CH3CHO···ClNH2 / CH3CHO···BrNH2 / CH3CHO···INH2C2-O1 / 1.217 / 1.218 / 1.219
C3-C2 / 1.497 / 1.495 / 1.493
H4-C2 / 1.104 / 1.104 / 1.103
H5-C3 / 1.086 / 1.086 / 1.086
H6-C3 / 1.091 / 1.091 / 1.091
H7-C3 / 1.091 / 1.091 / 1.091
X8-O1 / 2.918 / 2.843 / 2.844
N9-X8 / 1. 750 / 1.889 / 2.069
H10-N9 / 1.017 / 1.017 / 1.018
H11-N9 / 1.017 / 1.017 / 1.018
C3-C2-O1 / 124.2 / 124.2 / 124.0
H4-C2-O1 / 119.7 / 119.5 / 119.4
H5-C3-C2 / 110.8 / 110.8 / 110.8
H6-C3-C2 / 109.2 / 109.2 / 109.1
H7-C3-C2 / 109.2 / 109.2 / 109.1
X8-O1-C2 / 98.2 / 102.4 / 107.1
N9-X8-O1 / 166.9 / 169.1 / 171.0
H10-N9-X8 / 104.0 / 103.8 / 104.5
H11-N9-H10 / 105.5 / 105.1 / 104.9
H4-C2-O1-C3 / 180.0 / 180.0 / 180.0
H5-C3-C2-O1 / -0.04 / 0.02 / 0.004
H6-C3-C2-O1 / 121.6 / 121.7 / 121.7
H7-C3-C2-O1 / 238.3 / 238.3 / 238.2
X8-O1-C2-H4 / -0.2 / -0.1 / -0.1
N9-X8-O1-C2 / -0.8 / 0.2 / 0.02
H10-N9-X8-O1 / 236.7 / 234.4 / 234.9
H11-N9-H10-X8 / 109.1 / 108.8 / 109.7
Table S17: Optimized parameters for (CH3O)CHO···ClNH2, (CH3O)CHO···BrNH2 and (CH3O)CHO···INH2 complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / (CH3O)CHO…ClNH2 / (CH3O)CHO…BrNH2 / (CH3O)CHO…INH2C2-O1 / 1.209 / 1.211 / 1.213
O3-C2 / 1.339 / 1.336 / 1.331
C4-O3 / 1.439 / 1.440 / 1.442
H5-C2 / 1.093 / 1.093 / 1.093
H6-C4 / 1.087 / 1.087 / 1.087
H7-C4 / 1.087 / 1.087 / 1.087
H8-C4 / 1.084 / 1.083 / 1.083
X9-O1 / 2.971 / 2.880 / 2.874
N10-X9 / 1.749 / 1.887 / 2.067
X11-N10 / 1.017 / 1.017 / 1.018
H12-N10 / 1.017 / 1.017 / 1.018
O3-C2-O1 / 125.4 / 125.4 / 125.2
C4-O3-C2 / 114.0 / 114.1 / 114.2
H5-C2-O1 / 124. 8 / 124.6 / 124.
H6-C4-O3 / 110.1 / 110.1 / 110.0
H7-C4-O3 / 110.1 / 110.1 / 110.0
H8-C4-O3 / 105.4 / 105.4 / 105.3
X9-O1-C2 / 95.3 / 101.1 / 106.8
N10-X9-O1 / 166.5 / 170.0 / 172.1
X11-N10-X9 / 104.0 / 103.9 / 104.6
H12-N10-H11 / 105.5 / 105.2 / 104.9
C4-O3-C2-O1 / 0.0 / -0.004 / -0.01
H5-C2-O1-O3 / 180.0 / 180.0 / 180.0
H6-C4-O3-C2 / -60.3 / -60.3 / -60.3
H7-C4-O3-C2 / 60.3 / 60.4 / 60.3
H8-C4-O3-C2 / 180.0 / 180.0 / 180.0
X9-O1-C2-H5 / 0.7 / 0.1 / 0.4
N10-X9-O1-C2 / -0.01 / -0.2 / 2.7
X11-N10-X9-O1 / 235.0 / 235.4 / 231.3
H12-N10-H11-X9 / 109.1 / 108.9 / 109.7
Table S18: Optimized parameters for NH2CHO···ClNH2, NH2CHO···BrNH2 and NH2CHO···INH2 complexes at MP2/aug-cc-pVTZ(-PP) theoretical level (Distance are in Å and angles in degrees).
