Pentafluorophenyl salicylamine receptors in anion-π interaction studies

Article abstract of DOI:10.1080/10610278.2012.715648

A crystal structure analysis confirms the appropriateness of pentafluorophenyl salicylamine (1a) as a-acceptor for anion-interactions. Crystals of 1aHCl show that the OH-group fixes the anion in a η²-type binding motif above the electron-defici

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Supramolecular Chemistry
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Pentafluorophenyl salicylamine receptors in anion–π
interaction studies
Michael Giese a , Markus Albrecht a , Christian Plum a , Daniel Hintzen a , Arto Valkonen b &
Kari Rissanen b
a Institut für Organische Chemie, RWTH Aachen University , Landoltweg 1, 52074 , Aachen ,
Germany
b Department of Chemistry , Nanoscience Center, University of Jyväskylä , P.O. Box 35,
FIN-40014 , Jyväskylä , Finland
Published online: 31 Aug 2012.
To cite this article: Michael Giese , Markus Albrecht , Christian Plum , Daniel Hintzen , Arto Valkonen & Kari Rissanen (2012)
Pentafluorophenyl salicylamine receptors in anion–π interaction studies, Supramolecular Chemistry, 24:11, 755-761, DOI:
10.1080/10610278.2012.715648
To link to this article: http://dx.doi.org/10.1080/10610278.2012.715648
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Supramolecular Chemistry
Vol. 24, No. 11, November 2012, 755–761
Pentafluorophenyl salicylamine receptors in anion–p interaction studies
Michael Giesea, Markus Albrechta*, Christian Pluma, Daniel Hintzena, Arto Valkonenb and Kari Rissanenb
a
b
Institut fur Organische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany; Department of Chemistry,
¨
¨ ¨ ¨ ¨
Nanoscience Center, University of Jyvaskyla, P.O. Box 35, FIN-40014 Jyvaskyla, Finland
(Received 11 June 2012; final version received 18 July 2012)
A crystal structure analysis confirms the appropriateness of pentafluorophenyl salicylamine (1a) as a p-acceptor for anion–p
interactions. Crystals of 1a·HCl show that the OH-group fixes the anion in a h2-type binding motif above the electron-deficient
arene. Attempts to find some relevance for this weak intermolecular force in solution failed. Stronger CH–, NH– and
OH–anion interactions are dominant over the weak anion–p interactions. Due to the hydrogen bonding, the non-fluorinated
receptor exhibits the highest binding constants within this series.
Keywords: anion–p interaction; pentafluoro salicylamine; crystal structure; NMR titration
Introduction
However, serendipity leads to the remarkable stabilisation
of the sensitive tetraiodid dianion (I242) by anion–p
interactions (12). First attempts to find some relevance of
anion–p interactions in solution by studying pentafluor-
obenzyl phosphonium salts show no evidence for this
intermolecular force in chloroform (13).
Supramolecular chemistry relies on non-covalent bonds
(1), which vary from strong electrostatic attraction to
weakly dispersive. These intramolecular interactions
control self-assembly processes of multicomponent sys-
tems (2). Recent investigations show that arenes are
involved in natural as well as in synthetic self-organising
systems by p–p-stacking or cation–p interactions (3).
Within the last 20 years, an additional interaction between
anions and electron-deficient arenes has achieved con-
siderable attention (4). Earlier computational and structural
studies on anion–p interactions suggest the attractive
nature of the intermolecular force (5). Although the role of
anion–p interactions in the solid state (6) seems to be
understood, the relevance in solution (7) remains an open
question.
Results and discussion
The idea
As mentioned in the ‘Introduction’ section, the role of
anion–p interactions in solution is still unclear. First
studies focused on the interaction of pentafluorobenzyl
triphenyl phosphonium salts with anions in chloroform.
The results of these studies gave no insight into the anion–
p interaction in solution. The reason for that is the interplay
of different non-covalent interactions in the examined
system. To reduce the number of possible interactions, we
searched for appropriate uncharged receptors with penta-
fluorophenyl units. By the support of simple force field
calculations using Spartan 08 (MMFF), the pentafluor-
ophenyl salicyl amine (1a) was identified as a promising
candidate. We are well aware that force field calculations
are not appropriate to describe anion–p interactions. The
data obtained by this method are very rough but here they
only act as a starting point to visualise promising systems to
be synthesised. The phenolic OH-group should direct the
anion above the electron-deficient moiety and support the
anion–pinteraction.Moreover, theOH-groupcanbeusedas
reporter group during the NMR-titration experiments in
order to determine the binding constants for the investigated
anion–receptor complexes. A potential reference compound
is the corresponding dichlorophenyl salicyl amine (1b).
