A new coordination polymer constructed from Pb(NO3)2 and a benzylideneisonicotinohydrazide derivative: Coordination-induced generation of a π-hole towards a tetrel-bonding stabilized structure

Article abstract of DOI:10.1016/j.molstruc.2021.130139

We report on a new Pb(II) coordination polymer [Pb(HL)(NO₃)₂]_n (1), obtained from a direct reaction of Pb(NO₃)₂ with N'-4-(dimethylamino)benzylideneisonicotinohydrazide (HL). The coordination sphere a

Full text of DOI:10.1016/j.molstruc.2021.130139

Journal of Molecular Structure 1234 (2021) 130139
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Research paper
A new coordination polymer constructed from Pb(NO ) and a
3
2
benzylideneisonicotinohydrazide derivative: Coordination-induced
generation of a π-hole towards a tetrel-bonding stabilized structure
a,∗
a
b
c
Ghodrat Mahmoudi , Ardavan Masoudiasl , Farhad Akbari Afkhami , Jonathan M. White ,
d
e,f
g,∗
h,i,j,∗
Ennio Zangrando , Atash V. Gurbanov , Antonio Frontera , Damir A. Safin
a
Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
b
Department of Chemistry and Biochemistry, The University of Alabama, Box 870336, 250 Hackberry Lane, Tuscaloosa, AL, 35487, USA
BIO-21 Molecular Science and Biotechnology, University of Melbourne, Parkville, Victoria, 3052, Australia
Department of Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Department of Chemistry, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan
c
d
e
f
g
h
i
Departament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca, Baleares, Spain
University of Tyumen, Volodarskogo Str. 6, 625003 Tyumen, Russian Federaton
Kurgan State University, Sovetskaya Str. 63/4, 640020, Russian Federation
j
Innovation Center for Chemical and Pharmaceutical Technologies, Ural Federal University named after the First President of Russia B.N. Eltsin, Mira Str. 19,
Ekaterinburg 620002, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
We report on a new Pb(II) coordination polymer [Pb(HL)(NO ) ] (1), obtained from a direct reaction
3
2
n
Received 5 February 2021
Accepted 15 February 2021
Available online 25 February 2021
of Pb(NO3)2 with N’-4-(dimethylamino)benzylideneisonicotinohydrazide (HL). The coordination sphere
around the Pb(II) cation is built by the 1,4-N,O-chelating neutral HL, by six oxygen atoms from three
chelating nitrate anions, and by the pyridyl nitrogen donor from a symmetry related molecule. The lig-
and HL and one of the nitrate anions, acting as bridging species, yield two 1D zig-zag polymeric chains
along the crystallographic axes b and c, respectively. As a result, the overall structural architecture of 1
is a 2D layer, which is reinforced by the N–H···O hydrogen bonds and by π···π interactions, resulting
in a 4-connected uninodal sql/Shubnikov tetragonal plane net topology or a 3,5-connected binodal 3,5L1
net, once the N–H···O hydrogen bonds are considered. In addition of these conventional interactions, the
coordination of the hydrazide group to the Pb(II) ion provokes the formation of a π-hole at the carbonyl
group that establishes a tetrel bond with the oxygen atom of a nearby nitrato-ligand belonging to another
polymeric chain. This interaction has been studied energetically at the PBE0-D3/def2-TZVP level of theory
and also characterized by using a combination of MEP, QTAIM and NCIplot computational tools.
Keywords:
Lead(II)
Isonicotinohydrazide
Coordination polymer
Crystal structure
DFT
©
2021 Elsevier B.V. All rights reserved.
1
. Introduction
tion numbers being affected by the hemi- or holodirected coor-
dination geometry and the stereoactive electron lone pairs might
play a crucial role in forming various topological structures not ex-
hibited by the d-block transition metals [9–11]. Beside coordination
bonds, CPs also comprise other non-covalent bonds such as hydro-
gen bonds, π···π stacking or van der Waals interactions, resulting
in their structural diversity. Few years ago researchers have coined
the term «tetrel bonding» to highlight little-studied but powerful
non-covalent bonding between electron donors and the group 14
elements, that energetically is comparable to hydrogen bonds and
other σ-hole-based interactions [12–15]. These tetrel interactions
are often crucial in the self-assembly of Pb(II) coordination poly-
mers. Because of these characteristics, the coordination preference
During the past few decades, design and fabrication of coordi-
nation polymers (CPs) gain significant attention because of their
potential usage in catalytic reactions [1,2], luminescence [3], mag-
netic materials [4], photovoltaic conversion [5–7] and gas sensors
[
8]. The large ionic radius of Pb(II) and the presence of 6s2 lone
electron pair lead the metal to exhibit a wide range of coordina-
∗
Corresponding authors.
E-mail
addresses:
ghodratmahmoudi@gmail.com
(G.
Mahmoudi),
toni.frontera@uib.es (A. Frontera), damir.a.safin@gmail.com (D.A. Safin).
https://doi.org/10.1016/j.molstruc.2021.130139
0
022-2860/© 2021 Elsevier B.V. All rights reserved.

G. Mahmoudi, A. Masoudiasl, F.A. Afkhami et al.
Journal of Molecular Structure 1234 (2021) 130139
Chart 1. Diagrams of the N’-4-(dimethylamino)benzylidene(picolino/nicotino/
isonicotino)hydrazide (HA), N’-1-(4-(dimethylamino)phenyl)ethylidene(picolino/
nicotine/isonicotino)hydrazide (HB) and N’-(4-(dimethylamino)phenyl)(phenyl)
methylene(picolino/nicotine/isonicotino)hydrazide (HC).
of Pb(II) ion and its geometry are expected to be highly sensi-
tive to the selection of organic linkers and counter-ions [16–22].
Chelating-bridging ligands based on hydrazone-pyridine could po-
tentially coordinate to the metal centers through their chelating
fragment along with their pyridyl nitrogen atoms (bridging agent).
Moreover, their amide groups could potentially interact with each
other through hydrogen bonding, which is important for the con-
struction of supramolecular arrays.
With all this in mind and in continuation of our ongoing
interest in the coordination chemistry of the Pb(II) cation [23–27],
as well in study the role of non-covalent interactions in the
formation of extended structures, we have directed our atten-
tion to the N’−4-(dimethylamino)benzylideneisonicotinohydrazide
(
(
(
HL) ligand. HL belongs to a family of hydrazone derivatives, N’−4-
dimethylamino)benzylidene(picolino/nicotino/isonicotino)hydrazide
HA), N’−1-(4-(dimethylamino)phenyl)ethylidene(picolino/nicotine/
isonicotino)hydrazide (HB) and N’-(4-(dimethylamino)phenyl)
(
(
phenyl)methylene(picolino/nicotine/isonicotino)hydrazide
(HC)
Scheme 1. Synthesis of HL and 1.
Chart 1). A search in the Crystal Structure Database [28] retrieved
only six crystal structures of metallocomplexes exclusively with
HA, of which no crystal structures with Pb(II) were found. Thus,
the coordination chemistry of Pb(II) with benzylidenehydrazide
derivatives HA, HB and HC has not been explored and it is of
particular interest to clarify the interactions occurring in solid
state of these compounds.
2
.2. Synthesis of HL
A mixture of 4-dimethylaminobenzaldehyde (0.149 g, 1 mmol)
In this work we have shed light on the crystal structure of a
and isonicotinehydrazide (0.137 g, 1 mmol) in ethanol (30 mL) was
refluxed for 12 h. The resulting precipitate was filterd off, washed
with ethanol and dried in air. Yield: 0.228 g (85%). M.p.: 201–
new Pb(II) coordination polymer, [Pb(HL)(NO ) ]n (1), which was
3
2
readily obtained by self-assembly of Pb(NO3)2 with HL. In addition,
we describe the effect of the coordination of HL to Pb(II) via both
the hydrazido and the pyridine moieties on the electronic nature
of the hydrazido group, particularly focusing on the formation of a
π-hole over the carbonyl carbon atom. The energetic features and
the characterization of the C···O π-hole tetrel bonding interaction
are described in the theoretical part of this work.
