Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102021091/fr1402sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102021091/fr1402Isup2.hkl |
CCDC reference: 204025
1,9-Diamino-3,7-dithianonane, H2N(CH2)2S(CH2)3S(CH2)2NH2 (ete), was prepared using the published procedure of Dwyer et al. (1952). 1,9-Bis(2-hydroxy-1-naphthalenemethylimino)-3,7-dithianonane (H2L), was prepared as follows. Under vigorous stirring, 2-hydroxy-1-napthaldehyde (10 g) in ethanol (30 ml) was added slowly to ete (5 g) in ethanol (20 ml). Stripping off the ethanol from the mixture left a pale-yellow oil, which changed to a green-yellow solid after several days at 276 K. The product was recrystallized several times from ethanol (yield 7.5 g, 57%; m.p. 423–424 K). Analysis, found: C 69.22, H 6.11, N 5.62%; calculated: C 69.29, H 6.02, N 5.57%. The title compound was prepared by adding H2L (0.344 g, 0.0068 mol) to dimethyldichlorotin(IV) (0.365 g, 0.0017 mol) in ethanol (50 ml). After refluxing for 2 h, the yellow solid that separated from the solution was cooled and filtered. The product was recrystallized from acetonitrile to give a pale-yellow material, (I) (m.p. 481–483 K). Analysis, found: C 52.05, H 5.19, N 5.45%; calculated: C 51.92, H 5.15, N 5.50%.
The acetonitrile solvent molecule is disordered. The two methyl C atoms lie so close together that they are indistinguishable; the displacement parameters for each of the other sets of atoms [C33A/C33B and N3A/N3B; occupancy factor 0.80 (1) for C33A] were restrained to be equal. The H atoms for the minor orientation were not included because their positions could not be determined. The rotations of the idealized methyl H atoms around C30—Sn, C31—Sn and C32—C33A were varied. All other H atoms on C atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å. Is this added text OK? The H atoms attached to atoms N1 and N2 were initially refined isotropically and without restraints, but the resulting N—H distances [0.78 (4) and 0.67 (2) Å] deviated enough from the standard value that restraints [DFIX 0.86 0.01; SHELXL97 (Sheldrick, 1997)] were imposed on the two distances. The U values for H10 and H20 [0.080 (12) and 0.041 (7) Å2 in the restrained refinement] were sufficiently reasonable that the attachment of the H atoms to N1 and N2 (rather than to O1 and O2) was certain. Omitting atoms H10 and H20 from the least-squares refinement, the two highest peaks in the difference Fourier map (0.54 and 0.39 e Å−3) were located ca 1 Å from the N atoms and ca 2 Å from the O atoms.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990).
[Sn(CH3)2Cl2(C29H30N2O2S2)]·C2H3N | F(000) = 780 |
Mr = 763.38 | Dx = 1.448 Mg m−3 |
Triclinic, P1 | Melting point = 481–483 K |
a = 12.334 (2) Å | Mo Kα radiation, λ = 0.71070 Å |
b = 12.765 (2) Å | Cell parameters from 19845 reflections |
c = 12.832 (2) Å | θ = 2.9–25.0° |
α = 84.32 (2)° | µ = 1.04 mm−1 |
β = 66.41 (2)° | T = 293 K |
γ = 71.10 (2)° | Rod, yellow |
V = 1750.6 (6) Å3 | 0.5 × 0.3 × 0.2 mm |
Z = 2 |
Nonius KappaCCD area-detector diffractometer | 6059 independent reflections |
Radiation source: fine-focus sealed tube | 5462 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 18 pixels mm-1 | θmax = 25.0°, θmin = 2.9° |
ϕ and ω scans with 1.0° steps | h = −14→14 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −14→15 |
Tmin = 0.75, Tmax = 0.81 | l = −15→15 |
19845 measured reflections |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + 0.66P] where P = (Fo2 + 2Fc2)/3 |
