2-Cyano­anilinium iodide

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

doi:10.1107/S1600536813019314

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1288

doi:10.1107/S1600536813019314

Open

access

2-Cyanoanilinium iodide

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 11 July 2013; accepted 12 July 2013; online 20 July 2013)

The solid-state structure of the title salt, C₇H₇N₂^+.I⁻, consists of cation–anion sheets lying parallel to (110), with the components linked by N—H⋯I hydrogen bonds.

Related literature

For the structure of 2-cyano-1-methylpyridinium iodide, see: Kammer et al. (2013 ). For structures of other 2-cyanoanilinium salts, see: Cui & Chen (2010 ); Zhang (2009 ); Cui & Wen (2008 ); Oueslati et al. (2005 ). For the structures of 4-cyanoanilinium halides, see: Mague et al. (2012 ); Vumbaco et al. (2012 ); Colapietro et al. (1981 ).

Experimental

Crystal data

C₇H₇N₂⁺·I⁻
M_r = 246.05
Orthorhombic, P b c a
a = 10.1474 (15) Å
b = 8.6979 (13) Å
c = 18.073 (3) Å
V = 1595.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 3.94 mm⁻¹
T = 100 K
0.20 × 0.19 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: numerical (SADABS; Bruker, 2010 ) T_min = 0.43, T_max = 0.58
25911 measured reflections
2112 independent reflections
2030 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.041
S = 1.10
2112 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯I1	0.88	2.74	3.6069 (13)	169
N1—H1B⋯I1ⁱ	0.88	2.71	3.5501 (14)	160
N1—H1C⋯I1ⁱⁱ	0.88	2.84	3.6615 (13)	156
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXM (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019314/hb7106sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019314/hb7106Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019314/hb7106Isup3.cml

checkCIF report

Comment top

In the solid state, salts of the isomeric cyanoanilinium ions exhibit both layer and network structures. Thus, the iodide (Mague et al., 2012) and chloride (Colapietro et al., 1981) salts of the 4-cyanoanilinium ion as well as the chloride (Oueslati, et al., 2005) and nitrate (Cui & Wen, 2008) salts of the 2-cyanoanilinium ion have layer structures in which the –NH₃⁺ and anion moieties form a double layer with the organic portion of the cations protruding perpendicularly from both sides of this double layer. By contrast, the bromide (Zhang, 2009) and perchlorate (Cui & Chen, 2010) salts of the 2-cyanoanilinium ion form network structures while 4-cyanoanilinium bromide (Vumbaco et al., 2012) forms a stepped layer structure. A different structure type is found in the title compound where the basic unit is a zigzag chain of alternating cations and anions running parallel to a assembled by alternating short and long N—H···I hydrogen bonds (Table 1, Fig. 1). These chains are assembled into sheets parallel to (110) by intermediate length N—H···I hydrogen bonds between cations in one chain and anions in the next in which the cations in each chain are arranged in an "umbrella" fashion (Fig. 3) instead of projecting straight out towards the edges of the layer. It is also significantly different from the structure adopted by the isomeric compound 2-cyano-N-methylpyridinium iodide (Kammer et al., 2013), at least in part because the intermolecular C—H···I interactions in this compound are expected to be weaker than the N—H···I interactions in the title compound.

Related literature top

For the structure of 2-cyano-1-methylpyridinium iodide, see: Kammer et al. (2013). For structures of other 2-cyanoanilinium salts, see: Cui & Chen (2010); Zhang (2009); Cui & Wen (2008); Oueslati et al. (2005), Mague et al. (2012). For the structure of 4-cyanoanilinium chloride, see: Colapietro et al. (1981). For the structure of 4-cyanoanilinium bromide, see: Vumbaco et al. (2012).

Experimental top

2-Cyanoaniline (0.55 g) and 1.0 ml of aqueous hydroiodic acid (47% by mass) were combined in 10 ml of ethanol. This solution was slowly evaporated to dryness at room temperature to form colourless blocks of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXM (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view of the cation–anion pair showing the shortest interionic N—H···I hydrogen bonds and 50% probability displacement ellipsoids.
	Fig. 2. Packing viewed down the b axis with N—H···I interactions shown as dotted lines.
	Fig. 3. Packing viewed down the a axis with N—H···I interactions shown as dotted lines.

2-Cyanoanilinium iodide top

Crystal data top

C₇H₇N₂⁺·I⁻	D_x = 2.049 Mg m⁻³
M_r = 246.05	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9853 reflections
a = 10.1474 (15) Å	θ = 2.3–29.1°
b = 8.6979 (13) Å	µ = 3.94 mm⁻¹
c = 18.073 (3) Å	T = 100 K
V = 1595.2 (4) Å³	Block, colourless
Z = 8	0.20 × 0.19 × 0.16 mm
F(000) = 928

Data collection top

Bruker SMART APEX CCD diffractometer	2112 independent reflections
Radiation source: fine-focus sealed tube	2030 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 8.3660 pixels mm^-1	θ_max = 29.1°, θ_min = 2.3°
ϕ and ω scans	h = −13→13
Absorption correction: numerical (SADABS; Bruker, 2010)	k = −11→11
T_min = 0.43, T_max = 0.58	l = −24→24
25911 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.0208P)² + 0.7585P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.002
2112 reflections	Δρ_max = 0.59 e Å⁻³
92 parameters	Δρ_min = −0.58 e Å⁻³
0 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00151 (13)

Crystal data top

C₇H₇N₂⁺·I⁻	V = 1595.2 (4) Å³
M_r = 246.05	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.1474 (15) Å	µ = 3.94 mm⁻¹
b = 8.6979 (13) Å	T = 100 K
c = 18.073 (3) Å	0.20 × 0.19 × 0.16 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2112 independent reflections
Absorption correction: numerical (SADABS; Bruker, 2010)	2030 reflections with I > 2σ(I)
T_min = 0.43, T_max = 0.58	R_int = 0.039
25911 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.041	H-atom parameters constrained
S = 1.10	Δρ_max = 0.59 e Å⁻³
2112 reflections	Δρ_min = −0.58 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 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 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.

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

	x	y	z	U_iso*/U_eq
I1	0.58823 (2)	0.05477 (2)	0.13679 (2)	0.01326 (5)
N1	0.58054 (12)	0.44877 (14)	0.19889 (8)	0.0140 (3)
H1A	0.5870	0.3496	0.1900	0.017*
H1B	0.5590	0.4716	0.2448	0.017*
H1C	0.6593	0.4909	0.1973	0.017*
N2	0.28338 (14)	0.23930 (17)	0.21818 (8)	0.0246 (3)
C1	0.49549 (15)	0.51204 (18)	0.14089 (7)	0.0129 (3)
C2	0.54089 (14)	0.63213 (16)	0.09804 (8)	0.0149 (3)
H2	0.6252	0.6758	0.1071	0.018*
C3	0.46120 (15)	0.68861 (17)	0.04120 (8)	0.0170 (3)
H3	0.4916	0.7711	0.0113	0.020*
C4	0.33787 (15)	0.62516 (17)	0.02809 (8)	0.0183 (3)
H4	0.2854	0.6627	−0.0115	0.022*
C5	0.29073 (15)	0.50692 (19)	0.07257 (8)	0.0172 (3)
H5	0.2054	0.4654	0.0643	0.021*
C6	0.36974 (17)	0.44965 (16)	0.12950 (8)	0.0141 (3)
C7	0.32073 (14)	0.33165 (17)	0.17807 (8)	0.0167 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01359 (7)	0.01201 (7)	0.01419 (7)	−0.00040 (3)	−0.00112 (3)	−0.00004 (3)
N1	0.0147 (6)	0.0120 (6)	0.0152 (6)	−0.0004 (4)	−0.0008 (4)	0.0005 (4)
N2	0.0270 (7)	0.0236 (7)	0.0233 (7)	−0.0071 (6)	0.0076 (6)	−0.0023 (6)
C1	0.0145 (7)	0.0117 (7)	0.0126 (6)	0.0012 (5)	0.0003 (5)	−0.0022 (5)
C2	0.0153 (6)	0.0120 (6)	0.0174 (6)	−0.0003 (5)	0.0003 (5)	−0.0002 (5)
C3	0.0210 (7)	0.0127 (7)	0.0174 (7)	0.0019 (6)	0.0010 (5)	0.0009 (5)
C4	0.0213 (7)	0.0163 (7)	0.0174 (6)	0.0050 (6)	−0.0035 (5)	−0.0020 (6)
C5	0.0150 (6)	0.0166 (7)	0.0199 (7)	0.0020 (6)	−0.0011 (5)	−0.0058 (6)
C6	0.0142 (8)	0.0119 (7)	0.0161 (7)	0.0012 (5)	0.0029 (5)	−0.0033 (5)
C7	0.0143 (6)	0.0174 (7)	0.0182 (7)	−0.0017 (5)	0.0023 (5)	−0.0053 (6)

Geometric parameters (Å, º) top

N1—C1	1.4651 (19)	C2—H2	0.9500
N1—H1A	0.8800	C3—C4	1.388 (2)
N1—H1B	0.8800	C3—H3	0.9500
N1—H1C	0.8800	C4—C5	1.390 (2)
N2—C7	1.146 (2)	C4—H4	0.9500
C1—C2	1.380 (2)	C5—C6	1.396 (2)
C1—C6	1.402 (2)	C5—H5	0.9500
C2—C3	1.397 (2)	C6—C7	1.439 (2)

C1—N1—H1A	106.4	C4—C3—H3	119.7
C1—N1—H1B	116.3	C2—C3—H3	119.7
H1A—N1—H1B	114.3	C3—C4—C5	120.37 (14)
C1—N1—H1C	110.8	C3—C4—H4	119.8
H1A—N1—H1C	109.6	C5—C4—H4	119.8
H1B—N1—H1C	99.3	C4—C5—C6	119.51 (14)
C2—C1—C6	120.98 (13)	C4—C5—H5	120.2
C2—C1—N1	119.30 (13)	C6—C5—H5	120.2
C6—C1—N1	119.72 (13)	C5—C6—C1	119.52 (14)
C1—C2—C3	119.07 (14)	C5—C6—C7	120.37 (15)
C1—C2—H2	120.5	C1—C6—C7	120.07 (14)
C3—C2—H2	120.5	N2—C7—C6	178.30 (17)
C4—C3—C2	120.51 (14)

C6—C1—C2—C3	−1.9 (2)	C4—C5—C6—C7	177.45 (14)
N1—C1—C2—C3	177.87 (13)	C2—C1—C6—C5	1.9 (2)
C1—C2—C3—C4	0.2 (2)	N1—C1—C6—C5	−177.89 (13)
C2—C3—C4—C5	1.6 (2)	C2—C1—C6—C7	−175.70 (13)
C3—C4—C5—C6	−1.6 (2)	N1—C1—C6—C7	4.5 (2)
C4—C5—C6—C1	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1	0.88	2.74	3.6069 (13)	169
N1—H1B···I1ⁱ	0.88	2.71	3.5501 (14)	160
N1—H1C···I1ⁱⁱ	0.88	2.84	3.6615 (13)	156

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1	0.88	2.74	3.6069 (13)	169
N1—H1B···I1ⁱ	0.88	2.71	3.5501 (14)	160
N1—H1C···I1ⁱⁱ	0.88	2.84	3.6615 (13)	156

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

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 APEX diffractometer.

References

Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2010). APEX2, SAINT and SADABS, 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
Cui, L.-J. & Chen, X.-Y. (2010). Acta Cryst. E66, o467. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cui, L.-J. & Wen, X.-C. (2008). Acta Cryst. E64, o1620. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kammer, M. N., Koplitz, L. V. & Mague, J. T. (2013). Acta Cryst. E69, o1281. CSD CrossRef 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
Oueslati, A., Kefi, R., Akriche, S. & Ben Nasr, C. (2005). Z. Kristallogr. 220, 365. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vumbaco, D. J., Kammer, M. N., Koplitz, L. V. & Mague, J. T. (2012). Acta Cryst. E68, o2884. CSD CrossRef IUCr Journals Google Scholar
Zhang, L. (2009). Acta Cryst. E65, o2407. Web of Science CSD CrossRef IUCr Journals Google Scholar