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
CCDC reference: 165650
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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.
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.
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.
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).
4-[(3-Pyridylamino)methyl]phenol
top
Crystal data top
C12H12N2O | Dx = 1.316 Mg m−3 |
Mr = 200.24 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 2653 reflections |
a = 6.5392 (2) Å | θ = 2.0–29.5° |
b = 7.6077 (1) Å | µ = 0.09 mm−1 |
c = 20.3127 (5) Å | T = 293 K |
V = 1010.52 (4) Å3 | Rectangular block, yellow |
Z = 4 | 0.20 × 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 tube | Rint = 0.079 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
Detector resolution: 8.33 pixels mm-1 | h = −5→8 |
ω scans | k = −9→9 |
6968 measured reflections | l = −26→24 |
2308 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H 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 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C12H12N2O | V = 1010.52 (4) Å3 |
Mr = 200.24 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.5392 (2) Å | µ = 0.09 mm−1 |
b = 7.6077 (1) Å | T = 293 K |
c = 20.3127 (5) Å | 0.20 × 0.14 × 0.01 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 1400 reflections with I > 2σ(I) |
6968 measured reflections | Rint = 0.079 |
2308 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.16 e Å−3 |
2308 reflections | Δρmin = −0.19 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | −0.1374 (3) | −0.2800 (3) | 0.13307 (10) | 0.0513 (6) | |
N1 | 0.4632 (4) | −0.0819 (3) | 0.36769 (12) | 0.0474 (7) | |
N2 | 0.6644 (4) | 0.0710 (3) | 0.52458 (11) | 0.0565 (7) | |
C1 | 0.1771 (4) | −0.2875 (4) | 0.28009 (14) | 0.0429 (7) | |
H1C | 0.1673 | −0.3289 | 0.3230 | 0.051* | |
C2 | 0.0173 (5) | −0.3155 (4) | 0.23731 (13) | 0.0423 (7) | |
H2B | −0.0978 | −0.3767 | 0.2515 | 0.051* | |
C3 | 0.0265 (4) | −0.2536 (3) | 0.17339 (12) | 0.0382 (7) | |
C4 | 0.2022 (4) | −0.1703 (4) | 0.15207 (13) | 0.0434 (7) | |
H4A | 0.2124 | −0.1317 | 0.1088 | 0.052* | |
C5 | 0.3637 (5) | −0.1444 (3) | 0.19547 (13) | 0.0423 (7) | |
H5A | 0.4819 | −0.0895 | 0.1805 | 0.051* | |
C6 | 0.3529 (4) | −0.1985 (3) | 0.26062 (12) | 0.0378 (7) | |
C7 | 0.5280 (5) | −0.1666 (4) | 0.30710 (13) | 0.0449 (7) | |
H7A | 0.5924 | −0.2780 | 0.3176 | 0.054* | |
H7B | 0.6291 | −0.0933 | 0.2855 | 0.054* | |
C8 | 0.5991 (4) | −0.0572 (3) | 0.41807 (12) | 0.0387 (6) | |
C9 | 0.5452 (5) | 0.0443 (4) | 0.47296 (13) | 0.0489 (8) | |
H9A | 0.4166 | 0.0965 | 0.4731 | 0.059* | |
