2,2′-(1,1′-Azinodiethyl­idyne)diphenol

Tai, X.-S.; Xu, J.; Feng, Y.-M.; Liang, Z.-P.

doi:10.1107/S1600536808011318

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o905

doi:10.1107/S1600536808011318

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2,2′-(1,1′-Azinodiethylidyne)diphenol

Xi-Shi Tai,^a ^* Jun Xu,^b Yi-Min Feng ^a and Zu-Pei Liang ^a

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bWeifang Institute of Supervision and Inspection of Product Quality, Weifang 261061, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 18 April 2008; accepted 21 April 2008; online 26 April 2008)

In the title molecule, C₁₆H₁₆N₂O₂, the C—N bond lengths are 1.295 (5) and 1.300 (5) Å, which suggests that they are double bonds. The structure is stabilized by intramolecular O—H⋯N and C—H⋯N, and intermolecular C—H⋯O hydrogen-bond interactions.

Related literature

For related literature, see: Tai et al. (2003 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₂
M_r = 268.31
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.3358 (8) Å
b = 13.5625 (10) Å
c = 15.9956 (15) Å
V = 1374.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.38 × 0.15 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.968, T_max = 0.988
7170 measured reflections
1422 independent reflections
849 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.128
S = 1.08
1422 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.80	2.529 (5)	146
O2—H2⋯N2	0.82	1.80	2.529 (4)	147
C1—H1A⋯N2	0.96	2.32	2.739 (5)	106
C5—H5⋯O2ⁱ	0.93	2.59	3.403 (6)	147
C9—H9A⋯N1	0.96	2.30	2.724 (6)	106
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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 global, I. DOI: 10.1107/S1600536808011318/at2562sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011318/at2562Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of the coordination chemistry of Schiffbase ligands (Tai et al., 2003), we now report the synthesis and structure of the title compound, (I), (Fig. 1).

In the molecule of (I), both C2—N1 [1.295 (5) Å], and C10—N2 [1.300 (5) Å] are close to double-bond separations, indicating that the Lewis structure shown in the scheme is only an approximation to the electron distribution in the molecule. Otherwise, the geometrical parameters for (I) are normal. The structure is stabilized by intramolecular O—H···N and C—H···N, and intermolecular C—H···O hydrogen bonding interactions.

Related literature top

For related literature, see: Tai et al. (2003).

Experimental top

2 mmol of 2'-Hhydroxyacetophenone (2 mmol) was added to a solution of hydrazide (1 mmol) in 10 ml of 95% ethanol. The mixture was continuously stirred for 3 h at refluxing temperature, evaporating some ethanol, then, upon cooling, the solid product was collected by filtration and dried in vacuo (yield 58%). Clear blocks of (I) were obtained by evaporation from a methanol solution after 6 days.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 molecular structure of (I) showing 30% displacement ellipsoids.

