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Acta Cryst. (2008). E64, o895    [ doi:10.1107/S1600536808010568 ]

Quinoxaline-3-aminophenol-water (2/1/2)

A. Czapik and M. Gdaniec

Abstract top

The asymmetric unit of the title compound, 2C8H6N2·C6H7NO·2H2O, contains two quinoxaline molecules, one molecule of 3-aminophenol and two water molecules which are hydrogen bonded to form a two-dimensional polymeric structure. Each of the symmetry-independent quinoxaline molecules forms separate stacks of different symmetry. In one set of stacks, the molecules are related by a screw axis and are slightly tilted [dihedral angle = 7.12 (1)°]. In the second set of stacks, adjacent molecules are parallel and related by an inversion center [interplanar distances = 3.376 (4) and 3.473 (4) Å].

Comment top

3-Aminophenol shows the ability to direct the assembly of supramolecular ladders via hydrogen bonding and π–π stacking interactions in the solid state (Sokolov et al., 2006; Sokolov & MacGillivray, 2006). On the other hand, 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). In the course of our studies on molecular complexes of diazaaromatic heterocycles we cocrystallized quinoxaline with 3-aminophenol expecting to obtain ladder-type assemblies analogous to those observed in cocrystals of bipyridines with 3-aminophenol (Sokolov et al., 2006). Unfortunately, the molecular complex with the expected 2:1 component ratio crystallized as a dihydrate (Fig. 1) that had a significant impact on the organization of molecules in the crystal.

Crystal packing of the title compound is shown in Fig. 2. The asymmetric unit contains two quinoxaline molecules, one 3-aminophenol molecule and two water molecules. The water molecules are hydrogen-bonded (for the hydrogen-bond geometry see Table 2) to form a helix extending along the b axis with the amino group of the 3-aminophenol linked to the helix via N—H···O interactions in the manner shown in Fig. 3a. The quinoxaline B molecules join to this assembly via hydrogen bonds to the phenolic OH groups whereas the quinoxaline A molecules bridge the water helices via O—H···N bonding and π–π stacking interactions generating a supramolecular two dimensional polymeric structure (Figure 3 b). The quinoxaline B molecules are also organized into π–π stacks extending along the b axis. The B molecules in the stacks are related by a screw-axis and are slightly tilted [dihedral angle of 7.12 (1)°] whereas the A molecules are parallel and related by inversion centers [interplanar distances of 3.376 (4) and 3.473 (4) Å].

Related literature top

For supramolecular ladders, see: Sokolov & MacGillivray (2006); Sokolov et al. (2006). For complexes of aromatic diazaheterocycles with phenols, see: Thalladi et al. (2000); Kadzewski & Gdaniec (2006).

Experimental top

The title compound was obtained by dissolving quinoxaline (0.2 g, 1.54 mmol) and 3-aminophenol (0.084 g, 0.77 mmol) in 5 ml of methanol followed slow evaporation to yield colorless plates suitable for data collection.

