An old oxovanadium(IV) complex of N-(salicylidene)sulfanilamide: theoretical validity of experimental observations

Article abstract of DOI:10.1080/24701556.2019.1569682

Sulfa drug Schiff base complexes of oxovanadium are counted among highly significant molecular scaffolds of industrial and medicinal relevance. In order to present a theoretical validation of our earlier reported complex of this sort herein, a comparative

Full text of DOI:10.1080/24701556.2019.1569682

Inorganic and Nano-Metal Chemistry
ISSN: 2470-1556 (Print) 2470-1564 (Online) Journal homepage: https://www.tandfonline.com/loi/lsrt21
An old oxovanadium(IV) complex of N-
(salicylidene)sulfanilamide: theoretical validity of
experimental observations
Jan Mohammad Mir, Pradeep Kumar Vishwakarma, Bashir Ahmad Malik &
Ram Charitra Maurya
To cite this article: Jan Mohammad Mir, Pradeep Kumar Vishwakarma, Bashir Ahmad Malik &
Ram Charitra Maurya (2019): An old oxovanadium(IV) complex of N-(salicylidene)sulfanilamide:
theoretical validity of experimental observations, Inorganic and Nano-Metal Chemistry, DOI:
10.1080/24701556.2019.1569682
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INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2019.1569682
An old oxovanadium(IV) complex of N-(salicylidene)sulfanilamide: theoretical
validity of experimental observations
Jan Mohammad Mir , Pradeep Kumar Vishwakarma, Bashir Ahmad Malik, and Ram Charitra Maurya
Coordination, Bioinorganic and Computational Chemistry Laboratory, Department of P. G. Studies and Research in Chemistry and Pharmacy,
R. D. University, Jabalpur, India
ABSTRACT
ARTICLE HISTORY
Sulfa drug Schiff base complexes of oxovanadium are counted among highly significant molecular
scaffolds of industrial and medicinal relevance. In order to present a theoretical validation of our
earlier reported complex of this sort herein, a comparative experimental theoretical investigation
Received 2 January 2018
Accepted 2 January 2019
KEYWORDS
Sulfa drug;
Oxovanadium(IV) complex;
of N-(salicylidene)sulfanilamide Schiff base and its oxovanadium(IV) complex, [VO(sal-snm)
based on density functional theory calculations using the B3LYP as functional and 6-31þþG(d,p)
for ligand)/LANL2DZ (for Vanadium) basis set is being reported. The calculated vibrational fre-
2 2
(H O)]
(
[
2 2
VO(sal-snm) (H O)]; DFT
quencies have been compared with experimental FT-IR spectra of the selected compounds. The
Molecular geometry optimizations, frontier orbital analysis, hyperpolarizability calculations and
molecular electrostatic surface potential (MESP) topologies of the title compounds have been
sought in this work. From the molecular geometrical optimization of the oxovanadium(IV) complex
a suitable octahedral structure has been confirmed. The calculated HOMO and LUMO energies
show that charge transfer occurs within the molecules. The Non-linear optical properties encom-
passing the applicability of electric dipole moment (l), polarizability (a), mean polarizability (Da)
calculations; HOMO-LUMO;
NBO analysis; NLO; MESP
0
and hyperpolarizability (b ) values have been evaluated through quantum chemical calculations.
GRAPHICAL ABSTRACT
1
. Introduction
such metal complexes containing nitrogen and oxygen
[
6–9]
donors
have driven attention of researchers to carry out
Sulfa drug Schiff bases have been shown to possess well pro-
nounced biological implications and has led to considerable
interest in their coordination chemistry. Their broad spec-
trum biological activity has attracted researchers to investi-
gate the respective sensitivity in various fields of medicine
hyphenated experimental-density functional theory (DFT)
study of vamadium(IV) complexes of this form. This may
[
6,7]
be attributed due to coordination chemistry
of vanadium
has acquired renewed interest since the discovery of van-
adium in organisms such as certain ascidians and Amanita
muscaria mushrooms and as a constituent of the cofactors
in vanadate-dependent haloperoxidases and vanadium nitro-
suggested genase. Vanadium is a transition metal that, being ubiqui-
[
1]
(Maurya et al. 2015). Nagpal and Singh have reported
Sulfonamides as the first drugs found to have potentiality to
act against various diseases. Due to fascinating properties of
Sulphur containing organic chelates Sharaby
[
2]
these ligands among efficient coordination compounds. The tously distributed in soil, crude oil, water and air, also found
Schiff base complexes of this form have been found to have roles in biological systems and is an essential element in
catalytic significance in terms of both in vivo and in vitro most living beings. There are also several groups of organ-
[
3–5]
experiments.
The evidences of fascinating properties of isms which accumulate vanadium, employing it in their
CONTACT Jan Mohammad Mir
mirjanmohammad@gmail.com
Coordination, Bioinorganic and Computational Chemistry Laboratory, Department of P. G.
Studies and Research in Chemistry and Pharmacy, R. D. University, Jabalpur, M.P. 482001, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsrt.
Supplemental data for this article is available online at publisher’s website.
ß 2019 Taylor & Francis Group, LLC

2
J. M. MIR ET AL.
biological processes. It is not surprising to state that many
In connection of widely applications for Schiff base
vanadium based therapeutic drugs have been proposed for ligands and their oxovanadium(IV) complexes, herein syn-
the treatment of several types of diseases. Hence, both the thesis, characterization and theoretical evaluation of an
ligand and its complex enlightened in the current report are oxovanadium(IV) complex containing sulfa drug Schiff base
[
8]
equally significant in scientific research.
