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The single-crystal X-ray structure determinations of the title complexes, cis-dichloro-trans-dimethyl-cis-bis(N-methylpyrrolidin-2-one-O)tin(IV), [Sn(CH3)2Cl2(C5H9NO)2], cis-dibromo-trans-dimethyl-cis-bis(N-methylpyrrolidin-2-one-O)tin(IV), [SnBr2(CH3)2(C5H9NO)2], and cis-diiodo-trans-dimethyl-cis-bis(N-methylpyrrolidin-2-one-O)tin(IV), [Sn(CH3)2I2(C5H9NO)2], show that those tin complexes in which coordination of the lactam ligand to SnIV is realized via oxygen exhibit a distorted octahedral geometry.
Supporting information
CCDC references: 143237; 143238; 143239
All three compounds were prepared by a similar route. Freshly sublimed
dichlorodimethylstannane (2.20 g, 10 mmol), derived from the reaction of
dimethyltinoxide with HCl (Pfeiffer, 1902), or dibromodimethylstannane (3.09 g, 10 mmol) was mixed in an atmosphere of argon with a solution of absolute?
N-methylpyrrolidinone (1.98 g, 20 mmol) in dry diethyl ether (10 ml).
After stirring for 30 min the mixture was stored in a refrigerator at 278 K.
Colourless crystals were obtained in quantitative yield for the dichloro
compound, (I) (m.p. 318 K). The structure-relevant NMR parameters are
2J(119Sn—C-1H), 1J(119Sn-13C) and δ(119Sn). A solution of the
complex (70 mg) in C6D6 (420 mg) gave values of 86 Hz, 678 Hz and -47.5
p.p.m., respectively. These values represent an equilibrium which was, as
expected, shifted when a solution of the complex (40 mg) in NMP (590 mg) is
studied: 2J(119Sn—C-1H) = 104 Hz, 1J(119Sn-13C) = 865 Hz and
δ(119Sn) = -154.6 p.p.m. Colourless crystals were obtained in quantitative
yield for the dibromo compound, (II) (m.p. 315 K). A solution of the complex
(80 mg) in C6D6 (410 mg) gave the following values for the
structure-relevant NMR parameters: 2J(119Sn—C-1H) = 84 Hz,
1J(119Sn-13C) = 636 Hz and δ(119Sn) -94.0 p.p.m. The following values
are measured for the complex (40 mg) dissolved in NMP (410 mg):
2J(119Sn—C-1H) = 105 Hz, 1J(119Sn-13C) = 863 Hz, δ(119Sn) =
-204.5 p.p.m. Diiododimethylstannane was obtained according to the literature
method of (Armitage & Tarassoli, 1975) by a halide exchange reaction of
dichlorodimethylstannane with trimethyliodosilane and finally distilled in
vacuo before use. Following the described experimental route yellow
crystals of (III) were obtained in quantitative yield (mp. 326 K). A solution
of the complex (80 mg) in C6D6 (410 mg) gave the following values for the
structure-relevant NMR parameters: 2J(119Sn—C-1H) = 71 Hz,
1J(119Sn-13C) = 462 Hz and δ(119Sn) = -197.9 p.p.m. The following
values were obtained for the complex (60 mg) dissolved in NMP (370 mg):
2J(119Sn—C-1H) = 103 Hz, 1J(119Sn-13C) = 854 Hz and δ(119Sn)
= -284.8 p.p.m. Crystals for the diffraction experiments were obtained by slow
evaporation of solutions of the title compounds in diethyl ether.
All H atoms were placed in calculated positions and refined with a riding model
(including free rotation about C—C bonds), with Uiso constrained to
be 1.5 times Ueq of the carrier atom. The absolute configuration of
the crystal of the bromine derivative, (II), could not be determined reliably
[Flack (1983) parameter 0.366 (13), R1 = 0.0382 and wR2 = 0.1036]. The inverse
of the configuration presented in this paper resulted in poorer residuals
[Flack parameter 0.466 (15), R1 = 0.0400 and wR2= 0.1093] and was therefore
rejected. This means that with increasing halogen size the structure changes
from centrosymmetric P21/c for Cl in (I) to the acentric Pn
for Br in (II) to the acentric Pn but with the inverse configuration for I in
(III). The data were not corrected for absorption and a possible absorption
effect for the bromine derivative, (II), which is the strongest absorber of
the three compounds, cannot be excluded.
For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).
(I)
cis-dichloro-
trans-dimethyl-
cis-bis(
N-methylpyrrolidin-2-one-O)tin(IV)
top
Crystal data top
[SnCl2(CH3)2(C5H9NO)2] | F(000) = 840 |
Mr = 417.92 | Dx = 1.648 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8320 (16) Å | Cell parameters from 6276 reflections |
b = 25.703 (5) Å | θ = 2.6–25.7° |
c = 8.9840 (18) Å | µ = 1.83 mm−1 |
β = 111.38 (3)° | T = 173 K |
V = 1684.0 (6) Å3 | Parallelepiped, colourless |
Z = 4 | 0.15 × 0.10 × 0.10 mm |
Data collection top
Nonius KappaCCD diffractometer | 2598 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 25.7°, θmin = 2.6° |
Detector resolution: 10 vertical, 18 horizontal pixels mm-1 | h = −9→9 |
935 frames via ω–rotation (Δω = 1°) at different θ
values and 2 × 20 s per frame scans | k = −31→31 |
6276 measured reflections | l = −10→10 |
3188 independent reflections | |
Refinement top
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 0.98 | Calculated w = 1/[σ2(Fo2) + (0.0286P)2] where P = (Fo2 + 2Fc2)/3 |
3188 reflections | (Δ/σ)max = 0.005 |
176 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
Crystal data top
[SnCl2(CH3)2(C5H9NO)2] | V = 1684.0 (6) Å3 |
Mr = 417.92 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.8320 (16) Å | µ = 1.83 mm−1 |
