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

Abstract

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,

• a = 5.8386 (11) Å

• b = 13.399 (3) Å

• c = 13.169 (3) Å

• β = 90.519 (6)°

• V = 1030.1 (4) ų

• 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[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681104685X/xu5384Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2U_eq(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.

Figures

Fig. 1.

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

Crystal data

C12H12N2O	F(000) = 424
Mr = 200.24	Dx = 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

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

Refinement

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(Fo2) + (0.0752P)2 + 0.0952P] where P = (Fo2 + 2Fc2)/3
2358 reflections	(Δ/σ)max = 0.001
144 parameters	Δρmax = 0.26 e Å−3
2 restraints	Δρmin = −0.18 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.