4-Cyano­anilinium bromide

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

doi:10.1107/S1600536812037014

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2884

https://doi.org/10.1107/S1600536812037014

Open

access

4-Cyanoanilinium bromide

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

^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 ). 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

Crystal data

C₇H₇N₂⁺·Br⁻
M_r = 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 ) T_min = 0.631, T_max = 0.837
6534 measured reflections
1874 independent reflections
1802 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.051
S = 1.06
1874 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −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⋯Br1^iv	0.95	3.00	3.8063 (18)	144
N1—H1B⋯Br1^iv	0.88	2.54	3.4174 (16)	175
N1—H1C⋯Br1^v	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 ); cell refinement: SAINT (Bruker, 2009 ); data reduction: SAINT; 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.

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.

Structure description 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).

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

	Fig. 1. Perspective view of the asymmetric unit with displacement ellipsoids drawn at the 50% probability level
	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.
	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
M_r = 199.06	F(000) = 196
Triclinic, P1	D_x = 1.770 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.3102 (10) Å	Cell parameters from 5589 reflections
b = 6.1076 (13) Å	θ = 2.8–29.1°
c = 14.510 (3) Å	µ = 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 tube	1802 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 29.2°, θ_min = 2.8°
Absorption correction: numerical (SADABS; Sheldrick, 2009)	h = −5→5
T_min = 0.631, T_max = 0.837	k = −8→8
6534 measured reflections	l = −19→19

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.051	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0248P)² + 0.1891P] where P = (F_o² + 2F_c²)/3
1874 reflections	(Δ/σ)_max = 0.002
91 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₇H₇N₂⁺·Br⁻	γ = 101.428 (3)°
M_r = 199.06	V = 373.46 (14) Å³
Triclinic, P1	Z = 2
a = 4.3102 (10) Å	Mo Kα radiation
b = 6.1076 (13) Å	µ = 5.42 mm⁻¹
c = 14.510 (3) Å	T = 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)
T_min = 0.631, T_max = 0.837	R_int = 0.032
6534 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.051	H-atom parameters constrained
S = 1.06	Δρ_max = 0.86 e Å⁻³
1874 reflections	Δρ_min = −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

	x	y	z	U_iso*/U_eq
Br1	0.08172 (3)	0.73901 (2)	0.423553 (10)	0.01208 (7)
N1	0.5934 (3)	0.7244 (2)	0.60221 (10)	0.0128 (3)
H1A	0.4298	0.7029	0.5615	0.015*
H1B	0.6868	0.6102	0.5940	0.015*
H1C	0.7187	0.8527	0.5922	0.015*
N2	0.1311 (4)	0.7765 (3)	1.04130 (11)	0.0215 (3)
C1	0.4868 (4)	0.7327 (3)	0.69615 (11)	0.0117 (3)
C2	0.3482 (4)	0.9098 (3)	0.72253 (12)	0.0142 (3)
H2	0.3199	1.0208	0.6801	0.017*
C3	0.2514 (4)	0.9219 (3)	0.81193 (12)	0.0148 (3)
H3	0.1545	1.0409	0.8312	0.018*
C4	0.2980 (4)	0.7575 (3)	0.87320 (12)	0.0140 (3)
C5	0.4367 (4)	0.5796 (3)	0.84545 (12)	0.0158 (3)
H5	0.4650	0.4679	0.8875	0.019*
C6	0.5326 (4)	0.5674 (3)	0.75594 (12)	0.0142 (3)
H6	0.6278	0.4481	0.7361	0.017*
C7	0.2031 (4)	0.7694 (3)	0.96694 (13)	0.0168 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01341 (9)	0.01043 (10)	0.01308 (10)	0.00377 (6)	0.00081 (6)	0.00256 (6)
N1	0.0141 (6)	0.0118 (7)	0.0130 (7)	0.0032 (5)	0.0006 (5)	0.0018 (5)
N2	0.0304 (9)	0.0179 (8)	0.0179 (8)	0.0073 (7)	0.0055 (7)	0.0020 (6)
C1	0.0118 (7)	0.0123 (8)	0.0102 (7)	0.0013 (6)	−0.0010 (6)	−0.0002 (6)
C2	0.0159 (8)	0.0124 (8)	0.0149 (8)	0.0040 (6)	0.0000 (6)	0.0033 (6)
C3	0.0167 (8)	0.0127 (8)	0.0157 (8)	0.0050 (7)	0.0009 (6)	0.0001 (6)
C4	0.0141 (8)	0.0150 (8)	0.0122 (8)	0.0017 (6)	0.0007 (6)	0.0008 (6)
C5	0.0185 (8)	0.0143 (8)	0.0152 (8)	0.0047 (7)	0.0007 (6)	0.0038 (6)
C6	0.0165 (8)	0.0118 (8)	0.0152 (8)	0.0045 (6)	0.0008 (6)	0.0018 (6)
C7	0.0201 (8)	0.0125 (8)	0.0181 (9)	0.0038 (7)	0.0011 (7)	0.0026 (6)

Geometric parameters (Å, º) top

N1—C1	1.466 (2)	C2—H2	0.9500
N1—H1A	0.8800	C3—C4	1.397 (2)
N1—H1B	0.8801	C3—H3	0.9500
N1—H1C	0.8800	C4—C5	1.399 (2)
N2—C7	1.142 (3)	C4—C7	1.447 (2)
C1—C6	1.387 (2)	C5—C6	1.390 (2)
C1—C2	1.389 (2)	C5—H5	0.9500
C2—C3	1.390 (2)	C6—H6	0.9500

C1—N1—H1A	110.3	C2—C3—H3	120.3
C1—N1—H1B	110.7	C4—C3—H3	120.3
H1A—N1—H1B	106.0	C3—C4—C5	120.97 (16)
C1—N1—H1C	108.9	C3—C4—C7	120.11 (16)
H1A—N1—H1C	108.7	C5—C4—C7	118.91 (16)
H1B—N1—H1C	112.2	C6—C5—C4	119.56 (16)
C6—C1—C2	122.32 (16)	C6—C5—H5	120.2
C6—C1—N1	119.28 (15)	C4—C5—H5	120.2
C2—C1—N1	118.38 (15)	C1—C6—C5	118.79 (16)
C1—C2—C3	118.97 (16)	C1—C6—H6	120.6
C1—C2—H2	120.5	C5—C6—H6	120.6
C3—C2—H2	120.5	N2—C7—C4	178.9 (2)
C2—C3—C4	119.38 (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—C4	0.5 (3)	N1—C1—C6—C5	178.66 (15)
C2—C3—C4—C5	−0.8 (3)	C4—C5—C6—C1	−0.2 (3)
C2—C3—C4—C7	179.08 (16)	C3—C4—C7—N2	−162 (11)
C3—C4—C5—C6	0.7 (3)	C5—C4—C7—N2	18 (12)

Hydrogen-bond geometry (Å, º) top

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···Br1^iv	0.95	3.00	3.8063 (18)	144
N1—H1B···Br1^iv	0.88	2.54	3.4174 (16)	175
N1—H1C···Br1^v	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.

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·Br⁻
M_r	199.06
Crystal system, space group	Triclinic, 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)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.42
Crystal size (mm)	0.20 × 0.19 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Numerical (SADABS; Sheldrick, 2009)
T_min, T_max	0.631, 0.837
No. of measured, independent and observed [I > 2σ(I)] reflections	6534, 1874, 1802
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.051, 1.06
No. of reflections	1874
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (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···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···Br1^iv	0.95	3.00	3.8063 (18)	144
N1—H1B···Br1^iv	0.88	2.54	3.4174 (16)	175
N1—H1C···Br1^v	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.

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

Bruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Colapietro, M., Domenicano, A., Marciante, C. & Portalone, G. (1981). Acta Cryst. B37, 387–394. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Mague, J. T., Vumbaco, D. J., Kammer, M. N. & Koplitz, L. V. (2012). Acta Cryst. E68, o2623. CSD CrossRef IUCr Journals Google Scholar
Schweiss, B. P., Fuess, H., Fecher, G. & Weiss, A. (1983). Z. Naturforsch. Teil A, 38, 350–358. Google Scholar
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. Google Scholar
Sheldrick, G. M. (2004). SHELXM. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2009). SADABS. University of Göttingen, Germany. Google Scholar
Steiner, T. (1998). Acta Cryst. B54, 456–463. Web of Science CrossRef CAS IUCr Journals Google Scholar