Phenazine–naphthalene-1,5-diamine–water (1/1/2)

Agnieszka Czapik; Maria Gdaniec

doi:10.1107/S1600536809049009

. 2009 Nov 21;65(Pt 12):o3177. doi: 10.1107/S1600536809049009

Phenazine–naphthalene-1,5-diamine–water (1/1/2)

Agnieszka Czapik ^a, Maria Gdaniec ^a,^*

PMCID: PMC2972038 PMID: 21578891

Abstract

The asymmetric unit of the title compound, C₁₂H₈N₂·C₁₀H₁₀N₂·2H₂O, contains one half-molecule of phenazine, one half-molecule of naphthalene-1,5-diamine and one water molecule. The phenazine and naphthalene-1,5-diamine molecules are located on inversion centers. The water molecules serve as bridges between the naphthalene-1,5-diamine molecules and also between the naphthalene-1,5-diamine and phenazine molecules. The naphthalene-1,5-diamine and water molecules are connected via N—H⋯O and O—H⋯N hydrogen bonds, forming a T4(2) motif. They are arranged into a two-dimensional polymeric structure parallel to (10 Inline graphic ) in which the water molecule is a single donor and a double acceptor, whereas the amino group is a double donor and a single acceptor in the hydrogen bonding. These two-dimensional assemblies alternate with the layers of phenazine molecules arranged into a herringbone motif. Each phenazine molecule is hydrogen bonded to two water molecules and thus a three-dimensional framework of hydrogen-bonded molecules is generated.

Related literature

For the structures of co-crystals of aromatic diazaheterocycles with small aromatic molecules, see: Thalladi et al. (2000 ▶); Kadzewski & Gdaniec (2006 ▶); Czapik & Gdaniec (2008 ▶). For structures with similar T4(2) hydrogen-bond motifs, see: Anthony et al. (2007 ▶); Neely et al. (2007 ▶). For symbols of hydrogen-bond motifs, see: Infantes et al. (2003 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). graphic file with name e-65-o3177-scheme1.jpg

Experimental

Crystal data

C₁₂H₈N₂·C₁₀H₁₀N₂·2H₂O
M _r = 374.44
Monoclinic,
a = 13.0395 (10) Å
b = 4.9266 (2) Å
c = 15.7211 (12) Å
β = 112.508 (9)°
V = 933.00 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 130 K
0.25 × 0.25 × 0.25 mm

Data collection

Kuma KM-4-CCD κ-geometry diffractometer
Absorption correction: none
5251 measured reflections
1643 independent reflections
1357 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.140
S = 1.08
1643 reflections
143 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); 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, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049009/rz2392sup1.cif

e-65-o3177-sup1.cif^{(14.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049009/rz2392Isup2.hkl

e-65-o3177-Isup2.hkl^{(81KB, 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
N1A—H1N⋯O1W	0.91 (4)	2.10 (4)	2.999 (3)	169 (3)
N1A—H2N⋯O1W ⁱ	0.97 (3)	2.15 (3)	3.102 (3)	166 (2)
O1W—H1W⋯N1A ⁱⁱ	0.85 (5)	2.04 (5)	2.871 (3)	167 (4)
O1W—H2W⋯N1B	0.89 (3)	2.07 (3)	2.953 (3)	174 (3)

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

supplementary crystallographic information

Comment

The title compound has been obtained unintentionally during our attempts to co-crystallize phenazine with naphthalene-1,5-diamine. Heterocycles like phenazine and quinoxaline are known to form a robust host framework with one-dimensional channels filled with small aromatic guest molecules (Thalladi et al., 2000; Kadzewski & Gdaniec; 2006). Inclusion of water molecules have however a significant impact on arrangement of molecules in these co-crystals (Czapik & Gdaniec, 2008).

Crystal packing of the title compound is shown in Fig. 2. Phenazine and naphthalene-1,5-diamine molecules are situated around inversion centers and are arranged into stacks along [010] by π–π stacking interactions. The molecules of naphthalene-1,5-diamine and water are connected via N—H···O and O—H···N hydrogen bonds that form the T4(2) motif (Table 1, Fig. 3). These hydrogen bonds connect molecules into a two-dimensional polymeric structure parallel to (1 0 - 1) in which the water molecule is a single donor and a double acceptor whereas the amino group plays a role a double donor and a single acceptor (Fig. 3). The layers of naphthalene-1,5-diamine and water molecules alternate with the layers of phenazine in which these aromatic molecules show a herringbone arrangement (Fig. 4). The phenazine molecules are hydrogen bonded to two water molecules and thus a three-dimensional framework of hydrogen-bonded molecules is generated (Fig. 2).

The Cambridge Structural Database (Allen, 2002) was searched for the structures containing C—NH₂ groups and water molecules to look for the frequency of the T4(2) motif (Infantes et al., 2003) generated by primary amino groups and water molecules. The search was limited to organic compounds with polymeric and ionic structures excluded and gave only two structures with the CSD refcodes DISNEZ, (Anthony et al., 2007) and MIMWAH01 (Neely et al., 2007). In both cases the donor and acceptor functions of the amino group and water molecule were analogous to those in the title compound.

Experimental

The title compound was obtained by dissolving phenazine (0.100 g, 0.55 mmol) and naphthalene-1,5-diamine (0.088 g, 0.55 mmol) in 5 ml of acetone. Slow evaporation of the solution yielded red cuboid crystals.