supplementary materials


su2594 scheme

Acta Cryst. (2013). E69, o867-o868    [ doi:10.1107/S1600536813012245 ]

1-(4-Hydroxyphenyl)-2-(2-oxidonaphthalen-1-yl)diazen-1-ium methanol hemisolvate

M. A. Benaouida, S. Chetioui and S. E. Bouaoud

Abstract top

In the title compound, C16H12N2O2·0.5CH3OH, the H atom of the -OH group has been transfered to the N atom in the azo group, forming a zwitterion. Hence, there is an intramolecular N-H...O, rather than an O-H...N, hydrogen bond in the molecule. The molecule is almost planar, the dihedral angle between the benzene ring and the mean plane of the naphthalene ring system being 4.51 (6)°. In the crystal, molecules are linked to and bridged by O-H...O hydrogen bonds involving the methanol molecule, which is located about a twofold rotation axis, and hence half-occupied, forming zigzag chains along [001]. Molecules are also linked via C-H...[pi] and [pi]-[pi] interactions, the latter involving adjacent benzene and naphthalene rings and having a centroid-centroid distance of 3.6616 (13) Å, forming a three-dimensional network.

Comment top

Azo compounds are very important in the fields of dyes, pigments and advanced materials (Lee et al., 2004; Oueslati et al., 2004). Characterized by the azo linkage (–N=N–). Many azo compounds have been synthesized by the diazotization and a diazo coupling reaction (Wang et al., 2003), followed by a coupling reaction with 2-naphthol. This entails an electrophilic substitution reaction where an aryl diazonium cation attacks another aryl ring. Since diazonium salts are often unstable near room temperature, the azo coupling reactions are typically conducted near ice temperatures. The pH of the solution is quite important; it must be mildly acidic or neutral, since no reaction takes place if the pH is too low. We report herein on the crystal structure of the title compound, obtained through the diazotization of 4-hydroxyaniline followed by a coupling reaction with 2-naphthol. The synthesis and structure of a 4-methylaniline (Wang et al., 2003) and an aniline (Jin et al., 2008; Xu et al., 2010) analogue of the title compound have been described.

In the title molecule, Fig. 1, the bond lengths and angles are within normal ranges. Interestingly, the hydrogen atom of the OH group has been transfered to the N2 atom in the azo group to form a dipolar ion; the difference Fourier map indicated that the hydrogen atom site location is closer to the N atom of the azo group. Hence, there is an intramolecular N—H···O, rather than an O-H···N, hydrogen bond in the molecule (Fig. 1 and Table 1). The molecule is relatively plane, with mean plane of the naphthalene ring system (C1-C10) oriented at a dihedral angle of 4.51 (6) ° with respect to the benzene ring (C11-C16).

In the crystal, molecules are bridged by O-H···O hydrogen bonds, involving the methanol molecule which is located about a twofold rotation axis, forming chains along [001]; see Table 1 and Fig. 2. Molecules are also linked via C-H···π (Table 1) and ππ interactions interactions, forming a three-dimensional structure. The latter interactions involve adjacent benzene and naphthalene rings [Cg1···Cg3i = 3.6616 (13) Å; Cg1 is the centroid of ring C1-C6; Cg3 is the centroid of ring C11-C16; symmetry code: (i) x, y-1, z].

Related literature top

For azo compounds in the fields of dyes, pigments and advanced materials, see: Lee et al. (2004); Oueslati et al. (2004). For the synthesis of azo compounds, see: Wang et al. (2003). For the structures of related compounds, see: Jin et al. (2008); Xu et al. (2010).

Experimental top

The title compound was prepared by the method of (Wang et al., 2003) for similar aromatic azo–compounds. Red prismatic crystals of the title compound were obtained by slow evaporation of a solution in methanol.

