



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814014421/hb7237sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536814014421/hb7237Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536814014421/hb7237Isup3.cml |
CCDC reference: 1009069
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean
(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
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.
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.
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.
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).
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 |
C7H7N2+·ClO4− | V = 907.82 (14) Å3 |
Mr = 218.60 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1490 (7) Å | µ = 0.41 mm−1 |
b = 7.7338 (7) Å | T = 120 K |
c = 14.5297 (13) Å | 0.26 × 0.24 × 0.05 mm |
β = 97.522 (1)° |
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 = 0.98 | Rint = 0.031 |
15448 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.33 e Å−3 |
2364 reflections | Δρmin = −0.42 e Å−3 |
128 parameters |
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 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x+1, y, z. |
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) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x+1, y, z. |
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.