The structures of the monoclinic and the orthorhombic phases of type I langbeinite Tl2Cd2(SO4)3 have been determined at 121 and 85 K, respectively, by X-ray diffraction. A precise analysis of these structures shows the existence of some differences compared to langbeinites of type II. The monoclinic structure differs very little from the high-temperature cubic structure and the distortion relating the monoclinic structure to the cubic one is very small. SO4 tetrahedra seem to rotate under orthorhombic symmetry in the monoclinic phase. A symmetry distortion analysis of the ferroelectric monoclinic distortion discloses the importance of the secondary modes with orthorhombic symmetry, especially for the O atoms of the SO4 groups.
Supporting information
Data collection: DIF4 for 121K; CAD4VPC for (85K). Cell refinement: DIF4 for 121K; CAD4VPC for (85K). Data reduction: AVSORT, REDUCE, xtal_ABSORB for 121K; JANA98 for (85K). For both compounds, program(s) used to solve structure: JANA98; program(s) used to refine structure: JANA98; molecular graphics: ORTEP; software used to prepare material for publication: JANA98.
Crystal data top
Tl2Cd2(SO4)3 | F(000) = 1608 |
Mr = 921.7 | Dx = 5.515 Mg m−3 |
Monoclinic, P1121 | Synchrotron radiation, λ = 0.5502 Å |
Hall symbol: P 21 | Cell parameters from 27 reflections |
a = 10.356 (4) Å | θ = 7.4–29.2° |
b = 10.350 (2) Å | µ = 17.53 mm−1 |
c = 10.353 (6) Å | T = 121 K |
β = 90° | Parallelepiped, colourless |
V = 1109.7 (8) Å3 | 0.59 × 0.35 × 0.35 mm |
Z = 4 | |
Data collection top
Huber CAD-4 κ geometry diffractometer | 8392 reflections with I > 3σ(I) |
θ/2θ scans | θmax = 20.0°, θmin = 1.5° |
Absorption correction: analytical (Alcock, 1974) | h = −12→12 |
Tmin = 0.009, Tmax = 0.046 | k = −12→12 |
9312 measured reflections | l = −12→12 |
8392 independent reflections | 2 standard reflections every 20 min |
Refinement top
Refinement on F | Weighting scheme based on measured s.u.'s w = 1/σ2(F) |
R[F2 > 2σ(F2)] = 0.044 | (Δ/σ)max = 0.001 |
wR(F2) = 0.064 | Δρmax = 2.43 e Å−3 |
S = 13.78 | Δρmin = −1.86 e Å−3 |
8392 reflections | Extinction correction: B-C type 1 Gaussian isotropic |
132 parameters | Extinction coefficient: 0.182 (4) |
Crystal data top
Tl2Cd2(SO4)3 | V = 1109.7 (8) Å3 |
Mr = 921.7 | Z = 4 |
Monoclinic, P1121 | Synchrotron radiation, λ = 0.5502 Å |
a = 10.356 (4) Å | µ = 17.53 mm−1 |
b = 10.350 (2) Å | T = 121 K |
c = 10.353 (6) Å | 0.59 × 0.35 × 0.35 mm |
β = 90° | |
Data collection top
Huber CAD-4 κ geometry diffractometer | 8392 independent reflections |
Absorption correction: analytical (Alcock, 1974) | 8392 reflections with I > 3σ(I) |
Tmin = 0.009, Tmax = 0.046 | 2 standard reflections every 20 min |
9312 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 132 parameters |
wR(F2) = 0.064 | Δρmax = 2.43 e Å−3 |
S = 13.78 | Δρmin = −1.86 e Å−3 |
8392 reflections | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Tl21 | 0.80235 (4) | 0.05287 (4) | 0.043756 | 0.0136 (1) | |
Tl11 | 0.56739 (4) | 0.81699 (5) | 0.81002 (6) | 0.0144 (1) | |
Tl12 | 0.06866 (4) | 0.68261 (4) | 0.17413 (6) | 0.0149 (1) | |
Tl22 | 0.30273 (4) | 0.44800 (4) | 0.93967 (7) | 0.0145 (1) | |
Cd11 | 0.08851 (6) | 0.33194 (9) | 0.32064 (9) | 0.00722 (8) | |
Cd12 | 0.58546 (7) | 0.16893 (9) | 0.66497 (8) | 0.00957 (8) | |
Cd21 | 0.33856 (7) | 0.59002 (7) | 0.57932 (9) | 0.00526 (7) | |
Cd22 | 0.83717 (7) | 0.91000 (7) | 0.40177 (9) | 0.00797 (8) | |
S1a | 0.0298 (2) | 0.6217 (2) | 0.5043 (2) | 0.0046 (1) | |
O1a | −0.0582 (3) | 0.7173 (3) | 0.4514 (4) | 0.0130 (4) | |
O2a | 0.1604 (2) | 0.6676 (4) | 0.4767 (4) | 0.0054 (4) | |
O3a | 0.0059 (4) | 0.4974 (3) | 0.4361 (4) | 0.0118 (5) | |
O4a | 0.0049 (4) | 0.5999 (4) | 0.6455 (3) | 0.0154 (5) | |
S1b | 0.5331 (2) | 0.8839 (2) | 0.4799 (2) | 0.0046 (1) | |
O1b | 0.4452 (3) | 0.7855 (3) | 0.5279 (4) | 0.0130 (4) | |
O2b | 0.6637 (2) | 0.8377 (4) | 0.5066 (4) | 0.0054 (4) | |
O3b | 0.5080 (4) | 1.0049 (3) | 0.5533 (4) | 0.0118 (5) | |
O4b | 0.5091 (4) | 0.9117 (4) | 0.3397 (3) | 0.0154 (5) | |
S1c | 0.2647 (2) | 0.2710 (2) | 0.6201 (2) | 0.0046 (1) | |
O1c | 0.2257 (4) | 0.1843 (4) | 0.7233 (3) | 0.0130 (4) | |
O2c | 0.2252 (4) | 0.4008 (3) | 0.6593 (4) | 0.0054 (4) | |
O3c | 0.1942 (4) | 0.2321 (4) | 0.5011 (3) | 0.0118 (5) | |
O4c | 0.4065 (2) | 0.2596 (4) | 0.5928 (4) | 0.0154 (5) | |
S1d | 0.7626 (2) | 0.2300 (2) | 0.3648 (2) | 0.0046 (1) | |
O1d | 0.7322 (4) | 0.3210 (4) | 0.2625 (3) | 0.0130 (4) | |
O2d | 0.7187 (4) | 0.1033 (3) | 0.3205 (4) | 0.0054 (4) | |
O3d | 0.6891 (4) | 0.2692 (4) | 0.4818 (3) | 0.0118 (5) | |
O4d | 0.9036 (2) | 0.2339 (4) | 0.3982 (4) | 0.0154 (5) | |
S1e | 0.3767 (2) | 0.5145 (2) | 0.2718 (2) | 0.0046 (1) | |
O1e | 0.4782 (3) | 0.4691 (4) | 0.1864 (4) | 0.0130 (4) | |
O2e | 0.4319 (4) | 0.5181 (4) | 0.4018 (3) | 0.0054 (4) | |
O3e | 0.2692 (3) | 0.4192 (4) | 0.2669 (4) | 0.0118 (5) | |
O4e | 0.3244 (4) | 0.6423 (2) | 0.2277 (4) | 0.0154 (5) | |
S1f | 0.8772 (2) | 0.9859 (2) | 0.7125 (2) | 0.0046 (1) | |
O1f | 0.9815 (3) | 1.0335 (4) | 0.7933 (4) | 0.0130 (4) | |
O2f | 0.9290 (4) | 0.9755 (4) | 0.5816 (3) | 0.0054 (4) | |
O3f | 0.7713 (3) | 1.0830 (4) | 0.7157 (4) | 0.0118 (5) | |
O4f | 0.8239 (4) | 0.8610 (2) | 0.7636 (4) | 0.0154 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Tl21 | 0.0150 (2) | 0.0118 (2) | 0.0139 (2) | −0.0065 (2) | 0.0011 (2) | −0.0005 (2) |
Tl11 | 0.0134 (2) | 0.0177 (2) | 0.0121 (2) | −0.0051 (2) | 0.0017 (2) | −0.0004 (2) |
Tl12 | 0.0148 (2) | 0.0160 (2) | 0.0140 (2) | −0.0061 (2) | 0.0009 (2) | −0.0020 (2) |
Tl22 | 0.0160 (2) | 0.0126 (2) | 0.0147 (2) | −0.0057 (2) | −0.0005 (1) | 0.0003 (2) |
S1a | 0.0035 (2) | 0.0056 (2) | 0.0046 (1) | −0.0001 (1) | 0.0002 (1) | −0.0017 (1) |
O1a | 0.0094 (6) | 0.0119 (6) | 0.0178 (7) | 0.0010 (5) | −0.0071 (5) | −0.0009 (5) |
O2a | 0.0024 (5) | 0.0013 (6) | 0.012 (1) | 0.0003 (4) | 0.0027 (7) | −0.0003 (7) |
O3a | 0.014 (1) | 0.0086 (7) | 0.0124 (8) | −0.0013 (6) | 0.0040 (7) | 0.0012 (6) |
O4a | 0.026 (1) | 0.0070 (7) | 0.0132 (7) | 0.0019 (7) | 0.0053 (6) | 0.0029 (5) |
S1b | 0.0035 (2) | 0.0057 (2) | 0.0045 (1) | 0.0001 (1) | −0.0002 (1) | −0.0016 (1) |
O1b | 0.0093 (6) | 0.0120 (6) | 0.0178 (7) | −0.0013 (5) | 0.0070 (5) | −0.0012 (5) |
O2b | 0.0024 (5) | 0.0013 (6) | 0.012 (1) | −0.0001 (4) | −0.0028 (7) | −0.0008 (7) |
O3b | 0.014 (1) | 0.0086 (7) | 0.0125 (8) | 0.0015 (6) | −0.0039 (7) | 0.0010 (6) |
O4b | 0.026 (1) | 0.0067 (7) | 0.0134 (7) | −0.0016 (7) | −0.0053 (6) | 0.0025 (5) |
S1c | 0.0044 (1) | 0.0035 (2) | 0.0057 (2) | 0.0002 (1) | −0.0016 (1) | −0.0002 (1) |
O1c | 0.0191 (7) | 0.0081 (6) | 0.0119 (6) | −0.0061 (5) | −0.0010 (5) | 0.0014 (5) |
O2c | 0.012 (1) | 0.0031 (5) | 0.0013 (6) | 0.0037 (7) | −0.0010 (7) | 0.0000 (4) |
O3c | 0.0117 (8) | 0.015 (1) | 0.0087 (7) | 0.0037 (7) | 0.0009 (6) | −0.0018 (6) |
O4c | 0.0124 (7) | 0.027 (1) | 0.0066 (7) | 0.0041 (6) | 0.0021 (5) | 0.0007 (7) |
S1d | 0.0043 (1) | 0.0036 (2) | 0.0059 (2) | −0.0002 (1) | 0.0015 (1) | −0.0003 (1) |
O1d | 0.0195 (7) | 0.0075 (6) | 0.0120 (6) | 0.0055 (5) | 0.0015 (5) | 0.0015 (5) |
O2d | 0.011 (1) | 0.0034 (5) | 0.0014 (6) | −0.0041 (6) | 0.0013 (7) | −0.0002 (5) |
O3d | 0.0115 (8) | 0.015 (1) | 0.0086 (7) | −0.0034 (7) | −0.0010 (6) | −0.0017 (6) |
O4d | 0.0122 (7) | 0.028 (1) | 0.0065 (7) | −0.0033 (6) | −0.0019 (5) | 0.0012 (7) |
S1e | 0.0062 (2) | 0.0040 (2) | 0.0035 (2) | −0.0013 (1) | 0.0000 (1) | 0.0001 (1) |
O1e | 0.0128 (6) | 0.0148 (7) | 0.0115 (6) | −0.0019 (5) | 0.0027 (5) | −0.0076 (5) |
O2e | 0.0019 (6) | 0.012 (1) | 0.0018 (5) | −0.0025 (6) | 0.0001 (5) | 0.0011 (6) |
O3e | 0.0082 (7) | 0.0139 (9) | 0.013 (1) | 0.0001 (6) | −0.0020 (6) | 0.0037 (7) |
O4e | 0.0062 (7) | 0.0162 (7) | 0.024 (1) | 0.0017 (5) | 0.0012 (7) | 0.0072 (6) |
S1f | 0.0062 (2) | 0.0040 (2) | 0.0035 (2) | 0.0013 (1) | −0.0001 (1) | 0.0000 (1) |
O1f | 0.0127 (6) | 0.0140 (7) | 0.0124 (6) | 0.0016 (5) | −0.0029 (5) | −0.0077 (5) |
O2f | 0.0019 (6) | 0.012 (1) | 0.0017 (6) | 0.0027 (6) | −0.0002 (5) | 0.0006 (6) |
O3f | 0.0083 (7) | 0.0143 (9) | 0.013 (1) | 0.0002 (6) | 0.0022 (6) | 0.0036 (7) |
O4f | 0.0061 (7) | 0.0169 (7) | 0.023 (1) | −0.0014 (5) | −0.0005 (7) | 0.0076 (6) |
Geometric parameters (Å, º) top
Tl21—O2ai | 3.000 (4) | Cd12—O4bvi | 2.220 (4) |
Tl21—O1bi | 3.066 (4) | Cd12—O4c | 2.208 (3) |
Tl21—O3bi | 3.270 (4) | Cd12—O3d | 2.413 (4) |
Tl21—O1cii | 3.092 (4) | Cd12—O4evi | 2.260 (3) |
Tl21—O3cii | 2.983 (4) | Cd12—O3fxii | 2.185 (4) |
Tl21—O2d | 3.039 (4) | Cd21—O2a | 2.276 (3) |
Tl21—O1fiii | 3.195 (4) | Cd21—O1b | 2.365 (4) |
Tl21—O2fiv | 2.825 (4) | Cd21—O2c | 2.429 (3) |
Tl11—O1b | 3.200 (4) | Cd21—O1dvi | 2.232 (4) |
Tl11—O3bv | 3.218 (4) | Cd21—O1evi | 2.281 (4) |
Tl11—O4bv | 2.934 (4) | Cd21—O2e | 2.207 (3) |
Tl11—O3cvi | 3.205 (4) | Cd22—O1axiii | 2.328 (4) |
Tl11—O4cvi | 3.045 (5) | Cd22—O2b | 2.228 (3) |
Tl11—O2dvi | 3.078 (4) | Cd22—O1ci | 2.188 (4) |
Tl11—O1evi | 3.259 (4) | Cd22—O2dxiv | 2.494 (3) |
Tl11—O3evi | 3.008 (4) | Cd22—O1fxv | 2.265 (4) |
Tl11—O4f | 2.737 (4) | Cd22—O2f | 2.197 (3) |
Tl12—O1a | 3.177 (4) | S1a—O1a | 1.452 (4) |
Tl12—O2a | 3.277 (4) | S1a—O2a | 1.462 (3) |
Tl12—O3avii | 3.184 (4) | S1a—O3a | 1.488 (4) |
Tl12—O4avii | 3.035 (4) | S1a—O4a | 1.501 (4) |
Tl12—O2cvii | 3.166 (4) | S1b—O1b | 1.452 (4) |
Tl12—O3di | 3.241 (4) | S1b—O2b | 1.462 (3) |
Tl12—O4di | 2.998 (5) | S1b—O3b | 1.488 (4) |
Tl12—O4e | 2.738 (4) | S1b—O4b | 1.501 (4) |
Tl12—O1fviii | 3.229 (4) | S1c—O1c | 1.452 (4) |
Tl12—O3fviii | 2.969 (4) | S1c—O2c | 1.462 (4) |
Tl22—O1aix | 3.058 (4) | S1c—O3c | 1.488 (4) |
Tl22—O3aix | 3.247 (4) | S1c—O4c | 1.501 (3) |
Tl22—O2bvi | 3.057 (4) | S1d—O1d | 1.452 (4) |
Tl22—O2c | 3.051 (4) | S1d—O2d | 1.462 (4) |
Tl22—O1dvi | 3.036 (4) | S1d—O3d | 1.488 (4) |
Tl22—O3dvi | 2.960 (4) | S1d—O4d | 1.501 (3) |
Tl22—O1ex | 3.142 (4) | S1e—O1e | 1.452 (4) |
Tl22—O2evi | 2.798 (4) | S1e—O2e | 1.462 (4) |
Cd11—O3a | 2.258 (4) | S1e—O3e | 1.488 (4) |
Cd11—O4avii | 2.173 (4) | S1e—O4e | 1.501 (4) |
Cd11—O3c | 2.399 (4) | S1f—O1f | 1.452 (4) |
Cd11—O4dxi | 2.311 (3) | S1f—O2f | 1.462 (4) |
Cd11—O3e | 2.150 (4) | S1f—O3f | 1.488 (4) |
Cd11—O4fi | 2.272 (3) | S1f—O4f | 1.501 (4) |
Cd12—O3bxii | 2.205 (4) | | |
| | | |
O2ai—Tl21—O1bi | 64.44 (8) | O3aix—Tl22—O2c | 76.0 (1) |
O2ai—Tl21—O3bi | 107.99 (8) | O3aix—Tl22—O1dvi | 74.8 (1) |
O2ai—Tl21—O1cii | 156.4 (1) | O3aix—Tl22—O3dvi | 81.8 (1) |
O2ai—Tl21—O3cii | 156.6 (1) | O3aix—Tl22—O1ex | 124.5 (1) |
O2ai—Tl21—O2d | 95.1 (1) | O3aix—Tl22—O2evi | 160.7 (1) |
O2ai—Tl21—O1fiii | 78.4 (1) | O2bvi—Tl22—O2c | 95.2 (1) |
O2ai—Tl21—O2fiv | 90.4 (1) | O2bvi—Tl22—O1dvi | 155.9 (1) |
O1bi—Tl21—O3bi | 43.89 (9) | O2bvi—Tl22—O3dvi | 156.9 (1) |
O1bi—Tl21—O1cii | 112.8 (1) | O2bvi—Tl22—O1ex | 79.4 (1) |
O1bi—Tl21—O3cii | 122.8 (1) | O2bvi—Tl22—O2evi | 92.3 (1) |
O1bi—Tl21—O2d | 73.6 (1) | O2c—Tl22—O1dvi | 61.29 (9) |
O1bi—Tl21—O1fiii | 118.4 (1) | O2c—Tl22—O3dvi | 107.82 (8) |
O1bi—Tl21—O2fiv | 152.6 (1) | O2c—Tl22—O1ex | 159.5 (1) |
O3bi—Tl21—O1cii | 75.2 (1) | O2c—Tl22—O2evi | 98.3 (1) |
O3bi—Tl21—O3cii | 80.6 (1) | O1dvi—Tl22—O3dvi | 46.67 (9) |
O3bi—Tl21—O2d | 73.9 (1) | O1dvi—Tl22—O1ex | 120.4 (1) |
O3bi—Tl21—O1fiii | 125.7 (1) | O1dvi—Tl22—O2evi | 86.2 (1) |
O3bi—Tl21—O2fiv | 160.8 (1) | O3dvi—Tl22—O1ex | 78.2 (1) |
O1cii—Tl21—O3cii | 46.00 (9) | O3dvi—Tl22—O2evi | 82.5 (1) |
O1cii—Tl21—O2d | 62.80 (9) | O1ex—Tl22—O2evi | 62.44 (9) |
O1cii—Tl21—O1fiii | 119.5 (1) | O3a—Cd11—O4avii | 91.5 (2) |
O1cii—Tl21—O2fiv | 85.8 (1) | O3a—Cd11—O3c | 95.0 (1) |
O3cii—Tl21—O2d | 108.25 (8) | O3a—Cd11—O4dxi | 80.5 (2) |
O3cii—Tl21—O1fiii | 79.1 (1) | O3a—Cd11—O3e | 98.5 (2) |
O3cii—Tl21—O2fiv | 84.6 (1) | O3a—Cd11—O4fi | 163.0 (2) |
O2d—Tl21—O1fiii | 160.4 (1) | O4avii—Cd11—O3c | 173.1 (2) |
O2d—Tl21—O2fiv | 99.7 (1) | O4avii—Cd11—O4dxi | 93.7 (2) |
O1fiii—Tl21—O2fiv | 62.23 (9) | O4avii—Cd11—O3e | 92.0 (2) |
O1b—Tl11—O3bv | 132.6 (1) | O4avii—Cd11—O4fi | 104.3 (2) |
O1b—Tl11—O4bv | 94.93 (9) | O3c—Cd11—O4dxi | 85.3 (2) |
O1b—Tl11—O3cvi | 148.4 (1) | O3c—Cd11—O3e | 89.2 (2) |
O1b—Tl11—O4cvi | 152.4 (1) | O3c—Cd11—O4fi | 69.0 (2) |
O1b—Tl11—O2dvi | 71.3 (1) | O4dxi—Cd11—O3e | 174.3 (2) |
O1b—Tl11—O1evi | 59.48 (9) | O4dxi—Cd11—O4fi | 92.0 (2) |
O1b—Tl11—O3evi | 90.3 (1) | O3e—Cd11—O4fi | 87.4 (2) |
O1b—Tl11—O4f | 103.9 (1) | O3bxii—Cd12—O4bvi | 88.7 (2) |
O3bv—Tl11—O4bv | 45.89 (9) | O3bxii—Cd12—O4c | 81.1 (2) |
O3bv—Tl11—O3cvi | 78.2 (1) | O3bxii—Cd12—O3d | 94.6 (2) |
O3bv—Tl11—O4cvi | 54.4 (1) | O3bxii—Cd12—O4evi | 165.1 (2) |
O3bv—Tl11—O2dvi | 65.5 (1) | O3bxii—Cd12—O3fxii | 97.6 (2) |
O3bv—Tl11—O1evi | 142.44 (9) | O4bvi—Cd12—O4c | 93.7 (2) |
O3bv—Tl11—O3evi | 136.0 (1) | O4bvi—Cd12—O3d | 176.5 (2) |
O3bv—Tl11—O4f | 106.1 (1) | O4bvi—Cd12—O4evi | 105.8 (2) |
O4bv—Tl11—O3cvi | 107.2 (1) | O4bvi—Cd12—O3fxii | 92.3 (2) |
O4bv—Tl11—O4cvi | 99.9 (1) | O4c—Cd12—O3d | 85.7 (2) |
O4bv—Tl11—O2dvi | 58.6 (1) | O4c—Cd12—O4evi | 94.4 (2) |
O4bv—Tl11—O1evi | 150.6 (1) | O4c—Cd12—O3fxii | 173.8 (2) |
O4bv—Tl11—O3evi | 161.1 (1) | O3d—Cd12—O4evi | 70.8 (2) |
O4bv—Tl11—O4f | 97.0 (1) | O3d—Cd12—O3fxii | 88.4 (2) |
O3cvi—Tl11—O4cvi | 45.32 (8) | O4evi—Cd12—O3fxii | 85.4 (2) |
O3cvi—Tl11—O2dvi | 139.7 (1) | O2a—Cd21—O1b | 88.3 (1) |
O3cvi—Tl11—O1evi | 102.1 (1) | O2a—Cd21—O2c | 93.0 (1) |
O3cvi—Tl11—O3evi | 61.9 (1) | O2a—Cd21—O1dvi | 89.1 (2) |
O3cvi—Tl11—O4f | 52.2 (1) | O2a—Cd21—O1evi | 174.9 (2) |
O4cvi—Tl11—O2dvi | 97.0 (1) | O2a—Cd21—O2e | 94.9 (2) |
O4cvi—Tl11—O1evi | 98.8 (1) | O1b—Cd21—O2c | 172.7 (2) |
O4cvi—Tl11—O3evi | 83.2 (1) | O1b—Cd21—O1dvi | 89.5 (2) |
O4cvi—Tl11—O4f | 97.2 (1) | O1b—Cd21—O1evi | 87.2 (1) |
O2dvi—Tl11—O1evi | 96.81 (9) | O1b—Cd21—O2e | 84.1 (2) |
O2dvi—Tl11—O3evi | 139.96 (9) | O2c—Cd21—O1dvi | 83.4 (1) |
O2dvi—Tl11—O4f | 153.59 (8) | O2c—Cd21—O1evi | 91.1 (2) |
O1evi—Tl11—O3evi | 44.33 (9) | O2c—Cd21—O2e | 102.9 (1) |
O1evi—Tl11—O4f | 102.85 (9) | O1dvi—Cd21—O1evi | 88.4 (2) |
O3evi—Tl11—O4f | 64.07 (9) | O1dvi—Cd21—O2e | 172.3 (2) |
O1a—Tl12—O2a | 42.41 (9) | O1evi—Cd21—O2e | 87.1 (1) |
O1a—Tl12—O3avii | 131.7 (1) | O1axiii—Cd22—O2b | 88.9 (1) |
O1a—Tl12—O4avii | 95.38 (9) | O1axiii—Cd22—O1ci | 86.7 (2) |
O1a—Tl12—O2cvii | 71.2 (1) | O1axiii—Cd22—O2dxiv | 172.5 (2) |
O1a—Tl12—O3di | 149.05 (9) | O1axiii—Cd22—O1fxv | 86.8 (1) |
O1a—Tl12—O4di | 150.2 (1) | O1axiii—Cd22—O2f | 82.9 (2) |
O1a—Tl12—O4e | 103.5 (1) | O2b—Cd22—O1ci | 91.3 (2) |
O1a—Tl12—O1fviii | 59.03 (9) | O2b—Cd22—O2dxiv | 92.1 (1) |
O1a—Tl12—O3fviii | 90.4 (1) | O2b—Cd22—O1fxv | 175.3 (2) |
O2a—Tl12—O3avii | 141.5 (1) | O2b—Cd22—O2f | 92.3 (2) |
O2a—Tl12—O4avii | 96.92 (9) | O1ci—Cd22—O2dxiv | 85.8 (1) |
O2a—Tl12—O2cvii | 108.19 (9) | O1ci—Cd22—O1fxv | 86.7 (2) |
O2a—Tl12—O3di | 111.71 (8) | O1ci—Cd22—O2f | 168.9 (2) |
O2a—Tl12—O4di | 153.71 (8) | O2dxiv—Cd22—O1fxv | 92.0 (1) |
O2a—Tl12—O4e | 61.2 (1) | O2dxiv—Cd22—O2f | 104.6 (1) |
O2a—Tl12—O1fviii | 74.0 (1) | O1fxv—Cd22—O2f | 89.0 (1) |
O2a—Tl12—O3fviii | 74.8 (1) | O1a—S1a—O2a | 106.6 (3) |
O3avii—Tl12—O4avii | 45.57 (8) | O1a—S1a—O3a | 107.8 (3) |
O3avii—Tl12—O2cvii | 64.6 (1) | O1a—S1a—O4a | 111.2 (3) |
O3avii—Tl12—O3di | 78.6 (1) | O2a—S1a—O3a | 109.9 (3) |
O3avii—Tl12—O4di | 56.9 (1) | O2a—S1a—O4a | 113.5 (3) |
O3avii—Tl12—O4e | 107.6 (1) | O3a—S1a—O4a | 107.6 (3) |
O3avii—Tl12—O1fviii | 142.10 (9) | O1b—S1b—O2b | 106.6 (3) |
O3avii—Tl12—O3fviii | 136.5 (1) | O1b—S1b—O3b | 107.8 (3) |
O4avii—Tl12—O2cvii | 59.5 (1) | O1b—S1b—O4b | 111.2 (3) |
O4avii—Tl12—O3di | 106.4 (1) | O2b—S1b—O3b | 109.9 (3) |
O4avii—Tl12—O4di | 102.0 (1) | O2b—S1b—O4b | 113.5 (3) |
O4avii—Tl12—O4e | 96.6 (1) | O3b—S1b—O4b | 107.6 (3) |
O4avii—Tl12—O1fviii | 150.9 (1) | O1c—S1c—O2c | 106.6 (3) |
O4avii—Tl12—O3fviii | 160.2 (1) | O1c—S1c—O3c | 107.8 (3) |
O2cvii—Tl12—O3di | 139.1 (1) | O1c—S1c—O4c | 111.2 (3) |
O2cvii—Tl12—O4di | 97.14 (9) | O2c—S1c—O3c | 109.9 (3) |
O2cvii—Tl12—O4e | 153.87 (8) | O2c—S1c—O4c | 113.5 (3) |
O2cvii—Tl12—O1fviii | 96.40 (9) | O3c—S1c—O4c | 107.6 (3) |
O2cvii—Tl12—O3fviii | 139.96 (9) | O1d—S1d—O2d | 106.6 (3) |
O3di—Tl12—O4di | 45.28 (8) | O1d—S1d—O3d | 107.8 (3) |
O3di—Tl12—O4e | 53.1 (1) | O1d—S1d—O4d | 111.2 (3) |
O3di—Tl12—O1fviii | 102.7 (1) | O2d—S1d—O3d | 109.9 (3) |
O3di—Tl12—O3fviii | 62.1 (1) | O2d—S1d—O4d | 113.5 (3) |
O4di—Tl12—O4e | 98.3 (1) | O3d—S1d—O4d | 107.6 (3) |
O4di—Tl12—O1fviii | 96.7 (1) | O1e—S1e—O2e | 106.6 (2) |
O4di—Tl12—O3fviii | 81.3 (1) | O1e—S1e—O3e | 107.8 (3) |
O4e—Tl12—O1fviii | 102.56 (9) | O1e—S1e—O4e | 111.2 (3) |
O4e—Tl12—O3fviii | 63.63 (9) | O2e—S1e—O3e | 109.9 (3) |
O1fviii—Tl12—O3fviii | 44.84 (9) | O2e—S1e—O4e | 113.5 (3) |
O1aix—Tl22—O3aix | 44.15 (9) | O3e—S1e—O4e | 107.6 (3) |
O1aix—Tl22—O2bvi | 62.90 (8) | O1f—S1f—O2f | 106.6 (2) |
O1aix—Tl22—O2c | 74.4 (1) | O1f—S1f—O3f | 107.8 (2) |
O1aix—Tl22—O1dvi | 111.4 (1) | O1f—S1f—O4f | 111.2 (3) |
O1aix—Tl22—O3dvi | 124.8 (1) | O2f—S1f—O3f | 109.9 (3) |
O1aix—Tl22—O1ex | 119.0 (1) | O2f—S1f—O4f | 113.5 (3) |
O1aix—Tl22—O2evi | 152.7 (1) | O3f—S1f—O4f | 107.6 (2) |
O3aix—Tl22—O2bvi | 106.46 (8) | | |
Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) −x+1, −y, z−1/2; (iii) x, y−1, z−1; (iv) −x+2, −y+1, z−1/2; (v) −x+1, −y+2, z+1/2; (vi) −x+1, −y+1, z+1/2; (vii) −x, −y+1, z−1/2; (viii) −x+1, −y+2, z−1/2; (ix) −x, −y+1, z+1/2; (x) x, y, z+1; (xi) x−1, y, z; (xii) x, y−1, z; (xiii) x+1, y, z; (xiv) x, y+1, z; (xv) −x+2, −y+2, z−1/2. |
Crystal data top
Tl2Cd2(SO4)3 | F(000) = 1608 |
Mr = 921.7 | Dx = 5.505 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 10.327 (3) Å | θ = 5.1–28.7° |
b = 10.345 (4) Å | µ = 33.30 mm−1 |
c = 10.406 (5) Å | T = 85 K |
V = 1111.7 (8) Å3 | Spherical, colourless |
Z = 4 | 0.12 mm (radius) |
Data collection top
Enraf-Nonius CAD-4 diffractometer | θmax = 35.0°, θmin = 2.8° |
θ/2θ scans | h = 0→16 |
Absorption correction: for a sphere ? | k = 0→16 |
Tmin = 0.002, Tmax = 0.015 | l = −16→16 |
5303 measured reflections | 3 standard reflections every 120 min |
4985 independent reflections | intensity decay: 4% |
4028 reflections with I > 3σ(I) | |
Refinement top
Refinement on F | Weighting scheme based on measured s.u.'s w = 1/σ2(F) |
R[F2 > 2σ(F2)] = 0.057 | (Δ/σ)max = 0.0004 |
wR(F2) = 0.060 | Δρmax = 4.77 e Å−3 |
S = 1.94 | Δρmin = −4.73 e Å−3 |
4985 reflections | Extinction correction: B-C type 1 Gaussian isotropic |
67 parameters | Extinction coefficient: 0.015 (3) |
Crystal data top
Tl2Cd2(SO4)3 | V = 1111.7 (8) Å3 |
Mr = 921.7 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.327 (3) Å | µ = 33.30 mm−1 |
b = 10.345 (4) Å | T = 85 K |
c = 10.406 (5) Å | 0.12 mm (radius) |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 4985 independent reflections |
Absorption correction: for a sphere ? | 4028 reflections with I > 3σ(I) |
Tmin = 0.002, Tmax = 0.015 | 3 standard reflections every 120 min |
5303 measured reflections | intensity decay: 4% |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 67 parameters |
wR(F2) = 0.060 | Δρmax = 4.77 e Å−3 |
S = 1.94 | Δρmin = −4.73 e Å−3 |
4985 reflections | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Tl1 | 0.81231 (7) | 0.82841 (7) | 0.81649 (7) | 0.0076 (1) | |
Tl2 | 0.05831 (7) | 0.04009 (7) | 0.05051 (7) | 0.0093 (2) | |
Cd1 | 0.3325 (1) | 0.3163 (1) | 0.3408 (1) | 0.0050 (3) | |
Cd2 | 0.5790 (1) | 0.5998 (1) | 0.5943 (1) | 0.0052 (3) | |
S1ab | 0.2602 (4) | 0.6201 (4) | 0.5082 (3) | 0.0045 | |
O1ab | 0.175 (1) | 0.700 (1) | 0.434 (1) | 0.0118 | |
O2ab | 0.3937 (8) | 0.673 (1) | 0.496 (1) | 0.0095 | |
O3ab | 0.253 (1) | 0.4866 (8) | 0.454 (1) | 0.0094 | |
O4ab | 0.221 (1) | 0.616 (1) | 0.6443 (8) | 0.0071 | |
S1cd | 0.5234 (3) | 0.2850 (3) | 0.6269 (4) | 0.0045 | |
O1cd | 0.511 (1) | 0.195 (1) | 0.731 (1) | 0.0118 | |
O2cd | 0.491 (1) | 0.4162 (8) | 0.676 (1) | 0.0095 | |
O3cd | 0.429 (1) | 0.245 (1) | 0.5252 (9) | 0.0094 | |
O4cd | 0.6553 (8) | 0.284 (1) | 0.573 (1) | 0.0071 | |
S1ef | 0.6325 (4) | 0.5072 (3) | 0.2860 (3) | 0.0045 | |
O1ef | 0.736 (1) | 0.440 (1) | 0.222 (1) | 0.0118 | |
O2ef | 0.682 (1) | 0.554 (1) | 0.4122 (8) | 0.0095 | |
O3ef | 0.5245 (9) | 0.413 (1) | 0.305 (1) | 0.0094 | |
O4ef | 0.585 (1) | 0.6170 (8) | 0.209 (1) | 0.0071 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Tl1 | 0.0076 (3) | 0.0082 (2) | 0.0072 (3) | −0.0004 (2) | 0.0009 (2) | −0.0003 (2) |
Tl2 | 0.0078 (3) | 0.0109 (3) | 0.0090 (3) | −0.0005 (2) | −0.0005 (2) | −0.0001 (2) |
Cd1 | 0.0053 (5) | 0.0061 (5) | 0.0037 (5) | 0.0013 (4) | −0.0005 (3) | −0.0008 (4) |
Cd2 | 0.0049 (5) | 0.0069 (5) | 0.0037 (5) | −0.0016 (4) | 0.0007 (4) | −0.0001 (4) |
S1ab | 0.004938 | 0.00522 | 0.003451 | −0.002064 | 0.000933 | 0.000926 |
O1ab | 0.002104 | 0.020092 | 0.013215 | −0.001758 | −0.003367 | 0.002508 |
O2ab | 0.006196 | 0.004226 | 0.018101 | −0.002181 | 0.004078 | −0.002335 |
O3ab | 0.011804 | 0.006607 | 0.009694 | −0.001359 | −0.006412 | −0.000746 |
O4ab | 0.013867 | 0.005246 | 0.00233 | −0.006195 | 0.004542 | −0.003401 |
S1cd | 0.004339 | 0.00483 | 0.00444 | −0.000037 | 0.001905 | −0.001787 |
O1cd | 0.01683 | 0.001255 | 0.017326 | 0.000997 | 0.00408 | 0.001395 |
O2cd | 0.012085 | 0.008336 | 0.008102 | 0.004672 | −0.005264 | −0.005353 |
O3cd | 0.012734 | 0.007853 | 0.007518 | −0.006216 | −0.001687 | 0.000587 |
O4cd | 0.000513 | 0.013273 | 0.007657 | −0.002292 | 0.000937 | −0.007716 |
S1ef | 0.004607 | 0.004409 | 0.004593 | 0.000527 | −0.002543 | 0.000365 |
O1ef | 0.017813 | 0.012224 | 0.005374 | 0.004022 | −0.001294 | −0.006815 |
O2ef | 0.007401 | 0.016002 | 0.00512 | −0.00696 | −0.001327 | −0.000238 |
O3ef | 0.007353 | 0.005407 | 0.015345 | −0.001059 | 0.00104 | −0.004518 |
O4ef | 0.007545 | 0.002953 | 0.010945 | −0.004024 | −0.006654 | 0.005477 |
Geometric parameters (Å, º) top
Tl1—O1abi | 2.98 (1) | Cd1—O3cd | 2.29 (1) |
Tl1—O3abii | 2.98 (1) | Cd1—O4cdix | 2.287 (9) |
Tl1—O4abii | 3.03 (1) | Cd2—O1abi | 2.31 (1) |
Tl1—O1efiii | 2.99 (1) | Cd2—O2ab | 2.296 (9) |
Tl1—O3efiii | 3.01 (1) | Cd2—O1efiii | 2.36 (1) |
Tl1—O4efi | 2.89 (1) | Cd2—O2ef | 2.224 (9) |
Tl1—O2cdii | 3.27 (1) | Cd2—O1cdii | 2.27 (1) |
Tl1—O3cdii | 3.11 (1) | Cd2—O2cd | 2.269 (9) |
Tl1—O4cdiii | 2.92 (1) | S1ab—O1ab | 1.44 (1) |
Tl2—O1abiv | 2.93 (1) | S1ab—O2ab | 1.487 (9) |
Tl2—O2abv | 3.06 (1) | S1ab—O3ab | 1.50 (1) |
Tl2—O3abiv | 3.27 (1) | S1ab—O4ab | 1.475 (9) |
Tl2—O2efvi | 2.72 (1) | S1ef—O1ef | 1.44 (1) |
Tl2—O4efvii | 3.16 (1) | S1ef—O2ef | 1.49 (1) |
Tl2—O1cdviii | 3.16 (1) | S1ef—O3ef | 1.50 (1) |
Tl2—O2cdix | 2.96 (1) | S1ef—O4ef | 1.47 (1) |
Tl2—O3cdviii | 2.96 (1) | S1cd—O1cd | 1.44 (1) |
Cd1—O3ab | 2.27 (1) | S1cd—O2cd | 1.49 (1) |
Cd1—O4abv | 2.229 (9) | S1cd—O3cd | 1.50 (1) |
Cd1—O3ef | 2.251 (9) | S1cd—O4cd | 1.475 (9) |
Cd1—O4efvi | 2.289 (9) | | |
| | | |
O3ab—Cd1—O4abv | 98.2 (4) | O1efiii—Cd2—O2ef | 93.1 (4) |
O3ab—Cd1—O3ef | 93.5 (4) | O1efiii—Cd2—O1cdii | 87.7 (4) |
O3ab—Cd1—O4efvi | 161.7 (4) | O1efiii—Cd2—O2cd | 88.1 (4) |
O3ab—Cd1—O3cd | 88.5 (4) | O2ef—Cd2—O1cdii | 166.6 (4) |
O3ab—Cd1—O4cdix | 81.8 (4) | O2ef—Cd2—O2cd | 109.2 (4) |
O4abv—Cd1—O3ef | 85.7 (4) | O1cdii—Cd2—O2cd | 84.2 (4) |
O4abv—Cd1—O4efvi | 99.6 (4) | O1ab—S1ab—O2ab | 108.3 (6) |
O4abv—Cd1—O3cd | 168.2 (4) | O1ab—S1ab—O3ab | 107.4 (6) |
O4abv—Cd1—O4cdix | 107.8 (4) | O1ab—S1ab—O4ab | 111.2 (6) |
O3ef—Cd1—O4efvi | 92.0 (4) | O2ab—S1ab—O3ab | 110.6 (6) |
O3ef—Cd1—O3cd | 84.2 (4) | O2ab—S1ab—O4ab | 110.3 (6) |
O3ef—Cd1—O4cdix | 166.2 (4) | O3ab—S1ab—O4ab | 109.1 (6) |
O4efvi—Cd1—O3cd | 74.7 (4) | O1cd—S1cd—O2cd | 108.3 (6) |
O4efvi—Cd1—O4cdix | 88.8 (4) | O1cd—S1cd—O3cd | 107.4 (6) |
O3cd—Cd1—O4cdix | 82.7 (4) | O1cd—S1cd—O4cd | 111.2 (6) |
O1abi—Cd2—O2ab | 90.3 (4) | O2cd—S1cd—O3cd | 110.6 (6) |
O1abi—Cd2—O1efiii | 83.2 (4) | O2cd—S1cd—O4cd | 110.3 (6) |
O1abi—Cd2—O2ef | 83.2 (4) | O3cd—S1cd—O4cd | 109.1 (6) |
O1abi—Cd2—O1cdii | 83.6 (4) | O1ef—S1ef—O2ef | 108.3 (6) |
O1abi—Cd2—O2cd | 165.3 (4) | O1ef—S1ef—O3ef | 107.4 (6) |
O2ab—Cd2—O1efiii | 168.9 (4) | O1ef—S1ef—O4ef | 111.2 (6) |
O2ab—Cd2—O2ef | 95.1 (4) | O2ef—S1ef—O3ef | 110.6 (6) |
O2ab—Cd2—O1cdii | 82.5 (4) | O2ef—S1ef—O4ef | 110.3 (6) |
O2ab—Cd2—O2cd | 96.2 (4) | O3ef—S1ef—O4ef | 109.1 (6) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+3/2, −y+1, z+1/2; (iv) −x, y−1/2, −z+1/2; (v) −x+1/2, −y+1, z−1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x−1/2, −y+1/2, −z; (viii) −x+1/2, −y, z−1/2; (ix) x−1/2, −y+1/2, −z+1. |
Experimental details
| (121K) | (85K) |
Crystal data |
Chemical formula | Tl2Cd2(SO4)3 | Tl2Cd2(SO4)3 |
Mr | 921.7 | 921.7 |
Crystal system, space group | Monoclinic, P1121 | Orthorhombic, P212121 |
Temperature (K) | 121 | 85 |
a, b, c (Å) | 10.356 (4), 10.350 (2), 10.353 (6) | 10.327 (3), 10.345 (4), 10.406 (5) |
α, β, γ (°) | 90, 90, 90.04 (3) | 90, 90, 90 |
V (Å3) | 1109.7 (8) | 1111.7 (8) |
Z | 4 | 4 |
Radiation type | Synchrotron, λ = 0.5502 Å | Mo Kα |
µ (mm−1) | 17.53 | 33.30 |
Crystal size (mm) | 0.59 × 0.35 × 0.35 | 0.12 (radius) |
|
Data collection |
Diffractometer | Huber CAD-4 κ geometry diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Analytical (Alcock, 1974) | For a sphere |
Tmin, Tmax | 0.009, 0.046 | 0.002, 0.015 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 9312, 8392, 8392 | 5303, 4985, 4028 |
Rint | ? | ? |
(sin θ/λ)max (Å−1) | 0.622 | 0.806 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.064, 13.78 | 0.057, 0.060, 1.94 |
No. of reflections | 8392 | 4985 |
No. of parameters | 132 | 67 |
No. of restraints | ? | ? |
Δρmax, Δρmin (e Å−3) | 2.43, −1.86 | 4.77, −4.73 |
Selected geometric parameters (Å, º) for (121K) topTl21—O2ai | 3.000 (4) | Cd12—O4bvi | 2.220 (4) |
Tl21—O1bi | 3.066 (4) | Cd12—O4c | 2.208 (3) |
Tl21—O3bi | 3.270 (4) | Cd12—O3d | 2.413 (4) |
Tl21—O1cii | 3.092 (4) | Cd12—O4evi | 2.260 (3) |
Tl21—O3cii | 2.983 (4) | Cd12—O3fxii | 2.185 (4) |
Tl21—O2d | 3.039 (4) | Cd21—O2a | 2.276 (3) |
Tl21—O1fiii | 3.195 (4) | Cd21—O1b | 2.365 (4) |
Tl21—O2fiv | 2.825 (4) | Cd21—O2c | 2.429 (3) |
Tl11—O1b | 3.200 (4) | Cd21—O1dvi | 2.232 (4) |
Tl11—O3bv | 3.218 (4) | Cd21—O1evi | 2.281 (4) |
Tl11—O4bv | 2.934 (4) | Cd21—O2e | 2.207 (3) |
Tl11—O3cvi | 3.205 (4) | Cd22—O1axiii | 2.328 (4) |
Tl11—O4cvi | 3.045 (5) | Cd22—O2b | 2.228 (3) |
Tl11—O2dvi | 3.078 (4) | Cd22—O1ci | 2.188 (4) |
Tl11—O1evi | 3.259 (4) | Cd22—O2dxiv | 2.494 (3) |
Tl11—O3evi | 3.008 (4) | Cd22—O1fxv | 2.265 (4) |
Tl11—O4f | 2.737 (4) | Cd22—O2f | 2.197 (3) |
Tl12—O1a | 3.177 (4) | S1a—O1a | 1.452 (4) |
Tl12—O2a | 3.277 (4) | S1a—O2a | 1.462 (3) |
Tl12—O3avii | 3.184 (4) | S1a—O3a | 1.488 (4) |
Tl12—O4avii | 3.035 (4) | S1a—O4a | 1.501 (4) |
Tl12—O2cvii | 3.166 (4) | S1b—O1b | 1.452 (4) |
Tl12—O3di | 3.241 (4) | S1b—O2b | 1.462 (3) |
Tl12—O4di | 2.998 (5) | S1b—O3b | 1.488 (4) |
Tl12—O4e | 2.738 (4) | S1b—O4b | 1.501 (4) |
Tl12—O1fviii | 3.229 (4) | S1c—O1c | 1.452 (4) |
Tl12—O3fviii | 2.969 (4) | S1c—O2c | 1.462 (4) |
Tl22—O1aix | 3.058 (4) | S1c—O3c | 1.488 (4) |
Tl22—O3aix | 3.247 (4) | S1c—O4c | 1.501 (3) |
Tl22—O2bvi | 3.057 (4) | S1d—O1d | 1.452 (4) |
Tl22—O2c | 3.051 (4) | S1d—O2d | 1.462 (4) |
Tl22—O1dvi | 3.036 (4) | S1d—O3d | 1.488 (4) |
Tl22—O3dvi | 2.960 (4) | S1d—O4d | 1.501 (3) |
Tl22—O1ex | 3.142 (4) | S1e—O1e | 1.452 (4) |
Tl22—O2evi | 2.798 (4) | S1e—O2e | 1.462 (4) |
Cd11—O3a | 2.258 (4) | S1e—O3e | 1.488 (4) |
Cd11—O4avii | 2.173 (4) | S1e—O4e | 1.501 (4) |
Cd11—O3c | 2.399 (4) | S1f—O1f | 1.452 (4) |
Cd11—O4dxi | 2.311 (3) | S1f—O2f | 1.462 (4) |
Cd11—O3e | 2.150 (4) | S1f—O3f | 1.488 (4) |
Cd11—O4fi | 2.272 (3) | S1f—O4f | 1.501 (4) |
Cd12—O3bxii | 2.205 (4) | | |
| | | |
O1a—S1a—O2a | 106.6 (3) | O1d—S1d—O2d | 106.6 (3) |
O1a—S1a—O3a | 107.8 (3) | O1d—S1d—O3d | 107.8 (3) |
O1a—S1a—O4a | 111.2 (3) | O1d—S1d—O4d | 111.2 (3) |
O2a—S1a—O3a | 109.9 (3) | O2d—S1d—O3d | 109.9 (3) |
O2a—S1a—O4a | 113.5 (3) | O2d—S1d—O4d | 113.5 (3) |
O3a—S1a—O4a | 107.6 (3) | O3d—S1d—O4d | 107.6 (3) |
O1b—S1b—O2b | 106.6 (3) | O1e—S1e—O2e | 106.6 (2) |
O1b—S1b—O3b | 107.8 (3) | O1e—S1e—O3e | 107.8 (3) |
O1b—S1b—O4b | 111.2 (3) | O1e—S1e—O4e | 111.2 (3) |
O2b—S1b—O3b | 109.9 (3) | O2e—S1e—O3e | 109.9 (3) |
O2b—S1b—O4b | 113.5 (3) | O2e—S1e—O4e | 113.5 (3) |
O3b—S1b—O4b | 107.6 (3) | O3e—S1e—O4e | 107.6 (3) |
O1c—S1c—O2c | 106.6 (3) | O1f—S1f—O2f | 106.6 (2) |
O1c—S1c—O3c | 107.8 (3) | O1f—S1f—O3f | 107.8 (2) |
O1c—S1c—O4c | 111.2 (3) | O1f—S1f—O4f | 111.2 (3) |
O2c—S1c—O3c | 109.9 (3) | O2f—S1f—O3f | 109.9 (3) |
O2c—S1c—O4c | 113.5 (3) | O2f—S1f—O4f | 113.5 (3) |
O3c—S1c—O4c | 107.6 (3) | O3f—S1f—O4f | 107.6 (2) |
Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) −x+1, −y, z−1/2; (iii) x, y−1, z−1; (iv) −x+2, −y+1, z−1/2; (v) −x+1, −y+2, z+1/2; (vi) −x+1, −y+1, z+1/2; (vii) −x, −y+1, z−1/2; (viii) −x+1, −y+2, z−1/2; (ix) −x, −y+1, z+1/2; (x) x, y, z+1; (xi) x−1, y, z; (xii) x, y−1, z; (xiii) x+1, y, z; (xiv) x, y+1, z; (xv) −x+2, −y+2, z−1/2. |
f1 | 34.2 (2) |
f2 | 2.4 (2) |
f3 | 30.6 (2) |
f4 | 0.0 (2) |
f5 | 28.8 (2) |
f6 | 4.0 (2) |
Selected geometric parameters (Å, º) for (85K) topTl1—O1abi | 2.98 (1) | Cd1—O3cd | 2.29 (1) |
Tl1—O3abii | 2.98 (1) | Cd1—O4cdix | 2.287 (9) |
Tl1—O4abii | 3.03 (1) | Cd2—O1abi | 2.31 (1) |
Tl1—O1efiii | 2.99 (1) | Cd2—O2ab | 2.296 (9) |
Tl1—O3efiii | 3.01 (1) | Cd2—O1efiii | 2.36 (1) |
Tl1—O4efi | 2.89 (1) | Cd2—O2ef | 2.224 (9) |
Tl1—O2cdii | 3.27 (1) | Cd2—O1cdii | 2.27 (1) |
Tl1—O3cdii | 3.11 (1) | Cd2—O2cd | 2.269 (9) |
Tl1—O4cdiii | 2.92 (1) | S1ab—O1ab | 1.44 (1) |
Tl2—O1abiv | 2.93 (1) | S1ab—O2ab | 1.487 (9) |
Tl2—O2abv | 3.06 (1) | S1ab—O3ab | 1.50 (1) |
Tl2—O3abiv | 3.27 (1) | S1ab—O4ab | 1.475 (9) |
Tl2—O2efvi | 2.72 (1) | S1ef—O1ef | 1.44 (1) |
Tl2—O4efvii | 3.16 (1) | S1ef—O2ef | 1.49 (1) |
Tl2—O1cdviii | 3.16 (1) | S1ef—O3ef | 1.50 (1) |
Tl2—O2cdix | 2.96 (1) | S1ef—O4ef | 1.47 (1) |
Tl2—O3cdviii | 2.96 (1) | S1cd—O1cd | 1.44 (1) |
Cd1—O3ab | 2.27 (1) | S1cd—O2cd | 1.49 (1) |
Cd1—O4abv | 2.229 (9) | S1cd—O3cd | 1.50 (1) |
Cd1—O3ef | 2.251 (9) | S1cd—O4cd | 1.475 (9) |
Cd1—O4efvi | 2.289 (9) | | |
| | | |
O1ab—S1ab—O2ab | 108.3 (6) | O2cd—S1cd—O3cd | 110.6 (6) |
O1ab—S1ab—O3ab | 107.4 (6) | O2cd—S1cd—O4cd | 110.3 (6) |
O1ab—S1ab—O4ab | 111.2 (6) | O3cd—S1cd—O4cd | 109.1 (6) |
O2ab—S1ab—O3ab | 110.6 (6) | O1ef—S1ef—O2ef | 108.3 (6) |
O2ab—S1ab—O4ab | 110.3 (6) | O1ef—S1ef—O3ef | 107.4 (6) |
O3ab—S1ab—O4ab | 109.1 (6) | O1ef—S1ef—O4ef | 111.2 (6) |
O1cd—S1cd—O2cd | 108.3 (6) | O2ef—S1ef—O3ef | 110.6 (6) |
O1cd—S1cd—O3cd | 107.4 (6) | O2ef—S1ef—O4ef | 110.3 (6) |
O1cd—S1cd—O4cd | 111.2 (6) | O3ef—S1ef—O4ef | 109.1 (6) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+3/2, −y+1, z+1/2; (iv) −x, y−1/2, −z+1/2; (v) −x+1/2, −y+1, z−1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x−1/2, −y+1/2, −z; (viii) −x+1/2, −y, z−1/2; (ix) x−1/2, −y+1/2, −z+1. |
f1 | 79.1 (2) |
f2 | 10.5 (2) |
f3 | 10.4 (2) |