In 2008, we started our work on anion–p interactions in
pentafluorophenyl ammonium and phosphonium salts (8).
First crystallographic results revealed a high flexibility of
the anion position above the C6F5 unit. To describe the
observed binding motifs, the hapticity (h) nomenclature for
cation–p interactions was transferred to anion–p systems.
Further investigations could show that the position of the
anion above an electron-deficient arene can be controlled
by directing substituent of the periphery (9). Therefore,
CH– or NH–anion interactions were utilised. Moreover,
the influence of the electron-density of the p-system in the
interaction with anions was extensively studied, whereby
the attraction in high-fluorinated systems (four to five
fluorine atoms) turned to a repulsive force in low fluorinated
arenes (three to two fluorine atoms) (10). Crystallographic
studies on the role of the anions in anion–p interactions
show no dependence on the geometry of the anion (11).
*Corresponding author. Email: markus.albrecht@oc.rwth-aachen.de
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2012 Taylor & Francis
http://dx.doi.org/10.1080/10610278.2012.715648
http://www.tandfonline.com

756
M. Giese et al.
the monoclinic space group P21/n. The solid-state
structure of 1a shows that the anion is fixed above the
C6F5 unit (Figure 2) by a hydrogen-bridge of the OH-
˚
group [O· · ·Cl ¼ 3.086(2) A, OZH· · ·Cl ¼ 174(3)8]. Two
of the carbon–chloride distances are close to the sum of
the van der Waals (vdW) radii of the involved atoms
[C3/4· · ·Cl ¼ 3.506(3), 3.533(3) A]. A wider look on the
˚
crystalline packing of the ion pairs reveals that the anion
position is further fixed by two NZH· · ·Cl hydrogen-
bridges from neighbouring cations [N· · ·Cl ¼ 3.055(2),
˚
3.074(2) A; NZH· · ·Cl ¼ 170(2), 152(2)8, respectively].
It should be noted that due to the protonation of the
amine, the nitrogen is constrained to an sp3-hybridised
fashion. In the following solution studies, the free amine is
used, which is frequently inverted. Both results are not
directly comparable. But the crystal structure of 1a·HCl
shows that the phenolic OH-group is able to direct an
anion above the electron-deficient arene regardless of the
existent synergetic intermolecular hydrogen-bridges and
that the chosen receptor geometry is appropriate for
anion–p studies in solution.
Figure 1. Predicted interactions for receptors 1a and 1b with
bromide by molecular modelling (force field calculations).
For this no cooperative forces of the hydrogen-bridges (from
OH or NH) and the anion–p interaction were predicted
(Figure 1).
Synthesis of the phenyl salicylamines
In order to perform solution studies, the desired phenyl
salicylamines 1a and 1b have to be synthesised (Scheme 1).
Therefore, salicyl aldehyde (2) was reacted in an imine
condensation with the corresponding aniline derivatives(3a
or 3b). The resulting imines (4a and 4b) can be reduced by
mixture of sodium borohydride and silicon dioxide to the
desired amines 1a and 1b. All compounds and intermedi-
ates were fully characterised by standard analytical
methods (1H, 19F NMR, MS, IR and CHN).
Solution studies
In order to determine the binding constants for the anion–
receptor complexes, NMR-titration experiments were
performed in chloroform. Therefore, a 0.01 M stock
solution of the phenyl salicyl amines 1a and 1b and a
0.04 M guest solution of the tetrabutylammonium halides
were prepared. To exclude polarity effects, additional
titrations with tetrabutylammonium hexafluorophosphate
were carried out. The studied association equilibria are
summarised in Scheme 2.
X-ray structural analysis
Crystal structures are the result of the interplay of various
non-covalent interactions and steric effects. In the
following discussion only the relevant anion interactions
of the ion pairs are taken into account.
Before the association constants can be determined,
the stoichiometries of the investigated anion–receptor
complexes have to be checked by the method of Job.
