1-[(Phenyl­iminio)amino]-2-naphtho­late

Xu, J.-J.; Li, J.; Pi, M.; Jin, C.-M.

doi:10.1107/S1600536810023329

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1752

doi:10.1107/S1600536810023329

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1-[(Phenyliminio)amino]-2-naphtholate

Ji-Jun Xu,^a Jun Li,^a Min Pi ^a and Chuan-Ming Jin ^a ^*

^aHubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Environmental Engineering, Hubei Normal University, Huangshi, Hubei 435002, People's Republic of China
^*Correspondence e-mail: cmjin@email.hbnu.edu.cn

(Received 10 June 2010; accepted 16 June 2010; online 23 June 2010)

In the zwitterionic title compound, C₁₆H₁₂N₂O, the dihedral angle between the benzene ring and naphthalene ring system is 2.0 (1)°. The azo group adopts a trans configuration and an intramolecular N—H⋯O hydrogen bond is found. In the crystal, the molecules are packed by strong π–π interactions [centroid–centroid distance between aromatic rings = 3.375 (3) Å].

Related literature

For general background to the use of azo compounds as dyes, pigments and advanced materials, see: Lee et al. (2004 ); Oueslati et al. (2004 ). Many azo compounds have been synthesized by diazotization and diazo coupling reactions, see: Wang et al. (2003 ).

Experimental

Crystal data

C₁₆H₁₂N₂O
M_r = 248.28
Monoclinic, C 2/c
a = 27.8713 (4) Å
b = 6.0248 (1) Å
c = 14.9199 (2) Å
β = 103.570 (2)°
V = 2435.40 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.13 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.989, T_max = 0.993
8859 measured reflections
3002 independent reflections
2536 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.169
S = 1.08
3002 reflections
175 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.895 (19)	1.803 (18)	2.5545 (17)	140.0 (16)

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023329/rk2210sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023329/rk2210Isup2.hkl

checkCIF report

Comment top

Azo-compounds are very important in the fields of dyes, pigments and advanced materials (Lee et al., 2004; Oueslati et al., 2004). Azo-dyes are synthetic pigments that contain an azo-group, as part of the structure. Azo-groups do not occur naturally. Many azo-compounds have been synthesized by the diazotization and diazo coupling reaction (Wang et al., 2003). The title compound, I, was obtained through the diazotization of aniline followed by a coupling reaction with 2-naphthol.

The molecular structure of I is illustrated in Fig. 1. The molecule adopts an anti–configuration with the two aryl groups reside on the opposite side of azo–group. The dihedral angle between the benzene ring and naphthalene ring is 2.0 (1)°. An intramolecular N—H···O hydrogen bond is found (Table 1). It is more interesting, that hydrogen atom in the OH-group has transfer to N atom in the azo-group to form the structure of dipolar ion. Moreover, different Fourier map indicate hydrogen site location is closer to nitrogen atom of azo-group. In the crystal molecules are packed by the weak π–π interactions with the closest approach between centroids of aromatic rings is 3.375 (3)Å.

Related literature top

For general background to the use of azo compounds as dyes, pigments and advanced materials, see: Lee et al., (2004); Oueslati et al., (2004). Many azo compounds have been synthesized by diazotization and diazo coupling reactions, see: Wang et al., (2003).

Experimental top

The title compound was prepared by a similar method of other aromatic azo–compounds (Wang et al., 2003). Single crystals of I were obtained by slow evaporation from a petroleum ether ethyl acetate (2/1 v/v) solution system.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (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

Fig. 1. The structure of title compound showing the atom–numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

1-[(Phenyliminio)amino]-2-naphtholate top

Crystal data top

C₁₆H₁₂N₂O	F(000) = 1040
M_r = 248.28	D_x = 1.354 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2783 reflections
a = 27.8713 (4) Å	θ = 2.8–28.2°
b = 6.0248 (1) Å	µ = 0.09 mm⁻¹
c = 14.9199 (2) Å	T = 200 K
β = 103.570 (2)°	Block, red
V = 2435.40 (7) Å³	0.13 × 0.10 × 0.08 mm
Z = 8

