Tris(ethyl­enedi­amine)­cobalt(II) dichloride

Kristin Cooke; Andrei V Olenev; Kirill Kovnir

doi:10.1107/S1600536813013135

. 2013 May 18;69(Pt 6):m332. doi: 10.1107/S1600536813013135

Tris(ethylenediamine)cobalt(II) dichloride

Kristin Cooke ^a, Andrei V Olenev ^a, Kirill Kovnir ^a,^*

PMCID: PMC3684892 PMID: 23794994

Abstract

The title compound, [Co^II(C₂H₈N₂)₃]Cl₂, was obtained unexpectedly as the product of an attempted solvothermal synthesis of cobalt selenide from the elements in the presence of NH₄Cl in ethylenediamine solvent. The three chelate rings of the distorted octahedral [Co(C₂H₈N₂)₃]²⁺ complex cation adopt twisted conformations about their C—C bonds. The spread of cis-N—Co—N bond angles [80.17 (6)–98.10 (6)°] in the title compound is considerably greater than the equivalent data for [Co^III(C₂H₈N₂)₃]Cl₃ [Takamizawa et al. (2008 ▶). Angew. Chem. Int. Ed. 47, 1689–1692]. In the crystal, the components are linked by numerous N—H⋯Cl hydrogen bonds, generating a three-dimensional network in which the cationic complexes are stacked in columns along [010] and separated by columns of chloride anions.

Related literature

The corresponding Co^III–tris-ethylenediamine complex with chloride counter-anions has been reported by Takamizawa et al. (2008 ▶).

Experimental

Crystal data

[Co(C₂H₈N₂)₃]Cl₂
M _r = 310.14
Orthorhombic,
a = 8.1590 (8) Å
b = 17.047 (3) Å
c = 20.3974 (14) Å
V = 2837.0 (6) Å³
Z = 8
Cu Kα radiation
μ = 12.81 mm⁻¹
T = 90 K
0.31 × 0.17 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.109, T _max = 0.243
17930 measured reflections
2700 independent reflections
2437 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.059
S = 1.06
2700 reflections
232 parameters
All H-atom parameters refined
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(17.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813013135/hb7079sup1.cif

e-69-0m332-sup1.cif^{(17.7KB, cif)}

Click here for additional data file.^{(132.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013135/hb7079Isup2.hkl

e-69-0m332-Isup2.hkl^{(132.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Co—N1	2.1540 (15)
Co—N3	2.1558 (15)
Co—N2	2.1635 (15)
Co—N5	2.1748 (15)
Co—N4	2.1767 (15)
Co—N6	2.1791 (16)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cl2	0.82 (2)	2.48 (3)	3.2839 (17)	167 (2)
N1—H1A⋯Cl2ⁱ	0.86 (2)	2.57 (2)	3.3056 (16)	145.4 (18)
N2—H2A⋯Cl1ⁱⁱ	0.83 (2)	2.92 (2)	3.5494 (16)	133.6 (17)
N2—H2A⋯Cl2ⁱⁱⁱ	0.83 (2)	2.94 (2)	3.5887 (17)	135.8 (17)
N2—H2B⋯Cl1	0.88 (2)	2.65 (2)	3.4566 (17)	152.5 (18)
N5—H5B⋯Cl1ⁱⁱ	0.87 (2)	2.51 (2)	3.3770 (16)	173.1 (19)
N5—H5A⋯Cl1^iv	0.82 (2)	2.70 (2)	3.4514 (18)	152.4 (19)
N6—H6B⋯Cl1	0.88 (3)	2.66 (3)	3.4552 (18)	150.3 (19)
N6—H6A⋯Cl1^v	0.83 (2)	2.71 (2)	3.4653 (16)	152.9 (19)
N3—H3A⋯Cl1^iv	0.88 (2)	2.59 (2)	3.4075 (17)	154.2 (17)
N3—H3B⋯Cl2ⁱ	0.82 (2)	2.49 (2)	3.2560 (16)	156 (2)
N4—H4A⋯Cl2	0.85 (2)	2.68 (2)	3.5003 (17)	161 (2)
N4—H4B⋯Cl2ⁱⁱⁱ	0.87 (2)	2.55 (2)	3.2919 (16)	143.5 (19)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors thank the UC Davis ChemEnergy NSF REU Grant #CHE-1004925 for financial support.

supplementary crystallographic information

Comment

In the chiral Co(II)(en)₃ cationic complex (Fig. 1) N atoms form distorted octahedron around central Co atom, cis angles deviate from 90° by less than 10°. Both Λ and Δ isomers are present in equal amounts in the centrosymmetric crystal structure.

Co(en)₃ cationic complexes are stacked in columns along [010] direction (Figure 2) and separated by the columns of Cl anions. There two types of chlorine anions in the crystal structure. Cl1 has distorted octahedral coordination by 6 hydrogen atoms from 4 different Co(en)₃ complexes. Cl2 has distorted trigonal bipyramid coordination by 5 hydrogen atoms from 2 different Co(en)₃ complexes. H···Cl distances vary from 2.45 to 2.70 Å.

The corresponding Co(III) trisethylenediamine complex with chloride counter-anions has been reported. (Takamizawa et al., 2008). The Co(III)(en)₃ cationic complex is more regular: cis angles deviate from 90° by less than 4°.

Experimental

The title compound, [Co(C₂N₂H₈)₃]Cl₂, was obtained unintentionally as the product of an attempted synthesis of cobalt selenide. Co (64 mg), Se (86 mg), and NH₄Cl (100 mg) were reacted in ethylenediamine (en) solvent (30 ml). Reaction was performed in closed hydrothermal vessel at 180°C for 48 h. Degree of the vessel filling was 70%. Irregular moisture-sensitive yellow crystals of the title compound were recovered.