4-Cyano-1-methyl­pyridinium bromide

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

doi:10.1107/S1600536812030449

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2409

https://doi.org/10.1107/S1600536812030449

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4-Cyano-1-methylpyridinium bromide

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

^aDepartment of Physics, Loyola University, New Orleans, LA 70118, USA, ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and ^cDepartment of Chemistry, Loyola University, New Orleans, LA 70118, USA
^*Correspondence e-mail: joelt@tulane.edu

(Received 3 July 2012; accepted 3 July 2012; online 10 July 2012)

In the crystal of the title molecular salt, C₇H₇N₂⁺·Br⁻, the cations form inversion dimers via weak pairwise C—H⋯N hydrogen bonds; their mean planes are separated by 0.292 (6) Å. Weak C—H⋯Br interactions involving all of the remaining H atoms tie the cations and anions together into sets of interpenetrating sheets. The title compound is isostructural with its iodide analogue.

Related literature

For the structure of the 4-cyano-1-methylpyridinium iodide salt, see: Kammer et al. (2012 ). For the structure of 3-cyano-1-methylpyridinium bromide, see: Mague et al. (2005 ). For the structure of 3-cyano-1-methylpyridinium chloride, see: Koplitz et al. (2003 .

Experimental

Crystal data

C₇H₇N₂⁺·Br⁻
M_r = 199.06
Monoclinic, P 2₁ /c
a = 4.5447 (16) Å
b = 11.285 (4) Å
c = 15.551 (6) Å
β = 96.455 (5)°
V = 792.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 5.11 mm⁻¹
T = 100 K
0.26 × 0.22 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: numerical (SADABS; Bruker, 2009 ) T_min = 0.351, T_max = 0.563
12985 measured reflections
2050 independent reflections
1864 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.073
S = 1.07
2050 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N2ⁱ	0.95	2.48	3.357 (2)	153
C5—H5⋯Br1ⁱⁱ	0.95	2.72	3.626 (2)	160
C6—H6⋯Br1ⁱⁱⁱ	0.95	2.78	3.6779 (19)	157
C1—H1B⋯Br1^iv	0.98	2.89	3.735 (2)	144
C1—H1C⋯Br1ⁱⁱⁱ	0.98	2.82	3.755 (2)	160
C2—H2⋯Br1^v	0.95	2.79	3.6253 (18)	147
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) -x, -y+1, -z+2; (iii) x-1, y, z; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812030449/hb6887sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812030449/hb6887Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812030449/hb6887Isup3.cml

checkCIF report

Comment top

In the title compound the cations form dimers via weak, pairwise C2—H2···N2 hydrogen bonds. In these cations the six-membered rings are parallel within 0.10 ° with the mean planes separated by 0.292 (6) Å. The remaining hydrogen atoms form weak interactions with five neighboring bromide ions (Table 1) to generate a three dimensional network of interpenetrating planes (Fig. 2).

4-Cyano-1-methylpyridinium bromide is isostructural with the corresponding iodide (Kammer et al., 2012). By contrast, the structure of the bromide salt of the isomeric 3-cyano-1-methylpyridinium cation differs markedly from that of its iodide salt but is isostructural with its chloride salt (Koplitz et al., 2003; Mague et al., 2005). Also, in the title compound each anion participates in five C—H···Br contacts in the range 2.27–2.89 Å with a sixth, essentially van der Waals contact of 3.03 Å. This differs markedly from the isomeric 3-cyano-1-methylpyridinium bromide (Mague et al., 2005) where each bromide ion is contacted by four C—H groups all in the same plane.

Related literature top

For the structure of the 4-cyano-1-methylpyridinium iodide salt, see: Kammer et al. (2012). For the structure of 3-cyano-1-methylpyridinium bromide, see: Mague et al. (2005). For the structure of 3-cyano-1-methylpyridinium chloride, see: Koplitz et al. (2003.

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. An aqueous solution of this iodide salt was passed down a column of polymer-supported bromide ion-exchange resin (Aldrich calalogue No. 51,376–8) and the eluate evaporated to dryness. Yellow slabs for the structure determination were grown by slow evaporation of a solution of the compound in a 1:1 (v/v) mixture of acetonitrile and ethanol under ambient conditions (m.p. 213° C).

