Acta Cryst. (2008). E64, o1893 [ doi:10.1107/S1600536808028146 ]
The asymmetric unit of the title compound, 2C4H8N4·3H2O, contains two crystallographically independent 4-amino-3,5-dimethyl-1,2,4-triazole molecules and three water molecules. The structure exhibits N-H
O, O-HN and O-HO hydrogen bonds.
To a solution of mta (mta = 4-amino-3,5-dimethyl-1,2,4-triazole) (0.0228 g, 0.2 mmol) in CH3OH (5 ml), an aqueous solution (5 ml) of MnSO4.H2O (0.0169 g, 0.1 mmol) was added. The mixture was stirred for half an hour and filtered. The filtrate was allowed to evaporate slowly at room temperature. After several days, colorless block crystals were obtained in 5% yield (0.0007 g) based on mta.
H atoms bonded to O and N atoms were located in a difference map and freely refined. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.96 Å and with Uiso(H) = 1.5Uiso(C).
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bt2782fig1thm.gif)
| Fig. 1. The asymmetric unit of the title compound with 30% thermal ellipsoids. |
![[Figure 2]](./bt2782fig2thm.gif)
| Fig. 2. The three-dimensional supramolecular network of the title compound. The H atoms bonded to C atoms are omitted for clarity. |
| 2C4H8N4·3H2O | Z = 2 |
| Mr = 278.34 | F(000) = 300 |
| Triclinic, P1 | Dx = 1.225 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.194 (4) Å | Cell parameters from 785 reflections |
| b = 8.680 (4) Å | θ = 2.4–28.0° |
| c = 13.592 (7) Å | µ = 0.10 mm−1 |
| α = 72.332 (8)° | T = 293 K |
| β = 84.993 (8)° | Block, colourless |
| γ = 68.936 (7)° | 0.20 × 0.18 × 0.17 mm |
| V = 754.5 (6) Å3 |
| Bruker APEX CCD diffractometer | 2904 independent reflections |
| Radiation source: fine-focus sealed tube | 2447 reflections with I > 2σ(I) |
| graphite | Rint = 0.014 |
| φ and ω scan | θmax = 26.0°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −8→8 |
| Tmin = 0.981, Tmax = 0.984 | k = −10→10 |
| 5166 measured reflections | l = −16→12 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.0782P)2 + 0.0952P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 2904 reflections | Δρmax = 0.27 e Å−3 |
| 213 parameters | Δρmin = −0.22 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.151 (12) |
| 2C4H8N4·3H2O | γ = 68.936 (7)° |
| Mr = 278.34 | V = 754.5 (6) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.194 (4) Å | Mo Kα radiation |
| b = 8.680 (4) Å | µ = 0.10 mm−1 |
| c = 13.592 (7) Å | T = 293 K |
| α = 72.332 (8)° | 0.20 × 0.18 × 0.17 mm |
| β = 84.993 (8)° |
| Bruker APEX CCD diffractometer | 2904 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2447 reflections with I > 2σ(I) |
| Tmin = 0.981, Tmax = 0.984 | Rint = 0.014 |
| 5166 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.137 | Δρmax = 0.27 e Å−3 |
| S = 1.03 | Δρmin = −0.22 e Å−3 |
| 2904 reflections | Absolute structure: ? |
| 213 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| C1 | 0.2307 (2) | 0.21698 (19) | 0.03818 (12) | 0.0464 (4) | |
