Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100006016/na1470sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100006016/na1470Isup2.hkl |
CCDC reference: 147629
The title compound was obtained by chance during the preparation of trineophyltin iodide, Neophyl3SnI, from trineophyltin chloride via the corresponding distannoxane. For this purpose the chloride was hydrolyzed by concentrated potassium hydroxide solution in a heated toluene-water mixture. Most of the organic layer containing the distannoxane was decanted and worked up; the aqueous reaction mixture, which also contained a small amount of the organic solution, was left aside. After some weeks most of the solvent had evaporated and some clear transparent crystals of (I) had formed. It is known (Davies, 1997) that tetraorganodistannoxanes often separate from samples of triorganotin halides when stored for longer periods. A suitable single-crystal of (I) for X-ray structure determination was selected using a polarization microscope and mounted on top of a Lindemann capillary with a cyanoacrylate adhesive.
The positions of the H atoms on the OH groups were found in difference Fourier maps. Full ref?
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Sn4O2(OH)4(C10H13)8] | Z = 1 |
Mr = 1640.42 | F(000) = 836 |
Triclinic, P1 | Dx = 1.436 Mg m−3 |
a = 10.878 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.598 (3) Å | Cell parameters from 20 reflections |
c = 17.077 (2) Å | θ = 5.1–12.5° |
α = 73.19 (2)° | µ = 1.35 mm−1 |
β = 81.944 (19)° | T = 293 K |
γ = 66.91 (2)° | Block, colourless |
V = 1896.4 (7) Å3 | 0.43 × 0.29 × 0.25 mm |
Siemens P4 diffractometer | 5394 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
2θ/ω scans | h = −12→1 |
Absorption correction: ψ-scan SHELXTL (Sheldrick, 1997b) | k = −13→12 |
Tmin = 0.652, Tmax = 0.713 | l = −20→20 |
7739 measured reflections | 3 standard reflections every 97 reflections |
6615 independent reflections | intensity decay: none |
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)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0339P)2 + 0.3893P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.011 |
6615 reflections | Δρmax = 0.62 e Å−3 |
408 parameters | Δρmin = −0.51 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0007 (2) |
[Sn4O2(OH)4(C10H13)8] | γ = 66.91 (2)° |
Mr = 1640.42 | V = 1896.4 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.878 (2) Å | Mo Kα radiation |
b = 11.598 (3) Å | µ = 1.35 mm−1 |
c = 17.077 (2) Å | T = 293 K |
α = 73.19 (2)° | 0.43 × 0.29 × 0.25 mm |
β = 81.944 (19)° |
Siemens P4 diffractometer | 5394 reflections with I > 2σ(I) |
