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N-(Phospho­no­methyl)­glycine, glyphosate, reacts with bis­(tri­butyl­tin) oxide to form a ligand–tin (1:3) complex in which all five O atoms are coordinated to tin. The complex, [Sn3(C4H9)9(C3H5NO5P)], is polymeric, with the glyphosate and two tri­butyl­tin groups forming a two-dimensional network and with the third Sn atom alternately above and below the plane of the net. The Sn atoms in the network have a trigonal-bipyramidal coordination, with O atoms in the axial positions and C atoms in the equatorial positions; the pendant tri­butyl­tin group is tetrahedrally coordinated to one O atom and to three butyl groups. Sn—O distances vary from 2.030 (3) to 2.408 (3) Å. The Sn—O distances for O atoms trans to carboxyl­ate groups are shorter than those trans to phos­phonate groups and dSn—O decreases with increasing dC/P—OSn—O ≃ −4.6ΔC/P—O). The amino N atom in the ligand is neither protonated nor involved in coordination to the Sn atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100018898/av1061sup1.cif
Contains datablocks ntu, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100018898/av1061Isup2.hkl
Contains datablock I

CCDC reference: 162548

Comment top

Organotin(IV) compounds have been used as marine anti-fouling agents, agricultural fungicides, miticides and surface disinfectants (Davies & Smith, 1982). An interesting development is the synthesis of organotin compounds in which the organotin moiety is bonded to ligands which exhibit biocidal activity. One such ligand system is the widely used commercial herbicide, glyphosate, N-(phosphonomethyl)glycine, which forms complexes in which the carboxylate oxygen atoms, the phosphonate oxygen atoms or the nitrogen atom can coordinate to a metal atom (Appleton et al., 1994; Franz et al., 1997). The incorporation of organotin and phosphorus portions in one molecule leads to the possibility that each fragment may make a contribution to the compound's overall biocidal activity. We here report the synthesis and the crystal structure of the glyphosphate complex with bistributyltin oxide, (I). \sch

Regardless of the proportions of glyphosate and bis(tri-n-butyltin)oxide used, we obtained a product of which was shown by elemental microanalysis to be the 3:1 (tin:ligand) adduct (n-Bu3Sn)3(OCOCH2NHCH2PO3). The structure determination showed all five oxygen atoms of the glyphosate to be bonded to tin atoms (Fig. 1) to give a polymeric structure. The glyphosate moiety, together with Sn1 and Sn2, forms a two-dimensional network with the Sn3 atoms situated alternately above and below the plane of the network (Fig. 2). Sn1 and Sn2 are penta-coordinated to two oxygen atoms and to three n-butyl groups at the corners of a trigonal bipyramid with the oxygen atoms in the axial positions whereas Sn3 is tetrahedrally coordinated to one oxygen atom and to three n-butyl groups. The n-butyl groups around Sn2 are disordered. There is a wide spread in the Sn—O bond distances, 2.030 (3) to 2.408 (3) Å, the P—O distances are in the range 1.508 (3)–1.543 (3) Å and the C—O distances are 1.239 (4) and 1.263 (4) Å. The Sn—O distances for oxygen atoms trans to carboxylate groups are shorter than those trans to phosphonate groups and dSn—O decreases with increasing dC/P—OSn—O simeq -4.6ΔC/P—O). Only one hydrogen atom was observed on the nitrogen atom, in agreement with the observation of an NH stretching frequency of 3300 cm-1 together with the absence of ν(+NH)bands. The intramolecular contacts N1···O5(-1 - x, 1/2 + y,1 - z) [2.643 (4) Å] and N1···O3(-1 - x, 1/2 + y, 1 - z) [3.018 (4) Å] can be attributed to hydrogen bonding. The backbone of the glyphosate group is a nonplanar zigzag chain; O1—P1—C1—N1—C2 and N1—C2—C3—O4 form nearly planar groups with the C1—N1—C2—C3 torsion angle -154.1 (3)°. Comparison of the IR-spectra with that observed by Rajendram & Hoggard (1994) for glyphosate shows that the symmetric and asymmetric C—O stretching vibrations are lowered on bonding, from 1734 to 1578 cm-1 and from 1485 to 1404 cm-1. Similarly the symmetric and asymmetric P—O stretching frequencies and the O—P—O bending-stretching frequencies are lowered from 1160, 917 and 1095 cm-1 to 1138, 877 and 1065 cm-1. The sharp ν(N—H) stretching band observed at 3300 cm-1 (3230 cm-1 for glyphosate) and the absence of ν(+NH) indicate that the N amino atom in the ligand is neither protonated nor involved in coordination to the tin atoms. Δν = νasym(OCO) - νsym(OCO) is expected to be about 200 cm-1 for a bridging of chelating carboxyl group (Deacon & Phillips, 1980; Micera et al., 1984), the value found here is 174 cm-1.

Related literature top

For related literature, see: Appleton et al. (1994); Davies & Smith (1982); Deacon & Phillips (1980); Franz et al. (1997); Micera et al. (1984); Rajendram & Hoggard (1994).

