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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 10| October 2012| Page o2884
https://doi.org/10.1107/S1600536812037014

4-Cyano­anilinium bromide

David J. Vumbaco,a Michael N. Kammer,b Lynn V. Koplitzc and Joel T. Magued*

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

(Received 12 July 2012; accepted 27 August 2012; online 8 September 2012)

In the crystal structure of the title compound, C7H7N2+·Br−, the cations are associated into inversion dimers through weak pairwise C—H⋯N hydrogen bonds. The dimers further form stepped sheets via weak pairwise C—H⋯N hydrogen bonds. In the sheets, the spacing between the mean planes of the laterally displaced aromatic rings in adjacent dimers is 1.124 (6) Å. Three N—H⋯Br inter­actions and two weak C—H⋯Br inter­actions per cation tie the sheets together.

Related literature

For the structure of 4-cyano­anilinium choride, see: Colapietro et al. (1981[Colapietro, M., Domenicano, A., Marciante, C. & Portalone, G. (1981). Acta Cryst. B37, 387-394.]). For the structure of 4-cyano­anilinium iodide, see: Mague et al. (2012[Mague, J. T., Vumbaco, D. J., Kammer, M. N. & Koplitz, L. V. (2012). Acta Cryst. E68, o2623.]). For the structure of anilinium bromide, see: Schweiss et al. (1983[Schweiss, B. P., Fuess, H., Fecher, G. & Weiss, A. (1983). Z. Naturforsch. Teil A, 38, 350-358.]). For a discussion of C—H and N—H hydrogen bonding to halide ions, see: Steiner (1998[Steiner, T. (1998). Acta Cryst. B54, 456-463.]).

[Scheme 1]

Experimental

Crystal data

  • C7H7N2+·Br−

  • Mr = 199.06

  • Triclinic, [P \overline 1]

  • a = 4.3102 (10) Å

  • b = 6.1076 (13) Å

  • c = 14.510 (3) Å

  • α = 91.719 (3)°

  • β = 93.290 (3)°

  • γ = 101.428 (3)°

  • V = 373.46 (14) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 5.42 mm−1

  • T = 100 K

  • 0.20 × 0.19 × 0.16 mm
Data collection

  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: numerical (SADABS; Sheldrick, 2009[Sheldrick, G. M. (2009). SADABS. University of Göttingen, Germany.]) Tmin = 0.631, Tmax = 0.837

  • 6534 measured reflections

  • 1874 independent reflections

  • 1802 reflections with I > 2σ(I)

  • Rint = 0.032
Refinement

  • R[F2 > 2σ(F2)] = 0.020

  • wR(F2) = 0.051

  • S = 1.06

  • 1874 reflections

  • 91 parameters

  • H-atom parameters constrained

  • Δρmax = 0.86 e Å−3

  • Δρmin = −0.41 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯Br1 0.88 2.47 3.3209 (16) 162
C2—H2⋯Br1i 0.95 2.87 3.7316 (18) 151
C3—H3⋯N2ii 0.95 2.62 3.466 (2) 149
C5—H5⋯N2iii 0.95 2.69 3.517 (2) 146
C6—H6⋯Br1iv 0.95 3.00 3.8063 (18) 144
N1—H1B⋯Br1iv 0.88 2.54 3.4174 (16) 175
N1—H1C⋯Br1v 0.88 2.49 3.3400 (16) 162
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x, -y+2, -z+2; (iii) -x+1, -y+1, -z+2; (iv) -x+1, -y+1, -z+1; (v) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXM (Sheldrick, 1998[Sheldrick, G. M. (1998). SHELX: applications to macromolecules. In Direct Methods for Solving Macromolecular Structures edited by S. Fortier, pp. 401-411. Dordrecht: Kluwer Academic Publishers.], 2004[Sheldrick, G. M. (2004). SHELXM. University of Göttingen, Germany.]); 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812037014/jj2147sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037014/jj2147Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812037014/jj2147Isup3.cml

checkCIF report


Comment top

In the title compound, [C7H7N2]+ Br-, the cations are associated into dimers through weak, pairwise C3—H3···N2 intermolecular interactions (Fig. 1). The dimers further form stepped sheets via weak, pairwise C5—H5···N2 intermolecular interactions. In these sheets the spacing between the mean planes of the aromatic rings in adjacent dimers is 1.124 (6) Å (Table 1). The three hydrogen atoms of the anilinium group make contacts with the surrounding anions of 2.47 - 2.54 Å. These distances compare well with the mean value of 2.49 (2) Å for an N+—H···Br- hydrogen bond (Steiner, 1998) and serve, together with weak C2—H2···Br1 and C6—H6···Br1 interactions, to tie the stepped sheets into a layer structure (Fig. 2) with the layers 3.493 (7) Å apart and forming rectangular channels of width ca 12.8 Å (Fig. 3).

Related literature top

For the structure of 4-cyanoanilinium choride, see: Colapietro et al. (1981). For the structure of 4-cyanoanilinium iodide, see: Mague et al. (2012). For the structure of anilinium bromide, see: Schweiss et al. (1983). For a discussion of C—H and N—H hydrogen bonding to halide ions, see: Steiner (1998).

Experimental top

0.55 g of 4-cyanoaniline and 2.5 ml of aquous hydrobromic acid (2 M) were combined in 10 ml of ethanol. This solution was slowly evaporated to dryness under ambient conditions to form crystals of the title compound.

Refinement top

H-atoms attached to C were placed in calculated positions (C—H = 0.95 - 0.98 Å) while those attached to N were placed in sites determined from a difference map and their coordinates adjusted to give N—H = 0.88 Å. All H-atoms were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms.

Structure description top

In the title compound, [C7H7N2]+ Br-, the cations are associated into dimers through weak, pairwise C3—H3···N2 intermolecular interactions (Fig. 1). The dimers further form stepped sheets via weak, pairwise C5—H5···N2 intermolecular interactions. In these sheets the spacing between the mean planes of the aromatic rings in adjacent dimers is 1.124 (6) Å (Table 1). The three hydrogen atoms of the anilinium group make contacts with the surrounding anions of 2.47 - 2.54 Å. These distances compare well with the mean value of 2.49 (2) Å for an N+—H···Br- hydrogen bond (Steiner, 1998) and serve, together with weak C2—H2···Br1 and C6—H6···Br1 interactions, to tie the stepped sheets into a layer structure (Fig. 2) with the layers 3.493 (7) Å apart and forming rectangular channels of width ca 12.8 Å (Fig. 3).

