The elusive [Ni(H2O)2(15-crown-5)]2+ cation and related co-crystals of nickel(II) hydrates and 15-crown-5

Maxime A. Siegler; Sean Parkin; John P. Selegue; Carolyn Pratt Brock

doi:10.1107/S0108768108034058

The elusive [Ni(H₂O)₂(15-crown-5)]²⁺ cation and related co-crystals of nickel(II) hydrates and 15-crown-5

Maxime A. Siegler
, Sean Parkin
, John P. Selegue
, Carolyn Pratt Brock

Chemistry

Producción científica: Article › revisión exhaustiva

14 Citas (Scopus)

Resumen

Initial attempts to make [Ni(H₂O)₂(15-crown-5)](NO3) ₂, i.e. to insert the Ni²⁺ ion into the 15-crown-5 macrocycle, gave the mono- (two polymorphs) and dihydrate of a co-crystal of [Ni(H₂O)₆](NO₃)₂ and 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane = 15C5). Synthetic routes designed to restrict the water available to the Ni²⁺ cation gave three additional compounds, [Ni(H₂O)₆](NO₃)2-trans-[Ni(H ₂O)₄(MeOH)₂](NO₃) ₂·2(15C5), cis-[Ni(H₂O)₄(NO ₃)₂]-trans-[Ni(H₂O)₄(NO ₃)₂]·2(15C5) and [Ni(H₂O) ₂(MeCN)(NO₃)₂]·15C5·MeCN. All five compounds contain Ni²⁺ ions with two trans aqua ligands. In all six structures these aqua ligands make hydrogen bonds to the 15C5 molecules to form stacks in which the Ni complexes and 15C5 molecules alternate. The structures are surprisingly complicated: all are co-crystals, some are also solvates, and most have Z′ > 1. The target compound was finally prepared by heating pale green crystals of [Ni(H₂O) ₆](NO₃)₂·15C5·2H₂O to over 350 K and then cooling the resulting mixture of yellow crystals and solution to room temperature. Formation of the target compound seems to be favored at higher temperatures by a positive △_rxn S ^o and an increased rate of ligand exchange.

Idioma original	English
Páginas (desde-hasta)	725-737
Número de páginas	13
Publicación	Acta Crystallographica Section B: Structural Science
Volumen	64
N.º	6
DOI	https://doi.org/10.1107/S0108768108034058
Estado	Published - 2008

ASJC Scopus subject areas

General Biochemistry, Genetics and Molecular Biology

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10.1107/S0108768108034058

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title = "The elusive [Ni(H2O)2(15-crown-5)]2+ cation and related co-crystals of nickel(II) hydrates and 15-crown-5",

abstract = "Initial attempts to make [Ni(H2O)2(15-crown-5)](NO3) 2, i.e. to insert the Ni2+ ion into the 15-crown-5 macrocycle, gave the mono- (two polymorphs) and dihydrate of a co-crystal of [Ni(H2O)6](NO3)2 and 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane = 15C5). Synthetic routes designed to restrict the water available to the Ni2+ cation gave three additional compounds, [Ni(H2O)6](NO3)2-trans-[Ni(H 2O)4(MeOH)2](NO3) 2·2(15C5), cis-[Ni(H2O)4(NO 3)2]-trans-[Ni(H2O)4(NO 3)2]·2(15C5) and [Ni(H2O) 2(MeCN)(NO3)2]·15C5·MeCN. All five compounds contain Ni2+ ions with two trans aqua ligands. In all six structures these aqua ligands make hydrogen bonds to the 15C5 molecules to form stacks in which the Ni complexes and 15C5 molecules alternate. The structures are surprisingly complicated: all are co-crystals, some are also solvates, and most have Z′ > 1. The target compound was finally prepared by heating pale green crystals of [Ni(H2O) 6](NO3)2·15C5·2H2O to over 350 K and then cooling the resulting mixture of yellow crystals and solution to room temperature. Formation of the target compound seems to be favored at higher temperatures by a positive △rxn S o and an increased rate of ligand exchange.",

keywords = "Crown ligand, Hydrogen bonding, Ligand exchange, Macrocycles",

author = "Siegler, \{Maxime A.\} and Sean Parkin and Selegue, \{John P.\} and Brock, \{Carolyn Pratt\}",

year = "2008",

doi = "10.1107/S0108768108034058",

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T1 - The elusive [Ni(H2O)2(15-crown-5)]2+ cation and related co-crystals of nickel(II) hydrates and 15-crown-5

AU - Siegler, Maxime A.

AU - Parkin, Sean

AU - Selegue, John P.

AU - Brock, Carolyn Pratt

PY - 2008

Y1 - 2008

N2 - Initial attempts to make [Ni(H2O)2(15-crown-5)](NO3) 2, i.e. to insert the Ni2+ ion into the 15-crown-5 macrocycle, gave the mono- (two polymorphs) and dihydrate of a co-crystal of [Ni(H2O)6](NO3)2 and 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane = 15C5). Synthetic routes designed to restrict the water available to the Ni2+ cation gave three additional compounds, [Ni(H2O)6](NO3)2-trans-[Ni(H 2O)4(MeOH)2](NO3) 2·2(15C5), cis-[Ni(H2O)4(NO 3)2]-trans-[Ni(H2O)4(NO 3)2]·2(15C5) and [Ni(H2O) 2(MeCN)(NO3)2]·15C5·MeCN. All five compounds contain Ni2+ ions with two trans aqua ligands. In all six structures these aqua ligands make hydrogen bonds to the 15C5 molecules to form stacks in which the Ni complexes and 15C5 molecules alternate. The structures are surprisingly complicated: all are co-crystals, some are also solvates, and most have Z′ > 1. The target compound was finally prepared by heating pale green crystals of [Ni(H2O) 6](NO3)2·15C5·2H2O to over 350 K and then cooling the resulting mixture of yellow crystals and solution to room temperature. Formation of the target compound seems to be favored at higher temperatures by a positive △rxn S o and an increased rate of ligand exchange.

AB - Initial attempts to make [Ni(H2O)2(15-crown-5)](NO3) 2, i.e. to insert the Ni2+ ion into the 15-crown-5 macrocycle, gave the mono- (two polymorphs) and dihydrate of a co-crystal of [Ni(H2O)6](NO3)2 and 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane = 15C5). Synthetic routes designed to restrict the water available to the Ni2+ cation gave three additional compounds, [Ni(H2O)6](NO3)2-trans-[Ni(H 2O)4(MeOH)2](NO3) 2·2(15C5), cis-[Ni(H2O)4(NO 3)2]-trans-[Ni(H2O)4(NO 3)2]·2(15C5) and [Ni(H2O) 2(MeCN)(NO3)2]·15C5·MeCN. All five compounds contain Ni2+ ions with two trans aqua ligands. In all six structures these aqua ligands make hydrogen bonds to the 15C5 molecules to form stacks in which the Ni complexes and 15C5 molecules alternate. The structures are surprisingly complicated: all are co-crystals, some are also solvates, and most have Z′ > 1. The target compound was finally prepared by heating pale green crystals of [Ni(H2O) 6](NO3)2·15C5·2H2O to over 350 K and then cooling the resulting mixture of yellow crystals and solution to room temperature. Formation of the target compound seems to be favored at higher temperatures by a positive △rxn S o and an increased rate of ligand exchange.

KW - Crown ligand

KW - Hydrogen bonding

KW - Ligand exchange

KW - Macrocycles

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DO - 10.1107/S0108768108034058

M3 - Article

C2 - 19029702

AN - SCOPUS:56849105638

SN - 0108-7681

VL - 64

SP - 725

EP - 737

JO - Acta Crystallographica Section B: Structural Science

JF - Acta Crystallographica Section B: Structural Science

IS - 6

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