Underlining the non-covalent interactions and spectral properties of a new trimeric perfluoro-ortho-phenylenemercury supramolecular complex: Synthesis, structure and spectroscopy of [(o-C6F4Hg) 3·μ3-TCNB]

Article abstract of DOI:10.1007/s10870-014-0491-9

With its close proximity of Hg(II) atoms, elevated electron-withdrawing properties and accessibility to electrophilic sites on its molecular surface, cyclic trimeric perfluoro-ortho-phenylenemercury (o-(C₆F ₄Hg)₃) has been identified as one of the simplest Lewis acids. Given the marrying of these effects within the molecule, it has consistently demonstrated facility in forming supramolecular complexes with both neutral and anionic substrates. In an effort to expand the library of neutral substrates complexed by (o-C₆F₄Hg)₃, in this communication we highlight the structural and spectroscopic properties of the complex between (o-C₆F₄Hg)₃ and the organic acceptor TCNB (TCNB = 1,2,4,5-tetracyanobenzene). The supramolecular complex crystallized in the centrosymmetric triclinic space group Pbar{1} P 1 and exhibited unit cell dimensions of a = 10.9026(8) A, b = 11.1731(8) A, c = 14.0657(10) A, α = 89.839(6), β = 77.893(7) and γ = 69.328(8) for the title complex. Close inspection of the solid state structure revealed one-dimensional chains of non-covalent Hg...N interactions between the mercury atoms of (o-C₆F₄Hg) ₃ and the nitrogen atoms from nitrile groups lying trans to one another within the organic acceptor. A network of hydrogen bonding interactions between (o-C₆F₄Hg)₃ and TCNB as well as among dimers of TCNB was also observed. Infrared spectroscopic measurements were also completed and revealed a shifting of the nitrile vibrational frequency for TCNB relative to that for the free molecule. Graphical Abstract: Herein we present the structure and infrared spectroscopic properties of the supramolecular complex [(o-C₆F₄)₃·μ₃- TCNB], which couples the Lewis Acid trimeric perfluoro-ortho-phenylenemercury ((o-C₆F₄Hg)₃) with the organocyanide acceptor TCNB (TCNB = 1,2,4,5-tetracyanobenzene).[Figure not available: see fulltext.].

Full text of DOI:10.1007/s10870-014-0491-9

J Chem Crystallogr (2014) 44:123–130
DOI 10.1007/s10870-014-0491-9
ORIGINAL PAPER
Underlining the Non-Covalent Interactions and Spectral
Properties of a New Trimeric Perfluoro-Ortho-Phenylenemercury
Supramolecular Complex: Synthesis, Structure and Spectroscopy
of [(o-C6F4Hg)3ꢀl3-TCNB]
•
Steven P. Fisher Eric W. Reinheimer
Received: 25 August 2013 / Accepted: 8 January 2014 / Published online: 2 February 2014
Ó Springer Science+Business Media New York 2014
Abstract With its close proximity of Hg(II) atoms, ele-
vated electron-withdrawing properties and accessibility to
electrophilic sites on its molecular surface, cyclic trimeric
perfluoro-ortho-phenylenemercury (o-(C6F4Hg)3) has been
identified as one of the simplest Lewis acids. Given the
marrying of these effects within the molecule, it has con-
sistently demonstrated facility in forming supramolecular
complexes with both neutral and anionic substrates. In an
effort to expand the library of neutral substrates complexed
by (o-C6F4Hg)3, in this communication we highlight the
structural and spectroscopic properties of the complex
between (o-C6F4Hg)3 and the organic acceptor TCNB
(TCNB = 1,2,4,5-tetracyanobenzene). The supramolecular
complex crystallized in the centrosymmetric triclinic space
Keywords Supramolecular ꢀ TCNB ꢀ Trimeric perfluoro-
ortho-phenylenemercury
Introduction
Research into the applicability of multidentate Lewis acids
capable of complexing both neutral and anionic substrates has
persisted as an attractive field of research in supramolecular
chemistry for several decades [1–3]. Among the classes of
Lewis acids studied, polyfunctional organomercurials, con-
taining mercury atoms bridged by an organic framework have
beenidentified as promisingcandidatescapableofcomplexinga
wide range of neutral and anionic Lewis bases. As a result of
their inherent resistance to both water and oxygen, as well as the
highly unsaturated nature of their Hg(II) atoms which engender
high levels of Lewis acidity, several different classes of poly-
functional organomercurials have been identified capable
of functioning as acceptors for a multitude of substrates [4–9].
Among the fluorinated class of such acceptors, the triden-
tate derivative trimeric perfluoro-ortho-phenylenemercury
((o-C6F4Hg)3, Fig. 1a) remains the most often studied organo-
mercurial derivative due to its planarity, the proximity and
electrophilic nature of its constituent Hg(II) atoms and the
heightened electron-withdrawing properties authored by the
twelve fluorine atoms on the triphenylene core [10, 11]. To date,
(o-C6F4Hg)3 hasserved asareceptor molecule for metallocenes,
anions, nitriles, sulfoxides, aromatic subtrates, formamides,
sulfur-containing acetylcholinesterase inhibitors, carbonyls,
ethers and nitronyl nitroxides [10, 12–29]. In addition to those
substrates outlined above, the organocyanide acceptor TCNQ
(TCNQ = 7,7,8,8-tetracyanoquinodimethane), a component of
the first organic charge transfer complex to display metallic
conductivity, has also successfully formed a supramolecular
complexes with (o-C6F4Hg)3 [18, 30].
ꢀ
group P1 and exhibited unit cell dimensions of a =
˚
˚
˚
10.9026(8) A, b = 11.1731(8) A, c = 14.0657(10) A,
a = 89.839(6)°, b = 77.893(7)° and c = 69.328(8)° for
the title complex. Close inspection of the solid state
structure revealed one-dimensional chains of non-covalent
HgꢀꢀꢀN interactions between the mercury atoms of
(o-C6F4Hg)3 and the nitrogen atoms from nitrile groups
lying trans to one another within the organic acceptor.
A network of hydrogen bonding interactions between
(o-C6F4Hg)3 and TCNB as well as among dimers of TCNB
was also observed. Infrared spectroscopic measurements
were also completed and revealed a shifting of the nitrile
vibrational frequency for TCNB relative to that for the free
molecule.
S. P. Fisher ꢀ E. W. Reinheimer (&)
Department of Chemistry and Biochemistry and the W.M. Keck
Foundation Center for Molecular Structure, California State
University San Marcos, 333 S. Twin Oaks Valley Rd,
San Marcos, CA 92096, USA
e-mail: ereinhei@csusm.edu
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J Chem Crystallogr (2014) 44:123–130
The organocyanide acceptor TCNB (Fig. 1b), whose solid
state structure was first reported in 1973, forms charge transfer
complexes with various organic donors and aromatic solvents
[31–45]. Among the former category of co-crystallites, com-
plexes coupling TCNB with the donors anthracene, naphtha-
lene and phenanthrene displayed novel phase transitions and
evidence of orientational disorder in the donor sublattice [39,
46–49]. Co-crystals have also been prepared with trans-2-
stilbene, benzanthracene, p-phenylenediamine, pyrene, N,N-
dimethyl-p-phenylenediamine, bis(2-methylbenzyl-cyanide),
9-methylanthracene and chiral 1,10-bis-2-naphthol derivatives
[40, 45, 50–54].MaterialscouplingTCNBwithTTFandsome
of its derivatives have also been reported. These include TTF-
TCNB reported by Bandoli et al. as well as those complexes
with TMTTF (TMTTF = 2,3,6,7-tetramethyl-1,4,5,8-tetra-
thiafulvalene), BMDT-TTF (BMDT-TTF = bis(methylene-
dithio)tetrathiafulvalene or MT) and both the 1:1 triclinic and
2:1 monoclinic phases with o-Me2TTF reported by Reinhei-
mer et al. [55–59].
(a)
Given the facility by which (o-C6F4Hg)3 formed an
adduct with TCNQ, we were curious to observe if TCNB
could also successfully function as a substrate in a
(b)
Fig. 1 (o-C6F4Hg)3 (a) and TCNB (b)
Fig. 2 Asymmetric unit of
[(o-C6F4Hg)3ꢀl3-TCNB]
highlighting the HgꢀꢀꢀN
interactions between the
constituent molecules with
anistropic displacement
ellipsoids set to 30 %
probability. Hydrogen
atoms have been omitted
for the sake of clarity
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J Chem Crystallogr (2014) 44:123–130
125
˚
Table 1 X-ray crystallographic and refinement data for [(o-C6F4Hg)3ꢀ
l3-TCNB]
Table 2 Bond distances for [(o-C6F4Hg)3ꢀl3-TCNB] in A
Hg(1)–C(1)
Hg(1)–C(18)
Hg(2)–C(12)
Hg(2)–C(13)
Hg(3)–C(6)
Hg(3–C(7)
F(1)–C(2)
2.081 (10)
C(3)–C(4)
1.338 (14)
1.369 (14)
1.369 (13)
1.347 (12)
1.388 (13)
1.397 (14)
1.349 (15)
1.366 (13)
1.404 (13)
1.355 (13)
1.438 (13)
1.385 (13)
1.350 (15)
1.415 (14)
1.364 (12)
1.378 (11)
1.391 (11)
1.408 (11)
1.454 (11)
1.369 (11)
1.428 (11)
1.421 (11)
1.365 (11)
1.425 (11)
1.431 (11)
Complex
[(o-C6F4Hg)3ꢀl3-TCNB]
28H2F12Hg3N4
2.087 (9)
C(4)–C(5)
Formula
C
2.062 (8)
C(5)–C(6)
Formula weight (g/mol)
CCDC code
1224.11
941166
0.71073
170(2)
2.059 (9)
C(7)–C(8)
2.075 (10)
2.075 (9)
C(7)–C(12)
C(8)–C(9)
˚
Wavelength (A)
Temperature (K)
Crystal system
Space group
1.361 (11)
1.388 (13)
1.362 (11)
1.386 (10)
1.363 (11)
1.340 (9)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(13)–C(14)
C(13)–C(18)
C(14)–C(15)
C(15)–C(16)
C(16)–C(17)
C(17)–C(18)
C(19)–C(20)
C(19)–C(24)
C(20)–C(21)
C(20)–C(25)
C(21)–C(22)
C(21)–C(26)
C(22)–C(23)
C(23)–C(24)
C(23)–C(27)
C(24)–C(28)
Triclinic
F(2)–C(3)
ꢀ
P1
F(3)–C(4)
˚
a (A)
10.9026 (8)
11.1731 (8)
14.0657 (10)
89.839 (6)
77.893 (7)
69.328 (8)
1562.69 (19)
2
F(4)–C(5)
˚
b (A)
F(5)–C(8)
˚
c (A)
F(6)–C(9)
a (°)
b (°)
c (°)
F(7)–C(10)
F(8)–C(11)
F(9)–C(14)
F(10)–C(15)
F(11)–C(16)
F(12)–C(17)
N(1)–C(25)
N(2)–C(26)
N(4)–C(28)
N(3)–C(27)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
1.352 (12)
1.370 (11)
1.348 (12)
1.353 (11)
1.353 (10)
1.353 (12)
1.129 (10)
1.177 (10)
1.158 (10)
1.126 (11)
1.334 (13)
1.432 (12)
1.353 (15)
3
˚
Volume (A)
Z
qcalc (g/cm3)
l (mm1)
2.602
14.797
F (000)
1092
Crystal size (mm3)
h range for data collection (°)
Refl/Uniq
0.45 9 0.34 9 0.18
3.21–27.48
15501/7130
0.0671
R (int)
Absorption correction
REQAB
T
min/Tmax
0.0575/0.1759
Full matrix least squares on F2
7130/0/424
Refinement method
Data/restr/par
Experimental Section
a
b
Final R indices [I [ 2r]
R indices (all data)
Goodness-of-fit (F2)c
R1 = 0.0471, wR2 = 0.1018
Complex Preparation
a
b
R1 = 0.0663, wR2 = 0.1081
1.001
Given the extreme toxicity of organomercurials, all syn-
thetic procedures were completed in a well ventilated hood
and extreme care was exercised in order to avoid exposure
to solids and solutions known to contain mercury. The
Lewis Acid (o-C6F4Hg)3 was prepared according to liter-
-3
˚
Peak/hole (e/A
)
1.74 and -2.35
P
P
a
R1 = ||Fo|-|Fc||/ |Fo|
P
P
wR2 = [ [w(Fo2-Fc ) ]/ [w(Fo2)2]1/2
2 2
b
c
P
Goodness-of-fit = [ w(|Fo|-|Fc|)2/(Nobs-Nparameter)]1/2
¨
ature methods by the group of Professor Francois Gabbaı
and used as received without further purification [60]. The
acceptor TCNB was purchased from Sigma-Aldrich and
used without additional purification. The solvent CH2Cl2,
utilized in the preparation of the supramolecular complex,
was not dried prior to its use.
supramolecular complex with (o-C6F4Hg)3. The solid state
structure of the resulting material revealed alternating
stacks of (o-C6F4Hg)3 and TCNB molecules within which
close HgꢀꢀꢀN interactions between those molecules were
observed. Hydrogen bonding among isolated dimers of
TCNB acceptors and between (o-C6F4Hg)3 and TCNB was
also detected. Close analysis of the resulting infrared (IR)
spectroscopic data showed a shift in the nitrile vibrational
frequency relative to that of free TCNB, symptomatic of
non-covalent interactions among the unsaturated Hg(II)
atoms from (o-C6F4Hg)3 and the nitrogen atoms of the
TCNB substrate.
[(o-C6F4Hg)3ꢀl3-TCNB]
Colorless crystals of the title complex were grown by
slow evaporation of combined saturated CH2Cl2 solutions
containing (o-C6F4Hg)3 (0.0299 g, 2.00 9 10-5 mol) and
TCNB (0.0068 g, 3.86 9 10-5 mol) over a period of
2 weeks. The crystals were rinsed with a solution of cold
hexanes and allowed to dry in air; yield 0.0216 g (62 %).
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J Chem Crystallogr (2014) 44:123–130
X-ray Crystallography
X-ray diffraction data for a colorless plate-like crystal of
the title complex with dimensions 0.45 9 0.34 9 0.18
mm3 was collected using graphite-monochromated Mo Ka1
˚
radiation (= 0.71073 A) on a Rigaku SCXMini X-ray dif-
fractometer equipped with a Rigaku Mercury 70 CCD
camera at 170(2) K. Data collection, initial indexing, frame
integration, Lorentz-polarization corrections and final cell
parameter calculations were carried out using CrystalClear
[61]. Multi-scan absorption corrections were performed
using REQAB and the structure solved using direct meth-
ods via SHELXS-97 [62, 63]. The hydrogen atoms on the
aromatic ring of TCNB were located in the difference map,
then fixed and refined using the HFIX 43 command. The
space group was unambiguously verified using PLATON
[64]. Fourier recycling of the reflection data for
[(o-C6F4Hg)3ꢀl3-TCNB] resulted in the identification of
electron density peaks present in solvent accessible voids
3
˚
of 248 A that could not be satisfactorily modeled. The
data was treated using the SQUEEZE routine in PLA-
TON and then refined on F2 to acceptable levels [65].
The solid state structure for the complex with anisotropic
displacement ellipsoids at 30 % probability is depicted
in Fig. 2. Additional information regarding refinement
details as well as the bond distances for the complex are
listed in Tables 1 and 2. CCDC file 941166 contains the
supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Results and Discussion
X-ray Crystallographic Analysis
As stated previously, the solid state structure of
[(o-C6F4Hg)3ꢀl3-TCNB] crystallizes in the centrosymmet-
Fig. 3 One-dimensional supramolecular array of HgꢀꢀꢀN interactions
within the solid state structure of [(o-C6F4Hg)3ꢀl3-TCNB] which
persists in stacks nearly parallel to the crystallographic b-axis.
Anisotropic displacement ellipsoids have been set to 30 % probability
and both the hydrogen and fluorine atoms have been removed for the
sake of clarity
ꢀ
ric triclinic space group P1 with one molecule each of both
(o-C6F4Hg)3 and TCNB as the contents of its asymmetric
unit (Fig. 2). Similar to the complex of (o-C6F4Hg)3 with
TCNQ, the structure of the present complex is dominated
by non-covalent HgꢀꢀꢀN interactions between the divalent
mercury atoms of the Lewis acid and the nitrogen atoms
from two of the four cyanide groups on TCNB [18]. Pre-
liminary examination of the structure revealed a single set
of three non-covalent HgꢀꢀꢀN interactions with distances
below the sum of their corresponding van der Waals radii
the three mercury atoms of (o-C6F4Hg)3 at distances of
3.008(9) (Hg1ꢀꢀꢀN4), 3.111(8) (Hg2ꢀꢀꢀN4) and 3.341(8)
˚
(Hg3ꢀꢀꢀN4) A respectively (Fig. 2) [18, 66, 67].
Upon three-dimensional expansion of the asymmetric
unit, a second set of HgꢀꢀꢀN interactions with distances less
than the sum of their van der Waals radii was also observed
between Hg1ꢀꢀꢀN2, Hg2ꢀꢀꢀN2 and Hg3ꢀꢀꢀN2 at distances of
˚
(rvdw = 1.73–2.00 A for mercury; rvdw = 1.60 A for
˚
nitrogen) between the nitrogen atom N4 from TCNB and
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J Chem Crystallogr (2014) 44:123–130
127
Fig. 4 Array of Csp2-HꢀꢀꢀN and Csp2-HꢀꢀꢀF hydrogen bonding inter-
actions among dimers of TCNB acceptors and between TCNB and
(o-C6F4Hg)3 within the crystallographically derived structure of
[(o-C6F4Hg)3ꢀl3-TCNB]. Anisotropic displacement ellipsoids have
been set to 30 % probability
˚
3.021(8), 3.181(9) and 3.122(9) A respectively (Fig. 3).
analysis of the six angles (Hg1-centroid-N2, Hg2-centroid-
N2, Hg3-centroid-N2, Hg1-centroid-N4, Hg2-centroid-N4
and Hg3-centroid-N4) defined by the mercury atom, the
centroid of the mercury atom plane and the terminal
nitrogen atom of the coordinated nitrile. When compared to
the Hg-centroid-N angles in the [(o-C6F4Hg)3ꢀ(l3-CH3
CN)2] complex with its values of 90.7, 89.1 and 90.2°,
those in [(o-C6F4Hg)3ꢀl3-TCNB] with values of 84.7, 91.2,
90.5, 83.1, 89.7 and 100.4° demonstrate that the greater
steric bulk of TCNB in the latter complex is likely
responsible for its greater angular deviations from the 90.0°
expected of perpendicular orientations.
This latter set of HgꢀꢀꢀN interactions, in a manner akin to
the TCNQ complex, involved both the nitrile group trans to
that nitrile involved in the Hg1ꢀꢀꢀN4, Hg2ꢀꢀꢀN4 and
Hg3ꢀꢀꢀN4 and distances qualitatively similar to those in the
TCNQ complex [18]. The result is a one-dimensional
stacked arrangement of the constituent molecules, alter-
nating with respect to one another, along an axis offset
from the a-axis of the unit cell by an angle of *40°
(Fig. 3). Of further note, those nitriles involved in the
l3-coordination with the mercury atoms (N4-C28 and N2-
˚
C26) showed bond distances of 1.158(10) and 1.177(10) A
respectively, while those not coordinated (N1-C25 and N3-
˚
C27) possessed distances of 1.129(10) and 1.126(11) A.
In addition to those non-covalent HgꢀꢀꢀN interactions
between (o-C6F4Hg)3 and TCNB highlighted in the previous
section, Csp2-HꢀꢀꢀN and Csp2-HꢀꢀꢀF hydrogen bonding inter-
actions were also observed among neighboring TCNB
molecules as well as between TCNB and (o-C6F4Hg)3. As
one translates along the a-axis within the [111] plane, rib-
bons of hydrogen bonding interactions with the repeating
arrangement (o-C6F4Hg)3ꢀꢀꢀTCNBꢀꢀꢀTCNBꢀꢀꢀ(o-C6F4Hg)3
were observed due to two Csp2-HꢀꢀꢀF interactions of
The nitrile bond distances for those from TCNB involved
in non-covalent interactions with the mercury atoms appear
longer than the mean nitrile distance in free TCNB
˚
(1.141(2) A) [31]. Meanwhile, those bond distances for
their non-interactive analogues revealed distances consid-
erably shorter than that mean distance [31]. Despite this
disparity, the mean nitrile bond distance for TCNB within
[(o-C6F4Hg)3ꢀl3-TCNB] is only slightly greater than that
˚
2.51(10) A among F2 and H1 between (o-C6F4Hg)3 and
2
˚
˚
for its free form (1.147(10) vs. 1.141(2) A) [31].
TCNB and two Csp -HꢀꢀꢀN interactions at 2.71(9) A between
The motif whereby HgꢀꢀꢀN interactions were observed
both directly above and below the plane defined by the
three mercury atoms was described previously in the
complex [(o-C6F4Hg)3ꢀ(l3-CH3CN)2] [17]. In a fashion
very similar to that complex, the nitrile groups in
H2 and N3 of neighboring TCNB acceptors (Fig. 4) [68].
