(E)-2-Acetyl-4-[(3-methyl-phenyl-)diazen-yl]phenol: an X-ray and DFT study.

The title compound, C(15)H(14)N(2)O(2), an azo dye, displays a trans configuration with respect to the N=N bridge. The dihedral angle between the aromatic rings is 0.18 (14)°. There is a strong intra-molecular O-H⋯O hydrogen bond. Geometrical parameters, determined using X-ray diffraction techniques, are compared with those calculated by density functional theory (DFT), using hybrid exchange-correlation functional, B3LYP and semi-empirical (PM3) methods.

Related literature

For general background to azo compounds, see: Klaus (2003 ▶); Catino & Farris (1985 ▶); Zollinger (2003 ▶); Bahatti & Seshadri (2004 ▶); Taniike et al. (1996 ▶); Fadda et al. (1994 ▶). For a related structure, see: El-Ghamry et al. (2008 ▶). For background to DFT calculations, see: Becke (1988 ▶, 1993 ▶); Lee et al. (1988 ▶); Schmidt & Polik (2007 ▶)

Experimental

Crystal data

C15H14N2O2

M = 254.28

Monoclinic,

a = 8.6917 (3) Å

b = 10.9728 (3) Å

c = 14.6150 (5) Å

β = 112.881 (3)°

V = 1284.19 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 150 K

0.67 × 0.37 × 0.21 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.957, T max = 0.986

16525 measured reflections

2519 independent reflections

2034 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.175

S = 1.06

2519 reflections

176 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.26 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and GAUSSIAN (Frisch et al., 2004 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003491/bt5181sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003491/bt5181Isup2.hkl

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

C15H14N2O2	F(000) = 536
Mr = 254.28	Dx = 1.315 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 20945 reflections
a = 8.6917 (3) Å	θ = 1.9–28.0°
b = 10.9728 (3) Å	µ = 0.09 mm−1
c = 14.6150 (5) Å	T = 150 K
β = 112.881 (3)°	Prism, brown
V = 1284.19 (7) Å3	0.67 × 0.37 × 0.21 mm
Z = 4

Stoe IPDS II diffractometer	2519 independent reflections
Radiation source: fine-focus sealed tube	2034 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 6.67 pixels mm-1	θmax = 26.0°, θmin = 2.4°
ω scan	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.957, Tmax = 0.986	l = −18→18
16525 measured reflections

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0859P)2 + 0.7485P] where P = (Fo2 + 2Fc2)/3
2519 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Experimental. 330 frames, detector distance = 80 mm

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
C1	0.7697 (3)	0.49666 (19)	0.56898 (15)	0.0354 (5)
C2	0.7798 (2)	0.48461 (19)	0.66522 (14)	0.0337 (5)
H2	0.7188	0.5371	0.6882	0.040*
C3	0.8796 (3)	0.39527 (19)	0.72861 (15)	0.0340 (5)
C4	0.9690 (3)	0.3160 (2)	0.69197 (16)	0.0385 (5)
C5	0.9567 (3)	0.3271 (2)	0.59383 (17)	0.0433 (5)
H5	1.0150	0.2737	0.5695	0.052*
C6	0.8588 (3)	0.4165 (2)	0.53369 (15)	0.0410 (5)
H6	0.8517	0.4240	0.4688	0.049*
C7	0.8963 (3)	0.3858 (2)	0.83278 (16)	0.0396 (5)
C8	0.8087 (3)	0.4746 (3)	0.87272 (17)	0.0506 (6)
H8A	0.8323	0.4560	0.9410	0.076*
H8B	0.6905	0.4695	0.8350	0.076*
H8C	0.8467	0.5556	0.8679	0.076*
C9	0.5627 (3)	0.7083 (2)	0.37340 (17)	0.0392 (5)
C10	0.5540 (3)	0.7208 (2)	0.27821 (17)	0.0460 (6)
H10	0.6146	0.6692	0.2543	0.055*
C11	0.4544 (3)	0.8107 (2)	0.21837 (18)	0.0482 (6)
H11	0.4465	0.8197	0.1534	0.058*
C12	0.3654 (3)	0.8882 (2)	0.25587 (17)	0.0447 (6)
H12	0.2970	0.9479	0.2148	0.054*
C13	0.3764 (3)	0.8785 (2)	0.35255 (17)	0.0426 (5)
C14	0.4774 (3)	0.7866 (2)	0.41242 (16)	0.0426 (5)
H14	0.4875	0.7778	0.4778	0.051*
C15	0.2821 (3)	0.9642 (3)	0.39089 (19)	0.0546 (7)
H15A	0.3037	0.9448	0.4588	0.082*
H15B	0.1647	0.9566	0.3517	0.082*
H15C	0.3171	1.0463	0.3868	0.082*
N1	0.6655 (2)	0.60844 (18)	0.42943 (14)	0.0435 (5)
N2	0.6666 (2)	0.59649 (18)	0.51418 (13)	0.0431 (5)
O1	1.0685 (2)	0.22765 (17)	0.74768 (14)	0.0523 (5)
O2	0.9858 (2)	0.30620 (17)	0.88764 (12)	0.0522 (5)
H1	1.055 (4)	0.235 (3)	0.801 (3)	0.076 (11)*

