(Nitrato-κ2O,O′)bis­(1,10-phenanthroline-κ2N,N′)copper(II) tricyano­methanide

Lacková, K.; Potočňák, I.

doi:10.1107/S1600536812047757

Volume 68
Part 12
Pages m1553-m1554
December 2012

Received 24 October 2012
Accepted 20 November 2012
Online 28 November 2012

Key indicators
Single-crystal X-ray study
T = 183 K
Mean (C-C) = 0.004 Å
R = 0.040
wR = 0.097
Data-to-parameter ratio = 14.6
Details

(Nitrato-²O,O')bis(1,10-phenanthroline-²N,N')copper(II) tricyanomethanide

Katarína Lacková ^a ^* and Ivan Potocnák ^a

^aDepartment of Inorganic Chemistry, Faculty of Science, P.J. Safárik University, Moyzesova 11, SK-041 54 Kosice, Slovakia
Correspondence e-mail: katarina.lackova@student.upjs.sk

The title compound, [Cu(NO₃)(C₁₂H₈N₂)₂][C(CN)₃], is formed of discrete [Cu(NO₃)(phen)₂]⁺ complex cations (phen is 1,10-phenanthroline) and C(CN)₃^- counter-anions. The Cu^II atom has an asymmetric tetragonal-bipyramidal (4 + 1+1) stereochemistry with a pseudo-C₂ symmetry axis bisecting the nitrate ligand and passing through the Cu^II atom between the two phen ligands. The four N atoms of the phen ligands coordinate to the Cu^II atom with Cu-N distances in the range 1.974 (2)-2.126 (2) Å, while the two O atoms coordinate at substantially different distances [2.154 (2) and 2.586 (2) Å]. The structure is stabilized by C-HO hydrogen bonds and weak [pi] - [pi] interactions between nearly parallel benzene and pyridine rings of two adjacent phen molecules, with centroid-centroid distances of 3.684 (2) and 3.6111 (2) Å, and between [pi] -electrons of the tricyanomethanide anion and the pyridine or benzene rings [N(ring centroid) distances = 3.553 (3)-3.875 (3) Å].

Related literature

For five-coordinate Cu^II in [Cu(L)₂X]Y complexes [L = 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy); X = N(CN)₂^- or ONC(CN)₂^-, Y = 1^- anion], see: Potocnák et al. (2005, 2008). For complexes containing [Cu(NO₃)(phen)₂]⁺ cations, see: van Meerssche et al. (1981); Marsh (1997); Chen et al. (2005); Ovens et al. (2010). For complexes containing [Cu(bpy)₂NO₃]⁺ cations, see: Prasad et al. (1999); Marjani et al. (2005). For [pi] - [pi] interactions, see: Janiak (2000). For a description of the properties of the tricyanomethanide (tcm or C(CN)₃^-) anion, see: Golub et al. (1986). For [Cu(L)₂Y]tcm (Y = Cl^- or Br^-), see: Lacková (2012).

Experimental

Crystal data

[Cu(NO₃)(C₁₂H₈N₂)₂](C₄N₃)
M_r = 576.03
Monoclinic, P 2₁ /c
a = 13.3011 (4) Å
b = 10.1155 (3) Å
c = 19.5597 (6) Å
= 103.997 (3)°
V = 2553.56 (13) Å³
Z = 4
Mo K radiation
= 0.90 mm^-1
T = 183 K
0.38 × 0.31 × 0.26 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), based on expressions derived from Clark & Reid (1995)] T_min = 0.777, T_max = 0.825
10675 measured reflections
5283 independent reflections
4034 reflections with I > 2(I)
R_int = 0.024

Refinement

R[F² > 2(F²)] = 0.040
wR(F²) = 0.097
S = 1.01
5283 reflections
361 parameters
H-atom parameters constrained
_max = 0.40 e Å^-3
_min = -0.43 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
C12-H12O3ⁱ	0.93	2.52	3.206 (3)	131
C24-H24O2ⁱⁱ	0.93	2.44	3.231 (3)	144
C36-H36O3ⁱⁱⁱ	0.93	2.45	3.307 (3)	153
C46-H46O1^iv	0.93	2.47	3.201 (3)	136
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z+1; (iii) x, y+1, z; (iv) -x, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2531 ).

Acknowledgements

This work was supported by the Slovak Research and Development Agency under contract No. APVV-0132-11 and by the internal P·J. Safárik University grant system VVGS-PF-2012-24 and VVGS 1/12-13.

References

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