1-[(E)-2-(2-Hy­droxy-5-methyl­phen­yl)diazen-2-ium-1-yl]naphthalen-2-olate

Chetioui, S.; Boudraa, I.; Bouacida, S.; Bouchoul, A.; Bouaoud, S.E.

doi:10.1107/S160053681302014X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1322-o1323

doi:10.1107/S160053681302014X

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1-[(E)-2-(2-Hydroxy-5-methylphenyl)diazen-2-ium-1-yl]naphthalen-2-olate

Souheyla Chetioui,^a Issam Boudraa,^a ^* Sofiane Bouacida,^a Abdelkader Bouchoul ^a and Salah Eddine Bouaoud ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, (CHEMS), Faculté des Sciences Exactes, Département de Chimie, Université Constantine 1, 25000 Constantine, Algeria
^*Correspondence e-mail: issam.boudraa@gmail.com

(Received 8 July 2013; accepted 21 July 2013; online 27 July 2013)

The title zwitterion, C₁₇H₁₄N₂O₂, crystallizes with two independent molecules in the asymmetric unit, both of which are approximately planar, the dihedral angles between the benzene ring and the naphthalene ring system being 4.39 (12)° in one molecule and 5.83 (12)° in the other, and show an E conformation with respect to the azo double bond. An intramolecular N—H⋯O hydrogen bond in each molecule helps to establish their near planar conformation. In the crystal, molecules are linked through O—H⋯O hydrogen bonds into infinite chains running along the a-axis direction. In addition, the chains are stacked along the b axis via π–π interactions between the benzene and the naphthalene rings of adjacent molecules, the centroid–centroid distances being 3.722 (3) and 3.823 (4) Å.

Related literature

For general background to the use of azo compounds as dyes, pigments and advanced materials, see: Lee et al. (2004 ). For details of azo pigments, see: Herbst & Hunger (2004 ). For related structures of hydrazone derivatives, see: Olivieri et al. (1989 ); Oakes (2002 ). For bond-length data, see: Yazıcı et al. (2010 ); Karadayı et al. (2006 ). Many azo compounds have been synthesized by diazotization and diazo coupling reactions, see: Wang et al. (2003 ).

Experimental

Crystal data

C₁₇H₁₄N₂O₂
M_r = 278.31
Monoclinic, P 2₁ /a
a = 14.541 (5) Å
b = 6.052 (5) Å
c = 32.633 (5) Å
β = 101.871 (5)°
V = 2810 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.03 × 0.02 × 0.02 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.853, T_max = 0.995
20440 measured reflections
6447 independent reflections
3301 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.202
S = 1.05
6447 reflections
386 parameters
2 restraints
All H-atom parameters refined
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.88 (2)	1.82 (3)	2.536 (4)	138 (2)
O2—H2⋯O6	0.82	1.85	2.631 (3)	159
O5—H5⋯O1ⁱ	0.82	1.81	2.622 (3)	168
N6—H6⋯O6	0.88 (2)	1.82 (3)	2.546 (4)	138 (2)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks Chetioui-data, I. DOI: 10.1107/S160053681302014X/lr2112sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681302014X/lr2112Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681302014X/lr2112Isup3.cml

checkCIF report

Comment top

Azo compounds are very important in the fields of dyes, pigments and advanced materials (Lee et al., 2004). Azo dyes are synthetic colours that contain an azo group, as part of the structure. We are involved in the color generation mechanism of azo pigments typically characterized by the chromophore of the azo group (–N=N–). However, some types of azo pigments are also known to possess the hydrazone structure (=N–NH–), often leading to the formation of intramolecular hydrogen bonds (Herbst & Hunger 2004). The azo– hydrazone tautomerism in azo dyes has been known for more than a hundred years and is directly connected with the presence of at least one protic donor group in conjugation to the azo bridge (i.e. 2-naphthol) (Olivieri et al.., 1989). In particular, azo dyes that contain a naphtholic hydroxy group conjugated with the azo linkage exist in aqueous solution as an equilibrium mixture of two chemically distinct tautomers, the azo or hydrazone forms (Oakes, 2002).It is suggested that in a real azo compound the N=N double bond should have a length of 1.20–1.28 Å and the bond length of N–N single bonds, as in hydrazone tautomers, should be more than 1.4 Å. In the title compound, N–N bond lengths are 1.385 Å for N1–N2 and 1.305 Å for N5–N6, between the suggested N=N double bond and N–N single bond lengths.In the molecule, all bond lengths are in good agreement with those reported for other azo compounds (Yazıcı et al., 2010; Karadayı et al., 2006).

The molecular structure of the title compound is shown in Figure 1.There are two independent molecules in the asymmetric unit, each consists of a benzene ring linked to the first nitrogen atom of the N = N chromophore and two aromatic rings of the core 2-naphthol, with a trans configuration with respect to the azo double bond. The dihedral angles between the benzene ring and naphthalene ring system being 4.39 (12)° in one molecule and 5.83 (12)° in the other. Intramolecular N—H···O hydrogen bonds stabilize the planar geommetry in each of the independent molecules. In the crystal, the molecules are linked through O—H···O into infinite one-dimensional chains running along the a axis, Figure 2. In addition, the chains are stacked along the b axis via π-π interactions between the benzene and the naphthalene rings of adjacent molecules, the centroid-centroid distances being 3.722 (3) and 3.823 (4) Å.