Most interesting within this hydrogen bonding array is the
association of TCNB molecules into dimers via Csp2-HꢀꢀꢀN
hydrogen bonding, a motif present in not only the structures
of the free acceptor, but also those of its many complexes
[31–59]. While possessing this often observed pattern, and
especially given the shorter interatomic contacts between the
hydrogen and nitrogen atoms of the neighboring TCNB
substrates in [(o-C6F4Hg)3ꢀl3-TCNB], the complex’s
hydrogen bonds among neighboring substrates at distances
˚
[(o-C6F4Hg)3ꢀl3-TCNB] lie 2.339(3) and 2.357(3) A from
the mercury atom plane while the analogous distance in
˚
[(o-C6F4Hg)3ꢀ(l3-CH3CN)2] was 2.32 A [17]. The nearly
perpendicular nature of both nitriles relative to that mer-
cury atom plane can be further analyzed upon closer
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J Chem Crystallogr (2014) 44:123–130
Fig. 5 IR spectra for TCNB (a) and [(o-C6F4Hg)3ꢀl3-TCNB] (b)
˚
of 2.71(9) A appear qualitatively stronger than those in the
˚
structure of free TCNB at 2.87(2) A [31].
be used to understand its spectroscopic behavior in both
charge transfer and supramolecular complexes. Among
those bands, the cyanide stretching frequency at 2245 cm-1
is the most significant indicator. Within [(o-C6F4Hg)3ꢀ
l3-TCNB], only one frequency corresponding to cyanide
stretching was observed at 2247 cm-1 (Fig. 5). Work by
Tikhonova et al. [17] showed a similar qualitative spectro-
scopic response, as their CH3CN complex with its HgꢀꢀꢀN
interactions, showed a shifting of the nitrile peak to a higher
frequency region relative to the free nitrile. While the shift in
IR Spectroscopy
The IR spectra for [(o-C6F4Hg)3ꢀl3-TCNB] and TCNB were
recorded at room temperature on crystalline material using a
Thermo Nicolet iS10 spectrophotometer in the range
500–4000 cm-1 (Fig. 5). Work by Bator and coworkers [69]
highlighted vibrational frequencies within TCNB that could
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J Chem Crystallogr (2014) 44:123–130
129
[(o-C6F4Hg)3ꢀl3-TCNB] was *2 cm-1, shifts of this mag-
nitude were reported previously in complexes with carbonyl
substrates encompassing non-covalent HgꢀꢀꢀO interactions
[25]. Given the presence of interatomic distances between
mercury and nitrogen atoms less than the sum of their van der
Waals radii within the structure of [(o-C6F4Hg)3ꢀl3-TCNB],
as well as an orientation of its nitrile groups analogous to
those observed in the complexes with CH3CN and TCNQ, a
claim can be made that the nitrile frequency shift is the result
of non-covalent, supramolecular interactions between
(o-C6F4Hg)3 and the TCNB substrate [17, 18].
5. Hawthorne MF, Zheng Z (1997) Acc Chem Res 30:267
6. Hawthorne MF, Yang X, Zheng Z (1994) Pure Appl Chem
66:245
7. Shubina ES, Tikhonova IA, Bakhmutova EV, Dolgushin FM,
Antipin MY, Bakhmutov VI, Sivaev IB, Teplitskaya LN, Chiz-
hevsky IT, Pisareva IV, Bregadze VI, Epstein LM, Shur VB
(2001) Chem Eur J 7:3783
8. Chistyakov AL, Stankevich IV, Gambaryan NP, Struchkov YT,
Yanovsky AI, Tikhonova IA, Shur VB (1997) J Organomet Chem
536:413
9. Shur VB, Tikhonova IA, Dolgushin FM, Yanovsky AI, Struchkov
YT, Volkonsky AY, Solodova EV, Panov SY, Petrovskii PV,
Vol’pin ME (1993) J Organomet Chem 443:C19
10. Tikhonova IA, Dolgushin FM, Tugashov KI, Petrovskii PV, Furin
GG, Shur VB (2002) J Organomet Chem 654:123
11. Viets D, Lork E, Watson PG, Mews R (1997) Angew Chem Int
Ed Engl 36:623
Conclusion
¨
12. Haneline MR, Gabbaı FP (2004) Angew Chem Int Ed 43:5471
13. Shur VB, Tikhonova IA, Yanovskii AI, Struchkov YT, Petrovskii
PV, Panov SY, Furin GG, Vol’pin ME (1991) J Organomet Chem
418:C29
14. Shur VB, Tikhonova IA, Yanovskii AI, Struchkov YT, Petrovskii
PV, Panov SY, Furin GG, Vol’pin ME (1991) Dokl Akad Nauk
SSSR 321:1002
15. Tikhonova IA, Dolgushin FM, Yanovsky AI, Struchkov YT,
Gavrilova AN, Saitkulova LN, Shubina ES, Epstein LM, Furin
GG, Shur VB (1996) J Organomet Chem 508:271
Herein, we presented the structure and spectroscopic prop-
erties of the supramolecular complex coupling (o-C6F4Hg)3
with the organocyanide acceptor TCNB. While the com-
plex’s asymmetric unit illustrates three non-covalent HgꢀꢀꢀN
interactions between the constituent molecules, the appli-
cation of crystallographic symmetry and expansion of the
structure revealed that two of the four nitriles from TCNB
were engaged in a total of six such interactions and that the
constituent molecules stacked in an alternating motif along
an axis offset from the crystallographic a-axis by an angle of
*40°. In addition to the six HgꢀꢀꢀN interactions was an array
of Csp2-HꢀꢀꢀN and Csp2-HꢀꢀꢀF hydrogen bonding interactions
among isolated dimers of TCNB acceptors and between
(o-C6F4Hg)3 and TCNB within the [111] plane. These
interactions arrays, equivalent via symmetry, were also
found to be parallel to one another via translations along the
a-axis. Spectroscopic properties for [(o-C6F4Hg)3ꢀl3-TCNB]
were also measured and compared to those for free TCNB.
These spectra revealed a shifting of thenitrilepeak forTCNB
within the complex relative to its free form, qualitative
behavior analogous to the CH3CN complex. Work in the
preparation of additional supramolecular complexes pairing
(o-C6F4Hg)3 with organocyanide acceptors and those results
will be reported in future communications.
¨
16. Koomen JM, Lucas JE, Haneline MR, Beckwith King JD, Gabbaı
FP, Russell DH (2003) Int J Mass Spectrom 225:225
17. Tikhonova IA, Dolgushin FM, Yanovsky AI, Starikova ZA,
Petrovskii PV, Furin GG, Shur VB (2000) J Organomet Chem
613:60
¨
18. Haneline MR, Gabbaı FP (2004) C R Chim 7:871
19. Tikhonova IA, Dolgushin FM, Tugashov KI, Ellert OG, Novo-
tortsev VM, Furin GG, Antipin MY, Shur VB (2004) J Organo-
met Chem 689:82
¨
20. Tsunoda M, Gabbaı FP (2000) J Am Chem Soc 122:8335
21. Haneline MR, Tsunoda M, Gabbaı FP (2002) J Am Chem Soc
¨
124:3737
22. Omary MA, Kassab RM, Haneline MR, Bjeirami OE, Gabbaı FP
¨
(2003) Inorg Chem 42:2176
23. Baldamus J, Deacon GB, Hey-Hawkins E, Junk PC, Martin C
(2002) Aust J Chem 55:195
¨
24. Tsunoda M, Gabbaı FP (2005) Heteroatom Chem 16:292
25. King JB, Tsunoda M, Gabbaı FP (2002) Organometallics 21:4201
¨
¨
26. King JB, Haneline MR, Tsunoda M, Gabbaı FP (2002) J Am
Chem Soc 124:9350
27. Wuest JD, Zacharie B (1987) J Am Chem Soc 109:4714
¨
28. Gardinier JR Gabbaı FP J Chem Soc, Dalton Trans (2000) 2861
29. Haneline MR, Gabbaı FP (2005) Inorg Chem 44:6248
¨
Acknowledgments The authors wish to acknowledge California
State University San Marcos for the funds necessary to purchase the
Rigaku SCXMini X-ray diffractometer. The authors also wish to
¨
acknowledge Professor Francois Gabbaı of Texas A&M University
for his generous gift of (o-C6F4Hg)3 used in preparation of the
30. Ferraris J, Cowan DO, Walatka VJ, Perlstin JH (1973) J Am
Chem Soc 95:948
31. Prout CK, Tickle IJ (1973) J Chem Soc Perkin Trans II 520
32. Lefebvre J, Ecolivet C, Bourges P, Mierzejewski A, Luty T
(1991) Phase Trans 32:223
supramolecular complex reported in this communication.
