Table TS1: Optimized Parameters for HCHO and CH3CHO at B3LYP/6-31 G(D,P) (L1) And

Table TS1: Optimized parameters for HCHO and CH3CHO at B3LYP/6-31++G(d,p) (L1) and MP2/aug-cc-pVDZ (L2) theoretical levels.

Parameters / HCHO / Parameters / CH3CHO
L1 / L2 / L1 / L2
C2-O1 / 1.210 / 1.224 / C2-O1 / 1.213 / 1.227
H3-C2 / 1.108 / 1.098 / C3-C2 / 1.505 / 1.500
H4-C2 / 1.108 / 1.098 / H4-C2 / 1.113 / 1.104
H3-C2-O1 / 121.9 / 121.7 / H5-C3 / 1.092 / 1.087
H4-C2-O1 / 121.9 / 121.7 / H6-C3 / 1.097 / 1.091
H4-C2-O1-H3 / 180.00 / 180.0 / H7-C3 / 1.097 / 1.091
C3-C2-O1 / 124.7 / 124.4
H4-C2-O1 / 119.9 / 119.8
H5-C3-C2 / 110.9 / 110.4
H6-C3-C2 / 109.5 / 109.4
H7-C3-C2 / 109.5 / 109.4
H4-C2-O1-C3 / 180.0 / 180.0
H5-C3-C2-O1 / 0.001 / 0.001
H6-C3-C2-O1 / 121.7 / 121.4
H7-C3-C2-O1 / 238.3 / 238.6

TableTS2: Optimized parameters for X-Y molecules and its halogen-bonded complex with CH2Oat B3LYP/6-31++G(d,p) (L1) and MP2/aug-cc-pVDZ (L2) theoretical levels.

Parameters / BrCF3 / Parameters / CH2O···BrCF3
L1 / L2 / L1 / L2
F2-C1 / 1.338 / 1.343 / F2-C1 / 1.342 / 1.347
F3-C1 / 1.338 / 1.343 / F3-C1 / 1.343 / 1.348
F4-C1 / 1.338 / 1.343 / F4-C1 / 1.342 / 1.347
Br5-C1 / 1.937 / 1.920 / Br5-C1 / 1.932 / 1.915
F3-C1-F2 / 108.5 / 108.3 / O6-Br5 / 2.953 / 2.952
F4-C1-F2 / 108.5 / 108.3 / C7-O6 / 1.211 / 1.225
Br5-C1-F3 / 110.4 / 110.6 / H8-C7 / 1.107 / 1.097
F4-C1-F2-F3 / 117.7 / 117.3 / H9-C7 / 1.107 / 1.098
Br5-C1-F3-F4 / -121.1 / -121.3 / F3-C1-F2 / 108.1 / 107.9
F4-C1-F2 / 108.0 / 107.9
Br5-C1-F3 / 111.0 / 111.1
O6-Br5-C1 / 172.8 / 172.7
C7-O6-Br5 / 136.9 / 137.0
H8-C7-O6 / 121.8 / 121.7
H9-C7-H8 / 116.4 / 116.7
F4-C1-F2-F3 / 116.7 / 116.5
Br5-C1-F3-F4 / -121.6 / -121.8
O6-Br5-C1-F2 / -59.9 / -60.4
C7-O6-Br5-C1 / 180.0 / 178.8
H8-C7-O6-Br5 / 180.0 / 180.0
H9-C7-H8-O6 / 180.0 / 180.0

Table TS3

Parameters / ClCF3 / Parameters / CH2O···ClCF3
L1 / L2 / L1 / L2
F2-C1 / 1.338 / 1.343 / F2-C1 / 1.340 / 1.345
F3-C1 / 1.338 / 1.343 / F3-C1 / 1.341 / 1.345
F4-C1 / 1.338 / 1.343 / F4-C1 / 1.341 / 1.347
Cl5-C1 / 1.772 / 1.741 / Cl5-C1 / 1.765 / 1.737
F3-C1-F2 / 108.52 / 108.23 / O6-Cl5 / 3.070 / 3.029
F4-C1-F2 / 108.51 / 108.23 / C7-O6 / 1.210 / 1.225
Cl5-C1-F3 / 110.41 / 110.69 / H8-C7 / 1.108 / 1.098
F4-C1-F2-F3 / 117.72 / 117.11 / H9-C7 / 1.108 / 1.098
Cl5-C1-F3-F4 / -121.11 / -121.47 / F3-C1-F2 / 108.25 / 108.03
F4-C1-F2 / 108.23 / 107.90
Cl5-C1-F3 / 110.69 / 111.02
O6-Cl5-C1 / 178.12 / 168.54
C7-O6-Cl5 / 131.21 / 108.56
H8-C7-O6 / 121.69 / 121.62
H9-C7-H8 / 116.44 / 116.75
F4-C1-F2-F3 / 117.02 / 116.42
Cl5-C1-F3-F4 / -121.41 / -121.63
O6-Cl5-C1-F2 / -162.85 / -119.93
C7-O6-Cl5-C1 / -6.62 / -0.02
H8-C7-O6-Cl5 / 179.54 / 180.02
H9-C7-H8-O6 / 180.07 / 180.00

Table TS4

Parameters / BrCF2H / Parameters / CH2O···BrCF2H
L1 / L2 / L1 / L2
F2-C1 / 1.350 / 1.357 / F2-C1 / 1.357 / 1.363
F3-C1 / 1.350 / 1.357 / F3-C1 / 1.356 / 1.363
H4-C1 / 1.089 / 1.085 / H4-C1 / 1.090 / 1.086
Br5-C1 / 1.953 / 1.932 / Br5-C1 / 1.939 / 1.921
F3-C1-F2 / 108.3 / 108.1 / O6-Br5 / 3.056 / 3.040
H4-C1-F2 / 110.3 / 109.9 / C7-O6 / 1.210 / 1.225
Br5-C1-F3 / 109.7 / 109.7 / H8-C7 / 1.107 / 1.098
H4-C1-F2-F3 / 120.8 / 120.0 / H9-C7 / 1.108 / 1.098
Br5-C1-F3-H4 / -119.5 / -120.4 / F3-C1-F2 / 107.6 / 107.5
H4-C1-F2 / 109.5 / 109.2
Br5-C1-F3 / 110.1 / 110.1
O6-Br5-C1 / 169.5 / 169.8
C7-O6-Br5 / 131.1 / 131.3
H8-C7-O6 / 121.9 / 121.9
H9-C7-H8 / 116.3 / 116.6
H4-C1-F2-F3 / 119.0 / 118.4
Br5-C1-F3-H4 / -120.7 / 121.6
O6-Br5-C1-F2 / -138.0 / -122.9
C7-O6-Br5-C1 / 176.1 / -178.0
H8-C7-O6-Br5 / -179.8 / 179.8
H9-C7-H8-O6 / 180.0 / 180.0