b = 25.703 (5) Å | T = 173 K |
c = 8.9840 (18) Å | 0.15 × 0.10 × 0.10 mm |
β = 111.38 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 2598 reflections with I > 2σ(I) |
6276 measured reflections | Rint = 0.019 |
3188 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.32 e Å−3 |
3188 reflections | Δρmin = −0.59 e Å−3 |
176 parameters | |
Special details top
Experimental. The data collections covered the whole sphere of reciprocal space. The crystal
to detector distance was 3.5 cm. Crystal decay was monitored by repeating the
initial frames at the end of data collection. Analysing the duplicate
reflections there were no indications for any decay. The structures were
solved by direct methods (Sheldrick, 1990) and successive difference Fourier
syntheses. Refinement applied full-matrix least-squares methods (Sheldrick,
1997). |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sn1 | 0.55506 (2) | 0.875738 (6) | 0.147222 (16) | 0.02559 (7) | |
Cl1 | 0.44742 (8) | 0.81796 (2) | −0.08912 (7) | 0.03417 (15) | |
Cl2 | 0.28036 (8) | 0.93176 (2) | 0.03559 (6) | 0.03249 (14) | |
C1 | 0.4510 (3) | 0.83341 (8) | 0.2969 (3) | 0.0340 (6) | |
H1A | 0.4597 | 0.7968 | 0.2794 | 0.051* | |
H1B | 0.3249 | 0.8426 | 0.2728 | 0.051* | |
H1C | 0.5210 | 0.8415 | 0.4066 | 0.051* | |
C2 | 0.7403 (3) | 0.91839 (8) | 0.0742 (3) | 0.0322 (6) | |
H2A | 0.7093 | 0.9547 | 0.0682 | 0.048* | |
H2B | 0.7336 | 0.9065 | −0.0291 | 0.048* | |
H2C | 0.8626 | 0.9135 | 0.1500 | 0.048* | |
O1 | 0.8247 (2) | 0.82031 (6) | 0.26626 (19) | 0.0378 (4) | |
C11 | 0.8474 (3) | 0.77224 (9) | 0.2870 (3) | 0.0295 (5) | |
C12 | 0.7258 (3) | 0.73021 (8) | 0.1893 (3) | 0.0374 (6) | |
H12A | 0.7031 | 0.7352 | 0.0767 | 0.056* | |
H12B | 0.6093 | 0.7300 | 0.2043 | 0.056* | |
C13 | 0.8288 (4) | 0.67986 (9) | 0.2489 (3) | 0.0412 (6) | |
H13A | 0.8837 | 0.6672 | 0.1749 | 0.062* | |
H13B | 0.7476 | 0.6533 | 0.2624 | 0.062* | |
C14 | 0.9765 (3) | 0.69428 (9) | 0.4096 (3) | 0.0412 (6) | |
H14A | 0.9409 | 0.6836 | 0.4978 | 0.062* | |
H14B | 1.0929 | 0.6782 | 0.4218 | 0.062* | |
N1 | 0.9878 (3) | 0.75095 (7) | 0.4021 (2) | 0.0324 (5) | |
C15 | 1.1324 (3) | 0.77999 (10) | 0.5218 (3) | 0.0427 (7) | |
H15A | 1.1127 | 0.8166 | 0.5012 | 0.064* | |
H15B | 1.2489 | 0.7704 | 0.5175 | 0.064* | |
H15C | 1.1312 | 0.7722 | 0.6260 | 0.064* | |
O2 | 0.6735 (2) | 0.93132 (6) | 0.38595 (17) | 0.0361 (4) | |
C21 | 0.6857 (3) | 0.97906 (8) | 0.4134 (2) | 0.0259 (5) | |
C22 | 0.5857 (3) | 1.02161 (8) | 0.3011 (2) | 0.0305 (5) | |
H22A | 0.4543 | 1.0159 | 0.2631 | 0.046* | |
H22B | 0.6237 | 1.0232 | 0.2098 | 0.046* | |
C23 | 0.6370 (4) | 1.07148 (9) | 0.3986 (3) | 0.0427 (7) | |
H23A | 0.5321 | 1.0853 | 0.4186 | 0.064* | |
H23B | 0.6799 | 1.0976 | 0.3424 | 0.064* | |
C24 | 0.7897 (3) | 1.05659 (8) | 0.5557 (3) | 0.0339 (6) | |
H24A | 0.9066 | 1.0707 | 0.5609 | 0.051* | |
H24B | 0.7629 | 1.0692 | 0.6467 | 0.051* | |
N2 | 0.7915 (3) | 0.99975 (7) | 0.5524 (2) | 0.0277 (4) | |
C25 | 0.9070 (3) | 0.96993 (9) | 0.6887 (3) | 0.0361 (6) | |
H25A | 0.8876 | 0.9335 | 0.6656 | 0.054* | |
H25B | 0.8768 | 0.9783 | 0.7803 | 0.054* | |
H25C | 1.0333 | 0.9783 | 0.7104 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sn1 | 0.02834 (10) | 0.02253 (10) | 0.02124 (9) | −0.00205 (7) | 0.00352 (7) | 0.00138 (6) |
Cl1 | 0.0404 (4) | 0.0332 (3) | 0.0242 (3) | −0.0062 (3) | 0.0063 (3) | −0.0047 (3) |
Cl2 | 0.0303 (3) | 0.0328 (3) | 0.0296 (3) | 0.0037 (3) | 0.0053 (3) | 0.0060 (2) |
C1 | 0.0496 (16) | 0.0247 (12) | 0.0277 (12) | −0.0025 (11) | 0.0139 (11) | 0.0000 (10) |
C2 | 0.0342 (13) | 0.0252 (12) | 0.0362 (13) | −0.0035 (10) | 0.0117 (11) | −0.0012 (10) |
O1 | 0.0342 (10) | 0.0230 (8) | 0.0452 (10) | 0.0004 (7) | 0.0012 (8) | 0.0030 (7) |
C11 | 0.0305 (14) | 0.0300 (13) | 0.0295 (12) | 0.0012 (11) | 0.0128 (11) | 0.0018 (11) |
C12 | 0.0426 (16) | 0.0268 (12) | 0.0366 (13) | −0.0032 (11) | 0.0070 (12) | −0.0023 (11) |
C13 | 0.0468 (16) | 0.0278 (13) | 0.0532 (16) | −0.0026 (12) | 0.0233 (13) | −0.0054 (12) |
C14 | 0.0386 (15) | 0.0298 (13) | 0.0546 (16) | 0.0089 (11) | 0.0163 (13) | 0.0116 (12) |
N1 | 0.0286 (11) | 0.0281 (10) | 0.0379 (11) | 0.0045 (9) | 0.0092 (9) | 0.0035 (9) |
C15 | 0.0349 (15) | 0.0439 (15) | 0.0401 (15) | 0.0004 (12) | 0.0026 (12) | −0.0050 (12) |
O2 | 0.0479 (11) | 0.0270 (9) | 0.0249 (8) | −0.0030 (8) | 0.0032 (8) | −0.0011 (7) |
C21 | 0.0264 (13) | 0.0279 (12) | 0.0246 (11) | −0.0024 (10) | 0.0108 (10) | −0.0004 (10) |
C22 | 0.0316 (14) | 0.0333 (13) | 0.0246 (12) | 0.0006 (11) | 0.0078 (10) | 0.0034 (10) |
C23 | 0.0598 (18) | 0.0272 (12) | 0.0347 (14) | 0.0066 (12) | 0.0097 (13) | 0.0014 (11) |
C24 | 0.0423 (15) | 0.0280 (12) | 0.0304 (13) | −0.0031 (11) | 0.0118 (11) | −0.0043 (10) |
N2 | 0.0314 (11) | 0.0258 (9) | 0.0217 (10) | −0.0016 (8) | 0.0046 (8) | −0.0004 (8) |
C25 | 0.0375 (15) | 0.0373 (14) | 0.0260 (12) | −0.0005 (11) | 0.0027 (11) | 0.0027 (11) |
Geometric parameters (Å, º) top
Sn1—C2 | 2.105 (2) | C14—H14A | 0.9700 |
Sn1—C1 | 2.111 (2) | C14—H14B | 0.9700 |
Sn1—O1 | 2.4464 (16) | N1—C15 | 1.452 (3) |
Sn1—O2 | 2.4598 (15) | C15—H15A | 0.9600 |
Sn1—Cl1 | 2.4737 (7) | C15—H15B | 0.9600 |
Sn1—Cl2 | 2.4768 (8) | C15—H15C | 0.9600 |
C1—H1A | 0.9600 | O2—C21 | 1.248 (2) |
C1—H1B | 0.9600 | C21—N2 | 1.332 (3) |
C1—H1C | 0.9600 | C21—C22 | 1.500 (3) |
C2—H2A | 0.9600 | C22—C23 | 1.522 (3) |
C2—H2B | 0.9600 | C22—H22A | 0.9700 |
C2—H2C | 0.9600 | C22—H22B | 0.9700 |
O1—C11 | 1.253 (3) | C23—C24 | 1.529 (3) |
C11—N1 | 1.322 (3) | C23—H23A | 0.9700 |
C11—C12 | 1.495 (3) | C23—H23B | 0.9700 |
C12—C13 | 1.516 (3) | C24—N2 | 1.462 (3) |
C12—H12A | 0.9700 | C24—H24A | 0.9700 |
C12—H12B | 0.9700 | C24—H24B | 0.9700 |
C13—C14 | 1.531 (3) | N2—C25 | 1.448 (3) |
C13—H13A | 0.9700 | C25—H25A | 0.9600 |
C13—H13B | 0.9700 | C25—H25B | 0.9600 |
C14—N1 | 1.463 (3) | C25—H25C | 0.9600 |
| | | |
C2—Sn1—C1 | 159.57 (9) | C13—C14—H14A | 111.0 |
C2—Sn1—O1 | 81.74 (7) | N1—C14—H14B | 111.0 |
C1—Sn1—O1 | 83.89 (8) | C13—C14—H14B | 111.0 |
C2—Sn1—O2 | 83.44 (8) | H14A—C14—H14B | 109.0 |
C1—Sn1—O2 | 81.63 (7) | C11—N1—C15 | 124.6 (2) |
O1—Sn1—O2 | 88.06 (6) | C11—N1—C14 | 113.7 (2) |
C2—Sn1—Cl1 | 95.91 (7) | C15—N1—C14 | 121.43 (19) |
C1—Sn1—Cl1 | 98.48 (6) | N1—C15—H15A | 109.5 |
O1—Sn1—Cl1 | 89.73 (5) | N1—C15—H15B | 109.5 |
O2—Sn1—Cl1 | 177.76 (4) | H15A—C15—H15B | 109.5 |
C2—Sn1—Cl2 | 99.59 (7) | N1—C15—H15C | 109.5 |
C1—Sn1—Cl2 | 94.44 (7) | H15A—C15—H15C | 109.5 |
O1—Sn1—Cl2 | 178.02 (4) | H15B—C15—H15C | 109.5 |
O2—Sn1—Cl2 | 90.64 (5) | C21—O2—Sn1 | 136.09 (14) |
Cl1—Sn1—Cl2 | 91.58 (3) | O2—C21—N2 | 123.7 (2) |
Sn1—C1—H1A | 109.5 | O2—C21—C22 | 126.88 (19) |
Sn1—C1—H1B | 109.5 | N2—C21—C22 | 109.46 (18) |
H1A—C1—H1B | 109.5 | C21—C22—C23 | 105.27 (17) |
Sn1—C1—H1C | 109.5 | C21—C22—H22A | 110.7 |
H1A—C1—H1C | 109.5 | C23—C22—H22A | 110.7 |
H1B—C1—H1C | 109.5 | C21—C22—H22B | 110.7 |
Sn1—C2—H2A | 109.5 | C23—C22—H22B | 110.7 |
Sn1—C2—H2B | 109.5 | H22A—C22—H22B | 108.8 |
H2A—C2—H2B | 109.5 | C22—C23—C24 | 105.92 (17) |
Sn1—C2—H2C | 109.5 | C22—C23—H23A | 110.6 |
H2A—C2—H2C | 109.5 | C24—C23—H23A | 110.6 |
H2B—C2—H2C | 109.5 | C22—C23—H23B | 110.6 |
C11—O1—Sn1 | 133.83 (15) | C24—C23—H23B | 110.6 |
O1—C11—N1 | 123.9 (2) | H23A—C23—H23B | 108.7 |
O1—C11—C12 | 126.9 (2) | N2—C24—C23 | 103.98 (17) |
N1—C11—C12 | 109.28 (19) | N2—C24—H24A | 111.0 |
C11—C12—C13 | 105.46 (19) | C23—C24—H24A | 111.0 |
C11—C12—H12A | 110.6 | N2—C24—H24B | 111.0 |
C13—C12—H12A | 110.6 | C23—C24—H24B | 111.0 |
C11—C12—H12B | 110.6 | H24A—C24—H24B | 109.0 |
C13—C12—H12B | 110.6 | C21—N2—C25 | 124.38 (18) |
H12A—C12—H12B | 108.8 | C21—N2—C24 | 114.25 (17) |
C12—C13—C14 | 104.38 (18) | C25—N2—C24 | 121.30 (17) |
C12—C13—H13A | 110.9 | N2—C25—H25A | 109.5 |
C14—C13—H13A | 110.9 | N2—C25—H25B | 109.5 |
C12—C13—H13B | 110.9 | H25A—C25—H25B | 109.5 |
C14—C13—H13B | 110.9 | N2—C25—H25C | 109.5 |
H13A—C13—H13B | 108.9 | H25A—C25—H25C | 109.5 |
N1—C14—C13 | 103.58 (19) | H25B—C25—H25C | 109.5 |
N1—C14—H14A | 111.0 | | |
| | | |
C2—Sn1—O1—C11 | −144.8 (2) | C2—Sn1—O2—C21 | 56.5 (2) |
C1—Sn1—O1—C11 | 49.8 (2) | C1—Sn1—O2—C21 | −137.4 (2) |
O2—Sn1—O1—C11 | 131.6 (2) | O1—Sn1—O2—C21 | 138.4 (2) |
Cl1—Sn1—O1—C11 | −48.8 (2) | Cl1—Sn1—O2—C21 | 129.6 (9) |
Cl2—Sn1—O1—C11 | 82.7 (11) | Cl2—Sn1—O2—C21 | −43.0 (2) |
Sn1—O1—C11—N1 | −153.53 (18) | Sn1—O2—C21—N2 | −165.15 (16) |
Sn1—O1—C11—C12 | 26.9 (4) | Sn1—O2—C21—C22 | 15.9 (4) |
O1—C11—C12—C13 | 171.9 (2) | O2—C21—C22—C23 | 175.0 (2) |
N1—C11—C12—C13 | −7.8 (3) | N2—C21—C22—C23 | −4.1 (3) |
C11—C12—C13—C14 | 16.4 (3) | C21—C22—C23—C24 | 9.0 (3) |
C12—C13—C14—N1 | −18.7 (3) | C22—C23—C24—N2 | −10.5 (3) |
O1—C11—N1—C15 | 1.4 (4) | O2—C21—N2—C25 | 0.7 (4) |
C12—C11—N1—C15 | −178.9 (2) | C22—C21—N2—C25 | 179.8 (2) |
O1—C11—N1—C14 | 175.4 (2) | O2—C21—N2—C24 | 177.8 (2) |
C12—C11—N1—C14 | −4.9 (3) | C22—C21—N2—C24 | −3.0 (3) |
C13—C14—N1—C11 | 15.3 (3) | C23—C24—N2—C21 | 8.7 (3) |
C13—C14—N1—C15 | −170.5 (2) | C23—C24—N2—C25 | −174.1 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···Cl1i | 0.97 | 2.90 | 3.662 (3) | 139 |
C14—H14B···Cl1ii | 0.97 | 2.82 | 3.698 (3) | 152 |
C24—H24B···Cl2iii | 0.97 | 2.99 | 3.916 (3) | 159 |
C22—H22B···Cl2iv | 0.97 | 2.82 | 3.742 (3) | 158 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, −y+3/2, z+1/2; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+2, −z. |
(II)
cis-dibromo-
trans-dimethyl-
cis-bis(
N-methylpyrrolidin-2-one-O)tin(IV)
top
Crystal data top
[SnBr2(CH3)2(C5H9NO)2] | F(000) = 492 |
Mr = 506.84 | Dx = 1.874 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4750 (15) Å | Cell parameters from 3025 reflections |
b = 8.0300 (16) Å | θ = 2.5–25.7° |
c = 14.977 (3) Å | µ = 5.87 mm−1 |
β = 91.98 (3)° | T = 173 K |
V = 898.4 (3) Å3 | Parallelepiped, colourless |
Z = 2 | 0.1 × 0.1 × 0.1 mm |
Data collection top
Nonius KappaCCD diffractometer | 2893 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.005 |
Graphite monochromator | θmax = 25.7°, θmin = 2.5° |
Detector resolution: 19 vertical, 18 horizontal pixels mm-1 | h = −9→8 |
265 frames via ω–rotation (Δω=1°) at different θ values
and 2 × 60 s per frame scans | k = −9→9 |
