Structures and electronic properties of cobalt(II) selone coordination com­plexes

Purcell, S.M.; Reinheimer, E.W.; Ritch, J.S.

doi:10.1107/S2053229625010101

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 81| Part 12| December 2025| Pages 718-722

https://doi.org/10.1107/S2053229625010101

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Structures and electronic properties of cobalt(II) selone coordination complexes

Shaydel M. Purcell,^a Eric W. Reinheimer ^b and Jamie S. Ritch ^a ^*

^aDepartment of Chemistry, The University of Winnipeg, 515 Portage Ave, Winnipeg, MB R3B 2E9, Canada, and ^bRigaku Americas, The Woodlands, Texas 77381, USA
^*Correspondence e-mail: [email protected]

Edited by W. Lewis, University of Sydney, Australia (Received 9 October 2025; accepted 12 November 2025; online 26 November 2025)

The structural chemistry of selenourea ligands is quite diverse, though examples of their coordination to cobalt are rare. In this study, the solid-state structures of the selenourea 1,3-diethylimidazole-2-selone, C₇H₁₂N₂Se, and the cobalt complexes dichloridobis(1,3-diethylimidazole-2-selone-κSe)cobalt(II), [CoCl₂(C₇H₁₂N₂Se)₂] (1), and dichloridobis(1,3-diisopropylimidazole-2-selone-κSe)cobalt(II), [CoCl₂(C₉H₁₆N₂Se)₂] (2), are presented. Two crystallization methods for the coordination complexes are utilized. The structures of complexes 1 and 2 are compared with the few existing examples in the literature, revealing a similar trend for terminal binding modes, rather than bridging modes which are often seen for late d-block metal complexes. Density functional theory calculations reveal a trend in cobalt–selenium bond strengths for 1,3-dialkyl-substituted imidazole-2-selones of Me ≃ Et < ⁱPr.

Keywords: selenourea ligand; cobalt(II) complex; coordination chemistry; crystal structure; density functional theory; thermochemistry.

CCDC references: 2502265; 2502264; 2502263

1. Introduction

Cyclic selenoureas have a diverse and expansive coordination chemistry, serving as monodentate Se-centred ligands which can adopt terminal or bridging binding modes toward a variety of metals. The structural chemistry of late d-block metals, such as gold, copper and palladium, are particularly well-explored (Ritch, 2019 ). By contrast, examples of structurally-characterized first-row transition-metal complexes, such as those of cobalt, are much rarer. Early work on cobalt(II) selenourea chemistry involved IR and electronic spectral characterization on a series of thio- and selenourea complexes of cobalt(II) halides (Devillanova et al., 1981 ), though no solid-state structures were presented. Since that study, only two examples of cyclic selenourea cobalt(II) complexes have been structurally characterized (Williams et al., 1997 ; Jia et al., 2008 ).

Cobalt coordination complexes are of increasing importance in the homogeneous catalysis of organic transformations (Li et al., 2021 ), as a replacement for those based on rarer and more expensive second- and third-row metals. Also seeing rapid development are solid-state cobalt selenide phases with applications including electrocatalysis of water-splitting reactions (Zhang et al., 2019 ). In this context, fundamental studies of the coordination chemistry of cobalt towards selenium-centred ligands will help increase our understanding of structure–activity relationships and aid in the rational design of new molecules and materials. In this study, the crystal structures of one selenourea ligand and two cobalt(II) selenourea coordination complexes are reported (Scheme 1). Structural comparisons to reported examples are presented, along with a computational analysis of ligand binding strengths and the conformational energetics of the complexes.

2. Experimental

Syntheses were performed using standard techniques without any special precautions to exclude air or moisture. The reagents 1,3-diethylimidazolium iodide, 1,3-diethylimidazole-2-selone (deise) and 1,3-diisopropylimidazole-2-selone (diise) were made by modifications of a literature procedure (Williams et al., 1993 ). 1,3-Diisopropylimidazolium chloride was prepared via the reported procedure of Schaub & Radius (2005 ). Other reagents and solvents were purchased from commercial sources and used as received. NMR spectra were recorded on a Bruker Avance III 400 MHz NMR spectrometer.

2.1. Computational details

Geometry optimizations and frequency calculations were performed with the ORCA software package (Version 6.1.0; Neese, 2025 ) using the ωB97M-V functional (Mardirossian & Head-Gordon, 2016 ) and the def2-TZVP basis set (Weigend & Ahlrichs, 2005 ), with no symmetry constraints. Final single-point energies were computed at the wB97M-V/def2-QZVPP level. All calculations are gas phase, with no solvent corrections, and thermochemistry values are given for conditions of 298.15 K and 1 atm. Open-shell Co^II species were modelled using the unrestricted Kohn–Sham formalism with a quartet ground state. Relaxed potential energy scans were performed by optimizing the structures with the desired torsion angle constrained to values incremented from 0 to 180° in 10° steps. Natural atomic charges were evaluated using the NBO7 software package (Glendening et al., 2018 ).

2.2. Synthesis and crystallization

2.2.1. Synthesis of deise

1,3-Diethylimidazolium iodide (3.479 g, 13.8 mmol), Se (2.7516 g, 34.8 mmol), K₂CO₃ (3.8150 g, 27.6 mmol) and methanol (40 ml) were added to a 250 ml round-bottomed flask, which was equipped with a reflux condenser and heated to reflux for 21 h. After cooling to room temperature, the volatiles were removed using a rotary evaporator. Dichloromethane (30 ml) was added and the mixture was filtered through a medium-porosity fritted funnel. The filtrate was concentrated on a rotary evaporator to remove most of the solvent and the resulting pale-yellow liquid was left to crystallize at −25 °C. The remaining liquid was decanted and the solid was dried in air, affording a colourless crystalline product (yield: 1.3765 g, 6.8 mmol, 49%). NMR spectral data matched those reported in the literature. X-ray-quality crystals were selected from the as-prepared product.

2.2.2. Synthesis of diise

To a 100 ml round-bottomed flask equipped with a stirrer bar was added 1,3-diisopropylimidazolium chloride (251.2 mg, 1.33 mmol), Se (104.9 mg, 1.33 mmol), K₂CO₃ (223.1 mg, 1.61 mmol) and acetonitrile (50 ml). A reflux condenser was attached and the mixture was heated to reflux for 17 h. After cooling to room temperature, the volatiles were removed using a rotary evaporator. The resulting mixture was extracted with CH₂Cl₂ (25 ml) and filtered through a medium-porosity fritted funnel to afford a clear yellow solution. Removing the volatiles under vacuum and recrystallization from methanol at −25 °C afforded the product as colourless crystals (yield: 87.14 mg, 0.38 mmol, 28%). NMR spectral data matched those reported in the literature.

2.2.3. Synthesis of [CoCl₂(deise)] (1)

CoCl₂·6H₂O (204.6 mg, 0.50 mmol) was dissolved in triethyl orthoformate (2.5 ml) in a 10 ml round-bottomed flask. In a beaker, deise (204.6 mg, 1.0 mmol) was dissolved in triethyl orthoformate (2 ml) and dichloromethane (1 ml) with stirring, then added to the cobalt chloride solution. Immediate formation of a green suspension was observed. After stirring for 1 h, the product was isolated by vacuum filtration into a medium-porosity fritted funnel, washed with Et₂O (2 × 3 ml) and dried under suction. The procedure yielded a green fine powder. X-ray-quality crystals were obtained by slow evaporation of a methanol solution of the complex at room temperature.

2.2.4. Synthesis of [CoCl₂(diise)] (2)

The complex was prepared according to the method used for the preparation of the 1,3-dimethylimidazole-2-selone (dmise) analogue (Williams et al., 1997). CoCl₂·6H₂O (45.0 mg, 0.19 mmol), diise (86.5 mg, 0.37 mmol) and methanol (15 ml) were added to a 50 ml round-bottomed flask and the resulting solution concentrated by boiling until green in colour. Cooling afforded green crystals and a yellow solution. Decanting the liquid, then washing the solid with isopropanol (2 × 5 ml) and CHCl₃ (2 × 3 ml) afforded the product as green X-ray-quality crystals.

