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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1600–o1601.
Published online 2008 July 26. doi:  10.1107/S1600536808023064
PMCID: PMC2962213

6,6′-Dihydr­oxy-2,2′-[(pentane-1,5-diyl­dioxy)bis­(nitrilo­methyl­idyne)]diphenol

Abstract

The mol­ecule of the title compound, C19H22N2O6, assumes a W-shaped configuration with the dihedral angle between the two halves of the mol­ecule being 82.48 (5)°. There is one half-mol­ecule in the asymmetric unit with a crystallographic twofold rotation axis passing through the central C atom of the five methylene groups in the [—CH=N—O—(CH2)5—O—N=CH—] bridge. The dihedral angle formed by the two benzene rings in each mol­ecule of the title compound is 84.18 (4)°. There are strong intra­molecular O—H(...)N and O—H(...)O hydrogen bonds and weak inter­molecular π–π stacking inter­actions between neighbouring benzene rings, and the inter­molecular plane-to-plane distances are 3.488 (2) and 3.841 (3) Å along the b and c axes, respectively. In the crystal structure, inter­molecular O—H(...)O hydrogen bonds link each mol­ecule to two others, forming an infinite three-dimensional supra­molecular structure.

Related literature

For related literature, see: Akine et al. (2001 [triangle], 2005 [triangle], 2006 [triangle]); Atwood (1997 [triangle]); Dong & Feng (2006 [triangle]); Dong, Zhao et al. (2008 [triangle]); Dong, He et al. (2008 [triangle]); Duan et al. (2007 [triangle]); Venkataramanan et al. (2005 [triangle]); Yu et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1600-scheme1.jpg

Experimental

Crystal data

  • C19H22N2O6
  • M r = 374.39
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1600-efi2.jpg
  • a = 28.439 (3) Å
  • b = 4.6997 (6) Å
  • c = 14.0843 (17) Å
  • β = 100.354 (2)°
  • V = 1851.8 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 (2) K
  • 0.46 × 0.27 × 0.25 mm

Data collection

  • Siemens SMART 1000 CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.955, T max = 0.975
  • 4246 measured reflections
  • 1621 independent reflections
  • 837 reflections with I > 2σ(I)
  • R int = 0.062

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.135
  • S = 1.00
  • 1621 reflections
  • 123 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SMART; data reduction: SAINT (Siemens, 1996 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023064/hg2427sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023064/hg2427Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

Salen-type compounds are one of most versatile mixed-donor ligands in the field of coordination chemistry. There has been growing interest in salen-type ligands, mainly because of their wide application in the field of synthesis, biochemistry, photochemistry and catalysis (Akine et al., 2006; Atwood, 1997; Yu et al., 2008; Venkataramanan et al., 2005). Many salen-type complexes have been structurally characterized (Akine et al., 2006; Yu et al., 2008), but only a relatively small number of free salen-type compounds have been characterized (Akine et al., 2001). As an extension of our work (Dong & Feng, 2006; Duan et al., 2007; Dong, Zhao et al., 2008; Akine et al., 2005) on the structural characterization of salen-type bisoxime compounds, the title compound, (Fig. 1), is reported here.

The molecule assumes a W shape with the dihedral angle between the two halves of the molecule 82.48 (5)°. There is 1/2 molecule per asymmetric unit with a crystallographic twofold rotation axis passing through the central carbon (symmetry code: -x, y, 1/2 - z) of the five carbon atoms in the (—CH=N—O—(CH2)5—O—N═CH—) bridge. This structure is similar to what was observed in our previously reported salen-type bisoxime compound (Duan et al., 2007). The dihedral angle formed by the two benzene rings in each molecule of the title compound is 84.18 (4)°. There are strong intramolecular O—H···N and O—H···O hydrogen bonds and weak intermolecular π–π stacking interactions between the neighbouring benzene rings, and the inter-molecular plane-to-plane distances are 3.488 (2) and 3.841 (3) Å along b and c axis, respectively. In the crystal structure, intermolecular O—H···O hydrogen bonds link each molecule to 2 others into infinite three-dimensional supramolecular structure, which is the crystal structure firstly reported of salen-type bisoxime compounds containing pentamethene bridge.