C10 | 0.8513 (6) | −0.0047 (5) | 0.52411 (16) | 0.0633 (9) | |
H10A | 0.9368 | 0.0117 | 0.5602 | 0.076* | |
C11 | 0.9195 (5) | −0.1041 (4) | 0.47280 (15) | 0.0547 (8) | |
H11A | 1.0489 | −0.1546 | 0.4742 | 0.066* | |
C12 | 0.7959 (4) | −0.1290 (4) | 0.41932 (14) | 0.0472 (8) | |
H12A | 0.8430 | −0.1939 | 0.3836 | 0.057* | |
H1A | −0.132 (6) | −0.209 (5) | 0.0927 (18) | 0.099 (13)* | |
H1B | 0.364 (5) | −0.004 (4) | 0.3607 (16) | 0.077 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0491 (12) | 0.0528 (13) | 0.0519 (12) | −0.0139 (10) | −0.0053 (11) | 0.0062 (10) |
N1 | 0.0466 (15) | 0.0442 (14) | 0.0514 (14) | 0.0119 (13) | −0.0039 (13) | −0.0065 (12) |
N2 | 0.0592 (17) | 0.0591 (17) | 0.0512 (15) | −0.0067 (14) | −0.0055 (15) | −0.0101 (13) |
C1 | 0.0475 (18) | 0.0395 (17) | 0.0417 (14) | −0.0016 (14) | 0.0079 (15) | 0.0052 (12) |
C2 | 0.0416 (16) | 0.0336 (14) | 0.0518 (18) | −0.0043 (13) | 0.0103 (15) | 0.0045 (13) |
C3 | 0.0416 (17) | 0.0311 (14) | 0.0420 (15) | −0.0008 (13) | 0.0041 (14) | −0.0034 (12) |
C4 | 0.0516 (18) | 0.0425 (16) | 0.0362 (14) | −0.0050 (14) | 0.0119 (15) | −0.0013 (12) |
C5 | 0.0399 (16) | 0.0379 (15) | 0.0490 (17) | −0.0068 (13) | 0.0112 (15) | −0.0048 (13) |
C6 | 0.0392 (16) | 0.0315 (15) | 0.0429 (16) | 0.0062 (13) | 0.0069 (14) | −0.0026 (12) |
C7 | 0.0433 (17) | 0.0412 (16) | 0.0501 (17) | 0.0026 (14) | 0.0006 (15) | −0.0030 (13) |
C8 | 0.0415 (15) | 0.0315 (14) | 0.0431 (15) | −0.0012 (12) | −0.0048 (14) | 0.0034 (13) |
C9 | 0.0507 (18) | 0.0430 (17) | 0.0530 (17) | 0.0017 (15) | −0.0030 (17) | −0.0029 (14) |
C10 | 0.060 (2) | 0.070 (2) | 0.060 (2) | −0.007 (2) | −0.017 (2) | −0.0010 (17) |
C11 | 0.0487 (19) | 0.056 (2) | 0.0591 (19) | 0.0044 (15) | −0.0121 (17) | 0.0053 (16) |
C12 | 0.0470 (18) | 0.0414 (17) | 0.0532 (17) | 0.0042 (15) | 0.0014 (16) | 0.0022 (14) |
Geometric parameters (Å, º) top
O1—C3 | 1.363 (3) | C4—H4A | 0.9300 |
O1—H1A | 0.98 (4) | C5—C6 | 1.388 (3) |
N1—C8 | 1.368 (3) | C5—H5A | 0.9300 |
N1—C7 | 1.453 (3) | C6—C7 | 1.504 (4) |
N1—H1B | 0.89 (3) | C7—H7A | 0.9700 |
N2—C9 | 1.322 (3) | C7—H7B | 0.9700 |
N2—C10 | 1.351 (4) | C8—C12 | 1.398 (4) |
C1—C2 | 1.376 (4) | C8—C9 | 1.401 (4) |
C1—C6 | 1.392 (4) | C9—H9A | 0.9300 |
C1—H1C | 0.9300 | C10—C11 | 1.363 (4) |
C2—C3 | 1.383 (4) | C10—H10A | 0.9300 |
C2—H2B | 0.9300 | C11—C12 | 1.367 (4) |
C3—C4 | 1.382 (4) | C11—H11A | 0.9300 |
C4—C5 | 1.390 (4) | C12—H12A | 0.9300 |
| | | |
C3—O1—H1A | 113 (2) | C1—C6—C7 | 122.0 (2) |
C8—N1—C7 | 120.3 (2) | N1—C7—C6 | 112.4 (2) |
C8—N1—H1B | 120 (2) | N1—C7—H7A | 109.1 |
C7—N1—H1B | 112 (2) | C6—C7—H7A | 109.1 |
C9—N2—C10 | 117.5 (3) | N1—C7—H7B | 109.1 |
C2—C1—C6 | 121.6 (2) | C6—C7—H7B | 109.1 |
C2—C1—H1C | 119.2 | H7A—C7—H7B | 107.9 |
C6—C1—H1C | 119.2 | N1—C8—C12 | 123.9 (2) |
C1—C2—C3 | 120.5 (3) | N1—C8—C9 | 120.5 (3) |
C1—C2—H2B | 119.8 | C12—C8—C9 | 115.6 (2) |
C3—C2—H2B | 119.8 | N2—C9—C8 | 124.6 (3) |
O1—C3—C4 | 122.2 (2) | N2—C9—H9A | 117.7 |
O1—C3—C2 | 118.7 (2) | C8—C9—H9A | 117.7 |
C4—C3—C2 | 119.1 (3) | N2—C10—C11 | 122.5 (3) |
C3—C4—C5 | 119.9 (2) | N2—C10—H10A | 118.7 |
C3—C4—H4A | 120.1 | C11—C10—H10A | 118.7 |
C5—C4—H4A | 120.1 | C10—C11—C12 | 119.4 (3) |
C6—C5—C4 | 121.6 (3) | C10—C11—H11A | 120.3 |
C6—C5—H5A | 119.2 | C12—C11—H11A | 120.3 |
C4—C5—H5A | 119.2 | C11—C12—C8 | 120.3 (3) |
C5—C6—C1 | 117.2 (3) | C11—C12—H12A | 119.8 |
C5—C6—C7 | 120.8 (2) | C8—C12—H12A | 119.8 |
| | | |
C6—C1—C2—C3 | −0.8 (4) | C1—C6—C7—N1 | −53.4 (3) |
C1—C2—C3—O1 | −178.2 (2) | C7—N1—C8—C12 | −8.6 (4) |
C1—C2—C3—C4 | 3.0 (4) | C7—N1—C8—C9 | 171.6 (3) |
O1—C3—C4—C5 | 179.0 (2) | C10—N2—C9—C8 | 0.2 (4) |
C2—C3—C4—C5 | −2.3 (4) | N1—C8—C9—N2 | 178.0 (3) |
C3—C4—C5—C6 | −0.7 (4) | C12—C8—C9—N2 | −1.7 (4) |
C4—C5—C6—C1 | 2.9 (4) | C9—N2—C10—C11 | 0.6 (5) |
C4—C5—C6—C7 | −179.0 (2) | N2—C10—C11—C12 | 0.2 (5) |
C2—C1—C6—C5 | −2.2 (4) | C10—C11—C12—C8 | −1.8 (4) |
C2—C1—C6—C7 | 179.8 (2) | N1—C8—C12—C11 | −177.3 (3) |
C8—N1—C7—C6 | 174.1 (2) | C9—C8—C12—C11 | 2.5 (4) |
C5—C6—C7—N1 | 128.7 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N2i | 0.98 (4) | 1.75 (4) | 2.723 (3) | 170 (4) |
N1—H1B···O1ii | 0.89 (3) | 2.26 (3) | 3.133 (3) | 166 (3) |
Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C12H12N2O |
Mr | 200.24 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.5392 (2), 7.6077 (1), 20.3127 (5) |
V (Å3) | 1010.52 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.14 × 0.01 |
|
Data collection |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6968, 2308, 1400 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.133, 0.99 |
No. of reflections | 2308 |
No. of parameters | 144 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.19 |
Selected geometric parameters (Å, º) topO1—C3 | 1.363 (3) | N2—C9 | 1.322 (3) |
N1—C8 | 1.368 (3) | N2—C10 | 1.351 (4) |
N1—C7 | 1.453 (3) | | |
| | | |
C3—O1—H1A | 113 (2) | C7—N1—H1B | 112 (2) |
C8—N1—C7 | 120.3 (2) | C9—N2—C10 | 117.5 (3) |
C8—N1—H1B | 120 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N2i | 0.98 (4) | 1.75 (4) | 2.723 (3) | 170 (4) |
N1—H1B···O1ii | 0.89 (3) | 2.26 (3) | 3.133 (3) | 166 (3) |
Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x, y+1/2, −z+1/2. |
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)°.