2.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions and refined according to a riding model [C—H = 0.97 Å and U_iso(H) = 1.5U_eq(C) for tetrahedral carbon centres; C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for trigonal planar carbon centres]. The structure of deise features disorder of one ethyl group. This was modelled as an anisotropic mixture of the terminal C atom over two positions in a 80:20 occupancy, as refined by a free variable. The two partially overlapping C-atom positions were additionally restrained to have similar U^ij components.

Table 1
Experimental details

For all structures: Z = 4. Experiments were carried out with Mo Kα radiation. H-atom parameters were constrained.

	deise	1	2
Crystal data
Chemical formula	C₇H₁₂N₂Se	[CoCl₂(C₇H₁₂N₂Se)₂]	[CoCl₂(C₉H₁₆N₂Se)₂]
M_r	203.15	536.12	592.22
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c	Monoclinic, P2₁/n
Temperature (K)	293	293	302
a, b, c (Å)	6.8733 (4), 14.6494 (9), 9.0726 (5)	12.9700 (6), 12.1282 (6), 13.5313 (6)	10.1594 (2), 15.7281 (4), 15.8120 (4)
β (°)	94.493 (6)	92.715 (4)	91.000 (1)
V (Å³)	910.71 (9)	2126.12 (17)	2526.18 (10)
μ (mm⁻¹)	4.06	4.49	3.78
Crystal size (mm)	0.32 × 0.29 × 0.27	0.36 × 0.27 × 0.1	0.20 × 0.08 × 0.05

Data collection
Diffractometer	Rigaku XtaLAB Mini II	Rigaku XtaLAB Mini II	Bruker D8 QUEST ECO
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2025 )	Analytical (CrysAlis PRO; Rigaku OD, 2025)	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.623, 0.685	0.420, 0.754	0.630, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	5662, 1627, 1134	15089, 3747, 2710	61212, 5165, 3994
R_int	0.024	0.032	0.038
(sin θ/λ)_max (Å⁻¹)	0.598	0.595	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.074, 1.03	0.036, 0.070, 1.01	0.033, 0.084, 1.04
No. of reflections	1627	3747	5165
No. of parameters	104	212	252
No. of restraints	6	0	0
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.41	1.07, −0.78	0.64, −0.33
Computer programs: CrysAlis PRO (Rigaku OD, 2025), SAINT (Bruker, 2016), APEX3 (Bruker, 2016), SHELXT2014 and SHELXT2018 (Sheldrick, 2015a ), SHELXL2016 and SHELXL2018 (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

3. Results and discussion

The selenourea ligands diese and diise were used in this investigation. Preparations of both have been reported previously. Diese was prepared from the imidazolium bromide salt via deprotonation in the presence of elemental Se with either (i) K[N(SiMe₃)₂] at low temperature in tetrahydrofuran (THF; Barnett et al., 2021 ) or (ii) Na₂CO₃ in refluxing water (Huang et al., 2021 ). Diise was prepared in a similar manner from selenium and the imidazolium tetrafluoroborate salt and KO^tBu in THF at room temperature (van Weerdenburg et al., 2015 ) or from the bromide salt and Na[N(SiMe₃)₂] in THF at low temperature (Verlinden et al., 2015 ). We have found that both deise and diise can be prepared in a simpler protocol similar to that reported for the synthesis of dmise (Williams et al., 1993) using Se and K₂CO₃ and 1,3-diiethylimidazolium iodide or 1,3-diisopropylimidazolium chloride in refluxing solvent (methanol for deise and acetonitrile for diise). These reactions can be performed in air without any special precautions to exclude moisture.

While the ligand diise has been structurally characterized (van Weerdenburg et al., 2015), deise has not. The as-prepared crystals of deise were of X-ray quality and were determined to form in the space group P2₁/n. A displacement ellipsoid plot of deise is shown in Fig. 1. The C=Se bond length of 1.835 (4) Å is not significantly different from the reported distances for dmise and diise. The ethyl groups are in a syn conformation, presumably to increase packing efficiency. Other metrical parameters are also unremarkable and there are no significant intermolecular interactions.

Figure 1
Displacement ellipsoid plot (50% probability level) of deise. Atom C5A is one part of a two-part anisotropic disorder model; the minor component has been omitted for clarity.

The pseudotetrahedral Co^II complex of dmise, i.e. [CoCl₂(dmise)₂], has been reported previously (Williams et al., 1997). In that study, crystals were obtained by boiling down an ethanolic solution of ligand and CoCl₂·6H₂O. A helical coordination polymer complex of 1,1′-methylenebis(3-methylimidazoline-2-selone) (mbis), also with distorted tetrahedral coordination geometry, was made as a powder from CoCl₂ and ligand in THF followed by recrystallization from CH₃CN/Et₂O (Jia et al., 2008). To date, these represent the only structurally characterized complexes of cobalt(II) with a selenourea ligand. Several octahedral Co^III complexes containing selenourea ligands, SeC(NH₂)₂, have also been reported (Rija et al., 2011 ).

We found two methods suitable for preparing cobalt(II) complexes of deise and diise. The method of Williams et al. (1997) was used for the diise complex, 2, while for the deise complex, 1, a method used for preparing an iron(II) complex of dmise was used (Stadelman et al., 2016 ). In this procedure, a solvent mixture of triethyl orthoformate and dichloromethane is used, the former also acting as an in-situ dehydrating agent. The powdered product can be filtered out of the reaction mixture. The ethyl and isopropyl complexes are stable in crystalline form under ambient conditions (stored in a vial under air) for years. They can be recrystallized from concentrated solutions of methanol, though when dissolving in this solvent they give yellow solutions which evaporate to give crystals of both the free ligand and complex, indicating methanol is competitive with the ligands for coordination to cobalt(II).

Complexes 1 and 2 both crystallize from methanol in the space groups P2₁/c and P2₁/n, respectively, and their displacement ellipsoid plots are shown in Fig. 2. Each structure features one molecule in the asymmetric unit. The Co—Se distances in both complexes are in the narrow range of 2.4622 (5)–2.4720 (7) Å, and are consistent with the distances reported for the dmise complex (Williams et al., 1997). Likewise, the C=Se bond lengths in the complexes show a slight elongation of 1–2% in complexes 1 [1.879 (4)–1.883 (4) Å] and 2 [1.873 (3)–1.874 (3) Å] versus the free ligands deise [1.835 (4) Å] and diise [1.849 (2) Å], consistent with reports for the dmise complex.

Figure 2
Displacement ellipsoid plots (50% probability level) of (a) complex 1 and (b) complex 2.

While these complexes all share a common pseudotetrahedral CoSe₂Cl₂ core, the most dramatic difference in their structures is the relative orientation of the two selenourea ligands. The complexes exhibit values of the pseudo-torsion angle τ(C=Se⋯Se=C) of 97.9 (5)° for [CoCl₂(dmise)₂], 36.8 (1)° for 1 and 144.4 (1)° for 2. Notably, complexes 1 and 2, as well as all other structurally determined cobalt–selenourea complexes, show only terminal coordination of the selenourea ligand, with no bridging μ-Se interactions. Selenourea complexes of late d-block metals, including Cu^I, Ag^I and Pd^II have shown bridging in their solid-state structures via μ₂-Se or μ₂-halide motifs (Ritch, 2019).