33. Hosaka N, Obata M, Suzuki M, Saiki T, Takeda K, Kuwata-
Gonokami M (2008) Appl Phys Lett 92:110
34. Arnold BR, Schill AW, Poliakov PV (2001) J Phys Chem A
105:537
References
35. Ito Y, Nakabayashi H, Ohb S, Hosomi H (2000) Tetrahedron
56:7139
1. Schmidtchen FP, Berger M (1997) Chem Rev 97:1609
2. Piers WE, Irvine GJ, Williams VC (2000) Eur J Inorg Chem 2131
¨
3. Hoefelmeyer JD, Schulte M, Tschinkl M, Gabbaı FP (2002)
Coord Chem Rev 235:93
36. Dahl T (2000) Acta Crystallogr C56:708
37. Deperasinska I, Prochorow J, Dresner J (1998) J Lumin 79:65
38. Ito Y, Endo S, Ohba S (1997) J Am Chem Soc 119:5974
39. Lefebvre J, Rohleder K, Mierzejewski A, Luty T (1995) J Chem
Phys 102:2165
¨
4. Gabbaı FP, Taylor R, Maneline MR (2003) Chem Eur J 9:5188
123

130
J Chem Crystallogr (2014) 44:123–130
40. Ferguson G, Foster R, Iball J, Scrimgeour SN, Williams BC
(1990) Acta Crystallogr C46:2396
41. Lefebvre J, Miniwicz A, Kowal R (1989) Acta Crystallogr
C45:1372
42. Miniewicz A, Samoc M, Williams DF (1984) Mol Cryst Liq
Cryst 111:199
43. Wright JD, Ohta T, Kuroda H (1976) Bull Chem Soc Jpn 49:2961
44. Ohashi M, Nakayama N (1976) Chem Lett 1:1143
45. Tsuchiya H, Marumo F, Saito Y (1973) Acta Crystallogr B29:659
46. Bos FC, Schmidt J (1984) Chem Phys Lett 105:565
54. Imai Y, Kamon K, Kido S, Harada T, Tajima N, Sato T, Kuroda
R, Matsubara Y (2009) Cryst Eng Comm 11:620
55. Bandoli G, Lunardi Clemente DA (1993) J Crystallogr Spec Res 23:1
56. Reinheimer EW, Rivas MFB, Zhao H, Dunbar KR (2011) J Chem
Crystallogr 41:936
57. Fisher SP, Reinheimer EW (2013) J Chem Crystallogr 43:343
58. Reinheimer EW, Zhao H, Dunbar KR (2010) J Chem Crystallogr
40:514
59. Fisher SP, Reinheimer EW J Chem Crystallogr Submitted
60. Sartori P, Golloch A (1968) Chem Ber 101:2004
61. Pflugrath JW (1999) Acta Crystallogr D55:1718
62. Rigaku (1998) REQAB. Rigaku Corporation, Tokyo
63. Sheldrick GW (2008) Acta Crystallogr A64:112
64. Spek AL (2001) PLATON, a multipurpose crystallographic tool.
Utrecht University, Utrecht
¨
47. Erdle E, Mohwald M (1979) Chem Phys 36:283
48. Wright JD, Yakushi K, Kuroda H (1978) Acta Crystallogr
B34:1934
49. Lefebvre J, Odou G, Muller M, Mierzejewski A, Tadeusz L
(1989) Acta Crystallogr B45:323
50. Agostini G, Corvaja C, Giacometti G, Pasimeni L (1984) Chem
Phys 85:421
51. Prout CK, Morley T, Tickle IJ Wright JD (1973) J Chem Soc
Perkin Trans II 523
52. Ohashi Y (1973) Acta Crystallogr B29:2863
53. Hosomi H, Ohba S, Ito Y, Nakabayashi H (1997) Acta Crystal-
logr C46:IUC9700031
65. Sluis P, Spek AL (1990) Acta Crystallogr A46:194
66. Canty AJ, Deacon GB (1980) Inorg Chim Acta 45:L225
67. Pyykko P, Straka M (2000) Phys Chem Chem Phys 2:2489
´
68. Fourmigue M, Batail P (2004) Chem Rev 104:5379
69. Sawka-Dobrowolska W, Bator G, Czarnik-Matusewicz B, Sob-
´
czyk L, Pawlukojc A, Grech E, Nowicka-Scheibe J, Rundlof H
(2006) Chem Phys 327:237
¨
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