organic compounds
2,4-Diamino-6-methyl-1,3,5-triazine methanol solvate
aDepartment of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland
*Correspondence e-mail: mkubicki@amu.edu.pl
The 4H7N5·CH4O, is determined by an extensive network of hydrogen bonding. A sequence of centrosymmetric dimeric associations, formed by two different N—H(amino)⋯N(ring) hydrogen bonds, connects the triazine rings into a planar molecular tape. The methanol solvent molecules act as di-acceptors and mono-donors of hydrogen bonds and interlink, almost perpendicularly, the hydrogen-bonded tapes into a three-dimensional structure.
of the title compound, CRelated literature
For related literature, see: Allen (2002); Radecka-Paryzek et al. (2005); Šebenik et al. (1989); Tashiro & Oiwa (1981).
Experimental
Crystal data
|
Data collection
|
Refinement
|
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S160053680706607X/rz2183sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706607X/rz2183Isup2.hkl
To a solution of lanthanum(III) nitrate complex of Schiff base ligand, product of [2 + 1] condensation of one molecule of 2,4-diamino-6-methyl-1,3,5-triazine with two molecules of 2,6-diacetylpyridine (0.1 mmol), in methanol (10 ml), 2,4-diamino-6-methyl-1,3,5-triazine (0.1 mmol) dissolved in hot methanol (10 ml) was added in order to receive the [2 + 2] Schiff base macrocyclic complex. After standing at room temperature for several hours, transparent crystals of the title compound were obtained. The crystals were initially transparent but after few minutes in open air they became opaque and gradually lost their crystallinity. Therefore the crystal used for data collection was sealed in a glass capillary.
The methyl hydrogen atoms were positioned geometrically (AFIX 137) and refined using a riding model, with Uiso(H) = 1.3 Ueq(C). All other hydrogen atoms were located in difference Fourier maps and freely refined.
Triazine compounds are used in pharmaceutical industry as coupling agents for the synthesis of
and as side chain of antibiotics, as well as in formulating bactericides and fungicides. 2,4-Diamino-6-methyl-1,3,5-triazine (acetoguanamine) is used as an intermediate for pharmaceuticals and as a modifier and flexibilizer of formaldehyde resins (Šebenik et al. 1989, Tashiro et al.1981). The title compound, 2,4-diamino-6-methyl-1,3,5-triazine methanol solvate, was isolated during the efforts to prepare new lanthanide macrocyclic complexes as part of our research program involving the study of the coordination template effect in generating the supramolecular Schiff base macrocycles derived from various diamines and dicarbonyls (Radecka-Paryzek et al. 2005).The bond lengths within the ring are exceptionally uniform in all the 2,4-diaminotriazine derivatives. For 38 compounds found in the CSD (Allen, 2002; search conditions: only organics, no disorder, no errors) the mean standard deviation of the C?N bond lengths is as small as 0.007 Å. The same is true for the title compound, the mean value of the C?N bond distances being 1.346 (14) Å. The triazine ring is planar (Fig. 1), with a maximum deviation from the least-squares plane of 0.013 (1)Å for N5. The amino groups are almost coplanar with the ring plane, the dihedral angles between the NH2 groups and the ring plane are 6(3)° for N2H2 and 2(2)° for N4H2. Only the methyl carbon atom C61 deviates significantly from the plane by 0.055 (3) Å.
The
is determined by an extensive network of hydrogen bonds. Each NH2 group acts as a donor in hydrogen bond with the ring nitrogen atoms of neighboring molecules, related by two different centres of symmetry. The sequence of such hydrogen-bonded dimers creates an almost planar molecular tape of molecules along the [101] direction (Fig. 2). The tapes are interlinked by hydrogen bonds with the methanol solvent molecules, which act as di-acceptors and mono-donors of hydrogen bonds (Fig. 3). As a result, a three-dimensional structure of almost perpendicular tapes is formed in the crystal.For related literature, see: Allen (2002); Radecka-Paryzek et al. (2005); Šebenik et al. (1989); Tashiro & Oiwa (1981).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell
CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989) and WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).Fig. 1. Anisotropic displacement ellipsoid representation (at the 50% probability level) of the molecule of the title compound, together with the numbering scheme. The hydrogen atoms are drawn as spheres with arbitrary radii. The intermolecular hydrogen bond is depicted as a dashed line. | |
Fig. 2. The molecular tape along [101] direction. Hydrogen bonds are depicted as dashed lines. Symmetry codes: (i) x,y,z (ii) -x,2 - y,-2z (iii) 1/2 - x,5/2 - y,2 - z (iv) 1/2 + x,1/2 + y,z. | |
Fig. 3. The packing of the molecules as seen approximately along the a axis. Hydrogen bonds are shown as dashed lines. |
C4H7N5·CH4O | F(000) = 672 |
Mr = 157.19 | Dx = 1.285 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2082 reflections |
a = 21.024 (5) Å | θ = 4–22° |
b = 5.4726 (10) Å | µ = 0.10 mm−1 |
c = 14.198 (3) Å | T = 295 K |
β = 95.66 (2)° | Block, colourless |
V = 1625.6 (6) Å3 | 0.4 × 0.2 × 0.2 mm |
Z = 8 |
Kuma KM-4-CCD four-circle diffractometer | 1191 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 27.0°, θmin = 2.9° |
Detector resolution: 8.1929 pixels mm-1 | h = −26→26 |
ω scans | k = −4→6 |
5226 measured reflections | l = −18→18 |
1737 independent reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0834P)2 + 0.3526P] where P = (Fo2 + 2Fc2)/3 |
1737 reflections | (Δ/σ)max = 0.001 |
122 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C4H7N5·CH4O | V = 1625.6 (6) Å3 |
Mr = 157.19 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.024 (5) Å | µ = 0.10 mm−1 |
b = 5.4726 (10) Å | T = 295 K |
c = 14.198 (3) Å | 0.4 × 0.2 × 0.2 mm |
β = 95.66 (2)° |
Kuma KM-4-CCD four-circle diffractometer | 1191 reflections with I > 2σ(I) |
5226 measured reflections | Rint = 0.019 |
1737 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.17 e Å−3 |
1737 reflections | Δρmin = −0.29 e Å−3 |
122 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 | ||
N1 | 0.19697 (6) | 1.0111 (2) | 0.94292 (10) | 0.0405 (4) | |
C2 | 0.14975 (8) | 1.1070 (3) | 0.99110 (11) | 0.0375 (4) | |
N2 | 0.16650 (8) | 1.2910 (3) | 1.04951 (12) | 0.0491 (4) | |
H2B | 0.1372 (12) | 1.360 (4) | 1.0792 (17) | 0.069 (7)* | |
H2A | 0.2049 (11) | 1.346 (4) | 1.0518 (15) | 0.056 (6)* | |
N3 | 0.08942 (6) | 1.0268 (3) | 0.98441 (10) | 0.0410 (4) | |
C4 | 0.07625 (8) | 0.8402 (3) | 0.92379 (12) | 0.0400 (4) | |
N4 | 0.01687 (8) | 0.7548 (3) | 0.91381 (14) | 0.0576 (5) | |
H4B | 0.0074 (11) | 0.634 (4) | 0.8728 (16) | 0.065 (7)* | |
H4A | −0.0141 (11) | 0.813 (4) | 0.9441 (16) | 0.055 (6)* | |
N5 | 0.11934 (6) | 0.7355 (3) | 0.87109 (10) | 0.0412 (4) | |
C6 | 0.17841 (8) | 0.8266 (3) | 0.88561 (12) | 0.0388 (4) | |
C61 | 0.22793 (9) | 0.7086 (4) | 0.83245 (15) | 0.0521 (5) | |
H61A | 0.2682 | 0.7898 | 0.8472 | 0.068* | |
H61B | 0.2154 | 0.7205 | 0.7657 | 0.068* | |
H61C | 0.2321 | 0.5397 | 0.8502 | 0.068* | |
O1S | 0.08620 (7) | 0.4874 (2) | 0.69953 (10) | 0.0574 (4) | |
H1S | 0.0976 (14) | 0.579 (6) | 0.756 (3) | 0.113 (11)* | |
C1S | 0.08937 (12) | 0.2368 (4) | 0.71909 (17) | 0.0707 (7) | |
H1S1 | 0.1329 | 0.1916 | 0.7380 | 0.092* | |
H1S2 | 0.0739 | 0.1469 | 0.6634 | 0.092* | |
H1S3 | 0.0635 | 0.2000 | 0.7693 | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0315 (7) | 0.0499 (8) | 0.0406 (8) | −0.0021 (6) | 0.0066 (6) | −0.0054 (6) |
C2 | 0.0315 (8) | 0.0475 (9) | 0.0331 (8) | −0.0026 (7) | 0.0021 (6) | −0.0012 (7) |
N2 | 0.0350 (8) | 0.0597 (10) | 0.0532 (10) | −0.0065 (7) | 0.0078 (7) | −0.0180 (8) |
N3 | 0.0327 (8) | 0.0499 (8) | 0.0412 (8) | −0.0050 (6) | 0.0078 (6) | −0.0053 (6) |
C4 | 0.0344 (9) | 0.0465 (9) | 0.0397 (9) | −0.0035 (7) | 0.0056 (7) | −0.0003 (7) |
N4 | 0.0382 (9) | 0.0674 (11) | 0.0689 (11) | −0.0150 (8) | 0.0135 (8) | −0.0252 (10) |
N5 | 0.0387 (8) | 0.0436 (8) | 0.0419 (8) | −0.0041 (6) | 0.0068 (6) | −0.0049 (6) |
C6 | 0.0365 (9) | 0.0442 (9) | 0.0358 (9) | 0.0014 (7) | 0.0034 (7) | 0.0019 (7) |
C61 | 0.0441 (10) | 0.0601 (11) | 0.0534 (11) | 0.0022 (9) | 0.0113 (8) | −0.0105 (9) |
O1S | 0.0728 (10) | 0.0551 (8) | 0.0426 (8) | 0.0036 (7) | −0.0031 (7) | 0.0031 (6) |
C1S | 0.0870 (18) | 0.0544 (13) | 0.0731 (15) | −0.0019 (11) | 0.0203 (13) | −0.0045 (11) |
N1—C6 | 1.331 (2) | N5—C6 | 1.335 (2) |
N1—C2 | 1.365 (2) | C6—C61 | 1.492 (2) |
C2—N2 | 1.330 (2) | C61—H61A | 0.9600 |
C2—N3 | 1.337 (2) | C61—H61B | 0.9600 |
N2—H2B | 0.87 (3) | C61—H61C | 0.9600 |
N2—H2A | 0.86 (2) | O1S—C1S | 1.400 (2) |
N3—C4 | 1.347 (2) | O1S—H1S | 0.96 (4) |
C4—N4 | 1.328 (2) | C1S—H1S1 | 0.9600 |
C4—N5 | 1.358 (2) | C1S—H1S2 | 0.9600 |
N4—H4B | 0.89 (2) | C1S—H1S3 | 0.9600 |
N4—H4A | 0.88 (2) | ||
C6—N1—C2 | 114.47 (14) | N1—C6—C61 | 117.42 (15) |
N2—C2—N3 | 118.93 (16) | N5—C6—C61 | 116.44 (16) |
N2—C2—N1 | 116.28 (15) | C6—C61—H61A | 109.5 |
N3—C2—N1 | 124.78 (16) | C6—C61—H61B | 109.5 |
C2—N2—H2B | 118.5 (17) | H61A—C61—H61B | 109.5 |
C2—N2—H2A | 118.6 (14) | C6—C61—H61C | 109.5 |
H2B—N2—H2A | 123 (2) | H61A—C61—H61C | 109.5 |
C2—N3—C4 | 115.34 (14) | H61B—C61—H61C | 109.5 |
N4—C4—N3 | 117.85 (16) | C1S—O1S—H1S | 110 (2) |
N4—C4—N5 | 117.65 (17) | O1S—C1S—H1S1 | 109.5 |
N3—C4—N5 | 124.49 (15) | O1S—C1S—H1S2 | 109.5 |
C4—N4—H4B | 118.5 (15) | H1S1—C1S—H1S2 | 109.5 |
C4—N4—H4A | 123.7 (14) | O1S—C1S—H1S3 | 109.5 |
H4B—N4—H4A | 118 (2) | H1S1—C1S—H1S3 | 109.5 |
C6—N5—C4 | 114.73 (15) | H1S2—C1S—H1S3 | 109.5 |
N1—C6—N5 | 126.14 (15) | ||
C6—N1—C2—N2 | 179.66 (15) | N4—C4—N5—C6 | −178.87 (16) |
C6—N1—C2—N3 | 0.7 (2) | N3—C4—N5—C6 | 2.1 (3) |
N2—C2—N3—C4 | 179.99 (16) | C2—N1—C6—N5 | 1.3 (2) |
N1—C2—N3—C4 | −1.1 (3) | C2—N1—C6—C61 | −178.50 (15) |
C2—N3—C4—N4 | −179.45 (16) | C4—N5—C6—N1 | −2.6 (3) |
C2—N3—C4—N5 | −0.4 (3) | C4—N5—C6—C61 | 177.21 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1S—H1S···N5 | 0.96 (4) | 1.86 (4) | 2.816 (2) | 176 (3) |
N2—H2B···O1Si | 0.87 (3) | 2.26 (3) | 3.093 (2) | 160 (2) |
N2—H2A···N1ii | 0.86 (2) | 2.20 (2) | 3.060 (2) | 180 (2) |
N4—H4B···O1Siii | 0.89 (2) | 2.27 (2) | 2.956 (2) | 133.2 (19) |
N4—H4A···N3iv | 0.88 (2) | 2.15 (2) | 3.024 (2) | 177.3 (19) |
Symmetry codes: (i) x, −y+2, z+1/2; (ii) −x+1/2, −y+5/2, −z+2; (iii) −x, y, −z+3/2; (iv) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C4H7N5·CH4O |
Mr | 157.19 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 21.024 (5), 5.4726 (10), 14.198 (3) |
β (°) | 95.66 (2) |
V (Å3) | 1625.6 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.4 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Kuma KM-4-CCD four-circle |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5226, 1737, 1191 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.146, 1.07 |
No. of reflections | 1737 |
No. of parameters | 122 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.29 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Stereochemical Workstation Operation Manual (Siemens, 1989) and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1S—H1S···N5 | 0.96 (4) | 1.86 (4) | 2.816 (2) | 176 (3) |
N2—H2B···O1Si | 0.87 (3) | 2.26 (3) | 3.093 (2) | 160 (2) |
N2—H2A···N1ii | 0.86 (2) | 2.20 (2) | 3.060 (2) | 180 (2) |
N4—H4B···O1Siii | 0.89 (2) | 2.27 (2) | 2.956 (2) | 133.2 (19) |
N4—H4A···N3iv | 0.88 (2) | 2.15 (2) | 3.024 (2) | 177.3 (19) |
Symmetry codes: (i) x, −y+2, z+1/2; (ii) −x+1/2, −y+5/2, −z+2; (iii) −x, y, −z+3/2; (iv) −x, −y+2, −z+2. |
Acknowledgements
This work was supported by the Ministry of Science and Higher Education (grant No. N204 03117 33).
References
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Oxford Diffraction (2006). CrysAlis CCD (Version 1.171.31.5) and CrysAlis RED (Version 1.171.31.5). Oxford Diffraction Poland Sp. z o.o., Wrocław, Poland. Google Scholar
Radecka-Paryzek, W., Patroniak, V. & Lisowski, J. (2005). Coord. Chem. Rev. 249, 2156–2175. Web of Science CrossRef CAS Google Scholar
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Triazine compounds are used in pharmaceutical industry as coupling agents for the synthesis of peptides and as side chain of antibiotics, as well as in formulating bactericides and fungicides. 2,4-Diamino-6-methyl-1,3,5-triazine (acetoguanamine) is used as an intermediate for pharmaceuticals and as a modifier and flexibilizer of formaldehyde resins (Šebenik et al. 1989, Tashiro et al.1981). The title compound, 2,4-diamino-6-methyl-1,3,5-triazine methanol solvate, was isolated during the efforts to prepare new lanthanide macrocyclic complexes as part of our research program involving the study of the coordination template effect in generating the supramolecular Schiff base macrocycles derived from various diamines and dicarbonyls (Radecka-Paryzek et al. 2005).
The bond lengths within the ring are exceptionally uniform in all the 2,4-diaminotriazine derivatives. For 38 compounds found in the CSD (Allen, 2002; search conditions: only organics, no disorder, no errors) the mean standard deviation of the C?N bond lengths is as small as 0.007 Å. The same is true for the title compound, the mean value of the C?N bond distances being 1.346 (14) Å. The triazine ring is planar (Fig. 1), with a maximum deviation from the least-squares plane of 0.013 (1)Å for N5. The amino groups are almost coplanar with the ring plane, the dihedral angles between the NH2 groups and the ring plane are 6(3)° for N2H2 and 2(2)° for N4H2. Only the methyl carbon atom C61 deviates significantly from the plane by 0.055 (3) Å.
The crystal structure is determined by an extensive network of hydrogen bonds. Each NH2 group acts as a donor in hydrogen bond with the ring nitrogen atoms of neighboring molecules, related by two different centres of symmetry. The sequence of such hydrogen-bonded dimers creates an almost planar molecular tape of molecules along the [101] direction (Fig. 2). The tapes are interlinked by hydrogen bonds with the methanol solvent molecules, which act as di-acceptors and mono-donors of hydrogen bonds (Fig. 3). As a result, a three-dimensional structure of almost perpendicular tapes is formed in the crystal.