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The title compound, C12H12N2O, crystallizes in the non-centro­symmetric P212121 space group giving crystals showing a second harmonic generation (SHG) property. The crystal structure consists of discrete mol­ecules and forms a three-di­mensional network through intermolecular hydrogen bonding.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005037/na6064sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005037/na6064Isup2.hkl
Contains datablock I

CCDC reference: 165650

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.058
  • wR factor = 0.133
  • Data-to-parameter ratio = 16.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.47 From the CIF: _reflns_number_total 2308 Count of symmetry unique reflns 1366 Completeness (_total/calc) 168.96% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 942 Fraction of Friedel pairs measured 0.690 Are heavy atom types Z>Si present no ALERT: MoKa measured Friedel data cannot be used to determine absolute structure in a light-atom study EXCEPT under VERY special conditions. It is preferred that Friedel data is merged in such cases.

Comment top

The title compound, (I), is shown in Fig. 1. These molecules are packed in an acentric structure probably as a consequence of the two hydrogen-bonding interactions that are found involving the phenol hydroxyl group, which acts as both donor and acceptor, the amino group acting as donor, and the pyridine N atom acting as acceptor. O—H···N hydrogen bonds joins the molecules `head-to-tail' in chains running along the [001] direction with a C(11) motif (Etter et al., 1990), while N—H···O bonds joins the chains along [010] with a C(8) motif, the combination of the two chains resulting in sheets (see Fig. 2).

All bond lengths and angles are in the normal ranges. The dihedral angle between the two aromatic ring planes is 63.4 (2)°. The conformation along the C8—N1—N7—C6 central chain is given by the torsion angles C9—C8—N1—N7 of 171.6 (3), C8—N1—C7—C6 of 174.1 (2) and N1—C7—C6—C5 of 128.7 (3)°.

Experimental top

4-Hydroxybenzaldehyde (6.15 g, 50 mmol) and 3-aminopyridine (4.71 g, 50 mmol) in 100 ml of toluene was refluxed with a Dean–Stark trap for 12 h. Toluene was removed in vacuo, and the residue was dissolved in 100 ml of ethanol. NaBH4 (3.70 g, 100 mmol) was added to the ethanol solution and the resultant mixture was stirred at room temperature for 18 h. Excess NaBH4 was quenched with water and then with saturated NH4Cl solution at 343 K. A pale-yellow solid powder was obtained through filtration (yield: 7.20 g, 72.0%). Crystals suitable for single-crystal X-ray diffraction studies were obtained by hydrothermal treatment of W(CO)6 and 4-[(3-pyridinylamino)methyl]phenol in methanol at 353 K. The structure of the title compound was confirmed by IR analysis [3338 (s), 3021 (w), 2804 (w), 2680 (w), 1597 (s), 1576 (s), 1512 (s), 1463 (m), 1341 (m), 1320 (m), 1276 (s), 828 (m), 790 (m) and 698 (w)]. The powder test of the title compound shows a positive signal for SHG.

Refinement top

After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms, except for the H atoms involved in hydrogen bonding which were refined isotropically. It was not possible to define the correct absolute structure as all the atoms were too weak anomalous scatterers of Mo Kα radiation.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of (I) viewed down the a axis. O—H···N and N—H···O hydrogen-bond contacts are shown as dash lines.
4-[(3-Pyridylamino)methyl]phenol top
Crystal data top
C12H12N2ODx = 1.316 Mg m3
Mr = 200.24Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 2653 reflections
a = 6.5392 (2) Åθ = 2.0–29.5°
b = 7.6077 (1) ŵ = 0.09 mm1
c = 20.3127 (5) ÅT = 293 K
V = 1010.52 (4) Å3Rectangular block, yellow
Z = 40.20 × 0.14 × 0.01 mm
F(000) = 424
Data collection top
Siemens SMART CCD area-detector
diffractometer
1400 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.079
Graphite monochromatorθmax = 27.5°, θmin = 2.0°
Detector resolution: 8.33 pixels mm-1h = 58
ω scansk = 99
6968 measured reflectionsl = 2624
2308 independent reflections
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0525P)2]
where P = (Fo2 + 2Fc2)/3
2308 reflections(Δ/σ)max < 0.001
144 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C12H12N2OV = 1010.52 (4) Å3
Mr = 200.24Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.5392 (2) ŵ = 0.09 mm1
b = 7.6077 (1) ÅT = 293 K
c = 20.3127 (5) Å0.20 × 0.14 × 0.01 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
1400 reflections with I > 2σ(I)
6968 measured reflectionsRint = 0.079
2308 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.16 e Å3
2308 reflectionsΔρmin = 0.19 e Å3
144 parameters
Special details top

