Electronegativity and resonance parameters from the geometry of monosubstituted benzene rings
Anna Rita Campanelli Aldo Domenicano Marina Macchiagodena Fabio Ramondo
SUPPLEMENTARY MATERIAL
Table S1 Internal coordinates of the benzene ring and net charge transferred from the substituent into the -system of the benzene ring (or viceversa) in PhX molecules, from HF/6-31G* calculationsa,bSubstituentc,d / Molecular
symmetrye / / / / / a / b / c / q
H / D6h / 120.00 / 120.00 / 120.00 / 120.00 / 1.3862 / 1.3862 / 1.3862 / 0.000
Li / C2v / 114.42 / 123.28 / 120.01 / 119.01 / 1.4059 / 1.3880 / 1.3855 / 0.015
BeH / C2v / 116.59 / 121.98 / 119.81 / 119.82 / 1.4015 / 1.3853 / 1.3859 / 0.016
BeCl / C2v / 116.84 / 121.82 / 119.83 / 119.86 / 1.4011 / 1.3850 / 1.3859 / 0.012
BH2(c) / C2v / 117.67 / 121.41 / 119.57 / 120.39 / 1.4002 / 1.3833 / 1.3874 / 0.099
BH2(o) / C2v / 117.93 / 121.10 / 120.19 / 119.48 / 1.3946 / 1.3854 / 1.3853 / 0.010
BF2(c) / C2v / 118.62 / 120.82 / 119.69 / 120.37 / 1.3956 / 1.3837 / 1.3868 / 0.059
BF2(o) / C2v / 118.40 / 120.88 / 120.00 / 119.84 / 1.3933 / 1.3850 / 1.3853 / 0.012
BCl2(c) / C2v / 117.86 / 121.17 / 119.80 / 120.20 / 1.4003 / 1.3824 / 1.3864 / 0.101
BCl2(o) / C2v / 118.60 / 120.73 / 120.06 / 119.82 / 1.3933 / 1.3846 / 1.3854 / 0.014
BH3(o) / Cs / 114.97 / 122.89 / 120.43 / 118.39 / 1.4018 / 1.3869 / 1.3870 / 0.018
CH2(c) / C2v / 119.09 / 120.18 / 118.89 / 122.78 / 1.4366 / 1.3625 / 1.4030 / 0.551
CH2(o) / C2v / 122.08 / 118.29 / 120.44 / 120.46 / 1.3934 / 1.3836 / 1.3859 / 0.005
CH2(c) / C2v / 113.13 / 122.54 / 122.85 / 116.08 / 1.4483 / 1.3692 / 1.3995 / 0.524
CH2(o) / C2v / 113.63 / 123.57 / 120.44 / 118.34 / 1.4119 / 1.3877 / 1.3870 / 0.018
CH2(p') / Cs / 114.48 / 123.10 / 120.53 / 118.25 / 1.4062 / 1.3866 / 1.3873 / 0.035
Me(o) / Cs / 118.27 / 120.97 / 120.21 / 119.38 / 1.3902 / 1.3854 / 1.3852 / 0.009
CMe3(c) / Cs / 117.15 / 121.54 / 120.41 / 118.95 / 1.3937 / 1.3855 / 1.3839 / 0.006
CMe3(o) / Cs / 117.01 / 121.61 / 120.45 / 118.88 / 1.3940 / 1.3855 / 1.3835 / 0.006
CF3(o) / Cs / 120.27 / 119.79 / 120.04 / 120.08 / 1.3864 / 1.3844 / 1.3856 / 0.020
CCl3(c) / Cs / 119.19 / 120.31 / 120.32 / 119.55 / 1.3893 / 1.3841 / 1.3842 / 0.013
CCl3(o) / Cs / 119.08 / 120.35 / 120.35 / 119.50 / 1.3898 / 1.3841 / 1.3840 / 0.014
CHCH2(c) / Cs / 118.09 / 121.02 / 120.23 / 119.43 / 1.3935 / 1.3837 / 1.3855 / 0.006
CHCH2(o) / Cs / 118.71 / 120.68 / 120.17 / 119.59 / 1.3907 / 1.3856 / 1.3853 / 0.003
Ph(c) / D2h / 116.79 / 121.68 / 120.53 / 118.80 / 1.3962 / 1.3838 / 1.3836 / 0.000
Ph(o) / D2d / 118.72 / 120.67 / 120.16 / 119.62 / 1.3910 / 1.3857 / 1.3853 / 0.001
Ph(e) / D2 / 118.33 / 120.86 / 120.24 / 119.47 / 1.3928 / 1.3847 / 1.3853 / 0.000
CHNH(c) / Cs / 119.32 / 120.36 / 119.98 / 120.00 / 1.3907 / 1.3838 / 1.3865 / 0.035
CHNH(o) / Cs / 119.29 / 120.35 / 120.12 / 119.75 / 1.3885 / 1.3853 / 1.3854 / 0.002
CHO(c) / Cs / 119.94 / 120.06 / 119.76 / 120.43 / 1.3899 / 1.3834 / 1.3873 / 0.058
CHO(o) / Cs / 119.78 / 120.05 / 120.10 / 119.90 / 1.3879 / 1.3852 / 1.3855 / 0.003
COMe(c) / Cs / 119.13 / 120.47 / 119.95 / 120.04 / 1.3917 / 1.3837 / 1.3861 / 0.050
COMe(o) / Cs / 119.59 / 120.17 / 120.12 / 119.82 / 1.3880 / 1.3853 / 1.3854 / 0.001
COF(c) / Cs / 120.29 / 119.76 / 119.87 / 120.44 / 1.3904 / 1.3829 / 1.3868 / 0.060
COF(o) / Cs / 120.43 / 119.66 / 120.09 / 120.08 / 1.3867 / 1.3846 / 1.3856 / 0.007
COCl(c) / Cs / 119.89 / 119.95 / 119.97 / 120.26 / 1.3918 / 1.3825 / 1.3862 / 0.067
COCl(o) / Cs / 120.63 / 119.53 / 120.11 / 120.09 / 1.3862 / 1.3846 / 1.3856 / 0.007
CONH2(e) / C1 / 119.47 / 120.26 / 119.99 / 120.03 / 1.3901 / 1.3841 / 1.3860 / 0.037
COO(c) / C2v / 118.34 / 120.99 / 120.13 / 119.42 / 1.3900 / 1.3868 / 1.3870 / 0.008
COO(o) / C2v / 117.73 / 121.26 / 120.41 / 118.93 / 1.3919 / 1.3856 / 1.3867 / 0.027
COOH(c) / Cs / 120.03 / 119.92 / 119.91 / 120.31 / 1.3901 / 1.3833 / 1.3865 / 0.054
COOH(o) / Cs / 120.16 / 119.84 / 120.10 / 119.97 / 1.3864 / 1.3849 / 1.3855 / 0.005
COOMe(c) / Cs / 119.91 / 119.99 / 119.94 / 120.23 / 1.3901 / 1.3837 / 1.3864 / 0.050
COOMe(o) / Cs / 120.04 / 119.91 / 120.11 / 119.92 / 1.3865 / 1.3849 / 1.3855 / 0.004
CCH / C2v / 119.40 / 120.19 / 120.16 / 119.90 / 1.3925 / 1.3835 / 1.3861 / 0.013
CN / C2v / 120.47 / 119.58 / 120.02 / 120.32 / 1.3905 / 1.3831 / 1.3865 / 0.031
NH2(c) / C2v / 118.53 / 120.38 / 121.10 / 118.51 / 1.3957 / 1.3826 / 1.3858 / 0.130
NH2(o) / C2v / 118.65 / 120.75 / 120.11 / 119.63 / 1.3903 / 1.3858 / 1.3855 / 0.004
NH2(p) / Cs / 118.73 / 120.39 / 120.87 / 118.75 / 1.3926 / 1.3834 / 1.3856 / 0.097
NH2(p') / Cs / 119.01 / 120.53 / 120.17 / 119.58 / 1.3885 / 1.3857 / 1.3856 / 0.011
NF2(p) / Cs / 121.31 / 119.00 / 120.48 / 119.72 / 1.3837 / 1.3845 / 1.3851 / 0.018
NF2(p') / Cs / 121.82 / 118.92 / 119.97 / 120.40 / 1.3817 / 1.3844 / 1.3867 / 0.021
NCl2(p) / Cs / 119.37 / 119.94 / 120.95 / 118.85 / 1.3900 / 1.3843 / 1.3831 / 0.051
NCl2(p') / Cs / 120.95 / 119.38 / 120.08 / 120.12 / 1.3843 / 1.3847 / 1.3861 / 0.010
NHCOMe(c) / Cs / 119.32 / 119.98 / 120.91 / 118.90 / 1.3918 / 1.3841 / 1.3845 / 0.065
NHCOMe(o) / Cs / 119.83 / 120.08 / 120.07 / 119.86 / 1.3857 / 1.3851 / 1.3855 / 0.001
NH3(o) / Cs / 123.22 / 118.00 / 120.12 / 120.53 / 1.3793 / 1.3851 / 1.3866 / 0.003
NO2(c) / C2v / 122.33 / 118.51 / 120.09 / 120.47 / 1.3831 / 1.3833 / 1.3866 / 0.051
NO2(o) / C2v / 122.92 / 118.20 / 120.19 / 120.31 / 1.3780 / 1.3850 / 1.3861 / 0.009
NC / C2v / 120.89 / 119.29 / 120.31 / 119.92 / 1.3867 / 1.3837 / 1.3860 / 0.008
N2 / C2v / 125.17 / 116.65 / 119.94 / 121.66 / 1.3896 / 1.3786 / 1.3915 / 0.115
O / C2v / 113.66 / 122.51 / 122.18 / 116.96 / 1.4391 / 1.3756 / 1.3945 / 0.327
OH(c) / Cs / 120.12 / 119.63 / 120.76 / 119.10 / 1.3870 / 1.3842 / 1.3857 / 0.083
OH(o) / Cs / 120.34 / 119.68 / 120.35 / 119.60 / 1.3848 / 1.3855 / 1.3859 / 0.036
OMe(c) / Cs / 119.75 / 119.77 / 120.87 / 118.97 / 1.3897 / 1.3845 / 1.3852 / 0.084
OMe(o) / Cs / 120.30 / 119.69 / 120.36 / 119.59 / 1.3855 / 1.3854 / 1.3860 / 0.038
OH2(c) / C2v / 126.29 / 116.13 / 120.44 / 120.57 / 1.3693 / 1.3877 / 1.3864 / 0.019
OH2(o) / C2v / 126.19 / 116.25 / 120.14 / 121.03 / 1.3725 / 1.3864 / 1.3879 / 0.005
OH2(p) / Cs / 126.30 / 116.14 / 120.38 / 120.66 / 1.3698 / 1.3875 / 1.3867 / 0.015
OH2(p') / Cs / 126.26 / 116.20 / 120.16 / 121.00 / 1.3722 / 1.3865 / 1.3879 / 0.003
F / C2v / 122.35 / 118.46 / 120.50 / 119.71 / 1.3782 / 1.3857 / 1.3863 / 0.052
Na / C2v / 114.34 / 123.31 / 120.09 / 118.85 / 1.4056 / 1.3888 / 1.3855 / 0.010
MgCl / C2v / 116.18 / 122.21 / 119.93 / 119.54 / 1.4016 / 1.3866 / 1.3852 / 0.012
SiH2(c) / C2v / 119.17 / 120.21 / 119.43 / 121.54 / 1.4155 / 1.3741 / 1.3931 / 0.212
SiH2(o) / C2v / 119.92 / 119.76 / 119.91 / 120.74 / 1.4011 / 1.3813 / 1.3875 / 0.034
SiH2(c) / C2v / 114.90 / 122.39 / 121.44 / 117.44 / 1.4148 / 1.3789 / 1.3907 / 0.252
SiH2(o) / C2v / 115.36 / 122.61 / 120.24 / 118.93 / 1.4030 / 1.3888 / 1.3850 / 0.010
SiH2(p) / Cs / 115.42 / 122.59 / 120.47 / 118.47 / 1.4010 / 1.3861 / 1.3868 / 0.048
SiH2(p') / Cs / 115.56 / 122.59 / 120.22 / 118.82 / 1.3997 / 1.3881 / 1.3861 / 0.003
SiH3(o) / Cs / 117.85 / 121.22 / 119.94 / 119.83 / 1.3957 / 1.3853 / 1.3855 / 0.015
SiMe3(o) / Cs / 117.19 / 121.61 / 119.99 / 119.62 / 1.3970 / 1.3857 / 1.3851 / 0.015
SiPh3(e) / S4 / 117.38 / 121.46 / 120.02 / 119.67 / 1.3975 / 1.3858 / 1.3852 / 0.020
SiF3(o) / Cs / 118.69 / 120.70 / 119.83 / 120.25 / 1.3958 / 1.3840 / 1.3860 / 0.018
SiCl3(o) / Cs / 118.60 / 120.70 / 119.94 / 120.12 / 1.3965 / 1.3839 / 1.3855 / 0.031
PH2(c) / C2v / 119.06 / 120.22 / 120.70 / 119.11 / 1.3928 / 1.3836 / 1.3853 / 0.095
PH2(o) / C2v / 118.66 / 120.67 / 119.96 / 120.08 / 1.3957 / 1.3849 / 1.3856 / 0.023
PH2(p) / Cs / 118.56 / 120.73 / 120.23 / 119.51 / 1.3914 / 1.3853 / 1.3851 / 0.024
PH2(p') / Cs / 118.52 / 120.81 / 120.01 / 119.82 / 1.3925 / 1.3855 / 1.3854 / 0.007
PCl2(p) / Cs / 119.04 / 120.37 / 120.21 / 119.79 / 1.3931 / 1.3843 / 1.3848 / 0.005
PCl2(p') / Cs / 119.59 / 120.16 / 119.90 / 120.29 / 1.3924 / 1.3840 / 1.3862 / 0.030
PH3(o) / Cs / 121.02 / 119.18 / 119.88 / 120.87 / 1.3957 / 1.3811 / 1.3881 / 0.044
S / C2v / 115.64 / 122.14 / 121.06 / 117.96 / 1.4065 / 1.3832 / 1.3880 / 0.153
SH(c) / Cs / 119.53 / 120.05 / 120.51 / 119.35 / 1.3889 / 1.3846 / 1.3850 / 0.064
SH(o) / Cs / 119.68 / 120.10 / 120.10 / 119.91 / 1.3888 / 1.3855 / 1.3855 / 0.008
SMe(c) / Cs / 119.07 / 120.28 / 120.59 / 119.19 / 1.3907 / 1.3847 / 1.3848 / 0.072
SMe(o) / Cs / 119.37 / 120.28 / 120.09 / 119.88 / 1.3900 / 1.3855 / 1.3856 / 0.007
SO2Me(o) / Cs / 121.26 / 119.15 / 119.98 / 120.48 / 1.3871 / 1.3843 / 1.3865 / 0.015
SO2Cl(o) / Cs / 122.12 / 118.61 / 119.98 / 120.70 / 1.3864 / 1.3833 / 1.3868 / 0.023
Cl / C2v / 121.28 / 119.07 / 120.42 / 119.75 / 1.3831 / 1.3853 / 1.3855 / 0.045
ClO(c) / Cs / 123.29 / 117.87 / 120.40 / 120.18 / 1.3786 / 1.3857 / 1.3860 / 0.043
ClO3(o) / Cs / 124.26 / 117.33 / 120.16 / 120.77 / 1.3784 / 1.3847 / 1.3866 / 0.004
a Whenever necessary, the geometry of the benzene ring has been made consistent with C2v symmetry by averaging appropriate geometrical parameters.
b Angles are in degrees, bond distances in Å, -charges in electrons. A positive sign of qindicates that electron density is transferred from the -system of the benzene ring into an appropriate orbital of the substituent; a negative sign indicates the opposite transfer.
c The conformation of the substituent with respect to the benzene ring is denoted as (c), (o), (p), (p'), and (e) according to the definitions given in the text (section “The data sets”).
d The substituents which have been used to trace the electronegativity line are identified in bold.
e Symmetry constraint imposed in the optimization of molecular geometry.
Table S2 Internal coordinates of the benzene ring in PhX molecules, from HF/6-311++G** calculationsa,b
Substituentc,d / Molecular
symmetrye / / / / / a / b / c
H / D6h / 120.00 / 120.00 / 120.00 / 120.00 / 1.3862 / 1.3862 / 1.3862
Li / C2v / 114.26 / 123.37 / 120.01 / 118.97 / 1.4068 / 1.3890 / 1.3857
BeH / C2v / 116.63 / 121.94 / 119.84 / 119.81 / 1.4019 / 1.3857 / 1.3859
BeCl / C2v / 116.89 / 121.78 / 119.85 / 119.85 / 1.4010 / 1.3855 / 1.3857
BH2(c) / C2v / 117.68 / 121.38 / 119.58 / 120.39 / 1.4004 / 1.3835 / 1.3872
BH2(o) / C2v / 117.95 / 121.09 / 120.21 / 119.45 / 1.3942 / 1.3856 / 1.3851
BF2(c) / C2v / 118.67 / 120.79 / 119.69 / 120.38 / 1.3954 / 1.3836 / 1.3867
BF2(o) / C2v / 118.55 / 120.80 / 120.00 / 119.86 / 1.3926 / 1.3850 / 1.3852
BCl2(c) / C2v / 117.89 / 121.17 / 119.80 / 120.18 / 1.3995 / 1.3825 / 1.3862
BCl2(o) / C2v / 118.67 / 120.70 / 120.07 / 119.80 / 1.3924 / 1.3849 / 1.3851
BH3(o) / Cs / 115.14 / 122.78 / 120.45 / 118.39 / 1.4021 / 1.3877 / 1.3878
CH2(c) / C2v / 119.15 / 120.15 / 118.86 / 122.82 / 1.4354 / 1.3611 / 1.4023
CH2(o) / C2v / 122.15 / 118.27 / 120.43 / 120.46 / 1.3920 / 1.3833 / 1.3853
CH2(c) / C2v / 113.67 / 122.38 / 122.63 / 116.31 / 1.4438 / 1.3707 / 1.4008
CH2(o) / C2v / 114.48 / 123.04 / 120.54 / 118.36 / 1.4080 / 1.3887 / 1.3866
CH2(p') / Cs / 114.87 / 122.84 / 120.59 / 118.28 / 1.4053 / 1.3878 / 1.3874
Me(o) / Cs / 118.24 / 120.98 / 120.23 / 119.33 / 1.3900 / 1.3856 / 1.3852
CMe3(c) / Cs / 117.11 / 121.56 / 120.43 / 118.90 / 1.3934 / 1.3858 / 1.3838
CMe3(o) / Cs / 116.98 / 121.62 / 120.47 / 118.84 / 1.3938 / 1.3858 / 1.3835
CF3(o) / Cs / 120.40 / 119.71 / 120.05 / 120.07 / 1.3856 / 1.3844 / 1.3853
CCl3(c) / Cs / 119.18 / 120.34 / 120.31 / 119.52 / 1.3884 / 1.3839 / 1.3840
CCl3(o) / Cs / 119.10 / 120.37 / 120.35 / 119.46 / 1.3886 / 1.3839 / 1.3838
CHCH2(c) / Cs / 118.14 / 120.99 / 120.24 / 119.41 / 1.3929 / 1.3838 / 1.3855
CHCH2(o) / Cs / 118.73 / 120.66 / 120.20 / 119.55 / 1.3904 / 1.3858 / 1.3851
Ph(c) / D2h / 116.88 / 121.64 / 120.53 / 118.79 / 1.3954 / 1.3840 / 1.3836
Ph(o) / D2d / 118.78 / 120.64 / 120.18 / 119.58 / 1.3900 / 1.3859 / 1.3851
Ph(e) / D2 / 118.39 / 120.83 / 120.26 / 119.44 / 1.3920 / 1.3849 / 1.3851
CHNH(c) / Cs / 119.36 / 120.34 / 119.99 / 119.98 / 1.3902 / 1.3839 / 1.3864
CHNH(o) / Cs / 119.41 / 120.28 / 120.15 / 119.73 / 1.3879 / 1.3854 / 1.3853
CHO(c) / Cs / 119.94 / 120.06 / 119.78 / 120.39 / 1.3895 / 1.3834 / 1.3871
CHO(o) / Cs / 119.91 / 119.98 / 120.12 / 119.89 / 1.3871 / 1.3853 / 1.3854
COMe(c) / Cs / 119.13 / 120.47 / 119.96 / 120.02 / 1.3912 / 1.3839 / 1.3859
COMe(o) / Cs / 119.69 / 120.11 / 120.15 / 119.79 / 1.3871 / 1.3854 / 1.3853
COF(c) / Cs / 120.30 / 119.76 / 119.89 / 120.41 / 1.3898 / 1.3828 / 1.3865
COF(o) / Cs / 120.57 / 119.59 / 120.09 / 120.07 / 1.3855 / 1.3846 / 1.3853
COCl(c) / Cs / 119.89 / 119.96 / 119.98 / 120.23 / 1.3910 / 1.3826 / 1.3860
COCl(o) / Cs / 120.75 / 119.47 / 120.12 / 120.07 / 1.3850 / 1.3845 / 1.3854
CONH2(e) / C1 / 119.47 / 120.26 / 120.01 / 119.99 / 1.3895 / 1.3842 / 1.3857
COO(c) / C2v / 118.42 / 120.94 / 120.15 / 119.41 / 1.3902 / 1.3874 / 1.3872
COO(o) / C2v / 118.10 / 121.04 / 120.42 / 118.98 / 1.3907 / 1.3861 / 1.3870
COOH(c) / Cs / 120.03 / 119.93 / 119.92 / 120.27 / 1.3895 / 1.3835 / 1.3863
COOH(o) / Cs / 120.26 / 119.78 / 120.11 / 119.94 / 1.3854 / 1.3849 / 1.3853
COOMe(c) / Cs / 119.90 / 120.01 / 119.95 / 120.19 / 1.3894 / 1.3838 / 1.3862
COOMe(o) / Cs / 120.12 / 119.87 / 120.12 / 119.89 / 1.3855 / 1.3850 / 1.3853
CCH / C2v / 119.47 / 120.16 / 120.16 / 119.88 / 1.3918 / 1.3835 / 1.3859
CN / C2v / 120.51 / 119.57 / 120.03 / 120.28 / 1.3895 / 1.3830 / 1.3862
NH2(c) / C2v / 118.63 / 120.34 / 121.07 / 118.53 / 1.3947 / 1.3824 / 1.3859
NH2(o) / C2v / 118.72 / 120.70 / 120.15 / 119.58 / 1.3898 / 1.3859 / 1.3854
NH2(p) / Cs / 118.77 / 120.37 / 120.88 / 118.73 / 1.3922 / 1.3835 / 1.3856
NH2(p') / Cs / 119.00 / 120.53 / 120.21 / 119.52 / 1.3882 / 1.3859 / 1.3854
NF2(p) / Cs / 121.39 / 118.95 / 120.49 / 119.72 / 1.3830 / 1.3845 / 1.3847
NF2(p') / Cs / 121.83 / 118.91 / 119.98 / 120.39 / 1.3812 / 1.3844 / 1.3863
NCl2(p) / Cs / 119.33 / 119.97 / 120.95 / 118.82 / 1.3895 / 1.3842 / 1.3829
NCl2(p') / Cs / 120.92 / 119.42 / 120.10 / 120.05 / 1.3833 / 1.3846 / 1.3858
NHCOMe(c) / Cs / 119.31 / 119.99 / 120.92 / 118.88 / 1.3914 / 1.3841 / 1.3844
NHCOMe(o) / Cs / 119.88 / 120.06 / 120.09 / 119.82 / 1.3849 / 1.3851 / 1.3852
NH3(o) / Cs / 123.16 / 118.05 / 120.13 / 120.48 / 1.3782 / 1.3849 / 1.3857
NO2(c) / C2v / 122.42 / 118.46 / 120.11 / 120.44 / 1.3819 / 1.3833 / 1.3862
NO2(o) / C2v / 123.09 / 118.11 / 120.20 / 120.30 / 1.3767 / 1.3848 / 1.3857
NC / C2v / 121.04 / 119.21 / 120.32 / 119.90 / 1.3855 / 1.3836 / 1.3857
N2 / C2v / 125.33 / 116.57 / 119.96 / 121.61 / 1.3871 / 1.3786 / 1.3904
O / C2v / 113.99 / 122.33 / 122.16 / 117.04 / 1.4385 / 1.3768 / 1.3955
OH(c) / Cs / 120.13 / 119.64 / 120.76 / 119.06 / 1.3862 / 1.3843 / 1.3855
OH(o) / Cs / 120.34 / 119.68 / 120.38 / 119.53 / 1.3840 / 1.3856 / 1.3856
OMe(c) / Cs / 119.73 / 119.78 / 120.89 / 118.93 / 1.3895 / 1.3845 / 1.3851
OMe(o) / Cs / 120.25 / 119.72 / 120.39 / 119.54 / 1.3850 / 1.3854 / 1.3857
OH2(c) / C2v / 126.31 / 116.14 / 120.43 / 120.56 / 1.3677 / 1.3871 / 1.3856
OH2(o) / C2v / 126.21 / 116.25 / 120.15 / 120.99 / 1.3709 / 1.3857 / 1.3871
OH2(p) / Cs / 126.30 / 116.16 / 120.39 / 120.62 / 1.3682 / 1.3871 / 1.3858
OH2(p') / Cs / 126.19 / 116.25 / 120.17 / 120.97 / 1.3712 / 1.3864 / 1.3869
F / C2v / 122.44 / 118.43 / 120.51 / 119.69 / 1.3768 / 1.3857 / 1.3858
Na / C2v / 114.21 / 123.40 / 120.09 / 118.81 / 1.4061 / 1.3899 / 1.3858
MgCl / C2v / 116.05 / 122.28 / 119.95 / 119.49 / 1.4019 / 1.3871 / 1.3851
SiH2(c) / C2v / 119.20 / 120.20 / 119.44 / 121.52 / 1.4142 / 1.3739 / 1.3923
SiH2(o) / C2v / 119.91 / 119.78 / 119.91 / 120.70 / 1.3994 / 1.3811 / 1.3867
SiH2(c) / C2v / 115.29 / 122.24 / 121.28 / 117.67 / 1.4132 / 1.3794 / 1.3918
SiH2(o) / C2v / 115.70 / 122.40 / 120.25 / 119.00 / 1.4024 / 1.3889 / 1.3851
SiH2(p) / Cs / 115.61 / 122.48 / 120.46 / 118.51 / 1.4010 / 1.3866 / 1.3875
SiH2(p') / Cs / 115.72 / 122.49 / 120.22 / 118.85 / 1.3998 / 1.3887 / 1.3866
SiH3(o) / Cs / 117.84 / 121.23 / 119.96 / 119.79 / 1.3952 / 1.3856 / 1.3853
SiMe3(o) / Cs / 117.14 / 121.64 / 120.01 / 119.56 / 1.3965 / 1.3860 / 1.3850
SiPh3(e) / S4 / 117.38 / 121.48 / 120.01 / 119.64 / 1.3967 / 1.3860 / 1.3851
SiF3(o) / Cs / 118.67 / 120.71 / 119.85 / 120.23 / 1.3957 / 1.3839 / 1.3857
SiCl3(o) / Cs / 118.53 / 120.76 / 119.94 / 120.06 / 1.3953 / 1.3840 / 1.3852
PH2(c) / C2v / 119.06 / 120.22 / 120.69 / 119.11 / 1.3927 / 1.3834 / 1.3854
PH2(o) / C2v / 118.64 / 120.68 / 119.98 / 120.03 / 1.3950 / 1.3850 / 1.3853
PH2(p) / Cs / 118.56 / 120.74 / 120.23 / 119.49 / 1.3911 / 1.3853 / 1.3851
PH2(p') / Cs / 118.52 / 120.82 / 120.03 / 119.79 / 1.3922 / 1.3856 / 1.3853
PCl2(p) / Cs / 119.03 / 120.39 / 120.21 / 119.76 / 1.3923 / 1.3841 / 1.3846
PCl2(p') / Cs / 119.54 / 120.21 / 119.91 / 120.23 / 1.3914 / 1.3838 / 1.3859
PH3(o) / Cs / 121.00 / 119.21 / 119.89 / 120.81 / 1.3941 / 1.3810 / 1.3873
S / C2v / 115.84 / 122.03 / 121.05 / 117.99 / 1.4064 / 1.3836 / 1.3890
SH(c) / Cs / 119.53 / 120.05 / 120.53 / 119.30 / 1.3885 / 1.3847 / 1.3850
SH(o) / Cs / 119.66 / 120.11 / 120.13 / 119.85 / 1.3881 / 1.3856 / 1.3852
SMe(c) / Cs / 119.08 / 120.28 / 120.61 / 119.15 / 1.3904 / 1.3847 / 1.3847
SMe(o) / Cs / 119.38 / 120.28 / 120.11 / 119.83 / 1.3894 / 1.3856 / 1.3854
SO2Me(o) / Cs / 121.30 / 119.14 / 119.98 / 120.45 / 1.3860 / 1.3842 / 1.3862
SO2Cl(o) / Cs / 122.14 / 118.63 / 119.97 / 120.68 / 1.3850 / 1.3830 / 1.3865
Cl / C2v / 121.33 / 119.05 / 120.41 / 119.74 / 1.3821 / 1.3854 / 1.3851
ClO(c) / Cs / 123.42 / 117.79 / 120.41 / 120.18 / 1.3777 / 1.3856 / 1.3857
ClO3(o) / Cs / 124.58 / 117.16 / 120.16 / 120.78 / 1.3765 / 1.3845 / 1.3863
a Whenever necessary, the geometry of the benzene ring has been made consistent with C2v symmetry by averaging appropriate geometrical parameters.
b Angles are in degrees, bond distances in Å.
c The conformation of the substituent with respect to the benzene ring is denoted as (c), (o), (p), (p'), and (e) according to the definitions given in the text (section “The data sets”).
d The substituents which have been used to trace the electronegativity line are identified in bold.
e Symmetry constraint imposed in the optimization of molecular geometry.
Table S3 Internal coordinates of the benzene ring in PhX molecules, from B3LYP/6-311++G** calculationsa,b
Substituentc,d / Molecular
symmetrye / / / / / a / b / c
H / D6h / 120.00 / 120.00 / 120.00 / 120.00 / 1.3946 / 1.3946 / 1.3946
Li / C2v / 114.36 / 123.36 / 119.92 / 119.07 / 1.4141 / 1.3979 / 1.3942
BeH / C2v / 116.64 / 121.89 / 119.89 / 119.79 / 1.4114 / 1.3939 / 1.3943
BeCl / C2v / 116.86 / 121.74 / 119.92 / 119.80 / 1.4106 / 1.3938 / 1.3942
BH2(c) / C2v / 117.56 / 121.38 / 119.68 / 120.32 / 1.4116 / 1.3909 / 1.3961
BH2(o) / C2v / 117.85 / 121.07 / 120.28 / 119.44 / 1.4049 / 1.3938 / 1.3934
BF2(c) / C2v / 118.55 / 120.78 / 119.84 / 120.21 / 1.4058 / 1.3913 / 1.3953
BF2(o) / C2v / 118.45 / 120.79 / 120.08 / 119.82 / 1.4031 / 1.3933 / 1.3936
BCl2(c) / C2v / 117.77 / 121.17 / 119.95 / 120.00 / 1.4095 / 1.3904 / 1.3949
BCl2(o) / C2v / 118.48 / 120.74 / 120.14 / 119.76 / 1.4034 / 1.3932 / 1.3937
BH3(o) / Cs / 114.86 / 123.01 / 120.34 / 118.45 / 1.4114 / 1.3961 / 1.3969
CH2(c) / C2v / 119.34 / 119.88 / 119.32 / 122.26 / 1.4415 / 1.3729 / 1.4083
CH2(o) / C2v / 120.81 / 118.31 / 121.49 / 119.59 / 1.4183 / 1.3890 / 1.3910
CH2(c) / C2v / 113.52 / 122.74 / 122.13 / 116.73 / 1.4481 / 1.3822 / 1.4085
CH2(o) / C2v / 114.31 / 123.16 / 120.43 / 118.52 / 1.4189 / 1.3974 / 1.3957
CH2(p') / Cs / 114.58 / 123.04 / 120.44 / 118.45 / 1.4162 / 1.3965 / 1.3963
Me(o) / Cs / 118.18 / 121.03 / 120.17 / 119.42 / 1.3993 / 1.3937 / 1.3938
CMe3(c) / Cs / 117.25 / 121.51 / 120.35 / 119.03 / 1.4017 / 1.3939 / 1.3925
CMe3(o) / Cs / 117.12 / 121.57 / 120.38 / 118.97 / 1.4022 / 1.3940 / 1.3924
CF3(o) / Cs / 120.41 / 119.64 / 120.13 / 120.03 / 1.3955 / 1.3923 / 1.3940
CCl3(c) / Cs / 119.19 / 120.29 / 120.35 / 119.53 / 1.3984 / 1.3917 / 1.3928
CCl3(o) / Cs / 119.09 / 120.33 / 120.38 / 119.48 / 1.3989 / 1.3916 / 1.3926
CHCH2(c) / Cs / 117.92 / 121.09 / 120.23 / 119.45 / 1.4042 / 1.3911 / 1.3946
CHCH2(o) / Cs / 118.66 / 120.68 / 120.20 / 119.58 / 1.4003 / 1.3940 / 1.3938
Ph(c) / D2h / 116.80 / 121.68 / 120.48 / 118.88 / 1.4058 / 1.3916 / 1.3928
Ph(o) / D2d / 118.72 / 120.66 / 120.18 / 119.62 / 1.3998 / 1.3942 / 1.3938
Ph(e) / D2 / 118.14 / 120.95 / 120.26 / 119.44 / 1.4028 / 1.3925 / 1.3940
CHNH(c) / Cs / 119.19 / 120.39 / 120.04 / 119.95 / 1.4013 / 1.3911 / 1.3955
CHNH(o) / Cs / 119.33 / 120.30 / 120.16 / 119.75 / 1.3980 / 1.3936 / 1.3938
CHO(c) / Cs / 119.85 / 120.05 / 119.85 / 120.35 / 1.4004 / 1.3906 / 1.3962
CHO(o) / Cs / 119.84 / 119.97 / 120.16 / 119.89 / 1.3972 / 1.3936 / 1.3939
COMe(c) / Cs / 119.03 / 120.48 / 120.03 / 119.96 / 1.4016 / 1.3912 / 1.3949
COMe(o) / Cs / 119.60 / 120.13 / 120.17 / 119.80 / 1.3972 / 1.3936 / 1.3938
COF(c) / Cs / 120.11 / 119.78 / 120.03 / 120.27 / 1.4010 / 1.3902 / 1.3953
COF(o) / Cs / 120.42 / 119.59 / 120.20 / 120.01 / 1.3966 / 1.3926 / 1.3938
COCl(c) / Cs / 119.75 / 119.96 / 120.11 / 120.11 / 1.4021 / 1.3899 / 1.3949
COCl(o) / Cs / 120.62 / 119.46 / 120.23 / 120.01 / 1.3960 / 1.3925 / 1.3939
CONH2(e) / C1 / 119.26 / 120.34 / 120.08 / 119.88 / 1.3995 / 1.3921 / 1.3945
COO(c) / C2v / 118.37 / 120.99 / 120.14 / 119.36 / 1.3986 / 1.3952 / 1.3966
COO(o) / C2v / 117.85 / 121.20 / 120.38 / 119.00 / 1.4013 / 1.3943 / 1.3965
COOH(c) / Cs / 119.89 / 119.94 / 120.05 / 120.13 / 1.4000 / 1.3910 / 1.3951
COOH(o) / Cs / 120.09 / 119.83 / 120.18 / 119.91 / 1.3961 / 1.3931 / 1.3938
COOMe(c) / Cs / 119.76 / 120.02 / 120.07 / 120.05 / 1.3998 / 1.3914 / 1.3950
COOMe(o) / Cs / 119.94 / 119.93 / 120.17 / 119.87 / 1.3962 / 1.3931 / 1.3939
CCH / C2v / 119.09 / 120.27 / 120.28 / 119.80 / 1.4049 / 1.3911 / 1.3948
CN / C2v / 120.01 / 119.73 / 120.21 / 120.12 / 1.4028 / 1.3903 / 1.3946
NH2(c) / C2v / 118.45 / 120.49 / 120.92 / 118.75 / 1.4052 / 1.3906 / 1.3948
NH2(o) / C2v / 118.60 / 120.75 / 120.12 / 119.65 / 1.4001 / 1.3940 / 1.3941
NH2(p) / Cs / 118.60 / 120.48 / 120.78 / 118.89 / 1.4029 / 1.3912 / 1.3945
NH2(p') / Cs / 118.94 / 120.57 / 120.16 / 119.61 / 1.3979 / 1.3941 / 1.3940
NF2(p) / Cs / 121.46 / 118.85 / 120.50 / 119.83 / 1.3941 / 1.3921 / 1.3937
NF2(p') / Cs / 121.96 / 118.75 / 120.06 / 120.42 / 1.3922 / 1.3919 / 1.3953
NCl2(p) / Cs / 119.35 / 119.93 / 120.86 / 119.07 / 1.4014 / 1.3912 / 1.3924
NCl2(p') / Cs / 121.05 / 119.27 / 120.15 / 120.12 / 1.3940 / 1.3921 / 1.3948
NHCOMe(c) / Cs / 119.38 / 119.95 / 120.80 / 119.12 / 1.4018 / 1.3917 / 1.3935
NHCOMe(o) / Cs / 119.94 / 119.99 / 120.10 / 119.88 / 1.3946 / 1.3932 / 1.3939
NH3(o) / Cs / 123.30 / 117.92 / 120.17 / 120.51 / 1.3872 / 1.3937 / 1.3942
NO2(c) / C2v / 122.32 / 118.48 / 120.21 / 120.31 / 1.3914 / 1.3913 / 1.3951
NO2(o) / C2v / 122.83 / 118.20 / 120.28 / 120.21 / 1.3873 / 1.3932 / 1.3943
NC / C2v / 120.78 / 119.27 / 120.36 / 119.94 / 1.3980 / 1.3911 / 1.3945
N2 / C2v / 124.14 / 117.01 / 120.22 / 121.41 / 1.4070 / 1.3841 / 1.3999
O / C2v / 113.77 / 122.63 / 121.72 / 117.53 / 1.4467 / 1.3877 / 1.4034
OH(c) / Cs / 120.13 / 119.66 / 120.63 / 119.28 / 1.3959 / 1.3926 / 1.3943
OH(o) / Cs / 120.33 / 119.68 / 120.31 / 119.67 / 1.3938 / 1.3939 / 1.3943
OMe(c) / Cs / 119.82 / 119.74 / 120.77 / 119.15 / 1.3992 / 1.3927 / 1.3940
OMe(o) / Cs / 120.32 / 119.68 / 120.31 / 119.71 / 1.3947 / 1.3937 / 1.3945
OH2(c) / C2v / 126.70 / 115.89 / 120.46 / 120.60 / 1.3751 / 1.3970 / 1.3937
OH2(o) / C2v / 126.55 / 116.00 / 120.27 / 120.91 / 1.3787 / 1.3958 / 1.3950
OH2(p) / Cs / 126.73 / 115.88 / 120.42 / 120.67 / 1.3754 / 1.3972 / 1.3938
OH2(p') / Cs / 126.74 / 115.89 / 120.29 / 120.91 / 1.3778 / 1.3964 / 1.3949
F / C2v / 122.58 / 118.34 / 120.45 / 119.84 / 1.3862 / 1.3943 / 1.3946
Na / C2v / 115.20 / 122.85 / 120.03 / 119.03 / 1.4098 / 1.3989 / 1.3941
MgCl / C2v / 116.51 / 121.99 / 119.99 / 119.54 / 1.4090 / 1.3958 / 1.3936
SiH2(c) / C2v / 119.53 / 119.85 / 119.75 / 121.28 / 1.4237 / 1.3826 / 1.4007
SiH2(o) / C2v / 120.29 / 119.36 / 120.22 / 120.56 / 1.4103 / 1.3905 / 1.3945
SiH2(c) / C2v / 114.84 / 122.42 / 121.42 / 117.48 / 1.4294 / 1.3858 / 1.4044
SiH2(o) / C2v / 115.79 / 122.35 / 120.25 / 119.01 / 1.4112 / 1.3976 / 1.3944
SiH2(p) / Cs / 115.30 / 122.65 / 120.51 / 118.39 / 1.4127 / 1.3937 / 1.3979
SiH2(p') / Cs / 115.70 / 122.55 / 120.17 / 118.87 / 1.4080 / 1.3972 / 1.3957
SiH3(o) / Cs / 117.96 / 121.11 / 120.03 / 119.74 / 1.4041 / 1.3938 / 1.3939
SiMe3(o) / Cs / 117.27 / 121.54 / 120.04 / 119.55 / 1.4052 / 1.3943 / 1.3937
SiPh3(e) / S4 / 117.62 / 121.31 / 120.06 / 119.64 / 1.4052 / 1.3944 / 1.3938
SiF3(o) / Cs / 118.91 / 120.48 / 120.01 / 120.11 / 1.4047 / 1.3923 / 1.3941
SiCl3(o) / Cs / 118.82 / 120.52 / 120.08 / 119.97 / 1.4038 / 1.3924 / 1.3937
PH2(c) / C2v / 118.96 / 120.20 / 120.77 / 119.11 / 1.4046 / 1.3913 / 1.3946
PH2(o) / C2v / 118.79 / 120.54 / 120.10 / 119.93 / 1.4040 / 1.3934 / 1.3939
PH2(p) / Cs / 118.61 / 120.68 / 120.28 / 119.47 / 1.4005 / 1.3935 / 1.3937
PH2(p') / Cs / 118.63 / 120.71 / 120.11 / 119.73 / 1.4007 / 1.3940 / 1.3938
PCl2(p) / Cs / 119.17 / 120.25 / 120.28 / 119.75 / 1.4021 / 1.3922 / 1.3935
PCl2(p') / Cs / 119.79 / 120.00 / 120.02 / 120.16 / 1.4001 / 1.3921 / 1.3946
PH3(o) / Cs / 121.31 / 118.89 / 120.12 / 120.67 / 1.4035 / 1.3900 / 1.3952
S / C2v / 115.37 / 122.25 / 121.10 / 117.93 / 1.4209 / 1.3907 / 1.3996
SH(c) / Cs / 119.48 / 120.04 / 120.56 / 119.31 / 1.3988 / 1.3926 / 1.3938
SH(o) / Cs / 119.75 / 120.02 / 120.20 / 119.81 / 1.3972 / 1.3941 / 1.3939
SMe(c) / Cs / 119.12 / 120.21 / 120.63 / 119.21 / 1.4007 / 1.3925 / 1.3937
SMe(o) / Cs / 119.51 / 120.17 / 120.16 / 119.83 / 1.3985 / 1.3939 / 1.3941
SO2Me(o) / Cs / 121.71 / 118.87 / 120.10 / 120.35 / 1.3933 / 1.3933 / 1.3948
SO2Cl(o) / Cs / 122.70 / 118.22 / 120.16 / 120.54 / 1.3921 / 1.3921 / 1.3948
Cl / C2v / 121.50 / 118.91 / 120.45 / 119.77 / 1.3913 / 1.3942 / 1.3938
ClO(c) / Cs / 124.33 / 117.28 / 120.41 / 120.30 / 1.3836 / 1.3954 / 1.3951
ClO3(o) / Cs / 125.34 / 116.70 / 120.30 / 120.66 / 1.3813 / 1.3950 / 1.3948
a Whenever necessary, the geometry of the benzene ring has been made consistent with C2v symmetry by averaging appropriate geometrical parameters.
b Angles are in degrees, bond distances in Å.
c The conformation of the substituent with respect to the benzene ring is denoted as (c), (o), (p), (p'), and (e) according to the definitions given in the text (section “The data sets”).
d The substituents which have been used to trace the electronegativity line are identified in bold.
e Symmetry constraint imposed in the optimization of molecular geometry.
1