Experimental top

Bis(tri-n-butyltin)oxide was purchased from Aldrich Chemical Co. and used without further purification. N-(Phosphonomethyl)glycine was isolated by acidifying a solution of commercial "Roundup" with concentrated HCl and allowing the free acid to crystallize. IR spectra were recorded as KBr pellets on a Perkin-Elmer Model 1725 F T—IR instrument. The elemental analyses were performed at the School of Chemical Sciences, Universiti Sains Malaysia, Penang. To a stirred solution of glyphosate (0.85 g, 5 mmol) in 95% ethanol (50 ml) was added dicyclohexylamine (1 ml) followed by bis(tri-n-butyltin)oxide (4.5 g, 7.5 mmol). After refluxing for 3–4 h, the mixture was concentrated to ca 10 ml with a rotatory evaporator before allowing it to stand in the freezer overnight. A white solid (3.1 g, 60%) was obtained on filtration. Recrystallization in methanol afforded crystals (m.p. 359–361 K) of tris-tri-n-butyltin N-(phosphonomethyl)glycinate which were suitable for X-ray crystallographic studies. Elemental analysis: Calculated (found) for C39H86NO5PSn3: C 45.20 (45.23), H 8.38 (8.43), N 1.35 (1.18%). IR (KBr,ν, cm-1) 1578 s (CO2asym); 1404 (CO2sym); 1138 (PO3asym); 877 (PO3sym); 1065 (O—P—O bending-stretching); 3300 (NH stretch).

Refinement top

The butyl groups coordinated to Sn2 were disordered and were modelled by pairs of isotropic atoms with occupation 0.5. The hydrogen atoms were constrained to have C—H = 0.95 Å and Uiso = 1.2Ueq for the atom to which they are attached. The weighting scheme employed was w = 1/[σcs(F2)+0.03 F2]2. The largest peaks and holes in the final difference map were close to the tin atoms.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Cascarano et al., 1996) and KRYSTAL (Hazell, 1995); program(s) used to refine structure: modified ORFLS (Busing et al., 1962) and KRYSTAL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL; software used to prepare material for publication: KRYSTAL.

Figures top
[Figure 1] Fig. 1. View of the adduct showing the labelling of the non-H atoms. Displacement ellipsoids are shown at 50% probability levels. The disordered butyl groups C16A—C27A are shown bonded to Sn2 while C16B—C27B are shown bonded to Sn2ii. Symmetry codes: (i) x - 1, y, z; (ii) x - 1, 1/2 + y, 1 - z.
[Figure 2] Fig. 2. Packing diagram showing part of the two-dimensional network, tin atoms are represented by large circles, the butyl groups have been ommitted.
insert name here top
Crystal data top
[Sn3(C4H9)9(C3H5O5P)]F(000) = 1064
Mr = 1036.20Dx = 1.424 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2y1Cell parameters from 6517 reflections
a = 10.2144 (7) Åθ = 1.9–29.8°
b = 18.018 (1) ŵ = 1.61 mm1
c = 13.1304 (9) ÅT = 120 K
β = 90.177 (1)°Needle, colourless
V = 2416.6 (2) Å30.47 × 0.16 × 0.15 mm
Z = 2
Data collection top
Siemens SMART CCD
diffractometer
13624 independent reflections
Radiation source: x-ray tube12628 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω rotation scans with narrow framesθmax = 29.8°, θmin = 1.9°
Absorption correction: integration
(XPREP; Siemens, 1995)
h = 1414
Tmin = 0.501, Tmax = 0.799k = 2525
28299 measured reflectionsl = 1818
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: fullWeighting scheme based on measured s.u.'s
R[F2 > 2σ(F2)] = 0.029(Δ/σ)max = 0.002
wR(F2) = 0.071Δρmax = 2.2 (1) e Å3
S = 1.12Δρmin = 1.1 (1) e Å3
12628 reflectionsExtinction correction: B-C type 1 Lorentzian isotropic Becker and Coppens (1974)
431 parametersExtinction coefficient: 56 (6)
0 restraintsAbsolute structure: Rogers (1981)
0 constraintsRogers parameter: 0.73 (3)
Crystal data top
[Sn3(C4H9)9(C3H5O5P)]V = 2416.6 (2) Å3
Mr = 1036.20Z = 2
Monoclinic, P21Mo Kα radiation
a = 10.2144 (7) ŵ = 1.61 mm1
b = 18.018 (1) ÅT = 120 K
c = 13.1304 (9) Å0.47 × 0.16 × 0.15 mm
β = 90.177 (1)°
Data collection top
Siemens SMART CCD
diffractometer
13624 independent reflections
Absorption correction: integration
(XPREP; Siemens, 1995)
12628 reflections with I > 2σ(I)
Tmin = 0.501, Tmax = 0.799Rint = 0.032
28299 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.071Δρmax = 2.2 (1) e Å3
S = 1.12Δρmin = 1.1 (1) e Å3
12628 reflectionsAbsolute structure: Rogers (1981)
431 parametersRogers parameter: 0.73 (3)
0 restraints
Special details top

