Bis(N,N-di­ethyl­dithio­carbamato-κ2S,S′)(3-hy­droxy­pyridine-κN)zinc and bis­[N-(2-hy­droxy­eth­yl)-N-methyldithio­carbamato-κ2S,S′](3-hy­droxy­pyridine-κN)zinc: crystal structures and Hirshfeld surface analysis

Jotani, M.M.; Arman, H.D.; Poplaukhin, P.; Tiekink, E.R.T.

doi:10.1107/S205698901601728X

research communications

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ISSN: 2056-9890

Volume 72| Part 12| December 2016| Pages 1700-1709

https://doi.org/10.1107/S205698901601728X

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Bis(N,N-diethyldithiocarbamato-κ²S,S′)(3-hydroxypyridine-κN)zinc and bis[N-(2-hydroxyethyl)-N-methyldithiocarbamato-κ²S,S′](3-hydroxypyridine-κN)zinc: crystal structures and Hirshfeld surface analysis

Mukesh M. Jotani,^a ‡ Hadi D. Arman,^b Pavel Poplaukhin ^c and Edward R. T. Tiekink ^d ^*

^aDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, ^bDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, ^cChemical Abstracts Service, 2540 Olentangy River Rd, Columbus, Ohio, 43202, USA, and ^dResearch Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 25 October 2016; accepted 27 October 2016; online 1 November 2016)

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

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

CCDC references: 1511865; 1511864

1. Chemical context

The structures of binary zinc bis(dithiocarbamates) are always zero-dimensional (i.e. molecular) (Heard, 2005 ) in contrast to their cadmium (Tan et al., 2016b ) and mercury (Jotani et al., 2016 ) analogues; dithiocarbamate is ⁻S₂CNRR'. The zinc structures can be mononuclear, distorted tetrahedral as in Zn(S₂CNCy₂)₂ (Cox & Tiekink, 2009 ) or, far more commonly, binuclear as in the archetypical compound [Zn(S₂CNEt₂)₂]₂, where heavily distorted five-coordinate geometries are found for zinc as two of the ligands are chelating and the others are μ₂-tridentate (Bonamico et al., 1965 ; Tiekink, 2000 ), with the adoption of one form over the other often being related to the steric bulk of the R/R′ groups (Tiekink, 2003 ). However, there is no clear-cut delineation between the adoption of one structural motif over the other depending on steric bulk. This is nicely illustrated in the structure of Zn[S₂CN(i-Bu)₂]₂ which has equal numbers of both motifs (Ivanov et al., 2005 ). A popular process by which structures of greater dimensionality might be formed is by the addition of neutral, potentially bridging ligands. However, in the case of zinc dithiocarbamates, complexation with bidentate ligands usually results in the isolation of zero-dimensional, binuclear molecules, e.g. {Zn[S₂CN(Me)i-Pr)]₂}₂(Me₂NCH₂CH₂NMe₂) (Malik et al., 1997 ); [Zn(S₂CNMe₂)₂]₂(4,4′-bipyridyl) (Zha et al., 2010 ) and [Zn(S₂CNEt₂)₂]₂(Ph₂PCH₂CH₂PPh₂) (Zeng et al., 1994 ). Even when excess base is included in the reaction, e.g. trans-1,2-bis(4-pyridyl)ethylene (bpe), only the zero-dimensional binuclear compound is isolated with non-coordinating bpe solvate, i.e. Zn(S₂CNEt₂)₂]₂(bpe)·bpe (Lai & Tiekink, 2003 ). That this reluctance to form coordination polymers is related directly to the nature of the dithiocarbamate ligand is seen in the adoption of zigzag chains in analogous xanthate complexes, e.g. {[Zn(S₂COR)₂]₂(bpe)}_n, for R = Et and n-Bu (Kang et al., 2010 ). Steric effects come into play when R = Cy whereby a binuclear species is isolated, i.e. [Zn(S₂COCy)₂]₂(bpe) (Kang et al., 2010). This difference in chemistry arises to the significant (40%) contribution of the canonical structure ^(2-)S₂CN⁽⁺⁾RR′, with two formally negatively charged sulfur atoms, which makes dithiocarbamate a very effective chelating agent, thereby decreasing the Lewis acidity of the zinc atom.

An approach to increase the supramolecular aggregation in the crystal structures of zinc dithiocarbamates has been to introduce hydrogen bonding functionality into the ligands, i.e using dithiocarbamate anions of the type ⁻S₂CN(R)CH₂CH₂OH. This influence is seen in the recent report of the structures of Zn[S₂CN(R)CH₂CH₂OH]₂(2,2′-bipyridyl) for R = i-Pr and CH₂CH₂OH (Safbri et al., 2016 ). The common feature of these structures along with those of related species with no hydrogen bonding potential, e.g. Zn(S₂CNMe₂)₂(2,2′-bipyridyl) (Manohar et al., 1998 ), is the presence of a distorted octahedral N₂S₄ donor set about the zinc atom. The O—H⋯O hydrogen bonding in Zn[S₂CN(R)CH₂CH₂OH]₂(2,2′-bipyridyl), in the case when R = CH₂CH₂OH, isolated as a 1:1 hydrate, leads to supramolecular ladders and these extend in two dimensions via water-O—H⋯S(dithiocarbamate) hydrogen bonds. When R = i-Pr, layers are sustained by hydroxy-O—H⋯S hydrogen bonds (Safbri et al., 2016). As an extension of these studies, in the present report, Zn(S₂CNRR′)₂ has been complexed with 3-hydroxypyridine (pyOH) to yield two 1:1 complexes. Quite different aggregation patterns are observed when R = R′ = Et (I), and R = i-Pr and R′ = CH₂CH₂OH (II). The crystal and molecular structures of (I) and (II) are described herein along with an analysis of their Hirshfeld surfaces.

2. Structural commentary

Two independent molecules of Zn(S₂CNEt₂)₂(pyOH) comprise the asymmetric unit of (I), Fig. 1; pyOH is 3-hydroxypyridine. For the Zn1-containing molecule, Fig. 1a, the Zn^II atom is chelated by two dithiocarbamate ligands and one nitrogen atom derived from the monodentate pyOH ligand. The S1-dithiocarbamate ligand chelates the zinc atom forming quite different Zn—S bond lengths compared with the S3-dithiocarbamate ligand. This is quantified in the values of Δ(Zn—S), being the difference between the Zn—S_long and Zn—S_short bond lengths, Table 1, i.e. 0.43 and 0.15 Å, respectively. The Zn1—N3 bond length is significantly shorter than the Zn—S bonds. The NS₄ coordination geometry is highly distorted as seen in the value of τ of 0.48 (Addison et al., 1984 ). This value is almost exactly intermediate between the ideal square pyramidal geometry with τ = 0.0 and ideal trigonal pyramidal with τ = 1.0. The acute S—Zn—S chelate angles contribute to this distortion, Table 1. The widest angles in the coordination geometry are subtended by S_s—Zn—S_s (s = short) and, especially, the S_l—Zn—S_l (l = long) bond angles, Table 1. The coordination geometry for the Zn2 atom, Fig. 1b, is quite similar to that just described for the Zn1 atom. The values of Δ(Zn—S) of 0.21 and 0.25 Å are intermediate to those for the Zn1-molecule. Even so, the differences in the Zn—S bond lengths in both molecules are not that great with this observation reflected in the closeness of the C—S bond lengths, Table 1. The value of τ for the Zn2-molecule is 0.53, indicating an inclination towards trigonal bipyramidal cf. the Zn1-molecule.

Table 1
Geometric data (Å, °) for (I) and (II)

Parameter	Zn1-molecule in (I)	Zn2-molecule in (I)	(II)
Zn—S1	2.3201 (8)	–	2.3319 (6)
Zn—S2	2.7461 (8)	–	2.7514 (8)
Zn—S3	2.3417 (8)	–	2.3437 (7)
Zn—S4	2.4932 (8)	–	2.5275 (6)
Zn—S5	–	2.3399 (8)	–
Zn—S6	–	2.5453 (8)	–
Zn—S7	–	2.3517 (8)	–
Zn—S8	–	2.6051 (8)	–
Zn—N3	2.069 (2)	–	2.0375 (16)
Zn—N6	–	2.070 (2)	–
C—S1, S2	1.736 (3), 1.721 (3)	–	1.733 (2), 1.7119 (19)
C—S3, S4	1.741 (3), 1.720 (3)	–	1.7364 (19), 1.7140 (19)
C—S5, S6	–	1.743 (3), 1.720 (3)	–
C—S7, S8	–	1.734 (3), 1.730 (3)	–
S1—Zn—S2	70.99 (3)	–	70.825 (18)
S3—Zn—S4	75.54 (3)	–	74.41 (2)
S1—Zn—S3	136.44 (3)	–	139.04 (2)
S2—Zn—S4	165.17 (2)	–	148.839 (18)
S5—Zn—S6	–	74.34 (3)	–
S7—Zn—S8	–	73.08 (3)	–
S5—Zn—S7	–	137.08 (3)	–
S6—Zn—S8	–	168.91 (2)	–
S1,S2,C1/S3,S4,C	19.30 (12)	–	63.81 (15)
S5,S6,C1/S7,S8,C	–	38.87 (22)	–

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.

The molecular structure of (II), Zn[S₂CN(Me)CH₂CH₂OH]₂(pyOH), is shown in Fig. 2 and selected geometric parameters are included in Table 1. The coordination modes of the dithiocarbamate ligands in (II) are close to those observed for the Zn1-molecule in (I) with Δ(Zn—S) values of 0.42 and 0.19 Å. The difference between (I) and (II) is found in the coordination geometry which is close to square pyramidal in (II), as seen in the value of τ = 0.16. In this description, the S1–S4 atoms define the basal plane with the r.m.s. deviation being 0.0501 Å. The Zn atom lies 0.7514 (4) Å above the plane in the direction of the N3 atom. The dihedral angle between the chelate rings is 63.81 (15)°, an angle significantly greater than for the comparable angles in (I), Table 1.

