Two Zn^II coordination complexes assembled by tri­thio­cyanuric acid and two different N-donor auxiliary ligands

The dipyridyl-type building blocks 4-amino-3,5-bis­(pyridin-3-yl)-1,2,4-triazole (3-bpt) and 4,4′-bi­pyridine (bpy) have been used to assemble with Zn^II in the presence of tri­thio­cyanuric acid (ttcH₃) to afford two coordination compounds, namely bis­[4-amino-3,5-bis­(pyridin-3-yl)-1,2,4-triazole-κN³]bis­(trithio­cyanurato-κ²N,S)zinc(II), [Zn(C₃H₂N₃S₃)₂(C₁₂H₁₀N₆)₂]·2H₂O, (1), and catena-poly[[[bis­(tri­thio­cyanurato-κ²N,S)zinc(II)]-μ-4,4′-bi­pyridine-κ²N:N′] 4,4′-bi­pyridine mono­solvate], {[Zn₂(C₃H₂N₃S₃)₄(C₁₀H₈N₂)₃]·C₁₀H₈N₂}_n, (2). Single-crystal X-ray analysis indicates that complex (1) is a mononuclear structure, while complex (2) presents a one-dimensional chain coordination motif. In both complexes, the central Zn^II cation adopts an octa­hedral geometry, coordinated by four N- and two S-donor atoms. Notably, tri­thio­cyanurate (ttcH₂⁻) adopts the same bidentate chelating coordination mode in each complex and exists in the thione tautomeric form. The 3-bpt co-ligand in (1) adopts a monodentate coordination mode and serves as a terminal pendant ligand, whereas the 4,4′-bi­pyridine (bpy) ligand in (2) adopts a bidentate–bridging coordination mode. The different coordination characters of the different N-donor auxiliary ligands lead to structural diversity for complexes (1) and (2). Further analysis indicates that the resultant three-dimensional supra­molecular networks for (1) and (2) arise through inter­molecular N—H...S and N—H...N hydrogen bonds. Both complexes have been further characterized by FT–IR spectroscopy and elemental analyses.

S1. Introduction

During the past decade, the design of new coordination complexes has attracted ever-increasing attention in the fields of coordination chemistry and crystal engineering, the main aim being to discover new crystalline materials with useful functionality (Férey et al., 2005; Tanaka et al., 2010; Kobayashi et al., 2010; Yoon et al., 2012; Chen et al., 2008). The type of coordination polymer obtained is sensitive to many factors, including the type of organic ligand, the metal ion, the solvent, the counter-anion, the pH range etc. (Long, 2010; Moulton & Zaworotko, 2001; Li & Du, 2011; Du et al., 2009). Among these factors, the choice of organic ligands as building blocks is often the key factor in the final structures of coordination polymers.

To date, much research effort has been devoted to the coordination chemistry of pyridyl-based and polycarboxyl­ate ligands, for example 2,2'-bi­pyridyl, 4,4'-bi­pyridyl (bpy), benzene-1,4-di­carb­oxy­lic acid and benzene-1,3,5-tri­carb­oxy­lic acid (Du et al., 2004; Daiguebonne et al., 2006; Biradha et al., 2006). Recently, the angular di­pyridyl ligand 4-amino-3,5-bis­(pyridin-3-yl)-1,2,4-triazole (3-bpt), which can adopt three different conformations depending on the conditions (see Scheme 1), has been chosen to assemble with metal salts by ourselves and many other researchers (Du et al., 2008; Jiang et al., 2012; Yang et al., 2013). However, thio­cyanuric acid (ttcH₃), which can exist in either the thiol or thione tautomeric forms (see Scheme 2), has not been studied extensively in the field of metal–organic complexes compared with the above ligands. In fact, complexes involving ttcH₃ have potential applications in industry, biology, pharmacology and analytical chemistry, because anions of ttcH₃ have been used widely to remove heavy metals (Ag⁺, Hg²⁺, Cd²⁺, Pd²⁺ and Cu²⁺) from waste water (Matlock et al., 2001; Henke & Atwood, 1998; Henke et al., 2000). The ttcH₃ molecule has three S- and three N-donor atoms available and can behave as either a chelating or a bridging ligand (Mahon et al., 2003; Chan et al., 1996; Hunks et al., 1999). Moreover, the multiplicity of S and N atoms can provide potential sites for hydrogen-bonding inter­actions, which may further extend the dimensions of the crystalline architectures. Considering all the factors stated above, we present the results of the synthesis and characterization of two mixed-ligand complexes involving ttcH₃ with two kinds of di­pyridyl-type ligand.

In this work, we have used 4-amino-3,5-bis­(pyridin-3-yl)-1,2,4-triazole (3-bpt) and 4,4'-bi­pyridine (bpy), respectively, in combination with ttcH₃ to prepare two new Zn^II coordination complexes, namely, [Zn(ttcH₂)₂(3-bpt)₂]·2H₂O, (1), and {[Zn₂(ttcH₂)₄(bpy)₃]·bpy}_n, (2) (Scheme 3). Complex (1) is mononuclear, while (2) is a one-dimensional coordination polymer. These complexes have also been characterised using FT–IR spectroscopy and elemental analyses.

S2. Experimental

S2.1. Synthesis and crystallization

A methanol (5 ml) solution of 4-amino-3,5-bis­(pyridin-3-yl)-1,2,4-triazole (3-bpt) (12 mg, 0.05 mmol) was added to an aqueous solution (10 ml) of Zn(NO₃)₂·6H₂O (15 mg, 0.05 mmol) with continuous stirring for 10 min. A solution of tri­thio­cyanuric acid (ttcH₃) (9 mg, 0.05 mmol) in methanol (5 ml) was then added dropwise. The mixture was stirred at room temperature for 30 min, filtered, and the resulting solution left to stand at room temperature. Colourless block-shaped crystals of (1) were obtained by slow evaporation of the solvents after ca 2 d (yield 53%, 12.5 mg, based on 3-bpt). Analysis, calculated for C₃₀H₂₈N₁₈O₂S₆Zn, (1): C 38.73, H 3.03, N 27.10%; found: C 38.69, H 3.01, N 27.08%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3393 (b), 3124 (b), 1569 (s), 1498 (s), 1462 (m), 1412 (vs), 1360 (m), 1284 (w), 1244 (vs), 1183 (m), 1158 (vs), 990 (w), 883 (w), 817 (w), 700 (w), 634 (w), 507 (w), 457 (m).

