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ISSN: 2414-3146

7-Bromo-1,4-bis­­(prop-2-yn­yl)pyrido[2,3-b]pyrazine-2,3(1H,4H)-dione

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aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohammed Ben Abdellah, Fès, Morocco, bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014, Avenue Ibn Batouta, Rabat, Morocco
*Correspondence e-mail: sikine.meriem@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 February 2018; accepted 14 February 2018; online 23 February 2018)

In the title compound, C13H8BrN3O2, the pyrido-pyrazine fused-ring system is essentially planar (r.m.s. deviation = 0.061 Å). The prop-2-ynyl moieties are twisted away from the ring system in opposite directions. In the crystal, a single weak C—H⋯O inter­action generates [010] chains and aromatic ππ stacking inter­actions between the pyridine rings are observed.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Heterocycles containing a pyrido-pyrazine grouping possess useful medicinal properties (Zhang et al., 2012[Zhang, G., Liu, Y., Wang, S., Zhou, C., Huang, Q. & Gong, P. (2012). Arch. Pharm. Pharm. Med. Chem. 345, 49-56.]). They may also exhibit good inhibitory action on the corrosion of metals (Ouzidan et al., 2016[Ouzidan, Y., Ouazzani Chahdi, F., Essassi, E. M. & Hammouti, B. (2016). Pharma Chemica, 8, 85-95.]). As part of our studies in this area, we now report the synthesis of a new pyrido[2,3-b]pyrazine and its crystal structure.

The title compound crystallizes with one mol­ecule in the asymmetric unit (Fig. 1[link]). The pyrido-pyrazine moiety is essentially planar: the dihedral angle between the fused rings is 4.7 (6)°. The prop-2-ynyl moieties are twisted away from the mean plane of the pyrido-pyrazine ring [C8—C9—N2 = 114.0 (2)° and C12—C11—N1 = 110.1 (3)°] to avoid steric repulsion. In the crystal, a single weak C6—H6⋯O2 inter­action links the mol­ecules into [010] chains (Fig. 2[link] and Table 1[link]). In addition, weak ππ stacking between the pyridine rings is observed [centroid–centroid separation = 3.7089 (2) Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C6—H6⋯O2i 0.93 2.58 3.326 (4) 137
Symmetry code: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].
[Figure 1]
Figure 1
A view of the mol­ecular structure, showing displacement ellipsoids drawn at the 30% probability level.
[Figure 2]
Figure 2
A partial view along the c axis of the crystal packing. All H atoms except H6 have been omitted for clarity.

Synthesis and crystallization

To a solution of 7-bromo­pyrido[2,3-b]pyrazine-2,3(1H,4H)-dione (0.2 g, 0.826 mmol), K2CO3 (0.456 g, 3.304 mmol), tetra-n-bromide butyl ammonium (0.1 mmol) in DMF (15 ml) was added propargyl bromide (0.213 ml, 1.790 mmol), and the mixture was stirred for 24 h at room temperature. After the solvent was evaporated under reduced pressure, the product was isolated by chromatography on a silica gel column with ethyl acetate/hexane (1 /3) as the eluent. Red crystals were isolated when the solvent was allowed to evaporate (yield = 18%, m.p. 449 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C13H8BrN3O2
Mr 318.13
Crystal system, space group Monoclinic, P21/c
Temperature (K) 293
a, b, c (Å) 10.1922 (5), 17.347 (1), 7.0216 (4)
β (°) 92.382 (5)
V3) 1240.38 (12)
Z 4
Radiation type Cu Kα
μ (mm−1) 4.55
Crystal size (mm) 0.22 × 0.16 × 0.1
 
Data collection
Diffractometer Rigaku Oxford Diffraction
Absorption correction Multi-scan (CrysAlis PRO; Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.])
Tmin, Tmax 0.428, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 4477, 2361, 1994
Rint 0.025
(sin θ/λ)max−1) 0.614
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.101, 1.06
No. of reflections 2361
No. of parameters 172
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.50, −0.43
Computer programs: CrysAlis PRO (Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Structural data


Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

7-Bromo-1,4-bis(prop-2-ynyl)pyrido[2,3-b]pyrazine-2,3(1H,4H)-dione top
Crystal data top
C13H8BrN3O2F(000) = 632
Mr = 318.13Dx = 1.704 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
a = 10.1922 (5) ÅCell parameters from 1740 reflections
b = 17.347 (1) Åθ = 4.3–71.4°
c = 7.0216 (4) ŵ = 4.55 mm1
β = 92.382 (5)°T = 293 K
V = 1240.38 (12) Å3Prism, red
Z = 40.22 × 0.16 × 0.1 mm
Data collection top
Rigaku Oxford Diffraction model name?
diffractometer
2361 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source1994 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 16.0416 pixels mm-1θmax = 71.3°, θmin = 4.3°
ω scansh = 129
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2015)
k = 2018
Tmin = 0.428, Tmax = 1.000l = 87
4477 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.101 w = 1/[σ2(Fo2) + (0.0557P)2 + 0.1537P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2361 reflectionsΔρmax = 0.50 e Å3
172 parametersΔρmin = 0.43 e Å3
0 restraints
Special details top

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. All the H atoms were placed in their calculated positions and then refined using a riding model with bond lengths of 0.93 Å (CH) or 0.97 Å (CH2). Isotropic displacement parameters for all these atoms were set to 1.2 (CH, CH2) times Ueq of the parent atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.11401 (3)0.16664 (2)0.36163 (5)0.05288 (15)
O10.6397 (2)0.49748 (14)0.1531 (4)0.0559 (6)
O20.4267 (3)0.56084 (13)0.3097 (4)0.0620 (7)
N10.5551 (2)0.37741 (14)0.1875 (3)0.0396 (5)
N20.3293 (2)0.44352 (13)0.3284 (3)0.0363 (5)
N30.4718 (2)0.25464 (14)0.2338 (3)0.0402 (5)
C10.5508 (3)0.45577 (17)0.2002 (4)0.0416 (6)
C20.4292 (3)0.49169 (17)0.2831 (4)0.0419 (6)
C30.3366 (2)0.36362 (15)0.3063 (4)0.0325 (5)
C40.2339 (3)0.31484 (16)0.3433 (4)0.0370 (5)
H40.15370.33420.38000.044*
C50.2537 (3)0.23636 (15)0.3243 (4)0.0373 (5)
C60.3740 (3)0.20755 (16)0.2754 (4)0.0411 (6)
H60.38690.15450.27150.049*
C70.4528 (3)0.32983 (15)0.2449 (4)0.0347 (5)
C80.2161 (3)0.47795 (16)0.4219 (4)0.0422 (6)
H8A0.20100.44950.53790.051*
H8B0.23790.53060.45780.051*
C90.0952 (3)0.47845 (17)0.3036 (5)0.0436 (6)
C100.0066 (3)0.4782 (2)0.2184 (5)0.0535 (8)
H100.08710.47800.15110.064*
C110.6748 (3)0.34154 (19)0.1177 (5)0.0507 (7)
H11A0.65210.29440.04990.061*
H11B0.71600.37620.02970.061*
C120.7673 (3)0.32418 (18)0.2785 (6)0.0524 (8)
C130.8389 (4)0.3114 (3)0.4095 (7)0.0715 (11)
H130.89580.30120.51350.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0547 (2)0.0393 (2)0.0645 (2)0.01276 (13)0.00117 (15)0.00276 (13)
O10.0480 (12)0.0521 (13)0.0681 (15)0.0138 (10)0.0080 (10)0.0030 (11)
O20.0639 (14)0.0322 (11)0.0909 (19)0.0061 (10)0.0152 (13)0.0050 (11)
N10.0349 (11)0.0403 (12)0.0438 (13)0.0003 (9)0.0039 (9)0.0007 (10)
N20.0386 (11)0.0293 (10)0.0410 (12)0.0025 (9)0.0029 (9)0.0028 (9)
N30.0409 (12)0.0361 (11)0.0433 (12)0.0066 (9)0.0015 (9)0.0036 (10)
C10.0403 (14)0.0433 (15)0.0411 (14)0.0040 (12)0.0014 (11)0.0012 (12)
C20.0422 (14)0.0343 (14)0.0491 (16)0.0040 (11)0.0006 (11)0.0014 (11)
C30.0363 (12)0.0305 (12)0.0306 (12)0.0012 (10)0.0014 (9)0.0015 (10)
C40.0371 (13)0.0359 (13)0.0380 (13)0.0023 (11)0.0020 (10)0.0004 (11)
C50.0449 (14)0.0310 (13)0.0357 (13)0.0036 (11)0.0029 (10)0.0014 (10)
C60.0495 (15)0.0290 (13)0.0443 (15)0.0032 (11)0.0052 (12)0.0022 (11)
C70.0356 (12)0.0340 (13)0.0341 (13)0.0013 (10)0.0020 (9)0.0020 (10)
C80.0473 (15)0.0339 (13)0.0460 (15)0.0052 (11)0.0071 (12)0.0077 (11)
C90.0450 (16)0.0376 (14)0.0491 (16)0.0085 (11)0.0107 (12)0.0009 (12)
C100.0498 (18)0.0539 (18)0.0571 (19)0.0096 (14)0.0045 (14)0.0032 (15)
C110.0410 (15)0.0528 (18)0.0590 (19)0.0034 (12)0.0115 (13)0.0033 (14)
C120.0348 (14)0.0452 (16)0.078 (2)0.0002 (12)0.0109 (15)0.0023 (15)
C130.0465 (19)0.074 (3)0.094 (3)0.0025 (18)0.004 (2)0.012 (2)
Geometric parameters (Å, º) top
Br1—C51.894 (3)C4—H40.9300
O1—C11.217 (4)C4—C51.384 (4)
O2—C21.214 (4)C5—C61.381 (4)
N1—C11.363 (4)C6—H60.9300
N1—C71.402 (4)C8—H8A0.9700
N1—C111.472 (4)C8—H8B0.9700
N2—C21.365 (4)C8—C91.457 (5)
N2—C31.397 (3)C9—C101.176 (5)
N2—C81.477 (3)C10—H100.9300
N3—C61.331 (4)C11—H11A0.9700
N3—C71.322 (4)C11—H11B0.9700
C1—C21.524 (4)C11—C121.472 (5)
C3—C41.379 (4)C12—C131.172 (6)
C3—C71.405 (4)C13—H130.9300
C1—N1—C7122.8 (2)N3—C6—C5120.9 (2)
C1—N1—C11118.2 (2)N3—C6—H6119.5
C7—N1—C11118.9 (2)C5—C6—H6119.5
C2—N2—C3122.5 (2)N1—C7—C3119.3 (2)
C2—N2—C8117.4 (2)N3—C7—N1116.8 (2)
C3—N2—C8119.8 (2)N3—C7—C3123.9 (3)
C7—N3—C6118.7 (2)N2—C8—H8A108.8
O1—C1—N1123.3 (3)N2—C8—H8B108.8
O1—C1—C2119.2 (3)H8A—C8—H8B107.7
N1—C1—C2117.5 (2)C9—C8—N2114.0 (2)
O2—C2—N2123.2 (3)C9—C8—H8A108.8
O2—C2—C1119.0 (3)C9—C8—H8B108.8
N2—C2—C1117.7 (2)C10—C9—C8175.8 (3)
N2—C3—C7119.9 (2)C9—C10—H10180.0
C4—C3—N2122.9 (2)N1—C11—H11A109.6
C4—C3—C7117.3 (2)N1—C11—H11B109.6
C3—C4—H4121.0H11A—C11—H11B108.1
C3—C4—C5118.1 (2)C12—C11—N1110.1 (3)
C5—C4—H4121.0C12—C11—H11A109.6
C4—C5—Br1120.1 (2)C12—C11—H11B109.6
C6—C5—Br1118.9 (2)C13—C12—C11178.3 (4)
C6—C5—C4121.0 (3)C12—C13—H13180.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.583.326 (4)137
Symmetry code: (i) x+1, y1/2, z+1/2.
 

Funding information

JPJ acknowledges the NSF-MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationOuzidan, Y., Ouazzani Chahdi, F., Essassi, E. M. & Hammouti, B. (2016). Pharma Chemica, 8, 85–95.  Google Scholar
First citationRigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.  Google Scholar
First citationSheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationZhang, G., Liu, Y., Wang, S., Zhou, C., Huang, Q. & Gong, P. (2012). Arch. Pharm. Pharm. Med. Chem. 345, 49–56.  CrossRef CAS Google Scholar

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