1-(4-Hy-droxy-phen-yl)-2-(2-oxidonaphthalen-1-yl)diazen-1-ium methanol hemisolvate.

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 intra-molecular N-H⋯O, rather than an O-H⋯N, hydrogen bond in the mol-ecule. The mol-ecule 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, mol-ecules are linked to and bridged by O-H⋯O hydrogen bonds involving the methanol mol-ecule, which is located about a twofold rotation axis, and hence half-occupied, forming zigzag chains along [001]. Mol-ecules are also linked via C-H⋯π and π-π inter-actions, the latter involving adjacent benzene and naphthalene rings and having a centroid-centroid distance of 3.6616 (13) Å, forming a three-dimensional network.

Related literature

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

Crystal data

C16H12N2O2·0.5CH4O

M = 280.30

Monoclinic,

a = 26.942 (7) Å

b = 6.3479 (17) Å

c = 17.579 (5) Å

β = 113.985 (4)°

V = 2746.8 (13) Å3

Z = 8

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.26 × 0.06 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer

12992 measured reflections

4212 independent reflections

2286 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.154

S = 1.03

4212 reflections

202 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813012245/su2594sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012245/su2594Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813012245/su2594Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H12N2O2·0.5CH4O	F(000) = 1176
Mr = 280.30	Least-squares treatment of 25 SET4 setting angles.
Monoclinic, C2/c	Dx = 1.356 Mg m−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 26.942 (7) Å	Cell parameters from 1832 reflections
b = 6.3479 (17) Å	θ = 2.4–25.7°
c = 17.579 (5) Å	µ = 0.09 mm−1
β = 113.985 (4)°	T = 293 K
V = 2746.8 (13) Å3	Prismatic, red
Z = 8	0.26 × 0.06 × 0.05 mm

Bruker APEXII CCD diffractometer	2286 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 30.7°, θmin = 2.4°
phi and ω scans	h = −38→37
12992 measured reflections	k = −8→9
4212 independent reflections	l = −24→24

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154	H 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 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.05411 (5)	0.9010 (2)	0.10115 (8)	0.0693 (5)
O2	0.09325 (5)	1.7942 (2)	−0.17549 (9)	0.0775 (5)
N1	0.13875 (5)	0.98315 (19)	0.04654 (7)	0.0426 (4)
N2	0.09869 (5)	1.1128 (2)	0.02339 (7)	0.0454 (4)
C1	0.13793 (5)	0.8158 (2)	0.09375 (8)	0.0408 (4)
C2	0.09520 (6)	0.7749 (3)	0.12016 (10)	0.0516 (5)
C3	0.09810 (7)	0.5873 (3)	0.16635 (10)	0.0563 (6)
C4	0.13956 (6)	0.4517 (3)	0.18484 (9)	0.0510 (5)
C5	0.18354 (6)	0.4878 (2)	0.16088 (8)	0.0439 (5)
C6	0.18351 (5)	0.6722 (2)	0.11622 (8)	0.0402 (4)
C7	0.22698 (6)	0.3453 (3)	0.18175 (9)	0.0529 (5)
C8	0.26920 (7)	0.3855 (3)	0.16014 (10)	0.0590 (6)
C9	0.26971 (6)	0.5681 (3)	0.11681 (10)	0.0565 (6)
C10	0.22765 (6)	0.7090 (3)	0.09506 (9)	0.0482 (5)
C11	0.09846 (5)	1.2857 (2)	−0.02644 (8)	0.0421 (4)
C12	0.05513 (6)	1.4243 (3)	−0.04920 (10)	0.0505 (5)
C13	0.05257 (6)	1.5962 (3)	−0.09868 (10)	0.0555 (5)
C14	0.09319 (6)	1.6298 (2)	−0.12578 (9)	0.0507 (5)
C15	0.13698 (6)	1.4922 (2)	−0.10218 (9)	0.0497 (5)
C16	0.13961 (6)	1.3214 (2)	−0.05285 (9)	0.0467 (5)
O1S	−0.00722 (9)	2.0049 (3)	−0.21505 (14)	0.0490 (7)	0.500
C1S	0.00000	2.1846 (5)	−0.25000	0.0803 (14)
H2A	0.07230	1.09380	0.03830	0.0540*
H2B	0.06390	1.85490	−0.19190	0.1160*
H3A	0.07060	0.55830	0.18400	0.0680*
H4A	0.13970	0.32990	0.21430	0.0610*
H7A	0.22690	0.22250	0.21060	0.0630*
H8A	0.29780	0.29040	0.17440	0.0710*
H9A	0.29880	0.59470	0.10250	0.0680*
H10A	0.22840	0.83040	0.06590	0.0580*
H12A	0.02760	1.40130	−0.03110	0.0610*
H13A	0.02350	1.68920	−0.11370	0.0670*
H15A	0.16470	1.51600	−0.11990	0.0600*
H16A	0.16900	1.22980	−0.03720	0.0560*
H1SA	−0.035 (2)	2.289 (9)	−0.284 (3)	0.1210*	0.500
H1O	−0.02100	2.04990	−0.17790	0.0740*	0.500
H1SB	0.0081 (13)	2.124 (4)	−0.2876 (18)	0.1210*