Absorption correction: ψ-scan SHELXTL (Sheldrick, 1997b) | Rint = 0.033 |
Tmin = 0.652, Tmax = 0.713 | 3 standard reflections every 97 reflections |
7739 measured reflections | intensity decay: none |
6615 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.62 e Å−3 |
6615 reflections | Δρmin = −0.51 e Å−3 |
408 parameters |
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 | 0.96953 (2) | 0.86217 (2) | 0.54208 (1) | 0.03170 (7) | |
Sn2 | 0.89888 (2) | 1.03778 (2) | 0.68393 (1) | 0.03524 (8) | |
O1 | 0.9655 (2) | 1.0250 (2) | 0.56851 (13) | 0.0355 (5) | |
O2 | 0.9060 (3) | 0.8439 (3) | 0.66611 (15) | 0.0441 (6) | |
H2 | 0.9326 | 0.7693 | 0.6950 | 0.093 (3)* | |
O3 | 0.9227 (3) | 1.2114 (3) | 0.65745 (18) | 0.0542 (7) | |
H3 | 0.8497 | 1.2707 | 0.6482 | 0.093 (3)* | |
C110 | 1.1459 (4) | 0.6894 (4) | 0.5483 (3) | 0.0526 (10) | |
H110A | 1.1160 | 0.6174 | 0.5600 | 0.093 (3)* | |
H110B | 1.1870 | 0.6963 | 0.4938 | 0.093 (3)* | |
C111 | 1.2570 (4) | 0.6499 (4) | 0.6078 (3) | 0.0481 (9) | |
C112 | 1.2946 (5) | 0.7673 (5) | 0.5966 (4) | 0.0781 (16) | |
H112A | 1.3167 | 0.7979 | 0.5400 | 0.093 (3)* | |
H112B | 1.3704 | 0.7430 | 0.6291 | 0.093 (3)* | |
H112C | 1.2205 | 0.8349 | 0.6138 | 0.093 (3)* | |
C113 | 1.3800 (5) | 0.5422 (5) | 0.5817 (4) | 0.0803 (17) | |
H113A | 1.4047 | 0.5734 | 0.5257 | 0.093 (3)* | |
H113B | 1.3583 | 0.4675 | 0.5872 | 0.093 (3)* | |
H113C | 1.4533 | 0.5190 | 0.6159 | 0.093 (3)* | |
C114 | 1.2210 (5) | 0.5970 (4) | 0.6965 (3) | 0.0567 (11) | |
C115 | 1.1225 (8) | 0.5486 (7) | 0.7188 (4) | 0.099 (2) | |
H115 | 1.0736 | 0.5467 | 0.6790 | 0.093 (3)* | |
C116 | 1.0946 (12) | 0.5018 (10) | 0.8014 (6) | 0.162 (5) | |
H116 | 1.0273 | 0.4684 | 0.8162 | 0.093 (3)* | |
C117 | 1.1619 (16) | 0.5040 (11) | 0.8586 (6) | 0.183 (8) | |
H117 | 1.1381 | 0.4766 | 0.9133 | 0.093 (3)* | |
C118 | 1.2660 (14) | 0.5457 (9) | 0.8395 (5) | 0.153 (6) | |
H118 | 1.3179 | 0.5414 | 0.8800 | 0.093 (3)* | |
C119 | 1.2907 (8) | 0.5939 (6) | 0.7589 (4) | 0.100 (2) | |
H119 | 1.3586 | 0.6267 | 0.7452 | 0.093 (3)* | |
C120 | 0.7838 (4) | 0.8892 (3) | 0.4948 (2) | 0.0400 (7) | |
H120A | 0.7126 | 0.9502 | 0.5202 | 0.093 (3)* | |
H120B | 0.7849 | 0.9311 | 0.4368 | 0.093 (3)* | |
C121 | 0.7441 (4) | 0.7717 (4) | 0.5045 (2) | 0.0410 (8) | |
C122 | 0.8472 (5) | 0.6789 (5) | 0.4575 (3) | 0.0642 (13) | |
H122A | 0.8538 | 0.7251 | 0.4015 | 0.093 (3)* | |
H122B | 0.8194 | 0.6090 | 0.4597 | 0.093 (3)* | |
H122C | 0.9328 | 0.6446 | 0.4820 | 0.093 (3)* | |
C123 | 0.6102 (5) | 0.8214 (5) | 0.4628 (3) | 0.0617 (12) | |
H123A | 0.6196 | 0.8633 | 0.4061 | 0.093 (3)* | |
H123B | 0.5431 | 0.8823 | 0.4892 | 0.093 (3)* | |
H123C | 0.5841 | 0.7497 | 0.4669 | 0.093 (3)* | |
