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

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

doi:10.1107/S1600536809016833

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1329

doi:10.1107/S1600536809016833

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

Li-Yan Dai,^a ^* Fu-Liang Zhang,^b Liang Shen ^b and Ying-Qi Chen ^a

^aDepartment of Chemical Engineering, Zhejiang University, Hangzhou, People's Republic of China, and ^bCollege of Materials Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, People's Republic of China
^*Correspondence e-mail: dailiyan@zju.edu.cn

(Received 30 March 2009; accepted 5 May 2009; online 20 May 2009)

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

Related literature

For pyridine-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 the extinction correction, see: Larson (1970 ).

Experimental

Crystal data

C₈H₁₂N₂·H₂O
M_r = 154.21
Tetragonal, $[P \overline 42_1 c ]$
a = 19.5710 (9) Å
c = 4.8819 (2) Å
V = 1869.89 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.33 × 0.27 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.967, T_max = 0.984
17243 measured reflections
1250 independent reflections
951 reflections with F² > 2.0σ(F²)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.088
S = 1.00
1250 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.23 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—H101⋯N1	0.86	1.91	2.771 (2)	178
O1—H102⋯O1ⁱ	0.85	1.93	2.778 (2)	173
N2—H202⋯O1ⁱⁱ	0.87	2.17	3.009 (2)	161
Symmetry codes: (i) $[-y+{\script{1\over 2}}, -x+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) y, -x+1, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 2007 ); cell refinement: PROCESS-AUTO; 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 ).

Supporting information

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536809016833/fl2246sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016833/fl2246Isup2.hkl

checkCIF report

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 O_water—H···N_pyridine and N_amine—H···O_water hydrogen bonding (Table 1). Adjacent rings are connected to form a three-dimensional network via O_water—H···O_waterhydrogen-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.

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

	Fig. 1. Molecular structure showing 40% probability displacement ellipsoids.
	Fig. 2. Hydrogen-bonding interactions.

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

Crystal data top

C₈H₁₂N₂·H₂O	D_x = 1.095 Mg m⁻³
M_r = 154.21	Mo Kα radiation, λ = 0.71075 Å
Tetragonal, P42₁c	Cell parameters from 10766 reflections
Hall symbol: P -4 2n	θ = 3.3–27.4°
a = 19.5710 (9) Å	µ = 0.07 mm⁻¹
c = 4.8819 (2) Å	T = 296 K
V = 1869.89 (14) Å³	Chunk, colorless
Z = 8	0.33 × 0.27 × 0.22 mm
F(000) = 672.00

Data collection top

Rigaku R-AXIS RAPID diffractometer	951 reflections with F² > 2.0σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.045
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −25→25
T_min = 0.967, T_max = 0.984	k = −25→25
17243 measured reflections	l = −6→5
1250 independent reflections

Refinement top

Refinement on F²	w = 1/[0.0001F_o² + 1.1100σ(F_o²)]/(4F_o²)
R[F² > 2σ(F²)] = 0.035	(Δ/σ)_max < 0.001
wR(F²) = 0.088	Δρ_max = 0.23 e Å⁻³
S = 1.00	Δρ_min = −0.20 e Å⁻³
1250 reflections	Extinction correction: Larson (1970)
101 parameters	Extinction coefficient: 460 (64)
H-atom parameters constrained

Crystal data top

C₈H₁₂N₂·H₂O	Z = 8
M_r = 154.21	Mo Kα radiation
Tetragonal, P42₁c	µ = 0.07 mm⁻¹
a = 19.5710 (9) Å	T = 296 K
c = 4.8819 (2) Å	0.33 × 0.27 × 0.22 mm
V = 1869.89 (14) Å³

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)
T_min = 0.967, T_max = 0.984	R_int = 0.045
17243 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	101 parameters
wR(F²) = 0.088	H-atom parameters constrained
S = 1.00	Δρ_max = 0.23 e Å⁻³
1250 reflections	Δρ_min = −0.20 e Å⁻³

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

	x	y	z	U_iso*/U_eq
O1	0.25888 (6)	0.28901 (6)	0.2514 (3)	0.0571 (4)
N1	0.23938 (11)	0.42486 (10)	0.3906 (4)	0.0581 (6)
N2	0.19626 (9)	0.61921 (9)	0.6961 (4)	0.0534 (6)
C1	0.27642 (12)	0.47949 (12)	0.3109 (5)	0.0528 (7)
C2	0.26474 (11)	0.54519 (11)	0.4090 (5)	0.0472 (6)
C3	0.21206 (11)	0.55487 (11)	0.6011 (4)	0.0427 (6)
C4	0.17323 (12)	0.49824 (12)	0.6859 (4)	0.0465 (6)
C5	0.18992 (12)	0.43602 (12)	0.5762 (5)	0.0556 (8)
C6	0.33136 (13)	0.46412 (12)	0.1049 (7)	0.0756 (9)
C7	0.30672 (12)	0.60551 (12)	0.3136 (6)	0.0690 (9)
C8	0.11654 (12)	0.50507 (12)	0.8924 (5)	0.0603 (7)
H5	0.1649	0.3984	0.6350	0.067*
H61	0.3753	0.4674	0.1913	0.091*
H62	0.3251	0.4187	0.0345	0.091*
H63	0.3288	0.4964	−0.0428	0.091*
H71	0.3290	0.5943	0.1442	0.083*
H72	0.2774	0.6442	0.2865	0.083*
H73	0.3405	0.6163	0.4495	0.083*
H81	0.1353	0.5184	1.0660	0.072*
H82	0.0847	0.5391	0.8315	0.072*
H83	0.0935	0.4620	0.9113	0.072*
H101	0.2530	0.3317	0.2901	0.069*
H102	0.2457	0.2771	0.0921	0.069*
H201	0.1755	0.6229	0.8489	0.064*
H202	0.2266	0.6511	0.6743	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0663 (10)	0.0465 (9)	0.0584 (10)	0.0063 (8)	−0.0044 (9)	−0.0047 (9)
N1	0.0701 (14)	0.0454 (11)	0.0587 (14)	0.0003 (10)	0.0039 (14)	−0.0022 (11)
N2	0.0624 (13)	0.0433 (11)	0.0545 (12)	−0.0029 (9)	0.0092 (11)	−0.0006 (10)
C1	0.0563 (16)	0.0549 (16)	0.0471 (14)	0.0083 (12)	0.0024 (13)	−0.0024 (13)
C2	0.0504 (14)	0.0454 (14)	0.0459 (13)	0.0003 (11)	0.0032 (14)	0.0021 (13)
C3	0.0472 (13)	0.0398 (12)	0.0411 (12)	0.0003 (10)	−0.0022 (12)	0.0001 (12)
C4	0.0507 (14)	0.0452 (13)	0.0435 (12)	−0.0002 (12)	−0.0022 (12)	0.0036 (13)
C5	0.0658 (17)	0.0454 (15)	0.0557 (15)	−0.0047 (12)	0.0015 (15)	0.0042 (14)
C6	0.086 (2)	0.0690 (19)	0.0717 (19)	0.0162 (16)	0.021 (2)	−0.0020 (18)
C7	0.0674 (17)	0.0627 (17)	0.077 (2)	−0.0054 (14)	0.0164 (17)	0.0013 (16)
C8	0.0640 (16)	0.0609 (15)	0.0562 (14)	−0.0072 (13)	0.0067 (15)	0.0060 (16)

Geometric parameters (Å, º) top

N1—C1	1.349 (3)	N2—H201	0.852
N1—C5	1.344 (3)	N2—H202	0.868
N2—C3	1.377 (2)	C5—H5	0.930
C1—C2	1.391 (3)	C6—H61	0.960
C1—C6	1.503 (3)	C6—H62	0.960
C2—C3	1.407 (3)	C6—H63	0.960
C2—C7	1.512 (3)	C7—H71	0.960
C3—C4	1.406 (3)	C7—H72	0.960
C4—C5	1.370 (3)	C7—H73	0.960
C4—C8	1.505 (3)	C8—H81	0.960
O1—H101	0.864	C8—H82	0.960
O1—H102	0.852	C8—H83	0.960

C1—N1—C5	116.9 (2)	C4—C5—H5	117.3
N1—C1—C2	123.0 (2)	C1—C6—H61	109.5
N1—C1—C6	114.8 (2)	C1—C6—H62	109.5
C2—C1—C6	122.2 (2)	C1—C6—H63	109.5
C1—C2—C3	118.3 (2)	H61—C6—H62	109.5
C1—C2—C7	121.8 (2)	H61—C6—H63	109.5
C3—C2—C7	119.9 (2)	H62—C6—H63	109.5
N2—C3—C2	120.82 (19)	C2—C7—H71	109.5
N2—C3—C4	120.0 (2)	C2—C7—H72	109.5
C2—C3—C4	119.1 (2)	C2—C7—H73	109.5
C3—C4—C5	117.2 (2)	H71—C7—H72	109.5
C3—C4—C8	121.7 (2)	H71—C7—H73	109.5
C5—C4—C8	121.1 (2)	H72—C7—H73	109.5
N1—C5—C4	125.4 (2)	C4—C8—H81	109.5
H101—O1—H102	115.0	C4—C8—H82	109.5
C3—N2—H201	118.6	C4—C8—H83	109.5
C3—N2—H202	117.5	H81—C8—H82	109.5
H201—N2—H202	111.9	H81—C8—H83	109.5
N1—C5—H5	117.3	H82—C8—H83	109.5

C1—N1—C5—C4	1.5 (3)	C7—C2—C3—N2	2.6 (3)
C5—N1—C1—C2	−0.9 (3)	C7—C2—C3—C4	179.6 (2)
C5—N1—C1—C6	179.6 (2)	N2—C3—C4—C5	177.6 (2)
N1—C1—C2—C3	0.3 (3)	N2—C3—C4—C8	−3.5 (3)
N1—C1—C2—C7	−179.4 (2)	C2—C3—C4—C5	0.6 (3)
C6—C1—C2—C3	179.8 (2)	C2—C3—C4—C8	179.5 (2)
C6—C1—C2—C7	0.1 (2)	C3—C4—C5—N1	−1.3 (3)
C1—C2—C3—N2	−177.1 (2)	C8—C4—C5—N1	179.8 (2)
C1—C2—C3—C4	−0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H101···N1	0.86	1.91	2.771 (2)	178
O1—H102···O1ⁱ	0.85	1.93	2.778 (2)	173
N2—H202···O1ⁱⁱ	0.87	2.17	3.009 (2)	161

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N₂·H₂O
M_r	154.21
Crystal system, space group	Tetragonal, P42₁c
Temperature (K)	296
a, c (Å)	19.5710 (9), 4.8819 (2)
V (Å³)	1869.89 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.33 × 0.27 × 0.22

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.967, 0.984
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	17243, 1250, 951
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.088, 1.00
No. of reflections	1250
No. of parameters	101
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20

Computer programs: PROCESS-AUTO (Rigaku, 2007), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H101···N1	0.864	1.907	2.771 (2)	177.7
O1—H102···O1ⁱ	0.852	1.930	2.778 (2)	173.4
N2—H202···O1ⁱⁱ	0.868	2.174	3.009 (2)	161.1

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

Acknowledgements

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

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