Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021022/ci2380sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021022/ci2380Isup2.hkl |
CCDC reference: 651375
Key indicators
- Single-crystal X-ray study
- T = 223 K
- Mean (C-C) = 0.002 Å
- R factor = 0.046
- wR factor = 0.121
- Data-to-parameter ratio = 16.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT420_ALERT_2_C D-H Without Acceptor N11 - H11N ... ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
5-Amino-1-guanyl-3-phenyl-1,2,4-triazole (0.50 g, 2.5 mmol) was heated under reflux in acetone (8 ml) containing piperidine (0.05 ml, 0.5 mmol) for 12 h. After cooling, the precipitated solid was filtered, washed with acetone and recrystallized from ethanol (m.p. 482 K).
Atom H5N and H11N were located in a difference map and refined isotropically. The remaining H atoms were placed in calculated positions (N—H = 0.87 Å and C—H = 0.94 or 0.97 Å), and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(methyl C). A rotating group model was used for the methyl groups.
1,2,4-triazolo[1,5-a][1,3,5]triazines (5-azapurines) have been shown to exhibit many types of important biological activities (Dolzhenko et al., 2006). As a part of our ongoing investigation on the derivatives of this heterocyclic system (Dolzhenko, Dolzhenko & Chui, 2007), we report herein the crystallographic study of the title compound (I) which is a regioisomer of previously described 7,7-dimethyl-2-phenyl-6,7-dihydro[1,2,4]triazolo[1,5-a][1,3,5]triazin- 5-amine (Dolzhenko, Tan et al., 2007).
The title compound (I), C12H14N6, was prepared by cyclocondensation of 5-amino-1-guanyl-3-phenyl-1,2,4-triazole with acetone. In general, the synthesized compound might be involved in annular tautomerism with three possible tautomeric forms (Fig. 1). However, only one tautomeric form viz. 5,5-dimethyl-2-phenyl-4,5-dihydro[1,2,4]triazolo[1,5-a][1,3,5]triazin- 7-amine (I) was observed in the crystal.
Compound (I) crystallizes with two independent molecules, A (Fig. 2) and B (Fig. 3), in the asymmetric unit (Fig. 4). The triazine rings of the molecules A and B adopt similar conformations best described as an intermediate between a twist-boat and a half-boat with atom C10 (C22) at the bow. The mean planes of the triazole and phenyl rings make a dihedral angles of 11.30 (5)° and 8.40 (6)° for the molecules A and B, respectively. The crystal packing is stabilized by intermolecular N—H···N hydrogen-bonds (Table 1)
The 1,2,4-triazolo[1,5-a][1,3,5]triazine (5-azapurine) heterocyclic system has been reviewed by Dolzhenko et al. (2006). The crystal structure of 7,7-dimethyl-2-phenyl-6,7-dihydro[1,2,4]triazolo[1,5-a][1,3,5]triazin- 5-amine, which is regioisomeric with the title compound, (I), is reported in the previous paper (Dolzhenko, Tan et al., 2007). For related literature, see also Dolzhenko, Dolzhenko & Chui (2007).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL.
