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Acta Cryst. (2008). E64, o1749    [ doi:10.1107/S1600536808024847 ]

4-Ethoxypyridin-2-amine

L. Mao and Y. Chen

Abstract top

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.

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.

Refinement top

H atoms bonded to N atoms were located in a difference map and refined with distance restraints of N—H = 0.86Å, and with Uiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

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
[Figure 1] Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.
[Figure 2] 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
C7H10N2OZ = 4
Mr = 138.17F000 = 296
Triclinic, P1Dx = 1.232 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.167 (2) ÅCell parameters from 1699 reflections
b = 9.470 (2) Åθ = 2.8–23.1º
c = 9.541 (3) ŵ = 0.09 mm−1
α = 87.716 (3)ºT = 298 (2) K
β = 87.714 (4)ºBlock, yellow
γ = 64.189 (3)º0.60 × 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 tube2110 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −10→10
Tmin = 0.901, Tmax = 0.974k = −10→11
3749 measured reflectionsl = −11→7
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043  w = 1/[σ2(Fo2) + (0.0632P)2 + 0.1056P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.123(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.18 e Å−3
2582 reflectionsΔρmin = −0.16 e Å−3
182 parametersExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.040 (5)
Secondary atom site location: difference Fourier map
Crystal data top
C7H10N2Oγ = 64.189 (3)º
Mr = 138.17V = 744.8 (3) Å3
Triclinic, P1Z = 4
a = 9.167 (2) ÅMo Kα
b = 9.470 (2) ŵ = 0.09 mm−1
c = 9.541 (3) ÅT = 298 (2) K
α = 87.716 (3)º0.60 × 0.38 × 0.31 mm
β = 87.714 (4)º
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)
Tmin = 0.901, Tmax = 0.974Rint = 0.018
3749 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043182 parameters
wR(F2) = 0.123H-atom parameters constrained
S = 1.02Δρmax = 0.18 e Å−3
2582 reflectionsΔρmin = −0.16 e Å−3
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
xyzUiso*/Ueq
O10.59961 (14)0.31435 (14)0.17306 (12)0.0647 (3)
O20.09387 (12)0.83919 (12)0.15720 (11)0.0568 (3)
N10.93140 (16)0.44443 (15)0.33834 (14)0.0559 (4)
N20.8694 (2)0.3953 (2)0.56360 (15)0.0763 (5)
H2B0.94180.42210.59100.092*
H2C0.81500.36660.62420.092*
N30.44815 (15)0.88727 (15)0.37838 (14)0.0557 (4)
N40.26244 (17)1.10399 (17)0.49027 (15)0.0703 (5)
H4B0.34101.10610.53500.084*
H4C0.16491.17360.50560.084*
C10.84095 (18)0.39828 (17)0.42438 (16)0.0516 (4)
C20.72722 (18)0.35088 (17)0.37698 (16)0.0521 (4)
H2A0.66690.31890.44010.063*
C30.70648 (18)0.35259 (17)0.23495 (16)0.0508 (4)
C40.8027 (2)0.39719 (19)0.14405 (17)0.0576 (4)
H4A0.79380.39700.04730.069*
C50.9098 (2)0.44086 (19)0.20049 (17)0.0586 (4)
H5A0.97310.47070.13890.070*
C60.4922 (2)0.2715 (2)0.25818 (19)0.0682 (5)
H6A0.43400.35190.32600.082*
H6B0.55280.17320.30850.082*
C70.3764 (3)0.2550 (3)0.1622 (2)0.0951 (7)
H7A0.30230.22630.21590.143*
H7B0.43540.17520.09570.143*
H7C0.31710.35300.11320.143*
C80.29236 (18)0.99108 (18)0.39569 (15)0.0506 (4)
C90.16603 (18)0.98351 (18)0.32351 (16)0.0511 (4)
H9A0.05941.05730.33800.061*
C100.20318 (18)0.86432 (17)0.23054 (15)0.0480 (4)
C110.36506 (19)0.75665 (18)0.21075 (17)0.0568 (4)
H11A0.39410.67530.14830.068*
C120.47882 (19)0.77452 (19)0.28565 (18)0.0596 (4)
H12A0.58640.70290.27140.072*
C13−0.07465 (19)0.9457 (2)0.17306 (18)0.0605 (4)
H13A−0.09391.04860.13480.073*
H13B−0.10690.95570.27160.073*
C14−0.1699 (2)0.8813 (2)0.0962 (2)0.0806 (6)
H14A−0.28320.95080.10490.121*
H14B−0.15070.77990.13520.121*
H14C−0.13710.8718−0.00120.121*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0665 (7)0.0772 (8)0.0598 (7)−0.0395 (7)−0.0091 (6)−0.0017 (6)
O20.0522 (6)0.0562 (7)0.0601 (7)−0.0206 (5)−0.0068 (5)−0.0106 (5)
N10.0577 (8)0.0564 (8)0.0557 (8)−0.0264 (7)−0.0021 (6)−0.0038 (6)
N20.1046 (12)0.0994 (12)0.0514 (8)−0.0687 (11)−0.0128 (8)0.0064 (8)
N30.0489 (7)0.0531 (8)0.0580 (8)−0.0148 (6)−0.0073 (6)−0.0054 (6)
N40.0526 (8)0.0734 (10)0.0741 (10)−0.0143 (7)−0.0102 (7)−0.0284 (8)
C10.0562 (9)0.0425 (8)0.0532 (9)−0.0186 (7)−0.0054 (7)−0.0003 (6)
C20.0557 (9)0.0466 (9)0.0535 (9)−0.0219 (7)−0.0009 (7)0.0002 (7)
C30.0501 (8)0.0418 (8)0.0572 (9)−0.0164 (7)−0.0049 (7)−0.0040 (7)
C40.0648 (10)0.0591 (10)0.0486 (9)−0.0263 (8)−0.0019 (7)−0.0045 (7)
C50.0624 (10)0.0625 (10)0.0538 (9)−0.0303 (8)0.0052 (7)−0.0040 (7)
C60.0628 (10)0.0736 (12)0.0730 (11)−0.0342 (9)−0.0093 (9)0.0062 (9)
C70.0799 (14)0.1224 (19)0.1023 (16)−0.0620 (14)−0.0346 (12)0.0319 (14)
C80.0507 (9)0.0497 (9)0.0464 (8)−0.0167 (7)−0.0048 (6)−0.0018 (7)
C90.0450 (8)0.0487 (9)0.0523 (8)−0.0130 (7)−0.0030 (6)−0.0040 (7)
C100.0515 (8)0.0476 (8)0.0451 (8)−0.0216 (7)−0.0043 (6)0.0023 (6)
C110.0557 (9)0.0493 (9)0.0603 (9)−0.0172 (8)0.0001 (7)−0.0118 (7)
C120.0481 (9)0.0513 (9)0.0693 (10)−0.0116 (7)−0.0018 (8)−0.0083 (8)
C130.0528 (9)0.0603 (10)0.0650 (10)−0.0207 (8)−0.0045 (8)−0.0074 (8)
C140.0627 (11)0.0813 (13)0.1024 (15)−0.0335 (10)−0.0108 (10)−0.0174 (11)
Geometric parameters (Å, °) top
O1—C31.3460 (19)C5—H5A0.9300
O1—C61.433 (2)C6—C71.490 (3)
O2—C101.3518 (18)C6—H6A0.9700
O2—C131.4364 (19)C6—H6B0.9700
N1—C11.336 (2)C7—H7A0.9600
N1—C51.342 (2)C7—H7B0.9600
N2—C11.361 (2)C7—H7C0.9600
N2—H2B0.8600C8—C91.400 (2)
N2—H2C0.8600C9—C101.378 (2)
N3—C121.340 (2)C9—H9A0.9300
N3—C81.3434 (19)C10—C111.397 (2)
N4—C81.3545 (19)C11—C121.360 (2)
N4—H4B0.8600C11—H11A0.9300
N4—H4C0.8600C12—H12A0.9300
C1—C21.398 (2)C13—C141.491 (2)
C2—C31.374 (2)C13—H13A0.9700
C2—H2A0.9300C13—H13B0.9700
C3—C41.394 (2)C14—H14A0.9600
C4—C51.355 (2)C14—H14B0.9600
C4—H4A0.9300C14—H14C0.9600
C3—O1—C6119.52 (13)C6—C7—H7B109.5
C10—O2—C13118.61 (11)H7A—C7—H7B109.5
C1—N1—C5116.21 (13)C6—C7—H7C109.5
C1—N2—H2B120.0H7A—C7—H7C109.5
C1—N2—H2C120.0H7B—C7—H7C109.5
H2B—N2—H2C120.0N3—C8—N4116.04 (14)
C12—N3—C8116.47 (13)N3—C8—C9122.94 (14)
C8—N4—H4B120.0N4—C8—C9121.01 (14)
C8—N4—H4C120.0C10—C9—C8118.52 (14)
H4B—N4—H4C120.0C10—C9—H9A120.7
N1—C1—N2115.68 (14)C8—C9—H9A120.7
N1—C1—C2123.24 (14)O2—C10—C9125.11 (14)
N2—C1—C2121.06 (15)O2—C10—C11115.89 (13)
C3—C2—C1118.51 (14)C9—C10—C11118.98 (14)
C3—C2—H2A120.7C12—C11—C10117.94 (14)
C1—C2—H2A120.7C12—C11—H11A121.0
O1—C3—C2125.72 (14)C10—C11—H11A121.0
O1—C3—C4115.54 (14)N3—C12—C11125.14 (15)
C2—C3—C4118.74 (14)N3—C12—H12A117.4
C5—C4—C3118.19 (15)C11—C12—H12A117.4
C5—C4—H4A120.9O2—C13—C14107.85 (14)
C3—C4—H4A120.9O2—C13—H13A110.1
N1—C5—C4125.08 (15)C14—C13—H13A110.1
N1—C5—H5A117.5O2—C13—H13B110.1
C4—C5—H5A117.5C14—C13—H13B110.1
O1—C6—C7107.17 (15)H13A—C13—H13B108.4
O1—C6—H6A110.3C13—C14—H14A109.5
C7—C6—H6A110.3C13—C14—H14B109.5
O1—C6—H6B110.3H14A—C14—H14B109.5
C7—C6—H6B110.3C13—C14—H14C109.5
H6A—C6—H6B108.5H14A—C14—H14C109.5
C6—C7—H7A109.5H14B—C14—H14C109.5
C5—N1—C1—N2177.01 (15)C12—N3—C8—N4179.60 (15)
C5—N1—C1—C2−1.1 (2)C12—N3—C8—C90.8 (2)
N1—C1—C2—C3−0.4 (2)N3—C8—C9—C100.0 (2)
N2—C1—C2—C3−178.37 (15)N4—C8—C9—C10−178.74 (15)
C6—O1—C3—C21.9 (2)C13—O2—C10—C91.6 (2)
C6—O1—C3—C4−178.15 (14)C13—O2—C10—C11179.93 (13)
C1—C2—C3—O1−178.26 (14)C8—C9—C10—O2177.69 (14)
C1—C2—C3—C41.8 (2)C8—C9—C10—C11−0.6 (2)
O1—C3—C4—C5178.35 (14)O2—C10—C11—C12−178.04 (14)
C2—C3—C4—C5−1.7 (2)C9—C10—C11—C120.4 (2)
C1—N1—C5—C41.2 (2)C8—N3—C12—C11−1.1 (3)
C3—C4—C5—N10.2 (3)C10—C11—C12—N30.5 (3)
C3—O1—C6—C7173.22 (16)C10—O2—C13—C14−173.07 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N1i0.862.193.029 (2)164
N4—H4B···N3ii0.862.163.013 (2)173
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N1i0.862.193.029 (2)164
N4—H4B···N3ii0.862.163.013 (2)173
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.
Acknowledgements top

I do not need acknowledegements.

references
References top

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Cai, L., Brouwer, C., Sinclair, K., Cuevas, J. & Pike, V. W. (2006). Synthesis, 1, 133–145.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yale, H. L. (1976). US patent US 3 965 100.