2-Acetyl­pyridinium bromanilate

Thomas, L.H.; Boyle, B.; Clive, L.A.; Collins, A.; Currie, L.D.; Gogol, M.; Hastings, C.; Jones, A.O.F.; Kennedy, J.L.; Kerr, G.B.; Kidd, A.; Lawton, L.M.; Macintyre, S.J.; MacLean, N.M.; Martin, A.R.G.; McGonagle, K.; Melrose, S.; Rew, G.A.; Robinson, C.W.; Schmidtmann, M.; Turnbull, F.B.; Williams, L.G.; Wiseman, A.Y.; Wocial, M.H.; Wilson, C.C.

doi:10.1107/S1600536809016456

organic compounds

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2-Acetylpyridinium bromanilate

^aWestCHEM, Department of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, Scotland, and ^bDepartment of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, Scotland
^*Correspondence e-mail: lynnet@chem.gla.ac.uk

(Received 8 April 2009; accepted 1 May 2009; online 7 May 2009)

In the crystal of the title molecular salt (systematic name: 2-acetylpyridinium 2,5-dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-dienolate), C₇H₈NO⁺·C₆HBr₂O₄⁻, 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_r = 419.03
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.022
wR(F²) = 0.050
S = 1.04
3156 reflections
219 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.31 e Å⁻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) -x+2, -y+1, -z+1.

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 ).

Supporting information

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

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

checkCIF report

Comment top

The stucture of the molecular proton-transfer salt of bromanilic acid with 2-acetylpyridine at 100 K is reported (Fig. 1). A proton is transferred from the bromanilic acid molecule to the N atom on the acetylpyridine (Fig. 1). All previously reported structures containing bromanilic acid have shown the tendency for extended chains of molecules to form. In this case, hydrogen-bonded rings are formed between alternating cations and anions (Fig. 2) and these rings are held together to form a three-dimensional structure by one Br···O close contact of 3.243 (2)Å (cf the sum of the van der Waals radii for Br and O of 3.37Å) and one on the limit of the sum of the van der Waals radii of of 3.359 (2)Å (Fig. 3). The deprotonated hydroxyl group on the bromanilic acid molecule is stabilized by forming a moderate hydrogen bond [2.673 (2)Å] with the N atom on the 2-acetylpyridine molecule to which the proton has been transferred, and a short O···Br contact with another bromanilic acid molecule. The C—O bond length to the deprotonated oxygen is notably shortened compared to that to the protonated hydroxyl group [1.253 (2)Å versus 1.322 (2)Å]. The longer of the two O···Br close contacts is to the C═O group on the bromanilic acid [C═O bond length 1.221 (2)Å].

Related literature top

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 top

Red blocks of (I) were grown by slow evaporation of solvent from a 1:1 solution of bromanilic acid and 2-acetylpyridine in methanol.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); 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).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The hydrogen bonded ring between alternating bromanilic acid and acetylpyridine molecules. The hydrogen bonds are indicated by dashed lines. The * indicates the atoms are related by the symmetry code 2 - x, 1 - y, 1 - z.
	Fig. 3. The short bromine-oxygen close contacts connecting the hydrogen bonded rings. The short contacts and hydrogen bonds are indicated by dashed lines.

2-Acetylpyridinium bromanilate top

Crystal data top

C₇H₈NO⁺·C₆HBr₂O₄⁻	F(000) = 816
M_r = 419.03	D_x = 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

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2793 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: empirical (using intensity measurements) (CrystalClear; Rigaku/MSC, 2008)	h = −11→11
T_min = 0.561, T_max = 1.000	k = −17→17
17193 measured reflections	l = −15→15
3156 independent reflections

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)] = 0.022	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(F_o²) + (0.0229P)² + 0.7894P] where P = (F_o² + 2F_c²)/3
3156 reflections	(Δ/σ)_max = 0.001
219 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₇H₈NO⁺·C₆HBr₂O₄⁻	V = 1381.74 (13) Å³
M_r = 419.03	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1323 (5) Å	µ = 5.89 mm⁻¹
b = 13.3821 (7) Å	T = 100 K
c = 12.2287 (7) Å	0.25 × 0.2 × 0.1 mm
β = 112.396 (2)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	3156 independent reflections
Absorption correction: empirical (using intensity measurements) (CrystalClear; Rigaku/MSC, 2008)	2793 reflections with I > 2σ(I)
T_min = 0.561, T_max = 1.000	R_int = 0.036
17193 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.43 e Å⁻³
3156 reflections	Δρ_min = −0.31 e Å⁻³
219 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₈NO⁺·C₆HBr₂O₄⁻
M_r	419.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.1323 (5), 13.3821 (7), 12.2287 (7)
β (°)	112.396 (2)
V (Å³)	1381.74 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.89
Crystal size (mm)	0.25 × 0.2 × 0.1

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Empirical (using intensity measurements) (CrystalClear; Rigaku/MSC, 2008)
T_min, T_max	0.561, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17193, 3156, 2793
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.050, 1.04
No. of reflections	3156
No. of parameters	219
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.31

Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+1, −z+1.

References

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