(Benzyl­amine)chloridobis(ethane-1,2-diamine)cobalt(III) dichloride hemihydrate

K Ravichandran; P Ramesh; M Tamilselvan; K Anbalagan; M N Ponnuswamy

doi:10.1107/S1600536809034849

. 2009 Sep 5;65(Pt 10):m1174–m1175. doi: 10.1107/S1600536809034849

(Benzylamine)chloridobis(ethane-1,2-diamine)cobalt(III) dichloride hemihydrate

K Ravichandran ^a, P Ramesh ^a, M Tamilselvan ^b, K Anbalagan ^b, M N Ponnuswamy ^a,^*

PMCID: PMC2970310 PMID: 21577710

Abstract

In the title compound, [CoCl(C₂H₈N₂)₂(C₇H₉N)]Cl₂·0.5H₂O, there are two crystallographically independent cations and anions and one water molecule in the asymmetric unit. Both Co^III ions are bonded to two chelating ethylenediamine ligands, one benzylamine molecule and one chloride ion. The crystal packing is through N—H⋯O, N—H⋯Cl and O—H⋯Cl interactions.

Related literature

For the importance of metal complexes in the fields of biological catalysis and functions, see: Gray (2003 ▶); Wohrle & Pomogailo (2003 ▶). For the biomedical applications of cobalt complexes, see: Osinsky (2004 ▶); Roth et al. (2002 ▶). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). For related structures, see: Lee et al. (2007 ▶); Ramesh et al. (2008 ▶). cis-[Co^III(en)₂(BzNH₂)Cl]Cl₂·0.5H₂O was synthesized (Bailer & Clapp, 1945 ▶) by substituting the chloride ligand with benzyl amine in trans-[Co(en)₂Cl₂]Cl (Bailer & Rollinson, 1946 ▶).

Experimental

Crystal data

[CoCl(C₂H₈N₂)₂(C₇H₉N)]Cl₂·0.5H₂O
M _r = 401.65
Monoclinic,
a = 20.9361 (9) Å
b = 7.2447 (3) Å
c = 24.4340 (9) Å
β = 106.440 (2)°
V = 3554.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.718, T _max = 0.765
40140 measured reflections
8911 independent reflections
6475 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.096
S = 1.06
8911 reflections
458 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034849/bt5046sup1.cif

e-65-m1174-sup1.cif^{(31.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034849/bt5046Isup2.hkl

e-65-m1174-Isup2.hkl^{(427.1KB, 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—H1A⋯Cl3	0.81 (3)	2.67 (3)	3.406 (2)	151 (3)
N1—H1B⋯Cl2	0.87 (3)	2.36 (3)	3.211 (2)	163 (2)
N8—H8A⋯Cl3	0.91 (3)	2.33 (3)	3.179 (2)	156 (3)
N4′—H4D⋯O1	0.81 (3)	2.25 (3)	2.915 (3)	139 (2)
N8′—H8C⋯O1	0.87 (3)	2.15 (3)	2.964 (4)	155 (3)
N1′—H1C⋯Cl3′	0.82 (3)	2.43 (4)	3.246 (2)	174 (3)
N4—H4A⋯Cl2ⁱ	0.87 (3)	2.65 (3)	3.423 (2)	149 (2)
N5′—H5D⋯Cl2′	0.85 (3)	2.39 (3)	3.233 (2)	168 (3)
N8′—H8D⋯Cl3′	0.87 (3)	2.48 (3)	3.252 (2)	148 (3)
N4—H4B⋯Cl3ⁱⁱ	0.93 (3)	2.45 (3)	3.265 (2)	147 (2)
N8—H8B⋯Cl3ⁱⁱ	0.79 (3)	2.49 (3)	3.280 (2)	176 (3)
N9—H9A⋯Cl2ⁱⁱⁱ	0.84 (4)	2.57 (4)	3.391 (2)	166 (3)
N5′—H5C⋯Cl1ⁱ	0.91 (3)	2.63 (3)	3.380 (2)	141 (2)
N1′—H1D⋯Cl2′^iv	0.89 (3)	2.49 (3)	3.288 (2)	149 (2)
N9′—H9D⋯Cl2′^iv	0.85 (3)	2.81 (3)	3.615 (2)	158 (2)
N5—H5A⋯Cl2ⁱ	0.88 (3)	2.38 (3)	3.220 (2)	159 (2)
O1—H2W⋯Cl3′ⁱ	0.842 (17)	2.27 (2)	3.092 (3)	165 (4)

Open in a new tab

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

Acknowledgments

KR thanks Dr Babu Varghese, SAIF, IIT-Madras, India, for his help with the data collection and the management of Kandaswami Kandar’s College, Velur, Namakkal, India, for their encouragement to pursue the programme.

supplementary crystallographic information

Comment

Metal complexes find importance in the fields of biological catalysis and functions, such as in metabolism (Gray, 2003; Wohrle & Pomogailo, 2003). Cobalt complexes were also found to show biomedical applications and one such example is cancer therapy (Osinsky, 2004; Roth et al., 2002). Against this background and to ascertain the molecular conformation, the structure determination of the title compound has been carried out.

There are two crystallographically independent molecules in the asymmetric unit. The Co^III ion and the four N atoms almost lie in the same plane, whereas the other N and Cl atoms are approximately perpendicular to this plane. The Co—N and Co—Cl bond lengths are comparable with the related complexes (Lee et al., 2007; Ramesh et al., 2008). In the molecule A, the two five membered rings adopt twist conformation with the puckering parameters (Cremer & Pople, 1975) and the asymmetry parameters (Nardelli, 1983) [for the ring Co1/N1/C2/C3/N4 are: q₂ = 0.416 (3) Å, φ= 90.4 (3)° and Δ2(Co1)= 0.10 (2)°; and for the ring Co1/N5/C6/C7/N8 are: q₂ = 0.445 (3) Å, φ= 90.7 (3)° and Δ2(Co1)= 1.1 (2)°]. One of the five membered rings in the molecule B adopts twist conformation, whereas the other ring adopts envelope conformation [for the ring Co1'/N1'/C2'/C3'/N4' are: q₂ =0.393 (2) Å, φ= 89.0 (3)° and Δ2(Co1')= 1.2 (2)°; and for the ring Co1'/N5'/C6'/C7'/N8' are: q₂ = 0.443 (3) Å, φ= 281.0 (3)° and Δ2(Co1')= 11.1 (1)°].

The crystal packing is controlled by N—H···O, N—H···Cl, O—H···Cl and C—H···π types of intra and intermolecular interactions. The two intra molecular N—H···O hydrogen bonds form a S(6) ring motif. The combination of N4'-H4'D···O1, N8'-H8D···Cl3' and O1—H2W···Cl3' hydrogen bonds connects the molecule into one dimensional chain running along b–axis.

Experimental

Cis-[Co^III(en)₂(BzNH₂)Cl]Cl₂.1/2 H₂O was synthesized (Bailer and Clapp, 1945), by substituting chloride ligand with benzyl amine (Bz) in trans- [Co(en)₂Cl₂]Cl (Bailer and Rollinson, 1946). Two grams of the cobalt^(III) complex was suspended in 1 ml of water in a mortar. To this a definite amount of AnalaR benzylamine was added in drops with constant grinding to obtain a paste. A rosy red color was observed and the grinding was continued for another 1 hr to obtain a homogeneous solid mass. The paste was then allowed to stand overnight in a desicator. The Bz substituted complex was recrystallized twice using acidified water, dried and preserved in a desicator. Single crystal was grown by adding the metal complex in triply distilled water acidified with HCl and kept standing at 0°C for 2–3 weeks.