CRYSTAL
GROWTH
PerspectiVes
Anion-π Interactions in Crystal Structures: Commonplace or
Extraordinary?
Benjamin P. Hay* and Radu Custelcean
Oak Ridge National Laboratory, Chemical Sciences DiVision, Oak Ridge National Laboratory,
Oak Ridge, Tennessee 37831-6119
ReceiVed March 16, 2009
ABSTRACT: An in-depth analysis of the distribution of anions about planar six-membered rings in the Cambridge Structural
Database reveals anion-π interactions with charge-neutral π systems to be extremely rare in crystal structures. The predominant
interaction motif is C-H · · · anion hydrogen bonding.
Arenes, and in particular electron-deficient arenes, form stable
adducts with anions via several interaction motifs.1,2 One of
these motifs, the anion-π interaction, has garnered considerable
recent attention.2,3 Although discovered two decades ago,4
renewed interest was sparked by four 2002 reports of electronic
structure calculations suggesting the existence of complexes with
anions centered over the face of charge-neutral arenes such as
1,3,5-triazine,5 C6F6,6 trinitro and trifluorobenzene,7 and other
perfluorinated arenes.8 Observations of favorable interactions
between formally negatively charged species and the π electron
clouds of uncharged aromatic rings were initially counterintui-
tive, motivating further theoretical investigation. At this point
over 150 calculated geometries have been reported, yielding a
general consensus regarding the noncovalent nature of the
anion-π interaction and extensive evidence that this motif can
lead to stable anion-arene adducts in the gas phase.2 In an effort
to obtain corroborating experimental evidence, a number of
researchers have searched the Cambridge Structural Database
(CSD)9 for examples of anion-π complexes. Here, however,
consensus regarding the extent and interpretation of the crystal
structure evidence is lacking.
The first reported efforts involved searches for contacts
between any heteroatom bearing a lone pair (N, O, F, S, Cl,
Br, or I) and the π system of either C6X3(NO2)3 or C6F5X (X )
any atom).6,7 A hit was declared when a heteroatom contacted
all six arene carbons within the ∑vdw radii + 1.0 Å,10 in other
words, within relatively long contact distances of 4.17 (C · · · F)
to 4.68 (C · · · I) Å.11 A total of 271 lone pair-π interactions
were reported for C6X3(NO2)3, with 10 examples involving
anions.7 A total of 1944 lone pair-π interactions were observed
for C6F5X, with 27 examples involving anions.6 These results
were cited as experimental evidence for electron-rich species
to locate above electron-deficient arenes.
* Corresponding author. Phone: (865)-574-6717. E-mail: haybp@ornl.gov.
10.1021/cg900308b CCC: $40.75  2009 American Chemical Society
Published on Web 04/09/2009
& DESIGN
2009
VOL. 9, NO. 6
2539–2545
Although the majority of theoretical evidence concerns
halides, there are surprisingly few structural examples of
anion-π contacts involving halides. An extensive search of the
CSD was performed to locate all halide anions above arene π
systems.12 The search criterion retained all structures with any
halide anion located within 4.0 Å of the centroid of any electron-
deficient six-membered ring. With the constraints that the
π-system must be charge-neutral (not conjugated with a charged
species or bound to a metal cation), a total of 44 hits were
retained. Inspection of these structures revealed (i) that only a
couple of examples exhibited the characteristic directionality
expected for an anion-π interaction, that is, a halide located
above the ring centroid, and (ii) that there were no actual
examples for any of the anion-π complexes that had been
studied theoretically.
