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3-Cyano-N-methylpyridinium perchlorate

aDepartment of Physics, Loyola University, New Orleans, LA 70118, USA, bDepartment of Chemistry, 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 3 June 2014; accepted 19 June 2014; online 25 June 2014)

In the crystal of the title mol­ecular salt, C7H7N2+·ClO4, the components are linked by C—H⋯O and C—H⋯N inter­actions, generating zigzag chains running parallel to [100].

Keywords: crystal structure.

Related literature

For structures of other 3-cyano-1-methyl­pyridinium salts, see: Koplitz et al. (2003[Koplitz, L. V., Bay, K. D., DiGiovanni, N. & Mague, J. T. (2003). J. Chem. Crystallogr. 33, 391-402.]); Mague et al. (2005[Mague, J. T., Ivie, R. M., Hartsock, R. W., Koplitz, L. V. & Spulak, M. (2005). Acta Cryst. E61, o851-o853.]); Zhu et al. (1999[Zhu, D. & Kochi, J. K. (1999). Organometallics, 18, 161-172.]). For the structure of 4-cyano-1-methyl­pyridinium perchlorate, see: Nguyen et al. (2014[Nguyen, V. D., McCormick, C. A., Koplitz, L. V. & Mague, J. T. (2014). Acta Cryst. E70, o756-o757.]). 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.]). 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[Koplitz, L. V., Bay, K. D., DiGiovanni, N. & Mague, J. T. (2003). J. Chem. Crystallogr. 33, 391-402.]) and 2-cyano­anilinium nitrate (Cui & Wen, 2008[Cui, L.-J. & Wen, X.-C. (2008). Acta Cryst. E64, o1620.]) crystallize in flat layers of two-dimensional networks with only a few atoms protruding from the mirror plane while 3-cyano­anilinium nitrate (Wang, 2009[Wang, B. (2009). Acta Cryst. E65, o2395.]) forms a more open structure.

[Scheme 1]

Experimental

Crystal data
  • C7H7N2+·ClO4

  • Mr = 218.60

  • Monoclinic, P 21 /c

  • 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[Bruker (2010). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.89, Tmax = 0.98

  • 15448 measured reflections

  • 2364 independent reflections

  • 2187 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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) -x+1, -y, -z+1; (ii) x-1, y, z; (iii) x+1, y, z.

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

A perspective view of the title compound appears in Fig. 1 while Fig. 2 illustrates the zigzag rows of anions with cations bound on either side via C—H···O hydrogen bonds (Table 1). Additionally, there are C—H···N interactions between methyl H atoms of one cation and the cyano group of the next cation in the chain. An end view of these motifs is shown in Fig. 3. A notable feature is the close cation-anion contact (H1A···O2i = 2.56 Å (symmetry code: (i) 1 - x, -y, 1 - z) which is strikingly similar to the motif that dominates the structure of 2-cyano-1-methylpyridinium nitrate (Koplitz et al., 2003). These close contacts are likely the result of electrostatic cation-anion attraction with the orientation possibly reinforced by an anion-π interaction (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.

Related literature top

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 top

3-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 3-cyano-1-methylpyridinium iodide (m.p. 196° C, blood-red melt) 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 3-cyano-1-methylpyridinium perchlorate was slowly evaporated to dryness to form colorless plates 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 isotropic displacement parameters 1.2 - 1.5 times those of the attached carbon atoms.

Structure description top

A perspective view of the title compound appears in Fig. 1 while Fig. 2 illustrates the zigzag rows of anions with cations bound on either side via C—H···O hydrogen bonds (Table 1). Additionally, there are C—H···N interactions between methyl H atoms of one cation and the cyano group of the next cation in the chain. An end view of these motifs is shown in Fig. 3. A notable feature is the close cation-anion contact (H1A···O2i = 2.56 Å (symmetry code: (i) 1 - x, -y, 1 - z) which is strikingly similar to the motif that dominates the structure of 2-cyano-1-methylpyridinium nitrate (Koplitz et al., 2003). These close contacts are likely the result of electrostatic cation-anion attraction with the orientation possibly reinforced by an anion-π interaction (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.

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.

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. Perspective view of I with displacement ellipsoids drawn at the 50% probability level and H-atoms as spheres of arbitrary radius.
[Figure 2] Fig. 2. Packing projected down the b axis with C—H···O interactions shown as red dotted lines and C—H···N interactions as blue dotted lines.
[Figure 3] Fig. 3. Packing projected onto (100) with C—H···O interactions shown as red dotted lines and C—H···N interactions as blue dotted lines.
3-Cyano-N-methylpyridinium perchlorate top
Crystal data top
C7H7N2+·ClO4F(000) = 448
Mr = 218.60Dx = 1.599 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.1490 (7) ÅCell parameters from 9885 reflections
b = 7.7338 (7) Åθ = 2.5–29.1°
c = 14.5297 (13) ŵ = 0.41 mm1
β = 97.522 (1)°T = 120 K
V = 907.82 (14) Å3Plate, colourless
Z = 40.26 × 0.24 × 0.05 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
2364 independent reflections
Radiation source: fine-focus sealed tube2187 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
φ and ω scansθmax = 29.1°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = 1111
Tmin = 0.89, Tmax = 0.98k = 1010
15448 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-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 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
C7H7N2+·ClO4V = 907.82 (14) Å3
Mr = 218.60Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.1490 (7) ŵ = 0.41 mm1
b = 7.7338 (7) ÅT = 120 K
c = 14.5297 (13) Å0.26 × 0.24 × 0.05 mm
β = 97.522 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer
2364 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
2187 reflections with I > 2σ(I)
Tmin = 0.89, Tmax = 0.98Rint = 0.031
15448 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.10Δρmax = 0.33 e Å3
2364 reflectionsΔρmin = 0.42 e Å3
128 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.67687 (13)0.33669 (13)0.36093 (7)0.0178 (2)
N21.23923 (15)0.4848 (2)0.35273 (9)0.0343 (3)
C10.58669 (16)0.28809 (18)0.43927 (9)0.0243 (3)
H1A0.63090.17890.46630.036*
H1B0.46870.27430.41670.036*
H1C0.60080.37900.48670.036*
C20.84053 (15)0.36279 (16)0.37864 (9)0.0197 (2)
H20.89610.34540.43960.024*
C30.92864 (15)0.41495 (16)0.30835 (9)0.0193 (2)
C40.84807 (16)0.43730 (17)0.21847 (9)0.0215 (3)
H40.90720.47240.16950.026*
C50.67914 (16)0.40673 (19)0.20269 (9)0.0240 (3)
H50.62100.41970.14200.029*
C60.59519 (15)0.35749 (17)0.27498 (9)0.0212 (2)
H60.47910.33820.26400.025*
C71.10263 (16)0.45190 (19)0.33204 (9)0.0246 (3)
Cl10.21118 (3)0.17038 (4)0.56832 (2)0.01789 (10)
O10.05612 (12)0.26105 (14)0.56747 (7)0.0284 (2)
O20.22598 (14)0.10417 (15)0.47740 (7)0.0338 (3)
O30.21765 (14)0.02981 (14)0.63375 (7)0.0342 (3)
O40.34636 (12)0.28745 (14)0.59632 (8)0.0298 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0195 (5)0.0164 (5)0.0182 (5)0.0014 (4)0.0051 (4)0.0010 (4)
N20.0211 (6)0.0475 (8)0.0342 (7)0.0006 (5)0.0028 (5)0.0047 (6)
C10.0247 (6)0.0263 (6)0.0239 (6)0.0022 (5)0.0109 (5)0.0051 (5)
C20.0198 (6)0.0207 (6)0.0182 (5)0.0024 (4)0.0008 (4)0.0013 (4)
C30.0170 (5)0.0191 (5)0.0218 (6)0.0022 (4)0.0029 (4)0.0007 (4)
C40.0216 (6)0.0257 (6)0.0180 (5)0.0014 (5)0.0058 (4)0.0006 (5)
C50.0223 (6)0.0323 (7)0.0170 (5)0.0007 (5)0.0006 (4)0.0006 (5)
C60.0174 (5)0.0243 (6)0.0215 (6)0.0008 (4)0.0013 (4)0.0024 (5)
C70.0205 (6)0.0301 (7)0.0235 (6)0.0023 (5)0.0038 (5)0.0032 (5)
Cl10.01977 (16)0.01840 (16)0.01568 (16)0.00044 (9)0.00301 (10)0.00022 (9)
O10.0199 (4)0.0324 (5)0.0315 (5)0.0058 (4)0.0013 (4)0.0000 (4)
O20.0450 (6)0.0383 (6)0.0199 (5)0.0080 (5)0.0118 (4)0.0091 (4)
O30.0465 (6)0.0273 (5)0.0317 (5)0.0102 (5)0.0160 (5)0.0121 (4)
O40.0216 (5)0.0303 (5)0.0359 (6)0.0040 (4)0.0018 (4)0.0065 (4)
Geometric parameters (Å, º) top
N1—C21.3401 (16)C3—C71.4431 (17)
N1—C61.3457 (16)C4—C51.3860 (18)
N1—C11.4819 (16)C4—H40.9500
N2—C71.1430 (18)C5—C61.3799 (18)
C1—H1A0.9800C5—H50.9500
C1—H1B0.9800C6—H60.9500
C1—H1C0.9800Cl1—O21.4365 (10)
C2—C31.3832 (17)Cl1—O31.4406 (10)
C2—H20.9500Cl1—O41.4427 (10)
C3—C41.3935 (17)Cl1—O11.4437 (10)
C2—N1—C6121.27 (11)C5—C4—H4121.0
C2—N1—C1118.15 (11)C3—C4—H4121.0
C6—N1—C1120.56 (11)C6—C5—C4120.12 (12)
N1—C1—H1A109.5C6—C5—H5119.9
N1—C1—H1B109.5C4—C5—H5119.9
H1A—C1—H1B109.5N1—C6—C5120.34 (12)
N1—C1—H1C109.5N1—C6—H6119.8
H1A—C1—H1C109.5C5—C6—H6119.8
H1B—C1—H1C109.5N2—C7—C3177.92 (16)
N1—C2—C3120.12 (11)O2—Cl1—O3109.73 (7)
N1—C2—H2119.9O2—Cl1—O4109.28 (6)
C3—C2—H2119.9O3—Cl1—O4109.08 (7)
C2—C3—C4120.11 (11)O2—Cl1—O1110.12 (7)
C2—C3—C7118.06 (11)O3—Cl1—O1109.18 (6)
C4—C3—C7121.78 (11)O4—Cl1—O1109.44 (6)
C5—C4—C3118.02 (11)
C6—N1—C2—C31.11 (18)C7—C3—C4—C5176.95 (13)
C1—N1—C2—C3177.46 (11)C3—C4—C5—C60.7 (2)
N1—C2—C3—C41.25 (19)C2—N1—C6—C50.06 (19)
N1—C2—C3—C7176.16 (12)C1—N1—C6—C5178.47 (12)
C2—C3—C4—C50.36 (19)C4—C5—C6—N10.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O2i0.982.563.5377 (19)173
C1—H1A···O3i0.982.593.1868 (17)119
C1—H1B···N2ii0.982.563.3136 (19)134
C1—H1B···O20.982.623.3759 (17)134
C2—H2···O1iii0.952.223.1577 (16)168
Symmetry codes: (i) x+1, y, z+1; (ii) x1, y, z; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O2i0.982.563.5377 (19)173
C1—H1A···O3i0.982.593.1868 (17)119
C1—H1B···N2ii0.982.563.3136 (19)134
C1—H1B···O20.982.623.3759 (17)134
C2—H2···O1iii0.952.223.1577 (16)168
Symmetry codes: (i) x+1, y, z+1; (ii) x1, y, z; (iii) x+1, y, z.
 

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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