Crystal structure of 2-cyano-1-methyl-pyridinium tetra-fluoro-borate.

The asymmetric unit of the title salt, C7H7N2 (+)·BF4 (-), comprises two independent but nearly identical formula units. The solid-state structure comprises corrugated layers of cations and anions, formed by C-H⋯F hydrogen bonding, that are approximately parallel to (010). Further C-H⋯F hydrogen bonding consolidates the three-dimensional architecture. The sample was refined as a two-component non-merohedral twin.

Related literature

For structures of other salts of the 2-cyano-1-methyl­pyridinium cation, see: Koplitz et al. (2012 ▸); Kammer et al. (2013 ▸). For structures of salts of the isomeric 2-cyano­anilinium cation, see: Zhang (2009 ▸); Cui & Chen (2010 ▸).

Experimental

Crystal data

C7H7N2 +·BF4 −

M = 205.96

Monoclinic,

a = 7.9704 (16) Å

b = 7.5527 (15) Å

c = 14.570 (3) Å

β = 90.312 (3)°

V = 877.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 150 K

0.14 × 0.13 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T min = 0.70, T max = 0.99

16120 measured reflections

4566 independent reflections

3779 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.122

S = 1.08

4566 reflections

256 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: the absolute structure could not be determined with certainty in this light-atom structure

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016011/tk5380sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016011/tk5380Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016011/tk5380Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015016011/tk5380fig1.tif

Perspective view of the asymmetric unit with 50% probability ellipsoids. The C—H⋯F inter­action is shown by a dotted line.

Click here for additional data file.

a . DOI: 10.1107/S2056989015016011/tk5380fig2.tif

Packing viewed down the a axis showing an edge view of two corrugated layers and the C—H⋯F inter­actions (dotted lines) holding them together.

Click here for additional data file.

b . DOI: 10.1107/S2056989015016011/tk5380fig3.tif

Packing viewed down the b axis providing a plan view of the corrugated sheets with C—H⋯F inter­actions shown as dotted lines.

CCDC reference: 1420782

Additional supporting information: crystallographic information; 3D view; checkCIF report

C7H7N2+·BF4−	F(000) = 416
Mr = 205.96	Dx = 1.560 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.9704 (16) Å	Cell parameters from 8457 reflections
b = 7.5527 (15) Å	θ = 2.6–29.0°
c = 14.570 (3) Å	µ = 0.15 mm−1
β = 90.312 (3)°	T = 150 K
V = 877.1 (3) Å3	Block, colourless
Z = 4	0.14 × 0.13 × 0.08 mm

Bruker SMART APEX CCD diffractometer	4566 independent reflections
Radiation source: fine-focus sealed tube	3779 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 8.3660 pixels mm-1	θmax = 29.3°, θmin = 2.6°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −10→10
Tmin = 0.70, Tmax = 0.99	l = −19→19
16120 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050	H-atom parameters constrained
wR(F2) = 0.122	w = 1/[σ2(Fo2) + (0.0572P)2 + 0.091P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
4566 reflections	Δρmax = 0.33 e Å−3
256 parameters	Δρmin = −0.27 e Å−3
1 restraint	Absolute structure: The absolute structure could not be determined with certainty in this light-atom structure
Primary atom site location: structure-invariant direct methods

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, collected 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.

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 - 0.98 Å). All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. In the late stages of the refinement a consistent pattern of Fo2 >> Fc2 suggested twinning not yet accounted for. Use of the TwinRotMat routine in PLATON (Spek, 2009) generated the twin law -1 0 0 0 - 1 0 0 0 1, inclusion of which enabled satisfactory refinement as a 2-component twin.

