2,3-Diamino­phenazine tetra­hydrate

Xiao-Feng Li; Yan An; Yan-Sheng Yin

doi:10.1107/S1600536808009598

. 2008 May 7;64(Pt 6):o1000. doi: 10.1107/S1600536808009598

2,3-Diaminophenazine tetrahydrate

Xiao-Feng Li ^a,^*, Yan An ^a, Yan-Sheng Yin ^a

PMCID: PMC2961609 PMID: 21202528

Abstract

The title compound, C₁₂H₁₀N₄·4H₂O, was obtained from a room-temperature solution of o-phenylenediamine and copper acetate. In the crystal structure, there are significant π–π stacking interactions, with a centroid–centroid separation of 3.575 (2) Å. In addition, intermolecular O—H⋯O, N—H⋯O, N—H⋯N and O—H⋯N hydrogen bonds link 2,3-diaminophenazine molecules and water molecules, forming a three-dimensional framework.

Related literature

For related literature, see: Brownstein & Enright (1995 ▶); Doyle et al. (2001 ▶); Chłopek et al. (2005 ▶).

Experimental

Crystal data

C₁₂H₁₀N₄·4H₂O
M _r = 282.30
Orthorhombic,
a = 16.7593 (18) Å
b = 18.1200 (19) Å
c = 4.7834 (5) Å
V = 1452.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.37 × 0.32 × 0.23 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.965, T _max = 0.977
7735 measured reflections
1608 independent reflections
1432 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.140
S = 1.14
1608 reflections
225 parameters
17 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808009598/lh2601sup1.cif

e-64-o1000-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009598/lh2601Isup2.hkl

e-64-o1000-Isup2.hkl^{(79.3KB, 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
N4—H4B⋯O2Wⁱ	0.895 (10)	2.218 (12)	3.105 (5)	171 (3)
N4—H4C⋯N4ⁱⁱ	0.90 (3)	2.58 (3)	3.198 (3)	126 (3)
N3—H3B⋯O1Wⁱⁱⁱ	0.906 (10)	2.165 (16)	3.048 (6)	165 (4)
N3—H3C⋯N3ⁱⁱ	0.895 (11)	2.33 (2)	3.122 (4)	147 (3)
O4W—H4WA⋯O4W^iv	0.855 (19)	2.017 (19)	2.871 (3)	176 (4)
O4W—H4WB⋯N2	0.867 (17)	1.924 (19)	2.787 (3)	173 (4)
O3W—H3WB⋯N1	0.872 (19)	1.96 (3)	2.801 (3)	161 (6)
O2W—H2WA⋯O4W^v	0.84 (2)	2.01 (2)	2.843 (4)	178 (5)
O1W—H1WA⋯O1W^vi	0.84 (6)	2.15 (6)	2.860 (7)	142 (6)
O2W—H2WB⋯O2W^vii	0.87 (4)	1.97 (4)	2.812 (5)	161 (3)
O1W—H1WB⋯O3W	0.85 (3)	2.09 (3)	2.882 (6)	155 (5)

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

Acknowledgments

The authors thank the Program for Liaoning Excellent Talents in Universities for supporting this work (RC-05-11).

supplementary crystallographic information

Comment

The crystal structures of phenazinediamine (Doyle, et al., 2001) and examples of its derivatives (Brownstein, et al., 1995; Krzysztof, et al., 2005) have been published. As part of our studies of these types of compounds we report here the crystal structure of the title compound (I) which was synthesized at room temperature using o-Phenylenediamine and copper acetate.

In compound (I), the asymmetric unit contains a 2,3-Diamino-phenazine molecule and four water molecules (Fig. 1). In the crystal structure, 2,3-Diamino-phenazine molecules related by unit cell translations along the c axis form moderately strong π···π stacking interactions (Cg1···.Cg2(x, y, -1 + z) and Cg1···Cg3(x, y, 1 + z) = 3.575 (2) Å, where Cg1, Cg2 and Cg3 are the centroids defined by ring atoms N1/N2/C1/C6/C9/C10, C1—C6 and C7—C12, respectively). In addition, water molecules and 2,3-Diamino-phenazine molecules are linked by O—H···N, O—H···O, N—H···N and H—H···O hydrogen bonds to form a three-dimensional network (Table 1 & Fig.2).

Experimental

A mixture of o-Phenylenediamine(0.5 mmol, 0.054 g), Cu(CH₃COO)₂ (0.5 mmol,0.099 g), NaOH (1 mmol, 0.04 g), and water (10 ml) was placed in a 20 ml vial, stirring in air for 1 h. It was then sealed for 1 week and the resulting black block-shaped single crystals were collected. Yield: 67%. C&H analysis for C₁₂H₁₈N₄O₄ (found/calc): C, 51.03(51.06), H, 6.39(6.43).