Crystal structure of 2-cyano-1-methyl­pyridinium bromide

Nguyen, V.D.; McCormick, C.A.; Pascal, R.A. Jr; Mague, J.T.; Koplitz, L.V.

doi:10.1107/S2056989015019167

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 11| November 2015| Pages o854-o855

https://doi.org/10.1107/S2056989015019167

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Crystal structure of 2-cyano-1-methylpyridinium bromide

Vu D. Nguyen,^a Cameron A. McCormick,^a Robert A. Pascal Jr,^b Joel T. Mague ^b ^* and Lynn V. Koplitz ^a

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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 10 October 2015; accepted 10 October 2015; online 17 October 2015)

In the title molecular salt, C₇H₇N₂⁺·Br⁻, all the non-H atoms lie on crystallographic mirror planes. The packing consists of (010) cation–anion layers, with the cations forming dimeric units via very weak pairwise C—H⋯N interactions. Weak C—H⋯Br interactions link the cations to the anions.

Keywords: crystal structure; salt; 2-cyano-1-methylpyridinium bromide.

CCDC reference: 1430625

1. Related literature

For structures of other salts of the 2-cyano-1-methylpyridinium cation, see: Koplitz et al. (2012 ); Kammer et al. (2013 ); Vaccaro et al. (2015 ). For structures of salts of the isomeric 2-cyanoanilinium cation, see: Oueslati et al. (2005 ); Cui & Wen (2008 ); Zhang, L. (2009 ); Zhang, Y. (2009 ); Cui & Chen (2010 ); Vumbaco et al. (2013 ).

2. Experimental

2.1. Crystal data

C₇H₇N₂⁺·Br⁻
M_r = 199.06
Monoclinic, C 2/m
a = 13.3039 (12) Å
b = 6.5892 (6) Å
c = 9.3753 (8) Å
β = 92.419 (1)°
V = 821.13 (13) Å³
Z = 4
Mo Kα radiation
μ = 4.93 mm⁻¹
T = 150 K
0.20 × 0.15 × 0.06 mm

2.2. Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009 ) T_min = 0.44, T_max = 0.74
22367 measured reflections
1179 independent reflections
1084 reflections with I > 2σ(I)
R_int = 0.021

2.3. Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.048
S = 1.02
1179 reflections
62 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯N2ⁱ	0.95	2.66	3.549 (3)	155
C1—H1A⋯Br1ⁱⁱ	0.98	2.96	3.876 (2)	156
C2—H2⋯Br1ⁱⁱ	0.95	2.66	3.586 (2)	166
C3—H3⋯Br1ⁱⁱⁱ	0.95	2.77	3.711 (2)	170
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2014 ); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT and CELL_NOW (Sheldrick, 2008a ); program(s) used to solve structure: SHELXT (Sheldrick, 2015a ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b ).

Supporting information

CCDC reference: 1430625

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015019167/hb7523sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019167/hb7523Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015019167/hb7523Isup3.cml

checkCIF report

Comment top

The cation in the title compound has crystallographically imposed mirror symmetry with the methyl H atoms slightly disordered about the mirror. The packing thus consists of cation/anion layers (Fig. 2) with the cations forming dimeric units via weak, pairwise C5—H5···N2 interactions (Fig. 3 and Table 1). Within the layers weak C—H···Br interactions tie the cations and anions together (Fig. 3 and Table 1).

Related literature top

For structures of other salts of the 2-cyano-1-methylpyridinium cation, see: Koplitz et al. (2012); Kammer et al. (2013); Vaccaro et al. (2015). For structures of salts of the isomeric 2-cyanoanilinium cation, see: Oueslati et al. (2005); Cui & Wen (2008); Zhang, L. (2009); Zhang, Y. (2009); Cui & Chen (2010); Vumbaco et al. (2013).

Experimental top

2-Cyanopyridine (4.04 g, 38.8 mmol) was first melted in a warm water bath and then dissolved in toluene (15 ml). Gaseous bromomethane was condensed (roughly 5 ml, 170 mmol) and added to this solution slowly. The reaction mixture was thoroughly mixed to yield a light amber homogenous solution and left to evaporate slowly. Light yellow shiny flakes of 2-cyano-1-methylpyridinium bromide (m.p. 196.4–197.4 C) were collected by vacuum filtration.

