Synthesis, crystal structure and Hirshfeld analysis of trans-bis­{(2E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-yl­idene]hydrazinecarbo­thio­amidato-κ2N1,S}palladium(II)

Melo, A.P.L. de; Martins, B.B.; Bresolin, L.; Tirloni, B.; Oliveira, A.B. de

doi:10.1107/S2056989023008654

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 11| November 2023| Pages 993-998

https://doi.org/10.1107/S2056989023008654

Open

access

Synthesis, crystal structure and Hirshfeld analysis of trans-bis{(2E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-ylidene]hydrazinecarbothioamidato-κ²N¹,S}palladium(II)

Ana Paula Lopes de Melo,^a Bianca Barreto Martins,^a Leandro Bresolin,^a ^* Bárbara Tirloni ^b and Adriano Bof de Oliveira ^c

^aEscola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-900 Rio Grande-RS, Brazil, ^bDepartamento de Química, Universidade Federal de Santa Maria, Av. Roraima s/n, Campus Universitário, 97105-900 Santa Maria-RS, Brazil, and ^cDepartamento de Química, Universidade Federal de Sergipe, Av. Marcelo Deda Chagas s/n, Campus Universitário, 49107-230 São Cristóvão-SE, Brazil
^*Correspondence e-mail: leandro_bresolin@yahoo.com.br

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 4 September 2023; accepted 2 October 2023; online 5 October 2023)

The reaction of (2E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-ylidene]hydrazinecarbothioamide (common name: cinnamaldehyde-4-phenylthiosemicarbazone) deprotonated with NaOH in ethanol with an ethanolic suspension of Pd^II chloride in a 2:1 molar ratio yielded the title compound, [Pd(C₁₆H₁₄N₃S)₂]. The anionic ligands act as metal chelators, κ²N¹S-donors, forming five-membered rings with a trans-configuration. The Pd^II ion is fourfold coordinated in a slightly distorted square-planar geometry. For each ligand, one H⋯S and one H⋯N intramolecular interactions are observed, with S(5) and S(6) graph-set motifs. Concerning the H⋯S interactions, the coordination sphere resembles a hydrogen-bonded macrocyclic environment-type. In the crystal, the complexes are linked via pairs of H⋯S interactions, with graph-set motif R₂²(8), and building a mono-periodic hydrogen-bonded ribbon along [001]. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are: H⋯H (45.3%), H⋯C/C⋯H (28.0%), H⋯S/S⋯H (8.0%) and H⋯N/N⋯H (7.4%).

Keywords: palladium(II) thiosemicarbazone complex; cinnamaldehyde 4-phenylthiosemicarbazone; Hirshfeld surface analysis; crystal structure.

CCDC reference: 2163054

1. Chemical context

As far as we know, the thiosemicarbazone chemistry can be traced back to the beginning of the 1900s, when a thiosemicarbazide derivative, H₂N—N(H)C(=S)NR₁R₂, was used as chemical reagent for the characterization of aldehydes and ketones, R₃R₄C=O. It was pointed out that the main product of the characterization reaction was a thiosemicarbazone derivative, R₃R₄C=N—N(H)C(=S)NR₁R₂ (Freund & Schander, 1902 ). In the second half of the 1950s, the use of 4-phenylthiosemicarbazide as reagent for the characterization of cinnamaldehyde was reported and the cinnamaldehyde 4-phenylthiosemicarbazone molecule, the ligand of the title compound, was the major product of the reaction (Tišler, 1956 ).

From early times, as a product of qualitative analysis reactions in the organic chemistry, thiosemicarbazone chemistry emerged as a large class of compounds present in a wide range of scientific disciplines. For example, the cinnamaldehyde 4-phenylthiosemicarbazone derivative shows anti-corrosion activity for copper in nitric acid media (Mostafa, 2000 ).

One of the most important applications of thiosemicarbazone derivatives is in coordination chemistry. The N—N(H)—C(=S) fragment can be easily deprotonated and the negative charge is then delocalized over the N—N—C—S entity, which enables chemical bonding with many different metal centers, with different Lewis acidity, and a diversity of coordination modes, e.g., chelating and bridging. Complexes with anionic thiosemicarbazone derivatives are more common as a result of the charge density and the geometry adopted by the ligands (Lobana et al., 2009 ).

Many complexes with thiosemicarbazone ligands show relevant biological activity. For example, Pd^II heteroleptic complexes with a cinnamaldehyde-thiosemicarbazone derivative turned out to be very active on in vitro Human Topoisomerase IIα inhibition, a biological target of prime importance for cancer research (Rocha et al., 2019 ). Other Pd^II homoleptic and heteroleptic complexes with cinnamaldehyde-thiosemicarbazone as ligands were reported to be active against five human cancer cell lines in vitro: colon (Caco-2), cervix (HeLa), hepatocellular (HepG2), breast (MCF-7) and prostate (PC-3) (Nyawadea et al., 2021 ). Finally, Ni^II homoleptic cinnamaldehyde-4-ethylthiosemicarbazone and cinnamaldehyde-4-methylthiosemicarbazone derivative complexes showed, also in in vitro assays, inhibition of cell growth for two selected human tumour cell lines: breast (MCF-7) and lung (A549) (Farias et al., 2021 ).

Another interesting approach for cinnamaldehyde-thiosemicarbazone chemistry is the synthesis of nanostructured materials through thermal and solvothermal decomposition techniques, where thiosemicarbazone complexes are employed as single-molecule precursors. It was reported that the thermal and solvothermal decomposition of ZnL₂ and ZnCl₂(LH)₂ homo- and heteroleptic complexes results in the formation of ZnS nanocrystallites (for this section only, L = the anionic form of cinnamaldehyde-thiosemicarbazone and LH = the neutral form of it) (Palve & Garje, 2011 ). Similarly, Cd^II heteroleptic complexes CdCl₂(LH)₂ and CdI₂(LH)₂ were used as starting materials to obtain CdS nanoparticles (Pawar et al., 2016 ) and CoS or Co₉S₈ nanocrystallites were synthesized from CoL₂ and CoCl₂(LH)₂ homo- and heteroleptic complexes (Pawar & Garje, 2015 ).

Motivated by the bioinorganic chemistry and materials science of the cinnamaldehyde-thiosemicarbazone complexes, we report herein the synthesis, crystal structure and Hirshfeld analysis of a new Pd^II homoleptic complex where the cinnamaldehyde-4-phenylthiosemicarbazone molecules act as anionic ligands.

2. Structural commentary

The asymmetric unit comprises one molecule of the title compound, with all atoms being located in general positions (Fig. 1). The complex consists of one Pd^II metal center and two deprotonated cinnamaldehyde-4-phenylthiosemicarbazone ligands, which act as metal chelators, forming five-membered metallarings. The ligands are coordinated through N and S atoms in a trans-configuration, κ²N¹S-donors, and the N1—Pd1—N4 and the S1—Pd1—S2 angles are 178.31 (6) and 177.57 (2)°, respectively. The metal ion is fourfold coordinated in a slightly distorted square-planar geometry. The maximum deviation from the mean plane through the Pd1/N1/N4/S1/S2 fragment is 0.0227 (5) Å for Pd1 and the r.m.s. for the selected atoms is 0.0151 Å. Concerning the geometry of the N—N—C—S entities, the N1—N2—C10—S1 torsion angle is 0.6 (3)°, while N4—N5—C26—S2 is −0.4 (3)°. Both of the ligands are non-planar, with the angle between the mean planes through the C4–C9 and the C11–C16 aromatic rings being 15.7 (1)°, while that between the C20–C25 and the C27–C32 rings is 45.5 (8)°.

Figure 1
The molecular structure of the title compound, showing the atom labeling and displacement ellipsoids drawn at the 40% probability level.

Four intramolecular hydrogen-bonding interactions are observed (Fig. 2, Table 1): C1—H1⋯S2 and C17—H14⋯S1, with graph-set motif S(5), and C16—H13⋯N2 and C32—H26⋯N5, with graph-set motif S(6). Considering the S(5) rings, a hydrogen-bonded macrocyclic coordination environment-type can be suggested for the Pd^II metal center, while the S(6) rings contribute to the stabilization of the molecular structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯S2	0.93	2.60	3.230 (2)	126
C16—H13⋯N2	0.93	2.32	2.887 (3)	119
C17—H14⋯S1	0.93	2.72	3.355 (2)	126
C32—H26⋯N5	0.93	2.39	2.911 (3)	115
N3—H27⋯S2ⁱ	0.86	2.63	3.4805 (18)	171
N6—H28⋯S1ⁱⁱ	0.86	2.84	3.6554 (19)	159
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
C—H⋯S and C—H⋯N hydrogen intramolecular interactions of the title compound (dashed lines), forming rings of S(5) and S(6) graph-set motifs. A hydrogen-bonded macrocyclic coordination environment-type can be suggested for the Pd^II metal center.

Finally, the anionic form of the ligands was assigned because of the absence of hydrazinic H atoms and the change in the bond lengths of the N—N—C—S entities. For the neutral or free, i.e., non-coordinating thiosemicarbazones, the N—N and C—S bonds have lengths of double-bond character, while the N—C bond shows lengths of single-bond type, which can be written as a N=N(H)—C=S fragment. When the acidic H atom of the hydrazinic fragment is removed, the negative charge is delocalized over the N—N—C—S chain and the bond lengths change to intermediate values. Thus, the N—N and the C—S bond lengths assume single-bond character, being longer, and the N—C bond lengths assume double-bond character, being shorter. Information about the bond lengths of the N—N—C—S entities for the cinnamaldehyde-4-phenylthiosemicarbazone molecule, C₁₆H₁₅N₃S, and the Ni(C₁₆H₁₄N₃S)₂ (Song et al., 2014 ) and Pd(C₁₆H₁₄N₃S)₂ complexes, this work, are summarized in Table 2. These data are in agreement with reported bond lengths values for thiosemicarbazone derivatives (Oliveira et al., 2014 ).

Table 2
Bond lengths (Å) for the N—N—C—S entities in cinnamaldehyde-4-phenylthiosemicarbazone structures: as a neutral molecule and as an anionic ligand

	N—N	N—C	C—S
C₁₆H₁₅N₃S^a,^c	1.369 (2)	1.354 (2)	1.6704 (19)
Ni(C₁₆H₁₄N₃S)₂^b,^c	1.405 (5)	1.301 (6)	1.730 (5)
Pd(C₁₆H₁₄N₃S)₂^b,^d	1.390 (2)	1.293 (2)	1.7520 (19)
	1.393 (2)	1.291 (2)	1.7328 (19)
Notes: (a) Neutral, non-coordinated form of the cinnamaldehyde 4-phenylthiosemicarbazone; (b) anionic, coordinated form of the cinnamaldehyde 4-phenylthiosemicarbazone; (c) Song et al. (2014); (d) this work.

3. Supramolecular features

In the crystal, the molecules are connected via pairs of N—H⋯S interactions with graph-set motif $[R_{2}^{2}]$ (8), forming a mono-periodic hydrogen-bonded ribbon along [001] (Fig. 3, Table 1).

Figure 3
Crystal structure section of the title compound viewed along the b-axis. The N—H⋯S interactions are drawn as dashed lines, forming rings of $[R_{2}^{2}]$ (8) graph-set motif and linking the molecules along the c-axis. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ .]

The Hirshfeld surface analysis (Hirshfeld, 1977 ) of the crystal structure was performed with Crystal Explorer (Wolff et al., 2012 ). The graphical representations of the Hirshfeld surface for the title compound are represented using a ball-and-stick model with transparency, in two side-views and separate figures for clarity (Fig. 4). The locations of the strongest intermolecular contacts, i.e, the regions around the S1, H27, S2 and H28 atoms, are indicated in magenta. These atoms are those involved in the N—H⋯S intermolecular interactions represented in the previous figure (Fig. 3): N3—H27⋯S2ⁱ and N6—H28⋯S1ⁱⁱ [symmetry codes: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ]. The Hirshfeld surface analysis of the crystal structure also indicates that the most relevant intermolecular interactions for crystal packing are the following: (a) H⋯H (45.3%), (b) H⋯C/C⋯H (28.0%), (c) H⋯S/S⋯H (8.0%) and (d) H⋯N/N⋯H (7.4%). The contributions to the crystal packing are shown as two-dimensional Hirshfeld surface fingerprint plots with cyan dots (Fig. 5). The d_i (x-axis) and the d_e (y-axis) values are the closest internal and external distances from given points on the Hirshfeld surface (in Å).

