Structural variations and electronic substituent effects in phenylcubane derivatives: a quantum chemical study
Anna Rita Campanelli Aldo Domenicano Fabio Ramondo
SUPPLEMENTARY MATERIAL
Correlations between internal coordinates of the benzene ring in PhC8H6X and PhC(CH2CH2)3CX molecules
The values of the ring angles , , and of the a bond distances for PhC8H6X molecules (5), as obtained from HF/6-31G* and B3LYP/6-311++G** calculations, are reported in Tables S1 and S2, respectively. The corresponding values for PhC(CH2CH2)3CX molecules (2) are presented in Tables S3 and S4.
The ring angles span rather narrow intervals; it is only with that the range is wider than 1°. In both molecular systems , , and are linearly related to with high correlation coefficients, see Tables S5 and S6. In the case of further improvement of the fit is obtained by using a second degree polynomial
The CC bond distances are less affected than angles by the remote substituent X. The largest interval of values is that of the a distances, which is smaller than that of the angle by a factor of about 3.5 in 5 and 4.5 in 2, if normalized data are used. Scattergrams of a vs for both molecular systems show a regular decrease of a with increasing . Second degree polynomials fit the data with high correlation coefficients (Table S7).
Notwithstanding the narrow intervals of values, the concerted variation of the internal coordinates strongly suggests that a single electronic substituent effect is acting on the geometry of the phenyl probe.
Table S1 Selected internal coordinates of the benzene ring in PhC8H6X molecules (5), from HF/6-31G* calculationsa,bSubstituent / / / / / a
H / 118.214 / 120.957 / 120.240 / 119.391 / 1.3920
Li / 118.016 / 121.067 / 120.279 / 119.293 / 1.3925
BH3 / 117.658 / 121.249 / 120.370 / 119.103 / 1.3940
CH2 / 117.586 / 121.287 / 120.386 / 119.068 / 1.3943
Me / 118.226 / 120.952 / 120.236 / 119.398 / 1.3919
CF3 / 118.342 / 120.888 / 120.214 / 119.454 / 1.3916
Ph / 118.255 / 120.936 / 120.231 / 119.412 / 1.3918
CHO / 118.321 / 120.900 / 120.217 / 119.445 / 1.3917
COMe / 118.303 / 120.910 / 120.220 / 119.437 / 1.3917
COCl / 118.371 / 120.872 / 120.208 / 119.470 / 1.3915
COO / 117.774 / 121.189 / 120.342 / 119.163 / 1.3935
COOH / 118.312 / 120.905 / 120.220 / 119.439 / 1.3917
COOMe / 118.294 / 120.915 / 120.222 / 119.432 / 1.3917
CCH / 118.282 / 120.921 / 120.225 / 119.426 / 1.3918
CN / 118.384 / 120.865 / 120.205 / 119.476 / 1.3915
NH2 / 118.225 / 120.952 / 120.236 / 119.399 / 1.3919
NF2 / 118.351 / 120.883 / 120.212 / 119.460 / 1.3916
NH3 / 118.809 / 120.628 / 120.122 / 119.692 / 1.3907
NO2 / 118.409 / 120.850 / 120.201 / 119.489 / 1.3915
NC / 118.344 / 120.887 / 120.213 / 119.457 / 1.3916
O / 117.537 / 121.309 / 120.402 / 119.039 / 1.3946
OH / 118.260 / 120.933 / 120.230 / 119.415 / 1.3918
OMe / 118.251 / 120.938 / 120.231 / 119.411 / 1.3919
OH2 / 118.863 / 120.596 / 120.114 / 119.717 / 1.3907
F / 118.298 / 120.911 / 120.223 / 119.434 / 1.3917
MgCl / 118.227 / 120.953 / 120.235 / 119.398 / 1.3919
SiH3 / 118.268 / 120.929 / 120.228 / 119.418 / 1.3918
SiMe3 / 118.236 / 120.947 / 120.234 / 119.402 / 1.3919
PH2 / 118.277 / 120.924 / 120.226 / 119.423 / 1.3918
PH3 / 118.818 / 120.624 / 120.120 / 119.694 / 1.3907
S / 117.706 / 121.224 / 120.360 / 119.127 / 1.3938
SH / 118.301 / 120.910 / 120.223 / 119.433 / 1.3917
Cl / 118.329 / 120.894 / 120.217 / 119.448 / 1.3917
ClO3 / 118.496 / 120.801 / 120.187 / 119.527 / 1.3913
Range / 1.326 / 0.713 / 0.288 / 0.678 / 0.0039
a Bond angles are in degrees, bond distances in Å.
bThe small intervals of values spanned by some of the ring angles and the correlation introduced by geometrical constraints make it preferable to present bond angles with three decimal figures. Using only two would artificially spoil the correlations in Tables S5 and S7, without otherwise affecting the results of the present study.
