Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and decanuclear Li2Zn8 complexes

Article abstract of DOI:10.1016/j.poly.2019.03.013

A carboxylate containing polydentate ligand in combination with exogeneous succinate (suc) has been used to stabilize heterometallic octanuclear [Li₂Na₂Cu₄(cpdp)₂(suc)₂(CH₃OH)₂(H₂O)₄]Cl₂·6H₂O (1) and decanuclear Na(H₃O)₂[Li₂Zn₈(cpdp)₄(suc)₂(H₂O)₄]Cl₂Br₃·6MeOH·19H₂O (2) complexes. The reaction of ligand H₃cpdp (H₃cpdp = N,N'-bis[2-carboxybenzomethyl]-N,N'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol) with stoichiometric amounts of CuCl₂/sodium succinate, and ZnCl₂/sodium succinate, allowed isolation of complexes 1 and 2, respectively. Analyses of single crystal X-ray structures indicate that complex 1 is capped by two [Cu₂(cpdp)]⁺ molecular building units and two succinate linkers, while complex 2 is overlaid by four [Zn₂(cpdp)]⁺ molecular building units and two succinate linkers. Whereas complex 1 shows monodentate terminal and tridentate μ₃:η²:η¹:η¹ bridging coordination of carboxylate, and μ₄:η²:η¹:η¹:η¹ bridging mode of succinate, complex 2 displays monodentate terminal and anti-anti μ₂:η¹:η¹ bidentate bridging coordination of carboxylate, and μ₄:η¹:η¹:η¹:η¹ bridging mode of succinate. To our knowledge, 1 is the first example of copper/lithium/sodium-based hetero-octanuclear complex with any class of bridging or non-bridging ligand showing three different binding modes of carboxylates. Again, 2 is also the first example of a hetero-decanuclear metallomacrocyclic complex with any class of bridging or non-bridging ligand combining both lithium and zinc. Variable temperature magnetic investigation of 1 discloses sensible antiferromagnetic interactions intermediated among the copper centers. Thermal behavior of 1 and 2 has been examined by thermogravimetric analysis indicating that the complexes are stable up to ～430 °C.

Full text of DOI:10.1016/j.poly.2019.03.013

Polyhedron xxx (xxxx) xxx
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis, structure and properties of new heterometallic octanuclear
Li2Na2Cu4 and decanuclear Li2Zn8 complexes
Shobhraj Haldar a, Nityananda Dutta a, Gonela Vijaykumar b, Arpan Das b, Luca Carrella c, Allen Oliver d,
Manindranath Bera a,
⇑
a Department of Chemistry, University of Kalyani, Kalyani, West Bengal 741235, India
b Department of Chemical Sciences, Indian Institute of Science Education & Research Kolkata, Mohanpur, West Bengal 741246, India
c Institut fur Anorganische Chemie und Analytische Chemie, Johannes-Gutenberg Universität Mainz, Duesbergweg 10-14, D-55128 Mainz, Germany
d Department of Chemistry and Biochemistry, University of Notre Dame, 251 Nieuwland Science Hall, Notre Dame, IN 46556-5670, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
A carboxylate containing polydentate ligand in combination with exogeneous succinate (suc) has been
used to stabilize heterometallic octanuclear [Li2Na2Cu4(cpdp)2(suc)2(CH3OH)2(H2O)4]Cl2ꢀ6H2O (1) and
decanuclear Na(H3O)2[Li2Zn8(cpdp)4(suc)2(H2O)4]Cl2Br3ꢀ6MeOHꢀ19H2O (2) complexes. The reaction
of ligand H3cpdp (H3cpdp = N,N’-bis[2-carboxybenzomethyl]-N,N’-bis[2-pyridylmethyl]-1,3-diamino-
propan-2-ol) with stoichiometric amounts of CuCl2/sodium succinate, and ZnCl2/sodium succinate,
allowed isolation of complexes 1 and 2, respectively. Analyses of single crystal X-ray structures indicate
that complex 1 is capped by two [Cu2(cpdp)]+ molecular building units and two succinate linkers, while
complex 2 is overlaid by four [Zn2(cpdp)]+ molecular building units and two succinate linkers. Whereas
Received 2 January 2019
Accepted 9 March 2019
Available online xxxx
Keywords:
Hetero-multimetallic complex
Carboxylate bridging
Crystal structure
Magnetic properties
Thermal behavior
complex 1 shows monodentate terminal and tridentate l3
and l4
g1 bridging mode of succinate, complex 2 displays monodentate terminal and anti-anti
g1 bidentate bridging coordination of carboxylate, and l4 g1 bridging mode of succinate.
: : :g
g2 g1 1 bridging coordination of carboxylate,
:
g2 g1 g1
: : :
l2:
g1
:
: : : :
g1 g1 g1
To our knowledge, 1 is the first example of copper/lithium/sodium-based hetero-octanuclear complex
with any class of bridging or non-bridging ligand showing three different binding modes of carboxylates.
Again, 2 is also the first example of a hetero-decanuclear metallomacrocyclic complex with any class of
bridging or non-bridging ligand combining both lithium and zinc. Variable temperature magnetic
investigation of 1 discloses sensible antiferromagnetic interactions intermediated among the copper
centers. Thermal behavior of 1 and 2 has been examined by thermogravimetric analysis indicating that
the complexes are stable up to ꢁ430 °C.
Ó 2019 Elsevier Ltd. All rights reserved.
1. Introduction
out an extraordinary array of catalytic transformations have been
created by nature [15–18]. To comprehend and exploit such
In recent years, the study of multinuclear complexes of metals
in moderate oxidation states has become one of intense research
interest not only because of their attractive and diverse multidi-
mensional architectures, but also due to their many applications,
including magnetic properties [1–7]. Some examples with fascinat-
ing magnetic properties include single molecule magnets [8–11] or
magnetic refrigerants [12] and molecules with large spin ground
states [13] or large anisotropy barriers [14]. In multinuclear com-
plexes, the neighboring metal centers are likely to cooperate in
promoting reactions which have frequently been observed in bio-
logical systems. Many multinuclear protein complexes that carry
phenomena, additional examples of high nuclearity homo- and
heterometallic complexes are required, and this is a challenge to
the synthetic chemists. In contrast to the homometallic multinu-
clear complexes, the assembly of heterometallic multinuclear
complexes containing both transition and alkali metals has been
largely unexplored. Therefore, the search for appropriate organic
ligands to bridge the gap between transition and alkali metals is
an attractive but highly challenging task since these heterometallic
multinuclear complexes should provide the chance to produce
multifunctional materials. In this line, the presence of alkali metal
ions in the reaction system sometimes assist the assembling pro-
cess for construction of heterometallic multinuclear complexes
[19,20]. Therefore, the introduction of alkali metal Li/Na/K cations
into the metal-carboxylate frameworks is interesting for many
⇑
Corresponding author.
