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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1238.
Published online 2009 May 14. doi:  10.1107/S1600536809016584
PMCID: PMC2969628

2,2′-{1,1′-[Pentane-1,5-diylbis(oxy­nitrilo)]diethylidyne}di-1-naphthol

Abstract

The title compound, C29H30N2O4, adopts a distorted Z configuration with respect to the oxime group, which is almost coplanar with the adjacent naphthalene ring [dihedral angle = 4.11 (2)°]. There is one half-mol­ecule in the asymmetric unit, with a crystallographic twofold rotation axis passing through the central C atom of the –CH=N—O-(CH)5—O—N=CH– bridge. Within the mol­ecule, the dihedral angle formed by the two naphthalene rings is 79.08 (3)°, and there are two intra­molecular O—H(...)N hydrogen bonds.

Related literature

The condensation of primary amines with active carbonyl compounds can yield Schiff bases, see: Atwood & Harvey (2001 [triangle]); Casellato & Vigato (1977 [triangle]). For related structures, see: Dong et al. (2008a [triangle],b [triangle],c [triangle], 2009 [triangle]); Shi et al. (2007 [triangle]); Yeap et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1238-scheme1.jpg

Experimental

Crystal data

  • C29H30N2O4
  • M r = 470.55
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1238-efi1.jpg
  • a = 14.0683 (12) Å
  • b = 4.5659 (7) Å
  • c = 19.048 (2) Å
  • β = 97.321 (1)°
  • V = 1213.6 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 K
  • 0.49 × 0.45 × 0.21 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.959, T max = 0.982
  • 3170 measured reflections
  • 1218 independent reflections
  • 814 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.111
  • S = 1.02
  • 1218 reflections
  • 159 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.11 e Å−3
  • Δρmin = −0.13 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 global, I. DOI: 10.1107/S1600536809016584/at2776sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016584/at2776Isup2.hkl

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

Acknowledgments

The authors acknowledge finanical support from the ‘Jing Lan’ Talent Engineering Fund of Lanzhou Jiaotong University.

supplementary crystallographic information

Comment

The condensation of primary amines with active carbonyl compounds can yield Schiff bases (Casellato & Vigato, 1977; Atwood & Harvey, 2001) that are still now regarded as one of the most potential group of chelators for facile preparations of metallo-organic hybrid materials (Yeap et al., 2008). Many Schiff base complexes have been structurally characterized, but at present, a new class of salen-type bisoxime compounds have been synthesized by using an O-alkyloxime unit (–CH═N—O-(CH)n—O—N═CH–) instead of the (–CH═N-(CH)n—N═CH–) group (Dong et al., 2008a,b), the large electronegativity of O atoms is expected to affect strongly the electronic properties of N2O2 coordination sphere. Herein, we report on the synthesis and crystal structure of 2,2'-{1,1'-[pentane-1,5-diylbis(oxynitrilo)]diethylidyne}dinaphthol, (I), (Fig. 1).

The single-crystal structure of the title compound (I) is built up by only the C29H30N2O4 molecule, in which all bond lengths are in normal ranges. It adopts a distorted Z configuration with respect to the bisoxime group which is coplanar with the adjacent naphthalene ring (Dong et al., 2008c). The structure of (I) reveals the C1, C2, C3, C2# and C1# atoms in the (–CH═N—O-(CH)5—O—N═CH–) bridge lying on a plane. The dihedral angle formed by the two naphthalene rings in each molecule of the title compound is about 79.08°. Within each half of the molecule, the dihedral angle formed by the plane of the (–(CH)5–) bridge and the adjacent naphthalene ring is about 62.74°. There are two intramolecular hydrogen bonds, O2—H2···N1 (Table 1), indicating a strong hydrogen-bonding interaction.

Experimental

2,2'-{1,1'-[Pentane-1,5-diylbis(oxynitrilo)]diethylidyne}dinaphthol was synthesized according to an analogous method reported earlier (Shi et al., 2007; Dong et al., 2009). To an ethanol solution (5 ml) of 2-acetyl-1-naphthol (374.7 mg, 2.02 mmol) was added dropwise an ethanol solution (3 ml) of 1,5-bis(aminooxy)pentane (133.5 mg, 0.94 mmol). The mixture solution was stirred at 328–333 K for 70 h. After cooling to room temperature, the precipitate was filtered off, and washed successively three times with ethanol. The product was dried in vacuo and purified by recrystallization from ethanol to yield 367.5 mg (yield, 83.1%) of solid; m.p. 394–396 K. Colourless needle-like single crystals suitable for X-ray diffraction studies were obtained by slow evaporation from a solution of chloroform/methanol (1:1) of 2,2'-{1,1'-[pentane-1,5-diylbis(oxynitrilo)]diethylidyne}dinaphthol at room temperature for about three weeks. Analysis calculated for C29H30N2O4: C 74.02, H 6.43, N 5.99 (%); Found: C 74.05, H 6.39, N 6.07(%).

Refinement

H atoms were treated as riding atoms with distances C—H = 0.96 (CH3), C—H = 0.97 (CH2), 0.93 Å (CH), O—H = 0.82 Å [Uiso(H) = 1.2 Ueq(C) and 1.5 Ueq(C,O)].