Figure 2
The molecular structure of (II)

, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

Overlay diagrams of the three molecules in (I) and (II) are shown in Fig. 3. The molecules have been overlapped so that the pyOH rings are coincident. The differences in the conformations of the molecules comprising (I) are clearly seen, and especially between these and the conformation in (II). Such variability in structure reflects the flexibility in the binding modes of the dithiocarbamate ligands leading to quite distinctive coordination geometries.

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.

3. Supramolecular features

The key feature of the molecular packing of (I) is the formation of hydroxy-O—H⋯S(dithiocarbamate) hydrogen bonds that sustain centrosymmetric, dimeric aggregates, via a 14-membered {⋯HOC₂NZnS}₂ synthon, Fig. 4a and Table 2. Additional stabilization to the dimer is provided by an intra-dimer π–π interaction between the pyOH rings. The inter-centroid distance is 3.5484 (18) Å and the angle of inclination is 3.91 (14)° for symmetry operation 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z. The aggregates are further stabilized by pyOH-C—H⋯π interactions where the π-system is a chelate ring. Such C—H⋯π(chelate) interactions are increasingly being recognized as being important in the supramolecular chemistry of metal 1,1-dithiolates (Tiekink & Zukerman-Schpector, 2011 ; Tan et al., 2016a ) and, it should be noted, routinely appear in the output from PLATON (Spek, 2009 ). Connections between aggregates leading to supramolecular layers in the ab plane are also of the type C—H⋯π(chelate) but with methyl-H atoms as the donors, Fig. 4b. The connections between layers along the c direction are of the type methylene-C—H⋯O(hydroxy), Fig. 4c.

Table 2
Hydrogen-bond geometry (Å, °) for (I)

Cg1 and Cg2 are the centroids of the (Zn1,S1,S2,C1) and (Zn2,S7,S8,C21) chelate rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯S8ⁱ	0.84 (2)	2.45 (1)	3.289 (2)	173 (4)
O2—H2O⋯S2ⁱⁱ	0.84 (2)	2.31 (1)	3.143 (2)	170 (4)
C8—H8A⋯Cg2	0.98	2.98	3.855 (3)	150
C13—H13⋯Cg2ⁱ	0.95	2.79	3.631 (3)	148
C20—H20C⋯Cg1ⁱⁱⁱ	0.98	2.97	3.850 (3)	150
C28—H28⋯Cg1ⁱⁱ	0.95	2.96	3.738 (3)	140
C19—H19A⋯O2^iv	0.99	2.56	3.321 (3)	134
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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.

The addition of greater hydrogen-bonding potential in (II) results in an infinite chain, Table 3. There is an hydroxy-O—H⋯O(hydroxy) hydrogen bond involving the O2 and O1 atoms as the donor and acceptor, respectively. The O1-hydroxy group forms a hydrogen bond with a dithiocarbamate-S2 atom. As shown by the `1' in Fig. 5a, these hydrogen bonds lead to a centrosymmetric 22-membered {⋯SZnSCNC₂OH⋯OH}₂ synthon. On either side of these synthons, the pyOH hydroxy group hydrogen bonds to the O2-hydroxy atom and through symmetry, a centrosymmetric 24-membered {⋯OC₂NCSZnNC₂OH}₂ synthon is formed, highlighted as `2' in Fig. 5a. Alternating synthons generate a supramolecular chain aligned along the c axis. Methylene-C—H⋯π(chelate) interactions link molecules into dimeric units, Fig. 5b. The combination of the aforementioned interactions lead to supramolecular layers that stack along the b axis with no directional interactions between them, Fig. 5c.

Table 3
Hydrogen-bond geometry (Å, °) for (II)

Cg1 is the centroid of the (Zn,S3,S4,C5) chelate ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯S2	0.84 (2)	2.61 (2)	3.371 (2)	152 (3)
O2—H2O⋯O1ⁱ	0.83 (3)	1.94 (3)	2.734 (2)	161 (3)
O3—H3O⋯O2ⁱⁱ	0.84 (3)	1.79 (2)	2.619 (2)	170 (3)
C2—H2B⋯Cg1ⁱⁱⁱ	0.99	2.76	3.689 (2)	156
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+1, -z+1; (iii) -x+2, -y+1, -z.

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.

4. Hirshfeld surface analysis

The Hirshfeld surface analysis for (I) and (II) was performed as described recently (Cardoso et al., 2016 ). From the views of the Hirshfeld surface mapped over d_norm in the range −0.2 to + 1.3 au for the Zn1- and Zn2-containing molecules of (I), Fig. 6, the presence of bright-red spots near the hydroxy-H1O and -H2O, and dithiocarbamate-S2 and S8 atoms represent the donors and acceptors of the O—H⋯S hydrogen bonds; these are viewed as blue and red regions on the Hirshfeld surfaces mapped over electrostatic potential (mapped over the range −0.07 to +0.10 au), Fig. 7, corresponding to positive and negative potentials, respectively. The faint-red spots appearing near the hydroxy-O2 and methyl-C19 atoms in Fig. 6b and 6c are due to comparatively weaker intermolecular C—H⋯O interactions. The intra-dimer π–π stacking interaction between the pyOH rings, Fig. 4a, is evident through the appearance of faint-red spots near the arene-C13 and C26 atoms of the rings, Fig. 6a and 6b, forming a close interatomic C⋯C contact, Table 4. The diminutive-red spots near the pyOH-H13 and -H28 and dithiocarbamate-C21 atoms, Fig. 6a–c, characterize the influence of the C—H⋯π(chelate) interactions; in Fig. 7, the light-blue and red regions represent the respective donors and acceptors for these interactions. The immediate environments around reference molecules showing above intermolecular interactions are illustrated in Fig. 8.

Table 4
Summary of short interatomic contacts (Å) in (I) and (II)

Contact	Distance	Symmetry operation
(I)
C13⋯C26	3.314 (4)	1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
H5⋯H7B	2.36	−x, 1 − y, −z
O1⋯H18B	2.61	2 − x, 1 − y, 1 − z
S2⋯H20B	2.96	1 − x, 1 − y, −z
S4⋯H11	2.98	1 − x, 1 − y, 1 − z
S5⋯H7A	2.97	x, y, z
S5⋯H14	2.94	1 − x, 1 − y, −z
C1⋯H28	2.75	1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
C21⋯H13	2.65	1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
C29⋯H24A	2.84	1 + x, y, z
(II)
S4⋯S4	3.4765 (11)	2 − x, 1 − y, 1 − z
C8⋯C8	3.308 (3)	2 − x, −y, 1 − z
C1⋯H6A	2.87	x, 1 + y, z
C9⋯H7B	2.57	x, 1 + y, z
C10⋯H10B	2.88	x, 1 + y, z
H1O⋯H2O	2.37 (4)	1 − x, 1 − y, −z
H2O⋯H3O	2.18 (3)	1 − x, 1 − y, 1 − z
S3⋯H1O	2.91 (3)	1 − x, 1 − y, −z
S3⋯H7A	2.99	1 − x, 1 − y, −z
Zn⋯H2B	3.06	2 − x, 1 − y, −z
O1⋯H6A	2.68	x, 1 + y, z

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.

The presence of peripheral hydroxy groups participating in the O—H⋯O hydrogen bonds in the structure of (II) result in the distinct bright-red spots near the respective donors and acceptor atoms on the Hirshfeld surface mapped over d_norm, Fig. 9a and 9b, and result in the blue and red regions corresponding to positive and negative potential on the Hirshfeld surface mapped over electrostatic potential (mapped over the range −0.12 to +0.18 au), Fig. 9c. The faint-red spots near the S4, C8, C9 and H2B atoms in Fig. 9a and 9b indicate their involvement in short interatomic S⋯S, C⋯C and C⋯H/H⋯C contacts, Table 4. Fig. 10a illustrates the immediate environment about a reference molecule within Hirshfeld surfaces mapped over electrostatic potential and highlights the O—H⋯O hydrogen bonds. The C—H⋯π(chelate) and its reciprocal contact, i.e. π—H⋯C, and short interatomic S⋯S, C⋯C and C⋯H/H⋯C contacts, with labels 3–6, are shown in Fig. 10b.

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.

The overall two-dimensional fingerprint plot for individual Zn1- and Zn2-containing molecules, overall (I) and (II) are illustrated in Fig. 11a. The respective plots delineated into H⋯H, O⋯H/H⋯O, S⋯H/H⋯S, C⋯H/H⋯C, C⋯C and S⋯S contacts (McKinnon et al., 2007 ) are shown in Fig. 11b–g, respectively; the relative contributions from different contacts to the Hirshfeld surfaces of (I) and (II) are summarized in Table 5.

Table 5
Percentage contribution to interatomic contacts from the Hirshfeld surface for (I) and (II)

Contact	Zn1-molecule in (I)	Zn2-molecule in (I)	(I)	(II)
H⋯H	55.3	52.9	55.3	42.1
O⋯H/H⋯O	4.1	5.5	5.3	15.0
S⋯H/H⋯S	23.8	25.3	22.7	22.2
C⋯H/H⋯C	9.9	10.0	10.0	12.3
N⋯H/H⋯N	2.6	2.5	2.7	2.9
S⋯S	1.2	0.7	1.1	3.8
C⋯C	1.6	1.6	1.8	0.8
Zn⋯H/H⋯Zn	0.8	0.8	0.4	0.7
C⋯O/O⋯C	0.4	0.4	0.4	0.0
C⋯N/N⋯C	0.2	0.2	0.3	0.1
S⋯O/O⋯S	0.1	0.1	0.0	0.0
S⋯C/C⋯S	0.0	0.0	0.0	0.1

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.

The fingerprint plots delineated into H⋯H contacts for (I), Fig. 11b, show different distributions of points in the individual plots for Zn1- and Zn2-molecules. This, as well as their different percentage contributions to the Hirshfeld surface, Table 5, confirm their distinct chemical environments. The overall plot is the superimposition of these individual plots with a pair of small peaks, at (d_e, d_i) distances shorter than their van der Waals separations, corresponding to short interatomic H⋯H contacts, Table 4, between the hydrogen atoms of the Zn1-molecule.

