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4-Cyano-1-methyl­pyridinium perchlor­ate

aDepartment of Chemistry, Loyola University, New Orleans, LA 70118, USA, bDepartment of Physics, Loyola University, New Orleans, LA 70118, USA, and cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
*Correspondence e-mail: joelt@tulane.edu

(Received 30 May 2014; accepted 3 June 2014; online 7 June 2014)

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[McCormick, C. A., Nguyen, V. D., Renfro, H. E., Koplitz, L. V. & Mague, J. T. (2013). Acta Cryst. E69, o981-o982.]); Kammer et al. (2012a[Kammer, M. N., Koplitz, L. V. & Mague, J. T. (2012a). Acta Cryst. E68, o2514.],b[Kammer, M. N., Mague, J. T. & Koplitz, L. V. (2012b). Acta Cryst. E68, o2409.]); Hardacre et al. (2008[Hardacre, C., Holbrey, J. D., Mullan, C. L., Nieuwenhuyzen, M., Reichert, W. M., Seddon, K. R. & Teat, S. J. (2008). New J. Chem. 32, 1953-1967.], 2010[Hardacre, C., Holbrey, J. D., Mullan, C. L., Nieuwenhuyzen, M., Youngs, T. G. A., Bowron, D. T., Teat, S. J. (2010). Phys. Chem. Chem. Phys. 12, 1842-1853.]); Glavcheva et al. (2004[Glavcheva, Z., Nakanishi, H., Okdad, S. & Umezawa, H. (2004). Mater. Lett. 58, 2466-2471.]); Bockman & Kochi (1989[Bockman, T. M. & Kochi, J. K. (1989). J. Am. Chem. Soc. 111, 4669-4683.], 1992[Bockman, T. M. & Kochi, J. K. (1992). New J. Chem. 16, 39-49.]). For the structure of 3-cyano-1-methyl­pyridinium perchlorate, see: McCormick et al. (2014[McCormick, C. A., Nguyen, V. D., Koplitz, L. V. & Mague, J. T. (2014). Acta Cryst. E70, o811.]) and for the structure of 4-cyano­anilinium perchlorate, see: Dai (2008[Dai, J. (2008). Acta Cryst. E64, o2025.]). For a discussion of anion–π interactions, see: Frontera et al. (2011[Frontera, A., Gamez, P., Mascal, M., Mooibroeck, T. J. & Reedijk, J. (2011). Angew. Chem. Int. Ed. 50, 9564-9583.]).

[Scheme 1]

Experimental

Crystal data
  • C7H7N2+·ClO4

  • Mr = 218.60

  • Orthorhombic, P b c a

  • 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[Bruker (2010). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.86, Tmax = 0.95

  • 30647 measured reflections

  • 2475 independent reflections

  • 2235 reflections with I > 2σ(I)

  • Rint = 0.054

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (ii) -x, -y+2, -z+1; (iii) [-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (iv) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1].

Data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2010[Bruker (2010). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg & Putz, 2012[Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.])').

Supporting information


Comment top

The title compound, Fig. 1, 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, which are approximately parallel to (001) [see Table 1 and Fig. 2].

As with 3-cyano-1-methylpyridinium perchlorate (McCormick et al., 2014), the perchlorate ions are located near the pyridinium nitrogen atoms as the result of electrostatic attraction but the remainder of the two structures differ considerably due to the different position of the cyano group and the effect this has on the weak interionic interactions.

Related literature top

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 [please specify subject], see: Frontera et al. (2011).

Experimental top

4-Cyanopyridine (10.55 g) was dissolved in benzene (40 ml). Iodomethane (9.5 ml) was added to this solution slowly with stirring and the solution was refluxed for 75 minutes. Yellow solid 4-cyano-1-methylpyridinium iodide (m.p. 189–193° C) was collected by vacuum filtration. This solid (0.98 g) was then dissolved in a solution of silver perchlorate previously prepared by reacting Ag2O (0.47 g) with 0.5 M aqueous HClO4(8.0 ml). After stirring, precipitated AgI was removed by vacuum filtration and the filtrate containing 4-cyano-1-methylpyridinium perchlorate (m.p.114–119° C) was slowly evaporated to dryness to form crystals of the title compound.

Refinement top

H-atoms were placed in calculated positions (C—H = 0.95 - 0.98 Å) and included as riding contributions with Uiso(H) = 1.5Ueq(C-methyl) and = 1.2Ueq(C) for other H atoms.

Structure description top

The title compound, Fig. 1, 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, which are approximately parallel to (001) [see Table 1 and Fig. 2].

As with 3-cyano-1-methylpyridinium perchlorate (McCormick et al., 2014), the perchlorate ions are located near the pyridinium nitrogen atoms as the result of electrostatic attraction but the remainder of the two structures differ considerably due to the different position of the cyano group and the effect this has on the weak interionic interactions.

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 [please specify subject], see: Frontera et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); 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)').

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of the crystal packing along the b axis, with the C—H···O and C—H···N hydrogen bonds as red and blue dashed lines, respectively (see Table 1 for details).
4-Cyano-1-methylpyridinium perchlorate top
Crystal data top
C7H7N2+·ClO4F(000) = 896
Mr = 218.60Dx = 1.557 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 9543 reflections
a = 10.232 (2) Åθ = 3.0–29.1°
b = 10.872 (3) ŵ = 0.40 mm1
c = 16.769 (4) ÅT = 100 K
V = 1865.3 (7) Å3Block, colourless
Z = 80.23 × 0.16 × 0.12 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
2475 independent reflections
Radiation source: fine-focus sealed tube2235 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
φ and ω scansθmax = 29.1°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = 1314
Tmin = 0.86, Tmax = 0.95k = 1414
30647 measured reflectionsl = 2222
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-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 reflectionsΔρmax = 0.38 e Å3
129 parametersΔρmin = 0.39 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0061 (7)
Crystal data top
C7H7N2+·ClO4V = 1865.3 (7) Å3
Mr = 218.60Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 10.232 (2) ŵ = 0.40 mm1
b = 10.872 (3) ÅT = 100 K
c = 16.769 (4) Å0.23 × 0.16 × 0.12 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
2475 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
2235 reflections with I > 2σ(I)
Tmin = 0.86, Tmax = 0.95Rint = 0.054
30647 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.07Δρmax = 0.38 e Å3
2475 reflectionsΔρmin = 0.39 e Å3
129 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.07438 (11)0.87020 (10)0.65230 (6)0.0173 (2)
N20.23590 (12)0.56153 (11)0.49548 (7)0.0259 (3)
C10.15878 (14)0.95747 (13)0.69622 (9)0.0238 (3)
H1A0.23070.91250.72150.036*
H1B0.10710.99940.73720.036*
H1C0.19441.01830.65900.036*
C20.04511 (13)0.90672 (12)0.62884 (8)0.0201 (3)
H20.07300.98840.63940.024*
C30.12714 (13)0.82710 (12)0.58970 (8)0.0198 (3)
H30.21150.85300.57310.024*
C40.08458 (13)0.70782 (12)0.57475 (7)0.0175 (3)
C50.03964 (13)0.67124 (12)0.59898 (8)0.0204 (3)
H50.07000.59020.58870.024*
C60.11766 (14)0.75535 (13)0.63820 (8)0.0200 (3)
H60.20260.73200.65540.024*
C70.16859 (13)0.62451 (12)0.53131 (8)0.0201 (3)
Cl10.01260 (3)0.73669 (3)0.35515 (2)0.01939 (12)
O10.12396 (10)0.79937 (10)0.32127 (6)0.0253 (2)
O20.05193 (12)0.81513 (10)0.41181 (6)0.0285 (3)
O30.05528 (12)0.62622 (10)0.39448 (9)0.0386 (3)
O40.07787 (11)0.70787 (15)0.29216 (7)0.0432 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0169 (5)0.0170 (5)0.0180 (5)0.0015 (4)0.0016 (4)0.0016 (4)
N20.0280 (6)0.0231 (6)0.0265 (6)0.0034 (5)0.0028 (5)0.0021 (5)
C10.0233 (6)0.0201 (6)0.0278 (7)0.0042 (5)0.0028 (5)0.0017 (5)
C20.0206 (6)0.0157 (6)0.0241 (6)0.0022 (5)0.0010 (5)0.0026 (5)
C30.0177 (6)0.0184 (6)0.0232 (6)0.0023 (5)0.0001 (5)0.0039 (5)
C40.0187 (6)0.0182 (6)0.0155 (5)0.0011 (5)0.0017 (4)0.0020 (4)
C50.0200 (6)0.0183 (6)0.0229 (6)0.0040 (5)0.0013 (5)0.0013 (5)
C60.0160 (6)0.0210 (6)0.0229 (6)0.0030 (5)0.0007 (5)0.0007 (5)
C70.0208 (6)0.0184 (6)0.0211 (6)0.0010 (5)0.0005 (5)0.0041 (5)
Cl10.01679 (17)0.01989 (18)0.02150 (19)0.00045 (11)0.00104 (11)0.00297 (11)
O10.0221 (5)0.0261 (5)0.0277 (5)0.0036 (4)0.0033 (4)0.0018 (4)
O20.0401 (6)0.0236 (5)0.0217 (5)0.0050 (4)0.0099 (4)0.0012 (4)
O30.0292 (6)0.0213 (5)0.0654 (9)0.0055 (4)0.0110 (6)0.0133 (5)
O40.0193 (5)0.0806 (10)0.0297 (6)0.0081 (6)0.0003 (5)0.0213 (6)
Geometric parameters (Å, º) top
N1—C21.3443 (18)C3—H30.9500
N1—C61.3458 (17)C4—C51.3924 (19)
N1—C11.4793 (17)C4—C71.4456 (18)
N2—C71.1420 (18)C5—C61.3806 (19)
C1—H1A0.9800C5—H50.9500
C1—H1B0.9800C6—H60.9500
C1—H1C0.9800Cl1—O21.4373 (10)
C2—C31.3728 (19)Cl1—O31.4382 (12)
C2—H20.9500Cl1—O41.4389 (12)
C3—C41.3907 (18)Cl1—O11.4441 (10)
C2—N1—C6121.46 (12)C3—C4—C7119.27 (12)
C2—N1—C1119.16 (11)C5—C4—C7120.72 (12)
C6—N1—C1119.36 (11)C6—C5—C4118.54 (12)
N1—C1—H1A109.5C6—C5—H5120.7
N1—C1—H1B109.5C4—C5—H5120.7
H1A—C1—H1B109.5N1—C6—C5120.52 (12)
N1—C1—H1C109.5N1—C6—H6119.7
H1A—C1—H1C109.5C5—C6—H6119.7
H1B—C1—H1C109.5N2—C7—C4177.94 (14)
N1—C2—C3120.65 (12)O2—Cl1—O3109.38 (7)
N1—C2—H2119.7O2—Cl1—O4108.60 (7)
C3—C2—H2119.7O3—Cl1—O4110.50 (9)
C2—C3—C4118.86 (12)O2—Cl1—O1110.03 (7)
C2—C3—H3120.6O3—Cl1—O1109.56 (7)
C4—C3—H3120.6O4—Cl1—O1108.76 (7)
C3—C4—C5119.97 (12)
C6—N1—C2—C30.2 (2)C3—C4—C5—C60.48 (19)
C1—N1—C2—C3178.38 (12)C7—C4—C5—C6178.09 (12)
N1—C2—C3—C40.0 (2)C2—N1—C6—C50.1 (2)
C2—C3—C4—C50.4 (2)C1—N1—C6—C5178.49 (12)
C2—C3—C4—C7178.02 (12)C4—C5—C6—N10.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O4i0.982.373.245 (2)149
C1—H1C···O2ii0.982.613.2540 (19)123
C2—H2···O1ii0.952.463.4001 (18)173
C2—H2···O2ii0.952.633.2549 (18)123
C3—H3···N2iii0.952.673.3098 (18)125
C3—H3···O3iv0.952.463.300 (2)148
C6—H6···O4i0.952.503.351 (2)149
Symmetry codes: (i) x+1/2, y+3/2, z+1; (ii) x, y+2, z+1; (iii) x1/2, y+1/2, z; (iv) x1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O4i0.982.373.245 (2)149
C1—H1C···O2ii0.982.613.2540 (19)123
C2—H2···O1ii0.952.463.4001 (18)173
C2—H2···O2ii0.952.633.2549 (18)123
C3—H3···N2iii0.952.673.3098 (18)125
C3—H3···O3iv0.952.463.300 (2)148
C6—H6···O4i0.952.503.351 (2)149
Symmetry codes: (i) x+1/2, y+3/2, z+1; (ii) x, y+2, z+1; (iii) x1/2, y+1/2, z; (iv) x1/2, y+3/2, z+1.
 

Acknowledgements

We thank the Chemistry Department of Tulane University for support of the X-ray laboratory and the Louisiana Board of Regents through the Louisiana Educational Quality Support Fund [grant LEQSF (2003–2003)-ENH–TR-67] for the purchase of the APEX diffractometer.

References

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