Utilizing proton transfer to produce mol­ecular salts in bromanilic acid substituted-pyridine mol­ecular complexes – predictable synthons?

Controlled introduction of proton transfer into the design of a series of mol­ecular complexes is described, delivering the systematic production of ionic mol­ecular complexes (mol­ecular salts). The controlled production of mol­ecular salts has relevance as a potential strategy in the design of pharmaceutical materials. In nine mol­ecular complexes consisting of bromanilic acid with the N-heterocyclic compounds 2-, 3- and 4-picoline [bis(2/3/4-methylpyridinium) 2,5-dibromo-3,6-di­oxo­cyclohexa-1,4-diene-1,4-diolate, 2C₆H₈N⁺·C₆Br₂O₄²⁻], 2,3-, 2,4-, 2,5- and 3,5-lutidine [2,3/2,4/2,5/3,5-dimethylpyridin­ium 2,5-dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1-ol­ate, C₇H₁₀N⁺·C₆HBr₂O₄⁻], and 3-bromo-4-methylpyridine [3-bromo-4-methylpyridinium 2,5-dibromo-4-hydroxy-3,6-di­oxocyclohexa-1,4-dien-1-ol­ate, C₆H₇BrN⁺·C₆HBr₂O₄⁻] and 2-bromo-3-methyl­pyridine [2-bromo-3-methyl­pyridine–2,5-di­bromo-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione (1/1), C₆H₆BrN·C₆H₂Br₂O₄], proton transfer occurs readily between the bromanilic acid mol­ecule and the N heteroatom of the pyri­dine ring, in all cases producing a charge-assisted bifurcated N—H...O hydrogen bond. This reinforces the value of this motif as a design tool in the crystal engineering of such complexes. The protonation state (and stoichiometry) significantly affect the supra­molecular synthons obtained, but 1:2 stoichiometries reliably give rise to PBP synthons and 1:1 stoichiometries to PBBP synthons (where P indicates a methyl­pyridine co-mol­ecule and B a bromanilic acid mol­ecule). The influence of halogen inter­actions on the wider crystal packing is also discussed, with C—H...Br and Br...O inter­actions the most prevalent; only one Br...Br inter­action is found.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: APEX2 (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008) for ba2pic_100k_1-1, ba24lut, ba_3br4mepyr; SHELXL97 (Sheldrick, 2008) for ba3pic100k1121apr_0m, br3p14jan_0m, ba25lut_100k_11aug_0m, ba_35lut, ba23lut, ba_2br3mepyr.

(ba2pic_100k_1-1) Bis(2-picolinium) bromanilate

Crystal data

2C6H8N^+·C6Br2O4^2^−	Z = 4
Mr = 484.15	F(000) = 960
Monoclinic, P21/c	Dx = 1.799 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 16.3604 (13) Å	µ = 4.56 mm^−1
b = 7.7452 (6) Å	T = 100 K
c = 14.3658 (9) Å	Block, purple
β = 100.911 (3)°	0.3 × 0.25 × 0.15 mm
V = 1787.4 (2) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	3506 reflections with I > 2σ(I)
CCD; rotation images scans	Rint = 0.056
Absorption correction: multi-scan (SADABS; Blessing, 1995)	θmax = 29.4°, θmin = 1.3°
Tmin = 0.567, Tmax = 1.000	h = −22→22
20956 measured reflections	k = −10→10
4883 independent reflections	l = −19→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0356P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
4883 reflections	Δρmax = 0.64 e Å^−3
245 parameters	Δρmin = −0.45 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
C14	0.37734 (17)	0.6533 (4)	0.6404 (2)	0.0225 (6)
H14	0.3549	0.6463	0.6951	0.027*
N2	0.47738 (15)	0.7632 (3)	0.55824 (16)	0.0154 (5)
H2	0.5221 (18)	0.819 (3)	0.555 (2)	0.014 (8)*
C13	0.44575 (17)	0.7605 (3)	0.6381 (2)	0.0182 (6)
C16	0.37626 (17)	0.5683 (3)	0.4798 (2)	0.0198 (6)
H16	0.353	0.5058	0.426	0.024*
C17	0.44378 (18)	0.6720 (3)	0.4803 (2)	0.0190 (6)
H17	0.467	0.6799	0.4261	0.023*
C15	0.34340 (18)	0.5586 (4)	0.5619 (2)	0.0228 (6)
H15	0.298	0.4873	0.5637	0.027*
C18	0.48453 (18)	0.8700 (4)	0.7190 (2)	0.0233 (6)
H18A	0.518	0.7995	0.7665	0.035*
H18B	0.4418	0.9256	0.7457	0.035*
H18C	0.5189	0.956	0.6974	0.035*
Br1	0.77406 (2)	1.20048 (3)	0.68748 (2)	0.01821 (8)
Br2	0.69958 (2)	0.79178 (3)	0.26985 (2)	0.01666 (8)
O3	0.59107 (12)	0.8222 (2)	0.42497 (13)	0.0183 (4)
O1	0.87359 (12)	1.1929 (2)	0.52699 (13)	0.0204 (4)
O2	0.84955 (12)	1.0180 (3)	0.36536 (13)	0.0235 (5)
O4	0.62485 (11)	0.9647 (2)	0.59632 (13)	0.0184 (4)
C5	0.65969 (16)	0.8970 (3)	0.44594 (18)	0.0136 (5)
C6	0.67803 (17)	0.9850 (3)	0.54532 (18)	0.0143 (5)
C4	0.71999 (16)	0.9081 (3)	0.38883 (18)	0.0147 (5)
C2	0.80862 (16)	1.1020 (3)	0.50893 (18)	0.0154 (5)
C1	0.75152 (17)	1.0828 (3)	0.56894 (18)	0.0151 (5)
C3	0.79362 (16)	1.0039 (3)	0.41342 (18)	0.0151 (5)
N1	0.96988 (16)	1.2838 (3)	0.40231 (18)	0.0191 (5)
H1	0.934 (3)	1.254 (5)	0.426 (3)	0.058 (14)*
C10	1.09443 (19)	1.2292 (4)	0.3478 (2)	0.0225 (6)
H10	1.1357	1.1531	0.3371	0.027*
C9	1.09745 (17)	1.4029 (4)	0.32392 (18)	0.0206 (6)
H9	1.1408	1.4444	0.2966	0.025*
C8	1.03543 (17)	1.5140 (3)	0.34108 (18)	0.0191 (6)
H8	1.0379	1.6305	0.3262	0.023*
C7	0.97025 (17)	1.4529 (3)	0.37997 (18)	0.0166 (5)
C11	1.02907 (18)	1.1726 (3)	0.3874 (2)	0.0202 (6)
H11	1.0258	1.057	0.4039	0.024*
C12	0.89918 (18)	1.5601 (4)	0.3976 (2)	0.0241 (6)
H12A	0.8514	1.5385	0.3489	0.036*
H12B	0.9139	1.6801	0.397	0.036*
H12C	0.8865	1.531	0.4582	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C14	0.0175 (15)	0.0271 (15)	0.0244 (16)	0.0084 (12)	0.0076 (12)	0.0078 (13)
N2	0.0142 (12)	0.0156 (11)	0.0167 (12)	0.0021 (9)	0.0037 (9)	0.0031 (9)
C13	0.0193 (15)	0.0181 (13)	0.0176 (14)	0.0080 (10)	0.0046 (11)	0.0043 (11)
C16	0.0147 (14)	0.0196 (13)	0.0248 (15)	0.0022 (11)	0.0028 (11)	0.0003 (11)
C17	0.0188 (15)	0.0183 (13)	0.0201 (15)	0.0065 (11)	0.0038 (11)	0.0032 (11)
C15	0.0176 (15)	0.0217 (14)	0.0305 (17)	0.0022 (11)	0.0081 (12)	0.0073 (12)
C18	0.0213 (16)	0.0280 (15)	0.0206 (15)	0.0060 (12)	0.0036 (11)	0.0019 (13)
Br1	0.02134 (16)	0.02129 (14)	0.01274 (14)	−0.00143 (11)	0.00508 (10)	−0.00220 (11)
Br2	0.01661 (15)	0.01926 (13)	0.01452 (14)	−0.00167 (11)	0.00401 (10)	−0.00316 (11)
O3	0.0170 (10)	0.0197 (10)	0.0187 (10)	−0.0032 (8)	0.0046 (8)	−0.0016 (8)
O1	0.0224 (11)	0.0223 (10)	0.0176 (10)	−0.0088 (8)	0.0069 (8)	−0.0054 (8)
O2	0.0206 (11)	0.0298 (11)	0.0226 (11)	−0.0077 (9)	0.0103 (8)	−0.0060 (9)
O4	0.0168 (10)	0.0237 (10)	0.0166 (10)	−0.0008 (8)	0.0078 (8)	0.0018 (8)
C5	0.0127 (13)	0.0112 (11)	0.0170 (13)	0.0037 (10)	0.0028 (10)	0.0028 (10)
C6	0.0184 (15)	0.0126 (11)	0.0127 (13)	0.0040 (10)	0.0043 (10)	0.0039 (10)
C4	0.0160 (14)	0.0172 (12)	0.0108 (13)	−0.0002 (10)	0.0024 (10)	−0.0006 (10)
C2	0.0169 (14)	0.0139 (12)	0.0155 (13)	0.0023 (10)	0.0030 (10)	0.0011 (10)
C1	0.0206 (15)	0.0148 (12)	0.0111 (13)	0.0009 (10)	0.0057 (10)	−0.0010 (10)
C3	0.0159 (14)	0.0157 (12)	0.0145 (13)	−0.0005 (10)	0.0046 (10)	0.0004 (10)
N1	0.0160 (13)	0.0221 (12)	0.0198 (13)	−0.0042 (10)	0.0050 (10)	0.0015 (10)
C10	0.0236 (16)	0.0272 (15)	0.0156 (14)	0.0044 (12)	0.0011 (11)	−0.0013 (12)
C9	0.0181 (15)	0.0298 (15)	0.0141 (14)	−0.0074 (12)	0.0036 (10)	0.0014 (12)
C8	0.0224 (15)	0.0179 (13)	0.0152 (14)	−0.0029 (11)	−0.0005 (11)	−0.0002 (11)
C7	0.0177 (14)	0.0198 (13)	0.0109 (13)	−0.0004 (11)	−0.0010 (10)	−0.0002 (10)
C11	0.0210 (15)	0.0169 (13)	0.0217 (15)	−0.0009 (11)	0.0021 (11)	0.0015 (11)
C12	0.0243 (16)	0.0285 (15)	0.0177 (15)	0.0033 (12)	−0.0005 (12)	−0.0033 (12)

Geometric parameters (Å, º)

