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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2311.
Published online 2009 September 5. doi:  10.1107/S1600536809033959
PMCID: PMC2970437

2,2′-[1,1′-(Octane-1,8-diyldioxy­dinitrilo)diethyl­idyne]diphenol

Abstract

The title compound, C24H32N2O4, has a crystallographic inversion centre at the mid-point of the central C—C bond. At each end of the mol­ecule, intra­molecular O—H(...)N hydrogen bonds generate six-membered S(6) ring motifs. The crystal structure is stabilized by pairs of weak inter­molecular C—H(...)O hydrogen bonds that link neighbouring mol­ecules into R 2 2(40) ring motifs, which in turn form infinite one-dimensional supra­molecular ribbon structures.

Related literature

For background to oxime-based salen-type tetra­dentate ligands, see: Akine et al. (2005 [triangle]); Dong, He et al. (2009 [triangle]); Dong, Sun et al. (2009 [triangle]). For the synthesis, see: Dong et al. (2008 [triangle]). For related structures, see: Dong, Zhao et al. (2009 [triangle]); Etemadi et al. (2009 [triangle]). For information relating to C—H(...)O hydrogen bonds, see: Desiraju (1996 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2311-scheme1.jpg

Experimental

Crystal data

  • C24H32N2O4
  • M r = 412.52
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2311-efi3.jpg
  • a = 12.9524 (12) Å
  • b = 4.6667 (6) Å
  • c = 37.722 (3) Å
  • β = 99.379 (2)°
  • V = 2249.6 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 K
  • 0.50 × 0.48 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.960, T max = 0.984
  • 5371 measured reflections
  • 1979 independent reflections
  • 1172 reflections with I > 2σ(I)
  • R int = 0.069

Refinement

  • R[F 2 > 2σ(F 2)] = 0.074
  • wR(F 2) = 0.173
  • S = 1.11
  • 1979 reflections
  • 137 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.21 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]) and Mercury (Macrae et al., 2006 [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/S1600536809033959/pk2184sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033959/pk2184Isup2.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. 0904–11) and the ‘Jing Lan’ Talent Engineering Funds of Lanzhou Jiaotong University, which are gratefully acknowledged.

supplementary crystallographic information

Comment

Much attention has been focused on oxime-based salen-type tetradentate ligands in recent years due to their high stability against imine metathesis reactions (Akine et al., 2005; Dong, He et al. 2009). A number of their metal complexes have been prepared and reported (Dong, Sun et al. 2009), which demonstrates that bisoxime ligands have strong coordinating ability with transition metals and non-transition metals. In continuation of our previously reported works (Dong, Zhao et al. 2009), here we report synthesis and structure of salen-type bisoxime ligands, 2,2'-[1,1'-(octane-1,8-diyldioxydinitrilo)diethylidyne]diphenol.

The molecular structure of the title compound, as shown in Fig. 1, has a crystallographic inversion centre at the mid-point of the the central C—C bond. Thus there is half a molecule in the asymmetric unit. The two benzene rings are parallel to each other with a perpendicular interplanar spacing of ca 5.316 (2) Å. In each molecule, there exist two intramolecular O—H···N hydrogen bonds, that form two S(6) ring motifs (Fig. 1) (Bernstein et al., 1995). Pairs of weak intermolecular C—H···O hydrogen bonds (Desiraju, 1996) link neighbouring molecules into an infinite one-dimensional supramolecular structure with R22(40) ring motifs (Table 1, Fig. 2), similar to that described by Etemadi et al., (2009).

Experimental

2,2'-[1,1'-(Octane-1,8-diyldioxydinitrilo)diethylidyne]diphenol was synthesized according to our previous work (Dong et al., 2008). To an ethanol solution (4 ml) of 2'-hydroxyacetophenone (280.7 mg, 2.06 mmol) was added an ethanol solution (4 ml) of 1, 8-bis(aminooxy)octane (180.9 mg, 1.03 mmol). The mixture was stirred at 328–333 K for 48 h. When cooled to room temperature, the resulting white precipitate was filtered, and washed successively with ethanol and n-hexane. The product was dried under vacuum and purified by recrystallization from ethanol to yield 206.5 mg of the title compound. Yield, 49.01%. m. p. 345–347 K. Anal. Calcd. for C24H32N2O4: C, 69.88; H, 7.82; N, 6.79. Found: C, 69.50; H, 7.53; N, 6.87.

Colorless block-like single crystals suitable for X-ray diffraction studies were obtained after several days by slow evaporation from a diethyl ether solution.

