Crystal structure of bis-(piperazin-1-ium-κN4)bis-(thio-sulfato-κS)zinc(II) dihydrate.

In the title compound, [Zn(C4H11N2)2(S2O3)2]·2H2O, two thio-sulfate ions coordinate to the zinc(II) atom through the terminal S atoms. The tetra-hedral coordination around the ZnII ion is completed by ligating to two N atoms of two piperazinium ions. The remaining two N atoms of the piperazinium ions are diprotonated and do not coordinate to the metal centre. In the crystal, however, they are involved in N-H⋯Owater and N-H⋯Osulfato hydrogen bonds. Together, a series of N-H⋯O and O-H⋯O hydrogen bonds, involving the O atoms of the thio-sulfate ions and the water mol-ecules as acceptors and the hydrogen atoms of the piperazinium ions and the water mol-ecules as donors, form a three-dimensional supra-molecuar structure. Within this framework there are a number of intra- and inter-molecular C-H⋯O and C-H⋯S contacts present.

Chemical context

Over the last few decades, a large number of amine-templated n class="Chemical">metal complexes and compounds with extended structures have been synthesized in the presence of a number of inorganic anions (Férey, 2008 ▸). One series of anions, namely the sulfur-containing oxoanions, and in particular sulfates and sulfites, are widely used in the synthesis of higher dimensional inorganic compounds because of their multidentate coordin­ation capacity towards metal ions (Rao et al., 2006 ▸). In these examples, the anions bind to the metal cations through the oxygen atoms. The thio­sulfate ion is a new example of an sulfur oxoanion used in amine-templated synthesis, although the reactivity of this ligand is less than that of the sulfate and sulfite ions. In this heteroatomic ligand, the terminal S atom, as well as the O atoms, can bind to a range of metal ions. However, the long S—S bond is unstable under acidic conditions or at high temperature. Hence, the thio­sulfate anion has not, to date, been explored extensively as a network-building unit for higher dimensional structures (Paul et al., 2011 ▸). Despite these stability complications, Baggio and co-workers have synthesized a few mol­ecular and one-dimensional structures containing thio­sulfate anions that are connected to the metal through oxygen as well as sulfur atoms (Baggio et al., 1996 ▸, 1997 ▸; Freire et al., 2001 ▸; Harvey et al., 2004 ▸). Our continuing synthetic efforts using the thio­sulfate anion have resulted in the synthesis of some new three-dimensional structures in the family of cadmium–thio­sulfate hybrid compounds formed in the presence of organic linkers (Paul et al., 2009a ▸,b ▸, 2010 ▸). It is noteworthy that all of the reported metal–thio­sulfate compounds are synthesized in the presence of nitro­gen-containing aromatic organic linkers. Aromatic ligands play a dual role in metal–thio­sulfate formation as they increase the dimensionality of the local structure and increase structure stabilization via secondary inter­actions, such as hydrogen bonds. Recently, Natarajan and co-workers (Karthik & Natarajan, 2016 ▸) have reported on some three-dimensional zinc–thio­sulfate hybrid structures with aromatic N-donor organic linkers. Metal–thio­sulfate compounds prepared in the presence of aliphatic amines are, however, rare (Paul, 2016 ▸) and require investigation. The title compound, is the first example of an aliphatic-amine-templated zinc thio­sulfate compound. Its synthesis and crystal structure are reported on herein.

Structural commentary

The mol­ecular structure of the title compound is illustrated in Fig. 1 ▸. In the complex, the Zn2+ ion is coordinated by two n class="Chemical">sulfur atoms of the thio­sulfate ligands (S1 and S3) and two nitro­gen atoms from the piperazinium ions (N1 and N3), in an approximately tetra­hedral geometry (ZnS2N2, CN = 4). The Zn—S bond lengths are 2.2927 (4) Å for Zn1—S1 and 2.3324 (4) Å for Zn1—S3. The Zn—N bond lengths are 2.0879 (13) Å for Zn1—N1 and 2.0727 (12) Å for Zn1—N3. The N/S—Zn1—S/N bond angles lie in the range 101.24 (4) to 116.79 (2)°, confirming the tetra­hedral nature of the zinc ions. Within the two thio­sulfate ligands, the S—S bond lengths are 2.0511 (5) Å for S1—S2 and 2.0332 (5) Å for S3—S4. The S—O bond lengths vary from 1.4437 (14) to 1.4623 (13) Å, while the O—S—O angles vary from 104.53 (5) to 112.85 (10)°, which is indicative of a fairly regular tetra­hedral arrangement. In the mol­ecular unit, the two thio­sulfate units are bonded to the zinc(II) ion only through the terminal S atoms, and the oxygen atoms are uncoordinated. In addition, only one nitro­gen atom of each piperazinium ion is bonded to the zinc(II) ion, the second being diprotonated in each case.