C14—C15	1.371 (4)	C5—C4	1.400 (4)
C14—C13	1.399 (4)	C5—C6	1.559 (4)
C14—H14	0.93	C6—C1	1.407 (4)
N2—C13	1.346 (3)	C4—C3	1.402 (4)
N2—C17	1.350 (4)	C2—C1	1.394 (4)
N2—H2	0.86 (3)	C2—C3	1.547 (4)
C13—C18	1.481 (4)	N1—C11	1.343 (4)
C16—C17	1.365 (4)	N1—C7	1.349 (3)
C16—C15	1.388 (4)	N1—H1	0.77 (4)
C16—H16	0.93	C10—C11	1.375 (4)
C17—H17	0.93	C10—C9	1.392 (4)
C15—H15	0.93	C10—H10	0.93
C18—H18A	0.96	C9—C8	1.387 (4)
C18—H18B	0.96	C9—H9	0.93
C18—H18C	0.96	C8—C7	1.378 (4)
Br1—C1	1.905 (2)	C8—H8	0.93
Br2—C4	1.905 (3)	C7—C12	1.489 (4)
O3—C5	1.249 (3)	C11—H11	0.93
O1—C2	1.260 (3)	C12—H12A	0.96
O2—C3	1.251 (3)	C12—H12B	0.96
O4—C6	1.249 (3)	C12—H12C	0.96
C15—C14—C13	120.0 (3)	O1—C2—C1	124.8 (2)
C15—C14—H14	120	O1—C2—C3	116.3 (2)
C13—C14—H14	120	C1—C2—C3	118.9 (2)
C13—N2—C17	122.5 (3)	C2—C1—C6	123.4 (2)
C13—N2—H2	121.9 (19)	C2—C1—Br1	117.56 (19)
C17—N2—H2	115.5 (19)	C6—C1—Br1	119.02 (19)
N2—C13—C14	117.9 (3)	O2—C3—C4	126.2 (2)
N2—C13—C18	118.9 (3)	O2—C3—C2	115.9 (2)
C14—C13—C18	123.2 (3)	C4—C3—C2	117.9 (2)
C17—C16—C15	118.1 (3)	C11—N1—C7	123.3 (3)
C17—C16—H16	121	C11—N1—H1	121 (3)
C15—C16—H16	121	C7—N1—H1	116 (3)
N2—C17—C16	121.0 (3)	C11—C10—C9	118.5 (3)
N2—C17—H17	119.5	C11—C10—H10	120.8
C16—C17—H17	119.5	C9—C10—H10	120.8
C14—C15—C16	120.6 (3)	C8—C9—C10	119.6 (3)
C14—C15—H15	119.7	C8—C9—H9	120.2
C16—C15—H15	119.7	C10—C9—H9	120.2
C13—C18—H18A	109.5	C7—C8—C9	120.5 (3)
C13—C18—H18B	109.5	C7—C8—H8	119.7
H18A—C18—H18B	109.5	C9—C8—H8	119.7
C13—C18—H18C	109.5	N1—C7—C8	117.9 (3)
H18A—C18—H18C	109.5	N1—C7—C12	117.5 (3)
H18B—C18—H18C	109.5	C8—C7—C12	124.5 (3)
O3—C5—C4	126.0 (2)	N1—C11—C10	120.2 (3)
O3—C5—C6	115.6 (2)	N1—C11—H11	119.9
C4—C5—C6	118.4 (2)	C10—C11—H11	119.9
O4—C6—C1	125.8 (2)	C7—C12—H12A	109.5
O4—C6—C5	116.6 (2)	C7—C12—H12B	109.5
C1—C6—C5	117.6 (2)	H12A—C12—H12B	109.5
C5—C4—C3	123.5 (2)	C7—C12—H12C	109.5
C5—C4—Br2	118.27 (19)	H12A—C12—H12C	109.5
C3—C4—Br2	118.22 (19)	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4	0.86 (3)	2.02 (3)	2.838 (3)	159 (3)
N2—H2···O3	0.86 (3)	2.36 (3)	2.946 (3)	126 (2)
N1—H1···O1	0.77 (4)	1.96 (4)	2.693 (3)	160 (4)
N1—H1···O2	0.77 (4)	2.36 (4)	2.828 (3)	121 (4)

(ba3pic100k1121apr_0m) Bis(3-picolinium) bromanilate

Crystal data

2C6H8N^+·C6Br2O4^2^−	Z = 2
Mr = 484.15	F(000) = 480
Monoclinic, P21/c	Dx = 1.846 Mg m^−3
a = 8.9526 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6149 (8) Å	µ = 4.68 mm^−1
c = 10.4275 (8) Å	T = 100 K
β = 103.935 (4)°	Block, purple
V = 871.17 (12) Å^3	0.3 × 0.25 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2018 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
CCD; rotation images scans	θmax = 28.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −12→12
Tmin = 0.671, Tmax = 1.000	k = −13→11
9784 measured reflections	l = −11→14
2280 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: mixed
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0286P)^2 + 0.5432P] where P = (Fo^2 + 2Fc^2)/3
2280 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

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

	x	y	z	Uiso*/Ueq
H5	0.893 (4)	0.515 (3)	0.285 (3)	0.057 (10)*
Br1	0.43444 (2)	0.23608 (2)	0.18610 (2)	0.01678 (7)
O1	0.71755 (15)	0.42622 (14)	0.21943 (13)	0.0185 (3)
O2	0.23321 (14)	0.35789 (14)	−0.07254 (14)	0.0182 (3)
C1	0.4732 (2)	0.38635 (18)	0.07990 (18)	0.0137 (3)
C3	0.3575 (2)	0.41949 (18)	−0.03428 (18)	0.0136 (3)
C6	1.2623 (2)	0.61801 (19)	0.47325 (18)	0.0158 (4)
H6	1.3581	0.6454	0.5237	0.019*
C2	0.6123 (2)	0.45631 (18)	0.11904 (18)	0.0135 (3)
N1	0.98369 (19)	0.53679 (17)	0.32431 (16)	0.0179 (3)
C4	0.9917 (2)	0.64850 (19)	0.40243 (19)	0.0160 (4)
H4	0.9021	0.6963	0.4047	0.019*
C5	1.1315 (2)	0.69418 (19)	0.47996 (18)	0.0141 (3)
C7	1.2510 (2)	0.5025 (2)	0.39267 (19)	0.0181 (4)
H7	1.3384	0.4521	0.3886	0.022*
C9	1.1387 (2)	0.8178 (2)	0.5686 (2)	0.0210 (4)
H9A	1.1519	0.9007	0.5213	0.031*
H9B	1.2239	0.8077	0.6441	0.031*
H9C	1.0448	0.8242	0.5974	0.031*
C8	1.1086 (2)	0.4633 (2)	0.31852 (19)	0.0195 (4)
H8	1.0992	0.3854	0.2642	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01435 (10)	0.01840 (11)	0.01676 (11)	−0.00363 (7)	0.00212 (7)	0.00366 (7)
O1	0.0149 (6)	0.0217 (7)	0.0159 (7)	−0.0044 (5)	−0.0021 (5)	0.0023 (5)
O2	0.0133 (6)	0.0184 (7)	0.0207 (7)	−0.0043 (5)	−0.0004 (5)	0.0005 (5)
C1	0.0145 (8)	0.0134 (8)	0.0136 (9)	−0.0027 (6)	0.0042 (7)	0.0001 (7)
C3	0.0129 (8)	0.0138 (8)	0.0138 (9)	−0.0005 (6)	0.0027 (6)	−0.0032 (7)
C6	0.0113 (8)	0.0192 (9)	0.0159 (9)	−0.0013 (7)	0.0011 (7)	0.0013 (7)
C2	0.0136 (8)	0.0142 (8)	0.0127 (8)	−0.0006 (6)	0.0034 (7)	−0.0025 (7)
N1	0.0150 (8)	0.0223 (8)	0.0138 (8)	−0.0055 (6)	−0.0016 (6)	0.0051 (6)
C4	0.0127 (8)	0.0177 (9)	0.0168 (9)	0.0015 (7)	0.0023 (7)	0.0072 (7)
C5	0.0151 (8)	0.0138 (8)	0.0140 (9)	−0.0009 (7)	0.0044 (7)	0.0035 (7)
C7	0.0175 (9)	0.0182 (9)	0.0190 (9)	0.0034 (7)	0.0055 (7)	0.0016 (7)
C9	0.0212 (9)	0.0177 (9)	0.0259 (11)	0.0002 (7)	0.0091 (8)	−0.0029 (8)
C8	0.0258 (10)	0.0172 (9)	0.0151 (9)	−0.0035 (7)	0.0044 (8)	−0.0009 (7)

Geometric parameters (Å, º)

Br1—C1	1.9025 (18)	N1—C4	1.339 (3)
O1—C2	1.262 (2)	N1—H5	0.85 (3)
O2—C3	1.238 (2)	C4—C5	1.387 (3)
C1—C2	1.387 (2)	C4—H4	0.9300
C1—C3	1.414 (2)	C5—C9	1.498 (3)
C3—C2^i	1.548 (3)	C7—C8	1.375 (3)
C6—C7	1.381 (3)	C7—H7	0.9300
C6—C5	1.397 (3)	C9—H9A	0.9600
C6—H6	0.9300	C9—H9B	0.9600
C2—C3^i	1.548 (3)	C9—H9C	0.9600
N1—C8	1.336 (3)	C8—H8	0.9300
C2—C1—C3	124.22 (16)	C5—C4—H4	119.4
C2—C1—Br1	118.27 (13)	C4—C5—C6	117.00 (17)
C3—C1—Br1	117.51 (13)	C4—C5—C9	120.62 (17)
O2—C3—C1	125.66 (17)	C6—C5—C9	122.36 (16)
O2—C3—C2^i	116.88 (16)	C8—C7—C6	118.99 (18)
C1—C3—C2^i	117.47 (15)	C8—C7—H7	120.5
C7—C6—C5	120.83 (17)	C6—C7—H7	120.5
C7—C6—H6	119.6	C5—C9—H9A	109.5
C5—C6—H6	119.6	C5—C9—H9B	109.5
O1—C2—C1	124.82 (17)	H9A—C9—H9B	109.5
O1—C2—C3^i	116.88 (15)	C5—C9—H9C	109.5
C1—C2—C3^i	118.30 (15)	H9A—C9—H9C	109.5
C8—N1—C4	121.90 (16)	H9B—C9—H9C	109.5
C8—N1—H5	124 (2)	N1—C8—C7	120.14 (18)
C4—N1—H5	114 (2)	N1—C8—H8	119.9
N1—C4—C5	121.13 (17)	C7—C8—H8	119.9
N1—C4—H4	119.4
C2—C1—C3—O2	179.04 (18)	C8—N1—C4—C5	0.9 (3)
Br1—C1—C3—O2	−1.0 (3)	N1—C4—C5—C6	−0.4 (3)
C2—C1—C3—C2^i	−1.2 (3)	N1—C4—C5—C9	−178.95 (17)
Br1—C1—C3—C2^i	178.77 (12)	C7—C6—C5—C4	−0.1 (3)
C3—C1—C2—O1	−178.72 (18)	C7—C6—C5—C9	178.45 (18)
Br1—C1—C2—O1	1.4 (3)	C5—C6—C7—C8	0.1 (3)
C3—C1—C2—C3^i	1.2 (3)	C4—N1—C8—C7	−0.9 (3)
Br1—C1—C2—C3^i	−178.76 (12)	C6—C7—C8—N1	0.4 (3)

