1-Methyl-4-(4-nitro-benzo-yl)pyridinium perchlorate.

In the main mol-ecule of the title compound, C(13)H(11)N(2)O(3) (+)·ClO(4) (-), the two aromatic rings are twisted by 56.19 (3)° relative to each other and the nitro group is not coplanar with the benzene ring [36.43 (4)°]. The crystal packing is dominated by infinite aromatic stacks in the a-axis direction. These are formed by the benzene units of the mol-ecule featuring an alternating arrangement, which explains the two different distances of 3.3860 (4) and 3.4907 (4) Å for the aromatic units (these are the perpendicular distances of the centroid of one aromatic ring on the mean plane of the other other aromatic ring). Adjacent stacks are connected by π-π stacking between two pyridinium units [3.5949 (4) Å] and weak C-H⋯O inter-actions. The perchlorate anions are accomodated in the lattice voids connected to the cation via weak C-H⋯O contacts between the O atoms of the anion and various aromatic as well as methyl H atoms.

Related literature

For an alternative synthesis and the electrochemical and host/guest characteristics of the title compound, see: Fischer (1973 ▶); Leventis et al. (2004a ▶,b ▶); Rawashdeh et al. (2008 ▶). For related pyridinium ions, see: Kolev et al. (2001 ▶, 2005 ▶, 2006 ▶). For complexes of 4-benzoyl­pyridine with transistion metals, see: Araki et al. (2005 ▶); Mautner & Gohera (1998 ▶); Gohera & Mak (1998 ▶); Escuer et al. (2000 ▶); Gohera & Mautner (1999 ▶); Drew et al. (1985 ▶); Gotsis & White (1987 ▶). Respective co-crystals and derivatives are discussed in Sugiyama et al. (2002a ▶,b ▶) and Syed et al. (1984 ▶).

Experimental

Crystal data

C13H11N2O3 +·ClO4 −

M = 342.69

Triclinic,

a = 7.9240 (3) Å

b = 7.9800 (3) Å

c = 12.6350 (6) Å

α = 105.980 (2)°

β = 104.119 (1)°

γ = 99.138 (1)°

V = 722.67 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 153 K

0.45 × 0.39 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.875, T max = 0.919

20599 measured reflections

5199 independent reflections

4759 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.092

S = 1.06

5199 reflections

209 parameters

H-atom parameters constrained

Δρmax = 0.65 e Å−3

Δρmin = −0.46 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034945/im2313sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034945/im2313Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811034945/im2313Isup3.cml

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

C13H11N2O3+·ClO4−	Z = 2
Mr = 342.69	F(000) = 352
Triclinic, P1	Dx = 1.575 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9240 (3) Å	Cell parameters from 6858 reflections
b = 7.9800 (3) Å	θ = 2.7–44.1°
c = 12.6350 (6) Å	µ = 0.31 mm−1
α = 105.980 (2)°	T = 153 K
β = 104.119 (1)°	Piece, colourless
γ = 99.138 (1)°	0.45 × 0.39 × 0.15 mm
V = 722.67 (5) Å3

Bruker Kappa APEXII CCD diffractometer	5199 independent reflections
Radiation source: fine-focus sealed tube	4759 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 32.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→11
Tmin = 0.875, Tmax = 0.919	k = −12→12
20599 measured reflections	l = −19→19

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0551P)2 + 0.1728P] where P = (Fo2 + 2Fc2)/3
5199 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.65 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

Experimental. N-Methyl-4-(4-nitrobenzoyl)pyridinium iodide (II). To a stirred solution of 2.14?g (10?mmol) 4-(4-nitrobenzyl)pyridine in 20?ml toluene, 2.50 g (17.6 mmol) methyl iodide were added. While heating under reflux for 30 min, the colour of the solution changed from yellow to purple, and a solid precipitated, which was collected and recrystallized from acetone/methanol (1:1 v/v). After several days, II could be harvested as deep red crystals (1.65 g, 45%). M.p. 484–485 K. 1H-NMR (DMSO-d6) δ 4.50 (s, 3 H, CH3), 8.10 (d, 2 H, ArH-9, ArH-12), 8.45 (m, 4 H, ArH-2, ArH-3, ArH-5, ArH-6), 9.28 (d, 2 H, ArH-10, ArH-11); 13C-NMR (DMSO-d6) δ 48.44 (CH3), 123.92, 126.84 (2-, 6-, 9-, 12-ArC), 131.60 (3-, 5-ArC), 139.13 (4-ArC), 146.66 (8-ArC), 149.73, 150.44 (1-, 10-, 11-ArC), 191.03 (C=O).N-Methyl-4-(4-nitrobenzoyl)pyridinium perchlorate (I). A solution of 1.0 g (2.7 mmol) of II in 100 ml ethanol was reacted with 15 ml perchloric acid (70%) (Caution!) to yield colourless crystals of (I) after four weeks (230 mg, 25%). M.p. 464–465 K. 1H-NMR (DMSO-d6) δ 4.46 (s, 3 H, CH3), 8.06 (d, 2 H, ArH-9, ArH-12), 8.28 (m, 4 H, ArH-2, ArH-3, ArH-5, ArH-6), 9.21 (d, 2 H, ArH-10, ArH-11); 13C-NMR (DMSO-d6) δ 48.33 (CH3), 123.98, 126.91 (2-, 6-, 9-, 12-ArC), 131.57 (3-, 5-ArC), 139.22 (4-ArC), 146.70 (8-ArC), 149.84, 150.54 (1-, 10-, 11-ArC), 191.08 (C=O).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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	Uiso*/Ueq
O1	0.21076 (10)	0.03649 (11)	0.75601 (6)	0.02567 (14)
O2	0.48688 (9)	0.15551 (10)	0.77549 (6)	0.02398 (14)
O3	0.09175 (9)	−0.25751 (9)	0.16586 (6)	0.02171 (13)
N1	0.33202 (10)	0.07804 (10)	0.71642 (6)	0.01796 (13)
N2	0.23169 (10)	0.29598 (10)	0.06813 (6)	0.01774 (13)
C1	0.28772 (11)	0.03276 (11)	0.59073 (7)	0.01597 (13)
C2	0.16321 (11)	−0.12663 (11)	0.52203 (7)	0.01882 (15)
H2	0.1083	−0.2049	0.5553	0.023*
C3	0.12131 (11)	−0.16827 (11)	0.40303 (7)	0.01830 (14)
H3	0.0389	−0.2780	0.3535	0.022*
C4	0.20033 (11)	−0.04878 (10)	0.35605 (7)	0.01519 (13)
C5	0.32546 (11)	0.11108 (11)	0.42782 (7)	0.01684 (14)
H5	0.3786	0.1914	0.3952	0.020*
C6	0.37179 (11)	0.15206 (11)	0.54715 (7)	0.01746 (14)
H6	0.4585	0.2587	0.5973	0.021*
C7	0.15140 (10)	−0.10129 (11)	0.22792 (7)	0.01583 (13)
C8	0.17711 (10)	0.04177 (11)	0.17269 (7)	0.01528 (13)
C9	0.13320 (12)	0.20531 (11)	0.21083 (7)	0.01856 (15)
H9	0.0845	0.2303	0.2735	0.022*
C10	0.16116 (12)	0.33074 (12)	0.15649 (8)	0.01980 (15)
H10	0.1305	0.4423	0.1815	0.024*
C11	0.27066 (12)	0.13678 (12)	0.02789 (7)	0.01927 (15)
H11	0.3181	0.1145	−0.0354	0.023*
C12	0.24204 (12)	0.00559 (12)	0.07807 (7)	0.01801 (14)
H12	0.2664	−0.1079	0.0483	0.022*
C13	0.27377 (13)	0.43875 (13)	0.01795 (8)	0.02376 (17)
H13A	0.1777	0.5026	0.0122	0.036*
H13B	0.2839	0.3847	−0.0592	0.036*
H13C	0.3875	0.5235	0.0676	0.036*
Cl1	0.70498 (3)	0.38019 (2)	0.243705 (16)	0.01746 (6)
O4	0.58098 (11)	0.28582 (13)	0.28579 (8)	0.03593 (19)
O5	0.69466 (14)	0.27089 (12)	0.12976 (7)	0.0388 (2)
O6	0.66108 (14)	0.54567 (11)	0.23798 (8)	0.0376 (2)
O7	0.88363 (10)	0.41729 (10)	0.32064 (7)	0.02936 (16)

	U11	U22	U33	U12	U13	U23
O1	0.0294 (3)	0.0341 (4)	0.0188 (3)	0.0093 (3)	0.0123 (3)	0.0115 (3)
O2	0.0234 (3)	0.0258 (3)	0.0179 (3)	0.0067 (2)	−0.0007 (2)	0.0054 (2)
O3	0.0258 (3)	0.0173 (3)	0.0178 (3)	0.0018 (2)	0.0047 (2)	0.0028 (2)
N1	0.0216 (3)	0.0198 (3)	0.0142 (3)	0.0086 (2)	0.0048 (2)	0.0068 (2)
N2	0.0178 (3)	0.0209 (3)	0.0143 (3)	0.0026 (2)	0.0037 (2)	0.0078 (2)
C1	0.0170 (3)	0.0192 (3)	0.0127 (3)	0.0059 (3)	0.0044 (2)	0.0059 (3)
C2	0.0205 (3)	0.0196 (3)	0.0166 (3)	0.0020 (3)	0.0055 (3)	0.0081 (3)
C3	0.0196 (3)	0.0173 (3)	0.0159 (3)	0.0003 (3)	0.0041 (3)	0.0056 (3)
C4	0.0161 (3)	0.0160 (3)	0.0135 (3)	0.0033 (2)	0.0044 (2)	0.0052 (2)
C5	0.0180 (3)	0.0170 (3)	0.0150 (3)	0.0018 (3)	0.0053 (3)	0.0055 (3)
C6	0.0181 (3)	0.0174 (3)	0.0151 (3)	0.0021 (3)	0.0042 (3)	0.0045 (3)
C7	0.0154 (3)	0.0174 (3)	0.0144 (3)	0.0038 (2)	0.0042 (2)	0.0052 (3)
C8	0.0155 (3)	0.0177 (3)	0.0125 (3)	0.0041 (2)	0.0039 (2)	0.0049 (2)
C9	0.0213 (3)	0.0203 (3)	0.0183 (3)	0.0079 (3)	0.0100 (3)	0.0076 (3)
C10	0.0228 (4)	0.0201 (3)	0.0193 (4)	0.0075 (3)	0.0085 (3)	0.0077 (3)
C11	0.0210 (3)	0.0244 (4)	0.0129 (3)	0.0055 (3)	0.0062 (3)	0.0061 (3)
C12	0.0215 (3)	0.0205 (3)	0.0122 (3)	0.0068 (3)	0.0056 (3)	0.0041 (3)
C13	0.0254 (4)	0.0250 (4)	0.0209 (4)	0.0003 (3)	0.0053 (3)	0.0124 (3)
Cl1	0.01988 (9)	0.01675 (9)	0.01702 (9)	0.00538 (6)	0.00752 (7)	0.00529 (7)
O4	0.0248 (3)	0.0491 (5)	0.0350 (4)	−0.0025 (3)	0.0119 (3)	0.0193 (4)
O5	0.0544 (5)	0.0345 (4)	0.0236 (4)	0.0117 (4)	0.0172 (4)	−0.0019 (3)
O6	0.0580 (6)	0.0274 (4)	0.0320 (4)	0.0249 (4)	0.0095 (4)	0.0123 (3)
O7	0.0185 (3)	0.0273 (3)	0.0383 (4)	0.0036 (2)	0.0036 (3)	0.0102 (3)

O1—N1	1.2280 (10)	C6—H6	0.9500
O2—N1	1.2260 (10)	C7—C8	1.5052 (11)
O3—C7	1.2191 (10)	C8—C12	1.3910 (11)
N1—C1	1.4655 (10)	C8—C9	1.3915 (11)
N2—C11	1.3466 (11)	C9—C10	1.3800 (12)
N2—C10	1.3487 (11)	C9—H9	0.9500
N2—C13	1.4803 (11)	C10—H10	0.9500
C1—C6	1.3855 (11)	C11—C12	1.3819 (12)
C1—C2	1.3858 (11)	C11—H11	0.9500
C2—C3	1.3885 (11)	C12—H12	0.9500
C2—H2	0.9500	C13—H13A	0.9800
C3—C4	1.3988 (11)	C13—H13B	0.9800
C3—H3	0.9500	C13—H13C	0.9800
C4—C5	1.3984 (11)	Cl1—O4	1.4337 (8)
C4—C7	1.4885 (11)	Cl1—O6	1.4340 (8)
C5—C6	1.3911 (11)	Cl1—O5	1.4383 (8)
C5—H5	0.9500	Cl1—O7	1.4401 (8)
O2—N1—O1	124.08 (8)	C12—C8—C9	119.35 (7)
O2—N1—C1	118.26 (7)	C12—C8—C7	118.31 (7)
O1—N1—C1	117.66 (7)	C9—C8—C7	122.32 (7)
C11—N2—C10	121.28 (7)	C10—C9—C8	119.22 (7)
C11—N2—C13	119.58 (7)	C10—C9—H9	120.4
C10—N2—C13	119.09 (8)	C8—C9—H9	120.4
C6—C1—C2	123.63 (7)	N2—C10—C9	120.44 (8)
C6—C1—N1	118.23 (7)	N2—C10—H10	119.8
C2—C1—N1	118.14 (7)	C9—C10—H10	119.8
C1—C2—C3	117.82 (7)	N2—C11—C12	120.44 (7)
C1—C2—H2	121.1	N2—C11—H11	119.8
C3—C2—H2	121.1	C12—C11—H11	119.8
C2—C3—C4	120.07 (7)	C11—C12—C8	119.18 (8)
C2—C3—H3	120.0	C11—C12—H12	120.4
C4—C3—H3	120.0	C8—C12—H12	120.4
C5—C4—C3	120.66 (7)	N2—C13—H13A	109.5
C5—C4—C7	121.64 (7)	N2—C13—H13B	109.5
C3—C4—C7	117.66 (7)	H13A—C13—H13B	109.5
C6—C5—C4	119.76 (7)	N2—C13—H13C	109.5
C6—C5—H5	120.1	H13A—C13—H13C	109.5
C4—C5—H5	120.1	H13B—C13—H13C	109.5
C1—C6—C5	118.03 (7)	O4—Cl1—O6	110.12 (6)
C1—C6—H6	121.0	O4—Cl1—O5	109.24 (6)
C5—C6—H6	121.0	O6—Cl1—O5	108.89 (6)
O3—C7—C4	121.94 (7)	O4—Cl1—O7	109.05 (5)
O3—C7—C8	118.68 (7)	O6—Cl1—O7	109.59 (5)
C4—C7—C8	119.37 (7)	O5—Cl1—O7	109.94 (5)
O2—N1—C1—C6	−36.02 (11)	C5—C4—C7—C8	−23.70 (11)
O1—N1—C1—C6	143.63 (8)	C3—C4—C7—C8	158.50 (8)
O2—N1—C1—C2	144.34 (8)	O3—C7—C8—C12	−39.66 (11)
O1—N1—C1—C2	−36.01 (11)	C4—C7—C8—C12	139.93 (8)
C6—C1—C2—C3	0.10 (13)	O3—C7—C8—C9	138.36 (9)
N1—C1—C2—C3	179.72 (7)	C4—C7—C8—C9	−42.06 (11)
C1—C2—C3—C4	−1.68 (13)	C12—C8—C9—C10	−2.33 (13)
C2—C3—C4—C5	1.70 (13)	C7—C8—C9—C10	179.68 (8)
C2—C3—C4—C7	179.52 (8)	C11—N2—C10—C9	2.39 (13)
C3—C4—C5—C6	−0.10 (13)	C13—N2—C10—C9	−175.05 (8)
C7—C4—C5—C6	−177.83 (7)	C8—C9—C10—N2	−0.59 (13)
C2—C1—C6—C5	1.46 (13)	C10—N2—C11—C12	−1.20 (13)
N1—C1—C6—C5	−178.16 (7)	C13—N2—C11—C12	176.23 (8)
C4—C5—C6—C1	−1.43 (12)	N2—C11—C12—C8	−1.75 (13)
C5—C4—C7—O3	155.88 (8)	C9—C8—C12—C11	3.47 (12)
C3—C4—C7—O3	−21.92 (12)	C7—C8—C12—C11	−178.45 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O7i	0.95	2.60	3.478 (1)	153.
C3—H3···O7ii	0.95	2.42	3.277 (1)	150.
C5—H5···O4	0.95	2.51	3.394 (1)	154.
C9—H9···O7iii	0.95	2.42	3.132 (1)	132.
C10—H10···O3iv	0.95	2.52	3.392 (1)	153.
C11—H11···O1v	0.95	2.43	3.200 (1)	138.
C12—H12···O5vi	0.95	2.39	3.134 (1)	135.
C13—H13A···O3iv	0.98	2.63	3.373 (1)	133.
C13—H13B···O6vii	0.98	2.59	3.429 (1)	144.
C13—H13C···O2viii	0.98	2.63	3.446 (1)	141.
C13—H13C···O6	0.98	2.60	3.402 (1)	139.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O7i	0.95	2.60	3.478 (1)	153
C3—H3⋯O7ii	0.95	2.42	3.277 (1)	150
C5—H5⋯O4	0.95	2.51	3.394 (1)	154
C9—H9⋯O7iii	0.95	2.42	3.132 (1)	132
C10—H10⋯O3iv	0.95	2.52	3.392 (1)	153
C11—H11⋯O1v	0.95	2.43	3.200 (1)	138
C12—H12⋯O5vi	0.95	2.39	3.134 (1)	135
C13—H13A⋯O3iv	0.98	2.63	3.373 (1)	133
C13—H13B⋯O6vii	0.98	2.59	3.429 (1)	144
C13—H13C⋯O2viii	0.98	2.63	3.446 (1)	141
C13—H13C⋯O6	0.98	2.60	3.402 (1)	139

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