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Structural variety of 2-amidoethyltin compounds
Accepted Manuscript Structural variety of 2-amidoethyltin compounds Daniele C. Menezes, Geraldo M. de Lima, James L. Wardell, Jessica GomezBanderas, William T.A. Harrison PII:
S0022-328X(17)30500-4
DOI:
10.1016/j.jorganchem.2017.08.011
Reference:
JOM 20064
To appear in:
Journal of Organometallic Chemistry
Received Date: 31 May 2017 Revised Date:
18 August 2017
Accepted Date: 19 August 2017
Please cite this article as: D.C. Menezes, G.M. de Lima, J.L. Wardell, J. Gomez-Banderas, W.T.A. Harrison, Structural variety of 2-amidoethyltin compounds, Journal of Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2017.08.011. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Structural variety of 2-amidoethyltin compounds
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Daniele C. Menezes a*, Geraldo M. de Limab, James L. Wardellc,d, Jessica Gomez-Banderasc and William T. A. Harrisonc
Departamento de Química, Universidade Federal de Viçosa, 36570-000 Viçosa-MG, Brasil.
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a b
Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais,
c
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31270–901, Belo Horizonte–MG, Brasil.
Departament of Chemistry, University of Aberdeen, AB24 2UE, Aberdeen, Scotland d
Instituto de Tecnologia em Fármacos, Fundação Oswaldo Cruz, 21041-250,
Abstract
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Rio de Janeiro, RJ, Brasil.
The syntheses, spectroscopic data and crystal structures of (H2NCOCH2CH2-C)(R2NCS2-S,S/)3Sn (H2NCOCH2CH2-C,O)2SnCl2
(triclinic
polymorph)
(2),
(H2NCOCH2CH2-C,O)(2-
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(1),
H2NCOC6H4S-O,S)SnCl2 (3) and Sn(C11H9N2O2)Cl3 (4) are reported. The tin atom in compound 1 (R = Et) is coordinated by three chelating dithiocarbamate anions and a C-bound non-chelating
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amidoethyl ligand to generate a SnS6C pentagonal-bipyramidal coordination polyhedron. Compound 2, which features SnC2O2Cl2 octahedra, was crystallised from mixed solvents (ethanol and water) and complements the two known monoclinic forms. Compound 3 arose unexpectedly due to ligand disproportionation of the tin starting material and a “transesterification” reaction of the starting ligand: distorted SnCSO2Cl2 octahedra are seen in the crystal structure. Compound 4 arose from another ligand disproportionation reaction and features neutral complex molecules with N2OCl3 donor sets coordinating to the octahedral tin atoms.
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1. Introduction Functionally-substituted alkyltin halides, YCOCH2CR″2SnX3 and (YCOCH2CR″2)2SnX2 (e.g.: X = halide, Y = R′, OR′ or NR′2, R′ = alkyl or aryl, R″ = H or Me) were prepared in the 1970s as
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possible precursors of organotin mercaptides for use as PVC stabilisers [1]. While this use has not been realised, the coordination chemistry of 2-carbonylethyl-tin compounds has been extensively studied ever since [2]. The large volume of work reported for the so called “estertin” compounds, R′O2CCH2CH2SnX3 and (R′O2CCH2CH2)2SnX2, (where the ester C=O group closes
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the five-membered –Sn–C–C–C=O– chelate ring) contrasts with the few structural studies carried out on “ketotin” compounds, R′COCH2CR″2SnX3 and (R′COCH2CR″2)2SnX2 [3] and the “amidotin” species H2NCOCH2CH2SnX3 and (H2NCOCH2CH2)2SnX2 [4].
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Only within the last few years have amidotin compounds attracted systematic attention, which has led to reports of the syntheses and crystal structures of families of (H2NCOCH2CH2C,O)2SnX2 derivatives (X = halide, azide, chelating 1,2-dithiolato, etc.) [5], [(H2NCOCH2CH2C,O)SnCl2OR′]2 (R′ = H or alkyl) [6] and the complexes (H2NCOCH2CH2-C,O)(L)SnCl3 (L = amide [7], and L = sulfoxide) [8]. In all the reported amidotin species, the 2-carbonylethyl anion
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is a celating C,O-bidentate ligand with hexa-coordinated tin atoms, with the exception of (H2NCOCH2CH2-C,O)2SnI3 which has a penta-coordinated tin centre [4d]. We now describe three further amidotin compounds, including the seven-coordinate amidotintris-dithiocarbarmate, (H2NCOCH2CH2-C)(R2NCS2-S,S′)3Sn (1), a third (triclinic) polymorph of
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(H2NCOCH2CH2-C,O)2SnCl2 (2) and (H2NCOCH2CH2-C,O)(2-H2NCOC6H4S-O,S)SnCl2 (3), isolated as an unexpected product from a reaction mixture containing 2 and 2-mercaptobenzoic
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acid. Additionally, we report the crystal structure of the complex [(hydroxy)bis(pyridin-2yl)methanolato-N,O,N]SnCl3, 4, isolated from a reaction mixture containing (H2NCOCH2CH2C,O)SnCl3 and bis(pyridin-2-yl)ketone. Compounds 2–4 contain octahedral tin centres. These structures reveal further aspects of the chemistry of amidotin compounds, namely the relative chelating ability and the strong intermolecular hydrogen bonding ability of the amidoethyl ligand, as well as the ease of disproportionation of 2-amidoethyltin species and the unexpected hydrolytic stability of di(amidoethyl)tin dihalides.
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2. Experimental 2.1 General The amidoethyltin chlorides, (H2NCOCH2CH2-C,O)2SnCl2 and (H2NCOCH2CH2-C,O)SnCl3,
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were prepared from HCl and SnCl2 or Sn in diethyl ether solutions, as described in the literature [1a]; all the other materials and solvents are commercially available and were used as received. The NMR spectra were recorded using Bruker spectrometers and the infrared spectra were recorded as CsI disks using a Perkin-Elmer 238 FT-IR spectrometer.
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Sn Mössbauer-effect
199m
SnO3 source kept at room
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spectra were recorded at liquid N2 temperature using a Ba
temperature. Carbon, hydrogen and nitrogen microanalyses were performed on a Perkin-Elmer
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PE-2400 CHN analyser. The syntheses are summarised in scheme 1.
2.2 General synthesis of [(H2NCOCH2CH2-C,O)(S2CNR2)3Sn]
A suspension of MS2CNR2 (M = Na or NH4) (4.0 mmol) in ethanol (15 ml) was slowly added to a solution of (H2NCOCH2CH2-C,O)SnCl3 (1.0 mmol) in ethanol. After stirring at room temperature for 1 h, the reaction mixture was filtered. The obtained precipitate was washed
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successively with water and ethanol and then dried in a desiccator. X-ray quality crystals were obtained by recrystallization of solutions in an ethanol/water mixture (10:1). 2.2.1 [(S2CNEt2-S,S)3(CH2CH2CONH2-C,O)Sn], 1
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Prepared from Na(S2CNEt2). Yield 75%; m.p. 162–4 °C. Anal.: calc. for Sn18H36N4S6OSn: C 34.0, H 5.67, N 8.82%: found: C 33.1, H 4.98, N 8.12%. IR (cm-1): 3330–2700, 1654(s, C=O),
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396 (w. Sn–S), 998 (m, C–S), 1495 (s, C–N + C=N). 1H NMR: (CHCl3): δ: 1.30 (6H, t, J = 7.0 Hz, CH2CH3), 2.45 (2H, t, J = 8.5 Hz, CH2CH2CONH2), 2.85 (2H, t, J = 5 Hz, CH2CH2CONH2), 3.74 – 3.84 (4H, m, J = 7.0 Hz, CH2CH3), 5.62(1H, br), and 5.86(1H, br) (CH2CH2CONH2). 13C NMR (CDCl3): δ: 12.1 (CH2CH3), 33.3 (CH2CH2CONH2), 44.3 (CH2CH2CONH2), 50.1 (CH2CH3); 176 (CH2CH2CONH2), 199 (S2CN).
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Sn Mössbauer-effect
spectrum: δ (mm s–1) = 1.22; ∆ (mm s–1) = 1.87. These values are similar to those reported [9] for the seven coordinate SnIV compound MeSn(NO3)3 [δ (mm s–1) = 0.94, ∆ (mm s–1) = 2.35].
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2.2.2 [(S2CNMe2-S,S)3(CH2CH2CONH2-C,O)Sn], 1a Prepared from Na(S2CNMe2) as yellow blocks. Yield 84%; m.p. 200 οC (decomp.). Anal.: calc. for SnC12H24N4S6OSn: C 26.1, H 4.36, N 10.2%; found: C 26.8, H 3.94, N 9.25%. IR (cm-1): 3340–2720, 1655 (s, C=O), 384 (w, Sn–S), 982 (m, C–S), 1515 (s, C–N + C=N). 1H NMR
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(CDCl3): δ: 3.41 (6H, s, CH3), 2.47 (2H, t, J = 8.5 Hz, CH2CH2CONH2), 2.85 (2H, t, J = 8.5 Hz, CH2CH2CONH2), 5.45 (1H, br) and 5.78 (1H, br), (CH2CH2CONH2). 13C NMR (CDCl3) δ: 12.8 (CH3), 33.4 (CH2CH2CONH2), 45.7 (CH2CH2CONH2), 176 (CH2CH2CONH2), 201 (S2CN). Sn Mössbauer-effect spectrum: δ (mm s–1) = 1.18, ∆ (mm s–1) = 1.87.