| C2 | 0.2155 (3) | 0.3435 (2) | 0.09351 (15) | 0.0675 (5) | |
| H2A | 0.2195 | 0.4487 | 0.0448 | 0.101* | |
| H2B | 0.3249 | 0.2973 | 0.1422 | 0.101* | |
| H2C | 0.0922 | 0.3666 | 0.1295 | 0.101* | |
| C3 | 0.2508 (2) | −0.02273 (19) | 0.01050 (12) | 0.0450 (4) | |
| C4 | 0.2584 (3) | −0.2021 (2) | 0.02881 (14) | 0.0574 (4) | |
| H4A | 0.2743 | −0.2287 | −0.0357 | 0.086* | |
| H4B | 0.1369 | −0.2134 | 0.0596 | 0.086* | |
| H4C | 0.3691 | −0.2805 | 0.0744 | 0.086* | |
| C5 | 0.2491 (2) | 0.3310 (2) | −0.54342 (13) | 0.0518 (4) | |
| C6 | 0.2507 (4) | 0.2018 (3) | −0.59340 (17) | 0.0790 (6) | |
| H6A | 0.2633 | 0.0947 | −0.5416 | 0.119* | |
| H6B | 0.3612 | 0.1843 | −0.6389 | 0.119* | |
| H6C | 0.1286 | 0.2421 | −0.6324 | 0.119* | |
| C7 | 0.2362 (2) | 0.5735 (2) | −0.52294 (12) | 0.0500 (4) | |
| C8 | 0.2197 (3) | 0.7564 (2) | −0.54624 (15) | 0.0691 (5) | |
| H8A | 0.2259 | 0.7821 | −0.4830 | 0.104* | |
| H8B | 0.0951 | 0.8304 | −0.5817 | 0.104* | |
| H8C | 0.3274 | 0.7752 | −0.5892 | 0.104* | |
| N1 | 0.2638 (2) | 0.08533 (18) | −0.07827 (10) | 0.0528 (4) | |
| N2 | 0.2508 (2) | 0.23853 (17) | −0.06052 (10) | 0.0533 (4) | |
| N3 | 0.22893 (18) | 0.05496 (15) | 0.08561 (9) | 0.0433 (3) | |
| N4 | 0.2136 (3) | −0.02566 (19) | 0.19138 (10) | 0.0543 (4) | |
| H4D | 0.100 (3) | 0.047 (3) | 0.2139 (15) | 0.071 (6)* | |
| H4E | 0.320 (3) | −0.030 (3) | 0.2220 (15) | 0.071 (6)* | |
| N5 | 0.2546 (2) | 0.46293 (18) | −0.43183 (10) | 0.0568 (4) | |
| N6 | 0.2637 (2) | 0.30785 (18) | −0.44498 (11) | 0.0579 (4) | |
| N7 | 0.2326 (2) | 0.49581 (17) | −0.59485 (9) | 0.0511 (4) | |
| N8 | 0.2096 (4) | 0.5651 (3) | −0.70320 (12) | 0.0790 (6) | |
| H8D | 0.105 (4) | 0.659 (4) | −0.710 (2) | 0.109 (10)* | |
| H8E | 0.325 (5) | 0.589 (4) | −0.726 (2) | 0.119 (10)* | |
| O1W | −0.1595 (3) | 0.1723 (3) | 0.26863 (18) | 0.1022 (7) | |
| H1WA | −0.219 (5) | 0.280 (4) | 0.254 (2) | 0.132 (12)* | |
| H1WB | −0.248 (5) | 0.128 (4) | 0.254 (2) | 0.131 (11)* | |
| O2W | 0.3524 (2) | 0.47375 (18) | −0.23848 (12) | 0.0706 (4) | |
| H2WA | 0.308 (4) | 0.412 (3) | −0.186 (2) | 0.090 (7)* | |
| H2WB | 0.308 (4) | 0.466 (3) | −0.296 (2) | 0.101 (8)* | |
| O3W | 0.3962 (2) | 0.02300 (16) | −0.26616 (11) | 0.0610 (4) | |
| H3WA | 0.341 (3) | 0.055 (3) | −0.2121 (18) | 0.079 (6)* | |
| H3WB | 0.349 (4) | 0.114 (3) | −0.321 (2) | 0.093 (8)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0471 (8) | 0.0429 (8) | 0.0438 (8) | −0.0139 (6) | −0.0002 (6) | −0.0069 (6) |
| C2 | 0.0849 (13) | 0.0529 (10) | 0.0645 (11) | −0.0241 (9) | −0.0015 (10) | −0.0161 (9) |
| C3 | 0.0393 (7) | 0.0485 (8) | 0.0455 (8) | −0.0143 (6) | 0.0017 (6) | −0.0128 (7) |
| C4 | 0.0574 (10) | 0.0543 (10) | 0.0636 (11) | −0.0213 (8) | 0.0020 (8) | −0.0198 (8) |
| C5 | 0.0514 (9) | 0.0550 (9) | 0.0478 (9) | −0.0184 (7) | 0.0075 (7) | −0.0152 (7) |
| C6 | 0.0942 (15) | 0.0765 (13) | 0.0778 (14) | −0.0334 (11) | 0.0145 (11) | −0.0378 (11) |
| C7 | 0.0513 (9) | 0.0539 (9) | 0.0444 (9) | −0.0212 (7) | 0.0050 (7) | −0.0115 (7) |
| C8 | 0.0833 (13) | 0.0610 (11) | 0.0660 (12) | −0.0345 (10) | 0.0060 (10) | −0.0129 (9) |
| N1 | 0.0571 (8) | 0.0584 (8) | 0.0431 (7) | −0.0227 (6) | 0.0055 (6) | −0.0134 (6) |
| N2 | 0.0589 (8) | 0.0512 (8) | 0.0455 (8) | −0.0221 (6) | 0.0029 (6) | −0.0053 (6) |
| N3 | 0.0445 (7) | 0.0430 (7) | 0.0374 (7) | −0.0144 (5) | 0.0013 (5) | −0.0060 (5) |
| N4 | 0.0632 (9) | 0.0543 (8) | 0.0378 (7) | −0.0206 (7) | 0.0038 (7) | −0.0034 (6) |
| N5 | 0.0697 (9) | 0.0578 (8) | 0.0427 (8) | −0.0249 (7) | 0.0031 (6) | −0.0119 (6) |
| N6 | 0.0709 (9) | 0.0516 (8) | 0.0467 (8) | −0.0213 (7) | 0.0030 (6) | −0.0086 (6) |
| N7 | 0.0565 (8) | 0.0584 (8) | 0.0368 (7) | −0.0242 (6) | 0.0045 (6) | −0.0080 (6) |
| N8 | 0.1082 (16) | 0.0910 (14) | 0.0374 (8) | −0.0448 (13) | 0.0018 (9) | −0.0062 (8) |
| O1W | 0.0737 (10) | 0.0831 (12) | 0.170 (2) | −0.0312 (9) | 0.0195 (10) | −0.0655 (13) |
| O2W | 0.1040 (11) | 0.0668 (9) | 0.0514 (8) | −0.0482 (8) | −0.0005 (7) | −0.0090 (6) |
| O3W | 0.0781 (9) | 0.0496 (7) | 0.0488 (7) | −0.0161 (6) | 0.0067 (6) | −0.0143 (6) |
| C1—N2 | 1.300 (2) | C7—N7 | 1.352 (2) |
| C1—N3 | 1.362 (2) | C7—C8 | 1.483 (2) |
| C1—C2 | 1.478 (2) | C8—H8A | 0.9600 |
| C2—H2A | 0.9600 | C8—H8B | 0.9600 |
| C2—H2B | 0.9600 | C8—H8C | 0.9600 |
| C2—H2C | 0.9600 | N1—N2 | 1.391 (2) |
| C3—N1 | 1.304 (2) | N3—N4 | 1.4091 (18) |
| C3—N3 | 1.355 (2) | N4—H4D | 0.93 (2) |
| C3—C4 | 1.482 (2) | N4—H4E | 0.88 (2) |
| C4—H4A | 0.9600 | N5—N6 | 1.389 (2) |
| C4—H4B | 0.9600 | N7—N8 | 1.411 (2) |
| C4—H4C | 0.9600 | N8—H8D | 0.88 (3) |
| C5—N6 | 1.299 (2) | N8—H8E | 0.93 (3) |
| C5—N7 | 1.354 (2) | O1W—H1WA | 0.84 (3) |
| C5—C6 | 1.474 (3) | O1W—H1WB | 0.92 (3) |
| C6—H6A | 0.9600 | O2W—H2WA | 0.87 (3) |
| C6—H6B | 0.9600 | O2W—H2WB | 0.90 (3) |
| C6—H6C | 0.9600 | O3W—H3WA | 0.88 (2) |
| C7—N5 | 1.299 (2) | O3W—H3WB | 0.89 (3) |
| N2—C1—N3 | 109.30 (14) | N5—C7—C8 | 126.38 (16) |
| N2—C1—C2 | 126.85 (15) | N7—C7—C8 | 124.62 (15) |
| N3—C1—C2 | 123.85 (15) | C7—C8—H8A | 109.5 |
| C1—C2—H2A | 109.5 | C7—C8—H8B | 109.5 |
| C1—C2—H2B | 109.5 | H8A—C8—H8B | 109.5 |
| H2A—C2—H2B | 109.5 | C7—C8—H8C | 109.5 |
| C1—C2—H2C | 109.5 | H8A—C8—H8C | 109.5 |
| H2A—C2—H2C | 109.5 | H8B—C8—H8C | 109.5 |
| H2B—C2—H2C | 109.5 | C3—N1—N2 | 107.78 (13) |
| N1—C3—N3 | 109.02 (14) | C1—N2—N1 | 107.36 (12) |
| N1—C3—C4 | 126.61 (15) | C3—N3—C1 | 106.55 (13) |
| N3—C3—C4 | 124.37 (14) | C3—N3—N4 | 124.23 (13) |
| C3—C4—H4A | 109.5 | C1—N3—N4 | 129.20 (13) |
| C3—C4—H4B | 109.5 | N3—N4—H4D | 106.6 (12) |
| H4A—C4—H4B | 109.5 | N3—N4—H4E | 105.8 (13) |
| C3—C4—H4C | 109.5 | H4D—N4—H4E | 109.1 (17) |
| H4A—C4—H4C | 109.5 | C7—N5—N6 | 107.56 (14) |
| H4B—C4—H4C | 109.5 | C5—N6—N5 | 107.64 (13) |
| N6—C5—N7 | 108.89 (15) | C7—N7—C5 | 106.91 (14) |
| N6—C5—C6 | 126.70 (17) | C7—N7—N8 | 129.47 (15) |
| N7—C5—C6 | 124.41 (16) | C5—N7—N8 | 123.59 (15) |
| C5—C6—H6A | 109.5 | N7—N8—H8D | 102.0 (18) |
| C5—C6—H6B | 109.5 | N7—N8—H8E | 105.6 (17) |
| H6A—C6—H6B | 109.5 | H8D—N8—H8E | 112 (3) |
| C5—C6—H6C | 109.5 | H1WA—O1W—H1WB | 106 (3) |
| H6A—C6—H6C | 109.5 | H2WA—O2W—H2WB | 107 (2) |
| H6B—C6—H6C | 109.5 | H3WA—O3W—H3WB | 107 (2) |
| N5—C7—N7 | 109.00 (15) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4D···O1W | 0.93 (2) | 2.00 (2) | 2.924 (3) | 170.9 (18) |
| N4—H4E···O3Wi | 0.88 (2) | 2.21 (2) | 3.078 (3) | 168.3 (18) |
| N8—H8E···O2Wii | 0.93 (3) | 2.23 (3) | 3.104 (3) | 156 (2) |
| O1W—H1WA···O2Wiii | 0.84 (3) | 1.95 (3) | 2.793 (3) | 173 (3) |
| O1W—H1WB···O3Wiv | 0.92 (3) | 1.93 (3) | 2.810 (2) | 160 (3) |
| O2W—H2WA···N2 | 0.87 (3) | 2.02 (3) | 2.885 (2) | 171 (2) |
| O2W—H2WB···N5 | 0.90 (3) | 1.93 (3) | 2.816 (2) | 168 (2) |
| O3W—H3WA···N1 | 0.88 (2) | 1.92 (2) | 2.787 (2) | 168 (2) |
| O3W—H3WB···N6 | 0.89 (3) | 1.93 (3) | 2.827 (2) | 176 (2) |
| Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z−1; (iii) −x, −y+1, −z; (iv) −x, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4D···O1W | 0.93 (2) | 2.00 (2) | 2.924 (3) | 170.9 (18) |
| N4—H4E···O3Wi | 0.88 (2) | 2.21 (2) | 3.078 (3) | 168.3 (18) |
| N8—H8E···O2Wii | 0.93 (3) | 2.23 (3) | 3.104 (3) | 156 (2) |
| O1W—H1WA···O2Wiii | 0.84 (3) | 1.95 (3) | 2.793 (3) | 173 (3) |
| O1W—H1WB···O3Wiv | 0.92 (3) | 1.93 (3) | 2.810 (2) | 160 (3) |
| O2W—H2WA···N2 | 0.87 (3) | 2.02 (3) | 2.885 (2) | 171 (2) |
| O2W—H2WB···N5 | 0.90 (3) | 1.93 (3) | 2.816 (2) | 168 (2) |
| O3W—H3WA···N1 | 0.88 (2) | 1.92 (2) | 2.787 (2) | 168 (2) |
| O3W—H3WB···N6 | 0.89 (3) | 1.93 (3) | 2.827 (2) | 176 (2) |
| Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z−1; (iii) −x, −y+1, −z; (iv) −x, −y, −z. |
The authors thank the Program for Young Excellent Talents in Southeast University for financial support.
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The derivatives of 4-amino-1,2,4-triazoles have considerable importance in medicinal chemistry, agricultural and industrial chemistry (Bentiss et al. 1999; Collin et al. 2003; Curtis et al. 2004). They have also been used as multidentate ligands in coordination chemistry (Beckmann et al. 2003). Here, we report a hydrated 4-amino-1,2,4-triazole (mta)2.3H2O (mta = 4-amino-3,5-dimethyl-1,2,4-triazole).
The asymmetric unit of the title compound contains two crystallographically independent mta molecules and three water molecules. The C═N—N—C fragments of the tetrazine rings have the C═N distances of 1.299 (2), 1.300 (2) and 1.304 (2) Å, and the N—N distances of 1.392 (2) and 1.389 (2) Å. All other C—N distances are between 1.352 (2) and 1.362 (2) Å, which are considered to have part double-bond character. In the crystalline state, the mta and crystal water molecules are linked together by N—H···O, O—H···N and O—H···O hydrogen bonding.