Figure 4
Two side-views in separate figures of the Hirshfeld surface graphical representation (d_norm) for the title compound. The surface is drawn with transparency and simplified for clarity and the regions with strongest intermolecular interactions are shown in magenta. [d_norm range: −0.289 to 1.415]

Figure 5
The Hirshfeld surface two-dimensional fingerprint plot for the title compound showing the (a) H⋯H, (b) H⋯C/C⋯H, (c) H⋯S/S⋯H and (d) H⋯N/N⋯·H contacts in detail (cyan dots). The contributions of the interactions to the crystal cohesion amount to 45.3, 28.0, 8.0 and 7.4%, respectively. The d_i (x-axis) and the d_e (y-axis) values are the closest internal and external distances from given points on the Hirshfeld surface (in Å).

4. Database survey

To the best of our knowledge and using database tools such as SciFinder^TM (Chemical Abstracts Service, 2023 ), there is only one report of the crystal structure of a compound bearing cinnamaldehyde-4-phenylthiosemicarbazone as non-coordinated molecule (C₁₆H₁₅N₃S) and as a ligand, viz. in the homoleptic [Ni(C₁₆H₁₄N₃S)₂] complex (Song et al., 2014). The asymmetric unit of the reference coordination compound consists of one Ni^II ion, which lies on an inversion center, and two deprotonated cinnamaldehyde-4-phenylthiosemicarbazone ligands, in one of which the atoms are general positions while the second is generated by symmetry (Fig. 6) [symmetry code: (c) −x + 1, −y + 2, −z + 1]. The negative charge of the ligand was assigned by the absence of a hydrazinic H atom and the bond distances in the N—N—C—S chain (please see the remarks in the Structural commentary section of this work and also Table 2). The coordination environment of the Ni^II complex is quite similar to that for the Pd^II metal center of the title compound: the anionic ligands act as metal chelators, κ²N¹S-donors, with N and S atoms in trans-positions (180°), the metal center is fourfold coordinated in a square-planar geometry and the N—N—C—S entity torsion angle is 1.5 (6)°.

Figure 6
Part of the crystal structure of the reference compound, the centrosymmetric [Ni(C₁₆H₁₄N₃S)₂] complex (Song et al., 2014

). The H⋯C and H⋯N intermolecular contacts are drawn as dashed lines and the figure is simplified for clarity. [Symmetry codes: (a) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (b) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (c) −x + 1, −y + 2, −z + 1.]

Although the coordination sphere of the Pd^II title compound and the Ni^II analogue compound are similar, the supramolecular arrangement of the complexes is totally different. In the crystal, the molecules of the centrosymmetric Ni^II coordination compound are linked into a three-dimensional hydrogen-bonded network. The H⋯S intermolecular interactions, like those observed in the Pd^II complex (Fig. 3), are not present in this case and only very weak H⋯C and H⋯N intermolecular contacts are noted. The values for the hydrogen-bonding of the asymmetric part of the complex amount to: C6—H6⋯C5^a = 2.90 (5) Å, C6—H6⋯N1^a = 2.73 (5) Å, C9—H9⋯C14^b = 2.86 (6) Å and N1—H1A⋯C6^a = 2.90 (7) Å [symmetry codes: (a) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (b) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ] (Fig. 6). The H⋯C and H⋯N distances are slightly above the sum of the van der Waals radii for the respective atoms (Bondi, 1964 ; Rowland & Taylor, 1996 ) and they are the only intermolecular contacts observed for the supramolecular structure of the Ni^II complex.

The Hirshfeld surface analysis (Hirshfeld, 1977) of the crystal structure of the Ni^II coordination compound was also performed with CrystalExplorer (Wolff et al., 2012). The graphical representation of the Hirshfeld surface is represented using a ball-and-stick model with transparency and the locations of the strongest intermolecular contacts are draw in magenta, i.e., the regions around the C6, H6, N1, H1A, H9^# and C14^# atoms (Fig. 7) [symmetry code: (#) −x + 1, −y + 2, −z + 1]. These data are in agreement with the weak H⋯C and H⋯N intermolecular contacts observed in the previous figure (Fig. 6). The contributions to the crystal packing are shown as two-dimensional Hirshfeld surface fingerprint plots with cyan dots (Fig. 8). The Hirshfeld surface analysis of the crystal structure also suggests that the most important intermolecular interactions for crystal packing are the following: (a) H⋯H (47.4%), (b) H⋯C/C⋯H (27.6%), (c) H⋯N/N⋯H (7.0%) and (d) H⋯S/S⋯H (6.5%). The d_i (x-axis) and the d_e (y-axis) values are the closest internal and external distances from given points on the Hirshfeld surface contacts (in Å). While for the Pd^II title compound and the Ni^II reference compound the most important intermolecular contacts are H⋯H and the H⋯C/C⋯H, the order of importance changes for the H⋯S/S⋯H and H⋯N/N⋯H contacts. For the crystal packing of the Pd^II complex, the H⋯S/S⋯H contacts are more important then H⋯N/N⋯H contacts, while for the Ni^II complex this order is the opposite.

Figure 7
The Hirshfeld surface graphical representation [d_norm range: −0.045 to 1.492] for the centrosymmetric Ni^II complex (Song et al., 2014

). The surface is drawn with transparency and simplified for clarity. The surface regions with strongest intermolecular contacts are shown in magenta. [Symmetry code: (#) −x + 1, -y+2, −z + 1.]

Figure 8
The Hirshfeld surface two-dimensional fingerprint plot for the Ni^II coordination compound (Song et al., 2014

) showing the (a) H⋯H, (b) H⋯C/C⋯H, (c) H⋯N/N⋯H and (d) H⋯S/S⋯·H contacts in detail (cyan dots). The contributions of the interactions to the crystal cohesion amount to 47.4, 27.6, 7.0 and 6.5%, respectively. The d_i (x-axis) and the d_e (y-axis) values are the closest internal and external distances from given points on the Hirshfeld surface (in Å).

5. Synthesis and crystallization

The starting materials are commercially available and were used without further purification. The synthesis of the ligand was adapted from a previously reported procedure (Freund & Schander, 1902; Tišler, 1956). Cinnamaldehyde-4-phenylthiosemicarbazone was dissolved in ethanol (4 mmol, 50 mL) and deprotonated with one pellet of NaOH with stirring maintained for 2 h until the solution turned yellow. Simultaneously, an ethanolic suspension of palladium(II) chloride (2 mmol, 50 mL) was prepared under continuous stirring. A yellow-colored mixture of the ethanolic solution and the ethanolic suspension was maintained with stirring at room temperature for 8 h, until the PdCl₂ was consumed. Orange single crystals suitable for X-ray diffraction were obtained by the slow evaporation of the solvent.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were located in a difference-Fourier map, but were positioned with idealized geometry and refined isotropically using a riding model (HFIX command), with U_iso(H) = 1.2 U_eq(C, N), and with C—H = 0.93 Å and N—H = 0.86 Å.

Table 3
Experimental details

Crystal data
Chemical formula	[Pd(C₁₆H₁₄N₃S)₂]
M_r	667.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	299
a, b, c (Å)	15.084 (5), 11.418 (4), 17.097 (6)
β (°)	91.097 (9)
V (Å³)	2944.0 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.81
Crystal size (mm)	0.25 × 0.18 × 0.11

Data collection
Diffractometer	Bruker D8 Venture Photon 100 area detector diffractometer
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.699, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	87933, 7344, 6204
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.063, 1.05
No. of reflections	7344
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.50
Computer programs: APEX3 and SAINT (Bruker, 2015 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2006 ), CrystalExplorer (Wolff et al., 2012), WinGX (Farrugia, 2012 ), publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

Supporting information

CCDC reference: 2163054

Crystal structure: contains datablocks I, publication_text. DOI: https://doi.org/10.1107/S2056989023008654/zn2032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023008654/zn2032Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2006), CrystalExplorer (Wolff et al., 2012); software used to prepare material for publication: WinGX (Farrugia, 2012), publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

trans-Bis{(2E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-ylidene]hydrazinecarbothioamidato-κ²N¹,S}palladium(II) top

Crystal data top

[Pd(C₁₆H₁₄N₃S)₂]	F(000) = 1360
M_r = 667.12	D_x = 1.505 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.084 (5) Å	Cell parameters from 9138 reflections
b = 11.418 (4) Å	θ = 2.2–28.3°
c = 17.097 (6) Å	µ = 0.81 mm⁻¹
β = 91.097 (9)°	T = 299 K
V = 2944.0 (16) Å³	Block, orange
Z = 4	0.25 × 0.18 × 0.11 mm

Data collection top

Bruker D8 Venture Photon 100 area detector diffractometer	6204 reflections with I > 2σ(I)
Radiation source: microfocus X ray tube	R_int = 0.042
φ and ω scans	θ_max = 28.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −20→20
T_min = 0.699, T_max = 0.746	k = −15→15
87933 measured reflections	l = −22→22
7344 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.063	w = 1/[σ²(F_o²) + (0.0241P)² + 1.5227P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.003
7344 reflections	Δρ_max = 0.34 e Å⁻³
370 parameters	Δρ_min = −0.50 e Å⁻³
0 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.