2
2
03 °C. Anal. Calc. for C15H16 N O (268.32): C 67.15, H 6.01 and N
0.88%; found: С 67.69, Н 5.89 and N 20.59%.
4
2
.3. Synthesis of 1
The synthesis was carried out using a branched tube method
[
29] as previously udsed in these labs [21]. A mixture of Pb(NO3)2
2
. Experimental
(0.331 g, 1 mmol) and HL (0.268 g, 1 mmol) was placed in the
main arm of the branched tube, and methanol (25 mL) was care-
fully added to fill the arms. The tube was sealed and immersed in
an oil bath at 60 °C, while the branched arm was kept at ambient
temperature. After few days, brown block-like X-ray suitable crys-
tals were formed in the cooler arm. Crystals were isolated by filtra-
tion and dried in air. Yield: 0.354 g (59%). M.p.: 298–300 °C. Anal.
Calc. for C15H16 N O Pb (599.53): C 30.05, H 2.69 and N 14.02%;
2
.1. Materials and physical measurements
All reagents were provided from commercial sources and used
without further purification. Infrared spectra (KBr pellets) were
recorded with a JASCO-680 spectrometer in the range 400–4000
cm–1. Microanalyses were performed using a LECO-elemental ana-
lyzer.
6
7
found: С 29.88, Н 2.76 and N 14.08%.
2

G. Mahmoudi, A. Masoudiasl, F.A. Afkhami et al.
Journal of Molecular Structure 1234 (2021) 130139
Fig. 1. FTIR spectra of HL (black) and 1 (red).
Fig. 2. Crystal structure of the asymmetric unit of 1.
squares on F2 with anisotropic displacement parameters using the
program SHELXL-2014/7 [31]. Hydrogen atoms were placed at cal-
culated positions except that at N2 located on the Fourier map and
refined.
2
.4. Single-crystal X-ray diffraction
Diffraction data were collected at 100(1) K, using a MX2 beam-
˚
line[0] Australian Synchrotron (λ = 0.71073 A). Cell refinement,
indexing, and scaling of the data sets were performed using the
XSD program [30]. The structure was solved by direct meth-
ods [31]. Non-hydrogen atoms were refined by full-matrix least-
Crystal data: C15H16 N O Pb, M = 599.53 g mol 1, monoclinic,
−
6
7
r
space group P2 /c, a = 19.743(4), b = 12.236(2), c = 7.6650(15) A˚ ,
1
β = 98.56(3) °, V = 1831.1(6) A˚ 3, Z = 4, ρ = 2.175 g cm , μ(Mo-
−3
3

G. Mahmoudi, A. Masoudiasl, F.A. Afkhami et al.
Journal of Molecular Structure 1234 (2021) 130139
Fig. 3. (top) View of the 1D polymeric chain [Pb(HL)]n, developed along crystallographic axis b in the crystal structure of 1. (bottom) View of the 1D polymeric chain
[
Pb(NO3)2]n, developed along crystallographic axis c in the crystal structure of 1. Color code: N = blue, O = red, Pb = magenta.
Kα) = 9.269 mm 1, reflections: 32,711 collected, 4697 unique,
−
binding energies have been corrected using the Boys and Bernardi
counterpoise method [33]. The Grimme’s D3 dispersion correction
has been also used in the calculations [34]. To evaluate the interac-
tions in the solid state, the crystallographic coordinates were used
and only the position of the hydrogen bonds has been optimized.
This methodology and level of theory have previously been used to
analyze non-covalent interactions in the solid state [35,36]. The in-
teraction energies were estimated by calculating the difference be-
tween the energies of the isolated monomers and the ones of their
assembly. The QTAIM analysis [37] and NCIplot index [38] have
been computed at the same level of theory by means of the AIMAll
program [39].
R
= 0.037, R (all) = 0.0288, wR (all) = 0.0732, S = 1.113.
int
1
2
CCDC 2041087 contains the supplementary crystallographic
data. These data can be obtained free of charge via http://www.
ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crys-
tallographic Data centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: (+44) 1223–336–033; or e-mail: deposit@ccdc.cam.ac.uk.
2
.5. Theoretical methods
The non-covalent interactions were analyzed energetically us-
ing Gaussian-16 [32] at the PBE0-D3/def2-TZVP level of theory. The
4

G. Mahmoudi, A. Masoudiasl, F.A. Afkhami et al.
Journal of Molecular Structure 1234 (2021) 130139
Table 1
Selected bond lengths ( A˚ ) and angles (°) for 1.
Bond lengthsa
Pb–N3
Pb–N1_b#1
2.864(4)
2.648(3)
2.536(3)
2.637(3)
2.780(3)
2.568(3)
2.810(4)
2.700(3)
Pb–O3_d#2
O1–C6
2.796(3)
1.252(4)
1.289(4)
1.236(4)
1.243(4)
1.274(4)
1.250(4)
1.246(5)
Pb–O1
O2–N5
O3–N5
O4–N5
O5–N6
O6–N6
O7–N6
Pb–O2
Pb–O4
Pb–O5
Pb–O7
Pb–O2_d#2
Bond anglesa
O1–Pb–O2
O1–Pb–O4
O1–Pb–O5
O1–Pb–O7
O1–Pb–N3
O1–Pb–N1_b#1
O1–Pb–O2_d#2
O1–Pb–O3_d#2
O2–Pb–O4
O2–Pb–O5
O2–Pb–O7
O2–Pb–N3
O2–Pb–N1_b#1
O2–Pb–O2_d#2
O2–Pb–O3_d#2
O4–Pb–O5
O4–Pb–O7
O4–Pb–N3
O4–Pb–N1_b#1
O4–Pb–O2_d#2
O4–Pb–O3_d#2
O5–Pb–O7
Dihedral anglesb
PbNNCO···Py
PbNNCO···C6H4
84.80(9)
O5–Pb–N3
71.42(10)
81.34(10)
91.92(9)
125.22(9)
75.74(11)
113.33(10)
73.32(10)
82.45(10)
131.54(11)
148.39(10)
122.65(9)
68.64(10)
105.81(10)
46.66(9)
122.6(3)
98.5(2)
94.97(10)
77.11(10)
118.25(10)
60.60(10)
74.91(10)
143.13(9)
157.68(10)
47.37(9)
O5–Pb–N1_b#1
O5–Pb–O2_d#2
O5–Pb–O3_d#2
O7–Pb–N3
O7–Pb–N1_b#1
O7–Pb–O2_d#2
O7–Pb–O3_d#2
N3–Pb–N1_b#1
N3–Pb–O2_d#2
N3–Pb–O3_d#2
N1_b–Pb–O2_d#2
N1_b–Pb–O3_d#2
O2_d–Pb–O3_d#2
Pb–O1–C6
157.07(9)
155.01(10)
111.63(10)
80.42(9)
Fig. 4. (top) View of the crystal packing of 1. Color code: H = black, C = gold,
N = blue, O = red, Pb = magenta; cyan dashed line = N–H···O hydrogen bond.
94.26(9)
73.50(9)
(
middle) A simplified network of 1 with the 4-connected uninodal sql/Shubnikov
147.31(8)
116.33(10)
77.05(9)
Pb–O2–N5
4
2
tetragonal plane net topology defined by the point symbol of (4 •6 ). Color code:
Pb = magenta. (bottom) A simplified network of 1, considering N–H···O hydro-
gen bonds, with the 3,5-connected binodal 3,5L1 net topology defined by the point
Pb–O2–Pb_e#3
N5–O2–Pb_e#3
N5–O3–Pb_e#3
Pb–O4–N5
156.10(12)
98.6(2)
127.73(10)
111.36(9)
66.54(9)
95.4(2)
5
3
symbol of (4•5•6)(4•5 •6 •7). Color code: Pb = magenta, HL = blue.
92.9(2)
Pb–O5–N6
101.3(2)
90.5(2)
47.42(10)
Pb–O7–N6
3. Results and discussion
15.79
33.98
Py···C6H4
31.64(19)
Interaction of Pb(NO3)2 and HL in the MeOH medium has al-
a
Symmetry transformations used to generate equivalent atoms: #1
lowed to produce a new heteroleptic CP 1 (Scheme 1) in the form
of brown air- and moisture-stable block-like crystals. The isolated
complex 1 was successfuly characterized by the means of micro-
analysis, FTIR spectroscopy and single-crystal X-ray diffraction. Ac-
cording to the FTIR spectroscopy data, the parent organic ligand
presents in its neutral form in the structure of 1 as evidenced from
the broad band centered at about 3460 cm–1, corresponding to the
NH group (Fig. 1). The same group in the spectrum of free HL was
found at the same wavenumber (Fig. 1). Notably, the absorption
band of the C=O group of the ligand HL in the structure of 1 is
about 40 cm–1 shifted to low frequencies relative to that in the
FTIR spectrum of free HL. This strongly supports its participation
in the coordination towards the Pb(II) cation upon complexation.
–
x, 1/2 + y, 3/2 – z; #2 x, 3/2 – y, –1/2 + z; #3 x, 3/2 – y, 1/2 + z.
b
Dihedral angles between the least-square planes, formed by the
corresponding rings of the same [PbHL]2+ species.
Table 2
Hydrogen bond lengths ( A˚ ) and angles (°) for 1.a.
D–X···A
d(D–X)
d(X···A)
d(D···A)
ࢬ(DXA)
#
1
N2–H2A···O6
0.92(6)
2.04(6)
2.937(4)
166(4)
a
Symmetry transformations used to generate equivalent atoms:
#1 x, 1/2 – y, 1/2 + z.
Table 3
π···π interaction lengths (A) and angles (°) for 1.a,b.
˚
Finally, the NO – anions were found in the IR spectrum of 1 as a
3
Cg(I)···Cg(J)
d[Cg(I)···Cg(J)]
α
β
γ
slippage
band at about 1450 cm–1 (Fig. 1).
#
1
Py···Py
3.870(2)
3.870(2)
10.4(2)
10.4(2)
10.5
16.6
16.6
10.5
0.703
1.109
Complex 1 crystallizes in monoclinic space group P2 /c with
1
#
2
Py···Py
one complex molecule [Pb(HL)(NO ) ] in the asymmetric unit
3
2
a
(
Fig. 2). The Pb(II) cation is coordinated by the 1,4-N,O-chelating
Cg(I)···Cg(J): distance between ring centroids; α: dihedral angle be-
tween planes Cg(I) and Cg(J); β: angle Cg(I) → Cg(J) vector and normal
to plane I; γ : angle Cg(I) → Cg(J) vector and normal to plane J; slippage:
distance between Cg(I) and perpendicular projection of Cg(J) on ring I.
HL and by six oxygen atoms from three nitrate anions. The coor-
dination sphere is filled by the pyridyl nitrogen atom from a sym-
metry related molecule, thus, yielding a nonacoordinate environ-
ment, where the Pb(II) atom shows a holodirected coordination
sphere. Notably, the nitrate anions coordinate the metal in dif-
ferent modes: one is simply chelating, while the other is bridg-
ing/chelating, and thus the structural features of 1 are largely de-
termined by the crystal chemical behavior of the nitrate groups
b
Symmetry transformations used to generate equivalent atoms: #1 x,
1/2 – y, –1/2 + z; #2 x, 1/2 – y, 1/2 + z.
˚
and 5.222 A, respectively (Fig. 3). As a result, a 2D layer structure
is achieved, where the N–H···O hydrogen bonds, formed between
the amide hydrogen atom and the non-coordinated oxygen atom of
the terminal nitrate anion, as well as π···π interactions between
the pyridine rings reinforced the overall structure of 1 (Fig. 4,
Tables 2 and 3). This 2D layer, studied using the ToposPro soft-
ware [41], results in a 4-connected uninodal sql/Shubnikov tetrag-
[
40]. The Pb–N and Pb–O bond distances range from 2.536(3) to
˚
.864(4) A with the longest one pertaining to the nitrogen atom of
2
the isonicotinamide moiety (Table 1). The ligand HL is twisted with
a dihedral angle of about 32° between the planes formed by the
pyridine and phenyl rings (Table 1). Due to the bridging/chelating
coordination mode of HL and one of the nitrate anions, two differ-
ent 1D zig-zag polymeric chains are produced along the crystallo-
graphic axes b and c with the shortest Pb···Pb separations of 9.968
4
2
onal plane net topology defined by the point symbol of (4 •6 ) or
a 3,5-connected binodal 3,5L1 net topology defined by the point
5
3
symbol of (4•5•6)(4•5 •6 •7), when the N–H···O hydrogen bonds
are considered (Fig. 4).
5

G. Mahmoudi, A. Masoudiasl, F.A. Afkhami et al.
Journal of Molecular Structure 1234 (2021) 130139
Fig 5. Partial view of the crystal structure of 1 with indication of the C···O tetrel bonds. Hydrogen atoms were omitted for clarity. Color code: C = gold, N = blue, O = red,
Pb = magenta; cyan dashed line = C···O tetrel bond.
Fig. 6. MEP surfaces (isosurface 0.001 a.u.) of the theoretical models Pb2(HL)(NO3)4 (left), Pb(HL)(NO3)2 (middle) and the ligand HL (right) at the PBE0-D3/def2-TZVP level
of theory.
We have further applied the DFT (PBE0-D3/def2-TZVP) calcula-
tions to examine fine features of the crystal structure of 1. Par-
˚
ticularly, it was found that the C6···O6 separation of 3.196(5) A
˚
is shorter than the sum of the van der Waals radii (3.22 A), thus
suggesting an attractive interaction and the apparent existence of
a π-hole over the carbon atom of the hydrazido group (Fig. 5).
The molecular electrostatic potential (MEP) surface of two the-
oretical models and the ligand HL have been firstly computed
(
Fig. 6). We have used two different monomeric models of the
polymeric chain for the theoretical study. In the first model, de-
noted as Pb (HL)(NO ) , we have used two Pb(NO ) moieties:
2
3
4
3 2
one monodentated (coordinated to N1) and the other one biden-
tate (coordinated to O1 and N3). In the second model, denoted as
Pb(HL)(NO3)2 only one Pb(NO3)2 moiety is bidentately coordinated
to O1 and N3. In the three compounds, the maximum MEP value
is located at the N–H bond, ranging from +59 to +81 kcal/mol
depending on the number of Pb(II) ions coordinated to the lig-
and (from 0 to 2). The minimum MEP value (most negative) is
Fig. 7. Theoretical models and interaction energies of Pb2(HL)(NO3)4 (left),
Pb(HL)(NO3)2 (middle) and the ligand HL (right) interacting with the nitrate an-
ion at the PBE0-D3/def2-TZVP level of theory. The X-ray coordinates were used for
the construction of the models. Color code: H = black, C = gold, N = blue, O = red,
Pb = magenta; cyan dashed line = C···O tetrel bond.
located at the nitrato ligands in Pb (HL)(NO ) and Pb(HL)(NO3)2
2
3 4
Finally, to further support the existence of the π-hole tetrel
bonding interaction, we have used a combination of two meth-
ods, i.e. the quantum theory of atoms in molecules (QTAIM) and
noncovalent interaction plot (NCIplot). The distribution of critical
points and bond paths of the complex reveals the presence of
one bond critical point and bond path (dashed line) that intercon-
nect the oxygen atom of nitrate to the carbon atom of the car-
bonyl group (Fig. 8). This strange behavior of the bond path that
changes the trajectory close to the carbon atom and thus inter-
connecting the two electron rich atoms instead the electron rich
and electron poor atoms is quite common in π-hole interactions
models, and in the middle of the O1 and N3 atoms in the free
ligand (Fig. 6). An interesting finding is that the MEP values are
positive over the carbonyl carbon atom in the Pb (HL)(NO ) and
2
3 4
Pb(HL)(NO3)2 models (+39 and +24 kcal/mol, respectively) and
slightly negative in the ligand HL (Fig. 6), thus evidencing that the
existence of a π-hole over the carbon atom is due to the coordi-
nation of the ligand to the Pb(II) ions.
We have also evaluated energetically the C···O interaction in
the models and the free ligand. It can be observed that the in-
teraction is very strong in the complex of Pb (HL)(NO ) , ꢀE = –
2
3
4
1
2
3.9 kcal/mol, and moderately strong in the Pb(HL)(NO3)2 complex,
[
42], because of the lack of electrons in the electrophilic atom.
ꢀ
E2 = –15.5 kcal/mol (Fig. 7) in agreement with the MEP anal-
In this type of interaction, it is more convenient to use the NCI-
plot index (Fig. 8). It reveals the existence of a blue (meaning
strong) surface between the oxygen and the carbon atom, in line
with the energies commented above. The “on-top” representation
highlighted in Fig. 8 clearly shows that the isosurface is basically
located between the carbon and the oxygen atoms, thus charac-
terizing and further evidencing the existence of the C···O tetrel
bond.
ysis. Interestingly, the interaction energy is positive (repulsive) in
the NO – complex with the naked ligand HL, ꢀE3 = 2.9 kcal/mol
3
(
Fig. 7), thus strongly supporting the fact that the existence of the
π-hole C···O in the solid state of 1 is caused by the coordination of
the ligand to the Pb(II) metal centers. The large interaction energy
obtained for the complex of nitrate with the Pb (HL)(NO ) is a
2
3 4
clear indication of the importance of this interaction in the crystal
packing.
6

G. Mahmoudi, A. Masoudiasl, F.A. Afkhami et al.
Journal of Molecular Structure 1234 (2021) 130139
Declarations
To be used for non-life science journals Not applicable.
Ethical Approval Not applicable.
Consent to Participate Not applicable.
Consent to Publish Not applicable.
Authors Contributions G. M. – planning research and analysis
results; A. M. – conducting research and partial analysis of results;
F. A. A. – conducting research; J. M. W. – planning research, analy-
sis results, and preparing a manuscript; E. Z. – crystallography; A.
V. G. – conducting research and partial analysis of results; A. F. –
theoretical calculations; D. A. S. – planning research, analysis re-
sults, and preparing a manuscript.
Funding
None.
Availability of data and materials
None.
Code availability
Not applicable
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
This work has been partially supported by the Fundação para
a Ciência e a Tecnologia (FCT) 2020–2023 multiannual funding to
Centro de Quimica Estrutural (project UIDB/00100/2020). A.V. Gur-
banov acknowledges the FCT and Instituto Superior Técnico (DL
5
7/2016 and L 57/2017 Program, Contract no: IST-ID/110/2018). We
Fig. 8. Combined QTAIM (bond critical points in red and ring critical points in
acknowledge Australian Synchrotron for beamtime via the Col-
laborative Access Program (proposal 13618b). This research was
funded in part by MICIU/AEI, grant number CTQ2017–85821-R,
FEDER funds.
yellow) and NCIplot (isosurface
=
0.5 a.u., –0.02 < sign(λ2)ρ < 0.04) for the
Pb2(HL)(NO3)4 model interacting with the nitrate. The NCIplot has been represented
only for intermolecular interactions.
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8