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First crystal structures of metal complexes with a 4-nitropyrazole-3-carboxylic acid ligand and the third crystal form of the ligand

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Authors
Jaćimović, Željko K.
Novaković, Slađana B.
Bogdanović, Goran A.
Giester, Gerald
Kosović, Milica
Libowitzky, Eugen
Article (Published version)
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© 2019 International Union of Crystallography
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Abstract
Pyrazole (pz)-derived ligands can, besides exhibiting a strong coordination ability toward different metal ions, exhibit a great diversity in their coordination geometry and nuclearity, which can be achieved by varying the type and position of the pz substituents. The present study reports the synthesis and crystal structure of two binuclear complexes, namely bis(μ-4-nitro-1 H -imidazol-1-ide-5-carboxylato)-κ 3 N 1 , O : N 2 ;κ 3 N 2 : N 1 , O -bis[aqua(dimethylformamide-κ O )copper(II)], [Cu 2 (C 4 HN 3 O 4 ) 2 (C 3 H 7 NO) 2 (H 2 O) 2 ], (II), and bis(μ-4-nitro-1 H -imidazol-1-ide-5-carboxylato)-κ 2 N 1 , O : N 2 ;κ 2 N 2 : N 1 , O -bis[triaquacobalt(II)] dihydrate, [Co 2 (C 4 HN 3 O 4 ) 2 (H 2 O) 6 ]·2H 2 O, (III). These compounds represent rare examples of metal complexes comprising 3,4-substituted pz derivatives as a bridging ligand and also the first crystal structures of transition-metal complexes with ligands derived from 4-nitropyrazole-3-carboxylic acid. Recently, the crystal... structures of the same ligand in the neutral and mixed neutral/anionic forms have been reported. We present here the third form of this ligand, where it is present in a fully deprotonated anionic form within a salt, i.e. ammonium 4-nitropyrazole-3-carboxylate, NH 4 + ·C 4 H 2 N 3 O 4 − , (I). Single-crystal X-ray diffraction revealed that in the present complexes, the Cu II and Co II centres adopt distorted square-pyramidal and octahedral geometries, respectively. In both cases, the N , N ′, O -coordinated pz ligand shows simultaneously chelating and bridging coordination modes, leading to the formation of a nearly planar six-membered M 2 N 4 metallocycle. In all three crystal structures, the supramolecular arrangement is controlled by strong hydrogen bonds which primarily engage the carboxylate O atoms as acceptors, while the nitro group adopts the role of an acceptor only in structures with an increased number of donors, as is the case with Co II complex (III). The electrostatic potential, as a descriptor of reactivity, was also calculated in order to examine the changes in ligand electrostatic preferences upon coordination to metal ions.

Keywords:
pyrazole-derived ligand / binuclear complexes / bridging ligand / nitro substituent / hydrogen bonding / crystal structure
Source:
Acta Crystallographica Section C Structural Chemistry, 2019, 75, 3, 255-264
Funding / projects:
  • Ministry of Science of the Republic of Montenegro
  • Design, synthesis, characterization and assessment of practical applications of coordination and organometallic compounds (RS-172014)
  • Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)

DOI: 10.1107/S2053229619001244

ISSN: 2053-2296

PubMed: 30833519

WoS: 000460297900003

Scopus: 2-s2.0-85061568690
[ Google Scholar ]
3
3
URI
https://vinar.vin.bg.ac.rs/handle/123456789/8540
Collections
  • Radovi istraživača
Institution/Community
Vinča
TY  - JOUR
AU  - Jaćimović, Željko K.
AU  - Novaković, Slađana B.
AU  - Bogdanović, Goran A.
AU  - Giester, Gerald
AU  - Kosović, Milica
AU  - Libowitzky, Eugen
PY  - 2019
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/8540
AB  - Pyrazole (pz)-derived ligands can, besides exhibiting a strong coordination ability toward different metal ions, exhibit a great diversity in their coordination geometry and nuclearity, which can be achieved by varying the type and position of the pz substituents. The present study reports the synthesis and crystal structure of two binuclear complexes, namely bis(μ-4-nitro-1 H -imidazol-1-ide-5-carboxylato)-κ 3 N 1 , O : N 2 ;κ 3 N 2 : N 1 , O -bis[aqua(dimethylformamide-κ O )copper(II)], [Cu 2 (C 4 HN 3 O 4 ) 2 (C 3 H 7 NO) 2 (H 2 O) 2 ], (II), and bis(μ-4-nitro-1 H -imidazol-1-ide-5-carboxylato)-κ 2 N 1 , O : N 2 ;κ 2 N 2 : N 1 , O -bis[triaquacobalt(II)] dihydrate, [Co 2 (C 4 HN 3 O 4 ) 2 (H 2 O) 6 ]·2H 2 O, (III). These compounds represent rare examples of metal complexes comprising 3,4-substituted pz derivatives as a bridging ligand and also the first crystal structures of transition-metal complexes with ligands derived from 4-nitropyrazole-3-carboxylic acid. Recently, the crystal structures of the same ligand in the neutral and mixed neutral/anionic forms have been reported. We present here the third form of this ligand, where it is present in a fully deprotonated anionic form within a salt, i.e. ammonium 4-nitropyrazole-3-carboxylate, NH 4 + ·C 4 H 2 N 3 O 4 − , (I). Single-crystal X-ray diffraction revealed that in the present complexes, the Cu II and Co II centres adopt distorted square-pyramidal and octahedral geometries, respectively. In both cases, the N , N ′, O -coordinated pz ligand shows simultaneously chelating and bridging coordination modes, leading to the formation of a nearly planar six-membered M 2 N 4 metallocycle. In all three crystal structures, the supramolecular arrangement is controlled by strong hydrogen bonds which primarily engage the carboxylate O atoms as acceptors, while the nitro group adopts the role of an acceptor only in structures with an increased number of donors, as is the case with Co II complex (III). The electrostatic potential, as a descriptor of reactivity, was also calculated in order to examine the changes in ligand electrostatic preferences upon coordination to metal ions.
T2  - Acta Crystallographica Section C Structural Chemistry
T1  - First crystal structures of metal complexes with a 4-nitropyrazole-3-carboxylic acid ligand and the third crystal form of the ligand
VL  - 75
IS  - 3
SP  - 255
EP  - 264
DO  - 10.1107/S2053229619001244
ER  - 
@article{
author = "Jaćimović, Željko K. and Novaković, Slađana B. and Bogdanović, Goran A. and Giester, Gerald and Kosović, Milica and Libowitzky, Eugen",
year = "2019",
abstract = "Pyrazole (pz)-derived ligands can, besides exhibiting a strong coordination ability toward different metal ions, exhibit a great diversity in their coordination geometry and nuclearity, which can be achieved by varying the type and position of the pz substituents. The present study reports the synthesis and crystal structure of two binuclear complexes, namely bis(μ-4-nitro-1 H -imidazol-1-ide-5-carboxylato)-κ 3 N 1 , O : N 2 ;κ 3 N 2 : N 1 , O -bis[aqua(dimethylformamide-κ O )copper(II)], [Cu 2 (C 4 HN 3 O 4 ) 2 (C 3 H 7 NO) 2 (H 2 O) 2 ], (II), and bis(μ-4-nitro-1 H -imidazol-1-ide-5-carboxylato)-κ 2 N 1 , O : N 2 ;κ 2 N 2 : N 1 , O -bis[triaquacobalt(II)] dihydrate, [Co 2 (C 4 HN 3 O 4 ) 2 (H 2 O) 6 ]·2H 2 O, (III). These compounds represent rare examples of metal complexes comprising 3,4-substituted pz derivatives as a bridging ligand and also the first crystal structures of transition-metal complexes with ligands derived from 4-nitropyrazole-3-carboxylic acid. Recently, the crystal structures of the same ligand in the neutral and mixed neutral/anionic forms have been reported. We present here the third form of this ligand, where it is present in a fully deprotonated anionic form within a salt, i.e. ammonium 4-nitropyrazole-3-carboxylate, NH 4 + ·C 4 H 2 N 3 O 4 − , (I). Single-crystal X-ray diffraction revealed that in the present complexes, the Cu II and Co II centres adopt distorted square-pyramidal and octahedral geometries, respectively. In both cases, the N , N ′, O -coordinated pz ligand shows simultaneously chelating and bridging coordination modes, leading to the formation of a nearly planar six-membered M 2 N 4 metallocycle. In all three crystal structures, the supramolecular arrangement is controlled by strong hydrogen bonds which primarily engage the carboxylate O atoms as acceptors, while the nitro group adopts the role of an acceptor only in structures with an increased number of donors, as is the case with Co II complex (III). The electrostatic potential, as a descriptor of reactivity, was also calculated in order to examine the changes in ligand electrostatic preferences upon coordination to metal ions.",
journal = "Acta Crystallographica Section C Structural Chemistry",
title = "First crystal structures of metal complexes with a 4-nitropyrazole-3-carboxylic acid ligand and the third crystal form of the ligand",
volume = "75",
number = "3",
pages = "255-264",
doi = "10.1107/S2053229619001244"
}
Jaćimović, Ž. K., Novaković, S. B., Bogdanović, G. A., Giester, G., Kosović, M.,& Libowitzky, E.. (2019). First crystal structures of metal complexes with a 4-nitropyrazole-3-carboxylic acid ligand and the third crystal form of the ligand. in Acta Crystallographica Section C Structural Chemistry, 75(3), 255-264.
https://doi.org/10.1107/S2053229619001244
Jaćimović ŽK, Novaković SB, Bogdanović GA, Giester G, Kosović M, Libowitzky E. First crystal structures of metal complexes with a 4-nitropyrazole-3-carboxylic acid ligand and the third crystal form of the ligand. in Acta Crystallographica Section C Structural Chemistry. 2019;75(3):255-264.
doi:10.1107/S2053229619001244 .
Jaćimović, Željko K., Novaković, Slađana B., Bogdanović, Goran A., Giester, Gerald, Kosović, Milica, Libowitzky, Eugen, "First crystal structures of metal complexes with a 4-nitropyrazole-3-carboxylic acid ligand and the third crystal form of the ligand" in Acta Crystallographica Section C Structural Chemistry, 75, no. 3 (2019):255-264,
https://doi.org/10.1107/S2053229619001244 . .

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