Template synthesis and X-ray crystal structures of 15-membered unsymmetric monobenzotetraazaannulene nickel(II) complexes

Article abstract of DOI:10.1016/j.ica.2012.12.041

New nickel(II) complexes A and B having macrocyclic ligands 4,10-dimethyl-2,12-diphenyl-1,5,9,13-dimethylbenzotetraazacyclo[15]tetradecine and 4,10-dimethyl-2,12-diphenyl-1,5,9,13-nitrobenzotetraazacyclo[15]tetradecine, respectively, have been synthesized and characterized by spectroscopic methods, including single-crystal X-ray diffraction. The nickel and four nitrogen atoms in both of the unsymmetrical tetraaza[15]annulene-ligated complexes have a slightly distorted square-planar arrangement rather than a square-pyramidal one, despite ring strain from coordination with the propylenediamine group.

Full text of DOI:10.1016/j.ica.2012.12.041

Inorganica Chimica Acta 399 (2013) 62–66
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Template synthesis and X-ray crystal structures of 15-membered unsymmetric
monobenzotetraazaannulene nickel(II) complexes
⇑
Eunhee Kim, Hyosun Lee
Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, 1370 Sankyuk-dong, Buk-gu, Daegu-City 702-701, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
New nickel(II) complexes A and B having macrocyclic ligands 4,10-dimethyl-2,12-diphenyl-1,5,9,13-dim-
ethylbenzotetraazacyclo[15]tetradecine and 4,10-dimethyl-2,12-diphenyl-1,5,9,13-nitrobenzotetraaza-
cyclo[15]tetradecine, respectively, have been synthesized and characterized by spectroscopic methods,
including single-crystal X-ray diffraction. The nickel and four nitrogen atoms in both of the unsymmet-
rical tetraaza[15]annulene-ligated complexes have a slightly distorted square-planar arrangement rather
than a square-pyramidal one, despite ring strain from coordination with the propylenediamine group.
Ó 2013 Elsevier B.V. All rights reserved.
Received 11 November 2012
Received in revised form 16 December 2012
Accepted 17 December 2012
Available online 4 January 2013
Keywords:
Benzotetraaza[15]annulene
Substituted benzotetraaza[15]annulene
Template synthesis
Unsymmetric monobenzotetraazaannulene
nickel(II) complex
1. Introduction
methyl substituents on the macrocyclic rings. Park et al. [29–37]
have reported various synthetic routes to unsymmetrical tetra-
Macrocyclic tetraazaannulene complexes are of interest be-
cause of their utility as models for porphyrins, phthalocyanines,
and corrin rings, which are found in heme proteins, metalloen-
zymes, and other biological systems [1–9]. Recently, their applica-
tions have been extended to catalysis [10,11] and material
precursors such as electrically conductive polymers [12,13].
Synthesis of unsymmetric tetraazaannulene complexes generally
involves the reactions of symmetrical tetraazacyclo[14]annulene
nickel(II) complexes with electrophiles such as perfluorobenzoyl,
azobenzene, and benzoyl groups [14–18]. The reactivity of tetra-
azaannulene complexes toward various reagents may be used to
introduce structural modifications, which provide complexes suit-
able as model compounds for biologically important macrocyclic
systems. Unsymmetric tetraazaannulenes can be prepared by
demetallation of tetraazacyclo[14]annulene nickel(II) complexes
followed by insertion of the desired metals into the macroligands
[19,20]. An alternative approach is the reaction between an
unsymmetrical or symmetrical macrocyclic tetraazaannulene and
a metal-containing starting material [21]. However, most tetraaza-
annulene metal complexes prepared by the Jäger method [22–24]
are symmetric complexes with mainly 14-membered tetraazaan-
nulene macrocyclic rings [25–28]. The syntheses and applications
are much less developed for those metal complexes having unsym-
metrical 15-membered tetraazaannulenes with diphenyl and di-
methyl tetraazacyclo[14]annulene nickel(II) complexes, including
using the free ligand tetraazacyclo[14]tetradecine; they have also
determined their crystal structures and electrical properties and
explored their catalytic activities for the oxidation of styrene
derivatives.
