Copyright © 2013 by American Scientific Publishers Advanced Chemistry Letters

All rights reserved. Vol. 1, pp. 1–6, 2013

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Structural Aspects, Biological and

Nonlinear Optical Response of New
N,N –Di(2-tolyl)Formamidinium Tosylate
Ram Kishan1 , Taruna Singh1 , Sandeep Garg2 , N. Vijayan3 , Rustam Singh1 , Yogesh Kumar4 ,
B. Rupini5 , and Brijesh Rathi1, ∗ †
1
Department of Chemistry, University of Delhi, Delhi 110007, India
2
Department of Zoology, Smt. Chandibai Himathmal Mansukhani College (University of Mumbai) Ulhasnagar,
Thane, Maharashtra, India
3
National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110017, India
4
Department of Physics and Astrophysics, University of Delhi, Delhi 110007, India
5
Department of Agriculture, Environmental Studies, Indira Gandhi National Open University, New Delhi 110068, India

N,N –Di(2-tolyl)formamidine (1) was protonated with the aim to explore the structural and solid state properties
of the resulting salt. Compound 1 upon protonation with p-toluene sulphonic acid hydrate afforded N,N –Di(2-

ARTICLE
tolyl)formamidinium tosylate, [1H]+ OTs− in 90% yield. Compound 1 and [1H]+ OTs− were fully characterized
by analytical, IR and NMR (1 H & 13 C) spectroscopic data. The composition of [1H]+ OTs− was further con-
firmed by single crystal X-ray diffraction data. The tosylate salt [1H]+ OTs− crystallized in P21 /n space group
and exhibited moderate N–H· · · O and C–H· · · O hydrogen bonding pattern in the crystal lattice. The thermal
stability of [1H]+ OTs− was evaluated by TGA technique. Both the molecules were found to be moderately
active against bacterial strains Staphylococcus aureus, Listeria monocytogenes, Bacillus subtilis, Enterococ-
cus faecalis, Klebsiella pneumoniae, Escherichia coli and Pseudomonas aeruginosa. Further, [1H]+ OTs− was
evaluated for second harmonic generation response by Kurtz-Perry powder technique.

KEYWORDS: Organic Ionic Crystals, Noncovalent Interactions, Second Harmonic Generation, Nonlinear Optics,
Antimicrobial.

1. INTRODUCTION cationic form with appropriate anion has been a promis-

The fabrication of organic crystals as hydrogen bonded
networks,1 and nonlinear optical materials,2–3 continues to
attract immense attention in recent years, owing to their
synthetic flexibility and better solubility in low polar sol-
vents than pure inorganic materials.4 Designing synthons
for hydrogen-bonded supramolecular assemblies with sig-
nificant second harmonic generation (SHG) efficacy has
been a challenging task for chemists. The formation of
ordered-solid state networks with a desired arrangement
and direction is determined by non-covalent interactions
such as hydrogen bonding in the crystal lattice. The salt
methodology i.e., conversion of a neutral molecule into its
∗
Author to whom correspondence should be addressed.
†
Email: brathi@svc.ac.in
Present address: Department of Chemistry, Sri Venkateswara College,
University of Delhi, Dhaula Kuan, New Delhi 110021, India.
Received: 26 October 2012
Accepted: 2 December 2012
ing criterion in tailoring the crystal engineering and solid
state properties of organic materials.5 6 Organic ionic crys-
tals are shown to exhibit higher mechanical and thermal
stabilities than those of neutral organic molecules.7 The
cationic organic molecular materials possessing p-toluene
sulphonate anion were shown to exhibit enhanced nonlin-
ear optical (NLO) property6 8–11 and also as synthon for
hydrogen bonded frameworks.10 12–18 P -toluene sulphonate
anion was shown to possess significant SHG response
because of the presence of a methyl group as an electron
donor and a sulphonate group as an electron acceptor.13
Formamidines are of much interest due to their role
as N -donor ligands for numerous metal ions as in their
neutral and anionic forms19 and biological importance.20
In this paper, we report synthesis and structural charac-
terization of N ,N  –Di(2-tolyl)formamidinium tosylate salt,
[1H]+ OTs− . N ,N  –Di(2-tolyl)formamidine (1) was proto-
nated, anticipating that the resulting salt could obey greater
SHG efficacy than the former. We also report antimicrobial

