2-{[(Pyrazin-2-yl)amino]­meth­yl}phenol

Gao, S.; Ng, S.W.

doi:10.1107/S1600536812031339

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2472

https://doi.org/10.1107/S1600536812031339

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2-{[(Pyrazin-2-yl)amino]methyl}phenol

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 25 June 2012; accepted 10 July 2012; online 18 July 2012)

The two aromatic rings of the title compound, C₁₁H₁₁N₃O, are nearly perpendicular to one another, with a dihedral angle between their planes of 80.52 (18)°. In the crystal, the amino N atom is a hydrogen-bond donor to the pyrazine N¹ atom of an inversion-related molecule and the hydroxy O atom is a hydrogen-bond donor to the pyrazine N⁴ atom of another molecule. The two hydrogen bonds lead to the formation of a helical chain that runs along the b axis.

Related literature

For the related compound 2-(anilinomethyl)phenol, see: Qu et al. (2007 ).

Experimental

Crystal data

C₁₁H₁₁N₃O
M_r = 201.23
Monoclinic, P 2₁ /c
a = 9.7021 (14) Å
b = 13.0937 (17) Å
c = 7.8806 (13) Å
β = 95.746 (5)°
V = 996.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.26 × 0.22 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.977, T_max = 0.985
7686 measured reflections
1751 independent reflections
858 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.191
S = 1.06
1751 reflections
144 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.84 (1)	1.96 (1)	2.796 (4)	174 (4)
N3—H3⋯N1ⁱⁱ	0.89 (1)	2.12 (1)	3.007 (4)	175 (3)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -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/S1600536812031339/xu5580sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031339/xu5580Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031339/xu5580Isup3.cml

checkCIF report

Comment top

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. In 2-(anilinomethyl)phenol, the parent homolog, the hydroxy O atom is hydrogen-bonded to the amino N atom; another N–H···O hydrogen bond generates a dimer (Qu et al., 2007). The two aromatic rings of the reduced Schiff-base, C₁₁H₁₁N₃O (Scheme I), are twisted along the –CH₂–NH– single-bond by 80.5 (1) °. The presence of basic sites allows for additional hydrogen-bonding interactions. The amino N atom is hydrogen-bond donor to the pyraziny-N² atom of an inversion-related molecule and the hydroxy O atom is hydrogen-bond donor to the pyrazinyl-N⁴ atom another molecule. The two hydrogen bonds lead to the formation of a helical chain that runs along the b-axis of the monoclinic unit cell (Fig. 1, Table 1).

Related literature top

For the related compound 2-(anilinomethyl)phenol, see: Qu et al. (2007).

Experimental top

A solution of 2-aminopyrazine (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 in 75% yield.

Structure description top

For the related compound 2-(anilinomethyl)phenol, see: Qu et al. (2007).

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 C₁₁H₁₁N₃O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded chain motif.

2-{[(Pyrazin-2-yl)amino]methyl}phenol top

Crystal data top

C₁₁H₁₁N₃O	F(000) = 424
M_r = 201.23	D_x = 1.342 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3450 reflections
a = 9.7021 (14) Å	θ = 3.0–27.5°
b = 13.0937 (17) Å	µ = 0.09 mm⁻¹
c = 7.8806 (13) Å	T = 295 K
β = 95.746 (5)°	Prism, colorless
V = 996.1 (3) Å³	0.26 × 0.22 × 0.17 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1751 independent reflections
Radiation source: fine-focus sealed tube	858 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
ω scan	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.977, T_max = 0.985	k = −15→15
7686 measured reflections	l = −9→9

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0862P)² + 0.1018P] where P = (F_o² + 2F_c²)/3
1751 reflections	(Δ/σ)_max = 0.001
144 parameters	Δρ_max = 0.18 e Å⁻³
2 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₁H₁₁N₃O	V = 996.1 (3) Å³
M_r = 201.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7021 (14) Å	µ = 0.09 mm⁻¹
b = 13.0937 (17) Å	T = 295 K
c = 7.8806 (13) Å	0.26 × 0.22 × 0.17 mm
β = 95.746 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1751 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	858 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.985	R_int = 0.079
7686 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	2 restraints
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.18 e Å⁻³
1751 reflections	Δρ_min = −0.20 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	−0.0468 (3)	0.63270 (19)	0.2017 (3)	0.0656 (8)
N1	0.4697 (3)	0.3661 (2)	0.0705 (4)	0.0578 (8)
N2	0.2758 (3)	0.2358 (2)	0.1926 (4)	0.0691 (9)
N3	0.3227 (3)	0.5014 (2)	0.0842 (4)	0.0654 (9)
C1	0.4925 (4)	0.2662 (3)	0.0949 (5)	0.0684 (11)
H1A	0.5772	0.2396	0.0707	0.082*
C2	0.3983 (4)	0.2013 (3)	0.1530 (5)	0.0724 (12)
H2	0.4193	0.1322	0.1654	0.087*
C3	0.2500 (4)	0.3333 (3)	0.1698 (5)	0.0650 (10)
H3A	0.1651	0.3589	0.1953	0.078*
C4	0.3470 (3)	0.4010 (3)	0.1077 (4)	0.0530 (9)
C5	0.1935 (4)	0.5509 (3)	0.1131 (5)	0.0642 (10)
H5A	0.1176	0.5081	0.0658	0.077*
H5B	0.1875	0.6149	0.0508	0.077*
C6	0.1742 (3)	0.5727 (2)	0.2970 (5)	0.0521 (9)
C7	0.2751 (4)	0.5529 (3)	0.4289 (5)	0.0649 (11)
H7	0.3577	0.5226	0.4051	0.078*
C8	0.2562 (5)	0.5771 (3)	0.5957 (6)	0.0791 (13)
H8	0.3241	0.5620	0.6839	0.095*
C9	0.1347 (5)	0.6239 (3)	0.6285 (5)	0.0824 (13)
H9	0.1218	0.6427	0.7396	0.099*
C10	0.0329 (4)	0.6431 (3)	0.5000 (5)	0.0697 (11)
H10	−0.0494	0.6737	0.5242	0.084*
C11	0.0521 (4)	0.6171 (2)	0.3347 (5)	0.0524 (9)
H1	−0.116 (2)	0.661 (2)	0.239 (5)	0.077 (13)*
H3	0.388 (3)	0.538 (2)	0.040 (4)	0.070 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0572 (17)	0.0852 (18)	0.0555 (17)	0.0224 (13)	0.0117 (14)	−0.0003 (13)
N1	0.0494 (18)	0.0610 (19)	0.065 (2)	0.0002 (13)	0.0146 (15)	0.0000 (15)
N2	0.071 (2)	0.071 (2)	0.065 (2)	−0.0179 (17)	0.0064 (19)	0.0054 (16)
N3	0.054 (2)	0.066 (2)	0.080 (2)	0.0043 (16)	0.0281 (18)	0.0083 (17)
C1	0.060 (2)	0.069 (3)	0.078 (3)	0.0030 (19)	0.015 (2)	−0.002 (2)
C2	0.074 (3)	0.066 (2)	0.078 (3)	−0.004 (2)	0.010 (2)	0.004 (2)
C3	0.051 (2)	0.082 (3)	0.064 (3)	−0.0058 (19)	0.017 (2)	0.004 (2)
C4	0.046 (2)	0.066 (2)	0.048 (2)	−0.0072 (16)	0.0078 (17)	−0.0019 (17)
C5	0.054 (2)	0.077 (2)	0.064 (3)	0.0078 (18)	0.016 (2)	0.0054 (19)
C6	0.051 (2)	0.0549 (19)	0.051 (2)	−0.0027 (16)	0.0072 (18)	0.0043 (16)
C7	0.055 (2)	0.071 (2)	0.068 (3)	−0.0020 (18)	0.001 (2)	0.001 (2)
C8	0.087 (3)	0.084 (3)	0.063 (3)	−0.006 (2)	−0.015 (3)	0.004 (2)
C9	0.112 (4)	0.087 (3)	0.049 (3)	0.007 (3)	0.008 (3)	−0.012 (2)
C10	0.084 (3)	0.077 (3)	0.050 (3)	0.016 (2)	0.017 (2)	−0.001 (2)
C11	0.058 (2)	0.051 (2)	0.049 (2)	0.0017 (16)	0.0087 (19)	0.0025 (16)

Geometric parameters (Å, º) top

O1—C11	1.363 (4)	C5—C6	1.507 (5)
O1—H1	0.844 (10)	C5—H5A	0.9700
N1—C4	1.336 (4)	C5—H5B	0.9700
N1—C1	1.337 (4)	C6—C7	1.379 (5)
N2—C3	1.311 (4)	C6—C11	1.379 (5)
N2—C2	1.337 (4)	C7—C8	1.382 (5)
N3—C4	1.345 (4)	C7—H7	0.9300
N3—C5	1.449 (4)	C8—C9	1.375 (6)
N3—H3	0.888 (10)	C8—H8	0.9300
C1—C2	1.361 (5)	C9—C10	1.365 (5)
C1—H1A	0.9300	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.377 (5)
C3—C4	1.415 (5)	C10—H10	0.9300
C3—H3A	0.9300

C11—O1—H1	109 (3)	N3—C5—H5B	108.4
C4—N1—C1	116.2 (3)	C6—C5—H5B	108.4
C3—N2—C2	117.3 (3)	H5A—C5—H5B	107.5
C4—N3—C5	123.9 (3)	C7—C6—C11	118.5 (3)
C4—N3—H3	117 (2)	C7—C6—C5	122.8 (3)
C5—N3—H3	119 (2)	C11—C6—C5	118.6 (3)
N1—C1—C2	123.6 (3)	C6—C7—C8	121.4 (4)
N1—C1—H1A	118.2	C6—C7—H7	119.3
C2—C1—H1A	118.2	C8—C7—H7	119.3
N2—C2—C1	120.7 (4)	C9—C8—C7	118.6 (4)
N2—C2—H2	119.7	C9—C8—H8	120.7
C1—C2—H2	119.7	C7—C8—H8	120.7
N2—C3—C4	122.3 (3)	C10—C9—C8	120.9 (4)
N2—C3—H3A	118.9	C10—C9—H9	119.6
C4—C3—H3A	118.9	C8—C9—H9	119.6
N1—C4—N3	116.9 (3)	C9—C10—C11	120.0 (4)
N1—C4—C3	120.0 (3)	C9—C10—H10	120.0
N3—C4—C3	123.2 (3)	C11—C10—H10	120.0
N3—C5—C6	115.4 (3)	O1—C11—C10	122.6 (3)
N3—C5—H5A	108.4	O1—C11—C6	116.8 (3)
C6—C5—H5A	108.4	C10—C11—C6	120.5 (4)

C4—N1—C1—C2	0.4 (6)	N3—C5—C6—C11	−178.2 (3)
C3—N2—C2—C1	1.3 (6)	C11—C6—C7—C8	−0.4 (5)
N1—C1—C2—N2	−1.2 (7)	C5—C6—C7—C8	177.7 (3)
C2—N2—C3—C4	−0.7 (6)	C6—C7—C8—C9	−1.4 (6)
C1—N1—C4—N3	179.9 (3)	C7—C8—C9—C10	2.2 (6)
C1—N1—C4—C3	0.2 (5)	C8—C9—C10—C11	−1.2 (6)
C5—N3—C4—N1	177.9 (3)	C9—C10—C11—O1	178.8 (3)
C5—N3—C4—C3	−2.5 (6)	C9—C10—C11—C6	−0.7 (6)
N2—C3—C4—N1	−0.1 (6)	C7—C6—C11—O1	−178.0 (3)
N2—C3—C4—N3	−179.7 (4)	C5—C6—C11—O1	3.8 (4)
C4—N3—C5—C6	78.5 (5)	C7—C6—C11—C10	1.4 (5)
N3—C5—C6—C7	3.7 (5)	C5—C6—C11—C10	−176.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.84 (1)	1.96 (1)	2.796 (4)	174 (4)
N3—H3···N1ⁱⁱ	0.89 (1)	2.12 (1)	3.007 (4)	175 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁N₃O
M_r	201.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	9.7021 (14), 13.0937 (17), 7.8806 (13)
β (°)	95.746 (5)
V (Å³)	996.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.22 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.977, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	7686, 1751, 858
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.191, 1.06
No. of reflections	1751
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)	0.18, −0.20

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—H1···N2ⁱ	0.84 (1)	1.96 (1)	2.796 (4)	174 (4)
N3—H3···N1ⁱⁱ	0.89 (1)	2.12 (1)	3.007 (4)	175 (3)

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

Acknowledgements

The authors 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 (grant Nos. 12511z023, 2011CJHB006), the Innovation team of the Education Bureau of Heilongjiang Province (grant No. 2010 t d03), 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.

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