6,6′-Dieth­oxy-2,2′-[hexane-1,6-diylbis(nitrilo­methanylyl­idene)]diphenol

Ha, K.

doi:10.1107/S1600536811009445

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o918

doi:10.1107/S1600536811009445

Open

access

6,6′-Diethoxy-2,2′-[hexane-1,6-diylbis(nitrilomethanylylidene)]diphenol

Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 4 March 2011; accepted 11 March 2011; online 19 March 2011)

The title compound, C₂₄H₃₂N₂O₄, is a polydentate Schiff base and reveals strong intramolecular O—H⋯N hydrogen bonding between the hydroxy O atom and the imino N atom, with an O⋯N distance of 2.570 (3) Å. In the crystal, a centre of inversion is located at the mid-point of the compound. The diiminohexylene chain is almost ideally in the anti conformation, with an average dihedral angle of 179.0°.

Related literature

For related structures, see: Bermejo et al. (2007 ); Fun et al. (2009 ); Ha (2010 ).

Experimental

Crystal data

C₂₄H₃₂N₂O₄
M_r = 412.52
Triclinic, $[P \overline 1]$
a = 6.9094 (13) Å
b = 6.9184 (13) Å
c = 11.936 (2) Å
α = 91.271 (5)°
β = 99.677 (4)°
γ = 102.550 (4)°
V = 547.97 (18) Å³
Z = 1
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.26 × 0.23 × 0.23 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.862, T_max = 1.000
3505 measured reflections
2140 independent reflections
1258 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.168
S = 1.02
2140 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84	1.83	2.570 (3)	147

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: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009445/ds2098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009445/ds2098Isup2.hkl

checkCIF report

Comment top

The title compound crystallized in the triclinic space group P1, same to the analogous compounds with propylene chain (C₂₁H₂₆N₂O₄) (Ha, 2010) and butylene chain (C₂₂H₂₈N₂O₄) (Fun et al., 2009), whereas the related Schiff base with ethylene group (C₂₀H₂₄N₂O₄) crystallized in the monoclinic space group C2/c (Bermejo et al., 2007).

The asymmetric unit of the title molecule contains one half of the formula unit; a centre of inversion is located in the midpoint of the compound (Fig. 1). The Schiff base reveals strong intramolecular O—H···N hydrogen bonding between the hydroxy O atom and the imino N atom with d(O···N) = 2.570 (3) Å forming a nearly planar six-membered ring (Fig. 2, Table 1). The N1—C9/10 bond lengths and the C9—N1—C10 bond angle indicate that the imino N1 atom is sp²-hybridized [d(N1═C9) = 1.271 (3) Å and d(N1—C10) = 1.469 (3) Å; <C9—N1—C10 = 121.2 (2)°]. The torsion angles for the four atoms within the diiminohexylene chain indicate that the chain is almost perfectly in the anti conformation with <N1—C10—C11—C12 = 179.1 (2)° and <C10—C11—C12—C12ⁱ (symmetry code i: 1 - x, 2 - y, 1 - z) = 178.8 (3)°.

Related literature top

For related structures, see: Bermejo et al. (2007); Fun et al. (2009); Ha (2010).

Experimental top

1,6-Diaminohexane (0.8132 g, 6.998 mmol) and 3-ethoxysalicylaldehyde (2.3265 g, 14.000 mmol) in EtOH (20 ml) were stirred for 5 h at room temperature. After addition of pentane (30 ml) to the reaction mixture, the formed precipitate was separated by filtration, washed with ether, and dried at 50 °C, to give a yellow powder (2.3563 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a toluene solution.

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: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 50% probability level; H atoms are shown as small circles of arbitrary radius. Unlabelled atoms are related to the reference atoms by the (1 - x, 2 - y, 1 - z) symmetry transformation.
	Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.

