organic compounds
(7R)-6-Methyl-7,9-bis(prop-2-yn-1-yl)-7H,8H,9H-1,2,4-triazolo[4,3-b][1,2,4]triazepin-8-one
aLaboratoire de Chimie Organique Hétérocyclique, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Mohammed V University, Rabat, Morocco, bMedicinal Chemistry Laboratory, Faculty of Medicine and Pharmacy, Mohammed V University in Rabat, 10170 Rabat, Morocco, and cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
*Correspondence e-mail: youness.chimie14@gmail.com
In the title molecule, C12H11N5O, the seven-membered ring derived from triazepine adopts a boat conformation. Intermolecular C—H⋯N hydrogen bonds and C—H⋯π-ring interactions form columns of molecules parallel to the a axis, which are further associated into the three-dimensional by additional C—H⋯O hydrogen bonds.
Keywords: crystal structure; hydrogen bonds; alkyne; triazepine.
CCDC reference: 1497249
Structure description
Fused triazepines with a bridged nitrogen atom in heterocyclic systems exhibit interesting biological properties (Groszkowski & Wrona, 1978; Lenman et al., 1997). Triazepine derivatives have also been reported to possess antifungal activity (Gupta et al., 2011). As a continuation of our previous studies on the synthesis and reactivity of fused triazepines (Essassi et al., 1977; Zemama et al., 2009; Harmaoui et al., 2015), we report the synthesis and of the title compound (Fig. 1). A puckering analysis of the seven-membered ring yielded the parameters q2 = 0.847 (1) Å, φ2 = 228.47 (8)°, q3 = 0.235 (1) Å, and φ3 = 79.7 (3)°. These metrics indicate that the ring adopts a boat conformation.
The molecules are stacked parallel to the a axis through the action of intermolecular C7—H7⋯N4i hydrogen bonds [symmetry code: (i) 1 − x, 1 − y, 1 − z; Table 1] and C12—H12B⋯π(Cgii) interactions [symmetry code: (ii) 2 − x, 1 − y, 1 − z; Cg is the centroid of the C1/C4/N1/N4/N5 ring], characterized by H12B⋯Cgii = 3.217 Å and C12—H12B⋯Cgii = 138°. Finally, intermolecular C4—H4⋯O1iii hydrogen bonds [symmetry code: (iii) 1 − x, + y, − z; Table 1] tie the columns together to form the full three-dimensional structure (Fig. 2).
Synthesis and crystallization
To a solution of 6-methyl-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazepin-8(9H)-one (0.3 g, 1.82 mmol) in N,N-dimethylformamide (10 ml), was added potassium carbonate (0.25 g, 1.82 mmol), propargyl bromide (0.14 ml, 1.82 mmol) and a catalytic amount of tetra-n-butylammonium bromide. The reaction mixture was stirred for 12 h. The solution was then taken to dryness under reduced pressure and the residue was extracted with dichloromethane. The precipitate formed under cooling was filtered off and recrystallized from ethanol solutionto give colourless crystals in 30% yield.
Refinement
Crystal data, data collection and structure . The propynyl substituent attached to N3 is disordered over two sites, modelled with C12/C13/C14 [occupancy: 0.610 (15)] and C12A/C13A/C14A [occupancy:0.390 (15)]. The components of the disorder were refined with restraints on both the geometry and displacement parameters.
details are summarized in Table 2Structural data
CCDC reference: 1497249
10.1107/S2414314616012451/bh4010sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616012451/bh4010Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616012451/bh4010Isup3.cdx
Supporting information file. DOI: 10.1107/S2414314616012451/bh4010Isup4.cml
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C12H11N5O | F(000) = 504 |
Mr = 241.26 | Dx = 1.304 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5436 (3) Å | Cell parameters from 9984 reflections |
b = 15.6498 (6) Å | θ = 2.4–29.1° |
c = 10.9701 (4) Å | µ = 0.09 mm−1 |
β = 108.334 (1)° | T = 296 K |
V = 1229.34 (8) Å3 | Block, colourless |
Z = 4 | 0.42 × 0.42 × 0.31 mm |
Bruker SMART APEX CCD diffractometer | 3313 independent reflections |
Radiation source: fine-focus sealed tube | 2701 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 8.3333 pixels mm-1 | θmax = 29.2°, θmin = 2.4° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −21→21 |
Tmin = 0.89, Tmax = 0.97 | l = −15→14 |
23271 measured 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0829P)2 + 0.1647P] where P = (Fo2 + 2Fc2)/3 |
3313 reflections | (Δ/σ)max < 0.001 |
174 parameters | Δρmax = 0.49 e Å−3 |
28 restraints | Δρmin = −0.18 e Å−3 |
Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 7 sec/frame. |
Refinement. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å). All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. The propynyl substituent attached to N3 is disordered over two sites in a 61/39 ratio. The components of the disorder were refined with restraints that their geometries be comparable. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.53407 (14) | 0.26656 (6) | 0.38907 (9) | 0.0503 (3) | |
N1 | 0.54858 (14) | 0.52089 (6) | 0.27441 (9) | 0.0370 (2) | |
N2 | 0.46611 (15) | 0.48217 (7) | 0.15514 (9) | 0.0403 (2) | |
N3 | 0.66193 (13) | 0.39844 (6) | 0.41282 (9) | 0.0364 (2) | |
C1 | 0.64572 (15) | 0.48540 (7) | 0.38983 (10) | 0.0338 (2) | |
C4 | 0.5849 (2) | 0.60626 (8) | 0.29144 (14) | 0.0477 (3) | |
H4 | 0.5396 | 0.6474 | 0.2282 | 0.057* | |
N4 | 0.73180 (15) | 0.54449 (7) | 0.47134 (10) | 0.0434 (3) | |
C5 | 0.37243 (15) | 0.41413 (8) | 0.15763 (10) | 0.0366 (3) | |
N5 | 0.69043 (17) | 0.62237 (7) | 0.40691 (12) | 0.0508 (3) | |
C6 | 0.3048 (2) | 0.36453 (11) | 0.03514 (13) | 0.0561 (4) | |
H6A | 0.1733 | 0.3540 | 0.0149 | 0.084* | |
H6B | 0.3702 | 0.3111 | 0.0450 | 0.084* | |
H6C | 0.3274 | 0.3967 | −0.0330 | 0.084* | |
C7 | 0.33705 (15) | 0.38234 (7) | 0.27846 (10) | 0.0336 (2) | |
H7 | 0.3101 | 0.4323 | 0.3235 | 0.040* | |
C8 | 0.17263 (17) | 0.32044 (9) | 0.25592 (14) | 0.0477 (3) | |
H8A | 0.1948 | 0.2706 | 0.2103 | 0.057* | |
H8B | 0.1640 | 0.3016 | 0.3381 | 0.057* | |
C9 | −0.00402 (19) | 0.36025 (11) | 0.18177 (16) | 0.0561 (4) | |
C10 | −0.1441 (2) | 0.39323 (15) | 0.1201 (2) | 0.0803 (6) | |
H10 | −0.2545 | 0.4192 | 0.0715 | 0.096* | |
C11 | 0.51588 (15) | 0.34220 (7) | 0.36473 (10) | 0.0345 (2) | |
C12 | 0.8373 (10) | 0.3649 (11) | 0.5031 (6) | 0.0457 (7) | 0.610 (15) |
H12A | 0.8427 | 0.3038 | 0.4902 | 0.055* | 0.610 (15) |
H12B | 0.9420 | 0.3908 | 0.4835 | 0.055* | 0.610 (15) |
C13 | 0.8572 (15) | 0.3810 (5) | 0.6390 (6) | 0.0565 (12) | 0.610 (15) |
C14 | 0.8738 (13) | 0.3912 (7) | 0.7481 (6) | 0.0894 (19) | 0.610 (15) |
H14 | 0.8870 | 0.3992 | 0.8345 | 0.107* | 0.610 (15) |
C12A | 0.8455 (15) | 0.3695 (17) | 0.4981 (8) | 0.0457 (7) | 0.390 (15) |
H12C | 0.8769 | 0.3151 | 0.4677 | 0.055* | 0.390 (15) |
H12D | 0.9406 | 0.4106 | 0.4957 | 0.055* | 0.390 (15) |
C13A | 0.843 (2) | 0.3600 (8) | 0.6311 (9) | 0.0565 (12) | 0.390 (15) |
C14A | 0.853 (2) | 0.3561 (9) | 0.7398 (9) | 0.0894 (19) | 0.390 (15) |
H14A | 0.8603 | 0.3530 | 0.8260 | 0.107* | 0.390 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0540 (5) | 0.0310 (4) | 0.0566 (5) | −0.0013 (4) | 0.0044 (4) | 0.0021 (4) |
N1 | 0.0419 (5) | 0.0323 (5) | 0.0368 (5) | −0.0023 (4) | 0.0123 (4) | 0.0002 (3) |
N2 | 0.0458 (6) | 0.0431 (6) | 0.0320 (5) | 0.0004 (4) | 0.0122 (4) | 0.0007 (4) |
N3 | 0.0315 (5) | 0.0330 (5) | 0.0392 (5) | −0.0002 (4) | 0.0033 (4) | 0.0000 (4) |
C1 | 0.0316 (5) | 0.0337 (6) | 0.0362 (5) | −0.0023 (4) | 0.0108 (4) | −0.0026 (4) |
C4 | 0.0533 (7) | 0.0321 (6) | 0.0587 (8) | −0.0032 (5) | 0.0190 (6) | 0.0031 (5) |
N4 | 0.0440 (5) | 0.0382 (6) | 0.0459 (6) | −0.0079 (4) | 0.0109 (4) | −0.0092 (4) |
C5 | 0.0365 (6) | 0.0405 (6) | 0.0307 (5) | 0.0050 (4) | 0.0075 (4) | −0.0036 (4) |
N5 | 0.0528 (6) | 0.0351 (6) | 0.0637 (7) | −0.0073 (5) | 0.0173 (6) | −0.0077 (5) |
C6 | 0.0615 (9) | 0.0670 (9) | 0.0367 (6) | −0.0035 (7) | 0.0108 (6) | −0.0162 (6) |
C7 | 0.0320 (5) | 0.0339 (5) | 0.0328 (5) | −0.0019 (4) | 0.0074 (4) | −0.0033 (4) |
C8 | 0.0376 (6) | 0.0458 (7) | 0.0550 (7) | −0.0094 (5) | 0.0078 (5) | −0.0014 (5) |
C9 | 0.0356 (6) | 0.0638 (9) | 0.0651 (9) | −0.0079 (6) | 0.0105 (6) | −0.0065 (7) |
C10 | 0.0416 (8) | 0.1020 (16) | 0.0906 (14) | 0.0074 (9) | 0.0111 (8) | −0.0008 (11) |
C11 | 0.0356 (5) | 0.0321 (5) | 0.0337 (5) | −0.0020 (4) | 0.0078 (4) | −0.0024 (4) |
C12 | 0.0305 (8) | 0.0461 (15) | 0.0528 (8) | 0.0049 (9) | 0.0024 (6) | −0.0016 (7) |
C13 | 0.0455 (17) | 0.058 (4) | 0.0515 (11) | 0.014 (3) | −0.0054 (11) | −0.0008 (15) |
C14 | 0.088 (3) | 0.112 (5) | 0.0508 (13) | 0.049 (4) | −0.0025 (14) | −0.004 (2) |
C12A | 0.0305 (8) | 0.0461 (15) | 0.0528 (8) | 0.0049 (9) | 0.0024 (6) | −0.0016 (7) |
C13A | 0.0455 (17) | 0.058 (4) | 0.0515 (11) | 0.014 (3) | −0.0054 (11) | −0.0008 (15) |
C14A | 0.088 (3) | 0.112 (5) | 0.0508 (13) | 0.049 (4) | −0.0025 (14) | −0.004 (2) |
O1—C11 | 1.2117 (14) | C7—C11 | 1.5189 (15) |
N1—C4 | 1.3649 (16) | C7—C8 | 1.5314 (16) |
N1—C1 | 1.3657 (14) | C7—H7 | 0.9800 |
N1—N2 | 1.3979 (13) | C8—C9 | 1.4641 (19) |
N2—C5 | 1.2830 (16) | C8—H8A | 0.9700 |
N3—C11 | 1.3789 (14) | C8—H8B | 0.9700 |
N3—C1 | 1.3824 (15) | C9—C10 | 1.179 (2) |
N3—C12 | 1.4773 (18) | C10—H10 | 0.9300 |
N3—C12A | 1.477 (2) | C12—C13 | 1.472 (4) |
C1—N4 | 1.3082 (14) | C12—H12A | 0.9700 |
C4—N5 | 1.2913 (19) | C12—H12B | 0.9700 |
C4—H4 | 0.9300 | C13—C14 | 1.174 (3) |
N4—N5 | 1.3941 (16) | C14—H14 | 0.9300 |
C5—C6 | 1.4957 (16) | C12A—C13A | 1.472 (4) |
C5—C7 | 1.5160 (15) | C12A—H12C | 0.9700 |
C6—H6A | 0.9600 | C12A—H12D | 0.9700 |
C6—H6B | 0.9600 | C13A—C14A | 1.174 (3) |
C6—H6C | 0.9600 | C14A—H14A | 0.9300 |
C4—N1—C1 | 104.19 (10) | C11—C7—H7 | 107.5 |
C4—N1—N2 | 124.30 (10) | C8—C7—H7 | 107.5 |
C1—N1—N2 | 129.98 (10) | C9—C8—C7 | 111.70 (11) |
C5—N2—N1 | 115.21 (9) | C9—C8—H8A | 109.3 |
C11—N3—C1 | 122.98 (9) | C7—C8—H8A | 109.3 |
C11—N3—C12 | 118.0 (7) | C9—C8—H8B | 109.3 |
C1—N3—C12 | 118.8 (7) | C7—C8—H8B | 109.3 |
C11—N3—C12A | 121.5 (11) | H8A—C8—H8B | 107.9 |
C1—N3—C12A | 115.4 (11) | C10—C9—C8 | 178.34 (19) |
N4—C1—N1 | 110.63 (10) | C9—C10—H10 | 180.0 |
N4—C1—N3 | 125.09 (11) | O1—C11—N3 | 121.18 (10) |
N1—C1—N3 | 124.09 (10) | O1—C11—C7 | 123.93 (10) |
N5—C4—N1 | 111.14 (12) | N3—C11—C7 | 114.87 (9) |
N5—C4—H4 | 124.4 | C13—C12—N3 | 113.7 (6) |
N1—C4—H4 | 124.4 | C13—C12—H12A | 108.8 |
C1—N4—N5 | 106.72 (10) | N3—C12—H12A | 108.8 |
N2—C5—C6 | 116.50 (11) | C13—C12—H12B | 108.8 |
N2—C5—C7 | 122.72 (10) | N3—C12—H12B | 108.8 |
C6—C5—C7 | 120.73 (11) | H12A—C12—H12B | 107.7 |
C4—N5—N4 | 107.30 (10) | C14—C13—C12 | 177.9 (9) |
C5—C6—H6A | 109.5 | C13—C14—H14 | 180.0 |
C5—C6—H6B | 109.5 | C13A—C12A—N3 | 110.9 (8) |
H6A—C6—H6B | 109.5 | C13A—C12A—H12C | 109.5 |
C5—C6—H6C | 109.5 | N3—C12A—H12C | 109.5 |
H6A—C6—H6C | 109.5 | C13A—C12A—H12D | 109.5 |
H6B—C6—H6C | 109.5 | N3—C12A—H12D | 109.5 |
C5—C7—C11 | 108.32 (9) | H12C—C12A—H12D | 108.0 |
C5—C7—C8 | 115.01 (9) | C14A—C13A—C12A | 175.1 (17) |
C11—C7—C8 | 110.76 (9) | C13A—C14A—H14A | 180.0 |
C5—C7—H7 | 107.5 | ||
C4—N1—N2—C5 | −151.65 (12) | N2—C5—C7—C11 | −75.45 (14) |
C1—N1—N2—C5 | 44.75 (17) | C6—C5—C7—C11 | 102.00 (12) |
C4—N1—C1—N4 | 0.99 (13) | N2—C5—C7—C8 | 160.04 (11) |
N2—N1—C1—N4 | 167.07 (11) | C6—C5—C7—C8 | −22.50 (16) |
C4—N1—C1—N3 | −174.20 (11) | C5—C7—C8—C9 | −61.48 (15) |
N2—N1—C1—N3 | −8.12 (18) | C11—C7—C8—C9 | 175.30 (11) |
C11—N3—C1—N4 | 145.40 (12) | C1—N3—C11—O1 | −178.44 (11) |
C12—N3—C1—N4 | −28.4 (3) | C12—N3—C11—O1 | −4.6 (3) |
C12A—N3—C1—N4 | −31.9 (5) | C12A—N3—C11—O1 | −1.3 (5) |
C11—N3—C1—N1 | −40.11 (16) | C1—N3—C11—C7 | 2.93 (15) |
C12—N3—C1—N1 | 146.1 (3) | C12—N3—C11—C7 | 176.7 (3) |
C12A—N3—C1—N1 | 142.6 (5) | C12A—N3—C11—C7 | −179.9 (5) |
C1—N1—C4—N5 | −1.42 (15) | C5—C7—C11—O1 | −112.30 (13) |
N2—N1—C4—N5 | −168.53 (11) | C8—C7—C11—O1 | 14.70 (16) |
N1—C1—N4—N5 | −0.24 (13) | C5—C7—C11—N3 | 66.29 (12) |
N3—C1—N4—N5 | 174.88 (11) | C8—C7—C11—N3 | −166.71 (10) |
N1—N2—C5—C6 | −171.81 (11) | C11—N3—C12—C13 | −98.7 (11) |
N1—N2—C5—C7 | 5.75 (16) | C1—N3—C12—C13 | 75.3 (11) |
N1—C4—N5—N4 | 1.31 (16) | C11—N3—C12A—C13A | −80.7 (18) |
C1—N4—N5—C4 | −0.65 (15) | C1—N3—C12A—C13A | 96.7 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···N4i | 0.98 | 2.40 | 3.164 (2) | 135 |
C4—H4···O1ii | 0.93 | 2.23 | 3.147 (2) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
Acknowledgements
JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.
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