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access2-{[(Pyridin-2-yl)amino]methyl}phenol
aKey Laboratory of Functional Inorganic Materials Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my
The planes of the aromatic rings of the title compound, C12H12N2O, are twisted by 50.33 (15)°. The phenol O atom is a hydrogen-bond donor to the pyridine N atom, resulting in the formation of an eight-membered ring in the molecule. The amino N atom is a hydrogen-bond donor to the phenol O atom of an adjacent molecule; this hydrogen bond leads to the formation of a helical chain that runs along the a axis.
Related literature
For the related compound 2-{[(pyrazin-2-yl)amino]methyl}phenol, see: Gao & Ng (2012![[Gao, S. & Ng, S. W. (2012). Acta Cryst. E68, o2472.]](../../../../../../logos/arrows/e_arr.gif "Gao, S. & Ng, S. W. (2012). Acta Cryst. E68, o2472.")
). For 2-[(pyridin-3-ylamino)methyl]phenol, see: Xu et al. (2011). For the metal adducts of 2-[(pyridin-2-ylamino)methyl]phenol, see: Yalçın et al. (2007).
![[Scheme 1]](xu5581scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812031340/xu5581sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031340/xu5581Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812031340/xu5581Isup3.cml
A solution of 2-aminopyridine (1 mmol) and salicylaldehyde (1 mmol) in toluene (50 ml) was heated for 10 h. The solvent was removed under vacuum, and the residue was reduced in absolute methanol by sodium borohydride. Light yellow crystals were obtained by recrystallization from methanol in 80% yield.
Carbon-bound H-atoms were placed in calculated positions (C–H 0.93 Å) and were included in the in the riding model approximation, with U(H) set to 1.2U(C). The amino and hydroxy H-atoms were located in a difference Fourier map, and were refined with distance restraints N–H 0.88±0.01 Å and O–H 0.84±0.01 Å; their temperature factors were refined.
In the absence of heavy scatters, 980 Friedel pairs were merged.
Salicylaldehyde condenses with aromatic to yield which serve as chelating ligands to a plethora of metal systems. These can be readily reduce to the corresponding secondary which can also function as chelating ligands. Curiously, there are only few 2-(arylamino)methylphenols compared with the plethora of in the chemical literature. Among the aminopyridine derivatives, only the of 2-((pyridin-3-ylamino)methyl)phenol has been reported (Xu et al., 2011). The 2-((pyridin-2-ylamino)methyl)phenol analog (Scheme I) has been described as its metal adducts only (Yalçın et al., 2007).
The two aromatic rings of the reduced Schiff-base, C12H12N2O, are twisted along the –CH2–NH– single-bond by 50.3 (1) °. The hydroxy O atom is hydrogen-bond donor to the pyridyl N atom and an eight-membered ring is formed (Fig. 1). The slightly flattened secondary amino N atom is hydrogen-bond donor to the O atom of an adjacent molecule; this hydrogen bond leads to the formation of a helical chain that runs along the a-axis of the orthorhombic (Fig. 2, Table 1).
For the related compound 2-{[(pyrazin-2-yl)amino]methyl}phenol, see: Gao & Ng (2012). For 2-[(pyridin-3-ylamino)methyl]phenol, see: Xu et al. (2011). For the metal adducts of 2-[(pyridin-2-ylamino)methyl]phenol, see: Yalçın et al. (2007).
Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./xu5581fig1thm.gif) | Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C12H12N2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. |
![[Figure 2]](./xu5581fig2thm.gif) | Fig. 2. Hydrogen-bonded chain motif. |
| C12H12N2O | F(000) = 424 |
| Mr = 200.24 | Dx = 1.280 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 6231 reflections |
| a = 6.3331 (4) Å | θ = 3.3–27.4° |
| b = 10.6761 (9) Å | µ = 0.08 mm−1 |
| c = 15.3714 (10) Å | T = 295 K |
| V = 1039.30 (13) Å3 | Prism, faint yellow |
| Z = 4 | 0.25 × 0.19 × 0.15 mm |
| Rigaku R-AXIS RAPID IP diffractometer | 1391 independent reflections |
| Radiation source: fine-focus sealed tube | 887 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.047 |
| ω scan | θmax = 27.4°, θmin = 3.3° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
| Tmin = 0.979, Tmax = 0.988 | k = −13→13 |
| 10221 measured reflections | l = −19→19 |
| 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0773P)2] where P = (Fo2 + 2Fc2)/3 |
| 1391 reflections | (Δ/σ)max = 0.001 |
| 144 parameters | Δρmax = 0.13 e Å−3 |
| 2 restraints | Δρmin = −0.18 e Å−3 |
| C12H12N2O | V = 1039.30 (13) Å3 |
| Mr = 200.24 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 6.3331 (4) Å | µ = 0.08 mm−1 |
| b = 10.6761 (9) Å | T = 295 K |
| c = 15.3714 (10) Å | 0.25 × 0.19 × 0.15 mm |
| Rigaku R-AXIS RAPID IP diffractometer | 1391 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 887 reflections with I > 2σ(I) |
| Tmin = 0.979, Tmax = 0.988 | Rint = 0.047 |
| 10221 measured reflections |
| R[F2 > 2σ(F2)] = 0.043 | 2 restraints |
| wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.13 e Å−3 |
| 1391 reflections | Δρmin = −0.18 e Å−3 |
| 144 parameters |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.6052 (3) | 0.1233 (2) | 0.18887 (14) | 0.0752 (7) | |
| N1 | 0.8839 (3) | 0.0670 (2) | 0.06566 (14) | 0.0570 (6) | |
| N2 | 1.1470 (4) | 0.1185 (3) | 0.16368 (15) | 0.0672 (8) | |
| C1 | 0.8251 (6) | 0.0489 (3) | −0.01804 (18) | 0.0672 (8) | |
| H1A | 0.6882 | 0.0212 | −0.0286 | 0.081* | |
| C2 | 0.9537 (6) | 0.0687 (3) | −0.0877 (2) | 0.0762 (9) | |
| H2A | 0.9069 | 0.0534 | −0.1441 | 0.091* | |
| C3 | 1.1575 (6) | 0.1126 (3) | −0.0720 (2) | 0.0706 (9) | |
| H3 | 1.2483 | 0.1294 | −0.1181 | 0.085* | |
| C4 | 1.2220 (5) | 0.1305 (3) | 0.01124 (19) | 0.0636 (8) | |
| H4 | 1.3573 | 0.1600 | 0.0227 | 0.076* | |
| C5 | 1.0823 (4) | 0.1041 (3) | 0.08020 (17) | 0.0542 (7) | |
| C6 | 1.0371 (5) | 0.0617 (3) | 0.23756 (18) | 0.0652 (8) | |
| H6A | 1.1414 | 0.0269 | 0.2769 | 0.078* | |
| H6B | 0.9513 | −0.0071 | 0.2163 | 0.078* | |
| C7 | 0.8978 (4) | 0.1498 (3) | 0.28793 (17) | 0.0564 (7) | |
| C8 | 0.9675 (5) | 0.2047 (3) | 0.36466 (18) | 0.0672 (9) | |
| H8 | 1.1032 | 0.1872 | 0.3843 | 0.081* | |
| C9 | 0.8415 (6) | 0.2848 (3) | 0.4129 (2) | 0.0761 (9) | |
| H9 | 0.8911 | 0.3193 | 0.4645 | 0.091* | |
| C10 | 0.6432 (6) | 0.3126 (3) | 0.3835 (2) | 0.0763 (10) | |
| H10 | 0.5583 | 0.3673 | 0.4150 | 0.092* | |
| C11 | 0.5680 (5) | 0.2601 (3) | 0.30782 (18) | 0.0692 (8) | |
| H11 | 0.4334 | 0.2801 | 0.2881 | 0.083* | |
| C12 | 0.6935 (4) | 0.1769 (3) | 0.26072 (17) | 0.0567 (7) | |
| H1 | 0.694 (5) | 0.093 (4) | 0.153 (2) | 0.119 (17)* | |
| H2 | 1.2851 (18) | 0.126 (4) | 0.167 (2) | 0.092 (11)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0449 (10) | 0.1083 (19) | 0.0723 (13) | −0.0019 (12) | −0.0022 (11) | −0.0175 (13) |
| N1 | 0.0441 (11) | 0.0614 (15) | 0.0655 (13) | 0.0003 (11) | −0.0053 (11) | −0.0049 (11) |
| N2 | 0.0426 (12) | 0.099 (2) | 0.0599 (14) | −0.0044 (13) | −0.0005 (11) | −0.0014 (13) |
| C1 | 0.0658 (18) | 0.068 (2) | 0.0680 (18) | −0.0014 (15) | −0.0109 (16) | −0.0112 (15) |
| C2 | 0.094 (2) | 0.073 (2) | 0.0620 (16) | −0.001 (2) | −0.0054 (19) | −0.0145 (16) |
| C3 | 0.084 (2) | 0.064 (2) | 0.0638 (18) | 0.0032 (17) | 0.0141 (16) | −0.0084 (14) |
| C4 | 0.0585 (16) | 0.0609 (19) | 0.0715 (19) | −0.0017 (15) | 0.0113 (15) | −0.0067 (14) |
| C5 | 0.0471 (14) | 0.0553 (17) | 0.0601 (14) | 0.0020 (13) | 0.0012 (13) | −0.0030 (13) |
| C6 | 0.0544 (15) | 0.078 (2) | 0.0634 (16) | 0.0060 (15) | −0.0075 (14) | 0.0105 (15) |
| C7 | 0.0471 (14) | 0.0667 (19) | 0.0555 (14) | −0.0064 (13) | 0.0017 (13) | 0.0094 (13) |
| C8 | 0.0610 (17) | 0.082 (2) | 0.0581 (15) | −0.0153 (17) | −0.0026 (15) | 0.0086 (15) |
| C9 | 0.090 (2) | 0.077 (2) | 0.0616 (16) | −0.022 (2) | 0.0027 (18) | −0.0032 (17) |
| C10 | 0.087 (2) | 0.071 (2) | 0.0709 (18) | −0.0049 (19) | 0.0184 (18) | −0.0051 (16) |
| C11 | 0.0581 (16) | 0.078 (2) | 0.0713 (17) | 0.0046 (17) | 0.0107 (15) | 0.0055 (17) |
| C12 | 0.0497 (14) | 0.0644 (19) | 0.0561 (15) | −0.0075 (13) | 0.0031 (13) | −0.0002 (13) |
| O1—C12 | 1.364 (3) | C4—H4 | 0.9300 |
| O1—H1 | 0.851 (10) | C6—C7 | 1.504 (4) |
| N1—C5 | 1.336 (4) | C6—H6A | 0.9700 |
| N1—C1 | 1.353 (3) | C6—H6B | 0.9700 |
| N2—C5 | 1.356 (3) | C7—C8 | 1.389 (4) |
| N2—C6 | 1.464 (4) | C7—C12 | 1.390 (4) |
| N2—H2 | 0.879 (10) | C8—C9 | 1.384 (5) |
| C1—C2 | 1.362 (5) | C8—H8 | 0.9300 |
| C1—H1A | 0.9300 | C9—C10 | 1.367 (5) |
| C2—C3 | 1.395 (5) | C9—H9 | 0.9300 |
| C2—H2A | 0.9300 | C10—C11 | 1.377 (4) |
| C3—C4 | 1.357 (4) | C10—H10 | 0.9300 |
| C3—H3 | 0.9300 | C11—C12 | 1.394 (4) |
| C4—C5 | 1.409 (4) | C11—H11 | 0.9300 |
| C12—O1—H1 | 114 (3) | C7—C6—H6A | 108.6 |
| C5—N1—C1 | 117.4 (3) | N2—C6—H6B | 108.6 |
| C5—N2—C6 | 122.9 (3) | C7—C6—H6B | 108.6 |
| C5—N2—H2 | 111 (2) | H6A—C6—H6B | 107.5 |
| C6—N2—H2 | 118 (2) | C8—C7—C12 | 117.6 (3) |
| N1—C1—C2 | 124.1 (3) | C8—C7—C6 | 121.0 (3) |
| N1—C1—H1A | 118.0 | C12—C7—C6 | 121.4 (3) |
| C2—C1—H1A | 118.0 | C9—C8—C7 | 122.1 (3) |
| C1—C2—C3 | 118.0 (3) | C9—C8—H8 | 118.9 |
| C1—C2—H2A | 121.0 | C7—C8—H8 | 118.9 |
| C3—C2—H2A | 121.0 | C10—C9—C8 | 119.1 (3) |
| C4—C3—C2 | 119.3 (3) | C10—C9—H9 | 120.4 |
| C4—C3—H3 | 120.4 | C8—C9—H9 | 120.4 |
| C2—C3—H3 | 120.4 | C9—C10—C11 | 120.5 (3) |
| C3—C4—C5 | 119.5 (3) | C9—C10—H10 | 119.7 |
| C3—C4—H4 | 120.2 | C11—C10—H10 | 119.7 |
| C5—C4—H4 | 120.2 | C10—C11—C12 | 120.1 (3) |
| N1—C5—N2 | 118.4 (2) | C10—C11—H11 | 120.0 |
| N1—C5—C4 | 121.6 (3) | C12—C11—H11 | 120.0 |
| N2—C5—C4 | 120.0 (2) | O1—C12—C7 | 122.5 (3) |
| N2—C6—C7 | 114.8 (3) | O1—C12—C11 | 117.0 (3) |
| N2—C6—H6A | 108.6 | C7—C12—C11 | 120.5 (3) |
| C5—N1—C1—C2 | −1.4 (5) | N2—C6—C7—C12 | 82.9 (4) |
| N1—C1—C2—C3 | −1.3 (5) | C12—C7—C8—C9 | −0.6 (4) |
| C1—C2—C3—C4 | 1.8 (5) | C6—C7—C8—C9 | −179.1 (3) |
| C2—C3—C4—C5 | 0.2 (5) | C7—C8—C9—C10 | −1.1 (5) |
| C1—N1—C5—N2 | −177.7 (3) | C8—C9—C10—C11 | 1.1 (5) |
| C1—N1—C5—C4 | 3.6 (4) | C9—C10—C11—C12 | 0.6 (5) |
| C6—N2—C5—N1 | 18.7 (5) | C8—C7—C12—O1 | −176.6 (3) |
| C6—N2—C5—C4 | −162.5 (3) | C6—C7—C12—O1 | 1.9 (4) |
| C3—C4—C5—N1 | −3.0 (5) | C8—C7—C12—C11 | 2.3 (4) |
| C3—C4—C5—N2 | 178.2 (3) | C6—C7—C12—C11 | −179.2 (3) |
| C5—N2—C6—C7 | −101.6 (3) | C10—C11—C12—O1 | 176.6 (3) |
| N2—C6—C7—C8 | −98.6 (3) | C10—C11—C12—C7 | −2.3 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.85 (1) | 1.83 (2) | 2.658 (3) | 166 (5) |
| N2—H2···O1i | 0.88 (1) | 2.06 (1) | 2.928 (3) | 172 (3) |
| Symmetry code: (i) x+1, y, z. |
Experimental details
| Crystal data | |
| Chemical formula | C12H12N2O |
| Mr | 200.24 |
| Crystal system, space group | Orthorhombic, P212121 |
| Temperature (K) | 295 |
| a, b, c (Å) | 6.3331 (4), 10.6761 (9), 15.3714 (10) |
| V (Å3) | 1039.30 (13) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.08 |
| Crystal size (mm) | 0.25 × 0.19 × 0.15 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID IP |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.979, 0.988 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 10221, 1391, 887 |
| Rint | 0.047 |
| (sin θ/λ)max (Å−1) | 0.648 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.131, 1.04 |
| No. of reflections | 1391 |
| No. of parameters | 144 |
| No. of restraints | 2 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.13, −0.18 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.85 (1) | 1.83 (2) | 2.658 (3) | 166 (5) |
| N2—H2···O1i | 0.88 (1) | 2.06 (1) | 2.928 (3) | 172 (3) |
| Symmetry code: (i) x+1, y, z. |
Acknowledgements
We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (grant No. ZD200903), the Key Project of the Education Bureau of Heilongjiang Province (grants No. 12511z023 and No. 2011CJHB006), the Innovation Team of the Education Bureau of Heilongjiang Province (grant No. 2010td03), Heilongjiang University (grant No. Hdtd2010–04) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Salicylaldehyde condenses with aromatic amines to yield Schiff bases, which serve as chelating ligands to a plethora of metal systems. These Schiff bases can be readily reduce to the corresponding secondary amines, which can also function as chelating ligands. Curiously, there are only few 2-(arylamino)methylphenols compared with the plethora of Schiff bases in the chemical literature. Among the aminopyridine derivatives, only the crystal structure of 2-((pyridin-3-ylamino)methyl)phenol has been reported (Xu et al., 2011). The 2-((pyridin-2-ylamino)methyl)phenol analog (Scheme I) has been described as its metal adducts only (Yalçın et al., 2007).
The two aromatic rings of the reduced Schiff-base, C12H12N2O, are twisted along the –CH2–NH– single-bond by 50.3 (1) °. The hydroxy O atom is hydrogen-bond donor to the pyridyl N atom and an eight-membered ring is formed (Fig. 1). The slightly flattened secondary amino N atom is hydrogen-bond donor to the O atom of an adjacent molecule; this hydrogen bond leads to the formation of a helical chain that runs along the a-axis of the orthorhombic unit cell (Fig. 2, Table 1).