Crystal structures of (2,2'-bipyridyl-κ(2) N,N')bis-[N,N-bis-(2-hydroxy-eth-yl)di-thio-carbamato-κ(2) S,S']zinc dihydrate and (2,2'-bipyridyl-κ(2) N,N')bis-[N-(2-hydroxy-eth-yl)-N-iso-propyl-dithio-carbamato-κ(2) S,S']zinc.

The common feature of the title compounds, [Zn(C5H10NO2S2)2(C10H8N2)]·2H2O, (I), and [Zn(C6H12NOS2)2(C10H8N2)], (II), is the location of the Zn(II) atoms on a twofold rotation axis. Further, each Zn(II) atom is chelated by two symmetry-equivalent and symmetrically coordinating di-thio-carbamate ligands and a 2,2'-bi-pyridine ligand. The resulting N2S4 coordination geometry is based on a highly distorted octa-hedron in each case. In the mol-ecular packing of (I), supra-molecular ladders mediated by O-H⋯O hydrogen bonding are found whereby the uprights are defined by {⋯HO(water)⋯HO(hy-droxy)⋯} n chains parallel to the a axis and with the rungs defined by 'Zn[S2CN(CH2CH2)2]2'. The water mol-ecules connect the ladders into a supra-molecular layer parallel to the ab plane via water-O-H⋯S and pyridyl-C-H⋯O(water) inter-actions, with the connections between layers being of the type pyridyl-C-H⋯S. In (II), supra-molecular layers parallel to the ab plane are sustained by hy-droxy-O-H⋯S hydrogen bonds with connections between layers being of the type pyridyl-C-H⋯S.

Chemical context

The di­thio­carbamate ligand −S2CNRR′, is well known as an effective chelator of transition metals, main group elements and lanthanides (Hogarth, 2005 ▸; Heard, 2005 ▸). The resulting four-membered MS2C chelate ring has metalloaromatic character (Masui, 2001 ▸) and may act as an acceptor for C—H⋯π(chelate) inter­actions (Tiekink & Zukerman-Schpector, 2011 ▸) much in the same way as the now widely accepted C—H⋯π(arene) inter­actions. While other 1,1-di­thiol­ate species may also form analogous inter­actions – these were probably first discussed in cadmium xanthate (−S2COR) structures (Chen et al., 2003 ▸) – di­thio­carbamate compounds have a greater propensity to form C—H⋯π(chelate) inter­actions, an observation related to the relatively greater contribution of the canonical structure 2−S2C=N+ RR′ to the overall electronic structure that enhances the electron density in the chelate ring (Tiekink & Zukerman-Schpector, 2011 ▸). This factor explains the strong chelation ability of the di­thio­carbamate ligand and at the same time accounts for the reduced Lewis acidity of the metal cation in metal di­thio­carbamates which reduces the ability of these species to form extended architectures in their inter­actions with Lewis bases. One way of overcoming the relative inability of the metal cation to engage in supra­molecular association is to function­alize the di­thio­carbamate ligand with, relevant to the present report, hydrogen-bonding functionality. In this context and as a continuation of earlier studies of the zinc-triad elements with di­thio­carbamate ligands featuring hy­droxy­ethyl groups capable of forming hydrogen-bonding inter­actions (Benson et al., 2007 ▸; Broker & Tiekink, 2011 ▸; Zhong et al., 2004 ▸; Tan et al., 2013 ▸, 2016 ▸; Safbri et al., 2016 ▸; Howie et al., 2009 ▸), herein, the crystal and mol­ecular structures of two new zinc di­thio­carbamates, Zn[S2CN(CH2CH2OH)2]2(bipy)·2H2O, (I), and Zn[S2CN(iPr)CH2CH2OH]2(bipy), (II) where bipy = 2,2′-bi­pyridine are described.

Structural commentary

The mol­ecular structure of the zinc compound in (I) is shown in Fig. 1 ▸ and selected geometric parameters are given in Table 1 ▸. The zinc cation is located on a twofold rotation axis and is chelated by two symmetry-equivalent di­thio­carbamate ligands and the 2,2′-bi­pyridine ligand, which is bis­ected by the twofold rotation axis. The di­thio­carbamate ligand chelates in a symmetric mode with the difference between the Zn—Slong and Zn—Sshort bond lengths being 0.02 Å. The shorter Zn—S bond is approximately trans to a pyridyl-N atom. The N2S4 coordination geometry is based on an octa­hedron. In this description, one triangular face is defined by the S1, S2i and N2i atoms, and the other by the symmetry equivalent atoms [symmetry code: (i)  − x,  − y, z]. The dihedral angle between the two faces is 3.07 (4)° and the twist angle between them is approximately 35°, cf. 0 and 60° for ideal trigonal–prismatic and octa­hedral angles, respectively. The twist toward a trigonal prism is related in part to the acute bite angles subtended by the chelating ligands (Table 1 ▸).

Figure 1

The mol­ecular structure of the zinc compound in (I), showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level; the water mol­ecules of crystallization have been omitted. The unlabelled atoms are related by the symmetry operation  − x,  − y, z.

