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Volume 62 
Part 9 
Pages m2301-m2302  
September 2006  

Received 25 July 2006
Accepted 14 August 2006
Online 23 August 2006

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© International Union of Crystallography 2006

Key indicators
Single-crystal X-ray study
T = 150 K
Mean [sigma](C-C) = 0.003 Å
R = 0.036
wR = 0.069
Data-to-parameter ratio = 15.4
Details

Acetonitrilebis(nitrato-[kappa]2O,O')(1,10-phenanthroline)cobalt(II)

Frédéric Thébault,a Alexander J. Blake,a* Neil R. Champnessa and Martin Schrödera

aSchool of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England
Correspondence e-mail: a.j.blake@nottingham.ac.uk

In the title compound, [Co(NO3)2(C2H3N)(C12H8N2)], the cobalt(II) centre adopts a seven-coordinate distorted pentagonal-bipyramidal geometry, being coordinated by a bidentate 1,10-phenanthroline, two bidentate nitrate anions and an acetonitrile ligand. The two axial sites are occupied by the acetonitrile ligand and one N-atom donor from the phenanthroline. The major distortions from ideal geometry occur within the equatorial plane, and are due to the narrow bite angle of the bidentate nitrate anions.

Comment

The field of coordination frameworks and their potential applications have been increasingly growing over the last few decades (Braga et al., 2005[Braga, D., Brammer, L. & Champness, N. R. (2005). CrystEngComm, 7, 1-19.]; Champness et al., 2006[Champness, N. R. (2006). Dalton Trans. pp. 877-880.]). Our studies have led us to investigate a variety of transition metal(II) nitrate salts in combination with soft N-donor ligands (Barnett et al., 2001[Barnett, S. A., Blake, A. J., Champness, N. R., Nicolson, J. E. B. & Wilson, C. (2001). J. Chem. Soc. Dalton Trans. pp. 567-573.]; Barnett et al., 2003a[Barnett, S. A. & Champness, N. R. (2003a). Coord. Chem. Rev. 246, 145-168.],b[Barnett, S. A., Blake, A. J., Champness, N. R. & Wilson, C. (2003b). Dalton Trans. pp. 2387-2394.]; Blake et al., 2000[Blake, A. J., Champness, N. R., Khlobystov, A. N., Parsons, S. & Schröder, M. (2000). Angew. Chem. Int. Ed. 39, 2317-2320.]; Khlobystov et al., 2003[Khlobystov, A. N., Brett, M. T., Blake, A. J., Champness, N. R., Gill, P. M. W., O'Neill, D. P., Teat, S. J., Wilson, C. & Schröder, M. (2003). J. Am. Chem. Soc. 125, 6753-6761.]). During our investigations, we have encountered the title compound, (I), as a by-product from an attempt to prepare a coordination polymer with the ligand 4,4'-(1,4-phenylene)bis(3,6-dipyridin-2-ylpyridazine). Thus, a new crystal structure containing the widely studied 1,10-phenanthroline ligand has been obtained and characterized.

[Scheme 1]

The cobalt(II) centre adopts a seven-coordinate distorted pentagonal-bipyramidal geometry, the donor atoms being two N atoms supplied by a bidentate 1,10-phenanthroline, four O atoms from two bidentate nitrate anions and an N atom from an acetonitrile ligand. The two axial sites are occupied by the acetonitrile ligand and one N-atom donor from the phenanthroline; as the other phenanthroline N-atom donor occupies an equatorial site, this ligand bridges axial and equatorial sites. The major distortions from ideal geometry occur within the equatorial plane, and are due to the narrow bite angle (ca. 57°) of the nitrate anions.

A dihedral angle of 4.05 (14)° is observed between the least-squares planes through the two nitrate anions which occupy four of the five equatorial positions of the cobalt(II) coordination environment. Dihedral angles of 105.1 (12) and 108.7 (12)° are observed between the plane through the 1,10-phenanthroline group and those of the nitrates.

[Figure 1]
Figure 1
A view of the structure of the title compound, showing the atom-numbering scheme adopted. Displacement ellipsoids are drawn at the 50% probability level.

Experimental

The title compound was prepared by slow reaction of Co(NO3)2·6H2O (10 mg, 0.034 mmol) and 1,10-phenanthroline (6 mg, 0.033 mmol) in acetonitrile (10 ml) in the presence of 4,4'-(1,4-phenylene)bis(3,6-dipyridin-2-ylpyridazine). Crystals were left to grow over a period of six months before being taken from the mother liquor for single-crystal X-ray diffraction studies.

Crystal data

  • [Co(NO3)2(C2H3N)(C12H8N2)]

  • Mr = 404.2

  • Monoclinic, P 21 /c

  • a = 7.1414 (9) Å

  • b = 14.3837 (17) Å

  • c = 15.4670 (19) Å

  • [beta] = 92.906 (2)°

  • V = 1586.7 (3) Å3

  • Z = 4

  • Dx = 1.692 Mg m-3

  • Mo K[alpha] radiation

  • [mu] = 1.13 mm-1

  • T = 150 (2) K

  • Block, orange

  • 0.14 × 0.12 × 0.10 mm
Data collection

  • Bruker SMART 1000 CCD area-detector diffractometer

  • [omega] scans

  • Absorption correction: multi-scan (SHELXTL; Bruker, 2001[Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.36a), SHELXTL (Version 6.12) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.575, Tmax = 0.614 (expected range = 0.840-0.896)

  • 9772 measured reflections

  • 3637 independent reflections

  • 2323 reflections with I > 2[sigma](I)

  • Rint = 0.042

  • [theta]max = 27.5°
Refinement

  • Refinement on F2

  • R[F2 > 2[sigma](F2)] = 0.036

  • wR(F2) = 0.069

  • S = 0.88

  • 3637 reflections

  • 236 parameters

  • H-atom parameters constrained

  • w = 1/[[sigma]2(Fo2) + (0.0239P)2] where P = (Fo2 + 2Fc2)/3

  • ([Delta]/[sigma])max = 0.001

  • [Delta][rho]max = 0.37 e Å-3

  • [Delta][rho]min = -0.32 e Å-3

Table 1
Selected geometric parameters (Å, °)

Co-N1 2.1087 (19)
Co-N2 2.1180 (19)
Co-N5 2.079 (2)
Co-O1 2.2375 (17)
Co-O3 2.2583 (18)
Co-O4 2.3289 (19)
Co-O5 2.1224 (17)
N1-Co-N2 78.48 (7)
N1-Co-N5 95.89 (7)
N1-Co-O3 137.22 (7)
N1-Co-O4 86.07 (7)
N1-Co-O5 141.12 (7)
N1-Co-O1 82.23 (7)
N2-Co-N5 172.54 (8)
N2-Co-O1 87.36 (7)
N2-Co-O3 87.34 (7)
N2-Co-O4 98.85 (7)
N2-Co-O5 92.63 (7)
N5-Co-O1 87.02 (7)
N5-Co-O3 93.68 (7)
N5-Co-O4 85.53 (7)
N5-Co-O5 94.82 (7)
O1-Co-O3 56.74 (6)
O1-Co-O4 165.41 (6)
O1-Co-O5 135.63 (6)
O3-Co-O4 136.29 (6)
O3-Co-O5 78.93 (6)
O4-Co-O5 57.68 (6)

The methyl H atoms on the acetonitrile molecule were located in [Delta]F syntheses and refined as part of a rigid rotating group, with C-H = 0.98 Å and Uiso(H) = 1.5Ueq(C). Aryl H atoms were positioned geometrically and refined using a riding model, with C-H = 0.95 Å.

Data collection: SMART (Bruker, 2001[Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.36a), SHELXTL (Version 6.12) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.36a), SHELXTL (Version 6.12) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT and SHELXTL (Bruker, 2001[Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.36a), SHELXTL (Version 6.12) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: MERCURY (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., van de Towler, M. & Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: enCIFer (Allen et al., 2004[Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338.]), PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]) and publCIF (Westrip, 2006[Westrip, S. P. (2006). In preparation.]).

Acknowledgements

We thank EPSRC (UK) for support.

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338. [ISI] [CrossRef] [ChemPort] [details]
Barnett, S. A., Blake, A. J., Champness, N. R., Nicolson, J. E. B. & Wilson, C. (2001). J. Chem. Soc. Dalton Trans. pp. 567-573.
Barnett, S. A., Blake, A. J., Champness, N. R. & Wilson, C. (2003b). Dalton Trans. pp. 2387-2394.
Barnett, S. A. & Champness, N. R. (2003a). Coord. Chem. Rev. 246, 145-168. [CrossRef] [ChemPort]
Blake, A. J., Champness, N. R., Khlobystov, A. N., Parsons, S. & Schröder, M. (2000). Angew. Chem. Int. Ed. 39, 2317-2320. [CrossRef] [ChemPort]
Braga, D., Brammer, L. & Champness, N. R. (2005). CrystEngComm, 7, 1-19. [CrossRef] [ChemPort]
Bruker (2001). SADABS (Version 2.03), SAINT (Version 6.36a), SHELXTL (Version 6.12) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA.
Champness, N. R. (2006). Dalton Trans. pp. 877-880. [CrossRef]
Khlobystov, A. N., Brett, M. T., Blake, A. J., Champness, N. R., Gill, P. M. W., O'Neill, D. P., Teat, S. J., Wilson, C. & Schröder, M. (2003). J. Am. Chem. Soc. 125, 6753-6761. [CrossRef] [PubMed] [ChemPort]
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., van de Towler, M. & Streek, J. (2006). J. Appl. Cryst. 39, 453-457. [CrossRef] [details]
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13. [ISI] [CrossRef] [ChemPort] [details]
Westrip, S. P. (2006). In preparation.

Acta Cryst (2006). E62, m2301-m2302   [ doi:10.1107/S1600536806032016 ]