Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011963/qd0036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011963/qd0036Isup2.hkl |
CCDC reference: 152661
The title compound was prepared by the reaction of N-methylpyrrolidinone (0.71 g, 0.69 ml, 7.3 mmol) with freshly sublimed dichlorodimethylstannane (3.20 g, 14.6 mmol) derived from the reaction of dimethyltin oxide with HCl (Pfeiffer, 1902) in 10 ml of dry diethyl ether. The reaction mixture was stirred for 30 min and afterwards stored in a refrigerator at 278 K. Colourless crystals are obtained in quantitative yield after filtration and drying in vacuo (m.p. 329 K). A solution of the complex (80 mg) in C6D6 (470 mg) gives the following values for the structure-relevant NMR parameters: 2J (119Sn, 1H) = 79 Hz, 1J(119Sn–13C) = 590 Hz and d(119Sn) = 30.1 p.p.m.
The H atoms were placed in calculated positions with Uiso constrained to be 1.2Ueq of the carrier atom.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).
[Sn2Cl4(CH3)4(C5H9NO)] | Z = 2 |
Mr = 538.45 | F(000) = 516 |
Triclinic, P1 | Dx = 1.968 Mg m−3 |
a = 7.3650 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.311 (2) Å | Cell parameters from 5442 reflections |
c = 12.311 (3) Å | θ = 2.4–27.1° |
α = 78.45 (3)° | µ = 3.32 mm−1 |
β = 84.36 (3)° | T = 173 K |
γ = 84.38 (3)° | Parallelepiped, colourless |
V = 908.6 (3) Å3 | 0.1 × 0.08 × 0.08 mm |
Nonius KappaCCD diffractometer | 2466 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.046 |
Graphite monochromator | θmax = 27.1°, θmin = 2.4° |
Detector resolution: 10 vertical, 18 horizontal pixels mm-1 | h = −9→9 |
278 frames via ω–rotation (Δω = 1°) at different κ values and two times 25 s per frame scans | k = −12→13 |
5442 measured reflections | l = −14→15 |
3557 independent 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) = 0.063 | H-atom parameters constrained |
S = 0.80 | Calculated w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
3557 reflections | (Δ/σ)max = 0.012 |
159 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −0.85 e Å−3 |
[Sn2Cl4(CH3)4(C5H9NO)] | γ = 84.38 (3)° |
Mr = 538.45 | V = 908.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3650 (15) Å | Mo Kα radiation |
b = 10.311 (2) Å | µ = 3.32 mm−1 |
c = 12.311 (3) Å | T = 173 K |
α = 78.45 (3)° | 0.1 × 0.08 × 0.08 mm |
β = 84.36 (3)° |
Nonius KappaCCD diffractometer | 2466 reflections with I > 2σ(I) |
5442 measured reflections | Rint = 0.046 |
3557 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 0.80 | Δρmax = 0.76 e Å−3 |
3557 reflections | Δρmin = −0.85 e Å−3 |
159 parameters |
Experimental. The data collection covered almost the whole spere of reciprocal space, and the completeness of the data set up to θ=25° is 93.7%. crystal to detector distance was 35 mm. Crystal decay was monitored by repeating the initial frames at the end of data collection. Analysing the duplicate reflections there was no indication for any decay. |