Table 1

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

Parameter	(I)a	unsolvated (I)	(II)b
Zn—S1	2.5361 (5)	2.4632 (12)	2.5068 (5)
Zn—S2	2.5163 (5)	2.5968 (13)	2.5247 (5)
Zn—S3	2.5361 (5)	2.5030 (12)	2.5068 (5)
Zn—S4	2.5163 (5)	2.6045 (13)	2.5247 (5)
Zn—N2	2.1682 (15)	2.157 (4)	2.1695 (15)
Zn—N3	2.1682 (15)	2.154 (3)	2.1695 (15)
C—S	1.7198 (18)–1.7253 (18)	1.696 (4)–1.726 (5)	1.7221 (19)–1.7301 (18)
S1—Zn—S2	71.376 (15)	70.46 (4)	71.289 (16)
S3—Zn—S4	71.376 (15)	70.15 (4)	71.289 (16)
N2—Zn—N2	75.71 (8)	74.72 (12)	75.08 (8)

Notes: (a) S3, S4 and N3 are S1i, S2i and N2i for (i)  − x,  − y, z; (b) S3, S4 and N3 are S1i, S2i and N2i for (i) 1 − x, y,  − z.

Compound (I) was characterized herein as a dihydrate and may be compared with an unsolvated literature precedent (Deng et al., 2007 ▸) for which selected geometric data are also collected in Table 1 ▸. First and foremost, the mol­ecular symmetry observed in unsolvated (I) is lacking. Also, the range of Zn—S bond lengths is significantly broader at 0.14 Å, but the trend that the shorter Zn—S bonds are approximately trans to the pyridyl-N atoms persists. The dihedral angle between the trigonal faces is 5.33 (6)° and the twist between them is 31°, indicating an inter­mediate coordination geometry.

The mol­ecule of compound (II) (Fig. 2 ▸) is also located about a twofold rotation axis and presents geometric features closely resembling those of (I), Table 1 ▸. The angle between the triangular faces is 1.50 (5)° and the twist angle is approximately 30°, again indicating a highly distorted coordination geometry.

Figure 2

The mol­ecular structure of (II), showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The unlabelled atoms are related by the symmetry operation 1 − x, y,  − z.

Supra­molecular features

Geometric parameters characterizing the inter­molecular inter­actions operating in the crystal structures of (I) and (II) are collected in Tables 2 ▸ and 3 ▸, respectively.

Table 2

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O1	0.83 (2)	1.87 (2)	2.696 (2)	177 (3)
O1—H1O⋯O1W	0.83 (2)	1.88 (2)	2.7115 (19)	177 (2)
O1W—H1W⋯O2i	0.83 (2)	1.91 (2)	2.7216 (19)	166 (2)
O1W—H2W⋯S2ii	0.83 (2)	2.45 (2)	3.2733 (15)	170 (2)
C7—H7⋯O1W iii	0.95	2.58	3.517 (2)	171
C6—H6⋯S2iv	0.95	2.81	3.490 (2)	129
C9—H9⋯S1v	0.95	2.84	3.6857 (18)	149

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Table 3

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯S2i	0.84 (2)	2.45 (2)	3.2437 (16)	160 (2)
C5—H5B⋯O1i	0.98	2.54	3.512 (2)	175
C9—H9⋯S2ii	0.95	2.86	3.550 (2)	130

Symmetry codes: (i) ; (ii) .

In the mol­ecular packing of (I), supra­molecular ladders mediated by O—H⋯O hydrogen bonding are found. There is an intra­molecular hy­droxy-O—H⋯O(hy­droxy) hydrogen bond as well as inter­molecular hy­droxy-O—H⋯O(water) and water-O—H⋯O(hy­droxy) hydrogen bonds. This mode of association results in supra­molecular {⋯HO(water)⋯HO(hy­droxy)⋯HO(hy­droxy)⋯} jagged chains parallel to the a axis that serve as the uprights in the supra­molecular ladders whereby the rungs are defined by ‘Zn(S2CN(CH2CH2)2’ (Fig. 3 ▸ a). The water mol­ecules are pivotal in connecting the ladders into a supra­molecular layer parallel to the ab plane by forming water-O—H⋯S and pyridyl-C—H⋯O(water) inter­actions (Fig. 3 ▸ b). The connections between layers to consolidate the three-dimensional architecture are of the type pyridyl-C—H⋯S (Fig. 3 ▸ c).

Figure 3

Mol­ecular packing in (I), showing (a) the supra­molecular ladders aligned along the a axis and sustained by O—H⋯O hydrogen bonding, (b) the supra­molecular layers parallel to the ab plane whereby the ladders in (a) are connected by O—H⋯S and C—H⋯O inter­actions, and (c) a view of the unit-cell contents in projection down the a axis, showing C—H⋯S inter­actions along the c axis connecting the layers in (b). The O—H⋯O, O—H⋯S, C—H⋯O and C—H⋯S inter­actions are shown as orange, blue, pink and green dashed lines, respectively.