Hereby, the curves for the complexes of 1a show a 1:1
ratio. In contrast to this, 1b·I and 1b·PF6 deviate strongly
from the 1:1 ratio towards a 2:1 ratio (see Figure 3(a)).
Unfortunately, it was not possible to follow the OH-
Intense attempts to co-crystallise the phenyl salicyla-
mines with tetra-alkyl ammonium salts failed. However,
diffusion of gaseous HCl into a solution of pentafluor-
ophenyl salicylamine 1a in ethylacetate resulted in
colourless crystals. Hydrochloride 1a·HCl crystallises in
1
proton in the H NMR. The titration’s curves of 1a were
obtained by following the fluorine signals and for 1b the
R2
R2
NH2
R1
N
R1
R2
R1
R1
R2
OH
O
R1
R2
R1
R2
OH
OH HN
+
R1
R1
R1
2
3a: R1 = R2 = F
4a: R1 = R2 = F (32%)
1a: R1 = R2 = F (83%)
3b: R1 = H, R2 = Cl
4b: R1 = H, R2 = Cl (80%)
1b: R1 = H, R2 = Cl (75%)
Scheme 1. Synthesis of the phenyl salicylamines 1a and 1b.

Supramolecular Chemistry
757
Figure 2. Part of the crystal structure of 1a·HCl: (a) side-view and (b) top-view of the ion pair as well as the molecular packing as
observed in the crystal structure of 1a·HCl.
benzylic protons were used as probe. The binding
constants result from a standard method of nonlinear
regression and are summarised in Table 1.
affinity like 1a·Br. Due to the deviation of the 1b·I and
1b·PF6 complexes from a 1:1 ratio, the corresponding
binding constants were not calculated.
The comparison of the obtained binding constants for
1a and 1b shows no hint for the relevance of anion–p
interactions in the association of the receptor–anion
complexes in chloroform. The higher binding constant for
1b·Cl might be due to the cooperativity of OH–, NH– and
CH–anion interactions in 1b (Scheme 3(a)). In contrast to
this, the OH– hydrogen bridge in 1a can cooperate with the
NH-anion (Scheme 3(b)) or the anion–p interaction
(Scheme 3(c)). Furthermore, the binding constants of 1a
and 1b were determined by the following different NMR
signals (19F and 1H).
The binding constants for 1a vary slightly from 275 to
81 M21. Hereby, the following of the different fluorine
signals (ortho, meta or para) in the 19F NMR result in the
same association constants. A comparison of the deter-
mined values reveals a decreasing binding strength from
chloride, bromide to iodide. The association constant for
1a·PF6 is with 94 M21, somewhat higher than the 1a·I
binding constant. The reason for that might be the
dependence of the anion–receptor stability from the
polarizability of the anions.
Interestingly, the binding constant for 1b·Cl is
significantly higher than that for 1a·Cl. The corresponding
1b·Br complex shows with 143 M21 a comparable binding
Conclusion
In conclusion, the presented results show that anion–p
interactions of 1a·HCl can be observed in the solid state.
Due to the h2-hapticity of these complexes, it can be
deduced that the structural features of the receptor are not
finally optimised for a fixation of the anion above the
centre of the electron-deficient arene. Although only the
charged aggregate 1a·HCl could be observed in the solid,
NMR spectroscopic titrations show that the neutral
compound 1a is an appropriate anion receptor in solution.
The structure of the receptors in solution is flexible and the
pentafluoro salicylamine is a promising candidate for
anion–p studies with a neutral receptor.
Scheme 2. Investigated association equilibria.

758
M. Giese et al.
Figure 3. (a) Representative Job plots for receptor 1a with various anions (Cl, Br, I, BF4, PF6 added as n-Bu4N-salts) in deuteric
chloroform; (b) corresponding Job plots for receptor 1b; (c) selected 19F NMR spectra for a 0.01 M solution of 1a. A solution of n-Bu4NCl
in CDCl3 was successively added; (d) selected H NMR spectra for a 0.01 M solution of 1b. A solution of n-Bu4NCl in CDCl3 was
1
successively added.
