Syntheses and structures of dinuclear zinc(II) acetate-bridged coordination compounds with the aromatic Schiff base chelators N,N-dimethyl-2-[phen­yl(pyridin-2-yl)methyl­idene]hydrazine-1-carbothio­amide and N-ethyl-2-[phen­yl(pyridin-2-yl)methyl­idene]hydrazine-1-carbo­thio­amide

Parry, C.S.; Abraham, A.R.; Kwofie, S.K.; Wilson, M.D.; Ramadhar, T.R.; Butcher, R.J.

doi:10.1107/S2056989025005407

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 81| Part 7| July 2025| Pages 636-641

https://doi.org/10.1107/S2056989025005407

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Syntheses and structures of dinuclear zinc(II) acetate-bridged coordination compounds with the aromatic Schiff base chelators N,N-dimethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamide and N-ethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamide

Christian S. Parry,^a ^* Alex R. Abraham,^b Samuel K. Kwofie,^c Michael D. Wilson,^d Timothy R. Ramadhar ^b ^* and Raymond J. Butcher ^b ^*

^aDepartment of Microbiology, College of Medicine, Howard University, Washington, DC 20059, USA, ^bDepartment of Chemistry, College of Arts and Science, Howard University, Washington, DC 20059, USA, ^cDepartment of Biomedical Engineering, School of Engineering Sciences, College of Basic and Applied Sciences, University of Ghana, Legon, Accra, LG 77, Ghana, and ^dDepartment of Parasitology, Noguchi Memorial Institute for Medical Research, College of Health Sciences, University of Ghana, Legon, Accra, LG 581, Ghana
^*Correspondence e-mail: [email protected], [email protected], [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 5 April 2025; accepted 17 June 2025; online 24 June 2025)

In the centrosymmetric title complexes, di-μ-acetato-bis({N,N-dimethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamidato}zinc(II)), [Zn₂(C₁₅H₁₅N₄S)₂(C₂H₃O₂)₂] (I), and di-μ-acetato-bis({N-ethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamidato}zinc(II)), [Zn₂(C₁₆H₁₇N₄S)₂(C₂H₃O₂)₂] (II), the zinc ions are chelated by the N,N,S-tridentate ligands and bridged by pairs of acetate ions. The acetate ion in (I) is disordered over two orientations in a 0.756 (6):0.244 (6) ratio, leading to different zinc coordination modes for the major (5-coordinate) and minor (6-coordinate) disorder components. Geometrical indices [τ₅ = 0.32 and 0.30 for (I) (major component) and (II), respectively] suggest the zinc coordination in these phases to be distorted square pyramidal. This study forms part of our aim to discern the mechanism of metal binding in these chelators, their specificity and selectivity, and to gain insight into the role of cellular zinc in physiological processes such as infection, immunity and cancer.

Keywords: crystal structure; mobile zinc; lipophilicity; mixed donor set; coordination chemistry; cell biology.

CCDC references: 2427149; 2428884

1. Chemical context

Divalent zinc (Zn²⁺) is a highly abundant and essential nutrient in the human body and is required in nearly all cellular function including cell growth, DNA repair, and immune function (Berg & Shi, 1996 ; Lonergan & Skaar, 2019 ). Zinc is important in pharmacology, toxicology and in imaging as cellular probes (Pluth et al., 2011 ; Radford & Lippard, 2013 ). Like iron, both an excess and a deficiency of zinc lead to cellular and organism-level pathology. It is therefore necessary that the levels and distribution of labile zinc be exquisitely regulated within and outside the cell.

Comparatively, a lot is known about the role of zinc in proteins, as exemplified by the zinc finger structural motif (Frankel et al., 1987 ; Berg, 1990 ). This, however, may have overshadowed other essential roles of zinc, thus limiting our understanding of cell biology and our ability to design ligands that are able to modulate cellular homeostasis. There is a sizeable pool of `free' or `labile zinc' – non-protein bound zinc attached to a vast number of low molecular weight ligands – that take part in ligand binding and ligand exchange within and outside the cell. There is a need to investigate the function of labile zinc within cells and tissues. This requires tools that can detect 'free' zinc ion species in a quantitative manner, reporting their exact cellular location and precise interaction.

Zinc chelators are such tools, but they have not been well studied (Dean et al., 2012 ). Zinc chelators are important for zinc ion sequestration and transport, and can be used as probes for imaging. Zinc-chelating agents can be designed with respect to affinity, hydrophobicity, lipophilicity and specificity for diverse metals – the basis of zinc preference for donor atoms and coordination chemistry. Current zinc probes lack specificity and may also have side effects in living systems (Krężel & Maret, 2016 ; Catapano et al., 2018 ). The search for chelators of improved efficacy with no side effects remains a distant goal.

Chelating ligands have therapeutic and diagnostic use in the clinic and in research. The biological activities of metal-bound ligand complexes differ from those of either the ligand or the metal ion itself, and increased or decreased biological activity has been reported for several transition metal complexes. Of clinical interest, Richardson and coworkers have demonstrated that the Schiff base ligand series 2-(di-2-pyridinylmethylene)-N,N-dimethyl-hydrazinecarbothioamide (Dp44mT), N,N-dimethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazinecarbothioamide (Bp44mT), and di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC) used as iron chelators have strong anti-tumor response (Yuan et al., 2004 ; Yu et al., 2011 ; Heffeter et al., 2019 ). Bp44mT (neutral molecule C₁₅H₁₆N₄S, anion C₁₅H₁5N₄S⁻) is the ligand, L1. Richardson and colleagues also showed that these chelators in complex with metals have additional properties and are able to overcome clinical drug resistance. Specifically, the zinc complexes of Dp44mT, DpC and L1 have potent cytotoxic activity against cancer cells and are able to target the lysosome through transmetallation with copper (Yu et al., 2012 ; Sestak et al., 2015 ; Stacy et al., 2016 ). Metals, especially iron and zinc, are also crucial at the intersection of immunology and infectious diseases (Weinberg, 1984 ; Cassat & Skaar, 2013 ; Nairz & Weiss, 2020 ). Their coordination chemistry and stereochemistry are important with respect to their transport and recognition in the microbial niche (Winkelmann & Braun, 1981 ; Adjimani & Emery, 1988 ; Juttukonda et al., 2020 ). Recently, Skaar and coworkers have shown convincingly that dietary zinc deficiency critically degrades the immune response against pneumonia and promotes Acinetobacter baumannii lung infection in elders and in patients who require ventilation (Palmer et al., 2024 ).

The many excellent biological attributes of Zn²⁺ ion derive from its electronic structure as a 3d¹⁰ ion. As such, zinc lacks ligand field stabilization energy or preference for a specific geometry. Zinc has coordination flexibility that facilitates rapid adoption of different structural geometries depending on the ligand and the environment – the electrostatic and steric interactions around the ligands – and not by the ion's electronic ligand field stabilization energy. This also facilitates rapid ligand exchange. These properties endow zinc with its adaptability enabling it to participate in many biological functions and rapidly with diverse coordination and hapticity (Krężel & Maret, 2016). When zinc is penta-coordinate, it may adopt either a trigonal–bipyramidal or square-pyramidal structure. Also, the filled d orbitals precludes it from taking part in redox reactions. Zinc has a single normal oxidation state (+2) and the zinc ion only functions as a Lewis acid, a property crucial for its buffering and antioxidant role in the cell (Krężel & Maret, 2016). Biological zinc is predominantly coordinated by nitrogen donor atoms (as in histidine), sulfur donor atoms (as in cysteine residues), and with O donor atoms, as in glutamate or aspartate (Karlin et al., 1997 ).

