The role of the C-H...π interactions in the cyclisation reactions leading to new aryl-bridged tetraazamacrocyclic complexes of copper and nickel

Article abstract of DOI:10.1002/ejic.201000818

A series of neutral macrocyclic transition metal complexes of Cu ^II and Ni^II, with bridging polyether linkers joining them to aromatic fragments, has been synthesised and their crystal and molecular structures have been established b

Full text of DOI:10.1002/ejic.201000818

FULL PAPER
DOI: 10.1002/ejic.201000818
The Role of the C–H···π Interactions in the Cyclisation Reactions Leading to
New Aryl-Bridged Tetraazamacrocyclic Complexes of Copper and Nickel
Radosław Kamin´ski,[a] Jarosław Kowalski,[b] Iwona Mames,[b]
[b]
[a]
[a]
´
Bohdan Korybut-Daszkiewicz, Sławomir Domagała, and Krzysztof Wozniak*
Keywords: Macrocycles / Nickel / Copper / Cyclisation reactions / Density functional calculations
A series of neutral macrocyclic transition metal complexes of
CuII and NiII, with bridging polyether linkers joining them to
aromatic fragments, has been synthesised and their crystal
and molecular structures have been established by single-
crystal X-ray diffraction. These molecules adopt an “equato-
rial” conformation of the bridge due to formation of C–H···π
interactions. Because of these interactions only cyclic prod-
ucts are formed in the SN2 reaction. DFT calculations also
confirm experimental results.
torial” conformation due to C–H···π interactions with the
saturated part of the molecule and does not form any cavity
above the metal-coordinating macrocycle. Apparently, these
interactions, although very weak, do influence the confor-
mation of the studied molecules and are an elegant example
of the importance of weak C–H···π-electron hydrogen
bonds. We also support our experimental findings by theo-
retical calculations utilising the DFT methods.
Introduction
Molecular recognition occurs due to various intermo-
lecular interactions, such as hydrogen bonding, π···π stack-
ing and electrostatic interactions. An efficient recognition
may be achieved by cooperative action of many different
interactions. Acceptor···donor interactions of the charge
transfer type have recently been utilised in our group to
synthesise new catenanes involving +4-charged bismacro-
cyclic face-to-face complexes containing NiII and/or CuII
coordinating units. These units interact through a π···π
mechanism with electron-rich benzene rings of dibenzo-24-
crown-8.[1,2] Changing the oxidation states of the heteronu-
clear (Ni, Cu) catenane leads to a potential-driven intramo-
lecular motion of the interlocked crown ether molecular
fragment.
In all bismacrocycles composed of nearly planar tetra-
azamacrocyclic components, a face-to-face arrangement of
the tetraazamacrocyclic units is observed.[3–8] Sometimes
such units are slightly shifted, one relative to the other one.
Such molecules form box-like molecular objects that can,
and sometimes do, incorporate small guest molecules.
In this work, we incorporate transition metal ions into
macrobicyclic receptor molecules composed of a redox
switchable, neutral tetraazamacrocyclic complex[9] bridged
with a π-electron-rich aromatic linker. We use single-crystal
X-ray diffraction measurements to confirm the macrobicy-
clic structures of the synthesised neutral complexes. In con-
trast to similar polymethylene bridged macrobicyclic com-
plexes,[10,11] however, the aromatic bridges adopt the “equa-
Results and Synthesis
Synthesis
Aromatic dithiols 1e, 2e and 3e, applied as bridging
groups, were synthesised from the commercially available
compounds 1a, 2a and 3b by using the standard procedures
outlined in Scheme 1. Dithiols 1e, 2e and 3e, in the presence
of a base, react with symmetric dimesyl (or dichloro) deriv-
atives of neutral macrocyclic complexes of CuII or NiII
(4Ni, 5Ni and 5Cu) (Scheme 2) to form the bismacrocyclic-
bridged products CuPh, NiPh, NiNaph and Nibiph. Even in
the presence of an excess of dithiols, only cyclic 1:1 prod-
ucts were isolated from the reaction mixtures and the ex-
pected linear 2:1 reaction products were not formed.
The structures of the isolated bicyclic products were con-
firmed by elemental analyses, Field desorption mass spec-
1
trometry (FDMS), H and 13C NMR spectroscopy (for the
diamagnetic NiII complexes) and single-crystal X-ray crys-
tallography.
[a] Department of Chemistry, University of Warsaw,
Pasteura 1, 02-093 Warszawa, Poland
X-ray Diffraction Analysis
E-mail: kwozniak@chem.uw.edu.pl
[b] Institute of Organic Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warszawa, Poland
The atom labelling schemes of bicyclic molecules are
shown in Figure 1 and selected geometrical parameters pre-
sented in Table 1. The NiPh and NiNaph compounds crys-
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201000818.
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K. Woz´niak et al.
FULL PAPER
Scheme 1. Synthesis of bridged dithiols. Reagents: (a) HO–(CH2)3–OH; (b) MsCl, Et3N; (c) thiourea; (d) 1) NaOH(aq.), 2) HCl(aq.) (MsCl
= methanesulfonyl chloride).
Scheme 2. Synthesis of aryl-bridged tetraazamacrocyclic complexes of CuII and NiII.
¯
tallise in the triclinic P1 space group with one molecule in Ni(01)N(02)N(03)N(04)N(05)C(06)C(07)C(08)C(011)C(012)-
the asymmetric unit. CuPh and NibiPh crystallise in the C(013)] and the plane containing the aromatic fragment
monoclinic P21/c space group with two independent [C(38)C(39)–C(40)C(41)C(42)C(43)
or
C(038)C(039)-
molecules in the asymmetric unit. In all molecules, the angle C(040)C(041) C(042)C(043) for NiPh and CuPh, C(44)-
between respective macrocyclic least-squares planes C(45)C(46)C(47)C(48)C(49) or C(044)C(045) C(046)-
[Ni(1)N(2)N(3)N(4)N(5)C(6)C(7)C(8)C(11)C(12)C(13) or C(047)C(048)C(049) for NibiPh, C(38)C(39)C(40) C(41)-
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The Role of the C–H···π Interactions in Cyclisation Reactions
Figure 1. Labelling of atoms and estimation of atomic thermal motion as atomic displacement parameters (ADPs; selected non-hydrogen
atoms are treated isotropically; ellipsoids are drawn at 50% probability level). Hydrogen atoms were placed in idealized positions and
are omitted for clarity except those involved in C–H···π interactions. Disordered sulfur atoms in the NiPh structure are shown as partially
transparent. The colours of atoms are the same for all figures.
C(42)C(43) C(44)C(45) C(46)C(46) for NiNaph] indicates C(038)C(039)C(040)C(041)C(042)C(043) and C(44)C(45)-
that these two molecular fragments are nearly perpendicu- C(46)C(47)C(48)C(49) or C(044)C(045)C(046)C(047)-
lar to each other (the θM and θЈM parameters in Table 1 are C(048)C(049), respectively]. The values of these angles are
close to ca. 70°; the θЈM is obtained when two symmetry close to the theoretical ones (38.8–45.8°) obtained by means
independent molecules are within the asymmetric unit). In of computational chemistry methods.[12] Additionally, it is
the case of CuPh and NiNaph, the angle is smaller due to worth mentioning that both sulfur atoms in the NiPh struc-
the supramolecular arrangement. The metal ion in these ture are disordered over two positions with the site occupa-
complexes forms a square-planar coordination and the M– tion ratio 60:40.
