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VOL. 9, NO. 6

Anion-π Interactions in Crystal Structures: Commonplace or

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 Although the majority of theoretical evidence concerns
adducts with anions via several interaction motifs.1,2 One of halides, there are surprisingly few structural examples of
these motifs, the anion-π interaction, has garnered considerable anion-π contacts involving halides. An extensive search of the
recent attention.2,3 Although discovered two decades ago,4 CSD was performed to locate all halide anions above arene π
renewed interest was sparked by four 2002 reports of electronic systems.12 The search criterion retained all structures with any
structure calculations suggesting the existence of complexes with halide anion located within 4.0 Å of the centroid of any electron-
anions centered over the face of charge-neutral arenes such as deficient six-membered ring. With the constraints that the
1,3,5-triazine,5 C6F6,6 trinitro and trifluorobenzene,7 and other π-system must be charge-neutral (not conjugated with a charged
perfluorinated arenes.8 Observations of favorable interactions species or bound to a metal cation), a total of 44 hits were
between formally negatively charged species and the π electron retained. Inspection of these structures revealed (i) that only a
clouds of uncharged aromatic rings were initially counterintui- couple of examples exhibited the characteristic directionality
tive, motivating further theoretical investigation. At this point expected for an anion-π interaction, that is, a halide located
over 150 calculated geometries have been reported, yielding a above the ring centroid, and (ii) that there were no actual
general consensus regarding the noncovalent nature of the examples for any of the anion-π complexes that had been
anion-π interaction and extensive evidence that this motif can studied theoretically.
lead to stable anion-arene adducts in the gas phase.2 In an effort Noting that direct X-ray verification of anion binding to
to obtain corroborating experimental evidence, a number of uncharged organic π receptors was lacking, structural determi-
researchers have searched the Cambridge Structural Database nations were performed on a series of crystals combining halide
(CSD)9 for examples of anion-π complexes. Here, however, salts with highly electron-deficient arenes.13 These structures,
consensus regarding the extent and interpretation of the crystal and others,12 exhibited geometries inconsistent with the anion-π
structure evidence is lacking. interaction. Rather than residing above the ring centroid, the
The first reported efforts involved searches for contacts halide is located above the ring periphery in close contact,
between any heteroatom bearing a lone pair (N, O, F, S, Cl, e∑vdw radii, with one ring atom. Such geometries have since
Br, or I) and the π system of either C6X3(NO2)3 or C6F5X (X ) been shown to be characteristic of weakly covalent σ interactions
any atom).6,7 A hit was declared when a heteroatom contacted rather than noncovalent anion-π interactions.2,12
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) There have been two extensive searches for anion-π interac-
to 4.68 (C · · · I) Å.11 A total of 271 lone pair-π interactions tions involving anions other than halides. Differing search
were reported for C6X3(NO2)3, with 10 examples involving criteria have led to grossly different conclusions regarding the
anions.7 A total of 1944 lone pair-π interactions were observed occurrence of such interactions in the CSD. The first effort was
for C6F5X, with 27 examples involving anions.6 These results a search for anion-π interactions involving NO3-, ClO4-, BF4-,
were cited as experimental evidence for electron-rich species and PF6- with C6 (any phenyl ring) and C5N (pyridine,
to locate above electron-deficient arenes. bipyridine, terpyridine, and phenanthroline) rings.14 An anion
was considered to interact with the aromatic ring in a π fashion
* Corresponding author. Phone: (865)-574-6717. E-mail: when the distance from any anion atom to the centroid was
10.1021/cg900308b CCC: $40.75  2009 American Chemical Society
Published on Web 04/09/2009
2540 Crystal Growth & Design, Vol. 9, No. 6, 2009 Perspectives

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
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
Figure 1. Geometric parameters defining the location of an atom in
e3.5 Å and all six atom-centroid-ring atom angles were within contact with planar 6-membered ring collected during the search include
90 ( 10°. These criteria yielded 17 hits for C6 rings and 152 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
hits for C5N rings. The authors concluded: “The present atom-centroid vector and the ring plane, θ. The degree of displacement
investigation has shown that the π complexes with the anion in from the center of the ring, doffset, is given by (dcentroid2 - dplane2)1/2.
