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Acta Cryst. (2008). E64, o1000    [ doi:10.1107/S1600536808009598 ]

2,3-Diaminophenazine tetrahydrate

X.-F. Li, Y. An and Y.-S. Yin

Abstract top

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 [pi]-[pi] 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.

Comment top

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).

Related literature top

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

Experimental top

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).

Refinement top

In the absence of significant anomalous dispersion effects the Friedel pairs were merged. The H atoms were placed in calculated positions in the riding-model approximation (C—H 0.93 Å, N—H 0.90 Å), with their temperature factors were set to 1.2 times those of the equivalent isotropic temperature factors of the parent atoms. The water H atoms were located in difference Fourier maps and refined isotropically with distance restrains of O—H = 0.85 (2) and H···H = 1.39 (1) Å.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I).
[Figure 2] Fig. 2. Part of the crystal structure viewed along the c-axis. Dashed lines are drawn between the donor and acceptor atoms of the hydrogen bonds but H atoms are not showm.
2,3-Diaminophenazine tetrahydrate top
Crystal data top
C12H10N4·4H2OF000 = 600
Mr = 282.30Dx = 1.291 Mg m−3
Orthorhombic, Pca21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 3569 reflections
a = 16.7593 (18) Åθ = 2.7–24.3º
b = 18.1200 (19) ŵ = 0.10 mm−1
c = 4.7834 (5) ÅT = 293 (2) K
V = 1452.6 (3) Å3Block, black
Z = 40.37 × 0.32 × 0.23 mm
Data collection top
Bruker SMART APEX area-detector
diffractometer		1608 independent reflections
Radiation source: fine-focus sealed tube1432 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 293(2) Kθmax = 26.0º
φ and ω scansθmin = 1.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→18
Tmin = 0.965, Tmax = 0.977k = −19→22
7735 measured reflectionsl = −5→5
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.140  w = 1/[σ2(Fo2) + (0.0963P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
1608 reflectionsΔρmax = 0.29 e Å−3
225 parametersΔρmin = −0.12 e Å−3
17 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C12H10N4·4H2OV = 1452.6 (3) Å3
Mr = 282.30Z = 4
Orthorhombic, Pca21Mo Kα
a = 16.7593 (18) ŵ = 0.10 mm−1
b = 18.1200 (19) ÅT = 293 (2) K
c = 4.7834 (5) Å0.37 × 0.32 × 0.23 mm
