Synthesis and characterisation of pendant-arm alcohol derivatives of [9]aneN2S and complexation with CuII ([9]aneN2S = 1-thia-4,7-diazacyclononane)

Article abstract of DOI:10.1039/a801552j

An improved detosylation of 4,7-bis(tolyl-p-sulfonyl)-1-thia-4,7-diazacyclononane to give the free amine [9]aneN₂S has been accomplished using Li/NH₃ or HBr/acetic acid. Reaction of [9]aneN₂S with ethylene oxide, 1,1-dimethylethylene oxide and methylenecyclohexane oxide in alcoholic solution affords the potentially pentadentate ligands 4,7-bis(hydroxyethyl)-1-thia-4,7-diazacyclononane (H₂L¹), 4,7-bis(2-hydroxy-2-methylpropyl)-1-thia-4,7-diazacyclononane (H₂L²) and 4,7-bis(2-cyclohexyl-2-hydroxymethyl)-1-thia-4,7-diazacyclononane (H₂L³) respectively. The copper(II) complexes of these ligands have been prepared and reveal that increasing the steric bulk on the pendant arm has a marked effect upon the resultant co-ordination chemistry. Thus, the complex of H₂L¹ shows a dimeric structure [Cu₂(HL¹)₂][PF₆]₂ 1 in which one of the hydroxy groups has been deprotonated. With H₂L² two complexes can be isolated: the dimer [Cu₂(HL₂)₂][PF₆]₂ 2 and the monomer [Cu(HL₂)][PF₆] 3. In contrast, with H₂L³ only the monomer [Cu(HL³)][PF₆] 4 could be isolated. Single crystal structures of 1 and 3 have been determined. Magnetochemistry of 1 indicates that the two copper(II) centres are essentially non-coupled. ? Non-SI units employed: μ_B ≈ 9.27 × 10^-24 J T^-1, G = 10^-4 T.

Full text of DOI:10.1039/a801552j

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Synthesis and characterisation of pendant-arm alcohol derivatives of
[9]aneN2S and complexation with CuII ([9]aneN2S ؍ 1-thia-4,7-diaza-
cyclononane)†
Alexander J. Blake,a Jonathan P. Danks,a Andrew Harrison,b Simon Parsons,b Paul Schooler,b
Gavin Whittakerb and Martin Schröder*,a
a Department of Chemistry, The University of Nottingham, Nottingham, UK NG7 2RD
b Department of Chemistry, The University of Edinburgh, Edinburgh, UK EH9 3JJ
An improved detosylation of 4,7-bis(tolyl-p-sulfonyl)-1-thia-4,7-diazacyclononane to give the free amine
[9]aneN2S has been accomplished using Li/NH3 or HBr/acetic acid. Reaction of [9]aneN2S with ethylene oxide,
1,1-dimethylethylene oxide and methylenecyclohexane oxide in alcoholic solution affords the potentially
pentadentate ligands 4,7-bis(hydroxyethyl)-1-thia-4,7-diazacyclononane (H2L1), 4,7-bis(2-hydroxy-2-methyl-
propyl)-1-thia-4,7-diazacyclononane (H2L2) and 4,7-bis(2-cyclohexyl-2-hydroxymethyl)-1-thia-4,7-diazacyclo-
nonane (H2L3) respectively. The copper() complexes of these ligands have been prepared and reveal that
increasing the steric bulk on the pendant arm has a marked effect upon the resultant co-ordination chemistry.
Thus, the complex of H2L1 shows a dimeric structure [Cu2(HL1)2][PF6]2 1 in which one of the hydroxy groups has
been deprotonated. With H2L2 two complexes can be isolated: the dimer [Cu2(HL2)2][PF6]2 2 and the monomer
[Cu(HL2)][PF6] 3. In contrast, with H2L3 only the monomer [Cu(HL3)][PF6] 4 could be isolated. Single crystal
structures of 1 and 3 have been determined. Magnetochemistry of 1 indicates that the two copper() centres are
essentially non-coupled.
H2N
The co-ordination chemistry of the nine-membered ring crowns
SH
[9]aneN3,1,2 [9]aneN2S,3,4 [9]aneNS2 and [9]aneS3 has been
investigated over recent years. The synthesis of pendant arm
derivatives of [9]aneN3 has led to the isolation of an enormous
range of highly stable complexes.6,7 However, the vast majority
of these systems are based on trifunctionalisation of [9]aneN3,
leading to octahedral co-ordination to the metal centre. In con-
trast, there is relatively little published work on the synthesis of
pendant arm derivatives of [9]aneN2S leading to the formation
of potential five-co-ordinate metal complexes.8–10 Such com-
plexes are of particular interest since they lead to the possibility
of binding and activation of small molecules at the co-
ordinatively unsaturated metal centre.11 We report herein an
alternative route to [9]aneN2S and show that increasing the
steric bulk of the ligating arms has a marked effect upon the
co-ordination chemistry of the copper() complexes.
3
5
HCl
HCl
NH2
Cl
H2O/NaOH
TsCl/Et3N
H2O/Ether
H2N
S
NH2
TsN
H
S
S
NTs
H
NaOEt
TsO
OTs
TsN
NTs
TsN
Na
NTs
Na
dmf
S
Results and Discussion
Ligand synthesis
HBr/acetic acid
NH
The compound [9]aneN2S was first reported by Hancock and
co-workers12 and the synthesis of the ditosylated macrocycle
has since been improved (Scheme 1).12,13 The final step involves
detosylation of the protected macrocycle using the procedure
of Koyama and Yoshino.14 This entails a lengthy (48–72 h)
reflux with HBr/acetic acid and in our experience can result
in appreciable decomposition and inconsistent yields of the
desired material. We therefore decided to utilise a reductive
detosylation with lithium and liquid ammonia.15 The reaction is
complete in minutes and the crude free base is purified by con-
version into the HBr salt. The yields for this process are 60–70%
providing a short reaction time is observed: reaction times of
several hours lead to the isolation of a substantial quantity
of a product which, although it remains unidentified, probably
results from the degradation of the N2S-donor macrocyclic
ring.
HN
S
Scheme 1 Ts = Toluene-p-sulfonyl (tosyl)
We subsequently returned to the question of the use of
HBr/acetic acid for the deprotection of tosylated mixed N/S-
substituted crowns. In our hands, this method can be success-
fully used for the preparation of [9]aneN2S, although yields of
detosylated product can vary enormously from 0 up to 75%.
In parallel work, we have found this method of detosylation to
be consistently successful for the preparation of [9]aneNS2.16
Therefore, over a period of many months we monitored a
variety of commercially available batches of HBr/acetic acid
and found that yields of detosylated product varied according
to the source of HBr/acetic acid. In our hands, HBr/acetic acid
from Fluka was invariably the most successful reagent, suggest-
† Non-SI units employed: µB ≈ 9.27 × 10Ϫ24 J TϪ1, G = 10Ϫ4 T.
J. Chem. Soc., Dalton Trans., 1998, Pages 2335–2340
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O
R
R
HO
OH
HN
NH
N
N
R = H, Me
R2
R
R
R
R
S
S
=
HO
OH
N
N
N
N
S
H2L1
HO
Me Me
OH
Me Me
N
S
H2L2
HO
OH
N
Fig. 1 Crystal structure of [Cu2(HL1)2][PF6]2 1 with numbering
scheme adopted. Only one component of each disordered atom is
S
shown. The suffix A indicates the symmetry operation Ϫx, Ϫy, 1 Ϫ z
H2L3
Scheme 2
Table 1 Selected bond lengths (Å) and angles (Њ) for compound 1
ing that the level of purity and/or the presence of trace con-
taminants critically influence the detosylation to [9]aneN2S.
Interestingly, detosylation to [9]aneNS2 appears, in our hands,
not to be so dependent on the HBr/acetic acid source.
Cu(1) ؒ ؒ ؒ Cu(1A)
Cu(1)᎐O(43)
Cu(1)᎐O(43A)
Cu(1)᎐N(7)
2.941(2)
1.939(4)
1.931(4)
2.043(6)
Cu(1)᎐N(4)
Cu(1)᎐S(1)
Cu(1)᎐O(73)
2.003(6)
2.648(2)
2.757(6)
The reaction of secondary amines with epoxides to give alco-
hols is well documented.7,17 In the case of substituted epoxides
nucleophilic attack occurs at the least hindered carbon of the
three-membered ring and affords tertiary alcohols. The reaction
of [9]aneN2S with ethylene oxide, 1,1-dimethylethylene oxide
and methylenecyclohexane oxide (prepared by the route of
Corey and Chaykovsky18) in EtOH leads to the isolation of
H2L1, H2L2 and H2L3 in good yields (Scheme 2). Increasing the
steric bulk on the epoxides is known to decrease the rate of
the ring-opening reaction.19 Thus, reaction of [9]aneN2S with
ethylene oxide occurs in 20 h at room temperature, whereas
with 1,1-dimethylethylene oxide the reaction takes 10 d. No
reaction between [9]aneN2S and methylenecyclohexane oxide
was observed at room temperature but could be accomplished
in 4 d under reflux.
Cu(1)᎐O(43A)᎐Cu(1A)
Cu(1)᎐O(43)᎐Cu(1A)
O(43)᎐Cu(1)᎐O(43A)
O(43A)᎐Cu(1)᎐N(4)
O(43)᎐Cu(1)᎐N(4)
98.9(2)
98.9(2)
81.1(2)
162.1(2)
86.5(2)
101.9(2)
O(43)᎐Cu(1)᎐N(7)
N(4)᎐Cu(1)᎐N(7)
O(43)᎐Cu(1)᎐S(1)
N(4)᎐Cu(1)᎐S(1)
N(7)᎐Cu(1)᎐S(1)
164.9(2)
86.9(2)
108.4(2)
85.7(2)
84.6(2)
O(43A)᎐Cu(1)᎐N(7)
Symmetry operator: A Ϫx, Ϫy, 1 Ϫ z.
lengths and bond angles are given in Table 1. The two copper()
centres are separated by 2.941(2) Å and are bridged by two
alkoxides which result from the deprotonation of an alcohol
arm from each ligand. The Cu2O2 unit is planar. The geometry
about each CuII is Jahn–Teller distorted octahedral, with two
aza nitrogen and two alkoxide oxygens forming the close
equatorial positions. The axial positions are occupied by the
relatively poorly σ-donating sulfur and alcohol oxygen atoms.
Diffraction quality crystals were obtained for complex 3 by
diffusion of Et2O vapour into a solution of the complex in
MeCN. The structure determination of the complex confirmed
it to be the monomer [Cu(HL2)][PF6] (Fig. 2). Selected bond
lengths and bond angles for 3 are given in Table 2. The geom-
etry around the CuII is a distorted square-based pyramid, with
the two aza atoms and the two oxygen atoms forming the base
of the square, and the sulfur atom of the macrocyclic ring at the
apical site. One of the oxygen atoms is deprotonated and forms
an alkoxide interaction with the copper centre. The alcohol and
alkoxide donors lie at the same distance from the CuII, but this
is ascribed to disorder which causes scrambling of the alkoxide
and alcohol ligands. It was possible to locate the hydroxy
hydrogen H(45) [on O(45)] from a circular Fourier-difference
synthesis, while the position of H(75) [on O(75)] was not clear;
H(45) is therefore included in the model to represent one com-
ponent of the disorder, possibly the major one. Molecules
interact through pairwise hydrogen bonds [O(45)᎐H(45) ؒ ؒ ؒ
O(75) (Ϫx, 2 Ϫ y, Ϫz)] between centrosymmetrically related
molecules.
Metal complexation
Reaction of H2L1 with Cu(NO3)2ؒ3H2O followed by counter-
ion exchange with an excess of NH4PF4 afforded a green
complex (1). With H2L2 the same procedure produced a
black material, which on elution through a Sephadex column
afforded a green (2) and a blue product (3). With H2L3 a single
blue complex was obtained (4). Elemental analytical data for
the four complexes indicate a stoichiometry [Cu(HL)][PF6]
(L = L1, L2 or L3) in each case which suggests that deprotonation
of one of the alcohol arms has occurred leading to an alkoxide
interaction with CuII. The loss of a proton to form a co-
ordinated alkoxide is unusual for a metal() cation, as a metal()
cation is usually required to render the alcohol sufficiently
acidic.2,7,20 The FAB mass spectrum of complex 1 shows a peak
at m/z = 592 assigned to [Cu2(HL1)2 ϩ 1]ϩ indicating an overall
binuclear structure, while the spectrum for the green complex 2
also indicates a dimeric structure. This evidence supports the
formulation [Cu2(HL)2][PF6]2 for these complexes. The FAB
mass spectra of the blue complexes 3 and 4 do not show peaks
for a dimeric species, but molecular ions for monomeric 1:1
metal:ligand complexes.
Temperature-dependent susceptibility measurements on a
sample of the complex were carried out in the range 4–300 K
using a SQUID magnetometer. Fig. 3 shows plots of effective
moment (µeff) vs. temperature T and of susceptibility (χm) versus
T for [Cu2(HL1)2][PF6]2 1. The effective moment (µeff) was
Diffusion of Et2O vapour into a MeCN solution of the com-
plex 1 afforded deep green crystals suitable for X-ray analysis.
The single crystal determination confirms the dimeric structure
for the product [Cu2(HL1)2][PF6]2 (Fig. 1). Selected bond
2336
J. Chem. Soc., Dalton Trans., 1998, Pages 2335–2340

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Fig. 2 Crystal structure of [Cu(HL2)][PF6] 3 with numbering scheme
adopted. Only one component of each disordered atom is shown
Table 2 Selected bond lengths (Å) and angles (Њ) for compound 3
Cu᎐S(1)
Cu᎐N(7)
Cu᎐O(75)
2.502(4)
2.031(10)
1.948(9)
Cu᎐N(4)
Cu᎐O(45)
2.037(9)
1.938(10)
S(1)᎐Cu᎐N(4)
S(1)᎐Cu᎐O(45)
N(4)᎐Cu᎐N(7)
N(4)᎐Cu᎐O(75)
O(45)᎐Cu᎐O(75)
88.1(3)
105.1(3)
84.9(4)
160.9(4)
83.1(3)
S(1)᎐Cu᎐N(7)
S(1)᎐Cu᎐O(75)
N(4)᎐Cu᎐O(45)
N(7)᎐Cu᎐O(45)
89.3(3)
106.4(3)
83.5(4)
161.1(4)
O(45)᎐Cu᎐O(75) 103.9(3)
Fig. 3 Plots of (a) χm vs. temperature (ؒ ؒ ؒ obtained by modelled
Bleaney–Bowers expression21 for S1 = S2 = ¹; points are experimental
Table 3 Electronic spectrophotometric data
¯
²
data) and (b) of µeff vs. temperature for [Cu2(HL1)2][PF6]2 1
Complex
Colour
λmax/nm
εmax/Ϫ1 cmϪ1
tetragonally distorted octahedral copper complex, with a λmax
at 683 nm, and is similar to that of 2, implying that 1 and 2 have
similar geometries. The spectrum of the monomeric blue com-
plex 3 by contrast has a λmax at 630 nm, which is very similar to
that of 4 suggesting that the latter is also monomeric (Fig. 4).
Current work is aimed at developing this chemistry further
and to investigate further redox and magnetochemical proper-
ties of these and related systems.
1
2
3
4
Green
Green
Blue
683
668
630
639
85
81
56
70
Blue
measured to be 1.65 µB per Cu at 300 K. This is reasonably close
to the theoretical spin only (µSO) moment of 1.73 µB for a
mononuclear species, though due to orbital contributions the
effective magnetic moment is normally in the range 1.9–2.2 µB.22
The magnetic susceptibility χm decreases rapidly with increas-
ing temperature and fitting the data by the Bleaney–Bowers
equation21 gives a value for 2J of Ϫ0.001 cmϪ1 (R = 0.999937),
indicating that the two copper() centres are essentially non-
interacting. This is confirmed by EPR spectroscopy which
shows a signal consistent with a single paramagnetic d9 centre
with g|| = 2.15, g⊥ = 2.07. The size and sign of 2J has been demon-
strated previously to be directly dependent upon the Cu᎐O᎐Cu
angle (Φ) for hydroxo-bridged dimers, assuming planarity of
the Cu2O2 fragment.23 An angle below 97.5Њ or so results in
ferromagnetic coupling and a positive value for 2J, while for
Cu᎐O᎐Cu angles above 97.5Њ antiferromagnetic coupling is
observed. At angles approaching 97.5Њ there is little or no
exchange between the copper() centres. More recently,
Thompson et al.24 have shown that the crossover between
ferromagnetic and antiferromagnetic exchange in phenoxo-
bridged binuclear copper() centres occurs at an angle well
below 90Њ. Binuclear copper() centres with alkoxide bridges
also exhibit a general dependence of 2J upon Φ.25 The value of
Φ in 1 is 98.9(2)Њ suggesting that alkoxy-bridged binuclear CuII
species of this type show a crossover close to this angle. This is
generally consistent with experimental and theoretical studies
on alkoxo-bridged systems.24,25
Experimental
Unless otherwise stated, commercial grade chemicals were used
without further purification. Ethylene oxide and 1,1-dimethyl-
ethylene oxide were purchased from Lancaster Synthesis.
Instrumental methods
All elemental analyses were carried out by the University
of Edinburgh and the University of Nottingham analytical
services (Perkin-Elmer 240B analyser). Infrared spectra were
recorded on a Perkin-Elmer 1600 series FT-IR spectrometer,
NMR spectra (1H and 13C) on Bruker DPX300 and AC250
instruments, fast atom bombardment (FAB) and electron
impact (EI) mass spectra on VG Autospec VG7070E and
Kratos MS 50TC spectrometers and X-band EPR spectra on a
Bruker ER-2000 spectrometer employing 100 kHz modul-
ation, as frozen glasses at 77 K under a nitrogen atmosphere.
Magnetic measurements were carried out at the University of
Edinburgh using an MPMS2 SQUID magnetometer (Quantum
Design) operating with a magnetic field of 1000G. Diamagnetic
corrections were calculated using Pascal’s constants.
Preparations
The UV/VIS spectrophotometric data are summarised in
Table 3. The spectrum of the dimeric complex 1 is typical for a
1-Thia-4,7-diazacyclononane dihydrobromide, [9]aneN2Sؒ
2HBr. To a three-necked round-bottomed flask (2 l) was added
J. Chem. Soc., Dalton Trans., 1998, Pages 2335–2340
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and 2.73 (4 H, t, NCH2CH2S); δC 32.75 (NCH2CH2S), 46.08
(NCH2CH2S) and 46.84 (NCH2CH2N). EI Mass spectrum:
m/z = 147 ([M ϩ 1]ϩ).
Methylenecyclohexane oxide. Sodium hydride (8.8 g, 0.22
mol, 60% dispersion in oil) was added to a dry three-necked
round-bottomed flask (500 cm3) equipped with a condenser,
dropping funnel and a nitrogen inlet. The NaH was washed
with pentane (3 × 100 cm3) to remove the oil and after the final
washing the last traces of pentane were removed from the
flask under reduced pressure. Trimethylsulfonium iodide (50.6 g,
0.23 mol) was added to the NaH and the flask placed under a
positive nitrogen pressure. Dry dmso (120 cm3) was added via the
dropping funnel at such a rate as to keep the temperature below
50 ЊC (CAUTION: H2 is evolved). After the effervescence had
ceased, cyclohexanone (19.6 g, 20.7 cm3, 0.2 mol) was added via
the dropping funnel in one portion and the solution was stirred
at 50 ЊC for 1 h, then at room temperature for 12 h. Water (300
cm3) was added and the mixture extracted with Et2O (5 × 100
cm3). The combined extracts were dried over magnesium
sulfate and their volume reduced in vacuo to yield a very pale
yellow liquid. The crude oxirane was distilled under reduced
pressure to give a colourless liquid (14 g, 62%). NMR Spectra:
δH(CDCl3) 1.33 to 1.67 (10 H, m, cyclohexyl CH2) and 2.46 [2
H, s, (CH2)2CCH2O]; δC(CDCl3) 24.52, 24.90, 33.29 (cyclohexyl
CH2), 54.02 [(CH2)2CCH2O] and 58.53 (quaternary C). EI Mass
spectrum: m/z = 112 (Mϩ).
4,7-Bis(2-hydroxyethyl)-1-thia-4,7-diazacyclononane, H2L1.
1-Thia-4,7-diazacyclononane (300 mg, 2.0 mmol) was dissolved
in EtOH (10 cm3). To this was added ethylene oxide (300 mg,
6.8 mmol; CARE, toxic) and the resulting solution sealed and
left to stand for 20 h. Removal of the solvent in vacuo led to
the isolation of the product as a pale yellow oil (460 mg, 96%).
NMR Spectra: δH(CDCl3) 2.58–2.85 (16 H, m, NCH2CH2N,
SCH2CH2N, NCH2CH2OH) and 3.60 (4 H, t, NCH2CH2OH);
δC(CDCl3) 34.13 (SCH2), 53.97 (NCH2CH2N), 56.26 (SCH2-
CH2N) and 59.30 (NCH2CH2OH). EI Mass spectrum: m/z =
235 ([M ϩ 1]ϩ).
Fig. 4 Electronic spectra for complexes 1, 2, 3 and 4
N,NЈ-bis(tolyl-p-sulfonyl)-1-thia-4,7-diazacyclononane12,13 (10
g, 22 mmol). The flask was fitted with a mechanical stirrer,
an inlet for ammonia and an ammonia condenser. The whole
system was flushed with N2. Dry thf (250 cm3) and dry ethanol
(30 cm3) were added and the suspension was cooled in a solid
CO2–acetone bath. Liquid ammonia (1.2 l) was condensed into
the system and lithium metal (4.2 g, 0.61 mol) added over 30
min. The resulting deep blue colouration only persisted for a
few minutes. After stirring the resultant bright yellow solution
for 15 min the bath was removed and the ammonia distilled off
(CARE). Water (100 cm3) was added to the remaining solution
and solvent removed in vacuo to yield an off-white residue. The
solid was dissolved in hydrochloric acid (6 , 220 cm3, 1.32
mol), and washed with Et2O (2 × 100 cm3). The aqueous layer
was reduced in vacuo, redissolved in KOH solution (6 , 220
cm3, 1.32 mol) and extracted with CH2Cl2 (5 × 100 cm3). The
combined organic layers were dried over magnesium sulfate,
filtered, then reduced in vacuo to give the crude product as a
yellow oil. The oil was dissolved in EtOH–Et2O (2:1, 100 cm3)
and HBr (48% v/v) was added until no further precipitate
formed. The precipitate was filtered off and washed with
EtOH–Et2O (2:1) followed by Et2O to yield the product as the
HBr salt (3.21 g, 68.7%), m.p. 221–222 ЊC. NMR Spectra:
δH(D2O) 2.58 (4 H, t, J = 6.5, NCH2CH2S), 3.03 (4 H, t, J = 6.5
Hz, NCH2CH2S) and 3.33 (4 H, s, NCH2CH2N); δC(D2O) 25.11
(NCH2CH2S), 39.96 (NCH2CH2S) and 41.96 (NCH2CH2N).
4,7-Bis(2-hydroxy-2-methylpropyl)-1-thia-4,7-diazacyclo-
nonane, H2L2. This was prepared in the same way as H2L1
except that the reaction time was 10 d. Yield 386 mg, 81%. NMR
Spectra: δH(CDCl3) 2.37, 2.43 [8 H, NCH2CH2N, NCH2C-
(CH3)2OH], 2.47 (12 H, CH3), 2.79 (4 H, SCH2CH2N) and 2.86
(4 H, SCH2CH2N); δC(CDCl3) 27.68 (CH3), 34.81 (NCH2-
CH2S), 52.07 (NCH2CH2S), 56.59 (NCH2CH2N), 66.54
[NCH2C(CH3)2OH] and 70.34 [C(CH3)2OH]. EI Mass spec-
trum: m/z = 291 ([M ϩ 1]ϩ).
4,7-Bis(2-cyclohexyl-2-hydroxyethyl)-1-thia-4,7-diazacyclo-
nonane, H2L3. 1-Thia-4,7-diazacyclononane (500 mg, 3.43
mmol) and methylenecyclohexane oxide (1.6 g, 14.3 mmol)
were dissolved in EtOH (30 cm3) and the mixture refluxed for
4 d. The cooled solution was reduced in vacuo to give an oil
which was dissolved in CH2Cl2 (50 cm3) and washed with water
(5 × 50 cm3). The organic layer was dried over MgSO4 and
solvent removed to give a pale yellow oil (257 mg, 26%). NMR
Spectra: δH(CDCl3) 1.12–1.70 (20 H, s, cyclohexyl CH2), 2.49
(4 H, s, SCH2) 2.57–2.88 [12 H, m, NCH2CH2S, NCH2CH2N
and NCH2C(CH2)2OH] and 3.39 (2 H, s, OH); δC(CDCl3)
21.81, 25.80, 34.33 (cyclohexyl CH2), 36.53 (NCH2CH2S), 57.95
(NCH2CH2S), 58.85 (NCH2CH2N), 70.18 [NCH2C(CH2)2OH]
and 70.47 [C(CH2)2OH]. EI Mass spectrum: m/z = 372
([M ϩ 1]ϩ).
1-Thia-4,7-diazacyclononane. 1-Thia-4,7-diazacyclononane
dihydrobromide (1.8 g, 5.8 mmol) and sodium hydroxide (2.3 g,
58 mmol) were dissolved in water (20 cm3). Toluene (50 cm3)
was added and the resulting solution azeotroped using a Dean
and Stark apparatus until all the water was removed. The tolu-
ene was decanted off and a further portion of toluene (50 cm3)
added to the flask and the resulting solution refluxed for 1 h.
The combined organic fractions were reduced in vacuo to yield
the free base as a very pale oil (800 mg, 94%). NMR Spectra:
δH(CDCl3) 2.50–2.59 (8 H, m, NCH2CH2S and NCH2CH2N)
[Cu2(HL1)2][PF6]2 1. The compound H2L1 (50 mg, 0.2 mmol)
was dissolved in EtOH (2 cm3) and an equimolar solution of
Cu(NO3)2ؒ3H2O (62 mg, 0.2 mmol) in EtOH (2 cm3) was added
to yield immediately a deep green solution. After refrigeration
2338
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2 P. Chaudhuri and K. Wieghardt, Prog. Inorg. Chem., 1987, 25, 329.
3 J. P. Danks, N. R. Champness and M. Schröder, Coord. Chem. Rev.,
1998, in the press.
for 24 h green crystals of the product were isolated. There were
dissolved in water and were converted into the PF6Ϫ salt by the
addition of an excess of NH4PF6. A green solid was isolated
and dried in vacuo (70%) (Found: C, 27.2; H, 5.0; N, 6.2.
C10H21CuF6N2O2PS requires C, 27.2; H, 4.8; N, 6.3%). IR
spectrum (KBr disc): ν max/cmϪ1 3438s (OH), 2926m (CH),
4 U. Heinzel and R. Mattes, Polyhedron, 1991, 10, 19; A. McAuley,
D. G. Fortier, D. H. Macartney, T. W. Whitcombe and X. Chao,
J. Chem. Soc., Dalton Trans., 1994, 2071; U. Heinzel, A. Henke and
R. Mattes, J. Chem. Soc., Dalton Trans., 1997, 501 and refs. therein;
L. R. Gahan, V. A. Grillo, T. W. Hambley, G. R. Hanson, C. J.
Hawkins, E. M. Proudfoot, B. Moubaraki, K. S. Murray and D. M.
Wang, Inorg. Chem., 1996, 35, 1039; A. J. Blake, J. P. Danks,
S. Parsons and M. Schröder, Acta Crystallogr., Sect. C, 1996, 52,
3062; V. A. Grillo, G. R. Hanson, T. W. Hambley, L. R. Gahan,
K. S. Murray and B. Moubaraki, J. Chem. Soc., Dalton Trans., 1997,
501 and refs. therein.
Ϫ
836s and 558m (PF6 ). FAB mass spectrum: m/z = 592 ([M Ϫ
2PF6 ϩ 1]ϩ).
[Cu2(HL2)2][PF6]2 2 and [Cu(HL2)][PF6] 3. These complexes
were prepared using the same procedure as for 1, except that
after isolation of the PF6Ϫ salt the black solid was passed down a
Sephadex (LH-20) column with MeCN and two fractions 2 and
3 were isolated. [Cu2(HL2)2][PF6]2 2 (Found: C, 35.9; H, 6.2; N,
6.1. C19H29CuF6N2O2PS ϩ MeCN ϩ 0.3Et2O requires C, 35.8;
H, 6.2; N, 6.5%): IR spectrum (KBr disc) ν max/cmϪ1 3441s (OH),
5 A. J. Blake and M. Schröder, Adv. Inorg. Chem., 1990, 35, 1; S. R.
Cooper and S. C. Rawle, Struct. Bonding (Berlin), 1990, 72, 1.
6 For a review see, P. V. Bernhardt and G. A. Lawrence, Coord. Chem.
Rev., 1990, 104, 297; J. L. Sessler, J. Hugdahl, H. Kurosaki and
Y. Sasaki, Coord. Chem. Rev., 1988, 18, 93; S. G. Taylor, M. R. Snow
and T. W. Hambley, Aust. J. Chem., 1983, 36, 2359; K. Wieghardt,
E. Schoeffmann, N. B. Nuber and J. Weiss, Inorg. Chem., 1986, 25,
4877; K. Wieghardt, W. Schmidt, W. Hermann and H. J. Küppers,
Coord. Chem. Rev., 1990, 104, 297; Inorg. Chem., 1983, 22, 2953;
M. J. Van der Merwe, J. C. A. Boeyens and R. D. Hancock, Inorg.
Chem., 1985, 24, 1208; A. Riesen, T. A. Kaden, W. Ritter and H. R.
Macke, J. Chem. Soc., Chem. Commun., 1989, 460; D. Moore, P. E.
Fanwick and M. J. Welch, Inorg. Chem., 1989, 28, 1504; R. C.
Matthews, D. Parker, G. Ferguson, B. Kaitner, A. Harrison and
L. Royle, Polyhedron, 1991, 10, 1915; U. Bossek, D. Hanke and
K. Wieghardt, Polyhedron, 1993, 12, 1; D. A. Moore, P. E. Fanwick
and M. J. Welch, Inorg. Chem., 1990, 29, 672; T. Beissel, K. S.
Bürger, G. Voigt, K. Wieghardt, C. Butziaff and A. X. Trautwein,
Inorg. Chem., 1993, 32, 124; M. A. Konstantinovska, K. B.
Yatsimirski, B. K. Shcherbakov, Y. M. Polikarpov, T. Y. Medved
and M. I. Kabachnik, Russ. J. Inorg. Chem., 1985, 30, 1463; L. J.
Farrugia, N. M. Macdonald, R. D. Peacock and J. Robb,
Polyhedron, 1995, 14, 541; L. J. Farrugia, P. A. Lowatt and R. D.
Peacock, Inorg. Chim. Acta, 1996, 246, 343; G. T. Smith, P. R.
Mallinson, C. S. Frampton, L. J. Farrugia, R. D. Peacock and
J. A. K. Howard, J. Am. Chem. Soc., 1997, 119, 502; C. Stockheim,
L. Hoster, T. Weyhermuller, K. Wieghardt and B. Nuber, J. Chem.
Soc., Dalton Trans., 1996, 4409; A. Sokolowski, J. Muller,
T. Weyhermuller, R. Schnepf, P. Hildebrandt, K. Hildenbrand,
E. Bothe and K. Wieghardt, J. Am. Chem. Soc., 1997, 119, 8889;
B. Adam, E. Bill, E. Bothe, B. Goerdt, H. Haselhorst,
K. Hildenbrand, A. Sokolowski, S. Steenken, T. Weyhermuller and
K. Wieghardt, Chem. Eur. J., 1997, 3, 308 and refs. therein.
7 A. A. Belal, L. J. Farrugia, R. D. Peacock and J. J. Robb, J. Chem.
Soc., Dalton Trans., 1989, 931; A. A. Belal, P. Chaudhuri, I. A.
Fallis, L. J. Farrugia, R. Hartung, N. M. Macdonald, B. Nuber, R. D.
Peacock, J. Weiss and K. Wieghardt, Inorg. Chem., 1991, 30, 4397;
I. A. Fallis, L. J. Farrugia, N. M. Macdonald and R. D. Peacock,
Inorg. Chem., 1993, 32, 779; J. Chem. Soc., Dalton Trans., 1993,
2759; H. Al-Sagher, I. A. Fallis, L. J. Farrugia and R. D. Peacock,
J. Chem. Soc., Chem. Commun., 1993, 1499; A. J. Blake, I. A. Fallis,
S. Parsons, S. A. Ross and M. Schröder, J. Chem. Soc., Chem.
Commun., 1994, 2467; A. J. Blake, I. A. Fallis, A. Heppeler,
S. Parsons, S. A. Ross and M. Schröder, J. Chem. Soc., Dalton
Trans., 1996, 31; A. J. Blake, I. A. Fallis, S. Parsons, S. A. Ross and
M. Schröder, J. Chem. Soc., Dalton Trans., 1996, 525; A. J. Blake,
I. A. Fallis, R. O. Gould, S. Parsons, S. A. Ross and M. Schröder,
J. Chem. Soc., Dalton Trans., 1996, 4379 and refs. therein.
8 K. Wasielewski and R. Mattes, Acta Crystallogr., Sect. C, 1990, 46,
1826.
Ϫ
2930m, 2839w (CH), 836s and 561m (PF6 ); FAB mass spec-
trum m/z = 705 ([M Ϫ 2PF6]ϩ). [Cu(HL2)][PF6] 3 (Found: C,
34.2; H, 5.8; N, 6.4. C14H29CuF6N2O2PSؒ0.25MeCN requires
C, 34.3; H, 5.9; N, 6.2%): IR spectrum (KBr disc) ν max/cmϪ1
Ϫ
3430s (OH), 2921m, 2831w (CH), 841s and 558m (PF6 ); mass
spectrum m/z = 353 ([M Ϫ PF6 ϩ 1]ϩ).
[Cu(HL3)][PF6] 4. This was prepared using the same pro-
cedure as for compound 1 and the product was isolated as a
blue solid (Found: C, 41.7; H, 6.96; N, 4.3. C20H38CuF6N2O2PS
requires C, 41.7; H, 6.4; N, 4.8%). IR spectrum (KBr disc):
ν max/cmϪ1 3425s (OH), 2928m, 2804w (CH), 840s and 564m
Ϫ
(PF6 ). FAB Mass spectrum: m/z = 433 ([M Ϫ PF6]ϩ).
Crystallography
Single-crystal X-ray data were collected on a Stoë STADI-4
four circle diffractometer, fitted with an Oxford Cryosystems
low temperature device.26
Crystal data. C20H42Cu2F12N4O4P2S2 1, M = 883.72, ortho-
rhombic, space group Pnam, a = 20.566(3), b = 8.7516(10),
c = 17.013(2) Å, U = 3062.0(6) Å3, T = 150(2) K, Z = 4, µ(Mo-
Kα) = 1.741 mmϪ1, 2788 unique reflections measured and used
in all calculations. The final wR(F2) was 0.1813, R1 = 0.0670.
Atoms C(2), C(3), C(4) and C(42) were each equally disordered
Ϫ
over two sites. Disorder in the PF6 anion was treated by
restraining Uij components. The final ∆F extrema of 1.55 and
Ϫ
Ϫ1.66 e ÅϪ3 lie near the disordered PF6 and represent the
residual electron densities after disorder modelling.
C14H29CuF6N2O2PS 3, M = 498.0 monoclinic, space group
P21/c, a = 7.799(3), b = 13.563(3), c = 19.060(3) Å, β = 97.35(3)Њ,
U = 1999.6(10) Å3, T = 150(2) K, Z = 4, µ(Mo-Kα) = 1.343
mmϪ1, 4597 reflections measured, 3517 unique (Rint = 0.101).
The final wR(F2) was 0.241, R1 = 0.1103. It was possible to
locate the hydroxy hydrogen H(45) [on O(45)] from a circular
∆F synthesis, while the position of H(75) [on O(75)] was not
clear; H(45) is therefore included in the model to represent one
component of the disorder, possibly the major one. Disorder
throughout the ligand required modelling and the following
restraints were employed, S᎐C 1.82, C᎐C 1.52 Å within the
macrocyclic ring and C᎐C 1.54 Å elsewhere. Further disorder,
9 D. M. Wambeke, W. Lippens, G. G. Herman and A. M. Goeminne,
J. Chem. Soc., Dalton Trans., 1993, 2017.
10 B. Chak, A. McAuley and T. W. Whitcombe, Can. J. Chem., 1994,
72, 1525.
11 N. Baidya, M. Olmstead and P. K. Mascharak, Inorg. Chem., 1991,
30, 734; G. J. Colpas, M. J. Maroney, C. Bagginka, M. Kumar, W. S.
Willis, S. L. Siub, N. Baidya and P. V. Mascharak, Inorg. Chem.,
1991, 30, 920.
Ϫ
in the PF6 anion, was treated by the use of restraints to
distances, angles and Uij components.
CCDC reference number 186/1014.
12 S. M. Hart, J. C. A. Boeyens, J. P. Michael and R. D. Hancock,
J. Chem. Soc., Dalton Trans., 1983, 1601.
Acknowledgements
13 P. Hoffmann, A. Steinhoff and R. Mattes, Z. Naturforsch., Teil B,
1987, 42, 867.
14 H. Koyama and T. Yoshino, Bull. Chem. Soc. Jpn., 1972, 45, 481.
15 A. S. Craig, R. Kataky, R. C. Matthews, D. Parker, G. Ferguson,
A. Lough, H. Adams, N. Bailey and H. Schneider, J. Chem. Soc.,
Dalton Trans., 1990, 1523.
We thank the EPSRC for support, Dr. R. O. Gould for helpful
discussions and the EPSRC National Mass Spectrometry
Service, University of Swansea.
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