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Title: Halogen Bonds Involved in Copper(I) Complexes: A Study Based
On the Electronic Charge Density

Authors: Kaveh Farshadfar, Mohammad Piltan, and Stephenmark Roe

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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700369

Link to VoR: http://dx.doi.org/10.1002/ejic.201700369

European Journal of Inorganic Chemistry 10.1002/ejic.201700369

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Halogen Bonds Involved in Copper(I) Complexes: A Study Based
On the Electronic Charge Density
Mohammad Piltan,‡[a] Kaveh Farshadfar,*‡[a] and S. Mark Roe [b]

Abstract: This communication describes crystal structures of Cu(I)
complexes and their topological analysis with emphasis on the
Laplacian of the electron density to investigate the characteristic of
the halogen bonding (XB). To gain insight into the XBs we carried out
a survey of the wave function and DFT methods. Different XBs, Cl...
Cl¯, I ... I¯, Br ... N3¯, and I ... SCN¯ in the crystal packing of these
compounds, are categorized as a combination of a region of charge
depletion and a region of charge concentration in valence shell charge
concentration or hole−lump interactions. The full quantum potential
based lump−hole concept is more useful than the σ-hole concept in
which the electrostatic portion of potential is merely considered. Such
a view about halogen bonding can rationalize the geometry around
XBs. As well as non-covalent interaction reduced density gradient
(NCI-RDG) approach were pursued to real-space visualization and
quantitative investigation of the XBs.
Introduction
Noncovalent interactions have critical importance in a vast
diversity of chemical and biochemical systems. [1] Without doubt,
one of the most significant and attractive noncovalent interactions
is halogen bonding.[2] Studying XBs provides a deep and subtle
understanding of the nature and the significance of these
interactions. Thus, such studies make new possibilities in the field
of crystal engineering and supramolecular chemistry.[3] In 2013,
IUPAC presented a recommended definition for XBs according to
which[4] “A halogen bond occurs when there is evidence of a net
attractive interaction between an electrophilic region associated
with a halogen atom in a molecular entity and a nucleophilic
region in another, or the same, molecular entity.”
Notwithstanding halogen bonds were first interpreted as a charge-
transfer phenomenon, there are an increasing number of studies
exhibiting that the formation of XB is mainly governed by the
electrostatic effects due to the anisotropic distribution of electron
density around the halogen atom. Covalently bonded halogen
atoms have two different radii; a larger radius perpendicular to the
R-X bond and a shorter radius along this bond.[5] Organohalogen
derivatives show an electrostatically negative belt perpendicular
to the covalent bond and positive cap along the covalent bond
formed by the halogen. Entering nucleophiles, π-systems, and
anions can interact with this positive region to construct the
halogen bondings.[6]
Recently, topological analysis of the Laplacian of the electron
density, ∇2ρ, as a useful method for studying the XBs, has
attracted attentions.[2e, 7] This analysis indicates that a halogen
bond can be described as a combination of a region of charge
depletion “ hole ” (when ∇2ρ > 0), and a region of charge
concentration, “lump” (when ∇2ρ < 0), on the valence shell
charge concentration (VSCC).[2e,7a,7b,8] Another elegant approach
to assess the characteristics of the XBs is non-covalent
interaction (NCI) technique based on the reduced density gradient
(RDG) analysis.[9]
The main objective of this study was to topologically survey of
various metal contributed XBs. To this end distribution and
properties of the Laplacian of the electron density, NCI-RDG and
electrostatic potential maps were used.
In this contribution, we report new structure of Cu(I) complexes
with N^N donor ligands (Scheme 1). The existence of halogen
atoms (X = Cl, Br, I) on the ligand’s phenyl ring and coordinated
+
halide or pseudohalide anions (Cl¯, Br¯, N3¯, SCN¯) to Cu , provide
suitable conditions for the formation of XB in these molecular
skeletons.
.
Scheme 1. Schematic representation of synthesized complexes
Results and Discussion

Single crystals suitable for X-ray analysis were obtained by

[a] Department of Chemistry, Faculty of Science, Sanandaj Branch,
diffusion of diethyl ether in an acetonitrile and chloroform mixture
Islamic Azad University, Sanandaj, Iran
E-mail: Kavehfarshadfar@gmail.com solution of the complexes (for details of the experimental
Mohammadpiltan@yahoo.com procedures and ORTEP drawings see the Supporting
[b] Department of Chemistry, School of Life Sciences, University of Information).[10] All compounds give solvent-free crystalline
Sussex, Brighton, BN1 9QJ, UK.
material and ligands are coordinated to copper(I) cation in a
‡ These authors contributed equally.
bidentate chelating manner via nitrogen atoms of pyridine and
Supporting information for this article is given via a link at the end imine. The other coordination sites of the tetrahedral Cu(I) center
of the document
are occupied by a triphenylphosphine and Cl ¯, I¯, N3¯ or SCN¯ in

