Syntheses and structures of two coordination polymers formed by Ni(cyclam)2+ cations and sulfate anions
The asymmetric units of catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ4N1,N4,N8,N11)nickel(II)]-μ2-sulfato-κ2O3:O4], [Ni(SO4)(C10H24N4)]n (I), and catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ4N1,N4,N8,N11)nickel(II)]-μ2-sulfato-κ2O3:O4] hemi[4,4′,4′′,4′′′-(2,2′,4,4′,6,6′-hexamethyl-[1,1′-bip...
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| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
| Published: |
International Union of Crystallography
2025-02-01
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| Series: | Acta Crystallographica Section E: Crystallographic Communications |
| Subjects: | |
| Online Access: | https://journals.iucr.org/paper?S2056989024012337 |
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| Summary: | The asymmetric units of catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ4N1,N4,N8,N11)nickel(II)]-μ2-sulfato-κ2O3:O4], [Ni(SO4)(C10H24N4)]n (I), and catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ4N1,N4,N8,N11)nickel(II)]-μ2-sulfato-κ2O3:O4] hemi[4,4′,4′′,4′′′-(2,2′,4,4′,6,6′-hexamethyl-[1,1′-biphenyl]-3,3′,5,5′-tetrayl)tetrabenzoic acid] nonahydrate], {[Ni(SO4)(C10H24N4)]2·C46H38O8·18H2O}n (II), consist of two crystallographically unique centrosymmetric macrocyclic dications and a sulfate dianion. In II it includes additionally a molecule of the undissociated acid (2,2′,4,4′,6,6′-hexamethyl[1,1′-biphenyl]-3,3′,5,5′-tetrayl)tetra(benzoic acid) located on a crystallographic twofold axis and nine highly disordered water molecules of crystallization. In both compounds, the metal ions are coordinated in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable trans-III conformation. Two O atoms of the sulfate anions occupy the trans-axial positions resulting in a slightly tetragonally distorted trans-NiN4O2 octahedral coordination geometry. The crystals of both compounds are composed of parallel coordination polymeric chains running along the [101] and [100] directions in I and II, respectively. The distances between the neighboring metal ions in the chains are significantly different [6.5121 (6) Å in I and 6.0649 (3) Å in II] and this peculiarity is explained by the different spatial directivity of the Ni—O coordination bonds (different S—O—Ni angles). As a result of the C—H...O hydrogen bonds between the methylene groups of the macrocyclic ligands and the non-coordinated O atoms of the sulfate anion, the coordination-polymeric chains in I are arranged in the two-dimensional layers oriented parallel to the (010) and (101) planes, the intersection of which provides the three-dimensional coherence of the crystals. The three-dimensional supramolecular structure of the crystals II is determined by the network of strong hydrogen bonds formed by the carboxylic acid and the non-coordinated O atoms of the sulfate anions. |
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| ISSN: | 2056-9890 |