Structure description top

For the structure of the 4-cyano-1-methylpyridinium iodide salt, see: Kammer et al. (2012). For the structure of 3-cyano-1-methylpyridinium bromide, see: Mague et al. (2005). For the structure of 3-cyano-1-methylpyridinium chloride, see: Koplitz et al. (2003.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view of the asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing of the title compound showing the interpenetrating sheet structure. Color key: C = gray, H = orange, Br = red, N = blue.

4-Cyano-1-methylpyridinium bromide top

Crystal data top

C₇H₇N₂⁺·Br⁻	F(000) = 392
M_r = 199.06	D_x = 1.668 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9556 reflections
a = 4.5447 (16) Å	θ = 2.6–29.1°
b = 11.285 (4) Å	µ = 5.11 mm⁻¹
c = 15.551 (6) Å	T = 100 K
β = 96.455 (5)°	Slab, yellow
V = 792.5 (5) Å³	0.26 × 0.22 × 0.13 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2050 independent reflections
Radiation source: fine-focus sealed tube	1864 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
φ and ω scans	θ_max = 29.1°, θ_min = 2.2°
Absorption correction: numerical (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.351, T_max = 0.563	k = −15→15
12985 measured reflections	l = −20→20

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.039P)² + 0.1785P] where P = (F_o² + 2F_c²)/3
2050 reflections	(Δ/σ)_max = 0.002
92 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

C₇H₇N₂⁺·Br⁻	V = 792.5 (5) Å³
M_r = 199.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.5447 (16) Å	µ = 5.11 mm⁻¹
b = 11.285 (4) Å	T = 100 K
c = 15.551 (6) Å	0.26 × 0.22 × 0.13 mm
β = 96.455 (5)°

Data collection top

Bruker SMART APEX CCD diffractometer	2050 independent reflections
Absorption correction: numerical (SADABS; Bruker, 2009)	1864 reflections with I > 2σ(I)
T_min = 0.351, T_max = 0.563	R_int = 0.065
12985 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	Δρ_max = 0.42 e Å⁻³
2050 reflections	Δρ_min = −0.72 e Å⁻³
92 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 20sec/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

	x	y	z	U_iso*/U_eq
Br1	0.38940 (3)	0.377230 (14)	0.850526 (11)	0.01629 (9)
N1	−0.0140 (3)	0.65445 (13)	0.81550 (10)	0.0142 (3)
N2	0.3192 (4)	0.93928 (14)	1.08002 (11)	0.0246 (4)
C1	−0.1282 (4)	0.58354 (16)	0.73879 (11)	0.0181 (3)
H1A	0.0322	0.5352	0.7202	0.027*
H1B	−0.2044	0.6368	0.6917	0.027*
H1C	−0.2881	0.5318	0.7537	0.027*
C2	0.1619 (4)	0.74794 (15)	0.80376 (11)	0.0166 (3)
H2	0.2143	0.7655	0.7477	0.020*
C3	0.2658 (4)	0.81810 (15)	0.87348 (12)	0.0180 (3)
H3	0.3935	0.8832	0.8663	0.022*
C4	0.1801 (4)	0.79167 (15)	0.95433 (11)	0.0160 (3)
C5	0.0060 (4)	0.69212 (15)	0.96585 (12)	0.0184 (3)
H5	−0.0465	0.6717	1.0214	0.022*
C6	−0.0873 (4)	0.62429 (14)	0.89416 (13)	0.0172 (4)
H6	−0.2043	0.5557	0.9003	0.021*
C7	0.2641 (5)	0.87129 (15)	1.02619 (14)	0.0202 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01641 (13)	0.01499 (12)	0.01814 (14)	−0.00147 (5)	0.00490 (8)	−0.00055 (5)
N1	0.0167 (7)	0.0123 (6)	0.0134 (7)	0.0003 (5)	0.0003 (5)	−0.0007 (5)
N2	0.0304 (9)	0.0227 (8)	0.0205 (8)	−0.0056 (6)	0.0020 (7)	−0.0010 (6)
C1	0.0250 (9)	0.0148 (8)	0.0142 (8)	−0.0032 (6)	0.0000 (7)	−0.0033 (7)
C2	0.0178 (8)	0.0160 (7)	0.0161 (8)	−0.0006 (6)	0.0021 (6)	0.0031 (6)
C3	0.0193 (8)	0.0144 (7)	0.0198 (9)	−0.0036 (6)	0.0002 (6)	0.0025 (7)
C4	0.0172 (8)	0.0148 (7)	0.0156 (8)	0.0009 (6)	−0.0006 (6)	0.0004 (6)
C5	0.0207 (8)	0.0188 (8)	0.0161 (8)	−0.0014 (6)	0.0034 (6)	0.0018 (7)
C6	0.0203 (9)	0.0157 (8)	0.0156 (9)	−0.0020 (6)	0.0023 (7)	0.0018 (6)
C7	0.0209 (10)	0.0200 (9)	0.0196 (10)	−0.0022 (6)	0.0018 (8)	0.0030 (7)

Geometric parameters (Å, º) top

N1—C6	1.347 (2)	C2—H2	0.9500
N1—C2	1.349 (2)	C3—C4	1.390 (2)
N1—C1	1.481 (2)	C3—H3	0.9500
N2—C7	1.142 (3)	C4—C5	1.397 (2)
C1—H1A	0.9800	C4—C7	1.451 (3)
C1—H1B	0.9800	C5—C6	1.379 (3)
C1—H1C	0.9800	C5—H5	0.9500
C2—C3	1.382 (2)	C6—H6	0.9500

C6—N1—C2	122.10 (15)	C2—C3—H3	120.6
C6—N1—C1	119.66 (14)	C4—C3—H3	120.6
C2—N1—C1	118.24 (14)	C3—C4—C5	120.59 (16)
N1—C1—H1A	109.5	C3—C4—C7	119.17 (16)
N1—C1—H1B	109.5	C5—C4—C7	120.19 (16)
H1A—C1—H1B	109.5	C6—C5—C4	118.02 (16)
N1—C1—H1C	109.5	C6—C5—H5	121.0
H1A—C1—H1C	109.5	C4—C5—H5	121.0
H1B—C1—H1C	109.5	N1—C6—C5	120.58 (15)
N1—C2—C3	119.84 (16)	N1—C6—H6	119.7
N1—C2—H2	120.1	C5—C6—H6	119.7
C3—C2—H2	120.1	N2—C7—C4	175.7 (2)
C2—C3—C4	118.74 (16)

C6—N1—C2—C3	−1.9 (2)	C3—C4—C5—C6	−2.6 (2)
C1—N1—C2—C3	178.19 (16)	C7—C4—C5—C6	175.03 (17)
N1—C2—C3—C4	−1.4 (2)	C2—N1—C6—C5	2.9 (3)
C2—C3—C4—C5	3.6 (2)	C1—N1—C6—C5	−177.16 (16)
C2—C3—C4—C7	−174.06 (16)	C4—C5—C6—N1	−0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2ⁱ	0.95	2.48	3.357 (2)	153
C5—H5···Br1ⁱⁱ	0.95	2.72	3.626 (2)	160
C6—H6···Br1ⁱⁱⁱ	0.95	2.78	3.6779 (19)	157
C1—H1B···Br1^iv	0.98	2.89	3.735 (2)	144
C1—H1C···Br1ⁱⁱⁱ	0.98	2.82	3.755 (2)	160
C2—H2···Br1^v	0.95	2.79	3.6253 (18)	147

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·Br⁻
M_r	199.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	4.5447 (16), 11.285 (4), 15.551 (6)
β (°)	96.455 (5)
V (Å³)	792.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.11
Crystal size (mm)	0.26 × 0.22 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Numerical (SADABS; Bruker, 2009)
T_min, T_max	0.351, 0.563
No. of measured, independent and observed [I > 2σ(I)] reflections	12985, 2050, 1864
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.07
No. of reflections	2050
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.72

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2ⁱ	0.95	2.48	3.357 (2)	153
C5—H5···Br1ⁱⁱ	0.95	2.72	3.626 (2)	160
C6—H6···Br1ⁱⁱⁱ	0.95	2.78	3.6779 (19)	157
C1—H1B···Br1^iv	0.98	2.89	3.735 (2)	144
C1—H1C···Br1ⁱⁱⁱ	0.98	2.82	3.755 (2)	160
C2—H2···Br1^v	0.95	2.79	3.6253 (18)	147

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

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 No. LEQSF 2003-ENH-TR-67) for the purchase of the APEX diffractometer. MK was suppported by Louisiana Board of Regents grant No. LEQSF(2007–12)-ENH-PKSFI-PES-03 during the summer of 2011.

References

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