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 | ||
Sn2 | 0.15732 (4) | 0.68299 (3) | 0.01703 (2) | 0.02798 (11) | |
Sn1 | 0.26442 (3) | 0.58316 (3) | −0.38866 (2) | 0.02607 (11) | |
Cl1 | 0.32671 (13) | 0.60116 (11) | −0.58757 (9) | 0.0339 (3) | |
Cl4 | 0.18459 (14) | 0.53686 (12) | −0.13112 (9) | 0.0383 (3) | |
Cl2 | −0.01390 (14) | 0.71989 (12) | −0.39842 (10) | 0.0407 (3) | |
Cl3 | 0.39646 (14) | 0.81139 (12) | −0.07790 (10) | 0.0429 (3) | |
O1 | 0.1197 (3) | 0.8157 (3) | 0.1463 (2) | 0.0332 (8) | |
C2 | 0.1886 (5) | 0.3871 (4) | −0.3464 (3) | 0.0308 (11) | |
H2A | 0.2533 | 0.3399 | −0.2845 | 0.037* | |
H2B | 0.2187 | 0.3441 | −0.4088 | 0.037* | |
H2C | 0.0593 | 0.3879 | −0.3264 | 0.037* | |
C3 | 0.2802 (5) | 0.5299 (4) | 0.1326 (3) | 0.0345 (12) | |
H3A | 0.2443 | 0.5445 | 0.2066 | 0.041* | |
H3B | 0.4109 | 0.5290 | 0.1193 | 0.041* | |
H3C | 0.2416 | 0.4462 | 0.1248 | 0.041* | |
C1 | 0.4562 (5) | 0.7078 (4) | −0.3577 (3) | 0.0337 (11) | |
H1A | 0.4364 | 0.7194 | −0.2819 | 0.040* | |
H1B | 0.4415 | 0.7926 | −0.4065 | 0.040* | |
H1C | 0.5778 | 0.6682 | −0.3707 | 0.040* | |
N1 | 0.1412 (4) | 0.9352 (3) | 0.2788 (3) | 0.0284 (9) | |
C5 | 0.2134 (6) | 0.8677 (4) | 0.2037 (4) | 0.0285 (11) | |
C6 | 0.4188 (5) | 0.8692 (4) | 0.1933 (4) | 0.0328 (11) | |
H6A | 0.4606 | 0.9252 | 0.1241 | 0.039* | |
H6B | 0.4774 | 0.7803 | 0.1964 | 0.039* | |
C7 | −0.0538 (5) | 0.9594 (5) | 0.3041 (4) | 0.0429 (13) | |
H7A | −0.1187 | 0.9163 | 0.2593 | 0.051* | |
H7B | −0.0873 | 1.0532 | 0.2883 | 0.051* | |
H7C | −0.0847 | 0.9248 | 0.3813 | 0.051* | |
C4 | −0.0891 (5) | 0.7858 (5) | −0.0360 (4) | 0.0474 (14) | |
H4A | −0.1896 | 0.7522 | 0.0140 | 0.057* | |
H4B | −0.1051 | 0.7733 | −0.1096 | 0.057* | |
H4C | −0.0852 | 0.8787 | −0.0367 | 0.057* | |
C8 | 0.2747 (5) | 0.9906 (5) | 0.3324 (4) | 0.0442 (13) | |
H8A | 0.2534 | 0.9683 | 0.4127 | 0.053* | |
H8B | 0.2699 | 1.0865 | 0.3094 | 0.053* | |
C9 | 0.4596 (5) | 0.9255 (4) | 0.2925 (4) | 0.0319 (11) | |
H9A | 0.5495 | 0.9906 | 0.2708 | 0.038* | |
H9B | 0.5056 | 0.8555 | 0.3507 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn2 | 0.02822 (18) | 0.0325 (2) | 0.0236 (2) | −0.00442 (14) | −0.00504 (14) | −0.00406 (15) |
Sn1 | 0.02558 (18) | 0.0271 (2) | 0.0262 (2) | −0.00203 (13) | −0.00240 (14) | −0.00664 (15) |
Cl1 | 0.0363 (6) | 0.0395 (7) | 0.0247 (7) | −0.0024 (5) | −0.0034 (5) | −0.0034 (6) |
Cl4 | 0.0447 (7) | 0.0481 (8) | 0.0253 (7) | −0.0134 (6) | −0.0025 (5) | −0.0102 (6) |
Cl2 | 0.0341 (6) | 0.0407 (8) | 0.0485 (8) | 0.0096 (5) | −0.0082 (6) | −0.0154 (6) |
Cl3 | 0.0478 (7) | 0.0498 (8) | 0.0331 (7) | −0.0207 (6) | 0.0030 (6) | −0.0078 (6) |
O1 | 0.0299 (16) | 0.038 (2) | 0.035 (2) | −0.0046 (14) | −0.0026 (14) | −0.0142 (16) |
C2 | 0.029 (2) | 0.029 (3) | 0.035 (3) | 0.000 (2) | −0.005 (2) | −0.007 (2) |
