Literature DB >> 25705482

Crystal structure of 2-aza-niumyl-3-bromo-6-oxo-5,6-di-hydro-pyrido[1,2-a]quinoxalin-11-ium dibromide.

Md Serajul Haque Faizi¹, Natalia O Sharkina², Turganbay S Iskenderov².

Abstract

The title salt, C12H10BrN3O(2+)·2Br(-), was synthesized from the reaction of N (1),N (4)-bis-(pyridin-2-yl-methyl-idene)benzene-1,4-di-amine and bromine in a methanol solution. All non-H atoms of the 2-aza-niumyl-3-bromo-6-oxo-5,6-di-hydro-pyrido[1,2-a]quinoxalin-11-ium cation are nearly coplanar, the maximum deviation being 0.114 (4) Å. In the crystal, the cations and anions are linked through N-H⋯Br hydrogen bonds and weak C-H⋯Br inter-actions, forming a three-dimensional supra-molecular architecture. A short Br⋯Br contact [3.3088 (9) Å] is observed in the crystal.

Entities: CellLine Chemical Disease Species

Keywords: C—H⋯Br interactions; bromide; crystal structure; pyrido[1,2-a]quinoxalin-11-ium

Year: 2015 PMID： 25705482 PMCID： PMC4331889 DOI： 10.1107/S2056989014026127

Source DB: PubMed Journal: Acta Crystallogr E Crystallogr Commun

Related literature

For applications of quinoxalines, see: Duffy et al. (2002 ▸); Gazit et al. (1996 ▸); Harmenberg et al. (1991 ▸); Naylor et al. (1993 ▸). For types of quinoxalines and a structure similar to title compound, see: Eiden & Peter (1966 ▸); Koner & Ray (2008 ▸); Fritsky et al. (2006 ▸); Kanderal et al. (2005 ▸); Moroz et al. (2012 ▸). For background to and applications of related compounds, see: Faizi & Sen (2014 ▸); Faizi et al. (2014 ▸).

Experimental

Crystal data

C12H10BrN3O2+·2Br− M = 451.96 Monoclinic, a = 5.6782 (2) Å b = 11.9822 (4) Å c = 20.2528 (7) Å β = 90.891 (2)° V = 1377.78 (8) Å3 Z = 4 Mo Kα radiation μ = 8.78 mm−1 T = 100 K 0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▸) T min = 0.178, T max = 0.273 14369 measured reflections 2424 independent reflections 1804 reflections with I > 2σ(I) R int = 0.106

Refinement

R[F 2 > 2σ(F 2)] = 0.047 wR(F 2) = 0.130 S = 0.97 2424 reflections 173 parameters H-atom parameters constrained Δρmax = 1.23 e Å−3 Δρmin = −0.88 e Å−3

Data collection: SMART (Bruker, 2003 ▸); cell refinement: SAINT (Bruker, 2003 ▸); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: DIAMOND (Brandenberg & Putz, 2006 ▸); software used to prepare material for publication: DIAMOND. Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014026127/xu5829sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026127/xu5829Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S2056989014026127/xu5829Isup3.cml Click here for additional data file. . DOI: 10.1107/S2056989014026127/xu5829fig1.tif The molecular conformation and atom-numbering scheme for the title compound, with non-H atoms drawn as 40% probability displacement ellipsoids. CCDC reference: 1036569 Additional supporting information: crystallographic information; 3D view; checkCIF report

C₁₂H₁₀BrN₃O²⁺·2Br⁻	F(000) = 864
M_r = 451.96	D_x = 2.179 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 999 reflections
a = 5.6782 (2) Å	θ = 2.6–28.6°
b = 11.9822 (4) Å	µ = 8.78 mm⁻¹
c = 20.2528 (7) Å	T = 100 K
β = 90.891 (2)°	Block, yellow
V = 1377.78 (8) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker SMART APEX CCD diffractometer	2424 independent reflections
Radiation source: fine-focus sealed tube	1804 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.106
ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −6→6
T_min = 0.178, T_max = 0.273	k = −14→14
14369 measured reflections	l = −23→24

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) = 0.130	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0801P)²] where P = (F_o² + 2F_c²)/3
2424 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 1.23 e Å⁻³
0 restraints	Δρ_min = −0.88 e Å⁻³