Figures

Fig. 1.
The molecular structure of the title compound with atom-numbering scheme [symmetry code: (#1) - x, y, -z]. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.

Crystal data

C29H30N2O4F(000) = 500
Mr = 470.55Dx = 1.288 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 907 reflections
a = 14.0683 (12) Åθ = 2.9–22.5°
b = 4.5659 (7) ŵ = 0.09 mm1
c = 19.048 (2) ÅT = 298 K
β = 97.321 (1)°Block-like, yellow
V = 1213.6 (2) Å30.49 × 0.45 × 0.21 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer1218 independent reflections
Radiation source: fine-focus sealed tube814 reflections with I > 2σ(I)
graphiteRint = 0.034
[var phi] and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −16→9
Tmin = 0.959, Tmax = 0.982k = −5→5
3170 measured reflectionsl = −21→22

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3
1218 reflections(Δ/σ)max < 0.001
159 parametersΔρmax = 0.11 e Å3
1 restraintΔρmin = −0.13 e Å3

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)
N10.2185 (2)−0.0996 (7)0.16024 (12)0.0654 (8)
O10.24369 (16)−0.2609 (7)0.10176 (10)0.0807 (7)
O20.09872 (13)0.1007 (6)0.23812 (10)0.0734 (7)
H20.11570.00560.20540.110*
C10.1626 (2)−0.4239 (10)0.07147 (17)0.0768 (10)
H1A0.1376−0.53430.10860.092*
H1B0.1829−0.56330.03790.092*
C20.0834 (2)−0.2382 (10)0.03427 (15)0.0700 (9)
H2A0.1085−0.1218−0.00180.084*
H2B0.0606−0.10490.06810.084*
C30.0000−0.4226 (13)0.00000.0661 (13)
H3A−0.0223−0.54780.03570.079*0.50
H3B0.0223−0.5478−0.03570.079*0.50
C40.3854 (2)0.0583 (12)0.16832 (16)0.0890 (13)
H4A0.3863−0.06680.12790.134*
H4B0.4321−0.00870.20610.134*
H4C0.40040.25520.15590.134*
C50.2876 (2)0.0510 (9)0.19192 (15)0.0621 (9)
C60.1752 (2)0.2479 (9)0.27207 (14)0.0543 (8)
C70.2658 (2)0.2281 (8)0.25198 (13)0.0527 (8)
C80.3400 (2)0.3899 (9)0.29307 (16)0.0673 (10)
H80.40220.37710.28160.081*
C90.3230 (2)0.5610 (10)0.34806 (16)0.0710 (10)
H90.37310.66600.37280.085*
C100.2308 (2)0.5826 (8)0.36834 (14)0.0575 (8)
C110.1552 (2)0.4251 (8)0.32992 (14)0.0533 (7)
C120.0631 (2)0.4448 (10)0.35059 (15)0.0704 (10)
H120.01280.34200.32550.084*
C130.0467 (3)0.6102 (10)0.40623 (17)0.0794 (11)
H13−0.01450.61700.41980.095*
C140.1205 (3)0.7717 (11)0.44378 (16)0.0804 (11)
H140.10830.88830.48170.097*
C150.2101 (3)0.7583 (10)0.42496 (17)0.0722 (10)
H150.25890.86760.45010.087*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0693 (18)0.071 (2)0.0551 (13)0.0114 (18)0.0037 (13)0.0008 (16)
O10.0745 (15)0.0976 (19)0.0678 (13)0.0151 (17)0.0001 (12)−0.0131 (16)
O20.0503 (12)0.0963 (19)0.0721 (13)−0.0068 (14)0.0014 (10)−0.0109 (14)
C10.090 (2)0.067 (2)0.0693 (19)0.015 (3)−0.0063 (19)−0.006 (2)
C20.080 (2)0.066 (2)0.0609 (17)0.006 (2)−0.0040 (16)−0.003 (2)
C30.081 (3)0.061 (3)0.057 (2)0.0000.012 (2)0.000
C40.066 (2)0.132 (4)0.071 (2)0.001 (3)0.0156 (17)−0.012 (3)
C50.0552 (19)0.077 (2)0.0519 (17)0.010 (2)−0.0001 (15)0.0130 (19)
C60.0465 (17)0.065 (2)0.0489 (15)0.0020 (19)−0.0041 (13)0.0072 (18)
C70.0489 (18)0.062 (2)0.0458 (15)0.0028 (18)−0.0001 (13)0.0135 (17)
C80.0472 (18)0.088 (3)0.0649 (19)−0.006 (2)0.0019 (15)0.007 (2)
C90.054 (2)0.090 (3)0.0660 (19)−0.014 (2)−0.0010 (16)0.000 (2)
C100.0544 (18)0.065 (2)0.0518 (16)0.0001 (19)0.0018 (15)0.0119 (19)
C110.0501 (17)0.060 (2)0.0490 (15)0.0016 (17)0.0035 (13)0.0130 (18)
C120.055 (2)0.095 (3)0.0608 (18)−0.001 (2)0.0049 (15)0.001 (2)
C130.067 (2)0.100 (3)0.073 (2)0.008 (2)0.0121 (19)0.002 (2)
C140.089 (3)0.090 (3)0.0620 (19)0.008 (3)0.011 (2)−0.003 (2)
C150.074 (2)0.077 (3)0.0620 (18)−0.009 (2)−0.0031 (17)0.004 (2)