Geometry optimizations of dmise, deise and diise, as well as their CoCl₂L₂ complexes, were conducted at the ωB97M-V/def2-TZVP level of theory. The free ligands show a trend of slightly increasing C=Se bond length as the size of the alkyl chain increases, spanning a 1% difference from dmise to diise (dmise: 1.828 Å; deise: 1.836 Å; diise: 1.847 Å). This trend is not reflected in the experimental values, which are all equal within error due to the size of the standard uncertainties. Considering the two resonance forms of selenourea ligands (Fig. 3), the computed distances indicate that more electron-releasing alkyl groups slightly favour the C—Se resonance structure, where there is less p(Se)→p(C) donation and hence less π bonding between these atoms. This is corroborated in the energies of the Se(p)-type highest occupied molecular orbitals (HOMOs), which increase in energy for R = Me (−7.314 eV) > R = Et (−7.264) > R = ⁱPr (−7.186). Additionally, the atomic charges on the Se atoms obtained through natural population analysis show the trend R = Me (−0.31) < R = Et (−0.33) < R = ⁱPr (−0.34).

Figure 3
Resonance contributors to the structure of cyclic selenoureas.

To compare the ability of selenoureas to donate to a high-spin Co^II centre versus a more common phosphorus-centred ligand, their putative metathetical reactions with [CoCl₂(PPh₃)₂] to form [CoCl₂(L)₂] products [Equation (1)] were modelled at the ωB97M-V/def2-QZVPP level of theory. Gas-phase thermochemistry of the reactions is summarized in Table 2. The standard enthalpies of reaction for R = Me and Et are similar, being slightly exothermic, while R = ⁱPr shows a significantly more exothermic reaction. Since there is very little geometric distortion of any of the ligands upon coordination or dissociation, the ΔH° values are explained by the selenoureas forming stronger bonds to Co^II than triphenylphosphine, particularly the isopropyl-substituted variant. This is in keeping with the HOMO energies and indicates that for Co^II the isopropyl selenourea is a significantly more strongly donating ligand than the smaller alkyl chain variants or even PPh₃. The selenourea diise is thus expected to be a competent ligand for other low-valent transition metals.

Table 2
Thermochemical calculations for Equation (1)

Ligand L	ΔH° (kJ mol⁻¹)	ΔS° (J mol⁻¹ K⁻¹)	ΔG° (kJ mol⁻¹)
dmise	−6.5	27.6	−14.8
deise	−5.4	24.2	−12.7
diise	−65.1	23.8	−72.2

[CoCl₂(PPh₃)₂] + 2L → [CoCl₂(L)₂] + 2 PPh₃ (1)

Given the wide range of τ(C=Se⋯Se=C) angles observed in the structures of CoCl₂(L)₂, conformational analyses were conducted on each complex by a relaxed potential energy surface scan of this angle from 0–180° (i.e. from synplanar to antiplanar). Very similar results were seen in each case (Fig. 4), with a potential energy minimum around 70–90° and an overall range in energies of ca 20–23 kJ mol⁻¹, indicating a shallow potential energy surface about this angle. The differing conformers observed in the crystal structures are therefore not surprising and can be rationalized by varying packing forces in each case. In solution, a mixture of conformers can be reasonably expected.

Figure 4
Conformation energy diagram for cobalt(II) complexes of selenoureas (dmise: R = Me; deise: R = Et; diise: R = ⁱPr).

The structures presented herein provide rare new examples of cobalt(II) coordination complexes of selenoureas. They exhibit conformational flexibility, as well as long-term stability in the solid state, though in polar protic solvents the complexes are labile. The alkyl-substituted selenourea ligands dmise, deise and diise are computed to have a stronger interaction with Co^II than PPh₃, particularly the isopropyl variant. This knowledge will be utilized in the design of future ligand iterations aimed at preparing complexes with increased solution-state stability.

Supporting information

CCDC references: 2502265; 2502264; 2502263

Crystal structure: contains datablocks deise, 1, 2, global. DOI: https://doi.org/10.1107/S2053229625010101/wv3022sup1.cif

Structure factors: contains datablock deise. DOI: https://doi.org/10.1107/S2053229625010101/wv3022deisesup2.hkl

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2053229625010101/wv30221sup3.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2053229625010101/wv30222sup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229625010101/wv3022deisesup5.cml

Atomic coordinates and energies of all DFT-computed structures (.xyz format). DOI: https://doi.org/10.1107/S2053229625010101/wv3022sup6.txt

Computing details top

1,3-Diethylimidazole-2-selone (deise) top

Crystal data top

C₇H₁₂N₂Se	F(000) = 408
M_r = 203.15	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.8733 (4) Å	Cell parameters from 2191 reflections
b = 14.6494 (9) Å	θ = 2.6–22.1°
c = 9.0726 (5) Å	µ = 4.06 mm⁻¹
β = 94.493 (6)°	T = 293 K
V = 910.71 (9) Å³	Block, yellow
Z = 4	0.32 × 0.29 × 0.27 mm

Data collection top

Rigaku XtaLAB Mini II diffractometer	1134 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.024
ω scans	θ_max = 25.1°, θ_min = 2.7°
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2025)	h = −8→8
T_min = 0.623, T_max = 0.685	k = −17→17
5662 measured reflections	l = −10→10
1627 independent reflections

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0212P)² + 0.7775P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1627 reflections	Δρ_max = 0.38 e Å⁻³
104 parameters	Δρ_min = −0.41 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Se1	0.19846 (6)	0.42606 (3)	0.16905 (5)	0.06847 (18)
N1	0.5951 (4)	0.40778 (19)	0.2864 (3)	0.0534 (7)
N2	0.4314 (5)	0.2856 (2)	0.3194 (3)	0.0593 (8)
C1	0.4150 (5)	0.3711 (2)	0.2611 (3)	0.0495 (9)
C2	0.7199 (6)	0.3470 (3)	0.3602 (4)	0.0717 (11)
H2	0.850856	0.356713	0.389861	0.086*
C3	0.6177 (7)	0.2715 (3)	0.3812 (4)	0.0720 (12)
H3	0.664147	0.218737	0.429064	0.086*
C4	0.6527 (6)	0.4988 (3)	0.2382 (4)	0.0682 (11)
H4BC	0.783159	0.495590	0.204739	0.082*	0.800 (19)
H4BD	0.564734	0.517887	0.155099	0.082*	0.800 (19)
H4AA	0.536607	0.533928	0.208332	0.082*	0.200 (19)
H4AB	0.728666	0.492830	0.153018	0.082*	0.200 (19)
C6	0.2740 (7)	0.2174 (3)	0.3158 (4)	0.0828 (14)
H6A	0.323703	0.159393	0.283256	0.099*
H6B	0.169480	0.236210	0.244201	0.099*
C7	0.1939 (6)	0.2046 (3)	0.4615 (4)	0.0823 (13)
H7A	0.091909	0.159707	0.452907	0.124*
H7B	0.141967	0.261490	0.493525	0.124*
H7C	0.295821	0.184461	0.532399	0.124*
C5B	0.777 (7)	0.552 (2)	0.364 (3)	0.091 (3)	0.200 (19)
H5BA	0.697596	0.562732	0.445058	0.137*	0.200 (19)
H5BB	0.819795	0.608631	0.326427	0.137*	0.200 (19)
H5BC	0.887696	0.515398	0.398017	0.137*	0.200 (19)
C5A	0.650 (2)	0.5667 (5)	0.3549 (7)	0.091 (3)	0.800 (19)
H5AA	0.519124	0.573797	0.383089	0.137*	0.800 (19)
H5AB	0.695870	0.624058	0.319744	0.137*	0.800 (19)
H5AC	0.733278	0.547233	0.438887	0.137*	0.800 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0636 (3)	0.0690 (3)	0.0719 (3)	−0.0015 (2)	−0.00044 (19)	−0.0007 (2)
N1	0.0591 (18)	0.0470 (19)	0.0551 (18)	−0.0006 (16)	0.0104 (15)	0.0075 (14)
N2	0.085 (2)	0.0421 (19)	0.0524 (18)	−0.0058 (18)	0.0134 (17)	0.0020 (15)
C1	0.065 (2)	0.042 (2)	0.0425 (19)	−0.0073 (19)	0.0133 (17)	−0.0040 (17)
C2	0.066 (3)	0.076 (3)	0.074 (3)	0.012 (3)	0.009 (2)	0.014 (2)
C3	0.094 (3)	0.058 (3)	0.065 (3)	0.020 (3)	0.013 (2)	0.015 (2)
C4	0.069 (2)	0.066 (3)	0.070 (3)	−0.012 (2)	0.012 (2)	0.012 (2)
C6	0.130 (4)	0.049 (2)	0.071 (3)	−0.034 (3)	0.014 (3)	−0.006 (2)
C7	0.092 (3)	0.081 (3)	0.074 (3)	−0.028 (3)	0.006 (2)	0.009 (2)
C5B	0.136 (8)	0.059 (4)	0.079 (4)	−0.010 (6)	0.005 (6)	−0.003 (4)
C5A	0.136 (8)	0.059 (4)	0.078 (3)	−0.010 (5)	0.006 (5)	−0.003 (3)

