Crystal structure of 2-amino-1,3-di­bromo-6-oxo-5,6-di­hydro­pyrido[1,2-a]quinoxalin-11-ium bromide monohydrate

Faizi, M.S.H.; Parashchenko, Y.

doi:10.1107/S2056989015018253

Crystal structure of 2-amino-1,3-dibromo-6-oxo-5,6-dihydropyrido[1,2-a]quinoxalin-11-ium bromide monohydrate

In the title compound, the 2-amino-1,3-dibromo-6-oxo-5,6-dihydropyrido[1,2-a]quinoxalin-11-ium cations are non-planar and are linked through centrosymmetric hydrogen-bonded cyclic Br₂(H₂O)₂ anion–water units by N—H

Br, N—H

O and O—H

Br hydrogen bonds, forming one-dimensional ribbons, with the planes of the cations lying parallel to (100).

Keywords: crystal structure; hydrogen bonding; quinoxaline derivatives; pyrido[1,2-a]quinoxalines.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015018253/zs2343sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015018253/zs2343Isup2.hkl Contains datablock I

CCDC reference: 1428593

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.011 Å
R factor = 0.059
wR factor = 0.155
Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5676
PLAT023_ALERT_3_B Resolution (too) Low [sin(theta)/Lambda < 0.6]..      23.79 Degree

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.163
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.1 Note
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0111 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.175 Report
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.568         15 Report
PLAT975_ALERT_2_C Check Calcd Residual Density  0.84A From      O2       0.63 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.99A From      N3       0.46 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.61A From      N3       0.41 eA-3

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          5 Report
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00700 Degree
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          56 %

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   7 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 (Brandenberg & Putz, 2006).

2-Amino-1,3-dibromo-6-oxo-5,6-dihydropyrido[1,2-a]quinoxalin-11-ium bromide monohydrate top

Crystal data top

C₁₂H₈Br₂N₃O⁺·Br⁻·H₂O	Z = 2
M_r = 467.93	F(000) = 448
Triclinic, P1	D_x = 2.163 Mg m⁻³
a = 7.5069 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7435 (10) Å	Cell parameters from 1023 reflections
c = 10.782 (1) Å	θ = 1.5–23.5°
α = 88.490 (7)°	µ = 8.42 mm⁻¹
β = 73.798 (7)°	T = 100 K
γ = 71.981 (7)°	Block, yellow
V = 718.61 (12) Å³	0.20 × 0.15 × 0.11 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2187 independent reflections
Radiation source: fine-focus sealed tube	1681 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.163
/w–scans	θ_max = 23.8°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −8→8
T_min = 0.259, T_max = 0.365	k = −11→10
8077 measured reflections	l = −12→12

Refinement top

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0902P)²] where P = (F_o² + 2F_c²)/3
2187 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 1.18 e Å⁻³
0 restraints	Δρ_min = −1.16 e Å⁻³

Special details top

Experimental. The OH H-atom was located in difference Fourier map and refined with with U_iso(H) = 1.2U_eq(O). The N- and C-bound H-atoms were positioned geometrically and refined using a riding model: N—H = 0.86 Å and C—H = 0.93 Å with U_iso(H) = 1.2U_eq(parent atom).

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.

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

	x	y	z	U_iso*/U_eq
Br3	0.26076 (12)	0.03614 (8)	0.73364 (8)	0.0441 (3)
Br2	0.27561 (13)	0.36785 (8)	0.22264 (8)	0.0446 (3)
Br1	0.30008 (13)	0.45076 (9)	−0.29950 (8)	0.0480 (3)
C3	0.1893 (12)	0.8452 (10)	0.4590 (8)	0.048 (2)
H3	0.2041	0.8791	0.5342	0.058*
C1	0.1158 (12)	0.6740 (8)	0.3479 (7)	0.0388 (19)
H1	0.0617	0.5998	0.3495	0.047*
N1	0.1941 (9)	0.7217 (6)	0.2309 (6)	0.0316 (14)
C2	0.1146 (14)	0.7316 (9)	0.4612 (8)	0.048 (2)
H2	0.0644	0.6953	0.5393	0.057*
C4	0.2417 (12)	0.9077 (9)	0.3430 (8)	0.046 (2)
H4	0.2805	0.9898	0.3414	0.055*
C12	0.2134 (10)	0.6506 (7)	0.1102 (7)	0.0306 (17)
N2	0.2314 (10)	0.8738 (6)	0.0112 (6)	0.0377 (16)
H5	0.2190	0.9269	−0.0528	0.045*
C7	0.2241 (11)	0.7334 (7)	0.0019 (7)	0.0327 (18)
C11	0.2384 (11)	0.5009 (7)	0.0921 (7)	0.0318 (18)
C9	0.2558 (11)	0.5314 (8)	−0.1296 (8)	0.0362 (19)
C10	0.2586 (10)	0.4390 (7)	−0.0288 (7)	0.0324 (18)
C8	0.2379 (11)	0.6744 (7)	−0.1175 (8)	0.0349 (18)
H6	0.2351	0.7313	−0.1879	0.042*
C5	0.2364 (11)	0.8482 (8)	0.2307 (8)	0.0353 (18)
C6	0.2565 (12)	0.9308 (8)	0.1142 (8)	0.042 (2)
O1	0.2841 (12)	1.0476 (6)	0.1172 (7)	0.071 (2)
N3	0.2950 (11)	0.2940 (7)	−0.0508 (7)	0.0457 (18)
H3A	0.3064	0.2371	0.0109	0.055*
H3B	0.3066	0.2597	−0.1263	0.055*
O2	0.3545 (11)	0.2190 (7)	0.4635 (6)	0.072 (2)
H12	0.3415	0.2338	0.5459	0.108*
H11	0.4550	0.1520	0.4120	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br3	0.0499 (5)	0.0360 (5)	0.0489 (5)	−0.0143 (4)	−0.0173 (4)	0.0057 (4)
Br2	0.0516 (6)	0.0273 (5)	0.0573 (6)	−0.0140 (4)	−0.0184 (4)	0.0127 (4)
Br1	0.0565 (6)	0.0389 (5)	0.0510 (6)	−0.0130 (4)	−0.0206 (4)	−0.0041 (4)
C3	0.044 (5)	0.051 (6)	0.051 (5)	−0.013 (4)	−0.017 (4)	−0.003 (4)
C1	0.046 (5)	0.029 (4)	0.043 (5)	−0.014 (4)	−0.012 (4)	0.004 (4)
N1	0.033 (3)	0.022 (3)	0.045 (4)	−0.012 (3)	−0.016 (3)	0.007 (3)
C2	0.061 (6)	0.042 (5)	0.040 (5)	−0.016 (5)	−0.017 (4)	0.012 (4)
C4	0.052 (5)	0.033 (4)	0.060 (6)	−0.018 (4)	−0.021 (4)	−0.006 (4)
C12	0.032 (4)	0.022 (4)	0.040 (4)	−0.011 (3)	−0.010 (3)	0.000 (3)
N2	0.052 (4)	0.018 (3)	0.044 (4)	−0.010 (3)	−0.016 (3)	0.006 (3)
C7	0.036 (4)	0.016 (4)	0.047 (5)	−0.007 (3)	−0.015 (4)	0.006 (3)
C11	0.033 (4)	0.017 (4)	0.051 (5)	−0.014 (3)	−0.014 (3)	0.009 (3)
C9	0.037 (4)	0.030 (4)	0.048 (5)	−0.013 (4)	−0.018 (4)	−0.004 (4)
C10	0.029 (4)	0.016 (4)	0.053 (5)	−0.005 (3)	−0.017 (4)	0.004 (4)
C8	0.038 (4)	0.020 (4)	0.045 (5)	−0.008 (3)	−0.009 (4)	0.002 (3)
C5	0.036 (4)	0.018 (4)	0.049 (5)	−0.002 (3)	−0.014 (4)	−0.004 (3)
C6	0.053 (5)	0.017 (4)	0.057 (5)	−0.013 (4)	−0.016 (4)	0.002 (4)
O1	0.115 (6)	0.030 (3)	0.086 (5)	−0.041 (4)	−0.038 (4)	0.007 (3)
N3	0.069 (5)	0.022 (3)	0.052 (4)	−0.019 (3)	−0.022 (4)	0.003 (3)
O2	0.077 (5)	0.063 (4)	0.064 (4)	−0.005 (4)	−0.020 (4)	0.015 (4)

Geometric parameters (Å, º) top

Br2—C11	1.907 (7)	N2—C6	1.338 (10)
Br1—C9	1.912 (8)	N2—C7	1.393 (9)
C3—C2	1.384 (12)	N2—H5	0.8600
C3—C4	1.387 (12)	C7—C8	1.388 (11)
C3—H3	0.9300	C11—C10	1.400 (11)
C1—C2	1.355 (11)	C9—C8	1.364 (10)
C1—N1	1.370 (10)	C9—C10	1.394 (11)
C1—H1	0.9300	C10—N3	1.367 (9)
N1—C5	1.364 (9)	C8—H6	0.9300
N1—C12	1.440 (9)	C5—C6	1.471 (11)
C2—H2	0.9300	C6—O1	1.222 (9)
C4—C5	1.373 (11)	N3—H3A	0.8600
C4—H4	0.9300	N3—H3B	0.8600
C12—C7	1.399 (10)	O2—H12	0.8769
C12—C11	1.423 (9)	O2—H11	0.8900

C2—C3—C4	119.0 (8)	C12—C7—N2	120.3 (7)
C2—C3—H3	120.5	C10—C11—C12	121.3 (7)
C4—C3—H3	120.5	C10—C11—Br2	115.3 (5)
C2—C1—N1	122.1 (8)	C12—C11—Br2	123.0 (6)
C2—C1—H1	119.0	C8—C9—C10	124.3 (7)
N1—C1—H1	119.0	C8—C9—Br1	117.2 (6)
C5—N1—C1	118.1 (6)	C10—C9—Br1	118.3 (5)
C5—N1—C12	119.7 (6)	N3—C10—C11	122.5 (7)
C1—N1—C12	121.9 (6)	N3—C10—C9	121.0 (7)
C1—C2—C3	118.9 (8)	C11—C10—C9	116.3 (6)
C1—C2—H2	120.5	C9—C8—C7	118.8 (7)
C3—C2—H2	120.5	C9—C8—H6	120.6
C5—C4—C3	119.9 (8)	C7—C8—H6	120.6
C5—C4—H4	120.1	N1—C5—C4	120.2 (7)
C3—C4—H4	120.1	N1—C5—C6	120.8 (7)
C7—C12—C11	118.4 (7)	C4—C5—C6	118.7 (7)
C7—C12—N1	116.8 (6)	O1—C6—N2	123.8 (8)
C11—C12—N1	124.6 (6)	O1—C6—C5	120.2 (8)
C6—N2—C7	123.7 (6)	N2—C6—C5	115.9 (7)
C6—N2—H5	118.2	C10—N3—H3A	120.0
C7—N2—H5	118.2	C10—N3—H3B	120.0
C8—C7—C12	120.5 (7)	H3A—N3—H3B	120.0
C8—C7—N2	119.1 (7)	H12—O2—H11	123.0

C2—C1—N1—C5	−13.0 (11)	Br2—C11—C10—C9	−172.4 (6)
C2—C1—N1—C12	173.4 (7)	C8—C9—C10—N3	−173.9 (8)
N1—C1—C2—C3	2.1 (12)	Br1—C9—C10—N3	1.0 (10)
C4—C3—C2—C1	7.5 (12)	C8—C9—C10—C11	1.0 (12)
C2—C3—C4—C5	−6.1 (13)	Br1—C9—C10—C11	175.9 (5)
C5—N1—C12—C7	−16.6 (10)	C10—C9—C8—C7	0.9 (12)
C1—N1—C12—C7	156.8 (7)	Br1—C9—C8—C7	−174.0 (6)
C5—N1—C12—C11	157.9 (7)	C12—C7—C8—C9	−4.9 (11)
C1—N1—C12—C11	−28.7 (11)	N2—C7—C8—C9	171.8 (7)
C11—C12—C7—C8	6.7 (11)	C1—N1—C5—C4	14.3 (10)
N1—C12—C7—C8	−178.4 (7)	C12—N1—C5—C4	−172.0 (7)
C11—C12—C7—N2	−169.9 (7)	C1—N1—C5—C6	−159.2 (7)
N1—C12—C7—N2	5.0 (11)	C12—N1—C5—C6	14.4 (10)
C6—N2—C7—C8	−166.8 (7)	C3—C4—C5—N1	−5.0 (12)
C6—N2—C7—C12	9.8 (12)	C3—C4—C5—C6	168.7 (8)
C7—C12—C11—C10	−4.7 (11)	C7—N2—C6—O1	171.7 (9)
N1—C12—C11—C10	−179.2 (7)	C7—N2—C6—C5	−12.2 (11)
C7—C12—C11—Br2	168.1 (6)	N1—C5—C6—O1	176.1 (8)
N1—C12—C11—Br2	−6.4 (11)	C4—C5—C6—O1	2.5 (12)
C12—C11—C10—N3	175.8 (7)	N1—C5—C6—N2	−0.1 (11)
Br2—C11—C10—N3	2.4 (10)	C4—C5—C6—N2	−173.8 (7)
C12—C11—C10—C9	0.9 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H5···Br3ⁱ	0.86	2.49	3.332 (6)	166
N3—H3B···Br1	0.86	2.60	3.048 (7)	113
N3—H3B···Br3ⁱⁱ	0.86	2.84	3.581 (7)	145
N3—H3A···O1ⁱⁱⁱ	0.86	2.17	2.977 (9)	155
N3—H3A···Br2	0.86	2.56	3.006 (7)	113
O2—H11···Br3^iv	0.89	2.50	3.383 (6)	180
O2—H12···Br1^v	0.88	2.61	3.309 (7)	137
O2—H12···Br3	0.88	2.83	3.393 (6)	123

Symmetry codes: (i) x, y+1, z−1; (ii) x, y, z−1; (iii) x, y−1, z; (iv) −x+1, −y, −z+1; (v) x, y, z+1.

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Crystal structure of 2-amino-1,3-di­bromo-6-oxo-5,6-di­hydro­pyrido[1,2-a]quinoxalin-11-ium bromide monohydrate

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure of 2-amino-1,3-dibromo-6-oxo-5,6-dihydropyrido[1,2-a]quinoxalin-11-ium bromide monohydrate