2-Cyano-1-methyl­pyridinium iodide

Kammer, M.N.; Koplitz, L.V.; Mague, J.T.

doi:10.1107/S1600536813019302

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1281

doi:10.1107/S1600536813019302

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2-Cyano-1-methylpyridinium iodide

Michael N. Kammer,^a Lynn V. Koplitz ^b and Joel T. Mague ^c ^*

^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 ). 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

Crystal data

C₇H₇N₂⁺·I⁻
M_r = 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 ) T_min = 0.58, T_max = 0.77
58292 measured reflections
53390 independent reflections
40858 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.091
S = 1.03
53390 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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⋯I1^iv	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 ); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXTL (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 and CELL_NOW (Sheldrick, 2008b ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019302/tk5240sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019302/tk5240Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019302/tk5240Isup3.cml

checkCIF report

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.

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

	Fig. 1. Perspective view of the title compound with 50% probability ellipsoids.
	Fig. 2. Packing projected down a showing the side view of the layers.
	Fig. 3. Packing projected down b showing the top view of the layers.

2-Cyano-1-methylpyridinium iodide top

Crystal data top

C₇H₇N₂⁺·I⁻	D_x = 1.969 Mg m⁻³
M_r = 246.05	Melting point: 146 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 9.5785 (6) Å	Cell parameters from 4287 reflections
b = 8.5687 (5) Å	θ = 2.9–28.7°
c = 20.2229 (13) Å	µ = 3.79 mm⁻¹
V = 1659.80 (18) Å³	T = 100 K
Z = 8	Slab, yellow
F(000) = 928	0.16 × 0.14 × 0.07 mm

Data collection top

Bruker SMART APEX CCD diffractometer	53390 independent reflections
Radiation source: fine-focus sealed tube	40858 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 8.3660 pixels mm^-1	θ_max = 28.7°, θ_min = 2.0°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −11→11
T_min = 0.58, T_max = 0.77	l = −26→27
58292 measured reflections

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0143P)² + 0.7747P] where P = (F_o² + 2F_c²)/3
53390 reflections	(Δ/σ)_max < 0.001
93 parameters	Δρ_max = 1.14 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₇H₇N₂⁺·I⁻	V = 1659.80 (18) Å³
M_r = 246.05	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.5785 (6) Å	µ = 3.79 mm⁻¹
b = 8.5687 (5) Å	T = 100 K
c = 20.2229 (13) Å	0.16 × 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)
T_min = 0.58, T_max = 0.77	R_int = 0.047
58292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.03	Δρ_max = 1.14 e Å⁻³
53390 reflections	Δρ_min = −0.43 e Å⁻³
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

	x	y	z	U_iso*/U_eq
I1	0.41161 (3)	0.07802 (3)	0.10870 (2)	0.01550 (12)
N1	0.9765 (4)	1.0275 (5)	0.1442 (2)	0.0135 (9)
N2	0.7422 (4)	0.7530 (5)	0.2022 (2)	0.0205 (10)
C1	1.0446 (5)	0.9818 (6)	0.2072 (3)	0.0187 (11)
H1A	1.1337	1.0371	0.2116	0.028*
H1B	1.0615	0.8690	0.2072	0.028*
H1C	0.9837	1.0092	0.2443	0.028*
C2	0.8562 (5)	0.9559 (6)	0.1244 (3)	0.0142 (10)
C3	0.7917 (5)	0.9967 (6)	0.0661 (3)	0.0158 (11)
H3	0.7074	0.9471	0.0530	0.019*
C4	0.8517 (5)	1.1118 (6)	0.0268 (3)	0.0168 (11)
H4	0.8105	1.1395	−0.0143	0.020*
C5	0.9713 (5)	1.1848 (6)	0.0481 (3)	0.0166 (11)
H5	1.0122	1.2648	0.0220	0.020*
C6	1.0321 (5)	1.1424 (5)	0.1070 (3)	0.0149 (10)
H6	1.1140	1.1945	0.1216	0.018*
C7	0.7957 (5)	0.8415 (6)	0.1685 (3)	0.0165 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01513 (19)	0.01697 (18)	0.01439 (19)	0.00131 (12)	−0.00021 (13)	−0.00058 (13)
N1	0.013 (2)	0.014 (2)	0.014 (2)	0.0017 (16)	0.0001 (18)	−0.0019 (17)
N2	0.022 (2)	0.020 (2)	0.019 (2)	−0.0019 (19)	0.001 (2)	−0.0010 (19)
C1	0.020 (3)	0.022 (3)	0.014 (3)	−0.001 (2)	−0.004 (2)	0.001 (2)
C2	0.012 (2)	0.014 (2)	0.016 (3)	−0.0010 (19)	0.003 (2)	−0.003 (2)
C3	0.013 (3)	0.016 (2)	0.018 (3)	0.0006 (19)	0.000 (2)	−0.003 (2)
C4	0.019 (3)	0.017 (2)	0.014 (3)	0.004 (2)	−0.001 (2)	−0.002 (2)
C5	0.017 (3)	0.014 (2)	0.020 (3)	0.0014 (19)	0.003 (2)	0.000 (2)
C6	0.012 (2)	0.011 (2)	0.021 (3)	0.0023 (18)	0.003 (2)	−0.002 (2)
C7	0.015 (2)	0.019 (3)	0.016 (3)	0.001 (2)	−0.001 (2)	−0.006 (2)

Geometric parameters (Å, º) top

N1—C6	1.348 (6)	C2—C7	1.446 (7)
N1—C2	1.366 (6)	C3—C4	1.391 (7)
N1—C1	1.484 (6)	C3—H3	0.9500
N2—C7	1.141 (6)	C4—C5	1.375 (7)
C1—H1A	0.9800	C4—H4	0.9500
C1—H1B	0.9800	C5—C6	1.375 (7)
C1—H1C	0.9800	C5—H5	0.9500
C2—C3	1.375 (7)	C6—H6	0.9500

C6—N1—C2	119.8 (4)	C2—C3—H3	120.5
C6—N1—C1	119.9 (4)	C4—C3—H3	120.5
C2—N1—C1	120.3 (4)	C5—C4—C3	119.1 (5)
N1—C1—H1A	109.5	C5—C4—H4	120.4
N1—C1—H1B	109.5	C3—C4—H4	120.4
H1A—C1—H1B	109.5	C6—C5—C4	120.3 (5)
N1—C1—H1C	109.5	C6—C5—H5	119.8
H1A—C1—H1C	109.5	C4—C5—H5	119.8
H1B—C1—H1C	109.5	N1—C6—C5	120.6 (5)
N1—C2—C3	121.1 (4)	N1—C6—H6	119.7
N1—C2—C7	117.5 (4)	C5—C6—H6	119.7
C3—C2—C7	121.4 (5)	N2—C7—C2	176.9 (6)
C2—C3—C4	119.0 (5)

C6—N1—C2—C3	1.3 (7)	C2—C3—C4—C5	−2.0 (7)
C1—N1—C2—C3	−180.0 (5)	C3—C4—C5—C6	1.2 (7)
C6—N1—C2—C7	−175.6 (4)	C2—N1—C6—C5	−2.2 (7)
C1—N1—C2—C7	3.1 (7)	C1—N1—C6—C5	179.1 (4)
N1—C2—C3—C4	0.7 (7)	C4—C5—C6—N1	0.9 (7)
C7—C2—C3—C4	177.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···I1^iv	0.95	3.03	3.677 (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···A	D—H	H···A	D···A	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···I1^iv	0.95	3.03	3.677 (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

Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kammer, M. N., Koplitz, L. V. & Mague, J. T. (2012). Acta Cryst. E68, o2514. CSD CrossRef IUCr Journals Google Scholar
Kammer, M. N., Mague, J. T. & Koplitz, L. V. (2012). Acta Cryst. E68, o2409. CSD CrossRef IUCr Journals Google Scholar
Koplitz, L. V., Bay, K. D., DiGiovanni, N. & Mague, J. T. (2003). J. Chem. Crystallogr. 33, 391–402. Web of Science CSD CrossRef CAS Google Scholar
Koplitz, 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 Google Scholar
Mague, 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 Google Scholar
Sheldrick, G. M. (2008a). CELL_NOW. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2009). TWINABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2013). SHELXL2013. University of Göttingen, Göttingen, Germany. Google Scholar