Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008959/br6015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008959/br6015Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.004 Å
- R factor = 0.025
- wR factor = 0.059
- Data-to-parameter ratio = 20.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.658 0.808 Tmin and Tmax expected: 0.566 0.808 RR = 1.163 Please check that your absorption correction is appropriate.
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, H2O, HF, KBF4 and Sn(C2O4) in a molar ratio of 20:4:1:1:1. Solvothermal synthesis was conducted in a 23 ml capacity Teflon-lined Parr autoclave, at 423 K for 5 d. The BING-3 crystals were colourless plates, and were manually separated for single-crystal X-ray analysis.
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.
[Sn(C2O4)]KF | F(000) = 488 |
Mr = 264.81 | Dx = 3.181 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0692 (5) Å | Cell parameters from 4624 reflections |
b = 9.5398 (6) Å | θ = 5–63° |
c = 7.7245 (4) Å | µ = 5.33 mm−1 |
β = 111.600 (1)° | T = 273 K |
V = 552.86 (6) Å3 | Plate, colorless |
Z = 4 | 0.11 × 0.10 × 0.04 mm |
CCD area-detector diffractometer | 1685 independent reflections |
Radiation source: fine-focus sealed tube | 1443 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 30.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.658, Tmax = 0.808 | k = −13→13 |
10746 measured reflections | l = −11→11 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.025 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0288P)2 + 0.1128P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1685 reflections | Δρmax = 0.75 e Å−3 |
82 parameters | Δρmin = −0.45 e Å−3 |
[Sn(C2O4)]KF | V = 552.86 (6) Å3 |
Mr = 264.81 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0692 (5) Å | µ = 5.33 mm−1 |
b = 9.5398 (6) Å | T = 273 K |
c = 7.7245 (4) Å | 0.11 × 0.10 × 0.04 mm |
β = 111.600 (1)° |
CCD area-detector diffractometer | 1685 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1443 reflections with I > 2σ(I) |
Tmin = 0.658, Tmax = 0.808 | Rint = 0.039 |
10746 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 82 parameters |
wR(F2) = 0.059 | 0 restraints |
S = 1.06 | Δρmax = 0.75 e Å−3 |
1685 reflections | Δρmin = −0.45 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 | ||
Sn1 | 0.86411 (3) | 0.81285 (2) | 0.49210 (3) | 0.02678 (8) | |
K1 | 0.39785 (10) | 0.82173 (7) | 0.59318 (9) | 0.03195 (15) | |
F1 | 0.6033 (3) | 0.8618 (2) | 0.3982 (3) | 0.0390 (4) | |
O1 | 0.8055 (3) | 0.6245 (2) | 0.3074 (3) | 0.0327 (5) | |
O2 | 0.7907 (3) | 0.3916 (2) | 0.3044 (3) | 0.0337 (5) | |
O3 | 0.7898 (3) | 0.6360 (2) | 0.6399 (3) | 0.0330 (5) | |
O4 | 0.7184 (4) | 0.4100 (2) | 0.6296 (3) | 0.0405 (6) | |
C1 | 0.7884 (4) | 0.5046 (3) | 0.3763 (4) | 0.0234 (5) | |
C2 | 0.7617 (4) | 0.5140 (3) | 0.5653 (4) | 0.0256 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03053 (13) | 0.01964 (11) | 0.03241 (12) | −0.00227 (8) | 0.01424 (9) | −0.00087 (8) |
K1 | 0.0423 (4) | 0.0284 (3) | 0.0310 (3) | −0.0060 (3) | 0.0204 (3) | −0.0041 (3) |
F1 | 0.0317 (10) | 0.0521 (12) | 0.0368 (10) | 0.0048 (9) | 0.0167 (8) | 0.0045 (9) |
O1 | 0.0564 (15) | 0.0221 (11) | 0.0244 (10) | −0.0029 (10) | 0.0204 (10) | 0.0007 (8) |
O2 | 0.0496 (14) | 0.0218 (11) | 0.0350 (11) | −0.0027 (10) | 0.0218 (10) | −0.0073 (8) |
O3 | 0.0579 (16) | 0.0205 (10) | 0.0283 (10) | −0.0078 (10) | 0.0251 (10) | −0.0058 (8) |
O4 | 0.0742 (18) | 0.0224 (12) | 0.0334 (11) | −0.0091 (11) | 0.0297 (12) | 0.0000 (9) |
C1 | 0.0256 (14) | 0.0236 (14) | 0.0221 (12) | 0.0024 (11) | 0.0101 (11) | 0.0014 (10) |
C2 | 0.0327 (16) | 0.0223 (14) | 0.0234 (12) | −0.0044 (12) | 0.0122 (12) | −0.0017 (10) |
Sn1—F1 | 2.0122 (19) | K1—O1ii | 3.133 (3) |
Sn1—O1 | 2.234 (2) | F1—K1i | 2.913 (2) |
Sn1—O3 | 2.239 (2) | F1—K1vii | 3.020 (2) |
Sn1—O3i | 2.608 (2) | O1—C1 | 1.290 (3) |
Sn1—O1ii | 2.714 (2) | O1—K1i | 3.133 (3) |
Sn1—O2iii | 3.288 (2) | O2—C1 | 1.216 (3) |
K1—F1 | 2.6461 (19) | O2—K1iv | 2.823 (2) |
K1—O4iv | 2.746 (2) | O2—K1viii | 2.958 (2) |
K1—O4v | 2.767 (2) | O3—C2 | 1.281 (3) |
K1—O2iv | 2.823 (2) | O4—C2 | 1.217 (3) |
K1—F1ii | 2.913 (2) | O4—K1iv | 2.746 (2) |
K1—O2vi | 2.958 (2) | O4—K1ix | 2.767 (2) |
K1—F1vii | 3.020 (2) | C1—C2 | 1.555 (4) |
F1—Sn1—O1 | 90.50 (9) | O2iv—K1—F1vii | 135.08 (6) |
F1—Sn1—O3 | 85.28 (9) | F1ii—K1—F1vii | 126.04 (4) |
O1—Sn1—O3 | 71.68 (7) | O2vi—K1—F1vii | 78.07 (6) |
F1—Sn1—O3i | 76.83 (7) | F1—K1—O1ii | 61.39 (6) |
O1—Sn1—O3i | 64.60 (7) | O4iv—K1—O1ii | 120.87 (7) |
O3—Sn1—O3i | 132.15 (8) | O4v—K1—O1ii | 97.50 (7) |
F1—Sn1—O1ii | 76.57 (7) | O2iv—K1—O1ii | 122.65 (7) |
O1—Sn1—O1ii | 133.19 (7) | F1ii—K1—O1ii | 59.80 (6) |
O3—Sn1—O1ii | 62.65 (7) | O2vi—K1—O1ii | 123.39 (6) |
O3i—Sn1—O1ii | 147.81 (7) | F1vii—K1—O1ii | 80.54 (6) |
F1—Sn1—O2iii | 154.09 (7) | Sn1—F1—K1 | 123.54 (9) |
O1—Sn1—O2iii | 76.77 (7) | Sn1—F1—K1i | 111.13 (8) |
O3—Sn1—O2iii | 69.39 (7) | K1—F1—K1i | 94.84 (6) |
O3i—Sn1—O2iii | 116.03 (6) | Sn1—F1—K1vii | 103.61 (8) |
O1ii—Sn1—O2iii | 95.65 (6) | K1—F1—K1vii | 97.12 (6) |
F1—K1—O4iv | 84.30 (7) | K1i—F1—K1vii | 127.81 (7) |
F1—K1—O4v | 149.18 (7) | C1—O1—Sn1 | 118.67 (16) |
O4iv—K1—O4v | 126.51 (9) | C1—O1—K1i | 96.45 (18) |
F1—K1—O2iv | 141.16 (7) | Sn1—O1—K1i | 98.04 (8) |
O4iv—K1—O2iv | 60.01 (6) | C1—O2—K1iv | 114.24 (18) |
O4v—K1—O2iv | 68.34 (7) | C1—O2—K1viii | 125.83 (19) |
F1—K1—F1ii | 104.94 (7) | K1iv—O2—K1viii | 90.25 (6) |
O4iv—K1—F1ii | 89.11 (7) | C2—O3—Sn1 | 119.45 (17) |
O4v—K1—F1ii | 79.11 (6) | C2—O4—K1iv | 118.96 (18) |
O2iv—K1—F1ii | 62.95 (6) | C2—O4—K1ix | 142.55 (19) |
F1—K1—O2vi | 64.35 (6) | K1iv—O4—K1ix | 96.03 (7) |
O4iv—K1—O2vi | 66.69 (7) | O2—C1—O1 | 125.2 (2) |
O4v—K1—O2vi | 122.93 (7) | O2—C1—C2 | 120.7 (2) |
O2iv—K1—O2vi | 109.21 (8) | O1—C1—C2 | 114.1 (2) |
F1ii—K1—O2vi | 153.76 (6) | O4—C2—O3 | 126.0 (3) |
F1—K1—F1vii | 82.88 (6) | O4—C2—C1 | 119.7 (2) |
O4iv—K1—F1vii | 144.65 (7) | O3—C2—C1 | 114.3 (2) |
O4v—K1—F1vii | 70.97 (6) | ||
O1—C1—C2—O3 | −11.0 (4) | O2—C1—C2—O3 | 169.5 (3) |
O1—C1—C2—O4 | 169.3 (3) | O2—C1—C2—O4 | −10.1 (4) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, y+1/2, −z+3/2; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+1, −y+2, −z+1; (viii) −x+1, y−1/2, −z+1/2; (ix) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Sn(C2O4)]KF |
Mr | 264.81 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 8.0692 (5), 9.5398 (6), 7.7245 (4) |
β (°) | 111.600 (1) |
V (Å3) | 552.86 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.33 |
Crystal size (mm) | 0.11 × 0.10 × 0.04 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.658, 0.808 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10746, 1685, 1443 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.059, 1.06 |
No. of reflections | 1685 |
No. of parameters | 82 |
Δρmax, Δρmin (e Å−3) | 0.75, −0.45 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 1999), SHELXL97.
Sn1—F1 | 2.0122 (19) | K1—O4iv | 2.746 (2) |
Sn1—O1 | 2.234 (2) | K1—O2iv | 2.823 (2) |
Sn1—O3 | 2.239 (2) | O1—C1 | 1.290 (3) |
Sn1—O3i | 2.608 (2) | O2—C1 | 1.216 (3) |
Sn1—O1ii | 2.714 (2) | O3—C2 | 1.281 (3) |
Sn1—O2iii | 3.288 (2) | O4—C2 | 1.217 (3) |
K1—F1 | 2.6461 (19) | C1—C2 | 1.555 (4) |
F1—Sn1—O1 | 90.50 (9) | O1—Sn1—O3 | 71.68 (7) |
F1—Sn1—O3 | 85.28 (9) | ||
O1—C1—C2—O3 | −11.0 (4) | O2—C1—C2—O3 | 169.5 (3) |
O1—C1—C2—O4 | 169.3 (3) | O2—C1—C2—O4 | −10.1 (4) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1. |
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We are interested in group 14 metal-based extended materials for a variety of potential applications, particularly ion exchange and sensors. Our methods involve both commonly used, as well as non-traditional, templating agents. We have discovered a series of new materials, which we denote BING-n, where BING denotes State University of New York (SUNY) at Binghamton, and n denotes the structure type. These materials can be clusters (Oliver et al., 2001) or extended in one [BING-4, Sn(C2O4)(C5H5N); Oliver et al., 2001], two (BING-3, SnO3PC6H5; Oliver et al., 2001) or three [BING-1, Na4Sn4(C2O4)3F6; Salami et al., 2001] dimensions. Here, we report the crystal structure of BING-2, a layered tin–oxalate potassium fluoride material.
Two layered tin–oxalates have been reported recently by Cheetham and co-workers (Ayyappan et al., 1998; Natarajan et al., 1999). The tin centres are octahedral and possess three oxalate groups that bridge to neighbouring Sn atoms in the layer. Traditional cationic organic ammonium templating agents were used to produce these materials, and reside in the interlayer region.
One of the thrusts of our studies is the exclusion of traditional templating agents from the synthesis mixture, and the use instead of other possible building blocks or templating agents. BING-2 was isolated from a predominantly non-aqueous pyridine solvent, to which tin oxalate, hydrogen fluoride (50% aqueous) and potassium tetrafluoroborate were added. Potassium and fluoride in this case became a building-block for the resultant product, and combined with tin oxalate to create the BING-2 structure (Fig. 1).
The layer of BING-2 is a sandwich structure, with two tin–oxalate sheets that connect to a central potassium fluoride layer. The latter is buckled and shown in Fig. 1. This buckling allows the KF layer to bond to the two surrounding Sn–oxalate layers, which are made up of discrete tin–oxalate chains that propogate along the c axis (one such layer is shown in Fig. 2). The Sn centers are chelated to one oxalate group, and connect to two neighbouring oxalate groups in the chain through longer contact distances (shown by the broken line, Fig. 2). The O atoms on the other side of the oxalate groups connect to potassium centres of the potassium fluoride layer. The BING-2 layer is therefore a triple layer (Fig. 3).
The asymmetric unit is relatively simple, containing only one type of each atom in the formula unit (Fig. 4). The oxalate group in BING-2 is not planar (Table 1). This is the first time that we have seen this feature in our published BING-n structures (Salami et al., 2001), those of others (Ayyappan et al., 1998; Natarajan et al., 1999) as well an unpublished one-dimensional tin–oxalate structure (BING-4; Oliver et al., 2001). This non-planarity may allow the formation of a three-dimensional tin–oxalate open-framework. We are currently studying other combinations of tin–oxalate and various structure directing agents, in order to isolate inorganic materials capable of our target application of both anion and cation exchange.