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Acta Cryst. (2009). E65, o1329    [ doi:10.1107/S1600536809016833 ]

4-Amino-2,3,5-trimethylpyridine monohydrate

L.-Y. Dai, F.-L. Zhang, L. Shen and Y.-Q. Chen

Abstract top

In the title compound, C8H12N2·H2O, four substituted pyridine molecules alternate with four water molecules, forming a large ring via Owater-H...Npyridine and Namine-H...Owater hydrogen bonding. Adjacent rings are connected via Owater-H...Owater hydrogen-bonds, forming a three-dimensional network.

Comment top

There is continuing interest in pyridin-amine derivatives due to their significant bioactivities (Smith et al., 2005; Tsuzuki et al., 2005) and their role as important chemical intermediates in the formation of diverse molecules possessing biological activities (Birault et al., 2005; Gordon et al., 1996; Player et al., 2007). In general, compounds with amino groups can be used to prepare Schiff base ligands, which have played an important role in the development of coordination chemistry as they can readily form stable complexes with most metal ions (Lin et al., 2005; Yu et al., 2005; Zhou et al., 2005). As part of our continuing investigation of such compounds, we report here the synthesis and crystal structure of a new pyridinamine derivative (Fig.1). Hydrogen-bonding interactions play an important role in the solid-state structure of this compound as they have in similar structures reported earlier (Li et al., 2008; Xie et al., 2008). As shown in Fig.2, four pyridine molecules and four water molecules are linked together alternatively to form a big ring via Owater—H···Npyridine and Namine—H···Owater hydrogen bonding (Table 1). Adjacent rings are connected to form a three-dimensional network via Owater—H···Owater hydrogen-bonding. Channel can be seen within stacks of the hydrogen bonded rings. The inner walls of the channels are occupied by the methyl groups and no solvent was found.

Related literature top

For pyridin-amine derivatives, see: Smith et al. (2005); Tsuzuki et al. (2005). For their role as chemical intermediates in the formation of diverse molecules possessing biological activity, see: Birault et al. (2005); Gordon et al. (1996); Player et al. (2007). For related structures, see: Li et al. (2008); Lin et al. (2005); Xie et al. (2008); Yu et al. (2005); Zhou et al. (2005).

For related literature, see: Larson (1970).

Experimental top

4-nitro-2,3,5-trimethylpyridine-N-oxide(18.2 g, 100 mmol), Raney nickel (25 g, 426 mmol) and 200 ml of ethanol were placed combined a three-necked flask. 80% Hydrazine hydrate(25 ml, 400 mmol) was added dropwise, maintaining the temperature under 35 degrees centigrade. The mixture was heated to reflux and 80% hydrazine hydrate was added dropwise continually. The catalyst was suction-filtered. Half of the ethanol was concentrated under vacuum. The residue was left at room temperature for 7 days giving some colorless needle shaped crystals suitable for data collection.

Refinement top

Friedel equivalents were merged. All H atoms were placed in calculated positions, with C—H = 0.93 or 0.96Å and N—H = 0.869 or 0.877 Å and included in the final cycles of refinement with a riding model, with Uiso(H) = 1.2Ueq(C,N,O).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2007); cell refinement: PROCESS-AUTO (Rigaku, 2007); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Molecular structure showing 40% probability displacement ellipsoids.
[Figure 2] Fig. 2. Hydrogen-bonding interactions.
4-Amino-2,3,5-trimethylpyridine monohydrate top
Crystal data top
C8H12N2·H2OZ = 8
Mr = 154.21F000 = 672.00
Tetragonal, P421cDx = 1.095 Mg m−3
Hall symbol: P -4 2nMo Kα radiation
λ = 0.71075 Å
a = 19.5710 (9) ÅCell parameters from 10766 reflections
b = 19.5710 (9) Åθ = 3.3–27.4º
c = 4.8819 (2) ŵ = 0.07 mm−1
α = 90ºT = 296 K
β = 90ºChunk, colorless
γ = 90º0.33 × 0.27 × 0.22 mm
V = 1869.89 (14) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		951 reflections with F2 > 2.0σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.045
ω scansθmax = 27.4º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −25→25
Tmin = 0.967, Tmax = 0.984k = −25→25
17243 measured reflectionsl = −6→5
1250 independent reflections
Refinement top
Refinement on F2  w = 1/[0.0001Fo2 + 1.1100σ(Fo2)]/(4Fo2)
R[F2 > 2σ(F2)] = 0.035(Δ/σ)max < 0.001
wR(F2) = 0.088Δρmax = 0.23 e Å−3
S = 1.00Δρmin = −0.20 e Å−3
1250 reflectionsExtinction correction: Larson (1970)
101 parametersExtinction coefficient: 460 (64)
H-atom parameters constrained
Crystal data top
C8H12N2·H2Oγ = 90º
Mr = 154.21V = 1869.89 (14) Å3
Tetragonal, P421cZ = 8
a = 19.5710 (9) ÅMo Kα
b = 19.5710 (9) ŵ = 0.07 mm−1
c = 4.8819 (2) ÅT = 296 K
α = 90º0.33 × 0.27 × 0.22 mm
β = 90º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1250 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		951 reflections with F2 > 2.0σ(F2)
Tmin = 0.967, Tmax = 0.984Rint = 0.045
17243 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.088Δρmax = 0.23 e Å−3
S = 1.00Δρmin = −0.20 e Å−3
1250 reflectionsAbsolute structure: ?
101 parametersFlack parameter: ?
? restraintsRogers parameter: ?
Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.25888 (6)0.28901 (6)0.2514 (3)0.0571 (4)
N10.23938 (11)0.42486 (10)0.3906 (4)0.0581 (6)
N20.19626 (9)0.61921 (9)0.6961 (4)0.0534 (6)
C10.27642 (12)0.47949 (12)0.3109 (5)0.0528 (7)
C20.26474 (11)0.54519 (11)0.4090 (5)0.0472 (6)
C30.21206 (11)0.55487 (11)0.6011 (4)0.0427 (6)
C40.17323 (12)0.49824 (12)0.6859 (4)0.0465 (6)
C50.18992 (12)0.43602 (12)0.5762 (5)0.0556 (8)
C60.33136 (13)0.46412 (12)0.1049 (7)0.0756 (9)
C70.30672 (12)0.60551 (12)0.3136 (6)0.0690 (9)
C80.11654 (12)0.50507 (12)0.8924 (5)0.0603 (7)
H50.16490.39840.63500.067*
H610.37530.46740.19130.091*
H620.32510.41870.03450.091*
H630.32880.4964−0.04280.091*
H710.32900.59430.14420.083*
H720.27740.64420.28650.083*
H730.34050.61630.44950.083*
H810.13530.51841.06600.072*
H820.08470.53910.83150.072*
H830.09350.46200.91130.072*
H1010.25300.33170.29010.069*
H1020.24570.27710.09210.069*
H2010.17550.62290.84890.064*
H2020.22660.65110.67430.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0663 (10)0.0465 (9)0.0584 (10)0.0063 (8)−0.0044 (9)−0.0047 (9)
N10.0701 (14)0.0454 (11)0.0587 (14)0.0003 (10)0.0039 (14)−0.0022 (11)
N20.0624 (13)0.0433 (11)0.0545 (12)−0.0029 (9)0.0092 (11)−0.0006 (10)
C10.0563 (16)0.0549 (16)0.0471 (14)0.0083 (12)0.0024 (13)−0.0024 (13)
C20.0504 (14)0.0454 (14)0.0459 (13)0.0003 (11)0.0032 (14)0.0021 (13)
C30.0472 (13)0.0398 (12)0.0411 (12)0.0003 (10)−0.0022 (12)0.0001 (12)
C40.0507 (14)0.0452 (13)0.0435 (12)−0.0002 (12)−0.0022 (12)0.0036 (13)
C50.0658 (17)0.0454 (15)0.0557 (15)−0.0047 (12)0.0015 (15)0.0042 (14)
C60.086 (2)0.0690 (19)0.0717 (19)0.0162 (16)0.021 (2)−0.0020 (18)
C70.0674 (17)0.0627 (17)0.077 (2)−0.0054 (14)0.0164 (17)0.0013 (16)
C80.0640 (16)0.0609 (15)0.0562 (14)−0.0072 (13)0.0067 (15)0.0060 (16)
Geometric parameters (Å, °) top
N1—C11.349 (3)N2—H2010.852
N1—C51.344 (3)N2—H2020.868
N2—C31.377 (2)C5—H50.930
C1—C21.391 (3)C6—H610.960
C1—C61.503 (3)C6—H620.960
C2—C31.407 (3)C6—H630.960
C2—C71.512 (3)C7—H710.960
C3—C41.406 (3)C7—H720.960
C4—C51.370 (3)C7—H730.960
C4—C81.505 (3)C8—H810.960
O1—H1010.864C8—H820.960
O1—H1020.852C8—H830.960
C1—N1—C5116.9 (2)C4—C5—H5117.3
N1—C1—C2123.0 (2)C1—C6—H61109.5
N1—C1—C6114.8 (2)C1—C6—H62109.5
C2—C1—C6122.2 (2)C1—C6—H63109.5
C1—C2—C3118.3 (2)H61—C6—H62109.5
C1—C2—C7121.8 (2)H61—C6—H63109.5
C3—C2—C7119.9 (2)H62—C6—H63109.5
N2—C3—C2120.82 (19)C2—C7—H71109.5
N2—C3—C4120.0 (2)C2—C7—H72109.5
C2—C3—C4119.1 (2)C2—C7—H73109.5
C3—C4—C5117.2 (2)H71—C7—H72109.5
C3—C4—C8121.7 (2)H71—C7—H73109.5
C5—C4—C8121.1 (2)H72—C7—H73109.5
N1—C5—C4125.4 (2)C4—C8—H81109.5
H101—O1—H102115.0C4—C8—H82109.5
C3—N2—H201118.6C4—C8—H83109.5
C3—N2—H202117.5H81—C8—H82109.5
H201—N2—H202111.9H81—C8—H83109.5
N1—C5—H5117.3H82—C8—H83109.5
C1—N1—C5—C41.5 (3)C7—C2—C3—N22.6 (3)
C5—N1—C1—C2−0.9 (3)C7—C2—C3—C4179.6 (2)
C5—N1—C1—C6179.6 (2)N2—C3—C4—C5177.6 (2)
N1—C1—C2—C30.3 (3)N2—C3—C4—C8−3.5 (3)
N1—C1—C2—C7−179.4 (2)C2—C3—C4—C50.6 (3)
C6—C1—C2—C3179.8 (2)C2—C3—C4—C8179.5 (2)
C6—C1—C2—C70.1 (2)C3—C4—C5—N1−1.3 (3)
C1—C2—C3—N2−177.1 (2)C8—C4—C5—N1179.8 (2)
C1—C2—C3—C4−0.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H101···N10.861.912.771 (2)178
O1—H102···O1i0.851.932.778 (2)173
N2—H202···O1ii0.872.173.009 (2)161
Symmetry codes: (i) −y+1/2, −x+1/2, z−1/2; (ii) y, −x+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H101···N10.861.912.771 (2)178
O1—H102···O1i0.851.932.778 (2)173
N2—H202···O1ii0.872.173.009 (2)161
Symmetry codes: (i) −y+1/2, −x+1/2, z−1/2; (ii) y, −x+1, −z+1.
Acknowledgements top

We express our gratitude to Zhejiang University and Hangzhou Normal University for financial Support.

references
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