Table TS5

Parameters / ClCF2H / Parameters / CH2O···ClCF2H
L1 / L2 / L1 / L2
F2-C1 / 1.352 / 1.359 / F2-C1 / 1.355 / 1.362
F3-C1 / 1.352 / 1.359 / F3-C1 / 1.355 / 1.363
H4-C1 / 1.090 / 1.085 / H4-C1 / 1.090 / 1.085
Cl5-C1 / 1.782 / 1.749 / Cl5-C1 / 1.777 / 1.745
F3-C1-F2 / 108.0 / 107.6 / O6-Cl5 / 3.190 / 3.125
H4-C1-F2 / 109.9 / 109.4 / C7-O6 / 1.210 / 1.225
Cl5-C1-F3 / 109.7 / 109.8 / H8-C7 / 1.108 / 1.098
H4-C1-F2-F3 / 119.8 / 118.8 / H9-C7 / 1.108 / 1.098
Cl5-C1-F3-H4 / -120.7 / -121.8 / F3-C1-F2 / 107.7 / 107.3
H4-C1-F2 / 109.6 / 109.2
Cl5-C1-F3 / 109.9 / 109.8
O6-Cl5-C1 / 171.4 / 164.0
C7-O6-Cl5 / 108.5 / 99.1
H8-C7-O6 / 121.7 / 121.6
H9-C7-H8 / 116.4 / 116.8
H4-C1-F2-F3 / 119.2 / 118.2
Cl5-C1-F3-H4 / -121.1 / -122.1
O6-Cl5-C1-F2 / 64.7 / 97.5
C7-O6-Cl5-C1 / -2.4 / -7.2
H8-C7-O6-Cl5 / 179.7 / -177.0
H9-C7-H8-O6 / 180.0 / -179.9

TableTS6

Parameters / BrCFH2 / Parameters / CH2O···BrCFH2
L1 / L2 / L1 / L2
F2-C1 / 1.371 / 1.381 / F2-C1 / 1.378 / 1.388
H3-C1 / 1.088 / 1.084 / H3-C1 / 1.089 / 1.085
H4-C1 / 1.088 / 1.084 / H4-C1 / 1.089 / 1.085
Br5-C1 / 1.960 / 1.940 / Br5-C1 / 1.947 / 1.929
H3-C1-F2 / 109.3 / 108.9 / O6-Br5 / 3.132 / 3.113
H4-C1-F2 / 109.3 / 108.9 / C7-O6 / 1.210 / 1.225
Br5-C1-H3 / 106.9 / 107.6 / H8-C7 / 1.108 / 1.098
H4-C1-F2-H3 / 125.1 / 124.3 / H9-C7 / 1.108 / 1.098
Br5-C1-H3-H4 / -117.8 / -119.0 / H3-C1-F2 / 108.7 / 108.3
H4-C1-F2 / 108.7 / 108.3
Br5-C1-H3 / 107.7 / 108.3
O6-Br5-C1 / 170.1 / 170.6
C7-O6-Br5 / 124.4 / 120.7
H8-C7-O6 / 122.0 / 121.9
H9-C7-H8 / 116.3 / 116.6
H4-C1-F2-H3 / 123.1 / 122.5
Br5-C1-H3-H4 / -119.0 / -120.0
O6-Br5-C1-F2 / 157.4 / 170.2
C7-O6-Br5-C1 / 177.2 / 180.0
H8-C7-O6-Br5 / 178.6 / -179.0
H9-C7-H8-O6 / 180.0 / 180.0

TableTS7

Parameters / ClCFH2 / Parameters / CH2O···ClCFH2
L1 / L2 / L1 / L2
F2-C1 / 1.373 / 1.385 / F2-C1 / 1.378 / 1.388
H3-C1 / 1.090 / 1.085 / H3-C1 / 1.091 / 1.096
H4-C1 / 1.090 / 1.085 / H4-C1 / 1.092 / 1.096
Cl5-C1 / 1.793 / 1.760 / Cl5-C1 / 1.767 / 1.777
H3-C1-F2 / 108.8 / 108.0 / O6-Cl5 / 3.017 / 3.117
H4-C1-F2 / 108.8 / 108.0 / C7-O6 / 1.220 / 1.225
Cl5-C1-H3 / 108.0 / 109.0 / H8-C7 / 1.099 / 1.111
H4-C1-F2-H3 / 123.5 / 122.3 / H9-C7 / 1.098 / 1.110
Cl5-C1-H3-H4 / -119.4 / -121.2 / H3-C1-F2 / 108.3 / 108.5
H4-C1-F2 / 108.2 / 108.5
Cl5-C1-H3 / 108.2 / 108.5
O6-Cl5-C1 / 146.80 / 156.8
C7-O6-Cl5 / 88.61 / 91.6
H8-C7-O6 / 120.4 / 121.4
H9-C7-H8 / 116.3 / 117.1
H4-C1-F2-H3 / 120.5 / 123.2
Cl5-C1-H3-H4 / -119.6 / -120.4
O6-Cl5-C1-F2 / 0.005 / 0.9
C7-O6-Cl5-C1 / -0.001 / -0.4
H8-C7-O6-Cl5 / 178.4 / 179.5
H9-C7-H8-O6 / 179.9 / 180.0

TableTS8

Parameters / BrCN / Parameters / CH2O···BrCN
L1 / L2 / L1 / L2
C2-Br1 / 1.784 / 1.784 / C2-Br1 / 1.794 / 1.792
N3-C2 / 1.164 / 1.186 / N3-C2 / 1.164 / 1.185
N3-C2-Br1 / 180.0 / 180.0 / O4-Br1 / 2.854 / 2.864
C5-O4 / 1.212 / 1.226
H6-C5 / 1.107 / 1.097
H7-C5 / 1.106 / 1.097
N3-C2-Br1 / 179.7 / 179.7
O4-Br1-C2 / 174.7 / 175.0
C5-O4-Br1 / 147.2 / 148.7
H6-C5-O4 / 121.8 / 121.6
H7-C5-H6 / 116.6 / 116.9
O4-Br1-C2-N3 / -0.1 / -4.3
C5-O4-Br1-C2 / 179.5 / -176.0
H6-C5-O4-Br1 / -0.03 / -0.1
H7-C5-H6-O4 / -180.0 / -180.0

TableTS9

Parameters / ClCN / Parameters / CH2O···ClCN
L1 / L2 / L1 / L2
C2-Cl1 / 1.645 / 1.637 / C2-Cl1 / 1.646 / 1.636
N3-C2 / 1.164 / 1.185 / N3-C2 / 1.164 / 1.185
N3-C2-Cl1 / 180.0 / 180.0 / O4-Cl1 / 2.947 / 2.936
C5-O4 / 1.211 / 1.225
H6-C5 / 1.107 / 1.097
H7-C5 / 1.107 / 1.098
N3-C2-Cl1 / 179.9 / 179.9
O4-Cl1-C2 / 179.9 / 180.0
C5-O4-Cl1 / 142.1 / 144.8
H6-C5-O4 / 121.6 / 121.5
H7-C5-H6 / 116.5 / 116.8
O4-Cl1-C2-N3 / -56.7 / 110.5
C5-O4-Cl1-C2 / 58.1 / 72.2
H6-C5-O4-Cl1 / -180.0 / 179.8
H7-C5-H6-O4 / 180.0 / 180.0