Parameters / NH2CHO···ClNH2 / NH2CHO···BrNH2 / NH2CHO···INH2C2-O1 / 1.220 / 1.222 / 1.224
N3-C2 / 1.356 / 1.353 / 1.349
H4-C2 / 1.099 / 1.099 / 1.098
H5-N3 / 1.005 / 1.006 / 1.006
H6-N3 / 1.003 / 1.003 / 1.003
X7-O1 / 2.89 / 2.811 / 2.803
N8-X7 / 1.751 / 1.890 / 2.071
H9-N8 / 1.017 / 1.017 / 1.017
H10-N8 / 1.017 / 1.018 / 1.017
N3-C2-O1 / 124.5 / 124.4 / 124.2
H4-C2-O1 / 122.4 / 122.2 / 122.0
H5-N3-C2 / 119.4 / 119.4 / 119.4
H6-N3-C2 / 120.9 / 120.9 / 120.9
X7-O1-C2 / 96.8 / 101.4 / 106.5
N8-X7-O1 / 167.8 / 170.0 / 171.8
H9-N8-X7 / 104.0 / 103.9 / 104.6
H10-N8-H9 / 105.4 / 105.1 / 104.8
H4-C2-O1-N3 / 180.0 / 180.0 / 180.0
H5-N3-C2-O1 / -0.001 / -0.01 / -0.03
H6-N3-C2-O1 / 180.0 / 180.0 / 180.0
X7-O1-C2-H4 / -0.07 / 0.04 / -0.06
N8-X7-O1-C2 / -0.1 / 0.2 / -0.4
H9-N8-X7-O1 / 235.3 / 234.7 / 235.8
H10-N8-H9-X7 / 109.1 / 108.8 / 109.7
Figure S1: Optimized structures of the RCHO···HAX (R = -H, -CH3, -OCH3, -NH2; A = -O, -NH and X = -Cl, -Br, -I) hydrogen-bonded complexes along with the NPA charges (au, in brackets) on the atoms specified at MP2/aug-cc-pVTZ(-PP) level.
Table S19: The change of bond lengths (Å) and vibrational frequencies (cm-1) for the O-H, N-H or C-H bonds for HOX, HN(H)X (X = -Cl, -Br and -I) or RCHO (R = -H, -CH3, -OCH3 and -NH2) molecules respectively upon hydrogen bond formation at MP2/aug-cc-pVTZ(-PP for iodine) level. The occupancies for the σ*orbital from NBO analysis at MP2/aug-cc-pVTZ(-PP for iodine) level.
Complexes / ΔrH-O, H-N / ΔrC-H / ΔvH-O, H-N / ΔvC-H / Occupancies(σ*O-H)
CH2O···HOCl / 0.012 / -0.004 / -263.87 / +37.58 / 0.023
CH2O···HOBr / 0.012 / -0.004 / -254.12 / +35.55 / 0.021
CH2O···HOI / 0.011 / -0.003 / -235.78 / +30.39 / 0.018
CH3CHO···HOCl / 0.015 / -0.004 / -325.71 / +62.14 / 0.028
CH3CHO···HOBr / 0.017 / -0.003 / -352.16 / +50.73 / 0.028
CH3CHO···HOI / 0.014 / -0.004 / -291.58 / +56.35 / 0.022
(CH3O)CHO···HOCl / 0.014 / -0.002 / -298.33 / +33.99 / 0.026
(CH3O)CHO···HOBr / 0.014 / -0.002 / -290.11 / +32.75 / 0.024
(CH3O)CHO···HOI / 0.013 / -0.002 / -267.00 / +27.93 / 0.020
(H2N)CHO···HOCl / 0.019 / -0.015 / -401.88 / +61.20 / 0.033
(H2N)CHO···HOBr / 0.019 / -0.015 / -393.71 / +59.61 / 0.031
(H2N)CHO···HOI / 0.018 / -0.014 / -364.30 / +52.85 / 0.027
CH2O···HN(H)Cl / 0.005 / -0.002 / -56.85 / +20.82 / 0.013
CH2O···HN(H)Br / 0.005 / -0.002 / -57.82 / +20.24 / 0.011
CH2O···HN(H)I / 0.005 / -0.001 / -56.16 / +18.22 / 0.010
CH3CHO···HN(H)Cl / 0.006 / -0.002 / -78.59 / +38.38 / 0.014
CH3CHO···HN(H)Br / 0.007 / -0.002 / -80.23 / +37.62 / 0.013
CH3CHO···HN(H)I / 0.006 / -0.002 / -79.59 / +34.02 / 0.012
(CH3O)CHO···HN(H)Cl / 0.005 / -0.001 / -55.95 / +25.56 / 0.012
(CH3O)CHO···HN(H)Br / 0.006 / -0.001 / -58.76 / +26.41 / 0.011