Figure 1

The asymmetric unit of the title compound, with atom labelling and showing 50% probability displacement ellipsoids.

Supra­molecular features

The supra­molecular architecture (Fig. 2 ▸) arises from a three-dimensional network of N—H⋯O and O—H⋯O n class="Chemical">hydrogen bonds involving the uncoordinated oxygen atoms of the thio­sulfate ligands, the protonated piperazine units and the lattice water mol­ecules (Table 1 ▸). These inter­molecular inter­actions lead to the formation of a supra­molecular framework. Within this framework there are a number of intra- and inter­molecular C—H⋯O and C—H⋯S contacts present (Table 1 ▸).

Figure 2

A view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 ▸).

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.83 (2)	2.25 (2)	3.041 (2)	160 (2)
N2—H2AN⋯O6ii	0.95 (3)	1.80 (3)	2.730 (2)	166 (2)
N2—H2BN⋯O10	0.93 (2)	1.89 (2)	2.811 (3)	170 (2)
N3—H3⋯O3i	0.84 (2)	2.03 (2)	2.853 (2)	166 (2)
N4—H4AN⋯O20	0.87 (2)	2.09 (2)	2.892 (2)	154 (2)
N4—H4BN⋯O5iii	0.94 (2)	1.84 (2)	2.763 (2)	169 (2)
O10—H10A⋯O4	0.85 (3)	1.94 (4)	2.780 (2)	175 (3)
O10—H10B⋯O1iv	0.76 (3)	2.02 (3)	2.777 (2)	176 (4)
O20—H20A⋯O1v	0.82 (3)	2.02 (3)	2.804 (2)	163 (3)
O20—H20B⋯O5vi	0.74 (3)	2.17 (3)	2.866 (2)	158 (3)
C3—H3A⋯O6iv	0.97	2.45	3.221 (2)	136
C4—H4A⋯O3	0.97	2.49	3.175 (3)	128
C4—H4B⋯O4	0.97	2.54	3.463 (2)	159
C5—H5B⋯S3	0.97	2.86	3.453 (2)	120
C8—H8B⋯O2	0.97	2.50	3.318 (2)	142

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

Database survey

A search of the Cambridge Structural Database (CSD, Version 35.9, last update May 2017; Groom et al., 2016 ▸) for zinc–thio­sulfato complexes gave 12 hits, all involving aromatic amines and/or thio­ureas. Díaz de Vivar et al. (2006 ▸) have described a mol­ecular zinc–thio­n class="Chemical">sulfate complex prepared in the presence of a tridentate aromatic ligand, viz. aqua(thio­sulfato-κO,S)[2,4,6-tris­(2-pyrid­yl)-1,3,5-triazine-N,N′,N′′]zinc(II) hemihydrate (CSD refcode: WEHTOT). The thio­sulfate ligand is coordinated to the zinc ions through S and O atoms, forming octa­hedral zinc centres. In addition, a zinc–thio­sulfate complex containing both one-dimensional cationic and anionic chains has been reported by the same authors, viz. catena-[(μ2-4,4′-bi­pyridine-κN,N′)tetra­aqua­zinc(II) bis­(μ2-4,4′-bi­pyridine-κN,N′)(μ2-thio­sulfato-κO,S)bis­(thio­sulfato-κS)dizinc(II) dihydrate] [PEYLEL; Díaz de Vivar et al., 2007 ▸). Both types of chain contain 4,4′-bi­pyridine ligands as linkers.

