cis-Chlorido(methyl­amine)­bis­(propane-1,3-diamine)­cobalt(III) dichloride monohydrate

Velusamy Maheshwaran; Munisamy Manjunathan; Krishnamoorthy Anbalagan; Viswanathan Thiruselvam; Mondikalipudur Nanjappagounder Ponnuswamy

doi:10.1107/S1600536813006442

. 2013 Mar 13;69(Pt 4):m205–m206. doi: 10.1107/S1600536813006442

cis-Chlorido(methylamine)bis(propane-1,3-diamine)cobalt(III) dichloride monohydrate

Velusamy Maheshwaran ^a, Munisamy Manjunathan ^b, Krishnamoorthy Anbalagan ^b, Viswanathan Thiruselvam ^a, Mondikalipudur Nanjappagounder Ponnuswamy ^a,^*

PMCID: PMC3629484 PMID: 23634002

Abstract

In the title compound, [CoCl(CH₅N)(C₃H₁₀N₂)₂]Cl₂·H₂O, the Co^III ion has an octahedral coordination environment and is surrounded by four N atoms of two propane-1,3-diamine ligands in the equatorial plane, with another N atom of the methylamine ligand and a Cl atom occupying the axial positions. The crystal packing is stabilized by intermolecular N—H⋯O, N—H⋯Cl, and O—H⋯Cl interactions, generating a three-dimensional network.

Related literature

For the linear solvation energy relationship (LSER) method, see: Anbalagan (2011 ▶); Anbalagan et al. (2003 ▶, 2011 ▶). For the biological properties of cobalt(III) complexes, see: Chang et al. (2010 ▶). For related structures, see: Anbalagan et al. (2009 ▶); Lee et al. (2007 ▶); Ramesh et al. (2008 ▶); Ravichandran et al. (2009 ▶). For the preparation of (1,3-diaminopropane)cobalt(III), see: Bailar & Work (1946 ▶).

Experimental

Crystal data

[CoCl(CH₅N)(C₃H₁₀N₂)₂]Cl₂·H₂O
M _r = 362.62
Triclinic,
a = 7.4752 (6) Å
b = 7.9065 (6) Å
c = 14.4663 (13) Å
α = 76.022 (6)°
β = 76.907 (7)°
γ = 73.779 (4)°
V = 784.96 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 292 K
0.35 × 0.35 × 0.35 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.798, T _max = 1.000
5020 measured reflections
2764 independent reflections
2071 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.055
S = 0.92
2764 reflections
162 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Click here for additional data file.^{(19.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813006442/bt6894sup1.cif

e-69-0m205-sup1.cif^{(19.8KB, cif)}

Click here for additional data file.^{(135.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006442/bt6894Isup2.hkl

e-69-0m205-Isup2.hkl^{(135.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1	0.90	2.12	2.960 (3)	155
N1—H1D⋯Cl2	0.90	2.43	3.317 (2)	170
N2—H2C⋯Cl3ⁱ	0.90	2.57	3.462 (2)	172
N2—H2D⋯Cl3	0.90	2.44	3.3196 (19)	164
N3—H3C⋯O1	0.90	2.04	2.880 (3)	155
N3—H3D⋯Cl3	0.90	2.50	3.3041 (18)	149
N4—H4C⋯Cl3ⁱⁱ	0.90	2.65	3.486 (2)	155
N4—H4D⋯Cl2	0.90	2.45	3.348 (2)	177
N5—H5C⋯Cl3ⁱ	0.90	2.49	3.359 (2)	162
N5—H5D⋯Cl3ⁱⁱ	0.90	2.37	3.2649 (19)	172
O1—H1E⋯Cl2ⁱⁱⁱ	0.82 (4)	2.29 (4)	3.093 (3)	168 (4)
O1—H1F⋯Cl2^iv	0.87 (4)	2.25 (4)	3.112 (3)	174 (3)

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

Acknowledgments

KA is thankful to the CSIR, New Delhi (Lr. No. 01 (2570)/12/EMR-II/3.4.2012) for financial support through a major research project. The authors are thankful to Department of Chemistry, Pondicherry University, for the single-crystal XRD instrumentation facility.

supplementary crystallographic information

Comment

The interest in understanding the outer-sphere electron-transfer (OSET) reactions of transition metal complexes in mixed solvents has increased significantly in recent years. It was established that the method of linear solvation energy relationship (LSER) is a generalized treatment of solvation effects and can very well be used to understand the influence of solvent on reaction rates (Anbalagan et al., 2003). The present research is the design and synthesis of cobalt(III) complexes with an objective to understand the structure-reactivity correlation. Substituting an amino ligand for the MeNH₂ moiety can yield complexes of similar structure, but with differing electron transfer rate (Anbalagan, 2011; Anbalagan et al., 2011).

Such complexes can offer a clear correlation between structure and spectral characteristics, reactions in particular. The optical properties and mechanism of electron transfer reaction can be understood through the structure of these complexes.

In addition cobalt(III) complexes have received a sustained high level of attention due to their relevance in various redox processes in biological systems and act as promising agents for antitumor, anthelmintic, antiparasitic, antibiotics and antimicrobial activities, as well as their multiple applications in fields such as medicine and drug delivery (Chang et al.,2010). Against this background and to ascertain the molecular structure and conformation, the X-ray crystal structure determination of the title compound has been carried out.

The ORTEP plot of the molecule is shown in Fig. 1. The molecular structure is symmetric with respect to cobalt, the Co^III ion has an octahedral coordination environment and is surrounded by four N atoms in an equatorial plane, with the other N and Cl atoms occupying the axial positions. The bond lengths [Co—N] and [Co—Cl] are comparable with the values reported in the literature (Lee et al., 2007; Ramesh et al., 2008; Anbalagan et al., 2009; Ravichandran et al., 2009).

The packing of the molecules viewed down a axis is shown in Fig. 2. The molecules are stabilized by N—H···Cl, N—H···O and O—H···Cl intermolecular interactions generating a three-dimensional network.

Experimental

Two grams of trans-[CoIII(tn)₂Cl₂]Cl solid was made in to paste using 3–4 drops of water. To the solid mass, about 0.12M methyl amine (MeNH₂) was added in drops for 20 min and mixed by grinding (Bailar & Work 1946). The grinding of the resulting dull green paste was continued to obtain red mass. The reaction mixture was set aside until no further change occurred and the product was allowed to stand overnight. Finally, the solid was washed and recrystallized using acidified water pre-heated to 70°C. The pure crystals were filtered, washed with ethanol and dried over vacuum. The microcrystalline solid obtained was pink colored and the yield was estimated to be 0.85 g (85%). X-ray quality crystals were grown after repeated recrystallization and using hot acidified water.