2,2'-(1,1'-Azinodiethylidyne)diphenol top

Crystal data top

C₁₆H₁₆N₂O₂	F(000) = 568
M_r = 268.31	D_x = 1.297 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1489 reflections
a = 6.3358 (8) Å	θ = 2.9–20.4°
b = 13.5625 (10) Å	µ = 0.09 mm⁻¹
c = 15.9956 (15) Å	T = 298 K
V = 1374.5 (2) Å³	Block, colourless
Z = 4	0.38 × 0.15 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1422 independent reflections
Radiation source: fine-focus sealed tube	849 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→7
T_min = 0.968, T_max = 0.988	k = −16→13
7170 measured reflections	l = −17→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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0468P)² + 0.4138P] where P = (F_o² + 2F_c²)/3
1422 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₂	V = 1374.5 (2) Å³
M_r = 268.31	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.3358 (8) Å	µ = 0.09 mm⁻¹
b = 13.5625 (10) Å	T = 298 K
c = 15.9956 (15) Å	0.38 × 0.15 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1422 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	849 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.988	R_int = 0.044
7170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.08	Δρ_max = 0.15 e Å⁻³
1422 reflections	Δρ_min = −0.14 e Å⁻³
181 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
N1	0.5862 (6)	0.4828 (2)	0.5963 (2)	0.0489 (9)
N2	0.4075 (6)	0.4685 (2)	0.6456 (2)	0.0486 (9)
O1	0.8168 (6)	0.4367 (2)	0.47328 (19)	0.0824 (11)
H1	0.7174	0.4320	0.5059	0.124*
O2	0.1570 (5)	0.5228 (2)	0.75976 (17)	0.0670 (9)
H2	0.2602	0.5259	0.7290	0.101*
C1	0.6514 (8)	0.6288 (3)	0.6846 (3)	0.0719 (14)
H1A	0.5090	0.6183	0.7031	0.108*
H1B	0.6665	0.6953	0.6649	0.108*
H1C	0.7468	0.6177	0.7302	0.108*
C2	0.7010 (7)	0.5586 (3)	0.6150 (2)	0.0472 (10)
C3	0.8877 (7)	0.5753 (3)	0.5630 (2)	0.0487 (11)
C4	0.9357 (8)	0.5152 (3)	0.4941 (3)	0.0605 (13)
C5	1.1111 (9)	0.5351 (4)	0.4453 (3)	0.0779 (16)
H5	1.1417	0.4951	0.3996	0.093*
C6	1.2395 (9)	0.6130 (4)	0.4636 (3)	0.0778 (15)
H6	1.3570	0.6254	0.4304	0.093*
C7	1.1973 (8)	0.6727 (4)	0.5301 (3)	0.0698 (14)
H7	1.2848	0.7259	0.5422	0.084*
C8	1.0243 (7)	0.6535 (3)	0.5790 (3)	0.0589 (12)
H8	0.9973	0.6942	0.6246	0.071*
C9	0.3515 (10)	0.3201 (3)	0.5599 (3)	0.0861 (17)
H9A	0.4546	0.3497	0.5237	0.129*
H9B	0.2270	0.3046	0.5283	0.129*
H9C	0.4084	0.2608	0.5836	0.129*
C10	0.2963 (7)	0.3905 (3)	0.6284 (2)	0.0502 (11)
C11	0.1087 (7)	0.3741 (3)	0.6796 (3)	0.0500 (11)
C12	0.0460 (7)	0.4402 (3)	0.7423 (3)	0.0542 (11)
C13	−0.1329 (8)	0.4228 (4)	0.7893 (3)	0.0651 (13)
H13	−0.1705	0.4669	0.8312	0.078*
C14	−0.2557 (9)	0.3416 (4)	0.7750 (3)	0.0766 (15)
H14	−0.3769	0.3310	0.8065	0.092*
C15	−0.1990 (9)	0.2764 (3)	0.7141 (3)	0.0762 (15)
H15	−0.2824	0.2212	0.7041	0.091*
C16	−0.0201 (8)	0.2914 (3)	0.6674 (3)	0.0668 (13)
H16	0.0165	0.2456	0.6267	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.044 (2)	0.052 (2)	0.051 (2)	0.0052 (18)	0.0000 (18)	−0.0005 (16)
N2	0.046 (2)	0.047 (2)	0.053 (2)	0.0031 (18)	−0.0032 (18)	0.0000 (16)
O1	0.093 (3)	0.084 (2)	0.070 (2)	−0.013 (2)	0.021 (2)	−0.0175 (17)
O2	0.070 (2)	0.0691 (19)	0.0615 (19)	−0.0107 (19)	0.0074 (18)	−0.0083 (15)
C1	0.062 (3)	0.067 (3)	0.087 (3)	−0.006 (3)	0.012 (3)	−0.017 (3)
C2	0.049 (3)	0.044 (2)	0.049 (2)	0.010 (2)	−0.004 (2)	−0.0004 (18)
C3	0.048 (3)	0.052 (2)	0.047 (2)	0.009 (2)	−0.005 (2)	0.006 (2)
C4	0.068 (4)	0.062 (3)	0.052 (3)	−0.001 (3)	0.001 (3)	0.005 (2)
C5	0.087 (4)	0.092 (4)	0.054 (3)	0.005 (4)	0.020 (3)	0.004 (3)
C6	0.063 (3)	0.094 (4)	0.076 (4)	0.000 (3)	0.019 (3)	0.019 (3)
C7	0.056 (3)	0.076 (3)	0.076 (3)	−0.003 (3)	0.003 (3)	0.017 (3)
C8	0.053 (3)	0.063 (3)	0.061 (3)	0.003 (3)	−0.004 (3)	0.005 (2)
C9	0.079 (4)	0.072 (3)	0.107 (4)	−0.013 (3)	0.020 (3)	−0.035 (3)
C10	0.045 (3)	0.047 (2)	0.058 (3)	0.004 (2)	−0.004 (2)	−0.002 (2)
C11	0.049 (3)	0.045 (2)	0.056 (3)	0.001 (2)	−0.009 (2)	0.006 (2)
C12	0.055 (3)	0.054 (3)	0.054 (3)	0.001 (2)	−0.006 (2)	0.015 (2)
C13	0.063 (3)	0.070 (3)	0.063 (3)	0.005 (3)	0.002 (3)	0.015 (3)
C14	0.068 (3)	0.081 (3)	0.081 (4)	−0.002 (3)	0.009 (3)	0.031 (3)
C15	0.067 (4)	0.068 (3)	0.094 (4)	−0.019 (3)	−0.004 (3)	0.023 (3)
C16	0.068 (3)	0.057 (3)	0.075 (3)	−0.005 (3)	−0.009 (3)	0.003 (2)

