2,4-Diamino-6-methyl-1,3,5-triazin-1-ium chloride

Qian, H.-F.; Huang, W.

doi:10.1107/S1600536810007907

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o759

doi:10.1107/S1600536810007907

Open

access

2,4-Diamino-6-methyl-1,3,5-triazin-1-ium chloride

Hui-Fen Qian ^a ^* and Wei Huang ^b ‡

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn

(Received 22 January 2010; accepted 2 March 2010; online 6 March 2010)

In the title compound, C₄H₈N₅⁺·Cl⁻, a two-dimensional layer packing network is observed in which every chloride anion links three adjacent 2,4-diamino-6-methyl-1,3,5-triazin-1-ium cations by N—H⋯Cl hydrogen-bonding interactions, forming 12-membered and eight-membered hydrogen-bonded rings with graph-set motifs R₄⁴(12) and R₃³(8), respectively. In addition, N—H⋯N hydrogen bonds are found between adjacent cations, forming another type of eight-membered [R₂²(8)] hydrogen-bonded ring.

Related literature

For related complexes, see Delori et al. (2008 ); Fan et al. (2009 ); Perpétuo & Janczak (2007 ); Portalone & Colapietro (2007 ); Wijaya et al. (2004 ).

Experimental

Crystal data

C₄H₈N₅⁺·Cl⁻
M_r = 161.60
Triclinic, $[P \overline 1]$
a = 5.6449 (11) Å
b = 7.8723 (15) Å
c = 9.3476 (17) Å
α = 65.551 (3)°
β = 75.779 (2)°
γ = 71.027 (2)°
V = 354.61 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 291 K
0.16 × 0.14 × 0.10 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.929, T_max = 0.955
1871 measured reflections
1303 independent reflections
1042 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.111
S = 1.07
1303 reflections
96 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Cl1ⁱ	0.86 (1)	2.25 (1)	3.107 (2)	174 (3)
N4—H4D⋯Cl1ⁱⁱ	0.86	2.52	3.372 (2)	169
N4—H4E⋯N1ⁱⁱⁱ	0.86	2.32	3.171 (3)	170
N5—H5A⋯N2ⁱⁱ	0.86	2.15	3.008 (3)	174
N5—H5B⋯Cl1	0.86	2.40	3.125 (2)	143
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+1, -z+2; (iii) -x, -y, -z+2.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007907/nk2023sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007907/nk2023Isup2.hkl

checkCIF report

Comment top

To date, a series of clathrates and acid-base adducts of 2,4-diamino-6-methyl-1,3,5-triazine have been structurally reported (Delori et al., 2008; Fan et al., 2009; Perpétuo et al., 2007; Portalone et al., 2007; Wijaya et al., 2004). In this paper, we report the X-ray single-crystal structure of 2,4-diamino-6-methyl-1,3,5-triazin-1-ium chloride (I).

The molecular structure of (I) is illustrated in Fig. 1. The mean deviation from a least-squares plane for all the non-hydrogen atoms of the cations is 0.0039 (1) Å, while that for all the non-hydrogen atoms of (I) including the chloride anion is 0.0041 (1) Å. It is interesting to note that every chloride anion links three adjacent 2,4-diamino-6-methyl-1,3,5-triazin-1-ium cations by N—H···Cl hydrogen bonding interactions forming two kinds of twelve-membered [R₄⁴(12)] and eight-membered [R₃³(8)] hydrogen-bonded rings. In addition, N—H···N hydrogen bonding interactions are found between nitrogen atoms N1, N4 and N2, N5 from neighbouring cations, respectively, forming another type of eight-membered [R₂²(8)] hydrogen-bonded rings. With the help of above-mentioned N—H···N and N—H···Cl hydrogen bonds, a two-dimensional layer packing network is finally constituted (Fig. 2).

Related literature top

For related complexes, see Delori et al. (2008); Fan et al. (2009); Perpétuo & Janczak (2007); Portalone et al. (2007); Wijaya et al. (2004).

Experimental top

The title compound was purchased directly from Kangmanlin Co. in China and the colourless single crystals of (I) suitable for X-ray diffraction determination were obtained from a mixture of water and ethanol in a ration of 1:3 (v/v) by slow evaporation at room temperature in air for one week.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Perspective view of the hydrogen bonding interactions within one layer in (I), where the hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+1, -z+2, (iii) -x, -y, -z+2.]

2,4-Diamino-6-methyl-1,3,5-triazin-1-ium chloride top

Crystal data top

C₄H₈N₅⁺·Cl⁻	Z = 2
M_r = 161.60	F(000) = 168
Triclinic, P1	D_x = 1.513 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6449 (11) Å	Cell parameters from 890 reflections
b = 7.8723 (15) Å	θ = 2.4–28.0°
c = 9.3476 (17) Å	µ = 0.47 mm⁻¹
α = 65.551 (3)°	T = 291 K
β = 75.779 (2)°	Block, colourless
γ = 71.027 (2)°	0.16 × 0.14 × 0.10 mm
V = 354.61 (12) Å³

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1303 independent reflections
Radiation source: sealed tube	1042 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.082
ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.929, T_max = 0.955	k = −9→8
1871 measured reflections	l = −11→11

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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0566P)²] where P = (F_o² + 2F_c²)/3
1303 reflections	(Δ/σ)_max < 0.001
96 parameters	Δρ_max = 0.25 e Å⁻³
2 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₄H₈N₅⁺·Cl⁻	γ = 71.027 (2)°
M_r = 161.60	V = 354.61 (12) Å³
Triclinic, P1	Z = 2
a = 5.6449 (11) Å	Mo Kα radiation
b = 7.8723 (15) Å	µ = 0.47 mm⁻¹
c = 9.3476 (17) Å	T = 291 K
α = 65.551 (3)°	0.16 × 0.14 × 0.10 mm
β = 75.779 (2)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1303 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1042 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.955	R_int = 0.082
1871 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	2 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.25 e Å⁻³
1303 reflections	Δρ_min = −0.28 e Å⁻³
96 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2007) and successive difference Fourier syntheses.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.4096 (5)	0.1560 (3)	0.7585 (3)	0.0347 (6)
C2	0.2148 (4)	0.2118 (3)	0.9841 (3)	0.0321 (5)
C3	0.5223 (4)	0.3642 (3)	0.8366 (3)	0.0328 (6)
C4	0.4508 (5)	0.0666 (4)	0.6414 (3)	0.0458 (7)
H4A	0.4399	−0.0647	0.6949	0.069*
H4B	0.6152	0.0696	0.5817	0.069*
H4C	0.3244	0.1365	0.5709	0.069*
Cl1	1.09342 (12)	0.67148 (10)	0.58725 (8)	0.0492 (3)
N1	0.2385 (4)	0.1200 (3)	0.8830 (2)	0.0375 (5)
N2	0.3507 (4)	0.3320 (3)	0.9661 (2)	0.0338 (5)
N3	0.5556 (4)	0.2746 (3)	0.7331 (2)	0.0351 (5)
N4	0.0432 (4)	0.1740 (3)	1.1080 (2)	0.0433 (6)
H4D	0.0189	0.2262	1.1767	0.052*
H4E	−0.0452	0.0969	1.1205	0.052*
N5	0.6634 (4)	0.4803 (3)	0.8085 (2)	0.0443 (6)
H5A	0.6466	0.5365	0.8733	0.053*
H5B	0.7731	0.5003	0.7252	0.053*
H3	0.654 (4)	0.297 (4)	0.6445 (19)	0.058 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0390 (14)	0.0376 (13)	0.0335 (13)	−0.0099 (11)	0.0005 (10)	−0.0214 (10)
C2	0.0379 (13)	0.0339 (12)	0.0281 (12)	−0.0104 (10)	0.0016 (10)	−0.0170 (10)
C3	0.0378 (13)	0.0349 (12)	0.0309 (12)	−0.0106 (10)	−0.0010 (10)	−0.0177 (10)
C4	0.0544 (17)	0.0604 (17)	0.0401 (14)	−0.0242 (14)	0.0072 (12)	−0.0352 (13)
Cl1	0.0474 (5)	0.0639 (5)	0.0421 (4)	−0.0230 (3)	0.0105 (3)	−0.0272 (3)
N1	0.0442 (13)	0.0421 (12)	0.0352 (12)	−0.0180 (10)	0.0051 (10)	−0.0232 (9)
N2	0.0400 (12)	0.0386 (11)	0.0303 (10)	−0.0161 (9)	0.0038 (9)	−0.0198 (9)
N3	0.0403 (12)	0.0403 (11)	0.0312 (11)	−0.0145 (10)	0.0053 (9)	−0.0216 (9)
N4	0.0524 (13)	0.0533 (13)	0.0392 (12)	−0.0276 (11)	0.0114 (10)	−0.0300 (10)
N5	0.0539 (14)	0.0555 (13)	0.0393 (12)	−0.0311 (11)	0.0121 (10)	−0.0294 (10)

Geometric parameters (Å, º) top

C1—N1	1.311 (3)	C4—H4A	0.9600
C1—N3	1.352 (3)	C4—H4B	0.9600
C1—C4	1.468 (3)	C4—H4C	0.9600
C2—N4	1.312 (3)	N3—H3	0.862 (11)
C2—N2	1.337 (3)	N4—H4D	0.8600
C2—N1	1.369 (3)	N4—H4E	0.8600
C3—N5	1.308 (3)	N5—H5A	0.8600
C3—N2	1.341 (3)	N5—H5B	0.8600
C3—N3	1.363 (3)

N1—C1—N3	122.0 (2)	H4A—C4—H4C	109.5
N1—C1—C4	120.7 (2)	H4B—C4—H4C	109.5
N3—C1—C4	117.3 (2)	C1—N1—C2	115.85 (19)
N4—C2—N2	119.4 (2)	C2—N2—C3	116.07 (18)
N4—C2—N1	115.07 (19)	C1—N3—C3	119.81 (19)
N2—C2—N1	125.6 (2)	C1—N3—H3	115 (2)
N5—C3—N2	120.5 (2)	C3—N3—H3	124 (2)
N5—C3—N3	118.8 (2)	C2—N4—H4D	120.0
N2—C3—N3	120.7 (2)	C2—N4—H4E	120.0
C1—C4—H4A	109.5	H4D—N4—H4E	120.0
C1—C4—H4B	109.5	C3—N5—H5A	120.0
H4A—C4—H4B	109.5	C3—N5—H5B	120.0
C1—C4—H4C	109.5	H5A—N5—H5B	120.0

N3—C1—N1—C2	0.9 (3)	N5—C3—N2—C2	179.7 (2)
C4—C1—N1—C2	−179.6 (2)	N3—C3—N2—C2	−1.3 (3)
N4—C2—N1—C1	−179.9 (2)	N1—C1—N3—C3	−1.6 (4)
N2—C2—N1—C1	−0.3 (3)	C4—C1—N3—C3	178.8 (2)
N4—C2—N2—C3	−179.9 (2)	N5—C3—N3—C1	−179.1 (2)
N1—C2—N2—C3	0.6 (3)	N2—C3—N3—C1	1.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl1ⁱ	0.86 (1)	2.25 (1)	3.107 (2)	174 (3)
N4—H4D···Cl1ⁱⁱ	0.86	2.52	3.372 (2)	169
N4—H4E···N1ⁱⁱⁱ	0.86	2.32	3.171 (3)	170
N5—H5A···N2ⁱⁱ	0.86	2.15	3.008 (3)	174
N5—H5B···Cl1	0.86	2.40	3.125 (2)	143

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

Experimental details

Crystal data
Chemical formula	C₄H₈N₅⁺·Cl⁻
M_r	161.60
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	5.6449 (11), 7.8723 (15), 9.3476 (17)
α, β, γ (°)	65.551 (3), 75.779 (2), 71.027 (2)
V (Å³)	354.61 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.16 × 0.14 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.929, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	1871, 1303, 1042
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.111, 1.07
No. of reflections	1303
No. of parameters	96
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)	0.25, −0.28

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl1ⁱ	0.862 (11)	2.248 (11)	3.107 (2)	174 (3)
N4—H4D···Cl1ⁱⁱ	0.86	2.52	3.372 (2)	169
N4—H4E···N1ⁱⁱⁱ	0.86	2.32	3.171 (3)	170
N5—H5A···N2ⁱⁱ	0.86	2.15	3.008 (3)	174
N5—H5B···Cl1	0.86	2.40	3.125 (2)	143

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

Footnotes

‡Additional correspondence author.

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (No. 20871065) and the Jiangsu Province Department of Science and Technology (No. BK2009226) for financial aid.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Delori, A., Suresh, E. & Pedireddi, V.-R. (2008). Chem. Eur. J. 14, 6967–6977. Web of Science CSD CrossRef PubMed CAS Google Scholar
Fan, Y., You, W., Qian, H.-F., Liu, J.-L. & Huang, W. (2009). Acta Cryst. E65, o494. Web of Science CSD CrossRef IUCr Journals Google Scholar
Perpétuo, G. J. & Janczak, J. (2007). Acta Cryst. C63, o271–o273. Web of Science CSD CrossRef IUCr Journals Google Scholar
Portalone, G. & Colapietro, M. (2007). Acta Cryst. C63, o655–o658. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). 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
Wijaya, K., Moers, O., Henschel, D., Blaschette, A. & Jones, P.-G. (2004). Z. Naturforsch. Teil. B, 59, 747–756. CAS Google Scholar