3025 measured reflections | l = −18→18 |
3019 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | Calculated w = 1/[σ2(Fo2) + (0.0588P)2 + 2.0195P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.104 | (Δ/σ)max < 0.001 |
S = 1.12 | Δρmax = 0.89 e Å−3 |
3019 reflections | Δρmin = −0.85 e Å−3 |
177 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.0055 (14) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.370 (13) |
Crystal data top
[SnBr2(CH3)2(C5H9NO)2] | V = 898.4 (3) Å3 |
Mr = 506.84 | Z = 2 |
Monoclinic, Pn | Mo Kα radiation |
a = 7.4750 (15) Å | µ = 5.87 mm−1 |
b = 8.0300 (16) Å | T = 173 K |
c = 14.977 (3) Å | 0.1 × 0.1 × 0.1 mm |
β = 91.98 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 2893 reflections with I > 2σ(I) |
3025 measured reflections | Rint = 0.005 |
3019 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.104 | Δρmax = 0.89 e Å−3 |
S = 1.12 | Δρmin = −0.85 e Å−3 |
3019 reflections | Absolute structure: Flack (1983) |
177 parameters | Absolute structure parameter: 0.370 (13) |
2 restraints | |
Special details top
Experimental. The data collections covered the whole sphere of reciprocal space. The crystal
to detector distance was 3.5 cm. Crystal decay was monitored by repeating the
initial frames at the end of data collection. Analysing the duplicate
reflections there were no indications for any decay. The structures were
solved by direct methods (Sheldrick, 1990) and successive difference Fourier
syntheses. Refinement applied full-matrix least-squares methods (Sheldrick,
1997). |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sn1 | 0.82865 (5) | 1.17177 (6) | 0.73758 (4) | 0.02583 (18) | |
Br1 | 0.90045 (13) | 1.11171 (13) | 0.91089 (6) | 0.0458 (3) | |
Br2 | 0.67063 (11) | 1.46626 (11) | 0.76191 (6) | 0.0417 (3) | |
C1 | 0.5884 (11) | 1.0377 (11) | 0.7427 (6) | 0.038 (2) | |
H1A | 0.6133 | 0.9260 | 0.7623 | 0.057* | |
H1B | 0.5311 | 1.0352 | 0.6844 | 0.057* | |
H1C | 0.5108 | 1.0906 | 0.7839 | 0.057* | |
C2 | 1.0850 (12) | 1.2726 (13) | 0.7166 (7) | 0.044 (2) | |
H2A | 1.1375 | 1.2171 | 0.6672 | 0.066* | |
H2B | 1.1597 | 1.2572 | 0.7694 | 0.066* | |
H2C | 1.0741 | 1.3894 | 0.7038 | 0.066* | |
O1 | 0.9672 (8) | 0.9232 (7) | 0.6955 (4) | 0.0364 (13) | |
C11 | 0.9471 (11) | 0.8269 (10) | 0.6302 (6) | 0.0312 (18) | |
C12 | 0.7813 (12) | 0.7940 (12) | 0.5741 (7) | 0.040 (2) | |
H12A | 0.7218 | 0.8976 | 0.5579 | 0.060* | |
H12B | 0.6987 | 0.7245 | 0.6060 | 0.060* | |
C13 | 0.8458 (14) | 0.7046 (13) | 0.4912 (7) | 0.045 (2) | |
H13A | 0.8627 | 0.7824 | 0.4427 | 0.067* | |
H13B | 0.7615 | 0.6193 | 0.4715 | 0.067* | |
C14 | 1.0250 (12) | 0.6273 (11) | 0.5234 (6) | 0.0362 (19) | |
H14A | 1.0096 | 0.5123 | 0.5413 | 0.054* | |
H14B | 1.1124 | 0.6323 | 0.4771 | 0.054* | |
N1 | 1.0798 (10) | 0.7326 (9) | 0.6006 (5) | 0.0324 (15) | |
C15 | 1.2563 (12) | 0.7249 (13) | 0.6403 (6) | 0.040 (2) | |
H15A | 1.2797 | 0.6140 | 0.6616 | 0.060* | |
H15B | 1.2658 | 0.8017 | 0.6893 | 0.060* | |
H15C | 1.3419 | 0.7538 | 0.5965 | 0.060* | |
O2 | 0.7907 (8) | 1.2025 (8) | 0.5839 (4) | 0.0366 (14) | |
C21 | 0.6758 (11) | 1.2517 (10) | 0.5289 (5) | 0.0285 (17) | |
C22 | 0.4830 (14) | 1.2921 (15) | 0.5475 (7) | 0.048 (2) | |
H22A | 0.4752 | 1.3676 | 0.5977 | 0.073* | |
H22B | 0.4157 | 1.1919 | 0.5596 | 0.073* | |
C23 | 0.4142 (14) | 1.3758 (13) | 0.4597 (7) | 0.044 (2) | |
H23A | 0.2963 | 1.3344 | 0.4422 | 0.067* | |
H23B | 0.4077 | 1.4957 | 0.4669 | 0.067* | |
C24 | 0.5476 (14) | 1.3309 (10) | 0.3912 (6) | 0.039 (2) | |
H24A | 0.5013 | 1.2439 | 0.3519 | 0.058* | |
H24B | 0.5777 | 1.4271 | 0.3555 | 0.058* | |
N2 | 0.7022 (9) | 1.2728 (8) | 0.4433 (5) | 0.0318 (15) | |
C25 | 0.8664 (15) | 1.2261 (15) | 0.4017 (7) | 0.054 (3) | |
H25A | 0.9440 | 1.1709 | 0.4447 | 0.081* | |
H25B | 0.9246 | 1.3241 | 0.3802 | 0.081* | |
H25C | 0.8398 | 1.1523 | 0.3526 | 0.081* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sn1 | 0.0272 (3) | 0.0267 (3) | 0.0236 (3) | 0.0001 (2) | 0.00088 (17) | −0.0008 (2) |
Br1 | 0.0654 (6) | 0.0450 (6) | 0.0264 (4) | 0.0128 (5) | −0.0054 (4) | −0.0004 (4) |
Br2 | 0.0533 (6) | 0.0323 (5) | 0.0387 (5) | 0.0113 (4) | −0.0088 (4) | −0.0072 (4) |
C1 | 0.031 (4) | 0.039 (5) | 0.044 (5) | −0.008 (4) | 0.002 (4) | −0.003 (4) |
C2 | 0.034 (5) | 0.048 (5) | 0.050 (6) | −0.017 (4) | −0.002 (4) | −0.001 (4) |
O1 | 0.040 (3) | 0.037 (3) | 0.032 (3) | 0.010 (3) | −0.005 (3) | −0.010 (3) |
C11 | 0.030 (4) | 0.029 (4) | 0.035 (5) | −0.001 (3) | 0.001 (3) | 0.004 (3) |
C12 | 0.037 (5) | 0.037 (4) | 0.046 (6) | 0.009 (4) | −0.008 (4) | −0.008 (4) |
C13 | 0.049 (5) | 0.045 (5) | 0.038 (5) | 0.006 (4) | −0.007 (4) | −0.009 (4) |
C14 | 0.042 (5) | 0.029 (4) | 0.038 (5) | 0.003 (4) | 0.000 (4) | −0.007 (4) |
N1 | 0.033 (3) | 0.032 (4) | 0.032 (4) | −0.004 (3) | 0.000 (3) | −0.005 (3) |
C15 | 0.035 (4) | 0.049 (5) | 0.036 (5) | 0.002 (4) | 0.009 (4) | −0.002 (4) |
O2 | 0.035 (3) | 0.048 (3) | 0.027 (3) | 0.008 (3) | 0.005 (3) | 0.003 (3) |
C21 | 0.039 (4) | 0.029 (4) | 0.017 (4) | −0.003 (3) | 0.003 (3) | 0.001 (3) |