Geometric parameters (Å, º) top

N1—C2	1.295 (5)	C7—C8	1.371 (6)
N1—N2	1.394 (4)	C7—H7	0.9300
N2—C10	1.300 (5)	C8—H8	0.9300
O1—C4	1.346 (5)	C9—C10	1.495 (5)
O1—H1	0.8200	C9—H9A	0.9600
O2—C12	1.352 (5)	C9—H9B	0.9600
O2—H2	0.8200	C9—H9C	0.9600
C1—C2	1.497 (5)	C10—C11	1.460 (6)
C1—H1A	0.9600	C11—C16	1.401 (5)
C1—H1B	0.9600	C11—C12	1.403 (6)
C1—H1C	0.9600	C12—C13	1.380 (6)
C2—C3	1.464 (5)	C13—C14	1.368 (6)
C3—C8	1.392 (5)	C13—H13	0.9300
C3—C4	1.405 (6)	C14—C15	1.364 (6)
C4—C5	1.385 (7)	C14—H14	0.9300
C5—C6	1.365 (7)	C15—C16	1.372 (7)
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.364 (6)	C16—H16	0.9300
C6—H6	0.9300

C2—N1—N2	115.8 (3)	C7—C8—H8	118.8
C10—N2—N1	115.7 (3)	C3—C8—H8	118.8
C4—O1—H1	109.5	C10—C9—H9A	109.5
C12—O2—H2	109.5	C10—C9—H9B	109.5
C2—C1—H1A	109.5	H9A—C9—H9B	109.5
C2—C1—H1B	109.5	C10—C9—H9C	109.5
H1A—C1—H1B	109.5	H9A—C9—H9C	109.5
C2—C1—H1C	109.5	H9B—C9—H9C	109.5
H1A—C1—H1C	109.5	N2—C10—C11	116.5 (4)
H1B—C1—H1C	109.5	N2—C10—C9	123.2 (4)
N1—C2—C3	116.5 (4)	C11—C10—C9	120.3 (4)
N1—C2—C1	124.0 (4)	C16—C11—C12	116.5 (4)
C3—C2—C1	119.6 (4)	C16—C11—C10	121.2 (4)
C8—C3—C4	116.8 (4)	C12—C11—C10	122.3 (4)
C8—C3—C2	121.1 (4)	O2—C12—C13	117.1 (4)
C4—C3—C2	122.1 (4)	O2—C12—C11	122.0 (4)
O1—C4—C5	117.6 (4)	C13—C12—C11	120.9 (4)
O1—C4—C3	122.1 (4)	C14—C13—C12	120.9 (5)
C5—C4—C3	120.2 (5)	C14—C13—H13	119.5
C6—C5—C4	120.5 (5)	C12—C13—H13	119.5
C6—C5—H5	119.7	C15—C14—C13	119.5 (5)
C4—C5—H5	119.7	C15—C14—H14	120.3
C7—C6—C5	120.7 (5)	C13—C14—H14	120.3
C7—C6—H6	119.7	C14—C15—C16	120.6 (5)
C5—C6—H6	119.7	C14—C15—H15	119.7
C6—C7—C8	119.3 (5)	C16—C15—H15	119.7
C6—C7—H7	120.4	C15—C16—C11	121.7 (5)
C8—C7—H7	120.4	C15—C16—H16	119.2
C7—C8—C3	122.5 (5)	C11—C16—H16	119.2