	U11	U22	U33	U12	U13	U23
O1	0.0529 (7)	0.0772 (9)	0.0909 (9)	0.0092 (6)	0.0428 (6)	0.0195 (7)
O2	0.0765 (9)	0.0569 (8)	0.0916 (9)	0.0183 (7)	0.0265 (8)	0.0293 (7)
N1	0.0401 (6)	0.0436 (7)	0.0416 (6)	−0.0025 (5)	0.0140 (5)	−0.0025 (5)
N2	0.0390 (6)	0.0523 (8)	0.0480 (7)	−0.0009 (6)	0.0209 (5)	0.0012 (6)
C1	0.0407 (7)	0.0440 (8)	0.0368 (7)	−0.0082 (6)	0.0148 (6)	−0.0020 (6)
C2	0.0462 (8)	0.0579 (10)	0.0513 (8)	−0.0068 (7)	0.0206 (7)	0.0019 (8)
C3	0.0542 (9)	0.0640 (11)	0.0575 (9)	−0.0095 (8)	0.0298 (8)	0.0059 (8)
C4	0.0584 (9)	0.0525 (10)	0.0423 (8)	−0.0109 (8)	0.0207 (7)	0.0026 (7)
C5	0.0480 (8)	0.0463 (9)	0.0346 (7)	−0.0061 (7)	0.0139 (6)	−0.0019 (6)
C6	0.0420 (7)	0.0431 (8)	0.0339 (7)	−0.0057 (6)	0.0137 (5)	−0.0033 (6)
C7	0.0627 (10)	0.0472 (9)	0.0451 (8)	−0.0005 (8)	0.0181 (7)	0.0033 (7)
C8	0.0598 (10)	0.0561 (11)	0.0604 (10)	0.0137 (8)	0.0238 (8)	0.0054 (8)
C9	0.0508 (9)	0.0624 (11)	0.0618 (10)	0.0030 (8)	0.0284 (8)	0.0031 (8)
C10	0.0495 (8)	0.0500 (9)	0.0486 (8)	−0.0012 (7)	0.0235 (7)	0.0034 (7)
C11	0.0420 (7)	0.0430 (8)	0.0392 (7)	−0.0017 (6)	0.0144 (6)	−0.0034 (6)
C12	0.0401 (7)	0.0571 (10)	0.0548 (9)	0.0040 (7)	0.0197 (7)	−0.0062 (8)
C13	0.0443 (8)	0.0492 (10)	0.0638 (10)	0.0121 (7)	0.0124 (7)	−0.0031 (8)
C14	0.0518 (9)	0.0412 (9)	0.0516 (8)	0.0063 (7)	0.0134 (7)	0.0015 (7)
C15	0.0509 (8)	0.0481 (9)	0.0544 (9)	0.0072 (7)	0.0259 (7)	0.0060 (7)
C16	0.0436 (7)	0.0472 (9)	0.0506 (8)	0.0105 (7)	0.0205 (6)	0.0050 (7)
O1S	0.0556 (12)	0.0450 (13)	0.0529 (12)	0.0055 (11)	0.0286 (10)	0.0051 (10)
C1S	0.105 (3)	0.058 (2)	0.090 (2)	0.0000	0.052 (2)	0.0000

