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An unprecedented binuclear cadmium di ­ thio ­ carbamate adduct: bis ­ [ μ 2 - N -(2-hydroxy ­ eth ­ yl)- N -iso ­ propyl ­ carbamodi ­ thio ­ ato- κ 3 S : S , S ′ ]bis ­ {[ N -(2-hydroxy ­ eth ­ yl)- N -iso ­ propyl ­ carbamodi ­ thio ­ ato- κ 2 S , S ′ ](3-{(1 E )-[( E )-2-(pyridin-3-yl ­ methyl ­ idene)hydrazin-1-yl ­ idene]meth ­ yl}pyridine- κ N )cadmium]} dihydrate

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ABSTRACT

The asymmetric unit in the title binuclear compound, [Cd(C6H12NOS2)2(C12H10N4)]2·2H2O, comprises a CdII atom, two di­thio­carbamate (dtc) anions, a monodentate 3-pyridine­aldazine ligand and a lattice water mol­ecule. The binuclear mol­ecule is constructed by the application of inversion symmetry. One dtc ligand simultaneously chelates one cadmium atom and bridges the centrosymmetric mate, while the other dtc ligand is chelating only. This leads to a centrosymmetric [Cd(dtc)2]2 core to which are appended two 3-pyridine­aldazine ligands. The resulting NS5 donor set is based on an octa­hedron. The three-dimensional mol­ecular packing is sustained by hydroxyl-O—H(hydrox­yl) and water-O—H⋯O(hydrox­yl) hydrogen bonding, leading to supra­molecular layers parallel to (101) which are connected by water-O—H⋯N(pyrid­yl) hydrogen bonding; additional C—H⋯O, S π(chelate ring) inter­actions are also evident. The retention of the central [Cd(dtc)2]2 core upon adduct formation is unprecedented in the structural chemistry of the zinc-triad di­thio­carbamates.

No MeSH data available.


The mol­ecular structure of the binuclear title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry code: (i) 1 − x, −y, 1 − z.]
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fig1: The mol­ecular structure of the binuclear title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry code: (i) 1 − x, −y, 1 − z.]

Mentions: The mol­ecular structure of the binuclear title compound, isolated as a dihydrate, is shown in Fig. 1 ▸ and selected geometric parameters are collated in Table 1 ▸. The binuclear compound is disposed about a centre of inversion so the asymmetric comprises a Cd[S2CN(iPr)CH2CH2OH)]2 entity, a 3-pyridine­aldazine ligand and one water mol­ecule of solvation. One di­thio­carbamate (dtc) ligand coordinates in a chelating mode forming very similar Cd—S bond lengths, i.e. the difference between the Cd—Sshort and Cd—Slong bond lengths is only 0.033 Å; this equivalence is reflected in the equivalence in the associated C1—S1, S2 bond lengths, Table 1 ▸. The second independent dtc chelates one cadmium atom and at the same time bridges the other cadmium atom. The Cd—S3bridging bond lengths are close to being equal, differing by only 0.010 Å, and are longer by ca 0.1 Å than the non-bridging Cd—S4 bond length, Table 1 ▸. The differences in the number and strength of the Cd—S bond lengths for the S3-dtc ligand is reflected in the C7—S3, S4 separations with the C7—S4 bond length of 1.714 (2) Å being the shortest across the series. The sixth position in the distorted octa­hedral coordination geometry is occupied by a nitro­gen atom of the monodentate 3-pyridine­aldazine ligand. Distortions in angles about the cadmium atom are largely related to the restricted bite distances of the dtc ligands, Table 1 ▸. While not having crystallographic symmetry, the 3-pyridine­aldazine mol­ecule adopts an anti disposition about both imine bonds, i.e. C18=N4 = 1.283 (3) Å and C19=N5 = 1.277 (3) Å; the central, azo bond is 1.415 (2) Å. The pyridyl-N atoms are also anti but there are twists in the 3-pyridine­aldazine mol­ecule, as seen in the value of the dihedral angle between the two pyridyl rings of 22.78 (12)°.


An unprecedented binuclear cadmium di ­ thio ­ carbamate adduct: bis ­ [ μ 2 - N -(2-hydroxy ­ eth ­ yl)- N -iso ­ propyl ­ carbamodi ­ thio ­ ato- κ 3 S : S , S ′ ]bis ­ {[ N -(2-hydroxy ­ eth ­ yl)- N -iso ­ propyl ­ carbamodi ­ thio ­ ato- κ 2 S , S ′ ](3-{(1 E )-[( E )-2-(pyridin-3-yl ­ methyl ­ idene)hydrazin-1-yl ­ idene]meth ­ yl}pyridine- κ N )cadmium]} dihydrate
The mol­ecular structure of the binuclear title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry code: (i) 1 − x, −y, 1 − z.]
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC5120695&req=5

fig1: The mol­ecular structure of the binuclear title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry code: (i) 1 − x, −y, 1 − z.]
Mentions: The mol­ecular structure of the binuclear title compound, isolated as a dihydrate, is shown in Fig. 1 ▸ and selected geometric parameters are collated in Table 1 ▸. The binuclear compound is disposed about a centre of inversion so the asymmetric comprises a Cd[S2CN(iPr)CH2CH2OH)]2 entity, a 3-pyridine­aldazine ligand and one water mol­ecule of solvation. One di­thio­carbamate (dtc) ligand coordinates in a chelating mode forming very similar Cd—S bond lengths, i.e. the difference between the Cd—Sshort and Cd—Slong bond lengths is only 0.033 Å; this equivalence is reflected in the equivalence in the associated C1—S1, S2 bond lengths, Table 1 ▸. The second independent dtc chelates one cadmium atom and at the same time bridges the other cadmium atom. The Cd—S3bridging bond lengths are close to being equal, differing by only 0.010 Å, and are longer by ca 0.1 Å than the non-bridging Cd—S4 bond length, Table 1 ▸. The differences in the number and strength of the Cd—S bond lengths for the S3-dtc ligand is reflected in the C7—S3, S4 separations with the C7—S4 bond length of 1.714 (2) Å being the shortest across the series. The sixth position in the distorted octa­hedral coordination geometry is occupied by a nitro­gen atom of the monodentate 3-pyridine­aldazine ligand. Distortions in angles about the cadmium atom are largely related to the restricted bite distances of the dtc ligands, Table 1 ▸. While not having crystallographic symmetry, the 3-pyridine­aldazine mol­ecule adopts an anti disposition about both imine bonds, i.e. C18=N4 = 1.283 (3) Å and C19=N5 = 1.277 (3) Å; the central, azo bond is 1.415 (2) Å. The pyridyl-N atoms are also anti but there are twists in the 3-pyridine­aldazine mol­ecule, as seen in the value of the dihedral angle between the two pyridyl rings of 22.78 (12)°.

View Article: PubMed Central - HTML - PubMed

ABSTRACT

The asymmetric unit in the title binuclear compound, [Cd(C6H12NOS2)2(C12H10N4)]2·2H2O, comprises a CdII atom, two di­thio­carbamate (dtc) anions, a monodentate 3-pyridine­aldazine ligand and a lattice water mol­ecule. The binuclear mol­ecule is constructed by the application of inversion symmetry. One dtc ligand simultaneously chelates one cadmium atom and bridges the centrosymmetric mate, while the other dtc ligand is chelating only. This leads to a centrosymmetric [Cd(dtc)2]2 core to which are appended two 3-pyridine­aldazine ligands. The resulting NS5 donor set is based on an octa­hedron. The three-dimensional mol­ecular packing is sustained by hydroxyl-O—H(hydrox­yl) and water-O—H⋯O(hydrox­yl) hydrogen bonding, leading to supra­molecular layers parallel to (101) which are connected by water-O—H⋯N(pyrid­yl) hydrogen bonding; additional C—H⋯O, S π(chelate ring) inter­actions are also evident. The retention of the central [Cd(dtc)2]2 core upon adduct formation is unprecedented in the structural chemistry of the zinc-triad di­thio­carbamates.

No MeSH data available.