Data collection top
Bruker SMART APEX area-detector
diffractometer		1608 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1432 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.977Rint = 0.022
7735 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.140Δρmax = 0.29 e Å−3
S = 1.14Δρmin = −0.12 e Å−3
1608 reflectionsAbsolute structure: ?
225 parametersFlack parameter: ?
17 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.51508 (13)0.31719 (12)0.3965 (5)0.0417 (6)
N20.51933 (12)0.16406 (12)0.2821 (6)0.0410 (5)
C100.46946 (14)0.20894 (15)0.1460 (6)0.0393 (6)
C110.41763 (15)0.18021 (16)−0.0623 (7)0.0443 (7)
H11A0.41840.1299−0.10080.053*
C10.56542 (15)0.27142 (16)0.5338 (6)0.0418 (7)
C120.36660 (15)0.22488 (17)−0.2076 (6)0.0445 (7)
C80.41408 (16)0.33188 (16)0.0507 (7)0.0456 (7)
H8A0.41230.38230.08730.055*
C90.46739 (15)0.28738 (15)0.2042 (6)0.0394 (6)
N40.31334 (15)0.19700 (17)−0.3960 (7)0.0603 (8)
H4B0.3134 (18)0.1476 (6)−0.403 (10)0.072*
H4C0.2916 (19)0.2287 (16)−0.520 (7)0.072*
N30.30987 (17)0.34664 (19)−0.2858 (6)0.0630 (8)
H3B0.315 (2)0.3961 (7)−0.263 (12)0.076*
H3C0.2912 (19)0.333 (2)−0.454 (4)0.076*
C50.62032 (15)0.14891 (17)0.6301 (7)0.0498 (7)
H5A0.62220.09850.59420.060*
C60.56701 (14)0.19474 (15)0.4760 (6)0.0401 (6)
C20.61674 (16)0.30014 (19)0.7428 (7)0.0512 (8)
H2A0.61630.35040.78280.061*
C70.36499 (15)0.30342 (16)−0.1501 (6)0.0446 (7)
C40.66820 (16)0.1785 (2)0.8286 (7)0.0561 (8)
H4A0.70250.14800.92890.067*
C30.66680 (18)0.25428 (18)0.8851 (7)0.0576 (9)
H3A0.70040.27361.02130.069*
O4W0.54392 (14)0.01642 (12)0.1437 (6)0.0592 (6)
O3W0.53446 (19)0.47020 (15)0.4439 (8)0.0798 (8)
O2W0.29410 (18)0.02670 (19)0.5763 (7)0.0818 (8)
O1W0.7032 (3)0.4897 (3)0.3542 (10)0.1042 (11)
H4WB0.541 (2)0.0631 (11)0.182 (8)0.088 (14)*
H3WB0.535 (3)0.4238 (14)0.396 (16)0.16 (3)*
H4WA0.516 (2)0.0085 (18)−0.004 (7)0.070 (12)*
H3WA0.4832 (14)0.481 (2)0.455 (16)0.14 (2)*
H2WA0.3416 (11)0.014 (2)0.601 (11)0.102 (16)*
H1WA0.723 (3)0.469 (4)0.495 (12)0.22 (4)*
H2WB0.266 (2)0.016 (2)0.724 (8)0.093 (16)*
H1WB0.6547 (14)0.478 (2)0.330 (13)0.11 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0396 (11)0.0510 (12)0.0344 (13)−0.0021 (9)0.0026 (10)−0.0015 (11)
N20.0359 (11)0.0526 (12)0.0346 (12)0.0009 (9)0.0026 (11)−0.0002 (11)
C100.0319 (12)0.0550 (14)0.0311 (14)−0.0024 (10)0.0056 (12)0.0001 (12)
C110.0373 (13)0.0571 (15)0.0386 (15)−0.0018 (12)−0.0006 (13)−0.0059 (13)
C10.0337 (13)0.0606 (16)0.0309 (15)−0.0032 (11)0.0033 (11)0.0012 (12)
C120.0302 (13)0.0741 (18)0.0293 (14)−0.0081 (12)0.0057 (11)−0.0011 (14)
C80.0444 (14)0.0551 (14)0.0375 (16)0.0061 (12)0.0035 (13)0.0010 (13)
C90.0361 (12)0.0509 (14)0.0313 (16)0.0018 (11)0.0035 (11)−0.0008 (12)
N40.0465 (14)0.092 (2)0.0428 (16)−0.0086 (13)−0.0108 (13)−0.0011 (17)
N30.0539 (15)0.089 (2)0.0463 (17)0.0191 (14)−0.0071 (14)0.0025 (15)
C50.0394 (13)0.0697 (17)0.0401 (17)0.0079 (12)0.0028 (13)0.0071 (16)
C60.0303 (12)0.0586 (15)0.0315 (15)−0.0004 (10)0.0021 (12)0.0022 (13)
C20.0423 (15)0.0733 (18)0.0379 (17)−0.0112 (13)0.0007 (13)−0.0048 (16)
C70.0357 (13)0.0699 (18)0.0282 (15)0.0063 (12)0.0034 (12)0.0024 (13)
C40.0358 (14)0.090 (2)0.0421 (18)0.0057 (15)−0.0020 (13)0.0131 (17)
C30.0379 (15)0.098 (3)0.0366 (16)−0.0096 (15)−0.0058 (14)0.0019 (17)
O4W0.0671 (14)0.0536 (12)0.0569 (15)0.0009 (10)−0.0081 (13)0.0014 (12)
O3W0.103 (2)0.0588 (14)0.078 (2)−0.0099 (13)−0.003 (2)−0.0042 (14)
O2W0.0642 (17)0.118 (2)0.0636 (18)0.0089 (16)−0.0007 (16)0.0027 (17)
O1W0.097 (2)0.123 (3)0.092 (3)−0.006 (2)0.007 (2)0.011 (2)
Geometric parameters (Å, °) top
N1—C91.333 (3)N3—H3B0.906 (10)
N1—C11.353 (3)N3—H3C0.895 (11)
N2—C101.335 (3)C5—C41.353 (5)
N2—C61.345 (4)C5—C61.425 (4)
C10—C111.421 (4)C5—H5A0.9300
C10—C91.449 (4)C2—C31.363 (4)
C11—C121.367 (4)C2—H2A0.9300
C11—H11A0.9300C4—C31.400 (4)
C1—C61.417 (4)C4—H4A0.9300
C1—C21.417 (4)C3—H3A0.9300
C12—N41.366 (4)O4W—H4WB0.867 (17)
C12—C71.450 (4)O4W—H4WA0.855 (19)
C8—C71.366 (4)O3W—H3WB0.872 (19)
C8—C91.410 (4)O3W—H3WA0.883 (19)
C8—H8A0.9300O2W—H2WA0.837 (19)
N4—H4B0.895 (10)O2W—H2WB0.87 (4)
N4—H4C0.90 (3)O1W—H1WA0.84 (6)
N3—C71.374 (4)O1W—H1WB0.849 (18)
C9—N1—C1117.4 (2)C7—N3—H3C120 (3)
C10—N2—C6117.2 (2)H3B—N3—H3C114 (4)
N2—C10—C11120.1 (2)C4—C5—C6120.3 (3)
N2—C10—C9121.2 (2)C4—C5—H5A119.9
C11—C10—C9118.7 (2)C6—C5—H5A119.9
C12—C11—C10121.5 (3)N2—C6—C1121.9 (2)
C12—C11—H11A119.3N2—C6—C5119.2 (3)
C10—C11—H11A119.3C1—C6—C5118.8 (2)
N1—C1—C6121.2 (2)C3—C2—C1120.1 (3)
N1—C1—C2119.7 (3)C3—C2—H2A119.9
C6—C1—C2119.1 (3)C1—C2—H2A119.9
N4—C12—C11121.7 (3)C8—C7—N3121.5 (3)
N4—C12—C7118.4 (3)C8—C7—C12119.5 (3)
C11—C12—C7119.8 (3)N3—C7—C12118.9 (3)
C7—C8—C9122.2 (3)C5—C4—C3120.9 (3)
C7—C8—H8A118.9C5—C4—H4A119.6
C9—C8—H8A118.9C3—C4—H4A119.6
N1—C9—C8120.5 (3)C2—C3—C4120.8 (3)
N1—C9—C10121.1 (2)C2—C3—H3A119.6
C8—C9—C10118.4 (2)C4—C3—H3A119.6
C12—N4—H4B113 (3)H4WB—O4W—H4WA108 (2)
C12—N4—H4C118 (2)H3WB—O3W—H3WA105 (2)
H4B—N4—H4C128 (4)H2WA—O2W—H2WB109 (2)
