2-Cyano-1-methyl-pyridinium nitrate.

In the title compound, C(7)H(7)N(2) (+)·NO(3) (-), all atoms except the methyl H atoms lie on a crystallographic mirror plane. The inter-layer distance, including that between aligned N atoms from alternating cations and anions in adjacent layers, is exceptionally short at 3.055 (1) Å. Two-dimensional C-H⋯O hydrogen-bonded networks link cations to anions, while C-H⋯N inter-actions link cations within each layer. Anion-π inter-actions with the cations assist in binding the layers together.

Related literature

For the structure of 2-cyano­anilinium nitrate, see: Cui & Wen (2008 ▶). For the structures of other 2- and 3-cyano­anilinium salts, see: Zhang (2009 ▶); Wang (2009a ▶,b ▶); Wen (2008 ▶). For previous work on cyano-N-methyl­pyridinium salts, see: Koplitz et al. (2003 ▶); Mague et al. (2005 ▶). For a discussion of anion–π inter­actions, see: Frontera et al. (2011 ▶).

Experimental

Crystal data

C7H7N2 +·NO3 −

M = 181.16

Orthorhombic,

a = 16.302 (3) Å

b = 6.1012 (10) Å

c = 8.0318 (13) Å

V = 798.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 160 K

0.22 × 0.14 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (TWINABS; Sheldrick, 2009 ▶) T min = 0.652, T max = 0.985

25942 measured reflections

1143 independent reflections

1005 reflections with I > 2σ(I)

R int = 0.069

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.156

S = 1.14

1143 reflections

80 parameters

H-atom parameters constrained

Δρmax = 0.46 e Å−3

Δρmin = −0.78 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT and CELL_NOW (Sheldrick, 2008b ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a ▶); molecular graphics: SHELXTL (Sheldrick, 2008a ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812019460/hb6770sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019460/hb6770Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812019460/hb6770Isup3.cml

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

C7H7N2+·NO3−	F(000) = 376
Mr = 181.16	Dx = 1.506 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1462 reflections
a = 16.302 (3) Å	θ = 2.5–28.1°
b = 6.1012 (10) Å	µ = 0.12 mm−1
c = 8.0318 (13) Å	T = 160 K
V = 798.9 (2) Å3	Block, colourless
Z = 4	0.22 × 0.14 × 0.13 mm

Bruker SMART APEX CCD [or Bruker APEXII CCD?]diffractometer	1143 independent reflections
Radiation source: fine-focus sealed tube	1005 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
φ and ω scans	θmax = 29.1°, θmin = 2.5°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	h = 0→22
Tmin = 0.652, Tmax = 0.985	k = 0→8
25942 measured reflections	l = 0→10

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) = 0.156	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0984P)2 + 0.1829P] where P = (Fo2 + 2Fc2)/3
1143 reflections	(Δ/σ)max < 0.001
80 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.78 e Å−3

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5 °. in omega, colllected at phi = 0.00, 90.00 and 180.00 °. and 2 sets of 800 frames, each of width 0.45 ° in phi, collected at omega = -30.00 and 210.00 °. The scan time was sec/frame. Analysis of 576 reflections having I/σ(I) > 15 and chosen from the full data set with CELL_NOW (Sheldrick, 2008b) showed the crystal to belong to the orthorhombic system and to be twinned by a 180 ° rotation about c. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW.

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	Occ. (<1)
N1	0.39751 (10)	0.2500	0.27067 (17)	0.0183 (4)
N2	0.38257 (11)	0.2500	−0.1590 (2)	0.0370 (5)
C1	0.37563 (12)	0.2500	0.4325 (2)	0.0217 (4)
H1	0.4168	0.2500	0.5163	0.026*
C2	0.29366 (12)	0.2500	0.4776 (2)	0.0241 (4)
H2	0.2788	0.2500	0.5920	0.029*
C3	0.23350 (12)	0.2500	0.3566 (2)	0.0226 (4)
H3	0.1772	0.2500	0.3870	0.027*
C4	0.25634 (11)	0.2500	0.1886 (2)	0.0214 (4)
H4	0.2160	0.2500	0.1033	0.026*
C5	0.33831 (11)	0.2500	0.1499 (2)	0.0192 (4)
C6	0.36487 (12)	0.2500	−0.0215 (2)	0.0242 (4)
C7	0.48583 (12)	0.2500	0.2249 (2)	0.0249 (4)
H7A	0.4945	0.1532	0.1292	0.037*	0.50
H7B	0.5184	0.1975	0.3194	0.037*	0.50
H7C	0.5029	0.3993	0.1961	0.037*	0.50
N3	0.11091 (10)	0.2500	0.78367 (18)	0.0212 (4)
O1	0.18594 (9)	0.2500	0.81475 (19)	0.0292 (4)
O2	0.08669 (10)	0.2500	0.63510 (17)	0.0329 (4)
O3	0.06020 (10)	0.2500	0.9001 (2)	0.0383 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0241 (7)	0.0219 (7)	0.0090 (7)	0.000	−0.0007 (5)	0.000
N2	0.0305 (10)	0.0696 (14)	0.0110 (8)	0.000	−0.0001 (7)	0.000
C1	0.0325 (9)	0.0237 (8)	0.0090 (8)	0.000	−0.0007 (7)	0.000
C2	0.0378 (11)	0.0254 (9)	0.0092 (8)	0.000	0.0048 (7)	0.000
C3	0.0260 (9)	0.0262 (8)	0.0154 (8)	0.000	0.0050 (6)	0.000
C4	0.0261 (9)	0.0253 (9)	0.0127 (8)	0.000	−0.0017 (6)	0.000
C5	0.0263 (9)	0.0232 (8)	0.0081 (8)	0.000	−0.0019 (6)	0.000
C6	0.0241 (8)	0.0368 (10)	0.0118 (8)	0.000	−0.0005 (6)	0.000
C7	0.0233 (9)	0.0353 (10)	0.0161 (9)	0.000	−0.0005 (6)	0.000
N3	0.0283 (8)	0.0231 (7)	0.0123 (7)	0.000	0.0030 (5)	0.000
O1	0.0271 (8)	0.0407 (8)	0.0198 (7)	0.000	−0.0006 (5)	0.000
O2	0.0369 (9)	0.0490 (9)	0.0128 (7)	0.000	−0.0044 (5)	0.000
O3	0.0383 (9)	0.0558 (10)	0.0207 (8)	0.000	0.0152 (6)	0.000

N1—C1	1.348 (2)	C4—C5	1.372 (3)
N1—C5	1.368 (2)	C4—H4	0.9500
N1—C7	1.486 (2)	C5—C6	1.443 (2)
N2—C6	1.142 (2)	C7—H7A	0.9800
C1—C2	1.384 (3)	C7—H7B	0.9800
C1—H1	0.9500	C7—H7C	0.9800
C2—C3	1.381 (3)	N3—O3	1.248 (2)
C2—H2	0.9500	N3—O1	1.248 (2)
C3—C4	1.399 (2)	N3—O2	1.257 (2)
C3—H3	0.9500
C1—N1—C5	119.79 (16)	C3—C4—H4	120.7
C1—N1—C7	119.66 (15)	N1—C5—C4	121.77 (17)
C5—N1—C7	120.55 (15)	N1—C5—C6	117.69 (16)
N1—C1—C2	120.52 (17)	C4—C5—C6	120.55 (16)
N1—C1—H1	119.7	N2—C6—C5	177.2 (2)
C2—C1—H1	119.7	N1—C7—H7A	109.5
C3—C2—C1	120.08 (16)	N1—C7—H7B	109.5
C3—C2—H2	120.0	H7A—C7—H7B	109.5
C1—C2—H2	120.0	N1—C7—H7C	109.5
C2—C3—C4	119.32 (18)	H7A—C7—H7C	109.5
C2—C3—H3	120.3	H7B—C7—H7C	109.5
C4—C3—H3	120.3	O3—N3—O1	119.95 (16)
C5—C4—C3	118.52 (17)	O3—N3—O2	120.21 (17)
C5—C4—H4	120.7	O1—N3—O2	119.84 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.95	2.34	3.227 (2)	155
C3—H3···O2	0.95	2.48	3.276 (2)	141
C4—H4···O1i	0.95	2.37	3.215 (2)	148
C7—H7B···O3ii	0.98	2.38	3.247 (2)	148
C7—H7A···O2iii	0.98	2.67	3.326 (2)	125
C7—H7C···O2iv	0.98	2.64	3.3503 (11)	130
C1—H1···N2v	0.95	2.67	3.259 (2)	123
C2—H2···N2v	0.95	2.62	3.283 (2)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1	0.95	2.34	3.227 (2)	155
C3—H3⋯O2	0.95	2.48	3.276 (2)	141
C4—H4⋯O1i	0.95	2.37	3.215 (2)	148
C7—H7B⋯O3ii	0.98	2.38	3.247 (2)	148
C7—H7A⋯O2iii	0.98	2.67	3.326 (2)	125
C7—H7C⋯O2iv	0.98	2.64	3.3503 (11)	130
C1—H1⋯N2v	0.95	2.67	3.259 (2)	123
C2—H2⋯N2v	0.95	2.62	3.283 (2)	125

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