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Single crystals of the title compounds were prepared by solid–solid reaction using BaBr2 flux at 1373 K. The structures of these two new cobaltites were solved and refined. The two compounds are built from a close-packing of [BaO3] and [BaOBr] layers with stacking sequences (cchhcc′)3 and (cchhhcc′)2 for the 18R and 14H structures, respectively, which create Co3O12 trimers or Co4O15 tetramers of face-sharing octahedra connected at their extremities to isolated tetrahedra by corner-sharing. These new materials are strongly related to the 5H-Ba5Co5O14/12H-Ba0.9CoO2.6 and 10H-Ba5Co5ClO13/6H-Ba6Co6ClO16 materials, with the existence of common blocks. In Ba6Co5BrO14 and Ba7Co6BrO17, all the atoms in the vicinity of the [BaOBr] layers are disordered, whereas the rest of the structure is perfectly ordered.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768107029394/bp5003sup1.cif
Contains datablocks I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768107029394/bp5003Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768107029394/bp5003IIsup3.hkl
Contains datablock II

Computing details top

For both compounds, program(s) used to refine structure: (Jana2000; Petricek and Dusek, 2000); software used to prepare material for publication: (Jana2000; Petricek and Dusek, 2000).

(I) top
Crystal data top
Ba7BrCo6O17F(000) = 1450
Mr = 1666.9Dx = 5.940 Mg m3
Hexagonal, P63/mmcMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 6c;-2cµ = 21.93 mm1
a = 5.6611 (1) ÅT = 293 K
c = 33.5672 (8) ÅHexagonal platelets, black
V = 931.64 (3) Å30.12 × 0.09 × 0.06 mm
Z = 2
Data collection top
Bruker APEX 11, CCD 4K
diffractometer
1045 reflections with I > 3σ(I)
φ and ω scansRint = 0.045
Absorption correction: multi-scanθmax = 39.9°, θmin = 1.2°
Tmin = 0.139, Tmax = 0.518h = 1010
11909 measured reflectionsk = 58
1158 independent reflectionsl = 6060
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/σ2(F)
R[F2 > 2σ(F2)] = 0.048(Δ/σ)max = 0.001
wR(F2) = 0.066Δρmax = 7.98 e Å3
S = 4.70Δρmin = 5.50 e Å3
1158 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
53 parametersExtinction coefficient: 0.028 (8)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba1000.12114 (2)0.00937 (16)
Ba20.3333330.6666670.186738 (18)0.00824 (15)
Ba3000.250.0115 (2)
Ba40.30479 (11)0.6096 (2)0.96009 (3)0.0134 (5)0.3333
Co10.3333330.6666670.85919 (4)0.0063 (3)
Co20.3333330.6666670.78574 (4)0.0057 (3)
Co30.3333330.6666670.08606 (5)0.0089 (3)
Br1000.4804 (4)0.035 (2)0.437 (15)
Br2000.50.023 (6)0.13 (3)
O10.4955 (4)0.9911 (9)0.89323 (17)0.0139 (13)
O20.1872 (4)0.3744 (8)0.82175 (13)0.0080 (11)
O30.5170 (6)0.0339 (12)0.250.0092 (17)
O40.2798 (17)0.560 (3)0.0343 (5)0.036 (7)0.3333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.00775 (19)0.00775 (19)0.0126 (3)0.00387 (10)00
Ba20.00653 (19)0.00653 (19)0.0117 (3)0.00326 (10)00
Ba30.0070 (2)0.0070 (2)0.0205 (4)0.00348 (12)00
Ba40.0134 (4)0.0184 (8)0.0100 (3)0.0092 (4)0.00033 (16)0.0007 (3)
Co10.0058 (3)0.0058 (3)0.0072 (5)0.00292 (17)00
Co20.0046 (3)0.0046 (3)0.0078 (5)0.00231 (17)00
Co30.0086 (4)0.0086 (4)0.0096 (6)0.0043 (2)00
Br10.0261 (12)0.0261 (12)0.053 (7)0.0130 (6)00
Br20.033 (7)0.033 (7)0.003 (13)0.017 (3)00
O10.0129 (14)0.0121 (19)0.016 (2)0.0061 (10)0.0021 (9)0.0043 (17)
O20.0096 (14)0.0042 (16)0.0083 (15)0.0021 (8)0.0004 (7)0.0009 (13)
O30.0105 (19)0.010 (3)0.007 (2)0.0049 (13)00
O40.053 (9)0.033 (10)0.015 (7)0.017 (5)0.000 (3)0.001 (7)
(II) top
Crystal data top
Ba6BrCo5O14F(000) = 1854
Mr = 1422.6Dx = 5.920 Mg m3
Trigonal, R3mMo Kα radiation, λ = 0.71069 Å
Hall symbol: -R 3;-2"µ = 22.16 mm1
a = 5.6578 (3) ÅT = 293 K
c = 43.166 (4) ÅHexagonal platelets, black
V = 1196.65 (14) Å30.13 × 0.10 × 0.06 mm
Z = 3
Data collection top
Bruker APEX 11, CCD 4K
diffractometer
1117 reflections with I > 3σ(I)
φ and ω scansRint = 0.045
Absorption correction: multi-scanθmax = 43.8°, θmin = 1.4°
Tmin = 0.128, Tmax = 0.265h = 510
13868 measured reflectionsk = 1010
1232 independent reflectionsl = 8084
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/σ2(F)
R[F2 > 2σ(F2)] = 0.032(Δ/σ)max = 0.0004
wR(F2) = 0.047Δρmax = 4.36 e Å3
S = 3.86Δρmin = 4.12 e Å3
1232 reflectionsExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
46 parametersExtinction coefficient: 0.023 (5)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba1000.093083 (9)0.00958 (9)
Ba2000.810512 (9)0.00961 (9)
Ba30.30796 (8)0.30796 (8)0.031094 (14)0.0153 (2)0.3333
Co1000.44255 (2)0.00649 (16)
Co2000.50.0061 (2)
Co3000.73297 (2)0.00947 (18)
Br1000.98409 (11)0.0225 (19)0.23 (3)
Br20000.097 (14)0.55 (5)
O10.4941 (2)0.4941 (2)0.08305 (7)0.0152 (8)
O20.4809 (2)0.4809 (2)0.19494 (6)0.0091 (6)
O30.2800 (10)0.2800 (10)0.9726 (2)0.031 (3)0.3333
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.00808 (11)0.00808 (11)0.01257 (15)0.00404 (6)00
Ba20.00743 (11)0.00743 (11)0.01396 (16)0.00372 (6)00
Ba30.0154 (3)0.0154 (3)0.0119 (2)0.00541 (19)0.00141 (10)0.00141 (10)
Co10.00549 (19)0.00549 (19)0.0085 (3)0.00274 (9)00
Co20.0053 (2)0.0053 (2)0.0077 (4)0.00266 (12)00
Co30.0088 (2)0.0088 (2)0.0108 (3)0.00440 (11)00
Br10.022 (2)0.022 (2)0.023 (4)0.0112 (10)00
Br20.0425 (19)0.0425 (19)0.21 (4)0.0212 (9)00
O10.0137 (9)0.0137 (9)0.0217 (12)0.0096 (9)0.0014 (5)0.0014 (5)
O20.0093 (7)0.0093 (7)0.0102 (8)0.0059 (8)0.0006 (4)0.0006 (4)
O30.036 (4)0.036 (4)0.010 (3)0.009 (4)0.0028 (17)0.0028 (17)
 

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