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In the title mol­ecule, C13H12N2O2, the dihedral angle between the benzene ring system and the pyridine ring is 32.0 (1)°. An intra­molecular O—H...N hydrogen bond stabilizes the mol­ecular structure. Adjacent aromatic rings indicate the presence of π–π stacking inter­actions with a distance of 5.610 Å and a perpendicular distance of 2.432 Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023823/at2294sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023823/at2294Isup2.hkl
Contains datablock I

CCDC reference: 651502

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.032
  • wR factor = 0.084
  • Data-to-parameter ratio = 8.6

checkCIF/PLATON results

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Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.45 From the CIF: _reflns_number_total 1373 Count of symmetry unique reflns 1382 Completeness (_total/calc) 99.35% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and structure of the title compound, (I).

In the molecular structure of (I) (Fig. 1), the expected geometric parameters are observed. The benzaldehyde ring system (C7—C12) is planar, with an r.m.s. deviation for the fitted atoms of 0.0018 (6) Å, as is the pyridine ring (C1—C5/N2), with an r.m.s. deviation of 0.0069 (5) Å. The dihedral angle between these two planes is 32.0 (1)°. An intramolecular O—H···N hydrogen bond stabilizes the molecular conformation, and the distance of 5.610 Å of the adjacent aromactic rings indicates the presence of π-π stacking interactions, which stabilize the crystal packing, as illustrated in Fig.2.

Related literature top

For related literature, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).

Experimental top

An anhydrous ethanol solution (50 ml) of 2-hydroxy-3-methoxy-benzaldehyde (1.52 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of pyridin-3-ylamine (0.94 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N2, whereupon a yellow solution appeared. The solvent was removed and the residue was recrystallized from anhydrous ethanol. The product was isolated and then dried in vacuo to give pure compound (I) in 91% yield. Yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution.

Refinement top

The N-bound H atom was located in a difference Fourier map and its positional parameters were refined, with Uiso(H) = 1.2Ueq(N). C-bound H atoms were included in calculated positions, with C—H = 0.95 (aromatic) or 0.99 Å (methylene), and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Structure description top

In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and structure of the title compound, (I).

In the molecular structure of (I) (Fig. 1), the expected geometric parameters are observed. The benzaldehyde ring system (C7—C12) is planar, with an r.m.s. deviation for the fitted atoms of 0.0018 (6) Å, as is the pyridine ring (C1—C5/N2), with an r.m.s. deviation of 0.0069 (5) Å. The dihedral angle between these two planes is 32.0 (1)°. An intramolecular O—H···N hydrogen bond stabilizes the molecular conformation, and the distance of 5.610 Å of the adjacent aromactic rings indicates the presence of π-π stacking interactions, which stabilize the crystal packing, as illustrated in Fig.2.

For related literature, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of (I), shows its layered structure. H atoms have been omitted for clarity.
2-Methoxy-6-(pyridin-3-yliminomethyl)phenol top
Crystal data top
C13H12N2O2F(000) = 480
Mr = 228.25Dx = 1.342 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3145 reflections
a = 5.6101 (19) Åθ = 2.4–26.4°
b = 9.278 (3) ŵ = 0.09 mm1
c = 21.708 (7) ÅT = 294 K
V = 1129.9 (7) Å3Block, yellow
Z = 40.24 × 0.20 × 0.18 mm
Data collection top
Bruker SMART CCD area detector
diffractometer
1373 independent reflections
Radiation source: fine-focus sealed tube1187 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 26.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 76
Tmin = 0.978, Tmax = 0.984k = 115
6440 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0429P)2 + 0.1574P]
where P = (Fo2 + 2Fc2)/3
1373 reflections(Δ/σ)max < 0.001
159 parametersΔρmax = 0.10 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C13H12N2O2V = 1129.9 (7) Å3
Mr = 228.25Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.6101 (19) ŵ = 0.09 mm1
b = 9.278 (3) ÅT = 294 K
c = 21.708 (7) Å0.24 × 0.20 × 0.18 mm
Data collection top
Bruker SMART CCD area detector
diffractometer
1373 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1187 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.984Rint = 0.025
6440 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.10 e Å3
1373 reflectionsΔρmin = 0.16 e Å3
159 parameters
Special details top

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) top
xyzUiso*/Ueq
N10.2010 (4)0.4487 (2)0.29371 (9)0.0682 (6)
N20.3205 (3)0.39459 (18)0.19617 (7)0.0462 (4)
O10.5051 (3)0.54594 (16)0.10671 (7)0.0534 (4)
H1A0.399 (6)0.522 (3)0.1380 (13)0.097 (10)*
O20.8401 (3)0.57453 (15)0.02324 (6)0.0560 (4)
C10.0443 (4)0.4520 (3)0.24816 (11)0.0563 (6)
H10.08180.50710.21370.068*
C20.1715 (4)0.3796 (2)0.24799 (8)0.0435 (4)
C30.2295 (4)0.3008 (2)0.30003 (9)0.0506 (5)
H30.37420.25230.30260.061*
C40.0693 (5)0.2959 (3)0.34784 (10)0.0593 (6)
H40.10360.24350.38330.071*
C50.1414 (5)0.3690 (3)0.34257 (11)0.0657 (7)
H50.24950.36290.37490.079*
C60.4585 (4)0.2907 (2)0.18057 (8)0.0471 (5)
H60.44710.20360.20160.057*
C70.6313 (4)0.3041 (2)0.13150 (8)0.0426 (4)
C80.6514 (4)0.4326 (2)0.09765 (8)0.0415 (4)
C90.8327 (4)0.4450 (2)0.05357 (8)0.0441 (4)
C100.9883 (4)0.3325 (2)0.04384 (9)0.0498 (5)
H101.10880.34170.01470.060*
C110.9668 (5)0.2054 (2)0.07722 (9)0.0546 (5)
H111.07200.12970.07020.066*
C120.7905 (4)0.1918 (2)0.12035 (9)0.0518 (5)
H120.77670.10640.14250.062*
C131.0462 (4)0.6031 (3)0.01286 (10)0.0625 (6)
H13A1.18630.58970.01190.094*
H13B1.04080.70070.02750.094*
H13C1.05060.53830.04730.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0526 (11)0.0777 (13)0.0742 (12)0.0044 (12)0.0053 (11)0.0131 (12)
N20.0513 (10)0.0454 (9)0.0419 (8)0.0043 (9)0.0010 (8)0.0020 (7)
O10.0621 (9)0.0419 (7)0.0563 (8)0.0063 (8)0.0091 (8)0.0068 (7)
O20.0678 (9)0.0453 (8)0.0548 (8)0.0007 (9)0.0127 (8)0.0113 (6)
C10.0570 (14)0.0585 (13)0.0534 (11)0.0038 (12)0.0058 (11)0.0042 (11)
C20.0464 (11)0.0404 (10)0.0437 (9)0.0073 (10)0.0020 (9)0.0025 (8)
C30.0540 (12)0.0486 (11)0.0493 (10)0.0023 (11)0.0022 (10)0.0026 (9)
C40.0738 (16)0.0558 (12)0.0484 (11)0.0114 (13)0.0071 (11)0.0009 (10)
C50.0630 (15)0.0728 (15)0.0614 (13)0.0138 (15)0.0157 (12)0.0117 (13)
C60.0581 (12)0.0405 (10)0.0429 (10)0.0071 (11)0.0020 (10)0.0030 (9)
C70.0511 (11)0.0397 (9)0.0371 (8)0.0026 (10)0.0041 (9)0.0006 (8)
C80.0476 (10)0.0382 (9)0.0386 (9)0.0007 (10)0.0046 (8)0.0023 (7)
C90.0544 (11)0.0404 (9)0.0375 (9)0.0029 (11)0.0027 (9)0.0016 (8)
C100.0526 (12)0.0529 (12)0.0440 (10)0.0005 (11)0.0006 (10)0.0005 (9)
C110.0635 (14)0.0478 (11)0.0524 (11)0.0109 (12)0.0011 (11)0.0024 (10)
C120.0691 (14)0.0403 (10)0.0461 (10)0.0030 (11)0.0032 (11)0.0059 (9)
C130.0674 (14)0.0630 (14)0.0572 (12)0.0082 (13)0.0092 (12)0.0157 (11)
Geometric parameters (Å, º) top
N1—C11.324 (3)C5—H50.9300
N1—C51.335 (3)C6—C71.446 (3)
N2—C61.282 (3)C6—H60.9300
N2—C21.409 (3)C7—C121.394 (3)
O1—C81.348 (2)C7—C81.405 (3)
O1—H1A0.93 (3)C8—C91.401 (3)
O2—C91.371 (2)C9—C101.377 (3)
O2—C131.422 (3)C10—C111.389 (3)
C1—C21.385 (3)C10—H100.9300
C1—H10.9300C11—C121.367 (3)
C2—C31.384 (3)C11—H110.9300
C3—C41.374 (3)C12—H120.9300
C3—H30.9300C13—H13A0.9600
C4—C51.368 (4)C13—H13B0.9600
C4—H40.9300C13—H13C0.9600
C1—N1—C5116.1 (2)C12—C7—C6119.54 (17)
C6—N2—C2119.67 (17)C8—C7—C6120.82 (19)
C8—O1—H1A107.8 (18)O1—C8—C9118.53 (17)
C9—O2—C13116.95 (18)O1—C8—C7122.45 (18)
N1—C1—C2124.9 (2)C9—C8—C7119.01 (18)
N1—C1—H1117.6O2—C9—C10124.84 (18)
C2—C1—H1117.6O2—C9—C8114.96 (17)
C3—C2—C1117.4 (2)C10—C9—C8120.19 (17)
C3—C2—N2124.35 (19)C9—C10—C11120.5 (2)
C1—C2—N2118.23 (18)C9—C10—H10119.7
C4—C3—C2118.7 (2)C11—C10—H10119.7
C4—C3—H3120.6C12—C11—C10119.9 (2)
C2—C3—H3120.6C12—C11—H11120.1
C5—C4—C3119.0 (2)C10—C11—H11120.1
C5—C4—H4120.5C11—C12—C7120.87 (19)
C3—C4—H4120.5C11—C12—H12119.6
N1—C5—C4123.9 (2)C7—C12—H12119.6
N1—C5—H5118.0O2—C13—H13A109.5
C4—C5—H5118.0O2—C13—H13B109.5
N2—C6—C7122.32 (18)H13A—C13—H13B109.5
N2—C6—H6118.8O2—C13—H13C109.5
C7—C6—H6118.8H13A—C13—H13C109.5
C12—C7—C8119.49 (18)H13B—C13—H13C109.5
C5—N1—C1—C20.2 (3)C12—C7—C8—C90.4 (3)
N1—C1—C2—C31.7 (3)C6—C7—C8—C9175.32 (17)
N1—C1—C2—N2179.5 (2)C13—O2—C9—C1011.2 (3)
C6—N2—C2—C332.8 (3)C13—O2—C9—C8168.11 (17)
C6—N2—C2—C1149.52 (19)O1—C8—C9—O20.6 (3)
C1—C2—C3—C41.6 (3)C7—C8—C9—O2179.39 (17)
N2—C2—C3—C4179.30 (19)O1—C8—C9—C10178.80 (18)
C2—C3—C4—C50.2 (3)C7—C8—C9—C100.0 (3)
C1—N1—C5—C41.4 (4)O2—C9—C10—C11179.7 (2)
C3—C4—C5—N11.4 (4)C8—C9—C10—C110.4 (3)
C2—N2—C6—C7174.12 (17)C9—C10—C11—C120.3 (3)
N2—C6—C7—C12174.32 (18)C10—C11—C12—C70.1 (3)
N2—C6—C7—C81.4 (3)C8—C7—C12—C110.4 (3)
C12—C7—C8—O1179.15 (17)C6—C7—C12—C11175.31 (18)
C6—C7—C8—O13.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N20.93 (3)1.78 (3)2.611 (2)147 (3)

Experimental details

Crystal data
Chemical formulaC13H12N2O2
Mr228.25
Crystal system, space groupOrthorhombic, P212121
Temperature (K)294
a, b, c (Å)5.6101 (19), 9.278 (3), 21.708 (7)
V3)1129.9 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.24 × 0.20 × 0.18
Data collection
DiffractometerBruker SMART CCD area detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.978, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
6440, 1373, 1187
Rint0.025
(sin θ/λ)max1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.084, 1.04
No. of reflections1373
No. of parameters159
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.10, 0.16

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N20.93 (3)1.78 (3)2.611 (2)147 (3)
 

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