Naturally, the mol­ecular packing in the unsolvated form of (I) is distinct (Deng et al., 2007 ▸). However, a detailed analysis of the packing is restricted as one of the hy­droxy groups is disordered over two sites. Further, there are large voids in the crystal structure, amounting to approximately 570 Å3 or 19.2% of the available volume (Spek, 2009 ▸). This is reflected in the crystal packing index of 59.2% which compares to 71.3% in (I). Globally, the crystal structure comprises alternating layers of hydro­philic and hydro­phobic regions with the former arranged as supra­molecular rods, indicating significant hydrogen bonding in this region of the crystal structure.

In the mol­ecular packing of (II), hy­droxy-O—H⋯S hydrogen bonds lead to supra­molecular layers parallel to the ab plane (Fig. 4 ▸ a). Additional stabilization to this arrangement is provided by methyl-C—H⋯O(hy­droxy) inter­actions. Connections between layers to consolidate the three-dimensional packing are of the type pyridyl-C—H⋯S (Fig. 4 ▸ b).

Figure 4

Mol­ecular packing in (II), showing (a) the supra­molecular layers parallel to the ab plane sustained by O—H⋯S and C—H⋯O inter­actions, and (b) a view of the unit-cell contents in projection down the b axis, showing C—H⋯S inter­actions along the c axis connecting the layers in (b). The O—H⋯S, C—H⋯O and C—H⋯S inter­actions are shown as orange, blue and pink dashed lines, respectively.

Database survey

Binary zinc di­thio­carbamates are generally binuclear as a result of the presence of chelating and tridentate, μ2-bridging ligands, leading to penta-coordinate geometries (Tiekink, 2003 ▸). The exceptional structures arise when the steric bulk of at least one of the terminal substituents is too great to allow for supra­molecular association, e.g. R = cyclo­hexyl (Cox & Tiekink, 2009 ▸) and R = benzyl (Decken et al., 2004 ▸). However, there is a subtle energetic balance between the two forms as seen in the crystal structure of Zn[S2CN(i-Bu)2]2 which comprises equal numbers of mono- and bi-nuclear mol­ecules (Ivanov et al., 2005 ▸). As the R groups are generally aliphatic, there is limited scope for controlled supra­molecular aggregation between the mol­ecules. This changes in the case of the present study as at least one R group has an hy­droxy­ethyl substituent. Indeed, a rich tapestry of structures have been observed for zinc compounds with this family of di­thio­carbamate ligands.

The common feature of the mol­ecular structures of the known binary species, Zn[S2NC(R)CH2CH2OH]2, is the adoption of a binuclear motif (Benson et al., 2007 ▸; Tan et al., 2015 ▸). In the mol­ecular packing of these species, when R = CH2CH2OH, a three-dimensional architecture is constructed based on hydrogen bonding (Benson et al., 2007 ▸). When the hydrogen-bonding potential is reduced, as in the case when R = Et, linear supra­molecular chains are formed (Benson et al., 2007 ▸). When R = Me, and in the 2:1 adduct with the bridging ligand (3-pyrid­yl)CH2N(H)C(=O)C(=O)N(H)CH2(3-pyrid­yl), inter­woven supra­molecular chains are formed based on hydrogen bonding (Poplaukhin & Tiekink, 2010 ▸). Extensive hydrogen bonding is also noted in co-crystals, e.g. for R = Me in the 2:1 adduct with (3-pyrid­yl)CH2N(H)C(=S)C(=S)N(H)CH2(3-pyrid­yl), a 2:1 co-crystal with S8 has been characterized in which a two-dimensional array sustained by O—H⋯O hydrogen bonding is found (Poplaukhin et al., 2012 ▸). From the foregoing, it is clear that a rich structural chemistry exists for these compounds, well worthy of further investigation. Complementing these inter­ests are the observations that zinc compounds with these ligands (Tan et al., 2015 ▸), along with gold (Jamaludin et al., 2013 ▸) and bis­muth (Ishak et al., 2014 ▸) exhibit exciting anti-cancer potential.

Synthesis and crystallization

The potassium salts of the di­thio­carbamate anions (Howie et al., 2008 ▸; Tan et al., 2013 ▸) and zinc compounds (Benson et al., 2007 ▸) were prepared in accord with the literature methods. The 1:1 adducts with 2,2′-bi­pyridine were prepared in the following manner. Zn[S2CN(CH2CH2OH)2]2 (0.20 g, 0.47 mmol) and 2,2′-bi­pyridine (Sigma Aldrich; 0.07 g, 0.47 mmol) were dissolved in acetone (30 ml) and ethanol (10 ml), respectively. The solution of 2,2′-bi­pyridine was added dropwise into the other solution with stirring for about 30 mins, resulting in a change from a colourless to a light-yellow solution. The mixture was left to stand to allow for crystallization and crystals of (I) for X-ray analysis were harvested directly. Compound (II) was prepared and harvested similarly from the reaction of Zn[S2CN(iPr)CH2CH2OH]2 (0.20 g, 0.47 mmol) in chloro­form (30 ml) and 2,2′-bi­pyridine (0.07 g, 0.47 mmol) in acetone (10 ml).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. For each of (I) and (II), carbon-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 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 O-bound H atoms were located in a difference Fourier map 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 4

Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Zn(C5H10NO2S2)2(C10H8N2)]·2H2O	[Zn(C6H12NOS2)2(C10H8N2)]
M r	618.10	578.12
Crystal system, space group	Orthorhombic, P c c n	Monoclinic, C2/c
Temperature (K)	100	100
a, b, c (Å)	6.7730 (3), 23.1063 (11), 16.9483 (8)	19.4997 (11), 9.0027 (5), 15.5352 (8)
α, β, γ (°)	90, 90, 90	90, 98.031 (5), 90
V (Å3)	2652.4 (2)	2700.5 (3)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	1.28	1.25
Crystal size (mm)	0.40 × 0.30 × 0.20	0.25 × 0.25 × 0.15
Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector	Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012 ▸)	Multi-scan (CrysAlis PRO; Agilent, 2012 ▸)
T min, T max	0.778, 1.000	0.737, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	21039, 3047, 2607	11190, 3095, 2657
R int	0.049	0.048
(sin θ/λ)max (Å−1)	0.650	0.650
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.027, 0.066, 1.02	0.030, 0.073, 1.03
No. of reflections	3047	3095
No. of parameters	171	155
No. of restraints	4	1
Δρmax, Δρmin (e Å−3)	0.39, −0.34	0.38, −0.35

Computer programs: CrysAlis PRO (Agilent, 2012 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), DIAMOND (Brandenburg, 2006 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016000700/wm5262sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016000700/wm5262Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989016000700/wm5262IIsup3.hkl

CCDC references: 1447175, 1447174

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Zn(C5H10NO2S2)2(C10H8N2)]·2H2O	Dx = 1.548 Mg m−3
Mr = 618.10	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 5870 reflections
a = 6.7730 (3) Å	θ = 2.6–27.5°
b = 23.1063 (11) Å	µ = 1.28 mm−1
c = 16.9483 (8) Å	T = 100 K
V = 2652.4 (2) Å3	Prism, light-yellow
Z = 4	0.40 × 0.30 × 0.20 mm
F(000) = 1288

Agilent SuperNova Dual diffractometer with an Atlas detector	3047 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2607 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.049
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.6°
ω scan	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −30→29
Tmin = 0.778, Tmax = 1.000	l = −22→21
21039 measured reflections

Refinement on F2	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.027	w = 1/[σ2(Fo2) + (0.0256P)2 + 1.8882P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.066	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.39 e Å−3
3047 reflections	Δρmin = −0.34 e Å−3
171 parameters

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.

	x	y	z	Uiso*/Ueq
Zn	0.7500	0.2500	0.25218 (2)	0.01179 (9)
S1	0.88162 (6)	0.32477 (2)	0.15608 (3)	0.01323 (11)
S2	0.48554 (6)	0.32443 (2)	0.22814 (3)	0.01403 (11)
N1	0.5960 (2)	0.39933 (6)	0.11619 (8)	0.0123 (3)
N2	0.5960 (2)	0.21427 (6)	0.35319 (8)	0.0122 (3)
O1	0.8068 (2)	0.51852 (6)	0.09325 (9)	0.0221 (3)
H1O	0.899 (3)	0.5406 (9)	0.1051 (14)	0.033*
O2	0.4459 (2)	0.52831 (6)	0.15907 (9)	0.0273 (3)
H2O	0.559 (2)	0.5263 (11)	0.1401 (14)	0.041*
O1W	1.1132 (2)	0.58995 (6)	0.12670 (8)	0.0202 (3)
H1W	1.225 (2)	0.5761 (10)	0.1348 (14)	0.030*
H2W	1.096 (3)	0.6133 (8)	0.1634 (10)	0.030*
C1	0.6497 (3)	0.35475 (8)	0.16217 (10)	0.0123 (4)
C2	0.7307 (3)	0.42078 (8)	0.05455 (10)	0.0151 (4)
H2A	0.6521	0.4409	0.0137	0.018*
H2B	0.7958	0.3872	0.0291	0.018*
C3	0.8882 (3)	0.46162 (8)	0.08437 (11)	0.0178 (4)
H3A	0.9390	0.4478	0.1358	0.021*
H3B	0.9996	0.4627	0.0466	0.021*
C4	0.3983 (3)	0.42555 (8)	0.12367 (11)	0.0151 (4)
H4A	0.3018	0.3948	0.1369	0.018*
H4B	0.3597	0.4422	0.0721	0.018*
C5	0.3875 (3)	0.47266 (8)	0.18629 (12)	0.0200 (4)
H5A	0.2503	0.4750	0.2061	0.024*
H5B	0.4731	0.4615	0.2311	0.024*
C6	0.4312 (3)	0.18264 (8)	0.34890 (11)	0.0161 (4)
H6	0.3897	0.1689	0.2988	0.019*
C7	0.3183 (3)	0.16904 (8)	0.41461 (11)	0.0170 (4)
H7	0.2017	0.1465	0.4096	0.020*
C8	0.3791 (3)	0.18905 (8)	0.48773 (11)	0.0154 (4)
H8	0.3034	0.1810	0.5336	0.019*
C9	0.5519 (3)	0.22098 (8)	0.49310 (10)	0.0140 (4)
H9	0.5975	0.2346	0.5428	0.017*
C10	0.6574 (2)	0.23279 (7)	0.42442 (10)	0.0115 (3)

	U11	U22	U33	U12	U13	U23
Zn	0.01403 (15)	0.01109 (16)	0.01025 (15)	0.00054 (11)	0.000	0.000
S1	0.0126 (2)	0.0131 (2)	0.0140 (2)	0.00237 (17)	0.00144 (16)	0.00154 (16)
S2	0.0142 (2)	0.0131 (2)	0.0149 (2)	0.00035 (17)	0.00304 (17)	0.00135 (16)
N1	0.0122 (7)	0.0119 (7)	0.0127 (7)	0.0013 (6)	−0.0001 (6)	−0.0003 (6)
N2	0.0126 (7)	0.0115 (7)	0.0124 (7)	0.0007 (6)	−0.0003 (6)	−0.0006 (6)
O1	0.0191 (7)	0.0139 (7)	0.0332 (8)	−0.0013 (6)	0.0019 (6)	0.0008 (6)
O2	0.0186 (7)	0.0141 (7)	0.0491 (10)	0.0024 (6)	0.0051 (7)	−0.0030 (6)
O1W	0.0197 (7)	0.0191 (8)	0.0219 (7)	0.0019 (6)	0.0003 (6)	−0.0048 (6)
C1	0.0142 (9)	0.0118 (9)	0.0110 (8)	−0.0004 (7)	−0.0005 (7)	−0.0028 (6)
C2	0.0182 (9)	0.0148 (9)	0.0123 (9)	0.0008 (7)	0.0018 (7)	0.0027 (7)
C3	0.0151 (9)	0.0147 (10)	0.0236 (10)	0.0024 (7)	0.0032 (7)	0.0034 (8)
C4	0.0130 (9)	0.0145 (9)	0.0176 (9)	0.0033 (7)	−0.0019 (7)	0.0004 (7)
C5	0.0168 (9)	0.0196 (10)	0.0235 (10)	0.0026 (8)	0.0020 (8)	−0.0027 (8)
C6	0.0169 (9)	0.0149 (9)	0.0164 (9)	−0.0014 (7)	−0.0036 (7)	−0.0019 (7)
C7	0.0131 (9)	0.0150 (10)	0.0228 (10)	−0.0033 (7)	−0.0017 (7)	0.0023 (8)
C8	0.0137 (9)	0.0157 (9)	0.0169 (9)	0.0007 (7)	0.0027 (7)	0.0047 (7)
C9	0.0159 (9)	0.0131 (9)	0.0129 (9)	0.0007 (7)	−0.0003 (7)	0.0017 (7)
C10	0.0115 (8)	0.0093 (8)	0.0136 (9)	0.0004 (7)	−0.0017 (7)	0.0001 (7)

