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.

SASANKA MOHANTA

Chemistry

A BISWAS

S MONDAL

L MANDAL

A JANA

P CHAKRABORTY

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

Inorganica Chimica Acta

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

ChemistrySelect

Dimeric, Two-Dimensional and Metal-Centered Rectangular Heterometallic CuIIâ€“AgI/CdII/BaII Systems Derived from a Single Compartmental Ligand

The work in this investigation deals with syntheses, crystal structures and ESI-MS positive of five compounds of composition [(Cu II L) 2 Na I ](ClO 4 ) (1), [(Cu II L) 2 K I ](ClO 4 ) (2), [{Cu II L(H 2 O)}Ca II (Cu II L)](ClO 4 ) 2 (3), [(Cu II L)(µ-ClO 4 )Sr II {Cu II L(MeOH) 0.6 }](ClO 4 )·1.2MeOH (4) and [(Cu II L)(µ-ClO 4 )Ba II {Cu II L(MeOH)}](ClO 4 )·MeOH (5), where H 2 L = N,N′-bis(3-ethoxysalicylidene)-1,4-butanediamine. The s-block metal ion in all of these five compounds occupies an O 8 (four phenoxo and four ethoxy) site provided by two L 2− ligands. While Na I , K I and Ca II are eight-coordinated, Sr II and Ba II are nine-coordinated due to additional coordination by an oxygen atom of a bridging perchlorate ligand. In all of 1–5, the two Cu II and M I/II are positioned in almost linear way (Cu II –M I/II –Cu II angle range = 168.24–175.39°). The geometries of the coordination environments have been understood from SHAPE analyses. A disagreement has been observed for the first time between the results of SHAPE analyses and Addison geometric parameter for the pentacoordinated environment. Some interesting structural features regarding composition, metal-ligand bond lengths and twisting of the aromatic rings have been observed. UV-Vis spectra indicates two d-d absorption of copper(II) centers in each of the five compounds. ESI-MS positive reveals the appearance of some tri/di/mononuclear ions. © 2018 Elsevier B.V.

Fulltext

Linear trinuclear copper(II)-alkali/alkaline earth metal compounds derived from a compartmental ligand

This paper presents the syntheses, crystal structures and electrospray ionization mass spectra (ESI-MS) of four copper(II)–s-block metal ion compounds of composition [{CuIILNaI(H2O)2}(CuIIL)](ClO4) (1), [(CuIIL)2CaII](ClO4)2·2CH3CN·H2O (2), [CuIILSrII(ClO4)2(H2O)]n (3) and [CuIILBaII(ClO4)2(H2O)]n (4), where H2L is the compartmental acyclic Schiff base ligand, obtained on [2 + 1] condensation of 3-ethoxysalicylaldehyde and trans-1,2-diaminocyclohexane. Compound 1 is a [2 × 1 + 1 × 1] cocrystal of one dinuclear [CuIILNaI(H2O)2]+ moiety and one mononuclear [CuIIL] moiety; the reason of cocrystallization is the hydrogen bonding interaction of a coordinated water molecule of the dinuclear unit with the O(phenoxo)2O(ethoxy)2 compartment of the mononuclear unit. [(CuIIL)2CaII](ClO4)2·2CH3CN·H2O (2) is a trinuclear, non-sandwiched compound where the second metal ion (CaII) is situated in between two O(phenoxo)2O(ethoxy)2 compartments of two [CuIIL] moieties. [CuIILSrII(ClO4)2(H2O)]n (3) and [CuIILBaII(ClO4)2(H2O)]n (4) are isomorphous and dinuclear CuIIMII (M = Sr or Ba) based one-dimensional systems, where polymerization takes place through the perchlorate ligands. A number of peaks are observed in the ESI-MS and those are well assigned. Although the compositions of 1, 2 and 3/4 are different, the ESI-MS of all the four compounds reveal the appearance of trinuclear, dinuclear and mononuclear ions. The peculiar/interesting aspects of the four compounds are discussed. © 2017 Elsevier B.V.

Syntheses, crystal structures and ESI-MS of mononuclearâ€“dinuclear, trinuclear and dinuclear based one-dimensional copper(II)â€“s block metal ion complexes derived from a 3-ethoxysalicylaldehydeâ€“diamine ligand

This work presents the syntheses, crystal structures, lone pair functionality and electrospray ionization spectra in positive mode (ESI-MS positive) of two trinuclear CuIIPbIICuIIcompounds [(CuIIL1)2PbII(ClO4)2] (1) and [(CuIIL2)2PbII(NO3)2] (2), one dimer of trinuclear (CuIIPbIICuII)2compound [{(CuIIL2)2PbII}2(μ-adipate)](ClO4)2·2H2O (3) and one trinuclear CuIIPbIICuII–based one-dimensional (1D) compound [(CuIIL2)2PbII(μ1,5-dicyanamide)2]n(4), where H2L1and H2L2are the [2+1] condensation products of salicylaldehyde and, respectively, 1,3-diaminopropane and 2,2'-dimethyl-1,3-diaminopropane. The four compounds have been synthesized by treating the corresponding copper(II) metallo-ligand with a PbIIsalt (for 1 and 2) or with a PbIIsalt and a secondary bridging ligand (adipic acid for 3 and sodium dicyanamide for 4). In the trinuclear CuIIPbIICuIImoiety in all of 1–4, the PbIIcenter resides in between two [CuIIL1]/[CuIIL2] moieties and copper(II) and lead(II) for each of the two CuIIPbIIpairs are diphenoxo bridged. Two trinuclear units are interlinked by an adipate to form the dimeric hexanuclear compound 3. The neighbouring trinuclear units are interlinked by two dicyanamides, forming one-dimensional coordination polymer 4. ESI-MS positive spectra reveal the existence of mono/di/trinuclear and even unusual tetranuclear star type gaseous positive ions; the observed and simulated isotopic distribution patterns are nicely matched. The existence of stereochemically active/inactive lone pair of electrons of lead(II) has been explored. Salient and interesting features in the structures and ESI-MS have been discussed. © 2016 Elsevier B.V.

Syntheses, crystal structures, lone pair functionality and electrospray ionization mass spectral properties of trinuclear, dimer of trinuclear and trinuclear-based one-dimensional systems of copper(II) and lead(II)

Abstract The work in this report deals with the syntheses, characterization and crystal structures of four compounds of composition [NiIILOEt-pn(H<inf>2</inf>O)<inf>2</inf>PbIIBr<inf>2</inf>] (1), [NiIILOEt-pn(H<inf>2</inf>O)<inf>2</inf>PbII(NO<inf>3</inf>)<inf>2</inf>] (2), [{CuIILOEt-pn(μ-Br)PbII}<inf>2</inf>(μ-Br)<inf>2</inf>] (3) and [{CuII(NO<inf>3</inf>)LOEt-pnInIII(NO<inf>3</inf>)}<inf>2</inf>(μ-OH)<inf>2</inf>] (4), where H<inf>2</inf>LOEt-pn is N,N′-propanebis(3-ethoxysalicylaldimine). Copper(II)/nickel(II) in these compounds occupies the N(imine)<inf>2</inf>O(phenoxo)<inf>2</inf> compartment, while PbII/InIII occupies the O(phenoxo)<inf>2</inf>O(ethoxy)<inf>2</inf> compartment of the ligand. Compounds 1 and 2 are diphenoxo-bridged dinuclear, whereas two dinuclear units are dimerized in 3 and 4. Copper(II) and indium(III) in the dinuclear unit in 4 are diphenoxo-bridged, while copper(II) and lead(II) in 3 are triply bridged by bis(μ-phenoxo)-μ-bromide moiety. Dimerization takes place by two bridging bromides (that bridge two PbII centers) in 3 and by two bridging hydroxides (that bridge two InIII centers) in 4. Copper(II) in 3 and 4 are distorted square pyramidal, while nickel(II) centers in 1 and 2 are distorted octahedral. All the four oxygen atoms of the O(phenoxo)<inf>2</inf>O(ethoxy)<inf>2</inf> compartment are coordinated to the second metal ion (PbII/InIII) in 1-4. Coordination number of lead(II) is 6, 7 and 8 in 1, 3 and 2, respectively, while indium(III) in 4 is 8-coordinated. Salient features of the compounds are discussed. © 2015 Elsevier B.V. All rights reserved.

Heterometallic copper(II)-lead(II), nickel(II)-lead(II) and copper(II)-indium(III) compounds derived from an acyclic double-compartment Schiff base ligand

The work in this report presents the syntheses, characterization, crystal structures and electronic spectra of the six heteronuclear complexes [Cu IIL1NaI(μ-BF4)2Na IL1CuII]·2CH 3COCH3 (1), [CuIIL1Na I(NO3)(MeOH)] (2), [CuIIL1Zn II(H2O)2L1CuII](ClO 4)2 (3), [CuII(MeOH)L1Zn IICl2] (4), [CuIIL1Cd II(H2O)(MeOH)2](ClO4)2 (5) and [CuIIL1CdIICl2(MeOH)][CuII(MeOH) L1CdIICl2] (6), where H2L 1 is N,N′-ethylenebis(3-methoxysalicylaldimine). The crystal systems and space groups are as follows: 1 and 2, triclinic, P1̄; 3 and 6, monoclinic, P21/c; 4, orthorhombic, P21212 1; 5, monoclinic, C2/c. While the N(imine)2O(phenoxo) 2 compartment accommodates the copper(II) center, the larger and open O(phenoxo)2O(methoxy)2 compartment interacts with the second metal ion. Compounds 2, 4 and 5 are diphenoxo-bridged dinuclear systems, compound 3 is a trinuclear system in which the two CuIIZn II pairs are monophenoxo-bridged, compound 1 is a tetranuclear system in which two diphenoxo-bridged CuIINaI units are interlinked by two tetrafluoroborate moieties, and compound 6 is a [2×1+2×1] co-crystal of two dinuclear CuIICdII units. The solid state electronic spectra of compounds 1-6 and also the mononuclear compound [CuIIL1(H2O)] have been recorded in the range 400-800 nm. While correlating the d-d band position with the structural parameters and a previously proposed correlation, some inconsistency has been found, indicating that this area should be explored further. © 2013 Elsevier Ltd. All rights reserved.

Polyhedron

Syntheses, crystal structures and spectroscopy of di/tri/tetranuclear discrete and co-crystalline copper(II)-NaI/ZnII/Cd II complexes derived from a compartmental ligand: Inconsistency in the shifting of the copper(II) d-d band

This paper deals with the syntheses, characterization, crystal structures and UV-Vis spectroscopy of three diphenoxo-bridged dinuclear Cu II(UVIO2) compounds [CuII(MeCN) L1(UVIO2)(NO3)2] (1), [CuII(MeCN)L2 (UVIO2)(NO 3)2] (2) and [CuII(MeCN)L3(U VIO2)(NO3)2] (3) derived from the single-compartment Schiff base ligands H2L1 (2:1 condensation product of salicylaldehyde and 1, 3-diaminopropane), H2L2 (2:1 condensation product of salicylaldehyde and 1-ethyl-1, 3-diaminopropane) and H2L3 (2:1 condensation product of 2-hydroxyacetophenone and 1, 3-diaminopropane). While copper(II) occupies the N2O 2 compartment, uranium(VI) center is linked with Schiff base ligand through the two bridging phenoxo oxygen atoms. Copper(II) is pentacoordinated and distorted square pyramidal, while the uranium(VI) center is octaco-ordinated and distorted hexagonal bipyramidal in which the two uranyl oxygen atoms occupy the apical positions. Electronic spectra of 1-3 and the corresponding mononuclear CuII compounds have been recorded and a previously reported but practically unexplored correlation regarding d-d band position has been highlighted. Although the correlation is not valid for only mononuclear or only dinuclear compounds derived from different ligands, a nice correlation is found out on comparing the spectra of dinuclear compounds with the corresponding mononuclear compounds. © 2013 Elsevier B.V. All rights reserved.

First examples of 3d-uranium compounds derived from single-compartment Schiff base ligands: Syntheses, crystal structures and d-d band correlation

The work in this report presents the syntheses, characterization and crystal structures of [{CuIILop}2(H 5O2)](ClO4) (1), [{CuIIL hex}2(H5O2)](ClO4) (2) and [{CuIILen}2(H5O 2)](ClO4) (3) derived from three 3-ethoxysalicylaldehyde- diamine Schiff base compartmental ligands H2Lop, H 2Lhex and H2Len, in which the diimine moieties come from ortho-phenylenediamine, trans-1,2-diaminocyclohexane and ethylenediamine, respectively. Compounds 1 and 2 crystallize in triclinic crystal system having P1 space group, while the crystal system and space group of compound 3 is monoclinic P21/c. In the [{CuIIL op/hex/en}2(H5O2)]+ cation in 1-3, the two OH2 sites of the aquated proton, H 5O2+, interact with two O(phenoxo) 2O(ethoxy)2 compartments of the two [CuIIL op/hex/en] moieties by forming bifurcated hydrogen bonds and thus [{CuIILop/hex/en}2(H5O 2)]+ may be considered as a supramolecular dimer of two mononuclear moieties, self-assembled by H5O2+ as the tecton. On the basis of the extent of the difference in the two O-H distances involving the central hydrogen atom, H5O2 + moieties in 1-3 may be considered as H2O +-H⋯OH2 (in 1) or as the resonance hybrid of H 2O+-H⋯OH2 and [H 2O⋯H⋯OH2]+ (in 2 and 3). A unique aspect in the composition of 1-3 in terms of the interaction of metal complexes with an aquated proton has been discussed. © 2013 The Royal Society of Chemistry.

CrystEngComm

Metal complex analogues of crown ethers as the preorganized motif to stabilize aquated proton in solid state

This report presents the syntheses, characterization and crystal structures of [{CuIIL1}2·{(UVIO 2)(NO3)2(H2O)2}] (1), [{CuIIL2}2·{(UVIO 2)(NO3)2(H2O)2}]· 2H2O (2) and [{CuIIL3} 2{(UVIO2)(NO3)2(H 2O)2}]·2H2O (3) derived from three 3-methoxysalicylaldehyde-diamine Schiff base compartmental ligands H 2L1, H2L2 and H2L 3, in which the diimine moieties come from ethylenediamine, trans-1,2-diaminocyclohexane and ortho-phenylenediamine, respectively. Compounds 2 and 3 crystallize in triclinic crystal system having P1 space group, while compound 1 crystallizes in monoclinic symmetry with space group P2 1/c. The three structures are similar. The two coordinated water molecules in diaquadinitratouranyl(VI) occupy the two trans positions in the hexagonal basal plane of the hexagonal bipyramidal coordination environment. Each of these two water molecules interact, by forming bifurcated hydrogen bonds, with each of the two O(phenoxo)2O(methoxy)2 compartments resulting in the stabilization of the [1×2 + 1×1] trimetallic self-assemblies. The d-d spectra of 1-3 and the corresponding mononuclear copper(II) complexes [CuIIL1(H 2O)]/[CuIIL2(H2O)]/[Cu IIL3(H2O)] have been recorded. The previously proposed but little addressed correlation of d-d band position with the displacement of the copper(II) center from the least-squares basal plane has been highlighted, revealing the utilization of this correlation accompanied with the FT-IR data to judge the nature of water molecule in the mononuclear complexes. The unique features in the composition of 1-3 have been discussed. © 2013 Elsevier B.V. All rights reserved.

Diaquadinitratouranyl(VI) enforces the O(phenoxo)2O(methoxy) 2 compartment of 3-methoxysalicylaldehyde-diamine ligands to interact with water molecules

The work in the present investigation reports the syntheses, crystal structures and supramolecular topologies of 11 copper(II)-main group metal ion complexes [CuIILNaI(NO3)(H2O)] ·2CH3CN (1), [CuIILNaI(N 3)(CH3OH)]·CH3OH (2), [Cu IILNaI(ClO4)(CH3CN)]·0. 5CH3CN (3), [CuIILNaI(BF4)(CH 3OH)]·H2O (4), [{CuIILNa I(H2O)}2(CuIIL)](BPh 4)2 (5), [CuIILKI(ClO 4)(CH3COCH3)] (6), [CuIILCa II(ClO4)2(H2O)] (7), [{Cu IILCaII(NO3)(μ-NO3)(H 2O)}(CuIIL)]·H2O·CH 3COCH3 (8), [(CuIIL)2Ba II(NO3)2]·CH3OH (9), [Cu IILPbII(NO3)2]·CH 3OH (10) and [CuIILBiIII(NO3) 3]·CH3COCH3 (11), where H2L = N,N′-o-phenylenebis(3-ethoxysalicylaldimine). Among these, eight (1-4, 6, 7, 10 and 11) are dinuclear compounds, one (9) is trinuclear double-decker sandwich compound, one (8) is a [2 × 1 + 1 × 1] trimetallic cocrystal of a dinuclear and a mononuclear units and the remaining (5) is a [2 × 2 + 1 × 1] pentametallic cocrystal of two dinuclear and one mononuclear units. All the 11 compounds 1-11 contain one or more deprotonated ligand, L2-, the salen type N2O2 compartment of each of which is occupied by a CuII ion to result in the formation of a [CuIIL] moiety. On the other hand, the larger and open O(phenoxo)2O(ethoxy)2 compartment of the ligand in one or more [CuIIL] moieties interact (s) with the metal ions NaI (1-5)/KI (6)/CaII (7 and 8)/BaII (9)/Pb II (10)/BiIII (11) to produce the title compounds. It has been observed that the neighbouring di/trinuclear units in 1/3/4/6/9/10/11 are self-assembled to one-/two-dimensional topologies as a result of one or more CH⋯O/OH⋯O hydrogen bonding interaction (s). Following self-assemblies are observed: one-dimensional in 4, one-dimensional helical in 1, one-dimensional double-chain (ladder) in 3, 6 and 10, two-dimensional in 9 and 11. © 2011 Elsevier B.V. All rights reserved.

Journal of Molecular Structure

Syntheses, crystal structures and supramolecular topologies of copper(II)-main group metal complexes derived from N,Nâ€²-o-phenylenebis(3- ethoxysalicylaldimine)

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	Inorganica Chimica Acta
Publisher	-
ISSN	0020-1693
Open Access	No