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

Sikine, M.; Kandri Rodi, Y.; Ouzidan, Y.; Jasinski, J.P.; Kaur, M.; Essassi, E.M.

doi:10.1107/S2414314618002663

organic compounds

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ISSN: 2414-3146

Volume 3| Part 2| February 2018| x180266

https://doi.org/10.1107/S2414314618002663

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

Meriem Sikine,^a ^* Youssef Kandri Rodi,^a Younes Ouzidan,^a Jerry P. Jasinski,^b Manpreet Kaur ^b and El Mokhtar Essassi ^c

^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 π–π stacking interactions between the pyridine rings are observed.

Keywords: crystal structure; pyrido[2,3-b]pyrazine.

CCDC reference: 1823956

Structure description

Heterocycles containing a pyrido-pyrazine grouping possess useful medicinal properties (Zhang et al., 2012 ). They may also exhibit good inhibitory action on the corrosion of metals (Ouzidan et al., 2016 ). 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). 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 and Table 1). In addition, weak π–π 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	D⋯A	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
A view of the molecular structure, showing displacement ellipsoids drawn at the 30% probability level.

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.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₈BrN₃O₂
M_r	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)
V (Å³)	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 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.428, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4477, 2361, 1994
R_int	0.025
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (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 ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1823956

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618002663/hb4210sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618002663/hb4210Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618002663/hb4210Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314618002663/hb4210Isup4.cml

checkCIF report

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

C₁₃H₈BrN₃O₂	F(000) = 632
M_r = 318.13	D_x = 1.704 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.1922 (5) Å	Cell parameters from 1740 reflections
b = 17.347 (1) Å	θ = 4.3–71.4°
c = 7.0216 (4) Å	µ = 4.55 mm⁻¹
β = 92.382 (5)°	T = 293 K
V = 1240.38 (12) Å³	Prism, red
Z = 4	0.22 × 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 Source	1994 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.3°, θ_min = 4.3°
ω scans	h = −12→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −20→18
T_min = 0.428, T_max = 1.000	l = −8→7
4477 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0557P)² + 0.1537P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2361 reflections	Δρ_max = 0.50 e Å⁻³
172 parameters	Δρ_min = −0.43 e Å⁻³
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 U_eq of the parent atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.11401 (3)	0.16664 (2)	0.36163 (5)	0.05288 (15)
O1	0.6397 (2)	0.49748 (14)	0.1531 (4)	0.0559 (6)
O2	0.4267 (3)	0.56084 (13)	0.3097 (4)	0.0620 (7)
N1	0.5551 (2)	0.37741 (14)	0.1875 (3)	0.0396 (5)
N2	0.3293 (2)	0.44352 (13)	0.3284 (3)	0.0363 (5)
N3	0.4718 (2)	0.25464 (14)	0.2338 (3)	0.0402 (5)
C1	0.5508 (3)	0.45577 (17)	0.2002 (4)	0.0416 (6)
C2	0.4292 (3)	0.49169 (17)	0.2831 (4)	0.0419 (6)
C3	0.3366 (2)	0.36362 (15)	0.3063 (4)	0.0325 (5)
C4	0.2339 (3)	0.31484 (16)	0.3433 (4)	0.0370 (5)
H4	0.1537	0.3342	0.3800	0.044*
C5	0.2537 (3)	0.23636 (15)	0.3243 (4)	0.0373 (5)
C6	0.3740 (3)	0.20755 (16)	0.2754 (4)	0.0411 (6)
H6	0.3869	0.1545	0.2715	0.049*
C7	0.4528 (3)	0.32983 (15)	0.2449 (4)	0.0347 (5)
C8	0.2161 (3)	0.47795 (16)	0.4219 (4)	0.0422 (6)
H8A	0.2010	0.4495	0.5379	0.051*
H8B	0.2379	0.5306	0.4578	0.051*
C9	0.0952 (3)	0.47845 (17)	0.3036 (5)	0.0436 (6)
C10	−0.0066 (3)	0.4782 (2)	0.2184 (5)	0.0535 (8)
H10	−0.0871	0.4780	0.1511	0.064*
C11	0.6748 (3)	0.34154 (19)	0.1177 (5)	0.0507 (7)
H11A	0.6521	0.2944	0.0499	0.061*
H11B	0.7160	0.3762	0.0297	0.061*
C12	0.7673 (3)	0.32418 (18)	0.2785 (6)	0.0524 (8)
C13	0.8389 (4)	0.3114 (3)	0.4095 (7)	0.0715 (11)
H13	0.8958	0.3012	0.5135	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0547 (2)	0.0393 (2)	0.0645 (2)	−0.01276 (13)	0.00117 (15)	0.00276 (13)
O1	0.0480 (12)	0.0521 (13)	0.0681 (15)	−0.0138 (10)	0.0080 (10)	0.0030 (11)
O2	0.0639 (14)	0.0322 (11)	0.0909 (19)	−0.0061 (10)	0.0152 (13)	−0.0050 (11)
N1	0.0349 (11)	0.0403 (12)	0.0438 (13)	0.0003 (9)	0.0039 (9)	−0.0007 (10)
N2	0.0386 (11)	0.0293 (10)	0.0410 (12)	0.0025 (9)	0.0029 (9)	−0.0028 (9)
N3	0.0409 (12)	0.0361 (11)	0.0433 (12)	0.0066 (9)	−0.0015 (9)	−0.0036 (10)
C1	0.0403 (14)	0.0433 (15)	0.0411 (14)	−0.0040 (12)	−0.0014 (11)	0.0012 (12)
C2	0.0422 (14)	0.0343 (14)	0.0491 (16)	−0.0040 (11)	0.0006 (11)	−0.0014 (11)
C3	0.0363 (12)	0.0305 (12)	0.0306 (12)	0.0012 (10)	−0.0014 (9)	0.0015 (10)
C4	0.0371 (13)	0.0359 (13)	0.0380 (13)	0.0023 (11)	0.0020 (10)	−0.0004 (11)
C5	0.0449 (14)	0.0310 (13)	0.0357 (13)	−0.0036 (11)	−0.0029 (10)	0.0014 (10)
C6	0.0495 (15)	0.0290 (13)	0.0443 (15)	0.0032 (11)	−0.0052 (12)	−0.0022 (11)
C7	0.0356 (12)	0.0340 (13)	0.0341 (13)	0.0013 (10)	−0.0020 (9)	−0.0020 (10)
C8	0.0473 (15)	0.0339 (13)	0.0460 (15)	0.0052 (11)	0.0071 (12)	−0.0077 (11)
C9	0.0450 (16)	0.0376 (14)	0.0491 (16)	0.0085 (11)	0.0107 (12)	0.0009 (12)
C10	0.0498 (18)	0.0539 (18)	0.0571 (19)	0.0096 (14)	0.0045 (14)	−0.0032 (15)
C11	0.0410 (15)	0.0528 (18)	0.0590 (19)	0.0034 (12)	0.0115 (13)	−0.0033 (14)
C12	0.0348 (14)	0.0452 (16)	0.078 (2)	−0.0002 (12)	0.0109 (15)	0.0023 (15)
C13	0.0465 (19)	0.074 (3)	0.094 (3)	0.0025 (18)	−0.004 (2)	0.012 (2)

Geometric parameters (Å, º) top

Br1—C5	1.894 (3)	C4—H4	0.9300
O1—C1	1.217 (4)	C4—C5	1.384 (4)
O2—C2	1.214 (4)	C5—C6	1.381 (4)
N1—C1	1.363 (4)	C6—H6	0.9300
N1—C7	1.402 (4)	C8—H8A	0.9700
N1—C11	1.472 (4)	C8—H8B	0.9700
N2—C2	1.365 (4)	C8—C9	1.457 (5)
N2—C3	1.397 (3)	C9—C10	1.176 (5)
N2—C8	1.477 (3)	C10—H10	0.9300
N3—C6	1.331 (4)	C11—H11A	0.9700
N3—C7	1.322 (4)	C11—H11B	0.9700
C1—C2	1.524 (4)	C11—C12	1.472 (5)
C3—C4	1.379 (4)	C12—C13	1.172 (6)
C3—C7	1.405 (4)	C13—H13	0.9300

C1—N1—C7	122.8 (2)	N3—C6—C5	120.9 (2)
C1—N1—C11	118.2 (2)	N3—C6—H6	119.5
C7—N1—C11	118.9 (2)	C5—C6—H6	119.5
C2—N2—C3	122.5 (2)	N1—C7—C3	119.3 (2)
C2—N2—C8	117.4 (2)	N3—C7—N1	116.8 (2)
C3—N2—C8	119.8 (2)	N3—C7—C3	123.9 (3)
C7—N3—C6	118.7 (2)	N2—C8—H8A	108.8
O1—C1—N1	123.3 (3)	N2—C8—H8B	108.8
O1—C1—C2	119.2 (3)	H8A—C8—H8B	107.7
N1—C1—C2	117.5 (2)	C9—C8—N2	114.0 (2)
O2—C2—N2	123.2 (3)	C9—C8—H8A	108.8
O2—C2—C1	119.0 (3)	C9—C8—H8B	108.8
N2—C2—C1	117.7 (2)	C10—C9—C8	175.8 (3)
N2—C3—C7	119.9 (2)	C9—C10—H10	180.0
C4—C3—N2	122.9 (2)	N1—C11—H11A	109.6
C4—C3—C7	117.3 (2)	N1—C11—H11B	109.6
C3—C4—H4	121.0	H11A—C11—H11B	108.1
C3—C4—C5	118.1 (2)	C12—C11—N1	110.1 (3)
C5—C4—H4	121.0	C12—C11—H11A	109.6
C4—C5—Br1	120.1 (2)	C12—C11—H11B	109.6
C6—C5—Br1	118.9 (2)	C13—C12—C11	178.3 (4)
C6—C5—C4	121.0 (3)	C12—C13—H13	180.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.58	3.326 (4)	137

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Funding information

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

References

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