Chemistry:Bromoantimonates

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Short description: Chemical compounds

Bromoantimonates are compounds containing anions composed of bromide (Br) and antimony (Sb). They can be considered as double bromides, metallohalides or halometallates. They are in the category of halopnictates. Related compounds include the bromobismuthates, iodoantimonates, bromophosphates, and bromoarsenates.

Some examples of bromoantimonates

Bromoantimonates can have antimony in one of two oxidation states, either +3 or +5. These are designated by bromoantimonate(III) or bromoantimonate(V). Although antimony tribromide is known, SbBr5 on its own does not exist, despite the existence of SbRb
6
.[1] Compounds containing both Sb(III) and Sb(V) are mixed valence compounds. The antimony can be linked into chains, (which are called one-dimensional as it is like a line), or in pairs as Sb2 or singly as Sb (which are called zero-dimensional, as the anions are just point-like).

Tetrabromoantimonate(III) (SbBr4) has single antimony atoms in each anion.[2]

SbBr52− contains infinite chains of SbBr6 octahedra linked by corners.[3]

Hexabromoantimonate(III) SbBr63− also exists, forming zero-dimensional compounds.[4]

Nonabromodiantimonate(III) Sb2Br93− has a pair of octahedra of SbBr6 sharing a face. The angles formed by shared bromine at the antimony are reduced from the theoretical 90° to about 80°.[5]

Hexabromoantimonate(V) SbBr6 exists in equilibrium with SbBr4 and Br2 but real +5 oxidation state bromoantimonates exist even if SbBr5 is unstable and does not exist.[6][7] [8]

Intersecting classes are nonahalogenodiantimon(III)ates. Hexahaloantimonate(III) ions (SbX63−) can include chlorine or iodine as well as bromine.[9]

Related classes include halogeno-oxydiantimon(III)ates, and pentabromothio‐diantimonates.[10] Bromo-phenylantimonates(V) (C6H5SbBr5) have a phenyl group substituting for one bromine atom.[11] Chlorobromoantimonates(V) have some chlorine instead of bromine.[12]

The antimonide bromides are distinct as they do not have a bond between antimony and bromine. Tetrabromostibonium(V) contains cations (SbBr+
4
) rather than anions.[13]

Preparation

Bromoantimonates can be made using a water solution of antimony tribromide, hydrobromic acid, and an amine. Alternately antimony trioxide can be used. Variants can be made without using water, and heating the antimony tribromide with an amine hydrobromide.[14]

Some properties

Most of the bromoantimonate salts are yellow or orange.[15]

For SbBr
4
there are absorption bands at 224, 300, 245 and 216 nm. SbBr3−
6
has absorption bands centred on 359, 311, and 266 nm.[16]

Many alkylammonium salts are known. These can have different solid phases at different temperatures, as the alkyl group varies in disorder. Those with longer alkyl chains have a greater number of solid state phases.[17]

Methyl ammonium compounds are ferroelectric.[17]

The infrared spectrum includes wavenumbers (ν/c) of 110 to 130 cm−1 for the bridging bromine in Sb2Br9 and 135 to 220 cm−1 for non-bridging bromine to antimony stretching.[18]

Bond lengths in SbBr6 are 2.65 and 2.56 Å. In SbBr63− the lengths are greater, from 2.787 to 2.713 Å.[19]

Use

Bromoantimonates are researched for use in photovoltaics,[20] X-ray detectors,[21] and LEDs.[22]

