Water and hydrogen halides serve the same structural role in a series of 2+2 hydrogen-bonded dimers based on 2,6-bis(2-anilinoethynyl)pyridine sulfonamide receptors

Article abstract of DOI:10.1002/anie.200703971

Mix and match: A new series of receptors reveals an unusual propensity to form 2+2 hydrogen-bonded dimers with water or hydrogen halides. Remarkably, water and hydrogen chloride impart nearly identical structural features to the dimers. In fact, in one ca

Full text of DOI:10.1002/anie.200703971

Angewandte
Chemie
DOI: 10.1002/anie.200703971
Self-Assembled Dimers
Water and Hydrogen Halides Serve the Same Structural Role in a
Series of 2+2 Hydrogen-Bonded Dimers Based on
2,6-Bis(2-anilinoethynyl)pyridine Sulfonamide Receptors**
Orion B. Berryman, Charles A. Johnson II, Lev N. Zakharov, Michael M. Haley,* and
Darren W. Johnson*
The complex hydrogen-bonding interactions of the water
molecule are remarkable: water plays a vital role in a number
of systems ranging from the formation of hydrogen-bonded
water oligomers[1] to the increased conformational stability of
proteins[2] and the crucial synergistic hydrogen bonds formed
in enzymatic[3] or biomimetic[4] active sites. In many cases
these hydrogen bonds dictate both structure and function. In
supramolecular chemistry, synergistic hydrogen bonding
between water and organic molecules has helped to stabilize
vase-like conformations of hosts for organic molecules[5] and
to induce the formation of intricate hexameric nanoscale
capsules stitched together with the aid of eight water
molecules.[6] In both cases these hosts can be stabilized in
wet organic or purely aqueous solvents.[7] Anions, on the other
hand, tend not to share the structural hydrogen-bonding
diversity of water, in part as a result of the weak basicity of
anions and often because of a lack of directionality in their
hydrogen-bond formation.[8,9] Nevertheless, there is an
emerging use of anions as directing elements in self-assembly
reactions. Notable examples include a double-stranded helix
wrapped around two sulfate anions;[10] catenanes and other
structures templated by the formation of hydrogen bonds to
anions;[11] and supramolecular dimers, oligomers, and poly-
mers linked together by anions.[12] Herein we report new
receptors based on a 2,6-bis(2-anilinoethynyl)pyridine scaf-
fold that surprisingly form 2+2 dimers with either water,
halides, or both, depending on the protonation state of the
receptor. To our knowledge, this is the first example of both
halides and water molecules serving the same structural
hydrogen-bonding role in
system.[13]
Our initial venture into the use of aryl ethynyl scaffolds as
receptor molecules focused on sulfonamide-bearing 2,6-bis(2-
anilinoethynyl)pyridine derivatives 1 and 2 (Scheme 1, py =
a
synthetic self-assembled
Scheme 1.
pyridine), designed to target hydrogen-bonding guest mole-
cules (see the Supporting Information).[14] CAChe semiem-
pirical minimized molecular models suggested that selectivity
for different guest molecules could be tailored by protonating
the pyridine nitrogen atom, thus altering the cavity size, or by
exchanging the binding substituents. The aryl ethynyl core 3 is
prepared from 2-iodo-4-tert-butylaniline[15] in three steps in
60% overall yield. Conversion to sulfonamides 1 and 2 was
accomplished in excellent yield by treatment of 3 with the
corresponding sulfonyl chlorides (Scheme 1).
[*] O. B. Berryman, Dr. C. A. Johnson II, Dr. L. N. Zakharov,
Prof. Dr. M. M. Haley, Prof. Dr. D. W. Johnson
Department of Chemistry and Materials Science Institute
University of Oregon
Eugene, Oregon 97403-1253 (USA)
Fax: (+1)541-346-0487
E-mail: haley@uoregon.edu
Receptor molecules 1 and 2 have been characterized by
1H and 13C NMR, UV/Vis, fluorescence, and IR spectroscopy;
melting point; and single crystal X-ray diffraction (see the
Supporting Information). Interestingly, the 1H NMR spec-
troscopy signals of receptors 1 and 2 exhibit considerable
concentration dependence in organic solvents. Furthermore,
the sharp singlet typically observed at approximately d =
1.5 ppm for residual water in CDCl3 appears as a broad
downfield singlet (observed as far downfield as 4 ppm,
depending on concentration), hinting at the hydrogen-bond-
dwj@uoregon.edu
[**] This work was funded by the National Science Foundation (NSF)
and the University of Oregon (UO). O.B.B. acknowledges the NSF
for an Integrative Graduate Education and Research Traineeship
(DGE-0549503). C.A.J. thanks UO for a Doctoral Research Fellow-
ship. D.W.J. is a Cottrell Scholar of Research Corporation and
gratefully acknowledges the NSF for a CAREER award. We thank
Prof. Julius Rebek, Jr. for helpful discussions.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
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117

Communications
ing capability of receptors 1 and 2 in solution. This finding was
H2O, even in the presence of other potential neutral guest
molecules[20] and in solvents dried over 3-Š molecular sieves.