Geometric parameters (Å, °)

N1—C51.278 (4)C5—C71.465 (5)
N1—O11.417 (3)C6—C71.380 (4)
O1—C11.422 (4)C6—C111.424 (4)
O2—C61.360 (3)C7—C81.428 (4)
O2—H20.8200C8—C91.352 (4)
C1—C21.503 (4)C8—H80.9300
C1—H1A0.9700C9—C101.402 (4)
C1—H1B0.9700C9—H90.9300
C2—C31.522 (5)C10—C151.404 (5)
C2—H2A0.9700C10—C111.410 (4)
C2—H2B0.9700C11—C121.404 (4)
C3—C2i1.522 (5)C12—C131.345 (5)
C3—H3A0.9700C12—H120.9300
C3—H3B0.9700C13—C141.395 (5)
C4—C51.501 (4)C13—H130.9300
C4—H4A0.9600C14—C151.355 (4)
C4—H4B0.9600C14—H140.9300
C4—H4C0.9600C15—H150.9300
C5—N1—O1113.5 (3)O2—C6—C7122.6 (3)
N1—O1—C1108.8 (2)O2—C6—C11115.3 (2)
C6—O2—H2109.5C7—C6—C11122.2 (3)
O1—C1—C2113.8 (3)C6—C7—C8116.8 (3)
O1—C1—H1A108.8C6—C7—C5123.1 (3)
C2—C1—H1A108.8C8—C7—C5120.1 (3)
O1—C1—H1B108.8C9—C8—C7122.3 (3)
C2—C1—H1B108.8C9—C8—H8118.9
H1A—C1—H1B107.7C7—C8—H8118.9
C1—C2—C3112.0 (3)C8—C9—C10121.0 (3)
C1—C2—H2A109.2C8—C9—H9119.5
C3—C2—H2A109.2C10—C9—H9119.5
C1—C2—H2B109.2C9—C10—C15122.8 (3)
C3—C2—H2B109.2C9—C10—C11119.0 (3)
H2A—C2—H2B107.9C15—C10—C11118.2 (3)
C2—C3—C2i112.9 (5)C12—C11—C10119.0 (3)
C2—C3—H3A109.0C12—C11—C6122.3 (3)
C2i—C3—H3A109.0C10—C11—C6118.8 (3)
C2—C3—H3B109.0C13—C12—C11121.0 (3)
C2i—C3—H3B109.0C13—C12—H12119.5
H3A—C3—H3B107.8C11—C12—H12119.5
C5—C4—H4A109.5C12—C13—C14120.6 (3)
C5—C4—H4B109.5C12—C13—H13119.7
H4A—C4—H4B109.5C14—C13—H13119.7
C5—C4—H4C109.5C15—C14—C13119.8 (4)
H4A—C4—H4C109.5C15—C14—H14120.1
H4B—C4—H4C109.5C13—C14—H14120.1
N1—C5—C7116.3 (3)C14—C15—C10121.4 (4)
N1—C5—C4122.8 (3)C14—C15—H15119.3
C7—C5—C4120.9 (3)C10—C15—H15119.3
C5—N1—O1—C1178.9 (3)C8—C9—C10—C15−179.8 (4)
N1—O1—C1—C269.9 (4)C8—C9—C10—C11−0.7 (5)
O1—C1—C2—C3177.5 (2)C9—C10—C11—C12179.5 (3)
C1—C2—C3—C2i176.6 (3)C15—C10—C11—C12−1.4 (5)
O1—N1—C5—C7178.7 (3)C9—C10—C11—C60.4 (4)
O1—N1—C5—C40.9 (5)C15—C10—C11—C6179.5 (3)
O2—C6—C7—C8−178.8 (3)O2—C6—C11—C120.3 (5)
C11—C6—C7—C81.3 (5)C7—C6—C11—C12−179.8 (3)
O2—C6—C7—C50.9 (5)O2—C6—C11—C10179.4 (3)
C11—C6—C7—C5−179.0 (3)C7—C6—C11—C10−0.7 (5)
N1—C5—C7—C6−3.4 (5)C10—C11—C12—C13−0.2 (5)
C4—C5—C7—C6174.5 (4)C6—C11—C12—C13178.9 (3)
N1—C5—C7—C8176.3 (3)C11—C12—C13—C141.5 (6)
C4—C5—C7—C8−5.8 (5)C12—C13—C14—C15−1.2 (6)
C6—C7—C8—C9−1.6 (5)C13—C14—C15—C10−0.4 (6)
C5—C7—C8—C9178.6 (3)C9—C10—C15—C14−179.2 (4)
C7—C8—C9—C101.4 (5)C11—C10—C15—C141.7 (6)

Symmetry codes: (i) −x, y, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.832.552 (3)145

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2776).

References

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