Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002409/br6005sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002409/br6005Isup2.hkl |
CCDC reference: 159831
Key indicators
- Single-crystal X-ray study
- T = 293 K
- R factor = 0.034
- wR factor = 0.087
- Data-to-parameter ratio = 18.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
CHEMS_02 Please check that you have entered the correct _publ_requested_category classification of your compound; FI or CI or EI for inorganic; FM or CM or EM for metal-organic; FO or CO or EO for organic. From the CIF: _publ_requested_category EM From the CIF: _chemical_formula_sum :C6 F6 Na4 O12 Sn4 General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C6 F6 Na4 O12 Sn4 Atom count from _chemical_formula_moiety:C6 Na12 O12 Sn12
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The reaction mixture consisted of pyridine, H20, HF, NaBF4 and Sn(C2O4) in a molar ratio of 20:4:1:1:1. The pH of the starting mixture was aproximately 5.8. Solvothermal synthesis was conducted in a 23 ml capacity Teflon-lined Parr autoclave, at 423 K for 5 d. The BING-1 crystals were colourless plates and were manually separated for single-crystal X-ray analysis. Small black crystals were also present in the product as a minor side-product. The latter was identified, also by single-crystal X-ray analysis, as tin(II) oxide.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 1999); software used to prepare material for publication: SHELXL97.
Na4Sn4(C2O4)3F6 | Z = 1 |
Mr = 944.78 | F(000) = 430 |
Triclinic, P1 | Dx = 3.514 Mg m−3 |
a = 6.0283 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7916 (6) Å | Cell parameters from 4605 reflections |
c = 9.1191 (6) Å | θ = 4.8–61° |
α = 69.486 (1)° | µ = 5.75 mm−1 |
β = 81.508 (1)° | T = 293 K |
γ = 83.017 (1)° | Prism, colorless |
V = 446.41 (5) Å3 | 0.15 × 0.10 × 0.08 mm |
Siemens SMART CCD diffractometer | 2686 independent reflections |
Radiation source: fine-focus sealed tube | 2253 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 30.6°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.465, Tmax = 0.631 | k = −12→12 |
7096 measured reflections | l = −13→12 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.034 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0547P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
2686 reflections | Δρmax = 2.07 e Å−3 |
145 parameters | Δρmin = −1.48 e Å−3 |
Na4Sn4(C2O4)3F6 | γ = 83.017 (1)° |
Mr = 944.78 | V = 446.41 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.0283 (4) Å | Mo Kα radiation |
b = 8.7916 (6) Å | µ = 5.75 mm−1 |
c = 9.1191 (6) Å | T = 293 K |
α = 69.486 (1)° | 0.15 × 0.10 × 0.08 mm |
β = 81.508 (1)° |
Siemens SMART CCD diffractometer | 2686 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2253 reflections with I > 2σ(I) |
Tmin = 0.465, Tmax = 0.631 | Rint = 0.038 |
7096 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 145 parameters |
wR(F2) = 0.087 | 0 restraints |
S = 0.99 | Δρmax = 2.07 e Å−3 |
2686 reflections | Δρmin = −1.48 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 | ||
Na1 | −0.2913 (3) | 0.0444 (2) | −0.4217 (2) | 0.0316 (4) | |
Na2 | 0.1397 (3) | 0.2643 (2) | −0.3760 (2) | 0.0272 (4) | |
Sn1 | 0.16908 (4) | −0.13839 (3) | −0.13383 (3) | 0.02056 (9) | |
Sn2 | 0.16735 (5) | 0.43093 (3) | −0.82016 (3) | 0.02177 (10) | |
F1 | 0.3612 (4) | −0.0411 (3) | −0.3430 (3) | 0.0309 (6) | |
F2 | −0.0601 (4) | 0.0434 (3) | −0.2572 (3) | 0.0307 (6) | |
F3 | 0.1316 (5) | 0.2346 (3) | −0.6173 (3) | 0.0334 (6) | |
C1 | 0.4140 (7) | 0.0761 (5) | −0.0139 (5) | 0.0209 (8) | |
O1 | 0.2467 (5) | 0.0761 (4) | −0.0830 (4) | 0.0245 (6) | |
O2 | 0.4532 (6) | 0.1848 (4) | 0.0324 (4) | 0.0340 (8) | |
C2 | 0.6026 (7) | 0.5028 (5) | −0.7296 (5) | 0.0199 (7) | |
O3 | 0.5433 (5) | 0.4089 (4) | −0.7904 (4) | 0.0298 (7) | |
O4 | 0.7991 (5) | 0.5225 (4) | −0.7153 (4) | 0.0265 (7) | |
C3 | 0.4118 (6) | 0.6055 (5) | −0.6648 (5) | 0.0187 (7) | |
O5 | 0.2124 (5) | 0.5788 (4) | −0.6765 (4) | 0.0259 (6) | |
O6 | 0.4600 (5) | 0.7024 (4) | −0.6081 (4) | 0.0234 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0268 (9) | 0.0389 (11) | 0.0365 (10) | 0.0067 (8) | −0.0150 (8) | −0.0206 (9) |
Na2 | 0.0237 (8) | 0.0253 (9) | 0.0347 (10) | −0.0040 (7) | −0.0055 (7) | −0.0111 (8) |
Sn1 | 0.02303 (15) | 0.01670 (15) | 0.02039 (15) | −0.00257 (11) | −0.00571 (10) | −0.00269 (11) |
Sn2 | 0.02411 (16) | 0.01898 (15) | 0.02294 (16) | −0.00104 (11) | −0.00900 (11) | −0.00565 (12) |
F1 | 0.0356 (14) | 0.0366 (15) | 0.0188 (12) | −0.0098 (12) | −0.0003 (10) | −0.0063 (11) |
F2 | 0.0301 (13) | 0.0235 (13) | 0.0360 (15) | 0.0002 (11) | −0.0197 (11) | −0.0012 (11) |
F3 | 0.0479 (16) | 0.0207 (13) | 0.0283 (14) | 0.0021 (12) | −0.0110 (12) | −0.0029 (11) |
C1 | 0.0208 (18) | 0.0217 (19) | 0.0207 (19) | 0.0021 (15) | −0.0077 (15) | −0.0070 (16) |
O1 | 0.0267 (15) | 0.0196 (14) | 0.0285 (16) | 0.0016 (12) | −0.0122 (12) | −0.0070 (13) |
O2 | 0.0323 (17) | 0.0298 (17) | 0.048 (2) | 0.0049 (14) | −0.0183 (15) | −0.0209 (17) |
C2 | 0.0193 (17) | 0.0197 (18) | 0.0200 (18) | 0.0013 (14) | −0.0040 (14) | −0.0058 (15) |
O3 | 0.0218 (14) | 0.0314 (17) | 0.045 (2) | 0.0012 (13) | −0.0064 (13) | −0.0240 (16) |
O4 | 0.0153 (13) | 0.0307 (17) | 0.0368 (18) | 0.0025 (12) | −0.0055 (12) | −0.0160 (15) |
C3 | 0.0168 (17) | 0.0175 (18) | 0.0200 (18) | 0.0021 (14) | −0.0050 (14) | −0.0038 (15) |
O5 | 0.0169 (13) | 0.0289 (16) | 0.0381 (18) | 0.0004 (12) | −0.0079 (12) | −0.0179 (15) |
O6 | 0.0210 (13) | 0.0215 (15) | 0.0314 (16) | 0.0002 (11) | −0.0088 (12) | −0.0119 (13) |
Na1—F2 | 2.190 (3) | Sn2—O4i | 2.443 (3) |
Na1—F1i | 2.243 (3) | F1—Na1vi | 2.243 (3) |
Na1—F1ii | 2.257 (3) | F1—Na1ii | 2.257 (3) |
Na1—O6iii | 2.419 (3) | F3—Na1ii | 2.446 (3) |
Na1—F3ii | 2.446 (3) | C1—O2 | 1.231 (5) |
Na2—F2 | 2.260 (3) | C1—O1 | 1.265 (5) |
Na2—F3 | 2.313 (3) | C1—C1v | 1.559 (8) |
Na2—O4iv | 2.386 (4) | O2—Sn1v | 2.518 (3) |
Na2—O6iv | 2.443 (3) | C2—O4 | 1.249 (5) |
Na2—O5iii | 2.467 (3) | C2—O3 | 1.252 (5) |
Na2—O1 | 2.729 (4) | C2—C3 | 1.552 (5) |
Na2—F1 | 2.787 (3) | O4—Na2iv | 2.386 (4) |
Sn1—F1 | 2.039 (3) | O4—Sn2vi | 2.443 (3) |
Sn1—F2 | 2.095 (2) | C3—O6 | 1.221 (5) |
Sn1—O1 | 2.209 (3) | C3—O5 | 1.279 (5) |
Sn1—O2v | 2.518 (3) | O5—Na2iii | 2.467 (3) |
Sn2—F3 | 2.045 (3) | O6—Na1iii | 2.419 (3) |
Sn2—O5 | 2.206 (3) | O6—Na2iv | 2.443 (3) |
Sn2—O3 | 2.299 (3) | ||
Sn1···Sn2ii | 3.6304 (5) | Sn2···Sn2viii | 3.8563 (5) |
Sn1···Sn2vii | 3.8637 (5) | Na2···Sn1 | 3.4535 (19) |
F2—Na1—F1i | 123.02 (14) | O5—Sn2—O3 | 72.13 (11) |
F2—Na1—F1ii | 151.69 (14) | F3—Sn2—O4i | 82.99 (11) |
F1i—Na1—F1ii | 83.31 (11) | O5—Sn2—O4i | 70.63 (10) |
F2—Na1—O6iii | 86.26 (12) | O3—Sn2—O4i | 141.73 (11) |
F1i—Na1—O6iii | 84.98 (12) | Sn1—F1—Na1vi | 136.74 (14) |
F1ii—Na1—O6iii | 108.13 (13) | Sn1—F1—Na1ii | 125.32 (13) |
F2—Na1—F3ii | 84.90 (11) | Na1vi—F1—Na1ii | 96.69 (11) |
F1i—Na1—F3ii | 91.03 (12) | Sn1—F1—Na2 | 90.03 (10) |
F1ii—Na1—F3ii | 84.40 (11) | Na1vi—F1—Na2 | 96.49 (11) |
O6iii—Na1—F3ii | 166.25 (14) | Na1ii—F1—Na2 | 95.27 (12) |
F2—Na2—F3 | 89.83 (12) | Sn1—F2—Na1 | 131.65 (14) |
F2—Na2—O4iv | 130.33 (14) | Sn1—F2—Na2 | 104.88 (11) |
F3—Na2—O4iv | 136.59 (14) | Na1—F2—Na2 | 106.82 (13) |
F2—Na2—O6iv | 131.00 (13) | Sn2—F3—Na2 | 120.11 (13) |
F3—Na2—O6iv | 99.65 (13) | Sn2—F3—Na1ii | 126.73 (14) |
O4iv—Na2—O6iv | 68.27 (11) | Na2—F3—Na1ii | 103.70 (12) |
F2—Na2—O5iii | 85.20 (12) | O2—C1—O1 | 126.1 (4) |
F3—Na2—O5iii | 107.04 (12) | O2—C1—C1v | 117.4 (4) |
O4iv—Na2—O5iii | 67.42 (10) | O1—C1—C1v | 116.5 (4) |
O6iv—Na2—O5iii | 135.04 (12) | O4—C2—O3 | 127.0 (4) |
F2—Na2—O1 | 65.02 (10) | O4—C2—C3 | 116.5 (4) |
F3—Na2—O1 | 137.95 (12) | O3—C2—C3 | 116.5 (3) |
O4iv—Na2—O1 | 81.79 (11) | O6—C3—O5 | 125.6 (4) |
O6iv—Na2—O1 | 76.84 (11) | O6—C3—C2 | 119.4 (3) |
O5iii—Na2—O1 | 103.88 (12) | O5—C3—C2 | 115.0 (3) |
F2—Na2—F1 | 62.08 (10) | C1—O1—Sn1 | 123.0 (3) |
F3—Na2—F1 | 76.03 (10) | C1—O1—Na2 | 130.1 (3) |
O4iv—Na2—F1 | 132.73 (12) | C1—O2—Sn1v | 113.1 (3) |
O6iv—Na2—F1 | 73.80 (10) | C2—O3—Sn2 | 116.0 (3) |
O5iii—Na2—F1 | 147.25 (12) | C2—O4—Na2iv | 118.8 (3) |
O1—Na2—F1 | 62.63 (9) | C2—O4—Sn2vi | 132.8 (3) |
F1—Sn1—F2 | 79.39 (11) | C3—O5—Sn2 | 118.9 (3) |
F1—Sn1—O1 | 84.79 (11) | C3—O5—Na2iii | 126.9 (2) |
F2—Sn1—O1 | 77.99 (10) | C3—O6—Na1iii | 136.2 (3) |
F1—Sn1—O2v | 81.38 (12) | C3—O6—Na2iv | 116.3 (3) |
F2—Sn1—O2v | 143.05 (11) | Sn1—O1—Na2 | 88.10 (10) |
O1—Sn1—O2v | 69.06 (11) | Sn2—O5—Na2iii | 111.72 (12) |
F3—Sn2—O5 | 88.56 (11) | Na1iii—O6—Na2iv | 101.66 (12) |
F3—Sn2—O3 | 87.59 (12) | Na2iv—O4—Sn2vi | 106.53 (12) |
O1—C1—C1v—O2v | −0.3 (6) | O4—C2—C3—O6 | 2.1 (6) |
O3—C2—C3—O5 | 2.1 (6) |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z−1; (iii) −x, −y+1, −z−1; (iv) −x+1, −y+1, −z−1; (v) −x+1, −y, −z; (vi) x+1, y, z; (vii) x, y−1, z+1; (viii) −x, −y+1, −z−2. |
Experimental details
Crystal data | |
Chemical formula | Na4Sn4(C2O4)3F6 |
Mr | 944.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.0283 (4), 8.7916 (6), 9.1191 (6) |
α, β, γ (°) | 69.486 (1), 81.508 (1), 83.017 (1) |
V (Å3) | 446.41 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 5.75 |
Crystal size (mm) | 0.15 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.465, 0.631 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7096, 2686, 2253 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 0.99 |
No. of reflections | 2686 |
No. of parameters | 145 |
Δρmax, Δρmin (e Å−3) | 2.07, −1.48 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 1999), SHELXL97.
Na1—F2 | 2.190 (3) | Sn1—O2v | 2.518 (3) |
Na1—F1i | 2.243 (3) | Sn2—F3 | 2.045 (3) |
Na1—F1ii | 2.257 (3) | Sn2—O5 | 2.206 (3) |
Na1—O6iii | 2.419 (3) | Sn2—O3 | 2.299 (3) |
Na1—F3ii | 2.446 (3) | Sn2—O4i | 2.443 (3) |
Na2—F2 | 2.260 (3) | C1—O2 | 1.231 (5) |
Na2—F3 | 2.313 (3) | C1—O1 | 1.265 (5) |
Na2—O4iv | 2.386 (4) | C1—C1v | 1.559 (8) |
Na2—O6iv | 2.443 (3) | C2—O4 | 1.249 (5) |
Na2—O5iii | 2.467 (3) | C2—O3 | 1.252 (5) |
Sn1—F1 | 2.039 (3) | C2—C3 | 1.552 (5) |
Sn1—F2 | 2.095 (2) | C3—O6 | 1.221 (5) |
Sn1—O1 | 2.209 (3) | C3—O5 | 1.279 (5) |
Sn1···Sn2ii | 3.6304 (5) | Sn2···Sn2vii | 3.8563 (5) |
Sn1···Sn2vi | 3.8637 (5) | ||
O1—C1—C1v—O2v | −0.3 (6) | O4—C2—C3—O6 | 2.1 (6) |
O3—C2—C3—O5 | 2.1 (6) |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z−1; (iii) −x, −y+1, −z−1; (iv) −x+1, −y+1, −z−1; (v) −x+1, −y, −z; (vi) x, y−1, z+1; (vii) −x, −y+1, −z−2. |
We are currently focusing on the solvothermal synthesis of layered and open-framework materials based on lower Group 14 metals. In particular, we are interested in non-traditional templating agents for the formation of anionic and cationic germanates and stannates. In the course of our work on the Sn–HF–H2O–pyridine system, where the latter is the non-aqueous solvent, we have discovered a series of new metastable three-dimensional and lower dimensionality materials. We denote our structures as BING-n, where BING denotes State University of New York (SUNY) at Binghamton, and n denotes structure type.
Our structure is related to the series of tin oxalates recently reported by Cheetham and co-workers (Ayyappan et al., 1998; Natarajan et al., 1999). The latter are layered, where octahedral Sn atoms are three-connected in the plane of the layer by oxalate groups. The anionic layers are separated and charge-balanced by electrostatically bonded organic ammonium groups.
In the current work, we used a predominantly non-aqueous environment, where a small amount of water and hydrogen fluoride (50% aqueous) were added to a pyridine solvent. Sodium tetrafluoroborate was also added to the synthesis mixture, which is known to act as a mineralizer. Sodium and fluoride combined with tin oxalate to create the BING-1 three-dimensional framework (Fig. 1). The key feature of BING-1, which enables the formation of a framework, is the pentacoordinate Na1 and heptacoordinate Na2 atoms, which covalently bond to the fluorines and O atoms of the layers, and link the layers along the c axis.
There are two crystallographically unique tin centres, which are bonded to fluorines and O atoms on one side of the atoms (Fig. 2). The other side of the tin centres were in close proximity to other tins, and appear as bonds in Fig. 1. The distances, however, are on the order of 3.6 to 3.8 Å (Table 2), which is longer than those in metallic tin. The residual electron-density Fourier difference map could not resolve the nature of the tin–tin interaction.
Both Sn1 and Sn2 are four-coordinate with respect to fluorine and oxygen. Sn1 bonds to F1 and F2, as well as O1 and O2 of the C1—C1 oxalate group; the latter dimerizes the Sn1 to another Sn1. Sn2 bonds to one fluorine and three O atoms (Table 1). Two of these O atoms, O3 and O5, belong to one side of the C2—C3 oxalate group (torsion angles, Table 1). The third oxygen, O4, bonds to another oxalate group on the other side of Sn2, to define a tin oxalate chain that propogates along the a axis. The last oxgyen of the C2—C3 oxalate group, O6, bonds to two Na atoms [O6—Na1 2.419 (3) Å and O6—Na2 2.443 (3) Å]. The C—C distance of the oxalate groups [C1—C1 1.559 (8) Å and C2—C3 1.552 (5) Å] compares well with other metal oxalate structures (Belaj et al., 2000).