Crystal structure of the co-crystal salt 2-amino-6-bromo­pyridinium 2,3,5,6-tetra­fluoro­benzoate

The title compound crystallized from an equimolar mixture of 2-amino-6-bromo­pyridine and 2,3,5,6-tetra­fluoro­benzoic acid in absolute ethanol.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.026
• wR factor = 0.059
• Data-to-parameter ratio = 14.3

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PLAT480_ALERT_4_C Long H...A H-Bond Reported H4       ..BR1      .       3.13 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9       ..BR1      .       2.94 Ang.

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PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         10 Info

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Computing details

Data collection: SMART (Bruker, 2014); cell refinement: SMART (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

2-Amino-6-bromopyridinium 2,3,5,6-tetrafluorobenzoate

Crystal data

C5H6BrN2^+·C7HF4O2^−	F(000) = 720
Mr = 367.11	Dx = 1.900 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.7230 (9) Å	Cell parameters from 3850 reflections
b = 6.5757 (4) Å	θ = 2.7–25.7°
c = 15.3224 (10) Å	µ = 3.26 mm^−1
β = 111.841 (1)°	T = 100 K
V = 1283.42 (14) Å^3	Cut block, colourless
Z = 4	0.25 × 0.20 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer	2847 independent reflections
Radiation source: fine-focus sealed tube	2395 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 8.3660 pixels mm^-1	θmax = 27.1°, θmin = 1.6°
phi and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −8→8
Tmin = 0.788, Tmax = 1.000	l = −19→19
16099 measured reflections

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0271P)^2 + 0.3891P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
2847 reflections	Δρmax = 0.41 e Å^−3
199 parameters	Δρmin = −0.32 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.35106 (2)	0.41134 (3)	0.84202 (2)	0.01733 (7)
F1	0.10223 (10)	0.15160 (19)	0.49369 (9)	0.0248 (3)
F4	0.17441 (10)	0.8060 (2)	0.40322 (9)	0.0275 (3)
F2	−0.10146 (10)	0.2028 (2)	0.38905 (10)	0.0321 (3)
F3	−0.03037 (12)	0.8562 (2)	0.30158 (10)	0.0365 (4)
O1	0.27555 (11)	0.4079 (2)	0.59997 (10)	0.0188 (3)
O2	0.32636 (12)	0.4894 (3)	0.48172 (11)	0.0238 (4)
N1	0.46382 (13)	0.4100 (3)	0.72562 (12)	0.0130 (4)
H1	0.3977 (13)	0.404 (3)	0.6815 (14)	0.016*
N2	0.53368 (14)	0.4068 (3)	0.61009 (13)	0.0171 (4)
H2A	0.4701 (14)	0.424 (3)	0.5700 (14)	0.020*
H2B	0.5859 (15)	0.422 (3)	0.5919 (16)	0.020*
C4	0.57133 (17)	0.4158 (3)	0.88912 (15)	0.0170 (4)
H4	0.577544	0.416389	0.952978	0.020*
C2	0.65046 (17)	0.4148 (3)	0.77289 (15)	0.0172 (4)
H2	0.711166	0.414715	0.757094	0.021*
C12	0.25906 (16)	0.4564 (3)	0.51564 (15)	0.0155 (5)
C5	0.47591 (16)	0.4124 (3)	0.81748 (14)	0.0147 (4)
C1	0.54936 (16)	0.4114 (3)	0.70135 (15)	0.0136 (4)
C7	0.07144 (17)	0.3268 (3)	0.44649 (15)	0.0173 (5)
C3	0.66028 (17)	0.4183 (3)	0.86458 (15)	0.0182 (5)
H3	0.728259	0.422448	0.912677	0.022*
C11	0.10738 (17)	0.6527 (3)	0.40039 (15)	0.0183 (5)
C10	0.00175 (18)	0.6802 (4)	0.34810 (15)	0.0228 (5)
C8	−0.03368 (17)	0.3535 (4)	0.39179 (16)	0.0206 (5)
C6	0.14445 (16)	0.4777 (3)	0.45227 (14)	0.0157 (5)
C9	−0.06994 (18)	0.5308 (4)	0.34355 (15)	0.0241 (5)
H9	−0.142601	0.549773	0.307970	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01626 (12)	0.02221 (12)	0.01623 (12)	−0.00014 (9)	0.00917 (8)	0.00008 (9)
F1	0.0203 (7)	0.0188 (7)	0.0320 (8)	−0.0013 (5)	0.0061 (6)	0.0036 (6)
F4	0.0277 (8)	0.0257 (8)	0.0320 (8)	−0.0027 (6)	0.0144 (6)	0.0081 (6)
F2	0.0175 (7)	0.0384 (9)	0.0383 (9)	−0.0100 (6)	0.0081 (6)	−0.0041 (7)
F3	0.0341 (8)	0.0443 (9)	0.0320 (9)	0.0155 (7)	0.0133 (7)	0.0215 (7)
O1	0.0134 (7)	0.0282 (9)	0.0142 (8)	0.0001 (7)	0.0045 (6)	0.0028 (7)
O2	0.0150 (8)	0.0418 (10)	0.0171 (8)	−0.0004 (7)	0.0089 (7)	0.0003 (7)
N1	0.0101 (8)	0.0137 (9)	0.0154 (9)	0.0021 (7)	0.0051 (7)	0.0015 (7)
N2	0.0115 (9)	0.0234 (10)	0.0184 (10)	0.0008 (8)	0.0079 (8)	0.0027 (8)
C4	0.0196 (11)	0.0169 (11)	0.0134 (10)	0.0032 (9)	0.0049 (9)	−0.0012 (9)
C2	0.0135 (10)	0.0150 (11)	0.0231 (12)	0.0021 (9)	0.0070 (9)	0.0004 (9)
C12	0.0145 (11)	0.0167 (11)	0.0159 (11)	−0.0007 (8)	0.0062 (9)	−0.0057 (8)
C5	0.0153 (10)	0.0129 (10)	0.0173 (11)	0.0005 (9)	0.0077 (9)	0.0003 (9)
C1	0.0137 (10)	0.0093 (10)	0.0195 (11)	0.0009 (8)	0.0083 (8)	0.0018 (8)
C7	0.0174 (11)	0.0193 (11)	0.0154 (11)	0.0014 (9)	0.0062 (9)	−0.0003 (9)
C3	0.0143 (11)	0.0169 (11)	0.0191 (11)	0.0022 (9)	0.0011 (9)	−0.0012 (9)
C11	0.0192 (11)	0.0240 (12)	0.0152 (11)	−0.0010 (9)	0.0103 (9)	0.0006 (9)
C10	0.0226 (12)	0.0313 (14)	0.0159 (11)	0.0111 (11)	0.0088 (10)	0.0098 (10)
C8	0.0132 (11)	0.0312 (13)	0.0191 (12)	−0.0056 (10)	0.0080 (9)	−0.0057 (10)
C6	0.0150 (11)	0.0225 (12)	0.0118 (10)	0.0018 (9)	0.0075 (9)	−0.0036 (9)
C9	0.0129 (11)	0.0439 (16)	0.0144 (12)	0.0052 (10)	0.0037 (9)	0.0002 (10)