Refinement top

The hydrogen atom of the OH group was located in a difference Fourier map and found to be near to the N atom, N2, of the azo group. In the final cycles of refinement it was included in a calculated position and treated as a riding atom: N-H = 0.86 Å with Uiso(H) = 1.2Ueq(N). The C-bound H atoms were positioned geometrically and refined as riding: C-H = 0.93 Å with Uiso(H) = 1.2Ueq(C). The disordered methanol solvent OH and CH3 H atoms were located in a difference Fourier map and refined as riding atoms with Uiso(H) = 1.5Ueq(O,C). Two reflections (2 0 0 and 1 1 3) likely affected by the beamstop were omitted in the final cycles of refinement.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view along the axis of the crystal packing of the title compound. The various hydrogen bonds are shown as dashed lines (see Table 1 for details).
1-(4-Hydroxyphenyl)-2-(2-oxidonaphthalen-1-yl)diazen-1-ium methanol hemisolvate top
Crystal data top
C16H12N2O2·0.5CH4OF(000) = 1176
Mr = 280.30Least-squares treatment of 25 SET4 setting angles.
Monoclinic, C2/cDx = 1.356 Mg m3
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 26.942 (7) ÅCell parameters from 1832 reflections
b = 6.3479 (17) Åθ = 2.4–25.7°
c = 17.579 (5) ŵ = 0.09 mm1
β = 113.985 (4)°T = 293 K
V = 2746.8 (13) Å3Prismatic, red
Z = 80.26 × 0.06 × 0.05 mm
Data collection top
Bruker APEXII CCD
diffractometer
2286 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Graphite monochromatorθmax = 30.7°, θmin = 2.4°
phi and ω scansh = 3837
12992 measured reflectionsk = 89
4212 independent reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0652P)2 + 0.3604P]
where P = (Fo2 + 2Fc2)/3
4212 reflections(Δ/σ)max = 0.001
202 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C16H12N2O2·0.5CH4OV = 2746.8 (13) Å3
Mr = 280.30Z = 8
Monoclinic, C2/cMo Kα radiation
a = 26.942 (7) ŵ = 0.09 mm1
b = 6.3479 (17) ÅT = 293 K
c = 17.579 (5) Å0.26 × 0.06 × 0.05 mm
β = 113.985 (4)°
Data collection top
Bruker APEXII CCD
diffractometer
2286 reflections with I > 2σ(I)
12992 measured reflectionsRint = 0.032
4212 independent reflectionsθmax = 30.7°
Refinement top
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.154Δρmax = 0.18 e Å3
S = 1.03Δρmin = 0.18 e Å3
4212 reflectionsAbsolute structure: ?
202 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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*/UeqOcc. (<1)
O10.05411 (5)0.9010 (2)0.10115 (8)0.0693 (5)
O20.09325 (5)1.7942 (2)0.17549 (9)0.0775 (5)
N10.13875 (5)0.98315 (19)0.04654 (7)0.0426 (4)
N20.09869 (5)1.1128 (2)0.02339 (7)0.0454 (4)
C10.13793 (5)0.8158 (2)0.09375 (8)0.0408 (4)
C20.09520 (6)0.7749 (3)0.12016 (10)0.0516 (5)
C30.09810 (7)0.5873 (3)0.16635 (10)0.0563 (6)
C40.13956 (6)0.4517 (3)0.18484 (9)0.0510 (5)
C50.18354 (6)0.4878 (2)0.16088 (8)0.0439 (5)
C60.18351 (5)0.6722 (2)0.11622 (8)0.0402 (4)
C70.22698 (6)0.3453 (3)0.18175 (9)0.0529 (5)
C80.26920 (7)0.3855 (3)0.16014 (10)0.0590 (6)
C90.26971 (6)0.5681 (3)0.11681 (10)0.0565 (6)
C100.22765 (6)0.7090 (3)0.09506 (9)0.0482 (5)
C110.09846 (5)1.2857 (2)0.02644 (8)0.0421 (4)
C120.05513 (6)1.4243 (3)0.04920 (10)0.0505 (5)
C130.05257 (6)1.5962 (3)0.09868 (10)0.0555 (5)
C140.09319 (6)1.6298 (2)0.12578 (9)0.0507 (5)
C150.13698 (6)1.4922 (2)0.10218 (9)0.0497 (5)
C160.13961 (6)1.3214 (2)0.05285 (9)0.0467 (5)
O1S0.00722 (9)2.0049 (3)0.21505 (14)0.0490 (7)0.500
C1S0.000002.1846 (5)0.250000.0803 (14)
H2A0.072301.093800.038300.0540*
H2B0.063901.854900.191900.1160*
H3A0.070600.558300.184000.0680*
H4A0.139700.329900.214300.0610*
H7A0.226900.222500.210600.0630*
H8A0.297800.290400.174400.0710*
H9A0.298800.594700.102500.0680*
H10A0.228400.830400.065900.0580*
H12A0.027601.401300.031100.0610*
H13A0.023501.689200.113700.0670*
H15A0.164701.516000.119900.0600*
H16A0.169001.229800.037200.0560*
H1SA0.035 (2)2.289 (9)0.284 (3)0.1210*0.500
H1O0.021002.049900.177900.0740*0.500
H1SB0.0081 (13)2.124 (4)0.2876 (18)0.1210*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0529 (7)0.0772 (9)0.0909 (9)0.0092 (6)0.0428 (6)0.0195 (7)
O20.0765 (9)0.0569 (8)0.0916 (9)0.0183 (7)0.0265 (8)0.0293 (7)
N10.0401 (6)0.0436 (7)0.0416 (6)0.0025 (5)0.0140 (5)0.0025 (5)
N20.0390 (6)0.0523 (8)0.0480 (7)0.0009 (6)0.0209 (5)0.0012 (6)
C10.0407 (7)0.0440 (8)0.0368 (7)0.0082 (6)0.0148 (6)0.0020 (6)
C20.0462 (8)0.0579 (10)0.0513 (8)0.0068 (7)0.0206 (7)0.0019 (8)
C30.0542 (9)0.0640 (11)0.0575 (9)0.0095 (8)0.0298 (8)0.0059 (8)
C40.0584 (9)0.0525 (10)0.0423 (8)0.0109 (8)0.0207 (7)0.0026 (7)
C50.0480 (8)0.0463 (9)0.0346 (7)0.0061 (7)0.0139 (6)0.0019 (6)
C60.0420 (7)0.0431 (8)0.0339 (7)0.0057 (6)0.0137 (5)0.0033 (6)
C70.0627 (10)0.0472 (9)0.0451 (8)0.0005 (8)0.0181 (7)0.0033 (7)
C80.0598 (10)0.0561 (11)0.0604 (10)0.0137 (8)0.0238 (8)0.0054 (8)
C90.0508 (9)0.0624 (11)0.0618 (10)0.0030 (8)0.0284 (8)0.0031 (8)
C100.0495 (8)0.0500 (9)0.0486 (8)0.0012 (7)0.0235 (7)0.0034 (7)
C110.0420 (7)0.0430 (8)0.0392 (7)0.0017 (6)0.0144 (6)0.0034 (6)
C120.0401 (7)0.0571 (10)0.0548 (9)0.0040 (7)0.0197 (7)0.0062 (8)
C130.0443 (8)0.0492 (10)0.0638 (10)0.0121 (7)0.0124 (7)0.0031 (8)
C140.0518 (9)0.0412 (9)0.0516 (8)0.0063 (7)0.0134 (7)0.0015 (7)
C150.0509 (8)0.0481 (9)0.0544 (9)0.0072 (7)0.0259 (7)0.0060 (7)
C160.0436 (7)0.0472 (9)0.0506 (8)0.0105 (7)0.0205 (6)0.0050 (7)
O1S0.0556 (12)0.0450 (13)0.0529 (12)0.0055 (11)0.0286 (10)0.0051 (10)
C1S0.105 (3)0.058 (2)0.090 (2)0.00000.052 (2)0.0000
Geometric parameters (Å, º) top
O1—C21.295 (2)C11—C161.384 (2)
O2—C141.362 (2)C11—C121.385 (2)
O2—H2B0.8200C12—C131.380 (3)
O1S—C1S1.347 (3)C13—C141.376 (2)
O1S—H1SBi0.76 (3)C14—C151.389 (2)
O1S—H1O0.9200C15—C161.372 (2)
N1—N21.2848 (19)C3—H3A0.9300
N1—C11.3538 (18)C4—H4A0.9300
N2—C111.4027 (18)C7—H7A0.9300
N2—H2A0.8600C8—H8A0.9300
C1—C61.449 (2)C9—H9A0.9300
C1—C21.429 (2)C10—H10A0.9300
C2—C31.426 (3)C12—H12A0.9300
C3—C41.341 (3)C13—H13A0.9300
C4—C51.428 (2)C15—H15A0.9300
C5—C71.405 (2)C16—H16A0.9300
C5—C61.4093 (19)C1S—H1SA1.11 (6)
C6—C101.402 (2)C1S—H1SB0.87 (3)
C7—C81.362 (3)C1S—H1SAi1.11 (6)
C8—C91.390 (3)C1S—H1SBi0.87 (3)
C9—C101.370 (3)
C14—O2—H2B109.00C4—C3—H3A119.00
C1S—O1S—H1O104.00C2—C3—H3A119.00
C1S—O1S—H1SBi37 (2)C3—C4—H4A119.00
H1O—O1S—H1SBi67.00C5—C4—H4A119.00
N2—N1—C1118.42 (14)C5—C7—H7A120.00
N1—N2—C11119.27 (13)C8—C7—H7A120.00
N1—N2—H2A120.00C9—C8—H8A120.00
C11—N2—H2A120.00C7—C8—H8A120.00
C2—C1—C6120.15 (13)C8—C9—H9A120.00
N1—C1—C2123.90 (14)C10—C9—H9A120.00
N1—C1—C6115.94 (13)C6—C10—H10A120.00
O1—C2—C1121.39 (16)C9—C10—H10A120.00
O1—C2—C3120.43 (16)C11—C12—H12A120.00
C1—C2—C3118.16 (16)C13—C12—H12A120.00
C2—C3—C4121.44 (18)C12—C13—H13A120.00
C3—C4—C5122.32 (16)C14—C13—H13A120.00
C4—C5—C7121.51 (14)C16—C15—H15A120.00
C6—C5—C7119.48 (15)C14—C15—H15A120.00
C4—C5—C6119.01 (14)C11—C16—H16A120.00
C1—C6—C5118.87 (13)C15—C16—H16A120.00
C1—C6—C10122.60 (13)O1S—C1S—O1Si64.2 (2)
C5—C6—C10118.53 (14)O1S—C1S—H1SA120 (3)
C5—C7—C8120.54 (16)O1S—C1S—H1SB95.7 (18)
C7—C8—C9120.30 (18)O1S—C1S—H1SAi121 (3)
C8—C9—C10120.39 (17)O1S—C1S—H1SBi31.5 (18)
C6—C10—C9120.76 (16)H1SA—C1S—H1SB106 (3)
N2—C11—C12117.83 (14)O1Si—C1S—H1SA121 (3)
N2—C11—C16122.48 (13)H1SA—C1S—H1SAi107 (4)
C12—C11—C16119.70 (13)H1SA—C1S—H1SBi105 (4)
C11—C12—C13120.33 (16)O1Si—C1S—H1SB31.5 (18)
