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A single-crystal X-ray structure study of gadolinium triiron tetraborate, GdFe_3(BO_3)_4, at room temperature and at 90 K is reported. At room temperature GdFe_3(BO_3)_4 crystallizes in a trigonal space group, R32 (No. 155), the same as found for other members of the iron borate family RFe_3(BO_3)_4. At 90 K the structure of GdFe_3(BO_3)_4 transforms to the space group P3_{1}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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768105017362/lc5026sup1.cif
Contains datablocks global, LT, RT

txt

Text file https://doi.org/10.1107/S0108768105017362/lc5026sup2.txt
Supplementary material

txt

Text file https://doi.org/10.1107/S0108768105017362/lc5026sup3.txt
Supplementary material

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Chemical structural diagram (scheme 1) of the title compound
[Figure 2] Fig. 2. Perspective PLUTO drawing of the molecule illustrating the configuration and the adopted numbering scheme.
[Figure 3] Fig. 3. Molecular packing viewed down unit cell axes.
[Figure 4] Fig. 4. Perspective ORTEP drawing of the title compound. Displacement ellipsoids for non-H are represented at the 50% probability level.
(LT) top
Crystal data top
B4Fe3GdO12The final unit cell was obtained from the xyz centroids of 5439 reflections after integration using the SAINT software package (Bruker, 2000).
Mr = 560.04Dx = 4.699 Mg m3
Trigonal, P3121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 31 2"Cell parameters from 5439 reflections
a = 9.5305 (3) Åθ = 3.7–38.6°
c = 7.5479 (2) ŵ = 13.74 mm1
V = 593.73 (3) Å3T = 90 K
Z = 3Broken_block, light_green
F(000) = 7740.22 × 0.15 × 0.11 mm
Data collection top
Bruker Smart Apex
diffractometer
2217 independent reflections
Radiation source: fine focus sealed Siemens Mo tube1956 reflections with I > 2σ(I)
Parallel mounted graphite monochromatorRint = 0.034
Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm-1θmax = 38.6°, θmin = 2.5°
phi and ω scansh = 1616
Absorption correction: analytical
Bruker, 2000
k = 1616
Tmin = 0.062, Tmax = 0.251l = 1313
13868 measured reflections
Refinement top
Refinement on F2Secondary 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) = 0.045Δρmax = 0.82 e Å3
S = 0.86Δρmin = 0.51 e Å3
2217 reflectionsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
95 parametersExtinction coefficient: 0.0359 (10)
0 restraintsAbsolute 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 methodAbsolute structure parameter: 0.5
Crystal data top
B4Fe3GdO12Z = 3
Mr = 560.04Mo Kα radiation