Karthik & Natarajan (2016 ▸) have recently reported four higher-dimensional zinc–thio­n class="Chemical">sulfate compounds synthesized in the presence of various aromatic ligands, viz. catena-[bis­(μ-4,4′-bi­pyridine)­bis­(μ-thio­sulfato)­dizinc] (IJUWER), catena-[(μ-4,4′-propane-1,3-diyldi­pyridine)(μ-thio­sulfato)­zinc] (IJU­WIV), and catena-[bis­(μ-4,4′-ethene-1,2-diyldi­pyridine)­bis­(μ-thio­sulfato)­dizinc dihydrate] (IJUWOB) and catena-[bis­(μ-4,4′-ethane-1,2-diyldi­pyridine)­bis­(μ-thio­sulfato)­dizinc (μ-4,4′-ethane-1,2-diyldi­pyridine)(μ-thio­sulfato)­zinc trihydrate] (IJUWUH).

A number of mol­ecular cadmium–thio­sulfate and manganese–thio­n class="Chemical">sulfate structures have been reported by Baggio and co-workers (Baggio et al., 1996 ▸, 1997 ▸; Freire et al., 2001 ▸; Harvey et al., 2004 ▸). They were synthesized in the presence of 2,2′-bi­pyridine or 1,10-phenanthroline.

There are a few examples in which zero-dimensional cadmium–thio­sulfate compounds form simple dinuclear complexes, in which the thio­n class="Chemical">sulfate unit is bound to the metal through both the sulfur and the oxygen atoms. As expected, the structures are stabilized through C—H⋯O hydrogen-bonding inter­actions and π–π inter­actions. One cadmium thio­sulfate compound, bis­(propane-1,3-di­amine)(thio­sulfato)cadmium (CSD refcode: ORUJOC), which was reported recently, was isolated in the presence of the aliphatic amine 1,3-di­amino­propane (Paul, 2016 ▸). One mol­ecular piperazinium thio­sulfate monohydrate structure has been reported, (piperazinediium thio­sulfate monohydrate; CSD refcode: AROWUA; Srinivasan et al., 2011 ▸), in which the protonated aliphatic amine and thio­sulfate units are linked together through extensive hydrogen bonds. It is noteworthy that there are no previous examples in the literature of zinc–thio­sulfate structures that crystallize in the presence of aliphatic amines.

Synthesis and crystallization

Zn(NO3)2·6H2O (0.297 g, 1 mmol) was dissolved in 5 ml distilled n class="Chemical">water. Then (NH4)2S2O3 (0.296 g, 2 mmol) was added to the solution, which was stirred for 15 min. Piperazine (0.172 g, 2 mmol) was dissolved separately in distilled water (5 ml) and the solution poured into the initial reaction mixture until the pH was 8. The resulting solution was left undisturbed and after 1 week, colourless block-shaped crystals were obtained. The product was filtered and washed with cold water. The yield was approximately 85% based on Zn metal. Elemental analysis calculated for C8H26N4O8S4Zn: C 19.20, H 5.24, N 11.20%; found: C 19.27, H 5.29, N 11.16%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The NH, n class="Chemical">NH2 and water H atoms were located in difference-Fourier maps and freely refined. The C-bound H atoms were included in calculated positions and refined as riding: C—H = 0.97 Å with U iso(H) = 1.2U eq(C).

Table 2

Experimental details

Crystal data
Chemical formula	[Zn(C4H11N2)2(S2O3)2]·2H2O
M r	499.94
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c (Å)	8.7631 (1), 10.5623 (2), 11.6072 (2)
α, β, γ (°)	113.736 (1), 98.761 (1), 91.472 (1)
V (Å3)	967.49 (3)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.74
Crystal size (mm)	0.22 × 0.18 × 0.16
Data collection
Diffractometer	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000 ▸)
T min, T max	0.700, 0.768
No. of measured, independent and observed [I > 2σ(I)] reflections	19938, 7607, 5927
R int	0.027
(sin θ/λ)max (Å−1)	0.782
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.032, 0.079, 1.01
No. of reflections	7607
No. of parameters	266
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.47, −0.36

Computer programs: SMART and SAINT (Bruker, 2000 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2016/6 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989018000555/cq2022sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018000555/cq2022Isup2.hkl

