A macrocyclic ligand 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo-[b,i] [1,4,8,11]tetraazacyclotetradecine and its nickel(II) complex: Syntheses, reaction mechanism and structures

Article abstract of DOI:10.1016/j.inoche.2011.05.040

The template reaction of o-phenylenediamine, 1-benzoylacetone and nickelous acetate tetrahydrate results in two structure isomers, 6,17-dimethyl-8,15- diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinatonickel (II) (2) and 6,15-dimethyl-8,17-diphenyld

Full text of DOI:10.1016/j.inoche.2011.05.040

Inorganic Chemistry Communications 14 (2011) 1555–1560
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
A macrocyclic ligand 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo-[b,i]
[
1,4,8,11]tetraazacyclotetradecine and its nickel(II) complex: Syntheses, reaction
mechanism and structures
a,
a
a
a
b
b
b
Xuan Shen ⁎, Lu Sun , Bo-Kun Jiang , Xin Wang , Akio Nakashima , Naoki Miyamoto , Kazunori Sakata ,
a
a,
Yan Xu , Dun-Ru Zhu ⁎
a
State Key Laboratory of Materials-oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, PR China
Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, Kitakyushu 804-8550, Japan
b
a r t i c l e i n f o
a b s t r a c t
Article history:
The template reaction of o-phenylenediamine, 1-benzoylacetone and nickelous acetate tetrahydrate results in
two structure isomers, 6,17-dimethyl-8,15-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinatonickel
Received 19 April 2011
Accepted 25 May 2011
Available online 2 June 2011
(
II) (2) and 6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinatonickel (II) (4).
However, the latter has been neglected in the previous research because of its low yield in the template
reaction. The mechanism of this template reaction is discussed. Though the steric hindrance between the
phenyl ring and the benzo ring in 2 is greater than that in 4, the intermediate of the former shows better
structural stability than that of the latter, leading to obviously higher final yield of 2 compared with that of 4.
n-Butyl alcohol is used artfully to separate the crude product of the template reaction into almost pure 2 and a
mixture of 2 and 4 in a mole ratio of 1:5. The free base of 2, 5,14-dihydro-6,17-dimethyl-8,15-
diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (1), can be synthesized by demetalization of 2 with
gaseous HCl. The same treatment to the mixture of 2 and 4 in a mole ratio of 1:5 leads to the free base of 4,
Keywords:
Template reaction
Structure isomer
Reaction mechanism
Macrocyclic compound
Single-crystal structure
5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (3). The neglected
macrocyclic compounds 3 and 4 have been characterized unambiguously and their single-crystal structures
have also been determined by X-ray diffraction analysis for the first time.
©
2011 Elsevier B.V. All rights reserved.
Being similar to the catenulate Schiff base ligand 1,3-bis(salicylidene
iminoethylamino)-2-propanol [1], 5,14-Dihydro-6,8,15,17-tetramethyl-
dibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (H tmtaa), a versatile mac-
2
cinatonickel (II) (4, Fig. 1), have not been reported unambiguously. The
present study elucidates the syntheses and characterization of 3and 4. The
reaction mechanism is discussed and the single-crystal structures of 3 and
4 are determined by X-ray diffraction analysis for the first time.
rocyclic Schiff base ligand for transition and main group metal chemistry,
has stimulated continuing interest in a wide range of chemical areas [2–4].
Recently, Chandra et al. reported the preparation of 3 by the direct
condensation reaction of o-phenylenediamine and 1-benzoylacetone
[26]. However, no cogent data can certify the production of the target
compound. Furthermore, it has been made clear that this series of
macrocyclic Schiff base ligands are synthesized by demetalization of
their metal complexes prepared from the reaction of condensing o-
phenylenediamines with β-diketones in the presence of metal ions
(usually nickel (II)) [27]. The direct reaction of o-phenylenediamine
and 1-benzoylacetone without the existence of metal ion leads to
benzodiazepine instead of 1 or 3 (Scheme 1). In addition, Park et al.
