4-Cyano-1-methyl­pyridinium nitrate

McCormick, C.A.; Nguyen, V.D.; Renfro, H.E.; Koplitz, L.V.; Mague, J.T.

doi:10.1107/S1600536813014025

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages o981-o982

doi:10.1107/S1600536813014025

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4-Cyano-1-methylpyridinium nitrate

Cameron A. McCormick,^a Vu D. Nguyen,^b Heather E. Renfro,^b 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 29 April 2013; accepted 20 May 2013; online 31 May 2013)

The title molecular salt, C₇H₇N₂⁺·NO₃⁻, displays an interpenetrating sheet structure parallel to a with each sheet containing nearly coplanar cations and anions, each ion being bisected by a crystallographic mirror plane. C—H⋯O hydrogen bonds involving both ring and methyl H atoms in addition to cation–cation C—H⋯N hydrogen bonds (ring H to cyano N) serve to link the sheets together. In each set of parallel layers, the cations and anions stack with short distances of 3.094 (2) (between aligned nitrate N and pyridine N atoms) and 3.057 (2) Å (between a nitrate O atom and the ring centroid). This motif is strikingly similar to the one that features in the isomeric salt 2-cyano-1-methylpyridinium nitrate.

Related literature

For structures of other 4-cyano-1-methylpyridinium salts, see: Bockman & Kochi (1989 ); Bockman & Kochi (1992 ); Hardacre et al. (2008 , 2010 ); Kammer et al. (2012a ,b . For the structure of 2-cyano-1-methylpyridinium nitrate, see: Koplitz et al. (2012 ), of 3-cyano-1-methylpyridinium chloride, see: Koplitz et al. (2003 ) and of 3-cyano-N-methylpyridinium bromide, see: Mague et al. (2005 ). For a discussion of anion–π interactions, see: Frontera et al. (2011 ). For the structure of 2-cyanoanilinium nitrate, see: Cui & Wen (2008 ) and of 3-cyanoanilinium nitrate, see: Wang (2009 ).

Experimental

Crystal data

C₇H₇N₂⁺·NO₃⁻
M_r = 181.16
Orthorhombic, P m n 2₁
a = 8.195 (3) Å
b = 7.289 (3) Å
c = 6.721 (3) Å
V = 401.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.33 × 0.23 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009 ) T_min = 0.860, T_max = 0.985
6751 measured reflections
1116 independent reflections
1089 reflections with I > 2σ(I)
R_int = 0.091

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.092
S = 1.09
1116 reflections
71 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.40 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—H1A⋯O1ⁱ	0.96	2.71	3.3826 (19)	127
C1—H1A⋯O1ⁱⁱ	0.96	2.71	3.3826 (19)	127
C1—H1B⋯O1ⁱⁱⁱ	0.90	2.60	3.4485 (15)	159
C2—H2⋯O1^iv	0.95	2.65	3.3763 (17)	134
C2—H2⋯O2^iv	0.95	2.29	3.2379 (15)	172
C3—H3⋯N2^iv	0.95	2.51	3.2272 (15)	132
C3—H3⋯O1^v	0.95	2.56	3.2568 (17)	131
Symmetry codes: (i) x, y-1, z; (ii) -x+1, y-1, z; (iii) $[x-{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2009 ); data reduction: SAINT; program(s) used to solve structure: FLIPPER option in PLATON (Spek, 2009 ); 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).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813014025/hb7076sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813014025/hb7076Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813014025/hb7076Isup3.cml

checkCIF report

Comment top

A perspective view of the title compound appears in Fig. 1 while Fig. 2 illustrates the interpenetrating sets of parallel cation/anion sheets. Within each layer, the dihedral angle between mean cation and anion planes is 1.63 (3)° while the two sets of layers are inclined at an angle of 60.05 (4)°. The majority of the interionic interactions are C—H···O hydrogen bonds between cations in one set of layers and anions in the other set. Additionally there are C—H···N interactions between ring H atoms of cations in one set of layers and the cyano groups of cations in the other set (Table 1 and Fig. 3). A notable feature is the close interlayer cation-anion contact which is strikingly similar to the motif that dominates the structure of 2-cyano-1-methylpyridinium nitrate. (Koplitz et al., 2012). Thus, the N3—O2 bond of one anion is oriented with O2 lying directly over the centroid of the nearest parallel pyridinium ring at a distance of 3.057 (2) Å and N3 lying directly over the pyridinium nitrogen (N1) at a distance of 3.094 (2) Å. 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., 2012) 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 4-cyano-1-methylpyridinium salts, see: Bockman & Kochi (1989); Bockman & Kochi (1992); Hardacre et al. (2008, 2010); Kammer et al. (2012a,b. For the structure of 2-cyano-1-methylpyridinium nitrate, see: Koplitz et al. (2012), of 3-cyano-1-methylpyridinium chloride, see: Koplitz et al. (2003) and of 3-cyano-N-methylpyridinium bromide, see: Mague et al. (2005). For a discussion of anion–π interactions, see: Frontera et al. (2011). For the structure of 2-cyanoanilinium nitrate, see: Cui & Wen (2008) and of 3-cyanoanilinium nitrate, see: Wang (2009).

Experimental top

4-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 4-cyano-N-methylpyridinium iodide (m.p. 189–193° C) was collected by vacuum filtration. This solid (0.226 g) was then dissolved in ethanol (20.3 ml) along with an equimolar amount lead(II) nitrate (0.1487 g). Precipitated PbI₂ was removed by vacuum filtration and the filtrate containing 4-cyano-N-methylpyridinium nitrate was slowly evaporated to dryness to form colourless blocks of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: PLATON (Spek, 2009); 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

	Fig. 1. Perspective view of I with displacement ellipsoids drawn at the 50% probability level and H-atoms as spheres of arbitrary radius. Primed atoms are related to unprimed counterparts by 1-x, y, z.
	Fig. 2. Packing of I viewed down a showing the interpenetrating layers. The C—H···O and C—H···N interactions are shown as dashed lines.
	Fig. 3. Packing of I showing the anion–π interactions as dashed lines.

4-Cyano-1-methylpyridinium nitrate top

Crystal data top

C₇H₇N₂⁺·NO₃⁻	F(000) = 188
M_r = 181.16	D_x = 1.499 Mg m⁻³
Orthorhombic, Pmn2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2	Cell parameters from 5849 reflections
a = 8.195 (3) Å	θ = 2.8–29.1°
b = 7.289 (3) Å	µ = 0.12 mm⁻¹
c = 6.721 (3) Å	T = 100 K
V = 401.5 (3) Å³	Block, colourless
Z = 2	0.33 × 0.23 × 0.13 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1116 independent reflections
Radiation source: fine-focus sealed tube	1089 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
ϕ and ω scans	θ_max = 29.1°, θ_min = 2.8°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	h = −11→11
T_min = 0.860, T_max = 0.985	k = −9→9
6751 measured reflections	l = −9→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0602P)² + 0.031P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1116 reflections	Δρ_max = 0.40 e Å⁻³
71 parameters	Δρ_min = −0.43 e Å⁻³
1 restraint	Extinction correction: SHELXL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.098 (15)

Crystal data top

C₇H₇N₂⁺·NO₃⁻	V = 401.5 (3) Å³
M_r = 181.16	Z = 2
Orthorhombic, Pmn2₁	Mo Kα radiation
a = 8.195 (3) Å	µ = 0.12 mm⁻¹
b = 7.289 (3) Å	T = 100 K
c = 6.721 (3) Å	0.33 × 0.23 × 0.13 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1116 independent reflections
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	1089 reflections with I > 2σ(I)
T_min = 0.860, T_max = 0.985	R_int = 0.091
6751 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.092	H-atom parameters constrained
S = 1.09	Δρ_max = 0.40 e Å⁻³
1116 reflections	Δρ_min = −0.43 e Å⁻³
71 parameters

Special details top

Experimental. 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\5 in ϕ, collected at ω = -30.00 and 210.00°. The scan time was 15 sec/frame. Analysis of 427 reflections chosen from the full data set and having I/σ(I) > 15.0 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 with SAINT under control of the 2-component orientation file generated by CELL_NOW.

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 positions derived from a difference map and their coordinates adjusted to give C—H = 0.95 Å (aromatic) and 0.98 Å (aliphatic). All were 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

	x	y	z	U_iso*/U_eq
N1	0.5000	0.16216 (16)	0.63902 (16)	0.0149 (3)
N2	0.5000	0.51281 (19)	−0.0553 (2)	0.0246 (3)
C1	0.5000	0.0548 (2)	0.8274 (2)	0.0191 (3)
H1A	0.5000	−0.0746	0.7980	0.029*
H1B	0.4089	0.0825	0.8949	0.029*
C2	0.64416 (13)	0.20717 (15)	0.55473 (14)	0.0168 (2)
H2	0.7434	0.1753	0.6192	0.020*
C3	0.64799 (13)	0.29942 (14)	0.37491 (15)	0.0163 (2)
H3	0.7489	0.3309	0.3142	0.020*
C4	0.5000	0.34509 (18)	0.2849 (2)	0.0146 (3)
C5	0.5000	0.4394 (2)	0.0962 (2)	0.0175 (3)
N3	0.5000	0.80142 (16)	0.39635 (19)	0.0154 (3)
O1	0.63291 (10)	0.75855 (13)	0.47555 (13)	0.0244 (2)
O2	0.5000	0.89102 (15)	0.23498 (16)	0.0202 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0165 (7)	0.0168 (5)	0.0114 (6)	0.000	0.000	−0.0014 (5)
N2	0.0183 (7)	0.0289 (7)	0.0267 (6)	0.000	0.000	0.0087 (6)
C1	0.0233 (9)	0.0218 (7)	0.0121 (6)	0.000	0.000	0.0014 (5)
C2	0.0139 (5)	0.0200 (5)	0.0165 (5)	−0.0001 (3)	−0.0018 (4)	−0.0028 (4)
C3	0.0136 (5)	0.0189 (4)	0.0164 (5)	−0.0016 (4)	0.0010 (4)	−0.0009 (4)
C4	0.0161 (7)	0.0140 (6)	0.0138 (7)	0.000	0.000	−0.0018 (5)
C5	0.0134 (7)	0.0183 (6)	0.0209 (7)	0.000	0.000	0.0011 (5)
N3	0.0177 (7)	0.0144 (5)	0.0140 (6)	0.000	0.000	−0.0026 (5)
O1	0.0179 (4)	0.0329 (4)	0.0224 (4)	0.0042 (3)	−0.0036 (3)	0.0043 (3)
O2	0.0205 (6)	0.0265 (5)	0.0138 (5)	0.000	0.000	0.0035 (4)

Geometric parameters (Å, º) top

N1—C2ⁱ	1.3506 (12)	C3—C4	1.3955 (13)
N1—C2	1.3506 (12)	C3—H3	0.9500
N1—C1	1.4887 (18)	C4—C3ⁱ	1.3955 (13)
N2—C5	1.150 (2)	C4—C5	1.443 (2)
C1—H1A	0.9638	N3—O1ⁱ	1.2519 (11)
C1—H1B	0.8964	N3—O1	1.2520 (11)
C2—C3	1.3834 (15)	N3—O2	1.2660 (17)
C2—H2	0.9500

C2ⁱ—N1—C2	122.01 (12)	C2—C3—H3	120.8
C2ⁱ—N1—C1	118.98 (6)	C4—C3—H3	120.8
C2—N1—C1	118.98 (6)	C3ⁱ—C4—C3	120.70 (13)
N1—C1—H1A	109.9	C3ⁱ—C4—C5	119.65 (7)
N1—C1—H1B	108.2	C3—C4—C5	119.65 (7)
H1A—C1—H1B	108.9	N2—C5—C4	179.23 (15)
N1—C2—C3	120.29 (10)	O1ⁱ—N3—O1	120.92 (13)
N1—C2—H2	119.9	O1ⁱ—N3—O2	119.54 (6)
C3—C2—H2	119.9	O1—N3—O2	119.54 (6)
C2—C3—C4	118.35 (10)

C2ⁱ—N1—C2—C3	−1.14 (19)	C2—C3—C4—C3ⁱ	0.29 (18)
C1—N1—C2—C3	176.98 (10)	C2—C3—C4—C5	−179.29 (11)
N1—C2—C3—C4	0.41 (15)

Symmetry code: (i) −x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱⁱ	0.96	2.71	3.3826 (19)	127
C1—H1A···O1ⁱⁱⁱ	0.96	2.71	3.3826 (19)	127
C1—H1B···O1^iv	0.90	2.60	3.4485 (15)	159
C2—H2···O1^v	0.95	2.65	3.3763 (17)	134
C2—H2···O2^v	0.95	2.29	3.2379 (15)	172
C3—H3···N2^v	0.95	2.51	3.2272 (15)	132
C3—H3···O1^vi	0.95	2.56	3.2568 (17)	131

Symmetry codes: (ii) x, y−1, z; (iii) −x+1, y−1, z; (iv) x−1/2, −y+1, z+1/2; (v) −x+3/2, −y+1, z+1/2; (vi) −x+3/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·NO₃⁻
M_r	181.16
Crystal system, space group	Orthorhombic, Pmn2₁
Temperature (K)	100
a, b, c (Å)	8.195 (3), 7.289 (3), 6.721 (3)
V (Å³)	401.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.33 × 0.23 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (TWINABS; Sheldrick, 2009)
T_min, T_max	0.860, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	6751, 1116, 1089
R_int	0.091
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.092, 1.09
No. of reflections	1116
No. of parameters	71
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.43

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2012), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.96	2.71	3.3826 (19)	127
C1—H1A···O1ⁱⁱ	0.96	2.71	3.3826 (19)	127
C1—H1B···O1ⁱⁱⁱ	0.90	2.60	3.4485 (15)	159
C2—H2···O1^iv	0.95	2.65	3.3763 (17)	134
C2—H2···O2^iv	0.95	2.29	3.2379 (15)	172
C3—H3···N2^iv	0.95	2.51	3.2272 (15)	132
C3—H3···O1^v	0.95	2.56	3.2568 (17)	131

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1, z; (iii) x−1/2, −y+1, z+1/2; (iv) −x+3/2, −y+1, z+1/2; (v) −x+3/2, −y+1, z−1/2.

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 diffractometer.

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