The synthesis of (2) was similar to (1) except that 3-bpt was replaced by bpy (7.8 mg, 0.05 mmol), affording colourless block crystals of (2) in ca 40% yield (7.3 mg, based on bpy). Analysis, calculated for C₂₆H₂₀N₁₀S₆Zn, (2): C 42.76, H 2.76, N 19.18%; found: C 42.72, H 2.73, N 19.17%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3052 (b), 2907 (b), 1898 (b), 1600 (w), 1544 (vs), 1449 (m), 1365 (vs), 1255 (m), 1213 (s), 1135 (vs), 1057 (w), 999 (w), 806 (vs), 670 (w), 612 (s), 456 (vs).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were initially located in a difference Fourier map and then refined using a riding model, with C—H = 0.93, N—H = 0.89 and O—H = 0.85 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(N,O).

S3. Results and discussion

Single-crystal X-ray diffraction reveals that complex (1) adopts a mononuclear structure. The asymmetric coordination unit of (1) consists of one half-occupied Zn^II cation, one 3-bpt ligand, one ttcH₂^- anion existing in the thione tautomeric form and one solvent water molecule. As can be seen in Fig. 1, the central Zn^II is coordinated to four N atoms from two pyridyl rings of 3-bpt ligands and two ttcH₂^- anions, and two S-donor atoms from two monovalent ttcH₂^- anions, exhibiting a distorted o­cta­hedral geometry. The triazine ring of ttcH₂^- forms strong bonds with the Zn^II cation, as indicated by the bond distances [Zn—N1 = 2.1476 (15) Å and Zn—S1 = 2.5925 (6) Å; Table 2]. The 3-bpt ligand, showing an uncommon cisiod-II conformation (see Scheme 1), adopts a monodentate coordination mode, while the ttcH₂^- ligand adopts a bidentate–chelating coordination mode. For complex (1), adjacent mononuclear units are extended into a one-dimensional tubular array by N3—H3'···N9^v hydrogen bonds [symmetry code: (v) x + 1, y, z - 1] between the uncoordinated pyridyl ring of 3-bpt and the triazine ring of ttcH₂^-. In addition, adjacent one-dimensional arrays are inter­connected via N8—H8''···S3^vi [symmetry code: (vi) -x + 2, -y + 2, -z + 1] hydrogen bonds between the amino group of 3-bpt and uncoordinated S atoms of ttcH₂^-, resulting in a two-dimensional layered network (Fig. 2). The parallel two-dimensional layers are further extended via N2—H2'···S2^iv hydrogen bonds [symmetry code: (iv) -x + 1, -y + 2, -z + 1] between triazine and thione groups of ttcH₂^-, to give a three-dimensional supra­molecular network (Fig. 3). The structure of (1) is further stabilized by hydrogen-bonding inter­actions involving the solvent water molecules and the amino and triazole groups of 3-bpt via N8—H8'···O1, O1—H1A···N6 and O1—H1B···N5 hydrogen bonds (see Table 3).

Compound (2) crystallizes in the monoclinic C2/c space group, and is made up of a neutral Zn^II coordination unit and one uncoordinated bpy molecule. As can be seen in Fig. 4, the coordination polyhedron around the Zn^II cation has o­cta­hedral geometry, coordinated by four N atoms from the triazine and pyridyl rings of bpy, and two S atoms of ttcH₂^- existing in the thione tautomeric form. The ttcH₂^- ligands adopt bidentate–chelating coordination modes. The Zn—N bond lengths are in the normal range [2.141 (2)–2.187 (3) Å] and the Zn—S bond length is 2.600 (1) Å (Table 4). Adjacent Zn^II centres are extended to afford a one-dimensional polymeric chain via the bridging bpy ligand, with a Zn···Zn distance of 11.39 (1) Å. Adjacent one-dimensional chains are inter­connected via N3—H3···S2ⁱⁱ hydrogen bonds [symmetry code: (ii) -x + 1/2, -y - 1/2, -z + 1] between the thione and triazine groups of ttcH₂^-, producing a two-dimensional layered hydrogen-bonded network with (4,4) topology (Fig. 5). These two-dimensional sheets are further linked by the connection of inter­calated bpy in the crystalline lattice via N2—H2···N6ⁱ hydrogen bonds [symmetry code: (i) x - 1/2, -y + 1/2, z - 1/2] between the pyridyl ring of bpy and the triazine ring of ttcH₂^- (Fig. 6 and Table 5), resulting in an extended three-dimensional net.

From the above observations, it can be seen that self-assembly of ttcH₃ and 3-bpt/bpy with Zn^II under similar reaction conditions results in two kinds of coordination motif, viz. mononuclear for (1) and one-dimensional for (2). The structural difference can mainly be attributed to the introduction of different N-donor auxiliary ligands which show diverse coordination modes. In mononuclear structure (1), the 3-bpt ligand serves as the monodentate terminal around the metal centre, while the co-ligand bpy in (2) adopts a bidentate–bridging coordination mode. The central metal ions adopt the same o­cta­hedral geometry and the ttcH₂^- anions show the same bidentate–chelating coordination pattern in complexes (1) and (2). All the Zn—-S [2.5925 (6) and 2.600 (1) Å] and Zn—N [2.141 (2)–2.187 (3) Å] bond lengths are in normal ranges [Standard reference?]. In addition, both (1) and (2) are extended into three-dimensional supra­molecular networks via multiple hydrogen-bond inter­actions. Notably, the presence of bpy in the crystalline lattice plays an important role in directing the resultant three-dimensional supra­molecular net for (2).

In summary, two Zn^II coordination complexes have been assembled based on ttcH₃ and two di­pyridyl-type building blocks, 3-bpt and bpy, affording two types of coordination structure, mononuclear and one-dimensional, respectively. This structural variation may arise from the different coordination modes of the N-donor auxiliary ligand (monodentate for 3-bpt and bidentate-bridging for bpy). Notably, ttcH₂^- adopts the same bidentate chelating coordination mode [in each complex?], existing in the thione tautomeric form. The results prove that the choice of different organic co-ligands plays an important role in preparing new crystalline materials. We are currently extending this research to assemble complexes using ttcH₃ and different building blocks to enrich such inorganic–organic hybrid materials.