C22 | 0.042 (5) | 0.071 (7) | 0.032 (5) | 0.010 (5) | −0.001 (4) | 0.002 (5) |
C23 | 0.044 (5) | 0.047 (5) | 0.042 (5) | 0.007 (4) | −0.006 (4) | 0.000 (4) |
C24 | 0.057 (5) | 0.030 (4) | 0.029 (5) | 0.002 (4) | −0.011 (4) | 0.002 (3) |
N2 | 0.038 (4) | 0.026 (3) | 0.032 (4) | 0.000 (3) | 0.001 (3) | 0.001 (3) |
C25 | 0.058 (6) | 0.068 (7) | 0.037 (6) | 0.012 (5) | 0.017 (5) | 0.004 (5) |
Geometric parameters (Å, º) top
Sn1—C1 | 2.098 (8) | C14—H14A | 0.9700 |
Sn1—C2 | 2.114 (9) | C14—H14B | 0.9700 |
Sn1—O2 | 2.323 (6) | N1—C15 | 1.429 (12) |
Sn1—O1 | 2.345 (6) | C15—H15A | 0.9600 |
Sn1—Br2 | 2.6738 (10) | C15—H15B | 0.9600 |
Sn1—Br1 | 2.6761 (12) | C15—H15C | 0.9600 |
C1—H1A | 0.9600 | O2—C21 | 1.234 (10) |
C1—H1B | 0.9600 | C21—N2 | 1.315 (11) |
C1—H1C | 0.9600 | C21—C22 | 1.512 (13) |
C2—H2A | 0.9600 | C22—C23 | 1.549 (14) |
C2—H2B | 0.9600 | C22—H22A | 0.9700 |
C2—H2C | 0.9600 | C22—H22B | 0.9700 |
O1—C11 | 1.252 (10) | C23—C24 | 1.499 (15) |
C11—N1 | 1.336 (11) | C23—H23A | 0.9700 |
C11—C12 | 1.497 (12) | C23—H23B | 0.9700 |
C12—C13 | 1.527 (13) | C24—N2 | 1.449 (12) |
C12—H12A | 0.9700 | C24—H24A | 0.9700 |
C12—H12B | 0.9700 | C24—H24B | 0.9700 |
C13—C14 | 1.539 (13) | N2—C25 | 1.445 (12) |
C13—H13A | 0.9700 | C25—H25A | 0.9600 |
C13—H13B | 0.9700 | C25—H25B | 0.9600 |
C14—N1 | 1.478 (11) | C25—H25C | 0.9600 |
| | | |
C1—Sn1—C2 | 169.7 (4) | C13—C14—H14A | 111.1 |
C1—Sn1—O2 | 90.9 (3) | N1—C14—H14B | 111.1 |
C2—Sn1—O2 | 83.8 (3) | C13—C14—H14B | 111.1 |
C1—Sn1—O1 | 87.7 (3) | H14A—C14—H14B | 109.1 |
C2—Sn1—O1 | 82.8 (3) | C11—N1—C15 | 124.8 (7) |
O2—Sn1—O1 | 82.2 (2) | C11—N1—C14 | 113.3 (7) |
C1—Sn1—Br2 | 93.8 (3) | C15—N1—C14 | 121.8 (7) |
C2—Sn1—Br2 | 95.1 (3) | N1—C15—H15A | 109.5 |
O2—Sn1—Br2 | 90.11 (15) | N1—C15—H15B | 109.5 |
O1—Sn1—Br2 | 172.17 (15) | H15A—C15—H15B | 109.5 |
C1—Sn1—Br1 | 90.9 (3) | N1—C15—H15C | 109.5 |
C2—Sn1—Br1 | 93.5 (3) | H15A—C15—H15C | 109.5 |
O2—Sn1—Br1 | 173.67 (15) | H15B—C15—H15C | 109.5 |
O1—Sn1—Br1 | 91.81 (15) | C21—O2—Sn1 | 138.9 (5) |
Br2—Sn1—Br1 | 95.85 (3) | O2—C21—N2 | 124.6 (8) |
Sn1—C1—H1A | 109.5 | O2—C21—C22 | 126.3 (7) |
Sn1—C1—H1B | 109.5 | N2—C21—C22 | 109.1 (7) |
H1A—C1—H1B | 109.5 | C21—C22—C23 | 103.2 (8) |
Sn1—C1—H1C | 109.5 | C21—C22—H22A | 111.1 |
H1A—C1—H1C | 109.5 | C23—C22—H22A | 111.1 |
H1B—C1—H1C | 109.5 | C21—C22—H22B | 111.1 |
Sn1—C2—H2A | 109.5 | C23—C22—H22B | 111.1 |
Sn1—C2—H2B | 109.5 | H22A—C22—H22B | 109.1 |
H2A—C2—H2B | 109.5 | C24—C23—C22 | 105.5 (8) |
Sn1—C2—H2C | 109.5 | C24—C23—H23A | 110.6 |
H2A—C2—H2C | 109.5 | C22—C23—H23A | 110.6 |
H2B—C2—H2C | 109.5 | C24—C23—H23B | 110.6 |
C11—O1—Sn1 | 133.9 (5) | C22—C23—H23B | 110.6 |
O1—C11—N1 | 122.6 (8) | H23A—C23—H23B | 108.8 |
O1—C11—C12 | 128.5 (8) | N2—C24—C23 | 104.2 (8) |
N1—C11—C12 | 108.9 (7) | N2—C24—H24A | 110.9 |
C11—C12—C13 | 105.1 (7) | C23—C24—H24A | 110.9 |
C11—C12—H12A | 110.7 | N2—C24—H24B | 110.9 |
C13—C12—H12A | 110.7 | C23—C24—H24B | 110.9 |
C11—C12—H12B | 110.7 | H24A—C24—H24B | 108.9 |
C13—C12—H12B | 110.7 | C21—N2—C25 | 123.0 (8) |
H12A—C12—H12B | 108.8 | C21—N2—C24 | 115.0 (7) |
C12—C13—C14 | 103.3 (7) | C25—N2—C24 | 121.7 (8) |
C12—C13—H13A | 111.1 | N2—C25—H25A | 109.5 |
C14—C13—H13A | 111.1 | N2—C25—H25B | 109.5 |
C12—C13—H13B | 111.1 | H25A—C25—H25B | 109.5 |
C14—C13—H13B | 111.1 | N2—C25—H25C | 109.5 |
H13A—C13—H13B | 109.1 | H25A—C25—H25C | 109.5 |
N1—C14—C13 | 103.2 (7) | H25B—C25—H25C | 109.5 |
N1—C14—H14A | 111.1 | | |
| | | |
C1—Sn1—O1—C11 | 61.7 (8) | C1—Sn1—O2—C21 | 52.6 (9) |
C2—Sn1—O1—C11 | −114.2 (8) | C2—Sn1—O2—C21 | −136.3 (9) |
O2—Sn1—O1—C11 | −29.5 (8) | O1—Sn1—O2—C21 | 140.1 (9) |
Br2—Sn1—O1—C11 | −39.4 (17) | Br2—Sn1—O2—C21 | −41.2 (9) |
Br1—Sn1—O1—C11 | 152.5 (8) | Br1—Sn1—O2—C21 | 158.6 (11) |
Sn1—O1—C11—N1 | 152.4 (6) | Sn1—O2—C21—N2 | 171.3 (6) |
Sn1—O1—C11—C12 | −28.4 (13) | Sn1—O2—C21—C22 | −10.7 (15) |
O1—C11—C12—C13 | 165.2 (9) | O2—C21—C22—C23 | 170.4 (9) |
N1—C11—C12—C13 | −15.5 (10) | N2—C21—C22—C23 | −11.4 (10) |
C11—C12—C13—C14 | 23.7 (10) | C21—C22—C23—C24 | 16.7 (11) |
C12—C13—C14—N1 | −23.1 (10) | C22—C23—C24—N2 | −16.0 (10) |
O1—C11—N1—C15 | 2.2 (13) | O2—C21—N2—C25 | 5.7 (14) |
C12—C11—N1—C15 | −177.1 (8) | C22—C21—N2—C25 | −172.5 (9) |
O1—C11—N1—C14 | 179.4 (8) | O2—C21—N2—C24 | 179.7 (8) |
C12—C11—N1—C14 | 0.1 (10) | C22—C21—N2—C24 | 1.4 (10) |
C13—C14—N1—C11 | 15.1 (10) | C23—C24—N2—C21 | 9.7 (10) |
C13—C14—N1—C15 | −167.6 (8) | C23—C24—N2—C25 | −176.3 (9) |
(III)
cis-diiodo-
trans-dimethyl-
cis-bis(
N-methylpyrrolidin-2-one-O)tin(IV)
top
Crystal data top
[SnI2(CH3)2(C5H9NO)2] | F(000) = 564 |
Mr = 600.82 | Dx = 2.103 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71069 Å |
a = 7.396 (1) Å | Cell parameters from 7279 reflections |
b = 8.327 (2) Å | θ = 2.5–27.1° |
c = 15.406 (3) Å | µ = 4.60 mm−1 |
β = 90.31 (3)° | T = 173 K |
V = 948.8 (3) Å3 | Parallelepiped, pale yellow |
Z = 2 | 0.07 × 0.07 × 0.05 mm |
Data collection top
Nonius KappaCCD diffractometer | 3469 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 27.1°, θmin = 2.5° |
Detector resolution: 19 vertical, 18 horizontal pixels mm-1 | h = −9→9 |