Adv. Chem. Lett. 2013, Vol. 1, No. 2 2326-747X/2013/1/001/006 doi:10.1166/acl.2013.1025 1

 Structural Aspects, Biological and Nonlinear Optical Response of New N N  –Di(2-tolyl)Formamidinium Tosylate
activity of both the compounds against several bacterial
strains.
2. EXPERIMENTAL DETAILS
2.1. General Considerations
All reagents required for the present investigation were
obtained from commercial sources and used as received.
The FTIR spectral data were obtained on a Schimadzu
IR435 spectrometer. 1 H and 13 C NMR spectra were
recorded on a JEOL ECX 400 NMR spectrometer oper-
ating at 400 and 100 MHz, respectively. Chemical shifts
are reported in ppm relative to the signals of tetram-
ethylsilane or residual solvent signals. Coupling constant
(J  are given in Hz. The elemental analyses were per-
formed on an Elementar Analysensystem Gmbh Variol.
The TGA/DTA thermogram of [1H]+ OTs− was measured
on Perkin Elmer Diamond instrument under nitrogen atmo-
sphere at 10  C/min heating rate. The relative second
harmonic conversion efficiency was carried out using mod-
ified setup of Kurtz and Perry.21 The powder of identical
ARTICLE
particle size of potassium dihydrogen phosphate (KDP)
crystals was used as reference material for the present
measurement. The powdered samples were sieved with
the particle size of 120 micron and packed in triangular
cell and kept in a cell holder. The Nd:YAG laser source
produces nanosecond pulses (8 ns) of 1064 nm light and
the energy of the laser pulse was around 100 mJ. The
rotation at 10 s per frame with SMART. The mea-
beam emerging through the sample was focused on to a
CzernyTurner monochromator using a pair of lenses. The
detection was carried out using a Hamamatsu R928 photo-
multiplier tube. The signals were captured with an Agilent
infiniium digital storage oscilloscope interfaced to a com-
puter. The monochromator is set at 532 nm NLO signal
is captured by the oscilloscope through the photomulti-
plier tube. After the 4 average, the signal light is measured
(peak to peak volts).
2.2. Synthesis and Spectroscopic Data
N ,N  –Di(2-tolyl)formamidine (1) was prepared according
to the literature procedure.22 The salt [1H]+ OTs− was syn-
thesized as shown in Scheme 1 by the following proce-
dure. Compound 1 (500 mg, 223 mmol) was taken in a
50 mL RB flask, dissolved in acetonitrile (20 mL) and set
to stir for 15 minutes to obtain a transparent solution. To
the RB flask, p-toluene sulphonic acid hydrate (424 mg,
223 mmol) was added and the resulting clear solution was
allowed to stir at room temperature for 12 h. The reaction
mixture was concentrated using rotary evaporator to afford
colorless solid. The title compound was secured in 90%
yield. The solid was subsequently purified by crystalliza-
tion from hot acetonitrile at room temperature for several
days to obtain single crystals suitable for X-ray diffraction
data.
2 Adv. Chem. Lett., 1, 1–6, 2013
Kishan et al.
N ,N  –Di(2-tolyl)formamidine (1): IR (KBr, cm−1  max :
3151 (m, NH), 1667 (vs., C N). 1 H NMR (400 MHz,
CDCl3 , ppm): H = 232 (s, 6H, CH3 , 7.00–7.05 (m, 4H,
ArH), 7.16–7.20 (m, 4H, ArH), 8.06 (s, 1H, NH). 13 C {1 H}
NMR (100 MHz, CDCl3 , ppm): C = 180 (CH3 , 117.8,
123.5, 127.0, 128.8, 130.7, 144.0, 148.0 (ArC and C N).
N ,N  –Di(2-tolyl)formamidinium tosylate, [1H]+ OTs− :
IR (KBr, cm−1  max : 3186 (m, NH), 1686 (vs., C N). 1 H
NMR (400 MHz, CDCl3 , ppm): H = 236 (s, 3H, CH3 ,
2.46 (s, 6H, CH3 , 7.17 (d, JHH = 80 Hz, 5H, ArH),
7.24 (br, 2H, ArH), 7.77 (d, JHH = 80 Hz, 2H, ArH)
7.99–8.05 (t, 1H, ArH) 12.75 (d, JHH = 124 Hz, 2H,
ArH). 13 C {1 H} NMR (100 MHz, CDCl3 , ppm): C = 180
(CH3 , 20.6, 21.3 (CH3 , 121.5, 125.9, 127.4, 128.2, 128.8,
131.7, 131.9, 135.4, 140.3, 141.7 (ArC). Anal. Calcd. for
C22 H24 N2 O3 S (Mw: 396.5): C, 66.64; H, 6.10; N, 7.07, S,
8.09. Found: C, 67.01; H, 6.09; N, 7.01; S, 8.12.
2.3. Single Crystal X-Ray Structure Determination
Intensity data of suitably sized crystals of [1H]+ OTs−
were collected on Oxford Xcalibur S diffractormeter (4-
circle kappa goniometer, Sapphire-3 CCD detector, omega
scans, graphite monochromator, and a single wavelength
Enhance X-ray source with MoK radiation).23 Pre-
experiment, data collection, data reduction and absorp-
tion corrections were performed with the CrysAlisPro soft-
ware suite.24 The frames were collected by , and
2
sured intensities were reduced to F 2 and corrected for
absorption with SADABS.25 The structures were solved
by direct methods using SIR 9226 which revealed the
atomic positions, and refined using the SHELX-97 pro-
gram package27 and SHELXL9728 (within the WinGX
program package).29 Non-hydrogen atoms were refined
anisotropically. C–H hydrogen atoms were placed in geo-
metrically calculated positions by using a riding model.
The molecular structures were created with a Diamond
program.30
2.4. Biological Evaluation
For Antimicrobial activity, compound 1 and [1H]+ OTs−
were diluted at a concentration of 5 mg/L DMSO. Pure
Bacterial strains of Staphylococcus aureus ATCC 25293,
Listeria monocytogenes ATCC 7644, Bacillus subtilis
ATCC8, Enterococcus faecalis ATCC 19433, Klebsiella
pneumoniae ATCC 7561, Escherichia coli ATCC 25422
and Pseudomonas aeruginosa 27853 were procured from
Hi-media laboratories, Delhi. These strains were main-
tained as frozen stocks in 25% glycerol at −20  C and
were propagated twice in Tryptic Soy Broth at 30  C
for 24 h before experimental use. Antimicrobial activity
was determined by the agar well diffusion method.31 In
brief, 20 mL of cation adjusted molten Mueller Hinton
Agar No. 2 (Hi-media, India) was seeded with 0.5 mL of
Kishan et al. Structural Aspects, Biological and Nonlinear Optical Response of New N N  –Di(2-tolyl)Formamidinium Tosylate

H SO3H
H SO3
CH3CN
N N
H + N NH
CH3 CH3
H CH3
RT CH3
CH3
CH3

Scheme 1. Synthesis pathway of N ,N  –Di(2-tolyl)formamidinium tosylate, [1H]+ OTs− .

