(H
3O)
3Sb
2Br
9 [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 SbBr
3 in concentrated aqueous HBr. Single crystals were isolated from the mother liquor and investigated by single-crystal X-ray diffraction at 100 K. (H
3O)
3Sb
2Br
9 crystallizes with the Tl
3Bi
2I
9 structure type, which is a distorted defect variant of cubic perovskite. The crystal structure comprises characteristic
2[SbBr
3Br
3/2] double layers of corner-sharing SbBr
6 octahedra with a [001] stacking direction. Due to the small size of the H
3O
+ cation and O-H
Br hydrogen bonding, the octahedra are tilted.
Supporting information
CCDC reference: 1511674
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)3Sb2Br9 | F(000) = 1800 |
Mr = 1019.76 | Dx = 3.443 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.4679 (4) Å | Cell parameters from 3465 reflections |
b = 7.6319 (2) Å | θ = 3.0–26.2° |
c = 19.1397 (6) Å | µ = 21.01 mm−1 |
β = 90.240 (1)° | T = 100 K |
V = 1967.27 (10) Å3 | Block, yellow |
Z = 4 | 0.07 × 0.05 × 0.04 mm |
Data collection top
Bruker APEXII CCD diffractometer | 3551 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.028 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2009) | θmax = 27.5°, θmin = 1.9° |
Tmin = 0.582, Tmax = 0.746 | h = −17→17 |
22840 measured reflections | k = −9→7 |
4507 independent reflections | l = −24→24 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.058 | All 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 parameters | Δρmax = 0.94 e Å−3 |
0 restraints | Δρmin = −0.78 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Sb1 | 0.33714 (2) | 0.99661 (3) | 0.34753 (2) | 0.00912 (7) | |
Sb2 | 0.33370 (2) | 1.00541 (3) | 0.84467 (2) | 0.00913 (7) | |
Br1 | 0.00571 (4) | 0.42241 (7) | 0.75595 (3) | 0.02331 (12) | |
Br2 | 0.32633 (4) | 0.44788 (6) | 0.07711 (3) | 0.02106 (12) | |
Br3 | 0.32537 (4) | 0.55985 (7) | 0.57782 (3) | 0.02104 (12) | |
Br4 | 0.08301 (4) | 0.69674 (6) | 0.05644 (3) | 0.01888 (11) | |
Br5 | 0.05239 (3) | 0.70329 (6) | 0.57585 (3) | 0.01727 (11) | |
Br6 | 0.42333 (4) | 0.70854 (6) | 0.39338 (3) | 0.01891 (11) | |
Br7 | 0.38283 (4) | 0.71954 (6) | 0.91531 (3) | 0.01883 (11) | |
Br8 | 0.75719 (4) | 0.69343 (6) | 0.72033 (3) | 0.01818 (11) | |
Br9 | 0.70167 (3) | 0.68217 (6) | 0.24294 (3) | 0.02030 (11) | |
O1 | 0.4712 (3) | 0.5175 (5) | 0.2274 (3) | 0.0352 (10) | |
O2 | 0.1807 (3) | 0.4948 (6) | 0.4307 (2) | 0.0347 (10) | |
O3 | 0.6573 (3) | −0.0133 (5) | 0.3995 (2) | 0.0292 (9) | |
H1A | 0.482 (4) | 0.389 (9) | 0.234 (3) | 0.041 (11)* | |
H1B | 0.550 (5) | 0.557 (8) | 0.231 (3) | 0.041 (11)* | |
H1C | 0.435 (5) | 0.542 (8) | 0.275 (4) | 0.041 (11)* | |
H2A | 0.174 (5) | 0.605 (8) | 0.427 (3) | 0.037 (10)* | |
H2B | 0.107 (5) | 0.475 (8) | 0.436 (3) | 0.037 (10)* | |
H2C | 0.212 (5) | 0.459 (8) | 0.384 (3) | 0.037 (10)* | |
H3A | 0.619 (5) | −0.032 (9) | 0.438 (4) | 0.053 (12)* | |
H3B | 0.640 (5) | 0.053 (9) | 0.368 (4) | 0.053 (12)* | |
H3C | 0.725 (5) | −0.044 (9) | 0.403 (4) | 0.053 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb1 | 0.00861 (14) | 0.01001 (13) | 0.00876 (15) | 0.00043 (11) | 0.00000 (11) | −0.00060 (11) |
Sb2 | 0.00811 (14) | 0.00993 (13) | 0.00935 (16) | −0.00097 (11) | −0.00011 (11) | −0.00008 (11) |
Br1 | 0.0160 (2) | 0.0273 (3) | 0.0267 (3) | −0.0031 (2) | 0.0094 (2) | −0.0039 (2) |
Br2 | 0.0174 (2) | 0.0239 (2) | 0.0219 (3) | 0.00105 (18) | 0.0076 (2) | −0.00048 (19) |
Br3 | 0.0156 (2) | 0.0261 (3) | 0.0215 (3) | −0.00024 (19) | 0.0069 (2) | 0.0012 (2) |
Br4 | 0.0227 (2) | 0.0180 (2) | 0.0159 (3) | 0.00296 (18) | −0.0040 (2) | 0.00326 (18) |
Br5 | 0.0174 (2) | 0.0175 (2) | 0.0169 (3) | 0.00327 (17) | −0.00407 (19) | 0.00279 (17) |
Br6 | 0.0217 (2) | 0.0148 (2) | 0.0202 (3) | 0.00418 (18) | −0.0037 (2) | 0.00320 (18) |
Br7 | 0.0216 (2) | 0.0151 (2) | 0.0197 (3) | 0.00000 (18) | −0.0034 (2) | 0.00512 (18) |
Br8 | 0.0210 (2) | 0.0151 (2) | 0.0184 (3) | 0.00358 (17) | −0.0035 (2) | 0.00308 (18) |
Br9 | 0.0168 (2) | 0.0177 (2) | 0.0264 (3) | 0.00030 (18) | −0.0061 (2) | 0.00792 (19) |
O1 | 0.026 (2) | 0.030 (2) | 0.050 (3) | −0.0010 (17) | 0.006 (2) | −0.007 (2) |
O2 | 0.038 (3) | 0.031 (2) | 0.034 (2) | −0.009 (2) | 0.008 (2) | −0.007 (2) |
O3 | 0.023 (2) | 0.033 (2) | 0.032 (2) | 0.0070 (17) | 0.0060 (18) | 0.0126 (19) |
Geometric parameters (Å, º) top
Sb1—Br4i | 2.6175 (5) | Br4—Sb1viii | 2.6174 (5) |
Sb1—Br6 | 2.6349 (5) | Br5—Sb2vii | 2.6323 (5) |
Sb1—Br2i | 2.6631 (6) | Br8—Sb1iii | 2.9805 (5) |
Sb1—Br1ii | 2.9397 (6) | Br8—Sb1ix | 3.0279 (5) |
Sb1—Br8iii | 2.9805 (5) | Br9—Sb2iii | 2.9526 (5) |
Sb1—Br8iv | 3.0279 (5) | Br9—Sb2ii | 2.9955 (5) |
Sb2—Br5v | 2.6323 (5) | O1—H1A | 1.00 (7) |
Sb2—Br3v | 2.6436 (6) | O1—H1B | 1.10 (6) |
Sb2—Br7 | 2.6492 (5) | O1—H1C | 1.05 (7) |
Sb2—Br9iii | 2.9525 (5) | O2—H2A | 0.85 (6) |
Sb2—Br1v | 2.9704 (6) | O2—H2B | 1.01 (6) |
Sb2—Br9vi | 2.9956 (5) | O2—H2C | 1.03 (7) |
Br1—Sb1vi | 2.9398 (6) | O3—H3A | 0.91 (8) |
Br1—Sb2vii | 2.9704 (6) | O3—H3B | 0.81 (7) |
Br2—Sb1viii | 2.6631 (6) | O3—H3C | 0.95 (7) |
Br3—Sb2vii | 2.6437 (6) | | |
| | | |
Br4i—Sb1—Br6 | 94.236 (17) | Br5v—Sb2—Br1v | 94.181 (17) |
Br4i—Sb1—Br2i | 92.256 (18) | Br3v—Sb2—Br1v | 172.421 (18) |
Br6—Sb1—Br2i | 93.850 (18) | Br7—Sb2—Br1v | 88.527 (17) |
Br4i—Sb1—Br1ii | 88.849 (17) | Br9iii—Sb2—Br1v | 85.416 (16) |
Br6—Sb1—Br1ii | 91.932 (17) | Br5v—Sb2—Br9vi | 173.099 (18) |
Br2i—Sb1—Br1ii | 174.016 (18) | Br3v—Sb2—Br9vi | 87.685 (17) |
Br4i—Sb1—Br8iii | 90.919 (15) | Br7—Sb2—Br9vi | 94.847 (15) |
Br6—Sb1—Br8iii | 173.606 (18) | Br9iii—Sb2—Br9vi | 85.576 (9) |
Br2i—Sb1—Br8iii | 89.718 (17) | Br1v—Sb2—Br9vi | 84.748 (16) |
Br1ii—Sb1—Br8iii | 84.382 (15) | Sb1vi—Br1—Sb2vii | 155.23 (2) |
Br4i—Sb1—Br8iv | 171.042 (18) | Sb1iii—Br8—Sb1ix | 151.654 (19) |
Br6—Sb1—Br8iv | 91.306 (15) | Sb2iii—Br9—Sb2ii | 148.104 (18) |
Br2i—Sb1—Br8iv | 94.391 (16) | H1A—O1—H1B | 97 (5) |
Br1ii—Sb1—Br8iv | 83.929 (16) | H1A—O1—H1C | 97 (5) |
Br8iii—Sb1—Br8iv | 83.123 (8) | H1B—O1—H1C | 111 (5) |
Br5v—Sb2—Br3v | 93.282 (18) | H2A—O2—H2B | 93 (5) |
Br5v—Sb2—Br7 | 91.937 (16) | H2A—O2—H2C | 103 (6) |
Br3v—Sb2—Br7 | 92.544 (18) | H2B—O2—H2C | 117 (5) |
Br5v—Sb2—Br9iii | 87.544 (16) | H3A—O3—H3B | 122 (7) |
Br3v—Sb2—Br9iii | 93.588 (17) | H3A—O3—H3C | 118 (6) |
Br7—Sb2—Br9iii | 173.866 (19) | H3B—O3—H3C | 118 (7) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+1, −y+2, −z+1; (iv) x−1/2, −y+3/2, z−1/2; (v) −x+1/2, y+1/2, −z+3/2; (vi) x−1/2, −y+3/2, z+1/2; (vii) −x+1/2, y−1/2, −z+3/2; (viii) −x+1/2, y−1/2, −z+1/2; (ix) x+1/2, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···Br1x | 1.00 (7) | 2.43 (7) | 3.433 (4) | 178 (5) |
O1—H1B···Br9 | 1.10 (6) | 2.27 (6) | 3.361 (4) | 170 (5) |
O1—H1C···Br6 | 1.05 (7) | 2.61 (7) | 3.556 (5) | 150 (5) |
O1—H1C···Br8xi | 1.05 (7) | 3.15 (6) | 3.616 (4) | 108 (4) |
O2—H2A···Br2i | 0.85 (6) | 2.62 (6) | 3.463 (4) | 174 (6) |
O2—H2B···Br5xii | 1.01 (6) | 2.55 (6) | 3.485 (4) | 154 (5) |
O2—H2C···Br8xi | 1.03 (7) | 2.35 (7) | 3.338 (5) | 161 (5) |
O3—H3A···Br4xiii | 0.91 (8) | 2.65 (8) | 3.466 (4) | 151 (6) |
O3—H3B···Br1x | 0.81 (7) | 2.82 (7) | 3.486 (4) | 141 (6) |
O3—H3C···Br7x | 0.95 (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, z−1/2; (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 topAtom | W.p. | x | y | z | U11 | U22 | U33 | U12 | U13 | U23 | Ueq/Uiso |
Sb1 | 4e | 0.33714 (2) | 0.00339 (3) | 0.65247 (2) | 86 (1) | 100 (1) | 88 (2) | -4(1) | 0(1) | -6(1) | 91 (1) |
Sb2 | 4e | 0.33370 (2) | -0.00541 (3) | 0.15533 (2) | 81 (1) | 99 (1) | 93 (2) | 10 (1) | 1(1) | -1(1) | 91 (1) |
Br1 | 4e | 0.00571 (4) | 0.57759 (7) | 0.24405 (3) | 160 (2) | 273 (3) | 267 (3) | 31 (2) | -94 (2) | -39 (2) | 233 (1) |
Br2 | 4e | 0.32633 (4) | 0.55212 (6) | 0.92289 (3) | 174 (3) | 239 (2) | 219 (3) | -11 (2) | -77 (2) | -5(2) | 210 (1) |
Br3 | 4e | 0.32537 (4) | 0.44015 (7) | 0.42217 (3) | 156 (2) | 261 (3) | 215 (3) | 24 (2) | -69 (2) | 12 (2) | 210 (1) |
Br4 | 4e | 0.08300 (4) | 0.30326 (6) | 0.94356 (3) | 227 (3) | 180 (2) | 159 (3) | -30 (2) | 40 (2) | 33 (2) | 189 (1) |
Br5 | 4e | 0.05239 (3) | 0.29671 (6) | 0.42415 (3) | 173 (2) | 175 (2) | 169 (3) | -33 (2) | 41 (2) | 28 (2) | 173 (1) |
Br6 | 4e | 0.42333 (4) | 0.29146 (6) | 0.60662 (3) | 217 (3) | 148 (2) | 201 (3) | -42 (2) | 37 (2) | 32 (2) | 189 (1) |
Br7 | 4e | 0.38284 (4) | 0.28046 (6) | 0.08469 (3) | 217 (2) | 151 (2) | 197 (3) | 0(2) | 34 (2) | 51 (2) | 188 (1) |
Br8 | 4e | 0.75719 (4) | 0.30657 (6) | 0.27967 (3) | 210 (2) | 151 (2) | 184 (3) | -36 (2) | 35 (2) | 31 (2) | 182 (1) |
Br9 | 4e | 0.70166 (3) | 0.31783 (6) | 0.75705 (3) | 168 (2) | 176 (2) | 264 (3) | -3(2) | 61 (2) | 79 (2) | 203 (1) |
O1 | 4e | 0.4712 (3) | 0.5176 (5) | 0.2724 (3) | 257 (22) | 304 (22) | 496 (29) | -10 (17) | 62 (20) | -66 (20) | 352 (10) |
O2 | 4e | 0.1807 (4) | 0.4948 (6) | 0.4307 (3) | 385 (25) | 314 (22) | 343 (25) | -95 (20) | 85 (20) | -67 (20) | 347 (10) |
O3 | 4e | 0.6574 (3) | -0.0133 (5) | 0.3995 (2) | 231 (21) | 326 (22) | 321 (25) | 70 (17) | 60 (18) | 126 (19) | 292 (9) |
H1A | 4e | 0.482 (4) | 0.389 (9) | 0.234 (3) | | | | | | | 412 (106) |
H1B | 4e | 0.550 (5) | 0.556 (8) | 0.231 (3) | | | | | | | 412 (107) |
H1C | 4e | 0.435 (5) | 0.542 (8) | 0.275 (4) | | | | | | | 412 (107) |
H2A | 4e | 0.174 (5) | 0.605 (8) | 0.427 (3) | | | | | | | 367 (101) |
H2B | 4e | 0.107 (5) | 0.475 (8) | 0.436 (3) | | | | | | | 367 (101) |
H2C | 4e | 0.212 (5) | 0.459 (8) | 0.384 (3) | | | | | | | 367 (101) |
H3A | 4e | 0.379 (5) | -0.031 (9) | 0.437 (4) | | | | | | | 526 (124) |
H3B | 4e | 0.640 (5) | 0.053 (9) | 0.369 (4) | | | | | | | 526 (124) |
H3C | 4e | 0.725 (5) | -0.044 (9) | 0.403 (4) | | | | | | | 526 (124) |