	x	y	z	Uiso*/Ueq
N1	0.7369 (5)	0.1294 (4)	0.8819 (3)	0.0220 (7)
N2	0.3067 (5)	0.0851 (7)	0.8963 (3)	0.0416 (11)
C1	0.6868 (6)	0.1642 (6)	0.7854 (3)	0.0273 (10)
H1A	0.7826	0.2126	0.7518	0.041*
H1B	0.5943	0.2497	0.7841	0.041*
H1C	0.6504	0.0534	0.7565	0.041*
C2	0.8990 (6)	0.1331 (6)	0.9067 (3)	0.0264 (9)
H2	0.9807	0.1629	0.8620	0.032*
C3	0.9511 (6)	0.0952 (7)	0.9947 (3)	0.0299 (10)
H3	1.0671	0.0973	1.0100	0.036*
C4	0.8341 (6)	0.0543 (6)	1.0601 (3)	0.0283 (10)
H4	0.8678	0.0281	1.1213	0.034*
C5	0.6652 (6)	0.0520 (6)	1.0352 (3)	0.0274 (9)
H5	0.5819	0.0254	1.0795	0.033*
C6	0.6204 (5)	0.0884 (6)	0.9464 (3)	0.0232 (8)
C7	0.4472 (6)	0.0856 (7)	0.9165 (3)	0.0295 (10)
B1	0.7236 (7)	0.6589 (6)	0.8140 (3)	0.0242 (10)
F1	0.7151 (4)	0.5195 (3)	0.8770 (2)	0.0328 (6)
F2	0.8600 (4)	0.7654 (4)	0.8350 (2)	0.0361 (7)
F3	0.5771 (3)	0.7603 (4)	0.8200 (2)	0.0389 (7)
F4	0.7353 (4)	0.5925 (4)	0.72573 (19)	0.0446 (8)
N3	0.7497 (5)	0.3325 (5)	0.3758 (2)	0.0246 (8)
N4	1.1617 (6)	0.4550 (8)	0.3990 (3)	0.0454 (12)
C8	0.8099 (6)	0.3192 (7)	0.2807 (3)	0.0316 (10)
H8A	0.9110	0.2455	0.2790	0.047*
H8B	0.8361	0.4378	0.2575	0.047*
H8C	0.7225	0.2655	0.2421	0.047*
C9	0.5886 (6)	0.2988 (6)	0.3939 (3)	0.0292 (10)
H9	0.5148	0.2630	0.3460	0.035*
C10	0.5294 (6)	0.3159 (6)	0.4825 (3)	0.0302 (10)
H10	0.4148	0.2926	0.4954	0.036*
C11	0.6365 (6)	0.3668 (7)	0.5519 (3)	0.0310 (10)
H11	0.5962	0.3775	0.6129	0.037*
C12	0.8039 (6)	0.4028 (6)	0.5327 (3)	0.0304 (10)
H12	0.8794	0.4387	0.5798	0.036*
C13	0.8566 (6)	0.3847 (6)	0.4439 (3)	0.0255 (9)
C14	1.0267 (7)	0.4226 (7)	0.4190 (3)	0.0327 (10)
B2	0.7732 (7)	0.8421 (7)	0.3142 (3)	0.0273 (10)
F5	0.8153 (4)	0.9543 (4)	0.3856 (2)	0.0435 (8)
F6	0.6889 (5)	0.6960 (4)	0.3476 (2)	0.0500 (9)
F7	0.9153 (4)	0.7890 (6)	0.2691 (2)	0.0569 (10)
F8	0.6664 (4)	0.9294 (4)	0.2535 (2)	0.0464 (8)

