4-Ethoxy­pyridin-2-amine

Mao, L.; Chen, Y.

doi:10.1107/S1600536808024847

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1749

doi:10.1107/S1600536808024847

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4-Ethoxypyridin-2-amine

Lihua Mao ^a ^* and Yan Chen ^b

^aSchool of City Development, University of Jinan, Jinan 250002, People's Republic of China, and ^bShandong Blood Center, Jinan 250014, People's Republic of China
^*Correspondence e-mail: maolihua2008@yahoo.cn

(Received 1 August 2008; accepted 2 August 2008; online 13 August 2008)

The title compound, C₇H₁₀N₂O, crystallizes with two independent molecules in the asymmetric unit. The bond lengths and angles in the molecules are within normal ranges. The crystal structure is stabilized by intermolecular N—H⋯N hydrogen bonds, linking the two independent molecules into hydrogen-bonded dimers.

Related literature

For related literatures, see: Cai et al. (2006 ); Yale (1976 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₁₀N₂O
M_r = 138.17
Triclinic, $[P \overline 1]$
a = 9.167 (2) Å
b = 9.470 (2) Å
c = 9.541 (3) Å
α = 87.716 (3)°
β = 87.714 (4)°
γ = 64.189 (3)°
V = 744.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.60 × 0.38 × 0.31 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.901, T_max = 0.974
3749 measured reflections
2582 independent reflections
2110 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.02
2582 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N1ⁱ	0.86	2.19	3.029 (2)	164
N4—H4B⋯N3ⁱⁱ	0.86	2.16	3.013 (2)	173
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+2, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024847/bx2167sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024847/bx2167Isup2.hkl

checkCIF report

Comment top

2-Amino-4-ethoxypyridine is a useful intermediate for the synthesis of various heterocyclic compounds (Cai et al., 2006; Yale, 1976). In this paper, we report the crystal structure of the title compound (I). The title compound crystallizes with two independent molecules in the asymmetric unit. All bond lengths are normal (Allen et al., 1987). Intermolecular N—H···N hydrogen bonds link the two independent molecules into hydrogen-bonded dimers. The crystal packing is further stabilized by van der Waals forces.

Related literature top

For related literatures, see: Cai et al. (2006); Yale (1976). For bond-length data, see: Allen et al. (1987).

Experimental top

2-amino-4-chloropyridine (12.9 g, 0.1 mol) and sodium ethoxide (12.8 g, 0.2 mol) were reacted in 100 ml ethanol in a stainless steel bomb at 150°C for 3 h. The desired compound was obtained as a slightly yellow solid in 50% yield (1.9 g). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in a hexane/dichloromethane mixture (1:4 v/v) at room temperature over a period of one week.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

	Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.
	Fig. 2. Packing diagram of structure of (I), view along the c axis. Hydrogen bonds are shown as dashed lines.

4-Ethoxypyridin-2-amine top

Crystal data top

C₇H₁₀N₂O	Z = 4
M_r = 138.17	F(000) = 296
Triclinic, P1	D_x = 1.232 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.167 (2) Å	Cell parameters from 1699 reflections
b = 9.470 (2) Å	θ = 2.8–23.1°
c = 9.541 (3) Å	µ = 0.09 mm⁻¹
α = 87.716 (3)°	T = 298 K
β = 87.714 (4)°	Block, yellow
γ = 64.189 (3)°	0.60 × 0.38 × 0.31 mm
V = 744.8 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2582 independent reflections
Radiation source: fine-focus sealed tube	2110 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
T_min = 0.901, T_max = 0.974	k = −10→11
3749 measured reflections	l = −11→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0632P)² + 0.1056P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2582 reflections	Δρ_max = 0.18 e Å⁻³
182 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (5)

Crystal data top

C₇H₁₀N₂O	γ = 64.189 (3)°
M_r = 138.17	V = 744.8 (3) Å³
Triclinic, P1	Z = 4
a = 9.167 (2) Å	Mo Kα radiation
b = 9.470 (2) Å	µ = 0.09 mm⁻¹
c = 9.541 (3) Å	T = 298 K
α = 87.716 (3)°	0.60 × 0.38 × 0.31 mm
β = 87.714 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2582 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2110 reflections with I > 2σ(I)
T_min = 0.901, T_max = 0.974	R_int = 0.018
3749 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.02	Δρ_max = 0.18 e Å⁻³
2582 reflections	Δρ_min = −0.16 e Å⁻³
182 parameters

Special details top

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	U_iso*/U_eq
O1	0.59961 (14)	0.31435 (14)	0.17306 (12)	0.0647 (3)
O2	0.09387 (12)	0.83919 (12)	0.15720 (11)	0.0568 (3)
N1	0.93140 (16)	0.44443 (15)	0.33834 (14)	0.0559 (4)
N2	0.8694 (2)	0.3953 (2)	0.56360 (15)	0.0763 (5)
H2B	0.9418	0.4221	0.5910	0.092*
H2C	0.8150	0.3666	0.6242	0.092*
N3	0.44815 (15)	0.88727 (15)	0.37838 (14)	0.0557 (4)
N4	0.26244 (17)	1.10399 (17)	0.49027 (15)	0.0703 (5)
H4B	0.3410	1.1061	0.5350	0.084*
H4C	0.1649	1.1736	0.5056	0.084*
C1	0.84095 (18)	0.39828 (17)	0.42438 (16)	0.0516 (4)
C2	0.72722 (18)	0.35088 (17)	0.37698 (16)	0.0521 (4)
H2A	0.6669	0.3189	0.4401	0.063*
C3	0.70648 (18)	0.35259 (17)	0.23495 (16)	0.0508 (4)
C4	0.8027 (2)	0.39719 (19)	0.14405 (17)	0.0576 (4)
H4A	0.7938	0.3970	0.0473	0.069*
C5	0.9098 (2)	0.44086 (19)	0.20049 (17)	0.0586 (4)
H5A	0.9731	0.4707	0.1389	0.070*
C6	0.4922 (2)	0.2715 (2)	0.25818 (19)	0.0682 (5)
H6A	0.4340	0.3519	0.3260	0.082*
H6B	0.5528	0.1732	0.3085	0.082*
C7	0.3764 (3)	0.2550 (3)	0.1622 (2)	0.0951 (7)
H7A	0.3023	0.2263	0.2159	0.143*
H7B	0.4354	0.1752	0.0957	0.143*
H7C	0.3171	0.3530	0.1132	0.143*
C8	0.29236 (18)	0.99108 (18)	0.39569 (15)	0.0506 (4)
C9	0.16603 (18)	0.98351 (18)	0.32351 (16)	0.0511 (4)
H9A	0.0594	1.0573	0.3380	0.061*
C10	0.20318 (18)	0.86432 (17)	0.23054 (15)	0.0480 (4)
C11	0.36506 (19)	0.75665 (18)	0.21075 (17)	0.0568 (4)
H11A	0.3941	0.6753	0.1483	0.068*
C12	0.47882 (19)	0.77452 (19)	0.28565 (18)	0.0596 (4)
H12A	0.5864	0.7029	0.2714	0.072*
C13	−0.07465 (19)	0.9457 (2)	0.17306 (18)	0.0605 (4)
H13A	−0.0939	1.0486	0.1348	0.073*
H13B	−0.1069	0.9557	0.2716	0.073*
C14	−0.1699 (2)	0.8813 (2)	0.0962 (2)	0.0806 (6)
H14A	−0.2832	0.9508	0.1049	0.121*
H14B	−0.1507	0.7799	0.1352	0.121*
H14C	−0.1371	0.8718	−0.0012	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0665 (7)	0.0772 (8)	0.0598 (7)	−0.0395 (7)	−0.0091 (6)	−0.0017 (6)
O2	0.0522 (6)	0.0562 (7)	0.0601 (7)	−0.0206 (5)	−0.0068 (5)	−0.0106 (5)
N1	0.0577 (8)	0.0564 (8)	0.0557 (8)	−0.0264 (7)	−0.0021 (6)	−0.0038 (6)
N2	0.1046 (12)	0.0994 (12)	0.0514 (8)	−0.0687 (11)	−0.0128 (8)	0.0064 (8)
N3	0.0489 (7)	0.0531 (8)	0.0580 (8)	−0.0148 (6)	−0.0073 (6)	−0.0054 (6)
N4	0.0526 (8)	0.0734 (10)	0.0741 (10)	−0.0143 (7)	−0.0102 (7)	−0.0284 (8)
C1	0.0562 (9)	0.0425 (8)	0.0532 (9)	−0.0186 (7)	−0.0054 (7)	−0.0003 (6)
C2	0.0557 (9)	0.0466 (9)	0.0535 (9)	−0.0219 (7)	−0.0009 (7)	0.0002 (7)
C3	0.0501 (8)	0.0418 (8)	0.0572 (9)	−0.0164 (7)	−0.0049 (7)	−0.0040 (7)
C4	0.0648 (10)	0.0591 (10)	0.0486 (9)	−0.0263 (8)	−0.0019 (7)	−0.0045 (7)
C5	0.0624 (10)	0.0625 (10)	0.0538 (9)	−0.0303 (8)	0.0052 (7)	−0.0040 (7)
C6	0.0628 (10)	0.0736 (12)	0.0730 (11)	−0.0342 (9)	−0.0093 (9)	0.0062 (9)
C7	0.0799 (14)	0.1224 (19)	0.1023 (16)	−0.0620 (14)	−0.0346 (12)	0.0319 (14)
C8	0.0507 (9)	0.0497 (9)	0.0464 (8)	−0.0167 (7)	−0.0048 (6)	−0.0018 (7)
C9	0.0450 (8)	0.0487 (9)	0.0523 (8)	−0.0130 (7)	−0.0030 (6)	−0.0040 (7)
C10	0.0515 (8)	0.0476 (8)	0.0451 (8)	−0.0216 (7)	−0.0043 (6)	0.0023 (6)
C11	0.0557 (9)	0.0493 (9)	0.0603 (9)	−0.0172 (8)	0.0001 (7)	−0.0118 (7)
C12	0.0481 (9)	0.0513 (9)	0.0693 (10)	−0.0116 (7)	−0.0018 (8)	−0.0083 (8)
C13	0.0528 (9)	0.0603 (10)	0.0650 (10)	−0.0207 (8)	−0.0045 (8)	−0.0074 (8)
C14	0.0627 (11)	0.0813 (13)	0.1024 (15)	−0.0335 (10)	−0.0108 (10)	−0.0174 (11)

Geometric parameters (Å, º) top

O1—C3	1.3460 (19)	C5—H5A	0.9300
O1—C6	1.433 (2)	C6—C7	1.490 (3)
O2—C10	1.3518 (18)	C6—H6A	0.9700
O2—C13	1.4364 (19)	C6—H6B	0.9700
N1—C1	1.336 (2)	C7—H7A	0.9600
N1—C5	1.342 (2)	C7—H7B	0.9600
N2—C1	1.361 (2)	C7—H7C	0.9600
N2—H2B	0.8600	C8—C9	1.400 (2)
N2—H2C	0.8600	C9—C10	1.378 (2)
N3—C12	1.340 (2)	C9—H9A	0.9300
N3—C8	1.3434 (19)	C10—C11	1.397 (2)
N4—C8	1.3545 (19)	C11—C12	1.360 (2)
N4—H4B	0.8600	C11—H11A	0.9300
N4—H4C	0.8600	C12—H12A	0.9300
C1—C2	1.398 (2)	C13—C14	1.491 (2)
C2—C3	1.374 (2)	C13—H13A	0.9700
C2—H2A	0.9300	C13—H13B	0.9700
C3—C4	1.394 (2)	C14—H14A	0.9600
C4—C5	1.355 (2)	C14—H14B	0.9600
C4—H4A	0.9300	C14—H14C	0.9600

C3—O1—C6	119.52 (13)	C6—C7—H7B	109.5
C10—O2—C13	118.61 (11)	H7A—C7—H7B	109.5
C1—N1—C5	116.21 (13)	C6—C7—H7C	109.5
C1—N2—H2B	120.0	H7A—C7—H7C	109.5
C1—N2—H2C	120.0	H7B—C7—H7C	109.5
H2B—N2—H2C	120.0	N3—C8—N4	116.04 (14)
C12—N3—C8	116.47 (13)	N3—C8—C9	122.94 (14)
C8—N4—H4B	120.0	N4—C8—C9	121.01 (14)
C8—N4—H4C	120.0	C10—C9—C8	118.52 (14)
H4B—N4—H4C	120.0	C10—C9—H9A	120.7
N1—C1—N2	115.68 (14)	C8—C9—H9A	120.7
N1—C1—C2	123.24 (14)	O2—C10—C9	125.11 (14)
N2—C1—C2	121.06 (15)	O2—C10—C11	115.89 (13)
C3—C2—C1	118.51 (14)	C9—C10—C11	118.98 (14)
C3—C2—H2A	120.7	C12—C11—C10	117.94 (14)
C1—C2—H2A	120.7	C12—C11—H11A	121.0
O1—C3—C2	125.72 (14)	C10—C11—H11A	121.0
O1—C3—C4	115.54 (14)	N3—C12—C11	125.14 (15)
C2—C3—C4	118.74 (14)	N3—C12—H12A	117.4
C5—C4—C3	118.19 (15)	C11—C12—H12A	117.4
C5—C4—H4A	120.9	O2—C13—C14	107.85 (14)
C3—C4—H4A	120.9	O2—C13—H13A	110.1
N1—C5—C4	125.08 (15)	C14—C13—H13A	110.1
N1—C5—H5A	117.5	O2—C13—H13B	110.1
C4—C5—H5A	117.5	C14—C13—H13B	110.1
O1—C6—C7	107.17 (15)	H13A—C13—H13B	108.4
O1—C6—H6A	110.3	C13—C14—H14A	109.5
C7—C6—H6A	110.3	C13—C14—H14B	109.5
O1—C6—H6B	110.3	H14A—C14—H14B	109.5
C7—C6—H6B	110.3	C13—C14—H14C	109.5
H6A—C6—H6B	108.5	H14A—C14—H14C	109.5
C6—C7—H7A	109.5	H14B—C14—H14C	109.5

C5—N1—C1—N2	177.01 (15)	C12—N3—C8—N4	179.60 (15)
C5—N1—C1—C2	−1.1 (2)	C12—N3—C8—C9	0.8 (2)
N1—C1—C2—C3	−0.4 (2)	N3—C8—C9—C10	0.0 (2)
N2—C1—C2—C3	−178.37 (15)	N4—C8—C9—C10	−178.74 (15)
C6—O1—C3—C2	1.9 (2)	C13—O2—C10—C9	1.6 (2)
C6—O1—C3—C4	−178.15 (14)	C13—O2—C10—C11	179.93 (13)
C1—C2—C3—O1	−178.26 (14)	C8—C9—C10—O2	177.69 (14)
C1—C2—C3—C4	1.8 (2)	C8—C9—C10—C11	−0.6 (2)
O1—C3—C4—C5	178.35 (14)	O2—C10—C11—C12	−178.04 (14)
C2—C3—C4—C5	−1.7 (2)	C9—C10—C11—C12	0.4 (2)
C1—N1—C5—C4	1.2 (2)	C8—N3—C12—C11	−1.1 (3)
C3—C4—C5—N1	0.2 (3)	C10—C11—C12—N3	0.5 (3)
C3—O1—C6—C7	173.22 (16)	C10—O2—C13—C14	−173.07 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.86	2.19	3.029 (2)	164
N4—H4B···N3ⁱⁱ	0.86	2.16	3.013 (2)	173

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀N₂O
M_r	138.17
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.167 (2), 9.470 (2), 9.541 (3)
α, β, γ (°)	87.716 (3), 87.714 (4), 64.189 (3)
V (Å³)	744.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.60 × 0.38 × 0.31

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.901, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	3749, 2582, 2110
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.02
No. of reflections	2582
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.86	2.19	3.029 (2)	163.9
N4—H4B···N3ⁱⁱ	0.86	2.16	3.013 (2)	172.8

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cai, L., Brouwer, C., Sinclair, K., Cuevas, J. & Pike, V. W. (2006). Synthesis, pp. 133–145. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yale, H. L. (1976). US patent 3 965 100. Google Scholar

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Volume 64| Part 9| September 2008| Page o1749

doi:10.1107/S1600536808024847

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