C12—C13—C14119.86 (16)H1SAi—C1S—H1SB105 (4)
O2—C14—C13123.34 (15)H1SB—C1S—H1SBi127 (3)
C13—C14—C15119.84 (14)O1Si—C1S—H1SAi120 (3)
O2—C14—C15116.82 (15)O1Si—C1S—H1SBi95.7 (18)
C14—C15—C16120.34 (16)H1SAi—C1S—H1SBi106 (3)
C11—C16—C15119.93 (14)
C1—N1—N2—C11179.19 (12)C7—C5—C6—C1178.85 (13)
N2—N1—C1—C20.5 (2)C7—C5—C6—C101.0 (2)
N2—N1—C1—C6178.51 (12)C4—C5—C7—C8178.29 (15)
N1—N2—C11—C12178.98 (13)C6—C5—C7—C80.9 (2)
N1—N2—C11—C160.9 (2)C1—C6—C10—C9179.35 (14)
N1—C1—C2—O11.3 (2)C5—C6—C10—C90.5 (2)
N1—C1—C2—C3177.00 (14)C5—C7—C8—C90.2 (2)
C6—C1—C2—O1179.78 (14)C7—C8—C9—C100.3 (3)
C6—C1—C2—C32.0 (2)C8—C9—C10—C60.2 (2)
N1—C1—C6—C5176.08 (12)N2—C11—C12—C13179.50 (14)
N1—C1—C6—C103.72 (19)C16—C11—C12—C130.7 (2)
C2—C1—C6—C52.97 (19)N2—C11—C16—C15179.40 (13)
C2—C1—C6—C10177.23 (14)C12—C11—C16—C150.8 (2)
O1—C2—C3—C4178.23 (16)C11—C12—C13—C140.2 (2)
C1—C2—C3—C40.0 (2)C12—C13—C14—O2179.21 (15)
C2—C3—C4—C51.1 (3)C12—C13—C14—C150.9 (2)
C3—C4—C5—C60.0 (2)O2—C14—C15—C16179.31 (13)
C3—C4—C5—C7179.16 (15)C13—C14—C15—C160.8 (2)
C4—C5—C6—C11.97 (19)C14—C15—C16—C110.0 (2)
C4—C5—C6—C10178.22 (13)
Symmetry code: (i) x, y, z1/2.
Hydrogen-bond geometry (Å, º) top
Cg2 and Cg3 are the centroids of the C5–C10 and C11–C16 rings, respectively.
D—H···AD—HH···AD···AD—H···A
O1S—H1O···O1ii0.921.922.832 (3)171
N2—H2A···O10.861.842.540 (2)137
O2—H2B···O1S0.822.032.841 (3)172
O2—H2B···O1Si0.821.972.690 (3)146
C1S—H1SA···Cg3iii1.11 (6)2.58 (5)3.555 (2)147 (4)
C7—H7A···Cg2iv0.932.733.521 (2)144
Symmetry codes: (i) x, y, z1/2; (ii) x, y+3, z; (iii) x, y+1, z1/2; (iv) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
Cg2 and Cg3 are the centroids of the C5–C10 and C11–C16 rings, respectively.
D—H···AD—HH···AD···AD—H···A
O1S—H1O···O1i0.921.922.832 (3)171
N2—H2A···O10.861.842.540 (2)137
O2—H2B···O1S0.822.032.841 (3)172
O2—H2B···O1Sii0.821.972.690 (3)146
C1S—H1SA···Cg3iii1.11 (6)2.58 (5)3.555 (2)147 (4)
C7—H7A···Cg2iv0.932.733.521 (2)144
Symmetry codes: (i) x, y+3, z; (ii) x, y, z1/2; (iii) x, y+1, z1/2; (iv) x+1/2, y1/2, z+1/2.
Acknowledgements top

The authors, particularly MB (PNR project), thank the MESRS (Algeria) for financial support. Thanks are also due to Professor Ouahab, Director of Research at the Laboratory UMR LCSIM 6511, CNRS, Rennes I (France) for recording the diffraction data and help with the structure determination.

references
References top

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