Refinement top

All H atoms were located in electron-density difference maps. C-bonded H atoms were placed at calculated positions, with C—H = 0.93 Å, and were refined as riding on their carrier C atoms, with Uĩso~(H) = 1.2Ueq(C). The H atoms of the OH and NH groups were freely refined (coordinates and isotropic displacement parameters).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. : The molecular structure of the title compound with displacement ellipsoids shown at the 50% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. : Crystal packing viewed down the y axis. Hydrogen bonds are shown with dashed lines.
[Figure 3] Fig. 3. a) the H2O helix with the 3-aminophenol molecules attached to the helix via hydrogen bonds to the amino group, b) two-dimensional polymeric structure formed by hydrogen-bonded quinoxaline A molecules and water molecules.
Quinoxaline–3-aminophenol–water (2/1/2) top
Crystal data top
2C8H6N2·C6H7NO·2H2OF000 = 856
Mr = 405.45Dx = 1.309 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5665 reflections
a = 15.2951 (10) Åθ = 2.1–27.9º
b = 7.1383 (4) ŵ = 0.09 mm−1
c = 20.1614 (14) ÅT = 130.0 (2) K
β = 110.775 (8)ºPlate, colourless
V = 2058.1 (3) Å30.40 × 0.40 × 0.07 mm
Z = 4
Data collection top
Kuma KM-4-CCD κ-geometry
diffractometer		3620 independent reflections
Radiation source: fine-focus sealed tube2285 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
T = 130(2) Kθmax = 25.0º
ω scansθmin = 4.1º
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)		h = −18→17
Tmin = 0.966, Tmax = 1.000k = −8→8
16706 measured reflectionsl = −23→23
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.031  w = 1/[σ2(Fo2) + (0.0362P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.070(Δ/σ)max = 0.001
S = 0.91Δρmax = 0.20 e Å−3
3620 reflectionsΔρmin = −0.14 e Å−3
300 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0029 (5)
Secondary atom site location: difference Fourier map
Crystal data top
2C8H6N2·C6H7NO·2H2OV = 2058.1 (3) Å3
Mr = 405.45Z = 4
Monoclinic, P21/cMo Kα
a = 15.2951 (10) ŵ = 0.09 mm−1
b = 7.1383 (4) ÅT = 130.0 (2) K
c = 20.1614 (14) Å0.40 × 0.40 × 0.07 mm
β = 110.775 (8)º
Data collection top
Kuma KM-4-CCD κ-geometry
diffractometer		3620 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)		2285 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 1.000Rint = 0.037
16706 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031300 parameters
wR(F2) = 0.070H atoms treated by a mixture of
independent and constrained refinement
S = 0.91Δρmax = 0.20 e Å−3
3620 reflectionsΔρmin = −0.14 e Å−3
Special details top

Experimental. Absorption correction: SCALE3 ABSPACK scaling algorithm of the Crysalis RED program (Oxford Diffraction, 2007)

