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2-Cyano-1-methyl­pyridinium iodide

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 11 July 2013; accepted 12 July 2013; online 20 July 2013)

The cation in the title compound, C7H7N2+·I, is planar (r.m.s. deviation for the nine fitted non-H atoms = 0.040 Å). The crystal packing is best described as undulating layers of cations and anions associated via C—H⋯I inter­actions.

Related literature

For the structure of 2-cyano-N-methyl­pyridinium nitrate, see: Koplitz et al. (2012[Koplitz, L. V., Mague, J. T., Kammer, M. N., McCormick, C. A., Renfro, H. E. & Vumbaco, D. J. (2012). Acta Cryst. E68, o1653.]). For structures of 3-cyano-N-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.]). For structures of 4-cyano-N-methyl­pyridinium salts, see: Kammer, Koplitz & Mague (2012[Kammer, M. N., Koplitz, L. V. & Mague, J. T. (2012). Acta Cryst. E68, o2514.]); Kammer, Mague & Koplitz (2012[Kammer, M. N., Mague, J. T. & Koplitz, L. V. (2012). Acta Cryst. E68, o2409.]).

[Scheme 1]

Experimental

Crystal data
  • C7H7N2+·I

  • Mr = 246.05

  • Orthorhombic, P b c a

  • a = 9.5785 (6) Å

  • b = 8.5687 (5) Å

  • c = 20.2229 (13) Å

  • V = 1659.80 (18) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 3.79 mm−1

  • T = 100 K

  • 0.16 × 0.14 × 0.07 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (TWINABS; Sheldrick, 2009[Sheldrick, G. M. (2009). TWINABS. University of Göttingen, Germany.]) Tmin = 0.58, Tmax = 0.77

  • 58292 measured reflections

  • 53390 independent reflections

  • 40858 reflections with I > 2σ(I)

  • Rint = 0.047

Refinement
  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.091

  • S = 1.03

  • 53390 reflections

  • 93 parameters

  • H-atom parameters constrained

  • Δρmax = 1.14 e Å−3

  • Δρmin = −0.43 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1B⋯I1i 0.98 3.20 4.014 (5) 141
C1—H1C⋯I1ii 0.98 3.11 4.021 (5) 156
C5—H5⋯I1iii 0.95 3.12 3.810 (5) 131
C6—H6⋯I1iv 0.95 3.03 3.677 (5) 126
Symmetry codes: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]; (ii) [x+{\script{1\over 2}}, y+1, -z+{\script{1\over 2}}]; (iii) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]; (iv) x+1, y+1, z.

Data collection: APEX2 (Bruker, 2013[Bruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2013[Bruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013[Sheldrick, G. M. (2013). SHELXL2013. University of Göttingen, Göttingen, Germany.]); 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 and CELL_NOW (Sheldrick, 2008b[Sheldrick, G. M. (2008a). CELL_NOW. University of Göttingen, Germany.]).

Supporting information


Comment top

The three-dimensional, solid state structures of the salts of the three isomeric cyano-N-methylpyridinium cations are quite varied. These range from layered structures as seen in the chloride and bromide salts of the 3-cyano-N-methyl pyridinium cation (Koplitz, et al., 2003; Mague, et al., 2005) and in 2-cyano-N– methylpyridinium nitrate (Koplitz, et al., 2012) through an open channel structure for 3-cyano-N-methyl pyridinium iodide (Koplitz, et al., 2003) to complex networks as found for 4-cyano-N-methylpyridinium bromide and iodide (Kammer, Mague & Koplitz, 2012; Kammer, Koplitz & Mague, 2012). In all instances, the packing appears to be organized by weak C—H to anion hydrogen bonding and, in the case of 2-cyano-N-methylpyridinium nitrate, an anion–π interaction although we have yet to discern a pattern based on either the position of the cyano group on the ring or the size or shape of the anion. In the title compound, the packing of the cations and anions is organized by weak C—H···I hydrogen bonding (Table 1). It can be described as "wavy" layers extending parallel to c. Fig. 2 presents a side view of the layers while Fig. 3 is a top view. From both of these, it is evident that the weak interionic interactions organize a three-dimensional network which is intermediate in complexity between those seen for 3-cyano-N-methylpyridinium iodide and 4-cyano-N-methylpyridinium bromide.

Related literature top

For the structure of 2-cyano-N-methylpyridinium nitrate, see: Koplitz et al. (2012). For structures of 3-cyano-N-methylpyridinium salts, see: Koplitz et al. (2003); Mague et al. (2005). For structures of 4-cyano-N-methylpyridinium salts, see: Kammer, Koplitz & Mague (2012); Kammer, Mague & Koplitz (2012).

Experimental top

2-Cyanopyridine (10.5 g) was first melted in a warm water bath and then dissolved in benzene (40 ml). Iodomethane (9.5 ml) was added to this solution slowly with stirring and the solution was refluxed for 2 h. Yellow solid 2-cyano-N-methyl pyridinium iodide (m.p. 419–423 K) was collected by vacuum filtration.

Refinement top

The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, collected at ϕ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in ϕ, collected at ω = -30.00 and 210.00°. The scan time was 15 sec/frame. Analysis of 1649 reflections having I/σ(I) > 15 and chosen from the full data set with CELL_NOW (Sheldrick, 2008a) showed the crystal to belong to the orthorhombic system and to be twinned by a 180 ° rotation about c. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW. The model was refined as a two-component twin which, although giving somewhat higher values for R1 and wR2 and the residual peaks in the final difference map than refinement as 1-component using the single component reflection file extracted from the full data set with TWINABS, provided a more reasonable suggested weighting scheme. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å). All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. The maximum and minimum residual electron density peaks of 1.14 and 0.43 eÅ-3, respectively, were located 0.02 Å and 1.86 Å from the I1 and N1 atoms, respectively.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2008b); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with 50% probability ellipsoids.
[Figure 2] Fig. 2. Packing projected down a showing the side view of the layers.
[Figure 3] Fig. 3. Packing projected down b showing the top view of the layers.
2-Cyano-1-methylpyridinium iodide top
Crystal data top
C7H7N2+·IDx = 1.969 Mg m3
Mr = 246.05Melting point: 146 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
a = 9.5785 (6) ÅCell parameters from 4287 reflections
b = 8.5687 (5) Åθ = 2.9–28.7°
c = 20.2229 (13) ŵ = 3.79 mm1
V = 1659.80 (18) Å3T = 100 K
Z = 8Slab, yellow
F(000) = 9280.16 × 0.14 × 0.07 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
53390 independent reflections
Radiation source: fine-focus sealed tube40858 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
Detector resolution: 8.3660 pixels mm-1θmax = 28.7°, θmin = 2.0°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2009)
k = 1111
Tmin = 0.58, Tmax = 0.77l = 2627
58292 measured reflections
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0143P)2 + 0.7747P]
where P = (Fo2 + 2Fc2)/3
53390 reflections(Δ/σ)max < 0.001
93 parametersΔρmax = 1.14 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C7H7N2+·IV = 1659.80 (18) Å3
Mr = 246.05Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.5785 (6) ŵ = 3.79 mm1
b = 8.5687 (5) ÅT = 100 K
c = 20.2229 (13) Å0.16 × 0.14 × 0.07 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
53390 independent reflections
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2009)
40858 reflections with I > 2σ(I)
Tmin = 0.58, Tmax = 0.77Rint = 0.047
58292 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.03Δρmax = 1.14 e Å3
53390 reflectionsΔρmin = 0.43 e Å3
93 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.41161 (3)0.07802 (3)0.10870 (2)0.01550 (12)
N10.9765 (4)1.0275 (5)0.1442 (2)0.0135 (9)
N20.7422 (4)0.7530 (5)0.2022 (2)0.0205 (10)
C11.0446 (5)0.9818 (6)0.2072 (3)0.0187 (11)
H1A1.13371.03710.21160.028*
H1B1.06150.86900.20720.028*
H1C0.98371.00920.24430.028*
C20.8562 (5)0.9559 (6)0.1244 (3)0.0142 (10)
C30.7917 (5)0.9967 (6)0.0661 (3)0.0158 (11)
H30.70740.94710.05300.019*
C40.8517 (5)1.1118 (6)0.0268 (3)0.0168 (11)
H40.81051.13950.01430.020*
C50.9713 (5)1.1848 (6)0.0481 (3)0.0166 (11)
H51.01221.26480.02200.020*
C61.0321 (5)1.1424 (5)0.1070 (3)0.0149 (10)
H61.11401.19450.12160.018*
C70.7957 (5)0.8415 (6)0.1685 (3)0.0165 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01513 (19)0.01697 (18)0.01439 (19)0.00131 (12)0.00021 (13)0.00058 (13)
N10.013 (2)0.014 (2)0.014 (2)0.0017 (16)0.0001 (18)0.0019 (17)
N20.022 (2)0.020 (2)0.019 (2)0.0019 (19)0.001 (2)0.0010 (19)
C10.020 (3)0.022 (3)0.014 (3)0.001 (2)0.004 (2)0.001 (2)
C20.012 (2)0.014 (2)0.016 (3)0.0010 (19)0.003 (2)0.003 (2)
C30.013 (3)0.016 (2)0.018 (3)0.0006 (19)0.000 (2)0.003 (2)
C40.019 (3)0.017 (2)0.014 (3)0.004 (2)0.001 (2)0.002 (2)
C50.017 (3)0.014 (2)0.020 (3)0.0014 (19)0.003 (2)0.000 (2)
C60.012 (2)0.011 (2)0.021 (3)0.0023 (18)0.003 (2)0.002 (2)
C70.015 (2)0.019 (3)0.016 (3)0.001 (2)0.001 (2)0.006 (2)
Geometric parameters (Å, º) top
N1—C61.348 (6)C2—C71.446 (7)
N1—C21.366 (6)C3—C41.391 (7)
N1—C11.484 (6)C3—H30.9500
N2—C71.141 (6)C4—C51.375 (7)
C1—H1A0.9800C4—H40.9500
C1—H1B0.9800C5—C61.375 (7)
C1—H1C0.9800C5—H50.9500
C2—C31.375 (7)C6—H60.9500
C6—N1—C2119.8 (4)C2—C3—H3120.5
C6—N1—C1119.9 (4)C4—C3—H3120.5
C2—N1—C1120.3 (4)C5—C4—C3119.1 (5)
N1—C1—H1A109.5C5—C4—H4120.4
N1—C1—H1B109.5C3—C4—H4120.4
H1A—C1—H1B109.5C6—C5—C4120.3 (5)
N1—C1—H1C109.5C6—C5—H5119.8
H1A—C1—H1C109.5C4—C5—H5119.8
H1B—C1—H1C109.5N1—C6—C5120.6 (5)
N1—C2—C3121.1 (4)N1—C6—H6119.7
N1—C2—C7117.5 (4)C5—C6—H6119.7
C3—C2—C7121.4 (5)N2—C7—C2176.9 (6)
C2—C3—C4119.0 (5)
C6—N1—C2—C31.3 (7)C2—C3—C4—C52.0 (7)
C1—N1—C2—C3180.0 (5)C3—C4—C5—C61.2 (7)
C6—N1—C2—C7175.6 (4)C2—N1—C6—C52.2 (7)
C1—N1—C2—C73.1 (7)C1—N1—C6—C5179.1 (4)
N1—C2—C3—C40.7 (7)C4—C5—C6—N10.9 (7)
C7—C2—C3—C4177.5 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···I1i0.983.204.014 (5)141
C1—H1C···I1ii0.983.114.021 (5)156
C5—H5···I1iii0.953.123.810 (5)131
C6—H6···I1iv0.953.033.677 (5)126
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+1/2, y+1, z+1/2; (iii) x+1/2, y+3/2, z; (iv) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···I1i0.983.204.014 (5)141
C1—H1C···I1ii0.983.114.021 (5)156
C5—H5···I1iii0.953.123.810 (5)131
C6—H6···I1iv0.953.033.677 (5)126
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+1/2, y+1, z+1/2; (iii) x+1/2, y+3/2, z; (iv) x+1, y+1, 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. Michael Kammer was supported by Louisiana Board of Regents grant LEQSF(2007–12)-ENH-PKSFI-PES-03 during the summer of 2011.

References

First citationBrandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationBruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationKammer, M. N., Koplitz, L. V. & Mague, J. T. (2012). Acta Cryst. E68, o2514.  CSD CrossRef IUCr Journals
First citationKammer, M. N., Mague, J. T. & Koplitz, L. V. (2012). Acta Cryst. E68, o2409.  CSD CrossRef IUCr Journals
First citationKoplitz, L. V., Bay, K. D., DiGiovanni, N. & Mague, J. T. (2003). J. Chem. Crystallogr. 33, 391–402.  Web of Science CSD CrossRef CAS
First citationKoplitz, L. V., Mague, J. T., Kammer, M. N., McCormick, C. A., Renfro, H. E. & Vumbaco, D. J. (2012). Acta Cryst. E68, o1653.  CSD CrossRef IUCr Journals
First citationMague, J. T., Ivie, R. M., Hartsock, R. W., Koplitz, L. V. & Spulak, M. (2005). Acta Cryst. E61, o851–o853.  Web of Science CSD CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008a). CELL_NOW. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008b). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2009). TWINABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2013). SHELXL2013. University of Göttingen, Göttingen, Germany.

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