2-ethoxy-6-{[(6-{[(3-ethoxy-2- hydroxyphenyl)methylidene]amino}hexyl)imino]methyl}phenol top

Crystal data top

C₂₄H₃₂N₂O₄	Z = 1
M_r = 412.52	F(000) = 222
Triclinic, P1	D_x = 1.250 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9094 (13) Å	Cell parameters from 873 reflections
b = 6.9184 (13) Å	θ = 3.1–25.7°
c = 11.936 (2) Å	µ = 0.09 mm⁻¹
α = 91.271 (5)°	T = 200 K
β = 99.677 (4)°	Stick, yellow
γ = 102.550 (4)°	0.26 × 0.23 × 0.23 mm
V = 547.97 (18) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	2140 independent reflections
Radiation source: fine-focus sealed tube	1258 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
T_min = 0.862, T_max = 1.000	k = −8→8
3505 measured reflections	l = −14→11

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0725P)² + 0.0011P] where P = (F_o² + 2F_c²)/3
2140 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₄H₃₂N₂O₄	γ = 102.550 (4)°
M_r = 412.52	V = 547.97 (18) Å³
Triclinic, P1	Z = 1
a = 6.9094 (13) Å	Mo Kα radiation
b = 6.9184 (13) Å	µ = 0.09 mm⁻¹
c = 11.936 (2) Å	T = 200 K
α = 91.271 (5)°	0.26 × 0.23 × 0.23 mm
β = 99.677 (4)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2140 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1258 reflections with I > 2σ(I)
T_min = 0.862, T_max = 1.000	R_int = 0.031
3505 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
2140 reflections	Δρ_min = −0.21 e Å⁻³
138 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	0.5421 (2)	0.2477 (3)	0.24546 (17)	0.0424 (5)
H1	0.5714	0.3570	0.2834	0.064*
O2	0.5003 (2)	−0.0878 (2)	0.13057 (16)	0.0405 (5)
N1	0.7714 (3)	0.5589 (3)	0.35709 (19)	0.0383 (6)
C1	0.9039 (3)	0.3153 (3)	0.2687 (2)	0.0312 (6)
C2	0.7131 (3)	0.1965 (3)	0.2277 (2)	0.0318 (6)
C3	0.6946 (4)	0.0168 (4)	0.1652 (2)	0.0327 (6)
C4	0.8654 (4)	−0.0394 (4)	0.1439 (2)	0.0367 (7)
H4	0.8526	−0.1599	0.1007	0.044*
C5	1.0562 (4)	0.0782 (4)	0.1849 (2)	0.0399 (7)
H5	1.1729	0.0374	0.1705	0.048*