Trigonal, P3121µ = 13.74 mm1
a = 9.5305 (3) ÅT = 90 K
c = 7.5479 (2) Å0.22 × 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 = 0.251Rint = 0.034
13868 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0170 restraints
wR(F2) = 0.045Δρmax = 0.82 e Å3
S = 0.86Δρmin = 0.51 e Å3
2217 reflectionsAbsolute structure: Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5 Flack, H.D. & Bernardinelli, G. (1999, 2000)
95 parametersAbsolute 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
xyzUiso*/Ueq
Gd10.33342 (1)0.33342 (1)0.000000.0041 (1)
Fe10.11536 (5)0.11536 (5)0.000000.0036 (1)
Fe20.21410 (6)0.54975 (4)0.34154 (2)0.0037 (1)
O10.000000.07819 (15)0.166670.0072 (3)
O20.5832 (2)0.27090 (13)0.13774 (12)0.0069 (2)
O30.1194 (3)0.30445 (16)0.17980 (18)0.0057 (3)
O40.1467 (3)0.36234 (16)0.18479 (18)0.0058 (2)
O50.4755 (2)0.1451 (2)0.15980 (8)0.0057 (3)
O60.1877 (2)0.000000.166670.0053 (3)
O70.5235 (3)0.53811 (17)0.18533 (18)0.0056 (2)
B10.33204 (14)0.000000.166670.0045 (5)
B20.4473 (4)0.1201 (3)0.15617 (14)0.0053 (3)
B30.000000.2223 (3)0.166670.0049 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Gd10.0041 (1)0.0041 (1)0.0041 (1)0.0021 (1)0.0001 (1)0.0001 (1)
Fe10.0036 (1)0.0036 (1)0.0036 (1)0.0017 (1)0.0001 (1)0.0001 (1)
Fe20.0035 (1)0.0036 (1)0.0038 (1)0.0017 (1)0.0000 (1)0.0001 (1)
O10.0081 (6)0.0054 (4)0.0089 (4)0.0040 (3)0.0024 (4)0.0012 (2)
O20.0058 (3)0.0062 (3)0.0081 (3)0.0025 (3)0.0014 (3)0.0012 (3)
O30.0062 (4)0.0040 (5)0.0065 (4)0.0023 (4)0.0007 (3)0.0006 (3)
O40.0054 (4)0.0045 (4)0.0067 (4)0.0019 (4)0.0003 (3)0.0007 (3)
O50.0051 (4)0.0050 (4)0.0063 (5)0.0019 (5)0.0003 (3)0.0007 (3)
O60.0044 (4)0.0058 (6)0.0062 (5)0.0029 (3)0.0010 (2)0.0019 (5)
O70.0047 (4)0.0063 (4)0.0064 (4)0.0033 (4)0.0001 (3)0.0008 (3)
B10.0042 (8)0.0048 (9)0.0046 (11)0.0024 (4)0.0004 (2)0.0009 (5)
B20.0050 (6)0.0067 (7)0.0055 (5)0.0040 (4)0.0001 (4)0.0004 (5)
B30.0018 (8)0.0061 (6)0.0055 (7)0.0009 (4)0.0008 (6)0.0004 (3)
Geometric parameters (Å, º) top
Gd1—O32.3485 (18)Fe2—O41.9635 (14)
Gd1—O42.3830 (18)Fe2—O5v2.025 (2)
Gd1—O72.3474 (15)Fe2—O7vi1.971 (3)
Gd1—B22.985 (3)Fe2—O5vii2.017 (2)
Gd1—O3i2.3485 (16)Fe2—O2viii2.0332 (16)
Gd1—O4i2.3830 (16)Fe2—O2ix2.0490 (10)
Gd1—O7i2.3474 (16)O1—B31.373 (3)
Gd1—B2i2.985 (3)O2—B21.379 (3)
Fe1—O12.0411 (10)O3—B2i1.370 (3)
Fe1—O62.0061 (12)O4—B31.374 (3)
Fe1—O3ii1.958 (2)O5—B11.3761 (19)
Fe1—O6ii2.0061 (9)O6—B11.376 (2)
Fe1—O1iii2.0411 (10)O7—B2x1.360 (5)
Fe1—O3iv1.9583 (14)
O3—Gd1—O472.36 (6)O2viii—Fe2—O491.99 (6)
O3—Gd1—O790.99 (6)O2ix—Fe2—O4168.53 (8)
O3—Gd1—B2137.60 (6)O5v—Fe2—O7vi90.43 (9)
