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

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.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.039
• wR factor = 0.111
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.44
PLAT432_ALERT_2_C Short Inter X...Y Contact  C4     ..  C4      ..       3.10 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         17
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          3

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	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

Crystal data

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) Å^3

Data collection

Bruker SMART 1K CCD area-detector diffractometer	1303 independent reflections
Radiation source: sealed tube	1042 reflections with I > 2σ(I)
Graphite monochromator	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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: difference Fourier map
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0566P)^2] where P = (Fo^2 + 2Fc^2)/3
1303 reflections	(Δ/σ)max < 0.001
96 parameters	Δρmax = 0.25 e Å^−3
2 restraints	Δρmin = −0.28 e Å^−3

Special details

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 (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl1^i	0.86 (1)	2.25 (1)	3.107 (2)	174 (3)
N4—H4D···Cl1^ii	0.86	2.52	3.372 (2)	169
N4—H4E···N1^iii	0.86	2.32	3.171 (3)	170
N5—H5A···N2^ii	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.