We recently described a more and highly effective derivative chelating agent, the ligand (E)-N-ethyl-2-(phenyl(pyridin-2-yl)methylene)hydrazine-1-carbothioamide (neutral molecule C₁₆H₁₈N₃S, anion C₁₆H₁₇N₃S⁻) (L2). L2 is commonly called 2-phenyl-1-pyridin-2-yl-ethanone or PPYeT (Kumari et al., 2012 ) and is built on the common existing thiosemicarbazone (TSC) backbone (Parry et al., 2025 ; Bonaccorso et al., 2019 ), after ligand L1 (Yu et al., 2012). L2 has a more flexible scaffold compared to previously reported thiosemicarbazone BpT-based chelators and was more specific and had greater chelating effectiveness with fewer side effects (Kumari et al., 2012). L2 has also shown unusual effectiveness as an antiviral agent. The reported efficacy and desirable properties have spurred us to carry out detailed structural analyses of this new class of metal chelators. To that end, we have prepared the respective zinc compounds of L1 and L2 [(I) and (II), respectively] to gain insight to their structure, metal-bound complexes and coordination chemistry to elucidate their mechanism, the basis of their specificity and selectivity, and to expand their use.

2. Structural commentary

The crystal structure of the reaction product of zinc-ion binding to ligand L1 is a 2:2 complex (I), a dimer of monomeric zinc-bound ligands. Likewise, the structure of the reaction product of zinc and L2 is a 2:2 complex (II). In both compounds, the organic ligand is bound to zinc in a tridentate fashion through the N,N′,S donor set, as expected. Further, the two metal ions in the complex are bridged by two acetate linkers to form 2:2 complexes. Selected geometrical data are listed in Tables 1 and 2.

Table 1
Selected bond lengths (Å) for (I)

Zn1—S1	2.3705 (17)	Zn1—O2ⁱ	2.006 (5)
Zn1—N1	2.117 (3)	Zn1—O1A	2.114 (14)
Zn1—N4	2.159 (5)	Zn1—O1Aⁱ	2.052 (18)
Zn1—O1	2.018 (5)	Zn1—O2Aⁱ	2.410 (18)
Symmetry code: (i) .

Table 2
Selected bond lengths (Å) for (II)

Zn1—S1	2.3360 (6)	Zn1—N1	2.1017 (19)
Zn1—O1ⁱ	2.0547 (17)	Zn1—N3	2.1128 (19)
Zn1—O1	2.0567 (16)
Symmetry code: (i) .

We encountered disorder of the acetate ion in (I) during refinement. The disorder was modeled with two equivalent orientations (Müller et al., 2006 ; Herbst-Irmer, 2016 ; Archana et al., 2022 ). The major domain was assigned 76% occupancy; this is the orientation described above as five-coordinate (Fig. 1a). The alternate domain has a zinc metal center coordinating, as previously described, with the ligand anion through the N,N′,S donor set but with additional coordinate bonds to both oxygen atoms of an acetate linker and to a single O atom from the second acetate linker, so that each zinc center altogether forms a six-coordinate geometry (24% occupancy) (Fig. 1b). The two domains together, superimposed as in the crystal, are shown in Fig. 2, with zinc-coordinating bonds of the minor domain shown with dashed lines in white. A tilt of the C—C stem (bond C16A—C17A) of the acetate group can also be seen.

Figure 1
Disordered structure of (I): (a) the major disorder component, in which the zinc ion binds to ligand donors in 5-coordinate mode; (b) the minor disorder component, in which the zinc atom binds in a six-coordinate mode. Atoms with suffix a are generated by the symmetry operation −x, 1 − y, 1 − z.

Figure 2
Overlay of the major and minor components of (I). Coordinating bonds of the minor component are shown in dashed lines in white. Atoms with suffix a are generated by the symmetry operation −x, 1 − y, 1 − z.

The structure of (II), also a 2:2 complex, on the other hand, was not twinned. In this structure, a zinc ion coordinates the N,N′,S donor set of the L2 anionic ligand in (II) and with two oxygen atoms: one O atom from each of the two acetate linkers, in penta-coordinate mode. The other zinc ion makes similar coordination with the mixed donor set. In distinct contrast with either of the two zinc coordination modes seen in complex (I), in complex (II), one O atom in the acetate linker is left uncoordinated (Fig. 3).

Figure 3
The molecular structure of (II). Atoms with suffix a are generated by the symmetry operation −x, 1 − y, 1 − z.

Therefore, from the two crystal structures, we find three distinct zinc coordination modes (Fig. 4). Modes 1 and 2 correspond to the major and minor domains of complex (I) (Fig. 1; panels a and b, respectively), and mode 3 corresponds to the sole structure of (II).

Figure 4
The coordination modes of the zinc centers in the metal-bound complexes. Three distinct coordination modes are discernible in our analysis.

A notable feature of Zn²⁺ ions is inducing dimerization. Dimer formation would be favored especially in the context of heterocyclic ligands such as L1 and L2 presenting with a mixed donor set and the carboxylate group from the metal salt serving as a bridge. Dimerization allows the formation of more ordered structures with greater stability and enhanced functional efficacy including cooperative binding. Zinc ion-induced dimerization is common in proteins; examples are zinc fingers and class II major histocompatibility complex molecules (Wang et al., 2001 ; Li et al., 2007 ). Zinc ion-induced dimerization is also important in small molecule ligand interactions in cells and tissues.

Comparing the complexed structures in this study, the zinc coordinate bonds appear to be shorter in (II) than in (I): for example, the zinc–pyridine N bond length in (II), Zn1—N3 = 2.113 (2) Å is perceptibly shorter than in (I) [2.159 (5) Å]. This trend is true for zinc coordination to the donors within the ligand (pyridine N, imine N and sulfur S1) (Tables 1 and 2). Zinc coordinate bonding bridging the O atoms from the acetate anion remain tight in complex (II) [Zn1—O1ⁱ; symmetry code: (i) −x, −y + 1, −z + 1, Zn1—O1 average bond length = 2.055 Å]. Comparable bond lengths in complex (I) major domain are: Zn1—O2ⁱ = 2.006 (5) Å and Zn1—O1 = 2.018 (5) Å indicating there is strong bonding through the bridging O atoms in the major disorder component of (I). The corresponding bond lengths in the minor component are Zn1—O2Aⁱ = 2.410 (18) Å, Zn1—O1Aⁱ = 2.052 (18) Å and Zn1—O1A = 2.114 (14) Å (Tables 1 and 2).

In the major component of (I), the zinc center makes a coordinate bond with an O atom from each acetate group; the angle at the zinc center, O2ⁱ—Zn1—O1, is 121.0 (3)°. The second zinc center binds in the same manner in this dinuclear dimer structure. In the minor component of (I), the acetate group is rotated by 26.7 (16)° (C16—C17 bond versus C16A—C17A) compared to the acetate group in the major component (Fig. 2), so that both O atoms can coordinate with Zn1 [O2Aⁱ—Zn1—O1Aⁱ = 54.7 (6)°]. Atom O1Aⁱ coordinates further with Zn1ⁱ. The angle made by this distinctive bond, Zn1—O1Aⁱ—Zn1ⁱ is 125.1 (8)°. A comparable but different mode of coordination is seen in (II): one O atom of an acetate group bridges the two zinc centers with no involvement of the other O atom in the group and the second acetate group shows the same bonding mode by symmetry [Zn1—O—Zn1ⁱ = 101.26 (7)°].

