Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036586/fi2036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036586/fi2036Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (O-B) = 0.011 Å
- R factor = 0.044
- wR factor = 0.108
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT128_ALERT_4_C Non-standard setting of Space group P2/c .... P2/n
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Gd1 (3) 3.33 PLAT794_ALERT_5_G Check Predicted Bond Valency for Gd2 (3) 2.77 PLAT794_ALERT_5_G Check Predicted Bond Valency for Gd3 (3) 2.85 PLAT794_ALERT_5_G Check Predicted Bond Valency for Gd4 (3) 3.23 PLAT794_ALERT_5_G Check Predicted Bond Valency for Gd5 (3) 3.11
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 5 ALERT type 5 Informative message, check
Single crystals of CsLi2Gd4(BO3)5 were obtained in a Pt crucible by melting a mixture of analytically pure Cs2CO3 (1.3028 g, 4 mmol, XinJiang Research Institute of Non-ferrous Metals), Li2CO3 (0.2217, 3 mmol, Beijing Chemical Reagents Company), Gd2O3 (0.7250 g, 2 mmol, CIAC), H3BO3 (0.9829, 16 mmol, Beijing Chemical Reagents Company). The melt was cooled slowly from 1023 to 873 K at a rate of 1 K h-1 and then at a rate of 20 K h-1 to the room temperature. Block-shaped colourless crystals were recovered and separated from the initial reaction product. The Rb analogue of the title compound can be synthesized by solid-state reaction, with the determined composition of CsLi2Gd4(BO3)5.
Two space groups, Pn and P2/n, were proposed by the data preparation program. The noncentrosymmetric space group Pn was discarded for further consideration since detectable signal was not observed in a powder second harmonic generation test. Direct phase determination showed positions of 6 heavy atoms which were assigned to Gd. Subsequent difference Fourier syntheses revealed the positions of the oxygen atoms. Judging from its larger thermal parameters and much further coordination to the oxygen atoms one of the heavy atom was then assigned to Cs.
Rare earth borates are promising luminescent materials (Jubera et al., 2003; Sablayrolles et al., 2005) and their applications are found in Plasma Displays Panels (PDP) and efficient light conversion bulbs (Fouassier et al., 1981). Besides that, rare earth borates are good nonlinear optical materials, e.g. YCa4O(BO3)3 (Aka et al., 1997), CaLa2B10O19 (Wu et al., 2001), and self-frequency doubling laser crystals Nd3+:YAl3(BO3) (Dorozhkin et al., 1981). Recently, Li6Gd(BO3)3:Ce has received extensive attention as a new efficient thermal neutron detection material. (Czirr et al., 1999; Chaminade et al., 2001, van Eijk et al., 2001)
In the Li2O—Gd2O3—B2O3 system, there are four ternary compounds, LiGd6O5(BO3)3 (Chaminade et al., 1999), Li6Gd(BO3)3 (Mascetti et al., 1983), Li3Gd(BO3)2 and LiGd2O2BO3 (Jubera, Gravereau & Chaminade, 2001). In an attempt to synthesize compounds in the system using caesium borate as the flux, we obtained a new quaternary compound CsLi2Gd4(BO3)5, which is, to our knowledge, the first rare-earth borate containing caesium.
The structure of CsLi2Gd4(BO3)5 is shown in figure 1. In the asymmetric unit, all six boron atoms are three-coordinated yielding planar BO3 groups (B—O: 1.352 to 1.408 Å, average: 1.376 Å, which agrees with literature values). The site symmetry of B2 and B3 is 2.
The Gd atoms occupy five different crystallographic sites, Gd2, Gd4 and Gd5 being coordinated by seven O atoms and Gd1 and Gd3 coordinated to eight and nine oxygen atoms, respectively. Gd2, Gd3 lie on twofold axes. The GdOn polyhedra (Gd—O: 2.241 to 2.634 Å) share edges yielding two types of Gd—O chains. The chain containing Gd1, Gd3 and Gd5 atoms is terminated by two BO3 groups (Fig. 2). The three-element Gd3O17 chain (Fig. 3) joins other equivalent three-element chains to form an infinite zigzag chain. Both chains can be classified as fluorite-related ribbons, which are common in rare earth borate compounds (Ren et al., 1999; Jubera, Gravereau, Chaminade & Fouassier, 2001). Similar Bi—O ribbons are reported in bismuth compounds (Crumpton & Greaves, 2004; Darriet et al., 2005; Muktha & Row, 2006). The two chains in CsLi2Gd4(BO3)5 are interlocked by sharing the edges of Gd polyhedra to form a two dimensional [Gd8O16(BO3)2]14- layer in the ac plane. The layers are inter-linked by out of plane BO3 groups in the b direction into a 3 dimensional network.
Both Li atoms are five-coordinated (distorted square pyramids, Li—O: 1.885 to 2.145 Å). The Cs atom is coordinated by seven O atoms and resides in a big basket-like cage.
For related literature, see: Aka et al. (1997); Chaminade et al. (1999, 2001); Crumpton & Greaves (2004); Czirr et al. (1999); Darriet et al. (2005); Dorozhkin et al. (1981); Fouassier et al. (1981); Jubera et al. (2003); Jubera, Gravereau & Chaminade (2001); Jubera, Gravereau, Chaminade & Fouassier (2001); Mascetti et al. (1983); Muktha & Row (2006); Ren et al. (1999); Sablayrolles et al. (2005); Wu et al. (2001); van Eijk et al. (2001).