List

Name (full or part) Formula System Space group Unit cell (Å) Volume Density Notes Ref
ammonium [H4N]2SbBr6 tetragonal I41/amd a=10.66 c=21.52 black; Sb(III) and Sb(V) [7][23]
ammonium (NH4)3Sb2Br9 inefficient photovoltaic; soluble in ethanol [24]
ammonium (NH4)7Sb3Br16 [25]
guanidinium [C(NH2)3]SbBr6 black; Sb(V) [26]
guanidinium [C(NH2)3]3Sb2Br9 monoclinic C2/c a = 15.695 b = 9.039 c = 18.364 β = 96.94° Z=4 @143K; phase transition 435/450 K [27][28]
Tris(N,N,N',N'-tetramethylguanidinium) nonabromodiantimonate(III) [NH2C(N(CH3)2)2]3[Sb2Br9] triclinic P1 a 10.9824 b 12.1782 c 15.0405 α 71.064° β 88.199° γ 85.024° [29]
methylammonium (CH3NH3)3SbBr6 monoclinic P21/c a=13.577 b=8.254 c=21.665 β=134.05° Z=4 [30]
methylammonium bromoantimonate(III) (CH3NH3)3Sb2Br9 P3m1 a=8.188 c=9.927 Z=1 3.049 yellow [31][32]
dimethyl ammonium [(CH3)2NH2]3SbBr6 [30]
tris (dimethylammonium) nonabromodiantimonate(III) [(CH3)2NH2]3Sb2Br9 monoclinic P21/a a = 14.612 b = 9.228 c = 10.005 β = 94.91° Z = 2 [33]
[NH2(CH3)2]3Sb2Br9
tris(Trimethylammonium) nonabromodiantimonate(III) [(CH3)3NH]3Sb2Br9 orthorhomic a 11.40 b 10.31 c 12.91 [34]
tetramethylammonium [NMe4]3[Sb2Br9] hexagonal P63/mmc a=9.499 c=22.225 Z=2 crimson red [35][36]
tetramethylammonium [NMe4]3[Sb2Br9]•Br2 hexagonal P63/mmc a=9.585 c=22.667 Z=2 [37]
tetramethylammonium [(CH3)4N]3Sb3Br9•Br2 hexagonal P63/mmc a=9.5850 c=22.667 Z=2 2.48 red; yellow-orange when cold [38]
tetramethylammonium [(CH3)4N]3Sb2Br9•I2 triclinic P1 a=9.4869 b=9.5409 c=22.4906 α=92.058° β=90.933° γ=118.386° Z=2 1788.5 dark [39]
ethylammonium (C2H5NH3)2[SbBr5] orthorhombic Cmca a= 7.815 b=22.301 c=18.100 Z=8 3154.5 2.584 at 298K; yellow; phase transition at 158.5K; decompose >450K [15][30]
ethylammonium (C2H5NH3)2[SbBr5] orthorhombic Pbca a=7.684 b=22.413 c=17.780 Z=8 3062.1 2.661 at 90K; yellow [15]
ethylammonium (C2H5NH3)2[SbBr7] [40]
diethylammonium ([C2H5]2NH2)3SbBr6 hexagonal R3c a=15.155 c=20.085 Z=6 dissolves in acetone [41][34]
tetraethylammonium [(C2H5)4N]2SbBr6 very dark reddish brown [7]
tetraethylammonium [(C2H5)4N]3Sb2Br9 hexagonal P6322 a=10.3 c=24.4 Z=2 2242 2.02 yellow [42][43]
tetraethylammonium hexabromoantimonate(V) [(C2H5)4N]SbBr6 tetragonal I41md a=8.7008 c=24.797 Z=4 1877.3 2.59 dark red-brown [44][45]
n-propylammonium (n-C3H7NH3)2SbBr5 orthorhombic ? a =7.884 b=14.516 c=15.913 Z=4 1821.1 2.33 4 phase transitions: 189K, 165/163, 137/154 [46][30][47]
di-n-propylammonium [(n-C3H7)2NH2]3SbBr6 hexagonal R3c a=13.649 c=31.548 Z=6 dissolves in acetone [41]
tris(Tri-n-propylammonium) nonabromodiantimonate(III) [(n-C3H7)3NH]3Sb2Br9 orthorhombic ? a 12.91 b 14.51 c 20.0 [34]
bis(Isopropylammonium) pentabromoantimonate(III) [(i-C3H7)2NH2]2SbBr5 orthorhombic a 14.99 b 16.687 c 21.72 [34]
tetrapropylammonium [(C3H7)4N][SbBr4] orthorhombic Pbca a=15.566 b=13.822 c=19.574 Z=8 4211.5 yellow [48]
isopropylammonium [(CH3)2CHNH3]2SbBr5 orthorhombic a=12.013 b =12.134 c=12.525 phase transition at 171K, 180 K [49]
isopropylammonium [(CH3)2CHNH3]2SbBr5 monoclinic [50]