C3 | 0.035 (3) | 0.034 (3) | 0.034 (3) | −0.003 (2) | −0.010 (2) | −0.002 (2) |
C1 | 0.040 (3) | 0.035 (3) | 0.030 (3) | −0.007 (2) | −0.006 (2) | −0.012 (2) |
N1 | 0.0250 (19) | 0.028 (2) | 0.032 (2) | 0.0007 (16) | −0.0018 (17) | −0.0092 (18) |
C5 | 0.034 (3) | 0.020 (3) | 0.029 (3) | −0.002 (2) | −0.003 (2) | 0.004 (2) |
C6 | 0.029 (2) | 0.030 (3) | 0.039 (3) | 0.000 (2) | −0.001 (2) | −0.008 (2) |
C7 | 0.029 (3) | 0.049 (3) | 0.055 (4) | 0.001 (2) | −0.006 (2) | −0.020 (3) |
C4 | 0.046 (3) | 0.042 (3) | 0.055 (4) | 0.001 (2) | −0.028 (3) | −0.003 (3) |
C8 | 0.033 (3) | 0.055 (4) | 0.051 (3) | −0.001 (2) | −0.006 (2) | −0.026 (3) |
C9 | 0.030 (2) | 0.031 (3) | 0.036 (3) | −0.005 (2) | −0.004 (2) | −0.008 (2) |
Sn2—C3 | 2.100 (4) | C1—H1C | 0.9600 |
Sn2—C4 | 2.103 (4) | N1—C5 | 1.308 (5) |
Sn2—O1 | 2.278 (3) | N1—C7 | 1.447 (5) |
Sn2—Cl3 | 2.3777 (13) | N1—C8 | 1.455 (5) |
Sn2—Cl4 | 2.5704 (13) | C5—C6 | 1.507 (5) |
Sn1—C2 | 2.100 (4) | C6—C9 | 1.519 (5) |
Sn1—C1 | 2.109 (4) | C6—H6A | 0.9700 |
Sn1—Cl2 | 2.3702 (13) | C6—H6B | 0.9700 |
Sn1—Cl1 | 2.4197 (12) | C7—H7A | 0.9600 |
Sn1—Cl4 | 3.1159 (13) | C7—H7B | 0.9600 |
O1—C5 | 1.259 (5) | C7—H7C | 0.9600 |
C2—H2A | 0.9600 | C4—H4A | 0.9600 |
C2—H2B | 0.9600 | C4—H4B | 0.9600 |
C2—H2C | 0.9600 | C4—H4C | 0.9600 |
C3—H3A | 0.9600 | C8—C9 | 1.539 (5) |
C3—H3B | 0.9600 | C8—H8A | 0.9700 |
C3—H3C | 0.9600 | C8—H8B | 0.9700 |
C1—H1A | 0.9600 | C9—H9A | 0.9700 |
C1—H1B | 0.9600 | C9—H9B | 0.9700 |
C3—Sn2—C4 | 146.29 (17) | C5—N1—C7 | 124.0 (4) |
C3—Sn2—O1 | 89.91 (14) | C5—N1—C8 | 114.0 (3) |
C4—Sn2—O1 | 83.59 (15) | C7—N1—C8 | 121.9 (4) |
C3—Sn2—Cl3 | 106.58 (11) | O1—C5—N1 | 123.2 (4) |
C4—Sn2—Cl3 | 106.37 (13) | O1—C5—C6 | 126.5 (4) |
O1—Sn2—Cl3 | 89.24 (8) | N1—C5—C6 | 110.2 (4) |
C3—Sn2—Cl4 | 91.98 (12) | C5—C6—C9 | 104.2 (3) |
C4—Sn2—Cl4 | 93.81 (14) | C5—C6—H6A | 110.9 |
O1—Sn2—Cl4 | 177.35 (7) | C9—C6—H6A | 110.9 |
Cl3—Sn2—Cl4 | 92.00 (5) | C5—C6—H6B | 110.9 |
C2—Sn1—C1 | 142.33 (17) | C9—C6—H6B | 110.9 |
C2—Sn1—Cl2 | 105.64 (11) | H6A—C6—H6B | 108.9 |
C1—Sn1—Cl2 | 103.99 (12) | N1—C7—H7A | 109.5 |
C2—Sn1—Cl1 | 99.50 (12) | N1—C7—H7B | 109.5 |
C1—Sn1—Cl1 | 100.18 (12) | H7A—C7—H7B | 109.5 |
Cl2—Sn1—Cl1 | 95.67 (5) | N1—C7—H7C | 109.5 |
Sn1—Cl4—Sn2 | 135.56 (5) | H7A—C7—H7C | 109.5 |
C5—O1—Sn2 | 140.0 (3) | H7B—C7—H7C | 109.5 |
Sn1—C2—H2A | 109.5 | Sn2—C4—H4A | 109.5 |
Sn1—C2—H2B | 109.5 | Sn2—C4—H4B | 109.5 |
H2A—C2—H2B | 109.5 | H4A—C4—H4B | 109.5 |
Sn1—C2—H2C | 109.5 | Sn2—C4—H4C | 109.5 |
H2A—C2—H2C | 109.5 | H4A—C4—H4C | 109.5 |
H2B—C2—H2C | 109.5 | H4B—C4—H4C | 109.5 |
Sn2—C3—H3A | 109.5 | N1—C8—C9 | 103.9 (3) |
Sn2—C3—H3B | 109.5 | N1—C8—H8A | 111.0 |
H3A—C3—H3B | 109.5 | C9—C8—H8A | 111.0 |
Sn2—C3—H3C | 109.5 | N1—C8—H8B | 111.0 |
H3A—C3—H3C | 109.5 | C9—C8—H8B | 111.0 |
H3B—C3—H3C | 109.5 | H8A—C8—H8B | 109.0 |
Sn1—C1—H1A | 109.5 | C6—C9—C8 | 104.7 (3) |
Sn1—C1—H1B | 109.5 | C6—C9—H9A | 110.8 |
H1A—C1—H1B | 109.5 | C8—C9—H9A | 110.8 |
Sn1—C1—H1C | 109.5 | C6—C9—H9B | 110.8 |
H1A—C1—H1C | 109.5 | C8—C9—H9B | 110.8 |
H1B—C1—H1C | 109.5 | H9A—C9—H9B | 108.9 |
C3—Sn2—O1—C5 | 61.5 (4) | C7—N1—C5—C6 | 176.3 (4) |
C4—Sn2—O1—C5 | −151.6 (4) | C8—N1—C5—C6 | −1.0 (5) |
Cl3—Sn2—O1—C5 | −45.1 (4) | O1—C5—C6—C9 | −171.8 (4) |
Cl4—Sn2—O1—C5 | −163.0 (14) | N1—C5—C6—C9 | 11.5 (5) |
Sn2—O1—C5—N1 | −175.3 (3) | C5—N1—C8—C9 | −9.8 (5) |
Sn2—O1—C5—C6 | 8.3 (7) | C7—N1—C8—C9 | 172.9 (4) |
C7—N1—C5—O1 | −0.7 (7) | C5—C6—C9—C8 | −16.5 (5) |
C8—N1—C5—O1 | −177.9 (4) | N1—C8—C9—C6 | 16.0 (5) |
Experimental details
Crystal data | |
Chemical formula | [Sn2Cl4(CH3)4(C5H9NO)] |
Mr | 538.45 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 7.3650 (15), 10.311 (2), 12.311 (3) |
α, β, γ (°) | 78.45 (3), 84.36 (3), 84.38 (3) |
V (Å3) | 908.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.32 |
Crystal size (mm) | 0.1 × 0.08 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5442, 3557, 2466 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.640 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.063, 0.80 |
No. of reflections | 3557 |
No. of parameters | 159 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −0.85 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97 and PARST95 (Nardelli, 1995).
Sn2—C3 | 2.100 (4) | Sn1—C2 | 2.100 (4) |
Sn2—C4 | 2.103 (4) | Sn1—C1 | 2.109 (4) |
Sn2—O1 | 2.278 (3) | Sn1—Cl1 | 2.4197 (12) |
Sn2—Cl3 | 2.3777 (13) | Sn1—Cl4 | 3.1159 (13) |
Sn2—Cl4 | 2.5704 (13) | ||
C3—Sn2—C4 | 146.29 (17) | Cl3—Sn2—Cl4 | 92.00 (5) |
C3—Sn2—O1 | 89.91 (14) | C2—Sn1—C1 | 142.33 (17) |
C4—Sn2—O1 | 83.59 (15) | C2—Sn1—Cl2 | 105.64 (11) |
C3—Sn2—Cl3 | 106.58 (11) | C1—Sn1—Cl2 | 103.99 (12) |
C4—Sn2—Cl3 | 106.37 (13) | C2—Sn1—Cl1 | 99.50 (12) |
O1—Sn2—Cl3 | 89.24 (8) | C1—Sn1—Cl1 | 100.18 (12) |
C3—Sn2—Cl4 | 91.98 (12) | Cl2—Sn1—Cl1 | 95.67 (5) |
C4—Sn2—Cl4 | 93.81 (14) | Sn1—Cl4—Sn2 | 135.56 (5) |
O1—Sn2—Cl4 | 177.35 (7) |
One of the most interesting topics in structural organotin chemistry is the exhibition of pentacoordination at the Sn atom. The complexation of organotin compounds with N-methylpyrrolidinone (NMP) is well established. Articles describing molecular complexes derived from 1:1 and 1:2 complexation of dimethyltin dihalides by NMP have been published (König et al., 2000a,b). A 2:1 complexation of dimethyltin dichloride by NMP should help in the investigation of whether NMP is able to react as a bidentate ligand, which would lead to two different pentacoordinated dimethyltin dihalide adducts. The results show that, as predicted, NMP belongs to the group of monodentate ligands. Nevertheless, there are two pentacoordinated Sn atoms (Sn1 and Sn2) in the crystal of the title compound, (I). Both exhibit a distorted trigonal-bipyramidal geometry.
Atom Sn2 has Cl4 and NMP as apical ligands with an angle of 177.35 (7)° close to the ideal angle of 180°. The deviation from ideal geometry is illustrated more clearly by the widened C3—Sn2—C4 angle of 146.29 (17)° and by the narrowed C3—Sn2—Cl3 and C4—Sn2—Cl3 angles of 106.58 (11) and 106.37 (13)° compared with a value of 120° for an ideal angle in the equatorial plane. This plane contains two methyl groups and one chlorine. These ligands are somewhat displaced towards the axial NMP ligand. This becomes obvious on comparing the values of the angles between the equatorial and axial ligands: (a) C3—Sn2—O1 89.91 (14)°, C4—Sn2—O1 83.59 (15)°, O1—Sn2—Cl3 89.24 (8)°; (b) C3—Sn2—Cl4 91.98 (12)°, C4—Sn2—Cl4 93.81 (14)°, Cl3—Sn2—Cl4 92.00 (5)°. The Sn—O bond length in this compound [2.278 (3) Å] is shorter than in other pentacoordinated tin complexes (Dey et al., 1999; Cunningham et al., 1993). The two Sn2—Cl bond lengths differ; Sn2—Cl3 2.3777 (13) Å and Sn2—Cl4 2.5704 (13) Å. The Sn—Cl bond in the equatorial plane is a little longer than in known pentacoordinated tin complexes (Dey et al., 1999; Cunningham et al., 1993; Einstein & Penfold, 1968). The long axial Sn—Cl bond may be due to its bridging character, similar features having been observed in the structure of the anion of [Me2SnCl.terpy]+[Me2SnCl3]− (Einstein & Penfold, 1968). The values of the bond lengths and bond angles in the NMP ligand are comparable with those observed in other NMP coordinated organometallic compounds (Churchill et al., 1979) and in free NMP (Müller et al., 1996).
The other part of the complex also exhibits a distorted trigonal-bipyramidal coordination geometry around tin. Atom Sn1 has Cl1 and Cl4 as apical ligands with an angle of 175.67 (4)° close to the ideal angle of 180°. The deviation from ideal geometry is demonstrated most clearly by the widened C2—Sn1—C1 angle of 142.33 (17)° and by the narrowed C1—Sn1—Cl2 and C2—Sn2—Cl2 angles of 103.99 (12) and 105.64 (11)°, respectively, compared with a value of 120° for an ideal angle in the equatorial plane. This plane also consists of two methyl groups and one chlorine. The ligands are displaced towards the axial Cl4 ligand. This becomes evident when the angles between the axial and equatorial ligands are compared: (a) C1—Sn1—Cl4 82.82 (12)°, C2—Sn1—Cl4 76.30 (12)°, Cl2—Sn1—Cl4 86.58 (5)°; (b) C1—Sn1—Cl1 100.18 (12)°, C2—Sn1—Cl1 99.50 (12)°, Cl2—Sn1—Cl1 95.67 (5)°. There are three Sn—Cl bonds in this part of the complex represented by the following values: (a) Sn1—Cl1 2.4197 (12) Å, (b) Sn1—Cl2 2.3702 (13) Å, and (c) Sn1—Cl4 3.1159 (13) Å. As in the part of the complex described above, the bond between tin and the chlorine in the equatorial plane is a little longer than in known pentacoordinated tin complexes (Dey et al., 1999; Cunningham et al., 1993; Einstein & Penfold, 1968). On the other hand, the Sn—Cl1 bond is only a little longer than the Sn—Cl2 bond and therefore short. Also, the bond between Sn1 and the bridging chlorine Cl4 is short compared with other complexes containing bridging Cl ligands such as Me3SnCl (Hossain et al., 1979) and Me2SnCl2 (Davies et al., 1970).