A new quaternary oxide, BiGaTi4O11 (bismuth gallium tetratitanium undecaoxide), was prepared by heating a mixture of the binary oxides at 1373 K in air. BiGaTi4O11 melts at 1487 K and prismatic single crystals were obtained from a sample melted at 1523 K and solidified by furnace cooling. The structure of BiGaTi4O11 was analyzed using single-crystal X-ray diffraction to be of a new type that crystallized in the space group Cmcm. A Bi3+ site is coordinated by nine O2− anions, and three oxygen-coordinated octahedral sites are statistically occupied by Ga3+ and Ti4+ cations. A relative dielectric constant of 46 with a temperature coefficient of 57 ppm K−1 in the temperature range 297–448 K was measured for a polycrystalline ceramic sample at 150 Hz–1 MHz with a dielectric loss tan δ of less than 0.01. Electrical resistivities measured at 1073 K by alternating-current impedance spectroscopic and direct-current methods were 1.16 × 10−4 and 1.14 × 10−4 S cm−1, respectively, which indicates that electrons and/or holes were conduction carriers at high temperature. The optical band gap estimated by the results of diffuse reflectance analysis was 2.9–3.0 eV, while the band gap obtained from the activation energy for electrical conduction was 3.5 eV.
Supporting information
CCDC reference: 1913005
Data collection: APEX3 (Bruker, 2015); cell refinement: APEX3 (Bruker, 2015); data reduction: APEX3 (Bruker, 2015); program(s) used to solve structure: APEX3 (Bruker, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: VESTA (Momma & Izumi, 2011); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
Bismuth gallium tetratitanium undecaoxide
top
Crystal data top
BiGaTi4O11 | Dx = 5.253 Mg m−3 |
Mr = 646.30 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmcm | Cell parameters from 1471 reflections |
a = 3.7406 (1) Å | θ = 3.3–38.0° |
b = 12.2765 (3) Å | µ = 28.49 mm−1 |
c = 17.7955 (4) Å | T = 301 K |
V = 817.20 (3) Å3 | Prismatic, translucent colourless |
Z = 4 | 0.10 × 0.05 × 0.03 mm |
F(000) = 1160 | |
Data collection top
Bruker D8 goniometer diffractometer | 726 independent reflections |
Radiation source: micro focus sealed tube | 718 reflections with I > 2σ(I) |
Detector resolution: 7.4074 pixels mm-1 | Rint = 0.030 |
ω, φ scans | θmax = 30.5°, θmin = 3.3° |
Absorption correction: numerical (SADABS; Bruker, 2015) | h = −5→5 |
Tmin = 0.12, Tmax = 0.44 | k = −17→17 |
17075 measured reflections | l = −25→25 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0161P)2 + 1.0978P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.011 | (Δ/σ)max = 0.001 |
wR(F2) = 0.028 | Δρmax = 0.99 e Å−3 |
S = 1.20 | Δρmin = −0.54 e Å−3 |
726 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
59 parameters | Extinction coefficient: 0.00138 (11) |
1 restraint | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Bi1 | 0.0000 | 0.39623 (2) | 0.2500 | 0.01369 (6) | |
Ga1 | 0.0000 | 0.06700 (3) | 0.57301 (2) | 0.00515 (10) | 0.098 (2) |
Ti1 | 0.0000 | 0.06700 (3) | 0.57301 (2) | 0.00515 (10) | 0.902 (2) |
Ga2 | 0.0000 | 0.22780 (3) | 0.07172 (2) | 0.00542 (9) | 0.302 (2) |
Ti2 | 0.0000 | 0.22780 (3) | 0.07172 (2) | 0.00542 (9) | 0.698 (2) |
Ga3 | 0.0000 | 0.10601 (4) | 0.2500 | 0.00827 (15) | 0.201 (5) |
Ti3 | 0.0000 | 0.10601 (4) | 0.2500 | 0.00827 (15) | 0.799 (5) |
O1 | 0.0000 | 0.04439 (17) | 0.67786 (9) | 0.0123 (3) | |
O2 | 0.0000 | 0.07822 (13) | 0.04410 (9) | 0.0072 (3) | |
O3 | 0.0000 | 0.20679 (15) | 0.17342 (9) | 0.0104 (3) | |
O4 | 0.0000 | 0.23954 (13) | 0.55257 (9) | 0.0068 (3) | |
O5 | 0.0000 | 0.39331 (13) | 0.07868 (10) | 0.0082 (3) | |
O6 | 0.0000 | 0.5725 (2) | 0.2500 | 0.0107 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Bi1 | 0.00968 (8) | 0.00735 (8) | 0.02403 (9) | 0.000 | 0.000 | 0.000 |
Ga1 | 0.00529 (17) | 0.00558 (17) | 0.00459 (17) | 0.000 | 0.000 | −0.00031 (11) |
Ti1 | 0.00529 (17) | 0.00558 (17) | 0.00459 (17) | 0.000 | 0.000 | −0.00031 (11) |
Ga2 | 0.00503 (16) | 0.00517 (15) | 0.00606 (16) | 0.000 | 0.000 | −0.00043 (10) |
Ti2 | 0.00503 (16) | 0.00517 (15) | 0.00606 (16) | 0.000 | 0.000 | −0.00043 (10) |
Ga3 | 0.0056 (3) | 0.0070 (3) | 0.0122 (3) | 0.000 | 0.000 | 0.000 |
Ti3 | 0.0056 (3) | 0.0070 (3) | 0.0122 (3) | 0.000 | 0.000 | 0.000 |
O1 | 0.0108 (8) | 0.0206 (9) | 0.0054 (7) | 0.000 | 0.000 | 0.0012 (6) |
O2 | 0.0114 (8) | 0.0049 (6) | 0.0054 (7) | 0.000 | 0.000 | −0.0007 (5) |
O3 | 0.0147 (8) | 0.0110 (8) | 0.0054 (7) | 0.000 | 0.000 | 0.0019 (6) |
O4 | 0.0049 (7) | 0.0079 (7) | 0.0076 (7) | 0.000 | 0.000 | −0.0002 (5) |
O5 | 0.0056 (7) | 0.0067 (7) | 0.0122 (8) | 0.000 | 0.000 | −0.0006 (5) |
O6 | 0.0063 (10) | 0.0057 (10) | 0.0200 (12) | 0.000 | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Bi1—O6 | 2.164 (2) | Ga/Ti3—O3 | 1.8406 (17) |
Bi1—O1i | 2.3827 (11) | Ga/Ti3—O3v | 1.8406 (17) |
Bi1—O1ii | 2.3827 (11) | Ga/Ti3—O6xii | 1.9150 (5) |
Bi1—O1iii | 2.3827 (11) | Ga/Ti3—O6xiii | 1.9150 (5) |
Bi1—O1iv | 2.3827 (11) | Ga/Ti3—O1xiv | 2.249 (2) |
Bi1—O3 | 2.6955 (18) | Ga/Ti3—O1xi | 2.249 (2) |
Bi1—O3v | 2.6955 (18) | Ga3—Bi1xii | 3.1828 (4) |
Bi1—O5 | 3.0490 (19) | Ga3—Bi1xiii | 3.1828 (4) |
Bi1—O5v | 3.0490 (19) | O1—Ti3xi | 2.249 (2) |
Bi1—Ga3vi | 3.1827 (4) | O1—Ga3xi | 2.249 (2) |
Bi1—Ti3vi | 3.1827 (4) | O1—Bi1i | 2.3827 (11) |
Bi1—Ti3vii | 3.1827 (4) | O1—Bi1iv | 2.3827 (11) |
Bi1—Ga3vii | 3.1827 (4) | O2—Ti1xiv | 1.8555 (17) |
Ga/Ti1—O2viii | 1.8555 (17) | O2—Ga1xiv | 1.8555 (17) |
Ga/Ti1—O1 | 1.8864 (17) | O2—Ti1v | 2.0885 (17) |
Ga/Ti1—O5ix | 1.9353 (4) | O2—Ga1v | 2.0885 (17) |
Ga/Ti1—O5x | 1.9353 (4) | O4—Ti2ix | 1.9429 (5) |
Ga/Ti1—O2v | 2.0886 (17) | O4—Ga2ix | 1.9429 (5) |
Ga/Ti1—O4 | 2.1492 (17) | O4—Ti2x | 1.9429 (5) |
Ga1—Ti1xi | 3.0754 (7) | O4—Ga2x | 1.9429 (5) |
Ga1—Ti2ix | 3.1376 (4) | O4—Ti2v | 2.2165 (17) |
Ga1—Ti2x | 3.1376 (4) | O4—Ga2v | 2.2165 (17) |
Ga/Ti2—O3 | 1.8281 (17) | O5—Ti1iii | 1.9353 (4) |
Ga/Ti2—O2 | 1.9009 (16) | O5—Ga1iii | 1.9353 (4) |
Ga/Ti2—O4iii | 1.9429 (5) | O5—Ti1ii | 1.9353 (4) |
Ga/Ti2—O4ii | 1.9429 (5) | O5—Ga1ii | 1.9353 (4) |
Ga/Ti2—O5 | 2.0357 (16) | O6—Ti3vi | 1.9150 (5) |
Ga/Ti2—O4v | 2.2165 (17) | O6—Ga3vi | 1.9150 (5) |
Ga2—Ti1iii | 3.1376 (4) | O6—Ti3vii | 1.9150 (5) |
Ga2—Ti1ii | 3.1376 (4) | O6—Ga3vii | 1.9150 (5) |
| | | |
O6—Bi1—O1i | 72.19 (5) | O3—Ga2—Ti1iii | 96.09 (5) |
O6—Bi1—O1ii | 72.19 (5) | O2—Ga2—Ti1iii | 141.029 (18) |
O1i—Bi1—O1ii | 144.37 (9) | O4iii—Ga2—Ti1iii | 42.42 (5) |
O6—Bi1—O1iii | 72.19 (5) | O4ii—Ga2—Ti1iii | 114.17 (5) |
O1i—Bi1—O1iii | 65.20 (7) | O5—Ga2—Ti1iii | 36.693 (7) |
O1ii—Bi1—O1iii | 103.43 (7) | O4v—Ga2—Ti1iii | 87.42 (4) |
O6—Bi1—O1iv | 72.19 (5) | O3—Ga2—Ti1ii | 96.09 (5) |
O1i—Bi1—O1iv | 103.43 (7) | O2—Ga2—Ti1ii | 141.029 (18) |
O1ii—Bi1—O1iv | 65.20 (7) | O4iii—Ga2—Ti1ii | 114.17 (5) |
O1iii—Bi1—O1iv | 144.37 (9) | O4ii—Ga2—Ti1ii | 42.42 (5) |
O6—Bi1—O3 | 149.63 (3) | O5—Ga2—Ti1ii | 36.693 (7) |
O1i—Bi1—O3 | 122.43 (4) | O4v—Ga2—Ti1ii | 87.42 (4) |
O1ii—Bi1—O3 | 89.52 (5) | Ti1iii—Ga2—Ti1ii | 73.180 (11) |
O1iii—Bi1—O3 | 89.52 (5) | O3—Ga3—O3v | 95.52 (11) |
O1iv—Bi1—O3 | 122.43 (4) | O3—Ga3—O6xii | 98.30 (5) |
O6—Bi1—O3v | 149.63 (3) | O3v—Ga3—O6xii | 98.30 (5) |
O1i—Bi1—O3v | 89.52 (5) | O3—Ga3—O6xiii | 98.30 (5) |
O1ii—Bi1—O3v | 122.43 (4) | O3v—Ga3—O6xiii | 98.30 (5) |
O1iii—Bi1—O3v | 122.43 (4) | O6xii—Ga3—O6xiii | 155.19 (15) |
O1iv—Bi1—O3v | 89.52 (5) | O3—Ga3—O1xiv | 97.43 (7) |
O3—Bi1—O3v | 60.74 (7) | O3v—Ga3—O1xiv | 167.05 (7) |
O6—Bi1—Ga3vi | 35.990 (5) | O6xii—Ga3—O1xiv | 79.84 (6) |
O1i—Bi1—Ga3vi | 44.86 (5) | O6xiii—Ga3—O1xiv | 79.84 (6) |
O1ii—Bi1—Ga3vi | 102.34 (4) | O3—Ga3—O1xi | 167.05 (7) |
O1iii—Bi1—Ga3vi | 44.86 (5) | O3v—Ga3—O1xi | 97.43 (7) |
O1iv—Bi1—Ga3vi | 102.34 (4) | O6xii—Ga3—O1xi | 79.84 (6) |
O3—Bi1—Ga3vi | 134.28 (2) | O6xiii—Ga3—O1xi | 79.84 (6) |
O3v—Bi1—Ga3vi | 134.28 (2) | O1xiv—Ga3—O1xi | 69.62 (9) |
O6—Bi1—Ti3vi | 35.990 (5) | O3—Ga3—Bi1xii | 122.95 (4) |
O1i—Bi1—Ti3vi | 44.86 (5) | O3v—Ga3—Bi1xii | 122.95 (4) |
O1ii—Bi1—Ti3vi | 102.34 (4) | O6xii—Ga3—Bi1xii | 41.61 (7) |
O1iii—Bi1—Ti3vi | 44.86 (5) | O6xiii—Ga3—Bi1xii | 113.58 (7) |
O1iv—Bi1—Ti3vi | 102.34 (4) | O1xiv—Ga3—Bi1xii | 48.37 (3) |
O3—Bi1—Ti3vi | 134.28 (2) | O1xi—Ga3—Bi1xii | 48.37 (3) |
O3v—Bi1—Ti3vi | 134.28 (2) | O3—Ga3—Bi1xiii | 122.95 (4) |
Ga3vi—Bi1—Ti3vi | 0.000 (10) | O3v—Ga3—Bi1xiii | 122.95 (4) |
O6—Bi1—Ti3vii | 35.990 (5) | O6xii—Ga3—Bi1xiii | 113.58 (7) |
O1i—Bi1—Ti3vii | 102.34 (4) | O6xiii—Ga3—Bi1xiii | 41.61 (7) |
O1ii—Bi1—Ti3vii | 44.86 (5) | O1xiv—Ga3—Bi1xiii | 48.37 (3) |
O1iii—Bi1—Ti3vii | 102.34 (4) | O1xi—Ga3—Bi1xiii | 48.37 (3) |
O1iv—Bi1—Ti3vii | 44.86 (5) | Bi1xii—Ga3—Bi1xiii | 71.978 (11) |
O3—Bi1—Ti3vii | 134.28 (2) | Ga1—O1—Ti3xi | 133.27 (10) |
O3v—Bi1—Ti3vii | 134.28 (2) | Ga1—O1—Ga3xi | 133.27 (10) |
Ga3vi—Bi1—Ti3vii | 71.979 (11) | Ti3xi—O1—Ga3xi | 0.0 |
Ti3vi—Bi1—Ti3vii | 71.979 (11) | Ga1—O1—Bi1i | 119.20 (5) |
O6—Bi1—Ga3vii | 35.990 (5) | Ti3xi—O1—Bi1i | 86.77 (5) |
O1i—Bi1—Ga3vii | 102.34 (4) | Ga3xi—O1—Bi1i | 86.77 (5) |
O1ii—Bi1—Ga3vii | 44.86 (5) | Ga1—O1—Bi1iv | 119.20 (5) |
O1iii—Bi1—Ga3vii | 102.34 (4) | Ti3xi—O1—Bi1iv | 86.77 (5) |
O1iv—Bi1—Ga3vii | 44.86 (5) | Ga3xi—O1—Bi1iv | 86.77 (5) |
O3—Bi1—Ga3vii | 134.28 (2) | Bi1i—O1—Bi1iv | 103.43 (7) |
O3v—Bi1—Ga3vii | 134.28 (2) | Ti1xiv—O2—Ga1xiv | 0.0 |
Ga3vi—Bi1—Ga3vii | 71.979 (11) | Ti1xiv—O2—Ga2 | 148.92 (10) |
Ti3vi—Bi1—Ga3vii | 72.0 | Ga1xiv—O2—Ga2 | 148.92 (10) |
Ti3vii—Bi1—Ga3vii | 0.0 | Ti1xiv—O2—Ti1v | 102.31 (8) |
O2viii—Ga1—O1 | 97.63 (8) | Ga1xiv—O2—Ti1v | 102.31 (8) |
O2viii—Ga1—O5ix | 104.85 (5) | Ga2—O2—Ti1v | 108.76 (8) |
O1—Ga1—O5ix | 89.17 (6) | Ti1xiv—O2—Ga1v | 102.3 |
O2viii—Ga1—O5x | 104.85 (5) | Ga1xiv—O2—Ga1v | 102.31 (8) |
O1—Ga1—O5x | 89.17 (6) | Ga2—O2—Ga1v | 108.76 (8) |
O5ix—Ga1—O5x | 150.21 (9) | Ti1v—O2—Ga1v | 0.0 |
O2viii—Ga1—O2v | 77.69 (8) | Ga2—O3—Ga3 | 145.87 (11) |
O1—Ga1—O2v | 175.32 (8) | Ga2—O3—Bi1 | 112.26 (8) |
O5ix—Ga1—O2v | 92.03 (6) | Ga3—O3—Bi1 | 101.87 (7) |
O5x—Ga1—O2v | 92.03 (6) | Ti2ix—O4—Ga2ix | 0.0 |
O2viii—Ga1—O4 | 154.16 (8) | Ti2ix—O4—Ti2x | 148.57 (10) |
O1—Ga1—O4 | 108.21 (8) | Ga2ix—O4—Ti2x | 148.57 (10) |
O5ix—Ga1—O4 | 76.16 (5) | Ti2ix—O4—Ga2x | 148.6 |
O5x—Ga1—O4 | 76.16 (5) | Ga2ix—O4—Ga2x | 148.57 (10) |
O2v—Ga1—O4 | 76.48 (6) | Ti2x—O4—Ga2x | 0.0 |
O2viii—Ga1—Ti1xi | 41.57 (5) | Ti2ix—O4—Ga1 | 100.00 (5) |
O1—Ga1—Ti1xi | 139.20 (7) | Ga2ix—O4—Ga1 | 100.00 (5) |
O5ix—Ga1—Ti1xi | 100.29 (5) | Ti2x—O4—Ga1 | 100.00 (5) |
O5x—Ga1—Ti1xi | 100.29 (5) | Ga2x—O4—Ga1 | 100.00 (5) |
O2v—Ga1—Ti1xi | 36.12 (5) | Ti2ix—O4—Ti2v | 100.87 (5) |
O4—Ga1—Ti1xi | 112.59 (5) | Ga2ix—O4—Ti2v | 100.87 (5) |
O2viii—Ga1—Ti2ix | 140.30 (2) | Ti2x—O4—Ti2v | 100.87 (5) |
O1—Ga1—Ti2ix | 97.20 (5) | Ga2x—O4—Ti2v | 100.87 (5) |
O5ix—Ga1—Ti2ix | 38.94 (5) | Ga1—O4—Ti2v | 96.02 (7) |
O5x—Ga1—Ti2ix | 111.98 (5) | Ti2ix—O4—Ga2v | 100.9 |
O2v—Ga1—Ti2ix | 86.55 (4) | Ga2ix—O4—Ga2v | 100.87 (5) |
O4—Ga1—Ti2ix | 37.577 (11) | Ti2x—O4—Ga2v | 100.9 |
Ti1xi—Ga1—Ti2ix | 115.045 (14) | Ga2x—O4—Ga2v | 100.87 (5) |
O2viii—Ga1—Ti2x | 140.30 (2) | Ga1—O4—Ga2v | 96.02 (7) |
O1—Ga1—Ti2x | 97.20 (5) | Ti2v—O4—Ga2v | 0.0 |
O5ix—Ga1—Ti2x | 111.98 (5) | Ti1iii—O5—Ga1iii | 0.0 |
O5x—Ga1—Ti2x | 38.94 (5) | Ti1iii—O5—Ti1ii | 150.21 (9) |
O2v—Ga1—Ti2x | 86.55 (4) | Ga1iii—O5—Ti1ii | 150.21 (9) |
O4—Ga1—Ti2x | 37.577 (11) | Ti1iii—O5—Ga1ii | 150.2 |
Ti1xi—Ga1—Ti2x | 115.045 (14) | Ga1iii—O5—Ga1ii | 150.21 (9) |
Ti2ix—Ga1—Ti2x | 73.181 (11) | Ti1ii—O5—Ga1ii | 0.0 |
O3—Ga2—O2 | 96.88 (8) | Ti1iii—O5—Ga2 | 104.36 (5) |
O3—Ga2—O4iii | 101.70 (5) | Ga1iii—O5—Ga2 | 104.36 (5) |
O2—Ga2—O4iii | 98.86 (5) | Ti1ii—O5—Ga2 | 104.36 (5) |
O3—Ga2—O4ii | 101.70 (5) | Ga1ii—O5—Ga2 | 104.36 (5) |
O2—Ga2—O4ii | 98.86 (5) | Ti3vi—O6—Ga3vi | 0.0 |
O4iii—Ga2—O4ii | 148.57 (9) | Ti3vi—O6—Ti3vii | 155.19 (15) |
O3—Ga2—O5 | 94.62 (8) | Ga3vi—O6—Ti3vii | 155.19 (15) |
O2—Ga2—O5 | 168.50 (7) | Ti3vi—O6—Ga3vii | 155.2 |
O4iii—Ga2—O5 | 78.74 (5) | Ga3vi—O6—Ga3vii | 155.19 (15) |
O4ii—Ga2—O5 | 78.74 (5) | Ti3vii—O6—Ga3vii | 0.0 |
O3—Ga2—O4v | 175.62 (7) | Ti3vi—O6—Bi1 | 102.40 (7) |
O2—Ga2—O4v | 78.74 (7) | Ga3vi—O6—Bi1 | 102.40 (7) |
O4iii—Ga2—O4v | 79.14 (5) | Ti3vii—O6—Bi1 | 102.40 (7) |
O4ii—Ga2—O4v | 79.14 (5) | Ga3vii—O6—Bi1 | 102.40 (7) |
O5—Ga2—O4v | 89.76 (7) | | |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x−1/2, −y+1/2, z−1/2; (iii) −x+1/2, −y+1/2, z−1/2; (iv) −x−1/2, −y+1/2, −z+1; (v) x, y, −z+1/2; (vi) x+1/2, y+1/2, z; (vii) x−1/2, y+1/2, z; (viii) −x, −y, z+1/2; (ix) −x+1/2, −y+1/2, z+1/2; (x) −x−1/2, −y+1/2, z+1/2; (xi) −x, −y, −z+1; (xii) x−1/2, y−1/2, z; (xiii) x+1/2, y−1/2, z; (xiv) −x, −y, z−1/2. |