The present study deals with one dimer-of-dinuclear type compound, [{CuIILAgI(NO3)}2] (1), one pentametallic and metal-centered rectangle type compound, [BaII(CuIIL)4](ClO4)2 (2), and one dinuclear based two-dimensional coordination polymer, [CuIILCdII(μ1,5-dicyanamide)2]n (3), where H2L=N,N′-bis(salicylidene)-1,4-butanediamine. The syntheses and crystal structures of 1–3, electrospray ionization mass spectra in positive mode of 1 and 2 and variable-temperature magnetic properties of 2, are described. Two symmetry related diphenoxo-bridged dinuclear CuIIAgI moieties are interlinked in 1 by Ag–π (η2-) bonds to form dimer-of-dinuclear type structure. One diphenoxo-bridged dinuclear CuIICdII moiety is interlinked with four symmetry related dinuclear moieties by four μ1,5-dicyanamide ligands, which link CdII centers, to generate two-dimensional polymeric structure in 3. In the [BaII(CuIIL)4]2+ cation in 2, the BaII ion is coordinated to two μ-phenoxo oxygen atoms of each of the four [CuIIL] fragments; the four copper(II) ions are positioned to form an approximate rectangle, i. e., the pentametallic [BaII(CuIIL)4]2+ cation in 2 is a metal-centered rectangle. ESI-MS positive of 1 and 2 have been recorded and the ions in the spectra have been reasonably assigned. Variable-temperature magnetic studies of 2 reveal very weak antiferromagnetic interaction (J=–0.14 cm–1) between the copper(II) ions. The structure of 2 represents a new type among compounds from related ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

SASANKA MOHANTA

Chemistry

S MANDAL

N HARI

S MONDAL

University of Calcutta (informally known as Calcutta University or CU) is a collegiate public state university located in Kolkata, West Bengal, India.&nbsp;Within India it is recognized as a &quot;Five-Star University&quot; and accredited &quot;A&quot; Grade by National Assessment and Accreditation Council.

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The University of Calcutta has secured the Fifth position among the Universities of India in the prestigious &quot;Indian University Ranking 2019&quot; list, released by the NIRF of the Ministry of Human Resource Development, Government of India.

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It was established on 24 January 1857, and was one of the first institutions in Asia to be established as a multidisciplinary and Western-style university. Its alumni and faculty include several heads of state, heads of government, social reformers, prominent artists, only academy award winner and Dirac medal winner in India, many Fellows of the Royal Society and five Nobel laureates as of 2019 which is highest in South Asia.

University Of Calcutta

ChemistrySelect

Two copper metallo-ligands [CuL1(H2O)] and [CuL2-(H2O)] [H2L1 = N,N′-ethylenebis(3-methoxysalicylaldimine) and H2L2 = N,N′-ethylenebis(3-ethoxysalicylaldimine)] have been utilized for the preparation of heterobimetallic eight CuIISnIV complexes [CuL1]2·[SnMe2Cl4]2-·(H2ED)2+ (1), [CuL1]2·[SnEt2Cl4]2-·(H2ED)2+·0.5H2O (2), [CuL1]2·[Sn(n-Bu)2Cl4]2-·(H2ED)2+ (3), [CuL1]2·[SnPh2Cl4]2-·(H2ED)2+ (4), [CuL1]2·[SnPh2Cl4]2-·(H2ED)2+·2MeOH (5), [CuL2]2·[SnMe2Cl2(H2O)2]·0.2H2O (6), [CuL2]·[Sn(n-Bu)2Cl2(H2O)] (7), [CuL2]2·[SnPh2Cl4]2-·(H2ED)2+ (8), and two CuIISnII systems [CuL1SnCl]+·[SnCl3]- (9) and [CuL2SnCl]+·[SnCl3]- (10) (ED = 1,2-ethylenediamine). Single crystal X-ray structure analyses indicate that 1-5 and 8 are three-component [1×2+1×1+1×1] salt cocrystals of two neutral mononuclear [CuL1]/[CuL2] moieties, one organometallic dianion [SnR2Cl4]2- (R = Me, Et, n-Bu, and Ph), and one doubly protonated 1,2-ethylenediammonium dication H2ED2+, while compounds 6 and 7 are two-component [1×2+1×1]/[1×1+1×1] cocrystals of one/two neutral mononuclear [CuL2] and one neutral organotin(IV) moieties. Compounds 9 and 10 are two-component salts which are comprised of heterometallic, diphenoxido-bridged, dinuclear CuIISnII cation [CuLSnCl]+ and SnII anionic residue [SnCl3]-. Interestingly, the formation of the salt cocrystals or cocrystals 1-8 and salts 9 and 10 can be well rationalized in terms of several noncovalent weak interactions (O-H···O/N-H···O/N-H···Cl/Cu···Cl/Sn···Cl/Sn···Cu/π···π) which result in the generation of a tetrameric associate in 7, one-dimensional topology in 3-5 and 8-10 and two-dimensional supramolecular associate in 1 and 2. The first metallo-ligand [CuL1(H2O)] produces similar three-component CuII···SnIV···diprotonated diamine salt cocrystals (1-5), attesting to the selectivity toward the formation of this type of compound, while the latter one [CuL2-ing;(H2O)] displays a diverse structure forming capability by producing a CuII···SnIV···diprotonated diamine salt cocrystal (8) and two CuII···SnIV cocrystals (6 and 7). Interestingly, no such selectivity is observed for their heterometallic CuIISnII derivatives (9 and 10) which are similar two-component salts and completely different from 1-8. The current study illustrates an excellent example of structural diversity in heterometallic CuIISnII/IV complexes depending on the ligand substitution and metal oxidation state. Moreover, a heterometallic system, such as 1-5 and 8, containing ammonium-stannate adduct (X-NH3·SnX6, X = any) is not known according to the search made on the Cambridge Structural Database (CSD). © 2016 American Chemical Society.