(CH3O)CHO···HN(H)I / 0.005 / -0.001 / -57.68 / +22.12 / 0.010
(H2N)CHO···HN(H)Cl / 0.008 / -0.012 / -109.91 / +33.46 / 0.017
(H2N)CHO···HN(H)Br / 0.009 / -0.012 / -111.42 / +32.80 / 0.016
(H2N)CHO···HN(H)I / 0.008 / -0.012 / -109.99 / +29.75 / 0.014
Table S20: The change of bond lengths (Å) and vibrational frequencies (cm-1) for the O-X, N-X or C-H bonds for HOX, HN(H)X (X = -Cl, -Br and -I) or RCHO (R = -H, -CH3, -OCH3 and -NH2) molecules respectively upon halogen bond formation at MP2/aug-cc-pVTZ(-PP for iodine) level. The occupancies for the σ* orbital from NBO analysis at MP2/aug-cc-pVTZ(-PP for iodine) level
Complexes / ΔrX-O, X-N / ΔrC-H / ΔvX-O, X-N / ΔvC-H / Occupancies(σ*O-X)
CH2O···ClOH / 0.008 / -0.001 / -20.94 / +14.41 / 0.011
CH2O···BrOH / 0.014 / -0.001 / -23.32 / +23.58 / 0.021
CH2O···IOH / 0.013 / -0.002 / -22.02 / +32.39 / 0.030
CH3CHO···ClOH / 0.010 / -0.001 / -27.65 / +23.94 / 0.013
CH3CHO···BrOH / 0.018 / -0.002 / -25.45 / +36.53 / 0.025
CH3CHO···IOH / 0.017 / -0.003 / -26.64 / +47.46 / 0.036
(CH3O)CHO···ClOH / 0.008 / 0.0 / -20.52 / +10.02 / 0.011
(CH3O)CHO···BrOH / 0.015 / -0.001 / -23.30 / +15.31 / 0.021
(CH3O)CHO···IOH / 0.015 / -0.001 / -28.33 / +21.03 / 0.032
(H2N)CHO···ClOH / 0.013 / -0.011 / -32.37 / +22.39 / 0.016
(H2N)CHO···BrOH / 0.021 / -0.012 / -30.11 / +35.29 / 0.029
(H2N)CHO···IOH / 0.022 / -0.013 / -33.04 / +47.56 / 0.042
CH2O···ClNH2 / 0.003 / -0.001 / -4.09 / +4.85 / 0.006
CH2O···BrNH2 / 0.005 / -0.001 / -5.94 / +10.40 / 0.010
CH2O···INH2 / 0.006 / -0.001 / -9.86 / +22.67 / 0.017
CH3CHO···ClNH2 / 0.004 / -0.001 / -4.90 / +19.05 / 0.007
CH3CHO···BrNH2 / 0.007 / -0.001 / -6.01 / +22.56 / 0.011
CH3CHO···INH2 / 0.009 / -0.002 / -10.12 / +29.06 / 0.020
(CH3O)CHO···ClNH2 / 0.003 / 0.0 / -3.65 / +9.48 / 0.006
(CH3O)CHO···BrNH2 / 0.005 / 0.0 / -6.09 / +9.66 / 0.010
(CH3O)CHO···INH2 / 0.007 / 0.0 / -2.02 / +11.03 / 0.018
(H2N)CHO···ClNH2 / 0.005 / -0.011 / -5.59 / +16.26 / 0.007
(H2N)CHO···BrNH2 / 0.008 / -0.011 / -7.48 / +19.82 / 0.013
(H2N)CHO···INH2 / 0.011 / -0.012 / -12.62 / +27.81 / 0.023
Figure S3: Variation of MEP (kcal/mol) at H atom of hypohalous acids (HOCl, HOBr and HOI) and monohaloamines(NH2Cl, NH2Br and NH2I) with interaction energies for the hydrogen-bonded complexes RCHO···HAX (R = -H, -CH3, -OCH3 and -NH2; A = -O or -NH; X = -Cl, -Br or -I) at MP2/aug-cc-pVTZ(-PP) level.
Figure S4: Variation of MEP (kcal/mol) at X atom of hypohalous acids (HOCl, HOBr and HOI) and monohaloamines(NH2Cl, NH2Br and NH2I) with interaction energies for the halogen-bonded complexes RCHO···XAH (R = -H, -CH3, -OCH3 and -NH2; A = -O or -NH; X = -Cl, -Br or -I) at MP2/aug-cc-pVTZ(-PP) level.