3. Supramolecular features

There is an abundance of donor atoms in both structures. However, we found only three hydrogen bonds (Table 3) in complex (I) and none in complex (II). These contribute subtly but significantly to packing in both the major and minor disorder components of (I). In the minor domain, hydrogen atom H14 from a terminal methyl group (C14) interacts with the sulfur atom of an adjacent molecule; the same H atom forms a hydrogen bond with an O atom of an acetate bridging group. In the case of the major domain, H14 in the same manner interacts with sulfur atom S1 of an adjacent molecule; additionally, hydrogen atom H17 from the methyl group carbon C17 of the bridging acetate anion reaches to O atom (O1) of an acetate bridging group in a nearby molecule in the major domain configuration. Carbon has a low electronegativity value and is typically not considered a hydrogen-bond donor in the same regard as oxygen, nitrogen or fluorine. However, these carbon hydrogen-bond donors (C14 and C17) are connected to amide N and acetate –COO⁻ groups, respectively and contribute weak but significant interactions. The arrangement and cohesion of molecules in the structure of complex (I) does not depend solely on hydrogen bonds. The packing scheme reveals favorable interactions between phenyl rings and the aliphatic stem of neighboring molecules contributing favorable van der Waals interactions and weak dispersive forces.

Table 3
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯S1ⁱⁱ	0.96	3.00	3.832 (7)	146
C14—H14B⋯O2Aⁱⁱⁱ	0.96	2.65	3.36 (2)	131
C17—H17C⋯O1^iv	0.96	2.57	3.493 (9)	160
Symmetry codes: (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) .

It is notable that, even with the abundance of electron donors (hanging double-bonded O atom from the bridging group) and N and S donors from the ligand (Fig. 5), no hydrogen bonds are found in the extended structure of complex (II). Fig. 5 depicts packing in the crystal and shows a view down [100]. There are no electron acceptors in the vicinity of the O donors. The packing scheme shows additive alignment of hydrophobic groups (phenyl and aliphatic groups) in addition to potential dispersive forces. The distance between a terminal methyl group and a phenyl ring is 4.54 Å. There is an abundance of –CH₃ and –CH groups near the exposed double-bonded O atom that can contribute dispersive forces to packing. We detected no aromatic π–π stacking interactions. Though there is an abundance of donor groups in the starting ligand, the metal-bound complexes may have lipophilic profile and stability values different from the parent ligand, as we observe in this complex (II).

Figure 5
Packing structure of (II). A view down [100] is shown along with the unit cell.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.44, update September 2023; search date: March 14, 2025; Groom et al., 2016 ) for structures similar to L2 yielded no results. A search on L1 gave 36 unique hits, 11 of which are unbound ligands and 25 are metal-bound complexes. CSD refcode OBUHAW (Jayakumar et al., 2011 ) is recognized as ligand L1 in its unbound form, also JURBUX (Parry et al., 2025), that we used for our 2:2 zinc complex (I) being reported here. Notable in this set is structure RIYMUH (Valdés-Martínez et al., 1996 ), a derivative of OBUHAW that has been evaluated in phase 1 clinical trials for use against cancers (Heffeter et al., 2019).

The complexes we found in the search are in 1:1, 1:2 or 2:2 metal: ligand ratio and the ligands are tridentate. ARARAM is a centrosymmetric dimer of two monomeric complexes with two chloro groups bridging at the metal centers (Sreekanth & Kurup, 2003 ). ARAREQ is similar but it is a monomeric complex, with bromide instead of chloride (Sreekanth & Kurup, 2003). Coordination around the Cu center is square planar. A 1:2 Cu complex forms in AWEQUQ (Stacy et al., 2016), where the single positive charge at the copper center is balanced by the perchlorate anion ClO₄⁻. BIHSIX (Fang et al., 2018 ) is a 1:2 complex of zinc and L1. In BIHSIX, L1 is tridentate and coordinates with zinc at the L1 imine N, pyridine N and sulfur S atoms as in our structure (I); the second ligand in BIHSIX binds in the same manner. However, in distinct contrast with BIHSIX, our structure (I) is a 2:2 (dinuclear) dimer, though BIHSIX and our (I) complex both formed in space group P2₁/c.

It is the structure BOFKIS (Jayakumar et al., 2014 ), a complex of L1 with bound copper, to make a dinuclear dimer bridged by two acetate moiety O atoms, that best approximates how zinc is coordinated in our structures, specifically, the major domain of complex (I) (Fig. 1a). The other complexes that the search gave are of uncommon metals such as vanadium (DEMKEM; Sreekanth et al., 2006 ) and gold (QALDAJ; Sreekanth et al., 2004 ).

5. Synthesis and crystallization

The ligands L1 and L2 were synthesized for us by Enamine LLC (Monmouth Junction, New Jersey, USA) as >95% pure. The zinc-bound complexes of the ligands were obtained by incubating the ligands in a suitable solvent with zinc acetate. We obtained diffraction-quality crystals by vapor diffusion from acetonitrile [solvent for structure (I)] and from acetone [for structure (II)]. In either case we used diethyl ether as precipitant. Crystals were harvested from the vial and trimmed.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. We encountered non-merohedral twinning in the diffraction dataset from complex (I), and we did not merge the data, hence no R_int value is reported for this dataset. Hydrogen atoms were placed and allowed to refine using a riding model.

Table 4
Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Zn₂(C₁₅H₁₅N₄S)₂(C₂H₃O₂)₂]	[Zn₂(C₁₆H₁₇N₄S)₂(C₂H₃O₂)₂]
M_r	815.57	843.62
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	296	100
a, b, c (Å)	10.8384 (1), 20.0381 (2), 8.2914 (1)	9.3280 (2), 9.9979 (2), 10.5761 (2)
α, β, γ (°)	90, 91.342 (1), 90	67.101 (2), 83.267 (2), 87.150 (1)
V (Å³)	1800.24 (3)	902.33 (3)
Z	2	1
Radiation type	Cu Kα	Cu Kα
μ (mm⁻¹)	3.13	3.15
Crystal size (mm)	0.16 × 0.08 × 0.06	0.6 × 0.1 × 0.1

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO 1.171.42.49. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Gaussian (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO 1.171.42.49. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.736, 0.849	0.761, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8417, 8417, 7097	17092, 3599, 3314
R_int	?	0.037
(sin θ/λ)_max (Å⁻¹)	0.630	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.217, 1.05	0.035, 0.099, 1.07
No. of reflections	8417	3599
No. of parameters	244	237
No. of restraints	6	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −1.01	1.04, −0.61
Computer programs: CrysAlis PRO 1.171.42.49 (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO 1.171.42.49. Rigaku Oxford Diffraction, Yarnton, England.]$ ), CrysAlis PRO 1.171.43.91a (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO 1.171.43.91a. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), SHELXL2019/2 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2427149; 2428884

