Synthesis and 1-D double line supramolecular structure of a Ni(II) complex with N-alkylated dien

Article abstract of DOI:10.1081/SIM-200066988

A novel N-alkylated diethylenetriamine ligand L·3HCl (L=N, N′-bis(4-methoxylbenzyl)-diethylenetriamine) and its mononuclear Ni(II) complex [Ni(L)phenCl]ClO₄ (1) (phen = o-phenanthroline) were synthesized and spectroscopically characterized. X-ray analysis indicates that octahedral geometry of the Ni(II) center is finished by three N atoms of dien moiety of the ligand in meridional fashion, two N atoms of phen and one Cl anion. Along the a axis, the neighboring molecules are connected via hydrogen bonds involving ClO₄^- anions and N-H groups of the ligands, thus forming a 1-D linear structure which is further connected to the other symmetry-related line via π ... π stacking interactions of phen rings. The steric effect related to the molecular structure of L has been discussed. Copyright

Full text of DOI:10.1081/SIM-200066988

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Synthesis and 1-D Double Line Supramolecular
Structure of a Ni(II) Complex with N-alkylated Dien
Liu Xue-Ting a , Xie Yong-Shu b & Liu Qing-Liang b
a School of Chemical Engineering, Hefei University of Technology, Hefei, China
b Department of Chemistry, University of Science and Technology of China, Hefei, China
Version of record first published: 31 Jan 2012.
To cite this article: Liu Xue-Ting, Xie Yong-Shu & Liu Qing-Liang (2005): Synthesis and 1-D Double Line Supramolecular
Structure of a Ni(II) Complex with N-alkylated Dien, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
Chemistry, 35:6, 459-462
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Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 35:459–462, 2005
Copyright # 2005 Taylor & Francis, Inc.
ISSN: 0094-5714 print/1532-2440 online
DOI: 10.1081/SIM-200066988
Synthesis and 1-D Double Line Supramolecular Structure
of a Ni(II) Complex with N-alkylated Dien
Liu Xue-Ting
School of Chemical Engineering, Hefei University of Technology, Hefei, China
Xie Yong-Shu and Liu Qing-Liang
Department of Chemistry, University of Science and Technology of China, Hefei, China
corresponding complexes, due to the steric hindrance and elec-
novel N-alkylated diethylenetriamine ligand L 3HCl tronic effect induced by the modification. Herein, we syn-
.
A
(L55N, N0-bis(4-methoxylbenzyl)-diethylenetriamine) and its
.
thesized a novel derivative of dien ligand L 3HCl (L ¼ N,
mononuclear Ni(II) complex [Ni(L)phenCl]ClO4 (1) (phen 5
o-phenanthroline) were synthesized and spectroscopically charac-
terized. X-ray analysis indicates that octahedral geometry of the
Ni(II) center is finished by three N atoms of dien moiety of the
ligand in meridional fashion, two N atoms of phen and one Cl
anion. Along the a axis, the neighboring molecules are connected
via hydrogen bonds involving ClO24 anions and N-H groups of
the ligands, thus forming a 1-D linear structure which is further
N0-bis(4-methoxylbenzyl)-diethylenetriamine) and its mixed
ligand complex [Ni(L)phenCl]ClO4 (1) (phen ¼ o-
phenanthroline).
The self-assembly of supramolecular coordination assem-
blies has also caused extensive interest in recent years (Xie
et al., 2003; Munakata et al., 1996; Dai et al., 1997). The
amine groups in L and the ClO24 counteranions can act as
donors and acceptors of hydrogen bonding, while the ring of
. . .
connected to the other symmetry-related line via p p stacking
interactions of phen rings. The steric effect related to the molecu-
lar structure of L has been discussed.
