
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033715/gg2020sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033715/gg2020Isup2.hkl |
CCDC reference: 657590
The 2,5-dimercapto-1,3,4-thiadiazole (1 mmol) was added to the solution of methanol 20 ml with sodium methoxide (2 mmol), and the mixture was stirred for 30 minutes, then di(4-fluorobenzyl)tin (3 mmol) was added to the mixture, continuing the reaction for 12 h at 318k. After cooling down to room temperature, this was then filtered. The solvent of the filtrate was gradually removed by evaporation under vacuum until a solid product was obtained. The solid was then recrystallized from benzene and colorless crystals suitable for X-ray diffraction was obtained (m.p. 356 K). Analysis, calculated for C49H15F6N2O3S3Sn3: C 46.11, H 3.55, N 2.20; found: C 46.16, H 3.59, N 2.18%.
All H atoms were placed geometrically and treated as riding on their parent atoms, with thiadiazole C—H and methyl C—H distances at 0.96 Å. The Uiso(H) values were set at 1.5Ueq(C) for all H atoms.
From Fig. 1, like other trinuclear organotin-µ3oxo clusters (Ma et al., 2007), the complex (I) contains a tricyclic system formed from a N2Sn2O ring and two Sn2O2 rings: all three Sn atoms exhibit severely distorted trigonal bipyramidal configurations. The atoms Sn2 and Sn3 have similar environments, in which one O atom and two C atoms of the benzyl groups occupy the equatorial positions (C5, C12 and O1 for Sn2; C19, C26 and O1 for Sn3). The axial positions are occupied by one N atom of the HHdmt and one O atom of the methoxy group (N2 and O2 for Sn1; N1 and O3 for Sn3). The geometry of Sn1 is cis-R2SnO3, in which the axial positions are defined by O2 and O3 atoms of methoxy group, C33 and C40 atoms of benzyl groups and one O atom occupy the equatorial plane.
With regard to the role of reaction hydrolysis, three [(C7H7F)2Sn] units are bridged by one O atom and two O atoms of methoxy group, forming a trinuclear complex, containing two Sn2O2 rings. Three Sn atoms and three O atoms (Sn1, Sn2, Sn3, O1, O2, O3) comprise a fused ring system, which is similar to traditional hydrolytic products of ladder-type arrangement (Puff et al., 1983), but different from the staircase structure of C84H148N8O10Sn4 (Yin et al., 2006). The Sn—O distances lies in the range 2.038 (5) to 2.188 (5) Å (Table 1), which are consistent with those Sn—O bonds in the ladder structure reported (Harrison et al., 1980). All of above indicates that strong bridge-oxo coordination with Sn atoms exist in the complex. Moreover, the aromatic rings effectively surround the –O—CH3 group.
The HHdmt ligand forms a five-membered ring, where two N atoms bond to the two Sn atoms to form another five-membered N2Sn2O1 ring. The Sn—N bond lengths [Sn2—N2 2.225 (6) Å and Sn3—N1 2.217 (7) Å] approach the covalent radii of Sn and N (2.15 Å) and are much shorter than the van der Waal's radii of Sn and N atoms (3.74 Å) (Hubeey et al., 1993), proving that N is coordinated to Sn by strong chemical bonds.
For related literature please review the following: ladder-type Sn3O3 arrangements (Puff et al., 1983), trinuclear RSnO clusters (Ma et al., 2007), a staircase Sn4O10 structure (Yin et al., 2006), related Sn ladder systems (Harrison et al., 1980), and van der Waal's radii of Sn and N atoms (Hubeey et al., 1993).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
![]() | Fig. 1. The structure of the title complex (I), showing 30% probability displacement ellipsoids. |
![]() | Fig. 2. Unit cell of the title complex (I). |
[Sn3(C7H7F)6(CH3O)2(C2N2S3)O]·0.5C6H6 | F(000) = 2516 |
Mr = 1276.12 | Dx = 1.702 Mg m−3 |
Monoclinic, P21/c | Melting point: 356 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3309 (9) Å | Cell parameters from 9782 reflections |
b = 45.937 (4) Å | θ = 1.8–26.0° |
c = 13.5763 (8) Å | µ = 1.68 mm−1 |
β = 129.394 (4)° | T = 293 K |
V = 4979.1 (7) Å3 | Block, colorless |
Z = 4 | 0.18 × 0.16 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 9782 independent reflections |
Radiation source: fine-focus sealed tube | 8279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
φ and ω scans | θmax = 26.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.751, Tmax = 0.877 | k = −56→56 |
51752 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.123P)2 + 12.502P] where P = (Fo2 + 2Fc2)/3 |
9782 reflections | (Δ/σ)max = 0.003 |
591 parameters | Δρmax = 0.72 e Å−3 |
0 restraints | Δρmin = −1.78 e Å−3 |
[Sn3(C7H7F)6(CH3O)2(C2N2S3)O]·0.5C6H6 | V = 4979.1 (7) Å3 |
Mr = 1276.12 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.3309 (9) Å | µ = 1.68 mm−1 |
b = 45.937 (4) Å | T = 293 K |
c = 13.5763 (8) Å | 0.18 × 0.16 × 0.08 mm |
β = 129.394 (4)° |
Siemens SMART CCD area-detector diffractometer | 9782 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 8279 reflections with I > 2σ(I) |
Tmin = 0.751, Tmax = 0.877 | Rint = 0.048 |
51752 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.123P)2 + 12.502P] where P = (Fo2 + 2Fc2)/3 |
9782 reflections | Δρmax = 0.72 e Å−3 |
591 parameters | Δρmin = −1.78 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 | 1.09057 (6) | 0.872437 (11) | 0.26253 (5) | 0.04148 (16) | |
Sn2 | 0.99142 (6) | 0.942464 (10) | 0.27698 (4) | 0.03669 (15) | |
Sn3 | 0.68330 (6) | 0.880017 (10) | 0.12982 (5) | 0.03655 (15) | |
S1 | 0.2941 (3) | 0.90904 (5) | 0.0062 (3) | 0.0677 (6) | |
S2 | 0.4469 (3) | 0.96904 (4) | 0.1112 (2) | 0.0548 (5) | |
S3 | 0.7698 (3) | 1.00416 (5) | 0.2581 (2) | 0.0594 (5) | |
F1 | 0.8398 (10) | 0.88068 (14) | 0.6454 (7) | 0.094 (2) | |
F2 | 0.5363 (10) | 0.91417 (15) | −0.3438 (5) | 0.104 (2) | |
F3 | 0.7676 (14) | 0.74570 (16) | 0.3886 (12) | 0.152 (4) | |
F4 | 0.2991 (11) | 0.76864 (14) | −0.2917 (7) | 0.112 (3) | |
F5 | 0.9696 (12) | 0.77323 (17) | −0.1815 (9) | 0.125 (3) | |
F6 | 1.5752 (11) | 0.75227 (17) | 0.4952 (8) | 0.120 (3) | |
O1 | 0.9093 (5) | 0.90072 (10) | 0.2213 (4) | 0.0384 (10) | |
O2 | 1.1931 (6) | 0.91524 (11) | 0.3167 (5) | 0.0492 (13) | |
O3 | 0.8669 (6) | 0.84801 (11) | 0.1676 (5) | 0.0456 (12) | |
N1 | 0.6135 (7) | 0.92511 (12) | 0.1374 (6) | 0.0386 (13) | |
N2 | 0.7269 (7) | 0.94780 (12) | 0.1975 (5) | 0.0380 (12) | |
C1 | 0.4561 (10) | 0.93234 (17) | 0.0851 (8) | 0.0454 (17) | |
C2 | 0.6593 (9) | 0.97345 (16) | 0.1925 (7) | 0.0440 (16) | |
C3 | 1.3556 (10) | 0.9245 (2) | 0.3585 (10) | 0.065 (2) | |
H3A | 1.4285 | 0.9080 | 0.3885 | 0.097* | |
H3B | 1.4033 | 0.9385 | 0.4262 | 0.097* | |
H3C | 1.3423 | 0.9333 | 0.2883 | 0.097* | |
C4 | 0.8373 (12) | 0.81699 (16) | 0.1369 (8) | 0.056 (2) | |
H4A | 0.8231 | 0.8135 | 0.0608 | 0.084* | |
H4B | 0.7381 | 0.8111 | 0.1236 | 0.084* | |
H4C | 0.9314 | 0.8060 | 0.2061 | 0.084* | |
C5 | 1.1099 (11) | 0.95023 (19) | 0.4733 (7) | 0.054 (2) | |
H5A | 1.2292 | 0.9467 | 0.5247 | 0.065* | |
H5B | 1.0943 | 0.9705 | 0.4841 | 0.065* | |
C6 | 1.0403 (9) | 0.93103 (17) | 0.5198 (6) | 0.0423 (16) | |
C7 | 0.8973 (11) | 0.93993 (18) | 0.5021 (8) | 0.0502 (18) | |
H7 | 0.8468 | 0.9576 | 0.4622 | 0.060* | |
C8 | 0.8298 (12) | 0.9226 (2) | 0.5436 (9) | 0.063 (2) | |
H8 | 0.7330 | 0.9284 | 0.5294 | 0.076* | |
C9 | 0.9057 (13) | 0.8974 (2) | 0.6044 (8) | 0.062 (2) | |
C10 | 1.0485 (13) | 0.8888 (2) | 0.6276 (8) | 0.064 (2) | |
H10 | 1.1011 | 0.8716 | 0.6716 | 0.077* | |
C11 | 1.1143 (10) | 0.9055 (2) | 0.5860 (7) | 0.056 (2) | |
H11 | 1.2126 | 0.8995 | 0.6029 | 0.067* | |
C12 | 0.9649 (11) | 0.96861 (18) | 0.1346 (7) | 0.0516 (19) | |
H12A | 0.9217 | 0.9876 | 0.1320 | 0.062* | |
H12B | 1.0741 | 0.9714 | 0.1574 | 0.062* | |
C13 | 0.8495 (9) | 0.95493 (15) | 0.0050 (7) | 0.0399 (15) | |
C14 | 0.9149 (11) | 0.9391 (2) | −0.0428 (8) | 0.057 (2) | |
H14 | 1.0302 | 0.9375 | 0.0051 | 0.068* | |
C15 | 0.8075 (14) | 0.9260 (2) | −0.1618 (9) | 0.068 (3) | |
H15 | 0.8498 | 0.9159 | −0.1955 | 0.082* | |
C16 | 0.6388 (13) | 0.9280 (2) | −0.2283 (7) | 0.061 (2) | |
C17 | 0.5720 (11) | 0.94291 (17) | −0.1855 (8) | 0.053 (2) | |
H17 | 0.4564 | 0.9443 | −0.2338 | 0.064* | |
C18 | 0.6791 (10) | 0.95621 (16) | −0.0677 (7) | 0.0450 (17) | |
H18 | 0.6337 | 0.9664 | −0.0368 | 0.054* | |
C19 | 0.6611 (15) | 0.8640 (2) | 0.2674 (11) | 0.070 (3) | |
H19A | 0.7386 | 0.8749 | 0.3458 | 0.084* | |
H19B | 0.5489 | 0.8684 | 0.2364 | 0.084* | |
C20 | 0.6921 (10) | 0.83251 (17) | 0.2988 (7) | 0.0452 (17) | |
C21 | 0.5731 (12) | 0.8119 (2) | 0.2202 (9) | 0.067 (2) | |
H21 | 0.4712 | 0.8178 | 0.1447 | 0.081* | |
C22 | 0.5989 (17) | 0.7829 (2) | 0.2487 (14) | 0.086 (3) | |
H22 | 0.5172 | 0.7693 | 0.1928 | 0.104* | |
C23 | 0.7414 (18) | 0.7745 (2) | 0.3566 (15) | 0.084 (3) | |
C24 | 0.8651 (14) | 0.7927 (3) | 0.4403 (12) | 0.082 (3) | |
H24 | 0.9641 | 0.7858 | 0.5157 | 0.099* | |
C25 | 0.8414 (11) | 0.8229 (2) | 0.4110 (9) | 0.069 (3) | |
H25 | 0.9257 | 0.8361 | 0.4669 | 0.082* | |
C26 | 0.5420 (11) | 0.87894 (17) | −0.0712 (7) | 0.0494 (18) | |
H26A | 0.4479 | 0.8922 | −0.1101 | 0.059* | |
H26B | 0.6118 | 0.8860 | −0.0907 | 0.059* | |
C27 | 0.4760 (9) | 0.84916 (16) | −0.1307 (7) | 0.0440 (16) | |
C28 | 0.5399 (12) | 0.8352 (2) | −0.1822 (8) | 0.058 (2) | |
H28 | 0.6229 | 0.8440 | −0.1798 | 0.069* | |
C29 | 0.4788 (13) | 0.8078 (2) | −0.2377 (8) | 0.066 (2) | |
H29 | 0.5196 | 0.7984 | −0.2737 | 0.079* | |
C30 | 0.3596 (15) | 0.7950 (2) | −0.2388 (9) | 0.073 (3) | |
C31 | 0.2951 (13) | 0.8087 (2) | −0.1873 (9) | 0.069 (2) | |
H31 | 0.2128 | 0.7997 | −0.1891 | 0.082* | |
C32 | 0.3555 (10) | 0.83586 (18) | −0.1331 (8) | 0.0534 (19) | |
H32 | 0.3136 | 0.8453 | −0.0979 | 0.064* | |
C33 | 1.1616 (14) | 0.8670 (2) | 0.1472 (10) | 0.0653 (18) | |
H33A | 1.1257 | 0.8843 | 0.0947 | 0.078* | |
H33B | 1.2830 | 0.8668 | 0.2038 | 0.078* | |
C34 | 1.1027 (13) | 0.8414 (2) | 0.0609 (10) | 0.0653 (18) | |
C35 | 1.1589 (13) | 0.8136 (2) | 0.1060 (9) | 0.066 (2) | |
H35 | 1.2299 | 0.8102 | 0.1934 | 0.079* | |
C36 | 1.1128 (14) | 0.7909 (2) | 0.0253 (11) | 0.074 (3) | |
H36 | 1.1493 | 0.7721 | 0.0569 | 0.089* | |
C37 | 1.0143 (14) | 0.7959 (2) | −0.0998 (11) | 0.073 (3) | |
C38 | 0.9535 (16) | 0.8222 (3) | −0.1497 (11) | 0.089 (3) | |
H38 | 0.8808 | 0.8249 | −0.2375 | 0.107* | |
C39 | 1.0005 (14) | 0.8453 (2) | −0.0687 (10) | 0.072 (3) | |
H39 | 0.9623 | 0.8639 | −0.1024 | 0.087* | |
C40 | 1.2385 (11) | 0.8535 (2) | 0.4489 (8) | 0.060 (2) | |
H40A | 1.3207 | 0.8676 | 0.5105 | 0.072* | |
H40B | 1.1664 | 0.8490 | 0.4695 | 0.072* | |
C41 | 1.3267 (10) | 0.82649 (17) | 0.4604 (7) | 0.0479 (17) | |
C42 | 1.4822 (11) | 0.8276 (2) | 0.4905 (9) | 0.062 (2) | |
H42 | 1.5316 | 0.8456 | 0.5031 | 0.075* | |
C43 | 1.5658 (13) | 0.8028 (3) | 0.5021 (10) | 0.077 (3) | |
H43 | 1.6709 | 0.8040 | 0.5236 | 0.092* | |
C44 | 1.4915 (17) | 0.7767 (3) | 0.4816 (10) | 0.080 (3) | |
C45 | 1.3412 (15) | 0.7739 (2) | 0.4501 (10) | 0.079 (3) | |
H45 | 1.2937 | 0.7556 | 0.4359 | 0.095* | |
C46 | 1.2565 (12) | 0.7988 (2) | 0.4388 (8) | 0.062 (2) | |
H46 | 1.1511 | 0.7971 | 0.4164 | 0.074* | |
C47 | 0.5586 (14) | 1.0005 (2) | 0.4335 (10) | 0.069 (3) | |
H47 | 0.5976 | 1.0009 | 0.3878 | 0.082* | |
C48 | 0.6669 (13) | 0.99371 (17) | 0.5618 (10) | 0.060 (2) | |
H48 | 0.7787 | 0.9895 | 0.6031 | 0.072* | |
C49 | 0.6062 (14) | 0.9934 (2) | 0.6267 (9) | 0.070 (3) | |
H49 | 0.6780 | 0.9889 | 0.7131 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.0409 (3) | 0.0400 (3) | 0.0480 (3) | 0.0006 (2) | 0.0303 (2) | −0.0030 (2) |
Sn2 | 0.0393 (3) | 0.0357 (3) | 0.0343 (3) | −0.00752 (19) | 0.0230 (2) | −0.00782 (18) |
Sn3 | 0.0391 (3) | 0.0312 (3) | 0.0435 (3) | −0.00509 (18) | 0.0282 (2) | −0.00437 (18) |
S1 | 0.0481 (11) | 0.0596 (13) | 0.1021 (19) | −0.0090 (10) | 0.0509 (13) | −0.0123 (12) |
S2 | 0.0542 (11) | 0.0422 (10) | 0.0713 (14) | 0.0074 (9) | 0.0413 (11) | −0.0030 (9) |
S3 | 0.0691 (14) | 0.0409 (10) | 0.0666 (13) | −0.0066 (9) | 0.0423 (12) | −0.0162 (9) |
F1 | 0.134 (6) | 0.089 (4) | 0.103 (5) | −0.019 (4) | 0.096 (5) | 0.004 (4) |
F2 | 0.127 (6) | 0.101 (5) | 0.041 (3) | −0.002 (4) | 0.033 (3) | −0.019 (3) |
F3 | 0.208 (10) | 0.067 (5) | 0.267 (12) | 0.047 (5) | 0.190 (10) | 0.052 (6) |
F4 | 0.156 (7) | 0.060 (4) | 0.091 (5) | −0.026 (4) | 0.065 (5) | −0.032 (3) |
F5 | 0.171 (8) | 0.099 (5) | 0.151 (7) | −0.044 (5) | 0.123 (7) | −0.065 (5) |
F6 | 0.142 (7) | 0.101 (5) | 0.115 (6) | 0.059 (5) | 0.080 (5) | 0.009 (4) |
O1 | 0.033 (2) | 0.032 (2) | 0.045 (3) | −0.0005 (18) | 0.022 (2) | −0.0051 (19) |
O2 | 0.037 (3) | 0.050 (3) | 0.062 (3) | −0.009 (2) | 0.032 (3) | −0.015 (3) |
O3 | 0.046 (3) | 0.035 (3) | 0.062 (3) | −0.003 (2) | 0.037 (3) | −0.005 (2) |
N1 | 0.041 (3) | 0.034 (3) | 0.052 (3) | −0.001 (2) | 0.035 (3) | −0.004 (2) |
N2 | 0.037 (3) | 0.035 (3) | 0.039 (3) | −0.002 (2) | 0.023 (3) | −0.007 (2) |
C1 | 0.047 (4) | 0.044 (4) | 0.059 (5) | 0.001 (3) | 0.040 (4) | 0.003 (3) |
C2 | 0.048 (4) | 0.042 (4) | 0.045 (4) | 0.003 (3) | 0.031 (4) | −0.006 (3) |
C3 | 0.044 (4) | 0.066 (6) | 0.092 (7) | −0.005 (4) | 0.047 (5) | −0.005 (5) |
C4 | 0.069 (5) | 0.036 (4) | 0.062 (5) | 0.016 (4) | 0.041 (5) | −0.001 (4) |
C5 | 0.057 (5) | 0.061 (5) | 0.040 (4) | −0.013 (4) | 0.028 (4) | −0.017 (4) |
C6 | 0.042 (4) | 0.052 (4) | 0.028 (3) | −0.002 (3) | 0.020 (3) | −0.008 (3) |
C7 | 0.057 (5) | 0.052 (5) | 0.048 (4) | 0.003 (4) | 0.037 (4) | 0.002 (3) |
C8 | 0.065 (5) | 0.081 (6) | 0.064 (5) | 0.000 (5) | 0.050 (5) | −0.002 (5) |
C9 | 0.086 (7) | 0.058 (5) | 0.053 (5) | −0.013 (5) | 0.049 (5) | −0.001 (4) |
C10 | 0.079 (6) | 0.054 (5) | 0.050 (5) | 0.006 (5) | 0.037 (5) | 0.005 (4) |
C11 | 0.046 (4) | 0.072 (6) | 0.035 (4) | 0.004 (4) | 0.019 (4) | 0.000 (4) |
C12 | 0.058 (5) | 0.050 (4) | 0.050 (4) | −0.005 (4) | 0.036 (4) | 0.003 (4) |
C13 | 0.049 (4) | 0.036 (3) | 0.040 (4) | 0.006 (3) | 0.031 (3) | 0.005 (3) |
C14 | 0.054 (5) | 0.074 (6) | 0.044 (4) | 0.020 (4) | 0.032 (4) | 0.008 (4) |
C15 | 0.099 (8) | 0.070 (6) | 0.052 (5) | 0.028 (5) | 0.056 (6) | 0.007 (4) |
C16 | 0.076 (6) | 0.055 (5) | 0.032 (4) | 0.006 (4) | 0.025 (4) | 0.003 (3) |
C17 | 0.046 (4) | 0.049 (5) | 0.045 (4) | 0.005 (3) | 0.019 (4) | 0.014 (3) |
C18 | 0.053 (4) | 0.043 (4) | 0.050 (4) | 0.009 (3) | 0.038 (4) | 0.007 (3) |
C19 | 0.103 (8) | 0.062 (6) | 0.088 (7) | 0.010 (5) | 0.080 (7) | 0.012 (5) |
C20 | 0.054 (4) | 0.046 (4) | 0.053 (4) | −0.007 (3) | 0.042 (4) | −0.002 (3) |
C21 | 0.055 (5) | 0.073 (6) | 0.058 (5) | −0.017 (5) | 0.029 (4) | 0.002 (5) |
C22 | 0.101 (9) | 0.062 (7) | 0.124 (10) | −0.026 (6) | 0.085 (9) | −0.014 (7) |
C23 | 0.105 (9) | 0.051 (6) | 0.141 (11) | 0.010 (6) | 0.099 (9) | 0.022 (7) |
C24 | 0.069 (6) | 0.092 (8) | 0.105 (8) | 0.033 (6) | 0.064 (7) | 0.049 (7) |
C25 | 0.050 (5) | 0.085 (7) | 0.065 (6) | −0.019 (5) | 0.034 (5) | −0.005 (5) |
C26 | 0.057 (5) | 0.045 (4) | 0.044 (4) | −0.007 (3) | 0.032 (4) | −0.001 (3) |
C27 | 0.043 (4) | 0.043 (4) | 0.038 (4) | −0.003 (3) | 0.022 (3) | −0.002 (3) |
C28 | 0.064 (5) | 0.066 (5) | 0.050 (5) | 0.002 (4) | 0.039 (4) | −0.005 (4) |
C29 | 0.086 (7) | 0.062 (6) | 0.047 (5) | 0.007 (5) | 0.040 (5) | −0.007 (4) |
C30 | 0.099 (8) | 0.046 (5) | 0.054 (5) | −0.004 (5) | 0.039 (6) | −0.013 (4) |
C31 | 0.068 (6) | 0.057 (5) | 0.065 (6) | −0.016 (5) | 0.035 (5) | −0.009 (4) |
C32 | 0.052 (4) | 0.050 (4) | 0.050 (4) | −0.008 (4) | 0.028 (4) | −0.006 (4) |
C33 | 0.087 (5) | 0.062 (4) | 0.088 (5) | −0.019 (3) | 0.075 (4) | −0.016 (3) |
C34 | 0.087 (5) | 0.062 (4) | 0.088 (5) | −0.019 (3) | 0.075 (4) | −0.016 (3) |
C35 | 0.078 (6) | 0.073 (6) | 0.056 (5) | 0.014 (5) | 0.047 (5) | 0.011 (4) |
C36 | 0.098 (8) | 0.050 (5) | 0.104 (8) | 0.020 (5) | 0.078 (7) | 0.017 (5) |
C37 | 0.081 (7) | 0.071 (6) | 0.092 (8) | −0.018 (5) | 0.066 (7) | −0.027 (6) |
C38 | 0.094 (8) | 0.101 (9) | 0.054 (6) | 0.001 (7) | 0.038 (6) | −0.001 (6) |
C39 | 0.089 (7) | 0.061 (6) | 0.070 (6) | 0.022 (5) | 0.052 (6) | 0.022 (5) |
C40 | 0.060 (5) | 0.071 (6) | 0.048 (5) | 0.008 (4) | 0.034 (4) | −0.002 (4) |
C41 | 0.051 (4) | 0.052 (5) | 0.038 (4) | 0.005 (3) | 0.027 (4) | 0.006 (3) |
C42 | 0.049 (5) | 0.074 (6) | 0.059 (5) | −0.007 (4) | 0.032 (4) | −0.005 (4) |
C43 | 0.053 (5) | 0.101 (9) | 0.072 (6) | 0.019 (5) | 0.038 (5) | −0.004 (6) |
C44 | 0.101 (9) | 0.072 (7) | 0.056 (6) | 0.033 (6) | 0.045 (6) | 0.003 (5) |
C45 | 0.090 (8) | 0.051 (5) | 0.067 (6) | −0.003 (5) | 0.036 (6) | 0.000 (5) |
C46 | 0.063 (5) | 0.078 (6) | 0.043 (4) | 0.006 (5) | 0.032 (4) | 0.008 (4) |
C47 | 0.090 (7) | 0.057 (5) | 0.087 (7) | −0.032 (5) | 0.069 (6) | −0.022 (5) |
C48 | 0.070 (6) | 0.039 (4) | 0.083 (7) | −0.005 (4) | 0.054 (5) | −0.003 (4) |
C49 | 0.080 (7) | 0.061 (6) | 0.057 (5) | −0.015 (5) | 0.037 (5) | 0.000 (4) |
Sn1—O1 | 2.044 (4) | C18—H18 | 0.9300 |
Sn1—O3 | 2.116 (5) | C19—C20 | 1.486 (12) |
Sn1—C33 | 2.125 (8) | C19—H19A | 0.9700 |
Sn1—O2 | 2.131 (5) | C19—H19B | 0.9700 |
Sn1—C40 | 2.142 (9) | C20—C21 | 1.373 (12) |
Sn2—O1 | 2.038 (5) | C20—C25 | 1.383 (12) |
Sn2—C12 | 2.141 (7) | C21—C22 | 1.366 (15) |
Sn2—C5 | 2.142 (7) | C21—H21 | 0.9300 |
Sn2—O2 | 2.184 (5) | C22—C23 | 1.312 (17) |
Sn2—N2 | 2.225 (6) | C22—H22 | 0.9300 |
Sn3—O1 | 2.054 (4) | C23—C24 | 1.334 (18) |
Sn3—C26 | 2.127 (8) | C24—C25 | 1.419 (15) |
Sn3—C19 | 2.150 (8) | C24—H24 | 0.9300 |
Sn3—O3 | 2.188 (5) | C25—H25 | 0.9300 |
Sn3—N1 | 2.217 (5) | C26—C27 | 1.513 (10) |
S1—C1 | 1.679 (8) | C26—H26A | 0.9700 |
S2—C2 | 1.732 (8) | C26—H26B | 0.9700 |
S2—C1 | 1.738 (8) | C27—C32 | 1.369 (11) |
S3—C2 | 1.672 (8) | C27—C28 | 1.386 (11) |
F1—C9 | 1.358 (10) | C28—C29 | 1.394 (13) |
F2—C16 | 1.370 (10) | C28—H28 | 0.9300 |
F3—C23 | 1.367 (12) | C29—C30 | 1.357 (15) |
F4—C30 | 1.342 (11) | C29—H29 | 0.9300 |
F5—C37 | 1.371 (11) | C30—C31 | 1.386 (15) |
F6—C44 | 1.357 (11) | C31—C32 | 1.381 (12) |
O2—C3 | 1.454 (9) | C31—H31 | 0.9300 |
O3—C4 | 1.462 (9) | C32—H32 | 0.9300 |
N1—C1 | 1.339 (9) | C33—C34 | 1.488 (12) |
N1—N2 | 1.382 (8) | C33—H33A | 0.9700 |
N2—C2 | 1.349 (9) | C33—H33B | 0.9700 |
C3—H3A | 0.9600 | C34—C39 | 1.373 (14) |
C3—H3B | 0.9600 | C34—C35 | 1.377 (13) |
C3—H3C | 0.9600 | C35—C36 | 1.360 (14) |
C4—H4A | 0.9600 | C35—H35 | 0.9300 |
C4—H4B | 0.9600 | C36—C37 | 1.334 (15) |
C4—H4C | 0.9600 | C36—H36 | 0.9300 |
C5—C6 | 1.506 (11) | C37—C38 | 1.331 (16) |
C5—H5A | 0.9700 | C38—C39 | 1.375 (15) |
C5—H5B | 0.9700 | C38—H38 | 0.9300 |
C6—C11 | 1.376 (12) | C39—H39 | 0.9300 |
C6—C7 | 1.399 (11) | C40—C41 | 1.487 (12) |
C7—C8 | 1.390 (12) | C40—H40A | 0.9700 |
C7—H7 | 0.9300 | C40—H40B | 0.9700 |
C8—C9 | 1.348 (13) | C41—C42 | 1.385 (12) |
C8—H8 | 0.9300 | C41—C46 | 1.399 (12) |
C9—C10 | 1.357 (14) | C42—C43 | 1.375 (14) |
C10—C11 | 1.363 (13) | C42—H42 | 0.9300 |
C10—H10 | 0.9300 | C43—C44 | 1.353 (17) |
C11—H11 | 0.9300 | C43—H43 | 0.9300 |
C12—C13 | 1.500 (11) | C44—C45 | 1.330 (16) |
C12—H12A | 0.9700 | C45—C46 | 1.389 (14) |
C12—H12B | 0.9700 | C45—H45 | 0.9300 |
C13—C18 | 1.368 (10) | C46—H46 | 0.9300 |
C13—C14 | 1.400 (10) | C47—C49i | 1.372 (15) |
C14—C15 | 1.391 (13) | C47—C48 | 1.381 (14) |
C14—H14 | 0.9300 | C47—H47 | 0.9300 |
C15—C16 | 1.366 (14) | C48—C49 | 1.368 (13) |
C15—H15 | 0.9300 | C48—H48 | 0.9300 |
C16—C17 | 1.338 (13) | C49—C47i | 1.372 (15) |
C17—C18 | 1.382 (11) | C49—H49 | 0.9300 |
C17—H17 | 0.9300 | ||
O1—Sn1—O3 | 73.36 (18) | C13—C18—C17 | 122.3 (7) |
O1—Sn1—C33 | 123.9 (3) | C13—C18—H18 | 118.8 |
O3—Sn1—C33 | 104.1 (3) | C17—C18—H18 | 118.8 |
O1—Sn1—O2 | 71.11 (18) | C20—C19—Sn3 | 117.4 (6) |
O3—Sn1—O2 | 144.2 (2) | C20—C19—H19A | 108.0 |
C33—Sn1—O2 | 92.0 (3) | Sn3—C19—H19A | 108.0 |
O1—Sn1—C40 | 115.1 (3) | C20—C19—H19B | 108.0 |
O3—Sn1—C40 | 100.9 (3) | Sn3—C19—H19B | 108.0 |
C33—Sn1—C40 | 120.1 (4) | H19A—C19—H19B | 107.2 |
O2—Sn1—C40 | 98.1 (3) | C21—C20—C25 | 117.3 (8) |
O1—Sn2—C12 | 114.1 (3) | C21—C20—C19 | 121.8 (9) |
O1—Sn2—C5 | 113.1 (3) | C25—C20—C19 | 121.0 (8) |
C12—Sn2—C5 | 132.4 (3) | C22—C21—C20 | 122.4 (10) |
O1—Sn2—O2 | 70.13 (18) | C22—C21—H21 | 118.8 |
C12—Sn2—O2 | 95.7 (3) | C20—C21—H21 | 118.8 |
C5—Sn2—O2 | 94.9 (3) | C23—C22—C21 | 118.6 (11) |
O1—Sn2—N2 | 80.20 (19) | C23—C22—H22 | 120.7 |
C12—Sn2—N2 | 95.0 (3) | C21—C22—H22 | 120.7 |
C5—Sn2—N2 | 98.1 (3) | C22—C23—C24 | 124.0 (10) |
O2—Sn2—N2 | 150.29 (19) | C22—C23—F3 | 119.5 (13) |
O1—Sn3—C26 | 112.2 (3) | C24—C23—F3 | 116.5 (13) |
O1—Sn3—C19 | 109.9 (4) | C23—C24—C25 | 118.1 (10) |
C26—Sn3—C19 | 137.9 (4) | C23—C24—H24 | 121.0 |
O1—Sn3—O3 | 71.67 (18) | C25—C24—H24 | 121.0 |
C26—Sn3—O3 | 94.1 (3) | C20—C25—C24 | 119.6 (9) |
C19—Sn3—O3 | 97.0 (3) | C20—C25—H25 | 120.2 |
O1—Sn3—N1 | 79.50 (19) | C24—C25—H25 | 120.2 |
C26—Sn3—N1 | 95.9 (3) | C27—C26—Sn3 | 114.6 (5) |
C19—Sn3—N1 | 93.6 (3) | C27—C26—H26A | 108.6 |
O3—Sn3—N1 | 151.2 (2) | Sn3—C26—H26A | 108.6 |
C2—S2—C1 | 91.9 (4) | C27—C26—H26B | 108.6 |
Sn2—O1—Sn1 | 113.8 (2) | Sn3—C26—H26B | 108.6 |
Sn2—O1—Sn3 | 134.9 (2) | H26A—C26—H26B | 107.6 |
Sn1—O1—Sn3 | 111.3 (2) | C32—C27—C28 | 119.9 (8) |
C3—O2—Sn1 | 127.1 (5) | C32—C27—C26 | 120.7 (7) |
C3—O2—Sn2 | 127.8 (5) | C28—C27—C26 | 119.4 (7) |
Sn1—O2—Sn2 | 104.8 (2) | C27—C28—C29 | 119.6 (9) |
C4—O3—Sn1 | 129.8 (5) | C27—C28—H28 | 120.2 |
C4—O3—Sn3 | 126.5 (5) | C29—C28—H28 | 120.2 |
Sn1—O3—Sn3 | 103.6 (2) | C30—C29—C28 | 119.6 (9) |
C1—N1—N2 | 114.5 (6) | C30—C29—H29 | 120.2 |
C1—N1—Sn3 | 121.9 (5) | C28—C29—H29 | 120.2 |
N2—N1—Sn3 | 123.6 (4) | F4—C30—C29 | 120.6 (10) |
C2—N2—N1 | 114.3 (6) | F4—C30—C31 | 118.0 (11) |
C2—N2—Sn2 | 123.9 (5) | C29—C30—C31 | 121.4 (9) |
N1—N2—Sn2 | 121.5 (4) | C32—C31—C30 | 118.7 (9) |
N1—C1—S1 | 124.3 (6) | C32—C31—H31 | 120.7 |
N1—C1—S2 | 109.7 (5) | C30—C31—H31 | 120.7 |
S1—C1—S2 | 126.0 (5) | C27—C32—C31 | 120.9 (9) |
N2—C2—S3 | 123.6 (6) | C27—C32—H32 | 119.6 |
N2—C2—S2 | 109.6 (5) | C31—C32—H32 | 119.6 |
S3—C2—S2 | 126.8 (4) | C34—C33—Sn1 | 120.9 (6) |
O2—C3—H3A | 109.5 | C34—C33—H33A | 107.1 |
O2—C3—H3B | 109.5 | Sn1—C33—H33A | 107.1 |
H3A—C3—H3B | 109.5 | C34—C33—H33B | 107.1 |
O2—C3—H3C | 109.5 | Sn1—C33—H33B | 107.1 |
H3A—C3—H3C | 109.5 | H33A—C33—H33B | 106.8 |
H3B—C3—H3C | 109.5 | C39—C34—C35 | 117.0 (9) |
O3—C4—H4A | 109.5 | C39—C34—C33 | 120.3 (9) |
O3—C4—H4B | 109.5 | C35—C34—C33 | 122.5 (10) |
H4A—C4—H4B | 109.5 | C36—C35—C34 | 121.4 (9) |
O3—C4—H4C | 109.5 | C36—C35—H35 | 119.3 |
H4A—C4—H4C | 109.5 | C34—C35—H35 | 119.3 |
H4B—C4—H4C | 109.5 | C37—C36—C35 | 119.1 (9) |
C6—C5—Sn2 | 112.1 (5) | C37—C36—H36 | 120.4 |
C6—C5—H5A | 109.2 | C35—C36—H36 | 120.4 |
Sn2—C5—H5A | 109.2 | C38—C37—C36 | 122.5 (10) |
C6—C5—H5B | 109.2 | C38—C37—F5 | 118.1 (11) |
Sn2—C5—H5B | 109.2 | C36—C37—F5 | 119.4 (11) |
H5A—C5—H5B | 107.9 | C37—C38—C39 | 118.6 (10) |
C11—C6—C7 | 116.7 (7) | C37—C38—H38 | 120.7 |
C11—C6—C5 | 123.9 (7) | C39—C38—H38 | 120.7 |
C7—C6—C5 | 119.3 (7) | C34—C39—C38 | 121.3 (10) |
C8—C7—C6 | 120.6 (8) | C34—C39—H39 | 119.3 |
C8—C7—H7 | 119.7 | C38—C39—H39 | 119.3 |
C6—C7—H7 | 119.7 | C41—C40—Sn1 | 113.2 (5) |
C9—C8—C7 | 119.6 (9) | C41—C40—H40A | 108.9 |
C9—C8—H8 | 120.2 | Sn1—C40—H40A | 108.9 |
C7—C8—H8 | 120.2 | C41—C40—H40B | 108.9 |
C8—C9—C10 | 121.1 (8) | Sn1—C40—H40B | 108.9 |
C8—C9—F1 | 119.3 (9) | H40A—C40—H40B | 107.8 |
C10—C9—F1 | 119.6 (9) | C42—C41—C46 | 116.4 (8) |
C9—C10—C11 | 119.6 (9) | C42—C41—C40 | 121.3 (8) |
C9—C10—H10 | 120.2 | C46—C41—C40 | 122.3 (8) |
C11—C10—H10 | 120.2 | C43—C42—C41 | 122.0 (9) |
C10—C11—C6 | 122.3 (8) | C43—C42—H42 | 119.0 |
C10—C11—H11 | 118.9 | C41—C42—H42 | 119.0 |
C6—C11—H11 | 118.9 | C44—C43—C42 | 118.4 (10) |
C13—C12—Sn2 | 112.0 (5) | C44—C43—H43 | 120.8 |
C13—C12—H12A | 109.2 | C42—C43—H43 | 120.8 |
Sn2—C12—H12A | 109.2 | C45—C44—C43 | 123.2 (10) |
C13—C12—H12B | 109.2 | C45—C44—F6 | 118.4 (12) |
Sn2—C12—H12B | 109.2 | C43—C44—F6 | 118.5 (12) |
H12A—C12—H12B | 107.9 | C44—C45—C46 | 118.7 (10) |
C18—C13—C14 | 117.8 (7) | C44—C45—H45 | 120.7 |
C18—C13—C12 | 122.0 (7) | C46—C45—H45 | 120.7 |
C14—C13—C12 | 120.1 (7) | C45—C46—C41 | 121.3 (9) |
C15—C14—C13 | 120.0 (8) | C45—C46—H46 | 119.3 |
C15—C14—H14 | 120.0 | C41—C46—H46 | 119.3 |
C13—C14—H14 | 120.0 | C49i—C47—C48 | 120.2 (9) |
C16—C15—C14 | 118.7 (8) | C49i—C47—H47 | 119.9 |
C16—C15—H15 | 120.7 | C48—C47—H47 | 119.9 |
C14—C15—H15 | 120.7 | C49—C48—C47 | 118.7 (9) |
C17—C16—C15 | 122.8 (8) | C49—C48—H48 | 120.7 |
C17—C16—F2 | 119.8 (9) | C47—C48—H48 | 120.7 |
C15—C16—F2 | 117.4 (9) | C48—C49—C47i | 121.1 (9) |
C16—C17—C18 | 118.3 (8) | C48—C49—H49 | 119.4 |
C16—C17—H17 | 120.9 | C47i—C49—H49 | 119.4 |
C18—C17—H17 | 120.9 | ||
C12—Sn2—O1—Sn1 | 90.6 (3) | Sn2—C5—C6—C7 | −86.0 (8) |
C5—Sn2—O1—Sn1 | −83.6 (3) | C11—C6—C7—C8 | −3.7 (12) |
O2—Sn2—O1—Sn1 | 3.2 (2) | C5—C6—C7—C8 | 179.8 (7) |
N2—Sn2—O1—Sn1 | −178.3 (3) | C6—C7—C8—C9 | 1.8 (13) |
C12—Sn2—O1—Sn3 | −88.3 (4) | C7—C8—C9—C10 | 1.0 (14) |
C5—Sn2—O1—Sn3 | 97.5 (4) | C7—C8—C9—F1 | 179.6 (8) |
O2—Sn2—O1—Sn3 | −175.7 (4) | C8—C9—C10—C11 | −1.7 (14) |
N2—Sn2—O1—Sn3 | 2.8 (3) | F1—C9—C10—C11 | 179.7 (8) |
O3—Sn1—O1—Sn2 | −178.6 (3) | C9—C10—C11—C6 | −0.4 (13) |
C33—Sn1—O1—Sn2 | −82.6 (4) | C7—C6—C11—C10 | 3.0 (12) |
O2—Sn1—O1—Sn2 | −3.3 (2) | C5—C6—C11—C10 | 179.4 (7) |
C40—Sn1—O1—Sn2 | 87.0 (4) | O1—Sn2—C12—C13 | 15.3 (7) |
O3—Sn1—O1—Sn3 | 0.6 (2) | C5—Sn2—C12—C13 | −171.9 (5) |
C33—Sn1—O1—Sn3 | 96.6 (4) | O2—Sn2—C12—C13 | 86.1 (6) |
O2—Sn1—O1—Sn3 | 175.9 (3) | N2—Sn2—C12—C13 | −66.2 (6) |
C40—Sn1—O1—Sn3 | −93.8 (4) | Sn2—C12—C13—C18 | 78.7 (8) |
C26—Sn3—O1—Sn2 | 91.4 (4) | Sn2—C12—C13—C14 | −98.4 (8) |
C19—Sn3—O1—Sn2 | −90.7 (4) | C18—C13—C14—C15 | 1.5 (12) |
O3—Sn3—O1—Sn2 | 178.4 (4) | C12—C13—C14—C15 | 178.6 (8) |
N1—Sn3—O1—Sn2 | −0.7 (3) | C13—C14—C15—C16 | −2.0 (14) |
C26—Sn3—O1—Sn1 | −87.5 (3) | C14—C15—C16—C17 | 2.0 (15) |
C19—Sn3—O1—Sn1 | 90.4 (3) | C14—C15—C16—F2 | −178.3 (8) |
O3—Sn3—O1—Sn1 | −0.6 (2) | C15—C16—C17—C18 | −1.3 (13) |
N1—Sn3—O1—Sn1 | −179.6 (3) | F2—C16—C17—C18 | 178.9 (8) |
O1—Sn1—O2—C3 | −171.4 (7) | C14—C13—C18—C17 | −0.9 (11) |
O3—Sn1—O2—C3 | −163.7 (6) | C12—C13—C18—C17 | −178.0 (7) |
C33—Sn1—O2—C3 | −46.1 (7) | C16—C17—C18—C13 | 0.8 (12) |
C40—Sn1—O2—C3 | 74.7 (7) | O1—Sn3—C19—C20 | −101.4 (8) |
O1—Sn1—O2—Sn2 | 2.9 (2) | C26—Sn3—C19—C20 | 75.6 (10) |
O3—Sn1—O2—Sn2 | 10.6 (5) | O3—Sn3—C19—C20 | −28.5 (8) |
C33—Sn1—O2—Sn2 | 128.3 (4) | N1—Sn3—C19—C20 | 178.4 (8) |
C40—Sn1—O2—Sn2 | −111.0 (3) | Sn3—C19—C20—C21 | −78.9 (10) |
O1—Sn2—O2—C3 | 171.3 (7) | Sn3—C19—C20—C25 | 102.9 (9) |
C12—Sn2—O2—C3 | 57.8 (7) | C25—C20—C21—C22 | −0.8 (14) |
C5—Sn2—O2—C3 | −75.8 (7) | C19—C20—C21—C22 | −179.0 (9) |
N2—Sn2—O2—C3 | 168.3 (6) | C20—C21—C22—C23 | 1.5 (17) |
O1—Sn2—O2—Sn1 | −2.9 (2) | C21—C22—C23—C24 | −1.0 (19) |
C12—Sn2—O2—Sn1 | −116.5 (3) | C21—C22—C23—F3 | 178.0 (10) |
C5—Sn2—O2—Sn1 | 109.9 (3) | C22—C23—C24—C25 | −0.1 (18) |
N2—Sn2—O2—Sn1 | −6.0 (5) | F3—C23—C24—C25 | −179.1 (9) |
O1—Sn1—O3—C4 | −178.4 (7) | C21—C20—C25—C24 | −0.3 (13) |
C33—Sn1—O3—C4 | 59.9 (7) | C19—C20—C25—C24 | 177.9 (8) |
O2—Sn1—O3—C4 | 174.0 (6) | C23—C24—C25—C20 | 0.8 (15) |
C40—Sn1—O3—C4 | −65.2 (7) | O1—Sn3—C26—C27 | 129.7 (5) |
O1—Sn1—O3—Sn3 | −0.52 (19) | C19—Sn3—C26—C27 | −47.3 (8) |
C33—Sn1—O3—Sn3 | −122.2 (3) | O3—Sn3—C26—C27 | 57.9 (6) |
O2—Sn1—O3—Sn3 | −8.1 (5) | N1—Sn3—C26—C27 | −149.2 (6) |
C40—Sn1—O3—Sn3 | 112.7 (3) | Sn3—C26—C27—C32 | 67.6 (9) |
O1—Sn3—O3—C4 | 178.5 (6) | Sn3—C26—C27—C28 | −111.9 (7) |
C26—Sn3—O3—C4 | −69.5 (6) | C32—C27—C28—C29 | 0.9 (12) |
C19—Sn3—O3—C4 | 69.8 (7) | C26—C27—C28—C29 | −179.7 (8) |
N1—Sn3—O3—C4 | −179.7 (5) | C27—C28—C29—C30 | −1.0 (14) |
O1—Sn3—O3—Sn1 | 0.5 (2) | C28—C29—C30—F4 | 180.0 (9) |
C26—Sn3—O3—Sn1 | 112.6 (3) | C28—C29—C30—C31 | 0.9 (15) |
C19—Sn3—O3—Sn1 | −108.2 (4) | F4—C30—C31—C32 | −179.6 (9) |
N1—Sn3—O3—Sn1 | 2.4 (6) | C29—C30—C31—C32 | −0.5 (15) |
O1—Sn3—N1—C1 | 177.6 (6) | C28—C27—C32—C31 | −0.5 (13) |
C26—Sn3—N1—C1 | 66.1 (6) | C26—C27—C32—C31 | −179.9 (8) |
C19—Sn3—N1—C1 | −72.8 (6) | C30—C31—C32—C27 | 0.3 (14) |
O3—Sn3—N1—C1 | 175.8 (5) | O1—Sn1—C33—C34 | −102.5 (9) |
O1—Sn3—N1—N2 | −3.7 (5) | O3—Sn1—C33—C34 | −23.2 (10) |
C26—Sn3—N1—N2 | −115.2 (5) | O2—Sn1—C33—C34 | −170.9 (9) |
C19—Sn3—N1—N2 | 105.9 (6) | C40—Sn1—C33—C34 | 88.5 (10) |
O3—Sn3—N1—N2 | −5.5 (8) | Sn1—C33—C34—C39 | 116.1 (9) |
C1—N1—N2—C2 | −0.4 (9) | Sn1—C33—C34—C35 | −70.0 (12) |
Sn3—N1—N2—C2 | −179.2 (5) | C39—C34—C35—C36 | −1.1 (15) |
C1—N1—N2—Sn2 | −174.6 (5) | C33—C34—C35—C36 | −175.1 (9) |
Sn3—N1—N2—Sn2 | 6.6 (7) | C34—C35—C36—C37 | 1.7 (16) |
O1—Sn2—N2—C2 | −178.7 (6) | C35—C36—C37—C38 | −2.8 (17) |
C12—Sn2—N2—C2 | −65.0 (6) | C35—C36—C37—F5 | 178.9 (9) |
C5—Sn2—N2—C2 | 69.1 (6) | C36—C37—C38—C39 | 3.2 (19) |
O2—Sn2—N2—C2 | −175.8 (5) | F5—C37—C38—C39 | −178.5 (10) |
O1—Sn2—N2—N1 | −5.1 (5) | C35—C34—C39—C38 | 1.5 (16) |
C12—Sn2—N2—N1 | 108.5 (5) | C33—C34—C39—C38 | 175.7 (10) |
C5—Sn2—N2—N1 | −117.3 (5) | C37—C38—C39—C34 | −2.5 (19) |
O2—Sn2—N2—N1 | −2.2 (8) | O1—Sn1—C40—C41 | 160.7 (6) |
N2—N1—C1—S1 | 179.8 (5) | O3—Sn1—C40—C41 | 84.1 (7) |
Sn3—N1—C1—S1 | −1.4 (9) | C33—Sn1—C40—C41 | −29.3 (8) |
N2—N1—C1—S2 | 0.0 (8) | O2—Sn1—C40—C41 | −126.4 (6) |
Sn3—N1—C1—S2 | 178.8 (3) | Sn1—C40—C41—C42 | 86.6 (9) |
C2—S2—C1—N1 | 0.3 (6) | Sn1—C40—C41—C46 | −91.9 (8) |
C2—S2—C1—S1 | −179.5 (6) | C46—C41—C42—C43 | −1.8 (13) |
N1—N2—C2—S3 | 179.9 (5) | C40—C41—C42—C43 | 179.7 (8) |
Sn2—N2—C2—S3 | −6.1 (9) | C41—C42—C43—C44 | 1.0 (15) |
N1—N2—C2—S2 | 0.6 (8) | C42—C43—C44—C45 | 0.3 (16) |
Sn2—N2—C2—S2 | 174.6 (3) | C42—C43—C44—F6 | −178.9 (9) |
C1—S2—C2—N2 | −0.5 (6) | C43—C44—C45—C46 | −0.6 (16) |
C1—S2—C2—S3 | −179.7 (6) | F6—C44—C45—C46 | 178.6 (9) |
O1—Sn2—C5—C6 | −29.7 (7) | C44—C45—C46—C41 | −0.3 (15) |
C12—Sn2—C5—C6 | 157.5 (5) | C42—C41—C46—C45 | 1.5 (12) |
O2—Sn2—C5—C6 | −100.2 (6) | C40—C41—C46—C45 | 180.0 (8) |
N2—Sn2—C5—C6 | 53.1 (6) | C49i—C47—C48—C49 | −0.1 (15) |
Sn2—C5—C6—C11 | 97.7 (8) | C47—C48—C49—C47i | 0.1 (15) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Sn3(C7H7F)6(CH3O)2(C2N2S3)O]·0.5C6H6 |
Mr | 1276.12 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.3309 (9), 45.937 (4), 13.5763 (8) |
β (°) | 129.394 (4) |
V (Å3) | 4979.1 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.68 |
Crystal size (mm) | 0.18 × 0.16 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.751, 0.877 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 51752, 9782, 8279 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.184, 1.02 |
No. of reflections | 9782 |
No. of parameters | 591 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.123P)2 + 12.502P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.72, −1.78 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
From Fig. 1, like other trinuclear organotin-µ3oxo clusters (Ma et al., 2007), the complex (I) contains a tricyclic system formed from a N2Sn2O ring and two Sn2O2 rings: all three Sn atoms exhibit severely distorted trigonal bipyramidal configurations. The atoms Sn2 and Sn3 have similar environments, in which one O atom and two C atoms of the benzyl groups occupy the equatorial positions (C5, C12 and O1 for Sn2; C19, C26 and O1 for Sn3). The axial positions are occupied by one N atom of the HHdmt and one O atom of the methoxy group (N2 and O2 for Sn1; N1 and O3 for Sn3). The geometry of Sn1 is cis-R2SnO3, in which the axial positions are defined by O2 and O3 atoms of methoxy group, C33 and C40 atoms of benzyl groups and one O atom occupy the equatorial plane.
With regard to the role of reaction hydrolysis, three [(C7H7F)2Sn] units are bridged by one O atom and two O atoms of methoxy group, forming a trinuclear complex, containing two Sn2O2 rings. Three Sn atoms and three O atoms (Sn1, Sn2, Sn3, O1, O2, O3) comprise a fused ring system, which is similar to traditional hydrolytic products of ladder-type arrangement (Puff et al., 1983), but different from the staircase structure of C84H148N8O10Sn4 (Yin et al., 2006). The Sn—O distances lies in the range 2.038 (5) to 2.188 (5) Å (Table 1), which are consistent with those Sn—O bonds in the ladder structure reported (Harrison et al., 1980). All of above indicates that strong bridge-oxo coordination with Sn atoms exist in the complex. Moreover, the aromatic rings effectively surround the –O—CH3 group.
The HHdmt ligand forms a five-membered ring, where two N atoms bond to the two Sn atoms to form another five-membered N2Sn2O1 ring. The Sn—N bond lengths [Sn2—N2 2.225 (6) Å and Sn3—N1 2.217 (7) Å] approach the covalent radii of Sn and N (2.15 Å) and are much shorter than the van der Waal's radii of Sn and N atoms (3.74 Å) (Hubeey et al., 1993), proving that N is coordinated to Sn by strong chemical bonds.