In addition to aforementioned applications, the quantum being reported.
ligand derived from salicylaldehyde and sulfanilamide is
[
18]
The comparative experimental and theor-
chemical studies carried out using the density functional etical studies of the title compounds have been performed.
theory (DFT) have become an increasingly useful tool for Mulliken atomic charges, frontier molecular orbital, NLO
theoretical studies. The success of DFT is mainly due to the properties and MESP of the title compounds theoretically
[
9,10
fact that it describes the small molecules more reliably.
]
investigated by using various DFT methods including
Density-functional theory (DFT) serves as a powerful B3LYP, in 6-311 þ G(d,p)/LANL2DZ basis set.
method for predicting the geometry of vanadium com-
[
11–15]
pounds
investigation carried out by Jacob and Fiscker
even in the absence of X-ray data. DFT based
[
16]
2. Experimental
suggests
the application of this tool for large molecules as well. The 2.1. Materials and synthesis
Cartesian representation of the theoretical force constants
VSO ꢀ5H O and Salicylaldehyde (E. Merck, Germany), sulf-
4
2
are usually computed at optimized geometry by assuming
Cs point group symmetry. To show the existence of intra-
molecular charge transfer (ICT) within molecular system
energies of the highest occupied molecular orbital (HOMO)
and lowest unoccupied molecular orbital (LUMO) levels and
the molecular electrostatic surface potential (MESP) energy
anilamide (Sigma Aldrich Co., USA), ethanol (Bengal
Chemicals and Pharmaceuticals Ltd., Kolkata), were used as
supplied. All other chemicals used were of analytical
reagent grade.
The sulfa drug Schiff base N-(Salicylidene)sulfanilamide
[
18]
[
17]
was prepared as the method reported elsewhere.
nolic solution (10 mL) of salicylaldehyde (0.244 g, 0.209 mL,
mmol) was added to the ethanolic solution (20 mL) of sulf-
An etha-
surface studies are manipulated by DFT.
2
anilamide (0.344 g, 2 mmol). A colored solid mass separated
ꢁ
out when the mixture was heated at 80 C for ꢂ20 min. It
was filtered, washed several times with ethanol and diethyl
ether and subsequently, dried over anhydrous CaCl in a
2
desiccator. The sulfa drug containing oxovanadium(IV)
complex, [VO(sal-snm) (H O)] was prepared by using the
2
2
[
18]
method employed elsewhere.
Salicylidene)sulfanilamide (0.276 g, 1 mmol) in the min-
imum quantity of DMF was mixed with ethanol (ꢂ20 mL).
A suspension of N-
(
Figure 1. Optimized 3D-molecular structure of N-(Salicylidene)sulfanilamide.
2 2
Figure 2. Optimized 3D-molecular structure of [VO(sal-snm) (H O)].

INORGANIC AND NANO-METAL CHEMISTRY
3
The resulting mixture was refluxed with stirring on a mag- 2.3. Computational methods
netic stirrer equipped with heater for 1 h. to get a clear solu-
The Schiff base ligand, N-(salicylidene)sulfanilamide (sal-
snmH), and its oxovanadium(IV) complex, [VO(sal-
snm) (H O)], were first structurally optimized using Gaussian
tion. The salt of VOSO ꢀ5H O (0.1265 g, 1 mmol) was
4
2
dissolved in ethanol-water (4:1, 5 mL) and the solution so
obtained was added to a hot, stirred ethanolic solution of
the Schiff base. The resulting solution was refluxed for
ꢂ10 h, and then concentrated to half of its volume. The
resulting colored precipitate was then filtered and washed
several times with ethanol to remove any unreacted ligand
and the metal salt. The product was dried in vacuo.
2
2
[
19]
0
9W program package
at the Becke3–Lee–Yang–Parr
[
20,21]
(B3LYP) functional mentioned in the literature
with the
standard 6-31þþ G (d, p) and LANL2DZ basis sets, respect-
ively. The main reason for choosing the LANL2DZ basis set
is its inclusion of relativistic effects that is essential for heavy
transition elements, e.g. VO(IV). The vibrational frequencies
the corresponding to the normal modes were evaluated at the
[
19–21]
Table 1. Selected optimized geometrical parameter like bond lengths in (Å) optimized geometry using the same basis sets.
ꢁ
angle in ( ) obtained by theoretical calculation of the complex.
Bond length
V(57)–O(58)
V(57)–O(59)
V(57)–O(8)
1.6467
1.8500
1.9134
V(57)–N(9)
V(57)–O(28)
V(57)–N(29)
1.9709
1.9133
1.9816
3. Result and discussion
3
.1. Molecular geometry optimization
Bond angle
O(8)–V(57)–N(9)
O(8)–V(57)–O(28)
O(8)–V(57)–N(29)
O(8)–V(57)–O(58)
O(8)–V(57)–O(59)
N(9)–V(57)–O(28)
N(9)–V(57)–N(29)
N(9)–V(57)–O(58)
96.2883
175.9665
83.9969
94.5494
85.4593
84.0417
176.8550
87.9459
O(9)–V(57)–O(59)
O(28)–V(57)–N(29)
O(28)–V(57)–O(58)
O(28)–V(57)–O(59)
N(29)–V(57)–O(58)
N(29)–V(57)–O(59)
O(58)–V(57)–O(59)
92.0535
95.8950
89.4789
90.5124
88.9090
91.0915
The optimized molecular structures of the Schiff base ligand,
N-(Salicylidene)-sulfanilamide and its oxovanadium(IV) com-
plex have been given in Figures 1 and 2, respectively.