Zn—N2i	2.1682 (15)	C2—C3	1.511 (3)
Zn—N2	2.1682 (14)	C2—H2A	0.9900
Zn—S2i	2.5163 (5)	C2—H2B	0.9900
Zn—S2	2.5163 (5)	C3—H3A	0.9900
Zn—S1i	2.5361 (5)	C3—H3B	0.9900
Zn—S1	2.5361 (5)	C4—C5	1.522 (3)
S1—C1	1.7198 (18)	C4—H4A	0.9900
S2—C1	1.7253 (18)	C4—H4B	0.9900
N1—C1	1.342 (2)	C5—H5A	0.9900
N1—C2	1.473 (2)	C5—H5B	0.9900
N1—C4	1.475 (2)	C6—C7	1.387 (3)
N2—C6	1.336 (2)	C6—H6	0.9500
N2—C10	1.347 (2)	C7—C8	1.385 (3)
O1—C3	1.434 (2)	C7—H7	0.9500
O1—H1O	0.832 (10)	C8—C9	1.386 (3)
O2—C5	1.422 (2)	C8—H8	0.9500
O2—H2O	0.830 (10)	C9—C10	1.393 (2)
O1W—H1W	0.835 (10)	C9—H9	0.9500
O1W—H2W	0.832 (9)	C10—C10i	1.485 (3)
N2i—Zn—N2	75.71 (8)	H2A—C2—H2B	107.6
N2i—Zn—S2i	92.61 (4)	O1—C3—C2	109.67 (15)
N2—Zn—S2i	102.13 (4)	O1—C3—H3A	109.7
N2i—Zn—S2	102.13 (4)	C2—C3—H3A	109.7
N2—Zn—S2	92.61 (4)	O1—C3—H3B	109.7
S2i—Zn—S2	161.36 (2)	C2—C3—H3B	109.7
N2i—Zn—S1i	159.33 (4)	H3A—C3—H3B	108.2
N2—Zn—S1i	94.50 (4)	N1—C4—C5	113.40 (15)
S2i—Zn—S1i	71.377 (15)	N1—C4—H4A	108.9
S2—Zn—S1i	96.394 (15)	C5—C4—H4A	108.9
N2i—Zn—S1	94.50 (4)	N1—C4—H4B	108.9
N2—Zn—S1	159.33 (4)	C5—C4—H4B	108.9
S2i—Zn—S1	96.394 (15)	H4A—C4—H4B	107.7
S2—Zn—S1	71.376 (15)	O2—C5—C4	114.03 (16)
S1i—Zn—S1	100.09 (2)	O2—C5—H5A	108.7
C1—S1—Zn	85.11 (6)	C4—C5—H5A	108.7
C1—S2—Zn	85.62 (6)	O2—C5—H5B	108.7
C1—N1—C2	120.14 (14)	C4—C5—H5B	108.7
C1—N1—C4	120.76 (15)	H5A—C5—H5B	107.6
C2—N1—C4	119.02 (14)	N2—C6—C7	122.73 (17)
C6—N2—C10	118.74 (15)	N2—C6—H6	118.6
C6—N2—Zn	124.56 (12)	C7—C6—H6	118.6
C10—N2—Zn	115.97 (11)	C8—C7—C6	118.61 (17)
C3—O1—H1O	107.5 (17)	C8—C7—H7	120.7
C5—O2—H2O	109.3 (18)	C6—C7—H7	120.7
H1W—O1W—H2W	105 (2)	C7—C8—C9	119.16 (17)
N1—C1—S1	121.46 (13)	C7—C8—H8	120.4
N1—C1—S2	120.88 (13)	C9—C8—H8	120.4
S1—C1—S2	117.64 (10)	C8—C9—C10	118.85 (16)
N1—C2—C3	114.22 (15)	C8—C9—H9	120.6
N1—C2—H2A	108.7	C10—C9—H9	120.6
C3—C2—H2A	108.7	N2—C10—C9	121.89 (16)
N1—C2—H2B	108.7	N2—C10—C10i	115.54 (10)
C3—C2—H2B	108.7	C9—C10—C10i	122.56 (11)
C2—N1—C1—S1	4.9 (2)	N1—C4—C5—O2	85.17 (19)
C4—N1—C1—S1	−178.34 (12)	C10—N2—C6—C7	1.4 (3)
C2—N1—C1—S2	−173.68 (12)	Zn—N2—C6—C7	−168.48 (14)
C4—N1—C1—S2	3.1 (2)	N2—C6—C7—C8	−0.1 (3)
Zn—S1—C1—N1	−173.88 (14)	C6—C7—C8—C9	−1.1 (3)
Zn—S1—C1—S2	4.70 (9)	C7—C8—C9—C10	1.1 (3)
Zn—S2—C1—N1	173.85 (14)	C6—N2—C10—C9	−1.4 (3)
Zn—S2—C1—S1	−4.73 (9)	Zn—N2—C10—C9	169.27 (13)
C1—N1—C2—C3	−81.8 (2)	C6—N2—C10—C10i	179.44 (18)
C4—N1—C2—C3	101.31 (18)	Zn—N2—C10—C10i	−9.8 (2)
N1—C2—C3—O1	−80.47 (19)	C8—C9—C10—N2	0.2 (3)
C1—N1—C4—C5	86.7 (2)	C8—C9—C10—C10i	179.3 (2)
C2—N1—C4—C5	−96.50 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1	0.83 (2)	1.87 (2)	2.696 (2)	177 (3)
O1—H1O···O1W	0.83 (2)	1.88 (2)	2.7115 (19)	177 (2)
O1W—H1W···O2ii	0.83 (2)	1.91 (2)	2.7216 (19)	166 (2)
O1W—H2W···S2iii	0.83 (2)	2.45 (2)	3.2733 (15)	170 (2)
C7—H7···O1Wiv	0.95	2.58	3.517 (2)	171
C6—H6···S2v	0.95	2.81	3.490 (2)	129
C9—H9···S1vi	0.95	2.84	3.6857 (18)	149

[Zn(C6H12NOS2)2(C10H8N2)]	F(000) = 1208
Mr = 578.12	Dx = 1.422 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.4997 (11) Å	Cell parameters from 3771 reflections
b = 9.0027 (5) Å	θ = 2.3–27.5°
c = 15.5352 (8) Å	µ = 1.25 mm−1
β = 98.031 (5)°	T = 100 K
V = 2700.5 (3) Å3	Prism, light-yellow
Z = 4	0.25 × 0.25 × 0.15 mm

Agilent SuperNova Dual diffractometer with Atlas detector	3095 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2657 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.048
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.5°
ω scan	h = −21→25
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −11→10
Tmin = 0.737, Tmax = 1.000	l = −20→20
11190 measured reflections

Refinement on F2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.030	w = 1/[σ2(Fo2) + (0.0309P)2 + 1.2812P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.073	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.38 e Å−3
3095 reflections	Δρmin = −0.35 e Å−3
155 parameters

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.

	x	y	z	Uiso*/Ueq
Zn	0.5000	0.74113 (3)	0.7500	0.01278 (9)
S1	0.58946 (2)	0.56650 (5)	0.82428 (3)	0.01649 (12)
S2	0.58906 (2)	0.69208 (5)	0.65006 (3)	0.01671 (12)
O1	0.81368 (8)	0.48579 (17)	0.82921 (10)	0.0311 (4)
H1O	0.8403 (11)	0.416 (2)	0.8210 (17)	0.047*
N1	0.67544 (8)	0.47424 (17)	0.71467 (10)	0.0146 (3)
N2	0.46566 (8)	0.93220 (16)	0.67036 (10)	0.0138 (3)
C1	0.62467 (10)	0.56746 (19)	0.72861 (12)	0.0141 (4)
C2	0.70163 (10)	0.3630 (2)	0.78132 (12)	0.0193 (4)
H2A	0.7249	0.2822	0.7533	0.023*
H2B	0.6619	0.3191	0.8056	0.023*
C3	0.75234 (11)	0.4277 (2)	0.85548 (13)	0.0270 (5)
H3A	0.7288	0.5078	0.8837	0.032*
H3B	0.7651	0.3491	0.8994	0.032*
C4	0.69560 (10)	0.4583 (2)	0.62598 (12)	0.0182 (4)
H4	0.6837	0.5539	0.5946	0.022*
C5	0.65197 (11)	0.3372 (2)	0.57632 (13)	0.0256 (5)
H5A	0.6028	0.3617	0.5737	0.038*
H5B	0.6613	0.2419	0.6061	0.038*
H5C	0.6638	0.3301	0.5172	0.038*
C6	0.77272 (11)	0.4326 (3)	0.62649 (14)	0.0273 (5)
H6A	0.7989	0.5095	0.6617	0.041*
H6B	0.7836	0.4371	0.5668	0.041*
H6C	0.7854	0.3347	0.6513	0.041*
C7	0.43644 (10)	0.9239 (2)	0.58712 (12)	0.0169 (4)
H7	0.4245	0.8288	0.5631	0.020*
C8	0.42296 (10)	1.0474 (2)	0.53475 (12)	0.0208 (4)
H8	0.4014	1.0375	0.4763	0.025*
C9	0.44151 (11)	1.1856 (2)	0.56917 (13)	0.0242 (5)
H9	0.4330	1.2725	0.5346	0.029*
C10	0.47270 (11)	1.1956 (2)	0.65477 (13)	0.0212 (4)
H10	0.4863	1.2894	0.6795	0.025*
C11	0.48384 (10)	1.0669 (2)	0.70400 (11)	0.0151 (4)

	U11	U22	U33	U12	U13	U23
Zn	0.01357 (17)	0.01108 (16)	0.01328 (16)	0.000	0.00045 (12)	0.000
S1	0.0208 (3)	0.0152 (2)	0.0139 (2)	0.00390 (18)	0.00368 (19)	0.00164 (17)
S2	0.0166 (3)	0.0176 (3)	0.0158 (2)	0.00287 (19)	0.00185 (18)	0.00486 (18)
O1	0.0267 (9)	0.0260 (9)	0.0369 (9)	0.0060 (7)	−0.0081 (7)	−0.0051 (7)
N1	0.0148 (8)	0.0147 (8)	0.0139 (8)	0.0021 (6)	0.0006 (6)	−0.0012 (6)
N2	0.0136 (8)	0.0141 (8)	0.0135 (8)	−0.0003 (6)	0.0015 (6)	−0.0003 (6)
C1	0.0145 (10)	0.0128 (9)	0.0142 (9)	−0.0027 (7)	−0.0008 (7)	−0.0016 (7)
C2	0.0231 (11)	0.0150 (10)	0.0191 (10)	0.0072 (8)	0.0004 (8)	0.0017 (8)
C3	0.0301 (13)	0.0275 (12)	0.0208 (11)	0.0131 (9)	−0.0054 (9)	−0.0023 (9)
C4	0.0202 (10)	0.0195 (10)	0.0157 (10)	0.0018 (8)	0.0053 (8)	−0.0018 (7)
C5	0.0280 (12)	0.0292 (12)	0.0191 (10)	−0.0040 (9)	0.0020 (9)	−0.0073 (9)
C6	0.0200 (11)	0.0360 (13)	0.0266 (12)	0.0052 (9)	0.0051 (9)	−0.0051 (9)
C7	0.0150 (10)	0.0201 (10)	0.0152 (9)	−0.0009 (7)	0.0006 (7)	−0.0020 (7)
C8	0.0199 (11)	0.0300 (12)	0.0119 (9)	0.0049 (8)	0.0002 (8)	0.0041 (8)
C9	0.0296 (12)	0.0224 (11)	0.0211 (11)	0.0079 (9)	0.0058 (9)	0.0099 (8)
C10	0.0304 (12)	0.0127 (10)	0.0205 (10)	0.0032 (8)	0.0042 (9)	0.0015 (8)
C11	0.0166 (10)	0.0144 (9)	0.0149 (10)	0.0022 (7)	0.0041 (8)	−0.0007 (7)

Zn—N2i	2.1695 (15)	C3—H3B	0.9900
Zn—N2	2.1695 (15)	C4—C6	1.521 (3)
Zn—S1	2.5068 (5)	C4—C5	1.525 (3)
Zn—S1i	2.5068 (5)	C4—H4	1.0000
Zn—S2i	2.5247 (5)	C5—H5A	0.9800
Zn—S2	2.5247 (5)	C5—H5B	0.9800
S1—C1	1.7221 (19)	C5—H5C	0.9800
S2—C1	1.7301 (18)	C6—H6A	0.9800
O1—C3	1.417 (3)	C6—H6B	0.9800
O1—H1O	0.833 (10)	C6—H6C	0.9800
N1—C1	1.338 (2)	C7—C8	1.381 (3)
N1—C2	1.479 (2)	C7—H7	0.9500
N1—C4	1.492 (2)	C8—C9	1.382 (3)
N2—C7	1.340 (2)	C8—H8	0.9500
N2—C11	1.348 (2)	C9—C10	1.386 (3)
C2—C3	1.525 (3)	C9—H9	0.9500
C2—H2A	0.9900	C10—C11	1.388 (3)
C2—H2B	0.9900	C10—H10	0.9500
C3—H3A	0.9900	C11—C11i	1.479 (4)
N2i—Zn—N2	75.08 (8)	O1—C3—H3B	108.7
N2i—Zn—S1	95.47 (4)	C2—C3—H3B	108.7
N2—Zn—S1	154.06 (4)	H3A—C3—H3B	107.6
N2i—Zn—S1i	154.07 (4)	N1—C4—C6	113.45 (16)
N2—Zn—S1i	95.47 (4)	N1—C4—C5	109.62 (16)
S1—Zn—S1i	102.32 (2)	C6—C4—C5	112.05 (17)
N2i—Zn—S2i	88.40 (4)	N1—C4—H4	107.1
N2—Zn—S2i	107.78 (4)	C6—C4—H4	107.1
S1—Zn—S2i	95.822 (17)	C5—C4—H4	107.1
S1i—Zn—S2i	71.289 (16)	C4—C5—H5A	109.5
N2i—Zn—S2	107.78 (4)	C4—C5—H5B	109.5
N2—Zn—S2	88.39 (4)	H5A—C5—H5B	109.5
S1—Zn—S2	71.288 (16)	C4—C5—H5C	109.5
S1i—Zn—S2	95.822 (17)	H5A—C5—H5C	109.5
S2i—Zn—S2	159.86 (3)	H5B—C5—H5C	109.5
C1—S1—Zn	86.29 (6)	C4—C6—H6A	109.5
C1—S2—Zn	85.55 (6)	C4—C6—H6B	109.5
C3—O1—H1O	109.6 (19)	H6A—C6—H6B	109.5
C1—N1—C2	120.14 (15)	C4—C6—H6C	109.5
C1—N1—C4	120.40 (15)	H6A—C6—H6C	109.5
C2—N1—C4	118.15 (14)	H6B—C6—H6C	109.5
C7—N2—C11	118.51 (16)	N2—C7—C8	122.95 (17)
C7—N2—Zn	124.18 (12)	N2—C7—H7	118.5
C11—N2—Zn	116.66 (12)	C8—C7—H7	118.5
N1—C1—S1	121.98 (14)	C7—C8—C9	118.59 (18)
N1—C1—S2	121.71 (14)	C7—C8—H8	120.7
S1—C1—S2	116.28 (11)	C9—C8—H8	120.7
N1—C2—C3	113.23 (16)	C8—C9—C10	119.06 (18)
N1—C2—H2A	108.9	C8—C9—H9	120.5
C3—C2—H2A	108.9	C10—C9—H9	120.5
N1—C2—H2B	108.9	C9—C10—C11	119.24 (18)
C3—C2—H2B	108.9	C9—C10—H10	120.4
H2A—C2—H2B	107.7	C11—C10—H10	120.4
O1—C3—C2	114.06 (17)	N2—C11—C10	121.63 (17)
O1—C3—H3A	108.7	N2—C11—C11i	115.33 (10)
C2—C3—H3A	108.7	C10—C11—C11i	123.03 (11)
C2—N1—C1—S1	1.8 (2)	C1—N1—C4—C5	−89.1 (2)
C4—N1—C1—S1	168.55 (13)	C2—N1—C4—C5	77.9 (2)
C2—N1—C1—S2	−176.25 (13)	C11—N2—C7—C8	−1.2 (3)
C4—N1—C1—S2	−9.5 (2)	Zn—N2—C7—C8	−171.67 (14)
Zn—S1—C1—N1	−170.98 (15)	N2—C7—C8—C9	1.2 (3)
Zn—S1—C1—S2	7.21 (9)	C7—C8—C9—C10	−0.2 (3)
Zn—S2—C1—N1	171.03 (15)	C8—C9—C10—C11	−0.7 (3)
Zn—S2—C1—S1	−7.16 (9)	C7—N2—C11—C10	0.3 (3)
C1—N1—C2—C3	−79.6 (2)	Zn—N2—C11—C10	171.46 (14)
C4—N1—C2—C3	113.39 (18)	C7—N2—C11—C11i	−179.62 (19)
N1—C2—C3—O1	−62.3 (2)	Zn—N2—C11—C11i	−8.5 (3)
C1—N1—C4—C6	144.80 (18)	C9—C10—C11—N2	0.7 (3)
C2—N1—C4—C6	−48.2 (2)	C9—C10—C11—C11i	−179.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···S2ii	0.84 (2)	2.45 (2)	3.2437 (16)	160 (2)
C5—H5B···O1ii	0.98	2.54	3.512 (2)	175
C9—H9···S2iii	0.95	2.86	3.550 (2)	130