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
N1A0.40385 (8)0.19751 (16)0.55810 (6)0.0257 (3)
C2A0.33478 (10)0.1595 (2)0.49872 (7)0.0268 (4)
H2A0.27670.12840.50080.032*
C3A0.34523 (10)0.1639 (2)0.43241 (8)0.0272 (4)
H3A0.29370.13540.39230.033*
N4A0.42444 (8)0.20642 (17)0.42434 (6)0.0257 (3)
C5A0.58438 (10)0.3015 (2)0.48061 (8)0.0295 (4)
H5A0.59170.30430.43680.035*
C6A0.65726 (10)0.3465 (2)0.54049 (9)0.0346 (4)
H6A0.71440.37990.53730.042*
C7A0.64723 (10)0.3431 (2)0.60726 (8)0.0346 (4)
H7A0.69770.37440.64770.042*
C8A0.56397 (10)0.2943 (2)0.61310 (8)0.0295 (4)
H8A0.55780.29250.65740.035*
C9A0.48741 (9)0.24661 (19)0.55196 (7)0.0223 (3)
C10A0.49775 (9)0.25055 (19)0.48513 (7)0.0215 (3)
N1B−0.01606 (8)0.88628 (16)0.35287 (6)0.0237 (3)
C2B−0.10425 (10)0.88544 (19)0.34628 (7)0.0257 (4)
H2B−0.11940.89230.38700.031*
C3B−0.17739 (10)0.8745 (2)0.27975 (8)0.0294 (4)
H3B−0.23880.87490.27850.035*
N4B−0.16252 (8)0.86390 (17)0.21969 (6)0.0297 (3)
C5B−0.04863 (11)0.8530 (2)0.16312 (7)0.0312 (4)
H5B−0.09640.84530.11910.037*
C6B0.04198 (11)0.8538 (2)0.16717 (8)0.0333 (4)
H6B0.05580.84870.12590.040*
C7B0.11481 (11)0.8625 (2)0.23343 (8)0.0331 (4)
H7B0.17660.86170.23570.040*
C8B0.09583 (10)0.8720 (2)0.29450 (8)0.0294 (4)
H8B0.14450.87750.33810.035*
C9B0.00272 (9)0.87338 (19)0.29139 (7)0.0210 (3)
C10B−0.07063 (10)0.86356 (19)0.22497 (7)0.0229 (3)
C1C0.15035 (9)0.7993 (2)0.52107 (7)0.0208 (3)
O1C0.11852 (7)0.96292 (14)0.48513 (5)0.0286 (3)
H1C0.0737 (11)0.936 (2)0.4413 (9)0.061 (6)*
C2C0.22485 (9)0.8116 (2)0.58454 (7)0.0217 (3)
H2C0.25110.92800.60070.026*
C3C0.26114 (9)0.6520 (2)0.62471 (7)0.0240 (4)
N1C0.33268 (10)0.6689 (2)0.68974 (8)0.0443 (4)
H2NC0.3584 (10)0.561 (2)0.7146 (8)0.044 (5)*
H1NC0.3613 (10)0.780 (2)0.6997 (8)0.037 (5)*
C4C0.22258 (9)0.4776 (2)0.59862 (7)0.0274 (4)
H4C0.24720.36900.62380.033*
C5C0.14761 (10)0.4673 (2)0.53511 (7)0.0268 (4)
H5C0.12180.35090.51830.032*
C6C0.11020 (9)0.6262 (2)0.49608 (7)0.0249 (4)
H6C0.05920.61760.45390.030*
O1D0.40947 (7)0.06594 (16)0.69381 (7)0.0325 (3)
H1D0.4028 (12)0.121 (3)0.6539 (11)0.071 (7)*
H2D0.4209 (13)0.161 (3)0.7281 (11)0.089 (8)*
O1E0.43284 (8)0.14985 (16)0.28706 (6)0.0320 (3)
H1E0.4870 (14)0.078 (3)0.2927 (10)0.086 (7)*
H2E0.4315 (12)0.175 (3)0.3316 (11)0.077 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0264 (7)0.0255 (8)0.0254 (7)−0.0008 (5)0.0097 (6)0.0018 (5)
C2A0.0243 (8)0.0269 (10)0.0292 (9)−0.0017 (7)0.0095 (7)0.0011 (7)
C3A0.0255 (9)0.0251 (10)0.0263 (9)−0.0008 (7)0.0036 (7)−0.0005 (7)
N4A0.0280 (7)0.0239 (7)0.0249 (7)0.0011 (5)0.0090 (6)0.0006 (5)
C5A0.0293 (9)0.0268 (10)0.0378 (10)0.0035 (7)0.0185 (8)0.0019 (7)
