Acta Cryst. (2010). E66, o759 [ doi:10.1107/S1600536810007907 ]
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-HN hydrogen bonds are found between adjacent cations, forming another type of eight-membered [R22(8)] hydrogen-bonded ring.
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.
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.
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).
![[Figure 1]](./nk2023fig1thm.gif)
| 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]](./nk2023fig2thm.gif)
| 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.] |
| C4H8N5+·Cl− | Z = 2 |
| Mr = 161.60 | F(000) = 168 |
| Triclinic, P1 | Dx = 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 |
| Bruker SMART 1K CCD area-detector diffractometer | 1303 independent reflections |
| Radiation source: sealed tube | 1042 reflections with I > 2σ(I) |
| graphite | Rint = 0.082 |
| ω scans | θmax = 25.5°, θmin = 2.4° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→6 |
| Tmin = 0.929, Tmax = 0.955 | k = −9→8 |
| 1871 measured reflections | l = −11→11 |
| 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(Fo2) + (0.0566P)2] where P = (Fo2 + 2Fc2)/3 |
| 1303 reflections | (Δ/σ)max < 0.001 |
| 96 parameters | Δρmax = 0.25 e Å−3 |
| 2 restraints | Δρmin = −0.28 e Å−3 |
| C4H8N5+·Cl− | γ = 71.027 (2)° |
| Mr = 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)° |
| 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 = 0.955 | Rint = 0.082 |
| 1871 measured reflections | θmax = 25.5° |
| R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.111 | Δρmax = 0.25 e Å−3 |
| S = 1.07 | Δρmin = −0.28 e Å−3 |
| 1303 reflections | Absolute structure: ? |
| 96 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| 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)* |
| 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) |
| 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) |
| 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. |
| 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. |
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.
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Delori, A., Suresh, E. & Pedireddi, V.-R. (2008). Chem. Eur. J. 14, 6967–6977.
Fan, Y., You, W., Qian, H.-F., Liu, J.-L. & Huang, W. (2009). Acta Cryst. E65, o494.
Perpétuo, G. J. & Janczak, J. (2007). Acta Cryst. C63, o271–o273.
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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).