With the aim of checking whether the O(phenoxo)2O(methoxy) 2 compartment of 3-methoxysalicylaldehyde-diamine ligands can interact with an aquated proton, the work in this investigation presents the syntheses, characterization, crystal structures and diffuse reflectance spectra of the products obtained from the reactions of three mononuclear copper(II) compounds derived from three H2LOMe ligands (H 2LOMe-en, H2LOMe-op and H 2LOMe-hex) with perchloric acid in DMF, MeOH and MeOH-MeCN, where 'en', 'op' and 'hex' in the superscripts of the ligand symbols indicate that the diamine functionality comes from ethylenediamine, o-phenylenediamine and trans-1,2-diaminocyclohexane, respectively. From these reactions, the following six compounds have been isolated: [{Cu IILOMe-en}(Me2NH2)](ClO 4) (1), [{CuIILOMe-op}(Me2NH 2)](ClO4) (2), [{CuIILOMe-hex} (Me2NH2)](ClO4) (3), [{CuIIL OMe-en}2(enH2)](ClO4)2 (4, where enH2 means diprotonated ethylenediamine), [{Cu IILOMe-op}2(opdaH2)](ClO 4)2·2H2O (5, where opdaH2 means diprotonated o-phenylenediamine) and [{CuIIL OMe-hex}(MeOH2)](ClO4) (6). The Me 2NH2+ moiety in 1-3, NH3+ sites in 4 and 5 and MeOH2+ moiety in 6 interact with the O4 compartment by forming bifurcated hydrogen bonds. Interestingly, compound 6 is an unprecedented type of host-guest system. The individual units in 1-6 are self-assembled by non-covalent interactions to generate one, two and three-dimensional self-assemblies. A spectroscopic correlation has been enlightened. © 2014 Elsevier Masson SAS. All rights reserved.

SASANKA MOHANTA

Chemistry

P CHAKRABORTY

A JANA

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

Polyhedron

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

The present investigation reports the syntheses, characterizations, and crystal structures of nine copper(II)/nickel(II)-s/d10 complexes, [CuIIL1NaI(ClO4)(CH3CN)] (1), [CuIIL1KI(ClO4)(CH 3COCH3)] (2), [CuIIL2Zn IICl2]·CH3CN (3), [(Cu IIL2)2NaI](ClO4) ·CH3COCH3 (4), [(NiIIL1) 2KI](ClO4) (5), [(CuIIL 1)2CsI(ClO4)]·2CH 3CN (6), [(NiIIL1)2Cs I(ClO4)]·2H2O (7), [(Cu IIL2)2SrII(H2O) 2](NO3)2 (8), and [{CuIIL 2LiI(H2O)}2(μ-H 2O)](ClO4)2 (9), where H2L 1 and H2L2 are two 3-methoxysalicylaldehyde- diamine (H2LOMe) ligands in which the diamine moieties are o-phenylenediamine and trans-1,2-diaminocyclohexane, respectively. Among these nine compounds, three (1, 2, and 3) are dinuclear, five (4, 5, 6, 7, and 8) are trinuclear, and 9 is tetranuclear. Trinuclear 6 and 7 are double-decker sandwich systems. Some (in 3 and 9) or all (in 1, 2, and 4-8) of the four oxygens of the O(phenoxo)2O(methoxy)2 compartment(s) are coordinated to the second metal ion (NaI in 1 and 4, KI in 2 and 5, ZnII in 3, CsI in 6 and 7, SrII in 8, and LiI in 9). The di/tri/tetranuclear molecules in 2-9 are self-assembled by weak attractions, such as hydrogen bonds/cation (K I) π/C-H π interactions. The following self-assemblies are observed: 1-D in 3, 7, and 9, 1-D ladder in 4, 2-D in 8, and 3-D in 2 and 5. © 2013 Taylor and Francis Group, LLC.

Journal of Coordination Chemistry

Syntheses, characterizations, and crystal structures of 3d-s/d 10 metal complexes derived from two compartmental Schiff base ligands

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.

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 presents syntheses, characterization, crystal structures and magnetic properties of two diphenoxo-bridged heterodinuclear Cu IIMnII/CuIIFeII compounds [Cu IIL1MnII(H2O)3](ClO 4)2 (1) and [CuIIL1Fe II(H2O)3](ClO4)2 (2) and two tetranuclear CuII3MnII/CuII 3FeII compounds [{CuIIL2Mn II(H2O)(MeOH)2}(CuIIL 2)2](ClO4)2·MeOH (3) and [{CuIIL2FeII(H2O)(MeOH) 2}(CuIIL2)2](ClO4) 2·MeOH (4) derived from two 3-methoxysalicylaldehyde-diamine Schiff base compartmental ligands H2L1 and H 2L2, in which the diamine counterpart comes from 1,3-diaminopropane and o-phenylenediamine, respectively. The two compounds 1 and 2 crystallize in the same space group (monoclinic P21/n) with practically identical unit cell parameters and are isomorphous. Similarly, the two compounds 3 and 4 crystallize in the same space group (monoclinic P2 1/c) with practically identical unit cell parameters and are isomorphous. The tetranuclear [{CuIIL2M II(H2O)(MeOH)2}(CuIIL 2)2]2+ dication in 3 (M = Mn) and 4 (M = Fe) is a self-assembly of one diphenoxo-bridged dinuclear [CuIIL 2MII(H2O)(MeOH)2]2+ dication and two mononuclear [CuIIL2] units. One mononuclear unit is self-assembled with the dinuclear unit by four bifurcated water⋯phenoxo/methoxy (O-H⋯O) hydrogen bonds and three π⋯π stacking interactions, while the second mononuclear unit is interlinked with the dinuclear unit by one methanol⋯phenoxo (O-H⋯O) hydrogen bond only. Clearly, compounds 3 and 4 are [2 × 1 + 1 × 2] cocrystals of one dinuclear and two mononuclear units. Variable-temperature magnetic susceptibility measurements of all the four compounds have been carried out, revealing moderate antiferromagnetic interaction between the copper(ii) and manganese(ii)/iron(ii) in the dinuclear cores with J values (H = -2JS1S2) -29.1, -36.9, -15.9 and -20.2 cm-1, respectively. The magnetic properties are in line with those of previous related examples. Unique features in the structures of 1-4 have been discussed. © 2013 The Royal Society of Chemistry.

CrystEngComm

More surprising differences between two closely similar compartmental ligand families and another dinuclear synthon to stabilize dinuclear-mononuclear cocrystals

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.

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.

Inorganica Chimica Acta

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

Surprising difference between two closely similar O(phenoxo) 2O(ether)2 compartments as hosts for an aquated proton and a novel type of host-guest system

Journal	Data powered by TypesetPolyhedron
Publisher	Data powered by TypesetElsevier Ltd
ISSN	0277-5387
Open Access	No