TableTS10

Parameters / BrCCH / Parameters / CH2O···BrCCH
L1 / L2 / L1 / L2
C2-Br1 / 1.790 / 1.792 / C2-Br1 / 1.794 / 1.796
C3-C2 / 1.208 / 1.221 / C3-C2 / 1.209 / 1.222
H4-C3 / 1.065 / 1.063 / H4-C3 / 1.065 / 1.063
C3-C2-Br1 / 180.0 / 180.0 / O5-Br1 / 2.963 / 2.952
H4-C3-C2 / 180.0 / 179.9 / C6-O5 / 1.211 / 1.225
H4-C3-C2-Br1 / -150.8 / -55.4 / H7-C6 / 1.107 / 1.098
H8-C6 / 1.107 / 1.098
C3-C2-Br1 / 180.0 / 180.0
H4-C3-C2 / 180.0 / 180.0
O5-Br1-C2 / 180.0 / 180.0
C6-O5-Br1 / 180.0 / 179.9
H7-C6-O5 / 121.7 / 121.6
H8-C6-H7 / 116.5 / 116.8
H4-C3-C2-Br1 / -156.0 / 176.0
O5-Br1-C2-C3 / 124.1 / 109.7
C6-O5-Br1-C2 / -40.8 / -78.8
H7-C6-O5-Br1 / 136.1 / -38.4
H8-C6-H7-O5 / 180.0 / -180.0

TableTS11

Parameters / ClCCH / Parameters / CH2O···ClCCH
L1 / L2 / L1 / L2
C2-Cl1 / 1.650 / 1.645 / C2-Cl1 / 1.651 / 1.646
C3-C2 / 1.208 / 1.220 / C3-C2 / 1.209 / 1.221
H4-C3 / 1.065 / 1.063 / H4-C3 / 1.065 / 1.063
C3-C2-Cl1 / 180.0 / 180.0 / O5-Cl1 / 3.070 / 3.044
H4-C3-C2 / 179.9 / 179.9 / C6-O5 / 1.210 / 1.225
H4-C3-C2-Cl1 / -114.4 / -117.9 / H7-C6 / 1.108 / 1.098
H8-C6 / 1.108 / 1.098
C3-C2-Cl1 / 179.9 / 179.4
H4-C3-C2 / 179.9 / 179.3
O5-Cl1-C2 / 177.9 / 166.9
C6-O5-Cl1 / 131.4 / 104.2
H7-C6-O5 / 121.7 / 121.6
H8-C6-H7 / 116.4 / 116.8
H4-C3-C2-Cl1 / -180.0 / -172.0
O5-Cl1-C2-C3 / 0.9 / -172.9
C6-O5-Cl1-C2 / -0.8 / -0.05
H7-C6-O5-Cl1 / 179.9 / 179.9
H8-C6-H7-O5 / 180.0 / 180.0

TableTS12

Parameters / BrCCCN / Parameters / CH2O···BrCCCN
L1 / L2 / L1 / L2
C2-Br1 / 1.774 / 1.779 / C2-Br1 / 1.777 / 1.781
C3-C2 / 1.214 / 1.227 / C3-C2 / 1.215 / 1.228
C4-C3 / 1.368 / 1.371 / C4-C3 / 1.367 / 1.370
N5-C4 / 1.168 / 1.190 / N5-C4 / 1.169 / 1.191
C3-C2-Br1 / 180.0 / 180.0 / O6-Br1 / 2.856 / 2.860
C4-C3-C2 / 180.0 / 180.0 / C7-O6 / 1.211 / 1.226
N5-C4-C3 / 180.0 / 180.0 / H8-C7 / 1.106 / 1.097
C4-C3-C2-Br1 / 140.6 / 149.5 / H9-C7 / 1.106 / 1.097
N5-C4-C3-C2 / 18.6 / 10.1 / C3-C2-Br1 / 179.0 / 179.0
C4-C3-C2 / 180.0 / 179.9
N5-C4-C3 / 180.0 / 180.0
O6-Br1-C2 / 179.8 / 179.9
C7-O6-Br1 / 179.8 / 179.9
H8-C7-O6 / 121.6 / 121.5
H9-C7-H8 / 116.8 / 117.0
C4-C3-C2-Br1 / -178.2 / -179.8
N5-C4-C3-C2 / 1.4 / -175.5
O6-Br1-C2-C3 / -10.8 / 4.4
C7-O6-Br1-C2 / 17.8 / 23.3
H8-C7-O6-Br1 / 50.3 / 91.5
H9-C7-H8-O6 / 180.0 / -180.0

TableTS13

Parameters / ClCCCN / Parameters / CH2O···ClCCCN
L1 / L2 / L1 / L2
C2-Cl1 / 1.636 / 1.632 / C2-Cl1 / 1.636 / 1.632
C3-C2 / 1.213 / 1.226 / C3-C2 / 1.214 / 1.228
C4-C3 / 1.370 / 1.372 / C4-C3 / 1.369 / 1.372
N5-C4 / 1.168 / 1.190 / N5-C4 / 1.168 / 1.190
C3-C2-Cl1 / 180.0 / 180.0 / O6-Cl1 / 2.967 / 2.943
C4-C3-C2 / 180.0 / 180.0 / C7-O6 / 1.211 / 1.225
N5-C4-C3 / 180.0 / 180.0 / H8-C7 / 1.107 / 1.098
C4-C3-C2-Cl1 / -157.9 / -170.8 / H9-C7 / 1.107 / 1.097
N5-C4-C3-C2 / 173.8 / -176.1 / C3-C2-Cl1 / 179.8 / 173.5
C4-C3-C2 / 179.8 / 173.8
N5-C4-C3 / 179.9 / 178.8
O6-Cl1-C2 / 179.6 / 179.1
C7-O6-Cl1 / 147.0 / 147.5
H8-C7-O6 / 121.8 / 121.7
H9-C7-H8 / 116.5 / 116.8
C4-C3-C2-Cl1 / -121.1 / -179.7
N5-C4-C3-C2 / 7.3 / 178.6
O6-Cl1-C2-C3 / -108.6 / -115.2
C7-O6-Cl1-C2 / 167.8 / -123.9
H8-C7-O6-Cl1 / -0.03 / 0.9
H9-C7-H8-O6 / -180.0 / -180.0

Table TS14: Optimized parameters for the halogen-bonded complexes with CH3CHO at B3LYP/6-31++G(d,p) (L1) and MP2/aug-cc-pVDZ (L2) theoretical levels.

Parameters / CH3CHO···BrCF3 / Parameters / CH3CHO···ClCF3
L1 / L2 / L1 / L2
F2-C1 / 1.344 / 1.348 / F2-C1 / 1.341 / 1.346
F3-C1 / 1.343 / 1.348 / F3-C1 / 1.341 / 1.346
F4-C1 / 1.342 / 1.347 / F4-C1 / 1.342 / 1.348
Br5-C1 / 1.934 / 1.918 / Cl5-C1 / 1.763 / 1.735
O6-Br5 / 2.918 / 2.910 / O6-Cl5 / 3.061 / 3.010
C7-O6 / 1.215 / 1.228 / C7-O6 / 1.215 / 1.228
H8-C7 / 1.111 / 1.103 / H8-C7 / 1.112 / 1.103
C9-C7 / 1.502 / 1.498 / C9-C7 / 1.503 / 1.499
H10-C9 / 1.091 / 1.087 / H10-C9 / 1.092 / 1.087
H11-C9 / 1.097 / 1.091 / H11-C9 / 1.097 / 1.091
H12-C9 / 1.097 / 1.091 / H12-C9 / 1.097 / 1.091
F3-C1-F2 / 108.0 / 107.9 / F3-C1-F2 / 108.2 / 107.9
F4-C1-F2 / 108.0 / 107.9 / F4-C1-F2 / 108.1 / 107.8
Br5-C1-F3 / 110.9 / 111.1 / Cl5-C1-F3 / 110.8 / 111.1
O6-Br5-C1 / 173.4 / 172.2 / O6-Cl5-C1 / 179.7 / 177.9
C7-O6-Br5 / 143.0 / 142.6 / C7-O6-Cl5 / 142.7 / 131.7
H8-C7-O6 / 119.7 / 119.7 / H8-C7-O6 / 119.7 / 119.7
C9-C7-H8 / 115.5 / 116.0 / C9-C7-H8 / 115.5 / 116.0
H10-C9-C7 / 111.1 / 110.5 / H10-C9-C7 / 111.0 / 110.6
H11-C9-C7 / 109.4 / 109.4 / H11-C9-C7 / 109.5 / 109.4
H12-C9-C7 / 109.4 / 109.4 / H12-C9-C7 / 109.5 / 109.4
F4-C1-F2-F3 / 116.6 / 116.4 / F4-C1-F2-F3 / 116.8 / 116.2
Br5-C1-F3-F4 / -121.6 / -121.7 / Cl5-C1-F3-F4 / -121.5 / -121.8
O6-Br5-C1-F2 / -131.6 / -118.8 / O6-Cl5-C1-F2 / -43.5 / -117.8
C7-O6-Br5-C1 / -179.6 / 179.7 / C7-O6-Cl5-C1 / -50.6 / -2.5
H8-C7-O6-Br5 / -179.3 / -179.8 / H8-C7-O6-Cl5 / 178.5 / -179.4
C9-C7-H8-O6 / 180.0 / -180.0 / C9-C7-H8-O6 / 180.0 / -179.9
H10-C9-C7-O6 / 0.1 / 0.05 / H10-C9-C7-O6 / -0.1 / 0.3
H11-C9-C7-O6 / 121.8 / 121.5 / H11-C9-C7-O6 / 121.7 / 121.8
H12-C9-C7-O6 / -121.7 / -121.4 / H12-C9-C7-O6 / -121.8 / -121.1

Table TS15

Parameters / CH3CHO···BrCF2H / Parameters / CH3CHO···ClCF2H
L1 / L2 / L1 / L2
F2-C1 / 1.357 / 1.363 / F2-C1 / 1.356 / 1.363
F3-C1 / 1.357 / 1.363 / F3-C1 / 1.355 / 1.364
H4-C1 / 1.090 / 1.086 / H4-C1 / 1.090 / 1.085
Br5-C1 / 1.940 / 1.924 / Cl5-C1 / 1.775 / 1.744
O6-Br5 / 3.014 / 3.018 / O6-Cl5 / 3.209 / 3.124
C7-O6 / 1.215 / 1.228 / C7-O6 / 1.214 / 1.228
H8-C7 / 1.112 / 1.104 / H8-C7 / 1.112 / 1.104
C9-C7 / 1.503 / 1.499 / C9-C7 / 1.504 / 1.499
H10-C9 / 1.091 / 1.087 / H10-C9 / 1.091 / 1.086
H11-C9 / 1.097 / 1.091 / H11-C9 / 1.097 / 1.091
H12-C9 / 1.097 / 1.091 / H12-C9 / 1.097 / 1.091
F3-C1-F2 / 107.6 / 107.4 / F3-C1-F2 / 107.7 / 107.3
H4-C1-F2 / 109.4 / 109.2 / H4-C1-F2 / 109.5 / 109.2
Br5-C1-F3 / 110.2 / 110.1 / Cl5-C1-F3 / 109.9 / 109.9
O6-Br5-C1 / 169.4 / 170.5 / O6-Cl5-C1 / 178.5 / 175.7
C7-O6-Br5 / 139.1 / 127.7 / C7-O6-Cl5 / 132.0 / 121.9
H8-C7-O6 / 119.8 / 119.8 / H8-C7-O6 / 119.8 / 119.7
C9-C7-H8 / 115.5 / 116.1 / C9-C7-H8 / 115.5 / 115.9
H10-C9-C7 / 111.0 / 110.3 / H10-C9-C7 / 111.0 / 110.5
H11-C9-C7 / 109.5 / 109.4 / H11-C9-C7 / 109.4 / 109.4
H12-C9-C7 / 109.4 / 109.5 / H12-C9-C7 / 109.5 / 109.3
H4-C1-F2-F3 / 118.8 / 118.4 / H4-C1-F2-F3 / 119.0 / 118.0
Br5-C1-F3-H4 / -121.0 / -121.6 / Cl5-C1-F3-H4 / -121.2 / -122.2
O6-Br5-C1-F2 / -113.0 / -120.8 / O6-Cl5-C1-F2 / -143.6 / 109.8
C7-O6-Br5-C1 / -175.9 / 179.7 / C7-O6-Cl5-C1 / -169.5 / -23.6
H8-C7-O6-Br5 / 178.3 / -179.8 / H8-C7-O6-Cl5 / 178.4 / -165.5
C9-C7-H8-O6 / -179.9 / 180.0 / C9-C7-H8-O6 / -180.0 / 180.0
H10-C9-C7-O6 / 0.2 / -0.2 / H10-C9-C7-O6 / -0.2 / 0.2
H11-C9-C7-O6 / 122.0 / 121.1 / H11-C9-C7-O6 / 121.5 / 121.7
H12-C9-C7-O6 / -121.4 / -121.6 / H12-C9-C7-O6 / -122.0 / -121.2

Table TS16

Parameters / CH3CHO···BrCFH2 / Parameters / CH3CHO···ClCFH2
L1 / L2 / L1 / L2
F2-C1 / 1.379 / 1.387 / F2-C1 / 1.384 / 1.390
H3-C1 / 1.089 / 1.085 / H3-C1 / 1.091 / 1.096
H4-C1 / 1.089 / 1.085 / H4-C1 / 1.091 / 1.096
Br5-C1 / 1.947 / 1.931 / Cl5-C1 / 1.767 / 1.776
O6-Br5 / 3.085 / 3.097 / O6- Cl5 / 3.014 / 3.165
C7-O6 / 1.214 / 1.227 / C7-O6 / 1.222 / 1.227
H8-C7 / 1.112 / 1.104 / H8-C7 / 1.113 / 1.116
C9-C7 / 1.503 / 1.499 / C9-C7 / 1.512 / 1.507
H10-C9 / 1.091 / 1.086 / H10-C9 / 1.092 / 1.097
H11-C9 / 1.097 / 1.091 / H11-C9 / 1.101 / 1.103
H12-C9 / 1.097 / 1.091 / H12-C9 / 1.099 / 1.103
H3-C1-F2 / 108.6 / 108.3 / H3-C1-F2 / 109.1 / 108.4
H4-C1-F2 / 108.6 / 108.2 / H4-C1-F2 / 109.2 / 108.4
Br5-C1-H3 / 108.3 / 108.8 / Cl5-C1-H3 / 108.3 / 108.5
O6-Br5-C1 / 169.5 / 170.0 / O6- Cl5-C1 / 165.8 / 172.5
C7-O6-Br5 / 135.0 / 122.9 / C7-O6- Cl5 / 117.4 / 115.4
H8-C7-O6 / 119.9 / 119.9 / H8-C7-O6 / 118.7 / 119.8
C9-C7-H8 / 115.4 / 116.0 / C9-C7-H8 / 113.5 / 115.8
H10-C9-C7 / 110.8 / 110.1 / H10-C9-C7 / 109.9 / 110.8
H11-C9-C7 / 109.5 / 109.5 / H11-C9-C7 / 109.5 / 109.1
H12-C9-C7 / 109.4 / 109.5 / H12-C9-C7 / 109.5 / 109.1
H4-C1-F2-H3 / 122.9 / 122.5 / H4-C1-F2-H3 / 121.0 / 123.0
Br5-C1-H3-H4 / -119.1 / -120.1 / Cl5-C1-H3-H4 / -119.4 / -120.4
O6-Br5-C1-F2 / -118.6 / -115.5 / O6- Cl5-C1-F2 / -0.006 / -5.4
C7-O6-Br5-C1 / -174.8 / -174.2 / C7-O6- Cl5-C1 / 5.6 / 3.1
H8-C7-O6-Br5 / -178.9 / -177.7 / H8-C7-O6- Cl5 / 178.6 / 188.3
C9-C7-H8-O6 / -180.0 / 179.9 / C9-C7-H8-O6 / 178.0 / 180.0
H10-C9-C7-O6 / 0.6 / -0.01 / H10-C9-C7-O6 / 0.004 / -0.4
H11-C9-C7-O6 / 122.4 / 121.3 / H11-C9-C7-O6 / 120.4 / 121.4
H12-C9-C7-O6 / -120.9 / -121.3 / H12-C9-C7-O6 / 238.9 / 237.9

Table TS17

Parameters / CH3CHO···BrCN / Parameters / CH3CHO···ClCN
L1 / L2 / L1 / L2
C2-Br1 / 1.798 / 1.795 / C2-Cl1 / 1.647 / 1.638
N3-C2 / 1.164 / 1.186 / N3-C2 / 1.164 / 1.186
O4-Br1 / 2.795 / 2.811 / O4-Cl1 / 2.905 / 2.899
C5-O4 / 1.217 / 1.229 / C5-O4 / 1.216 / 1.228
H6-C5 / 1.110 / 1.103 / H6-C5 / 1.111 / 1.103
C7-C5 / 1.499 / 1.496 / C7-C5 / 1.502 / 1.498
H8-C7 / 1.097 / 1.091 / H8-C7 / 1.097 / 1.091
H9-C7 / 1.097 / 1.091 / H9-C7 / 1.091 / 1.086
H10-C7 / 1.091 / 1.086 / H10-C7 / 1.097 / 1.091
N3-C2-Br1 / 179.7 / 179.7 / N3-C2-Cl1 / 179.8 / 180.0
O4-Br1-C2 / 175.9 / 176.0 / O4-Cl1-C2 / 180.0 / 180.0
C5-O4-Br1 / 140.6 / 144.1 / C5-O4-Cl1 / 138.0 / 138.0
H6-C5-O4 / 119.8 / 119.7 / H6-C5-O4 / 119.8 / 119.7
C7-C5-H6 / 116.0 / 116.3 / C7-C5-H6 / 115.7 / 116.0
H8-C7-C5 / 109.4 / 109.4 / H8-C7-C5 / 109.4 / 109.4
H9-C7-C5 / 109.4 / 109.4 / H9-C7-C5 / 111.0 / 110.4
H10-C7-C5 / 111.0 / 110.4 / H10-C7-C5 / 109.4 / 109.4
O4-Br1-C2-N3 / -1.8 / 1.4 / O4-Cl1-C2-N3 / 92.6 / -145.5
C5-O4-Br1-C2 / -176.8 / 179.4 / C5-O4-Cl1-C2 / 128.2 / 134.1
H6-C5-O4-Br1 / -0.2 / 0.4 / H6-C5-O4-Cl1 / -0.01 / -0.2
C7-C5-H6-O4 / 180.0 / -180.0 / C7-C5-H6-O4 / -180.0 / 180.0
H8-C7-C5-H6 / -58.6 / -58.4 / H8-C7-C5-H6 / 58.4 / 58.6
H9-C7-C5-H6 / 57.7 / 58.6 / H9-C7-C5-H6 / -179.9 / -180.0
H10-C7-C5-H6 / 179.6 / -179.9 / H10-C7-C5-H6 / -58.1 / -58.5

Table TS18

Parameters / CH3CHO···BrCCH / Parameters / CH3CHO···ClCCH
L1 / L2 / L1 / L2
C2-Br1 / 1.795 / 1.796 / C2-Cl1 / 1.651 / 1.646
C3-C2 / 1.209 / 1.222 / C3-C2 / 1.209 / 1.221
H4-C3 / 1.067 / 1.063 / H4-C3 / 1.065 / 1.063
O5-Br1 / 2.926 / 2.918 / O5-Cl1 / 3.055 / 3.023
C6-O5 / 1.215 / 1.228 / C6-O5 / 1.215 / 1.228
H7-C6 / 1.111 / 1.103 / H7-C6 / 1.112 / 1.104
C8-C6 / 1.503 / 1.498 / C8-C6 / 1.504 / 1.499
H9-C8 / 1.093 / 1.087 / H9-C8 / 1.092 / 1.087
H10-C8 / 1.099 / 1.091 / H10-C8 / 1.097 / 1.091
H11-C8 / 1.099 / 1.091 / H11-C8 / 1.097 / 1.091
C3-C2-Br1 / 179.8 / 179.7 / C3-C2-Cl1 / 179.9 / 179.2
H4-C3-C2 / 179.9 / 179.8 / H4-C3-C2 / 179.8 / 179.1
O5-Br1-C2 / 179.5 / 179.7 / O5-Cl1-C2 / 179.2 / 176.1
C6-O5-Br1 / 177.2 / 179.9 / C6-O5-Cl1 / 141.7 / 127.2
H7-C6-O5 / 119.7 / 119.7 / H7-C6-O5 / 119.7 / 119.7
C8-C6-H7 / 115.8 / 116.1 / C8-C6-H7 / 115.5 / 116.0
H9-C8-C6 / 111.0 / 110.4 / H9-C8-C6 / 111.0 / 110.5
H10-C8-C6 / 109.5 / 109.4 / H10-C8-C6 / 109.5 / 109.4
H11-C8-C6 / 109.5 / 109.4 / H11-C8-C6 / 109.5 / 109.3
H4-C3-C2-Br1 / 179.7 / 173.2 / H4-C3-C2-Cl1 / 179.6 / 176.0
O5-Br1-C2-C3 / 0.2 / -171.6 / O5-Cl1-C2-C3 / 1.0 / -160.6
C6-O5-Br1-C2 / 0.4 / 164.6 / C6-O5-Cl1-C2 / -0.5 / -17.3
H7-C6-O5-Br1 / -0.9 / 9.8 / H7-C6-O5-Cl1 / 179.5 / 179.1
C8-C6-H7-O5 / -180.0 / -180.0 / C8-C6-H7-O5 / -180.0 / -179.9
H9-C8-C6-O5 / 0.0 / 0.3 / H9-C8-C6-O5 / 0.0 / 0.8
H10-C8-C6-O5 / 121.7 / 121.8 / H10-C8-C6-O5 / 121.8 / 122.3
H11-C8-C6-O5 / -121.7 / -121.1 / H11-C8-C6-O5 / -121.7 / -120.5

Table TS19

Parameters / CH3CHO···BrCCCN / Parameters / CH3CHO···ClCCCN
L1 / L2 / L1 / L2
C2-Br1 / 1.777 / 1.781 / C2-Cl1 / 1.636 / 1.633
C3-C2 / 1.215 / 1.228 / C3-C2 / 1.214 / 1.228
C4-C3 / 1.367 / 1.370 / C4-C3 / 1.369 / 1.372
N5-C4 / 1.169 / 1.191 / N5-C4 / 1.168 / 1.190
O6-Br1 / 2.819 / 2.824 / O6-Cl1 / 2.927 / 2.908
C7-O6 / 1.217 / 1.229 / C7-O6 / 1.216 / 1.228
H8-C7 / 1.110 / 1.102 / H8-C7 / 1.111 / 1.104
C9-C7 / 1.501 / 1.497 / C9-C7 / 1.502 / 1.498
H10-C9 / 1.091 / 1.086 / H10-C9 / 1.091 / 1.086
H11-C9 / 1.097 / 1.091 / H11-C9 / 1.097 / 1.091
H12-C9 / 1.097 / 1.091 / H12-C9 / 1.097 / 1.091
C3-C2-Br1 / 179.0 / 179.0 / C3-C2-Cl1 / 179.0 / 173.6
C4-C3-C2 / 180.0 / 179.9 / C4-C3-C2 / 179.6 / 174.0
N5-C4-C3 / 180.0 / 180.0 / N5-C4-C3 / 179.9 / 178.9
O6-Br1-C2 / 179.9 / 179.9 / O6-Cl1-C2 / 179.5 / 179.1
C7-O6-Br1 / 179.8 / 179.7 / C7-O6-Cl1 / 142.1 / 135.9
H8-C7-O6 / 119.6 / 119.5 / H8-C7-O6 / 119.8 / 119.7
C9-C7-H8 / 115.9 / 116.3 / C9-C7-H8 / 115.7 / 116.0
H10-C9-C7 / 111.1 / 110.5 / H10-C9-C7 / 111.0 / 110.4
H11-C9-C7 / 109.3 / 109.4 / H11-C9-C7 / 109.4 / 109.4
H12-C9-C7 / 109.5 / 109.3 / H12-C9-C7 / 109.4 / 109.3
C4-C3-C2-Br1 / 162.7 / -178.1 / C4-C3-C2-Cl1 / -170.9 / 179.8
N5-C4-C3-C2 / 0.9 / 178.6 / N5-C4-C3-C2 / 149.1 / -179.4
O6-Br1-C2-C3 / 118.0 / -156.3 / O6-Cl1-C2-C3 / -95.8 / -164.1
C7-O6-Br1-C2 / 164.7 / 60.7 / C7-O6-Cl1-C2 / 170.0 / -7.4
H8-C7-O6-Br1 / 108.3 / 107.1 / H8-C7-O6-Cl1 / -0.03 / 0.03
C9-C7-H8-O6 / -179.9 / -180.0 / C9-C7-H8-O6 / 180.0 / -179.9
H10-C9-C7-O6 / -0.4 / 0.1 / H10-C9-C7-O6 / -0.04 / 1.0
H11-C9-C7-O6 / 121.3 / 121.6 / H11-C9-C7-O6 / 121.7 / 122.5
H12-C9-C7-O6 / -122.3 / -121.4 / H12-C9-C7-O6 / -121.8 / -120.4

Table TS20: The percentage s-character of C hybrid of C-X bond in monomers and complexesat MP2/aug-cc-pVDZ level.

Monomers / %s (C) / Complexes / %s (C)
BrCF3 / 27.05 / CH2O···BrCF3
CH3CHO···BrCF3 / 27.93
28.11
ClCF3 / 27.72 / CH2O···ClCF3
CH3CHO···ClCF3 / 28.22
28.35
BrCF2H / 23.85 / CH2O···BrCF2H
CH3CHO···BrCF2H / 24.31
24.43
ClCF2H / 24.25 / CH2O···ClCF2H
CH3CHO···ClCF2H / 24.89
25.00
BrCFH2 / 20.84 / CH2O···BrCFH2
CH3CHO···BrCFH2 / 21.34
21.46
ClCFH2 / 21.19 / CH2O···ClCFH2
CH3CHO···ClCFH2 / 21.63
21.75
BrCN / 47.51 / CH2O···BrCN
CH3CHO···BrCN / 48.86
49.15
ClCN / 46.37 / CH2O···ClCN
CH3CHO···ClCN / 47.31
47.48
BrCCH / 41.80 / CH2O···BrCCH
CH3CHO···BrCCH / 42.85
42.98
ClCCH / 40.93 / CH2O···ClCCH
CH3CHO···ClCCH / 41.69
41.88
BrCCCN / 43.05 / CH2O···BrCCCN
CH3CHO···BrCCCN / 44.17
44.31
ClCCCN / 41.75 / CH2O···ClCCCN
CH3CHO···ClCCCN / 42.71
42.89

Table TS21: Atomic charges (NPA) obtained using NBO analysis at MP2/aug-cc-pVDZ level.

Complexes / Atomic
charges
CH2O···BrCF3
CH3CHO···BrCF3 / qO(qBr) / -0.629 (0.109)
-0.661 (0.112)
CH2O···ClCF3
CH3CHO···ClCF3 / qO(qCl) / -0.618 (0.041)
-0.651 (0.048)
CH2O···BrCF2H
CH3CHO···BrCF2H / qO(qBr) / -0.621 (0.049)
-0.650 (0.049)
CH2O···ClCF2H
CH3CHO···ClCF2H / qO(qCl) / -0.614 (-0.013)
-0.645 (-0.005)
CH2O···BrCFH2
CH3CHO···BrCFH2 / qO(qBr) / -0.613 (0.008)
-0.642 (0.010)
CH2O···ClCFH2
CH3CHO···ClCFH2 / qO(qCl) / -0.614 (-0.064)
-0.640 (-0.057)
CH2O···BrCN
CH3CHO···BrCN / qO(qBr) / -0.643 (0.257)
-0.674 (0.260)
CH2O···ClCN
CH3CHO···ClCN / qO(qCl) / -0.632 (0.167)
-0.661 (0.170)
CH2O···BrCCH
CH3CHO···BrCCH / qO(qBr) / -0.631 (0.230)
-0.662 (0.234)
CH2O···ClCCH
CH3CHO···ClCCH / qO(qCl) / -0.615 (0.131)
-0.646 (0.137)
CH2O···BrCCCN
CH3CHO···BrCCCN / qO(qBr) / -0.646 (0.290)
-0.678 (0.294)
CH2O···ClCCCN
CH3CHO···ClCCCN / qO(qCl) / -0.631 (0.191)
-0.659 (0.194)

Table TS22: The differences of the halogen bonding distances between the values in the complex and in the isolated X-Y molecule for C-X (X=Br, Cl) bond and for C=O bond of carbonyl molecules at MP2/aug-cc-pVDZ level.

Adduct / Δd (C-X) / Δd (C=O)
CH2O···BrCF3
CH3CHO···BrCF3 / -0.005
-0.002 / +0.001
+0.001
CH2O···ClCF3
CH3CHO···ClCF3 / -0.004
-0.006 / +0.001
+0.001
CH2O···BrCF2H
CH3CHO···BrCF2H / -0.011
-0.008 / +0.001
+0.001
CH2O···ClCF2H
CH3CHO···ClCF2H] / -0.004
-0.005 / +0.001
+0.001
CH2O···BrCFH2
CH3CHO···BrCFH2 / -0.011
-0.009 / +0.001
+0.001
CH2O···ClCFH2
CH3CHO···ClCFH2 / -0.004
-0.005 / +0.001
+0.001
CH2O···BrCN
CH3CHO···BrCN / +0.008
+0.011 / +0.002
+0.002
CH2O···ClCN
CH3CHO···ClCN / -0.001
+0.001 / +0.001
+0.001
CH2O···BrCCH
CH3CHO-BrCCH / +0.004
+0.004 / +0.001
+0.001
CH2O···ClCCH
CH3CHO···ClCCH / +0.001
+0.001 / +0.001
+0.001
CH2O···BrCCCN
CH3CHO···BrCCCN / +0.002
+0.002 / +0.002
+0.002
CH2O···ClCCCN
CH3CHO···ClCCCN / 0.00
+0.001 / +0.001
+0.001

Figure S1: Correlation between halogen-bonded interaction energies of the complexes with SAPT interaction energiesat MP2/aug-cc-pVDZ level.

