3-Cyano-N-methylpyridinium perchlorate.

In the crystal of the title mol-ecular salt, C7H7N2 (+)·ClO4 (-), the components are linked by C-H⋯O and C-H⋯N inter-actions, generating zigzag chains running parallel to [100].

Related literature

For structures of other 3-cyano-1-methyl­pyridinium salts, see: Koplitz et al. (2003 ▶); Mague et al. (2005 ▶); Zhu et al. (1999 ▶). For the structure of 4-cyano-1-methyl­pyridinium perchlorate, see: Nguyen et al. (2014 ▶). For a discussion of anion–π inter­actions, see: Frontera et al. (2011 ▶). In contrast to the structure found for the title compound, the structures of the isomeric salts 2-cyano-1-methyl­pyridinium nitrate (Koplitz et al., 2003 ▶) and 2-cyano­anilinium nitrate (Cui & Wen, 2008 ▶) crystallize in flat layers of two-dimensional networks with only a few atoms protruding from the mirror plane while 3-cyano­anilinium nitrate (Wang, 2009 ▶) forms a more open structure.

Experimental

Crystal data

C7H7N2 +·ClO4 −

M = 218.60

Monoclinic,

a = 8.1490 (7) Å

b = 7.7338 (7) Å

c = 14.5297 (13) Å

β = 97.522 (1)°

V = 907.82 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.41 mm−1

T = 120 K

0.26 × 0.24 × 0.05 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2010 ▶) T min = 0.89, T max = 0.98

15448 measured reflections

2364 independent reflections

2187 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.089

S = 1.10

2364 reflections

128 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814014421/hb7237sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814014421/hb7237Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814014421/hb7237Isup3.cml

CCDC reference: 1009069

Additional supporting information: crystallographic information; 3D view; checkCIF report

C7H7N2+·ClO4−	F(000) = 448
Mr = 218.60	Dx = 1.599 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.1490 (7) Å	Cell parameters from 9885 reflections
b = 7.7338 (7) Å	θ = 2.5–29.1°
c = 14.5297 (13) Å	µ = 0.41 mm−1
β = 97.522 (1)°	T = 120 K
V = 907.82 (14) Å3	Plate, colourless
Z = 4	0.26 × 0.24 × 0.05 mm

Bruker SMART APEX CCD diffractometer	2364 independent reflections
Radiation source: fine-focus sealed tube	2187 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 29.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −11→11
Tmin = 0.89, Tmax = 0.98	k = −10→10
15448 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0451P)2 + 0.4231P] where P = (Fo2 + 2Fc2)/3
2364 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.42 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 15 sec/frame.

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. H-atoms were placed in calculated positions (C—H = 0.95 - 0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached carbon atoms.

	x	y	z	Uiso*/Ueq
N1	0.67687 (13)	0.33669 (13)	0.36093 (7)	0.0178 (2)
N2	1.23923 (15)	0.4848 (2)	0.35273 (9)	0.0343 (3)
C1	0.58669 (16)	0.28809 (18)	0.43927 (9)	0.0243 (3)
H1A	0.6309	0.1789	0.4663	0.036*
H1B	0.4687	0.2743	0.4167	0.036*
H1C	0.6008	0.3790	0.4867	0.036*
C2	0.84053 (15)	0.36279 (16)	0.37864 (9)	0.0197 (2)
H2	0.8961	0.3454	0.4396	0.024*
C3	0.92864 (15)	0.41495 (16)	0.30835 (9)	0.0193 (2)
C4	0.84807 (16)	0.43730 (17)	0.21847 (9)	0.0215 (3)
H4	0.9072	0.4724	0.1695	0.026*
C5	0.67914 (16)	0.40673 (19)	0.20269 (9)	0.0240 (3)
H5	0.6210	0.4197	0.1420	0.029*
C6	0.59519 (15)	0.35749 (17)	0.27498 (9)	0.0212 (2)
H6	0.4791	0.3382	0.2640	0.025*
C7	1.10263 (16)	0.45190 (19)	0.33204 (9)	0.0246 (3)
Cl1	0.21118 (3)	0.17038 (4)	0.56832 (2)	0.01789 (10)
O1	0.05612 (12)	0.26105 (14)	0.56747 (7)	0.0284 (2)
O2	0.22598 (14)	0.10417 (15)	0.47740 (7)	0.0338 (3)
O3	0.21765 (14)	0.02981 (14)	0.63375 (7)	0.0342 (3)
O4	0.34636 (12)	0.28745 (14)	0.59632 (8)	0.0298 (2)

	U11	U22	U33	U12	U13	U23
N1	0.0195 (5)	0.0164 (5)	0.0182 (5)	0.0014 (4)	0.0051 (4)	0.0010 (4)
N2	0.0211 (6)	0.0475 (8)	0.0342 (7)	0.0006 (5)	0.0028 (5)	0.0047 (6)
C1	0.0247 (6)	0.0263 (6)	0.0239 (6)	0.0022 (5)	0.0109 (5)	0.0051 (5)
C2	0.0198 (6)	0.0207 (6)	0.0182 (5)	0.0024 (4)	0.0008 (4)	0.0013 (4)
C3	0.0170 (5)	0.0191 (5)	0.0218 (6)	0.0022 (4)	0.0029 (4)	0.0007 (4)
C4	0.0216 (6)	0.0257 (6)	0.0180 (5)	0.0014 (5)	0.0058 (4)	0.0006 (5)
C5	0.0223 (6)	0.0323 (7)	0.0170 (5)	0.0007 (5)	0.0006 (4)	−0.0006 (5)
C6	0.0174 (5)	0.0243 (6)	0.0215 (6)	−0.0008 (4)	0.0013 (4)	−0.0024 (5)
C7	0.0205 (6)	0.0301 (7)	0.0235 (6)	0.0023 (5)	0.0038 (5)	0.0032 (5)
Cl1	0.01977 (16)	0.01840 (16)	0.01568 (16)	0.00044 (9)	0.00301 (10)	−0.00022 (9)
O1	0.0199 (4)	0.0324 (5)	0.0315 (5)	0.0058 (4)	−0.0013 (4)	0.0000 (4)
O2	0.0450 (6)	0.0383 (6)	0.0199 (5)	−0.0080 (5)	0.0118 (4)	−0.0091 (4)
O3	0.0465 (6)	0.0273 (5)	0.0317 (5)	0.0102 (5)	0.0160 (5)	0.0121 (4)
O4	0.0216 (5)	0.0303 (5)	0.0359 (6)	−0.0040 (4)	−0.0018 (4)	−0.0065 (4)

N1—C2	1.3401 (16)	C3—C7	1.4431 (17)
N1—C6	1.3457 (16)	C4—C5	1.3860 (18)
N1—C1	1.4819 (16)	C4—H4	0.9500
N2—C7	1.1430 (18)	C5—C6	1.3799 (18)
C1—H1A	0.9800	C5—H5	0.9500
C1—H1B	0.9800	C6—H6	0.9500
C1—H1C	0.9800	Cl1—O2	1.4365 (10)
C2—C3	1.3832 (17)	Cl1—O3	1.4406 (10)
C2—H2	0.9500	Cl1—O4	1.4427 (10)
C3—C4	1.3935 (17)	Cl1—O1	1.4437 (10)
C2—N1—C6	121.27 (11)	C5—C4—H4	121.0
C2—N1—C1	118.15 (11)	C3—C4—H4	121.0
C6—N1—C1	120.56 (11)	C6—C5—C4	120.12 (12)
N1—C1—H1A	109.5	C6—C5—H5	119.9
N1—C1—H1B	109.5	C4—C5—H5	119.9
H1A—C1—H1B	109.5	N1—C6—C5	120.34 (12)
N1—C1—H1C	109.5	N1—C6—H6	119.8
H1A—C1—H1C	109.5	C5—C6—H6	119.8
H1B—C1—H1C	109.5	N2—C7—C3	177.92 (16)
N1—C2—C3	120.12 (11)	O2—Cl1—O3	109.73 (7)
N1—C2—H2	119.9	O2—Cl1—O4	109.28 (6)
C3—C2—H2	119.9	O3—Cl1—O4	109.08 (7)
C2—C3—C4	120.11 (11)	O2—Cl1—O1	110.12 (7)
C2—C3—C7	118.06 (11)	O3—Cl1—O1	109.18 (6)
C4—C3—C7	121.78 (11)	O4—Cl1—O1	109.44 (6)
C5—C4—C3	118.02 (11)
C6—N1—C2—C3	1.11 (18)	C7—C3—C4—C5	−176.95 (13)
C1—N1—C2—C3	−177.46 (11)	C3—C4—C5—C6	0.7 (2)
N1—C2—C3—C4	−1.25 (19)	C2—N1—C6—C5	−0.06 (19)
N1—C2—C3—C7	176.16 (12)	C1—N1—C6—C5	178.47 (12)
C2—C3—C4—C5	0.36 (19)	C4—C5—C6—N1	−0.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2i	0.98	2.56	3.5377 (19)	173
C1—H1A···O3i	0.98	2.59	3.1868 (17)	119
C1—H1B···N2ii	0.98	2.56	3.3136 (19)	134
C1—H1B···O2	0.98	2.62	3.3759 (17)	134
C2—H2···O1iii	0.95	2.22	3.1577 (16)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O2i	0.98	2.56	3.5377 (19)	173
C1—H1A⋯O3i	0.98	2.59	3.1868 (17)	119
C1—H1B⋯N2ii	0.98	2.56	3.3136 (19)	134
C1—H1B⋯O2	0.98	2.62	3.3759 (17)	134
C2—H2⋯O1iii	0.95	2.22	3.1577 (16)	168

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