2,2′-[1,1′-(Hexane-1,6-diyldioxy­dinitrilo)diethyl­idyne]diphenol

Dong, W.-K.; He, X.-N.; Sun, Y.-X.; Xu, L.; Tong, J.-F.

doi:10.1107/S1600536808024902

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1726

doi:10.1107/S1600536808024902

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2,2′-[1,1′-(Hexane-1,6-diyldioxydinitrilo)diethylidyne]diphenol

Wen-Kui Dong,^a ^* Xue-Ni He,^a Yin-Xia Sun,^a Li Xu ^a and Jun-Feng Tong ^a

^aSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: dongwk@mail.lzjtu.cn

(Received 18 July 2008; accepted 3 August 2008; online 9 August 2008)

The molecule of the title compound, C₂₂H₂₈N₂O₂, lies across an inversion centre with one half-molecule in the asymmetric unit. The molecule adopts an E configuration with respect to the azomethine C=N bond and the imino group is coplanar with the aromatic ring. Within the molecule, the planar units are parallel, but extend in opposite directions from the hexamethylene bridge. There are intramolecular O—H⋯N hydrogen bonds between the hydroxyl groups and the oxime N atoms. There are also weak intermolecular C—H⋯O bonds that link each molecule to two others, forming chains along the a axis.

Related literature

For related literature, see: Atwood (1997 ); Canali & Sherrington (1999 ); Dong et al. (2007 , 2008a ,b ,c ); Jarrahpour et al. (2004 ); Sun et al. (2004 ); Venkataramanan et al. (2005 ); Wang et al. (2007 ); Yu et al. (2008 ).

Experimental

Crystal data

C₂₂H₂₈N₂O₄
M_r = 384.46
Monoclinic, C 2/c
a = 13.0052 (19) Å
b = 4.6441 (6) Å
c = 34.221 (3) Å
β = 95.000 (2)°
V = 2059.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.50 × 0.43 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.959, T_max = 0.982
4854 measured reflections
1816 independent reflections
1025 reflections with I > 2σ(I)
R_int = 0.081

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.185
S = 1.06
1816 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.82	1.83	2.549 (3)	145
C4—H4B⋯O2ⁱ	0.96	2.70	3.476 (4)	138
C11—H11⋯O2ⁱ	0.93	2.69	3.587 (4)	163
Symmetry code: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); 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/S1600536808024902/fl2214sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024902/fl2214Isup2.hkl

checkCIF report

Comment top

Salen-type compounds have received a great deal of attention because of their versatility (Atwood et al., 1997; Yu et al., 2008; Venkataramanan et al., 2005). Some, along with their transition metal complexes, exhibit anticancer and anticoagulant activity (Sun et al., 2004) as well as antibacterial and antifungal properties (Jarrahpour et al., 2004). In addition, some of the salen-type species can be used as catalysts, especially in the area of asymmetric catalysis (Canali et al., 1999). Recently, we have reported the structures of a number molecules similar to the title compound (Wang et al., 2007; Dong et al., 2007, 2008a).

The title compound crystallized around a crystallographic inversion centre passing through the central C-C bond of the hexamethylene bridge (symmetry code: -x, -y, -z) to give 1/2 molecule per asymmetric unit (FIG. 1). It adopts an E configuration with respect to the azomethine C=N bond and the imino group is coplanar with the aromatic ring. Within the molecule, the planar units are parallel, but extend in opposite directions from the hexamethylene bridge. Intramolecular O(2)—H(2)···N(1) hydrogen bonds are found between the hydroxyl groups and the oxime N atoms (Table 1). This is similar to what was observed in our previously reported salen-type bisoxime compounds (Wang et al., 2007; Dong et al., 2007, 2008a).

In the unit cell there are also weak intermolecular C-H···O interactions that link each molecule to 2 others to form chains along the a axis (Table 1, Fig. 2), This differs from packing interactions found for 1,1'-[(hexane-1,6-diyldioxy)bis(nitrilomethylidyne)]dinaphthalene (Dong et al., 2008b) and 6,6'-dimethoxy-2,2'-[(hexane-1,6-diyldioxy)bis(nitrilomethylidyne)]diphenol (Dong et al., 2008c) in which the molecules exhibit three-dimensional supramolecular structures formed through strong intermolecular π-π stacking interactions or weak intermolecular hydrogen bonds.

Related literature top

For related literature, see: Atwood (1997); Canali & Sherrington (1999); Dong et al. (2007, 2008a,b,c); Jarrahpour et al. (2004); Sun et al. (2004); Venkataramanan et al. (2005); Wang et al. (2007); Yu et al. (2008).

Experimental top

The title compound was synthesized according to an analogous method reported earlier (Dong et al., 2007). To an ethanol solution (5 ml) of 2'-hydroxyacetophenone (561.4 mg, 4.00 mmol) was added an ethanol solution (4 ml) of 1,6-bis(aminooxy)hexane (296.5 mg, 2.00 mmol). The reaction mixture was stirred at 328 K for 4 h. The resulting precipitate was separated by filtration, and washed successively with ethanol and ethanol-hexane (1:4). The product was dried under vacuum to yield 434.0 mg of the title compound. Yield, 56.4%. mp. 343 K. Anal. Calc. for C₂₂H₂₈N₂O₂: C, 74.97; H, 8.01; N, 7.95. Found: C, 75.08; H, 7.85; N, 7.82.

Colorless block-shaped single crystals suitable for X-ray diffraction studies were obtained after several weeks by slow evaporation from an acetone solution.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 the title compound with the atom numbering scheme [Symmetry codes: -x, -y + 2, -z + 1]. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.
	Fig. 2. Three-dimensional packing diagram of the title compound along the b axis. Intra- and intermolecular hydrogen bonds are shown as dashed lines.

2,2'-[1,1'-(Hexane-1,6-diyldioxydinitrilo)diethylidyne]diphenol top

Crystal data top

C₂₂H₂₈N₂O₄	F(000) = 824
M_r = 384.46	D_x = 1.240 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C -2yc	Cell parameters from 1018 reflections
a = 13.0052 (19) Å	θ = 2.4–23.2°
b = 4.6441 (6) Å	µ = 0.09 mm⁻¹
c = 34.221 (3) Å	T = 298 K
β = 95.000 (2)°	Block-shaped, colorless
V = 2059.0 (4) Å³	0.50 × 0.43 × 0.22 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1816 independent reflections
Radiation source: fine-focus sealed tube	1025 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→15
T_min = 0.959, T_max = 0.982	k = −5→5
4854 measured reflections	l = −36→40