For the structure of 4-cyanoanilinium choride, see: Colapietro et al. (1981). For the structure of 4-cyanoanilinium iodide, see: Mague et al. (2012). For the structure of anilinium bromide, see: Schweiss et al. (1983). For a discussion of C—H and N—H hydrogen bonding to halide ions, see: Steiner (1998).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXM (Sheldrick, 1998, 2004); 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 with displacement ellipsoids drawn at the 50% probability level
[Figure 2] Fig. 2. Packing showing the stepped layer structure. N—H···Br, C—H···N and C—H···Br interactions are shown as dashed lines. Color key: C = gray, H = orange, Br = red, N = blue.
[Figure 3] Fig. 3. Packing showing the rectangular channels. N—H···Br, C—H···N and C—H···Br interactions are shown as dashed lines. Color key: C = gray, H = orange, Br = red, N = blue.
4-Cyanoanilinium bromide top
Crystal data top
C7H7N2+·Br−Z = 2
Mr = 199.06F(000) = 196
Triclinic, P1Dx = 1.770 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.3102 (10) ÅCell parameters from 5589 reflections
b = 6.1076 (13) Åθ = 2.8–29.1°
c = 14.510 (3) ŵ = 5.42 mm−1
α = 91.719 (3)°T = 100 K
β = 93.290 (3)°Block, colourless
γ = 101.428 (3)°0.20 × 0.19 × 0.16 mm
V = 373.46 (14) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		1874 independent reflections
Radiation source: fine-focus sealed tube1802 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
φ and ω scansθmax = 29.2°, θmin = 2.8°
Absorption correction: numerical
(SADABS; Sheldrick, 2009)		h = −5→5
Tmin = 0.631, Tmax = 0.837k = −8→8
6534 measured reflectionsl = −19→19
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)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0248P)2 + 0.1891P]
where P = (Fo2 + 2Fc2)/3
1874 reflections(Δ/σ)max = 0.002
91 parametersΔρmax = 0.86 e Å−3
0 restraintsΔρmin = −0.41 e Å−3
Crystal data top
C7H7N2+·Br−γ = 101.428 (3)°
Mr = 199.06V = 373.46 (14) Å3
Triclinic, P1Z = 2
a = 4.3102 (10) ÅMo Kα radiation
b = 6.1076 (13) ŵ = 5.42 mm−1
c = 14.510 (3) ÅT = 100 K
α = 91.719 (3)°0.20 × 0.19 × 0.16 mm
β = 93.290 (3)°
Data collection top
Bruker SMART APEX CCD
diffractometer		1874 independent reflections
Absorption correction: numerical
(SADABS; Sheldrick, 2009)		1802 reflections with I > 2σ(I)
Tmin = 0.631, Tmax = 0.837Rint = 0.032
6534 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.051H-atom parameters constrained
S = 1.06Δρmax = 0.86 e Å−3
1874 reflectionsΔρmin = −0.41 e Å−3
91 parameters
Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5 °. in omega, collected 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 10 sec/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 attached to carbon were placed in calculated positions (C—H = 0.95 Å) while those attached to nitrogen were placed in locations derived from a difference map and then their coordinates adjusted to give an N—H distance of 0.88 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.08172 (3)0.73901 (2)0.423553 (10)0.01208 (7)
N10.5934 (3)0.7244 (2)0.60221 (10)0.0128 (3)
H1A0.42980.70290.56150.015*
H1B0.68680.61020.59400.015*
H1C0.71870.85270.59220.015*
N20.1311 (4)0.7765 (3)1.04130 (11)0.0215 (3)
C10.4868 (4)0.7327 (3)0.69615 (11)0.0117 (3)
C20.3482 (4)0.9098 (3)0.72253 (12)0.0142 (3)
H20.31991.02080.68010.017*
C30.2514 (4)0.9219 (3)0.81193 (12)0.0148 (3)
H30.15451.04090.83120.018*
C40.2980 (4)0.7575 (3)0.87320 (12)0.0140 (3)
C50.4367 (4)0.5796 (3)0.84545 (12)0.0158 (3)
H50.46500.46790.88750.019*
C60.5326 (4)0.5674 (3)0.75594 (12)0.0142 (3)
H60.62780.44810.73610.017*
C70.2031 (4)0.7694 (3)0.96694 (13)0.0168 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01341 (9)0.01043 (10)0.01308 (10)0.00377 (6)0.00081 (6)0.00256 (6)
N10.0141 (6)0.0118 (7)0.0130 (7)0.0032 (5)0.0006 (5)0.0018 (5)
N20.0304 (9)0.0179 (8)0.0179 (8)0.0073 (7)0.0055 (7)0.0020 (6)
C10.0118 (7)0.0123 (8)0.0102 (7)0.0013 (6)−0.0010 (6)−0.0002 (6)
C20.0159 (8)0.0124 (8)0.0149 (8)0.0040 (6)0.0000 (6)0.0033 (6)
C30.0167 (8)0.0127 (8)0.0157 (8)0.0050 (7)0.0009 (6)0.0001 (6)
C40.0141 (8)0.0150 (8)0.0122 (8)0.0017 (6)0.0007 (6)0.0008 (6)
C50.0185 (8)0.0143 (8)0.0152 (8)0.0047 (7)0.0007 (6)0.0038 (6)
C60.0165 (8)0.0118 (8)0.0152 (8)0.0045 (6)0.0008 (6)0.0018 (6)
C70.0201 (8)0.0125 (8)0.0181 (9)0.0038 (7)0.0011 (7)0.0026 (6)
Geometric parameters (Å, º) top
N1—C11.466 (2)C2—H20.9500
N1—H1A0.8800C3—C41.397 (2)
N1—H1B0.8801C3—H30.9500
N1—H1C0.8800C4—C51.399 (2)
N2—C71.142 (3)C4—C71.447 (2)
C1—C61.387 (2)C5—C61.390 (2)
C1—C21.389 (2)C5—H50.9500
C2—C31.390 (2)C6—H60.9500
C1—N1—H1A110.3C2—C3—H3120.3
C1—N1—H1B110.7C4—C3—H3120.3
H1A—N1—H1B106.0C3—C4—C5120.97 (16)
C1—N1—H1C108.9C3—C4—C7120.11 (16)
H1A—N1—H1C108.7C5—C4—C7118.91 (16)
H1B—N1—H1C112.2C6—C5—C4119.56 (16)
C6—C1—C2122.32 (16)C6—C5—H5120.2
C6—C1—N1119.28 (15)C4—C5—H5120.2
C2—C1—N1118.38 (15)C1—C6—C5118.79 (16)
C1—C2—C3118.97 (16)C1—C6—H6120.6
C1—C2—H2120.5C5—C6—H6120.6
C3—C2—H2120.5N2—C7—C4178.9 (2)
C2—C3—C4119.38 (16)
C6—C1—C2—C3−0.1 (3)C7—C4—C5—C6−179.23 (17)
N1—C1—C2—C3−178.82 (15)C2—C1—C6—C5−0.1 (3)
C1—C2—C3—C40.5 (3)N1—C1—C6—C5178.66 (15)
C2—C3—C4—C5−0.8 (3)C4—C5—C6—C1−0.2 (3)
C2—C3—C4—C7179.08 (16)C3—C4—C7—N2−162 (11)
C3—C4—C5—C60.7 (3)C5—C4—C7—N218 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Br10.882.473.3209 (16)162
C2—H2···Br1i0.952.873.7316 (18)151
C3—H3···N2ii0.952.623.466 (2)149
C5—H5···N2iii0.952.693.517 (2)146
C6—H6···Br1iv0.953.003.8063 (18)144
N1—H1B···Br1iv0.882.543.4174 (16)175
N1—H1C···Br1v0.882.493.3400 (16)162
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+2, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formulaC7H7N2+·Br−
Mr199.06
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)4.3102 (10), 6.1076 (13), 14.510 (3)
α, β, γ (°)91.719 (3), 93.290 (3), 101.428 (3)
V (Å3)373.46 (14)
Z2
Radiation typeMo Kα
µ (mm−1)5.42
Crystal size (mm)0.20 × 0.19 × 0.16
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionNumerical
(SADABS; Sheldrick, 2009)
Tmin, Tmax0.631, 0.837
No. of measured, independent and
observed [I > 2σ(I)] reflections		6534, 1874, 1802
Rint0.032
(sin θ/λ)max (Å−1)0.686
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.051, 1.06
No. of reflections1874
No. of parameters91
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.86, −0.41

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), SHELXM (Sheldrick, 1998, 2004), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Br10.882.473.3209 (16)162
C2—H2···Br1i0.952.873.7316 (18)151
C3—H3···N2ii0.952.623.466 (2)149
C5—H5···N2iii0.952.693.517 (2)146
C6—H6···Br1iv0.953.003.8063 (18)144
N1—H1B···Br1iv0.882.543.4174 (16)175
N1—H1C···Br1v0.882.493.3400 (16)162
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+2, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+1.
 

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.

References

First citationBruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationColapietro, M., Domenicano, A., Marciante, C. & Portalone, G. (1981). Acta Cryst. B37, 387–394.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationMague, J. T., Vumbaco, D. J., Kammer, M. N. & Koplitz, L. V. (2012). Acta Cryst. E68, o2623.  CSD CrossRef IUCr Journals Google Scholar
 First citationSchweiss, B. P., Fuess, H., Fecher, G. & Weiss, A. (1983). Z. Naturforsch. Teil A, 38, 350–358.  Google Scholar
 First citationSheldrick, G. M. (1998). SHELX: applications to macromolecules. In Direct Methods for Solving Macromolecular Structures edited by S. Fortier, pp. 401–411. Dordrecht: Kluwer Academic Publishers.  Google Scholar
 First citationSheldrick, G. M. (2004). SHELXM. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2009). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSteiner, T. (1998). Acta Cryst. B54, 456–463.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 10| October 2012| Page o2884
https://doi.org/10.1107/S1600536812037014
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