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

	x	y	z	U_iso*/U_eq
C1	0.93114 (12)	0.25646 (18)	0.41478 (10)	0.0408 (4)
H1	0.911357	0.222755	0.368099	0.049*
C2	1.02188 (12)	0.29262 (18)	0.41878 (11)	0.0429 (4)
H2	1.042322	0.334403	0.462190	0.052*
C3	1.07777 (12)	0.26780 (19)	0.36174 (11)	0.0434 (4)
H3	1.054715	0.228656	0.318196	0.052*
C4	1.17186 (12)	0.29659 (18)	0.36156 (11)	0.0436 (4)
C5	1.20873 (15)	0.3801 (2)	0.41107 (14)	0.0566 (5)
H4	1.172634	0.422924	0.444057	0.068*
C6	1.29897 (17)	0.4000 (3)	0.41148 (17)	0.0738 (8)
H5	1.323135	0.457206	0.444183	0.089*
C7	1.35360 (16)	0.3362 (3)	0.36419 (19)	0.0765 (8)
H6	1.414532	0.348617	0.366163	0.092*
C8	1.31865 (17)	0.2555 (3)	0.31492 (18)	0.0745 (8)
H7	1.355493	0.212955	0.282440	0.089*
C9	1.22814 (15)	0.2358 (2)	0.31256 (14)	0.0613 (6)
H8	1.204591	0.181127	0.277638	0.074*
C10	0.85343 (12)	0.31504 (17)	0.59615 (10)	0.0377 (4)
C11	0.95766 (12)	0.42049 (17)	0.68829 (10)	0.0397 (4)
C12	0.95571 (14)	0.48633 (19)	0.75646 (11)	0.0466 (5)
H9	0.904012	0.489377	0.785175	0.056*
C13	1.02970 (15)	0.5473 (2)	0.78205 (13)	0.0559 (5)
H10	1.027308	0.591307	0.827731	0.067*
C14	1.10674 (15)	0.5437 (2)	0.74084 (14)	0.0584 (6)
H11	1.156512	0.585126	0.757969	0.070*
C15	1.10894 (14)	0.4777 (2)	0.67371 (14)	0.0597 (6)
H12	1.161063	0.474407	0.645610	0.072*
C16	1.03566 (13)	0.4160 (2)	0.64695 (12)	0.0516 (5)
H13	1.038671	0.371677	0.601430	0.062*
C17	0.55839 (12)	0.16720 (18)	0.50233 (11)	0.0416 (4)
H14	0.578917	0.185524	0.552491	0.050*
C18	0.46597 (12)	0.14045 (18)	0.49358 (11)	0.0429 (4)
H15	0.444566	0.115183	0.445071	0.052*
C19	0.40947 (13)	0.15030 (19)	0.55209 (12)	0.0472 (5)
H16	0.433316	0.172755	0.600361	0.057*
C20	0.31419 (13)	0.12958 (18)	0.54837 (12)	0.0454 (4)
C21	0.27211 (14)	0.0746 (2)	0.48604 (13)	0.0513 (5)
H17	0.305174	0.047797	0.444312	0.062*
C22	0.18134 (15)	0.0590 (2)	0.48519 (16)	0.0644 (6)
H18	0.153934	0.021536	0.442935	0.077*
C23	0.13142 (16)	0.0979 (3)	0.54540 (18)	0.0713 (8)
H19	0.070293	0.087173	0.544212	0.086*
C24	0.17159 (17)	0.1526 (3)	0.60741 (18)	0.0739 (8)
H20	0.137628	0.180199	0.648339	0.089*
C25	0.26240 (16)	0.1673 (2)	0.60978 (15)	0.0653 (6)
H21	0.289272	0.202928	0.653032	0.078*
C26	0.63696 (12)	0.14116 (18)	0.31857 (11)	0.0406 (4)
C27	0.52836 (12)	0.06730 (19)	0.21755 (12)	0.0456 (5)
C28	0.50883 (17)	0.0809 (2)	0.13948 (14)	0.0657 (7)
H22	0.547569	0.121832	0.107827	0.079*
C29	0.4319 (2)	0.0341 (3)	0.10764 (19)	0.0878 (10)
H23	0.418657	0.044846	0.054772	0.105*
C30	0.37560 (18)	−0.0272 (3)	0.1525 (2)	0.0837 (9)
H24	0.323855	−0.058496	0.130698	0.100*
C31	0.39511 (18)	−0.0431 (3)	0.23033 (19)	0.0803 (8)
H25	0.356585	−0.085945	0.261047	0.096*
C32	0.47140 (16)	0.0038 (2)	0.26388 (15)	0.0633 (6)
H26	0.484228	−0.007087	0.316803	0.076*
N1	0.87363 (10)	0.26614 (14)	0.47008 (8)	0.0375 (3)
N2	0.90767 (10)	0.31587 (16)	0.53850 (9)	0.0428 (4)
N3	0.87873 (10)	0.36111 (16)	0.66658 (9)	0.0442 (4)
H27	0.841082	0.352842	0.703313	0.053*
N4	0.61600 (10)	0.16837 (14)	0.44748 (9)	0.0383 (3)
N5	0.58090 (10)	0.13619 (16)	0.37463 (9)	0.0437 (4)
N6	0.61038 (11)	0.11296 (18)	0.24427 (9)	0.0521 (5)
H28	0.649000	0.124627	0.208750	0.063*
Pd1	0.74528 (2)	0.21629 (2)	0.46039 (2)	0.03379 (5)
S1	0.74605 (3)	0.25655 (5)	0.59231 (3)	0.04797 (12)
S2	0.74676 (3)	0.18416 (6)	0.32859 (3)	0.04861 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0320 (9)	0.0589 (11)	0.0314 (9)	−0.0018 (8)	0.0020 (7)	−0.0014 (8)
C2	0.0327 (9)	0.0625 (12)	0.0337 (9)	−0.0045 (8)	−0.0002 (7)	0.0005 (8)
C3	0.0337 (9)	0.0606 (12)	0.0358 (9)	−0.0037 (9)	0.0015 (7)	0.0006 (9)
C4	0.0326 (9)	0.0575 (12)	0.0407 (10)	−0.0026 (8)	0.0018 (7)	0.0101 (9)
C5	0.0445 (12)	0.0656 (14)	0.0596 (13)	−0.0060 (10)	−0.0040 (10)	0.0032 (11)
C6	0.0551 (15)	0.0816 (18)	0.0838 (18)	−0.0223 (14)	−0.0209 (14)	0.0151 (15)
C7	0.0348 (12)	0.094 (2)	0.100 (2)	−0.0080 (13)	−0.0040 (13)	0.0419 (18)
C8	0.0416 (13)	0.097 (2)	0.0858 (19)	0.0078 (13)	0.0206 (13)	0.0207 (17)
C9	0.0445 (12)	0.0805 (17)	0.0594 (14)	−0.0030 (11)	0.0151 (10)	−0.0011 (12)
C10	0.0314 (9)	0.0475 (10)	0.0343 (9)	0.0002 (7)	0.0017 (7)	−0.0005 (7)
C11	0.0351 (9)	0.0486 (10)	0.0354 (9)	0.0000 (8)	−0.0029 (7)	0.0001 (8)
C12	0.0446 (11)	0.0557 (12)	0.0396 (10)	−0.0024 (9)	0.0016 (8)	−0.0032 (9)
C13	0.0578 (13)	0.0596 (13)	0.0499 (12)	−0.0054 (11)	−0.0067 (10)	−0.0103 (10)
C14	0.0443 (12)	0.0655 (14)	0.0650 (14)	−0.0103 (10)	−0.0128 (10)	−0.0005 (11)
C15	0.0341 (10)	0.0826 (17)	0.0624 (14)	−0.0034 (11)	0.0010 (10)	−0.0032 (12)
C16	0.0361 (10)	0.0735 (14)	0.0453 (11)	0.0009 (10)	0.0016 (8)	−0.0096 (10)
C17	0.0360 (9)	0.0542 (11)	0.0347 (9)	−0.0016 (8)	0.0036 (7)	−0.0037 (8)
C18	0.0356 (9)	0.0542 (11)	0.0392 (10)	−0.0007 (8)	0.0053 (8)	−0.0008 (8)
C19	0.0413 (10)	0.0586 (12)	0.0420 (10)	−0.0018 (9)	0.0078 (8)	−0.0009 (9)
C20	0.0390 (10)	0.0505 (11)	0.0471 (11)	0.0018 (8)	0.0116 (8)	0.0071 (9)
C21	0.0415 (11)	0.0609 (13)	0.0516 (12)	0.0024 (10)	0.0072 (9)	0.0081 (10)
C22	0.0468 (13)	0.0740 (16)	0.0722 (16)	−0.0050 (12)	−0.0071 (11)	0.0167 (13)
C23	0.0379 (12)	0.0804 (18)	0.096 (2)	0.0040 (12)	0.0149 (13)	0.0283 (16)
C24	0.0539 (14)	0.0804 (18)	0.089 (2)	0.0055 (13)	0.0362 (14)	0.0086 (16)
C25	0.0539 (14)	0.0782 (16)	0.0645 (15)	−0.0027 (12)	0.0246 (11)	−0.0050 (13)
C26	0.0315 (9)	0.0554 (11)	0.0351 (9)	−0.0013 (8)	0.0021 (7)	−0.0016 (8)
C27	0.0323 (9)	0.0553 (12)	0.0488 (11)	0.0009 (8)	−0.0040 (8)	−0.0101 (9)
C28	0.0631 (15)	0.0751 (16)	0.0582 (14)	−0.0127 (13)	−0.0205 (12)	0.0074 (12)
C29	0.084 (2)	0.095 (2)	0.083 (2)	−0.0132 (18)	−0.0477 (17)	0.0046 (17)
C30	0.0520 (15)	0.089 (2)	0.109 (2)	−0.0128 (14)	−0.0269 (16)	−0.0201 (18)
C31	0.0566 (15)	0.087 (2)	0.098 (2)	−0.0283 (14)	0.0074 (15)	−0.0243 (17)
C32	0.0520 (13)	0.0787 (16)	0.0592 (14)	−0.0154 (12)	0.0031 (11)	−0.0121 (12)
N1	0.0299 (7)	0.0523 (9)	0.0303 (7)	−0.0014 (6)	0.0009 (6)	−0.0023 (6)
N2	0.0324 (8)	0.0645 (10)	0.0316 (8)	−0.0058 (7)	0.0017 (6)	−0.0059 (7)
N3	0.0348 (8)	0.0659 (11)	0.0319 (8)	−0.0070 (8)	0.0045 (6)	−0.0067 (7)
N4	0.0304 (7)	0.0496 (9)	0.0349 (8)	−0.0023 (7)	0.0030 (6)	−0.0023 (7)
N5	0.0322 (8)	0.0646 (11)	0.0342 (8)	−0.0057 (7)	0.0027 (6)	−0.0055 (7)
N6	0.0341 (8)	0.0878 (14)	0.0346 (8)	−0.0110 (9)	0.0028 (7)	−0.0081 (8)
Pd1	0.02574 (7)	0.04563 (8)	0.03007 (7)	−0.00040 (5)	0.00212 (5)	−0.00124 (5)
S1	0.0344 (2)	0.0749 (3)	0.0349 (2)	−0.0119 (2)	0.00699 (18)	−0.0100 (2)
S2	0.0275 (2)	0.0866 (4)	0.0319 (2)	−0.0068 (2)	0.00370 (17)	−0.0071 (2)

Geometric parameters (Å, º) top

C1—N1	1.300 (2)	C18—H15	0.9300
C1—C2	1.430 (3)	C19—C20	1.457 (3)
C1—H1	0.9300	C19—H16	0.9300
C2—C3	1.332 (3)	C20—C21	1.381 (3)
C2—H2	0.9300	C20—C25	1.389 (3)
C3—C4	1.457 (3)	C21—C22	1.380 (3)
C3—H3	0.9300	C21—H17	0.9300
C4—C5	1.385 (3)	C22—C23	1.361 (4)
C4—C9	1.389 (3)	C22—H18	0.9300
C5—C6	1.380 (3)	C23—C24	1.363 (4)
C5—H4	0.9300	C23—H19	0.9300
C6—C7	1.374 (4)	C24—C25	1.380 (3)
C6—H5	0.9300	C24—H20	0.9300
C7—C8	1.349 (4)	C25—H21	0.9300
C7—H6	0.9300	C26—N5	1.291 (2)
C8—C9	1.383 (3)	C26—N6	1.363 (2)
C8—H7	0.9300	C26—S2	1.7328 (19)
C9—H8	0.9300	C27—C28	1.370 (3)
C10—N2	1.293 (2)	C27—C32	1.384 (3)
C10—N3	1.362 (2)	C27—N6	1.410 (2)
C10—S1	1.7520 (19)	C28—C29	1.380 (3)
C11—C16	1.385 (3)	C28—H22	0.9300
C11—C12	1.388 (3)	C29—C30	1.351 (4)
C11—N3	1.413 (2)	C29—H23	0.9300
C12—C13	1.380 (3)	C30—C31	1.369 (4)
C12—H9	0.9300	C30—H24	0.9300
C13—C14	1.371 (3)	C31—C32	1.384 (3)
C13—H10	0.9300	C31—H25	0.9300
C14—C15	1.374 (3)	C32—H26	0.9300
C14—H11	0.9300	N1—N2	1.390 (2)
C15—C16	1.381 (3)	N1—Pd1	2.0217 (16)
C15—H12	0.9300	N3—H27	0.8600
C16—H13	0.9300	N4—N5	1.393 (2)
C17—N4	1.291 (2)	N4—Pd1	2.0333 (16)
C17—C18	1.432 (3)	N6—H28	0.8600
C17—H14	0.9300	Pd1—S2	2.2836 (9)
C18—C19	1.331 (3)	Pd1—S1	2.3016 (9)

N1—C1—C2	126.30 (17)	C25—C20—C19	119.0 (2)
N1—C1—H1	116.8	C22—C21—C20	120.5 (2)
C2—C1—H1	116.8	C22—C21—H17	119.7
C3—C2—C1	121.49 (18)	C20—C21—H17	119.7
C3—C2—H2	119.3	C23—C22—C21	120.9 (3)
C1—C2—H2	119.3	C23—C22—H18	119.6
C2—C3—C4	125.73 (19)	C21—C22—H18	119.6
C2—C3—H3	117.1	C22—C23—C24	119.6 (2)
C4—C3—H3	117.1	C22—C23—H19	120.2
C5—C4—C9	118.0 (2)	C24—C23—H19	120.2
C5—C4—C3	122.27 (19)	C23—C24—C25	120.3 (2)
C9—C4—C3	119.7 (2)	C23—C24—H20	119.8
C6—C5—C4	120.0 (2)	C25—C24—H20	119.8
C6—C5—H4	120.0	C24—C25—C20	120.8 (3)
C4—C5—H4	120.0	C24—C25—H21	119.6
C7—C6—C5	120.8 (3)	C20—C25—H21	119.6
C7—C6—H5	119.6	N5—C26—N6	119.74 (17)
C5—C6—H5	119.6	N5—C26—S2	125.25 (14)
C8—C7—C6	119.9 (2)	N6—C26—S2	115.00 (13)
C8—C7—H6	120.1	C28—C27—C32	119.5 (2)
C6—C7—H6	120.1	C28—C27—N6	116.4 (2)
C7—C8—C9	120.2 (3)	C32—C27—N6	123.9 (2)
C7—C8—H7	119.9	C27—C28—C29	120.3 (3)
C9—C8—H7	119.9	C27—C28—H22	119.9
C8—C9—C4	121.0 (3)	C29—C28—H22	119.9
C8—C9—H8	119.5	C30—C29—C28	120.6 (3)
C4—C9—H8	119.5	C30—C29—H23	119.7
N2—C10—N3	120.03 (17)	C28—C29—H23	119.7
N2—C10—S1	124.91 (14)	C29—C30—C31	119.7 (2)
N3—C10—S1	115.06 (13)	C29—C30—H24	120.2
C16—C11—C12	118.73 (18)	C31—C30—H24	120.2
C16—C11—N3	124.58 (18)	C30—C31—C32	120.9 (3)
C12—C11—N3	116.68 (17)	C30—C31—H25	119.6
C13—C12—C11	120.6 (2)	C32—C31—H25	119.6
C13—C12—H9	119.7	C31—C32—C27	119.0 (2)
C11—C12—H9	119.7	C31—C32—H26	120.5
C14—C13—C12	120.7 (2)	C27—C32—H26	120.5
C14—C13—H10	119.7	C1—N1—N2	113.95 (15)
C12—C13—H10	119.7	C1—N1—Pd1	124.60 (13)
C13—C14—C15	118.7 (2)	N2—N1—Pd1	121.45 (11)
C13—C14—H11	120.7	C10—N2—N1	114.18 (15)
C15—C14—H11	120.7	C10—N3—C11	129.63 (16)
C14—C15—C16	121.6 (2)	C10—N3—H27	115.2
C14—C15—H12	119.2	C11—N3—H27	115.2
C16—C15—H12	119.2	C17—N4—N5	113.40 (15)
C15—C16—C11	119.6 (2)	C17—N4—Pd1	125.56 (13)
C15—C16—H13	120.2	N5—N4—Pd1	121.01 (11)
C11—C16—H13	120.2	C26—N5—N4	114.13 (15)
N4—C17—C18	126.43 (17)	C26—N6—C27	129.03 (17)
N4—C17—H14	116.8	C26—N6—H28	115.5
C18—C17—H14	116.8	C27—N6—H28	115.5
C19—C18—C17	122.63 (19)	N1—Pd1—N4	178.31 (6)
C19—C18—H15	118.7	N1—Pd1—S2	95.66 (4)
C17—C18—H15	118.7	N4—Pd1—S2	82.94 (4)
C18—C19—C20	126.8 (2)	N1—Pd1—S1	82.92 (4)
C18—C19—H16	116.6	N4—Pd1—S1	98.45 (4)
C20—C19—H16	116.6	S2—Pd1—S1	177.57 (2)
C21—C20—C25	117.9 (2)	C10—S1—Pd1	95.74 (6)
C21—C20—C19	123.10 (18)	C26—S2—Pd1	96.65 (6)

N1—C1—C2—C3	172.9 (2)	C32—C27—C28—C29	1.5 (4)
C1—C2—C3—C4	−177.50 (19)	N6—C27—C28—C29	177.0 (3)
C2—C3—C4—C5	−17.8 (3)	C27—C28—C29—C30	−1.1 (5)
C2—C3—C4—C9	159.6 (2)	C28—C29—C30—C31	0.0 (5)
C9—C4—C5—C6	−0.8 (3)	C29—C30—C31—C32	0.6 (5)
C3—C4—C5—C6	176.7 (2)	C30—C31—C32—C27	−0.1 (4)
C4—C5—C6—C7	−1.2 (4)	C28—C27—C32—C31	−0.9 (4)
C5—C6—C7—C8	2.0 (4)	N6—C27—C32—C31	−176.0 (2)
C6—C7—C8—C9	−0.8 (4)	C2—C1—N1—N2	−0.7 (3)
C7—C8—C9—C4	−1.3 (4)	C2—C1—N1—Pd1	178.74 (16)
C5—C4—C9—C8	2.0 (4)	N3—C10—N2—N1	179.95 (17)
C3—C4—C9—C8	−175.5 (2)	S1—C10—N2—N1	0.6 (3)
C16—C11—C12—C13	0.8 (3)	C1—N1—N2—C10	−173.45 (18)
N3—C11—C12—C13	−179.92 (19)	Pd1—N1—N2—C10	7.1 (2)
C11—C12—C13—C14	−0.3 (3)	N2—C10—N3—C11	4.6 (3)
C12—C13—C14—C15	−0.3 (4)	S1—C10—N3—C11	−175.92 (16)
C13—C14—C15—C16	0.4 (4)	C16—C11—N3—C10	−18.5 (3)
C14—C15—C16—C11	0.2 (4)	C12—C11—N3—C10	162.2 (2)
C12—C11—C16—C15	−0.7 (3)	C18—C17—N4—N5	−2.1 (3)
N3—C11—C16—C15	−180.0 (2)	C18—C17—N4—Pd1	176.05 (16)
N4—C17—C18—C19	−174.5 (2)	N6—C26—N5—N4	−179.31 (18)
C17—C18—C19—C20	177.5 (2)	S2—C26—N5—N4	−0.4 (3)
C18—C19—C20—C21	13.0 (4)	C17—N4—N5—C26	177.55 (18)
C18—C19—C20—C25	−166.5 (2)	Pd1—N4—N5—C26	−0.7 (2)
C25—C20—C21—C22	0.5 (3)	N5—C26—N6—C27	−6.0 (4)
C19—C20—C21—C22	−178.9 (2)	S2—C26—N6—C27	175.02 (18)
C20—C21—C22—C23	0.3 (4)	C28—C27—N6—C26	160.2 (2)
C21—C22—C23—C24	−0.2 (4)	C32—C27—N6—C26	−24.6 (4)
C22—C23—C24—C25	−0.8 (4)	N2—C10—S1—Pd1	−6.03 (18)
C23—C24—C25—C20	1.7 (4)	N3—C10—S1—Pd1	174.54 (14)
C21—C20—C25—C24	−1.5 (4)	N5—C26—S2—Pd1	1.1 (2)
C19—C20—C25—C24	178.0 (2)	N6—C26—S2—Pd1	179.99 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···S2	0.93	2.60	3.230 (2)	126
C16—H13···N2	0.93	2.32	2.887 (3)	119
C17—H14···S1	0.93	2.72	3.355 (2)	126
C32—H26···N5	0.93	2.39	2.911 (3)	115
N3—H27···S2ⁱ	0.86	2.63	3.4805 (18)	171
N6—H28···S1ⁱⁱ	0.86	2.84	3.6554 (19)	159

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

Bond lengths (Å) for the N—N—C—S entities in cinnamaldehyde-4-phenylthiosemicarbazone structures: as a neutral molecule and as an anionic ligand top

	N—N	N—C	C—S
C₁₆H₁₅N₃S^a^,^c	1.369 (2)	1.354 (2)	1.6704 (19)
Ni(C₁₆H₁₄N₃S)₂^b^,^c	1.405 (5)	1.301 (6)	1.730 (5)
Pd(C₁₆H₁₄N₃S)₂^b^,^d	1.390 (2)	1.293 (2)	1.7520 (19)
	1.393 (2)	1.291 (2)	1.7328 (19)

Notes: (a) Neutral, non-coordinated form of the cinnamaldehyde 4-phenylthiosemicarbazone; (b) anionic, coordinated form of the cinnamaldehyde 4-phenylthiosemicarbazone; (c) Song et al. (2014); (d) this work.

Acknowledgements

APLM thanks CAPES for the award of a PhD scholarship. The authors thank the Department of Chemistry of the Federal University of Santa Maria/Brazil for the access to the X-ray diffraction facility.

Funding information

Funding for this research was provided by: Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brazil (CAPES), Finance code 001.

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2015). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chemical Abstracts Service (2023). Columbus, Ohio, USA (accessed via SciFinder on September 1, 2023). Google Scholar
Farias, R. L., Polez, A. M. R., Silva, A. D. E. S., Zanetti, R. D., Moreira, M. B., Batista, V. S., Reis, B. L., Nascimento-Júnior, N. M., Rocha, F. V., Lima, M. A., Oliveira, A. B., Ellena, J., Scarim, C. B., Zambom, C. R., Brito, L. D., Garrido, S. S., Melo, A. P. L., Bresolin, L., Tirloni, B., Pereira, J. C. M. & Netto, A. V. G. (2021). Mater. Sci. Eng. C, 121, 111815, 1–12. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Freund, M. & Schander, A. (1902). Ber. Dtsch. Chem. Ges. 35, 2602–2606. CrossRef CAS Google Scholar
Hirshfeld, H. L. (1977). Theor. Chim. Acta, 44, 129–138. CrossRef CAS Web of Science Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Lobana, T. S., Sharma, R., Bawa, G. & Khanna, S. (2009). Coord. Chem. Rev. 253, 977–1055. Web of Science CrossRef CAS Google Scholar
Mostafa, H. A. (2000). Electrochim. Acta, 18, 45–53. CrossRef CAS Google Scholar
Nyawadea, E. A., Sibuyi, N. R. S., Meyer, M., Lalancette, R. & Onani, M. O. (2021). Inorg. Chim. Acta, 515, 120036, 1–10. Google Scholar
Oliveira, A. B. de, Feitosa, B. R. S., Näther, C. & Jess, I. (2014). Acta Cryst. E70, 101–103. CSD CrossRef IUCr Journals Google Scholar
Palve, A. M. & Garje, S. S. (2011). J. Cryst. Growth, 326, 157–162. Web of Science CrossRef CAS Google Scholar
Pawar, A. S. & Garje, S. S. (2015). Bull. Mater. Sci. 38, 1843–1850. Web of Science CrossRef CAS Google Scholar
Pawar, A. S., Masikane, S. C., Mlowe, S., Garje, S. S. & Revaprasadu, N. (2016). Eur. J. Inorg. Chem. pp. 366–372. Web of Science CrossRef Google Scholar
Rocha, F. V., Farias, R. L., Lima, M. A., Batista, V. S., Nascimento-Júnior, N. M., Garrido, S. S., Leopoldino, A. M., Goto, R. N., Oliveira, A. B., Beck, J., Landvogt, C., Mauro, A. E. & Netto, A. V. G. (2019). J. Inorg. Biochem. 199, 110725, 1–9. Google Scholar
Rowland, R. S. & Taylor, R. (1996). J. Phys. Chem. 100, 7384–7391. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Song, J., Zhu, F., Wang, H. & Zhao, P. (2014). Spectrochim. Acta A Mol. Biomol. Spectrosc. 129, 227–234. Web of Science CSD CrossRef CAS PubMed Google Scholar
Tišler, M. (1956). Z. Anal. Chem. 149, 164–172. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer 3.1. University of Western Australia, Australia. 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.