organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4-Cyano-1-methyl­pyridinium bromide

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[Kammer, M. N., Koplitz, L. V. & Mague, J. T. (2012). Acta Cryst. E68. Submitted.]). For the structure of 3-cyano-1-methyl­pyridinium bromide, see: 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 the structure of 3-cyano-1-methyl­pyridinium chloride, see: Koplitz et al. (2003[Koplitz, L. V., Bay, K. D., DiGiovanni, N. & Mague, J. T. (2003). J. Chem. Crystallogr. 33, 391-402.].

[Scheme 1]

Experimental

Crystal data
  • C7H7N2+·Br

  • Mr = 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[Bruker (2009). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.351, Tmax = 0.563

  • 12985 measured reflections

  • 2050 independent reflections

  • 1864 reflections with I > 2σ(I)

  • Rint = 0.065

Refinement
  • R[F2 > 2σ(F2)] = 0.027

  • wR(F2) = 0.073

  • S = 1.07

  • 2050 reflections

  • 92 parameters

  • H-atom parameters constrained

  • Δρmax = 0.42 e Å−3

  • Δρmin = −0.72 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯Br1iv 0.98 2.89 3.735 (2) 144
C1—H1C⋯Br1iii 0.98 2.82 3.755 (2) 160
C2—H2⋯Br1v 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[Bruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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).

Refinement top

H-atoms attached to carbon 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.

Structure description 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.

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
[Figure 1] Fig. 1. Perspective view of the asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] 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+·BrF(000) = 392
Mr = 199.06Dx = 1.668 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9556 reflections
a = 4.5447 (16) Åθ = 2.6–29.1°
b = 11.285 (4) ŵ = 5.11 mm1
c = 15.551 (6) ÅT = 100 K
β = 96.455 (5)°Slab, yellow
V = 792.5 (5) Å30.26 × 0.22 × 0.13 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
2050 independent reflections
Radiation source: fine-focus sealed tube1864 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
φ and ω scansθmax = 29.1°, θmin = 2.2°
Absorption correction: numerical
(SADABS; Bruker, 2009)
h = 66
Tmin = 0.351, Tmax = 0.563k = 1515
12985 measured reflectionsl = 2020
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.039P)2 + 0.1785P]
where P = (Fo2 + 2Fc2)/3
2050 reflections(Δ/σ)max = 0.002
92 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.72 e Å3
Crystal data top
C7H7N2+·BrV = 792.5 (5) Å3
Mr = 199.06Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.5447 (16) ŵ = 5.11 mm1
b = 11.285 (4) ÅT = 100 K
c = 15.551 (6) Å0.26 × 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)
Tmin = 0.351, Tmax = 0.563Rint = 0.065
12985 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.073H-atom parameters constrained
S = 1.07Δρmax = 0.42 e Å3
2050 reflectionsΔρmin = 0.72 e Å3
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
xyzUiso*/Ueq
Br10.38940 (3)0.377230 (14)0.850526 (11)0.01629 (9)
N10.0140 (3)0.65445 (13)0.81550 (10)0.0142 (3)
N20.3192 (4)0.93928 (14)1.08002 (11)0.0246 (4)
C10.1282 (4)0.58354 (16)0.73879 (11)0.0181 (3)
H1A0.03220.53520.72020.027*
H1B0.20440.63680.69170.027*
H1C0.28810.53180.75370.027*
C20.1619 (4)0.74794 (15)0.80376 (11)0.0166 (3)
H20.21430.76550.74770.020*
C30.2658 (4)0.81810 (15)0.87348 (12)0.0180 (3)
H30.39350.88320.86630.022*
C40.1801 (4)0.79167 (15)0.95433 (11)0.0160 (3)
C50.0060 (4)0.69212 (15)0.96585 (12)0.0184 (3)
H50.04650.67171.02140.022*
C60.0873 (4)0.62429 (14)0.89416 (13)0.0172 (4)
H60.20430.55570.90030.021*
C70.2641 (5)0.87129 (15)1.02619 (14)0.0202 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01641 (13)0.01499 (12)0.01814 (14)0.00147 (5)0.00490 (8)0.00055 (5)
N10.0167 (7)0.0123 (6)0.0134 (7)0.0003 (5)0.0003 (5)0.0007 (5)
N20.0304 (9)0.0227 (8)0.0205 (8)0.0056 (6)0.0020 (7)0.0010 (6)
C10.0250 (9)0.0148 (8)0.0142 (8)0.0032 (6)0.0000 (7)0.0033 (7)
C20.0178 (8)0.0160 (7)0.0161 (8)0.0006 (6)0.0021 (6)0.0031 (6)
C30.0193 (8)0.0144 (7)0.0198 (9)0.0036 (6)0.0002 (6)0.0025 (7)
C40.0172 (8)0.0148 (7)0.0156 (8)0.0009 (6)0.0006 (6)0.0004 (6)
C50.0207 (8)0.0188 (8)0.0161 (8)0.0014 (6)0.0034 (6)0.0018 (7)
C60.0203 (9)0.0157 (8)0.0156 (9)0.0020 (6)0.0023 (7)0.0018 (6)
C70.0209 (10)0.0200 (9)0.0196 (10)0.0022 (6)0.0018 (8)0.0030 (7)
Geometric parameters (Å, º) top
N1—C61.347 (2)C2—H20.9500
N1—C21.349 (2)C3—C41.390 (2)
N1—C11.481 (2)C3—H30.9500
N2—C71.142 (3)C4—C51.397 (2)
C1—H1A0.9800C4—C71.451 (3)
C1—H1B0.9800C5—C61.379 (3)
C1—H1C0.9800C5—H50.9500
C2—C31.382 (2)C6—H60.9500
C6—N1—C2122.10 (15)C2—C3—H3120.6
C6—N1—C1119.66 (14)C4—C3—H3120.6
C2—N1—C1118.24 (14)C3—C4—C5120.59 (16)
N1—C1—H1A109.5C3—C4—C7119.17 (16)
N1—C1—H1B109.5C5—C4—C7120.19 (16)
H1A—C1—H1B109.5C6—C5—C4118.02 (16)
N1—C1—H1C109.5C6—C5—H5121.0
H1A—C1—H1C109.5C4—C5—H5121.0
H1B—C1—H1C109.5N1—C6—C5120.58 (15)
N1—C2—C3119.84 (16)N1—C6—H6119.7
N1—C2—H2120.1C5—C6—H6119.7
C3—C2—H2120.1N2—C7—C4175.7 (2)
C2—C3—C4118.74 (16)
C6—N1—C2—C31.9 (2)C3—C4—C5—C62.6 (2)
C1—N1—C2—C3178.19 (16)C7—C4—C5—C6175.03 (17)
N1—C2—C3—C41.4 (2)C2—N1—C6—C52.9 (3)
C2—C3—C4—C53.6 (2)C1—N1—C6—C5177.16 (16)
C2—C3—C4—C7174.06 (16)C4—C5—C6—N10.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N2i0.952.483.357 (2)153
C5—H5···Br1ii0.952.723.626 (2)160
C6—H6···Br1iii0.952.783.6779 (19)157
C1—H1B···Br1iv0.982.893.735 (2)144
C1—H1C···Br1iii0.982.823.755 (2)160
C2—H2···Br1v0.952.793.6253 (18)147
Symmetry codes: (i) x+1, y+2, z+2; (ii) x, y+1, z+2; (iii) x1, y, z; (iv) x, y+1/2, z+3/2; (v) x+1, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC7H7N2+·Br
Mr199.06
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)4.5447 (16), 11.285 (4), 15.551 (6)
β (°) 96.455 (5)
V3)792.5 (5)
Z4
Radiation typeMo Kα
µ (mm1)5.11
Crystal size (mm)0.26 × 0.22 × 0.13
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionNumerical
(SADABS; Bruker, 2009)
Tmin, Tmax0.351, 0.563
No. of measured, independent and
observed [I > 2σ(I)] reflections
12985, 2050, 1864
Rint0.065
(sin θ/λ)max1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.073, 1.07
No. of reflections2050
No. of parameters92
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C3—H3···N2i0.952.483.357 (2)153
C5—H5···Br1ii0.952.723.626 (2)160
C6—H6···Br1iii0.952.783.6779 (19)157
C1—H1B···Br1iv0.982.893.735 (2)144
C1—H1C···Br1iii0.982.823.755 (2)160
C2—H2···Br1v0.952.793.6253 (18)147
Symmetry codes: (i) x+1, y+2, z+2; (ii) x, y+1, z+2; (iii) x1, 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

First citationBruker (2009). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationKammer, M. N., Koplitz, L. V. & Mague, J. T. (2012). Acta Cryst. E68. Submitted.  CrossRef IUCr Journals Google Scholar
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 Google Scholar
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 Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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