Bis(N, N-di-ethyl-dithio-carbamato-κ2S, S')(3-hy-droxy-pyridine-κ N)zinc and bis-[ N-(2-hy-droxy-eth-yl)- N-methyldithio-carbamato-κ2S, S'](3-hy-droxy-pyridine-κ N)zinc: crystal structures and Hirshfeld surface analysis

Abstract

The common feature of the mol-ecular structures of the title compounds, [Zn(C₅H₁₀NS₂)₂(C₅H₅NO)], (I), and [Zn(C₄H₈NOS₂)₂(C₅H₅NO)], (II), are NS₄ donor sets derived from N-bound hy-droxy-pyridyl ligands and asymmetrically chelating di-thio-carbamate ligands. The resulting coordination geometries are highly distorted, being inter-mediate between square pyramidal and trigonal bipyramidal for both independent mol-ecules comprising the asymmetric unit of (I), and significantly closer towards square pyramidal in (II). The key feature of the mol-ecular packing in (I) is the formation of centrosymmetric, dimeric aggregates sustained by pairs of hy-droxy-O-H⋯S(di-thio-carbamate) hydrogen bonds. The aggregates are connected into a three-dimensional architecture by methyl-ene-C-H⋯O(hy-droxy) and methyl-C-H⋯π(chelate) inter-actions. With greater hydrogen-bonding potential, supra-molecular chains along the c axis are formed in the crystal of (II), sustained by hy-droxy-O-H⋯O(hy-droxy) hydrogen bonds, with ethyl-hydroxy and pyridyl-hydroxy groups as the donors, along with ethyl-hydroxy-O-H⋯S(di-thio-carbamate) hydrogen bonds. Chains are connected into layers in the ac plane by methyl-ene-C-H⋯π(chelate) inter-actions and these stack along the b axis, with no directional inter-actions between them. An analysis of the Hirshfeld surfaces clearly distinguished the independent mol-ecules of (I) and reveals the importance of the C-H⋯π(chelate) inter-actions in the packing of both (I) and (II).

Keywords: Hirshfeld surface analysis; crystal structure; di­thio­carbamate; hydrogen bonding; hy­droxy­pyridine; zinc.

Figure 1

The mol­ecular structures of the two independent mol­ecules comprising the asymmetric unit in (I), showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

Figure 2

The mol­ecular structure of (II), showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

Figure 3

Overlay diagrams for the Zn1- and Zn2-mol­ecules in (I) and the mol­ecule in (II) shown as red, green and blue images, respectively: (a) approximately side-on to the pyOH ring and (b) along the N—Zn bond. The mol­ecules are overlapped so that the pyOH rings are coincident.

Figure 4

The mol­ecular packing in (I), showing (a) detail of the hy­droxy-O—H⋯S(di­thio­carbamate) hydrogen bonding, shown as orange dashed lines, leading to dimeric aggregates, (b) supra­molecular layer where the aggregates in (a) are linked by C—H⋯π(chelate) inter­actions, shown as purple dashed lines and (c) view of the unit-cell contents shown in projection down the a axis, with links between layers being of the type C—H⋯O, shown as blue dashed lines.

Figure 5

The mol­ecular packing in (II), (a) supra­molecular chain mediated by hy­droxy-O—H⋯O(hy­droxyl), S(dithiocarbamate) hydrogen bonding, shown as orange and blue dashed lines, respectively, and non-acidic H atoms omitted, (b) detail of methyl­ene-C—H⋯π(chelate) inter­actions shown as purple dashed lines and (c) view of the unit-cell contents shown in projection down the a axis, with one layer shown in space-filling mode.

Figure 6

Views of the Hirshfeld surfaces for (I) mapped over d _norm for the (a) Zn1-mol­ecule and, (b) and (c) Zn2-mol­ecule.

Figure 7

Views of the Hirshfeld surfaces mapped over electrostatic potential for (I): (a) Zn1-mol­ecule and (b) Zn2-mol­ecule.

Figure 8

(a) View of the Hirshfeld surface mapped over d _norm for (I) showing O—H⋯S hydrogen bonds and short inter­atomic C⋯C and C⋯H/H⋯C contacts, indicated by black, white and red dashed lines, respectively, about the reference mol­ecule. (b) and (c) Views of Hirshfeld surface mapped with shape-index property about the Zn1 and Zn2-containing mol­ecules, respectively. The dotted blue lines labelled with 1-4 indicates C—H⋯π(chelate) inter­actions and the red dotted line shows the π–π stacking inter­action.

Figure 9

Views of the Hirshfeld surfaces for (II) mapped over (a) and (b) d _norm and (c) electrostatic potential.

Figure 10

(a) and (b) Views of the Hirshfeld surface mapped over electrostatic potential for (II) showing O—H⋯S hydrogen bonds about the reference mol­ecule. The hydrogen bonds are indicated with black dashed lines and labelled as ‘1’ and ‘2’ in (a). In (b), the inter­molecular C—H⋯O (labelled with a ‘6’ and shown as red-dashed lines) and C—H⋯π/π⋯H—C (‘3’, red and blue) inter­actions, and short inter­atomic S⋯S (‘4’, black) and C⋯H (‘5’, white) contacts are indicated by arrows.

Figure 11

(a) The overall two-dimensional fingerprint plots for the Zn1-mol­ecule in (I), Zn2-mol­ecule in (I), (I) and (II), respectively, and those delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) S⋯H/H⋯S, (e) C⋯H/H⋯C, (f) C⋯C and (g) S⋯S contacts.