	U11	U22	U33	U12	U13	U23
N1	0.0256 (18)	0.0142 (16)	0.0263 (17)	0.0013 (14)	0.0025 (15)	−0.0004 (14)
N2	0.029 (2)	0.059 (3)	0.038 (2)	0.004 (2)	0.0041 (18)	−0.002 (2)
C1	0.037 (3)	0.022 (2)	0.023 (2)	−0.0010 (18)	−0.0026 (18)	0.0022 (17)
C2	0.023 (2)	0.023 (2)	0.033 (2)	−0.0011 (16)	0.0046 (19)	−0.0008 (19)
C3	0.025 (2)	0.033 (2)	0.032 (2)	0.0022 (19)	−0.0025 (19)	−0.002 (2)
C4	0.031 (2)	0.029 (2)	0.025 (2)	0.0000 (18)	−0.0006 (18)	−0.0012 (18)
C5	0.031 (2)	0.024 (2)	0.027 (2)	0.0002 (18)	0.0039 (19)	−0.0005 (18)
C6	0.023 (2)	0.0174 (19)	0.029 (2)	0.0007 (16)	0.0041 (17)	−0.0020 (17)
C7	0.029 (2)	0.028 (2)	0.032 (2)	0.0002 (18)	0.0046 (19)	−0.001 (2)
B1	0.029 (2)	0.018 (2)	0.026 (2)	−0.0007 (19)	0.001 (2)	0.0018 (18)
F1	0.0440 (15)	0.0189 (12)	0.0355 (14)	−0.0006 (12)	−0.0028 (13)	0.0047 (10)
F2	0.0336 (15)	0.0254 (14)	0.0492 (17)	−0.0069 (12)	−0.0028 (13)	0.0005 (12)
F3	0.0311 (15)	0.0235 (13)	0.062 (2)	0.0040 (12)	0.0021 (14)	0.0036 (13)
F4	0.069 (2)	0.0343 (16)	0.0304 (14)	−0.0020 (16)	0.0062 (15)	−0.0067 (13)
N3	0.0326 (19)	0.0141 (15)	0.0270 (18)	0.0007 (14)	0.0007 (15)	−0.0004 (14)
N4	0.034 (2)	0.060 (3)	0.042 (2)	−0.008 (2)	0.000 (2)	0.005 (2)
C8	0.041 (3)	0.025 (2)	0.028 (2)	−0.004 (2)	0.004 (2)	0.0001 (19)
C9	0.031 (2)	0.023 (2)	0.034 (2)	−0.0023 (17)	−0.005 (2)	0.0003 (19)
C10	0.029 (2)	0.023 (2)	0.039 (3)	−0.0003 (18)	0.0034 (19)	0.005 (2)
C11	0.037 (2)	0.029 (2)	0.027 (2)	0.0017 (19)	0.001 (2)	0.0019 (19)
C12	0.034 (2)	0.026 (2)	0.032 (2)	0.000 (2)	−0.003 (2)	0.0016 (19)
C13	0.029 (2)	0.0147 (18)	0.033 (2)	0.0023 (16)	−0.0026 (19)	0.0026 (17)
C14	0.035 (3)	0.031 (2)	0.032 (2)	−0.001 (2)	−0.002 (2)	0.002 (2)
B2	0.033 (3)	0.023 (2)	0.026 (2)	−0.002 (2)	0.002 (2)	0.004 (2)
F5	0.061 (2)	0.0328 (16)	0.0363 (16)	0.0103 (14)	−0.0076 (16)	−0.0078 (13)
F6	0.072 (2)	0.0196 (14)	0.059 (2)	0.0019 (15)	0.0198 (17)	0.0098 (14)
F7	0.0376 (17)	0.072 (3)	0.061 (2)	0.0042 (17)	0.0157 (15)	−0.0251 (19)
F8	0.057 (2)	0.0294 (16)	0.0522 (18)	−0.0021 (14)	−0.0197 (17)	0.0099 (14)