tris(N-ethyl-N,N-dipropylpropan-1-aminium) tetrakis(μ-bromo)-octabromo-tri-antimony (Et(n-Pr)3N)3[Sb3Br12] triclinic P1 a 10.6469 b 14.8847 c 18.3714 α 86.082° β 85.502° γ 84.116° [51]
isobutyl (i-C4H9NH3)2SbBr5 [52]
ethanediammonium [NH3(CH2)2NH3]5(Sb2Br11)2·4H2O monoclinic P21/a a = 14.346 b = 13.206 c = 17.027 β = 113.05° Z = 2 2.941 [53]
N,N,N',N'-tetramethylethylendiammonium [tetrabromidoantimonate(III)-μ-bromido] hemihydrate (C6H18N2)2[Sb2Br10]·H2O orthorhombic Pbca a = 18.0860 b = 19.1755 c = 19.4619 Z=8 6749.5 2.553 yellow [54]
anilinium (C6H5NH3)2SbBr5 orthorhombic Pbca a = 19.704 b = 7.914 c = 25.556, Z = 8 3985 2.365 yellow green; insoluble water [3]
dihydrazinium pentabromoantimonite (N2H5)2SbBr5 yellow [25]
Trihydrazinium nonabromodiantimonite (N2H5)3Sb2Br9 yellow [25]
Undecahydrazinium heptadecabromodiantimonite (N2H5)11Sb2Br17 yellow; melt 165° [25]
Decahydrazinium nonadecabromotriantimonite (N2H5)10Sb3Br19 yellow [25]
triazolinium (C2H4N3)2[SbBr5]·(C2H4N3)Br orthorhombic P212121 a=8.6087 b=11.7985 c=20.5457 [55]
1,2,4-triazolium (C2N3H4)3[SbBr6] tetragonal P42/m a=11.149 c=8.318 Z=2 1033.9 2.606 @320K [56]
1,2,4-triazolium (C2N3H4)3[SbBr6] monoclinic a=15.699 b=16.294 c=15.018 β = 90.41 Z=8 4097 2.631 @293K
allylammonium (C3H5NH3)3SbBr6 monoclinic C2/m 4 phases [57]
butylammonium [n-C4H9NH3]2•[SbBr5] orthorhombic Pnma a=16.845 b=54.899 c=15.697 340K deep yellow; 3 phases [58]
butylammonium [n-C4H9NH3]2•[SbBr5] monoclinic P2/m a=15.597, b=62.854, c=16.771 β=92.05° 300K [58]
tris(n-Butylammonium) hexabromo-antimony(III) [n-C4H9NH3]3•[SbBr6] a 11.47 b 15.07 c 18.57 [34]
di-n-butylammonium [(n-C4H9)2NH2]3•[SbBr6] monoclinic P21/c a 13.03 b 13.51 c 18.94 β 94.0° [30][34]
tetra-n-butylammonium hexa-bromoantimonate(V) [(n-C4H9)4N]•[SbBr6] [44]
pentylammonium [n-C5H11NH3]2•[SbBr5] orthorhombic Pna21 a=17.0105 b=32.875 c=7.8882 298K; 3 phases transitions at 388K 224K [17]
pentylammonium [n-C5H11NH3]2•[SbBr5] orthorhombic P212121 a=16.9234 b=32.3689 c=7.7418 86K [17]
2,2-difluoroethylammonium [C2H6F2N]3SbBr6 monoclinic P121/n1 a=8.0145 b=12.1192 c=21.2967 β=91.686 Z=4 2067.6 2.722 yellow [59]
N-ethyl-1,3-propanediammonium [C5N2H16]2SbBr5 monoclinic P21/c a=21.426 b=7.889 c=19.96 β=116.79° Z=8 3012 [60]
N-ethyl-1,3-propanediammonium [C5N2H16]2SbBr5 orthorhombic Pnma a=19.23 b=7.894 c=10.118 Z=4 1536 yellow [60]
bis(N,N-diethylethylendiammonium) decabromodiantimoinate(III) [C6H18N2]2Sb2Br10 monoclinic P21/c a = 10.7309 b = 10.5842 c = 14.5551 β = 96.962° Z = 4. yellow [61]
1,5-pentanediammonium pentabromoantimonate (III) [NH3(CH2)5NH3]SbBr5 orthorhombic P212121 a 7.964 b 13.9424 c 14.065 @293K [62]
1,5-pentanediammonium pentabromoantimonate (III) [NH3(CH2)5NH3]SbBr5 orthorhombic Pnma a 14.04 b 8.04 c 13.97 @393K [62]
Ethyldimethylphenylammonium [EtMe2PhN]3[Sb2Br9] orthorhombic Pnma a = 35.620 b = 9.954 c = 12.761 Z = 4 [63]
Tris(N,N-dimethylanilinium) tri--bromido-bis[tribromidoantimonate(III)] (C8H12N)3[Sb2Br9] triclinic P1 a 9.7857(b 13.7658(c 17.0297(α 66.581( β 78.689( γ 72.601( Z=2 [64]
[CH3SC(NH2)2]2SbBr5 11.4258 b=8.9079 c=17.3627 β=92.225 Z=4 1765.8 2.647 [65]
cyclopropylammonium [C3H8N]2SbBr5 monoclinic P21/c a=11.8937 b=19.0986 c=7.8047 β = 108.908° 1168.0 2.525 270K [66]
cyclopropylammonium [C3H8N]2SbBr5 orthorhombic Pnca a=22.5314 b=18.9885 c=7.8845 Z=8 2336.0 2.511 300K [66]
cyclopropylammonium [C3H8N]2SbBr5 orthorhombic Bbcm a=22.4485 b=18.9653 c=7.9488 Z=8 2256 2.503 325K; band gap 2.41 eV; phase changes at 290 K and = 315 K [66]
Benzeneethanammonium (C8NH12)2SbBr5 yellow [67]
phenylmethylammonium (C6H5CH2NH3)3SbBr6 monoclinic P21/c a 15.2246 b 8.0632 c 24.3042 β 100.005° Z=4 2938.2 2.093 yellow [68]
(R)-(−)-1-cyclohexylethylammonium (R-CHEAH)Sb3Br10 monoclinic P21 a=12.76938 b=30.1777 c=13.2336 β=90.818 [69]
Pyrrolidinium [C4H9N]2SbBr8 monoclinic a=31.4 b=9.71 c=15.0 β=99.0° Z=8 4517 2.50 black [70]
2-Pyrolidonium [C4H6ONH]2SbBr8 black; orange red when cold [70]
N-methylpyrrolidinium [C4H9NCH3]3Sb2Br9 trigonal R3c a=15.6943 c=15.6943 Z=6 5018.8 2.424 yellow @293K [71]
N-methylpyrrolidinium [C4H9NCH3]3Sb2Br9 trigonal R3c a=15.9951 c=23.1124 Z=5 5120.9 2.376 @335K [71]
Piperidinium [C5H11N]2SbBr8 monoclinic a=28.8 b=19.8 c=18.7 β=116.28 Z=16 9561 2.58 black [70]
Piperazine-1,4-diium (C4H12N2)[SbBr5]·H2O monoclinic P21/n a=9.9162 b=14.4090 c=10.3898 β=99.432 Z=4 1464.45 2.846 [72]
Morpholinium [NH2(C2H4)2O]SbBr4 orthorhombic Pbca a=12.273 b=8.397 c=23.276 Z=8 2399 2.933 yellow [73]
Morpholinium [NH2(C2H4)2O]2[SbBr5] orthorhombic P212121 a 9.274 b 10.325 c 18.472 Z=4 1768.8 2.620 yellow; piezoelectric [74]
Morpholinium [C4H9ONH]2SbBr8 orthorhombic Pna21 a=28.01 b=8.31 c=10.02 Z=4 2332 2.64 black; red when cold [70]
Pyridinium (C5H5NH)SbBr4 triclinic P1 @116K [75]
Pyridinium (C5H5NH)SbBr4 monoclinic C2/c a=11.825 b=13.048 c=7.798 β=93.87° Z=4 2.922 @297K [57][75]
Pyridinium (C5H5NH)6SbIIISbV3Br24 orthorhombic CmC21 a=17.51 b=23.77 c=16.46 Z=4 6851 2.80 black [70]
benzylammonium (C6H5CH2NH3)2SbBr5 monoclinic P21/a a=8.0254 b=19.5087 c=14.5079 β=107.451 Z=4 2166.89 2.261 yellow [76]
1-methylpyridinium (1−CH3C5H4NH)SbBr4 monoclinic P21/c a=12.73 b=13.54 c=7.59 β=107.3 Z=4 1250 2.85 pale yellow [77]
bis(1-methylpyridin-1-ium) hexabromo-antimony tribromide (1−CH3C5H4NH)2SbBr6•Br3 triclinic P1 a 7.4567 b 9.4488 c 9.6777 α 68.629° β 89.848° γ 73.002° 1029.2 [78] (1)
2-methylpyridinium (2−CH3C5H4NH)SbBr4 monoclinic P21/c a=12.84 b=13.31 c=7.65 β=106.6 Z=4 1252 2.84 pale yellow [77]
3-methylpyridinium (3−CH3C5H4NH)SbBr4 monoclinic P21/c a=12.51 b=13.64 c=7.72 β=106.9 Z=4 1260 2.76 pale yellow [77]
bis(2-bromo-5-methylpyridinium) hexabromoantimonate tribromide (2-Br-5-MePy)2[SbBr6](Br3) monoclinic Im a 8.4041 b 13.341 c 12.237 β 95.731° [79]
3-carboxylpyridinium (3−COOHC5H4NH)2SbBr5 monoclinic C2/c a=14.10 b=19.43 c=8.01 β=98.6° Z=4 2169 2.36 lemon yellow [77]
4-methylpyridinium (4−CH3C5H4NH)SbBr4 monoclinic P21/c a 12.011 b 13.581 c 7.7637 β 90.341° [80]
4-methylpyridinium (4−CH3C5H4NH)2SbBr5 triclinic P1 a=10.66 b=10.86 c=9.30 α=108.8° β=97.7° γ=99.2° Z=2 985 2.39 yellow needles [57][77][81]
4-methylpyridinium (4−CH3C5H4NH)3Sb2Br9•I2 monoclinic P21 a=8.3290 b=23.5510 c=9.4722 β=104.388 Z=2 1799.7 [39]
4-methylpyridinium (4−CH3C5H4NH)2SbBr5•I2 monoclinic P21/n a=7.5955 b=14.6757 c=9.5902 β=91.607 Z=2 2182.85 [39]
4-methylpyridinium (4-C6H7NH)2SbVBr9 monoclinic C2/m a=18.39 b=7.440 c=9.84 β=113.14° 2.760 red [82]
α-picolinium (2−CH3C5H4NH)2SbBr9 triclinic P1 a 9.249 b 9.750 c 7.645 α 90.07° β 107.46° γ 70.52° Z=2 2.77 black; orange at −174° [70][83]
β-picolinium (3−CH3C5H4NH)2SbBr9 monoclinic Z=2 2.74 black; orange at −174° [70]
γ-picolinium (4−CH3C5H4NH)2SbBr9 monoclinic Z=2 2.77 black; red at −174° [70]
1-fluoropyridinium (1-FPy)3[Sb2Br9] monoclinic C2/c a=21.85 b=21.15 c=13.85 β=104.6° Z=8 6179 2.70 deep yellow [77]
1-bromopyridinium ? monoclinic C2/c a=11.83 b=13.03 c=7.70 β=93.9° 1183 2.4 light orange [77]
2-chloropyridinium (2-ClPyH)2SbBr5 monoclinic P21/a a=10.64 b=15.87 c=5.88 β=105.3° Z=2 957 2.60 orange [77]
2-chloropyridinium (2-ClPyH)SbBr6 monoclinic P21/c a=13.0770 b=7.3498 c=16.5301 β=112.117° Sb(V) [84]
2-bromopyridinium (2-BrPyH)2SbBr5 monoclinic P21/a a=10.53 b=16.17 c=5.89 β=104.8° Z=2 989 2.82 red [77]
2-bromopyridinium (2-BrPyH)SbBr6 monoclinic P21/c a=13.111 b=7.3787 c=16.555 β=111.179° Sb(V) [84]
bis(2-iodopyridinium) hexabromoantimonate tribromide (2-IPyH)2[SbBr6](Br3) monoclinic P21/n a 8.1800 b 12.9394 c 12.5865 β 105.412° [79]
3-chloropyridinium (3-ClPyH)SbBr6 orthorhombic Pca21 a=16.6414 b=7.3471 c=24.2543 Z=8 2965.5 cherry-red [85]
3-bromopyridinium (3-BrPyH)2SbBr5 monoclinic P21/c a=18.37 b=11.98 c=9.35 β=102.5° Z=4 2009 2.77 pale yellow [77]
3-bromopyridinium (3-BrPyH)SbBr6 orthorhombic Pca21 cherry-red [85]
3-iodopyridinium (3-IPyH)2SbBr5 monoclinic P21/c a=17.99 b=12.31 c=9.35 β=91.5° Z=4 2070 2.99 pale yellow [77]
4-bromopyridinium pentabromoantimonate(III) (4-BrC5H4NH)2SbBr5 triclinic P1 a = 9.186 b = 10.622 c = 10.703 α = 99.665° β = 97.393° γ = 108.539° Z = 2 [86]
bis(4-bromopyridinium) hexabromoantimonate tribromide (4-BrPyH)2[SbBr6](Br3) monoclinic P21/c a 7.3255 b 20.667 c 16.5665 β 95.627° [79]
2,6-dichloropyridinium (2,6-ClPyH)[SbBr4] monoclinic P2/m a=10.45 b=10.76 c=13.45 β=110.2 Z=4 1491 2.76 pale yellow [77]
2,6-dibromopyridinium (2,6-BrPyH)3[SbBr6](Br3) · 2H2O monoclinic C2/c a=32.8242 b=9.6155 c=14.7877 β=101.732° [87]
3,5-dichloropyridinium (3,5-ClPyH)2[SbBr5] orthorhombic Pbca a=21,77 b=8.14 c=24.38 Z=8 4320 2.52 deep yellow [77]
N-ethylpyridinium EtPySbBr6 [88]
N-propylpyridinium 1-n-PrPySbBr6 monoclinic P21/n a=7.3687 b=16.4706 c=13.8620 β=97.054 Z=4 1669.65 [79] (1)
N-butylpyridinium 1-n=BuPySbBr6 orthorhombic P212121 a=7.4277 b=14.1293 c=16.7699 Z=4 1760.0 [79] (2)
2-aminopyridinium [2-NH2C5H4NH][SbBr4] monoclinic P21/c a 12.484 b 13.106 c 7.492 β 105.84° Z=4 1179.1 3.022 @100K phase transition at 396/412K [89]
4-aminopyridinium (4-NH2C5H4NH)SbBr4 monoclinic P21/c a 11.548 b 14.029 c 7.432 β 93.19° @220K [90]
tetrakis(2,2'-bipyridin-1-ium) tetrakis(μ-bromo)-hexadecabromo-tetra-antimony (2,2′-bipyH)4[Sb4Br20] monoclinic P21/c a 14.5026 b 14.6945 c 16.5497 β 109.991° [51]
bis(pyridinium)ethane (PyC2){[SbBr6](Br3)} triclinic P1 a=7.3269 b=9.1941 c=9.7994  α=64.474 β=80.207 γ=86.244 Z=1 586.99 cherry-red [91]
