Article

pubs.acs.org/crystal

Adducts of S/Se Donors with Dihalogens as a Source of Information

for Categorizing the Halogen Bonding
Published as part of the Crystal Growth & Design virtual special issue on Halogen Bonding in Crystal
Engineering: Fundamentals and Applications
M. Carla Aragoni, Massimiliano Arca, Francesco A. Devillanova,* Francesco Isaia, and Vito Lippolis
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato -
Cagliari, Italy

ABSTRACT: The great variety of products ensuing from the reactions

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between chalcogen donors and dihalogens and their assemblies in the crystal
lattice provides a wide experimental basis useful to disembroil the ongoing
debate on how to define the halogen bonding. In this paper we present a
critical analysis/study of the structural features retrieved from the Cambridge
Publication Date (Web): May 11, 2012 | doi: 10.1021/cg201328y

Structural Database (CSD) for linear three-body systems involving either

halogens, X−X−X (X = Br, I), or halogen(s) and chalcogen(s) atoms, E−X−
Y, X−E−Y, and E−X−E (E = S, Se; X = Y = Cl, Br, I; X = I, Y = Cl, Br, I). The
relative elongations (δ) of the two bonds in the examined three-body systems
with respect to the sum of the relevant atomic radii can be fitted by a common
nonlinear least-squares equation derived from the bond-valence model. The
similarities observed in the structural features suggest a common nature of the
chemical bond in all systems considered and indicate that the charge transfer
and the 3c-4e models can be successfully applied to all the cases considered to
explain the nature of the chemical bonding.

■ INTRODUCTION
It is well-known that the reaction between molecules containing
chalcogen donor atoms, E (E = S, Se), and dihalogens, XY (X =
Y = I, Br; X = I, Y = Br, Cl), can afford a great variety of
products including neutral charge-transfer (CT) adducts
featuring an almost linear E−X−Y moiety, and insertion
adducts containing a “T-shaped” X−E−Y fragment.1−12
According to the notation introduced by Martin and cow-
orkers,13,14 these adducts are respectively referred to as 10-X-2
and 10-E-3 hypervalent compounds, indicating that the central
atom is formally associated with five electron pairs (10
electrons), among which 2 or 3, respectively, are bond
pairs.15,16 Both types of adducts feature the central atom in a
hypervalent state, the two different three-body systems (E−X−
Y and X−E−Y) being linear and about 10−12% longer than the
sum of the corresponding covalent radii.15 The chemical bond
in linear E−X−Y and X−E−Y fragments, as well as in trihalides
X3−,15 can be described by using the 3c-4e bonding scheme,14
according to which these moieties are characterized by a total
bond order of 1, with each one of the two bonds exhibiting
bond orders varying from 0 to 1 (see Figure 1 for selected
examples).15 However, besides the adducts containing the E−
X−Y and X−E−Y fragments, other different structural
archetypes were established by X-ray structural analysis and
vibrational spectroscopy for the products of the reactions of
chalcogen donors with dihalogens, depending both on the acid/
base nature of the reactants and the experimental conditions
used.1−12 In an attempt to evaluate whether the different
products obtainable from these reactions could ensue from a
common intermediate species, Husebye et al.10 proposed the
cation [>C−E−X]+ as a transitional species. This cation could
undergo a nucleophile attack on either the chalcogen or the
halogen site, and, depending on the nature of the nucleophile,
the formation of the above-mentioned adducts, the formation
of dications [>C−E−E−C<]+2 bearing a chalcogen-chalcogen
single bond, and the formation of [>C−E−X−E−C<]+ cations
featuring a central X+ coordinated by two donor molecules, can
be explained easily.2a,10,11 Notwithstanding the fact that the
existence of this intermediate in solution has only been proven
in a few cases,17 the charge distribution calculated on the cation
[>C−E−X]+ assumed as a theoretical transitional species can
help in predicting the nature of the final product.2a,11b
■ RESULTS AND DISCUSSION
It has been shown that the reaction between chalcogen donors
and dihalogens can yield a plethora of products. Among these a
recurrent structural motif is the presence of linear three-body
systems, recognizable either as fundamental molecular con-
Received: October 7, 2011
Revised: April 5, 2012
Published: April 23, 2012

© 2012 American Chemical Society 2769 dx.doi.org/10.1021/cg201328y | Cryst. Growth Des. 2012, 12, 2769−2779
 Crystal Growth & Design Article