Receptor molecules 1 and 2 share a common design trait:
their ability to alter guest selectivity by simple changes in the
protonation state of the receptors. By protonating the
pyridine nitrogen atoms of receptors 1 and 2, the anion-
binding capacity of these receptors is activated. The halide-
binding properties of H1+ have been investigated in the solid
state. Single crystals of the chloride and bromide complexes
are prepared by dissolving receptor 1 or 2 in ethyl acetate and
bubbling HCl or HBr gas through the solution. Crystallization
is induced by layering hexanes onto the yellow ethyl acetate
solutions. Strikingly, the crystal structures of the H2+·ClÀ and
H1+·BrÀcomplexes revealed nearly isostructural dimers to
those observed for the neutral (1·H2O)2 and (2·H2O)2 water
dimers.[21,22] In the solid state, the (H2+·ClÀ)2 and (H1+·BrÀ)2
dimers (Figures 2a and 3d, respectively) are held together by
confirmed by single crystal X-ray diffraction analysis of
neutral receptors 1 and 2 (Figure 1).[16,17]
Figure 1. Crystal structures of receptors (1·H2O)2 (left) and (2·H2O)2
(right) illustrate the 2+2 dimer formed with water. The hydrogen
bonds involving water as the donor atom form a helical twist through
the center of the binding cavity. All hydrogen bonds are depicted as
dashes. For clarity, H atoms not involved in hydrogen bonds were
omitted, and only one position for the disordered H atom in the
bridging solvent water molecule is shown.
À
four sulfonamide hydrogen bonds (3.156(2)–3.229(2) Š, N
À
H···Cl angles 151(2)–171(3)8; 3.338(5)–3.440(6) Š, N H···Br
Colorless single crystals of receptors 1 and 2 suitable for
X-ray diffraction were grown by layering hexane onto ethyl
acetate solutions of each receptor. As suggested from the
1H NMR spectroscopic data, complexes (1·H2O)2 and
¯
(2·H2O)2 both crystallize as dimers in space group P1 with
two receptor molecules and two water molecules per unit cell;
consequently, each dimer has crystallographic inversion
symmetry. A prominent feature of each crystal structure is
the presence of two hydrogen-bonding water molecules
stitching the receptor dimers together. The two pyridine
nitrogen atoms accept hydrogen bonds from different water
Figure 2. a) Space-filling representation of the crystal structure of
(H2+·ClÀ)2. b) Crystal structure of the water–chloride heterodimer
(H1+·ClÀ)·(1·H2O). Both water and hydrogen chloride stabilize dimer
formation, with seven hydrogen bonds within the binding cavity of the
heterodimer. Only one position of the disordered water molecule and
chloride ion is shown for clarity. Cl green, S yellow, Nblue, O red,
C gray, H light gray.
À
molecules (2.797(4)–2.804(2) Š, O H···N angles 172(4)–
175(3)8), while one water–water hydrogen bond is present
À
(2.917(5)–3.006(7) Š, O H···O angles 164(4)–178(6)8). All of
the N-substituted sulfonamides adopt the energetically most
favored staggered conformation,[18] and each sulfonamide
proton on the receptors donates a hydrogen bond to a
different water molecule (2.855(4)–2.860(3) Š, 157(2)–
164(3)8 and 3.028(4)–3.039(3) Š, 158(2)–164(3)8) such that
the 2+2 dimer structure is held together by four sulfonamide–
water hydrogen bonds, two pyridine–water hydrogen bonds,
one water–water hydrogen bond, and two p-stacking inter-
actions between the receptors ranging from 3.42–3.44 Š
(Figure 1).
The dimerization of receptor 1 was further investigated in
CDCl3 solution. Receptor 1 was dissolved in water-saturated
À
CDCl3 to a concentration of 197 mm. The sulfonamide N H
and water H NMR spectroscopic resonances during a series
1
of dilutions resulted in data that could be fit to a 1:1
dimerization with the nonlinear regression curve fitting
software WinEQNMR[19] (see the Supporting Information).
In CDCl3, receptor 1 is shown to dimerize with a modest
Figure 3. Wireframe representations of the crystal structures of
a) (1·H2O)2, b) (H1+·ClÀ)·(1·H2O), c) (H2+·ClÀ)2, and c) (H1+·BrÀ)2
highlighting the interchangeable role that halides and water play in the
dimerization of 2,6-bis(2-anilinoethynyl)pyridine sulfonamide recep-
tors. Hydrogen bonds are illustrated as dashes (sulfonamide in red
and all others in black). Hydrogen atoms not involved in H-bonds are
omitted for clarity. Cl green, Br maroon, S yellow, Nblue, O red, C gray,
H light gray.
K
dim = 42mÀ1. Evidence supporting dimerization in CDCl3
solutions resulted from the NOE observed between the
protons on the guest water molecules and the sulfonamide
protons of the receptor (see the Supporting Information).
Receptor 1 exhibits a propensity to crystallize as a dimer with
118
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Angewandte
Chemie
À
À
angles 136(4)–168(4)8), two pyridinium N H hydrogen bonds
(3.157(3)–3.181(3) Š, N H···X angles 158(3)–167(3)8) and
additionally forms a helical hydrogen-bonding pattern run-
ning between the pyridinium nitrogen atom, chloride ion,
water molecule, and pyridine nitrogen atom (2.926(3)–3.10 Š,
to the anions (3.022(2) Š, 175(3)8 for (H2+·ClÀ)2 and
3.127(6) Š, 173(4)8 for (H1+·BrÀ)2), two Caryl H···X hydrogen
À
bonds (3.69–3.90 Š), and two p-stacking interactions between
receptors (3.49 Š for (H2+·ClÀ)2 and 3.61 Š for (H1+·BrÀ)2).
The numerous hydrogen bonds and unique dimerization bring
the negatively charged halides into close proximity, with
halide–halide distances of 3.92 Š for (H2+·ClÀ)2 and 4.08 Š
for (H1+·BrÀ)2.
À
164(3)–176(4)8). Two Caryl H···Cl hydrogen bonds (3.76–
3.93 Š) also stabilize the dimer.
In conclusion, we have investigated the host–guest
chemistry of a new class of hydrogen-bonding receptors.
Sulfonamide-substituted
2,6-bis(2-anilinoethynyl)pyridine
CAChe semiempirical calculations of the 2,6-bis(2-anili-
noethynyl)pyridine receptors suggested that larger poly-
atomic anions would not fit within the binding pocket of the
receptor. As predicted, the single crystal X-ray structure of
the HBF4 salt H1+·BF4À reveals that the binding pocket is too
small to accommodate the interaction of the large BF4À guest
with either sulfonamide proton.[14] Dilution experiments with
H1+·BF4À revealed minimal change in the 1H NMR spectrum
upon addition of CDCl3, thus indicating negligible dimeriza-
tion in solution as predicted by the receptor conformation
observed in the crystal structure.[14] However, titrations of
derivatives exhibit guest-assisted dimerization with H2O,
hydrogen halides, or both, where water and halide anions
surprisingly share the same structural role, depending on the
protonation state of the receptor. In fact, on the basis of the
heterodimer (H1+·ClÀ)·(1·H2O) (Figure 3), water and hydro-
gen chloride appear to be completely interchangeable struc-
tural partners in facilitating the dimerization. The persistence
of guest-assisted dimerization has also been observed in
solution. In particular, 1H NMR spectroscopy dilution experi-
ments have been used to observe the dimerization behavior of
the neutral sulfonamide with water and the protonated
sulfonamide with chloride. Both UV/Vis and 1H NMR
spectroscopy have been used to assess the association of
H1+ with anions in solution (ClÀ, BrÀ, and IÀ), and further
investigations are underway to quantify the strength of the
interactions in solution. We are interested in using our
modular approach to synthesize 2,6-bis(2-anilinoethynyl)pyr-
idines designed to target different guest molecules, depending
on the binding substituent attached to the receptor. The
extended conjugation inherent in 2,6-bis(2-anilinoethynyl)-
pyridine derivatives produces distinct emission properties
that will be used to monitor interactions with guest mole-
cules.[14] This observation bodes well for the use of 2,6-bis(2-
anilinoethynyl)pyridine derivatives as sensors for the selec-
tive recognition of guest molecules.
H1+·BF4 with tetra-n-butylammonium halide salts do indi-
À
cate that anion binding occurs in solution between the
receptor and halides.[23] Furthermore, the concentration
dependence observed in the 1H NMR spectrum upon dilution
of (H1+·ClÀ)2 in CDCl3 indicates the presence of a receptor–
halide dimer in solution. A supersaturated solution of
(H1+·ClÀ)2 (60 mm) was obtained by passing HCl gas through
a CDCl3 solution of neutral receptor 1. Plotting the changes in
chemical shift upon dilution and subsequent fitting of this
data to a 1:1 dimerization model with the nonlinear least
squares regression program WinEQNMR resulted in a Kdim
=
250mÀ1 in CDCl3.[24] Further evidence of dimerization was
obtained by mixing receptor 1 and a p-methoxyphenyl
sulfonamide derivative in a 1:1 ratio.[14] When equimolar
mixtures of these receptors are prepared in CDCl3 (10 mm)
and HCl gas is passed through the solution, the resulting
1H NMR spectroscopy signals are shifted from the signals Experimental Section
Full experimental details, including structural details for all com-
pounds described (in cif format), general X-ray diffraction
observed for either of the analogous homodimers prepared in
the same way at the same concentration. This result suggests
that both homodimers and a third species, the heterodimer,
are present in solution but equilibrate quickly on the NMR
timescale. From all of these experiments, it is evident that
dimerization of both the neutral and protonated forms of 2,6-
bis(2-anilinoethynyl)pyridine receptors occurs and that these
dimers persist in the solid state and in solution.
a
experimental section (including discussion of disorder modeling),
syntheses of all receptors from key intermediate 3, NOE spectrum of
(1·H2O)2, details of crystallization and dimerization experiments,
video representation of the (1·H2O)2 crystal structure, and any
associated references are available in the Supporting Information.
CCDC-657490, 657491, 957492, 657943, and 657494 contain 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.
Remarkably, a different type of heterodimer, (H1+·ClÀ)·
1·H2O), was also crystallized in the presence of concentrated
HCl with one water molecule and one chloride in the binding
pocket (Figures 2b and 3b).[25] The heterodimer contains one
protonated receptor that binds a chloride anion, while the
other receptor in the dimer is neutral and bound to a water
molecule. Water and hydrogen chloride are freely exchange-
able in this binding pocket and provide structural features
that are intermediate to those in the H2O and hydrogen halide
dimers. Analogous to the other dimers presented, the
heterodimer is stabilized by p-stacking interactions between
the two receptors (3.43 Š) and by a series of seven guest-
assisted hydrogen bonds. Each guest water molecule and
Received: August 29, 2007
Published online: November 8, 2007
Keywords: anions · dimers · hydrogen bonds · receptors ·
.
self-assembly
[1] K. Liu, J. D. Cruzan, R. J. Saykally, Science 1996, 271, 929.
[2] Y. M. Rhee, E. J. Sorin, G. Jayachandran, E. Lindahl, V. S.
Pande, Proc. Natl. Acad. Sci. USA 2004, 101, 6456.
À
chloride ion accepts two sulfonamide N H hydrogen bonds
Angew. Chem. Int. Ed. 2008, 47, 117 –120
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119

Communications
[3] a) J. Friedman, Y. T. Meharenna, A. Wilks, T. L. Poulos, J. Biol.
[19] M. J. Hynes, J. Chem. Soc. Dalton Trans. 1993, 311.
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[20] Other potential guest molecules that did not cocrystallize with
sulfonamide receptors include methanol, ethanol, isopropyl
alcohol, acetone, acetonitrile, dimethylsulfoxide, tetrahydro-
[4] C. E. MacBeth, A. P. Golombek, V. G. Young, Jr., C. Yang, K.
Kuczera, M. P. Hendrich, A. S. Borovik, Science 2000, 289, 938.
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[7] a) J. L. Atwood, L. J. Barbour, A. Jerga, Chem. Commun. 2001,
2376; b) S. M. Biros, J. Rebek, Jr., Chem. Soc. Rev. 2007, 36, 93 .
[8] J. L. Sessler, P. A. Gale, W.-S. Cho, Anion Receptor Chemistry,
Royal Society of Chemistry, Cambridge, 2006.
[9] An understanding of the coordination preferences of anions is
emerging, but the directionality is still less defined than for their
cationic counterparts. For a detailed discussion, see: S. O. Kang,
M. A. Hossain, K. Bowman-James, Coord. Chem. Rev. 2006, 250,
3038.
furan, tetra-n-butylammonium halides, and HSO4À
.
[21] Crystal data for (H1+·BrÀ)2: (C43H44BrN3O4S2)2, Mr = 1621.68,
¯
0.21 ” 0.07 ” 0.02 mm, triclinic, space group P1, a = 9.632(16),
b = 13.33(2), c = 17.47(3) Š, a = 108.39(4), b = 94.56(5), g =
106.51(4)8, V= 2005(6) Š3, Z = 1, 1calcd = 1.343 gmLÀ1
, m =
1.175 mmÀ1, 2qmax = 54.008, T= 173(2) K, R1 = 0.0598 for 5748
reflections (599 parameters) with I > 2s(I), and R1 = 0.1021,
wR2 = 0.1527, and GOF = 1.035 for all 8622 data, max/min
À3
residual electron density + 0.680/À0.371 eŠ
.
[22] Crystal data for (H2+·ClÀ)2: (C41H38ClN5O8S2)2, Mr = 1656.66,
¯
0.30 ” 0.25 ” 0.02 mm, triclinic, space group P1, a = 9.8907(13),
b = 12.9533(17), c = 17.012(2) Š, a = 107.831(2), b = 95.845(2),
g = 103.618(2)8, V= 1980.5(4) Š3, Z = 1, 1calcd = 1.389 gmLÀ1
,
m = 0.262 mmÀ1, 2qmax = 54.008, T= 173(2) K, R1 = 0.0572 for
6572 reflections (594 parameters) with I > 2s(I), and R1 =
[10] J. Sanchez-Quesada, C. Seel, P. Prados, J. de Mendoza, I. Dalcol,
E. Giralt, J. Am. Chem. Soc. 1996, 118, 277.
[11] R. Vilar, Angew. Chem. 2003, 115, 1498; Angew. Chem. Int. Ed.
2003, 42, 1460.
[12] a) P. A. Gale, K. Navakhun, S. Camiolo, M. E. Light, M. B.
Hursthouse, J. Am. Chem. Soc. 2002, 124, 11228; b) K. A.
Nielsen, W.-S. Cho, G. H. Sarova, B. M. Petersen, A. D. Bond, J.
Becher, F. Jensen, D. M. Guldi, J. L. Sessler, J. O. Jeppesen,
Angew. Chem. 2006, 118, 7002; Angew. Chem. Int. Ed. 2006, 45,
6848; c) S. J. Coles, J. G. Frey, P. A. Gale, M. B. Hursthouse,
M. E. Light, K. Navakhun, G. L. Thomas, Chem. Commun. 2003,
568.
0.0744, wR2 = 0.1594, and GOF = 1.045 for all 8472 data, max/
À3
min residual electron density + 0.564/À0.290 eŠ
.
[23] The UV/Vis spectrum of H1+·BF4À is consistent with the yellow
color of the protonated receptor in organic solutions. Upon
protonation, receptor 1 exhibits a new absorption peak with
lmax = 400 nm. The unique absorption characteristics of receptor
H1+ were used to study the host–guest interactions of this
molecule in solution. Specifically, tetra-n-butylammonium hal-
ides were titrated into CH2Cl2 solutions of H1+·BF4 while
À
maintaining constant receptor concentrations. Evident changes
in the UV/Vis spectra were observed upon addition of halide
anions. In all cases, the absorption bands at 240, 290, and 330 nm
were shown to increase in intensity throughout the titration,
while the intensity of the absorption band at 400 nm decreased,
exemplifying isosbestic behavior. Unfortunately, at low concen-
trations equilibrium conditions were not observed, precluding
the determination of binding constants by UV/Vis spectropho-
tometric titrations. 1H NMR spectroscopic titrations in CDCl3
were employed to examine the anion-binding capability of
receptor H1+ for tetra-n-butylammonium halides. The binding
[13] For an example of water and halides occupying the same binding
sites in a protein, see: T. J. Fiedler, C. A. Davey, R. E. Fenna, J.
Biol. Chem. 2000, 275, 11964.
[14] a) C. A. Johnson II, Ph.D. Thesis, University of Oregon, 2007;
b) C. A. Johnson II, O. B. Berryman, M. J. Hynes, L. N.
Zakharov, D. W. Johnson, M. M. Haley, unpublished results.
[15] W. B. Wan, M. M. Haley, J. Org. Chem. 2001, 66, 3893.
[16] Crystal data for (1·H2O)2: (C43H45N3O5S2)2, Mr = 1495.88, 0.31 ”
0.18 ” 0.15 mm, triclinic, space group P1, a = 10.0377(17), b =
isotherms obtained from titrations of H1+·BF4 with halides
À
¯
12.755(2), c = 17.357(3) Š, a = 111.270(3), b = 96.113(3), g =
exhibit a steep linear increase up to one equivalent of halide,
with chloride affecting the steepest binding isotherm and iodide
the shallowest. The second portion of the equilibrium exhibits a
much smaller influence on the overall chemical shift of the
complex. The second portion of the binding isotherm has made it
difficult to determine association constants. Host–guest equili-
bria will be reported in due course.
102.966(3)8, V= 1974.4(6) Š3, Z = 1 (one dimer per unit cell),
1calcd = 1.258 gmLÀ1
,
m = 0.183mm À1
,
2qmax = 54.008, T=
173(2) K, R1 = 0.0470 for 6966 reflections (662 parameters)
with I > 2s(I), and R1 = 0.0580, wR2 = 0.1222, and GOF = 1.028
for all 8480 data, max/min residual electron density + 0.502/
À3
À0.682 eŠ
.
[17] Crystal data for (2·H2O)2: (C41H39N5O9S2)2, Mr = 1619.78, 0.30 ”
[24] Subsequent iterations of this experiment resulted in the for-
mation of precipitate, suggesting that the first trial was super-
saturated. The relatively low solubility of this complex in organic
solvents has hindered further determination of association
constants.
¯
0.20 ” 0.01 mm, triclinic, space group P1, a = 10.1068(15), b =
12.5999(19), c = 17.186(3) Š, a = 110.709(3), b = 97.006(3), g =
100.306(3)8, V= 1972.9(5) Š3, Z = 1, 1calcd = 1.363 gmLÀ1, m =
0.198 mmÀ1, 2qmax = 54.008, T= 173(2) K, R1 = 0.0642 for 4980
reflections (674 parameters) with I > 2s(I), and R1 = 0.1233,
[25] Crystal data for (H1+ClÀ)·(1·H2O): (C43H43N3O4S2)2·H2O·HCl,
¯
wR2 = 0.1462, and GOF = 1.034 for all 8413 data, max/min
Mr = 1514.32, 0.20 ” 0.08 ” 0.02 mm, triclinic, space group P1, a =
À3
residual electron density + 0.312/À0.432 eŠ
.
9.9702(13), b = 12.8868(17), c = 17.363(2) Š, a = 111.314(2), b =
[18] The “staggered” conformation for sulfonamides refers to the
conformation in which the lone pair of the nitrogen atom bisects
95.475(3), g = 103.737(2)8, V= 1977.7(4) Š3, Z = 1, 1calcd
=
1.271 gmLÀ1
,
m = 0.215 mmÀ1
,
2qmax = 54.008, T= 173(2) K,
À
the O-S-O angle (the lone pair is antiperiplanar to the S C
R1 = 0.0671 for 5583reflections (559 parameters) with I >
2s(I), and R1 = 0.1074, wR2 = 0.1673, and GOF = 1.027 for all
bond), see: A. K. H. Hirsch, S. Lauw, P. Gersbach, W. B.
Schweizer, F. Rohdich, W. Eisenreich, A. Bacher, F. Diederich,
ChemMedChem 2007, 2, 806.
8485 data, max/min residual electron density + 0.842/
À3
À0.723eŠ
.
120
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Angew. Chem. Int. Ed. 2008, 47, 117 –120