E-mail address: mbera2009@klyuniv.ac.in (M. Bera).
https://doi.org/10.1016/j.poly.2019.03.013
0277-5387/Ó 2019 Elsevier Ltd. All rights reserved.
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

2
S. Haldar et al. / Polyhedron xxx (xxxx) xxx
potential applications as well as in directing the formation of mult-
inuclear complexes with diverse and aesthetically pleasant struc-
tural design. On the other hand, succinate (suc) being a linear
dicarboxylate exhibiting multidimensional metal–oxygen connec-
tivity in their complexes, provides an effective means for the syn-
thesis of multinuclear complexes with novel topologies and other
properties [21,22].
ature range of 2–300 K under an applied field of 1 Tesla. Experi-
mental susceptibility data were corrected for the underlying
diamagnetism using Pascal’s constant [29]. The temperature
dependent magnetic contribution of the holder was determined
experimentally and subtracted from the measured susceptibility
data. The program phi [30] was used for spin Hamiltonian simula-
tions of the data.
Careful literature search also shows that succinate has been lit-
tle employed as bridging ligand in the synthesis of heterometallic
multinuclear complexes; only very few high nuclearity (N ꢂ 6)
transition metal complexes are structurally characterized [23,24].
Therefore, yielding these heterometallic complexes by using two,
or more, different metal ions is a smart synthetic target. However,
in spite of great synthetic challenge, there are significant potential
rewards with real possibility of control/design over the discrete
magnetic parameters that add to their overall molecular properties
[25]. In this field, we have explored the feasibility of carboxylate-
based polydentate ligands in presence of different exogeneous
bridging groups to influence the nuclearity and topology of multi-
nuclear complexes [26–28]. We have since observed the modifica-
tion of ligands and reaction conditions to allow access to different
multinuclear complexes, the assembly of which can be understood
in terms of bridging potential of different endo- and exogeneous
functionalities. This article discusses the simple and facile
approach to synthesize succinate incorporated, two novel
heterometallic, an octanuclear Li2Na2Cu4 and a decanuclear Li2Zn8
complexes of a polydentate ligand showing rare and interesting
coordination chemistry. Additionally, structural aspects, magnetic
and thermal behavior have been discussed.
2.3. Synthesis of N,N0-bis[2-carboxybenzomethyl]-N,N0-bis[2-
pyridylmethyl]-1,3-diaminopropan-2-ol, H3cpdp
The ligand H3cpdp used in this work was prepared following
our previously published procedure [31]. The elemental and ther-
mogravimetric analyses confirmed the composition of the ligand
as H3cpdpꢀLiClꢀ3LiBrꢀ14H2O. Yield: 4.018 g (77%). Anal. Calc. for
C
31H32N4O5ꢀLiClꢀ3LiBrꢀ14H2O: C, 33.98%; H, 5.51%; N, 5.11%; Cl,
3.24%; Br, 21.88%. Found: C, 33.88%; H, 5.54%; N, 5.27%; Cl,
2.91%; Br, 21.49%. FTIR (cmꢃ1):
m
= 3389(b), 2084(b), 1634(s),
1567(vs), 1441(s), 1399(s), 1298(s), 1154(s), 1094(s), 972(s), 761
(s). 1H NMR (400 MHz, D2O, room temperature, d): 8.47 (d, 2H),
7.81 (t, 2H), 7.64 (d, 2H), 7.39–7.51 (m, 8H), 7.27 (d, 2H), 4.47 (d,
8H), 4.01–4.20 (m, 1H), 3.38 (d, 2H), 3.13 (t, 2H). 13C NMR
(100 MHz, D2O, room temperature, d): 174.65, 149.32, 148.91,
143.99, 141.31, 138.87, 137.23, 133.20, 130.88, 130.44, 125.01,
124.68, 60.47, 60.25, 57.50, 57.11. Mass spectrum (ESI): m/z 565
(100%) (M+ = {H3cpdpꢀH2O + Li}+), 559 (81%) (M+ = {H3cpdpꢀH2O
+ H}+). TGA analysis: loss of H2O {136–273 °C: 23.00% (Calcd.);
23.35% (Found)}; loss of CO2 {290–367 °C: 8.03% (Calcd.); 8.39%
(Found)}.
2.4. Synthesis of [Li2Na2Cu4(cpdp)2(suc)2(CH3OH)2(H2O)4]Cl2ꢀ6H2O (1)
2. Experimental
A
methanol solution (10 mL) of CuCl2ꢀ2H2O (0.157 g,
2.1. Reagents and solvents
0.92 mmol) was added to a solution of H3cpdpꢀLiClꢀ3LiBrꢀ14H2O
(0.511 g, 0.46 mmol) and NaOH (0.055 g, 1.38 mmol) in methanol
(10 mL). The reaction mixture was stirred for 1 h at room temper-
ature resulting in a light green solution. Then, an aqueous solution
(5 mL) of sodium succinate hexahydrate (0.124 g, 0.46 mmol) was
added to this solution and the stirring was continued for another
1 h. Then, the solution became turbid with blue in colour. To
remove any insoluble precipitate, the solution was filtered. After
one week, blue needle-shaped crystals suitable for X-ray diffrac-
tion were obtained by slow diethyl ether diffusion into the clear fil-
trate at room temperature. Yield: 0.350 g (78%). Anal. Calc. for
2-Carboxybenzaldehyde, 2-picolylchloride hydrochloride, 1,3-
diamino-2-propanol, sodium borohydride and lithium hydroxide
were purchased from Sigma-Aldrich Chemie GmbH, Germany
and were used as received. Copper(II) chloride dihydrate, zinc(II)
chloride and sodium succinate hexahydrate were purchased from
Merck, India. All other chemicals and solvents were reagent grade
materials and were used as received without further purification.
2.2. Physical measurements
C
72H94N8O30Cl2Li2Na2Cu4 C, 44.66; H, 4.89; N, 5.79; Cu, 13.13.
Found: C, 44.27; H, 4.92; N, 5.83; Cu, 13.11. FTIR (cmꢃ1):
= 3419(b), 2947(b), 1609(s), 1589(s), 1580(s), 1563(s), 1459(s),
Microanalyses analyses of the ligand as well as complexes were
carried out by a Perkin-Elmer 2400 Series II elemental analyzer.
FTIR spectra were recorded as KBr pellets on a Perkin-Elmer
L120-000A spectrometer operating at 400–4000 cmꢃ1. UV–Vis
spectra were recorded at room temperature using a UV 1800
(200–900 nm) (1 cm quartz cell) spectrophotometer. 1H and 13C
NMR spectra were obtained on a Bruker AC 400 NMR spectrometer.
