Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The three title complexes, namely pentasodium tris(2,2'-oxydi­acetato)­neodymium(III) bis­(tetra­fluoro­borate) hexahydrate and its samarium(III) and gadolinium(III) analogues, (I)-(III), respectively, are isomorphous and isostructural and have crystallographic D3 symmetry. The lanthanide metal ions are nine-coordinate, binding to three O atoms of three oxodi­acetate ligands. One Na+ ion is octahedrally coordinated to six O atoms and the other Na+ ion is octahedrally coordinated to four O atoms and two F atoms. The structure is effectively an infinite three-dimensional polymer, consistent with the exceptional crystal quality. The racemic solutions spontaneously resolve on crystallization. For the individual crystals selected for structural analysis, the Nd and Sm complexes have the [Lambda] configuration, while the Gd complex has the [Delta] configuration. The lanthanide-oxy­gen distances show the expected contraction of ca 0.02 Å with increasing atomic number for the lanthanide metal.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012087/qa0369sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012087/qa0369Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012087/qa0369IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012087/qa0369IIIsup4.hkl
Contains datablock III

CCDC references: 152650; 152651; 152652

Comment top

NO COMMENT

Experimental top

The three title complexes were synthesized in an identical manner. The oxide M2O3 (0.5 mmol) (M = Nd, Sm or Gd) was stirred in an aqueous solution of diglycollic acid (3.0 mmol in 30 ml water) and sodium bicarbonate (3.0 mmol). After an hour, NaBF4 (2.0 mmol) was added, and the solution allowed to evaporate in air, yielding large well formed crystals of the complexes. Small samples for the crystallographic analyses were cleaved from larger crystals.

Refinement top

The methylene H atoms were placed in calculated positions (C—H = 0.96 Å) and refined with a riding model. The initial positions of the H atoms of the water molecules were determined from a difference Fourier map and the H atoms were then refined with a riding model and a common isotropic displacement parameter. All calculations were carried out using the WinGX package (Farrugia, 1999).

Computing details top

For all compounds, data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I) top
Crystal data top
Na5[Nd(C4H4O5)3](BF4)2·6H2ODx = 2.012 Mg m3
Mr = 937.12Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32Cell parameters from 25 reflections
Hall symbol: R 3 2"θ = 18.5–21.2°
a = 9.7508 (7) ŵ = 1.88 mm1
c = 28.177 (2) ÅT = 291 K
V = 2320.1 (3) Å3Cleaved from large crystal, pale violet
Z = 30.55 × 0.45 × 0.1 mm
F(000) = 1383
Data collection top
Enraf Nonius CAD-4
diffractometer
1001 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590Rint = 0.030
Graphite monochromatorθmax = 30.0°, θmin = 2.5°
non–profiled ω scansh = 113
Absorption correction: ψ scan