CCDC reference: 1571150

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

[Zn(C4H11N2)2(S2O3)2]·2H2O	Z = 2
Mr = 499.94	F(000) = 520
Triclinic, P1	Dx = 1.716 Mg m−3
a = 8.7631 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5623 (2) Å	Cell parameters from 3790 reflections
c = 11.6072 (2) Å	θ = 2.0–26.0°
α = 113.736 (1)°	µ = 1.74 mm−1
β = 98.761 (1)°	T = 293 K
γ = 91.472 (1)°	Block, colorless
V = 967.49 (3) Å3	0.22 × 0.18 × 0.16 mm

Bruker SMART APEX CCD area detector diffractometer	7607 independent reflections
Radiation source: fine-focus sealed tube	5927 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 33.7°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
Tmin = 0.700, Tmax = 0.768	k = −16→9
19938 measured reflections	l = −18→17

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) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3
7607 reflections	(Δ/σ)max < 0.001
266 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

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
Zn1	0.36403 (2)	0.36678 (2)	0.17364 (2)	0.02307 (5)
S1	0.19769 (4)	0.23705 (4)	−0.01347 (4)	0.02921 (8)
S2	0.28149 (4)	0.31755 (4)	−0.12806 (4)	0.02866 (8)
S3	0.31486 (6)	0.34577 (4)	0.35739 (4)	0.03543 (10)
S4	0.27051 (4)	0.13632 (4)	0.29154 (4)	0.02567 (8)
O1	0.22237 (19)	0.21735 (14)	−0.25891 (12)	0.0508 (4)
O2	0.22392 (19)	0.45077 (14)	−0.10572 (15)	0.0541 (4)
O3	0.44978 (15)	0.32601 (19)	−0.09909 (15)	0.0612 (4)
O4	0.40860 (15)	0.06807 (14)	0.25701 (14)	0.0486 (3)
O5	0.2234 (2)	0.11500 (13)	0.39847 (14)	0.0544 (4)
O6	0.14635 (14)	0.09045 (13)	0.18082 (13)	0.0435 (3)
N1	0.59630 (14)	0.33597 (13)	0.16071 (13)	0.0261 (2)
H1	0.627 (2)	0.3885 (19)	0.1297 (18)	0.033 (5)*
N2	0.86568 (17)	0.19550 (17)	0.20334 (16)	0.0381 (3)
H2AN	0.968 (3)	0.172 (2)	0.194 (2)	0.053 (6)*
H2BN	0.831 (3)	0.149 (2)	0.249 (2)	0.058 (7)*
N3	0.34859 (14)	0.57724 (12)	0.22385 (12)	0.0225 (2)
H3	0.396 (2)	0.5979 (17)	0.1754 (17)	0.024 (4)*
N4	0.24360 (17)	0.84404 (13)	0.37115 (13)	0.0298 (3)
H4AN	0.186 (2)	0.8219 (19)	0.4161 (19)	0.037 (5)*
H4BN	0.229 (2)	0.937 (2)	0.3879 (19)	0.043 (5)*
C1	0.69716 (19)	0.37986 (18)	0.28807 (16)	0.0381 (4)
H1A	0.654430	0.334114	0.335305	0.046*
H1B	0.696156	0.479233	0.335289	0.046*
C2	0.8636 (2)	0.34663 (19)	0.2805 (2)	0.0454 (5)
H2A	0.911324	0.399270	0.241316	0.055*
H2B	0.922320	0.372326	0.365901	0.055*
C3	0.7752 (2)	0.1542 (2)	0.07222 (18)	0.0421 (4)
H3A	0.777441	0.055408	0.022780	0.051*
H3B	0.821264	0.203770	0.029594	0.051*
C4	0.60942 (19)	0.18742 (16)	0.07979 (15)	0.0315 (3)
H4A	0.552976	0.164170	−0.005869	0.038*
H4B	0.561198	0.129930	0.114233	0.038*
C5	0.4203 (2)	0.66344 (15)	0.35818 (15)	0.0327 (3)
H5A	0.528902	0.647499	0.370824	0.039*
H5B	0.370312	0.634514	0.413833	0.039*
C6	0.40821 (19)	0.81761 (15)	0.39612 (16)	0.0330 (3)
H6A	0.450934	0.868622	0.486215	0.040*
H6B	0.467790	0.849836	0.347563	0.040*
C7	0.17408 (19)	0.76190 (16)	0.23399 (16)	0.0333 (3)
H7A	0.227849	0.791358	0.180529	0.040*
H7B	0.065948	0.778454	0.219288	0.040*
C8	0.18624 (17)	0.60873 (15)	0.19857 (16)	0.0308 (3)
H8A	0.124751	0.578258	0.247102	0.037*
H8B	0.143694	0.557112	0.108512	0.037*
O10	0.72416 (18)	0.05969 (17)	0.32966 (15)	0.0460 (3)
H10A	0.629 (4)	0.060 (3)	0.303 (3)	0.098 (11)*
H10B	0.742 (3)	−0.015 (3)	0.313 (3)	0.074 (10)*
O20	−0.01440 (19)	0.7318 (2)	0.44092 (18)	0.0557 (4)
H20A	−0.082 (4)	0.729 (3)	0.383 (3)	0.092 (11)*
H20B	−0.048 (3)	0.776 (3)	0.497 (3)	0.070 (9)*