Geometric parameters (Å, º) top

Se1—C1	1.835 (4)	C4—C5B	1.57 (3)
N1—C1	1.352 (4)	C4—C5A	1.454 (7)
N1—C2	1.374 (4)	C6—H6A	0.9700
N1—C4	1.468 (4)	C6—H6B	0.9700
N2—C1	1.360 (4)	C6—C7	1.483 (5)
N2—C3	1.373 (5)	C7—H7A	0.9600
N2—C6	1.472 (5)	C7—H7B	0.9600
C2—H2	0.9300	C7—H7C	0.9600
C2—C3	1.332 (5)	C5B—H5BA	0.9600
C3—H3	0.9300	C5B—H5BB	0.9600
C4—H4BC	0.9700	C5B—H5BC	0.9600
C4—H4BD	0.9700	C5A—H5AA	0.9600
C4—H4AA	0.9700	C5A—H5AB	0.9600
C4—H4AB	0.9700	C5A—H5AC	0.9600

C1—N1—C2	110.7 (3)	C5A—C4—H4BD	109.0
C1—N1—C4	125.2 (3)	N2—C6—H6A	109.0
C2—N1—C4	124.1 (3)	N2—C6—H6B	109.0
C1—N2—C3	110.1 (3)	N2—C6—C7	112.9 (3)
C1—N2—C6	125.4 (4)	H6A—C6—H6B	107.8
C3—N2—C6	124.5 (4)	C7—C6—H6A	109.0
N1—C1—Se1	127.0 (3)	C7—C6—H6B	109.0
N1—C1—N2	104.7 (3)	C6—C7—H7A	109.5
N2—C1—Se1	128.3 (3)	C6—C7—H7B	109.5
N1—C2—H2	126.5	C6—C7—H7C	109.5
C3—C2—N1	107.0 (4)	H7A—C7—H7B	109.5
C3—C2—H2	126.5	H7A—C7—H7C	109.5
N2—C3—H3	126.2	H7B—C7—H7C	109.5
C2—C3—N2	107.5 (4)	C4—C5B—H5BA	109.5
C2—C3—H3	126.2	C4—C5B—H5BB	109.5
N1—C4—H4BC	109.0	C4—C5B—H5BC	109.5
N1—C4—H4BD	109.0	H5BA—C5B—H5BB	109.5
N1—C4—H4AA	109.2	H5BA—C5B—H5BC	109.5
N1—C4—H4AB	109.2	H5BB—C5B—H5BC	109.5
N1—C4—C5B	111.9 (12)	C4—C5A—H5AA	109.5
H4BC—C4—H4BD	107.8	C4—C5A—H5AB	109.5
H4AA—C4—H4AB	107.9	C4—C5A—H5AC	109.5
C5B—C4—H4AA	109.2	H5AA—C5A—H5AB	109.5
C5B—C4—H4AB	109.2	H5AA—C5A—H5AC	109.5
C5A—C4—N1	112.7 (4)	H5AB—C5A—H5AC	109.5
C5A—C4—H4BC	109.0

N1—C2—C3—N2	0.5 (4)	C3—N2—C1—Se1	−178.7 (3)
C1—N1—C2—C3	0.1 (4)	C3—N2—C1—N1	1.0 (4)
C1—N1—C4—C5B	135 (2)	C3—N2—C6—C7	74.4 (5)
C1—N1—C4—C5A	98.3 (7)	C4—N1—C1—Se1	−2.7 (5)
C1—N2—C3—C2	−1.0 (4)	C4—N1—C1—N2	177.6 (3)
C1—N2—C6—C7	−106.4 (4)	C4—N1—C2—C3	−178.2 (3)
C2—N1—C1—Se1	179.0 (2)	C6—N2—C1—Se1	2.0 (5)
C2—N1—C1—N2	−0.7 (4)	C6—N2—C1—N1	−178.3 (3)
C2—N1—C4—C5B	−47 (2)	C6—N2—C3—C2	178.4 (3)
C2—N1—C4—C5A	−83.6 (7)

Dichloridobis(1,3-diethylimidazole-2-selone-κSe)cobalt(II) (1) top

Crystal data top

[CoCl₂(C₇H₁₂N₂Se)₂]	F(000) = 1060
M_r = 536.12	D_x = 1.675 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.9700 (6) Å	Cell parameters from 4729 reflections
b = 12.1282 (6) Å	θ = 2.3–24.8°
c = 13.5313 (6) Å	µ = 4.49 mm⁻¹
β = 92.715 (4)°	T = 293 K
V = 2126.12 (17) Å³	Plate, clear black
Z = 4	0.36 × 0.27 × 0.1 mm