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—H5···O1	0.84 (3)	1.78 (3)	2.598 (2)	165 (3)
N1—H5···O2^i	0.84 (3)	2.54 (3)	3.039 (2)	119 (3)
C4—H4···Br1^ii	0.93	2.96	3.7977 (18)	151

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

(br3p14jan_0m) Bis(4-picolinium) bromanilate

Crystal data

2C6H8N^+·C6Br2O4^2^−	Z = 2
Mr = 484.15	F(000) = 480
Monoclinic, P21/c	Dx = 1.817 Mg m^−3
a = 8.1345 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.1517 (6) Å	µ = 4.61 mm^−1
c = 17.7868 (17) Å	T = 100 K
β = 96.177 (7)°	Block, purple
V = 884.90 (15) Å^3	0.35 × 0.25 × 0.2 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2464 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
CCD; rotation images scans	θmax = 32.8°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −11→12
Tmin = 0.576, Tmax = 1.000	k = −9→8
14105 measured reflections	l = −26→25
3234 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: mixed
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 0.2356P] where P = (Fo^2 + 2Fc^2)/3
3234 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

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

	x	y	z	Uiso*/Ueq
H3	−0.105 (4)	0.310 (6)	−0.2171 (19)	0.047 (10)*
Br1	0.25110 (3)	0.07121 (3)	0.02493 (2)	0.01863 (8)
O1	0.07011 (19)	0.2668 (2)	−0.12123 (8)	0.0186 (3)
O2	−0.1218 (2)	0.6144 (3)	−0.14197 (9)	0.0189 (3)
C3	−0.0715 (3)	0.5690 (3)	−0.07520 (12)	0.0154 (4)
C5	−0.3229 (3)	−0.0633 (3)	−0.26829 (13)	0.0196 (4)
H5	−0.3546	−0.2000	−0.2528	0.024*
C6	−0.2127 (3)	0.0570 (4)	−0.22235 (13)	0.0215 (5)
H6	−0.1685	0.0014	−0.1759	0.026*
C2	0.0452 (2)	0.3690 (3)	−0.06305 (12)	0.0146 (4)
N1	−0.1680 (3)	0.2553 (3)	−0.24406 (11)	0.0214 (4)
C4	−0.3880 (3)	0.0175 (4)	−0.33817 (13)	0.0176 (4)
C1	0.1120 (3)	0.3196 (3)	0.01073 (12)	0.0157 (4)
C7	−0.2265 (3)	0.3409 (4)	−0.31087 (13)	0.0213 (4)
H7	−0.1925	0.4781	−0.3247	0.026*
C8	−0.3370 (3)	0.2240 (4)	−0.35860 (12)	0.0195 (4)
H8	−0.3783	0.2827	−0.4050	0.023*
C9	−0.5047 (3)	−0.1147 (4)	−0.39065 (15)	0.0275 (5)
H9A	−0.4464	−0.1745	−0.4300	0.041*
H9B	−0.5930	−0.0237	−0.4126	0.041*
H9C	−0.5494	−0.2306	−0.3630	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02148 (12)	0.01545 (11)	0.01885 (12)	0.00438 (8)	0.00160 (8)	0.00058 (8)
O1	0.0216 (8)	0.0192 (7)	0.0148 (7)	0.0018 (6)	0.0013 (6)	−0.0037 (6)
O2	0.0247 (8)	0.0181 (7)	0.0134 (7)	0.0011 (6)	−0.0003 (6)	0.0014 (6)
C3	0.0152 (10)	0.0133 (9)	0.0176 (10)	−0.0028 (7)	0.0019 (8)	0.0003 (8)
C5	0.0230 (11)	0.0147 (10)	0.0222 (11)	0.0006 (8)	0.0080 (9)	0.0022 (8)
C6	0.0255 (12)	0.0250 (12)	0.0141 (10)	0.0041 (9)	0.0021 (9)	0.0035 (8)
C2	0.0130 (9)	0.0139 (9)	0.0168 (9)	−0.0020 (7)	0.0015 (8)	−0.0001 (8)
N1	0.0219 (10)	0.0261 (11)	0.0165 (9)	−0.0058 (8)	0.0030 (8)	−0.0047 (8)
C4	0.0155 (10)	0.0185 (10)	0.0196 (10)	0.0018 (8)	0.0048 (8)	−0.0046 (8)
C1	0.0151 (10)	0.0125 (9)	0.0193 (10)	0.0015 (7)	0.0001 (8)	0.0000 (8)
C7	0.0251 (11)	0.0171 (11)	0.0221 (11)	−0.0041 (9)	0.0045 (9)	0.0014 (9)
C8	0.0212 (11)	0.0211 (11)	0.0160 (10)	0.0010 (8)	0.0016 (8)	0.0039 (8)
C9	0.0214 (12)	0.0289 (12)	0.0319 (13)	−0.0045 (9)	0.0015 (10)	−0.0092 (10)

Geometric parameters (Å, º)

Br1—C1	1.902 (2)	N1—C7	1.339 (3)
O1—C2	1.246 (2)	N1—H3	0.74 (3)
O2—C3	1.246 (3)	C4—C8	1.396 (3)
C3—C1^i	1.405 (3)	C4—C9	1.498 (3)
C3—C2	1.554 (3)	C1—C3^i	1.405 (3)
C5—C6	1.364 (3)	C7—C8	1.372 (3)
C5—C4	1.390 (3)	C7—H7	0.9300
C5—H5	0.9300	C8—H8	0.9300
C6—N1	1.341 (3)	C9—H9A	0.9600
C6—H6	0.9300	C9—H9B	0.9600
C2—C1	1.399 (3)	C9—H9C	0.9600
O2—C3—C1^i	125.9 (2)	C8—C4—C9	121.2 (2)
O2—C3—C2	116.31 (18)	C2—C1—C3^i	123.93 (19)
C1^i—C3—C2	117.75 (18)	C2—C1—Br1	117.69 (15)
C6—C5—C4	120.3 (2)	C3^i—C1—Br1	118.15 (15)
C6—C5—H5	119.9	N1—C7—C8	119.3 (2)
C4—C5—H5	119.9	N1—C7—H7	120.3
N1—C6—C5	120.1 (2)	C8—C7—H7	120.3
N1—C6—H6	119.9	C7—C8—C4	120.6 (2)
C5—C6—H6	119.9	C7—C8—H8	119.7
O1—C2—C1	126.0 (2)	C4—C8—H8	119.7
O1—C2—C3	115.80 (18)	C4—C9—H9A	109.5
C1—C2—C3	118.17 (18)	C4—C9—H9B	109.5
C7—N1—C6	122.1 (2)	H9A—C9—H9B	109.5
C7—N1—H3	123 (3)	C4—C9—H9C	109.5
C6—N1—H3	115 (3)	H9A—C9—H9C	109.5
C5—C4—C8	117.6 (2)	H9B—C9—H9C	109.5
C5—C4—C9	121.2 (2)
C4—C5—C6—N1	0.8 (3)	O1—C2—C1—C3^i	−175.6 (2)
O2—C3—C2—O1	−3.6 (3)	C3—C2—C1—C3^i	4.4 (3)
C1^i—C3—C2—O1	175.83 (19)	O1—C2—C1—Br1	−1.1 (3)
O2—C3—C2—C1	176.4 (2)	C3—C2—C1—Br1	178.82 (14)
C1^i—C3—C2—C1	−4.1 (3)	C6—N1—C7—C8	0.7 (3)
C5—C6—N1—C7	−1.0 (3)	N1—C7—C8—C4	−0.2 (3)
C6—C5—C4—C8	−0.3 (3)	C5—C4—C8—C7	0.0 (3)
C6—C5—C4—C9	177.9 (2)	C9—C4—C8—C7	−178.2 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3···O1	0.74 (3)	2.12 (3)	2.760 (3)	145 (4)
N1—H3···O2	0.74 (3)	2.31 (3)	2.859 (3)	131 (3)

(ba24lut) 2,4-Dimethylpyridinium bromanilate

Crystal data

C7H10N^+·C6HBr2O4^−	Z = 4
Mr = 405.04	F(000) = 792
Monoclinic, P21/c	Dx = 1.962 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.2948 (2) Å	µ = 5.92 mm^−1
b = 12.1560 (4) Å	T = 100 K
c = 13.9544 (5) Å	Block, purple
β = 102.966 (2)°	0.25 × 0.2 × 0.1 mm
V = 1371.17 (8) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	4537 reflections with I > 2σ(I)
CCD; rotation images scans	Rint = 0.042
Absorption correction: multi-scan (SADABS; Blessing, 1995)	θmax = 36.0°, θmin = 2.3°
Tmin = 0.631, Tmax = 1.000	h = −13→12
22482 measured reflections	k = −20→19
6064 independent reflections	l = −22→22

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0416P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.002
6064 reflections	Δρmax = 0.85 e Å^−3
191 parameters	Δρmin = −0.56 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
C1	0.9045 (2)	0.19237 (15)	0.55371 (13)	0.0139 (3)
C6	1.0303 (2)	0.18822 (15)	0.49598 (13)	0.0143 (3)
C5	1.00553 (19)	0.10938 (15)	0.40704 (12)	0.0128 (3)
C4	0.8566 (2)	0.05013 (15)	0.38346 (12)	0.0128 (3)
C3	0.73806 (19)	0.05285 (15)	0.44130 (12)	0.0124 (3)
C2	0.77015 (19)	0.12614 (15)	0.53102 (12)	0.0122 (3)
O1	0.65618 (16)	0.12722 (12)	0.58359 (10)	0.0172 (3)
O2	0.60467 (15)	0.00124 (12)	0.42410 (9)	0.0180 (3)
Br2	0.81175 (2)	−0.03915 (2)	0.26962 (2)	0.01608 (5)
O3	1.12026 (14)	0.10678 (11)	0.36234 (9)	0.0160 (3)
O4	1.15299 (15)	0.24626 (13)	0.51291 (10)	0.0211 (3)
Br1	0.93387 (2)	0.29327 (2)	0.65786 (2)	0.01894 (5)
C7	0.4727 (2)	0.23284 (18)	0.31075 (13)	0.0184 (4)
C8	0.6120 (2)	0.29544 (18)	0.30788 (15)	0.0226 (4)
H8	0.6627	0.2868	0.2553	0.027*
C9	0.6772 (2)	0.37030 (18)	0.38125 (17)	0.0246 (4)
C10	0.5959 (2)	0.38279 (17)	0.45817 (17)	0.0233 (4)
H10	0.6353	0.4328	0.5084	0.028*
C11	0.4577 (2)	0.32110 (17)	0.45937 (15)	0.0195 (4)
H11	0.4038	0.3295	0.5106	0.023*
N1	0.39987 (18)	0.24877 (15)	0.38719 (12)	0.0157 (3)
C13	0.8327 (3)	0.4343 (2)	0.3811 (2)	0.0379 (6)
H13A	0.9259	0.3972	0.4213	0.057*
H13B	0.8235	0.5067	0.4068	0.057*
H13C	0.8478	0.4397	0.315	0.057*
C12	0.4002 (2)	0.1503 (2)	0.23501 (14)	0.0271 (5)
H12A	0.352	0.0916	0.2651	0.041*
H12B	0.4854	0.1214	0.2056	0.041*
H12C	0.3164	0.1846	0.1853	0.041*
H1	0.595 (4)	0.091 (3)	0.565 (2)	0.050 (10)*
H2	0.332 (3)	0.211 (2)	0.3888 (18)	0.023 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0158 (7)	0.0135 (9)	0.0136 (7)	−0.0006 (6)	0.0059 (6)	−0.0020 (6)
C6	0.0143 (7)	0.0151 (9)	0.0141 (7)	−0.0005 (6)	0.0046 (6)	−0.0010 (6)
C5	0.0135 (6)	0.0135 (9)	0.0117 (7)	0.0013 (6)	0.0030 (5)	0.0020 (6)
C4	0.0152 (6)	0.0128 (9)	0.0107 (7)	−0.0010 (6)	0.0034 (5)	−0.0008 (6)
C3	0.0147 (7)	0.0115 (8)	0.0113 (7)	−0.0002 (6)	0.0032 (5)	0.0006 (6)
C2	0.0130 (6)	0.0113 (8)	0.0134 (7)	−0.0007 (6)	0.0055 (5)	0.0000 (6)
O1	0.0162 (5)	0.0178 (7)	0.0205 (6)	−0.0055 (5)	0.0100 (5)	−0.0057 (6)
O2	0.0168 (5)	0.0204 (7)	0.0178 (6)	−0.0071 (5)	0.0060 (5)	−0.0027 (5)
Br2	0.01998 (8)	0.01664 (10)	0.01232 (8)	−0.00307 (6)	0.00512 (6)	−0.00285 (6)
O3	0.0151 (5)	0.0199 (7)	0.0146 (6)	−0.0007 (5)	0.0065 (4)	−0.0012 (5)
O4	0.0179 (6)	0.0250 (8)	0.0229 (7)	−0.0080 (5)	0.0097 (5)	−0.0073 (6)
Br1	0.02109 (9)	0.01842 (10)	0.02018 (9)	−0.00729 (7)	0.01073 (7)	−0.00876 (7)
C7	0.0149 (7)	0.0253 (11)	0.0158 (8)	0.0077 (7)	0.0052 (6)	0.0057 (7)
C8	0.0162 (7)	0.0307 (12)	0.0236 (9)	0.0079 (7)	0.0103 (7)	0.0126 (8)
C9	0.0157 (7)	0.0214 (11)	0.0390 (11)	0.0032 (7)	0.0109 (7)	0.0132 (9)
C10	0.0179 (8)	0.0169 (10)	0.0365 (11)	−0.0020 (7)	0.0091 (7)	−0.0020 (9)
C11	0.0191 (7)	0.0170 (10)	0.0251 (9)	0.0001 (7)	0.0107 (7)	−0.0008 (8)
N1	0.0138 (6)	0.0166 (8)	0.0181 (7)	−0.0002 (6)	0.0065 (5)	0.0023 (6)
C13	0.0202 (9)	0.0312 (14)	0.0657 (18)	0.0011 (9)	0.0168 (10)	0.0192 (13)
C12	0.0233 (9)	0.0417 (14)	0.0159 (8)	0.0069 (9)	0.0037 (7)	−0.0048 (9)

Geometric parameters (Å, º)

C1—C2	1.353 (2)	C3—C2	1.511 (2)
C1—C6	1.455 (2)	C2—O1	1.3204 (19)
C1—Br1	1.8753 (18)	C7—N1	1.352 (2)
C6—O4	1.217 (2)	C7—C8	1.392 (3)
C6—C5	1.545 (2)	C7—C12	1.483 (3)
C5—O3	1.2499 (19)	C8—C9	1.386 (3)
C5—C4	1.404 (2)	C9—C10	1.398 (3)
C4—C3	1.405 (2)	C9—C13	1.506 (3)
C4—Br2	1.8907 (17)	C10—C11	1.373 (3)
C3—O2	1.248 (2)	C11—N1	1.342 (3)
C2—C1—C6	120.32 (16)	C4—C3—C2	118.29 (14)
C2—C1—Br1	121.83 (12)	O1—C2—C1	121.24 (16)
C6—C1—Br1	117.85 (12)	O1—C2—C3	116.83 (14)
O4—C6—C1	123.00 (16)	C1—C2—C3	121.83 (14)
O4—C6—C5	118.05 (14)	N1—C7—C8	117.71 (19)
C1—C6—C5	118.92 (14)	N1—C7—C12	118.54 (17)
O3—C5—C4	126.77 (16)	C8—C7—C12	123.75 (17)
O3—C5—C6	115.96 (14)	C9—C8—C7	121.78 (17)
C4—C5—C6	117.26 (14)	C8—C9—C10	117.57 (17)
C5—C4—C3	123.06 (15)	C8—C9—C13	122.0 (2)
C5—C4—Br2	119.22 (12)	C10—C9—C13	120.4 (2)
C3—C4—Br2	117.72 (12)	C11—C10—C9	119.9 (2)
O2—C3—C4	125.60 (16)	N1—C11—C10	120.51 (18)
O2—C3—C2	116.09 (14)	C11—N1—C7	122.55 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.68 (3)	2.03 (3)	2.6509 (18)	151 (3)
O1—H1···O2	0.68 (3)	2.26 (3)	2.6559 (19)	119 (3)
N1—H2···O3^ii	0.72 (2)	2.14 (2)	2.849 (2)	168 (3)
N1—H2···O4^ii	0.72 (2)	2.56 (2)	2.9807 (18)	119 (2)

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

(ba25lut_100k_11aug_0m) 2,5-Dimethylpyridinium bromanilate

Crystal data

C7H10N^+·C6HBr2O4^−	Z = 4
Mr = 405.05	F(000) = 792
Monoclinic, P21/c	Dx = 1.981 Mg m^−3
a = 7.7357 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1416 (6) Å	µ = 5.98 mm^−1
c = 15.8011 (9) Å	T = 100 K
β = 94.269 (3)°	Block, purple
V = 1358.09 (13) Å^3	0.35 × 0.25 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	6083 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
CCD; rotation images scans	θmax = 42.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −14→14
Tmin = 0.404, Tmax = 1.000	k = −20→20
38096 measured reflections	l = −28→29
9404 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0448P)^2 + 0.0632P] where P = (Fo^2 + 2Fc^2)/3
9404 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 1.34 e Å^−3
0 restraints	Δρmin = −1.29 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

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

	x	y	z	Uiso*/Ueq
Br1	0.47843 (2)	0.233106 (16)	0.109383 (11)	0.01484 (4)
Br2	0.31634 (2)	−0.007081 (16)	−0.274211 (11)	0.01501 (4)
C3	0.2818 (2)	0.10008 (15)	−0.01690 (11)	0.0119 (3)
C6	0.5275 (2)	0.11978 (14)	−0.14671 (11)	0.0123 (3)
O1	0.09913 (16)	−0.00774 (12)	−0.12129 (9)	0.0173 (3)
H1	0.0473	−0.01	−0.0779	0.026*
C4	0.4370 (2)	0.16251 (15)	0.00124 (11)	0.0122 (3)
N1	0.96656 (18)	0.26704 (13)	−0.16218 (11)	0.0155 (3)
H1A	0.8804	0.2191	−0.1584	0.019*
O3	0.70419 (18)	0.22877 (14)	−0.04465 (10)	0.0258 (3)
O2	0.16434 (16)	0.08351 (13)	0.03197 (9)	0.0195 (3)
C1	0.3631 (2)	0.05998 (14)	−0.16580 (10)	0.0117 (3)
C2	0.24886 (19)	0.04840 (14)	−0.10558 (11)	0.0117 (3)
C5	0.5638 (2)	0.17603 (16)	−0.05714 (11)	0.0141 (3)
O4	0.63921 (16)	0.12894 (12)	−0.19711 (9)	0.0187 (3)
C7	1.0291 (2)	0.28251 (16)	−0.23903 (12)	0.0156 (3)
C8	1.1653 (2)	0.36261 (16)	−0.24409 (13)	0.0177 (3)
H8	1.2113	0.3762	−0.296	0.021*
C10	1.1676 (2)	0.40233 (16)	−0.09342 (12)	0.0165 (3)
C11	1.0320 (2)	0.32284 (16)	−0.09082 (12)	0.0162 (3)
H11	0.9849	0.3073	−0.0395	0.019*
C12	0.9487 (3)	0.21602 (18)	−0.31284 (13)	0.0212 (4)
H12A	0.9596	0.1313	−0.3026	0.032*
H12B	1.0061	0.2367	−0.3626	0.032*
H12C	0.8282	0.2369	−0.3212	0.032*
C13	1.2407 (3)	0.46639 (19)	−0.01483 (14)	0.0233 (4)
H13A	1.1682	0.4516	0.0308	0.035*
H13B	1.245	0.5511	−0.0258	0.035*
H13C	1.3556	0.4373	0.0006	0.035*
C9	1.2329 (2)	0.42230 (17)	−0.17244 (12)	0.0173 (3)
H9	1.3231	0.4766	−0.1768	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01520 (7)	0.01706 (8)	0.01267 (8)	−0.00345 (6)	0.00383 (5)	−0.00279 (6)
Br2	0.01336 (7)	0.02117 (9)	0.01085 (8)	−0.00387 (6)	0.00315 (5)	−0.00109 (6)
C3	0.0101 (6)	0.0137 (7)	0.0126 (7)	−0.0014 (5)	0.0046 (5)	−0.0004 (5)
C6	0.0107 (6)	0.0128 (7)	0.0139 (7)	−0.0009 (5)	0.0047 (5)	−0.0004 (5)
O1	0.0122 (5)	0.0264 (7)	0.0141 (6)	−0.0088 (5)	0.0056 (4)	−0.0027 (5)
C4	0.0106 (6)	0.0134 (7)	0.0130 (7)	−0.0015 (5)	0.0033 (5)	−0.0013 (5)
N1	0.0104 (5)	0.0156 (6)	0.0206 (7)	−0.0011 (5)	0.0030 (5)	0.0043 (5)
O3	0.0161 (6)	0.0394 (8)	0.0232 (7)	−0.0155 (6)	0.0089 (5)	−0.0115 (6)
O2	0.0149 (5)	0.0284 (7)	0.0164 (6)	−0.0087 (5)	0.0086 (4)	−0.0036 (5)
C1	0.0102 (6)	0.0125 (7)	0.0126 (7)	−0.0016 (5)	0.0034 (5)	−0.0008 (5)
C2	0.0089 (6)	0.0122 (7)	0.0144 (7)	−0.0015 (5)	0.0037 (5)	0.0007 (5)
C5	0.0112 (6)	0.0163 (7)	0.0154 (8)	−0.0030 (5)	0.0049 (5)	−0.0018 (6)
O4	0.0137 (5)	0.0258 (7)	0.0179 (6)	−0.0056 (5)	0.0098 (4)	−0.0045 (5)
C7	0.0117 (6)	0.0160 (7)	0.0195 (8)	0.0045 (5)	0.0048 (6)	0.0026 (6)
C8	0.0133 (7)	0.0199 (8)	0.0211 (9)	0.0024 (6)	0.0094 (6)	0.0057 (7)
C10	0.0098 (6)	0.0179 (8)	0.0220 (9)	0.0013 (6)	0.0013 (6)	0.0051 (6)
C11	0.0118 (6)	0.0193 (8)	0.0178 (8)	−0.0002 (6)	0.0033 (6)	0.0051 (6)
C12	0.0208 (8)	0.0214 (9)	0.0216 (9)	0.0021 (7)	0.0040 (7)	−0.0025 (7)
C13	0.0202 (8)	0.0280 (10)	0.0214 (9)	−0.0036 (7)	−0.0010 (7)	0.0036 (8)
C9	0.0111 (6)	0.0178 (8)	0.0236 (9)	−0.0003 (6)	0.0043 (6)	0.0054 (6)

Geometric parameters (Å, º)

Br1—C4	1.8868 (17)	C7—C8	1.387 (2)
Br2—C1	1.8792 (17)	C7—C12	1.479 (3)
C3—O2	1.2495 (19)	C8—C9	1.382 (3)
C3—C4	1.398 (2)	C8—H8	0.93
C3—C2	1.519 (2)	C10—C11	1.376 (2)
C6—O4	1.2224 (19)	C10—C9	1.399 (3)
C6—C1	1.447 (2)	C10—C13	1.506 (3)
C6—C5	1.554 (2)	C11—H11	0.93
O1—C2	1.3235 (19)	C12—H12A	0.96
O1—H1	0.82	C12—H12B	0.96
C4—C5	1.403 (2)	C12—H12C	0.96
N1—C7	1.351 (2)	C13—H13A	0.96
N1—C11	1.352 (2)	C13—H13B	0.96
N1—H1A	0.86	C13—H13C	0.96
O3—C5	1.238 (2)	C9—H9	0.93
C1—C2	1.352 (2)
O2—C3—C4	126.84 (16)	C9—C8—C7	120.33 (17)
O2—C3—C2	115.73 (14)	C9—C8—H8	119.8
C4—C3—C2	117.41 (14)	C7—C8—H8	119.8
O4—C6—C1	123.74 (16)	C11—C10—C9	117.11 (17)
O4—C6—C5	118.11 (14)	C11—C10—C13	121.42 (17)
C1—C6—C5	118.15 (13)	C9—C10—C13	121.47 (16)
C2—O1—H1	109.5	N1—C11—C10	120.66 (16)
C3—C4—C5	123.35 (15)	N1—C11—H11	119.7
C3—C4—Br1	118.58 (12)	C10—C11—H11	119.7
C5—C4—Br1	118.07 (12)	C7—C12—H12A	109.5
C7—N1—C11	123.63 (15)	C7—C12—H12B	109.5
C7—N1—H1A	118.2	H12A—C12—H12B	109.5
C11—N1—H1A	118.2	C7—C12—H12C	109.5
C2—C1—C6	120.49 (15)	H12A—C12—H12C	109.5
C2—C1—Br2	120.78 (12)	H12B—C12—H12C	109.5
C6—C1—Br2	118.67 (11)	C10—C13—H13A	109.5
O1—C2—C1	121.46 (15)	C10—C13—H13B	109.5
O1—C2—C3	115.90 (13)	H13A—C13—H13B	109.5
C1—C2—C3	122.63 (14)	C10—C13—H13C	109.5
O3—C5—C4	126.44 (16)	H13A—C13—H13C	109.5
O3—C5—C6	115.69 (14)	H13B—C13—H13C	109.5
C4—C5—C6	117.88 (14)	C8—C9—C10	120.99 (16)
N1—C7—C8	117.26 (17)	C8—C9—H9	119.5
N1—C7—C12	119.15 (16)	C10—C9—H9	119.5
C8—C7—C12	123.59 (17)
O2—C3—C4—C5	179.27 (17)	Br1—C4—C5—O3	1.3 (3)
C2—C3—C4—C5	−2.0 (2)	C3—C4—C5—C6	0.8 (3)
O2—C3—C4—Br1	−1.1 (2)	Br1—C4—C5—C6	−178.86 (12)
C2—C3—C4—Br1	177.66 (11)	O4—C6—C5—O3	1.5 (3)
O4—C6—C1—C2	176.91 (17)	C1—C6—C5—O3	−178.24 (16)
C5—C6—C1—C2	−3.3 (2)	O4—C6—C5—C4	−178.34 (16)
O4—C6—C1—Br2	−0.4 (2)	C1—C6—C5—C4	1.9 (2)
C5—C6—C1—Br2	179.37 (12)	C11—N1—C7—C8	−1.6 (2)
C6—C1—C2—O1	−178.85 (15)	C11—N1—C7—C12	179.42 (16)
Br2—C1—C2—O1	−1.6 (2)	N1—C7—C8—C9	0.5 (2)
C6—C1—C2—C3	2.2 (2)	C12—C7—C8—C9	179.45 (17)
Br2—C1—C2—C3	179.44 (12)	C7—N1—C11—C10	1.3 (3)
O2—C3—C2—O1	0.4 (2)	C9—C10—C11—N1	0.1 (3)
C4—C3—C2—O1	−178.49 (15)	C13—C10—C11—N1	179.28 (16)
O2—C3—C2—C1	179.37 (16)	C7—C8—C9—C10	0.8 (3)
C4—C3—C2—C1	0.5 (2)	C11—C10—C9—C8	−1.2 (3)
C3—C4—C5—O3	−179.05 (18)	C13—C10—C9—C8	179.70 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	2.01	2.6994 (17)	141
O1—H1···O2	0.82	2.16	2.6403 (19)	117
N1—H1A···O4	0.86	2.17	2.9794 (19)	158
N1—H1A···O3	0.86	2.34	2.883 (2)	122

Symmetry code: (i) −x, −y, −z.

(ba_35lut) 3,5-Dimethylpyridinium bromanilate

Crystal data

C7H10N^+·C6HBr2O4^−	Z = 4
Mr = 405.04	F(000) = 792
Monoclinic, P21/c	Dx = 1.929 Mg m^−3
a = 11.6766 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4926 (5) Å	µ = 5.82 mm^−1
c = 11.5221 (5) Å	T = 100 K
β = 98.834 (2)°	Block, purple
V = 1394.92 (11) Å^3	0.25 × 0.2 × 0.1 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3131 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
CCD; rotation images scans	θmax = 31.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −13→12
Tmin = 0.684, Tmax = 1.000	k = −14→15
14020 measured reflections	l = −16→16
3817 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 0.6408P] where P = (Fo^2 + 2Fc^2)/3
3817 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 were placed on calculated positions modelled as riding on the atoms to which they were bonded except those involved in hydrogen bonding H1 and H2 (bonded to O1 and N1, respectively) which were identified in a Fourier difference map and the position and isotropic thermal parameters allowed to freely refine.

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

	x	y	z	Uiso*/Ueq
C1	0.1510 (2)	0.0322 (2)	0.38903 (18)	0.0123 (5)
C6	0.0825 (2)	0.1413 (2)	0.41310 (18)	0.0123 (4)
C5	0.1428 (2)	0.2483 (2)	0.49363 (18)	0.0123 (4)
C4	0.2597 (2)	0.2332 (2)	0.53947 (18)	0.0112 (4)
C3	0.3269 (2)	0.1288 (2)	0.51195 (18)	0.0120 (5)
C2	0.2658 (2)	0.0288 (2)	0.42894 (18)	0.0122 (5)
O1	0.33345 (18)	−0.06415 (16)	0.40007 (15)	0.0165 (4)
O2	0.43032 (15)	0.10769 (16)	0.55024 (13)	0.0158 (3)
Br2	0.32803 (2)	0.35454 (2)	0.649891 (18)	0.01431 (7)
O3	0.08053 (15)	0.33992 (15)	0.51253 (15)	0.0173 (4)
O4	−0.01960 (15)	0.15499 (16)	0.37320 (14)	0.0183 (4)
Br1	0.07565 (2)	−0.09875 (2)	0.295328 (19)	0.01606 (7)
C10	0.3537 (2)	0.6732 (2)	0.55142 (19)	0.0144 (5)
C9	0.3628 (2)	0.6104 (2)	0.44682 (19)	0.0155 (5)
H9	0.4359	0.5971	0.4263	0.019*
C8	0.2654 (2)	0.5670 (2)	0.37211 (18)	0.0151 (5)
C7	0.1590 (2)	0.5907 (2)	0.40512 (19)	0.0144 (5)
H7	0.092	0.5631	0.3574	0.017*
N1	0.15066 (19)	0.65280 (18)	0.50482 (16)	0.0137 (4)
C11	0.2440 (2)	0.6936 (2)	0.57811 (19)	0.0142 (5)
H11	0.2347	0.7358	0.647	0.017*
C12	0.2730 (2)	0.4943 (3)	0.2616 (2)	0.0239 (6)
H12A	0.2701	0.4045	0.277	0.036*
H12B	0.3446	0.5144	0.2344	0.036*
H12C	0.2092	0.5174	0.2025	0.036*
C13	0.4582 (2)	0.7162 (3)	0.6358 (2)	0.0230 (6)
H13A	0.4606	0.8076	0.6379	0.034*
H13B	0.5273	0.6842	0.6104	0.034*
H13C	0.4531	0.684	0.7129	0.034*
H2	0.078 (3)	0.664 (3)	0.528 (3)	0.037 (9)*
H1	0.393 (3)	−0.058 (3)	0.428 (3)	0.026 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0128 (14)	0.0138 (10)	0.0105 (9)	0.0014 (8)	0.0030 (8)	0.0005 (7)
C6	0.0116 (14)	0.0143 (10)	0.0115 (9)	0.0005 (9)	0.0030 (8)	0.0019 (8)
C5	0.0120 (13)	0.0126 (10)	0.0132 (9)	0.0006 (8)	0.0045 (8)	0.0022 (8)
C4	0.0086 (13)	0.0133 (10)	0.0120 (9)	0.0000 (8)	0.0023 (8)	−0.0001 (7)
C3	0.0101 (14)	0.0153 (10)	0.0114 (9)	0.0018 (8)	0.0044 (8)	0.0050 (8)
C2	0.0143 (14)	0.0112 (10)	0.0118 (9)	0.0040 (8)	0.0046 (8)	0.0035 (7)
O1	0.0109 (11)	0.0174 (8)	0.0212 (8)	0.0056 (7)	0.0021 (7)	−0.0023 (6)
O2	0.0097 (10)	0.0202 (8)	0.0177 (7)	0.0050 (7)	0.0024 (6)	0.0006 (6)
Br2	0.01108 (15)	0.01456 (11)	0.01695 (11)	0.00013 (8)	0.00107 (8)	−0.00140 (8)
O3	0.0115 (10)	0.0145 (8)	0.0259 (8)	0.0028 (6)	0.0028 (7)	−0.0038 (6)
O4	0.0117 (10)	0.0202 (8)	0.0220 (8)	0.0041 (7)	−0.0012 (7)	−0.0033 (7)
Br1	0.01622 (16)	0.01440 (11)	0.01679 (11)	0.00185 (9)	0.00011 (9)	−0.00278 (8)
C10	0.0115 (14)	0.0145 (10)	0.0165 (10)	−0.0007 (9)	−0.0003 (9)	0.0033 (8)
C9	0.0094 (14)	0.0203 (11)	0.0175 (10)	0.0042 (9)	0.0043 (9)	0.0052 (9)
C8	0.0182 (15)	0.0146 (10)	0.0126 (9)	0.0049 (9)	0.0028 (9)	0.0020 (8)
C7	0.0138 (14)	0.0128 (10)	0.0156 (10)	0.0014 (9)	−0.0012 (9)	−0.0005 (8)
N1	0.0077 (12)	0.0167 (9)	0.0171 (9)	0.0023 (8)	0.0034 (8)	0.0004 (7)
C11	0.0149 (14)	0.0132 (10)	0.0149 (9)	0.0002 (9)	0.0037 (9)	−0.0010 (8)
C12	0.0264 (16)	0.0267 (13)	0.0187 (11)	0.0071 (11)	0.0036 (10)	−0.0055 (10)
C13	0.0160 (15)	0.0315 (14)	0.0204 (11)	−0.0066 (11)	−0.0008 (10)	0.0020 (10)

Geometric parameters (Å, º)

C1—C2	1.349 (3)	C3—C2	1.522 (3)
C1—C6	1.447 (3)	C2—O1	1.329 (3)
C1—Br1	1.881 (2)	C10—C11	1.379 (3)
C6—O4	1.219 (3)	C10—C9	1.392 (3)
C6—C5	1.554 (3)	C10—C13	1.507 (3)
C5—O3	1.245 (3)	C9—C8	1.394 (3)
C5—C4	1.395 (3)	C8—C7	1.376 (4)
C4—C3	1.412 (3)	C8—C12	1.499 (3)
C4—Br2	1.888 (2)	C7—N1	1.337 (3)
C3—O2	1.240 (3)	N1—C11	1.343 (3)
C2—C1—C6	120.4 (2)	C4—C3—C2	116.9 (2)
C2—C1—Br1	121.94 (17)	O1—C2—C1	122.1 (2)
C6—C1—Br1	117.65 (17)	O1—C2—C3	115.1 (2)
O4—C6—C1	124.0 (2)	C1—C2—C3	122.8 (2)
O4—C6—C5	117.8 (2)	C11—C10—C9	117.6 (2)
C1—C6—C5	118.2 (2)	C11—C10—C13	119.8 (2)
O3—C5—C4	125.8 (2)	C9—C10—C13	122.6 (2)
O3—C5—C6	116.0 (2)	C10—C9—C8	121.7 (2)
C4—C5—C6	118.1 (2)	C7—C8—C9	117.1 (2)
C5—C4—C3	123.3 (2)	C7—C8—C12	120.0 (2)
C5—C4—Br2	117.77 (16)	C9—C8—C12	122.8 (2)
C3—C4—Br2	118.86 (17)	N1—C7—C8	120.9 (2)
O2—C3—C4	127.1 (2)	C7—N1—C11	122.5 (2)
O2—C3—C2	115.96 (19)	N1—C11—C10	120.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O3^i	0.93 (3)	1.84 (3)	2.677 (3)	148 (3)
N1—H2···O4^i	0.93 (3)	2.37 (3)	3.008 (3)	125 (3)
O1—H1···O2^ii	0.72 (3)	2.11 (3)	2.768 (3)	152 (3)
O1—H1···O2	0.72 (3)	2.23 (3)	2.631 (2)	116 (3)

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

(ba_3br4mepyr) 3-Bromo-4-methylpyridinium bromanilate

Crystal data

C6H7BrN^+·C6HBr2O4^−	Z = 4
Mr = 469.91	F(000) = 896
Monoclinic, P21/c	Dx = 2.244 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.2229 (4) Å	µ = 8.71 mm^−1
b = 5.5760 (2) Å	T = 100 K
c = 24.5300 (9) Å	Block, purple
β = 95.802 (3)°	0.25 × 0.15 × 0.1 mm
V = 1391.12 (9) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	3311 reflections with I > 2σ(I)
CCD; rotation images scans	Rint = 0.057
Absorption correction: multi-scan (SADABS; Blessing, 1995)	θmax = 32.2°, θmin = 1.7°
Tmin = 0.499, Tmax = 1.000	h = −15→15
19916 measured reflections	k = −8→6
4796 independent reflections	l = −36→36

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0482P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
4796 reflections	Δρmax = 1.23 e Å^−3
190 parameters	Δρmin = −1.13 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
C4	0.2394 (3)	0.2669 (7)	0.91013 (13)	0.0159 (7)
C3	0.1456 (3)	0.1217 (7)	0.93350 (13)	0.0167 (7)
C2	0.0747 (3)	−0.0693 (7)	0.89770 (13)	0.0168 (7)
C1	0.1034 (3)	−0.1083 (7)	0.84602 (13)	0.0157 (7)
C6	0.2048 (3)	0.0288 (7)	0.82360 (13)	0.0158 (7)
C5	0.2691 (3)	0.2388 (7)	0.85643 (13)	0.0158 (7)
O3	0.3444 (3)	0.3718 (5)	0.83178 (9)	0.0205 (6)
O4	0.2426 (3)	−0.0150 (5)	0.77843 (9)	0.0200 (6)
Br1	0.01728 (3)	−0.34997 (7)	0.80172 (2)	0.01880 (10)
O1	−0.0141 (3)	−0.1955 (5)	0.92133 (10)	0.0217 (6)
O2	0.1142 (2)	0.1390 (5)	0.98099 (9)	0.0203 (6)
Br2	0.31926 (4)	0.51666 (7)	0.95403 (2)	0.01953 (10)
C8	0.7096 (3)	0.1138 (7)	0.86016 (14)	0.0171 (7)
C9	0.6171 (3)	−0.0257 (7)	0.88470 (13)	0.0174 (7)
C10	0.5522 (4)	−0.2030 (7)	0.85268 (14)	0.0201 (8)
H10	0.49	−0.2991	0.8673	0.024*
C11	0.5796 (4)	−0.2372 (7)	0.79908 (14)	0.0211 (8)
H11	0.538	−0.3595	0.7782	0.025*
N1	0.6657 (3)	−0.0950 (6)	0.77734 (13)	0.0208 (7)
C7	0.7321 (4)	0.0788 (7)	0.80625 (14)	0.0194 (8)
H7	0.7924	0.1739	0.7902	0.023*
C12	0.5888 (4)	0.0144 (8)	0.94276 (14)	0.0240 (9)
H12A	0.5601	0.1767	0.947	0.036*
H12B	0.6671	−0.0138	0.9669	0.036*
H12C	0.521	−0.0939	0.9516	0.036*
Br3	0.80539 (4)	0.35718 (7)	0.89969 (2)	0.02332 (10)
H1	−0.027 (4)	−0.120 (8)	0.9513 (18)	0.031 (13)*
H5	0.681 (5)	−0.102 (9)	0.746 (2)	0.039 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C4	0.0167 (16)	0.020 (2)	0.0113 (15)	−0.0020 (14)	0.0024 (11)	−0.0030 (13)
C3	0.0160 (16)	0.024 (2)	0.0099 (14)	0.0002 (14)	0.0005 (11)	0.0011 (13)
C2	0.0186 (17)	0.017 (2)	0.0146 (16)	0.0008 (14)	0.0012 (12)	0.0012 (13)
C1	0.0190 (17)	0.015 (2)	0.0127 (15)	−0.0025 (14)	0.0012 (12)	−0.0008 (13)
C6	0.0162 (16)	0.020 (2)	0.0117 (15)	0.0027 (14)	0.0027 (12)	0.0014 (13)
C5	0.0174 (16)	0.017 (2)	0.0130 (15)	−0.0007 (14)	0.0032 (12)	0.0012 (13)
O3	0.0263 (14)	0.0234 (16)	0.0124 (11)	−0.0063 (11)	0.0055 (9)	0.0011 (10)
O4	0.0253 (13)	0.0241 (16)	0.0116 (11)	−0.0030 (11)	0.0069 (9)	−0.0005 (10)
Br1	0.02324 (18)	0.0218 (2)	0.01161 (15)	−0.00572 (15)	0.00313 (12)	−0.00253 (13)
O1	0.0270 (14)	0.0285 (17)	0.0109 (11)	−0.0101 (12)	0.0085 (10)	−0.0047 (11)
O2	0.0224 (13)	0.0304 (17)	0.0088 (11)	−0.0073 (11)	0.0052 (9)	−0.0036 (10)
Br2	0.02441 (18)	0.0226 (2)	0.01180 (15)	−0.00683 (15)	0.00318 (12)	−0.00302 (14)
C8	0.0183 (17)	0.019 (2)	0.0146 (15)	−0.0029 (14)	0.0028 (12)	0.0006 (13)
C9	0.0184 (17)	0.020 (2)	0.0132 (15)	−0.0006 (14)	0.0009 (12)	0.0007 (14)
C10	0.0229 (18)	0.023 (2)	0.0154 (16)	−0.0045 (15)	0.0065 (13)	−0.0004 (14)
C11	0.0223 (18)	0.023 (2)	0.0178 (17)	0.0000 (16)	0.0008 (13)	−0.0060 (15)
N1	0.0246 (16)	0.025 (2)	0.0134 (14)	0.0067 (14)	0.0058 (12)	0.0001 (13)
C7	0.0212 (18)	0.021 (2)	0.0162 (16)	0.0007 (15)	0.0044 (13)	0.0009 (14)
C12	0.029 (2)	0.033 (3)	0.0117 (15)	−0.0061 (17)	0.0074 (13)	−0.0020 (15)
Br3	0.0249 (2)	0.0231 (2)	0.02254 (19)	−0.00646 (16)	0.00484 (14)	−0.00396 (15)

Geometric parameters (Å, º)

C4—C5	1.390 (4)	C6—C5	1.531 (5)
C4—C3	1.420 (5)	C5—O3	1.266 (4)
C4—Br2	1.894 (4)	C8—C7	1.379 (5)
C3—O2	1.243 (4)	C8—C9	1.406 (5)
C3—C2	1.517 (5)	C8—Br3	1.884 (4)
C2—O1	1.327 (4)	C9—C10	1.389 (5)
C2—C1	1.347 (5)	C9—C12	1.499 (5)
C1—C6	1.442 (5)	C10—C11	1.385 (5)
C1—Br1	1.892 (3)	C11—N1	1.335 (5)
C6—O4	1.234 (4)	N1—C7	1.344 (5)
C5—C4—C3	122.7 (3)	C1—C6—C5	119.5 (3)
C5—C4—Br2	119.9 (3)	O3—C5—C4	126.0 (3)
C3—C4—Br2	117.4 (2)	O3—C5—C6	116.5 (3)
O2—C3—C4	125.7 (3)	C4—C5—C6	117.5 (3)
O2—C3—C2	116.3 (3)	C7—C8—C9	121.2 (3)
C4—C3—C2	118.0 (3)	C7—C8—Br3	117.8 (3)
O1—C2—C1	123.3 (3)	C9—C8—Br3	121.0 (3)
O1—C2—C3	115.3 (3)	C10—C9—C8	117.1 (3)
C1—C2—C3	121.4 (3)	C10—C9—C12	121.1 (3)
C2—C1—C6	120.4 (3)	C8—C9—C12	121.8 (3)
C2—C1—Br1	121.5 (3)	C11—C10—C9	120.3 (3)
C6—C1—Br1	118.0 (2)	N1—C11—C10	120.2 (4)
O4—C6—C1	122.7 (3)	C11—N1—C7	122.4 (3)
O4—C6—C5	117.9 (3)	N1—C7—C8	118.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.87 (5)	1.97 (5)	2.717 (3)	144 (4)
O1—H1···O2	0.87 (5)	2.12 (4)	2.637 (4)	118 (4)
N1—H5···O3^ii	0.79 (5)	1.91 (5)	2.675 (4)	161 (5)
N1—H5···O4^ii	0.79 (5)	2.53 (5)	2.915 (4)	112 (4)

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

(ba23lut) 2,3-Dimethylpyridinium bromanilate

Crystal data

C7H10N^+·C6HBr2O4^−	Z = 4
Mr = 405.04	F(000) = 792
Monoclinic, P21/n	Dx = 1.932 Mg m^−3
a = 4.9786 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 23.181 (3) Å	µ = 5.83 mm^−1
c = 12.2811 (13) Å	T = 100 K
β = 100.794 (3)°	Block, purple
V = 1392.3 (2) Å^3	0.2 × 0.1 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1664 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
CCD; rotation images scans	θmax = 23.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −5→5
Tmin = 0.791, Tmax = 1.000	k = −26→25
9783 measured reflections	l = −13→13
2053 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0301P)^2 + 0.8134P] where P = (Fo^2 + 2Fc^2)/3
2053 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

All H atoms were placed on calculated positions and refined as riding on the atom to which they were bonded with the exception of H1 where the position was allowed to freely refine but the thermal parameter was constrained to take a value of 1.2 times the U_eq of the atom to which it was bonded (O1).

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

	x	y	z	Uiso*/Ueq
C1	0.6253 (8)	0.29473 (17)	0.0801 (3)	0.0161 (9)
C2	0.6786 (8)	0.29433 (17)	0.1910 (3)	0.0163 (9)
C3	0.5234 (8)	0.33215 (18)	0.2594 (3)	0.0182 (10)
C4	0.3191 (8)	0.36859 (17)	0.2012 (3)	0.0174 (10)
C5	0.2523 (8)	0.37123 (17)	0.0857 (3)	0.0173 (9)
C6	0.4239 (8)	0.33427 (17)	0.0198 (3)	0.0174 (10)
O4	0.3842 (6)	0.33949 (12)	−0.0808 (2)	0.0226 (7)
O3	0.0655 (6)	0.40095 (12)	0.0294 (2)	0.0232 (7)
Br2	0.11288 (8)	0.413330 (18)	0.28551 (3)	0.02328 (15)
O2	0.5924 (6)	0.32675 (12)	0.3614 (2)	0.0226 (7)
O1	0.8656 (6)	0.25996 (12)	0.2500 (2)	0.0222 (7)
H1	0.8817	0.2679	0.316	0.033*
Br1	0.81832 (8)	0.247086 (17)	−0.00350 (3)	0.01960 (14)
C7	0.6455 (8)	0.43225 (18)	−0.2235 (3)	0.0188 (10)
C8	0.5129 (8)	0.43486 (17)	−0.3345 (3)	0.0179 (9)
C9	0.5929 (9)	0.39720 (18)	−0.4105 (3)	0.0226 (10)
H9	0.5042	0.3981	−0.4842	0.027*
C10	0.8046 (8)	0.35822 (19)	−0.3772 (3)	0.0260 (11)
H10	0.8596	0.3333	−0.4281	0.031*
C11	0.9303 (8)	0.35721 (18)	−0.2685 (3)	0.0220 (10)
H11	1.0725	0.3315	−0.2447	0.026*
N1	0.8484 (7)	0.39346 (15)	−0.1956 (3)	0.0211 (8)
H1A	0.93	0.3918	−0.1274	0.025*
C13	0.2859 (9)	0.47821 (18)	−0.3707 (4)	0.0270 (11)
H13A	0.2121	0.473	−0.4481	0.041*
H13B	0.3577	0.5166	−0.3586	0.041*
H13C	0.1441	0.4725	−0.3285	0.041*
C12	0.5747 (9)	0.46959 (18)	−0.1333 (3)	0.0244 (10)
H12A	0.6972	0.4613	−0.0649	0.037*
H12B	0.3902	0.4619	−0.125	0.037*
H12C	0.5915	0.5094	−0.1522	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.017 (2)	0.016 (2)	0.016 (2)	−0.0026 (18)	0.0050 (18)	−0.0026 (18)
C2	0.015 (2)	0.015 (2)	0.019 (2)	−0.0042 (19)	0.0012 (18)	0.0037 (19)
C3	0.018 (2)	0.019 (2)	0.019 (3)	−0.0088 (19)	0.0044 (19)	−0.0001 (19)
C4	0.015 (2)	0.017 (2)	0.021 (2)	−0.0028 (18)	0.0053 (18)	−0.0057 (19)
C5	0.014 (2)	0.018 (2)	0.020 (2)	−0.0024 (19)	0.0030 (18)	−0.001 (2)
C6	0.018 (2)	0.013 (2)	0.020 (3)	−0.0045 (18)	0.0005 (19)	−0.0008 (19)
O4	0.0213 (17)	0.0315 (18)	0.0144 (17)	0.0028 (13)	0.0022 (12)	0.0009 (13)
O3	0.0213 (17)	0.0252 (17)	0.0208 (16)	0.0035 (14)	−0.0015 (13)	−0.0016 (14)
Br2	0.0204 (3)	0.0277 (3)	0.0230 (3)	−0.0018 (2)	0.00735 (18)	−0.0073 (2)
O2	0.0240 (17)	0.0306 (18)	0.0128 (16)	−0.0069 (14)	0.0021 (13)	0.0015 (13)
O1	0.0238 (17)	0.0273 (18)	0.0137 (15)	0.0049 (14)	−0.0008 (13)	0.0021 (14)
Br1	0.0197 (3)	0.0216 (3)	0.0173 (2)	0.00247 (19)	0.00311 (17)	−0.0020 (2)
C7	0.015 (2)	0.019 (2)	0.024 (2)	−0.0028 (19)	0.0073 (18)	−0.001 (2)
C8	0.014 (2)	0.016 (2)	0.022 (2)	−0.0031 (18)	−0.0009 (18)	−0.0011 (19)
C9	0.023 (3)	0.026 (3)	0.017 (2)	−0.001 (2)	−0.0019 (18)	−0.001 (2)
C10	0.024 (3)	0.031 (3)	0.022 (3)	0.001 (2)	0.003 (2)	−0.006 (2)
C11	0.021 (3)	0.023 (3)	0.020 (2)	0.006 (2)	−0.0002 (19)	0.001 (2)
N1	0.018 (2)	0.027 (2)	0.0167 (19)	−0.0008 (17)	−0.0005 (15)	−0.0006 (17)
C13	0.022 (3)	0.028 (3)	0.029 (3)	0.005 (2)	0.002 (2)	0.000 (2)
C12	0.026 (3)	0.023 (3)	0.026 (2)	0.002 (2)	0.009 (2)	−0.002 (2)

Geometric parameters (Å, º)

C1—C2	1.338 (5)	C5—C6	1.542 (6)
C1—C6	1.455 (6)	C6—O4	1.220 (5)
C1—Br1	1.889 (4)	C7—N1	1.348 (5)
C2—O1	1.332 (4)	C7—C8	1.399 (6)
C2—C3	1.522 (6)	C7—C12	1.499 (5)
C3—O2	1.242 (4)	C8—C9	1.390 (6)
C3—C4	1.409 (6)	C8—C13	1.515 (6)
C4—C5	1.397 (5)	C9—C10	1.391 (6)
C4—Br2	1.897 (4)	C10—C11	1.364 (5)
C5—O3	1.255 (5)	C11—N1	1.346 (5)
C2—C1—C6	120.6 (4)	C4—C5—C6	117.3 (4)
C2—C1—Br1	121.7 (3)	O4—C6—C1	122.9 (4)
C6—C1—Br1	117.7 (3)	O4—C6—C5	118.4 (4)
O1—C2—C1	122.9 (4)	C1—C6—C5	118.7 (3)
O1—C2—C3	114.8 (3)	N1—C7—C8	118.1 (4)
C1—C2—C3	122.3 (4)	N1—C7—C12	117.7 (4)
O2—C3—C4	127.5 (4)	C8—C7—C12	124.1 (4)
O2—C3—C2	115.2 (4)	C9—C8—C7	119.0 (4)
C4—C3—C2	117.3 (3)	C9—C8—C13	120.7 (4)
C5—C4—C3	123.6 (4)	C7—C8—C13	120.3 (4)
C5—C4—Br2	118.7 (3)	C8—C9—C10	120.5 (4)
C3—C4—Br2	117.6 (3)	C11—C10—C9	118.9 (4)
O3—C5—C4	126.4 (4)	N1—C11—C10	120.0 (4)
O3—C5—C6	116.2 (3)	C11—N1—C7	123.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.13	2.611 (4)	117
O1—H1···Br1^i	0.82	2.82	3.423 (3)	132
N1—H1A···O3^ii	0.86	1.93	2.777 (4)	168
N1—H1A···O4^ii	0.86	2.54	3.043 (4)	119

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

(ba_2br3mepyr) 2-Bromo-3-methylpyridine–bromanilic acid (1/1)

Crystal data

C6H6BrN·C6H2Br2O4	Z = 4
Mr = 469.91	F(000) = 896
Monoclinic, P21/c	Dx = 2.168 Mg m^−3
a = 5.2866 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.3814 (8) Å	µ = 8.42 mm^−1
c = 20.3576 (13) Å	T = 100 K
β = 91.556 (4)°	Block, red
V = 1439.61 (15) Å^3	0.25 × 0.2 × 0.1 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2267 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
CCD; rotation images scans	θmax = 27.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −6→5
Tmin = 0.465, Tmax = 1.000	k = −17→17
14350 measured reflections	l = −26→26
3202 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0324P)^2] where P = (Fo^2 + 2Fc^2)/3
3202 reflections	(Δ/σ)max = 0.001
188 parameters	Δρmax = 0.77 e Å^−3
1 restraint	Δρmin = −0.67 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

All H atoms were placed on calculated positions and modelled as riding on the atoms to which they were bonded except H1 and H2. H1 was constrained to take a thermal parameter 1.2 times the U_eq of the atom to which it was bonded (O1) to ensure that a sensible thermal parameter was obtained. The methyl group positons were based on the electron density but with the bond lengths and angles constrained to take standard values for a methyl group.

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

	x	y	z	Uiso*/Ueq
C1	0.6951 (8)	0.5218 (3)	0.4532 (2)	0.0142 (10)
C3	0.6017 (8)	0.5990 (3)	0.4964 (2)	0.0153 (10)
C2	0.6005 (8)	0.4285 (3)	0.4553 (2)	0.0134 (10)
O1	0.6758 (6)	0.3552 (2)	0.41693 (17)	0.0226 (8)
O2	0.6701 (6)	0.6863 (2)	0.49613 (16)	0.0244 (8)
Br1	0.95526 (9)	0.55598 (3)	0.39596 (2)	0.01783 (14)
C4	0.6894 (8)	0.0737 (3)	0.5152 (2)	0.0149 (10)
C6	0.5333 (8)	0.0834 (3)	0.4566 (2)	0.0148 (10)
C5	0.3339 (8)	0.0032 (3)	0.4423 (2)	0.0141 (10)
O3	0.1920 (6)	0.0119 (2)	0.38894 (16)	0.0188 (8)
O4	0.5461 (6)	0.1528 (2)	0.41714 (16)	0.0190 (7)
Br2	0.93951 (9)	0.17269 (3)	0.52850 (2)	0.01781 (14)
C7	0.3385 (8)	0.1755 (3)	0.2548 (2)	0.0169 (11)
C8	0.3281 (9)	0.2589 (4)	0.2135 (2)	0.0205 (11)
C9	0.1496 (9)	0.3294 (4)	0.2290 (2)	0.0244 (12)
H9	0.1296	0.3858	0.2027	0.029*
C10	0.0000 (9)	0.3180 (3)	0.2830 (2)	0.0239 (12)
H10	−0.1194	0.3661	0.2933	0.029*
C11	0.0310 (9)	0.2333 (4)	0.3214 (2)	0.0233 (12)
H11	−0.0658	0.2259	0.3586	0.028*
N1	0.1966 (7)	0.1620 (3)	0.30642 (18)	0.0161 (9)
C12	0.4994 (9)	0.2719 (4)	0.1563 (2)	0.0308 (13)
H12A	0.4070	0.2577	0.1162	0.046*
H12B	0.6400	0.2268	0.1609	0.046*
H12C	0.5604	0.3394	0.1554	0.046*
Br3	0.56870 (10)	0.06825 (4)	0.23905 (3)	0.02778 (16)
H1	0.601 (8)	0.301 (2)	0.427 (2)	0.033*
H2	0.227 (10)	0.064 (4)	0.361 (3)	0.042 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.013 (3)	0.018 (2)	0.012 (2)	−0.0009 (19)	0.0048 (19)	0.0018 (19)
C3	0.014 (3)	0.015 (2)	0.018 (3)	0.0006 (19)	0.001 (2)	0.005 (2)
C2	0.012 (3)	0.013 (2)	0.015 (2)	−0.0030 (18)	0.0001 (19)	0.0026 (19)
O1	0.028 (2)	0.0113 (17)	0.029 (2)	−0.0051 (15)	0.0139 (16)	−0.0011 (15)
O2	0.029 (2)	0.0144 (19)	0.030 (2)	−0.0055 (15)	0.0083 (16)	−0.0055 (15)
Br1	0.0156 (3)	0.0173 (3)	0.0208 (3)	−0.00355 (18)	0.0055 (2)	0.0019 (2)
C4	0.015 (3)	0.013 (2)	0.017 (2)	−0.0071 (18)	0.004 (2)	−0.0015 (19)
C6	0.009 (3)	0.013 (2)	0.022 (3)	0.0018 (18)	0.005 (2)	−0.001 (2)
C5	0.015 (3)	0.011 (2)	0.017 (3)	−0.0012 (19)	0.005 (2)	−0.002 (2)
O3	0.021 (2)	0.0135 (18)	0.022 (2)	−0.0048 (14)	−0.0002 (16)	0.0040 (15)
O4	0.023 (2)	0.0131 (17)	0.0206 (18)	−0.0049 (14)	0.0025 (15)	0.0047 (14)
Br2	0.0172 (3)	0.0130 (2)	0.0234 (3)	−0.00624 (19)	0.0034 (2)	−0.0012 (2)
C7	0.011 (3)	0.018 (3)	0.022 (3)	−0.0001 (19)	−0.002 (2)	−0.002 (2)
C8	0.021 (3)	0.026 (3)	0.014 (3)	−0.007 (2)	−0.004 (2)	−0.003 (2)
C9	0.030 (3)	0.019 (3)	0.024 (3)	−0.008 (2)	−0.001 (2)	0.004 (2)
C10	0.025 (3)	0.017 (3)	0.029 (3)	0.003 (2)	0.003 (2)	−0.004 (2)
C11	0.025 (3)	0.025 (3)	0.020 (3)	−0.001 (2)	0.007 (2)	0.001 (2)
N1	0.019 (2)	0.013 (2)	0.017 (2)	−0.0002 (16)	−0.0008 (17)	−0.0014 (17)
C12	0.029 (3)	0.044 (3)	0.019 (3)	−0.008 (3)	0.001 (2)	0.014 (3)
Br3	0.0233 (3)	0.0317 (3)	0.0284 (3)	0.0097 (2)	0.0017 (2)	−0.0022 (2)

Geometric parameters (Å, º)

C1—C2	1.346 (6)	O3—H2	0.92 (5)
C1—C3	1.453 (6)	C7—N1	1.321 (6)
C1—Br1	1.882 (4)	C7—C8	1.397 (6)
C3—O2	1.223 (5)	C7—Br3	1.914 (4)
C3—C2^i	1.517 (6)	C8—C9	1.378 (7)
C2—O1	1.322 (5)	C8—C12	1.504 (7)
C2—C3^i	1.517 (6)	C9—C10	1.379 (7)
O1—H1	0.857 (19)	C9—H9	0.9300
C4—C5^ii	1.353 (6)	C10—C11	1.384 (6)
C4—C6	1.437 (6)	C10—H10	0.9300
C4—Br2	1.886 (4)	C11—N1	1.336 (6)
C6—O4	1.230 (5)	C11—H11	0.9300
C6—C5	1.527 (6)	C12—H12A	0.9600
C5—O3	1.308 (5)	C12—H12B	0.9600
C5—C4^ii	1.353 (6)	C12—H12C	0.9600
C2—C1—C3	120.5 (4)	N1—C7—Br3	114.1 (3)
C2—C1—Br1	121.6 (3)	C8—C7—Br3	120.9 (4)
C3—C1—Br1	117.9 (3)	C9—C8—C7	115.2 (4)
O2—C3—C1	124.9 (4)	C9—C8—C12	121.9 (4)
O2—C3—C2^i	116.6 (4)	C7—C8—C12	122.9 (4)
C1—C3—C2^i	118.5 (4)	C8—C9—C10	121.2 (5)
O1—C2—C1	123.4 (4)	C8—C9—H9	119.4
O1—C2—C3^i	115.6 (4)	C10—C9—H9	119.4
C1—C2—C3^i	121.0 (4)	C9—C10—C11	118.7 (5)
C2—O1—H1	110 (4)	C9—C10—H10	120.7
C5^ii—C4—C6	122.7 (4)	C11—C10—H10	120.7
C5^ii—C4—Br2	121.2 (3)	N1—C11—C10	121.6 (5)
C6—C4—Br2	116.1 (3)	N1—C11—H11	119.2
O4—C6—C4	124.7 (4)	C10—C11—H11	119.2
O4—C6—C5	117.1 (4)	C7—N1—C11	118.3 (4)
C4—C6—C5	118.2 (4)	C8—C12—H12A	109.5
O3—C5—C4^ii	122.6 (4)	C8—C12—H12B	109.5
O3—C5—C6	118.3 (4)	H12A—C12—H12B	109.5
C4^ii—C5—C6	119.1 (4)	C8—C12—H12C	109.5
C5—O3—H2	117 (3)	H12A—C12—H12C	109.5
N1—C7—C8	125.1 (4)	H12B—C12—H12C	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.86 (2)	2.01 (3)	2.794 (4)	151 (5)
O1—H1···O2^i	0.86 (2)	2.15 (5)	2.638 (5)	115 (4)
O3—H2···N1	0.92 (5)	1.73 (5)	2.619 (5)	163 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.