(Wuli Huaxue Xuebao)

Acta Phys. -Chim. Sin. 2012, 28 (12), 2809-2816

December

doi: 10.3866/PKU.WHXB201209263

[Article]

2809
www.whxb.pku.edu.cn

1- N-

(, 116029)
:

B3LYP MP2 1- N-

, 1-
. : NHOC r(HO),
; NHOC r(HO), . (NBO):
, ,
; . NHOC n(O) NH
*(NH), .
NHOC .
:

; ; ; ;

O641

Effect of Substituents on Hydrogen Bond Strength in Hydrogen-Bonded

N-methylacetamide and Uracil Complexes
LIU Dong-Jia

WANG Chang-Sheng*

(School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China)
Abstract: Theoretical calculations on a series of N HOC hydrogen-bonded complexes containing
1-methyluracil and N-methylacetamide were carried out using B3LYP and MP2 methods. Substituent
effects in the hydrogen bond acceptor molecule (1-methyluracil) on the hydrogen bond strength and
hydrogen bond cooperativity were explored. The calculation results show that electron donating groups
shorten the HO distance and strengthen the NHOC hydrogen bond, whereas electron withdrawing
groups lengthen the HO distance and weaken the N HOC hydrogen bond. Natural bond orbital
(NBO) analysis further indicates that electron donating groups result in a larger positive charge on the H
atom and a larger negative charge on the O atom in the NHOC bond, and result in increased charge
transfer between the proton donor and acceptor molecules. Electron withdrawing groups show the opposite
results. NBO analysis also indicates that electron donating groups result in larger second-order interaction
energies between the oxygen lone pair and the N H antibonding orbital when compared to the
1-methyluracil-containing complex (R=H), while electron withdrawing groups result in smaller second-order
interaction energies.
Key Words:

Hydrogen-bonded complex; Substituent;

analysis; Hydrogen bond cooperativity

Hydrogen bond strength;

Natural bond orbital

Received: July 27, 2012; Revised: September 25, 2012; Published on Web: September 26, 2012.

Corresponding author. Email: chwangcs@lnnu.edu.cn; Tel: +86-411-82159391.

The project was supported by the National Natural Science Foundation of China (20973088, 21173109, 21133005) and Specialized Research Fund
for the Doctoral Program of Higher Education of China (20102136110001).
(20973088, 21173109, 21133005)(20102136110001)

Editorial office of Acta Physico-Chimica Sinica

2810

Acta Phys. -Chim. Sin. 2012

, ,
.1-12
Mohajeri Nobandegani5 15
NHN NHO .
Kolew 9
. Dong 13

, -
-. Vargas 14
N- NH
OC , N-
NHOC -36.0
kJmol-1, NHOC
-29.7 kJmol-1. Kawahara 15,16
MP2 -
AX-UCX-G ,
. Wang
17-22
, ,
(BSSE) MP2
. Dannenberg 23-25 B3LYP/D95**

. Wu Zhao26,27 , -
310-. Tan 28

Fig.1

Vol.28

B3LYP/cc-pVTZ N-
,
.

,
. Hunter 29

N1 . Jeong
30 -RNA
. Cheng Frankel31 HF/6-31G(d)
28 -,
21 .
ProtNA-ASA 214
-DNA 28 -RNA .32
MP2 1- N-
NHOC
,
NHOC
.

1
. NHOC
HB1HB2HB3 .
B3LYP/6-31+G(d, p)
, ,

1
Structures of hydrogen-bonded complexes

No.12

: 1- N-

BSSE MP2/6-311 ++ G(d, p) MP2/6-311 ++

G(3df, 2p).
, B3LYP/6-31+G(d,
p).
Gaussian 03 33 .

3.1

36 ,
2 15
. 21
S1 ( Supporting Information).

Fig.2

2811

, R=H 1- N-
NHOC ,
HB1 r(HO)HB1 0.2016 nm, HB2
r(HO)HB2 0.1950 nm. R NH2
EtMe , HB1 HB2
R=H , HB1 . : R=
NH2, r(HO)HB1 0.1987 nm, 0.0029 nm;
r(HO)HB2 0.1947 nm, 0.0003 nm.
R BH2COMeCONH2CHOCF3CNNO2
SO3H , R=H , HB1
HB2 . : R=NO2 , r(HO)HB1
0.2076 nm, 0.0060 nm; r(HO)HB2 0.1965

2 15
Optimal geometries of 15 hydrogen-bonded complexes
bond length in nm, bond angle in degree

2812

Vol.28

Acta Phys. -Chim. Sin. 2012

nm, 0.0015 nm, HB1

.
.
HB1
, HB1 ,
HB1 .
HB2 , HB2
. ,
, .
3.2
1 36

. 1 ,
1-
.
NH2EtMe , ;
BH2COMeCONH2CHOCF3
CNNO2SO3H , . BSSE
MP2/6-311++G(d, p),
, R=H , HB1 EHB1=-22.6
kJmol-1; H NH2 , EHB1=-24.5
kJmol-1, 1.9 kJmol-1; H
SO3H , EHB1=-16.9 kJmol-1,

1 36
Table 1 Hydrogen bond energies and hydrogen bond distances of thirty-six hydrogen-bonded complexes
MP2/6-311++G(d, p)
with BSSE

B3LYP/6-31+G(d, p)
R
dimer

trimer

tetramer

NH2
Et
Me
H
BH2
COMe
CONH2
CHO
CF3
CN
NO2
SO3H
NH2
Et
Me
H
BH2
COMe
CONH2
CHO
CF3
CN
NO2
SO3H
NH2
Et
Me
H
BH2
COMe
CONH2
CHO
CF3
CN
NO2
SO3H

r(HO)HB1 r(HO)HB2 r(HO)HB3

nm
nm
nm
0.2025
0.2042
0.2042
0.2055
0.2080
0.2079
0.2078
0.2093
0.2086
0.2102
0.2111
0.2112
0.1987
0.2004
0.2004
0.2016
0.2042
0.2043
0.2046
0.2056
0.2052
0.2067
0.2076
0.2077
0.1969
0.1986
0.1986
0.1998
0.2023
0.2024
0.2024
0.2037
0.2038
0.2048
0.2058
0.2064

0.1947
0.1950
0.1949
0.1950
0.1956
0.1958
0.1960
0.1959
0.1963
0.1963
0.1965
0.1969
0.1919
0.1920
0.1921
0.1923
0.1929
0.1931
0.1931
0.1933
0.1934
0.1936
0.1938
0.1939

0.1930
0.1930
0.1929
0.1930
0.1932
0.1933
0.1933
0.1934
0.1933
0.1935
0.1935
0.1935

EHB1
(kJmol-1)
-24.5
-23.7
-23.7
-22.6
-20.2
-20.3
-20.2
-19.3
-19.3
-18.1
-17.9
-16.9
-28.2
-27.3
-27.3
-25.9
-22.7
-22.5
-22.3
-21.4
-21.0
-19.6
-19.0
-17.3
-29.0
-28.0
-27.9
-26.4
-22.9
-22.8
-22.7
-21.4
-21.2
-19.4
-19.0
-17.6

EHB2
(kJmol-1)

-34.4
-34.3
-34.3
-34.0
-33.3
-33.0
-32.8
-32.8
-32.5
-32.3
-32.0
-31.2
-41.3
-41.3
-41.2
-40.7
-39.6
-39.4
-39.3
-39.0
-38.7
-38.3
-38.0
-37.4

MP2/6-311++G(3df, 2p)
with BSSE

EHB3
(kJmol-1)

-36.9
-36.9
-36.8
-36.6
-36.3
-36.4
-36.5
-36.0
-36.3
-35.9
-35.9
-36.2

EHB1
(kJmol-1)
-26.8
-25.6
-25.6
-24.4
-21.8
-21.9
-21.9
-20.8
-21.2
-19.5
-19.3
-18.6
-31.4
-30.0
-30.0
-28.5
-25.0
-24.8
-24.6
-23.6
-23.6
-21.6
-21.2
-19.8

EHB2
(kJmol-1)

-37.8
-37.6
-37.6
-37.3
-36.4
-36.1
-36.0
-36.0
-35.7
-35.3
-35.2
-34.5

No.12

: 1- N-

5.7 kJmol-1. , R=H , EHB1=-25.9 kJ

mol-1, EHB2=-34.0 kJmol-1; H NH2
, EHB1=-28.2 kJmol-1, 2.3 kJ
mol-1, EHB2=-34.4 kJmol-1, 0.4 kJ
mol-1; H SO3H , EHB1=-17.3 kJ
mol-1, 8.6 kJmol-1, EHB2=-31.2 kJ
mol-1, 2.8 kJmol-1. , R=H
, EHB1
EHB2 EHB3 -26.4
-40.7
-36.6 kJmol-1;
H NH2 , EHB1EHB2 EHB3
-29.0-41.3-36.9 kJmol-1,
2.6
0.6
0.3 kJmol-1; H SO3H ,
EHB1EHB2 EHB3 -17.6-37.4-36.2 kJmol-1,
8.83.30.4 kJmol-1. ,
,
,
.
EHB1 ,
EHB1 EHB1,
EHB1 EHB1, ,
HB1 . EHB2
, EHB2 EHB2,
, HB2 . ,
, ,
1- N- NH
OC .
3.3 (NBO)
2 B3LYP/6-31+G(d, p)
36 (NBO).
, qH , qO
, qt
, Eij

n(O) NH
*(NH).
.
R=H HB1
0.4592e, -0.6784e ( 2 3
4 ); HB2 0.4621e,
-0.6947e ( 2 7
8 ). R=H
, NH2 , HB1 qH
0.4614e, 0.0022e, qO -0.6984e,
0.0200e; HB2 qH 0.4625e,
0.0004e, qO -0.6969e,

2813

0.0022e. NH2 , 1-
,
, ,
.
R SO3H , HB1 qH
0.4543e, 0.0049e, qO -0.6506e,
0.0278e; HB2 qH 0.4612e,
0.0009e, qO -0.6908e,
0.0039e. SO3H , 1-
,
, ,
.
, ,
,
, ,
.
2 5 , HB1 , R=H

0.0194e; 2 9 , HB2
, R=H
0.0282e. NH2
, HB1 HB2
0.0214e 0.0286e, R=H
0.0020e 0.0004e.
SO3H , HB1 HB2
0.0145e 0.0257e, R=H
0.0049e 0.0025e. ,

,
. 2 , HB1
HB1
HB2
.
2 6 10 , R=H
HB1 HB2
41.9 59.8 kJmol-1. ,
Me , Eij(HB1) 43.9 kJmol-1,
2.0 kJmol-1, Eij(HB2) 60.0 kJmol-1,
0.2 kJmol-1. BH2 , Eij(HB1)
36.6 kJmol-1, 5.3 kJmol-1, Eij(HB2) 58.5
kJmol-1, 1.3 kJmol-1. ,
,
, HB1

2814

Vol.28

Acta Phys. -Chim. Sin. 2012

2 n*(NBO)
Table 2 n* second-order interaction energies and nature bond orbital (NBO) analysis for the hydrogen-bond complexes
HB1
R
dimer

NH2
Et
Me

H
BH2
COMe
CONH2
CHO
CF3
CN
NO2
SO3H
trimer
NH2
Et
Me
H
BH2
COMe
CONH2
CHO
CF3
CN
NO2
SO3H
tetramer NH2
Et
Me
H
BH2
COMe
CONH2
CHO
CF3
CN
NO2
SO3H

HB2

qH/e

qO/e

qt/e

0.4554
0.4545
0.4545

-0.6886
-0.6759
-0.6758

0.0189
0.0175
0.0176

0.4540
0.4511
0.4511
0.4515
0.4503
0.4499
0.4492
0.4486
0.4482
0.4614
0.4602
0.4601
0.4592
0.4572
0.4573
0.4575
0.4562
0.4568
0.4554
0.4543
0.4543
0.4632
0.4621
0.4620
0.4610
0.4588
0.4587
0.4590
0.4577
0.4581
0.4570
0.4561
0.4559

-0.6696
-0.6527
-0.6531
-0.6538
-0.6484
-0.6523
-0.6468
-0.6395
-0.6402
-0.6984
-0.6840
-0.6839
-0.6784
-0.6617
-0.6640
-0.6655
-0.6581
-0.6631
-0.6562
-0.6496
-0.6506
-0.7043
-0.6899
-0.6882
-0.6803
-0.6659
-0.6657
-0.6678
-0.6601
-0.6655
-0.6586
-0.6525
-0.6538

0.0169
0.0151
0.0153
0.0154
0.0143
0.0151
0.0135
0.0134
0.0132
0.0214
0.0204
0.0204
0.0194
0.0178
0.0174
0.0166
0.0164
0.0162
0.0156
0.0152
0.0145
0.0230
0.0216
0.0216
0.0209
0.0190
0.0187
0.0185
0.0177
0.0178
0.0168
0.0162
0.0154

Eij(HB1)
(kJmol-1)

HB3

qH/e

qO/e

qt/e

Eij(HB2)
(kJmol-1)

0.4625
0.4621
0.4621
0.4621
0.4617
0.4619
0.4620
0.4613
0.4616
0.4612
0.4610
0.4612
0.4689
0.4686
0.4685
0.4683
0.4680
0.4677
0.4679
0.4674
0.4677
0.4673
0.4671
0.4670

-0.6969
-0.6959
-0.6957
-0.6947
-0.6948
-0.6924
-0.6928
-0.6943
-0.6959
-0.6916
-0.6898
-0.6908
-0.7092
-0.7076
-0.7088
-0.7091
-0.7041
-0.7053
-0.7045
-0.7061
-0.7032
-0.7030
-0.7015
-0.7019

0.0286
0.0283
0.0283
0.0282
0.0275
0.0273
0.0270
0.0273
0.0269
0.0268
0.0265
0.0257
0.0306
0.0305
0.0303
0.0300
0.0292
0.0288
0.0283
0.0287
0.0287
0.0283
0.0280
0.0279

60.6
60.0
60.0
59.8
58.5
58.1
57.6
57.8
57.2
57.2
56.7
55.2
63.2
63.5
62.9
62.5
61.0
60.0
60.0
59.8
59.6
59.0
58.5
58.1

41.7
38.7
38.9
37.3
33.9
34.3
34.4
32.0
33.8
30.8
30.3
30.0
46.2
43.9
43.9
41.9
36.6
38.2
36.6
35.9
35.5
34.4
33.5
32.3
48.8
45.8
45.8
44.4
40.9
41.0
39.9
39.0
38.1
36.7
35.4
33.8

qH/e

qO/e

qt/e

Eij(HB3)
(kJmol-1)

0.4646
0.4648
0.4648
0.4644
0.4645
0.4644
0.4644
0.4643
0.4644
0.4641
0.4642
0.4641

-0.7068
-0.7069
-0.7074
-0.7092
-0.7053
-0.7056
-0.7048
-0.7077
-0.7048
-0.7054
-0.7042
-0.7043

0.0310
0.0306
0.0307
0.0305
0.0304
0.0304
0.0305
0.0303
0.0303
0.0302
0.0301
0.0301

64.9
64.6
64.9
64.4
64.1
64.1
64.2
63.9
63.8
63.7
63.5
63.5

qH and qO are the partial charges of the hydrogen and oxygen atoms involved in a hydrogen bond, respectively, qt is the charge transfer between the
hydrogen bond proton donor and acceptor molecules, Eij is the second-order interaction energy between the oxygen lone pair
and the NH antibonding orbital.

.
,
.
HB1 qtEij(HB1)
, HB1 qtEij(HB1)
HB1 qtEij(HB1), HB1 qtEij(HB1)
HB1 qtEij(HB1), ,
HB1 qt Eij(HB1) .
HB2 qtEij(HB2), HB2 qtEij(HB2)

HB2 qtEij(HB2),
, HB2 qt Eij(HB2). ,
,
,
n(O)
NH *(NH)
. , 1-
N- NHOC

No.12

: 1- N-

2815

3 E qt
Eij
Fig.3 Relationship between E and qt, Eij
E is the relative hydrogen bonding energy obtained by subtracting the hydrogen bonding energy of the R=H system.
qt is the relative charge transfer and Eij is the relative second-order interaction energy obtained using the similiar way as E.

.
3 E
R=H , qt
R=H
, Eij
R=H
. 3 , E qt Eij .

(
), E qt Eij
, R=H ,

, ,
.

, NH
OC n(O) NH
*(NH)
;
. 1- N- N
HOC

.
Supporting Information:

The optimal geometries of hydro-

gen-bonded complexes at the B3LYP/6-31+G(d, p) level have

been included. This information is available free of charge via
the internet at http://www.whxb.pku.edu.cn.
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