Synthesis, crystal structure, Hirshfeld surface analysis and DFT calculations of the coordination compound tetra­aqua­bis­{2-[(5-methyl-1,3,4-thia­diazol-2-yl)sulfan­yl]acetato-κO}cobalt(II)

Kinshakova, E.; Torambetov, B.; Kaur, S.; Ashurov, J.; Kadirova, S.

doi:10.1107/S2056989024011939

research communications

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ISSN: 2056-9890

Volume 81| Part 1| January 2025| Pages 63-68

https://doi.org/10.1107/S2056989024011939

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Synthesis, crystal structure, Hirshfeld surface analysis and DFT calculations of the coordination compound tetraaquabis{2-[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetato-κO}cobalt(II)

Ekaterina Kinshakova,^a Batirbay Torambetov,^a,^b ^* Simranjeet Kaur,^b,^c Jamshid Ashurov ^d and Shakhnoza Kadirova ^a

^aNational University of Uzbekistan named after Mirzo Ulugbek, 4 University St, Tashkent, 100174, Uzbekistan, ^bPhysical and Material Chemistry Division, CSIR-National Chemical Laboratory, Pune, 411008, India, ^cAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India, and ^dInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, M. Ulugbek St, 83, Tashkent, 100125, Uzbekistan
^*Correspondence e-mail: torambetov_b@mail.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 October 2024; accepted 9 December 2024; online 1 January 2025)

A novel coordination compound, [Co(L)₂(H₂O)₄], was synthesized from aqueous solutions of Co(NO₃)₂ and the ligand 2-[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetic acid (HL, C₅H₆N₂O₂S₂). In the monoclinic crystals (space group P2₁/c), the cobalt(II) ion is located about a centre of symmetry and is octahedrally coordinated by two L⁻ anions in a monodentate fashion through carboxyl O atoms and by four water molecules. A relatively strong hydrogen bond between one of the water molecules and the non-coordinating carboxylate O atom consolidates the conformation. In the crystal, intermolecular hydrogen bonds lead to the formation of a complex tri-periodic structure. Hirshfeld surface analysis revealed that 30.1% of the intermolecular interactions are from H⋯H contacts and 20.8% are from N⋯H/H⋯N contacts. DFT calculations were performed to assess the stability and chemical reactivity of the compound by determining the energy differences between the HOMO and LUMO.

Keywords: crystal structure; cobalt(II); 1,3,4-thiadiazole; hydrogen bonding; Hirshfeld surface analysis; DFT calculation.

CCDC reference: 2408680

1. Chemical context

1,3,4-Thiadiazole derivatives are versatile compounds with significant applications in various fields, notably as ligands in the formation of metal complexes (Frija et al., 2016 ). Their ability to coordinate metal ions through multiple donor atoms allows for the creation of stable and diverse complexes (Atashov et al., 2024 ; Lavrenova et al., 2023 ; Serbest et al., 2008 ), which can be tailored for specific applications in medicine (Masaryk et al., 2022 ; Patil et al., 2020 ; Karcz et al., 2020 ), agriculture (Smaili et al., 2017 ; Chandra et al., 2015 ) or materials science (Bawazeer et al., 2020 ; Karasmani et al., 2018 ; Wang et al., 2012 ).

[(5-Methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetic acid (HL) is a derivative of 5-methyl-1,3,4-thiadiazole-2-thiol by S-alkylation. It is a sulfur-containing carboxylic acid, which is widely used due to its unique properties. It is a non-toxic and water-soluble compound in which the substituent is located in the form of a pharmacophore, which can lead to higher reactivity and biological activity through complexation. In this context, we report here on the title coordination compound [Co(L)₂(H₂O)₄].