C6	1.0750 (4)	0.2543 (4)	0.2467 (2)	0.0357 (7)
H6	1.2051	0.3348	0.2745	0.043*
C7	0.4707 (4)	−0.2781 (3)	0.0726 (2)	0.0400 (7)
H7A	0.5449	−0.3639	0.1196	0.048*
H7B	0.5193	−0.2641	−0.0009	0.048*
C8	0.2475 (4)	−0.3664 (4)	0.0530 (3)	0.0492 (8)
H8A	0.2003	−0.3725	0.1261	0.074*
H8B	0.2202	−0.5005	0.0170	0.074*
H8C	0.1767	−0.2835	0.0032	0.074*
C9	0.9234 (4)	0.5017 (4)	0.3333 (2)	0.0351 (6)
H9	1.0540	0.5831	0.3585	0.042*
C10	0.7949 (4)	0.7477 (4)	0.4222 (2)	0.0394 (7)
H10A	0.8727	0.8568	0.3846	0.047*
H10B	0.8707	0.7421	0.4998	0.047*
C11	0.5920 (4)	0.7884 (3)	0.4300 (2)	0.0384 (7)
H11A	0.5143	0.6766	0.4657	0.046*
H11B	0.5179	0.7939	0.3520	0.046*
C12	0.6021 (3)	0.9794 (4)	0.4974 (2)	0.0366 (7)
H12A	0.6735	0.9729	0.5760	0.044*
H12B	0.6819	1.0911	0.4626	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0309 (10)	0.0439 (11)	0.0537 (13)	0.0112 (8)	0.0094 (9)	−0.0110 (9)
O2	0.0304 (10)	0.0369 (10)	0.0523 (13)	0.0049 (7)	0.0070 (9)	−0.0091 (9)
N1	0.0373 (12)	0.0389 (13)	0.0416 (14)	0.0150 (10)	0.0080 (11)	−0.0040 (11)
C1	0.0289 (13)	0.0342 (14)	0.0323 (15)	0.0099 (10)	0.0068 (12)	0.0001 (12)
C2	0.0278 (13)	0.0360 (14)	0.0356 (16)	0.0128 (11)	0.0096 (12)	0.0012 (12)
C3	0.0330 (14)	0.0323 (14)	0.0331 (15)	0.0076 (11)	0.0061 (12)	0.0017 (12)
C4	0.0387 (14)	0.0367 (14)	0.0372 (16)	0.0129 (11)	0.0087 (13)	−0.0053 (12)
C5	0.0318 (14)	0.0461 (16)	0.0465 (18)	0.0148 (12)	0.0127 (13)	−0.0029 (14)
C6	0.0282 (13)	0.0389 (15)	0.0401 (16)	0.0075 (11)	0.0066 (12)	−0.0007 (12)
C7	0.0397 (15)	0.0322 (15)	0.0469 (18)	0.0078 (11)	0.0052 (13)	−0.0025 (13)
C8	0.0450 (16)	0.0375 (16)	0.060 (2)	−0.0003 (12)	0.0075 (15)	−0.0070 (14)
C9	0.0305 (13)	0.0347 (14)	0.0387 (16)	0.0049 (11)	0.0056 (12)	−0.0011 (12)
C10	0.0410 (15)	0.0387 (15)	0.0385 (17)	0.0123 (12)	0.0037 (13)	−0.0083 (13)
C11	0.0401 (15)	0.0351 (15)	0.0429 (17)	0.0121 (11)	0.0112 (13)	−0.0035 (13)
C12	0.0381 (15)	0.0336 (15)	0.0387 (16)	0.0107 (11)	0.0056 (13)	−0.0032 (12)

