Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.
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Supporting Information
Three Centered Hydrogen Bond of the type C=O…H(N)…X-C in
diphenyloxamide derivatives involving halogens and a rotating CF3
group: NMR, QTAIM, NCI and NBO Studies
A. Lakshmipriyaa,b, Sachin Rama Chaudharia,b, AbhishekShahic, E. Arunanc, N. Suryaprakasha,b,
aNMR
Research Centre, bSolid State and Structural Chemistry Unit, cInorganic and Physical
Chemistry, Indian Institute of Science, Bangalore 560012, India
E:mail: nsp@sif.iisc.ernet.in, Tel: +918022933300, Fax: +918023601550
INDEX
S1: 2D Coupled 1H-15N HSQC spectrum showing scalar coupling 1JNH for molecule 1 recorded
on a 400 MHz NMR spectrometer.
S2::2D Coupled 1H-15N HSQC spectrum showing scalar coupling 1JNH for molecule 2 recorded
on a 400 MHz NMR spectrometer.
S3:2D Coupled 1H-15N HSQC spectrum showing scalar coupling 1JNH for molecule 3 recorded
on a 400 MHz NMR spectrometer.
S4:2D Coupled 1H-15N HSQC spectrum showing scalar coupling 1JNH for molecule 4 recorded
on a 400 MHz NMR spectrometer.
S5:2D Coupled 1H-15N HSQC spectrum showing scalar coupling 1JNH for molecule5 recorded on
a 400 MHz NMR spectrometer.
S6:2D Coupled 1H-15N HSQC spectrum showing scalar coupling 1JNH for molecule6 recorded on
a 400 MHz NMR spectrometer.
S7: Stack plot of selected regions of 1H spectrum of molecules 1-6 with assignments.
S8: Experimental Parameters
S9: Table of 1JNHand chemicalshifts in diphenyloxamide (1) and its derivatives (2-6).
S10: General Procedure for Synthesis of compounds
1
S11: Reference
2
2D Coupled 1H-15N HSQC spectrum showing scalar coupling1JNH for the molecule 1.
S1
3
2D Coupled 1H-15N HSQC spectrum showing scalar coupling 1JNH for the molecule 2.
S2
4
2D Coupled 1H-15N HSQC spectrum showing scalar coupling1JNH for the molecule 3.
S3
5
2D Coupled 1H-15N HSQC spectrum showing scalar coupling1JNH for the molecule 4.
S4
6
2D Coupled 1H-15N HSQC spectrum showing scalar coupling1JNH for the molecule 5.
S5
7
2D Coupled 1H-15N HSQC spectrum showing scalar coupling1JNH for the molecule 6.
S6
8
S7
9
2D 1H-15N HSQC experimental parameters
parameter
Number of data points
Spectral width (Hz)
Window function used
F1 (15N)
256
40.559
QSINE
F2 (1H)
2048
400.128
QSINE
Pulse sequence used: hsqcetgp
Pulse width: 14.30μs
2D 1H-19F HOESY experimental parameters
Pulse sequence used: hoesyph
parameter
Number of data points
Spectral width (Hz)
Window function used
F1 (19 F)
256
240.108
SINE
F2 (1H)
880
3765.437
SINE
S8
10
Table: 1JNH and 15N chemical shiftvalues measured from 1H-15N HSQC
Spectra.
Molecule
1
2
3
4
5
6
1J
NH (CDCl3)
15N chemical shift of amide
proton (in ppm)
-91.3
-92.9
-92.0
-91.8
-90.8
-93.1
Coupling values
JFH
JNF
123.5
110.4
118.9
123.7
132.1
115.8
Molecule 2
CDCl3(Hz)
DMSO(Hz)
-2.9
+0.85
-0.4
-1.25
Molecule 6
DMSO(Hz)
CDCl3(Hz)
1.8
---1.5
---
S9
11
Experimental:
All the reagents were purchased from Aldrich and used without further purification. The
investigated molecules were synthesized according to the following procedure. The spectra were
recorded using Bruker 400 and 500 MHz NMR spectrometers. TheEurotherm temperature
control unit was utilized to set the temperature to an accuracy of ±1.0 K. The 1H chemical shifts
were referenced relative to TMS.15N spectra are referenced to external nitromethane, 19F spectra
are referenced to trifluoroacetic acid.
Synthesis Procedure:
All the investigated molecules 1-8 were synthesizes using the following procedure.
The substituted aniline (4mM, 2 eq) was dissolved in chloroform (4ml) and it was added drop by
drop to Oxalyl chloride (2mM, 1 eq ) at 00C.After stirring fornearly 10minsthe white solid
formed was washed with distilled water, and the compound was recrystallized from chloroform.
S10
12
G09 Reference:
Gaussian 09, Revision D.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji,
H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J.
L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.;
Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.;
Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.;
Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.;
Rega, N.; Millam, M. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo,
J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski,
J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg,
J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox,
D. J. Gaussian, Inc., Wallingford CT, 2009.
S11
13