Data collection top

Rigaku XtaLAB Mini II diffractometer	2710 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.032
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2025)	h = −15→15
T_min = 0.420, T_max = 0.754	k = −12→14
15089 measured reflections	l = −15→16
3747 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0169P)² + 3.2994P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3747 reflections	Δρ_max = 1.07 e Å⁻³
212 parameters	Δρ_min = −0.78 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Se1	0.64817 (4)	0.32279 (4)	0.25123 (3)	0.05347 (14)
Se2	0.87553 (3)	0.47554 (3)	0.36399 (3)	0.05112 (14)
Co1	0.74116 (4)	0.49858 (4)	0.23054 (4)	0.04501 (16)
Cl1	0.80321 (9)	0.49522 (10)	0.07687 (8)	0.0627 (3)
Cl2	0.64714 (10)	0.65086 (10)	0.25290 (10)	0.0760 (4)
N1	0.4775 (3)	0.3905 (3)	0.1205 (2)	0.0490 (9)
N2	0.5827 (3)	0.2834 (3)	0.0480 (2)	0.0479 (9)
N3	1.0054 (3)	0.6637 (3)	0.3287 (3)	0.0550 (9)
N4	0.8831 (3)	0.7036 (3)	0.4255 (2)	0.0466 (9)
C1	0.5649 (3)	0.3326 (3)	0.1341 (3)	0.0430 (10)
C2	0.4395 (3)	0.3767 (4)	0.0242 (3)	0.0561 (12)
H2	0.379583	0.407855	−0.004118	0.067*
C3	0.5047 (3)	0.3102 (4)	−0.0206 (3)	0.0569 (12)
H3	0.498654	0.286376	−0.085942	0.068*
C4	0.4295 (4)	0.4546 (5)	0.1987 (4)	0.0807 (17)
H4A	0.443199	0.417435	0.261357	0.097*
H4B	0.462656	0.526276	0.203098	0.097*
C5	0.3212 (4)	0.4710 (5)	0.1852 (4)	0.105 (2)
H5A	0.306708	0.512528	0.125782	0.157*
H5B	0.296538	0.510643	0.240754	0.157*
H5C	0.287210	0.400747	0.179995	0.157*
C6	0.6668 (4)	0.2065 (4)	0.0300 (3)	0.0727 (15)
H6A	0.722638	0.217753	0.079207	0.087*
H6B	0.693204	0.220854	−0.034640	0.087*
C7	0.6306 (5)	0.0905 (5)	0.0345 (5)	0.119 (2)
H7A	0.579032	0.077768	−0.017501	0.178*
H7B	0.601663	0.077174	0.097336	0.178*
H7C	0.687833	0.041596	0.026423	0.178*
C8	0.9230 (3)	0.6222 (3)	0.3718 (3)	0.0416 (10)
C9	1.0164 (4)	0.7729 (4)	0.3550 (4)	0.0708 (14)
H9	1.066997	0.820925	0.334417	0.085*
C10	0.9414 (4)	0.7972 (4)	0.4152 (3)	0.0638 (13)
H10	0.930435	0.865103	0.444921	0.077*
C11	1.0746 (4)	0.6044 (4)	0.2644 (4)	0.0799 (16)
H11A	1.145086	0.613449	0.290419	0.096*
H11B	1.058335	0.526379	0.266460	0.096*
C12	1.0684 (5)	0.6407 (5)	0.1620 (4)	0.0956 (19)
H12A	1.120892	0.604467	0.126248	0.143*
H12B	1.078483	0.719023	0.159409	0.143*
H12C	1.001713	0.622540	0.132656	0.143*
C13	0.7941 (3)	0.6954 (4)	0.4874 (3)	0.0616 (13)
H13A	0.745517	0.642513	0.458169	0.074*
H13B	0.759830	0.766397	0.488909	0.074*
C14	0.8231 (4)	0.6608 (5)	0.5904 (4)	0.0938 (19)
H14A	0.856704	0.590326	0.589472	0.141*
H14B	0.762087	0.655474	0.627675	0.141*
H14C	0.869123	0.714285	0.620641	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0616 (3)	0.0612 (3)	0.0367 (2)	−0.0156 (2)	−0.0074 (2)	0.0031 (2)
Se2	0.0520 (3)	0.0387 (2)	0.0611 (3)	−0.0006 (2)	−0.0130 (2)	−0.0023 (2)
Co1	0.0438 (3)	0.0442 (3)	0.0463 (3)	0.0000 (3)	−0.0044 (2)	−0.0044 (3)
Cl1	0.0659 (8)	0.0681 (8)	0.0548 (7)	0.0093 (6)	0.0102 (6)	0.0140 (6)
Cl2	0.0764 (9)	0.0624 (8)	0.0866 (9)	0.0244 (7)	−0.0225 (7)	−0.0205 (7)
N1	0.039 (2)	0.057 (2)	0.051 (2)	−0.0001 (18)	0.0001 (16)	−0.0159 (18)
N2	0.047 (2)	0.057 (2)	0.0387 (19)	0.0093 (18)	−0.0040 (16)	−0.0098 (17)
N3	0.053 (2)	0.053 (2)	0.060 (2)	−0.0045 (19)	0.0113 (19)	0.003 (2)
N4	0.054 (2)	0.042 (2)	0.044 (2)	−0.0025 (18)	0.0040 (17)	−0.0059 (17)
C1	0.041 (3)	0.051 (3)	0.036 (2)	−0.006 (2)	0.0021 (18)	−0.001 (2)
C2	0.042 (3)	0.062 (3)	0.063 (3)	0.004 (2)	−0.013 (2)	−0.007 (3)
C3	0.054 (3)	0.072 (3)	0.044 (3)	0.008 (2)	−0.014 (2)	−0.008 (2)
C4	0.052 (3)	0.102 (4)	0.089 (4)	0.010 (3)	0.006 (3)	−0.049 (3)
C5	0.072 (4)	0.148 (6)	0.095 (4)	0.028 (4)	0.015 (3)	−0.036 (4)
C6	0.070 (3)	0.094 (4)	0.052 (3)	0.034 (3)	−0.010 (2)	−0.021 (3)
C7	0.168 (7)	0.081 (5)	0.110 (5)	0.048 (5)	0.029 (5)	0.008 (4)
C8	0.041 (2)	0.041 (2)	0.042 (2)	0.000 (2)	−0.0073 (19)	−0.004 (2)
C9	0.080 (4)	0.057 (3)	0.076 (4)	−0.028 (3)	0.005 (3)	0.004 (3)
C10	0.088 (4)	0.043 (3)	0.061 (3)	−0.017 (3)	0.003 (3)	−0.006 (2)
C11	0.065 (4)	0.084 (4)	0.093 (4)	0.015 (3)	0.031 (3)	0.002 (3)
C12	0.121 (5)	0.104 (5)	0.062 (4)	0.031 (4)	0.013 (3)	−0.002 (3)
C13	0.060 (3)	0.055 (3)	0.071 (3)	0.008 (2)	0.012 (3)	−0.010 (3)
C14	0.103 (5)	0.117 (5)	0.062 (3)	−0.021 (4)	0.019 (3)	0.009 (3)

Geometric parameters (Å, º) top

Se1—Co1	2.4720 (7)	C5—H5A	0.9600
Se1—C1	1.879 (4)	C5—H5B	0.9600
Se2—Co1	2.4653 (7)	C5—H5C	0.9600
Se2—C8	1.883 (4)	C6—H6A	0.9700
Co1—Cl1	2.2654 (12)	C6—H6B	0.9700
Co1—Cl2	2.2415 (13)	C6—C7	1.485 (7)
N1—C1	1.338 (5)	C7—H7A	0.9600
N1—C2	1.381 (5)	C7—H7B	0.9600
N1—C4	1.475 (5)	C7—H7C	0.9600
N2—C1	1.339 (5)	C9—H9	0.9300
N2—C3	1.380 (5)	C9—C10	1.331 (6)
N2—C6	1.465 (5)	C10—H10	0.9300
N3—C8	1.340 (5)	C11—H11A	0.9700
N3—C9	1.377 (5)	C11—H11B	0.9700
N3—C11	1.468 (5)	C11—C12	1.452 (6)
N4—C8	1.344 (5)	C12—H12A	0.9600
N4—C10	1.375 (5)	C12—H12B	0.9600
N4—C13	1.462 (5)	C12—H12C	0.9600
C2—H2	0.9300	C13—H13A	0.9700
C2—C3	1.335 (6)	C13—H13B	0.9700
C3—H3	0.9300	C13—C14	1.487 (6)
C4—H4A	0.9700	C14—H14A	0.9600
C4—H4B	0.9700	C14—H14B	0.9600
C4—C5	1.422 (6)	C14—H14C	0.9600

C1—Se1—Co1	96.54 (12)	N2—C6—C7	111.0 (5)
C8—Se2—Co1	98.72 (11)	H6A—C6—H6B	108.0
Se2—Co1—Se1	98.69 (2)	C7—C6—H6A	109.4
Cl1—Co1—Se1	106.55 (4)	C7—C6—H6B	109.4
Cl1—Co1—Se2	113.63 (4)	C6—C7—H7A	109.5
Cl2—Co1—Se1	115.08 (4)	C6—C7—H7B	109.5
Cl2—Co1—Se2	111.39 (4)	C6—C7—H7C	109.5
Cl2—Co1—Cl1	110.97 (5)	H7A—C7—H7B	109.5
C1—N1—C2	109.2 (3)	H7A—C7—H7C	109.5
C1—N1—C4	124.2 (4)	H7B—C7—H7C	109.5
C2—N1—C4	126.6 (4)	N3—C8—Se2	126.6 (3)
C1—N2—C3	109.2 (3)	N3—C8—N4	107.1 (3)
C1—N2—C6	126.2 (3)	N4—C8—Se2	126.2 (3)
C3—N2—C6	124.5 (3)	N3—C9—H9	126.2
C8—N3—C9	108.9 (4)	C10—C9—N3	107.6 (4)
C8—N3—C11	126.6 (4)	C10—C9—H9	126.2
C9—N3—C11	124.5 (4)	N4—C10—H10	126.3
C8—N4—C10	109.0 (4)	C9—C10—N4	107.4 (4)
C8—N4—C13	126.5 (4)	C9—C10—H10	126.3
C10—N4—C13	124.5 (4)	N3—C11—H11A	108.7
N1—C1—Se1	126.8 (3)	N3—C11—H11B	108.7
N1—C1—N2	107.1 (3)	H11A—C11—H11B	107.6
N2—C1—Se1	126.1 (3)	C12—C11—N3	114.2 (4)
N1—C2—H2	126.4	C12—C11—H11A	108.7
C3—C2—N1	107.2 (4)	C12—C11—H11B	108.7
C3—C2—H2	126.4	C11—C12—H12A	109.5
N2—C3—H3	126.4	C11—C12—H12B	109.5
C2—C3—N2	107.3 (4)	C11—C12—H12C	109.5
C2—C3—H3	126.4	H12A—C12—H12B	109.5
N1—C4—H4A	108.4	H12A—C12—H12C	109.5
N1—C4—H4B	108.4	H12B—C12—H12C	109.5
H4A—C4—H4B	107.5	N4—C13—H13A	109.1
C5—C4—N1	115.5 (4)	N4—C13—H13B	109.1
C5—C4—H4A	108.4	N4—C13—C14	112.7 (4)
C5—C4—H4B	108.4	H13A—C13—H13B	107.8
C4—C5—H5A	109.5	C14—C13—H13A	109.1
C4—C5—H5B	109.5	C14—C13—H13B	109.1
C4—C5—H5C	109.5	C13—C14—H14A	109.5
H5A—C5—H5B	109.5	C13—C14—H14B	109.5
H5A—C5—H5C	109.5	C13—C14—H14C	109.5
H5B—C5—H5C	109.5	H14A—C14—H14B	109.5
N2—C6—H6A	109.4	H14A—C14—H14C	109.5
N2—C6—H6B	109.4	H14B—C14—H14C	109.5

Co1—Se1—C1—N1	−81.2 (4)	C6—N2—C1—Se1	4.4 (6)
Co1—Se1—C1—N2	98.1 (3)	C6—N2—C1—N1	−176.2 (4)
Co1—Se2—C8—N3	−97.2 (3)	C6—N2—C3—C2	176.1 (4)
Co1—Se2—C8—N4	86.2 (3)	C8—N3—C9—C10	0.9 (5)
N1—C2—C3—N2	−0.1 (5)	C8—N3—C11—C12	112.0 (5)
N3—C9—C10—N4	−0.7 (5)	C8—N4—C10—C9	0.2 (5)
C1—N1—C2—C3	−0.2 (5)	C8—N4—C13—C14	88.8 (5)
C1—N1—C4—C5	−154.5 (5)	C9—N3—C8—Se2	−177.9 (3)
C1—N2—C3—C2	0.4 (5)	C9—N3—C8—N4	−0.8 (5)
C1—N2—C6—C7	98.2 (5)	C9—N3—C11—C12	−68.4 (7)
C2—N1—C1—Se1	179.9 (3)	C10—N4—C8—Se2	177.5 (3)
C2—N1—C1—N2	0.4 (5)	C10—N4—C8—N3	0.3 (5)
C2—N1—C4—C5	23.0 (8)	C10—N4—C13—C14	−89.5 (5)
C3—N2—C1—Se1	−179.9 (3)	C11—N3—C8—Se2	1.7 (6)
C3—N2—C1—N1	−0.5 (5)	C11—N3—C8—N4	178.8 (4)
C3—N2—C6—C7	−76.8 (6)	C11—N3—C9—C10	−178.7 (4)
C4—N1—C1—Se1	−2.2 (6)	C13—N4—C8—Se2	−1.0 (6)
C4—N1—C1—N2	178.3 (4)	C13—N4—C8—N3	−178.2 (4)
C4—N1—C2—C3	−178.0 (4)	C13—N4—C10—C9	178.8 (4)

Dichloridobis(1,3-diisopropylimidazole-2-selone-κSe)cobalt(II) (2) top

Crystal data top

[CoCl₂(C₉H₁₆N₂Se)₂]	F(000) = 1188
M_r = 592.22	D_x = 1.557 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.1594 (2) Å	Cell parameters from 9597 reflections
b = 15.7281 (4) Å	θ = 2.6–25.1°
c = 15.8120 (4) Å	µ = 3.78 mm⁻¹
β = 91.000 (1)°	T = 302 K
V = 2526.18 (10) Å³	Block, clear green
Z = 4	0.20 × 0.08 × 0.05 mm

Data collection top

Bruker D8 QUEST ECO diffractometer	5165 independent reflections
Graphite monochromator	3994 reflections with I > 2σ(I)
Detector resolution: 7.391 pixels mm^-1	R_int = 0.038
φ and ω scans	θ_max = 26.4°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −12→12
T_min = 0.630, T_max = 0.746	k = −19→19
61212 measured reflections	l = −19→19