Structure description top

For structures of other salts of the 2-cyano-1-methylpyridinium cation, see: Koplitz et al. (2012); Kammer et al. (2013); Vaccaro et al. (2015). For structures of salts of the isomeric 2-cyanoanilinium cation, see: Oueslati et al. (2005); Cui & Wen (2008); Zhang, L. (2009); Zhang, Y. (2009); Cui & Chen (2010); Vumbaco et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014) and CELL_NOW (Sheldrick, 2008a); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

	Fig. 1. The title compound with labeling scheme and 50% probability ellipsoids.
	Fig. 2. Packing viewed down the c axis showing the layer structure.
	Fig. 3. Packing viewed down the b axis showing the weak C—H···N (blue dotted lines) and C—H···Br (orange dotted lines) interactions.

2-Cyano-1-methylpyridinium bromide top

Crystal data top

C₇H₇N₂⁺·Br⁻	F(000) = 392
M_r = 199.06	D_x = 1.610 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 13.3039 (12) Å	Cell parameters from 9936 reflections
b = 6.5892 (6) Å	θ = 2.2–29.1°
c = 9.3753 (8) Å	µ = 4.93 mm⁻¹
β = 92.419 (1)°	T = 150 K
V = 821.13 (13) Å³	Block, colourless
Z = 4	0.20 × 0.15 × 0.06 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1179 independent reflections
Radiation source: fine-focus sealed tube	1084 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 8.3660 pixels mm^-1	θ_max = 29.1°, θ_min = 2.2°
φ and ω scans	h = −18→18
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −8→8
T_min = 0.44, T_max = 0.74	l = −12→12
22367 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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.048	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0234P)²] where P = (F_o² + 2F_c²)/3
1179 reflections	(Δ/σ)_max = 0.001
62 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₇H₇N₂⁺·Br⁻	V = 821.13 (13) Å³
M_r = 199.06	Z = 4
Monoclinic, C2/m	Mo Kα radiation
a = 13.3039 (12) Å	µ = 4.93 mm⁻¹
b = 6.5892 (6) Å	T = 150 K
c = 9.3753 (8) Å	0.20 × 0.15 × 0.06 mm
β = 92.419 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	1179 independent reflections
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	1084 reflections with I > 2σ(I)
T_min = 0.44, T_max = 0.74	R_int = 0.021
22367 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.048	H-atom parameters constrained
S = 1.02	Δρ_max = 0.51 e Å⁻³
1179 reflections	Δρ_min = −0.44 e Å⁻³
62 parameters

Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected 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 20 sec/frame. Analysis of 1897 reflections having I/σ(I) > 13 and chosen from the full data set with CELL_NOW (Sheldrick, 2008a) showed the crystal to belong to the monoclinic system and to be twinned by a 180 ° rotation about a*. The raw data were processed using the multi-component version of SAINT under control of the two-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 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. Trial refinements with the single-component reflection file extracted from the full dataset with TWINABS and with the full, 2-component reflection file indicated the former refinement to be superior.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.29873 (14)	0.0000	0.32868 (18)	0.0177 (4)
N2	0.53530 (17)	0.0000	0.1900 (3)	0.0399 (6)
C1	0.36322 (18)	0.0000	0.4616 (2)	0.0239 (5)
H1A	0.3212	0.0177	0.5440	0.036*	0.5
H1B	0.4118	0.1116	0.4584	0.036*	0.5
H1C	0.3993	−0.1293	0.4701	0.036*	0.5
C2	0.19853 (17)	0.0000	0.3369 (2)	0.0218 (5)
H2	0.1698	0.0000	0.4280	0.026*
C3	0.13619 (18)	0.0000	0.2157 (2)	0.0269 (5)
H3	0.0652	0.0000	0.2229	0.032*
C4	0.17863 (19)	0.0000	0.0830 (3)	0.0273 (5)
H4	0.1368	0.0000	−0.0017	0.033*
C5	0.28191 (18)	0.0000	0.0749 (2)	0.0237 (5)
H5	0.3120	0.0000	−0.0152	0.028*
C6	0.34090 (17)	0.0000	0.1994 (2)	0.0198 (4)
C7	0.44985 (19)	0.0000	0.1969 (3)	0.0280 (5)
Br1	0.36532 (2)	0.5000	0.29528 (2)	0.02252 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0207 (9)	0.0176 (8)	0.0152 (9)	0.000	0.0033 (7)	0.000
N2	0.0292 (12)	0.0484 (15)	0.0431 (14)	0.000	0.0139 (10)	0.000
C1	0.0261 (12)	0.0271 (12)	0.0182 (11)	0.000	−0.0025 (9)	0.000
C2	0.0220 (11)	0.0245 (11)	0.0196 (11)	0.000	0.0076 (8)	0.000
C3	0.0219 (11)	0.0337 (13)	0.0251 (12)	0.000	0.0018 (9)	0.000
C4	0.0300 (13)	0.0314 (13)	0.0203 (11)	0.000	−0.0022 (9)	0.000
C5	0.0315 (13)	0.0232 (11)	0.0170 (10)	0.000	0.0085 (9)	0.000
C6	0.0207 (11)	0.0178 (10)	0.0216 (11)	0.000	0.0080 (8)	0.000
C7	0.0274 (13)	0.0294 (13)	0.0280 (13)	0.000	0.0104 (10)	0.000
Br1	0.02982 (14)	0.02142 (12)	0.01687 (12)	0.000	0.00747 (8)	0.000

Geometric parameters (Å, º) top

N1—C2	1.339 (3)	C2—H2	0.9500
N1—C6	1.357 (3)	C3—C4	1.388 (3)
N1—C1	1.482 (3)	C3—H3	0.9500
N2—C7	1.141 (3)	C4—C5	1.379 (3)
C1—H1A	0.9800	C4—H4	0.9500
C1—H1B	0.9800	C5—C6	1.379 (3)
C1—H1C	0.9800	C5—H5	0.9500
C2—C3	1.378 (3)	C6—C7	1.451 (3)

C2—N1—C6	120.12 (19)	C2—C3—H3	120.5
C2—N1—C1	119.61 (18)	C4—C3—H3	120.5
C6—N1—C1	120.28 (18)	C5—C4—C3	119.5 (2)
N1—C1—H1A	109.5	C5—C4—H4	120.2
N1—C1—H1B	109.5	C3—C4—H4	120.2
H1A—C1—H1B	109.5	C6—C5—C4	119.1 (2)
N1—C1—H1C	109.5	C6—C5—H5	120.4
H1A—C1—H1C	109.5	C4—C5—H5	120.4
H1B—C1—H1C	109.5	N1—C6—C5	120.9 (2)
N1—C2—C3	121.25 (19)	N1—C6—C7	117.8 (2)
N1—C2—H2	119.4	C5—C6—C7	121.3 (2)
C3—C2—H2	119.4	N2—C7—C6	177.7 (3)
C2—C3—C4	119.1 (2)

C6—N1—C2—C3	0.000 (1)	C1—N1—C6—C5	180.000 (1)
C1—N1—C2—C3	180.000 (1)	C2—N1—C6—C7	180.000 (1)
N1—C2—C3—C4	0.000 (1)	C1—N1—C6—C7	0.000 (1)
C2—C3—C4—C5	0.000 (1)	C4—C5—C6—N1	0.000 (1)
C3—C4—C5—C6	0.000 (1)	C4—C5—C6—C7	180.0
C2—N1—C6—C5	0.000 (1)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N2ⁱ	0.95	2.66	3.549 (3)	155
C1—H1A···Br1ⁱⁱ	0.98	2.96	3.876 (2)	156
C2—H2···Br1ⁱⁱ	0.95	2.66	3.586 (2)	166
C3—H3···Br1ⁱⁱⁱ	0.95	2.77	3.711 (2)	170

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N2ⁱ	0.95	2.66	3.549 (3)	155
C1—H1A···Br1ⁱⁱ	0.98	2.96	3.876 (2)	156
C2—H2···Br1ⁱⁱ	0.95	2.66	3.586 (2)	166
C3—H3···Br1ⁱⁱⁱ	0.95	2.77	3.711 (2)	170

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

Acknowledgements

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

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