reported the template synthesis of 4 by the reaction of o-phenylene-
diamine, 1-benzoylacetone and nickelous acetate tetrahydrate
The extensive applications of H
derivatives in fields of catalyst [5–11], sensor [12], conductive material
13,14], liquid crystal material [15], corrosive inhibitor [16] and DNA/RNA
2
tmtaa and its complexes or their
[
binding agents [17–19] show capacious research foreground of these
macrocyclic compounds. 5,14-Dihydro-6,17-dimethyl-8,15-diphenyldi-
benzo[b,i][1,4,8,11]tetraazacyclotetradecine (1, Fig. 1), which is an
2
extension of H tmtaa's maternal analog by two phenyls, and the nickel
(II) complex of 1, 6,17-dimethyl-8,15-diphenyldibenzo[b,i]-[1,4,8,11]
tetraazacyclotetradecinatonickel (II) (2, Fig. 1), have been fully investi-
gated [20–25]. However, syntheses and characterization of the isomeric
macrocyclic compounds of 1 and 2, 5,14-dihydro-6,15-dimethyl-8,17-
diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (3, Fig. 1) and
(NiAc
2
·4H
H NMR data, the product should be 2, while not 4 [28, Fig. S2, S4].
and 2 were first reported by Eilmes et al. In their work, 1 was
synthesized by the demetalization of 2 prepared from the template
reaction of o-phenylenediamine, 1-benzoylacetone and NiAc ·4H
[20]. The single-crystal structures of 1 and 2 were also determined by
2
O). Nevertheless, judging from the synthetic method and
1
6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraaza-cyclotetrade-
1
2
2
O
⁎
Corresponding authors. Tel.: +86 25 8358 7717; fax: +86 25 8336 5813.
E-mail addresses: shenxuan@njut.edu.cn (X. Shen), zhudr@njut.edu.cn (D.-R. Zhu).
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.05.040

1556
X. Shen et al. / Inorganic Chemistry Communications 14 (2011) 1555–1560
1
2
7
7
6
8
6
8
4
1
5
9
10
4
1
5
9
10
N
HN
N
N
3
2
11
12
3
2
11
12
Ni
16
NH
N
N
N
18
14 13
18
14
1
3
1
7
15
17
15
1
6
3
4
7
7
6
8
6
8
4
1
5
9
10
4
1
5
9
10
N
HN
N
N
N
3
2
11
12
3
2
11
12
Ni
16
NH
N
N
18
14 13
18
14 13
1
7
15
17
15
1
6
Fig. 1. Suggested structures of 1–4.
the same researchers in their subsequent work [22]. However,
syntheses and characterization of the structure isomers of 1,2, 3 and
mole ratio of 2 and 4 is ca. 1:5 [SI]. Pure 2 can be obtained by
recrystallization of crude 2, while pure 4 cannot be acquired in the
same way because of the high content of 2 in crude 4. Demetalization
of pure 2 with gaseous HCl leads to pure 1 [SI]. Pure 3 can be obtained
by demetalization of crude 4[29] and pure 4 is able to be acquired by
4, were not mentioned in their work. In this template reaction, 2's
structure isomer, 4, should also yield theoretically at the same time. In
this work, macrocyclic compounds 1–4 are synthesized according to
the routes shown in Scheme 2. Treating the crude product of the
template reaction with filtration, washing and chromatographic
separation leads to a mixture of 2 and 4. 2 and 4 cannot be separated
absolutely by ordinary methods, even by chromatographic separation
due to their extremely analogous physical and chemical properties.
After unnumbered attempts, we detect that 2 and 4 show different
solubility in some solvents, for instance, n-butyl alcohol. Thus, n-butyl
alcohol is used to separate the mixture of 2 and 4 to give crude 2 in
which the mole ratio of 2 and 4 is ca. 33:1 and crude 4 in which the
the reaction of 3 and NiAc
Generally speaking, the template reaction of o-phenylenediamine,
1-benzoylacetone and NiAc ·4H O should result in 2 and 4 in a mole
2 2
·4H O in a high yield [30].
2
2
ration of 1:1 according to probability theory. However, the macrocy-
clic ligand 3 and its nickel(II) complex 4 have been neglected in the
previous works. This may be due to the extremely low yield of 4 in the
template reaction. The possible mechanism of the formation of 2 and 4
in the template reaction of o-phenylenediamine, 1-benzoylacetone and
2 2
NiAc ·4H O is shown in Scheme 3. The first reaction step is that two 1-
N
N
NH2
NH2
+
O
O
N
HN
N
HN
N
or
NH
N
NH
1
3
Scheme 1. The condensation reaction of o-phenylenediamine and 1-benzoylacetone.