The NMR studies in deuteric chloroform give no
Table 1. Binding constants Ka (M21) for the complexes of the
phenyl salicylamines 1a and 1b with various anions (Cl, Br, I and
PF6 added as tetrabutyl ammonium salts).
indication for the relevance of anion–p interactions in the
investigated receptors. In contrast to our expectations, the
non-fluorinated anion receptor 1b shows a significant
higher affinity to chloride than to 1a. Since binding
constants are averages over all non-covalent interactions of
the system (competing and cooperative), in solution the
observed results become explainable. Due to the weakness
of the anion–p interaction, it can easily be covered by
other intermolecular effects. Further attempts have to
exclude these effects to find conclusive evidence for
anion–p interaction in solution.
Cl
Br
I
PF6
1a
1b
Fortho
Fmeta
Fpara
275
256
256
478
161
159
146
143
81
82
96
94
81
96
a
a
Hbenzyl
Notes: The binding constants were determined by 1H/19
F
NMR titration
experiments in CDCl3. Errors are estimated to be lower than 20%.
a Not calculated due to the deviation from a 1:1 ratio.

Supramolecular Chemistry
759
Scheme 3. Competing and cooperating interactions with the anion.
Experimental
Haryl), 7.06 (d, J ¼ 8.0 Hz, 1H, Haryl), 6.99 (dt,
J ¼ 8.0/1.4 Hz, 1H, Haryl). 19F NMR (CDCl3, 300 MHz):
d (ppm) ¼ 2151.91 (m, 2 F, Fortho), 2158.08 (m, 1 F,
(%) ¼ 286.8 (100, [M]þ, C13H6F5NOþ). IR (KBr):
n (cm21) ¼ 3424 (m), 3334 (m), 3138 (m), 2654 (w),
2477 (w), 2325 (w), 2201 (m), 2145 (m), 1926 (w), 1705
(w), 1611 (s), 1573 (w), 1503 (vs), 1367 (m), 1274 (m), 1205
(m), 1151 (m), 1112 (m), 975 (vs), 901 (m), 759 (vs), 665
(w). C13H6F5NO: C 54.35, H 2.09, N 4.84, found: C 54.49,
H 1.93, N 4.94.
The commercially available reagents were used as received
without further purification. The solvents were used after
distillation. For NMR spectra, a Varian Mercury 300 NMR
spectrometer (1H: 300 MHz, 19F: 282 MHz) was used. The
samples were solved in deuteric chloroform. Mass
spectrometric data were obtained via a Finnigan SSQ
7000 and Thermo Deca XP as EI (70 eV) or ESI. IR spectra
were measured on a PerkinElmer FT-IR spectrometer
Spektrum 100. All samples were measured in KBr at
4000–650 cm21. CHN-O-Rapid Vario EL from Heraeus
was used for elemental analysis. Melting points were
determined on a Bu¨chi B540 without further correction.
X-ray data were collected at 123(2) K with Bruker-Nonius
KappaCCD diffractometer equipped with APEXII detec-
tor, using graphite monochromatised Mo Ka radiation
Fpara), 2162.32 (m, 2 F, Fmeta). MS (EI, 70 eV): m/z
3,5-Dichlorophenyl salicylimine 4b
Yield: 871 mg colourless solid (M ¼ 266.12 g/mol,
3.27 mmol, 80%). m.p.: 878C. 1H NMR (CDCl3,
300 MHz): d (ppm) ¼ 12.55 (s, 1H, OH), 8.58 (s, 1H,
CHN), 7.41 (d, J ¼ 3.2 Hz, 1 Haryl), 7.27 (t, J ¼ 1.8 Hz, 1H,
˚
(l ¼ 0.71073 A). COLLECT (14a) software was used for
data collection and data were processed with DENZO-
SMN (14b). The structure was solved by direct methods,
using SIR-2004 (14c) and refined on F 2, using SHELXL-
97 (14d). The multi-scan absorption correction (SADABS
(14e)) was applied to data. The H atoms bonded to C atoms
were calculated to their idealised positions with isotropic
temperature factors (1.2 times the C atom temperature
factor) and refined as riding atoms. The H atoms bonded to
N or O atoms were found from electron density map and
H
aryl), 7.26(s, 1H, Haryl), 7.17(d, J ¼ 1.7 Hz, 1H, Haryl), 7.05
(s, 1H, Haryl), 7.02 (s, 1 H, Haryl), 6.97 (dt, J ¼ 8.0/11.2Hz,
1H, Haryl). MS (ESI): m/z (%) ¼ 264.0 (100, [M 2 H]2,
C13H8Cl2NO). IR (KBr): n (cm21) ¼ 3129 (w), 3079 (m),
2988 (w), 2722 (w), 2653 (w), 2328(m), 2098 (m), 1996(w),
1948 (w), 1675 (m), 1618 (s), 1563 (s), 1494 (m), 1455 (s),
1422 (m), 1362 (s), 1278 (s), 1235 (m), 1192 (s), 1150 (s),
1104 (s), 1031 (w), 991 (w), 942 (s), 850 (s), 802 (s), 748 (s),
669 (s). C13H9NCl2O: C 58.62, H 3.41, N 5.26, found:
C 58.50, H 3.30, N 5.30.
˚
restrained to distances of 0.91 (N) or 0.84 A from N/O atom
(DFIX, s ¼ 0.02) with isotropic temperature factors [1.2
(N) or 1.5 (O) times the parent atom temperature factor].
Synthesis of the phenyl salicylamines
Synthesis of the phenyl salicylimines
Imine 4a or 4b was mixed with 5.0 equiv. of sodium
borhydride, 1.00 g silica gel and a few drops of
chloroform. The slurry was grounded five times for
15 min. In between the slurry was rested for 20 min. To the
mixture was added 30 mL of chloroform and the non-
soluble solid was filtered off. After removing the solvent
the obtained white solid was dried in vacuo.
Equimolar amounts of salicylaldehyde and the corre-
sponding aniline derivative (pentafluoroanilin or 3,5-
dichloroanilin) were stirred at 1008C for 6–8 h. The
resulting solid was washed sparely with cold hexane and
dried under vacuo.
Pentafluorophenyl salicylimine 4a
Pentafluorophenyl salicylamine 1a
Yield:410 mgyellow solid(M ¼ 287.18 g/mol, 1.40 mmol,
32%). m.p.: 1408C. 1H NMR (CDCl3, 300 MHz): d
(ppm) ¼ 12.24 (s, 1H, OH), 8.83 (s, 1H, CHN), 7.47 (dt,
J ¼ 8.0/1.4 Hz, 1H, Haryl), 7.41 (dd, J ¼ 8.0/1.4 Hz, 1H,
Yield: 286 mg colourless solid (M ¼ 289.20 g/mol,
1.00 mmol, 83%). m.p.: 788C. 1H NMR (CDCl3,
300 MHz): d (ppm) ¼ 7.22 (dt, J ¼ 7.6/1.6 Hz, 1H, Haryl),

760
M. Giese et al.
7.14 (dt, J ¼ 7.6/1.6 Hz, 1H, Haryl), 6.92–6.84 (m, 2H,
aryl), 6.42 (s, 1H, OH), 4.44 (s, 2H, Hbenzyl), 4.05 (s, 1H,
References
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NH). 19F NMR (CDCl3, 300 MHz): d (ppm) ¼ 2156.02
(m, 2F, Fortho), 2163.45 (m, 2F, Fmeta), 2167.08 (m, 1F,
Fpara). MS (EI, 70 eV): m/z (%) ¼ 289.1 (17, [M]þ,
C13H8F5NOþ). IR (KBr): n (cm21) ¼ 3333 (m), 3151
(w), 3026(w), 2963(w), 2877(w), 2092(w), 2007(w), 1948
(w), 1697 (w), 1656 (w), 1593 (m), 1511 (vs), 1459 (s), 1356
(m), 1299 (w), 1246 (s), 1184 (w), 1152 (w), 1108 (w), 1057
(m), 1016 (vs), 987 (s), 956 (s), 892 (w), 870 (m), 850 (w),
819 (m), 780 (m), 756 (s), 729 (m), 662 (w). C13H8F5NO:
C 53.99, H 2.79, N 4.84, found: C 53.88, H 2.73, N 4.85.
Single crystals of 1a·HCl were obtained by slow
diffusion of HCl into a solution of 1a in ethylacetate.
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3,5-Dichlorophenyl salicylamine 1b
Yield: 374 mg colourless solid (M ¼ 268.14 g/mol,
1.40 mmol, 75%). m.p.: 748C. 1H NMR (CDCl3,
300 MHz): d (ppm) ¼ 7.23–7.18 (m, 2H, Haryl), 6.92 (dd,
J ¼ 9.0/1.2 Hz, 1H, Haryl), 6.88 (dd, J ¼ 8.0/0.9 Hz, 1H,
Haryl), 6.82 (t, J ¼ 1.8 Hz, 1H, Haryl), 6.66 (s, 1H, Haryl),
6.65 (s, 1H, Haryl), 4.35 (s, 2 H, Hbenzyl). MS (EI, 70 eV): m/z
(%) ¼ 268.0 (100, [M]þ, C13H11Cl2NO). IR (KBr): n
(cm21) ¼ 3407 (s), 3327 (m), 3043 (w), 2921 (w), 2871
(w), 2697 (w), 2324 (w), 2105 (w), 1991 (w), 1949 (w),
1913 (w), 1695 (w), 1586 (s), 1490 (s), 1449 (s), 1407 (m),
1353 (m), 1317 (m), 1267 (m), 1235 (s), 1181 (m), 1105 (s),
1068 (s), 1037 (m), 982 (m), 925 (m), 856 (m), 824 (s), 792
(s), 755 (s), 706 (w), 663 (s). C13H11NCl2O: C 58.23, H
4.13, N 5.22, found: C 57.98, H 4.05, N 5.18.
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Compound 1a·HCl
Colourless prisms from EtOAc, C13H9ClF5NO,
F.W. ¼ 325.66, crystal size 0.38 £ 0.36 £ 0.16 mm, mono-
clinic, space group P21/n (no. 14), a ¼ 9.9652(3),
`
Deya, P.M. J. Phys. Chem. A 2005, 109, 4632–4637; (e)
Frontera, A.; Quinonero, D.; Costa, A.; Ballester, P.; Deya,
`
P.M. New J. Chem. 2007, 31, 556–560; (f) Demeshko, S.;
Dechert, S.; Meyer, F. J. Am. Chem. Soc. 2004, 126, 4508–
4509; (g) Campos-Fernandez, C.S.; Schottel,
B.L.; Chifotides, H.T.; Bera, J.K.; Bacsa, J.; Koomen,
J.M.; Russell, D.H.; Dunbar, K.R. J. Am. Chem. Soc. 2005,
127, 12909–12923; (h) Schottel, B.L.; Bacsa, J.; Dunbar,
K.R. Chem. Commun. 2005, 46–47; (i) Schottel,
B.L.; Chifotides, H.T.; Shatruk, M.; Chouai, A.; Bacsa, J.;
˚
b ¼ 13.1330(3), c ¼ 10.4590(3) A, b ¼ 97.193(2)8,
3
V ¼ 1358.03(6) A , Z ¼ 4, Dcalc ¼ 1.593 g/cm3, m ¼
˚
0.337 mm21, F(0 0 0) ¼ 656, 4767 collected reflections
(umax ¼ 25.258) of which 2454 are independent [Rint
¼
0.0316], full-matrix least-squares on F 2 with 3 restraints
and 199 parameters, GOF ¼ 1.046, R1 ¼ 0.0400 [I .
2s(I)], wR2 (all data) ¼ 0.1036, largest peak/hole ¼
´
Perez, L.M.; Dunbar, K.R. J. Am. Chem. Soc. 2006, 128,
23
˚
0.321/20.252 e A
.
5895–5912; (j) Furkawa, S.; Okubo, T.; Masaoka, S.;
Tanaka, D.; Chang, H.; Kitagawa, S. Angew. Chem. 2005,
117, 2760–2756; Angew. Chem. Int. Ed. 2005, 44, 2700–
2704; (k) Maheswari, P.U.; Modec, B.; Pevec, A.;
Kozlevcar, B.; Massera, C.; Gamez, P.; Reedijk, J. Inorg.
Chem. 2006, 45, 6637–6645; (l) Casellas, H.; Massera, C.;
Buda, F.; Gamez, P.; Reedijk, J. New J. Chem. 2006, 30,
1561–1566; (m) Galstyan, A.; Miguel, P.J. S.; Lippert, B.
Chem. Eur. J. 2010, 16, 5577–5580.
Crystal data CCDC-883887 (1a·HCl) without structure
factors can be obtained free of charge from Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
conts/retrieving.html.
Acknowledgement
The Academy of Finland is gratefully acknowledged for funding
(grant nos 130629, 122350 and 140718 to KR).
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¨
SADABS, University of Gottingen, Germany, 1996.