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Version 1.0c; Westrip, 2007).
CsLi2Gd4(BO3)5 | F(000) = 1848 |
Mr = 1069.84 | Dx = 5.326 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 23 reflections |
a = 10.644 (2) Å | θ = 6.5–11.7° |
b = 6.4661 (15) Å | µ = 22.40 mm−1 |
c = 20.093 (4) Å | T = 295 K |
β = 105.250 (16)° | Block, colourless |
V = 1334.3 (5) Å3 | 0.16 × 0.12 × 0.08 mm |
Z = 4 |
Bruker P4 diffractometer | 2829 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.060 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω scans | h = −13→13 |
Absorption correction: ψ scan (North et al., 1968) | k = −8→8 |
Tmin = 0.042, Tmax = 0.167 | l = −26→25 |
7381 measured reflections | 3 standard reflections every 97 reflections |
3068 independent reflections | intensity decay: none |
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)] = 0.044 | w = 1/[σ2(Fo2) + (0.069P)2 + 1.5286P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.108 | (Δ/σ)max = 0.002 |
S = 1.11 | Δρmax = 4.05 e Å−3 |
3068 reflections | Δρmin = −2.81 e Å−3 |
248 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0133 (4) |
CsLi2Gd4(BO3)5 | V = 1334.3 (5) Å3 |
Mr = 1069.84 | Z = 4 |
Monoclinic, P2/n | Mo Kα radiation |
a = 10.644 (2) Å | µ = 22.40 mm−1 |
b = 6.4661 (15) Å | T = 295 K |
c = 20.093 (4) Å | 0.16 × 0.12 × 0.08 mm |
β = 105.250 (16)° |
Bruker P4 diffractometer | 2829 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.060 |
Tmin = 0.042, Tmax = 0.167 | 3 standard reflections every 97 reflections |
7381 measured reflections | intensity decay: none |
3068 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 248 parameters |
wR(F2) = 0.108 | 0 restraints |
S = 1.11 | Δρmax = 4.05 e Å−3 |
3068 reflections | Δρmin = −2.81 e Å−3 |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Gd1 | 0.45528 (3) | 0.34144 (6) | 0.649931 (16) | 0.01704 (15) | |
Gd2 | 0.2500 | 0.59641 (9) | 0.7500 | 0.02208 (16) | |
Gd3 | 0.7500 | 0.59044 (8) | 0.7500 | 0.01776 (16) | |
Gd4 | 0.35686 (3) | 0.64428 (6) | 0.946524 (18) | 0.01724 (14) | |
Gd5 | 0.84343 (3) | 0.64848 (6) | 0.953592 (16) | 0.01731 (15) | |
Cs1 | 0.55501 (4) | 0.09547 (9) | 0.85836 (2) | 0.02535 (16) | |
B1 | 0.4515 (6) | 0.7837 (16) | 0.6497 (4) | 0.0190 (16) | |
B2 | 0.2500 | 0.1655 (18) | 0.7500 | 0.020 (2) | |
B3 | 0.7500 | 0.1618 (19) | 0.7500 | 0.023 (3) | |
B4 | 0.3429 (7) | 0.1954 (19) | 0.9500 (4) | 0.0238 (19) | |
B5 | 0.8570 (8) | 0.2030 (17) | 0.9562 (4) | 0.0216 (17) | |
B6 | 0.5418 (7) | 0.5930 (13) | 0.8231 (4) | 0.0200 (15) | |
Li1 | 0.6372 (11) | 0.978 (2) | 0.6532 (7) | 0.027 (3) | |
Li2 | 0.2786 (11) | 0.987 (2) | 0.6582 (6) | 0.022 (2) | |
O1 | 0.4590 (4) | 0.9903 (9) | 0.6603 (3) | 0.0231 (11) | |
O2 | 0.3386 (5) | 0.6737 (8) | 0.6485 (3) | 0.0198 (11) | |
O3 | 0.5582 (5) | 0.6740 (8) | 0.6405 (3) | 0.0189 (10) | |
O4 | 0.2500 | −0.0436 (13) | 0.7500 | 0.0252 (17) | |
O5 | 0.2777 (4) | 0.2764 (8) | 0.6974 (2) | 0.0207 (10) | |
O6 | 0.7500 | −0.0510 (13) | 0.7500 | 0.0226 (17) | |
O7 | 0.8179 (4) | 0.2672 (9) | 0.8072 (2) | 0.0206 (10) | |
O8 | 0.3404 (4) | −0.0048 (9) | 0.9297 (3) | 0.0190 (10) | |
O9 | 0.4550 (4) | 0.3091 (9) | 0.9728 (3) | 0.0237 (11) | |
O10 | 0.2302 (4) | 0.3107 (8) | 0.9469 (3) | 0.0202 (10) | |
O11 | 0.8424 (5) | −0.0004 (10) | 0.9383 (3) | 0.0203 (10) | |
O12 | 0.9664 (5) | 0.3213 (8) | 0.9531 (3) | 0.0191 (10) | |
O13 | 0.7622 (4) | 0.3197 (8) | 0.9754 (3) | 0.0220 (10) | |
O14 | 0.5248 (5) | 0.4966 (10) | 0.7606 (3) | 0.0265 (11) | |
O15 | 0.6689 (4) | 0.6496 (9) | 0.8568 (3) | 0.0219 (11) | |
O16 | 0.4352 (5) | 0.6364 (9) | 0.8473 (3) | 0.0233 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Gd1 | 0.0196 (2) | 0.0201 (2) | 0.0127 (2) | 0.00018 (11) | 0.00648 (15) | 0.00003 (12) |
Gd2 | 0.0354 (3) | 0.0193 (3) | 0.0130 (3) | 0.000 | 0.0089 (2) | 0.000 |
Gd3 | 0.0211 (2) | 0.0196 (3) | 0.0133 (3) | 0.000 | 0.00573 (18) | 0.000 |
Gd4 | 0.0186 (2) | 0.0209 (2) | 0.0129 (2) | 0.00014 (12) | 0.00551 (14) | 0.00020 (13) |
Gd5 | 0.0198 (2) | 0.0214 (3) | 0.0120 (2) | −0.00005 (12) | 0.00639 (15) | 0.00026 (13) |
Cs1 | 0.0253 (3) | 0.0283 (3) | 0.0243 (3) | −0.00007 (17) | 0.00982 (19) | −0.00019 (19) |
B1 | 0.021 (3) | 0.024 (4) | 0.013 (4) | 0.003 (3) | 0.004 (3) | 0.006 (3) |
B2 | 0.019 (5) | 0.016 (6) | 0.027 (6) | 0.000 | 0.009 (4) | 0.000 |
B3 | 0.022 (5) | 0.021 (6) | 0.027 (6) | 0.000 | 0.009 (4) | 0.000 |
B4 | 0.023 (3) | 0.037 (5) | 0.012 (4) | 0.001 (3) | 0.004 (3) | 0.007 (3) |
B5 | 0.026 (3) | 0.030 (5) | 0.009 (3) | 0.003 (3) | 0.005 (3) | −0.001 (3) |
B6 | 0.020 (3) | 0.025 (4) | 0.016 (4) | −0.004 (3) | 0.007 (3) | −0.003 (3) |
Li1 | 0.026 (5) | 0.033 (7) | 0.023 (6) | −0.004 (5) | 0.009 (5) | −0.010 (6) |
Li2 | 0.028 (5) | 0.024 (6) | 0.015 (5) | −0.004 (5) | 0.009 (4) | 0.004 (5) |
