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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.


Mol­ecular packing: (a) view of the supra­molecular layer sustained by hy­droxy-O—H⋯O(hy­droxy) and hy­droxy-O—H⋯O(water) hydrogen bonds, shown as orange dashed lines. Only the pyridyl N atoms of the 3-pyridine­aldazine ligands are shown. (b) A side-on view of the layer in (a) extended to show the two central 3-pyridine­aldazine ligands (see text). The putative water-O—H⋯N(pyrid­yl) hydrogen bonds are shown as blue dashed lines. In both images, only acidic hydrogen atoms are included.
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fig2: Mol­ecular packing: (a) view of the supra­molecular layer sustained by hy­droxy-O—H⋯O(hy­droxy) and hy­droxy-O—H⋯O(water) hydrogen bonds, shown as orange dashed lines. Only the pyridyl N atoms of the 3-pyridine­aldazine ligands are shown. (b) A side-on view of the layer in (a) extended to show the two central 3-pyridine­aldazine ligands (see text). The putative water-O—H⋯N(pyrid­yl) hydrogen bonds are shown as blue dashed lines. In both images, only acidic hydrogen atoms are included.

Mentions: Significant O—H⋯O hydrogen bonding is found in the mol­ecular packing of the binuclear title compound as would be expected from the chemical composition. Thus, mol­ecules are assembled into layers approximately parallel to (101) by hy­droxy-O—H⋯O(hydrox­yl) and hy­droxy-O—H⋯O(water) hydrogen bonds as detailed in Table 2 ▸. Thus, strings of {⋯Ohy­droxy—H⋯Ohy­droxy—H⋯Owater—H}n chains are formed as shown in Fig. 2 ▸a. The water mol­ecules also form water-O—H⋯N(pyrid­yl) hydrogen bonds on either side of the supra­molecular layers sustained by O—H⋯O hydrogen bonds, Fig. 2 ▸b. The pendent pyridyl-N atoms of Fig. 2 ▸b are coordinating to cadmium atoms of successive layers so that a three-dimensional architecture results. Globally, and as seen from Fig. 3 ▸, the mol­ecular packing comprises alternating layers of {Cd[S2CN(iPr)CH2CH2OH)]2}2 and 3-pyridine­aldazine with the key links between them being hydrogen and coordinate bonding. Within this framework stabilized primarily by hydrogen-bonding inter­actions, there are some second tier inter­actions worthy of comment (Spek, 2009 ▸). Thus, referring to data in Table 2 ▸, the hydroxyl-O1 atom also accepts a contact from a pyridyl-C—H atom as the 3-pyridine­aldazine ligand is orientated so that the non-coord­inating end is directed over the hy­droxy/water-rich region of the structure. Within the layers shown in Fig. 2 ▸a, methine-C—H⋯S inter­actions are seen and between layers pyridyl-C—H⋯S contacts, inter­estingly, both involving the S2 atom. Finally, as has increasingly been noted in recent descriptions of the structural chemistry of metal di­thio­carbamates, C—H⋯π(chelate) inter­actions are present (Tiekink & Zukerman-Schpector, 2011 ▸). Here, a pyridyl-C—H atom sits almost perpendicular to the chelate ring involving the S1-di­thio­carbamate ligand, i.e. the C—H⋯ring centroid(chelate ring) angle is 178°, in the inter-layer region, Table 2 ▸.


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
Mol­ecular packing: (a) view of the supra­molecular layer sustained by hy­droxy-O—H⋯O(hy­droxy) and hy­droxy-O—H⋯O(water) hydrogen bonds, shown as orange dashed lines. Only the pyridyl N atoms of the 3-pyridine­aldazine ligands are shown. (b) A side-on view of the layer in (a) extended to show the two central 3-pyridine­aldazine ligands (see text). The putative water-O—H⋯N(pyrid­yl) hydrogen bonds are shown as blue dashed lines. In both images, only acidic hydrogen atoms are included.
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Related In: Results  -  Collection

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Show All Figures
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fig2: Mol­ecular packing: (a) view of the supra­molecular layer sustained by hy­droxy-O—H⋯O(hy­droxy) and hy­droxy-O—H⋯O(water) hydrogen bonds, shown as orange dashed lines. Only the pyridyl N atoms of the 3-pyridine­aldazine ligands are shown. (b) A side-on view of the layer in (a) extended to show the two central 3-pyridine­aldazine ligands (see text). The putative water-O—H⋯N(pyrid­yl) hydrogen bonds are shown as blue dashed lines. In both images, only acidic hydrogen atoms are included.
Mentions: Significant O—H⋯O hydrogen bonding is found in the mol­ecular packing of the binuclear title compound as would be expected from the chemical composition. Thus, mol­ecules are assembled into layers approximately parallel to (101) by hy­droxy-O—H⋯O(hydrox­yl) and hy­droxy-O—H⋯O(water) hydrogen bonds as detailed in Table 2 ▸. Thus, strings of {⋯Ohy­droxy—H⋯Ohy­droxy—H⋯Owater—H}n chains are formed as shown in Fig. 2 ▸a. The water mol­ecules also form water-O—H⋯N(pyrid­yl) hydrogen bonds on either side of the supra­molecular layers sustained by O—H⋯O hydrogen bonds, Fig. 2 ▸b. The pendent pyridyl-N atoms of Fig. 2 ▸b are coordinating to cadmium atoms of successive layers so that a three-dimensional architecture results. Globally, and as seen from Fig. 3 ▸, the mol­ecular packing comprises alternating layers of {Cd[S2CN(iPr)CH2CH2OH)]2}2 and 3-pyridine­aldazine with the key links between them being hydrogen and coordinate bonding. Within this framework stabilized primarily by hydrogen-bonding inter­actions, there are some second tier inter­actions worthy of comment (Spek, 2009 ▸). Thus, referring to data in Table 2 ▸, the hydroxyl-O1 atom also accepts a contact from a pyridyl-C—H atom as the 3-pyridine­aldazine ligand is orientated so that the non-coord­inating end is directed over the hy­droxy/water-rich region of the structure. Within the layers shown in Fig. 2 ▸a, methine-C—H⋯S inter­actions are seen and between layers pyridyl-C—H⋯S contacts, inter­estingly, both involving the S2 atom. Finally, as has increasingly been noted in recent descriptions of the structural chemistry of metal di­thio­carbamates, C—H⋯π(chelate) inter­actions are present (Tiekink & Zukerman-Schpector, 2011 ▸). Here, a pyridyl-C—H atom sits almost perpendicular to the chelate ring involving the S1-di­thio­carbamate ligand, i.e. the C—H⋯ring centroid(chelate ring) angle is 178°, in the inter-layer region, Table 2 ▸.

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.