N bond lengths are typical of this type of compounds (ca.
The conformation of the molecules seems to be imposed
1.85 Å for NiPh, NibiPh and NiNaph). The Cu–N bond by the C–H···π interactions of the hydrogen atoms from the
lengths in CuPh are slightly longer than the Ni–N ones (ca. macrocyclic ethylene bridges to the aromatic rings (Fig-
0.06–0.09 Å). The S–C bond lengths are typical, in the ure 1, Table 2). Apparently, such interactions can work as a
range 1.71 Å to 1.93 Å. The benzene rings of the biphenyl template in the cyclisation reactions and they exclude the
moieties in the NibiPh structure, described by the angle be- possibility of the formation of linear products. The pro-
tween two least-squares planes, are twisted by 37.8(3)° and posed mechanism of such a transformation is shown in
38.8(3)° for the two symmetrically independent molecules Scheme 3. The first step is the deprotonation of the SH
[see parameters θP and θЈP in Table 1 defined as the angles group and a further SN2 reaction with the macrocyclic com-
between the planes C(38)C(39)C(40)C(41)C(42)C(43) or pound. The reaction intermediate formed then undergoes
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K. Woz´niak et al.
Table 1. Selected geometrical parameters for the studied com- supramolecular arrangement. The intramolecular π···π in-
FULL PAPER
pounds.[a]
.
teractions are probably not favourable within the crystalline
state due to a large number of other short intermolecular
contacts (see Table S1 in the Supporting Information).
The 3D molecular structure of NiPh is quite simple and
it consists of chains of macrocyclic fragments bound by
weak C–H···O interactions. Such chains are weakly con-
nected, which is confirmed by the positions of the disor-
dered sulfur atom and C–H···S contacts. The chain-type
moieties form layers (Figure 2), which are held together by
weak C–H···π and C–H···O interactions.
Parameter
θ [°], d [Å]
Compound
NiPh
CuPh
NibiPh
NiNaph
θM
θЈM
69.9(3)
–
1.826(13)
1.836(13)
1.816(11)
1.846(11)
–
–
65.3(5)
44.5(7)
1.910(20)
1.909(21)
1.852(25)
1.949(21)
1.978(19)
1.915(20)
1.952(21)
1.919(19)
1.737(22)
–
1.811(20)
1.814(25)
–
1.809(22)
1.729(23)
–
76.7(1)
67.1(2)
1.867(5)
1.858(5)
1.858(5)
1.862(5)
1.863(5)
1.861(5)
1.854(5)
1.856(5)
–
1.731(8)
1.857(6)
–
1.804(6)
1.702(9)
–
1.745(8)
1.773(8)
–
1.811(7)
1.830(7)
37.8(3)
38.8(3)
55.73(3)
–
1.847(2)
1.843(2)
1.846(2)
1.851(2)
–
–
dM(1)–N(2)
dM(1)–N(3)
dM(1)–N(4)
dM(1)–N(5)
dM(01)–N(02)
dM(01)–N(03)
dM(01)–N(04)
dM(01)–N(05)
dS(22)–C(27)
dS(22)–C(28)
dS(22)–C(32)
dS(23)–C(30)
dS(23)–C(31)
dS(23)–C(35)
dS(022)–C(027)
dS(022)–C(028)
dS(022)–C(032)
dS(023)–C(030)
dS(023)–C(031)
dS(023)–C(035)
θP
–
–
–
–
–
1.928(32)
–
1.843(25)
1.709(27)
1.813(2)
1.804(2)
–
1.801(2)
1.809(2)
–
–
–
–
–
–
–
–
–
1.905(33)
–
–
–
–
–
–
–
–
1.810(21)
1.803(26)
–
1.816(23)
–
θЈP
–
[a] M = Ni or Cu; d = distance; in the case of disorder only the
major component part is taken into account [for NiPh only the
S(22A) and S(23A) atoms are considered].
Figure 2. Layers based on C–H···O and C–H···π interactions within
the NiPh crystal structure.
conformational changes from the linear form to the bent
one with some extra stabilisation offered by the C–H···π
interactions (Scheme 3, a).
In the CuPh molecular structure, the supramolecular ar-
rangement of molecules is also based on π···π interactions
between the macrocyclic fragments of neighbouring sym-
metry-independent molecules (Figure 3, a). The C–H···π,
C–H···O and C–H···S interactions, also present in this
structure, serve as a support. In the 3D structure, an inter-
esting intermolecular net is formed with symmetry-indepen-
dent molecules creating a pseudochain (Figure 3, b). The
main difference between the NiPh and CuPh structures is
the number of symmetry independent molecules within the
asymmetric unit (one and two, respectively).
The NibiPh structure also shows π···π interactions be-
tween the macrocyclic fragments. Its supramolecular struc-
ture is based on two symmetry independent molecules con-
nected by weak C–H···π interactions between the aromatic
and macrocyclic molecular fragments, and C–H···O interac-
tions forming trimeric structures with another molecule
(Figure 4, a). Such supramolecular trimers are formed and
packed efficiently within the crystal lattice (Figure 4, b).
Some weak C–H···S hydrogen bonds are also present and
these join together two neighbouring units (Figure 4, c).
In the case of the NiNaph structure, C–H···π interactions
Table 2. Geometry of intramolecular C–H···π interactions.[a]
Interaction
dD–H dH···A dD···A
θD–H···A
[Å]
[Å]
[Å]
[°]
NiPh
CuPh
C(9)–H(9B)···C(38)π
C(10)–H(10B)···C(41)π
C(9)–H(9B)···C(43)π
C(10)–H(10B)···C(41)π
C(09)–H(09D)···C(038)π
0.99
0.99
0.99
0.99
0.99
2.91 3.700(30) 137
2.73 3.520(30) 137
2.91 3.770(30) 146
2.79 3.630(40) 143
3.04 3.860(30) 141
2.92 3.880(30) 165
C(010)–H(10D)···C(040)π 0.99
NibiPh C(9)–H(9A)···C(44)π
C(10)–H(10A)···C(47)π
C(09)–H(9D)···C(038)π
C(010)–H(10D)···C(041)π 0.99
NiNaph C(9)–H(9A)···C(39)π
0.99
0.99
0.99
2.73 3.609(8)
2.71 3.388(8)
3.06 3.667(8)
2.92 3.697(9)
2.95 3.824(3)
2.87 3.769(3)
2.79 3.573(3)
2.67 3.432(3)
148
126
121
136
147
151
137
134
0.99
0.99
0.99
0.99
C(9)–H(9A)···C(40)π
C(10)–H(10B)···C(41)π
C(10)–H(10B)···C(42)π
[a] D denotes the donor of the D–H···A interaction, A acceptor;
C–H···Aπ stands for the shortest C–H···π contacts.
The next step in the formation of the bismacrocycles is
the deprotonation of the remaining SH group, which allows occur to form dimers (Figure 5, a). The naphthyl rings are
the intramolecular SN2 reaction to proceed. The same result bound to the macrocyclic fragments by C–H···π interac-
can be obtained by π···π interactions between the macro- tions and as a consequence, molecular chains are formed
cyclic and aryl molecular fragments (Scheme 3, b). How- (Figure 5, b). The chains are connected by very weak C–
ever, this possibility is not realised within the crystal struc- H···O and C–H···S contacts and packed like rods parallel
ture. A possible justification for this can be found in the one to another.
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The Role of the C–H···π Interactions in Cyclisation Reactions
Scheme 3. Proposed mechanism of the cyclisation reaction templated by (a) C–H···π interactions between the ethylene bridges and aryl
group or (b) possible π···π interactions between the macrocyclic and aryl molecular fragments (as in NiPh or CuPh).
Figure 3. (a) The π···π interactions between neighbouring symmetry independent CuPh molecules; (b) chains of molecules based on weak
interactions.
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Figure 4. (a) Three NibiPh molecules connected by C–H···π and C–H···O interactions, (b) packing of dimers, (c) weak C–H···S interactions
between the neighbouring dimers.
Theoretical Calculations
To rationalise the proposed mechanism, quantum-chemical
DFT calculations for the NiPh compound were carried out
with the ADF package.[13] Three possible conformations of
the protonated reaction intermediate were taken into ac-
count: K1 – linear, K2 – bent with assumed C–H···π interac-
tions (starting geometry close to those obtained from crys-
tal structures) and K3 – bent with assumed π···π interac-
tions between the parallel macrocyclic and phenyl rings
with a distance between of approximately 3.5 Å selected as
the starting point. The geometries of these three conformers
were optimised and their relative energies (ΔE) were calcu-
Figure 5. (a) Dimers of NiNaph in the crystalline state based on C–
lated and compared (Figure 6). Selected geometrical pa-
H···π and C–H···O interactions; (b) the structural motif within the
rameters concerning weak interactions are presented in
Table 3.
chains of molecules based on the C–H···π interactions between the
naphthyl rings and the macrocyclic molecular fragment.
Figure 6. Geometries for three possible conformers (K1, K2 and K3) and their relative energies obtained from theoretical calculations.
Some hydrogen atoms are omitted for clarity.
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The Role of the C–H···π Interactions in Cyclisation Reactions
Synthesis: Biphenyl-4,4Ј-diol (1a), naphthalene-1,5-diol (2a), 1,4-
bis(2-hydroxyethoxy)benzene (3b), solvents and reagents used in
these studies were reagent grade or better. Complexes 5Ni and 5Cu
were prepared according to procedures described elsewhere.[15]
Table 3. Selected geometrical parameters for C–H···π interactions
for two calculated conformers of NiPh.[a]
Conformer Interaction
dD–H dH···A
[Å] [Å]
dD···A
θD–H···A [°]
[Å]
4,4Ј-Bis(3-hydroxypropoxy)biphenyl (1b): Biphenyl-4,4Ј-diol (25 g,
0.134 mol), 3-chloropropan-1-ol (50 mL, 0.598 mol) and Cs2CO3
(97.8 g, 0.3 mol) were added to stirred acetonitrile (50 mL). The
mixture was refluxed for 6 h and the solids were removed by fil-
tration and washed with warm acetonitrile (3ϫ50 mL). The solu-
tion was treated with small amount of concentrated HCl(aq.) until
it became acidic. The mixture was then partially evaporated and
left in the refrigerator for few hours. The crystalline product was
then filtered off and washed with cold acetonitrile (3ϫ20 mL). The
filtrate was again concentrated, crystallised and filtered off. This
procedure was repeated few times. The combined solids were dried
in vacuo over P2O5; yield 23.5 g (58%); m.p. 199–200 °C. IR (nu-
K2
K3
C(9)–H(9B)···C(38)π
C(10)–H(10B)···C(41)π 1.101 3.4329 4.2461 131.77
C(9)–H(9B)···C(39)π
1.100 2.8677 3.6237 125.87
1.103 2.8164 3.8897 164.24
[a] D denotes the donor of the D–H···A interaction, A is the ac-
ceptor; D–H···Aπ denotes the shortest contact of D–H···π interac-
tion.
Although the calculated energy differences between the
three conformations are small (probably due to the known
restrictions of DFT methods to model weak interac-
tions[14]), several useful features can be found. The two bent
conformers K2 and K3 are lower in energy than the linear
K1. After optimisation, the conformer K3, the lowest in en-
ergy and with π···π interactions (compared to Scheme 2, b),
does not show the presence of these interactions and it is
stabilised by C–H···π interactions; both bent conformations
jol): ν = 3270 (br. s), 1604 (s) cm–1. 1H NMR ([D6]DMSO,
˜
200 MHz): δ = 1.93 (p, J = 6.0 Hz, 4 H, CH2 β to OH), 2.65 (t, J
= 5.5 Hz, 2 H, OH), 3.67 (q, J = 5.9 Hz, 4 H, CH2 α to OH), 4.09
(t, J = 6.3 Hz, 4 H, CH2 γ to OH), 6.96 (m, 4 H, ring CH pos.
2,2Ј,6 and 6Ј), 7.50 (m, 4 H, ring CH pos. 3,3Ј,5 and 5Ј) ppm. 13C
NMR ([D6]DMSO, 100 MHz): δ = 58.1 (CH2 α to OH), 32.9 (CH2
are stabilised in a similar way. The difference between the β to OH), 65.3 (CH2 γ to OH), 115.5 (ring CH pos. 3,3Ј,5 and 5Ј),
127.9 (ring CH pos. 2,2Ј,6 and 6Ј), 132.9 (ring C pos. 1 and 1Ј),
158.5 (ring CO) ppm.
bent conformations is caused by different geometry of the
weak interaction. In the case of K3, the interaction is much
closer to linearity than for two cooperative interactions in
K2. In this case, the presence of π···π interactions is ex-
cluded due to a long distance between the macrocyclic and
phenyl rings (ca. 4 Å). Therefore, the previously proposed
mechanism of the cyclisation reaction should be revised –
the π···π interactions in the (b) pathway should be replaced
by different geometry of π···π interactions or an additional
pathway “(c)” could be introduced (compared to
Scheme 2). In fact, all bent conformations led to the prod-
ucts of the cyclisation reaction.
1,5-Bis(3-hydroxypropoxy)naphthalene (2b): This compound was
synthesised from 2a using the procedure for 1b; yield 45%; m.p.
139–140 °C. 1H NMR (CDCl3, 200 MHz): δ = 2.27 (q, J = 5.9 Hz,
4 H, CH2 β to OH), 4.05 (t, J = 6.0 Hz, 4 H, CH2 α to OH), 4.37
(t, J = 5.9 Hz, 4 H, CH2 γ to OH), 6.95 (d, J= 7.6 Hz, 2 H, ring
CH pos. 4 and 8), 7.44 (t, J = 8.0 Hz, 2 H, ring CH pos. 3 and 7),
7.88 (d, J = 8.7 Hz, 2 H, ring CH pos. 2 and 6) ppm. 13C NMR
(CDCl3, 50 MHz): δ = 32.5 (CH2 β to OH), 60.8 (CH2 α to OH),
66.0 (CH2 γ to OH), 105.8 (ring CH pos. 2 and 6), 114.5 (ring CH
pos. 4 and 8), 125.5 (ring CH pos. 3 and 7), 127.0 (ring pos. 9 and
10), 154.2 (ring CO) ppm.
1,4-Bis[2-(methylsulfonyloxy)ethoxy]benzene
(3c):
1,4-Bis(2-
hydroxyethoxy)benzene (5 g, 25.2 mmol) was suspended in dry
dichloromethane (200 mL). Triethylamine (7.7 mL, 55.2 mmol) and
methanesulfonyl chloride (4.3 mL, 55.2 mmol) were added with
stirring and the resulting mixture was stirred under reflux for 9 h.
The solution was washed with water (3ϫ75 mL), dried with
MgSO4, filtered and partially evaporated to a volume of 50 mL.
Hexane (25 mL) was then added and the mixture was heated until
dissolution and left in refrigerator. The crude product was recrys-
tallised from a 1:1 mixture of hexane/dichloromethane. The prod-
uct was filtered off and dried in vacuo; yield 6.37 g (71.3%). IR
Conclusion
In conclusion, we have prepared a series of neutral
macrocyclic transition metal complexes of CuII and NiII
with bridging polyether linkers joining them to aromatic
fragments. We have obtained molecular and crystal struc-
tures of four such compounds. It appears that these mole-
cules do not form intramolecular cavities but adopt an
“equatorial” conformation of the bridge due to C–H···π in-
teractions. These interactions are responsible for the forma-
tion of cyclic products, independent of the ratio of sub-
strates. DFT calculations confirm our experimental find-
ings.
1
(nujol): ν = 1603 (s), 1344 (s) cm–1. H NMR (CDCl , 200 MHz):
˜
3
δ = 3.17 (s, 6 H, CH3), 4.28 (m, 4 H, CH2-O-), 4.63 (m, 4 H,
CH2OMs), 6.93 (m, 4 H, ring CH) ppm. 13C NMR (CDCl3,
50 MHz): δ = 38.1 (CH3), 66.9 (CH2OMs), 68.4 (CH2-O-), 116.2
(ring CH), 153.1 (ring CO) ppm.
4,4Ј-Bis[3-(methylsulfonyloxy)propoxy]biphenyl (1c): The compound
was synthesised from 1b following the procedure used for 3c; yield
67%; m.p. 132–133 °C. H NMR (CDCl3, 200 MHz): δ = 2.25 (q,
Experimental Section
1
General: NMR spectra were obtained on Varian Mercury 400 or
Varian Gemini 2000BB spectrometers. Signals are reported in ppm
relative to the residual solvent signal. IR spectra (paraffin oil mulls)
were recorded with a Perkin–Elmer Spectrum 2000 FTIR spec-
trometer. ESIMS and FDMS were measured on Mariner Perseptive
Biosystem and Walters Micromass GCT Premier mass spectrome-
ters, respectively.
J = 6.0 Hz, 4 H, CH2 β to OMs), 3.00 (s, 6 H, S-CH3), 4.13 (t, J
= 5.8 Hz, 4 H, CH2 γ to OMs), 4.47 (t, J = 6.1 Hz, 4 H, CH2 α to
OMs), 6.95 (m, 4 H, ring CH pos. 2,2Ј,6 and 6Ј), 7.47 (m, 4 H, ring
CH pos. 3,3Ј,5 and 5Ј) ppm. 13C NMR (CDCl3, 50 MHz): δ = 29.5
(CH2 β to OMs), 37.6 (S-CH3), 63.7 (CH2 α to OMs), 67.1 (CH2
γ to OMs), 115.1 (ring CH pos. 3,3Ј,5 and 5Ј), 128.1 (ring CH pos.
2,2Ј,6 and 6Ј), 134.1 (ring C pos. 1 and 1Ј), 157.9 (ring CO) ppm.
Eur. J. Inorg. Chem. 2011, 479–488
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
485

K. Woz´niak et al.
FULL PAPER
1,5-Bis[3-(methylsulfonyloxy)propoxy]naphthalene (2c): The product
was obtained from 2b according to the procedure for 3c; yield
= 6.5 Hz, 4 H, CH2 β to SH), 2.73 (q, J = 7.4 Hz, 4 H, CH2 α to
SH), 4.10 (t, J = 6.0 Hz, 4 H, CH2 γ to SH), 6.95 (m, 4 H, ring
78.8%; m.p. 109–110 °C. 1H NMR (CDCl3, 200 MHz): δ = 2.46 CH pos. 2,2Ј,6 and 6Ј), 7.48 (m, 4 H, ring CH pos. 3,3Ј,5 and 5Ј)
(q, J = 6.2 Hz, 4 H, CH2 β to OMs), 3.04 (s, 6 H, S-CH3), 4.35 (t, ppm. 13C NMR (CD2Cl2, 100 MHz): δ = 21.6 (CH2 α to SH), 33.8
J = 5.8 Hz, 4 H, CH2 γ to OMs), 4.64 (t, J = 6.1 Hz, 4 H, CH2 α
to OMs), 6.94 (d, J = 7.4 Hz, 2 H, ring CH pos. 4 and 8), 7.45 (t,
J = 8.0 Hz, 2 H, ring CH pos. 3 and 7), 7.90 (d, J = 8.5 Hz, 2 H,
ring CH pos. 2 and 6) ppm. 13C NMR (CDCl3, 50 MHz): δ = 29.6
(CH2 β to OMs), 37.5 (S-CH3), 63.8 (CH2 α to OMs), 67.2 (CH2
γ to OMs), 105.9 (ring CH pos. 2 and 6), 114.7 (ring CH pos. 4
and 8), 125.6 (ring CH pos. 3 and 7), 126.9 (ring C pos. 9 and 10),
154.3 (ring CO) ppm.
(CH2 β to SH), 66.2 (CH2 γ to SH), 115.1 (ring CH pos. 3,3Ј,5 and
5Ј), 127.9 (ring CH pos. 2,2Ј,6 and 6Ј), 133.6 (ring C pos. 1 and
1Ј), 158.4 (ring CO) ppm.