6059 reflections | (Δ/σ)max = 0.003 |
406 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[Sn(CH3)2Cl2(C29H30N2O2S2)]·C2H3N | γ = 71.10 (2)° |
Mr = 763.38 | V = 1750.6 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.334 (2) Å | Mo Kα radiation |
b = 12.765 (2) Å | µ = 1.04 mm−1 |
c = 12.832 (2) Å | T = 293 K |
α = 84.32 (2)° | 0.5 × 0.3 × 0.2 mm |
β = 66.41 (2)° |
Nonius KappaCCD area-detector diffractometer | 6059 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 5462 reflections with I > 2σ(I) |
Tmin = 0.75, Tmax = 0.81 | Rint = 0.038 |
19845 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.33 e Å−3 |
6059 reflections | Δρmin = −0.53 e Å−3 |
406 parameters |
Experimental. The crystal-to-detector distance was 25 mm. Each frame was measured for 240 s. The number of scan sets measured was 3; the total number of frames measured was 263. |
Refinement. The N-atom end of the acetonitrile solvent molecule is disordered over two sites (occupancy 0.804 (9) for the major orientation.) Atoms N3A and N3B and atoms C33A and C33B were required to have the same anisotropic displacement parameters. The H atoms for the methyl group of the minor orientation were omitted. The H atoms attached to N1 and N2 were first refined isotropically and without restraints, but the resulting N—H distances (0.78 (4) and 0.67 (2) Å) deviated enough from the standard value that restraints (DFIX 0.86 0.01) were imposed on the two distances. Rotations of the CH3 groups around the bonds Sn—C30, Sn—C31, and C33A—C32 were varied. All other H atoms were placed in idealized positions and constrained to ride on the attached atom. The major features in the final difference Fourier map are near the Sn atom. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Sn | 0.294379 (15) | 0.234569 (13) | 0.309742 (14) | 0.03861 (8) | |
Cl1 | 0.23802 (8) | 0.21348 (7) | 0.14574 (7) | 0.0636 (2) | |
Cl2 | 0.34657 (7) | 0.25051 (6) | 0.48914 (6) | 0.05563 (18) | |
S1 | 0.07621 (8) | 0.52430 (6) | 0.84959 (6) | 0.0601 (2) | |
S2 | 0.16512 (8) | 0.06745 (6) | 0.85720 (6) | 0.0595 (2) | |
O1 | 0.2064 (2) | 0.41709 (15) | 0.33493 (16) | 0.0536 (5) | |
O2 | 0.38426 (19) | 0.05605 (15) | 0.32520 (16) | 0.0531 (5) | |
N1 | 0.1961 (2) | 0.52287 (19) | 0.50354 (19) | 0.0474 (5) | |
H10 | 0.204 (3) | 0.4628 (18) | 0.473 (3) | 0.080 (12)* | |
N2 | 0.3625 (2) | −0.02522 (18) | 0.52340 (18) | 0.0432 (5) | |
H20 | 0.361 (2) | 0.0297 (15) | 0.4812 (19) | 0.041 (7)* | |
C1 | 0.2077 (2) | 0.5063 (2) | 0.2758 (2) | 0.0456 (6) | |
C2 | 0.2257 (3) | 0.5059 (3) | 0.1592 (3) | 0.0568 (7) | |
H2 | 0.2377 | 0.4406 | 0.1237 | 0.068* | |
C3 | 0.2257 (3) | 0.5991 (3) | 0.0995 (3) | 0.0617 (8) | |
H3 | 0.2400 | 0.5956 | 0.0229 | 0.074* | |
C4 | 0.2049 (3) | 0.7021 (3) | 0.1487 (3) | 0.0556 (7) | |
C5 | 0.2063 (3) | 0.7976 (3) | 0.0835 (3) | 0.0758 (10) | |
H5 | 0.2227 | 0.7928 | 0.0065 | 0.091* | |
C6 | 0.1843 (4) | 0.8961 (3) | 0.1311 (4) | 0.0846 (12) | |
H6 | 0.1871 | 0.9581 | 0.0868 | 0.101* | |
C7 | 0.1575 (3) | 0.9041 (3) | 0.2463 (4) | 0.0734 (10) | |
H7 | 0.1398 | 0.9725 | 0.2793 | 0.088* | |
C8 | 0.1568 (3) | 0.8127 (2) | 0.3124 (3) | 0.0595 (8) | |
H8 | 0.1389 | 0.8200 | 0.3895 | 0.071* | |
C9 | 0.1829 (2) | 0.7081 (2) | 0.2649 (2) | 0.0466 (6) | |
C10 | 0.1890 (2) | 0.6073 (2) | 0.3286 (2) | 0.0417 (6) | |
C11 | 0.1862 (2) | 0.6078 (2) | 0.4393 (2) | 0.0436 (6) | |
H11 | 0.1764 | 0.6753 | 0.4693 | 0.052* | |
C12 | 0.2001 (3) | 0.5249 (2) | 0.6156 (2) | 0.0505 (7) | |
