1,3-Bis(pyridin-2-yl)-1H-benzimidazol-3-ium tetra-fluoridoborate.

The asymmetric unit of the title compound, C(17)H(13)N(4) (+)·BF(4) (-), contains one half of the benzimidazolium cation and one half of the tetra-fluoridoborate anion, with crystallographic mirror planes bis-ecting the mol-ecules. One F atom of the tetra-fluoridoborate is equally disordered about a crystallographic mirror plane. In the crystal, C-H⋯F inter-actions link the cations and anions into layers parallel to (100). The crystal packing is further stabilized by F⋯π contacts involving the tetra-fluoridoborate anions and the five-membered rings [F⋯centroid = 2.811 (2) Å].

Related literature

For applications of N,N′-bis­(2-pyrid­yl)aryl­diamines, see: Stoessel et al. (2010 ▶); Goldfarb (2009 ▶) and of imidazolium salts, see: Berlin et al. (2007 ▶); Bold et al. (2005 ▶); Huang et al. (2005 ▶); Murakami et al. (2007 ▶); Teles et al. (1996 ▶). For pharmaceuticals based on the aniline–pyridine scaffold, see: Kim et al. (1996 ▶); Wu et al. (2001 ▶). For the synthesis of the starting material N,N′-bis­(pyridin-2-yl)benzene-1,2-diamine, see: Gdaniec et al. (2004 ▶).

Experimental

Crystal data

C17H13N4 +·BF4 −

M = 360.12

Orthorhombic,

a = 7.3412 (2) Å

b = 17.5051 (5) Å

c = 12.2426 (3) Å

V = 1573.28 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 183 K

0.44 × 0.31 × 0.11 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby detector

Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010 ▶) based on Clark & Reid (1995 ▶)] T min = 0.964, T max = 0.991

8816 measured reflections

2014 independent reflections

1543 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.117

S = 1.08

2014 reflections

130 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶), ORTEP-3 for Windows (Farrugia, 1997) ▶ and POV-RAY for Windows (Cason, 2003 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811027942/su2291sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027942/su2291Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811027942/su2291Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H13N4+·BF4−	F(000) = 736
Mr = 360.12	Dx = 1.52 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 4054 reflections
a = 7.3412 (2) Å	θ = 2.8–32.6°
b = 17.5051 (5) Å	µ = 0.13 mm−1
c = 12.2426 (3) Å	T = 183 K
V = 1573.28 (7) Å3	Plate, red
Z = 4	0.44 × 0.31 × 0.11 mm

Oxford Diffraction Xcalibur diffractometer with a Ruby detector	1543 reflections with I > 2σ(I)
ω scans	Rint = 0.022
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010) based on expressions derived by Clark & Reid (1995)]	θmax = 28.3°, θmin = 3.2°
Tmin = 0.964, Tmax = 0.991	h = −9→9
8816 measured reflections	k = −20→23
2014 independent reflections	l = −12→16

Refinement on F2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.042	w = 1/[σ2(Fo2) + (0.062P)2 + 0.2418P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.117	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.27 e Å−3
2014 reflections	Δρmin = −0.36 e Å−3
130 parameters

Experimental. Spectroscopic data for the title compound:1H-NMR in CD3CN: δ = 10.07 (s, 1H), δ = 8.837 (dd, 2H), δ = 8.48 (m, 2H), δ = 8.29 (m,2H), δ = 8.04 (t, 1H), δ = 8.01 (t, 1H), δ = 7.87 (m, 2H) δ = 7.77 (m, 2H).13C-NMR in CD3CN: δ = 150.95, 141.60, 129.49, 126.93, 118.83, 118.26,116.86.19F-NMR in CD3CN: δ = -152.32.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.7110 (2)	0.25	0.56060 (15)	0.0232 (4)
C2	0.64692 (16)	0.21032 (7)	0.39260 (10)	0.0211 (3)
C3	0.60860 (17)	0.16850 (8)	0.29898 (10)	0.0243 (3)
H3	0.6088	0.1154	0.299	0.029*
C4	0.57020 (17)	0.20992 (8)	0.20603 (11)	0.0263 (3)
H4	0.5436	0.1841	0.1416	0.032*
C5	0.69854 (17)	0.11073 (8)	0.53968 (11)	0.0245 (3)
C6	0.6441 (2)	0.09450 (9)	0.64542 (12)	0.0336 (3)
H6	0.6026	0.1324	0.6925	0.04*
C7	0.6546 (2)	0.01864 (9)	0.67741 (13)	0.0397 (4)
H7	0.622	0.0045	0.748	0.048*
C8	0.7136 (2)	−0.03573 (9)	0.60414 (14)	0.0374 (4)
H8	0.7192	−0.087	0.624	0.045*
C9	0.7640 (2)	−0.01265 (8)	0.50081 (14)	0.0345 (4)
H9	0.8038	−0.0496	0.4517	0.041*
N1	0.68805 (14)	0.18768 (6)	0.49998 (9)	0.0223 (3)
N2	0.75864 (17)	0.06028 (7)	0.46749 (10)	0.0302 (3)
F1	0.58623 (16)	0.18658 (7)	0.89742 (12)	0.0763 (4)
F2	0.8041 (3)	0.2711 (2)	0.98569 (15)	0.0680 (16)	0.5
F3	0.8073 (2)	0.25	0.80661 (11)	0.0577 (4)
B1	0.6969 (3)	0.25	0.89769 (19)	0.0338 (5)
H1	0.743 (3)	0.25	0.6360 (19)	0.024 (5)*

	U11	U22	U33	U12	U13	U23
C1	0.0249 (9)	0.0230 (10)	0.0217 (9)	0	−0.0010 (7)	0
C2	0.0210 (6)	0.0224 (7)	0.0200 (6)	0.0008 (5)	0.0019 (5)	0.0021 (5)
C3	0.0254 (6)	0.0229 (7)	0.0245 (7)	−0.0016 (5)	0.0012 (5)	−0.0029 (5)
C4	0.0263 (6)	0.0313 (7)	0.0212 (6)	−0.0013 (5)	0.0002 (5)	−0.0043 (5)
C5	0.0257 (6)	0.0215 (7)	0.0263 (7)	−0.0014 (5)	−0.0046 (5)	0.0030 (5)
C6	0.0450 (8)	0.0289 (8)	0.0269 (7)	−0.0052 (6)	−0.0002 (6)	0.0010 (6)
C7	0.0521 (9)	0.0371 (9)	0.0297 (7)	−0.0092 (7)	−0.0045 (7)	0.0114 (7)
C8	0.0416 (9)	0.0249 (8)	0.0457 (9)	−0.0009 (6)	−0.0092 (7)	0.0117 (7)
C9	0.0388 (8)	0.0235 (8)	0.0411 (8)	0.0055 (6)	−0.0036 (6)	0.0020 (6)
N1	0.0258 (5)	0.0211 (6)	0.0200 (5)	0.0001 (4)	−0.0006 (4)	0.0015 (4)
N2	0.0353 (6)	0.0230 (6)	0.0325 (6)	0.0033 (5)	0.0002 (5)	0.0019 (5)
F1	0.0558 (7)	0.0436 (7)	0.1295 (12)	−0.0010 (5)	0.0195 (7)	0.0143 (7)
F2	0.0400 (9)	0.132 (5)	0.0315 (9)	−0.0042 (12)	−0.0083 (7)	−0.0174 (14)
F3	0.0646 (10)	0.0810 (12)	0.0276 (7)	0	0.0114 (6)	0
B1	0.0284 (11)	0.0494 (16)	0.0236 (11)	0	−0.0016 (9)	0

C1—N1	1.3302 (15)	C6—C7	1.387 (2)
C1—H1	0.95 (2)	C6—H6	0.93
C2—C3	1.3887 (18)	C7—C8	1.378 (2)
C2—C2i	1.389 (3)	C7—H7	0.93
C2—N1	1.4060 (16)	C8—C9	1.379 (2)
C3—C4	1.3784 (18)	C8—H8	0.93
C3—H3	0.93	C9—N2	1.3408 (19)
C4—C4i	1.403 (3)	C9—H9	0.93
C4—H4	0.93	F1—B1	1.3756 (18)
C5—N2	1.3249 (18)	F2—B1	1.384 (3)
C5—C6	1.384 (2)	F3—B1	1.379 (3)
C5—N1	1.4341 (17)
N1—C1—N1i	110.20 (16)	C8—C7—H7	120.2
N1—C1—H1	124.88 (9)	C6—C7—H7	120.2
N1i—C1—H1	124.88 (9)	C7—C8—C9	118.64 (14)
C3—C2—C2i	121.81 (8)	C7—C8—H8	120.7
C3—C2—N1	131.81 (12)	C9—C8—H8	120.7
C2i—C2—N1	106.37 (7)	N2—C9—C8	123.39 (15)
C4—C3—C2	116.46 (13)	N2—C9—H9	118.3
C4—C3—H3	121.8	C8—C9—H9	118.3
C2—C3—H3	121.8	C1—N1—C2	108.53 (11)
C3—C4—C4i	121.74 (8)	C1—N1—C5	125.06 (12)
C3—C4—H4	119.1	C2—N1—C5	126.39 (11)
C4i—C4—H4	119.1	C5—N2—C9	116.19 (13)
N2—C5—C6	125.68 (13)	F1—B1—F1i	107.61 (19)
N2—C5—N1	114.70 (12)	F1—B1—F3	110.21 (13)
C6—C5—N1	119.61 (12)	F1—B1—F2i	97.01 (18)
C5—C6—C7	116.38 (14)	F1—B1—F2	123.6 (2)
C5—C6—H6	121.8	F1i—B1—F2	97.01 (18)
C7—C6—H6	121.8	F3—B1—F2	107.17 (18)
C8—C7—C6	119.69 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F3	0.95 (2)	2.14 (2)	3.094 (2)	178.(2)
C9—H9···F1ii	0.93	2.62	3.4759 (19)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯F3	0.95 (2)	2.14 (2)	3.094 (2)	178 (2)
C9—H9⋯F1i	0.93	2.62	3.4759 (19)	154

Symmetry code: (i) .