2.2.3 [{S2CN(C4H8)-S,S}3(CH2CH2CONH2-C,O)Sn], 1b
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Prepared from NH4(S2CN(CH2)4. Yield 75%; m.p. 180 °C (decomp.). Anal.: calc. for C15H30N4S6OSn: C 28.6, H 4.77, N 8.91%: found C 27.7, H 4.17, N, 8.00%. IR (cm-1): 3330– 2670, 1658(s, C=O), 324 (w, Sn–S); 949 (m, C–S); 1483 (s, C–N + C=N). 1H NMR: (CHCl3): δ: 2.06 (4H, m, NCH2CH2), 2.48 (2H, t, J = 8.5 Hz, CH2CH2CONH2,), 2.86 (2H, t, J = 8.5 Hz, CH2CH2CONH2,), 3.70 (4H, m, NCH2CH2), 5.41(1H, br) and 5.87 (1H, br), (CH2CH2CONH2). C NMR (CDCl3): δ: 26.2 (CH2CH2), 33.4 (CH2CH2CONH2), 50.9 (CH2CH2CONH2), 55.1
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∆ (mm s-1) = 1.86.
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Sn Mössbauer spectrum: δ (mm s-1) = 1.25;
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(NCH2CH2), 178 (CH2CH2CONH2), 196 (S2CN).
2.3. Crystallisation of (H2NCOCH2CH2-C,O)2SnCl2 , 2
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(H2NCOCH2CH2-C,O)2SnCl2 as described above was recrystallized from a solvent mixture of ethanol and water in the form of colourless blocks.
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2.4. Preparation of (H2NCOCH2CH2-C,O)(2-H2NCOC6H4S-O,S)SnCl2, 3 Solutions of (H2NCOCH2CH2-C,O)2SnCl2 (0.30 g, 1 mmol) in ethanol (10 ml) and 2HSC6H4CO2H (0.16 g, 1 mmol) in ethanol were mixed and refluxed for 30 minutes. The reaction mixture was concentrated to 10 ml and left at room temperature. The solid, which slowly formed, was collected after three days, and further recrystallized twice from cold ethanol solution to yield colourless blocks of 3. Final yield, 0.08 g (40%), m.p. 175–178 οC. 1HNMR (DMSO) δ: 7.68(d, 1H), 7.35(br, d, 1H), 7.08(m, 1H), 6.98(m, 1H), [all aryl H atoms] 5.85(br, 1H, NH), 5.62(br, 1H, NH), 2.85(t, J = 7Hz, 2H, CH2), 2.45(t, J = 7Hz), 2H, CH2). Anal.: calc. for C10H12Cl2N2O2SSn: C 29.02, H 2.44, N 6.76%: found: C 29.24, H 2.41, N 6.92%. IR (cm-1) 3300–2700, 1645(s). 4
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2.5 Preparation of [(hydroxy)bis(pyridin-2-yl)methanolato-N,O,N]SnCl3, 4 A solution of (H2NCOCH2CH2-C,O)SnCl3 (0.30g, 1.0 mmol) and bis(pyridin-2-yl)ketone (0.19 g, 1.0 mmol) in ethanol (15 ml) was heated under reflux for 1h and the solvent removed by
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rotary evaporation. TLC of the crude product indicated several mobile phases. The crude product was extracted twice into cold ethanol, rotary evaporated and the residue was recrystallized three times from ethanol solution: the first two recrystallizations yielded poorly crystalline material, while the third produced a small amount of better crystals, one of which was used in the X-ray structure determination. Melting characteristics: above 90 οC, the white solid gradually darkens
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in colour; at 185 οC a black amorphous powder is produced. IR (cm–1) 3000–2300(s,br), 1606(s), 1570(m). Anal.: calc. for C11H9Cl3N2O2Sn: C 30.98, H 2.35, N 6.57%: found: C 31.09, H 2.50, N
2.6 Crystal-structure determinations
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6.41%. There was insufficient amount of sample to obtain NMR data for 4.
The intensity data were collected using a Nonius KappaCCD (1) or Rigaku Mercury CCD diffractometer (2–4) using Mo Kα radiation, λ = 0.71073 Å (T = –173 °C). For 1, a yellow block of dimensions 0.40 × 0.32 × 0.16 mm was chosen for data collection; for 2, colourless
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block, 0.36 × 0.28 × 0.14 mm; for 3, colourless slab, 0.18 × 0.16 × 0.08 mm; for 4, colourless fragment, 0.08 × 0.06 × 0.04 mm. Empirical (multi-scan) absorption corrections were applied at the data-reduction stage.
All the structures were straightforwardly solved by direct methods using SHELXS-97 and the
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atomic models were developed and refined against |F|2 with SHELXL-2014 [10]. The O- and Nbonded H atoms were found in difference maps, relocated to idealised positions (O–H = 0.82, N–
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H = 0.92 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(carrier). The C-bonded H atoms were geometrically placed and modelled as riding atoms with C–H = 0.95–0.98 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density. The structures were analysed and verified with PLATON [11] and the molecular graphics were generated with ORTEP-3 [12]. The crystal used for data collection for 2 was twinned by rotation about [010] and the crystal of 3 was found to be an inversion twin [refined value of the Flack absolute structure parameter [13] = 0.475 (18)]. Crystal data for 1–4 are summarized in Table 1 and full details are available as supplementary material (cif format).
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3. Results and discussion
3.1 [(S2CNR2-S,S)3(CH2CH2CONH2-C)Sn] compounds 1, 1a, 1b
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Compounds 1, 1a and 1b were prepared from reactions between (H2NCOH2CH2-C,O)SnCl3 and the appropriate dithiocarbamate salt. The Mössbauer and IR spectroscopic data (vide supra) for all these compounds are indicative of similar coordination environments about the tin centres. The crystal structure of 1 (vide infra) shows the presence of a seven-coordinate tin(IV) centre in
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the solid state with a monodentate-C 2-amidoethyl anion and three S,S-bidentate dithiocarbmate ligands. While seven-coordinate tin compounds are well known [14], this is the first report of an amidotin compound with a seven-coordinate tin centre and the presence of a monodentate
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amidotin ligand. The two proton NMR signals for the NH2 group are presumably indicative of different hydrogen-bonding environments for the ‘dangling’ amide group rather than a change of coordination mode in solution.
There are parallels with estertin dithiocarbamato complexes: Zoufala et al. [15] reported that tris(N,N-diethyldithiocarbamato-S,S')-3-methoxypropyltin,
[(S2CNMe2-S,S′)3(CH2CH2CO2Me-
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C)Sn] had a seven-coordinate tin atom with a monodentate 2-MeCO2CH2CH2 ligand and three bidenrate dtc ligands, thus confirming proposals from earlier spectroscopic data [16]. By comparison, X-ray crystallographic studies indicated that the hexa-coordinated [(S2CNMe2S,S′)2(MeO2CCH2CH2-C)SnCl] complex had also two chelating dtc ligands and a non-chelating
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2-amidoethyl ligand [17] as did [(S2CNMe2-S,S′)(MeO2CCH2CH2-C)SnS]2 [18]. In contrast, [(S2CNMe2-S,S′)(MeOOCCH2CH2-C,O)SnCl2 ] was shown to possess a chelating 2-amidoethyl
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ligand [16]. Furthermore, [(PDTC)2(CH2CH2CO2R)2Sn] compounds (PDTC = pyrrolidinodithiocarbamato) have been recently shown to possess seven coordinate tin atoms with chelating PDTC groups, one chelating CH2CH2CO2R and one monodentate CH2CH2CO2R ligand [19]. From these reports, it is clear that these (2-carbonylethyl)tin-dtc complexes have a preference for bidentate dtc ligands over bidentate amido ligands. This may be rationalised in terms of the fact that dtc ligands are more powerful chelators than are the RCOCH2CH2 ligands (R = R′O or H2N) towards tin centres. The only ketotin dtc compound, [(Et2NCS2-S,S′](MeCOCMe2CH2C,O)SnCl2] is a six-coordinate complex [4b]. 6
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Other estertin complexes in which the 2-ROCOCH2CH2 ligands only act as monodentate ligands include the six-coordinate (MeO2CCH2CH2-C)Sn((PZ)3BH)X2 (X = Cl–, NCS–, [((PZ)3BH) = tris(pyrazolyl)borate) [20], the seven-coordinate [2-(methoxycarbonyl)ethyl]tris(8-quinolinato)tin, which possesses a [CN3O3Sn] pentagonal bipyramidal environment formed by chelating 8-
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quinolinato-N,O ligands and a monodentate 2-amidoethyl ligand [21], six-coordinate [(methoxy)bis(pyridin-2-yl)methanolato-N,O,N](CH2CH2CO2Me-C)SnCl2) [22] and the four coordinate [(MeO2CCH2CH2-C)2SnS]3 [18]. In the latter trimeric compound, which features an Sn3S3 ring, the presence of the sulfido ligands results in a much reduced Lewis acidity at the tin
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atom. 3.2. Crystal structure of 1
consists of one [(S2CNMe2-S,S/)3(CH2CH2CONH2-
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The molecular structure of 1 (Fig. 1)
C,O)Sn] molecule in space group P21/n in which the three dithiocarboxylate ligands chelate to the tin atom and the seven-coordination of the metal is completed by a monodentate-C-bonded 2amidoethyl anion. For the C4 ligand, the Sn1–S1 [2.4916 (4) Å] and Sn1–S2 [2.7720 (2) Å] bond lengths are significantly different [∆ = 0.2804 (3) Å]. The ligand C4–S1 and C4–S2 bond lengths of 1.7445 (15) and 1.7043 (15) Å, respectively, are characteristic of C–S single bonds whereas
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the C4–N2 separation of 1.3324 (19) Å clearly indicates a C=N double bond, indicating that the R2N+=C–(S–,S–) resonance form for the ligand makes a major contribution to the structure [23]. The C9 ligand shows a somewhat less asymmetric coordination [Sn1–S3 = 2.6463 (4), Sn1–S4 =
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2.7808 (4), ∆ = 0.1345 (6) Å] and again, the C–S bonds are similar [C9–S3 = 1.7355 (16), C9– S4 = 1.7111 (17) Å] and the C9–N3 bond length of 1.334 (2) Å is normal for a double bond. The C14 ligand shows the smallest difference between the Sn–S bonds [Sn1–S5 = 2.6974 (4), Sn1–
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S6 = 2.6455 (4), ∆ = 0.0519 (6) Å]. The C14–S5, C14–S6 and C14–N4 bond lengths are 1.7152 (17), 1.7357 (16) and 1.331 (2) Å, respectively. For each ligand, the C2N=CS2 grouping is almost planar (r.m.s. deviations = 0.017, 0.028 and 0.033 Å for the C4, C9 and C14 ligands, respectively) and one of the terminal –CH3 groups points ‘up’ with respect to this plane and the other points ‘down’, perhaps for steric reasons. The tin atom deviates from the ligand planes just mentioned by 0.3157 (12), 0.0667 (12) and –0.1889 (12) Å for the C4, C9 and C14 ligands, respectively. The Sn1–C1 bond length of 2.1647 (15) Å for the 2-amidoethyl anion in 1 is a little longer than the distances reported for six coordinated 7
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(chelating) bis-(amido)2tin compounds, e.g., in (H2NCOCH2CH2-C,O)2SnX2, the Sn–C bond lengths lie between 2.127 (3) and 2.146 (3) Å [5] The untethered ligand in 1 adopts an extended conformation [C1–C2–C3–O1 = –168.73 (15)ο]. The tin coordination polyhedron for 1 (Fig. 2) is well described as a pentagonal bipyramid with
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C1 and S1 occupying the axial sites [C1–Sn1–S1 = 165.99 (4)ο] and the other sulphur atoms defining the equatorial sites. The chelate bite-angles [S3–Sn1–S4 = 65.689 (12) and S5–Sn1–S6 = 66.773 (12)ο] are somewhat smaller than the other equatorial S–Sn–S angles. The bite angle
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for S1–Sn1–S2 of 68.306 (12)ο, is slightly larger than the others, which possibly correlates with its coordination role in the pentagonal bipyramid, although it must be noted that the difference is
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small.
In the crystal of 1, the molecules are linked by N–HLO and N–HLS hydrogen bonds (Table 2). By themselves, each lead to inversion dimers with
(8) and
(14) graph-set descriptors [24],
respectively and together they generate [010] chains (supplementary Fig. S1). The chains are consolidated and cross-linked by various C–HLO links.
3.3. Triclinic polymorph of (H2NCOCH2CH2-C,O)2SnCl2, 2
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Previously, the monoclinic C2/c and P21/c polymorphs of (H2NCOCH2CH2-C,O)2SnCl2 have been reported [5]. The former phase was obtained by recrystallization of 2 from an ethanol solution, and the latter was fortuitously isolated from a reaction mixture containing 2 and sodium
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chlorodifluoroacetate dissolved in acetone. The third, triclinic, polymorph, which we now report, was obtained by recrystallization of 2 from an aqueous–ethanol solution (1:1 v:v). The recovery of (H2NCOCH2CH2-C,O)2SnCl2 from this solvent mixture points to its significant hydrolytic
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stability, in contrast to those of simple di-organotin dihalides, which react to give organotin oxyhalides and organotin oxides. 3.4. Crystal structure of 2
The new triclinic polymorph of 2 (Fig. 3), crystallises with two molecules (A containing Sn1 and B containing Sn2) in the asymmetric unit. Octahedral SnC2O2Cl2 donor sets arise in which the C atoms are mutually trans [C–Sn–C = 164.2 (2)ο in both A and B] and the O atoms are trans to chloride ions [O–Sn–Cl = 169.13 (10) and 169.72 (11)ο in A; 170.33 (11) and 170.59 (11)ο in B); the pairs of O and Cl atoms are mutually cis. The distinction between the Sn–C, Sn–O and Sn–Cl 8
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bond lengths is very clear (Table 3). The chelate bite angles cover the narrow range from 77.28 (18) to 78.29 (18)ο. The tin octahedra could be described as moderately distorted [ranges of cis angles for A and B = 77.63 (17)–97.05 (5)ο and 77.28 (18)–96.85 (5)ο, respectively]: in each
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case, the largest angle is for the Cl–Sn–Cl grouping. The molecules differ in terms of the conformations of their chelate rings: for A, the C1 ligand is well described as an envelope with C1 itself as the flap, deviating by –0.390 (8) Å from the other atoms (r.m.s. deviation = 0.018 Å), as is the C4 ligand, in which C4 deviates from the other atoms (r.m.s. deviation = 0.016 Å) by –0.481 (7) Å. For B, both chelate rings are puckered about
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their Sn–C bonds: Sn2 and C7 deviate by 0.22 (2) and –0.367 (18) Å, respectively, from C8/C9/O3; for Sn2 and C10, the respective deviations with respect to C11/C12/O4 are 0.36 (2)
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and –0.191 (18) Å.
As might be expected, the extended structure of 2 features numerous hydrogen bonds arising from the NH2 groups. Taken by itself, the Sn1 molecule forms inversion dimers via a pair of N– HLO links and N–HLCl links connect the dimers into sheets. The Sn2 molecule does not form N–HLO links, but N–HLCl bonds generate [110] chains (supplementary Fig. S2).
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Collectively, a three-dimensional network arises. Two weak C–HLO bonds are also observed. The same hydrogen bonds are observed in the C2/c polymorph, which is also three-dimensional in terms of its directional intermolecular interactions, whereas the P21/c polymorph is layered [5].
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3.5. (H2NCOCH2CH2-C,O)SnCl2(OCNH2C6H4S-2-O,S), 3 Compound 3 was an unexpected product isolated from the reaction between (H2NCOCH2CH2-
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C,O)2SnCl2 and 2-HSC6H4CO2H in ethanol solution: it indicates that considerable changes in both reagents have occurred, including a ligand disproportionation of (H2NCOCH2CH2C,O)2SnCl2 (see equation 1 below), and that the benzoic acid group has been transformed to an amide (see equation 2 below). Ligand disproportionation reactions of organotin halides are wellknown and in the presence of chelating ligands can occur particularly readily [25]: the trichloride is a much stronger Lewis acid than the monochloride and will preferentially react with ligands. 2 (H2NCOCH2CH2-C,O)2SnCl2 → (H2NCOCH2CH2-C,O)SnCl3 + (H2NCOCH2CH2-C,O)3SnCl
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(1)
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The formation of 2-HSC6H4CONH2 is considered to arise from a “trans-esterification” reaction (equation 2). Similar reactions have been reported for a number of organotin carboxylate esters, including amidoethyltin compounds [19, 26].
(HOCOCH2CH2-C,O)nSnCl3–n + 2-HSC6H4CONH2 (2)
3.6 Crystal structure of 3
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(H2NCOCH2CH2-C,O)nSnCl3–n + 2-HSC6H4CO2H →
The asymmetric unit of 3 (Fig. 4) consists of two molecules (A containing Sn1 and B containing
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Sn2), each with a chelating 2-amidoethyl anion, an O,S-chelating thiol ligand and two chloride ions (Table 4). The disposition of the ligands about the octahedral tin atoms lead to one transS,C pairing [C–Sn–S = 163.43 (11)ο for A and 163.33 (11)ο for B] and two trans-O,Cl pairings
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[172.07 (9) and 177.08 (7)ο for A; 169.02 (9) and 177.80 (7)ο for B]: the pairs of O atoms and Cl atoms are mutually cis. The 2-amidoethyl bite angles [77.88 (13)ο for A and 79.05 (13)ο for B] are similar to those in 2. The bite angles for the O,S ligand are 86.84 (8)° and 86.04 (9)ο, for A and B respectively. Octahedral distortions may be quantified in terms of angular variances [27] of 37.3°2 for Sn1 and 40.7°2 for Sn2.
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The molecular conformations of the two molecules are slightly different. For A, the C1 (amide) chelate ring is an envelope with C1 deviating by –0.525 (7) Å from the other four atoms (r.m.s. deviation = 0.005 Å) whereas the C10 (thiol) ring is a distorted boat, with the dihedral angle between the C4/C5/C10/S1 (r.m.s. deviation = 0.0006 Å) and the Sn1/S1/O2 groupings being
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49.80 (16)°. Molecule B features a twisted conformation for the C13 (amide) ring, with atoms C11 and C12 deviating by 0.16 (1) and –0.22 (1) Å, respectively, from the plane of C13/O5/Sn2.
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The thiol (C20) ring is a distorted boat: the dihedral angle between C14/C15/C20/S2 (r.m.s. deviation = 0.006 Å) and Sn2/S2/O6 being 51.29 (17)°. In the crystal of 3, N–HLCl hydrogen bonds dominate the packing and an N–HLO and possible C–HLS link are also observed: together, these intermolecular bonds generate a three-dimensional network in the crystal. 3.7 [(HO)bis(pyridin-2-yl)methanolato-N,O,N]SnCl3 or Sn(C11H9N2O2)Cl3, 4 Various complexes have been prepared from reactions of bis(pyridin-2-yl)ketone with metal halides [22, 28], including reactions with tin and organotin halides. Reactions between bis(pyridin-2-yl)ketone and SnX4 (X = Cl or Br) and RSnCl3 in R′OH were shown to produce 10
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[(RO)bis(pyridin-2-yl)methanolato-N,O,N]SnX3)
and
[(RO)bis(pyridin-2-yl)methanolato-
N,O,N]RSnX2, respectively, including for [(CH2CH2CO2Me-C,O)SnCl3] [22]. The attempt to produce the analogous product with [Sn(CH2CH2CONH2C,O)SnCl3] failed, with 4 being the only reaction of the amidotin starting material has occurred. 3.8. Crystal structure of 4
RI PT
product identified. The formation of this product suggests that another ligand disproportionation
The molecular structure of 4 is a neutral molecular complex (Fig. 5) consisting of an N,N,O-
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tridentate ligand deprotonated at O1, i.e.: C11H9N2O2–, and three chloride ions bound to the tin atom to generate an octahedral SnN2OCl3 donor set (Table 5) with the chloride ions defining one triangular face of the octahedron.