Related literature top

For general background to the use of azo compounds as dyes, pigments and advanced materials, see: Lee et al. (2004). For details of azo pigments, see: Herbst & Hunger (2004). For related structures of hydrazone derivatives, see: Olivieri et al. (1989); Oakes (2002). For bond-length data, see: Yazıcı et al. (2010); Karadayı et al. (2006). Many azo compounds have been synthesized by diazotization and diazo coupling reactions, see: Wang et al. (2003).

Experimental top

The title compound (E)-1-((2-hydroxy-5-methylphenyl)diazenyl)naphthalen-2-ol was prepared following the classical method of synthesis of other aromatic azo-compounds (Wang et al., 2003). Diazotization of 2-amino-4-methylphenol followed by a coupling reaction with 2-naphthol. This gives a red powder which was recrystallized from ethanol leading to crystals in the form of red prisms.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of (I), with 50% probability displacement ellipsoids for non-H atoms.The dashed lines indicate N—H···O hydrogen bond.
	Fig. 2. A view of the crystal packing showing the infinite one-dimensional chains.

1-[(E)-2-(2-Hydroxy-5-methylphenyl)diazen-2-ium-1-yl]naphthalen-2-olate top

Crystal data top

C₁₇H₁₄N₂O₂	F(000) = 1168
M_r = 278.31	D_x = 1.316 Mg m⁻³
Monoclinic, P2₁/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 2052 reflections
a = 14.541 (5) Å	θ = 3.1–28.6°
b = 6.052 (5) Å	µ = 0.09 mm⁻¹
c = 32.633 (5) Å	T = 150 K
β = 101.871 (5)°	Prism, red
V = 2810 (3) Å³	0.03 × 0.02 × 0.02 mm
Z = 8

Data collection top

Bruker APEXII diffractometer	6447 independent reflections
Radiation source: fine-focus sealed tube	3301 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
CCD rotation images, thin slices ω scans	θ_max = 27.6°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −15→18
T_min = 0.853, T_max = 0.995	k = −7→7
20440 measured reflections	l = −42→42

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.068	All H-atom parameters refined
wR(F²) = 0.202	w = 1/[σ²(F_o²) + (0.0877P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
6447 reflections	Δρ_max = 0.44 e Å⁻³
386 parameters	Δρ_min = −0.40 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0045 (9)

Crystal data top

C₁₇H₁₄N₂O₂	V = 2810 (3) Å³
M_r = 278.31	Z = 8
Monoclinic, P2₁/a	Mo Kα radiation
a = 14.541 (5) Å	µ = 0.09 mm⁻¹
b = 6.052 (5) Å	T = 150 K
c = 32.633 (5) Å	0.03 × 0.02 × 0.02 mm
β = 101.871 (5)°

Data collection top

Bruker APEXII diffractometer	6447 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	3301 reflections with I > 2σ(I)
T_min = 0.853, T_max = 0.995	R_int = 0.078
20440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	2 restraints
wR(F²) = 0.202	All H-atom parameters refined
S = 1.05	Δρ_max = 0.44 e Å⁻³
6447 reflections	Δρ_min = −0.40 e Å⁻³
386 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.85799 (14)	0.2548 (4)	0.70663 (5)	0.0333 (7)
O2	0.71941 (15)	0.6953 (4)	0.72953 (5)	0.0412 (8)
N1	0.76040 (16)	0.5426 (4)	0.66053 (6)	0.0258 (8)
N2	0.78287 (15)	0.4506 (4)	0.62766 (6)	0.0242 (8)
C1	0.83515 (19)	0.2673 (5)	0.63285 (7)	0.0231 (9)
C2	0.87195 (19)	0.1652 (5)	0.67294 (8)	0.0266 (9)
C3	0.9241 (2)	−0.0362 (5)	0.67367 (9)	0.0313 (10)
C4	0.9385 (2)	−0.1299 (6)	0.63794 (9)	0.0353 (10)
C5	0.9043 (2)	−0.0319 (5)	0.59751 (9)	0.0314 (10)
C6	0.85416 (19)	0.1681 (5)	0.59467 (8)	0.0269 (9)
C7	0.8225 (2)	0.2665 (6)	0.55501 (8)	0.0323 (10)
C8	0.8408 (2)	0.1641 (7)	0.51963 (9)	0.0405 (13)
C9	0.8902 (2)	−0.0332 (7)	0.52232 (9)	0.0460 (13)
C10	0.9220 (2)	−0.1313 (6)	0.56069 (10)	0.0417 (11)
C11	0.67371 (18)	0.8433 (5)	0.61950 (8)	0.0260 (9)
C12	0.70569 (19)	0.7317 (5)	0.65715 (7)	0.0239 (9)
C13	0.6843 (2)	0.8137 (5)	0.69426 (8)	0.0294 (10)
C14	0.6314 (2)	1.0036 (6)	0.69274 (9)	0.0329 (10)
C15	0.6020 (2)	1.1148 (5)	0.65539 (9)	0.0329 (10)
C16	0.62311 (19)	1.0343 (5)	0.61810 (8)	0.0290 (9)
C17	0.5923 (2)	1.1604 (6)	0.57752 (8)	0.0381 (11)
O5	0.48488 (15)	0.3516 (4)	0.77309 (5)	0.0463 (8)
O6	0.65278 (14)	0.7820 (4)	0.79689 (5)	0.0320 (7)
N5	0.65874 (15)	0.5554 (4)	0.87388 (6)	0.0237 (7)
N6	0.60151 (16)	0.4768 (4)	0.84100 (6)	0.0242 (7)
C18	0.70644 (18)	0.7387 (5)	0.87009 (7)	0.0221 (9)
C19	0.70315 (19)	0.8573 (5)	0.83094 (8)	0.0258 (9)
C20	0.7571 (2)	1.0531 (5)	0.83189 (9)	0.0328 (10)
C21	0.8074 (2)	1.1348 (5)	0.86792 (9)	0.0334 (10)
C22	0.81280 (19)	1.0263 (5)	0.90750 (8)	0.0296 (10)
C23	0.76401 (18)	0.8269 (5)	0.90856 (8)	0.0271 (9)
C24	0.7715 (2)	0.7172 (6)	0.94742 (8)	0.0318 (10)
C25	0.8247 (2)	0.8060 (7)	0.98344 (9)	0.0409 (13)
C26	0.8725 (2)	1.0028 (7)	0.98229 (9)	0.0445 (13)
C27	0.8668 (2)	1.1131 (6)	0.94502 (10)	0.0398 (11)
C28	0.55747 (18)	0.1612 (5)	0.88028 (8)	0.0253 (9)
C29	0.54976 (19)	0.2860 (5)	0.84352 (8)	0.0241 (9)
C30	0.4884 (2)	0.2180 (5)	0.80699 (8)	0.0290 (9)
C31	0.4377 (2)	0.0253 (5)	0.80731 (8)	0.0328 (10)
C32	0.4475 (2)	−0.0984 (5)	0.84354 (8)	0.0313 (10)
C33	0.5071 (2)	−0.0301 (5)	0.88087 (8)	0.0274 (9)
C34	0.5164 (2)	−0.1643 (6)	0.92034 (8)	0.0367 (10)
H1	0.781 (2)	0.481 (5)	0.6851 (5)	0.0489*
H2	0.70371	0.75370	0.74970	0.0619*
H3	0.94842	−0.10365	0.69920	0.0376*
H4	0.97170	−0.26203	0.63954	0.0423*
H7	0.78964	0.39927	0.55271	0.0386*
H8	0.81957	0.22875	0.49355	0.0487*
H9	0.90187	−0.09938	0.49818	0.0552*
H10	0.95517	−0.26348	0.56240	0.0499*
H11	0.68711	0.78663	0.59490	0.0311*
H14	0.61529	1.05717	0.71705	0.0396*
H15	0.56774	1.24489	0.65496	0.0396*
H17A	0.55759	1.28918	0.58247	0.0573*
H17B	0.55310	1.06748	0.55729	0.0573*
H17C	0.64657	1.20441	0.56707	0.0573*
H5	0.44769	0.30035	0.75300	0.0694*
H6	0.598 (2)	0.545 (5)	0.8168 (5)	0.0489*
H20	0.75780	1.12678	0.80695	0.0393*
H21	0.83982	1.26671	0.86719	0.0401*
H24	0.74025	0.58398	0.94863	0.0381*
H25	0.82845	0.73308	1.00881	0.0489*
H26	0.90867	1.06058	1.00680	0.0532*
H27	0.89877	1.24589	0.94449	0.0476*
H28	0.59739	0.20899	0.90469	0.0303*
H31	0.39691	−0.02143	0.78307	0.0393*