Geometric parameters (Å, º) top

O1—C2	1.353 (3)	C7—C8	1.506 (4)
O1—H1	0.8400	C7—H7A	0.9900
O2—C3	1.369 (3)	C7—H7B	0.9900
O2—C7	1.431 (3)	C8—H8A	0.9800
N1—C9	1.271 (3)	C8—H8B	0.9800
N1—C10	1.469 (3)	C8—H8C	0.9800
C1—C2	1.396 (3)	C9—H9	0.9500
C1—C6	1.401 (3)	C10—C11	1.506 (3)
C1—C9	1.456 (3)	C10—H10A	0.9900
C2—C3	1.406 (3)	C10—H10B	0.9900
C3—C4	1.379 (3)	C11—C12	1.514 (3)
C4—C5	1.393 (3)	C11—H11A	0.9900
C4—H4	0.9500	C11—H11B	0.9900
C5—C6	1.380 (3)	C12—C12ⁱ	1.510 (4)
C5—H5	0.9500	C12—H12A	0.9900
C6—H6	0.9500	C12—H12B	0.9900

C2—O1—H1	109.5	C7—C8—H8A	109.5
C3—O2—C7	117.46 (18)	C7—C8—H8B	109.5
C9—N1—C10	121.2 (2)	H8A—C8—H8B	109.5
C2—C1—C6	119.5 (2)	C7—C8—H8C	109.5
C2—C1—C9	119.9 (2)	H8A—C8—H8C	109.5
C6—C1—C9	120.6 (2)	H8B—C8—H8C	109.5
O1—C2—C1	122.4 (2)	N1—C9—C1	122.2 (2)
O1—C2—C3	117.9 (2)	N1—C9—H9	118.9
C1—C2—C3	119.8 (2)	C1—C9—H9	118.9
O2—C3—C4	126.0 (2)	N1—C10—C11	110.5 (2)
O2—C3—C2	114.4 (2)	N1—C10—H10A	109.6
C4—C3—C2	119.6 (2)	C11—C10—H10A	109.6
C3—C4—C5	120.9 (2)	N1—C10—H10B	109.6
C3—C4—H4	119.6	C11—C10—H10B	109.6
C5—C4—H4	119.6	H10A—C10—H10B	108.1
C6—C5—C4	119.7 (2)	C10—C11—C12	114.0 (2)
C6—C5—H5	120.2	C10—C11—H11A	108.7
C4—C5—H5	120.2	C12—C11—H11A	108.7
C5—C6—C1	120.6 (2)	C10—C11—H11B	108.7
C5—C6—H6	119.7	C12—C11—H11B	108.7
C1—C6—H6	119.7	H11A—C11—H11B	107.6
O2—C7—C8	106.4 (2)	C12ⁱ—C12—C11	113.5 (3)
O2—C7—H7A	110.4	C12ⁱ—C12—H12A	108.9
C8—C7—H7A	110.4	C11—C12—H12A	108.9
O2—C7—H7B	110.4	C12ⁱ—C12—H12B	108.9
C8—C7—H7B	110.4	C11—C12—H12B	108.9
H7A—C7—H7B	108.6	H12A—C12—H12B	107.7

C6—C1—C2—O1	−179.6 (2)	C3—C4—C5—C6	−0.7 (4)
C9—C1—C2—O1	0.1 (4)	C4—C5—C6—C1	0.2 (4)
C6—C1—C2—C3	0.2 (4)	C2—C1—C6—C5	0.0 (4)
C9—C1—C2—C3	179.9 (2)	C9—C1—C6—C5	−179.6 (3)
C7—O2—C3—C4	3.8 (4)	C3—O2—C7—C8	175.5 (2)
C7—O2—C3—C2	−176.2 (2)	C10—N1—C9—C1	−179.9 (3)
O1—C2—C3—O2	−0.9 (4)	C2—C1—C9—N1	2.1 (4)
C1—C2—C3—O2	179.3 (2)	C6—C1—C9—N1	−178.3 (3)
O1—C2—C3—C4	179.1 (2)	C9—N1—C10—C11	175.2 (3)
C1—C2—C3—C4	−0.7 (4)	N1—C10—C11—C12	179.1 (2)
O2—C3—C4—C5	−179.1 (2)	C10—C11—C12—C12ⁱ	178.8 (3)
C2—C3—C4—C5	0.9 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.83	2.570 (3)	147

Experimental details

Crystal data
Chemical formula	C₂₄H₃₂N₂O₄
M_r	412.52
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	6.9094 (13), 6.9184 (13), 11.936 (2)
α, β, γ (°)	91.271 (5), 99.677 (4), 102.550 (4)
V (Å³)	547.97 (18)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.23 × 0.23

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.862, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3505, 2140, 1258
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.168, 1.02
No. of reflections	2140
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.83	2.570 (3)	147

Acknowledgements

This work was supported by Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010–0029626).

References

Bermejo, M. R., Fernández, M. I., Gómez-Fórneas, E., González-Noya, A., Maneiro, M., Pedrido, R. & Rodríguez, M. J. (2007). Eur. J. Inorg. Chem. pp. 3789–3797. Web of Science CSD CrossRef Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Fun, H.-K., Kia, R., Kargar, H. & Jamshidvand, A. (2009). Acta Cryst. E65, o706. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ha, K. (2010). Z. Kristallogr. New Cryst. Struct. 225, 737–738. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar