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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o754.
Published online 2009 March 14. doi:  10.1107/S1600536809008757
PMCID: PMC2968897

(E,E)-6,6′-Dimeth­oxy-2,2′-[o-phenyl­ene­bis(nitrilo­methyl­idyne)]diphenol

Abstract

In the title compound, C22H20N2O4, the central benzene ring forms dihedral angles of 3.2 (2) and 61.1 (1)° with the two outer substituted benzene rings. Intra­molecular O—H(...)N hydrogen bonds are formed by both hydroxyl groups.

Related literature

For background literature concerning salen-type ligands, see: Zhang et al. (1990 [triangle]). For related structures, see: Lo et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o754-scheme1.jpg

Experimental

Crystal data

  • C22H20N2O4
  • M r = 376.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o754-efi1.jpg
  • a = 6.5863 (8) Å
  • b = 16.726 (2) Å
  • c = 17.023 (3) Å
  • β = 97.926 (2)°
  • V = 1857.3 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 K
  • 0.33 × 0.15 × 0.09 mm

Data collection

  • Siemens SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.970, T max = 0.992
  • 9269 measured reflections
  • 3263 independent reflections
  • 1217 reflections with I > 2σ(I)
  • R int = 0.098

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.128
  • S = 0.82
  • 3263 reflections
  • 257 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.16 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 I, global. DOI: 10.1107/S1600536809008757/bi2352sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008757/bi2352Isup2.hkl

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

Acknowledgments

The authors acknowledge the support of the National Natural Science Foundation of Liaocheng University (No. X051040).

supplementary crystallographic information

Comment

Salen-type ligands are amongst the oldest ligands in coordination chemistry and have received considerable interest since Jacobsen and Katsuki first reported their significant success using chiral manganese(III) salen Schiff-base catalysts in the asymmetric epoxidation of unfunctionalized olefins (Zhang, et al., 1990).

The title compound (Fig. 1) was obtained by reaction of o-phenylenediamine and 2-hydroxy-3-methoxybenzaldehyde. The bond lengths and angles are comparable to those in the related compound N,N'-bis(3- methoxysalicylidene)phenylene-1,2-diamine (Lo et al., 2006). The central benzene ring is almost coplanar with the benzene ring C16–C21; the dihedral angle between the two planes is 3.21 (22) °. However, the dihedral angle of the central benzene ring and the benzene ring C8–C13 is 61.13 (11)°. Intramolecular O—H···N hydrogen bonds are formed by both hydroxyl groups (Table 1).

Experimental

To a solution of o-phenylenediamine (3 mmol) in ethanol (30 ml) was added 2-hydroxy-3-methoxybenzaldehyde (6 mmol). The mixture was refluxed with stirring for 20 min and an orange precipitate was obtained. Orange crystals suitable for X-ray diffraction analysis formed after several weeks on slow evaporation of an ethanol solution at room temperature. Elemental analysis: calculated for C22H20N2O4: C 70.20, H 5.36, N 7.44%; found: C 70.28, H 5.32, N 7.49%.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 or 0.96 Å and Uiso(H) = 1.2 or 1.5Ueq(C). The H atoms of the hydroxyl groups were placed in idealized positions and constrained to ride on their parent atoms with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
Molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms.

Crystal data

C22H20N2O4F(000) = 792
Mr = 376.40Dx = 1.346 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 802 reflections
a = 6.5863 (8) Åθ = 2.4–25.3°
b = 16.726 (2) ŵ = 0.09 mm1
c = 17.023 (3) ÅT = 298 K
β = 97.926 (2)°Block, orange
V = 1857.3 (4) Å30.33 × 0.15 × 0.09 mm
Z = 4

Data collection

Siemens SMART CCD diffractometer3263 independent reflections
Radiation source: fine-focus sealed tube1217 reflections with I > 2σ(I)
graphiteRint = 0.098
ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −7→7
Tmin = 0.970, Tmax = 0.992k = −19→19
9269 measured reflectionsl = −10→20

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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 0.82w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3
3263 reflections(Δ/σ)max < 0.001
257 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = −0.16 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*/Ueq
N1−0.1935 (4)0.21173 (18)0.39296 (16)0.0568 (8)
N20.0295 (4)0.26464 (15)0.52584 (18)0.0579 (8)
O10.0593 (4)0.15813 (15)0.30030 (15)0.0719 (7)
H10.01400.18990.33030.108*
O20.1592 (4)0.04788 (15)0.20699 (16)0.0868 (9)
O30.2802 (3)0.15729 (14)0.49515 (14)0.0676 (7)
H30.17190.18220.49030.101*
O40.6184 (3)0.08108 (14)0.53290 (13)0.0698 (7)
C1−0.2767 (6)0.2731 (2)0.4365 (2)0.0575 (10)
C2−0.1578 (6)0.3022 (2)0.5035 (2)0.0572 (10)
C3−0.2322 (6)0.3642 (2)0.5450 (2)0.0715 (11)
H3A−0.15400.38430.59030.086*
C4−0.4199 (7)0.3955 (2)0.5195 (3)0.0834 (13)
H4−0.46890.43740.54750.100*
C5−0.5373 (6)0.3668 (3)0.4537 (3)0.0797 (13)
H5−0.66590.38870.43710.096*
C6−0.4654 (6)0.3057 (2)0.4120 (2)0.0719 (11)
H6−0.54510.28620.36670.086*
C7−0.3021 (5)0.1499 (2)0.37462 (19)0.0581 (10)
H7−0.42850.14520.39280.070*
C8−0.2348 (5)0.0871 (2)0.3265 (2)0.0555 (9)
C9−0.0623 (6)0.0944 (2)0.2904 (2)0.0552 (9)
C10−0.0088 (6)0.0337 (2)0.2413 (2)0.0590 (10)
C11−0.1242 (7)−0.0340 (2)0.2324 (2)0.0754 (12)
H11−0.0887−0.07490.19980.090*
C12−0.2921 (7)−0.0425 (3)0.2709 (3)0.0910 (14)
H12−0.3674−0.08970.26560.109*
C13−0.3491 (6)0.0175 (3)0.3167 (2)0.0819 (12)
H13−0.46540.01190.34160.098*
C140.2181 (7)−0.0106 (2)0.1550 (3)0.1190 (17)
H14A0.2234−0.06190.18050.178*
H14B0.35100.00230.14140.178*
H14C0.1202−0.01210.10770.178*
C150.1427 (6)0.27815 (19)0.5911 (2)0.0595 (10)
H150.10030.31520.62620.071*
C160.3323 (5)0.23818 (19)0.6117 (2)0.0522 (9)
C170.3958 (5)0.1790 (2)0.5627 (2)0.0516 (9)
C180.5797 (5)0.1401 (2)0.5837 (2)0.0543 (9)
C190.7041 (5)0.1621 (2)0.6500 (2)0.0668 (11)
H190.83030.13710.66310.080*
C200.6450 (7)0.2217 (2)0.6987 (2)0.0743 (12)
H200.73140.23640.74430.089*
C210.4615 (6)0.2584 (2)0.6800 (2)0.0709 (11)
H210.42180.29770.71340.085*
C220.8046 (5)0.0386 (2)0.5504 (2)0.0837 (13)
H22A0.91760.07510.55220.125*
H22B0.8139−0.00080.51000.125*
H22C0.80880.01260.60090.125*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.064 (2)0.059 (2)0.0483 (18)0.0109 (17)0.0112 (15)0.0045 (17)
N20.059 (2)0.0576 (19)0.057 (2)0.0020 (16)0.0072 (16)−0.0030 (17)
O10.0748 (18)0.0689 (18)0.076 (2)−0.0043 (14)0.0235 (13)−0.0008 (15)
O20.096 (2)0.085 (2)0.089 (2)0.0161 (16)0.0462 (17)0.0009 (17)
O30.0697 (18)0.0699 (17)0.0598 (16)0.0129 (13)−0.0036 (13)−0.0172 (14)
O40.0727 (18)0.0755 (17)0.0601 (16)0.0191 (14)0.0055 (13)−0.0091 (15)
C10.067 (3)0.054 (2)0.054 (3)0.009 (2)0.020 (2)0.016 (2)
C20.066 (3)0.050 (2)0.059 (3)0.005 (2)0.019 (2)0.006 (2)
C30.076 (3)0.063 (3)0.077 (3)0.012 (2)0.017 (2)−0.005 (2)
C40.106 (4)0.069 (3)0.081 (3)0.029 (3)0.035 (3)0.006 (3)
C50.081 (3)0.079 (3)0.083 (3)0.035 (3)0.027 (3)0.025 (3)
C60.077 (3)0.080 (3)0.059 (3)0.024 (2)0.013 (2)0.015 (2)
C70.060 (2)0.068 (3)0.047 (2)0.007 (2)0.0104 (18)0.010 (2)
C80.054 (2)0.062 (3)0.052 (2)0.001 (2)0.0114 (19)0.008 (2)
C90.062 (3)0.052 (2)0.050 (2)0.002 (2)0.0035 (19)0.007 (2)
C100.072 (3)0.061 (3)0.045 (2)0.009 (2)0.013 (2)0.011 (2)
C110.094 (3)0.071 (3)0.060 (3)0.007 (3)0.007 (2)−0.004 (2)
C120.103 (4)0.076 (3)0.096 (4)−0.021 (3)0.021 (3)−0.015 (3)
C130.077 (3)0.085 (3)0.089 (3)−0.018 (3)0.027 (2)−0.006 (3)
C140.157 (4)0.110 (4)0.106 (4)0.039 (3)0.073 (3)−0.011 (3)
C150.076 (3)0.048 (2)0.058 (3)0.002 (2)0.020 (2)−0.004 (2)
C160.061 (2)0.044 (2)0.053 (2)−0.0026 (18)0.0124 (19)−0.0024 (19)
C170.058 (2)0.053 (2)0.043 (2)−0.0057 (19)0.0038 (18)0.0003 (19)
C180.059 (2)0.058 (2)0.045 (2)0.005 (2)0.0057 (19)0.001 (2)
C190.064 (3)0.078 (3)0.058 (3)0.003 (2)0.007 (2)0.008 (2)
C200.088 (3)0.079 (3)0.052 (3)−0.009 (2)−0.002 (2)−0.007 (2)
C210.088 (3)0.068 (3)0.055 (3)−0.001 (2)0.002 (2)−0.015 (2)
C220.075 (3)0.090 (3)0.086 (3)0.034 (2)0.013 (2)−0.002 (3)

Geometric parameters (Å, °)

N1—C71.272 (4)C8—C131.383 (4)
N1—C11.419 (4)C9—C101.391 (4)
N2—C151.270 (4)C10—C111.360 (5)
N2—C21.389 (4)C11—C121.368 (5)
O1—C91.330 (4)C11—H110.930
O1—H10.820C12—C131.357 (5)
O2—C101.342 (4)C12—H120.930
O2—C141.409 (4)C13—H130.930
O3—C171.339 (3)C14—H14A0.960
O3—H30.820C14—H14B0.960
O4—C181.360 (4)C14—H14C0.960
O4—C221.413 (3)C15—C161.417 (4)
C1—C61.370 (4)C15—H150.930
C1—C21.381 (4)C16—C211.385 (4)
C2—C31.381 (4)C16—C171.395 (4)
C3—C41.358 (4)C17—C181.377 (4)
C3—H3A0.930C18—C191.351 (4)
C4—C51.358 (5)C19—C201.385 (4)
C4—H40.930C19—H190.930
C5—C61.365 (5)C20—C211.354 (4)
C5—H50.930C20—H200.930
C6—H60.930C21—H210.930
C7—C81.439 (4)C22—H22A0.960
C7—H70.930C22—H22B0.960
C8—C91.370 (4)C22—H22C0.960
C7—N1—C1118.1 (3)C13—C12—C11120.3 (4)
C15—N2—C2123.4 (3)C13—C12—H12119.8
C9—O1—H1109.5C11—C12—H12119.8
C10—O2—C14117.7 (3)C12—C13—C8120.2 (4)
C17—O3—H3109.5C12—C13—H13119.9
C18—O4—C22117.7 (3)C8—C13—H13119.9
C6—C1—C2119.9 (4)O2—C14—H14A109.5
C6—C1—N1121.9 (4)O2—C14—H14B109.5
C2—C1—N1118.1 (3)H14A—C14—H14B109.5
C1—C2—C3119.1 (4)O2—C14—H14C109.5
C1—C2—N2116.6 (3)H14A—C14—H14C109.5
C3—C2—N2124.3 (4)H14B—C14—H14C109.5
C4—C3—C2119.9 (4)N2—C15—C16121.6 (3)
C4—C3—H3A120.1N2—C15—H15119.2
C2—C3—H3A120.1C16—C15—H15119.2
C5—C4—C3121.1 (4)C21—C16—C17118.3 (3)
C5—C4—H4119.4C21—C16—C15120.8 (4)
C3—C4—H4119.4C17—C16—C15120.9 (3)
C4—C5—C6119.7 (4)O3—C17—C18118.1 (3)
C4—C5—H5120.2O3—C17—C16121.6 (3)
C6—C5—H5120.2C18—C17—C16120.4 (3)
C5—C6—C1120.4 (4)C19—C18—O4125.7 (3)
C5—C6—H6119.8C19—C18—C17119.9 (4)
C1—C6—H6119.8O4—C18—C17114.4 (3)
N1—C7—C8121.8 (4)C18—C19—C20120.5 (4)
N1—C7—H7119.1C18—C19—H19119.8
C8—C7—H7119.1C20—C19—H19119.8
C9—C8—C13119.5 (4)C21—C20—C19120.1 (3)
C9—C8—C7122.0 (4)C21—C20—H20120.0
C13—C8—C7118.5 (4)C19—C20—H20120.0
O1—C9—C8122.5 (4)C20—C21—C16120.8 (4)
O1—C9—C10117.6 (4)C20—C21—H21119.6
C8—C9—C10119.9 (4)C16—C21—H21119.6
O2—C10—C11125.5 (4)O4—C22—H22A109.5
O2—C10—C9115.1 (4)O4—C22—H22B109.5
C11—C10—C9119.4 (4)H22A—C22—H22B109.5
C10—C11—C12120.6 (4)O4—C22—H22C109.5
C10—C11—H11119.7H22A—C22—H22C109.5
C12—C11—H11119.7H22B—C22—H22C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.882.605 (4)146
O3—H3···N20.821.822.542 (3)146

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2352).

References

  • Lo, W.-K., Wong, W.-K., Wong, W.-Y., Guo, J. P., Yeung, K.-T., Cheng, Y.-K., Yang, X. P. & Jones, R. A. (2006). Inorg. Chem.45, 9315–9325. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Zhang, W., Loebach, J. L., Wilson, S. R. & Jacobsen, E. N. (1990). J. Am. Chem. Soc.112, 2801–2804.

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