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Molecular Architectures Derived from Metal Ions and the Flexible 3,3'-Bipyridine Ligand: Unexpected Dimer with Hg(II).

Khutia A, Sanz Miguel PJ, Lippert B - Bioinorg Chem Appl (2010)

Bottom Line: H(2)O}(n) (1), with all other metal entities cyclic structures were formed.Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities.With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer.

View Article: PubMed Central - PubMed

Affiliation: Fakultät Chemie, Technische Universität Dortmund, 44221 Dortmund, Germany.

ABSTRACT
The flexible ditopic ligand 3,3'-bipyridine (3,3'-bpy) has been reacted with a series of transition metal species (Ag(+), Hg(2+), cis-a(2)M(2+) (a = NH(3) or a(2) = en; M = Pt, Pd), trans-a(2)Pt(2+) (a = NH(3))) in an attempt to produce discrete cyclic constructs. While Ag(+) gave a polymeric structure {[Ag(3,3'-bpy)](ClO(4)) . H(2)O}(n) (1), with all other metal entities cyclic structures were formed. Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities. With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer. With trans-(NH(3))(2)Pt(2+), different species are formed according to (1)H NMR spectroscopy, the nature of which was not established.

No MeSH data available.


(a) Section of the packing pattern in 1 (excluding H2O and ClO4−), including voids along the b direction. (b) Water-perchlorate hydrogen bonded polymer inserted along the packing tunnels of 1.
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fig4: (a) Section of the packing pattern in 1 (excluding H2O and ClO4−), including voids along the b direction. (b) Water-perchlorate hydrogen bonded polymer inserted along the packing tunnels of 1.

Mentions: The crystal structure of {[Ag(3,3′-bpy)](ClO4) · H2O}n (1) reveals a polymeric structure rather than a discrete cyclic structure as we had hoped for. The silver atom (Ag1) shows a distorted octahedral coordination sphere (Figure 3(a)), with two 3,3′-bpy ligands at the apical positions (Ag1-N1, 2.181(3) Å; Ag1-N11, 2.189(3) Å). The equatorial coordination is completed by a water molecule (Ag1-O1w, 2.722(3) Å), two perchlorate counter anions (Ag1-O13, 2.773(4) Å; Ag1-O13′, 2.861(4) Å), and an argentophilic interaction [27, 28] with a neighbor silver atom (Ag ⋯ Ag, 3.3751(8) Å). Angles and distances involving the coordination sphere of Ag1 are listed in Table 2. The polymeric structure is assembled by coordination of additional silver units to the bridging 3,3′-bpy ligands of the apical positions, with a –Ag–[N11-3,3′-bpy-N21]–Ag– basic motif, which extends along the [1 0 1] direction (Figure 3(b)). The 3,3′-bpy ligands adopt transconformations with a twist angle of 27.9(1)° between pyridine halves. The dihedral angle between two pyridyl rings coordinated to Ag1 is 7.2(1)°. The crystal packing is based on π − π stacking and argentophilic interactions between polymer strands. An upper view of the ac plane evidences the presence of voids in the structure (Figure 4(a)). They are essentially rectangular tunnels along the b axis, which house two sets of hydrogen bond-based perchlorate-water polymers. These polymers are built by connecting water molecules of crystallization and perchlorate anions. Each O1w forms two hydrogen bonds with two perchlorate anions: ⋯ O14-Cl1-O12 ⋯ (H1w)O1w(H2w) ⋯ O14-Cl1-O12 ⋯ (Figure 4(b)). Distances and angles involving O1w are O1w ⋯ O12, 2.969(5) Å; O1w ⋯ O14, 2.886(5) Å; O12 ⋯ O1w ⋯ O14, 119.5(2)°.


Molecular Architectures Derived from Metal Ions and the Flexible 3,3'-Bipyridine Ligand: Unexpected Dimer with Hg(II).

Khutia A, Sanz Miguel PJ, Lippert B - Bioinorg Chem Appl (2010)

(a) Section of the packing pattern in 1 (excluding H2O and ClO4−), including voids along the b direction. (b) Water-perchlorate hydrogen bonded polymer inserted along the packing tunnels of 1.
© Copyright Policy - open-access
Related In: Results  -  Collection

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getmorefigures.php?uid=PMC2901620&req=5

fig4: (a) Section of the packing pattern in 1 (excluding H2O and ClO4−), including voids along the b direction. (b) Water-perchlorate hydrogen bonded polymer inserted along the packing tunnels of 1.
Mentions: The crystal structure of {[Ag(3,3′-bpy)](ClO4) · H2O}n (1) reveals a polymeric structure rather than a discrete cyclic structure as we had hoped for. The silver atom (Ag1) shows a distorted octahedral coordination sphere (Figure 3(a)), with two 3,3′-bpy ligands at the apical positions (Ag1-N1, 2.181(3) Å; Ag1-N11, 2.189(3) Å). The equatorial coordination is completed by a water molecule (Ag1-O1w, 2.722(3) Å), two perchlorate counter anions (Ag1-O13, 2.773(4) Å; Ag1-O13′, 2.861(4) Å), and an argentophilic interaction [27, 28] with a neighbor silver atom (Ag ⋯ Ag, 3.3751(8) Å). Angles and distances involving the coordination sphere of Ag1 are listed in Table 2. The polymeric structure is assembled by coordination of additional silver units to the bridging 3,3′-bpy ligands of the apical positions, with a –Ag–[N11-3,3′-bpy-N21]–Ag– basic motif, which extends along the [1 0 1] direction (Figure 3(b)). The 3,3′-bpy ligands adopt transconformations with a twist angle of 27.9(1)° between pyridine halves. The dihedral angle between two pyridyl rings coordinated to Ag1 is 7.2(1)°. The crystal packing is based on π − π stacking and argentophilic interactions between polymer strands. An upper view of the ac plane evidences the presence of voids in the structure (Figure 4(a)). They are essentially rectangular tunnels along the b axis, which house two sets of hydrogen bond-based perchlorate-water polymers. These polymers are built by connecting water molecules of crystallization and perchlorate anions. Each O1w forms two hydrogen bonds with two perchlorate anions: ⋯ O14-Cl1-O12 ⋯ (H1w)O1w(H2w) ⋯ O14-Cl1-O12 ⋯ (Figure 4(b)). Distances and angles involving O1w are O1w ⋯ O12, 2.969(5) Å; O1w ⋯ O14, 2.886(5) Å; O12 ⋯ O1w ⋯ O14, 119.5(2)°.

Bottom Line: H(2)O}(n) (1), with all other metal entities cyclic structures were formed.Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities.With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer.

View Article: PubMed Central - PubMed

Affiliation: Fakultät Chemie, Technische Universität Dortmund, 44221 Dortmund, Germany.

ABSTRACT
The flexible ditopic ligand 3,3'-bipyridine (3,3'-bpy) has been reacted with a series of transition metal species (Ag(+), Hg(2+), cis-a(2)M(2+) (a = NH(3) or a(2) = en; M = Pt, Pd), trans-a(2)Pt(2+) (a = NH(3))) in an attempt to produce discrete cyclic constructs. While Ag(+) gave a polymeric structure {[Ag(3,3'-bpy)](ClO(4)) . H(2)O}(n) (1), with all other metal entities cyclic structures were formed. Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities. With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer. With trans-(NH(3))(2)Pt(2+), different species are formed according to (1)H NMR spectroscopy, the nature of which was not established.

No MeSH data available.