652 frames via ω–rotation (Δω=1°) at different θ values
and 2 × 50 s per frame scans | k = −10→10 |
7279 measured reflections | l = −19→18 |
3944 independent reflections | |
Refinement top
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)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.043 | Calculated w = 1/[σ2(Fo2) + (0.0075P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
3944 reflections | Δρmax = 0.54 e Å−3 |
176 parameters | Δρmin = −0.58 e Å−3 |
2 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (2) |
Crystal data top
[SnI2(CH3)2(C5H9NO)2] | V = 948.8 (3) Å3 |
Mr = 600.82 | Z = 2 |
Monoclinic, Pn | Mo Kα radiation |
a = 7.396 (1) Å | µ = 4.60 mm−1 |
b = 8.327 (2) Å | T = 173 K |
c = 15.406 (3) Å | 0.07 × 0.07 × 0.05 mm |
β = 90.31 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 3469 reflections with I > 2σ(I) |
7279 measured reflections | Rint = 0.026 |
3944 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.043 | Δρmax = 0.54 e Å−3 |
S = 0.95 | Δρmin = −0.58 e Å−3 |
3944 reflections | Absolute structure: Flack (1983) |
176 parameters | Absolute structure parameter: −0.01 (2) |
2 restraints | |
Special details top
Experimental. The data collections covered the whole sphere of reciprocal space. The crystal
to detector distance was 3.5 cm. Crystal decay was monitored by repeating the
initial frames at the end of data collection. Analysing the duplicate
reflections there were no indications for any decay. The structures were
solved by direct methods (Sheldrick, 1990) and successive difference Fourier
syntheses. Refinement applied full-matrix least-squares methods (Sheldrick,
1997). |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sn1 | 0.17025 (3) | −0.16182 (3) | 0.265668 (19) | 0.02513 (8) | |
I1 | 0.11786 (4) | −0.09018 (4) | 0.08104 (2) | 0.04197 (9) | |
I2 | 0.32774 (4) | −0.47681 (4) | 0.23350 (2) | 0.04508 (10) | |
C1 | 0.4183 (6) | −0.0370 (6) | 0.2654 (3) | 0.0345 (11) | |
H1A | 0.3985 | 0.0732 | 0.2451 | 0.052* | |
H1B | 0.5031 | −0.0914 | 0.2265 | 0.052* | |
H1C | 0.4687 | −0.0350 | 0.3243 | 0.052* | |
C2 | −0.0948 (6) | −0.2547 (6) | 0.2792 (4) | 0.0440 (13) | |
H2A | −0.1287 | −0.2537 | 0.3406 | 0.066* | |
H2B | −0.0986 | −0.3652 | 0.2573 | 0.066* | |
H2C | −0.1798 | −0.1882 | 0.2460 | 0.066* | |
O1 | 0.0322 (4) | 0.0772 (3) | 0.3068 (2) | 0.0358 (8) | |
C11 | 0.0500 (6) | 0.1724 (5) | 0.3689 (3) | 0.0275 (10) | |
C12 | 0.2110 (6) | 0.1945 (6) | 0.4272 (3) | 0.0366 (12) | |
H12A | 0.3104 | 0.2493 | 0.3962 | 0.055* | |
H12B | 0.2555 | 0.0898 | 0.4491 | 0.055* | |
C13 | 0.1407 (7) | 0.2984 (6) | 0.5017 (4) | 0.0465 (13) | |
H13A | 0.1078 | 0.2313 | 0.5522 | 0.070* | |
H13B | 0.2328 | 0.3778 | 0.5201 | 0.070* | |
C14 | −0.0251 (6) | 0.3819 (5) | 0.4641 (3) | 0.0362 (11) | |
H14A | −0.1228 | 0.3895 | 0.5076 | 0.054* | |
H14B | 0.0049 | 0.4911 | 0.4432 | 0.054* | |
N1 | −0.0771 (4) | 0.2763 (4) | 0.3920 (2) | 0.0274 (8) | |
C15 | −0.2502 (6) | 0.2939 (5) | 0.3471 (3) | 0.0383 (12) | |
H15A | −0.2545 | 0.3984 | 0.3179 | 0.057* | |
H15B | −0.3487 | 0.2869 | 0.3892 | 0.057* | |
H15C | −0.2635 | 0.2081 | 0.3040 | 0.057* | |
O2 | 0.1951 (4) | −0.2021 (4) | 0.41256 (19) | 0.0334 (7) | |
C21 | 0.3060 (6) | −0.2570 (5) | 0.4671 (3) | 0.0305 (11) | |
C22 | 0.4945 (7) | −0.3164 (7) | 0.4517 (3) | 0.0509 (15) | |
H22A | 0.5742 | −0.2269 | 0.4338 | 0.076* | |
H22B | 0.4951 | −0.3994 | 0.4057 | 0.076* | |
C23 | 0.5574 (7) | −0.3862 (6) | 0.5369 (3) | 0.0443 (13) | |
H23A | 0.6777 | −0.3432 | 0.5531 | 0.066* | |
H23B | 0.5651 | −0.5047 | 0.5333 | 0.066* | |
C24 | 0.4133 (7) | −0.3349 (6) | 0.6040 (3) | 0.0410 (13) | |
H24A | 0.3692 | −0.4285 | 0.6374 | 0.062* | |
H24B | 0.4626 | −0.2541 | 0.6449 | 0.062* | |
N2 | 0.2699 (5) | −0.2668 (4) | 0.5505 (2) | 0.0318 (9) | |
C25 | 0.1064 (7) | −0.2000 (7) | 0.5897 (4) | 0.0589 (15) | |
H25A | 0.1395 | −0.1110 | 0.6283 | 0.088* | |
H25B | 0.0450 | −0.2837 | 0.6232 | 0.088* | |
H25C | 0.0253 | −0.1607 | 0.5439 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sn1 | 0.02255 (15) | 0.02833 (15) | 0.02450 (16) | 0.00168 (13) | −0.00268 (12) | −0.00072 (13) |
I1 | 0.0527 (2) | 0.04596 (19) | 0.02711 (18) | 0.01084 (16) | −0.00914 (14) | −0.00003 (15) |
I2 | 0.0610 (2) | 0.03703 (17) | 0.03705 (19) | 0.01835 (17) | −0.01809 (16) | −0.01022 (16) |
C1 | 0.028 (3) | 0.042 (3) | 0.033 (3) | −0.003 (2) | 0.003 (2) | 0.006 (2) |
C2 | 0.021 (3) | 0.051 (3) | 0.060 (3) | −0.006 (2) | 0.004 (2) | 0.006 (3) |
O1 | 0.0325 (18) | 0.0388 (18) | 0.0359 (19) | 0.0064 (15) | −0.0073 (15) | −0.0111 (16) |
C11 | 0.030 (3) | 0.026 (2) | 0.027 (3) | 0.002 (2) | −0.001 (2) | 0.000 (2) |
C12 | 0.030 (3) | 0.039 (3) | 0.040 (3) | 0.002 (2) | −0.007 (2) | −0.003 (2) |
C13 | 0.046 (3) | 0.048 (3) | 0.045 (3) | 0.000 (2) | −0.014 (2) | −0.014 (3) |
C14 | 0.039 (3) | 0.033 (3) | 0.037 (3) | 0.000 (2) | 0.000 (2) | −0.010 (2) |
N1 | 0.024 (2) | 0.032 (2) | 0.026 (2) | 0.0019 (16) | −0.0032 (16) | −0.0011 (16) |
C15 | 0.027 (3) | 0.040 (3) | 0.047 (3) | 0.008 (2) | −0.006 (2) | −0.003 (2) |
