Bis(2,9-dimethyl-1,10-phenanthroline)copper(I) penta­cyanido­nitro­soferrate(II)

Julia A Rusanova; Olesia V Kozachuk; Valentyna V Semenaka; Viktoriya V Dyakonenko

doi:10.1107/S1600536813031760

. 2013 Nov 27;69(Pt 12):m684–m685. doi: 10.1107/S1600536813031760

Bis(2,9-dimethyl-1,10-phenanthroline)copper(I) pentacyanidonitrosoferrate(II)

Julia A Rusanova ^a, Olesia V Kozachuk ^a,^*, Valentyna V Semenaka ^a, Viktoriya V Dyakonenko ^b

PMCID: PMC3885010 PMID: 24454185

Abstract

The asymmetric unit of the title complex [Cu(C₁₄H₁₂N₂)₂]₂[Fe(CN)₅(NO)], consists of a [Cu(dmp)₂]⁺ cation (dmp is 2,9-dimethyl-1,10-phenanthroline) and half an [Fe(CN)₅(NO)]²⁻ anion. The anion is disordered across an inversion center with the Fe^II ion slightly offset (ca 0.205Å) from the inversion center in the direction of the disordered trans-coordinating CN/NO ligands. The anion has a distorted octahedral coordination geometry. The Cu^I ion is coordinated by two phenanthroline ligands in a distorted tetrahedral geometry. The dihedral angle between the phenanthroline ligands is 77.16 (4) Å. In the crystal, the cations are connected to the anions by weak C—H⋯N hydrogen bonds. In addition, weak π–π stacking interactions are observed, with centroid–centroid distances in the range 3.512 (3)–3.859 (3) Å.

Related literature

For background to the direct synthesis of coordination compounds, see: Kokozay & Vassilyeva (2002 ▶); Nesterova et al. (2008 ▶). For the direct synthesis of heterometallic Cu-containing complexes, see: Buvaylo et al. (2005 ▶); Nesterova et al. (2004 ▶, 2005 ▶); Pryma et al. (2003 ▶). For the application of anionic complexes in the preparation of heterometallic compounds, see: Nikitina et al. (2008 ▶, 2009 ▶). For the structures of related complexes, see: Blake et al. (1998 ▶); Chen et al. (2002 ▶); Morpurgo et al. (1984 ▶); Cuttell et al. (2002 ▶); King et al. (2005 ▶); Soria et al. (2002 ▶); Shevyakova et al. (2002 ▶); Peresypkina & Vostrikova (2012 ▶). graphic file with name e-69-0m684-scheme1.jpg

Experimental

Crystal data

[Cu(C₁₄H₁₂N₂)₂]₂[Fe(CN)₅(NO)]
M _r = 1176.06
Triclinic,
a = 7.371 (3) Å
b = 13.741 (3) Å
c = 15.065 (4) Å
α = 115.269 (4)°
β = 95.327 (3)°
γ = 101.323 (4)°
V = 1325.9 (7) Å³
Z = 1
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 293 K
0.50 × 0.40 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur3 diffractometer
Absorption correction: numerical (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.604, T _max = 0.807
8613 measured reflections
5112 independent reflections
3100 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.109
S = 0.93
5112 reflections
377 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813031760/lh5667sup1.cif

e-69-0m684-sup1.cif^{(31.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813031760/lh5667Isup2.hkl

e-69-0m684-Isup2.hkl^{(250.4KB, 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
C17—H17⋯N6ⁱ	0.93	2.55	3.393 (6)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was partly supported by the State Fund for Fundamental Researches of Ukraine (project 54.3/005).

supplementary crystallographic information

1. Comment

The title compound was obtained as part of our research in the field of direct synthesis of coordination compounds (Buvaylo et al., 2005; Kokozay et al., 2002; Nikitina et al., 2008, 2009; Nesterova et al., 2004, 2005, 2008; Pryma et al.,2003). Complexes of copper chelated with phenanthroline (in particular 2,9-dimethyl-1,10-phenanthroline) have attracted attention due to their longlived excited states and potential use in solar energy conversion (Blake et al., 1998; Chen et al., 2002; Morpurgo et al., 1984; Cuttell et al., 2002; King et al., 2005).

In this paper we present a novel Cu/Fe heterometallic ionic complex [Cu(dmp)₂]₂[Fe(CN)₅NO] which consists of discrete [Cu(dmp)₂]⁺ and [Fe(CN)₅NO]^2- ions (Fig. 1). The Cu^I ion adopts a distorted tetrahedral environment by coordinating with four nitrogen atoms from two dmp ligands. The dihedral angle between the two dmp ligands (77.16 (4) Å) as well as the range of Cu—N bond distances of 2.034 (3) - 2.079 (3) Å is in good agreement with the previously reported values for analagous complexes (King et al., 2005 and references therein). The nitroprusside anion lies on an inversion centre and disordered over two positions so that iron atom occupies two very close positions (Fe···Fe distance is 0.410 (15) Å) corresponding to the coordination of two disordered CN and NO groups in the axial sites with very close positions. However, geometric parameters (average Fe—CN and Fe—NO bond distances of 1.96 Å and 1.63 Å respectively) are in a good agreement with literature values (Soria et al. (2002); Shevyakova et al. (2002); Peresypkina et al. (2012).

In the crystal, cations are connected to the anions by weak C—H···N hydrogen bonds. In addition weak π–π stacking interactions with centroid–centroid distances in the range 3.512 (3)–3.859 (3)° are observed (Fig. 2).

2. Experimental

Copper powder (0.04 g, 0.63 mmol), NH₄Br (0.123 g, 1.25 mmol), Na₂[Fe(CN)₅(NO)]^.2H₂O (0.188 g, 0.63 mmol) and dmp (0.262 g, 1.26 mmol) in DMF (30 ml) were heated to 333–343 K and stirred magnetically until total dissolution of copper was observed (2.5 h). Red needle-shaped crystals suitable for X-ray crystallography was isolated from the resulting dark-red solution with addition of 2-propanol and diethyl ether in a few days. The crystals (0.1 g, yield 30%) were filtered off, washed with dry methanol, and finally dried in vacuo at room temperature.