Table 1. Number of Fragments (Structures) in Selected Linear (Angle > 165°) Three-Body Systems Found in the CSD21 with
Interatomic Distances Ranging from the Sum of the Covalent Radii up to That of Van der Waals Radii
I Br Cl
S Se S Se S Se
X−X−X 1618 (1084) 181 (127) 10 (10)
E−X−X 147 (104) 43 (32) 11 (11) 10 (7)
X−E−X 1 (1) 7 (6) 8 (7) 194 (86) 8 (7) 155 (68)
E−E−X 36 (17) 13 (7) 85 (29) 42 (18) 56 (24) 23 (13)
E−X−E 12 (11) 7 (6) 4 (3) 2 (2)
E−E−E 109 (81) 85 (58)

stituents or as supramolecular assemblies in competition with
other intermolecular interactions, in the crystal lattice.1−12,18−20
In order to identify the existing sequences of chalcogen and
halogen atoms involved in linear three-body systems, a search
on the Cambridge Structural Database (CSD)21 was performed
on the fragments A−B−C (A, B, C = S, Se, Cl, Br, I) by
imposing linearity (A−B−C angle > 165°) and bond distance
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0
sAB = e(dAB− dAB) / kAB (2)
where d0AB, calculated as a sum of listed empirical parame-
ters,28,29 represents the A−B distance in isolated systems with
sAB = 1, and dAB is the distance in a perturbed system (sAB < 1).
kAB is a parameter which only marginally depends on the nature
of the atomic species A and B and shows values of about 0.37 Å

values ranging between single bonds and the sum of the van der for most bonds.29a
Waals radii of the involved atoms (Table 1). Occurrences were By assuming that in A−B···A systems, the relationship sA−B +
found in the CSD for almost all the considered combinations, sB···A = 1 holds, it can be shown that23
Publication Date (Web): May 11, 2012 | doi: 10.1021/cg201328y

and Figure 1 reports the scatter plots of the two bond distances 0
(dAB vs. dBC) for some selected systems showing a considerable
0
dAB = dAB − kAB ln[1 − e−(dAB− dAB) / kAB] (3)
incidence. It is important to point out that the imposed CSD By extending this equation to A−B···C three-body systems,
search conditions do not take in consideration the charge borne the following equation can be written:
by the fragment, so that, for example, the structural data relative
0
to the tri-iodine systems (Figure 1a) not only include discrete 0
dAB = dAB − kAB ln[1 − e−(dBC− dBC) / kBC] (4)
I3− anions but also all the sequences of three iodine atoms
following the imposed conditions. If d0AB and d0BC are approximated to the sum of covalent
It is important to stress that among the considered three- radii, rA + rB and rB + rC, respectively,30 and eq 1 is introduced
body systems, those featuring a central halogen atom are in eq 4, eq 5 can be obtained:
currently classified as cases in which a halogen bonding kAB 0
occurs.22 Thus, information obtained from the analysis of the δAB = − 0
ln[1 − e−δBCdBC/ kBC]
data in the CSD can help obtain a deeper insight into the dAB (5)
nature of the halogen bond in its widest definition within an On the condition that
A−X−B system (A, B elements, X halogen). The scatter plots
shown in Figure 1 indicate that the two bond distances in the kAB kBC
= =k
considered three-body systems are correlated and follow similar 0
dAB 0
dBC (6)
trends, although the bond values directly depend on the nature
of the atoms involved. In order to quantitatively compare all which implies that the relationship δAB = f(δBC) should be
retrieved data, it is possible to consider for each couple of A−B symmetric with respect to the straight line of equation δAB =
and B−C distances (dAB and dBC, respectively) in an A−B−C δBC (the symmetry of δAB = f(δBC) with respect to the bisector
three-body system their normalized elongations with respect to of the I quadrant is required because in a A−B···C three-body
the sum of the covalent radii of the atomic species involved (rA, system A and C can be swapped). Eq 5 can be simplified in eq
rB, and rC): 7:

d − (rA + rB) d − (rB + rC) δAB = −k ln[1 − e−δBC/ k] (7)