Figure S5:Comparison between interaction energies (kcal/mol) and second order stabilization energy (kcal/mol) for the hydrogen-bonded complexes RCHO···HAX (R = H, CH3, OCH3 and NH2; A = O or NH; X = Cl, Br or I) at MP2/aug-cc-pVTZ(-PP) level.
Figure S6:Comparison between interaction energies (kcal/mol) and second order stabilization energy (kcal/mol) for the halogen-bonded complexes RCHO···XAH (R = H, CH3, OCH3 and NH2; A = O or NH; X = Cl, Br or I) at MP2/aug-cc-pVTZ(-PP) level.
Figure S7: Relationship between change in % s-character of O or N hybrids of H-O or H-N bonds, respectively; and the interaction energies (ΔECorr) for the hydrogen-bonded complexes RCHO···HAX (R = -H, -CH3, -OCH3 and -NH2; A = -O or -NH; X = -Cl, -Br or -I) at MP2/aug-cc-pVTZ(-PP) level.
Figure S8: Relationship between change in % s-character of O or N hybrids of X-O or X-N bonds, respectively; and the interaction energies (ΔECorr) for the halogen-bonded complexes RCHO···XAH (R = -H, -CH3, -OCH3 and -NH2; A = -O or -NH; X = -Cl, -Br or -I) at MP2/aug-cc-pVTZ(-PP) level.
Table S21:The topological and energy properties at the bond critical points (bcps) (All the values are in au) for the hydrogen-bonded complexes RCHO···HAX at MP2/aug-cc-pVTZ(-PP) theoretical level using QTAIM analysis.
Complexes / ρb / 2ρb / Gb / Vb / Hb / Gb/VbCH2O···HOCl / 0.0309 / 0.1318 / +0.0291 / -0.0253 / -0.0038 / -1.15
CH2O···HOBr / 0.0300 / 0.1280 / +0.0281 / -0.0243 / -0.0039 / -1.16
CH2O···HOI / 0.0286 / 0.1225 / +0.0267 / -0.0228 / -0.0039 / -1.17
CH3CHO···HOCl / 0.0343 / 0.1439 / +0.0326 / -0.0292 / -0.0034 / -1.12
CH3CHO···HOBr / 0.0354 / 0.1440 / +0.0332 / -0.0305 / -0.0027 / -1.09
CH3CHO···HOI / 0.0316 / 0.1347 / +0.0299 / -0.0262 / -0.0038 / -1.14
(CH3O)CHO···HOCl / 0.0332 / 0.1425 / +0.0319 / -0.0282 / -0.0037 / -1.13
(CH3O)CHO···HOBr / 0.0316 / 0.1387 / + / - / - / -
(CH3O)CHO···HOI / 0.0306 / 0.1327 / +0.0292 / -0.0252 / -0.0040 / -1.16
(H2N)CHO···HOCl / 0.0383 / 0.1584 / +0.0370 / -0.0344 / -0.0026 / -1.07
(H2N)CHO···HOBr / 0.0373 / 0.1556 / +0.0361 / -0.0332 / -0.0028 / -1.09
(H2N)CHO···HOI / 0.0353 / 0.1499 / +0.0341 / -0.0307 / -0.0034 / -1.11
CH2O···HN(H)Cl / 0.0199 / 0.0693 / +0.0166 / -0.0159 / -0.0007 / -1.04
CH2O···HN(H)Br / 0.0199 / 0.0694 / +0.0167 / -0.0160 / -0.0007 / -1.04
CH2O···HN(H)I / 0.0195 / 0.0678 / +0.0163 / -0.0157 / -0.0006 / -1.04
CH3CHO···HN(H)Cl / 0.0218 / 0.0776 / +0.0183 / -0.0172 / -0.0011 / -1.06
CH3CHO···HN(H)Br / 0.0219 / 0.0779 / +0.0184 / -0.0174 / -0.0010 / -1.06
CH3CHO···HN(H)I / 0.0211 / 0.0747 / +0.0178 / -0.0169 / -0.0009 / -1.05
(CH3O)CHO···HN(H)Cl / 0.0202 / 0.0745 / +0.0170 / -0.0154 / -0.0016 / -1.10
(CH3O)CHO···HN(H)Br / 0.0200 / 0.0739 / + / - / -
(CH3O)CHO···HN(H)I / 0.0197 / 0.0730 / +0.0167 / -0.0151 / -0.0016 / -1.10
(H2N)CHO···HN(H)Cl / 0.0243 / 0.0890 / +0.0207 / -0.0192 / -0.0015 / -1.08
(H2N)CHO···HN(H)Br / 0.0240 / 0.0870 / +0.0208 / -0.0194 / -0.0014 / -1.07
(H2N)CHO···HN(H)I / 0.0239 / 0.0868 / +0.0204 / -0.0191 / -0.0013 / -1.07
Table S22:The topological and energy properties at the bond critical points (bcps) (All the values are in au) for the halogen-bonded complexes RCHO···XAH at MP2/aug-cc-pVTZ(-PP) theoretical level using QTAIM analysis.