O2 | 0.0301 (18) | 0.0442 (18) | 0.0258 (18) | 0.0063 (14) | −0.0006 (15) | 0.0022 (15) |
C21 | 0.037 (3) | 0.024 (2) | 0.030 (3) | 0.001 (2) | −0.004 (2) | −0.004 (2) |
C22 | 0.037 (3) | 0.089 (4) | 0.027 (3) | 0.020 (3) | −0.012 (2) | −0.014 (3) |
C23 | 0.050 (3) | 0.046 (3) | 0.037 (3) | 0.010 (2) | −0.010 (3) | −0.009 (2) |
C24 | 0.055 (3) | 0.038 (3) | 0.030 (3) | −0.005 (2) | −0.013 (3) | 0.004 (2) |
N2 | 0.038 (2) | 0.032 (2) | 0.025 (2) | −0.0008 (18) | 0.0040 (17) | −0.0008 (18) |
C25 | 0.051 (4) | 0.078 (4) | 0.048 (3) | 0.013 (3) | 0.022 (3) | 0.005 (3) |
Geometric parameters (Å, º) top
Sn1—C1 | 2.109 (4) | C14—H14A | 0.9900 |
Sn1—C2 | 2.119 (4) | C14—H14B | 0.9900 |
Sn1—O2 | 2.294 (3) | N1—C15 | 1.459 (5) |
Sn1—O1 | 2.326 (3) | C15—H15A | 0.9800 |
Sn1—I2 | 2.9135 (7) | C15—H15B | 0.9800 |
Sn1—I1 | 2.9299 (7) | C15—H15C | 0.9800 |
C1—H1A | 0.9800 | O2—C21 | 1.257 (5) |
C1—H1B | 0.9800 | C21—N2 | 1.317 (5) |
C1—H1C | 0.9800 | C21—C22 | 1.500 (6) |
C2—H2A | 0.9800 | C22—C23 | 1.508 (7) |
C2—H2B | 0.9800 | C22—H22A | 0.9900 |
C2—H2C | 0.9800 | C22—H22B | 0.9900 |
O1—C11 | 1.249 (5) | C23—C24 | 1.549 (7) |
C11—N1 | 1.328 (5) | C23—H23A | 0.9900 |
C11—C12 | 1.499 (6) | C23—H23B | 0.9900 |
C12—C13 | 1.530 (6) | C24—N2 | 1.455 (6) |
C12—H12A | 0.9900 | C24—H24A | 0.9900 |
C12—H12B | 0.9900 | C24—H24B | 0.9900 |
C13—C14 | 1.521 (7) | N2—C25 | 1.464 (6) |
C13—H13A | 0.9900 | C25—H25A | 0.9800 |
C13—H13B | 0.9900 | C25—H25B | 0.9800 |
C14—N1 | 1.467 (6) | C25—H25C | 0.9800 |
| | | |
C1—Sn1—C2 | 170.3 (2) | C13—C14—H14A | 111.2 |
C1—Sn1—O2 | 90.53 (15) | N1—C14—H14B | 111.2 |
C2—Sn1—O2 | 85.33 (16) | C13—C14—H14B | 111.2 |
C1—Sn1—O1 | 87.84 (15) | H14A—C14—H14B | 109.1 |
C2—Sn1—O1 | 82.98 (16) | C11—N1—C15 | 124.0 (4) |
O2—Sn1—O1 | 83.63 (11) | C11—N1—C14 | 114.3 (3) |
C1—Sn1—I2 | 95.42 (13) | C15—N1—C14 | 121.6 (3) |
C2—Sn1—I2 | 93.39 (14) | N1—C15—H15A | 109.5 |
O2—Sn1—I2 | 90.35 (7) | N1—C15—H15B | 109.5 |
O1—Sn1—I2 | 173.19 (8) | H15A—C15—H15B | 109.5 |
C1—Sn1—I1 | 90.46 (13) | N1—C15—H15C | 109.5 |
C2—Sn1—I1 | 93.01 (15) | H15A—C15—H15C | 109.5 |
O2—Sn1—I1 | 175.46 (7) | H15B—C15—H15C | 109.5 |
O1—Sn1—I1 | 91.98 (8) | C21—O2—Sn1 | 139.6 (3) |
I2—Sn1—I1 | 93.960 (17) | O2—C21—N2 | 122.7 (4) |
Sn1—C1—H1A | 109.5 | O2—C21—C22 | 128.2 (4) |
Sn1—C1—H1B | 109.5 | N2—C21—C22 | 109.1 (4) |
H1A—C1—H1B | 109.5 | C21—C22—C23 | 105.8 (4) |
Sn1—C1—H1C | 109.5 | C21—C22—H22A | 110.6 |
H1A—C1—H1C | 109.5 | C23—C22—H22A | 110.6 |
H1B—C1—H1C | 109.5 | C21—C22—H22B | 110.6 |
Sn1—C2—H2A | 109.5 | C23—C22—H22B | 110.6 |
Sn1—C2—H2B | 109.5 | H22A—C22—H22B | 108.7 |
H2A—C2—H2B | 109.5 | C22—C23—C24 | 105.4 (4) |
Sn1—C2—H2C | 109.5 | C22—C23—H23A | 110.7 |
H2A—C2—H2C | 109.5 | C24—C23—H23A | 110.7 |
H2B—C2—H2C | 109.5 | C22—C23—H23B | 110.7 |
C11—O1—Sn1 | 135.0 (3) | C24—C23—H23B | 110.7 |
O1—C11—N1 | 123.2 (4) | H23A—C23—H23B | 108.8 |
O1—C11—C12 | 128.1 (4) | N2—C24—C23 | 103.4 (4) |
N1—C11—C12 | 108.7 (4) | N2—C24—H24A | 111.1 |
C11—C12—C13 | 104.3 (4) | C23—C24—H24A | 111.1 |
C11—C12—H12A | 110.9 | N2—C24—H24B | 111.1 |
C13—C12—H12A | 110.9 | C23—C24—H24B | 111.1 |
C11—C12—H12B | 110.9 | H24A—C24—H24B | 109.1 |
C13—C12—H12B | 110.9 | C21—N2—C24 | 115.2 (4) |
H12A—C12—H12B | 108.9 | C21—N2—C25 | 123.5 (4) |
C14—C13—C12 | 104.5 (4) | C24—N2—C25 | 121.0 (4) |
C14—C13—H13A | 110.9 | N2—C25—H25A | 109.5 |
C12—C13—H13A | 110.9 | N2—C25—H25B | 109.5 |
C14—C13—H13B | 110.9 | H25A—C25—H25B | 109.5 |
C12—C13—H13B | 110.9 | N2—C25—H25C | 109.5 |
H13A—C13—H13B | 108.9 | H25A—C25—H25C | 109.5 |
N1—C14—C13 | 102.8 (3) | H25B—C25—H25C | 109.5 |
N1—C14—H14A | 111.2 | | |
| | | |
C1—Sn1—O1—C11 | −58.1 (4) | C1—Sn1—O2—C21 | −52.9 (4) |
C2—Sn1—O1—C11 | 118.7 (4) | C2—Sn1—O2—C21 | 135.9 (4) |
O2—Sn1—O1—C11 | 32.6 (4) | O1—Sn1—O2—C21 | −140.7 (4) |
I2—Sn1—O1—C11 | 60.7 (9) | I2—Sn1—O2—C21 | 42.5 (4) |
I1—Sn1—O1—C11 | −148.5 (4) | I1—Sn1—O2—C21 | −155.5 (7) |
Sn1—O1—C11—N1 | −160.0 (3) | Sn1—O2—C21—N2 | −177.4 (3) |
Sn1—O1—C11—C12 | 21.8 (7) | Sn1—O2—C21—C22 | 4.2 (8) |
O1—C11—C12—C13 | −168.1 (4) | O2—C21—C22—C23 | −173.4 (4) |
N1—C11—C12—C13 | 13.5 (5) | N2—C21—C22—C23 | 8.0 (5) |
C11—C12—C13—C14 | −22.1 (5) | C21—C22—C23—C24 | −10.5 (5) |
C12—C13—C14—N1 | 22.3 (5) | C22—C23—C24—N2 | 9.3 (5) |
O1—C11—N1—C15 | −1.2 (6) | O2—C21—N2—C24 | 179.4 (4) |
C12—C11—N1—C15 | 177.3 (4) | C22—C21—N2—C24 | −1.9 (5) |
O1—C11—N1—C14 | −177.3 (4) | O2—C21—N2—C25 | −6.7 (7) |
C12—C11—N1—C14 | 1.2 (5) | C22—C21—N2—C25 | 172.0 (4) |
C13—C14—N1—C11 | −15.4 (5) | C23—C24—N2—C21 | −4.8 (5) |
C13—C14—N1—C15 | 168.4 (4) | C23—C24—N2—C25 | −178.8 (4) |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | [SnCl2(CH3)2(C5H9NO)2] | [SnBr2(CH3)2(C5H9NO)2] | [SnI2(CH3)2(C5H9NO)2] |
Mr | 417.92 | 506.84 | 600.82 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, Pn | Monoclinic, Pn |
Temperature (K) | 173 | 173 | 173 |
a, b, c (Å) | 7.8320 (16), 25.703 (5), 8.9840 (18) | 7.4750 (15), 8.0300 (16), 14.977 (3) | 7.396 (1), 8.327 (2), 15.406 (3) |
β (°) | 111.38 (3) | 91.98 (3) | 90.31 (3) |
V (Å3) | 1684.0 (6) | 898.4 (3) | 948.8 (3) |
Z | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.83 | 5.87 | 4.60 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 | 0.1 × 0.1 × 0.1 | 0.07 × 0.07 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6276, 3188, 2598 | 3025, 3019, 2893 | 7279, 3944, 3469 |
Rint | 0.019 | 0.005 | 0.026 |
(sin θ/λ)max (Å−1) | 0.609 | 0.609 | 0.641 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.050, 0.98 | 0.038, 0.104, 1.12 | 0.024, 0.043, 0.95 |
No. of reflections | 3188 | 3019 | 3944 |
No. of parameters | 176 | 177 | 176 |
No. of restraints | 0 | 2 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.59 | 0.89, −0.85 | 0.54, −0.58 |
Absolute structure | ? | Flack (1983) | Flack (1983) |
Absolute structure parameter | ? | 0.370 (13) | −0.01 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···Cl1i | 0.97 | 2.90 | 3.662 (3) | 139 |
C14—H14B···Cl1ii | 0.97 | 2.82 | 3.698 (3) | 152 |
C24—H24B···Cl2iii | 0.97 | 2.99 | 3.916 (3) | 159 |
C22—H22B···Cl2iv | 0.97 | 2.82 | 3.742 (3) | 158 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, −y+3/2, z+1/2; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+2, −z. |
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Molecular complexes of dimethyltin dihalides with electron-donor solvents such as dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF) have been explored extensively (Tanaka, 1967; Isaacs et al., 1968; Aslanov et al., 1978). Studies of complexes of the related N-methylpyrrolidinone (NMP) ligand have not been published to date. The structures of the title complexes, cis-dichloro-trans-dimethyl-cis-bis(N-methylpyrrolidin-2-one-O)tin(IV), (I), cis-dibromo-trans-dimethyl-cis-bis(N-methylpyrrolidin-2-one-O)tin(IV), (II) and cis-diiodo-trans-dimethyl-cis-bis(N-methylpyrrolidin-2-one-O)tin(IV), (III), are part of our study on the Stille reaction in which the compounds investigated can be formed as by-products. These complexes are of great promise in studying solvent effects on organometallic reactions. \scheme
In all three cases, the crystals exhibit distorted octahedral geometry. The degree of distortion becomes obvious when the angles C—Sn—C and O—Sn-halogen are compared. The values are as follows: (I) C—Sn—C 159.57 (9), O—Sn—Cl 177.76 (4) and 178.02 (4)°, (II) C—Sn—C 169.7 (4), O—Sn—Br 172.17 (15) and 173.67 (15)°, and (III) C—Sn—C 170.3 (2), O—Sn—I 173.19 (8) and 175.46 (7)°.
The bond lengths and angles in the NMP ligand of complexes (I)-(III) agree well with those in the uncoordinated ligand (Müller et al., 1996). In the dichloro compound, (I), the torsion angles of both NMP ligands are within the range previously reported. In the dibromo compound, (II), the torsion angle C11—C12—C13—C14 increases to 23.7 (10)°, while in the diiodo compound, (III), the torsion angle C12—C13—C14—N1 is 22.3 (5)°. In these three compounds the deviation from planarity is larger than in the uncomplexed NMP. The orientation of the NMP ligands can be described by the following torsion angles. Sn—O1—C11—N1 - 153.53 (18) in (I), 152.4 (6) in (II) and -160.0 (3)° in (III); Sn—O2—C21—N2 - 165.15 (16) in (I), 171.3 (6) in (II) and -177.4 (3)° in (III). These orientations could be determined by the C15—H···O1 and C25—H···O2 interactions with H···O distances in the range from 2.41 to 2.47 Å, C···O distances in the range from 2.811 (12) to 2.850 (3) Å and C—H···O angles in the range from 103 to 104°.
There are only slight differences between the bond lengths in the Sn—C fragment [2.105 (2) and 2.111 (2) Å in (I), 2.098 (8) and 2.114 (9) Å in (II), and 2.109 (4) and 2.119 (4) Å in (III)] and they are comparable with reported values (Skinner & Sutton, 1944; Fujii & Kimura, 1971; Aslanov et al., 1978). The Sn-halogen bonds are longer [2.4737 (7) and 2.4768 (8) Å in (I), 2.6738 (10) and 2.6761 (12) Å in (II), and 2.9135 (7) and 2.9299 (7) Å in (III)] than in the uncomplexed compounds and correlate with the values for related organotin complexes with DMF or DMSO (Isaacs & Kennard, 1970; Aslanov et al., 1978).
A comparative study of the values of the Sn—O bond lengths leads to the unexpected result that the Sn—O bonds in the dichloro compound are the longest in the series [2.4464 (16) and 2.4598 (15) Å] and are thus a little longer than in the related DMF compound (2.390 Å; Aslanov et al., 1978). In the dibromo [2.323 (6) and 2.345 (6) Å] and the diiodo [2.294 (3) and 2.326 (3) Å] compounds the Sn—O bond lengths are almost the same. This can be explained by the tendency of Cl to react as an electron acceptor. In the trinuclear, almost linear, fragment ONMP—Sn—Cl, the Cl can draw out of the Sn—O bond the electron density delivered by O. Consequently, the Sn—Cl bond becomes shorter and the Sn—O bond length increases (Aslanov et al., 1978). This effect might well be expected to be even greater on going from Br to I, but the size of the ligand in fact seems to become predominant.
In (II) and (III) there are no intermolecular interactions exceeding van der Waals forces, whereas in (I) weak C—H···Cl interactions are also effective.