Refinement. Sfls: Fsd calc weight full matrix

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.13286 (2)0.077700.57743 (2)0.0182 (1)
Sn20.30283 (2)0.21062 (2)0.50253 (2)0.0215 (1)
Sn30.31729 (2)0.09175 (2)0.83472 (2)0.0299 (1)
P10.19697 (8)0.12219 (5)0.60470 (7)0.0196 (4)
O10.0614 (2)0.1294 (1)0.5600 (2)0.022 (1)
O20.1898 (2)0.1193 (1)0.7220 (2)0.028 (1)
O30.2918 (2)0.3182 (1)0.4305 (2)0.027 (1)
O40.3164 (2)0.0881 (2)0.5750 (2)0.036 (2)
O50.3427 (2)0.0341 (1)0.5918 (2)0.026 (1)
N10.6002 (3)0.0286 (2)0.6094 (2)0.022 (1)
C10.7312 (3)0.0352 (2)0.5655 (3)0.023 (2)
C20.5328 (3)0.0392 (2)0.5792 (3)0.026 (2)
C30.3847 (3)0.0316 (2)0.5827 (3)0.024 (2)
C40.1346 (4)0.0412 (2)0.4220 (3)0.031 (2)
C50.0060 (4)0.0422 (2)0.3657 (3)0.030 (2)
C60.0137 (4)0.0197 (3)0.2546 (3)0.038 (2)
C70.1156 (6)0.0221 (4)0.2006 (4)0.066 (4)
C80.2155 (4)0.1841 (2)0.6090 (3)0.028 (2)
C90.1506 (5)0.2296 (2)0.6932 (3)0.043 (3)
C100.2206 (7)0.3041 (3)0.7136 (4)0.060 (3)
C110.2168 (8)0.3563 (3)0.6241 (4)0.074 (4)
C120.0736 (3)0.0043 (2)0.6973 (3)0.024 (2)
C130.1255 (4)0.0237 (2)0.8011 (3)0.033 (2)
C140.0780 (5)0.0294 (2)0.8843 (3)0.039 (2)
C150.1311 (6)0.0117 (3)0.9892 (4)0.057 (3)
C280.3272 (4)0.0264 (3)0.8453 (3)0.036 (2)
C290.4670 (4)0.0560 (3)0.8529 (3)0.036 (2)
C300.4757 (4)0.1401 (3)0.8617 (3)0.038 (2)
C310.6140 (5)0.1687 (3)0.8683 (4)0.048 (3)
C320.2067 (4)0.1373 (3)0.9587 (3)0.049 (3)
C330.1218 (5)0.2050 (3)0.9344 (3)0.044 (2)
C340.0431 (5)0.2332 (3)1.0246 (4)0.050 (3)
C350.0500 (6)0.2948 (3)0.9959 (5)0.064 (3)
C360.4932 (4)0.1521 (3)0.8063 (3)0.038 (2)
C370.5532 (4)0.1851 (3)0.9027 (4)0.046 (3)
C380.5912 (4)0.1273 (3)0.9807 (4)0.049 (3)
C390.6601 (5)0.1593 (4)1.0756 (4)0.060 (3)
C16A0.1080 (6)0.2113 (4)0.5524 (5)0.023 (1)*0.5
C17A0.0853 (8)0.2412 (5)0.6615 (6)0.035 (2)*0.5
C18A0.0576 (9)0.2530 (5)0.6888 (7)0.036 (2)*0.5
C19A0.1390 (11)0.1812 (6)0.6870 (8)0.045 (2)*0.5
C16B0.1416 (7)0.2177 (4)0.6106 (6)0.026 (1)*0.5
C17B0.0114 (7)0.1865 (4)0.5743 (6)0.030 (2)*0.5
C18B0.0952 (9)0.1819 (5)0.6554 (7)0.036 (2)*0.5
C19B0.1342 (9)0.2552 (5)0.7019 (7)0.040 (2)*0.5
C20A0.4723 (7)0.2447 (4)0.5967 (6)0.028 (1)*0.5
C21A0.5072 (8)0.3270 (5)0.6109 (7)0.029 (2)*0.5
C22A0.4129 (9)0.3695 (6)0.6732 (7)0.038 (2)*0.5
C23A0.4619 (11)0.4476 (7)0.6923 (8)0.047 (2)*0.5
C20B0.4934 (7)0.2268 (4)0.5567 (6)0.027 (1)*0.5
C21B0.5302 (7)0.3061 (4)0.5826 (6)0.026 (1)*0.5
C22B0.4495 (9)0.3388 (5)0.6649 (7)0.038 (2)*0.5
C23B0.4921 (12)0.4160 (7)0.6968 (9)0.058 (3)*0.5
C24A0.3607 (7)0.1559 (4)0.3663 (6)0.029 (2)*0.5
C25A0.2686 (9)0.1644 (5)0.2777 (7)0.038 (2)*0.5
C26A0.2941 (10)0.1114 (5)0.1893 (8)0.044 (2)*0.5
C27A0.4311 (11)0.1159 (6)0.1500 (9)0.053 (2)*0.5
C24B0.2683 (8)0.1580 (4)0.3582 (6)0.032 (2)*0.5
C25B0.3963 (8)0.1339 (5)0.3045 (6)0.035 (2)*0.5
C26B0.3716 (10)0.1032 (5)0.1964 (7)0.042 (2)*0.5
C27B0.5017 (9)0.0884 (5)0.1455 (7)0.042 (2)*0.5
HN10.54960.06990.58790.027*
H1a0.72560.03380.49330.028*
H1b0.78410.00470.58850.028*
H2a0.55790.07800.62410.031*
H2b0.55830.05140.51170.031*
H4a0.16600.00840.42130.037*
H4b0.19380.07220.38570.037*
H5a0.02810.09130.36890.036*
H5b0.05230.00920.39930.036*
H6a0.04660.02960.25100.046*
H6b0.07230.05230.22070.046*
H7a0.11080.00790.13100.079*
H7b0.14850.07130.20420.079*
H7c0.17430.01060.23450.079*
