Crystal structure of bis­(piperazin-1-ium-κN4)bis­(thio­sulfato-κS)zinc(II) dihydrate

Paul, A.K.

doi:10.1107/S2056989018000555

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 2| February 2018| Pages 176-179

https://doi.org/10.1107/S2056989018000555

Open

access

Crystal structure of bis(piperazin-1-ium-κN⁴)bis(thiosulfato-κS)zinc(II) dihydrate

Avijit Kumar Paul ^a ^*

^aDepartment of Chemistry, National Institute of Technology Kurukshetra, Haryana 136 119, India
^*Correspondence e-mail: apaul@nitkkr.ac.in

Edited by A. M. Chippindale, University of Reading, England (Received 27 October 2017; accepted 9 January 2018; online 19 January 2018)

In the title compound, [Zn(C₄H₁₁N₂)₂(S₂O₃)₂]·2H₂O, two thiosulfate ions coordinate to the zinc(II) atom through the terminal S atoms. The tetrahedral coordination around the Zn^II 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⋯O_water 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 thiosulfate ions and the water molecules as acceptors and the hydrogen atoms of the piperazinium ions and the water molecules as donors, form a three-dimensional supramolecuar structure. Within this framework there are a number of intra- and intermolecular C—H⋯O and C—H⋯S contacts present.

Keywords: crystal structure; zinc thiosulfate; piperazine; hydrogen bonding.

CCDC reference: 1571150

1. Chemical context

Over the last few decades, a large number of amine-templated 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.

2. Structural commentary

The molecular structure of the title compound is illustrated in Fig. 1. In the complex, the Zn²⁺ ion is coordinated by two 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.

3. Supramolecular features

The supramolecular architecture (Fig. 2) arises from a three-dimensional network of N—H⋯O and O—H⋯O 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).

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⋯O1^iv	0.76 (3)	2.02 (3)	2.777 (2)	176 (4)
O20—H20A⋯O1^v	0.82 (3)	2.02 (3)	2.804 (2)	163 (3)
O20—H20B⋯O5^vi	0.74 (3)	2.17 (3)	2.866 (2)	158 (3)
C3—H3A⋯O6^iv	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) -x+1, -y+1, -z; (ii) x+1, y, z; (iii) x, y+1, z; (iv) -x+1, -y, -z; (v) -x, -y+1, -z; (vi) -x, -y+1, -z+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

4. 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–thiosulfate 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–thiosulfate 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–thiosulfate 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 thiosulfate 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.

5. Synthesis and crystallization

Zn(NO₃)₂·6H₂O (0.297 g, 1 mmol) was dissolved in 5 ml distilled 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%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH, 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 $[\overline{1}]$
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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC reference: 1571150

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2056989018000555/cq2022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018000555/cq2022Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2016/6 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Bis(piperazin-1-ium-κN⁴)bis(thiosulfato-κS)zinc(II) dihydrate top

Crystal data top

[Zn(C₄H₁₁N₂)₂(S₂O₃)₂]·2H₂O	Z = 2
M_r = 499.94	F(000) = 520
Triclinic, P1	D_x = 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

Data collection top

Bruker SMART APEX CCD area detector diffractometer	7607 independent reflections
Radiation source: fine-focus sealed tube	5927 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 33.7°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
T_min = 0.700, T_max = 0.768	k = −16→9
19938 measured reflections	l = −18→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)] = 0.032	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(F_o²) + (0.040P)²] where P = (F_o² + 2F_c²)/3
7607 reflections	(Δ/σ)_max < 0.001
266 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

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	0.36403 (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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.76 (3)	2.02 (3)	2.777 (2)	176 (4)
O20—H20A···O1^v	0.82 (3)	2.02 (3)	2.804 (2)	163 (3)
O20—H20B···O5^vi	0.74 (3)	2.17 (3)	2.866 (2)	158 (3)
C3—H3A···O6^iv	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) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) x, y+1, z; (iv) −x+1, −y, −z; (v) −x, −y+1, −z; (vi) −x, −y+1, −z+1.

Acknowledgements

The author thanks Professor S. Natarajan for providing facilities.

Funding information

The author thanks the SERB and DST, India, for research grants.

References

Baggio, R., Baggio, S., Pardo, M. I. & Garland, M. T. (1996). Acta Cryst. C52, 1939–1942. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Baggio, S., Pardo, M. I., Baggio, R. & Garland, M. T. (1997). Acta Cryst. C53, 727–729. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Díaz de Vivar, M. E., Baggio, S. & Baggio, R. (2006). Acta Cryst. C62, m192–m194. CSD CrossRef IUCr Journals Google Scholar
Díaz de Vivar, M. E., Baggio, S., Garland, M. T. & Baggio, R. (2007). Acta Cryst. C63, m123–m125. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Férey, G. (2008). Chem. Soc. Rev. 37, 191–214. Web of Science PubMed Google Scholar
Freire, E., Baggio, S., Baggio, R. & Mombrú, A. (2001). Acta Cryst. C57, 14–17. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Harvey, M., Baggio, S., Pardo, H. & Baggio, R. (2004). Acta Cryst. C60, m79–m81. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Karthik, R. & Natarajan, S. (2016). Cryst. Growth Des. 16, 2239–2248. CSD CrossRef CAS Google Scholar
Paul, A. K. (2016). J. Mol. Struct. 1125, 696–704. CSD CrossRef CAS Google Scholar
Paul, A. K., Karthik, R. & Natarajan, S. (2011). Cryst. Growth Des. 11, 5741–5749. Web of Science CSD CrossRef CAS Google Scholar
Paul, A. K., Madras, G. & Natarajan, S. (2009a). CrystEngComm, 11, 55–57. CSD CrossRef CAS Google Scholar
Paul, A. K., Madras, G. & Natarajan, S. (2009b). Phys. Chem. Chem. Phys. 11, 11285–11296. PubMed Google Scholar
Paul, A. K., Madras, G. & Natarajan, S. (2010). Dalton Trans. 39, 2263–2279. CSD CrossRef CAS PubMed Google Scholar
Rao, C. N. R., Behera, J. N. & Dan, M. (2006). Chem. Soc. Rev. 35, 375–387. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Srinivasan, B. R., Naik, A. R., Dhuri, S. N., Näther, C. & Bensch, W. (2011). J. Chem. Sci. 123, 55–61. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.