δAB = AB ; δ BC = BC
rA + rB rB + rC (1)
In analogy with previous analysis of systems featuring a
hydrogen bonding, several model functions f(δ) could be
adopted for correlating δAB and δBC. In particular, the O−H and
H···O distances in O−H···O systems have been fitted23 by
adopting an expression directly derived from the bond valence
model,24−29 which has been widely applied as a tool for the
interpretation and prediction of bond lengths in inorganic
crystals.25 Notably, this model, which was rationalized in terms
of the molecular orbital theory,26 has been successfully applied
not only to ionic interactions, but also to covalent compounds,
including those characterized by metallic bonding.27 According
to this model, the bond-valence24c sAB and the length dAB of an
A−B bond are related by the approximated equation:
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Equation 7 provides a direct simplified relationship between δAB
and δBC in A−B−C systems following a bond-valence model,
dependent on the single adimensional parameter k and
independent of the nature of the atomic species A, B, and C.
Therefore, eq 7 would allow for the direct comparison of δAB
and δBC values in three-body systems featuring different
composing atoms.
In the following, A−B−C systems will be analyzed on the
basis of the nature of the composing atoms.
E−X−Y Fragments. These fragments are mainly found in
CT adducts of sulfur and selenium compounds, and, among the
consistent number of structures reported, many examples
pertain to CT adducts formed by sulfur donors (E = S) and
diiodine (X = Y = I). In the past we proposed a classification of
these CT complexes into three categories: (i) weak or medium-
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Figure 1. Scatter plots of the experimental bond distances (Å) for selected A−B−C (A, B, C = S, Se, Cl, Br, I) three-body systems obtained from a
CSD21 search by imposing the linearity of the fragments (angle > 165°) and interatomic distances lower than the sum of van der Waals radii of the
involved species: (a) I−I−I 1618 (1084); (b) Br−Br−Br 181 (127); (c) S−I−I 147 (104); (d) Se−I−I 43 (32); (e) Cl−Se−Cl 155 (68); (f) Br−
Se−Br 194 fragments (86 structures).

weak adducts, in which the S···I2 interaction can be seen as a
perturbation induced by the donor on the diiodine molecule. In
these systems the I−I bond order nI−I, defined according to
original Pauling’s equation31 as a function of the distance dI−I
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between the iodine atoms ranges from values slightly lower
than 1 to about 0.6 (dI−I < 2.86 Å). (ii) Very strong adducts in
which the donor−acceptor interaction is so strong that nI−I
becomes lower than 0.4 (dI−I > 3.01 Å). (iii) Strong adducts
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 Crystal Growth & Design
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Figure 2. Structural data of the S−I−I fragments found in the CSD
reported as scatter plot of δ1 vs δ2 where δ1 = δS−I and δ2 = δI−I (see eq
1). The solid curve represents the least-squares fit of the data adopting
eq 7 as a model. The red point has not been included in the fitting.
Fitted parameter k = 0.161; rmsd = 0.036; normalized rmsd = 0.133.
Figure 3. Structural data of the S−X−Y fragments [S−I−Br (red open
circles); S−I−Cl (red open squares); S−Br−Br (red open triangles)]
reported as scatter plot of δ1 vs δ2 where δ1 = δS−X and δ2 = δX−Y (see
eq 1). The least-squares fit (eq 7) of the data provides k = 0.156 (rmsd
= 0.028; normalized rmsd = 0.103). The solid curve represents the
least-squares fit of data including the systems featuring the S−I−I
fragments (Figure 2): k = 0.160; rmsd = 0.035; normalized rmsd =
0.100. The red point in the scattergraph depicted in Figure 2 has not
been considered in the overall fit.
embracing all the intermediate cases characterized by quite
balanced bond orders (0.4 < nI−I < 0.6; 2.86 Å < dI−I < 3.01
Å).1,3a,31 This classification is supported by FT-Raman
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Figure 4. Structural data of the Se−X−Y fragments overlapped with
those of the structural data reported in the scatter plot of Figure 3
depicted as dots [S−X−Y (·); Se−I−I (red open circles); Se−I−Br
(red open squares); Se−I−Cl (red plus signs); Se−Br−Br (red open
triangles)] reported as scatter plot of δ1 vs δ2 where δ1 = δSe−X and δ2 =
δX−Y (see eq 1). The solid curve represents the least-squares fit of all
data adopting eq 7 as a model. Data with δX−Y > 0.35 along with the
red point in Figure 2 have been omitted from the fitting. Fitted
parameter k = 0.158; rmsd = 0.034; normalized rmsd = 0.089.
spectroscopy.15,32 In fact, the first class of compounds shows
FT-Raman spectra characterized by only one peak due to the
νI−I stretching vibration falling in the low frequency region at
frequencies lower than 213 cm−1 (gas phase) depending
directly on the entity of the donor−acceptor interaction
between the S donor molecule and diiodine. In the spectra of
the very strong adducts, no peaks assignable to the iodine−
iodine stretching vibration are found, thus supporting a
description of these very polarized systems as [>C−S−I]+···I−
CT adducts. For strong adducts, FT-Raman spectra are
characterized by three peaks in the low frequency region as
expected for a S−I−I three-body system.
The present class of compounds, where a continuous
variation of dS−I vs dI−I bond lengths (Figure 1c) is observed
in the condensed phases, shows close structural analogies with
systems featuring hydrogen bonding situations. In his review of
the hydrogen bonding in the solid state, Steiner observed that,
having defined X−H as the donor group and A as the hydrogen
bonding acceptor, “the hydrogen bond phenomenon is a very
broad one: there are dozens of different X−H···A interactions
that occur commonly in the condensed phases” and that
“dissociation energies span more than two orders of magnitude,
about 0.2−40 kcal·mol−1”, concluding that “the nature of the
interaction is not constant but includes electrostatic, covalent,
and dispersion contributions in varying weights”.33 Therefore,
while an electrostatic model could satisfactory explain the
chemical bonding in unbalanced S−I−I fragments in which one
of the two bond distances approach the sum of the relevant van
der Waals radii, the other bond being substantially a single
covalent bond, it becomes more and more inadequate to
describe the chemical bonding on approaching more balanced
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Figure 5. Structural data of the X−E−Y fragments overlapped with
those of the structural data reported in the scatter plot of Figure 4
depicted as dots [E−X−Y (·); Br−S−Br (red open triangles); I−S−I
(red open circles); Cl−S−Cl (red open squares); I−Se−I (green open
circles); I−Se−Br (red solid circles); Br−Se−Br (green open
triangles); Cl−Se−Br (green solid circles); Cl−Se−Cl (green open
squares)] reported as scatter plot of δ1 vs δ2 where δ1 = δX−E and δ2 =
δE−Y (see eq 1). The solid curve represents the least-squares fit of all
data adopting eq 7 as a model. The data with a red circle around them
and those not considered in the fitting of Figures 2 and 4 have not
been taken into account in the overall fit. Fitted parameter k = 0.157;
rmsd = 0.050; normalized rmsd = 0.067.
systems. This is the reason why, in our opinion, both the well-
known CT molecular orbital (CTMO) scheme and the
simplified molecular orbital model for electron-rich 3-center
4-electron (3c-4e) systems by Rundle-Pimentel34,35 can
appropriately describe these systems.1,15b Obviously, in the
case of the 3c-4e bond model, the three pz orbitals of the three
aligned atoms will contribute differently to the three molecular
orbitals having different positions in the energy scale.
In Figure 2 the structural data for S−I−I systems are
reported as a scatter plot of δS−I vs δI−I (see eq 1). A least-
squares fit of the data according to eq 7 [root-mean-square
deviation (rmsd) = 0.036] leads to a k value of 0.161. Because
parameter δ is used instead of the absolute values of the bond
distances, the same scatter plot (Figure 3) can also include data
from the CSD relative to sulfur CT adducts with I−Br, I−Cl,
and Br−Br (red symbols). Interestingly, all structural data for
sulfur CT adducts fall in the same correlation following the
application of eq 7 (rmsd on all data = 0.035; k = 0.160). As
expected on the basis of the higher acidity of Br2, IBr, and ICl
with respect to I2, the data relative to the corresponding S-
adducts are located on the right-hand side of the scatter plot
with respect to the straight line of equation δSX = δXY (see
Figure 3).
If the use of δ structural parameters is extended to the
analogous systems featuring a Se−X−Y moiety (X = Y = I, Br;
X = I, Y = Br, Cl), and all data related to the E−X−Y (E = S,
Se) fragments retrieved from the CSD are processed together,
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Figure 6. Structural data of the E−X−E fragments overlapped with
those of the structural data reported in the scatter plot of Figure 5
depicted as dots [E−X−Y (·); X−E−Y (·); E−X−E (○)] reported as
scatter plot of δ1 vs δ2 where δ1 = δE−X and δ2 = δX−E (see eq 1). Data
for GIGBED, TUNCAG, and VIYRIE were neglected since they
feature atomic positions with mixed occupancies. Because of the
peculiar structure of the bromoselenate(I) anion [Se16Br18]2− in
MUHGUR the two points circled in blue were also neglected. The
solid curve represents the least-squares fit of all data (excluding blue-
circled data and those not considered in the fitting of Figures 2, 4, and
5) adopting eq 7 as a model. Fitted parameter k = 0.157; rmsd =
0.049; normalized rmsd = 0.066.
we obtain the scatter plot shown in Figure 4, in which the solid
line represents the least-squares fit of the data according to eq
7. All δE‑X/δX‑Y data with few exceptions, share the same
correlation (k = 0.158; rmsd = 0.034), with those related to
selenium containing systems gathering on the right-hand side of
the scatter plot in agreement with the stronger donor ability of
selenium donors as compared to the sulfur congeners.
X−E−Y Fragments. These fragments are mainly found in
T-shaped 10-E-3 adducts between chalcogenone donors and
dihalogens featuring the central chalcogen atom in a hyper-
valent state. This class of compounds represents the only other
possibility to linearly arrange one chalcogen and two halogen
atoms. In Figure 5 all data found in the CSD for all the
combinations X−E−Y (E = S, Se; X, Y = I, Br, Cl) are reported
as a scattergraph of the parameters δX−E and δE−Y. The data
relative to the systems E−X−Y previously discussed have also
been introduced in the diagram as dots. All data from E−X−Y
and X−E−Y systems, with few exceptions, share the same
correlation curve following application of eq 7 (k = 0.157; rmsd
= 0.050).
E−X−E Fragments. Among the products that can be
obtained from the reactions of chalcogen donors and
dihalogens, E−X−E fragments are mainly found in [>C−E−
X−E−C<]+ so-called halonium complexes. These compounds
formally feature a central X+ (X = halogen) linearly coordinated
by two donor molecules. So far, most of these compounds
reported in the literature feature a central I+ interacting with
either S- or Se-donors.3,15b,36−38 As for the linear three-body
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 Crystal Growth & Design
Table 2. Number of Fragments (Structures) Belonging to Linear X−Y−Z (X, Y, Z = Cl, Br, I) Three-Body Systems Found in the
CSD21 for the Considered Sequences with Interatomic Distances Ranging from the Sum of the Covalent Radii up to That of
Van der Waals Radii
Y−Z = I−I I−Br
X=I 1618 (1084) 13 (9)
Br 13 (9) 68 (51)
Cl 8 (8) 4 (4)
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Figure 7. Structural data of the Br−Br−Br fragments overlapped with
those of the structural data reported in the scatter plot of Figure 6
depicted as dots [E−X−Y (·); X−E−Y (·); E−X−E (·); Br−Br−Br
(○)]. The data are reported as scatter plot of δ1 vs δ2 where δ1 =
δBr1−Br2 and δ2 = δBr2−Br3 (see eq 1). Data for NOFYUC have not been
considered since they feature Br−Br bond distances shorter than the
sum of two bromine covalent radii; the point circled in green
corresponds to the tribromide in TIJLII whose structure was solved
with an R factor of 11.08%. The solid curve represents the least-
squares fit of all data (excluding the circled point as well as those not
considered in the fitting of Figures 2 and 4−6) adopting eq 7 as a
model. Fitted parameter for Br−Br−Br fragment: k = 0.164, rmsd =
0.029, normalized rmsd = 0.048; for all data: k = 0.158; rmsd = 0.046;
normalized rmsd = 0.061.
systems discussed above, a correlation holds between the two
E−X bond distances: on reinforcing one bond, a lengthening of
the other is observed, so that the total length of the E−I−E
framework is almost independent of the nature of the organic
fragments bearing the chalcogens. Accordingly, the structural
data relative to these fragments reported as δE−X vs δX−E (eq 1)
can be fitted along with those related to the three-body systems
described above (eq 7; k = 0.157; rmsd = 0.049; Figure 6).
With the exception of two points, all the other points related to
E−X−E systems gather in the restricted area typical of systems
having fairly well balanced bonds. Two main reasons account
for this: (i) the potential energy surfaces (PESs) calculated for
the [HS−I−SH]− and [HSe−I−SeH]− model compounds are
steeper than those calculated for CT and “T-shaped” adducts
(see below); (ii) the organic framework incorporating the
chalcogen donor can shield the E−X−E fragment from further
intermolecular interactions, differently from what can happen
Article
I−Cl Br−Br Br−Cl Cl−Cl
9 (9) 2 (2) 5 (4)
4 (4) 181 (127) 4 (4)
74 (59) 4 (4) 4 (2) 10 (10)
Figure 8. Structural data of the I−I−I fragments overlapped with those
of the structural data reported in the scatter plot of Figure 7 depicted
as dots [E−X−Y (·); X−E−Y (·); E−X−E (·); Br−Br−Br (·); I−I−I
(○)]. The data are reported as a scatterplot of δ1 vs δ2 where δ1 =
δI1−I2 and δ2 = δI2−I3 (see eq 1). Data for AVIPIE, IWOFAB,
TEQCOH, and ZOLQUM have been neglected since they feature I−I
bond distances shorter than the sum of two iodine covalent radii. The
solid curve represents the least-squares fit of all data (excluding those
not considered in the fittings in Figures 2 and 4−7, and those featuring
δI−I > 0.35; see text) adopting eq 7 as a model. Fitted parameter for I−
I−I fragments: k = 0.150, rmsd = 0.010, normalized rmsd = 0.026; for
all data: k = 0.152; rmsd = 0.042; normalized rmsd = 0.057.
for E−X−Y and X−E−Y fragments (see above), where the
terminal halogen atoms of the three-body systems can be easily
involved in intermolecular contacts.
X−Y−Z Trihalogen Fragments. A survey of the crystal
structures deposited into the CSD containing any linear
sequence of three halogen atoms, having each of the two
interatomic distances spanning from the sum of the covalent
radii to the sum of the van der Waals radii provided the results
collected in Table 2. While no examples of I−Br−Cl and Br−
Cl−Cl sequences were found, all the other combinations occur,
the I−I−I systems being the most numerous followed by Br−
Br−Br, Cl−I−Cl, and Br−I−Br ones (Table 2). For our
purposes, the discussion can be limited to triiodine and
tribromine sequences, which are the most numerous. In these
cases also, the structural data, expressed as δBr−Br and δI−I (eq
1) share the same correlation found for the data corresponding
to the three-body systems discussed above and reported as dots
in Figures 7 and 8, respectively. Remarkably, a certain number
of data, mainly belonging to triiodine fragments, spread out in
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Figure 9. Potential energy surfaces (PESs) calculated for X2, X3− and for the model adducts [HE−X−X]− [E = S, Se; X = I (a), Br (b)]. d(X−X) −
d(X2)eq represents the difference between the X−X bond lengths d(X−X) with respect to the optimized ones d(X2)eq in the free dihalogens.

the regions of the scatter plot corresponding to very
unbalanced bonds. It is evident that for these three-body
systems the correlation between the two bonds, expected
according to the 3c-4e model, is lost, one of the bonds being
longer than expected and the total bond order being lower than
1. In our opinion, this can be reasonably explained by
considering that the influence of the surrounding chemical
environment on the chemical bonding within the three-body
systems becomes stronger and stronger on moving toward
bond distances that approach the sum of van der Waals radii.
This notwithstanding, the great majority of triiodine systems
(δI−I ≤ 0.35, corresponding to dI−I ≤ 3.6 Å; 87% of the data)
2775
share the correlation defined by the points corresponding to all
the other three-body systems considered so far (k = 0.152;
rmsd = 0.042 for the cumulative fitting curve in Figure 8).
These experimental observations represent the main reason
why the 3c-4e or CT models in our opinion are more adequate
to describe the “halogen bond” in linear systems featuring a
central halogen atom than a purely electrostatic model based on
the interaction between the positive electrostatic potential on
the outer side of the halogen (σ-hole) and the negative site of a
Lewis base (LB), which remains important in any case in
driving the approach of LB to the halogen site.39 The use of the
3c-4e model to describe linear three-body systems belonging to
dx.doi.org/10.1021/cg201328y | Cryst. Growth Des. 2012, 12, 2769−2779
 Crystal Growth & Design
Figure 10. Potential energy surfaces (PESs) calculated for model T-
shaped adducts [X−HE−X]− systems (E = S, Se; X = Cl, Br, and I).
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d(X−E) − d(X−E)eq represents the differences between the HE−X
bond lengths d(X−E) with respect to the optimized ones d(X−E)eq.
Publication Date (Web): May 11, 2012 | doi: 10.1021/cg201328y
Figure 11. Structural data of the Se−Se−Se fragments overlapped with
those of the structural data reported in the scatter plot of Figure 8
depicted as dots [E−X−Y (·); X−E−Y (·); E−X−E (·); X−X−X (·);
Se−Se−Se (○)]. The data are reported as a scatter plot of δ1 vs δ2
where δ1 = δSe1−Se2 and δ2 = δSe2−Se3 (see eq 1). Fitted parameter for all
data (excluding those not considered in the fittings depicted in Figures
2 and 4−8): k = 0.153; rmsd =0.043; normalized rmsd =0.057.
chalcogen-dihalogen adducts has been recently supported by
applying the quantum theory of atoms in molecules (QTAIM)
to a series of different adducts of selone donors with dihalogens
and pseudo-halogens among which are some very polarized T-
shaped compounds containing the I−Se−Cl, I−Se−Br, and I−
Se−CN fragments.12 In all three cases, the three-center
delocalization index δ(A,B,C) introduced by Ponec and co-
workers40 to better distinguish between hypervalent 3c-4e
compounds (A−B−C) and 2c-2e systems (A−B) within the
QTAIM framework indicate for all three compounds a 3c-4e
bond nature [δ(I,Se,X) = −0.203, −0.243, and −0.074 for X =
Cl, Br, and CN, respectively]. In particular, in the case of the
adduct with ICN featuring the fragment I−Se−CN, both the
calculated negative value of the local electronic energy density,
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Article
H (−0.00220 au), at the Se−I bond critical point (BCP), and
the calculated Wiberg index (0.23) for this very polarized bond
indicate a partial covalent nature for it. Analogous results were
obtained for adducts featuring Se−X−Y moieties (X = Y = I; X
= I, Y = Br, Cl) with QTAIM parameters at the BCPs of the
Se−X and X−Y bonds, indicating a 3c-4e nature also for these
systems.
In order to better understand the reasons why the considered
three-body systems feature such bonding variability, potential
energy surfaces (PESs) were calculated at the DFT level for
some representative model systems (see the Experimental
Section). For the sake of comparison, the corresponding
surface calculations were extended to dihalogen molecules (X2).
In Figure 9, the PES curves calculated for X2, X3−, and the
model CT adducts [HS−X−X]− and [HSe−X−X]− are
depicted (X = I, a; X = Br, b). The PESs calculated for the
three-body systems present a wide flat region around the
energy minima as compared to the PES curves calculated for
the 2c-2e systems X2. Because of the flat potential holes,
distortions imposed by the organic framework or weak packing
interactions of few kcal mol−1 are sufficient to impose the small
energy variations required to move the three-body systems
from the equilibrium distances. PES curves calculated for the
model systems [X−HE−X]− (E = S, Se; X = Cl, Br, I) feature
similar trends as those discussed above for trihalides (Figure
10).
Se−Se−Se Fragments. Recently, analogies and differences
between polychalcogenides and polyhalides, mainly tritellurides
and triiodides, have been comparatively discussed with the help
of quantum chemical DFT calculations, and it was shown that
homo- and heteronuclear trichalcogen systems behave as three-
body systems strictly related to those discussed above.41 The
main difference between isoelectronic (22 e) X3− trihalides and
E 3 4− trichalcogenides is the overall charge, with the
consequence that trihalides are stable anions, while trichalco-
genides cannot exist without a delocalization of the negative
charge. This is the reason why linear trichalcogen fragments can
only be found when the chalcogen atoms are bonded to organic
fragments or are part of metal complexes.
As a study case, we have searched the CSD looking for Se−
Se−Se linear systems. All data found are reported in Figure 11
as δSe−Se parameters, together with the data relative to all the
other systems previously considered (Figure 8), showing that
all share a common correlation following application of eq 7 (k
= 0.153, rmsd = 0.043). Also for Se−Se−Se fragments, several
points in the scatter plot belong to symmetric or slightly
asymmetric systems (higher covalent contribution); however,
the points corresponding to very asymmetric systems (higher
electrostatic contribution) are equally numerous. As observed
in systems featuring hydrogen bonding,33 also in Se−Se−Se
three-body systems there is no indication of a critical distance at
which the bond switches from the substantially covalent to the
predominantly electrostatic nature. However, also in this case,
although the electrostatic interaction can explain the very
unbalanced situations satisfactorily, it becomes more and more
inadequate to explain the nature of the chemical bonding in
more symmetric cases.
Interestingly, the trend of the calculated PES curve for the
[H2Se−HSe−SeH2]+ model compound (Figure 12) shows that
also in this case few kcal mol−1 are enough to displace the
three-body system from the point of minimum energy.
dx.doi.org/10.1021/cg201328y | Cryst. Growth Des. 2012, 12, 2769−2779
 Crystal Growth & Design
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Figure 12. Potential energy surface (PES) calculated for the hypothetical model compound [H2Se−HSe−SeH2]+. d(Se−Se) − d(Se−Se)eq
represents the differences between the Se−Se bond lengths d(Se−Se) with respect to the optimized one d(Se−Se)eq.
■
Publication Date (Web): May 11, 2012 | doi: 10.1021/cg201328y
CONCLUSIONS
Sequences of three aligned halogen, chalcogen, or mixed
halogen/chalcogen atoms represent recurrent motifs either as a
functional group in some archetypes of products ensuing from
the reaction of dihalogens and chalcogen donors, or as
supramolecular assemblies in many other solid products,
including polyhalides. Sequences for almost all possible
combinations of three aligned chalcogen/halogen atoms are
found in the CSD, some of them being very numerous. The
analysis of the retrieved data indicates that all systems must be
considered strictly correlated, sharing the same nature in terms
of chemical bonding. Except for the case of the E−X−E
fragment, all the other linear three-body systems here
considered show a continuous variation of the distances of
the two bonds from balanced situations up to very unbalanced
ones without indications of critical distances at which the bonds
switch from the substantially covalent to the predominantly
electrostatic nature. Indeed, by expressing all bond distances as
relative variation δ with respect to the sum of the covalent radii
of the involved atomic species, all data belonging to systems as
varied as CT adducts of chalcogen donors with halogens and
interhalogens (Figures 2−4), hypervalent chalcogen T-shaped
adducts (Figure 5), halonium complexes of chalcogen donors
(Figure 6), sequences of three halogen atoms (Figures 7−8),
can be fitted with a single semiempirical equation resulting
from the bond-valence model. Remarkably, the same
correlation can be extended to polychalcogenides, as
demonstrated for the compounds featuring Se−Se−Se frag-
ments, confirming the analogies in the electronic structures of
all the considered systems.
It is important to point out that many among the three-body
systems considered here display a central halogen atom and
therefore represent peculiar cases of arrangements in which a
halogen bonding is operating. If we had to limit the presence of
a halogen bonding to the cases in which one of the two bonds
A−X, X−B is close to the sum of the relevant van der Waals
radii, an electrostatic model could be adequate to the
description of this interaction. However, the lack of
discontinuity in the correlation between the two distances in
the classes of three-body arrangements considered renders it
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mandatory to consider the presence of a halogen bonding also
in the cases featuring balanced A−X and X−B distances. Under
such circumstances, both the CT and the 3c-4e bond models
seem to be more appropriate to describe the nature of the
halogen bonding, since the different match in the energies of
the combining orbitals is responsible for the different covalent
and electrostatic contributions.
■ EXPERIMENTAL SECTION
Structural data were retrieved from CSD by means of the
software Conquest v5.32.21 The nonlinear least-squares fit42 of
experimental data was carried out adopting eq 7 as a model
(initial guess of k = 0.37). Theoretical calculations were carried
out on dihalogens X2, trihalides X3− (X = Cl, Br, and I),
hypervalent [X−HE−X]− systems (E = S, Se; X = Cl, Br, and
I), charge transfer (CT) adducts HE·X2− (E = S, Se; X = Br and
I) and, for the sake of comparison, on the 22-electron three-
body system [H2Se−HSe−SeH2]+ with the commercial suite of
programs Gaussian 09 package.43 On the grounds of the results
reported previously and comparing different functionals in
closely related systems,2b,44 the mPW1PW functional45 was
adopted along with the Schäfer, Horn, and Ahlrichs basis set46
for hydrogen and the completely uncontracted basis sets
LANL0847 for halogen and chalcogen species with effective
core potentials (ECPs), supplemented by d-type polarization
functions. In a few cases, such as for [X−HE−Cl]− (E = S, Se;
X = Cl, Br), a quadratically convergent SCF procedure was
needed. For all species, the molecular geometry was optimized
(with the tight cutoffs on forces and step size) and verified by a
frequency calculation, carried out by determining the second
derivatives of the energy with respect to the Cartesian
coordinates of the nuclei. For three-body systems of the type
X−Y−Z, PESs were subsequently carried out by calculating the
total electronic energy at geometries obtained by systematically
scanning the variation of the X−Y and Y−Z bond distances,
with the geometrical constraint of keeping constant the X−Z
distance. All other bonds, such as chalcogen−hydrogen bonds,
were not subject to any constraints. All calculations were
carried out with an E4 Workstation equipped with four quad-
core Opteron processors and 16 GB of RAM. Molden 5.048 and
dx.doi.org/10.1021/cg201328y | Cryst. Growth Des. 2012, 12, 2769−2779
 Crystal Growth & Design
GaussView 5.049 were exploited for analyzing the results of the
calculations.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: devilla@unica.it.
Notes
The authors declare no competing financial interest.
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