O3—Gd1—O3i120.92 (5)O5v—Fe2—O5vii167.41 (9)
O3—Gd1—O4i89.54 (6)O2viii—Fe2—O5v76.55 (8)
O3—Gd1—O7i140.62 (6)O2ix—Fe2—O5v95.92 (7)
O3—Gd1—B2i26.49 (5)O5vii—Fe2—O7vi98.38 (9)
O4—Gd1—O7124.29 (5)O2viii—Fe2—O7vi162.76 (8)
O4—Gd1—B2113.24 (5)O2ix—Fe2—O7vi83.30 (7)
O3i—Gd1—O489.54 (5)O2viii—Fe2—O5vii92.94 (8)
O4—Gd1—O4i143.21 (5)O2ix—Fe2—O5vii76.33 (6)
O4—Gd1—O7i86.70 (6)O2viii—Fe2—O2ix86.82 (6)
O4—Gd1—B2i60.35 (5)Fe1—O1—B3129.38 (5)
O7—Gd1—B2114.15 (7)Fe1—O1—Fe1ii101.24 (5)
O3i—Gd1—O7140.62 (7)Fe1ii—O1—B3129.38 (7)
O4i—Gd1—O786.70 (5)Fe2xi—O2—B2128.74 (13)
O7—Gd1—O7i73.47 (5)Fe2xii—O2—B2124.47 (10)
O7—Gd1—B2i81.11 (7)Fe2xi—O2—Fe2xii102.46 (6)
O3i—Gd1—B226.49 (7)Gd1—O3—Fe1iii121.40 (8)
O4i—Gd1—B260.35 (5)Gd1—O3—B2i103.63 (13)
O7i—Gd1—B281.11 (6)Fe1iii—O3—B2i134.71 (15)
B2—Gd1—B2i161.73 (7)Gd1—O4—Fe2122.30 (8)
O3i—Gd1—O4i72.36 (5)Gd1—O4—B3106.58 (10)
O3i—Gd1—O7i90.99 (5)Fe2—O4—B3130.89 (13)
O3i—Gd1—B2i137.60 (6)Fe2xiii—O5—B1127.32 (10)
O4i—Gd1—O7i124.29 (6)Fe2xiv—O5—B1128.71 (9)
O4i—Gd1—B2i113.24 (5)Fe2xiii—O5—Fe2xiv103.91 (8)
O7i—Gd1—B2i114.15 (6)Fe1—O6—B1128.15 (4)
O1—Fe1—O693.94 (3)Fe1—O6—Fe1iii103.71 (9)
O1—Fe1—O3ii86.00 (7)Fe1iii—O6—B1128.15 (5)
O1—Fe1—O6ii77.53 (5)Gd1—O7—Fe2xv117.67 (9)
O1—Fe1—O1iii87.69 (3)Gd1—O7—B2x113.03 (12)
O1—Fe1—O3iv167.95 (9)Fe2xv—O7—B2x129.29 (13)
O3ii—Fe1—O692.67 (7)O5—B1—O6119.41 (10)
O6—Fe1—O6ii168.27 (6)O5—B1—O5iv121.21 (17)
O1iii—Fe1—O677.53 (5)O5iv—B1—O6119.38 (12)
O3iv—Fe1—O694.71 (6)Gd1—B2—O273.87 (12)
O3ii—Fe1—O6ii94.71 (6)Gd1—B2—O7xvi150.31 (12)
O1iii—Fe1—O3ii167.95 (8)Gd1—B2—O3i49.88 (10)
O3ii—Fe1—O3iv101.96 (10)O2—B2—O7xvi119.6 (3)
O1iii—Fe1—O6ii93.94 (5)O2—B2—O3i115.6 (2)
O3iv—Fe1—O6ii92.67 (8)O3i—B2—O7xvi124.9 (2)
O1iii—Fe1—O3iv86.00 (6)O1—B3—O4117.55 (13)
O4—Fe2—O5v94.90 (7)O1—B3—O4xvii117.6 (2)
O4—Fe2—O7vi100.45 (7)O4—B3—O4xvii124.9 (2)
O4—Fe2—O5vii92.35 (7)
O4—Gd1—O3—Fe1iii126.76 (9)O3i—Gd1—B2—O2146.23 (14)
O4—Gd1—O3—B2i58.28 (12)O4i—Gd1—B2—O2102.65 (10)
O7—Gd1—O3—Fe1iii107.39 (9)O7i—Gd1—B2—O235.53 (8)
O7—Gd1—O3—B2i67.57 (12)O3—Gd1—O3i—B2136.72 (11)
B2—Gd1—O3—Fe1iii21.35 (13)O4—Gd1—O3i—B2154.27 (11)
B2—Gd1—O3—B2i163.69 (11)O7—Gd1—O3i—B22.87 (15)
O3—Gd1—O4—Fe2127.20 (9)O4—Gd1—B2i—O3111.13 (14)
O3—Gd1—O4—B357.76 (10)O7—Gd1—B2i—O3110.69 (12)
O7—Gd1—O4—Fe248.43 (11)O6—Fe1—O1—B38.13 (11)
O7—Gd1—O4—B3136.53 (9)O1—Fe1—O6—B193.24 (3)
B2—Gd1—O4—Fe297.83 (9)O5v—Fe2—O4—Gd198.55 (10)
B2—Gd1—O4—B377.21 (11)O5v—Fe2—O4—B387.73 (16)
O3i—Gd1—O4—Fe2110.00 (9)O7vi—Fe2—O4—Gd1170.11 (9)
O3i—Gd1—O4—B365.04 (10)O7vi—Fe2—O4—B33.61 (17)
O4i—Gd1—O4—Fe2168.87 (7)O5vii—Fe2—O4—Gd171.13 (10)
O4i—Gd1—O4—B36.17 (15)O5vii—Fe2—O4—B3102.58 (16)