(North et al., 1968)
k = 111
Tmin = 0.425, Tmax = 0.834l = 339
1134 measured reflections3 standard reflections every 120 min
1001 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.055 w = 1/[σ2(Fo2) + (0.0427P)2 + 0.7263P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max = 0.001
1001 reflectionsΔρmax = 0.47 e Å3
77 parametersΔρmin = 0.51 e Å3
0 restraintsAbsolute structure: Flack (1983), 121 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.010 (18)
Crystal data top
Na5[Nd(C4H4O5)3](BF4)2·6H2OZ = 3
Mr = 937.12Mo Kα radiation
Trigonal, R32µ = 1.88 mm1
a = 9.7508 (7) ÅT = 291 K
c = 28.177 (2) Å0.55 × 0.45 × 0.1 mm
V = 2320.1 (3) Å3
Data collection top
Enraf Nonius CAD-4
diffractometer
1001 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.030
Tmin = 0.425, Tmax = 0.8343 standard reflections every 120 min
1134 measured reflections intensity decay: none
1001 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.055Δρmax = 0.47 e Å3
S = 1.13Δρmin = 0.51 e Å3
1001 reflectionsAbsolute structure: Flack (1983), 121 Friedel pairs
77 parametersAbsolute structure parameter: 0.010 (18)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Nd10000.02133 (9)
O10.2598 (3)0.2598 (3)00.0327 (7)
O20.1957 (3)0.0335 (3)0.05928 (8)0.0350 (5)
O30.4177 (3)0.1676 (4)0.10017 (9)0.0496 (7)
C10.3851 (4)0.2912 (4)0.03223 (12)0.0380 (6)
H1A0.41420.38740.04990.046*
H1B0.47730.30620.01480.046*
C20.3305 (3)0.1520 (9)0.06642 (9)0.0309 (10)
B10.33330.33330.2366 (2)0.0459 (11)
F10.33330.33330.28508 (15)0.0914 (17)
F20.2506 (9)0.2633 (9)0.21964 (11)0.0779 (9)
Na10.66670.33330.13419 (7)0.0344 (3)
Na20.33330.0479 (3)0.16670.0596 (6)
O40.5888 (3)0.1118 (4)0.19083 (9)0.0489 (8)
H410.56630.13280.22030.21 (4)*
H420.70310.14640.19130.21 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Nd10.02158 (10)0.02158 (10)0.02081 (12)0.01079 (5)00
O10.0262 (10)0.0262 (10)0.0382 (14)0.0073 (11)0.0034 (6)0.0034 (6)
O20.0301 (10)0.0357 (12)0.0360 (10)0.0140 (9)0.0084 (8)0.0017 (8)
O30.0419 (13)0.0515 (16)0.0494 (12)0.0189 (11)0.0205 (11)0.0010 (11)
C10.0264 (13)0.0367 (16)0.0423 (15)0.0094 (12)0.0074 (12)0.0002 (13)
C20.0285 (11)0.031 (3)0.0353 (10)0.0169 (14)0.0073 (9)0.0050 (13)
B10.0472 (18)0.0472 (18)0.043 (2)0.0236 (9)00
F10.115 (3)0.115 (3)0.0435 (18)0.0577 (14)00
F20.065 (2)0.100 (4)0.0878 (17)0.0559 (18)0.012 (3)0.000 (3)
Na10.0327 (5)0.0327 (5)0.0377 (8)0.0164 (3)00
Na20.0418 (13)0.0579 (12)0.0737 (16)0.0209 (7)0.0014 (12)0.0007 (6)
O40.0508 (19)0.0616 (17)0.0414 (10)0.0335 (13)0.0063 (10)0.0081 (12)
Geometric parameters (Å, º) top
Nd1—O2i2.432 (2)B1—F21.377 (3)
Nd1—O22.432 (2)B1—F2vi1.377 (3)
Nd1—O2ii2.432 (2)B1—F2vii1.377 (3)
Nd1—O2iii2.432 (2)F2—Na22.365 (6)
Nd1—O2iv2.432 (2)Na1—O3viii2.345 (3)
Nd1—O2v2.432 (2)Na1—O3ix2.345 (3)
Nd1—O12.533 (3)Na1—O4viii2.480 (3)
Nd1—O1ii2.533 (3)Na1—O42.480 (3)
Nd1—O1iv2.533 (3)Na1—O4ix2.480 (3)
O1—C11.427 (3)Na1—Na2viii3.6247 (18)
O1—C1v1.427 (3)Na1—Na23.6247 (18)
O2—C21.259 (4)Na1—Na2ix3.6247 (18)
O3—C21.233 (4)Na2—O42.284 (3)
O3—Na12.345 (3)Na2—O4x2.284 (3)
O3—Na22.622 (3)Na2—F2x2.365 (6)
C1—C21.527 (7)Na2—O3x2.622 (3)
B1—F11.367 (7)Na2—Na1xi3.6247 (18)
O2i—Nd1—O2150.09 (12)O3viii—Na1—O485.72 (10)
O2i—Nd1—O2ii125.30 (11)O3—Na1—O484.40 (10)
O2—Nd1—O2ii78.02 (9)O3ix—Na1—O4164.04 (12)
O2i—Nd1—O2iii78.02 (9)O4viii—Na1—O483.03 (11)
O2—Nd1—O2iii88.31 (12)O3viii—Na1—O4ix164.04 (12)
O2ii—Nd1—O2iii150.09 (12)O3—Na1—O4ix85.72 (10)
O2i—Nd1—O2iv88.31 (12)O3ix—Na1—O4ix84.40 (10)
O2—Nd1—O2iv78.02 (9)O4viii—Na1—O4ix83.03 (11)
O2ii—Nd1—O2iv78.02 (9)O4—Na1—O4ix83.03 (11)
O2iii—Nd1—O2iv125.30 (11)O3viii—Na1—Na2viii46.22 (7)
O2i—Nd1—O2v78.02 (9)O3—Na1—Na2viii146.46 (8)
O2—Nd1—O2v125.30 (11)O3ix—Na1—Na2viii99.67 (9)
O2ii—Nd1—O2v88.31 (12)O4viii—Na1—Na2viii38.49 (7)
O2iii—Nd1—O2v78.02 (9)O4—Na1—Na2viii78.30 (8)
O2iv—Nd1—O2v150.09 (12)O4ix—Na1—Na2viii119.87 (8)
O2i—Nd1—O1135.85 (6)O3viii—Na1—Na299.67 (9)
O2—Nd1—O162.65 (6)O3—Na1—Na246.22 (7)
O2ii—Nd1—O175.05 (6)O3ix—Na1—Na2146.46 (8)
O2iii—Nd1—O175.05 (6)O4viii—Na1—Na2119.87 (8)
O2iv—Nd1—O1135.85 (6)O4—Na1—Na238.49 (7)
O2v—Nd1—O162.65 (6)O4ix—Na1—Na278.30 (8)
O2i—Nd1—O1ii62.65 (6)Na2viii—Na1—Na2113.85 (2)
O2—Nd1—O1ii135.85 (6)O3viii—Na1—Na2ix146.46 (9)
O2ii—Nd1—O1ii62.65 (6)O3—Na1—Na2ix99.67 (9)
O2iii—Nd1—O1ii135.85 (6)O3ix—Na1—Na2ix46.22 (7)
O2iv—Nd1—O1ii75.05 (6)O4viii—Na1—Na2ix78.30 (8)
O2v—Nd1—O1ii75.05 (6)O4—Na1—Na2ix119.87 (8)
O1—Nd1—O1ii120O4ix—Na1—Na2ix38.49 (7)
O2i—Nd1—O1iv75.05 (6)Na2viii—Na1—Na2ix113.85 (2)
O2—Nd1—O1iv75.05 (6)Na2—Na1—Na2ix113.85 (2)
O2ii—Nd1—O1iv135.85 (6)O4—Na2—O4x164.3 (2)
O2iii—Nd1—O1iv62.65 (6)O4—Na2—F2x90.39 (18)
O2iv—Nd1—O1iv62.65 (6)O4x—Na2—F2x100.90 (19)
O2v—Nd1—O1iv135.85 (6)O4—Na2—F2100.89 (19)
O1—Nd1—O1iv120O4x—Na2—F290.39 (18)
O1ii—Nd1—O1iv120F2x—Na2—F288.35 (18)
C1—O1—C1v115.3 (4)O4—Na2—O382.43 (11)
C1—O1—Nd1122.36 (18)O4x—Na2—O387.46 (10)
C1v—O1—Nd1122.36 (18)F2x—Na2—O386.05 (10)
C2—O2—Nd1128.5 (3)F2—Na2—O3173.51 (16)
C2—O3—Na1144.3 (3)O4—Na2—O3x87.46 (10)
C2—O3—Na2122.1 (3)O4x—Na2—O3x82.43 (11)
Na1—O3—Na293.56 (9)F2x—Na2—O3x173.51 (16)
O1—C1—C2109.3 (2)F2—Na2—O3x86.05 (10)
O3—C2—O2125.1 (5)O3—Na2—O3x99.73 (17)
O3—C2—C1117.7 (4)O4—Na2—Na142.51 (8)
O2—C2—C1117.1 (3)O4x—Na2—Na1125.42 (11)
F1—B1—F2110.3 (3)F2x—Na2—Na191.44 (10)
F1—B1—F2vi110.3 (3)F2—Na2—Na1143.40 (16)
F2—B1—F2vi108.7 (3)O3—Na2—Na140.22 (6)
F1—B1—F2vii110.3 (3)O3x—Na2—Na191.11 (10)
F2—B1—F2vii108.7 (3)O4—Na2—Na1xi125.42 (11)
F2vi—B1—F2vii108.7 (3)O4x—Na2—Na1xi42.51 (8)
B1—F2—Na2129.4 (4)F2x—Na2—Na1xi143.40 (16)
O3viii—Na1—O3104.44 (10)F2—Na2—Na1xi91.44 (10)
O3viii—Na1—O3ix104.44 (10)O3—Na2—Na1xi91.11 (10)
O3—Na1—O3ix104.44 (10)O3x—Na2—Na1xi40.22 (6)
O3viii—Na1—O4viii84.40 (10)Na1—Na2—Na1xi109.49 (8)
O3—Na1—O4viii164.04 (12)Na2—O4—Na199.00 (11)
O3ix—Na1—O4viii85.72 (10)
Symmetry codes: (i) x, x+y, z; (ii) y, xy, z; (iii) xy, y, z; (iv) x+y, x, z; (v) y, x, z; (vi) y, xy1, z; (vii) x+y+1, x, z; (viii) y+1, xy, z; (ix) x+y+1, x+1, z; (x) x+2/3, x+y+1/3, z+1/3; (xi) y1/3, x2/3, z+1/3.
(II) top
Crystal data top
Na5[Sm(C4H4O5)3](BF4)2·6H2ODx = 2.045 Mg m3
Mr = 943.23Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32Cell parameters from 25 reflections
Hall symbol: R 3 2"θ = 20.9–22.3°
a = 9.7223 (11) ŵ = 2.12 mm1
c = 28.0728 (14) ÅT = 291 K
V = 2298.0 (4) Å3Irregular block cleaved from larger crystal, colourless
Z = 30.6 × 0.4 × 0.4 mm
F(000) = 1389
Data collection top
Enraf Nonius CAD4
diffractometer
1085 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590Rint = 0.025
Graphite monochromatorθmax = 30.0°, θmin = 2.5°
non–profiled ω scansh = 121
Absorption correction: ψ scan
(North et al., 1968)
k = 121
Tmin = 0.352, Tmax = 0.427l = 3939
2301 measured reflections3 standard reflections every 120 min
1085 independent reflections intensity decay: 2%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.014 w = 1/[σ2(Fo2) + (0.0227P)2 + 0.043P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.037(Δ/σ)max = 0.001
S = 1.13Δρmax = 0.47 e Å3
1085 reflectionsΔρmin = 0.37 e Å3
78 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0034 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 209 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.014 (11)
Crystal data top
Na5[Sm(C4H4O5)3](BF4)2·6H2OZ = 3
Mr = 943.23Mo Kα radiation
Trigonal, R32µ = 2.12 mm1
a = 9.7223 (11) ÅT = 291 K
c = 28.0728 (14) Å0.6 × 0.4 × 0.4 mm
V = 2298.0 (4) Å3
Data collection top
Enraf Nonius CAD4
diffractometer
1085 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.025
Tmin = 0.352, Tmax = 0.4273 standard reflections every 120 min
2301 measured reflections intensity decay: 2%
1085 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.014H-atom parameters constrained
wR(F2) = 0.037Δρmax = 0.47 e Å3
S = 1.13Δρmin = 0.37 e Å3
1085 reflectionsAbsolute structure: Flack (1983), 209 Friedel pairs
78 parametersAbsolute structure parameter: 0.014 (11)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sm10000.01790 (7)
O10.2581 (2)0.2581 (2)00.0284 (4)
O20.19341 (17)0.03111 (19)0.05890 (5)0.0290 (3)
O30.4165 (2)0.1649 (2)0.09996 (6)0.0415 (4)
C10.3830 (3)0.2891 (3)0.03217 (8)0.0334 (5)
H1A0.41190.38520.050.04*
H1B0.47560.30470.01460.04*
C20.3291 (2)0.1499 (5)0.06618 (6)0.0254 (7)
B10.33330.33330.23666 (14)0.0402 (8)
F10.33330.33330.28527 (9)0.0805 (10)
F20.2504 (6)0.2633 (6)0.21968 (7)0.0688 (5)
Na10.66670.33330.13396 (5)0.0308 (2)
Na20.33330.0479 (2)0.16670.0526 (4)
O40.5909 (2)0.1130 (3)0.19069 (6)0.0429 (5)
H410.56650.13350.21990.107 (11)*
H420.60060.03770.20150.107 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sm10.02018 (8)0.02018 (8)0.01336 (10)0.01009 (4)00
O10.0249 (6)0.0249 (6)0.0274 (10)0.0064 (8)0.0040 (4)0.0040 (4)
O20.0276 (6)0.0325 (8)0.0242 (7)0.0130 (6)0.0080 (5)0.0009 (6)
O30.0369 (8)0.0449 (9)0.0372 (8)0.0162 (7)0.0170 (7)0.0004 (7)
C10.0258 (9)0.0349 (11)0.0320 (11)0.0095 (9)0.0064 (8)0.0013 (9)
C20.0254 (7)0.0275 (18)0.0242 (8)0.0139 (8)0.0041 (6)0.0024 (8)
B10.0429 (11)0.0429 (11)0.0347 (17)0.0214 (6)00
F10.1029 (16)0.1029 (16)0.0357 (12)0.0514 (8)00
F20.0615 (15)0.087 (2)0.0753 (10)0.0506 (11)0.008 (2)0.003 (2)
Na10.0318 (3)0.0318 (3)0.0288 (5)0.01588 (17)00
Na20.0389 (8)0.0534 (7)0.0606 (10)0.0194 (4)0.0018 (8)0.0009 (4)
O40.0489 (12)0.0558 (10)0.0315 (7)0.0316 (8)0.0073 (7)0.0084 (8)
Geometric parameters (Å, º) top
Sm1—O2i2.4068 (13)B1—F21.375 (2)
Sm1—O22.4068 (13)B1—F2vi1.375 (2)
Sm1—O2ii2.4068 (13)B1—F2vii1.375 (2)
Sm1—O2iii2.4068 (13)F2—Na22.358 (4)
Sm1—O2iv2.4068 (13)Na1—O3viii2.3504 (17)
Sm1—O2v2.4068 (13)Na1—O3ix2.3504 (17)
Sm1—O12.509 (2)Na1—O4viii2.468 (2)
Sm1—O1ii2.509 (2)Na1—O42.468 (2)
Sm1—O1iv2.509 (2)Na1—O4ix2.468 (2)
O1—C1v1.419 (2)Na1—Na2viii3.6156 (12)
O1—C11.419 (2)Na1—Na23.6156 (12)
O2—C21.262 (3)Na1—Na2ix3.6156 (12)
O3—C21.233 (2)Na2—O42.292 (2)
O3—Na12.3504 (17)Na2—O4x2.292 (2)
O3—Na22.602 (2)Na2—F2x2.358 (4)
C1—C21.519 (4)Na2—O3x2.602 (2)
B1—F11.365 (5)Na2—Na1xi3.6157 (12)
O2i—Sm1—O2149.27 (8)O3viii—Na1—O485.70 (6)
O2i—Sm1—O2ii126.07 (7)O3—Na1—O484.34 (6)
O2—Sm1—O2ii78.00 (6)O3ix—Na1—O4163.74 (8)
O2i—Sm1—O2iii78.00 (6)O4viii—Na1—O482.83 (7)
O2—Sm1—O2iii88.15 (7)O3viii—Na1—O4ix163.74 (8)
O2ii—Sm1—O2iii149.27 (8)O3—Na1—O4ix85.70 (6)
O2i—Sm1—O2iv88.15 (7)O3ix—Na1—O4ix84.34 (6)
O2—Sm1—O2iv78.00 (6)O4viii—Na1—O4ix82.83 (7)
O2ii—Sm1—O2iv78.00 (6)O4—Na1—O4ix82.83 (7)
O2iii—Sm1—O2iv126.07 (7)O3viii—Na1—Na2viii45.89 (5)
O2i—Sm1—O2v78.00 (6)O3—Na1—Na2viii146.07 (5)
O2—Sm1—O2v126.07 (7)O3ix—Na1—Na2viii100.12 (5)
O2ii—Sm1—O2v88.15 (7)O4viii—Na1—Na2viii38.79 (5)
O2iii—Sm1—O2v78.00 (6)O4—Na1—Na2viii77.88 (5)
O2iv—Sm1—O2v149.27 (8)O4ix—Na1—Na2viii119.85 (5)
O2i—Sm1—O1135.93 (4)O3viii—Na1—Na2100.12 (5)
O2—Sm1—O163.03 (4)O3—Na1—Na245.89 (5)
O2ii—Sm1—O174.63 (4)O3ix—Na1—Na2146.07 (5)
O2iii—Sm1—O174.63 (4)O4viii—Na1—Na2119.85 (5)
O2iv—Sm1—O1135.93 (4)O4—Na1—Na238.79 (5)
O2v—Sm1—O163.03 (4)O4ix—Na1—Na277.88 (5)
O2i—Sm1—O1ii63.03 (4)Na2viii—Na1—Na2113.784 (17)
O2—Sm1—O1ii135.93 (4)O3viii—Na1—Na2ix146.07 (5)
O2ii—Sm1—O1ii63.03 (4)O3—Na1—Na2ix100.12 (5)
O2iii—Sm1—O1ii135.93 (4)O3ix—Na1—Na2ix45.89 (5)
O2iv—Sm1—O1ii74.63 (4)O4viii—Na1—Na2ix77.88 (5)
O2v—Sm1—O1ii74.63 (4)O4—Na1—Na2ix119.85 (5)
O1—Sm1—O1ii120O4ix—Na1—Na2ix38.79 (5)
O2i—Sm1—O1iv74.63 (4)Na2viii—Na1—Na2ix113.784 (17)
O2—Sm1—O1iv74.63 (4)Na2—Na1—Na2ix113.784 (17)
O2ii—Sm1—O1iv135.93 (4)O4—Na2—O4x164.31 (14)
O2iii—Sm1—O1iv63.03 (4)O4—Na2—F2x90.19 (12)
O2iv—Sm1—O1iv63.03 (4)O4x—Na2—F2x101.09 (12)
O2v—Sm1—O1iv135.93 (4)O4—Na2—F2101.09 (12)
O1—Sm1—O1iv120O4x—Na2—F290.19 (12)
O1ii—Sm1—O1iv120F2x—Na2—F288.42 (11)
C1v—O1—C1115.5 (2)O4—Na2—O382.52 (7)
C1v—O1—Sm1122.27 (12)O4x—Na2—O387.46 (7)
C1—O1—Sm1122.27 (12)F2x—Na2—O385.67 (6)
C2—O2—Sm1128.29 (18)F2—Na2—O3173.09 (10)
C2—O3—Na1143.8 (2)O4—Na2—O3x87.46 (7)
C2—O3—Na2122.54 (19)O4x—Na2—O3x82.51 (7)
Na1—O3—Na293.66 (6)F2x—Na2—O3x173.09 (10)
O1—C1—C2109.47 (17)F2—Na2—O3x85.67 (6)
O3—C2—O2125.2 (3)O3—Na2—O3x100.45 (11)
O3—C2—C1117.9 (2)O4—Na2—Na142.41 (6)
O2—C2—C1116.79 (19)O4x—Na2—Na1125.51 (7)
F1—B1—F2110.28 (17)F2x—Na2—Na191.34 (7)
F1—B1—F2vi110.28 (17)F2—Na2—Na1143.50 (11)
F2—B1—F2vi108.65 (18)O3—Na2—Na140.45 (4)
F1—B1—F2vii110.28 (17)O3x—Na2—Na191.30 (6)
F2—B1—F2vii108.65 (18)O4—Na2—Na1xi125.51 (7)
F2vi—B1—F2vii108.65 (18)O4x—Na2—Na1xi42.41 (6)
B1—F2—Na2129.3 (3)F2x—Na2—Na1xi143.51 (11)
O3viii—Na1—O3104.63 (6)F2—Na2—Na1xi91.34 (6)
O3viii—Na1—O3ix104.63 (6)O3—Na2—Na1xi91.30 (6)
O3—Na1—O3ix104.63 (6)O3x—Na2—Na1xi40.45 (4)
O3viii—Na1—O4viii84.34 (6)Na1—Na2—Na1xi109.51 (5)
O3—Na1—O4viii163.74 (8)Na2—O4—Na198.79 (7)
O3ix—Na1—O4viii85.70 (6)
Symmetry codes: (i) x, x+y, z; (ii) y, xy, z; (iii) xy, y, z; (iv) x+y, x, z; (v) y, x, z; (vi) y, xy1, z; (vii) x+y+1, x, z; (viii) y+1, xy, z; (ix) x+y+1, x+1, z; (x) x+2/3, x+y+1/3, z+1/3; (xi) y1/3, x2/3, z+1/3.
(III) top
Crystal data top
Na5[Gd(C4H4O5)3](BF4)2·6H2ODx = 2.071 Mg m3
Mr = 950.13Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32Cell parameters from 25 reflections
Hall symbol: R 3 2"θ = 12.1–15.2°
a = 9.7041 (10) ŵ = 2.38 mm1
c = 28.025 (6) ÅT = 291 K
V = 2285.5 (6) Å3Prism, colourless
Z = 30.5 × 0.45 × 0.35 mm
F(000) = 1395
Data collection top
Enraf Nonius CAD-4
diffractometer
1078 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590Rint = 0.013
Graphite monochromatorθmax = 30.0°, θmin = 2.5°
non–profiled ω scansh = 131
Absorption correction: ψ scan
(North et al., 1968)
k = 111
Tmin = 0.336, Tmax = 0.433l = 3939
2033 measured reflections3 standard reflections every 120 min
1078 independent reflections intensity decay: 3%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.012 w = 1/[σ2(Fo2) + (0.0226P)2 + 0.5279P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.032(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.38 e Å3
1078 reflectionsΔρmin = 0.26 e Å3
78 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.00258 (15)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 206 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.005 (10)
Crystal data top
Na5[Gd(C4H4O5)3](BF4)2·6H2OZ = 3
Mr = 950.13Mo Kα radiation
Trigonal, R32µ = 2.38 mm1
a = 9.7041 (10) ÅT = 291 K
c = 28.025 (6) Å0.5 × 0.45 × 0.35 mm
V = 2285.5 (6) Å3
Data collection top
Enraf Nonius CAD-4
diffractometer
1078 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.013
Tmin = 0.336, Tmax = 0.4333 standard reflections every 120 min
2033 measured reflections intensity decay: 3%
1078 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.012H-atom parameters constrained
wR(F2) = 0.032Δρmax = 0.38 e Å3
S = 1.07Δρmin = 0.26 e Å3
1078 reflectionsAbsolute structure: Flack (1983), 206 Friedel pairs
78 parametersAbsolute structure parameter: 0.005 (10)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Gd10000.01797 (6)
O10.2566 (2)0.2566 (2)00.0279 (4)
O20.19123 (16)0.02868 (17)0.05864 (5)0.0283 (3)
O30.4154 (2)0.1616 (2)0.09977 (5)0.0404 (4)
C10.3823 (2)0.2874 (3)0.03196 (7)0.0319 (4)
H1A0.47460.30220.01420.038*
H1B0.41220.3840.04980.038*
C20.32749 (19)0.1480 (4)0.06592 (5)0.0251 (6)
B10.33330.33330.23679 (12)0.0393 (7)
F10.33330.33330.28550 (8)0.0783 (9)
F20.2482 (5)0.2641 (5)0.21977 (7)0.0668 (5)
Na10.66670.33330.13370 (4)0.0309 (2)
Na20.33330.04815 (18)0.16670.0499 (4)
O40.5922 (2)0.1134 (2)0.19064 (6)0.0418 (4)
H410.56760.13350.21930.079 (8)*
H420.58540.03830.20180.079 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Gd10.02037 (7)0.02037 (7)0.01318 (7)0.01019 (3)00
O10.0249 (6)0.0249 (6)0.0271 (8)0.0074 (7)0.0050 (4)0.0050 (4)
O20.0272 (6)0.0311 (7)0.0242 (5)0.0129 (6)0.0066 (5)0.0015 (5)
O30.0356 (7)0.0447 (8)0.0358 (6)0.0163 (7)0.0160 (6)0.0012 (6)
C10.0255 (8)0.0324 (9)0.0302 (8)0.0087 (8)0.0073 (7)0.0028 (8)
C20.0262 (6)0.0287 (17)0.0230 (6)0.0155 (7)0.0041 (5)0.0021 (7)
B10.0421 (10)0.0421 (10)0.0337 (14)0.0211 (5)00
F10.1010 (15)0.1010 (15)0.0328 (10)0.0505 (7)00
F20.0650 (15)0.077 (2)0.0740 (9)0.0476 (10)0.0099 (18)0.0011 (19)
Na10.0321 (3)0.0321 (3)0.0284 (4)0.01606 (16)00
Na20.0390 (8)0.0519 (7)0.0545 (8)0.0195 (4)0.0020 (7)0.0010 (3)
O40.0476 (11)0.0552 (10)0.0290 (6)0.0304 (8)0.0060 (6)0.0082 (7)
Geometric parameters (Å, º) top
Gd1—O2i2.3887 (13)B1—F21.384 (2)
Gd1—O22.3887 (13)B1—F2vi1.384 (2)
Gd1—O2ii2.3887 (13)B1—F2vii1.384 (2)
Gd1—O2iii2.3887 (13)F2—Na22.358 (4)
Gd1—O2iv2.3887 (13)Na1—O3viii2.3585 (16)
Gd1—O2v2.3887 (13)Na1—O3ix2.3585 (16)
Gd1—O12.490 (2)Na1—O42.466 (2)
Gd1—O1ii2.490 (2)Na1—O4viii2.466 (2)
Gd1—O1iv2.490 (2)Na1—O4ix2.466 (2)
O1—C11.420 (2)Na1—Na2viii3.6120 (11)
O1—C1v1.420 (2)Na1—Na23.6120 (11)
O2—C21.265 (2)Na1—Na2ix3.6120 (11)
O3—C21.238 (2)Na2—O42.2985 (18)
O3—Na12.3585 (16)Na2—O4x2.2985 (18)
O3—Na22.583 (2)Na2—F2x2.357 (4)
C1—C21.516 (4)Na2—O3x2.583 (2)
B1—F11.365 (4)Na2—Na1xi3.6121 (11)
O2i—Gd1—O2148.44 (7)O3viii—Na1—O4viii84.12 (6)
O2i—Gd1—O2ii126.94 (7)O3—Na1—O4viii163.41 (7)
O2—Gd1—O2ii77.87 (5)O3ix—Na1—O4viii85.80 (6)
O2i—Gd1—O2iii77.87 (5)O4—Na1—O4viii82.64 (6)
O2—Gd1—O2iii88.12 (7)O3viii—Na1—O4ix163.41 (7)
O2ii—Gd1—O2iii148.44 (7)O3—Na1—O4ix85.80 (6)
O2i—Gd1—O2iv88.12 (7)O3ix—Na1—O4ix84.12 (6)
O2—Gd1—O2iv77.87 (5)O4—Na1—O4ix82.64 (6)
O2ii—Gd1—O2iv77.87 (5)O4viii—Na1—O4ix82.64 (6)
O2iii—Gd1—O2iv126.94 (7)O3viii—Na1—Na2viii45.52 (4)
O2i—Gd1—O2v77.87 (5)O3—Na1—Na2viii145.60 (5)
O2—Gd1—O2v126.94 (7)O3ix—Na1—Na2viii100.65 (5)
O2ii—Gd1—O2v88.12 (7)O4—Na1—Na2viii77.53 (5)
O2iii—Gd1—O2v77.87 (5)O4viii—Na1—Na2viii39.00 (4)
O2iv—Gd1—O2v148.44 (7)O4ix—Na1—Na2viii119.76 (5)
O2i—Gd1—O1135.94 (3)O3viii—Na1—Na2100.65 (5)
O2—Gd1—O163.47 (3)O3—Na1—Na245.52 (4)
O2ii—Gd1—O174.22 (4)O3ix—Na1—Na2145.60 (5)
O2iii—Gd1—O174.22 (4)O4—Na1—Na239.00 (4)
O2iv—Gd1—O1135.94 (3)O4viii—Na1—Na2119.76 (5)
O2v—Gd1—O163.47 (3)O4ix—Na1—Na277.53 (5)
O2i—Gd1—O1ii63.47 (3)Na2viii—Na1—Na2113.693 (15)
O2—Gd1—O1ii135.94 (3)O3viii—Na1—Na2ix145.60 (5)
O2ii—Gd1—O1ii63.47 (3)O3—Na1—Na2ix100.65 (5)
O2iii—Gd1—O1ii135.94 (3)O3ix—Na1—Na2ix45.52 (4)
O2iv—Gd1—O1ii74.22 (4)O4—Na1—Na2ix119.76 (5)
O2v—Gd1—O1ii74.22 (4)O4viii—Na1—Na2ix77.53 (5)
O1—Gd1—O1ii120O4ix—Na1—Na2ix39.00 (4)
O2i—Gd1—O1iv74.22 (4)Na2viii—Na1—Na2ix113.693 (15)
O2—Gd1—O1iv74.22 (4)Na2—Na1—Na2ix113.693 (15)
O2ii—Gd1—O1iv135.94 (3)O4—Na2—O4x164.42 (13)
O2iii—Gd1—O1iv63.47 (3)O4—Na2—F2x89.66 (11)
O2iv—Gd1—O1iv63.47 (3)O4x—Na2—F2x101.50 (12)
O2v—Gd1—O1iv135.94 (3)O4—Na2—F2101.50 (12)
O1—Gd1—O1iv120O4x—Na2—F289.66 (11)
O1ii—Gd1—O1iv120F2x—Na2—F288.91 (11)
C1—O1—C1v115.3 (2)O4—Na2—O382.73 (7)
C1—O1—Gd1122.36 (11)O4x—Na2—O387.41 (6)
C1v—O1—Gd1122.36 (11)F2x—Na2—O385.03 (6)
C2—O2—Gd1127.83 (15)F2—Na2—O3172.60 (10)
C2—O3—Na1142.97 (18)O4—Na2—O3x87.41 (6)
C2—O3—Na2123.19 (17)O4x—Na2—O3x82.73 (7)
Na1—O3—Na293.82 (5)F2x—Na2—O3x172.60 (10)
O1—C1—C2109.07 (15)F2—Na2—O3x85.03 (6)
O3—C2—O2124.8 (3)O3—Na2—O3x101.32 (10)
O3—C2—C1118.0 (2)O4—Na2—Na142.47 (5)
O2—C2—C1117.09 (17)O4x—Na2—Na1125.54 (7)
F1—B1—F2110.16 (15)F2x—Na2—Na190.87 (7)
F1—B1—F2vi110.16 (15)F2—Na2—Na1143.97 (10)
F2—B1—F2vi108.78 (16)O3—Na2—Na140.66 (4)
F1—B1—F2vii110.16 (15)O3x—Na2—Na191.55 (6)
F2—B1—F2vii108.78 (16)O4—Na2—Na1xi125.54 (7)
F2vi—B1—F2vii108.78 (16)O4x—Na2—Na1xi42.47 (5)
B1—F2—Na2128.3 (3)F2x—Na2—Na1xi143.97 (10)
O3viii—Na1—O3104.84 (5)F2—Na2—Na1xi90.87 (7)
O3viii—Na1—O3ix104.84 (5)O3—Na2—Na1xi91.55 (6)
O3—Na1—O3ix104.84 (5)O3x—Na2—Na1xi40.65 (4)
O3viii—Na1—O485.80 (6)Na1—Na2—Na1xi109.50 (5)
O3—Na1—O484.12 (6)Na2—O4—Na198.53 (7)
O3ix—Na1—O4163.41 (7)
Symmetry codes: (i) x, x+y, z; (ii) y, xy, z; (iii) xy, y, z; (iv) x+y, x, z; (v) y, x, z; (vi) y, xy+1, z; (vii) x+y1, x, z; (viii) y1, xy, z; (ix) x+y1, x1, z; (x) x2/3, x+y1/3, z1/3; (xi) y+1/3, x+2/3, z1/3.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaNa5[Nd(C4H4O5)3](BF4)2·6H2ONa5[Sm(C4H4O5)3](BF4)2·6H2ONa5[Gd(C4H4O5)3](BF4)2·6H2O
Mr937.12943.23950.13
Crystal system, space groupTrigonal, R32Trigonal, R32Trigonal, R32
Temperature (K)291291291
a, c (Å)9.7508 (7), 28.177 (2)9.7223 (11), 28.0728 (14)9.7041 (10), 28.025 (6)
V3)2320.1 (3)2298.0 (4)2285.5 (6)
Z333
Radiation typeMo KαMo KαMo Kα
µ (mm1)1.882.122.38
Crystal size (mm)0.55 × 0.45 × 0.10.6 × 0.4 × 0.40.5 × 0.45 × 0.35
Data collection
DiffractometerEnraf Nonius CAD-4
diffractometer
Enraf Nonius CAD4
diffractometer
Enraf Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
ψ scan
(North et al., 1968)
ψ scan
(North et al., 1968)
Tmin, Tmax0.425, 0.8340.352, 0.4270.336, 0.433
No. of measured, independent and
observed [I > 2σ(I)] reflections
1134, 1001, 1001 2301, 1085, 1085 2033, 1078, 1078
Rint0.0300.0250.013
(sin θ/λ)max1)0.7030.7030.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.055, 1.13 0.014, 0.037, 1.13 0.012, 0.032, 1.07
No. of reflections100110851078
No. of parameters777878
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.47, 0.510.47, 0.370.38, 0.26
Absolute structureFlack (1983), 121 Friedel pairsFlack (1983), 209 Friedel pairsFlack (1983), 206 Friedel pairs
Absolute structure parameter0.010 (18)0.014 (11)0.005 (10)

Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999).

 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds