Remote Substituents as Potential Control Elements for the Solid-State Structures of Hypervalent Iodine(III) Compounds

Article abstract of DOI:10.1021/acs.inorgchem.1c00339

Hypervalent iodine (HVI) compounds are very important selective oxidants often employed in organic syntheses. Most HVI compounds are strongly associated in the solid state involving interactions between the electropositive iodine centers and nearby electr

Full text of DOI:10.1021/acs.inorgchem.1c00339

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Remote Substituents as Potential Control Elements for the Solid-
State Structures of Hypervalent Iodine(III) Compounds
Guobi Li, Arnold L. Rheingold, and John D. Protasiewicz*
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ABSTRACT: Hypervalent iodine (HVI) compounds are very important
selective oxidants often employed in organic syntheses. Most HVI
compounds are strongly associated in the solid state involving interactions
between the electropositive iodine centers and nearby electron lone pairs
of electronegative atoms. This study examines the impact of remote
substituents on select families of HVI compounds as means to achieve
predictable two-dimensional extended solid-state materials. Crystallo-
graphic analyses of 10 HVI compounds from several related classes of λ3
organoiodine(III) compounds, (diacetoxyiodo)benzenes,
(dibenzoatoiodo)benzenes, [bis(trifluoroacetoxy)iodo]benzenes, and μ-
oxo-[(carboxylateiodo)benzenes], provide insights into how remote
substituents and the choice of carboxylate groups can impact
intermolecular interactions in the solid state.
design element for crystal engineering of the heavier p-block
compounds.25
INTRODUCTION
■
Hypervalent iodine (HVI) compounds have often been
employed as mild and highly selective oxidants in organic
syntheses.1−4 HVI compounds have also recently found new
applications as versatile catalysts and reagents for oxidative
addition, reductive elimination, ligand exchange, and coupling
reactions.5−10 HVI compounds thus offer promise as metal-
free alternatives to traditional transition metal compounds in
catalytic applications. Compared with transition metal
compounds, HVI compounds offer several advantageous
characteristics, which include the facts that they are more
environmentally benign, less toxic, and earth abundant.11−14
While advantages for HVI compounds are apparent,
challenges for using some HVI compounds remain due to
limited solubility, which is often caused by extensive
aggregation in the solid state.15,16 HVI compounds feature
electropositive iodine centers, and these sites of positive
charge interact with electronegative atoms much in the same
way hydrogen atoms form hydrogen bonds that dictate the
solid-state structures of many materials.17−20 In a 1972
review, Alcock described intermolecular contacts involving
nonmetallic elements that are closer than the sum of the van
der Waals radii and are approximately linear as secondary
bonds.21 The analogy between secondary bonds and
hydrogen bonds was explored by Hoffmann, noting the
interplay between electrostatic and donor−acceptor inter-
actions.22,23 The important acceptor functionality was
identified as a σ* orbital. Crabtree has reviewed the
connections among hypervalency, secondary bonding, halo-
gen bonding, and hydrogen bonding.24 Orpen recognized
early on the potential to utilize secondary bonding as a
While the term secondary bonding was originally
introduced for intermolecular interactions between heavier
main group compounds, the term halogen bonding has
evolved to describe similar intermolecular interactions
between halogens and neighboring sites of electron density
(R−X···B).26 Specifically, IUPAC defines halogen bonding as
follows. “A halogen bond occurs when there is evidence of a
net attractive interaction between an electrophilic region
associated with a halogen atom in a molecular entity and a
nucleophilic region in another, or the same, molecular
entity”.27 Common in many halogen bonding interactions
involving organoiodine species are a number of notable
physical attributes, which include (a) roughly linear arrays of
R−I···D (D = donor atom) and (b) I···D distances that are
smaller than the sum of van der Waals radii.
Halogen bonding involving organoiodine compounds has
been attributed to the presence of regions of positive
electrostatic potential at the iodine center, known as σ
holes, that can favorably interact with negatively charged
atoms.28−31 A number of reports have examined the
theoretical basis for these I···E interactions,32 and Justik has
Received: February 5, 2021
Published: May 10, 2021
https://doi.org/10.1021/acs.inorgchem.1c00339
© 2021 American Chemical Society
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recently discussed the history and connections between
secondary bonding and halogen bonds, in the context of
reviewing structural HVI chemistry.33 Kiprof has shown ab
initio molecular orbital calculations focusing on iodine oxygen
bonds in hypervalent 10-I-3 iodine compounds.34
Among well-studied λ3 HVI compounds, organoiodine-
(III)-carboxylates represent prototypical examples of HVI
compounds and versatile platforms for ready variations at the
c a r b o x y l a t e a n d i o d o a r e n e s i t e s . N o t a b l y ,
(dicarboxalatoiodo)benzenes have even been used as cross-
linkers to produce functional polymers.58,59 Many HVIs of
the form ArI(O2CR)2 have already been reported as their
synthesis from appropriate ArI is usually straightfor-
ward.11,60,61 Those that have been structurally characterized
display significant I···O interactions between the carboxylate
oxygen atoms and the iodine centers. In most of these
structures, both carboxylate oxygen atoms coordinate to the
iodine center via I···O interactions yielding a local “bow tie”
type of structure (Figure 2A) with the CO2, I, and Cipso
The solubility and extended aggregation of HVI com-
pounds can be modulated greatly by introduction of suitable
intramolecular substituents to occupy coordination sites
about the iodine center that might otherwise be involved in
intermolecular interactions.15−17 Understanding of how these
species are arranged in the solid state would allow access to
evaluate the impact of substituents on structures and crystal
design. For example, our group has found that introduction
of an ortho tert-butyl-sulfonyl group in iodosylbenzene
transforms the polymeric and insoluble iodosylbenzene into
a pseudocyclic soluble compound.35 The Zhdankin group
reported a series of HVI (III) compounds bearing intra-
molecular I···O (IntraI···O) with an array of substituents, such
as an ester of 2-iodoxybenzoic acid, acetoxy of benziodoxole,
and benziodazoles.36−38 Amino acid-derived benziodazoles
can use I···E interactions to self-assemble into macrocyles.39
Togni has shown that perfluoroorganyl benziodoxolones can
undergo aggregation to yield polymeric supramolecular
structures.40 Wirth and colleagues also explored intra-
molecular I···E interactions using furan and thiophene
moieties in the vicinity of the iodine(III) center and found
new applications.41,42 The Huber group showed the
intermolecular I···O (InterI···O) of iodonium salts to
coordinate with diester and diamide.43 Other functional
groups have also been employed to modify the properties of
HVI species.44−51
Though intentionally designed intramolecular I···E inter-
actions are prominent in HVI chemistry, studies of
intentionally designed intermolecular I···E interactions using
remote substituents have been a limited area of research. By
contrast, crystal engineering using substituted organoiodine-
(I) compounds has been well developed over recent
years.26,29,52,53 Interestingly, these interactions in the solid
state can even lead to different photophysical properties,
including new types of organic phosphorescent materi-
als.54−56
This study reports on a systematic investigation of the
impact of remote substituents (Z) on halogen bonding
involving organoiodine(III) compounds in the solid state.
Our specific approach focused on para-Z-substituted common
(and stable) λ3 HVI species, represented by the general
structure in Figure 1. A simple design goal was to ascertain if
Figure 2. Commonly observed I···O interactions in
(dicarboxylatoiodo)arenes. Intramolecular and intermolecular I···O
interactions are colored red and blue, respectively.
atoms in the same plane. Rotation about the I−Cipso bond in
this form (i.e., the plane of the iodoaryl ring) occurs to
varying extents. Less common are examples in which only
one of the two carboxylate oxygen atoms coordinates and
allows the iodine engage in external I···E interactions (Figure
2B). Given the high propensity of the iodine center to engage
in intramolecular I···O interactions with one or more of the
carboxylate groups, Z units are capable of offering donor
atoms that might compete with the chelated carboxylate
groups. Specifically, Z groups having lone pairs of electrons
such as fluorine (F), nitro (NO2), cyano (CN), and
methoxycarbonyl [CO(O)Me] were thus chosen to promote
intermolecular I···E interactions over intramolecular I···O
interactions and form extended structures. The resulting
structures were analyzed and compared to previously
reported structures of related (dicarboxylatoiodo)arenes.
RESULTS AND DISCUSSION
■
Synthesis of (Dicarboxylatoiodo)arenes. A series of p-
Z-PhI [Z = F, CN, C(O)OMe, or NO2] were oxidized in
acetic acid to afford the previously reported corresponding p-
Z-PhI(OAc)2 (1a−1d).60−65 A variety of specific conditions
have been reported for the synthesis of ArI(OAc)2. Three
synthetic methodologies, differing in oxidants, were examined
to optimize the yield for each compound (Scheme 1).
Method I used sodium perborate.60 Method II employed m-
CPBA.61 Method III utilized solid sodium hypochlorite
pentahydrate.62 In our hands, method I proved to be optimal
for 1a, while method III gave the best results for 1b−1d.
Nuclear magnetic resonance (NMR) spectra for 1a−1d were
consistent with reported data (see the Supporting Informa-
tion). The synthesis and handling of HVI compounds in
general should be done carefully and on small scales, owing
Figure 1. Potential oligomeric solid-state structure driven by
intermolecular I···E interactions.
oligomeric or polymeric arrays would be established in the
crystalline state driven by these novel intermolecular
interactions. Evidence that this approach may be general is
provided by several para-Z-λ3-iodanes. Of particular note are
p-NO2-PhICl2 and the diaryliodonium salt [(p-NO2-PhI)Ph]-
BF4 that form extended coordination polymers in the solid
state linked by I···O2N secondary bonds with a range of
3.00−3.56 Å.47,57
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a
Scheme 1. Synthesis of 1−3
a
Method I: 10 equiv of NaBO4·4H2O in AcOH for 6 h at 40-45 °C.
Method II: 1.1 equiv of m-CPBA in AcOH for 9−48 h at 55 °C.
Method III: 1.0 equiv of NaClO·5H2O in AcOH at room temperature
for 10 min. Asterisks indicate compounds structurally characterized in
this study. TFA is trifluoroacetic acid, BZA is benzoic acid.
to reports of explosive decomposition under heating and/or
extensive drying.1,66,67
Compounds 1a−1d provided access, via carboxylate
exchange reactions, to related (dibenzoateiodo)arenes 2a−
2d and [bis(trifluoroacetoxy)iodo]arenes 3a−3c. The two
types of crystals of μ-oxo-λ3-iodanes 4c (OAc) and 5d
(O2CCF3) were obtained from the slow evaporation of 1c
from glacial acetic acid and the slow evaporation of 1d from
trifluoroacetic acid, respectively. (Dibenzoateiodo)arenes 2a−
2d, 3c, and μ-oxo-λ3-iodanes 4c and 5d are new, while the
other (dicarboxylatoiodo)arene synthesis has been reported.
Figure 3. ORTEP representations of 1a−1d. Ellipsoids drawn at the
50% probability level. Violet atoms are iodine, red atoms oxygen,
green atoms fluorine, and blue atoms nitrogen. Hydrogens have
been omitted for the sake of clarity.
Table 1. Comparison of Key Distances of 1a−1d and
Related Compounds
IntraI···O (Å)/I−O (Å)
Refcode
1
All compounds were authenticated by H and 13C{1H}NMR
Z
p-F (1a)
p-CN (1b)
p-C(O)OMe (1c)
p-NO2 (1d)
p-C(O)OEt
[2.826/2.140]; [2.846/2.172]
[2.765/2.166]; [2.850/2.117]
[2.803/2.138]; [2.844/2.143]
[2.740/2.137]; [2.826/2.161]
[2.819/2.147]; [2.864/2.139]
[2.780/2.133]; [2.801/2.141]
[2.779/2.149]; [2.820/2.160]
[2.825/2.139]; [2.847/2.164]
[2.776/2.134]; [2.857/2.172]
[2.817/2.158]; [2.851/2.153]
[2.805/2.144]; [2.867/2.163]
[2.818/2.153]; [2.850/2.161]
this work
this work
this work
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TUKPAT69
NIVHUW49
NEZTET48
NEZTAP48
IBZDAC70
IBZDAC1171
IBZDAC1272
IBZDAC1373
spectroscopy.
Structural Analyses of (Dicarboxylatoiodo)arenes.
Crystals suitable for single-crystal X-ray diffraction analyses
for 1a were grown by layering a solution of 1a in CH2Cl2
with hexanes. Crystals for X-ray studies of 1b−1d were
grown by slow evaporation of the solvent from concentrated
solutions (1b and 1c, ClCH2CH2Cl; 1d, acetic acid). The
four crystal structures, displayed in Figure 3, conform to the
generic structure shown in Figure 2A. The IntraI···O distances
in 1a−1d varied within the range of 2.74−2.85 Å (Table 1).
No significant intermolecular interactions with para-Z
substituents were noted, with the exception that a potential
weak interaction between a p-NO2 oxygen atom might be
ascribed to a long I···O contact distance of 3.48(1) Å, just
below the sum of the I−O van der Waal radii of 3.50 Å
[compared to an I1···O4 distance of 2.82(6) Å].68 The I−O
bond lengths span the range of 2.11−2.18 Å and are
consistent with the mean I−O bond length of 2.14 Å and in
the range of 1.84−2.47 Å.34 A large number of ArI(O2CR)2
have been structurally characterized; eight of these structures
are of the form p-Z-PhI(OAc)2, and these are listed in Table
1 for comparison.48,49,69−73
i
p-S(O2)OCH2 Pr
p-Cl
p-CH3
H
H
H
H
evaporation from trifluoroacetic acid solutions (3c). Not all
derivatives produced crystals of sufficient quality for single X-
ray diffraction experiments, and in some cases, excess
handling led to hydrolysis and formation of crystalline μ-
oxo-λ3-iodanes (4c and 5d).
Structurally characterizations of ArI(ArCO2)2 have been
limited to two examples, PhI(o-MePhCO2)2 and PhI-
(C6F5CO2)2. To complement these data, crystals of p-F-
PhI(PhCO2)2 (2a) and PhI(PhCO2)2 (2e) were successfully
grown, and the resulting structures are shown in Figure 4.
Summary data for all four structures are listed in Table 2.74,75
Both PhI(o-MePhCO2)2 and 2a conform to the generalized
structure A in Figure 2. Structural analysis shows compound
2e is in the solid state; however, one of the two benzoate
arms is rotated by 61.8° (as calculated by planes of two CO2
subunits). This rotation leads to significant asymmetry to the
IntraI···O bonds [2.88(0) and 3.04(8) Å]. The weakened
IntraI···O interaction, however, is compensated by formation of
It thus appears that it is rather challenging for InterI···O
bonds to compete with the internal I···O bonds provided by
the vicinal carboxylates. Recognizing that I···O interactions
are driven in large part by electrostatic attractions, we
investigated carboxylates that have less electron rich oxygens
−
−
(CF3CO2 and PhCO2 ) and hence presumably weaker
IntraI···O interactions. Crystals suitable for X-ray analysis were
grown either by layering a solution of (dicarboxylatoiodo)-
arenes in CH2Cl2 with hexanes (2a, 2e, and 3a) or by slow
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Upon comparison of the (diarylcarboxylateiodo)arenes to
the (diacetoxyiodo)arenes, it seems that the likelihood of
departing from structure A is increased by the decreased
basicity of the carboxylate unit. Upon further extension of
this argument, it would portend that trifluoroacetoxy-
containing iodoarenes would have even greater propensity
for structural flexibility, as is seen in 3a and 3c (Figure 4). All
four previously structurally characterized ArI(CF3CO2)2
species (data listed in Table 3) indeed show a marked
Table 3. Comparison of Key Distances of 3a, 3c, and
Related Compounds
Z
IntraI···O (Å)/I−O (Å)//InterI···O (Å)
Refcode
p-F (3a)
[2.970/2.156//3.049]; [3.151/2.132//
3.049]
this work
p-C(O)OMe
(3c)
m-COOH
[2.962/2.175//3.019]; [3.159/2.126//
3.019]
this work
[3.083/2.182//3.042]; [3.144/2.141//
YIVHER76
BIHFUW45
CEZBEO77
CEZBEO0178
KELBUY79
a
3.042]
p-CH3
[3.001/2.169//2.987]; [3.137/2.137//
2.987]
[3.001/2.171//3.057]; [3.153/2.133//
3.057]
[3.000/2.186//3.038]; [3.133/2.139//
3.038]
[3.075/2.147//3.190]; [3.121/2.128//
3.190]
H
H
F5(ArC6F5)
a
Average of five independent molecules in unit cell.
preference for structure type B, having one of the carboxylate
groups shifted away to allow intermolecular I···O interactions
and dimeric associations.45,76−79 The dimers within the
structure of ArI(CF3CO2)2 where Ar = 3-COOH are also
aggregated by bifurcated hydrogen bonding, leading to
interesting polymer arrays.76
During the search for conditions to grow X-ray quality
crystal types of 1 and 3, crystals of the hydrolysis products μ-
oxo-λ3-iodanes 4c and 5d were obtained (Scheme 2 and
Scheme 2. Formation of 4c and 5d
Figure 4. ORTEP representations of 2a, 2e, 3a, 3c, and 4c.
Ellipsoids drawn at the 50% probability level. Violet atoms are
iodine, red atoms oxygen, green atoms fluorine, and blue atoms
nitrogen. Hydrogens have been omitted for the sake of clarity.
Table 2. Comparison of Key Distances of 2a, 2e, and
Related Compounds
IntraI···O (Å)/I−O (Å)//InterI···O
Figure 5). This led to the opportunity to expand this study to
analogues of (dicarboxylatoiodo)arenes having an oxo-iodane
group replacing one of the carboxylates. Previously
characterized μ-oxo-λ3-iodanes fall into two main classes,
compounds that arise by hydrolysis of two independent
(dicarboxylatoiodo)arenes, and heterocyclic compounds
based on diaryl and dinaphthyl backbones. The former are
more relevant for structural comparisons here. Structural
details for these four compounds are summarized along with
details for 4c and 5d in Table 4.80−83 The four reported μ-
oxo-λ3-iodanes and 4c all feature extensive intermolecular
bonding I···O interactions of varying degrees [structures C,
D, and D′ (Figure 6)]. In structure type C, there are a pair
of [I−O−I]···OC interactions that hold together a dimeric
assembly of two molecules.80 In structure types D and D′,
one of the [I−O−I]···OC interactions involves a third
molecule, thus forming a polymeric assembly in the solid
Z
Ar
Ph
Ph
(Å)
Refcode
p-F (2a)
H (2e)
[2.751/2.173]; [2.879/2.138]
[2.880/2.159//3.065];
[3.048/2.122//3.065]
this work
this work
H
o-tolyl [2.934/2.136]; [2.934/2.136]
RBIHOZ74
CAJMAB75
F5(ArC6F5) C6F5
[3.120/2.101//2.957];
[3.132/2.135//2.957]
an InterI···O bond [3.06(5) Å] that affords a dimeric array of
structure type B for 2e (Figure 4). Interestingly, in the
reported structure of C6F5I(O2CC6F5)2, both carboxylate
entities have moved away from that as depicted in structure
A to increase the accessibility of the iodine center across
from the phenyl ring.79 In the solid state, this compound
exists as a loosely associated dimer with a single InterI···O
bond at 2.95(7) Å, while the IntraI···O bond is around 3.13 Å.
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Figure 5. ORTEP representations of 5d showed two crystallographically independent molecules and their independent polymer chains formed
via InterI···O interactions (highlighted in blue dashed lines). Select bond lengths (angstroms) and angles (degrees): I2···O6, 3.15(8); I2···O7,
3.20(6); I1···O8, 2.99(1); I1···O9, 3.44(4); I1′···O6′, 3.32(1); I1′···O7′, 3.07(4); I2′···O8′, 2.96(9); I1′···O1′, 2.98(7); I1···O6, 3.03(9).
Ellipsoids drawn at the 50% probability level. Violet atoms are iodine, green atoms fluorine, red atoms oxygen, and blue atoms nitrogen.
Hydrogens have been omitted for the sake of clarity.
Table 4. Comparison of Key Distances of 4c, 5d, and Related Compounds
structure
Z
R
type
IntraI···O (Å)/I−OAc (Å)//InterI···O (Å)
[2.894/2.235//3.704]; [2.991/2.215//3.303]
Refcode
p-C(O)OMe
(4c)
CH3
C
this work
p-NO2 (5d)
CF3
E/E′
[2.987/2.287//3.074/3.321]; [3.039/2.279//3.158/3.206]; [3.150/2.257//3.444/2.991];
[3.175/2.261//2.969]
this work
H
H
m-CH3
p-CH3
CH3
CF3
CF3
CF3
C
[2.856/2.214//3.381]; [3.020/2.245//3.096]
AHORIZ80
DAJTUD81
FAVBEJ82
RIMXEQ83
D′
D′
D
[2.938/2.258//3.497/3.389 (I···F)]; [3.273/2.287//3.083]
[3.128/2.295//3.364/3.381 (I···F)]; [3.188/2.297//3.315]
[3.060/2.248//3.216]; [3.452/2.288//3.080]
state.81−83 A weak I···FCF2 interaction [3.38(9) Å]
approximately trans to the I−Cipso bond in DAJTUD is
present.83
often been reproduced in a number of theoretical studies.32
While these structures are largely consistent in the solid state,
in solution the acetoxy groups are actually dynamic and
exchange oxygen atoms connected to the iodine atoms.84,85
The fluxional process was proposed to involve intramolecular
[1,3] sigmatropic shift of iodine as supported by density
functional theory calculations. The barrier to exchange of
these oxygens for PhI(OAc)2, as estimated by 17O DNMR
spectroscopy, is a ΔG# of 45.5 kJ/mol with negligible entropy
or solvent dependency. The same study showed nearly
identical barriers for the p-OMe and p-NO2 compounds.
Interestingly, it was found that the 17O and 13C NMR
resonances were insensitive to variation of para substituents.
Similarly, the 13C NMR shifts for Cipso carbons across the
series were very narrow.
Compound 5b, however, presents a completely new type of
structure format. First, the crystals of 5b contain two
independent molecules that differ mainly in the projection
of the aryl units with respect to one another (highlighted in
green in Figure 6). Second, each iodine center engages in
halogen bonding between the p-nitro groups of neighboring
molecules to assemble two parallel infinite coordination
polymer chains E and E′. It thus appears that by combination
of using the highly electron withdrawing CF3 carboxylate, in
conjunction with replacement of one of the hindering
carboxylates by an oxo unit, the HVI center can finally
take advantage of the opportunity to engage in intermolecular
interactions with the remote nitro substituent.
One very recent computational effort particularly relevant
to our study calculated the structures of a series of p-Z-
C6H4I(OAc)2 and predicted redox potentials.86 This inves-
tigation determined that changes of p-Z from H to NO2
increased the compound’s oxidation potential by 0.05 V.
Using their methodology, we have extended their calculations
SUMMARY AND FURTHER ANALYSIS
■
As mentioned above, (diacetoxyiodo)arenes predominantly
exhibit “bow tie” structures having two intramolecular short
I···O contacts in the solid state. This structural feature has
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Figure 6. Structural representations for μ-oxo-λ3-iodane compounds.
to include Bader’s quantum theory of atoms in molecules
(QTAIM) and noncovalent interactions on p-Z-C6H4I(OAc)2
(Z = H, NO2, or OMe).87−89 These results revealed very
minor changes for Mulliken charges on iodine or the acetoxy
oxygen atoms across the series, consistent with the NMR
studies discussed above. The determined bond critical points
and NCI plot for PhI(OAc)2 are shown in Figure 7.
the I−C bond (0.14). Notably, no bond critical points are
found to indicate significant covalent bonding between iodine
and remote oxygen atoms, in line with a previous study.90
The NCI plot, however, suggests the presence of weak
attractive interactions of a magnitude similar to that of van
der Waals interactions. Analyses of the p-NO2 and p-OMe
analogues are very similar (see the Supporting Information).
These intramolecular I···O interactions appear to be
dominated by Coulombic attractions.
As one might anticipate, the values of ρ(r) for the two
hypervalent I−O bonds (0.099) are much smaller than for
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Figure 7. Computed bond critical points and NCI plots of PhI(OAc)2. The surface color red indicates repulsions, green van der Waals
attractions and/or weak interactions, and blue stronger attractive interactions.
In a preliminary computational attempt to examine
polymer 5b, we carried out similar analyses for a subsection
(a dimer based on X-ray coordinates) of one of the two
coordination polymers within the crystal of 5b. Figure 8
reveals several noteworthy points (full pictures available in
the Supporting Information). First, the p-NO2 oxygen atoms
that are positioned approximately trans to the C−I bond and
at a distance ≤3.32 Å now yield bond critical points,
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Figure 8. Computed bond critical points and NCI plots of 5b. The surface color red indicates repulsions, green van der Waals attractions and/
or weak interactions, and blue stronger attractive interactions.
suggesting the donation of electron density into σ* orbitals in
addition to the electrostatic attractions. Second, the p-NO2-
C6H4 rings that lie above one another have attractive van der
Waals surfaces between them, which might also be a
stabilizing force to drive this type of coordination polymer
formation.
CONCLUSION
■
Carboxylate derivatives of λ3-iodanes comprise a huge and
important class of HVI compounds. A systematic effort to
introduce remote para substituents to promote intermolecular
I···O interactions and formation of extended structures was
found to be challenging as intramolecular and intermolecular
I···O interactions between the oxygen atoms of the carboxyl
groups dominated the solid-state structures. By employing
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
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Accession Codes
CCDC 2056489 and 2056498−2056506 contain the
supplementary crystallographic data for this paper. These
data can be obtained free of charge via www.ccdc.cam.ac.uk/
data_request/cif, or by emailing data_request@ccdc.cam.ac.
uk, or by contacting The Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
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AUTHOR INFORMATION
Corresponding Author
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2014, 275, 54−62.
John D. Protasiewicz − Department of Chemistry, Case
Western Reserve University, Cleveland, Ohio 44106, United
States; orcid.org/0000-0002-3332-6985;
Email: protasiewicz@case.edu
Authors
Guobi Li − Department of Chemistry, Case Western Reserve
University, Cleveland, Ohio 44106, United States;
orcid.org/0000-0001-9439-7069
Arnold L. Rheingold − Department of Chemistry and
Biochemistry, University of California, San Diego, La Jolla,
California 92903, United States; orcid.org/0000-0003-
4472-8127
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Terraneo, G. Halogen Bonding in Hypervalent Iodine Compounds.
Top. Curr. Chem. 2016, 373, 289−309.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.1c00339
Notes
The authors declare no competing financial interest.
(20) Bishop, R. Organic crystal engineering beyond the Pauling
hydrogen bond. CrystEngComm 2015, 17, 7448−7460.
ACKNOWLEDGMENTS
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The authors appreciate the helpful advice of Dr. Kazunori
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The authors also thank Zakary Ekstrom from Case Western
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