In this paper, we report the synthesis and characterization of new
15-membered unsymmetrical tetraazacycloannulene nickel(II)
complexes having dimethyl-diphenyl and nitro-diphenyl substitu-
ents on the macrocyclic rings, i.e., 4,10-dimethyl-2,12-diphenyl-
1,5,9,13-dimethylbenzotetraazacyclo[15]tetradecinato nickel(II)
(A) and 4,10-dimethyl-2,12-diphenyl-1,5,9,13-nitrobenzotetraaza-
cyclo[15]tetradecinato nickel(II) (B). The spectral and structural
properties of the unsymmetrical tetraazacyclo[15]annulene nicke-
l(II) complexes were determined using 1H and 13C NMR, electronic
absorption, and X-ray diffraction.
2. Experimental
2.1. Materials and Instrumentation
Ni(OAc)2ꢀ4H2O, benzoylacetone, 3,4-dimethylphenylenedi-
amine, 1,3-propanediamine were purchased from Aldrich and
anhydrous solvents such as ethanol, dichloromethane were pur-
chased from Merck and used without further purification. 1H
NMR (400 MHz) and 13C NMR (100.61 MHz) were recorded on a
Bruker Advance Digital 400 spectrometer and chemical shifts were
recorded in ppm units using SiMe4 as an internal standard.
⇑
Corresponding author.
E-mail address: hyosunlee@knu.ac.kr (H. Lee).
0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2012.12.041

E. Kim, H. Lee / Inorganica Chimica Acta 399 (2013) 62–66
63
Ni(OAc)2 4H2O
R1
R2
NH2
NH2
N
N
N
O
O
O
O
O
R1
R2
+
R1
R2
H2N(CH2)3NH2
Ni
Ni
Ni
O
O
EtOH
N
O
N
N
R1 = R2 = Me [A]
R1 = H, R2 = NO2 [ ]
B
Scheme 1. Template synthetic scheme for the preparation of complexes A and B.
Coupling constants are reported in Hertz (Hz). Infrared spectra
were recorded on a Matteson Instruments, Inc. Galaxy 7020 A
using KBr Pellets. EI mass spectra were determined with a JEOL
MS-DX 300 gas chromatograph mass spectrometer at 70 eV using
a direct inlet system. Electronic absorption spectra were obtained
on a Shimadzu UV-265 spectrophotometer. Elemental analysis
and ICP (Inductively Coupled Plasma) were performed by Fison-
EA1108 and Thermo IRIS XDL duo, respectively.
5.18 and 5.25 (s, 2H, NCCHCN), 5.82 (d, 1H, J = 6.4 Hz, aromatic),
6.73 (d, 1H, J = 6.4 aromatic), 7.02 (t, 1H, J = 6.4 Hz, aromatic),
7.26 (m, 10H, substituted phenyl). 13C-NMR (CDCl3, 400 MHz):
22.46, 22.56 (methyl), 31.31 (NCH2CH2CH2N), 51.24 and 51.61
(NCH2CH2CH2N), 106.96 and 108.84 (NCCHCN), 156.20, 156.99,
163.37, 164.129 (NCCHCN), 115.65, 116.35, 138.06, 138.397,
146.17, 152.34 (aromatic), 119.73, 128.88, 128.90, 128.94,
128.98, 139.19 (substituted phenyl). EIMS: m/z 536 [M]+.
2.3. X-ray crystallographic analysis
2.2. Synthesis of Ni(II) complexes
Preliminary examination and data collection for crystal of Ni(II)
2.2.1. 4,10-Dimethyl-2,12-diphenyl-1,5,9,13-
complex were performed with Mo Ka radiation (k = 0.71073 Å) on
dimethylbenzotetraazacyclo[15]tetradecinato (2-)nickel(II) (A)
Benzoyl acetone (6.5 g, 0.04 mol) was added to nickel(II) acetate
tetrahydrate (5.0 g, 0.02 mol) in absolute ethanol. The mixture was
heated under reflux for 20 min. and 3,4-dimethylphenylenedi-
amine (2.72 g 0.02 mol) in ethanol (10 mL) was added to the
mixture solution. After 5 min. stirring of mixture of solution,
1,3-propanediamine (1.48 g, 0.02 mol) was slowly dropped to the
solution. The reaction mixture was refluxed for 12 h under
bubbling nitrogen gas in the solution to protect it from moisture.
The reaction mixture was then left to stand for 24 h at room tem-
perature and the solid was filtered, washed ethanol (50 mL ꢁ 3),
and dried in vacuum. The crude solid was chromatographed onto
an activated aluminum oxide and eluted with dichloromethane.
The dark red crystal was obtained by recrystallization from a 1:2
mixture of dichloromethane and n-hexane. Yield: 3.74 g, 37.0%.
Anal. Calc. for C62H64N8Ni2: C, 71.70; H, 6.21; N, 10.79. Found: C,
71.79; H, 6.35; N, 10.99%. IR (KBr disc, cmꢂ1): v(C@C), 1452;
v(C@N), 1540; v(aromatic), 746 and 699. 1H NMR (CDCl3,
400 MHz): 1.65 and 2.04 (s, 12H, methyl), 2.32 (m, 2H, NCH2CH2-
CH2N), 2.97 (t, 4H, J = 6.0 Hz, NCH2CH2CH2N), 5.02 (s, 2H, NCCHCN),
5.63 (s, 2H, aromatic), 7.25 (m, 10H, substituted phenyl). 13C
NMR(CDCl3, 400 MHz): 19.50, 22.21 (methyl), 32.03 (NCH2CH2CH2N),
51.39 (NCH2CH2CH2N), 105.48 (NCCHCN), 156.71, 161.68
(NCCHCN), 122.71, 139.69, 144.02 (aromatic), 127.28, 128.07,
128.33, 129.19 (substituted phenyl). EIMS: m/z 519 [M]+.
an Enraf–Nonius CAD4 computer controlled k-axis diffractometer
equipped with a graphite crystal, incident-beam monochromator.
Cell constants and orientation matrices for data collection were ob-
tained from least-squares refinement, using the setting angles of
25 reflections. The data were collected for Lorentz-polarization
and absorption corrections were applied to the data. The structure
was solved by direct methods using SHELXS-86 and refined by full-
matrix least-squares calculations with SHELX-97 [38,39]. All the
non-hydrogen atoms were refined anisotropically, and hydrogen
atoms were added to their geometrically ideal positions.
3. Results and discussion
3.1. Synthesis and electronic absorption data of complexes A and B
The unsymmetrical macrocyclic complexes A and B were pre-
pared by the synthetic procedure as illustrated in Scheme 1. Tem-
plate condensation of a (1:1) mixture of appropriate 4,5-dimetnyl
(or 4-nitro)-1,2-phenylenediamine and propylenediamine with
2,4-pentanedione in the presence of nickel(II) ion gave the substi-
tuted complexes of the 4,10-dimethyl-2,12-diphenyl-1,5,9,13-
dimethylbenzotetraazacyclo[15]tetradecinato nickel(II) (A) and
4,10-dimethyl-2,12-diphenyl-1,5,9,13-nitrobenzotetraazacyclo[15]
tetradecinato nickel(II) (B) were synthesized in 37% and 29% yields,
respectively. Purifications of the crude products were achieved by
column chromatography on activated aluminum oxide and recrys-
tallized from dichloromethane and n-hexane.
2.2.2. 4,10-Dimethyl-2,12-diphenyl-1,5,9,13-
nitrobenzotetraazacyclo[15]tetradecinato(2-) nickel(II) (B)
The complex B was prepared by analogous method as described
for complex A except utilizing 4-nitrophenylenediamine (3.07 g,
0.02 mol). The dark green crystal was obtained by recrystallization
from a 1:2 mixture of dichloromethane and n-hexane. Yield:
2.82 g, 29%. Anal. Calc. for C29H27N5O2Ni(%): C, 64.95; H, 5.07; N,
13.06. Found: C, 64.66; H, 5.12; N, 12.99. IR(KBr disc, cmꢂ1):
v(C@C), 1473; v(C@N), 1554; v(aromatic), 756 and 702, v(NO2),
136. 1H NMR (CDCl3, 400 MHz): 2.10 and 2.11 (s, 6H, methyl),
2.34 (m, 2H, NCH2CH2CH2N), 3.06 (t, 4H, J = 6.0 Hz, NCH2CH2CH2N),
The IR spectra of complexes A and B showed bands at about
1452 and 1540 cmꢂ1 for the C@C group and 1473 and 1554 cmꢂ1
for the C@N function, respectively. The aromatic C–H absorption
bands of the macrocycles and of the substituted phenyl groups ap-
peared at about 746 and 758 cmꢂ1, and 699 and 703 cmꢂ1, respec-
tively. These data were comparable to those for nickel(II)
complexes of tetraazacyclo[14]annulenes [3,40]. The electronic
absorption spectra of complexes
A
and
B
exhibited bands,
and 409 nm
respectively, at 394 )
(
e
max = 23460 Mꢂ1 cmꢂ1

64
E. Kim, H. Lee / Inorganica Chimica Acta 399 (2013) 62–66
complexes A and B are saddle-shaped, similar to those of unsym-
1.5
1.0
0.5
0.0
metrical 14-membered tetraazaannulene nickel(II) complexes hav-
ing ethylenediamine units on the macrocycles [36]. Both complex
A and B consist of four rings with a central Ni atom, i.e., a five-
membered ring that is formed with phenylenediamine, two unsat-
urated six-membered rings, and one saturated six-membered ring
that is coordinated to propylenediamine. The average bond lengths
of Ni1–N1 and Ni1–N2, which are bonds to the phenylenediamine,
are 1.888(3) Å for complex A and 1.871(3) Å for complex B,
whereas the average lengths of Ni1–N3 and Ni1–N4, which are
bonds to propylenediamine, are 1.917(3) Å for complex A and
1.915(3) Å for complex B. The average bond lengths of Ni1–N1
and Ni1–N2 were slightly shorter than those of Ni1–N3 and Ni1–
N4, i.e., by about 0.03 Å. This shortening may be related to the dif-
ferences in ring strains and basicities between phenylenediamine
(pKa1 and pKa2, 1.81 and 4.61, respectively) and propylenediamine
(pKa1 and pKa2, 8.64 and 10.47, respectively) [41–43]. Because
A
B
400
500
600
700
Wave length (nm)
Fig. 1. Electronic absorption spectra of complexes
(2.0 ꢁ 10ꢂ5 M) at room temperature.
A
and
B
in chloroform
(e
max = 30260 Mꢂ1 cmꢂ1), which are attributed to
tions, and in the visible region at 584 (
max = 3220 Mꢂ1 cmꢂ1) and
577 nm (
max = 4320 Mꢂ1 cmꢂ1), which are attributed to ligand-
p?
p⁄ transi-
e
e
to-Ni metal charge transfer (LMCT) from the highest-occupied
molecular orbital of the ligand to the lowest unoccupied
d-orbital of nickel (Fig. 1). Complex B with a nitro group on the
macrocyclic ring exhibited an additional band at 471 nm
(e
max = 7160 Mꢂ1 cmꢂ1), which may be a charge transfer band.
The absorption bands for the dimethyl and diphenyl groups on
the macrocyclic ring in complexes A and B were shifted to longer
wavelengths than observed for the unsymmetrical tetramethyl
groups on the macrocyclic ring in the tetraazaannulene nickel(II)
complex [27]. This shift might be a consequence of an extended
p-conjugation effect by the two substituted phenyl rings on the
macrocyclic ring [29]. The results of 1H-NMR, 13C NMR, and ele-
mental analyses were consistent with the formation of Ni(II) com-
plexes. The proton peaks for the methine sites in complexes A and
B were shifted about d 0.2–0.4 downfield from those for the
tetramethyltetraazaannulene nickel(II) complex [35]. The proton
peaks for the NCCHCN sites of complex A appeared as a singlet at
d 5.02 because of the same affected by dimethyl group on benzene
ring, but for complex B they appeared as two singlets at d 5.18 and
5.25 due to not the same affected by nitro group of that. This indi-
cates that the NCCHCN sites are affected by extended
p-conjuga-
tion of the two phenyl rings and the substituted dimethyl group
in complex A or the nitro group in complex B. The trends in the
13C and 1H NMR chemical shifts were similar. Both spectra were
more affected by the electron withdrawing group, NO2, than by
the electron donating group, CH3, on the phenyl ring of the
macrocycle.
Fig. 2. ORTEP Drawings of complex A. Top (a) and side (b) views with thermal
ellipsoids at 50% probability. All hydrogen atoms have been omitted for clarity.
Selected bond lengths (Å) and angles (o) are Ni(1)–N(1) 1.892(3), Ni(1)–N(2)
1.884(3), Ni(1)–N(4) 1.916(3), Ni(1)–N(3) 1.918(3), N(2)–C(6) 1.404(4), N(2)–C(9)
1.343(4), N(3)–C(19) 1.470(4), N(3)–C(17) 1.322(5), C(16)–C(17) 1.409(5), C(9)–
C(16) 1.388(5); N(1)–Ni(1)–N(2) 82.81(11), N(3)–Ni(1)–N(4) 94.33(12), N(1)–
Ni(1)–N(4) 92.22(12), N(2)–Ni(1)–N(3) 90.66(12), N(2)–Ni(1)–N(4) 174.41(11),
N(1)–Ni(1)–N(3) 173.45(11), Ni(1)–N(2)–C(6) 111.0(2), Ni(1)–N(2)–C(9) 127.7(2),
C(6)–N(2)–C(9) 123.8(3), N(2)–C(9)–C(16) 121.5(3), N(2)–C(9)–C(10) 122.0(3),
C(9)–C(16)–C(17) 123.9(3), Ni(1)–N(3)–C(19) 122.1(2), Ni(1)–N(3)–C(17) 122.9(2),
C(17)–N(3)–C(19) 114.9(3), N(3)–C(17)–C(18) 121.1(3), N(3)–C(17)–C(16) 123.7(3).
3.2. X-ray crystallographic analysis of complexes A and B
The plan and side views of the two complexes including the se-
lected bond lengths and angles in complexes A and B are illustrated
in Figs. 2 and 3. Crystal structure data, details of data collection,
and refinement parameters of the two complexes are listed in
Table 1.
The Ni atom bonded to the four nitrogen atoms has a slightly
distorted square-planar coordination. The overall structures of

E. Kim, H. Lee / Inorganica Chimica Acta 399 (2013) 62–66
65
phenylenediamine is less basic than propylenediamine, both com-
plexes had shorter average bond lengths for Ni1–N1 and Ni1–N2
than for Ni1–N3 and Ni1–N4. The size of the phenylenediamine–
nickel five-membered ring may also be influential: it is smaller
and more strained than the propylenediamine–nickel six-mem-
bered ring.
The average bond lengths of C1–N1 and C6–N2, which are con-
nected to the phenylenediamine unit, are 1.410(3) Å for complex A
and 1.397(3) Å for complex B, whereas the average lengths of C19–
N3 and C21–N4, which are connected to the propylenediamine
unit, are 1.473(3) Å for complex A and 1.478(3) Å for complex B.
The average bond lengths of C1–N1 and C6–N2 were slightly short-
er than those of C19–N3 and C21–N4, i.e., by 0.06(1) Å for complex
A and 0.08(1) Å for complex B. Considering that the average C–C
bond length in benzene is 1.40 Å, a
p
-conjugation effect is clearly
present between the five-membered ring that is formed with
phenylenediamine and the two unsaturated six-membered rings.
The N1–Ni1–N2 bite angle of the five-membered ring was
82.8(2)° and 82.7(2)° in complexes A and B, respectively. This is
comparable to the angle of 85.4(4)° in the symmetrical tetra-
aza[14]annulene nickel(II) [36].
However, the N3–Ni1–N4 bite angle in the saturated six-mem-
bered ring connected to the propylene unit was 94.3(2)° for com-
plex
A and 99.8(2)° for complex B. In comparison, the
corresponding bond angle of the saturated five-membered ring
connected to the ethylene unit in the unsymmetrical tetra-
aza[14]annulene nickel(II) complex [37] was 88.03(10)°. This dif-
ference is attributable to relief of ring strain when moving from a
five- to a six-membered ring in macrocyclic complexes. The aver-
age N1–Ni1–N4 and N2–Ni1–N3 bite angle in the two unsaturated
six-membered rings was 91.5(2)° for A and 90.8(2)° for B. The cor-
responding bite angle in the unsymmetrical tetraaza[14]annulene
nickel(II) complex was 93.16(10)°. Thus, the bond angles for the
two unsaturated six-membered rings in the unsymmetrical tetra-
aza[15]annulene- and tetraaza[14]annulene nickel(II) complexes
were not affected by the change in ring size from six-membered
associated with the propylene unit to five-membered associated
with the ethylene unit.
The N1–Ni1–N3 and N2–Ni1–N4 diagonal angles were
173.45(11)° and 174.41(11)°, respectively, for complex A and
173.65(13)°and 172.87(13)°, respectively, for the complex B. These
Table 1
Crystal data and structure refinements of complexes A and B.
Empirical formula
C62H64N8Ni2 (A)
C29H27N5NiO2 (B)
Formula weight
T (K)
Crystal system
Space group
Unit cell dimensions
a (Å)
1038.63
173(2)
triclinic
P1
536.27
173(2)
triclinic
P1
9.5642(7)
10.2389(6)
11.0827(6)
12.3450(7)
78.2840(10)
67.2970(10)
79.3300(10)
1238.86(12)
2
b (Å)
c (Å)
12.4445(9)
12.6253(10)
104.5020(10)
99.8040(10)
111.8220(10)
1291.27(17)
1
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc
1.336 Mg/m3
0.778 mmꢂ1
548
1.438 Mg/m3
0.821 mmꢂ1
560
Absorption coefficient
F(000)
F(0000)
548.82
560.85
Crystal size (mm)
Theta range for data
collection
0.40 ꢁ 0.30 ꢁ 0.25
0.40 ꢁ 0.25 ꢁ 0.10
1.74° to 26.37°
1.83° to 26.37°
Index ranges
ꢂ11 6 h 6 11,
ꢂ15 6 k 6 15,
ꢂ15 6 l 6 14
7531
ꢂ12 6 h 6 12,
ꢂ13 6 k 6 13,
ꢂ14 6 l 6 15
7280
Reflections collected
Independent reflections
5183 (0.0598)
4962(0.0433)
(Rint
)
Data completeness
Refinement method
0.982
0.979
Full-matrix least-
squares on F2
Full-matrix least-
squares on F2
Fig. 3. ORTEP drawings of complex B. Top (a) and side (b) views with thermal
ellipsoids at 50% probability. All hydrogen atoms have been omitted for clarity.
Selected bond lengths (Å) and angles (°) are Ni(1)–N(1) 1.864(3), Ni(1)–N(2)
1.878(3), Ni(1)–N(3) 1.914(3), Ni(1)–N(4) 1.916(3), N(1)–C(1) 1.399(5), N(1)–C(23)
1.363(5), N(4)–C(19) 1.480(5), N(4)–C(20) 1.316(5), C(20)–C(22) 1.427(5), C(22)–
C(23) 1.367(5); N(1)–Ni(1)–N(2) 82.68(12), N(3)–Ni(1)–N(4) 95.76(13), N(2)–
Ni(1)–N(3) 91.20(13), N(1)–Ni(1)–N(4) 90.41(13), N(1)–Ni(1)–N(3) 173.65(13),
N(2)–Ni(1)–N(4) 172.87(13), Ni(1)–N(1)–C(1) 111.4(2), Ni(1)–N(1)–C(23)
123.5(2), C(1)–N(1)–C(23) 124.2(3), N(1)–C(23)–C(22) 120.7(3), N(1)–C(23)–C(24)
119.5(3), C(20)–C(22)–C(23) 123.7(3), Ni(1)–N(4)–C(19) 120.3(2), Ni(1)–N(4)–
C(20) 123.8(3), C(19)–N(4)–C(20) 115.7(3), N(4)–C(20)–C(21) 121.6(4), N(4)–
C(20)–C(22) 122.6(3).
Data/restraints/
parameters
Tmin, Tmax
5183/0/325
4962/0/334
0.756, 0.823
0.733
1.072
R1 = 0.0548,
wR2 = 0.1386
R1 = 0.0670,
wR2 = 0.1463
0.673 and ꢂ0.776
0.782, 0.921
0.720
1.097
R1 = 0.0562,
wR2 = 0.1370
R1 = 0.0703,
wR2 = 0.1440
1.157 and ꢂ0.554
Tmin’
Goodness-of-fit on F2
Final R indices [I > 2(I)]
R indices (all data)
Largest diff. peak and
hole (e Åꢂ3
)

66
E. Kim, H. Lee / Inorganica Chimica Acta 399 (2013) 62–66
[4] M. Tsutui, R.L. Bobsein, G. Cash, R. Pettersen, Inorg. Chem. 18 (1979) 758.
can be compared to 177.4(5)° for the N1–Ni1–N3 angle and
178.8(5)° for the N2–Ni–N4 angle in the tetraaza[14]annulene
nickel(II) complex. The difference in the angles stems from the sat-
urated six-membered ring, which is connected to propylenedi-
amine. The structural differences between the unsymmetrical
tetraaza[15]annulene nickel(II) complexes A and B and the unsym-
metrical tetraaza[14]annulene nickel(II) complex are not sufficient
to impose a square-pyramidal arrangement because of ring strain
related to coordination to propylenediamine. Complexes A and B
seem to be distorted from square planarity compared with other
macro N4–Ni(II) complexes [44–47]. Also, the two phenyl rings
´
´
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Acknowledgments
This article is dedicated to emeritus Professor Yu-Chul Park at
Kyungpook National University for his valuable comments and
help. This research was supported by the National Research
Foundation of Korea (NRF), funded by the Ministry of the
Education, Science, and Technology (MEST) (Grant No. 2012-
R1A2A2A01045730).
Appendix A. Supplementary material
CCDC 000000 contains the supplementary crystallographic data
for complexes A and B. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif. Supplementary data associated
with this article can be found, in the online version, at http://
dx.doi.org/10.1016/j.ica.2012.12.041.
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