Related literature

For related literature, see: Biradha et al. (2006); Chan et al. (1996); Chen et al. (2008); Daiguebonne et al. (2006); Du et al. (2004, 2008, 2009); Férey et al. (2005); Henke & Atwood (1998); Henke et al. (2000); Hunks et al. (1999); Jiang et al. (2012); Kobayashi et al. (2010); Li & Du (2011); Long (2010); Mahon et al. (2003); Matlock et al. (2001); Moulton & Zaworotko (2001); Tanaka et al. (2010); Yang et al. (2013); Yoon et al. (2012).

Computing details

Data collection: CrystalClear (Rigaku, 2009) for (1); SMART (Bruker, 2002) for (2). Cell refinement: CrystalClear (Rigaku, 2009) for (1); SMART (Bruker, 2002) for (2). Data reduction: CrystalClear (Rigaku, 2009) for (1); SAINT (Bruker, 2002) for (2). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the coordination environment of the Zn^II cation of complex (1), with the atom-numbering scheme. H atoms have been omitted for clarity. [Symmetry code: (A) -x + 2, -y + 1, -z + 1.]
	Fig. 2. The two-dimensional network of complex (1), constructed via N3—H3'···N9^v and N8—H8''···S3^vi hydrogen bonds (red dashed lines?). [Symmetry codes: (v) x + 1, y, z - 1; (vi) -x + 2, -y + 2, -z + 1.]
	Fig. 3. The resultant three-dimensional supramolecular network of complex (1), connected via N2—H2'···S2^iv hydrogen bonds (red dashed lines?). [Symmetry code: (iv) -x + 1, -y + 2, -z + 1.]
	Fig. 4. A local view of the coordination environment of the Zn^II cation of complex (2), with the atom-numbering scheme. H atoms have been omitted for clarity. [Symmetry codes: (A) -x, y, -z + 1/2; (B) x, y - 1, z; (C) -x, -y + 1, -z + 2.]
	Fig. 5. The two-dimensional hydrogen-bonding network of complex (2), showing N3—H3···S2^ii hydrogen bonds (red dashed lines?). [Symmetry code: (ii) -x + 1/2, -y - 1/2, -z + 1.]
	Fig. 6. The three-dimensional supramolecular network of complex (2), connected via the intercalated bpy ligands in the crystalline lattice through N2—H2···N6^i hydrogen bonds (red dashed lines?). [Symmetry code:(i) x - 1/2, -y + 1/2, z - 1/2.]

(1) Bis[4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole-κN³]bis(trithiocyanurato-κ²N,S)zinc(II)

Crystal data

[Zn(C3H2N3S3)2(C12H10N6)2]·2H2O	Z = 1
Mr = 930.43	F(000) = 476
Triclinic, P1	Dx = 1.581 Mg m^−3
a = 7.7509 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8253 (1) Å	Cell parameters from 2767 reflections
c = 12.5824 (11) Å	θ = 3.0–27.5°
α = 77.543 (16)°	µ = 1.01 mm^−1
β = 81.089 (18)°	T = 294 K
γ = 72.256 (16)°	Platelet, colourless
V = 977.32 (10) Å^3	0.25 × 0.09 × 0.03 mm

Data collection

Rigaku Mercury 375R diffractometer	4460 independent reflections
Radiation source: fine-focus sealed tube	3822 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
profile data from ω scans	h = −10→10
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −14→14
Tmin = 0.787, Tmax = 0.970	l = −16→16
10320 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0269P)^2 + 0.222P] where P = (Fo^2 + 2Fc^2)/3
4460 reflections	(Δ/σ)max = 0.001
283 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.58 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	1.0000	0.5000	0.5000	0.02827 (10)
N1	0.90763 (19)	0.71110 (14)	0.45831 (12)	0.0253 (3)
N2	0.7712 (2)	0.93764 (16)	0.43796 (13)	0.0290 (3)
H2'	0.682 (3)	1.005 (2)	0.4494 (16)	0.026 (5)*
N3	1.0662 (2)	0.86390 (16)	0.36717 (13)	0.0296 (3)
H3'	1.159 (3)	0.884 (2)	0.3354 (19)	0.043 (7)*
N4	1.0848 (2)	0.52174 (16)	0.64929 (12)	0.0288 (3)
N5	0.7123 (2)	0.62519 (18)	0.92162 (14)	0.0369 (4)
N6	0.6065 (2)	0.69480 (19)	0.99985 (14)	0.0374 (4)
N7	0.8535 (2)	0.75829 (16)	0.95354 (12)	0.0278 (3)
N8	0.9760 (3)	0.8347 (2)	0.94497 (18)	0.0391 (4)
H8'	1.073 (4)	0.776 (3)	0.982 (2)	0.057 (8)*
H8''	0.994 (3)	0.859 (3)	0.883 (2)	0.044 (7)*
N9	0.3782 (2)	0.92061 (19)	1.24065 (14)	0.0386 (4)
O1	0.2645 (2)	0.6503 (2)	0.06706 (16)	0.0519 (4)
H1A	0.368 (5)	0.659 (4)	0.049 (3)	0.089 (11)*
H1B	0.276 (5)	0.564 (4)	0.085 (3)	0.106 (14)*
S1	1.24443 (6)	0.60758 (5)	0.38892 (4)	0.03241 (12)
S2	0.56113 (6)	0.78511 (5)	0.53560 (4)	0.03580 (13)
S3	0.93140 (7)	1.12356 (5)	0.34464 (4)	0.03862 (13)
C1	1.0623 (2)	0.73607 (18)	0.40536 (14)	0.0261 (4)
C2	0.7575 (2)	0.81119 (18)	0.47446 (14)	0.0254 (3)
C3	0.9230 (2)	0.96850 (18)	0.38512 (14)	0.0275 (4)
C4	1.2610 (3)	0.4899 (2)	0.66538 (16)	0.0359 (4)
H4	1.3476	0.4483	0.6148	0.043*
C5	1.3190 (3)	0.5164 (2)	0.75407 (17)	0.0416 (5)
H5	1.4426	0.4942	0.7622	0.050*
C6	1.1914 (3)	0.5765 (2)	0.83083 (15)	0.0366 (4)
H6	1.2277	0.5955	0.8911	0.044*
C7	1.0085 (2)	0.60788 (18)	0.81607 (14)	0.0274 (4)
C8	0.9610 (2)	0.57932 (18)	0.72355 (14)	0.0279 (4)
H8	0.8384	0.6011	0.7130	0.033*
C9	0.8606 (2)	0.66347 (19)	0.89558 (14)	0.0290 (4)
C10	0.6921 (2)	0.77514 (19)	1.01836 (14)	0.0284 (4)
C11	0.6178 (2)	0.8636 (2)	1.09825 (14)	0.0286 (4)
C12	0.6829 (3)	0.9658 (2)	1.10905 (18)	0.0391 (5)
H12	0.7856	0.9811	1.0657	0.047*
C13	0.5929 (3)	1.0449 (2)	1.18517 (19)	0.0443 (5)
H13	0.6347	1.1139	1.1936	0.053*
C14	0.4411 (3)	1.0204 (2)	1.24816 (17)	0.0397 (5)
H14	0.3798	1.0752	1.2978	0.048*
C15	0.4651 (3)	0.8448 (2)	1.16783 (16)	0.0368 (5)
H15	0.4220	0.7751	1.1628	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03719 (18)	0.02164 (16)	0.02543 (15)	−0.00764 (13)	0.00109 (11)	−0.00688 (12)
N1	0.0232 (7)	0.0197 (7)	0.0294 (7)	−0.0025 (6)	0.0049 (6)	−0.0071 (6)
N2	0.0245 (7)	0.0199 (7)	0.0366 (8)	−0.0012 (6)	0.0037 (6)	−0.0044 (7)
N3	0.0270 (8)	0.0231 (8)	0.0343 (8)	−0.0068 (7)	0.0086 (6)	−0.0047 (7)
N4	0.0308 (8)	0.0269 (8)	0.0264 (7)	−0.0037 (7)	0.0023 (6)	−0.0097 (6)
N5	0.0411 (9)	0.0391 (10)	0.0353 (8)	−0.0176 (8)	0.0126 (7)	−0.0192 (8)
N6	0.0387 (9)	0.0441 (10)	0.0361 (8)	−0.0205 (8)	0.0133 (7)	−0.0207 (8)
N7	0.0280 (8)	0.0297 (8)	0.0278 (7)	−0.0110 (7)	0.0062 (6)	−0.0117 (6)
N8	0.0360 (10)	0.0451 (11)	0.0429 (10)	−0.0214 (9)	0.0130 (8)	−0.0198 (9)
N9	0.0382 (9)	0.0417 (10)	0.0367 (9)	−0.0128 (8)	0.0128 (7)	−0.0181 (8)
O1	0.0420 (9)	0.0588 (12)	0.0632 (11)	−0.0231 (9)	−0.0007 (8)	−0.0187 (10)
S1	0.0244 (2)	0.0265 (2)	0.0402 (3)	−0.00143 (19)	0.00929 (18)	−0.0102 (2)
S2	0.0242 (2)	0.0254 (2)	0.0525 (3)	−0.00490 (19)	0.01038 (19)	−0.0090 (2)
S3	0.0448 (3)	0.0212 (2)	0.0451 (3)	−0.0098 (2)	0.0075 (2)	−0.0032 (2)
C1	0.0265 (8)	0.0227 (9)	0.0261 (8)	−0.0044 (7)	0.0038 (6)	−0.0065 (7)
C2	0.0251 (8)	0.0218 (8)	0.0267 (8)	−0.0031 (7)	0.0011 (6)	−0.0063 (7)
C3	0.0299 (9)	0.0234 (9)	0.0268 (8)	−0.0060 (7)	0.0026 (7)	−0.0050 (7)
C4	0.0295 (9)	0.0397 (11)	0.0328 (9)	0.0016 (8)	0.0015 (7)	−0.0138 (9)
C5	0.0277 (9)	0.0530 (14)	0.0377 (10)	0.0042 (9)	−0.0033 (8)	−0.0170 (10)
C6	0.0373 (10)	0.0434 (12)	0.0276 (9)	−0.0037 (9)	−0.0035 (8)	−0.0137 (9)
C7	0.0319 (9)	0.0239 (9)	0.0242 (8)	−0.0064 (7)	0.0060 (7)	−0.0078 (7)
C8	0.0278 (9)	0.0255 (9)	0.0285 (8)	−0.0045 (7)	0.0030 (7)	−0.0092 (7)
C9	0.0329 (9)	0.0288 (9)	0.0245 (8)	−0.0085 (8)	0.0044 (7)	−0.0081 (7)
C10	0.0287 (9)	0.0301 (9)	0.0270 (8)	−0.0104 (8)	0.0060 (7)	−0.0095 (8)
C11	0.0272 (8)	0.0309 (9)	0.0269 (8)	−0.0063 (8)	0.0035 (7)	−0.0107 (8)
C12	0.0371 (11)	0.0447 (12)	0.0420 (11)	−0.0188 (10)	0.0099 (8)	−0.0205 (10)
C13	0.0457 (12)	0.0473 (13)	0.0497 (12)	−0.0209 (11)	0.0060 (10)	−0.0253 (11)
C14	0.0425 (11)	0.0432 (12)	0.0356 (10)	−0.0095 (10)	0.0060 (8)	−0.0222 (9)
C15	0.0383 (10)	0.0369 (11)	0.0383 (10)	−0.0160 (9)	0.0124 (8)	−0.0171 (9)

Geometric parameters (Å, º)

Zn1—N1^i	2.1476 (15)	N9—C14	1.339 (3)
Zn1—N1	2.1476 (15)	O1—H1A	0.83 (4)
Zn1—N4	2.1640 (15)	O1—H1B	0.89 (4)
Zn1—N4^i	2.1640 (15)	S1—C1	1.6754 (18)
Zn1—S1	2.5925 (6)	S2—C2	1.6712 (18)
Zn1—S1^i	2.5925 (6)	S3—C3	1.6640 (19)
N1—C2	1.350 (2)	C4—C5	1.379 (3)
N1—C1	1.352 (2)	C4—H4	0.9300
N2—C3	1.356 (2)	C5—C6	1.385 (3)
N2—C2	1.378 (2)	C5—H5	0.9300
N2—H2'	0.86 (2)	C6—C7	1.386 (3)
N3—C3	1.354 (2)	C6—H6	0.9300
N3—C1	1.371 (2)	C7—C8	1.394 (2)
N3—H3'	0.83 (2)	C7—C9	1.470 (2)
N4—C8	1.339 (2)	C8—H8	0.9300
N4—C4	1.340 (2)	C10—C11	1.469 (2)
N5—C9	1.310 (2)	C11—C12	1.387 (3)
N5—N6	1.379 (2)	C11—C15	1.399 (2)
N6—C10	1.319 (2)	C12—C13	1.385 (3)
N7—C9	1.366 (2)	C12—H12	0.9300
N7—C10	1.368 (2)	C13—C14	1.377 (3)
N7—N8	1.416 (2)	C13—H13	0.9300
N8—H8'	0.94 (3)	C14—H14	0.9300
N8—H8''	0.77 (3)	C15—H15	0.9300
N9—C15	1.328 (2)
N1^i—Zn1—N1	180	N1—C2—S2	122.13 (14)
N1^i—Zn1—N4	91.55 (6)	N2—C2—S2	120.54 (13)
N1—Zn1—N4	88.45 (6)	N3—C3—N2	114.99 (16)
N1^i—Zn1—N4^i	88.45 (6)	N3—C3—S3	122.65 (14)
N1—Zn1—N4^i	91.55 (6)	N2—C3—S3	122.36 (14)
N4—Zn1—N4^i	180	N4—C4—C5	122.53 (17)
N1^i—Zn1—S1	114.22 (4)	N4—C4—H4	118.7
N1—Zn1—S1	65.78 (4)	C5—C4—H4	118.7
N4—Zn1—S1	89.26 (4)	C4—C5—C6	119.33 (18)
N4^i—Zn1—S1	90.74 (4)	C4—C5—H5	120.3
N1^i—Zn1—S1^i	65.78 (4)	C6—C5—H5	120.3
N1—Zn1—S1^i	114.22 (4)	C5—C6—C7	118.69 (18)
N4—Zn1—S1^i	90.74 (4)	C5—C6—H6	120.7
N4^i—Zn1—S1^i	89.26 (4)	C7—C6—H6	120.7
S1—Zn1—S1^i	180	C6—C7—C8	118.52 (16)
C2—N1—C1	120.42 (16)	C6—C7—C9	123.61 (16)
C2—N1—Zn1	139.52 (12)	C8—C7—C9	117.79 (16)
C1—N1—Zn1	99.97 (11)	N4—C8—C7	122.60 (17)
C3—N2—C2	124.78 (16)	N4—C8—H8	118.7
C3—N2—H2'	113.9 (13)	C7—C8—H8	118.7
C2—N2—H2'	121.3 (13)	N5—C9—N7	109.66 (15)
C3—N3—C1	122.63 (15)	N5—C9—C7	122.94 (17)
C3—N3—H3'	114.3 (18)	N7—C9—C7	127.39 (16)
C1—N3—H3'	122.9 (18)	N6—C10—N7	108.60 (16)
C8—N4—C4	118.33 (16)	N6—C10—C11	122.64 (16)
C8—N4—Zn1	119.88 (13)	N7—C10—C11	128.76 (16)
C4—N4—Zn1	121.51 (12)	C12—C11—C15	117.22 (17)
C9—N5—N6	107.42 (15)	C12—C11—C10	125.83 (17)
C10—N6—N5	108.25 (15)	C15—C11—C10	116.93 (17)
C9—N7—C10	106.06 (15)	C13—C12—C11	119.17 (18)
C9—N7—N8	128.96 (15)	C13—C12—H12	120.4
C10—N7—N8	124.78 (15)	C11—C12—H12	120.4
N7—N8—H8'	102.6 (16)	C14—C13—C12	119.27 (19)
N7—N8—H8''	104.7 (19)	C14—C13—H13	120.4
H8'—N8—H8''	118 (3)	C12—C13—H13	120.4
C15—N9—C14	117.99 (17)	N9—C14—C13	122.54 (19)
H1A—O1—H1B	108 (4)	N9—C14—H14	118.7
