Transition metal salts dependent intramolecular cyclization of a diimine

Article abstract of DOI:10.1016/j.jorganchem.2009.10.012

1,4-Bis(N-tosylethylamino)-2,3-diphenyl-1,4-diaza-1,3-butadiene (L¹) was separated from a condensation reaction of benzil with N-tosyl-ethylenediamine. It was shown that the intramolecular cyclization of L¹ has much dependence on the transition metal salts. The transformation of L¹ in the absence of any transition metal salts gave product 1-tosylaminoethyl-2-tosylaminomethyl-4,5-diphenyl-1H- imidazole (L²) at a temperature above 100 °C. Similar reactions assisted by Ni(CH₃COO)₂·4H₂O, MnCl₂·4H₂O, Mn(CH₃COO)₂·4H₂O, NiCl₂·6H₂O or NiSO₄·7H₂O could also give L² at a much lower temperature and a much higher yield. However, the presence of Cu(CH₃COO)₂·H₂O in a similar transformation reaction led to the formation of a bicyclic derivative 1-tosyl-5,6-diphenyl-1H-2,3-dihydroimidazo[1,2-a]imidazole (L³). But both L² and L³ were not detected when Co(CH₃COO)₂·4H₂O was used in a similar reaction and all attempts to transform L² into L³ failed.

Full text of DOI:10.1016/j.jorganchem.2009.10.012

Journal of Organometallic Chemistry 695 (2010) 189–194
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Transition metal salts dependent intramolecular cyclization of a diimine
*
*
Zilu Chen , Jing Miao, Zhong Zhang, Fupei Liang , Qiang Wu
School of Chemistry and Chemical Engineering of Guangxi Normal University, Guilin 541004, PR China
a r t i c l e i n f o
a b s t r a c t
1,4-Bis(N-tosylethylamino)-2,3-diphenyl-1,4-diaza-1,3-butadiene (L1) was separated from a condensa-
tion reaction of benzil with N-tosyl-ethylenediamine. It was shown that the intramolecular cyclization
of L1 has much dependence on the transition metal salts. The transformation of L1 in the absence of
any transition metal salts gave product 1-tosylaminoethyl-2-tosylaminomethyl-4,5-diphenyl-1H- imid-
azole (L2) at a temperature above 100 °C. Similar reactions assisted by Ni(CH3COO)2ꢀ4H2O, MnCl2ꢀ4H2O,
Mn(CH3COO)2ꢀ4H2O, NiCl2ꢀ6H2O or NiSO4ꢀ7H2O could also give L2 at a much lower temperature and a
much higher yield. However, the presence of Cu(CH3COO)2ꢀH2O in a similar transformation reaction
led to the formation of a bicyclic derivative 1-tosyl-5,6-diphenyl-1H-2,3-dihydroimidazo[1,2-a]imidazole
(L3). But both L2 and L3 were not detected when Co(CH3COO)2ꢀ4H2O was used in a similar reaction and all
attempts to transform L2 into L3 failed.
Article history:
Received 1 September 2009
Received in revised form 1 October 2009
Accepted 13 October 2009
Available online 10 November 2009
Keywords:
Transition metal
Imidazole
Intramolecular cyclization
Diimine
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
mine and the studies on the effect of transition metal salts on the
formation imidazole ring and its bicyclic derivative from the
The synthesis of imidazole and its derivatives presents much
interests in recent years due to their wide applications in biochem-
ical processes [1,2], catalysis [3–7], electron transport systems [8]
and nanoparticle electrosynthesis [9–11]. This might be partly as-
cribed to the application of a large class of imidazoles as ionic li-
quid and the imidazoles related N-heterocyclic carbenes [1,12].
There are numerous methods reported in literatures for the syn-
thesis of imidazoles [12]. In summary, they can be divided into
two types: intermolecular cyclization from multi-components
and intramolecular cyclization from one component. The synthesis
of imidazole ring via intermolecular cyclization from multi-compo-
nents have been extensively studied, such as the reaction of dii-
mine with a CH2 donor [3,13–15] and the four component
condensation of aryl glyoxals, primary amines, carboxylic acids
and isocyanides on wang resin [16]. However, the intramolecular
cyclization to form imidazole ring from one component was much
less studied [17–19]. And only one was reported to form imidazole
ring from diimine via intramolecular cyclization catalyzed by tran-
sition metal salts [19]. In recent years, the use of transition metal
complexes as catalysts has received considerable interest in differ-
ent areas of organic transformations to afford the product in excel-
lent yields owing to the advantages such as inexpensive non-toxic
and eco-friendly nature. Based on this fact, we intend to introduce
transition metal salts to mediate the synthesis of imidazole ring via
intramolecular cyclization. Therefore we report here the synthesis
of a diimine from the reaction of benzil with N-tosyl-ethylenedia-
diimine.
2. Results and discussion
2.1. Synthesis of L1, L2, Ni(L2)2 and L3
The synthesis of L1 and the transition metal salts mediated
transformation of L1 into L2 and L3 are described in Scheme 1.
N-Tosyl-ethylenediamine was synthesized from the reaction of
ethylenediamine with 4-toluene sulfonyl chloride according to a
literature method [20,21]. The reaction of N-tosyl-ethylenediamine
with benzil in ethanol at 90 °C gave L1 in a yield of 70% after recrys-
tallization from ethanol. Attempts to carry out this reaction at low-
er temperature (60 °C and 80 °C) failed to obtain the product of L1.
The 1H NMR spectrum of compound L1 shows two multiplet sig-
nals at 3.35–3.26 and 3.25–3.20 ppm for the four CH2 groups and
a singlet at 2.43 ppm for the two chemically identical CH3 groups.
The 13C NMR spectrum of compound L1 reveals also two signals at
52.8 and 43.7 ppm for the four CH2 groups and a singlet at
21.4 ppm for the two chemically identical CH3 groups. The NMR
information reveals the formation of compound L1.
The transformation of L1 in the presence of Ni(CH3COO)2ꢀ4H2O
in a solvothermal reaction was carried out in methanol at 100 °C
for 3 days, giving L2 in a yield of 72%. Similar reactions using
MnCl2ꢀ4H2O, Mn(CH3COO)2ꢀ4H2O, NiCl2ꢀ6H2O or NiSO4ꢀ7H2O in-
stead of Ni(CH3COO)2ꢀ4H2O gave also L2 as shown in Table 1. It is
noteworthy that no product was identified when the reaction in
the presence of Mn(CH3COO)2ꢀ4H2O was carried out at or below
* Corresponding authors. Fax: +86 (0)773 5832294 (Z. Chen).
E-mail address: chenziluczl@yahoo.co.uk (Z. Chen).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.10.012

190
Z. Chen et al. / Journal of Organometallic Chemistry 695 (2010) 189–194
Scheme 1. Schematic summary of the synthesis of L1 and the transition metal salts mediated transformation of L1 into L2 and L3.
suggest that different transition metal salts have some contribu-
Table 1
tion on the transformation of L1 into L2.
Transformation of L1 into L2 or L3 mediated by different transition metal salts in
hydrothermal reactions with a molar ratio of transition metal salt: L1 = 1:1 under
100 °C for 3 days.
To confirm further the contribution of transition metal salts on
the transformation of L1 into L2, the reactions in the absence or
presence of Ni(CH3COO)2ꢀ4H2O with different ratios of Ni(CH3-
COO)2ꢀ4H2O to L1 were monitored at different temperatures by
TLC techniques in routine solution reactions, as shown in Table 2.
It was shown that no product was identified when the reaction
mixture in the absence of Ni(CH3COO)2ꢀ4H2O was kept at or below
the temperature of 80 °C. The attempted transformation of L1 into
L2 at 50 °C in the presence of Ni(CH3COO)2ꢀ4H2O with a 1:1 ratio of
Ni(CH3COO)2ꢀ4H2O to L1 failed also to afford any product. However
the transformation of L1 into L2 in the presence of Ni(CH3-
COO)2ꢀ4H2O with a 1:1 ratio of Ni(CH3COO)2ꢀ4H2O to L1 is com-
pleted within 2 h at 60 °C and 1.5 h at 80 °C. When the ratios of
Ni(CH3COO)2ꢀ4H2O to L1 were changed into 1:2 and 1:10, the sim-
ilar transformation reactions at 80 °C were completed within 3.5
and 9 h, respectively, as shown in Table 2. All of these confirm that
Ni(CH3COO)2ꢀ4H2O have some contribution in the transformation
of L1 into L2. The transformation of L1 into L2 mediated by Ni(CH3-
COO)2ꢀ4H2O was also tried by solvothermal reactions in a 25 mL
Teflon-lined autoclave. The difference from the corresponding
routine solution reaction mentioned above is that the solvothermal
reaction at 50 °C gave also a very small amount of product L2.
Transition metal salt
Solvent
Product
Yield (%)
1
2
3
4
5
6
7
8
Ni(CH3COO)2ꢀ4H2O
Ni(CH3COO)2ꢀ4H2O
NiCl2ꢀ6H2O
Methanol
Ethanol
Methanol
Methanol
Methanol
Ethanol
L2
L2
L2
L2
L2
L2
L2
L3
72
68
58
70
68
64
50
60
Ni SO4ꢀ7 H2O
Mn(CH3COO)2ꢀ4H2O
Mn(CH3COO)2ꢀ4H2O
MnCl2ꢀ4H2O
Methanol
Methanol
Cu(CH3COO)2ꢀH2O
80 °C. Furthermore, it was found that the presence of Ni(CH3-
COO)2ꢀ4H2O in the solvothermal transformation reaction for 3 days
led to part transformation of L1 into L2 at 60 °C and overall trans-
formation of L1 into L2 above 80 °C. However, using NiCl2ꢀ6H2O in-
stead of Ni(CH3COO)2ꢀ4H2O, the solvothermal transformation
reaction with a duration of 3 days gave no L2 at 60 °C, but induced
an overall transformation of L1 into L2 above 80 °C. In contrast, the
similar reaction was also carried out in the absence of any transi-
tion metal salts. It gave also product L2, but only at a temperature
above 100 °C and in a much lower yield. All of these facts seem to
Table 2
Investigation on the transformation of L1 into L2 assisted by Ni(CH3COO)2ꢀ4H2O in routine solution reactions at different temperatures monitored by TLC technique.
Catalyst
Catalyst:substrate
0.1 mmol:0.1 mmol
Solvent
T (°C)
Time (h)
Product
1
2
3
4
5
6
7
8
Ni(CH3COO)2ꢀ4H2O
No transition metal salt
Ni(CH3COO)2ꢀ4H2O
No transition metal salt
Ni(CH3COO)2ꢀ4H2O
No transition metal salt
Ni(CH3COO)2ꢀ4H2O
Ni(CH3COO)2ꢀ4H2O
Methanol
Methanol
Methanol
Methanol
Ethanol
Ethanol
Ethanol
Ethanol
50
50
60
60
80
80
80
80
10
10
2
10
1.5
10
3.5
9
No reaction
No reaction
0.1 mmol:0.1 mmol
0.1 mmol:0.1 mmol
L2
No reaction
L2
No reaction
0.1 mmol:0.2 mmol
0.1 mmol:1 mmol
L2
L2

Z. Chen et al. / Journal of Organometallic Chemistry 695 (2010) 189–194
191
However the solvothermal reaction at 120 °C gave a complex of L2,
Ni(L2)2, not just L2.
reported by the group of Datta [19] and the group of Yaylayan
[22]. In the case reported by Datta the binding of L (L = 1:2 conden-
sate of benzil and 2-(aminomethyl)pyridine) to zinc seems to be a
prerequisite for the formation of imidazole ring. However it seems
to be not necessary for the formation of L2 in our case because the
formation of L2 could also occur even with the absence of transi-
tion metal salts as revealed by the experimental facts. Neverthe-
less, the presence of transition metal salts makes it much easier
for the formation of L2 probably due to the much easier release
of H+ from L1 upon its coordination to transition metal ions. For
the formation of L3 from L1 the coordination of L1 to Cu2+ seems
to be a prerequisite as suggested by the experimental studies de-
scribed above in the context. The tentative mechanism for the for-
mation of L3 is demonstrated by the experimental fact of failing to
transform L2 into L3. In the last step of the proposed mechanisms
for the transformation of L1 into L2 and L3 an aerial oxidation is
implicated to complete the formation of the corresponding imidaz-
ole rings. To confirm the occurrence of aerial oxidation during the
reaction course for the formation of both L2 and L3, we carried out
the solvothermal transformation reactions under N2 atmosphere in
the presence of Ni(CH3COO)2ꢀ4H2O and Cu(CH3COO)2ꢀH2O, respec-
The solvent effect on the formation of L2 was investigated by
the use of dichloromethane, ethanol, methanol and H2O as solvents
in the transformation reactions of L1 into L2 in the presence of
Ni(CH3COO)2ꢀ4H2O in a sealed 25 mL Teflon-lined autoclave at
60 °C. It was shown that only methanol and ethanol can serve as
the solvents in the reactions. The reactions using dichloromethane
and water as solvents failed to give L2.
L2 was identified by elemental analysis, infrared spectroscopy,
mass spectroscopy, NMR and single crystal X-ray diffraction anal-
ysis. The existence of three chemically different CH2 groups in
compound L2 are confirmed by one doublet at 4.35 ppm, one triplet
at 3.94 ppm and one quadralet at 2.85 ppm in the 1H NMR spec-
trum of L2 and three signals at 44.2, 42.6 and 39.3 ppm in the
13C NMR spectrum of compound L2. It is further shown that there
are two chemically different CH3 groups revealed by two singlet at
2.44 and 2.42 ppm in the 1H NMR spectrum of L2. All of the NMR
information demonstrates the formation of compound L2 from L1,
consistent with the X-ray diffraction analysis result.
However, the solvothermal transformation of L1 mediated by
Cu(CH3COO)2ꢀH2O instead of other transition metal salts men-
tioned above at 100 °C for 3 days produced a bicyclic derivative
L3 in a yield of 60%. L3 was identified by elemental analysis, infra-
red spectroscopy, mass spectroscopy, NMR and single crystal X-ray
diffraction analysis. Compound L3 exhibits two triplets at 4.30 and
3.90 ppm in the 1H NMR spectrum and two signals at 51.6 and
41.4 ppm in the 13C NMR spectrum for the two chemically different
CH2 groups and one singlet at 2.44 ppm in the 1H NMR spectrum
and one signal at 21.7 ppm in the 13C NMR spectrum for the only
one CH3 group. This is consistent with the structure of compound
L3 confirmed by the X-ray diffraction analysis.
But both L2 and L3 were not detected when Co(CH3COO)2ꢀ4H2O
was used in a similar reaction. All attempts to transform L2 into L3
in the presence of any transition metal salts mentioned above
failed.
Proposed mechanisms for the transformation of L1 into L2 and
L3 are shown in Scheme 2. It reveals some similarities to those
Fig. 1. ORTEP view of the structure of L2 showing the atom-labeling scheme and 30%
thermal ellipsoids.
Scheme 2. Proposed mechanisms for the transformation of L1 into L2 and L3.
Fig. 2. ORTEP view of the structure of Ni(L2)2 showing the atom-labeling scheme and
[O] = oxidation.
30% thermal ellipsoids.

192
Z. Chen et al. / Journal of Organometallic Chemistry 695 (2010) 189–194
360FT-IR spectrometer. Elemental analyses (C, H and N) were per-
formed on a Vario EL analyzer. 1H and 13C NMR spectra were re-
corded on Bruker AV 500 spectrometer at 500.13 and
a
125.23 MHz, respectively. All proton and carbon chemical shifts
are reported in d units with reference to SiMe4. Melting points
were measured on an X-6 melting point apparatus and were
uncorrected. Analytical TLC’s were performed on pre-coated Merck
silica gel 60 F254 plates; the spots were detected either under UV
light or by placing in iodine chamber.
4.2. Synthesis of L1
N-Tosyl-ethylenediamine (0.856 g, 4 mmol) was dissolved in
20 mL ethanol, which was stirred using a magnetic stirrer. Benzil
(0.42 g, 2 mmol) dissolved in a 10 mL of ethanol was added drop-
wise using a dropping funnel to the above solution. The mixture
was heated in an oil bath at 90 °C, the completion of reaction
was monitored by TLC. Twenty hours later, the solution was cooled
to ambient temperature over a period of 6 h. The thus formed
white-yellow crystalline product was collected by filtration,
washed with ethanol twice (2 ꢂ 5 mL) and dried in vacuo. Finally
the product was recrystallized from ethanol to give pure needle
crystals (yield: 70%). m.p.: 159ꢁ161 °C. Elemental analysis calcd
(%) for C32H34O4N4S2: C, 63.76; H, 5.69; N, 9.29. Found: C, 63.42;
H, 5.92; N, 9.50. 1H NMR (CDCl3, ppm): d = 7.76 (d, J = 8.5 Hz,
4H), 7.63 (d, J = 7.5 Hz, 4H), 7.46 (t, J = 7.5 Hz, 2H), 7.37 (t,
J = 8 Hz, 4H), 7.29 (t, J = 8.5 Hz, CHꢁC(CH3)@CH, 4H), 3.35ꢁ3.26
(m, C@NꢁCH2, 4H), 3.25–3.20 (m, SꢁNꢁCH2, 4H), 2.43 (s, CH3,
6H). 13C NMR (CDCl3, TMS): d = 21.4 (s, CH3), 43.7 (SꢁNꢁCH2),
52.8 (C@NꢁCH2), 127.1, 127.2, 128.9, 129.6, 131.4, 135.0 (N@CꢁC),
143.3 (CH3ꢁC), 167.2 (C@N) ppm. IR (KBr, pellet)/cmꢁ1: 3445m,
3153m, 2902w, 1626m, 1598m, 1578w, 1494w, 1449m, 1327s,
1305m, 1291m, 1252w, 1169s, 1108m, 1091m, 1073m, 1033w,
928m, 900w, 815m, 774m, 695m, 661m, 598w, 577m, 550m.
MS[m/z]: 601.94. (MꢁH+).
Fig. 3. ORTEP view of the structure of L3 showing the atom-labeling scheme and 30%
thermal ellipsoids.
tively. As expected, no product L2 or L3 was found in both cases due
to the absence of oxygen.
2.2. Crystal structure studies of L2, Ni(L2) and L3
An ORTEP view of the structure of L2 is shown in Fig. 1. It is shown
that N1, C1, C2, N3 and C15 are nearly located in one plane and the
N1–C1, C1–C2, C2–N3, N3–C15 and C15–N1 bond lengths and the
corresponding bond angles (Table 4) in the ring are comparable to
those in the imidazole ring reported [23–26]. This confirms the
existence of the imidazole ring in compound L2.
The crystal structure of Ni(L2)2 (Fig. 2) shows the chelation of L2
to the Ni(II) ion using one imidazole ring nitrogen atom and one
amino nitrogen atom. Each Ni(II) ion is four-coordinated by two
[L2]ꢁ ions to form a severely distorted tetrahedral geometry. The
bond lengths and angles (Table 4) in the ring are comparable to
the corresponding ones in L2.
4.3. Synthesis of L2
A
mixture of nickle(II) acetate tetrahydrate (0.0248 g,
The crystal structure of L3 is shown in Fig. 3. It reveals the pres-
ence of an imidazole ring N1C1C2N3C17 in compound L3 as dem-
onstrated by the bond lengths and angles shown in Table 4. It
demonstrates also the formation of another five-membered het-
erocyclic ring of N1C15C16N2C17.
0.1 mmol), L1 (0.0602 g, 0.1 mmol) and methanol (10 mL) was
sealed in a 23 mL Teflon-lined autoclave and heated at 100 °C for
3 days. Then it was cooled over a period of 24 h and filtered. The
evaporation of the filtrate at ambient temperature for 2 days gave
colorless crystals of compound (L2). Yield: 0.0433 g (72%). m.p.:
215ꢁ218 °C. Elemental analysis calcd (%) for C32H32O4N4S2: C,
63.98; H, 5.37; N, 9.33. Found: C, 63.54; H, 5.05; N, 9.65. 1H NMR
(CDCl3, ppm): 7.79 (d, J = 8 Hz, 2H), 7.68 (d, J = 8 Hz, 2H), 7.42 (t,
J = 7 Hz,1H), 7.36ꢁ7.30 (m, 6H), 7.17ꢁ7.04 (m, 5H), 6.93 (d,
J = 7 Hz, 2H), 4.35 (d, J = 5.5 Hz, ꢁCꢁCH2ꢁNHꢁSO2ꢁ, 2H), 3.94 (t,
3. Conclusion
In this research work, a diimine was separated from a conden-
sation reaction of benzil with N-tosyl-ethylenediamine. The transi-
tion metal salts mediated intramolecular cyclization of the diimine
was investigated. It was shown that the presence of Ni(CH3-
COO)2ꢀ4H2O, MnCl2ꢀ4H2O, Mn(CH3COO)2ꢀ4H2O, NiCl2ꢀ6H2O or Ni-
SO4ꢀ7H2O could lead to the formation of a substituted imidazole
with one imidazole ring at a much lower temperature and a much
higher yield than the similar case in the absence of any transition
metal salts. However, a similar transformation reaction in the pres-
ence of Cu(CH3COO)2ꢀH2O gave a bicyclic derivative. But both prod-
ucts were not detected when Co(CH3COO)2ꢀ4H2O was used in a
similar reaction and all attempts to transform L2 into L3 failed.
3
J = 6 Hz, ꢁNꢁCH2ꢁCH2ꢁNHꢁSO2ꢁ, 2H), 2.85 (q, JHH = 6.0 Hz,
3JHH = 6.5 Hz, CH2ꢁCH2ꢁNHꢁSO2ꢁ, 2H), 2.44 (s, CH3, 3H), 2.42 (s,
CH3, 3H). 13C NMR (CDCl3, ppm): d = 143.8, 143.6, 143.0, 136.7,
136.4, 131.0, 129.9, 129.8, 129.4, 128.3, 127.1, 127.0, 126.6, 44.2,
42.6, 39.3, 21.5. IR (KBr, pellet)/cmꢁ1: 3438s, 3262m, 1630m,
1598m, 1498w, 1426m, 1385m, 1342s, 1312m, 1165s, 1147s,
1122m, 1093s, 976w, 811m, 774m, 699m, 577w, 554m, 527w.
4.4. Synthesis of Ni(L2)2
Nickle(II) acetate tetrahydrate (0.0248 g, 0.1 mmol) was added
into a methanol solution (10 mL) of L1 (0.0602 g, 0.1 mmol). The re-
sulted mixture was transferred into a 23 mL Teflon-lined auto-
clave, heated at 120 °C for 2 days. It was then cooled over a
period of 10 h and filtered. The filtrate was allowed to evaporate
at ambient temperature for 4 h, giving purple crystals of Ni(L2)2
in a yield of 85%. Elemental analysis calcd (%) for C64H62N8NiO8S4:
4. Experimental
4.1. General procedures
All chemicals were used as obtained without further purifica-
tion. Infrared spectra were recorded as KBr pellet using a Nicolet

Z. Chen et al. / Journal of Organometallic Chemistry 695 (2010) 189–194
193
Table 4
C, 61.10; H, 4.97; N, 8.91. Found: C, 60.74; H, 5.31; N, 8.74. IR (KBr,
Selected bond lengths (Å) and angles (°) for compounds L2, Ni(L2)2 and L3.
pellet)/cmꢁ1: 3446m, 3186m, 3060w, 2925w, 1627w, 1600m,
1493s, 1441m, 1335s, 1269m, 1161vs, 1144vs, 1125s, 1103m,
1082m, 1053w, 1021w, 997m, 954m, 817m, 783m, 771m, 734m,
708m, 688s, 664s, 587m, 555s, 517w.
L2
C1–C2
C1–N1
C2–N3
N1–C15
C15–N3
C15–C16 1.493(4)
C16–N2
N3–C24
1.372(4)
1.390(3)
1.390(3)
1.321(3)
1.360(3)
C2–C1–N1
C2–C1–C9
N1–C1–C9
C1–C2–N3
C1–C2–C3
N3–C2–C3
C15–N1–C1
N1–C15–N3
109.6(2)
128.4(3)
121.9(2)
105.7(2)
129.8(3)
124.0(2)
106.0(2)
111.3(2)
N3–C15–C16 124.8(2)
N2–C16–C15 115.6(2)
C16–N2–S1
C15–N3–C2
123.7(2)
107.4(2)
4.5. Synthesis of L3
C15–N3–C24 126.9(2)
C2–N3–C24 125.4(2)
1.459(4)
1.467(3)
N3–C24–C25 113.1(2)
N4–C25–C24 112.8(2)
A
mixture of copper(II) acetate tetrahydrate (0.0200 g,
0.1 mmol), L1 (0.0602 g, 0.1 mmol), and methanol (10 mL) was
sealed in a 23 mL Teflon-lined autoclave and heated at 100 °C for
3 days. It was then cooled over a period of 10 h and filtered. The fil-
trate was allowed to evaporate at ambient temperature for 2 days,
giving crystals of compound L3 in a yield of 60% (0.0349 g). Ele-
mental analysis calcd (%) for C24H21N3O2S: C, 69.37; H, 5.09; N,
10.11. Found: C, 69.72; H, 5.42; N, 9.90. 1H NMR (CDCl3, ppm):
d = 8.03 (d, J = 7.5 Hz, 2H), 7.60 (d, J = 6 Hz, 2H), 7.36ꢁ7.19 (m,
10H), 4.30 (t, J = 7 Hz, PhꢁCꢁNꢁCH2, 2H), 3.90 (t, J = 7 Hz,
TsꢁNꢁCH2, 2H), 2.44 (s, CH3, 3H). 13C NMR (CDCl3, TMS):
d = 145.0, 134.8, 133.5, 130.1, 129.8, 128.9, 128.5, 128.3, 128.1,
127.9, 127.4, 126.8, 51.6 (PhꢁCꢁNꢁCH2), 41.4 (s, TsꢁNꢁCH2,),
21.7 (s, CH3). IR (KBr pellet)/cmꢁ1: 3436s, 3059w, 2933w, 1603m,
1578w, 1546s, 1490m, 1449m, 1443m, 1369s, 1350m, 1299m,
1242w, 1186s, 1170vs, 1136m, 1091m, 1008m, 943w, 815m,
792m, 734m, 708s, 700s, 672s, 650m, 586s, 550m.
C24–C25 1.509(4)
N1–C15–C16 123.9(2)
C25–N4
1.470(4)
Ni(L2)2
Ni1–N1
Ni1–N5
Ni1–N6
Ni1–N2
C8–C9
C8–N1
C9–N2
C9–N3
1.935(5)
1.954(5)
1.983(5)
2.004(6)
1.480(9)
1.481(8)
1.315(8)
1.362(8)
C41–N7
C42–C49
C42–N6
C49–N7
C56–N7
1.342(8)
1.364(9)
1.380(8)
1.399(8)
1.463(8)
N4–C25–C24 113.0(6)
N5–C40–C41 105.5(5)
N6–C41–N7
110.8(5)
N6–C41–C40 120.3(6)
N7–C41–C40 128.8(6)
C56–C57
C57–N8
1.511(10) C49–C42–N6 108.9(5)
1.462(9)
138.0(2)
128.7(2)
81.7(2)
82.1(2)
126.2(2)
98.6(2)
C42–C49–N7 106.1(5)
N7–C56–C57 113.9(6)
N8–C57–C56 111.1(5)
N1–Ni1–N5
N1–Ni1–N6
N5–Ni1–N6
N1–Ni1–N2
N5–Ni1–N2
C10–C17 1.366(9)
C10–N2
C17–N3
C24–N3
1.399(8)
1.400(8)
1.455(8)
C9–N2–C10
C9–N3–C17
C9–N3–C24
107.1(5)
107.1(5)
126.5(5)
C24–C25 1.506(10) N6–Ni1–N2
C17–N3–C24 126.3(5)
C41–N6–C42 106.9(5)
C41–N7–C49 107.3(5)
C41–N7–C56 126.1(5)
C49–N7–C56 126.6(5)
C25–N4
C40–N5
1.448(9)
1.459(8)
N2–C9–N3
110.9(5)
C17–C10–N2 108.6(5)
C10–C17–N3 106.3(5)
N3–C24–C25 113.1(6)
C40–C41 1.488(9)
C41–N6
1.327(8)
L3
4.6. X-ray crystallography
C1–C2
C1–N1
C1–C9
C2–N3
N1–C17
N1–C15
1.376(3)
1.388(3)
1.472(3)
1.410(3)
1.345(3)
1.455(3)
N2–C17
C17–N3
C17–N2–C16 106.0(2)
N3–C17–N1
N3–C17–N2
N1–C17–N2
C17–N3–C2
1.411(3)
1.308(3)
C2–C1–N1
C1–C2–N3
C17–N1–C1
C17–N1–C15 111.9(2)
C1–N1–C15 137.0(2)
104.3(2)
111.5(2)
106.82(19)
The selected single crystals of L2, Ni(L2)2 and L3 were put in a
sealed tube and the measurement was performed on a Bruker
Smart Apex-II CCD diffractometer using graphite-monochromated
114.9(2)
134.5(2)
110.3(2)
102.4(2)
N1–C15–C16 101.1(2)
N2–C16–C15 104.39(19)
Mo Ka
radiation (k = 0.71073 Å). Absorption correction were ap-
C15–C16 1.524(4)
C16–N2 1.500(3)
Table 3
Crystal data and structure refinement parameters for compounds L2, Ni(L2)2 and L3.
plied by using the multi-scan program SADABS [27]. All of the struc-
tures were solved by direct methods using the Program SHELXS-97
[28] and refined by the full-matrix least-squares methods on all
F2 data with SHELXL-97 [29]. The program PLATON [30] was used to
check the result of the X-ray analysis and the program ORTEP [31]
used to give a representation of the structures. H atoms on C atoms
were placed in calculated positions. Experimental details for the
structure analysis of L2, Ni(L2)2 and L3 are given in Table 3. The se-
lected bond distances and angles for L2, Ni(L2)2 and L3 are listed in
Table 4.
L2
Ni(L2)2
L3
Formula
Fw
T (K)
C32H32N4O4S2
600.74
296(2)
C64H62N8NiO8S4
1258.17
296(2)
C24H21N3O2S
415.50
296(2)
k (Å)
0.71073
Triclinic
0.71073
Triclinic
0.71073
Monoclinic
P21/n
12.6496(16)
10.2211(13)
17.033(2)
90
106.417(2)
90
2112.4(5)
4
Crystal system
Space group
a (Å)
b (Å)
c (Å)
ꢀ
ꢀ
P1
P1
10.2330(16)
10.8187(17)
15.153(3)
94.647(2)
101.098(2)
112.845(2)
1494.4(4)
2
14.561(9)
15.519(13)
16.677(14)
64.053(10)
82.914(18)
71.91(3)
3221(4)
2
a
(°)
b (°)
c
(°)
Supplementary material
V (Å3)
Z
Dc (g cmꢁ3
)
1.335
0.222
1.297
0.490
1.306
0.179
CCDC 744553, 744554 and 744555 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
l
(mmꢁ1
)
F(0 0 0)
632
1316
872
Crystal size (mm) 0.20 ꢂ 0.15 ꢂ 0.15 0.25 ꢂ 0.20 ꢂ 0.20 0.20 ꢂ 0.20 ꢂ 0.15
h (°)
2.07–25.01
7792/5174
2.02–25.01
16,397/11,061
2.35–27.45
12,900/4799
Reflections
collected/
unique
Rint
Acknowledgments
0.0256
1.060
0.0522
0.1154
0.0904
0.1377
0.0255
1.090
0.0824
0.2608
0.1089
0.2792
0.0518
1.007
R1 = 0.0545
wR2 = 0.1051
R1 = 0.1185
wR2 = 0.1291
The authors thank the financial support by National Natural
Science Foundation of China (Grant No. 20962003), Guangxi Natu-
ral Science Foundation(Grant No. 0991008) and Innovation Project
of Guangxi Graduate Education (2009106020703M43).
GOF on F2
R1 (I > 2
r
(I))a
(I))b
wR2 (I > 2
r
R1 (all data)a
wR2 (all data)b
Largest difference 0.187 and ꢁ0.308 1.248 and ꢁ0.444 0.193 and ꢁ0.360
in peak and
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