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0707P)² + 0.7764P] where P = (F_o² + 2F_c²)/3
1816 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₂H₂₈N₂O₄	V = 2059.0 (4) Å³
M_r = 384.46	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.0052 (19) Å	µ = 0.09 mm⁻¹
b = 4.6441 (6) Å	T = 298 K
c = 34.221 (3) Å	0.50 × 0.43 × 0.22 mm
β = 95.000 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1816 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1025 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.982	R_int = 0.081
4854 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 1.06	Δρ_max = 0.16 e Å⁻³
1816 reflections	Δρ_min = −0.17 e Å⁻³
127 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	0.20750 (18)	0.7620 (6)	0.39536 (6)	0.0558 (7)
O1	0.25649 (15)	0.9218 (5)	0.42661 (6)	0.0689 (7)
O2	0.04940 (15)	0.5889 (6)	0.35249 (6)	0.0814 (8)
H2	0.0805	0.6818	0.3702	0.122*
C1	0.1805 (2)	1.0874 (8)	0.44434 (8)	0.0634 (9)
H1A	0.1380	1.1879	0.4240	0.076*
H1B	0.2149	1.2310	0.4614	0.076*
C2	0.1115 (2)	0.9044 (7)	0.46802 (8)	0.0568 (8)
H2A	0.0712	0.7748	0.4505	0.068*
H2B	0.1541	0.7885	0.4866	0.068*
C3	0.0392 (2)	1.0874 (7)	0.49000 (7)	0.0545 (8)
H3A	0.0796	1.2005	0.5096	0.065*
H3B	0.0030	1.2202	0.4717	0.065*
C4	0.3827 (2)	0.5826 (10)	0.38989 (9)	0.0837 (12)
H4A	0.4084	0.7690	0.3980	0.126*
H4B	0.4184	0.5160	0.3682	0.126*
H4C	0.3938	0.4498	0.4113	0.126*
C5	0.2690 (2)	0.6031 (7)	0.37758 (8)	0.0501 (7)
C6	0.2230 (2)	0.4313 (7)	0.34493 (7)	0.0496 (7)
C7	0.1174 (2)	0.4300 (8)	0.33391 (8)	0.0606 (8)
C8	0.0770 (3)	0.2574 (9)	0.30335 (9)	0.0776 (10)
H8	0.0062	0.2574	0.2965	0.093*
C9	0.1397 (3)	0.0870 (9)	0.28307 (9)	0.0786 (11)
H9	0.1116	−0.0283	0.2626	0.094*
C10	0.2445 (3)	0.0870 (8)	0.29310 (9)	0.0751 (10)
H10	0.2876	−0.0278	0.2794	0.090*
C11	0.2846 (2)	0.2562 (8)	0.32321 (8)	0.0626 (9)
H11	0.3556	0.2553	0.3296	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0568 (14)	0.0595 (17)	0.0530 (13)	−0.0017 (15)	0.0155 (11)	−0.0068 (13)
O1	0.0583 (12)	0.0827 (17)	0.0685 (12)	−0.0034 (13)	0.0215 (10)	−0.0199 (12)
O2	0.0554 (13)	0.093 (2)	0.0976 (16)	0.0061 (14)	0.0143 (12)	−0.0252 (15)
C1	0.0693 (19)	0.059 (2)	0.0651 (17)	−0.0062 (18)	0.0267 (15)	−0.0163 (16)
C2	0.0571 (17)	0.056 (2)	0.0589 (16)	0.0034 (17)	0.0163 (13)	−0.0037 (16)
C3	0.0593 (17)	0.0524 (19)	0.0535 (16)	0.0009 (16)	0.0144 (13)	−0.0038 (15)
C4	0.0543 (19)	0.108 (3)	0.089 (2)	0.011 (2)	0.0101 (16)	−0.027 (2)
C5	0.0506 (16)	0.0483 (18)	0.0542 (15)	0.0036 (15)	0.0202 (13)	0.0017 (15)
C6	0.0562 (17)	0.0486 (18)	0.0464 (14)	0.0036 (16)	0.0172 (12)	0.0078 (14)
C7	0.0634 (19)	0.059 (2)	0.0610 (18)	0.0055 (18)	0.0157 (15)	0.0015 (17)
C8	0.077 (2)	0.079 (3)	0.077 (2)	−0.004 (2)	0.0061 (18)	−0.007 (2)
C9	0.108 (3)	0.070 (3)	0.0583 (19)	−0.003 (2)	0.008 (2)	−0.0042 (18)
C10	0.107 (3)	0.064 (2)	0.0571 (19)	0.019 (2)	0.0239 (18)	−0.0010 (18)
C11	0.074 (2)	0.061 (2)	0.0547 (17)	0.012 (2)	0.0190 (15)	0.0036 (17)

Geometric parameters (Å, º) top

N1—C5	1.281 (3)	C4—H4A	0.9600
N1—O1	1.408 (3)	C4—H4B	0.9600
O1—C1	1.429 (3)	C4—H4C	0.9600
O2—C7	1.352 (4)	C5—C6	1.458 (4)
O2—H2	0.8200	C6—C7	1.393 (4)
C1—C2	1.520 (4)	C6—C11	1.399 (4)
C1—H1A	0.9700	C7—C8	1.384 (5)
C1—H1B	0.9700	C8—C9	1.368 (5)
C2—C3	1.515 (4)	C8—H8	0.9300
C2—H2A	0.9700	C9—C10	1.376 (5)
C2—H2B	0.9700	C9—H9	0.9300
C3—C3ⁱ	1.512 (5)	C10—C11	1.363 (5)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	C11—H11	0.9300
C4—C5	1.504 (4)

C5—N1—O1	113.9 (2)	C5—C4—H4C	109.5
N1—O1—C1	108.8 (2)	H4A—C4—H4C	109.5
C7—O2—H2	109.5	H4B—C4—H4C	109.5
O1—C1—C2	112.8 (3)	N1—C5—C6	116.6 (2)
O1—C1—H1A	109.0	N1—C5—C4	122.9 (3)
C2—C1—H1A	109.0	C6—C5—C4	120.5 (3)
O1—C1—H1B	109.0	C7—C6—C11	116.8 (3)
C2—C1—H1B	109.0	C7—C6—C5	122.6 (3)
H1A—C1—H1B	107.8	C11—C6—C5	120.6 (3)
C3—C2—C1	111.8 (2)	O2—C7—C8	116.8 (3)
C3—C2—H2A	109.3	O2—C7—C6	122.7 (3)
C1—C2—H2A	109.3	C8—C7—C6	120.5 (3)
C3—C2—H2B	109.3	C9—C8—C7	120.9 (3)
C1—C2—H2B	109.3	C9—C8—H8	119.5
H2A—C2—H2B	107.9	C7—C8—H8	119.5
C3ⁱ—C3—C2	113.3 (3)	C8—C9—C10	119.6 (3)
C3ⁱ—C3—H3A	108.9	C8—C9—H9	120.2
C2—C3—H3A	108.9	C10—C9—H9	120.2
C3ⁱ—C3—H3B	108.9	C11—C10—C9	119.6 (3)
C2—C3—H3B	108.9	C11—C10—H10	120.2
H3A—C3—H3B	107.7	C9—C10—H10	120.2
C5—C4—H4A	109.5	C10—C11—C6	122.5 (3)
C5—C4—H4B	109.5	C10—C11—H11	118.8
H4A—C4—H4B	109.5	C6—C11—H11	118.8

C5—N1—O1—C1	−179.4 (2)	C5—C6—C7—O2	0.3 (5)
N1—O1—C1—C2	72.4 (3)	C11—C6—C7—C8	1.3 (5)
O1—C1—C2—C3	173.9 (2)	C5—C6—C7—C8	−178.3 (3)
C1—C2—C3—C3ⁱ	173.2 (3)	O2—C7—C8—C9	−179.4 (3)
O1—N1—C5—C6	179.9 (2)	C6—C7—C8—C9	−0.7 (5)
O1—N1—C5—C4	1.9 (4)	C7—C8—C9—C10	−0.1 (5)
N1—C5—C6—C7	−1.9 (4)	C8—C9—C10—C11	0.2 (5)
C4—C5—C6—C7	176.1 (3)	C9—C10—C11—C6	0.5 (5)
N1—C5—C6—C11	178.5 (3)	C7—C6—C11—C10	−1.2 (4)
C4—C5—C6—C11	−3.4 (4)	C5—C6—C11—C10	178.4 (3)
C11—C6—C7—O2	179.9 (3)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.83	2.549 (3)	145
C4—H4B···O2ⁱⁱ	0.96	2.70	3.476 (4)	138
C11—H11···O2ⁱⁱ	0.93	2.69	3.587 (4)	163

Symmetry code: (ii) x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₈N₂O₄
M_r	384.46
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	13.0052 (19), 4.6441 (6), 34.221 (3)
β (°)	95.000 (2)
V (Å³)	2059.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.43 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.959, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	4854, 1816, 1025
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.185, 1.06
No. of reflections	1816
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
O2—H2···N1	0.82	1.83	2.549 (3)	145.0
C4—H4B···O2ⁱ	0.96	2.70	3.476 (4)	138.3
C11—H11···O2ⁱ	0.93	2.69	3.587 (4)	163.0

Symmetry code: (i) x+1/2, y−1/2, z.

Acknowledgements

This work was supported by the Foundation of the Education Department of Gansu Province (No. 0604–01) and the `Qing Lan' Talent Engineering Funds of Lanzhou Jiaotong University (No. QL-03–01 A), which are gratefully acknowledged.

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