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The dihedral angle between the pyridine rings is 69.4 (3)ο. The Sn atom deviates from the N1 ring by –0.270 (15) Å; conversely it is exactly co-planar with the N2 ring [deviation = 0.000 (16) Å. The bridging C5–C6–C7 bond angle is 109.0 (8)ο and the tin atom deviates from the O1/C6/O2 plane by 0.15 (2) Å. The cis octahedral bond angles vary from 74.6 (3) to 97.97 (9)°, with the smaller values corresponding to chelate bite angles [O1–Sn1–N2 = 75.5 (3)°, O1–Sn1–
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N2 = 74.6 (3)°, N1–Sn1–N2 = 81.7 (3)°]. Both chelate rings (Sn1/N1/C5/C6/O1 and Sn1/N2/C7/C6/O1) can be described as envelopes, with O1 being the flap in each case [deviations = –0.814 (10) and 0.784 (11) Å, respectively]. In the extended structure of 4, dimers related by a crystallographic twofold axis and linked by
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pairs of O–HLO hydrogen bonds (supplementary Fig. S3) occur, generating
(8) loops.
Several weak C–HLCl links are also present.
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4 Conclusions
Four new tin complexes have been prepared and spectroscopically and structurally characterised. Compound 1, (H2NCOCH2CH2-C)(Et2NCS2-S,S′)3Sn, features the uncommon situation of a nonchelating amidoethyl ligand as part of a pentagonal bipyramidal SnS6C coordination polyhedron. Compound 2, (H2NCOCH2CH2-C,O)2SnCl2, is a triclinic polymorph crystallised from mixed solvents (water and ethanol) of two previously described monoclinic forms: its formation is surprising given the tendency for diamidoethyltin dihalides to hydrolyse. Compound 3, (H2NCOCH2CH2-C,O)(2-H2NCOC6H4S-O,S)SnCl2, was isolated as an unexpected product from 11
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a reaction that featured both ligand disproportionation and trans-esterification of the starting materials. Compound 4, Sn(C11H9N2O2)Cl3, is a classical complex, which must also arise from a
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facile ligand disproportionation of the starting di(amidoethyl)tin compound.
Acknowledgements
We thank the EPSRC National Crystallography Service (University of Southampton) for the intensity data collection
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References
(a) R.E. Hutton, V. Oakes, Adv. Chem. Ser. 157 (1976) 123; (b) D. Lanigen, E.L. Weinberg, Adv. Chem. Ser. 157 (1976) 134; (c) J.W. Burley, O. Hope, R.E. Hutton, J. Groenenboom, J. Organomet. Chem. 170 (1979) 21; (d) J.W. Burley, R.D. Dworkin, J. Vinyl Tech. 8 (1986) 15.
[2]
(a) R.A. Howie, E.S. Paterson, J.L. Wardell, J.W. Burley, J. W. (1986). J. Organomet. Chem. 304 (1986) 301; (b) R. Balasubramanian, Z.H. Chohan, S.M.S.V. Doidge-Harrison, R.A. Howie, J.L. Wardell, Polyhedron 16 (1997) 4283; (c) L.J. Tian, Z. Zhou, Q. Yu, X. Liu, X. (2003). Synth. React. Inorg. Met.-Org. Chem. 33 (2003) 259; (d) L.J. Tian, Q. Yu, Z. Shang, Y. Sun, L. Zhang, L. (2005). Appl. Organomet. Chem. 19 (2005) 677; (e) L.J. Tian, Y.X. Sun, X.J. Liu, G.M. Yang, Z.C. Shang, Z. C. (2005). Polyhedron 24 (2005) 2027.
[3]
(a) B.F. Milne, R.P. Pereira, A.M. Rocco, J.M.S. Skakle, A.J. Travis, J.L. Wardell, J. L. & Wardell, S. M. S. V. Appl. Organomet. Chem, 19 (2005) 363; (b) R.A. Howie, J.L. Wardell, Acta Cryst. C57 (2001) 1041; (c) E.R.T. Tiekink, J.L. Wardell, W.B. Welte, Acta Cryst. E62 (2006) m1763 (a) P.G. Harrison, T.J. King, M.A. Healy, J. Organomet. Chem. 182 (1979) 17; (b) E.R.T. Tiekink, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2006). Acta Cryst. E62 (2006) m971; (c) S.M.S.V. Wardell, W.T.A. Harrison, E.R.T. Tiekink, G.M. de Lima, J.L. Wardell, J. L. (2010). Acta Cryst. E66 (2010) m312; (d) G.M. de Lima, E.R.T. Tiekink, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2011). Acta Cryst. E67 (2011) m1536. R.A. Howie, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, N.M. Comerlato, N. M. (2011). Z. Krist. 226 (2011) 535–552. R.A. Howie, W.T.A. Harrison, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2011). Z. Krist. 226 (2011) 739.
[5] [6]
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[4]
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[1]
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[20] [21] [22] [23] [24] [25]
[26] [27] [28]
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M AN U
[15] [16] [17] [18] [19]
TE D
[9] [10] [11] [12] [13] [14]
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[8]
R.A. Howie, G.M. de Lima, E.R.T. Tiekink, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2011). Z. Krist. 226 (2011) 837. R.A. Howie, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, W. T. A. Harrison, J. Organomet. Chem. 716 (2012) 62. D. Potts, H.D. Sharma, A.J. Carty, A. Walker, Inorg. Chem. 13 (1974) 1205. G.M. Sheldrick, Acta Cryst. C71 (2015) 3. A.L. Spek, Acta Cryst. D65 (2009) 148. L.J. Farrugia, J. Appl. Cryst. 45 (2012) 849. H.D. Flack, Acta Cryst. A39 (1983) 876–881. (a) J.S. Morris, E.O. Schlemper, J. Cryst. Mol. Struct. 8 (1978) 295; (b) J.S. Morris, E.O. Schlemper, J. Cryst. Mol. Struct. 9 (1979) 1. P. Zoufala, I. Cisarova, A. Ruzicka, Main Group Met. Chem. 26 (2003) 53. O.S. Jung, J.-H. Jeong, Y.S. Sohn, Polyhedron 8 (1989) 1413. O.S. Jung, J.-H. Jeong, Y.S. Sohn, Acta Cryst. C46 1990) 31. O.S. Jung, J.-H. Jeong, Y.S. Sohn, Polyhedron, 8 (1989) 2557–2563. B.P.de Morais, C.L. Donnici, B.L. Rodrigues, G.M. de Lima, J.L. Wardell, R.S. Bitzer, J. Organomet. Chem. 832 (2017) 57. O.S. Jung, J.-H. Jeong, Y.S. Sohn, J. Organomet. Chem. 399 (1990) 235. L.J. Tian, S. Zhang, Y.Z. Yao, X.W. Shi, Main Group Met. Chem. 39(2016) 209. R.A. Howie, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, Polyhedron 29 (2010) 739. E.R.T. Tiekink, Appl. Organomet. Chem. 22 (2008) 533. J. Bernstein, R.E. Davis, L. Shimoni, N. Chang, Angew. Chem. Int. Ed. 34 (1995) 1555. (a) S.J. Blunden, P. Harston, R. Hill, R. J.L. Wardell, J. L. (1990). Appl. Organomet. Chem. 4, 383; (b) C. Pettinari, F. Marchetti, R. Pettinari, A. Cingolani, A. Drozdov, S. Troyanov, J. Chem. Soc. Dalton Trans. (2002) 1884; (c) D.V. Airapetyan, V.S.., Petrosyan, S.V. Gruener, K.V., Zaitsev, D.E. Arkhipov, A.A. Korlyukov, J. Organomet. Chem. 747 (2013) 241. Y. Xu, W. An, W. Ding, H. Liu, L. Tian, Commun. Inorg. Synth. 1 (2013) 60. K. Robinson, G.V. Gibbs, P.H. Ribbe, Science (Washington, DC) 172 (1971), 567. T.C. Stamatatos, C.G. Efthymiou, C.C. Stoumpos, S.P. Perlepes, Eur. J. Inorg. Chem. (2009) 3361.
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[7]
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Figure captions
Figure 1: the molecular structure of 1 showing 50% displacement ellipsoids. The H atoms of the
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dithiocarbamate ligands are omitted for clarity. Figure 2: detail of 1 showing the distorted pentagonal bipyramidal coordination of the tin atom. Figure 3: the molecular structure of the Sn1 molecule in 2 showing 50% displacement ellipsoids.
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Figure 4: the molecular structure of the Sn1 molecule in 3 showing 50% displacement ellipsoids.
Supplementary Figure captions
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Figure 5: the molecular structure of 4 showing 50% displacement ellipsoids.
Figure S1: fragment of a hydrogen-bonded chain in the crystal of 1: symmetry codes as in Table
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2.
Figure S2: fragment of a hydrogen-bonded chain in the crystal of 2: symmetry codes as in Table 3.
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Figure S3: a dimer with twofold symmetry in the crystal structure of 4 linked by a pair of O–
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HO hydrogen bonds. Symmetry code as in Table 5.