1,5-Bis(3-sulfanylpropoxy)naphthalene (2e): The compound was
synthesised from 2d following the procedure for 3e; yield 93.4%;
m.p. 250 °C (dec.). C16H20O2S2 (308.45): calcd. C 62.30, H 6.54;
1
found C 61.60, H 6.67. IR (nujol): ν = 1593 (s), 1269 (s) cm–1. H
˜
NMR (CDCl3, 200 MHz): δ = 1.52 (t, J = 8.2 Hz, 2 H, SH), 2.30
(p, J = 6.4 Hz, 4 H, CH2 β to SH), 2.93 (q, J = 7.4 Hz, 4 H, CH2
α to SH), 4.33 (t, J = 5.8 Hz, 4 H, CH2 γ to SH), 6.93 (d, J =
7.6 Hz, 2 H, ring CH pos. 4 and 8), 7.44 (t, J = 8.4 Hz, 2 H, ring
CH pos. 3 and 7), 7.90 (d, J = 8.7 Hz, 2 H, ring CH pos. 2 and 6)
ppm. 13C NMR (CDCl3, 50 MHz): δ = 21.8 (CH2 α to SH), 33.8
(CH2 β to SH), 66.2 (CH2 γ to SH), 105.8 (ring CH pos. 2 and 6),
114.6 (ring CH pos. 4 and 8), 125.4 (ring CH pos. 3 and 7), 127.0
(ring C pos. 9 and 10), 154.6 (ring CO) ppm.
S,SЈ-p-Phenylenebis(1-oxy-2-ethyl)bis(isothiouronium) Di(methane-
sulfonate) (3d): 3c (1.62 g, 4.58 mmol) was added to a stirred sus-
pension of thiourea (1.74 g, 22.9 mmol) in ethanol (50 mL). The
mixture was refluxed for 4 h and then evaporated to dryness. The
solid was suspended in 2-propanol (100 mL) and the mixture was
stirred under reflux for 30 min. The product was filtered off,
washed well with 2-propanol and dried in vacuo over P2O5; yield
1
2.17 g (93.4%) of colourless crystals; m.p. 100 °C (dec.). H NMR
(D2O, 200 MHz): δ = 2.70 (s, 6 H, S-CH3), 3.44 (br. t, J = 5.2 Hz,
4 H, CH2-S-), 4.24 (br. t, J = 5.2 Hz, 4 H, CH2-O-), 6.91 (s, 4 H,
ring CH) ppm. 13C NMR (D2O, 50 MHz): δ = 31.1 (CH2-S), 38.7
(S-CH3), 67.9 (CH2-O-), 116.6 (ring CH), 152.7 (ring CO) ppm.
{6,13-Bis[(2-chloroethoxy)carbonyl]-1,4,8,11-tetraazacyclotetradeca-
4,6,11,13-tetraenato(2–)-κ4N}nickel(II) (4Ni): The product was syn-
thesised following the procedure for the synthesis of 5Ni[15] using
corresponding diol as a substrate. However, the dichloro derivative
was isolated instead of the expected dimesylate; yield 86.3%. IR
S,SЈ-[4,4Ј-Biphenylylenebis(1-oxy-3-propyl)]bis(isothiouronium) Di-
(methanesulfonate) (1d): 1d was synthesised from 1c using the same
(nujol): ν = 1672 (s), 1600 (s), 1548 (m), 761 (m) cm–1. MS
˜
procedure as for 3d; yield 82%; m.p. 205 °C (dec.). IR (nujol): ν =
˜
(ESI, CHCl3): m/z = 425.3 [C16H20N4O4Cl2Ni – Cl–], 460.2
(C16H20N4O4Cl2Ni – e–). 1H NMR (CDCl3, 200 MHz): δ = 3.40
(br. s, 8 H, N-CH2CH2-N), 3.72 (t, J = 5.7 Hz, 4 H, CH2Cl), 4.41
(t, J = 5.7 Hz, 4 H, CH2-O-), 7.83 (s, 4 H, ring CH-N) ppm. 13C
NMR (CDCl3, 50 MHz): δ = 42.5 (CH2Cl), 58.7 (N-CH2CH2-N),
63.0 (CH2O), 97.7 (endocyclic, 4 °C), 155.0 (endocyclic CHN),
167.2 (C=O) ppm.
3257 (br. m), 3210 (br. m), 1670 (s) cm–1. 1H NMR (D2O,
200 MHz): δ = 2.16 (p, J = 6.1 Hz, 4 H, CH2 β to S), 2.72 (s, 6 H,
S-CH3), 3.27 (t, J = 6.9 Hz, 4 H, CH2 α to S), 4.16 (t, J = 5.8 Hz,
4 H, CH2 γ to S), 7.04 (m, 4 H, ring CH pos. 2,2Ј,6 and 6Ј), 7.55
(m, 4 H, ring CH pos. 3,3Ј,5 and 5Ј) ppm.
S,SЈ-[1,5-Naphthylenebis(1-oxy-3-propyl)]bis(isothiouronium)
Di-
(methanesulfonate) (2d): The product was synthesised from 2c fol-
lowing the same procedure as for 3d; yield 79.6%; m.p. 209–210 °C.
1H NMR [CD3CN/D2O (3:1), 200 MHz]: δ = 2.46 (p, J = 6.0 Hz,
4 H, CH2 β to S), 2.82 (s, 6 H, S-CH3), 3.54 (t, J = 6.8 Hz, 4 H,
CH2 γ to S), 4.42 (t, J = 5.5 Hz, 4 H, CH2 α to S), 7.14 (d, J=
7.8 Hz, 2 H, ring CH pos. 4 and 8), 7.59 (t, J = 8.2 Hz, 2 H, ring
CH pos. 3 and 7), 8.02 (d, J = 8.5 Hz, 2 H, CH pos. 2 and 6) ppm.
13C NMR [CD3CN/D2O (3:1), 50 MHz]: δ = 28.2 (CH2 β to S),
28.2 (CH2 α to S), 38.9 (S-CH3), 66.4 (CH2 γ to S), 106.4 (ring CH
pos. 2 and 6), 114.6 (ring CH pos. 4 and 8), 126.0 (ring CH pos. 3
and 7), 126.7 (ring C pos. 9 and 10), 154.3 (ring CO), 171.7 [S-
C(NH2)2+] ppm.
[2,20-Dioxo-13,16,110,113-tetraaza-3,10,12,19-tetraoxa-7,15-dithia-
1(1,8)-cyclotetradecana-11(1,4)-benzenaeicosacyclophano-
11,16,18,113-tetraenato(2–)-κ4N]nickel(II) (NiPh): The reaction was
carried out under argon. 5Ni (0.152 g, 0.25 mmol) and 3e (0.058 g,
0.25 mmol) were dissolved in DMF (10 mL) at 50 °C. Cs2CO3
(0.25 g, 0.767 mmol) was then added and stirring was continued for
5 h at 50 °C. After this time, concentrated hydrochloric acid (1 mL)
in water (50 mL) was added. The orange precipitate was then fil-
tered off and washed several times with small amounts of water.
The dry solid was dissolved in dichloromethane. The solution was
washed with water and the organic layer was dried with Na2SO4.
The product was purified on silica gel using CH2Cl2/MeOH (99:1)
as an eluent. Further purification was carried out by crystallisation
from CH2Cl2/MeOH upon slow evaporation of solvent. The prod-
uct was dried in vacuo over P2 O5 ; yield 0.032 g (20 %).
C28H36N4NiO6S2 (647.43): calcd. C 51.94, H 5.60, N 8.65; found
C 51.74, H 5.51, N 8.89. MS (FD, CH2Cl2): m/z = 646.1
[C28H36N4O6S2Ni – e–], 669.3 (C28H36N4O6S2Ni + Na+). 1H NMR
(CD3Cl, 200 MHz): δ = 2.10 (br. p, J = 6.0 Hz, 4 H, CH2 β to
CO2), 2.80 (t, J = 7.1 Hz, 4 H, CH2 β to O-CAr), 2.98 (t, J = 8.1 Hz,
4 H, CH2 γ to CO2), 3.16 (br. s), 3.35 (br. s, 8 H, N-CH2CH2-N),
4.07 (t, J = 7.0 Hz, 4 H, CH2 α to O-CAr), 4.31 (br. t, J = 4.6 Hz,
4 H, CH2 α to CO2), 7.6 (s, 4 H, CHN) ppm.
1,4-Bis(2-sulfanylethoxy)benzene (3e): 3d (0.528 g, 1 mmol) was dis-
solved in deoxygenated water (5 mL) under argon. Under vigorous
stirring, the mixture was treated with NaOH (1.15 g, 28.8 mmol).
The temperature was kept below 20 °C. After 1 h, concentrated hy-
drochloric acid (4 mL) was added keeping the temperature below
40 °C. After few minutes the precipitated solid was filtered off and
washed well with deoxygenated water. The wet precipitate was
dried in vacuo over P2O5; yield 0.201 g (87.4%); m.p. 64–66 °C
1
(dec.). H NMR (CDCl3, 200 MHz): δ = 1.75 (t, J = 8.4 Hz, 2 H,
SH), 2.94 (dt, J1 = 6.4, J2 = 8.4 Hz, 4 H, CH2-S-), 4.14 (t, J =
6.4 Hz, 4 H, CH2-O-), 6.92 (s, 4 H, ring CH) ppm. 13C NMR
(CDCl3, 50 MHz): δ = 24.3 (CH2-S-), 70.6 (CH2-O-), 116.1 (ring
CH), 153.0 (ring CO) ppm.
[2,20-Dioxo-13,16,110,113-tetraaza-3,10,12,19-tetraoxa-7,15-dithia-
1(1,8)-cyclotetradecana-11(1,4)-benzenaeicosacyclophano-
11,16,18,113-tetraenato(2–)-κ4N]copper(II) (CuPh): This compound
was synthesised from 5Cu and 3e following the procedure for NiPh;
yield 27.8%. C28H36CuN4O6S2 (652.28): calcd. C 51.56, H 5.56, N
4,4Ј-Bis(3-sulfanylpropoxy)biphenyl (1e): The compound was syn-
thesised from 1d following the procedure for 3e; yield 81.2%; m.p.
119–121 °C. IR (nujol): ν = 2550 (w), 1605 (m) cm–1. 1H NMR
˜
(CD2Cl2, 400 MHz): δ = 1.46 (t, J = 8.3 Hz, 2 H, SH), 2.08 (p, J
486
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 479–488

The Role of the C–H···π Interactions in Cyclisation Reactions
8.59; found C 51.51, H 5.53, N 8.76. MS (FD, CH2Cl2): m/z = values during the refinement or no reasonable model of disorder
651.2 [C28H36N4O6S2Cu – e–], 674.3 (C28H36N4O6S2Cu + Na+).
could be found (due to the low quality of crystals). All hydrogen
atoms were placed in idealised positions. In the case of CuPh struc-
ture, the AFIX 66 instruction was used during the refinement to
restrain the geometry of aromatic rings.
[2,21-Dioxo-13,16,110,113-tetraaza-3,10,13,20-tetraoxa-6,17-dithia-
1(1,8)-cyclotetradecana-11(1,4),12(4,1)-dibenzenaeicosacyclophano-
11,16,18,113-tetraenato(2–)-κ4 N]nickel(II) (NibiPh): The compound
was synthesised from 4Ni and 1e following the procedure for NiPh;
yield 29%. C34H40N4NiO6S2 (723.53): calcd. C 56.44, H 5.57, N
7.74, S 8.86; found C 56.67, H 5.80, N 7.99, S 9.05. MS (FD,
CCDC-770713 (for CuPh), -770714 (for NibiPh), -770715 (for
NiNaph), and -770716 (for NiPh) contain the supplementary crys-
tallographic 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.
1
CH2Cl2): m/z = 722.2 (C34H40N4NiO6S2 – e–). H NMR (CDCl3,
200 MHz): δ = 2.08 (br. p, J = 6.2 Hz, 4 H, CH2 β to O–CAr), 2.76
(t, J = 6.4 Hz, 4 H, CH2 β CO2), 2.85 (t, J = 7.0 Hz, 4 H, CH2 γ
to O-CAr), 3.03 (br. s, 8 H, N-CH2CH2-N), 4.10 (t, J = 5.8 Hz, 4
H, CH2 α to O-CAr), 4.32 (t, J = 6.4 Hz, 4 H, CH2 α to CO2), 6.95
(m, 4 H, biphenyl ring CH pos. 2,2Ј,6 and 6Ј), 7.49 (m, 4 H, bi-
phenyl ring CH pos. 3,3Ј,5 and 5Ј), 7.63 (s, 4 H, ring CHN) ppm.
13C NMR (CDCl3, 125 MHz): δ = 28.8 (CH2 β to O-Car.), 30.0
(CH2 γ to O-CAr), 31.7 (CH2 β to CO2), 58.8 (N-CH2CH2-N), 63.4
(CH2 α to CO2), 66.3 (CH2 α to O-CAr), 98.3 (endocyclic, 4 °C),
115.3 (biphenyl ring CH pos. 3,3Ј,5 and 5Ј), 127.8 (biphenyl ring
CH pos. 2,2Ј,6 and 6Ј), 133.4 (biphenyl ring CH pos. 1 and 1Ј),
155.0 (endocyclic CHN), 158.1 (biphenyl ring CO pos. 4 and 4Ј),
167.6 (C=O) ppm.
CuPh: C28H36CuN4O6S2; molecular weight: 652.27 a.u.; T = 100(2)
K; monoclinic; space group, P21/c; unit cell dimensions, a =
17.345(6) Å, b = 9.2771(17) Å, c = 37.075(9) Å, α = 90°, β =
100.59(2)°, γ = 90°, V = 5864(3) Å3; Z = 8; dcalc = 1.478 gcm–3;
absorption coefficient, μ = 0.936 mm–1; F(000) = 2728; crystal size:
0.28ϫ0.09ϫ0.07 mm3; θ range for data collection: 2.65–25.00°; in-
dex ranges: –16ϽhϽ20, –11ϽkϽ11, –44ϽlϽ37; reflections col-
lected: 22714/unique: 9440 (Rint = 0.2644); absorption correction:
muti-scan; refinement method: full-matrix least-squares on F2;
goodness-of-fit on F2, GooF = 0.967; data/restraints/parameters,
9440/16/306; final R indices [IϾ2σ(I)]: R1 = 0.1893, wR2 = 0.3747;
2
R indices (all data): R1 = 0.5007, wR2 = 0.4560; weight: 1/[σ2(Fo
)
+ (0.0775P)2 + 0.28P], where P = [max(Fo2,0) + 2Fc ]/3; largest
2
[2,22-Dioxo-13,16,110,113-tetraaza-3,11,13,21-tetraoxa-7,17-dithia-
1(1,8)-cyclotetradecana-12(1,5)-naphthalenadocosacyclophano-
11,16,18,113-tetraenato(2–)-κ4N]nickel(II) (NiNaph): This com-
pounds was obtained from 5Ni and 2e using the procedure for
NiPh; yield 10.2%. C34H42N4NiO6S2 (725.54): calcd. C 56.28, H
5.83, N 7.72; found C 56.21, H 5.78, N 7.83. MS (FD, CH2Cl2):
m/z = 724.1 [C34H42N4O6S2Ni – e–], 747.2 (C34H42N4O6S2Ni +
diffraction peak and hole: 1.038 and –1.088 eÅ–3.
NibiPh: C34H40N4NiO6S2; molecular weight: 723.53 a.u.; T =
100(2) K; monoclinic; space group, P21/c; unit cell dimensions, a =
12.1749(5) Å, b = 20.5721(10) Å, c = 26.5008(11) Å, α = 90°, β =
94.916(4)°, γ = 90°, V = 6613.1(5) Å3; Z = 8; dcalc = 1.453 gcm–3;
absorption coefficient, μ = 0.765 mm–1; F(000) = 3040; crystal size:
0.35ϫ0.10ϫ0.09 mm3; θ range for data collection: 2.60–28.70°; in-
dex ranges: –16ϽhϽ16, –27ϽkϽ27, –35ϽlϽ35; reflections col-
lected: 98058/unique: 16179 (Rint = 0.1615); absorption correction:
muti-scan; refinement: full-matrix least-squares on F2; goodness-
of-fit on F2, GooF = 0.832; data/restraints/parameters, 16179/144/
748; final R indices [IϾ2σ(I)]: R1 = 0.0752, wR2 = 0.1797; R in-
dices (all data): R1 = 0.2056, wR2 = 0.2043; weight: 1/[σ2(Fo2) +
1
Na+). H NMR (CDCl3, 500 MHz): δ = 2.00 (br. p, J = 6.2 Hz, 4
H, CH2 β to CO2), 2.23(p, J = 6.8 Hz, 4 H, CH2 β to O-CAr), 2.74
(t, J = 7.2 Hz, 4 H, CH2 γ CO2), 2.80 (br. s, 8 H, N-CH2CH2-N-),
2.85 (t, J = 7.1 Hz, 4 H, CH2 γ to O-CAr), 4.23 (t, J = 6.3 Hz, 4
H, CH2 α to O-CAr), 4.26 (t, J = 5.3 Hz, 4 H, CH2 α to CO2), 6.86
(d, J = 7.6 Hz, 2 H, ring CH pos. 4 and 8), 7.64 (s, 4 H, ring CHN),
7.36 (t, J = 8.0 Hz, 2 H, ring CH pos. 3 and 7), 7.79 (d, J = 8.5 Hz,
2 H, ring CH pos. 2 and 6) ppm. 13C NMR (CDCl3, 125 MHz): δ
= 29.1 (CH2 β to O-CAr), 29.5 (CH2 γ to O-CAr), 29.5 (CH2 γ to
2
(0.0775P)2 + 0.28P], where P = [max(Fo2,0) + 2Fc ]/3; largest dif-
fraction peak and hole: 2.672 and – 1.061 eÅ–3.
O-CAr), 29.6 (CH2 β to CO2), 58.3 (N-CH2CH2-N), 61.8 (CH2
α
NiNaph: C34H42N4NiO6S2; molecular weight: 725.55 a.u.; T =
100(2) K; triclinic; space group, P1; unit cell dimensions, a =
to CO2), 66.4 (CH2 α to O-CAr), 98.0 (endocyclic, 4 °C), 105.3 (ring
CH pos. 2 and 6), 114.1 (ring CH pos. 4 and 8), 125.4 (ring CH
pos. 3 and 7), 126.5 (naphthalene C pos. 9 and 10), 154.3 (naphth-
alene ring CO), 154.6 (endocyclic CHN), 167.6 (C=O) ppm.
¯
11.3728(14) Å, b = 11.8373(12) Å, c = 12.7849(12) Å, α =
88.970(8)°, β = 77.895(9)°, γ = 83.531(9)°, V = 1672.1(3) Å3; Z =
2; dcalc = 1.441 gcm–3; absorption coefficient, μ = 0.756 mm–1
;
F(000) = 764; crystal size: 0.32ϫ0.14ϫ0.08 mm3; θ range for data
collection: 2.67– 25.00°; index ranges: –13ϽhϽ13, –14ϽkϽ14,
X-ray: Single crystal X-ray measurements for NiPh, CuPh, NibiPh
and NiNaph were performed on a Kuma KM4CCD κ-axis dif-
fractometer with graphite-monochromated Mo-Kα radiation (λ =
0.71073 Å) equipped with an Oxford Cryosystems nitrogen gas-
flow LT attachment. Crystals were positioned at 62 mm from the
KM4CCD camera. The data were corrected for Lorentz and pola-
risation effects. Data reduction and analysis were carried out with
the Oxford Diffraction Ltd. suite of programs. All structures were
solved by direct methods using SHELXS-97[16] and refined using
SHELXL-97.[16] The refinement was based on F2 for all reflections
except those with very negative F2. Weighted R factors (wR) and
all goodness-of-fit (GooF) values are based on F2. Conventional
R factors are based on F with F set to zero for negative F2. The
Fo2 Ͼ2σ(Fo2) criterion was used only for calculating R factors and
is not relevant to the choice of reflections for the refinement. The
R factors based on F2 are about twice as large as those based on
F. Scattering factors were taken from International Tables for Crys-
tallography.[17] Most non-hydrogen atoms were refined anisotropi-
cally except for some for which their ADPs were not going to real
–15 Ͻ l Ͻ 15; reflections collected: 26215/unique: 5886 (Rint
=
0.0519); absorption correction: muti-scan; refinement method: full-
matrix least-squares on F2; goodness-of-fit on F2, GooF = 0.786;
data/restraints/parameters, 5886/0/424; final R indices [IϾ2σ(I)]:
R1 = 0.0292, wR2 = 0.0468; R indices (all data): R1 = 0.0622,
wR2 = 0.0503; weight: 1/[σ2(Fo2) + (0.0775P)2 + 0.28P], where P
2
= [max(Fo2,0) + 2Fc ]/3; largest diffraction peak and hole: 0.353
and –0.271 eÅ–3.
