5,6-Dioxo-1,10-phenanthrolin-1-ium nitrate

Alireza Abbasi; Alireza Badiei; Sara Tarighi

doi:10.1107/S1600536807066172

. 2007 Dec 18;64(Pt 1):o290. doi: 10.1107/S1600536807066172

5,6-Dioxo-1,10-phenanthrolin-1-ium nitrate

Alireza Abbasi ^a,^*, Alireza Badiei ^a, Sara Tarighi ^a

PMCID: PMC2915341 PMID: 21200855

Abstract

In the title salt, C₁₂H₇N₂O₂ ⁺·NO₃ ⁻, the monoprotonated cation is connected to the nitrate anion by a hydrogen bond. Weak C—H⋯O hydrogen bonds hold the planar cations together in a layer structure.

Related literature

For related literature, see Fujihara et al. (2004 ▶); Larsson & Ohström (2004 ▶). For the bromide salt, see: Bomfim et al. (2003 ▶).

Experimental

Crystal data

C₁₂H₇N₂O₂ ⁺·NO₃ ⁻
M _r = 273.21
Monoclinic,
a = 14.4860 (19) Å
b = 12.5177 (13) Å
c = 13.4535 (16) Å
β = 101.720 (12)°
V = 2388.7 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 290 (2) K
0.30 × 0.10 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur 3 CCD diffractometer
Absorption correction: numerical (X-RED; Stoe & Cie, 1997 ▶) T _min = 0.960, T _max = 0.989
7311 measured reflections
2095 independent reflections
635 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.060
S = 0.83
2095 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2003 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066172/ng2405sup1.cif

e-64-0o290-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066172/ng2405Isup2.hkl

e-64-0o290-Isup2.hkl^{(103.1KB, 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
N1—H1⋯O5	0.86	1.95	2.703 (4)	145
C8—H8⋯O5ⁱ	0.93	2.48	3.396 (4)	167
C9—H9⋯O4ⁱ	0.93	2.71	3.359 (5)	128
C4—H4⋯O4ⁱⁱ	0.93	2.61	3.323 (4)	134
C3—H3⋯O3ⁱⁱ	0.93	2.40	3.209 (4)	146
C10—H10⋯O1ⁱⁱⁱ	0.93	2.47	3.318 (5)	151
C5—H5⋯O2^iv	0.93	2.37	3.266 (5)	162

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

Acknowledgments

This work was supported by grants from the University of Tehran and the Swedish Research Council. The authors are grateful to Professor Magnus Sandström for his support.

supplementary crystallographic information

Comment

From a survey of the Cambridge Structural Database [version 5.28, updated Jan. 2007], we found two complexes containing O-protonated pdon (Fujihara, et al., 2004; Larsson, & Ohström, 2004). However, up to now, only one molecule is reported for the N-protonated pdon (C₁₂H₇N₂O₂⁺, Hpdon) with bromide ions as counter ion (Bomfim et al., 2003).

The molecular structure and atom-labeling scheme for (I) are shown in Fig. 1. There is a relatively strong hydrogen bond between the nitrate ion and to the protonated nitrogen atom in Hpdon (N1—H1···O5, 2.703 (4) Å). Weak C–H···O hydrogen bonds hold the approximately planar cations together in a layer structure (Fig. 2). The packing of the layers is similar to that in the bromide salt of Hpdon (Bomfim et al., 2003) without specific directional interactions between the layers. Ring A (C1–C5/N1), B (C6–C10/N2) and C (C1/C2/C12/C11/C7/C6) in the cation (C₁₂H₇N₂O₂⁺, Hpdon) is approximately planar. The interplanar angle between the least-square planes defined by ring A and two other rings, B and C, are 1.69 (5)° and 1.17 (5)°, respectively. While, rings B and C are almost planar, 0.52 (5)°. However, the C—N—C angle is affected by protonation and causes to increase from 116.6 (3)° to 122.7 (3)° in the rings B and A, respectively. Similar effect has also been shown in the previously reported Hpdon bromide by increasing from 116.8 (3)° to 123.2 (3)° for the corresponding values. The comparison of the torsion angle, O1—C12—C11—O2, 2.5 (6)°, in (I) with the molecular pdon indicates that the N-protonation in (I) doesn't significantly affect on dione groups.

Experimental

The title compound was obtained during the reaction of thorium nitrate, Th(NO₃)₄.5H₂O (Merck, 99%), and 1,10-phenanthroline-5,6-dione (Aldrich, 97%) in ethanolic solution. Pale-yellow crystals of Hpdon were taken from the obtained greenish precipitates. The presence of water in the ethanolic solution and the high basicity of dione ligand can be the reason for the protonation, providing the C₁₂H₇N₂O₂⁺, Hpdon cation. Thin fragile layer crystals were obtained by recrystallization from acetonitrile.