Table S2 Selected internal coordinates of the benzene ring in PhC8H6X molecules (5), from B3LYP/6-311++G** calculationsa,b
Substituent / / / / / a
H / 118.145 / 120.978 / 120.232 / 119.435 / 1.4020
Li / 117.946 / 121.091 / 120.267 / 119.337 / 1.4027
BH3 / 117.572 / 121.283 / 120.366 / 119.129 / 1.4047
CH2 / 117.492 / 121.330 / 120.378 / 119.090 / 1.4049
Me / 118.160 / 120.968 / 120.234 / 119.435 / 1.4020
CF3 / 118.293 / 120.892 / 120.212 / 119.496 / 1.4016
Ph / 118.185 / 120.953 / 120.228 / 119.452 / 1.4020
CHO / 118.264 / 120.910 / 120.215 / 119.485 / 1.4017
COMe / 118.249 / 120.918 / 120.218 / 119.447 / 1.4017
COCl / 118.306 / 120.884 / 120.210 / 119.505 / 1.4016
COO / 117.700 / 121.215 / 120.337 / 119.194 / 1.4041
COOH / 118.238 / 120.923 / 120.219 / 119.476 / 1.4018
COOMe / 118.224 / 120.932 / 120.223 / 119.466 / 1.4018
CCH / 118.229 / 120.928 / 120.223 / 119.467 / 1.4018
CN / 118.319 / 120.877 / 120.208 / 119.510 / 1.4016
NH2 / 118.141 / 120.979 / 120.234 / 119.431 / 1.4021
NF2 / 118.309 / 120.885 / 120.208 / 119.505 / 1.4015
NH3 / 118.748 / 120.624 / 120.137 / 119.730 / 1.4009
NO2 / 118.333 / 120.870 / 120.204 / 119.518 / 1.4015
NC / 118.287 / 120.894 / 120.212 / 119.500 / 1.4017
O / 117.503 / 121.311 / 120.394 / 119.085 / 1.4055
OH / 118.195 / 120.948 / 120.228 / 119.453 / 1.4019
OMe / 118.168 / 120.964 / 120.231 / 119.443 / 1.4020
OH2 / 118.812 / 120.582 / 120.133 / 119.758 / 1.4009
F / 118.220 / 120.933 / 120.222 / 119.469 / 1.4019
MgCl / 118.177 / 120.962 / 120.227 / 119.445 / 1.4019
SiH3 / 118.205 / 120.945 / 120.224 / 119.457 / 1.4018
SiMe3 / 118.160 / 120.968 / 120.232 / 119.439 / 1.4020
PH2 / 118.200 / 120.947 / 120.225 / 119.456 / 1.4019
PH3 / 118.775 / 120.611 / 120.132 / 119.739 / 1.4007
S / 117.619 / 121.258 / 120.352 / 119.158 / 1.4045
SH / 118.231 / 120.930 / 120.220 / 119.469 / 1.4018
Cl / 118.237 / 120.922 / 120.221 / 119.476 / 1.4018
ClO3 / 118.433 / 120.809 / 120.196 / 119.557 / 1.4013
Range / 1.320 / 0.748 / 0.262 / 0.673 / 0.0048
aBond angles are in degrees, bond distances in Å.
bThe small intervals of values spanned by some of the ring angles and the correlation introduced by geometrical constraints make it preferable to present bond angles with three decimal figures. Using only two would artificially spoil the correlations in Table S5 and S7, without otherwise affecting the results of the present study.
Table S3 Selected internal coordinates of the benzene ring in PhC(CH2CH2)3CX molecules (2), from HF/6-31G* calculationsa,b
Substituent / / / / / a
H / 116.695 / 121.766 / 120.506 / 118.759 / 1.3951
Li / 116.507 / 121.874 / 120.535 / 118.673 / 1.3956
BH3 / 116.203 / 122.040 / 120.596 / 118.524 / 1.3967
CH2 / 116.192 / 122.047 / 120.600 / 118.514 / 1.3967
Me / 116.713 / 121.756 / 120.502 / 118.768 / 1.3951
CF3 / 116.814 / 121.698 / 120.487 / 118.814 / 1.3948
Ph / 116.725 / 121.749 / 120.501 / 118.774 / 1.3950
CHO / 116.781 / 121.717 / 120.493 / 118.798 / 1.3949
COMe / 116.756 / 121.731 / 120.497 / 118.787 / 1.3950
COCl / 116.829 / 121.689 / 120.486 / 118.818 / 1.3948
COO / 116.310 / 121.981 / 120.578 / 118.571 / 1.3963
COOH / 116.782 / 121.716 / 120.494 / 118.795 / 1.3949
COOMe / 116.761 / 121.728 / 120.497 / 118.788 / 1.3949
CCH / 116.765 / 121.726 / 120.497 / 118.789 / 1.3949
CN / 116.845 / 121.679 / 120.484 / 118.825 / 1.3947
NH2 / 116.738 / 121.742 / 120.499 / 118.778 / 1.3950
NF2 / 116.838 / 121.685 / 120.484 / 118.822 / 1.3948
NH3 / 117.268 / 121.434 / 120.421 / 119.019 / 1.3940
NO2 / 116.871 / 121.665 / 120.479 / 118.837 / 1.3947
NC / 116.848 / 121.679 / 120.483 / 118.826 / 1.3947
O / 116.108 / 122.093 / 120.611 / 118.481 / 1.3970
OH / 116.758 / 121.731 / 120.497 / 118.783 / 1.3949
OMe / 116.732 / 121.745 / 120.500 / 118.776 / 1.3950
OH2 / 117.341 / 121.391 / 120.411 / 119.051 / 1.3939
F / 116.798 / 121.708 / 120.489 / 118.804 / 1.3948
MgCl / 116.696 / 121.766 / 120.503 / 118.762 / 1.3951
SiH3 / 116.723 / 121.749 / 120.500 / 118.775 / 1.3951
SiMe3 / 116.707 / 121.760 / 120.503 / 118.766 / 1.3951
PH2 / 116.759 / 121.730 / 120.496 / 118.788 / 1.3949
PH3 / 117.233 / 121.454 / 120.425 / 119.004 / 1.3940
S / 116.274 / 122.001 / 120.586 / 118.552 / 1.3965
SH / 116.775 / 121.721 / 120.493 / 118.795 / 1.3949
Cl / 116.816 / 121.698 / 120.486 / 118.813 / 1.3948
ClO3 / 116.959 / 121.614 / 120.467 / 118.877 / 1.3945
Range / 1.233 / 0.702 / 0.200 / 0.570 / 0.0031
aBond angles are in degrees, bond distances in Å.
bThe small intervals of values spanned by some of the ring angles and the correlation introduced by geometrical constraints make it preferable to present bond angles with three decimal figures. Using only two would artificially spoil the correlations in Tables S6 and S7, without otherwise affecting the results of the present study.
Table S4 Selected internal coordinates of the benzene ring in PhC(CH2CH2)3CX molecules (2), from B3LYP/6-311++G** calculationsa,b
Substituent / / / / / a
H / 116.840 / 121.712 / 120.432 / 118.871 / 1.4033
Li / 116.679 / 121.813 / 120.447 / 118.801 / 1.4037
BH3 / 116.363 / 121.994 / 120.501 / 118.648 / 1.4049
CH2 / 116.385 / 121.977 / 120.513 / 118.636 / 1.4051
Me / 116.860 / 121.701 / 120.426 / 118.884 / 1.4033
CF3 / 116.964 / 121.639 / 120.415 / 118.927 / 1.4030
Ph / 116.879 / 121.690 / 120.424 / 118.893 / 1.4032
CHO / 116.932 / 121.658 / 120.420 / 118.911 / 1.4031
COMe / 116.906 / 121.674 / 120.421 / 118.903 / 1.4031
COCl / 116.990 / 121.625 / 120.412 / 118.936 / 1.4029
COO / 116.460 / 121.936 / 120.488 / 118.690 / 1.4046
COOH / 116.927 / 121.661 / 120.420 / 118.909 / 1.4031
COOMe / 116.898 / 121.679 / 120.423 / 118.899 / 1.4031
CCH / 116.915 / 121.667 / 120.423 / 118.904 / 1.4031
CN / 116.987 / 121.625 / 120.413 / 118.936 / 1.4029
NH2 / 116.886 / 121.687 / 120.423 / 118.892 / 1.4032
NF2 / 116.998 / 121.621 / 120.409 / 118.942 / 1.4029
NH3 / 117.408 / 121.364 / 120.367 / 119.127 / 1.4022
NO2 / 117.000 / 121.618 / 120.410 / 118.943 / 1.4029
NC / 116.985 / 121.626 / 120.412 / 118.937 / 1.4029
O / 116.311 / 122.021 / 120.509 / 118.628 / 1.4053
OH / 116.886 / 121.685 / 120.423 / 118.898 / 1.4032
OMe / 116.886 / 121.686 / 120.423 / 118.894 / 1.4032
OH2 / 117.517 / 121.299 / 120.356 / 119.170 / 1.4021
F / 116.938 / 121.655 / 120.416 / 118.919 / 1.4031
MgCl / 116.864 / 121.701 / 120.423 / 118.885 / 1.4032
SiH3 / 116.885 / 121.688 / 120.423 / 118.893 / 1.4032
SiMe3 / 116.860 / 121.702 / 120.427 / 118.881 / 1.4033
PH2 / 116.901 / 121.678 / 120.421 / 118.901 / 1.4031
PH3 / 117.395 / 121.374 / 120.366 / 119.124 / 1.4021
S / 116.435 / 121.952 / 120.492 / 118.677 / 1.4048
SH / 116.920 / 121.666 / 120.417 / 118.912 / 1.4031
Cl / 116.956 / 121.644 / 120.414 / 118.927 / 1.4030
ClO3 / 117.111 / 121.550 / 120.400 / 118.988 / 1.4026
Range / 1.206 / 0.722 / 0.157 / 0.542 / 0.0032
aBond angles are in degrees, bond distances in Å.
bThe small intervals of values spanned by some of the ring angles and the correlation introduced by geometrical constraints make it preferable to present bond angles with three decimal figures. Using only two would artificially spoil the correlations in Tables S6 and S7, without otherwise affecting the results of the present study.
Table S5 Linear regressions between angular parameters of the benzene ringa in phenylcubane derivatives (5), from HF/6-31G* and B3LYP/6-311++G** calculations
Regressionb / Level of calculation / Angular coefficient / Intercept (°) / Correlation coefficient
vs / HF / 0.537(2) / 0.003(4) / 0.9997
B3LYP / 0.556(4) / 0.059(7) / 0.9992
vs c / HF / 0.218(3) / 0.147(5) / 0.9971
B3LYP / 0.197(5) / 0.124(10) / 0.9890
vs / HF / 0.511(1) / 0.302(3) / 0.9999
B3LYP / 0.508(3) / 0.368(6) / 0.9993
D4 vs D6d / HF / 2.84(3) / 0.93(3) / 0.9979
B3LYP / 2.62(5) / 0.83(6) / 0.9941
a = 120°, etc.
b The number of data points is 34.
cA better fit is obtained with a second degree polynomial (the correlation coefficient becomes 0.9997 at the HF level, 0.9978 at the B3LYP level).
dA better fit is obtained with a second degree polynomial (the correlation coefficient becomes 0.9997 at the HF level, 0.9983 at the B3LYP level).
Table S6 Linear regressions between angular parameters of the benzene ringain phenylbicyclo[2.2.2]octane derivatives (2), from HF/6-31G* and B3LYP/6-311++G** calculations
Regressionb / Level of calculation / Angular coefficient / Intercept (°) / Correlation coefficient
vs / HF / 0.568(2) / 0.112(5) / 0.9999
B3LYP / 0.598(2) / 0.178(7) / 0.9998
vs c / HF / 0.167(3) / 0.043(9) / 0.9961
B3LYP / 0.134(4) / 0.010(12) / 0.9871
vs / HF / 0.467(2) / 0.300(8) / 0.9996
B3LYP / 0.462(4) / 0.330(12) / 0.9989
D4 vs D6d / HF / 2.33(2) / 0.41(4) / 0.9986
B3LYP / 2.11(3) / 0.23(5) / 0.9973
a = 120°, etc.
b The number of data points is 34.
cA better fit is obtained with a second degree polynomial (the correlation coefficient becomes 0.9993 at the HF level, 0.9965 at the B3LYP level).
dA better fit is obtained with a second degree polynomial (the correlation coefficient becomes 0.9997 at the HF level, 0.9990 at the B3LYP level).
Table S7 Quadratic regressions between the a bond distance and the angle of the benzene ring (Å, degrees) in phenylcubane derivatives (5) and phenylbicyclo[2.2.2]octane derivatives (2), from HF/6-31G* and B3LYP/6-311++G** calculationsa
Molecular system / Level of calculation / Coefficients of the equation a = c2()2 + c1 + c0, where = 120° / Correlation coefficient
c2 / c1 / c0
5 / HF / 0.00141(4) / 0.0022(1) / 1.3913(1) / 0.9994
B3LYP / 0.00227(12) / 0.0051(4) / 1.4036(4) / 0.9964
2 / HF / 0.00116(5) / 0.0050(3) / 1.3991(5) / 0.9989
B3LYP / 0.00157(8) / 0.0070(5) / 1.4098(8) / 0.9976
a The number of data points is 34.
Table S8 Structural substituent parameters SE and SR for PhX molecules (1), from HF/6-31G* and B3LYP/6-311++G** calculationsa,b
Substituentc / HF/6-31G* / B3LYP/6-311++G**
SE / SR / SE / SR
H / 0.00 / 0.25 / 0.00 / 0.34
Li / 7.28 / 0.29 / 7.40 / 0.38
BH3 (o) / 6.62 / 0.64 / 6.79 / 0.53
CH2 (c) / 7.93 / 4.79 / 7.67 / 3.63
Me (o) / 2.27 / 0.17 / 2.37 / 0.05
CF3(o) / 0.41 / 0.21 / 0.65 / 0.16
Ph (o) / 1.61 / 0.02 / 1.60 / 0.01
CHO (c) / 0.03 / 0.80 / 0.10 / 0.73
COMe (c) / 1.06 / 0.43 / 1.15 / 0.36
COCl (c) / 0.02 / 0.44 / 0.11 / 0.28
COO (c) / 2.23 / 0.05 / 2.21 / 0.06
COOH (c) / 0.16 / 0.53 / 0.01 / 0.36
COOMe (c) / 0.01 / 0.46 / 0.17 / 0.30
CCH / 0.62 / 0.05 / 0.92 / 0.05
CN / 0.80 / 0.35 / 0.31 / 0.14
NH2(p) / 1.48 / 1.40 / 1.60 / 1.14
NF2(p) / 1.85 / 0.65 / 2.14 / 0.50
NH3 (o) / 4.30 / 0.04 / 4.44 / 0.14
NO2 (c) / 3.17 / 0.14 / 3.18 / 0.06
NC / 1.31 / 0.28 / 1.27 / 0.21
O / 7.38 / 3.51 / 7.26 / 2.69
OH (c) / 0.30 / 1.22 / 0.33 / 0.86
OMe (c) / 0.12 / 1.39 / 0.02 / 1.09
OH2(p) / 8.30 / 0.55 / 8.88 / 0.36
F / 3.10 / 0.80 / 3.42 / 0.52
MgCl / 4.91 / 0.49 / 4.47 / 0.38
SiH3 (o) / 2.73 / 0.46 / 2.56 / 0.32
SiMe3 (o) / 3.60 / 0.36 / 3.49 / 0.26
PH2(p) / 1.80 / 0.16 / 1.71 / 0.19
PH3 (o) / 1.68 / 0.76 / 2.13 / 0.45
S / 5.49 / 1.75 / 5.74 / 1.82
SH (c) / 0.48 / 0.70 / 0.49 / 0.71
Cl / 1.77 / 0.56 / 2.10 / 0.47
ClO3 (o) / 5.73 / 0.01 / 7.09 / 0.10
a The SE and SR values are taken, with some additions and updating, from our previous studies on PhX molecules [2, 3] and from Ref. [12].
b All values are in degrees.
c To specify the conformation of a nonlinear group with respect to the benzene ring, we make use of the following terms and abbreviations. Coplanar conformation (c): this term applies to planar substituents that are coplanar with the benzene ring. We include cases such as COMe, COOMe, and OMe, where coplanarity refers to the non-hydrogen atoms of the substituent. Orthogonal conformation (o): this term applies to planar substituents when the substituent plane is orthogonal to the plane of the ring and passes through the ipso and para carbons. It also applies to substituents having C3v symmetry, if one of their symmetry planes is orthogonal to the plane of the ring. Pyramidal conformation (p): we use this term when the first atom of the substituent has a pyramidal bond configuration with a lone electron pair protruding from the ring plane, as in the equilibrium structure of aniline.
Table S9 Regression statistics for the structural substituent parameter SFCUB versus SFBCO and the resonance parameter SRa
Level of calculation / Explanatory variablesb / R2 c / Radj2 d / Fe / Pf
HF / SFBCO / 0.9950 / 0.9949 / 6386.91 / <0.0001
SFBCO, SR / 0.9982 / 0.9981 / 8733.77 / <0.0001
B3LYP / SFBCO / 0.9898 / 0.9895 / 3114.01 / <0.0001
SFBCO, SR / 0.9965 / 0.9962 / 4359.48 / <0.0001
aThe number of data points is 34.
bSR values refer to PhX molecules and are taken from Table S8.
c Multiple correlation coefficient, squared.
d Adjusted multiple correlation coefficient, squared.
e Fisher test of variance for overall correlation.
f Probability of being wrong in concluding that there is an association between SFCUB and the explanatory variables.
Table S10 Regression statistics for the structural substituent parameter SFCUB versus experimental measures of field and resonance effects
Level of calculation / Number of data points / Explanatory variablesa,b / R2 c / Radj2 d / Fe / Pf
HF / 16 / F / 0.9359 / 0.9314 / 204.55 / <0.0001
16 / F,R0 / 0.9902 / 0.9887 / 654.89 / <0.0001
B3LYP / 16 / F / 0.8855 / 0.8774 / 108.32 / <0.0001
16 / F,R0 / 0.9871 / 0.9851 / 498.02 / <0.0001
HF / 8 / GoH GoX / 0.9697 / 0.9646 / 191.79 / <0.0001
8 / GoH GoX,R0 / 0.9904 / 0.9866 / 258.36 / <0.0001
B3LYP / 8 / GoH GoX / 0.9344 / 0.9235 / 85.47 / <0.0001
8 / GoH GoX,R0 / 0.9948 / 0.9927 / 474.57 / <0.0001
aThe experimental measure of the field effect used as an explanatory variable is either F, a parameter derived from the 19F NMR chemical shifts of p-FC6H4C(CH2CH2)3CX molecules in cyclohexane solution (values from Table 1 of Ref. [13]), or GoH G°X, the gas-phase acidity of HOOCC(CH2CH2)3CX molecules as determined by ion cyclotron resonance spectroscopy (values from Table 1 of Ref. [15]).
bThe experimental measure of the resonance effect used as an explanatory variable isR0, a parameter derived from infrared intensities of substituted benzene derivatives (values from Table 5 and 6 of Ref. [14]).
c Multiple correlation coefficient, squared.
d Adjusted multiple correlation coefficient, squared.
e Fisher test of variance for overall correlation.
f Probability of being wrong in concluding that there is an association between SFCUB and the explanatory variables.
Table S11 Selected internal coordinates of the cubane cage in PhC8H6X molecules (5), from HF/6-31G* calculationsa,b
Substituent / 1 / a1 / r(CC)1
H / 89.92 / 1.5589 / 2.7127
Li / 87.56 / 1.5845 / 2.7618
BH3 / 88.39 / 1.5743 / 2.7457
CH2 / 87.91 / 1.5902 / 2.7571
Me / 89.62 / 1.5624 / 2.7179
CF3 / 90.33 / 1.5556 / 2.7024
Ph / 89.31 / 1.5665 / 2.7251
CHO / 89.86 / 1.5623 / 2.7126
COMe / 89.73 / 1.5628 / 2.7154
COCl / 90.07 / 1.5604 / 2.7080
COO / 89.72 / 1.5587 / 2.7164
COOH / 90.00 / 1.5593 / 2.7097
COOMe / 90.00 / 1.5591 / 2.7098
CCH / 89.55 / 1.5649 / 2.7197
CN / 89.83 / 1.5629 / 2.7139
NH2 / 89.94 / 1.5611 / 2.7111
NF2 / 91.06 / 1.5490 / 2.6865
NH3 / 91.31 / 1.5513 / 2.6823
NO2 / 91.18 / 1.5478 / 2.6839
NC / 90.35 / 1.5567 / 2.7024
O / 86.72 / 1.6245 / 2.7883
OH / 90.45 / 1.5566 / 2.7003
OMe / 90.35 / 1.5589 / 2.7026
OH2 / 92.83 / 1.5384 / 2.6481
F / 91.28 / 1.5475 / 2.6828
MgCl / 88.09 / 1.5808 / 2.7504
SiH3 / 88.85 / 1.5722 / 2.7343
SiMe3 / 88.68 / 1.5737 / 2.7380
PH2 / 89.45 / 1.5655 / 2.7205
PH3 / 89.57 / 1.5743 / 2.7191
S / 88.82 / 1.5719 / 2.7358
SH / 90.08 / 1.5590 / 2.7068
Cl / 90.90 / 1.5502 / 2.6889
ClO3 / 91.98 / 1.5439 / 2.6645
Range / 6.11 / 0.0861 / 0.1402
aBond angles are in degrees, distances in Å.
bBond distances and angles have been averaged so as to conform to C3vsymmetry.
Table S12 Selected internal coordinates of the cubane cage in PhC8H6X molecules (5), from B3LYP/6-311++G** calculationsa,b
Substituent / 1 / a1 / r(CC)1
H / 89.92 / 1.5713 / 2.7348
Li / 87.40 / 1.6006 / 2.7867
BH3 / 88.40 / 1.5894 / 2.7664
CH2 / 87.08 / 1.6291 / 2.7976
Me / 89.61 / 1.5761 / 2.7400
CF3 / 90.25 / 1.5699 / 2.7263
Ph / 89.23 / 1.5814 / 2.7491
CHO / 89.71 / 1.5785 / 2.7372
COMe / 89.59 / 1.5783 / 2.7402
COCl / 89.84 / 1.5767 / 2.7346
COO / 89.59 / 1.5751 / 2.7407
COOH / 89.82 / 1.5745 / 2.7360
COOMe / 89.81 / 1.5743 / 2.7360
CCH / 89.21 / 1.5834 / 2.7495
CN / 89.49 / 1.5808 / 2.7434
NH2 / 89.87 / 1.5767 / 2.7340
NF2 / 90.89 / 1.5660 / 2.7113
NH3 / 91.58 / 1.5609 / 2.6974
NO2 / 91.08 / 1.5624 / 2.7074
NC / 90.18 / 1.5733 / 2.7283
O / 86.61 / 1.6488 / 2.8101
OH / 90.52 / 1.5707 / 2.7194
OMe / 90.39 / 1.5740 / 2.7229
OH2 / 93.81 / 1.5415 / 2.6445
F / 91.50 / 1.5595 / 2.6987
MgCl / 88.18 / 1.5938 / 2.7698
SiH3 / 88.89 / 1.5856 / 2.7551
SiMe3 / 88.68 / 1.5873 / 2.7600
PH2 / 89.49 / 1.5788 / 2.7413
PH3 / 89.72 / 1.5860 / 2.7368
S / 88.56 / 1.5936 / 2.7624
SH / 90.09 / 1.5732 / 2.7274
Cl / 91.00 / 1.5633 / 2.7074
ClO3 / 92.64 / 1.5507 / 2.6687
Range / 7.20 / 0.1073 / 0.1656
aBond angles are in degrees, distances in Å.
bBond distances and angles have been averaged so as to conform to C3vsymmetry.
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