H8a0.21180.21240.54800.034*
H8b0.30430.17660.62760.034*
H9a0.15090.20130.75420.052*
H9b0.06280.23970.67390.052*
H10a0.30950.29420.72970.073*
H10b0.17930.32760.77000.073*
H11a0.25990.40210.63670.089*
H11b0.12790.36620.60800.089*
H11c0.25810.33280.56780.089*
H12a0.10310.04420.68070.028*
H12b0.01930.00460.70080.028*
H13a0.09770.07250.81790.040*
H13b0.21850.02210.79880.040*
H14a0.10450.07830.86660.047*
H14b0.01480.02710.88710.047*
H15a0.10160.04471.04090.069*
H15b0.10470.03721.00700.069*
H15c0.22400.01400.98640.069*
H28a0.28050.04160.90420.044*
H28b0.28710.04700.78640.044*
H29a0.51320.04110.79370.043*
H29b0.50720.03480.91140.043*
H30a0.43020.15510.92130.046*
H30b0.43500.16150.80350.046*
H31a0.61950.22120.87380.057*
H31b0.65950.15370.80870.057*
H31c0.65470.14740.92650.057*
H32a0.15080.09940.98350.058*
H32b0.26700.15131.01050.058*
H33a0.17720.24390.91160.052*
H33b0.06240.19200.88150.052*
H34a0.00600.19311.05180.061*
H34b0.10220.25131.07490.061*
H35a0.09910.31241.05230.076*
H35b0.00090.33490.96870.076*
H35c0.10900.27680.94570.076*
H36a0.55510.11950.77630.046*
H36b0.47400.19140.76030.046*
H37a0.62940.21210.88430.055*
H37b0.49130.21780.93260.055*
H38a0.51410.10241.00220.059*
H38b0.64870.09280.94930.059*
H39a0.68400.12291.12470.072*
H39b0.73730.18411.05410.072*
H39c0.60270.19381.10700.072*
H16Aa0.05910.24130.50680.027*0.5
H16Ab0.07640.16170.55000.027*0.5
H17Aa0.12140.20670.70840.042*0.5
H17Ab0.12940.28740.66770.042*0.5
H18Aa0.06220.27350.75540.044*0.5
H18Ab0.09430.28690.64140.044*0.5
H19Aa0.22850.18850.70410.054*0.5
H19Ab0.13440.16060.62040.054*0.5
H19Ac0.10230.14720.73440.054*0.5
H16Ba0.16610.19130.67020.032*0.5
H16Bb0.12880.26850.62690.032*0.5
H17Ba0.01960.21730.52080.036*0.5
H17Bb0.02640.13780.54890.036*0.5
H18Ba0.17070.16050.62520.043*0.5
H18Bb0.06460.15060.70840.043*0.5
H19Ba0.20060.25230.75250.048*0.5
H19Bb0.05860.27660.73200.048*0.5
H19Bc0.16470.28650.64880.048*0.5
H20Aa0.45730.22520.66290.034*0.5
H20Ab0.54720.22170.56760.034*0.5
H21Aa0.59040.32980.64270.035*0.5
H21Ab0.51180.34940.54540.035*0.5
H22Aa0.33160.37190.63850.045*0.5
H22AB0.40110.34510.73670.045*0.5
H23Aa0.40130.47500.73240.056*0.5
H23Ab0.54320.44520.72700.056*0.5
H23Ac0.47370.47210.62880.056*0.5
H20Ba0.50330.19780.61660.032*0.5
H20Bb0.55250.20970.50590.032*0.5
H21Ba0.61920.30680.60340.032*0.5
H21Bb0.52030.33560.52320.032*0.5
H22Ba0.36150.34140.64190.046*0.5
H22Bb0.45420.30710.72260.046*0.5
H23Ba0.44030.43700.74960.070*0.5
H23Bb0.58010.41340.71970.070*0.5
H23Bc0.48740.44760.63910.070*0.5
H24Aa0.44360.17510.34640.035*0.5
H24Ab0.36870.10440.38080.035*0.5
H25Aa0.18200.15620.30160.046*0.5
H25Ab0.27610.21370.25280.046*0.5
H26Aa0.27790.06210.21180.053*0.5
H26Ab0.23580.12330.13540.053*0.5
H27Aa0.44700.08290.09490.064*0.5
H27Ab0.44730.16520.12750.064*0.5
H27Ac0.48940.10400.20380.064*0.5
H24Ba0.21540.11530.36900.039*0.5
H24Bb0.22330.19190.31530.039*0.5
H25Ba0.45270.17570.29950.042*0.5
H25Bb0.43710.09640.34410.042*0.5
H26Ba0.32310.05830.20080.050*0.5
H26Bb0.32380.13850.15780.050*0.5
H27Ba0.48650.06950.07900.051*0.5
H27Bb0.55020.13330.14110.051*0.5
H27Bc0.54960.05310.18410.051*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0147 (1)0.0171 (1)0.0229 (1)0.0012 (1)0.0029 (1)0.0022 (1)
Sn20.0174 (1)0.0239 (1)0.0230 (1)0.0053 (1)0.0003 (1)0.0019 (1)
Sn30.0197 (1)0.0451 (2)0.0248 (1)0.0025 (1)0.0001 (1)0.0022 (1)
P10.0154 (3)0.0194 (4)0.0242 (4)0.0031 (3)0.0035 (3)0.0010 (3)
O10.017 (1)0.021 (1)0.029 (1)0.003 (1)0.003 (1)0.000 (1)
O20.022 (1)0.036 (1)0.025 (1)0.002 (1)0.003 (1)0.002 (1)
O30.021 (1)0.023 (1)0.037 (1)0.006 (1)0.006 (1)0.002 (1)
O40.020 (1)0.034 (1)0.053 (2)0.003 (1)0.002 (1)0.021 (1)
O50.016 (1)0.029 (1)0.035 (1)0.004 (1)0.004 (1)0.003 (1)
N10.013 (1)0.025 (1)0.029 (2)0.000 (1)0.002 (1)0.007 (1)
C10.017 (1)0.023 (2)0.030 (2)0.001 (1)0.001 (1)0.006 (1)
C20.017 (1)0.029 (2)0.032 (2)0.000 (1)0.002 (1)0.010 (1)
C30.017 (1)0.035 (2)0.019 (2)0.000 (1)0.004 (1)0.008 (1)
C40.027 (2)0.041 (2)0.026 (2)0.010 (1)0.002 (1)0.001 (2)
C50.025 (2)0.043 (2)0.022 (2)0.002 (1)0.001 (1)0.005 (2)
C60.046 (2)0.046 (2)0.022 (2)0.000 (2)0.000 (2)0.002 (2)
C70.049 (3)0.121 (6)0.028 (3)0.022 (3)0.004 (2)0.002 (3)
C80.028 (2)0.025 (2)0.033 (2)0.007 (1)0.007 (1)0.007 (1)
C90.074 (3)0.026 (2)0.029 (2)0.019 (2)0.002 (2)0.000 (2)
C100.109 (5)0.041 (3)0.032 (2)0.040 (3)0.000 (3)0.006 (2)
C110.155 (7)0.024 (2)0.042 (3)0.028 (3)0.003 (3)0.002 (2)
C120.019 (1)0.023 (2)0.030 (2)0.001 (1)0.001 (1)0.004 (1)
C130.040 (2)0.029 (2)0.031 (2)0.003 (2)0.000 (2)0.002 (2)
C140.054 (3)0.038 (2)0.026 (2)0.008 (2)0.002 (2)0.006 (2)
C150.086 (4)0.055 (3)0.030 (2)0.019 (3)0.004 (2)0.006 (2)
C280.027 (2)0.052 (3)0.031 (2)0.005 (2)0.001 (2)0.003 (2)
C290.027 (2)0.052 (2)0.030 (2)0.001 (2)0.003 (2)0.004 (2)
C300.035 (2)0.049 (2)0.031 (2)0.001 (2)0.003 (2)0.007 (2)
C310.047 (3)0.051 (3)0.046 (3)0.009 (2)0.007 (2)0.006 (2)
C320.034 (2)0.087 (4)0.026 (2)0.005 (2)0.004 (2)0.003 (2)
C330.052 (3)0.044 (2)0.035 (2)0.012 (2)0.017 (2)0.009 (2)
C340.036 (2)0.075 (3)0.041 (3)0.007 (2)0.006 (2)0.019 (2)
C350.072 (4)0.050 (3)0.069 (3)0.005 (3)0.020 (3)0.024 (3)
C360.029 (2)0.049 (2)0.037 (2)0.006 (2)0.001 (2)0.007 (2)
C370.032 (2)0.051 (3)0.055 (3)0.007 (2)0.002 (2)0.020 (2)
C380.032 (2)0.071 (3)0.045 (3)0.009 (2)0.007 (2)0.022 (2)
C390.041 (3)0.094 (4)0.047 (3)0.005 (3)0.004 (2)0.027 (3)
Geometric parameters (Å, º) top
Sn1—C42.144 (4)C13—H13a0.950
Sn1—C82.135 (4)C13—H13b0.950
Sn1—C122.142 (3)C14—H14a0.950
Sn1—O12.205 (2)C14—H14b0.950
Sn1—O52.292 (2)C15—H15a0.950
Sn2—C16A2.093 (6)C15—H15b0.950
Sn2—C20A2.217 (8)C15—H15c0.950
Sn2—C24A2.124 (8)C28—H28a0.950
Sn2—C16B2.174 (7)C28—H28b0.950
Sn2—C20B2.095 (7)C29—H29a0.950
Sn2—C24B2.149 (8)C29—H29b0.950
Sn2—O32.160 (3)C30—H30a0.950
Sn2—O42.408 (3)C30—H30b0.950
Sn3—C282.136 (5)C31—H31a0.950
Sn3—C322.147 (5)C31—H31b0.950
Sn3—C362.134 (4)C31—H31c0.950
Sn3—O22.030 (3)C32—H32a0.950
P1—O11.508 (2)C32—H32b0.950
P1—O21.543 (3)C33—H33a0.950
P1—O3i1.519 (2)C33—H33b0.950
P1—C1ii1.806 (3)C34—H34a0.950
N1—C11.460 (4)C34—H34b0.950
N1—C21.458 (4)C35—H35a0.950
C2—C31.519 (4)C35—H35b0.950
O4—C31.239 (4)C35—H35c0.950
O5—C31.263 (4)C36—H36a0.950
C4—C51.510 (5)C36—H36b0.950
C5—C61.517 (5)C37—H37a0.950
C6—C71.501 (7)C37—H37b0.950
C8—C91.527 (6)C38—H38a0.950
C9—C101.545 (6)C38—H38b0.950
C10—C111.505 (7)C39—H39a0.950
C12—C131.505 (5)C39—H39b0.950
C13—C141.530 (6)C39—H39c0.950
C14—C151.516 (7)C16A—H16Aa0.950
C28—C291.527 (6)C16A—H16Ab0.950
C29—C301.522 (7)C17A—H17Aa0.950
C30—C311.506 (6)C17A—H17Ab0.950
C32—C331.530 (7)C18A—H18Aa0.950
C33—C341.521 (6)C18A—H18Ab0.950
C34—C351.509 (8)C19A—H19Aa0.950
C36—C371.525 (6)C19A—H19Ab0.950
C37—C381.510 (8)C19A—H19Ac0.950
C38—C391.540 (7)C16B—H16Ba0.950
C16A—C17A1.548 (11)C16B—H16Bb0.950
C17A—C18A1.517 (12)C17B—H17Ba0.950
C18A—C19A1.538 (14)C17B—H17Bb0.950
C16B—C17B1.522 (10)C18B—H18Ba0.950
C17B—C18B1.522 (12)C18B—H18Bb0.950
C18B—C19B1.508 (13)C19B—H19Ba0.950
C20A—C21A1.536 (11)C19B—H19Bb0.950
C21A—C22A1.477 (13)C19B—H19Bc0.950
C22A—C23A1.515 (15)C20A—H20Aa0.950
C20B—C21B1.515 (11)C20A—H20Ab0.950
C21B—C22B1.480 (12)C21A—H21Aa0.950
C22B—C23B1.518 (16)C21A—H21Ab0.950
C24A—C25A1.507 (12)C22A—H22Aa0.950
C25A—C26A1.524 (13)C22A—H22AB0.950
C26A—C27A1.493 (14)C23A—H23Aa0.950
C24B—C25B1.546 (11)C23A—H23Ab0.950
C25B—C26B1.544 (13)C23A—H23Ac0.950
C26B—C27B1.509 (13)C20B—H20Ba0.950
N1—HN10.950C20B—H20Bb0.950
C1—H1a0.950C21B—H21Ba0.950
C1—H1b0.950C21B—H21Bb0.950
C2—H2a0.950C22B—H22Ba0.950
C2—H2b0.950C22B—H22Bb0.950
C4—H4a0.950C23B—H23Bc0.950
C4—H4b0.950C24A—H24Aa0.950
C5—H5a0.950C24A—H24Ab0.950
C5—H5b0.950C25A—H25Aa0.950
C6—H6a0.950C25A—H25Ab0.950
C6—H6b0.950C26A—H26Aa0.950
C7—H7a0.950C26A—H26Ab0.950
C7—H7b0.950C27A—H27Aa0.950
C7—H7c0.950C27A—H27Ab0.950
C8—H8a0.950C27A—H27Ac0.950
C8—H8b0.950C24B—H24Ba0.950
C9—H9a0.950C24B—H24Bb0.950
C9—H9b0.950C25B—H25Ba0.950
C10—H10a0.950C25B—H25Bb0.950
C10—H10b0.950C26B—H26Ba0.950
C11—H11a0.950C26B—H26Bb0.950
C11—H11b0.950C27B—H27Ba0.950
C11—H11c0.950C27B—H27Bb0.950
C12—H12a0.950C27B—H27Bc0.950
C12—H12b0.950
C4—Sn1—C8117.2 (2)C14—C15—H15a113.8
C4—Sn1—C12120.8 (1)H15b—C15—H15c109.5
C4—Sn1—O192.0 (1)C14—C15—H15b108.4
C4—Sn1—O588.2 (1)C14—C15—H15c108.4
C8—Sn1—C12121.5 (1)H28a—C28—H28b109.5
C8—Sn1—O189.8 (1)C29—C28—H28a108.5
C8—Sn1—O585.5 (1)C29—C28—H28b108.5
O1—Sn1—C1294.9 (1)H29a—C29—H29b109.5
O1—Sn1—O5174.85 (9)C30—C29—H29a108.3
O5—Sn1—C1289.4 (1)C28—C29—H29a108.3
C16A—Sn2—C20A124.5 (3)C30—C29—H29b108.3
C16A—Sn2—C24A121.9 (3)C28—C29—H29b108.3
C20A—Sn2—C24A112.5 (3)H30a—C30—H30b109.5
O3—Sn2—C16A94.6 (2)C31—C30—H30a108.4
O3—Sn2—C20A92.1 (2)C29—C30—H30a108.4
O3—Sn2—C24A93.6 (2)C31—C30—H30b108.4
O4—Sn2—C16A86.4 (2)C29—C30—H30b108.4
O4—Sn2—C20A89.3 (2)H31a—C31—H31b108.4
O4—Sn2—C24A83.7 (2)H31a—C31—H31c108.4
O3—Sn2—O4177.3 (1)C30—C31—H31a113.5
C16B—Sn2—C20B118.2 (3)H31b—C31—H31c109.5
C16B—Sn2—C24B118.4 (3)C30—C31—H31b108.4
C20B—Sn2—C24B121.1 (3)C30—C31—H31c108.4
O3—Sn2—C16B101.1 (2)H32a—C32—H32b109.5
O3—Sn2—C20B94.2 (2)C33—C32—H32a107.7
O3—Sn2—C24B90.1 (2)C33—C32—H32b107.7
O4—Sn2—C16B80.8 (2)H33a—C33—H33b109.5
O4—Sn2—C20B86.5 (2)C34—C33—H33a108.4
O4—Sn2—C24B87.4 (2)C32—C33—H33a108.4
C28—Sn3—C32110.9 (2)C34—C33—H33b108.4
C28—Sn3—C36118.7 (2)C32—C33—H33b108.4
C32—Sn3—C36112.5 (2)H34a—C34—H34b109.5
O2—Sn3—C28108.8 (1)C35—C34—H34a108.7
O2—Sn3—C3297.0 (1)C33—C34—H34a108.7
O2—Sn3—C36106.6 (1)C35—C34—H34b108.7
Sn1—C4—C5117.2 (2)C33—C34—H34b108.7
Sn1—C8—C9116.9 (3)H35a—C35—H35b108.7
Sn1—C12—C13115.0 (2)H35a—C35—H35c108.7
Sn1—O1—P1138.5 (1)C34—C35—H35a112.7
Sn1—O5—C3129.1 (2)H35b—C35—H35c109.5
Sn2—C16A—C17A115.5 (5)C34—C35—H35b108.7
Sn2—C20A—C21A121.1 (5)C34—C35—H35c108.7
Sn2—C24A—C25A115.5 (5)H36a—C36—H36b109.5
Sn2—O3—P1iii143.3 (2)C37—C36—H36a108.6
Sn2—O4—C3145.0 (2)C37—C36—H36b108.6
Sn2—C16B—C17B115.8 (5)H37a—C37—H37b109.5
Sn2—C20B—C21B116.1 (5)C38—C37—H37a108.5
Sn2—C24B—C25B112.7 (5)C36—C37—H37a108.5
Sn3—C28—C29113.4 (3)C38—C37—H37b108.5
Sn3—C32—C33116.5 (3)C36—C37—H37b108.5
Sn3—C36—C37113.0 (3)H38a—C38—H38b109.5
Sn3—O2—P1134.7 (2)C37—C38—H38a108.3
O1—P1—O3i113.9 (1)C39—C38—H38a108.3
O1—P1—O2110.2 (1)C37—C38—H38b108.3
O1—P1—C1ii109.7 (1)C39—C38—H38b108.3
O2—P1—O3i111.1 (2)H39a—C39—H39b108.3
O3i—P1—C1ii105.5 (2)H39a—C39—H39c108.3
O2—P1—C1ii106.0 (2)C38—C39—H39a114.0
C1—N1—C2113.2 (3)H39b—C39—H39c109.5
P1iv—C1—N1109.3 (2)C38—C39—H39b108.3
N1—C2—C3112.8 (3)C38—C39—H39c108.3
O4—C3—O5125.9 (3)H16Aa—C16A—H16Ab109.5
O4—C3—C2118.9 (3)C17A—C16A—H16Aa107.9
O5—C3—C2115.2 (3)C17A—C16A—H16Ab107.9
C4—C5—C6115.2 (3)H17Aa—C17A—H17Ab109.5
C5—C6—C7113.8 (4)C18A—C17A—H17Aa108.3
C8—C9—C10113.1 (4)C16A—C17A—H17Aa108.3
C9—C10—C11113.2 (4)C18A—C17A—H17Ab108.3
C12—C13—C14112.9 (3)C16A—C17A—H17Ab108.3
C13—C14—C15113.8 (4)H18Aa—C18A—H18Ab109.5
C28—C29—C30114.0 (4)C17A—C18A—H18Aa108.5
C29—C30—C31113.6 (4)C19A—C18A—H18Aa108.5
C32—C33—C34113.9 (4)C17A—C18A—H18Ab108.5
C33—C34—C35112.7 (5)C19A—C18A—H18Ab108.5
C36—C37—C38113.4 (4)H19Aa—C19A—H19Ab108.5
C37—C38—C39114.0 (5)H19Aa—C19A—H19Ac108.5
C16A—C17A—C18A114.1 (7)H19Ab—C19A—H19Ac109.5
C17A—C18A—C19A113.5 (8)C18A—C19A—H19Aa113.5
C20A—C21A—C22A114.6 (7)C18A—C19A—H19Ab108.5
C21A—C22A—C23A111.0 (8)C18A—C19A—H19Ac108.5
C24A—C25A—C26A114.8 (7)H16Ba—C16B—H16Bb109.5
C25A—C26A—C27A112.8 (8)C17B—C16B—H16Ba107.9
C16B—C17B—C18B115.1 (7)C17B—C16B—H16Bb107.9
C17B—C18B—C19B115.0 (7)H17Ba—C17B—H17Bb109.5
C20B—C21B—C22B113.6 (7)C16B—C17B—H17Ba108.0
C21B—C22B—C23B114.0 (8)C18B—C17B—H17Ba108.0
C24B—C25B—C26B112.3 (7)C16B—C17B—H17Bb108.0
C25B—C26B—C27B109.0 (8)C18B—C17B—H17Bb108.0
Sn1—C4—H4a107.5H18Ba—C18B—H18Bb109.5
Sn1—C4—H4b107.5C17B—C18B—H18Ba108.1
Sn1—C8—H8a107.6C17B—C18B—H18Bb108.1
Sn1—C8—H8b107.6C19B—C18B—H18Ba108.1
Sn1—C12—H12a108.1C19B—C18B—H18Bb108.1
Sn1—C12—H12b108.1H19Ba—C19B—H19Bb108.1
Sn2—C16A—H16Aa107.9H19Ba—C19B—H19Bc108.1
Sn2—C16A—H16Ab107.9H19Bb—C19B—H19Bc109.5
Sn2—C16B—H16Ba107.9C18B—C19B—H19Ba115.0
Sn2—C16B—H16Bb107.9C18B—C19B—H19Bb108.1
Sn2—C20A—H20Aa106.5C18B—C19B—H19Bc108.1
Sn2—C20A—H20Ab106.5H20Aa—C20A—H20Ab109.5
Sn2—C20B—H20Ba107.8C21A—C20A—H20Aa106.5
Sn2—C20B—H20Bb107.8C21A—C20A—H20Ab106.5
Sn2—C24B—H24Ba108.7H21Aa—C21A—H21Ab109.5
Sn2—C24B—H24Bb108.7C22A—C21A—H21Aa108.2
Sn3—C28—H28a108.5C20A—C21A—H21Aa108.2
Sn3—C28—H28b108.5C22A—C21A—H21Ab108.2
Sn3—C32—H32a107.7C20A—C21A—H21Ab108.2
Sn3—C32—H32b107.7H22Aa—C22A—H22AB109.5
Sn3—C36—H36a108.6C21A—C22A—H22Aa109.1
Sn3—C36—H36b108.6C23A—C22A—H22Aa109.1
C2—N1—HN1108.5C21A—C22A—H22AB109.1
C1—N1—HN1108.5C23A—C22A—H22AB109.1
H1a—C1—H1b109.5H23Aa—C23A—H23Ab109.1
N1—C1—H1a109.5H23Aa—C23A—H23Ac109.1
N1—C1—H1b109.5H23Ab—C23A—H23Ac109.5
P1iv—C1—H1a109.5C22A—C23A—H23Ab109.1
P1iv—C1—H1b109.5C22A—C23A—H23Ac109.1
H2a—C2—H2b109.5C22A—C23A—H23Aa111.0
N1—C2—H2a108.6H20Ba—C20B—H20Bb109.5
C3—C2—H2a108.6C21B—C20B—H20Ba107.8
N1—C2—H2b108.6C21B—C20B—H20Bb107.8
C3—C2—H2b108.6H21Ba—C21B—H21Bb109.5
H4a—C4—H4b109.5C22B—C21B—H21Ba108.4
C5—C4—H4a107.5C20B—C21B—H21Ba108.4
C5—C4—H4b107.5C22B—C21B—H21Bb108.4
H5a—C5—H5b109.5C20B—C21B—H21Bb108.4
C4—C5—H5a108.0H22Ba—C22B—H22Bb109.5
C6—C5—H5a108.0C21B—C22B—H22Ba108.3
C4—C5—H5b108.0C23B—C22B—H22Ba108.3
C6—C5—H5b108.0C21B—C22B—H22Bb108.3
H6a—C6—H6b109.5C23B—C22B—H22Bb108.3
C7—C6—H6a108.4H23Ba—C23B—H23Bb108.3
C5—C6—H6a108.4H23Ba—C23B—H23Bc108.3
C7—C6—H6b108.4H23Bb—C23B—H23Bc109.5
C5—C6—H6b108.4C22B—C23B—H23Bb108.3
H7a—C7—H7b108.4C22B—C23B—H23Bc108.3
H7a—C7—H7c108.4C22B—C23B—H23Ba114.0
C6—C7—H7a113.8H24Aa—C24A—H24Ab109.5
H7b—C7—H7c109.5C25A—C24A—H24Aa107.9
C6—C7—H7b108.4C25A—C24A—H24Ab107.9
C6—C7—H7c108.4H25Aa—C25A—H25Ab109.5
H8a—C8—H8b109.5C24A—C25A—H25Ab108.1
C9—C8—H8a107.6C26A—C25A—H25Ab108.1
C9—C8—H8b107.6C24A—C25A—H25Aa108.1
H9a—C9—H9b109.5C26A—C25A—H25Aa108.1
C8—C9—H9a108.6H26Aa—C26A—H26Ab109.5
C10—C9—H9a108.6C27A—C26A—H26Aa108.6
C8—C9—H9b108.6C25A—C26A—H26Aa108.6
C10—C9—H9b108.6C27A—C26A—H26Ab108.6
H10a—C10—H10b109.5C25A—C26A—H26Ab108.6
C11—C10—H10a108.5H27Aa—C27A—H27Ab108.6
C9—C10—H10a108.5H27Aa—C27A—H27Ac108.6
C11—C10—H10b108.5H27Ab—C27A—H27Ac109.5
C9—C10—H10b108.5C26A—C27A—H27Aa112.8
H11a—C11—H11b108.5C26A—C27A—H27Ab108.6
H11a—C11—H11c108.5C26A—C27A—H27Ac108.6
C10—C11—H11a113.2H24Ba—C24B—H24Bb109.5
H11b—C11—H11c109.5C25B—C24B—H24Ba108.7
C10—C11—H11b108.5C25B—C24B—H24Bb108.7
C10—C11—H11c108.5H25Ba—C25B—H25Bb109.5
H12a—C12—H12b109.5C26B—C25B—H25Ba108.8
C13—C12—H12a108.1C24B—C25B—H25Ba108.8
C13—C12—H12b108.1C26B—C25B—H25Bb108.8
H13a—C13—H13b109.5C24B—C25B—H25Bb108.8
C12—C13—H13a108.6H26Ba—C26B—H26Bb109.5
C14—C13—H13a108.6C27B—C26B—H26Ba109.6
C12—C13—H13b108.6C25B—C26B—H26Ba109.6
C14—C13—H13b108.6C27B—C26B—H26Bb109.6
H14a—C14—H14b109.5C25B—C26B—H26Bb109.6
C15—C14—H14a108.4H27Ba—C27B—H27Bb109.6
C13—C14—H14a108.4H27Ba—C27B—H27Bc109.6
C15—C14—H14b108.4H27Bb—C27B—H27Bc109.5
C13—C14—H14b108.4C26B—C27B—H27Ba109.0
H15a—C15—H15b108.4C26B—C27B—H27Bb109.6
H15a—C15—H15c108.4C26B—C27B—H27Bc109.6
O1iv—P1iv—C1—N1179.8 (3)N1—C2—C3—O4168.4 (3)
P1iv—C1—N1—C2178.2 (2)N1—C2—C3—O512.6 (4)
C1—N1—C2—C3154.1 (3)
Symmetry codes: (i) x, y1/2, z+1; (ii) x+1, y, z; (iii) x, y+1/2, z+1; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formula[Sn3(C4H9)9(C3H5O5P)]
Mr1036.20
Crystal system, space groupMonoclinic, P21
Temperature (K)120
a, b, c (Å)10.2144 (7), 18.018 (1), 13.1304 (9)
β (°) 90.177 (1)
V3)2416.6 (2)
Z2
Radiation typeMo Kα
µ (mm1)1.61
Crystal size (mm)0.47 × 0.16 × 0.15
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionIntegration
(XPREP; Siemens, 1995)
Tmin, Tmax0.501, 0.799
No. of measured, independent and
observed [I > 2σ(I)] reflections
28299, 13624, 12628
Rint0.032
(sin θ/λ)max1)0.699
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.071, 1.12
No. of reflections12628
No. of parameters431
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)2.2 (1), 1.1 (1)
Absolute structureRogers (1981)
Rogers parameter0.73 (3)

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SIR97 (Cascarano et al., 1996) and KRYSTAL (Hazell, 1995), modified ORFLS (Busing et al., 1962) and KRYSTAL, ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL, KRYSTAL.

Selected bond lengths (Å) top
Sn1—C42.144 (4)Sn2—C20B2.095 (7)
Sn1—C82.135 (4)Sn2—C24B2.149 (8)
Sn1—C122.142 (3)Sn2—O32.160 (3)
Sn1—O12.205 (2)Sn2—O42.408 (3)
Sn1—O52.292 (2)Sn3—C282.136 (5)
Sn2—C16A2.093 (6)Sn3—C322.147 (5)
Sn2—C20A2.217 (8)Sn3—C362.134 (4)
Sn2—C24A2.124 (8)Sn3—O22.030 (3)
Sn2—C16B2.174 (7)
 

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