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Volume 69 
Part 7 
Pages i42-i43  
July 2013  

Received 14 June 2013
Accepted 25 June 2013
Online 29 June 2013

Key indicators
Powder X-ray study
T = 293 K
Mean [sigma](O-N) = 0.020 Å
R = 0.064
wR = 0.073
Data-to-parameter ratio = 19.8
Details
Open access

Tetraammine(carbonato-[kappa]2O,O')cobalt(III) nitrate: a powder X-ray diffraction study

aUniversité du Maine, Institut des Molécules et des Matériaux du Mans, CNRS UMR 6283, 72085 Le Mans, France
Correspondence e-mail: armel.le_bail@univ-lemans.fr

Practical chemistry courses at universities very frequently propose the synthesis and characterization of [Co(CO3)(NH3)4]NO3, but this goal is never achieved since students only obtain the hemihydrated form. The anhydrous form can be prepared, however, and its structure is presented here. Similar to the hemihydrate form, the anhydrous phase contains the CoIII ion in an octahedral O2N4 coordination by a chelating carbonate group and four ammine ligands. The structure reveals an intricate array of N-H...O hydrogen bonds involving both the chelating and the non-chelating O atoms of the carbonate ligand as hydrogen-bond acceptors of the amine H atoms, which are also involved in hydrogen-bonding interactions with the nitrate O atoms. The structure of the anhydrous form is close to that of the hemihydrate phase, suggesting a probable topotactic reaction with relatively small rotations and translations of the [Co(CO3)(NH3)4]+ and NO3- groups during the dehydration process, which produces an unusual volume increase of 4.3%.

Related literature

For the crystal structure of the hemihydrate, see: Bernal & Cetrullo (1990[Bernal, I. & Cetrullo, J. (1990). Struct. Chem. 1, 227-234.]); Junk & Steed (1999[Junk, P. C. & Steed, J. W. (1999). Polyhedron, 18, 3593-3597.]); Christensen & Hazell (1999[Christensen, A. N. & Hazell, R. G. (1999). Acta Chem. Scand. 53, 399-402.]). For the synthesis of the hemihydrate, see: Schlessinger (1960[Schlessinger, G. (1960). Inorg. Synth. 6, 173-175.]). For powder diffraction indexing figures of merit, see: de Wolff (1968[Wolff, P. M. de (1968). J. Appl. Cryst. 1, 108-113.]); Smith & Snyder (1979[Smith, G. S. & Snyder, R. L. (1979). J. Appl. Cryst. 12, 60-65.]). For profile refinement by the Le Bail method, see: Le Bail (2005[Le Bail, A. (2005). Powder Diffr. 20, 316-326.]). For preferred orientation correction, see: Dollase (1986[Dollase, W. A. (1986). J. Appl. Cryst. 19, 267-272.]).

Experimental

Crystal data
  • [Co(CO3)(NH3)4]NO3

  • Mr = 249.09

  • Monoclinic, P 21 /c

  • a = 7.8520 (6) Å

  • b = 6.7922 (5) Å

  • c = 17.5394 (9) Å

  • [beta] = 95.440 (3)°

  • V = 931.21 (11) Å3

  • Z = 4

  • Cu K[alpha] radiation, [lambda] = 1.5418 Å

  • T = 293 K

  • flat sheet, 8 × 8 mm

Data collection
  • Siemens D500 diffractometer

  • Specimen mounting: packed on the holder

  • Data collection mode: reflection

  • Scan method: step

  • 2[theta]min = 6.001°, 2[theta]max = 79.961°, 2[theta]step = 0.020°

Refinement
  • Rp = 0.054

  • Rwp = 0.072

  • Rexp = 0.025

  • RBragg = 0.030

  • R(F) = 0.026

  • [chi]2 = 8.123

  • 3751 data points

  • 114 parameters

  • 55 restraints

  • H atoms treated by a mixture of independent and constrained refinement

Table 1
Selected bond lengths (Å)

