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S. Roy, M. G. B. Drew, A. Frontera and A. Bauza, Dalton Trans., 2017, DOI: 10.1039/C6DT04906K.
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Page 1 of 38 Dalton Transactions
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DOI: 10.1039/C6DT04906K
Estimation of conventional C-H∙∙∙π (arene), unconventional C-H∙∙∙π
(chelate) and C-H∙∙∙π (thiocyanate) interactions in hetero-nuclear
nickel-cadmium complexes with a compartmental Schiff base: Novel
Dalton Transactions Accepted Manuscript

Published on 16 March 2017. Downloaded by Freie Universitaet Berlin on 16/03/2017 16:15:40.
example of a diamine bridged hetero-polynuclear complex having
NiO2Cd core
Sourav Roy,a Michael G. B. Drew,b Antonio Bauzá,c Antonio Frontera,*c
Shouvik Chattopadhyay*a
a
Department of Chemistry, Inorganic Section, Jadavpur University, Kolkata - 700032, India.
Tel: +91-33-24572941, e-mail: shouvik.chem@gmail.com

b
School of Chemistry, The University of Reading, P.O. Box 224, Whiteknights, Reading RG6
6AD, United Kingdom, e-mail: m.g.b.drew@reading.ac.uk

c
Departamento de Química, Universitat de les Illes Balears, Crta. deValldemossa km 7.5, 07122
Palma, Baleares, Spain. e-mail: toni.frontera@uib.es
Abstract: Three new heteronuclear nickel(II)/cadmium(II) complexes,
[(SCN)(Cl)Cd(L)Ni(DMF)2] (1), [(SCN)(CH3CO2)Cd(L)Ni(CH3OH)2] (2) and
[(SCN)(Cl)Cd(L)Ni(NH2CH2CH2CH2NH2)]n (3) {where H2L = N,N'-bis(3-ethoxysalicylidene)
propane-1,3-diamine is a potential octadentate compartmental Schiff base}, have been
synthesized and characterized by elemental analysis, IR, UV-Vis and fluorescence spectroscopy.
The structures of the complexes have been confirmed by single crystal X-ray diffraction studies.
In each complex, nickel(II) is placed in the inner N2O2 environment and cadmium(II) is placed in
Dalton Transactions Page 2 of 38
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the outer O4 compartment of the compartmental Schiff base. Furthermore, the importance of
unconventional C-H∙∙∙π (chelate) interactions in the solid state of complexes 1 and 2 have been
described by means of DFT and MEP calculations and characterized using NCI plots. All
complexes show photoluminescence at room temperature upon the irradiation of ultraviolet light.

The lifetimes of excited states are in the range of 2-6 ns.
Keywords: Cadmium(II); Nickel(II); Heteronuclear; Compartmental Schiff base; Polymer;
Photoluminescence, C-H∙∙∙π interactions, DFT studies.
Introduction
Synthetic inorganic chemists have prepared various homo and hetero-polynuclear
transition and non-transition metal complexes with well-known salen type compartmental Schiff
bases (with inner N2O2 and outer O4 cores), prepared by the condensation of 3-
alkoxysalicyalaldehyde with several diamines.1 The bridging ability of the phenoxy oxygen
atoms of salen type Schiff bases made them popular in preparing such complexes2 which have
been used in non-linear optics, biological modelling application, magnetism, catalysis, opto-
electronic devices, molecular architectures etc over many years.3 Although many complexes
have been found to show ferromagnetic properties,4 lack of magnetic exchange interactions in
heteronuclear nickel(II)/cadmium(II) complexes did not make them attractive to scientists
working on magnetic materials. However, the importance of the cadmium(II) complexes lies in
their strong luminescence properties and potential applications in electronic and optoelectronic
devices.5 Focusing on the coordination chemistry, nickel(II) is a very attractive species for its
flexibility in attaining square planar, trigonal bipyramidal, square pyramidal, octahedral etc
geometries with coordination numbers varying from 4 to 6.6 Cadmium, on the other hand, with a
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d10 electronic configuration may also adopt varieties of geometries with no CFSE in any
geometry.7
Several bridging co-ligands e.g. acetate, thiocyanate, nitrate, dicyanamide, bipyridine,
azide etc have also been used to prepare such complexes.8 However, the use of a diamine to

bridge the hetero-binuclear units to prepare a polynuclear complex has not previously been
reported in the literature. Interactions based on π-systems are well established in crystal
engineering, which conventionally involve aryl rings. Among them, C-H∙∙∙π interactions9 are
important in stabilizing crystal structures and can be routinely evaluated during the analysis of
packing patterns in crystal structures. More recently, “unconventional” C-H∙∙∙π interactions
where the accepting π-system is a chelate ring have been defined and described.10 This emerging
type of supramolecular interaction is not usually taken into account by scientists working in
crystal engineering, despite the fact that the situation is analogous to an aromatic π-system owing
to the delocalisation of the π-electron density over the chelate ring. Thus, if chelate rings can
participate in π(chelate)···π(chelate) and π(chelate)···π stacking interactions as systematically
described work by Zaric and coworkers,11 so should chelate rings also participate in C-H∙∙∙π
(chelate) interactions. In fact Zaric and coworkers have identified, C-H∙∙∙π (chelate) interactions
in square-planar transition-metal acetylacetonate structures.12 Other works available in the
literature also mention to some extent the existence of C-H∙∙∙π (chelate) interactions; however
their utilization is quite rare.13
In the present work, a compartmental Schiff base has been used to prepare three hetero-
nuclear nickel(II)/cadmium(II) complexes. Interestingly, one of these complexes, namely 3
represents a diamine bridged polynuclear nickel(II)/cadmium(II) complex with NiO2Cd core.

