Mixed-ligand Mn-II and Cu-II complexes with alternating 2,2 '-bipyrimidine and terephthalate bridges
Abstract
The novel polymeric complexes catena-poly[[diaquamanganese(II)]-mu-2,2'-bipyrimidine-kappa N-4(1),N-1':N-3,N-3'-[diaquamanganese(II)]-bis(mu-terephthalato-kappa O-2(1):O-4)], [Mn-2(C8H4O4)(2)(C8H6N4)(H2O)(4)](n), (I), and catena-poly[[[aquacopper(II)]-mu-aqua-mu-hydroxido-mu-terephthalato-kappa O-2(1):O-1'-copper(II)-mu-aqua-mu-hydroxido-mu-terephthalato-kappa O-2(1):O-1'-[aquacopper(II)]-mu-2,2'-bipyrimidine-kappa N-4(1),N-1':N-3,N-3'] tetrahydrate], {[Cu-3(C8H4O4)(2)- (OH)(2)(C8H6N4)(H2O)(4)]center dot 4H(2)O}(n), (II), containing bridging 2,2'-bipyrimidine (bpym) ligands coordinated as bis-chelates, have been prepared via a ligand-exchange reaction. In both cases, quite unusual coordination modes of the terephthalate (tpht(2-)) anions were found. In (I), two tpht(2-) anions acting as bis-monodentate ligands bridge the Mn-II centres in a parallel fashion. In (II), the tpht(2-) anions act as endo-bridges and connect two Cu-II centres in combination with additional aqua and hydroxide b...ridges. In this way, the binuclear [Mn-2(tpht)(2)(bpym)(H2O)(4)] entity in (I) and the trinuclear [Cu-3(tpht)(2)(OH)(2)(bpym)(H2O)(4)]center dot 4H(2)O coordination entity in (II) build up one-dimensional polymeric chains along the b axis. In (I), the Mn-II cation lies on a twofold axis, whereas the four central C atoms of the bpym ligand are located on a mirror plane. In (II), the central Cu-II cation is also on a special position (site symmetry 1). In the crystal structures, the packing of the chains is further strengthened by a system of hydrogen bonds [in both (I) and (II)] and weak face-to-face pi-pi interactions [in (I)], forming three-dimensional metal-organic frameworks. The Mn-II cation in (I) has a trigonally deformed octahedral geometry, whereas the Cu-II cations in (II) are in distorted octahedral environments. The Cu-II polyhedra are inclined relative to each other and share common edges.
Keywords:
crystal structure / one-dimensional coordination polymers / copper(II) complex / manganese(II) complex / terephthalate anion / 2,2 '-bipyrimidine / metal-organic frameworks / magnetic interactionsSource:
Acta Crystallographica Section C: Structural Chemistry, 2015, 71, 2, 110-115Publisher:
- International Union of Crystallography
Funding / projects:
DOI: 10.1107/S2053229614028113
ISSN: 2053-2296
PubMed: 25652277
WoS: 000349441600007
Scopus: 2-s2.0-84922559772
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Tehnološko-metalurški fakultetTY - JOUR AU - Poleti, Dejan AU - Rogan, Jelena AU - Rodić, Marko V. AU - Radovanović, Lidija PY - 2015 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/3028 AB - The novel polymeric complexes catena-poly[[diaquamanganese(II)]-mu-2,2'-bipyrimidine-kappa N-4(1),N-1':N-3,N-3'-[diaquamanganese(II)]-bis(mu-terephthalato-kappa O-2(1):O-4)], [Mn-2(C8H4O4)(2)(C8H6N4)(H2O)(4)](n), (I), and catena-poly[[[aquacopper(II)]-mu-aqua-mu-hydroxido-mu-terephthalato-kappa O-2(1):O-1'-copper(II)-mu-aqua-mu-hydroxido-mu-terephthalato-kappa O-2(1):O-1'-[aquacopper(II)]-mu-2,2'-bipyrimidine-kappa N-4(1),N-1':N-3,N-3'] tetrahydrate], {[Cu-3(C8H4O4)(2)- (OH)(2)(C8H6N4)(H2O)(4)]center dot 4H(2)O}(n), (II), containing bridging 2,2'-bipyrimidine (bpym) ligands coordinated as bis-chelates, have been prepared via a ligand-exchange reaction. In both cases, quite unusual coordination modes of the terephthalate (tpht(2-)) anions were found. In (I), two tpht(2-) anions acting as bis-monodentate ligands bridge the Mn-II centres in a parallel fashion. In (II), the tpht(2-) anions act as endo-bridges and connect two Cu-II centres in combination with additional aqua and hydroxide bridges. In this way, the binuclear [Mn-2(tpht)(2)(bpym)(H2O)(4)] entity in (I) and the trinuclear [Cu-3(tpht)(2)(OH)(2)(bpym)(H2O)(4)]center dot 4H(2)O coordination entity in (II) build up one-dimensional polymeric chains along the b axis. In (I), the Mn-II cation lies on a twofold axis, whereas the four central C atoms of the bpym ligand are located on a mirror plane. In (II), the central Cu-II cation is also on a special position (site symmetry 1). In the crystal structures, the packing of the chains is further strengthened by a system of hydrogen bonds [in both (I) and (II)] and weak face-to-face pi-pi interactions [in (I)], forming three-dimensional metal-organic frameworks. The Mn-II cation in (I) has a trigonally deformed octahedral geometry, whereas the Cu-II cations in (II) are in distorted octahedral environments. The Cu-II polyhedra are inclined relative to each other and share common edges. PB - International Union of Crystallography T2 - Acta Crystallographica Section C: Structural Chemistry T1 - Mixed-ligand Mn-II and Cu-II complexes with alternating 2,2 '-bipyrimidine and terephthalate bridges EP - 115 IS - 2 SP - 110 VL - 71 DO - 10.1107/S2053229614028113 ER -
@article{ author = "Poleti, Dejan and Rogan, Jelena and Rodić, Marko V. and Radovanović, Lidija", year = "2015", abstract = "The novel polymeric complexes catena-poly[[diaquamanganese(II)]-mu-2,2'-bipyrimidine-kappa N-4(1),N-1':N-3,N-3'-[diaquamanganese(II)]-bis(mu-terephthalato-kappa O-2(1):O-4)], [Mn-2(C8H4O4)(2)(C8H6N4)(H2O)(4)](n), (I), and catena-poly[[[aquacopper(II)]-mu-aqua-mu-hydroxido-mu-terephthalato-kappa O-2(1):O-1'-copper(II)-mu-aqua-mu-hydroxido-mu-terephthalato-kappa O-2(1):O-1'-[aquacopper(II)]-mu-2,2'-bipyrimidine-kappa N-4(1),N-1':N-3,N-3'] tetrahydrate], {[Cu-3(C8H4O4)(2)- (OH)(2)(C8H6N4)(H2O)(4)]center dot 4H(2)O}(n), (II), containing bridging 2,2'-bipyrimidine (bpym) ligands coordinated as bis-chelates, have been prepared via a ligand-exchange reaction. In both cases, quite unusual coordination modes of the terephthalate (tpht(2-)) anions were found. In (I), two tpht(2-) anions acting as bis-monodentate ligands bridge the Mn-II centres in a parallel fashion. In (II), the tpht(2-) anions act as endo-bridges and connect two Cu-II centres in combination with additional aqua and hydroxide bridges. In this way, the binuclear [Mn-2(tpht)(2)(bpym)(H2O)(4)] entity in (I) and the trinuclear [Cu-3(tpht)(2)(OH)(2)(bpym)(H2O)(4)]center dot 4H(2)O coordination entity in (II) build up one-dimensional polymeric chains along the b axis. In (I), the Mn-II cation lies on a twofold axis, whereas the four central C atoms of the bpym ligand are located on a mirror plane. In (II), the central Cu-II cation is also on a special position (site symmetry 1). In the crystal structures, the packing of the chains is further strengthened by a system of hydrogen bonds [in both (I) and (II)] and weak face-to-face pi-pi interactions [in (I)], forming three-dimensional metal-organic frameworks. The Mn-II cation in (I) has a trigonally deformed octahedral geometry, whereas the Cu-II cations in (II) are in distorted octahedral environments. The Cu-II polyhedra are inclined relative to each other and share common edges.", publisher = "International Union of Crystallography", journal = "Acta Crystallographica Section C: Structural Chemistry", title = "Mixed-ligand Mn-II and Cu-II complexes with alternating 2,2 '-bipyrimidine and terephthalate bridges", pages = "115-110", number = "2", volume = "71", doi = "10.1107/S2053229614028113" }
Poleti, D., Rogan, J., Rodić, M. V.,& Radovanović, L.. (2015). Mixed-ligand Mn-II and Cu-II complexes with alternating 2,2 '-bipyrimidine and terephthalate bridges. in Acta Crystallographica Section C: Structural Chemistry International Union of Crystallography., 71(2), 110-115. https://doi.org/10.1107/S2053229614028113
Poleti D, Rogan J, Rodić MV, Radovanović L. Mixed-ligand Mn-II and Cu-II complexes with alternating 2,2 '-bipyrimidine and terephthalate bridges. in Acta Crystallographica Section C: Structural Chemistry. 2015;71(2):110-115. doi:10.1107/S2053229614028113 .
Poleti, Dejan, Rogan, Jelena, Rodić, Marko V., Radovanović, Lidija, "Mixed-ligand Mn-II and Cu-II complexes with alternating 2,2 '-bipyrimidine and terephthalate bridges" in Acta Crystallographica Section C: Structural Chemistry, 71, no. 2 (2015):110-115, https://doi.org/10.1107/S2053229614028113 . .