Crystal Growth and Design

Heterometallic Copper(II)-Tin(II/IV) Salts, Cocrystals, and Salt Cocrystals: Selectivity and Structural Diversity Depending on Ligand Substitution and the Metal Oxidation State

With the aim of exploring metal complexes from single-/double-compartmental acyclic Schiff base ligands having a less utilized diamine counterpart, this work presents the syntheses, characterization, crystal structures and diffuse reflectance spectra of two mononuclear compounds, [CuIIL1]·MeOH and [NiIIL1], and six heteronuclear complexes [CuII(acetone)L1(UVIO2)(NO3)2]·1.5CH3COCH3 (1), [CuII(H2O)L3(UVIO2)(NO3)2]·MeCN (2), [NiIIL1(UVIO2)(NO3)2]·CH3COCH3 (3), [{CuIIL1AgI(NO3)}2] (4), [{CuIIL2AgI(NO3)}2] (5) and [(CuIIL2)2CdII(ClO4)2] (6), where H2L1, H2L2 and H2L3 are the [1+2] condensation products of 2,2-dimethyl-1,3-diaminopropane and, respectively, 2-hydroxyacetophenone, salicylaldehyde and 3-ethoxysalicylaldehyde. The crystal structures of [CuIIL1]·MeOH and 1-6 have been determined. Compounds 1-3 are diphenoxo-bridged dinuclear copper(II)/nickel(II)-uranyl(VI) systems, compounds 4 and 5 are dimer-of-dinuclear [CuIIAgI]2 systems where two diphenoxo-bridged dinuclear CuIIAgI units are interlinked by an AgI-C (η2 arene) bond and silver(I)⋯silver(I) interaction (in 4) or by CuII⋯O (nitrate) semi-coordination and silver(I)⋯silver(I) interaction (in 5), and compound 6 is a trinuclear linear CuIICdIICuII system where copper(II) and cadmium(II) are bridged by a bis(μ-phenoxo)-μ-perchlorate moiety. Diffuse reflectance spectra of 1-6 and the corresponding mononuclear copper(II)/nickel(II) compounds have been recorded and it has been explored how much the d-d band position of copper(II) is correlated with the shifting of the copper(II) center from the least-squares basal plane. Salient features in the structures have been discussed. © 2014 Elsevier Ltd. All rights reserved.

Polyhedron

Mononuclear and heterometallic dinuclear, trinuclear and dimer-of-dinuclear complexes derived from single- and double-compartment Schiff base ligands having a less utilized diamine

The work in this report describes the syntheses, electrospray ionization mass spectromtery, structures, and experimental and density functional theoretical (DFT) magnetic properties of four tetrametallic stars of composition [MII(CuIIL)3](ClO4)2 (1, M = Mn; 2, M = Ni; 3, M = Cu; 4, M = Zn) derived from a single-compartment Schiff base ligand, N,N-bis(salicylidene)-1,4-butanediamine (H2L), which is the [2 + 1] condensation product of salicylaldehyde and 1,4-diaminobutane. The central metal ion (MnII, NiII, CuII, or ZnII) is linked with two μ2-phenoxo bridges of each of the three [CuIIL] moieties, and thus the central metal ion is encapsulated in between three [CuIIL] units. The title compounds are rare or sole examples of stars having these metal-ion combinations. In the cases of 1, 3, and 4, the four metal ions form a centered isosceles triangle, while the four metal ions in 2 form a centered equilateral triangle. Both the variable-temperature magnetic susceptibility and variable-field magnetization (at 2-10 K) of 1-3 have been measured and simulated contemporaneously. While the MnIICuII3 compound 1 exhibits ferromagnetic interaction with J = 1.02 cm-1, the NiIICuII3 compound 2 and CuIICuII3 compound 3 exhibit antiferromagnetic interaction with J = -3.53 and -35.5 cm-1, respectively. Variable-temperature magnetic susceptibility data of the ZnIICuII3 compound 4 indicate very weak antiferromagnetic interaction of -1.4 cm-1, as expected. On the basis of known correlations, the magnetic properties of 1-3 are unusual; it seems that ferromagnetic interaction in 1 and weak/moderate antiferromagnetic interaction in 2 and 3 are possibly related to the distorted coordination environment of the peripheral copper(II) centers (intermediate between square-planar and tetrahedral). DFT calculations have been done to elucidate the magnetic properties. The DFT-computed J values are quantitatively (for 1) or qualitatively (for 2 and 3) matched well with the experimental values. Spin densities and magnetic orbitals (natural bond orbitals) correspond well with the trend of observed/computed magnetic exchange interactions. © 2014 American Chemical Society.

Inorganic Chemistry

A series of M II Cu II 3 stars (M = Mn, Ni, Cu, Zn) exhibiting unusual magnetic properties

The work in this paper deals with five new complexes of composition [Cu II (MeCN)L(U VI O 2 )(NO 3 ) 2 ] MeCN (1), [(Cu II L) 3 Cd II ](ClO 4 ) 2 (2) and [(Cu II L) 2 M II (μ 1,5 -dicyanamide) 2 ] n (M = Co (3), M = Ni (4) and M = Zn (5)) derived from a single-compartment Schiff base ligand H 2 L, which is the [2 + 1] condensation product of salicylaldehyde and 1,4-diaminobutane. Single crystal X-ray structures of all the five complexes have been determined. Compound 1 is a diphenoxo-bridged Cu II (U VI O 2 ) system, compound 2 is a star-shaped tetranuclear system where the cadmium(II) center is encapsulated in between three [Cu II L] moieties and the three isomorphous compounds 3-5 are trinuclear Cu II M II Cu II -based (M = Co, Ni, Zn) two-dimensional, square-grid systems where the trinuclear units are bridged by μ 1,5 -dicyanamide ligands. In addition to the exploration of much less investigated Schiff base ligand family having four carbon atoms between the two imine nitrogen atoms, the types of structures presented here either have some novelties or are new examples and therefore deserves importance. The d-d spectra of copper(II)-diamagnetic metal ion complexes (1, 2 and 5) and the corresponding mononuclear copper(II) compound have been recorded with the aim to shed light on the correlation of d-d band position with the displacement of copper(II) from the least-squares basal plane, revealing excellent correlation. © 2014 Elsevier B.V. All rights reserved.

Inorganica Chimica Acta

Dinuclear, star-shaped tetranuclear and trinuclear-based two-dimensional metal complexes derived from a less investigated Schiff base ligand: Syntheses, crystal structures and spectroscopic correlation

The work in this report describes the syntheses and crystal structures of nine copper(II)-silver(I) compounds derived from some single-compartment N(imine)2O(phenoxo)2 or double-compartment N(imine) 2O(phenoxo)2-O(phenoxo)2O(methoxy/ethoxy) 2 acyclic Schiff base ligands. The nine compounds are [{Cu II(ClO4)Lsal-enAgI} 2{CuII(ClO4)Lsal-enAg I(H2O)}]n (1), [CuIIL sal-pnAgI(ClO4)]n (2), [{Cu IILsal-pnAgI(NO3)}2] (3), [(CuIILacpn-en)2AgI(MeCN) 2](ClO4) (4), [{CuIILOMe-enAg I(NO3)}2] (5), [{CuIIL OMe-pnAgI(NO3)}2] (6), [{Cu IILOMe-pnAgI(NO3)} 2]·2H2O (7), [{CuIIL OEt-enAgI(NO3)}2] (8) and [{Cu IILOEt-opAgI(MeOH)}2](ClO 4)2 (9), where the superscripts in the ligand symbols mean the following: (i) sal, acpn, OMe and OEt indicate that the aldehyde counterpart is salicylaldehyde, 2-hydroxyacetophenone, 3-methoxysalicylaldehyde and 3-ethoxysalicylaldehyde, respectively; (ii) en, pn and op indicate that the diamine counterpart is ethylenediamine, 1,3-diaminopropane and o-phenylenediamine, respectively. Copper(II) in all these compounds occupies a N2O2 compartment and the two phenoxo oxygen atoms in all cases bridge one copper(II) and one silver(I) centers. Compound 4 is a trinuclear CuIIAgICuII system. Compounds 3 and 5-9 are dimer-of-dinuclear compounds, in which the dimerization takes place due to interdinuclear Cu-O(nitrate) and Ag⋯Ag interactions in 3, 5 and 6 and due to Ag-π (η1-/η2-) bonds in 7-9. Compounds 2 and 1 are one-dimensional coordination polymers due to Ag-π (η2-)/Ag-π (η3-) bonds. CSD search/analysis reveals some definite significant aspects in both the Ag-π and Ag⋯Ag bonded systems in the present investigation. © 2014 Elsevier B.V. All rights reserved.

Exploration of heterometallic systems containing silver(I) in acyclic Schiff base ligands: Finite and infinite self-assemblies as a result of silver(I)-carbon bond and silver(I)â‹¯silver(I) interaction

Journal	Data powered by TypesetChemistrySelect
Publisher	Data powered by TypesetWiley-Blackwell
ISSN	2365-6549
Open Access	No