Geometric parameters (Å, º)

Br1—C5	1.886 (2)	C4—C3	1.405 (3)
F1—C7	1.342 (2)	C4—H4	0.9500
F4—C11	1.355 (3)	C2—C3	1.361 (3)
F2—C8	1.349 (3)	C2—C1	1.413 (3)
F3—C10	1.345 (3)	C2—H2	0.9500
O1—C12	1.267 (2)	C12—C6	1.517 (3)
O2—C12	1.236 (2)	C7—C8	1.384 (3)
N1—C5	1.355 (3)	C7—C6	1.389 (3)
N1—C1	1.357 (3)	C3—H3	0.9500
N1—H1	0.909 (16)	C11—C10	1.383 (3)
N2—C1	1.334 (3)	C11—C6	1.383 (3)
N2—H2A	0.868 (16)	C10—C9	1.374 (3)
N2—H2B	0.866 (16)	C8—C9	1.371 (3)
C4—C5	1.360 (3)	C9—H9	0.9500
C5—N1—C1	120.04 (18)	F1—C7—C8	118.9 (2)
C5—N1—H1	118.4 (15)	F1—C7—C6	120.24 (19)
C1—N1—H1	121.5 (15)	C8—C7—C6	120.8 (2)
C1—N2—H2A	117.8 (16)	C2—C3—C4	120.9 (2)
C1—N2—H2B	120.3 (16)	C2—C3—H3	119.5
H2A—N2—H2B	119 (2)	C4—C3—H3	119.5
C5—C4—C3	117.10 (19)	F4—C11—C10	118.3 (2)
C5—C4—H4	121.4	F4—C11—C6	120.04 (19)
C3—C4—H4	121.4	C10—C11—C6	121.6 (2)
C3—C2—C1	119.5 (2)	F3—C10—C9	120.1 (2)
C3—C2—H2	120.2	F3—C10—C11	119.1 (2)
C1—C2—H2	120.2	C9—C10—C11	120.8 (2)
O2—C12—O1	126.5 (2)	F2—C8—C9	120.0 (2)
O2—C12—C6	118.28 (19)	F2—C8—C7	118.5 (2)
O1—C12—C6	115.18 (18)	C9—C8—C7	121.5 (2)
N1—C5—C4	123.21 (19)	C11—C6—C7	117.1 (2)
N1—C5—Br1	115.97 (15)	C11—C6—C12	121.12 (19)
C4—C5—Br1	120.82 (16)	C7—C6—C12	121.8 (2)
N2—C1—N1	117.94 (19)	C8—C9—C10	118.1 (2)
N2—C1—C2	122.87 (19)	C8—C9—H9	120.9
N1—C1—C2	119.18 (19)	C10—C9—H9	120.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.91 (2)	1.68 (2)	2.585 (2)	177 (2)
N2—H2A···O2	0.87 (2)	1.98 (2)	2.845 (2)	175 (2)
N2—H2B···O2^i	0.87 (2)	2.02 (2)	2.854 (2)	162 (2)
C4—H4···Br1^ii	0.95	3.13	4.017 (2)	155
C9—H9···Br1^iii	0.95	2.94	3.867 (2)	166

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