C124 | 0.7278 (4) | 0.7055 (4) | 0.5943 (3) | 0.0456 (8) | |
C125 | 0.8010 (7) | 0.5764 (5) | 0.6290 (4) | 0.0800 (16) | |
H125 | 0.8655 | 0.5275 | 0.5973 | 0.093 (3)* | |
C126 | 0.7802 (13) | 0.5198 (9) | 0.7085 (5) | 0.140 (4) | |
H126 | 0.8306 | 0.4325 | 0.7299 | 0.093 (3)* | |
C127 | 0.6902 (12) | 0.5848 (11) | 0.7568 (5) | 0.136 (4) | |
H127 | 0.6774 | 0.5436 | 0.8110 | 0.093 (3)* | |
C128 | 0.6151 (8) | 0.7156 (10) | 0.7253 (4) | 0.106 (3) | |
H128 | 0.5527 | 0.7627 | 0.7586 | 0.093 (3)* | |
C129 | 0.6338 (5) | 0.7759 (6) | 0.6434 (3) | 0.0680 (13) | |
H129 | 0.5832 | 0.8631 | 0.6220 | 0.093 (3)* | |
C210 | 0.6841 (4) | 1.1042 (4) | 0.6894 (2) | 0.0456 (8) | |
H210A | 0.6509 | 1.1802 | 0.6441 | 0.093 (3)* | |
H210B | 0.6596 | 1.0375 | 0.6801 | 0.093 (3)* | |
C211 | 0.6086 (4) | 1.1391 (4) | 0.7683 (2) | 0.0474 (9) | |
C212 | 0.4584 (5) | 1.1717 (7) | 0.7597 (3) | 0.0750 (15) | |
H212A | 0.4461 | 1.0972 | 0.7536 | 0.093 (3)* | |
H212B | 0.4260 | 1.2426 | 0.7124 | 0.093 (3)* | |
H212C | 0.4097 | 1.1954 | 0.8076 | 0.093 (3)* | |
C213 | 0.6257 (5) | 1.2592 (5) | 0.7779 (3) | 0.0626 (12) | |
H213A | 0.5948 | 1.3292 | 0.7299 | 0.093 (3)* | |
H213B | 0.7184 | 1.2398 | 0.7847 | 0.093 (3)* | |
H213C | 0.5745 | 1.2839 | 0.8250 | 0.093 (3)* | |
C214 | 0.6568 (4) | 1.0241 (4) | 0.8438 (3) | 0.0510 (9) | |
C215 | 0.6991 (7) | 0.8980 (6) | 0.8386 (4) | 0.0809 (17) | |
H215 | 0.7018 | 0.8814 | 0.7881 | 0.093 (3)* | |
C216 | 0.7379 (9) | 0.7947 (7) | 0.9084 (5) | 0.115 (3) | |
H216 | 0.7684 | 0.7098 | 0.9040 | 0.093 (3)* | |
C217 | 0.7309 (9) | 0.8186 (10) | 0.9830 (5) | 0.124 (3) | |
H217 | 0.7534 | 0.7499 | 1.0297 | 0.093 (3)* | |
C218 | 0.6923 (10) | 0.9392 (9) | 0.9890 (4) | 0.120 (3) | |
H218 | 0.6898 | 0.9549 | 1.0397 | 0.093 (3)* | |
C219 | 0.6554 (7) | 1.0424 (7) | 0.9197 (3) | 0.0845 (18) | |
H219 | 0.6290 | 1.1264 | 0.9250 | 0.093 (3)* | |
C220 | 1.0341 (4) | 0.9157 (4) | 0.7812 (2) | 0.0512 (9) | |
H220A | 0.9841 | 0.8744 | 0.8235 | 0.093 (3)* | |
H220B | 1.1022 | 0.8475 | 0.7598 | 0.093 (3)* | |
C221 | 1.1078 (4) | 0.9687 (5) | 0.8242 (2) | 0.0513 (10) | |
C222 | 1.0077 (6) | 1.0730 (5) | 0.8635 (3) | 0.0765 (16) | |
H222A | 0.9516 | 1.0368 | 0.9027 | 0.093 (3)* | |
H222B | 0.9535 | 1.1433 | 0.8219 | 0.093 (3)* | |
H222C | 1.0550 | 1.1045 | 0.8904 | 0.093 (3)* | |
C223 | 1.1962 (6) | 1.0253 (7) | 0.7624 (4) | 0.0871 (19) | |
H223A | 1.2590 | 0.9595 | 0.7378 | 0.093 (3)* | |
H223B | 1.2436 | 1.0568 | 0.7893 | 0.093 (3)* | |
H223C | 1.1421 | 1.0956 | 0.7208 | 0.093 (3)* | |
C224 | 1.1910 (4) | 0.8556 (5) | 0.8928 (2) | 0.0538 (10) | |
C225 | 1.1296 (5) | 0.7897 (6) | 0.9551 (3) | 0.0694 (14) | |
H225 | 1.0374 | 0.8134 | 0.9553 | 0.093 (3)* | |
C226 | 1.2025 (7) | 0.6880 (7) | 1.0180 (3) | 0.0905 (19) | |
H226 | 1.1587 | 0.6451 | 1.0595 | 0.093 (3)* | |
C227 | 1.3371 (7) | 0.6517 (7) | 1.0188 (4) | 0.091 (2) | |
H227 | 1.3856 | 0.5834 | 1.0605 | 0.093 (3)* | |
C228 | 1.4005 (6) | 0.7147 (7) | 0.9589 (4) | 0.091 (2) | |
H228 | 1.4928 | 0.6899 | 0.9595 | 0.093 (3)* | |
C229 | 1.3286 (5) | 0.8163 (6) | 0.8966 (3) | 0.0718 (14) | |
H229 | 1.3737 | 0.8593 | 0.8561 | 0.093 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03413 (12) | 0.03008 (12) | 0.03403 (12) | −0.01365 (9) | 0.00007 (9) | −0.01091 (9) |
Sn2 | 0.03640 (13) | 0.04182 (14) | 0.03069 (12) | −0.01563 (10) | 0.00221 (9) | −0.01395 (9) |
O1 | 0.0442 (13) | 0.0367 (12) | 0.0320 (11) | −0.0205 (10) | 0.0059 (10) | −0.0138 (9) |
O2 | 0.0587 (16) | 0.0450 (14) | 0.0352 (12) | −0.0269 (12) | 0.0035 (11) | −0.0115 (10) |
O3 | 0.0604 (18) | 0.0539 (17) | 0.0576 (17) | −0.0292 (14) | 0.0028 (14) | −0.0191 (14) |
C110 | 0.057 (2) | 0.044 (2) | 0.049 (2) | −0.0029 (18) | −0.0052 (18) | −0.0215 (17) |
C111 | 0.0381 (19) | 0.0386 (19) | 0.057 (2) | −0.0037 (16) | −0.0035 (16) | −0.0102 (17) |
C112 | 0.048 (3) | 0.063 (3) | 0.119 (5) | −0.021 (2) | −0.014 (3) | −0.012 (3) |
C113 | 0.059 (3) | 0.064 (3) | 0.087 (4) | 0.010 (2) | 0.000 (3) | −0.020 (3) |
C114 | 0.057 (2) | 0.041 (2) | 0.057 (2) | −0.0021 (18) | −0.012 (2) | −0.0079 (18) |
C115 | 0.098 (5) | 0.091 (5) | 0.090 (4) | −0.043 (4) | −0.002 (4) | 0.015 (4) |
C116 | 0.159 (10) | 0.150 (9) | 0.114 (7) | −0.060 (8) | 0.018 (7) | 0.050 (7) |
C117 | 0.239 (17) | 0.109 (8) | 0.076 (5) | 0.016 (9) | 0.030 (8) | 0.028 (5) |
C118 | 0.234 (15) | 0.095 (6) | 0.075 (5) | 0.021 (7) | −0.066 (7) | −0.024 (5) |
C119 | 0.133 (6) | 0.069 (4) | 0.076 (4) | 0.002 (4) | −0.049 (4) | −0.019 (3) |
C120 | 0.0386 (18) | 0.0370 (17) | 0.0461 (19) | −0.0162 (15) | −0.0049 (14) | −0.0087 (14) |
C121 | 0.0434 (19) | 0.0400 (18) | 0.0477 (19) | −0.0212 (16) | −0.0007 (15) | −0.0153 (15) |
C122 | 0.070 (3) | 0.067 (3) | 0.083 (3) | −0.040 (2) | 0.021 (2) | −0.048 (3) |
C123 | 0.062 (3) | 0.069 (3) | 0.070 (3) | −0.039 (2) | −0.015 (2) | −0.015 (2) |
C124 | 0.047 (2) | 0.046 (2) | 0.055 (2) | −0.0300 (18) | 0.0005 (17) | −0.0133 (17) |
C125 | 0.109 (5) | 0.045 (3) | 0.087 (4) | −0.038 (3) | −0.016 (3) | 0.000 (2) |
C126 | 0.239 (13) | 0.094 (6) | 0.099 (6) | −0.103 (8) | −0.049 (7) | 0.037 (5) |
C127 | 0.215 (12) | 0.164 (10) | 0.071 (4) | −0.147 (10) | 0.004 (6) | 0.013 (5) |
C128 | 0.119 (6) | 0.177 (8) | 0.074 (4) | −0.106 (6) | 0.038 (4) | −0.054 (5) |
C129 | 0.064 (3) | 0.091 (4) | 0.063 (3) | −0.042 (3) | 0.014 (2) | −0.030 (3) |
C210 | 0.0390 (19) | 0.060 (2) | 0.0410 (18) | −0.0204 (17) | 0.0020 (15) | −0.0162 (17) |
C211 | 0.0381 (19) | 0.060 (2) | 0.045 (2) | −0.0180 (17) | 0.0034 (15) | −0.0173 (17) |
C212 | 0.038 (2) | 0.113 (5) | 0.071 (3) | −0.023 (3) | 0.006 (2) | −0.031 (3) |
C213 | 0.059 (3) | 0.056 (3) | 0.067 (3) | −0.012 (2) | 0.004 (2) | −0.025 (2) |
C214 | 0.042 (2) | 0.061 (2) | 0.051 (2) | −0.0236 (19) | 0.0055 (17) | −0.0139 (19) |
C215 | 0.103 (5) | 0.068 (3) | 0.072 (3) | −0.042 (3) | 0.027 (3) | −0.017 (3) |
C216 | 0.120 (6) | 0.068 (4) | 0.128 (7) | −0.035 (4) | 0.026 (5) | 0.002 (4) |
C217 | 0.128 (7) | 0.128 (7) | 0.085 (5) | −0.058 (6) | −0.010 (5) | 0.035 (5) |
C218 | 0.183 (9) | 0.132 (7) | 0.057 (3) | −0.083 (7) | −0.023 (4) | 0.003 (4) |
C219 | 0.115 (5) | 0.095 (4) | 0.051 (3) | −0.049 (4) | −0.004 (3) | −0.015 (3) |
C220 | 0.056 (2) | 0.056 (2) | 0.0403 (19) | −0.0179 (19) | −0.0104 (17) | −0.0095 (17) |
C221 | 0.046 (2) | 0.068 (3) | 0.0433 (19) | −0.019 (2) | −0.0057 (16) | −0.0198 (19) |
C222 | 0.084 (4) | 0.073 (3) | 0.070 (3) | −0.008 (3) | −0.023 (3) | −0.036 (3) |
C223 | 0.066 (3) | 0.123 (5) | 0.075 (3) | −0.054 (4) | −0.017 (3) | 0.006 (3) |
C224 | 0.048 (2) | 0.072 (3) | 0.041 (2) | −0.016 (2) | −0.0050 (17) | −0.023 (2) |
C225 | 0.056 (3) | 0.091 (4) | 0.048 (2) | −0.018 (3) | −0.003 (2) | −0.012 (2) |
C226 | 0.102 (5) | 0.100 (5) | 0.051 (3) | −0.026 (4) | −0.012 (3) | −0.004 (3) |
C227 | 0.090 (4) | 0.087 (4) | 0.068 (3) | 0.004 (3) | −0.032 (3) | −0.019 (3) |
C228 | 0.060 (3) | 0.108 (5) | 0.090 (4) | −0.008 (3) | −0.025 (3) | −0.025 (4) |
C229 | 0.051 (3) | 0.095 (4) | 0.063 (3) | −0.015 (3) | −0.010 (2) | −0.024 (3) |
Sn1—O1 | 2.049 (2) | C124—C129 | 1.385 (7) |
Sn1—O2 | 2.110 (2) | C125—C126 | 1.357 (10) |
Sn1—C110 | 2.151 (4) | C126—C127 | 1.328 (14) |
Sn1—C120 | 2.155 (4) | C127—C128 | 1.391 (13) |
Sn1—O1i | 2.168 (2) | C128—C129 | 1.396 (8) |
Sn2—O1 | 2.029 (2) | C210—C211 | 1.549 (5) |
Sn2—O3 | 2.043 (3) | C211—C213 | 1.531 (6) |
Sn2—C220 | 2.149 (4) | C211—C214 | 1.536 (6) |
Sn2—C210 | 2.151 (4) | C211—C212 | 1.545 (6) |
Sn2—O2 | 2.325 (3) | C214—C219 | 1.370 (7) |
O1—Sn1i | 2.168 (2) | C214—C215 | 1.375 (7) |
C110—C111 | 1.530 (6) | C215—C216 | 1.397 (9) |
C111—C114 | 1.519 (6) | C216—C217 | 1.366 (12) |
C111—C112 | 1.525 (7) | C217—C218 | 1.324 (12) |
C111—C113 | 1.546 (6) | C218—C219 | 1.390 (9) |
C114—C115 | 1.358 (8) | C220—C221 | 1.539 (6) |
C114—C119 | 1.378 (8) | C221—C223 | 1.510 (7) |
C115—C116 | 1.393 (10) | C221—C222 | 1.527 (6) |
C116—C117 | 1.312 (18) | C221—C224 | 1.545 (6) |
C117—C118 | 1.363 (18) | C224—C225 | 1.376 (7) |
C118—C119 | 1.360 (12) | C224—C229 | 1.388 (7) |
C120—C121 | 1.543 (5) | C225—C226 | 1.395 (8) |
C121—C124 | 1.523 (5) | C226—C227 | 1.356 (10) |
C121—C123 | 1.536 (6) | C227—C228 | 1.350 (10) |
C121—C122 | 1.537 (5) | C228—C229 | 1.384 (8) |
C124—C125 | 1.383 (7) | ||
O1—Sn1—O2 | 74.57 (10) | C123—C121—C122 | 106.6 (4) |
O1—Sn1—C110 | 123.75 (15) | C124—C121—C120 | 111.6 (3) |
O2—Sn1—C110 | 102.28 (14) | C123—C121—C120 | 107.8 (3) |
O1—Sn1—C120 | 112.75 (12) | C122—C121—C120 | 109.0 (3) |
O2—Sn1—C120 | 97.29 (13) | C125—C124—C129 | 118.0 (5) |
C110—Sn1—C120 | 123.19 (16) | C125—C124—C121 | 122.8 (4) |
O1—Sn1—O1i | 73.19 (9) | C129—C124—C121 | 119.2 (4) |
O2—Sn1—O1i | 147.75 (9) | C126—C125—C124 | 121.0 (8) |
C110—Sn1—O1i | 94.94 (14) | C127—C126—C125 | 122.2 (9) |
C120—Sn1—O1i | 95.71 (12) | C126—C127—C128 | 119.1 (7) |
O1—Sn2—O3 | 88.71 (11) | C127—C128—C129 | 119.9 (7) |
O1—Sn2—C220 | 117.14 (14) | C124—C129—C128 | 119.8 (6) |
O3—Sn2—C220 | 104.28 (15) | C211—C210—Sn2 | 118.6 (3) |
O1—Sn2—C210 | 109.07 (12) | C213—C211—C214 | 111.5 (4) |
O3—Sn2—C210 | 99.93 (15) | C213—C211—C212 | 108.5 (4) |
C220—Sn2—C210 | 127.61 (16) | C214—C211—C212 | 107.8 (4) |
O1—Sn2—O2 | 70.34 (9) | C213—C211—C210 | 109.5 (3) |
O3—Sn2—O2 | 159.00 (10) | C214—C211—C210 | 111.2 (3) |
C220—Sn2—O2 | 84.83 (14) | C212—C211—C210 | 108.3 (4) |
C210—Sn2—O2 | 88.70 (14) | C219—C214—C215 | 116.9 (5) |
Sn2—O1—Sn1 | 114.13 (11) | C219—C214—C211 | 121.6 (5) |
Sn2—O1—Sn1i | 139.02 (12) | C215—C214—C211 | 121.5 (4) |
Sn1—O1—Sn1i | 106.81 (9) | C214—C215—C216 | 120.7 (6) |
Sn1—O2—Sn2 | 100.87 (10) | C217—C216—C215 | 119.9 (8) |
C111—C110—Sn1 | 121.9 (3) | C218—C217—C216 | 120.2 (7) |
C114—C111—C112 | 111.9 (4) | C217—C218—C219 | 120.1 (7) |
C114—C111—C110 | 114.0 (4) | C214—C219—C218 | 122.1 (7) |
C112—C111—C110 | 107.5 (4) | C221—C220—Sn2 | 122.4 (3) |
C114—C111—C113 | 107.9 (4) | C223—C221—C222 | 109.6 (5) |
C112—C111—C113 | 107.8 (4) | C223—C221—C220 | 109.3 (4) |
C110—C111—C113 | 107.5 (4) | C222—C221—C220 | 110.4 (4) |
C115—C114—C119 | 116.5 (6) | C223—C221—C224 | 111.2 (4) |
C115—C114—C111 | 123.0 (5) | C222—C221—C224 | 108.2 (4) |
C119—C114—C111 | 120.5 (6) | C220—C221—C224 | 108.1 (4) |
C114—C115—C116 | 120.0 (9) | C225—C224—C229 | 116.4 (5) |
C117—C116—C115 | 121.1 (12) | C225—C224—C221 | 120.5 (4) |
C116—C117—C118 | 121.3 (10) | C229—C224—C221 | 123.1 (5) |
C119—C118—C117 | 117.2 (11) | C224—C225—C226 | 121.5 (5) |
C118—C119—C114 | 123.8 (10) | C227—C226—C225 | 120.1 (6) |
C121—C120—Sn1 | 120.2 (2) | C228—C227—C226 | 119.9 (6) |
C124—C121—C123 | 108.9 (3) | C227—C228—C229 | 120.2 (6) |
C124—C121—C122 | 112.7 (4) | C228—C229—C224 | 121.8 (6) |
Symmetry code: (i) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Sn4O2(OH)4(C10H13)8] |
Mr | 1640.42 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.878 (2), 11.598 (3), 17.077 (2) |
α, β, γ (°) | 73.19 (2), 81.944 (19), 66.91 (2) |
V (Å3) | 1896.4 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.35 |
Crystal size (mm) | 0.43 × 0.29 × 0.25 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ-scan SHELXTL (Sheldrick, 1997b) |
Tmin, Tmax | 0.652, 0.713 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7739, 6615, 5394 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.072, 1.03 |
No. of reflections | 6615 |
No. of parameters | 408 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.62, −0.51 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Sheldrick, 1997b), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL.
Sn1—O1 | 2.049 (2) | Sn2—O1 | 2.029 (2) |
Sn1—O2 | 2.110 (2) | Sn2—O3 | 2.043 (3) |
Sn1—C110 | 2.151 (4) | Sn2—C220 | 2.149 (4) |
Sn1—C120 | 2.155 (4) | Sn2—C210 | 2.151 (4) |
Sn1—O1i | 2.168 (2) | Sn2—O2 | 2.325 (3) |
O1—Sn1—O2 | 74.57 (10) | O3—Sn2—C220 | 104.28 (15) |
O1—Sn1—C110 | 123.75 (15) | O1—Sn2—C210 | 109.07 (12) |
O2—Sn1—C110 | 102.28 (14) | O3—Sn2—C210 | 99.93 (15) |
O1—Sn1—C120 | 112.75 (12) | C220—Sn2—C210 | 127.61 (16) |
O2—Sn1—C120 | 97.29 (13) | O1—Sn2—O2 | 70.34 (9) |
C110—Sn1—C120 | 123.19 (16) | O3—Sn2—O2 | 159.00 (10) |
O1—Sn1—O1i | 73.19 (9) | C220—Sn2—O2 | 84.83 (14) |
O2—Sn1—O1i | 147.75 (9) | C210—Sn2—O2 | 88.70 (14) |
C110—Sn1—O1i | 94.94 (14) | Sn2—O1—Sn1 | 114.13 (11) |
C120—Sn1—O1i | 95.71 (12) | Sn2—O1—Sn1i | 139.02 (12) |
O1—Sn2—O3 | 88.71 (11) | Sn1—O1—Sn1i | 106.81 (9) |
O1—Sn2—C220 | 117.14 (14) | Sn1—O2—Sn2 | 100.87 (10) |
Symmetry code: (i) −x+2, −y+2, −z+1. |
Although the first step of the hydrolysis of diorganotin dihalides, R2SnX2, (1) (X = Cl, Br or I), namely, the formation of a dimeric `hydroxide halide' R2Sn(OH)X, (2) (Puff et al., 1985), is common to all kinds of organic groups R, further hydrolysis products depend on the size of the two organic ligands. Thus, the complete hydrolysis of (1) with bulky organic groups such as tert-butyl (Puff, Schuh et al., 1981) or mesityl (Weber et al., 1982) results in the formation of soluble trimeric `oxides' (R2SnO)3, (3), with tetrahedrally coordinated Sn. In the case of small organic groups such as isopropyl or phenyl, however, complete hydrolysis leads to the formation of insoluble polymeric `oxides' (R2SnO)n, (4), the structure of which is unknown. On the way to this final product, three intermediates can be isolated, all showing the so-called `ladder-type structure', because their inorganic framework consists of three four-membered rings, with fivefold trigonal-bipyramidally coordinated Sn. According to the degree of hydrolysis and condensation one can distinguish between the so-called `dihalides' [(R2SnX)(R2SnX)O]2, (5), `hydroxide halides' [(R2SnX)(R2SnOH)O]2, (6) and `dihydroxides' [(R2SnOH)(R2SnOH)O]2, (7). Although in the literature there are numerous examples described for compounds of types (5) (Harrison et al., 1980; Puff, Friedrichs & Visel, 1981; Graziani et al., 1983; Dakternieks et al., 1984; Vollano et al., 1984; Hamalainen & Turpeinen, 1987; Beckmann et al., 1998) and (6) (Vollano et al., 1984; Puff et al., 1983; Tiekink, 1991; Kresinski et al., 1994; Cox & Tiekink, 1994), only one compound with R = trimethylsilylmethyl (Puff, Friedrichs & Visel, 1981) is known to be of type (7), because this step in the course of the hydrolysis is difficult to prepare. Only by chance we found, in our study of tris(2,2-dimethyl-2-phenylethyl)tin halides (Neophyl3SnX, X = F, Cl, Br or I; Neophyl = 2,2-dimethyl-2-phenylethyl), a second compound of this type (7), the title compound, (I). \sch
The crystal structure of (I) consists of centrosymmetric [Neophyl2SnOH)(Neophyl2SnOH)O]2 molecules with an almost planar Sn—O framework. This is characterized by a central four-membered Sn—O ring with small O1—Sn1—O1i angles [73.19 (9)°] and broadened Sn1—O1—Sn1i angles [106.81 (9)°] [symmetry code: (i) 2 − x, 2 − y, 1 − z]. These values are typical for such a building unit and are also found for example in (5) and (6), as well as in cassiterite, SnO2 (Bolzan et al., 1997). The two outer four-membered Sn—O rings differ from this geometry because only the oxygen atom O1 is of the µ3-type; the other one belongs to a µ2-OH function and therefore the bond lengths and angles are different. In particular, the bridging OH group shows great differences in bond lengths: 2.325 (3) to the outer and 2.110 (2) Å to the inner Sn atom. The bond angles are O1—Sn1—O2 = 74.57 (19) and O1—Sn2—O2 = 70.34 (9)°; Sn1—O2—Sn2 = 100.87 (19) at the µ3-O and Sn2—O1—Sn1 = 114.13 (11)° at the µ2-OH group.
Both Sn atoms have a distorted trigonal bipyramidal coordination, with two O atoms in the axial positions and two C and one further O in the equatorial positions. However, the axes of these trigonal bipyramids are to some extent bent, as shown by the angles O2—Sn1—O1i = 147.75 (9) and O2—Sn2—O3 = 159.0 (1)°. Similar distortion can also be found in the ladder-type structures of (5) and (6). The mean Sn—C distance is 2.152 Å, which is slightly shorter than the Sn—C distance in the corresponding tetraneopyhltin compound (2.186 Å; Reuter & Pawlak, 1998).
The organic groups in (I) shield the Sn—O framework and prevent it from further condensation and from the formation of intermolecular hydrogen bonding.