Synthesis and structure of catena-poly[[[aquazinc(II)]-μ-2-({[amino­(sulfanid­yl)methyl­idene]amino}­imino)-2-phenyl­acetato-κ4O,N,S:O′] monohydrate]

Akhatov, J.; Tillaeva, G.; Turaev, K.; Choriyev, O.; Primkulova, M.; Ibragimov, B.; Ashurov, J.M.

doi:10.1107/S2056989026010169

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ISSN: 2056-9890

Volume 82| Part 11| November 2026|

https://doi.org/10.1107/S2056989026010169

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Synthesis and structure of catena-poly[[[aquazinc(II)]-μ-2-({[amino(sulfanidyl)methylidene]amino}imino)-2-phenylacetato-κ⁴O,N,S:O′] monohydrate]

Javokhirkhon Akhatov,^a Gulnora Tillaeva,^b Khayit Turaev,^a Odyl Choriyev,^c Maftuna Primkulova,^d Bakhtiyar Ibragimov ^c and Jamshid Mengnorovich Ashurov ^c ^*

^aTermez State University, Barkamol Avlod St. 43, 190111, Termez, Uzbekistan, ^bTashkent Pharmaceutical Institute A. Aybek St. 45, Tashkent, 100015, Uzbekistan, ^cInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, 100125, M. Ulugbek Str 83, Tashkent, Uzbekistan, and ^dDenov Institute of Entrepreneurship and Pedagogy Bog St. 112, Denov, 733500, Uzbekistan
^*Correspondence e-mail: [email protected]

Edited by M. Weil, Vienna University of Technology, Austria (Received 7 September 2026; accepted 29 September 2026; online 2 October 2026)

In the polymeric title compound, {[Zn(C₉H₇N₃O₂S)(H₂O)]·H₂O}_n, the dianion of phenylglyoxylic acid thiosemicarbazone (benzketozone) chelates one Zn^II cation through carboxylate O, azomethine N and thiolate S atoms and bridges to the next Zn^II ion through its second carboxylate O atom. Each Zn^II ion is five-coordinate, with the aqua ligand completing the coordination sphere, which has a shape intermediate between square-pyramidal and trigonal-bipyramidal. The coordination motif generates a chain extending parallel to [010], with an adjacent Zn⋯Zn separation of 4.8378 (4) Å. O—H⋯O, O—H⋯S and N—H⋯N hydrogen bonds connect the polymeric chains and non-coordinating water molecules into a three-periodic network; a weak N—H⋯π contact is also present. Hirshfeld surface analysis identifies H⋯H (34.8%), C⋯H/H⋯C (16.1%), H⋯S/S⋯H (13.2%), O⋯H/H⋯O (11.0%) and N⋯H/H⋯N (8.4%) as the principal contact contributions.

Keywords: zinc(II); coordination polymer; benzketozone; phenylglyoxylic acid thiosemicarbazone; crystal structure; Hirshfeld surface analysis; hydrogen bonding.

CCDC reference: 2591804

1. Chemical context

Thiosemicarbazones are versatile Schiff-base ligands whose coordination behaviour is strongly influenced by the parent carbonyl compound, the central metal cation and the degree of ligand deprotonation. They commonly bind through the azomethine N and thione/thiolate S atoms, while additional donor groups can lead to tridentate or higher-denticity coordination modes (Casas et al., 2000 ; Lobana et al., 2009 ; Dilworth & Hueting, 2012 ). Their structural diversity, together with the broad biological activity of thiosemicarbazone derivatives and their metal complexes, continues to attract considerable interest (Zahra et al., 2025 ). Anticancer, antimicrobial, antiviral, antimalarial and antioxidant activities have been reported, together with interactions involving albumin, DNA and biologically relevant enzymes (Devi et al., 2024 ; Nascimento et al., 2024 ; Chen et al., 2025 ; Ucar et al., 2025 ). Selected radiometal bis(thiosemicarbazone) complexes have also been investigated for diagnostic PET/SPECT imaging and therapeutic applications (Dilworth & Hueting, 2012).

Thiosemicarbazones derived from α-keto carboxylic acids are particularly attractive because the carboxylate group provides an additional O-donor site. Deprotonation of both the carboxyl group and the hydrazinic N atom thus can generate a dianionic O,N,S donor set, while the second carboxylate O atom may participate in bridging, thereby allowing both discrete chelating modes and the formation of coordination polymers. Glyoxylic acid thiosemicarbazone (H₂GAT) illustrates this structural diversity: Co^II and Ni^II form mononuclear octahedral bis-chelate complexes (Huseynova et al., 2018 a), Zn^II gives discrete complexes under some conditions (Huseynova et al., 2020 , 2022 ), whereas Cu^II and Zn^II can form one-periodic polymers through hydrazinic-N and carboxylate-O bridging, respectively (Burshtein et al., 1987 ; Huseynova et al., 2019a ,b ). Related Zn^II coordination polymers have also been investigated using crystallographic, Hirshfeld surface and theoretical approaches (Rasulovich et al., 2024 ; Nuralieva et al., 2025 ).

The aryl-substituted analogue phenylglyoxylic acid thiosemicarbazone (H₂PGTS; benzketozone) has previously been structurally characterized as its free monohydrate (Tillaeva et al., 2022 ), but its metal coordination chemistry remains much less explored.

In this context, the title compound, (I), was synthesized and its crystal structure determined by single-crystal X-ray diffraction, with intermolecular interactions quantified by Hirshfeld surface analysis.

2. Structural commentary

The asymmetric unit of (I) contains one Zn^II cation, one doubly deprotonated phenylglyoxylic acid thiosemicarbazonate ligand, one aqua ligand and one non-coordinating water molecule (Fig. 1). Zn1 is five-coordinate, bonded to the carboxylate atom O1 and the water O atom O1W in the asymmetric unit and to atoms O2ⁱ, N1ⁱ and S1ⁱ of a symmetry-related ligand [symmetry code: (i) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ]. The coordination environment, with τ₅ = 0.42 (Addison et al., 1984 ), is between the ideal square-pyramidal (τ₅ = 0) and trigonal-bipyramidal (τ₅ = 1) limits, and therefore slightly closer to square-pyramidal. In this description, S1ⁱ and O2ⁱ define the axial direction [S1ⁱ—Zn1—O2ⁱ = 155.77 (4)°], whereas O1, O1W and N1ⁱ form the equatorial set of atoms. The three equatorial angles sum up to 358.69 (12)°, and Zn1 is displaced by 0.132 (1) Å from the O1/O1W/N1ⁱ least-squares plane. The Zn—O distances are 2.0052 (13), 2.0350 (15) and 2.0976 (13) Å, while Zn—N1ⁱ and Zn—S1ⁱ are 2.1042 (15) and 2.3907 (5) Å, respectively. The two fused five-membered chelate rings, Zn1/N1ⁱ/N2ⁱ/C9ⁱ/S1ⁱ and Zn1/N1ⁱ/C7ⁱ/C8ⁱ/O2ⁱ, are nearly planar, with maximum deviations of 0.053 (2) Å (C9ⁱ) and 0.074 (1) Å (O2ⁱ), respectively, and bite angles of 79.98 (4) and 77.11 (5)°.

Figure 1
The coordination environment of Zn1 in compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as spheres of arbitrary radius. The red dotted line indicates the O—H⋯O hydrogen bond to the non-coordinating water molecule. [Symmetry code: (i) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

The ligand is doubly deprotonated, specifically at the carboxyl group and at the hydrazinic atom N2, and coordinates in the thiolate form. The C9—S1 distance of 1.7402 (18) Å lies between values expected for localized C=S and C—S bonds. The N2—C9 and N3—C9 distances [1.328 (2) and 1.339 (3) Å] are very similar, indicating substantial delocalization over the thioamide fragment. The azomethine bond N1=C7 [1.284 (2) Å] and the N1—N2 bond [1.365 (2) Å] are unexceptional. The two carboxylate C—O distances [C8—O1 = 1.270 (2) and C8—O2 = 1.245 (2) Å] are consistent with a deprotonated carboxylate group. The least-squares planes through S1/N1/N2/N3/C1/C7/C9 and O1/O2/C1/C7/C8 are roughly coplanar, forming a dihedral angle of 7.89 (7)°. This is consistent with the torsion angles Zn1—N1ⁱ—N2ⁱ—C9ⁱ = −3.3 (2)° and N1—C7—C8—O2 = 7.1 (2)°.

The phenyl ring is almost perpendicular to the chelating part of the ligand: it forms dihedral angles of 70.99 (8) and 78.56 (9)° with the thiosemicarbazide (S1/N1/N2/N3/C1/C7/C9) and carboxylate (O1/O2/C1/C7/C8) planes, respectively, and the C2—C1—C7—N1 torsion angle is 71.5 (2)°.

Because the two carboxylate O atoms coordinate to adjacent Zn^II cations, each ligand bridges two metal ions and the structure forms a one-periodic coordination polymer. The chain is generated by the 2₁ screw axis and propagates parallel to [010], with an adjacent Zn1⋯Zn1ⁱ separation of 4.8378 (4) Å (Fig. 2). The bridging carboxylate group adopts a syn–anti mode, as shown by the torsion angles Zn1—O1—C8—O2 = −9.7 (2)° and Zn1—O2ⁱ—C8ⁱ—O1ⁱ = 165.62 (15)°. Consecutive phenyl rings protrude alternately towards opposite sides of the chain.

Figure 2
Part of the polymeric chain in (I)

, propagating parallel to [010] through carboxylate bridges and the tridentate O,N,S-chelation of the ligand. H atoms have been omitted for clarity.

2.1. Supramolecular features

Hydrogen-bonding involves both water molecules and the terminal amino group N3 (Table 1). Within each coordination chain, the aqua ligand O1W donates H1WB to the thiolate atom S1 of a screw axis-related repeat unit; this nearly linear O—H⋯S contact is the only conventional hydrogen bond within an individual polymeric chain. The second H atom of the aqua ligand, H1WA, is donated to the non-coordinating water molecule O2W, which in turn acts as a double donor: H2WA is directed to the carboxylate atom O1 of a neighbouring coordination chain, while H2WB is donated to a symmetry-related non-coordinating water molecule. Consequently, the non-coordinating water molecules form a hydrogen-bonded chain extending parallel to [010] and simultaneously cross-link neighbouring Zn^II coordination chains.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O2W	0.84 (1)	2.02 (2)	2.809 (3)	155 (3)
O1W—H1WB⋯S1ⁱ	0.84 (1)	2.33 (1)	3.1718 (17)	175 (3)
O2W—H2WA⋯O1ⁱⁱ	0.84 (1)	2.19 (1)	3.011 (2)	168 (4)
O2W—H2WB⋯O2Wⁱⁱ	0.84 (1)	2.18 (1)	3.0162 (14)	178 (4)
N3—H3B⋯N2ⁱⁱⁱ	0.86 (1)	2.28 (1)	3.106 (2)	162 (2)
N3—H3A⋯Cgⁱⁱⁱ	0.85 (1)	2.61 (3)	3.173 (2)	125 (2)
Symmetry codes: (i) $[-x+1, y-{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) .

The terminal amino group N3 provides an additional interchain linkage: N3—H3B⋯N2 hydrogen bonds between inversion-related chains generate a centrosymmetric R₂²(8) motif (Etter et al., 1990 ). The second amino H atom, H3A, does not participate in a conventional hydrogen bond but is directed towards the centroid Cg of the C1–C6 phenyl ring of the same inversion-related chain, consistent with a weak N—H⋯π contact (Table 1). No significant π–π stacking is observed between the phenyl rings. The shortest centroid-to-centroid separation, 5.6580 (9) Å, occurs between rings related by translation along the b axis; although these rings are parallel, their centroids are laterally offset by 5.019 (2) Å, so that there is no face-to-face overlap. Thus, the supramolecular assembly is governed primarily by O—H⋯O, O—H⋯S and N—H⋯N hydrogen bonds, assisted by the weak N—H⋯π contact. The intrachain O—H⋯S interactions, together with the water- and amine-mediated interchain contacts, link the mono-periodic coordination polymers into a tri-periodic hydrogen-bonded network (Fig. 3).

Figure 3
Part of the crystal structure of (I)

, viewed along the b axis, showing the hydrogen bonds (dashed lines) that link neighbouring chains and the non-coordinating water molecules. H atoms not involved in hydrogen bonding have been omitted for clarity.

3. Hirshfeld surface analysis

To quantify the intermolecular contacts contributing to the crystal packing, a Hirshfeld surface analysis (McKinnon et al., 2007 ; Spackman & Jayatilaka, 2009 ) was performed using CrystalExplorer (Spackman et al., 2021 ). The surface was generated for the complex part of the asymmetric unit, i.e. one [Zn(C₉H₇N₃O₂S)(H₂O)] repeat unit of the coordination chain. The non-coordinating water molecule was excluded from this fragment in order to examine its interactions with the polymeric chain; however, it was retained as a neighbouring molecule, so that its contacts with the repeat unit, both as a hydrogen-bond donor and as an acceptor, are mapped onto the surface and included in the fingerprint plots. Because the polymer is truncated at the bridging carboxylate group, the Zn⋯O, Zn⋯H and Zn⋯C contacts (6.1% in total) arise mainly from this truncation rather than from genuine intermolecular packing contacts.

The Hirshfeld surface mapped over d_norm is shown in Fig. 4. The most intense red regions, located near the Zn^II cation and the carboxylate O atoms, correspond to the Zn—O coordination bonds to the adjacent units of the chain, which are cut by the truncation of the polymer. The other red spots correspond to the O—H⋯O, O—H⋯S and N—H⋯N hydrogen bonds listed in Table 1. The contacts with the non-coordinating water molecule are shown explicitly in Fig. 4b: O2W accepts a hydrogen bond from the aqua ligand and donates a hydrogen bond to the carboxylate atom O1 of a neighbouring chain, and both interactions appear as distinct red spots on the surface. The remaining surface is predominantly white to blue, indicating contacts close to or longer than the sum of the van der Waals radii.

Figure 4
The Hirshfeld surface of (I)

mapped over d_norm: (a) two views related by a 180° rotation and (b) a view showing the O—H⋯O hydrogen bonds (dashed lines) to the neighbouring non-coordinating water molecules (O2W).

The two-dimensional fingerprint plots (Spackman & McKinnon, 2002 ) for the full surface and those delineated into the principal contact types, together with their percentage contributions, are shown in Fig. 5. H⋯H contacts make the largest contribution, followed by C⋯H/H⋯C, H⋯S/S⋯H, O⋯H/H⋯O and N⋯H/H⋯N contacts; each of the remaining contact types not shown in Fig. 5 contributes less than 2%. The relatively large H⋯S/S⋯H contribution reflects the exposed thiolate S atom, which both coordinates to Zn^II and acts as an acceptor in the O—H⋯S hydrogen bond. Overall, the crystal packing is dominated by contacts involving H atoms, consistent with the hydrogen-bonding network described above, while the very small C⋯C contribution (0.6%) confirms the absence of significant π–π stacking.

Figure 5
Two-dimensional fingerprint plots for (I)

, showing the full fingerprint plot and those delineated into H⋯H, C⋯H/H⋯C, H⋯S/S⋯H, O⋯H/H⋯O, N⋯H/H⋯N, Zn⋯O/O⋯Zn, O⋯C/C⋯O and O⋯O contacts, and their relative percentage contributions.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 6.01, November 2025, including the February 2026 updates; Groom et al., 2016 ) was carried out using ConQuest, restricted to metal-containing structures and using the α-oxo-carboxylate thiosemicarbazone fragment O—C(O)—C—N—N—C(S)—N with all bond types unspecified. The search returned 97 hits. In most of them, the substituent at the azomethine C atom is H, methyl, ethyl or 2-carboxyethyl, corresponding to derivatives of glyoxylic, pyruvic, 2-oxobutyric or 2-oxoglutaric acid. The closest aryl-substituted analogue is PIZTOH (Sonawane et al., 1994 ), which carries a benzyl substituent. No metal complex with a phenyl group directly bonded to the azomethine C atom was found, so that compound (I) is the first structurally characterized metal complex of this ligand type.

Comparison with the free ligand, H₂PGTS·H₂O (GEJFAG; Tillaeva et al., 2022), shows the changes caused by deprotonation and coordination. In GEJFAG, the ligand is neutral, with protonated carboxyl and hydrazinic N2 groups, and the C9—S1 bond [1.690 (2) Å] corresponds to a thione form. In the crystal structure of (I), C9—S1 is lengthened to 1.7402 (18) Å, consistent with the thiolate form. At the same time, N2—C9 is shortened from 1.351 (3) to 1.328 (2) Å and N3—C9 is lengthened from 1.306 (3) to 1.339 (3) Å, so that the two C—N bonds of the thioamide fragment become nearly equal, indicating charge delocalization after deprotonation of N2. Coordination also changes the ligand conformation considerably. In GEJFAG, the phenyl ring forms dihedral angles of 22.6 (1) and 47.9 (1)° with the thiosemicarbazide (S1/N1/N2/N3/C1/C7/C9) and carboxyl (O1/O2/C1/C7/C8) planes, respectively, and the C2—C1—C7—N1 torsion angle is −27.2 (3)°. In (I), the corresponding values are 70.99 (8), 78.56 (9) and 71.5 (2)°. This rotation is presumably required to relieve steric repulsion between the phenyl ring and the planar, fused O,N,S-chelate system.

Among complexes of the parent glyoxylic acid thiosemicarbazone (H₂GAT), both discrete and polymeric structures are known. Co^II and Ni^II form mononuclear octahedrally coordinated bis-chelates (ODOWUC and ODOXAJ; Huseynova et al., 2018). Ni^II also forms discrete bis-chelates, [Zn(HGAT)₂]·xH₂O (FOTPAI, x = 5/3; Huseynova et al., 2020; VADFEP, x = 3/2; Huseynova et al., 2022), in which two monoanionic ligands coordinate to the overall six-coordinate Zn^II cation. In FOTPAI, the Zn—O [2.105 (3)–2.197 (3) Å], Zn—N [2.138 (3)–2.175 (3) Å] and Zn—S [2.4974 (12)–2.5874 (13) Å] bonds are all longer than the corresponding bonds in the structure of (I) [2.0052 (13)–2.0976 (13), 2.1042 (15) and 2.3907 (5) Å, respectively], as expected for the lower coordination number and the dianionic ligand in (I).

Only nine of the 97 hits are one-periodic coordination polymers: six Cu, two Pb and one Zn complexes. The Zn^II polymer of H₂GAT (LOXNAQ; Huseynova et al., 2019b) is the closest analogue of (I). In both structures, the dianionic ligand chelates one five-coordinate Zn^II cation through the O,N,S donor set, a water molecule completes the coordination sphere, and the second carboxylate O atom bridges to the next Zn^II ion. Unlike in (I), however, LOXNAQ contains no non-coordinating water molecule, so that the water-mediated cross-linking of the chains observed in (I) is absent. A different mode of chain propagation is found in the Cu^II polymer of the same ligand (GERPAU, Burshtein et al., 1987; redetermined as GERPAU01, Huseynova et al., 2019a). Here, the square-pyramidally coordinated Cu^II cations are linked through the hydrazinic N atom, and the carboxylate group acts only as a chelating donor. Replacing the H atom of H₂GAT by a phenyl group in (I) therefore does not change the carboxylate-bridged chain motif. However, the phenyl rings, which protrude alternately to opposite sides of the chain, prevent close packing of the chains and preclude π–π stacking, so that the chains are linked only through hydrogen bonds involving the water molecules and the amino group.

5. Synthesis and crystallization

The ligand H₂PGTS·H₂O was prepared according to the published procedure (Tillaeva et al., 2022). A solution of Zn(CH₃COO)₂·2H₂O (0.220 g, 1.00 mmol) in water (5 ml) was added to a solution of H₂PGTS·H₂O (0.242 g, 1.00 mmol) in ethanol (5 ml). The reaction mixture was stirred at 333 K at 500 rpm for 10 min and then allowed to evaporate slowly at room temperature. After 5 d, colourless block-shaped crystals suitable for single-crystal X-ray diffraction were obtained (yield 55%). Analysis calculated for C₉H₁₁N₃O₄SZn (M_r = 322.64): C, 33.50; H, 3.44; N, 13.02; S, 9.94%. Found: C, 33.45; H, 3.39; N, 12.98; S, 9.97%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms attached to C atoms were placed in calculated positions (C—H = 0.93 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C). The H atoms of the aqua ligand, the non-coordinating water molecule and of the amino group were located in difference-Fourier maps and refined with restrained O—H and N—H distances of 0.85 (1) and 0.86 (1) Å, respectively. Their positional and isotropic displacement parameters were refined independently. A total of six distance restraints were applied.

Table 2
Experimental details

Crystal data
Chemical formula	[Zn(C₉H₇N₃O₂S)(H₂O)]·H₂O
M_r	322.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	10.5337 (1), 5.6580 (1), 21.0089 (3)
β (°)	100.760 (1)
V (Å³)	1230.11 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.49
Crystal size (mm)	0.3 × 0.2 × 0.12

Data collection
Diffractometer	Xcalibur, Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 )
T_min, T_max	0.572, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7561, 2514, 2354
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.078, 1.06
No. of reflections	2514
No. of parameters	188
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.31
Computer programs: CrysAlis PRO (Rigaku OD, 2023), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2591804

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026010169/wm5813sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026010169/wm5813Isup2.hkl

checkCIF report

Computing details top

catena-Poly[[[aquazinc(II)]-µ-2-({[amino(sulfanidyl)methylidene]amino}imino)-2-phenylacetato-κ⁴O,N,S:O'] monohydrate] top

Crystal data top

[Zn(C₉H₇N₃O₂S)(H₂O)]·H₂O	F(000) = 656
M_r = 322.64	D_x = 1.742 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.5337 (1) Å	Cell parameters from 5766 reflections
b = 5.6580 (1) Å	θ = 4.2–76.1°
c = 21.0089 (3) Å	µ = 4.49 mm⁻¹
β = 100.760 (1)°	T = 291 K
V = 1230.11 (3) Å³	Block, colourless
Z = 4	0.3 × 0.2 × 0.12 mm

Data collection top

Xcalibur, Ruby diffractometer	2514 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2354 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 10.2576 pixels mm^-1	θ_max = 76.4°, θ_min = 4.3°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −7→5
T_min = 0.572, T_max = 1.000	l = −22→26
7561 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0492P)² + 0.2444P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.29 e Å⁻³
2514 reflections	Δρ_min = −0.31 e Å⁻³
188 parameters	Extinction correction: SHELXL2025/1 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0015 (2)

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	0.33743 (2)	0.15367 (4)	0.18671 (2)	0.02765 (12)
S1	0.76756 (4)	0.93004 (9)	0.39192 (2)	0.03347 (14)
O1	0.32015 (13)	0.3021 (2)	0.27135 (6)	0.0330 (3)
O1W	0.19866 (16)	−0.0979 (3)	0.18463 (10)	0.0505 (4)
H1WA	0.1198 (13)	−0.091 (6)	0.1870 (17)	0.074 (10)*
H1WB	0.210 (3)	−0.227 (3)	0.1666 (15)	0.073 (10)*
O2	0.52699 (13)	0.3937 (2)	0.27595 (7)	0.0339 (3)
N1	0.51936 (14)	0.6934 (3)	0.37017 (7)	0.0271 (3)
N2	0.52557 (16)	0.8524 (3)	0.41950 (8)	0.0324 (4)
N3	0.64759 (19)	1.1381 (4)	0.47600 (10)	0.0444 (5)
C1	0.29820 (16)	0.5810 (3)	0.38054 (8)	0.0271 (4)
C2	0.21642 (19)	0.7747 (4)	0.36741 (9)	0.0340 (4)
H2	0.238097	0.898891	0.342474	0.041*
C3	0.1029 (2)	0.7831 (4)	0.39137 (11)	0.0410 (5)
H3	0.047601	0.911604	0.381886	0.049*
C4	0.0713 (2)	0.6005 (4)	0.42947 (10)	0.0413 (5)
H4	−0.004767	0.607332	0.445818	0.050*
C5	0.1526 (2)	0.4085 (4)	0.44320 (10)	0.0417 (5)
H5	0.131217	0.286301	0.468878	0.050*
C6	0.2663 (2)	0.3973 (4)	0.41872 (10)	0.0349 (4)
H6	0.320883	0.267589	0.427841	0.042*
C7	0.41709 (17)	0.5678 (3)	0.35307 (8)	0.0267 (4)
C8	0.42359 (17)	0.4086 (3)	0.29632 (8)	0.0274 (4)
C9	0.63595 (17)	0.9720 (3)	0.42991 (8)	0.0300 (4)
O2W	−0.03563 (18)	−0.1447 (4)	0.22900 (11)	0.0613 (5)
H2WA	−0.1165 (10)	−0.148 (6)	0.2234 (19)	0.081 (11)*
H2WB	−0.016 (4)	−0.283 (3)	0.2415 (19)	0.088 (12)*
H3A	0.7214 (14)	1.202 (4)	0.4853 (13)	0.044 (7)*
H3B	0.5869 (19)	1.153 (4)	0.4977 (11)	0.046 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02673 (16)	0.03423 (18)	0.02422 (16)	−0.00090 (9)	0.01046 (10)	−0.00270 (9)
S1	0.0263 (2)	0.0425 (3)	0.0332 (2)	−0.00429 (17)	0.00958 (17)	−0.00229 (18)
O1	0.0305 (7)	0.0431 (7)	0.0263 (6)	−0.0046 (5)	0.0078 (5)	−0.0097 (5)
O1W	0.0379 (8)	0.0392 (8)	0.0795 (12)	−0.0112 (7)	0.0243 (8)	−0.0157 (8)
O2	0.0345 (7)	0.0385 (7)	0.0324 (7)	−0.0053 (6)	0.0155 (5)	−0.0094 (6)
N1	0.0258 (7)	0.0354 (8)	0.0211 (7)	−0.0024 (6)	0.0070 (5)	−0.0035 (6)
N2	0.0296 (8)	0.0430 (9)	0.0260 (7)	−0.0071 (6)	0.0091 (6)	−0.0111 (6)
N3	0.0385 (10)	0.0562 (12)	0.0412 (10)	−0.0172 (8)	0.0145 (8)	−0.0212 (9)
C1	0.0244 (8)	0.0367 (9)	0.0208 (7)	−0.0034 (7)	0.0058 (6)	−0.0052 (7)
C2	0.0327 (9)	0.0378 (10)	0.0319 (9)	0.0002 (8)	0.0071 (7)	0.0019 (8)
C3	0.0300 (10)	0.0527 (12)	0.0403 (11)	0.0087 (9)	0.0066 (8)	−0.0028 (9)
C4	0.0290 (9)	0.0630 (13)	0.0349 (10)	−0.0016 (9)	0.0137 (8)	−0.0040 (9)
C5	0.0421 (11)	0.0508 (12)	0.0364 (10)	−0.0075 (9)	0.0181 (9)	0.0036 (9)
C6	0.0357 (10)	0.0388 (10)	0.0324 (9)	0.0021 (8)	0.0115 (8)	0.0030 (8)
C7	0.0261 (8)	0.0335 (9)	0.0212 (8)	−0.0021 (7)	0.0064 (6)	−0.0014 (7)
C8	0.0307 (9)	0.0309 (9)	0.0215 (8)	−0.0005 (7)	0.0069 (6)	−0.0004 (7)
C9	0.0289 (8)	0.0377 (10)	0.0237 (8)	−0.0021 (7)	0.0060 (6)	−0.0012 (7)
O2W	0.0398 (10)	0.0780 (14)	0.0641 (12)	−0.0045 (9)	0.0040 (8)	0.0210 (10)

Geometric parameters (Å, º) top

Zn1—S1ⁱ	2.3907 (5)	C1—C2	1.389 (3)
Zn1—O1	2.0052 (13)	C1—C6	1.392 (3)
Zn1—O1W	2.0350 (15)	C1—C7	1.475 (2)
Zn1—O2ⁱ	2.0976 (13)	C2—H2	0.9300
Zn1—N1ⁱ	2.1042 (15)	C2—C3	1.382 (3)
S1—C9	1.7402 (18)	C3—H3	0.9300
O1—C8	1.270 (2)	C3—C4	1.385 (3)
O1W—H1WA	0.843 (10)	C4—H4	0.9300
O1W—H1WB	0.844 (10)	C4—C5	1.380 (3)
O2—C8	1.245 (2)	C5—H5	0.9300
N1—N2	1.365 (2)	C5—C6	1.391 (3)
N1—C7	1.284 (2)	C6—H6	0.9300
N2—C9	1.328 (2)	C7—C8	1.506 (2)
N3—C9	1.339 (3)	O2W—H2WA	0.838 (10)
N3—H3A	0.847 (10)	O2W—H2WB	0.840 (10)
N3—H3B	0.856 (10)

O1—Zn1—S1ⁱ	103.41 (4)	C1—C2—H2	120.0
O1—Zn1—O1W	97.37 (7)	C3—C2—C1	120.07 (19)
O1—Zn1—O2ⁱ	97.49 (6)	C3—C2—H2	120.0
O1—Zn1—N1ⁱ	130.72 (6)	C2—C3—H3	119.9
O1W—Zn1—S1ⁱ	101.83 (6)	C2—C3—C4	120.2 (2)
O1W—Zn1—O2ⁱ	87.34 (7)	C4—C3—H3	119.9
O1W—Zn1—N1ⁱ	130.60 (7)	C3—C4—H4	119.9
O2ⁱ—Zn1—S1ⁱ	155.77 (4)	C5—C4—C3	120.11 (19)
O2ⁱ—Zn1—N1ⁱ	77.11 (5)	C5—C4—H4	119.9
N1ⁱ—Zn1—S1ⁱ	79.98 (4)	C4—C5—H5	119.9
C9—S1—Zn1ⁱⁱ	95.78 (6)	C4—C5—C6	120.1 (2)
C8—O1—Zn1	110.63 (11)	C6—C5—H5	119.9
Zn1—O1W—H1WA	133 (2)	C1—C6—H6	120.1
Zn1—O1W—H1WB	117 (2)	C5—C6—C1	119.77 (19)
H1WA—O1W—H1WB	107 (3)	C5—C6—H6	120.1
C8—O2—Zn1ⁱⁱ	113.71 (11)	N1—C7—C1	126.26 (16)
N2—N1—Zn1ⁱⁱ	124.33 (11)	N1—C7—C8	113.11 (15)
C7—N1—Zn1ⁱⁱ	115.78 (12)	C1—C7—C8	120.49 (15)
C7—N1—N2	119.72 (15)	O1—C8—C7	116.67 (15)
C9—N2—N1	112.18 (15)	O2—C8—O1	124.32 (16)
C9—N3—H3A	115.1 (18)	O2—C8—C7	118.99 (16)
C9—N3—H3B	118.7 (18)	N2—C9—S1	127.08 (14)
H3A—N3—H3B	125 (3)	N2—C9—N3	115.87 (17)
C2—C1—C6	119.74 (17)	N3—C9—S1	117.02 (14)
C2—C1—C7	120.16 (17)	H2WA—O2W—H2WB	102 (3)
C6—C1—C7	120.10 (17)

Zn1ⁱⁱ—S1—C9—N2	8.01 (18)	C1—C2—C3—C4	1.1 (3)
Zn1ⁱⁱ—S1—C9—N3	−174.01 (16)	C1—C7—C8—O1	4.7 (3)
Zn1—O1—C8—O2	−9.7 (2)	C1—C7—C8—O2	−176.99 (17)
Zn1—O1—C8—C7	168.47 (12)	C2—C1—C6—C5	0.3 (3)
Zn1ⁱⁱ—O2—C8—O1	165.62 (15)	C2—C1—C7—N1	71.5 (2)
Zn1ⁱⁱ—O2—C8—C7	−12.5 (2)	C2—C1—C7—C8	−103.8 (2)
Zn1ⁱⁱ—N1—N2—C9	−3.3 (2)	C2—C3—C4—C5	−0.6 (3)
Zn1ⁱⁱ—N1—C7—C1	−173.36 (14)	C3—C4—C5—C6	−0.1 (3)
Zn1ⁱⁱ—N1—C7—C8	2.2 (2)	C4—C5—C6—C1	0.3 (3)
N1—N2—C9—S1	−4.4 (2)	C6—C1—C2—C3	−1.0 (3)
N1—N2—C9—N3	177.57 (17)	C6—C1—C7—N1	−109.7 (2)
N1—C7—C8—O1	−171.16 (16)	C6—C1—C7—C8	75.0 (2)
N1—C7—C8—O2	7.1 (2)	C7—N1—N2—C9	−178.26 (17)
N2—N1—C7—C1	2.1 (3)	C7—C1—C2—C3	177.80 (18)
N2—N1—C7—C8	177.66 (15)	C7—C1—C6—C5	−178.50 (17)

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2W	0.84 (1)	2.02 (2)	2.809 (3)	155 (3)
O1W—H1WB···S1ⁱⁱⁱ	0.84 (1)	2.33 (1)	3.1718 (17)	175 (3)
O2W—H2WA···O1^iv	0.84 (1)	2.19 (1)	3.011 (2)	168 (4)
O2W—H2WB···O2W^iv	0.84 (1)	2.18 (1)	3.0162 (14)	178 (4)
N3—H3B···N2^v	0.86 (1)	2.28 (1)	3.106 (2)	162 (2)
N3—H3A···Cg^v	0.85 (1)	2.61 (3)	3.173 (2)	125 (2)

Symmetry codes: (iii) −x+1, y−3/2, −z+1/2; (iv) −x, y−1/2, −z+1/2; (v) −x+1, −y+2, −z+1.

Acknowledgements

The authors thank the Center for Collective Use of Scientific Equipment at the Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, for access to the single-crystal X-ray diffractometer and for technical assistance with the X-ray diffraction measurements.

Funding information

This research was conducted at the Laboratory of Complex Compounds, Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, with financial support from the Government of the Republic of Uzbekistan.

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