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Table 1: Key crystallographic data for 1–4
C18H36N4OS6Sn
C6H12Cl2N2O2Sn
C10H12Cl2N2O2SSn
C11H9Cl3N2O2Sn
Mr
635.56
333.77
413.87
426.24
Crystal system
Monoclinic
Triclinic
Orthorhombic
Orthorhombic
Space group
P21/n (No. 14)
1 (No. 2)
Pca21 (No. 29)
Pcca (No. 54)
a (Å)
14.40360 (10)
8.0191 (6)
10.8998 (2)
14.9717 (10)
b (Å)
12.4098 (2)
10.7786 (8)
7.7467 (2)
11.8709 (8)
c (Å)
17.1388 (2)
13.2081 (9)
33.411 (2)
15.6014 (11)
α (°)
90
89.365 (7)
90
90
β (°)
113.7167 (7)
77.118 (6)
90
90
90
88.339 (7)
90
90
V (Å )
2804.76 (6)
1112.42 (14)
2821.14 (19)
2772.8 (3)
Z
4
4
8
8
1304
648
1616
1648
ρcalc (g cm )
1.505
1.993
1.949
2.048
µ (mm–1)
1.375
2.750
2.332
2.418
Data collected
29904
5007
28981
25446
Unique data
6414
5007*
6439
3213
RInt
0.033
–
0.022
0.079
0.046
0.017
0.083
0.112
0.036
0.152
1547170
1547171
1547172
F(000) –3
R(F) [I > 2?(I)]
0.020
2
wR(F ) (all data) 0.048 CCDC code
%
1547169
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3
TE D
γ (°)
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Emp. formula
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1 2 3 4 _____________________________________________________________________________________________
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_________________________________
*Refined as a non-merohedral twin and data not merged %
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Full crystallographic data for these structures including atom positions and geometrical parameters can be accessed at: http://www.ccdc.cam.ac.uk/Community/Requestastructure/Pages/DataRequest.aspx by citing the code number shown.
15
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Table 2: selected geometrical data (Å,°) for 1 2.1647 (15)
Sn1–S1
2.4916 (4)
Sn1–S6
2.6455 (4)
Sn1–S3
2.6463 (4)
Sn1–S5
2.6974 (4)
Sn1–S2
2.7720 (4)
Sn1–S4
2.7808 (4)
C1–Sn1–S1
165.99 (4)
C1–Sn1–S6
98.02 (4)
S1–Sn1–S6
95.453 (13)
C1–Sn1–S3
97.83 (4)
S1–Sn1–S3
88.828 (13)
S6–Sn1–S3
77.415 (12)
C1–Sn1–S5
91.67 (4)
S1–Sn1–S5
S6–Sn1–S5
66.773 (12)
S3–Sn1–S5
C1–Sn1–S2
98.75 (4)
S1–Sn1–S2
S6–Sn1–S2
138.605 (13)
S3–Sn1–S2
136.535 (12)
S5–Sn1–S2
75.162 (12)
C1–Sn1–S4
86.09 (4)
S1–Sn1–S4
85.450 (13)
S6–Sn1–S4
143.079 (13)
S3–Sn1–S4
65.689 (12)
S5–Sn1–S4
150.086 (13)
S2–Sn1–S4
75.719 (12)
C5–H5aLS2
iii iv
C12–H12bLO1 C13–H13aLO1 C16–H16aLS2
v
vi
90.112 (13)
143.899 (12)
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68.306 (12)
0.88
2.12
2.9969 (17)
173
0.88
2.75
3.5897 (14)
160
0.99
2.91
3.7852 (17)
148
0.99
2.52
3.462 (2)
159
0.98
2.53
3.492 (2)
167
0.98
2.90
3.5702 (18)
126
TE D
N1–H1dLS3
ii
EP
N1–H1cLO1i
RI PT
Sn1–C1
SC
_________________________________________
____________________________________________________________________________
AC C
Symmetry codes: (i) 1–x, 2–y, –z; (ii) 1–x, 1–y, –z; (iii) ½–x, y–½, ½–z; (iv) 3/2–x, y–½, ½–z; (v) ½+x, 3/2–y, ½+z; (vi) x–½, 3/2–y, z–½.
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Table 3: selected geometrical data (Å,°) for 2 _________________________________________ 2.129 (5)
Sn1–C1
2.129 (5)
Sn1–O1
2.275 (4)
Sn1–O2
2.310 (4)
Sn1–Cl1
2.4972 (13)
Sn1–Cl2
2.5019 (13)
Sn2–C10
2.116 (6)
Sn2–C7
Sn2–O4
2.299 (4)
Sn2–O3
Sn2–Cl3
2.4939 (13)
Sn2–Cl4
N1–H1cLCl2i
RI PT
Sn1–C4
2.120 (5)
2.310 (4)
2.5200 (13)
2.60
3.461 (5)
N1–H1dLCl2
0.88
2.63
3.421 (5)
149
iii
0.88
2.05
2.865 (6)
153
N2–H2dLCl1
0.88
2.60
3.344 (6)
143
N2–H2dLCl4
0.88
2.79
3.422 (7)
130
C5–H5bLCl3
0.99
2.90
3.631 (5)
132
2.53
3.396 (5)
166
2.92
3.594 (5)
135
2.80
3.484 (5)
136
2.45
3.297 (5)
161
2.96
3.874 (6)
154
iv
0.88
iii
0.88
ii
0.88
vi
N4–H4dLCl3
0.88
C11–H11aLCl2vii
0.99
N3–H3aLCl4
N3–H3bLCl1
N3–H3bLCl4
TE D
v
M AN U
N2–H2LO2
167
SC
0.88
ii
___________________________________________________________________________ Symmetry codes: (i) 1–x, 1–y, 1–z; (ii) x–1, y, z; (iii) 1–x, –y, 1–z; (iv) 2–x, –y, 1–z; (v) 1–x, –y,
AC C
EP
–z; (vi) 2–x, 1–y, –z; (vii) x, y, z–1.
17
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Table 4: selected geometrical data (Å,°) for 3 _________________________________________ 2.132 (4)
Sn1–O2
2.179 (3)
Sn1–O1
2.308 (3)
Sn1–S1
2.4141 (10)
Sn1–Cl2
2.4436 (10)
Sn1–Cl1
2.5541 (10)
Sn2–C11
2.137 (4)
Sn2–O6
Sn2–O5
2.303 (3)
Sn2–S2
Sn2–Cl5
2.4385 (10)
Sn2–Cl4
RI PT
Sn1–C1
2.199 (3)
2.4152 (11)
2.5328 (10)
N1–H1cLCl4i
0.88
2.49
3.335 (4)
ii
0.88
2.40
3.262 (4)
168
iii
0.99
2.90
3.651 (6)
134
iv
0.95
2.73
3.675 (4)
173
SC
C6–H6LCl2
M AN U
C2–H2bLS1
v
0.95 (5)
2.55 (5)
3.397 (4)
147 (4)
vi
0.79 (5)
2.57 (5)
3.343 (4)
166 (4)
vii
0.88
2.40
3.261 (4)
164
viii
0.88
2.44
3.274 (4)
159
ix
0.91 (5)
2.67 (5)
3.466 (4)
147 (4)
x
0.92 (5)
2.42 (5)
3.308 (4)
163 (4)
0.95
2.68
3.619 (4)
171
N2–H1nLCl2
N2–H2nLCl1 N3–H3cLCl1
N3–H3dLCl1 N4–H7nLCl5
N4–H8nLCl4
C16–H16LCl5iii
TE D
N1–H1dLO5
162
___________________________________________________________________________ Symmetry codes: (i) ½–x, y, z–½ ; (ii) 1–x, –y, z–½; (iii) ½+x, –y, z; (iv) x–½, 1–y, z;
(v) x–½ ,
AC C
EP
–y, z; (vi) x, y–1, z; (vii) 1–x, 1–y, ½+z; (viii) ½–x, y, ½+z; (ix) ½+x, 1–y, z; (x) x, 1+y, z.
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Table 5: selected geometrical data (Å,°) for 4 _________________________________________ 2.045 (6)
Sn1–N2
2.224 (8)
Sn1–N1
2.250 (8)
Sn1–Cl1
2.361 (3)
Sn1–Cl2
2.370 (3)
Sn1–Cl3
2.372 (3)
0.82
1.94
2.690 (9)
C1–H1LCl3
ii
0.93
2.94
3.539 (11)
C4–H4LCl2
iii
0.93
2.98
3.552 (10)
C4–H4LCl3
i
0.93
2.92
3.759 (11)
C8–H8LCl1
iii
0.93
2.86
3.534 (10)
153
124
121
151
SC
O2–H2aLO1i
RI PT
Sn1–O1
130
____________________________________________________________________________
AC C
EP
TE D
M AN U
Symmetry codes: (i) –x, –y, ½–z; (ii) –x, –y, –z; (iii) ½–x, y, ½+z.
