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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].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814014421/hb7237sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536814014421/hb7237Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536814014421/hb7237Isup3.cml
Supplementary material

CCDC reference: 1009069

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.032
  • wR factor = 0.089
  • Data-to-parameter ratio = 18.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT480_ALERT_4_C Long H...A H-Bond Reported H1B .. O2 .. 2.62 Ang.
Alert level G PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 73 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 1 ALERT level C = Check. Ensure it is not caused by an omission or oversight 2 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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.
 

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