Table TS23: Optimized parameters for theICF3, CH2O···ClCF3and CH3CHO···ICF3at MP2/aug-cc-pVDZ-PP theoretical level.

Parameters / ICF3 / Parameters / CH2O···ICF3 / Parameters / CH3CHO···ICF3
F2-C1 / 1.347 / F2-C1 / 1.352 / F2-C1 / 1.353
F3-C1 / 1.348 / F3-C1 / 1.353 / F3-C1 / 1.353
F4-C1 / 1.348 / F4-C1 / 1.352 / F4-C1 / 1.352
I5-C1 / 2.143 / I5-C1 / 2.141 / I5-C1 / 2.140
F3-C1-F2 / 108.2 / O6-I5 / 2.963 / O6-I5 / 2.941
F4-C1-F2 / 108.2 / C7-O6 / 1.227 / C7-O6 / 1.229
I5-C1-F3 / 110.7 / H8-C7 / 1.109 / H8-C7 / 1.114
F4-C1-F2-F3 / 117.1 / H9-C7 / 1.110 / C9-C7 / 1.504
I5-C1-F3-F4 / -121.5 / F3-C1-F2 / 107.7 / H10-C9 / 1.098
F4-C1-F2 / 107.7 / H11-C9 / 1.103
I5-C1-F3 / 111.1 / H12-C9 / 1.103
O6-I5-C1 / 172.6 / F3-C1-F2 / 107.6
C7-O6-I5 / 109.0 / F4-C1-F2 / 107.6
H8-C7-O6 / 121.3 / I5-C1-F3 / 111.3
H9-C7-H8 / 117.4 / O6-I5-C1 / 179.7
F4-C1-F2-F3 / 115.9 / C7-O6-I5 / 125.9
I5-C1-F3-F4 / -122.0 / H8-C7-O6 / 119.2
O6-I5-C1-F2 / 119.8 / C9-C7-H8 / 116.1
C7-O6-I5-C1 / -0.1 / H10-C9-C7 / 111.2
H8-C7-O6-I5 / 180.0 / H11-C9-C7 / 109.0
H9-C7-H8-O6 / 180.0 / H12-C9-C7 / 109.0
F4-C1-F2-F3 / 115.8
I5-C1-F3-F4 / -122.1
O6-I5-C1-F2 / 55.7
C7-O6-I5-C1 / 8.5
H8-C7-O6-I5 / 179.7
C9-C7-H8-O6 / -180.0
H10-C9-C7-O6 / -0.05
H11-C9-C7-O6 / 121.7
H12-C9-C7-O6 / -121.9

Table TS24: Optimized parameters for ICF2H, CH2O···ICF2H and CH3CHO···ICF2H at MP2/aug-cc-pVDZ-PP theoretical level.

Parameters / ICF2H / Parameters / CH2O···ICF2H / Parameters / CH3CHO···ICF2H
F2-C1 / 1.363 / F2-C1 / 1.368 / F2-C1 / 1.369
F3-C1 / 1.363 / F3-C1 / 1.369 / F3-C1 / 1.369
H4-C1 / 1.097 / H4-C1 / 1.097 / H4-C1 / 1.097
I5-C1 / 2.151 / I5-C1 / 2.146 / I5-C1 / 2.145
F3-C1-F2 / 107.9 / O6-I5 / 3.026 / O6-I5 / 3.044
H4-C1-F2 / 109.8 / C7-O6 / 1.226 / C7-O6 / 1.229
I5-C1-F3 / 109.8 / H8-C7 / 1.109 / H8-C7 / 1.115
H4-C1-F2-F3 / 119.7 / H9-C7 / 1.110 / C9-C7 / 1.505
I5-C1-F3-H4 / -120.7 / F3-C1-F2 / 107.6 / H10-C9 / 1.098
H4-C1-F2 / 109.3 / H11-C9 / 1.103
I5-C1-F3 / 110.1 / H12-C9 / 1.103
O6-I5-C1 / 171.3 / F3-C1-F2 / 107.5
C7-O6-I5 / 107.2 / H4-C1-F2 / 109.2
H8-C7-O6 / 121.3 / I5-C1-F3 / 110.2
H9-C7-H8 / 117.3 / O6-I5-C1 / 178.7
H4-C1-F2-F3 / 118.5 / C7-O6-I5 / 124.5
I5-C1-F3-H4 / -121.4 / H8-C7-O6 / 119.4
O6-I5-C1-F2 / 133.2 / C9-C7-H8 / 116.1
C7-O6-I5-C1 / -8.8 / H10-C9-C7 / 110.9
H8-C7-O6-I5 / 177.3 / H11-C9-C7 / 109.0
H9-C7-H8-O6 / 179.8 / H12-C9-C7 / 109.1
H4-C1-F2-F3 / 118.3
I5-C1-F3-H4 / -121.6
O6-I5-C1-F2 / 77.2
C7-O6-I5-C1 / -17.6
H8-C7-O6-I5 / 179.1
C9-C7-H8-O6 / 179.9
H10-C9-C7-O6 / -0.9
H11-C9-C7-O6 / 120.7
H12-C9-C7-O6 / -122.8

Table TS25: Optimized parameters for ICFH2, CH2O···ICFH2 and CH3CHO···ICFH2 at MP2/aug-cc-pVDZ-PP theoretical level.

Parameters / ICFH2 / Parameters / CH2O···ICFH2 / Parameters / CH3CHO···ICFH2
F2-C1 / 1.387 / F2-C1 / 1.393 / F2-C1 / 1.394
H3-C1 / 1.096 / H3-C1 / 1.096 / H3-C1 / 1.096
H4-C1 / 1.096 / H4-C1 / 1.096 / H4-C1 / 1.096
I5-C1 / 2.150 / I5-C1 / 2.147 / I5-C1 / 2.147
H3-C1-F2 / 109.1 / O6-I5 / 3.111 / O6-I5 / 3.104
H4-C1-F2 / 109.1 / C7-O6 / 1.226 / C7-O6 / 1.228
I5-C1-H3 / 107.5 / H8-C7 / 1.110 / H8-C7 / 1.115
H4-C1-F2-H3 / 124.3 / H9-C7 / 1.111 / C9-C7 / 1.506
I5-C1-H3-H4 / -118.6 / H3-C1-F2 / 108.8 / H10-C9 / 1.098
H4-C1-F2 / 108.7 / H11-C9 / 1.103
I5-C1-H3 / 108.0 / H12-C9 / 1.103
O6-I5-C1 / 171.1 / H3-C1-F2 / 108.7
C7-O6-I5 / 104.6 / H4-C1-F2 / 108.7
H8-C7-O6 / 121.4 / I5-C1-H3 / 108.2
H9-C7-H8 / 117.3 / O6-I5-C1 / 177.5
H4-C1-F2-H3 / 123.2 / C7-O6-I5 / 122.9
I5-C1-H3-H4 / -119.3 / H8-C7-O6 / 119.5
O6-I5-C1-F2 / 49.7 / C9-C7-H8 / 116.0
C7-O6-I5-C1 / -15.2 / H10-C9-C7 / 110.9
H8-C7-O6-I5 / -179.0 / H11-C9-C7 / 109.1
H9-C7-H8-O6 / -180.0 / H12-C9-C7 / 109.1
H4-C1-F2-H3 / 123.0
I5-C1-H3-H4 / -119.5
O6-I5-C1-F2 / 0.9
C7-O6-X5-C1 / -0.9
H8-C7-O6-I5 / 179.9
C9-C7-H8-O6 / 180.0
H10-C9-C7-O6 / 0.01
H11-C9-C7-O6 / 121.7
H12-C9-C7-O6 / -121.7

Table TS26: Optimized parameters for ICN, CH2O···ICN and CH3CHO···ICN at MP2/aug-cc-pVDZ-PP theoretical level.