19
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C18 C10
C11 S6
C6
S1
SC
C9
C12
TE D S2
S5 C1 C2
AC C
C7
C16
C4
EP
N2
N1
C8
C3 O1
N4 C15
Sn1
S4
C5
C14
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N3
C13
C17
RI PT
S3
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S6
SC
RI PT
C1
Sn1
AC C
EP
TE D
S5
S2
S1
S3 S4
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RI PT
N2
C6
SC
O2
M AN U
N1 C3
EP
TE D
O1
AC C
C2
C5
C4
Sn1
C1 Cl1
Cl2
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N2 O2
N1
C1
SC
C10
RI PT
C2
M AN U
C9
O1
Cl2
C4
Sn1
TE D
C8
C3
C7
AC C
EP
C5
C6
S1
Cl1
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C8
O2 C4
RI PT
C3
C6
C2
M AN U
SC
C5
C9
C7 C10
O1
EP
C11 Sn1
AC C
C1
TE D
N1
N2
Cl1
Cl3 Cl2
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O
N
NH 2
RI PT
S
S
S
Sn
S
N
S
S
1
M AN U
SC
N
Et2N=CS2 -
O
SnCl2 HCl, EtOEt
NH 2
Cl Cl
Sn
TE D
Cl
NH 2
O
HCl
pyCOpy, moist EtOH
Sn, EtOEt
Cl O
N HO
O
Cl Sn
N
O Sn Cl
AC C
2
EP
NH 2
Cl
2-HS-C6H4CO2H
4
H 2N
S Cl Sn
3
Cl
O Cl O H 2N
NH 2
ACCEPTED MANUSCRIPT Highlights New types of amidotehyl tin complexes are presented
•
Ligand disproportionation and trans-esterification reactions occur
•
New insights into polymorphism and hydrolytic stability are offered
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•
S0022-328X(17)30500-4
DOI:
10.1016/j.jorganchem.2017.08.011
Reference:
JOM 20064
To appear in:
Journal of Organometallic Chemistry
Received Date: 31 May 2017 Revised Date:
18 August 2017
Accepted Date: 19 August 2017
Please cite this article as: D.C. Menezes, G.M. de Lima, J.L. Wardell, J. Gomez-Banderas, W.T.A. Harrison, Structural variety of 2-amidoethyltin compounds, Journal of Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2017.08.011. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Structural variety of 2-amidoethyltin compounds
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Daniele C. Menezes a*, Geraldo M. de Limab, James L. Wardellc,d, Jessica Gomez-Banderasc and William T. A. Harrisonc
Departamento de Química, Universidade Federal de Viçosa, 36570-000 Viçosa-MG, Brasil.
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a b
Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais,
c
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31270–901, Belo Horizonte–MG, Brasil.
Departament of Chemistry, University of Aberdeen, AB24 2UE, Aberdeen, Scotland d
Instituto de Tecnologia em Fármacos, Fundação Oswaldo Cruz, 21041-250,
Abstract
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Rio de Janeiro, RJ, Brasil.
The syntheses, spectroscopic data and crystal structures of (H2NCOCH2CH2-C)(R2NCS2-S,S/)3Sn (H2NCOCH2CH2-C,O)2SnCl2
(triclinic
polymorph)
(2),
(H2NCOCH2CH2-C,O)(2-
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(1),
H2NCOC6H4S-O,S)SnCl2 (3) and Sn(C11H9N2O2)Cl3 (4) are reported. The tin atom in compound 1 (R = Et) is coordinated by three chelating dithiocarbamate anions and a C-bound non-chelating
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amidoethyl ligand to generate a SnS6C pentagonal-bipyramidal coordination polyhedron. Compound 2, which features SnC2O2Cl2 octahedra, was crystallised from mixed solvents (ethanol and water) and complements the two known monoclinic forms. Compound 3 arose unexpectedly due to ligand disproportionation of the tin starting material and a “transesterification” reaction of the starting ligand: distorted SnCSO2Cl2 octahedra are seen in the crystal structure. Compound 4 arose from another ligand disproportionation reaction and features neutral complex molecules with N2OCl3 donor sets coordinating to the octahedral tin atoms.
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1. Introduction Functionally-substituted alkyltin halides, YCOCH2CR″2SnX3 and (YCOCH2CR″2)2SnX2 (e.g.: X = halide, Y = R′, OR′ or NR′2, R′ = alkyl or aryl, R″ = H or Me) were prepared in the 1970s as
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possible precursors of organotin mercaptides for use as PVC stabilisers [1]. While this use has not been realised, the coordination chemistry of 2-carbonylethyl-tin compounds has been extensively studied ever since [2]. The large volume of work reported for the so called “estertin” compounds, R′O2CCH2CH2SnX3 and (R′O2CCH2CH2)2SnX2, (where the ester C=O group closes
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the five-membered –Sn–C–C–C=O– chelate ring) contrasts with the few structural studies carried out on “ketotin” compounds, R′COCH2CR″2SnX3 and (R′COCH2CR″2)2SnX2 [3] and the “amidotin” species H2NCOCH2CH2SnX3 and (H2NCOCH2CH2)2SnX2 [4].
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Only within the last few years have amidotin compounds attracted systematic attention, which has led to reports of the syntheses and crystal structures of families of (H2NCOCH2CH2C,O)2SnX2 derivatives (X = halide, azide, chelating 1,2-dithiolato, etc.) [5], [(H2NCOCH2CH2C,O)SnCl2OR′]2 (R′ = H or alkyl) [6] and the complexes (H2NCOCH2CH2-C,O)(L)SnCl3 (L = amide [7], and L = sulfoxide) [8]. In all the reported amidotin species, the 2-carbonylethyl anion
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is a celating C,O-bidentate ligand with hexa-coordinated tin atoms, with the exception of (H2NCOCH2CH2-C,O)2SnI3 which has a penta-coordinated tin centre [4d]. We now describe three further amidotin compounds, including the seven-coordinate amidotintris-dithiocarbarmate, (H2NCOCH2CH2-C)(R2NCS2-S,S′)3Sn (1), a third (triclinic) polymorph of
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(H2NCOCH2CH2-C,O)2SnCl2 (2) and (H2NCOCH2CH2-C,O)(2-H2NCOC6H4S-O,S)SnCl2 (3), isolated as an unexpected product from a reaction mixture containing 2 and 2-mercaptobenzoic
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acid. Additionally, we report the crystal structure of the complex [(hydroxy)bis(pyridin-2yl)methanolato-N,O,N]SnCl3, 4, isolated from a reaction mixture containing (H2NCOCH2CH2C,O)SnCl3 and bis(pyridin-2-yl)ketone. Compounds 2–4 contain octahedral tin centres. These structures reveal further aspects of the chemistry of amidotin compounds, namely the relative chelating ability and the strong intermolecular hydrogen bonding ability of the amidoethyl ligand, as well as the ease of disproportionation of 2-amidoethyltin species and the unexpected hydrolytic stability of di(amidoethyl)tin dihalides.
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2. Experimental 2.1 General The amidoethyltin chlorides, (H2NCOCH2CH2-C,O)2SnCl2 and (H2NCOCH2CH2-C,O)SnCl3,
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were prepared from HCl and SnCl2 or Sn in diethyl ether solutions, as described in the literature [1a]; all the other materials and solvents are commercially available and were used as received. The NMR spectra were recorded using Bruker spectrometers and the infrared spectra were recorded as CsI disks using a Perkin-Elmer 238 FT-IR spectrometer.
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Sn Mössbauer-effect
199m
SnO3 source kept at room
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spectra were recorded at liquid N2 temperature using a Ba
temperature. Carbon, hydrogen and nitrogen microanalyses were performed on a Perkin-Elmer
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PE-2400 CHN analyser. The syntheses are summarised in scheme 1.
2.2 General synthesis of [(H2NCOCH2CH2-C,O)(S2CNR2)3Sn]
A suspension of MS2CNR2 (M = Na or NH4) (4.0 mmol) in ethanol (15 ml) was slowly added to a solution of (H2NCOCH2CH2-C,O)SnCl3 (1.0 mmol) in ethanol. After stirring at room temperature for 1 h, the reaction mixture was filtered. The obtained precipitate was washed
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successively with water and ethanol and then dried in a desiccator. X-ray quality crystals were obtained by recrystallization of solutions in an ethanol/water mixture (10:1). 2.2.1 [(S2CNEt2-S,S)3(CH2CH2CONH2-C,O)Sn], 1
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Prepared from Na(S2CNEt2). Yield 75%; m.p. 162–4 °C. Anal.: calc. for Sn18H36N4S6OSn: C 34.0, H 5.67, N 8.82%: found: C 33.1, H 4.98, N 8.12%. IR (cm-1): 3330–2700, 1654(s, C=O),
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396 (w. Sn–S), 998 (m, C–S), 1495 (s, C–N + C=N). 1H NMR: (CHCl3): δ: 1.30 (6H, t, J = 7.0 Hz, CH2CH3), 2.45 (2H, t, J = 8.5 Hz, CH2CH2CONH2), 2.85 (2H, t, J = 5 Hz, CH2CH2CONH2), 3.74 – 3.84 (4H, m, J = 7.0 Hz, CH2CH3), 5.62(1H, br), and 5.86(1H, br) (CH2CH2CONH2). 13C NMR (CDCl3): δ: 12.1 (CH2CH3), 33.3 (CH2CH2CONH2), 44.3 (CH2CH2CONH2), 50.1 (CH2CH3); 176 (CH2CH2CONH2), 199 (S2CN).
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Sn Mössbauer-effect
spectrum: δ (mm s–1) = 1.22; ∆ (mm s–1) = 1.87. These values are similar to those reported [9] for the seven coordinate SnIV compound MeSn(NO3)3 [δ (mm s–1) = 0.94, ∆ (mm s–1) = 2.35].
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2.2.2 [(S2CNMe2-S,S)3(CH2CH2CONH2-C,O)Sn], 1a Prepared from Na(S2CNMe2) as yellow blocks. Yield 84%; m.p. 200 οC (decomp.). Anal.: calc. for SnC12H24N4S6OSn: C 26.1, H 4.36, N 10.2%; found: C 26.8, H 3.94, N 9.25%. IR (cm-1): 3340–2720, 1655 (s, C=O), 384 (w, Sn–S), 982 (m, C–S), 1515 (s, C–N + C=N). 1H NMR
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(CDCl3): δ: 3.41 (6H, s, CH3), 2.47 (2H, t, J = 8.5 Hz, CH2CH2CONH2), 2.85 (2H, t, J = 8.5 Hz, CH2CH2CONH2), 5.45 (1H, br) and 5.78 (1H, br), (CH2CH2CONH2). 13C NMR (CDCl3) δ: 12.8 (CH3), 33.4 (CH2CH2CONH2), 45.7 (CH2CH2CONH2), 176 (CH2CH2CONH2), 201 (S2CN). Sn Mössbauer-effect spectrum: δ (mm s–1) = 1.18, ∆ (mm s–1) = 1.87.
