scholarly journals Hydrogen and Halogen Bond Mediated Coordination Polymers of Chloro-Substituted Pyrazin-2-Amine Copper(I) Bromide Complexes

Chemistry ◽  
2020 ◽  
Vol 2 (3) ◽  
pp. 700-713
Author(s):  
Aaron Mailman ◽  
Rakesh Puttreddy ◽  
Manu Lahtinen ◽  
Noora Svahn ◽  
Kari Rissanen

A new class of six mono- (1; 3-Cl-, 2; 5-Cl-, 3; 6-Cl-) and di-(4; 3,6-Cl, 5; 5,6-Cl-, 6; 3,5-Cl-) chloro-substituted pyrazin-2-amine ligands (1–6) form complexes with copper (I) bromide, to give 1D and 2D coordination polymers through a combination of halogen and hydrogen bonding that were characterized by X-ray diffraction analysis. These Cu(I) complexes were prepared indirectly from the ligands and CuBr2 via an in situ redox process in moderate to high yields. Four of the pyrazine ligands, 1, 4–6 were found to favor a monodentate mode of coordination to one CuI ion. The absence of a C6-chloro substituent in ligands 1, 2 and 6 supported N1–Cu coordination over the alternative N4–Cu coordination mode evidenced for ligands 4 and 5. These monodentate systems afforded predominantly hydrogen bond (HB) networks containing a catenated (μ3-bromo)-CuI ‘staircase’ motif, with a network of ‘cooperative’ halogen bonds (XB), leading to infinite polymeric structures. Alternatively, ligands 2 and 3 preferred a μ2-N,N’ bridging mode leading to three different polymeric structures. These adopt the (μ3-bromo)-CuI ‘staircase’ motif observed in the monodentate ligands, a unique single (μ2-bromo)-CuI chain, or a discrete Cu2Br2 rhomboid (μ2-bromo)-CuI dimer. Two main HB patterns afforded by self-complimentary dimerization of the amino pyrazines described by the graph set notation R22(8) and non-cyclic intermolecular N–H∙∙∙N’ or N–H∙∙∙Br–Cu leading to infinite polymeric structures are discussed. The cooperative halogen bonding between C–Cl∙∙∙Cl–C and the C–Cl∙∙∙Br–Cu XB contacts are less than the sum of the van der Waals radii of participating atoms, with the latter ranging from 3.4178(14) to 3.582(15) Å. In all cases, the mode of coordination and pyrazine ring substituents affect the pattern of HBs and XBs in these supramolecular structures.

Materials ◽  
2019 ◽  
Vol 12 (20) ◽  
pp. 3305 ◽  
Author(s):  
Carolina von Essen ◽  
Kari Rissanen ◽  
Rakesh Puttreddy

Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2−X2···A–Cu and C5−X5···A–Cu halogen bonds. The reaction of the 2,5-dihalopyridines and Cu(I) salts allows the synthesis of eight 1-D coordination polymers and a discrete structure. The resulting Cu(I)-complexes are linked by C−X···A–Cu halogen bonds forming 3-D supramolecular networks. The C−X···A–Cu halogen bonds formed between halopyridine ligands and copper(I)-bound halide ions are stronger than C−X···X’–C interactions between two 2,5-dihalopyridine ligands. The C5−I5···I–Cu and C5−Br5···Br–Cu halogens bonds are shorter for C2-fluorine than C2-chlorine due to the greater electron-withdrawing power of fluorine. In 2,5-diiodopyridine-Cu(I)Br complex, the shorter C2−I2···Br–Cu [3.473(5) Å] distances are due to the combined polarization of C2-iodine by C2−I2···Cu interactions and para-electronic effects offered by the C5-iodine, whilst the long halogen bond contacts for C5−I5···Br–Cu [3.537(5) Å] are indicative that C2-iodine has a less para-electronic influence on the C5-iodine. In 2-fluoro-5-X-pyridine-Cu(I) complexes, the C2-fluorine is halogen bond passive, while the other C2-halogens in 2,5-dihalopyridine-Cu(I), including C2-chlorine, participate in halogen bonding interactions.


Crystals ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 319 ◽  
Author(s):  
Xin Ding ◽  
Matti Tuikka ◽  
Kari Rissanen ◽  
Matti Haukka

The ruthenium carbonyl compounds, Ru(bpy)(CO)2X2 (X = Cl, Br or I) act as neutral halogen bond (XB) acceptors when co-crystallized with 1,4-diiodotetrafluoro-benzene (DITFB). The halogen bonding strength of the Ru-X⋅⋅⋅I halogen bonds follow the nucleophilic character of the halido ligand. The strongest halogen bond occurs between the chlorido ligand and the iodide atoms of the DITFB. All three halogen bonded complexes form polymeric assemblies in the solid state. In Ru(bpy)(CO)2Cl2⋅DITFB (1) and in Ru(bpy)(CO)2Br2⋅DITFB (2) both halido ligands are halogen bonded to only one DITFB donor. In Ru(bpy)(CO)2I2⋅DITFB (3) only one of the halido ligands is involved in halogen bonding acting as ditopic center for two DITFB donors. The polymeric structures of 1 and 2 are isomorphic wave-like single chain systems, while the iodine complexes form pairs of linear chains attached together with weak F⋅⋅⋅O≡C interactions between the closest neighbors. The stronger polarization of the iodide ligand compared to the Cl or Br ligands favors nearly linear C-I⋅⋅⋅I angles between the XB donor and the metal complex supporting the linear arrangement of the halogen bonded chain.


Molecules ◽  
2020 ◽  
Vol 25 (7) ◽  
pp. 1589 ◽  
Author(s):  
Yunwen Tao ◽  
Yue Qiu ◽  
Wenli Zou ◽  
Sadisha Nanayakkara ◽  
Seth Yannacone ◽  
...  

Periodic local vibrational modes were calculated with the rev-vdW-DF2 density functional to quantify the intrinsic strength of the X-I⋯OA-type halogen bonding (X = I or Cl; OA: carbonyl, ether and N-oxide groups) in 32 model systems originating from 20 molecular crystals. We found that the halogen bonding between the donor dihalogen X-I and the wide collection of acceptor molecules OA features considerable variations of the local stretching force constants (0.1–0.8 mdyn/Å) for I⋯O halogen bonds, demonstrating its powerful tunability in bond strength. Strong correlations between bond length and local stretching force constant were observed in crystals for both the donor X-I bonds and I⋯O halogen bonds, extending for the first time the generalized Badger’s rule to crystals. It is demonstrated that the halogen atom X controlling the electrostatic attraction between the σ -hole on atom I and the acceptor atom O dominates the intrinsic strength of I⋯O halogen bonds. Different oxygen-containing acceptor molecules OA and even subtle changes induced by substituents can tweak the n → σ ∗ (X-I) charge transfer character, which is the second important factor determining the I⋯O bond strength. In addition, the presence of the second halogen bond with atom X of the donor X-I bond in crystals can substantially weaken the target I⋯O halogen bond. In summary, this study performing the in situ measurement of halogen bonding strength in crystalline structures demonstrates the vast potential of the periodic local vibrational mode theory for characterizing and understanding non-covalent interactions in materials.


Crystals ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 505 ◽  
Author(s):  
Phil Liebing ◽  
Florian Oehler ◽  
Juliane Witzorke

In the construction of heterobimetallic coordination polymers based on dithiocarbamato–carboxylate (DTCC ligands), platinum as a thiophilic metal center can be replaced by the cheaper nickel or palladium. The compounds Zn[Pd(HL)2] and Zn2[M(L)2] (M = Ni, Pd; L = {SSC-N(CH2COO)2}3−) were prepared in a sequential approach starting from K3(L). The products were characterized by IR and NMR spectroscopy, thermal analyses, and single-crystal X-ray diffraction. The products decompose under nitrogen between 300 and 400 °C. Zn[Pd(HL)2] · 6H2O forms polymeric chains in the solid state, and the Zn2[M(L)2] · 14H2O (M = Ni, Pd) exhibit two-dimensional polymeric structures, each being isotypic with the respective Zn/Pt analogs. While the carboxylate groups in all these products are coordinated to zinc in a κO-monodentate mode, a structural variant of Zn2[Ni(L)2] having κO:κO′-briding carboxylate groups was also obtained. Exchange of the metal sites in the two Ni/Zn compounds was not observed, and these compounds are therefore diamagnetic.


2019 ◽  
Vol 48 (44) ◽  
pp. 16756-16763 ◽  
Author(s):  
Martina Lippi ◽  
Massimo Cametti ◽  
Javier Martí-Rujas

The first ab initio synchrotron powder XRD structure solution of a desolvated 1D bispidine coordination polymer (CP) is reported, providing valuable insights into the stability, dynamic and guest responsive behavior of a new class of CPs.


2018 ◽  
Vol 47 (45) ◽  
pp. 16264-16278 ◽  
Author(s):  
Chote Lal Yadav ◽  
Gunjan Rajput ◽  
Krishna K. Manar ◽  
Kavita Kumari ◽  
Michael G. B. Drew ◽  
...  

Eight novel luminescent and semiconducting Tl(i) β-oxodithioester complexes forming 1D/2D coordination polymeric structures were investigated using single crystal X-ray diffraction.


Author(s):  
Marco Saccone ◽  
Giancarlo Terraneo ◽  
Tullio Pilati ◽  
Gabriella Cavallo ◽  
Arri Priimagi ◽  
...  

Halogen bonding is emerging as a powerful non-covalent interaction in the context of supramolecular photoresponsive materials design, particularly due to its high directionality. In order to obtain further insight into the solid-state features of halogen-bonded photoactive molecules, three halogen-bonded co-crystals containing an azobenzene-based difunctional halogen-bond donor molecule, (E)-bis(4-iodo-2,3,5,6-tetrafluorophenyl)diazene, C12F8I2N2, have been synthesized and structurally characterized by single-crystal X-ray diffraction. The crystal structure of the non-iodinated homologue (E)-bis(2,3,5,6-tetrafluorophenyl)diazene, C12H2F8N2, is also reported. It is demonstrated that the studied halogen-bond donor molecule is a reliable tecton for assembling halogen-bonded co-crystals with potential photoresponsive behaviour. The azo group is not involved in any specific intermolecular interactions in any of the co-crystals studied, which is an interesting feature in the context of enhanced photoisomerization behaviour and photoactive properties of the material systems.


IUCrJ ◽  
2015 ◽  
Vol 2 (2) ◽  
pp. 188-197 ◽  
Author(s):  
James S. Wright ◽  
Iñigo J. Vitórica-Yrezábal ◽  
Harry Adams ◽  
Stephen P. Thompson ◽  
Adrian H. Hill ◽  
...  

A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene)n]·m(arene),1(arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2],2aand/or2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of1in the selectivity for formation of either polymorph is explored, and the templating effect of toluene andp-xylene overo-xylene orm-xylene in the formation of arene-containing architecture1is also demonstrated. The formation of arene-free phase2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from1-tol·tol[Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η1,η1manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers1to2aand2bis also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, includingin situdiffraction studies of some transformations.


2018 ◽  
Vol 233 (6) ◽  
pp. 371-377 ◽  
Author(s):  
Margarita Bulatova ◽  
Anna A. Melekhova ◽  
Alexander S. Novikov ◽  
Daniil. M. Ivanov ◽  
Nadezhda A. Bokach

AbstractThe crystal structure of [Cu2(μ-O)(μ-I)2(CNXyl)4]·I2(2·I2) was determined from single-crystal X-ray diffraction data. The adduct2·I2represents the first example of structurally characterized isocyanide-copper(II) complexes. In the structure of2·I2,2forms independent chains connected through molecular iodine via I···I–I···I halogen bonding. The DFT calculations and topological analysis of the electron density distribution within the formalism of Bader’s theory (QTAIM method) were performed for model complex2·I2and the obtained results allowed the attribution of these contacts to moderate strength (3.8–5.3 kcal/mol) non-covalent contacts exhibiting some covalent character.


Materials ◽  
2020 ◽  
Vol 13 (10) ◽  
pp. 2370
Author(s):  
Nikola Bedeković ◽  
Valentina Martinez ◽  
Edi Topić ◽  
Vladimir Stilinović ◽  
Dominik Cinčić

In this work, we explore the halogen-bonded cocrystallization potential of cobaloxime complexes in the synthesis of cocrystals with perhalogenated benzenes. We demonstrate a strategy for synthesizing halogen-bonded metal–organic cocrystals by utilizing cobaloximes whose pendant bromide group and oxime oxygen enable halogen bonding. By combining three well-known halogen bond donor molecules differing in binding geometry and composition with three cobaloxime units, we obtained a total of four previously unreported cocrystals. Single crystal X-ray diffraction experiments showed that the majority of obtained cocrystals exhibited the formation of the targeted I···O and I···Br motives. These results illustrate the potential of cobaloximes as halogen bond acceptors and indicate that this type of halogen bond acceptors may offer a novel route to metal–organic halogen-bonded cocrystals.


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