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Coverage of the unique set is 100% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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
O10.1374 (3)0.2800 (3)0.13307 (10)0.0513 (6)
N10.4632 (4)0.0819 (3)0.36769 (12)0.0474 (7)
N20.6644 (4)0.0710 (3)0.52458 (11)0.0565 (7)
C10.1771 (4)0.2875 (4)0.28009 (14)0.0429 (7)
H1C0.16730.32890.32300.051*
C20.0173 (5)0.3155 (4)0.23731 (13)0.0423 (7)
H2B0.09780.37670.25150.051*
C30.0265 (4)0.2536 (3)0.17339 (12)0.0382 (7)
C40.2022 (4)0.1703 (4)0.15207 (13)0.0434 (7)
H4A0.21240.13170.10880.052*
C50.3637 (5)0.1444 (3)0.19547 (13)0.0423 (7)
H5A0.48190.08950.18050.051*
C60.3529 (4)0.1985 (3)0.26062 (12)0.0378 (7)
C70.5280 (5)0.1666 (4)0.30710 (13)0.0449 (7)
H7A0.59240.27800.31760.054*
H7B0.62910.09330.28550.054*
C80.5991 (4)0.0572 (3)0.41807 (12)0.0387 (6)
C90.5452 (5)0.0443 (4)0.47296 (13)0.0489 (8)
H9A0.41660.09650.47310.059*
C100.8513 (6)0.0047 (5)0.52411 (16)0.0633 (9)
H10A0.93680.01170.56020.076*
C110.9195 (5)0.1041 (4)0.47280 (15)0.0547 (8)
H11A1.04890.15460.47420.066*
C120.7959 (4)0.1290 (4)0.41932 (14)0.0472 (8)
H12A0.84300.19390.38360.057*
H1A0.132 (6)0.209 (5)0.0927 (18)0.099 (13)*
H1B0.364 (5)0.004 (4)0.3607 (16)0.077 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0491 (12)0.0528 (13)0.0519 (12)0.0139 (10)0.0053 (11)0.0062 (10)
N10.0466 (15)0.0442 (14)0.0514 (14)0.0119 (13)0.0039 (13)0.0065 (12)
N20.0592 (17)0.0591 (17)0.0512 (15)0.0067 (14)0.0055 (15)0.0101 (13)
C10.0475 (18)0.0395 (17)0.0417 (14)0.0016 (14)0.0079 (15)0.0052 (12)
C20.0416 (16)0.0336 (14)0.0518 (18)0.0043 (13)0.0103 (15)0.0045 (13)
C30.0416 (17)0.0311 (14)0.0420 (15)0.0008 (13)0.0041 (14)0.0034 (12)
C40.0516 (18)0.0425 (16)0.0362 (14)0.0050 (14)0.0119 (15)0.0013 (12)
C50.0399 (16)0.0379 (15)0.0490 (17)0.0068 (13)0.0112 (15)0.0048 (13)
C60.0392 (16)0.0315 (15)0.0429 (16)0.0062 (13)0.0069 (14)0.0026 (12)
C70.0433 (17)0.0412 (16)0.0501 (17)0.0026 (14)0.0006 (15)0.0030 (13)
C80.0415 (15)0.0315 (14)0.0431 (15)0.0012 (12)0.0048 (14)0.0034 (13)
C90.0507 (18)0.0430 (17)0.0530 (17)0.0017 (15)0.0030 (17)0.0029 (14)
C100.060 (2)0.070 (2)0.060 (2)0.007 (2)0.017 (2)0.0010 (17)
C110.0487 (19)0.056 (2)0.0591 (19)0.0044 (15)0.0121 (17)0.0053 (16)
C120.0470 (18)0.0414 (17)0.0532 (17)0.0042 (15)0.0014 (16)0.0022 (14)
Geometric parameters (Å, º) top
O1—C31.363 (3)C4—H4A0.9300
O1—H1A0.98 (4)C5—C61.388 (3)
N1—C81.368 (3)C5—H5A0.9300
N1—C71.453 (3)C6—C71.504 (4)
N1—H1B0.89 (3)C7—H7A0.9700
N2—C91.322 (3)C7—H7B0.9700
N2—C101.351 (4)C8—C121.398 (4)
C1—C21.376 (4)C8—C91.401 (4)
C1—C61.392 (4)C9—H9A0.9300
C1—H1C0.9300C10—C111.363 (4)
C2—C31.383 (4)C10—H10A0.9300
C2—H2B0.9300C11—C121.367 (4)
C3—C41.382 (4)C11—H11A0.9300
C4—C51.390 (4)C12—H12A0.9300
C3—O1—H1A113 (2)C1—C6—C7122.0 (2)
C8—N1—C7120.3 (2)N1—C7—C6112.4 (2)
C8—N1—H1B120 (2)N1—C7—H7A109.1
C7—N1—H1B112 (2)C6—C7—H7A109.1
C9—N2—C10117.5 (3)N1—C7—H7B109.1
C2—C1—C6121.6 (2)C6—C7—H7B109.1
C2—C1—H1C119.2H7A—C7—H7B107.9
C6—C1—H1C119.2N1—C8—C12123.9 (2)
C1—C2—C3120.5 (3)N1—C8—C9120.5 (3)
C1—C2—H2B119.8C12—C8—C9115.6 (2)
C3—C2—H2B119.8N2—C9—C8124.6 (3)
O1—C3—C4122.2 (2)N2—C9—H9A117.7
O1—C3—C2118.7 (2)C8—C9—H9A117.7
C4—C3—C2119.1 (3)N2—C10—C11122.5 (3)
C3—C4—C5119.9 (2)N2—C10—H10A118.7
C3—C4—H4A120.1C11—C10—H10A118.7
C5—C4—H4A120.1C10—C11—C12119.4 (3)
C6—C5—C4121.6 (3)C10—C11—H11A120.3
C6—C5—H5A119.2C12—C11—H11A120.3
C4—C5—H5A119.2C11—C12—C8120.3 (3)
C5—C6—C1117.2 (3)C11—C12—H12A119.8
C5—C6—C7120.8 (2)C8—C12—H12A119.8
C6—C1—C2—C30.8 (4)C1—C6—C7—N153.4 (3)
C1—C2—C3—O1178.2 (2)C7—N1—C8—C128.6 (4)
C1—C2—C3—C43.0 (4)C7—N1—C8—C9171.6 (3)
O1—C3—C4—C5179.0 (2)C10—N2—C9—C80.2 (4)
C2—C3—C4—C52.3 (4)N1—C8—C9—N2178.0 (3)
C3—C4—C5—C60.7 (4)C12—C8—C9—N21.7 (4)
C4—C5—C6—C12.9 (4)C9—N2—C10—C110.6 (5)
C4—C5—C6—C7179.0 (2)N2—C10—C11—C120.2 (5)
C2—C1—C6—C52.2 (4)C10—C11—C12—C81.8 (4)
C2—C1—C6—C7179.8 (2)N1—C8—C12—C11177.3 (3)
C8—N1—C7—C6174.1 (2)C9—C8—C12—C112.5 (4)
C5—C6—C7—N1128.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N2i0.98 (4)1.75 (4)2.723 (3)170 (4)
N1—H1B···O1ii0.89 (3)2.26 (3)3.133 (3)166 (3)
Symmetry codes: (i) x+1/2, y, z1/2; (ii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H12N2O
Mr200.24
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)6.5392 (2), 7.6077 (1), 20.3127 (5)
V3)1010.52 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.14 × 0.01
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6968, 2308, 1400
Rint0.079
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.133, 0.99
No. of reflections2308
No. of parameters144
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.16, 0.19

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT and SADABS (Sheldrick, 1996), SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
O1—C31.363 (3)N2—C91.322 (3)
N1—C81.368 (3)N2—C101.351 (4)
N1—C71.453 (3)
C3—O1—H1A113 (2)C7—N1—H1B112 (2)
C8—N1—C7120.3 (2)C9—N2—C10117.5 (3)
C8—N1—H1B120 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N2i0.98 (4)1.75 (4)2.723 (3)170 (4)
N1—H1B···O1ii0.89 (3)2.26 (3)3.133 (3)166 (3)
Symmetry codes: (i) x+1/2, y, z1/2; (ii) x, y+1/2, z+1/2.
 

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