O7i—Gd1—O4—Fe218.98 (8)O2viii—Fe2—O4—Gd121.89 (9)
O7i—Gd1—O4—B3156.07 (10)O2viii—Fe2—O4—B3164.40 (15)
B2i—Gd1—O4—Fe2101.31 (10)O4—Fe2—O7vi—B2ii10.8 (2)
B2i—Gd1—O4—B383.65 (11)O4—Fe2—O2viii—B2viii69.01 (16)
O3—Gd1—O7—Fe2xv25.80 (7)Fe1—O1—B3—O4133.57 (9)
O3—Gd1—O7—B2x155.03 (12)Fe2xi—O2—B2—Gd1119.34 (12)
O4—Gd1—O7—Fe2xv43.40 (9)Fe2xi—O2—B2—O7xvi31.78 (19)
O4—Gd1—O7—B2x135.77 (12)Fe2xi—O2—B2—O3i147.46 (11)
B2—Gd1—O7—Fe2xv170.60 (6)Fe2xii—O2—B2—Gd188.25 (12)
B2—Gd1—O7—B2x10.22 (13)Fe2xii—O2—B2—O7xvi120.64 (14)
O3—Gd1—B2—O2153.06 (8)Fe2xii—O2—B2—O3i60.13 (18)
O3—Gd1—B2—O7xvi31.1 (4)Gd1—O4—B3—O143.05 (8)
O3—Gd1—B2—O3i60.72 (13)Gd1—O4—B3—O4xvii136.96 (9)
O4—Gd1—B2—O2118.03 (8)Fe2—O4—B3—O1131.41 (12)
O4—Gd1—B2—O7xvi120.0 (3)Fe2—O4—B3—O4xvii48.59 (17)
O4—Gd1—B2—O3i28.20 (13)Fe2xiii—O5—B1—O655.03 (12)
O7—Gd1—B2—O231.78 (9)Fe2xiv—O5—B1—O6128.13 (12)
O7—Gd1—B2—O7xvi90.2 (4)Fe1—O6—B1—O550.40 (3)
O7—Gd1—B2—O3i178.01 (10)
Symmetry codes: (i) y, x, z; (ii) y, xy, z+1/3; (iii) x+y, x, z1/3; (iv) xy, y, z1/3; (v) y, xy1, z+1/3; (vi) x+y, x1, z+2/3; (vii) x+y, x, z+2/3; (viii) x1, x+y1, z+1/3; (ix) xy, y1, z+2/3; (x) x+y1, x1, z1/3; (xi) x1, x+y, z+1/3; (xii) xy1, y1, z+2/3; (xiii) y, xy, z2/3; (xiv) x+y+1, x, z1/3; (xv) y1, xy1, z2/3; (xvi) y1, xy, z+1/3; (xvii) x, x+y, z+1/3.
(RT) top
Crystal data top
B4Fe3GdO12The final unit cell was obtained from the xyz centroids of 4767 reflections after integration using the SAINT software package (Bruker, 2000).
Mr = 560.04Dx = 4.712 Mg m3
Trigonal, R32Mo Kα radiation, λ = 0.71073 Å
Hall symbol: R 3 2"Cell parameters from 4767 reflections
a = 9.5203 (6) Åθ = 3.7–38.7°
c = 7.5439 (5) ŵ = 13.77 mm1
V = 592.15 (7) Å3T = 297 K
Z = 3Broken_block, light_green
F(000) = 7740.22 × 0.15 × 0.11 mm
Data collection top
Bruker Smart Apex
diffractometer
755 independent reflections
Radiation source: fine focus sealed Siemens Mo tube755 reflections with I > 2σ(I)
Parallel mounted graphite monochromatorRint = 0.034
Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm-1θmax = 38.7°, θmin = 3.7°
phi and ω scansh = 1616
Absorption correction: analytical
Bruker, 2000)
k = 1616
Tmin = 0.056, Tmax = 0.252l = 1313
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)] = 0.015Δρmax = 0.62 e Å3
wR(F2) = 0.037Δρmin = 0.97 e Å3
S = 1.08Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
755 reflectionsExtinction coefficient: 0.0371 (12)
35 parametersAbsolute structure: Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5 Flack, H.D. & Bernardinelli, G. (1999, 2000)
0 restraintsAbsolute structure parameter: 0.50
Primary atom site location: from Campá et al.
Crystal data top
B4Fe3GdO12Z = 3
Mr = 560.04Mo Kα radiation
Trigonal, R32µ = 13.77 mm1
a = 9.5203 (6) ÅT = 297 K
c = 7.5439 (5) Å0.22 × 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 = 0.252Rint = 0.034
4700 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0150 restraints
wR(F2) = 0.037Δρmax = 0.62 e Å3
S = 1.08Δρmin = 0.97 e Å3
755 reflectionsAbsolute structure: Enantiomorph twin refinement resulted in 0.50(1) so ultimately set to 0.5 Flack, H.D. & Bernardinelli, G. (1999, 2000)
35 parametersAbsolute 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
xyzUiso*/Ueq
Gd0.000000.000000.000000.0087 (1)
Fe0.21659 (5)0.333330.333330.0065 (1)
O10.1442 (2)0.1442 (2)0.500000.0083 (3)
O20.4087 (3)0.4087 (3)0.500000.0132 (5)
O30.02538 (19)0.2125 (2)0.1824 (2)0.0095 (3)
B10.000000.000000.500000.0066 (6)
B20.5526 (3)0.5526 (3)0.500000.0077 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Gd0.0089 (1)0.0089 (1)0.0083 (1)0.0044 (1)0.00000.0000
Fe0.0059 (1)0.0064 (1)0.0075 (2)0.0032 (1)0.0000 (1)0.0001 (1)
O10.0058 (5)0.0058 (5)0.0109 (7)0.0011 (6)0.0014 (3)0.0014 (3)
O20.0076 (6)0.0076 (6)0.0182 (11)0.0009 (8)0.0047 (5)0.0047 (5)
O30.0065 (5)0.0112 (5)0.0111 (5)0.0046 (4)0.0021 (4)0.0025 (5)
B10.0058 (9)0.0058 (9)0.0081 (14)0.0029 (4)0.00000.0000
B20.0070 (7)0.0070 (7)0.0093 (8)0.0036 (11)0.0007 (4)0.0007 (4)
Geometric parameters (Å, º) top
Gd—O32.3571 (17)Fe—O31.9595 (18)
Gd—O3i2.357 (2)Fe—O1vi2.0138 (13)
Gd—O3ii2.357 (3)Fe—O2vi2.031 (3)
Gd—O3iii2.3571 (19)Fe—O3vii1.959 (2)
Gd—O3iv2.357 (2)O1—B11.3728 (18)
Gd—O3v2.3570 (18)O2—B21.370 (4)
Fe—O12.0142 (13)O3—B2viii1.366 (4)
Fe—O22.032 (2)
O3—Gd—O3i89.36 (7)O2—Fe—O3vii86.81 (10)
O3—Gd—O3ii89.36 (6)O1vi—Fe—O395.59 (7)
O3—Gd—O3iii122.58 (6)O2vi—Fe—O386.83 (10)
O3—Gd—O3iv72.39 (6)O3—Fe—O3vii101.11 (9)
O3—Gd—O3v141.88 (9)O1vi—Fe—O2vi76.96 (9)
O3i—Gd—O3ii89.36 (7)O1vi—Fe—O3vii92.05 (8)
O3i—Gd—O3iii141.88 (7)O2vi—Fe—O3vii167.11 (10)
O3i—Gd—O3iv122.57 (8)Fe—O1—B1128.17 (9)
O3i—Gd—O3v72.39 (6)Fe—O1—Feix103.65 (8)
O3ii—Gd—O3iii72.39 (7)Feix—O1—B1128.17 (8)
O3ii—Gd—O3iv141.87 (7)Fe—O2—B2128.80 (14)
O3ii—Gd—O3v122.57 (7)Fe—O2—Feix102.40 (12)