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0431P)² + 1.2037P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
5165 reflections	Δρ_max = 0.64 e Å⁻³
252 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Se1	0.49689 (3)	0.60942 (2)	0.42899 (2)	0.04739 (10)
Se2	0.56221 (3)	0.83625 (2)	0.33077 (2)	0.05913 (12)
Co1	0.43903 (4)	0.70301 (3)	0.30889 (2)	0.04266 (12)
Cl1	0.21918 (7)	0.72163 (6)	0.30370 (6)	0.0606 (2)
Cl2	0.52060 (9)	0.64938 (7)	0.18903 (5)	0.0722 (3)
N3	0.7258 (2)	0.82717 (17)	0.48080 (15)	0.0479 (6)
N2	0.4366 (2)	0.46173 (16)	0.32603 (15)	0.0443 (6)
N1	0.6447 (2)	0.47637 (16)	0.35023 (15)	0.0483 (6)
N4	0.5201 (2)	0.83627 (16)	0.51072 (16)	0.0482 (6)
C10	0.6043 (3)	0.83196 (17)	0.44647 (18)	0.0415 (6)
C1	0.5273 (3)	0.51150 (18)	0.36469 (17)	0.0407 (6)
C14	0.8504 (3)	0.8176 (2)	0.4339 (2)	0.0588 (9)
H14	0.829055	0.812021	0.373515	0.071*
C3	0.4989 (3)	0.3952 (2)	0.2873 (2)	0.0546 (8)
H3	0.458511	0.351831	0.256403	0.065*
C5	0.7735 (3)	0.5108 (2)	0.3785 (2)	0.0633 (10)
H5	0.756686	0.556243	0.419342	0.076*
C2	0.6278 (3)	0.4040 (2)	0.3022 (2)	0.0603 (9)
H2	0.693854	0.367947	0.283626	0.072*
C11	0.7178 (3)	0.8284 (2)	0.56727 (19)	0.0566 (8)
H11	0.787986	0.825807	0.605735	0.068*
C8	0.2927 (3)	0.4757 (2)	0.3233 (2)	0.0573 (8)
H8	0.273475	0.529112	0.352563	0.069*
C12	0.5907 (3)	0.8340 (2)	0.5859 (2)	0.0591 (9)
H12	0.555897	0.835987	0.639878	0.071*
C13	0.9361 (4)	0.8947 (2)	0.4467 (3)	0.0783 (11)
H13A	0.892959	0.943569	0.422647	0.117*
H13B	1.018709	0.885972	0.419430	0.117*
H13C	0.951307	0.903737	0.506095	0.117*
C17	0.3750 (3)	0.8453 (2)	0.5028 (2)	0.0588 (9)
H17	0.349407	0.832007	0.444221	0.071*
C4	0.8429 (4)	0.5496 (3)	0.3050 (3)	0.0899 (14)
H4A	0.856564	0.507024	0.262586	0.135*
H4B	0.926418	0.571850	0.323852	0.135*
H4C	0.790252	0.594803	0.281625	0.135*
C9	0.2259 (3)	0.4042 (3)	0.3690 (2)	0.0777 (11)
H9A	0.241686	0.351688	0.339937	0.117*
H9B	0.132874	0.414824	0.370329	0.117*
H9C	0.260432	0.400533	0.425728	0.117*
C6	0.8517 (4)	0.4424 (3)	0.4237 (3)	0.0939 (14)
H6A	0.801078	0.420016	0.469363	0.141*
H6B	0.932215	0.466182	0.445856	0.141*
H6C	0.871417	0.397587	0.384770	0.141*
C15	0.9208 (4)	0.7371 (3)	0.4635 (3)	0.0868 (13)
H15A	0.993763	0.725916	0.427377	0.130*
H15B	0.860680	0.690078	0.461233	0.130*
H15C	0.952446	0.744698	0.520594	0.130*
C7	0.2468 (4)	0.4838 (3)	0.2318 (3)	0.0836 (13)
H7A	0.295362	0.528192	0.204759	0.125*
H7B	0.154603	0.497286	0.229786	0.125*
H7C	0.261272	0.430991	0.202958	0.125*
C18	0.3076 (4)	0.7829 (3)	0.5593 (3)	0.0911 (14)
H18A	0.340916	0.726796	0.548973	0.137*
H18B	0.214513	0.783982	0.547755	0.137*
H18C	0.324163	0.797971	0.617353	0.137*
C16	0.3358 (4)	0.9362 (3)	0.5201 (4)	0.1051 (17)
H16A	0.362045	0.951250	0.576801	0.158*
H16B	0.242084	0.941862	0.513783	0.158*
H16C	0.378407	0.973214	0.480850	0.158*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0572 (2)	0.04962 (18)	0.03503 (17)	0.00957 (14)	−0.00817 (13)	−0.00374 (13)
Se2	0.0584 (2)	0.0724 (2)	0.04602 (19)	−0.02501 (17)	−0.01580 (15)	0.01839 (16)
Co1	0.0353 (2)	0.0560 (2)	0.0364 (2)	−0.00119 (17)	−0.00691 (16)	0.00249 (17)
Cl1	0.0375 (4)	0.0739 (5)	0.0701 (6)	0.0050 (4)	−0.0084 (4)	0.0064 (4)
Cl2	0.0558 (5)	0.1205 (8)	0.0402 (4)	0.0033 (5)	−0.0004 (4)	−0.0102 (5)
N3	0.0364 (13)	0.0657 (16)	0.0413 (14)	−0.0039 (11)	−0.0055 (11)	−0.0036 (12)
N2	0.0356 (13)	0.0536 (14)	0.0436 (14)	0.0019 (11)	−0.0049 (10)	−0.0050 (11)
N1	0.0332 (13)	0.0634 (16)	0.0484 (15)	−0.0015 (11)	0.0001 (11)	−0.0175 (12)
N4	0.0389 (13)	0.0555 (15)	0.0500 (15)	−0.0005 (11)	−0.0054 (11)	−0.0043 (12)
C10	0.0372 (15)	0.0461 (16)	0.0411 (16)	−0.0057 (12)	−0.0061 (13)	0.0028 (13)
C1	0.0404 (16)	0.0510 (16)	0.0307 (14)	−0.0003 (13)	−0.0024 (12)	0.0000 (12)
C14	0.0428 (18)	0.086 (2)	0.0478 (19)	−0.0083 (17)	−0.0014 (14)	−0.0079 (17)
C3	0.0472 (18)	0.0581 (19)	0.058 (2)	−0.0037 (15)	−0.0051 (15)	−0.0195 (16)
C5	0.0370 (17)	0.083 (2)	0.069 (2)	−0.0063 (17)	−0.0016 (16)	−0.032 (2)
C2	0.0472 (19)	0.069 (2)	0.065 (2)	0.0057 (16)	0.0003 (16)	−0.0299 (18)
C11	0.0482 (19)	0.080 (2)	0.0409 (18)	0.0030 (16)	−0.0111 (14)	−0.0076 (16)
C8	0.0369 (16)	0.062 (2)	0.072 (2)	0.0047 (15)	−0.0083 (15)	−0.0116 (17)
C12	0.055 (2)	0.082 (2)	0.0401 (18)	−0.0008 (17)	−0.0014 (15)	−0.0087 (16)
C13	0.065 (2)	0.081 (3)	0.089 (3)	−0.020 (2)	0.013 (2)	0.002 (2)
C17	0.0375 (17)	0.065 (2)	0.074 (2)	0.0019 (15)	−0.0019 (16)	−0.0130 (18)
C4	0.064 (2)	0.093 (3)	0.113 (4)	−0.025 (2)	0.020 (2)	−0.025 (3)
C9	0.049 (2)	0.110 (3)	0.074 (3)	−0.008 (2)	0.0094 (19)	0.004 (2)
C6	0.046 (2)	0.135 (4)	0.100 (3)	0.000 (2)	−0.025 (2)	−0.015 (3)
C15	0.064 (3)	0.081 (3)	0.116 (4)	0.006 (2)	0.024 (2)	−0.014 (3)
C7	0.063 (2)	0.095 (3)	0.092 (3)	−0.008 (2)	−0.038 (2)	0.018 (2)
C18	0.053 (2)	0.094 (3)	0.126 (4)	−0.003 (2)	0.024 (2)	0.001 (3)
C16	0.060 (2)	0.073 (3)	0.182 (5)	0.016 (2)	−0.015 (3)	−0.019 (3)

Geometric parameters (Å, º) top

Se1—Co1	2.4657 (5)	C8—C9	1.505 (5)
Se1—C1	1.874 (3)	C8—C7	1.517 (5)
Se2—Co1	2.4622 (5)	C12—H12	0.9300
Se2—C10	1.873 (3)	C13—H13A	0.9600
Co1—Cl1	2.2528 (8)	C13—H13B	0.9600
Co1—Cl2	2.2461 (9)	C13—H13C	0.9600
N3—C10	1.342 (3)	C17—H17	0.9800
N3—C14	1.485 (4)	C17—C18	1.501 (5)
N3—C11	1.371 (4)	C17—C16	1.511 (5)
N2—C1	1.347 (3)	C4—H4A	0.9600
N2—C3	1.372 (4)	C4—H4B	0.9600
N2—C8	1.479 (4)	C4—H4C	0.9600
N1—C1	1.338 (4)	C9—H9A	0.9600
N1—C5	1.478 (4)	C9—H9B	0.9600
N1—C2	1.378 (4)	C9—H9C	0.9600
N4—C10	1.341 (4)	C6—H6A	0.9600
N4—C12	1.378 (4)	C6—H6B	0.9600
N4—C17	1.484 (4)	C6—H6C	0.9600
C14—H14	0.9800	C15—H15A	0.9600
C14—C13	1.505 (5)	C15—H15B	0.9600
C14—C15	1.523 (5)	C15—H15C	0.9600
C3—H3	0.9300	C7—H7A	0.9600
C3—C2	1.334 (4)	C7—H7B	0.9600
C5—H5	0.9800	C7—H7C	0.9600
C5—C4	1.499 (5)	C18—H18A	0.9600
C5—C6	1.510 (6)	C18—H18B	0.9600
C2—H2	0.9300	C18—H18C	0.9600
C11—H11	0.9300	C16—H16A	0.9600
C11—C12	1.332 (4)	C16—H16B	0.9600
C8—H8	0.9800	C16—H16C	0.9600

