A single-crystal X-ray structure study of gadolinium triiron tetraborate, GdFe
(BO
)
, at room temperature and at 90 K is reported. At room temperature GdFe
(BO
)
crystallizes in a trigonal space group,
32 (No. 155), the same as found for other members of the iron borate family
RFe
(BO
)
. At 90 K the structure of GdFe
(BO
)
transforms to the space group
3
21 (No. 152). The low-temperature structure determination gives new insight into the weakly first-order structural phase transition at 156 K and into the related Raman phonon anomalies. The presence of two inequivalent iron chains in the low-temperature structure provides a new perspective on the interpretation of the low-temperature magnetic properties.
Supporting information
For both compounds, data collection: SMART, Bruker Version 5.624, 2001; cell refinement: SAINT, Bruker Version 6.02A, 2000; data reduction: XPREP, Bruker Version 5.1/NT, 2000. Program(s) used to solve structure: SIR97 (Altomare et al., 1997) for LT; Coordinates from Campá et al. for RT. For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTO (Meetsma, 2003) ORTEP (Farrugia, 1997; Johnson et al., 2000) PLATON (Spek, 1994); software used to prepare material for publication: PLATON (Spek, 1990).
Crystal data top
B4Fe3GdO12 | The final unit cell was obtained from the xyz centroids of
5439 reflections after integration using the SAINT software
package (Bruker, 2000). |
Mr = 560.04 | Dx = 4.699 Mg m−3 |
Trigonal, P3121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 31 2" | Cell parameters from 5439 reflections |
a = 9.5305 (3) Å | θ = 3.7–38.6° |
c = 7.5479 (2) Å | µ = 13.74 mm−1 |
V = 593.73 (3) Å3 | T = 90 K |
Z = 3 | Broken_block, light_green |
F(000) = 774 | 0.22 × 0.15 × 0.11 mm |
Data collection top
Bruker Smart Apex diffractometer | 2217 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 1956 reflections with I > 2σ(I) |
Parallel mounted graphite monochromator | Rint = 0.034 |
Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm-1 | θmax = 38.6°, θmin = 2.5° |
phi and ω scans | h = −16→16 |
Absorption correction: analytical Bruker, 2000 | k = −16→16 |
Tmin = 0.062, Tmax = 0.251 | l = −13→13 |
13868 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0312P)2 + 0.P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.017 | (Δ/σ)max = 0.003 |
wR(F2) = 0.045 | Δρmax = 0.82 e Å−3 |
S = 0.86 | Δρmin = −0.51 e Å−3 |
2217 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
95 parameters | Extinction coefficient: 0.0359 (10) |
0 restraints | Absolute structure: Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5
Flack, H.D. & Bernardinelli, G. (1999, 2000) |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.5 |
Crystal data top
B4Fe3GdO12 | Z = 3 |
Mr = 560.04 | Mo Kα radiation |
Trigonal, P3121 | µ = 13.74 mm−1 |
a = 9.5305 (3) Å | T = 90 K |
c = 7.5479 (2) Å | 0.22 × 0.15 × 0.11 mm |
V = 593.73 (3) Å3 | |
Data collection top
Bruker Smart Apex diffractometer | 2217 independent reflections |
Absorption correction: analytical Bruker, 2000 | 1956 reflections with I > 2σ(I) |
Tmin = 0.062, Tmax = 0.251 | Rint = 0.034 |
13868 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.045 | Δρmax = 0.82 e Å−3 |
S = 0.86 | Δρmin = −0.51 e Å−3 |
2217 reflections | Absolute structure: Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5
Flack, H.D. & Bernardinelli, G. (1999, 2000) |
95 parameters | Absolute structure parameter: 0.5 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Gd1 | −0.33342 (1) | −0.33342 (1) | 0.00000 | 0.0041 (1) | |
Fe1 | 0.11536 (5) | 0.11536 (5) | 0.00000 | 0.0036 (1) | |
Fe2 | −0.21410 (6) | −0.54975 (4) | 0.34154 (2) | 0.0037 (1) | |
O1 | 0.00000 | −0.07819 (15) | 0.16667 | 0.0072 (3) | |
O2 | −0.5832 (2) | −0.27090 (13) | 0.13774 (12) | 0.0069 (2) | |
O3 | −0.1194 (3) | −0.30445 (16) | −0.17980 (18) | 0.0057 (3) | |
O4 | −0.1467 (3) | −0.36234 (16) | 0.18479 (18) | 0.0058 (2) | |
O5 | 0.4755 (2) | 0.1451 (2) | −0.15980 (8) | 0.0057 (3) | |
O6 | 0.1877 (2) | 0.00000 | −0.16667 | 0.0053 (3) | |
O7 | −0.5235 (3) | −0.53811 (17) | −0.18533 (18) | 0.0056 (2) | |
B1 | 0.33204 (14) | 0.00000 | −0.16667 | 0.0045 (5) | |
B2 | −0.4473 (4) | −0.1201 (3) | 0.15617 (14) | 0.0053 (3) | |
B3 | 0.00000 | −0.2223 (3) | 0.16667 | 0.0049 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Gd1 | 0.0041 (1) | 0.0041 (1) | 0.0041 (1) | 0.0021 (1) | −0.0001 (1) | 0.0001 (1) |
Fe1 | 0.0036 (1) | 0.0036 (1) | 0.0036 (1) | 0.0017 (1) | −0.0001 (1) | 0.0001 (1) |
Fe2 | 0.0035 (1) | 0.0036 (1) | 0.0038 (1) | 0.0017 (1) | 0.0000 (1) | 0.0001 (1) |
O1 | 0.0081 (6) | 0.0054 (4) | 0.0089 (4) | 0.0040 (3) | 0.0024 (4) | 0.0012 (2) |
O2 | 0.0058 (3) | 0.0062 (3) | 0.0081 (3) | 0.0025 (3) | −0.0014 (3) | 0.0012 (3) |
O3 | 0.0062 (4) | 0.0040 (5) | 0.0065 (4) | 0.0023 (4) | 0.0007 (3) | 0.0006 (3) |
O4 | 0.0054 (4) | 0.0045 (4) | 0.0067 (4) | 0.0019 (4) | −0.0003 (3) | 0.0007 (3) |
O5 | 0.0051 (4) | 0.0050 (4) | 0.0063 (5) | 0.0019 (5) | −0.0003 (3) | 0.0007 (3) |
O6 | 0.0044 (4) | 0.0058 (6) | 0.0062 (5) | 0.0029 (3) | −0.0010 (2) | −0.0019 (5) |
O7 | 0.0047 (4) | 0.0063 (4) | 0.0064 (4) | 0.0033 (4) | −0.0001 (3) | −0.0008 (3) |
B1 | 0.0042 (8) | 0.0048 (9) | 0.0046 (11) | 0.0024 (4) | 0.0004 (2) | 0.0009 (5) |
B2 | 0.0050 (6) | 0.0067 (7) | 0.0055 (5) | 0.0040 (4) | 0.0001 (4) | 0.0004 (5) |
B3 | 0.0018 (8) | 0.0061 (6) | 0.0055 (7) | 0.0009 (4) | 0.0008 (6) | 0.0004 (3) |
Geometric parameters (Å, º) top
Gd1—O3 | 2.3485 (18) | Fe2—O4 | 1.9635 (14) |
Gd1—O4 | 2.3830 (18) | Fe2—O5v | 2.025 (2) |
Gd1—O7 | 2.3474 (15) | Fe2—O7vi | 1.971 (3) |
Gd1—B2 | 2.985 (3) | Fe2—O5vii | 2.017 (2) |
Gd1—O3i | 2.3485 (16) | Fe2—O2viii | 2.0332 (16) |
Gd1—O4i | 2.3830 (16) | Fe2—O2ix | 2.0490 (10) |
Gd1—O7i | 2.3474 (16) | O1—B3 | 1.373 (3) |
Gd1—B2i | 2.985 (3) | O2—B2 | 1.379 (3) |
