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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o70.
Published online 2009 December 9. doi:  10.1107/S160053680905020X
PMCID: PMC2980064

6,6′-Dimeth­oxy-2,2′-[pyridine-2,3-diylbis(nitrilo­methyl­idyne)]diphenol

Abstract

In the title compound, C21H19N3O4, two intramolecular N—H(...)O hydrogen bonds generate two six-membered rings. The dihedral angles between the central heterocyclic ring and the two pendant rings are 61.5 (2) and 63.5 (1)°.

Related literature

For related crystal structures, see: Cimerman et al. (1992 [triangle]); Bi et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-00o70-scheme1.jpg

Experimental

Crystal data

  • C21H19N3O4
  • M r = 377.39
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00o70-efi1.jpg
  • a = 6.7006 (9) Å
  • b = 16.699 (2) Å
  • c = 17.490 (2) Å
  • β = 98.772 (2)°
  • V = 1934.2 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.25 × 0.21 × 0.19 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a [triangle]) T min = 0.978, T max = 0.983
  • 9149 measured reflections
  • 3293 independent reflections
  • 1929 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.184
  • S = 1.04
  • 3293 reflections
  • 257 parameters
  • H-atom parameters constrained
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008b [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/S160053680905020X/hg2604sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680905020X/hg2604Isup2.hkl

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

supplementary crystallographic information

Comment

Transition metal complexes with salen-type Schiff-bases as ligands, which has been known as one of the oldest ligands in coordination chemistry, have been intensely studied. Here, we report a new Schiff-base ligand based on 2,3-diaminopyridine and 2-hydroxy-3-methoxybenzaldehyde.

The geometry and labeling scheme for the crystal structure of the title compound are depicted in Figure 1. As can be seen from Figure 1, the title compound affords the potentially tetradentate ligand contributed from the O2N2 donor unit. The imide bond lengths are 1.267 (4)Å for N1—C12 and 1.288 (4)Å for N2—C20, respectively, which are basically consistent with the corresponding distances found in other diaminopyridine-based Schiff base ligand (Cimerman, et al., 1992; Bi et al., 2007). There exists relative strong intramolecular O-H···N hydrogen bonding in this compound with the N···O distance 2.683 (3)Å and the bond angle 145.8 ° for O1—N1 and 2.568 (3))Å , 146.1° for O3—N2, respectively; and is similar to its analogues above mentioned.

Experimental

The title Schiff base ligand was synthesized by condensation 2,3-diaminopyridine and 2-hydroxy-3-methoxybenzaldehyde with the ratio 1:2 in ethanol. Single crystals suitable for X-ray diffraction were obtained after the solvent was partially evaporated.

Refinement

All the H atoms were placed using the HFIX commands in SHELXL-97, with C—H distances of 0.93, 0.96 Å and O—H 0.82 Å, and were allowed for as riding atoms with Uiso(H) = 1.5Ueq(C), Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.2Ueq(O), respectively.

Figures

Fig. 1.
View of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C21H19N3O4F(000) = 792
Mr = 377.39Dx = 1.296 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1473 reflections
a = 6.7006 (9) Åθ = 2.4–22.1°
b = 16.699 (2) ŵ = 0.09 mm1
c = 17.490 (2) ÅT = 293 K
β = 98.772 (2)°Needle, yellow
V = 1934.2 (5) Å30.25 × 0.21 × 0.19 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer3293 independent reflections
Radiation source: fine-focus sealed tube1929 reflections with I > 2σ(I)
graphiteRint = 0.039
[var phi] and ω scansθmax = 24.9°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)h = −7→7
Tmin = 0.978, Tmax = 0.983k = −16→19
9149 measured reflectionsl = −18→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)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0889P)2 + 0.4093P] where P = (Fo2 + 2Fc2)/3
3293 reflections(Δ/σ)max = 0.001
257 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = −0.44 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
O10.0595 (3)0.84140 (12)0.30034 (13)0.0651 (6)
H10.01640.80970.32970.098*
O20.1593 (4)0.95259 (14)0.20681 (15)0.0796 (8)
O30.2804 (3)0.84262 (13)0.49519 (12)0.0597 (6)
H30.17570.81640.48880.090*
O40.6184 (3)0.91857 (13)0.53308 (12)0.0627 (6)
N1−0.1950 (4)0.78816 (15)0.39342 (14)0.0500 (6)
N20.0306 (4)0.73504 (13)0.52610 (15)0.0521 (6)
N3−0.4678 (4)0.69480 (18)0.41075 (18)0.0764 (9)
C1−0.2765 (5)0.72718 (19)0.4364 (2)0.0616 (9)
C2−0.1580 (5)0.69766 (19)0.5039 (2)0.0609 (9)
C3−0.2348 (6)0.63538 (19)0.5445 (2)0.0692 (10)
H3A−0.15860.61510.58920.083*
C4−0.4230 (5)0.6040 (2)0.5184 (2)0.0695 (10)
H4−0.47250.56260.54570.083*
C5−0.5373 (6)0.6328 (2)0.4533 (2)0.0688 (10)
H5−0.66410.61080.43690.083*
C6−0.2355 (4)0.91289 (17)0.32671 (16)0.0498 (7)
C7−0.0614 (4)0.90562 (17)0.29041 (16)0.0484 (7)
C8−0.0096 (5)0.96657 (19)0.24156 (17)0.0546 (8)
C9−0.1249 (6)1.0343 (2)0.2327 (2)0.0692 (10)
H9−0.09091.07540.20120.083*
C10−0.2936 (6)1.0428 (2)0.2704 (2)0.0818 (11)
H10−0.36871.08990.26440.098*
C11−0.3493 (5)0.9826 (2)0.3159 (2)0.0739 (10)
H11−0.46360.98850.33970.089*
C12−0.3019 (5)0.84972 (19)0.37466 (16)0.0521 (8)
H12−0.42590.85480.39190.062*
C130.2168 (7)1.0121 (3)0.1557 (3)0.1097 (16)
H13A0.11661.01510.11030.165*
H13B0.34470.99800.14110.165*
H13C0.22791.06310.18130.165*
C140.3338 (5)0.76176 (16)0.61150 (16)0.0486 (7)
C150.3942 (4)0.82084 (16)0.56241 (16)0.0449 (7)
C160.5794 (4)0.86010 (17)0.58366 (16)0.0473 (7)
C170.7038 (5)0.8378 (2)0.65066 (18)0.0590 (8)
H170.82860.86260.66390.071*
C180.6446 (5)0.7784 (2)0.69882 (19)0.0663 (9)
H180.72960.76420.74390.080*
C190.4630 (6)0.74141 (19)0.68010 (19)0.0642 (9)
H190.42370.70240.71270.077*
C200.1429 (5)0.72198 (18)0.59146 (19)0.0562 (8)
H200.09970.68620.62630.067*
C210.8030 (5)0.9613 (2)0.5508 (2)0.0764 (10)
H21A0.81040.98550.60100.115*
H21B0.80901.00220.51270.115*
H21C0.91420.92510.55080.115*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0634 (14)0.0594 (14)0.0767 (16)0.0037 (11)0.0238 (12)0.0013 (11)
O20.0888 (18)0.0737 (16)0.0857 (17)−0.0129 (13)0.0431 (15)0.0000 (13)
O30.0569 (14)0.0611 (14)0.0566 (13)−0.0124 (10)−0.0058 (11)0.0136 (10)
O40.0603 (14)0.0705 (14)0.0561 (13)−0.0203 (11)0.0054 (10)0.0077 (11)
N10.0526 (15)0.0518 (15)0.0452 (14)−0.0090 (12)0.0067 (12)−0.0050 (12)
N20.0538 (16)0.0436 (13)0.0595 (17)−0.0028 (11)0.0103 (13)0.0042 (12)
N30.077 (2)0.075 (2)0.079 (2)−0.0199 (16)0.0192 (17)−0.0153 (16)
C10.064 (2)0.059 (2)0.065 (2)−0.0197 (17)0.0220 (18)−0.0158 (17)
C20.065 (2)0.0572 (19)0.065 (2)−0.0172 (17)0.0225 (18)−0.0119 (17)
C30.079 (2)0.0536 (19)0.078 (2)−0.0128 (17)0.0222 (19)0.0057 (17)
C40.073 (2)0.064 (2)0.075 (3)−0.0230 (19)0.024 (2)−0.0108 (19)
C50.071 (2)0.066 (2)0.073 (2)−0.0255 (18)0.021 (2)−0.0150 (19)
C60.0500 (18)0.0562 (18)0.0426 (16)0.0026 (14)0.0048 (13)−0.0032 (14)
C70.0541 (18)0.0462 (17)0.0439 (17)−0.0047 (14)0.0048 (14)−0.0100 (14)
C80.0592 (19)0.0589 (19)0.0462 (18)−0.0128 (16)0.0097 (15)−0.0099 (15)
C90.089 (3)0.060 (2)0.056 (2)−0.0070 (19)0.0038 (19)0.0060 (16)
C100.086 (3)0.070 (2)0.090 (3)0.019 (2)0.016 (2)0.015 (2)
C110.070 (2)0.074 (2)0.081 (3)0.0126 (19)0.0208 (19)0.005 (2)
C120.0511 (18)0.064 (2)0.0417 (17)−0.0053 (16)0.0087 (14)−0.0109 (15)
C130.138 (4)0.103 (3)0.104 (3)−0.029 (3)0.070 (3)0.011 (3)
C140.0553 (19)0.0439 (16)0.0463 (18)0.0002 (14)0.0066 (14)0.0010 (14)
C150.0475 (17)0.0463 (16)0.0398 (16)0.0043 (13)0.0035 (13)0.0029 (13)
C160.0494 (18)0.0504 (17)0.0429 (17)−0.0016 (14)0.0092 (14)−0.0024 (14)
C170.0512 (19)0.070 (2)0.054 (2)0.0026 (16)0.0015 (15)−0.0093 (16)
C180.073 (2)0.072 (2)0.0492 (19)0.0068 (19)−0.0065 (17)0.0083 (17)
C190.084 (3)0.0557 (19)0.051 (2)0.0035 (18)0.0050 (18)0.0115 (16)
C200.071 (2)0.0481 (17)0.052 (2)−0.0018 (15)0.0177 (17)0.0073 (15)
C210.061 (2)0.080 (2)0.087 (3)−0.0251 (19)0.0094 (19)0.002 (2)

Geometric parameters (Å, °)

O1—C71.340 (3)C8—C91.366 (5)
O1—H10.8200C9—C101.400 (5)
O2—C81.383 (4)C9—H90.9300
O2—C131.428 (4)C10—C111.369 (5)
O3—C151.350 (3)C10—H100.9300
O3—H30.8200C11—H110.9300
O4—C161.369 (3)C12—H120.9300
O4—C211.421 (4)C13—H13A0.9600
N1—C121.267 (4)C13—H13B0.9600
N1—C11.423 (4)C13—H13C0.9600
N2—C201.288 (4)C14—C151.407 (4)
N2—C21.410 (4)C14—C191.410 (4)
N3—C51.397 (4)C14—C201.436 (4)
N3—C11.400 (4)C15—C161.402 (4)
C1—C21.408 (5)C16—C171.382 (4)
C2—C31.401 (4)C17—C181.397 (4)
C3—C41.377 (5)C17—H170.9300
C3—H3A0.9300C18—C191.360 (5)
C4—C51.359 (5)C18—H180.9300
C4—H40.9300C19—H190.9300
C5—H50.9300C20—H200.9300
C6—C111.389 (4)C21—H21A0.9600
C6—C71.416 (4)C21—H21B0.9600
C6—C121.459 (4)C21—H21C0.9600
C7—C81.406 (4)
C7—O1—H1109.5C10—C11—H11120.0
C8—O2—C13118.3 (3)C6—C11—H11120.0
C15—O3—H3109.5N1—C12—C6121.7 (3)
C16—O4—C21117.5 (2)N1—C12—H12119.1
C12—N1—C1118.0 (3)C6—C12—H12119.1
C20—N2—C2123.2 (3)O2—C13—H13A109.5
C5—N3—C1118.6 (3)O2—C13—H13B109.5
N3—C1—C2120.3 (3)H13A—C13—H13B109.5
N3—C1—N1120.9 (3)O2—C13—H13C109.5
C2—C1—N1118.7 (3)H13A—C13—H13C109.5
C3—C2—C1118.8 (3)H13B—C13—H13C109.5
C3—C2—N2124.9 (3)C15—C14—C19119.5 (3)
C1—C2—N2116.3 (3)C15—C14—C20120.3 (3)
C4—C3—C2120.2 (4)C19—C14—C20120.3 (3)
C4—C3—H3A119.9O3—C15—C16117.7 (2)
C2—C3—H3A119.9O3—C15—C14122.9 (3)
C5—C4—C3120.9 (3)C16—C15—C14119.4 (3)
C5—C4—H4119.5O4—C16—C17126.2 (3)
C3—C4—H4119.5O4—C16—C15114.2 (2)
C4—C5—N3121.1 (3)C17—C16—C15119.6 (3)
C4—C5—H5119.4C16—C17—C18120.8 (3)
N3—C5—H5119.4C16—C17—H17119.6
C11—C6—C7118.9 (3)C18—C17—H17119.6
C11—C6—C12118.4 (3)C19—C18—C17120.3 (3)
C7—C6—C12122.7 (3)C19—C18—H18119.9
O1—C7—C8117.2 (3)C17—C18—H18119.9
O1—C7—C6122.3 (3)C18—C19—C14120.4 (3)
C8—C7—C6120.5 (3)C18—C19—H19119.8
C9—C8—O2125.2 (3)C14—C19—H19119.8
C9—C8—C7118.7 (3)N2—C20—C14121.1 (3)
O2—C8—C7116.1 (3)N2—C20—H20119.5
C8—C9—C10120.9 (3)C14—C20—H20119.5
C8—C9—H9119.5O4—C21—H21A109.5
C10—C9—H9119.5O4—C21—H21B109.5
C11—C10—C9120.7 (3)H21A—C21—H21B109.5
C11—C10—H10119.6O4—C21—H21C109.5
C9—C10—H10119.6H21A—C21—H21C109.5
C10—C11—C6120.1 (3)H21B—C21—H21C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.962.683 (3)146
O3—H3···N20.821.852.568 (3)146

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2604).

References

  • Bi, W.-Y., Lü, X.-Q., Cai, W.-L., Song, J.-R. & Ng, S. W. (2007). Acta Cryst. E63, o1615–o1616.
  • Bruker (2001). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cimerman, Z., Galesic, N. & Bosner, B. (1992). J. Mol. Struct 274, 131–144.
  • Sheldrick, G. M. (2008a). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. [PubMed]

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