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. 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 > 2sigma(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	U_iso*/U_eq
C1	1.1684 (11)	0.3466 (5)	0.6250 (3)	0.0348 (16)
H1	1.1805	0.3779	0.5821	0.042*
C2	1.3279 (12)	0.3771 (5)	0.6724 (3)	0.0404 (17)
H2	1.4479	0.4297	0.6628	0.049*
C3	1.3135 (12)	0.3313 (6)	0.7341 (3)	0.0432 (18)
H3	1.4246	0.3511	0.7676	0.052*
C4	1.1375 (12)	0.2564 (6)	0.7472 (3)	0.0408 (17)
H4	1.1293	0.2230	0.7896	0.049*
C5	0.9719 (11)	0.2291 (5)	0.6989 (3)	0.0308 (15)
C6	0.7750 (11)	0.1557 (5)	0.7166 (3)	0.0327 (15)
C7	0.6487 (11)	0.1672 (5)	0.6019 (3)	0.0284 (14)
C8	0.4824 (11)	0.1344 (5)	0.5543 (3)	0.0297 (14)
H8	0.3582	0.0851	0.5655	0.036*
C9	0.5012 (11)	0.1750 (5)	0.4905 (3)	0.0287 (14)
C10	0.6803 (11)	0.2482 (5)	0.4745 (3)	0.0272 (14)
C11	0.8407 (11)	0.2812 (5)	0.5212 (3)	0.0294 (14)
H11	0.9619	0.3323	0.5104	0.035*
C12	0.8249 (11)	0.2387 (5)	0.5857 (3)	0.0252 (14)
N1	0.9939 (8)	0.2736 (4)	0.6368 (2)	0.0262 (11)
N2	0.6287 (9)	0.1254 (4)	0.6658 (2)	0.0319 (12)
H2A	0.5160	0.0770	0.6737	0.038*
N3	0.6987 (9)	0.2912 (4)	0.4080 (2)	0.0343 (13)
H1N3	0.8278	0.3360	0.4054	0.052*
H2N3	0.5673	0.3314	0.3976	0.052*
H3N3	0.7126	0.2334	0.3792	0.052*
O1	0.7430 (8)	0.1251 (4)	0.7735 (2)	0.0428 (12)
Br1	0.82448 (12)	0.04974 (5)	0.33038 (3)	0.0399 (2)
Br2	0.21399 (13)	0.05913 (6)	0.91141 (4)	0.0478 (3)
Br3	0.26693 (12)	0.12868 (6)	0.42784 (3)	0.0388 (2)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.035 (4)	0.036 (4)	0.033 (4)	−0.004 (3)	0.000 (3)	0.003 (3)
C2	0.038 (4)	0.036 (4)	0.047 (4)	−0.002 (3)	−0.002 (3)	−0.002 (3)
C3	0.038 (5)	0.053 (5)	0.038 (4)	0.003 (4)	−0.005 (3)	−0.015 (4)
C4	0.039 (4)	0.053 (4)	0.030 (4)	0.001 (3)	−0.002 (3)	−0.007 (3)
C5	0.031 (4)	0.040 (4)	0.021 (3)	0.004 (3)	0.002 (3)	−0.005 (3)
C6	0.030 (4)	0.040 (4)	0.028 (4)	0.006 (3)	−0.002 (3)	−0.008 (3)
C7	0.036 (4)	0.031 (4)	0.018 (3)	0.002 (3)	0.002 (3)	−0.001 (3)
C8	0.026 (4)	0.031 (3)	0.032 (4)	0.001 (3)	0.004 (3)	0.000 (3)
C9	0.029 (4)	0.033 (3)	0.024 (3)	0.004 (3)	−0.008 (3)	−0.005 (3)
C10	0.030 (4)	0.035 (4)	0.016 (3)	0.005 (3)	0.006 (2)	−0.002 (3)
C11	0.023 (4)	0.035 (4)	0.030 (3)	−0.002 (3)	0.007 (3)	−0.002 (3)
C12	0.026 (4)	0.027 (3)	0.022 (3)	0.000 (3)	0.003 (3)	−0.002 (3)
N1	0.026 (3)	0.030 (3)	0.023 (3)	0.001 (2)	0.001 (2)	−0.002 (2)
N2	0.033 (3)	0.037 (3)	0.026 (3)	−0.002 (2)	0.005 (2)	0.002 (2)
N3	0.041 (4)	0.043 (3)	0.020 (3)	0.005 (2)	0.004 (2)	0.002 (2)
O1	0.050 (3)	0.062 (3)	0.016 (2)	−0.007 (2)	0.008 (2)	0.004 (2)
Br1	0.0317 (5)	0.0464 (5)	0.0415 (4)	−0.0044 (3)	0.0032 (3)	−0.0017 (3)
Br2	0.0423 (5)	0.0435 (5)	0.0579 (5)	−0.0028 (3)	0.0115 (4)	−0.0072 (3)
Br3	0.0370 (5)	0.0460 (5)	0.0333 (4)	0.0011 (3)	−0.0044 (3)	−0.0048 (3)

C1—N1	1.346 (7)	C7—N2	1.394 (7)
C1—C2	1.359 (9)	C8—C9	1.387 (8)
C1—H1	0.9500	C8—H8	0.9500
C2—C3	1.368 (9)	C9—C10	1.385 (9)
C2—H2	0.9500	C9—Br3	1.907 (6)
C3—C4	1.372 (10)	C10—C11	1.362 (8)
C3—H3	0.9500	C10—N3	1.449 (7)
C4—C5	1.384 (8)	C11—C12	1.405 (8)
C4—H4	0.9500	C11—H11	0.9500
C5—N1	1.374 (7)	C12—N1	1.462 (7)
C5—C6	1.471 (9)	N2—H2A	0.8800
C6—O1	1.225 (7)	N3—H1N3	0.9100
C6—N2	1.361 (8)	N3—H2N3	0.9100
C7—C12	1.361 (8)	N3—H3N3	0.9100
C7—C8	1.395 (8)

N1—C1—C2	122.3 (6)	C8—C9—C10	120.5 (6)
N1—C1—H1	118.9	C8—C9—Br3	117.1 (5)
C2—C1—H1	118.9	C10—C9—Br3	122.4 (4)
C1—C2—C3	119.2 (7)	C11—C10—C9	120.5 (5)
C1—C2—H2	120.4	C11—C10—N3	119.0 (6)
C3—C2—H2	120.4	C9—C10—N3	120.5 (5)
C2—C3—C4	119.6 (6)	C10—C11—C12	119.2 (6)
C2—C3—H3	120.2	C10—C11—H11	120.4
C4—C3—H3	120.2	C12—C11—H11	120.4
C3—C4—C5	120.4 (6)	C7—C12—C11	120.7 (6)
C3—C4—H4	119.8	C7—C12—N1	119.1 (5)
C5—C4—H4	119.8	C11—C12—N1	120.2 (5)
N1—C5—C4	119.0 (6)	C1—N1—C5	119.5 (5)
N1—C5—C6	122.3 (5)	C1—N1—C12	122.5 (5)
C4—C5—C6	118.7 (6)	C5—N1—C12	118.0 (5)
O1—C6—N2	122.2 (6)	C6—N2—C7	123.2 (5)
O1—C6—C5	122.1 (6)	C6—N2—H2A	118.4
N2—C6—C5	115.7 (5)	C7—N2—H2A	118.4
C12—C7—C8	120.2 (5)	C10—N3—H1N3	109.5
C12—C7—N2	121.4 (5)	C10—N3—H2N3	109.5
C8—C7—N2	118.5 (6)	H1N3—N3—H2N3	109.5
C9—C8—C7	119.0 (6)	C10—N3—H3N3	109.5
C9—C8—H8	120.5	H1N3—N3—H3N3	109.5
C7—C8—H8	120.5	H2N3—N3—H3N3	109.5

N1—C1—C2—C3	0.9 (10)	N2—C7—C12—C11	−179.2 (5)
C1—C2—C3—C4	−0.7 (11)	C8—C7—C12—N1	178.6 (5)
C2—C3—C4—C5	−1.5 (11)	N2—C7—C12—N1	−1.1 (9)
C3—C4—C5—N1	3.4 (10)	C10—C11—C12—C7	−1.4 (9)
C3—C4—C5—C6	−175.0 (6)	C10—C11—C12—N1	−179.5 (5)
N1—C5—C6—O1	−172.7 (6)	C2—C1—N1—C5	1.1 (9)
C4—C5—C6—O1	5.7 (9)	C2—C1—N1—C12	−178.7 (6)
N1—C5—C6—N2	6.4 (8)	C4—C5—N1—C1	−3.2 (9)
C4—C5—C6—N2	−175.2 (6)	C6—C5—N1—C1	175.2 (5)
C12—C7—C8—C9	0.6 (9)	C4—C5—N1—C12	176.5 (5)
N2—C7—C8—C9	−179.7 (5)	C6—C5—N1—C12	−5.1 (8)
C7—C8—C9—C10	−0.9 (9)	C7—C12—N1—C1	−178.0 (6)
C7—C8—C9—Br3	−179.4 (4)	C11—C12—N1—C1	0.1 (9)
C8—C9—C10—C11	0.1 (9)	C7—C12—N1—C5	2.3 (8)
Br3—C9—C10—C11	178.4 (4)	C11—C12—N1—C5	−179.6 (5)
C8—C9—C10—N3	−179.5 (5)	O1—C6—N2—C7	174.0 (6)
Br3—C9—C10—N3	−1.1 (8)	C5—C6—N2—C7	−5.1 (8)
C9—C10—C11—C12	1.1 (9)	C12—C7—N2—C6	2.7 (9)
N3—C10—C11—C12	−179.3 (5)	C8—C7—N2—C6	−177.0 (5)
C8—C7—C12—C11	0.6 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br1ⁱ	0.88	2.46	3.322 (5)	167
N3—H1N3···Br2ⁱⁱ	0.91	2.53	3.432 (5)	171
N3—H2N3···Br2ⁱⁱⁱ	0.91	2.42	3.287 (5)	160
N3—H3N3···Br1	0.91	2.50	3.374 (5)	162
C2—H2···Br2^iv	0.95	2.91	3.813 (6)	160
C3—H3···Br1^v	0.95	2.85	3.752 (7)	160
C8—H8···Br1ⁱ	0.95	2.86	3.672 (6)	144
C11—H11···Br2ⁱⁱ	0.95	2.80	3.639 (6)	148

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2ABr1ⁱ	0.88	2.46	3.322(5)	167
N3H1N3Br2ⁱⁱ	0.91	2.53	3.432(5)	171
N3H2N3Br2ⁱⁱⁱ	0.91	2.42	3.287(5)	160
N3H3N3Br1	0.91	2.50	3.374(5)	162
C2H2Br2^iv	0.95	2.91	3.813(6)	160
C3H3Br1^v	0.95	2.85	3.752(7)	160
C8H8Br1ⁱ	0.95	2.86	3.672(6)	144
C11H11Br2ⁱⁱ	0.95	2.80	3.639(6)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

11 in total

1. Efficient stabilization of copper(III) in tetraaza pseudo-macrocyclic oxime-and-hydrazide ligands with adjustable cavity size.

Authors: Igor O Fritsky; Henryk Kozłowski; Olga M Kanderal; Matti Haukka; Jolanta Swiatek-Kozłowska; Elzbieta Gumienna-Kontecka; Franc Meyer
Journal: Chem Commun (Camb) Date: 2006-08-22 Impact factor: 6.222

2. Effect of metal ionic radius and chelate ring alternation motif on stabilization of trivalent nickel and copper in binuclear complexes with double cis-oximato bridges.

Authors: Olga M Kanderal; Henryk Kozlowski; Agnieszka Dobosz; Jolanta Swiatek-Kozlowska; Franc Meyer; Igor O Fritsky
Journal: Dalton Trans Date: 2005-03-15 Impact factor: 4.390

3. Regular high-nuclearity species from square building blocks: a triangular 3 × [2 × 2] Ni12 complex generated by the self-assembly of three [2 × 2] Ni4 molecular grids.

Authors: Yurii S Moroz; Serhiy Demeshko; Matti Haukka; Andriy Mokhir; Utpal Mitra; Michael Stocker; Paul Müller; Franc Meyer; Igor O Fritsky
Journal: Inorg Chem Date: 2012-07-05 Impact factor: 5.165

4. Tyrphostins. 5. Potent inhibitors of platelet-derived growth factor receptor tyrosine kinase: structure-activity relationships in quinoxalines, quinolines, and indole tyrphostins.

Authors: A Gazit; H App; G McMahon; J Chen; A Levitzki; F D Bohmer
Journal: J Med Chem Date: 1996-05-24 Impact factor: 7.446

5. [Reactions with chelidonic acid. 3. On re-arrangements of pyranylidene-carbonic acid derivatives with diamines. 10. Studies on gamma-pyrones].

Authors: F Eiden; P Peter
Journal: Arch Pharm Ber Dtsch Pharm Ges Date: 1966-02

6. The mechanism of action of the anti-herpes virus compound 2,3-dimethyl-6(2-dimethylaminoethyl)-6H-indolo-(2,3-b)quinoxaline.

Authors: J Harmenberg; A Akesson-Johansson; A Gräslund; T Malmfors; J Bergman; B Wahren; S Akerfeldt; L Lundblad; S Cox
Journal: Antiviral Res Date: 1991 Mar-Apr Impact factor: 5.970

7. Cu(II)-mediated synthesis of a new fluorescent pyrido[1,2-a]quinoxalin-11-ium derivative.

Authors: Rik Rani Koner; Manabendra Ray
Journal: Inorg Chem Date: 2008-09-17 Impact factor: 5.165

8. Heterocyclic mono-N-oxides with potential applications as bioreductive anti-tumour drugs: Part 1. 8-Alkylamino-substituted phenylimidazo [1,2-a] quinoxalines.

Authors: M A Naylor; M A Stephens; J Nolan; B Sutton; J H Tocher; E M Fielden; G E Adams; I J Stratford
Journal: Anticancer Drug Des Date: 1993-12

9. N (1)-[(1H-Imidazol-2-yl)methyl-idene]-N (4)-phenyl-benzene-1,4-di-amine.

Authors: Md Serajul Haque Faizi; Ashraf Mashrai; M Shahid; Musheer Ahmad
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2014-06-25

10. [Bis(quinolin-2-ylcarbon-yl)amido-κ(3) N,N',N'']bromido-(N,N-di-methyl-formamide-κO)copper(II).

Authors: Md Serajul Haque Faizi; Pratik Sen
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2014-05-10