H12A | 0.2176 | 0.5913 | 0.6252 | 0.061* | |
H12B | 0.2667 | 0.4613 | 0.6211 | 0.061* | |
C13 | 0.0776 (3) | 0.5227 (3) | 0.7092 (2) | 0.0540 (7) | |
H13A | 0.0603 | 0.4567 | 0.6983 | 0.065* | |
H13B | 0.0116 | 0.5864 | 0.7030 | 0.065* | |
C14 | 0.1789 (3) | 0.3880 (2) | 0.8546 (2) | 0.0487 (6) | |
H14A | 0.2584 | 0.3778 | 0.7912 | 0.058* | |
H14B | 0.1932 | 0.3834 | 0.9241 | 0.058* | |
C15 | 0.1301 (3) | 0.2944 (2) | 0.8499 (3) | 0.0534 (7) | |
H15A | 0.1195 | 0.2959 | 0.7788 | 0.064* | |
H15B | 0.0494 | 0.3049 | 0.9117 | 0.064* | |
C16 | 0.2190 (3) | 0.1827 (2) | 0.8592 (2) | 0.0483 (6) | |
H16A | 0.2311 | 0.1827 | 0.9294 | 0.058* | |
H16B | 0.2992 | 0.1725 | 0.7966 | 0.058* | |
C17 | 0.1996 (3) | 0.0552 (2) | 0.7076 (2) | 0.0469 (6) | |
H17A | 0.1449 | 0.0204 | 0.6977 | 0.056* | |
H17B | 0.1842 | 0.1285 | 0.6766 | 0.056* | |
C18 | 0.3335 (3) | −0.0129 (2) | 0.6437 (2) | 0.0501 (7) | |
H18A | 0.3880 | 0.0226 | 0.6529 | 0.060* | |
H18B | 0.3490 | −0.0856 | 0.6759 | 0.060* | |
C19 | 0.3931 (2) | −0.1184 (2) | 0.4709 (2) | 0.0408 (6) | |
H19 | 0.3959 | −0.1810 | 0.5147 | 0.049* | |
C20 | 0.4159 (2) | −0.0429 (2) | 0.2827 (2) | 0.0405 (6) | |
C21 | 0.4467 (3) | −0.0608 (2) | 0.1654 (2) | 0.0507 (7) | |
H21 | 0.4437 | −0.0009 | 0.1178 | 0.061* | |
C22 | 0.4799 (3) | −0.1637 (2) | 0.1226 (2) | 0.0543 (7) | |
H22 | 0.5000 | −0.1733 | 0.0454 | 0.065* | |
C23 | 0.4855 (2) | −0.2583 (2) | 0.1907 (2) | 0.0473 (6) | |
C24 | 0.5182 (3) | −0.3649 (3) | 0.1431 (3) | 0.0613 (8) | |
H24 | 0.5353 | −0.3730 | 0.0663 | 0.074* | |
C25 | 0.5251 (3) | −0.4555 (3) | 0.2078 (3) | 0.0688 (9) | |
H25 | 0.5468 | −0.5252 | 0.1754 | 0.083* | |
C26 | 0.4995 (3) | −0.4444 (2) | 0.3231 (3) | 0.0652 (9) | |
H26 | 0.5042 | −0.5068 | 0.3672 | 0.078* | |
C27 | 0.4675 (3) | −0.3418 (2) | 0.3721 (3) | 0.0527 (7) | |
H27 | 0.4521 | −0.3358 | 0.4488 | 0.063* | |
C28 | 0.4579 (2) | −0.2454 (2) | 0.3073 (2) | 0.0421 (6) | |
C29 | 0.4226 (2) | −0.1350 (2) | 0.3544 (2) | 0.0384 (5) | |
C30 | 0.4683 (3) | 0.2524 (3) | 0.2013 (3) | 0.0571 (7) | |
H30A | 0.4567 | 0.3082 | 0.1475 | 0.086* | |
H30B | 0.5223 | 0.1831 | 0.1614 | 0.086* | |
H30C | 0.5050 | 0.2738 | 0.2457 | 0.086* | |
C31 | 0.1234 (3) | 0.2187 (3) | 0.4290 (3) | 0.0592 (8) | |
H31A | 0.1391 | 0.1541 | 0.4726 | 0.089* | |
H31B | 0.0743 | 0.2116 | 0.3896 | 0.089* | |
H31C | 0.0791 | 0.2832 | 0.4791 | 0.089* | |
C32 | 0.0501 (4) | 0.8214 (4) | 0.8547 (4) | 0.0904 (12) | |
H32A | 0.0338 | 0.8951 | 0.8804 | 0.136* | 0.804 (9) |
H32B | 0.1052 | 0.7696 | 0.8851 | 0.136* | 0.804 (9) |
H32C | −0.0268 | 0.8045 | 0.8801 | 0.136* | 0.804 (9) |
C33A | 0.1076 (5) | 0.8137 (4) | 0.7314 (5) | 0.0786 (17) | 0.804 (9) |
N3A | 0.1507 (6) | 0.8078 (4) | 0.6353 (5) | 0.119 (2) | 0.804 (9) |
C33B | 0.175 (2) | 0.7750 (17) | 0.772 (2) | 0.0786 (17) | 0.196 (9) |
N3B | 0.263 (2) | 0.7464 (18) | 0.6983 (18) | 0.119 (2) | 0.196 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.03960 (11) | 0.03938 (11) | 0.03585 (11) | −0.00729 (7) | −0.01700 (8) | −0.00174 (7) |
Cl1 | 0.0709 (5) | 0.0777 (5) | 0.0511 (4) | −0.0161 (4) | −0.0362 (4) | −0.0072 (4) |
Cl2 | 0.0716 (5) | 0.0486 (4) | 0.0541 (4) | −0.0070 (3) | −0.0399 (4) | −0.0040 (3) |
S1 | 0.0755 (5) | 0.0490 (4) | 0.0388 (4) | −0.0023 (4) | −0.0173 (3) | −0.0047 (3) |
S2 | 0.0809 (5) | 0.0560 (4) | 0.0349 (4) | −0.0278 (4) | −0.0102 (3) | −0.0008 (3) |
O1 | 0.0733 (13) | 0.0376 (10) | 0.0465 (11) | −0.0053 (9) | −0.0289 (10) | −0.0002 (8) |
O2 | 0.0713 (13) | 0.0368 (10) | 0.0494 (11) | −0.0045 (9) | −0.0302 (10) | −0.0041 (8) |
N1 | 0.0563 (14) | 0.0428 (13) | 0.0382 (12) | −0.0099 (10) | −0.0169 (10) | −0.0021 (10) |
N2 | 0.0488 (12) | 0.0412 (12) | 0.0342 (11) | −0.0049 (10) | −0.0169 (10) | −0.0035 (10) |
C1 | 0.0414 (14) | 0.0468 (15) | 0.0439 (15) | −0.0032 (11) | −0.0205 (11) | 0.0023 (12) |
C2 | 0.0584 (17) | 0.0624 (18) | 0.0471 (16) | −0.0090 (14) | −0.0251 (14) | −0.0023 (14) |
C3 | 0.0658 (19) | 0.078 (2) | 0.0448 (16) | −0.0206 (16) | −0.0291 (15) | 0.0135 (15) |
C4 | 0.0451 (15) | 0.0637 (19) | 0.0599 (18) | −0.0150 (13) | −0.0274 (14) | 0.0180 (15) |
C5 | 0.076 (2) | 0.088 (3) | 0.076 (2) | −0.033 (2) | −0.044 (2) | 0.037 (2) |
C6 | 0.091 (3) | 0.073 (3) | 0.106 (3) | −0.034 (2) | −0.058 (2) | 0.046 (2) |
C7 | 0.066 (2) | 0.0479 (18) | 0.107 (3) | −0.0186 (15) | −0.038 (2) | 0.0198 (18) |
C8 | 0.0486 (16) | 0.0488 (17) | 0.075 (2) | −0.0123 (13) | −0.0215 (15) | 0.0089 (15) |
C9 | 0.0317 (12) | 0.0477 (15) | 0.0571 (17) | −0.0088 (11) | −0.0185 (12) | 0.0091 (12) |
C10 | 0.0343 (12) | 0.0399 (13) | 0.0429 (14) | −0.0038 (10) | −0.0131 (11) | 0.0003 (11) |
C11 | 0.0356 (13) | 0.0399 (14) | 0.0453 (15) | −0.0039 (10) | −0.0106 (11) | −0.0046 (11) |
C12 | 0.0549 (16) | 0.0535 (16) | 0.0403 (15) | −0.0112 (13) | −0.0189 (13) | −0.0039 (12) |
C13 | 0.0540 (16) | 0.0552 (17) | 0.0413 (15) | −0.0035 (13) | −0.0179 (13) | 0.0027 (12) |
C14 | 0.0549 (16) | 0.0501 (15) | 0.0419 (15) | −0.0118 (12) | −0.0231 (12) | 0.0008 (12) |
C15 | 0.0524 (16) | 0.0535 (17) | 0.0543 (17) | −0.0111 (13) | −0.0241 (14) | −0.0018 (13) |
C16 | 0.0559 (16) | 0.0499 (15) | 0.0401 (14) | −0.0124 (12) | −0.0223 (12) | −0.0023 (12) |
C17 | 0.0533 (16) | 0.0487 (15) | 0.0398 (14) | −0.0164 (12) | −0.0176 (12) | −0.0045 (11) |
C18 | 0.0542 (16) | 0.0569 (16) | 0.0357 (14) | −0.0055 (13) | −0.0218 (12) | −0.0051 (12) |
C19 | 0.0354 (13) | 0.0415 (14) | 0.0419 (14) | −0.0068 (10) | −0.0151 (11) | −0.0003 (11) |
C20 | 0.0377 (13) | 0.0411 (14) | 0.0393 (13) | −0.0044 (10) | −0.0161 (10) | −0.0069 (10) |
C21 | 0.0552 (16) | 0.0512 (16) | 0.0420 (15) | −0.0098 (13) | −0.0196 (13) | −0.0023 (12) |
C22 | 0.0537 (16) | 0.0631 (19) | 0.0397 (15) | −0.0097 (13) | −0.0154 (13) | −0.0126 (13) |
C23 | 0.0379 (13) | 0.0469 (15) | 0.0522 (16) | −0.0070 (11) | −0.0136 (12) | −0.0165 (12) |
C24 | 0.0533 (17) | 0.0604 (19) | 0.064 (2) | −0.0122 (14) | −0.0148 (15) | −0.0268 (16) |
C25 | 0.0581 (19) | 0.0493 (18) | 0.090 (3) | −0.0149 (14) | −0.0150 (17) | −0.0255 (18) |
C26 | 0.0540 (17) | 0.0407 (16) | 0.094 (3) | −0.0123 (13) | −0.0238 (17) | −0.0005 (16) |
C27 | 0.0507 (16) | 0.0429 (15) | 0.0598 (18) | −0.0116 (12) | −0.0181 (13) | −0.0037 (13) |
C28 | 0.0303 (12) | 0.0415 (14) | 0.0508 (15) | −0.0072 (10) | −0.0132 (11) | −0.0080 (11) |
C29 | 0.0334 (12) | 0.0382 (13) | 0.0412 (14) | −0.0066 (10) | −0.0141 (10) | −0.0064 (10) |
C30 | 0.0524 (16) | 0.0651 (19) | 0.0520 (17) | −0.0209 (14) | −0.0175 (13) | 0.0067 (14) |
C31 | 0.0468 (16) | 0.072 (2) | 0.0515 (17) | −0.0171 (14) | −0.0137 (13) | 0.0035 (14) |
C32 | 0.099 (3) | 0.087 (3) | 0.082 (3) | −0.039 (2) | −0.023 (2) | −0.006 (2) |
C33A | 0.082 (4) | 0.068 (3) | 0.079 (4) | −0.041 (3) | −0.006 (2) | −0.018 (2) |
N3A | 0.145 (5) | 0.107 (4) | 0.092 (4) | −0.080 (4) | 0.005 (3) | −0.030 (3) |
C33B | 0.082 (4) | 0.068 (3) | 0.079 (4) | −0.041 (3) | −0.006 (2) | −0.018 (2) |
N3B | 0.145 (5) | 0.107 (4) | 0.092 (4) | −0.080 (4) | 0.005 (3) | −0.030 (3) |
Sn—Cl1 | 2.5276 (7) | C27—C28 | 1.414 (4) |
Sn—Cl2 | 2.6681 (7) | C28—C29 | 1.450 (3) |
Sn—O1 | 2.223 (2) | C32—C33A | 1.450 (7) |
Sn—O2 | 2.216 (2) | C33A—N3A | 1.130 (7) |
Sn—C30 | 2.110 (3) | C32—C33B | 1.44 (2) |
Sn—C31 | 2.113 (3) | C33B—N3B | 1.10 (3) |
S1—C13 | 1.797 (3) | C2—H2 | 0.93 |
S1—C14 | 1.803 (3) | C3—H3 | 0.93 |
S2—C16 | 1.806 (3) | C5—H5 | 0.93 |
S2—C17 | 1.804 (3) | C6—H6 | 0.93 |
O1—C1 | 1.306 (3) | C7—H7 | 0.93 |
O2—C20 | 1.300 (3) | C8—H8 | 0.93 |
N1—C11 | 1.299 (3) | C11—H11 | 0.93 |
N1—C12 | 1.462 (4) | C12—H12A | 0.97 |
N1—H10 | 0.86 (3) | C12—H12B | 0.97 |
N2—C18 | 1.452 (3) | C13—H13A | 0.97 |
N2—C19 | 1.294 (3) | C13—H13B | 0.97 |
N2—H20 | 0.84 (3) | C14—H14A | 0.97 |
C1—C2 | 1.422 (4) | C14—H14B | 0.97 |
C1—C10 | 1.425 (4) | C15—H15A | 0.97 |
C2—C3 | 1.350 (4) | C15—H15B | 0.97 |
C3—C4 | 1.416 (5) | C16—H16A | 0.97 |
C4—C5 | 1.410 (5) | C16—H16B | 0.97 |
C4—C9 | 1.411 (4) | C17—H17A | 0.97 |
C5—C6 | 1.350 (6) | C17—H17B | 0.97 |
C6—C7 | 1.386 (6) | C18—H18A | 0.97 |
C7—C8 | 1.374 (4) | C18—H18B | 0.97 |
C8—C9 | 1.409 (4) | C19—H19 | 0.93 |
C9—C10 | 1.452 (4) | C21—H21 | 0.93 |
C10—C11 | 1.408 (4) | C22—H22 | 0.93 |
C12—C13 | 1.514 (4) | C24—H24 | 0.93 |
C14—C15 | 1.516 (4) | C25—H25 | 0.93 |
C15—C16 | 1.520 (4) | C26—H26 | 0.93 |
C17—C18 | 1.511 (4) | C27—H27 | 0.93 |
C19—C29 | 1.410 (4) | C30—H30A | 0.96 |
C20—C21 | 1.421 (4) | C30—H30B | 0.96 |
C20—C29 | 1.421 (4) | C30—H30C | 0.96 |
C21—C22 | 1.346 (4) | C31—H31A | 0.96 |
C22—C23 | 1.418 (4) | C31—H31B | 0.96 |
C23—C24 | 1.414 (4) | C31—H31C | 0.96 |
C23—C28 | 1.410 (4) | C32—H32A | 0.96 |
C24—C25 | 1.356 (5) | C32—H32B | 0.96 |
C25—C26 | 1.395 (5) | C32—H32C | 0.96 |
C26—C27 | 1.377 (4) | ||
Cl1—Sn—Cl2 | 177.06 (3) | C2—C3—H3 | 118.6 |
Cl1—Sn—O1 | 96.68 (5) | C4—C3—H3 | 118.6 |
Cl1—Sn—O2 | 96.95 (5) | C4—C5—H5 | 119.5 |
Cl2—Sn—O1 | 84.62 (5) | C6—C5—H5 | 119.5 |
Cl2—Sn—O2 | 81.62 (5) | C5—C6—H6 | 120.1 |
Cl1—Sn—C30 | 93.13 (9) | C7—C6—H6 | 120.1 |
Cl1—Sn—C31 | 91.27 (9) | C6—C7—H7 | 119.5 |
Cl2—Sn—C30 | 89.46 (9) | C8—C7—H7 | 119.5 |
Cl2—Sn—C31 | 86.15 (9) | C7—C8—H8 | 119.6 |
O1—Sn—O2 | 166.03 (7) | C9—C8—H8 | 119.6 |
O1—Sn—C30 | 91.72 (11) | N1—C11—H11 | 116.9 |
O1—Sn—C31 | 87.57 (11) | C10—C11—H11 | 116.9 |
O2—Sn—C30 | 90.56 (10) | N1—C12—H12A | 109.5 |
O2—Sn—C31 | 89.10 (11) | N1—C12—H12B | 109.5 |
C30—Sn—C31 | 175.59 (12) | C13—C12—H12A | 109.5 |
C13—S1—C14 | 102.10 (13) | C13—C12—H12B | 109.5 |
C16—S2—C17 | 100.87 (13) | S1—C13—H13A | 108.9 |
Sn—O1—C1 | 139.17 (17) | S1—C13—H13B | 108.9 |
Sn—O2—C20 | 144.59 (17) | C12—C13—H13A | 108.9 |
C11—N1—C12 | 124.7 (2) | C12—C13—H13B | 108.9 |
C11—N1—H10 | 114 (3) | S1—C14—H14A | 108.7 |
C12—N1—H10 | 122 (3) | S1—C14—H14B | 108.7 |
C18—N2—C19 | 124.7 (2) | C15—C14—H14A | 108.7 |
C18—N2—H20 | 121 (2) | C15—C14—H14B | 108.7 |
C19—N2—H20 | 114 (2) | C14—C15—H15A | 109.4 |
O1—C1—C2 | 121.5 (3) | C14—C15—H15B | 109.4 |
O1—C1—C10 | 119.8 (2) | C16—C15—H15A | 109.4 |
C2—C1—C10 | 118.7 (3) | C16—C15—H15B | 109.4 |
C1—C2—C3 | 120.7 (3) | S2—C16—H16A | 108.9 |
C2—C3—C4 | 122.8 (3) | S2—C16—H16B | 108.9 |
C3—C4—C5 | 121.2 (3) | C15—C16—H16A | 108.9 |
C3—C4—C9 | 118.9 (3) | C15—C16—H16B | 108.9 |
C5—C4—C9 | 119.8 (3) | S2—C17—H17A | 109.4 |
C4—C5—C6 | 121.0 (4) | S2—C17—H17B | 109.4 |
C5—C6—C7 | 119.7 (3) | C18—C17—H17A | 109.4 |
C6—C7—C8 | 121.1 (4) | C18—C17—H17B | 109.4 |
C7—C8—C9 | 120.7 (3) | N2—C18—H18A | 109.3 |
C4—C9—C8 | 117.5 (3) | N2—C18—H18B | 109.3 |
C4—C9—C10 | 118.8 (3) | C17—C18—H18A | 109.3 |
C8—C9—C10 | 123.7 (3) | C17—C18—H18B | 109.3 |
C1—C10—C9 | 119.9 (2) | N2—C19—H19 | 116.5 |
C1—C10—C11 | 120.1 (2) | C29—C19—H19 | 116.5 |
C9—C10—C11 | 119.8 (2) | C20—C21—H21 | 119.8 |
N1—C11—C10 | 126.1 (3) | C22—C21—H21 | 119.8 |
N1—C12—C13 | 110.9 (2) | C21—C22—H22 | 118.7 |
S1—C13—C12 | 113.4 (2) | C23—C22—H22 | 118.7 |
S1—C14—C15 | 114.2 (2) | C23—C24—H24 | 119.6 |
C14—C15—C16 | 111.1 (2) | C25—C24—H24 | 119.6 |
S2—C16—C15 | 113.5 (2) | C24—C25—H25 | 120.0 |
S2—C17—C18 | 111.0 (2) | C26—C25—H25 | 120.0 |
N2—C18—C17 | 111.8 (2) | C25—C26—H26 | 119.7 |
N2—C19—C29 | 126.9 (2) | C27—C26—H26 | 119.7 |
O2—C20—C21 | 121.1 (2) | C26—C27—H27 | 119.6 |
O2—C20—C29 | 119.4 (2) | C28—C27—H27 | 119.6 |
C21—C20—C29 | 119.4 (2) | Sn—C30—H30A | 109.5 |
C20—C21—C22 | 120.4 (3) | Sn—C30—H30B | 109.5 |
C21—C22—C23 | 122.5 (3) | Sn—C30—H30C | 109.5 |
C22—C23—C24 | 120.8 (3) | Sn—C31—H31A | 109.5 |
C22—C23—C28 | 119.4 (2) | Sn—C31—H31B | 109.5 |
C24—C23—C28 | 119.8 (3) | Sn—C31—H31C | 109.5 |
C23—C24—C25 | 120.8 (3) | H12A—C12—H12B | 108.0 |
C24—C25—C26 | 120.1 (3) | H13A—C13—H13B | 107.7 |
C25—C26—C27 | 120.5 (3) | H14A—C14—H14B | 107.6 |
C26—C27—C28 | 120.8 (3) | H15A—C15—H15B | 108.0 |
C23—C28—C27 | 117.9 (2) | H16A—C16—H16B | 107.7 |
C23—C28—C29 | 118.7 (2) | H17A—C17—H17B | 108.0 |
C27—C28—C29 | 123.4 (3) | H18A—C18—H18B | 107.9 |
C19—C29—C20 | 120.0 (2) | H30A—C30—H30B | 109.5 |
C19—C29—C28 | 120.5 (2) | H30A—C30—H30C | 109.5 |
C20—C29—C28 | 119.6 (2) | H30B—C30—H30C | 109.5 |
N3A—C33A—C32 | 179.0 (6) | H31A—C31—H31B | 109.5 |
N3B—C33B—C32 | 170 (2) | H31A—C31—H31C | 109.5 |
C1—C2—H2 | 119.6 | H31B—C31—H31C | 109.5 |
C3—C2—H2 | 119.6 | ||
C30—Sn—O1—C1 | 40.5 (3) | N1—C12—C13—S1 | 179.7 (2) |
C31—Sn—O1—C1 | −143.9 (3) | C14—S1—C13—C12 | −70.6 (2) |
Cl1—Sn—O1—C1 | −52.9 (3) | C13—S1—C14—C15 | −65.7 (2) |
Cl2—Sn—O1—C1 | 129.8 (3) | S1—C14—C15—C16 | −177.7 (2) |
C30—Sn—O2—C20 | −91.5 (3) | C14—C15—C16—S2 | 178.8 (2) |
C31—Sn—O2—C20 | 92.9 (3) | C17—S2—C16—C15 | 77.1 (2) |
Cl1—Sn—O2—C20 | 1.8 (3) | C16—S2—C17—C18 | 84.0 (2) |
Cl2—Sn—O2—C20 | 179.2 (3) | C19—N2—C18—C17 | −115.3 (3) |
Sn—O1—C1—C2 | 32.7 (4) | S2—C17—C18—N2 | 179.0 (2) |
Sn—O1—C1—C10 | −148.3 (2) | C18—N2—C19—C29 | −179.7 (2) |
O1—C1—C2—C3 | 179.4 (3) | Sn—O2—C20—C29 | −151.2 (2) |
C10—C1—C2—C3 | 0.3 (4) | Sn—O2—C20—C21 | 30.1 (4) |
C1—C2—C3—C4 | −1.7 (5) | O2—C20—C21—C22 | 179.6 (3) |
C2—C3—C4—C5 | 179.6 (3) | C29—C20—C21—C22 | 1.0 (4) |
C2—C3—C4—C9 | −0.1 (5) | C20—C21—C22—C23 | 0.4 (4) |
C9—C4—C5—C6 | −1.5 (5) | C21—C22—C23—C28 | −1.4 (4) |
C3—C4—C5—C6 | 178.8 (3) | C21—C22—C23—C24 | 178.6 (3) |
C4—C5—C6—C7 | −1.2 (6) | C28—C23—C24—C25 | −0.8 (4) |
C5—C6—C7—C8 | 2.1 (6) | C22—C23—C24—C25 | 179.2 (3) |
C6—C7—C8—C9 | −0.2 (5) | C23—C24—C25—C26 | 0.0 (5) |
C7—C8—C9—C4 | −2.4 (4) | C24—C25—C26—C27 | −0.1 (5) |
C7—C8—C9—C10 | 177.3 (3) | C25—C26—C27—C28 | 1.0 (5) |
C5—C4—C9—C8 | 3.2 (4) | C24—C23—C28—C27 | 1.6 (4) |
C3—C4—C9—C8 | −177.1 (3) | C22—C23—C28—C27 | −178.4 (2) |
C5—C4—C9—C10 | −176.5 (3) | C24—C23—C28—C29 | −179.0 (2) |
C3—C4—C9—C10 | 3.2 (4) | C22—C23—C28—C29 | 1.0 (4) |
O1—C1—C10—C11 | 8.8 (4) | C26—C27—C28—C23 | −1.7 (4) |
C2—C1—C10—C11 | −172.2 (2) | C26—C27—C28—C29 | 178.9 (3) |
O1—C1—C10—C9 | −176.3 (2) | N2—C19—C29—C20 | −2.4 (4) |
C2—C1—C10—C9 | 2.8 (4) | N2—C19—C29—C28 | 178.6 (2) |
C8—C9—C10—C11 | −9.2 (4) | O2—C20—C29—C19 | 1.0 (4) |
C4—C9—C10—C11 | 170.4 (2) | C21—C20—C29—C19 | 179.6 (2) |
C8—C9—C10—C1 | 175.8 (2) | O2—C20—C29—C28 | 180.0 (2) |
C4—C9—C10—C1 | −4.5 (4) | C21—C20—C29—C28 | −1.4 (4) |
C12—N1—C11—C10 | 176.3 (2) | C23—C28—C29—C19 | 179.3 (2) |
C1—C10—C11—N1 | −2.0 (4) | C27—C28—C29—C19 | −1.3 (4) |
C9—C10—C11—N1 | −176.9 (2) | C23—C28—C29—C20 | 0.3 (3) |
C11—N1—C12—C13 | 105.1 (3) | C27—C28—C29—C20 | 179.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H10···O1 | 0.86 (3) | 1.90 (4) | 2.601 (3) | 138 (3) |
N2—H20···O2 | 0.84 (3) | 1.92 (3) | 2.594 (3) | 137 (3) |
Experimental details
Crystal data | |
Chemical formula | [Sn(CH3)2Cl2(C29H30N2O2S2)]·C2H3N |
Mr | 763.38 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 12.334 (2), 12.765 (2), 12.832 (2) |
α, β, γ (°) | 84.32 (2), 66.41 (2), 71.10 (2) |
V (Å3) | 1750.6 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.04 |
Crystal size (mm) | 0.5 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.75, 0.81 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19845, 6059, 5462 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.077, 1.06 |
No. of reflections | 6059 |
No. of parameters | 406 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.53 |
Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1990).
Sn—Cl1 | 2.5276 (7) | N1—C12 | 1.462 (4) |
Sn—Cl2 | 2.6681 (7) | N2—C18 | 1.452 (3) |
Sn—O1 | 2.223 (2) | N2—C19 | 1.294 (3) |
Sn—O2 | 2.216 (2) | C1—C10 | 1.425 (4) |
Sn—C30 | 2.110 (3) | C2—C3 | 1.350 (4) |
Sn—C31 | 2.113 (3) | C10—C11 | 1.408 (4) |
O1—C1 | 1.306 (3) | C19—C29 | 1.410 (4) |
O2—C20 | 1.300 (3) | C20—C29 | 1.421 (4) |
N1—C11 | 1.299 (3) | C21—C22 | 1.346 (4) |
Cl1—Sn—Cl2 | 177.06 (3) | Cl2—Sn—C31 | 86.15 (9) |
Cl1—Sn—O1 | 96.68 (5) | O1—Sn—O2 | 166.03 (7) |
Cl1—Sn—O2 | 96.95 (5) | O1—Sn—C30 | 91.72 (11) |
Cl2—Sn—O1 | 84.62 (5) | O1—Sn—C31 | 87.57 (11) |
Cl2—Sn—O2 | 81.62 (5) | O2—Sn—C30 | 90.56 (10) |
Cl1—Sn—C30 | 93.13 (9) | O2—Sn—C31 | 89.10 (11) |
Cl1—Sn—C31 | 91.27 (9) | C30—Sn—C31 | 175.59 (12) |
Cl2—Sn—C30 | 89.46 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H10···O1 | 0.86 (3) | 1.90 (4) | 2.601 (3) | 138 (3) |
N2—H20···O2 | 0.84 (3) | 1.92 (3) | 2.594 (3) | 137 (3) |
The structure of the title complex, (I), was determined as part of a continuing study (see Bajue et al., 1998) of organotin adducts of potentially hexadentate Schiff base ligands. In most of the known structures of this type, there are two (or more) metal centers per ligand (e.g. Bajue et al., 1998; Degaonkar et al., 1994; Wang et al., 1994), but in (I) there is only one. The number of donor atoms bonded to the Sn varies from two to six in the comparison structures, but in (I) the ligand is bidentate. In this structure, the two ends of the long ligand wrap around the trans-SnCl2Me2 fragment so that the most basic ligand donors, the O atoms, coordinate in a trans arrangement. \sch
The refined structure of (I) shows that the hydroxyl H atoms of the dinaphthol ligand migrate during the coordination reaction to the N atoms; a double zwitterion is formed if there is no rearrangement of the double bonds. The distances (Table 1) suggest, however, that the naphthoxy resonance forms (see Scheme below) without local charges, and in which O1—C1, O2—C20, C10—C11 and C29—C19 are all double bonds, may also be important. Resonance forms in which one side of the ligand is zwitterionic and the other uncharged must also be considered. The transfer of the H atoms from the O to the N atoms upon coordination can be attributed to an increase in the acidity of the naphthols upon coordination to the Lewis acidic SnIV center. The coordinated O atoms are weaker bases than are the uncoordinated N atoms.
In the Cambridge Structural Database (CSD, Version?; Allen, 2002), there are five structures, with R factors of 0.05 or less, of six-coordinate Sn complexes that have two halo ligands, two C ligands and one or two Schiff base aryloxide ligands: DAHVEN (Kamwaya & Khoo, 1985), KUDKID (Teoh et al., 1991), LAZXEP (Hazell et al., 1994), NOZMEU (Yeap & Ishizawa, 1998) and SODBUI (Fun et al., 1991). In all five structures, the C1—C10 bond (numbering as in Fig. 1) is at least 0.048 Å longer than the C2—C3 bond; the maximum difference is 0.076 Å. These differences suggest that the uncharged resonance form having a carbonyl group is important. The two bond-length differences in this study [both 0.075 (6) Å] are among the largest found.
The structures in the literature have all been formulated as zwitterions; the precedent for this description seems to be Bullock et al. (1979). Further justification for the conclusion that the resonance forms with charge separation are more important than the uncharged forms comes from the comparison of the Sn—O and C—O bond lengths in the six Schiff base aryloxide complexes [the five literature structures plus (I)] with the corresponding Sn—O and C—O bonds in the three true Sn-ketone structures found in the CSD using search criteria analogous to those listed above. The Sn-ketone structures are BENFOP10 (Ng et al., 1982), MASYUA (Howie & Wardell, 2000) and SUZWOZ (Howie & Wardell, 2001). The average Sn—O distance in the true ketone complexes [2.444 (7) Å from four contributing values] is 0.206 (7) Å longer than in the Schiff base aryloxide complexes [2.238 (2) Å from seven contributing values]. The average C—O distance in the ketone complexes [1.227 (1) Å] is 0.077 (2) Å shorter than in the Schiff base aryloxide complexes [1.304 (2) Å].
We conclude that there is charge separation in the most important resonance forms of the Schiff base aryloxide ligand in six-coordinate Sn complexes. The non-zwitterionic resonance forms, however, are also important.
Formulating a name for the compound proved difficult. The oxidation state of the Sn atom is IV, but if the ligand is a double zwitterion then the formal charge on the Sn is −2.
The O—Sn—O bond in (I) is nonlinear (Table 1 and Fig. 1), because the SnCl2Me2 fragment cannot fit further down into the ligand pocket. The determining contacts appear to be between Cl2 and the (calculated) H atoms on C12 (2.99 Å) and C17 (3.11 Å). The exact rotation of the SnCl2Me2 unit around the O1···O2 vector and the overall distortions of the molecule from potential mirror symmetry are almost certainly determined by both intra- and intermolecular contacts. There might be room in the ligand pocket for the SnCl2Me2 unit to make 180° jumps, but there is no evidence of the Cl/Me disorder that would result from 90° jumps.
The difference in lengths of the Sn—Cl bonds [0.140 (1) Å] is noteworthy, because all other pairs of chemically equivalent bonds are essentially equal in length. The longer Sn—Cl bond, which is inside the ligand pocket, may be the result of steric crowding. The distances of Cl2 to H10 and H20 (H atoms attached to N1 and N2) are 2.75 and 2.77 Å, while the sum of the van der Waals radii for Cl and H (Bondi, 1964) is 2.95 Å. These Cl2···H distances would be even shorter if the Sn—Cl2 bond were as short as the Sn—Cl1 bond.
The packing diagram for (I) (Fig. 2) is surprisingly simple. The widths of the naphthyl units and of the S(CH2)3S units are similar, so that 2:1 stacks are formed. There is no evidence, however, of strong π–π stacking interactions; distances between corresponding C atoms in overlapping naphthyl fragments vary from 3.65 to 4.16 Å. The SnCl2Me2 units are substantially thinner than the repeat unit of the 2:1 stack, so acetonitrile molecules are included in the unit cell. The shortest S···S contact [3.646 (1) Å] is between two S1 atoms related by an inversion center; the shortest contacts involving S2 are to the disordered solvent molecule.