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European Journal of Inorganic Chemistry
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CI, CII, CIII and CIV respectively. A summary of the crystallographic
data and bond lengths and angles around copper(I) is listed in
Table S1 and Table S2, respectively. Asymmetric unit of CIV has
two conformer (A and B) states that have equal contribution in the
crystal packing (Figure S2).
In the crystal structure of all compounds, halogen bonding has a
major role in the crystal growth. Pairwise XBs generate dimers
between two adjacent molecules in CI, CII and CIII compounds. In
a different manner, in CIV the I...S XB links the chains formed of
each conformer. As expected, depending on which conformer is
halogen donor or acceptor, two unequal XB in terms of distance
and angle are established in the crystal structure of CIV (CIV-A...
CIV-B and CIV-B...CIV-A); Table 1 and Figure 1.
Figure 1. Dimeric aggregates formed by pairwise XBs in CI, CII and CIII and
linking adjacent conformer chains in CIV by XB
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10.1002/ejic.201700369
It is worth remembering that the electron configuration of halogen
atoms ends in s2px2py2pz1. When a halogen atom forms a covalent
bond with other atoms such as carbon, the electron in the p z1
orbital moves to the center of the C−X axis. This leads to a
negative electrostatic potential belt (lump) perpendicular to the
C−X axis caused by the other pairs of unshared electrons and the
formation of a positive potential (hole) on the outermost portion of
the halogen in the front of C−X bond. [2c] Halides have a full
valence shell so the zone around the halogen ion is not distorted
and can act as a lump in any direction. This charge distribution
around halide anions is responsible for the formation of the
corresponding halogen bonding with a hole of an organohalogen.
Table 1. XB Geometries for CI, CII, CIII and CIV Compounds. (All distances in Å
and angles in °)
Reduction of
Compound XB d(XB) C-X1-X2 X2-X1-Z[a] the sum of the
VDW radii (%)
CI Cl...Cl¯ 3.4180(6) 167.83(6) 149.87(2) 2.34
CI I...I¯ 3.530(1) 177.7(5) 104.04(4) 10.86
CIII Br...N3¯ 3.075(4) 170.0(1) 106.6(2) 9.56
CIV-A-CIV-B I...SCN¯ 3.483(1) 172.3(1) 76.6(2) 7.86
CIV-B-CIV-A I...SCN¯ 3.318(2) 169.2(1) 88.6(2) 12.22
[a] “Z” is related to Cu in CI and CII and middle N3¯ and SCN¯ atoms in CIII and
CIV
Contour maps of the ∇2ρ distribution along XBs for CI, CII, CIII and
CIV are shown in figure 2. Congener atoms in the XB systems of
CI and CII display different roles with dissimilar features due to the
different direct linkage to the copper cation and carbon. Halogen
which is connected to metal (X2) have the least anisotropy in
VSCC but attached halogen to carbon (X1) is aspheric. In CI, Cl2
has an obvious basic region (red region that involves green point
in figure 2) where the electronic charge in total around the
outermost zone of VSCC is locally concentrated. Such area have
a critical point which is referred to as “lump”. In the VSCC of Cl1,
along C-Cl bond, the acidic region (pink point region), which the
electronic charge is locally depleted was referred to as “hole”. In
organohalogens (C-X ... X-C), establishing of XBs need a low
+
angle between two C-X moieties. But in the case of C-X...X¯M ,
the existence of the lump in all-around the halide anion obviates
this need. Thus halides can form halogen bonds with the bond
+
angle of X...X¯M nearly equal to 180 degrees. In a similar case
to CI, the distribution of the electron density Laplacian reveals that
CII possess a lump around I2 in the outermost negative region of
∇2ρ and there is a hole in the region of positive ∇2ρ for I1 along
XB as a positive cap in the VSCC. Belt of negative electrostatic
potential around organohalogen central part is due to lone pairs
of the halogen atoms (Figure 2). These lumps and holes might be
better seen in the envelope isosurfaces and relief maps of ∇2ρ
(Figure S2).
In CIII and CIV two participant atoms in XB are not the same.
Moreover, there is no direct connection between copper metal
and corresponding XB atom. The anisotropic charge distribution
on the both XB atoms can be clearly seen in figures 2, S3 and S4.
The electron density Laplacian of CIII shows the charge
concentration region (negative values of ∇2ρ) for nitrogen is
extensive insofar as cover the VSCC of it on each side. The
European Journal of Inorganic Chemistry
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molecules of CIII are oriented so that the hole in the VSCC of the
bromine atom as Lewis acid is aligned with the lump in the VSCC
of the nitrogen atom as Lewis base. ∇2ρ of CIV illustrates the most
of charge concentration in the VSCC of the sulfur atom is located
as a belt around sulfur and perpendicular to the NCS ¯ covalent
bond axis. Even though the hole of iodine along C-I bond is
responsible for XB formation, but the negative belt around iodine
seems to form another interaction with the hole around carbon in
the SCN¯ anion (right part of figure 2). Bond distances of two
Figure 2. Contour maps of the Laplacian of the electron density (∇2ρ). Red and blue lines correspond to the negative and positive values of ∇2ρ, respectively.
Pink and green points are hole and lump critical points, respectively.
NCI approach. The non-covalent interaction (NCI) reduced
density gradient (RDG) technique has been recently developed
as a theoretical strategy to distinguish weak interactions. To some
extent, The NCI-RDG analysis can be regarded as an extension
of AIM that visualizes the properties around bond critical points.[11]
The NCI-RDG method is a useful tool to distinguish and visualize
different types of noncovalent interactions. This theory rests on
the analysis and the graphical interpretation of electron density
(ρ) and its derivatives, namely the λ eigenvalue of its Hessian and
its reduced gradient s(ρ)[12], defined as:
1 |𝛻𝜌|
𝑠=
2(3𝜋 2 )1/3 𝜌4/3
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10.1002/ejic.201700369
individual XBs between the CIV chains, CIV-A...CIV-B and CIV-B...CIV-
A, equals to 3.483 and 3.318 Å, respectively. Despite the longer
bond distance in the CIV-A...CIV-B, the lower angle of CIV-B...CIV-A
XB (76.65°) in comparison to CIV-A...CIV-B (88.63°) facilitates the
mentioned iodine’s lump-thiocyanate’s hole interaction and
compensates prolongation of its XB. The Br-N-N angle in CIII,
which doesn’t have the ability to form such hole-lump
backbonding equals to 106.65°.
Where ∇ρ is the gradient of ρ. Accordingly, the NCI indexes are
located in the low RDG regions and density. Analysis of sign(λ2)
of the electron density Hessian distinguishes different types of the
interactions. For the strong ones such as H-bonds, sign(λ2)ρ < 0,
for the weak van der Waals types, sign(λ2)ρ ≈ 0 and for the non-
bonded interactions like steric repulsion, sign(λ2)ρ > 0.[12]
XB spikes ρ value of CI, CII, CIII, CIV-A...CIV-B and CIV-B...CIV-A are
observed in -0.007, -0.014, -0.013, -0.012 and -0.016 a.u.,
respectively. NCI 2D plots demonstrate that aside from Cl ... Cl
case, XB is the strongest interaction in the specified systems. The
spike of the shorter I...S bond in CIV is located in more negative
values and the isosurface of the longer XB with a lower angle in
agreement with the electron density Laplacian survey results
shows there is an interaction between sulfur and thiocyanate’s
carbon.
European Journal of Inorganic Chemistry 10.1002/ejic.201700369

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Figure 3. The NCI-RDG s vs. sign(λ2)ρ plots (left) and coloured RDG-based NCI isosurfaces (right) of associations caused by XBs in all compounds.

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European Journal of Inorganic Chemistry
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Conclusions
In summary, to study the characteristic of the halogen bonding,
the diverse XBs, Cl...Cl¯, I...I¯, Br...N3¯ and I...SCN¯, which were
established in the crystal packing of Cu(I) complexes, were used
in the topological analysis of the Laplacian of the electron density
distribution. The results of theoretical study methods on the
experimental compounds revealed that in all of these interactions,
regions of charge depletion (hole) and charge concentration
(lump) in the VSCC of participating atoms, combine together to
constitute halogen bonds. The hole-lump concept due to using full
quantum potential in the definition of the Laplacian was a helpful
approach for justification of noncovalent interactions. Our results
showed that the distribution of electron density around halides is
isotropic but contrariwise, covalently bonded halogen atoms are
aspheric in the VSCC and this anisotropy increases in the heavier
halogens. As well as NCI-RDG results reinforced the fact that
larger halo-atom XBs are robust supramolecular synthons and
especially indicate that XBs involving iodine atom, have a
stronger halogen bonds, likewise type of XB atoms, the geometry
of interaction are also significant. ∇2ρ and NCI index manifested
that there is a unique back halogen bond between C-I and NCS¯,
which can rationalize its low bond angle.
Acknowledgements
Financial support of this work by Islamic Azad University of
Sanandaj Branch is gratefully acknowledged.
Keywords: Halogen bonding • Laplacian of the electron density
• copper(I) complexes • NCI approach
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European Journal of Inorganic Chemistry 10.1002/ejic.201700369

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Preparing the conditions for the Rationalization the halogen bonding
establishing an interaction in the by survey the electron density
opposite direction to the main Laplacian*
halogen bond, causes the low angle
Mohammad Piltan, Kaveh Farshadfar,*
of 76.6° between C-I and SCN¯.
and S. Mark Roe

Page No. – Page No.

Halogen Bonds Involved in Copper(I)

Complexes: A Study Based On the
Electronic Charge Density

*New Insight into Halogen Bonding

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