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3002 independent reflections
Radiation source: fine–focus sealed tube	2536 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −35→36
T_min = 0.989, T_max = 0.993	k = −8→8
8859 measured reflections	l = −15→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0799P)² + 1.0846P] where P = (F_o² + 2F_c²)/3
3002 reflections	(Δ/σ)_max = 0.001
175 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₆H₁₂N₂O	V = 2435.40 (7) Å³
M_r = 248.28	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 27.8713 (4) Å	µ = 0.09 mm⁻¹
b = 6.0248 (1) Å	T = 200 K
c = 14.9199 (2) Å	0.13 × 0.10 × 0.08 mm
β = 103.570 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3002 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2536 reflections with I > 2σ(I)
T_min = 0.989, T_max = 0.993	R_int = 0.088
8859 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.48 e Å⁻³
3002 reflections	Δρ_min = −0.23 e Å⁻³
175 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
C1	0.14696 (5)	0.0629 (2)	0.09018 (10)	0.0244 (3)
C2	0.19947 (5)	0.0124 (3)	0.11604 (10)	0.0287 (3)
C3	0.21439 (6)	−0.1846 (3)	0.17062 (11)	0.0330 (4)
H3	0.2485	−0.2197	0.1901	0.040*
C4	0.18102 (6)	−0.3195 (3)	0.19449 (11)	0.0319 (4)
H4	0.1924	−0.4484	0.2298	0.038*
C5	0.12895 (5)	−0.2771 (2)	0.16900 (10)	0.0256 (3)
C6	0.09522 (6)	−0.4260 (3)	0.19251 (11)	0.0314 (4)
H6	0.1070	−0.5575	0.2256	0.038*
C7	0.04557 (6)	−0.3840 (3)	0.16840 (11)	0.0337 (4)
H7	0.0230	−0.4870	0.1839	0.040*
C8	0.02823 (6)	−0.1896 (3)	0.12098 (11)	0.0324 (4)
H8	−0.0062	−0.1594	0.1052	0.039*
C9	0.06067 (5)	−0.0409 (2)	0.09676 (10)	0.0282 (3)
H9	0.0484	0.0912	0.0648	0.034*
C10	0.11155 (5)	−0.0826 (2)	0.11877 (9)	0.0237 (3)
C11	0.13828 (6)	0.5505 (2)	−0.04777 (9)	0.0255 (3)
C12	0.17170 (6)	0.6926 (3)	−0.07488 (11)	0.0311 (4)
H12	0.2061	0.6623	−0.0576	0.037*
C13	0.15433 (7)	0.8788 (3)	−0.12732 (11)	0.0355 (4)
H13	0.1769	0.9765	−0.1460	0.043*
C14	0.10432 (6)	0.9226 (3)	−0.15249 (11)	0.0340 (4)
H14	0.0925	1.0507	−0.1879	0.041*
C15	0.07150 (6)	0.7790 (3)	−0.12588 (11)	0.0329 (4)
H15	0.0371	0.8088	−0.1438	0.039*
C16	0.08806 (6)	0.5922 (2)	−0.07338 (11)	0.0292 (3)
H16	0.0653	0.4944	−0.0553	0.035*
N1	0.12797 (5)	0.23592 (19)	0.03768 (8)	0.0253 (3)
N2	0.15775 (5)	0.3675 (2)	0.00730 (9)	0.0268 (3)
H2A	0.1899 (7)	0.333 (3)	0.0227 (13)	0.032*
O1	0.23107 (4)	0.1341 (2)	0.09144 (9)	0.0387 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0285 (7)	0.0253 (7)	0.0190 (7)	0.0024 (5)	0.0050 (5)	−0.0008 (5)
C2	0.0281 (7)	0.0323 (8)	0.0243 (7)	0.0009 (6)	0.0030 (6)	−0.0012 (6)
C3	0.0263 (7)	0.0406 (9)	0.0288 (8)	0.0067 (6)	−0.0003 (6)	0.0043 (7)
C4	0.0357 (8)	0.0321 (8)	0.0255 (8)	0.0084 (6)	0.0020 (6)	0.0068 (6)
C5	0.0327 (8)	0.0274 (7)	0.0166 (7)	0.0027 (6)	0.0058 (6)	−0.0008 (5)
C6	0.0416 (9)	0.0292 (7)	0.0250 (8)	0.0036 (6)	0.0110 (6)	0.0037 (6)
C7	0.0381 (9)	0.0335 (8)	0.0329 (9)	−0.0032 (6)	0.0151 (7)	0.0020 (6)
C8	0.0292 (8)	0.0388 (9)	0.0306 (8)	0.0029 (6)	0.0097 (6)	0.0001 (6)
C9	0.0300 (7)	0.0307 (7)	0.0241 (7)	0.0059 (6)	0.0069 (6)	0.0034 (6)
C10	0.0292 (7)	0.0258 (7)	0.0163 (6)	0.0032 (5)	0.0059 (5)	−0.0013 (5)
C11	0.0351 (8)	0.0239 (7)	0.0184 (7)	0.0026 (6)	0.0080 (6)	−0.0009 (5)
C12	0.0343 (8)	0.0324 (8)	0.0284 (8)	0.0010 (6)	0.0113 (6)	0.0007 (6)
C13	0.0489 (10)	0.0314 (8)	0.0304 (8)	−0.0022 (7)	0.0180 (7)	0.0031 (6)
C14	0.0521 (10)	0.0271 (7)	0.0232 (8)	0.0076 (7)	0.0100 (7)	0.0030 (6)
C15	0.0387 (8)	0.0315 (8)	0.0274 (8)	0.0071 (6)	0.0057 (7)	−0.0008 (6)
C16	0.0340 (8)	0.0273 (7)	0.0276 (8)	0.0001 (6)	0.0101 (6)	0.0001 (6)
N1	0.0317 (7)	0.0257 (6)	0.0192 (6)	0.0011 (5)	0.0073 (5)	−0.0017 (4)
N2	0.0284 (6)	0.0271 (6)	0.0253 (7)	0.0019 (5)	0.0071 (5)	0.0023 (5)
O1	0.0284 (6)	0.0426 (7)	0.0437 (7)	−0.0017 (5)	0.0058 (5)	0.0084 (5)