O3iii—Gd—O3iv89.36 (7)Feix—O2—B2128.80 (16)
O3iii—Gd—O3v89.36 (7)Gd—O3—Fe120.64 (9)
O3iv—Gd—O3v89.36 (7)Gd—O3—B2viii107.75 (12)
O1—Fe—O276.98 (8)Fe—O3—B2viii131.47 (13)
O1—Fe—O392.05 (7)O1—B1—O1i120.00 (13)
O1—Fe—O1vi167.97 (11)O1—B1—O1ii120.00 (14)
O1—Fe—O2vi94.23 (8)O1i—B1—O1ii120.00 (15)
O1—Fe—O3vii95.60 (6)O2—B2—O3x117.5 (3)
O2—Fe—O3167.13 (9)O2—B2—O3xi117.5 (2)
O1vi—Fe—O294.23 (9)O3x—B2—O3xi125.0 (2)
O2—Fe—O2vi87.31 (11)
O3i—Gd—O3—Fe110.73 (9)O2—Fe—O1—B1179.98 (15)
O3ii—Gd—O3—Fe21.37 (9)O3—Fe—O1—B16.79 (14)
O3iii—Gd—O3—Fe47.15 (11)O1—Fe—O2—B2180.0 (3)
O3iv—Gd—O3—Fe124.62 (10)O1—Fe—O3—Gd72.16 (9)
O3v—Gd—O3—Fe170.44 (7)O3vii—Fe—O3—Gd168.27 (8)
Symmetry codes: (i) y, xy, z; (ii) x+y, x, z; (iii) y, x, z; (iv) x, x+y, z; (v) xy, y, z; (vi) x+y+1/3, x+2/3, z1/3; (vii) xy+1/3, y+2/3, z+2/3; (viii) x2/3, y1/3, z1/3; (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 formulaB4Fe3GdO12B4Fe3GdO12
Mr560.04560.04
Crystal system, space groupTrigonal, P3121Trigonal, R32
Temperature (K)90297
a, c (Å)9.5305 (3), 7.5479 (2)9.5203 (6), 7.5439 (5)
V3)593.73 (3)592.15 (7)
Z33
Radiation typeMo KαMo Kα
µ (mm1)13.7413.77
Crystal size (mm)0.22 × 0.15 × 0.110.22 × 0.15 × 0.11
Data collection
DiffractometerBruker Smart Apex
diffractometer
Bruker Smart Apex
diffractometer
Absorption correctionAnalytical
Bruker, 2000
Analytical
Bruker, 2000)
Tmin, Tmax0.062, 0.2510.056, 0.252
No. of measured, independent and
observed [I > 2σ(I)] reflections
13868, 2217, 1956 4700, 755, 755
Rint0.0340.034
(sin θ/λ)max1)0.8770.880
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.017, 0.045, 0.86 0.015, 0.037, 1.08
No. of reflections2217755
No. of parameters9535
Δρmax, Δρmin (e Å3)0.82, 0.510.62, 0.97
Absolute structureEnantiomorph 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 parameter0.50.50

Computer programs: SMART, Bruker Version 5.624, 2001, SAINT, Bruker Version 6.02A, 2000, XPREP, Bruker Version 5.1/NT, 2000, SIR97 (Altomare et al., 1997), Coordinates from Campá et al., SHELXL97 (Sheldrick, 1997), PLUTO (Meetsma, 2003) ORTEP (Farrugia, 1997; Johnson et al., 2000) PLATON (Spek, 1994), PLATON (Spek, 1990).

