TY - JOUR

T1 - Synthesis and structure of manganese(ii) coordination polymers with 1,4-diazabicyclo[2.2.2]octane N, N′-dioxide: solvent and template effects

AU - Demakov, P. A.

AU - Romanov, A. S.

AU - Samsonenko, D. G.

AU - Dybtsev, D. N.

AU - Fedin, V. P.

PY - 2020/8/1

Y1 - 2020/8/1

N2 - New metal-organic frameworks [Mn(DMF)2(odabco)2](ClO4)2 · H2O (1), [Mn(H2O)2− (HCOO)2] · odabco (2), and [Mn(Hodabco)2(odabco)3](NO3)4 (3) were synthesized by the reaction of manganese Perchlorate with 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide (odabco) in N, N-dimethylformamide (DMF) under varying reaction conditions. The reaction in N-methylpyrrolidone afforded the metal-organic framework [Mn(odabco)3](NO3)2 (4). The structures of compounds [Mn(DMF)2(odabco)2](ClO4)2 · DMF · H2O (1 · DMF · H2O), [Mn(DMF)2(odabco)2](ClO4)2 · THF (1 · THF), 2, 3, and 4 were determined by single-crystal X-ray diffraction analysis. In compounds 1 · DMF · H2O, 1 · THF, 3, and 4, odabco acts as a bridging ligand; in 2, as a guest template. Compound 1 · DMF · H2O has a layered structure and contains a system of intersecting channels occupied by perchlorate anions and disordered solvent molecules. The framework of 1 proved to be stable during the post-synthetic exchange of DMF by THF. The coordination framework of the adduct 1 · THF containing localized THF molecules has a similar structure. The layered (2) and chain-like (3) compounds are stabilized by extensive hydrogen-bonding systems, giving rise to pseudo-three-dimensional close-packed structures. The replacement of DMF by N-methylpyrrolidone under conditions similar to the synthesis of 3 affects the coordination ability of odabco and affords compound 4 having a three-dimensional framework with pcu topology.

AB - New metal-organic frameworks [Mn(DMF)2(odabco)2](ClO4)2 · H2O (1), [Mn(H2O)2− (HCOO)2] · odabco (2), and [Mn(Hodabco)2(odabco)3](NO3)4 (3) were synthesized by the reaction of manganese Perchlorate with 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide (odabco) in N, N-dimethylformamide (DMF) under varying reaction conditions. The reaction in N-methylpyrrolidone afforded the metal-organic framework [Mn(odabco)3](NO3)2 (4). The structures of compounds [Mn(DMF)2(odabco)2](ClO4)2 · DMF · H2O (1 · DMF · H2O), [Mn(DMF)2(odabco)2](ClO4)2 · THF (1 · THF), 2, 3, and 4 were determined by single-crystal X-ray diffraction analysis. In compounds 1 · DMF · H2O, 1 · THF, 3, and 4, odabco acts as a bridging ligand; in 2, as a guest template. Compound 1 · DMF · H2O has a layered structure and contains a system of intersecting channels occupied by perchlorate anions and disordered solvent molecules. The framework of 1 proved to be stable during the post-synthetic exchange of DMF by THF. The coordination framework of the adduct 1 · THF containing localized THF molecules has a similar structure. The layered (2) and chain-like (3) compounds are stabilized by extensive hydrogen-bonding systems, giving rise to pseudo-three-dimensional close-packed structures. The replacement of DMF by N-methylpyrrolidone under conditions similar to the synthesis of 3 affects the coordination ability of odabco and affords compound 4 having a three-dimensional framework with pcu topology.

KW - manganese(ii)

KW - metal-organic frameworks

KW - N-oxides

KW - template effect

KW - X-ray diffraction

KW - TOPOLOGY

KW - COMPLEXES

KW - GAS SORPTION

KW - CRYSTAL-STRUCTURES

KW - 2D

KW - METAL-ORGANIC FRAMEWORKS

KW - FORMAMIDE

KW - RECENT PROGRESS

KW - LIGAND

UR - http://www.scopus.com/inward/record.url?scp=85091213101&partnerID=8YFLogxK

U2 - 10.1007/s11172-020-2930-4

DO - 10.1007/s11172-020-2930-4

M3 - Article

AN - SCOPUS:85091213101

VL - 69

SP - 1511

EP - 1519

JO - Russian Chemical Bulletin

JF - Russian Chemical Bulletin

SN - 1066-5285

IS - 8

ER -