C2—N1—N2—C10	−177.9 (4)	N1—N2—C10—C11	179.9 (3)
N2—N1—C2—C3	−179.2 (3)	N1—N2—C10—C9	−0.6 (6)
N2—N1—C2—C1	−0.2 (5)	N2—C10—C11—C16	−178.7 (4)
N1—C2—C3—C8	−178.6 (4)	C9—C10—C11—C16	1.7 (6)
C1—C2—C3—C8	2.3 (5)	N2—C10—C11—C12	2.2 (5)
N1—C2—C3—C4	2.7 (5)	C9—C10—C11—C12	−177.4 (4)
C1—C2—C3—C4	−176.4 (4)	C16—C11—C12—O2	−179.8 (4)
C8—C3—C4—O1	179.0 (4)	C10—C11—C12—O2	−0.7 (6)
C2—C3—C4—O1	−2.3 (6)	C16—C11—C12—C13	0.5 (6)
C8—C3—C4—C5	−0.3 (6)	C10—C11—C12—C13	179.6 (4)
C2—C3—C4—C5	178.4 (4)	O2—C12—C13—C14	179.2 (4)
O1—C4—C5—C6	−179.2 (4)	C11—C12—C13—C14	−1.1 (6)
C3—C4—C5—C6	0.1 (7)	C12—C13—C14—C15	0.8 (7)
C4—C5—C6—C7	−0.1 (8)	C13—C14—C15—C16	0.2 (7)
C5—C6—C7—C8	0.3 (7)	C14—C15—C16—C11	−0.8 (7)
C6—C7—C8—C3	−0.6 (6)	C12—C11—C16—C15	0.5 (6)
C4—C3—C8—C7	0.6 (6)	C10—C11—C16—C15	−178.7 (4)
C2—C3—C8—C7	−178.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.80	2.529 (5)	146
O2—H2···N2	0.82	1.80	2.529 (4)	147
C1—H1A···N2	0.96	2.32	2.739 (5)	106
C5—H5···O2ⁱ	0.93	2.59	3.403 (6)	147
C9—H9A···N1	0.96	2.30	2.724 (6)	106

Symmetry code: (i) −x+3/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₂
M_r	268.31
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.3358 (8), 13.5625 (10), 15.9956 (15)
V (Å³)	1374.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.38 × 0.15 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.968, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7170, 1422, 849
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.128, 1.08
No. of reflections	1422
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
O1—H1···N1	0.82	1.80	2.529 (5)	146
O2—H2···N2	0.82	1.80	2.529 (4)	147
C1—H1A···N2	0.96	2.32	2.739 (5)	106
C5—H5···O2ⁱ	0.93	2.59	3.403 (6)	147
C9—H9A···N1	0.96	2.30	2.724 (6)	106

Symmetry code: (i) −x+3/2, −y+1, z−1/2.

Acknowledgements

The authors thank the National Natural Science Foundation of China (20671073), the Natural Science Foundation of Shandong (Y2007B60) and the Science and Technology Foundation of Weifang and Weifang University for research grants.

References

Bruker (2000). SMART, SAINT and 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
Tai, X.-S., Yin, X.-H., Tan, M.-Y. & Li, Y.-Z. (2003). Acta Cryst. E59, o681–o682. Web of Science CSD CrossRef IUCr Journals Google Scholar