Crystal structure: contains datablocks I, II. DOI: https://doi.org/10.1107/S2056989025005407/hb8133sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025005407/hb8133Isup4.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989025005407/hb8133IIsup5.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025005407/hb8133Isup6.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989025005407/hb8133IIsup7.cml

checkCIF report

Computing details top

Di-µ-acetato-bis({N,N-dimethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamidato}zinc(II)) (I) top

Crystal data top

[Zn₂(C₁₅H₁₅N₄S)₂(C₂H₃O₂)₂]	F(000) = 840
M_r = 815.57	D_x = 1.505 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.8384 (1) Å	Cell parameters from 16893 reflections
b = 20.0381 (2) Å	θ = 4.0–75.6°
c = 8.2914 (1) Å	µ = 3.13 mm⁻¹
β = 91.342 (1)°	T = 296 K
V = 1800.24 (3) Å³	Prism, orange
Z = 2	0.16 × 0.08 × 0.06 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	8417 measured reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	8417 independent reflections
Mirror monochromator	7097 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	θ_max = 76.3°, θ_min = 4.1°
ω scans	h = −13→13
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2022)	k = −24→25
T_min = 0.736, T_max = 0.849	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.069	H-atom parameters constrained
wR(F²) = 0.217	w = 1/[σ²(F_o²) + (0.1154P)² + 1.5821P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
8417 reflections	Δρ_max = 0.57 e Å⁻³
244 parameters	Δρ_min = −1.01 e Å⁻³
6 restraints

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.

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	−0.12170 (6)	0.44522 (3)	0.57934 (7)	0.0620 (3)
S1	−0.01854 (11)	0.34367 (8)	0.5248 (2)	0.0798 (4)
N1	−0.2602 (3)	0.37741 (17)	0.6499 (4)	0.0536 (8)
N2	−0.2478 (3)	0.31082 (16)	0.6317 (5)	0.0547 (8)
N3	−0.1212 (4)	0.2251 (2)	0.5758 (6)	0.0748 (12)
N4	−0.2609 (5)	0.50729 (19)	0.6857 (5)	0.0677 (10)
C1	−0.3636 (5)	0.4755 (2)	0.7234 (5)	0.0601 (10)
C2	−0.4601 (6)	0.5100 (3)	0.7907 (8)	0.0817 (16)
H2	−0.532393	0.487759	0.816378	0.098*
C3	−0.4488 (9)	0.5777 (3)	0.8195 (9)	0.101 (2)
H3	−0.513822	0.601271	0.863438	0.122*
C4	−0.3429 (9)	0.6096 (3)	0.7837 (8)	0.099 (2)
H4	−0.333412	0.654999	0.803916	0.119*
C5	−0.2483 (8)	0.5725 (3)	0.7156 (7)	0.0875 (19)
H5	−0.174815	0.593646	0.690438	0.105*
C6	−0.4746 (4)	0.3618 (2)	0.7337 (5)	0.0530 (9)
C7	−0.4657 (5)	0.3067 (2)	0.8357 (6)	0.0615 (10)
H7	−0.389071	0.293653	0.877574	0.074*
C8	−0.5704 (6)	0.2714 (3)	0.8748 (8)	0.0812 (17)
H8	−0.564362	0.235186	0.944869	0.097*
C9	−0.6835 (6)	0.2896 (4)	0.8104 (11)	0.101 (3)
H9	−0.753922	0.266196	0.838511	0.121*
C10	−0.6930 (5)	0.3419 (4)	0.7054 (10)	0.094 (2)
H10	−0.769334	0.352862	0.658977	0.113*
C11	−0.5889 (5)	0.3791 (3)	0.6674 (7)	0.0726 (13)
H11	−0.596052	0.415381	0.597929	0.087*
C12	−0.3637 (4)	0.4022 (2)	0.6978 (5)	0.0523 (9)
C13	−0.1374 (4)	0.2914 (2)	0.5811 (5)	0.0606 (10)
C14	−0.2110 (6)	0.1788 (3)	0.6350 (8)	0.0811 (15)
H14A	−0.280989	0.202972	0.673169	0.122*
H14B	−0.174896	0.153228	0.721951	0.122*
H14C	−0.236959	0.149318	0.549520	0.122*
C15	−0.0079 (7)	0.1946 (4)	0.5192 (11)	0.107 (2)
H15A	0.046817	0.186037	0.609514	0.161*
H15B	0.031277	0.224407	0.445524	0.161*
H15C	−0.027236	0.153412	0.465239	0.161*
O1	−0.0062 (5)	0.4927 (4)	0.7356 (7)	0.0946 (18)	0.756 (6)
O2	0.1716 (5)	0.5131 (3)	0.6323 (6)	0.0787 (15)	0.756 (6)
C16	0.1073 (7)	0.4970 (7)	0.7512 (8)	0.0500 (16)	0.756 (6)
C17	0.1712 (9)	0.4881 (5)	0.9105 (9)	0.076 (2)	0.756 (6)
H17A	0.246371	0.513441	0.913051	0.114*	0.756 (6)
H17B	0.189858	0.441711	0.926914	0.114*	0.756 (6)
H17C	0.118602	0.503386	0.994452	0.114*	0.756 (6)
O1A	0.0452 (14)	0.4995 (11)	0.601 (2)	0.0946 (18)	0.244 (6)
O2A	0.2194 (16)	0.5302 (11)	0.678 (2)	0.0787 (15)	0.244 (6)
C16A	0.120 (3)	0.502 (2)	0.715 (4)	0.0500 (16)	0.244 (6)
C17A	0.122 (3)	0.4713 (16)	0.875 (3)	0.076 (2)	0.244 (6)
H17D	0.202769	0.453691	0.899451	0.114*	0.244 (6)
H17E	0.062579	0.435778	0.877541	0.114*	0.244 (6)
H17F	0.101735	0.504297	0.954302	0.114*	0.244 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0618 (4)	0.0728 (4)	0.0514 (4)	−0.0222 (3)	−0.0024 (3)	0.0105 (2)
S1	0.0484 (6)	0.1006 (10)	0.0910 (10)	−0.0045 (5)	0.0119 (6)	0.0123 (7)
N1	0.0529 (18)	0.0538 (17)	0.0539 (19)	−0.0059 (13)	−0.0001 (15)	0.0022 (14)
N2	0.0465 (17)	0.0509 (17)	0.067 (2)	−0.0003 (13)	0.0030 (15)	0.0026 (14)
N3	0.064 (2)	0.074 (3)	0.087 (3)	0.0191 (18)	0.005 (2)	0.002 (2)
N4	0.097 (3)	0.0536 (19)	0.052 (2)	−0.0192 (18)	−0.0040 (19)	0.0056 (15)
C1	0.080 (3)	0.054 (2)	0.046 (2)	−0.0020 (19)	0.000 (2)	0.0037 (16)
C2	0.105 (4)	0.058 (3)	0.084 (4)	0.005 (3)	0.019 (3)	−0.007 (2)
C3	0.151 (7)	0.059 (3)	0.095 (4)	0.019 (4)	0.018 (4)	−0.004 (3)
C4	0.175 (8)	0.046 (2)	0.077 (4)	−0.006 (3)	0.005 (4)	−0.002 (2)
C5	0.142 (6)	0.057 (3)	0.062 (3)	−0.028 (3)	−0.008 (3)	0.011 (2)
C6	0.049 (2)	0.057 (2)	0.053 (2)	−0.0027 (15)	0.0048 (17)	−0.0061 (16)
C7	0.063 (3)	0.062 (2)	0.059 (3)	−0.0090 (18)	0.006 (2)	0.0016 (18)
C8	0.091 (4)	0.066 (3)	0.088 (4)	−0.021 (3)	0.032 (3)	−0.009 (2)
C9	0.067 (3)	0.096 (4)	0.141 (6)	−0.030 (3)	0.045 (4)	−0.052 (4)
C10	0.047 (2)	0.105 (5)	0.131 (6)	0.000 (3)	0.003 (3)	−0.052 (4)
C11	0.059 (3)	0.078 (3)	0.080 (3)	0.012 (2)	−0.006 (2)	−0.014 (2)
C12	0.052 (2)	0.054 (2)	0.050 (2)	−0.0024 (16)	0.0000 (17)	0.0023 (16)
C13	0.054 (2)	0.070 (3)	0.058 (3)	0.0034 (18)	−0.0021 (19)	0.0053 (19)
C14	0.080 (3)	0.059 (3)	0.103 (4)	0.009 (2)	−0.015 (3)	0.008 (3)
C15	0.087 (4)	0.104 (5)	0.131 (6)	0.040 (4)	0.020 (4)	−0.007 (4)
O1	0.059 (3)	0.153 (5)	0.072 (3)	−0.036 (3)	0.008 (2)	−0.036 (3)
O2	0.051 (3)	0.123 (4)	0.061 (3)	−0.003 (3)	−0.005 (2)	0.024 (3)
C16	0.055 (3)	0.052 (3)	0.043 (4)	0.004 (2)	0.005 (3)	−0.003 (4)
C17	0.081 (6)	0.096 (6)	0.050 (4)	0.011 (4)	0.002 (3)	0.005 (3)
O1A	0.059 (3)	0.153 (5)	0.072 (3)	−0.036 (3)	0.008 (2)	−0.036 (3)
O2A	0.051 (3)	0.123 (4)	0.061 (3)	−0.003 (3)	−0.005 (2)	0.024 (3)
C16A	0.055 (3)	0.052 (3)	0.043 (4)	0.004 (2)	0.005 (3)	−0.003 (4)
C17A	0.081 (6)	0.096 (6)	0.050 (4)	0.011 (4)	0.002 (3)	0.005 (3)

