3,4,7,8-Tetra­methyl-1,10-phenanthrolin-1-ium nitrate monohydrate

Ke-Jie Zhang; Yan-Fang Zhang

doi:10.1107/S1600536812023318

. 2012 May 31;68(Pt 6):o1931–o1932. doi: 10.1107/S1600536812023318

3,4,7,8-Tetramethyl-1,10-phenanthrolin-1-ium nitrate monohydrate

Ke-Jie Zhang ^a,^*, Yan-Fang Zhang ^b

PMCID: PMC3379486 PMID: 22719684

Abstract

In the crystal of the title compound, C₁₆H₁₇N₂ ⁺·NO₃ ⁻·H₂O, the tetramethyl-1,10-phenanthrolinium cations, nitrate anions and lattice water molecules are all located on a mirror plane with the methyl H atoms of the cation equally disordered over two sites about the mirror plane. The cation, anion and water molecule are linked by O—H⋯O and N—H⋯O hydrogen bonds into a sheet parallel to the bc plane. π–π stacking between phenanthroline ring systems is observed in the crystal structure, the centroid–centroid distance being 3.4745 (6) Å.

Related literature

For proton-transfer structures of phenanthroline and its derivatives, see: Bei et al. (2004 ▶); Buttery et al. (2006 ▶); Gillard et al. (1998 ▶); Harvey et al. (2008 ▶); Hensen et al. (1998 ▶, 2000 ▶); Kolev et al. (2009 ▶); Lin et al. (2009 ▶); Maresca et al. (1989 ▶); Milani et al. (1997 ▶); Montagu-Bourin et al. (1981 ▶); Shang et al. (2006 ▶); Thevenet & Rodier (1978 ▶); Thevenet et al. (1977 ▶, 1978 ▶, 1980 ▶); Wang et al. (1999 ▶); Yu et al. (2006 ▶).

Experimental

Crystal data

C₁₆H₁₇N₂ ⁺·NO₃ ⁻·H₂O
M _r = 317.34
Orthorhombic,
a = 6.7401 (8) Å
b = 24.090 (3) Å
c = 19.254 (2) Å
V = 3126.1 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.37 × 0.30 × 0.21 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
11308 measured reflections
1585 independent reflections
1149 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.153
S = 1.03
1585 reflections
143 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; 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, global. DOI: 10.1107/S1600536812023318/xu5537sup1.cif

e-68-o1931-sup1.cif^{(24.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023318/xu5537Isup2.hkl

e-68-o1931-Isup2.hkl^{(78.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812023318/xu5537Isup3.cml

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
N2—H2⋯O4ⁱ	0.86	1.86	2.692 (3)	164
O4—H1W⋯O1ⁱⁱ	0.84	1.97	2.808 (4)	174
O4—H2W⋯O1ⁱⁱⁱ	0.83	2.07	2.886 (4)	170

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

Acknowledgments

Financial support from the National Natural Science Foundation of Henan Educational Committee, China (2011 C550002) is gratefully acknowledged.

supplementary crystallographic information

Comment

1,10-Phenanthroline and its derivatives have been recognized as good proton acceptors, and usually are considered a suitable agent in the synthesis of proton-transfer systems. Some proton-transfer complexes based on 1,10-phenanthroline (Buttery et al. 2006; Gillard et al. 1998; Hensen et al. 1998, 2000; Kolev et al. 2009; Maresca et al. 1989; Milani et al. 1997; Montagu-Bourin, Levillain, Ceolin, Thevenet & Souleau 1981; Shang et al. 2006; Thevenet & Rodier 1978; Thevenet et al. 1977, 1980; Thevenet, Rodier & Khodadad 1978; Wang et al. 1999), 2,9-dimethyl-1,10-phenanthroline (Harvey et al. 2008; Yu et al. 2006), and 6-nitro-1,10-phenanthroline (Bei et al. 2004), 5,6-dihydroxy-phenanthroline (Lin et al. 2009) have been synthesized. In the recent work, the title compound (I), C₁₆H₁₇N₂]NO₃.H₂O, was obtained unintentionally as a major product in the reaction of Tb(NO₃)₃.6H₂O with the 3,4,7,8-tetramethyl-1,10-phenanthroline in water. To the best our knowledge, this is the first example of proton-transfer system containing 3,4,7,8-tetramethyl-1,10- 1,10-phenanthroline.

The numbering scheme of (I) is given in Fig. 1, and the selected bond lengths and bond angles are provided in the cif file. The crystal contains one protonated 3,4,7,8-tetramethyl-1,10- 1,10-phenanthroline cation, one nitrate anion and one water molecule. In the crystal structure, the cations, anions and water molecules are linked into two dimensional layers parallel to the bc plane by N—H···O and O—H···O hydrogen bonds (Table 1). Among them, N—H···O hydrogen bonds play a very important role in the formation of proton-transfer compounds. Additionally, the monoprotonated 3,4,7,8-tetramethyl-1,10- 1,10-phenanthroline cations are parallel to each other in the crystal packing, showing π-π interactions (Fig. 2); the centroid–centroid distance is 3.4745 (6) Å.

Experimental

A aqueous solution (12 ml) of Tb(NO₃)₃.6H₂O (1 mmol) and 3,4,7,8-tetramethyl-1,10-phenanthroline (1 mmol) was stirred. The mixture was then transferred to a 25-ml Teflon reactor and kept at 433 K for 3 d under autogenous pressure, and then cooled to room temperature at a rate of 10 K h^-1. Colorless crystals of the title compound were obtained.