2-Acetyl-pyridinium bromanilate.

In the crystal of the title mol-ecular salt (systematic name: 2-acetyl-pyridinium 2,5-dibromo-4-hydr-oxy-3,6-dioxocyclo-hexa-1,4-dienolate), C(7)H(8)NO(+)·C(6)HBr(2)O(4) (-), centrosymmetric rings consisting of two cations and two anions are formed, with the components linked by alternating O-H⋯O and N-H⋯O hydrogen bonds. Short O⋯Br contacts [3.243 (2) and 3.359 (2) Å] may help to consolidate the packing.

Related literature

For the structure of bromanilic acid, see: Robl (1987 ▶). For related structures, see: Tomura & Yamashita (2000 ▶); Zaman et al. (2001 ▶, 2004 ▶); Horiuchi et al. (2005 ▶).

Experimental

Crystal data

C7H8NO+·C6HBr2O4 −

M = 419.03

Monoclinic,

a = 9.1323 (5) Å

b = 13.3821 (7) Å

c = 12.2287 (7) Å

β = 112.396 (2)°

V = 1381.74 (13) Å3

Z = 4

Mo Kα radiation

μ = 5.89 mm−1

T = 100 K

0.25 × 0.2 × 0.1 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: empirical (using intensity measurements) (CrystalClear; Rigaku/MSC, 2008 ▶) T min = 0.561, T max = 1.000 (expected range = 0.311–0.555)

17193 measured reflections

3156 independent reflections

2793 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.050

S = 1.04

3156 reflections

219 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016456/hb2948sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016456/hb2948Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C7H8NO+·C6HBr2O4−	F(000) = 816
Mr = 419.03	Dx = 2.014 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13698 reflections
a = 9.1323 (5) Å	θ = 6.1–55.2°
b = 13.3821 (7) Å	µ = 5.89 mm−1
c = 12.2287 (7) Å	T = 100 K
β = 112.396 (2)°	Block, red
V = 1381.74 (13) Å3	0.25 × 0.2 × 0.1 mm
Z = 4

Rigaku R-AXIS RAPID IP diffractometer	2793 reflections with I > 2σ(I)
graphite	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: empirical (using intensity measurements) (CrystalClear; Rigaku/MSC, 2008)	h = −11→11
Tmin = 0.561, Tmax = 1.000	k = −17→17
17193 measured reflections	l = −15→15
3156 independent 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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F2) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0229P)2 + 0.7894P] where P = (Fo2 + 2Fc2)/3
3156 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 > 2σ(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. The isotropic displacement parameters for the hydrogen atoms involved in hydrogenbonds are refined freely. All other hydrogen atoms are refined against the atoms to which they are bonded.