Geometric parameters (Å, º) top

Zn1—S1	2.3705 (17)	C6—C12	1.485 (6)
Zn1—N1	2.117 (3)	C7—H7	0.9300
Zn1—N4	2.159 (5)	C7—C8	1.383 (7)
Zn1—O1	2.018 (5)	C8—H8	0.9300
Zn1—O2ⁱ	2.006 (5)	C8—C9	1.375 (11)
Zn1—O1A	2.114 (14)	C9—H9	0.9300
Zn1—O1Aⁱ	2.052 (18)	C9—C10	1.365 (12)
Zn1—O2Aⁱ	2.410 (18)	C10—H10	0.9300
S1—C13	1.733 (5)	C10—C11	1.394 (9)
N1—N2	1.350 (5)	C11—H11	0.9300
N1—C12	1.298 (6)	C14—H14A	0.9600
N2—C13	1.334 (6)	C14—H14B	0.9600
N3—C13	1.342 (7)	C14—H14C	0.9600
N3—C14	1.438 (8)	C15—H15A	0.9600
N3—C15	1.459 (7)	C15—H15B	0.9600
N4—C1	1.327 (7)	C15—H15C	0.9600
N4—C5	1.336 (7)	O1—C16	1.237 (9)
C1—C2	1.382 (8)	O2—C16	1.262 (8)
C1—C12	1.485 (6)	C16—C17	1.488 (10)
C2—H2	0.9300	C17—H17A	0.9600
C2—C3	1.383 (8)	C17—H17B	0.9600
C3—H3	0.9300	C17—H17C	0.9600
C3—C4	1.352 (11)	O1A—C16A	1.24 (2)
C4—H4	0.9300	O2A—C16A	1.26 (2)
C4—C5	1.397 (11)	C16A—C17A	1.46 (2)
C5—H5	0.9300	C17A—H17D	0.9600
C6—C7	1.392 (6)	C17A—H17E	0.9600
C6—C11	1.387 (7)	C17A—H17F	0.9600

S1—Zn1—O2Aⁱ	101.9 (5)	C6—C7—H7	119.9
N1—Zn1—S1	80.93 (10)	C8—C7—C6	120.2 (5)
N1—Zn1—N4	75.53 (14)	C8—C7—H7	119.9
N1—Zn1—O2Aⁱ	94.4 (4)	C7—C8—H8	119.9
N4—Zn1—S1	155.44 (10)	C9—C8—C7	120.1 (6)
N4—Zn1—O2Aⁱ	87.0 (5)	C9—C8—H8	119.9
O1—Zn1—S1	103.8 (2)	C8—C9—H9	119.8
O1—Zn1—N1	123.9 (2)	C10—C9—C8	120.4 (5)
O1—Zn1—N4	84.0 (2)	C10—C9—H9	119.8
O1—Zn1—O1Aⁱ	87.6 (4)	C9—C10—H10	119.8
O1—Zn1—O2Aⁱ	136.5 (6)	C9—C10—C11	120.3 (6)
O2ⁱ—Zn1—S1	108.03 (19)	C11—C10—H10	119.8
O2ⁱ—Zn1—N1	109.3 (2)	C6—C11—C10	119.8 (6)
O2ⁱ—Zn1—N4	86.6 (2)	C6—C11—H11	120.1
O2ⁱ—Zn1—O1	121.0 (3)	C10—C11—H11	120.1
O2ⁱ—Zn1—O1Aⁱ	40.8 (5)	N1—C12—C1	115.1 (4)
O2ⁱ—Zn1—O2Aⁱ	15.7 (5)	N1—C12—C6	124.2 (4)
O1A—Zn1—S1	92.9 (6)	C1—C12—C6	120.6 (4)
O1Aⁱ—Zn1—S1	97.1 (6)	N2—C13—S1	125.9 (4)
O1Aⁱ—Zn1—N1	148.1 (4)	N2—C13—N3	114.7 (4)
O1A—Zn1—N1	156.5 (6)	N3—C13—S1	119.4 (3)
O1A—Zn1—N4	105.9 (5)	N3—C14—H14A	109.5
O1Aⁱ—Zn1—N4	106.5 (6)	N3—C14—H14B	109.5
O1Aⁱ—Zn1—O1A	54.9 (8)	N3—C14—H14C	109.5
O1A—Zn1—O2Aⁱ	109.1 (7)	H14A—C14—H14B	109.5
O1Aⁱ—Zn1—O2Aⁱ	54.7 (6)	H14A—C14—H14C	109.5
C13—S1—Zn1	96.33 (16)	H14B—C14—H14C	109.5
N2—N1—Zn1	122.0 (3)	N3—C15—H15A	109.5
C12—N1—Zn1	117.6 (3)	N3—C15—H15B	109.5
C12—N1—N2	120.1 (3)	N3—C15—H15C	109.5
C13—N2—N1	114.6 (3)	H15A—C15—H15B	109.5
C13—N3—C14	122.5 (4)	H15A—C15—H15C	109.5
C13—N3—C15	122.4 (5)	H15B—C15—H15C	109.5
C14—N3—C15	114.9 (5)	C16—O1—Zn1	134.4 (6)
C1—N4—Zn1	114.7 (3)	C16—O2—Zn1ⁱ	130.3 (6)
C1—N4—C5	120.6 (5)	O1—C16—O2	120.1 (7)
C5—N4—Zn1	124.7 (4)	O1—C16—C17	121.7 (6)
N4—C1—C2	120.2 (4)	O2—C16—C17	118.0 (7)
N4—C1—C12	116.0 (4)	C16—C17—H17A	109.5
C2—C1—C12	123.7 (4)	C16—C17—H17B	109.5
C1—C2—H2	120.2	C16—C17—H17C	109.5
C1—C2—C3	119.7 (6)	H17A—C17—H17B	109.5
C3—C2—H2	120.2	H17A—C17—H17C	109.5
C2—C3—H3	120.0	H17B—C17—H17C	109.5
C4—C3—C2	119.9 (6)	Zn1ⁱ—O1A—Zn1	125.1 (8)
C4—C3—H3	120.0	C16A—O1A—Zn1	129.3 (18)
C3—C4—H4	120.9	O1A—C16A—O2A	112 (2)
C3—C4—C5	118.1 (5)	O1A—C16A—C17A	132 (3)
C5—C4—H4	120.9	O2A—C16A—C17A	115 (2)
N4—C5—C4	121.5 (6)	C16A—C17A—H17D	109.5
N4—C5—H5	119.2	C16A—C17A—H17E	109.5
C4—C5—H5	119.2	C16A—C17A—H17F	109.5
C7—C6—C12	120.6 (4)	H17D—C17A—H17E	109.5
C11—C6—C7	119.2 (4)	H17D—C17A—H17F	109.5
C11—C6—C12	120.3 (4)	H17E—C17A—H17F	109.5

Zn1—S1—C13—N2	1.8 (4)	C1—C2—C3—C4	−0.8 (11)
Zn1—S1—C13—N3	−178.0 (4)	C2—C1—C12—N1	−172.7 (5)
Zn1—N1—N2—C13	6.3 (5)	C2—C1—C12—C6	4.5 (7)
Zn1—N1—C12—C1	−10.1 (5)	C2—C3—C4—C5	1.0 (11)
Zn1—N1—C12—C6	172.9 (3)	C3—C4—C5—N4	0.1 (10)
Zn1—N4—C1—C2	−179.3 (4)	C5—N4—C1—C2	1.6 (8)
Zn1—N4—C1—C12	4.1 (5)	C5—N4—C1—C12	−175.0 (5)
Zn1—N4—C5—C4	179.5 (5)	C6—C7—C8—C9	1.4 (8)
Zn1—O1—C16—O2	51.2 (18)	C7—C6—C11—C10	0.9 (7)
Zn1—O1—C16—C17	−133.0 (9)	C7—C6—C12—N1	50.6 (6)
Zn1ⁱ—O2—C16—O1	15.9 (18)	C7—C6—C12—C1	−126.3 (5)
Zn1ⁱ—O2—C16—C17	−160.0 (7)	C7—C8—C9—C10	1.1 (9)
Zn1—O1A—C16A—O2A	169 (2)	C8—C9—C10—C11	−2.6 (9)
Zn1ⁱ—O1A—C16A—O2A	−7 (5)	C9—C10—C11—C6	1.6 (8)
Zn1—O1A—C16A—C17A	−2 (8)	C11—C6—C7—C8	−2.4 (7)
Zn1ⁱ—O1A—C16A—C17A	−178 (5)	C11—C6—C12—N1	−130.3 (5)
Zn1ⁱ—O2A—C16A—O1A	5 (4)	C11—C6—C12—C1	52.8 (6)
Zn1ⁱ—O2A—C16A—C17A	178 (4)	C12—N1—N2—C13	179.7 (4)
N1—N2—C13—S1	−5.2 (6)	C12—C1—C2—C3	175.9 (6)
N1—N2—C13—N3	174.7 (4)	C12—C6—C7—C8	176.7 (4)
N2—N1—C12—C1	176.3 (4)	C12—C6—C11—C10	−178.2 (4)
N2—N1—C12—C6	−0.8 (6)	C14—N3—C13—S1	173.9 (4)
N4—C1—C2—C3	−0.5 (9)	C14—N3—C13—N2	−5.9 (8)
N4—C1—C12—N1	3.8 (6)	C15—N3—C13—S1	−2.0 (8)
N4—C1—C12—C6	−179.1 (4)	C15—N3—C13—N2	178.2 (6)
C1—N4—C5—C4	−1.4 (8)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···S1ⁱⁱ	0.96	3.00	3.832 (7)	146
C14—H14B···O2Aⁱⁱⁱ	0.96	2.65	3.36 (2)	131
C17—H17C···O1^iv	0.96	2.57	3.493 (9)	160

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

Di-µ-acetato-bis({N-ethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamidato}zinc(II)) (II) top

Crystal data top

[Zn₂(C₁₆H₁₇N₄S)₂(C₂H₃O₂)₂]	Z = 1
M_r = 843.62	F(000) = 436
Triclinic, P1	D_x = 1.553 Mg m⁻³
a = 9.3280 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.9979 (2) Å	Cell parameters from 10059 reflections
c = 10.5761 (2) Å	θ = 4.6–75.5°
α = 67.101 (2)°	µ = 3.15 mm⁻¹
β = 83.267 (2)°	T = 100 K
γ = 87.150 (1)°	Needle, metallic orangish yellow
V = 902.33 (3) Å³	0.6 × 0.1 × 0.1 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3599 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3314 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.037
Detector resolution: 10.0000 pixels mm^-1	θ_max = 75.9°, θ_min = 4.6°
ω scans	h = −11→11
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2022)	k = −12→12
T_min = 0.761, T_max = 1.000	l = −13→8
17092 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0496P)² + 0.808P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3599 reflections	Δρ_max = 1.04 e Å⁻³
237 parameters	Δρ_min = −0.61 e Å⁻³
0 restraints

Special details top

Refinement. n/a

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.13763 (3)	0.56946 (3)	0.52595 (3)	0.02666 (12)
S1	0.07920 (7)	0.80673 (6)	0.50446 (7)	0.03498 (16)
O1	0.03886 (17)	0.55584 (18)	0.36744 (17)	0.0314 (4)
O2	0.20742 (19)	0.6904 (2)	0.2109 (2)	0.0420 (4)
N1	0.2769 (2)	0.5869 (2)	0.66120 (19)	0.0257 (4)
N2	0.2572 (2)	0.6924 (2)	0.7140 (2)	0.0291 (4)
N3	0.2913 (2)	0.4029 (2)	0.54080 (19)	0.0267 (4)
C1	0.3747 (2)	0.4885 (2)	0.7032 (2)	0.0261 (5)
C2	0.1670 (2)	0.7967 (2)	0.6451 (2)	0.0294 (5)
N5	0.1441 (2)	0.9069 (2)	0.6877 (2)	0.0350 (5)
H5	0.081887	0.974927	0.647316	0.042*
C4	0.2163 (3)	0.9198 (3)	0.7967 (3)	0.0380 (6)
H4A	0.320567	0.937002	0.766181	0.046*
H4B	0.205478	0.828339	0.879667	0.046*
C5	0.1511 (4)	1.0449 (3)	0.8317 (3)	0.0474 (7)
H5A	0.166587	1.135871	0.750695	0.071*
H5B	0.197324	1.050581	0.908014	0.071*
H5C	0.047298	1.028886	0.859057	0.071*
C6	0.3890 (2)	0.3859 (2)	0.6315 (2)	0.0243 (4)
C7	0.4979 (2)	0.2824 (2)	0.6496 (2)	0.0274 (5)
H7	0.566977	0.272140	0.712077	0.033*
C8	0.5045 (2)	0.1939 (2)	0.5752 (2)	0.0292 (5)
H8	0.578194	0.122378	0.586622	0.035*
C9	0.4035 (3)	0.2103 (3)	0.4844 (2)	0.0305 (5)
H9	0.405956	0.150358	0.433217	0.037*
C10	0.2986 (3)	0.3169 (3)	0.4703 (2)	0.0298 (5)
H10	0.229027	0.329140	0.407845	0.036*
C11	0.4011 (3)	0.3593 (3)	0.9519 (2)	0.0299 (5)
C12	0.4561 (3)	0.2191 (3)	1.0019 (3)	0.0428 (6)
H12	0.540830	0.195757	0.955343	0.051*
C13	0.3887 (4)	0.1127 (3)	1.1191 (3)	0.0528 (8)
H13	0.426549	0.016658	1.151237	0.063*
C14	0.2658 (3)	0.1459 (4)	1.1899 (3)	0.0489 (7)
H14	0.217569	0.072526	1.268490	0.059*
C15	0.2151 (3)	0.2871 (4)	1.1442 (3)	0.0478 (7)
H15	0.133473	0.311632	1.193703	0.057*
C16	0.2825 (3)	0.3938 (3)	1.0261 (3)	0.0377 (6)
H16	0.247096	0.490733	0.996116	0.045*
C17	0.4658 (2)	0.4735 (3)	0.8165 (2)	0.0290 (5)
H17A	0.470220	0.567857	0.825991	0.035*
H17B	0.565358	0.444870	0.793100	0.035*
C18	0.0920 (2)	0.6274 (3)	0.2411 (2)	0.0298 (5)
C19	0.0001 (3)	0.6270 (3)	0.1320 (3)	0.0386 (6)
H19A	−0.021844	0.526672	0.147366	0.058*
H19B	0.052749	0.674272	0.040290	0.058*
H19C	−0.090138	0.679880	0.137940	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02338 (17)	0.02572 (18)	0.02823 (18)	0.00230 (12)	−0.00559 (12)	−0.00704 (13)
S1	0.0350 (3)	0.0272 (3)	0.0430 (3)	0.0064 (2)	−0.0152 (3)	−0.0116 (3)
O1	0.0300 (8)	0.0344 (9)	0.0279 (8)	0.0010 (7)	−0.0068 (7)	−0.0090 (7)
O2	0.0272 (9)	0.0545 (12)	0.0426 (10)	−0.0061 (8)	−0.0036 (7)	−0.0160 (9)
N1	0.0243 (9)	0.0238 (9)	0.0266 (9)	−0.0006 (7)	−0.0023 (7)	−0.0072 (8)
N2	0.0277 (9)	0.0264 (10)	0.0331 (10)	−0.0004 (7)	−0.0029 (8)	−0.0114 (8)
N3	0.0224 (9)	0.0263 (9)	0.0283 (9)	0.0003 (7)	−0.0036 (7)	−0.0069 (8)
C1	0.0211 (10)	0.0276 (11)	0.0254 (11)	−0.0028 (8)	0.0012 (8)	−0.0063 (9)
C2	0.0265 (11)	0.0249 (11)	0.0342 (12)	−0.0021 (9)	0.0014 (9)	−0.0096 (9)
N5	0.0344 (11)	0.0277 (10)	0.0427 (12)	0.0028 (8)	−0.0059 (9)	−0.0132 (9)
C4	0.0404 (14)	0.0359 (13)	0.0375 (13)	−0.0054 (11)	−0.0013 (11)	−0.0142 (11)
C5	0.0574 (18)	0.0422 (15)	0.0453 (16)	−0.0035 (13)	0.0029 (13)	−0.0216 (13)
C6	0.0202 (10)	0.0241 (10)	0.0238 (10)	−0.0016 (8)	−0.0016 (8)	−0.0041 (8)
C7	0.0234 (10)	0.0272 (11)	0.0263 (11)	−0.0016 (8)	−0.0017 (8)	−0.0046 (9)
C8	0.0254 (11)	0.0259 (11)	0.0307 (11)	0.0020 (9)	0.0003 (9)	−0.0062 (9)
C9	0.0311 (12)	0.0308 (12)	0.0303 (12)	−0.0016 (9)	−0.0016 (9)	−0.0129 (10)
C10	0.0285 (11)	0.0310 (12)	0.0298 (11)	−0.0015 (9)	−0.0052 (9)	−0.0107 (10)
C11	0.0286 (11)	0.0360 (12)	0.0263 (11)	−0.0004 (9)	−0.0085 (9)	−0.0118 (10)
C12	0.0521 (16)	0.0403 (15)	0.0295 (13)	0.0093 (12)	−0.0064 (11)	−0.0069 (11)
C13	0.076 (2)	0.0392 (16)	0.0337 (14)	0.0041 (15)	−0.0108 (14)	−0.0030 (12)
C14	0.0525 (17)	0.0581 (19)	0.0267 (13)	−0.0123 (14)	−0.0095 (12)	−0.0032 (12)
C15	0.0347 (14)	0.072 (2)	0.0317 (13)	−0.0006 (13)	−0.0037 (11)	−0.0143 (14)
C16	0.0329 (13)	0.0474 (15)	0.0316 (12)	0.0021 (11)	−0.0061 (10)	−0.0135 (11)
C17	0.0254 (11)	0.0322 (12)	0.0288 (11)	0.0007 (9)	−0.0051 (9)	−0.0105 (10)
C18	0.0246 (11)	0.0317 (12)	0.0311 (12)	0.0041 (9)	−0.0028 (9)	−0.0105 (10)
C19	0.0358 (13)	0.0487 (15)	0.0290 (12)	−0.0040 (11)	−0.0029 (10)	−0.0122 (11)

Geometric parameters (Å, º) top

Zn1—S1	2.3360 (6)	C7—H7	0.9500
Zn1—O1ⁱ	2.0547 (17)	C7—C8	1.390 (3)
Zn1—O1	2.0567 (16)	C8—H8	0.9500
Zn1—N1	2.1017 (19)	C8—C9	1.381 (3)
Zn1—N3	2.1128 (19)	C9—H9	0.9500
S1—C2	1.748 (3)	C9—C10	1.386 (3)
O1—C18	1.296 (3)	C10—H10	0.9500
O2—C18	1.220 (3)	C11—C12	1.386 (4)
N1—N2	1.369 (3)	C11—C16	1.389 (4)
N1—C1	1.290 (3)	C11—C17	1.521 (3)
N2—C2	1.338 (3)	C12—H12	0.9500
N3—C6	1.358 (3)	C12—C13	1.385 (4)
N3—C10	1.335 (3)	C13—H13	0.9500
C1—C6	1.488 (3)	C13—C14	1.393 (5)
C1—C17	1.506 (3)	C14—H14	0.9500
C2—N5	1.342 (3)	C14—C15	1.380 (5)
N5—H5	0.8800	C15—H15	0.9500
N5—C4	1.451 (3)	C15—C16	1.392 (4)
C4—H4A	0.9900	C16—H16	0.9500
C4—H4B	0.9900	C17—H17A	0.9900
C4—C5	1.518 (4)	C17—H17B	0.9900
C5—H5A	0.9800	C18—C19	1.517 (3)
C5—H5B	0.9800	C19—H19A	0.9800
C5—H5C	0.9800	C19—H19B	0.9800
C6—C7	1.388 (3)	C19—H19C	0.9800

O1—Zn1—S1	101.39 (5)	C6—C7—H7	120.5
O1ⁱ—Zn1—S1	106.55 (5)	C6—C7—C8	119.1 (2)
O1ⁱ—Zn1—O1	78.74 (7)	C8—C7—H7	120.5
O1ⁱ—Zn1—N1	111.25 (7)	C7—C8—H8	120.1
O1—Zn1—N1	168.46 (7)	C9—C8—C7	119.8 (2)
O1ⁱ—Zn1—N3	99.24 (7)	C9—C8—H8	120.1
O1—Zn1—N3	96.75 (7)	C8—C9—H9	121.0
N1—Zn1—S1	81.70 (5)	C8—C9—C10	118.1 (2)
N1—Zn1—N3	76.34 (7)	C10—C9—H9	121.0
N3—Zn1—S1	150.82 (6)	N3—C10—C9	122.7 (2)
C2—S1—Zn1	94.80 (8)	N3—C10—H10	118.6
Zn1ⁱ—O1—Zn1	101.26 (7)	C9—C10—H10	118.6
C18—O1—Zn1	119.22 (15)	C12—C11—C16	118.8 (2)
C18—O1—Zn1ⁱ	139.34 (15)	C12—C11—C17	121.3 (2)
N2—N1—Zn1	121.20 (14)	C16—C11—C17	119.9 (2)
C1—N1—Zn1	118.57 (16)	C11—C12—H12	119.6
C1—N1—N2	119.98 (19)	C13—C12—C11	120.8 (3)
C2—N2—N1	111.85 (19)	C13—C12—H12	119.6
C6—N3—Zn1	114.71 (15)	C12—C13—H13	119.9
C10—N3—Zn1	125.89 (16)	C12—C13—C14	120.3 (3)
C10—N3—C6	119.41 (19)	C14—C13—H13	119.9
N1—C1—C6	114.0 (2)	C13—C14—H14	120.5
N1—C1—C17	124.3 (2)	C15—C14—C13	119.0 (3)
C6—C1—C17	121.69 (19)	C15—C14—H14	120.5
N2—C2—S1	127.26 (18)	C14—C15—H15	119.7
N2—C2—N5	116.0 (2)	C14—C15—C16	120.6 (3)
N5—C2—S1	116.74 (18)	C16—C15—H15	119.7
C2—N5—H5	118.2	C11—C16—C15	120.4 (3)
C2—N5—C4	123.5 (2)	C11—C16—H16	119.8
C4—N5—H5	118.2	C15—C16—H16	119.8
N5—C4—H4A	109.7	C1—C17—C11	109.73 (18)
N5—C4—H4B	109.7	C1—C17—H17A	109.7
N5—C4—C5	109.7 (2)	C1—C17—H17B	109.7
H4A—C4—H4B	108.2	C11—C17—H17A	109.7
C5—C4—H4A	109.7	C11—C17—H17B	109.7
C5—C4—H4B	109.7	H17A—C17—H17B	108.2
C4—C5—H5A	109.5	O1—C18—C19	115.0 (2)
C4—C5—H5B	109.5	O2—C18—O1	123.0 (2)
C4—C5—H5C	109.5	O2—C18—C19	122.0 (2)
H5A—C5—H5B	109.5	C18—C19—H19A	109.5
H5A—C5—H5C	109.5	C18—C19—H19B	109.5
H5B—C5—H5C	109.5	C18—C19—H19C	109.5
N3—C6—C1	115.76 (19)	H19A—C19—H19B	109.5
N3—C6—C7	120.8 (2)	H19A—C19—H19C	109.5
C7—C6—C1	123.3 (2)	H19B—C19—H19C	109.5

Zn1—S1—C2—N2	11.2 (2)	C1—N1—N2—C2	170.9 (2)
Zn1—S1—C2—N5	−170.12 (17)	C1—C6—C7—C8	−178.3 (2)
Zn1—O1—C18—O2	8.3 (3)	C2—N5—C4—C5	−172.4 (2)
Zn1ⁱ—O1—C18—O2	−177.72 (18)	C6—N3—C10—C9	−0.6 (3)
Zn1ⁱ—O1—C18—C19	2.2 (4)	C6—C1—C17—C11	−81.4 (2)
Zn1—O1—C18—C19	−171.85 (16)	C6—C7—C8—C9	0.2 (3)
Zn1—N1—N2—C2	−15.0 (2)	C7—C8—C9—C10	0.5 (3)
Zn1—N1—C1—C6	8.8 (2)	C8—C9—C10—N3	−0.3 (3)
Zn1—N1—C1—C17	−169.86 (16)	C10—N3—C6—C1	178.71 (19)
Zn1—N3—C6—C1	−1.3 (2)	C10—N3—C6—C7	1.3 (3)
Zn1—N3—C6—C7	−178.70 (16)	C11—C12—C13—C14	−1.1 (5)
Zn1—N3—C10—C9	179.39 (17)	C12—C11—C16—C15	−3.7 (4)
S1—C2—N5—C4	−175.73 (18)	C12—C11—C17—C1	100.0 (3)
N1—N2—C2—S1	0.3 (3)	C12—C13—C14—C15	−2.0 (5)
N1—N2—C2—N5	−178.42 (19)	C13—C14—C15—C16	2.3 (4)
N1—C1—C6—N3	−4.8 (3)	C14—C15—C16—C11	0.6 (4)
N1—C1—C6—C7	172.5 (2)	C16—C11—C12—C13	4.0 (4)
N1—C1—C17—C11	97.2 (3)	C16—C11—C17—C1	−78.4 (3)
N2—N1—C1—C6	−176.93 (18)	C17—C1—C6—N3	173.91 (19)
N2—N1—C1—C17	4.4 (3)	C17—C1—C6—C7	−8.8 (3)
N2—C2—N5—C4	3.1 (3)	C17—C11—C12—C13	−174.4 (3)
N3—C6—C7—C8	−1.1 (3)	C17—C11—C16—C15	174.7 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

We thank Ms Maame Kobe Asiamah and Ms Hanna Wosen for help with crystallization trials.

Funding information

Funding for this research was provided by: Howard University College of Medicine (project U100272, Fund #19, Program #02); National Science Foundation, Directorate for Mathematical and Physical Sciences (MRI grant DMR-2117502 for the X-ray diffractometer); National Institutes of Health, National Center on Minority Health and Health Disparities (award No. 2U54MD007597). The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health.

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Syntheses and structures of dinuclear zinc(II) acetate-bridged coordination compounds with the aromatic Schiff base chelators N,N-di­methyl-2-[phen­yl(pyridin-2-yl)methyl­­idene]hydrazine-1-carbo­thio­amide and N-ethyl-2-[phen­yl(pyridin-2-yl)methyl­­idene]hydrazine-1-carbo­thio­amide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Syntheses and structures of dinuclear zinc(II) acetate-bridged coordination compounds with the aromatic Schiff base chelators N,N-dimethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamide and N-ethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazine-1-carbothioamide

3. Supramolecular features