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Poly­[tin(II)-μ-phenyl­phospho­nato], [Sn(C6H5O3P)]n, was synthesized solvothermally at 423 K and crystallized in the monoclinic system, space group Cc. The inorganic layers consist of alternating pyramidal Sn and tetrahedral P centers, joined by doubly bridging O atoms. The corner-sharing SnO3 and PO3C6H5 polyhedra define a corrugated layer of six-membered rings. The layers are connected along the unique b axis by interdigitated phenyl rings of the phenyl­phospho­nate groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101010034/br1323sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101010034/br1323Isup2.hkl
Contains datablock I

CCDC reference: 173356

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The crystallographic projection of (I) along a, highlighting the separation of the tin phosphonate layers by interdigitated phenyl rings (Sn - largest grey circles, P - medium grey circles, O - darkest grey circles, C - small grey circles and H - smallest grey circles).
[Figure 2] Fig. 2. The b projection of one tin phosphonate layer of (I), with H atoms omitted for clarity. Shading scheme as for Fig. 1.
[Figure 3] Fig. 3. The molecular structure of (I), with the atom-labelling scheme and 50% probability displacement ellipsoids [symmetry codes: (i) 1 + x, 1 - y, 1/2 + z; (ii) x, 1 - y, 1/2 + z]. H atoms are shown as small spheres of arbitrary radii.
Tin(II) Phenyl Phosphonate top
Crystal data top
C6H5O3PSnF(000) = 520
Mr = 274.76Dx = 2.319 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 4.8149 (3) ÅCell parameters from 4836 reflections
b = 24.6603 (15) Åθ = 6.6–62.7°
c = 6.9111 (4) ŵ = 3.40 mm1
β = 106.418 (1)°T = 293 K
V = 787.14 (8) Å3Needle, colourless
Z = 40.28 × 0.07 × 0.02 mm
Data collection top
Bruker Smart Apex CCD area-detector
diffractometer
2295 independent reflections
Radiation source: fine-focus sealed tube2165 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ω scansθmax = 31.6°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 67
Tmin = 0.729, Tmax = 0.934k = 3434
6264 measured reflectionsl = 109
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)] = 0.029All H-atom parameters refined
wR(F2) = 0.066 w = 1/[σ2(Fo2) + (0.0362P)2]
S = 1.07(Δ/σ)max < 0.001
2295 reflectionsΔρmax = 1.23 e Å3
120 parametersΔρmin = 0.81 e Å3
7 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.50 (3)
Crystal data top
C6H5O3PSnV = 787.14 (8) Å3
Mr = 274.76Z = 4
Monoclinic, CcMo Kα radiation
a = 4.8149 (3) ŵ = 3.40 mm1
b = 24.6603 (15) ÅT = 293 K
c = 6.9111 (4) Å0.28 × 0.07 × 0.02 mm
β = 106.418 (1)°
Data collection top
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 = 0.934Rint = 0.038
6264 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029All H-atom parameters refined
wR(F2) = 0.066Δρmax = 1.23 e Å3
S = 1.07Δρmin = 0.81 e Å3
2295 reflectionsAbsolute structure: Flack (1983)
120 parametersAbsolute structure parameter: 0.50 (3)
7 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn11.10170 (6)0.446853 (9)0.92033 (6)0.02331 (8)
P10.7106 (2)0.55920 (4)0.76814 (16)0.0210 (2)
O10.9214 (6)0.52416 (12)0.9234 (5)0.0272 (6)
O20.4205 (6)0.52912 (14)0.6892 (5)0.0291 (6)
O30.8275 (7)0.57804 (14)0.5967 (5)0.0295 (6)
C10.6549 (8)0.61930 (17)0.8977 (7)0.0241 (8)
C20.5193 (13)0.6161 (2)1.0496 (10)0.0426 (12)
H20.451 (12)0.5812 (13)1.069 (9)0.029 (16)*
C30.4941 (17)0.6627 (2)1.1584 (10)0.0545 (16)
H30.418 (13)0.657 (3)1.266 (6)0.042 (16)*
C40.6004 (16)0.7110 (3)1.1184 (12)0.0575 (17)
H40.595 (14)0.7421 (18)1.197 (9)0.049 (17)*
C50.733 (2)0.7136 (3)0.9632 (15)0.079 (3)
H50.79 (2)0.7480 (18)0.937 (15)0.09 (2)*
C60.7573 (18)0.6686 (2)0.8560 (11)0.0579 (18)
H60.890 (16)0.667 (4)0.779 (12)0.08 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.02194 (11)0.03032 (13)0.01749 (11)0.00397 (15)0.00530 (7)0.00193 (16)
P10.0173 (4)0.0248 (5)0.0197 (5)0.0014 (3)0.0033 (3)0.0006 (4)
O10.0246 (13)0.0308 (16)0.0234 (14)0.0050 (11)0.0023 (11)0.0012 (12)
O20.0199 (13)0.0355 (17)0.0278 (15)0.0029 (12)0.0000 (11)0.0011 (13)
O30.0322 (16)0.0349 (17)0.0244 (15)0.0048 (13)0.0127 (12)0.0014 (13)
C10.024 (2)0.0257 (19)0.024 (2)0.0032 (13)0.0076 (16)0.0012 (16)
C20.052 (3)0.041 (3)0.045 (3)0.007 (2)0.030 (3)0.005 (2)
C30.086 (5)0.043 (3)0.051 (3)0.003 (3)0.047 (3)0.010 (3)
C40.076 (4)0.038 (3)0.073 (4)0.004 (3)0.044 (4)0.018 (3)
C50.136 (8)0.035 (3)0.099 (7)0.021 (4)0.086 (7)0.015 (4)
C60.085 (5)0.038 (3)0.072 (5)0.007 (3)0.056 (4)0.001 (3)
Geometric parameters (Å, º) top
Sn1—O12.097 (3)C1—C21.387 (8)
Sn1—O3i2.125 (3)C2—C31.398 (8)
Sn1—O2ii2.133 (3)C2—H20.944 (19)
P1—O11.521 (3)C3—C41.355 (9)
P1—O31.521 (3)C3—H30.93 (2)
P1—O21.539 (3)C4—C51.395 (9)
P1—C11.791 (4)C4—H40.94 (2)
O2—Sn1iii2.133 (3)C5—C61.359 (9)
O3—Sn1iv2.125 (3)C5—H50.93 (2)
C1—C61.372 (7)C6—H60.94 (2)
Sn1···O2v3.226 (3)Sn1···Sn1i4.3373 (3)
Sn1···O1iv3.373 (3)Sn1···Sn1iv4.3373 (3)
Sn1···O3ii3.416 (3)
O1—Sn1—O3i86.03 (13)P1—O1—Sn1134.83 (19)
O1—Sn1—O2ii86.37 (12)P1—O2—Sn1iii122.18 (19)
O3i—Sn1—O2ii89.49 (12)P1—O3—Sn1iv141.8 (2)
O1—Sn1—O2v71.91 (10)C6—C1—C2119.0 (4)
O3i—Sn1—O2v157.71 (11)C6—C1—P1121.0 (3)
O2ii—Sn1—O2v86.03 (8)C2—C1—P1120.0 (3)
O1—Sn1—O1iv80.18 (9)C1—C2—C3119.4 (5)
O3i—Sn1—O1iv128.51 (10)C1—C2—H2115 (3)
O2ii—Sn1—O1iv138.01 (11)C3—C2—H2126 (4)
O2v—Sn1—O1iv51.98 (7)C4—C3—C2121.1 (5)
O1—Sn1—O3ii122.98 (10)C4—C3—H3123 (4)
O3i—Sn1—O3ii118.83 (13)C2—C3—H3116 (4)
O2ii—Sn1—O3ii47.72 (10)C3—C4—C5118.6 (5)
O2v—Sn1—O3ii73.01 (8)C3—C4—H4121 (4)
O1iv—Sn1—O3ii110.14 (7)C5—C4—H4120 (4)
O1—P1—O3113.76 (18)C6—C5—C4120.6 (6)
O1—P1—O2109.53 (19)C6—C5—H5124 (6)
O3—P1—O2111.71 (18)C4—C5—H5115 (6)
O1—P1—C1106.39 (19)C5—C6—C1121.2 (5)
O3—P1—C1106.10 (19)C5—C6—H6121 (6)
O2—P1—C1109.07 (19)C1—C6—H6115 (6)
O1—P1—C1—C265.5 (4)O2ii—Sn1—O1—P1162.3 (3)
O2—P1—C1—C252.6 (5)O3i—Sn1—O1—P1108.0 (3)
O3—P1—C1—C2173.1 (4)O1iii—Sn1iii—O2—P1162.4 (2)
Sn1—O1—P1—C1177.1 (2)O3vi—Sn1iii—O2—P1111.6 (2)
Sn1iii—O2—P1—C179.9 (3)O1iv—Sn1iv—O3—P139.5 (3)
Sn1iv—O3—P1—C1149.7 (3)O2v—Sn1iv—O3—P146.9 (3)
Symmetry codes: (i) x, y+1, z+1/2; (ii) x+1, y+1, z+1/2; (iii) x1, y+1, z1/2; (iv) x, y+1, z1/2; (v) x+1, y, z; (vi) x1, y, z.