1,1′-(1,2-ethanediyl)bis(pyridine) PyC22+SbBr5 triclinic P1 a 10.1060 b 10.2956 c 11.1394 α 105.030° β 101.709° γ 117.233° [92]
1,1′-(1,2-ethanediyl)bis(3,5-dimethylpyridine) 3,5-MePyC22+SbBr5 monoclinic P2/n a 6.2898 b 8.7454 c 20.408 β 90.438° [92]
1,1′-(1,2-ethanediyl)bis(pyridine) (C2Py)2[Sb2Br10] triclinic P1 a 6.1343 b 9.2857 c 17.2041 α 90.331° β 100.259° γ 99.912° [92]
1,1′-(1,2-ethanediyl)bis(pyridine) (C2Py)2[Sb2Br10] monoclinic C2/c a 19.6880 b 10.0152 c 20.8410 β 111.104° [92]
1,1′-(1,2-ethanediyl)bis(3,5-dimethylpyridine) (3,5-MePy){[SbBr4]} monoclinic P21/n a 20.5536 b 7.2974 c 21.2510 β 117.694° [92]
bis(pyridinium)propane (PyC3)2[Sb2Br9][SbBr6] orthorhombic Pmmm a=20.3785 b=15.5018 c=7.4618 Z=2 2357.2 mixed III V valence [91]
bis(pyridinium)butane (PyC4){[SbBr6](Br3)} triclinic P1 a=7.8627 b=9.1285 c=10.1514 α=68.392° β=89.669° γ=72.048° Z=1 639.63 [91]
4-ethylpyridinium (4−CH3CH2C5H4NH)3Sb2Br14 orthorhombic Pna21 Z=4 2.55 black; orange-red at −174° [70]
1,1′-(propane-1,3-diyl)bis(4-methylpyridin)-1-ium (4-MePyC3)2[SbBr6]2[Br5]2 monoclinic P21/n a=7.7157 b=16.1786 c=24.292 β=96.972° Sb(V) [93]
propanediyl-bis(3-methylpyridinium) (3-MePyC3)3[Sb4Br16] monoclinic P21/n a 11.6777 b 42.282 c 16.5504 β 95.618° [94]
1,1'-(ethane-1,2-diyl)bis(3-methylpyridin-1-ium) (3-MePyC2)3[Sb2Br9]2 triclinic P1 a 10.6368 b 10.8059 c 15.4810 α 76.034° β 81.735° γ 83.387° [94]
bis(1,1'-(butane-1,4-diyl)bis(3-methylpyridin-1-ium)) hexakis(μ-bromo)-decabromo-tetra-antimony(iii) (3-MePyC4)3[Sb4Br16] monoclinic P21/n a 14.2410 b 11.2731 c 19.0662 β 110.674° [94]
4,4'-dimethyl-1,1'-butanediylbis(pyridinium) (4-MePyC4)[Sb2Br8] monoclinic P 2/c a 26.313 b 6.4010 c 17.9886 β 109.026° [95]
4,4'-dimethyl-1,1'-butanediylbis(pyridinium) (4-MePyC4)2[Sb4Br16] monoclinic P21/n a 11.4661 b 19.7236 c 12.5217 β 92.726° [95]
1,3,4-trimethylpyridin-1-ium 1,3,4-MePy[SbBr6] triclinic P1 a 8.3195 b 8.9921 c 12.3360 α 86.146° β 76.520° γ 71.872° Sb(V) [96]
1,4-dimethylpyridin-1-ium 1,4-MePy[SbBr6] triclinic P1 a 7.6803 b 8.5900 c 12.6261 α 75.226° β 88.079° γ 79.872° Sb(V) [96]
1,2-dimethylpyridinium (1,2-MePy)2[SbBr6](Br3) monoclinic P21/n a=7.3284 b=10.5875 c=16.7538 β=96.005° Sb(V) [96]
1,3-dimethylpyridinium (1,3-MePy)2[SbBr6](Br3) triclinic P1 a 7.2611 b 9.086 c 11.1895 α 67.617° β 87.457° γ 72.16° [79] (5)
2,4-dimethylpyridinium ? orthorhombic Pmmn a=12.06 b=12.97 c=11.49 1797 2.2 yellow [77]
2,6-dimethylpyridinium (2,6-MePy)3[Sb2Br9] monoclinic P21/c a=12.10 b=15.56 c=21.27 β=115.7 Z=4° 3629 2.36 pale yellow [77]
1-ethyl-3-methylpyridinium (1-Et-3-MePy)2[SbBr6](Br3) triclinic P1 a 7.2472 b 9.4088 c 11.5541 α 69.263° β 81.162° γ 71.303° [79]
4-ethyl-1-methylpyridinium (4-Et-1-MePy)2[SbBr6](Br3) monoclinic P21/n a 8.4645 b 13.0802 c 13.1574 β 105.702° [79]
bis(2,6-dimethylpyridin-1-ium) hexabromo-antimony pentabromide (2,6-MePy)2[SbBr6](Br5) monoclinic P21/c a 7.4584 b 18.0860 c 21.626 β 93.607° Z=4 2911.4 [78] (3)
bis(1,3,5-trimethylpyridin-1-ium) hexabromo-antimony tribromide (1,3,5-MePy)2[SbBr6](Br3) triclinic P1 a 8.1964 b 8.2015 c 12.5202 α 92.883° β 103.923° γ 115.467° Z=4 1085.3 100K [78] (4)
2,4,6-trimethylpyridinium (2,4,6-MePy)3[Sb2Br9] monoclinic P21/n a=10.36 b=42.36 c=9.09 β=100.2° Z=4 3926 2.25 yellow-tan [77]
2,4,6-trimethylpyridinium (2,4,6-MePy)[SbBr]•0.5Br2 monoclinic P21/n a 10.4938 b 13.6198 c 12.8807 β 90.339° Z=4 1840.9 100k [78] (5)
bis(3,5-dimethylpyridin-1-ium) hexabromo-antimony tribromide (3,5--MePy)2[SbBr6](Br3) orthorhombic Pnnm a 17.1097 b 10.4401 c 7.3438 Z=2 1311.8 [78] (2)
bis(1-ethyl-3-methylpyridinium) hexabromoantimonate tribromide (1-Et-3-MePy)2[SbBr6](Br3) triclinic P1 a 7.2472 b 9.4088 c 11.5541 α 69.263° β 81.162° γ 71.303° [79]
1-ethyl-4-methylpyridin-1-ium (1-Et-4-MePy)2[SbBr6](Br3) monoclinic P21/n a=11.4927 b=7.3613 c=16.9266 β=100.782° Sb(V) [96]
1-ethyl-2-methylpyridin-1-ium (1-Et-2-MePy)2[SbBr6](Br3) monoclinic P21/n a=8.3421 b=13.196 c=13.183 β=105.40° Sb(V) [96]
1-ethyl-2,6-dimethylpyridin-1-ium hexabromoantimonate (1-Et-2,6-MePy)[SbBr6] monoclinic P21/c a 9.9470 b 11.5017 c 16.4632 β 107.201° [79]
(PyC3)3[Sb2Br9]2 [97]
(PyC4)[Sb2Br8] [97]
(PyC5)2[α-Sb4Br16] [97]
(PyC6)2[Sb2Br10] [97]
(4-MePyC2)2[Sb2Br10] [97]
(4‑MePyC3)2[α-Sb4Br16] [97]
(4-MePyC5)2[α-Sb4Br16] [97]
1-benzylpyridin-1-ium hexabromoantimonate C6H5CH2PySbBr6 orthorhombic Pnma a=12.6594 b=17.3414 c=8.6389 Z=4 1896.5 [78] (6)
bis(1-benzyl-2-methylpyridinium) hexabromoantimonate tribromide (CH3-C6H5CH2Py)2SbBr6(Br3) triclinic P1 a 8.9834 b 10.2599 c 10.3601 α 94.223° β 102.737° γ 111.846° [79] (7)
bis(1-(4-bromobenzyl)pyridinium) hexabromoantimonate tribromide (BrC6H4CH2Py)2SbBr6(Br3) monoclinic P21/c a 8.6483 b 15.1885 c 13.3520 β 98.887° [79]
2,2'-bipyridinium pentabromoantimonate (III) (2,2'-C10H8N2H2)SbBr5 monoclinic P21/c a = 14.575 b = 14.726 c = 16.775 β = 110.34° Z = 8 [98]
4,4'-bipyridinium pentabromoantimonate (III) (4,4'-C10H8N2H2)SbBr5 triclinic P1 a = 11.28.7 b = 10.121 c = 8.548 α = 98.94° β = 101.06° γ = 113.57° Z = 2 [98]
imidazolium (C3N2H5)3SbBr6.H2O monoclinic P21/c a=8.9137 b=19.2032 c=12.7984 β=90.650° [99]
imidazolium (C3N2H5)5Sb2Br11 monoclinic P21/n a 9.1399 b 15.150 c 13.969 β 96.19° ferroelectric Curie Point 145K; 4 phases [99][100]
thiazolium (C3H4NS)6Sb4Br18·2H2O triclinic P1 a 11.060 b 11.465 c 12.957 α 116.21° β 100.71° γ 98.87° [101]
quinolinium monoclinic Cc a=15.28 b=14.04 c=7.44 β =118.3 Z=4 1405 2.70 light yellow [77]
quinolinium (C9H7NH)2SbBr9 monoclinic P21/n as=7.518 b=11.316 c=16.351 β =97.41 Z=2 Sb(V) [102]
3-Bromoquinolinium (3-BrQuinH)4[Sb2Br10] monoclinic C2/c a 15.3947 b 13.7967 c 22.8880 β 92.039° [103]2
5-Bromoquinolinium (5-BrQuinH)2[SbBr5] monoclinic C2/c a 23.8681 b 12.2567 c 8.6474 β 106.128° [103]3
3-Bromo-1-methylquinolinium (1-Me-3-BrQuin)3[Sb3Br12] triclinic P1 a 9.8582 b 11.7183 c 21.6576, α 98.981° β 96.402° γ 92.371° [103]5
isoquinolinium isoquinHSbBr4 monoclinic P21/a a=13.11 b=14.14 c=7.57 β=91.4 Z=4 1403 2.71 light tan [77]
N-methyl quinolinium (N-MeQuin)2{[SbBr6](Br3)} triclinic P1 a=8.0902 b=8.5656 c=11.6475 𝛼 = 68.901° β = 79.204° 𝛾 = 77.120° Z=1 728.98 [104]