O1 | 0.023 (2) | 0.021 (3) | 0.028 (3) | 0.001 (2) | 0.013 (2) | 0.001 (2) |
O2 | 0.020 (2) | 0.023 (3) | 0.018 (2) | −0.0011 (19) | 0.0078 (19) | 0.000 (2) |
O3 | 0.023 (2) | 0.020 (2) | 0.016 (2) | 0.0020 (19) | 0.0085 (18) | 0.000 (2) |
O4 | 0.040 (4) | 0.021 (4) | 0.019 (4) | 0.000 | 0.015 (3) | 0.000 |
O5 | 0.028 (2) | 0.021 (2) | 0.016 (2) | 0.000 (2) | 0.0109 (18) | 0.000 (2) |
O6 | 0.025 (3) | 0.028 (4) | 0.015 (3) | 0.000 | 0.005 (3) | 0.000 |
O7 | 0.0218 (19) | 0.027 (3) | 0.013 (2) | −0.002 (2) | 0.0046 (17) | 0.001 (2) |
O8 | 0.023 (2) | 0.015 (2) | 0.018 (2) | 0.0030 (19) | 0.0021 (18) | −0.001 (2) |
O9 | 0.022 (2) | 0.026 (3) | 0.023 (3) | −0.002 (2) | 0.0060 (19) | −0.001 (2) |
O10 | 0.022 (2) | 0.024 (2) | 0.017 (2) | 0.003 (2) | 0.0088 (18) | 0.001 (2) |
O11 | 0.028 (2) | 0.016 (2) | 0.019 (2) | 0.000 (2) | 0.0092 (19) | 0.001 (2) |
O12 | 0.020 (2) | 0.023 (3) | 0.015 (2) | −0.0036 (19) | 0.0058 (18) | 0.000 (2) |
O13 | 0.023 (2) | 0.021 (2) | 0.025 (3) | −0.001 (2) | 0.013 (2) | 0.000 (2) |
O14 | 0.034 (2) | 0.032 (3) | 0.016 (2) | 0.000 (3) | 0.011 (2) | −0.002 (2) |
O15 | 0.018 (2) | 0.029 (3) | 0.019 (3) | −0.0022 (19) | 0.0048 (19) | −0.004 (2) |
O16 | 0.021 (2) | 0.029 (3) | 0.023 (3) | 0.000 (2) | 0.012 (2) | −0.002 (2) |
Gd1—O1i | 2.279 (6) | B1—Li1 | 2.329 (15) |
Gd1—O5 | 2.368 (4) | B2—O4 | 1.352 (14) |
Gd1—O14 | 2.373 (5) | B2—O5ii | 1.372 (8) |
Gd1—O10ii | 2.389 (5) | B2—O5 | 1.372 (8) |
Gd1—O7iii | 2.389 (4) | B2—Li2viii | 2.265 (14) |
Gd1—O12iii | 2.431 (5) | B2—Li2i | 2.265 (14) |
Gd1—O3 | 2.443 (5) | B2—Cs1ii | 3.4305 (18) |
Gd1—O2 | 2.478 (5) | B3—O7iii | 1.367 (8) |
Gd1—B1 | 2.860 (11) | B3—O7 | 1.368 (8) |
Gd1—Li2i | 2.999 (12) | B3—O6 | 1.375 (15) |
Gd1—Li1i | 3.033 (14) | B3—Li1ix | 2.323 (14) |
Gd1—Gd3 | 3.6274 (8) | B3—Li1i | 2.323 (14) |
Gd2—O4iv | 2.328 (8) | B3—Cs1iii | 3.4075 (17) |
Gd2—O5 | 2.377 (5) | B4—O8 | 1.355 (13) |
Gd2—O5ii | 2.377 (5) | B4—O9 | 1.374 (10) |
Gd2—O16ii | 2.398 (5) | B4—O10 | 1.400 (10) |
Gd2—O16 | 2.398 (5) | B4—Li2viii | 2.597 (15) |
Gd2—O2 | 2.511 (5) | B5—O11 | 1.362 (12) |
Gd2—O2ii | 2.511 (5) | B5—O13 | 1.393 (10) |
Gd2—B2 | 2.786 (12) | B5—O12 | 1.408 (10) |
Gd2—B6ii | 3.067 (7) | B5—Li1ix | 2.650 (17) |
Gd2—B6 | 3.067 (7) | B6—O14 | 1.372 (9) |
Gd3—O6iv | 2.319 (8) | B6—O16 | 1.376 (9) |
Gd3—O7 | 2.403 (5) | B6—O15 | 1.393 (8) |
Gd3—O7iii | 2.403 (5) | B6—Cs1iv | 3.320 (8) |
Gd3—O14 | 2.535 (5) | Li1—O11x | 1.913 (14) |
Gd3—O14iii | 2.535 (5) | Li1—O1 | 1.941 (13) |
Gd3—O15iii | 2.544 (5) | Li1—O6iv | 2.007 (13) |
Gd3—O15 | 2.544 (5) | Li1—O7x | 2.036 (15) |
Gd3—O3iii | 2.634 (5) | Li1—O3 | 2.130 (15) |
Gd3—O3 | 2.634 (5) | Li1—B3iv | 2.323 (14) |
Gd3—B3 | 2.772 (13) | Li1—B5x | 2.650 (17) |
Gd3—B6 | 2.963 (7) | Li1—Gd1iv | 3.033 (14) |
Gd3—B6iii | 2.963 (7) | Li1—Gd5iii | 3.072 (13) |
Gd4—O9v | 2.241 (5) | Li1—Cs1x | 3.429 (12) |
Gd4—O13v | 2.273 (5) | Li2—O8xi | 1.885 (13) |
Gd4—O8iv | 2.294 (6) | Li2—O1 | 1.909 (12) |
Gd4—O16 | 2.356 (6) | Li2—O4iv | 1.957 (12) |
Gd4—O9 | 2.404 (5) | Li2—O5iv | 2.034 (14) |
Gd4—O2ii | 2.433 (5) | Li2—O2 | 2.145 (14) |
Gd4—O10 | 2.545 (5) | Li2—B2iv | 2.265 (14) |
Gd4—B4 | 2.908 (12) | Li2—B4xi | 2.597 (15) |
Gd4—Li2ii | 3.132 (13) | Li2—Gd1iv | 2.999 (12) |
Gd4—Gd4v | 3.7337 (10) | Li2—Gd4ii | 3.132 (13) |
Gd4—Gd5v | 3.7958 (8) | Li2—Cs1xi | 3.549 (12) |
Gd5—O11iv | 2.291 (6) | O1—Gd1iv | 2.279 (6) |
Gd5—O15 | 2.309 (5) | O2—Gd4ii | 2.433 (5) |
Gd5—O12vi | 2.378 (5) | O3—Gd5iii | 2.396 (5) |
Gd5—O13 | 2.379 (5) | O4—Li2viii | 1.957 (12) |
Gd5—O3iii | 2.396 (5) | O4—Li2i | 1.957 (12) |
Gd5—O12 | 2.489 (5) | O4—Gd2i | 2.328 (8) |
Gd5—B5 | 2.884 (11) | O4—Cs1ii | 3.517 (2) |
Gd5—Li1iii | 3.072 (13) | O5—Li2i | 2.034 (14) |
Gd5—Gd4v | 3.7957 (7) | O5—Cs1ii | 3.616 (5) |
Gd5—Gd1vii | 3.8099 (9) | O6—Li1ix | 2.007 (13) |
Gd5—Gd5vi | 3.8737 (10) | O6—Li1i | 2.007 (13) |
Cs1—O8 | 3.069 (5) | O6—Gd3i | 2.319 (8) |
Cs1—O9 | 3.101 (5) | O6—Cs1iii | 3.510 (2) |
Cs1—O11 | 3.121 (5) | O7—Li1ix | 2.036 (15) |
Cs1—O13 | 3.126 (5) | O7—Gd1iii | 2.389 (4) |
Cs1—O15i | 3.131 (5) | O8—Li2viii | 1.885 (13) |
Cs1—O16i | 3.215 (6) | O8—Gd4i | 2.294 (6) |
Cs1—O14 | 3.219 (6) | O9—Gd4v | 2.241 (5) |
Cs1—B6 | 3.289 (9) | O10—Gd5v | 2.346 (5) |
Cs1—B6i | 3.320 (9) | O10—Gd1ii | 2.389 (5) |
Cs1—B4 | 3.331 (9) | O11—Li1ix | 1.913 (14) |
Cs1—B5 | 3.370 (8) | O11—Gd5i | 2.291 (6) |
Cs1—B3 | 3.4074 (19) | O12—Gd5vi | 2.378 (5) |
B1—O1 | 1.352 (12) | O12—Gd1iii | 2.431 (5) |
B1—O2 | 1.391 (9) | O13—Gd4v | 2.273 (5) |
B1—O3 | 1.392 (9) | O15—Cs1iv | 3.131 (5) |
B1—Li2 | 2.302 (15) | O16—Cs1iv | 3.215 (6) |
O1i—Gd1—O5 | 77.44 (17) | B5—Cs1—B3 | 72.48 (14) |
O1i—Gd1—O14 | 110.0 (2) | O1—B1—O2 | 121.5 (6) |
O5—Gd1—O14 | 77.49 (17) | O1—B1—O3 | 120.6 (7) |
O1i—Gd1—O10ii | 88.99 (18) | O2—B1—O3 | 117.9 (8) |
O5—Gd1—O10ii | 74.75 (16) | O1—B1—Li2 | 56.0 (5) |
O14—Gd1—O10ii | 141.81 (18) | O2—B1—Li2 | 65.7 (5) |
O1i—Gd1—O7iii | 77.01 (18) | O3—B1—Li2 | 174.9 (7) |
