Tris(2,2′-bipyridine)­copper(II) penta­cyanido­nitro­soferrate(II) methanol disolvate monohydrate

Julia A Rusanova; Oksana V Nesterova; Roman I Zubatyuk; Olesia V Kozachuk

doi:10.1107/S1600536813006867

. 2013 Mar 16;69(Pt 4):m212–m213. doi: 10.1107/S1600536813006867

Tris(2,2′-bipyridine)copper(II) pentacyanidonitrosoferrate(II) methanol disolvate monohydrate

Julia A Rusanova ^a, Oksana V Nesterova ^a, Roman I Zubatyuk ^b, Olesia V Kozachuk ^a,^*

PMCID: PMC3629489 PMID: 23634007

Abstract

The title complex [Cu(C₁₀H₈N₂)₃][Fe(CN)₅(NO)]·2CH₃OH·H₂O, consists of discrete [Cu(bpy)₃]²⁺ cations (bpy is 2,2′-bipyridine), [Fe(CN)₅NO]²⁻ anions and solvent molecules of crystallization (two methanol molecules and one water molecules per asymmetric unit). The Cu^II ion adopts a distorted octahedral environment, coordinated by six N atoms from three bpy ligands. The cation charge is balanced by a nitroprusside counter-anion, which has a slightly distorted octahedral coordination geometry. In the crystal, anions and solvent molecules are involved in O—H⋯N and O—H⋯O hydrogen bonds, which form chains along [100]. The cations are located between these chains.

Related literature

For background to the direct synthesis of coordination compounds, see: Buvaylo et al. (2005 ▶); Babich et al. (1996 ▶); Kovbasyuk et al. (1998 ▶); Makhankova et al. (2002 ▶); Nesterov et al. (2006 ▶); Pryma et al. (2003 ▶); Vinogradova et al. (2002 ▶). For the structures of related complexes, see: Nikitina et al. (2008 ▶); Vreshch et al. (2009a ▶,b ▶); Shyu et al. (1997 ▶); Shyu & Wei (1999 ▶); Dong et al. (2003 ▶); Wang et al. (2007 ▶); Zhang et al. (2004 ▶). graphic file with name e-69-0m212-scheme1.jpg

Experimental

Crystal data

[Cu(C₁₀H₈N₂)₃][Fe(CN)₅(NO)]·2CH₄O·H₂O
M _r = 830.15
Monoclinic,
a = 11.1308 (8) Å
b = 14.7928 (9) Å
c = 23.1448 (17) Å
β = 90.916 (8)°
V = 3810.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: numerical (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.74, T _max = 0.91
22593 measured reflections
7368 independent reflections
3799 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.110
S = 1.01
7368 reflections
496 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.63 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

Click here for additional data file.^{(35.5KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813006867/lh5592sup1.cif

e-69-0m212-sup1.cif^{(35.5KB, cif)}

Click here for additional data file.^{(360.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006867/lh5592Isup2.hkl

e-69-0m212-Isup2.hkl^{(360.4KB, 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
O3S—H3SB⋯N9	0.85	2.04	2.870 (5)	165
O3S—H3SA⋯N7ⁱ	0.85	2.25	3.058 (5)	158
O1S—H1S⋯N8ⁱⁱ	0.82	2.08	2.831 (5)	151
O2S—H2S⋯O3S ⁱⁱⁱ	0.82	1.96	2.746 (7)	161

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

supplementary crystallographic information

Comment

This work is a continuation of our research in the field of direct synthesis of coordination compounds (Buvaylo et al., 2005; Babich et al., 1996; Kovbasyuk et al., 1998; Makhankova et al., 2002; Nesterov et al., 2006; Pryma et al., 2003; Vinogradova et al., 2002). We have shown recently the possibility of using anionic complexes as a source of metalloligands in direct synthesis of heterometallic compounds (Nikitina et al., 2008; Vreshch et al., 2009a,b).

In this paper we present a novel Cu/Fe heterometallic ionic complex [Cu(bpy)₃][Fe(CN)₅NO]^.2CH₃OH^.H₂O which consists of discrete [Cu(bpy)₃]²⁺ and [Fe(CN)₅NO]^2- ions (Fig. 1). The Cu^II ion adopts a distorted octahedral environment by coordinating with six nitrogen atoms from three bpy ligands. The range of Cu—N bond distances of 1.999 (3) - 2.035 (3)Å is in good agreement with the previously reported values for analagous complexes (Shyu et al., 1999; Wang et al., 2007). The anion geometry is unremarkable and in good agreement with reported values for other nitroprussides (Shyu et al. 1997; 1999; Dong et al. 2003; Zhang et al., 2004). In the crystal, anions are involved in the formation of O—H···O hydrogen bonds with solvent molecules to form one-dimensional chains along [100] (Fig. 2). The complex cations are located between these chains.

Experimental

Copper powder (0.04 g, 0.63 mmol), NH₄HSO₄ (0.145 g, 1.26 mmol), Na₂[Fe(CN)₅(NO)]^.2H₂O (0.188 g, 0.63 mmol) and bpy (0.296 g, 1.89 mmol) in methanol (30 ml) were heated to 323-333K and stirred magnetically until total dissolution of copper was observed (30 min). Dark-red crystals suitable for X-ray crystallography was isolated from the resulting dark-red solution with addition of 2-propanol in six days. The crystals (0.1 g, yield 30%) were filtered off, washed with dry methanol, and finally dried in vacuo at room temperature.