Noting that direct X-ray verification of anion binding to
uncharged organic π receptors was lacking, structural determi-
nations were performed on a series of crystals combining halide
salts with highly electron-deficient arenes.13 These structures,
and others,12 exhibited geometries inconsistent with the anion-π
interaction. Rather than residing above the ring centroid, the
halide is located above the ring periphery in close contact,
e∑vdw radii, with one ring atom. Such geometries have since
been shown to be characteristic of weakly covalent σ interactions
rather than noncovalent anion-π interactions.2,12
There have been two extensive searches for anion-π interac-
tions involving anions other than halides. Differing search
criteria have led to grossly different conclusions regarding the
occurrence of such interactions in the CSD. The first effort was
a search for anion-π interactions involving NO3-, ClO4-, BF4-,
and PF6- with C6 (any phenyl ring) and C5N (pyridine,
bipyridine, terpyridine, and phenanthroline) rings.14 An anion
was considered to interact with the aromatic ring in a π fashion
when the distance from any anion atom to the centroid was
2540 Crystal Growth & Design, Vol. 9, No. 6, 2009
Table 1. Reported Frequencies of Anion-π Interactions with C6
and C5N Rings in the CSD
arene methoda Cl- NO3- ClO4- BF4- PF6- total
C6 A na 1 4 4 8 17
C6 B 19 63 175 167 235 659
C5N A na 14 62 14 62 152
C5N B 21 359 1454 314 1079 3227
a
Search method A identifies an anion-arene contact as an anion-π
interaction when any atom of the anion is e3.5 Å from the arene
centroid and all six anion atom-centroid-arene atom angles are within
90 ( 10°.14 Search method B identifies an anion-arene contact as an
anion-π interaction when any atom of the anion is within 4.0 Å of all
six ring atoms.15
e3.5 Å and all six atom-centroid-ring atom angles were within
90 ( 10°. These criteria yielded 17 hits for C6 rings and 152
hits for C5N rings. The authors concluded: “The present
investigation has shown that the π complexes with the anion in
the case of a simple phenyl ring are extremely rare. Recent
investigations pointing out the uniqueness of π complexes with
triazine or fluorinated benzenes are fully justified.”
The second effort was a search for anion-π interactions
involving halides, NO3-, ClO4-, BF4-, and PF6- with all C6-nNn
rings (n ) 0 to 6).15 A hit occurred when any anion atom
contacted each of the six ring atoms within e4.0 Å. Use of
this looser criterion yielded a total of 4,771 hits, with the
majority of these observations occurring from contacts with C6
(659 hits) and C5N (3227 hits) rings. Table 1 compares the
number of hits per anion obtained in the second study against
those obtained in the first study, illustrating order-of-magnitude
differences. The authors of this second study concluded:
“Anion-π contacts are in fact not particularly exceptional in
solid-state structures” and “We believe that the sole observation
of an anion-π close contact therefore should not be sufficient
to justify its simple report as a separate or special publication.”
Although prior searches differ significantly in the definition
of what constitutes a contact, all of them use criteria that would
locate anions above arene π systems and, thus, would locate
examples of anion-π interactions that might exist in the CSD.
It is important to realize, however, that the observation of an
anion in the vicinity of an arene π system is necessary, but not
sufficient, evidence of an anion-π interaction. There are literally
thousands of crystal structures that contain both anions and arene
π systems in the CSD.14,15 Because both the anions and arenes
must necessarily pack within the crystal lattice, it should come
as no surprise that these structures contain tens of thousands of
anion-arene contacts. To claim that any of these contacts
provide convincing examples of the anion-π interactions
predicted by theory, several additional criteria must be satisfied.
First and foremost, the contacts should display geometries
that closely correspond to those predicted by electronic structure
calculations. In all calculated structures, the anion contacts the
arene ring atoms at distances <∑vdw radii and is centered over
the arene π system. Unequivocal examples of anion-π interac-
tions would exhibit these geometric features. When examining
large numbers of structures, the repeated observation of contacts
that are <∑vdw radii is generally considered as strong evidence
for the existence of an attractive intermolecular interaction.16
Weak electrostatic interactions may exhibit contacts that are
slightly longer than the ∑vdw radii. In the C-H · · · O hydrogen
bond, for example, although the ∑vdw radii for an H · · · O
contact is 2.73 Å,11 cutoff distances that are 0.1 to 0.3 Å longer
have been used to search for them.17 In the current study, an
example of an experimentally observed structure that closely
resembles the expected anion-π geometry is defined to be one
in which contact distances are e∑vdw radii + 0.2 Å.