the case of a simple phenyl ring are extremely rare. Recent
investigations pointing out the uniqueness of π complexes with Second, unlike van der Waals contacts, which are isotropic,
triazine or fluorinated benzenes are fully justified.” anion-π contacts are inherently directional. In addition to a
The second effort was a search for anion-π interactions short contact distance, the anion must be located above the arene
involving halides, NO3-, ClO4-, BF4-, and PF6- with all C6-nNn centroid. When analyzing thousands of contacts, if a directional
rings (n ) 0 to 6).15 A hit occurred when any anion atom interaction is common, then directionality should be apparent
contacted each of the six ring atoms within e4.0 Å. Use of in the distribution of data. For example, convincing evidence
this looser criterion yielded a total of 4,771 hits, with the in support of C-H · · · O hydrogen bonding was obtained by
majority of these observations occurring from contacts with C6 demonstrating directional behavior with a preference for linear
(659 hits) and C5N (3227 hits) rings. Table 1 compares the contact geometries.17 Accordingly, if the anion-π interaction
number of hits per anion obtained in the second study against is prevalent in the CSD, then the frequency of contacts over
those obtained in the first study, illustrating order-of-magnitude the center of an arene π system should be greater than expected
differences. The authors of this second study concluded: from random van der Waals contacts.
“Anion-π contacts are in fact not particularly exceptional in Finally, the term “anion-π interaction” was first used in
solid-state structures” and “We believe that the sole observation reference to C6F6 complexes6 and early reports on the anion-π
of an anion-π close contact therefore should not be sufficient interaction all involved uncharged arenes.4–7 The fact that a
to justify its simple report as a separate or special publication.” negatively charged species could be attracted to a charge-neutral
Although prior searches differ significantly in the definition π-electron cloud is what made these systems so intriguing,18
of what constitutes a contact, all of them use criteria that would leading to extensive theoretical studies of anion-π adducts with
locate anions above arene π systems and, thus, would locate uncharged arenes.2 Therefore, bona fide crystal structure
examples of anion-π interactions that might exist in the CSD. examples representing the structures obtained in the majority
It is important to realize, however, that the observation of an of theoretical studies on the anion-π interaction must neces-
anion in the vicinity of an arene π system is necessary, but not sarily involve charge-neutral arenes.
sufficient, evidence of an anion-π interaction. There are literally These additional criteria have not been evaluated in previous
thousands of crystal structures that contain both anions and arene studies, and the question remains as to whether the 10s to 1000s
π systems in the CSD.14,15 Because both the anions and arenes of “contacts” that have been reported actually represent valid
must necessarily pack within the crystal lattice, it should come examples of anion-π interactions. Herein we address this
as no surprise that these structures contain tens of thousands of question through further interrogation of the CSD. Unlike prior
anion-arene contacts. To claim that any of these contacts efforts, which constrained searches to a limited volume of space
provide convincing examples of the anion-π interactions centered above the arene π system, the search criterion used
predicted by theory, several additional criteria must be satisfied. here was designed to locate all contacts between the arene and
First and foremost, the contacts should display geometries the contacting species. Hits were retained if any atom of the
that closely correspond to those predicted by electronic structure contacting species was within e7.0 Å of the arene centroid.
calculations. In all calculated structures, the anion contacts the After filtering out data that might be of poorer quality (no errors,
arene ring atoms at distances <∑vdw radii and is centered over no disorder, and an rfac e 0.10), geometric parameters defined
the arene π system. Unequivocal examples of anion-π interac- in Figure 1 were collected for each contact. In what follows,
tions would exhibit these geometric features. When examining graphical representations and statistical analysis of this data yield
large numbers of structures, the repeated observation of contacts some some new insight into the location of anions about C6
that are <∑vdw radii is generally considered as strong evidence and C5N rings. Contrary to previous reports, the current analysis
for the existence of an attractive intermolecular interaction.16 reveals that the CSD completely fails to provide any convincing
Weak electrostatic interactions may exhibit contacts that are crystal structure evidence for anion-π interactions involving
slightly longer than the ∑vdw radii. In the C-H · · · O hydrogen charge-neutral, 6-membered rings with Cl-, Br-, I-, NO3-,
bond, for example, although the ∑vdw radii for an H · · · O ClO4-, BF4-, and PF6- anions.
contact is 2.73 Å,11 cutoff distances that are 0.1 to 0.3 Å longer To provide a baseline for the interpretation of anion-arene
have been used to search for them.17 In the current study, an contacts, we first examine the behavior exhibited in the absence
example of an experimentally observed structure that closely of any significant interaction by searching for contacts between
resembles the expected anion-π geometry is defined to be one the hydrogen atoms of terminal methyl groups in CR3CH3 (R
in which contact distances are e∑vdw radii + 0.2 Å. ) C or H) and C6H6. Although C-H · · · π interactions involving
Perspectives Crystal Growth & Design, Vol. 9, No. 6, 2009 2541

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. 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
aliphatic C-H donors are known, theoretical calculations Å above the C6H6 plane. (b) Comparison of histograms for experimental
establish them to be very weak, e1 kcal/mol.19 Thus, such versus random (thin black bars) doffset distributions.
contacts are expected not to exhibit any detectable directionality, directionality is anticipated, the cation-π interaction.21 The
and this expectation is confirmed by the CSD search results. methods described above for R3CH3 · · · C6H6 contacts were
Two methods are used to graphically display the distribution applied to locate and evaluate contacts between K+ and C6
of contacts about the arene. The first method is to plot doffset arenes. As before, the doffset vs dplane plot (Figure 4a) shows a
versus dplane (see Figure 1) where each point represents the cloud of contacts distributed over the entire C6 surface, but now
location of a contacting atom. The inside of this atom distribu- with a noticeable clustering above the arene π system. Com-
tion, where the arene is located, is hollow with a perimeter that parison of experimental vs random tilt angle distributions (Figure
is approximated by an oblate ellipsoid. This inner perimeter 4b) reveals a statistically significant excess of K+ cations at θ
represents the van der Waals contact distance between the values >75°, indicative of a preference to locate over the arene
surfaces of the contacting species and the arene. It is clear that centroid. This preference becomes very apparent on viewing
for an atom to be considered in contact with the arene, it must the placement of 267 K+ cations located 3.16 ( 0.5 Å above
be within 1 Å of this interior elliptical perimeter. Therefore, all the C6 plane (Figure 4c) and the comparison of experimental
data sets are trimmed to retain only the hits that meet this vs random doffset distributions (Figure 4d).
requirement. Figure 2a shows this plot for 2239 aliphatic methyl In addition to exhibiting a greater than random preference to
hydrogen atoms that are in contact with C6H6 by this definition. reside above the π system, further inspection of the data reveals
As expected, the spatial distribution of hydrogen atoms corre- that a number of these contacts meet the two additional criteria
sponds closely to what one would expect for simple van der needed to qualify as bona fide crystal structure examples for
Waals behavior. That is, the frequency of contacts at any the cation-π interaction, that is, the contacts involve charge-
position is simply proportional to the amount of exposed arene neutral arenes and exhibit geometries closely resembling the
surface area at that position. This is graphically illustrated in theoretically predicted geometry for this interaction. Whereas
Figure 2b by showing that the experimental tilt angle, θ, the charge of the arene can be unambiguously verified by visual
distribution for this data corresponds closely to that expected inspection, the definition of what constitutes a close resemblance
for a statistically random distribution.20 requires some clarification.
The second method involves generating a view of a subset In cation-π interactions involving alkali metals, the cation
of the data meeting the following criteria: doffset e 3 Å and dplane is located directly over the centroid, with a θ value of 90°.
within the ∑vdw radii for ring atom contact ( 0.5 Å. This Allowing for some degree of distortion in the tilt angle, contacts
selects a 1 Å thick disk of data centered above the surface of with θ ) 90 ( 10° will be considered acceptable. The other
the arene π system. Figure 3a shows the position of 444 aliphatic geometric requirement is that the K+ be in close contact with
methyl hydrogen atoms located 2.9 ( 0.5 Å above the C6H6 the arene. Allowing for some degree of distortion, a close
plane. The observed distribution again corresponds closely to resemblance is achieved when the contact is within 0.2 Å of
that expected for simple van der Waals behavior. This is calculated values for the K+ · · · C6H6 complex, dplane ) 2.85 to
graphically illustrated in Figure 3b by showing that the 2.90 Å,22 in other words, dplane e 3.10 Å. After removing
experimental offset distance, doffset, distribution for this data contacts that fail to meet these structural restrictions, there
corresponds closely to that expected for a statistically random remain 34 contacts with uncharged C6 arenes that closely
distribution.20 resemble the theoretically predicted geometry. On the basis of
Having examined the behavior of a case where there is no these results it is concluded that the CSD provides unambiguous
significant directionality, we next evaluate a case where some evidence in support of the cation-π interaction.
2542 Crystal Growth & Design, Vol. 9, No. 6, 2009 Perspectives

Figure 4. Distribution of contacts between K+ cations and C6 arenes.

(a) Plot of doffset versus dplane shows the position of 1314 K+ cations Figure 5. Distribution of contacts between Cl- anions and C6 arenes.
within (1 Å of an oblate ellipsoid (a ) b ) 5.0 Å, c ) 3.3 Å). (b) (a) Plot of doffset vs dplane shows the position of 9082 Cl- anions within
Comparison of histograms for experimental versus random (thin black (1 Å of an oblate ellipsoid (a ) b ) 5.0 Å, c ) 3.3 Å). (b) Comparison
bars) tilt angle, θ, distributions. (c) Looking down from above with of histograms for experimental versus random (thin black bars) tilt
doffset e 3 Å, the plot shows the location of 267 K+ cations 2.66 to angle, θ, distributions. (c) Looking down from above with doffset e 3
3.66 Å above the C6 plane. (d) Comparison of histograms for Å, the plot shows the location of 248 Cl- anions 2.66 to 3.66 Å above
experimental versus random (thin black bars) doffset distributions. 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 (Figure 5d) reveals a significant preference for Cl- to be
and evaluate contacts between Cl- and C6 arenes. The doffset vs positioned outside, rather than above, the C6 arene π system.
dplane plot (Figure 5a) shows a cloud of 9082 Cl- anions This is not at all surprising given that the majority of the arenes
distributed over the entire C6 surface. This distribution is quite located in this search are not electron-deficient, and therefore
different from that observed for K+ cations (Figure 4a). There would not be expected to form stable anion-π interactions.
is no noticeable clustering over the π system, but rather a Although not showing any statistical preference for position-
pronounced, dense clustering at the arene periphery. Comparison ing above the π system, Figure 5c shows that a small number
of experimental vs random tilt angle distributions (Figure 5b) of Cl- contacts, only 17 out of the total 9082, are above the
reveals a large excess of Cl- anions at θ values <20°. As arene plane and within the perimeter of the arene ring. Do any
discussed in detail elsewhere, these contacts result from the of these contacts represent examples of anion-π interactions,
dominant interaction motif, C-H · · · Cl- hydrogen bonding.2,23,24 that is, do they involve charge-neutral arenes and do they closely
A general lack of a preference to reside over a C6 arene π system resemble the geometries predicted by theoretical calculations?
is observed on viewing the placement of 248 Cl- anions located In calculated anion-π geometries involving Cl- and C6
3.16 ( 0.5 Å above the C6 plane (Figure 5c). In fact, a arenes,2 the Cl- is directly above the ring centroid and in close
comparison of experimental vs random doffset distributions 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 Figure 9. Molecular structures and CSD reference codes for all contacts
surprised to discover that not one clear example of an between halides, NO3-, ClO4-, BF4-, and PF6- anions and any planar
anion-π interaction with a charge-neutral arene was located six-membered ring that exhibit characteristic anion-π geometries: the
in the entire CSD database. We are, however, aware of three anion centroid is located over the ring centroid (θ ) 90 ( 10°); halides
examples involving halides that do exhibit characteristic contact all six ring atoms within ∑vdw radii + 0.2 Å; other anions
anion-π geometries, but not identified with our criteria. Two 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
of them, one with Cl- above a triazine ring27 and one with more than one six-membered ring is present, the interacting ring is
F- sandwiched between two cyanuric acid rings,28 were indicated by thicker lines.
discarded due to disorder. Another recent crystal structure
example, with Cl- above a triazine ring,29 was not found
heteroatoms (N, O, F, S, Cl, Br, and I) in contact with C6F5X (X
because it was not in the CSD at the time of these searches.