The fingerprint plots delineated into O⋯H/H⋯O contacts, Fig. 11c, also exhibit slightly different profiles for the independent molecules. The respective peaks at d_e + d_i ∼ 2.7 Å and ∼ 2.6 Å correspond to donors (upper region) and the acceptors (lower region) for the Zn1-molecule, whereas these appear as a pair of peaks at the same d_e + d_i ∼ 2.6 Å distance for the Zn2-molecule. This is likely due to the interacting oxygen and hydrogen atoms for the Zn1-molecule being at their van der Waals separation in the donor region, i.e. at 2.72 Å, while in the acceptor region the peak corresponds to a short interatomic O⋯H contact, Table 4. In the plot for the Zn2-molecule, this contact gives rise to the pair of peaks at d_e + d_i ∼ 2.6 Å.

The pair of spikes with their tips at different d_e + d_i distances in the fingerprint plots delineated into S⋯H/H⋯S contacts, Fig. 11d, for the Zn1- and Zn2-molecules result from different hydroxy-O—H⋯S(dithiocarbamate) hydrogen bonds. The tips at d_e + d_i ∼ 2.4 Å in the donor region of the plot for the Zn1-molecule and in the acceptor region for the Zn2-molecule are due to the formation of O—H⋯S hydrogen bonds between the hydroxy-O1 and dithiocarbamate-S8 atoms; the other hydrogen bond, involving the O2 and S2 atoms, gives rise to tips at d_e + d_i ∼ 2.3 Å in the respective donor and acceptor regions of the plots, Fig. 11d. The plot for the overall structure results from the superimposition of individual plots and shows the symmetric distribution of points as a pair of long spikes having tips at d_e + d_i ∼ 2.3 Å. The short interatomic S⋯H/H⋯S contacts in the crystal of (I), Table 4, appear as a pair of aligned green points beginning at d_e + d_i ∼ 3.0 Å in the respective plots.

Almost the same percentage contribution from C⋯H/H⋯C contacts to the overall surface is made by the Zn1- and Zn2-molecules, Table 5, and the respective fingerprint plots, Fig. 11e, have the same shape with tips at d_e + d_i ∼ 2.7 Å which are due to the short interatomic C⋯H/H⋯C contacts, Table 4, involving the atoms forming the C—H⋯π(chelate) interactions; the points corresponding to the other short C⋯H/H⋯C contacts are within the plot. The C⋯C contacts assigned to intra-dimer π–π stacking interactions between pyOH-rings have a small, i.e. 1.8%, but recognizable contribution to the Hirshfeld surface and appear as an arrow-like distribution of points around d_e = d_i = 1.8 Å in Fig. 11f. As indicated in Fig. 11g, S⋯S contacts do not figure prominently in the molecular packing of (I).

The corresponding two-dimensional fingerprint plots for (II) are also given in Fig. 11. In the fingerprint plots delineated into H⋯H contacts, Fig. 11b, a pair of very thin spikes having their tips at d_e + d_i ∼ 2.3 Å indicate the presence of short interatomic H⋯H contacts between hydroxy-H1O and -H2O atoms, Table 4. Also, the intermolecular O—H⋯O hydrogen bond between the pyOH-O3 and hydroxy-O2 atoms results in a short interatomic H⋯H contact between the H2O and H3O atoms, Table 4. The increase in the percentage contribution from O⋯H/H⋯O contacts to the Hirshfeld surface and the corresponding decrease in the contribution from H⋯H contacts in (II), cf. (I), Table 5, is due to the presence of dominating O—H⋯O hydrogen bonds in the crystal of (II) and is characterized as a pair of long spikes terminating at d_e + d_i ∼ 1.8 Å, Fig. 11c. The tips corresponding to the O1⋯H6A contact, Table 4, are diminished within the long spikes corresponding to dominant O—H⋯O hydrogen bonds.

The S⋯H/H⋯S contacts with the nearly same contribution to the surface of (II) as for (I), i.e. 22.2 and 22.7%, respectively, reflect the O—H⋯S hydrogen bonds and additional S⋯H contacts resulting in tips at d_e + d_i ∼ 2.9 Å in Fig. 11d and Table 4. The 12.3% contribution from C⋯H/H⋯C contacts to the surface with the tips at d_e + d_i ∼ 2.6 Å in the plot, Fig. 11e, results from the C—H⋯π(chelate) and short interatomic C⋯H/H⋯C contacts, Table 4. The presence of C—H⋯π(chelate) interactions is also indicated by the short interatomic Zn⋯H/H⋯Zn contacts summarized in Table 4. The presence of short interatomic C⋯C contacts between symmetry-related methyl-C8 atoms is identified in the respective plot, Fig. 11f, as the pair of tips at d_e + d_i ∼1.7 Å. Finally, a cone-shaped distribution of points with a 3.8% contribution to the surface from S⋯S contacts having a vertex at d_e = d_i ∼ 1.7 Å in the fingerprint plot, Fig. 11g, results from short interatomic contacts between S4 atoms, Table 4; the absence of analogous contacts in (I) results in a very low percentage contribution to its surface (see above).

5. Database survey

As alluded to in the Chemical context, the presence of hydroxyethyl groups in zinc dithiocarbamates leads to a higher degree of recognizable supramolecular aggregation owing to hydrogen bonding, usually of the type hydroxy-O—H⋯O(hydroxy) but, sometimes also of the type hydroxy-O—H⋯S(dithiocarbamate) (Tan et al., 2013 ; Jamaludin et al., 2016 ). The following is a brief overview of some previous structures with ethylhydroxydithiocarbamate ligands highlighting the important role of hydrogen bonding in the supramolecular aggregation. In the what might be termed the parent binary compound, i.e. {Zn[S₂CN(CH₂CH₂OH)₂]₂}₂, the usual dimeric motif is evident but these self-assemble via strong hydrogen bonding into three-dimensional architectures in both of the polymorphs characterized thus far, with the difference between the structures being the topology of supramolecular layers, i.e. flattened (Manohar et al., 1998) and undulating (Benson et al., 2007 ). When one ethylhydroxy group is replaced by an ethyl group, as in {Zn[S₂CN(Et)CH₂CH₂OH]₂}₂, the reduced hydrogen bonding leads to supramolecular chains (Benson et al., 2007). Bridging ligands lead to zero-dimensional aggregates, e.g. in {Zn[S₂CN(Me)CH₂CH₂OH)₂]₂}₂L, where L is (3-pyridyl)CH₂N(H)C(=O)C(=O)N(H)CH₂(3-pyridyl). However, hydrogen bonding of the type hydroxy-O—H⋯O(hydroxy) links the molecules into inter-woven double chains (Poplaukhin & Tiekink, 2008 ). The interesting structural chemistry is complimented by observations that some of these compounds exhibit exciting, cell-specific, anti-cancer potential (Tan et al., 2015 ). The foregoing suggests this is a fertile area of research, well deserving of continuing attention.

6. Synthesis and crystallization

Synthesis of (I): In a 2:1:0.5 molar ratio, Zn(S₂CNEt₂)₂, N,N′-bis(pyridin-3-ylmethyl)ethanedithiodiamide (Zukerman-Schpector et al., 2015 ) and 3-hydroxy pyridine were dissolved in chloroform. Solvent diffusion of hexane into this solution produced pink crystals. FT–IR (cm⁻¹): ν(C=N) 1482 (s, br); ν(C—S) 987 (s). ¹H NMR (d₆-DMSO, 300 MHz): δ 9.91 (s, 1H, OH), 8.20–8.00 (m, 2H, aromatic-H), 7.30–7.10 (m, 2H, aromatic-H), 3.82 (8H, q, NCH₂, J = 7.00 Hz); 1.22 (12H, t, CH₃, J = 7.20 Hz).

Synthesis of (II): In a 1:1 molar ratio, Zn[S₂N(Me)CH₂CH₂OH]₂ and 3-hydroxy pyridine were dissolved in a MeOH/EtOH (1:1 v/v) solution. Solvent diffusion of hexane into this solution led to the formation of colourless crystals. FT–IR (cm⁻¹): ν(C=N) 1480 (s); ν(C—S) 1002 (s). ¹H NMR (d₆-DMSO, 300 MHz): δ 9.91 (s, 1H, aromatic-OH), 8.20–8.00 (m, 2H, aromatic-H), 7.30–7.10 (m, 2H, aromatic-H), 4.91 (2H, t, OH, J = 5.50 Hz); 3.90 (4H, t, NCH₂, J = 6.25 Hz); 3.70 (4H, dt, CH₂O, J = 5.50, 5.50 Hz); 3.41 (6H, s, CH₃).

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 6. The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). The oxygen-bound H-atoms were located in difference Fourier maps but were refined with a distance restraint of O—H = 0.84±0.01 Å, and with U_iso(H) set to 1.5U_eq(O).

Table 6
Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Zn(C₅H₁₀NS₂)₂(C₅H₅NO)]	[Zn(C₄H₈NOS₂)₂(C₅H₅NO)]
M_r	456.99	460.94
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	98	98
a, b, c (Å)	10.032 (2), 31.955 (7), 13.233 (3)	8.8645 (19), 9.956 (2), 11.473 (3)
α, β, γ (°)	90, 105.920 (2), 90	102.154 (4), 106.989 (4), 93.466 (3)
V (Å³)	4079.4 (15)	938.6 (4)
Z	8	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.62	1.77
Crystal size (mm)	0.50 × 0.40 × 0.15	0.37 × 0.25 × 0.25

Data collection
Diffractometer	Rigaku AFC12κ/SATURN724	Rigaku AFC12κ/SATURN724
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.687, 1.000	0.860, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25139, 9202, 8401	6836, 4249, 4133
R_int	0.037	0.026
(sin θ/λ)_max (Å⁻¹)	0.650	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.106, 1.06	0.032, 0.080, 1.06
No. of reflections	9202	4249
No. of parameters	447	228
No. of restraints	2	3
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.45	0.43, −0.60
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), QMol (Gans & Shalloway, 2001 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1511865; 1511864

Crystal structure: contains datablock . DOI: https://doi.org/10.1107/S205698901601728X/hb7628sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901601728X/hb7628Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S205698901601728X/hb7628IIsup3.hkl

checkCIF report

Computing details top

For both compounds, data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015). Molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001), DIAMOND (Brandenburg, 2006) for (I); ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006) for (II). For both compounds, software used to prepare material for publication: publCIF (Westrip, 2010).

