Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101010034/br1323sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101010034/br1323Isup2.hkl |
CCDC reference: 173356
The reaction mixture consisted of pyridine, hydrogen fluoride, phenylphosphonic acid and [Sn(C2O4)] in a molar ratio of 16:2:4:1, respectively. Solvothermal synthesis was conducted in a 23 ml capacity Teflon-lined Parr autoclave at 423 K for 3 d. The crystals of (I) were colourless plates and the product was determined to be phase-pure using powder X-ray diffraction.
The Flack (1983) parameter of 0.5 indicated inverse twinning, which was refined and resulted in a 1:1 ratio of the direct and inverted structures. However, refinement from a different crystal yielded a ratio of 1:4.
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.
C6H5O3PSn | F(000) = 520 |
Mr = 274.76 | Dx = 2.319 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 4.8149 (3) Å | Cell parameters from 4836 reflections |
b = 24.6603 (15) Å | θ = 6.6–62.7° |
c = 6.9111 (4) Å | µ = 3.40 mm−1 |
β = 106.418 (1)° | T = 293 K |
V = 787.14 (8) Å3 | Needle, colourless |
Z = 4 | 0.28 × 0.07 × 0.02 mm |
Bruker Smart Apex CCD area-detector diffractometer | 2295 independent reflections |
Radiation source: fine-focus sealed tube | 2165 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 31.6°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→7 |
Tmin = 0.729, Tmax = 0.934 | k = −34→34 |
6264 measured reflections | l = −10→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | All H-atom parameters refined |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0362P)2] |
S = 1.07 | (Δ/σ)max < 0.001 |
2295 reflections | Δρmax = 1.23 e Å−3 |
120 parameters | Δρmin = −0.81 e Å−3 |
7 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.50 (3) |
C6H5O3PSn | V = 787.14 (8) Å3 |
Mr = 274.76 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 4.8149 (3) Å | µ = 3.40 mm−1 |
b = 24.6603 (15) Å | T = 293 K |
c = 6.9111 (4) Å | 0.28 × 0.07 × 0.02 mm |
β = 106.418 (1)° |
Bruker Smart Apex CCD area-detector diffractometer | 2295 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2165 reflections with I > 2σ(I) |
Tmin = 0.729, Tmax = 0.934 | Rint = 0.038 |
6264 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | All H-atom parameters refined |
wR(F2) = 0.066 | Δρmax = 1.23 e Å−3 |
S = 1.07 | Δρmin = −0.81 e Å−3 |
2295 reflections | Absolute structure: Flack (1983) |
120 parameters | Absolute structure parameter: 0.50 (3) |
7 restraints |
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. Mean-plane data from final SHELXL refinement run: Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.4917 (0.0116) x - 5.0214 (0.0822) y + 2.9439 (0.0209) z = 1.8122 (0.0564) * 0.0073 (0.0045) C1 * -0.0024 (0.0049) C2 * -0.0045 (0.0059) C3 * 0.0065 (0.0063) C4 * -0.0016 (0.0071) C5 * -0.0053 (0.0065) C6 0.1225 (0.0093) P1 - 0.0686 (0.0123) O3 Rms deviation of fitted atoms = 0.0051 |
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 | 1.10170 (6) | 0.446853 (9) | 0.92033 (6) | 0.02331 (8) | |
P1 | 0.7106 (2) | 0.55920 (4) | 0.76814 (16) | 0.0210 (2) | |
O1 | 0.9214 (6) | 0.52416 (12) | 0.9234 (5) | 0.0272 (6) | |
O2 | 0.4205 (6) | 0.52912 (14) | 0.6892 (5) | 0.0291 (6) | |
O3 | 0.8275 (7) | 0.57804 (14) | 0.5967 (5) | 0.0295 (6) | |
C1 | 0.6549 (8) | 0.61930 (17) | 0.8977 (7) | 0.0241 (8) | |
C2 | 0.5193 (13) | 0.6161 (2) | 1.0496 (10) | 0.0426 (12) | |
H2 | 0.451 (12) | 0.5812 (13) | 1.069 (9) | 0.029 (16)* | |
C3 | 0.4941 (17) | 0.6627 (2) | 1.1584 (10) | 0.0545 (16) | |
H3 | 0.418 (13) | 0.657 (3) | 1.266 (6) | 0.042 (16)* | |
C4 | 0.6004 (16) | 0.7110 (3) | 1.1184 (12) | 0.0575 (17) | |
H4 | 0.595 (14) | 0.7421 (18) | 1.197 (9) | 0.049 (17)* | |
C5 | 0.733 (2) | 0.7136 (3) | 0.9632 (15) | 0.079 (3) | |
H5 | 0.79 (2) | 0.7480 (18) | 0.937 (15) | 0.09 (2)* | |
C6 | 0.7573 (18) | 0.6686 (2) | 0.8560 (11) | 0.0579 (18) | |
H6 | 0.890 (16) | 0.667 (4) | 0.779 (12) | 0.08 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.02194 (11) | 0.03032 (13) | 0.01749 (11) | 0.00397 (15) | 0.00530 (7) | −0.00193 (16) |
P1 | 0.0173 (4) | 0.0248 (5) | 0.0197 (5) | 0.0014 (3) | 0.0033 (3) | −0.0006 (4) |
O1 | 0.0246 (13) | 0.0308 (16) | 0.0234 (14) | 0.0050 (11) | 0.0023 (11) | 0.0012 (12) |
O2 | 0.0199 (13) | 0.0355 (17) | 0.0278 (15) | −0.0029 (12) | 0.0000 (11) | −0.0011 (13) |
O3 | 0.0322 (16) | 0.0349 (17) | 0.0244 (15) | 0.0048 (13) | 0.0127 (12) | 0.0014 (13) |
C1 | 0.024 (2) | 0.0257 (19) | 0.024 (2) | 0.0032 (13) | 0.0076 (16) | 0.0012 (16) |
C2 | 0.052 (3) | 0.041 (3) | 0.045 (3) | −0.007 (2) | 0.030 (3) | −0.005 (2) |
C3 | 0.086 (5) | 0.043 (3) | 0.051 (3) | −0.003 (3) | 0.047 (3) | −0.010 (3) |
C4 | 0.076 (4) | 0.038 (3) | 0.073 (4) | −0.004 (3) | 0.044 (4) | −0.018 (3) |
C5 | 0.136 (8) | 0.035 (3) | 0.099 (7) | −0.021 (4) | 0.086 (7) | −0.015 (4) |
C6 | 0.085 (5) | 0.038 (3) | 0.072 (5) | −0.007 (3) | 0.056 (4) | −0.001 (3) |
Sn1—O1 | 2.097 (3) | C1—C2 | 1.387 (8) |
Sn1—O3i | 2.125 (3) | C2—C3 | 1.398 (8) |
Sn1—O2ii | 2.133 (3) | C2—H2 | 0.944 (19) |
P1—O1 | 1.521 (3) | C3—C4 | 1.355 (9) |
P1—O3 | 1.521 (3) | C3—H3 | 0.93 (2) |
P1—O2 | 1.539 (3) | C4—C5 | 1.395 (9) |
P1—C1 | 1.791 (4) | C4—H4 | 0.94 (2) |
O2—Sn1iii | 2.133 (3) | C5—C6 | 1.359 (9) |
O3—Sn1iv | 2.125 (3) | C5—H5 | 0.93 (2) |
C1—C6 | 1.372 (7) | C6—H6 | 0.94 (2) |
Sn1···O2v | 3.226 (3) | Sn1···Sn1i | 4.3373 (3) |
Sn1···O1iv | 3.373 (3) | Sn1···Sn1iv | 4.3373 (3) |
Sn1···O3ii | 3.416 (3) | ||
O1—Sn1—O3i | 86.03 (13) | P1—O1—Sn1 | 134.83 (19) |
O1—Sn1—O2ii | 86.37 (12) | P1—O2—Sn1iii | 122.18 (19) |
O3i—Sn1—O2ii | 89.49 (12) | P1—O3—Sn1iv | 141.8 (2) |
O1—Sn1—O2v | 71.91 (10) | C6—C1—C2 | 119.0 (4) |
O3i—Sn1—O2v | 157.71 (11) | C6—C1—P1 | 121.0 (3) |
O2ii—Sn1—O2v | 86.03 (8) | C2—C1—P1 | 120.0 (3) |
O1—Sn1—O1iv | 80.18 (9) | C1—C2—C3 | 119.4 (5) |
O3i—Sn1—O1iv | 128.51 (10) | C1—C2—H2 | 115 (3) |
O2ii—Sn1—O1iv | 138.01 (11) | C3—C2—H2 | 126 (4) |
O2v—Sn1—O1iv | 51.98 (7) | C4—C3—C2 | 121.1 (5) |
O1—Sn1—O3ii | 122.98 (10) | C4—C3—H3 | 123 (4) |
O3i—Sn1—O3ii | 118.83 (13) | C2—C3—H3 | 116 (4) |
O2ii—Sn1—O3ii | 47.72 (10) | C3—C4—C5 | 118.6 (5) |
O2v—Sn1—O3ii | 73.01 (8) | C3—C4—H4 | 121 (4) |
O1iv—Sn1—O3ii | 110.14 (7) | C5—C4—H4 | 120 (4) |
O1—P1—O3 | 113.76 (18) | C6—C5—C4 | 120.6 (6) |
O1—P1—O2 | 109.53 (19) | C6—C5—H5 | 124 (6) |
O3—P1—O2 | 111.71 (18) | C4—C5—H5 | 115 (6) |
O1—P1—C1 | 106.39 (19) | C5—C6—C1 | 121.2 (5) |
O3—P1—C1 | 106.10 (19) | C5—C6—H6 | 121 (6) |
O2—P1—C1 | 109.07 (19) | C1—C6—H6 | 115 (6) |
O1—P1—C1—C2 | −65.5 (4) | O2ii—Sn1—O1—P1 | 162.3 (3) |
O2—P1—C1—C2 | 52.6 (5) | O3i—Sn1—O1—P1 | −108.0 (3) |
O3—P1—C1—C2 | 173.1 (4) | O1iii—Sn1iii—O2—P1 | 162.4 (2) |
Sn1—O1—P1—C1 | 177.1 (2) | O3vi—Sn1iii—O2—P1 | −111.6 (2) |
Sn1iii—O2—P1—C1 | 79.9 (3) | O1iv—Sn1iv—O3—P1 | 39.5 (3) |
Sn1iv—O3—P1—C1 | 149.7 (3) | O2v—Sn1iv—O3—P1 | −46.9 (3) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x+1, −y+1, z+1/2; (iii) x−1, −y+1, z−1/2; (iv) x, −y+1, z−1/2; (v) x+1, y, z; (vi) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C6H5O3PSn |
Mr | 274.76 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 293 |
a, b, c (Å) | 4.8149 (3), 24.6603 (15), 6.9111 (4) |
β (°) | 106.418 (1) |
V (Å3) | 787.14 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.40 |
Crystal size (mm) | 0.28 × 0.07 × 0.02 |
Data collection | |
Diffractometer | Bruker Smart Apex CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.729, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6264, 2295, 2165 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.737 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.066, 1.07 |
No. of reflections | 2295 |
No. of parameters | 120 |
No. of restraints | 7 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 1.23, −0.81 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.50 (3) |
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—O1 | 2.097 (3) | P1—O3 | 1.521 (3) |
Sn1—O3i | 2.125 (3) | P1—O2 | 1.539 (3) |
Sn1—O2ii | 2.133 (3) | P1—C1 | 1.791 (4) |
P1—O1 | 1.521 (3) | ||
Sn1···O2iii | 3.226 (3) | Sn1···Sn1i | 4.3373 (3) |
Sn1···O1iv | 3.373 (3) | Sn1···Sn1iv | 4.3373 (3) |
Sn1···O3ii | 3.416 (3) | ||
O1—Sn1—O3i | 86.03 (13) | O1—P1—C1 | 106.39 (19) |
O1—Sn1—O2ii | 86.37 (12) | O3—P1—C1 | 106.10 (19) |
O3i—Sn1—O2ii | 89.49 (12) | O2—P1—C1 | 109.07 (19) |
O1—P1—O3 | 113.76 (18) | P1—O1—Sn1 | 134.83 (19) |
O1—P1—O2 | 109.53 (19) | P1—O2—Sn1v | 122.18 (19) |
O3—P1—O2 | 111.71 (18) | P1—O3—Sn1iv | 141.8 (2) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x+1, −y+1, z+1/2; (iii) x+1, y, z; (iv) x, −y+1, z−1/2; (v) x−1, −y+1, z−1/2. |
We are currently interested in the synthesis and characterization of extended germanates and stannates, the primary target being new materials for ion-exchange and catalytic applications. Using both traditional organic amine and non-traditional templating agents, we have a discovered a series of framework and lower dimensionality materials based on lower group 14 metals (Salami et al., 2001). We name these new materials BING-n, where BING is an acronym for the State University of New York (SUNY) at Binghamton, and n stands for a particular material.
Cheetham and coworkers have recently described a series of tin oxalates (Ayyappan et al., 1998; Natarajan et al., 1999) and tin phosphates (Natarajan & Cheetham, 1997; Natarajan et al., 1998; Ayyappan et al., 2000; Liu et al., 2000). The latter contain interlayer or extra-framework organic ammonium groups. Cheetham and coworkers have also recently reported a tin oxalate methyl phosphonate (Adair et al., 1998). Here, we describe the crystal structure of BING-3, a layered tin phenylphosphonate, (I). \sch
Compound (I) was synthesized in a non-aqueous pyridine solvent containing tin oxalate, hydrogen fluoride and phenylphosphonic acid. The structure consists of a tin phosphonate layer, where the Sn and P centres are three-coordinate in the plane of the layer via O atoms (Figs. 1 and 2). The fourth coordination site for the P atoms is an out-of-plane phenyl group; these groups alternate above and below the plane of the layer (Fig. 1). The Sn centres have pyramidal coordination, with three O atoms bridging to neighbouring P centres. A lone pair of electrons is also present on the Sn atom. Oxalate is not present in the structure and was obviously eliminated from the Sn reagent under the synthetic conditions used.
The P and Sn atoms alternate in the layer and, with respect to the metal atoms, define a graphite-like arrangement of edge-sharing six-membered rings in the ac plane (Fig. 2). The interdigitated phenyl rings create a hydrophobic interlayer region that caps and separates the layers. The asymmetric unit is relatively simple, containing only one Sn atom and one P atom (Fig. 3).
Due to our interest in open-framework paramagnetic materials for magnetic-based applications, we have also performed the analogous synthesis with an equimolar amount of managanese sulfate in place of the tin oxalate. We obtained a crystalline material, [Mn(C6H5O3P)], whose crystal structure turned out to have been previously reported by Mallouk and coworkers (Cao et al., 1988). Due to the success of both systems in making layered materials solvothermally, we are currently investigating Sn—Mn mixed-metal systems as a way of controlling paramagnetic site separation and therefore the magnetic properties of the resultant materials.