6,6′-Dihydr­oxy-2,2′-[(butane-1,4-diyldi­oxy)bis­(nitrilo­methyl­idyne)]diphenol

Dong, W.-K.; He, X.-N.; Sun, Y.-X.; Xu, L.; Guan, Y.-H.

doi:10.1107/S1600536808028468

organic compounds

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doi:10.1107/S1600536808028468

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6,6′-Dihydroxy-2,2′-[(butane-1,4-diyldioxy)bis(nitrilomethylidyne)]diphenol

Wen-Kui Dong,^a ^* Xue-Ni He,^a Yin-Xia Sun,^a Li Xu ^a and Yong-Hong Guan ^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 12 August 2008; accepted 5 September 2008; online 13 September 2008)

The molecule of the centrosymmetric title compound, C₁₈H₂₀N₂O₆, assumes an E configuration with respect to the azomethine C=N bond. The imino group is coplanar with the aromatic ring. Intramolecular O—H⋯O and O—H⋯N bonds are found between the hydroxyl groups and adjacent O (or N) atoms. In the crystal structure, intermolecular O—H⋯O bonds link each molecule to two others, forming a layered network.

Related literature

For background information, see: Sharma (2002 ). For related structures, see: Fan et al. (2006 ); Wang et al. (2003 ); Akine et al. (2006 ). Dong et al. (2007 , 2008a ,b ); Wang et al. (2007 ).

Experimental

Crystal data

C₁₈H₂₀N₂O₆
M_r = 360.36
Mmonoclinic, C 2/c
a = 27.484 (3) Å
b = 4.7106 (7) Å
c = 14.0081 (19) Å
β = 104.306 (2)°
V = 1757.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 (2) K
0.55 × 0.53 × 0.48 mm

Data collection

Siemens Smart 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.945, T_max = 0.952
4086 measured reflections
1555 independent reflections
1112 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.106
S = 1.10
1555 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.15 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	1.94	2.648 (2)	145
O3—H3⋯O2	0.82	2.26	2.706 (2)	115
O3—H3⋯O1ⁱ	0.82	2.26	2.930 (2)	139
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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/S1600536808028468/fl2218sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028468/fl2218Isup2.hkl

checkCIF report

Comment top

The design of supramolecular structures involves molecules for which intermolecular hydrogen bonds act as driving, directional and cohesive forces (Sharma, 2002). Although many stable and well documented structures have been reported (Fan et al., 2006; Wang et al., 2003), the supramolecular structures of salen-type bisoxime compounds have rarely been determined. The first reported supramolecular salen-type bisoxime compound, 6,6'-dihydroxy-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol has an intermolecular hydrogen bond network involving four hydroxyl groups and cocrystallized water molecules (Akine et al., 2006). In this article, we report the synthesis and structure of the title compound (I) (Fig. 1).

(I) lies across a crystallographic inversion centre to give 1/2 molecule per asymmetric unit. It assumes an E configuration with respect to the azomethine C═N bond. The imino group is coplanar with the aromatic ring. The planar units are parallel to one another but extend in opposite directions from the tetramethylene bridge. Strong intramolecular O(3)—H(3)···O(2) and O(2)—H(2)···N(1) bonds are found between the hydroxyl groups and adjacent O (or 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; Dong et al., 2008a).

In the crystal packing weak intermolecular O—H···O hydrogen bonds link each molecule to 4 others, forming an infinite three-dimensional supramolecular structure (Figs. 2 and 3) that differs from the structures of 6,6'-dihydroxy-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol (Akine et al., 2006) and 6,6'-dihydroxy-2,2'-[(pentane-1,5-diyldioxy)bis(nitrilomethylidyne)]diphenol (Dong et al., 2008b), in which the molecules exhibit one-dimensional chains formed through strong intermolecular π–π stacking interactions or weak intermolecular hydrogen bonds.

Related literature top

For background information, see: Sharma (2002). For related structures, see: Fan et al. (2006); Wang et al. (2003); Akine et al. (2006). Dong et al. (2007, 2008a,b); Wang et al. (2007).

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 2,3-dihydroxybenzaldehyde (276.6 mg, 2.0 mmol) was added an ethanol solution (5 ml) of 1,4-bis(aminooxy)butane (120.0 mg, 1.0 mmol). After the solution had been stirred at 328 K for 3 h, the reaction mixture was separated by filtration, washed successively with ethanol and ethanol/hexane (1:4), respectively. The product was dried under reduced pressure and purified with recrystallization from ethanol to yield 59.9 mg of pale-brown crystalline solid. Yield, 17.2%, m.p. 388–389 K. Anal. Calc. (%) for C₁₈H₂₀N₂O₆: C, 59.99; H, 5.59; N, 7.77. Found: C, 60.23; H, 5.45; N, 7.60.

Block-shaped crystals of (I) suitable for X-ray crystal analysis were grown from a mixture of tetrahydrofuran/ethanol (1:1) solution by slow evaporation at room temperature, which afforded pale-brown crystals.

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 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 c axis showing the E configuration.
	Fig. 3. Part of the supramolecular structure of the title compound along b axis. Intra- and intermolecular hydrogen bonds are shown as dashed lines.

6,6'-Dihydroxy-2,2'-[(butane-1,4-diyldioxy)bis(nitrilomethylidyne)]diphenol top

Crystal data top

C₁₈H₂₀N₂O₆	Z = 4
M_r = 360.36	F(000) = 760
Mmonoclinic, C2/c	D_x = 1.362 Mg m⁻³
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 27.484 (3) Å	Cell parameters from 1695 reflections
b = 4.7106 (7) Å	θ = 2.4–27.8°
c = 14.0081 (19) Å	µ = 0.10 mm⁻¹
α = 90°	T = 298 K
β = 104.306 (2)°	Block-shaped, pale-brown
γ = 90°	0.55 × 0.53 × 0.48 mm
V = 1757.4 (4) Å³

Data collection top

Bruker Smart 1000 CCD area-detector diffractometer	1555 independent reflections
Radiation source: fine-focus sealed tube	1112 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→32
T_min = 0.945, T_max = 0.952	k = −5→5
4086 measured reflections	l = −16→16

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0457P)² + 0.5441P] where P = (F_o² + 2F_c²)/3
1555 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₈H₂₀N₂O₆	γ = 90°
M_r = 360.36	V = 1757.4 (4) Å³
Mmonoclinic, C2/c	Z = 4
a = 27.484 (3) Å	Mo Kα radiation
b = 4.7106 (7) Å	µ = 0.10 mm⁻¹
c = 14.0081 (19) Å	T = 298 K
α = 90°	0.55 × 0.53 × 0.48 mm
β = 104.306 (2)°

Data collection top

Bruker Smart 1000 CCD area-detector diffractometer	1555 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1112 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.952	R_int = 0.026
4086 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.10	Δρ_max = 0.16 e Å⁻³
1555 reflections	Δρ_min = −0.16 e Å⁻³
118 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	0.08963 (5)	0.5854 (3)	0.37586 (9)	0.0445 (4)
O1	0.07135 (4)	0.7516 (3)	0.44261 (7)	0.0505 (3)
O2	0.09612 (4)	0.3675 (3)	0.20520 (8)	0.0595 (4)
H2	0.0848	0.4741	0.2407	0.089*
O3	0.14491 (5)	0.0061 (3)	0.11078 (8)	0.0719 (5)
H3	0.1213	0.1137	0.0890	0.108*
C1	0.02835 (6)	0.9102 (4)	0.39001 (12)	0.0484 (4)
H1A	0.0020	0.7819	0.3565	0.058*
H1B	0.0375	1.0312	0.3411	0.058*
C2	0.01029 (6)	1.0875 (4)	0.46377 (12)	0.0486 (5)
H2A	−0.0158	1.2150	0.4287	0.058*
H2B	0.0379	1.2027	0.5002	0.058*
C3	0.12781 (6)	0.4381 (4)	0.41858 (12)	0.0444 (4)
H3A	0.1401	0.4526	0.4865	0.053*
C4	0.15231 (5)	0.2489 (3)	0.36349 (11)	0.0396 (4)
C5	0.13584 (6)	0.2207 (4)	0.26086 (11)	0.0420 (4)
C6	0.16024 (6)	0.0352 (4)	0.21112 (12)	0.0474 (4)
C7	0.20050 (7)	−0.1205 (4)	0.26152 (13)	0.0531 (5)
H7	0.2165	−0.2451	0.2277	0.064*
C8	0.21755 (6)	−0.0930 (4)	0.36307 (13)	0.0534 (5)
H8	0.2451	−0.1977	0.3971	0.064*
C9	0.19369 (6)	0.0890 (4)	0.41324 (12)	0.0475 (4)
H9	0.2052	0.1062	0.4812	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0463 (8)	0.0494 (9)	0.0400 (7)	−0.0006 (7)	0.0146 (6)	−0.0072 (7)
O1	0.0512 (7)	0.0609 (8)	0.0389 (6)	0.0100 (6)	0.0105 (5)	−0.0093 (6)
O2	0.0598 (8)	0.0715 (9)	0.0411 (6)	0.0174 (6)	0.0011 (6)	−0.0067 (6)
O3	0.0830 (9)	0.0906 (11)	0.0404 (7)	0.0200 (8)	0.0123 (6)	−0.0101 (7)
C1	0.0467 (9)	0.0537 (11)	0.0438 (9)	0.0022 (8)	0.0094 (7)	0.0009 (8)
C2	0.0488 (10)	0.0465 (11)	0.0524 (10)	0.0047 (8)	0.0158 (8)	0.0026 (8)
C3	0.0451 (9)	0.0513 (11)	0.0359 (8)	−0.0040 (8)	0.0088 (7)	−0.0031 (8)
C4	0.0384 (8)	0.0428 (10)	0.0379 (8)	−0.0055 (7)	0.0102 (7)	−0.0011 (7)
C5	0.0396 (9)	0.0452 (10)	0.0400 (9)	−0.0013 (7)	0.0077 (7)	0.0014 (8)
C6	0.0525 (10)	0.0513 (11)	0.0405 (9)	−0.0021 (9)	0.0153 (8)	−0.0034 (8)
C7	0.0529 (10)	0.0528 (11)	0.0586 (11)	0.0045 (9)	0.0232 (9)	−0.0016 (9)
C8	0.0454 (10)	0.0570 (12)	0.0578 (11)	0.0078 (9)	0.0124 (8)	0.0099 (9)
C9	0.0448 (9)	0.0565 (11)	0.0402 (9)	−0.0010 (8)	0.0083 (7)	0.0053 (8)

Geometric parameters (Å, º) top

N1—C3	1.277 (2)	C2—H2B	0.9700
N1—O1	1.4041 (16)	C3—C4	1.449 (2)
O1—C1	1.4377 (19)	C3—H3A	0.9300
O2—C5	1.3627 (19)	C4—C9	1.398 (2)
O2—H2	0.8200	C4—C5	1.403 (2)
O3—C6	1.3709 (19)	C5—C6	1.389 (2)
O3—H3	0.8200	C6—C7	1.369 (2)
C1—C2	1.505 (2)	C7—C8	1.389 (2)
C1—H1A	0.9700	C7—H7	0.9300
C1—H1B	0.9700	C8—C9	1.373 (2)
C2—C2ⁱ	1.521 (3)	C8—H8	0.9300
C2—H2A	0.9700	C9—H9	0.9300

C3—N1—O1	112.25 (12)	C9—C4—C5	118.48 (15)
N1—O1—C1	109.42 (11)	C9—C4—C3	119.58 (14)
C5—O2—H2	109.5	C5—C4—C3	121.94 (14)
C6—O3—H3	109.5	O2—C5—C6	116.75 (14)
O1—C1—C2	107.79 (13)	O2—C5—C4	123.26 (15)
O1—C1—H1A	110.1	C6—C5—C4	119.99 (15)
C2—C1—H1A	110.1	C7—C6—O3	118.65 (16)
O1—C1—H1B	110.1	C7—C6—C5	120.48 (15)
C2—C1—H1B	110.1	O3—C6—C5	120.87 (15)
H1A—C1—H1B	108.5	C6—C7—C8	120.18 (17)
C1—C2—C2ⁱ	113.41 (18)	C6—C7—H7	119.9
C1—C2—H2A	108.9	C8—C7—H7	119.9
C2ⁱ—C2—H2A	108.9	C9—C8—C7	119.96 (16)
C1—C2—H2B	108.9	C9—C8—H8	120.0
C2ⁱ—C2—H2B	108.9	C7—C8—H8	120.0
H2A—C2—H2B	107.7	C8—C9—C4	120.90 (16)
N1—C3—C4	121.39 (14)	C8—C9—H9	119.6
N1—C3—H3A	119.3	C4—C9—H9	119.6
C4—C3—H3A	119.3

C3—N1—O1—C1	−179.64 (14)	O2—C5—C6—C7	−179.99 (15)
N1—O1—C1—C2	−179.36 (12)	C4—C5—C6—C7	−0.2 (3)
O1—C1—C2—C2ⁱ	−66.3 (2)	O2—C5—C6—O3	0.7 (2)
O1—N1—C3—C4	179.32 (13)	C4—C5—C6—O3	−179.56 (16)
N1—C3—C4—C9	−179.32 (15)	O3—C6—C7—C8	178.97 (17)
N1—C3—C4—C5	0.8 (2)	C5—C6—C7—C8	−0.4 (3)
C9—C4—C5—O2	−179.62 (14)	C6—C7—C8—C9	0.6 (3)
C3—C4—C5—O2	0.2 (3)	C7—C8—C9—C4	−0.2 (3)
C9—C4—C5—C6	0.6 (2)	C5—C4—C9—C8	−0.4 (2)
C3—C4—C5—C6	−179.53 (15)	C3—C4—C9—C8	179.71 (15)

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	1.94	2.648 (2)	145
O3—H3···O2	0.82	2.26	2.706 (2)	115
O3—H3···O1ⁱⁱ	0.82	2.26	2.930 (2)	139

Symmetry code: (ii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₀N₂O₆
M_r	360.36
Crystal system, space group	Mmonoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	27.484 (3), 4.7106 (7), 14.0081 (19)
α, β, γ (°)	90, 104.306 (2), 90
V (Å³)	1757.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.55 × 0.53 × 0.48

Data collection
Diffractometer	Bruker Smart 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.945, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	4086, 1555, 1112
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.106, 1.10
No. of reflections	1555
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16

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	0.820	1.937	2.648 (2)	144.51
O3—H3···O2	0.820	2.261	2.706 (2)	114.47
O3—H3···O1ⁱ	0.820	2.259	2.930 (2)	139.30

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

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

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6,6′-Dihydr­­oxy-2,2′-[(butane-1,4-diyldi­­oxy)bis­­(nitrilo­methyl­­idyne)]diphenol

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

6,6′-Dihydroxy-2,2′-[(butane-1,4-diyldioxy)bis(nitrilomethylidyne)]diphenol