(I) Bis(N,N-diethyldithiocarbamato-κ²S,S')(3-hydroxypyridine-κN)zinc top

Crystal data top

[Zn(C₅H₁₀NS₂)₂(C₅H₅NO)]	F(000) = 1904
M_r = 456.99	D_x = 1.488 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.032 (2) Å	Cell parameters from 16430 reflections
b = 31.955 (7) Å	θ = 2.5–40.7°
c = 13.233 (3) Å	µ = 1.62 mm⁻¹
β = 105.920 (2)°	T = 98 K
V = 4079.4 (15) Å³	Slab, pink
Z = 8	0.50 × 0.40 × 0.15 mm

Data collection top

Rigaku AFC12κ/SATURN724 diffractometer	9202 independent reflections
Radiation source: fine-focus sealed tube	8401 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→13
T_min = 0.687, T_max = 1.000	k = −41→41
25139 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: mixed
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0477P)² + 4.2267P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
9202 reflections	Δρ_max = 0.73 e Å⁻³
447 parameters	Δρ_min = −0.45 e Å⁻³
2 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.22939 (3)	0.51145 (2)	0.27529 (3)	0.02233 (8)
S1	0.06711 (7)	0.51485 (2)	0.37067 (5)	0.02470 (14)
S2	−0.01500 (6)	0.54220 (2)	0.14827 (5)	0.02127 (13)
S3	0.27656 (6)	0.46663 (2)	0.14937 (5)	0.02206 (13)
S4	0.42106 (7)	0.46582 (2)	0.37705 (5)	0.02349 (14)
O1	0.5087 (2)	0.64627 (6)	0.45759 (17)	0.0305 (4)
H1O	0.524 (4)	0.6717 (4)	0.449 (3)	0.046*
N1	−0.1829 (2)	0.54510 (7)	0.27436 (17)	0.0206 (4)
N2	0.4941 (2)	0.41780 (7)	0.23507 (18)	0.0218 (4)
N3	0.3333 (2)	0.56740 (7)	0.27551 (18)	0.0209 (4)
C1	−0.0580 (3)	0.53538 (8)	0.2645 (2)	0.0194 (5)
C2	−0.2190 (3)	0.54050 (9)	0.3748 (2)	0.0257 (5)
H2A	−0.1631	0.5176	0.4162	0.031*
H2B	−0.3180	0.5327	0.3602	0.031*
C3	−0.1933 (3)	0.58063 (10)	0.4389 (2)	0.0339 (7)
H3A	−0.0933	0.5856	0.4649	0.051*
H3B	−0.2330	0.5780	0.4985	0.051*
H3C	−0.2371	0.6041	0.3946	0.051*
C4	−0.2961 (3)	0.55989 (9)	0.1855 (2)	0.0265 (5)
H4A	−0.2567	0.5750	0.1350	0.032*
H4B	−0.3553	0.5796	0.2114	0.032*
C5	−0.3837 (3)	0.52333 (10)	0.1301 (2)	0.0334 (6)
H5A	−0.3275	0.5054	0.0978	0.050*
H5B	−0.4634	0.5340	0.0756	0.050*
H5C	−0.4166	0.5071	0.1813	0.050*
C6	0.4075 (3)	0.44668 (8)	0.2532 (2)	0.0203 (5)
C7	0.4939 (3)	0.40561 (9)	0.1276 (2)	0.0268 (6)
H7A	0.5897	0.3983	0.1272	0.032*
H7B	0.4644	0.4299	0.0804	0.032*
C8	0.3997 (3)	0.36900 (10)	0.0850 (3)	0.0353 (7)
H8A	0.4218	0.3457	0.1350	0.053*
H8B	0.4134	0.3602	0.0177	0.053*
H8C	0.3030	0.3774	0.0748	0.053*
C9	0.6003 (3)	0.39774 (8)	0.3208 (2)	0.0261 (5)
H9A	0.6182	0.3691	0.2992	0.031*
H9B	0.5651	0.3954	0.3836	0.031*
C10	0.7353 (3)	0.42242 (10)	0.3491 (2)	0.0313 (6)
H10A	0.7667	0.4266	0.2860	0.047*
H10B	0.8060	0.4069	0.4015	0.047*
H10C	0.7201	0.4497	0.3782	0.047*
C11	0.3950 (3)	0.58787 (8)	0.3647 (2)	0.0236 (5)
H11	0.4004	0.5749	0.4303	0.028*
C12	0.4514 (3)	0.62776 (8)	0.3636 (2)	0.0236 (5)
C13	0.4457 (3)	0.64633 (8)	0.2680 (2)	0.0242 (5)
H13	0.4834	0.6734	0.2653	0.029*
C14	0.3839 (3)	0.62468 (9)	0.1761 (2)	0.0266 (5)
H14	0.3798	0.6366	0.1096	0.032*
C15	0.3287 (3)	0.58556 (9)	0.1827 (2)	0.0233 (5)
H15	0.2859	0.5709	0.1197	0.028*
Zn2	0.68820 (3)	0.27217 (2)	0.19561 (3)	0.02217 (8)
S5	0.75317 (6)	0.32449 (2)	0.09483 (5)	0.02196 (13)
S6	0.89261 (7)	0.30961 (2)	0.31945 (5)	0.02480 (14)
S7	0.52971 (7)	0.26483 (2)	0.29651 (5)	0.02464 (14)
S8	0.45448 (6)	0.24765 (2)	0.06815 (5)	0.02173 (13)
O2	0.9810 (2)	0.13960 (6)	0.36656 (16)	0.0293 (4)
H2O	0.997 (4)	0.1141 (4)	0.358 (3)	0.044*
N4	0.9764 (2)	0.36702 (7)	0.20279 (18)	0.0214 (4)
N5	0.2806 (2)	0.23709 (7)	0.18746 (18)	0.0218 (4)
N6	0.7917 (2)	0.21685 (7)	0.18654 (18)	0.0214 (4)
C16	0.8854 (3)	0.33725 (8)	0.2066 (2)	0.0196 (5)
C17	1.0857 (3)	0.37985 (9)	0.2973 (2)	0.0270 (6)
H17A	1.0512	0.3764	0.3601	0.032*
H17B	1.1075	0.4098	0.2914	0.032*
C18	1.2165 (3)	0.35417 (10)	0.3110 (3)	0.0358 (7)
H18A	1.1964	0.3247	0.3211	0.054*
H18B	1.2880	0.3642	0.3725	0.054*
H18C	1.2497	0.3570	0.2482	0.054*
C19	0.9748 (3)	0.38995 (8)	0.1058 (2)	0.0246 (5)
H19A	0.9319	0.3722	0.0442	0.030*
H19B	1.0713	0.3959	0.1050	0.030*
C20	0.8951 (3)	0.43075 (9)	0.0970 (2)	0.0284 (6)
H20A	0.7968	0.4248	0.0881	0.043*
H20B	0.9056	0.4466	0.0362	0.043*
H20C	0.9315	0.4473	0.1610	0.043*
C21	0.4063 (3)	0.24864 (8)	0.1840 (2)	0.0206 (5)
C22	0.2413 (3)	0.23388 (9)	0.2868 (2)	0.0247 (5)
H22A	0.1416	0.2405	0.2736	0.030*
H22B	0.2948	0.2546	0.3377	0.030*
C23	0.2691 (3)	0.19034 (10)	0.3332 (2)	0.0310 (6)
H23A	0.2249	0.1696	0.2800	0.047*
H23B	0.2311	0.1879	0.3937	0.047*
H23C	0.3693	0.1853	0.3559	0.047*
C24	0.1702 (3)	0.22577 (9)	0.0921 (2)	0.0262 (6)
H24A	0.1135	0.2028	0.1086	0.031*
H24B	0.2125	0.2158	0.0371	0.031*
C25	0.0776 (3)	0.26349 (11)	0.0511 (3)	0.0371 (7)
H25A	0.0353	0.2732	0.1053	0.056*
H25B	0.0047	0.2554	−0.0118	0.056*
H25C	0.1335	0.2860	0.0333	0.056*
C26	0.8547 (3)	0.19591 (8)	0.2743 (2)	0.0225 (5)
H26	0.8552	0.2078	0.3402	0.027*
C27	0.9194 (3)	0.15755 (8)	0.2729 (2)	0.0223 (5)
C28	0.9185 (3)	0.14053 (8)	0.1761 (2)	0.0249 (5)
H28	0.9612	0.1143	0.1720	0.030*
C29	0.8541 (3)	0.16261 (9)	0.0855 (2)	0.0261 (5)
H29	0.8533	0.1517	0.0185	0.031*
C30	0.7912 (3)	0.20054 (9)	0.0932 (2)	0.0242 (5)
H30	0.7466	0.2154	0.0308	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02198 (15)	0.01845 (15)	0.02877 (17)	−0.00025 (11)	0.01071 (12)	−0.00238 (12)
S1	0.0212 (3)	0.0328 (3)	0.0206 (3)	0.0046 (2)	0.0065 (2)	0.0053 (3)
S2	0.0235 (3)	0.0222 (3)	0.0186 (3)	−0.0006 (2)	0.0066 (2)	−0.0003 (2)
S3	0.0209 (3)	0.0226 (3)	0.0217 (3)	0.0009 (2)	0.0042 (2)	−0.0024 (2)
S4	0.0270 (3)	0.0237 (3)	0.0202 (3)	0.0043 (2)	0.0073 (2)	−0.0009 (2)
O1	0.0391 (11)	0.0230 (10)	0.0248 (10)	−0.0026 (8)	0.0011 (9)	−0.0029 (8)
N1	0.0190 (10)	0.0225 (10)	0.0192 (11)	0.0006 (8)	0.0032 (8)	0.0007 (8)
N2	0.0232 (10)	0.0208 (10)	0.0222 (11)	0.0011 (8)	0.0074 (9)	−0.0022 (8)
N3	0.0192 (10)	0.0210 (10)	0.0222 (11)	0.0010 (8)	0.0052 (8)	0.0012 (8)
C1	0.0226 (12)	0.0163 (11)	0.0192 (12)	−0.0006 (9)	0.0054 (9)	−0.0002 (9)
C2	0.0212 (12)	0.0324 (14)	0.0251 (14)	0.0000 (10)	0.0090 (10)	0.0014 (11)
C3	0.0349 (15)	0.0411 (17)	0.0294 (15)	−0.0047 (13)	0.0148 (13)	−0.0096 (13)
C4	0.0208 (12)	0.0296 (14)	0.0270 (14)	0.0024 (10)	0.0031 (10)	0.0054 (11)
C5	0.0261 (13)	0.0419 (17)	0.0280 (15)	−0.0048 (12)	0.0002 (11)	0.0000 (13)
C6	0.0201 (11)	0.0168 (11)	0.0256 (13)	−0.0016 (9)	0.0088 (10)	0.0004 (10)
C7	0.0258 (13)	0.0278 (13)	0.0286 (14)	0.0034 (10)	0.0108 (11)	−0.0057 (11)
C8	0.0338 (15)	0.0347 (16)	0.0362 (17)	−0.0002 (12)	0.0075 (13)	−0.0166 (13)
C9	0.0273 (13)	0.0213 (12)	0.0293 (14)	0.0061 (10)	0.0069 (11)	0.0023 (11)
C10	0.0265 (13)	0.0316 (15)	0.0326 (16)	0.0047 (11)	0.0028 (12)	0.0020 (12)
C11	0.0240 (12)	0.0229 (12)	0.0226 (13)	0.0019 (10)	0.0040 (10)	0.0006 (10)
C12	0.0181 (11)	0.0239 (13)	0.0263 (14)	0.0028 (9)	0.0020 (10)	−0.0041 (10)
C13	0.0223 (12)	0.0202 (12)	0.0312 (15)	−0.0001 (9)	0.0090 (11)	0.0007 (10)
C14	0.0278 (13)	0.0280 (14)	0.0250 (14)	0.0036 (10)	0.0087 (11)	0.0039 (11)
C15	0.0218 (12)	0.0263 (13)	0.0211 (13)	0.0003 (10)	0.0045 (10)	−0.0001 (10)
Zn2	0.02096 (15)	0.01850 (15)	0.02802 (17)	−0.00040 (10)	0.00836 (12)	0.00219 (11)
S5	0.0212 (3)	0.0211 (3)	0.0224 (3)	−0.0027 (2)	0.0039 (2)	0.0019 (2)
S6	0.0299 (3)	0.0234 (3)	0.0208 (3)	−0.0021 (2)	0.0064 (3)	0.0019 (2)
S7	0.0225 (3)	0.0297 (3)	0.0209 (3)	−0.0035 (2)	0.0046 (2)	−0.0031 (3)
S8	0.0221 (3)	0.0229 (3)	0.0200 (3)	−0.0008 (2)	0.0055 (2)	0.0026 (2)
O2	0.0397 (11)	0.0231 (10)	0.0245 (10)	0.0017 (8)	0.0078 (9)	0.0027 (8)
N4	0.0217 (10)	0.0207 (10)	0.0210 (11)	−0.0033 (8)	0.0043 (8)	−0.0025 (8)
N5	0.0224 (10)	0.0221 (10)	0.0209 (11)	0.0000 (8)	0.0059 (9)	0.0010 (9)
N6	0.0186 (10)	0.0204 (10)	0.0247 (11)	−0.0032 (8)	0.0053 (8)	0.0005 (9)
C16	0.0222 (11)	0.0186 (11)	0.0195 (12)	0.0002 (9)	0.0083 (9)	−0.0007 (9)
C17	0.0295 (13)	0.0257 (13)	0.0222 (13)	−0.0072 (10)	0.0010 (11)	−0.0053 (10)
C18	0.0297 (14)	0.0371 (16)	0.0357 (17)	−0.0021 (12)	0.0008 (13)	−0.0001 (13)
C19	0.0286 (13)	0.0251 (13)	0.0223 (13)	−0.0056 (10)	0.0104 (11)	0.0005 (10)
C20	0.0348 (14)	0.0229 (13)	0.0280 (15)	−0.0049 (11)	0.0094 (12)	0.0033 (11)
C21	0.0228 (12)	0.0173 (11)	0.0203 (12)	0.0024 (9)	0.0038 (10)	0.0031 (9)
C22	0.0224 (12)	0.0294 (13)	0.0241 (14)	0.0006 (10)	0.0097 (10)	0.0002 (11)
C23	0.0300 (14)	0.0353 (15)	0.0291 (15)	0.0021 (12)	0.0102 (12)	0.0061 (12)
C24	0.0191 (12)	0.0310 (14)	0.0252 (14)	−0.0042 (10)	0.0006 (10)	−0.0010 (11)
C25	0.0282 (14)	0.0408 (17)	0.0348 (17)	0.0039 (12)	−0.0037 (13)	0.0059 (14)
C26	0.0235 (12)	0.0221 (12)	0.0214 (13)	−0.0022 (9)	0.0052 (10)	−0.0016 (10)
C27	0.0241 (12)	0.0186 (12)	0.0242 (13)	−0.0030 (9)	0.0068 (10)	0.0014 (10)
C28	0.0284 (13)	0.0197 (12)	0.0288 (14)	0.0000 (10)	0.0113 (11)	−0.0013 (10)
C29	0.0335 (14)	0.0259 (13)	0.0200 (13)	−0.0018 (11)	0.0091 (11)	−0.0006 (10)
C30	0.0244 (12)	0.0252 (13)	0.0227 (13)	−0.0014 (10)	0.0063 (10)	0.0038 (10)