Refinement

Non-H atoms were refined anisotropically. H atoms were treated as riding atoms with distances C—H = 0.96 Å (CH3), 0.97 Å (CH2), 0.93 Å (CH), 0.82 Å (OH), and Uiso(H) = 1.20 Ueq(C) for methylene and methylidyne, 1.50 Ueq(C) for methyl, 1.50 Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme. Unlabelled atoms are related to their labelled counterparts by the inversion operation [-x + 3/2,-y + 3/2,-z + 1]. Displacement ellipsoids for non-hydrogen atoms are drawn at ...
Fig. 2.
Part of the one-dimensional supramolecular structure of the title compound. Intramolecular and intermolecular hydrogen bonds are shown as dashed lines. Colour code: dark gray: C; red: O; blue: N; pale green: H (Macrae et al., 2006).

Crystal data

C24H32N2O4F(000) = 888
Mr = 412.52Dx = 1.218 Mg m3
Monoclinic, C2/cMelting point = 345–347 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 12.9524 (12) ÅCell parameters from 1491 reflections
b = 4.6667 (6) Åθ = 2.2–27.2°
c = 37.722 (3) ŵ = 0.08 mm1
β = 99.379 (2)°T = 298 K
V = 2249.6 (4) Å3Block-like, colorless
Z = 40.50 × 0.48 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer1979 independent reflections
Radiation source: fine-focus sealed tube1172 reflections with I > 2σ(I)
graphiteRint = 0.069
[var phi] and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −14→15
Tmin = 0.960, Tmax = 0.984k = −5→5
5371 measured reflectionsl = −37→44

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.074H-atom parameters constrained
wR(F2) = 0.173w = 1/[σ2(Fo2) + (0.0225P)2 + 4.9486P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
1979 reflectionsΔρmax = 0.20 e Å3
137 parametersΔρmin = −0.21 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0080 (9)

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*/Ueq
N10.3869 (2)0.5102 (7)0.38238 (7)0.0490 (8)
O10.35769 (17)0.6700 (6)0.41082 (6)0.0617 (8)
O20.51778 (18)0.3352 (7)0.34323 (7)0.0746 (9)
H20.49800.42880.35930.112*
C10.4459 (3)0.8346 (9)0.42728 (9)0.0570 (10)
H1A0.42240.97860.44270.068*
H1B0.47570.93350.40870.068*
C20.5297 (2)0.6538 (9)0.44922 (9)0.0513 (9)
H2A0.55940.52540.43330.062*
H2B0.49830.53770.46590.062*
C30.6162 (2)0.8345 (9)0.46995 (9)0.0518 (9)
H3A0.58700.95130.48720.062*
H3B0.64300.96270.45340.062*
C40.7063 (2)0.6595 (9)0.48983 (9)0.0540 (10)
H4A0.67960.53330.50670.065*
H4B0.73470.54060.47270.065*
C50.3132 (2)0.3491 (8)0.36639 (8)0.0440 (9)
C60.2085 (3)0.3295 (12)0.37779 (11)0.0786 (14)
H6A0.19700.13710.38520.118*
H6B0.15520.38050.35800.118*
H6C0.20590.45850.39750.118*
C70.3382 (2)0.1742 (8)0.33664 (8)0.0447 (9)
C80.4372 (3)0.1723 (9)0.32643 (10)0.0547 (10)
C90.4582 (3)0.0008 (10)0.29864 (11)0.0699 (12)
H90.52470.00130.29240.084*
C100.3815 (4)−0.1708 (10)0.28013 (10)0.0714 (12)
H100.3961−0.28620.26150.086*
C110.2835 (4)−0.1710 (10)0.28930 (10)0.0699 (12)
H110.2313−0.28590.27670.084*
C120.2619 (3)−0.0026 (9)0.31692 (9)0.0587 (11)
H120.1948−0.00540.32280.070*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0372 (16)0.058 (2)0.0459 (16)0.0005 (15)−0.0117 (12)−0.0031 (17)
O10.0381 (14)0.081 (2)0.0591 (15)0.0022 (14)−0.0132 (11)−0.0207 (16)
O20.0399 (14)0.092 (2)0.0886 (19)−0.0111 (16)0.0020 (13)−0.0267 (19)
C10.044 (2)0.061 (2)0.057 (2)0.001 (2)−0.0190 (16)−0.017 (2)
C20.0416 (19)0.060 (2)0.0460 (19)−0.0056 (19)−0.0126 (15)−0.001 (2)
C30.0413 (19)0.060 (2)0.0483 (19)−0.002 (2)−0.0097 (15)−0.012 (2)
C40.0395 (19)0.061 (2)0.056 (2)−0.004 (2)−0.0099 (15)−0.009 (2)
C50.0320 (18)0.050 (2)0.0437 (18)−0.0007 (17)−0.0128 (14)0.0062 (19)
C60.045 (2)0.108 (4)0.080 (3)−0.017 (3)0.0029 (19)−0.024 (3)
C70.0380 (19)0.046 (2)0.0433 (18)−0.0042 (17)−0.0124 (14)0.0072 (18)
C80.050 (2)0.054 (2)0.055 (2)−0.001 (2)−0.0078 (17)−0.003 (2)
C90.061 (3)0.080 (3)0.067 (3)0.002 (3)0.005 (2)−0.003 (3)
C100.092 (3)0.068 (3)0.051 (2)0.005 (3)0.001 (2)−0.002 (2)
C110.083 (3)0.066 (3)0.051 (2)−0.019 (3)−0.016 (2)0.003 (2)
C120.055 (2)0.064 (3)0.051 (2)−0.012 (2)−0.0112 (17)0.009 (2)

