Trigonal dodecahedral sodium coordination in a trinuclear copper(II)-sodium complex incorporating a salen-Type compartmental Schiff base

Article abstract of DOI:10.1515/znb-2016-0208

A new trinuclear heterometallic complex, [(CuL)Na(CuL)] ClO₄ (1), has been prepared using a Schiff base, H₂L (where H2L N,N-(1,2-phenylene)-bis(3-methoxysalicylideneimine) and characterized by elemental analysis, Fourier transform in

Full text of DOI:10.1515/znb-2016-0208

Z. Naturforsch. 2017; aop
Madhusudan Nandy, Debnath Saha, Corrado Rizzoli and Shyamapada Shit*
Trigonal dodecahedral sodium coordination in a
trinuclear copper(II)-sodium complex incorporating
a salen-type compartmental Schiff base
DOI 10.1515/znb-2016-0208
of complexing agents such as crown ethers, cryptands
etc. other simpler and easily affordable ligands are also
used for this purpose and help to study the structure/
selectivity relationship of the alkali metal ions [4–6].
The salicylaldimine or acetylacetoneimine complexes
of divalent metal ions serve the role of these complex-
ing agents for their abilities to bridge other metal ions
through their phenoxo oxygen atoms. Thus these classes
of ‘ligand complexes’ play an important role for construct-
ing varieties of homo-/heterometallic complexes includ-
ing alkali metal ions, p- and d-block elements [7–9]. The
role of compartmental dinucleating ligands can also be
mentioned in this regard for their abilities to form homo-/
heterometallic complexes. These compartmental ligands
may either by obtained by 2ꢀ:ꢀ1 condensation of varieties
of substituted salicylaldehyde (3-methoxy/3-ethoxy/3-
carboxy) and a diamine or by 2ꢀ:ꢀ1ꢀ:ꢀ1 condensation of a
Received September 14, 2016; accepted October 19, 2016
Abstract: A new trinuclear heterometallic complex,
[(CuL)Na(CuL)]·ClO4 (1), has been prepared using a
Schiff base, H2L (where H2Lꢀ=ꢀN,N′-(1,2-phenylene)-bis(3-
methoxysalicylideneimine) and characterized by elemental
analysis, Fourier transform infra-red (FT-IR) spectroscopy,
UV/Vis, magnetic, electrochemical, and single crystal X-ray
diffraction methods. The structure analysis reveals that two
metallo-ligand [(CuL)] units are connected to each other by
+
a sodium ion resulting in the cationic unit [(CuL)Na(CuL)] .
Both the copper(II) ions display an almost square planar
geometry while the sodium ion adopts a trigonal-dodeca-
hedral coordination geometry. The spectroscopic and other
physicochemical studies are in good agreement with the
crystal structure of the complex.
Keywords: crystal structure; cyclic voltammetry; Schiff diformyl compound with two different diamines (such as
base; trigonal dodecahedral sodium coordination; tri- 4-methyl-2,6-diformylphenol, 1,3-propanediamine, and
nuclear copper(II)-sodium.
ethylenediamine) leading to two dissimilar or similar
compartments with respect to the donor sets and capable
of accommodating two metal ions of similar/different
types generating varieties of homo-/heterometallic dinu-
clear compounds [10]. Moreover, both ‘ligand complexes’
and dinuclear compounds derived from bicompartmen-
tal Schiff bases are further considered as small building
blocks which in combination with other metal ions or
even in the presence/absence of other secondary bridg-
ing ligands can undergo self-assembly to produce oligo-
nuclear and polymeric systems, which is one of the most
important developments in the field of supramolecular
chemistry [7, 10, 11]. Inclusion of small molecules/ions by
these ‘ligand complexes’ or complexes of compartmental
Schiff bases plays an important role in host-guest chemis-
try [7, 12]. Due to the presence of highly unsaturated and
delocalized ligand moieties the electron enrichment in
these complexes is possible because of π multiple metal-
ligand interactions which made these complexes as elec-
tron reservoirs for molecular activation processes. These
complexes also find application as carriers for polar orga-
nometallics, and ferroelectricity [13].
1 Introduction
The coordination chemistry of the alkali metal ions
received enormous interest over the past several decades
aiming to develop molecular systems that can mimic nat-
urally occurring molecules responsible for the selective
transport of ions [1–3]. Besides several well-known classes
*Corresponding author: Shyamapada Shit, Department
of Chemistry, Jalpaiguri Government Engineering College,
Jalpaiguri-735 102, West Bengal, India, Tel.: +ꢀ91-9433261720,
Fax: +ꢀ91 3561 256143, E-mail: shyamakgcchem@gmail.com
Madhusudan Nandy: Department of Basic Engineering Science and
Humanities, Netaji Subhash Engineering College, Panchpota, Garia,
Kolkata-700 152, India
Debnath Saha: Department of Chemistry, Jalpaiguri Government
Engineering College, Jalpaiguri-735 102, West Bengal, India; and
A. P. C. Roy Government College, Matigara, Siliguri-734010, West
Bengal, India
Compartmental salen-type Schiff bases as
multi-nucleating agents based on different flexible
Corrado Rizzoli: Università degli Studi di Parma, Dipartimento di
Chimica, Parco Area delle Scienze 17/A, I-43123 Parma, Italy
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aliphatic diamines were well explored while their ali- the azomethine (–CH=N–) stretching vibration of the coor-
cyclic and aromatic diamine analogs are few in number dinated ligand is observed at 1603 cmꢀ−ꢀ1 in comparison to
[10, 14–18]. In this context, the role of the compart- 1615 cmꢀ−ꢀ1 observed for the free Schiff base [28]. Phenolic
mental Schiff base, H2L, N,N′-(1,2-phenylene)-bis(3- –OH stretching vibration of the Schiff base observed as a
methoxysalicylideneimine) (Scheme 1), obtained by the broad band centred at 3349 cmꢀ−ꢀ1 is absent in the spectrum
condensation of 3-methoxysalicylaldehyde and o-phe- of the complex indicating deprotonation of this group
nylenediamine, as multi-nucleating agents was explored during complexation, further confirmed by the observed
in a number of heteronuclear 3d/ns [3, 10, 19], and 3d/nf lowering of the phenolic C–O stretching bands in compar-
[14, 20–22], 3d/np [23, 24] metal compounds, where the 3d ison to that of the ligand [28]. The phenolic C–O stretching
metal ion gets accommodated in the inner N2O2 core while bands for the complex were observed at 1226 and 1145 cmꢀ−ꢀ1
the outer O2O2 compartment suits for the ns/np/nd/nf in comparison to 1298 and 1236 cmꢀ−ꢀ1 observed for the
metal ions. The compounds isolated can be formulated ligand [29, 30]. The band at 3055 cmꢀ−ꢀ1 may be assigned
as LMM′X or LMLnX, where L is the ligand, M is the 3d to alkyl C–H bond stretching of the methoxy group [12].
metal ion [mainly, Cu(II)/Zn(II)], Ln is the 4f/5f metal ion, Coordination of nitrogen atoms to the copper(II) center
and X is the anionic species [25, 26].
(νCu−N) is also evident by the appearance of weak bands
However, trinuclear cationic M2M′ compounds derived at 484 and 425 cmꢀ−ꢀ1 for 1. A sharp and strong peak at
from this compartmental ligand (H2L) with ClO4− as a counter 1087 cmꢀ−ꢀ1 in the spectra of 1 may be assigned to perchlo-
ion are extremely rare [27]. Herein, we report the synthesis, rate stretching vibration and this single peak without
spectral and structural characterization of a new trinuclear splitting is evident for the presence of a non-coordinating
compound [(CuL)Na(CuL)]ClO4 (1). The structural character- perchlorate anion [31].
ization identifies the sodium ion in a trigonal dodecahedral
coordination geometry which is believed to be rare in this
class of compounds. Room temperature magnetic and elec- 2.2 UV/Vis spectrum
trochemical properties of the complex we also investigated.
The electronic spectrum of 1 was recorded in acetonitrile
at room temperature. The spectrum shows a very broad
and low intensity absorption band at 562 nm correspond-
2 Results and discussion
ing to the dꢀ→ꢀd transitions of the square planar coordina-
tion of the copper(II) ion [3]. The complex also shows a
2.1 Fourier transform infrared (FT-IR)
spectrum
The FT-IR spectrum of the complex is in accordance with region (272 and 222 nm) associated with πꢀ→ꢀπ* transitions
the structure of the compound. The spectrum reveals that of the coordinated ligand are also observed [3, 11, 32, 33].
strong and intense band at 366 nm which is believed to be
due to ligand-to-metal charge transfer transitions (LMCT).
Two very strong and intense bands in the higher energy
H
H
O
O
CHO
NH2
+
N
N
O−
OH
:
−2 H+
1
2 ratio, methanol
reflux, 1 h
NH2
O−
OH
N
OH
N
O
O
O
H
H
H2L
Scheme 1:ꢂSynthetic scheme of Schiff base (H2L) and coordination modes of L2ꢀ−ꢀ
L2−
.
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are slightly but significantly tetrahedrally distorted, the
deviation from the planarity ranging from −ꢀ0.051(7) to
2.3 Crystal structure of [(CuL)Na(CuL)]·ClO4 (1)
An Ortep view of the molecular structure of 1 is shown 0.042(4) Å and from −ꢀ0.72(4) to 0.81(4) Å for N1/N2/O2/O3
in Fig. 1 and the relevant bonding parameters are sum- and N3/N4/O6/O7, respectively.
marized in Table 1. The crystal structure reveals that
The mean Cu–O (1.885(3) and 1.886(5) Å for Cu1 and
the complex consists of a discrete trinuclear cationic Cu2) and Cu–N (1.921(8) and 1.928(5) Å for Cu1 and Cu2)
+
unit [(CuL)Na(CuL)] and a disordered perchlorate ion bond lengths are not significantly different and in good
as counter anion. In the cationic unit two CuL moieties agreement with values reported in the literature [11].
are held together by a sodium ion. In the complex, the Moreover, Cu–O distances are significantly longer with
deprotonated Schiff base (L2ꢀ−ꢀ) simultaneously holds the respect to those observed in similar reported mononuclear
copper(II) ion in its inner core using the imine nitrogen complexes, possibly as a consequence of the bridging
and phenolato oxygen atoms while it holds the sodium role of the phenolato oxygen atoms [2]. The transiod and
ion in its outer core through the same phenolato oxygen cisoid angles deviate from their ideal values of 180 and
atoms involved in the coordination of the copper metals 90° (Table 1) and the mean trans basal angles are the same
and the methoxo oxygen atoms. Thus each copper(II) within experimental errors [176(2) and 176(4)° for Cu1 and
center is tetra-coordinated by two imine nitrogen (N1 and Cu2], indicating that both copper(II) atoms have a very
N2 for Cu1; N3 and N4 for Cu2) and two phenolato oxygen similar distorted square planar coordination geometry.
atoms (O2 and O3 for Cu1; O6 and O7 for Cu2) and adopts On the other hand, the sodium center is connected to two
an approximately square-planar geometry as evident from CuL moieties through the coordination of four phenolato
the bonding parameters (Table 1). The Cu1 and Cu2 atoms oxygen (O2, O3, O6, and O7) and four methoxy oxygen (O1,
protrude by 0.636 (6) and 0.0628(5) Å from the respective O4, O5, and O8) atoms. Thus both copper(II) and sodium
least-squares coordination planes. The N2O2 donor sets ions are connected directly through double μ-phenolato
Fig. 1:ꢂThe molecular structure of 1 with displacement ellipsoids drawn at the 40% probability level. Only the major component of the
disordered perchlorate anion is shown.
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Table 1:ꢂSelected bond lengths (Å) and angles (deg) for complex 1.
Cu1–O2
Cu1–O3
Cu1–N1
Cu1–N2
Cu2–O6
Cu2–O7
Cu2–N3
Cu2–N4
O2–Cu1–O3ꢃ
O2–Cu1–N1ꢃ
O3–Cu1–N1ꢃ
O2–Cu1–N2ꢃ
O3–Cu1–N2ꢃ
N1–Cu1–N2ꢃ
O6–Cu2–O7ꢃ
O6–Cu2–N3ꢃ
O7–Cu2–N3ꢃ
O6–Cu2–N4ꢃ
O7–Cu2–N4ꢃ
N3–Cu2–N4ꢃ
O6–Na1–O2ꢃ
O6–Na1–O7ꢃ
O2–Na1–O7ꢃ
O6–Na1–O3ꢃ
O2–Na1–O3ꢃ
O7–Na1–O3ꢃ
O6–Na1–O5ꢃ
O2–Na1–O5ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
1.885(3)ꢃ
1.885(3)ꢃ
Na1–O6
Na1–O2
Na1–O7
Na1–O3
Na1–O5
Na1–O1
Na1–O8
Na1–O4
O7–Na1–O5ꢃ
O3–Na1–O5ꢃ
O6–Na1–O1ꢃ
O2–Na1–O1ꢃ
O7–Na1–O1ꢃ
O3–Na1–O1ꢃ
O5–Na1–O1ꢃ
O6–Na1–O8ꢃ
O2–Na1–O8ꢃ
O7–Na1–O8ꢃ
O3–Na1–O8ꢃ
O5–Na1–O8ꢃ
O1–Na1–O8ꢃ
O6–Na1–O4ꢃ
O2–Na1–O4ꢃ
O7–Na1–O4ꢃ
O3–Na1–O4ꢃ
O5–Na1–O4ꢃ
O1–Na1–O4ꢃ
O8–Na1–O4ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
2.499(3)
2.503(3)
1.912(4)ꢃ
2.518(3)
1.929(4)ꢃ
2.531(3
1.880(3)ꢃ
2.604(3)
1.890(3)ꢃ
2.608(3)
1.923(4)ꢃ
2.627(3)
1.932(3)ꢃ
2.641(3)
84.91(12)ꢃ
95.82(17)ꢃ
173.91(14)ꢃ
177.99(14)ꢃ
94.43(16)ꢃ
84.63(19)ꢃ
84.71(12)ꢃ
95.44(15)ꢃ
179.83(16)ꢃ
172.71(13)ꢃ
95.36(14)ꢃ
84.48(17)ꢃ
142.05(12)ꢃ
60.84(10)ꢃ
124.73(11)ꢃ
142.80(11)ꢃ
60.73(10)ꢃ
141.21(12)ꢃ
60.57(10)ꢃ
103.20(11)ꢃ
121.35(11)
89.04(10)
86.77(11)
60.74(10)
80.11(10)
121.24(11)
99.21(11)
120.75(11)
78.94(10)
60.00(9)
87.52(10)
174.38(12)
86.38(11)
88.72(10)
120.49(11)
104.15(10)
59.91(9)
72.06(10)
171.27(12)
102.35(11)
Fig. 2:ꢂTrigonal dodecahedral coordination geometry of the
sodium ion in 1.
In the coordination environment, the Na–O
(phenolato) distances [mean value 2.53(3) Å] are signifi-
cantly shorter than the Na–O(methoxo) distances [mean
value 2.620(9) Å] which is in good agreement with the
compounds reported earlier [10]. The intra-molecular
Cu1···Cu2 separation is 7.0594 (8) Å while the Cu1···Na
and Cu2···Na separations are of 3.556 and 3.5491(1) Å,
respectively.
Table 2:ꢂHydrogen bonding parameters (Å, deg) for 1.a
D–H···A
D–H
H···A
D···A
∠ D–H···A
The packing of the molecules reveals that the per-
chlorate anions and the trinuclear cationic units are
connected through unclassical C–H···O interactions
(Table 2) leading to a three-dimensional supramolecular
structure.
C9–H9···O10#1
0.93
0.96
0.93
0.93
2.53
2.51
2.57
2.51
3.207(8)
3.457(8)
3.417(10)
3.383(9)
130
170
152
157
C22–H22A···O11#2
C27–H27···O12#3
C29–H29···O12#3
aEquivalent atoms generated by symmetry codes: #11ꢀ−ꢀx, −ꢀy, 1ꢀ−ꢀz;
#21ꢀ−ꢀx, 1/2ꢀ+ꢀy, 1/2ꢀ−ꢀz; #3−ꢀx, 1/2ꢀ+ꢀy, 1/2ꢀ−ꢀz.
2.4 Magnetic study
bridges as well as through the coordination of methoxo
oxygen atoms of the Schiff base moieties. The O4 donor Room temperature magnetic susceptibility measurements
sets of the Schiff bases are essentially planar (r.m.s. devia- for 1 gave an effective magnetic moment (μeff) of 1.74 BM.
tion of 0.006 and 0.002 Å for O1/O2/O3/O4 and O5/O6/O7/ This behavior is very similar to the spin-only magnetic
O8, respectively) and almost orthogonal to each other, moment of an isolated copper(II) system (d9, Sꢀ=ꢀ½), sup-
forming a dihedral angle of 77.09(6)°.
porting the presence of magnetically non-coupled square
The geometry around sodium is best described as planar copper(II) ions in the complex.
trigonal dodecaherdral (Fig. 2) which is rarely occurring
except for sodium coordinated with adequate crown ether
ligands. To the best of our knowledge this is the third 2.5 Electrochemical study
example of its kind of trinuclear complexes [10, 27] and
believed to be first within the copper(II)-sodium polynu- A cyclic voltammogram of 1 (Fig. 3) was recorded at room
clear family bearing this compartmental ligand.
temperature in acetonitrile within the potential range of
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Fig. 3:ꢂCyclic voltammogram of 1 (vs. SCE) recorded in acetonitrile at room temperature.
−ꢀ1.5 to +ꢀ1.5 V using tetrabutylammonium perchlorate as
supporting electrolyte measured at scan rates of 50, 100
3 Conclusion
and 150 mV s−ꢀ1. With cathodic scan a reductive response Herein we have reported the synthesis and spectrocscopic
observed at −ꢀ0.61, −ꢀ0.66, and −ꢀ0.69 V (versus SCE) may characterization of a rare trinuclear copper(II)–sodium
be assigned to Cu(II)ꢀ→ꢀCu(I) reduction while with anodic complex incorporating an o-phenylene based salen-type
scan an oxidative response assignable to Cu(I)ꢀ→ꢀCu(II) compartmental Schiff base which is capable to form trinu-
oxidation is observed at −ꢀ0.92, −ꢀ0.88, and −ꢀ0.87 V (versus clear compounds. The structural characterization reveals
SCE) at the same scan rates of 50, 100, and 150 mV sꢀ−ꢀ1, that the sodium ion in the complex adopts a trigonal
respectively [7]. The irreversible nature of the redox dodecahedral coordination geometry which is very rare in
process is indicated by the peak-to-peak separations of this class of compounds. The electrochemical properties
310, 220, and 180 mV, at their respective scan rates. It can reveal a behavior similar to those observed in mononu-
be further observed that on increasing the scan rate, the clear copper(II)-salen-type compounds.
cathodic peak positions shift to more negative values and
the anodic peak positions are observed at more positive
values while peak currents increase in both scans and Ipc,
4 Experimental section
is always more than Ipa, also confirming the irreversibility
of the redox process.
Moreover, the presence of only one redox couple sug- 4.1 Materials
gests that both copper(II) ions present in the compound
are in a similar chemical environment as revealed by the Caution! Perchlorate salts of metal ions in presence of
single crystal X-ray structure of the compound. However, organic ligand are potentially explosive. Though we did
other irreversible oxidative response, tentatively assigned not encounter any problem, the compound should be pre-
for the oxidation of the coordinated Schiff base, are pared in small amount and handled with utmost care.
observed at +ꢀ0.91, +ꢀ0.98, and +ꢀ1.04 V during the anodic
scan for the respective scan rates.
All chemicals and solvents used in the synthesis were
of analytical grade. Sodium perchlorate monohydrate was
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purchased from E. Merck (Mumbai, India). O-Vanillin, (10 mL) of copper(II) perchlorate hexahydrate (0.741 g,
o-phenylenediamine, and copper(II) perchlorate hexahy- 2 mmol) with slow stirring. A greenish brown precipitate
drate were purchased from Aldrich Chemical Co. Inc. (Sigma immediately separated out which was filtered and air dried.
Aldrich, St. Louis, MO, USA) and were used as received.
The precipitate was then dissolved in 20 mL iso-propanol
with slow stirring. To the resulting solution another iso-pro-
panolic solution (10 mL) of sodium perchlorate monohy-
drate (0.141 g, 1 mmol) was added dropwise with constant
stirring. The reaction mixture was again stirred for another
hour and filtered. The filtrate was kept undisturbed at room
temperature. Diffraction quality air stable deep brown
single crystals of 1 were separated after 3 weeks. Yield:
0.635 g (72%) with respect to metal substrate.
4.2 Physical techniques
Elemental analyzes (carbon, hydrogen and nitrogen) were
carried out with a Perkin Elmer 2400 II elemental analyzer
(Perkin Elmer, MA, USA). Copper(II) content in the complex
was estimated quantitatively using a standard iodomet-
ric procedure. The FT-IR spectra (4000–400 cmꢀ−ꢀ1) were
recorded on a Perkin Elmer Spectrum RX I FT-IR system
(Perkin Elmer, MA, USA) with solid KBr pellets. UV/Vis
spectra in solution were recorded at room temperature on a
PerkinElmer Lambda 40 UV/Vis spectrophotometer (Perkin
Elmer, SC, USA) using acetonitrile in 1 cm quartz cuvettes.
Magnetic susceptibilities were measured with a model
155 PAR vibrating sample magnetometer (E Mc Grath Inc.,
Salem, USA) fitted with a Waker Scientific 175 FBAL magnet
using Hg[Co(SCN)4] as the standard. Necessary diamagnetic
corrections for the ligand were performed using Pascal’s
table. Electrochemical measurements were performed using
a PAR VersaStat-potentiostat/Galvanostat II electrochemical
analysis system (Princeton Applied research, Oak Ridge,
USA) under dry argon using conventional three-electrode
configurations in acetonitrile with tetrabutylammonium
perchlorate as the supporting electrolyte. A platinized plati-
num millielectrode and a saturated calomel electrode (SCE)
were used as working and reference electrodes, respectively,
4.3.3 Physical and spectroscopic data
For H2L: – UV/Vis (CH3CN): λmax (lg εmax)ꢀ=ꢀ332 (3.58), 282
(4.72), and 211 nm (4.75). – IR (KBr disc): νꢀ=ꢀ3349 (phe-
nolic –OH), 1615 (–CH=N–), 1298, and 1236 (phenolic C–O)
cmꢀ−ꢀ1. – C22H20N2O4 (376.41): calcd. C 70.20, H 5.36, N 7.44;
found C 70.14, H 5.30, N 7.38.
For 1: – UV/Vis (CH3CN): λmax (lg εmax)ꢀ=ꢀ562 (2.74),
366 (4.40), 272 (4.56), and 222 nm (4.59). – IR (KBr disc):
νꢀ=ꢀ3427, 3055 (methoxy C–H), 1627, 1603 (–CH=N–), 1580,
1518, 1494, 1423, 1341, 1319, 1307, 1226, and 1145 (phenolic
ꢀ−ꢀ
C–O), 1111, 1087 (ClO4 ), 950, 852, 782, 738, 724, 653, 621,
575, 509, 484 (Cu–N), 457, 425 (Cu–N) cmꢀ−ꢀ1. – C44H36Cl-
Cu2N4NaO12 (998.31): calcd. C 52.94, H 3.63, N 5.61, Cu 12.73;
found C 52.87, H 3.58, N 5.58, Cu 12.65.
along with a platinum counter electrode in cyclic voltamme- 4.4 Crystal structure determination
try performed at a scan rate of νꢀ=ꢀ50, 100, and 150 mV sꢀ−ꢀ1.
A diffraction quality air stable block shaped brown crystal
of 1 was mounted on a Bruker SMART APEX II CCD area
4.3 Preparation of the ligand and complex
detector diffractometer equipped with a fine-focus,
sealed tube X-ray source with graphite monochromated
4.3.1 Schiff base ligand: N,N′-(1,2-phenylene)-bis(3-
MoKα radiation (λꢀ=ꢀ0.71073 Å). The data were collected
methoxysalicylideneimine (H2L)
by ϕ and ω scan modes at 294(2) K. Data collection was
performed with the Bruker Apex2 [34] (Bruker AXS Inc.,
The Schiff base ligand, H2L, was prepared by refluxing
Madison, WI, USA) software while cell refinement and
o-vanillin (1.52 g, 10 mmol) o-phenylenediamine (0.540 g,
data reduction were performed with the Bruker Saint
5 mmol) in 50 mL methanol for 1 h. The reaction mixture
program [34] (Bruker AXS Inc., Madison, WI, USA). Multi-
was filtered. The filtrate kept at room temperature for slow
scan absorption corrections were applied to the intensity
evaporation of the solvent. Deep orange crystals of the
values (Tmaxꢀ=ꢀ0.900 and Tminꢀ=ꢀ0.769) using Sadabs [34]
Schiff base ligand H2L were separated which is filtered and
(Bruker AXS Inc., Madison, WI, USA). The structure of 1
air dried. Yield: 1.64 g (87%)
was solved by Direct Methods using the program Shelxt
[35] (Institut Anorg. Chemie, Göttingen, Germany) and
4.3.2 [(CuL)Na(CuL)]·ClO4 (1)
refined with full-matrix least-squares based on F2 using
Shelxl-2014/7 [36, 37] (Institut Anorg. Chemie, Göttingen,
A methanolic solution (20 mL) of the Schiff base H2L Germany). All non-hydrogen atoms were refined with ani-
(0.790 g, 2 mmol) was added to a methanolic solution sotropic displacement parameters. The hydrogen atoms
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M. Nandy et al.: Trigonal dodecahedral sodium coordination in a heterometallic complexꢀ
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Table 3:ꢂCrystal data and structure refinement data for complex 1.
References
Complex
1
[1] D. Cunningham, P. McArdle, M. Mitchell, N. Níchonchubhair, M.
Ơ. Gara, F.Franceschi, C. Floriani, Inorg. Chem. 2000, 39, 1639.
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[3] N. Mahlooji, M. Behzad, H. A. Rudbari, G. Bruno, B. Ghanbari,
Inorg. Chim. Acta 2016, 445, 124.
Empirical formula
C44H36ClCu2N4NaO12
998.31
Mr
Crystal system
Monoclinic
0.14ꢀ×ꢀ0.10ꢀ×ꢀ0.09
P21/c (No. 14)
12.1098(5)
17.6606(7)
19.3747(7)
92.119(2)
4140.8(3)
4
Crystal size, mm3
Space group
a, Å
[4] Y.-M. Jeon, J. Kim, D. Whang, K. Kim, J. Am. Chem. Soc. 1996,
118, 9790.
b, Å
c, Å
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β, deg
V, Å3
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G. Aromi, R. E. P. Winpenny, Dalton Trans. 2003, 2318.
[7] P. Mukherjee, M. G. B. Drew, A. Figuerola, A. Ghosh, Polyhe-
dron 2008, 27, 3343, and references therein.
[8] S. Ghosh, S. Giri, A. Ghosh, Polyhedron 2015, 102, 366.
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152, references therein.
Z
T (K)
294(2)
μ(MoKα), cmꢀ−ꢀ1
1.2
D
calcd., g cmꢀ−ꢀ3
1.60
F(000), e
2040
θ range for data collection, deg
hkl ranges
Total/unique data/Rint
Observed data [Iꢀ>ꢀ2 σ(I)]
Ref. parameters
Final R1/wR2 indices [Iꢀ>ꢀ2 σ(I)]
Final R1/wR2 indices (all data)
Goodness-of-fit on F2
Δρ (max/min), e Åꢀ−ꢀ3
1.561–25.499
ꢀ14, ꢀ21, ꢀ23
60832/7718/0.075
4741
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600
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Acta 2013, 405, 196.
0.0495/0.1119
0.0929/0.1343
1.017
–ꢀ0.38/0.44
[15] A. Biswas, M. Ghosh, P. Lemoine, S. Sarkar, S. Hazra, S.
Mohanta, Eur. J. Inorg. Chem. 2010, 3125.
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Mohanta, J. Mol. Struct. 2011, 1006, 216.
were placed geometrically and refined with isotropic
thermal parameters using a riding model approximation.
The perchlorate anion is disordered over two orientations
sharing three oxygen atoms with refined occupancy ratio
0.524(10)ꢀ:ꢀ0.476(10). In order to prevent inflated anisotropy
to the anisotropic displacement parameters, the Cl and O
atoms of the disordered perchlorate anion were restrained
to be approximately isotropic using the ISOR instruction
in Shelxl-2014 [36, 37] (Institut Anorg. Chemie, Göttin-
gen, Germany) with an effective standard deviation of
0.12 Å. All calculations and graphical illustrations for the
complex have been performed using Shelxl-2014/7 [36,
37] (Institut Anorg. Chemie, Göttingen, Germany), and
Ortep [38, 39] programs (Oak Ridge National Labora-
tory, Oak Ridge, USA). Selected crystallographic data and
important structure refinement parameters of 1 are sum-
marized in Table 3.
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Struct. 2011, 1004, 204.
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R.A. Jones, Z. Anorg. Allg. Chem. 2008, 634, 1795.
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CCDC 1501781 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained
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Acknowledgments: S. Shit gratefully acknowledges Uni-
versity Grants Commission, New Delhi, India for financial
assistance [Minor Research Project No. F. PSW–65/12–13
(ERO)].
[30] S. Shit, D. Saha, D. Saha, T. N. Guru Row, C. Rizzoli, Inorg.
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[31] K. Nakamoto, Infrared Spectra of Inorganic Compounds, Wiley,
New York, 1970, pp. 242.
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ꢁM. Nandy et al.: Trigonal dodecahedral sodium coordination in a heterometallic complex
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[32] P. Bhowmik, S. Jana, P. P. Jana, K. Harms, S. Chattopadhyay,
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Z. Naturforsch.ꢁ
ꢁ2017 | Volume x | Issue x(b)
Graphical synopsis
Madhusudan Nandy, Debnath Saha,
Corrado Rizzoli and Shyamapada Shit
Trigonal dodecahedral sodium coor-
dination in a trinuclear copper(II)-
sodium complex incorporating a
salen-type compartmental Schiff
base
DOI 10.1515/znb-2016-0208
Z. Naturforsch. 2017; x(x)b: xxx–xxx
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