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ISSN: 2056-9890

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

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[Delori, A., Suresh, E. & Pedireddi, V.-R. (2008). Chem. Eur. J. 14, 6967-6977.]); Fan et al. (2009[Fan, Y., You, W., Qian, H.-F., Liu, J.-L. & Huang, W. (2009). Acta Cryst. E65, o494.]); Perpétuo & Janczak (2007[Perpétuo, G. J. & Janczak, J. (2007). Acta Cryst. C63, o271-o273.]); Portalone & Colapietro (2007[Portalone, G. & Colapietro, M. (2007). Acta Cryst. C63, o655-o658.]); Wijaya et al. (2004[Wijaya, K., Moers, O., Henschel, D., Blaschette, A. & Jones, P.-G. (2004). Z. Naturforsch. Teil. B, 59, 747-756.]).

[Scheme 1]

Experimental

Crystal data
  • C4H8N5+·Cl

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.929, Tmax = 0.955

  • 1871 measured reflections

  • 1303 independent reflections

  • 1042 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

The H atoms bonded to carbon atoms were placed in geometrically idealized positions and refined as riding with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C). The H atom bonded to nitrogen atom was located in the difference synthesis and were refined isotropically.

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
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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+·ClZ = 2
Mr = 161.60F(000) = 168
Triclinic, P1Dx = 1.513 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.6449 (11) ÅCell parameters from 890 reflections
b = 7.8723 (15) Åθ = 2.4–28.0°
c = 9.3476 (17) ŵ = 0.47 mm1
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 tube1042 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
ω scansθmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 66
Tmin = 0.929, Tmax = 0.955k = 98
1871 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: difference Fourier map
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0566P)2]
where P = (Fo2 + 2Fc2)/3
1303 reflections(Δ/σ)max < 0.001
96 parametersΔρmax = 0.25 e Å3
2 restraintsΔρmin = 0.28 e Å3
Crystal data top
C4H8N5+·Clγ = 71.027 (2)°
Mr = 161.60V = 354.61 (12) Å3
Triclinic, P1Z = 2
a = 5.6449 (11) ÅMo Kα radiation
b = 7.8723 (15) ŵ = 0.47 mm1
c = 9.3476 (17) ÅT = 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)
Tmin = 0.929, Tmax = 0.955Rint = 0.082
1871 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0392 restraints
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.25 e Å3
1303 reflectionsΔρmin = 0.28 e Å3
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
xyzUiso*/Ueq
C10.4096 (5)0.1560 (3)0.7585 (3)0.0347 (6)
C20.2148 (4)0.2118 (3)0.9841 (3)0.0321 (5)
C30.5223 (4)0.3642 (3)0.8366 (3)0.0328 (6)
C40.4508 (5)0.0666 (4)0.6414 (3)0.0458 (7)
H4A0.43990.06470.69490.069*
H4B0.61520.06960.58170.069*
H4C0.32440.13650.57090.069*
Cl11.09342 (12)0.67148 (10)0.58725 (8)0.0492 (3)
N10.2385 (4)0.1200 (3)0.8830 (2)0.0375 (5)
N20.3507 (4)0.3320 (3)0.9661 (2)0.0338 (5)
N30.5556 (4)0.2746 (3)0.7331 (2)0.0351 (5)
N40.0432 (4)0.1740 (3)1.1080 (2)0.0433 (6)
H4D0.01890.22621.17670.052*
H4E0.04520.09691.12050.052*
N50.6634 (4)0.4803 (3)0.8085 (2)0.0443 (6)
H5A0.64660.53650.87330.053*
H5B0.77310.50030.72520.053*
H30.654 (4)0.297 (4)0.6445 (19)0.058 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0390 (14)0.0376 (13)0.0335 (13)0.0099 (11)0.0005 (10)0.0214 (10)
C20.0379 (13)0.0339 (12)0.0281 (12)0.0104 (10)0.0016 (10)0.0170 (10)
C30.0378 (13)0.0349 (12)0.0309 (12)0.0106 (10)0.0010 (10)0.0177 (10)
C40.0544 (17)0.0604 (17)0.0401 (14)0.0242 (14)0.0072 (12)0.0352 (13)
Cl10.0474 (5)0.0639 (5)0.0421 (4)0.0230 (3)0.0105 (3)0.0272 (3)
N10.0442 (13)0.0421 (12)0.0352 (12)0.0180 (10)0.0051 (10)0.0232 (9)
N20.0400 (12)0.0386 (11)0.0303 (10)0.0161 (9)0.0038 (9)0.0198 (9)
N30.0403 (12)0.0403 (11)0.0312 (11)0.0145 (10)0.0053 (9)0.0216 (9)
N40.0524 (13)0.0533 (13)0.0392 (12)0.0276 (11)0.0114 (10)0.0300 (10)
N50.0539 (14)0.0555 (13)0.0393 (12)0.0311 (11)0.0121 (10)0.0294 (10)
Geometric parameters (Å, º) top
C1—N11.311 (3)C4—H4A0.9600
C1—N31.352 (3)C4—H4B0.9600
C1—C41.468 (3)C4—H4C0.9600
C2—N41.312 (3)N3—H30.862 (11)
C2—N21.337 (3)N4—H4D0.8600
C2—N11.369 (3)N4—H4E0.8600
C3—N51.308 (3)N5—H5A0.8600
C3—N21.341 (3)N5—H5B0.8600
C3—N31.363 (3)
N1—C1—N3122.0 (2)H4A—C4—H4C109.5
N1—C1—C4120.7 (2)H4B—C4—H4C109.5
N3—C1—C4117.3 (2)C1—N1—C2115.85 (19)
N4—C2—N2119.4 (2)C2—N2—C3116.07 (18)
N4—C2—N1115.07 (19)C1—N3—C3119.81 (19)
N2—C2—N1125.6 (2)C1—N3—H3115 (2)
N5—C3—N2120.5 (2)C3—N3—H3124 (2)
N5—C3—N3118.8 (2)C2—N4—H4D120.0
N2—C3—N3120.7 (2)C2—N4—H4E120.0
C1—C4—H4A109.5H4D—N4—H4E120.0
C1—C4—H4B109.5C3—N5—H5A120.0
H4A—C4—H4B109.5C3—N5—H5B120.0
C1—C4—H4C109.5H5A—N5—H5B120.0
N3—C1—N1—C20.9 (3)N5—C3—N2—C2179.7 (2)
C4—C1—N1—C2179.6 (2)N3—C3—N2—C21.3 (3)
N4—C2—N1—C1179.9 (2)N1—C1—N3—C31.6 (4)
N2—C2—N1—C10.3 (3)C4—C1—N3—C3178.8 (2)
N4—C2—N2—C3179.9 (2)N5—C3—N3—C1179.1 (2)
N1—C2—N2—C30.6 (3)N2—C3—N3—C11.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···Cl1i0.86 (1)2.25 (1)3.107 (2)174 (3)
N4—H4D···Cl1ii0.862.523.372 (2)169
N4—H4E···N1iii0.862.323.171 (3)170
N5—H5A···N2ii0.862.153.008 (3)174
N5—H5B···Cl10.862.403.125 (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 formulaC4H8N5+·Cl
Mr161.60
Crystal system, space groupTriclinic, 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)
V3)354.61 (12)
Z2
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.16 × 0.14 × 0.10
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.929, 0.955
No. of measured, independent and
observed [I > 2σ(I)] reflections
1871, 1303, 1042
Rint0.082
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.111, 1.07
No. of reflections1303
No. of parameters96
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.28

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···Cl1i0.862 (11)2.248 (11)3.107 (2)174 (3)
N4—H4D···Cl1ii0.862.523.372 (2)169
N4—H4E···N1iii0.862.323.171 (3)170
N5—H5A···N2ii0.862.153.008 (3)174
N5—H5B···Cl10.862.403.125 (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

First citationBruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationDelori, A., Suresh, E. & Pedireddi, V.-R. (2008). Chem. Eur. J. 14, 6967–6977.  Web of Science CSD CrossRef PubMed CAS
First citationFan, Y., You, W., Qian, H.-F., Liu, J.-L. & Huang, W. (2009). Acta Cryst. E65, o494.  Web of Science CSD CrossRef IUCr Journals
First citationPerpétuo, G. J. & Janczak, J. (2007). Acta Cryst. C63, o271–o273.  Web of Science CSD CrossRef IUCr Journals
First citationPortalone, G. & Colapietro, M. (2007). Acta Cryst. C63, o655–o658.  Web of Science CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWijaya, K., Moers, O., Henschel, D., Blaschette, A. & Jones, P.-G. (2004). Z. Naturforsch. Teil. B, 59, 747–756.  CAS

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