Fe1—O1 | 2.0411 (10) | O3—B2i | 1.370 (3) |
Fe1—O6 | 2.0061 (12) | O4—B3 | 1.374 (3) |
Fe1—O3ii | 1.958 (2) | O5—B1 | 1.3761 (19) |
Fe1—O6ii | 2.0061 (9) | O6—B1 | 1.376 (2) |
Fe1—O1iii | 2.0411 (10) | O7—B2x | 1.360 (5) |
Fe1—O3iv | 1.9583 (14) | | |
| | | |
O3—Gd1—O4 | 72.36 (6) | O2viii—Fe2—O4 | 91.99 (6) |
O3—Gd1—O7 | 90.99 (6) | O2ix—Fe2—O4 | 168.53 (8) |
O3—Gd1—B2 | 137.60 (6) | O5v—Fe2—O7vi | 90.43 (9) |
O3—Gd1—O3i | 120.92 (5) | O5v—Fe2—O5vii | 167.41 (9) |
O3—Gd1—O4i | 89.54 (6) | O2viii—Fe2—O5v | 76.55 (8) |
O3—Gd1—O7i | 140.62 (6) | O2ix—Fe2—O5v | 95.92 (7) |
O3—Gd1—B2i | 26.49 (5) | O5vii—Fe2—O7vi | 98.38 (9) |
O4—Gd1—O7 | 124.29 (5) | O2viii—Fe2—O7vi | 162.76 (8) |
O4—Gd1—B2 | 113.24 (5) | O2ix—Fe2—O7vi | 83.30 (7) |
O3i—Gd1—O4 | 89.54 (5) | O2viii—Fe2—O5vii | 92.94 (8) |
O4—Gd1—O4i | 143.21 (5) | O2ix—Fe2—O5vii | 76.33 (6) |
O4—Gd1—O7i | 86.70 (6) | O2viii—Fe2—O2ix | 86.82 (6) |
O4—Gd1—B2i | 60.35 (5) | Fe1—O1—B3 | 129.38 (5) |
O7—Gd1—B2 | 114.15 (7) | Fe1—O1—Fe1ii | 101.24 (5) |
O3i—Gd1—O7 | 140.62 (7) | Fe1ii—O1—B3 | 129.38 (7) |
O4i—Gd1—O7 | 86.70 (5) | Fe2xi—O2—B2 | 128.74 (13) |
O7—Gd1—O7i | 73.47 (5) | Fe2xii—O2—B2 | 124.47 (10) |
O7—Gd1—B2i | 81.11 (7) | Fe2xi—O2—Fe2xii | 102.46 (6) |
O3i—Gd1—B2 | 26.49 (7) | Gd1—O3—Fe1iii | 121.40 (8) |
O4i—Gd1—B2 | 60.35 (5) | Gd1—O3—B2i | 103.63 (13) |
O7i—Gd1—B2 | 81.11 (6) | Fe1iii—O3—B2i | 134.71 (15) |
B2—Gd1—B2i | 161.73 (7) | Gd1—O4—Fe2 | 122.30 (8) |
O3i—Gd1—O4i | 72.36 (5) | Gd1—O4—B3 | 106.58 (10) |
O3i—Gd1—O7i | 90.99 (5) | Fe2—O4—B3 | 130.89 (13) |
O3i—Gd1—B2i | 137.60 (6) | Fe2xiii—O5—B1 | 127.32 (10) |
O4i—Gd1—O7i | 124.29 (6) | Fe2xiv—O5—B1 | 128.71 (9) |
O4i—Gd1—B2i | 113.24 (5) | Fe2xiii—O5—Fe2xiv | 103.91 (8) |
O7i—Gd1—B2i | 114.15 (6) | Fe1—O6—B1 | 128.15 (4) |
O1—Fe1—O6 | 93.94 (3) | Fe1—O6—Fe1iii | 103.71 (9) |
O1—Fe1—O3ii | 86.00 (7) | Fe1iii—O6—B1 | 128.15 (5) |
O1—Fe1—O6ii | 77.53 (5) | Gd1—O7—Fe2xv | 117.67 (9) |
O1—Fe1—O1iii | 87.69 (3) | Gd1—O7—B2x | 113.03 (12) |
O1—Fe1—O3iv | 167.95 (9) | Fe2xv—O7—B2x | 129.29 (13) |
O3ii—Fe1—O6 | 92.67 (7) | O5—B1—O6 | 119.41 (10) |
O6—Fe1—O6ii | 168.27 (6) | O5—B1—O5iv | 121.21 (17) |
O1iii—Fe1—O6 | 77.53 (5) | O5iv—B1—O6 | 119.38 (12) |
O3iv—Fe1—O6 | 94.71 (6) | Gd1—B2—O2 | 73.87 (12) |
O3ii—Fe1—O6ii | 94.71 (6) | Gd1—B2—O7xvi | 150.31 (12) |
O1iii—Fe1—O3ii | 167.95 (8) | Gd1—B2—O3i | 49.88 (10) |
O3ii—Fe1—O3iv | 101.96 (10) | O2—B2—O7xvi | 119.6 (3) |
O1iii—Fe1—O6ii | 93.94 (5) | O2—B2—O3i | 115.6 (2) |
O3iv—Fe1—O6ii | 92.67 (8) | O3i—B2—O7xvi | 124.9 (2) |
O1iii—Fe1—O3iv | 86.00 (6) | O1—B3—O4 | 117.55 (13) |
O4—Fe2—O5v | 94.90 (7) | O1—B3—O4xvii | 117.6 (2) |
O4—Fe2—O7vi | 100.45 (7) | O4—B3—O4xvii | 124.9 (2) |
O4—Fe2—O5vii | 92.35 (7) | | |
| | | |
O4—Gd1—O3—Fe1iii | −126.76 (9) | O3i—Gd1—B2—O2 | −146.23 (14) |
O4—Gd1—O3—B2i | 58.28 (12) | O4i—Gd1—B2—O2 | 102.65 (10) |
O7—Gd1—O3—Fe1iii | 107.39 (9) | O7i—Gd1—B2—O2 | −35.53 (8) |
O7—Gd1—O3—B2i | −67.57 (12) | O3—Gd1—O3i—B2 | 136.72 (11) |
B2—Gd1—O3—Fe1iii | −21.35 (13) | O4—Gd1—O3i—B2 | −154.27 (11) |
B2—Gd1—O3—B2i | 163.69 (11) | O7—Gd1—O3i—B2 | −2.87 (15) |
O3—Gd1—O4—Fe2 | −127.20 (9) | O4—Gd1—B2i—O3 | −111.13 (14) |
O3—Gd1—O4—B3 | 57.76 (10) | O7—Gd1—B2i—O3 | 110.69 (12) |
O7—Gd1—O4—Fe2 | −48.43 (11) | O6—Fe1—O1—B3 | 8.13 (11) |
O7—Gd1—O4—B3 | 136.53 (9) | O1—Fe1—O6—B1 | −93.24 (3) |
B2—Gd1—O4—Fe2 | 97.83 (9) | O5v—Fe2—O4—Gd1 | 98.55 (10) |
B2—Gd1—O4—B3 | −77.21 (11) | O5v—Fe2—O4—B3 | −87.73 (16) |
O3i—Gd1—O4—Fe2 | 110.00 (9) | O7vi—Fe2—O4—Gd1 | −170.11 (9) |
O3i—Gd1—O4—B3 | −65.04 (10) | O7vi—Fe2—O4—B3 | 3.61 (17) |
O4i—Gd1—O4—Fe2 | 168.87 (7) | O5vii—Fe2—O4—Gd1 | −71.13 (10) |
O4i—Gd1—O4—B3 | −6.17 (15) | O5vii—Fe2—O4—B3 | 102.58 (16) |
O7i—Gd1—O4—Fe2 | 18.98 (8) | O2viii—Fe2—O4—Gd1 | 21.89 (9) |
O7i—Gd1—O4—B3 | −156.07 (10) | O2viii—Fe2—O4—B3 | −164.40 (15) |
B2i—Gd1—O4—Fe2 | −101.31 (10) | O4—Fe2—O7vi—B2ii | 10.8 (2) |
B2i—Gd1—O4—B3 | 83.65 (11) | O4—Fe2—O2viii—B2viii | −69.01 (16) |
O3—Gd1—O7—Fe2xv | 25.80 (7) | Fe1—O1—B3—O4 | −133.57 (9) |
O3—Gd1—O7—B2x | −155.03 (12) | Fe2xi—O2—B2—Gd1 | −119.34 (12) |
O4—Gd1—O7—Fe2xv | −43.40 (9) | Fe2xi—O2—B2—O7xvi | 31.78 (19) |
O4—Gd1—O7—B2x | 135.77 (12) | Fe2xi—O2—B2—O3i | −147.46 (11) |
B2—Gd1—O7—Fe2xv | 170.60 (6) | Fe2xii—O2—B2—Gd1 | 88.25 (12) |
B2—Gd1—O7—B2x | −10.22 (13) | Fe2xii—O2—B2—O7xvi | −120.64 (14) |
O3—Gd1—B2—O2 | 153.06 (8) | Fe2xii—O2—B2—O3i | 60.13 (18) |
O3—Gd1—B2—O7xvi | 31.1 (4) | Gd1—O4—B3—O1 | 43.05 (8) |
O3—Gd1—B2—O3i | −60.72 (13) | Gd1—O4—B3—O4xvii | −136.96 (9) |
O4—Gd1—B2—O2 | −118.03 (8) | Fe2—O4—B3—O1 | −131.41 (12) |
O4—Gd1—B2—O7xvi | 120.0 (3) | Fe2—O4—B3—O4xvii | 48.59 (17) |
O4—Gd1—B2—O3i | 28.20 (13) | Fe2xiii—O5—B1—O6 | −55.03 (12) |
O7—Gd1—B2—O2 | 31.78 (9) | Fe2xiv—O5—B1—O6 | 128.13 (12) |
O7—Gd1—B2—O7xvi | −90.2 (4) | Fe1—O6—B1—O5 | −50.40 (3) |
O7—Gd1—B2—O3i | 178.01 (10) | | |
Symmetry codes: (i) y, x, −z; (ii) −y, x−y, z+1/3; (iii) −x+y, −x, z−1/3; (iv) x−y, −y, −z−1/3; (v) −y, x−y−1, z+1/3; (vi) −x+y, −x−1, z+2/3; (vii) −x+y, −x, z+2/3; (viii) −x−1, −x+y−1, −z+1/3; (ix) x−y, −y−1, −z+2/3; (x) −x+y−1, −x−1, z−1/3; (xi) −x−1, −x+y, −z+1/3; (xii) x−y−1, −y−1, −z+2/3; (xiii) −y, x−y, z−2/3; (xiv) −x+y+1, −x, z−1/3; (xv) −y−1, x−y−1, z−2/3; (xvi) −y−1, x−y, z+1/3; (xvii) −x, −x+y, −z+1/3. |
Crystal data top
B4Fe3GdO12 | The final unit cell was obtained from the xyz centroids of
4767 reflections after integration using the SAINT software
package (Bruker, 2000). |
Mr = 560.04 | Dx = 4.712 Mg m−3 |
Trigonal, R32 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: R 3 2" | Cell parameters from 4767 reflections |
a = 9.5203 (6) Å | θ = 3.7–38.7° |
c = 7.5439 (5) Å | µ = 13.77 mm−1 |
V = 592.15 (7) Å3 | T = 297 K |
Z = 3 | Broken_block, light_green |
F(000) = 774 | 0.22 × 0.15 × 0.11 mm |
Data collection top
Bruker Smart Apex diffractometer | 755 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 755 reflections with I > 2σ(I) |
Parallel mounted graphite monochromator | Rint = 0.034 |
Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm-1 | θmax = 38.7°, θmin = 3.7° |
phi and ω scans | h = −16→16 |
Absorption correction: analytical Bruker, 2000) | k = −16→16 |
Tmin = 0.056, Tmax = 0.252 | l = −13→13 |
4700 measured reflections | |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0272P)2 + 0.P] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max < 0.001 |
R[F2 > 2σ(F2)] = 0.015 | Δρmax = 0.62 e Å−3 |
wR(F2) = 0.037 | Δρmin = −0.97 e Å−3 |
S = 1.08 | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
755 reflections | Extinction coefficient: 0.0371 (12) |
35 parameters | Absolute structure: Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5
Flack, H.D. & Bernardinelli, G. (1999, 2000) |
0 restraints | Absolute structure parameter: 0.50 |
Primary atom site location: from Campá et al. | |
Crystal data top
B4Fe3GdO12 | Z = 3 |
Mr = 560.04 | Mo Kα radiation |
Trigonal, R32 | µ = 13.77 mm−1 |
a = 9.5203 (6) Å | T = 297 K |
c = 7.5439 (5) Å | 0.22 × 0.15 × 0.11 mm |
V = 592.15 (7) Å3 | |
Data collection top
Bruker Smart Apex diffractometer | 755 independent reflections |
Absorption correction: analytical Bruker, 2000) | 755 reflections with I > 2σ(I) |
Tmin = 0.056, Tmax = 0.252 | Rint = 0.034 |
4700 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.015 | 0 restraints |
wR(F2) = 0.037 | Δρmax = 0.62 e Å−3 |
S = 1.08 | Δρmin = −0.97 e Å−3 |
755 reflections | Absolute structure: Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5
Flack, H.D. & Bernardinelli, G. (1999, 2000) |
35 parameters | Absolute structure parameter: 0.50 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Gd | 0.00000 | 0.00000 | 0.00000 | 0.0087 (1) | |
Fe | 0.21659 (5) | 0.33333 | 0.33333 | 0.0065 (1) | |
O1 | 0.1442 (2) | 0.1442 (2) | 0.50000 | 0.0083 (3) | |
O2 | 0.4087 (3) | 0.4087 (3) | 0.50000 | 0.0132 (5) | |
O3 | 0.02538 (19) | 0.2125 (2) | 0.1824 (2) | 0.0095 (3) | |
B1 | 0.00000 | 0.00000 | 0.50000 | 0.0066 (6) | |
B2 | 0.5526 (3) | 0.5526 (3) | 0.50000 | 0.0077 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Gd | 0.0089 (1) | 0.0089 (1) | 0.0083 (1) | 0.0044 (1) | 0.0000 | 0.0000 |
Fe | 0.0059 (1) | 0.0064 (1) | 0.0075 (2) | 0.0032 (1) | 0.0000 (1) | −0.0001 (1) |
O1 | 0.0058 (5) | 0.0058 (5) | 0.0109 (7) | 0.0011 (6) | −0.0014 (3) | 0.0014 (3) |
O2 | 0.0076 (6) | 0.0076 (6) | 0.0182 (11) | −0.0009 (8) | −0.0047 (5) | 0.0047 (5) |
O3 | 0.0065 (5) | 0.0112 (5) | 0.0111 (5) | 0.0046 (4) | −0.0021 (4) | −0.0025 (5) |
B1 | 0.0058 (9) | 0.0058 (9) | 0.0081 (14) | 0.0029 (4) | 0.0000 | 0.0000 |
B2 | 0.0070 (7) | 0.0070 (7) | 0.0093 (8) | 0.0036 (11) | −0.0007 (4) | 0.0007 (4) |
Geometric parameters (Å, º) top
Gd—O3 | 2.3571 (17) | Fe—O3 | 1.9595 (18) |
Gd—O3i | 2.357 (2) | Fe—O1vi | 2.0138 (13) |
Gd—O3ii | 2.357 (3) | Fe—O2vi | 2.031 (3) |
Gd—O3iii | 2.3571 (19) | Fe—O3vii | 1.959 (2) |
Gd—O3iv | 2.357 (2) | O1—B1 | 1.3728 (18) |
Gd—O3v | 2.3570 (18) | O2—B2 | 1.370 (4) |
Fe—O1 | 2.0142 (13) | O3—B2viii | 1.366 (4) |
Fe—O2 | 2.032 (2) | | |
| | | |
O3—Gd—O3i | 89.36 (7) | O2—Fe—O3vii | 86.81 (10) |
O3—Gd—O3ii | 89.36 (6) | O1vi—Fe—O3 | 95.59 (7) |
O3—Gd—O3iii | 122.58 (6) | O2vi—Fe—O3 | 86.83 (10) |
O3—Gd—O3iv | 72.39 (6) | O3—Fe—O3vii | 101.11 (9) |
O3—Gd—O3v | 141.88 (9) | O1vi—Fe—O2vi | 76.96 (9) |
O3i—Gd—O3ii | 89.36 (7) | O1vi—Fe—O3vii | 92.05 (8) |
O3i—Gd—O3iii | 141.88 (7) | O2vi—Fe—O3vii | 167.11 (10) |
O3i—Gd—O3iv | 122.57 (8) | Fe—O1—B1 | 128.17 (9) |
O3i—Gd—O3v | 72.39 (6) | Fe—O1—Feix | 103.65 (8) |
O3ii—Gd—O3iii | 72.39 (7) | Feix—O1—B1 | 128.17 (8) |
O3ii—Gd—O3iv | 141.87 (7) | Fe—O2—B2 | 128.80 (14) |
O3ii—Gd—O3v | 122.57 (7) | Fe—O2—Feix | 102.40 (12) |
O3iii—Gd—O3iv | 89.36 (7) | Feix—O2—B2 | 128.80 (16) |
O3iii—Gd—O3v | 89.36 (7) | Gd—O3—Fe | 120.64 (9) |
O3iv—Gd—O3v | 89.36 (7) | Gd—O3—B2viii | 107.75 (12) |
O1—Fe—O2 | 76.98 (8) | Fe—O3—B2viii | 131.47 (13) |
O1—Fe—O3 | 92.05 (7) | O1—B1—O1i | 120.00 (13) |
O1—Fe—O1vi | 167.97 (11) | O1—B1—O1ii | 120.00 (14) |
O1—Fe—O2vi | 94.23 (8) | O1i—B1—O1ii | 120.00 (15) |
O1—Fe—O3vii | 95.60 (6) | O2—B2—O3x | 117.5 (3) |
O2—Fe—O3 | 167.13 (9) | O2—B2—O3xi | 117.5 (2) |
O1vi—Fe—O2 | 94.23 (9) | O3x—B2—O3xi | 125.0 (2) |
O2—Fe—O2vi | 87.31 (11) | | |
| | | |
O3i—Gd—O3—Fe | 110.73 (9) | O2—Fe—O1—B1 | 179.98 (15) |
O3ii—Gd—O3—Fe | 21.37 (9) | O3—Fe—O1—B1 | −6.79 (14) |
O3iii—Gd—O3—Fe | −47.15 (11) | O1—Fe—O2—B2 | 180.0 (3) |
O3iv—Gd—O3—Fe | −124.62 (10) | O1—Fe—O3—Gd | −72.16 (9) |
O3v—Gd—O3—Fe | 170.44 (7) | O3vii—Fe—O3—Gd | −168.27 (8) |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) y, x, −z; (iv) −x, −x+y, −z; (v) x−y, −y, −z; (vi) −x+y+1/3, −x+2/3, z−1/3; (vii) x−y+1/3, −y+2/3, −z+2/3; (viii) x−2/3, y−1/3, z−1/3; (ix) y, x, −z+1; (x) y+1/3, x+2/3, −z+2/3; (xi) x+2/3, y+1/3, z+1/3. |
Experimental details
| (LT) | (RT) |
Crystal data |
Chemical formula | B4Fe3GdO12 | B4Fe3GdO12 |
Mr | 560.04 | 560.04 |
Crystal system, space group | Trigonal, P3121 | Trigonal, R32 |
Temperature (K) | 90 | 297 |
a, c (Å) | 9.5305 (3), 7.5479 (2) | 9.5203 (6), 7.5439 (5) |
V (Å3) | 593.73 (3) | 592.15 (7) |
Z | 3 | 3 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 13.74 | 13.77 |
Crystal size (mm) | 0.22 × 0.15 × 0.11 | 0.22 × 0.15 × 0.11 |
|
Data collection |
Diffractometer | Bruker Smart Apex diffractometer | Bruker Smart Apex diffractometer |
Absorption correction | Analytical Bruker, 2000 | Analytical Bruker, 2000) |
Tmin, Tmax | 0.062, 0.251 | 0.056, 0.252 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13868, 2217, 1956 | 4700, 755, 755 |
Rint | 0.034 | 0.034 |
(sin θ/λ)max (Å−1) | 0.877 | 0.880 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.045, 0.86 | 0.015, 0.037, 1.08 |
No. of reflections | 2217 | 755 |
No. of parameters | 95 | 35 |
Δρmax, Δρmin (e Å−3) | 0.82, −0.51 | 0.62, −0.97 |
Absolute structure | Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5
Flack, H.D. & Bernardinelli, G. (1999, 2000) | Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5
Flack, H.D. & Bernardinelli, G. (1999, 2000) |
Absolute structure parameter | 0.5 | 0.50 |
Selected geometric parameters (Å, º) for (LT) topGd1—O3 | 2.3485 (18) | Fe2—O4 | 1.9635 (14) |
Gd1—O4 | 2.3830 (18) | Fe2—O5v | 2.025 (2) |
Gd1—O7 | 2.3474 (15) | Fe2—O7vi | 1.971 (3) |
Gd1—B2 | 2.985 (3) | Fe2—O5vii | 2.017 (2) |
Gd1—O3i | 2.3485 (16) | Fe2—O2viii | 2.0332 (16) |
Gd1—O4i | 2.3830 (16) | Fe2—O2ix | 2.0490 (10) |
Gd1—O7i | 2.3474 (16) | O1—B3 | 1.373 (3) |
Gd1—B2i | 2.985 (3) | O2—B2 | 1.379 (3) |
Fe1—O1 | 2.0411 (10) | O3—B2i | 1.370 (3) |
Fe1—O6 | 2.0061 (12) | O4—B3 | 1.374 (3) |
Fe1—O3ii | 1.958 (2) | O5—B1 | 1.3761 (19) |
Fe1—O6ii | 2.0061 (9) | O6—B1 | 1.376 (2) |
Fe1—O1iii | 2.0411 (10) | O7—B2x | 1.360 (5) |
Fe1—O3iv | 1.9583 (14) | | |
| | | |
O3—Gd1—O4 | 72.36 (6) | O2viii—Fe2—O4 | 91.99 (6) |
O3—Gd1—O7 | 90.99 (6) | O2ix—Fe2—O4 | 168.53 (8) |
O3—Gd1—B2 | 137.60 (6) | O5v—Fe2—O7vi | 90.43 (9) |
O3—Gd1—O3i | 120.92 (5) | O5v—Fe2—O5vii | 167.41 (9) |
O3—Gd1—O4i | 89.54 (6) | O2viii—Fe2—O5v | 76.55 (8) |
O3—Gd1—O7i | 140.62 (6) | O2ix—Fe2—O5v | 95.92 (7) |
O3—Gd1—B2i | 26.49 (5) | O5vii—Fe2—O7vi | 98.38 (9) |
O4—Gd1—O7 | 124.29 (5) | O2viii—Fe2—O7vi | 162.76 (8) |
O4—Gd1—B2 | 113.24 (5) | O2ix—Fe2—O7vi | 83.30 (7) |
O3i—Gd1—O4 | 89.54 (5) | O2viii—Fe2—O5vii | 92.94 (8) |
O4—Gd1—O4i | 143.21 (5) | O2ix—Fe2—O5vii | 76.33 (6) |
O4—Gd1—O7i | 86.70 (6) | O2viii—Fe2—O2ix | 86.82 (6) |
O4—Gd1—B2i | 60.35 (5) | Fe1—O1—B3 | 129.38 (5) |
O7—Gd1—B2 | 114.15 (7) | Fe1—O1—Fe1ii | 101.24 (5) |
O3i—Gd1—O7 | 140.62 (7) | Fe1ii—O1—B3 | 129.38 (7) |
O4i—Gd1—O7 | 86.70 (5) | Fe2xi—O2—B2 | 128.74 (13) |
O7—Gd1—O7i | 73.47 (5) | Fe2xii—O2—B2 | 124.47 (10) |
O7—Gd1—B2i | 81.11 (7) | Fe2xi—O2—Fe2xii | 102.46 (6) |
O3i—Gd1—B2 | 26.49 (7) | Gd1—O3—Fe1iii | 121.40 (8) |
O4i—Gd1—B2 | 60.35 (5) | Gd1—O3—B2i | 103.63 (13) |
O7i—Gd1—B2 | 81.11 (6) | Fe1iii—O3—B2i | 134.71 (15) |
B2—Gd1—B2i | 161.73 (7) | Gd1—O4—Fe2 | 122.30 (8) |
O3i—Gd1—O4i | 72.36 (5) | Gd1—O4—B3 | 106.58 (10) |
O3i—Gd1—O7i | 90.99 (5) | Fe2—O4—B3 | 130.89 (13) |
O3i—Gd1—B2i | 137.60 (6) | Fe2xiii—O5—B1 | 127.32 (10) |
O4i—Gd1—O7i | 124.29 (6) | Fe2xiv—O5—B1 | 128.71 (9) |
O4i—Gd1—B2i | 113.24 (5) | Fe2xiii—O5—Fe2xiv | 103.91 (8) |
O7i—Gd1—B2i | 114.15 (6) | Fe1—O6—B1 | 128.15 (4) |
O1—Fe1—O6 | 93.94 (3) | Fe1—O6—Fe1iii | 103.71 (9) |
O1—Fe1—O3ii | 86.00 (7) | Fe1iii—O6—B1 | 128.15 (5) |
O1—Fe1—O6ii | 77.53 (5) | Gd1—O7—Fe2xv | 117.67 (9) |
O1—Fe1—O1iii | 87.69 (3) | Gd1—O7—B2x | 113.03 (12) |
O1—Fe1—O3iv | 167.95 (9) | Fe2xv—O7—B2x | 129.29 (13) |
O3ii—Fe1—O6 | 92.67 (7) | O5—B1—O6 | 119.41 (10) |
O6—Fe1—O6ii | 168.27 (6) | O5—B1—O5iv | 121.21 (17) |
O1iii—Fe1—O6 | 77.53 (5) | O5iv—B1—O6 | 119.38 (12) |
O3iv—Fe1—O6 | 94.71 (6) | Gd1—B2—O2 | 73.87 (12) |
O3ii—Fe1—O6ii | 94.71 (6) | Gd1—B2—O7xvi | 150.31 (12) |
O1iii—Fe1—O3ii | 167.95 (8) | Gd1—B2—O3i | 49.88 (10) |
O3ii—Fe1—O3iv | 101.96 (10) | O2—B2—O7xvi | 119.6 (3) |
O1iii—Fe1—O6ii | 93.94 (5) | O2—B2—O3i | 115.6 (2) |
O3iv—Fe1—O6ii | 92.67 (8) | O3i—B2—O7xvi | 124.9 (2) |
O1iii—Fe1—O3iv | 86.00 (6) | O1—B3—O4 | 117.55 (13) |
O4—Fe2—O5v | 94.90 (7) | O1—B3—O4xvii | 117.6 (2) |
O4—Fe2—O7vi | 100.45 (7) | O4—B3—O4xvii | 124.9 (2) |
O4—Fe2—O5vii | 92.35 (7) | | |
Symmetry codes: (i) y, x, −z; (ii) −y, x−y, z+1/3; (iii) −x+y, −x, z−1/3; (iv) x−y, −y, −z−1/3; (v) −y, x−y−1, z+1/3; (vi) −x+y, −x−1, z+2/3; (vii) −x+y, −x, z+2/3; (viii) −x−1, −x+y−1, −z+1/3; (ix) x−y, −y−1, −z+2/3; (x) −x+y−1, −x−1, z−1/3; (xi) −x−1, −x+y, −z+1/3; (xii) x−y−1, −y−1, −z+2/3; (xiii) −y, x−y, z−2/3; (xiv) −x+y+1, −x, z−1/3; (xv) −y−1, x−y−1, z−2/3; (xvi) −y−1, x−y, z+1/3; (xvii) −x, −x+y, −z+1/3. |
Selected geometric parameters (Å, º) for (RT) topGd—O3 | 2.3571 (17) | Fe—O3 | 1.9595 (18) |
Gd—O3i | 2.357 (2) | Fe—O1vi | 2.0138 (13) |
Gd—O3ii | 2.357 (3) | Fe—O2vi | 2.031 (3) |
Gd—O3iii | 2.3571 (19) | Fe—O3vii | 1.959 (2) |
Gd—O3iv | 2.357 (2) | O1—B1 | 1.3728 (18) |
Gd—O3v | 2.3570 (18) | O2—B2 | 1.370 (4) |
Fe—O1 | 2.0142 (13) | O3—B2viii | 1.366 (4) |
Fe—O2 | 2.032 (2) | | |
| | | |
O3—Gd—O3i | 89.36 (7) | O2—Fe—O3vii | 86.81 (10) |
O3—Gd—O3ii | 89.36 (6) | O1vi—Fe—O3 | 95.59 (7) |
O3—Gd—O3iii | 122.58 (6) | O2vi—Fe—O3 | 86.83 (10) |
O3—Gd—O3iv | 72.39 (6) | O3—Fe—O3vii | 101.11 (9) |
O3—Gd—O3v | 141.88 (9) | O1vi—Fe—O2vi | 76.96 (9) |
O3i—Gd—O3ii | 89.36 (7) | O1vi—Fe—O3vii | 92.05 (8) |
O3i—Gd—O3iii | 141.88 (7) | O2vi—Fe—O3vii | 167.11 (10) |
O3i—Gd—O3iv | 122.57 (8) | Fe—O1—B1 | 128.17 (9) |
O3i—Gd—O3v | 72.39 (6) | Fe—O1—Feix | 103.65 (8) |
O3ii—Gd—O3iii | 72.39 (7) | Feix—O1—B1 | 128.17 (8) |
O3ii—Gd—O3iv | 141.87 (7) | Fe—O2—B2 | 128.80 (14) |
O3ii—Gd—O3v | 122.57 (7) | Fe—O2—Feix | 102.40 (12) |
O3iii—Gd—O3iv | 89.36 (7) | Feix—O2—B2 | 128.80 (16) |
O3iii—Gd—O3v | 89.36 (7) | Gd—O3—Fe | 120.64 (9) |
O3iv—Gd—O3v | 89.36 (7) | Gd—O3—B2viii | 107.75 (12) |
O1—Fe—O2 | 76.98 (8) | Fe—O3—B2viii | 131.47 (13) |
O1—Fe—O3 | 92.05 (7) | O1—B1—O1i | 120.00 (13) |
O1—Fe—O1vi | 167.97 (11) | O1—B1—O1ii | 120.00 (14) |
O1—Fe—O2vi | 94.23 (8) | O1i—B1—O1ii | 120.00 (15) |
O1—Fe—O3vii | 95.60 (6) | O2—B2—O3x | 117.5 (3) |
O2—Fe—O3 | 167.13 (9) | O2—B2—O3xi | 117.5 (2) |
O1vi—Fe—O2 | 94.23 (9) | O3x—B2—O3xi | 125.0 (2) |
O2—Fe—O2vi | 87.31 (11) | | |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) y, x, −z; (iv) −x, −x+y, −z; (v) x−y, −y, −z; (vi) −x+y+1/3, −x+2/3, z−1/3; (vii) x−y+1/3, −y+2/3, −z+2/3; (viii) x−2/3, y−1/3, z−1/3; (ix) y, x, −z+1; (x) y+1/3, x+2/3, −z+2/3; (xi) x+2/3, y+1/3, z+1/3. |