2-[(Pyridin-3-yl­amino)­meth­yl]phenol

Xu, J.; Gao, S.; Ng, S.W.

doi:10.1107/S160053681104685X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3259

https://doi.org/10.1107/S160053681104685X

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2-[(Pyridin-3-ylamino)methyl]phenol

Jing Xu,^a Shan Gao ^a and Seik Weng Ng ^b,^c ^*

^aKey Laboratory of Functional Inorganic Material 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

(Received 4 November 2011; accepted 7 November 2011; online 12 November 2011)

In the title compound, C₁₂H₁₂N₂O, the aromatic rings at either ends of the –CH₂–NH– link are twisted by 68.79 (7)°. In the crystal, the hydroxy substituent is a hydrogen-bond donor to the N atom of the pyridine ring of an adjacent molecule, and the hydrogen bond generates a chain along the b axis; it is also a hydrogen-bond acceptor to the amino group of another adjacent molecule. The two hydrogen bonds lead to the formation of a layer structure.

Related literature

For the N-salicylidene-3-aminopyridine precursor, see: Csaszar (1990 ); Kaya & Guelel (2005 ); Robert et al. (2009 ). For a related structure, see: Xu et al. (2011 ).

Experimental

Crystal data

C₁₂H₁₂N₂O
M_r = 200.24
Monoclinic, P 2₁ /c
a = 5.8386 (11) Å
b = 13.399 (3) Å
c = 13.169 (3) Å
β = 90.519 (6)°
V = 1030.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.21 × 0.12 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.983, T_max = 0.990
9845 measured reflections
2358 independent reflections
1879 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.137
S = 1.08
2358 reflections
144 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N2ⁱ	0.86 (1)	1.80 (1)	2.6568 (16)	175 (2)
N1—H1n⋯O1ⁱⁱ	0.88 (1)	2.38 (1)	3.2296 (17)	163 (1)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681104685X/xu5384sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681104685X/xu5384Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681104685X/xu5384Isup3.cml

checkCIF report

Comment top

There are numerous studies on the Schiff bases derived by condensing salicyldehyde and an aromatic amine. In this study, the azomethine double-bond of N-salicylidene-3-aminopyridine (Csaszar, 1990; Kaya & Guelel, 2005; Robert et al. 2009) is reduced by sodium borohydride to yield the title secondary amine (Scheme I). The two aromatic rings at either ends of the –CH₂–NH– link of C₁₂H₁₂N₂O are twisted by 68.79 (7)° (Fig. 1). The hydroxy substituent is hydrogen-bond donor to the N atom of the pyridyl ring of an adjacent molecule, and the hydrogen bond generates a linear chain along the b-axis. It is also hydrogen-bond acceptor to the amino group of another adjacent molecule; the two hydrogen bonds lead to the formation of a layer structure (Table 1).

Related literature top

For the N-salicylidene-3-aminopyridine precursor, see: Csaszar (1990); Kaya & Guelel (2005); Robert et al. (2009). For a related structure, see: Xu et al. (2011).

Experimental top

A solution of 3-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. Colorless crystals were obtained by recrystallization from methanol; yield 80%.

Structure description top

For the N-salicylidene-3-aminopyridine precursor, see: Csaszar (1990); Kaya & Guelel (2005); Robert et al. (2009). For a related structure, see: Xu et al. (2011).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: 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).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₂H₁₂N₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-[(Pyridin-3-ylamino)methyl]phenol top

Crystal data top

C₁₂H₁₂N₂O	F(000) = 424
M_r = 200.24	D_x = 1.291 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5377 reflections
a = 5.8386 (11) Å	θ = 3.0–27.5°
b = 13.399 (3) Å	µ = 0.08 mm⁻¹
c = 13.169 (3) Å	T = 293 K
β = 90.519 (6)°	Prism, colorless
V = 1030.1 (4) Å³	0.21 × 0.12 × 0.12 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2358 independent reflections
Radiation source: fine-focus sealed tube	1879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scan	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→7
T_min = 0.983, T_max = 0.990	k = −17→17
9845 measured reflections	l = −17→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0752P)² + 0.0952P] where P = (F_o² + 2F_c²)/3
2358 reflections	(Δ/σ)_max = 0.001
144 parameters	Δρ_max = 0.26 e Å⁻³
2 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₁₂N₂O	V = 1030.1 (4) Å³
M_r = 200.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8386 (11) Å	µ = 0.08 mm⁻¹
b = 13.399 (3) Å	T = 293 K
c = 13.169 (3) Å	0.21 × 0.12 × 0.12 mm
β = 90.519 (6)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2358 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1879 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.990	R_int = 0.042
9845 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	2 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.26 e Å⁻³
2358 reflections	Δρ_min = −0.18 e Å⁻³
144 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.17862 (17)	0.30493 (7)	0.38420 (7)	0.0517 (3)
H1O	1.249 (3)	0.2486 (9)	0.3790 (12)	0.073 (5)*
N1	0.6391 (2)	0.42170 (9)	0.32008 (9)	0.0512 (3)
H1N	0.534 (2)	0.3813 (10)	0.3444 (11)	0.059 (4)*
N2	0.61025 (18)	0.63154 (8)	0.14353 (8)	0.0493 (3)
C1	1.0374 (2)	0.30367 (9)	0.46539 (9)	0.0396 (3)
C2	1.0673 (2)	0.23629 (11)	0.54458 (10)	0.0499 (3)
H2	1.1882	0.1911	0.5429	0.060*
C3	0.9202 (3)	0.23577 (13)	0.62516 (10)	0.0591 (4)
H3	0.9407	0.1897	0.6773	0.071*
C4	0.7428 (3)	0.30289 (14)	0.62928 (11)	0.0669 (5)
H4	0.6418	0.3022	0.6835	0.080*
C5	0.7166 (3)	0.37110 (12)	0.55208 (11)	0.0597 (4)
H5	0.5982	0.4173	0.5557	0.072*
C6	0.8605 (2)	0.37334 (9)	0.46929 (9)	0.0431 (3)
C7	0.8270 (2)	0.44915 (10)	0.38681 (11)	0.0484 (3)
H7A	0.7961	0.5138	0.4169	0.058*
H7B	0.9664	0.4547	0.3477	0.058*
C8	0.5640 (2)	0.48446 (9)	0.24474 (9)	0.0416 (3)
C9	0.6833 (2)	0.57012 (10)	0.21638 (10)	0.0449 (3)
H9	0.8200	0.5850	0.2499	0.054*
C10	0.4163 (2)	0.61131 (11)	0.09441 (11)	0.0545 (4)
H10	0.3659	0.6543	0.0434	0.065*
C11	0.2877 (2)	0.52808 (12)	0.11717 (11)	0.0586 (4)
H11	0.1522	0.5152	0.0819	0.070*
C12	0.3611 (2)	0.46471 (11)	0.19197 (10)	0.0528 (4)
H12	0.2755	0.4083	0.2077	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0596 (6)	0.0440 (5)	0.0517 (6)	0.0094 (4)	0.0165 (5)	0.0042 (4)
N1	0.0588 (7)	0.0428 (6)	0.0519 (6)	−0.0104 (5)	−0.0083 (5)	0.0094 (5)
N2	0.0515 (6)	0.0442 (6)	0.0522 (6)	−0.0019 (5)	0.0093 (5)	0.0090 (5)
C1	0.0424 (6)	0.0385 (6)	0.0380 (6)	0.0015 (5)	0.0016 (5)	−0.0046 (5)
C2	0.0494 (7)	0.0527 (8)	0.0476 (7)	0.0131 (6)	0.0022 (6)	0.0037 (6)
C3	0.0645 (9)	0.0721 (10)	0.0408 (7)	0.0146 (7)	0.0030 (6)	0.0107 (6)
C4	0.0663 (9)	0.0880 (12)	0.0467 (8)	0.0213 (8)	0.0168 (7)	0.0033 (7)
C5	0.0570 (8)	0.0670 (10)	0.0551 (8)	0.0241 (7)	0.0097 (7)	−0.0013 (7)
C6	0.0448 (6)	0.0413 (7)	0.0432 (6)	0.0053 (5)	−0.0032 (5)	−0.0040 (5)
C7	0.0465 (7)	0.0396 (7)	0.0589 (8)	0.0025 (5)	−0.0045 (6)	0.0019 (6)
C8	0.0473 (6)	0.0377 (6)	0.0400 (6)	−0.0011 (5)	0.0038 (5)	−0.0009 (5)
C9	0.0403 (6)	0.0434 (7)	0.0511 (7)	−0.0022 (5)	0.0045 (5)	0.0029 (5)
C10	0.0592 (8)	0.0578 (8)	0.0465 (7)	0.0034 (6)	0.0008 (6)	0.0120 (6)
C11	0.0558 (8)	0.0701 (10)	0.0498 (8)	−0.0095 (7)	−0.0094 (6)	0.0057 (7)
C12	0.0584 (8)	0.0518 (8)	0.0481 (7)	−0.0169 (6)	−0.0026 (6)	0.0037 (6)

Geometric parameters (Å, º) top

O1—C1	1.3562 (15)	C4—H4	0.9300
O1—H1O	0.86 (1)	C5—C6	1.383 (2)
N1—C8	1.3695 (16)	C5—H5	0.9300
N1—C7	1.4472 (17)	C6—C7	1.4986 (17)
N1—H1N	0.88 (1)	C7—H7A	0.9700
N2—C10	1.3269 (18)	C7—H7B	0.9700
N2—C9	1.3312 (16)	C8—C12	1.3936 (18)
C1—C2	1.3892 (18)	C8—C9	1.3953 (18)
C1—C6	1.3933 (17)	C9—H9	0.9300
C2—C3	1.371 (2)	C10—C11	1.379 (2)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.373 (2)	C11—C12	1.366 (2)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.374 (2)	C12—H12	0.9300

C1—O1—H1O	110.3 (12)	C1—C6—C7	121.29 (12)
C8—N1—C7	121.31 (11)	N1—C7—C6	111.17 (11)
C8—N1—H1N	114.9 (10)	N1—C7—H7A	109.4
C7—N1—H1N	117.6 (10)	C6—C7—H7A	109.4
C10—N2—C9	119.43 (11)	N1—C7—H7B	109.4
O1—C1—C2	121.78 (11)	C6—C7—H7B	109.4
O1—C1—C6	118.47 (11)	H7A—C7—H7B	108.0
C2—C1—C6	119.73 (12)	N1—C8—C12	120.65 (11)
C3—C2—C1	120.58 (12)	N1—C8—C9	122.81 (11)
C3—C2—H2	119.7	C12—C8—C9	116.54 (12)
C1—C2—H2	119.7	N2—C9—C8	122.96 (12)
C2—C3—C4	120.35 (13)	N2—C9—H9	118.5
C2—C3—H3	119.8	C8—C9—H9	118.5
C4—C3—H3	119.8	N2—C10—C11	121.55 (12)
C3—C4—C5	119.01 (14)	N2—C10—H10	119.2
C3—C4—H4	120.5	C11—C10—H10	119.2
C5—C4—H4	120.5	C12—C11—C10	119.44 (13)
C4—C5—C6	122.24 (13)	C12—C11—H11	120.3
C4—C5—H5	118.9	C10—C11—H11	120.3
C6—C5—H5	118.9	C11—C12—C8	120.07 (12)
C5—C6—C1	118.05 (12)	C11—C12—H12	120.0
C5—C6—C7	120.66 (11)	C8—C12—H12	120.0

O1—C1—C2—C3	−179.14 (13)	C5—C6—C7—N1	−77.50 (16)
C6—C1—C2—C3	1.9 (2)	C1—C6—C7—N1	102.91 (14)
C1—C2—C3—C4	−0.9 (2)	C7—N1—C8—C12	−169.54 (13)
C2—C3—C4—C5	−0.7 (3)	C7—N1—C8—C9	10.6 (2)
C3—C4—C5—C6	1.2 (3)	C10—N2—C9—C8	−0.4 (2)
C4—C5—C6—C1	−0.2 (2)	N1—C8—C9—N2	−179.66 (12)
C4—C5—C6—C7	−179.76 (14)	C12—C8—C9—N2	0.5 (2)
O1—C1—C6—C5	179.63 (12)	C9—N2—C10—C11	0.2 (2)
C2—C1—C6—C5	−1.41 (19)	N2—C10—C11—C12	0.0 (2)
O1—C1—C6—C7	−0.77 (17)	C10—C11—C12—C8	0.1 (2)
C2—C1—C6—C7	178.19 (11)	N1—C8—C12—C11	179.81 (14)
C8—N1—C7—C6	174.01 (12)	C9—C8—C12—C11	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N2ⁱ	0.86 (1)	1.80 (1)	2.6568 (16)	175 (2)
N1—H1n···O1ⁱⁱ	0.88 (1)	2.38 (1)	3.2296 (17)	163 (1)

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O
M_r	200.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.8386 (11), 13.399 (3), 13.169 (3)
β (°)	90.519 (6)
V (Å³)	1030.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.21 × 0.12 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.983, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	9845, 2358, 1879
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.137, 1.08
No. of reflections	2358
No. of parameters	144
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −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).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N2ⁱ	0.862 (14)	1.797 (14)	2.6568 (16)	175.0 (16)
N1—H1n···O1ⁱⁱ	0.881 (13)	2.376 (12)	3.2296 (17)	163.2 (12)

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x−1, y, z.

Acknowledgements

This work was supported by the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Key Project of the Education Bureau of Heilongjiang Province (No. 12511z023), Heilongjiang University (Hdtd2010–04) and the University of Malaya.

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