O1—C2	1.295 (2)	C11—C16	1.384 (2)
O2—C14	1.362 (2)	C11—C12	1.385 (2)
O2—H2B	0.8200	C12—C13	1.380 (3)
O1S—C1S	1.347 (3)	C13—C14	1.376 (2)
O1S—H1SBi	0.76 (3)	C14—C15	1.389 (2)
O1S—H1O	0.9200	C15—C16	1.372 (2)
N1—N2	1.2848 (19)	C3—H3A	0.9300
N1—C1	1.3538 (18)	C4—H4A	0.9300
N2—C11	1.4027 (18)	C7—H7A	0.9300
N2—H2A	0.8600	C8—H8A	0.9300
C1—C6	1.449 (2)	C9—H9A	0.9300
C1—C2	1.429 (2)	C10—H10A	0.9300
C2—C3	1.426 (3)	C12—H12A	0.9300
C3—C4	1.341 (3)	C13—H13A	0.9300
C4—C5	1.428 (2)	C15—H15A	0.9300
C5—C7	1.405 (2)	C16—H16A	0.9300
C5—C6	1.4093 (19)	C1S—H1SA	1.11 (6)
C6—C10	1.402 (2)	C1S—H1SB	0.87 (3)
C7—C8	1.362 (3)	C1S—H1SAi	1.11 (6)
C8—C9	1.390 (3)	C1S—H1SBi	0.87 (3)
C9—C10	1.370 (3)
C14—O2—H2B	109.00	C4—C3—H3A	119.00
C1S—O1S—H1O	104.00	C2—C3—H3A	119.00
C1S—O1S—H1SBi	37 (2)	C3—C4—H4A	119.00
H1O—O1S—H1SBi	67.00	C5—C4—H4A	119.00
N2—N1—C1	118.42 (14)	C5—C7—H7A	120.00
N1—N2—C11	119.27 (13)	C8—C7—H7A	120.00
N1—N2—H2A	120.00	C9—C8—H8A	120.00
C11—N2—H2A	120.00	C7—C8—H8A	120.00
C2—C1—C6	120.15 (13)	C8—C9—H9A	120.00
N1—C1—C2	123.90 (14)	C10—C9—H9A	120.00
N1—C1—C6	115.94 (13)	C6—C10—H10A	120.00
O1—C2—C1	121.39 (16)	C9—C10—H10A	120.00
O1—C2—C3	120.43 (16)	C11—C12—H12A	120.00
C1—C2—C3	118.16 (16)	C13—C12—H12A	120.00
C2—C3—C4	121.44 (18)	C12—C13—H13A	120.00
C3—C4—C5	122.32 (16)	C14—C13—H13A	120.00
C4—C5—C7	121.51 (14)	C16—C15—H15A	120.00
C6—C5—C7	119.48 (15)	C14—C15—H15A	120.00
C4—C5—C6	119.01 (14)	C11—C16—H16A	120.00
C1—C6—C5	118.87 (13)	C15—C16—H16A	120.00
C1—C6—C10	122.60 (13)	O1S—C1S—O1Si	64.2 (2)
C5—C6—C10	118.53 (14)	O1S—C1S—H1SA	120 (3)
C5—C7—C8	120.54 (16)	O1S—C1S—H1SB	95.7 (18)
C7—C8—C9	120.30 (18)	O1S—C1S—H1SAi	121 (3)
C8—C9—C10	120.39 (17)	O1S—C1S—H1SBi	31.5 (18)
C6—C10—C9	120.76 (16)	H1SA—C1S—H1SB	106 (3)
N2—C11—C12	117.83 (14)	O1Si—C1S—H1SA	121 (3)
N2—C11—C16	122.48 (13)	H1SA—C1S—H1SAi	107 (4)
C12—C11—C16	119.70 (13)	H1SA—C1S—H1SBi	105 (4)
C11—C12—C13	120.33 (16)	O1Si—C1S—H1SB	31.5 (18)
C12—C13—C14	119.86 (16)	H1SAi—C1S—H1SB	105 (4)
O2—C14—C13	123.34 (15)	H1SB—C1S—H1SBi	127 (3)
C13—C14—C15	119.84 (14)	O1Si—C1S—H1SAi	120 (3)
O2—C14—C15	116.82 (15)	O1Si—C1S—H1SBi	95.7 (18)
C14—C15—C16	120.34 (16)	H1SAi—C1S—H1SBi	106 (3)
C11—C16—C15	119.93 (14)
C1—N1—N2—C11	−179.19 (12)	C7—C5—C6—C1	178.85 (13)
N2—N1—C1—C2	−0.5 (2)	C7—C5—C6—C10	−1.0 (2)
N2—N1—C1—C6	178.51 (12)	C4—C5—C7—C8	−178.29 (15)
N1—N2—C11—C12	−178.98 (13)	C6—C5—C7—C8	0.9 (2)
N1—N2—C11—C16	0.9 (2)	C1—C6—C10—C9	−179.35 (14)
N1—C1—C2—O1	−1.3 (2)	C5—C6—C10—C9	0.5 (2)
N1—C1—C2—C3	177.00 (14)	C5—C7—C8—C9	−0.2 (2)
C6—C1—C2—O1	179.78 (14)	C7—C8—C9—C10	−0.3 (3)
C6—C1—C2—C3	−2.0 (2)	C8—C9—C10—C6	0.2 (2)
N1—C1—C6—C5	−176.08 (12)	N2—C11—C12—C13	−179.50 (14)
N1—C1—C6—C10	3.72 (19)	C16—C11—C12—C13	0.7 (2)
C2—C1—C6—C5	2.97 (19)	N2—C11—C16—C15	179.40 (13)
C2—C1—C6—C10	−177.23 (14)	C12—C11—C16—C15	−0.8 (2)
O1—C2—C3—C4	178.23 (16)	C11—C12—C13—C14	0.2 (2)
C1—C2—C3—C4	0.0 (2)	C12—C13—C14—O2	179.21 (15)
C2—C3—C4—C5	1.1 (3)	C12—C13—C14—C15	−0.9 (2)
C3—C4—C5—C6	0.0 (2)	O2—C14—C15—C16	−179.31 (13)
C3—C4—C5—C7	179.16 (15)	C13—C14—C15—C16	0.8 (2)
C4—C5—C6—C1	−1.97 (19)	C14—C15—C16—C11	0.0 (2)
C4—C5—C6—C10	178.22 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1O···O1ii	0.92	1.92	2.832 (3)	171
N2—H2A···O1	0.86	1.84	2.540 (2)	137
O2—H2B···O1S	0.82	2.03	2.841 (3)	172
O2—H2B···O1Si	0.82	1.97	2.690 (3)	146
C1S—H1SA···Cg3iii	1.11 (6)	2.58 (5)	3.555 (2)	147 (4)
C7—H7A···Cg2iv	0.93	2.73	3.521 (2)	144

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the C5–C10 and C11–C16 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1O⋯O1i	0.92	1.92	2.832 (3)	171
N2—H2A⋯O1	0.86	1.84	2.540 (2)	137
O2—H2B⋯O1S	0.82	2.03	2.841 (3)	172
O2—H2B⋯O1S ii	0.82	1.97	2.690 (3)	146
C1S—H1SA⋯Cg3iii	1.11 (6)	2.58 (5)	3.555 (2)	147 (4)
C7—H7A⋯Cg2iv	0.93	2.73	3.521 (2)	144

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .