Publication Type Journal Article
Title Heterometallic Copper(II)-Tin(II/IV) Salts, Cocrystals, and Salt Cocrystals: Selectivity and Structural Diversity Depending on Ligand Substitution and the Metal Oxidation State
Authors Susanta Hazra Priyanka Chakraborty Sasankasekhar Mohanta
Groups CCC
Journal CRYSTAL GROWTH \& DESIGN
Year 2016
Month July
Volume 16
Number 7
Pages 3777-3790
Abstract Two copper metallo-ligands [CuL1(H2O)] and [CuL2 subset of(H2O)] [H2L1 = N,N -ethylenebis(3-methoxysalicylaldimine) and H2L2 = N,N -ethylenebis(3-ethoxysalicylaldimine)] have been utilized for the preparation of heterobimetallic eight (CuSnIV)-Sn-II complexes [CuL1](2)center dot[SnMe2Cl4](2-)center dot(H2ED)(2+) (1), [CuL1](2)center dot[SnEt2Cl4](2-)center dot(H2ED)(2+)center dot 0.5H(2)O (2), [CuL1](2)center dot[Sn(n-Bu)(2)Cl-4](2-)center dot (H2ED)(2+) (3), [CuL1](2)center dot[SnPh2Cl4](2+)center dot(H2ED)(2+) (4), [CuL1](2)center dot[SnPh2Cl4](2-)center dot(H2ED)(2+)center dot 2MeOH (5), [CuL2](2)center dot[SnMe2Cl2(H2O)(2)]center dot 0.2H(2)O (6), [CuL2]center dot[Sn(n-Bu)(2)Cl-2(H2O) (7), [CUL2](2)center dot[SnPh2Cl4](2-)center dot(H2ED)(2+) (8), and two (CuSnII)-Sn-II systems [(CuLSnCl)-Sn-1](+)center dot[SnCL3](-) (9) and [(CuLSnCl)-Sn-2](+)center dot[SnCl3](-) (10) (ED = 1,2-ethylenediamine). Single crystal X-ray structure analyses indicate that 1-5 and 8 are three-component [1x2+1x1+1x1] 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 [1x2+1x1]/[1x1+1x1] 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 (CuSnII)-Sn-II cation [CuLSnCl](+) and Sn-II 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 center dot center dot center dot O/N-H center dot center dot center dot O/N-H center dot center dot center dot Cl/Cu center dot center dot center dot Cl/Sn center dot center dot center dot Cl/Sn center dot center dot center dot Cu/pi center dot center dot center dot pi) 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 Cu-II center dot center dot center dot Sn-IV center dot center dot center dot diprotonated diamine salt cocrystals (1-5), attesting to the selectivity toward the formation of this type of compound, while the latter one [CuL2 subset of(H2O)] displays a diverse structure forming capability by producing a Cu-II center dot center dot center dot Sn-IV center dot center dot center dot diprotonated diamine salt cocrystal (8) and two Cu-II center dot center dot center dot Sn-IV cocrystals (6 and 7). Interestingly, no such selectivity is observed for their heterometallic (CuSnII)-Sn-II 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 (CuSnII/IV)-Sn-II 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 center dot SnX6, X = any) is not known according to the search made on the Cambridge Structural Database (CSD).
DOI http://dx.doi.org/10.1021/acs.cgd.6b00321
ISBN
Publisher AMER CHEMICAL SOC
Book Title
ISSN 1528-7483
EISSN 1528-7505
Conference Name
Bibtex ID ISI:000379456700029
Observations
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