Metal-Bound Nitrate Anion as an Acceptor for Halogen Bonds in Mono-Halopyridine-Copper(II) Nitrate Complexes

Puttreddy, Rakesh; Peuronen, Anssi; Lahtinen, Manu

doi:10.1021/acs.cgd.9b00284

Cited by 7 publications

(2 citation statements)

References 52 publications

(75 reference statements)

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“…Will the chlorine substituents and metal-bound halides establish halogen bonds (XBs) [40][41][42][43][44], and halogen•••halogen interactions [45][46][47][48]? This knowledge of XBs in metal complexes is derived from our previous experiences in halopyridine-Cu(I)/Cu(II) compounds [49][50][51][52]. When the bulky chlorines are installed close to an N-atom, can this affect the N-M coordination?…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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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.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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“…The examination of halogen bonds in coordination compounds is still an underrepresented topic in halogen bond (XB) research [6,7,8,9,10,11,12,13,14,15]. mono -Halopyridines are common organic moieties used for exploring halogen bonds in coordination complexes [16,17,18,19].…”

Section: Introductionmentioning

confidence: 99%

Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers

Eßen

Puttreddy

2019

Materials

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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.

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Halogen Bonding: An Introduction

Decato

John

Berryman

2021

Halogen Bonding in Solution

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Metal-Bound Nitrate Anion as an Acceptor for Halogen Bonds in Mono-Halopyridine-Copper(II) Nitrate Complexes

Abstract: This is a self-archived version of an original article. This version may differ from the original in pagination and typographic details.

Cited by 7 publications

References 52 publications

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

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

Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers

Halogen Bonding: An Introduction

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