Bis(ethyl­enediamine-κ2 N,N′)(nitrato-κ2 O,O′)cobalt(III) hydroxide nitrate

Ji-Bo Zhang; Xiao-Shu Qu

doi:10.1107/S160053680903219X

. 2009 Aug 19;65(Pt 9):m1099–m1100. doi: 10.1107/S160053680903219X

Bis(ethylenediamine-κ² N,N′)(nitrato-κ² O,O′)cobalt(III) hydroxide nitrate

Ji-Bo Zhang ^a, Xiao-Shu Qu ^b,^*

PMCID: PMC2969983 PMID: 21577449

Abstract

The Co ion in the title salt, [Co(NO₃)(H₂NCH₂CH₂NH₂)₂](OH)(NO₃), has oxidation state + III and is coordinated by four N atoms from two ethylenediamine molecules and two O atoms from a nitrate anion in a distorted octahedral geometry. The charge of the complex cation is balanced by a hydroxide anion and a nitrate anion. The cations and anions are connected by N—H⋯O and O—H⋯O hydrogen bonds, resulting in a three-dimensional supramolecular framework. There are two independent ion pairs with similar configurations in the unit cell. Both uncoordinated nitrate counter-anions are disordered.

Related literature

For diethylenediamine-chelated Co(III) complexes with Cl⁻ or SO₄ ²⁻ as the second ligand, see: Anderson et al. (1977 ▶); Niederhoffer et al. (1986 ▶); Sharma et al. (2006a ▶,b ▶,c ▶). For comparison Co—N and Co—O distances, see: Bruggemann & Thewalt (1994 ▶); Sharma et al. (2005 ▶).

Experimental

Crystal data

[Co(NO₃)(C₂H₈N₂)₂](OH)(NO₃)
M _r = 320.17
Monoclinic,
a = 9.5212 (13) Å
b = 23.163 (3) Å
c = 12.6473 (13) Å
β = 118.491 (7)°
V = 2451.4 (5) Å³
Z = 8
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 296 K
0.38 × 0.34 × 0.28 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.585, T _max = 0.660
13327 measured reflections
4801 independent reflections
3864 reflections with I > 2σ(I)
R _int = 0.080

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.116
S = 1.00
4801 reflections
379 parameters
156 restraints
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903219X/ng2611sup1.cif

e-65-m1099-sup1.cif^{(25.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903219X/ng2611Isup2.hkl

e-65-m1099-Isup2.hkl^{(235.2KB, 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
O13—H13⋯O10	0.98	1.97	2.906 (8)	158
O14—H14⋯O8	0.87	2.04	2.78 (3)	143
N1—H1A⋯O4ⁱ	0.90	2.17	3.032 (3)	160
N1—H1B⋯O5ⁱⁱ	0.90	2.19	2.995 (3)	148
N2—H2A⋯O14ⁱⁱⁱ	0.90	2.00	2.888 (4)	168
N2—H2B⋯O8^iv	0.90	2.25	3.045 (19)	148
N3—H3A⋯O6ⁱⁱ	0.90	2.10	2.986 (3)	169
N3—H3B⋯O9ⁱ	0.90	2.33	3.14 (2)	150
N4—H4A⋯O3^v	0.90	2.22	3.004 (3)	145
N4—H4B⋯O12	0.90	2.26	3.071 (14)	150
N6—H5A⋯O12ⁱ	0.90	2.10	2.973 (14)	163
N6—H5B⋯O13^vi	0.90	2.53	3.258 (4)	138
N7—H6A⋯O2^v	0.90	1.99	2.881 (3)	168
N7—H6B⋯O1	0.90	1.98	2.873 (3)	169
N8—H7A⋯O7	0.90	2.18	2.988 (7)	149
N8—H7B⋯O6^vii	0.90	2.01	2.887 (3)	163
N9—H8A⋯O11^viii	0.90	2.29	3.088 (9)	147
N9—H8A⋯O12ⁱ	0.90	2.58	3.08 (2)	115
N9—H8B⋯O3	0.90	2.19	3.065 (3)	163

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

Acknowledgments

The authors are grateful for financial support from the Jilin Province Science and Technology Development Plan (200705 C18)

supplementary crystallographic information

Comment

Recently, a lot of diethylenediamine chelated Co(III) complexes which Cl^- or SO₄^2- appeared as the second ligands have been reported (Niederhoffer et al., 1986; Anderson et al., 1977; Sharma et al., 2006a,b,c). However, nitrite coordinated diethylenediamine chelated Co(III) complexes have not been reported. In this work, a new diethylenediamine chelated Co(III) complexes coordinated by a nitrite have been synthesized, and its structure is reported here.

The structure of the cation is given in Fig. 1. There are two crystallographically independent molecules in the asymmetric unit. The two molecules are almost identical. The cation consists of cobalt(III) coordinated by four nitrogen atoms from two ethylenediamine and two oxygen atoms from one nitrite. There is also a hydroxide and a nitrite appeared as the counter ions in the crystal. The Co—N and Co—O distances are normal (Sharma et al., 2005, Bruggemann et al., 1994).

In the crystal structure of title compound, there is strongly multipoint directional hydrogen bonds interactions among the [Co(en)₂(NO₃)] ²⁺ subunit, hydroxide and nitrite anions in the range of 0.278 (3) nm-0.3424 (12) nm. Thus, the complex cations and the hydroxide and nitrite anions are connected to result in a three-dimensional supramolecular framework through O–H···O and N–H···O hydrogen-bonding interactions.

Experimental

The K₆ H₂[Nb₆O₁₉](H₂O)₁₃ oxidant (0.15 g, 0.11 mmol), Co(NO₃)₂ (0.15 g, 0.8 mmol) and 0.5 ml en in water (15 ml) was stirred for a hour at 80 °C. The resulting solution was filtered. Purple single crystals were obtained by slow evaporation of the filtrate at room temperature (yield 56% based on Co).