C1—S1—Zn1	76.12 (6)	C13—C14—H14	118.7
N1—C1—N3	119.73 (16)	N9—C15—C11	123.78 (18)
N1—C1—S1	118.08 (13)	N9—C15—H15	118.1
N3—C1—S1	122.19 (13)	C11—C15—H15	118.1
N1—C2—N2	117.33 (15)
N4—Zn1—N1—C2	−87.69 (19)	C8—N4—C4—C5	−1.2 (3)
N4^i—Zn1—N1—C2	92.31 (19)	Zn1—N4—C4—C5	172.61 (17)
S1—Zn1—N1—C2	−177.6 (2)	N4—C4—C5—C6	0.9 (3)
S1^i—Zn1—N1—C2	2.4 (2)	C4—C5—C6—C7	0.2 (3)
N4—Zn1—N1—C1	88.34 (11)	C5—C6—C7—C8	−1.0 (3)
N4^i—Zn1—N1—C1	−91.66 (11)	C5—C6—C7—C9	175.7 (2)
S1—Zn1—N1—C1	−1.54 (9)	C4—N4—C8—C7	0.4 (3)
S1^i—Zn1—N1—C1	178.46 (9)	Zn1—N4—C8—C7	−173.55 (13)
N1^i—Zn1—N4—C8	−117.30 (14)	C6—C7—C8—N4	0.7 (3)
N1—Zn1—N4—C8	62.70 (14)	C9—C7—C8—N4	−176.16 (17)
S1—Zn1—N4—C8	128.50 (14)	N6—N5—C9—N7	−1.0 (2)
S1^i—Zn1—N4—C8	−51.50 (14)	N6—N5—C9—C7	178.41 (18)
N1^i—Zn1—N4—C4	68.96 (16)	C10—N7—C9—N5	0.8 (2)
N1—Zn1—N4—C4	−111.04 (16)	N8—N7—C9—N5	−174.2 (2)
S1—Zn1—N4—C4	−45.25 (15)	C10—N7—C9—C7	−178.61 (19)
S1^i—Zn1—N4—C4	134.75 (15)	N8—N7—C9—C7	6.4 (3)
C9—N5—N6—C10	0.9 (2)	C6—C7—C9—N5	−138.1 (2)
N1^i—Zn1—S1—C1	−178.74 (8)	C8—C7—C9—N5	38.6 (3)
N1—Zn1—S1—C1	1.26 (8)	C6—C7—C9—N7	41.3 (3)
N4—Zn1—S1—C1	−87.37 (8)	C8—C7—C9—N7	−142.05 (19)
N4^i—Zn1—S1—C1	92.63 (8)	N5—N6—C10—N7	−0.4 (2)
C2—N1—C1—N3	−0.5 (3)	N5—N6—C10—C11	−179.53 (18)
Zn1—N1—C1—N3	−177.47 (14)	C9—N7—C10—N6	−0.2 (2)
C2—N1—C1—S1	179.48 (13)	N8—N7—C10—N6	175.0 (2)
Zn1—N1—C1—S1	2.46 (15)	C9—N7—C10—C11	178.86 (19)
C3—N3—C1—N1	3.6 (3)	N8—N7—C10—C11	−5.9 (3)
C3—N3—C1—S1	−176.37 (14)	N6—C10—C11—C12	−168.2 (2)
Zn1—S1—C1—N1	−2.07 (13)	N7—C10—C11—C12	12.8 (3)
Zn1—S1—C1—N3	177.86 (16)	N6—C10—C11—C15	10.2 (3)
C1—N1—C2—N2	−1.9 (3)	N7—C10—C11—C15	−168.8 (2)
Zn1—N1—C2—N2	173.55 (13)	C15—C11—C12—C13	−1.4 (3)
C1—N1—C2—S2	177.83 (13)	C10—C11—C12—C13	177.0 (2)
Zn1—N1—C2—S2	−6.7 (3)	C11—C12—C13—C14	−0.1 (4)
C3—N2—C2—N1	1.5 (3)	C15—N9—C14—C13	−1.3 (3)
C3—N2—C2—S2	−178.25 (14)	C12—C13—C14—N9	1.5 (4)
C1—N3—C3—N2	−3.9 (3)	C14—N9—C15—C11	−0.4 (3)
C1—N3—C3—S3	176.60 (14)	C12—C11—C15—N9	1.7 (3)
C2—N2—C3—N3	1.3 (3)	C10—C11—C15—N9	−176.9 (2)
C2—N2—C3—S3	−179.14 (14)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8′···O1^ii	0.94 (3)	1.96 (3)	2.892 (3)	177 (2)
O1—H1A···N6^iii	0.83 (4)	1.98 (4)	2.807 (2)	175 (4)
O1—H1B···N5^iv	0.89 (4)	2.05 (4)	2.906 (3)	163 (4)
N2—H2′···S2^v	0.86 (2)	2.49 (2)	3.3478 (17)	173.6 (18)
N3—H3′···N9^vi	0.83 (2)	2.01 (2)	2.837 (2)	172 (2)
N8—H8′′···S3^vii	0.77 (3)	2.81 (3)	3.560 (2)	165 (3)