O5—Gd1—O7iii | 131.07 (17) | O1—B1—Li1 | 56.4 (5) |
O14—Gd1—O7iii | 73.17 (17) | O2—B1—Li1 | 177.9 (7) |
O10ii—Gd1—O7iii | 144.84 (17) | O3—B1—Li1 | 64.2 (5) |
O1i—Gd1—O12iii | 91.33 (18) | Li2—B1—Li1 | 112.2 (7) |
O5—Gd1—O12iii | 145.34 (17) | O1—B1—Gd1 | 171.0 (5) |
O14—Gd1—O12iii | 136.74 (18) | O2—B1—Gd1 | 60.0 (4) |
O10ii—Gd1—O12iii | 72.34 (17) | O3—B1—Gd1 | 58.6 (4) |
O7iii—Gd1—O12iii | 75.88 (16) | Li2—B1—Gd1 | 125.5 (4) |
O1i—Gd1—O3 | 152.44 (16) | Li1—B1—Gd1 | 121.9 (5) |
O5—Gd1—O3 | 127.53 (17) | O4—B2—O5ii | 121.5 (5) |
O14—Gd1—O3 | 70.40 (19) | O4—B2—O5 | 121.5 (5) |
O10ii—Gd1—O3 | 107.56 (17) | O5ii—B2—O5 | 117.0 (9) |
O7iii—Gd1—O3 | 76.93 (18) | O4—B2—Li2viii | 59.3 (4) |
O12iii—Gd1—O3 | 73.74 (17) | O5ii—B2—Li2viii | 62.4 (4) |
O1i—Gd1—O2 | 149.44 (16) | O5—B2—Li2viii | 175.3 (4) |
O5—Gd1—O2 | 73.01 (17) | O4—B2—Li2i | 59.3 (4) |
O14—Gd1—O2 | 71.09 (19) | O5ii—B2—Li2i | 175.3 (4) |
O10ii—Gd1—O2 | 76.03 (18) | O5—B2—Li2i | 62.4 (4) |
O7iii—Gd1—O2 | 129.38 (17) | Li2viii—B2—Li2i | 118.6 (8) |
O12iii—Gd1—O2 | 108.66 (17) | O4—B2—Gd2 | 180.000 (3) |
O3—Gd1—O2 | 57.97 (17) | O5ii—B2—Gd2 | 58.5 (5) |
O1i—Gd1—B1 | 174.87 (19) | O5—B2—Gd2 | 58.5 (5) |
O5—Gd1—B1 | 99.54 (19) | Li2viii—B2—Gd2 | 120.7 (4) |
O14—Gd1—B1 | 65.1 (2) | Li2i—B2—Gd2 | 120.7 (4) |
O10ii—Gd1—B1 | 94.24 (19) | O4—B2—Cs1 | 82.41 (19) |
O7iii—Gd1—B1 | 102.36 (19) | O5ii—B2—Cs1 | 86.51 (19) |
O12iii—Gd1—B1 | 93.45 (19) | O5—B2—Cs1 | 101.5 (2) |
O3—Gd1—B1 | 29.10 (17) | Li2viii—B2—Cs1 | 73.9 (3) |
O2—Gd1—B1 | 29.11 (17) | Li2i—B2—Cs1 | 98.2 (3) |
O1i—Gd1—Li2i | 39.5 (3) | Gd2—B2—Cs1 | 97.59 (19) |
O5—Gd1—Li2i | 42.5 (3) | O4—B2—Cs1ii | 82.41 (19) |
O14—Gd1—Li2i | 108.5 (3) | O5ii—B2—Cs1ii | 101.5 (2) |
O10ii—Gd1—Li2i | 65.5 (3) | O5—B2—Cs1ii | 86.51 (19) |
O7iii—Gd1—Li2i | 114.5 (3) | Li2viii—B2—Cs1ii | 98.2 (3) |
O12iii—Gd1—Li2i | 111.5 (3) | Li2i—B2—Cs1ii | 73.9 (3) |
O3—Gd1—Li2i | 168.0 (3) | Gd2—B2—Cs1ii | 97.59 (19) |
O2—Gd1—Li2i | 110.1 (3) | Cs1—B2—Cs1ii | 164.8 (4) |
B1—Gd1—Li2i | 139.1 (3) | O7iii—B3—O7 | 120.2 (10) |
O1i—Gd1—Li1i | 39.8 (3) | O7iii—B3—O6 | 119.9 (5) |
O5—Gd1—Li1i | 115.2 (3) | O7—B3—O6 | 119.9 (5) |
O14—Gd1—Li1i | 105.5 (3) | O7iii—B3—Li1ix | 179.0 (7) |
O10ii—Gd1—Li1i | 109.9 (3) | O7—B3—Li1ix | 60.6 (5) |
O7iii—Gd1—Li1i | 42.1 (3) | O6—B3—Li1ix | 59.3 (5) |
O12iii—Gd1—Li1i | 67.5 (3) | O7iii—B3—Li1i | 60.6 (5) |
O3—Gd1—Li1i | 112.7 (3) | O7—B3—Li1i | 179.1 (7) |
O2—Gd1—Li1i | 170.6 (3) | O6—B3—Li1i | 59.3 (5) |
B1—Gd1—Li1i | 141.5 (3) | Li1ix—B3—Li1i | 118.7 (9) |
Li2i—Gd1—Li1i | 79.2 (4) | O7iii—B3—Gd3 | 60.1 (5) |
O1i—Gd1—Gd3 | 113.56 (12) | O7—B3—Gd3 | 60.1 (5) |
O5—Gd1—Gd3 | 121.42 (12) | O6—B3—Gd3 | 180.000 (3) |
O14—Gd1—Gd3 | 44.10 (12) | Li1ix—B3—Gd3 | 120.7 (5) |
O10ii—Gd1—Gd3 | 153.86 (13) | Li1i—B3—Gd3 | 120.7 (5) |
O7iii—Gd1—Gd3 | 40.95 (13) | O7iii—B3—Cs1 | 108.9 (2) |
O12iii—Gd1—Gd3 | 93.18 (12) | O7—B3—Cs1 | 78.59 (19) |
O3—Gd1—Gd3 | 46.54 (11) | O6—B3—Cs1 | 82.8 (2) |
O2—Gd1—Gd3 | 88.82 (12) | Li1ix—B3—Cs1 | 70.6 (3) |
B1—Gd1—Gd3 | 64.33 (13) | Li1i—B3—Cs1 | 101.7 (4) |
Li2i—Gd1—Gd3 | 140.6 (2) | Gd3—B3—Cs1 | 97.2 (2) |
Li1i—Gd1—Gd3 | 82.9 (2) | O7iii—B3—Cs1iii | 78.59 (18) |
O4iv—Gd2—O5 | 150.52 (11) | O7—B3—Cs1iii | 108.9 (2) |
O4iv—Gd2—O5ii | 150.52 (11) | O6—B3—Cs1iii | 82.8 (2) |
O5—Gd2—O5ii | 59.0 (2) | Li1ix—B3—Cs1iii | 101.7 (4) |
O4iv—Gd2—O16ii | 83.80 (14) | Li1i—B3—Cs1iii | 70.6 (3) |
O5—Gd2—O16ii | 84.42 (18) | Gd3—B3—Cs1iii | 97.2 (2) |
O5ii—Gd2—O16ii | 106.56 (18) | Cs1—B3—Cs1iii | 165.5 (4) |
O4iv—Gd2—O16 | 83.80 (14) | O8—B4—O9 | 123.9 (7) |
O5—Gd2—O16 | 106.56 (17) | O8—B4—O10 | 123.1 (7) |
O5ii—Gd2—O16 | 84.42 (18) | O9—B4—O10 | 112.9 (9) |
O16ii—Gd2—O16 | 167.6 (3) | O9—B4—Li2viii | 139.0 (6) |
O4iv—Gd2—O2 | 78.52 (12) | O10—B4—Li2viii | 90.4 (5) |
O5—Gd2—O2 | 72.26 (16) | O8—B4—Gd4 | 160.6 (5) |
O5ii—Gd2—O2 | 130.64 (17) | O9—B4—Gd4 | 55.1 (5) |
O16ii—Gd2—O2 | 73.76 (17) | O10—B4—Gd4 | 61.1 (5) |
O16—Gd2—O2 | 103.69 (17) | Li2viii—B4—Gd4 | 121.1 (4) |
O4iv—Gd2—O2ii | 78.52 (12) | O8—B4—Cs1 | 67.1 (4) |
O5—Gd2—O2ii | 130.64 (17) | O9—B4—Cs1 | 68.4 (4) |
O5ii—Gd2—O2ii | 72.26 (16) | O10—B4—Cs1 | 140.9 (5) |
O16ii—Gd2—O2ii | 103.69 (17) | Li2viii—B4—Cs1 | 72.4 (3) |
O16—Gd2—O2ii | 73.76 (17) | Gd4—B4—Cs1 | 97.7 (3) |
O2—Gd2—O2ii | 157.0 (2) | O11—B5—O13 | 123.8 (7) |
O4iv—Gd2—B2 | 180.000 (4) | O11—B5—O12 | 123.4 (7) |
O5—Gd2—B2 | 29.48 (11) | O13—B5—O12 | 112.7 (8) |
O5ii—Gd2—B2 | 29.48 (11) | O13—B5—Li1ix | 134.7 (6) |
O16ii—Gd2—B2 | 96.20 (14) | O12—B5—Li1ix | 93.5 (5) |
O16—Gd2—B2 | 96.20 (14) | O11—B5—Gd5 | 163.4 (5) |
O2—Gd2—B2 | 101.48 (12) | O13—B5—Gd5 | 55.1 (4) |
O2ii—Gd2—B2 | 101.48 (12) | O12—B5—Gd5 | 59.6 (4) |
O4iv—Gd2—O14ii | 102.64 (13) | Li1ix—B5—Gd5 | 123.0 (4) |
O5—Gd2—O14ii | 90.81 (16) | O11—B5—Cs1 | 67.8 (4) |
O5ii—Gd2—O14ii | 66.72 (16) | O13—B5—Cs1 | 67.9 (4) |
O16ii—Gd2—O14ii | 51.50 (16) | O12—B5—Cs1 | 139.4 (5) |
O16—Gd2—O14ii | 132.05 (16) | Li1ix—B5—Cs1 | 68.3 (3) |
O2—Gd2—O14ii | 124.22 (15) | Gd5—B5—Cs1 | 99.2 (2) |
O2ii—Gd2—O14ii | 61.62 (15) | O14—B6—O16 | 119.6 (6) |
B2—Gd2—O14ii | 77.36 (13) | O14—B6—O15 | 116.2 (6) |
O4iv—Gd2—O14 | 102.64 (13) | O16—B6—O15 | 124.1 (7) |
O5—Gd2—O14 | 66.72 (16) | O14—B6—Gd3 | 58.6 (3) |
O5ii—Gd2—O14 | 90.81 (16) | O16—B6—Gd3 | 165.9 (6) |
O16ii—Gd2—O14 | 132.05 (16) | O15—B6—Gd3 | 59.0 (3) |
O16—Gd2—O14 | 51.50 (16) | O14—B6—Gd2 | 72.0 (4) |
O2—Gd2—O14 | 61.62 (15) | O16—B6—Gd2 | 48.9 (3) |
O2ii—Gd2—O14 | 124.22 (15) | O15—B6—Gd2 | 164.3 (6) |
B2—Gd2—O14 | 77.36 (13) | Gd3—B6—Gd2 | 123.9 (3) |
O14ii—Gd2—O14 | 154.7 (3) | O14—B6—Cs1 | 75.0 (4) |
O4iv—Gd2—B6ii | 90.41 (16) | O16—B6—Cs1 | 96.7 (5) |
O5—Gd2—B6ii | 90.52 (19) | O15—B6—Cs1 | 99.9 (5) |
O5ii—Gd2—B6ii | 88.76 (19) | Gd3—B6—Cs1 | 96.1 (2) |
O16ii—Gd2—B6ii | 25.60 (19) | Gd2—B6—Cs1 | 95.2 (2) |
O16—Gd2—B6ii | 154.60 (19) | O14—B6—Cs1iv | 128.9 (5) |
O2—Gd2—B6ii | 99.31 (18) | O16—B6—Cs1iv | 73.6 (4) |
O2ii—Gd2—B6ii | 80.86 (18) | O15—B6—Cs1iv | 70.0 (4) |
B2—Gd2—B6ii | 89.59 (16) | Gd3—B6—Cs1iv | 96.7 (2) |
O14ii—Gd2—B6ii | 26.27 (17) | Gd2—B6—Cs1iv | 94.4 (2) |
O14—Gd2—B6ii | 153.33 (18) | Cs1—B6—Cs1iv | 156.1 (3) |
O4iv—Gd2—B6 | 90.41 (16) | O11x—Li1—O1 | 115.3 (7) |
O5—Gd2—B6 | 88.76 (19) | O11x—Li1—O6iv | 138.4 (7) |
O5ii—Gd2—B6 | 90.52 (19) | O1—Li1—O6iv | 106.2 (6) |
O16ii—Gd2—B6 | 154.60 (19) | O11x—Li1—O7x | 103.6 (7) |
O16—Gd2—B6 | 25.60 (19) | O1—Li1—O7x | 93.9 (6) |
O2—Gd2—B6 | 80.86 (18) | O6iv—Li1—O7x | 71.9 (5) |
O2ii—Gd2—B6 | 99.31 (18) | O11x—Li1—O3 | 95.3 (6) |
B2—Gd2—B6 | 89.59 (16) | O1—Li1—O3 | 71.5 (5) |
O14ii—Gd2—B6 | 153.33 (18) | O6iv—Li1—O3 | 98.4 (7) |
O14—Gd2—B6 | 26.27 (17) | O7x—Li1—O3 | 159.9 (7) |
B6ii—Gd2—B6 | 179.2 (3) | O11x—Li1—B3iv | 127.1 (7) |
O6iv—Gd3—O7 | 150.44 (11) | O1—Li1—B3iv | 102.6 (6) |
O6iv—Gd3—O7iii | 150.44 (11) | O6iv—Li1—B3iv | 36.1 (4) |
O7—Gd3—O7iii | 59.1 (2) | O7x—Li1—B3iv | 35.8 (4) |
O6iv—Gd3—O14 | 103.85 (15) | O3—Li1—B3iv | 132.3 (7) |
O7—Gd3—O14 | 85.64 (17) | O11x—Li1—B1 | 108.6 (6) |
O7iii—Gd3—O14 | 70.10 (17) | O1—Li1—B1 | 35.4 (4) |
O6iv—Gd3—O14iii | 103.85 (15) | O6iv—Li1—B1 | 105.3 (6) |
O7—Gd3—O14iii | 70.10 (17) | O7x—Li1—B1 | 128.1 (6) |
O7iii—Gd3—O14iii | 85.64 (17) | O3—Li1—B1 | 36.0 (3) |
O14—Gd3—O14iii | 152.3 (3) | B3iv—Li1—B1 | 123.3 (6) |
O6iv—Gd3—O15iii | 81.35 (13) | O11x—Li1—B5x | 29.5 (4) |
O7—Gd3—O15iii | 114.08 (16) | O1—Li1—B5x | 106.0 (6) |
O7iii—Gd3—O15iii | 81.59 (17) | O6iv—Li1—B5x | 135.8 (7) |
O14—Gd3—O15iii | 130.14 (16) | O7x—Li1—B5x | 76.6 (5) |
O14iii—Gd3—O15iii | 55.07 (16) | O3—Li1—B5x | 120.1 (6) |
O6iv—Gd3—O15 | 81.34 (13) | B3iv—Li1—B5x | 107.2 (6) |
O7—Gd3—O15 | 81.59 (17) | B1—Li1—B5x | 118.4 (6) |
O7iii—Gd3—O15 | 114.08 (17) | O11x—Li1—Gd1iv | 99.0 (6) |
O14—Gd3—O15 | 55.07 (16) | O1—Li1—Gd1iv | 48.7 (4) |
O14iii—Gd3—O15 | 130.14 (16) | O6iv—Li1—Gd1iv | 108.1 (5) |
O15iii—Gd3—O15 | 162.7 (3) | O7x—Li1—Gd1iv | 51.8 (3) |
O6iv—Gd3—O3iii | 78.17 (11) | O3—Li1—Gd1iv | 118.9 (5) |
O7—Gd3—O3iii | 73.11 (16) | B3iv—Li1—Gd1iv | 79.0 (4) |
O7iii—Gd3—O3iii | 130.34 (16) | B1—Li1—Gd1iv | 83.4 (4) |
O14—Gd3—O3iii | 121.44 (16) | B5x—Li1—Gd1iv | 73.3 (4) |
O14iii—Gd3—O3iii | 64.95 (16) | O11x—Li1—Gd5iii | 48.1 (4) |
O15iii—Gd3—O3iii | 108.25 (16) | O1—Li1—Gd5iii | 109.0 (5) |
O15—Gd3—O3iii | 67.98 (16) | O6iv—Li1—Gd5iii | 118.6 (6) |
O6iv—Gd3—O3 | 78.17 (11) | O7x—Li1—Gd5iii | 149.1 (6) |
O7—Gd3—O3 | 130.34 (16) | O3—Li1—Gd5iii | 51.0 (3) |
O7iii—Gd3—O3 | 73.11 (16) | B3iv—Li1—Gd5iii | 145.5 (5) |
O14—Gd3—O3 | 64.95 (16) | B1—Li1—Gd5iii | 79.4 (4) |
O14iii—Gd3—O3 | 121.44 (16) | B5x—Li1—Gd5iii | 77.3 (4) |
O15iii—Gd3—O3 | 67.98 (16) | Gd1iv—Li1—Gd5iii | 133.0 (4) |
O15—Gd3—O3 | 108.25 (16) | O11x—Li1—Gd3 | 121.3 (6) |
O3iii—Gd3—O3 | 156.3 (2) | O1—Li1—Gd3 | 101.7 (6) |
O6iv—Gd3—B3 | 180.000 (3) | O6iv—Li1—Gd3 | 46.0 (4) |
O7—Gd3—B3 | 29.56 (11) | O7x—Li1—Gd3 | 117.9 (5) |
O7iii—Gd3—B3 | 29.56 (11) | O3—Li1—Gd3 | 54.7 (4) |
O14—Gd3—B3 | 76.15 (15) | B3iv—Li1—Gd3 | 82.1 (5) |
O14iii—Gd3—B3 | 76.15 (15) | B1—Li1—Gd3 | 77.0 (5) |
O15iii—Gd3—B3 | 98.65 (13) | B5x—Li1—Gd3 | 147.7 (5) |
O15—Gd3—B3 | 98.66 (13) | Gd1iv—Li1—Gd3 | 138.9 (4) |
O3iii—Gd3—B3 | 101.83 (11) | Gd5iii—Li1—Gd3 | 78.3 (3) |
O3—Gd3—B3 | 101.83 (11) | O11x—Li1—Cs1x | 64.3 (4) |
O6iv—Gd3—B6 | 89.68 (16) | O1—Li1—Cs1x | 165.0 (7) |
O7—Gd3—B6 | 86.45 (19) | O6iv—Li1—Cs1x | 75.4 (3) |
O7iii—Gd3—B6 | 94.11 (19) | O7x—Li1—Cs1x | 72.2 (4) |
O14—Gd3—B6 | 27.51 (18) | O3—Li1—Cs1x | 123.4 (5) |
O14iii—Gd3—B6 | 152.8 (2) | B3iv—Li1—Cs1x | 69.6 (3) |
O15iii—Gd3—B6 | 151.79 (18) | B1—Li1—Cs1x | 159.3 (6) |
O15—Gd3—B6 | 28.00 (18) | B5x—Li1—Cs1x | 65.9 (3) |
O3iii—Gd3—B6 | 95.82 (18) | Gd1iv—Li1—Cs1x | 116.3 (4) |
O3—Gd3—B6 | 84.05 (19) | Gd5iii—Li1—Cs1x | 82.2 (3) |
B3—Gd3—B6 | 90.32 (17) | Gd3—Li1—Cs1x | 90.1 (3) |
O6iv—Gd3—B6iii | 89.68 (17) | O8xi—Li2—O1 | 116.4 (7) |
O7—Gd3—B6iii | 94.11 (19) | O8xi—Li2—O4iv | 130.8 (6) |
O7iii—Gd3—B6iii | 86.45 (19) | O1—Li2—O4iv | 112.7 (6) |
O14—Gd3—B6iii | 152.8 (2) | O8xi—Li2—O5iv | 105.4 (6) |
O14iii—Gd3—B6iii | 27.51 (18) | O1—Li2—O5iv | 95.0 (6) |
O15iii—Gd3—B6iii | 28.00 (18) | O4iv—Li2—O5iv | 73.1 (5) |
O15—Gd3—B6iii | 151.79 (19) | O8xi—Li2—O2 | 94.9 (6) |
O3iii—Gd3—B6iii | 84.05 (19) | O1—Li2—O2 | 72.1 (5) |
O3—Gd3—B6iii | 95.82 (18) | O4iv—Li2—O2 | 96.6 (6) |
B3—Gd3—B6iii | 90.32 (16) | O5iv—Li2—O2 | 159.4 (7) |
B6—Gd3—B6iii | 179.4 (3) | O8xi—Li2—B2iv | 123.2 (6) |
O9v—Gd4—O13v | 92.37 (18) | O1—Li2—B2iv | 109.0 (6) |
O9v—Gd4—O8iv | 89.57 (18) | O4iv—Li2—B2iv | 36.4 (4) |
O13v—Gd4—O8iv | 88.01 (18) | O5iv—Li2—B2iv | 36.7 (4) |
O9v—Gd4—O16 | 99.64 (19) | O2—Li2—B2iv | 131.5 (6) |
O13v—Gd4—O16 | 166.45 (18) | O8xi—Li2—B1 | 107.5 (6) |
O8iv—Gd4—O16 | 85.83 (19) | O1—Li2—B1 | 35.9 (4) |
O9v—Gd4—O9 | 73.0 (2) | O4iv—Li2—B1 | 109.8 (6) |
O13v—Gd4—O9 | 103.30 (18) | O5iv—Li2—B1 | 129.7 (6) |
O8iv—Gd4—O9 | 159.41 (17) | O2—Li2—B1 | 36.3 (3) |
O16—Gd4—O9 | 86.33 (19) | B2iv—Li2—B1 | 129.2 (6) |
O9v—Gd4—O2ii | 166.9 (2) | O8xi—Li2—B4xi | 30.2 (3) |
O13v—Gd4—O2ii | 90.96 (17) | O1—Li2—B4xi | 106.8 (6) |
O8iv—Gd4—O2ii | 77.92 (17) | O4iv—Li2—B4xi | 132.4 (6) |
O16—Gd4—O2ii | 75.95 (18) | O5iv—Li2—B4xi | 78.1 (5) |
O9—Gd4—O2ii | 118.38 (17) | O2—Li2—B4xi | 120.6 (6) |
O9v—Gd4—O10 | 119.01 (18) | B2iv—Li2—B4xi | 105.8 (6) |
O13v—Gd4—O10 | 72.09 (17) | B1—Li2—B4xi | 117.8 (6) |
O8iv—Gd4—O10 | 144.98 (16) | O8xi—Li2—Gd1iv | 101.7 (5) |
O16—Gd4—O10 | 106.88 (18) | O1—Li2—Gd1iv | 49.5 (3) |
O9—Gd4—O10 | 55.60 (16) | O4iv—Li2—Gd1iv | 112.6 (5) |
O2ii—Gd4—O10 | 74.02 (17) | O5iv—Li2—Gd1iv | 51.9 (3) |
O9v—Gd4—B4 | 99.1 (2) | O2—Li2—Gd1iv | 120.7 (5) |
O13v—Gd4—B4 | 92.5 (2) | B2iv—Li2—Gd1iv | 82.8 (4) |
O8iv—Gd4—B4 | 171.27 (19) | B1—Li2—Gd1iv | 84.7 (4) |
O16—Gd4—B4 | 91.8 (2) | B4xi—Li2—Gd1iv | 74.8 (4) |
O9—Gd4—B4 | 27.96 (18) | O8xi—Li2—Gd4ii | 46.7 (3) |
O2ii—Gd4—B4 | 93.36 (19) | O1—Li2—Gd4ii | 107.9 (6) |
O10—Gd4—B4 | 28.77 (18) | O4iv—Li2—Gd4ii | 113.9 (5) |
O9v—Gd4—Li2ii | 123.9 (3) | O5iv—Li2—Gd4ii | 149.6 (5) |
O13v—Gd4—Li2ii | 98.6 (2) | O2—Li2—Gd4ii | 50.8 (3) |
O8iv—Gd4—Li2ii | 36.7 (3) | B2iv—Li2—Gd4ii | 140.5 (5) |
O16—Gd4—Li2ii | 69.5 (3) | B1—Li2—Gd4ii | 77.5 (4) |
O9—Gd4—Li2ii | 151.8 (3) | B4xi—Li2—Gd4ii | 76.4 (4) |
O2ii—Gd4—Li2ii | 43.1 (3) | Gd1iv—Li2—Gd4ii | 133.5 (4) |
O10—Gd4—Li2ii | 116.8 (3) | O8xi—Li2—Gd2 | 115.0 (5) |
B4—Gd4—Li2ii | 134.8 (3) | O1—Li2—Gd2 | 104.2 (5) |
O9v—Gd4—Gd4v | 38.01 (14) | O4iv—Li2—Gd2 | 46.6 (4) |
O13v—Gd4—Gd4v | 99.95 (13) | O5iv—Li2—Gd2 | 119.6 (5) |
O8iv—Gd4—Gd4v | 126.73 (12) | O2—Li2—Gd2 | 51.8 (3) |
O16—Gd4—Gd4v | 93.40 (13) | B2iv—Li2—Gd2 | 83.1 (4) |
O9—Gd4—Gd4v | 35.04 (12) | B1—Li2—Gd2 | 78.0 (4) |
O2ii—Gd4—Gd4v | 152.96 (13) | B4xi—Li2—Gd2 | 142.5 (5) |
O10—Gd4—Gd4v | 85.84 (11) | Gd1iv—Li2—Gd2 | 142.6 (4) |
B4—Gd4—Gd4v | 61.74 (15) | Gd4ii—Li2—Gd2 | 74.5 (3) |
Li2ii—Gd4—Gd4v | 154.4 (2) | O8xi—Li2—Cs1xi | 59.8 (3) |
O9v—Gd4—Gd5v | 101.76 (14) | O1—Li2—Cs1xi | 167.2 (6) |
O13v—Gd4—Gd5v | 36.24 (13) | O4iv—Li2—Cs1xi | 73.0 (3) |
O8iv—Gd4—Gd5v | 122.64 (13) | O5iv—Li2—Cs1xi | 75.3 (4) |
O16—Gd4—Gd5v | 144.10 (14) | O2—Li2—Cs1xi | 119.5 (5) |
O9—Gd4—Gd5v | 72.93 (12) | B2iv—Li2—Cs1xi | 68.2 (3) |
O2ii—Gd4—Gd5v | 88.34 (12) | B1—Li2—Cs1xi | 154.9 (6) |
O10—Gd4—Gd5v | 37.24 (11) | B4xi—Li2—Cs1xi | 63.4 (3) |
B4—Gd4—Gd5v | 56.64 (16) | Gd1iv—Li2—Cs1xi | 118.0 (4) |
Li2ii—Gd4—Gd5v | 119.0 (2) | Gd4ii—Li2—Cs1xi | 78.7 (3) |
Gd4v—Gd4—Gd5v | 86.18 (2) | Gd2—Li2—Cs1xi | 88.0 (3) |
O9v—Gd4—Gd2 | 136.44 (13) | B1—O1—Li2 | 88.1 (6) |
O13v—Gd4—Gd2 | 130.73 (13) | B1—O1—Li1 | 88.2 (6) |
O8iv—Gd4—Gd2 | 86.43 (12) | Li2—O1—Li1 | 173.9 (7) |
O16—Gd4—Gd2 | 36.82 (13) | B1—O1—Gd1iv | 166.2 (5) |
O9—Gd4—Gd2 | 98.50 (13) | Li2—O1—Gd1iv | 91.0 (5) |
O2ii—Gd4—Gd2 | 40.10 (12) | Li1—O1—Gd1iv | 91.5 (5) |
O10—Gd4—Gd2 | 85.46 (11) | B1—O2—Li2 | 78.0 (5) |
B4—Gd4—Gd2 | 86.62 (15) | B1—O2—Gd4ii | 127.6 (4) |
Li2ii—Gd4—Gd2 | 53.4 (2) | Li2—O2—Gd4ii | 86.1 (4) |
Gd4v—Gd4—Gd2 | 122.01 (2) | B1—O2—Gd1 | 90.8 (5) |
Gd5v—Gd4—Gd2 | 116.732 (17) | Li2—O2—Gd1 | 167.6 (4) |
O11iv—Gd5—O15 | 84.81 (19) | Gd4ii—O2—Gd1 | 105.3 (2) |
O11iv—Gd5—O10v | 90.68 (19) | B1—O2—Gd2 | 126.5 (4) |
O15—Gd5—O10v | 110.01 (17) | Li2—O2—Gd2 | 86.0 (4) |
O11iv—Gd5—O12vi | 89.85 (18) | Gd4ii—O2—Gd2 | 101.29 (17) |
O15—Gd5—O12vi | 173.27 (18) | Gd1—O2—Gd2 | 96.45 (18) |
O10v—Gd5—O12vi | 74.05 (18) | B1—O3—Li1 | 79.8 (6) |
O11iv—Gd5—O13 | 157.13 (17) | B1—O3—Gd5iii | 132.9 (4) |
O15—Gd5—O13 | 84.69 (18) | Li1—O3—Gd5iii | 85.3 (4) |
O10v—Gd5—O13 | 74.01 (19) | B1—O3—Gd1 | 92.3 (5) |
O12vi—Gd5—O13 | 101.74 (17) | Li1—O3—Gd1 | 167.3 (4) |
O11iv—Gd5—O3iii | 79.26 (19) | Gd5iii—O3—Gd1 | 107.36 (19) |
O15—Gd5—O3iii | 75.92 (18) | B1—O3—Gd3 | 118.3 (4) |
O10v—Gd5—O3iii | 167.96 (19) | Li1—O3—Gd3 | 83.9 (4) |
O12vi—Gd5—O3iii | 99.10 (17) | Gd5iii—O3—Gd3 | 103.96 (17) |
O13—Gd5—O3iii | 117.54 (17) | Gd1—O3—Gd3 | 91.14 (16) |
O11iv—Gd5—O12 | 145.68 (17) | B2—O4—Li2viii | 84.3 (5) |
O15—Gd5—O12 | 107.87 (18) | B2—O4—Li2i | 84.3 (5) |
O10v—Gd5—O12 | 113.12 (17) | Li2viii—O4—Li2i | 168.6 (9) |
O12vi—Gd5—O12 | 74.52 (19) | B2—O4—Gd2i | 180.000 (2) |
O13—Gd5—O12 | 57.18 (16) | Li2viii—O4—Gd2i | 95.7 (5) |
O3iii—Gd5—O12 | 73.51 (17) | Li2i—O4—Gd2i | 95.7 (5) |
O11iv—Gd5—B5 | 172.2 (2) | B2—O4—Cs1 | 75.18 (13) |
O15—Gd5—B5 | 92.5 (2) | Li2viii—O4—Cs1 | 74.8 (4) |
O10v—Gd5—B5 | 97.1 (2) | Li2i—O4—Cs1 | 102.2 (4) |
O12vi—Gd5—B5 | 92.3 (2) | Gd2i—O4—Cs1 | 104.82 (13) |
O13—Gd5—B5 | 28.69 (19) | B2—O4—Cs1ii | 75.19 (13) |
O3iii—Gd5—B5 | 93.0 (2) | Li2viii—O4—Cs1ii | 102.2 (4) |
O12—Gd5—B5 | 29.22 (19) | Li2i—O4—Cs1ii | 74.8 (3) |
O11iv—Gd5—Li1iii | 38.4 (3) | Gd2i—O4—Cs1ii | 104.81 (13) |
O15—Gd5—Li1iii | 66.2 (3) | Cs1—O4—Cs1ii | 150.4 (3) |
O10v—Gd5—Li1iii | 128.0 (3) | B2—O5—Li2i | 80.8 (6) |
O12vi—Gd5—Li1iii | 107.1 (3) | B2—O5—Gd1 | 139.4 (3) |
O13—Gd5—Li1iii | 147.6 (3) | Li2i—O5—Gd1 | 85.5 (4) |
O3iii—Gd5—Li1iii | 43.7 (3) | B2—O5—Gd2 | 92.0 (5) |
O12—Gd5—Li1iii | 117.1 (3) | Li2i—O5—Gd2 | 171.2 (4) |
B5—Gd5—Li1iii | 134.0 (3) | Gd1—O5—Gd2 | 103.29 (19) |
O11iv—Gd5—Gd4v | 125.57 (13) | B2—O5—Cs1ii | 71.2 (2) |
O15—Gd5—Gd4v | 90.44 (13) | Li2i—O5—Cs1ii | 71.7 (4) |
O10v—Gd5—Gd4v | 41.03 (13) | Gd1—O5—Cs1ii | 138.87 (17) |
O12vi—Gd5—Gd4v | 95.99 (12) | Gd2—O5—Cs1ii | 101.16 (14) |
O13—Gd5—Gd4v | 34.40 (12) | B3—O6—Li1ix | 84.6 (5) |
O3iii—Gd5—Gd4v | 150.98 (12) | B3—O6—Li1i | 84.6 (5) |
O12—Gd5—Gd4v | 86.96 (12) | Li1ix—O6—Li1i | 169.1 (10) |
B5—Gd5—Gd4v | 61.61 (16) | B3—O6—Gd3i | 180.000 (2) |
Li1iii—Gd5—Gd4v | 150.0 (2) | Li1ix—O6—Gd3i | 95.4 (5) |
O11iv—Gd5—Gd1vii | 96.38 (14) | Li1i—O6—Gd3i | 95.4 (5) |
O15—Gd5—Gd1vii | 146.63 (13) | B3—O6—Cs1 | 74.35 (13) |
O10v—Gd5—Gd1vii | 36.80 (12) | Li1ix—O6—Cs1 | 71.0 (4) |
O12vi—Gd5—Gd1vii | 38.09 (12) | Li1i—O6—Cs1 | 105.9 (4) |
O13—Gd5—Gd1vii | 81.61 (13) | Gd3i—O6—Cs1 | 105.65 (13) |
O3iii—Gd5—Gd1vii | 137.19 (12) | B3—O6—Cs1iii | 74.35 (13) |
O12—Gd5—Gd1vii | 89.83 (12) | Li1ix—O6—Cs1iii | 105.9 (4) |
B5—Gd5—Gd1vii | 89.87 (15) | Li1i—O6—Cs1iii | 71.0 (4) |
Li1iii—Gd5—Gd1vii | 130.7 (3) | Gd3i—O6—Cs1iii | 105.65 (13) |
Gd4v—Gd5—Gd1vii | 61.771 (15) | Cs1—O6—Cs1iii | 148.7 (3) |
O11iv—Gd5—Gd5vi | 121.94 (13) | B3—O7—Li1ix | 83.6 (7) |
O15—Gd5—Gd5vi | 143.78 (13) | B3—O7—Gd1iii | 131.6 (3) |
O10v—Gd5—Gd5vi | 94.80 (12) | Li1ix—O7—Gd1iii | 86.1 (4) |
O12vi—Gd5—Gd5vi | 38.26 (13) | B3—O7—Gd3 | 90.3 (5) |
O13—Gd5—Gd5vi | 77.09 (12) | Li1ix—O7—Gd3 | 173.9 (5) |
O3iii—Gd5—Gd5vi | 85.11 (12) | Gd1iii—O7—Gd3 | 98.39 (18) |
O12—Gd5—Gd5vi | 36.27 (11) | B3—O7—Cs1 | 78.3 (2) |
B5—Gd5—Gd5vi | 57.56 (16) | Li1ix—O7—Cs1 | 73.2 (4) |
Li1iii—Gd5—Gd5vi | 118.3 (2) | Gd1iii—O7—Cs1 | 142.00 (18) |
Gd4v—Gd5—Gd5vi | 91.72 (2) | Gd3—O7—Cs1 | 105.05 (14) |
Gd1vii—Gd5—Gd5vi | 60.984 (16) | B4—O8—Li2viii | 105.4 (6) |
O8—Cs1—O9 | 45.95 (14) | B4—O8—Gd4i | 154.9 (5) |
O8—Cs1—O11 | 117.84 (15) | Li2viii—O8—Gd4i | 96.6 (5) |
O9—Cs1—O11 | 100.84 (14) | B4—O8—Cs1 | 88.9 (4) |
O8—Cs1—O13 | 102.18 (13) | Li2viii—O8—Cs1 | 88.2 (4) |
O9—Cs1—O13 | 63.08 (13) | Gd4i—O8—Cs1 | 103.90 (17) |
O11—Cs1—O13 | 45.78 (14) | B4—O9—Gd4v | 147.7 (5) |
O8—Cs1—O15i | 98.52 (14) | B4—O9—Gd4 | 96.9 (5) |
O9—Cs1—O15i | 128.84 (14) | Gd4v—O9—Gd4 | 107.0 (2) |
O11—Cs1—O15i | 59.50 (14) | B4—O9—Cs1 | 87.3 (5) |
O13—Cs1—O15i | 103.66 (13) | Gd4v—O9—Cs1 | 100.41 (16) |
O8—Cs1—O16i | 60.46 (14) | Gd4—O9—Cs1 | 116.95 (19) |
O9—Cs1—O16i | 104.80 (14) | B4—O10—Gd5v | 119.8 (4) |
O11—Cs1—O16i | 99.76 (15) | B4—O10—Gd1ii | 126.6 (5) |
O13—Cs1—O16i | 131.98 (13) | Gd5v—O10—Gd1ii | 107.16 (18) |
O15i—Cs1—O16i | 45.32 (14) | B4—O10—Gd4 | 90.2 (5) |
O8—Cs1—O14 | 119.24 (13) | Gd5v—O10—Gd4 | 101.73 (19) |
O9—Cs1—O14 | 95.46 (14) | Gd1ii—O10—Gd4 | 104.58 (19) |
O11—Cs1—O14 | 113.65 (14) | B5—O11—Li1ix | 106.8 (7) |
O13—Cs1—O14 | 91.31 (14) | B5—O11—Gd5i | 157.8 (5) |
O15i—Cs1—O14 | 135.44 (14) | Li1ix—O11—Gd5i | 93.4 (5) |
O16i—Cs1—O14 | 136.69 (14) | B5—O11—Cs1 | 88.4 (4) |
O8—Cs1—B6 | 108.20 (17) | Li1ix—O11—Cs1 | 82.1 (4) |
O9—Cs1—B6 | 73.76 (17) | Gd5i—O11—Cs1 | 103.60 (18) |
O11—Cs1—B6 | 106.59 (17) | B5—O12—Gd5vi | 123.5 (4) |
O13—Cs1—B6 | 71.94 (16) | B5—O12—Gd1iii | 122.7 (4) |
O15i—Cs1—B6 | 153.27 (16) | Gd5vi—O12—Gd1iii | 104.79 (18) |
O16i—Cs1—B6 | 153.43 (16) | B5—O12—Gd5 | 91.1 (5) |
O14—Cs1—B6 | 24.31 (16) | Gd5vi—O12—Gd5 | 105.47 (19) |
O8—Cs1—B6i | 84.15 (16) | Gd1iii—O12—Gd5 | 104.85 (19) |
O9—Cs1—B6i | 126.20 (17) | B5—O13—Gd4v | 145.3 (5) |
O11—Cs1—B6i | 84.04 (17) | B5—O13—Gd5 | 96.2 (5) |
O13—Cs1—B6i | 126.61 (16) | Gd4v—O13—Gd5 | 109.4 (2) |
O15i—Cs1—B6i | 24.72 (15) | B5—O13—Cs1 | 87.7 (4) |
O16i—Cs1—B6i | 24.23 (15) | Gd4v—O13—Cs1 | 98.94 (15) |
O14—Cs1—B6i | 131.79 (18) | Gd5—O13—Cs1 | 119.64 (19) |
B6—Cs1—B6i | 156.1 (3) | B6—O14—Gd1 | 169.7 (4) |
O8—Cs1—B4 | 24.0 (2) | B6—O14—Gd3 | 93.9 (4) |
O9—Cs1—B4 | 24.33 (19) | Gd1—O14—Gd3 | 95.26 (17) |
O11—Cs1—B4 | 117.98 (16) | B6—O14—Gd2 | 81.7 (4) |
O13—Cs1—B4 | 86.60 (18) | Gd1—O14—Gd2 | 88.05 (15) |
O15i—Cs1—B4 | 120.3 (2) | Gd3—O14—Gd2 | 152.1 (3) |
O16i—Cs1—B4 | 84.4 (2) | B6—O14—Cs1 | 80.7 (4) |
O14—Cs1—B4 | 102.0 (2) | Gd1—O14—Cs1 | 100.8 (2) |
B6—Cs1—B4 | 86.1 (2) | Gd3—O14—Cs1 | 107.41 (18) |
B6i—Cs1—B4 | 108.1 (2) | Gd2—O14—Cs1 | 99.10 (15) |
O8—Cs1—B5 | 118.94 (16) | B6—O15—Gd5 | 150.6 (5) |
O9—Cs1—B5 | 86.34 (17) | B6—O15—Gd3 | 93.0 (4) |
O11—Cs1—B5 | 23.8 (2) | Gd5—O15—Gd3 | 109.51 (18) |
O13—Cs1—B5 | 24.39 (17) | B6—O15—Cs1iv | 85.3 (4) |
O15i—Cs1—B5 | 83.3 (2) | Gd5—O15—Cs1iv | 102.85 (18) |
O16i—Cs1—B5 | 122.1 (2) | Gd3—O15—Cs1iv | 111.43 (19) |
O14—Cs1—B5 | 96.7 (2) | B6—O15—Cs1 | 58.9 (4) |
B6—Cs1—B5 | 84.5 (2) | Gd5—O15—Cs1 | 100.28 (17) |
B6i—Cs1—B5 | 107.9 (2) | Gd3—O15—Cs1 | 92.58 (15) |
B4—Cs1—B5 | 108.6 (2) | Cs1iv—O15—Cs1 | 138.22 (15) |
O8—Cs1—B3 | 168.12 (13) | B6—O16—Gd4 | 144.3 (5) |
O9—Cs1—B3 | 143.5 (2) | B6—O16—Gd2 | 105.5 (4) |
O11—Cs1—B3 | 71.00 (12) | Gd4—O16—Gd2 | 107.11 (19) |
O13—Cs1—B3 | 89.69 (14) | B6—O16—Cs1iv | 82.2 (4) |
O15i—Cs1—B3 | 78.9 (2) | Gd4—O16—Cs1iv | 98.27 (18) |
O16i—Cs1—B3 | 111.7 (2) | Gd2—O16—Cs1iv | 112.5 (2) |
O14—Cs1—B3 | 59.2 (2) | B6—O16—Cs1 | 61.7 (4) |
B6—Cs1—B3 | 74.8 (3) | Gd4—O16—Cs1 | 99.34 (18) |
B6i—Cs1—B3 | 89.2 (2) | Gd2—O16—Cs1 | 98.23 (17) |
B4—Cs1—B3 | 160.8 (3) | Cs1iv—O16—Cs1 | 137.95 (15) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y, −z+3/2; (iii) −x+3/2, y, −z+3/2; (iv) x, y+1, z; (v) −x+1, −y+1, −z+2; (vi) −x+2, −y+1, −z+2; (vii) x+1/2, −y+1, z+1/2; (viii) −x+1/2, y−1, −z+3/2; (ix) −x+3/2, y−1, −z+3/2; (x) −x+3/2, y+1, −z+3/2; (xi) −x+1/2, y+1, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | CsLi2Gd4(BO3)5 |
Mr | 1069.84 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 295 |
a, b, c (Å) | 10.644 (2), 6.4661 (15), 20.093 (4) |
β (°) | 105.250 (16) |
V (Å3) | 1334.3 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 22.40 |
Crystal size (mm) | 0.16 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.042, 0.167 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7381, 3068, 2829 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.108, 1.11 |
No. of reflections | 3068 |
No. of parameters | 248 |
Δρmax, Δρmin (e Å−3) | 4.05, −2.81 |
Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Version 1.0c; Westrip, 2007).
Rare earth borates are promising luminescent materials (Jubera et al., 2003; Sablayrolles et al., 2005) and their applications are found in Plasma Displays Panels (PDP) and efficient light conversion bulbs (Fouassier et al., 1981). Besides that, rare earth borates are good nonlinear optical materials, e.g. YCa4O(BO3)3 (Aka et al., 1997), CaLa2B10O19 (Wu et al., 2001), and self-frequency doubling laser crystals Nd3+:YAl3(BO3) (Dorozhkin et al., 1981). Recently, Li6Gd(BO3)3:Ce has received extensive attention as a new efficient thermal neutron detection material. (Czirr et al., 1999; Chaminade et al., 2001, van Eijk et al., 2001)
In the Li2O—Gd2O3—B2O3 system, there are four ternary compounds, LiGd6O5(BO3)3 (Chaminade et al., 1999), Li6Gd(BO3)3 (Mascetti et al., 1983), Li3Gd(BO3)2 and LiGd2O2BO3 (Jubera, Gravereau & Chaminade, 2001). In an attempt to synthesize compounds in the system using caesium borate as the flux, we obtained a new quaternary compound CsLi2Gd4(BO3)5, which is, to our knowledge, the first rare-earth borate containing caesium.
The structure of CsLi2Gd4(BO3)5 is shown in figure 1. In the asymmetric unit, all six boron atoms are three-coordinated yielding planar BO3 groups (B—O: 1.352 to 1.408 Å, average: 1.376 Å, which agrees with literature values). The site symmetry of B2 and B3 is 2.
The Gd atoms occupy five different crystallographic sites, Gd2, Gd4 and Gd5 being coordinated by seven O atoms and Gd1 and Gd3 coordinated to eight and nine oxygen atoms, respectively. Gd2, Gd3 lie on twofold axes. The GdOn polyhedra (Gd—O: 2.241 to 2.634 Å) share edges yielding two types of Gd—O chains. The chain containing Gd1, Gd3 and Gd5 atoms is terminated by two BO3 groups (Fig. 2). The three-element Gd3O17 chain (Fig. 3) joins other equivalent three-element chains to form an infinite zigzag chain. Both chains can be classified as fluorite-related ribbons, which are common in rare earth borate compounds (Ren et al., 1999; Jubera, Gravereau, Chaminade & Fouassier, 2001). Similar Bi—O ribbons are reported in bismuth compounds (Crumpton & Greaves, 2004; Darriet et al., 2005; Muktha & Row, 2006). The two chains in CsLi2Gd4(BO3)5 are interlocked by sharing the edges of Gd polyhedra to form a two dimensional [Gd8O16(BO3)2]14- layer in the ac plane. The layers are inter-linked by out of plane BO3 groups in the b direction into a 3 dimensional network.
Both Li atoms are five-coordinated (distorted square pyramids, Li—O: 1.885 to 2.145 Å). The Cs atom is coordinated by seven O atoms and resides in a big basket-like cage.