inoculum (107 cfu/mL) and poured into sterile petri dishes 2.6. Statistical Analysis
(85 mm, Tarsons, India)). The plates were allowed to set,
after which wells (9 mm) were made in the plates with Data was statistically evaluated using statistical software
the help of a metal cup-borer. Each well was filled with SPSS, version 11.5. Values (p < 005) were considered as
0.1 mL of 1 and [1H]+ OTs− under aseptic conditions. significant.
Prepared plates were incubated at 37  C for 24 h. The
wells loaded with pure solvents (DMSO) and with pure
Ampiciliin (AMP) served as controls. Microbial growth
3. RESULTS AND DISCUSSION
was determined by measuring the diameter of the zone of 3.1. Characterization
inhibition. All assays were done in 4 replicates and the
mean values are presented. The IR spectrum of 1 revealed a band at 3150 cm−1
attributed to NH stretch and a band at 1667 cm−1

ARTICLE
attributed to C N stretch. A band appeared at 3186
2.5. Cytotoxicity/Cell Viability Test owing to the NH stretch and a band at 1686 cm−1
The toxicity of compounds 1 and [1H]+ OTs− was studied
by using MTT colorimetric assay.32 In brief, MCF-7 cells
were maintained in RPMI-1640 medium supplemented
with heat inactivated FCS (10% v/v) and 100 U/mL of
streptomycin. The cells were cultured in a humidified
5% CO2 atmosphere at 37  C. MCF-7 cells were seeded
onto 96-well plates at a density of 2 × 105 cells/well
and incubated for 16 h for adherence. Afterwards, the
media was aspirated from the wells and the cells were
washed once with RPMI-1640 without FCS. Compound
1 and [1H]+ OTs− with control Ampiciliin and DMSO
in concentration from 10–20 mg/L RPMI-1640 without
FCS in a final volume of 75 L, were added to separate
wells, followed by incubation at 37  C in humidified
5% CO2 atmosphere for 4 h. Then the media contain-
ing compounds was replaced with 200 l of normal
growth medium and cells were further incubated for 48 h
under same conditions. After 48 h media was replaced
by 200 L of MTT (3-(4,5-dimethylthiazol-2-yl)-2, 5-
diphenyltetrazolium bromide) (0.5 mg/mL of RPMI-1640)
and further incubated for 2 h. The formazan crystals
so formed were suspended in 100 L iso-propanol con-
taining 0.06 M HCl and 0.5% SDS and aliquots were
drawn from each well. Colour intensity of these aliquots
was measured spectrophotometrically in an ELISA plate
reader at 540 nm. Untreated cells were taken as control
with 100% viability and cells without addition of MTT
electrons are
were used as blank. The relative cell viability (%) com-
pared to control cells was calculated by [abs] sample/[abs]
control × 100.
Adv. Chem. Lett., 1, 1–6, 2013
region attributed to the C N stretch of the tosylate
salt, [1H]+ OTs− . 1 H NMR of compound 1 showed a
sharp singlet at H = 232 ppm corresponding to CH3 of
formamidine. N ,N  –Di(2-tolyl)formamidine tosylate salt
[1H]+ OTs− showed an upfield shift at H = 246 ppm
for CH3 protons in 1 H NMR spectrum. In the 1 H NMR
spectrum of [1H]+ OTs− a singlet was appeared at H =
236 ppm attributed to CH3 of p-toluenesulphonate anion.
13
C NMR of compound 1 showed signals at C = 180 and
148.0 ppm attributed to CH3 and C N, respectively. 13 C
NMR of compound [1H]+ OTs− showed signals at C =
180 and 21.3 ppm attributed to CH3 group of formamidine
and tosylate anion respectively. Upon protonation, the 13 C
NMR signal for C N shifted to 153.3 ppm in comparison
to the neutral formamidine (1) signal at 148.0 ppm.
3.2. Molecular Structure of [1H]+ OTs−
The molecular structure of [1H]+ OTs− with atom label-
ing scheme is shown in Figure 1. The selected bond
parameters are listed in Table I and the crystallographic
details are listed in Table II. The salt [1H]+ OTs− crys-
tallized in space group P 21 /n, monoclinic crystal system
and possesses a central carbon atom to which two nitro-
gen are covalently bonded. The elongated and nearly equal
C–N bond distances, 1.311(2) and 1.308(2) Å in the com-
pound [1H]+ OTs− reflects elongation of the C N bond
upon protonation. Upon protonation the
delocalized across the CN2 system and hence both C–N
and C N bond distances become nearly equal. The salt
[1H]+ OTs− is stabilized by moderate N–H· · · O and weak
3
 Structural Aspects, Biological and Nonlinear Optical Response of New N N  –Di(2-tolyl)Formamidinium Tosylate Kishan et al.