Geometric parameters (Å, º) top

Zn1—N3	2.069 (2)	Zn2—N6	2.070 (2)
Zn1—S1	2.3201 (8)	Zn2—S5	2.3399 (8)
Zn1—S3	2.3417 (8)	Zn2—S7	2.3517 (8)
Zn1—S4	2.4932 (8)	Zn2—S6	2.5453 (8)
Zn1—S2	2.7461 (8)	Zn2—S8	2.6051 (8)
S1—C1	1.736 (3)	S5—C16	1.743 (3)
S2—C1	1.721 (3)	S6—C16	1.720 (3)
S3—C6	1.741 (3)	S7—C21	1.734 (3)
S4—C6	1.720 (3)	S8—C21	1.730 (3)
O1—C12	1.355 (3)	O2—C27	1.352 (3)
O1—H1O	0.842 (10)	O2—H2O	0.844 (10)
N1—C1	1.332 (3)	N4—C16	1.328 (3)
N1—C4	1.470 (3)	N4—C19	1.474 (3)
N1—C2	1.477 (3)	N4—C17	1.478 (3)
N2—C6	1.333 (3)	N5—C21	1.326 (3)
N2—C9	1.473 (3)	N5—C22	1.476 (3)
N2—C7	1.474 (3)	N5—C24	1.478 (3)
N3—C11	1.343 (3)	N6—C26	1.339 (3)
N3—C15	1.347 (3)	N6—C30	1.340 (4)
C2—C3	1.520 (4)	C17—C18	1.515 (4)
C2—H2A	0.9900	C17—H17A	0.9900
C2—H2B	0.9900	C17—H17B	0.9900
C3—H3A	0.9800	C18—H18A	0.9800
C3—H3B	0.9800	C18—H18B	0.9800
C3—H3C	0.9800	C18—H18C	0.9800
C4—C5	1.524 (4)	C19—C20	1.517 (4)
C4—H4A	0.9900	C19—H19A	0.9900
C4—H4B	0.9900	C19—H19B	0.9900
C5—H5A	0.9800	C20—H20A	0.9800
C5—H5B	0.9800	C20—H20B	0.9800
C5—H5C	0.9800	C20—H20C	0.9800
C7—C8	1.512 (4)	C22—C23	1.515 (4)
C7—H7A	0.9900	C22—H22A	0.9900
C7—H7B	0.9900	C22—H22B	0.9900
C8—H8A	0.9800	C23—H23A	0.9800
C8—H8B	0.9800	C23—H23B	0.9800
C8—H8C	0.9800	C23—H23C	0.9800
C9—C10	1.523 (4)	C24—C25	1.528 (4)
C9—H9A	0.9900	C24—H24A	0.9900
C9—H9B	0.9900	C24—H24B	0.9900
C10—H10A	0.9800	C25—H25A	0.9800
C10—H10B	0.9800	C25—H25B	0.9800
C10—H10C	0.9800	C25—H25C	0.9800
C11—C12	1.397 (4)	C26—C27	1.390 (4)
C11—H11	0.9500	C26—H26	0.9500
C12—C13	1.384 (4)	C27—C28	1.389 (4)
C13—C14	1.388 (4)	C28—C29	1.389 (4)
C13—H13	0.9500	C28—H28	0.9500
C14—C15	1.380 (4)	C29—C30	1.383 (4)
C14—H14	0.9500	C29—H29	0.9500
C15—H15	0.9500	C30—H30	0.9500