NiPh: C28H36N4NiO6S2; molecular weight: 647.44 a.u.; T = 100(2)
¯
K; triclinic; space group, P1; unit cell dimensions, a = 6.6872(18) Å,
b = 14.941(4) Å, c = 15.205(3) Å, α = 100.901(19)°, β = 97.514(18)°,
γ = 95.49(2)°, V = 1467.6(6) Å3; Z = 2; dcalc = 1.465 gcm–3; absorp-
tion coefficient, μ = 0.852 mm–1; F(000) = 680; crystal size:
0.18ϫ0.14ϫ0.09 mm3; θ range for data collection: 2.76–25.00°; in-
dex ranges: –7 Ͻh Ͻ7, –17ϽkϽ17, –18ϽlϽ18; reflections col-
lected: 14598/unique: 5139 (Rint = 0.2699); absorption correction:
muti-scan; refinement method: full-matrix least-squares on F2;
Eur. J. Inorg. Chem. 2011, 479–488
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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487

K. Woz´niak et al.
FULL PAPER
goodness-of-fit on F2, GooF = 0.926; data/restraints/parameters,
[3] D. H. Busch, S. C. Jackels, R. W. Callahan, J. Grzybowski,
L. L. Zimmer, M. Kojima, D. J. Olszanski, W. P. Schammel,
J. C. Stevens, K. A. Holter, J. Mocak, Inorg. Chem. 1981, 20,
2834–2844.
5139/27/199; final R indices [IϾ2σ(I)]: R1 = 0.1320, wR2 = 0.2249;
R indices (all data): R1 = 0.3367, wR2 = 0.3075; weight: 1/[σ2(Fo
)
2
+ (0.0775P)2 + 0.28P], where P = [max(Fo2,0) + 2Fc ]/3; largest
2
[4] J. Chen, N. Ye, N. W. Alcock, D. H. Busch, Inorg. Chem. 1993,
diffraction peak and hole: 0.826 and –0.475 eÅ–3.
32, 904–910.
[5] D. H. Busch, G. G. Christoph, L. L. Zimmer, S. C. Jackels, J.
Grzybowski, R. W. Callahan, M. Kojima, K. A. Holter, J. Mo-
cak, N. Herron, M. Y. Chavan, W. P. Schammel, J. Am. Chem.
Soc. 1981, 103, 5107–5114.
[6] K. Szczepaniak, U. E. Wawrzyniak, J. Kowalski, I. Mames, R.
Bilewicz, P. Kalicki, B. Korybut-Daszkiewicz, Inorg. Chem.
2010, 49, 4491–4498.
[7] A. Wieckowska, R. Bilewicz, S. Domagała, K. Wozniak, B. Ko-
rybut-Daszkiewicz, A. Tomkiewicz, J. Mrozinski, Inorg. Chem.
2003, 42, 5513–5522.
[8] S. Domagała, A. Wieckowska, J. Kowalski, A. Rogowska, J.
Szydłowska, B. Korybut-Daszkiewicz, R. Bilewicz, K. Woz-
niak, Chem. Eur. J. 2006, 12, 2967–2981.
Computational Details: The geometry optimisations, calculations of
vibrational frequencies and population analyses were carried out
with the ADF2008 package[13] by means of DFT methods with the
GGA BP86 functional and ZORA approximation[18] using frozen-
core (for optimisation and frequencies) and all-electron (for exact
energy calculation) TZP (triple-ζ with polarisation function) basis
set as implemented in the package. The vibrational frequencies
were computed within the harmonic approximation. The Cartesian
coordinates for optimised geometries are presented in the Support-
ing Information.
Supporting Information (see also the footnote on the first page of
this article): Geometrical parameters for selected weak intermo-
lecular interactions in the studied crystal structures, Cartesian co-
ordinates for conformers K1, K2 and K3 and selected proton and
carbon NMR spectra in CD3Cl solution.
[9]
A. Rybka, R. Kolin´ski, J. Kowalski, R. Szmigielski, S. Doma-
gała, K. Woz´niak, A. Wieckowska, R. Bilewicz, B. Korybut-
˛
Daszkiewicz, Eur. J. Inorg. Chem. 2007, 172–185.
D. H. Busch, N. W. Alcock, Chem. Rev. 1994, 94, 585–623.
[10]
[11] J. H. Cameron, M. Kojima, B. Korybut-Daszkiewicz, B. K.
Coltrain, T. J. Meade, N. W. Alcock, D. H. Busch, Inorg. Chem.
1987, 26, 427–439.
Acknowledgments
[12] M. P. Johansson, J. Olsen, J. Chem. Theory Comput. 2008, 4,
The X-ray single-crystal measurements were accomplished at the
Structural Research Laboratory (Department of Chemistry, Uni-
versity of Warsaw, Poland), established with a financial support
from the European Regional Development Fund (grant number
WKP_1/1.4.3./1/2004/72/72/165/2005/U, Sectoral Operational Pro-
gramme, Improvement of the Competitiveness of Enterprises,
2004–2006). K. W. thanks the Foundation for Polish Science for
financial support within the Mistrz program. This work was sup-
ported through a grant from the Ministry of Science and Higher
Education (N204 074 32/2022). The authors gratefully acknow-
ledge the Wrocław Centre for Networking and Supercomputing in
Wrocław for providing computer facilities. R. K. would like to
thank the Ministry of Science and Higher Education for a student-
ship.
1460–1471.
[13] G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. Fon-
seca Guerra, E. J. Baerends, J. G. Snijders, T. Ziegler, J. Com-
put. Chem. 2001, 22, 931–967.
[14] For recent examples, see: a) M. Lein, J. F. Dobson, E. K. U.
Gross, J. Comput. Chem. 1999, 20, 12–22; b) H. Valdes, J. A.
Sordo, J. Comput. Chem. 2002, 23, 444–455; c) F. Tran, J. We-
ber, T. A. Wesolowski, F. Cheikh, Y. Ellinger, F. Pauzat, J.
Phys. Chem. B 2002, 106, 8689–8696; d) L. Zhechkov, T. Heine,
S. Patchkovskii, G. Seifert, H. A. Duarte, J. Chem. Theory
Comput. 2005, 1, 841–847.
[15] U. Wawrzyniak, M. Woz´ny, J. Kowalski, S. Domagała, E.
Maicka, R. Bilewicz, K. Woz´niak, B. Korybut-Daszkiewicz,
Chem. Eur. J. 2008, 15, 149–167.
[16] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
[17] H. Fuess (Ed.), International Tables for Crystallography, vol.
C, Mathematical, Physical and Chemical Tables, 1st online ed.,
Chester, International Union of Crystallography, 2006.
[1] B. Korybut-Daszkiewicz, A. Wieckowska, R. Bilewicz, S. Do-
˛
magała, K. Woz´niak, J. Am. Chem. Soc. 2001, 123, 9356–9366. [18] J. Li, G. Schreckenbach, T. Ziegler, J. Am. Chem. Soc. 1995,
[2] B. Korybut-Daszkiewicz, A. Wieckowska, R. Bilewicz, S. Do-
˛
117, 486–494.
magała, K. Woz´niak, Angew. Chem. Int. Ed. 2004, 43, 1668–
1672; Angew. Chem. 2004, 116, 1700–1704.
Received: July 28, 2010
Published Online: December 22, 2010
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