C6A0.0228 (9)0.0256 (10)0.0568 (12)−0.0007 (7)0.0158 (8)−0.0005 (8)
C7A0.0274 (9)0.0274 (10)0.0396 (10)0.0002 (7)0.0001 (8)−0.0030 (8)
C8A0.0312 (9)0.0283 (9)0.0253 (9)−0.0006 (7)0.0054 (7)−0.0015 (7)
C9A0.0239 (8)0.0169 (9)0.0256 (9)0.0009 (6)0.0083 (7)0.0018 (6)
C10A0.0247 (8)0.0155 (9)0.0248 (9)0.0030 (6)0.0094 (7)0.0005 (6)
N1B0.0234 (7)0.0231 (8)0.0242 (7)0.0012 (5)0.0078 (6)0.0024 (5)
C2B0.0298 (9)0.0242 (9)0.0269 (9)0.0032 (7)0.0146 (7)0.0049 (7)
C3B0.0218 (8)0.0331 (10)0.0348 (10)0.0012 (7)0.0120 (7)0.0063 (7)
N4B0.0254 (7)0.0345 (9)0.0283 (7)0.0002 (6)0.0083 (6)0.0050 (6)
C5B0.0410 (10)0.0298 (10)0.0233 (9)0.0000 (7)0.0120 (8)0.0015 (7)
C6B0.0486 (11)0.0281 (10)0.0331 (10)0.0024 (8)0.0266 (8)0.0046 (7)
C7B0.0314 (9)0.0270 (10)0.0492 (11)0.0029 (7)0.0246 (8)0.0043 (8)
C8B0.0233 (9)0.0296 (10)0.0339 (9)0.0026 (7)0.0084 (7)0.0029 (7)
C9B0.0241 (8)0.0164 (8)0.0235 (8)0.0019 (6)0.0099 (7)0.0027 (6)
C10B0.0261 (8)0.0183 (9)0.0247 (8)0.0013 (6)0.0093 (7)0.0038 (6)
C1C0.0210 (8)0.0218 (9)0.0215 (8)0.0031 (7)0.0100 (7)0.0026 (7)
O1C0.0286 (6)0.0246 (7)0.0255 (6)−0.0010 (5)0.0009 (5)0.0019 (5)
C2C0.0192 (8)0.0232 (9)0.0239 (8)−0.0042 (6)0.0088 (6)−0.0024 (6)
C3C0.0173 (8)0.0311 (10)0.0243 (8)−0.0010 (7)0.0082 (7)0.0038 (7)
N1C0.0365 (9)0.0366 (10)0.0408 (9)−0.0100 (8)−0.0099 (7)0.0144 (8)
C4C0.0256 (9)0.0270 (10)0.0314 (9)0.0025 (7)0.0124 (7)0.0085 (7)
C5C0.0298 (9)0.0236 (9)0.0294 (9)−0.0049 (7)0.0136 (7)−0.0030 (7)
C6C0.0244 (8)0.0272 (10)0.0221 (8)−0.0031 (7)0.0069 (7)−0.0014 (7)
O1D0.0400 (7)0.0326 (7)0.0252 (7)−0.0059 (5)0.0119 (5)−0.0024 (6)
O1E0.0382 (7)0.0348 (7)0.0229 (6)0.0000 (5)0.0106 (5)0.0005 (5)
Geometric parameters (Å, °) top
N1A—C2A1.3136 (16)C6B—C7B1.405 (2)
N1A—C9A1.3725 (17)C6B—H6B0.9300
C2A—C3A1.402 (2)C7B—C8B1.363 (2)
C2A—H2A0.9300C7B—H7B0.9300
C3A—N4A1.3138 (17)C8B—C9B1.4031 (18)
C3A—H3A0.9300C8B—H8B0.9300
N4A—C10A1.3726 (16)C9B—C10B1.4111 (18)
C5A—C6A1.3597 (19)C1C—O1C1.3697 (16)
C5A—C10A1.4078 (18)C1C—C2C1.3818 (17)
C5A—H5A0.9300C1C—C6C1.3919 (19)
C6A—C7A1.408 (2)O1C—H1C0.927 (17)
C6A—H6A0.9300C2C—C3C1.3940 (19)
C7A—C8A1.365 (2)C2C—H2C0.9300
C7A—H7A0.9300C3C—N1C1.3832 (18)
C8A—C9A1.4080 (18)C3C—C4C1.398 (2)
C8A—H8A0.9300N1C—H2NC0.927 (16)
C9A—C10A1.4116 (19)N1C—H1NC0.891 (16)
N1B—C2B1.3077 (16)C4C—C5C1.3850 (18)
N1B—C9B1.3711 (17)C4C—H4C0.9300
C2B—C3B1.4114 (19)C5C—C6C1.3839 (19)
C2B—H2B0.9300C5C—H5C0.9300
C3B—N4B1.3112 (18)C6C—H6C0.9300
C3B—H3B0.9300O1D—H1D0.87 (2)
N4B—C10B1.3714 (16)O1D—H2D0.94 (2)
C5B—C6B1.3591 (19)O1E—H1E0.95 (2)
C5B—C10B1.404 (2)O1E—H2E0.92 (2)
C5B—H5B0.9300
C2A—N1A—C9A116.37 (12)C5B—C6B—H6B119.8