Co1-O1 1.928 (8)
Co1-O2 1.913 (9)
Co1-N1 2.004 (8)
Co1-N2 1.953 (9)
Co1-N3 1.953 (9)
Co1-N4 2.012 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N1-H1...O4i 0.952 (10) 2.476 (15) 3.392 (16) 161.3 (11)
N1-H2...O4ii 0.949 (14) 2.481 (16) 3.218 (13) 134.5 (11)
N2-H4...O3iii 0.962 (13) 2.400 (15) 3.261 (13) 148.8 (12)
N2-H5...O3iv 0.962 (11) 2.190 (15) 3.021 (12) 144.0 (12)
N2-H6...O4ii 0.962 (10) 2.511 (16) 3.331 (13) 143.1 (11)
N3-H7...O3iv 0.957 (13) 2.448 (15) 3.278 (13) 145.0 (11)
N3-H8...O6v 0.963 (13) 2.151 (17) 2.762 (16) 120.0 (12)
N3-H8...O2vi 0.963 (13) 2.496 (17) 3.184 (12) 128.3 (10)
N3-H9...O5 0.969 (10) 2.102 (14) 3.047 (14) 164.4 (13)
N4-H10...O3iv 0.946 (10) 2.180 (11) 3.069 (12) 156.1 (12)
N4-H11...O1iii 0.948 (13) 1.993 (12) 2.911 (10) 162.5 (12)
N4-H12...O2vi 0.955 (13) 2.231 (11) 3.059 (10) 144.5 (11)
Symmetry codes: (i) x, y+1, z; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) -x+1, -y+1, -z+1; (iv) x, y-1, z; (v) [-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (vi) -x+2, -y+1, -z+1.

Data collection: DIFFRAC-AT (Siemens & Socabim, 1993[Siemens & Socabim (1993). DIFFRAC-AT. Siemens Analytical X-ray Instruments, Inc., Madison, Wisconsin, USA, and Socabim SA, Paris, France.]); cell refinement: McMaille (Le Bail, 2004[Le Bail, A. (2004). Powder Diffr. 19, 249-254.]); data reduction: DIFFRAC-AT; program(s) used to solve structure: ESPOIR (Le Bail, 2001[Le Bail, A. (2001). Mater. Sci. Forum, 378, 65-70.]); program(s) used to refine structure: FULLPROF (Rodriguez-Carvajal, 1993[Rodriguez-Carvajal, J. (1993). Physica B, 192, 55-69.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: VN2075 ).


Acknowledgements

The author thanks J. H. Zhu and H. X. Wu for the synthesis of the hemihydrate phase and A. M. Mercier for the TGA and DSC experiments.

References

Bernal, I. & Cetrullo, J. (1990). Struct. Chem. 1, 227-234.  [CrossRef] [ChemPort]
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Christensen, A. N. & Hazell, R. G. (1999). Acta Chem. Scand. 53, 399-402.  [CrossRef] [ChemPort]
Dollase, W. A. (1986). J. Appl. Cryst. 19, 267-272.  [CrossRef] [ChemPort] [Web of Science] [IUCr Journals]
Junk, P. C. & Steed, J. W. (1999). Polyhedron, 18, 3593-3597.  [CrossRef] [ChemPort]
Le Bail, A. (2001). Mater. Sci. Forum, 378, 65-70.  [CrossRef]
Le Bail, A. (2004). Powder Diffr. 19, 249-254.  [Web of Science] [CrossRef] [ChemPort]
Le Bail, A. (2005). Powder Diffr. 20, 316-326.  [Web of Science] [CrossRef] [ChemPort]
Rodriguez-Carvajal, J. (1993). Physica B, 192, 55-69.  [CrossRef] [ChemPort]
Schlessinger, G. (1960). Inorg. Synth. 6, 173-175.  [CrossRef] [ChemPort]
Siemens & Socabim (1993). DIFFRAC-AT. Siemens Analytical X-ray Instruments, Inc., Madison, Wisconsin, USA, and Socabim SA, Paris, France.
Smith, G. S. & Snyder, R. L. (1979). J. Appl. Cryst. 12, 60-65.  [CrossRef] [ChemPort] [IUCr Journals] [Web of Science]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Wolff, P. M. de (1968). J. Appl. Cryst. 1, 108-113.  [CrossRef] [IUCr Journals] [Web of Science]


Acta Cryst (2013). E69, i42-i43   [ doi:10.1107/S1600536813017522 ]

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