As shown in Figure 1, the selected bond lengths of N-
179.9912 (Salicylidene)sulfanilamide are: C(5)ꢃO(8), 1.3440 Å and
C(7)¼N(9), 1.2957 Å. The C ꢃ C bond lengths in the
Figure 3. Experimental (a) and (b) Theoritical IR spectrum of N-(Salicylidene)sulfanilamide.

4
J. M. MIR ET AL.
Figure 4. Expermental (a) Theoretical (b) IR spectrum of [VO(sal-snm)(H
2
2
O)]ꢀH O.
aromatic ring are C(1)ꢃC(6), 1.4161 Å and C(1)ꢃC(2), the Schiff base ligand are shown in Figure 3. The corre-
.3861Å, indicating the single and double bond respectively. sponding bands (experimental/theoretical) viz. 3600/3630,
1
On the other hand, the structural properties such as bond 3365/3206, 3500/3202, 3056/3052, 1671/1666, 1604/1602,
ꢁ
lengths (Å) and bond angles ( ) of the complex are given in 1302/1304, 1136/1122 are assignable to ꢀ(NH ), ꢀ(OH)
2
Table 1. From the tabulated data it is observed that the differ- (phenolic), ꢀ(NH), ꢀ(CH), d(NH ), ꢀ(C ¼ N)(azomethine),
2
ent bond lengths confined to coordination sphere are ꢀ (SO ), ꢀ (SO ), respectively. These data are in excellent
as
2
s
2
[
23]
V ¼ O(58), 1.6466; VbO(59), 1.8500; Vꢃ O(8), 1.9134; agreement reported by Maurya and Rajput.
ꢀ
VbN(9), 1.9709; VbO(28), 1.9133 and VbN(29), 1.9816 (Å)
On the other hand, comparative experimental-theoretical
and the significant bond angles useful in describing geometry spectral diagram of the complex (Figure 4) indicates that the
ꢃ1
of the complex viz. N(9)bVbO(29), 176.8550; O(8)bVbO(28), band around 3365 cm
75.9664 and O(10)bVbO(18), 179.9912 for
has disappeared and a new band
ꢃ1
1
the appeared at 1317/1288 cm [due to v(C–O)] indicating the
oxidovanadium(IV) complex are very close to the experimen- coordination of oxygen atom after deprotonation. But due to
[
22]
tal values reported by Parihar et al.
The above geometrical the presence of a broad band (vide-infra) for lattice and coor-
data suggest that the complex bears octahedral geometry.
dinated water molecule. The coordination of phenolic oxygen
is further supported by the appearance of a non-ligand band
ꢃ1
[24]
at 578/537 cm , due to ꢀ(V–O)
in the complex. The
3.2. Infrared spectral studies
absorption due to azomethine group (–C ¼ N–) at 1604/
ꢃ1
The Schiff base under study contains five potential donor 1602 cm found in the IR spectrum of the ligand has been
sites: (i) the phenolic oxygen, (ii) the azomethine nitrogen shifted to 1584/1590 cm in the spectrum of the complex.
ꢃ1
(
(
iii) the sulfonamide oxygens (iv) sulfonamide sulfur and This is indicative of the coordination of azomethine nitrogen
iv) the primary amine nitrogen along the sulfonamide side. to the metal center. This is further supported by the appear-
ꢃ1
The combined experimental and theoretical IR spectra of ance of new band at 459/447 cm due to the ꢀ(V–N) band

INORGANIC AND NANO-METAL CHEMISTRY
5
Figure 5. Bar diagram representation of Mulliken atomic charges of complex.
3
.3. Mulliken atomic charges
The Mulliken atomic charges of title compounds obtained by
[
30]
Mulliken population analysis
have been illustrated in
Figures 5 and S1 in supplementary materials. The color range
in the scale of positive and negative charge for Mulliken
atomic charges of the compounds are is shown in Figures 6
and S2 in supplementary materials. Mulliken atomic charge
calculation has a significant role in the application of quan-
tum chemical calculations to molecular systems because of
atomic charges affect some properties of molecular systems
including dipole moment, and molecular polarizability. The
results show that the atoms namely Sulfur and all hydrogen
are positively charged and the oxygen’s, namely and nitrogen
are negatively charged in the analyses. While some carbons
are positively charged rest are negatively charged. While in
This is the complex, metal has bigger positive atomic charge (0.693e)
Figure 6. The color range in the scale of positive and negative charge for
Mulliken atomic charges of complex in atomic units (a.u.).
[25]
similar to the result reported by Maurya et al.
logical in terms of six-member chelate ring formation includ- than the other atoms. This is coordinated to two nitrogen and
ing metal on account of bidentate coordination of azomethine four oxygen atoms namely N (–0.256e), N29(–0.243e), O (–0.
9
8
nitrogen and phenyl oxygen from ortho position. It is here to 681e), O28(–0.660e), O58(–0.329e) and O59(–0.664e) they are
mention that the applied formalism in DFT calculations are negative charged atoms. Moreover, Mulliken atomic charges
often expected to possess systematic errors. In order to give a also confirm that a vanadium and two sulfur atom in the
clear cut relevance of such factors scaling procedures are complex is more acidic due to more positive charge they are
bind with negatively charges atoms.
applied in theoretical calculations. Researchers have always
been seeking such a simple linear scaling empirical factor close
to 1. In the present case 0.8 was established as a scaling factor.
Most of the oxovanadium(IV) complexes display a strong
3
.4. Frontier molecular orbitals analysis
ꢃ1
[26]
band near 1000 cm assignable to v(V ¼ O).
Contrary to HOMO and LUMO are very important parameters to charac-
this, several oxovanadium(IV) complexes have been found terize the electronic structure of molecules. We can determine
in which this stretching mode appears at quite lower indi- the way the molecule interacts with other species. Hence, they
[
24,27]
ꢃ1
cated in the literature
wave numbers around 900 cm
are called the frontier orbitals. The HOMO is the orbital that
due to presence of a –V ¼ O–V ¼ O– chain structure, which primarily acts as an electron donor and the LUMO is the
is formed by the interaction of vanadyl oxygen of one mol- orbital that largely acts as the electron acceptor, and the gap
[
28]
ecule with a vanadium metal in another molecule.
In between HOMO and LUMO characterizes the molecular
ꢃ1
[31]
case of present complex, v(V ¼ O) is found at 943/936 cm
chemical stability.
The molecular orbitals (MOs) denoted
suggesting the absence of a –V ¼ O–V ¼ O–chain. The pres- as HOMO ꢃ 2, HOMO ꢃ 1, HOMO, LUMO, LUMO þ 1,
ence of a coordinated water molecule in this complex LUMO þ 2 have been worked out for Schiff base sal-snmH
(
discussed above) supports this fact. The presence of coordi- and its oxovanadium(IV) complex. The respective energies
nated water in the complex is revealed by the presence of a and energy gap (DE) of the molecular orbitals in both of the
ꢃ1
broad band at 3406/3249 cm i2s9]comparable to the similar compounds are shown in Figures 7 and S3 in supplementary
[
study reported by Maurya et al.
materials, respectively. It is well known that the energy gap

6
J. M. MIR ET AL.
Figure 7. FMOs (HOMO þ LUMO) with energy level three-dimensional structure of the complex.
Table 2. Some theoretical parameters and their values of title compounds.
complex, [VO(sal-snm) (H O)] calculated using equations
2
2
(i) to (iv) are represented in Table 2. There is very short gap
Parameters
Sal-snmH
B3LYP
6-31 G(D,P)
[VO(sal-snm)
2 2
(H O)]
between HOMO and LUMO in the complex as compared
with the Schiff base ligand. That is to say, smaller energy
gap corresponds to a higher reactivity. Comparing the band
gap (DE) of the ligand and its corresponding complex
oxovanadium(IV) complex can be considered as the less
reactive and more stable. Other important properties related
to the dipole moment and hardness is electrophilicity index
Calculation method
Basic set
Charge
Spin
Total energy
RMS gradient
Dipole moment
Point group
B3LYP
LANL2DZ
0
þþ
0
Singlet
doublet
ꢃ1235.9672
ꢃ52155.6152
0.0016
1.0247
4.5826
C1
ꢃ3.979
ꢃ4.4780
ꢃ1.99
7.2832 Debye
C1
DE
0.2272
(
x), global softness (S) shown in below equation. The values
Absolute electronegativity (vabs
Absolute hardness (g)
Electrophilicity index (x)
Global softness (S)
)
ꢃ3.8087
ꢃ0.11375
of x and S are given in Table 2.
ꢃ605.5408
ꢃ0.5025
ꢃ2497.7556 eV
ꢃ8.7912
2
x ¼ l =2g
(v)
S ¼ 1=g
(vi)
retains a close connection to some molecular properties. We
consider the energy gap since it is known to be an index of
both kinetic stability (reactivity) and electrical conductiv-
[
32]
3.5. Non linear optical properties
ity.
The magnetic properties of the title compounds on the
basis of electron filling in MOs paired electron in HOMO of
Schiff base sal-snmH justify its diamagnetic behavior while
one unpaired electron in oxovanadium(IV) complex justify
paramagnetic behavior.
The energy of the frontier orbitals for molecules in term
of ionization energy (IE) and electron affinity (EA) of the
Nonlinear optical properties viz., dipole moment (l), mean
polarizability (a) and the total first static Hyperpolarizability
(b0) for sal-snmH and its oxovanadium (IV) complex,
[
VO(sal-snm) (H O)] to be calculated in terms of x, y, z
2
2
components and is given by following equations: and calcu-
lated value in the Table 3. The first hyperpolarizability (b0)
sal-snmH and its oxovanadium(IV) complex, [VO(sal- of this novel molecular system is calculated using DFT
snm) (H O)] from Koopmans’s theorem is:
method, based on the finite field approach. In the presence
of an applied electric field, the energy of a system is a func-
tion of the electric field. First hyperpolarizability is a third
rank tensor that can be described by a 3 ꢄ 3ꢄ3 matrix. The
2
2
ꢃEHOMO ¼ IE
(i)
ꢃELUMO ¼ EA
(ii)
2
7 components of the 3D matrix can be reduced to 10 com-
[
34]
The absolute electronegativity (vabs) and absolute hard- ponents due to the Kleinman symmetry.
ness (g) are related to IA and EA as given below:
ꢀ
ꢁ
1
=2
l ¼ lx2 þ ly þ lz
2
2
(vii)
vabs ¼ ðIE þ IAÞ=2
(iii)
(iv)
a ¼ 1=3ðaxx þ ayy þ azzÞ
(viii)
g ¼ ðIE ꢃ IAÞ=2
Hard molecules have a large HOMO-LUMO gap, and
a
soft molecules have a small HOMO-LUMO gap as reported
ꢂ
ꢃ
1=
2
2
2
2
[
33]
ðaXXꢃaYYÞ þ ðaYYꢃaZZÞ þ ðaZZꢃaXXÞ
in literature.
The absolute electronegativity (vabs), abso-
Da ¼
(ix)
2
lute hardness (g) of sal-snmH and its oxovanadium(IV)

INORGANIC AND NANO-METAL CHEMISTRY
7
Table 3 The calculated electric dipole moment (l) in Debye, isotropic polariz-
ability (a), anisotropy of the polarizability (Da) and hyperpolarizability (b) com-
ponents of title compounds.
Parameters
Compounds
Dipole moment (l)
sal-snmH
[VO(sal-snm) (H O)]
2 2
l
l
l
x
y
z
ꢃ2.7966
ꢃ2.5343
2.5992
ꢃ1.8498
ꢃ0.3408
ꢃ7.0359
7.2830
l total
4.5825
Polarizability (a)
a
a
a
a
a
a
a
xx
ꢃ116.1728
ꢃ116.5457
ꢃ121.6447
3.2654
ꢃ435.0854
ꢃ205.6737
ꢃ262.9041
14.5191
78.8148
5.7444
yy
zz
xy
xz
20.2814
yz
ꢃ3.4364
ꢃ24
ꢃ24
total
ꢃ17.506ꢄ10
ꢃ44.641ꢄ10
ꢃ24
ꢃ24
Da
0.785ꢄ10
30.651ꢄ10
Hyperpolarizability (b)
b
b
b
b
b
b
b
b
b
b
b
XXX
YYY
ZZZ
XYY
XXY
XXZ
XZZ
YZZ
YYZ
XYZ
0
ꢃ92.2285
ꢃ9.6121
7.0456
ꢃ135.0300
ꢃ0.5757
ꢃ26.1616
3.2338
2.0220
ꢃ54.2008
107.8275
36.4942
7.9490
4.7491
ꢃ109.4038
41.1363
ꢃ0.7852
ꢃ10.5246
26.7184
ꢃ0.2436
ꢃ17.6293
ꢃ31
ꢃ31
10.967ꢄ10
14.857ꢄ10
þþ
Figure 8. B3LYP/6-31 G(D,P) and LANL2DZ calculated 3D molecular electro-
static potential of sal-snmH (a) and its Oxovanadium(IV) complex, [VO(sal-
2 2
snm) (H O)] (b) respectively in atomic units (a.u.) mapped on the electronic
density isosurface of 0.02 a.u.
ꢀ
ꢁ
1
=2
2
2
2
b ¼ b þ by þ bz
(x)
0
x
and
known that the higher values of dipole moment, molecular
polarizability, and hyperpolarizability are important for
more active NLO properties. The calculated dipole moment
bx ¼ b þ bxyy þ bxzz
xxx
(
l), the polarizability (a), anisotropy of the polarizability
by ¼ b þ bxxy þ byzz
yyy
(
Da) and the first static calculated hyperpolarizability (b ) of
0
the title compounds are represents in Table 3. For sal-snmH
the respective values in the same order are 4.5825 D,
bz ¼ b
zzz
þ bxxz þ byyz
ꢃ24
ꢃ24
ꢃ31
ꢃ17.506 ꢄ 10 , 0.785 ꢄ 10
and 10.967 ꢄ 10
esu. For
(or)
the complex compound respective values in the same order
h
ꢄ
ꢅ
ꢄ
ꢅ
2
2
ꢃ24
ꢃ24
b0 ¼ bxxx þ bxyy þ bxzz þ b þ byzz þ byxx
are 7.2830 D, ꢃ44.641 ꢄ 10
,
30.651 ꢄ 10
and
yyy
ꢃ31
ꢄ
ꢅ
2
1=2
14.857 ꢄ 10 esu. The calculated NLO parameters for the
þ b þ bzxx þ bzyy
ꢅ
(xi)
zzz
compounds are in order as: [VO(sal-snm) (H O)]> sal-
2
2
It may be noted that the calculated electric dipole snmH. The complex is good nonlinear optical compounds
[
35,36]
moment l (Debye), isotropic polarizability (a) anisotropy of in the literature.
the polarizability (Da), all hyperpolarizability (b ) compo-
0
nents values have been converted from atomic units (a.u.)
ꢃ24
3.6. Molecular electrostatic potential (MESP)
into electrostatic units (esu). [a: 1a.u.¼0.1482 ꢄ 10
esu; b:
ꢃ33
1
a.u.¼8.6393 ꢄ 10
esu]. From the tabulated data of NLO The MESP surface diagram is a molecular charge topograph-
properties it may be mentioned here that the conventional ical presentation based on color coding system to under-
sign is important in finding the difference of this section stand the reactive behavior of a molecule, in that negative
between ligand and its complex. IN case of the dipole ten- regions can be regarded as nucleophilic centers, whereas
sors the metal complex shows considerable decrease in its the positive regions are potential electrophonic sites.
stretch and in hyperpolarizability extracted values the nega- The molecular electrostatic potential surface as reported
[
37–41]
tive and positive signs are significant. Negative values indi- elsewhere
represents molecular shape, size and electro-
cate emission tensor and positive indicates absorptive effect. static potential values. The MESP maps of N-(salicylidene)-
The calculated values are indicative of the fact that due to sulfanilamide and its Oxovanadium(IV) complex, [VO(sal-
metallic constituent these emissive properties are well pro- snm) (H O)] given in Figure 8 show that the carbonyl oxygen/
2
2
nounced. Theoretical investigation plays an important role sulfonamide oxygens represent the most negative potential
in understanding the structural property relationship which region, while hydroxyl/enolic oxygen is the region of moder-
is able to help in designing novel NLO materials. It is well ate negative potential. The hydrogen and carbon atoms of

8
J. M. MIR ET AL.
the two molecules bear positive potentials. The predomin-
ance of green region in the MESP surfaces corresponds to a
potential halfway between the two extremes red and dark
blue color.
6. Chohan, Z. H.; Shad, H. A.; Youssoufi, M. H.; Hadda, T. B.
Some New Biologically Active Metal-based Sulfonamide. Eur. J.
Med. Chem. 2010, 45, 2893–2901.
7.
Back, D. F.; de Oliveira, G. M.; Roman, D.; Ballin, M. A.; Kober,
R.; Piquini, P. C. Synthesis of Symmetric N,O-donor Ligands
Derived from Pyridoxal (Vitamin B6): DFT Studies and
Structural Features of Their Binuclear Chelate Complexes with
the Oxofilic Uranyl and Vanadyl(V) Cations. Inorg. Chim. Acta
4
. Conclusions
2
014, 412, 6–14. DOI: 10.1016/j.ica.2013.12.008.
In the present work, DFT-experimental study of N-
8
.
.
Bhattacharjee, C. R.; Datta, C.; Das, G.; Mondal, P.
Oxovanadium (IV) Complexes of Bidentate [N,O] Donor Schiff-
base Ligands: Synthesis and Mesomorphism. Syn. Mesomorphism
Phase Trans.: A Multinatl. J. 2012, 85, 956–972. DOI: 10.1080/
(Salicylidene)sulfanilamide and its oxovanadium(IV)
Complex with special attention towards molecular Structure,
FT-IR Spectrum, HOMO-LUMO and Non-linear Properties
have been studied using B3LYP method with 6-31þþG(D,
P)/LANL2DZ basis set. On the basis of the calculated and
experimental results, assignments of the fundamental fre-
quencies were examined. The calculated HOMO and LUMO
energies show that charge transfer occurs within the mole-
cules. Nonlinear optical (NLO) properties of the molecules
was investigated by the determination of the electric dipole
01411594.2012.666667.
9
Biernacki, K.; Magalhaes, A. L.; Freire, C.; Rangel, M. A DFT
Quantum Mechanical Study of 3-Hydroxy-4-Pyrone and 3-
Hydroxy-4-Pyridinone Based Oxidovanadium(IV) Complexes.
Struct. Chem. 2011, 22, 697–706. DOI: 10.1007/s11224-011-9748-5.
1
0. Malik BA, Mir JM. Synthesis, characterization and DFT aspects
of some oxovanadium (IV) and manganese (II) complexes
involving dehydroacetic acid and b-diketones. Jou. of Coord.
Chemist. 2018, 71 (1), 104–119.
moment (l), polarizability (a), mean polarizability (Da) and 11. Garribba, E.; Lodyga-Chruscinska, E.; Micera, G. Complex
Formation in Aqueous Solution and in the Solid State of the
hyperpolarizability (b ) values using B3LYP quantum chem-
ical calculations. Hence, the level of theory applied in the
study validates the experimental data of this complex
0
Potent Insulin-Enhancing V(IV)O2þ Compounds Formed by
Picolinate and Quinolinate Derivatives. Inorg. Chem. 2011, 50,
883–889.
reported earlier.
12. Rodrigues, G. S.; Da Silva, C. I.; Silva, G. G.; De Noronha,
A. L. O.; De Abreu, H. A.; Duarte, H. A. DFT Study of Vanadyl
(
IV) Complexes with Low Molecular Mass Ligands: Picolinate,
Oxalate, Malonate, and Maltolate. Int. J. Quantum Chem. 2011,
11, 1395. DOI: 10.1002/qua.22577.
Acknowledgements
1
The authors are thankful to Prof. Kapil Dev Mishra, Vice-Chancellor,
Rani Durgavati University, Jabalpur, for encouragement. Analytical
facilities provided by the Central Drug Research Institute, Lucknow,
India, and the Regional Sophisticated Instrumentation Centre, Indian
Institute of Technology, Mumbai, India, are gratefully acknowledged.
1
3. Jana, A.; Konar, S.; Mandal, T. N.; Das, K.; Ray, S.; Sarkar, A.;
Liu, C. M.; Kar, S. K. Synthesis and Studies of Rare
Acylhydrazine Bridged Strong Antiferromagnetically Coupled
Dicopper(II) and Dioxovanadium(V) Complexes of a Pyridyl-
Pyrazole Derived Schiff Base Ligand. Polyhedron. 2012, 46,
1
05–112. ꢃ DOI: 10.1016/j.poly.2012.07.076.
1
4. Maurya, M. R.; Bisht, M.; Kumar, A.; Kuznetsov, M. L.; Avecilla,
F.; Pesso, J. C. Synthesis, Characterization, Reactivity and
Catalytic Activity of Oxidovanadium(IV), Oxidovanadium(V)
and Dioxidovanadium(V) Complexes of Benzimidazole Modified
Ligands. Dalton Trans. 2011, 40, 6968–6983.
ORCID
Jan Mohammad Mir
Ram Charitra Maurya
http://orcid.org/0000-0003-3231-0014
http://orcid.org/0000-0001-9314-9872
1
5. Ebrahimipour, S. Y.; Abaszadeh, M.; Castro, J.; Seifi, M.
Synthesis, X-ray Crystal Structure, DFT Calculation and
Catalytic Activity of Two New Oxido-Vanadium(V) Complexes
Containing ONO Tridentate Schiff Bases. Polyhedron. 2014, 79,
Reference
1
38–150. DOI: 10.1016/j.poly.2014.04.069.
1.
Nagpal, P.; Singh, R. V. Toxicological Effects, Biological Aspects
and Spectral Characterization of Organoboron(III) Complexes of
Sulfonamide-Imines. Appl. Organometal. Chem. 2004, 18,
1
6. Jacob, R.; Fischer, G. Infrared Absorption Spectra and Structures
of Zwitterions of Glycyl-l-alanine and Its N-Deuterated
Isotopomer in a KBr Matrix. J. Mol. Struct. 2002, 613, 175.
7. Maurya, R. C.; Malik, B. A.; Mir, J. M.; Vishwakarma, P. K.
Oxidovanadium(IV) Complexes Involving Dehydroacetic Acid
and b-Diketones of Bioinorganic and Medicinal Relevance: Their
Synthesis, Characterization, Thermal Behavior and DFT Aspects.
J. Mol. Struct. 2015, 1083, 343–356. DOI: 10.1016/
j.molstruc.2014.11.032.
8. Maurya, R. C.; Sutradhar, D.; Martin, M. H.; Roy, S.; Chourasia,
J.; Sharma, A. K.; Vishwakarma, P. Oxovanadium(IV)
Complexes of Medicinal Relevance: Synthesis, Characterization,
and 3D-molecular Modeling and Analysis of Some
Oxovanadium(IV) Complexes in O,N-donor Coordination
Matrix of Sulfa Drug Schiff Bases Derived from a 2-pyrazolin-5-
one Derivative. Arabian. J. Chem. 2015, 8, 78–92. DOI: 10.1016/
j.arabjc.2011.01.009.
221–226. DOI: 10.1002/aoc.610.
1
2.
Sharaby, C. M. Synthesis, Spectroscopic, Thermal and
Antimicrobial Studies of Some Novel Metal Complexes of
Schiff Base Derived from [N1-(4-Methoxy-1,2,5-Thiadiazol-
3-yl)Sulfanilamide]
and
2-Thiophene
Carboxaldehyde.
Spectrochim. Acta A Mol. Biomol. Spectrosc. 2007, 66, 1271–1278.
Mohamed, G. G.; Zayed, M. A.; Abdallah, S. M. Metal
Complexes of a Novel Schiff Base Derived from Sulphametrole
and Varelaldehyde. Synthesis, Spectral, Thermal Characterization
and Biological Activity. J. Mole Struct. 2010, 979, 62–67. DOI:
3.
1
10.1016/j.molstruc.2010.06.002.
4
.
.
Chen, D.; Martel, A. E. Dioxygen Affinities of Synthetic Cobalt
Schiff Base Complexes. Inorg. Chem. 1987, 26, 1026–1030. DOI:
10.1021/ic00254a013.
5
Costamagna, J.; Vargas, J.; Latorre, R.; Alvarado, A.; Mena, G. 19. Frisch, M. J. Gaussian 09, Revision A11.4, Gaussian, Inc.:
Coordination Compounds of Copper, Nickel and Iron with
Pittsburgh. PA, 2010.
Schiff Bases Derived from Hydroxynaphthaldehydes and 20. Becke, A. D. Density-functional Thermochemistry. III. The Role
Salicylaldehydes. Coord. Chem. Rev. 1992, 119, 67–88. DOI:
of Exact Exchange. J. Chem. Phys. 1993, 98, 5648–5652. DOI:
10.1016/0010-8545(92)80030-U.
10.1063/1.464913.

INORGANIC AND NANO-METAL CHEMISTRY
9
21. Lee, C.; Yang, W.; Parr, R. C. Development of the Colle-Salvetti
Correlation-energy Formula into a Functional of the Electron
Studies of Salen-type Schiff Base Complexes. Spectrochim. Acta A
Mol. Biomol. Spectrosc. 2014, 117, 485–492.
Density. Phys. Rev. B. 1988, 37, 785–789. DOI: 10.1103/ 31. Fukui, K. Role of Frontier Orbitals in Chemical Reactions.
PhysRevB.37.785.
Science. 1982, 218, 747–754.
2. Parihar, S.; Pathan, S.; Jadeja, R. N.; Patel, A.; Gupta, V. K. 32. Samiee, S.; Mahdavifar, Z. Theoretical Studies of n-Membered
2
Synthesis and Crystal Structure of an Oxovanadium(IV)
Complex with Pyrazolone Ligand and Its Use as
Heterogeneous Catalyst for the Oxidation of Styrene Under Mild
Conditions. Inorg. Chem. 2012, 51, 1152–1161.
Ring Chelate Complexes of Ni(II), Pd(II) and Pt(II) Derived
from Bidentate Phosphorus Ylides. Polyhedron. 2014, 72, 72–82.
DOI: 10.1016/j.poly.2014.01.029.
a
a
3
3
3. Pearson, R. G. The Principle of Maximum Hardness. Acc. Chem.
2
3. Maurya, R. C.; Rajput, S. Oxovanadium(IV) Complexes of
Bioinorganic and Medicinal Relevance: Synthesis, Characterization
and 3D Molecular Modeling and Analysis of Some
Oxovanadium(IV) Complexes Involving the O, N-Donor
Environment of Pyrazolone-based Sulfa Drug Schiff Bases. J. Mol.
Struct. 2006, 794, 24–34. DOI: 10.1016/j.molstruc.2006.01.031.
4. Maurya, R. C.; Patel, P.; Sutradhar, D. Synthesis, Magnetic,
Thermal, and Spectral Studies of Some Chelates of Cu(II), Ni(II),
Zn(II), Co(II), Mn(II), Sm(III), and Th(IV) Involving
Aroylhydrazones Derived from Isonicotinic Acid Hydrazide and
Res. 1993, 26, 250–256. DOI: 10.1021/ar00029a004.
4. Kleinman, D. A. Nonlinear Dielectric Polarization in Optical
Media. Phys. Rev. 1962, 126, 1977–1979. DOI: 10.1103/
PhysRev.126.1977.
5. Karthick, T.; Balachandran, V.; Perumal, S.; Nataraj, A.
Rotational Isomers, Vibrational Assignments, HOMO–LUMO,
NLO Properties and Molecular Electrostatic Potential Surface of
N-(2 Bromoethyl) Phthalimide. J. Mol. Struct 2011, 1005,
3
3
2
202–213. DOI: 10.1016/j.molstruc.2011.08.051.
6. Xavier, R. J.; Dinesh, P. Spectroscopic (FTIR, FT-Raman, 13C
and 1H NMR) Investigation, Molecular Electrostatic Potential,
Polarizability and First-order Hyperpolarizability, FMO and
NBO Analysis of 1-Methyl-2-Imidazolethiol. Spectrochim. Acta A
Mol. Biomol. Spectrosc. 2014, 118, 999–1011.
2
-Furyl Methyl and 2-Thienyl Methyl Ketone. Synth. React.
Inorg. Met-Org. Chem 2003, 33, 1857–1876. DOI: 10.1081/SIM-
20026553.
1
2
5. Maurya, R. C.; Sutradhar, D.; Martin, M. H.; Roy, S.; Chourasia,
J.; Sharma, A. K.; Vishwakarma, P. Oxovanadium(IV)
Complexes of Medicinal Relevance: Synthesis, Characterization, 37. Vishwakarma, P. K.; Mir, J. M.; Maurya, R. C. Pyrone-based
and 3D-Molecular Modeling and Analysis of Some
Oxovanadium(IV) Complexes in O,N-Donor Coordination
Matrix of Sulfa Drug Schiff Bases Derived from a 2-pyrazolin-5-
one Derivative. Arab. J. Chem. 2015, 8, 78–92. DOI: 10.1016/
j.arabjc.2011.01.009.
Cu(II) Complexes, Their Characterization, DFT Based
Conformational Drift from Square Planar to Square Pyramidal
Geometry and Biological Activities. J. Chem. Sci. 2016, 128,
511–522. DOI: 10.1007/s12039-016-1048-6.
38. Mir, J. M.; Jain, N.; Jaget, P. S.; Khan, W.; Vishwakarma, P. K.;
Rajak, D. K.; Malik, B. A.; Maurya, R. C. Urinary tract anti-
infectious potential of DFT-experimental composite analyzed
ruthenium nitrosyl complex of N-dehydroacetic acid-thiosemi-
carbazide, Journal of King Saud University-Science 2019, 31,
2
6. Selbin, J. Oxovanadium(IV) Complexes. Coord. Chem. Rev. 1966,
1
, 293. DOI: 10.1016/S0010-8545(00)80142-3.
2
7. Maurya, R. C.; Singh, H.; Pandey, A.; Singh, T. Metal chelates of
bioinorganic and catalytic relevance: Synthesis, magnetic and
spectral studies of some mononuclear and binuclear
oxovanadium(IV) and dioxotungsten(VI) complexes involving
Schiff bases derived from 4-butyryl-3-methyl-1-phenyl-2-pyrazo-
lin-5-one and certain aromatic amines. Ind. J. Chem 2001, 40A,
89–100.
3
9. Mir, J. M.; Jain, N.; Jaget, P. S.; Maurya, R. C. Density
Functionalized [RuII(NO)(Salen)(Cl)] Complex: Computational
Photodynamics and in Vitro Anticancer Facets. Photodiagnosis
Photodyn. Ther. 2017, 19, 363–374.
1
053ꢃ1063.
2
8. Boas, L. V.; Pessoa, J. C.; Wilkinson, G.; Gillard, R. D.;
McCleverty, J. A. Comprehensive Coordination Chemistry, 1st ed.
Pergamon Press: Oxford, 1987.
4
0. Mir, J. M.; Jain, N.; Malik, B. A.; Chourasia, R.; Vishwakarma,
P. K.; Rajak, D. K.; Maurya, R. C. Urinary Tract Infection
Fighting Potential of Newly Synthesized Ruthenium Carbonyl
2
9. Maurya, R. C.; Patel, P.; Rajput, S. Synthesis and
Characterization of Mixed-Ligand Complexes of Cu(II), Ni(II),
0
Complex of N-dehydroacetic acid-N -o-vanillin-Ethylenediamine.
Inorg. Chimica Acta 2017, 467, 80–92. DOI: 10.1016/
j.ica.2017.07.051.
Co(II), Zn(II), Sm(III), and U(VI)O
2
, with a Schiff Base Derived
0
from the Sulfa Drug Sulfamerazine and 2,2 -Bipyridine. Synth.
React. Inorg. Met.-Org. Chem. 2003, 33, 801–816. DOI: 10.1081/
SIM-120021647.
4
1. Mir, J. M.; Maurya, R. C. A New Ru(II) Carbonyl Complex of 2-
Benzoylpyridine: Medicinal and Material Evaluation at the
Computational–Experimental Convergence. J. Chin. Adv. Mater.
Soc 2018, 6, 156–168. DOI: 10.1080/22243682.2018.1442743.
3
0. Ebrahimi, H. P.; Hadi, J. S.; Abdulnabi, Z. A.; Bolandnazar, Z.
Spectroscopic, Thermal Analysis and DFT Computational