Geometric parameters (Å, º) top

C1—N1	1.3364 (18)	C9—C10	1.401 (2)
C1—C2	1.455 (2)	C9—H9	0.9500
C1—C10	1.457 (2)	C11—C16	1.385 (2)
C2—O1	1.2650 (18)	C11—C12	1.393 (2)
C2—C3	1.444 (2)	C11—N2	1.4058 (18)
C3—C4	1.344 (2)	C12—C13	1.389 (2)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.434 (2)	C13—C14	1.381 (2)
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.402 (2)	C14—C15	1.383 (2)
C5—C10	1.4141 (19)	C14—H14	0.9500
C6—C7	1.369 (2)	C15—C16	1.387 (2)
C6—H6	0.9500	C15—H15	0.9500
C7—C8	1.395 (2)	C16—H16	0.9500
C7—H7	0.9500	N1—N2	1.3033 (17)
C8—C9	1.380 (2)	N2—H2A	0.895 (19)
C8—H8	0.9500

N1—C1—C2	123.63 (13)	C10—C9—H9	119.6
N1—C1—C10	116.02 (13)	C9—C10—C5	118.37 (13)
C2—C1—C10	120.32 (13)	C9—C10—C1	122.79 (13)
O1—C2—C3	120.81 (14)	C5—C10—C1	118.82 (13)
O1—C2—C1	121.82 (13)	C16—C11—C12	120.65 (13)
C3—C2—C1	117.37 (13)	C16—C11—N2	122.01 (13)
C4—C3—C2	121.37 (14)	C12—C11—N2	117.33 (14)
C4—C3—H3	119.3	C13—C12—C11	119.46 (15)
C2—C3—H3	119.3	C13—C12—H12	120.3
C3—C4—C5	122.82 (14)	C11—C12—H12	120.3
C3—C4—H4	118.6	C14—C13—C12	120.23 (15)
C5—C4—H4	118.6	C14—C13—H13	119.9
C6—C5—C10	119.73 (14)	C12—C13—H13	119.9
C6—C5—C4	121.06 (13)	C13—C14—C15	119.73 (14)
C10—C5—C4	119.21 (13)	C13—C14—H14	120.1
C7—C6—C5	120.78 (14)	C15—C14—H14	120.1
C7—C6—H6	119.6	C14—C15—C16	120.98 (15)
C5—C6—H6	119.6	C14—C15—H15	119.5
C6—C7—C8	119.79 (14)	C16—C15—H15	119.5
C6—C7—H7	120.1	C11—C16—C15	118.95 (14)
C8—C7—H7	120.1	C11—C16—H16	120.5
C9—C8—C7	120.52 (14)	C15—C16—H16	120.5
C9—C8—H8	119.7	N2—N1—C1	118.77 (12)
C7—C8—H8	119.7	N1—N2—C11	119.36 (13)
C8—C9—C10	120.77 (14)	N1—N2—H2A	116.7 (11)
C8—C9—H9	119.6	C11—N2—H2A	123.9 (11)

N1—C1—C2—O1	1.5 (2)	C4—C5—C10—C1	3.3 (2)
C10—C1—C2—O1	179.23 (13)	N1—C1—C10—C9	−2.8 (2)
N1—C1—C2—C3	−177.99 (13)	C2—C1—C10—C9	179.28 (13)
C10—C1—C2—C3	−0.2 (2)	N1—C1—C10—C5	175.65 (12)
O1—C2—C3—C4	−177.66 (15)	C2—C1—C10—C5	−2.3 (2)
C1—C2—C3—C4	1.8 (2)	C16—C11—C12—C13	0.6 (2)
C2—C3—C4—C5	−0.8 (2)	N2—C11—C12—C13	−178.35 (13)
C3—C4—C5—C6	177.74 (15)	C11—C12—C13—C14	−0.1 (2)
C3—C4—C5—C10	−1.8 (2)	C12—C13—C14—C15	−0.5 (2)
C10—C5—C6—C7	−0.8 (2)	C13—C14—C15—C16	0.6 (2)
C4—C5—C6—C7	179.65 (15)	C12—C11—C16—C15	−0.6 (2)
C5—C6—C7—C8	−0.9 (2)	N2—C11—C16—C15	178.39 (13)
C6—C7—C8—C9	1.1 (2)	C14—C15—C16—C11	−0.1 (2)
C7—C8—C9—C10	0.4 (2)	C2—C1—N1—N2	0.2 (2)
C8—C9—C10—C5	−2.0 (2)	C10—C1—N1—N2	−177.61 (12)
C8—C9—C10—C1	176.43 (13)	C1—N1—N2—C11	−179.81 (12)
C6—C5—C10—C9	2.2 (2)	C16—C11—N2—N1	−2.1 (2)
C4—C5—C10—C9	−178.23 (13)	C12—C11—N2—N1	176.92 (12)
C6—C5—C10—C1	−176.27 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.895 (19)	1.803 (18)	2.5545 (17)	140.0 (16)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂N₂O
M_r	248.28
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	27.8713 (4), 6.0248 (1), 14.9199 (2)
β (°)	103.570 (2)
V (Å³)	2435.40 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.13 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.989, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	8859, 3002, 2536
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.169, 1.08
No. of reflections	3002
No. of parameters	175
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.23

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.895 (19)	1.803 (18)	2.5545 (17)	140.0 (16)

Acknowledgements

We gratefully acknowledge the financial support of the Natural Science Foundation of Hubei Province (2009CDB349, 2006ABB038), the Distinguished Young Scholars Programs, HBDE (Q200722003, Z201022001, CXY2009B028) and the Science and Technology Foundation for Creative Research Group of HBNU (2009).

References

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