Halobismuth(III) salts with substituted amino­pyridinium cations

The crystal structures of six halobismuth(III) salts of variously substituted amino­pyridinium cations display discrete mononuclear [BiCl₆]³⁻ and dinuclear [Bi₂X₁₀]⁴⁻ anions (X = Cl or Br), and polymeric cis-double-halo-bridged [Bi_nX_4n]ⁿ⁻ anionic chains (X = Br or I). Bis(2-amino-3-ammonio­pyridinium) hexa­chlorido­bis­muth(III) chloride monohydrate, (C₅H₉N₃)₂[BiCl₆]Cl·H₂O, (1), contains discrete mononuclear [BiCl₆]³⁻ and chloride anions. Tetra­kis(2-amino-3-methyl­pyridinium) di-μ-chlorido-bis­[tetra­chlorido­bis­muth(III)], (C₆H₉N₂)₄[Bi₂Cl₁₀], (2), tetra­kis­(2-amino-3-methyl­pyridinium) di-μ-bromido-bis­[tetra­bro­mido­bis­muth(III)], (C₆H₉N₂)₄[Bi₂Br₁₀], (3), and bis­(4-amino-3-ammonio­pyri­din­ium) di-μ-chlorido-bis­[tetra­chlorido­bis­muth(III)] dihydrate, (C₅H₉N₃)₂[Bi₂Cl₁₀]·2H₂O, (4), incorporate discrete [Bi₂X₁₀]⁴⁻ anions (X = Cl or Br), while catena-poly[2,6-di­amino­pyridinium [[cis-di­iodido­bis­muth(III)]-di-μ-iodido]], {(C₅H₈N₃)[BiI₄]}_n, (5), and catena-poly[2,6-di­amino­pyridinium [[cis-di­bromido­bis­muth(III)]-di-μ-bromido]], {(C₅H₇N₂)[BiBr₄]}_n, (6), include [Bi_nX_4n]ⁿ⁻ anionic chains (X = Br or I). Structures (2) and (3) are isostructural, while that of (5) is a pseudomerohedral twin. There is no discernible correlation between the type of anionic species obtained and the cation or halide ligand used. The Bi^III centres always have a slightly distorted octa­hedral geometry and there is a correlation between the Bi—X bond lengths and the number of classic N—H...X hydrogen bonds that the X ligand accepts, with a greater number of inter­actions corresponding with slightly longer Bi—X distances. The supra­molecular networks formed by classic N—H...X hydrogen bonds include ladders, bilayers and three-dimensional frameworks.

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b) and PLATON (Spek, 2015, 2020).

Bis(2-amino-3-ammoniopyridinium) hexachloridobismuth(III) chloride monohydrate (1)

Crystal data

(C5H9N3)2[BiCl6]Cl·H2O	Z = 2
Mr = 697.45	F(000) = 664
Triclinic, P1	Dx = 2.135 Mg m^−3
a = 9.1612 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8591 (6) Å	Cell parameters from 5333 reflections
c = 11.7273 (7) Å	θ = 3.5–29.2°
α = 94.303 (4)°	µ = 9.00 mm^−1
β = 101.914 (4)°	T = 160 K
γ = 106.254 (4)°	Prism, red
V = 1084.89 (10) Å^3	0.25 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction SuperNova dual radiation diffractometer	5056 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray source	4589 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.040
Detector resolution: 10.3801 pixels mm^-1	θmax = 29.4°, θmin = 2.9°
ω scans	h = −11→9
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	k = −14→14
Tmin = 0.551, Tmax = 1.000	l = −16→13
8459 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom & difmap
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0172P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
5054 reflections	Δρmax = 3.53 e Å^−3
237 parameters	Δρmin = −1.74 e Å^−3
2 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.00175 (19)

Special details

Experimental. Data collection and full structure determination done by Prof. Anthony Linden: [e-mail]

Solvent used: 2M HCl Cooling Device: Oxford Instruments Cryojet XL Crystal mount: on a glass fibre Frames collected: 272 Seconds exposure per frame: 1.5 Degrees rotation per frame: 1.0 Crystal-detector distance (mm): 55.0 Client: Levi Senior Sample code: LS009

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.

Refinement. The water H-atoms were refined isotropically with O-H distance restraints of 0.84 (1) Å. All other H atoms were placed in calculated positions and allowed to ride on their parent atoms.

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

	x	y	z	Uiso*/Ueq
Bi1	0.33379 (2)	0.65001 (2)	0.77021 (2)	0.01333 (8)
Cl1	0.30114 (15)	0.87093 (12)	0.86367 (13)	0.0217 (3)
Cl2	0.62022 (15)	0.67918 (13)	0.92734 (13)	0.0205 (3)
Cl3	0.13301 (14)	0.50002 (12)	0.90309 (12)	0.0197 (3)
Cl4	0.35744 (16)	0.43435 (12)	0.65545 (13)	0.0234 (3)
Cl5	0.06380 (14)	0.62274 (12)	0.62347 (12)	0.0165 (3)
Cl6	0.47286 (14)	0.77900 (12)	0.62570 (13)	0.0190 (3)
Cl7	1.20723 (15)	0.98098 (13)	0.50220 (13)	0.0216 (3)
O1	0.7385 (4)	0.6577 (4)	0.6206 (4)	0.0200 (8)
H11	0.714 (7)	0.619 (5)	0.552 (2)	0.033 (19)*
H12	0.666 (5)	0.687 (6)	0.630 (6)	0.039 (19)*
N1	1.0249 (5)	1.1946 (4)	0.8540 (4)	0.0219 (11)
H1	1.077768	1.277490	0.863992	0.026*
N2	1.1604 (5)	1.1615 (4)	0.7142 (4)	0.0239 (11)
H21	1.210656	1.245035	0.725912	0.029*
H22	1.180074	1.109362	0.662307	0.029*
N3	0.9957 (5)	0.8895 (4)	0.6795 (4)	0.0207 (11)
H31	1.013412	0.926401	0.614533	0.031*
H32	0.910623	0.817732	0.658148	0.031*
H33	1.080894	0.866756	0.714239	0.031*
C1	1.0544 (6)	1.1142 (5)	0.7748 (5)	0.0163 (11)
C2	0.9672 (6)	0.9818 (5)	0.7621 (5)	0.0138 (10)
C3	0.8594 (6)	0.9399 (5)	0.8260 (5)	0.0166 (11)
H3	0.801713	0.850647	0.816354	0.020*
C4	0.8338 (7)	1.0302 (5)	0.9070 (5)	0.0237 (13)
H41	0.758216	1.002400	0.951731	0.028*
C5	0.9173 (6)	1.1551 (5)	0.9200 (5)	0.0227 (13)
H5	0.902074	1.216442	0.974894	0.027*
N4	0.6479 (5)	0.1627 (4)	0.6711 (4)	0.0182 (10)
H4	0.660330	0.111762	0.614219	0.022*
N5	0.8359 (5)	0.3288 (4)	0.6238 (4)	0.0236 (11)
H51	0.847672	0.273505	0.570243	0.028*
H52	0.892155	0.410810	0.634629	0.028*
N6	0.7879 (5)	0.5058 (4)	0.7981 (4)	0.0163 (10)
H61	0.764422	0.540181	0.730778	0.024*
H62	0.892872	0.518114	0.819174	0.024*
H63	0.758381	0.545460	0.856654	0.024*
C6	0.7327 (6)	0.2881 (5)	0.6888 (5)	0.0147 (11)
C7	0.7050 (6)	0.3677 (5)	0.7784 (5)	0.0139 (10)
C8	0.6028 (5)	0.3158 (5)	0.8446 (5)	0.0163 (11)
H8	0.585925	0.369955	0.904868	0.020*
C9	0.5238 (6)	0.1843 (5)	0.8239 (5)	0.0205 (12)
H9	0.455741	0.147067	0.871621	0.025*
C10	0.5452 (6)	0.1091 (5)	0.7341 (5)	0.0191 (12)
H10	0.488022	0.019523	0.716078	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01174 (11)	0.01138 (11)	0.01661 (13)	0.00237 (7)	0.00483 (8)	0.00072 (8)
Cl1	0.0263 (7)	0.0161 (7)	0.0216 (8)	0.0048 (5)	0.0082 (6)	−0.0046 (6)
Cl2	0.0183 (6)	0.0211 (7)	0.0211 (8)	0.0060 (5)	0.0035 (6)	0.0002 (6)
Cl3	0.0194 (6)	0.0190 (7)	0.0191 (8)	0.0026 (5)	0.0055 (6)	0.0032 (6)
Cl4	0.0300 (7)	0.0165 (7)	0.0251 (8)	0.0083 (5)	0.0090 (6)	−0.0004 (6)
Cl5	0.0154 (6)	0.0157 (6)	0.0166 (7)	0.0032 (5)	0.0028 (5)	−0.0004 (5)
Cl6	0.0194 (6)	0.0180 (7)	0.0231 (8)	0.0070 (5)	0.0096 (6)	0.0057 (6)
Cl7	0.0239 (7)	0.0247 (7)	0.0199 (8)	0.0109 (5)	0.0088 (6)	0.0025 (6)
O1	0.0153 (19)	0.024 (2)	0.022 (3)	0.0085 (16)	0.0050 (18)	−0.0008 (19)
N1	0.023 (2)	0.012 (2)	0.030 (3)	0.0060 (18)	0.004 (2)	0.002 (2)
N2	0.028 (3)	0.011 (2)	0.030 (3)	−0.0012 (19)	0.014 (2)	−0.004 (2)
N3	0.027 (3)	0.010 (2)	0.026 (3)	0.0038 (18)	0.013 (2)	0.002 (2)
C1	0.014 (2)	0.016 (3)	0.021 (3)	0.006 (2)	0.004 (2)	0.004 (2)
C2	0.016 (2)	0.015 (3)	0.011 (3)	0.007 (2)	0.001 (2)	0.001 (2)
C3	0.015 (2)	0.019 (3)	0.013 (3)	0.002 (2)	0.002 (2)	0.000 (2)
C4	0.022 (3)	0.030 (3)	0.023 (4)	0.011 (2)	0.012 (3)	0.005 (3)
C5	0.023 (3)	0.031 (3)	0.017 (3)	0.013 (2)	0.006 (3)	−0.001 (3)
N4	0.019 (2)	0.015 (2)	0.017 (3)	0.0016 (18)	0.004 (2)	−0.003 (2)
N5	0.030 (3)	0.018 (2)	0.025 (3)	0.0024 (19)	0.016 (2)	0.001 (2)
N6	0.016 (2)	0.013 (2)	0.019 (3)	0.0041 (17)	0.005 (2)	−0.0023 (19)
C6	0.013 (2)	0.016 (3)	0.012 (3)	0.004 (2)	−0.001 (2)	−0.003 (2)
C7	0.013 (2)	0.013 (3)	0.014 (3)	0.0051 (19)	0.000 (2)	0.002 (2)
C8	0.013 (2)	0.019 (3)	0.016 (3)	0.004 (2)	0.002 (2)	0.000 (2)
C9	0.016 (3)	0.017 (3)	0.029 (4)	0.002 (2)	0.011 (3)	0.002 (3)
C10	0.016 (3)	0.016 (3)	0.023 (3)	0.000 (2)	0.005 (2)	0.005 (2)

Geometric parameters (Å, º)

Bi1—Cl1	2.6812 (12)	C3—H3	0.9500
Bi1—Cl2	2.7986 (14)	C4—C5	1.337 (8)
Bi1—Cl3	2.8899 (12)	C4—H41	0.9500
Bi1—Cl4	2.6970 (13)	C5—H5	0.9500
Bi1—Cl5	2.6312 (13)	N4—C6	1.342 (6)
Bi1—Cl6	2.5896 (12)	N4—C10	1.348 (6)
O1—H11	0.837 (10)	N4—H4	0.8800
O1—H12	0.836 (10)	N5—C6	1.335 (6)
N1—C1	1.346 (7)	N5—H51	0.8800
N1—C5	1.373 (7)	N5—H52	0.8800
N1—H1	0.8800	N6—C7	1.455 (6)
N2—C1	1.331 (6)	N6—H61	0.9100
N2—H21	0.8800	N6—H62	0.9100
N2—H22	0.8800	N6—H63	0.9100
N3—C2	1.454 (6)	C6—C7	1.418 (7)
N3—H31	0.9100	C7—C8	1.367 (6)
N3—H32	0.9100	C8—C9	1.385 (7)
N3—H33	0.9100	C8—H8	0.9500
C1—C2	1.415 (7)	C9—C10	1.364 (7)
C2—C3	1.360 (7)	C9—H9	0.9500
C3—C4	1.414 (7)	C10—H10	0.9500
Cl6—Bi1—Cl5	88.69 (4)	C2—C3—H3	120.3
Cl6—Bi1—Cl1	88.51 (4)	C4—C3—H3	120.3
Cl5—Bi1—Cl1	85.39 (4)	C5—C4—C3	119.3 (5)
Cl6—Bi1—Cl4	87.53 (4)	C5—C4—H41	120.4
Cl5—Bi1—Cl4	90.58 (4)	C3—C4—H41	120.4
Cl1—Bi1—Cl4	174.42 (4)	C4—C5—N1	120.0 (5)
Cl6—Bi1—Cl2	91.56 (4)	C4—C5—H5	120.0
Cl5—Bi1—Cl2	179.68 (4)	N1—C5—H5	120.0
Cl1—Bi1—Cl2	94.42 (4)	C6—N4—C10	124.7 (5)
Cl4—Bi1—Cl2	89.62 (4)	C6—N4—H4	117.6
Cl6—Bi1—Cl3	170.83 (4)	C10—N4—H4	117.6
Cl5—Bi1—Cl3	82.16 (4)	C6—N5—H51	120.0
Cl1—Bi1—Cl3	91.37 (4)	C6—N5—H52	120.0
Cl4—Bi1—Cl3	91.91 (4)	H51—N5—H52	120.0
Cl2—Bi1—Cl3	97.59 (4)	C7—N6—H61	109.5
H11—O1—H12	108 (6)	C7—N6—H62	109.5
C1—N1—C5	123.9 (5)	H61—N6—H62	109.5
C1—N1—H1	118.1	C7—N6—H63	109.5
C5—N1—H1	118.1	H61—N6—H63	109.5
C1—N2—H21	120.0	H62—N6—H63	109.5
C1—N2—H22	120.0	N5—C6—N4	119.2 (5)
H21—N2—H22	120.0	N5—C6—C7	125.0 (5)
C2—N3—H31	109.5	N4—C6—C7	115.8 (4)
C2—N3—H32	109.5	C8—C7—C6	120.7 (5)
H31—N3—H32	109.5	C8—C7—N6	120.8 (4)
C2—N3—H33	109.5	C6—C7—N6	118.4 (4)
H31—N3—H33	109.5	C7—C8—C9	120.0 (5)
H32—N3—H33	109.5	C7—C8—H8	120.0
N2—C1—N1	119.7 (5)	C9—C8—H8	120.0
N2—C1—C2	124.3 (5)	C10—C9—C8	119.1 (5)
N1—C1—C2	116.0 (4)	C10—C9—H9	120.5
C3—C2—C1	121.4 (5)	C8—C9—H9	120.5
C3—C2—N3	119.9 (5)	N4—C10—C9	119.5 (5)
C1—C2—N3	118.7 (4)	N4—C10—H10	120.3
C2—C3—C4	119.4 (5)	C9—C10—H10	120.3
C5—N1—C1—N2	179.5 (5)	C10—N4—C6—N5	177.1 (5)
C5—N1—C1—C2	−0.3 (8)	C10—N4—C6—C7	−2.2 (8)
N2—C1—C2—C3	−179.3 (5)	N5—C6—C7—C8	−176.4 (5)
N1—C1—C2—C3	0.5 (8)	N4—C6—C7—C8	2.8 (7)
N2—C1—C2—N3	1.3 (8)	N5—C6—C7—N6	3.6 (8)
N1—C1—C2—N3	−178.9 (5)	N4—C6—C7—N6	−177.2 (5)
C1—C2—C3—C4	−0.1 (8)	C6—C7—C8—C9	−0.6 (8)
N3—C2—C3—C4	179.3 (5)	N6—C7—C8—C9	179.4 (5)
C2—C3—C4—C5	−0.6 (8)	C7—C8—C9—C10	−2.5 (8)
C3—C4—C5—N1	0.8 (9)	C6—N4—C10—C9	−0.8 (8)
C1—N1—C5—C4	−0.4 (9)	C8—C9—C10—N4	3.2 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl3^i	0.88	2.31	3.154 (5)	160
N2—H21···Cl4^i	0.88	2.43	3.215 (4)	150
N2—H22···Cl7	0.88	2.35	3.223 (5)	171
N3—H31···Cl7^ii	0.91	2.68	3.202 (5)	118
N3—H32···O1	0.91	1.94	2.848 (6)	176
N3—H33···Cl1^iii	0.91	2.37	3.228 (5)	157
N4—H4···Cl7^iv	0.88	2.35	3.181 (4)	158
N5—H51···Cl7^iv	0.88	2.70	3.453 (5)	144
N5—H52···Cl5^iii	0.88	2.43	3.290 (5)	167
N6—H61···O1	0.91	1.91	2.794 (6)	163
N6—H62···Cl3^iii	0.91	2.29	3.167 (4)	163
N6—H63···Cl2	0.91	2.38	3.218 (4)	153
O1—H11···Cl4^v	0.84 (1)	2.36 (2)	3.177 (5)	165 (6)
O1—H12···Cl6	0.84 (1)	2.26 (2)	3.083 (4)	170 (6)

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

Tetrakis(2-amino-3-methylpyridinium) di-µ-chlorido-bis[tetrachloridobismuth(III)] (2)

Crystal data

(C6H9N2)4[Bi2Cl10]	Z = 1
Mr = 1209.07	F(000) = 572
Triclinic, P1	Dx = 2.109 Mg m^−3
a = 8.8144 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9982 (3) Å	Cell parameters from 6026 reflections
c = 12.3440 (4) Å	θ = 3.2–29.2°
α = 76.784 (3)°	µ = 9.96 mm^−1
β = 87.111 (3)°	T = 160 K
γ = 88.514 (3)°	Block, colourless
V = 951.80 (6) Å^3	0.25 × 0.15 × 0.07 mm

Data collection

Oxford Diffraction SuperNova dual radiation diffractometer	4463 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray source	4137 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.026
Detector resolution: 10.3801 pixels mm^-1	θmax = 29.5°, θmin = 2.8°
ω scans	h = −11→11
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	k = −10→11
Tmin = 0.660, Tmax = 1.000	l = −11→16
8469 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.049	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.015P)^2] where P = (Fo^2 + 2Fc^2)/3
4463 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.89 e Å^−3
54 restraints	Δρmin = −1.03 e Å^−3

Special details

Experimental. Data collection and full structure determination done by Prof. Anthony Linden: [e-mail]

Solvent used: 2M HCl Cooling Device: Oxford Instruments Cryojet XL Crystal mount: on a glass fibre Frames collected: 312 Seconds exposure per frame: 3.0 Degrees rotation per frame: 1.0 Crystal-detector distance (mm): 55.0 Client: Levi Senior Sample code: LS010

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.

Refinement. Rigid body restraints were applied to the atoms of the cation containing atom N3.

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

	x	y	z	Uiso*/Ueq
Bi1	0.50769 (2)	0.39447 (2)	0.17732 (2)	0.01904 (5)
Cl1	0.50021 (11)	0.12800 (10)	0.30547 (8)	0.0342 (2)
Cl2	0.53940 (10)	0.53069 (11)	0.33900 (8)	0.0316 (2)
Cl3	0.80433 (10)	0.36762 (11)	0.14781 (9)	0.0311 (2)
Cl4	0.19902 (10)	0.42985 (10)	0.20710 (8)	0.0275 (2)
Cl5	0.47878 (12)	0.29835 (11)	−0.02343 (8)	0.0339 (2)
N1	0.1469 (3)	0.6424 (3)	0.3902 (2)	0.0236 (7)
H1	0.190004	0.588325	0.345739	0.028*
N2	−0.0854 (3)	0.5797 (3)	0.3363 (2)	0.0241 (7)
H21	−0.037783	0.526435	0.293025	0.029*
H22	−0.185334	0.584809	0.339472	0.029*
C1	−0.0069 (4)	0.6519 (4)	0.3964 (3)	0.0201 (7)
C2	−0.0762 (4)	0.7402 (4)	0.4683 (3)	0.0220 (8)
C3	0.0177 (4)	0.8060 (4)	0.5287 (3)	0.0270 (8)
H31	−0.026500	0.862991	0.578447	0.032*
C4	0.1757 (4)	0.7925 (4)	0.5199 (3)	0.0314 (9)
H4	0.238106	0.839019	0.562910	0.038*
C5	0.2381 (4)	0.7110 (4)	0.4482 (3)	0.0296 (9)
H5	0.345384	0.702426	0.438924	0.036*
C6	−0.2452 (4)	0.7578 (4)	0.4745 (3)	0.0290 (9)
H61	−0.280318	0.809261	0.401056	0.044*
H62	−0.274901	0.818780	0.528682	0.044*
H63	−0.291321	0.656853	0.497726	0.044*
N3	0.1583 (4)	0.8106 (4)	0.0943 (3)	0.0449 (10)
H3	0.207612	0.748010	0.059175	0.054*
N4	−0.0581 (4)	0.7233 (4)	0.0399 (3)	0.0435 (9)
H41	−0.002586	0.663843	0.005540	0.052*
H42	−0.157750	0.722971	0.038404	0.052*
C7	0.0078 (5)	0.8122 (4)	0.0933 (3)	0.0361 (9)
C8	−0.0776 (5)	0.9127 (4)	0.1492 (3)	0.0274 (8)
C9	0.0085 (5)	1.0004 (5)	0.1983 (4)	0.0380 (10)
H9	−0.043656	1.069626	0.235317	0.046*
C10	0.1659 (6)	0.9968 (5)	0.1985 (4)	0.0499 (12)
H10	0.218704	1.061239	0.234552	0.060*
C11	0.2436 (6)	0.8974 (5)	0.1452 (4)	0.0447 (11)
H11	0.351336	0.889422	0.143717	0.054*
C12	−0.2428 (5)	0.9150 (5)	0.1498 (4)	0.0398 (10)
H121	−0.275546	0.939059	0.072959	0.060*
H122	−0.282958	0.992859	0.188067	0.060*
H123	−0.281062	0.814759	0.188748	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01407 (8)	0.02466 (8)	0.01962 (8)	−0.00037 (5)	−0.00009 (5)	−0.00777 (5)
Cl1	0.0329 (6)	0.0299 (5)	0.0370 (6)	0.0011 (4)	0.0011 (4)	−0.0027 (4)
Cl2	0.0246 (5)	0.0464 (6)	0.0298 (5)	−0.0023 (4)	−0.0013 (4)	−0.0209 (4)
Cl3	0.0145 (4)	0.0381 (5)	0.0427 (6)	0.0007 (4)	0.0013 (4)	−0.0142 (4)
Cl4	0.0141 (4)	0.0353 (5)	0.0360 (6)	0.0007 (4)	−0.0006 (4)	−0.0143 (4)
Cl5	0.0458 (6)	0.0310 (5)	0.0280 (5)	−0.0058 (4)	−0.0029 (4)	−0.0126 (4)
N1	0.0229 (17)	0.0233 (15)	0.0240 (17)	0.0039 (13)	0.0030 (13)	−0.0054 (12)
N2	0.0221 (16)	0.0282 (16)	0.0238 (17)	0.0011 (13)	0.0025 (13)	−0.0101 (13)
C1	0.0217 (19)	0.0178 (17)	0.0170 (18)	0.0010 (14)	0.0022 (14)	0.0032 (13)
C2	0.026 (2)	0.0184 (17)	0.0192 (19)	0.0037 (15)	0.0026 (15)	−0.0012 (13)
C3	0.034 (2)	0.0233 (19)	0.025 (2)	0.0027 (16)	−0.0008 (17)	−0.0080 (15)
C4	0.028 (2)	0.029 (2)	0.040 (3)	0.0005 (17)	−0.0092 (18)	−0.0118 (17)
C5	0.021 (2)	0.027 (2)	0.038 (2)	−0.0004 (16)	−0.0019 (17)	−0.0014 (17)
C6	0.025 (2)	0.031 (2)	0.032 (2)	0.0051 (16)	0.0019 (17)	−0.0095 (16)
N3	0.033 (2)	0.035 (2)	0.054 (3)	0.0113 (15)	0.0176 (18)	0.0107 (16)
N4	0.061 (3)	0.0355 (19)	0.036 (2)	−0.0048 (18)	0.0116 (18)	−0.0150 (16)
C7	0.047 (2)	0.024 (2)	0.032 (2)	−0.0013 (17)	0.0063 (19)	0.0032 (16)
C8	0.034 (2)	0.0230 (18)	0.023 (2)	0.0018 (16)	0.0053 (16)	−0.0009 (14)
C9	0.039 (2)	0.033 (2)	0.038 (3)	−0.0009 (18)	−0.003 (2)	0.0019 (18)
C10	0.052 (3)	0.049 (3)	0.045 (3)	−0.016 (2)	−0.015 (2)	0.002 (2)
C11	0.046 (3)	0.036 (2)	0.043 (3)	−0.002 (2)	0.004 (2)	0.0077 (19)
C12	0.037 (2)	0.043 (3)	0.039 (3)	−0.001 (2)	0.001 (2)	−0.010 (2)

Geometric parameters (Å, º)

Bi1—Cl1	2.5533 (10)	C6—H61	0.9800
Bi1—Cl2	2.5992 (9)	C6—H62	0.9800
Bi1—Cl3	2.6342 (9)	C6—H63	0.9800
Bi1—Cl4	2.7471 (8)	N3—C7	1.327 (5)
Bi1—Cl5	2.8300 (9)	N3—C11	1.368 (6)
Bi1—Cl5^i	2.9760 (10)	N3—H3	0.8800
N1—C5	1.351 (5)	N4—C7	1.310 (5)
N1—C1	1.356 (4)	N4—H41	0.8800
N1—H1	0.8800	N4—H42	0.8800
N2—C1	1.323 (4)	C7—C8	1.435 (5)
N2—H21	0.8800	C8—C9	1.364 (6)
N2—H22	0.8800	C8—C12	1.455 (6)
C1—C2	1.426 (5)	C9—C10	1.387 (6)
C2—C3	1.372 (5)	C9—H9	0.9500
C2—C6	1.494 (5)	C10—C11	1.377 (6)
C3—C4	1.396 (5)	C10—H10	0.9500
C3—H31	0.9500	C11—H11	0.9500
C4—C5	1.360 (5)	C12—H121	0.9800
C4—H4	0.9500	C12—H122	0.9800
C5—H5	0.9500	C12—H123	0.9800
Cl1—Bi1—Cl2	93.93 (3)	N1—C5—H5	120.1
Cl1—Bi1—Cl3	90.08 (3)	C4—C5—H5	120.1
Cl2—Bi1—Cl3	91.38 (3)	C2—C6—H61	109.5
Cl1—Bi1—Cl4	91.13 (3)	C2—C6—H62	109.5
Cl2—Bi1—Cl4	87.92 (3)	H61—C6—H62	109.5
Cl3—Bi1—Cl4	178.64 (3)	C2—C6—H63	109.5
Cl1—Bi1—Cl5	96.18 (3)	H61—C6—H63	109.5
Cl2—Bi1—Cl5	169.86 (3)	H62—C6—H63	109.5
Cl3—Bi1—Cl5	87.88 (3)	C7—N3—C11	125.8 (4)
Cl4—Bi1—Cl5	92.59 (3)	C7—N3—H3	117.1
Cl1—Bi1—Cl5^i	178.47 (3)	C11—N3—H3	117.1
Cl2—Bi1—Cl5^i	87.27 (3)	C7—N4—H41	120.0
Cl3—Bi1—Cl5^i	88.94 (3)	C7—N4—H42	120.0
Cl4—Bi1—Cl5^i	89.86 (3)	H41—N4—H42	120.0
Cl5—Bi1—Cl5^i	82.60 (3)	N4—C7—N3	118.8 (4)
Bi1—Cl5—Bi1^i	97.40 (3)	N4—C7—C8	122.1 (4)
C5—N1—C1	124.0 (3)	N3—C7—C8	119.1 (4)
C5—N1—H1	118.0	C9—C8—C7	114.6 (4)
C1—N1—H1	118.0	C9—C8—C12	125.5 (4)
C1—N2—H21	120.0	C7—C8—C12	119.8 (4)
C1—N2—H22	120.0	C8—C9—C10	125.4 (4)
H21—N2—H22	120.0	C8—C9—H9	117.3
N2—C1—N1	119.0 (3)	C10—C9—H9	117.3
N2—C1—C2	123.1 (3)	C11—C10—C9	118.2 (5)
N1—C1—C2	117.9 (3)	C11—C10—H10	120.9
C3—C2—C1	117.5 (3)	C9—C10—H10	120.9
C3—C2—C6	123.1 (3)	N3—C11—C10	116.8 (4)
C1—C2—C6	119.5 (3)	N3—C11—H11	121.6
C2—C3—C4	122.6 (3)	C10—C11—H11	121.6
C2—C3—H31	118.7	C8—C12—H121	109.5
C4—C3—H31	118.7	C8—C12—H122	109.5
C5—C4—C3	118.3 (4)	H121—C12—H122	109.5
C5—C4—H4	120.8	C8—C12—H123	109.5
C3—C4—H4	120.8	H121—C12—H123	109.5
N1—C5—C4	119.7 (3)	H122—C12—H123	109.5
C5—N1—C1—N2	−179.8 (3)	C11—N3—C7—N4	179.3 (4)
C5—N1—C1—C2	0.2 (5)	C11—N3—C7—C8	0.2 (6)
N2—C1—C2—C3	178.2 (3)	N4—C7—C8—C9	−178.4 (4)
N1—C1—C2—C3	−1.8 (5)	N3—C7—C8—C9	0.7 (6)
N2—C1—C2—C6	−2.1 (5)	N4—C7—C8—C12	1.5 (6)
N1—C1—C2—C6	177.9 (3)	N3—C7—C8—C12	−179.4 (4)
C1—C2—C3—C4	1.6 (5)	C7—C8—C9—C10	−0.9 (6)
C6—C2—C3—C4	−178.1 (3)	C12—C8—C9—C10	179.3 (4)
C2—C3—C4—C5	0.2 (6)	C8—C9—C10—C11	0.1 (7)
C1—N1—C5—C4	1.6 (6)	C7—N3—C11—C10	−1.0 (7)
C3—C4—C5—N1	−1.8 (6)	C9—C10—C11—N3	0.9 (6)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl4	0.88	2.46	3.287 (3)	156
N2—H21···Cl4	0.88	2.52	3.324 (3)	153
N2—H22···Cl2^ii	0.88	2.49	3.345 (3)	165
N3—H3···Cl5^i	0.88	2.81	3.451 (4)	131
N4—H41···Cl3^i	0.88	2.57	3.360 (3)	150
N4—H42···Cl5^iii	0.88	2.86	3.737 (4)	175

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

Tetrakis(2-amino-3-methylpyridinium) di-µ-bromido-bis[tetrabromidobismuth(III)] (3)

Crystal data

(C6H9N2)4[Bi2Br10]	Z = 1
Mr = 1653.67	F(000) = 752
Triclinic, P1	Dx = 2.692 Mg m^−3
a = 9.2145 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0678 (2) Å	Cell parameters from 11813 reflections
c = 12.6314 (4) Å	θ = 3.2–29.1°
α = 75.476 (3)°	µ = 18.43 mm^−1
β = 86.926 (3)°	T = 160 K
γ = 89.221 (2)°	Needle, yellow
V = 1020.22 (5) Å^3	0.15 × 0.14 × 0.07 mm

Data collection

Oxford Diffraction SuperNova dual radiation diffractometer	5122 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray source	4575 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.046
Detector resolution: 10.3801 pixels mm^-1	θmax = 29.6°, θmin = 2.8°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	k = −12→11
Tmin = 0.274, Tmax = 1.000	l = −17→17
22534 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0239P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5122 reflections	Δρmax = 1.52 e Å^−3
202 parameters	Δρmin = −1.77 e Å^−3
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.00191 (12)

Special details

Experimental. Data collection and full structure determination done by Prof. Anthony Linden: [e-mail]

Solvent used: 2M HBr Cooling Device: Oxford Instruments Cryojet XL Crystal mount: on a glass fibre Frames collected: 779 Seconds exposure per frame: 4.0 Degrees rotation per frame: 1.0 Crystal-detector distance (mm): 55.0 Client: Levi Senior Sample code: LS015

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
Bi1	0.50924 (2)	0.39135 (2)	0.18009 (2)	0.01729 (6)
Br1	0.49907 (5)	0.10892 (4)	0.31794 (3)	0.03099 (11)
Br2	0.54101 (5)	0.53721 (5)	0.34378 (3)	0.03024 (11)
Br3	0.80913 (4)	0.36706 (5)	0.14958 (4)	0.02761 (10)
Br4	0.19658 (4)	0.42565 (5)	0.20682 (3)	0.02398 (10)
Br5	0.47475 (5)	0.28502 (5)	−0.02029 (3)	0.02953 (11)
N1	0.1423 (4)	0.6474 (4)	0.3917 (3)	0.0233 (7)
H1	0.182106	0.594938	0.347717	0.028*
N2	−0.0819 (4)	0.5842 (4)	0.3417 (3)	0.0236 (7)
H21	−0.038140	0.531909	0.299312	0.028*
H22	−0.177440	0.589217	0.346206	0.028*
C1	−0.0037 (4)	0.6559 (4)	0.3992 (3)	0.0186 (8)
C2	−0.0686 (4)	0.7419 (4)	0.4696 (3)	0.0203 (8)
C3	0.0223 (5)	0.8057 (4)	0.5276 (3)	0.0261 (9)
H31	−0.018820	0.860328	0.576999	0.031*
C4	0.1735 (5)	0.7937 (5)	0.5173 (4)	0.0307 (10)
H4	0.233970	0.840133	0.558282	0.037*
C5	0.2323 (5)	0.7145 (5)	0.4475 (4)	0.0302 (10)
H5	0.334778	0.706145	0.437882	0.036*
C6	−0.2303 (5)	0.7586 (5)	0.4778 (3)	0.0287 (10)
H61	−0.264979	0.808926	0.405592	0.043*
H62	−0.256672	0.820236	0.529537	0.043*
H63	−0.275192	0.657767	0.503642	0.043*
N3	0.1565 (5)	0.8165 (4)	0.0970 (3)	0.0442 (11)
H3	0.203006	0.755442	0.062552	0.053*
N4	−0.0543 (5)	0.7318 (4)	0.0450 (3)	0.0449 (11)
H41	−0.003796	0.673130	0.010658	0.054*
H42	−0.149760	0.732884	0.044756	0.054*
C7	0.0126 (6)	0.8173 (5)	0.0962 (4)	0.0335 (11)
C8	−0.0674 (5)	0.9164 (4)	0.1518 (3)	0.0259 (9)
C9	0.0146 (5)	1.0014 (5)	0.1998 (4)	0.0341 (11)
H9	−0.034406	1.068018	0.237036	0.041*
C10	0.1645 (6)	0.9982 (6)	0.1983 (4)	0.0490 (15)
H10	0.215978	1.061851	0.232809	0.059*
C11	0.2389 (6)	0.9005 (5)	0.1457 (4)	0.0445 (13)
H11	0.341889	0.892861	0.143944	0.053*
C12	−0.2276 (5)	0.9185 (5)	0.1540 (4)	0.0398 (12)
H121	−0.259677	0.944393	0.078855	0.060*
H122	−0.264395	0.994630	0.191737	0.060*
H123	−0.265109	0.817750	0.192919	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01270 (9)	0.02202 (9)	0.01806 (9)	0.00003 (6)	−0.00008 (6)	−0.00686 (6)
Br1	0.0271 (3)	0.0268 (2)	0.0350 (3)	0.00156 (19)	0.0008 (2)	−0.00079 (19)
Br2	0.0243 (2)	0.0457 (3)	0.0272 (2)	−0.0019 (2)	−0.00147 (18)	−0.02122 (19)
Br3	0.0127 (2)	0.0323 (2)	0.0384 (2)	0.00028 (17)	0.00157 (18)	−0.01046 (19)
Br4	0.0124 (2)	0.0303 (2)	0.0308 (2)	0.00217 (16)	−0.00031 (17)	−0.01082 (17)
Br5	0.0410 (3)	0.0264 (2)	0.0239 (2)	−0.00511 (19)	−0.00182 (19)	−0.01101 (17)
N1	0.022 (2)	0.0224 (17)	0.0241 (17)	0.0033 (14)	0.0047 (15)	−0.0044 (14)
N2	0.023 (2)	0.0247 (17)	0.0255 (18)	0.0037 (14)	0.0000 (15)	−0.0101 (14)
C1	0.022 (2)	0.0142 (18)	0.0164 (18)	0.0039 (16)	−0.0002 (16)	0.0020 (14)
C2	0.022 (2)	0.0163 (18)	0.0195 (19)	0.0019 (16)	−0.0004 (17)	0.0000 (15)
C3	0.034 (3)	0.020 (2)	0.023 (2)	0.0015 (18)	−0.0022 (19)	−0.0051 (17)
C4	0.026 (3)	0.030 (2)	0.038 (3)	−0.0017 (19)	−0.011 (2)	−0.010 (2)
C5	0.022 (2)	0.030 (2)	0.035 (2)	−0.0020 (19)	−0.004 (2)	−0.0022 (19)
C6	0.026 (3)	0.034 (2)	0.029 (2)	0.0040 (19)	0.0025 (19)	−0.0127 (19)
N3	0.039 (3)	0.033 (2)	0.049 (3)	0.0100 (19)	0.018 (2)	0.0064 (19)
N4	0.064 (3)	0.037 (2)	0.036 (2)	−0.010 (2)	0.014 (2)	−0.0153 (19)
C7	0.044 (3)	0.023 (2)	0.027 (2)	−0.006 (2)	0.008 (2)	0.0039 (18)
C8	0.036 (3)	0.021 (2)	0.019 (2)	0.0014 (19)	−0.0012 (19)	−0.0025 (16)
C9	0.029 (3)	0.033 (2)	0.037 (3)	0.004 (2)	−0.006 (2)	0.001 (2)
C10	0.056 (4)	0.036 (3)	0.050 (3)	−0.012 (3)	−0.021 (3)	0.004 (2)
C11	0.044 (3)	0.032 (3)	0.048 (3)	−0.002 (2)	0.008 (3)	0.005 (2)
C12	0.033 (3)	0.044 (3)	0.041 (3)	−0.001 (2)	0.001 (2)	−0.009 (2)

Geometric parameters (Å, º)

Bi1—Br1	2.7114 (4)	C6—H61	0.9800
Bi1—Br2	2.7491 (4)	C6—H62	0.9800
Bi1—Br3	2.7830 (4)	C6—H63	0.9800
Bi1—Br4	2.9043 (4)	N3—C7	1.327 (6)
Bi1—Br5	2.9590 (4)	N3—C11	1.355 (7)
Bi1—Br5^i	3.1172 (4)	N3—H3	0.8800
N1—C1	1.347 (5)	N4—C7	1.306 (6)
N1—C5	1.360 (5)	N4—H41	0.8800
N1—H1	0.8800	N4—H42	0.8800
N2—C1	1.331 (5)	C7—C8	1.445 (6)
N2—H21	0.8800	C8—C9	1.354 (6)
N2—H22	0.8800	C8—C12	1.475 (6)
C1—C2	1.426 (5)	C9—C10	1.381 (7)
C2—C3	1.366 (6)	C9—H9	0.9500
C2—C6	1.497 (6)	C10—C11	1.388 (8)
C3—C4	1.397 (6)	C10—H10	0.9500
C3—H31	0.9500	C11—H11	0.9500
C4—C5	1.357 (6)	C12—H121	0.9800
C4—H4	0.9500	C12—H122	0.9800
C5—H5	0.9500	C12—H123	0.9800
Br1—Bi1—Br2	94.306 (14)	C4—C5—H5	120.5
Br1—Bi1—Br3	90.383 (13)	N1—C5—H5	120.5
Br2—Bi1—Br3	91.286 (13)	C2—C6—H61	109.5
Br1—Bi1—Br4	91.388 (13)	C2—C6—H62	109.5
Br2—Bi1—Br4	88.747 (13)	H61—C6—H62	109.5
Br3—Bi1—Br4	178.221 (12)	C2—C6—H63	109.5
Br1—Bi1—Br5	95.067 (13)	H61—C6—H63	109.5
Br2—Bi1—Br5	170.620 (13)	H62—C6—H63	109.5
Br3—Bi1—Br5	89.036 (13)	C7—N3—C11	126.4 (5)
Br4—Bi1—Br5	90.642 (13)	C7—N3—H3	116.8
Br1—Bi1—Br5^i	179.186 (13)	C11—N3—H3	116.8
Br2—Bi1—Br5^i	85.969 (13)	C7—N4—H41	120.0
Br3—Bi1—Br5^i	88.844 (13)	C7—N4—H42	120.0
Br4—Bi1—Br5^i	89.383 (13)	H41—N4—H42	120.0
Br5—Bi1—Br5^i	84.665 (12)	N4—C7—N3	120.5 (5)
Bi1—Br5—Bi1^i	95.335 (12)	N4—C7—C8	121.2 (5)
C1—N1—C5	124.3 (4)	N3—C7—C8	118.3 (4)
C1—N1—H1	117.9	C9—C8—C7	115.4 (4)
C5—N1—H1	117.9	C9—C8—C12	124.8 (4)
C1—N2—H21	120.0	C7—C8—C12	119.8 (4)
C1—N2—H22	120.0	C8—C9—C10	124.6 (5)
H21—N2—H22	120.0	C8—C9—H9	117.7
N2—C1—N1	119.4 (3)	C10—C9—H9	117.7
N2—C1—C2	122.5 (4)	C9—C10—C11	118.9 (5)
N1—C1—C2	118.0 (4)	C9—C10—H10	120.5
C3—C2—C1	117.4 (4)	C11—C10—H10	120.5
C3—C2—C6	122.7 (4)	N3—C11—C10	116.3 (5)
C1—C2—C6	119.9 (4)	N3—C11—H11	121.8
C2—C3—C4	122.6 (4)	C10—C11—H11	121.8
C2—C3—H31	118.7	C8—C12—H121	109.5
C4—C3—H31	118.7	C8—C12—H122	109.5
C5—C4—C3	118.7 (4)	H121—C12—H122	109.5
C5—C4—H4	120.6	C8—C12—H123	109.5
C3—C4—H4	120.6	H121—C12—H123	109.5
C4—C5—N1	119.0 (4)	H122—C12—H123	109.5
C5—N1—C1—N2	−179.2 (4)	C11—N3—C7—N4	179.2 (4)
C5—N1—C1—C2	0.6 (5)	C11—N3—C7—C8	0.1 (7)
N2—C1—C2—C3	177.6 (3)	N4—C7—C8—C9	−178.6 (4)
N1—C1—C2—C3	−2.2 (5)	N3—C7—C8—C9	0.4 (6)
N2—C1—C2—C6	−2.2 (6)	N4—C7—C8—C12	1.8 (6)
N1—C1—C2—C6	178.0 (3)	N3—C7—C8—C12	−179.1 (4)
C1—C2—C3—C4	2.2 (6)	C7—C8—C9—C10	−0.1 (7)
C6—C2—C3—C4	−178.0 (4)	C12—C8—C9—C10	179.4 (4)
C2—C3—C4—C5	−0.6 (6)	C8—C9—C10—C11	−0.8 (7)
C3—C4—C5—N1	−1.2 (6)	C7—N3—C11—C10	−1.0 (7)
C1—N1—C5—C4	1.2 (6)	C9—C10—C11—N3	1.3 (7)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br4	0.88	2.62	3.456 (3)	158
N2—H21···Br4	0.88	2.68	3.496 (3)	154
N2—H22···Br2^ii	0.88	2.65	3.504 (4)	165
N3—H3···Br5^i	0.88	3.02	3.653 (4)	130
N4—H41···Br3^i	0.88	2.72	3.521 (4)	152
N4—H42···Br5^iii	0.88	3.04	3.912 (5)	173

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

Bis(4-amino-3-ammoniopyridinium) di-µ-chlorido-bis[tetrachloridobismuth(III)] dihydrate (4)

Crystal data

(C5H9N3)2[Bi2Cl10]·2H2O	F(000) = 1904
Mr = 1030.79	Dx = 2.409 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.0583 (2) Å	Cell parameters from 20128 reflections
b = 12.07450 (12) Å	θ = 3.4–29.4°
c = 13.43800 (15) Å	µ = 13.33 mm^−1
β = 104.0805 (11)°	T = 160 K
V = 2842.05 (5) Å^3	Block, colourless
Z = 4	0.20 × 0.18 × 0.08 mm

Data collection

Oxford Diffraction SuperNova dual radiation diffractometer	3742 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray source	3505 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.034
Detector resolution: 10.3801 pixels mm^-1	θmax = 29.5°, θmin = 2.7°
ω scans	h = −24→24
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	k = −16→16
Tmin = 0.348, Tmax = 1.000	l = −18→17
30758 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom & difmap
R[F^2 > 2σ(F^2)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.030	w = 1/[σ^2(Fo^2) + (0.0104P)^2 + 2.6097P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.003
3742 reflections	Δρmax = 0.66 e Å^−3
182 parameters	Δρmin = −0.55 e Å^−3
12 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.000247 (12)

Special details

Experimental. Data collection and full structure determination done by Prof. Anthony Linden: [e-mail]

Solvent used: 2M HCl Cooling Device: Oxford Instruments Cryojet XL Crystal mount: on a glass fibre Frames collected: 817 Seconds exposure per frame: 8.0 Degrees rotation per frame: 1.0 Crystal-detector distance (mm): 55.0 Client: Levi Senior Sample code: LS033

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.

Refinement. Anion sites across a centre of inversion. Two sites for water molecules disordered about twofold axes. Distance and angle restraints applied to the water H atoms. Distance restraints applied to all N-H H atoms.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0.35117 (2)	0.72988 (2)	−0.05830 (2)	0.01728 (3)
Cl1	0.46209 (3)	0.86237 (5)	−0.03702 (5)	0.03036 (13)
Cl2	0.40227 (4)	0.59985 (5)	−0.18555 (4)	0.03157 (14)
Cl3	0.27578 (3)	0.85878 (4)	−0.21265 (4)	0.02234 (11)
Cl4	0.42774 (3)	0.60321 (4)	0.10076 (4)	0.02130 (11)
Cl5	0.30319 (3)	0.86838 (5)	0.08236 (4)	0.02636 (12)
N1	0.61203 (12)	0.66820 (18)	−0.07273 (15)	0.0298 (5)
H1	0.6008 (16)	0.6206 (19)	−0.1237 (16)	0.048 (9)*
N2	0.60265 (10)	0.68466 (17)	0.19552 (14)	0.0213 (4)
H21	0.5785 (14)	0.6189 (13)	0.190 (2)	0.040 (8)*
H22	0.5709 (13)	0.7352 (17)	0.213 (2)	0.033 (8)*
H23	0.6480 (8)	0.679 (2)	0.2424 (15)	0.031 (7)*
N3	0.66863 (13)	0.89037 (18)	0.16324 (18)	0.0349 (5)
H31	0.6629 (16)	0.876 (2)	0.2255 (11)	0.046 (9)*
H32	0.6898 (17)	0.9524 (15)	0.152 (2)	0.062 (10)*
C1	0.59972 (12)	0.64156 (19)	0.01852 (16)	0.0230 (5)
H11	0.577815	0.571984	0.027900	0.028*
C2	0.61865 (12)	0.71426 (17)	0.09767 (16)	0.0186 (4)
C3	0.65074 (12)	0.81845 (19)	0.08692 (17)	0.0227 (5)
C4	0.66180 (13)	0.8418 (2)	−0.01215 (19)	0.0303 (5)
H4	0.683158	0.910721	−0.024913	0.036*
C5	0.64214 (15)	0.7667 (2)	−0.0878 (2)	0.0334 (6)
H5	0.649733	0.783718	−0.153616	0.040*
O1	0.5074 (3)	0.8331 (3)	0.2772 (2)	0.0267 (8)	0.5
H1A	0.532 (3)	0.846 (4)	0.3376 (15)	0.040*	0.5
H1B	0.503 (5)	0.889 (2)	0.239 (3)	0.040*	0.5
O2	0.4782 (2)	1.0460 (4)	0.2339 (6)	0.0560 (17)	0.5
H2A	0.4319 (12)	1.062 (6)	0.223 (6)	0.084*	0.5
H2B	0.502 (3)	1.089 (5)	0.204 (5)	0.084*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01610 (5)	0.01685 (5)	0.01932 (5)	0.00110 (3)	0.00514 (3)	0.00141 (3)
Cl1	0.0208 (3)	0.0294 (3)	0.0389 (3)	−0.0061 (2)	0.0032 (2)	0.0049 (3)
Cl2	0.0496 (4)	0.0243 (3)	0.0239 (3)	0.0113 (3)	0.0149 (3)	0.0031 (2)
Cl3	0.0222 (3)	0.0179 (2)	0.0242 (3)	−0.0008 (2)	0.0003 (2)	0.0013 (2)
Cl4	0.0250 (3)	0.0189 (3)	0.0195 (2)	0.0009 (2)	0.0044 (2)	−0.0004 (2)
Cl5	0.0290 (3)	0.0219 (3)	0.0299 (3)	−0.0061 (2)	0.0106 (2)	−0.0054 (2)
N1	0.0356 (11)	0.0328 (12)	0.0222 (10)	−0.0038 (9)	0.0092 (9)	−0.0067 (9)
N2	0.0210 (10)	0.0248 (10)	0.0177 (9)	−0.0010 (9)	0.0037 (8)	0.0018 (8)
N3	0.0453 (13)	0.0210 (11)	0.0346 (13)	−0.0111 (10)	0.0021 (11)	−0.0022 (9)
C1	0.0225 (11)	0.0235 (12)	0.0228 (11)	−0.0024 (9)	0.0054 (9)	−0.0002 (9)
C2	0.0170 (10)	0.0203 (11)	0.0182 (10)	0.0015 (8)	0.0038 (8)	0.0046 (8)
C3	0.0198 (11)	0.0205 (12)	0.0247 (11)	−0.0004 (9)	−0.0007 (9)	0.0024 (9)
C4	0.0276 (12)	0.0292 (13)	0.0331 (13)	−0.0053 (10)	0.0057 (10)	0.0121 (11)
C5	0.0315 (14)	0.0452 (16)	0.0261 (13)	−0.0016 (12)	0.0118 (11)	0.0083 (11)
O1	0.030 (2)	0.0257 (17)	0.023 (2)	0.0002 (16)	0.003 (2)	0.0021 (12)
O2	0.069 (5)	0.044 (2)	0.064 (5)	0.016 (2)	0.034 (4)	0.017 (3)

Geometric parameters (Å, º)

Bi1—Cl1	2.5247 (5)	N3—H31	0.885 (10)
Bi1—Cl2	2.6474 (5)	N3—H32	0.871 (10)
Bi1—Cl3	2.6840 (5)	C1—C2	1.357 (3)
Bi1—Cl4	2.7170 (5)	C1—H11	0.9500
Bi1—Cl5	2.8136 (5)	C2—C3	1.407 (3)
Bi1—Cl5^i	2.9738 (5)	C3—C4	1.422 (3)
N1—C1	1.338 (3)	C4—C5	1.344 (4)
N1—C5	1.344 (3)	C4—H4	0.9500
N1—H1	0.880 (10)	C5—H5	0.9500
N2—C2	1.458 (3)	O1—H1A	0.839 (10)
N2—H21	0.900 (10)	O1—H1B	0.840 (10)
N2—H22	0.907 (10)	O2—H2A	0.837 (10)
N2—H23	0.906 (10)	O2—H2B	0.842 (10)
N3—C3	1.323 (3)
Cl1—Bi1—Cl2	93.29 (2)	H21—N2—H23	109 (2)
Cl1—Bi1—Cl3	87.673 (17)	H22—N2—H23	113 (2)
Cl2—Bi1—Cl3	92.048 (17)	C3—N3—H31	123 (2)
Cl1—Bi1—Cl4	91.700 (17)	C3—N3—H32	118 (2)
Cl2—Bi1—Cl4	89.060 (16)	H31—N3—H32	120 (3)
Cl3—Bi1—Cl4	178.756 (16)	N1—C1—C2	119.8 (2)
Cl1—Bi1—Cl5	84.998 (18)	N1—C1—H11	120.1
Cl2—Bi1—Cl5	177.559 (18)	C2—C1—H11	120.1
Cl3—Bi1—Cl5	89.619 (17)	C1—C2—C3	122.0 (2)
Cl4—Bi1—Cl5	89.256 (16)	C1—C2—N2	118.75 (19)
Cl1—Bi1—Cl5^i	164.142 (18)	C3—C2—N2	119.26 (19)
Cl2—Bi1—Cl5^i	99.089 (18)	N3—C3—C2	122.4 (2)
Cl3—Bi1—Cl5^i	82.042 (16)	N3—C3—C4	122.2 (2)
Cl4—Bi1—Cl5^i	98.344 (16)	C2—C3—C4	115.4 (2)
Cl5—Bi1—Cl5^i	82.905 (16)	C5—C4—C3	120.2 (2)
Bi1—Cl5—Bi1^i	97.096 (16)	C5—C4—H4	119.9
C1—N1—C5	121.0 (2)	C3—C4—H4	119.9
C1—N1—H1	119.9 (19)	N1—C5—C4	121.7 (2)
C5—N1—H1	119.1 (19)	N1—C5—H5	119.1
C2—N2—H21	110.3 (17)	C4—C5—H5	119.1
C2—N2—H22	110.1 (17)	H1A—O1—H1B	113.1 (19)
H21—N2—H22	107 (2)	H2A—O2—H2B	112.9 (19)
C2—N2—H23	107.5 (16)
C5—N1—C1—C2	−0.8 (3)	N2—C2—C3—C4	−177.80 (19)
N1—C1—C2—C3	0.4 (3)	N3—C3—C4—C5	−179.4 (2)
N1—C1—C2—N2	178.2 (2)	C2—C3—C4—C5	−0.1 (3)
C1—C2—C3—N3	179.3 (2)	C1—N1—C5—C4	0.7 (4)
N2—C2—C3—N3	1.5 (3)	C3—C4—C5—N1	−0.2 (4)
C1—C2—C3—C4	0.0 (3)

Symmetry code: (i) −x+1/2, −y+3/2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2^ii	0.88 (1)	2.56 (2)	3.300 (2)	142 (2)
N1—H1···Cl4^iii	0.88 (1)	2.78 (2)	3.356 (2)	124 (2)
N2—H21···Cl2^iii	0.90 (1)	2.67 (2)	3.438 (2)	144 (2)
N2—H21···Cl4	0.90 (1)	2.70 (2)	3.2570 (19)	121 (2)
N2—H22···O1	0.91 (1)	1.98 (1)	2.879 (5)	169 (3)
N2—H22···O1^iv	0.91 (1)	1.87 (1)	2.766 (5)	168 (3)
N2—H23···Cl3^v	0.91 (1)	2.28 (1)	3.1137 (19)	152 (2)
N3—H31···Cl5^iv	0.89 (1)	2.51 (2)	3.342 (2)	158 (3)
N3—H32···Cl3^vi	0.87 (1)	2.45 (2)	3.209 (2)	146 (3)
O1—H1A···Cl1^iv	0.84 (1)	2.66 (3)	3.418 (3)	151 (5)
O1—H1B···O2	0.84 (1)	1.94 (4)	2.661 (5)	143 (6)
O2—H2B···Cl1^vi	0.84 (1)	2.55 (4)	3.282 (7)	147 (7)

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

catena-Poly[2,6-diaminopyridinium [[cis-diiodidobismuth(III)]-di-µ-iodido]] (5)

Crystal data

(C5H8N3)[BiI4]	F(000) = 1416
Mr = 826.72	Dx = 3.816 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.02106 (15) Å	Cell parameters from 19181 reflections
b = 7.80880 (9) Å	θ = 3.1–30.3°
c = 15.3298 (2) Å	µ = 20.80 mm^−1
β = 90.0530 (11)°	T = 160 K
V = 1439.01 (3) Å^3	Prism, red
Z = 4	0.16 × 0.10 × 0.04 mm

Data collection

Oxford Diffraction SuperNova dual radiation diffractometer	4076 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray source	3831 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.041
Detector resolution: 10.3801 pixels mm^-1	θmax = 30.4°, θmin = 2.9°
ω scans	h = −15→16
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	k = −11→11
Tmin = 0.259, Tmax = 1.000	l = −21→21
35690 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.040	w = 1/[σ^2(Fo^2) + (0.0158P)^2 + 1.0108P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
4076 reflections	Δρmax = 1.21 e Å^−3
120 parameters	Δρmin = −1.04 e Å^−3
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.00085 (3)

Special details

Experimental. Data collection and full structure determination done by Prof. Anthony Linden: [e-mail]

Solvent used: 2M HI Cooling Device: Oxford Instruments Cryojet XL Crystal mount: on a glass fibre Frames collected: 843 Seconds exposure per frame: 4.0 Degrees rotation per frame: 1.0 Crystal-detector distance (mm): 55.0 Client: Levi Senior Sample code: LS014

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.

Refinement. Refined as a pseudomerohedral twin.

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

	x	y	z	Uiso*/Ueq
Bi1	0.50460 (2)	0.74323 (2)	0.58217 (2)	0.01486 (5)
I1	0.34952 (2)	0.87654 (3)	0.71421 (2)	0.02166 (7)
I2	0.67606 (2)	0.60869 (3)	0.69839 (2)	0.02465 (7)
I3	0.64735 (2)	1.07351 (3)	0.57417 (2)	0.01894 (6)
I4	0.37076 (2)	0.40914 (3)	0.58707 (2)	0.01862 (6)
N1	0.9263 (3)	0.8116 (4)	0.5537 (2)	0.0208 (7)
H1	0.866088	0.859132	0.575544	0.025*
N2	0.8629 (3)	0.8991 (4)	0.4191 (3)	0.0284 (9)
H2A	0.806907	0.948964	0.445890	0.034*
H2B	0.868236	0.904688	0.361884	0.034*
N3	0.9804 (4)	0.7490 (5)	0.6951 (3)	0.0351 (10)
H3A	0.920276	0.801655	0.713883	0.042*
H3B	1.027092	0.703144	0.732718	0.042*
C1	0.9402 (3)	0.8146 (5)	0.4653 (3)	0.0210 (9)
C2	1.0331 (4)	0.7373 (5)	0.4300 (3)	0.0230 (9)
H2	1.045469	0.738032	0.368830	0.028*
C3	1.1076 (4)	0.6590 (5)	0.4857 (3)	0.0229 (9)
H3	1.170743	0.602856	0.461827	0.028*
C4	1.0934 (3)	0.6595 (5)	0.5748 (3)	0.0218 (9)
H4	1.146698	0.606093	0.611665	0.026*
C5	1.0007 (4)	0.7388 (5)	0.6103 (3)	0.0223 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01475 (8)	0.01618 (7)	0.01365 (8)	−0.00005 (5)	0.00050 (6)	−0.00046 (6)
I1	0.02187 (14)	0.02647 (13)	0.01666 (13)	0.00351 (10)	0.00292 (11)	−0.00414 (10)
I2	0.02031 (14)	0.02924 (14)	0.02440 (15)	0.00093 (11)	−0.00569 (12)	0.00617 (11)
I3	0.01781 (13)	0.01897 (12)	0.02003 (13)	−0.00332 (10)	−0.00335 (11)	0.00159 (10)
I4	0.01745 (13)	0.01773 (12)	0.02070 (14)	−0.00210 (9)	0.00599 (10)	−0.00229 (10)
N1	0.0154 (17)	0.0211 (16)	0.026 (2)	0.0028 (14)	0.0027 (14)	−0.0034 (15)
N2	0.025 (2)	0.0316 (19)	0.028 (2)	0.0045 (16)	−0.0034 (17)	0.0052 (17)
N3	0.035 (3)	0.049 (2)	0.021 (2)	0.0148 (19)	0.0009 (19)	0.0006 (18)
C1	0.020 (2)	0.0187 (19)	0.024 (2)	−0.0040 (16)	−0.0041 (17)	0.0000 (17)
C2	0.022 (2)	0.025 (2)	0.021 (2)	−0.0032 (16)	0.0051 (18)	−0.0031 (17)
C3	0.019 (2)	0.0167 (19)	0.033 (3)	−0.0024 (16)	0.0040 (18)	−0.0040 (18)
C4	0.018 (2)	0.0191 (19)	0.028 (2)	0.0007 (16)	−0.0001 (18)	0.0011 (18)
C5	0.018 (2)	0.022 (2)	0.026 (2)	−0.0007 (15)	−0.0005 (19)	0.0017 (17)

Geometric parameters (Å, º)

Bi1—I1	2.9432 (3)	N2—H2B	0.8800
Bi1—I2	2.9187 (3)	N3—C5	1.325 (6)
Bi1—I3	3.1003 (3)	N3—H3A	0.8800
Bi1—I3^i	3.3348 (3)	N3—H3B	0.8800
Bi1—I4	3.0660 (3)	C1—C2	1.381 (6)
Bi1—I4^ii	3.2248 (3)	C2—C3	1.380 (6)
N1—C1	1.365 (6)	C2—H2	0.9500
N1—C5	1.369 (5)	C3—C4	1.376 (6)
N1—H1	0.8800	C3—H3	0.9500
N2—C1	1.342 (5)	C4—C5	1.387 (6)
N2—H2A	0.8800	C4—H4	0.9500
I2—Bi1—I1	98.912 (9)	C1—N2—H2B	120.0
I2—Bi1—I4	92.810 (8)	H2A—N2—H2B	120.0
I1—Bi1—I4	87.214 (8)	C5—N3—H3A	120.0
I2—Bi1—I3	86.160 (8)	C5—N3—H3B	120.0
I1—Bi1—I3	94.815 (8)	H3A—N3—H3B	120.0
I4—Bi1—I3	177.843 (9)	N2—C1—N1	116.6 (4)
I2—Bi1—I4^ii	91.716 (9)	N2—C1—C2	124.6 (4)
I1—Bi1—I4^ii	168.189 (9)	N1—C1—C2	118.7 (4)
I4—Bi1—I4^ii	87.131 (8)	C3—C2—C1	118.4 (4)
I3—Bi1—I4^ii	91.004 (8)	C3—C2—H2	120.8
I2—Bi1—I3^i	168.288 (10)	C1—C2—H2	120.8
I1—Bi1—I3^i	89.748 (8)	C4—C3—C2	122.1 (4)
I4—Bi1—I3^i	95.489 (8)	C4—C3—H3	118.9
I3—Bi1—I3^i	85.263 (7)	C2—C3—H3	118.9
I4^ii—Bi1—I3^i	80.483 (8)	C3—C4—C5	119.4 (4)
Bi1—I3—Bi1^i	94.738 (7)	C3—C4—H4	120.3
Bi1—I4—Bi1^ii	92.869 (8)	C5—C4—H4	120.3
C1—N1—C5	123.8 (4)	N3—C5—N1	118.5 (4)
C1—N1—H1	118.1	N3—C5—C4	124.1 (4)
C5—N1—H1	118.1	N1—C5—C4	117.5 (4)
C1—N2—H2A	120.0
C5—N1—C1—N2	−176.4 (4)	C2—C3—C4—C5	1.0 (6)
C5—N1—C1—C2	1.4 (6)	C1—N1—C5—N3	177.6 (4)
N2—C1—C2—C3	178.1 (4)	C1—N1—C5—C4	−2.0 (6)
N1—C1—C2—C3	0.5 (6)	C3—C4—C5—N3	−178.8 (4)
C1—C2—C3—C4	−1.7 (6)	C3—C4—C5—N1	0.8 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I3	0.88	3.12	3.941 (3)	157
N2—H2A···I3	0.88	2.92	3.773 (4)	165
N2—H2B···I1^iii	0.88	3.16	3.811 (4)	132
N3—H3A···I2^iv	0.88	2.98	3.754 (4)	147
N3—H3B···I1^v	0.88	3.06	3.816 (4)	145

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

catena-Poly[2,6-diaminopyridinium [[cis-dibromidobismuth(III)]-di-µ-bromido]] (6)

Crystal data

(C5H7N2)[BiBr4]	F(000) = 1096
Mr = 623.75	Dx = 3.443 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.66220 (15) Å	Cell parameters from 13232 reflections
b = 14.08143 (19) Å	θ = 3.5–29.3°
c = 7.35193 (9) Å	µ = 27.89 mm^−1
β = 94.7149 (13)°	T = 160 K
V = 1203.25 (3) Å^3	Block, colourless
Z = 4	0.21 × 0.08 × 0.06 mm

Data collection

Oxford Diffraction SuperNova dual radiation diffractometer	3128 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray source	2794 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.040
Detector resolution: 10.3801 pixels mm^-1	θmax = 29.5°, θmin = 2.9°
ω scans	h = −16→15
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	k = −19→19
Tmin = 0.735, Tmax = 1.000	l = −10→9
26081 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: geom & difmap
wR(F^2) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0231P)^2 + 0.9774P] where P = (Fo^2 + 2Fc^2)/3
3127 reflections	(Δ/σ)max = 0.001
121 parameters	Δρmax = 1.26 e Å^−3
0 restraints	Δρmin = −2.21 e Å^−3

Special details

Experimental. Data collection and full structure determination done by Prof. Anthony Linden: [e-mail]

Solvent used: 2M HBr Cooling Device: Oxford Instruments Cryojet XL Crystal mount: on a glass fibre Frames collected: 813 Seconds exposure per frame: 8.0 Degrees rotation per frame: 1.0 Crystal-detector distance (mm): 55.0 Client: Levi Senior Sample code: LS036

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
Bi1	0.26448 (2)	0.33482 (2)	0.52386 (2)	0.01425 (5)
Br1	0.13501 (3)	0.47782 (3)	0.37005 (5)	0.02171 (10)
Br2	0.41622 (3)	0.45100 (3)	0.69260 (5)	0.01968 (9)
Br3	0.11987 (3)	0.33214 (3)	0.82384 (5)	0.01866 (9)
Br4	0.40032 (3)	0.32819 (3)	0.21440 (5)	0.01834 (9)
N1	0.1705 (4)	0.5749 (3)	0.9120 (6)	0.0401 (11)
H1	0.144 (5)	0.523 (5)	0.881 (8)	0.06 (2)*
N2	0.3249 (4)	0.8303 (3)	1.0181 (6)	0.0306 (9)
H21	0.285 (5)	0.878 (5)	0.978 (8)	0.059 (19)*
H22	0.389 (5)	0.830 (4)	1.079 (8)	0.056 (19)*
C1	0.2767 (5)	0.5783 (4)	1.0033 (6)	0.0393 (13)
H11	0.314405	0.520835	1.040512	0.047*
C2	0.3290 (4)	0.6616 (3)	1.0414 (6)	0.0274 (10)
H2	0.402901	0.662979	1.106108	0.033*
C3	0.2741 (3)	0.7471 (3)	0.9855 (5)	0.0191 (8)
C4	0.1635 (3)	0.7410 (3)	0.8953 (5)	0.0237 (9)
H4	0.122560	0.797233	0.859612	0.028*
C5	0.1155 (4)	0.6550 (3)	0.8594 (6)	0.0307 (11)
H5	0.041453	0.651245	0.795595	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01459 (8)	0.01259 (9)	0.01554 (8)	−0.00020 (5)	0.00109 (6)	0.00034 (5)
Br1	0.01822 (19)	0.0174 (2)	0.0288 (2)	0.00216 (16)	−0.00217 (16)	0.00382 (16)
Br2	0.01819 (18)	0.0172 (2)	0.0231 (2)	−0.00246 (15)	−0.00186 (15)	−0.00160 (15)
Br3	0.01692 (19)	0.0173 (2)	0.0222 (2)	0.00106 (15)	0.00430 (15)	0.00167 (14)
Br4	0.01725 (19)	0.0181 (2)	0.01999 (19)	−0.00329 (15)	0.00321 (15)	−0.00210 (14)
N1	0.062 (3)	0.020 (2)	0.042 (2)	−0.017 (2)	0.025 (2)	−0.0098 (19)
N2	0.025 (2)	0.027 (2)	0.038 (2)	−0.0059 (18)	−0.0059 (19)	0.0008 (18)
C1	0.063 (4)	0.025 (3)	0.034 (3)	0.019 (3)	0.026 (3)	0.010 (2)
C2	0.029 (2)	0.032 (3)	0.021 (2)	0.012 (2)	0.0059 (18)	0.0051 (18)
C3	0.0204 (19)	0.021 (2)	0.0162 (19)	−0.0004 (17)	0.0027 (15)	0.0018 (16)
C4	0.022 (2)	0.023 (2)	0.026 (2)	0.0014 (18)	0.0000 (17)	−0.0011 (17)
C5	0.028 (2)	0.033 (3)	0.032 (2)	−0.012 (2)	0.007 (2)	−0.006 (2)

Geometric parameters (Å, º)

Bi1—Br1	2.7079 (4)	N2—H21	0.85 (6)
Bi1—Br2	2.6431 (4)	N2—H22	0.84 (6)
Bi1—Br3	2.8846 (4)	C1—C2	1.341 (7)
Bi1—Br3^i	3.1822 (4)	C1—H11	0.9500
Bi1—Br4	2.8787 (4)	C2—C3	1.408 (6)
Bi1—Br4^ii	3.0620 (4)	C2—H2	0.9500
N1—C5	1.338 (7)	C3—C4	1.403 (5)
N1—C1	1.361 (7)	C4—C5	1.352 (6)
N1—H1	0.81 (6)	C4—H4	0.9500
N2—C3	1.326 (6)	C5—H5	0.9500
Br2—Bi1—Br1	93.702 (13)	C1—N1—H1	118 (4)
Br2—Bi1—Br4	90.017 (12)	C3—N2—H21	114 (4)
Br1—Bi1—Br4	91.046 (12)	C3—N2—H22	117 (4)
Br2—Bi1—Br3	93.452 (12)	H21—N2—H22	128 (6)
Br1—Bi1—Br3	89.314 (12)	C2—C1—N1	120.9 (5)
Br4—Bi1—Br3	176.482 (12)	C2—C1—H11	119.6
Br2—Bi1—Br4^ii	87.020 (12)	N1—C1—H11	119.6
Br1—Bi1—Br4^ii	176.605 (12)	C1—C2—C3	119.9 (5)
Br4—Bi1—Br4^ii	92.272 (11)	C1—C2—H2	120.0
Br3—Bi1—Br4^ii	87.331 (11)	C3—C2—H2	120.0
Br2—Bi1—Br3^i	169.462 (12)	N2—C3—C4	121.2 (4)
Br1—Bi1—Br3^i	95.756 (12)	N2—C3—C2	121.1 (4)
Br4—Bi1—Br3^i	85.182 (11)	C4—C3—C2	117.7 (4)
Br3—Bi1—Br3^i	91.301 (11)	C5—C4—C3	119.7 (4)
Br4^ii—Bi1—Br3^i	83.810 (12)	C5—C4—H4	120.1
Bi1—Br3—Bi1^ii	92.407 (11)	C3—C4—H4	120.1
Bi1—Br4—Bi1^i	95.064 (11)	N1—C5—C4	121.2 (5)
C5—N1—C1	120.6 (4)	N1—C5—H5	119.4
C5—N1—H1	121 (4)	C4—C5—H5	119.4
C5—N1—C1—C2	−0.5 (7)	N2—C3—C4—C5	178.1 (4)
N1—C1—C2—C3	−0.5 (7)	C2—C3—C4—C5	−2.4 (6)
C1—C2—C3—N2	−178.6 (4)	C1—N1—C5—C4	−0.1 (7)
C1—C2—C3—C4	1.9 (6)	C3—C4—C5—N1	1.5 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br3	0.81 (6)	2.74 (6)	3.521 (4)	163 (6)
N2—H21···Br1^iii	0.85 (6)	2.76 (7)	3.605 (5)	173 (5)
N2—H22···Br4^iv	0.84 (6)	2.78 (6)	3.620 (4)	179 (5)

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