N3—Zn1—S1	112.77 (6)	N6—Zn2—S5	110.78 (6)
N3—Zn1—S3	109.24 (6)	N6—Zn2—S7	112.06 (6)
S1—Zn1—S3	136.44 (3)	S5—Zn2—S7	137.08 (3)
N3—Zn1—S4	101.02 (6)	N6—Zn2—S6	96.34 (6)
S1—Zn1—S4	106.61 (3)	S5—Zn2—S6	74.34 (3)
S3—Zn1—S4	75.54 (3)	S7—Zn2—S6	103.42 (3)
N3—Zn1—S2	93.23 (6)	N6—Zn2—S8	94.71 (6)
S1—Zn1—S2	70.99 (3)	S5—Zn2—S8	100.83 (3)
S3—Zn1—S2	95.97 (3)	S7—Zn2—S8	73.08 (3)
S4—Zn1—S2	165.17 (2)	S6—Zn2—S8	168.91 (2)
C1—S1—Zn1	92.11 (9)	C16—S5—Zn2	87.12 (9)
C1—S2—Zn1	78.96 (9)	C16—S6—Zn2	81.24 (9)
C6—S3—Zn1	85.32 (9)	C21—S7—Zn2	88.69 (9)
C6—S4—Zn1	81.11 (9)	C21—S8—Zn2	80.88 (9)
C12—O1—H1O	110 (3)	C27—O2—H2O	110 (3)
C1—N1—C4	122.5 (2)	C16—N4—C19	123.1 (2)
C1—N1—C2	122.3 (2)	C16—N4—C17	121.7 (2)
C4—N1—C2	115.2 (2)	C19—N4—C17	115.3 (2)
C6—N2—C9	122.1 (2)	C21—N5—C22	122.6 (2)
C6—N2—C7	121.9 (2)	C21—N5—C24	122.4 (2)
C9—N2—C7	116.0 (2)	C22—N5—C24	115.0 (2)
C11—N3—C15	118.9 (2)	C26—N6—C30	119.1 (2)
C11—N3—Zn1	122.19 (18)	C26—N6—Zn2	120.10 (18)
C15—N3—Zn1	118.67 (18)	C30—N6—Zn2	120.70 (18)
N1—C1—S2	122.1 (2)	N4—C16—S6	122.3 (2)
N1—C1—S1	119.98 (19)	N4—C16—S5	120.4 (2)
S2—C1—S1	117.91 (14)	S6—C16—S5	117.23 (14)
N1—C2—C3	111.8 (2)	N4—C17—C18	111.6 (2)
N1—C2—H2A	109.2	N4—C17—H17A	109.3
C3—C2—H2A	109.2	C18—C17—H17A	109.3
N1—C2—H2B	109.2	N4—C17—H17B	109.3
C3—C2—H2B	109.2	C18—C17—H17B	109.3
H2A—C2—H2B	107.9	H17A—C17—H17B	108.0
C2—C3—H3A	109.5	C17—C18—H18A	109.5
C2—C3—H3B	109.5	C17—C18—H18B	109.5
H3A—C3—H3B	109.5	H18A—C18—H18B	109.5
C2—C3—H3C	109.5	C17—C18—H18C	109.5
H3A—C3—H3C	109.5	H18A—C18—H18C	109.5
H3B—C3—H3C	109.5	H18B—C18—H18C	109.5
N1—C4—C5	110.8 (2)	N4—C19—C20	111.9 (2)
N1—C4—H4A	109.5	N4—C19—H19A	109.2
C5—C4—H4A	109.5	C20—C19—H19A	109.2
N1—C4—H4B	109.5	N4—C19—H19B	109.2
C5—C4—H4B	109.5	C20—C19—H19B	109.2
H4A—C4—H4B	108.1	H19A—C19—H19B	107.9
C4—C5—H5A	109.5	C19—C20—H20A	109.5
C4—C5—H5B	109.5	C19—C20—H20B	109.5
H5A—C5—H5B	109.5	H20A—C20—H20B	109.5
C4—C5—H5C	109.5	C19—C20—H20C	109.5
H5A—C5—H5C	109.5	H20A—C20—H20C	109.5
H5B—C5—H5C	109.5	H20B—C20—H20C	109.5
N2—C6—S4	122.2 (2)	N5—C21—S8	121.7 (2)
N2—C6—S3	120.0 (2)	N5—C21—S7	121.0 (2)
S4—C6—S3	117.86 (14)	S8—C21—S7	117.32 (15)
N2—C7—C8	113.5 (2)	N5—C22—C23	111.1 (2)
N2—C7—H7A	108.9	N5—C22—H22A	109.4
C8—C7—H7A	108.9	C23—C22—H22A	109.4
N2—C7—H7B	108.9	N5—C22—H22B	109.4
C8—C7—H7B	108.9	C23—C22—H22B	109.4
H7A—C7—H7B	107.7	H22A—C22—H22B	108.0
C7—C8—H8A	109.5	C22—C23—H23A	109.5
C7—C8—H8B	109.5	C22—C23—H23B	109.5
H8A—C8—H8B	109.5	H23A—C23—H23B	109.5
C7—C8—H8C	109.5	C22—C23—H23C	109.5
H8A—C8—H8C	109.5	H23A—C23—H23C	109.5
H8B—C8—H8C	109.5	H23B—C23—H23C	109.5
N2—C9—C10	111.8 (2)	N5—C24—C25	110.5 (2)
N2—C9—H9A	109.3	N5—C24—H24A	109.5
C10—C9—H9A	109.3	C25—C24—H24A	109.5
N2—C9—H9B	109.3	N5—C24—H24B	109.5
C10—C9—H9B	109.3	C25—C24—H24B	109.5
H9A—C9—H9B	107.9	H24A—C24—H24B	108.1
C9—C10—H10A	109.5	C24—C25—H25A	109.5
C9—C10—H10B	109.5	C24—C25—H25B	109.5
H10A—C10—H10B	109.5	H25A—C25—H25B	109.5
C9—C10—H10C	109.5	C24—C25—H25C	109.5
H10A—C10—H10C	109.5	H25A—C25—H25C	109.5
H10B—C10—H10C	109.5	H25B—C25—H25C	109.5
N3—C11—C12	121.7 (3)	N6—C26—C27	122.7 (3)
N3—C11—H11	119.2	N6—C26—H26	118.7
C12—C11—H11	119.2	C27—C26—H26	118.7
O1—C12—C13	123.6 (3)	O2—C27—C28	124.4 (2)
O1—C12—C11	117.4 (3)	O2—C27—C26	117.3 (2)
C13—C12—C11	119.1 (3)	C28—C27—C26	118.3 (3)
C12—C13—C14	118.9 (3)	C27—C28—C29	118.7 (3)
C12—C13—H13	120.5	C27—C28—H28	120.6
C14—C13—H13	120.5	C29—C28—H28	120.6
C15—C14—C13	119.1 (3)	C30—C29—C28	119.7 (3)
C15—C14—H14	120.5	C30—C29—H29	120.2
C13—C14—H14	120.5	C28—C29—H29	120.2
N3—C15—C14	122.3 (3)	N6—C30—C29	121.5 (3)
N3—C15—H15	118.8	N6—C30—H30	119.3
C14—C15—H15	118.8	C29—C30—H30	119.3

C4—N1—C1—S2	3.9 (3)	C19—N4—C16—S6	177.68 (19)
C2—N1—C1—S2	−178.13 (19)	C17—N4—C16—S6	−3.3 (3)
C4—N1—C1—S1	−175.75 (19)	C19—N4—C16—S5	−1.8 (3)
C2—N1—C1—S1	2.2 (3)	C17—N4—C16—S5	177.20 (19)
Zn1—S2—C1—N1	179.1 (2)	Zn2—S6—C16—N4	−177.2 (2)
Zn1—S2—C1—S1	−1.28 (12)	Zn2—S6—C16—S5	2.33 (12)
Zn1—S1—C1—N1	−178.9 (2)	Zn2—S5—C16—N4	177.0 (2)
Zn1—S1—C1—S2	1.49 (14)	Zn2—S5—C16—S6	−2.51 (13)
C1—N1—C2—C3	92.4 (3)	C16—N4—C17—C18	89.7 (3)
C4—N1—C2—C3	−89.5 (3)	C19—N4—C17—C18	−91.2 (3)
C1—N1—C4—C5	91.2 (3)	C16—N4—C19—C20	94.5 (3)
C2—N1—C4—C5	−86.9 (3)	C17—N4—C19—C20	−84.6 (3)
C9—N2—C6—S4	5.1 (3)	C22—N5—C21—S8	174.11 (19)
C7—N2—C6—S4	−171.71 (19)	C24—N5—C21—S8	−4.8 (3)
C9—N2—C6—S3	−175.58 (19)	C22—N5—C21—S7	−5.2 (3)
C7—N2—C6—S3	7.6 (3)	C24—N5—C21—S7	175.93 (19)
Zn1—S4—C6—N2	175.6 (2)	Zn2—S8—C21—N5	−177.8 (2)
Zn1—S4—C6—S3	−3.74 (12)	Zn2—S8—C21—S7	1.50 (12)
Zn1—S3—C6—N2	−175.4 (2)	Zn2—S7—C21—N5	177.7 (2)
Zn1—S3—C6—S4	3.94 (13)	Zn2—S7—C21—S8	−1.64 (14)
C6—N2—C7—C8	−91.5 (3)	C21—N5—C22—C23	−90.3 (3)
C9—N2—C7—C8	91.5 (3)	C24—N5—C22—C23	88.7 (3)
C6—N2—C9—C10	−88.5 (3)	C21—N5—C24—C25	−95.2 (3)
C7—N2—C9—C10	88.5 (3)	C22—N5—C24—C25	85.8 (3)
C15—N3—C11—C12	1.5 (4)	C30—N6—C26—C27	−0.4 (4)
Zn1—N3—C11—C12	−172.77 (19)	Zn2—N6—C26—C27	176.51 (19)
N3—C11—C12—O1	178.6 (2)	N6—C26—C27—O2	179.3 (2)
N3—C11—C12—C13	−1.2 (4)	N6—C26—C27—C28	0.2 (4)
O1—C12—C13—C14	−179.7 (2)	O2—C27—C28—C29	−178.6 (2)
C11—C12—C13—C14	0.0 (4)	C26—C27—C28—C29	0.4 (4)
C12—C13—C14—C15	0.8 (4)	C27—C28—C29—C30	−0.8 (4)
C11—N3—C15—C14	−0.7 (4)	C26—N6—C30—C29	0.1 (4)
Zn1—N3—C15—C14	173.8 (2)	Zn2—N6—C30—C29	−176.88 (19)
C13—C14—C15—N3	−0.4 (4)	C28—C29—C30—N6	0.6 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the (Zn1,S1,S2,C1) and (Zn2,S7,S8,C21) chelate rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···S8ⁱ	0.84 (2)	2.45 (1)	3.289 (2)	173 (4)
O2—H2O···S2ⁱⁱ	0.84 (2)	2.31 (1)	3.143 (2)	170 (4)
C8—H8A···Cg2	0.98	2.98	3.855 (3)	150
C13—H13···Cg2ⁱ	0.95	2.79	3.631 (3)	148
C20—H20C···Cg1ⁱⁱⁱ	0.98	2.97	3.850 (3)	150
C28—H28···Cg1ⁱⁱ	0.95	2.96	3.738 (3)	140
C19—H19A···O2^iv	0.99	2.56	3.321 (3)	134

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) x, −y+1/2, z−1/2.

(II) Bis[N-(2-hydroxyethyl)-N-methyldithiocarbamato-κ²S,S'](3-hydroxypyridine-κN)zinc top

Crystal data top

[Zn(C₄H₈NOS₂)₂(C₅H₅NO)]	Z = 2
M_r = 460.94	F(000) = 476
Triclinic, P1	D_x = 1.631 Mg m⁻³
a = 8.8645 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.956 (2) Å	Cell parameters from 4145 reflections
c = 11.473 (3) Å	θ = 2.5–40.6°
α = 102.154 (4)°	µ = 1.77 mm⁻¹
β = 106.989 (4)°	T = 98 K
γ = 93.466 (3)°	Slab, colourless
V = 938.6 (4) Å³	0.37 × 0.25 × 0.25 mm

Data collection top

Rigaku AFC12κ/SATURN724 diffractometer	4249 independent reflections
Radiation source: fine-focus sealed tube	4133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.860, T_max = 1.000	k = −12→12
6836 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: mixed
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.037P)² + 0.6872P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4249 reflections	Δρ_max = 0.43 e Å⁻³
228 parameters	Δρ_min = −0.60 e Å⁻³
3 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn	0.76357 (3)	0.49975 (2)	0.25271 (2)	0.01863 (8)
S1	0.97385 (5)	0.65936 (5)	0.26357 (4)	0.01674 (11)
S2	0.69910 (6)	0.58080 (5)	0.03011 (5)	0.01835 (11)
S3	0.64889 (6)	0.27205 (5)	0.14638 (4)	0.01739 (11)
S4	0.90377 (6)	0.34805 (5)	0.38990 (4)	0.01782 (11)
O1	0.74043 (18)	0.85049 (17)	−0.09808 (15)	0.0260 (3)
H1O	0.695 (3)	0.783 (2)	−0.083 (3)	0.039*
O2	0.45844 (17)	0.01078 (16)	0.24736 (13)	0.0218 (3)
H2O	0.413 (3)	0.051 (3)	0.193 (2)	0.033*
O3	0.67339 (19)	0.91603 (16)	0.57620 (15)	0.0285 (3)
H3O	0.624 (3)	0.945 (3)	0.627 (2)	0.043*
N1	0.98304 (19)	0.70602 (17)	0.04700 (15)	0.0176 (3)
N2	0.78664 (19)	0.08741 (16)	0.26777 (15)	0.0161 (3)
N3	0.62518 (19)	0.59446 (17)	0.35049 (15)	0.0169 (3)
C1	0.8924 (2)	0.65371 (18)	0.10539 (18)	0.0149 (3)
C2	0.9350 (2)	0.6846 (2)	−0.09003 (18)	0.0191 (4)
H2A	0.8502	0.6046	−0.1285	0.023*
H2B	1.0271	0.6612	−0.1190	0.023*
C3	0.8749 (2)	0.8097 (2)	−0.1355 (2)	0.0221 (4)
H3A	0.9619	0.8882	−0.1017	0.027*
H3B	0.8450	0.7881	−0.2282	0.027*
C4	1.1446 (2)	0.7770 (2)	0.1154 (2)	0.0252 (4)
H4A	1.1454	0.8372	0.1951	0.038*
H4B	1.1789	0.8330	0.0647	0.038*
H4C	1.2175	0.7081	0.1321	0.038*
C5	0.7800 (2)	0.22057 (19)	0.26907 (17)	0.0143 (3)
C6	0.6826 (2)	−0.02451 (19)	0.16625 (18)	0.0181 (4)
H6A	0.7468	−0.0971	0.1421	0.022*
H6B	0.6353	0.0126	0.0920	0.022*
C7	0.5502 (2)	−0.0887 (2)	0.20439 (18)	0.0193 (4)
H7A	0.4796	−0.1595	0.1316	0.023*
H7B	0.5972	−0.1359	0.2718	0.023*
C8	0.8976 (2)	0.0451 (2)	0.3718 (2)	0.0232 (4)
H8A	1.0069	0.0797	0.3796	0.035*
H8B	0.8852	−0.0562	0.3554	0.035*
H8C	0.8751	0.0837	0.4499	0.035*
C9	0.6861 (2)	0.7161 (2)	0.43240 (18)	0.0175 (4)
H9	0.7921	0.7530	0.4436	0.021*
C10	0.6007 (2)	0.7911 (2)	0.50204 (18)	0.0194 (4)
C11	0.4471 (2)	0.7342 (2)	0.48828 (19)	0.0226 (4)
H11	0.3855	0.7818	0.5347	0.027*
C12	0.3863 (2)	0.6063 (2)	0.4053 (2)	0.0249 (4)
H12	0.2826	0.5646	0.3953	0.030*
C13	0.4768 (2)	0.5400 (2)	0.33723 (19)	0.0221 (4)
H13	0.4331	0.4534	0.2794	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.02010 (13)	0.01232 (12)	0.02810 (14)	0.00449 (9)	0.01447 (10)	0.00421 (9)
S1	0.0155 (2)	0.0171 (2)	0.0178 (2)	0.00248 (17)	0.00462 (17)	0.00523 (17)
S2	0.0154 (2)	0.0194 (2)	0.0201 (2)	0.00046 (17)	0.00437 (18)	0.00651 (18)
S3	0.0217 (2)	0.0157 (2)	0.0149 (2)	0.00533 (17)	0.00362 (18)	0.00587 (17)
S4	0.0180 (2)	0.0143 (2)	0.0184 (2)	0.00276 (16)	0.00247 (18)	0.00227 (17)
O1	0.0257 (8)	0.0311 (8)	0.0317 (8)	0.0137 (6)	0.0166 (7)	0.0160 (7)
O2	0.0232 (7)	0.0268 (8)	0.0184 (7)	0.0090 (6)	0.0094 (6)	0.0064 (6)
O3	0.0326 (8)	0.0227 (8)	0.0321 (8)	0.0011 (6)	0.0208 (7)	−0.0037 (6)
N1	0.0157 (7)	0.0191 (8)	0.0198 (8)	0.0025 (6)	0.0077 (6)	0.0058 (6)
N2	0.0165 (7)	0.0140 (7)	0.0165 (7)	0.0040 (6)	0.0024 (6)	0.0043 (6)
N3	0.0157 (7)	0.0179 (8)	0.0192 (7)	0.0071 (6)	0.0063 (6)	0.0062 (6)
C1	0.0160 (8)	0.0107 (8)	0.0193 (8)	0.0053 (6)	0.0071 (7)	0.0037 (7)
C2	0.0236 (10)	0.0199 (9)	0.0181 (9)	0.0071 (7)	0.0114 (8)	0.0058 (7)
C3	0.0250 (10)	0.0261 (10)	0.0232 (9)	0.0091 (8)	0.0140 (8)	0.0118 (8)
C4	0.0167 (9)	0.0301 (11)	0.0295 (11)	−0.0018 (8)	0.0078 (8)	0.0093 (9)
C5	0.0151 (8)	0.0149 (8)	0.0154 (8)	0.0046 (6)	0.0076 (7)	0.0038 (7)
C6	0.0217 (9)	0.0125 (8)	0.0177 (8)	0.0037 (7)	0.0053 (7)	−0.0004 (7)
C7	0.0215 (9)	0.0157 (9)	0.0195 (9)	0.0036 (7)	0.0047 (7)	0.0038 (7)
C8	0.0228 (10)	0.0181 (9)	0.0257 (10)	0.0065 (8)	−0.0005 (8)	0.0091 (8)
C9	0.0176 (9)	0.0180 (9)	0.0195 (9)	0.0059 (7)	0.0077 (7)	0.0066 (7)
C10	0.0221 (9)	0.0212 (10)	0.0173 (9)	0.0065 (8)	0.0080 (8)	0.0060 (7)
C11	0.0204 (9)	0.0311 (11)	0.0196 (9)	0.0094 (8)	0.0101 (8)	0.0058 (8)
C12	0.0139 (9)	0.0333 (12)	0.0256 (10)	0.0040 (8)	0.0061 (8)	0.0026 (9)
C13	0.0177 (9)	0.0264 (10)	0.0201 (9)	0.0037 (8)	0.0053 (8)	0.0016 (8)

Geometric parameters (Å, º) top

Zn—N3	2.0375 (16)	C2—H2A	0.9900
Zn—S1	2.3319 (6)	C2—H2B	0.9900
Zn—S3	2.3437 (7)	C3—H3A	0.9900
Zn—S4	2.5275 (6)	C3—H3B	0.9900
Zn—S2	2.7514 (8)	C4—H4A	0.9800
S1—C1	1.733 (2)	C4—H4B	0.9800
S2—C1	1.7119 (19)	C4—H4C	0.9800
S3—C5	1.7364 (19)	C6—C7	1.518 (3)
S4—C5	1.7140 (19)	C6—H6A	0.9900
O1—C3	1.433 (2)	C6—H6B	0.9900
O1—H1O	0.833 (10)	C7—H7A	0.9900
O2—C7	1.418 (2)	C7—H7B	0.9900
O2—H2O	0.833 (10)	C8—H8A	0.9800
O3—C10	1.350 (2)	C8—H8B	0.9800
O3—H3O	0.834 (10)	C8—H8C	0.9800
N1—C1	1.333 (2)	C9—C10	1.393 (3)
N1—C4	1.468 (2)	C9—H9	0.9500
N1—C2	1.468 (2)	C10—C11	1.394 (3)
N2—C5	1.328 (2)	C11—C12	1.387 (3)
N2—C8	1.464 (2)	C11—H11	0.9500
N2—C6	1.466 (2)	C12—C13	1.379 (3)
N3—C9	1.337 (3)	C12—H12	0.9500
N3—C13	1.345 (3)	C13—H13	0.9500
C2—C3	1.516 (3)

N3—Zn—S1	109.72 (5)	N1—C4—H4B	109.5
N3—Zn—S3	110.80 (5)	H4A—C4—H4B	109.5
S1—Zn—S3	139.04 (2)	N1—C4—H4C	109.5
N3—Zn—S4	103.07 (5)	H4A—C4—H4C	109.5
S1—Zn—S4	102.00 (2)	H4B—C4—H4C	109.5
S3—Zn—S4	74.41 (2)	N2—C5—S4	121.34 (14)
N3—Zn—S2	107.89 (5)	N2—C5—S3	121.19 (14)
S1—Zn—S2	70.825 (18)	S4—C5—S3	117.46 (11)
S3—Zn—S2	91.20 (2)	N2—C6—C7	112.02 (16)
S4—Zn—S2	148.839 (18)	N2—C6—H6A	109.2
C1—S1—Zn	90.54 (6)	C7—C6—H6A	109.2
C1—S2—Zn	77.85 (7)	N2—C6—H6B	109.2
C5—S3—Zn	86.67 (6)	C7—C6—H6B	109.2
C5—S4—Zn	81.43 (7)	H6A—C6—H6B	107.9
C3—O1—H1O	109 (2)	O2—C7—C6	112.50 (16)
C7—O2—H2O	113 (2)	O2—C7—H7A	109.1
C10—O3—H3O	110 (2)	C6—C7—H7A	109.1
C1—N1—C4	121.53 (17)	O2—C7—H7B	109.1
C1—N1—C2	122.52 (16)	C6—C7—H7B	109.1
C4—N1—C2	115.68 (16)	H7A—C7—H7B	107.8
C5—N2—C8	120.74 (16)	N2—C8—H8A	109.5
C5—N2—C6	122.91 (16)	N2—C8—H8B	109.5
C8—N2—C6	116.33 (15)	H8A—C8—H8B	109.5
C9—N3—C13	118.73 (17)	N2—C8—H8C	109.5
C9—N3—Zn	118.04 (13)	H8A—C8—H8C	109.5
C13—N3—Zn	123.22 (14)	H8B—C8—H8C	109.5
N1—C1—S2	122.54 (15)	N3—C9—C10	122.79 (18)
N1—C1—S1	118.66 (14)	N3—C9—H9	118.6
S2—C1—S1	118.79 (11)	C10—C9—H9	118.6
N1—C2—C3	113.44 (16)	O3—C10—C9	116.64 (18)
N1—C2—H2A	108.9	O3—C10—C11	125.07 (18)
C3—C2—H2A	108.9	C9—C10—C11	118.27 (19)
N1—C2—H2B	108.9	C12—C11—C10	118.52 (19)
C3—C2—H2B	108.9	C12—C11—H11	120.7
H2A—C2—H2B	107.7	C10—C11—H11	120.7
O1—C3—C2	112.64 (16)	C13—C12—C11	119.77 (19)
O1—C3—H3A	109.1	C13—C12—H12	120.1
C2—C3—H3A	109.1	C11—C12—H12	120.1
O1—C3—H3B	109.1	N3—C13—C12	121.87 (19)
C2—C3—H3B	109.1	N3—C13—H13	119.1
H3A—C3—H3B	107.8	C12—C13—H13	119.1
N1—C4—H4A	109.5

C4—N1—C1—S2	175.51 (15)	Zn—S4—C5—S3	−1.66 (9)
C2—N1—C1—S2	−10.8 (2)	Zn—S3—C5—N2	−176.68 (15)
C4—N1—C1—S1	−4.7 (2)	Zn—S3—C5—S4	1.77 (10)
C2—N1—C1—S1	169.02 (14)	C5—N2—C6—C7	−103.9 (2)
Zn—S2—C1—N1	167.26 (16)	C8—N2—C6—C7	74.4 (2)
Zn—S2—C1—S1	−12.55 (9)	N2—C6—C7—O2	55.4 (2)
Zn—S1—C1—N1	−165.30 (14)	C13—N3—C9—C10	−2.0 (3)
Zn—S1—C1—S2	14.52 (10)	Zn—N3—C9—C10	178.55 (14)
C1—N1—C2—C3	102.8 (2)	N3—C9—C10—O3	−176.43 (17)
C4—N1—C2—C3	−83.2 (2)	N3—C9—C10—C11	2.1 (3)
N1—C2—C3—O1	−58.9 (2)	O3—C10—C11—C12	177.9 (2)
C8—N2—C5—S4	1.6 (3)	C9—C10—C11—C12	−0.5 (3)
C6—N2—C5—S4	179.87 (14)	C10—C11—C12—C13	−1.1 (3)
C8—N2—C5—S3	−179.97 (15)	C9—N3—C13—C12	0.2 (3)
C6—N2—C5—S3	−1.7 (3)	Zn—N3—C13—C12	179.67 (16)
Zn—S4—C5—N2	176.79 (16)	C11—C12—C13—N3	1.3 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the (Zn,S3,S4,C5) chelate ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···S2	0.84 (2)	2.61 (2)	3.371 (2)	152 (3)
O2—H2O···O1ⁱ	0.83 (3)	1.94 (3)	2.734 (2)	161 (3)
O3—H3O···O2ⁱⁱ	0.84 (3)	1.79 (2)	2.619 (2)	170 (3)
C2—H2B···Cg1ⁱⁱⁱ	0.99	2.76	3.689 (2)	156

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z.

Geometric data (Å, °) for (I), unsolvated (I) and for (II) top

Parameter	Zn1-molecule in (I)	Zn2-molecule in (I)	(II)
Zn—S1	2.3201 (8)	–	2.3319 (6)
Zn—S2	2.7461 (8)	–	2.7514 (8)
Zn—S3	2.3417 (8)	–	2.3437 (7)
Zn—S4	2.4932 (8)	–	2.5275 (6)
Zn—S5	–	2.3399 (8)	–
Zn—S6	–	2.5453 (8)	–
Zn—S7	–	2.3517 (8)	–
Zn—S8	–	2.6051 (8)	–
Zn—N3	2.069 (2)	–	2.0375 (16)
Zn—N6	–	2.070 (2)	–
C—S1, S2	1.736 (3), 1.721 (3)	–	1.733 (2), 1.7119 (19)
C—S3, S4	1.741 (3), 1.720 (3)	–	1.7364 (19), 1.7140 (19)
C—S5, S6	–	1.743 (3), 1.720 (3)	–
C—S7, S8	–	1.734 (3), 1.730 (3)	–
S1—Zn—S2	70.99 (3)	–	70.825 (18)
S3—Zn—S4	75.54 (3)	–	74.41 (2)
S1—Zn—S3	136.44 (3)	–	139.04 (2)
S2—Zn—S4	165.17 (2)	–	148.839 (18)
S5—Zn—S6	–	74.34 (3)	–
S7—Zn—S8	–	73.08 (3)	–
S5—Zn—S7	–	137.08 (3)	–
S6—Zn—S8	–	168.91 (2)	–
S1,S2,C1/S3,S4,C	19.30 (12)	–	63.81 (15)
S5,S6,C1/S7,S8,C	–	38.87 (22)	–

Summary of short interatomic contacts (Å) in (I) and (II) top

Contact	Distance	Symmetry operation
(I)
C13···C26	3.314 (4)	1 - x, 1/2 + y, 1/2 - z
H5···H7B	2.36	-x, 1 - y, -z
O1···H18B	2.61	2 - x, 1 - y, 1 - z
S2···H20B	2.96	1 - x, 1 - y, -z
S4···H11	2.98	1 - x, 1 - y, 1 - z
S5···H7A	2.97	x, y, z
S5···H14	2.94	1 - x, 1 - y, -z
C1···H28	2.75	1 - x, 1/2 + y, 1/2 - z
C21···H13	2.65	1 - x, -1/2 + y, 1/2 - z
C29···H24A	2.84	1 + x, y, z
(II)
S4···S4	3.4765 (11)	2 - x, 1 - y, 1 - z
C8···C8	3.308 (3)	2 - x, -y, 1 - z
C1···H6A	2.87	x, 1 + y, z
C9···H7B	2.57	x, 1 + y, z
C10···H10B	2.88	x, 1+y, z
H1O···H2O	2.37 (4)	1 - x, 1 - y, -z
H2O···H3O	2.18 (3)	1 - x, 1 - y, 1 - z
S3···H1O	2.91 (3)	1 - x, 1 - y, -z
S3···H7A	2.99	1 - x, 1 - y, -z
Zn···H2B	3.06	2 - x, 1 - y, -z
O1···H6A	2.68	x, 1 + y, z

Percentage contribution to interatomic contacts from the Hirshfeld surface for (I) and (II) top

Contact	Zn1-molecule in (I)	Zn2-molecule in (I)	(I)	(II)
H···H	55.3	52.9	55.3	42.1
O···H/H···O	4.1	5.5	5.3	15.0
S···H/H···S	23.8	25.3	22.7	22.2
C···H/H···C	9.9	10.0	10.0	12.3
N···H/H···N	2.6	2.5	2.7	2.9
S···S	1.2	0.7	1.1	3.8
C···C	1.6	1.6	1.8	0.8
Zn···H/H···Zn	0.8	0.8	0.4	0.7
C···O/O···C	0.4	0.4	0.4	0.0
C···N/N···C	0.2	0.2	0.3	0.1
S···O/O···S	0.1	0.1	0.0	0.0
S···C/C···S	0.0	0.0	0.0	0.1

Footnotes

‡Additional correspondence author, e-mail: mmjotani@rediffmail.com.

Acknowledgements

We thank Sunway University for support of biological and crystal engineering studies of metal dithiocarbamates.

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