N1A—C2A—C3A122.51 (14)C7B—C6B—H6B119.8
N1A—C2A—H2A118.7C8B—C7B—C6B120.66 (14)
C3A—C2A—H2A118.7C8B—C7B—H7B119.7
N4A—C3A—C2A123.05 (13)C6B—C7B—H7B119.7
N4A—C3A—H3A118.5C7B—C8B—C9B119.86 (14)
C2A—C3A—H3A118.5C7B—C8B—H8B120.1
C3A—N4A—C10A116.07 (12)C9B—C8B—H8B120.1
C6A—C5A—C10A119.83 (15)N1B—C9B—C8B119.66 (12)
C6A—C5A—H5A120.1N1B—C9B—C10B120.68 (12)
C10A—C5A—H5A120.1C8B—C9B—C10B119.65 (13)
C5A—C6A—C7A120.79 (15)N4B—C10B—C5B119.54 (13)
C5A—C6A—H6A119.6N4B—C10B—C9B121.44 (13)
C7A—C6A—H6A119.6C5B—C10B—C9B119.02 (13)
C8A—C7A—C6A120.54 (14)O1C—C1C—C2C117.20 (13)
C8A—C7A—H7A119.7O1C—C1C—C6C122.48 (12)
C6A—C7A—H7A119.7C2C—C1C—C6C120.32 (13)
C7A—C8A—C9A119.86 (14)C1C—O1C—H1C109.2 (11)
C7A—C8A—H8A120.1C1C—C2C—C3C120.90 (13)
C9A—C8A—H8A120.1C1C—C2C—H2C119.6
N1A—C9A—C8A119.65 (13)C3C—C2C—H2C119.6
N1A—C9A—C10A120.96 (12)N1C—C3C—C2C119.84 (14)
C8A—C9A—C10A119.40 (13)N1C—C3C—C4C121.36 (14)
N4A—C10A—C5A119.40 (13)C2C—C3C—C4C118.78 (13)
N4A—C10A—C9A121.01 (13)C3C—N1C—H2NC118.7 (10)
C5A—C10A—C9A119.59 (13)C3C—N1C—H1NC116.8 (10)
C2B—N1B—C9B116.56 (11)H2NC—N1C—H1NC122.4 (14)
N1B—C2B—C3B122.56 (14)C5C—C4C—C3C119.71 (13)
N1B—C2B—H2B118.7C5C—C4C—H4C120.1
C3B—C2B—H2B118.7C3C—C4C—H4C120.1
N4B—C3B—C2B122.83 (14)C6C—C5C—C4C121.45 (14)
N4B—C3B—H3B118.6C6C—C5C—H5C119.3
C2B—C3B—H3B118.6C4C—C5C—H5C119.3
C3B—N4B—C10B115.92 (12)C5C—C6C—C1C118.79 (13)
C6B—C5B—C10B120.46 (14)C5C—C6C—H6C120.6
C6B—C5B—H5B119.8C1C—C6C—H6C120.6
C10B—C5B—H5B119.8H1D—O1D—H2D106.6 (18)
C5B—C6B—C7B120.34 (14)H1E—O1E—H2E107.9 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1C—H1C···N1B0.927 (17)1.857 (17)2.7844 (14)178.7 (16)
N1C—H2NC···O1Ei0.927 (16)2.125 (17)3.0400 (19)168.8 (14)
N1C—H1NC···O1Dii0.891 (16)2.191 (17)3.058 (2)164.4 (13)
O1D—H1D···N1A0.87 (2)2.01 (2)2.8651 (17)166.8 (17)
O1D—H2D···O1Ei0.94 (2)1.77 (2)2.7022 (16)174.5 (19)
O1E—H1E···O1Diii0.95 (2)1.82 (2)2.7711 (17)177.8 (19)
O1E—H2E···N4A0.92 (2)1.92 (2)2.8446 (16)175.4 (18)
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y+1, z; (iii) −x+1, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1C—H1C···N1B0.927 (17)1.857 (17)2.7844 (14)178.7 (16)
N1C—H2NC···O1Ei0.927 (16)2.125 (17)3.0400 (19)168.8 (14)
N1C—H1NC···O1Dii0.891 (16)2.191 (17)3.058 (2)164.4 (13)
O1D—H1D···N1A0.87 (2)2.01 (2)2.8651 (17)166.8 (17)
O1D—H2D···O1Ei0.94 (2)1.77 (2)2.7022 (16)174.5 (19)
O1E—H1E···O1Diii0.95 (2)1.82 (2)2.7711 (17)177.8 (19)
O1E—H2E···N4A0.92 (2)1.92 (2)2.8446 (16)175.4 (18)
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y+1, z; (iii) −x+1, −y, −z+1.
references
References top

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