Mass spectra of the ligand was obtained using a Micromass Q-Tof
MicroTM (Waters) mass spectrometer. The potentiometric titration
of the ligand H3cpdp was performed with a Mettler Toledo Seven
Compact S220 digital Ion/pH meter using AgNO3 in aqueous solu-
tion. The percentage of chloride and bromide present in the ligand
were confirmed by potentiometric titration experiment. Thermo-
gravimetric analyses (TGA) were performed with a NETZSCH STA
449F3 thermal analyzer. The XRD measurements were carried
out with a Rigaku (Mini Flex II, Japan) powder X-ray diffractometer
m
1403(s), 1301(s), 1285(s), 1244(s), 1211(s), 1154(s), 1100(s),
1074(s), 1050(s), 1029(s), 996(s), 860(s), 827(s), 763(s), 715(s),
673(s), 524(s). UV–Vis spectra (MeOH): kmax (e
, Mꢃ1cmꢃ1) = 693
(460), 259 (64956).
2.5. Synthesis of Na(H3O)2[Li2Zn8(cpdp)4(suc)2(H2O)4]
Cl2Br3ꢀ6MeOHꢀ19H2O (2)
A methanol solution (10 mL) of ZnCl2 (0.125 g, 0.92 mmol) was
added to
a
solution of H3cpdpꢀLiClꢀ3LiBrꢀ14H2O (0.511 g,
0.46 mmol) and NaOH (0.055 g, 1.38 mmol) in methanol (10 mL).
The reaction mixture was refluxed for 1 h, resulting in a light yel-
low solution. Then, an aqueous solution (5 mL) of sodium succinate
hexahydrate (0.124 g, 0.46 mmol) was added to this solution and
the mixture was refluxed for another 1 h. Then, the light yellow
solution was cooled and filtered. Slow diethyl ether diffusion into
the clear filtrate at room temperature produced light yellow
block-shaped single crystals suitable for X-ray diffraction after 5–
7 days. Yield: 0.365 g (82%). Anal. Calc. for C138H200N16O59Cl2Br3Li2-
having Cu Ka = 1.54059 Å radiation. Porosity measurements of 1
and 2 were performed using a Bel Sorp-max instrument from Bel
Japan. The variable temperature magnetic susceptibilities of pow-
dered microcrystalline samples of complex 1 were measured using
a SQUID magnetometer (MPMS-7, Quantum Design) in the temper-
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

S. Haldar et al. / Polyhedron xxx (xxxx) xxx
3
NaZn8: C, 42.52; H, 5.17; N, 5.75; Zn, 13.42. Found: C, 42.59; H,
5.08; N, 5.61; Zn, 13.35. FTIR (cmꢃ1):
= 3424(b), 2922(b), 1608
3. Results and discussion
m
(s), 1595(s),1588(s), 1571(s), 1483(s), 1447(s), 1430(s), 1394(s),
1299(s), 1247(s), 1159(s),1108(s), 1057(s), 1032(s), 944(s), 894
(s), 870(s), 829(s), 770(s), 722(s), 618(s). 1H NMR (400 MHz, CD3-
OD, room temperature): d (ppm) = 3.09 (t, 8H, succinate), 3.12–
4.24 (m, 52H, aliphatic), 6.72–7.64 (m, 64H, aromatic). 13C NMR
(100 MHz, CD3OD, room temperature): d (ppm) = 54.82 (4C, CH2,
succinate), 55.07 (8C, CH2), 61.81 (8C, CH2), 63.69 (8C, CH2),
63.80 (4C, aliphatic CH), 122.89 (8C, aromatic CH), 123.00 (8C, aro-
matic CH), 128.32 (8C, aromatic CH), 128.95 (8C, aromatic CH),
129.14 (8C, aromatic CH), 131.38 (8C, aromatic CH), 131.58 (8C,
aromatic CH), 139.61 (8C, aromatic CH), 139.79 (8C, aromatic
CH), 146.78 (8C, aromatic CH), 157.05 (8C, aromatic CH), 176.11
(4C, monodentate terminal carboxylate, aromatic), 176.22 (4C,
bidentate bridging carboxylate, aromatic), 180.70 (4C, bidentate
bridging carboxylate, succinate), 180.91 (4C, bidentate bridging
3.1. Synthesis and general characterization
The ligand adopted for the aforesaid work is H3cpdp (Scheme 1)
[31], which was recently used in our laboratory to build PO43ꢃ
/
HPO24ꢃ, AsO43ꢃ/HAsO42ꢃ, phthalate/terephthalate and OH–-bridged
iron(III), copper(II) and zinc(II) multinuclear complexes [26,39–
41]. Very recently, it was also utilized for the construction of a
CO23– incorporated staircase-like decanuclear copper(II) complex
[28]. In fact, room temperature reaction among H3cpdp, CuCl2
and sodium succinate in a 1:2:1 molar ratio, respectively, in
MeOH/H2O (4:1; v/v) in the presence of NaOH afforded a blue
heterometallic octanuclear complex, [Li2Na2Cu4(cpdp)2(suc)2(CH3-
OH)2(H2O)4]Cl2ꢀ6H2O (1) (Scheme 2). However, the pale yellow
heterometallic decanuclear complex, Na(H3O)2[Li2Zn8(cpdp)4
(suc)2(H2O)4]Cl2Br3ꢀ6MeOHꢀ19H2O (2) (Scheme 2) was produced
by reaction of H3cpdp with ZnCl2 and sodium succinate in a
2:4:1 molar ratio, respectively, in MeOH/H2O (4:1; v/v) in the pres-
ence of NaOH under refluxing conditions. Elemental analysis, FTIR,
UV–Vis, 1H and 13C NMR spectroscopic techniques, TGA analysis,
magnetic measurement, and single crystal X-ray method were
employed to characterize complexes 1 and 2. The composition of
1 and 2 was established by elemental and thermal analyses and
single crystal X-ray diffraction study.
carboxylate, succinate). UV–Vis spectra (MeOH): kmax (e
, Mꢃ1
cmꢃ1) = 264 (50518).
