organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

(E)-1-[2-(3,4-Di­methyl­phen­yl)diazen-2-ium-1-yl]naphthalen-2-olate

aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Faculté des Sciences Exactes, Département de Chimie, Université des Frères Mentouri Constantine, Constantine 25000, Algeria, bLaboratoire de Chimie Appliquée et Environnement, LCAE-URAC18, COSTE, Faculté des Sciences, Université Mohamed Premier, BP524, 60000, Oujda, Morocco, and cFaculté Pluridisciplinaire Nador BP 300, Selouane, 62702, Nador, Morocco
*Correspondence e-mail: souheilachetioui@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 1 February 2017; accepted 14 February 2017; online 17 February 2017)

The title zwitterion, C18H16N2O, features an intra­molecular N—H⋯O hydrogen bond. The di­methyl­benzene ring is rotationally disordered about the N—C bond over two adjacent orientations in a 0.75:0.25 ratio. The dihedral angle between the major orientation of the benzene ring and the naphthalene ring system is 6.06 (2)°. In the crystal, aromatic ππ stacking occurs [shortest centroid–centroid distance = 3.574 (3) Å] and C—H⋯O inter­actions are also observed.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

For general background to azo compounds and their use in dyes, pigments and advanced materials, see: Navarro & Sanz (1999[Navarro, A. & Sanz, F. (1999). Dyes Pigments, 40, 131-139.]); Tao et al. (1999[Tao, J., Mao, G. & Daehne, L. (1999). J. Am. Chem. Soc. 121, 3475-3485.]).

The title azo dye adopts the zwitterionic form in the crystal (Fig. 1[link]), with proton transfer from the phenol group to the azo group, which allows for the formation of an intra­molecular N—H⋯O hydrogen bond (Table 1[link]). The dimethyl benzene ring is disordered by ∼180° rotation about the N2—C11 bond over two adjacent orientations in a 0.75:0.25 ratio. The dihedral angle between the major orientation of the benzene ring and the naphthalene ring system is 6.06 (2)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2⋯O1 0.86 1.82 2.5347 (15) 140
C12A—H12A⋯O1i 0.93 2.54 3.325 (2) 143
Symmetry code: (i) -x+1, -y+1, -z.
[Figure 1]
Figure 1
The mol­ecular structure of the title compound, with 50% probability displacement ellipsoids.

In the crystal, mol­ecules are linked by aromatic ππ stacking between the benzene rings and the naphthalene ring systems of adjacent mol­ecules, the centroid–centroid distances of 3.574 (3) and 3.5754 (12) Å, respectively, between the C5–C10 and C11B–C16B(x, y − 1, z) rings and between the C5–C10 and C11A–C16A(x, y − 1, z) rings. C—H—O hydrogen bonds are also observed, forming chains running parallel to the a-axis direction (Table 1[link], Fig. 2[link]).

[Figure 2]
Figure 2
The crystal packing of the title compound, viewed along the b-axis direction.

Synthesis and crystallization

The title compound was synthesized according to a literature method (Wang et al., 2003[Wang, M., Funabiki, K. & Matsui, M. (2003). Dyes Pigments, 57, 77-86.]), viz. the diazo­tization of 3,4-di­methyl­aniline followed by a coupling reaction with 2-naphthol. Red prisms were obtained by slow evaporation of an acetone solution at room temperature (yield 88%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C18H16N2O
Mr 276.33
Crystal system, space group Monoclinic, P21/c
Temperature (K) 173
a, b, c (Å) 11.6326 (5), 6.1866 (2), 20.1712 (8)
β (°) 98.023 (2)
V3) 1437.44 (10)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.08
Crystal size (mm) 0.15 × 0.08 × 0.08
 
Data collection
Diffractometer Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections 13963, 3654, 2479
Rint 0.027
(sin θ/λ)max−1) 0.672
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.121, 1.04
No. of reflections 3654
No. of parameters 254
No. of restraints 7
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.25, −0.23
Computer programs: APEX2 and SAINT (Bruker, 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Structural data


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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(E)-1-[2-(3,4-Dimethylphenyl)diazen-2-ium-1-yl]naphthalen-2-olate top
Crystal data top
C18H16N2OF(000) = 584
Mr = 276.33Dx = 1.277 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3155 reflections
a = 11.6326 (5) Åθ = 2.5–28.1°
b = 6.1866 (2) ŵ = 0.08 mm1
c = 20.1712 (8) ÅT = 173 K
β = 98.023 (2)°Prism, red
V = 1437.44 (10) Å30.15 × 0.08 × 0.08 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
2479 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.027
Graphite monochromatorθmax = 28.5°, θmin = 2.9°
φ and ω scansh = 1515
13963 measured reflectionsk = 88
3654 independent reflectionsl = 2727
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0491P)2 + 0.2765P]
where P = (Fo2 + 2Fc2)/3
3654 reflections(Δ/σ)max < 0.001
254 parametersΔρmax = 0.25 e Å3
7 restraintsΔρmin = 0.23 e Å3
0 constraints
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)
O10.53655 (9)0.28137 (15)0.04401 (5)0.0423 (3)
N10.71280 (9)0.43066 (15)0.14740 (5)0.0306 (3)
N20.69480 (9)0.54119 (16)0.09243 (6)0.0330 (3)
C10.75035 (12)0.2025 (2)0.26821 (7)0.0410 (5)
C20.77274 (15)0.0808 (3)0.32550 (8)0.0542 (6)
C30.71594 (15)0.1166 (3)0.33086 (8)0.0572 (6)
C40.63748 (13)0.1890 (2)0.27889 (8)0.0450 (5)
C50.61249 (11)0.0680 (2)0.21974 (7)0.0331 (4)
C60.53071 (11)0.1422 (2)0.16480 (7)0.0353 (4)
C70.50626 (11)0.0288 (2)0.10759 (7)0.0347 (4)
C80.56216 (11)0.17470 (19)0.09888 (6)0.0306 (4)
C90.64717 (10)0.25164 (18)0.15195 (6)0.0271 (3)
C100.67092 (10)0.13066 (19)0.21396 (6)0.0300 (4)
C11A0.75837 (19)0.7234 (4)0.08101 (11)0.0240 (6)0.750
C12A0.73667 (19)0.8278 (4)0.01928 (10)0.0317 (6)0.750
C13A0.7995 (2)1.0103 (3)0.00825 (12)0.0358 (6)0.750
C14A0.8830 (2)1.0934 (3)0.05681 (16)0.0308 (7)0.750
C15A0.9037 (2)0.9908 (4)0.11911 (16)0.0308 (7)0.750
C16A0.8410 (3)0.8045 (6)0.13063 (13)0.0296 (8)0.750
C17A0.94946 (19)1.2939 (3)0.04259 (12)0.0460 (7)0.750
C18A0.98974 (19)1.0814 (3)0.17419 (11)0.0488 (7)0.750
C17B0.9986 (5)1.2864 (9)0.0922 (4)0.0434 (19)0.250
C11B0.7842 (8)0.7320 (16)0.1026 (4)0.0278 (12)0.250
C12B0.8620 (9)0.7828 (16)0.1558 (4)0.029 (2)0.250
C13B0.9316 (6)0.9638 (11)0.1505 (4)0.0309 (19)0.250
C14B0.9186 (6)1.0878 (11)0.0925 (4)0.0277 (19)0.250
C15B0.8400 (7)1.0352 (11)0.0381 (4)0.0278 (12)0.250
C16B0.7699 (5)0.8488 (11)0.0447 (3)0.0278 (12)0.250
C18B0.8259 (5)1.1641 (8)0.0252 (3)0.0397 (17)0.250
H10.788300.333800.265400.0490*
H16A0.855100.735000.171900.0360*0.750
H17A0.944501.398800.077200.0690*0.750
H17B0.916701.353100.000100.0690*0.750
H17C1.029301.257200.041400.0690*0.750
H18A0.967201.225600.184400.0730*0.750
H18B1.065301.084500.160200.0730*0.750
H18C0.991900.992300.213300.0730*0.750
H20.640800.499500.061500.0400*
H2A0.826000.129900.361000.0650*
H30.731600.198400.369800.0690*
H40.600100.320300.282700.0540*
H60.493200.273300.168800.0420*
H70.452400.082900.073200.0420*
H12A0.680400.775000.014100.0380*0.750
H13A0.785201.079200.033100.0430*0.750
H12B0.869200.700400.194700.0340*0.250
H13B0.987301.002000.186300.0370*0.250
H16B0.714300.807100.009400.0330*0.250
H17D0.952301.414200.083300.0650*0.250
H17E1.047701.268900.058000.0650*0.250
H17F1.045801.299600.135000.0650*0.250
H18D0.796601.305000.016800.0600*0.250
H18E0.772501.091900.058500.0600*0.250
H18F0.899801.178000.040900.0600*0.250
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0527 (6)0.0378 (5)0.0358 (5)0.0014 (5)0.0037 (4)0.0018 (4)
N10.0310 (6)0.0229 (5)0.0405 (6)0.0030 (4)0.0137 (5)0.0008 (4)
N20.0350 (6)0.0236 (5)0.0429 (6)0.0000 (4)0.0146 (5)0.0035 (5)
C10.0379 (8)0.0428 (8)0.0426 (8)0.0006 (6)0.0067 (6)0.0035 (6)
C20.0505 (10)0.0671 (11)0.0436 (9)0.0047 (8)0.0014 (7)0.0092 (8)
C30.0562 (10)0.0673 (11)0.0509 (9)0.0157 (9)0.0169 (8)0.0304 (8)
C40.0427 (8)0.0402 (8)0.0569 (9)0.0067 (7)0.0239 (7)0.0183 (7)
C50.0315 (7)0.0277 (6)0.0442 (7)0.0046 (5)0.0197 (6)0.0058 (6)
C60.0343 (7)0.0210 (6)0.0554 (9)0.0021 (5)0.0233 (6)0.0022 (6)
C70.0338 (7)0.0283 (6)0.0438 (7)0.0032 (5)0.0121 (6)0.0086 (6)
C80.0338 (7)0.0256 (6)0.0347 (7)0.0023 (5)0.0132 (5)0.0022 (5)
C90.0282 (6)0.0207 (6)0.0346 (6)0.0012 (5)0.0124 (5)0.0003 (5)
C100.0287 (6)0.0268 (6)0.0368 (7)0.0044 (5)0.0132 (5)0.0029 (5)
C11A0.0219 (11)0.0186 (8)0.0329 (13)0.0009 (8)0.0090 (8)0.0007 (10)
C12A0.0317 (11)0.0314 (9)0.0328 (11)0.0002 (8)0.0078 (8)0.0052 (9)
C13A0.0395 (12)0.0331 (10)0.0369 (11)0.0019 (9)0.0127 (9)0.0109 (9)
C14A0.0312 (13)0.0248 (11)0.0390 (14)0.0043 (9)0.0146 (10)0.0043 (11)
C15A0.0263 (12)0.0271 (12)0.0398 (14)0.0049 (9)0.0070 (11)0.0004 (12)
C16A0.0292 (16)0.0276 (11)0.0326 (15)0.0044 (10)0.0065 (13)0.0048 (13)
C17A0.0479 (12)0.0290 (9)0.0653 (14)0.0034 (9)0.0227 (11)0.0082 (10)
C18A0.0447 (12)0.0417 (11)0.0579 (13)0.0088 (10)0.0004 (10)0.0026 (10)
C17B0.038 (3)0.026 (3)0.067 (4)0.010 (2)0.010 (3)0.001 (3)
C11B0.024 (2)0.030 (2)0.028 (2)0.0008 (17)0.0014 (16)0.0009 (19)
C12B0.023 (4)0.023 (3)0.039 (5)0.004 (3)0.001 (4)0.000 (4)
C13B0.018 (3)0.034 (3)0.039 (4)0.002 (3)0.002 (3)0.005 (3)
C14B0.032 (3)0.022 (3)0.032 (4)0.002 (2)0.015 (3)0.011 (3)
C15B0.024 (2)0.030 (2)0.028 (2)0.0008 (17)0.0014 (16)0.0009 (19)
C16B0.024 (2)0.030 (2)0.028 (2)0.0008 (17)0.0014 (16)0.0009 (19)
C18B0.045 (3)0.027 (3)0.052 (3)0.001 (2)0.024 (3)0.014 (2)
Geometric parameters (Å, º) top
O1—C81.2873 (15)C15A—C18A1.497 (4)
N1—N21.2946 (15)C15A—C16A1.401 (4)
N1—C91.3555 (15)C15B—C16B1.429 (10)
N2—C11A1.385 (3)C15B—C18B1.495 (10)
N2—C11B1.568 (10)C1—H10.9300
N2—H20.8600C2—H2A0.9300
C1—C21.373 (2)C3—H30.9300
C1—C101.4023 (18)C4—H40.9300
C2—C31.400 (3)C6—H60.9300
C3—C41.366 (2)C7—H70.9300
C4—C51.404 (2)C12A—H12A0.9300
C5—C101.4171 (17)C12B—H12B0.9300
C5—C61.4316 (19)C13A—H13A0.9300
C6—C71.3465 (19)C13B—H13B0.9300
C7—C81.4390 (17)C16A—H16A0.9300
C8—C91.4335 (17)C16B—H16B0.9300
C9—C101.4507 (17)C17A—H17C0.9600
C11A—C12A1.394 (3)C17A—H17A0.9600
C11A—C16A1.382 (4)C17A—H17B0.9600
C11B—C16B1.364 (11)C17B—H17E0.9600
C11B—C12B1.341 (12)C17B—H17F0.9600
C12A—C13A1.380 (3)C17B—H17D0.9600
C12B—C13B1.395 (12)C18A—H18C0.9600
C13A—C14A1.379 (4)C18A—H18A0.9600
C13B—C14B1.390 (11)C18A—H18B0.9600
C14A—C17A1.510 (3)C18B—H18D0.9600
C14A—C15A1.398 (4)C18B—H18E0.9600
C14B—C17B1.542 (9)C18B—H18F0.9600
C14B—C15B1.366 (11)
N2—N1—C9117.66 (10)C2—C1—H1120.00
N1—N2—C11A123.10 (13)C10—C1—H1120.00
N1—N2—C11B105.1 (3)C1—C2—H2A120.00
C11B—N2—H2136.00C3—C2—H2A120.00
N1—N2—H2118.00C2—C3—H3120.00
C11A—N2—H2118.00C4—C3—H3120.00
C2—C1—C10120.65 (13)C3—C4—H4120.00
C1—C2—C3120.47 (15)C5—C4—H4119.00
C2—C3—C4119.93 (15)C5—C6—H6119.00
C3—C4—C5120.95 (13)C7—C6—H6119.00
C6—C5—C10119.27 (12)C6—C7—H7119.00
C4—C5—C6121.55 (12)C8—C7—H7120.00
C4—C5—C10119.18 (12)C11A—C12A—H12A120.00
C5—C6—C7122.30 (12)C13A—C12A—H12A120.00
C6—C7—C8121.03 (12)C11B—C12B—H12B121.00
O1—C8—C7119.95 (11)C13B—C12B—H12B121.00
O1—C8—C9121.64 (11)C12A—C13A—H13A119.00
C7—C8—C9118.41 (11)C14A—C13A—H13A119.00
N1—C9—C10116.02 (10)C14B—C13B—H13B120.00
C8—C9—C10120.07 (10)C12B—C13B—H13B120.00
N1—C9—C8123.86 (11)C15A—C16A—H16A120.00
C1—C10—C9122.33 (11)C11A—C16A—H16A120.00
C1—C10—C5118.82 (11)C11B—C16B—H16B120.00
C5—C10—C9118.85 (11)C15B—C16B—H16B120.00
N2—C11A—C12A119.43 (19)H17A—C17A—H17B110.00
N2—C11A—C16A120.6 (2)H17A—C17A—H17C110.00
C12A—C11A—C16A120.0 (2)C14A—C17A—H17A109.00
N2—C11B—C12B130.0 (8)C14A—C17A—H17B109.00
C12B—C11B—C16B123.3 (9)C14A—C17A—H17C109.00
N2—C11B—C16B106.7 (6)H17B—C17A—H17C109.00
C11A—C12A—C13A119.3 (2)C14B—C17B—H17D110.00
C11B—C12B—C13B117.5 (8)H17D—C17B—H17E109.00
C12A—C13A—C14A121.8 (2)H17D—C17B—H17F110.00
C12B—C13B—C14B120.8 (7)H17E—C17B—H17F109.00
C13A—C14A—C15A119.0 (2)C14B—C17B—H17E109.00
C15A—C14A—C17A121.0 (2)C14B—C17B—H17F110.00
C13A—C14A—C17A120.0 (2)H18B—C18A—H18C109.00
C13B—C14B—C17B116.6 (7)H18A—C18A—H18B109.00
C13B—C14B—C15B121.8 (7)H18A—C18A—H18C110.00
C15B—C14B—C17B121.6 (7)C15A—C18A—H18A109.00
C14A—C15A—C16A119.6 (2)C15A—C18A—H18B110.00
C14A—C15A—C18A120.7 (2)C15A—C18A—H18C109.00
C16A—C15A—C18A119.7 (3)C15B—C18B—H18D109.00
C14B—C15B—C16B116.4 (7)C15B—C18B—H18E109.00
C14B—C15B—C18B122.7 (6)C15B—C18B—H18F109.00
C16B—C15B—C18B120.9 (6)H18D—C18B—H18E110.00
C11A—C16A—C15A120.3 (3)H18D—C18B—H18F109.00
C11B—C16B—C15B120.3 (7)H18E—C18B—H18F109.00
C9—N1—N2—C11A178.13 (15)O1—C8—C9—N14.99 (19)
N2—N1—C9—C82.05 (17)O1—C8—C9—C10177.92 (11)
N2—N1—C9—C10179.25 (10)C7—C8—C9—N1174.01 (11)
N1—N2—C11A—C12A177.29 (17)C7—C8—C9—C103.08 (17)
N1—N2—C11A—C16A4.1 (3)N1—C9—C10—C14.86 (17)
C10—C1—C2—C30.4 (2)N1—C9—C10—C5174.62 (11)
C2—C1—C10—C51.2 (2)C8—C9—C10—C1177.83 (12)
C2—C1—C10—C9178.34 (13)C8—C9—C10—C52.69 (17)
C1—C2—C3—C40.1 (3)N2—C11A—C12A—C13A179.48 (19)
C2—C3—C4—C50.1 (2)C16A—C11A—C12A—C13A0.8 (4)
C3—C4—C5—C6179.81 (14)N2—C11A—C16A—C15A179.0 (2)
C3—C4—C5—C100.8 (2)C12A—C11A—C16A—C15A0.4 (4)
C4—C5—C6—C7179.60 (13)C11A—C12A—C13A—C14A0.4 (3)
C10—C5—C6—C70.6 (2)C12A—C13A—C14A—C15A0.6 (3)
C4—C5—C10—C11.30 (19)C12A—C13A—C14A—C17A179.8 (2)
C4—C5—C10—C9178.20 (12)C13A—C14A—C15A—C16A1.1 (4)
C6—C5—C10—C1179.63 (12)C13A—C14A—C15A—C18A177.2 (2)
C6—C5—C10—C90.87 (18)C17A—C14A—C15A—C16A179.7 (2)
C5—C6—C7—C80.1 (2)C17A—C14A—C15A—C18A2.0 (3)
C6—C7—C8—O1179.29 (12)C14A—C15A—C16A—C11A0.6 (4)
C6—C7—C8—C91.69 (19)C18A—C15A—C16A—C11A177.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.861.822.5347 (15)140
C12A—H12A···O1i0.932.543.325 (2)143
Symmetry code: (i) x+1, y+1, z.
 

Funding information

Funding for this research was provided by: Ministère de l'Enseignement Supérieur et de la Recherche ScientifiqueDirection Générale de la Recherche Scientifique et du Développement TechnologiqueUniversity of Constantine

References

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