Selected geometric parameters (Å, º) for (LT) top
Gd1—O32.3485 (18)Fe2—O41.9635 (14)
Gd1—O42.3830 (18)Fe2—O5v2.025 (2)
Gd1—O72.3474 (15)Fe2—O7vi1.971 (3)
Gd1—B22.985 (3)Fe2—O5vii2.017 (2)
Gd1—O3i2.3485 (16)Fe2—O2viii2.0332 (16)
Gd1—O4i2.3830 (16)Fe2—O2ix2.0490 (10)
Gd1—O7i2.3474 (16)O1—B31.373 (3)
Gd1—B2i2.985 (3)O2—B21.379 (3)
Fe1—O12.0411 (10)O3—B2i1.370 (3)
Fe1—O62.0061 (12)O4—B31.374 (3)
Fe1—O3ii1.958 (2)O5—B11.3761 (19)
Fe1—O6ii2.0061 (9)O6—B11.376 (2)
Fe1—O1iii2.0411 (10)O7—B2x1.360 (5)
Fe1—O3iv1.9583 (14)
O3—Gd1—O472.36 (6)O2viii—Fe2—O491.99 (6)
O3—Gd1—O790.99 (6)O2ix—Fe2—O4168.53 (8)
O3—Gd1—B2137.60 (6)O5v—Fe2—O7vi90.43 (9)
O3—Gd1—O3i120.92 (5)O5v—Fe2—O5vii167.41 (9)
O3—Gd1—O4i89.54 (6)O2viii—Fe2—O5v76.55 (8)
O3—Gd1—O7i140.62 (6)O2ix—Fe2—O5v95.92 (7)
O3—Gd1—B2i26.49 (5)O5vii—Fe2—O7vi98.38 (9)
O4—Gd1—O7124.29 (5)O2viii—Fe2—O7vi162.76 (8)
O4—Gd1—B2113.24 (5)O2ix—Fe2—O7vi83.30 (7)
O3i—Gd1—O489.54 (5)O2viii—Fe2—O5vii92.94 (8)
O4—Gd1—O4i143.21 (5)O2ix—Fe2—O5vii76.33 (6)
O4—Gd1—O7i86.70 (6)O2viii—Fe2—O2ix86.82 (6)
O4—Gd1—B2i60.35 (5)Fe1—O1—B3129.38 (5)
O7—Gd1—B2114.15 (7)Fe1—O1—Fe1ii101.24 (5)
O3i—Gd1—O7140.62 (7)Fe1ii—O1—B3129.38 (7)
O4i—Gd1—O786.70 (5)Fe2xi—O2—B2128.74 (13)
O7—Gd1—O7i73.47 (5)Fe2xii—O2—B2124.47 (10)
O7—Gd1—B2i81.11 (7)Fe2xi—O2—Fe2xii102.46 (6)
O3i—Gd1—B226.49 (7)Gd1—O3—Fe1iii121.40 (8)
O4i—Gd1—B260.35 (5)Gd1—O3—B2i103.63 (13)
O7i—Gd1—B281.11 (6)Fe1iii—O3—B2i134.71 (15)
B2—Gd1—B2i161.73 (7)Gd1—O4—Fe2122.30 (8)
O3i—Gd1—O4i72.36 (5)Gd1—O4—B3106.58 (10)
O3i—Gd1—O7i90.99 (5)Fe2—O4—B3130.89 (13)
O3i—Gd1—B2i137.60 (6)Fe2xiii—O5—B1127.32 (10)
O4i—Gd1—O7i124.29 (6)Fe2xiv—O5—B1128.71 (9)
O4i—Gd1—B2i113.24 (5)Fe2xiii—O5—Fe2xiv103.91 (8)
O7i—Gd1—B2i114.15 (6)Fe1—O6—B1128.15 (4)
O1—Fe1—O693.94 (3)Fe1—O6—Fe1iii103.71 (9)
O1—Fe1—O3ii86.00 (7)Fe1iii—O6—B1128.15 (5)
O1—Fe1—O6ii77.53 (5)Gd1—O7—Fe2xv117.67 (9)
O1—Fe1—O1iii87.69 (3)Gd1—O7—B2x113.03 (12)
O1—Fe1—O3iv167.95 (9)Fe2xv—O7—B2x129.29 (13)
O3ii—Fe1—O692.67 (7)O5—B1—O6119.41 (10)
O6—Fe1—O6ii168.27 (6)O5—B1—O5iv121.21 (17)
O1iii—Fe1—O677.53 (5)O5iv—B1—O6119.38 (12)
O3iv—Fe1—O694.71 (6)Gd1—B2—O273.87 (12)
O3ii—Fe1—O6ii94.71 (6)Gd1—B2—O7xvi150.31 (12)
O1iii—Fe1—O3ii167.95 (8)Gd1—B2—O3i49.88 (10)
O3ii—Fe1—O3iv101.96 (10)O2—B2—O7xvi119.6 (3)
O1iii—Fe1—O6ii93.94 (5)O2—B2—O3i115.6 (2)
O3iv—Fe1—O6ii92.67 (8)O3i—B2—O7xvi124.9 (2)
O1iii—Fe1—O3iv86.00 (6)O1—B3—O4117.55 (13)
O4—Fe2—O5v94.90 (7)O1—B3—O4xvii117.6 (2)
O4—Fe2—O7vi100.45 (7)O4—B3—O4xvii124.9 (2)
O4—Fe2—O5vii92.35 (7)
Symmetry codes: (i) y, x, z; (ii) y, xy, z+1/3; (iii) x+y, x, z1/3; (iv) xy, y, z1/3; (v) y, xy1, z+1/3; (vi) x+y, x1, z+2/3; (vii) x+y, x, z+2/3; (viii) x1, x+y1, z+1/3; (ix) xy, y1, z+2/3; (x) x+y1, x1, z1/3; (xi) x1, x+y, z+1/3; (xii) xy1, y1, z+2/3; (xiii) y, xy, z2/3; (xiv) x+y+1, x, z1/3; (xv) y1, xy1, z2/3; (xvi) y1, xy, z+1/3; (xvii) x, x+y, z+1/3.