2.6. X-ray crystal structure determination and refinement
The single crystal X-ray data for 1 were collected on a diffrac-
tometer with Bruker SMART CCD area detector using a graphite-
monochromated Mo Ka radiation (k = 0.71073 Å) and the data for
2 were collected on a diffractometer with SuperNova, Dual, Cu at
zero, Eos area detector [32,33], using a graphite-monochromated
3.2. Description of the X-ray crystal structure of 1
Mo K
a
radiation (k = 0.71073 Å). The statistical tests were used
ꢃ
Complex 1 cryꢃstallized in the triclinic system and the structure
to determine the triclinic space group P 1 for both 1 and 2. A total
of 9768 data were measured with Miller indices hmin = ꢃ15,
hmax = 15, kmin = ꢃ18, kmax = 18, lmin = ꢃ18, lmax = 18, in the range
of 3.014 < h < 27.553° for 1, and a total of 19 241 data were mea-
sured with Miller indices hmin = ꢃ17, hmax = 17, kmin = ꢃ23,
was solved in P 1 space group. The asymmetric unit of crystal
structure of 1 (Fig. S1, Supplementary Information) contains one
lithium(I), one sodium(I) and two copper(II) ions, one cpdp3ꢃ and
one succinate ligand, and one coordinated methanol and two coor-
dinated water molecules. Two chloride ions as counter anions and
six lattice waters are also present in the asymmetric unit. The full
structure is generated by growing the asymmetric unit through
center of inversion. A view of the crystal structure of hetero-
octanuclear unit of 1 is illustrated in Fig. 1. It consists of an octanu-
clear core in which a cyclic [Li2Na2] central unit is linked to two
dinuclear [Cu2] complexes by endogeneous carboxylate and exoge-
neous succinate bridges. Two carboxylate groups of two cpdp3ꢃ
kmax = 22,
lmin = ꢃ24,
lmax = 24,
in
the
range
of
1.7241 < h < 28.0495° for 2, using
x
oscillation frames. The data
were corrected for absorption by the multi-scan method [34] giv-
ing minimum and maximum transmission factors. The structures
of both 1 and 2 were solved by direct methods using the software
SIR-97 [35], and refined by full-matrix least-squares methods
against F2 with the programs SHELXL [36,37] embedded in the rou-
tine Olex2 [38]. The residual electron densities in 1 and 2 were
in the range of ꢃ1.163 to 2.009 eꢀÅꢃ3 and +1.359 to ꢃ0.716 eꢀÅꢃ3
,
ligands exhibit a rare l3: : :g
g2 g1 1 tridentate bridging mode (a mon-
odentate and an anti-anti bidentate bridge) (Chart 1), with each
bridging among one copper, one lithium and one sodium ion. This
type of tridentate bridges in metal-carboxylate chemistry is
respectively. The difference Fourier map was used to locate the
hydrogen atoms. The hydrogen atoms were fixed at ideal positions
and refined as riding models.
Scheme 1. Synthetic pathway of ligand H3cpdp.
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

4
S. Haldar et al. / Polyhedron xxx (xxxx) xxx
Scheme 2. Synthetic pathway of complexes 1 and 2.
mode is rare [43]. It is fascinating to mention that an eleven mem-
bered metallomacrocyclic ring defined by Cu(2)–O(7)–C(32)–C
(33)–C(34)–C(35)–O(9)–Na(1)–O(5)–C(31)–O(4) is formed on
either side of the [Li2Na2] core (Fig. 2).
The coordination sites at the copper centers are occupied by
two N-donors provided by one tertiary amine and one pyridyl
amine group, and three O-donors provided by one bridging alkox-
ide, one terminal carboxylate and one bridging succinate group.
Geometric constraints imposed by the succinate ligands lead to a
distorted square pyramidal (s = 0.290 for Cu1 and s = 0.205 for
Cu2) [44] copper coordination environments. The deviations of
the copper centers from the basal planes are 0.164 (Cu1) and
0.193 Å (Cu2). The coordination environment of lithium(I) ion
may be defined by the distorted tetrahedral geometry, with one
succinate oxygen, one carboxylate oxygen, one water oxygen and
one methanol oxygen atom. On the other hand, the coordination
environment of sodium(I) ion may be best described by the dis-
torted trigonal bipyramidal geometry, with two succinate oxygen,
one carboxylate oxygen and two water oxygen atoms. The Cu–
Oalkoxide and Cu–Ocarboxylate bond distances range from 1.896(3) to
2.214(4) Å, and Cu–Namine bond distances range from 1.986(4) to
2.033(4) Å. [31,41] The intra-metallic separation between the cop-
per centers bridged across the alkoxide group is 3.447(5) Å. Note-
worthy here is that the X-ray structure of 1 features carboxylate/
water/methanol susceptible hydrogen bonding interactions that
contribute towards the stabilization of the crystal lattice (Fig. 3).
Fig. 1. X-ray crystal structure of 1 with atom numbering scheme. Hydrogen atoms
are omitted for clarity.
uncommon [42]. The two independent succinate ligands utilize all
four coordinating groups showing an unprecedented l4
bridging mode (Chart 1) linking two copper, one lithium and one
sodium ion. Although the l4
g1 bridging mode of succi-
nate is quite common in the literature, the l4
g1 bridging
: : : :
g2 g1 g1 g1
:
g1 g1 g1
: : :
:
g2 g1 g1
: : :
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

S. Haldar et al. / Polyhedron xxx (xxxx) xxx
5
Chart 1. Observed coordination modes of the ligand cpdp3ꢃ (a, b, c) and succinate (d, e) in complexes 1 and 2.
Fig. 3. Packing diagram of 1 showing hydrogen bonding interactions.
Fig. 2. Core framework of 1 showing metallomacrocyclic topologies.
two [Zn4(cpdp)2(suc)] complexes. Consequently, a metallomacro-
cyclic ring demarcated by Li(1)–O(10)–C(62)–O(9)–Zn(4)–O(6)–
Zn(3)–O(7)–C(48)–O(8)–Li(10)–O(100)–C(620)–O(90)–Zn(40)–O(60)–
Zn(30)–O(70)–C(480)–O(80) is shaped through the symmetrical
arrangement of two lithium and four zinc ions with four and five
coordination environments, respectively (Fig. 5). The core of each
tetranuclear [Zn4(cpdp)2(suc)] species is constructed by two [Zn2
3.3. Description of the X-ray crystal structure of 2
Complex 2 cryꢃstallized in the triclinic system and the structure
was solved in P 1 space group. The asymmetric unit of crystal
structure of 2 (Fig. S2, Supplementary Information) consists of
one lithium(I), one sodium(I) and four zinc(II) ions, two cpdp3ꢃ
and one succinate ligand, and two coordinated water molecules.
The asymmetric unit also contains two chloride and three bromide
ions as counter ions along with six methanol and nineteen water
molecules as solvents of crystallization. The full structure is gener-
ated by growing the asymmetric unit through center of inversion.
To balance the total charge, two protons have to be included in the
structure. However, the protons could not be located precisely
from Fourier density map. A view of the crystal structure of het-
ero-decanuclear unit of 2 is illustrated in Fig. 4. Formation of this
hetero-decanuclear complex is accomplished by the self-assembly
of two tetranuclear [Zn4(cpdp)2(suc)] complexes and two [Li
(H2O)2]+ ions linked entirely by four carboxylate groups of cpdp3ꢃ
(cpdp)]+ units bridged by a succinate group in a l4 g1 g1 g1 g1
: : : :
mode (Chart 1). The two zinc centers within each [Zn2(cpdp)]+ unit
are bridged and chelated by an alkoxide oxygen of cpdp3ꢃ ligand
and a COO– linkage of succinate. The solid state structure of 2 also
consists of a 20-membered large size cavity of ꢁ5.4 Å.
The eight zinc sites have identical coordination environments,
with each site exhibiting a highly distorted trigonal bipyramidal
geometry (s = 0.672 for Zn1,s = 0.828 for Zn2, s = 0.814 for Zn3,
and = 0.740 for Zn4) [44]. Each zinc center is surrounded by a
s
bridging alkoxide oxygen, a terminal carboxylate oxygen, a tertiary
amine nitrogen, a pyridine nitrogen from a cpdp3ꢃ ligand, and one
bridging succinate oxygen. From the basal planes, the zinc ions are
deviated by 0.190 (Zn1), 0.215 (Zn2), 0.200 (Zn3) and 0.185 Å
(Zn4). The coordination environment of lithium(I) ion shows a dis-
torted tetrahedral geometry, with two carboxylate oxygen and two
ligands in a l2
: :
g1 g1 anti-anti bidentate fashion (Chart 1). In
essence, two [Li(H2O)2]+ ions act as interconnectors between the
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

6
S. Haldar et al. / Polyhedron xxx (xxxx) xxx
Fig. 4. X-ray crystal structure of 2 with atom numbering scheme. Hydrogen atoms are omitted for clarity.
parameters for 1 and 2 are summarized in Table S1. Selected bond
lengths and angles are given in Table 1.
3.4. Spectroscopic studies
In the FTIR spectrum of 1, the strong bands appearing at 1589,
1580 and 1563 cmꢃ1, and 1459, 1430 and 1403 cmꢃ1 are assigned
to the
m m
as(COO–) and s(COO–) vibrations of the carboxylates,
respectively (Fig. S4, Supplementary Information). The relatively
higher difference of
ascribed to the monodentate terminal as well as monodentate
D
(
D
=
m
as(COO–) –
m
s(COO–)) of ꢁ186 cmꢃ1 is
bridging mode of carboxylate coordination [45,46]. The value of
D
at ꢁ150 cmꢃ1 frequently indicates the syn-syn bidentate bridg-
ing coordination of succinate [45,46]. The occurrence of syn-anti
bidentate bridging mode of carboxylate and chelating binding
mode of succinate is manifested by significantly lower value of
D
Fig. 5. Core framework of 2 showing a metallomacrocyclic ring.
at ꢁ104 cmꢃ1 [45,46]. The FTIR spectrum of 2 exhibits the strong
bands at 1595, 1588 and 1571 cmꢃ1
, and 1447, 1430 and
water oxygen atoms. Again, the coordination environment of
sodium(I) ion exhibits a highly distorted octahedral geometry com-
pleted by two carboxylate oxygen and four water oxygen atoms.
1394 cmꢃ1 which correspond to the as(COO–) and s(COO–) vibra-
m m
tions of the carboxylates, respectively (Fig. S5, Supplementary
Information). The monodentate terminal coordination of carboxy-
The Zn–Obridging
bond distances [Zn1–O1, 1.950(4); Zn2–
late group is indicated by the relatively higher difference of
D
at
alkoxide
O1, 1.950(4), Zn3–O6, 1.962(4) and Zn4–O6, 1.946(3) Å] are within
the range of those reported previously [26], and the values indicate
that Zn–O alkoxide bridge is asymmetric. The Zn–Obridging succinate
bond distances [Zn1–O11, 2.025(4); Zn2–O12, 2.047(4), Zn3–O13,
2.043(3); Zn4–O14, 2.023(4) Å] indicate that the Zn-O succinate
bridge is also symmetric. Within each tetranuclear [Zn4(cpdp)2
(suc)] complex, the average intra-dimeric Znꢀ ꢀ ꢀZn separation is
3.487 Å and the average inter-dimeric Znꢀ ꢀ ꢀZn separation is
6.839 Å. It may be significant to mention that the moderate
ꢁ201 cmꢃ1. The comparatively lower values of
D
at ꢁ158 and
124 cmꢃ1 specify the existence of syn-syn bidentate bridging mode
of succinate and anti-anti bidentate bridging mode of carboxylate,
respectively [45,46]. In addition, the strong bands at 1609 (1) and
1608 (2) cmꢃ1 are indicative of
m(C@N) stretching vibrations of
pyridyl functionality of the ligand backbone.
We have carried out electronic absorption spectroscopy of both
1 and 2 by recording their spectra (Fig. S6, Supplementary Informa-
tion) in methanol solution in the range of 200–900 nm. Broad
intramolecular
p
ꢀ ꢀ ꢀ
p
stacking interactions have been observed
absorption band with maxima at 693 nm (
e
, 460 Mꢃ1 cmꢃ1) for 1,
within each tetranuclear species due to face-to-face sequential
arrangement of benzoate-pyridyl-pyridyl-benzoate rings (Fig. S3,
Supplementary Information). Close analysis of X-ray structure
specifies such interactions between the adjacent benzoate-pyridyl,
pyridyl-pyridyl, and pyridyl-benzoate rings, with average closest
contacts of 4.026, 3.762, and 3.604 Å, respectively. 2 can also be
viewed as a rare example of a hetero-decanuclear Li2Zn8 complex
displaying three different binding modes of carboxylates (terminal,
corresponds to the d-d transition. The intense absorption bands
at 259 nm (e e
, 64956 Mꢃ1 cmꢃ1) for 1, and 264 nm ( , 50518 Mꢃ1
cmꢃ1) for 2 are observed, due to the metal ion-bound ligand-based
charge transfer transitions.
The 1H NMR spectrum complex 2 shows a triplet at 3.09 ppm
for eight hydrogens of succinate and a broad multiplet in the range
of 3.12–4.24 ppm for fifty two –CH2– protons of the ligands. The
presence of sixty four aromatic protons has been exhibited by
broad multiplets in the range of 6.72–7.64 ppm. In the 13C NMR
anti-anti l2: : : : : :g
g1 g1 and l4 g1 g1 g1 1). Crystal data and refinement
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

S. Haldar et al. / Polyhedron xxx (xxxx) xxx
7
carboxylate of cpdp3ꢃ ligand and two similar bidentate bridging
succinate carboxylates but under different dimetallic coordination
environments, respectively. The 13C NMR signals appeared in the
range of 51.81–63.72 ppm and 122.88–157.57 ppm, correspond
to the aliphatic and aromatic carbons, respectively.
Table 1
Selected bond distances (Å) and angles (°) for [Li2Na2Cu4(cpdp)2(suc)2(CH3OH)2(H2-
O)4]Cl2ꢀ6H2O (1) and Na(H3O)2[Li2Zn8(cpdp)4(suc)2(H2O)4]Cl2Br3ꢀ6MeOHꢀ19H2O (2).
Bond distances [Å]
1
2
Cu(1)–O(1) 1.896(3)
Cu(1)–O(6) 1.931(3)
Cu(1)–N(3) 1.986(4)
Cu(1)–N(1) 2.033(4)
Cu(1)–O(2) 2.214(3)
Cu(2)– O(1) 1.896(3)
Cu(2)–O(7) 1.962(3)
Cu(2)–N(4) 1.982(4)
Cu(2)–N(2) 2.042(4)
Cu(2)–O(4) 2.192(3)
Li(1)–O(5) 1.956(9)
Li(1)–O(2 W) 2.012(9)
Li(1)–O(10) 1.899(10)
Li(1)–O(8) 1.904(9)
Na(1)–O(8) 2.506(4)
Na(1)–O(9) 2.314(4)
Na(1)–O(2 W) 2.308(4)
Na(1)–O(1 W) 2.318(5)
Na(1)–O(5) 2.307(4)
Zn(1)–O(1) 1.950(4)
Zn(1)–O(2) 1.987(4)
Zn(1)–O(11) 2.025(4)
Zn(1)–N(1) 2.222(4)
Zn(1)–N(3) 2.054(4)
Zn(2)–O(1) 1.949(4)
Zn(2)–O(4) 1.985(4)
Zn(2)–O(12) 2.048(4)
Zn(2)–N(2) 2.214(4)
Zn(2)–N(4) 2.047(4)
Zn(3)–O(6) 1.962(3)
Zn(3)–O(7) 1.981(4)
Zn(3)–O(13) 2.043(3)
Zn(3)–N(5) 2.203(4)
Zn(3)–N(7) 2.065(4)
Zn(4)–O(6) 1.945(3)
Zn(4)–O(9) 1.976(4)
Zn(4)–O(14) 2.023(4)
Zn(4)–N(6) 2.215(4)
Zn(4)–N(8) 2.074(5)
Li(1)–O(8) 1.892(10)
Li(1)–O(16) 1.879(11)
Li(1)–O(10) 1.936(11)
Li(1)–O(15) 1.941(10)
3.5. Thermal property and stability
Thermogravimetric analysis (TGA) of 1 (Fig. 6) shows an initial
weight loss of 5.46% (calcd: 5.50%) in the temperature range of
97–180 °C corresponding to the loss of six lattice waters. Subse-
quently, the second weight loss of 7.45% (calcd: 7.40%) from 251
to 280 °C and the third weight loss of 17.90% (calcd: 18.00%) from
281 to 443 °C could be attributed to the losses of four coordinated
water and two coordinated methanol molecules, and eight CO2
molecules, respectively. Further decomposition of metal–organic
framework is observed between 479 and 811 °C, resulting in the
formation of Li2O, Na2O and CuO as possible final residues. The
TGA plot of 2 (Fig. 6) exhibits the first weight loss of 9.65% (calcd:
9.69%) in the temperature range of 30–101 °C indicating the loss of
twenty one lattice waters. The second weight loss of 4.88% (calcd:
4.92%) in the temperature range of 257–287 °C shows the removal
of six uncoordinated methanol molecules. The third and fourth
weight losses of 1.82% (calcd: 1.84%) from 305 to 317 °C and
15.28% (calcd: 15.37%) from 324 to 420 °C correspond to the losses
of four coordinated water molecules, and twelve CO2 molecules,
respectively. Then, the metal–organic framework undergoes
decomposition between 472 and 745 °C, giving rise to Li2O, Na2O
and ZnO as possible final residues
We have performed the PXRD experiment with Bragg angular
range, i.e., 2h (5°<2h < 90°) at room temperature for both com-
plexes 1 and 2 using the microcrystalline samples obtained upon
drying the crystals in the vacuum desicator. Then we have heated
both these microcrystalline samples at ꢁ100 and 180 °C and again
performed their PXRD measurement. The patterns of PXRD spectra
(Figs. S8 & S9, Supplementary Information) obtained for 1 and 2
before and after heating the samples, are more or less same
without any significant change. Additionally, no characteristic
new peaks are observed within the limits of experiment, suggest-
ing that the structures are thermally stable up to a certain temper-
ature. However, for both 1 and 2, there are minor changes of the
intensity of the peaks before and after heating the samples. There
is hardly any shift of the peaks in the spectra obtained before and
after heating the samples. This results also indicate that upon the
Bond angles [°]
1
2
O(1)–Cu(1)–O(6) 96.66(14)
O(1)–Cu(1)–N(3) 157.44(16)
O(6)–Cu(1)–N(3) 91.88(15)
O(1)–Cu(1)–N(1) 85.99(15)
O(6)–Cu(1)–N(1) 174.85(15)
N(3)–Cu(1)–N(1) 84.08(16)
O(1)–Cu(1)–O(2) 97.84(14)
O(6)–Cu(1)–O(2) 92.13(14)
N(3)–Cu(1)–O(2) 102.67(15)
N(1)–Cu(1)–O(2) 91.87(14)
O(1)–Cu(2)–O(7) 96.48(13)
O(1)–Cu(2)–N(4) 160.68(15)
O(7)–Cu(2)–N(4) 93.01(14)
O(1)–Cu(2)–N(2) 85.23(14)
O(7)–Cu(2)–N(2) 173.00(14)
N(4)–Cu(2)–N(2) 83.44(15)
O(1)–Cu(2)–O(4) 99.17(13)
O(7)–Cu(2)–O(4) 94.40(12)
N(4)–Cu(2)–O(4) 96.83(14)
N(2)–Cu(2)–O(4) 92.01(13)
Li(1)–O(5)–Na(1) 89.0(3)
Li(1)–O(8)–Na91) 112.6(3)
O(5)–Na(1)–O(2 W) 82.01(13)
O(5)–Na(1)–O(9) 128.98(14)
O(2 W)–Na(1)–O(9) 147.30(15)
O(5)–Na(1)–O(1 W) 100.43(15)
O(1)–Zn(1)–O(2) 107.65(15)
O(1)–Zn(1)–O(11) 98.17(14)
O(1)–Zn(1)–N(1) 83.05(15)
O(1)–Zn(1)–N(3) 117.13(16)
O(2)–Zn(1)–O(11) 95.64(15)
O(2)–Zn(1)–N(1) 90.71(16)
O(2)–Zn(1)–N(3) 132.44(16)
O(11)–Zn(1)–N(1) 172.81(16)
O(11)–Zn(1)–N(3) 93.22(17)
N(3)–Zn(1)–N(1) 79.98(17)
O(1)–Zn(2)–O(4) 116.07(16)
O(1)–Zn(2)–O(12) 97.48(15)
O(1)–Zn(2)–N(2) 81.23(15)
O(1)–Zn(2)–N(4) 123.10(17)
O(4)–Zn(2)–O(12) 95.02(16)
O(4)–Zn(2)–N(2) 91.91(17)
O(4)–Zn(2)–N(4) 117.40(17)
O(12)–Zn(2)–N(2) 172.78(16)
N(4)–Zn(2)–O(12) 95.96(16)
N(4)–Zn(2)–N(2) 79.00(16)
O(6)– Zn(3)–O(7) 114.06(16)
O(6)–Zn(3)–O(13) 98.78(14)
O(6)–Zn(3)–N(5) 81.83(15)
O(6)–Zn(3)–N(7) 124.99(15)
O(7)–Zn(3)–O(13) 93.39(15)
O(7)–Zn(3)–N(5) 91.93(16)
O(7)–Zn(3)–N(7) 117.96(16)
O(13)–Zn(3)–N(5) 173.85(15)
O(13)–Zn(3)–N(7) 94.89(15)
N(7)–Zn(3)–N(5) 79.87(16)
O(6)–Zn(4)–O(9) 112.92(16)
O(6)–Zn(4)–O(14) 96.98(15)
O(6)–Zn(4)–N(6) 82.23(15)
O(6)–Zn(4)–N(8) 119.94(17)
O(9)–Zn(4)–O(14) 97.95(18)
O(9)–Zn(4)– N(6) 92.44(17)
O(9)–Zn(4)–N(8) 124.58(17)
O(14)–Zn(4)–N(6) 168.98(19)
O(14)–Zn(4)–N(8) 91.33(19)
N(8)–Zn(4)–N(6) 79.70(17)
spectrum of complex 2 (Fig. S7, Supplementary Information),
characteristic peaks at 176.11, 176.22, 180.70 and 180.91 ppm
are observed due to the presence of one type of monodentate ter-
minal carboxylate of cpdp3ꢃ ligand, one type of bidentate bridging
Fig. 6. TGA plot of 1 and 2 under N2 gas atmosphere at heating rate of 10 °C minꢃ1
.
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

8
S. Haldar et al. / Polyhedron xxx (xxxx) xxx
mode of succinate in 1, and anti-anti l2
mode of carboxylate and l4
1 bridging mode of succinate
in 2 are quite sporadic. The presence of Li/Na ions and l4
g1 bridging mode of succinate appears to provide
: :
g1 g1 bidentate bridging
:
g1 g1 g1
: : :g
:
g2 g1 g1
: : :
g1 g1 g1 g1
/l4: : : :
the stabilizing factors for the heterometallic octanuclear
[Li2Na2Cu4] and decanuclear [Li2Zn8] cores. Variable temperature
magnetic studies of 1 show antiferromagnetic interactions among
the copper centers with J = –22.03 cmꢃ1. This work not only offers
an outlook towards the development of new heterometallic mult-
inuclear complexes, but also suggests the potential for advancing
new classes of multifunctional materials by using multinuclear
transition metal complexes. Currently, we are pursuing our
research work to prepare different heterometallic multinuclear
complexes of other 3d transition metals based on these unique
coordination-cum-bridging abilities of succinate as well as glu-
tarate/adipate ions supported by the polydentate ligand, H3cpdp.
Acknowledgements
Fig. 7. Temperature dependence of vMT for 1. The red solid line corresponds to the
best fit obtained with the isotropic exchange Hamilton described in the text.
The work was strongly supported by The Council of Scientific &
Industrial Research (CSIR) (Grant No.: 01(2732)/13/EMR-II), New
Delhi. The DST-FIST and UGC-SAP programs are acknowledged
for providing the instrumental facilities in the Department of
Chemistry, University of Kalyani. The Contingency Grant provided
by the DST-PURSE program in the Department of Chemistry is also
acknowledged. S.H. greatly acknowledges the RGNF received from
UGC, New Delhi.
loss of lattice waters from complexes 1 and 2, their structures are
retained.
3.6. Magnetic properties
Variable temperature magnetic susceptibility data were col-
lected for 1 in a temperature range of 2–300 K under an applied
field of 1 Tesla on powdered microcrystalline sample with a SQUID
magnetometer (MPMS-7, Quantum Design, Fig. 7). For the
interpretation of the magnetic data, only the asymmetric unit
Appendix A. Supplementary data
CCDC 1860696 and 1860697 contains the supplementary
crystallographic data for complexes 1 and 2. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data
to this article can be found online at https://doi.org/10.1016/j.
poly.2019.03.013.
was taken into account. At room temperature a
vMT-value of
0.85 cm3 Kmolꢃ1, which is very close to the expected value of
0.75 cm3 Kmolꢃ1 for two uncoupled spins with S1 = S2 = 1/2. By
lowering the temperature up to 100 K, a gradual decrease in
vMT
value is documented. Further cooling results in a sharp decrease
reaching to a value of 0.32 cm3 Kmolꢃ1 at 2 K. This reflects the fact
that the magnetic behavior of the title complex is determined by
moderate antiferromagnetic interactions within the molecule.
The coupling within this complex can be described by the simplest
possible Heisenberg Spin Hamiltonian multiplied by 2 in order to
account for the two [Cu2] dimers: H = 2 ꢄ [ꢃ2JS1S2]. This is because
the coupling between the [Cu2] dimers is expected to be negligible
in front of the moderate antiferromagnetism observed within the
intradimers. Indeed, the copper(II) ions of different pairs which
are separated by 10.839 Å are connected only by the alkali metal
ions bridged by succinate and carboxylate moieties at the two
ends. A good fit of the data can be obtained by including the weakly
coupled paramagnetic impurities. The magnetic data can be simu-
lated in adequate manner with J = –22.03 cmꢃ1 and g1 = g2 = 2.05. A
TIP of 400 ꢄ 10ꢃ6 cm3 Kmolꢃ1 was included while simulating the
magnetic data.
References
[1] V. Chandrasekhar, D. Sahoo, R.S. Narayanan, R.J. Butcher, F. Lloret, E. Pardo,
Dalton Trans. 42 (2013) 8192.
[2] A.A. Dar, S. Sen, S.K. Gupta, G.N. Patwari, R. Murugavel, Inorg. Chem. 54 (2015)
9458.
[3] C.H. Chiang, Y.W. Tzeng, C.I. Yang, M. Nakano, W.L. Wan, L.L. Lai, G.H. Leed,
Dalton Trans. 46 (2017) 1237.
[4] T.R. Zheng, L.L. Qian, M. Li, Z.X. Wang, K. Li, Y.Q. Zhang, L. Li, Bao Bing Wu,
Dalton Trans. 47 (2018) 9103.
[5] J.J. Henkelis, L.F. Jones, M.P. De, C.A. Miranda, H.M.A. Kilner, Inorg. Chem. 49
(2010) 11127.
[6] E.C. Constable, C.E. Housecroft, J.A. Zampese, G. Zhang, Polyhedron 44 (2012)
150.
[7] H. Zhang, Jin Zhang, Y. Rui Liu, W. Li, W Li Liu, Eur. J. Inorg. Chem. (2016) 4134.
[8] T. Glaser, Chem. Commun. 47 (2011) 116.
[9] S.A. Corrales, J.M. Cain, K.A. Uhlig, A.M. Mowson, C. Papatriantafyllopoulou, M.
K. Peprah, A. Ozarowski, A.J. Tasiopoulos, G. Christou, M.W. Meisel, C.
Lampropoulos, Inorg. Chem. 55 (2016) 1367.
4. Conclusion
[10] T. Jenkins, A.M. Garnero, S.A. Corrales, E.R. Williams, A.M. Mowson, A.
Ozarowski, W. Wernsdorfer, G. Christou, C. Lampropoulos, Inorg. Chem. 56
(2017) 14755.
[11] M. Charalambous, Eleni E. Moushi, T.N. Nguyen, A.M. Mowson, G. Christou, A,,
J., Tasiopoulos,, Eur. J. Inorg. Chem. (2018) 3905.
[12] Y.Z. Zheng, E.M. Pineda, M. Helliwell, R.E.P. Winpenny, Chem. Eur. J. 18 (2012)
4161.
[13] A.M. Ako, I.J. Hewitt, V. Mereacre, R. Clrac, W. Wernsdorfer, C.E. Anson, A.K.
Powell, Angew. Chem. 118 (2006) 5048, Angew. Chem., Int. Ed. 45 (2006)
4926-4929.
In conclusion, complexation of copper(II) and zinc(II) ions with
H3cpdp and succinate ligands led to the isolation of two unprece-
dented metallomacrocyclic octanuclear [Li2Na2Cu4] (1) and
decanuclear [Li2Zn8] (2) complexes. Both 1 and 2 represent the first
examples of succinate-bridged heterometallic high nuclearity
complexes (N ꢂ 6) with any class of bridging or non-bridging
ligand. Complexes 1 and 2 display several versatile coordination-
cum-binding modes of the carboxylate and succinate groups stud-
[14] C.J. Milios, A. Vinslava, W. Wernsdorfer, S. Moggach, S. Parsons, S.P. Perlepes, G.
Christou, E.K. Brechin, J. Am. Chem. Soc. 129 (2007) 2754.
[15] D.A. Whittington, S.J. Lippard, J. Am. Chem. Soc. 123 (2001) 827.
[16] C. Gerdemann, C. Eicken, B. Krebs, Acc. Chem. Res. 35 (2002) 183.
ied by X-ray crystallography and FTIR. Among these, tridentate l3
:
g2
:
g1
:g
1 bridging mode of carboxylate and l4 1 bridging
: : : :g
g2 g1 g1
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013

S. Haldar et al. / Polyhedron xxx (xxxx) xxx
9
[17] C.E. Elwell, N.L. Gagnon, B.D. Neisen, D. Dhar, A.D. Spaeth, G.M. Yee, W.B.
Tolman, Chem. Rev. 117 (2017) 2059.
[33] Data Reduction, SAINT Software Reference Manual, Bruker-AXS, Madison, WI,
1998.
[18] E.I. Solomon, D.E. Heppner, E.M. Johnston, J.W. Ginsbach, J. Cirera, M. Qayyum,
E.M.T. Kieber, C.H. Kjaergaard, R.G. Hadt, Li., Tian,, Chem. Rev. 114 (2014)
3659.
[19] A. Patra, S.K. Saha, T.K. Sen, L. Carrella, G.T. Musie, A.R. Khuda-Bukhsh, M. Bera,
Eur. J. Inorg. Chem. (2014) 5217.
[34] G.M. Sheldrick, SADABS, University of Göttingen, Germany, Program for Multi-
Scan Absorption Correction of Area Detector Data, 2002.
[35] C. Giacovazzo, A. Guagliardi, A.G.G. Moliterni, G. Polidori, R. Spagna, J. Appl.
Crystallogr. 32 (1999) 115.
[36] (a) G. M. Sheldrick, SHELXL. Version 6.10 Reference Manual. Bruker-AXS,
Madison, WI, 2000; (b) International Tables for Crystallography, Vol C, Tables
6.1.1.4, 4.2.6.8, and 4.2.4.2, Kluwer: Boston, 1995.
[20] Z. Chen, Y. Shen, L. Li, H. Zou, X. Fu, Z. Liu, K. Wang, F. Liang, Dalton Trans. 46
(2017) 15032.
[21] D. Ghoshal, T.K. Maji, S.G. Mostafa, T.H. Sain, J. Lu, E. Zangrando, J. Ribas, N.R.
Chaudhuri, Dalton Trans. (2004) 1687.
[37] G.M. Sheldrick, Crystal structure refinement with SHELXL, Acta Cryst. C 71
(2015) 3.
[22] D.F. Li, Z. Liao, Y. Wei, F. Du, M. Wang, W. Chen, W. Li, X. Mao, Dalton Trans.
(2003) 2164.
[23] A.K. Ghosh, D. Ghoshal, E. Zangrando, J. Ribas, N.R. Chaudhuri, Inorg. Chem. 46
(2007) 3057.
[24] P.M. Forster, A.K. Cheetham, Angew. Chem., Int. Ed. 41 (2006) 457.
[25] J.P. Costes, J.P. Laurent, J.M.M. Sanchez, J.S. Varela, M. Ahlgren, M. Sundberg,
Inorg. Chem. 36 (1997) 4641.
[38] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, OLEX2:
a complete structure solution, refinement and analysis program, J. Appl. Cryst.
42 (2009) 339.
[39] S. Haldar, G. Vijaykumar, A.K. Ghosh, L. Carrella, M. Bera, Polyhedron 121
(2017) 130.
[40] N. Dutta, S. Haldar, G. Vijaykumar, S. Paul, A.P. Chattopadhyay, L. Carrella, M.
Bera, Inorg. Chem. 57 (2018) 10802.
[26] S. Haldar, G. Vijaykumar, L. Carrella, S. Batha, G.T. Musie, M. Bera, ACS Omega 2
(2017) 1535.
[41] A. Patra, T.K. Sen, A. Ghorai, G.T. Musie, S.K. Mandal, U. Ghosh, M. Bera, Inorg.
Chem. 52 (2013) 2880.
[27] M. Bera, G.T. Musie, D.R. Powell, Inorg. Chem. 48 (2009) 4625.
[28] S. Haldar, G. Vijaykumar, L. Carrella, G.T. Musie, M. Bera, New J. Chem. 42
(2018) 1276.
[42] R.L. Rardin, W.B. Tolman, S.J. Lippard, New J. Chem. 15 (1991) 417.
[43] N. Scales, Y. Zhang, M. Bhadbhade, I. Karatchevtseva, L. Kong, G.R. Lumpkin, F.
Li, Polyhedron 102 (2015) 130.
[29] R.L. Carlin, Magnetochemistry, Springer-Verlag, New York, 1986.
[30] N.F. Chilton, R.P. Anderson, L.D. Turner, A. Soncini, K.S. Murray, PHI, J. Comput.
Chem. 34 (2013) 1164.
[31] A. Patra, S. Haldar, G. Vijaykumar, L. Carrella, A.K. Ghosh, M. Bera, Inorg. Chim.
Acta 436 (2015) 195.
[44] A. Addison, T.N. Rao, J. Reedijk, J. van Rijn, G.C. Verschoor, J. Chem. Soc., Dalton
Trans. (1984) 1349.
[45] G.B. Deacon, R.J. Phillips, Coord. Chem. Rev. 33 (1980) 227.
[46] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, 4th ed., Wiley, New York, 1986, pp 231-233, 251, 253.
[32] Data Collection, SMART Software Reference Manual, Bruker-AXS, Madison, WI,
1998.
Please cite this article as: S. Haldar, N. Dutta, G. Vijaykumar et al., Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and
decanuclear Li2Zn8 complexes, Polyhedron, https://doi.org/10.1016/j.poly.2019.03.013