C12H14N6 | Z = 4 |
Mr = 242.29 | F(000) = 512 |
Triclinic, P1 | Dx = 1.331 Mg m−3 |
Hall symbol: -P 1 | Melting point: 482 K |
a = 9.7224 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.9752 (6) Å | Cell parameters from 4987 reflections |
c = 12.4432 (6) Å | θ = 2.3–27.4° |
α = 112.200 (1)° | µ = 0.09 mm−1 |
β = 103.737 (1)° | T = 223 K |
γ = 104.161 (1)° | Block, colourless |
V = 1209.58 (10) Å3 | 0.40 × 0.38 × 0.20 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5549 independent reflections |
Radiation source: fine-focus sealed tube, Bruker SMART APEX CCD area-detector | 4621 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −12→12 |
Tmin = 0.931, Tmax = 0.980 | k = −15→15 |
15995 measured reflections | l = −16→16 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0629P)2 + 0.25P] where P = (Fo2 + 2Fc2)/3 |
5549 reflections | (Δ/σ)max = 0.001 |
337 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C12H14N6 | γ = 104.161 (1)° |
Mr = 242.29 | V = 1209.58 (10) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.7224 (5) Å | Mo Kα radiation |
b = 11.9752 (6) Å | µ = 0.09 mm−1 |
c = 12.4432 (6) Å | T = 223 K |
α = 112.200 (1)° | 0.40 × 0.38 × 0.20 mm |
β = 103.737 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 5549 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 4621 reflections with I > 2σ(I) |
Tmin = 0.931, Tmax = 0.980 | Rint = 0.026 |
15995 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.30 e Å−3 |
5549 reflections | Δρmin = −0.29 e Å−3 |
337 parameters |
Experimental. The su's on the cell Angles are rounded values. |
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 > 2σ(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 | 0.43352 (12) | 0.53590 (11) | 0.34655 (11) | 0.0283 (3) | |
N2 | 0.49145 (12) | 0.35638 (10) | 0.32551 (10) | 0.0257 (2) | |
N3 | 0.62201 (12) | 0.46598 (10) | 0.37342 (10) | 0.0254 (2) | |
N4 | 0.88222 (12) | 0.58752 (11) | 0.46028 (11) | 0.0270 (2) | |
N5 | 0.69510 (13) | 0.68668 (11) | 0.43546 (12) | 0.0316 (3) | |
H5N | 0.6728 (19) | 0.7549 (16) | 0.4426 (15) | 0.037 (4)* | |
N6 | 0.79574 (13) | 0.37717 (11) | 0.43315 (12) | 0.0331 (3) | |
H6A | 0.8877 | 0.3806 | 0.4644 | 0.040* | |
H6B | 0.7177 | 0.3068 | 0.4073 | 0.040* | |
C1 | 0.11373 (16) | 0.38462 (14) | 0.25729 (13) | 0.0317 (3) | |
H1 | 0.1475 | 0.4758 | 0.2972 | 0.038* | |
C2 | −0.04123 (17) | 0.31081 (16) | 0.20182 (14) | 0.0381 (3) | |
H2 | −0.1120 | 0.3521 | 0.2045 | 0.046* | |
C3 | −0.09205 (17) | 0.17701 (16) | 0.14279 (14) | 0.0409 (4) | |
H3 | −0.1972 | 0.1270 | 0.1044 | 0.049* | |
C4 | 0.01239 (18) | 0.11703 (15) | 0.14052 (15) | 0.0406 (4) | |
H4 | −0.0222 | 0.0258 | 0.1007 | 0.049* | |
C5 | 0.16773 (16) | 0.18946 (14) | 0.19612 (14) | 0.0336 (3) | |
H5 | 0.2377 | 0.1474 | 0.1945 | 0.040* | |
C6 | 0.21989 (14) | 0.32455 (13) | 0.25427 (12) | 0.0261 (3) | |
C7 | 0.38395 (14) | 0.40484 (12) | 0.31078 (12) | 0.0248 (3) | |
C8 | 0.58319 (15) | 0.57033 (12) | 0.38609 (12) | 0.0257 (3) | |
C9 | 0.77452 (14) | 0.48004 (12) | 0.42477 (12) | 0.0244 (3) | |
C10 | 0.84763 (14) | 0.68883 (13) | 0.43383 (13) | 0.0264 (3) | |
C11 | 0.85505 (18) | 0.66838 (16) | 0.30710 (14) | 0.0391 (4) | |
H11A | 0.9524 | 0.6628 | 0.3052 | 0.059* | |
H11B | 0.8443 | 0.7409 | 0.2934 | 0.059* | |
H11C | 0.7731 | 0.5884 | 0.2421 | 0.059* | |
C12 | 0.96425 (16) | 0.82034 (14) | 0.53578 (14) | 0.0345 (3) | |
H12A | 0.9585 | 0.8319 | 0.6159 | 0.052* | |
H12B | 0.9430 | 0.8885 | 0.5191 | 0.052* | |
H12C | 1.0657 | 0.8246 | 0.5374 | 0.052* | |
N7 | 0.64515 (12) | 0.91698 (10) | 0.41712 (10) | 0.0253 (2) | |
N8 | 0.62672 (13) | 1.09681 (10) | 0.40021 (10) | 0.0257 (2) | |
N9 | 0.58770 (13) | 0.99346 (10) | 0.28465 (10) | 0.0257 (2) | |
N10 | 0.51588 (14) | 0.88737 (11) | 0.06878 (10) | 0.0311 (3) | |
N11 | 0.55846 (14) | 0.77685 (11) | 0.19483 (11) | 0.0289 (3) | |
H11N | 0.562 (2) | 0.7133 (19) | 0.2025 (17) | 0.050 (5)* | |
N12 | 0.50404 (15) | 1.08991 (12) | 0.16469 (11) | 0.0351 (3) | |
H12D | 0.4693 | 1.0909 | 0.0940 | 0.042* | |
H12E | 0.5189 | 1.1555 | 0.2341 | 0.042* | |
C13 | 0.77339 (18) | 1.06873 (15) | 0.68743 (14) | 0.0354 (3) | |
H13 | 0.7666 | 0.9821 | 0.6513 | 0.043* | |
C14 | 0.8361 (2) | 1.14393 (17) | 0.81604 (14) | 0.0442 (4) | |
H14 | 0.8716 | 1.1077 | 0.8669 | 0.053* | |
C15 | 0.84680 (19) | 1.27077 (16) | 0.86998 (14) | 0.0415 (4) | |
H15 | 0.8915 | 1.3216 | 0.9571 | 0.050* | |
C16 | 0.79161 (18) | 1.32329 (15) | 0.79563 (14) | 0.0380 (3) | |
H16 | 0.7973 | 1.4096 | 0.8324 | 0.046* | |
C17 | 0.72806 (16) | 1.24939 (13) | 0.66731 (13) | 0.0303 (3) | |
H17 | 0.6898 | 1.2854 | 0.6172 | 0.036* | |
C18 | 0.72058 (14) | 1.12204 (12) | 0.61204 (12) | 0.0246 (3) | |
C19 | 0.66055 (14) | 1.04497 (12) | 0.47514 (12) | 0.0229 (3) | |
C20 | 0.59803 (14) | 0.88878 (12) | 0.29832 (12) | 0.0241 (3) | |
C21 | 0.53451 (15) | 0.98768 (13) | 0.16659 (12) | 0.0259 (3) | |
C22 | 0.56405 (17) | 0.78425 (13) | 0.07957 (12) | 0.0299 (3) | |
C23 | 0.7259 (2) | 0.81007 (18) | 0.08085 (16) | 0.0448 (4) | |
H23A | 0.7305 | 0.8189 | 0.0073 | 0.067* | |
H23B | 0.7550 | 0.7382 | 0.0809 | 0.067* | |
H23C | 0.7954 | 0.8896 | 0.1551 | 0.067* | |
C24 | 0.4530 (2) | 0.65590 (15) | −0.03085 (14) | 0.0453 (4) | |
H24A | 0.3509 | 0.6423 | −0.0298 | 0.068* | |
H24B | 0.4821 | 0.5857 | −0.0255 | 0.068* | |
H24C | 0.4550 | 0.6576 | −0.1078 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0236 (5) | 0.0251 (6) | 0.0355 (6) | 0.0100 (5) | 0.0086 (5) | 0.0139 (5) |
N2 | 0.0229 (5) | 0.0228 (5) | 0.0289 (6) | 0.0065 (4) | 0.0076 (4) | 0.0118 (5) |
N3 | 0.0225 (5) | 0.0214 (5) | 0.0321 (6) | 0.0084 (4) | 0.0077 (4) | 0.0134 (5) |
N4 | 0.0233 (5) | 0.0258 (6) | 0.0344 (6) | 0.0108 (5) | 0.0077 (5) | 0.0171 (5) |
N5 | 0.0244 (6) | 0.0218 (6) | 0.0500 (7) | 0.0107 (5) | 0.0111 (5) | 0.0182 (5) |
N6 | 0.0245 (6) | 0.0271 (6) | 0.0507 (7) | 0.0111 (5) | 0.0087 (5) | 0.0231 (6) |
C1 | 0.0294 (7) | 0.0337 (7) | 0.0312 (7) | 0.0123 (6) | 0.0099 (6) | 0.0147 (6) |
C2 | 0.0272 (7) | 0.0524 (9) | 0.0390 (8) | 0.0170 (7) | 0.0117 (6) | 0.0242 (7) |
C3 | 0.0247 (7) | 0.0509 (10) | 0.0348 (8) | 0.0019 (6) | 0.0068 (6) | 0.0178 (7) |
C4 | 0.0362 (8) | 0.0330 (8) | 0.0391 (8) | 0.0014 (6) | 0.0133 (7) | 0.0110 (7) |
C5 | 0.0314 (7) | 0.0307 (7) | 0.0369 (8) | 0.0098 (6) | 0.0142 (6) | 0.0141 (6) |
C6 | 0.0247 (6) | 0.0289 (7) | 0.0249 (6) | 0.0088 (5) | 0.0094 (5) | 0.0131 (5) |
C7 | 0.0250 (6) | 0.0255 (6) | 0.0243 (6) | 0.0095 (5) | 0.0089 (5) | 0.0119 (5) |
C8 | 0.0261 (6) | 0.0247 (6) | 0.0287 (7) | 0.0123 (5) | 0.0091 (5) | 0.0138 (5) |
C9 | 0.0234 (6) | 0.0265 (6) | 0.0258 (6) | 0.0118 (5) | 0.0083 (5) | 0.0135 (5) |
C10 | 0.0226 (6) | 0.0254 (6) | 0.0337 (7) | 0.0102 (5) | 0.0079 (5) | 0.0170 (6) |
C11 | 0.0401 (8) | 0.0437 (9) | 0.0374 (8) | 0.0147 (7) | 0.0127 (7) | 0.0240 (7) |
C12 | 0.0282 (7) | 0.0275 (7) | 0.0421 (8) | 0.0079 (6) | 0.0079 (6) | 0.0150 (6) |
N7 | 0.0292 (6) | 0.0240 (5) | 0.0253 (5) | 0.0106 (4) | 0.0097 (5) | 0.0136 (5) |
N8 | 0.0303 (6) | 0.0235 (5) | 0.0230 (5) | 0.0106 (5) | 0.0087 (4) | 0.0108 (4) |
N9 | 0.0338 (6) | 0.0217 (5) | 0.0234 (5) | 0.0120 (5) | 0.0089 (5) | 0.0120 (4) |
N10 | 0.0444 (7) | 0.0268 (6) | 0.0256 (6) | 0.0168 (5) | 0.0106 (5) | 0.0145 (5) |
N11 | 0.0423 (7) | 0.0218 (6) | 0.0277 (6) | 0.0149 (5) | 0.0131 (5) | 0.0145 (5) |
N12 | 0.0555 (8) | 0.0305 (6) | 0.0254 (6) | 0.0247 (6) | 0.0116 (5) | 0.0154 (5) |
C13 | 0.0460 (9) | 0.0344 (8) | 0.0307 (7) | 0.0201 (7) | 0.0126 (6) | 0.0175 (6) |
C14 | 0.0575 (10) | 0.0513 (10) | 0.0294 (8) | 0.0273 (8) | 0.0115 (7) | 0.0226 (7) |
C15 | 0.0479 (9) | 0.0456 (9) | 0.0238 (7) | 0.0158 (7) | 0.0103 (6) | 0.0115 (7) |
C16 | 0.0460 (9) | 0.0313 (8) | 0.0320 (8) | 0.0129 (7) | 0.0155 (7) | 0.0104 (6) |
C17 | 0.0342 (7) | 0.0301 (7) | 0.0305 (7) | 0.0134 (6) | 0.0132 (6) | 0.0161 (6) |
C18 | 0.0227 (6) | 0.0271 (7) | 0.0258 (6) | 0.0090 (5) | 0.0099 (5) | 0.0136 (5) |
C19 | 0.0204 (6) | 0.0227 (6) | 0.0277 (6) | 0.0074 (5) | 0.0092 (5) | 0.0141 (5) |
C20 | 0.0244 (6) | 0.0233 (6) | 0.0286 (6) | 0.0097 (5) | 0.0099 (5) | 0.0153 (5) |
C21 | 0.0286 (7) | 0.0258 (6) | 0.0250 (6) | 0.0105 (5) | 0.0080 (5) | 0.0144 (5) |
C22 | 0.0424 (8) | 0.0254 (7) | 0.0255 (7) | 0.0158 (6) | 0.0121 (6) | 0.0135 (6) |
C23 | 0.0535 (10) | 0.0545 (10) | 0.0475 (9) | 0.0301 (9) | 0.0285 (8) | 0.0322 (8) |
C24 | 0.0689 (12) | 0.0285 (8) | 0.0302 (8) | 0.0170 (8) | 0.0100 (8) | 0.0111 (6) |
N1—C8 | 1.3200 (17) | N7—C20 | 1.3170 (17) |
N1—C7 | 1.3761 (17) | N7—C19 | 1.3758 (16) |
N2—C7 | 1.3224 (17) | N8—C19 | 1.3246 (16) |
N2—N3 | 1.3869 (15) | N8—N9 | 1.3818 (15) |
N3—C8 | 1.3561 (16) | N9—C20 | 1.3508 (16) |
N3—C9 | 1.4078 (16) | N9—C21 | 1.4054 (16) |
N4—C9 | 1.2803 (17) | N10—C21 | 1.2811 (17) |
N4—C10 | 1.4636 (16) | N10—C22 | 1.4631 (17) |
N5—C8 | 1.3403 (17) | N11—C20 | 1.3457 (17) |
N5—C10 | 1.4819 (17) | N11—C22 | 1.4828 (17) |
N5—H5N | 0.874 (17) | N11—H11N | 0.810 (19) |
N6—C9 | 1.3350 (16) | N12—C21 | 1.3353 (17) |
N6—H6A | 0.87 | N12—H12D | 0.87 |
N6—H6B | 0.87 | N12—H12E | 0.87 |
C1—C2 | 1.386 (2) | C13—C14 | 1.387 (2) |
C1—C6 | 1.3948 (19) | C13—C18 | 1.3912 (19) |
C1—H1 | 0.94 | C13—H13 | 0.94 |
C2—C3 | 1.379 (2) | C14—C15 | 1.374 (2) |
C2—H2 | 0.94 | C14—H14 | 0.94 |
C3—C4 | 1.379 (2) | C15—C16 | 1.381 (2) |
C3—H3 | 0.94 | C15—H15 | 0.94 |
C4—C5 | 1.386 (2) | C16—C17 | 1.382 (2) |
C4—H4 | 0.94 | C16—H16 | 0.94 |
C5—C6 | 1.3919 (19) | C17—C18 | 1.3905 (19) |
C5—H5 | 0.94 | C17—H17 | 0.94 |
C6—C7 | 1.4728 (18) | C18—C19 | 1.4732 (18) |
C10—C12 | 1.5193 (19) | C22—C24 | 1.518 (2) |
C10—C11 | 1.524 (2) | C22—C23 | 1.523 (2) |
C11—H11A | 0.97 | C23—H23A | 0.97 |
C11—H11B | 0.97 | C23—H23B | 0.97 |
C11—H11C | 0.97 | C23—H23C | 0.97 |
C12—H12A | 0.97 | C24—H24A | 0.97 |
C12—H12B | 0.97 | C24—H24B | 0.97 |
C12—H12C | 0.97 | C24—H24C | 0.97 |
C8—N1—C7 | 102.36 (11) | C20—N7—C19 | 102.43 (10) |
C7—N2—N3 | 101.17 (10) | C19—N8—N9 | 101.35 (10) |
C8—N3—N2 | 109.71 (10) | C20—N9—N8 | 109.76 (10) |
C8—N3—C9 | 121.45 (11) | C20—N9—C21 | 122.04 (11) |
N2—N3—C9 | 127.86 (10) | N8—N9—C21 | 128.07 (10) |
C9—N4—C10 | 119.88 (11) | C21—N10—C22 | 120.53 (11) |
C8—N5—C10 | 117.54 (11) | C20—N11—C22 | 117.96 (11) |
C8—N5—H5N | 120.0 (11) | C20—N11—H11N | 118.6 (13) |
C10—N5—H5N | 118.8 (11) | C22—N11—H11N | 119.8 (13) |
C9—N6—H6A | 120.0 | C21—N12—H12D | 120.0 |
C9—N6—H6B | 120.0 | C21—N12—H12E | 120.0 |
H6A—N6—H6B | 120.0 | H12D—N12—H12E | 120.0 |
C2—C1—C6 | 120.45 (14) | C14—C13—C18 | 119.75 (14) |
C2—C1—H1 | 119.8 | C14—C13—H13 | 120.1 |
C6—C1—H1 | 119.8 | C18—C13—H13 | 120.1 |
C3—C2—C1 | 120.26 (14) | C15—C14—C13 | 120.70 (14) |
C3—C2—H2 | 119.9 | C15—C14—H14 | 119.7 |
C1—C2—H2 | 119.9 | C13—C14—H14 | 119.7 |
C2—C3—C4 | 119.56 (14) | C14—C15—C16 | 119.75 (14) |
C2—C3—H3 | 120.2 | C14—C15—H15 | 120.1 |
C4—C3—H3 | 120.2 | C16—C15—H15 | 120.1 |
C3—C4—C5 | 120.88 (15) | C15—C16—C17 | 120.25 (14) |
C3—C4—H4 | 119.6 | C15—C16—H16 | 119.9 |
C5—C4—H4 | 119.6 | C17—C16—H16 | 119.9 |
C4—C5—C6 | 119.89 (14) | C16—C17—C18 | 120.23 (13) |
C4—C5—H5 | 120.1 | C16—C17—H17 | 119.9 |
C6—C5—H5 | 120.1 | C18—C17—H17 | 119.9 |
C5—C6—C1 | 118.95 (13) | C17—C18—C13 | 119.28 (13) |
C5—C6—C7 | 121.50 (12) | C17—C18—C19 | 120.54 (12) |
C1—C6—C7 | 119.54 (12) | C13—C18—C19 | 120.16 (12) |
N2—C7—N1 | 116.11 (11) | N8—C19—N7 | 115.68 (11) |
N2—C7—C6 | 123.05 (12) | N8—C19—C18 | 121.99 (11) |
N1—C7—C6 | 120.78 (11) | N7—C19—C18 | 122.21 (11) |
N1—C8—N5 | 130.97 (12) | N7—C20—N11 | 130.98 (12) |
N1—C8—N3 | 110.62 (11) | N7—C20—N9 | 110.77 (11) |
N5—C8—N3 | 118.40 (12) | N11—C20—N9 | 118.24 (11) |
N4—C9—N6 | 124.39 (12) | N10—C21—N12 | 123.95 (12) |
N4—C9—N3 | 119.53 (11) | N10—C21—N9 | 119.94 (12) |
N6—C9—N3 | 116.08 (11) | N12—C21—N9 | 116.11 (11) |
N4—C10—N5 | 110.85 (10) | N10—C22—N11 | 111.25 (11) |
N4—C10—C12 | 108.60 (11) | N10—C22—C24 | 107.89 (12) |
N5—C10—C12 | 107.48 (11) | N11—C22—C24 | 107.66 (12) |
N4—C10—C11 | 109.05 (11) | N10—C22—C23 | 109.33 (12) |
N5—C10—C11 | 110.48 (11) | N11—C22—C23 | 109.52 (12) |
C12—C10—C11 | 110.36 (12) | C24—C22—C23 | 111.19 (13) |
C10—C11—H11A | 109.5 | C22—C23—H23A | 109.5 |
C10—C11—H11B | 109.5 | C22—C23—H23B | 109.5 |
H11A—C11—H11B | 109.5 | H23A—C23—H23B | 109.5 |
C10—C11—H11C | 109.5 | C22—C23—H23C | 109.5 |
H11A—C11—H11C | 109.5 | H23A—C23—H23C | 109.5 |
H11B—C11—H11C | 109.5 | H23B—C23—H23C | 109.5 |
C10—C12—H12A | 109.5 | C22—C24—H24A | 109.5 |
C10—C12—H12B | 109.5 | C22—C24—H24B | 109.5 |
H12A—C12—H12B | 109.5 | H24A—C24—H24B | 109.5 |
C10—C12—H12C | 109.5 | C22—C24—H24C | 109.5 |
H12A—C12—H12C | 109.5 | H24A—C24—H24C | 109.5 |
H12B—C12—H12C | 109.5 | H24B—C24—H24C | 109.5 |
C7—N2—N3—C8 | 1.37 (13) | C19—N8—N9—C20 | 1.11 (13) |
C7—N2—N3—C9 | 170.10 (12) | C19—N8—N9—C21 | 177.04 (12) |
C6—C1—C2—C3 | −0.1 (2) | C18—C13—C14—C15 | −0.1 (3) |
C1—C2—C3—C4 | 0.7 (2) | C13—C14—C15—C16 | 1.4 (3) |
C2—C3—C4—C5 | −0.4 (2) | C14—C15—C16—C17 | −1.1 (2) |
C3—C4—C5—C6 | −0.5 (2) | C15—C16—C17—C18 | −0.6 (2) |
C4—C5—C6—C1 | 1.1 (2) | C16—C17—C18—C13 | 2.0 (2) |
C4—C5—C6—C7 | −177.98 (13) | C16—C17—C18—C19 | −176.71 (13) |
C2—C1—C6—C5 | −0.8 (2) | C14—C13—C18—C17 | −1.6 (2) |
C2—C1—C6—C7 | 178.33 (13) | C14—C13—C18—C19 | 177.07 (14) |
N3—N2—C7—N1 | −0.93 (14) | N9—N8—C19—N7 | −0.54 (14) |
N3—N2—C7—C6 | 176.30 (11) | N9—N8—C19—C18 | 175.52 (11) |
C8—N1—C7—N2 | 0.12 (15) | C20—N7—C19—N8 | −0.24 (14) |
C8—N1—C7—C6 | −177.18 (12) | C20—N7—C19—C18 | −176.29 (11) |
C5—C6—C7—N2 | −9.5 (2) | C17—C18—C19—N8 | 7.11 (19) |
C1—C6—C7—N2 | 171.34 (12) | C13—C18—C19—N8 | −171.56 (13) |
C5—C6—C7—N1 | 167.56 (13) | C17—C18—C19—N7 | −177.08 (12) |
C1—C6—C7—N1 | −11.56 (19) | C13—C18—C19—N7 | 4.24 (19) |
C7—N1—C8—N5 | −178.18 (14) | C19—N7—C20—N11 | −177.73 (14) |
C7—N1—C8—N3 | 0.80 (14) | C19—N7—C20—N9 | 0.96 (14) |
C10—N5—C8—N1 | −161.07 (14) | C22—N11—C20—N7 | −158.17 (13) |
C10—N5—C8—N3 | 20.01 (18) | C22—N11—C20—N9 | 23.22 (18) |
N2—N3—C8—N1 | −1.44 (15) | N8—N9—C20—N7 | −1.38 (15) |
C9—N3—C8—N1 | −171.02 (11) | C21—N9—C20—N7 | −177.60 (11) |
N2—N3—C8—N5 | 177.69 (11) | N8—N9—C20—N11 | 177.50 (11) |
C9—N3—C8—N5 | 8.11 (19) | C21—N9—C20—N11 | 1.28 (19) |
C10—N4—C9—N6 | 172.98 (13) | C22—N10—C21—N12 | 174.81 (13) |
C10—N4—C9—N3 | −7.26 (19) | C22—N10—C21—N9 | −6.3 (2) |
C8—N3—C9—N4 | −15.29 (19) | C20—N9—C21—N10 | −10.5 (2) |
N2—N3—C9—N4 | 177.17 (12) | N8—N9—C21—N10 | 174.01 (13) |
C8—N3—C9—N6 | 164.48 (12) | C20—N9—C21—N12 | 168.51 (12) |
N2—N3—C9—N6 | −3.06 (19) | N8—N9—C21—N12 | −7.0 (2) |
C9—N4—C10—N5 | 32.61 (17) | C21—N10—C22—N11 | 28.29 (18) |
C9—N4—C10—C12 | 150.47 (13) | C21—N10—C22—C24 | 146.15 (14) |
C9—N4—C10—C11 | −89.23 (15) | C21—N10—C22—C23 | −92.80 (16) |
C8—N5—C10—N4 | −39.04 (16) | C20—N11—C22—N10 | −36.86 (17) |
C8—N5—C10—C12 | −157.58 (12) | C20—N11—C22—C24 | −154.87 (13) |
C8—N5—C10—C11 | 81.96 (15) | C20—N11—C22—C23 | 84.11 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···N7 | 0.874 (17) | 2.150 (17) | 2.9955 (16) | 163 (2) |
N6—H6A···N4i | 0.87 | 2.08 | 2.9491 (16) | 172 |
N12—H12D···N10ii | 0.87 | 2.17 | 2.9844 (16) | 156 |
N12—H12E···N2iii | 0.87 | 2.35 | 3.1119 (16) | 146 |
N6—H6B···N8iv | 0.87 | 2.41 | 3.1751 (16) | 147 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) x, y+1, z; (iv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C12H14N6 |
Mr | 242.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 223 |
a, b, c (Å) | 9.7224 (5), 11.9752 (6), 12.4432 (6) |
α, β, γ (°) | 112.200 (1), 103.737 (1), 104.161 (1) |
V (Å3) | 1209.58 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.38 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.931, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15995, 5549, 4621 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.121, 1.06 |
No. of reflections | 5549 |
No. of parameters | 337 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.29 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···N7 | 0.874 (17) | 2.150 (17) | 2.9955 (16) | 163 (2) |
N6—H6A···N4i | 0.87 | 2.08 | 2.9491 (16) | 172 |
N12—H12D···N10ii | 0.87 | 2.17 | 2.9844 (16) | 156 |
N12—H12E···N2iii | 0.87 | 2.35 | 3.1119 (16) | 146 |
N6—H6B···N8iv | 0.87 | 2.41 | 3.1751 (16) | 147 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) x, y+1, z; (iv) x, y−1, z. |
1,2,4-triazolo[1,5-a][1,3,5]triazines (5-azapurines) have been shown to exhibit many types of important biological activities (Dolzhenko et al., 2006). As a part of our ongoing investigation on the derivatives of this heterocyclic system (Dolzhenko, Dolzhenko & Chui, 2007), we report herein the crystallographic study of the title compound (I) which is a regioisomer of previously described 7,7-dimethyl-2-phenyl-6,7-dihydro[1,2,4]triazolo[1,5-a][1,3,5]triazin- 5-amine (Dolzhenko, Tan et al., 2007).
The title compound (I), C12H14N6, was prepared by cyclocondensation of 5-amino-1-guanyl-3-phenyl-1,2,4-triazole with acetone. In general, the synthesized compound might be involved in annular tautomerism with three possible tautomeric forms (Fig. 1). However, only one tautomeric form viz. 5,5-dimethyl-2-phenyl-4,5-dihydro[1,2,4]triazolo[1,5-a][1,3,5]triazin- 7-amine (I) was observed in the crystal.
Compound (I) crystallizes with two independent molecules, A (Fig. 2) and B (Fig. 3), in the asymmetric unit (Fig. 4). The triazine rings of the molecules A and B adopt similar conformations best described as an intermediate between a twist-boat and a half-boat with atom C10 (C22) at the bow. The mean planes of the triazole and phenyl rings make a dihedral angles of 11.30 (5)° and 8.40 (6)° for the molecules A and B, respectively. The crystal packing is stabilized by intermolecular N—H···N hydrogen-bonds (Table 1)