N1—C2	1.340 (6)	N3—C9	1.336 (6)
N1—C6	1.360 (6)	N3—C13	1.362 (6)
N1—C1	1.484 (6)	N3—C8	1.473 (6)
N2—C7	1.157 (6)	N4—C14	1.143 (7)
C1—H1A	0.9800	C8—H8A	0.9800
C1—H1B	0.9800	C8—H8B	0.9800
C1—H1C	0.9800	C8—H8C	0.9800
C2—C3	1.376 (7)	C9—C10	1.382 (7)
C2—H2	0.9500	C9—H9	0.9500
C3—C4	1.372 (7)	C10—C11	1.375 (7)
C3—H3	0.9500	C10—H10	0.9500
C4—C5	1.392 (6)	C11—C12	1.392 (7)
C4—H4	0.9500	C11—H11	0.9500
C5—C6	1.369 (6)	C12—C13	1.370 (6)
C5—H5	0.9500	C12—H12	0.9500
C6—C7	1.446 (6)	C13—C14	1.434 (7)
B1—F4	1.384 (6)	B2—F7	1.372 (6)
B1—F2	1.385 (6)	B2—F6	1.382 (6)
B1—F1	1.398 (5)	B2—F5	1.382 (6)
B1—F3	1.400 (6)	B2—F8	1.391 (6)
C2—N1—C6	118.7 (4)	C9—N3—C13	120.6 (4)
C2—N1—C1	120.4 (4)	C9—N3—C8	119.4 (4)
C6—N1—C1	120.9 (4)	C13—N3—C8	119.9 (4)
N1—C1—H1A	109.5	N3—C8—H8A	109.5
N1—C1—H1B	109.5	N3—C8—H8B	109.5
H1A—C1—H1B	109.5	H8A—C8—H8B	109.5
N1—C1—H1C	109.5	N3—C8—H8C	109.5
H1A—C1—H1C	109.5	H8A—C8—H8C	109.5
H1B—C1—H1C	109.5	H8B—C8—H8C	109.5
N1—C2—C3	122.1 (4)	N3—C9—C10	119.9 (5)
N1—C2—H2	118.9	N3—C9—H9	120.0
C3—C2—H2	118.9	C10—C9—H9	120.0
C4—C3—C2	119.5 (4)	C11—C10—C9	120.0 (4)
C4—C3—H3	120.3	C11—C10—H10	120.0
C2—C3—H3	120.3	C9—C10—H10	120.0
C3—C4—C5	118.8 (4)	C10—C11—C12	119.9 (4)
C3—C4—H4	120.6	C10—C11—H11	120.0
C5—C4—H4	120.6	C12—C11—H11	120.0
C6—C5—C4	119.4 (4)	C13—C12—C11	118.0 (5)
C6—C5—H5	120.3	C13—C12—H12	121.0
C4—C5—H5	120.3	C11—C12—H12	121.0
N1—C6—C5	121.5 (4)	N3—C13—C12	121.5 (4)
N1—C6—C7	116.7 (4)	N3—C13—C14	117.6 (4)
C5—C6—C7	121.7 (4)	C12—C13—C14	120.9 (5)
N2—C7—C6	177.1 (5)	N4—C14—C13	179.1 (6)
F4—B1—F2	111.1 (4)	F7—B2—F6	109.9 (4)
F4—B1—F1	109.9 (4)	F7—B2—F5	110.0 (4)
F2—B1—F1	109.5 (4)	F6—B2—F5	110.0 (4)
F4—B1—F3	108.5 (4)	F7—B2—F8	109.7 (4)
F2—B1—F3	108.8 (4)	F6—B2—F8	107.8 (4)
F1—B1—F3	109.1 (4)	F5—B2—F8	109.5 (4)
C6—N1—C2—C3	0.7 (7)	C13—N3—C9—C10	−0.4 (7)
C1—N1—C2—C3	−177.6 (4)	C8—N3—C9—C10	−178.0 (4)
N1—C2—C3—C4	−0.9 (8)	N3—C9—C10—C11	−0.3 (7)
C2—C3—C4—C5	0.2 (8)	C9—C10—C11—C12	0.7 (8)
C3—C4—C5—C6	0.7 (7)	C10—C11—C12—C13	−0.3 (7)
C2—N1—C6—C5	0.2 (6)	C9—N3—C13—C12	0.7 (7)
C1—N1—C6—C5	178.5 (4)	C8—N3—C13—C12	178.4 (4)
C2—N1—C6—C7	−179.9 (4)	C9—N3—C13—C14	−178.6 (4)
C1—N1—C6—C7	−1.6 (6)	C8—N3—C13—C14	−0.9 (7)
C4—C5—C6—N1	−0.9 (7)	C11—C12—C13—N3	−0.3 (7)
C4—C5—C6—C7	179.2 (5)	C11—C12—C13—C14	178.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F7i	0.98	2.50	3.407 (6)	154
C1—H1B···F8ii	0.98	2.54	3.498 (6)	166
C1—H1C···F3iii	0.98	2.47	3.214 (5)	132
C2—H2···F7i	0.95	2.29	3.190 (5)	157
C3—H3···F1iv	0.95	2.46	3.294 (6)	147
C5—H5···F1v	0.95	2.45	3.306 (5)	149
C8—H8A···F2i	0.98	2.48	3.159 (6)	126
C8—H8C···F3ii	0.98	2.55	3.437 (6)	151
C9—H9···F3ii	0.95	2.52	3.392 (6)	152
C9—H9···F4ii	0.95	2.59	3.476 (6)	156
C10—H10···F6ii	0.95	2.54	3.167 (6)	123
C12—H12···F5i	0.95	2.49	3.277 (6)	141

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C1H1AF7i	0.98	2.50	3.407(6)	154
C1H1BF8ii	0.98	2.54	3.498(6)	166
C1H1CF3iii	0.98	2.47	3.214(5)	132
C2H2F7i	0.95	2.29	3.190(5)	157
C3H3F1iv	0.95	2.46	3.294(6)	147
C5H5F1v	0.95	2.45	3.306(5)	149
C8H8AF2i	0.98	2.48	3.159(6)	126
C8H8CF3ii	0.98	2.55	3.437(6)	151
C9H9F3ii	0.95	2.52	3.392(6)	152
C9H9F4ii	0.95	2.59	3.476(6)	156
C10H10F6ii	0.95	2.54	3.167(6)	123
C12H12F5i	0.95	2.49	3.277(6)	141

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .