Effect

Received: July 27, 2012; Revised: September 25, 2012; Published on Web: September 26, 2012.Corresponding author. Email: [email protected]; 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

1-N- *

(, 116029)

: B3LYPMP21-N-,1-.:NHOC r(HO),;NHOC r(HO),.(NBO):,,;.NHOCn(O)NH*(NH),.NHOC.

: ; ; ; ; : O641

Effect of Substituents on Hydrogen Bond Strength in Hydrogen-BondedN-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 NHOC hydrogen-bonded complexes containing1-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 withdrawinggroups lengthen the HO distance and weaken the NHOC 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 chargetransfer 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 the1-methyluracil-containing complex (R=H), while electron withdrawing groups result in smaller second-order

interaction energies.

Key Words: Hydrogen-bonded complex; Substituent; Hydrogen bond strength; Natural bond orbital

analysis; Hydrogen bond cooperativity

[Article] doi: 10.3866/PKU.WHXB201209263 www.whxb.pku.edu.cn

(Wuli Huaxue Xuebao)Acta Phys. -Chim. Sin. 2012, 28 (12), 2809-2816December 2809

Acta Phys. -Chim. Sin. 2012 Vol.28

1

, ,.1-12MohajeriNobandegani515NHNNHO.Kolew 9. Dong 13, --. Vargas 14N-NHOC,N-NHOC-36.0kJmol-1, NHOC-29.7 kJmol-1. Kawahara 15,16MP2-AX-UCX-G,. Wang 17-22, , (BSSE)MP2. Dannenberg 23-25 B3LYP/D95**. WuZhao26,27,-310-. Tan 28

B3LYP/cc-pVTZN-,.

, . Hunter 29N1. Jeong 30-RNA. Cheng Frankel31HF/6-31G(d) 28-,21. ProtNA-ASA 214-DNA 28-RNA.32MP2 1-N-NHOC,NHOC.

2 1

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

1 Fig.1 Structures of hydrogen-bonded complexes

2810

:1-N-No.12

BSSEMP2/6-311++G(d, p)MP2/6-311++G(3df, 2p)., B3LYP/6-31+G(d,p).Gaussian 03 33.

3 3.1 36,

215.21 S1 ( Supporting Information).

, R=H1-N-NHOC,HB1 r(HO)HB10.2016 nm,HB2 r(HO)HB2 0.1950 nm. R NH2EtMe,HB1HB2R=H, HB1. : R=NH2, r(HO)HB1 0.1987 nm, 0.0029 nm;r(HO)HB2 0.1947 nm, 0.0003 nm. R BH2COMeCONH2CHOCF3CNNO2SO3H,R=H,HB1HB2. : R=NO2, r(HO)HB10.2076 nm,0.0060 nm; r(HO)HB20.1965

2 15Fig.2 Optimal geometries of 15 hydrogen-bonded complexes

bond length in nm, bond angle in degree

2811


nm,0.0015 nm,HB1..HB1

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

.1, 1-.NH2EtMe,; BH2COMeCONH2CHOCF3CNNO2SO3H, . BSSEMP2/6-311++G(d, p),, R=H,HB1EHB1=-22.6kJmol-1; HNH2, EHB1=-24.5kJmol-1,1.9 kJmol-1;HSO3H, EHB1=-16.9 kJmol-1,

1 36Table 1 Hydrogen bond energies and hydrogen bond distances of thirty-six hydrogen-bonded complexes

dimer

trimer

tetramer

R

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

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

r(HO)HB1nm

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

r(HO)HB2nm

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

r(HO)HB3nm

0.1930

0.1930

0.1929

0.1930

0.1932

0.1933

0.1933

0.1934

0.1933

0.1935

0.1935

0.1935

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

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

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

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

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

2812

:1-N-No.12

5.7 kJmol-1. , R=H, EHB1=-25.9 kJmol-1, EHB2=-34.0 kJmol-1; HNH2, EHB1=-28.2 kJmol-1, 2.3 kJmol-1, EHB2=-34.4 kJmol-1, 0.4 kJmol-1;HSO3H, EHB1=-17.3 kJmol-1, 8.6 kJmol-1, EHB2=-31.2 kJmol-1,2.8 kJmol-1., R=H, EHB1EHB2EHB3-26.4-40.7-36.6 kJmol-1;HNH2, EHB1EHB2 EHB3-29.0-41.3-36.9 kJmol-1,2.60.60.3 kJmol-1;H SO3H,EHB1EHB2EHB3-17.6-37.4-36.2 kJmol-1, 8.83.30.4 kJmol-1.,,,.EHB1,

EHB1EHB1, EHB1EHB1,,HB1.EHB2,EHB2EHB2,,HB2.,, , 1- N-NHOC.3.3 (NBO) 2B3LYP/6-31+G(d, p)

36(NBO)., qH, qO, qt, Eijn(O)NH*(NH)..R=HHB1

0.4592e,-0.6784e (234);HB2 0.4621e,-0.6947e (278).R=H,NH2,HB1qH0.4614e,0.0022e, qO-0.6984e,0.0200e;HB2qH0.4625e, 0.0004e, qO-0.6969e,

0.0022e.NH2,1-,,,.RSO3H,HB1qH0.4543e,0.0049e, qO-0.6506e,0.0278e;HB2qH0.4612e, 0.0009e, qO -0.6908e, 0.0039e.SO3H,1-,, , ., , ,, , .25,HB1, R=H

0.0194e;29,HB2, R=H0.0282e.NH2,HB1HB2 0.0214e 0.0286e,R=H 0.0020e 0.0004e.SO3H,HB1HB2 0.0145e 0.0257e,R=H0.0049e0.0025e.,,.2,HB1HB1HB2. 2 6 10, R=H

HB1HB241.959.8 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) 58.5kJmol-1, 1.3 kJmol-1.,,,HB1

2813


.,

.HB1qtEij(HB1)

, HB1 qtEij(HB1)HB1qtEij(HB1),HB1qtEij(HB1)HB1 qtEij(HB1),,HB1 qt Eij(HB1). HB2 qtEij(HB2),HB2 qtEij(HB2)

HB2 qtEij(HB2), , HB2qtEij(HB2).,,, n(O)NH*(NH)., 1-N-NHOC

dimer

trimer

tetramer

R

NH2Et

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

HB1

qH/e

0.4554

0.4545

0.4545

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

qO/e

-0.6886

-0.6759

-0.6758

-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

qt/e

0.0189

0.0175

0.0176

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)

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

HB2

qH/e

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

qO/e

-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

qt/e

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

Eij(HB2)(kJmol-1)

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

HB3

qH/e

0.4646

0.4648

0.4648

0.4644

0.4645

0.4644

0.4644

0.4643

0.4644

0.4641

0.4642

0.4641

qO/e

-0.7068

-0.7069

-0.7074

-0.7092

-0.7053

-0.7056

-0.7048

-0.7077

-0.7048

-0.7054

-0.7042

-0.7043

qt/e

0.0310

0.0306

0.0307

0.0305

0.0304

0.0304

0.0305

0.0303

0.0303

0.0302

0.0301

0.0301

Eij(HB3)(kJmol-1)

64.9

64.6

64.9

64.4

64.1

64.1

64.2

63.9

63.8

63.7

63.5

63.5

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

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.

2814

:1-N-No.12

. 3E

R=H, qtR=H, EijR=H.3, EqtEij.(),EqtEij,R=H,,, , .

4 ,

NHOC., r(HO), ; , r(HO),.(NBO),NHOC, ,

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

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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