1,10-Phenanthroline-5,6-dione ethanol monosolvate

Jing-Wei Dai; Zhao-Yang Li; Osamu Sato

doi:10.1107/S1600536814008241

. 2014 Apr 18;70(Pt 5):o573. doi: 10.1107/S1600536814008241

1,10-Phenanthroline-5,6-dione ethanol monosolvate

Jing-Wei Dai ^a, Zhao-Yang Li ^b, Osamu Sato ^a,^*

PMCID: PMC4011276 PMID: 24860377

Abstract

In the title compound, C₁₂H₆N₂O₂·C₂H₅OH, the molecule of the 1,10-phenanthroline-5,6-dione is approximately planar, with a maximum deviation of 0.051 (1) Å. In the crystal, molecules are linked by O—H⋯N and weak C—H⋯O hydrogen bonds, forming supramolecular chains propagating along [110]. π–π stacking interactions are observed between the pyridine rings of neighbouring chains, the centroid–centroid separations being 3.6226 (11) and 3.7543 (11) Å.

Related literature

For background to and applications of 1,10-phenanthroline-5,6-dione, see: Smith & Cagle (1947 ▶); Ma et al. (2010 ▶); Goss & Abruna (1985 ▶); Murphy et al. (2011 ▶); Wu et al. (1996 ▶); Pinczewska et al. (2012 ▶); Poteet & MacDonnell (2013 ▶); Wu et al. (2002 ▶); Poteet et al. 2013 ▶); Paw et al. (1998 ▶). For the synthesis, see: Paw & Eisenberg (1997 ▶). For a related structure, see: Calderazzo et al. (1999 ▶). graphic file with name e-70-0o573-scheme1.jpg

Experimental

Crystal data

C₁₂H₆N₂O₂·C₂H₆O
M _r = 256.26
Triclinic,
a = 7.3064 (15) Å
b = 9.1055 (18) Å
c = 9.7291 (19) Å
α = 96.47 (3)°
β = 101.68 (3)°
γ = 109.83 (3)°
V = 584.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 123 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Saturn724+ diffractometer
5059 measured reflections
2252 independent reflections
2074 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.114
S = 1.06
2252 reflections
185 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814008241/xu5783sup1.cif

e-70-0o573-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008241/xu5783Isup2.hkl

e-70-0o573-Isup2.hkl^{(110.7KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814008241/xu5783Isup3.cml

CCDC reference: 996896

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯N1ⁱ	0.85 (1)	2.08 (1)	2.8258 (19)	146 (2)
C1—H1⋯O2ⁱⁱ	0.95	2.53	3.3381 (19)	143

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

Acknowledgments

The authors would like to thank the China Scholarship Council (CSC).

supplementary crystallographic information

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

The title compound was prepared according to literature method (Paw & Eisenberg, 1997). An ice-cold mixture of concentrated H₂SO₄ (40 mL) and HNO₃ (20 mL) was added to 4 g of 1,10-phenanthroline (0.02 mol) and 4 g of KBr (0.03 mol). The mixture was heated at 90 ^oC for 3 h. The hot yellow solution was poured over 200 mL of ice and neutralized carefully with sodium hydroxide until neutral to slightly acidic pH. Extraction with CH₂Cl₂ (4*100 mL) followed by drying with Na₂SO₄ and removal of solvent gave 2.8 g (yield = 67%) of 1,10-phenanthroline-5,6-dione. This product was purified further by crystallization from ethanol.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Carbon-bound H-atoms were placed in calculated positions and were included in the refinement in the riding model approximation with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the others. The hydroxy H atom was located in a difference Fourier map, and was refined with distance restraints of O—H = 0.84±0.01, U_iso(H) = 1.2U_eq(O).

3. Results and discussion

1,10-Phenanthroline-5,6-dione has been known for many years (Smith & Cagle, 1947), and its chelating ability as either a diimine or a catecholate was important in coordination chemistry (Ma et al., 2010, Goss & Abruna, 1985, Murphy et al., 2011), analytical chemistry (Wu et al., 1996, Pinczewska et al., 2012) and biophysical chemistry (Poteet & MacDonnell, 2013, Wu et al., 2002, Poteet et al., 2013). Moreover, it can become as the bridging ligand, which has shown very interesting function in multinuclear complexes (Paw et al., 1998, Paw & Eisenberg, 1997, Calderazzo et al., 1999).

According to the structural analysis, the bond lengths and angles of the title compound are generally within normal ranges. The asymmetric unit of the title compound consists of one 1,10-phenanthroline-5,6-dione molecule and one ethanol molecule. Between molecules, O—H···N and C—H···O hydrogen bonds can be found that further form one-dimensional chain. The weak π···π stacking interactions between adjacent chains are also observed [centroid– centroid separations being 3.6226 (11) and 3.7543 (11) Å].