	U11	U22	U33	U12	U13	U23
Zn1	0.02461 (8)	0.02117 (8)	0.02345 (8)	0.00381 (6)	0.00452 (6)	0.00900 (6)
S1	0.02902 (18)	0.03198 (19)	0.02573 (17)	−0.00689 (14)	0.00212 (13)	0.01250 (15)
S2	0.02756 (17)	0.0354 (2)	0.02670 (18)	0.00130 (14)	0.00454 (13)	0.01668 (15)
S3	0.0560 (3)	0.02537 (18)	0.02544 (18)	−0.00262 (17)	0.01059 (17)	0.01015 (15)
S4	0.02671 (16)	0.02414 (17)	0.03090 (18)	0.00813 (13)	0.01197 (13)	0.01342 (14)
O1	0.0746 (10)	0.0502 (8)	0.0237 (6)	0.0060 (7)	0.0030 (6)	0.0132 (5)
O2	0.0744 (10)	0.0403 (7)	0.0630 (9)	0.0151 (7)	0.0259 (8)	0.0316 (7)
O3	0.0291 (6)	0.1148 (13)	0.0692 (10)	−0.0021 (7)	0.0074 (6)	0.0689 (10)
O4	0.0356 (7)	0.0524 (8)	0.0618 (9)	0.0251 (6)	0.0179 (6)	0.0229 (7)
O5	0.0985 (12)	0.0319 (6)	0.0513 (8)	0.0170 (7)	0.0449 (8)	0.0242 (6)
O6	0.0308 (6)	0.0364 (7)	0.0466 (7)	0.0042 (5)	0.0010 (5)	0.0021 (5)
N1	0.0255 (6)	0.0260 (6)	0.0290 (6)	0.0060 (5)	0.0052 (5)	0.0132 (5)
N2	0.0270 (7)	0.0479 (9)	0.0476 (9)	0.0152 (6)	0.0120 (6)	0.0253 (7)
N3	0.0239 (5)	0.0217 (5)	0.0234 (6)	0.0036 (4)	0.0068 (4)	0.0097 (5)
N4	0.0379 (7)	0.0219 (6)	0.0331 (7)	0.0078 (5)	0.0141 (6)	0.0119 (5)
C1	0.0325 (8)	0.0364 (9)	0.0334 (8)	0.0085 (7)	−0.0011 (6)	0.0040 (7)
C2	0.0257 (8)	0.0450 (10)	0.0570 (12)	0.0036 (7)	−0.0024 (8)	0.0156 (9)
C3	0.0425 (9)	0.0500 (11)	0.0373 (9)	0.0219 (8)	0.0164 (7)	0.0172 (8)
C4	0.0335 (8)	0.0311 (8)	0.0273 (7)	0.0101 (6)	0.0061 (6)	0.0087 (6)
C5	0.0377 (8)	0.0255 (7)	0.0294 (7)	0.0066 (6)	−0.0024 (6)	0.0085 (6)
C6	0.0351 (8)	0.0231 (7)	0.0342 (8)	0.0025 (6)	0.0018 (6)	0.0065 (6)
C7	0.0349 (8)	0.0307 (8)	0.0336 (8)	0.0105 (6)	0.0027 (6)	0.0133 (6)
C8	0.0248 (7)	0.0269 (7)	0.0361 (8)	0.0044 (5)	0.0028 (6)	0.0091 (6)
O10	0.0428 (8)	0.0457 (8)	0.0492 (8)	0.0068 (6)	0.0067 (6)	0.0197 (7)
O20	0.0445 (8)	0.0857 (12)	0.0441 (9)	0.0215 (8)	0.0168 (7)	0.0300 (9)

Zn1—N3	2.0727 (12)	N4—H4BN	0.93 (2)
Zn1—N1	2.0879 (13)	C1—C2	1.516 (2)
Zn1—S1	2.2927 (4)	C1—H1A	0.9700
Zn1—S3	2.3324 (4)	C1—H1B	0.9700
S1—S2	2.0511 (5)	C2—H2A	0.9700
S2—O2	1.4437 (14)	C2—H2B	0.9700
S2—O3	1.4539 (14)	C3—C4	1.510 (2)
S2—O1	1.4606 (13)	C3—H3A	0.9700
S3—S4	2.0332 (5)	C3—H3B	0.9700
S4—O4	1.4507 (12)	C4—H4A	0.9700
S4—O6	1.4546 (13)	C4—H4B	0.9700
S4—O5	1.4623 (13)	C5—C6	1.518 (2)
N1—C1	1.487 (2)	C5—H5A	0.9700
N1—C4	1.4876 (19)	C5—H5B	0.9700
N1—H1	0.83 (2)	C6—H6A	0.9700
N2—C2	1.485 (2)	C6—H6B	0.9700
N2—C3	1.489 (2)	C7—C8	1.511 (2)
N2—H2AN	0.95 (2)	C7—H7A	0.9700
N2—H2BN	0.93 (2)	C7—H7B	0.9700
N3—C5	1.4779 (19)	C8—H8A	0.9700
N3—C8	1.4820 (18)	C8—H8B	0.9700
N3—H3	0.837 (18)	O10—H10A	0.85 (3)
N4—C6	1.484 (2)	O10—H10B	0.76 (3)
N4—C7	1.491 (2)	O20—H20A	0.81 (3)
N4—H4AN	0.87 (2)	O20—H20B	0.74 (3)
N3—Zn1—N1	105.78 (5)	N1—C1—H1B	108.9
N3—Zn1—S1	110.79 (3)	C2—C1—H1B	108.9
N1—Zn1—S1	112.90 (4)	H1A—C1—H1B	107.7
N3—Zn1—S3	101.24 (4)	N2—C2—C1	109.22 (14)
N1—Zn1—S3	108.21 (4)	N2—C2—H2A	109.8
S1—Zn1—S3	116.788 (16)	C1—C2—H2A	109.8
S2—S1—Zn1	98.167 (18)	N2—C2—H2B	109.8
O2—S2—O3	112.85 (10)	C1—C2—H2B	109.8
O2—S2—O1	110.61 (9)	H2A—C2—H2B	108.3
O3—S2—O1	111.04 (10)	N2—C3—C4	109.77 (14)
O2—S2—S1	109.71 (6)	N2—C3—H3A	109.7
O3—S2—S1	107.00 (6)	C4—C3—H3A	109.7
O1—S2—S1	105.27 (6)	N2—C3—H3B	109.7
S4—S3—Zn1	101.05 (2)	C4—C3—H3B	109.7
O4—S4—O6	110.47 (8)	H3A—C3—H3B	108.2
O4—S4—O5	111.17 (9)	N1—C4—C3	113.09 (14)
O6—S4—O5	112.02 (9)	N1—C4—H4A	109.0
O4—S4—S3	110.45 (6)	C3—C4—H4A	109.0
O6—S4—S3	108.00 (6)	N1—C4—H4B	109.0
O5—S4—S3	104.53 (5)	C3—C4—H4B	109.0
C1—N1—C4	110.39 (12)	H4A—C4—H4B	107.8
C1—N1—Zn1	112.60 (10)	N3—C5—C6	113.06 (12)
C4—N1—Zn1	109.65 (9)	N3—C5—H5A	109.0
C1—N1—H1	105.4 (13)	C6—C5—H5A	109.0
C4—N1—H1	112.1 (13)	N3—C5—H5B	109.0
Zn1—N1—H1	106.6 (13)	C6—C5—H5B	109.0
C2—N2—C3	110.50 (14)	H5A—C5—H5B	107.8
C2—N2—H2AN	111.5 (13)	N4—C6—C5	110.10 (13)
C3—N2—H2AN	107.0 (14)	N4—C6—H6A	109.6
C2—N2—H2BN	107.5 (14)	C5—C6—H6A	109.6
C3—N2—H2BN	114.4 (14)	N4—C6—H6B	109.6
H2AN—N2—H2BN	106.1 (19)	C5—C6—H6B	109.6
C5—N3—C8	110.20 (12)	H6A—C6—H6B	108.2
C5—N3—Zn1	112.71 (9)	N4—C7—C8	110.19 (13)
C8—N3—Zn1	111.95 (9)	N4—C7—H7A	109.6
C5—N3—H3	109.2 (12)	C8—C7—H7A	109.6
C8—N3—H3	106.3 (12)	N4—C7—H7B	109.6
Zn1—N3—H3	106.2 (12)	C8—C7—H7B	109.6
C6—N4—C7	110.40 (12)	H7A—C7—H7B	108.1
C6—N4—H4AN	113.4 (13)	N3—C8—C7	112.29 (12)
C7—N4—H4AN	107.0 (13)	N3—C8—H8A	109.1
C6—N4—H4BN	114.3 (13)	C7—C8—H8A	109.1
C7—N4—H4BN	106.1 (13)	N3—C8—H8B	109.1
H4AN—N4—H4BN	105.1 (17)	C7—C8—H8B	109.1
N1—C1—C2	113.43 (15)	H8A—C8—H8B	107.9
N1—C1—H1A	108.9	H10A—O10—H10B	109 (3)
C2—C1—H1A	108.9	H20A—O20—H20B	100 (3)
C4—N1—C1—C2	52.0 (2)	C8—N3—C5—C6	−53.62 (19)
Zn1—N1—C1—C2	174.88 (12)	Zn1—N3—C5—C6	−179.47 (11)
C3—N2—C2—C1	59.1 (2)	C7—N4—C6—C5	−57.01 (18)
N1—C1—C2—N2	−56.1 (2)	N3—C5—C6—N4	55.66 (19)
C2—N2—C3—C4	−59.4 (2)	C6—N4—C7—C8	58.03 (18)
C1—N1—C4—C3	−51.76 (19)	C5—N3—C8—C7	54.16 (18)
Zn1—N1—C4—C3	−176.37 (11)	Zn1—N3—C8—C7	−179.56 (11)
N2—C3—C4—N1	56.0 (2)	N4—C7—C8—N3	−56.96 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.83 (2)	2.25 (2)	3.041 (2)	160 (2)
N2—H2AN···O6ii	0.95 (3)	1.80 (3)	2.730 (2)	166 (2)
N2—H2BN···O10	0.93 (2)	1.89 (2)	2.811 (3)	170 (2)
N3—H3···O3i	0.84 (2)	2.03 (2)	2.853 (2)	166 (2)
N4—H4AN···O20	0.87 (2)	2.09 (2)	2.892 (2)	154 (2)
N4—H4BN···O5iii	0.94 (2)	1.84 (2)	2.763 (2)	169 (2)
O10—H10A···O4	0.85 (3)	1.94 (4)	2.780 (2)	175 (3)
O10—H10B···O1iv	0.76 (3)	2.02 (3)	2.777 (2)	176 (4)
O20—H20A···O1v	0.82 (3)	2.02 (3)	2.804 (2)	163 (3)
O20—H20B···O5vi	0.74 (3)	2.17 (3)	2.866 (2)	158 (3)
C3—H3A···O6iv	0.97	2.45	3.221 (2)	136
C4—H4A···O3	0.97	2.49	3.175 (3)	128
C4—H4B···O4	0.97	2.54	3.463 (2)	159
C5—H5B···S3	0.97	2.86	3.453 (2)	120
C8—H8B···O2	0.97	2.50	3.318 (2)	142