C7—N3—H3B117 (3)H1WA—O1W—H1WB112 (3)
C6—N2—C10—C11179.8 (2)N1—C1—C6—N20.5 (4)
C6—N2—C10—C90.4 (4)C2—C1—C6—N2179.4 (3)
N2—C10—C11—C12−179.2 (2)N1—C1—C6—C5−179.0 (3)
C9—C10—C11—C120.2 (4)C2—C1—C6—C50.0 (4)
C9—N1—C1—C6−0.3 (4)C4—C5—C6—N2−179.2 (3)
C9—N1—C1—C2−179.2 (2)C4—C5—C6—C10.2 (4)
C10—C11—C12—N4−176.0 (3)N1—C1—C2—C3179.0 (3)
C10—C11—C12—C70.2 (4)C6—C1—C2—C30.0 (4)
C1—N1—C9—C8−179.3 (2)C9—C8—C7—N3175.9 (3)
C1—N1—C9—C100.2 (4)C9—C8—C7—C120.6 (4)
C7—C8—C9—N1179.2 (2)N4—C12—C7—C8175.8 (3)
C7—C8—C9—C10−0.2 (4)C11—C12—C7—C8−0.6 (4)
N2—C10—C9—N1−0.3 (3)N4—C12—C7—N30.4 (4)
C11—C10—C9—N1−179.6 (3)C11—C12—C7—N3−176.0 (3)
N2—C10—C9—C8179.2 (3)C6—C5—C4—C3−0.5 (4)
C11—C10—C9—C8−0.2 (3)C1—C2—C3—C4−0.3 (5)
C10—N2—C6—C1−0.5 (4)C5—C4—C3—C20.5 (5)
C10—N2—C6—C5179.0 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···O2Wi0.895 (10)2.218 (12)3.105 (5)171 (3)
N4—H4C···N4ii0.90 (3)2.58 (3)3.198 (3)126 (3)
N3—H3B···O1Wiii0.906 (10)2.165 (16)3.048 (6)165 (4)
N3—H3C···N3ii0.895 (11)2.33 (2)3.122 (4)147 (3)
O4W—H4WA···O4Wiv0.855 (19)2.017 (19)2.871 (3)176 (4)
O4W—H4WB···N20.867 (17)1.924 (19)2.787 (3)173 (4)
O3W—H3WB···N10.872 (19)1.96 (3)2.801 (3)161 (6)
O2W—H2WA···O4Wv0.84 (2)2.01 (2)2.843 (4)178 (5)
O1W—H1WA···O1Wvi0.84 (6)2.15 (6)2.860 (7)142 (6)
O2W—H2WB···O2Wvii0.87 (4)1.97 (4)2.812 (5)161 (3)
O1W—H1WB···O3W0.85 (3)2.09 (3)2.882 (6)155 (5)
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y, z−1/2; (iii) −x+1, −y+1, z−1/2; (iv) −x+1, −y, z−1/2; (v) −x+1, −y, z+1/2; (vi) −x+3/2, y, z+1/2; (vii) −x+1/2, y, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···O2Wi0.895 (10)2.218 (12)3.105 (5)171 (3)
N4—H4C···N4ii0.90 (3)2.58 (3)3.198 (3)126 (3)
N3—H3B···O1Wiii0.906 (10)2.165 (16)3.048 (6)165 (4)
N3—H3C···N3ii0.895 (11)2.33 (2)3.122 (4)147 (3)
O4W—H4WA···O4Wiv0.855 (19)2.017 (19)2.871 (3)176 (4)
O4W—H4WB···N20.867 (17)1.924 (19)2.787 (3)173 (4)
O3W—H3WB···N10.872 (19)1.96 (3)2.801 (3)161 (6)
O2W—H2WA···O4Wv0.84 (2)2.01 (2)2.843 (4)178 (5)
O1W—H1WA···O1Wvi0.84 (6)2.15 (6)2.860 (7)142 (6)
O2W—H2WB···O2Wvii0.87 (4)1.97 (4)2.812 (5)161 (3)
O1W—H1WB···O3W0.85 (3)2.09 (3)2.882 (6)155 (5)
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y, z−1/2; (iii) −x+1, −y+1, z−1/2; (iv) −x+1, −y, z−1/2; (v) −x+1, −y, z+1/2; (vi) −x+3/2, y, z+1/2; (vii) −x+1/2, y, z+1/2.
Acknowledgements top

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

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.