Geometric parameters (Å, °)

N1—C51.285 (4)C4—H4B0.9700
N1—O11.408 (3)C5—C71.466 (5)
O1—C11.432 (4)C5—C61.491 (5)
O2—C81.361 (4)C6—H6A0.9600
O2—H20.8200C6—H6B0.9600
C1—C21.511 (5)C6—H6C0.9600
C1—H1A0.9700C7—C81.398 (5)
C1—H1B0.9700C7—C121.404 (5)
C2—C31.514 (5)C8—C91.380 (5)
C2—H2A0.9700C9—C101.375 (6)
C2—H2B0.9700C9—H90.9300
C3—C41.518 (5)C10—C111.369 (5)
C3—H3A0.9700C10—H100.9300
C3—H3B0.9700C11—C121.370 (5)
C4—C4i1.517 (6)C11—H110.9300
C4—H4A0.9700C12—H120.9300
C5—N1—O1113.3 (3)N1—C5—C7116.5 (3)
N1—O1—C1108.7 (3)N1—C5—C6122.8 (3)
C8—O2—H2109.5C7—C5—C6120.7 (3)
O1—C1—C2112.9 (3)C5—C6—H6A109.5
O1—C1—H1A109.0C5—C6—H6B109.5
C2—C1—H1A109.0H6A—C6—H6B109.5
O1—C1—H1B109.0C5—C6—H6C109.5
C2—C1—H1B109.0H6A—C6—H6C109.5
H1A—C1—H1B107.8H6B—C6—H6C109.5
C1—C2—C3112.1 (3)C8—C7—C12116.7 (3)
C1—C2—H2A109.2C8—C7—C5122.7 (3)
C3—C2—H2A109.2C12—C7—C5120.6 (3)
C1—C2—H2B109.2O2—C8—C9116.5 (4)
C3—C2—H2B109.2O2—C8—C7122.4 (3)
H2A—C2—H2B107.9C9—C8—C7121.0 (4)
C2—C3—C4113.6 (3)C10—C9—C8120.5 (4)
C2—C3—H3A108.8C10—C9—H9119.7
C4—C3—H3A108.8C8—C9—H9119.7
C2—C3—H3B108.8C11—C10—C9119.7 (4)
C4—C3—H3B108.8C11—C10—H10120.2
H3A—C3—H3B107.7C9—C10—H10120.2
C4i—C4—C3113.6 (4)C10—C11—C12120.3 (4)
C4i—C4—H4A108.8C10—C11—H11119.9
C3—C4—H4A108.8C12—C11—H11119.9
C4i—C4—H4B108.8C11—C12—C7121.8 (4)
C3—C4—H4B108.8C11—C12—H12119.1
H4A—C4—H4B107.7C7—C12—H12119.1
C5—N1—O1—C1178.4 (3)C12—C7—C8—O2179.6 (3)
N1—O1—C1—C2−72.6 (4)C5—C7—C8—O2−0.6 (6)
O1—C1—C2—C3−173.2 (3)C12—C7—C8—C9−1.0 (5)
C1—C2—C3—C4−175.1 (3)C5—C7—C8—C9178.8 (3)
C2—C3—C4—C4i179.2 (4)O2—C8—C9—C10−180.0 (4)
O1—N1—C5—C7−179.5 (3)C7—C8—C9—C100.6 (6)
O1—N1—C5—C6−1.6 (5)C8—C9—C10—C110.1 (6)
N1—C5—C7—C82.0 (5)C9—C10—C11—C12−0.4 (6)
C6—C5—C7—C8−176.0 (4)C10—C11—C12—C70.0 (6)
N1—C5—C7—C12−178.2 (3)C8—C7—C12—C110.7 (5)
C6—C5—C7—C123.8 (5)C5—C7—C12—C11−179.1 (4)

Symmetry codes: (i) −x+3/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.842.558 (4)145
C12—H12···O2ii0.932.643.544 (5)164

Symmetry codes: (ii) x−1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2184).

References

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