. . .
phen can be involved in p p stacking interactions. Thus,
in the crystal structure of complex 1, a double line 1-D supra-
molecular structure is formed by multiple hydrogen bonds and
Keywords 1-D double line supramolecular structure, N-alkylated
diethylenetriamine, Ni(II) complex, steric effect
. . .
p p stacking interactions. The steric hindrance concerning
the modification of dien is discussed.
EXPERIMENTAL
INTRODUCTION
Materials and Physical Measurements
Great efforts have been devoted to the research of transition
metal coordination compounds of dien(diethylene triamine)
(Hynes et al., 1996; Mukherjee et al., 1994). Dien ligand has
three coordination atoms which often coordinate metal center
in facial or meridional fashion, thus forming stable tridentate
chelate structure. There exist a wide range of applications of
the transition metal coordination compounds of dien in the
template synthesis of new compounds, preparation of low
dimensional materials (Zheng et al., 1999). N-alkylation of
dien can modify the structures and properties of the
All of the solvents and raw materials were analytical grade
and used as received without further purification.
I.R. spectra were recorded on a Bruker Vector-22 spec-
trometer (KBr Disc.). The 1H NMR measurements were
carried out on a Bruker 300 ultrashield NMR spectrometer in
D2O (99.85%). Elemental analyses (C, H and N) were
performed on Elementar Vario EL-III elemental analyzer.
Electronic spectra were measured by a UV-2401PC spectro-
photometer in DMSO.
.
Preparation of L 3HCl (L 5 N,
N0-bis(4-methoxylbenzyl)-diethylenetriamine)
To the methanol solution of 4-methoxyl-phenylaldehyde
(10.0 g, 0.073 mol) was added diethylenetriamine (3.8 g,
0.037 mol). After stirring for one day, KBH4 (4.6 g) was
added in small portions to the yellow-orange solution. The
solution gradually faded to nearly colorless. Two hours later,
the pH of the solution was adjusted to about 5 with
Received 30 December 2004; accepted 25 March 2005.
This work was financially supported by the National Science Foun-
dation of China (No.30270321) and Science Development Foundation
of Hefei University of Technology (No. 030601F).
Address correspondence to Liu Qing-Liang, Department of Chemi-
stry, University of Science and Technology of China, Hefei 230026,
China. E-mail: qliu@ustc.edu.cn
459

460
L. XUE-TING ET AL.
hydrochloric acid, and then to about 9 with NaOH. After fil- (0.079 g, 0.40 mmol) was added. Two hours later, the residue
tration, the resulting solution was concentrated in vacuo. The was filtered off. The resulting light green solution was concen-
residue was extracted with water and CH2Cl2. The CH2Cl2 trated in vacuo and left undisturbed at room temperature for
layers were collected and dried overnight with Na2SO4. After two weeks, yielding light green crystals suitable for X-ray
filtration, the resulting solution was concentrated in vacuo to diffraction analysis. Yield: 0.120 g, 41.8%. Anal. Calc. for
give light yellow oily residue. Upon adding hydrochloric C32H37Cl2N5NiO6: C, 53.6; H, 5.2; N, 9.8%. Found: C, 53.9;
acid, a white solid precipitated, which was collected, washed H, 5.0; N, 9.6%. I.R. (KBr Disc, cm21): 3441(m), 3284(m),
with cold ethanol and dried. Yield: 10.1 g, 60.7%. Anal. Calc. 2927(m), 2360(w), 1611(m), 1584(w), 1512(s), 1445(m),
for: C20H32N3O2Cl3, C, 53.0; H, 7.1; N, 9.3%. Found: C, 52.7; 1426(s), 1336(w), 1304(w), 1247(s), 1208(w), 1177(m),
H, 7.1; N, 9.6%. I.R. (KBr Disc, cm21): 2935(s), 2725(br, s), 1140(w), 1099(s), 1026(s), 996(w), 958(s), 919(w), 878(w),
2556(m), 2426(s), 1615(s), 1585(m), 1518(vs), 1451(m), 840(s), 813(m), 754(w), 725(m), 622(s), 522(w), 424(w).
1303(m), 1254(vs), 1185(m), 1033(s), 972(w), 818(s), 757(w),
561(w), 532(w). 1H NMR. (D2O): 4.25 (4H, s, Ar-CH2-),
Crystallographic Data Collection and Refinement
3.38–3.45 (8H, d, NH-(CH2)2-NH), 7.05–7.45(8H, m, Ar-H),
3.85 (6H, s, -OCH3).
of the Structure
Single crystal of 1 was mounted on a glass-fiber. All
measurements were made on a Rigaku RAXIS-IV image
Preparation of [Ni(L)phenCl]ClO4 (1)
.
To the methanol solution of L 3HCl (0.181 g, 0.40 mmol)
.
was added Ni(ClO4)2 6H2O (0.146(g), 0.40 mmol) with con-
plate area detector with graphite monochromated Mo-Ka radi-
ation. The data were collected at 18 8C and corrected for
Lorentz and polarization effects. The correction for secondary
extinction was applied. The structure was solved by direct
methods, and expanded using Fourier techniques. The non-
hydrogen atoms were refined anisotropically. Hydrogen
atoms were included but not refined. The final cycle of full-
matrix least-squares refinement was based on observed reflec-
tions (I . 2.00s (I)) and variable parameters. All calculations
were performed using SHELX-97 software package (Sheldrick,
1997). Crystallographic data for 1 are listed in Table 1.
Selected bond lengths and angles for 1 are listed in Table 2.
tinuous stirring, followed by addition of aqueous solution of
NaOH (4 N, 0.30 ml). After refluxing for 1 hour, phen
TABLE 1
Crystallographic data for 1
Empirical formula
Formula weight
Temperature
C32H37Cl2N5NiO6
717.28
291(2) K
˚
0.71073 A
Wavelength
Crystal system, space group monoclinic, P2 (1)/c
RESULTS AND DISCUSSION
˚
Unit cell dimensions
a ¼ 8.9670(18) A, a ¼ 908
Spectroscopic Characterization of 1
˚
b ¼ 15.274(3) A,
The medium band in the IR spectrum at 3284 cm21 is
related to n(NH) of the ligand, and two strong bands at
1099 cm21 and 622 cm21 are characteristic of uncoordinated
ClO24 . Upon coordination, two obvious absorption bands for
free phen at 1421 cm21 and 853 cm21 are each shifted
b ¼ 92.22(3)8
˚
c ¼ 24.161(5) A, g ¼ 908
3
˚
Volume
3306.6(12) A
23
.
4, 1.441 Mg m
0.800 mm21
1496
Z, Calculated density
Absorption coefficient
F(000)
upfield and downfield, i.e., to 1426 cm21 and 840 cm21
,
Crystal size
u range for data collection
Index ranges
0.22 ꢀ 0.20 ꢀ 0.20 mm
1.588 to 24.008
0 ꢁ h ꢁ 10, 217 ꢁ k ꢁ 17,
227 ꢁ l ꢁ 27
TABLE 2
˚
Selected bond lengths (A) and bond angles (8) for 1
Reflections collected/unique 7680/4472 [R(int) ¼ 0.0972]
Completeness to 2u ¼ 24.00 88.6%
Ni(1)-N(4)
Ni(1)-N(1)
Ni(1)-N(3)
2.069(5) Ni(1)-N(2)
2.122(4) Ni(1)-N(5)
2.183(5) Ni(1)-Cl(1)
2.080(4)
2.135(5)
2.447(2)
97.4(2)
Max. and min. transmission
Refinement method
0.8564 and 0.8437
Full-matrix least-squares on F2
4472/0/428
N(4)-Ni(1)-N(2) 173.3(2)
N(2)-Ni(1)-N(1)
N(4)-Ni(1)-N(5)
N(4)-Ni(1)-N(1)
N(2)-Ni(1)-N(5)
Data/restraints/parameters
Goodness-of-fit on F2
78.5(2)
81.6(2)
93.9(2)
1.005
a
N(2)-Ni(1)-Cl(1) 91.7(1)
N(1)-Ni(1)-Cl(1) 169.0(1)
N(5)-Ni(1)-Cl(1) 85.1(2)
N(3)-Ni(1)-Cl(1) 86.0(1)
N(5)-Ni(1)-N(3) 161.0(2)
b
Final R indices [I . 2s (I)]
R indices (all data)
Extinction coefficient
R1 ¼ 0.0685, wR2 ¼ 0.1709 N(1)-Ni(1)-N(5) 100.5(2)
a
b
R1 ¼ 0.0967, wR2 ¼ 0.1844 N(4)-Ni(1)-N(3)
0.0037(7)
N(2)-Ni(1)-N(3) 103.1(2)
0.620 and 20.697 e.A
N(1)-Ni(1)-N(3) 91.2(2)
N(4)-Ni(1)-Cl(1) 92.8(2)
82.1(2)
23
˚
Largest diff. peak and hole
aR1 ¼ SjjFoj 2 jFcjj/SjFoj;bwR2 ¼ SjjFoj 2 jFcjjw1/2/SjFoj w1/2
.

SYNTHESIS AND STRUCTURE OF A NI(II) COMPLEX
461
dien moiety of the ligand in meridional fashion, two N
atoms of phen and one Cl2 anion. The distortion can be evi-
denced by the relative small trans angles (about between
161 ꢀ 1738), very large variation of cis angles (about from
˚
788 to 978) and Ni(1)-N distances (from 2.08 to 2.18 A)
(Table 2). In 1, two long Ni(1)-N bonds and one short
Ni(1)-N bond are each corresponding to two terminal NH
groups and one middle NH group of L. The difference of
Ni(1)-N distances may be derived from the large steric hin-
drance of benzyl group, which may also cause three N
atoms of dien moiety of L to coordinate to Ni(II) in meridional
fashion in 1. In contrast, the introduction of methyl group to
the middle NH group of dien may favor three N atoms of
dien in facial configuration as in [Ni(medien)(NCS)(m-
SCN)]n (medien ¼ N-(2-aminoethyl)-N-methyl-1, 2-ethane-
diamine) (Nayak et al., 1998). The two bite angles of dien
for Ni(II) center (N(4)-Ni(1)-N(3) ¼ 82.1(2)8, N(4)-Ni(1)-
N(5) ¼ 81.6(2)8) are smaller than 908 is the result of steric
constraints imposed by ethylene bridges, while that its trans
angle is smaller than 1808 is caused by steric constraint
imposed by tridentate coordination mode of dien (Johns and
Malik, 2002). Selected torsion angles of 1 are listed in Table 3.
Two torsion angles of dien, N(5)-C(13)-C(14)-N(4)
(53.5(7)8) and N(4)-C(15)-C(16)-N(3) (258.1(6)8), indicate
that two ethylenediamine groups are each in gauche(l) and
gauche(d) geometries respectively, i.e., ld geometry, which
is consistent with that of the reported Ni(II) complex of dien
(Johns and Malik, 2002). It is interesting that there exists
FIG. 1. ORTEP view of complex 1 at the 30% probability level.
respectively. For dien, there exist several rotation isomers, e.g.,
cis, trans, gauche(l), gauche(d); however, upon coordination,
gauche isomers are most commonly observed (Kazuo, 1986).
In contrast to free L, the appearance of one weak band of 1
at 919 cm21 suggests that, when coordinated, two ethylenedia-
mine moieties of L are both in gauche geometry (vide infra)
(Kazuo, 1986).
. . .
strong intramolecular p p stacking interaction in edge to
edge fashion between one phenyl ring of L and phen ring,
the shortest distance between carbon atoms of them being
In the electronic spectra of 1, two weak bands located at
565 nm and 818 nm may be assigned to two d-d transitions
˚
about 3.38 A.
3
of the octahedrally coordinated Ni(II) complex, A2 g
Along the a axis, 1D supramolecular structure, consisting of
symmetry related double lines, is constructed (Figure 2). In
each line, the adjacent molecules are connected through
hydrogen bonds forming between ClO24 anions and N-H
groups of the ligands (Table 4). It is worth noting that, like
intramolecular aromatic stacking interaction (vide supra),
3
3
3
(F) ! T1 g (F) and A2 g (F) ! T2 g (F), but, the third d-d
3
3
transition for A2 g (F) ! T1 g (P) is overlapped by other
strong bands of higher energy.
Description of the Structure
. . .
obvious p p stacking interactions in edge to edge fashion
also occur between phen rings from intermolecular double
lines where the shortest distance between carbon atoms of
X-ray diffraction analysis indicates that 1 consists of one
[Ni(L4) phenCl]þ cation and one ClO24 anion (Figure 1).
The Ni(II) center is situated in distorted octahedral coordi-
nation environment, which is composed of three N atoms of
˚
phen rings is about 3.44 A.
TABLE 3
Selected torsion angles (8) for 1
C(25)-N(5)-C(13)-C(14) 2169.5(5) Ni(1)-N(5)-C(13)-C(14)
C(15)-N(4)-C(14)-C(13) 2170.8(5) Ni(1)-N(4)-C(14)-C(13)
232.9(6)
247.4(6)
169.6(5)
178.1(5)
258.1(6)
262.3(6)
234.9(8)
N(5)-C(13)-C(14)-N(4)
Ni(1)-N(4)-C(15)-C(16)
Ni(1)-N(3)-C(16)-C(15)
C(16)-N(3)-C(17)-C(18)
N(3)-C(17)-C(18)-C(19)
53.5(7) C(14)-N(4)-C(15)-C(16)
46.2(6) C(17)-N(3)-C(16)-C(15)
39.4(5) N(4)-C(15)-C(16)-N(3)
169.5(5) Ni(1)-N(3)-C(17)-C(18)
147.4(6) N(3)-C(17)-C(18)-C(23)

462
L. XUE-TING ET AL.
obtained free of charge from The Director, CCDC, 12 Union
Road, Cambridge, CB2 IEZ, UK (fax: þ44-1223-336033;
E-mail: deposit@ccdc.cam.ac.uk or www.ccdc.cam.ac.uk).
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.
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.
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TABLE 4
˚
Hydrogen bond lengths (A) and angles (8) for 1
D-H
d(D-H) d(H.A) ,DHA d(D.A) A (symmetry
operations)
N4-H4E 0.85
N3-H3E 0.93
2.32
2.60
149
148
3.07 O3
3.41 O5 [x-1, y, z]
In conclusion, a novel derivative of dien and its mixed
ligand mononuclear Ni(II) complex 1 were synthesized and
characterized. Crystal structure research indicates that the
Ni(II) center is coordinated by three dien N atoms of the
ligand in meridional fashion, two phen N atoms and one Cl2
anion, thus forming distorted octahedral geometry. Along the
a axis, 1D double line supramolecular structure is assembled
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methyl-1,2-ethanediamine. Acta. Cryst. Sect. C. 1998, 54,
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ment, University of Gottigen, Germany, 1997.
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. . .
via intermolecular hydrogen bonds and p p stacking inter-
actions. The steric effect concerning the molecular structure
of L has also been discussed.
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One- and two-dimensional materials containing vanadium oxide:
Supplementary Data
Crystal structure data of 1 have been deposited at the
Cambridge Crystallographic Data Centre and allocated the
deposition number 244550. Copies of this information can be
.
structures and magnetic properties of Cu(dien)V2O6 H2O and
Ni(dien)V2O6 (dien ¼ diethylenetriamine). J. Chem. Soc. Dalton.
Trans. 1999, 6, 939–943.