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This is the first example of any diamine bridged polynuclear nickel(II)/cadmium(II) complex
with a compartmental Schiff base.
Moreover, the ability of both chelate-rings (nickel and cadmium) to establish C-
H∙∙∙π(chelate) interactions has been studied by means of DFT calculations. This type of

interaction, which is present in the solid state of complexes 1 and 2 has been evaluated
energetically and characterized using the non-covalent interaction plot (NCI plot) and molecular
electrostatic potential (MEP) surface computational tools. All three complexes exhibit
photoluminescence in DMF solution at room temperature upon the irradiation of ultraviolet light.
Experimental Section
Nickel(II) thiocyanate tetrahydrate was prepared in our laboratory following the literature
method.14 All other materials were commercially available, reagent grade and used as purchased
from Sigma-Aldrich without further purification.
Synthesis
Synthesis of the ligand H2L [N,N'-bis(3-ethoxysalicylidene)propane-1,3-diamine]
A methanol solution (10 ml) of 3-ethoxysalicylaldehyde (332 mg, 2 mmol) and 1,3-
diaminopropane (0.13 ml, 1 mmol) was refluxed for ca. 1 h to form the hexadentate ligand H2L.
The ligand was not isolated and used directly for the synthesis of the complexes.
Synthesis of the complex [(SCN)(Cl)Cd(L)Ni(DMF)2] (1)
A methanol (10 ml) solution of cadmium(II) chloride dihydrate (219 mg, 1 mmol) was
added to the methanol solution (20 ml) of H2L. The resulting solution was stirred for 15 min. A
methanol (10 ml) solution of nickel(II) thiocyanate tetrahydrate (250 mg, 1 mmol) was then
added . The stirring was continued for about 2h. A few drops of DMF were then added to the
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solution. Single crystals, suitable for X-ray diffraction, were obtained after 3-4 days on slow
evaporation of the solution in open atmosphere.
Yield: 288 mg (74%); based on nickel(II). Anal. Calc. for C28H38CdClN5NiO6S (FW
=779.25): C, 43.18; H, 4.90; N, 9.91; Found: C, 43.2; H, 4.9; N, 8.9%. ESI-MS (positive ion

mode, DMF) m/z: 449.09 [100%, Ni(L)Na]+; 427.11 [Ni(L)H]+. FT-IR (KBr, cm-1): 1652 (C=N);
2077 (NCS). UV-VIS [λmax(nm)] [εmax(Lmol-1cm-1)] (DMF): 273 (1.9104) [π-π*]; 357 (1.0104)
[n-π*]; 585 (1.8 101) [3T1g(F)  3A2g(F)]; 805(4.11) [3T2g(F)  3A2g(F)]. Fluorescence: [exi
(nm)] = 360, [emi (nm)] = 402. Lifetime [τavg (ns)] = 6. Fluorescence quantum yield = 0.004;
Magnetic moment = 3.11 BM. Experimental PXRD patterns of the bulk products are in good
agreement with the simulated XRD patterns from single crystal X-ray diffraction results,
indicating consistency of the bulk samples.
Synthesis of the complex [(SCN)(CH3CO2)Cd(L)Ni(CH3OH)2] (2)
Complex 2 was prepared in a similar method as that of complex 1, except that
cadmium(II) acetate dihydrate (266 mg, 1 mmol) was used instead of cadmium(II) chloride.
Single crystals, suitable for X-ray diffraction, were obtained after 3-4 days on slow evaporation
of the solution in open atmosphere.
Yield: 260 mg (72%); based on nickel(II). Anal. Calc. for C26H35CdN3NiO8S (FW
2087 (NCS). UV-VIS [λmax(nm)] [εmax(Lmol-1cm-1)] (DMF): 274 (2.2104) [π-π*]; 356 (1.1104)
[n-π*]; 567 (1.5101) [3T1g(F)  3A2g(F)]; 802 (5.12) [3T2g(F)  3A2g(F)]. Fluorescence: [exi
(nm)] = 356, [emi (nm)] = 398. Lifetime [τavg (ns)] = 2. Fluorescence quantum yield = 0.003,
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Magnetic moment = 3.10 BM. Experimental PXRD patterns of the bulk products are in good
agreement with the simulated XRD patterns from single crystal X-ray diffraction results,
indicating consistency of the bulk samples.
Synthesis of the complex [(SCN)(Cl)Cd(L)Ni(NH2CH2CH2CH2NH2)]n (3)

A methanol (10 ml) solution of cadmium(II) chloride dihydrate (219 mg, 1 mmol) was
added to the methanol solution (20 ml) of H2L. The resulting solution was stirred for 15 min. A
methanol (10 ml) solution of nickel(II) thiocyanate tetrahydrate (250 mg, 1 mmol) was then
added to it and stirred for 15 min. Subsequently 1 mmol of 1,3-diaminopropane (0.13 ml) was
added. The stirring was continued for about 2h. Single crystals, suitable for X-ray diffraction,
were obtained after 3-4 days on slow evaporation of the solution in open atmosphere.
Yield: 262 mg (74%); based on nickel(II). Anal. Calc. for C25H34CdClN5NiO4S (FW
2081 (NCS). UV-VIS [λmax(nm)] [εmax(Lmol-1cm-1)] (DMF): 272 (1.7104) [π-π*]; 357
(0.78103) [n-π*]; 565 (0.21102) [3T1g(F)  3A2g(F)]; 906 (8.22) [3T2g(F)  3A2g(F)].
Fluorescence: [exi (nm)] = 350, [emi (nm)] = 390. Lifetime [τavg (ns)] = 2. Fluorescence quantum
yield = 0.005, Magnetic moment = 3.13 BM. Experimental PXRD patterns of the bulk products
are in good agreement with the simulated XRD patterns from single crystal X-ray diffraction
results, indicating consistency of the bulk samples.

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Physical measurements
Elemental analyses (carbon, hydrogen and nitrogen) were performed using a Perkin
Elmer 240C elemental analyzer. IR spectra in KBr (4500-500 cm-1) were recorded with a Perkin
Elmer Spectrum Two spectrophotometer. Electronic spectra in DMF were recorded on a Perkin

Elmer Lambda 35 UV-visible spectrophotometer. Steady state photoluminescence spectra in
DMF were obtained in Shimadzu RF-5301PC spectrofluorometer at room temperature. Time
dependent photoluminescence spectra were recorded using Hamamatsu MCP photomultiplier
(R3809) and were analyzed by using IBHDAS6 software. The emission in the complexes is
tentatively attributed to intra-ligand transitions modified by metal coordination. The relative
fluorescence quantum yields for all complexes were measured in DMF using quinine sulfate (in
0.5 (M) H2SO4,  = 0.54) as the quantum yield standard. Intensity decay profiles were fitted to
the sum of exponential series I  t    exp   , where α

i
i
t
i i was a factor representing the
fractional contribution to the time resolved decay of the component with a lifetime of i. A bi-
exponential function was used to fit the decay profile for complexes, with obtaining χ2 close to 1.
The intensity-averaged lifetimes (av) were determined from the result of the exponential model
 i i
2
using  av  i
, where αi and I are the pre-exponential factors and excited state
 
i
i i
luminescence decay time associated with the i-th component, respectively. The magnetic
susceptibility measurements were performed with an EG and PAR vibrating sample
magnetometer, model 155 at room temperature (300 K) in a 5000G magnetic field, and
diamagnetic corrections were performed using Pascal's constants. Effective magnetic moments
were calculated using the formula µeff = 2.828(χMT)1/2, where χM is the corrected molar
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susceptibility. The instrument was calibrated using metallic nickel. Powder X-ray diffraction
measurements were obtained on a Bruker D8 instrument with Cu K radiation. In this process,
the complexes were ground with a mortar and pestle to fine powders which were then dispersed
with alcohol onto a zero background holder (ZBH). The alcohol was allowed to evaporate to

provide an even coating of powder adhered to the sample holder. The simulated PXRD patterns
of complexes were calculated from the single crystal structural data (Cifs) using the CCDC
Mercury software.
X-ray crystallography
Suitable crystals of complexes 1-3 were picked, mounted on a glass fibre and diffraction
intensities were measured with an Oxford Diffraction XCalibur diffractometer equipped with
Mo-Kα radiation (λ =0.71073 Å, 50 kV, 40 mA) at an ambient temperature (150 K). Data
collection and reduction were performed with the Crysalis software.15 The structures of the three
complexes were solved by direct methods using SHELXS-97 and refined by full-matrix least
squares on F2, using the SHELXL-97 package16. Non-hydrogen atoms were refined
anisotropically. The hydrogen atoms were placed in their geometrically idealized positions and
constrained to ride on their parent atoms. Hydrogen atoms attached with nitrogen and oxygen
atoms were located by difference Fourier maps. Programs used included PLATON,17
DIAMOND,18 ORTEP19 and MERCURY.20 Details of crystallographic data and refinement are
given in Table 1.
Theoretical methods
The calculations of the non-covalent interactions of complexes 1 and 2 were carried out
21
with TURBOMOLE software, version 7.0 using the M06-2X/def2-TZVP level of theory. To
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evaluate interactions in the solid state, crystallographic coordinates have been used. This
procedure and level of theory have been successfully used to evaluate similar interactions.22 The
interaction energies were computed by calculating the difference between the energies of isolated
monomers and their assembly. The interaction energies were corrected for the Basis Set

Superposition Error (BSSE) using the counterpoise method.23 The MEP surface calculations
have been performed by means of the G09 software at the M06-2X/6-31+G* level of theory.24
The NCI plot is a visualization index based on the electron density and its derivatives, and
enables identification and visualization of non-covalent interactions efficiently. The isosurfaces
correspond to both favourable and unfavourable interactions, as differentiated by the signs of the
second density Hessian eigenvalues and defined by the isosurface colour. NCI analysis allows an
assessment of host-guest complementarity and the extent to which weak interactions stabilize a
complex. The information provided by NCI plots is essentially qualitative, i.e. which molecular
regions interact. The colour scheme is a red-yellow-green-blue scale with red for ρ+cut (repulsive)
and blue for ρ−cut (attractive). Yellow and green surfaces correspond to weak repulsive and weak
attractive interactions, respectively.25 It should be mentioned that the theoretical DFT study has
been carried out only for complexes 1 and 2 because we have focused our attention to the
analysis of the C-H···π (chelate ring) interactions, which are not observed in complex 3.
Moreover, the intrinsic polymeric nature of complex 3 complicates the analysis of the non-
covalent interactions in the solid state.
Results and Discussion
Synthesis
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1,3-diaminopropane has been refluxed with 3-ethoxysalicylaldehyde in 1:2 ratio to form a
potential octadentate compartmental Schiff base ligand, H2L, following the literature method.26
This Schiff base (H2L) on reaction with cadmium(II) chloride dihydrate followed by the addition
of nickel(II) thiocyanate tetrahydrate in DMF gives rise to complex 1. The same Schiff base

(H2L) on reaction with cadmium(II) acetate dihydrate followed by the addition of nickel(II)
thiocyanate tetrahydrate in methanol forms complex 2. On the other hand, complex 3 has been
produced by reaction with cadmium(II) chloride dihydrate followed by the addition of nickel(II)
thiocyanate tetrahydrate and 1,3-diaminopropane to the methanol solution of H2L. Addition of
1,3-diaminopropane to the methanol solution of complex 1 also produces complex 3. Formation
of complexes is shown in Scheme 1.

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Scheme 1: Preparation of ligand and complexes.
Structure description
[(DMF)2NiLCd(NCS)(Cl)] (1) and [(SCN)(CH3CO2)Cd(L)Ni(CH3OH)2] (2)
The X-ray crystal structure determinations reveal that both complexes crystallize in
orthorhombic space groups P212121. Important bond lengths and bond angles are gathered in
Tables 2 and 3 respectively.
The molecular structures of complexes 1 and 2 are built from isolated hetero-binuclear
molecules of [(DMF)2NiLCd(NCS)(Cl)] and [(SCN)(CH3CO2)Cd(L)Ni(CH3OH)2] respectively.
Perspective view of complexes 1 and 2 are depicted in Figures 1 and 2, respectively. The Schiff
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base, H2L, is a potential octadentate compartmental Schiff base having inner N2O2 and outer O4
compartments with nickel(II) occupying the inner N2O2 cavity and cadmium(II) occupying the
outer O4 cavity. In both complexes, nickel(II) and cadmium(II) centres are hexa-coordinated.
The nickel(II) centres, Ni(1), have distorted octahedral geometry, where two imine nitrogen

atoms, N(19) and N(23) and two phenoxo oxygen atoms, O(11) and O(31), of the deprotonated
di-Schiff base constitute the equatorial plane. Bond lengths in the two molecules are similar as
shown in Table 2. In the equatorial plane the Ni-O and Ni-N bond distances are similar being in
the range 2.015(3)-2.041(3) Å. The deviation of the coordinating atoms, O(11), O(31), N(23)
and N(19), in the basal plane from the mean plane passing through them are 0.023(3), -0.024(2),
0.020(3) and -0.021(3) Å, respectively in complex 1 and -0.027(3), 0.018(3), -0.025(4) and
0.014(4) Å respectively in complex 2. The deviation of Ni(1) from the same plane is negligible
being 0.0022(5) Å in complex 1 and 0.0195(6) Å in complex 2. In complex 1 the nickel(II) is
coordinated axially by two oxygen atoms, O(1) and O(5) from two DMF molecules at distances
of 2.109(3), 2.109(3)Å , whereas in complex 2, the nickel(II) centre is coordinated axially by two
oxygen atoms, O(1) and O(5) from two methanol molecules at 2.174(4), 2.118(3) Å thus
completing the distorted octahedral coordination sphere around nickel(II).
The coordination sphere around the nickel(II) atom in both complexes is only slightly
distorted from octahedral with all angles less than 10o away from the ideal values of 90o and
180o. On the other hand, while the cadmium(II) in each complex is hexa-coordinated, its
environment is highly distorted octahedral with Ligand-Cd(II)-Ligand angles varying from 65o to
155o. Cadmium(II) is coordinated by two phenoxo oxygen atoms, O(11) and O(31) in the range
2.243(3)-2.260(3) Å, and two ethoxy oxygen atoms, O(131) and O(291), in the significantly
longer range 2.507(4)-2.591(2)Å. The two other positions are occupied by monodentate anions.
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Both complexes contain a nitrogen atom, N(1), from a terminal thiocyanate at 2.214(4), 2.169(5)
Å respectively while the sixth coordination site is occupied by a chlorine atom, Cl(2), in complex
1 at 2.429(9) Å and by an oxygen atom, O(61), at 2.159(4) Å from an acetate group in complex
2. The bridging angles, Ni(1)-O(11)-Cd(1) and Ni(1)-O(31)-Cd(1), are 103.0(1)° and 102.7(1)°

respectively for complex 1, 103.6(1)° and 103.2(1)° respectively for complex 2. The dihedral
angles between the Ni(1),O(31),O(11) and Cd(1),O(31),O(11) planes are 5.49° in complex 1 and
5.40° in complex 2 indicating that the complex core Ni(1),O(31),O(11),Cd(1) is almost planar.
The intra-dimer nickel(II)∙∙∙cadmium(II) distance is 3.355(1) Å in complex 1 and 3.352(1) Å in
complex 2. The saturated six membered chelate ring [Ni(1)-N(19)-C(20)-C(21)-C(22)-N(23)]
has an envelope conformations with puckering parameters q = 0.530(4) Å; θ = 39.4(4);  =
189.5(7) for complex 1 and q = 0.526(6) Å; θ = 134.6(5);  = 6.4(8) for complex 2.27
In complex 2, the oxygen atom, O(63), of an acetate molecule forms two acceptor
hydrogen bonds, one intramolecular with the hydrogen atom, H(51), attached to oxygen atom,
O(1), and one intermolecular with symmetry related hydrogen atom, H(41)a, {Symmetry
transformation, a = 1+x, y, z} attached to oxygen atom, O(5), to form a 1D polymeric structure
(Fig. 3). The details of the geometric features of the hydrogen bonding interactions are given in
Table 4.
[(SCN)(Cl)Cd(L)Ni(NH2CH2CH2CH2NH2)]n (3)
The X-ray crystal structure determination reveals that complex 3 also crystallizes in
orthorhombic space group P212121. Important bond lengths and bond angles have been given in
Tables 2 and 3 respectively.

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Complex 3 consists of a chain system with the repeating hetero-binuclear neutral units,
[(SCN)(Cl)Cd(L)Ni(NH2CH2CH2CH2NH2)], joined through a single end-to-end, 1,3-
diaminopropane bridge. In each bimetallic unit, the nickel(II) and cadmium(II) centres
respectively occupy the inner N2O2 and outer O4 sites of the potential octadentate deprotonated

Schiff base, L2-. A perspective view of the binuclear unit with the corresponding atom labelling
scheme is depicted in Fig. 4. Nickel(II) and cadmium(II) centres are bridged by two phenoxo
oxygen atoms, O(11) and O(31), with Ni(1)∙∙∙Cd(1) distance of 3.386(1) Å. The bridging angles,
Ni(1)-O(11)-Cd(1) and Ni(1)-O(31)-Cd(1), are 102.2(2)° and 103.8(2)° respectively. The angles
O(11)-Ni(1)-O(31) and O(11)-Cd(1)-O(31) are 81.3(1)° and 71.9(2)° respectively. Both
nickel(II) and cadmium(II) have six-coordinate environments similar to those found in 1 and 2,
thus being slightly distorted octahedral and highly distorted respectively. Ni(1) is coordinated by
two imine nitrogen atoms, N(19) and N(23), two phenoxo oxygen atoms, O(11) and O(31), of
the deprotonated potential octadentate Schiff base ligand L2- which constitute the equatorial
plane. The fifth coordination site is occupied by one nitrogen atom, N(2) from a 1,3-
diaminopropane molecule. A nitrogen atom, N(6)#, from a symmetry related (1/2-x,-y,1/2+z)
end-to-end bridged 1,3-daminopropane occupy the sixth coordination site of nickel(II) to form a
tetragonally distorted octahedron. On the other hand, cadmium(II) is coordinated by two
phenoxo oxygen atoms, O(11) and O(31) at 2.278(4), 2.265(4)Å, two ethoxy oxygen atoms,
O(131) and O(291), at 2.635(4), 2.564(5)Å. The other two coordination sites are occupied by a
nitrogen atom, N(1) from a terminal thiocyanate at 2.167(6) Å and a chlorine atom, Cl(2) at
2.442(2). The saturated six membered chelate ring [Ni(1)-N(19)-C(20)-C(21)-C(22)-N(23)] has
an envelope conformation with puckering parameters q = 0.528(8) Å; θ = 133.6(8);  =
357.6(11).27
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The hydrogen atom, H(6A), attached to the nitrogen atom, N(6), is involved in a strong
hydrogen bonding interaction with the sulphur atom, S(1), of a symmetry related (-x,y-1/2, 1/2-z)
thiocyanate from a neighbouring molecule (Figure 5a). This produces a three dimensional
architecture (Fig 5b). The details of the geometric features of the hydrogen bonding interactions

are given in Table 4.
Chirality of complexes
All three complexes crystallize in Sohncke space group, P212121. From the flack
parameter values {0.010(15) [complex 1], 0.05(2) [complex 2], 0.02(3) [complex 3]}, it could be
concluded that the crystals are all enantiopure. The absolute configuration coordination
compounds are represented by the symbols  or . The absolute configuration are determined by
representing the chelate rings in non-orthogonal projection. A chelate ring of six coordinated
complex, whose ligators form an approximate octahedron, is represented by the edge formed by
its two ligators. If two such edges are skew, the pair could be associated with either (a) or (b) of
Fig. 6. Figures 6(a) and 6(b) represent right handed and left handed helices, respectively. In the
present case, all three complexes have  configurations (right handed helix) based on the ligand
environment around cadmium(II). A closer look of the ligand environment around cadmium(II)
in each complex is shown in Figure 7 along with the representation of pairs of non-orthogonal
skew lines indicating the nature of chirality.
Theoretical study of C-H∙∙∙π (chelate) interactions
Remarkably, complex 1 forms an infinite 1D chain in the solid state (Fig. 8a) that is
governed (among other interactions) by the formation of two concurrent C-H∙∙∙π (chelate)
interactions, one (C-H aromatic) with the six-membered nickel(II) chelate ring and the other (C-
H exocyclic belonging to the C=N group) with the five-membered cadmium(II) chelate ring. The
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details of the geometric features of the C-H∙∙∙π(chelate) interaction are given in Table 5. To the
best of our knowledge, this is the first study that describes this type of interesting arrangement.
The conventional C-H∙∙∙π noncovalent bonding involves the interactions of the electron rich π-
cloud of an aromatic ring with the partially positive H atom. This type of interaction is well

known33 and database studies have shown that C-H∙∙∙π(aromatic) distances typically range from
2.8 to 3.2 Å and that a C-H∙∙∙π interaction is considered short when it is < 3.05 Å.9 A Table (S2)
has been incorporated containing the details of geometric features of the C-H∙∙∙π(aromatic) in the
ESI (Electronic Supplementary Information). Initially, in order to rationalize these interactions,
active Lewis acid/base sites using the overall electrostatic potential plotted on the van der Waals
surface of complex 1 (Fig. 8b) have been calculated. It can be observed that the electrostatic
potential is positive in the aromatic and exocyclic C-H bonds (16 kcal/mol and 24 kcal/mol)
respectively. Moreover, the MEP value over the aryl ring of the ligand is negative (-15 kcal/mol).
Interestingly, it is more negative over the chelate ring, especially over the five-membered
cadmium(II) chelate ring likely due to the presence of two oxygen atoms. Thus, the MEP results
indicate that the C-H∙∙∙π interactions involving the chelate rings are electrostatically more
favoured than that involving the aryl ring. A dimer of the X-ray structure has been extracted and
the interaction energy has been evaluated, which is large and negative (ΔE1 = -22.9 kcal/mol,
Fig. 8c) due to the formation of both C-H∙∙∙π (chelate) interactions in addition to other van der
Waals interactions. Both C-H∙∙∙π distances (from hydrogen atom to the ring centroid) are ca 3 Å
a value typical of C-H∙∙∙π (arene) interaction.9 In order to characterize weak van der Waals
interactions shown in Fig. 8c, non-covalent interactions (NCI plot) of this model dimer have
been computed. The NCI plot is a visualization index that enables efficient identification and
visualization of non-covalent interactions. The NCI analysis allows an assessment of host-guest

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complementarity and the extent to which weak interactions stabilize a complex (see the
Computational Methods section). The information provided is essentially qualitative, that is,
which molecular regions interact. The representation of the NCI plot computed for the dimer of
complex 1 is shown in Fig. 8d. An extended region can be observed between the fused five-

membered cadmium(II) and six-membered nickel(II) chelate rings and the C-H bonds, thus
confirming the interaction. Other regions are also present between the C-H bonds and the
coordinated DMF thus indicating the existence of additional van der Waals interactions and
explaining the large interaction energy.
Complex 2 also forms an infinite 1D chain where short C-H∙∙∙π(chelate) interactions are
established (blue dashed lines in Fig. 9a) in addition to conventional C-H∙∙∙π(chelate) interactions
(black dashed lines). The MEP surface of complex 2 (Fig. 9b) has been computed and it can be
observed that the six-membered nickel(II) chelate ring is not accessible to π-interactions due to
the presence of the coordinated methanol molecule. In contrast the other chelate ring is well
suited for establishing π-interactions because the adjacent axial ligand is linear thiocyanate. The
MEP value over the center of the chelate ring is -19 kcal/mol, appropriate for interacting with
Lewis acids. The MEP value at the hydrogen atom of the coordinated methanol is the most
positive one (+40 kcal/mol) and the MEP value at the thiocyanate ligand is negative (-45
kcal/mol). The interaction energy of one dimer retrieved from the infinite 1D chain (Fig. 9c)
which includes three different short C-H∙∙∙π interactions has been calculated. These consist of
two, unconventional interactions involving C-H∙∙∙π(chelate) and C-H∙∙∙π(thiocyanate) interactions
and one conventional C-H∙∙∙π(arene) interaction. It should be mentioned that the observed
distance for the C-H∙∙∙π(chelate) interaction is very short (3.17 Å from the carbon atom).
Moreover, a strong hydrogen bonding interaction between the coordinated methanol and the
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acetate ligand is also formed. This striking combination of interactions explain the large binding
energy (ΔE2 = -46.6 kcal/mol). In an effort to roughly evaluate the contribution of the two
unconventional C-H∙∙∙π(chelate) and C-H∙∙∙π(thiocyanate) interactions a theoretical model has
been used where the acetate anion has been replaced by a formate anion (small arrow in Fig. 9d)

so that all these three interactions are removed. As a result, the binding energy is reduced to ΔE3
= -12.8 kcal/mol and the difference (-2.1 kcal/mol) is a rough estimation of the energy of the
unconventional C-H∙∙∙π(chelate) and C-H∙∙∙π(thiocyanate) interactions. This binding energy is
similar to that reported for conventional C-H∙∙∙π(arene) interactions.9 In order to characterize the
interactions shown in Fig. 9c, non-covalent interactions (NCI plot) of this model dimer have
been computed. The representation of the NCI plot is shown in Fig. 9e and a large green region
can be identified over the five-membered cadmium(II) chelate ring and directed towards the
relevant C-H bond thus confirming the C-H∙∙∙π interaction. Interestingly this isosurface
encompasses the whole five-membered cadmium(II) ring thus indicating that the interaction is
with the whole methyl group of the acetate. An extended green isosurface also characterizes the
conventional C-H∙∙∙π(arene) interaction. Finally, a small blue isosurface characterizes the
hydrogen bonding and C-H∙∙∙π(thiocyanate) contacts, thus indicating that they are stronger
interactions.
CSD Search
In order to provide additional evidence of the relevance of C-H∙∙∙π(chelate ring)
interactions in the solid state, the Cambridge Structural Database (CSD)34 search for similar
systems have been done. In particular the fragment depicted in Fig. 10a has been used where a
Schiff base tetradentate compartmental ligand is coordinated to two transition metals and,
consequently, two types of chelate rings are present (five and six-membered rings). Two separate
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searches have been performed, one using the six-membered chelate ring and the other one using
the five membered chelate ring. Several geometric criteria has been used for performing the
searches (Fig. 10a). First the distance between the ring centroid and the hydrogen atom should
range from 2.5 to 3.2 Å for selecting a hit. Second, to ensure that the hydrogen atom is located

approximately over the centre of the chelate ring, three angles (αn, n = 1-3) have been defined
and imposed that their values should be comprised between 70º and 110º for selecting a hit. For
the six-membered chelate ring search, 57 structures and a total of 102 fragments have been
retrieved from the CSD showing C-H∙∙∙π(chelate ring) interactions. The histogram plot (number
of fragments vs distance) for this search is given in Fig. 10b. It can be observed that the majority
of hits are comprised at distances between 2.95 and 3.10 Å, similarly to C-H∙∙∙π(arene)
interactions.9 The results for the five-membered chelate ring search are shown in Fig. 10c. The
number of structures/fragments obtained from the CSD search is similar to that found for the six-
membered chelate ring. However, the histogram plot is slightly different, likely due to the
smaller size of the ring. In this case the major number of hits are observed at distances > 3.0Å.
Finally, in Fig. 11, two selected examples from the afore mentioned searches have been
shown to illustrate the C-H∙∙∙π(chelate ring) interactions in the solid state. The first one
corresponds to the CUMVOW34 structure where the six membered manganese chelate ring
establishes two concurrent interactions. One of them is intramolecular (2.73 Å) with the
coordinated methanol molecule where one C-H bond of the methanol interacts with the chelate
ring. Moreover, a non-coordinated methanol molecule is also establishing a C-H∙∙∙π(chelate ring)
interaction at the opposite side of the chelate ring (2.97 Å), (Fig. 11a). As an example of five
membered chelate ring, we have selected FIPKUK35 that forms self-assembled supramolecular
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dimers in the solid state where two symmetrically equivalent C-H∙∙∙π(chelate ring) interactions
(2.93 Å) are important stabilizing the assembly, see Fig 11b.
Concluding Remarks

In summary, synthesis and X-ray characterization of few hetero-nuclear
nickel(II)/cadmium(II) complexes containing NiO2Cd cores are described is this paper. Most
interesting feature is the facile synthesis of a diamine bridged hetero-polynuclear complex,
which is eventually the first example of any nickel(II)/cadmium(II) complex with N2O4 donor
compartmental Schiff base. Complex 1 forms an infinite 1D chain in the solid state governed
mainly by the formation of C-H∙∙∙π(chelate) interactions, one with the six-membered nickel(II)
chelate ring [Ni(1)-O(11)-C(12)-C(17)-C(18)-N(19)] and the other one with the five-membered
cadmium(II) chelate ring [Cd(1)-O(11)-C(12)-C(13)-O(131)]. The MEP value over the chelate
ring is more negative than that over the aryl ring of the ligand, indicating the C-H∙∙∙π interactions
involving the chelate rings are electrostatically more favoured than that involving the aryl ring.
Complex 2 also forms an infinite 1D chain where short C-H∙∙∙π(chelate) interactions are
established in addition to unconventional C-H∙∙∙π(thiocyanate) and conventional C-H∙∙∙π(arene)
interactions. A rough estimation of the unconventional C-H∙∙∙π(chelate) and C-H∙∙∙π
(thiocyanate) interactions was also computed (-2.1 kcal/mol). The existence of the proposed
noncovalent interactions in complexes 1 and 2 are also confirmed using the NCI plot. Finally, we
have explored the CSD to provide further support to the importance of this interaction in the
solid state.
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Notes and References
Electronic supplementary information (ESI) available: Figures S1-S13 and Tables S1 and S2.
CCDC 1487862, 1487863 and 1487864 contain the supplementary crystallographic data for 1, 2
and 3 respectively.

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Table 1: Crystal data and refinement details of complexes 1-3.
Formula C28H38CdClN5NiO6S C26H35CdN3NiO8S C25H34CdClN5NiO4S
Formula Weight 779.25 720.74 707.19

Temperature(K) 150 150 150

Crystal system Orthorhombic Orthorhombic Orthorhombic
Space group P212121 P212121 P212121
a (Å) 12.8958(5) 7.7212(4) 13.4856(10)
b (Å) 15.5589(4) 16.2457(10) 13.7310(12)
c (Å) 16.5707(5) 23.8774(13) 15.4020(9)
Z 4 4 4
dcalc(g cm-3) 1.557 1.598 1.647
μ (mm-1) 1.395 1.459 1.612
F (000) 1592 1472 1440
Flack Parameter 0.010(15) 0.05(2) 0.02(3)
Total Reflections 9946 16951 17512
Unique Reflections 8117 7895 7872
Observed data 7390 7070
7119
[I > 2 σ (I)]
No. of parameters 394 382 345
R (int) 0.023 0.038 0.052
R1, wR2 (all data) 0.0449, 0.0836 0.0693, 0.1130 0.0768, 0.1831
R1, wR2 [I > 2 σ (I)] 0.0385, 0.0807 0.0595, 0.1097 0.0695, 0.1765
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Table 2: Selected bond lengths (Å) for complexes 1-3.
Complex 1 2 3
Cd(1)-O(11) 2.260(3) 2.243(3) 2.278(4)
Cd(1)-O(31) 2.259(2) 2.255(3) 2.265(4)

Cd(1)-O(131) 2.591(2) 2.507(4) 2.635(4)

Cd(1)-O(291) 2.573(3) 2.585(3) 2.564(5)
Cd(1)-N(1) 2.214(4) 2.169(5) 2.167(6)
Ni(1)-O(11) 2.024(2) 2.017(3) 2.070(4)
Ni(1)-O(31) 2.033(3) 2.018(3) 2.034(4)
Ni(1)-N(19) 2.041(3) 2.040(5) 2.037(6)
Ni(1)-N(23) 2.015(3) 2.016(5) 2.048(5)
Ni(1)-O(1) 2.109(3) 2.174(4) -
Ni(1)-O(5) 2.109(3) 2.118(3) -
Cd(1)-Cl(2) 2.429(9) - 2.442(2)
Cd(1)-O(61) - 2.159(4) -
Ni(1)-N(2) - - 2.180(6)
Ni(1)-N(6)a - - 2.127(5)
Symmetry transformations: a = 1/2-x,2-y,1/2+z.
Table 3: Selected bond angles (°) for complexes 1-3.
Complex 1 2 3
O(11)-Cd(1)-O(131) 65.00(8) 66.76(13) 64.5(2)
O(11)-Cd(1)-O(291) 137.66(8) 136.65(12) 137.0(2)
O(11)-Cd(1)-O(31) 72.09(9) 71.51(12) 71.9(2)
O(11)-Cd(1)-N(1) 106.50(11) 106.82(19) 112.7(2)
O(31)-Cd(1)-O(291) 66.31(8) 65.14(12) 65.1(2)
O(31)-Cd(1)-O(131) 137.02(9) 137.35(13) 136.4(2)
O(31)-Cd(1)-N(1) 107.83(10) 114.29(17) 110.7(2)
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DOI: 10.1039/C6DT04906K
O(131)-Cd(1)-O(291) 155.01(8) 155.34(14) 158.5(2)

O(291)-Cd(1)-N(1) 79.78(10) 91.54(19) 83.2(2)
O(131)-Cd(1)-N(1) 82.92(10) 86.44(18) 87.2(2)
O(11)-Ni(1)-O(31) 81.91(10) 81.32(13) 81.0(2)
O(1)-Ni(1)-N(19) 86.58(12) 90.46(17) 90.5(2)

O(1)-Ni(1)-N(23) 87.05(11) 93.48(15) 172.1(2)

O(31)-Ni(1)-N(19) 171.89(11) 171.50(16) 171.3(2)
O(31)-Ni(1)-N(23) 89.72(10) 89.92(17) 91.3(2)
N(19)-Ni(1)-N(23) 98.29(12) 98.58(19) 97.2(2)
O(5)-Ni(1)-O(11) 91.38(10) 93.66(14) -
O(1)-Ni(1)-O(11) 94.47(10) 83.80(14) -
O(1)-Ni(1)-O(31) 92.55(10) 88.64(16) -
O(5)-Ni(1)-O(31) 87.29(10) 90.47(16) -
O(11)-Ni(1)-N(19) 90.11(12) 90.18(16) -
O(11)-Ni(1)-N(23) 171.54(11) 170.87(17) -
O(1)-Ni(1)-O(5) 174.07(10) 177.41(15) -
O(5)-Ni(1)-N(19) 94.41(12) 90.06(17) -
O(5)-Ni(1)-N(23) 87.02(11) 88.96(15) -
Cl(2)-Cd(1)-O(11) 107.55(7) - 110.68(13)
Cl(2)-Cd(1)-O(131) 88.84(6) - 83.40(11)
Cl(2)-Cd(1)-O(291) 91.70(6) - 86.71(13)
Cl(2)-Cd(1)-O(31) 106.57(7) - 112.54(13)
Cl(2)-Cd(1)-N(1) 137.35(9) - 125.74(19)
O(11)-Cd(1)-O(32) - 122.43(15) -
O(31)-Cd(1)-O(61) - 110.84(15) -
O(61)-Cd(1)-O(131) - 85.14(16) -
O(61)-Cd(1)-O(291) - 74.87(15) -
O(61)-Cd(1)-N(1) - 121.0(2) -
O(11)-Ni(1)-N(2) - - 87.3(2)
O(11)-Ni(1)-N(6)a - - 86.0(2)
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DOI: 10.1039/C6DT04906K
O(31)-Ni(1)-N(2) - - 89.8(2)
O(31)-Ni(1)-N(6)a - - 85.0(2)
N(2)-Ni(1)-N(19) - - 87.8(2)
N(2)-Ni(1)-N(23) - - 94.3(2)
N(2)-Ni(1)-N(6)a - - 172.1(2)

N(6)a- Ni(1)-N(19) - - 96.4(2)

N(6)a- Ni(1)-N(23) - - 91.8(2)
Symmetry transformation: a = 1/2-x,2-y,1/2+z.
Table 4: Hydrogen bond distances (A˚) and angles () for complexes 2 and 3.
Complex D-H···A H···A(Å) D-H(Å) D···A (Å) D-H···A
O(5)-H(41)···O(63)a 1.98(3) 0.84(2) 2.781(6) 161(6)

2
O(1)-H(51)···O(63) 1.96(4) 0.83(3) 2.681(6) 144(6)
3 N(6)-H(6A)…S(1)b 2.90 0.90 3.684(7) 147
Symmetry transformations: a = -1+x,y,z; b = -x,y-1/2, 1/2-z.
Table 5. Details of the C-H∙∙∙π(chelate) interactions in complexes 1 and 2, the atomic charges of
hydrogen (QH) and sum of Mulliken atomic charges (C,O,N) in the chelate ring (ΣQCR) at the
M06-2X/def2-TZVP level of theory.
Complex C-H (Atom Chelate ring H···Cg QH ΣQCR

labels) distance
1 C(26)-H(26) Ni1O11C12C17C18N19 3.050 0.11 -0.71
1 C(24)-H(24) Cd1O11C12C13O131 3.185 0.13 -0.70
2 C64–H64C Cd1C29C30O31O291 2.632 0.16 -0.56

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DOI: 10.1039/C6DT04906K

Fig. 1: Perspective view of complex 1 with atom numbering scheme. Hydrogen atoms have been
omitted for clarity.

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DOI: 10.1039/C6DT04906K

Fig. 2: Perspective view of complex 2 with atom numbering scheme. Hydrogen atoms have been
omitted for clarity.

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DOI: 10.1039/C6DT04906K

Fig. 3: Perspective view of the hydrogen bonding interactions in complex 2. Only the relevant
a
atoms are shown in the figure. Symmetry transformation: = -
1+x,y,z.
Fig. 4: Perspective view of complex 3 with selective atom numbering scheme. Hydrogen atoms
have been omitted for clarity.

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DOI: 10.1039/C6DT04906K

(a)
(b)
Fig. 5: (a) Highlighted hydrogen bonding interaction of complex 3. Only hydrogen atoms
a
have been omitted for clarity. Symmetry transformation: = (-x,y-1/2, 1/2-z). (b) Three
dimensional architecture of complex 3 generated through hydrogen bonding interactions.

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DOI: 10.1039/C6DT04906K

Fig 6: The figure shows pairs of non-orthogonal skew lines in projection upon a plane parallel to
both lines, where (a) corresponds to right handed helix leading to Δ configuration and (b)
corresponds to left handed helix leading to  configuration.
(a)
(b)
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DOI: 10.1039/C6DT04906K

(c)
Fig 7: Perspective views of the ligand environments around cadmium(II) in complexes 1-3 (a-c
respectively) and the pairs of non-orthogonal skew lines in projection upon a plane parallel to
both lines corresponding to Δ configurations.
Fig. 8: (a) X-ray fragment of complex 1 showing C-H∙∙∙π interactions as dotted lines. (b) MEP
surface with indication of electrostatic potential values at selected points. (c) Theoretical model
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DOI: 10.1039/C6DT04906K
used to evaluate the C-H∙∙∙π (chelate) interactions. Distances in Å. (d) NCI plot of the self-
assembled dimer of complex 1. NCI plot only shows the intermolecular interactions.

Fig. 9: (a) X-ray fragment of complex 2 with C-H…π interactions shown as dotted lines. (b)
MEP surface with indication of electrostatic potential values (kcal/mol) at selected points. (c,d)
Theoretical models used to evaluate the C-H∙∙∙π(chelate) interactions, shown as dotted lines.
Distances in Å. (e) NCI plot of the self-assembled dimer of complex 2. NCI plot only shows the
intermolecular interactions.
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DOI: 10.1039/C6DT04906K

Fig. 10: (a) Query and criteria used for the CSD searches. (b,c) Histogram plots for the C-H∙∙∙π
interactions (N = number of fragments, d = distance from the ring centroid to the interacting H
atom).
Fig. 11: CUMVOW (a) and FIPKUK (b) structures exhibiting C-H∙∙∙π(chelate ring) interactions.
Distances in Å.

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Estimation of conventional C-H∙∙∙π (arene), unconventional C-H∙∙∙π

(chelate) and C-H∙∙∙π (thiocyanate) interactions in hetero-nuclear

nickel-cadmium complexes with a compartmental Schiff base: Novel

Dalton Transactions Accepted Manuscript

example of a diamine bridged hetero-polynuclear complex having

Sourav Roy,a Michael G. B. Drew,b Antonio Bauzá,c Antonio Frontera,*c

Tel: +91-33-24572941, e-mail: shouvik.chem@gmail.com

6AD, United Kingdom, e-mail: m.g.b.drew@reading.ac.uk

Palma, Baleares, Spain. e-mail: toni.frontera@uib.es

Abstract: Three new heteronuclear nickel(II)/cadmium(II) complexes,

[(SCN)(Cl)Cd(L)Ni(DMF)2] (1), [(SCN)(CH3CO2)Cd(L)Ni(CH3OH)2] (2) and

[(SCN)(Cl)Cd(L)Ni(NH2CH2CH2CH2NH2)]n (3) {where H2L = N,N'-bis(3-ethoxysalicylidene)

propane-1,3-diamine is a potential octadentate compartmental Schiff base}, have been

Dalton Transactions Accepted Manuscript

The lifetimes of excited states are in the range of 2-6 ns.

Keywords: Cadmium(II); Nickel(II); Heteronuclear; Compartmental Schiff base; Polymer;

Photoluminescence, C-H∙∙∙π interactions, DFT studies.

Synthetic inorganic chemists have prepared various homo and hetero-polynuclear

heteronuclear nickel(II)/cadmium(II) complexes did not make them attractive to scientists

Several bridging co-ligands e.g. acetate, thiocyanate, nitrate, dicyanamide, bipyridine,

Dalton Transactions Accepted Manuscript

packing patterns in crystal structures. More recently, “unconventional” C-H∙∙∙π interactions

participate in π(chelate)···π(chelate) and π(chelate)···π stacking interactions as systematically

in square-planar transition-metal acetylacetonate structures.12 Other works available in the

their utilization is quite rare.13

nuclear nickel(II)/cadmium(II) complexes. Interestingly, one of these complexes, namely 3

represents a diamine bridged polynuclear nickel(II)/cadmium(II) complex with NiO2Cd core.

with a compartmental Schiff base.

Moreover, the ability of both chelate-rings (nickel and cadmium) to establish C-

Dalton Transactions Accepted Manuscript

from Sigma-Aldrich without further purification.

Synthesis of the ligand H2L [N,N'-bis(3-ethoxysalicylidene)propane-1,3-diamine]

Synthesis of the complex [(SCN)(Cl)Cd(L)Ni(DMF)2] (1)

evaporation of the solution in open atmosphere.

Dalton Transactions Accepted Manuscript

indicating consistency of the bulk samples.

Synthesis of the complex [(SCN)(CH3CO2)Cd(L)Ni(CH3OH)2] (2)

Complex 2 was prepared in a similar method as that of complex 1, except that

of the solution in open atmosphere.

indicating consistency of the bulk samples.

Synthesis of the complex [(SCN)(Cl)Cd(L)Ni(NH2CH2CH2CH2NH2)]n (3)

Dalton Transactions Accepted Manuscript

results, indicating consistency of the bulk samples.

Dalton Transactions Accepted Manuscript

Elmer Lambda 35 UV-visible spectrophotometer. Steady state photoluminescence spectra in

DMF were obtained in Shimadzu RF-5301PC spectrofluorometer at room temperature. Time

dependent photoluminescence spectra were recorded using Hamamatsu MCP photomultiplier

tentatively attributed to intra-ligand transitions modified by metal coordination. The relative

the sum of exponential series I  t    exp   , where α

susceptibility measurements were performed with an EG and PAR vibrating sample

measurements were obtained on a Bruker D8 instrument with Cu K radiation. In this process,

Dalton Transactions Accepted Manuscript

Dalton Transactions Accepted Manuscript

enables identification and visualization of non-covalent interactions efficiently. The isosurfaces

covalent interactions in the solid state.

Results and Discussion

1,3-diaminopropane has been refluxed with 3-ethoxysalicylaldehyde in 1:2 ratio to form a

Dalton Transactions Accepted Manuscript

thiocyanate tetrahydrate and 1,3-diaminopropane to the methanol solution of H2L. Addition of