Complexes / ρb / 2ρb / Gb / Vb / Hb / -Gb/VbCH2O···ClOH / 0.0177 / 0.0727 / +0.0165 / -0.0149 / -0.0016 / -1.11
CH2O···BrOH / 0.0228 / 0.0871 / +0.0205 / -0.0192 / -0.0013 / -1.09
CH2O···IOH / 0.0260 / 0.0859 / +0.0217 / -0.0218 / +0.0002 / -0.99
CH3CHO···ClOH / 0.0193 / 0.0790 / +0.0181 / -0.0164 / -0.0017 / -1.10
CH3CHO···BrOH / 0.0250 / 0.0946 / +0.0225 / -0.0213 / -0.0012 / -1.06
CH3CHO···IOH / 0.0277 / 0.0934 / +0.0239 / -0.0245 / +0.0006 / -0.97
(CH3O)CHO···ClOH / 0.0172 / 0.0709 / +0.0161 / -0.0145 / -0.0016 / -1.11
(CH3O)CHO···BrOH / 0.0224 / 0.0800 / + / -
(CH3O)CHO···IOH / 0.0255 / 0.0879 / +0.0221 / -0.0222 / +0.0001 / -0.99
(H2N)CHO···ClOH / 0.0206 / 0.0838 / +0.0193 / -0.0176 / -0.0017 / -1.10
(H2N)CHO···BrOH / 0.0247 / 0.1000 / +0.0240 / -0.0230 / -0.0010 / -1.04
(H2N)CHO···IOH / 0.0300 / 0.1004 / +0.0260 / -0.0270 / +0.0009 / -0.96
CH2O···ClNH2 / 0.0111 / 0.0445 / +0.0099 / -0.0086 / -0.0013 / -1.15
CH2O···BrNH2 / 0.0148 / 0.0560 / +0.0127 / -0.0115 / -0.0013 / -1.10
CH2O···INH2 / 0.0182 / 0.0620 / +0.0149 / -0.0144 / -0.0006 / -1.03
CH3CHO···ClNH2 / 0.0119 / 0.0482 / +0.0107 / -0.0094 / -0.0013 / -1.14
CH3CHO···BrNH2 / 0.0162 / 0.0610 / +0.0139 / -0.0126 / -0.0013 / -1.10
CH3CHO···INH2 / 0.0199 / 0.0672 / +0.0164 / -0.0159 / -0.0004 / -1.03
(CH3O)CHO···ClNH2 / 0.0107 / 0.0431 / +0.0095 / -0.0083 / -0.0013 / -1.14
(CH3O)CHO···BrNH2 / 0.0155 / 0.0534 / + / - / -
(CH3O)CHO···INH2 / 0.0184 / 0.0634 / +0.0152 / -0.0146 / -0.0006 / -1.04
(H2N)CHO···ClNH2 / 0.0125 / 0.0500 / +0.0112 / -0.0098 / -0.0013 / -1.14
(H2N)CHO···BrNH2 / 0.0173 / 0.0648 / +0.0149 / -0.0136 / -0.0013 / -1.09
(H2N)CHO···INH2 / 0.0215 / 0.0721 / +0.0177 / -0.0174 / -0.0003 / -1.02
Figure S9: Relationship between the ρb at bcp and the interaction energies (ΔECorr) for the hydrogen-bonded complexes RCHO···HAX (R = H, CH3, OCH3 and NH2; A = O or NH; X = Cl, Br or I) at MP2/aug-cc-pVTZ(-PP) level.
Figure S10: Relationship between the ρb at bcp and the interaction energies (ΔECorr) for the halogen-bonded complexes RCHO···XAH (R = H, CH3, OCH3 and NH2; A = O or NH; X = Cl, Br or I) at MP2/aug-cc-pVTZ(-PP) level.