Experimental

6,6'-Dihydroxy-2,2'-[(pentane-1,5-diyldioxy)bis(nitrilomethylidyne)]diphenol was synthesized according to an analogous method reported earlier (Dong & Feng, 2006; Dong, He et al., 2008). To an ethanol solution (3 ml) of 2,3-dihydroxybenzaldehyde (138.4 mg, 1.0 mmol) was added an ethanol solution (2 ml) of 1,5-bis(aminooxy)pentane (67.4 mg, 0.5 mmol). The reaction mixture was stirred at 328 K for 8 h. After cooling to room temperature, the formed precipitate was separated by filtration, and washed successively with ethanol and ethanol–hexane (1:4), respectively. The product was dried under vacuum to yield 109.3 mg of the title compound. Yield, 58.4%. mp. 408.5–409.5 K. Anal. Calc. for C19H22N2O6: C, 60.95; H, 5.92; N, 7.48. Found: C, 60.75; H, 5.99; N, 7.42.

Pale-brown needle-like single crystals suitable for X-ray diffraction studies were obtained after two weeks by slow evaporation from a ethanol–chloroform mixed solution of the title compound.

Refinement

Non-H atoms were refined anisotropically. H atoms were treated as riding atoms with distances C—H = 0.97 (CH2), or 0.93 Å (CH), O—H = 0.82 Å, and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound with atom numbering scheme [Symmetry codes: -x + 1, y, -z + 3/2]. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.
Fig. 2.
The W shape configuration of the title compound.
Fig. 3.
Part of the supramolecular structure of the title compound along b axis. Intra- and intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C19H22N2O6F000 = 792
Mr = 374.39Dx = 1.343 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 875 reflections
a = 28.439 (3) Åθ = 2.9–22.4º
b = 4.6997 (6) ŵ = 0.10 mm1
c = 14.0843 (17) ÅT = 298 (2) K
β = 100.354 (2)ºNeedle-like, pale-brown
V = 1851.8 (4) Å30.46 × 0.27 × 0.25 mm
Z = 4

Data collection

Siemens SMART 1000 CCD area-detector diffractometer1621 independent reflections
Radiation source: fine-focus sealed tube837 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.062
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −33→30
Tmin = 0.955, Tmax = 0.975k = −5→5
4246 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.135  w = 1/[σ2(Fo2) + (0.0407P)2 + 1.5785P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1621 reflectionsΔρmax = 0.24 e Å3
123 parametersΔρmin = −0.24 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/UeqOcc. (<1)
N10.40208 (8)−0.0702 (5)0.51037 (15)0.0479 (7)
O10.41975 (7)−0.2344 (4)0.59236 (12)0.0542 (6)
O20.39611 (7)0.1384 (5)0.33535 (13)0.0637 (7)
H20.40760.03850.38150.095*
O30.34987 (8)0.4908 (5)0.19941 (14)0.0782 (8)
H30.37300.38700.19910.117*
C10.46067 (10)−0.3889 (7)0.57460 (19)0.0535 (9)
H1A0.4849−0.25760.56100.064*
H1B0.4518−0.51260.51920.064*
C20.47987 (11)−0.5624 (7)0.66243 (18)0.0543 (9)
H2A0.5048−0.68680.64780.065*
H2B0.4544−0.68140.67800.065*
C30.5000−0.3833 (9)0.75000.0500 (11)
H3A0.4749−0.26170.76570.060*0.50
H3B0.5251−0.26170.73430.060*0.50
C40.36573 (10)0.0763 (7)0.52087 (19)0.0470 (8)
H40.35400.06440.57830.056*
C50.34239 (9)0.2611 (6)0.44479 (18)0.0418 (7)
C60.35833 (10)0.2865 (6)0.35701 (19)0.0439 (7)
C70.33496 (11)0.4666 (7)0.28589 (19)0.0509 (8)
C80.29684 (11)0.6252 (7)0.3023 (2)0.0573 (9)
H80.28190.74980.25500.069*
C90.28046 (11)0.6018 (7)0.3883 (2)0.0590 (9)
H90.25420.70750.39850.071*
C100.30300 (10)0.4222 (7)0.4586 (2)0.0538 (9)
H100.29180.40750.51650.065*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0471 (15)0.0517 (18)0.0431 (13)0.0017 (13)0.0029 (11)0.0029 (12)
O10.0510 (13)0.0670 (16)0.0443 (11)0.0114 (12)0.0076 (9)0.0072 (10)
O20.0557 (14)0.0800 (17)0.0593 (13)0.0191 (13)0.0211 (10)0.0113 (11)
O30.0804 (16)0.099 (2)0.0575 (13)0.0188 (15)0.0195 (12)0.0206 (13)
C10.0520 (19)0.056 (2)0.0516 (17)0.0052 (17)0.0074 (15)−0.0072 (15)
C20.058 (2)0.049 (2)0.0529 (17)0.0074 (17)0.0018 (15)−0.0022 (15)
C30.044 (2)0.049 (3)0.055 (2)0.0000.0043 (19)0.000
C40.0450 (18)0.056 (2)0.0408 (15)−0.0017 (16)0.0093 (13)−0.0038 (15)
C50.0342 (16)0.045 (2)0.0447 (15)−0.0038 (15)0.0033 (13)−0.0061 (13)
C60.0365 (16)0.046 (2)0.0498 (16)−0.0021 (15)0.0093 (13)−0.0063 (14)
C70.053 (2)0.055 (2)0.0440 (16)−0.0018 (17)0.0059 (14)0.0002 (15)
C80.054 (2)0.055 (2)0.0579 (19)0.0044 (18)−0.0037 (16)0.0007 (16)
C90.0465 (19)0.063 (2)0.066 (2)0.0112 (17)0.0040 (16)−0.0084 (18)
C100.0471 (19)0.062 (2)0.0521 (17)0.0012 (17)0.0099 (14)−0.0109 (16)

Geometric parameters (Å, °)

N1—C41.273 (3)C3—H3A0.9700
N1—O11.405 (3)C3—H3B0.9700
O1—C11.431 (3)C4—C51.444 (4)
O2—C61.360 (3)C4—H40.9300
O2—H20.8200C5—C101.394 (4)
O3—C71.364 (3)C5—C61.396 (3)
O3—H30.8200C6—C71.386 (4)
C1—C21.500 (4)C7—C81.369 (4)
C1—H1A0.9700C8—C91.378 (4)
C1—H1B0.9700C8—H80.9300
C2—C31.518 (4)C9—C101.370 (4)
C2—H2A0.9700C9—H90.9300
C2—H2B0.9700C10—H100.9300
C3—C2i1.518 (4)
C4—N1—O1112.3 (2)N1—C4—C5120.9 (3)
N1—O1—C1108.47 (19)N1—C4—H4119.5
C6—O2—H2109.5C5—C4—H4119.5
C7—O3—H3109.5C10—C5—C6118.3 (3)
O1—C1—C2108.6 (2)C10—C5—C4119.8 (3)
O1—C1—H1A110.0C6—C5—C4122.0 (3)
C2—C1—H1A110.0O2—C6—C7116.5 (3)
O1—C1—H1B110.0O2—C6—C5123.4 (3)
C2—C1—H1B110.0C7—C6—C5120.2 (3)
H1A—C1—H1B108.4O3—C7—C8119.2 (3)
C1—C2—C3113.4 (3)O3—C7—C6120.7 (3)
C1—C2—H2A108.9C8—C7—C6120.1 (3)
C3—C2—H2A108.9C7—C8—C9120.5 (3)
C1—C2—H2B108.9C7—C8—H8119.8
C3—C2—H2B108.9C9—C8—H8119.8
H2A—C2—H2B107.7C10—C9—C8119.8 (3)
C2—C3—C2i112.6 (4)C10—C9—H9120.1
C2—C3—H3A109.1C8—C9—H9120.1
C2i—C3—H3A109.1C9—C10—C5121.2 (3)
C2—C3—H3B109.1C9—C10—H10119.4
C2i—C3—H3B109.1C5—C10—H10119.4
H3A—C3—H3B107.8
C4—N1—O1—C1−179.4 (2)O2—C6—C7—O3−0.2 (4)
N1—O1—C1—C2179.5 (2)C5—C6—C7—O3−179.2 (3)
O1—C1—C2—C3−66.3 (3)O2—C6—C7—C8−179.4 (3)
C1—C2—C3—C2i−178.9 (3)C5—C6—C7—C81.5 (4)
O1—N1—C4—C5179.6 (2)O3—C7—C8—C9178.9 (3)
N1—C4—C5—C10−179.2 (3)C6—C7—C8—C9−1.9 (5)
N1—C4—C5—C60.2 (4)C7—C8—C9—C101.2 (5)
C10—C5—C6—O2−179.5 (2)C8—C9—C10—C5−0.1 (5)
C4—C5—C6—O21.1 (4)C6—C5—C10—C9−0.2 (4)
C10—C5—C6—C7−0.5 (4)C4—C5—C10—C9179.2 (3)
C4—C5—C6—C7−179.9 (3)

Symmetry codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.922.630 (3)144
O3—H3···O20.822.242.689 (3)115
O3—H3···O1ii0.822.292.958 (3)139

Symmetry codes: (ii) x, −y, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2427).

References

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