	U11	U22	U33	U12	U13	U23
C1	0.0362 (10)	0.0347 (11)	0.0302 (10)	−0.0037 (8)	0.0074 (8)	0.0012 (8)
C2	0.0342 (10)	0.0327 (10)	0.0320 (10)	−0.0026 (8)	0.0106 (8)	−0.0006 (8)
C3	0.0347 (10)	0.0348 (11)	0.0299 (10)	−0.0039 (8)	0.0098 (8)	0.0018 (8)
C4	0.0386 (11)	0.0354 (11)	0.0376 (11)	0.0018 (9)	0.0104 (9)	0.0055 (9)
C5	0.0475 (13)	0.0427 (13)	0.0401 (12)	0.0041 (10)	0.0174 (10)	−0.0026 (10)
C6	0.0460 (12)	0.0458 (13)	0.0286 (10)	−0.0039 (10)	0.0118 (9)	0.0002 (9)
C7	0.0359 (11)	0.0473 (13)	0.0320 (10)	−0.0061 (10)	0.0091 (9)	0.0061 (9)
C8	0.0533 (14)	0.0671 (16)	0.0326 (11)	0.0004 (12)	0.0181 (10)	0.0003 (11)
C9	0.0378 (11)	0.0343 (11)	0.0432 (11)	−0.0041 (9)	0.0133 (9)	0.0002 (9)
C10	0.0511 (13)	0.0437 (13)	0.0426 (12)	−0.0030 (11)	0.0177 (11)	−0.0016 (10)
C11	0.0524 (14)	0.0438 (13)	0.0435 (12)	−0.0035 (11)	0.0133 (11)	0.0023 (10)
C12	0.0467 (12)	0.0375 (12)	0.0401 (12)	−0.0023 (10)	0.0062 (10)	0.0058 (9)
C13	0.0404 (12)	0.0379 (12)	0.0430 (12)	−0.0038 (10)	0.0093 (10)	0.0027 (10)
C14	0.0436 (12)	0.0471 (13)	0.0341 (11)	−0.0097 (10)	0.0119 (9)	0.0002 (9)
C15	0.0554 (15)	0.0574 (16)	0.0500 (14)	0.0057 (12)	0.0196 (12)	0.0049 (12)
N1	0.0464 (11)	0.0442 (11)	0.0375 (10)	−0.0024 (9)	0.0137 (8)	0.0008 (8)
N2	0.0430 (10)	0.0478 (11)	0.0309 (9)	−0.0097 (9)	0.0060 (8)	0.0069 (8)
O1	0.0587 (11)	0.0491 (10)	0.0484 (10)	0.0193 (8)	0.0201 (9)	0.0144 (8)
O2	0.0554 (10)	0.0611 (11)	0.0381 (8)	0.0056 (8)	0.0161 (8)	0.0179 (8)

C1—C2	1.381 (3)	C9—C10	1.371 (3)
C1—C6	1.396 (3)	C9—C14	1.393 (3)
C1—N2	1.444 (3)	C9—N1	1.450 (3)
C2—C3	1.395 (3)	C10—C11	1.378 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.404 (3)	C11—C12	1.397 (4)
C3—C7	1.476 (3)	C11—H11	0.9300
C4—O1	1.343 (3)	C12—C13	1.383 (3)
C4—C5	1.402 (3)	C12—H12	0.9300
C5—C6	1.371 (3)	C13—C14	1.398 (3)
C5—H5	0.9300	C13—C15	1.493 (4)
C6—H6	0.9300	C14—H14	0.9300
C7—O2	1.235 (3)	C15—H15A	0.9600
C7—C8	1.488 (3)	C15—H15B	0.9600
C8—H8A	0.9600	C15—H15C	0.9600
C8—H8B	0.9600	N1—N2	1.242 (3)
C8—H8C	0.9600	O1—H1	0.83 (4)
C2—C1—C6	119.43 (19)	C10—C9—C14	121.7 (2)
C2—C1—N2	114.66 (19)	C10—C9—N1	115.3 (2)
C6—C1—N2	125.89 (19)	C14—C9—N1	123.0 (2)
C1—C2—C3	121.3 (2)	C9—C10—C11	119.3 (2)
C1—C2—H2	119.3	C9—C10—H10	120.4
C3—C2—H2	119.3	C11—C10—H10	120.4
C2—C3—C4	118.39 (19)	C10—C11—C12	119.6 (2)
C2—C3—C7	121.4 (2)	C10—C11—H11	120.2
C4—C3—C7	120.20 (19)	C12—C11—H11	120.2
O1—C4—C5	117.2 (2)	C13—C12—C11	121.7 (2)
O1—C4—C3	122.5 (2)	C13—C12—H12	119.2
C5—C4—C3	120.23 (19)	C11—C12—H12	119.2
C6—C5—C4	120.0 (2)	C12—C13—C14	118.2 (2)
C6—C5—H5	120.0	C12—C13—C15	120.3 (2)
C4—C5—H5	120.0	C14—C13—C15	121.5 (2)
C5—C6—C1	120.6 (2)	C9—C14—C13	119.5 (2)
C5—C6—H6	119.7	C9—C14—H14	120.2
C1—C6—H6	119.7	C13—C14—H14	120.2
O2—C7—C3	120.3 (2)	C13—C15—H15A	109.5
O2—C7—C8	119.8 (2)	C13—C15—H15B	109.5
C3—C7—C8	119.90 (19)	H15A—C15—H15B	109.5
C7—C8—H8A	109.5	C13—C15—H15C	109.5
C7—C8—H8B	109.5	H15A—C15—H15C	109.5
H8A—C8—H8B	109.5	H15B—C15—H15C	109.5
C7—C8—H8C	109.5	N2—N1—C9	114.0 (2)
H8A—C8—H8C	109.5	N1—N2—C1	113.3 (2)
H8B—C8—H8C	109.5	C4—O1—H1	102 (2)
C6—C1—C2—C3	1.1 (3)	C4—C3—C7—C8	176.5 (2)
N2—C1—C2—C3	−177.57 (18)	C14—C9—C10—C11	−2.0 (3)
C1—C2—C3—C4	−0.8 (3)	N1—C9—C10—C11	177.8 (2)
C1—C2—C3—C7	177.24 (19)	C9—C10—C11—C12	0.6 (3)
C2—C3—C4—O1	179.8 (2)	C10—C11—C12—C13	1.0 (4)
C7—C3—C4—O1	1.7 (3)	C11—C12—C13—C14	−1.3 (3)
C2—C3—C4—C5	−0.2 (3)	C11—C12—C13—C15	178.9 (2)
C7—C3—C4—C5	−178.3 (2)	C10—C9—C14—C13	1.8 (3)
O1—C4—C5—C6	−179.1 (2)	N1—C9—C14—C13	−178.01 (19)
C3—C4—C5—C6	0.9 (3)	C12—C13—C14—C9	−0.1 (3)
C4—C5—C6—C1	−0.5 (3)	C15—C13—C14—C9	179.7 (2)
C2—C1—C6—C5	−0.5 (3)	C10—C9—N1—N2	−177.6 (2)
N2—C1—C6—C5	178.1 (2)	C14—C9—N1—N2	2.2 (3)
C2—C3—C7—O2	−179.8 (2)	C9—N1—N2—C1	−179.99 (17)
C4—C3—C7—O2	−1.8 (3)	C2—C1—N2—N1	177.09 (19)
C2—C3—C7—C8	−1.4 (3)	C6—C1—N2—N1	−1.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84 (4)	1.78 (4)	2.567 (3)	156 (4)

Parameters	X-ray	PM3	DFT/B3LYP*
C4—O1	1.343 (3)	1.351	1.331
C7—O2	1.235 (3)	1.228	1.242
C7—C8	1.488 (3)	1.502	1.513
C13—C15	1.493 (4)	1.486	1.511
C1—N2	1.444 (3)	1.445	1.411
N1—N2	1.242 (3)	1.232	1.263
C9—N1	1.450 (3)	1.447	1.417
O2—C7—C8	119.8 (2)	120.465	118.986
O1—C4—C5	117.2 (2)	115.387	118.123
C7—C3—C4—O1	1.7 (3)	-0.016	0.002
C9—N1—N2—C1	-179.99 (17)	-179.965	-179.975
C2—C1—N2—N1	177.09 (19)	-178.543	179.996
C10—C9—N1—N2	-177.6 (2)	-172.651	179.997

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84 (4)	1.78 (4)	2.567 (3)	156 (4)

Table 2

Selected geometric parameters (Å, °) calculated with X-ray, PM3 and DFT

Parameters	X-ray	PM3	DFT/B3LYP*
C4—O1	1.343 (3)	1.351	1.331
C7—O2	1.235 (3)	1.228	1.242
C7—C8	1.488 (3)	1.502	1.513
C13—C15	1.493 (4)	1.486	1.511
C1—N2	1.444 (3)	1.445	1.411
N1—N2	1.242 (3)	1.232	1.263
C9—N1	1.450 (3)	1.447	1.417
O2—C7—C8	119.8 (2)	120.465	118.986
O1—C4—C5	117.2 (2)	115.387	118.123
C7—C3—C4—O1	1.7 (3)	−0.016	0.002
C9—N1—N2—C1	−179.99 (17)	−179.965	−179.975
C2—C1—N2—N1	177.09 (19)	−178.543	179.996
C10—C9—N1—N2	−177.6 (2)	−172.651	179.997

*6–31G(d,p).