H32	0.41389	−0.22936	0.84320	0.0375*
H34A	0.47613	−0.29120	0.91504	0.0551*
H34B	0.49865	−0.07553	0.94183	0.0551*
H34C	0.58041	−0.21161	0.92933	0.0551*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0407 (12)	0.0334 (14)	0.0234 (10)	0.0083 (11)	0.0008 (8)	0.0036 (9)
O2	0.0582 (14)	0.0441 (16)	0.0211 (10)	0.0199 (12)	0.0074 (9)	0.0021 (9)
N1	0.0326 (14)	0.0233 (15)	0.0205 (11)	0.0021 (12)	0.0034 (10)	0.0014 (10)
N2	0.0271 (13)	0.0227 (15)	0.0225 (11)	−0.0016 (11)	0.0046 (9)	−0.0026 (10)
C1	0.0230 (14)	0.0216 (17)	0.0234 (13)	−0.0017 (13)	0.0017 (10)	−0.0033 (11)
C2	0.0272 (15)	0.0227 (18)	0.0289 (14)	−0.0002 (13)	0.0036 (11)	0.0022 (12)
C3	0.0305 (16)	0.0249 (19)	0.0352 (15)	0.0003 (14)	−0.0011 (12)	0.0072 (13)
C4	0.0309 (17)	0.0232 (19)	0.0505 (18)	0.0022 (15)	0.0055 (14)	−0.0014 (14)
C5	0.0243 (15)	0.028 (2)	0.0412 (16)	−0.0043 (14)	0.0054 (12)	−0.0087 (14)
C6	0.0255 (15)	0.0253 (19)	0.0278 (14)	−0.0042 (13)	0.0007 (11)	−0.0077 (12)
C7	0.0341 (16)	0.035 (2)	0.0264 (14)	−0.0017 (15)	0.0028 (12)	−0.0045 (13)
C8	0.0388 (18)	0.053 (3)	0.0277 (15)	−0.0015 (18)	0.0021 (13)	−0.0096 (15)
C9	0.0393 (19)	0.058 (3)	0.0396 (18)	−0.0005 (19)	0.0056 (15)	−0.0256 (17)
C10	0.0335 (18)	0.036 (2)	0.055 (2)	0.0026 (16)	0.0075 (15)	−0.0217 (16)
C11	0.0275 (15)	0.0258 (18)	0.0242 (13)	−0.0018 (14)	0.0045 (11)	0.0009 (12)
C12	0.0259 (14)	0.0203 (17)	0.0254 (13)	0.0013 (13)	0.0052 (11)	−0.0005 (11)
C13	0.0329 (16)	0.028 (2)	0.0274 (14)	0.0023 (15)	0.0065 (12)	0.0018 (12)
C14	0.0348 (17)	0.031 (2)	0.0335 (15)	0.0025 (15)	0.0087 (13)	−0.0045 (13)
C15	0.0305 (16)	0.0223 (19)	0.0460 (17)	0.0037 (14)	0.0078 (13)	0.0015 (14)
C16	0.0237 (15)	0.0267 (19)	0.0362 (15)	−0.0006 (14)	0.0052 (12)	0.0091 (13)
C17	0.0390 (18)	0.034 (2)	0.0411 (17)	0.0098 (16)	0.0079 (14)	0.0145 (14)
O5	0.0615 (15)	0.0451 (16)	0.0242 (10)	−0.0219 (13)	−0.0100 (10)	0.0046 (10)
O6	0.0402 (12)	0.0312 (14)	0.0244 (10)	−0.0030 (10)	0.0061 (8)	0.0013 (9)
N5	0.0246 (12)	0.0242 (15)	0.0209 (10)	−0.0002 (11)	0.0018 (9)	−0.0020 (10)
N6	0.0290 (13)	0.0226 (15)	0.0188 (10)	−0.0024 (11)	−0.0002 (10)	−0.0003 (10)
C18	0.0240 (14)	0.0196 (17)	0.0225 (13)	0.0014 (13)	0.0044 (10)	−0.0018 (11)
C19	0.0286 (15)	0.0236 (18)	0.0258 (14)	0.0041 (14)	0.0067 (11)	−0.0002 (12)
C20	0.0340 (17)	0.0259 (19)	0.0403 (16)	−0.0018 (15)	0.0121 (14)	0.0067 (14)
C21	0.0298 (16)	0.0188 (18)	0.0541 (18)	−0.0031 (14)	0.0144 (14)	−0.0020 (14)
C22	0.0276 (16)	0.0257 (19)	0.0364 (15)	0.0008 (14)	0.0085 (12)	−0.0077 (13)
C23	0.0231 (15)	0.0278 (19)	0.0293 (14)	0.0016 (13)	0.0028 (11)	−0.0093 (12)
C24	0.0301 (16)	0.037 (2)	0.0271 (14)	−0.0033 (15)	0.0034 (12)	−0.0060 (13)
C25	0.0365 (18)	0.059 (3)	0.0262 (15)	−0.0017 (18)	0.0040 (12)	−0.0110 (15)
C26	0.0336 (18)	0.063 (3)	0.0361 (17)	−0.0065 (18)	0.0055 (14)	−0.0266 (17)
C27	0.0325 (17)	0.033 (2)	0.0536 (19)	−0.0080 (16)	0.0085 (14)	−0.0188 (16)
C28	0.0251 (15)	0.0258 (18)	0.0237 (13)	0.0019 (13)	0.0022 (11)	0.0017 (12)
C29	0.0250 (14)	0.0210 (17)	0.0254 (13)	0.0002 (13)	0.0030 (11)	−0.0023 (11)
C30	0.0345 (16)	0.0289 (19)	0.0217 (13)	−0.0034 (15)	0.0013 (11)	−0.0002 (12)
C31	0.0326 (17)	0.032 (2)	0.0313 (15)	−0.0076 (15)	0.0006 (12)	−0.0062 (13)
C32	0.0290 (16)	0.0216 (18)	0.0426 (16)	−0.0057 (14)	0.0060 (13)	0.0007 (13)
C33	0.0269 (15)	0.0209 (18)	0.0356 (15)	0.0038 (14)	0.0090 (12)	0.0042 (12)
C34	0.0333 (17)	0.033 (2)	0.0441 (17)	−0.0015 (16)	0.0088 (13)	0.0099 (14)

