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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1810.
Published online 2008 August 23. doi:  10.1107/S1600536808026731
PMCID: PMC2960728

6,6′-Dihydr­oxy-2,2′-[(propane-1,3-diyl­dioxy)bis­(nitrilo­methyl­idyne)]diphenol

Abstract

The mol­ecule of the title compound, C17H18N2O6, adopts a V-shaped conformation, the dihedral angle between the two halves of the mol­ecule being 81.31 (4) °. There is one half-mol­ecule in the asymmetric unit, with a crystallographic twofold rotation axis passing through the central C atom. There are strong intra­molecular O—H(...)N and O—H(...)O hydrogen bonds involving the hydr­oxy group and adjacent O and N atoms. In the crystal structure, inter­molecular O—H(...)O hydrogen bonds link the mol­ecules, forming an infinite three-dimensional supra­molecular structure.

Related literature

For related literature, see: Akine et al. (2006 [triangle]); Dong & Feng (2006 [triangle]); Dong et al. (2008a [triangle],b [triangle],c [triangle]); Duan et al. (2007 [triangle]); Sharma (2002 [triangle]); Sun et al. (2004 [triangle]); Venkataramanan et al. (2005 [triangle]); Wang et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1810-scheme1.jpg

Experimental

Crystal data

  • C17H18N2O6
  • M r = 346.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1810-efi2.jpg
  • a = 27.836 (3) Å
  • b = 4.5949 (5) Å
  • c = 13.8081 (10) Å
  • β = 109.363 (2)°
  • V = 1666.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 298 (2) K
  • 0.43 × 0.40 × 0.31 mm

Data collection

  • Brucker SMART 1000 CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.956, T max = 0.968
  • 4032 measured reflections
  • 1476 independent reflections
  • 1025 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.186
  • S = 1.05
  • 1476 reflections
  • 114 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; 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 2, I. DOI: 10.1107/S1600536808026731/pv2099sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026731/pv2099Isup2.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 (No. 0604–01) and the ‘Qing Lan’ Talent Engineering Funds of Lanzhou Jiaotong University (No. QL-03–01 A), which are gratefully acknowledged.

supplementary crystallographic information

Comment

Salen-type compounds are chelate ligands, which have received great attention during the last decades (Sharma 2002; Akine et al., 2006; Dong et al., 2008a) due to their excellent complexing abilities towards various metal ions, especially in view of their potential use as ligands for preparation of functional complex materials (Venkataramanan et al., 2005). They are widely used in supramolecular chemistry for the construction of some one-dimensional chains, two-dimensional planar or three-dimensional network structural supramolecular complexes. To our interest, some salen-type compounds can be used as elemental building blocks for construction of supramolecular structures via intermolecular hydrogen bonding or short contact interaction (Sun et al., 2004; Akine et al., 2006; Wang et al., 2007). As an extension of our work (Dong & Feng 2006; Dong et al., 2008b; Dong et al., 2008c) on the structural characterization of salen-type bisoxime compounds, we report the structure of the title compound in this paper here.

The molecule of title compound adopts a V-shaped conformation with the dihedral angle between the two halves of the molecule is 81.31 (4) ° (Fig. 1). There is a half molecule in an asymmetric unit with a crystallographic twofold rotation axis passing through the central carbon of the three carbon atoms in the (—CH=N—O—(CH2)3—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 the molecule of the title compound is 82.22 (5) °. There are strong intramolecular O—H···N and O—H···O hydrogen bonds involving the hydroxy group and an adjacent O (or N) atoms (Table 1). In the crystal structure, intermolecular O—H···O hydrogen bonds link each molecule to 2 others into infinite three-dimensional supramolecular structure (Fig. 2), which is not similar to what was observed in our previously reported series salen-type compounds containing two- (Akine et al., 2006) and five-methene (Dong et al., 2008a) bridge.

Experimental

6,6'-Dihydroxy-2,2'-[(pentane-1,5-diyldioxy)bis(nitrilomethylidyne)]diphenol was synthesized according to an analogous method reported earlier (Dong et al., 2006; Dong et al., 2008a). 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, 3-bis(aminooxy)propane (106.8 mg, 1.0 mmol). After the solution had been stirred at 328 K for 3 h, the mixture was filtered, washed successively with ethanol and ethanol/hexane (1:4), respectively. The product was dried under reduced pressure and purified by recrystallization from ethanol to yield 204.8 mg of pale-brown crystalline solid.

Pale-brown prismatical crystals of the title compound suitable for X-ray crystal analysis were grown up from a tetrahydrofuran-ethanol (3:4) mixed solution by slow evaporation of the solvent at room temperature.

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) = 1.2 Ueq(C) and 1.5 Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound with atom numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level. [Symmetry code: -x + 1,y,-z + 5/2]
Fig. 2.
The packing diagram of the title compound showing intermolecular hydrogen bonds. H atoms are omitted for clarity.

Crystal data

C17H18N2O6F000 = 728
Mr = 346.33Dx = 1.381 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1493 reflections
a = 27.836 (3) Åθ = 2.8–27.7º
b = 4.5949 (5) ŵ = 0.11 mm1
c = 13.8081 (10) ÅT = 298 (2) K
β = 109.363 (2)ºPrismatic, pale-brown
V = 1666.2 (3) Å30.43 × 0.40 × 0.31 mm
Z = 4

Data collection

Brucker SMART 1000 CCD area-detector diffractometer1476 independent reflections
Radiation source: fine-focus sealed tube1025 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 298(2) Kθmax = 25.0º
phi and ω scansθmin = 1.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −32→27
Tmin = 0.956, Tmax = 0.968k = −5→5
4032 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)] = 0.066H-atom parameters constrained
wR(F2) = 0.186  w = 1/[σ2(Fo2) + (0.0856P)2 + 2.8739P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1476 reflectionsΔρmax = 0.20 e Å3
114 parametersΔρmin = −0.25 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Experimental. Yield, 59.1%, mp. 425–427 K. Anal. Calc. for C17H18N2O6: C, 59.96; H, 5.24; N, 8.09. Found: C, 60.17; H, 5.31; N, 7.92.
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)
O10.43592 (8)0.2306 (5)1.15521 (16)0.0466 (6)
O20.41085 (8)0.6412 (6)0.88832 (17)0.0539 (7)
H20.42360.53670.93850.081*
O30.36020 (10)1.0086 (6)0.73677 (18)0.0671 (9)
H30.38550.90800.74390.101*
N10.41732 (9)0.4035 (6)1.06706 (18)0.0413 (7)
C10.48064 (12)0.0823 (7)1.1531 (2)0.0456 (8)
H1A0.50630.22141.15000.055*
H1B0.4727−0.04311.09330.055*
C20.5000−0.0961 (11)1.25000.0529 (13)
H2A0.4727−0.22071.25450.063*0.50
H2B0.5273−0.22071.24550.063*0.50
C40.37794 (11)0.5439 (7)1.0649 (2)0.0409 (8)
H40.36500.52101.11850.049*
C50.35228 (11)0.7400 (7)0.9813 (2)0.0372 (7)
C60.36954 (11)0.7802 (7)0.8979 (2)0.0387 (8)
C70.34391 (12)0.9687 (7)0.8197 (2)0.0446 (8)
C80.30183 (13)1.1161 (8)0.8225 (3)0.0499 (9)
H80.28501.24230.76950.060*
C90.28425 (12)1.0774 (8)0.9046 (3)0.0490 (9)
H90.25551.17720.90660.059*
C100.30912 (12)0.8929 (8)0.9822 (2)0.0443 (8)
H100.29710.86821.03690.053*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0425 (12)0.0521 (15)0.0435 (13)0.0042 (11)0.0119 (10)0.0151 (11)
O20.0523 (14)0.0655 (16)0.0510 (14)0.0138 (12)0.0267 (11)0.0107 (12)
O30.0821 (19)0.0788 (19)0.0470 (15)0.0177 (15)0.0303 (13)0.0176 (13)
N10.0411 (15)0.0424 (16)0.0377 (14)−0.0041 (13)0.0096 (11)0.0029 (12)
C10.0406 (18)0.044 (2)0.0480 (19)0.0026 (15)0.0094 (15)−0.0031 (16)
C20.049 (3)0.044 (3)0.056 (3)0.0000.005 (2)0.000
C40.0387 (17)0.047 (2)0.0377 (17)−0.0033 (15)0.0133 (14)−0.0002 (15)
C50.0364 (16)0.0367 (18)0.0360 (16)−0.0084 (14)0.0088 (13)−0.0060 (14)
C60.0352 (16)0.0391 (18)0.0407 (17)−0.0009 (14)0.0110 (13)−0.0033 (15)
C70.051 (2)0.047 (2)0.0352 (17)−0.0083 (16)0.0123 (15)−0.0008 (15)
C80.0468 (19)0.048 (2)0.0446 (19)0.0064 (17)0.0017 (15)0.0040 (16)
C90.0396 (18)0.054 (2)0.050 (2)0.0042 (17)0.0106 (15)−0.0062 (18)
C100.0418 (18)0.050 (2)0.0429 (18)−0.0044 (16)0.0165 (14)−0.0055 (16)

Geometric parameters (Å, °)

O1—N11.401 (3)C2—H2B0.9700
O1—C11.428 (4)C4—C51.452 (4)
O2—C61.359 (4)C4—H40.9300
O2—H20.8207C5—C101.395 (4)
O3—C71.377 (4)C5—C61.400 (4)
O3—H30.8195C6—C71.383 (4)
N1—C41.264 (4)C7—C81.365 (5)
C1—C21.508 (4)C8—C91.387 (5)
C1—H1A0.9700C8—H80.9300
C1—H1B0.9700C9—C101.362 (5)
C2—C1i1.508 (4)C9—H90.9300
C2—H2A0.9700C10—H100.9300
N1—O1—C1109.0 (2)C10—C5—C6118.2 (3)
C6—O2—H2109.7C10—C5—C4120.2 (3)
C7—O3—H3109.3C6—C5—C4121.6 (3)
C4—N1—O1112.2 (2)O2—C6—C7116.9 (3)
O1—C1—C2107.4 (2)O2—C6—C5123.4 (3)
O1—C1—H1A110.2C7—C6—C5119.7 (3)
C2—C1—H1A110.2C8—C7—O3118.7 (3)
O1—C1—H1B110.2C8—C7—C6121.0 (3)
C2—C1—H1B110.2O3—C7—C6120.3 (3)
H1A—C1—H1B108.5C7—C8—C9119.9 (3)
C1i—C2—C1114.2 (4)C7—C8—H8120.1
C1i—C2—H2A108.7C9—C8—H8120.1
C1—C2—H2A108.7C10—C9—C8119.9 (3)
C1i—C2—H2B108.7C10—C9—H9120.1
C1—C2—H2B108.7C8—C9—H9120.1
H2A—C2—H2B107.6C9—C10—C5121.4 (3)
N1—C4—C5122.0 (3)C9—C10—H10119.3
N1—C4—H4119.0C5—C10—H10119.3
C5—C4—H4119.0
C1—O1—N1—C4−179.2 (3)O2—C6—C7—C8179.6 (3)
N1—O1—C1—C2178.9 (3)C5—C6—C7—C8−0.2 (5)
O1—C1—C2—C1i−66.8 (2)O2—C6—C7—O30.3 (5)
O1—N1—C4—C5179.3 (3)C5—C6—C7—O3−179.5 (3)
N1—C4—C5—C10−179.5 (3)O3—C7—C8—C9179.3 (3)
N1—C4—C5—C60.9 (5)C6—C7—C8—C90.0 (5)
C10—C5—C6—O2−179.4 (3)C7—C8—C9—C100.1 (5)
C4—C5—C6—O20.2 (5)C8—C9—C10—C50.0 (5)
C10—C5—C6—C70.3 (4)C6—C5—C10—C9−0.2 (5)
C4—C5—C6—C7179.9 (3)C4—C5—C10—C9−179.8 (3)

Symmetry codes: (i) −x+1, y, −z+5/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.942.650 (3)144
O3—H3···O20.822.252.694 (4)115
O3—H3···O1ii0.822.242.914 (4)140

Symmetry codes: (ii) x, −y+1, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2099).

References

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