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Crystal structure of tricarbon-yl(N-di-phenyl-phosphanyl-N,N'-diisopropyl-P-phenyl-phospho-nous di-amide-κ(2) P,P')cobalt(I) tetra-carbonyl-cobaltate(-I) toluene 0.25-solvate.

Dura L, Spannenberg A, Beweries T - Acta Crystallogr Sect E Struct Rep Online (2014)

Bottom Line: In the cations, a Co/P/N/P four-membered slightly bent metallacycle is the key structural element.The pendant NH group is not coordinated to the Co(I) atom, which displays a distorted trigonal-bipyramidal coordination geometry.Weak inter-ionic hydrogen bonds are observed between the NH groups and a carbonyl group of the tetrahedral [Co(CO)4](-) anions.

View Article: PubMed Central - HTML - PubMed

Affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany.

ABSTRACT
The asymmetric unit of the title compound, [Co(C24H30N2P2)(CO)3][Co(CO)4]·0.25C7H8, consists of two crystallographically independent cations with similar conformations, two anions, and one-half of a toluene mol-ecule disordered about an inversion centre. In the cations, a Co/P/N/P four-membered slightly bent metallacycle is the key structural element. The pendant NH group is not coordinated to the Co(I) atom, which displays a distorted trigonal-bipyramidal coordination geometry. Weak inter-ionic hydrogen bonds are observed between the NH groups and a carbonyl group of the tetrahedral [Co(CO)4](-) anions.

No MeSH data available.


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The asymmetric unit of the title compound. Hydrogen atoms are omitted for clarity. Displacement ellipsoids correspond to the 30% probability level. Only one orientation of the disordered toluene mol­ecule is shown.
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fig1: The asymmetric unit of the title compound. Hydrogen atoms are omitted for clarity. Displacement ellipsoids correspond to the 30% probability level. Only one orientation of the disordered toluene mol­ecule is shown.

Mentions: The title compound crystallizes in the monoclinic space group P21/n with eight cations, eight anions as well as two mol­ecules of toluene in the unit cell. The toluene solvent mol­ecules are found to be disordered about inversion centres. The asymmetric unit is shown in Fig. 1 ▶. In the cation, the CoI atom is fivefold coordinated by three carbonyl ligands and the PNPNH ligand, which is bound via both P atoms (Fig. 2 ▶). Thus, the bidentate ligand forms a four-membered metallacycle at the CoI atom with the central N atom being tilted out of the plane formed by the Co and the two P atoms [the dihedral angles between the CoP2 and NP2 planes are 15.73 (10) and 14.44 (9)°]. The terminal secondary amine is not involved in complexation with the CoI atom and acts as a spectator group. In the cyclic units the following bond lengths are observed: Co1—P1 2.1948 (7), P1—N2 1.698 (2), N2—P2 1.695 (2), P2—Co1 2.1800 (7), Co2—P3 2.1884 (7), P3—N4 1.695 (2), N4—P4 1.702 (2), P4—Co2 2.1971 (7) Å. A similar coordination mode was previously found for this ligand in a variety of transition metal complexes (Aluri et al., 2010 ▶). In the cationic parts, one of the Co—C distances [Co1—C3 1.821 (3) and Co2—C30 1.832 (3) Å] is slightly longer than the other two values. In the anion, the geometry at the cobalt atom is found to be distorted tetra­hedral; all C—Co—C angles are found to be between 105.75 (13) and 111.89 (14)°, thus indicating a minor deviation from ideal Td symmetry. The Co—C bond lengths in the anions vary from 1.754 (4)–1.770 (3) Å and are comparable to those observed for a range of complexes displaying tetra­carbonyl­cobaltate anions (vide supra), including ionic salts of tetra­carbonyl­cobaltate with alkali (Klüfers, 1984a ▶,b ▶) and ammonium cations (Brammer et al. 1992 ▶; Brammer & Zhao, 1995 ▶).


Crystal structure of tricarbon-yl(N-di-phenyl-phosphanyl-N,N'-diisopropyl-P-phenyl-phospho-nous di-amide-κ(2) P,P')cobalt(I) tetra-carbonyl-cobaltate(-I) toluene 0.25-solvate.

Dura L, Spannenberg A, Beweries T - Acta Crystallogr Sect E Struct Rep Online (2014)

The asymmetric unit of the title compound. Hydrogen atoms are omitted for clarity. Displacement ellipsoids correspond to the 30% probability level. Only one orientation of the disordered toluene mol­ecule is shown.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4257381&req=5

fig1: The asymmetric unit of the title compound. Hydrogen atoms are omitted for clarity. Displacement ellipsoids correspond to the 30% probability level. Only one orientation of the disordered toluene mol­ecule is shown.
Mentions: The title compound crystallizes in the monoclinic space group P21/n with eight cations, eight anions as well as two mol­ecules of toluene in the unit cell. The toluene solvent mol­ecules are found to be disordered about inversion centres. The asymmetric unit is shown in Fig. 1 ▶. In the cation, the CoI atom is fivefold coordinated by three carbonyl ligands and the PNPNH ligand, which is bound via both P atoms (Fig. 2 ▶). Thus, the bidentate ligand forms a four-membered metallacycle at the CoI atom with the central N atom being tilted out of the plane formed by the Co and the two P atoms [the dihedral angles between the CoP2 and NP2 planes are 15.73 (10) and 14.44 (9)°]. The terminal secondary amine is not involved in complexation with the CoI atom and acts as a spectator group. In the cyclic units the following bond lengths are observed: Co1—P1 2.1948 (7), P1—N2 1.698 (2), N2—P2 1.695 (2), P2—Co1 2.1800 (7), Co2—P3 2.1884 (7), P3—N4 1.695 (2), N4—P4 1.702 (2), P4—Co2 2.1971 (7) Å. A similar coordination mode was previously found for this ligand in a variety of transition metal complexes (Aluri et al., 2010 ▶). In the cationic parts, one of the Co—C distances [Co1—C3 1.821 (3) and Co2—C30 1.832 (3) Å] is slightly longer than the other two values. In the anion, the geometry at the cobalt atom is found to be distorted tetra­hedral; all C—Co—C angles are found to be between 105.75 (13) and 111.89 (14)°, thus indicating a minor deviation from ideal Td symmetry. The Co—C bond lengths in the anions vary from 1.754 (4)–1.770 (3) Å and are comparable to those observed for a range of complexes displaying tetra­carbonyl­cobaltate anions (vide supra), including ionic salts of tetra­carbonyl­cobaltate with alkali (Klüfers, 1984a ▶,b ▶) and ammonium cations (Brammer et al. 1992 ▶; Brammer & Zhao, 1995 ▶).

Bottom Line: In the cations, a Co/P/N/P four-membered slightly bent metallacycle is the key structural element.The pendant NH group is not coordinated to the Co(I) atom, which displays a distorted trigonal-bipyramidal coordination geometry.Weak inter-ionic hydrogen bonds are observed between the NH groups and a carbonyl group of the tetrahedral [Co(CO)4](-) anions.

View Article: PubMed Central - HTML - PubMed

Affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany.

ABSTRACT
The asymmetric unit of the title compound, [Co(C24H30N2P2)(CO)3][Co(CO)4]·0.25C7H8, consists of two crystallographically independent cations with similar conformations, two anions, and one-half of a toluene mol-ecule disordered about an inversion centre. In the cations, a Co/P/N/P four-membered slightly bent metallacycle is the key structural element. The pendant NH group is not coordinated to the Co(I) atom, which displays a distorted trigonal-bipyramidal coordination geometry. Weak inter-ionic hydrogen bonds are observed between the NH groups and a carbonyl group of the tetrahedral [Co(CO)4](-) anions.

No MeSH data available.


Related in: MedlinePlus