Table II. Crystallographic data of [1H]+ OTs− .

[1H]+ OTs−

CCDC no 874687
Formula C22 H24 N2 O3 S
Fw 396.50
T/K 298(2)
/Å 0.71073
Crystsyst Monoclinic
Space group P 21/n
a/Å 12.3233(6)
b/Å 8.1100(4)
c/Å 20.4677(12)
/deg 90
Fig. 1. Molecular diagram of [1H]+ OTs− at 40% probability. /deg 100.454(5)
/deg 90
V/Å3 2011.63(18)
C–H· · · O hydrogen bonding in the crystal lattice. Hydro- Z 4
gen bonding geometries for the salt are listed in Table III. Dcalcd /g/cm−3 1.306
The formamidinium cation in [1H]+ OTs− binds to the F (000) 836
/mm−1 0.186
tosylate anion through N–H· · · O hydrogen bonding. The
range/deg 3.19–26.37
two amine nitrogen N1 and N2 are involved in N–H· · · O Reflns measured 7720
hydrogen bonding with two oxygen atoms O2 and O3 Reflns used 6259
of the tosylate anion (Fig. 2). The oxygen atom O1, O2 Parameters 256
ARTICLE

R1 0.0449
and O3 of the tosylate anion are also involved in weak
wR2 0.1647
C–H· · · O hydrogen bonding to give a chain along ab plane Goodness of fit on F 2 1.408
and the two molecules are related by 2-fold screw axis
symmetry (Fig. 3).
Table III. Hydrogen bonding geometries for [1H]+ OTs− .

3.3. Measurement of Nonlinear Optical D–H· · · A D–H H–A D–A D–H· · · A

Efficiency of [1H]+ OTs− N(1)–H(1)–O(2) 0.861 1.965 2.802 166
N(2)–H(2)–O(3) 0.860 2.209 2.960 146
It was anticipated that upon protonation the resulting salt C(1)–H(1A)–O(1) 0.930 2.354 2.999 126
could be a better agent for SHG purpose than the neu- C(3)–H(3)–O(3) 0.930 2.369 3.286 169
tral formamidine. In the protonated salts charge transfer C(14)–H(14)–O(2) 0.930 3.337 3.847 117
C(15)–H(15C)–O(3) 0.960 2.691 3.524 145
between cation and anion takes place and SHG response
is enhanced. The tosylate salt [1H]+ OTs− was subjected Symmetry code: (i) 1 − x, 2 − y, −z; (ii) 1 − x, 1 − y, −z.
to second harmonic efficiency (SHG) measurement by
adopting Kurtz powder technique and KDP was used as
reference. The salt [1H]+ OTs− was shown to possess
SHG response however, the neutral compound 1 did not
respond. The observed SHG signals height for [1H]+ OTs−
and standard are represented in Figure 4.


Table I. Selected bond distance (Å) and bond angles (in ) for
[1H]+ OTs− .

S1–O1 1.421(2) O1–S1–C16 107.6(8)

S1–O2 1.449(1) O2–S1–C16 105.6(8)
S1–O3 1.445(2) C1–N1–C2 124.1(1)
S1–C16 1.769(2) C1–N1–H1 118.0(1)
N1–C1 1.308(2) C2–N1–H1 118.0(1)
N2–C1 1.311(2) C1–N2–C9 124.9(1)
N1–C2 1.426(2) C1–N2–H2 117.6(1)
N2–C9 1.422(2) C9–N2–H2 117.5(1)
O1–S1–O3 115.4(9) N1–C1–N2 122.4(2)
O1–S1–O2 112.9(9) N1–C1–H1A 118.8(2)
O3–S1–O2 109.8(8) N2–C1–H1A 118.8(2)
Fig. 2. Representation of N–H· · · O hydrogen bonding in [1H]+ OTs− .

4 Adv. Chem. Lett., 1, 1–6, 2013

Kishan et al. Structural Aspects, Biological and Nonlinear Optical Response of New N N  –Di(2-tolyl)Formamidinium Tosylate

Fig. 3. Representation of C–H· · · O hydrogen bonding in [1H]+ OTs− .

3.4. Thermal Studies 3.5. Antimicrobial Activity and Cell Toxicity

Figure 5 shows the TGA thermograms of 1 and The results of antimicrobial activity of N  N  –Di(2-
[1H]+ OTs− compounds. The compound 1 (shown as dot- tolyl)formamidine and its tosylate salt, [1H]+ OTs− were
ted line) has the onset of weight loss at 127  C and compared with a known antibiotic Ampiciliin and are sum-

completely decomposed at 292  C. No weight loss up to
100  C in both the compounds is indicative of absence
of any water molecule. The compound [1H]+ OTs− has
the onset of decomposition near to 220  C, which indi-
cates that the thermal stability of the compound has been
increased after salt formation. The TGA thermogram of
[1H]+ OTs− shows two steps weight loss, the first one (I)
at 365  C is probably due to liberation of tosylate group
and step (II) at 536  C is due to characteristics weight loss
of decomposition of compound 1. These two thermograms
distinctly shown that the thermal stability has also been
increased in terms of 100% decomposition takes place at
292  C in case of compound 1 in comparison to the salt
[1H]+ OTs− at 545  C.
ARTICLE
marized in Table IV. The zone of inhibition (mm) showed
by both the compounds with all gram +ve and −ve bac-
terial strains was moderate but significantly (p < 005
lower when compared to Ampiciliin. Though, no signifi-
cant (p > 005 difference was observed in zone of inhibi-
tion showed by compound [1H]+ OTs− compared to zone
of inhibition of compound 1.
In vitro cell viability was moderate for compound 1
and [1H]+ OTs− and the results are presented in Figure 6.
Though no significant (p > 005 difference was observed
among the cell viability of all the tested compounds and
controls.

100
1

80 [1H]+ OTs–

60
Weight%

40

(I)
20

(II)
0

–20

100 200 300 400 500 600 700 800 900

Temprature ºC

Fig. 4. Recorded SHG pattern of [1H]+ OTs− in comparision with KDP. Fig. 5. TGA plots of compound 1 and [1H]+ OTs− .

Adv. Chem. Lett., 1, 1–6, 2013 5

 Structural Aspects, Biological and Nonlinear Optical Response of New N N  –Di(2-tolyl)Formamidinium Tosylate Kishan et al.

Table IV. Antimicrobial analysis of 1 and [1H]+ OTs− . Vols. 1 and 2; (b) S. R. Marder, J. E. Sohn, and J. D. Stucky (eds.),
Materials for Nonlinear Optics: Chemical Perspective, Eds ACS
Zone of inhibition (mm) Symp. Ser., American Chemical Society, Washington, DC (1991),
p. 455.
Strain AMP (+) DMSO (−) 1 [1H]+ OTs−
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Staphylococcus aureus 10.2 1.1 9.7 8.2 B. Rathi, M. A. Wahab, and G. Bhagavanarayana, Spectrochim. Acta
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Bacillus subtilis 10.5 2.9 8.1 7.3 Babu, K. Nagarajan, D. Haranath, and G. Bhagavannarayana, OPTIK
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10
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