Geometric parameters (Å, º) top

O1—C2	1.279 (3)	C10—H10	0.9300
O2—C13	1.363 (3)	C11—H11	0.9300
O2—H2	0.8200	C14—H14	0.9300
O5—C30	1.363 (4)	C15—H15	0.9300
O6—C19	1.282 (3)	C17—H17B	0.9600
O5—H5	0.8200	C17—H17A	0.9600
N1—C12	1.385 (4)	C17—H17C	0.9600
N1—N2	1.308 (3)	C18—C19	1.458 (4)
N2—C1	1.336 (4)	C18—C23	1.459 (4)
N1—H1	0.88 (2)	C19—C20	1.418 (4)
N5—C18	1.328 (4)	C20—C21	1.345 (4)
N5—N6	1.305 (3)	C21—C22	1.437 (4)
N6—C29	1.390 (4)	C22—C27	1.413 (4)
N6—H6	0.88 (2)	C22—C23	1.404 (4)
C1—C2	1.446 (4)	C23—C24	1.416 (4)
C1—C6	1.460 (4)	C24—C25	1.377 (4)
C2—C3	1.433 (4)	C25—C26	1.383 (6)
C3—C4	1.351 (4)	C26—C27	1.375 (5)
C4—C5	1.439 (4)	C28—C33	1.372 (4)
C5—C10	1.414 (5)	C28—C29	1.402 (4)
C5—C6	1.406 (4)	C29—C30	1.396 (4)
C6—C7	1.413 (4)	C30—C31	1.381 (4)
C7—C8	1.384 (4)	C31—C32	1.382 (4)
C8—C9	1.387 (6)	C32—C33	1.404 (4)
C9—C10	1.377 (5)	C33—C34	1.505 (4)
C11—C12	1.395 (4)	C20—H20	0.9300
C11—C16	1.366 (4)	C21—H21	0.9300
C12—C13	1.402 (4)	C24—H24	0.9300
C13—C14	1.378 (5)	C25—H25	0.9300
C14—C15	1.381 (4)	C26—H26	0.9300
C15—C16	1.402 (4)	C27—H27	0.9300
C16—C17	1.514 (4)	C28—H28	0.9300
C3—H3	0.9300	C31—H31	0.9300
C4—H4	0.9300	C32—H32	0.9300
C7—H7	0.9300	C34—H34A	0.9600
C8—H8	0.9300	C34—H34B	0.9600
C9—H9	0.9300	C34—H34C	0.9600

O1···N1	2.536 (4)	C17···H9^vi	2.8800
O1···N2	2.843 (4)	C18···H34C^iv	2.9400
O1···O5ⁱ	2.622 (3)	C19···H2	2.7300
O2···O6	2.631 (3)	C19···H6	2.42 (3)
O2···N1	2.614 (4)	C20···H32ⁱ	2.9700
O5···C3ⁱⁱ	3.373 (4)	C21···H32ⁱ	3.1000
O5···O1ⁱⁱ	2.622 (3)	C22···H34Aⁱ	2.7400
O5···N6	2.611 (4)	C23···H34C^iv	2.9000
O5···C2ⁱⁱ	3.344 (4)	C23···H34Aⁱ	3.0600
O6···N6	2.546 (4)	C24···H34C^iv	2.7500
O6···N5	2.848 (4)	C25···H24^vii	3.0800
O6···O2	2.631 (3)	C26···H24^vii	3.0900
O1···H1	1.82 (3)	C27···H34Aⁱ	2.8100
O1···H5ⁱ	1.8100	C31···H21^viii	2.9300
O2···H1	2.26 (3)	C32···H21^viii	2.7500
O5···H3ⁱⁱ	2.8100	C33···H21^viii	2.8700
O5···H6	2.27 (3)	C34···H26^ix	2.9200
O6···H6	1.82 (3)	H1···O2	2.26 (3)
O6···H2	1.8500	H1···C2	2.40 (3)
N1···C15ⁱⁱⁱ	3.446 (5)	H1···O1	1.82 (3)
N1···O1	2.536 (4)	H2···H14	2.3700
N1···O2	2.614 (4)	H2···O6	1.8500
N2···O1	2.843 (4)	H2···C19	2.7300
N2···C4^iv	3.372 (5)	H3···O5ⁱ	2.8100
N2···C16ⁱⁱⁱ	3.398 (5)	H3···H5ⁱ	2.5400
N2···C17ⁱⁱⁱ	3.402 (5)	H4···C15ⁱ	2.8300
N5···O6	2.848 (4)	H4···H10	2.4800
N5···C33^iv	3.378 (5)	H4···C14ⁱ	2.9800
N5···C34^iv	3.279 (5)	H4···C16ⁱ	2.9500
N5···C21ⁱⁱⁱ	3.371 (5)	H5···C2ⁱⁱ	2.6300
N6···O5	2.611 (4)	H5···C3ⁱⁱ	2.9100
N6···O6	2.546 (4)	H5···H3ⁱⁱ	2.5400
N6···C32^iv	3.422 (5)	H5···H31	2.3700
N2···H7	2.4900	H5···O1ⁱⁱ	1.8100
N2···H11	2.5700	H6···C19	2.42 (3)
N2···H17Cⁱⁱⁱ	2.9100	H6···O5	2.27 (3)
N5···H34C^iv	2.7200	H6···O6	1.82 (3)
N5···H24	2.4900	H7···N2	2.4900
N5···H28	2.5600	H7···H17Cⁱⁱⁱ	2.5200
C1···C11ⁱⁱⁱ	3.445 (5)	H9···C17^x	2.8800
C1···C16ⁱⁱⁱ	3.334 (5)	H9···H17C^x	2.4100
C2···C12ⁱⁱⁱ	3.533 (5)	H10···H4	2.4800
C2···O5ⁱ	3.344 (4)	H10···C17ⁱ	3.1000
C3···O5ⁱ	3.373 (4)	H10···H17Bⁱ	2.3500
C3···C12ⁱⁱⁱ	3.413 (5)	H11···N2	2.5700
C4···N2ⁱⁱⁱ	3.372 (5)	H14···H2	2.3700
C6···C11ⁱⁱⁱ	3.504 (5)	H15···H17A	2.3500
C11···C6^iv	3.504 (5)	H15···C2^viii	3.0700
C11···C1^iv	3.445 (5)	H15···C3^viii	2.8900
C12···C3^iv	3.413 (5)	H15···C4^viii	2.9700
C12···C2^iv	3.533 (5)	H17A···H15	2.3500
C15···N1^iv	3.446 (5)	H17A···C5^viii	2.8000
C16···C1^iv	3.334 (5)	H17A···C6^viii	3.0800
C16···N2^iv	3.398 (5)	H17A···C10^viii	2.8500
C17···N2^iv	3.402 (5)	H17B···H10ⁱⁱ	2.3500
C18···C33^iv	3.302 (5)	H17C···N2^iv	2.9100
C18···C28^iv	3.411 (5)	H17C···C6^iv	2.9800
C18···C34^iv	3.540 (5)	H17C···C7^iv	2.6900
C19···C28^iv	3.445 (5)	H17C···H7^iv	2.5200
C19···C29^iv	3.500 (5)	H17C···H9^vi	2.4100
C20···C29^iv	3.419 (5)	H21···H27	2.4900
C21···N5^iv	3.371 (5)	H21···C31^v	2.9300
C23···C28^iv	3.581 (5)	H21···C32^v	2.7500
C28···C19ⁱⁱⁱ	3.445 (5)	H21···C33^v	2.8700
C28···C18ⁱⁱⁱ	3.411 (5)	H24···N5	2.4900
C28···C23ⁱⁱⁱ	3.581 (5)	H24···H34C^iv	2.5900
C29···C19ⁱⁱⁱ	3.500 (5)	H24···C25^xi	3.0800
C29···C20ⁱⁱⁱ	3.419 (5)	H24···C26^xi	3.0900
C32···N6ⁱⁱⁱ	3.422 (5)	H26···C34^xii	2.9200
C33···C18ⁱⁱⁱ	3.302 (5)	H26···H34C^xii	2.4800
C33···N5ⁱⁱⁱ	3.378 (5)	H27···H21	2.4900
C34···N5ⁱⁱⁱ	3.279 (5)	H27···H34B^v	2.4800
C34···C18ⁱⁱⁱ	3.540 (5)	H28···N5	2.5600
C2···H15^v	3.0700	H31···H5	2.3700
C2···H1	2.40 (3)	H32···H34A	2.3600
C2···H5ⁱ	2.6300	H32···C20ⁱⁱ	2.9700
C3···H15^v	2.8900	H32···C21ⁱⁱ	3.1000
C3···H5ⁱ	2.9100	H34A···H32	2.3600
C4···H15^v	2.9700	H34A···C22ⁱⁱ	2.7400
C5···H17A^v	2.8000	H34A···C23ⁱⁱ	3.0600
C6···H17A^v	3.0800	H34A···C27ⁱⁱ	2.8100
C6···H17Cⁱⁱⁱ	2.9800	H34B···H27^viii	2.4800
C7···H17Cⁱⁱⁱ	2.6900	H34C···N5ⁱⁱⁱ	2.7200
C10···H17A^v	2.8500	H34C···C18ⁱⁱⁱ	2.9400
C14···H4ⁱⁱ	2.9800	H34C···C23ⁱⁱⁱ	2.9000
C15···H4ⁱⁱ	2.8300	H34C···C24ⁱⁱⁱ	2.7500
C16···H4ⁱⁱ	2.9500	H34C···H24ⁱⁱⁱ	2.5900
C17···H10ⁱⁱ	3.1000	H34C···H26^ix	2.4800

C13—O2—H2	109.00	H17B—C17—H17C	109.00
C30—O5—H5	109.00	C16—C17—H17A	109.00
N2—N1—C12	121.5 (2)	C16—C17—H17B	109.00
N1—N2—C1	118.8 (2)	H17A—C17—H17B	109.00
N2—N1—H1	118.1 (18)	C16—C17—H17C	109.00
C12—N1—H1	120.4 (18)	N5—C18—C23	116.4 (2)
N6—N5—C18	119.0 (2)	C19—C18—C23	118.9 (3)
N5—N6—C29	121.0 (2)	N5—C18—C19	124.7 (2)
N5—N6—H6	118.3 (18)	O6—C19—C20	122.1 (3)
C29—N6—H6	120.6 (18)	O6—C19—C18	119.6 (3)
N2—C1—C6	115.9 (2)	C18—C19—C20	118.3 (2)
C2—C1—C6	119.8 (3)	C19—C20—C21	121.7 (3)
N2—C1—C2	124.4 (2)	C20—C21—C22	122.5 (3)
O1—C2—C3	121.6 (2)	C23—C22—C27	119.5 (3)
C1—C2—C3	118.3 (2)	C21—C22—C23	118.7 (2)
O1—C2—C1	120.1 (3)	C21—C22—C27	121.8 (3)
C2—C3—C4	121.2 (3)	C18—C23—C22	119.8 (2)
C3—C4—C5	122.2 (3)	C18—C23—C24	121.6 (3)
C4—C5—C6	119.5 (3)	C22—C23—C24	118.6 (3)
C4—C5—C10	121.0 (3)	C23—C24—C25	120.5 (3)
C6—C5—C10	119.5 (3)	C24—C25—C26	120.7 (3)
C1—C6—C7	121.7 (3)	C25—C26—C27	120.2 (3)
C1—C6—C5	119.0 (2)	C22—C27—C26	120.5 (3)
C5—C6—C7	119.3 (3)	C29—C28—C33	121.2 (2)
C6—C7—C8	119.6 (3)	N6—C29—C28	123.3 (2)
C7—C8—C9	121.3 (3)	N6—C29—C30	116.9 (2)
C8—C9—C10	120.1 (3)	C28—C29—C30	119.8 (3)
C5—C10—C9	120.2 (3)	O5—C30—C29	115.4 (3)
C12—C11—C16	121.3 (2)	O5—C30—C31	125.2 (2)
N1—C12—C11	123.5 (2)	C29—C30—C31	119.4 (3)
N1—C12—C13	116.7 (2)	C30—C31—C32	120.2 (3)
C11—C12—C13	119.8 (3)	C31—C32—C33	121.3 (3)
O2—C13—C14	125.3 (2)	C28—C33—C32	118.2 (2)
C12—C13—C14	119.1 (3)	C28—C33—C34	120.9 (2)
O2—C13—C12	115.6 (3)	C32—C33—C34	121.0 (3)
C13—C14—C15	120.5 (3)	C19—C20—H20	119.00
C14—C15—C16	120.9 (3)	C21—C20—H20	119.00
C15—C16—C17	120.4 (3)	C20—C21—H21	119.00
C11—C16—C15	118.5 (3)	C22—C21—H21	119.00
C11—C16—C17	121.1 (2)	C23—C24—H24	120.00
C4—C3—H3	119.00	C25—C24—H24	120.00
C2—C3—H3	119.00	C24—C25—H25	120.00
C5—C4—H4	119.00	C26—C25—H25	120.00
C3—C4—H4	119.00	C25—C26—H26	120.00
C6—C7—H7	120.00	C27—C26—H26	120.00
C8—C7—H7	120.00	C22—C27—H27	120.00
C7—C8—H8	119.00	C26—C27—H27	120.00
C9—C8—H8	119.00	C29—C28—H28	119.00
C8—C9—H9	120.00	C33—C28—H28	119.00
C10—C9—H9	120.00	C30—C31—H31	120.00
C5—C10—H10	120.00	C32—C31—H31	120.00
C9—C10—H10	120.00	C31—C32—H32	119.00
C16—C11—H11	119.00	C33—C32—H32	119.00
C12—C11—H11	119.00	C33—C34—H34A	109.00
C13—C14—H14	120.00	C33—C34—H34B	109.00
C15—C14—H14	120.00	C33—C34—H34C	109.00
C14—C15—H15	120.00	H34A—C34—H34B	109.00
C16—C15—H15	120.00	H34A—C34—H34C	109.00
H17A—C17—H17C	109.00	H34B—C34—H34C	109.00

C12—N1—N2—C1	−179.4 (3)	O2—C13—C14—C15	177.8 (3)
N2—N1—C12—C11	−2.7 (4)	C12—C13—C14—C15	−1.7 (5)
N2—N1—C12—C13	178.8 (3)	C13—C14—C15—C16	1.7 (5)
N1—N2—C1—C2	−2.1 (4)	C14—C15—C16—C17	−178.7 (3)
N1—N2—C1—C6	177.4 (2)	C14—C15—C16—C11	−0.2 (4)
N6—N5—C18—C19	−2.8 (4)	N5—C18—C19—O6	−1.4 (4)
N6—N5—C18—C23	175.7 (2)	N5—C18—C19—C20	179.1 (3)
C18—N5—N6—C29	−179.7 (3)	C23—C18—C19—O6	−179.9 (3)
N5—N6—C29—C28	−2.5 (4)	C23—C18—C19—C20	0.6 (4)
N5—N6—C29—C30	178.2 (3)	N5—C18—C23—C22	−176.8 (3)
N2—C1—C6—C5	−176.5 (3)	N5—C18—C23—C24	2.6 (4)
N2—C1—C6—C7	2.7 (4)	C19—C18—C23—C22	1.8 (4)
N2—C1—C2—O1	−2.6 (4)	C19—C18—C23—C24	−178.8 (3)
N2—C1—C2—C3	177.7 (3)	O6—C19—C20—C21	177.9 (3)
C6—C1—C2—O1	177.9 (3)	C18—C19—C20—C21	−2.7 (4)
C6—C1—C2—C3	−1.9 (4)	C19—C20—C21—C22	2.3 (5)
C2—C1—C6—C5	3.1 (4)	C20—C21—C22—C23	0.3 (4)
C2—C1—C6—C7	−177.7 (3)	C20—C21—C22—C27	179.3 (3)
C1—C2—C3—C4	−0.3 (4)	C21—C22—C23—C18	−2.3 (4)
O1—C2—C3—C4	180.0 (3)	C21—C22—C23—C24	178.3 (3)
C2—C3—C4—C5	1.2 (5)	C27—C22—C23—C18	178.7 (3)
C3—C4—C5—C6	0.0 (5)	C27—C22—C23—C24	−0.8 (4)
C3—C4—C5—C10	178.7 (3)	C21—C22—C27—C26	−178.4 (3)
C4—C5—C6—C7	178.6 (3)	C23—C22—C27—C26	0.6 (5)
C4—C5—C6—C1	−2.2 (4)	C18—C23—C24—C25	−178.7 (3)
C10—C5—C6—C7	−0.1 (4)	C22—C23—C24—C25	0.8 (4)
C4—C5—C10—C9	−178.8 (3)	C23—C24—C25—C26	−0.6 (5)
C10—C5—C6—C1	179.1 (3)	C24—C25—C26—C27	0.5 (5)
C6—C5—C10—C9	−0.1 (5)	C25—C26—C27—C22	−0.5 (5)
C5—C6—C7—C8	0.4 (4)	C33—C28—C29—N6	−177.9 (3)
C1—C6—C7—C8	−178.8 (3)	C33—C28—C29—C30	1.4 (4)
C6—C7—C8—C9	−0.4 (5)	C29—C28—C33—C32	0.1 (4)
C7—C8—C9—C10	0.1 (5)	C29—C28—C33—C34	179.4 (3)
C8—C9—C10—C5	0.2 (5)	N6—C29—C30—O5	−1.6 (4)
C16—C11—C12—N1	−177.3 (3)	N6—C29—C30—C31	177.7 (3)
C12—C11—C16—C17	177.2 (3)	C28—C29—C30—O5	179.1 (3)
C12—C11—C16—C15	−1.3 (4)	C28—C29—C30—C31	−1.6 (4)
C16—C11—C12—C13	1.2 (4)	O5—C30—C31—C32	179.4 (3)
N1—C12—C13—C14	178.9 (3)	C29—C30—C31—C32	0.2 (4)
N1—C12—C13—O2	−0.6 (4)	C30—C31—C32—C33	1.4 (5)
C11—C12—C13—C14	0.3 (4)	C31—C32—C33—C28	−1.5 (4)
C11—C12—C13—O2	−179.3 (3)	C31—C32—C33—C34	179.2 (3)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x−1/2, −y+1/2, z; (iii) x, y−1, z; (iv) x, y+1, z; (v) x+1/2, −y+3/2, z; (vi) −x+3/2, y+3/2, −z+1; (vii) −x+3/2, y+1/2, −z+2; (viii) x−1/2, −y+3/2, z; (ix) −x+3/2, y−3/2, −z+2; (x) −x+3/2, y−3/2, −z+1; (xi) −x+3/2, y−1/2, −z+2; (xii) −x+3/2, y+3/2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88 (2)	1.82 (3)	2.536 (4)	138 (2)
O2—H2···O6	0.82	1.85	2.631 (3)	159
O5—H5···O1ⁱⁱ	0.82	1.81	2.622 (3)	168
N6—H6···O6	0.88 (2)	1.82 (3)	2.546 (4)	138 (2)

Symmetry code: (ii) x−1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88 (2)	1.82 (3)	2.536 (4)	138 (2)
O2—H2···O6	0.82	1.85	2.631 (3)	159
O5—H5···O1ⁱ	0.82	1.81	2.622 (3)	168
N6—H6···O6	0.88 (2)	1.82 (3)	2.546 (4)	138 (2)

Symmetry code: (i) x−1/2, −y+1/2, z.

Acknowledgements

We thank all researchers of the CHEMS Research Unit, University of Constantine, Algeria, for their valuable assistance. Thanks are due to the MESRS (Ministère de l'Enseignement Supérieur et de la Recherche Scientifique –Algérie) for financial support. We also express our gratitude to Professor L. 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

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Herbst, W. & Hunger, K. (2004). Industrial Organic Pigments, pp. 183–419. Weinheim: VCH. Google Scholar
Karadayı, N., Albayrak, Ç., Odabaşoğlu, M. & Büyükgüngör, O. (2006). Acta Cryst. E62, o3695–o3696. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lee, S. H., Kim, J. Y., Ko, J., Lee, J. Y. & Kim, J. S. (2004). J. Org. Chem. 69, 2902–2905. Web of Science CrossRef PubMed CAS Google Scholar
Oakes, J. (2002). Rev. Prog. Color. pp. 32-63. Google Scholar
Olivieri, A. C., Wilson, R. B., Paul, I. C. & Curtin, D. Y. (1989). J. Am. Chem. Soc. 111, 5525–5532. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2002). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, M., Funabiki, K. & Matsui, M. (2003). Dyes Pigments, 57, 77–86. Web of Science CrossRef CAS Google Scholar
Yazıcı, S., Albayrak, Ç., Gümrükçüoğlu, İ., Şenel, İ. & Büyükgüngör, O. (2010). Acta Cryst. E66, o559–o560. Web of Science CSD CrossRef IUCr Journals Google Scholar