2-Amino-5-bromo-pyridin-1-ium (2-amino-5-bromo-pyridine-κN (1))trichloridozincate.

The structure of the title salt, (C5H6BrN2)[ZnCl3(C5H5BrN2)], consists of discrete 2-amino-5-bromo-pyridin-1-ium cations and distorted tetra-hedral (2-amino-5-bromo-pyridine)-tri-chlorido-zincate anions. In the crystal, the complex anions and cations are linked via N-H⋯Cl hydrogen bonds into layers parallel to (101). Short Br⋯Cl contacts of 3.4239 (11) and 3.4503 (12) Å are observed, as well as π-π stacking inter-actions between the pyridine and pyridinium rings, with alternating centroid-to-centroid distances of 3.653 (2) and 3.845 (2) Å.

Related literature

For background to the chemistry of substituted pyridines, see: Janiak et al. (1999 ▶); Hubrich et al. (2010 ▶); Wei et al. (2012 ▶). For the biological activities and electrochemical properties of pyridine derivatives, see: Jo et al. (2004 ▶); Xiao et al. (2012 ▶).

Experimental

Crystal data

(C5H6BrN2)[ZnCl3(C5H5BrN2)]

M = 518.77

Monoclinic,

a = 9.4238 (4) Å

b = 13.6544 (6) Å

c = 13.5679 (6) Å

β = 104.349 (1)°

V = 1691.40 (13) Å3

Z = 4

Mo Kα radiation

μ = 6.64 mm−1

T = 293 K

0.26 × 0.16 × 0.08 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.286, T max = 0.576

18043 measured reflections

2979 independent reflections

2491 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.086

S = 1.02

2979 reflections

196 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.23 e Å−3

Δρmin = −0.40 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813011884/wm2739sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011884/wm2739Isup2.hkl

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

(C5H6BrN2)[ZnCl3(C5H5BrN2)]	F(000) = 1000
Mr = 518.77	Dx = 2.037 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4332 reflections
a = 9.4238 (4) Å	θ = 2.2–24.1°
b = 13.6544 (6) Å	µ = 6.64 mm−1
c = 13.5679 (6) Å	T = 293 K
β = 104.349 (1)°	Block, brown
V = 1691.40 (13) Å3	0.26 × 0.16 × 0.08 mm
Z = 4

Bruker APEX CCD area-detector diffractometer	2979 independent reflections
Radiation source: fine-focus sealed tube	2491 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
0.3° ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→11
Tmin = 0.286, Tmax = 0.576	k = −16→16
18043 measured reflections	l = −16→16

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0386P)2 + 2.1357P] where P = (Fo2 + 2Fc2)/3
2979 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 1.23 e Å−3
5 restraints	Δρmin = −0.40 e Å−3

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
Zn1	0.84827 (5)	0.03227 (3)	0.27004 (3)	0.04549 (14)
N1	0.9443 (3)	0.1421 (2)	0.2061 (2)	0.0424 (7)
N2	0.8519 (5)	0.2686 (3)	0.2841 (3)	0.0656 (10)
H2A	0.816 (5)	0.226 (3)	0.320 (3)	0.079*
H2B	0.843 (5)	0.3311 (17)	0.295 (4)	0.079*
N3	0.1587 (4)	0.1505 (2)	0.4873 (3)	0.0519 (8)
H3A	0.104 (4)	0.112 (3)	0.513 (3)	0.062*
N4	0.0611 (5)	0.2750 (3)	0.5635 (3)	0.0642 (10)
H4A	0.019 (5)	0.234 (3)	0.597 (3)	0.077*
H4B	0.056 (5)	0.3368 (17)	0.579 (4)	0.077*
Cl1	0.81449 (12)	0.07487 (8)	0.42275 (8)	0.0559 (3)
Cl2	0.63220 (11)	0.00231 (7)	0.15590 (7)	0.0509 (2)
Cl3	1.00795 (13)	−0.09311 (7)	0.29181 (8)	0.0589 (3)
C1	0.9311 (4)	0.2387 (3)	0.2208 (3)	0.0461 (9)
C2	1.0012 (5)	0.3065 (3)	0.1699 (3)	0.0588 (11)
H2	0.9933	0.3733	0.1810	0.071*
C3	1.0794 (5)	0.2747 (3)	0.1055 (3)	0.0614 (12)
H3	1.1252	0.3191	0.0716	0.074*
C4	1.0908 (4)	0.1746 (3)	0.0904 (3)	0.0521 (10)
C5	1.0238 (4)	0.1116 (3)	0.1420 (3)	0.0461 (9)
H5	1.0333	0.0446	0.1326	0.055*
C6	0.1411 (4)	0.2466 (3)	0.5014 (3)	0.0469 (9)
C7	0.2104 (5)	0.3113 (3)	0.4476 (3)	0.0538 (10)
H7	0.2005	0.3786	0.4547	0.065*
C8	0.2913 (4)	0.2767 (3)	0.3856 (3)	0.0552 (10)
H8	0.3366	0.3199	0.3501	0.066*
C9	0.3068 (4)	0.1754 (3)	0.3750 (3)	0.0528 (10)
C10	0.2379 (5)	0.1142 (3)	0.4251 (3)	0.0536 (10)
H10	0.2447	0.0469	0.4171	0.064*
Br1	1.19546 (6)	0.12257 (4)	0.00001 (4)	0.07623 (18)
Br2	0.42174 (6)	0.12277 (5)	0.29263 (4)	0.07970 (19)

	U11	U22	U33	U12	U13	U23
Zn1	0.0510 (3)	0.0391 (2)	0.0496 (3)	−0.00250 (19)	0.0187 (2)	0.00095 (19)
N1	0.0439 (17)	0.0370 (16)	0.0489 (18)	−0.0010 (13)	0.0163 (14)	0.0004 (13)
N2	0.086 (3)	0.040 (2)	0.079 (3)	0.0100 (19)	0.036 (2)	−0.0003 (19)
N3	0.056 (2)	0.0417 (19)	0.061 (2)	−0.0096 (15)	0.0204 (17)	−0.0032 (16)
N4	0.076 (3)	0.055 (2)	0.070 (2)	−0.005 (2)	0.033 (2)	−0.006 (2)
Cl1	0.0633 (6)	0.0595 (6)	0.0492 (6)	0.0011 (5)	0.0218 (5)	−0.0012 (5)
Cl2	0.0517 (6)	0.0443 (5)	0.0568 (6)	−0.0039 (4)	0.0137 (5)	0.0020 (4)
Cl3	0.0694 (7)	0.0455 (5)	0.0646 (6)	0.0112 (5)	0.0219 (5)	0.0063 (5)
C1	0.047 (2)	0.039 (2)	0.049 (2)	−0.0024 (16)	0.0062 (18)	0.0020 (17)
C2	0.072 (3)	0.042 (2)	0.060 (3)	−0.008 (2)	0.011 (2)	0.0033 (19)
C3	0.070 (3)	0.054 (3)	0.058 (3)	−0.019 (2)	0.012 (2)	0.011 (2)
C4	0.048 (2)	0.065 (3)	0.044 (2)	−0.0064 (19)	0.0119 (18)	0.0017 (19)
C5	0.047 (2)	0.043 (2)	0.049 (2)	−0.0042 (17)	0.0143 (18)	0.0007 (17)
C6	0.043 (2)	0.045 (2)	0.050 (2)	−0.0043 (17)	0.0064 (18)	−0.0033 (17)
C7	0.058 (3)	0.040 (2)	0.062 (3)	−0.0053 (18)	0.010 (2)	0.0050 (19)
C8	0.051 (2)	0.061 (3)	0.055 (2)	−0.008 (2)	0.014 (2)	0.008 (2)
C9	0.039 (2)	0.068 (3)	0.052 (2)	0.0020 (19)	0.0130 (18)	−0.001 (2)
C10	0.052 (2)	0.052 (2)	0.057 (2)	0.0014 (19)	0.015 (2)	−0.005 (2)
Br1	0.0751 (3)	0.1016 (4)	0.0625 (3)	−0.0195 (3)	0.0369 (3)	−0.0081 (3)
Br2	0.0638 (3)	0.1060 (4)	0.0769 (4)	0.0159 (3)	0.0318 (3)	0.0004 (3)

Zn1—N1	2.052 (3)	C2—C3	1.347 (6)
Zn1—Cl1	2.2494 (11)	C2—H2	0.9300
Zn1—Cl3	2.2499 (11)	C3—C4	1.390 (6)
Zn1—Cl2	2.2691 (11)	C3—H3	0.9300
N1—C1	1.344 (5)	C4—C5	1.359 (5)
N1—C5	1.347 (5)	C4—Br1	1.892 (4)
N2—C1	1.334 (5)	C5—H5	0.9300
N2—H2A	0.874 (19)	C6—C7	1.406 (6)
N2—H2B	0.873 (19)	C7—C8	1.354 (6)
N3—C6	1.342 (5)	C7—H7	0.9300
N3—C10	1.351 (5)	C8—C9	1.401 (6)
N3—H3A	0.868 (19)	C8—H8	0.9300
N4—C6	1.320 (6)	C9—C10	1.342 (6)
N4—H4A	0.881 (19)	C9—Br2	1.882 (4)
N4—H4B	0.874 (19)	C10—H10	0.9300
C1—C2	1.413 (6)
N1—Zn1—Cl1	112.23 (9)	C2—C3—C4	119.2 (4)
N1—Zn1—Cl3	105.12 (9)	C2—C3—H3	120.4
Cl1—Zn1—Cl3	108.58 (4)	C4—C3—H3	120.4
N1—Zn1—Cl2	104.99 (9)	C5—C4—C3	118.9 (4)
Cl1—Zn1—Cl2	111.55 (4)	C5—C4—Br1	118.6 (3)
Cl3—Zn1—Cl2	114.22 (4)	C3—C4—Br1	122.5 (3)
C1—N1—C5	119.1 (3)	N1—C5—C4	122.7 (4)
C1—N1—Zn1	126.0 (3)	N1—C5—H5	118.7
C5—N1—Zn1	114.9 (2)	C4—C5—H5	118.7
C1—N2—H2A	121 (3)	N4—C6—N3	119.3 (4)
C1—N2—H2B	120 (3)	N4—C6—C7	123.9 (4)
H2A—N2—H2B	119 (5)	N3—C6—C7	116.8 (4)
C6—N3—C10	123.7 (4)	C8—C7—C6	120.6 (4)
C6—N3—H3A	116 (3)	C8—C7—H7	119.7
C10—N3—H3A	120 (3)	C6—C7—H7	119.7
C6—N4—H4A	123 (3)	C7—C8—C9	119.8 (4)
C6—N4—H4B	121 (3)	C7—C8—H8	120.1
H4A—N4—H4B	115 (5)	C9—C8—H8	120.1
N2—C1—N1	118.9 (4)	C10—C9—C8	119.2 (4)
N2—C1—C2	121.2 (4)	C10—C9—Br2	119.0 (3)
N1—C1—C2	120.0 (4)	C8—C9—Br2	121.9 (3)
C3—C2—C1	120.1 (4)	C9—C10—N3	119.9 (4)
C3—C2—H2	119.9	C9—C10—H10	120.0
C1—C2—H2	119.9	N3—C10—H10	120.0
Cl1—Zn1—N1—C1	−29.5 (3)	C1—N1—C5—C4	−0.6 (6)
Cl3—Zn1—N1—C1	−147.3 (3)	Zn1—N1—C5—C4	177.7 (3)
Cl2—Zn1—N1—C1	91.9 (3)	C3—C4—C5—N1	1.2 (6)
Cl1—Zn1—N1—C5	152.4 (2)	Br1—C4—C5—N1	−178.5 (3)
Cl3—Zn1—N1—C5	34.5 (3)	C10—N3—C6—N4	179.7 (4)
Cl2—Zn1—N1—C5	−86.3 (3)	C10—N3—C6—C7	0.0 (6)
C5—N1—C1—N2	179.8 (4)	N4—C6—C7—C8	179.7 (4)
Zn1—N1—C1—N2	1.7 (5)	N3—C6—C7—C8	−0.5 (6)
C5—N1—C1—C2	−0.5 (5)	C6—C7—C8—C9	−0.2 (6)
Zn1—N1—C1—C2	−178.6 (3)	C7—C8—C9—C10	1.5 (6)
N2—C1—C2—C3	−179.3 (4)	C7—C8—C9—Br2	−178.4 (3)
N1—C1—C2—C3	1.0 (6)	C8—C9—C10—N3	−2.0 (6)
C1—C2—C3—C4	−0.4 (7)	Br2—C9—C10—N3	177.8 (3)
C2—C3—C4—C5	−0.7 (6)	C6—N3—C10—C9	1.3 (6)
C2—C3—C4—Br1	179.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.87 (2)	2.50 (3)	3.315 (4)	156 (4)
N2—H2B···Cl2i	0.87 (2)	2.43 (2)	3.288 (4)	169 (5)
N3—H3A···Cl1ii	0.87 (2)	2.75 (4)	3.309 (4)	124 (3)
N3—H3A···Cl1iii	0.87 (2)	2.74 (4)	3.297 (4)	123 (4)
N4—H4A···Cl3iii	0.88 (2)	2.49 (3)	3.328 (4)	159 (4)
N4—H4B···Cl2iv	0.87 (2)	2.46 (3)	3.295 (4)	160 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl1	0.87 (2)	2.50 (3)	3.315 (4)	156 (4)
N2—H2B⋯Cl2i	0.87 (2)	2.43 (2)	3.288 (4)	169 (5)
N3—H3A⋯Cl1ii	0.87 (2)	2.75 (4)	3.309 (4)	124 (3)
N3—H3A⋯Cl1iii	0.87 (2)	2.74 (4)	3.297 (4)	123 (4)
N4—H4A⋯Cl3iii	0.88 (2)	2.49 (3)	3.328 (4)	159 (4)
N4—H4B⋯Cl2iv	0.87 (2)	2.46 (3)	3.295 (4)	160 (4)

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