Experimental details

Crystal data
Chemical formulaC6H5O3PSn
Mr274.76
Crystal system, space groupMonoclinic, Cc
Temperature (K)293
a, b, c (Å)4.8149 (3), 24.6603 (15), 6.9111 (4)
β (°) 106.418 (1)
V3)787.14 (8)
Z4
Radiation typeMo Kα
µ (mm1)3.40
Crystal size (mm)0.28 × 0.07 × 0.02
Data collection
DiffractometerBruker Smart Apex CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.729, 0.934
No. of measured, independent and
observed [I > 2σ(I)] reflections
6264, 2295, 2165
Rint0.038
(sin θ/λ)max1)0.737
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.066, 1.07
No. of reflections2295
No. of parameters120
No. of restraints7
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)1.23, 0.81
Absolute structureFlack (1983)
Absolute structure parameter0.50 (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.

Selected geometric parameters (Å, º) top
Sn1—O12.097 (3)P1—O31.521 (3)
Sn1—O3i2.125 (3)P1—O21.539 (3)
Sn1—O2ii2.133 (3)P1—C11.791 (4)
P1—O11.521 (3)
Sn1···O2iii3.226 (3)Sn1···Sn1i4.3373 (3)
Sn1···O1iv3.373 (3)Sn1···Sn1iv4.3373 (3)
Sn1···O3ii3.416 (3)
O1—Sn1—O3i86.03 (13)O1—P1—C1106.39 (19)
O1—Sn1—O2ii86.37 (12)O3—P1—C1106.10 (19)
O3i—Sn1—O2ii89.49 (12)O2—P1—C1109.07 (19)
O1—P1—O3113.76 (18)P1—O1—Sn1134.83 (19)
O1—P1—O2109.53 (19)P1—O2—Sn1v122.18 (19)
O3—P1—O2111.71 (18)P1—O3—Sn1iv141.8 (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, z1/2; (v) x1, y+1, z1/2.
 

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