Tris(ethyl­enediamine)­cobalt(III) diformatodioxalatoindate(III) dihydrate

Juying Tong; Qinhe Pan

doi:10.1107/S1600536811013109

. 2011 Apr 13;67(Pt 5):m579–m580. doi: 10.1107/S1600536811013109

Tris(ethylenediamine)cobalt(III) diformatodioxalatoindate(III) dihydrate

Juying Tong ^a, Qinhe Pan ^b,^*

PMCID: PMC3089116 PMID: 21754305

Abstract

In the cation of the title compound, [Co(C₂H₈N₂)₃][In(C₂O₄)₂(CHO₂)₂]·2H₂O, the Co—N bond lengths lie in the range 1.960 (5)–1.997 (5) Å. In the anion, the In^III atom is coordinated by four O atoms from two oxalato ligands and two O atoms from two formato ligands in a distorted octahedral geometry. Intermolecular O—H⋯O and N—H⋯O hydrogen bonds form an extensive hydrogen-bonding network, which link the cations, anions and water molecules into three-dimensional structure.

Related literature

For related structures, see: Chen et al. (2005 ▶); Du et al. (2004 ▶); Pan et al. (2005 ▶, 2008 ▶, 2010a ▶,b ▶, 2011 ▶); Stalder & Wilkinson (1997 ▶); Wang et al. (2003a ▶,b ▶,c ▶, 2004 ▶); Yu et al. (2001 ▶); Zhang et al. (2003a ▶,b ▶).

Experimental

Crystal data

[Co(C₂H₈N₂)₃][In(C₂O₄)₂(CHO₂)₂]·2H₂O
M _r = 656.17
Triclinic,
a = 8.2048 (16) Å
b = 12.016 (2) Å
c = 12.052 (2) Å
α = 79.09 (3)°
β = 81.45 (3)°
γ = 88.43 (3)°
V = 1153.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 293 K
0.2 × 0.18 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 ▶) T _min = 0.686, T _max = 1
12132 measured reflections
5263 independent reflections
3963 reflections with I > 2σ(I)
R _int = 0.084

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.168
S = 1.05
5263 reflections
311 parameters
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −1.13 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013109/cv5068sup1.cif

e-67-0m579-sup1.cif^{(22KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013109/cv5068Isup2.hkl

e-67-0m579-Isup2.hkl^{(257.7KB, 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—H1A⋯O7ⁱ	0.90	2.22	3.019 (7)	148
N1—H1B⋯O6ⁱⁱ	0.90	2.25	2.981 (7)	139
N2—H2A⋯O1Wⁱⁱⁱ	0.90	2.02	2.857 (7)	155
N2—H2B⋯O4^iv	0.90	2.14	3.017 (6)	166
N3—H3A⋯O2W^v	0.90	2.23	3.017 (7)	146
N3—H3B⋯O6ⁱⁱ	0.90	2.17	3.002 (7)	154
N3—H3B⋯O8ⁱⁱ	0.90	2.50	3.153 (7)	130
N4—H4A⋯O2	0.90	2.11	2.915 (6)	148
N4—H4B⋯O10^iv	0.90	2.33	3.102 (7)	144
N4—H4B⋯O2^iv	0.90	2.53	3.166 (7)	128
N5—H5A⋯O8ⁱ	0.90	2.16	2.986 (6)	153
N5—H5B⋯O4^iv	0.90	2.27	3.022 (6)	141
N5—H5B⋯O2^iv	0.90	2.28	3.060 (6)	145
N6—H6A⋯O1	0.90	2.05	2.917 (7)	161
N6—H6B⋯O6ⁱⁱ	0.90	2.19	3.024 (7)	154
O2W—H2WA⋯O3^vi	0.55	2.36	2.889 (6)	163
O2W—H2WB⋯O12^vii	0.55	2.22	2.751 (7)	166
O1W—H1WA⋯O2W	0.80	2.03	2.821 (7)	169
O1W—H1WB⋯O4	0.80	2.09	2.836 (6)	156

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

Acknowledgments

This work was supported by the Priming Scientific Research Foundation of Hainan University (grant No. kyqd1051).

supplementary crystallographic information

Comment

Template synthesis is an important method to get new materials. One of the interesting strategies is employing chiral metal complexes as a template, because they are versatile and can be made with a wide of shapes, charges and particularly chirality. Up to now, aluminophosphates such as [d-Co(en)₃]Al₃P₄O₁₆.2H₂O (Stalder et al., 1997) and [d-Co(en)₃]AlP₂O₈.6.5H₂O (Chen et al., 2005), gallium phosphates such as [d-Co(en)₃][H₃Ga₂P₄O₁₆] (Stalder et al., 1997) and [Co(en)₃][Ga₃(H₂PO₄)₆(HPO₄)₃] (Wang et al., 2003a), zinc phosphates such as [Co(en)₃][Zn₈P₆O₂₄Cl].2H₂O (Yu et al., 2001) and [Co(dien)₂.H₃O][Zn₂(HPO₄)₄] (Wang et al., 2003b), indium phosphate [Co(en)₃][In₃(H₂PO₄)₆(HPO₄)₃].H₂O (Du et al., 2004), germanates such as [Ni(1,2-PDA)₃]₂(HOCH₂CH₂CH₂NH₃)₃(H₃O)₂[Ge₇O₁₄X₃]₃ (X = F, OH) (Pan et al., 2008) and [Ni(dien)₂]₂[GeO₇O₁₃(OH)₂F₃]Cl (Zhang et al., 2003a), and fluorogermanates such as [Ni(dien)₂][GeF₆] (Zhang et al., 2003b), [Ni(en)(TETA)][GeF₆] (Wang et al., 2004), and [Ni(en)₃][GeF₆] (Pan et al., 2005), have been reported. Also a new concept of chirality transfer of the metal complex into the inorganic host framework has been demonstrated (Wang et al., 2003c). Recently, we reported some metal oxalate using metal complex cations as template (Pan et al., 2010a,b, 2011). When formate anions were introduced to the system, the title compound (I) - a formate oxalate mixed coordinated complex - was obtained.

The crystal structure of (I) consists of a discrete [In(C₂O₄)₂(HCO₂)₂]^3- anions and [Co(en)₃]³⁺ cations (Fig. 1). The In(iii) ion is coordinated by two formate anions in a monodentate mode and two oxalate anions. The asymmetric part contains two crystalline water molecules. Intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) form an extensive hydrogen-bonding network, which link cations, anions and crystalline water molecules into three-dimensional crystal structure.

Experimental

In a typical synthesis, a mixture of In(NO₃)₃.5H₂O (1 mmol), Co(en)₃Cl₃ (0.43 mmol), K₂C₂O₄.H₂O (2 mmol) and DMF (10 ml), was added to a 20 ml Teflon-lined reactor under autogenous pressure at 120 °C for 3 days.