	x	y	z	Uiso*/Ueq
H6	0.611 (3)	0.307 (2)	0.195 (3)	0.041 (8)*
O5	0.50649 (17)	0.44777 (11)	0.25644 (13)	0.0201 (3)
N1	0.5396 (2)	0.29814 (12)	0.11977 (16)	0.0152 (3)
C12	0.4282 (2)	0.45501 (15)	0.15172 (18)	0.0160 (4)
C11	0.5549 (2)	0.22016 (16)	0.05849 (19)	0.0200 (4)
H5	0.637 (3)	0.1735 (18)	0.102 (2)	0.024*
C8	0.3294 (2)	0.36207 (16)	−0.04572 (18)	0.0173 (4)
H2	0.263 (3)	0.4122 (18)	−0.076 (2)	0.021*
C10	0.4555 (3)	0.20854 (17)	−0.0595 (2)	0.0223 (5)
H4	0.468 (3)	0.156 (2)	−0.099 (2)	0.027*
C7	0.4298 (2)	0.37017 (14)	0.07151 (17)	0.0145 (4)
C9	0.3417 (3)	0.28035 (17)	−0.11190 (19)	0.0217 (4)
H3	0.274 (3)	0.2759 (19)	−0.195 (2)	0.026*
C13	0.3272 (3)	0.54328 (17)	0.0970 (2)	0.0232 (5)
H9	0.351 (3)	0.595 (2)	0.152 (2)	0.028*
H7	0.340 (3)	0.5618 (19)	0.027 (2)	0.028*
H8	0.222 (3)	0.5245 (19)	0.076 (2)	0.028*
H1	0.663 (4)	0.511 (2)	0.426 (3)	0.050 (10)*
Br1	0.92699 (2)	0.416206 (15)	0.738904 (17)	0.01764 (6)
Br2	0.98903 (2)	0.811177 (15)	0.427719 (17)	0.01869 (6)
O1	1.19471 (16)	0.56928 (11)	0.79086 (12)	0.0180 (3)
O2	1.22536 (16)	0.73058 (10)	0.67034 (12)	0.0186 (3)
O3	0.73311 (16)	0.64428 (11)	0.37219 (12)	0.0198 (3)
C5	0.9790 (2)	0.69726 (14)	0.51628 (17)	0.0150 (4)
O4	0.70848 (17)	0.48853 (11)	0.48976 (14)	0.0197 (3)
C1	0.8359 (2)	0.54445 (15)	0.54043 (18)	0.0152 (4)
C6	0.8462 (2)	0.63450 (15)	0.46801 (17)	0.0149 (4)
C4	1.1029 (2)	0.67882 (14)	0.62391 (18)	0.0139 (4)
C3	1.0879 (2)	0.58650 (14)	0.69581 (17)	0.0143 (4)
C2	0.9474 (2)	0.52459 (14)	0.64757 (17)	0.0145 (4)

	U11	U22	U33	U12	U13	U23
O5	0.0225 (8)	0.0205 (7)	0.0161 (7)	−0.0024 (6)	0.0059 (6)	−0.0021 (6)
N1	0.0126 (8)	0.0165 (8)	0.0135 (8)	0.0001 (6)	0.0014 (7)	0.0008 (7)
C12	0.0157 (10)	0.0161 (10)	0.0184 (10)	−0.0023 (7)	0.0088 (8)	0.0005 (8)
C11	0.0178 (10)	0.0179 (10)	0.0219 (11)	0.0044 (8)	0.0048 (9)	0.0002 (8)
C8	0.0129 (10)	0.0206 (10)	0.0158 (10)	0.0007 (8)	0.0024 (8)	0.0035 (8)
C10	0.0277 (12)	0.0212 (11)	0.0185 (11)	0.0005 (9)	0.0093 (9)	−0.0056 (9)
C7	0.0138 (9)	0.0143 (9)	0.0158 (10)	−0.0004 (7)	0.0062 (8)	0.0011 (8)
C9	0.0242 (11)	0.0246 (11)	0.0137 (10)	−0.0027 (9)	0.0045 (9)	−0.0002 (8)
C13	0.0271 (12)	0.0209 (11)	0.0249 (12)	0.0057 (9)	0.0135 (10)	0.0023 (9)
Br1	0.01649 (11)	0.01824 (11)	0.01617 (11)	−0.00241 (7)	0.00395 (8)	0.00493 (7)
Br2	0.02145 (12)	0.01616 (11)	0.01540 (11)	−0.00364 (7)	0.00360 (9)	0.00339 (7)
O1	0.0164 (7)	0.0188 (7)	0.0144 (7)	−0.0007 (5)	0.0011 (6)	0.0018 (6)
O2	0.0172 (7)	0.0158 (7)	0.0185 (7)	−0.0026 (5)	0.0020 (6)	0.0016 (6)
O3	0.0182 (7)	0.0229 (8)	0.0137 (7)	−0.0020 (6)	0.0008 (6)	0.0032 (6)
C5	0.0184 (10)	0.0128 (9)	0.0129 (9)	−0.0001 (7)	0.0051 (8)	0.0021 (7)
O4	0.0168 (8)	0.0208 (8)	0.0154 (7)	−0.0058 (6)	−0.0008 (6)	0.0026 (6)
C1	0.0155 (10)	0.0153 (9)	0.0154 (10)	−0.0005 (7)	0.0065 (8)	−0.0014 (8)
C6	0.0156 (10)	0.0165 (10)	0.0127 (9)	0.0016 (7)	0.0057 (8)	0.0005 (8)
C4	0.0147 (10)	0.0122 (9)	0.0152 (10)	0.0003 (7)	0.0061 (8)	−0.0013 (7)
C3	0.0164 (10)	0.0136 (9)	0.0145 (10)	0.0013 (7)	0.0077 (8)	−0.0015 (7)
C2	0.0167 (10)	0.0130 (9)	0.0151 (9)	−0.0001 (7)	0.0075 (8)	0.0012 (7)

O5—C12	1.209 (2)	C13—H7	0.94 (3)
N1—C11	1.323 (3)	C13—H8	0.93 (3)
N1—C7	1.353 (2)	Br1—C2	1.8826 (19)
N1—H6	0.91 (3)	Br2—C5	1.8922 (19)
C12—C13	1.491 (3)	O1—C3	1.221 (2)
C12—C7	1.504 (3)	O2—C4	1.253 (2)
C11—C10	1.390 (3)	O3—C6	1.239 (2)
C11—H5	0.96 (3)	C5—C4	1.392 (3)
C8—C7	1.381 (3)	C5—C6	1.407 (3)
C8—C9	1.390 (3)	O4—C1	1.322 (2)
C8—H2	0.89 (2)	O4—H1	0.79 (3)
C10—C9	1.381 (3)	C1—C2	1.344 (3)
C10—H4	0.88 (3)	C1—C6	1.520 (3)
C9—H3	0.97 (3)	C4—C3	1.552 (3)
C13—H9	0.93 (3)	C3—C2	1.451 (3)
C11—N1—C7	122.38 (18)	H9—C13—H7	112 (2)
C11—N1—H6	119.2 (18)	C12—C13—H8	107.8 (16)
C7—N1—H6	118.2 (18)	H9—C13—H8	110 (2)
O5—C12—C13	123.61 (19)	H7—C13—H8	107 (2)
O5—C12—C7	118.77 (18)	C4—C5—C6	123.42 (18)
C13—C12—C7	117.62 (18)	C4—C5—Br2	119.00 (14)
N1—C11—C10	120.53 (19)	C6—C5—Br2	117.57 (14)
N1—C11—H5	115.3 (15)	C1—O4—H1	107 (2)
C10—C11—H5	124.2 (15)	O4—C1—C2	123.31 (19)
C7—C8—C9	119.83 (19)	O4—C1—C6	114.51 (17)
C7—C8—H2	117.2 (16)	C2—C1—C6	122.18 (17)
C9—C8—H2	122.9 (16)	O3—C6—C5	127.49 (19)
C9—C10—C11	118.8 (2)	O3—C6—C1	114.86 (17)
C9—C10—H4	122.0 (16)	C5—C6—C1	117.65 (17)
C11—C10—H4	119.1 (16)	O2—C4—C5	126.44 (18)
N1—C7—C8	119.03 (18)	O2—C4—C3	116.07 (17)
N1—C7—C12	116.30 (17)	C5—C4—C3	117.48 (17)
C8—C7—C12	124.67 (18)	O1—C3—C2	122.78 (18)
C10—C9—C8	119.39 (19)	O1—C3—C4	118.58 (17)
C10—C9—H3	120.6 (15)	C2—C3—C4	118.64 (17)
C8—C9—H3	119.9 (15)	C1—C2—C3	120.51 (18)
C12—C13—H9	109.4 (16)	C1—C2—Br1	121.41 (15)
C12—C13—H7	110.4 (16)	C3—C2—Br1	118.08 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O5	0.78 (3)	2.20 (3)	2.798 (2)	134 (3)
N1—H6···O2i	0.91 (3)	1.83 (3)	2.673 (2)	154 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1⋯O5	0.78 (3)	2.20 (3)	2.798 (2)	134 (3)
N1—H6⋯O2i	0.91 (3)	1.83 (3)	2.673 (2)	154 (3)

Symmetry code: (i) .