2. Structural commentary

The molecular structure of [Co(L)₂(H₂O)₄] is shown in Fig. 1. The asymmetric unit comprises half a molecule of the complex, with the Co^II atom located about a centre of symmetry. The Co^II atom exhibits a slightly distorted octahedral coordination environment formed by carboxylate and water O atoms. The carboxylate group coordinates monodentately through O1, O1ⁱ together with water O atoms O4 and O4ⁱ in the equatorial plane [symmetry code: (i) –x + 1, –y + 1, –z + 1], whereas the two water O atoms O3 and O3ⁱ are in axial positions. The corresponding distances are listed in Table 1. The cis-bond angles in the coordination polyhedron vary from 84.80 (8) to 95.20 (8)°. Bond lengths and angles of the 5-methyl-1,3,4-thiadiazole-2-thiolate ligand are similar to the standard values observed in similar structures (see section 6). The positions of the ligands allow for the formation of one rather strong hydrogen bond between a water molecule (O3—H3B) and the non-coordinating carboxylate O4 atom (Table 2), which is shorter than the stated distance (2.85 Å) in liquid water (Eisenberg & Kauzmann, 2005 ). This hydrogen bond leads to a six-membered ring motif with designation S(6) (Etter, 1990 ; Etter et al., 1990 ; Grabowski, 2020 ). Moreover, crystal-packing effects result in the C4—H4C⋯S distances (Table 2) being smaller than the sum of the van der Waals radii, and the existing short intramolecular contacts can be considered from a geometrical and topological point of view as a weak hydrogen bond contributing to the overall cohesion of the molecular conformation (Fargher et al., 2022 ; Domagała et al., 2003 ; Surange et al., 1997 ).

Table 1
Selected bond lengths (Å)

Co1—O1	2.088 (2)	Co1—O4	2.036 (2)
Co1—O3	2.146 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O2	0.87 (2)	1.91 (3)	2.700 (3)	151 (5)
C4—H4C⋯S1	0.97	2.79	3.181 (3)	105
O4—H4A⋯N2ⁱ	0.85	1.95	2.764 (4)	160
O4—H4B⋯O1ⁱⁱ	0.85	1.91	2.757 (3)	172
O3—H3A⋯N1ⁱ	0.84 (5)	2.17 (5)	2.979 (4)	162 (5)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) .

Figure 1
The molecular structure of the title complex [Co(L)₂(H₂O)₄]. Displacement ellipsoids are shown at the 20% probability level. Non-labelled atoms are generated by inversion symmetry [symmetry operation: 1 − x, 1 − y, 1 − z].

3. Supramolecular features and energy framework calculations

In the crystal structure of [Co(L)₂(H₂O)₄], further hydrogen bonds are observed (Table 2). Neighboring cobalt complexes are connected parallel to the a axis by O4—H4B⋯O1ⁱ and O4ⁱ—H4Bⁱ ⋯O1 interactions; the corresponding Co1⋯Co1ⁱ distance is 5.195 Å (Fig. 2a). Neighboring central atoms are located at distances of 10.035 (1) and 18.909 (1) Å, respectively, along the b- and c-axis directions, and cohesion in the crystal is achieved due to the O3—H3A⋯N1 and O4—H4A⋯N2 hydrogen bonds (Fig. 2b).

Figure 2
Overview of hydrogen-bonding interactions and the crystal packing: (a) Interactions along the a axis; (b) interactions along the b and c axes, highlighting the O3—H3A⋯N1 and O4—H4A⋯N2 hydrogen bonds (as per symmetry operators).

The interaction energies of the hydrogen-bonding system were calculated using the HF method (HF/3-21G) in CrystalExplorer (Spackman et al., 2021 ). The result is represented graphically in Fig. 3, showing the total energy (E_tot), which is the sum of the Coulombic (E_ele), polar (E_pol), dispersion (E_dis) and repulsive (E_rep) contributions. The four energy components were scaled for the total energy calculation (E_tot = 1.019E_ele + 0.651E_pol + 0.901E_dis + 0.811E_rep). The interaction energies were investigated for a 3.8 Å cluster around the reference molecule and are depicted in Fig. 4a as framework energy diagrams. The components of the interaction energies (E), symmetry operations concerning the reference molecule (Symop), the centroid-to-centroid distances between the reference molecule and interacting molecules (R), and the number of pair(s) of interacting molecules to the reference molecule (N) are listed in Fig. 4b. The total interaction energy is −274.5 kJ mol⁻¹, involving the electrostatic (–257.2 kJ mol⁻¹), polarization (–74.6 kJ mol⁻¹), dispersion (–129.3 kJ mol⁻¹), and repulsion (186.6 kJ mol⁻¹) energies. The main attractive interactions (Coulombic, dispersion and the sum total energy) show a stronger bonding effect along the crystallographic a-axis direction.

Figure 3
Calculated interaction energies in the title compound. The thickness of the tubes correspond to the value of the energy, revealing strong interactions along the crystallographic a-axis direction (the largest values are represented here). The total energy framework (in red) and its two main components, dispersion (in green) and Coulombic energy (in blue), shown for a cluster around a reference molecule, also exhibit stronger interactions along the crystallographic a-axis direction.

Figure 4
(a) Energy framework diagram for compound [Co(L)₂(H₂O)₄]; (b) the color-coded interaction mapping within 3.8 Å of the center molecule (gray) calculated with the CE—HF⋯HF/3–21 G model (R is the distance between molecular centroids (main atomic position) in Å, all interaction energies in kJ mol⁻¹).

4. Hirshfeld surface analysis

To further investigate the intermolecular interactions present in the title compound, a Hirshfeld surface (HS) analysis was performed, and the two-dimensional fingerprint plots were generated with CrystalExplorer (Spackman et al., 2021). Fig. 5 shows the three-dimensional Hirshfeld surface of the complex plotted over d_norm (normalized contact distance). The hydrogen-bonding interactions given in Table 2 play a key role in the molecular packing of the complex.

Figure 5
View of the three-dimensional Hirshfeld surface of [Co(L)₂(H₂O)₄] (central part). The full two-dimensional fingerprint plots for the title complex, showing all interactions and delineated into separate interactions with the percentage contribution of various interatomic contacts occurring in the crystal are shown at the top and bottom.

The overall two-dimensional fingerprint plot and those delineated into interatomic interactions are given in Fig. 5. The HS analysis shows that the most important contributions are from H⋯H, N⋯H/H⋯N, O⋯H/H⋯O and S⋯H/H⋯S contacts, while other contributions (C⋯H/H⋯C, S⋯O/O⋯S, S⋯C/C⋯S and S⋯N/N⋯S) are considered as minor contacts. The percentage contributions of the various interatomic contacts occurring in the crystal are also shown in Fig. 5.

5. Density functional theory (DFT) calculations

The molecular structure of the complex was optimized in the gas phase by the B3LYP (Lee et al., 1988 ) DFT method using the LanL2dz basis set (Grimme, 2006 ) for the Co atom and 6-311G (d,p) basis set (de Castro & Jorge, 1998 ) for non-metal atoms. Calculations were conducted using the Gaussian09 program (Frisch et al., 2009 ) to evaluate the stability of the compound and its chemical reactivity by determining the HOMO–LUMO (highest occupied molecular orbital - lowest unoccupied molecular orbital) energy differences, the ionization potential (I), the affinity electronics (A), the electrophilicity index (ω), the chemical potential (μ), the hardness (η) and the softness (S). The optimized potential surface molecular electrostatic potential (MEP) was also determined to characterize the effects of various substituent groups. Additionally, an analysis was performed to identify regions of electron richness and deficiency.

It is well known that for a closed-shell molecule (all electrons are paired) the HOMO–LUMO energy gap is related to its stability. The same argument is used for open-shell systems (unrestricted calculation). In this case, it is taken into account that the energies of both α- and β-spin orbitals designate the orbital with the highest energy as SOMO (singly occupied molecular orbital). Similarly, the LUMO is defined among both α and β, and the corresponding gap is considered as the SOMO–LUMO gap (Abella et al., 2021 ). Fig. 6 shows the SOMO and LUMO of the title cobalt complex, as well as the DOS (density of states) spectrum displaying the group contributions to the molecular orbitals and the calculation of the density of states (Gauss-Sum 3.0). The DOS spectra were obtained by combining the molecular orbital information with the extraction from Gaussian (O'boyle et al., 2008 ). The descriptors of the reactivity of the complex derived from the electronic properties of the specified molecule (Padmanabhan et al., 2007 ; Hekim & Pekdemir, 2022 ) based on the energies of the HOMO (SOMO) and LUMO orbitals, are shown in Table 3.

Table 3
Global reactivity indices

E SOMO (eV)	−6.64
E LUMO (eV)	−2.39
ΔE	4.25
I	6.64
A	2.39
χ	4.515
η	2.125
μ	−4.515
S	0.235
ω	0.235

Figure 6
DOS spectrum, SOMO and LUMO energies and energy gap in the title complex.

The electrophilic and nucleophilic nature of the interactions, as well as hydrogen bonds, can be explained using the molecular electrostatic potential (MEP), which is related to the electron density. The total electron density surface and the surface of the contour in the form of two-dimensional surface curves of the title complex is given in Fig. 7, which has color codes from red to blue, representing negative to positive potential distributions. The optimum electrophilic reaction zones are localized on N atoms, the maximum positive regions that determine nucleophilic reactions are concentrated at the hydrogen atoms of the water molecules. These locations provide insight into the regions of the molecule that engage in non-covalent interactions.

Figure 7
The total electron density surface and the surface of the contour in the form of two dimensional surface curves of [Co(L)₂(H₂O)₄].

6. Database survey

A survey of the Cambridge Structural Database (CSD, Version 5.45, last updated March 2024; Groom et al., 2016 ) indicates that crystal structures have been reported for complexes of 2-methyl-1,3,4-thiadiazole derivatives with several metal ions, including Co, Ni, Cu, Zn, Ru, Ag, Pd, Cd, Sn, Pr, Nd, Pt, Hg, and Bi. Notably, there are ten reported metal complex structures featuring 2-[(5-methyl-1,3,4-thiadiazol-2-yl)thio]acetate (denoted as L), specifically: DEKGAE, DEKGEI (Pan & Zheng, 2017 ); ICOVED, ICOVIH (Pan, 2011 ); QAFRAS, QAFREW (Pan et al., 2010 ) and UNENAD, UNENEH, UNENIL, UNENOR (Ma et al., 2010 ). In these structures, L coordinates to the metal ions through the oxygen atom of the carboxylic group. Notably, in the UNENEH structure, L does not directly coordinate to the Co^II cation. It is interesting to note that the title compound differs from the UNENAD structure by the absence of one water molecule.

7. Synthesis and crystallization

A solution of Co(NO₃)₂·6H₂O (0.291 g, 0.1 mmol) in C₂H₅OH (3 ml) was added to a solution of HL (0.38 g, 0.2 mmol) in C₂H₅OH/H₂O (5 ml, 1:1), the pH of which was adjusted to 7.0 with dilute sodium hydroxide (1 mol/l). The mixture was stirred at room temperature for 5 h to obtain a clear solution, which was then filtered. Slow evaporation of the filtrate after two weeks gave pink single crystals in the form of blocks suitable for X-ray diffraction. Yield: 0.367 g (72%).

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All hydrogen atoms were located in difference-Fourier maps and reﬁned using an isotropic approximation. The water hydrogen atoms were constrained to an ideal geometry with distances fixed at 0.87 (4) Å and U_iso(H) = 1.5U_eq(O). Two reflections ( $[\overline{3}]$ 10 9; $[\overline{1}]$ 11 11) were omitted from the refinement..

Table 4
Experimental details

Crystal data
Chemical formula	[Co(C₅H₅N₂O₂S₂)₂(H₂O)₄]
M_r	509.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.1950 (2), 10.0347 (3), 18.9090 (6)
β (°)	91.892 (3)
V (Å³)	985.19 (6)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	11.23
Crystal size (mm)	0.08 × 0.06 × 0.04

Data collection
Diffractometer	Xcalibur, Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.808, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6554, 2023, 1770
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.098, 1.06
No. of reflections	2023
No. of parameters	137
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.27
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2408680

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024011939/wm5739sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024011939/wm5739Isup3.hkl

checkCIF report

Computing details top

Tetraaquabis{2-[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetato-κO}cobalt(II) top

Crystal data top

[Co(C₅H₅N₂O₂S₂)₂(H₂O)₄]	F(000) = 522
M_r = 509.45	D_x = 1.717 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 5.1950 (2) Å	Cell parameters from 2568 reflections
b = 10.0347 (3) Å	θ = 4.4–74.9°
c = 18.9090 (6) Å	µ = 11.23 mm⁻¹
β = 91.892 (3)°	T = 293 K
V = 985.19 (6) Å³	Block, pink
Z = 2	0.08 × 0.06 × 0.04 mm

Data collection top

Xcalibur, Ruby diffractometer	2023 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	1770 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 10.2576 pixels mm^-1	θ_max = 76.1°, θ_min = 4.7°
ω scans	h = −6→5
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	k = −12→7
T_min = 0.808, T_max = 1.000	l = −22→23
6554 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)] = 0.038	w = 1/[σ²(F_o²) + (0.0423P)² + 0.2531P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.34 e Å⁻³
2023 reflections	Δρ_min = −0.27 e Å⁻³
137 parameters	Extinction correction: SHELXL (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0100 (6)
Primary atom site location: dual

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
Co1	0.500000	0.500000	0.500000	0.0225 (2)
S2	0.93444 (16)	0.67263 (8)	0.23436 (4)	0.0363 (2)
S1	0.51630 (16)	0.46582 (8)	0.19232 (4)	0.0352 (2)
O1	0.7298 (4)	0.4971 (2)	0.41151 (11)	0.0301 (5)
O3	0.3120 (5)	0.6845 (2)	0.47316 (12)	0.0319 (5)
O2	0.5470 (5)	0.6628 (2)	0.34843 (12)	0.0381 (5)
O4	0.7849 (4)	0.5994 (2)	0.55445 (14)	0.0403 (6)
H4A	0.754101	0.661162	0.583781	0.060*
H4B	0.939850	0.576984	0.564102	0.060*
N2	0.6147 (6)	0.6755 (3)	0.12306 (16)	0.0439 (7)
N1	0.4211 (7)	0.6115 (3)	0.08461 (16)	0.0466 (7)
C5	0.7135 (6)	0.5770 (3)	0.35950 (15)	0.0261 (6)
C4	0.9347 (6)	0.5598 (3)	0.30843 (16)	0.0308 (6)
H4C	0.929270	0.469381	0.290307	0.037*
H4D	1.096227	0.570265	0.335059	0.037*
C2	0.6821 (6)	0.6126 (3)	0.18058 (16)	0.0314 (6)
C1	0.3501 (7)	0.5011 (3)	0.11352 (17)	0.0350 (7)
C3	0.1401 (8)	0.4148 (4)	0.0839 (2)	0.0464 (8)
H3C	0.208492	0.355386	0.049477	0.070*
H3D	0.008604	0.469362	0.061893	0.070*
H3E	0.067607	0.363860	0.121388	0.070*
H3A	0.311 (9)	0.750 (5)	0.501 (2)	0.061 (14)*
H3B	0.383 (9)	0.707 (5)	0.4341 (17)	0.070 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0219 (3)	0.0233 (3)	0.0222 (3)	0.0038 (2)	−0.0007 (2)	−0.0002 (2)
S2	0.0405 (5)	0.0368 (4)	0.0316 (4)	−0.0094 (3)	0.0025 (3)	0.0057 (3)
S1	0.0430 (5)	0.0323 (4)	0.0301 (4)	−0.0059 (3)	−0.0032 (3)	0.0096 (3)
O1	0.0298 (11)	0.0348 (11)	0.0259 (10)	0.0063 (8)	0.0038 (8)	0.0037 (8)
O3	0.0374 (13)	0.0277 (10)	0.0304 (11)	0.0073 (9)	−0.0013 (9)	−0.0001 (8)
O2	0.0392 (13)	0.0426 (12)	0.0326 (11)	0.0156 (10)	0.0032 (10)	0.0060 (9)
O4	0.0248 (11)	0.0418 (13)	0.0534 (15)	0.0074 (9)	−0.0121 (10)	−0.0217 (10)
N2	0.0510 (18)	0.0427 (16)	0.0375 (15)	−0.0075 (13)	−0.0077 (13)	0.0156 (12)
N1	0.0571 (19)	0.0473 (17)	0.0348 (15)	−0.0039 (14)	−0.0077 (14)	0.0123 (13)
C5	0.0263 (14)	0.0275 (13)	0.0242 (13)	−0.0011 (11)	−0.0008 (11)	−0.0012 (10)
C4	0.0299 (15)	0.0350 (15)	0.0276 (14)	0.0044 (12)	0.0018 (11)	0.0022 (11)
C2	0.0373 (17)	0.0302 (14)	0.0270 (14)	0.0016 (12)	0.0036 (12)	0.0062 (11)
C1	0.0422 (19)	0.0347 (16)	0.0281 (15)	0.0056 (13)	0.0010 (13)	0.0047 (11)
C3	0.048 (2)	0.0464 (19)	0.0437 (19)	−0.0003 (16)	−0.0115 (16)	0.0015 (15)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.088 (2)	O2—C5	1.233 (4)
Co1—O1	2.088 (2)	O4—H4A	0.8501
Co1—O3	2.146 (2)	O4—H4B	0.8500
Co1—O3ⁱ	2.146 (2)	N2—N1	1.380 (4)
Co1—O4	2.036 (2)	N2—C2	1.296 (4)
Co1—O4ⁱ	2.036 (2)	N1—C1	1.295 (4)
S2—C4	1.801 (3)	C5—C4	1.535 (4)
S2—C2	1.740 (3)	C4—H4C	0.9700
S1—C2	1.724 (3)	C4—H4D	0.9700
S1—C1	1.734 (3)	C1—C3	1.488 (5)
O1—C5	1.270 (3)	C3—H3C	0.9600
O3—H3A	0.84 (5)	C3—H3D	0.9600
O3—H3B	0.868 (19)	C3—H3E	0.9600

O1ⁱ—Co1—O1	180.0	C2—N2—N1	112.8 (3)
O1—Co1—O3	95.20 (8)	C1—N1—N2	112.9 (3)
O1ⁱ—Co1—O3ⁱ	95.20 (8)	O1—C5—C4	112.6 (2)
O1—Co1—O3ⁱ	84.80 (8)	O2—C5—O1	127.0 (3)
O1ⁱ—Co1—O3	84.80 (8)	O2—C5—C4	120.5 (3)
O3—Co1—O3ⁱ	180.0	S2—C4—H4C	108.3
O4—Co1—O1ⁱ	90.76 (10)	S2—C4—H4D	108.3
O4ⁱ—Co1—O1	90.76 (10)	C5—C4—S2	115.9 (2)
O4ⁱ—Co1—O1ⁱ	89.24 (10)	C5—C4—H4C	108.3
O4—Co1—O1	89.24 (10)	C5—C4—H4D	108.3
O4—Co1—O3	90.83 (9)	H4C—C4—H4D	107.4
O4—Co1—O3ⁱ	89.17 (9)	S1—C2—S2	126.18 (18)
O4ⁱ—Co1—O3	89.17 (9)	N2—C2—S2	120.0 (2)
O4ⁱ—Co1—O3ⁱ	90.83 (9)	N2—C2—S1	113.7 (3)
O4—Co1—O4ⁱ	180.00 (11)	N1—C1—S1	113.4 (3)
C2—S2—C4	102.60 (15)	N1—C1—C3	123.7 (3)
C2—S1—C1	87.22 (15)	C3—C1—S1	122.8 (2)
C5—O1—Co1	125.90 (19)	C1—C3—H3C	109.5
Co1—O3—H3A	123 (3)	C1—C3—H3D	109.5
Co1—O3—H3B	103 (3)	C1—C3—H3E	109.5
H3A—O3—H3B	109 (4)	H3C—C3—H3D	109.5
Co1—O4—H4A	122.5	H3C—C3—H3E	109.5
Co1—O4—H4B	130.3	H3D—C3—H3E	109.5
H4A—O4—H4B	104.5

Co1—O1—C5—O2	−6.9 (4)	C4—S2—C2—S1	−8.8 (3)
Co1—O1—C5—C4	171.97 (18)	C4—S2—C2—N2	176.0 (3)
O1—C5—C4—S2	−178.0 (2)	C2—S2—C4—C5	−73.2 (2)
O2—C5—C4—S2	0.9 (4)	C2—S1—C1—N1	0.1 (3)
N2—N1—C1—S1	0.4 (4)	C2—S1—C1—C3	−177.7 (3)
N2—N1—C1—C3	178.3 (3)	C2—N2—N1—C1	−1.0 (5)
N1—N2—C2—S2	176.8 (2)	C1—S1—C2—S2	−176.1 (2)
N1—N2—C2—S1	1.1 (4)	C1—S1—C2—N2	−0.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2	0.87 (2)	1.91 (3)	2.700 (3)	151 (5)
C4—H4C···S1	0.97	2.79	3.181 (3)	105
O4—H4A···N2ⁱⁱ	0.85	1.95	2.764 (4)	160
O4—H4B···O1ⁱⁱⁱ	0.85	1.91	2.757 (3)	172
O3—H3A···N1ⁱⁱ	0.84 (5)	2.17 (5)	2.979 (4)	162 (5)

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

Global reactivity indices top

E SOMO (eV)	-6.64
E LUMO (eV)	-2.39
ΔE	4.25
I	6.64
A	2.39
χ	4.515
η	2.125
µ	-4.515
S	0.235
ω	0.235

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