) any atom). Restricting this data set with the criterion that the
Thus, we conclude that genuine examples of anion-π
heteroatom must contact all carbon atoms at distances of e∑vdw
interactions with uncharged arenes are extraordinary. Even
in cases where the arene is positively charged, only a small radii + 1.0 Å, contacts located within the gray bullet shaped area
number of structures actually exhibit the geometry expected were cited as evidence of a preference for electron-rich species to
for an anion-π interaction. locate over the arene centroid, thereby supporting the existence of
We also conclude that some care is required in the interpretation anion-π interactions with perfluorinated arenes.6,10 On analysis
of CSD search results. Although the use of loose contact criteria, of the entire data distribution, however, it becomes clear that (i)
in which an interaction is claimed when an atom contacts all six the majority of the contacts within the search volume are not located
ring atoms at distances of g4 Å, can indeed locate thousands of above the ring centroid and (ii) the contacts show no statistical
contacts, (i) this result does not by itself provide evidence for the preference to cluster over the centroid, in other words, heteroatoms
existence of an interaction and (ii) most of the contacts actually are distributed randomly over this π system.12 Repeating this search
bear little resemblance to the expected interaction geometry. This using criteria that the contact distance must be e∑vdw radii +
is illustrated graphically in Figure 10, showing the distribution of 0.2 Å and the tilt angle must be 90 ( 10°, only one out of the
Perspectives Crystal Growth & Design, Vol. 9, No. 6, 2009 2545

(12) Berryman, O. B.; Bryantsev, V. S.; Stay, D. P.; Johnson, D. W.; Hay,
B. P. J. Am. Chem. Soc. 2007, 129, 48.
(13) Rosokha, Y. S.; Lindeman, S. V.; Rosokha, S. V.; Kochi, J. K. Angew.
Chem., Int. Ed. 2004, 43, 4650.
(14) Ahuja, R.; Samuelson, A. G. CrystEngComm 2003, 5, 395.
(15) Mooibroek, T. J.; Black, C. A.; Gamez, P.; Reedijk, J. Cryst. Growth
Des. 2008, 8, 1082.
(16) (a) Lommerse, J. P. M.; Stone, A. J.; Taylor, R.; Allen, F. H. J. Am.
Chem. Soc. 1996, 118, 3108. (b) Han, B.; Lu, J.; Kochi, J. K. Cryst.
Growth Des. 2008, 8, 1327.
(17) (a) Steiner, T.; Desiraju, G. R. Chem. Commun. 1998, 891. (b) Desiraju,
G. R.; Steiner, T. In The Weak Hydrogen Bond in Structural Chemistry
and Biology; Oxford University Press: New York, 1999. (c) Steiner,
Figure 10. Distribution of 13,646 intermolecular contacts between any T. Angew. Chem. 2002, 41, 48.
N, O, S, F, Cl, Br, or I atom and any C6F5X ring (X ) any atom) in (18) Although anions have also been shown to bind the π systems of
the CSD. The gray area indicates data selected when the atom contacts cationic 6-membered arenes, the occurrence of such ion pairing is far
all six ring carbon atoms within 4.2 Å. less surprising. (a) Alkorta, I.; Elguero, J. J. Phys. Chem. 2003, 107,
9428. (b) Garau, C.; Quinoñero, D.; Frontera, A.; Ballester, P.; Costa,
13,646 contacts shown in Figure 10 actually resembles the A.; Deyà, P. M. New J. Chem. 2003, 370, 7. (c) Estarellas, C.; Frontera,
A.; Quinoñero, D.; Deyà, P. M. J. Chem. Theory Comput. 2008, 4,
geometry anticipated for a lone pair-π interaction.29
1981. (d) Quinoñero, D.; Frontera, A.; Deyà, P. M. ChemPhysChem
2008, 9, 397.
Acknowledgment. This research was sponsored by the (19) (a) Malone, J. F.; Murray, C. M.; Charlton, M. H.; Docherty, R.;
Division of Chemical Sciences, Geosciences, and Biosciences, Lavery, A. J. J. Chem. Soc., Faraday Trans. 1997, 93, 3429. (b) Novoa,
Office of Basic Energy Sciences, U.S. Department of Energy, J. J.; Mota, F. Chem. Phys. Lett. 2000, 318, 345. (c) Bogdanovic, G. A.;
under Contract No. DE-AC05-00OR22725 with Oak Ridge Spasojevic-de Bire, A.; Zaric, S. D. Eur. J. Inorg. Chem. 2002, 1599.
National Laboratory managed by UT-Battelle, LLC. (20) Full details on methods used to generate random distribution histograms
are given as Supporting Information.
(21) (a) Dougherty, D. A.; Stauffer, D. A. Science 1990, 250, 1558. (b)
Supporting Information Available: Details of CSD search speci-
Ma, J. C.; Dougherty, D. A. Chem. ReV. 1997, 95, 1303.
fications, derivation of histograms corresponding to random distribu-
(22) (a) Kumpf, R. A.; Daugherty, D. A. Science 1993, 261, 1708. (b)
tions, and experimental distributions for anions around C6 and C5N Caldwell, J. W.; Kollman, P. A. J. Am. Chem. Soc. 1995, 117, 4177.
rings. This material is available free of charge via the Internet at http:// (c) Nicholas, J. B.; Hay, B. P.; Dixon, D. A. J. Phys. Chem. A 1999, 103, 1394.
(23) (a) Bryantsev, V. S.; Hay, B. P. J. Am. Chem. Soc. 2005, 127, 8282–
References 8283. (b) Bryantsev, V. S.; Hay, B. P. Org. Lett. 2005, 7, 5031–5034.
(24) (a) Aakeröy, C. B.; Evans, T. A.; Seddon, K. R.; Palinko, I. New
(1) Paul, G. J. C.; Kebarle, P. J. Am. Chem. Soc. 1991, 113, 1148. J. Chem. 1999, 145. (b) van den Berg, J.-A.; Seddon, K. R. Cryst.
(2) Hay, B. P.; Bryantsev, V. S. Chem. Commun. 2008, 2417. Growth Des. 2003, 3, 643.
(3) (a) Gamez, P.; Mooibroek, T. J.; Teat, S. J.; Reedijk, J. Acc. Chem. (25) (a) Kim, D.; Tarakeshwar, P.; Kim, K. S. J. Phys. Chem. A 2004,
Res. 2007, 40, 435. (b) Schottel, B. L.; Chifotides, H. T.; Dunbar, 108, 1250. (b) Garau, C.; Quinoñero, D.; Frontera, A.; Escudero, D.;
K. R. Chem. Soc. ReV. 2008, 37, 68. Ballester, P.; Costa, A.; Deyà, P. M. Chem. Phys. Lett. 2007, 438,
(4) (a) Hiraoka, K.; Mizuse, S.; Yamabe, S. J. Phys. Chem. 1987, 91, 104. (c) Barrios, L. A.; Aromi, G.; Frontera, A.; Quinoñero, D.; Deyà,
5294. (b) Chowdhury, S.; Kebarle, P. J. Chem. Phys. 1986, 85, 4989. P. M.; Gamez, P.; Roubeau, O.; Shotton, E. J.; Teat, S. J. Inorg. Chem.
(5) Mascal, M.; Armstrong, A.; Bartberger, M. D. J. Am. Chem. Soc. 2002, 2008, 47, 5873.
124, 6247. (26) Other symmetrical orientations of tetrahedral and octahedral anions
(6) Quinoñero, D.; Garau, C.; Rotger, C.; Frontera, A.; Ballester, P.; Costa, above the arene plane, for example, contacting the π system with only
A.; Deyà, P. M. Angew. Chem., Int. Ed. 2002, 41, 3389. one or two anion atoms, have been reported.25b,c Such alternate
(7) Quinoñero, D.; Garau, C.; Frontera, A.; Ballester, P.; Costa, A.; Deyà, orientations (i) do not represent minima on the potential surface and
P. M. Chem. Phys. Lett. 2002, 359, 486. (ii) are significantly less stable than the actual minimum in which the
(8) Alkorta, I.; Rozas, I.; Elguero, J. J. Am. Chem. Soc. 2002, 124, 8593. anion contacts the π system via three atoms.
(9) Cambridge Structural Database, Version 5.29, November 2007. (b) (27) Demeshko, S.; Dechert, S.; Meyer, F. J. Am. Chem. Soc. 2004, 126,
Allen, F. H. Acta Crystallogr. 2002, B58, 380. 4508.
(10) Prior reports state that a nonbonded contact existed between a (28) Mascal, M.; Yakovlev, I.; Nikitin, E. B.; Fettinger, J. C. Angew. Chem.
heteroatom and an arene carbon atom when the contact distance was 2007, 46, 8782.
e∑vdw radii.6,7 However, the actual contact distance used was e∑vdw (29) (a) The distribution shown in Figure 10 raises concerns over the validity
radii + 1.0 Å. Personal communication with C. Garau, Universitat de of a recent study claiming evidence for thousands of lone pair-π
les Illes Balears, Palma de Mallorca, Spain. interactions in the CSD. (b) Mooibroek, T. J.; Gamez, P.; Reedijk, J.
(11) (a) Default CSD van der Waals radii were used in this study: H, 1.20 CrystEngComm. 2008, 1501.
Å; C, 1.70 Å; N, 1.55 Å; O, 1.52 Å; F, 1.47 Å; Cl, 1.75 Å; Br, 1.85;
I, 1.98 Å. (b) Bondi, A. J. Phys. Chem. 1964, 68, 441. CG900308B