Symmetry codes: (ii) x+1, y, z+1; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+1; (vi) x+1, y, z−1; (vii) −x+2, −y+2, −z+1.

(2) catena-Poly[[[bis(trithiocyanurato-κ²N,S)zinc(II)]-µ-4,4'-bipyridine-κ²N:N'] 4,4'-bipyridine monosolvate]

Crystal data

[Zn(C3H2N3S3)2(C10H8N2)]·C10H8N2	F(000) = 1488
Mr = 730.25	Dx = 1.658 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.3778 (10) Å	Cell parameters from 3176 reflections
b = 11.3937 (9) Å	θ = 2.4–28.3°
c = 19.2967 (14) Å	µ = 1.31 mm^−1
β = 96.044 (1)°	T = 173 K
V = 2924.9 (4) Å^3	Block, colourless
Z = 4	0.14 × 0.08 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3633 independent reflections
Radiation source: fine-focus sealed tube	3159 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −17→14
Tmin = 0.838, Tmax = 0.950	k = −12→15
10681 measured reflections	l = −25→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 9.7684P] where P = (Fo^2 + 2Fc^2)/3
3633 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.73 e Å^−3
146 restraints	Δρmin = −1.02 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.0000	−0.25751 (4)	0.2500	0.01235 (12)
S1	−0.15626 (5)	−0.23586 (6)	0.31854 (3)	0.01206 (14)
S2	0.23120 (5)	−0.27432 (7)	0.38709 (3)	0.01784 (16)
S3	0.00163 (6)	−0.11977 (9)	0.57434 (4)	0.0273 (2)
N1	0.03446 (15)	−0.24435 (19)	0.36060 (11)	0.0107 (4)
N2	−0.06795 (16)	−0.1810 (2)	0.44531 (11)	0.0134 (4)
H2	−0.1302 (12)	−0.159 (4)	0.452 (2)	0.045 (12)*
N3	0.10238 (17)	−0.2033 (2)	0.47401 (11)	0.0150 (5)
H3	0.1554 (16)	−0.204 (3)	0.5060 (13)	0.028 (10)*
N4	0.0000	−0.0656 (3)	0.2500	0.0117 (6)
N5	0.0000	0.5559 (3)	0.2500	0.0109 (6)
N6	0.24493 (17)	0.6013 (2)	0.97455 (12)	0.0174 (5)
C1	−0.05729 (19)	−0.2188 (2)	0.37983 (13)	0.0107 (5)
C2	0.11676 (19)	−0.2389 (2)	0.40807 (13)	0.0120 (5)
C3	0.0122 (2)	−0.1694 (3)	0.49499 (14)	0.0161 (5)
C4	0.08277 (19)	−0.0048 (2)	0.27253 (13)	0.0120 (5)
H4	0.1418	−0.0470	0.2889	0.014*
C5	0.08640 (19)	0.1160 (2)	0.27312 (13)	0.0120 (5)
H5	0.1470	0.1555	0.2891	0.014*
C6	0.0000	0.1803 (3)	0.2500	0.0102 (7)
C7	0.0000	0.3096 (3)	0.2500	0.0102 (7)
C8	0.08786 (19)	0.3736 (2)	0.24401 (14)	0.0131 (5)
H8	0.1491	0.3340	0.2389	0.016*
C9	0.08491 (19)	0.4946 (2)	0.24564 (14)	0.0140 (5)
H9	0.1459	0.5366	0.2436	0.017*
C10	0.2264 (2)	0.5473 (3)	1.03241 (17)	0.0288 (7)
H10	0.2807	0.5360	1.0677	0.035*
C11	0.1323 (2)	0.5063 (3)	1.04454 (17)	0.0297 (8)
H11	0.1234	0.4686	1.0874	0.036*
C12	0.05152 (19)	0.5201 (2)	0.99461 (13)	0.0137 (5)
C13	0.0710 (3)	0.5755 (4)	0.93421 (17)	0.0411 (10)
H13	0.0185	0.5866	0.8977	0.049*
C14	0.1672 (3)	0.6151 (4)	0.92657 (18)	0.0417 (10)
H14	0.1781	0.6543	0.8846	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0152 (2)	0.0111 (2)	0.0107 (2)	0.000	0.00138 (16)	0.000
S1	0.0080 (3)	0.0162 (3)	0.0113 (3)	0.0008 (2)	−0.0017 (2)	−0.0023 (2)
S2	0.0085 (3)	0.0333 (4)	0.0113 (3)	0.0054 (3)	−0.0008 (2)	−0.0028 (3)
S3	0.0171 (4)	0.0548 (6)	0.0096 (3)	0.0058 (3)	−0.0004 (3)	−0.0109 (3)
N1	0.0089 (10)	0.0156 (11)	0.0072 (9)	0.0023 (8)	−0.0008 (8)	−0.0012 (8)
N2	0.0094 (10)	0.0210 (12)	0.0098 (10)	0.0018 (8)	0.0005 (8)	−0.0024 (8)
N3	0.0103 (10)	0.0266 (12)	0.0076 (10)	0.0035 (9)	−0.0021 (8)	−0.0030 (9)
N4	0.0143 (14)	0.0100 (14)	0.0110 (14)	0.000	0.0019 (11)	0.000
N5	0.0114 (14)	0.0111 (14)	0.0099 (13)	0.000	−0.0001 (11)	0.000
N6	0.0149 (11)	0.0220 (12)	0.0154 (11)	−0.0055 (9)	0.0019 (9)	−0.0010 (9)
C1	0.0108 (11)	0.0106 (11)	0.0107 (11)	0.0004 (9)	0.0003 (9)	0.0024 (9)
C2	0.0098 (11)	0.0156 (12)	0.0100 (11)	0.0010 (9)	−0.0012 (9)	−0.0002 (9)
C3	0.0122 (12)	0.0243 (14)	0.0115 (12)	0.0008 (10)	−0.0006 (9)	−0.0001 (10)
C4	0.0108 (11)	0.0120 (12)	0.0128 (11)	0.0013 (9)	−0.0006 (9)	0.0002 (9)
C5	0.0095 (11)	0.0139 (12)	0.0121 (11)	−0.0019 (9)	−0.0005 (9)	−0.0009 (9)
C6	0.0116 (16)	0.0098 (16)	0.0097 (15)	0.000	0.0032 (12)	0.000
C7	0.0113 (15)	0.0115 (16)	0.0075 (15)	0.000	−0.0011 (12)	0.000
C8	0.0097 (11)	0.0136 (12)	0.0159 (12)	0.0021 (9)	0.0010 (9)	0.0008 (10)
C9	0.0109 (12)	0.0138 (12)	0.0171 (12)	−0.0015 (9)	0.0003 (9)	0.0003 (10)
C10	0.0146 (14)	0.0458 (19)	0.0257 (15)	0.0003 (13)	0.0008 (12)	0.0144 (14)
C11	0.0163 (14)	0.048 (2)	0.0252 (15)	0.0009 (13)	0.0036 (12)	0.0194 (14)
C12	0.0156 (13)	0.0131 (12)	0.0129 (12)	−0.0032 (10)	0.0037 (10)	−0.0022 (9)
C13	0.0267 (17)	0.077 (3)	0.0178 (15)	−0.0265 (17)	−0.0077 (13)	0.0154 (16)
C14	0.0270 (17)	0.075 (3)	0.0217 (16)	−0.0269 (17)	−0.0027 (13)	0.0192 (16)

Geometric parameters (Å, º)

Zn1—N5^i	2.126 (3)	N6—C10	1.321 (4)
Zn1—N1^ii	2.141 (2)	N6—C14	1.326 (4)
Zn1—N1	2.141 (2)	C4—C5	1.377 (4)
Zn1—N4	2.187 (3)	C4—H4	0.9500
Zn1—S1^ii	2.6004 (6)	C5—C6	1.401 (3)
Zn1—S1	2.6004 (6)	C5—H5	0.9500
S1—C1	1.691 (3)	C6—C5^ii	1.401 (3)
S2—C2	1.674 (3)	C6—C7	1.474 (5)
S3—C3	1.652 (3)	C7—C8	1.398 (3)
N1—C1	1.351 (3)	C7—C8^ii	1.398 (3)
N1—C2	1.358 (3)	C8—C9	1.380 (4)
N2—C1	1.357 (3)	C8—H8	0.9500
N2—C3	1.368 (3)	C9—H9	0.9500
N2—H2	0.8900 (11)	C10—C11	1.387 (4)
N3—C3	1.367 (3)	C10—H10	0.9500
N3—C2	1.368 (3)	C11—C12	1.379 (4)
N3—H3	0.8899 (11)	C11—H11	0.9500
N4—C4	1.339 (3)	C12—C13	1.374 (4)
N4—C4^ii	1.340 (3)	C12—C12^iv	1.488 (5)
N5—C9^ii	1.343 (3)	C13—C14	1.387 (4)
N5—C9	1.343 (3)	C13—H13	0.9500
N5—Zn1^iii	2.126 (3)	C14—H14	0.9500
N5^i—Zn1—N1^ii	94.02 (6)	N3—C2—S2	121.21 (19)
N5^i—Zn1—N1	94.02 (6)	N3—C3—N2	114.6 (2)
N1^ii—Zn1—N1	171.97 (12)	N3—C3—S3	122.4 (2)
N5^i—Zn1—N4	180	N2—C3—S3	123.0 (2)
N1^ii—Zn1—N4	85.98 (6)	N4—C4—C5	123.2 (2)
N1—Zn1—N4	85.98 (6)	N4—C4—H4	118.4
N5^i—Zn1—S1^ii	95.444 (17)	C5—C4—H4	118.4
N1^ii—Zn1—S1^ii	65.58 (6)	C4—C5—C6	119.5 (2)
N1—Zn1—S1^ii	113.59 (6)	C4—C5—H5	120.2
N4—Zn1—S1^ii	84.556 (17)	C6—C5—H5	120.2
N5^i—Zn1—S1	95.444 (17)	C5^ii—C6—C5	117.0 (3)
N1^ii—Zn1—S1	113.59 (6)	C5^ii—C6—C7	121.50 (16)
N1—Zn1—S1	65.58 (6)	C5—C6—C7	121.50 (16)
N4—Zn1—S1	84.556 (17)	C8—C7—C8^ii	117.2 (3)
S1^ii—Zn1—S1	169.11 (3)	C8—C7—C6	121.42 (17)
C1—S1—Zn1	75.79 (9)	C8^ii—C7—C6	121.42 (17)
C1—N1—C2	120.0 (2)	C9—C8—C7	119.5 (2)
C1—N1—Zn1	100.51 (15)	C9—C8—H8	120.2
C2—N1—Zn1	138.61 (17)	C7—C8—H8	120.2
C1—N2—C3	122.1 (2)	N5—C9—C8	123.2 (2)
C1—N2—H2	114 (3)	N5—C9—H9	118.4
C3—N2—H2	124 (3)	C8—C9—H9	118.4
C3—N3—C2	125.0 (2)	N6—C10—C11	123.6 (3)
C3—N3—H3	117 (2)	N6—C10—H10	118.2
C2—N3—H3	118 (2)	C11—C10—H10	118.2
C4—N4—C4^ii	117.7 (3)	C12—C11—C10	120.2 (3)
C4—N4—Zn1	121.16 (16)	C12—C11—H11	119.9
C4^ii—N4—Zn1	121.16 (16)	C10—C11—H11	119.9
C9^ii—N5—C9	117.4 (3)	C13—C12—C11	116.1 (3)
C9^ii—N5—Zn1^iii	121.31 (16)	C13—C12—C12^iv	121.4 (3)
C9—N5—Zn1^iii	121.31 (16)	C11—C12—C12^iv	122.5 (3)
C10—N6—C14	116.3 (3)	C12—C13—C14	120.1 (3)
N1—C1—N2	120.8 (2)	C12—C13—H13	120.0
N1—C1—S1	116.75 (19)	C14—C13—H13	120.0
N2—C1—S1	122.45 (19)	N6—C14—C13	123.7 (3)
N1—C2—N3	117.2 (2)	N6—C14—H14	118.1
N1—C2—S2	121.55 (19)	C13—C14—H14	118.1
N5^i—Zn1—S1—C1	98.25 (9)	C1—N1—C2—S2	177.9 (2)
N1^ii—Zn1—S1—C1	−164.95 (11)	Zn1—N1—C2—S2	−15.0 (4)
N1—Zn1—S1—C1	6.31 (11)	C3—N3—C2—N1	−2.2 (4)
N4—Zn1—S1—C1	−81.75 (9)	C3—N3—C2—S2	177.9 (2)
S1^ii—Zn1—S1—C1	−81.75 (9)	C2—N3—C3—N2	4.3 (4)
N5^i—Zn1—N1—C1	−101.95 (15)	C2—N3—C3—S3	−176.2 (2)
N4—Zn1—N1—C1	78.05 (15)	C1—N2—C3—N3	−2.5 (4)
S1^ii—Zn1—N1—C1	160.32 (14)	C1—N2—C3—S3	178.1 (2)
S1—Zn1—N1—C1	−7.79 (14)	C4^ii—N4—C4—C5	−0.37 (18)
N5^i—Zn1—N1—C2	89.4 (3)	Zn1—N4—C4—C5	179.63 (18)
N4—Zn1—N1—C2	−90.6 (3)	N4—C4—C5—C6	0.7 (4)
S1^ii—Zn1—N1—C2	−8.3 (3)	C4—C5—C6—C5^ii	−0.34 (17)
S1—Zn1—N1—C2	−176.4 (3)	C4—C5—C6—C7	179.65 (17)
N1^ii—Zn1—N4—C4	−118.52 (14)	C5^ii—C6—C7—C8	−152.66 (17)
N1—Zn1—N4—C4	61.48 (14)	C5—C6—C7—C8	27.34 (17)
S1^ii—Zn1—N4—C4	−52.70 (13)	C5^ii—C6—C7—C8^ii	27.34 (17)
S1—Zn1—N4—C4	127.30 (13)	C5—C6—C7—C8^ii	−152.66 (17)
N1^ii—Zn1—N4—C4^ii	61.48 (14)	C8^ii—C7—C8—C9	1.29 (17)
N1—Zn1—N4—C4^ii	−118.52 (14)	C6—C7—C8—C9	−178.71 (17)
S1^ii—Zn1—N4—C4^ii	127.30 (13)	C9^ii—N5—C9—C8	1.39 (19)
S1—Zn1—N4—C4^ii	−52.70 (13)	Zn1^iii—N5—C9—C8	−178.61 (19)
C2—N1—C1—N2	3.8 (4)	C7—C8—C9—N5	−2.7 (4)
Zn1—N1—C1—N2	−167.6 (2)	C14—N6—C10—C11	−0.2 (6)
C2—N1—C1—S1	−176.37 (19)	N6—C10—C11—C12	0.5 (6)
Zn1—N1—C1—S1	12.3 (2)	C10—C11—C12—C13	0.1 (5)
C3—N2—C1—N1	−1.4 (4)	C10—C11—C12—C12^iv	−178.7 (4)
C3—N2—C1—S1	178.8 (2)	C11—C12—C13—C14	−0.8 (6)
Zn1—S1—C1—N1	−10.22 (18)	C12^iv—C12—C13—C14	178.0 (4)
Zn1—S1—C1—N2	169.6 (2)	C10—N6—C14—C13	−0.6 (6)
C1—N1—C2—N3	−2.1 (4)	C12—C13—C14—N6	1.2 (7)
Zn1—N1—C2—N3	165.0 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N6^v	0.89 (1)	1.89 (1)	2.776 (3)	173 (4)
N3—H3···S2^vi	0.89 (1)	2.44 (1)	3.309 (2)	165 (3)

Symmetry codes: (v) x−1/2, −y+1/2, z−1/2; (vi) −x+1/2, −y−1/2, −z+1.