Redetermination of cis-bis­(ethyl­ene­diamine-κ2N,N′)bis­(nitrito-κN)cobalt(III) (ethyl­enediamine-κ2N,N′)tetra­kis­(nitrito-κN)cobaltate(III) monohydrate

Burrow, R.A.; Vicenti, J.R.M.

doi:10.1107/S1600536812050325

Volume 69
Part 1
Pages m56-m57
January 2013

Received 19 November 2012
Accepted 10 December 2012
Online 15 December 2012

Key indicators
Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R = 0.035
wR = 0.087
Data-to-parameter ratio = 18.5
Details

Redetermination of cis-bis(ethylenediamine-²N,N')bis(nitrito-N)cobalt(III) (ethylenediamine-²N,N')tetrakis(nitrito-N)cobaltate(III) monohydrate

Robert A. Burrow ^a ^* and Juliano R. de Menezes Vicenti ^a

^aLaboratório de Materiais Inorgânicos, Universidade Federal de Santa Maria, 97105-900 Santa Maria, RS, Brazil
Correspondence e-mail: rburrow@ewald.base.ufsm.br

The structure of the title compound, [Co(NO₂)₂(NH₂CH₂CH₂NH₂)₂][Co(NO₂)₄(NH₂CH₂CH₂NH₂)]·H₂O, was redetermined with a modern CCD-equipped diffractometer. In comparison with the original determination based on photographic data [Kushi et al. (1976). Inorg. Nucl. Chem. Lett. 12, 629-633], the current study allows the location of reliable postions for the H atoms and thus leads to better understanding of the interionic and intermolecular interactions. The crystal structure consists of an octahedrally coordinated cationic Co^III complex ion, an octahedrally coordinated anionic Co^III complex ion and a lattice water molecule. The complex cation, complex anion and lattice water molecule are connected by an intricate network of O-HO and N-HO hydrogen bonds, forming a three-dimensional structure.

Related literature

For background to Co^III complexes, see: Angelici (1969); Bernal (1985); Bernal & Kauffman (1987); Murmann (1955). For a previous report of the crystal structure of the title compound, see: Kushi et al. (1976). For synthetic details, see: Bailor & Rollinson (1946); Sharrock (1980). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental

Crystal data

[Co(NO₂)₂(C₂H₈N₂)₂][Co(NO₂)₄(C₂H₈N₂)]·H₂O
M_r = 592.25
Monoclinic, P 2₁ /n
a = 14.7580 (5) Å
b = 6.7060 (2) Å
c = 20.6845 (7) Å
= 96.969 (2)°
V = 2031.96 (11) Å³
Z = 4
Mo K radiation
= 1.73 mm^-1
T = 100 K
0.40 × 0.15 × 0.05 mm

Data collection

Bruker X8 Kappa APEXII diffractometer
Absorption correction: numerical (SADABS; Bruker, 2012) T_min = 0.692, T_max = 0.925
63576 measured reflections
6280 independent reflections
4801 reflections with I > 2(I)
R_int = 0.073

Refinement

R[F² > 2(F²)] = 0.035
wR(F²) = 0.087
S = 1.07
6280 reflections
340 parameters
H atoms treated by a mixture of independent and constrained refinement
_max = 0.72 e Å^-3
_min = -0.84 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N11-H11AO11ⁱ	0.83 (3)	2.26 (3)	3.048 (2)	158 (2)
N11-H11BO23ⁱⁱ	0.79 (3)	2.23 (3)	2.991 (2)	163 (2)
N11-H11BO13ⁱⁱⁱ	0.79 (3)	2.57 (2)	2.966 (2)	113 (2)
N12-H12AO24^iv	0.86 (3)	2.22 (3)	3.060 (2)	164 (2)
N12-H12BO12^v	0.80 (3)	2.38 (3)	3.030 (2)	139 (2)
N13-H13AO22^vi	0.84 (3)	2.42 (3)	3.186 (2)	152 (2)
N13-H13BO13ⁱⁱⁱ	0.87 (3)	2.47 (3)	3.206 (2)	143 (2)
N14-H14AO27ⁱⁱ	0.94 (3)	2.12 (3)	3.038 (2)	164 (2)
N14-H14BO24^iv	0.85 (2)	2.42 (2)	3.060 (2)	132 (2)
N21-H21AO28^vii	0.82 (3)	2.56 (3)	3.185 (2)	134 (2)
N22-H22AO27^viii	0.83 (2)	2.18 (3)	2.981 (2)	164 (2)
N22-H22BO1	0.89 (2)	2.16 (3)	2.967 (2)	151 (2)
O1-H1AO26^iv	0.84 (3)	2.19 (3)	2.953 (2)	152 (3)
O1-H1AO24^iv	0.84 (3)	2.53 (3)	3.081 (2)	124 (2)
O1-H1BO25^viii	0.82 (3)	2.07 (3)	2.866 (2)	162 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z; (iii) x, y-1, z; (iv) -x+1, -y+1, -z; (v) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) x+1, y, z; (vii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (viii) x, y+1, z.

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2706 ).

Acknowledgements

Financial support from the Conselho Nacional de Desenvolvimento Científico (CNPq, Brazil; grants 485245/2007-8 and 479747/2009-1), the Fundação de Amparo à Pesquisa (FAPERGS, Rio Grande do Sul; grant 10/1645-9) is gratefully acknowledged, as are fellowships from CNPq (JRMV & RAB; grant 308731/2009-3) and the Coordenação de Aperfeiçoamento de Pessoas de Nível Superior (CAPES, Brazil; JRMV). The diffractometer was funded by a CT-INFRA grant from the Financiadora de Estrutos e Projetos (FINEP, Brazil).

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.
Angelici, R. J. (1969). Synthesis and Technique in Inorganic Chemistry, Philadelphia: W. B. Saunders.
Bailor, J. C. & Rollinson, L. L. (1946). Inorg. Synth. 2, 222-225.
Bernal, I. (1985). Inorg. Chim. Acta, 96, 99-110.
Bernal, I. & Kauffman, G. B. (1987). J. Chem. Educ. 64, 604-610.
Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Kushi, Y., Kuramoto, M., Yamamoto, S. & Yoneda, H. (1976). Inorg. Nucl. Chem. Lett. 12, 629-633.
Murmann, R. K. (1955). J. Am. Chem. Soc. 77, 5190-5190.
Sharrock, P. (1980). J. Chem. Educ. 57, 778-778.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.

metal-organic compounds

Redetermination of cis-bis(ethylenediamine-2N,N')bis(nitrito-N)cobalt(III) (ethylenediamine-2N,N')tetrakis(nitrito-N)cobaltate(III) monohydrate