4-Cyano-1-methyl-pyridinium perchlor-ate.

The title salt, C7H7N2 (+)·ClO4 (-), crystallizes with alternating cations and anions in wavy sheets, which are formed by a number of C-H⋯O and C-H⋯N hydrogen bonds, lying approximately parallel to (001).

Related literature

For the crystal structures of other 4-cyano-1-methyl­pyridinium salts, see: McCormick et al. (2013 ▶); Kammer et al. (2012a ▶,b ▶); Hardacre et al. (2008 ▶, 2010 ▶); Glavcheva et al. (2004 ▶); Bockman & Kochi (1989 ▶, 1992 ▶). For the structure of 3-cyano-1-methyl­pyridinium perchlorate, see: McCormick et al. (2014 ▶) and for the structure of 4-cyano­anilinium perchlorate, see: Dai (2008 ▶). For a discussion of anion–π interactions, see: Frontera et al. (2011 ▶).

Experimental

Crystal data

C7H7N2 +·ClO4 −

M = 218.60

Orthorhombic,

a = 10.232 (2) Å

b = 10.872 (3) Å

c = 16.769 (4) Å

V = 1865.3 (7) Å3

Z = 8

Mo Kα radiation

μ = 0.40 mm−1

T = 100 K

0.23 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2010 ▶) T min = 0.86, T max = 0.95

30647 measured reflections

2475 independent reflections

2235 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.097

S = 1.07

2475 reflections

129 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.39 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/S1600536814012860/su2740sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012860/su2740Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814012860/su2740Isup3.cml

CCDC reference: 1006394

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

C7H7N2+·ClO4−	F(000) = 896
Mr = 218.60	Dx = 1.557 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9543 reflections
a = 10.232 (2) Å	θ = 3.0–29.1°
b = 10.872 (3) Å	µ = 0.40 mm−1
c = 16.769 (4) Å	T = 100 K
V = 1865.3 (7) Å3	Block, colourless
Z = 8	0.23 × 0.16 × 0.12 mm

Bruker SMART APEX CCD diffractometer	2475 independent reflections
Radiation source: fine-focus sealed tube	2235 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
φ and ω scans	θmax = 29.1°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −13→14
Tmin = 0.86, Tmax = 0.95	k = −14→14
30647 measured reflections	l = −22→22

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0474P)2 + 1.204P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2475 reflections	Δρmax = 0.38 e Å−3
129 parameters	Δρmin = −0.39 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (7)

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	0.07438 (11)	0.87020 (10)	0.65230 (6)	0.0173 (2)
N2	−0.23590 (12)	0.56153 (11)	0.49548 (7)	0.0259 (3)
C1	0.15878 (14)	0.95747 (13)	0.69622 (9)	0.0238 (3)
H1A	0.2307	0.9125	0.7215	0.036*
H1B	0.1071	0.9994	0.7372	0.036*
H1C	0.1944	1.0183	0.6590	0.036*
C2	−0.04511 (13)	0.90672 (12)	0.62884 (8)	0.0201 (3)
H2	−0.0730	0.9884	0.6394	0.024*
C3	−0.12714 (13)	0.82710 (12)	0.58970 (8)	0.0198 (3)
H3	−0.2115	0.8530	0.5731	0.024*
C4	−0.08458 (13)	0.70782 (12)	0.57475 (7)	0.0175 (3)
C5	0.03964 (13)	0.67124 (12)	0.59898 (8)	0.0204 (3)
H5	0.0700	0.5902	0.5887	0.024*
C6	0.11766 (14)	0.75535 (13)	0.63820 (8)	0.0200 (3)
H6	0.2026	0.7320	0.6554	0.024*
C7	−0.16859 (13)	0.62451 (12)	0.53131 (8)	0.0201 (3)
Cl1	0.01260 (3)	0.73669 (3)	0.35515 (2)	0.01939 (12)
O1	0.12396 (10)	0.79937 (10)	0.32127 (6)	0.0253 (2)
O2	−0.05193 (12)	0.81513 (10)	0.41181 (6)	0.0285 (3)
O3	0.05528 (12)	0.62622 (10)	0.39448 (9)	0.0386 (3)
O4	−0.07787 (11)	0.70787 (15)	0.29216 (7)	0.0432 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0169 (5)	0.0170 (5)	0.0180 (5)	−0.0015 (4)	0.0016 (4)	0.0016 (4)
N2	0.0280 (6)	0.0231 (6)	0.0265 (6)	−0.0034 (5)	−0.0028 (5)	0.0021 (5)
C1	0.0233 (6)	0.0201 (6)	0.0278 (7)	−0.0042 (5)	−0.0028 (5)	−0.0017 (5)
C2	0.0206 (6)	0.0157 (6)	0.0241 (6)	0.0022 (5)	0.0010 (5)	0.0026 (5)
C3	0.0177 (6)	0.0184 (6)	0.0232 (6)	0.0023 (5)	−0.0001 (5)	0.0039 (5)
C4	0.0187 (6)	0.0182 (6)	0.0155 (5)	−0.0011 (5)	0.0017 (4)	0.0020 (4)
C5	0.0200 (6)	0.0183 (6)	0.0229 (6)	0.0040 (5)	0.0013 (5)	−0.0013 (5)
C6	0.0160 (6)	0.0210 (6)	0.0229 (6)	0.0030 (5)	0.0007 (5)	0.0007 (5)
C7	0.0208 (6)	0.0184 (6)	0.0211 (6)	0.0010 (5)	0.0005 (5)	0.0041 (5)
Cl1	0.01679 (17)	0.01989 (18)	0.02150 (19)	0.00045 (11)	0.00104 (11)	−0.00297 (11)
O1	0.0221 (5)	0.0261 (5)	0.0277 (5)	−0.0036 (4)	0.0033 (4)	0.0018 (4)
O2	0.0401 (6)	0.0236 (5)	0.0217 (5)	0.0050 (4)	0.0099 (4)	−0.0012 (4)
O3	0.0292 (6)	0.0213 (5)	0.0654 (9)	0.0055 (4)	0.0110 (6)	0.0133 (5)
O4	0.0193 (5)	0.0806 (10)	0.0297 (6)	−0.0081 (6)	−0.0003 (5)	−0.0213 (6)

N1—C2	1.3443 (18)	C3—H3	0.9500
N1—C6	1.3458 (17)	C4—C5	1.3924 (19)
N1—C1	1.4793 (17)	C4—C7	1.4456 (18)
N2—C7	1.1420 (18)	C5—C6	1.3806 (19)
C1—H1A	0.9800	C5—H5	0.9500
C1—H1B	0.9800	C6—H6	0.9500
C1—H1C	0.9800	Cl1—O2	1.4373 (10)
C2—C3	1.3728 (19)	Cl1—O3	1.4382 (12)
C2—H2	0.9500	Cl1—O4	1.4389 (12)
C3—C4	1.3907 (18)	Cl1—O1	1.4441 (10)
C2—N1—C6	121.46 (12)	C3—C4—C7	119.27 (12)
C2—N1—C1	119.16 (11)	C5—C4—C7	120.72 (12)
C6—N1—C1	119.36 (11)	C6—C5—C4	118.54 (12)
N1—C1—H1A	109.5	C6—C5—H5	120.7
N1—C1—H1B	109.5	C4—C5—H5	120.7
H1A—C1—H1B	109.5	N1—C6—C5	120.52 (12)
N1—C1—H1C	109.5	N1—C6—H6	119.7
H1A—C1—H1C	109.5	C5—C6—H6	119.7
H1B—C1—H1C	109.5	N2—C7—C4	177.94 (14)
N1—C2—C3	120.65 (12)	O2—Cl1—O3	109.38 (7)
N1—C2—H2	119.7	O2—Cl1—O4	108.60 (7)
C3—C2—H2	119.7	O3—Cl1—O4	110.50 (9)
C2—C3—C4	118.86 (12)	O2—Cl1—O1	110.03 (7)
C2—C3—H3	120.6	O3—Cl1—O1	109.56 (7)
C4—C3—H3	120.6	O4—Cl1—O1	108.76 (7)
C3—C4—C5	119.97 (12)
C6—N1—C2—C3	0.2 (2)	C3—C4—C5—C6	0.48 (19)
C1—N1—C2—C3	−178.38 (12)	C7—C4—C5—C6	178.09 (12)
N1—C2—C3—C4	0.0 (2)	C2—N1—C6—C5	−0.1 (2)
C2—C3—C4—C5	−0.4 (2)	C1—N1—C6—C5	178.49 (12)
C2—C3—C4—C7	−178.02 (12)	C4—C5—C6—N1	−0.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4i	0.98	2.37	3.245 (2)	149
C1—H1C···O2ii	0.98	2.61	3.2540 (19)	123
C2—H2···O1ii	0.95	2.46	3.4001 (18)	173
C2—H2···O2ii	0.95	2.63	3.2549 (18)	123
C3—H3···N2iii	0.95	2.67	3.3098 (18)	125
C3—H3···O3iv	0.95	2.46	3.300 (2)	148
C6—H6···O4i	0.95	2.50	3.351 (2)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4i	0.98	2.37	3.245 (2)	149
C1—H1C⋯O2ii	0.98	2.61	3.2540 (19)	123
C2—H2⋯O1ii	0.95	2.46	3.4001 (18)	173
C2—H2⋯O2ii	0.95	2.63	3.2549 (18)	123
C3—H3⋯N2iii	0.95	2.67	3.3098 (18)	125
C3—H3⋯O3iv	0.95	2.46	3.300 (2)	148
C6—H6⋯O4i	0.95	2.50	3.351 (2)	149

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