Selected geometric parameters (Å, º) for (RT) top
Gd—O32.3571 (17)Fe—O31.9595 (18)
Gd—O3i2.357 (2)Fe—O1vi2.0138 (13)
Gd—O3ii2.357 (3)Fe—O2vi2.031 (3)
Gd—O3iii2.3571 (19)Fe—O3vii1.959 (2)
Gd—O3iv2.357 (2)O1—B11.3728 (18)
Gd—O3v2.3570 (18)O2—B21.370 (4)
Fe—O12.0142 (13)O3—B2viii1.366 (4)
Fe—O22.032 (2)
O3—Gd—O3i89.36 (7)O2—Fe—O3vii86.81 (10)
O3—Gd—O3ii89.36 (6)O1vi—Fe—O395.59 (7)
O3—Gd—O3iii122.58 (6)O2vi—Fe—O386.83 (10)
O3—Gd—O3iv72.39 (6)O3—Fe—O3vii101.11 (9)
O3—Gd—O3v141.88 (9)O1vi—Fe—O2vi76.96 (9)
O3i—Gd—O3ii89.36 (7)O1vi—Fe—O3vii92.05 (8)
O3i—Gd—O3iii141.88 (7)O2vi—Fe—O3vii167.11 (10)
O3i—Gd—O3iv122.57 (8)Fe—O1—B1128.17 (9)
O3i—Gd—O3v72.39 (6)Fe—O1—Feix103.65 (8)
O3ii—Gd—O3iii72.39 (7)Feix—O1—B1128.17 (8)
O3ii—Gd—O3iv141.87 (7)Fe—O2—B2128.80 (14)
O3ii—Gd—O3v122.57 (7)Fe—O2—Feix102.40 (12)
O3iii—Gd—O3iv89.36 (7)Feix—O2—B2128.80 (16)
O3iii—Gd—O3v89.36 (7)Gd—O3—Fe120.64 (9)
O3iv—Gd—O3v89.36 (7)Gd—O3—B2viii107.75 (12)
O1—Fe—O276.98 (8)Fe—O3—B2viii131.47 (13)
O1—Fe—O392.05 (7)O1—B1—O1i120.00 (13)
O1—Fe—O1vi167.97 (11)O1—B1—O1ii120.00 (14)
O1—Fe—O2vi94.23 (8)O1i—B1—O1ii120.00 (15)
O1—Fe—O3vii95.60 (6)O2—B2—O3x117.5 (3)
O2—Fe—O3167.13 (9)O2—B2—O3xi117.5 (2)
O1vi—Fe—O294.23 (9)O3x—B2—O3xi125.0 (2)
O2—Fe—O2vi87.31 (11)
Symmetry codes: (i) y, xy, z; (ii) x+y, x, z; (iii) y, x, z; (iv) x, x+y, z; (v) xy, y, z; (vi) x+y+1/3, x+2/3, z1/3; (vii) xy+1/3, y+2/3, z+2/3; (viii) x2/3, y1/3, z1/3; (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.
 

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