2-Cyano­anilinium tetra­fluoro­borate

Zhang, Y.

doi:10.1107/S1600536809032863

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2373

doi:10.1107/S1600536809032863

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2-Cyanoanilinium tetrafluoroborate

Yi Zhang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China, and Department of Physics, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 6 August 2009; accepted 18 August 2009; online 9 September 2009)

In the title compound, C₇H₇N₂⁺·BF₄⁻, the non-H atoms of the cation are almost coplanar (r.m.s. deviation = 0.035 Å). The cations and anions are connected by intermolecular N—H⋯F and N—H⋯N hydrogen bonds, forming a two-dimensional network parallel to (10 $[\overline{1}]$ ).

Related literature

For the application of metal-organic coordination compounds, see: Fu et al. (2007 ); Chen et al. (2000 ); Fu & Xiong (2008 ); Xiong et al. (1999 ); Xie et al. (2003 ); Zhang et al. (2001 ). For general background to nitrile derivatives, see: Fu et al. (2008 ); Wang et al. (2002 ).

Experimental

Crystal data

C₇H₇N₂⁺·BF₄⁻
M_r = 205.96
Monoclinic, P 2₁ /n
a = 10.971 (2) Å
b = 7.3565 (15) Å
c = 11.022 (2) Å
β = 103.11 (3)°
V = 866.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.96, T_max = 1.00 (expected range = 0.931–0.969)
8625 measured reflections
1978 independent reflections
1417 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.141
S = 1.08
1978 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.89	2.54	3.179 (3)	130
N1—H1A⋯F4ⁱⁱ	0.89	2.12	2.896 (2)	146
N1—H1B⋯F4ⁱⁱⁱ	0.89	2.21	2.993 (2)	147
N1—H1C⋯F3	0.89	1.95	2.799 (2)	160
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032863/ci2881sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032863/ci2881Isup2.hkl

checkCIF report

Comment top

The construction of metal-organic coordination compounds has attracted much attention owing to potential functions, such as permittivity, fluorescence, magnetism and optical properties (Fu et al., 2007; Chen et al., 2000; Fu & Xiong (2008); Xie et al., 2003; Zhang et al.,2001; Xiong et al., 1999). Nitrile derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks. (Wang et al. 2002; Fu et al., 2008). We report here the crystal structure of the title compound, 2-cyanobenzenaminium tetrafluoroborate.

In the 2-cyanobenzenaminium cation (Fig.1), the nitrile group and the benzene ring are almost coplanar. The nitrile group C7≡N2 bond length of 1.150 (3) Å is within the normal range.

In the crystal structure, all the amine group H atoms are involved in N—H···F hydrogen bonds (Table 1) with F atoms of the BF₄^- anion. These hydrogen bonds along with N—H···N hydrogen bonds link the ionic units into a two-dimensional network (Fig. 2) parallel to the (101).

Related literature top

For the application of metal-organic coordination compounds, see: Fu et al. (2007); Chen et al. (2000); Fu & Xiong (2008); Xiong et al. (1999); Xie et al. (2003); Zhang et al. (2001). For general background to nitrile derivatives, see: Fu et al. (2008); Wang et al. (2002).

Experimental top

The commercial 2-aminobenzonitrile (3 mmol, 0.55 g) and HBF₄ (0.5 ml) were dissolved in ethanol (20 ml). Colourless block-shaped crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines. C-bound H atoms have been omitted for clarity

2-Cyanoanilinium tetrafluoroborate top

Crystal data top

C₇H₇N₂⁺·BF₄⁻	F(000) = 416
M_r = 205.96	D_x = 1.579 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1417 reflections
a = 10.971 (2) Å	θ = 3.4–27.5°
b = 7.3565 (15) Å	µ = 0.16 mm⁻¹
c = 11.022 (2) Å	T = 298 K
β = 103.11 (3)°	Block, colourless
V = 866.4 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1978 independent reflections
Radiation source: fine-focus sealed tube	1417 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
CCD profile fitting scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.96, T_max = 1.00	l = −14→14
8625 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0571P)² + 0.4139P] where P = (F_o² + 2F_c²)/3
1978 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₇H₇N₂⁺·BF₄⁻	V = 866.4 (3) Å³
M_r = 205.96	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.971 (2) Å	µ = 0.16 mm⁻¹
b = 7.3565 (15) Å	T = 298 K
c = 11.022 (2) Å	0.30 × 0.25 × 0.20 mm
β = 103.11 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1978 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1417 reflections with I > 2σ(I)
T_min = 0.96, T_max = 1.00	R_int = 0.041
8625 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.08	Δρ_max = 0.32 e Å⁻³
1978 reflections	Δρ_min = −0.32 e Å⁻³
128 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
F4	0.36113 (13)	0.72246 (19)	0.25229 (13)	0.0500 (4)
F3	0.48625 (14)	0.7353 (2)	0.44366 (13)	0.0575 (4)
N1	0.59296 (16)	0.6600 (3)	0.69414 (15)	0.0337 (4)
H1A	0.6182	0.5482	0.6812	0.051*
H1B	0.6589	0.7275	0.7293	0.051*
H1C	0.5548	0.7094	0.6218	0.051*
F2	0.34337 (15)	0.9602 (2)	0.37300 (16)	0.0625 (5)
C1	0.50557 (18)	0.6518 (3)	0.77689 (18)	0.0302 (5)
F1	0.51445 (14)	0.9330 (3)	0.29556 (18)	0.0737 (6)
C2	0.5337 (2)	0.7425 (3)	0.89064 (19)	0.0348 (5)
C6	0.3969 (2)	0.5547 (3)	0.7402 (2)	0.0437 (6)
H6	0.3792	0.4939	0.6643	0.052*
N2	0.7317 (2)	0.9429 (3)	0.9488 (2)	0.0586 (6)
C7	0.6444 (2)	0.8517 (3)	0.9248 (2)	0.0428 (6)
B1	0.4282 (2)	0.8402 (3)	0.3425 (2)	0.0359 (6)
C4	0.3405 (3)	0.6365 (4)	0.9311 (3)	0.0580 (8)
H4	0.2840	0.6313	0.9824	0.070*
C3	0.4507 (2)	0.7323 (3)	0.9687 (2)	0.0483 (6)
H3	0.4693	0.7897	1.0458	0.058*
C5	0.3138 (2)	0.5485 (4)	0.8180 (3)	0.0570 (7)
H5	0.2393	0.4842	0.7934	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F4	0.0566 (9)	0.0453 (8)	0.0442 (8)	−0.0023 (6)	0.0037 (7)	−0.0056 (6)
F3	0.0587 (9)	0.0613 (10)	0.0455 (8)	0.0069 (7)	−0.0029 (7)	0.0162 (7)
N1	0.0376 (10)	0.0351 (9)	0.0291 (9)	0.0028 (8)	0.0092 (7)	−0.0004 (7)
F2	0.0658 (9)	0.0467 (9)	0.0762 (11)	0.0167 (7)	0.0186 (8)	−0.0097 (8)
C1	0.0324 (10)	0.0288 (10)	0.0303 (10)	0.0072 (8)	0.0091 (8)	0.0036 (8)
F1	0.0435 (8)	0.0830 (12)	0.0922 (13)	−0.0162 (8)	0.0107 (8)	0.0342 (10)
C2	0.0420 (11)	0.0316 (11)	0.0311 (11)	0.0065 (9)	0.0091 (9)	0.0001 (9)
C6	0.0356 (12)	0.0447 (14)	0.0491 (14)	0.0034 (10)	0.0058 (10)	−0.0046 (11)
N2	0.0597 (14)	0.0587 (14)	0.0558 (14)	−0.0010 (12)	0.0095 (11)	−0.0178 (11)
C7	0.0542 (15)	0.0392 (13)	0.0347 (12)	0.0088 (12)	0.0094 (11)	−0.0075 (10)
B1	0.0324 (12)	0.0315 (12)	0.0412 (13)	0.0004 (10)	0.0030 (10)	0.0053 (11)
C4	0.0609 (17)	0.0541 (17)	0.0729 (19)	0.0135 (14)	0.0445 (15)	0.0118 (14)
C3	0.0670 (16)	0.0430 (13)	0.0422 (13)	0.0147 (12)	0.0277 (12)	0.0018 (10)
C5	0.0375 (13)	0.0529 (16)	0.085 (2)	0.0011 (12)	0.0223 (13)	0.0022 (14)

Geometric parameters (Å, º) top

F4—B1	1.396 (3)	C2—C3	1.389 (3)
F3—B1	1.387 (3)	C2—C7	1.434 (3)
N1—C1	1.467 (2)	C6—C5	1.387 (4)
N1—H1A	0.89	C6—H6	0.93
N1—H1B	0.89	N2—C7	1.150 (3)
N1—H1C	0.89	C4—C5	1.376 (4)
F2—B1	1.379 (3)	C4—C3	1.379 (4)
C1—C6	1.370 (3)	C4—H4	0.93
C1—C2	1.392 (3)	C3—H3	0.93
F1—B1	1.361 (3)	C5—H5	0.93

C1—N1—H1A	109.5	F1—B1—F2	109.7 (2)
C1—N1—H1B	109.5	F1—B1—F3	110.68 (19)
H1A—N1—H1B	109.5	F2—B1—F3	111.9 (2)
C1—N1—H1C	109.5	F1—B1—F4	109.9 (2)
H1A—N1—H1C	109.5	F2—B1—F4	107.16 (18)
H1B—N1—H1C	109.5	F3—B1—F4	107.42 (19)
C6—C1—C2	121.1 (2)	C5—C4—C3	120.3 (2)
C6—C1—N1	119.06 (19)	C5—C4—H4	119.9
C2—C1—N1	119.87 (19)	C3—C4—H4	119.9
C3—C2—C1	119.3 (2)	C4—C3—C2	119.7 (2)
C3—C2—C7	120.2 (2)	C4—C3—H3	120.2
C1—C2—C7	120.42 (19)	C2—C3—H3	120.2
C1—C6—C5	119.0 (2)	C4—C5—C6	120.6 (2)
C1—C6—H6	120.5	C4—C5—H5	119.7
C5—C6—H6	120.5	C6—C5—H5	119.7
N2—C7—C2	177.7 (3)

C6—C1—C2—C3	0.8 (3)	C5—C4—C3—C2	1.2 (4)
N1—C1—C2—C3	−179.40 (19)	C1—C2—C3—C4	−1.6 (3)
C6—C1—C2—C7	−176.6 (2)	C7—C2—C3—C4	175.8 (2)
N1—C1—C2—C7	3.2 (3)	C3—C4—C5—C6	0.0 (4)
C2—C1—C6—C5	0.4 (3)	C1—C6—C5—C4	−0.8 (4)
N1—C1—C6—C5	−179.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.89	2.54	3.179 (3)	130
N1—H1A···F4ⁱⁱ	0.89	2.12	2.896 (2)	146
N1—H1B···F4ⁱⁱⁱ	0.89	2.21	2.993 (2)	147
N1—H1C···F3	0.89	1.95	2.799 (2)	160

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·BF₄⁻
M_r	205.96
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	10.971 (2), 7.3565 (15), 11.022 (2)
β (°)	103.11 (3)
V (Å³)	866.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.96, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	8625, 1978, 1417
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.141, 1.08
No. of reflections	1978
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.32

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), 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···N2ⁱ	0.89	2.54	3.179 (3)	130
N1—H1A···F4ⁱⁱ	0.89	2.12	2.896 (2)	146
N1—H1B···F4ⁱⁱⁱ	0.89	2.21	2.993 (2)	147
N1—H1C···F3	0.89	1.95	2.799 (2)	160

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

Acknowledgements

This work was supported by the Outstanding Doctoral Dissertation Fund of Southeast University.

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