Perspectives
Figure 1. Geometric parameters defining the location of an atom in
contact with planar 6-membered ring collected during the search include
the distance from the atom to the ring centroid, dcentroid, the distance
from the atom to the ring plane, dplane, and the tilt angle between the
atom-centroid vector and the ring plane, θ. The degree of displacement
from the center of the ring, doffset, is given by (dcentroid2 - dplane2)1/2.
Second, unlike van der Waals contacts, which are isotropic,
anion-π contacts are inherently directional. In addition to a
short contact distance, the anion must be located above the arene
centroid. When analyzing thousands of contacts, if a directional
interaction is common, then directionality should be apparent
in the distribution of data. For example, convincing evidence
in support of C-H · · · O hydrogen bonding was obtained by
demonstrating directional behavior with a preference for linear
contact geometries.17 Accordingly, if the anion-π interaction
is prevalent in the CSD, then the frequency of contacts over
the center of an arene π system should be greater than expected
from random van der Waals contacts.
Finally, the term “anion-π interaction” was first used in
reference to C6F6 complexes6 and early reports on the anion-π
interaction all involved uncharged arenes.4–7 The fact that a
negatively charged species could be attracted to a charge-neutral
π-electron cloud is what made these systems so intriguing,18
leading to extensive theoretical studies of anion-π adducts with
uncharged arenes.2 Therefore, bona fide crystal structure
examples representing the structures obtained in the majority
of theoretical studies on the anion-π interaction must neces-
sarily involve charge-neutral arenes.
These additional criteria have not been evaluated in previous
studies, and the question remains as to whether the 10s to 1000s
of “contacts” that have been reported actually represent valid
examples of anion-π interactions. Herein we address this
question through further interrogation of the CSD. Unlike prior
efforts, which constrained searches to a limited volume of space
centered above the arene π system, the search criterion used
here was designed to locate all contacts between the arene and
the contacting species. Hits were retained if any atom of the
contacting species was within e7.0 Å of the arene centroid.
After filtering out data that might be of poorer quality (no errors,
no disorder, and an rfac e 0.10), geometric parameters defined
in Figure 1 were collected for each contact. In what follows,
graphical representations and statistical analysis of this data yield
some some new insight into the location of anions about C6
and C5N rings. Contrary to previous reports, the current analysis
reveals that the CSD completely fails to provide any convincing
crystal structure evidence for anion-π interactions involving
charge-neutral, 6-membered rings with Cl-, Br-, I-, NO3-,
ClO4-, BF4-, and PF6- anions.
To provide a baseline for the interpretation of anion-arene
contacts, we first examine the behavior exhibited in the absence
of any significant interaction by searching for contacts between
the hydrogen atoms of terminal methyl groups in CR3CH3 (R
) C or H) and C6H6. Although C-H · · · π interactions involving
Perspectives
Figure 2. Distribution of intermolecular contacts between CR3CH3
methyl hydrogen atoms and C6H6. (a) Plot of doffset versus dplane shows
the position of 2239 hydrogen atoms within (1 Å of an oblate ellipsoid
(a ) b ) 4.4 Å, c ) 2.9 Å). The mesh over the benzene molecule is
the electron density isosurface rendered at a value of 0.002 e/Å3. (b)
Comparison of histograms for experimental versus random (thin black
bars) tilt angle, θ, distributions.
aliphatic C-H donors are known, theoretical calculations
establish them to be very weak, e1 kcal/mol.19 Thus, such
contacts are expected not to exhibit any detectable directionality,
and this expectation is confirmed by the CSD search results.
Two methods are used to graphically display the distribution
of contacts about the arene. The first method is to plot doffset
versus dplane (see Figure 1) where each point represents the
location of a contacting atom. The inside of this atom distribu-
tion, where the arene is located, is hollow with a perimeter that
is approximated by an oblate ellipsoid. This inner perimeter
represents the van der Waals contact distance between the
surfaces of the contacting species and the arene. It is clear that
for an atom to be considered in contact with the arene, it must
be within 1 Å of this interior elliptical perimeter. Therefore, all
data sets are trimmed to retain only the hits that meet this
requirement. Figure 2a shows this plot for 2239 aliphatic methyl
hydrogen atoms that are in contact with C6H6 by this definition.
As expected, the spatial distribution of hydrogen atoms corre-
sponds closely to what one would expect for simple van der
Waals behavior. That is, the frequency of contacts at any
position is simply proportional to the amount of exposed arene
surface area at that position. This is graphically illustrated in
Figure 2b by showing that the experimental tilt angle, θ,
distribution for this data corresponds closely to that expected
for a statistically random distribution.20
The second method involves generating a view of a subset
of the data meeting the following criteria: doffset e 3 Å and dplane
within the ∑vdw radii for ring atom contact ( 0.5 Å. This
selects a 1 Å thick disk of data centered above the surface of
the arene π system. Figure 3a shows the position of 444 aliphatic
methyl hydrogen atoms located 2.9 ( 0.5 Å above the C6H6
plane. The observed distribution again corresponds closely to
that expected for simple van der Waals behavior. This is
graphically illustrated in Figure 3b by showing that the
experimental offset distance, doffset, distribution for this data
corresponds closely to that expected for a statistically random
distribution.20
Having examined the behavior of a case where there is no
significant directionality, we next evaluate a case where some
Crystal Growth & Design, Vol. 9, No. 6, 2009 2541
Figure 3. (a) Looking down from above with doffset e 3 Å, the plot
shows the position of 444 CR3CH3 methyl hydrogen atoms 2.4 to 3.4
Å above the C6H6 plane. (b) Comparison of histograms for experimental
versus random (thin black bars) doffset distributions.
directionality is anticipated, the cation-π interaction.21 The
methods described above for R3CH3 · · · C6H6 contacts were
applied to locate and evaluate contacts between K+ and C6
arenes. As before, the doffset vs dplane plot (Figure 4a) shows a
cloud of contacts distributed over the entire C6 surface, but now
with a noticeable clustering above the arene π system. Com-
parison of experimental vs random tilt angle distributions (Figure
4b) reveals a statistically significant excess of K+ cations at θ
values >75°, indicative of a preference to locate over the arene
centroid. This preference becomes very apparent on viewing
the placement of 267 K+ cations located 3.16 ( 0.5 Å above
the C6 plane (Figure 4c) and the comparison of experimental
vs random doffset distributions (Figure 4d).
In addition to exhibiting a greater than random preference to
reside above the π system, further inspection of the data reveals
that a number of these contacts meet the two additional criteria
needed to qualify as bona fide crystal structure examples for
the cation-π interaction, that is, the contacts involve charge-
neutral arenes and exhibit geometries closely resembling the
theoretically predicted geometry for this interaction. Whereas
the charge of the arene can be unambiguously verified by visual
inspection, the definition of what constitutes a close resemblance
requires some clarification.
In cation-π interactions involving alkali metals, the cation
is located directly over the centroid, with a θ value of 90°.
Allowing for some degree of distortion in the tilt angle, contacts
with θ ) 90 ( 10° will be considered acceptable. The other
geometric requirement is that the K+ be in close contact with
the arene. Allowing for some degree of distortion, a close
resemblance is achieved when the contact is within 0.2 Å of
calculated values for the K+ · · · C6H6 complex, dplane ) 2.85 to
2.90 Å,22 in other words, dplane e 3.10 Å. After removing
contacts that fail to meet these structural restrictions, there
remain 34 contacts with uncharged C6 arenes that closely
resemble the theoretically predicted geometry. On the basis of
these results it is concluded that the CSD provides unambiguous
evidence in support of the cation-π interaction.
2542 Crystal Growth & Design, Vol. 9, No. 6, 2009
Figure 4. Distribution of contacts between K+ cations and C6 arenes.
(a) Plot of doffset versus dplane shows the position of 1314 K+ cations
within (1 Å of an oblate ellipsoid (a ) b ) 5.0 Å, c ) 3.3 Å). (b)
Comparison of histograms for experimental versus random (thin black
bars) tilt angle, θ, distributions. (c) Looking down from above with
doffset e 3 Å, the plot shows the location of 267 K+ cations 2.66 to
3.66 Å above the C6 plane. (d) Comparison of histograms for
experimental versus random (thin black bars) doffset distributions.
We now turn our attention to the anion-π interaction. The
same methods used in the prior two cases were applied to locate
and evaluate contacts between Cl- and C6 arenes. The doffset vs
dplane plot (Figure 5a) shows a cloud of 9082 Cl- anions
distributed over the entire C6 surface. This distribution is quite
different from that observed for K+ cations (Figure 4a). There
is no noticeable clustering over the π system, but rather a
pronounced, dense clustering at the arene periphery. Comparison
of experimental vs random tilt angle distributions (Figure 5b)
reveals a large excess of Cl- anions at θ values <20°. As
discussed in detail elsewhere, these contacts result from the
dominant interaction motif, C-H · · · Cl- hydrogen bonding.2,23,24
A general lack of a preference to reside over a C6 arene π system
is observed on viewing the placement of 248 Cl- anions located
3.16 ( 0.5 Å above the C6 plane (Figure 5c). In fact, a
comparison of experimental vs random doffset distributions
Perspectives
Figure 5. Distribution of contacts between Cl- anions and C6 arenes.
(a) Plot of doffset vs dplane shows the position of 9082 Cl- anions within
(1 Å of an oblate ellipsoid (a ) b ) 5.0 Å, c ) 3.3 Å). (b) Comparison
of histograms for experimental versus random (thin black bars) tilt
angle, θ, distributions. (c) Looking down from above with doffset e 3
Å, the plot shows the location of 248 Cl- anions 2.66 to 3.66 Å above
the C6 plane. (d) Comparison of histograms for experimental versus
random (thin black bars) doffset distributions.
(Figure 5d) reveals a significant preference for Cl- to be
positioned outside, rather than above, the C6 arene π system.
This is not at all surprising given that the majority of the arenes
located in this search are not electron-deficient, and therefore
would not be expected to form stable anion-π interactions.
Although not showing any statistical preference for position-
ing above the π system, Figure 5c shows that a small number
of Cl- contacts, only 17 out of the total 9082, are above the
arene plane and within the perimeter of the arene ring. Do any
of these contacts represent examples of anion-π interactions,
that is, do they involve charge-neutral arenes and do they closely
resemble the geometries predicted by theoretical calculations?
In calculated anion-π geometries involving Cl- and C6
arenes,2 the Cl- is directly above the ring centroid and in close
contact with all six arene carbon atoms, that is, all six Cl- · · · C
Perspectives Crystal Growth & Design, Vol. 9, No. 6, 2009 2543

Figure 6. Molecular structure and CSD reference codes for the only
two contacts between Cl- and C6 arenes that exhibit the characteristic
anion-π geometry: Cl- located above the ring centroid (θ ) 90 (
10°); Cl- contacts all six carbon atoms within 3.65 Å (∑vdw radii +
0.2 Å). The interacting ring is indicated by thicker lines.

contacts <∑vdw radii or <3.45 Å.11 This translates to dplane

values <3.16 Å. Again allowing for a reasonable degree of
structural distortion, we define a convincing crystal structure
example of what has been theoretically predicted as having Cl-
in contact with all six ring carbons to within ∑vdw + 0.2 Å
(dplane e 3.37 Å) and a tilt angle of θ ) 90 ( 10°.
Only two contacts, Figure 6, meet these requirements. One
contact, TAJXEI, involves an arene that is not electron-deficient
and, therefore, actually represents a repulsive interaction. The
other contact, SEGSED, occurs with a π system that is bound
directly to a metal cation, thus failing to meet the requirement
of charge neutrality. The remaining 15 contacts, which are either
too far above the arene and/or too far off center, are inconclu-
sive. These represent either considerably distorted examples of
anion-π interactions or simple van der Waals interactions. It
could be argued that the latter is more likely given the observed
data distributions (Figure 5). Thus, use of the current search
criteria (vide supra) fails to locate even one convincing example
of an anion-π interaction between Cl- and a charge-neutral
C6 arene.
Searches for contacts between C6 arenes and NO3-, ClO4-,
BF4-, and PF6- anions revealed strictly analogous behavior to
that exhibited by Cl-. Distributions in doffset vs dplane plots (Figure
7) again show a depletion of contacts above the π system and
a concentration of contacts at the ring periphery. Comparisons
of tilt angle distributions, the location of contacts above the
ring, and comparisons of doffset distributions all indicate that
anions are in general attracted to the ring periphery and repelled
by the π system (see Supporting Information). As with Cl-, a Figure 7. Plots of doffset versus dplane show the distribution of other
anions in contact with C6 arenes. From top to bottom: NO3-, position
very small percentage of the total contacts actually occur in of 3,155 nitrogen atoms within (1 Å of an oblate ellipsoid (a ) b )
the region above the arene centroid and the question again arises 5.0 Å, c ) 3.3 Å); ClO4-, position of 14,007 chlorine atoms within
as to whether any of these contacts actually represent examples (1 Å of an oblate ellipsoid (a ) b ) 5.5 Å, c ) 3.8 Å); BF4-, position
of anion-π interactions. of 11,092 boron atoms within (1 Å of an oblate ellipsoid (a ) b )
Electronic structure calculations predict that noncovalent 5.5 Å, c ) 3.8 Å); PF6-, position of 15,834 phosphorus atoms within
interactions between the arene π system and polyatomic anions (1 Å of an oblate ellipsoid (a ) b ) 5.7 Å, c ) 4.0 Å).
exhibit some common structural features.2,6,25 First, the center
of the anion is positioned over the center of the arene. Second, occur in 11,092 BF4- contacts, and 6 examples occur in 15,834
one face of the anion is parallel to the arene face such that PF6- contacts. Without exception the arenes in these examples
three of the anion atoms are each in close contact, <∑vdw radii, are either bound directly to metal cations or positively charged
with one ring carbon atom.26 In other words, three oxygen atoms organic species. Thus, as with Cl-, this CSD search fails to
of NO3- and ClO4- have dplane values <3.22 Å and three fluorine provide any corroboration that these anions engage in anion-π
atoms of BF4- and PF6- have dplane values <3.17 Å.11 As interactions with charge-neutral C6 arenes.
discussed above, a convincing crystal structure example of what Although prior searches indicate that C5N rings exhibit more
has been theoretically predicted would have the anion centroid anion-π interactions than C6 rings (see Table 1), current search
located over the arene centroid with a tilt angle of 90 ( 10° and analysis methods do not support this claim. Data and plots
and three O or F atoms in contact with alternating arene carbon for contacts of the different anions with C5N rings exhibit the
atoms to within ∑vdw + 0.2 Å (e3.42 Å for O and e3.37 Å same behavior observed for C6 rings (see Supporting Informa-
for F). tion). The distributions reveal a strong preference for all
Application of these criteria to the data in Figure 7 once again monovalent anions to locate at the ring periphery and no
reveals that very few contacts exhibit geometries that resemble preference to locate above the C5N π system. As with C6 rings
those predicted by electronic structure calculations. These are very few contacts, only 11 examples from a total of 51,065
summarized in Figure 8. No examples occur in 3,155 NO3- contacts, bear a close resemblance to geometries expected for
contacts, 3 examples occur in 14,007 ClO4- contacts, 4 examples anion-π interactions (see Figure 9).
2544 Crystal Growth & Design, Vol. 9, No. 6, 2009 Perspectives

Figure 8. Molecular structures and CSD reference codes for the contacts
between ClO4-, BF4-, and PF6- anions and planar C6 rings that exhibit
characteristic anion-π geometries: the anion centroid is located over
the ring centroid (θ ) 90 ( 10°); anions contact the ring with three O
or F atoms such that each of the three contacting atoms are within
∑vdw radii + 0.2 Å of a ring atom. When more than one six-membered
ring is present, the interacting ring is indicated by thicker lines.

To locate all other possible examples of anion-π interactions

involving the anions under consideration in this study, a final
series of searches was performed to locate contacts with any
planar X6 ring (X ) any atom) that exhibited characteristic
anion-π geometries as defined above. In addition to the 14
examples located for C6 rings (see above), analysis of all other
planar six-membered rings yielded the additional 32 examples
in Figure 9. As with the C6 rings, the π systems in these
examples are all positively charged by protonation, alkylation,
or metalation.
With the search criteria used in this study (plus the added
constraints of rfac e 0.10, no error, no disorder), we were
surprised to discover that not one clear example of an
anion-π interaction with a charge-neutral arene was located
in the entire CSD database. We are, however, aware of three
examples involving halides that do exhibit characteristic
anion-π geometries, but not identified with our criteria. Two
of them, one with Cl- above a triazine ring27 and one with
F- sandwiched between two cyanuric acid rings,28 were
discarded due to disorder. Another recent crystal structure
example, with Cl- above a triazine ring,29 was not found
because it was not in the CSD at the time of these searches.
Thus, we conclude that genuine examples of anion-π
interactions with uncharged arenes are extraordinary. Even
in cases where the arene is positively charged, only a small
number of structures actually exhibit the geometry expected
for an anion-π interaction.
We also conclude that some care is required in the interpretation
of CSD search results. Although the use of loose contact criteria,
in which an interaction is claimed when an atom contacts all six
ring atoms at distances of g4 Å, can indeed locate thousands of
contacts, (i) this result does not by itself provide evidence for the
existence of an interaction and (ii) most of the contacts actually
bear little resemblance to the expected interaction geometry. This
is illustrated graphically in Figure 10, showing the distribution of
Figure 9. Molecular structures and CSD reference codes for all contacts
between halides, NO3-, ClO4-, BF4-, and PF6- anions and any planar
six-membered ring that exhibit characteristic anion-π geometries: the
anion centroid is located over the ring centroid (θ ) 90 ( 10°); halides
contact all six ring atoms within ∑vdw radii + 0.2 Å; other anions
contact the ring with three O or F atoms such that each of the three
contacting atoms are within ∑vdw radii + 0.2 Å of a ring atom. When
more than one six-membered ring is present, the interacting ring is
indicated by thicker lines.
heteroatoms (N, O, F, S, Cl, Br, and I) in contact with C6F5X (X
) any atom). Restricting this data set with the criterion that the
heteroatom must contact all carbon atoms at distances of e∑vdw
radii + 1.0 Å, contacts located within the gray bullet shaped area
were cited as evidence of a preference for electron-rich species to
locate over the arene centroid, thereby supporting the existence of
anion-π interactions with perfluorinated arenes.6,10 On analysis
of the entire data distribution, however, it becomes clear that (i)
the majority of the contacts within the search volume are not located
above the ring centroid and (ii) the contacts show no statistical
preference to cluster over the centroid, in other words, heteroatoms
are distributed randomly over this π system.12 Repeating this search
using criteria that the contact distance must be e∑vdw radii +
0.2 Å and the tilt angle must be 90 ( 10°, only one out of the
Perspectives
Figure 10. Distribution of 13,646 intermolecular contacts between any
N, O, S, F, Cl, Br, or I atom and any C6F5X ring (X ) any atom) in
the CSD. The gray area indicates data selected when the atom contacts
all six ring carbon atoms within 4.2 Å.
13,646 contacts shown in Figure 10 actually resembles the
geometry anticipated for a lone pair-π interaction.29
Acknowledgment. This research was sponsored by the
Division of Chemical Sciences, Geosciences, and Biosciences,
Office of Basic Energy Sciences, U.S. Department of Energy,
under Contract No. DE-AC05-00OR22725 with Oak Ridge
National Laboratory managed by UT-Battelle, LLC.
Supporting Information Available: Details of CSD search speci-
fications, derivation of histograms corresponding to random distribu-
tions, and experimental distributions for anions around C6 and C5N
rings. This material is available free of charge via the Internet at http://
pubs.acs.org.
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(20) Full details on methods used to generate random distribution histograms
are given as Supporting Information.
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(26) Other symmetrical orientations of tetrahedral and octahedral anions
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one or two anion atoms, have been reported.25b,c Such alternate
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