Parameters / ICN / Parameters / CH2O···ICN / Parameters / CH3CHO···ICN
C2-I1 / 2.004 / C2-I1 / 2.018 / C2-I1 / 2.021
N3-C2 / 1.193 / N3-C2 / 1.193 / N3-C2 / 1.193
N3-C2-I1 / 180.0 / O4-I1 / 2.855 / O4-I1 / 2.806
C5-O4 / 1.228 / C5-O4 / 1.231
H6-C5 / 1.110 / H6-C5 / 1.114
H7-C5 / 1.108 / C7-C5 / 1.500
N3-C2-I1 / 179.8 / H8-C7 / 1.103
O4-I1-C2 / 174.9 / H9-C7 / 1.103
C5-O4-I1 / 114.2 / H10-C7 / 1.097
H6-C5-O4 / 121.4 / N3-C2-I1 / 179.7
H7-C5-H6 / 117.5 / O4-I1-C2 / 175.0
O4-I1-C2-N3 / -0.40 / C5-O4-I1 / 113.1
C5-O4-I1-C2 / -0.04 / H6-C5-O4 / 119.4
H6-C5-O4-I1 / 0.02 / C7-C5-H6 / 116.6
H7-C5-H6-O4 / -180.0 / H8-C7-C5 / 109.0
H9-C7-C5 / 109.0
H10-C7-C5 / 110.8
O4-I1-C2-N3 / -0.8
C5-O4-I1-C2 / 0.3
H6-C5-O4-I1 / -0.1
C7-C5-H6-O4 / 180.0
H8-C7-C5-H6 / -58.3
H9-C7-C5-H6 / 58.1
H10-C7-C5-H6 / 179.9

Table TS27: Optimized parameters for ICCH, CH2O···ICCH and CH3CHO···ICCH at MP2/aug-cc-pVDZ-PP theoretical level.

Parameters / ICCH / Parameters / CH2O···ICCH / Parameters / CH3CHO···ICCH
C2-I1 / 2.002 / C2-I1 / 2.008 / C2-I1 / 2.014
C3-C2 / 1.236 / C3-C2 / 1.236 / C3-C2 / 1.237
H4-C3 / 1.075 / H4-C3 / 1.074 / H4-C3 / 1.074
C3-C2-I1 / 179.9 / O5-I1 / 2.999 / O5-I1 / 2.922
H4-C3-C2 / 179.9 / C6-O5 / 1.225 / C6-O5 / 1.230
H4-C3-C2-I1 / -163.2 / H7-C6 / 1.110 / H7-C6 / 1.114
H8-C6 / 1.110 / C8-C6 / 1.504
C3-C2-I1 / 180.0 / H9-C8 / 1.098
H4-C3-C2 / 180.0 / H10-C8 / 1.103
O5-I1-C2 / 180.0 / H11-C8 / 1.103
C6-O5-I1 / 179.9 / C3-C2-I1 / 179.8
H7-C6-O5 / 121.5 / H4-C3-C2 / 179.7
H8-C6-H7 / 117.1 / O5-I1-C2 / 179.8
H4-C3-C2-I1 / 8.9 / C6-O5-I1 / 126.4
O5-I1-C2-C3 / 99.4 / H7-C6-O5 / 119.2
C6-O5-I1-C2 / -140.0 / C8-C6-H7 / 116.2
H7-C6-O5-I1 / 160.0 / H9-C8-C6 / 111.0
H8-C6-H7-O5 / 180.0 / H10-C8-C6 / 109.0
H11-C8-C6 / 109.0
H4-C3-C2-I1 / -180.0
O5-I1-C2-C3 / -0.9
C6-O5-I1-C2 / 0.2
H7-C6-O5-I1 / -180.0
C8-C6-H7-O5 / 180.0
H9-C8-C6-O5 / -0.01
H10-C8-C6-O5 / 121.7
H11-C8-C6-O5 / -121.8

Table TS28: Optimized parameters for ICCCN, CH2O···ICCCN and CH3CHO···ICCCN at MP2/aug-cc-pVDZ-PP theoretical level.

Parameters / ICCCN / Parameters / CH2O···ICCCN / Parameters / CH3CHO···ICCCN
C2-I1 / 1.990 / C2-I1 / 1.996 / C2-I1 / 2.004
C3-C2 / 1.242 / C3-C2 / 1.243 / C3-C2 / 1.244
C4-C3 / 1.379 / C4-C3 / 1.379 / C4-C3 / 1.379
N5-C4 / 1.195 / N5-C4 / 1.195 / N5-C4 / 1.195
C3-C2-I1 / 180.0 / O6-I1 / 2.932 / O6-I1 / 2.847
C4-C3-C2 / 180.0 / C7-O6 / 1.225 / C7-O6 / 1.231
N5-C4-C3 / 180.0 / H8-C7 / 1.109 / H8-C7 / 1.113
C4-C3-C2-I1 / 147.5 / H9-C7 / 1.109 / C9-C7 / 1.503
N5-C4-C3-C2 / 12.3 / C3-C2-I1 / 180.0 / H10-C9 / 1.098
C4-C3-C2 / 180.0 / H11-C9 / 1.103
N5-C4-C3 / 180.0 / H12-C9 / 1.103
O6-I1-C2 / 180.0 / C3-C2-I1 / 179.6
C7-O6-I1 / 179.7 / C4-C3-C2 / 179.9
H8-C7-O6 / 121.4 / N5-C4-C3 / 179.9
H9-C7-H8 / 117.2 / O6-I1-C2 / 179.5
C4-C3-C2-I1 / 62.7 / C7-O6-I1 / 128.7
N5-C4-C3-C2 / -104.0 / H8-C7-O6 / 119.1
O6-I1-C2-C3 / 117.1 / C9-C7-H8 / 116.4
C7-O6-I1-C2 / 127.9 / H10-C9-C7 / 111.1
H8-C7-O6-I1 / 22.7 / H11-C9-C7 / 109.0
H9-C7-H8-O6 / -180.0 / H12-C9-C7 / 109.0
C4-C3-C2-I1 / 178.7
N5-C4-C3-C2 / -178.3
O6-I1-C2-C3 / -179.6
C7-O6-I1-C2 / 179.5
H8-C7-O6-I1 / -179.9
C9-C7-H8-O6 / 180.0
H10-C9-C7-O6 / -0.02
H11-C9-C7-O6 / 121.8
H12-C9-C7-O6 / -121.8