Supporting Information
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2011
The Role of Molecular Electrostatic Potentials in the
Formation of a Halogen Bond in Furan···XY and
Thiophene···XY Complexes**
Yanli Zeng, Xueying Zhang, Xiaoyan Li, Lingpeng Meng, and Shijun Zheng*[a]
cphc_201100008_sm_miscellaneous_information.pdf
Br
Cl
F
C(2)
Cl
Cl
Cl
C(3)
O(1)
C(2)
O(1)
C(4)
C(5)
C(3)
O(1)
C(4)
C(5)
furan...ClF (I)
C(2)
C(3)
C(4)
C(5)
furan...Cl2 (I)
furan...ClBr (I)
Cl
Br
Br
Br
F
Br
C(2)
C(2)
C(3)
O(1)
C(3)
C(2)
O(1)
C(4)
C(5)
C(4)
C(5)
furan...BrF (I)
C(3)
O(1)
C(5)
C(4)
furan...Br2 (I)
furan...BrCl (I)
Cl
Br
Cl
Cl
F
Cl
C(2)
C(2) C(3)
C(3)
S(1)
C(2)
C(5)
C(4)
C(4)
C(5)
C(5)
thiophene...Cl2 (I)
thiophene...ClF (I)
C(3)
S(1)
S(1)
C(4)
thiophene...ClBr (I)
Br
Cl
F
C(2)
C(3)
S(1)
C(2) C(3)
C(4)
thiophene...BrF (I)
C(2)
C(3)
S(1)
S(1)
C(5)
Br
Br
Br
C(5)
C(4)
thiophene...BrCl (I)
C(5)
C(4)
thiophene...Br2 (I)
Figure 1 Molecular graphs of furan···XY(I) and thiophene···XY(I) complexes
1
F
Cl
Br
Cl
Cl
Cl
O(1)
C(2)
C(2) C(3)
C(2)
C(3)
O(1)
C(5)
O(1)
C(3)
C(5)
furan...Cl2 (II)
furan...ClF (II)
furan...ClBr (II)
Br
Cl
F
Br
Br
O(1)
Br
O(1)
C(2)
C(4)
C(5)
C(4)
C(4)
C(2)
O(1)
C(2)
C(3)
C(5)
C(3)
C(5)
C(5)
C(3)
C(4)
C(4)
C(4)
furan...BrCl (II)
furan...BrF (II)
furan...Br2 (II)
Br
Cl
F
Cl
Cl
Cl
C(2) C(3)
C(2) C(3)
C(2) C(3)
S(1)
S(1)
S(1)
C(5)
C(4)
C(5)
thiophene...ClF (II)
C(4)
C(5)
thiophene...Cl2 (II)
C(4)
thiophene...ClBr (II)
Br
Cl
F
Br
Br
Br
C(2)
C(3)
S(1)
C(5)
C(4)
thiophene...BrF (II)
C(2) C(3)
C(2) C(3)
S(1)
S(1)
C(5)
C(4)
thiophene...BrCl (II)
C(5)
C(4)
thiophene...Br2 (II)
Figure 2 Molecular graphs of furan···XY(II) and thiophene···XY(II) complexes
2
integral values of interatomic surface / a.u.
0.48
0.46
0.44
0.42
0.40
0.38
0.36
0.34
0.32
0.30
0.28
0.26
0.24
0.22
0.20
0.18
0.16
0.14
0.12
furan...XY (I)
furan...XY (II)
thiophene...XY (I)
thiophene...XY (II)
R=0.9877
R=0.9554
R=0.9934
R=0.9842
0.008 0.010 0.012 0.014 0.016 0.018 0.020 0.022 0.024 0.026 0.028 0.030
integral values of interatomic surface / a.u.
electron density at the BCP of halogen bond / a.u.
(a)
0.44
furan...XY (I)
furan...XY (II)
thiophene...XY (I)
thiophene...XY (II)
0.42
0.40
0.38
0.36
R=0.9886
R=0.9644
R=0.9486
R=0.9755
0.34
0.32
0.30
0.28
0.26
0.24
0.22
0.20
0.18
0.16
0.14
0.12
15
20
25
30
(b)
35
40
45
50
55
60
65
VS,max / (kcal/mol)
Figure 3 Linear relations of the integration of electron density over interatomic surface versus electron density ρb at the halogen bond BCP and VS,max of X atom. (a)
The integration of electron density over interatomic surface versus electron density ρb, (b) The integration of electron density over interatomic surface versus VS,max
of X atom
3