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(H3O)3Sb2Br9 [trihydroxonium enneabromidodiantimonate(III)] is the first representative of the M3E2X9 family (M = cation, E = Sb and Bi, and X = Br and I) with oxonium cations. The metastable compound was obtained in trace amounts from a solution of CsBr and SbBr3 in con­cen­trated aqueous HBr. Single crystals were isolated from the mother liquor and investigated by single-crystal X-ray diffraction at 100 K. (H3O)3Sb2Br9 crystallizes with the Tl3Bi2I9 structure type, which is a distorted defect variant of cubic perovskite. The crystal structure comprises characteristic 2[SbBr3Br3/2] double layers of corner-sharing SbBr6 octa­hedra with a [001] stacking direction. Due to the small size of the H3O+ cation and O—H...Br hydrogen bonding, the octa­hedra are tilted.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616017198/yo3024sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616017198/yo3024Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616017198/yo3024sup3.pdf
Degree of distortion information and the EDX spectrum

CCDC reference: 1511674

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Trihydroxonium enneabromidodiantimonate(III) top
Crystal data top
(H3O)3Sb2Br9F(000) = 1800
Mr = 1019.76Dx = 3.443 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 13.4679 (4) ÅCell parameters from 3465 reflections
b = 7.6319 (2) Åθ = 3.0–26.2°
c = 19.1397 (6) ŵ = 21.01 mm1
β = 90.240 (1)°T = 100 K
V = 1967.27 (10) Å3Block, yellow
Z = 40.07 × 0.05 × 0.04 mm
Data collection top
Bruker APEXII CCD
diffractometer
3551 reflections with I > 2σ(I)
φ and ω scansRint = 0.028
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 2009)
θmax = 27.5°, θmin = 1.9°
Tmin = 0.582, Tmax = 0.746h = 1717
22840 measured reflectionsk = 97
4507 independent reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: difference Fourier map
wR(F2) = 0.058All H-atom parameters refined
S = 1.02 w = 1/[σ2(Fo2) + (0.0269P)2 + 3.125P],
where P = (Fo2 + 2Fc2)/3
4507 reflections(Δ/σ)max = 0.087
158 parametersΔρmax = 0.94 e Å3
0 restraintsΔρmin = 0.78 e Å3
Special details top

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 (Å2) top
xyzUiso*/Ueq
Sb10.33714 (2)0.99661 (3)0.34753 (2)0.00912 (7)
Sb20.33370 (2)1.00541 (3)0.84467 (2)0.00913 (7)
Br10.00571 (4)0.42241 (7)0.75595 (3)0.02331 (12)
Br20.32633 (4)0.44788 (6)0.07711 (3)0.02106 (12)
Br30.32537 (4)0.55985 (7)0.57782 (3)0.02104 (12)
Br40.08301 (4)0.69674 (6)0.05644 (3)0.01888 (11)
Br50.05239 (3)0.70329 (6)0.57585 (3)0.01727 (11)
Br60.42333 (4)0.70854 (6)0.39338 (3)0.01891 (11)
Br70.38283 (4)0.71954 (6)0.91531 (3)0.01883 (11)
Br80.75719 (4)0.69343 (6)0.72033 (3)0.01818 (11)
Br90.70167 (3)0.68217 (6)0.24294 (3)0.02030 (11)
O10.4712 (3)0.5175 (5)0.2274 (3)0.0352 (10)
O20.1807 (3)0.4948 (6)0.4307 (2)0.0347 (10)
O30.6573 (3)0.0133 (5)0.3995 (2)0.0292 (9)
H1A0.482 (4)0.389 (9)0.234 (3)0.041 (11)*
H1B0.550 (5)0.557 (8)0.231 (3)0.041 (11)*
H1C0.435 (5)0.542 (8)0.275 (4)0.041 (11)*
H2A0.174 (5)0.605 (8)0.427 (3)0.037 (10)*
H2B0.107 (5)0.475 (8)0.436 (3)0.037 (10)*
H2C0.212 (5)0.459 (8)0.384 (3)0.037 (10)*
H3A0.619 (5)0.032 (9)0.438 (4)0.053 (12)*
H3B0.640 (5)0.053 (9)0.368 (4)0.053 (12)*
H3C0.725 (5)0.044 (9)0.403 (4)0.053 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.00861 (14)0.01001 (13)0.00876 (15)0.00043 (11)0.00000 (11)0.00060 (11)
Sb20.00811 (14)0.00993 (13)0.00935 (16)0.00097 (11)0.00011 (11)0.00008 (11)
Br10.0160 (2)0.0273 (3)0.0267 (3)0.0031 (2)0.0094 (2)0.0039 (2)
Br20.0174 (2)0.0239 (2)0.0219 (3)0.00105 (18)0.0076 (2)0.00048 (19)
Br30.0156 (2)0.0261 (3)0.0215 (3)0.00024 (19)0.0069 (2)0.0012 (2)
Br40.0227 (2)0.0180 (2)0.0159 (3)0.00296 (18)0.0040 (2)0.00326 (18)
Br50.0174 (2)0.0175 (2)0.0169 (3)0.00327 (17)0.00407 (19)0.00279 (17)
Br60.0217 (2)0.0148 (2)0.0202 (3)0.00418 (18)0.0037 (2)0.00320 (18)
Br70.0216 (2)0.0151 (2)0.0197 (3)0.00000 (18)0.0034 (2)0.00512 (18)
Br80.0210 (2)0.0151 (2)0.0184 (3)0.00358 (17)0.0035 (2)0.00308 (18)
Br90.0168 (2)0.0177 (2)0.0264 (3)0.00030 (18)0.0061 (2)0.00792 (19)
O10.026 (2)0.030 (2)0.050 (3)0.0010 (17)0.006 (2)0.007 (2)
O20.038 (3)0.031 (2)0.034 (2)0.009 (2)0.008 (2)0.007 (2)
O30.023 (2)0.033 (2)0.032 (2)0.0070 (17)0.0060 (18)0.0126 (19)
Geometric parameters (Å, º) top
Sb1—Br4i2.6175 (5)Br4—Sb1viii2.6174 (5)
Sb1—Br62.6349 (5)Br5—Sb2vii2.6323 (5)
Sb1—Br2i2.6631 (6)Br8—Sb1iii2.9805 (5)
Sb1—Br1ii2.9397 (6)Br8—Sb1ix3.0279 (5)
Sb1—Br8iii2.9805 (5)Br9—Sb2iii2.9526 (5)
Sb1—Br8iv3.0279 (5)Br9—Sb2ii2.9955 (5)
Sb2—Br5v2.6323 (5)O1—H1A1.00 (7)
Sb2—Br3v2.6436 (6)O1—H1B1.10 (6)
Sb2—Br72.6492 (5)O1—H1C1.05 (7)
Sb2—Br9iii2.9525 (5)O2—H2A0.85 (6)
Sb2—Br1v2.9704 (6)O2—H2B1.01 (6)
Sb2—Br9vi2.9956 (5)O2—H2C1.03 (7)
Br1—Sb1vi2.9398 (6)O3—H3A0.91 (8)
Br1—Sb2vii2.9704 (6)O3—H3B0.81 (7)
Br2—Sb1viii2.6631 (6)O3—H3C0.95 (7)
Br3—Sb2vii2.6437 (6)
Br4i—Sb1—Br694.236 (17)Br5v—Sb2—Br1v94.181 (17)
Br4i—Sb1—Br2i92.256 (18)Br3v—Sb2—Br1v172.421 (18)
Br6—Sb1—Br2i93.850 (18)Br7—Sb2—Br1v88.527 (17)
Br4i—Sb1—Br1ii88.849 (17)Br9iii—Sb2—Br1v85.416 (16)
Br6—Sb1—Br1ii91.932 (17)Br5v—Sb2—Br9vi173.099 (18)
Br2i—Sb1—Br1ii174.016 (18)Br3v—Sb2—Br9vi87.685 (17)
Br4i—Sb1—Br8iii90.919 (15)Br7—Sb2—Br9vi94.847 (15)
Br6—Sb1—Br8iii173.606 (18)Br9iii—Sb2—Br9vi85.576 (9)
Br2i—Sb1—Br8iii89.718 (17)Br1v—Sb2—Br9vi84.748 (16)
Br1ii—Sb1—Br8iii84.382 (15)Sb1vi—Br1—Sb2vii155.23 (2)
Br4i—Sb1—Br8iv171.042 (18)Sb1iii—Br8—Sb1ix151.654 (19)
Br6—Sb1—Br8iv91.306 (15)Sb2iii—Br9—Sb2ii148.104 (18)
Br2i—Sb1—Br8iv94.391 (16)H1A—O1—H1B97 (5)
Br1ii—Sb1—Br8iv83.929 (16)H1A—O1—H1C97 (5)
Br8iii—Sb1—Br8iv83.123 (8)H1B—O1—H1C111 (5)
Br5v—Sb2—Br3v93.282 (18)H2A—O2—H2B93 (5)
Br5v—Sb2—Br791.937 (16)H2A—O2—H2C103 (6)
Br3v—Sb2—Br792.544 (18)H2B—O2—H2C117 (5)
Br5v—Sb2—Br9iii87.544 (16)H3A—O3—H3B122 (7)
Br3v—Sb2—Br9iii93.588 (17)H3A—O3—H3C118 (6)
Br7—Sb2—Br9iii173.866 (19)H3B—O3—H3C118 (7)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y+3/2, z1/2; (iii) x+1, y+2, z+1; (iv) x1/2, y+3/2, z1/2; (v) x+1/2, y+1/2, z+3/2; (vi) x1/2, y+3/2, z+1/2; (vii) x+1/2, y1/2, z+3/2; (viii) x+1/2, y1/2, z+1/2; (ix) x+1/2, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br1x1.00 (7)2.43 (7)3.433 (4)178 (5)
O1—H1B···Br91.10 (6)2.27 (6)3.361 (4)170 (5)
O1—H1C···Br61.05 (7)2.61 (7)3.556 (5)150 (5)
O1—H1C···Br8xi1.05 (7)3.15 (6)3.616 (4)108 (4)
O2—H2A···Br2i0.85 (6)2.62 (6)3.463 (4)174 (6)
O2—H2B···Br5xii1.01 (6)2.55 (6)3.485 (4)154 (5)
O2—H2C···Br8xi1.03 (7)2.35 (7)3.338 (5)161 (5)
O3—H3A···Br4xiii0.91 (8)2.65 (8)3.466 (4)151 (6)
O3—H3B···Br1x0.81 (7)2.82 (7)3.486 (4)141 (6)
O3—H3C···Br7x0.95 (7)2.52 (7)3.433 (4)162 (6)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (x) x+1/2, y+1/2, z1/2; (xi) x+1, y+1, z+1; (xii) x, y+1, z+1; (xiii) x+1/2, y+1/2, z+1/2.
Wyckoff positions, coordinates and displacement parameters Uij (pm2) for the atoms in (H3O)3Sb2Br9 at 100 (2) K. The exponent of the anisotropic displacement factor U23]. Ueq is defined as one third of the trace of the orthogonalized Uij tensor top
AtomW.p.xyzU11U22U33U12U13U23Ueq/Uiso
Sb14e0.33714 (2)0.00339 (3)0.65247 (2)86 (1)100 (1)88 (2)-4(1)0(1)-6(1)91 (1)
Sb24e0.33370 (2)-0.00541 (3)0.15533 (2)81 (1)99 (1)93 (2)10 (1)1(1)-1(1)91 (1)
Br14e0.00571 (4)0.57759 (7)0.24405 (3)160 (2)273 (3)267 (3)31 (2)-94 (2)-39 (2)233 (1)
Br24e0.32633 (4)0.55212 (6)0.92289 (3)174 (3)239 (2)219 (3)-11 (2)-77 (2)-5(2)210 (1)
Br34e0.32537 (4)0.44015 (7)0.42217 (3)156 (2)261 (3)215 (3)24 (2)-69 (2)12 (2)210 (1)
Br44e0.08300 (4)0.30326 (6)0.94356 (3)227 (3)180 (2)159 (3)-30 (2)40 (2)33 (2)189 (1)
Br54e0.05239 (3)0.29671 (6)0.42415 (3)173 (2)175 (2)169 (3)-33 (2)41 (2)28 (2)173 (1)
Br64e0.42333 (4)0.29146 (6)0.60662 (3)217 (3)148 (2)201 (3)-42 (2)37 (2)32 (2)189 (1)
Br74e0.38284 (4)0.28046 (6)0.08469 (3)217 (2)151 (2)197 (3)0(2)34 (2)51 (2)188 (1)
Br84e0.75719 (4)0.30657 (6)0.27967 (3)210 (2)151 (2)184 (3)-36 (2)35 (2)31 (2)182 (1)
Br94e0.70166 (3)0.31783 (6)0.75705 (3)168 (2)176 (2)264 (3)-3(2)61 (2)79 (2)203 (1)
O14e0.4712 (3)0.5176 (5)0.2724 (3)257 (22)304 (22)496 (29)-10 (17)62 (20)-66 (20)352 (10)
O24e0.1807 (4)0.4948 (6)0.4307 (3)385 (25)314 (22)343 (25)-95 (20)85 (20)-67 (20)347 (10)
O34e0.6574 (3)-0.0133 (5)0.3995 (2)231 (21)326 (22)321 (25)70 (17)60 (18)126 (19)292 (9)
H1A4e0.482 (4)0.389 (9)0.234 (3)412 (106)
H1B4e0.550 (5)0.556 (8)0.231 (3)412 (107)
H1C4e0.435 (5)0.542 (8)0.275 (4)412 (107)
H2A4e0.174 (5)0.605 (8)0.427 (3)367 (101)
H2B4e0.107 (5)0.475 (8)0.436 (3)367 (101)
H2C4e0.212 (5)0.459 (8)0.384 (3)367 (101)
H3A4e0.379 (5)-0.031 (9)0.437 (4)526 (124)
H3B4e0.640 (5)0.053 (9)0.369 (4)526 (124)
H3C4e0.725 (5)-0.044 (9)0.403 (4)526 (124)
 

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