C1—Se1—Co1	96.44 (8)	C11—C12—H12	126.2
C10—Se2—Co1	102.32 (8)	C14—C13—H13A	109.5
Se2—Co1—Se1	106.627 (17)	C14—C13—H13B	109.5
Cl1—Co1—Se1	109.18 (3)	C14—C13—H13C	109.5
Cl1—Co1—Se2	113.30 (3)	H13A—C13—H13B	109.5
Cl2—Co1—Se1	109.83 (3)	H13A—C13—H13C	109.5
Cl2—Co1—Se2	104.13 (3)	H13B—C13—H13C	109.5
Cl2—Co1—Cl1	113.47 (4)	N4—C17—H17	107.9
C10—N3—C14	126.1 (2)	N4—C17—C18	110.5 (3)
C10—N3—C11	109.4 (2)	N4—C17—C16	109.9 (3)
C11—N3—C14	124.4 (2)	C18—C17—H17	107.9
C1—N2—C3	109.2 (2)	C18—C17—C16	112.7 (3)
C1—N2—C8	126.5 (3)	C16—C17—H17	107.9
C3—N2—C8	124.3 (2)	C5—C4—H4A	109.5
C1—N1—C5	125.7 (3)	C5—C4—H4B	109.5
C1—N1—C2	109.4 (2)	C5—C4—H4C	109.5
C2—N1—C5	124.8 (3)	H4A—C4—H4B	109.5
C10—N4—C12	108.9 (2)	H4A—C4—H4C	109.5
C10—N4—C17	125.9 (3)	H4B—C4—H4C	109.5
C12—N4—C17	125.2 (3)	C8—C9—H9A	109.5
N3—C10—Se2	126.1 (2)	C8—C9—H9B	109.5
N4—C10—Se2	126.9 (2)	C8—C9—H9C	109.5
N4—C10—N3	106.9 (2)	H9A—C9—H9B	109.5
N2—C1—Se1	127.3 (2)	H9A—C9—H9C	109.5
N1—C1—Se1	126.0 (2)	H9B—C9—H9C	109.5
N1—C1—N2	106.7 (2)	C5—C6—H6A	109.5
N3—C14—H14	108.7	C5—C6—H6B	109.5
N3—C14—C13	110.3 (3)	C5—C6—H6C	109.5
N3—C14—C15	109.3 (3)	H6A—C6—H6B	109.5
C13—C14—H14	108.7	H6A—C6—H6C	109.5
C13—C14—C15	111.1 (3)	H6B—C6—H6C	109.5
C15—C14—H14	108.7	C14—C15—H15A	109.5
N2—C3—H3	126.2	C14—C15—H15B	109.5
C2—C3—N2	107.5 (3)	C14—C15—H15C	109.5
C2—C3—H3	126.2	H15A—C15—H15B	109.5
N1—C5—H5	107.7	H15A—C15—H15C	109.5
N1—C5—C4	109.9 (3)	H15B—C15—H15C	109.5
N1—C5—C6	109.7 (3)	C8—C7—H7A	109.5
C4—C5—H5	107.7	C8—C7—H7B	109.5
C4—C5—C6	114.0 (3)	C8—C7—H7C	109.5
C6—C5—H5	107.7	H7A—C7—H7B	109.5
N1—C2—H2	126.4	H7A—C7—H7C	109.5
C3—C2—N1	107.2 (3)	H7B—C7—H7C	109.5
C3—C2—H2	126.4	C17—C18—H18A	109.5
N3—C11—H11	126.4	C17—C18—H18B	109.5
C12—C11—N3	107.2 (3)	C17—C18—H18C	109.5
C12—C11—H11	126.4	H18A—C18—H18B	109.5
N2—C8—H8	108.6	H18A—C18—H18C	109.5
N2—C8—C9	109.2 (3)	H18B—C18—H18C	109.5
N2—C8—C7	109.1 (3)	C17—C16—H16A	109.5
C9—C8—H8	108.6	C17—C16—H16B	109.5
C9—C8—C7	112.7 (3)	C17—C16—H16C	109.5
C7—C8—H8	108.6	H16A—C16—H16B	109.5
N4—C12—H12	126.2	H16A—C16—H16C	109.5
C11—C12—N4	107.6 (3)	H16B—C16—H16C	109.5

Co1—Se1—C1—N2	−73.7 (2)	C3—N2—C8—C9	65.3 (4)
Co1—Se1—C1—N1	108.1 (2)	C3—N2—C8—C7	−58.3 (4)
Co1—Se2—C10—N3	115.9 (2)	C5—N1—C1—Se1	−3.5 (4)
Co1—Se2—C10—N4	−66.8 (3)	C5—N1—C1—N2	178.0 (3)
N3—C11—C12—N4	0.0 (4)	C5—N1—C2—C3	−178.0 (3)
N2—C3—C2—N1	0.0 (4)	C2—N1—C1—Se1	178.5 (2)
C10—N3—C14—C13	115.9 (3)	C2—N1—C1—N2	−0.1 (3)
C10—N3—C14—C15	−121.6 (3)	C2—N1—C5—C4	72.7 (4)
C10—N3—C11—C12	0.0 (4)	C2—N1—C5—C6	−53.4 (5)
C10—N4—C12—C11	0.1 (4)	C11—N3—C10—Se2	177.8 (2)
C10—N4—C17—C18	132.9 (3)	C11—N3—C10—N4	0.1 (3)
C10—N4—C17—C16	−102.1 (4)	C11—N3—C14—C13	−67.5 (4)
C1—N2—C3—C2	0.0 (4)	C11—N3—C14—C15	55.1 (4)
C1—N2—C8—C9	−115.9 (3)	C8—N2—C1—Se1	2.6 (4)
C1—N2—C8—C7	120.5 (3)	C8—N2—C1—N1	−179.0 (3)
C1—N1—C5—C4	−105.1 (4)	C8—N2—C3—C2	179.0 (3)
C1—N1—C5—C6	128.9 (3)	C12—N4—C10—Se2	−177.8 (2)
C1—N1—C2—C3	0.1 (4)	C12—N4—C10—N3	−0.1 (3)
C14—N3—C10—Se2	−5.1 (4)	C12—N4—C17—C18	−49.5 (4)
C14—N3—C10—N4	177.2 (3)	C12—N4—C17—C16	75.5 (5)
C14—N3—C11—C12	−177.2 (3)	C17—N4—C10—Se2	0.1 (4)
C3—N2—C1—Se1	−178.5 (2)	C17—N4—C10—N3	177.8 (3)
C3—N2—C1—N1	0.0 (3)	C17—N4—C12—C11	−177.8 (3)

Thermochemical calculations for Equation 1. top

Ligand L	ΔH° (kJ mol^-1)	ΔS° (J mol^-1 K^-1)	ΔG° (kJ mol^-1)
dmise	-6.5	27.6	-14.8
deise	-5.4	24.2	-12.7
diise	-65.1	23.8	-72.2

Acknowledgements

We thank the Digital Research Alliance of Canada for access to computing resources.

Funding information

Funding for this research was provided by: The University of Winnipeg; Natural Sciences and Engineering Research Council of Canada (grant No. RGPIN-2019-06725); Canada Foundation for Innovation (grant No. 42109); Research Manitoba.

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

Structures and electronic properties of cobalt(II) selone coordination com­plexes

1. Introduction

2. Experimental

2.1. Computational details

2.2. Synthesis and crystallization

2.2.1. Synthesis of deise

2.2.2. Synthesis of diise

2.2.3. Synthesis of [CoCl2(deise)] (1)

2.2.4. Synthesis of [CoCl2(diise)] (2)

2.3. Refinement

3. Results and discussion

Supporting information

Acknowledgements

Funding information

References

research papers

Structures and electronic properties of cobalt(II) selone coordination complexes

2.2.3. Synthesis of [CoCl₂(deise)] (1)

2.2.4. Synthesis of [CoCl₂(diise)] (2)