N-methyl isoquinolinium (N-MeIsoquin)2{[SbBr6](Br3)} monoclinic P21/c a=12.9656 b=9.3423 c=12.5920 β = 107.233° Z=2 1456.8 [104]
N-ethyl quinolinium (N-EtQuin)[SbBr6] orthorhombic Pnma a=14.5122 b=11.4005 c=11.2135° Z=4 1855.2 [104]
tris(6-methylquinolinium) hexabromoantimonate(III) (6-MeQuin)3[SbBr6] [105]
2-methyl-1,3-benzoxazole SbBr5(boxH)2 triclinic P1 a=8.560 b=11.008 c=12.751 α=102.836° β=106.173° γ=93.398° [106]
quinuclidinium (C9H7NH)2SbVBr9 monoclinic P21/n a=7.518 b=11.316 c=16.351 β=97.41° Z=2 2.67 red [107]
quinuclidinium (C7H13NH)4SbIIISbVBr12.2Br2 cubic Fm3m a=13.873 2670 2.45 black [108]
3-ammoniumpropyl imidazolium pentabromoantimonate (III) [C6H13N3]2+[SbBr5]2− orthorhombic P212121 8.7120 b = 12.6608 c = 14.3498 Z = 4 [109]
trihydroxonium enneabromidodiantimonate(III) (H3O)3Sb2Br9 monoclinic P21/n a = 13.4679 b = 7.6319 c = 19.1397 β = 90.240° Z=4 1967.3 3.443 yellow [110]
hexabromoantimonic(V) acid trihydrate HSbBr6 · 3H2O monoclinic P21/c a = 7.110 b = 13.532 c = 12.846 β = 94.87 Z=4 melt 330K [111]
tetramethylphosphonium [(CH3)4P]3[Sb2Br9] hexagonal P31/c a 9.7931 c 22.697 deep yellow [112]
trimethylphosphonium [(CH3)3PH][SbBr4] monoclinic P21/c a=10.9103 b=19.8342 c=11.3617 β=100.744 Z=4 2415.54 2.851 colourless [113]
Methyltriphenylphosphonium (MTP)6SbBr6Sb2Br9⋅H2O trigonal R3 a=19.7793 c=27.2770 Z=3 9241 1.749 [114]
Methyltriphenylphosphonium (MTP)2SbBr5 monoclinic P21/c a=12.7399 b=12.3833 c=26.0206 β=96.373 Z=4 4079.7 1.752 [114]
tetraphenylphosphonium P(C6H5)4SbBr6 monoclinic C2/c a = 16.887 b = 7.357 c = 23.367 β = 93.98° Z=4 2896.1 yellow [115]
triphenyl(9-phenyl-9H-carbazol-3-yl) phosphonium antimony bromide TPPcarzSbBr4 triclinic P1 a=9.77183 b=11.42472 16.15939 α=88.2199° β=80.7810° γ=71.8474°, Z = 2 1691.77 1.857 red LED [22]
Tetraphenylphosphonium Ikosioctabromooctaantimonate(III) (PPh4)4Sb8Br28 triclinic P1 a=12.491 b=13.078 c=21.523 α=102.93° β=100.83° γ= 100.42°, Z = 2 3273 2.318 [116]
Tris-Chlorobromophosphazeno-carbenium [C(NP(Br0,78Cl0,22)3)3]SbBr6 orthorhombic Pbca a = 27.92 b = 11.23 c = 17.54 Z = 8 [117]
Rb3Sb2Br9 monoclinic P21/n [118][119]
Rb4Sb2Br12 tetragonal I41/amd a = 10.70 and c = 21.69 Z=8 4.17 black [26][120][19]
Rb7Sb3Br16 orthorhombic Cmcm a = 23.4716 b = 13.57.89 c = 35.3947 yellow [119][121]
[RuNOPy4Br]4[Sb2Br8][Sb3Br12]2 monoclinic P21/c a=12.021 b=22.454 c=26.372 β=92.506° Z=8 7112 2.634 light orange [122]
1,4-bis(ammoniomethyl)cyclohexane (C8H20N2)2AgMBr8 triclinic P1 a 8.0820 b 8.161 c 11.814 α 90.185° β 95.390° γ 90.121° band gap 2.600 eV [123]
histammonium (HIS)2AgSbBr8 monoclinic C2/c a=11.5632 b=12.2529 c=18.694 β=94.264 Z=4 2641.3 2.754 semiconductor; pale yellow [21]
Cs3Sb2Br9 a=7.9165 c=9.7139 yellow; orange at 300°C; perovskite [124]
Cs4Sb2Br12 tetragonal I41/amd a=10.842 c=21.913 Z=2 2576 black @300K [26][125]
Cs2AgSbBr6 cubic Fm3m a = 11.1583 Z=4 1389.2 4.661 black; bandgap 1.64 eV [117]
Benzeneethanammonium (C8NH12)4Bi0.57Sb0.43Br7⋅H2O triclinic P1 a=13.0207 b=13.1304 c=13.3192 α=93.818° β=102.408° γ=108.610° Z=2 2085.1 1.971 light green [67]

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