X. Shen et al. / Inorganic Chemistry Communications 14 (2011) 1555–1560
1557
1
(pure)
NH2
NH2
HCl(g)
crystallization
+
2 (crude)
4 (crude)
2 (pure)
3 (pure)
O
O
n-butyl alcohol
2
+ 4
separation of
structure isomers
HCl(g)
+
NiAc ·4H O
2
2
Ni(II)
(pure)
4
Scheme 2. Synthetic routes of 1–4.
benzoylacetone molecules react with one o-phenylenediamine mole-
cule and one NiAc ·4H O molecule, leading to the intermediates, (Z)-
in the product will also rise. Nevertheless, high reaction tempera-
ture will lead to the decomposition of the intermediates and cause
the total yield of 2 and 4 to decrease [Table S2]. Thus, considering
these factors synthetically, ethanol has been selected as the reaction
solvent for the template reaction and 4 is obtained in a relatively high
yield.
3 crystallizes in the triclinic space group P-1 [31] with two similar
molecules in the asymmetric unit (Figs. 2 and 3). Two phenyl
substituents in 3 are adjacent to two different benzo rings, while those
in 1 are adjacent to the same benzo ring. Being similar to this series of
macrocyclic compounds, both molecules A and B show a saddle-shaped
deformation of the macrocycle because of the mutual repulsion of
the methyl, phenyl and benzo groups, while exhibiting a distincter
guache conformation compared with that of 1. Being very different from
2
2
NiDAO and (E)-NiDAO. Existence and characterization of (Z)-NiDAO
have been reported [22]. Secondly, the reaction of (Z)-NiDAO or (E)-
NiDAO with another o-phenylenediamine molecule results in corre-
sponding macrocyclic compound 2 or 4. Because two phenyl substit-
uents in 2 are in the cis positions and those in 4 are in the trans positions,
the steric hindrance between phenyl ring and benzo ring in 2 should be
greater than that in 4. Thus, it seems that 4 can be presumed as the
more stable product of the template reaction and the yield of 4 in the
reaction should be higher. However, judging from the structures of
the intermediates, (Z)-NiDAO and (E)-NiDAO, the former should be
the more stable product, because in order to overcome the steric
hindrance, two phenyl rings have a trend depart from the benzo ring.
Thus, (Z)-NiDAO is the chief product and (E)-NiDAO is the secondary
product in the first step of the template reaction, which leading the
higher final yield of 2 than 4. Methanol, ethanol, n-butyl alcohol and
2
the unsubstituted highly π-conjugated macrocyclic H tmtaa or its de-
rivatives, four N atoms in 3 show great uncoplanarity. Δmax values of N
atoms in molecules A and B are 0.676 and 0.568 Å, respectively. This may
be due to the great distorting effect of the methyl and phenyl
2
-methoxyl ethanol are used as reaction solvents respectively and
the template reactions are carried out under reflux. It can be found
that with the rise of the reaction temperature, the mole ratio of 4
substituents to the N
also enlarges the dihedral angles of the almost flat N
4
plane. Meanwhile, the great distorting effect
plane and other
4
N
Ni
N
O
O
N
N
N
N
Ni
O
+
O
NH2
NH2
NH
2
2
(
Z)-NiDAO
NH
2
+
+
NiAc ·4H O
2
2
N
N
O
O
N
N
N
N
Ni
Ni
(
E)-NiDAO
4
2 2
Scheme 3. The possible mechanism of the formation of 2 and 4 in the template reaction of o-phenylenediamine, 1-benzoylacetone and NiAc ·4H O.

1558
X. Shen et al. / Inorganic Chemistry Communications 14 (2011) 1555–1560
Fig. 2. Partial view of the unit cell of 3, showing two similar molecules (A (right) and B (left)) in the asymmetric unit. Selected bond distances (Å) and angles (°) for A and B: N1\C2
.305(10) (A) 1.310(9) (B), N2\C4 1.364(10) (A) 1.360(9) (B), N3\C18 1.295(10) (A) 1.312(10) (B), N4\C20 1.355(9) (A) 1.367(9) (B), C4\C5 1.506(11) (A) 1.477(11) (B),
C20\C21 1.483(11) (A), 1.471(11) (B); C2\N1\C32 124.2(6) (A) 124.4(6) (B), C4\N2\C11 131.1(6) (A) 129.5(6) (B), C18\N3\C16 125.6(6) (A) 124.5(6) (B), C20\N4\C27
1
1
1
33.1(7) (A) 130.0(6) (B), N1\C2\C3 119.9(7) (A) 118.7(7) (B), C2\C3\C4 127.3(7) (A) 128.6(7) (B), C3\C4\N2 121.5(7) (A) 120.1(7) (B), N3\C18\C19 121.2(7) (A)
19.5(7) (B), C18\C19\C20 127.0(7) (A) 128.1(7) (B), C19\C20\N4 121.4(7) (A) 119.7(7) (B).
planes of the macrocycle: ∠([N
4
]\[N1\C32\C27\N4])=29.00° (A)
]\[N2\C11\C16\N3])=26.77° (A) (26.99°
]\[C(11\16)])=33.23° (A) (33.28° (B)), ∠([N ]\[C
27\32)])=35.99° (A) (31.63° (B)), ∠([N ]\[N1\C2\C4\N2])=
2.89° (A) (21.41° (B)), ∠([N ]\[N3\C18\C20\N4])=25.37° (A)
24.76° (B)), ∠([N ]\[C2\C3\C4])=25.59° (A) (20.52° (B)), ∠([N ]\
C18\C19\C20])=25.37° (A) (27.66° (B)), ∠([N ]\[C(5–10)])=
0.31° (A) (39.94° (B)), ∠([N ]\[C(21–26)])=44.79° (A) (34.91°
B)). Though the aforementioned dihedral angles in 1 and 3 show
considerable difference, for example, the dihedral angles of the benzo
rings and the N plane in 3 are larger than those in 1, while the dihedral
angles of the diiminato fragments and the N plane in 3 are smaller than
those in 1, both 1 and 3 keep the optimal conformations to overcome the
steric hindrance between the multiple substituents and the macrocycles.
In 3, two NH groups are on the side of the phenyl substituents. Thus,
C2\N1, C18\N3 are imino C_N bonds and C4\N2, C20\N4 are amino
C\N bonds. These results can also be verified by the lengths of the
corresponding bonds. The bond lengths of C2\N1 and C18\N3 are
1.305 and 1.295 Å (A) (1.310 and 1.312 Å (B)), respectively, which are
obviously shorter than those of C4\N2 and C20\N4 (1.364 and 1.355 Å
(A), 1.360 and 1.367 Å (B)). Furthermore, imino N1 and N3 including
C\N\C bond angle values (C2\N1\C32 124.2° (A) 124.4° (B),
C18\N3\C16 125.6° (A) 124.5° (B)) are obviously smaller than
amino N2 and N4 including ones (C4\N2\C11 131.1° (A) 129.5° (B),
(
(
(
25.53° (B)), ∠([N
B)), ∠([N
4
4
4
4
2
4
(
4
4
[
4
(
4
4
4
4
Fig. 3. ORTEP drawings of 3 (left) and 4 (right). The H atoms are omitted for clarity. Selected bond distances (Å) and angles (°) for 4: Ni1\N1 1.870(3), Ni1\N2 1.848(3), Ni1\N3
1
1
.880(3), Ni1\N4 1.853(3), N1\C2 1.330(4), N2\C4 1.348(4), N3\C18 1.326(4), N4\C20 1.347(4), C4\C5 1.491(5), C20\C21 1.496(5); N1\Ni1\N3 176.29(12), N2\Ni1\N4
75.24(12), N1\Ni1\N2 94.45(12), N2\Ni1\N3 85.48(12), N3\Ni1\N4 95.86(12), N4\Ni1\N1 84.52(12).

X. Shen et al. / Inorganic Chemistry Communications 14 (2011) 1555–1560
1559
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bigger than that of H tmtaa (1.902 Å) [3].
is obtained from the reaction of NiAc
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space group P2 /n [31]. ORTEP view of 4 is shown in Fig. 3. 4 assumes
the same saddle-shaped conformation of 3 with two benzo rings and
two diiminato fragments pointing to opposite directions. However,
4
almost all dihedral angles of the N plane and other planes of the
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‘core size’ of 3 is 2.040 Å
(
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.273 Å. This may be due to the strong distorting effect of the methyl
and phenyl substituents to the N plane. The average Ni\N bond
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including amino N (Ni1\N2 1.848 and Ni1\N4 1.853 Å), correspond-
ing to bigger N1\Ni1\N3 angle (176.29°) with respect to
N2\Ni1\N4 angle (175.24°). The N\Ni\N angles in the five-
member ring (N4\Ni1\N1 84.52 and N2\Ni1\N3 85.48°) are
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[
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, the lengths of C\N bonds in two diiminato fragments are all
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[
9
2
2
[
than that of its structure isomer, 2, leading to the negligence of 4 in
previous works. n-Butyl alcohol has been artfully used to purify 4 from
the crude product of the template reaction. 3, the macrocyclic free
base of 4, has also been synthesized and characterized unambiguous-
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X-ray diffraction analysis for the first time. Because of the flattening
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discovery of 3 and 4 will expend the research field of this series of
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We are grateful to the Natural Science Foundation of the Jiangsu
Higher Education Institutions of China (grant no. 09KJB150003) and
the Open Project Program of the State Key Laboratory of Materials-
Oriented Chemical Engineering, China (grant no. KL10-14) for
financial support.
macrocyclic Schiff bases complexes, Bull. Acad. Pol. Sci. Ser. Chim. 28 (1980)
371–376.
[
21] H. Schumann, Dynamic 7Li NMR investigation of dianionic dibenzotetraaza[14]-
annulene derivatives in solution, Polyhedron 15 (1996) 2327–2333.
[22] J. Eilmes, M. Basato, G. Valle, Nickel complexes of tetradentate asymmetric ligands
Inorg, Chim. Acta 290 (1999) 14–20.
[
23] D.V. Soldatov, P.R. Diamente, C.I. Ratcliffe, J.A. Ripmeester, (6,17-Dimethyl-8,15-
diphenyldibenzo[b,i][1,4,8,11]tetraaza[14]annulenato)nickel(II) in solids: two
guest-free polymorphs and inclusion compounds with methylene chloride and
fullerene (C(60)) carbon disulfide, Inorg. Chem. 40 (2001) 5660–5667.
24] J. Eilmes, O. Michalski, K. Woźniak, New chiral receptors based on dibenzo-
tetraaza[14]annulenes, Inorg. Chim. Acta 317 (2001) 103–113.
Appendix A. Supplementary material
[
CCDC 657136 and 764814 contain the supplementary crystallo-
graphic data for compounds 3 and 4. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via http://
www.ccdc.cam.ac.uk/data_request/cif.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.inoche.2011.05.040.
[25] J. Eilmes, M. Ptaszek, Ł. Dobrzycki, K. Woźniak, New alkoxycarbonyl derivatives of
dibenzotetraaza[14]annulene. Crystal and molecular structure of [5,14-dihydro-
7
,16-diisopropoxycarbonyl-8,15-dimethyl-6,17-diphenyldibenzo[b, i][1,4,8,11]-
4
tetraazacyclotetradecinato(2-)-κ N]nickel(II), Polyhedron 22 (2003) 3299–3305.
[26] S. Chandra, M. Tyagi, S. Agrawal, Synthesis and characterization of a tetraaza-
macrocyclic ligand and its cobalt(II), nickel(II) and copper(II) complexes, J. Serb.
Chem. Soc. 75 (2010) 935–941.
[
27] A.R. Cutler, C.S. Alleyne, D. Dolphin, [N, N″-(1,3-propanediylidene)bis(1,2-
benzenediaminato)]nickel(II) complexes: intermediates in the template synthe-
sis of dibenzotetraaza[14]annulenes, Inorg. Chem. 24 (1985) 2281–2286.
References
[1] C.-X. Ding, J. Ni, C.-H. He, F.-H. Zeng, W.-H. Zhu, Y.-S. Xie, A zipper-like double
chain coordination polymer constructed from novel pseudo-macrocyclic
[28] Y.W. Park, S. Oh, Studies on reactions of a nickel complex of a new completely
conjugated macrocyclic ligand, Bull. Korean Chem. Soc. 8 (1987) 476–479.
a
binuclear Cu(II) complex, Inorg. Chem. Commun. 14 (2011) 370–373.
2] E.G. Jäger, Aminomethylen-β-dicarbonylverbindungen als Komplexliganden. V.
Neue konjugiert-ungesättigte Neutralkomplexe mit vierzehngliedrigen makro-
zyklischen Liganden, Z. Anorg. Allg. Chem. 364 (1969) 177–191.
[29] Synthesis of 3: a mixture of 2 and 4 in a mole ratio of 1:5 (3.009 g, 5.73 mmol) and
[
ethanol (100 mL) were added in
a 200 mL three-necked flask to form a
suspension. With the cooling of water bath, hydrogen chloride gas was blown
slowly into the stirred suspension as far as the color of the solution changed and

1560
X. Shen et al. / Inorganic Chemistry Communications 14 (2011) 1555–1560
yellow-white precipitates appeared. After the reaction mixture was stirred
chloroform was slowly added dropwise and the reaction mixture was refluxed for
2 h. The solvent was removed by evaporation and the product was purified and
separated on an alumina chromatographic column using chloroform as elutriant.
After the filtrate was reduced to ca. 20 mL by evaporation, 20 mL acetone was
further added in. The solution was allowed to stand overnight at room
temperature to give dark green crystals of 3 in a yield of 1.351 g (96.3%). Perfect
crystals were chosen out for X-ray crystal structure analysis. Anal. Calc. for 4
overnight at room temperature, the solid was collected by filtration and washed
with ethanol. Then this hydrochloride was dissolved in distilled water. After the
insoluble residues were removed by filtration, the filtrate was neutralized by
adding potassium carbonate to give dark orange precipitates. Then the
neutralized suspension was poured into a separating funnel and extracted with
50 mL dichloromethane three times. After being dried with magnesium sulfate,
the extract was evaporated to give powder. Dissolving the powder in
dichloromethane formed a saturated solution in which a little hexane was then
added. The mixture was allowed to stand overnight at room temperature to give
tawny block crystals of 3 which were suitable for X-ray crystal structure analysis
(C32
H N Ni, 524.15): C, 73.17; H, 4.99; N, 10.67. Found: C, 73.24; H, 4.91; N,
26 4
−
1
10.55%. M.p.: 385–388 °C (DSC). IR (KBr, cm ): ν(C_C, C_N) 1539, 1514, 1472,
1366. FAB+ MS: 525 (M+1)+
.
1
H NMR (400 MHz, CDCl
), 6.41 (m, 2H, C ), 6.16 (m, 2H, C
), 5.03 (s, 2H, CH), 2.22 (s, 6H, CH ).
, M
(3) Å, b=11.602(9) Å, c=19.546(6) Å, α=89.95(4)º, β=92.27(2)º, γ=98.64
3
) (ppm): δ 7.33 (m, 10H,
C
C
6
H
H
5
), 6.75 (m, 2H, C
6
H
4
6
H
4
6 4
H ), 5.67 (m, 2H,
in a yield of 1.281 g (47.7%). Anal. Calc. for 3 (C32
H
28
N
4
, 468.23): C, 82.02; H, 6.02;
6
4
3
N, 11.96. Found: C, 81.93.15; H, 6.07; N, 11.95%. M.p.: 268–271 °C (DSC). IR (KBr,
[31] Crystallographic data for 3: C32
H
28
N
4
r
=468.60, triclinic P-1 with a=11.207
cm ): ν(C_C, C_N) 1612, 1551, 1508, 1450. FAB MS: 469 (M+1)+
400 MHz, CDCl ) (ppm): δ 12.68 (s, 2H, NH), 7.36–7.40 (m, 10H, C ), 6.90 (m,
H, C ), 6.83 (m, 2H, C ), 6.63 (m, 2H, C ), 6.23 (m, 2H, C ), 5.16 (s, 2H,
CH), 2.32 (s, 6H, CH ).
30] Synthesis of 4: after ethanol (70 mL) and NiAc
−
1
+
.
1
H NMR
3
− 3
(
2
3
6
H
5
(4)º, V=2511(2) Å , Z=4,
=0.0575, ωR =0.2033, (IN2σ(I)),
Crystallographic data for 4: C32 Ni, M
a = 8.9847(14) Å, b = 10.5286(16) Å, c = 26.155(4) Å, β = 98.726(2)º,
D
c
=1.240 g cm
=0.0617, ωR
=525.28, monoclinic P2
,
F(000)=992, GOF=0.975,
=0.2186 (all data).
/n with
6
H
4
6
H
4
6
H
4
6
H
4
R
1
2
R
1
2
3
H
26
N
4
r
1
[
2 2
·4H O (0.801 g, 3.21 mmol) were
3
− 3
added in a 200 mL three-necked flask, the mixture was heated with stirring as far
as the solids dissolved completely. Then a solution of 3 (1.254 g, 2.67 mmol) in
V= 2445.5(7) Å , Z =4,
D
c
=1.427 g cm
,
F(000)=1096, GOF=1.014,
R
1
=0.0453, ωR =0.1038, (IN2σ(I)), R
2
1
=0.0815, ωR
2
=0.1258 (all data).