2.2.3 [{S2CN(C4H8)-S,S}3(CH2CH2CONH2-C,O)Sn], 1b
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Prepared from NH4(S2CN(CH2)4. Yield 75%; m.p. 180 °C (decomp.). Anal.: calc. for C15H30N4S6OSn: C 28.6, H 4.77, N 8.91%: found C 27.7, H 4.17, N, 8.00%. IR (cm-1): 3330– 2670, 1658(s, C=O), 324 (w, Sn–S); 949 (m, C–S); 1483 (s, C–N + C=N). 1H NMR: (CHCl3): δ: 2.06 (4H, m, NCH2CH2), 2.48 (2H, t, J = 8.5 Hz, CH2CH2CONH2,), 2.86 (2H, t, J = 8.5 Hz, CH2CH2CONH2,), 3.70 (4H, m, NCH2CH2), 5.41(1H, br) and 5.87 (1H, br), (CH2CH2CONH2). C NMR (CDCl3): δ: 26.2 (CH2CH2), 33.4 (CH2CH2CONH2), 50.9 (CH2CH2CONH2), 55.1
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∆ (mm s-1) = 1.86.
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Sn Mössbauer spectrum: δ (mm s-1) = 1.25;
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(NCH2CH2), 178 (CH2CH2CONH2), 196 (S2CN).
2.3. Crystallisation of (H2NCOCH2CH2-C,O)2SnCl2 , 2
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(H2NCOCH2CH2-C,O)2SnCl2 as described above was recrystallized from a solvent mixture of ethanol and water in the form of colourless blocks.
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2.4. Preparation of (H2NCOCH2CH2-C,O)(2-H2NCOC6H4S-O,S)SnCl2, 3 Solutions of (H2NCOCH2CH2-C,O)2SnCl2 (0.30 g, 1 mmol) in ethanol (10 ml) and 2HSC6H4CO2H (0.16 g, 1 mmol) in ethanol were mixed and refluxed for 30 minutes. The reaction mixture was concentrated to 10 ml and left at room temperature. The solid, which slowly formed, was collected after three days, and further recrystallized twice from cold ethanol solution to yield colourless blocks of 3. Final yield, 0.08 g (40%), m.p. 175–178 οC. 1HNMR (DMSO) δ: 7.68(d, 1H), 7.35(br, d, 1H), 7.08(m, 1H), 6.98(m, 1H), [all aryl H atoms] 5.85(br, 1H, NH), 5.62(br, 1H, NH), 2.85(t, J = 7Hz, 2H, CH2), 2.45(t, J = 7Hz), 2H, CH2). Anal.: calc. for C10H12Cl2N2O2SSn: C 29.02, H 2.44, N 6.76%: found: C 29.24, H 2.41, N 6.92%. IR (cm-1) 3300–2700, 1645(s). 4
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2.5 Preparation of [(hydroxy)bis(pyridin-2-yl)methanolato-N,O,N]SnCl3, 4 A solution of (H2NCOCH2CH2-C,O)SnCl3 (0.30g, 1.0 mmol) and bis(pyridin-2-yl)ketone (0.19 g, 1.0 mmol) in ethanol (15 ml) was heated under reflux for 1h and the solvent removed by
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rotary evaporation. TLC of the crude product indicated several mobile phases. The crude product was extracted twice into cold ethanol, rotary evaporated and the residue was recrystallized three times from ethanol solution: the first two recrystallizations yielded poorly crystalline material, while the third produced a small amount of better crystals, one of which was used in the X-ray structure determination. Melting characteristics: above 90 οC, the white solid gradually darkens
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in colour; at 185 οC a black amorphous powder is produced. IR (cm–1) 3000–2300(s,br), 1606(s), 1570(m). Anal.: calc. for C11H9Cl3N2O2Sn: C 30.98, H 2.35, N 6.57%: found: C 31.09, H 2.50, N
2.6 Crystal-structure determinations
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6.41%. There was insufficient amount of sample to obtain NMR data for 4.
The intensity data were collected using a Nonius KappaCCD (1) or Rigaku Mercury CCD diffractometer (2–4) using Mo Kα radiation, λ = 0.71073 Å (T = –173 °C). For 1, a yellow block of dimensions 0.40 × 0.32 × 0.16 mm was chosen for data collection; for 2, colourless
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block, 0.36 × 0.28 × 0.14 mm; for 3, colourless slab, 0.18 × 0.16 × 0.08 mm; for 4, colourless fragment, 0.08 × 0.06 × 0.04 mm. Empirical (multi-scan) absorption corrections were applied at the data-reduction stage.
All the structures were straightforwardly solved by direct methods using SHELXS-97 and the
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atomic models were developed and refined against |F|2 with SHELXL-2014 [10]. The O- and Nbonded H atoms were found in difference maps, relocated to idealised positions (O–H = 0.82, N–
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H = 0.92 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(carrier). The C-bonded H atoms were geometrically placed and modelled as riding atoms with C–H = 0.95–0.98 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density. The structures were analysed and verified with PLATON [11] and the molecular graphics were generated with ORTEP-3 [12]. The crystal used for data collection for 2 was twinned by rotation about [010] and the crystal of 3 was found to be an inversion twin [refined value of the Flack absolute structure parameter [13] = 0.475 (18)]. Crystal data for 1–4 are summarized in Table 1 and full details are available as supplementary material (cif format).
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3. Results and discussion
3.1 [(S2CNR2-S,S)3(CH2CH2CONH2-C)Sn] compounds 1, 1a, 1b
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Compounds 1, 1a and 1b were prepared from reactions between (H2NCOH2CH2-C,O)SnCl3 and the appropriate dithiocarbamate salt. The Mössbauer and IR spectroscopic data (vide supra) for all these compounds are indicative of similar coordination environments about the tin centres. The crystal structure of 1 (vide infra) shows the presence of a seven-coordinate tin(IV) centre in
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the solid state with a monodentate-C 2-amidoethyl anion and three S,S-bidentate dithiocarbmate ligands. While seven-coordinate tin compounds are well known [14], this is the first report of an amidotin compound with a seven-coordinate tin centre and the presence of a monodentate
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amidotin ligand. The two proton NMR signals for the NH2 group are presumably indicative of different hydrogen-bonding environments for the ‘dangling’ amide group rather than a change of coordination mode in solution.
There are parallels with estertin dithiocarbamato complexes: Zoufala et al. [15] reported that tris(N,N-diethyldithiocarbamato-S,S')-3-methoxypropyltin,
[(S2CNMe2-S,S′)3(CH2CH2CO2Me-
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C)Sn] had a seven-coordinate tin atom with a monodentate 2-MeCO2CH2CH2 ligand and three bidenrate dtc ligands, thus confirming proposals from earlier spectroscopic data [16]. By comparison, X-ray crystallographic studies indicated that the hexa-coordinated [(S2CNMe2S,S′)2(MeO2CCH2CH2-C)SnCl] complex had also two chelating dtc ligands and a non-chelating
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2-amidoethyl ligand [17] as did [(S2CNMe2-S,S′)(MeO2CCH2CH2-C)SnS]2 [18]. In contrast, [(S2CNMe2-S,S′)(MeOOCCH2CH2-C,O)SnCl2 ] was shown to possess a chelating 2-amidoethyl
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ligand [16]. Furthermore, [(PDTC)2(CH2CH2CO2R)2Sn] compounds (PDTC = pyrrolidinodithiocarbamato) have been recently shown to possess seven coordinate tin atoms with chelating PDTC groups, one chelating CH2CH2CO2R and one monodentate CH2CH2CO2R ligand [19]. From these reports, it is clear that these (2-carbonylethyl)tin-dtc complexes have a preference for bidentate dtc ligands over bidentate amido ligands. This may be rationalised in terms of the fact that dtc ligands are more powerful chelators than are the RCOCH2CH2 ligands (R = R′O or H2N) towards tin centres. The only ketotin dtc compound, [(Et2NCS2-S,S′](MeCOCMe2CH2C,O)SnCl2] is a six-coordinate complex [4b]. 6
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Other estertin complexes in which the 2-ROCOCH2CH2 ligands only act as monodentate ligands include the six-coordinate (MeO2CCH2CH2-C)Sn((PZ)3BH)X2 (X = Cl–, NCS–, [((PZ)3BH) = tris(pyrazolyl)borate) [20], the seven-coordinate [2-(methoxycarbonyl)ethyl]tris(8-quinolinato)tin, which possesses a [CN3O3Sn] pentagonal bipyramidal environment formed by chelating 8-
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quinolinato-N,O ligands and a monodentate 2-amidoethyl ligand [21], six-coordinate [(methoxy)bis(pyridin-2-yl)methanolato-N,O,N](CH2CH2CO2Me-C)SnCl2) [22] and the four coordinate [(MeO2CCH2CH2-C)2SnS]3 [18]. In the latter trimeric compound, which features an Sn3S3 ring, the presence of the sulfido ligands results in a much reduced Lewis acidity at the tin
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atom. 3.2. Crystal structure of 1
consists of one [(S2CNMe2-S,S/)3(CH2CH2CONH2-
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The molecular structure of 1 (Fig. 1)
C,O)Sn] molecule in space group P21/n in which the three dithiocarboxylate ligands chelate to the tin atom and the seven-coordination of the metal is completed by a monodentate-C-bonded 2amidoethyl anion. For the C4 ligand, the Sn1–S1 [2.4916 (4) Å] and Sn1–S2 [2.7720 (2) Å] bond lengths are significantly different [∆ = 0.2804 (3) Å]. The ligand C4–S1 and C4–S2 bond lengths of 1.7445 (15) and 1.7043 (15) Å, respectively, are characteristic of C–S single bonds whereas
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the C4–N2 separation of 1.3324 (19) Å clearly indicates a C=N double bond, indicating that the R2N+=C–(S–,S–) resonance form for the ligand makes a major contribution to the structure [23]. The C9 ligand shows a somewhat less asymmetric coordination [Sn1–S3 = 2.6463 (4), Sn1–S4 =
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2.7808 (4), ∆ = 0.1345 (6) Å] and again, the C–S bonds are similar [C9–S3 = 1.7355 (16), C9– S4 = 1.7111 (17) Å] and the C9–N3 bond length of 1.334 (2) Å is normal for a double bond. The C14 ligand shows the smallest difference between the Sn–S bonds [Sn1–S5 = 2.6974 (4), Sn1–
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S6 = 2.6455 (4), ∆ = 0.0519 (6) Å]. The C14–S5, C14–S6 and C14–N4 bond lengths are 1.7152 (17), 1.7357 (16) and 1.331 (2) Å, respectively. For each ligand, the C2N=CS2 grouping is almost planar (r.m.s. deviations = 0.017, 0.028 and 0.033 Å for the C4, C9 and C14 ligands, respectively) and one of the terminal –CH3 groups points ‘up’ with respect to this plane and the other points ‘down’, perhaps for steric reasons. The tin atom deviates from the ligand planes just mentioned by 0.3157 (12), 0.0667 (12) and –0.1889 (12) Å for the C4, C9 and C14 ligands, respectively. The Sn1–C1 bond length of 2.1647 (15) Å for the 2-amidoethyl anion in 1 is a little longer than the distances reported for six coordinated 7
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(chelating) bis-(amido)2tin compounds, e.g., in (H2NCOCH2CH2-C,O)2SnX2, the Sn–C bond lengths lie between 2.127 (3) and 2.146 (3) Å [5] The untethered ligand in 1 adopts an extended conformation [C1–C2–C3–O1 = –168.73 (15)ο]. The tin coordination polyhedron for 1 (Fig. 2) is well described as a pentagonal bipyramid with
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C1 and S1 occupying the axial sites [C1–Sn1–S1 = 165.99 (4)ο] and the other sulphur atoms defining the equatorial sites. The chelate bite-angles [S3–Sn1–S4 = 65.689 (12) and S5–Sn1–S6 = 66.773 (12)ο] are somewhat smaller than the other equatorial S–Sn–S angles. The bite angle
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for S1–Sn1–S2 of 68.306 (12)ο, is slightly larger than the others, which possibly correlates with its coordination role in the pentagonal bipyramid, although it must be noted that the difference is
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small.
In the crystal of 1, the molecules are linked by N–HLO and N–HLS hydrogen bonds (Table 2). By themselves, each lead to inversion dimers with
(8) and
(14) graph-set descriptors [24],
respectively and together they generate [010] chains (supplementary Fig. S1). The chains are consolidated and cross-linked by various C–HLO links.
3.3. Triclinic polymorph of (H2NCOCH2CH2-C,O)2SnCl2, 2
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Previously, the monoclinic C2/c and P21/c polymorphs of (H2NCOCH2CH2-C,O)2SnCl2 have been reported [5]. The former phase was obtained by recrystallization of 2 from an ethanol solution, and the latter was fortuitously isolated from a reaction mixture containing 2 and sodium
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chlorodifluoroacetate dissolved in acetone. The third, triclinic, polymorph, which we now report, was obtained by recrystallization of 2 from an aqueous–ethanol solution (1:1 v:v). The recovery of (H2NCOCH2CH2-C,O)2SnCl2 from this solvent mixture points to its significant hydrolytic
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stability, in contrast to those of simple di-organotin dihalides, which react to give organotin oxyhalides and organotin oxides. 3.4. Crystal structure of 2
The new triclinic polymorph of 2 (Fig. 3), crystallises with two molecules (A containing Sn1 and B containing Sn2) in the asymmetric unit. Octahedral SnC2O2Cl2 donor sets arise in which the C atoms are mutually trans [C–Sn–C = 164.2 (2)ο in both A and B] and the O atoms are trans to chloride ions [O–Sn–Cl = 169.13 (10) and 169.72 (11)ο in A; 170.33 (11) and 170.59 (11)ο in B); the pairs of O and Cl atoms are mutually cis. The distinction between the Sn–C, Sn–O and Sn–Cl 8
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bond lengths is very clear (Table 3). The chelate bite angles cover the narrow range from 77.28 (18) to 78.29 (18)ο. The tin octahedra could be described as moderately distorted [ranges of cis angles for A and B = 77.63 (17)–97.05 (5)ο and 77.28 (18)–96.85 (5)ο, respectively]: in each
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case, the largest angle is for the Cl–Sn–Cl grouping. The molecules differ in terms of the conformations of their chelate rings: for A, the C1 ligand is well described as an envelope with C1 itself as the flap, deviating by –0.390 (8) Å from the other atoms (r.m.s. deviation = 0.018 Å), as is the C4 ligand, in which C4 deviates from the other atoms (r.m.s. deviation = 0.016 Å) by –0.481 (7) Å. For B, both chelate rings are puckered about
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their Sn–C bonds: Sn2 and C7 deviate by 0.22 (2) and –0.367 (18) Å, respectively, from C8/C9/O3; for Sn2 and C10, the respective deviations with respect to C11/C12/O4 are 0.36 (2)
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and –0.191 (18) Å.
As might be expected, the extended structure of 2 features numerous hydrogen bonds arising from the NH2 groups. Taken by itself, the Sn1 molecule forms inversion dimers via a pair of N– HLO links and N–HLCl links connect the dimers into sheets. The Sn2 molecule does not form N–HLO links, but N–HLCl bonds generate [110] chains (supplementary Fig. S2).
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Collectively, a three-dimensional network arises. Two weak C–HLO bonds are also observed. The same hydrogen bonds are observed in the C2/c polymorph, which is also three-dimensional in terms of its directional intermolecular interactions, whereas the P21/c polymorph is layered [5].
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3.5. (H2NCOCH2CH2-C,O)SnCl2(OCNH2C6H4S-2-O,S), 3 Compound 3 was an unexpected product isolated from the reaction between (H2NCOCH2CH2-
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C,O)2SnCl2 and 2-HSC6H4CO2H in ethanol solution: it indicates that considerable changes in both reagents have occurred, including a ligand disproportionation of (H2NCOCH2CH2C,O)2SnCl2 (see equation 1 below), and that the benzoic acid group has been transformed to an amide (see equation 2 below). Ligand disproportionation reactions of organotin halides are wellknown and in the presence of chelating ligands can occur particularly readily [25]: the trichloride is a much stronger Lewis acid than the monochloride and will preferentially react with ligands. 2 (H2NCOCH2CH2-C,O)2SnCl2 → (H2NCOCH2CH2-C,O)SnCl3 + (H2NCOCH2CH2-C,O)3SnCl
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(1)
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The formation of 2-HSC6H4CONH2 is considered to arise from a “trans-esterification” reaction (equation 2). Similar reactions have been reported for a number of organotin carboxylate esters, including amidoethyltin compounds [19, 26].
(HOCOCH2CH2-C,O)nSnCl3–n + 2-HSC6H4CONH2 (2)
3.6 Crystal structure of 3
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(H2NCOCH2CH2-C,O)nSnCl3–n + 2-HSC6H4CO2H →
The asymmetric unit of 3 (Fig. 4) consists of two molecules (A containing Sn1 and B containing
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Sn2), each with a chelating 2-amidoethyl anion, an O,S-chelating thiol ligand and two chloride ions (Table 4). The disposition of the ligands about the octahedral tin atoms lead to one transS,C pairing [C–Sn–S = 163.43 (11)ο for A and 163.33 (11)ο for B] and two trans-O,Cl pairings
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[172.07 (9) and 177.08 (7)ο for A; 169.02 (9) and 177.80 (7)ο for B]: the pairs of O atoms and Cl atoms are mutually cis. The 2-amidoethyl bite angles [77.88 (13)ο for A and 79.05 (13)ο for B] are similar to those in 2. The bite angles for the O,S ligand are 86.84 (8)° and 86.04 (9)ο, for A and B respectively. Octahedral distortions may be quantified in terms of angular variances [27] of 37.3°2 for Sn1 and 40.7°2 for Sn2.
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The molecular conformations of the two molecules are slightly different. For A, the C1 (amide) chelate ring is an envelope with C1 deviating by –0.525 (7) Å from the other four atoms (r.m.s. deviation = 0.005 Å) whereas the C10 (thiol) ring is a distorted boat, with the dihedral angle between the C4/C5/C10/S1 (r.m.s. deviation = 0.0006 Å) and the Sn1/S1/O2 groupings being
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49.80 (16)°. Molecule B features a twisted conformation for the C13 (amide) ring, with atoms C11 and C12 deviating by 0.16 (1) and –0.22 (1) Å, respectively, from the plane of C13/O5/Sn2.
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The thiol (C20) ring is a distorted boat: the dihedral angle between C14/C15/C20/S2 (r.m.s. deviation = 0.006 Å) and Sn2/S2/O6 being 51.29 (17)°. In the crystal of 3, N–HLCl hydrogen bonds dominate the packing and an N–HLO and possible C–HLS link are also observed: together, these intermolecular bonds generate a three-dimensional network in the crystal. 3.7 [(HO)bis(pyridin-2-yl)methanolato-N,O,N]SnCl3 or Sn(C11H9N2O2)Cl3, 4 Various complexes have been prepared from reactions of bis(pyridin-2-yl)ketone with metal halides [22, 28], including reactions with tin and organotin halides. Reactions between bis(pyridin-2-yl)ketone and SnX4 (X = Cl or Br) and RSnCl3 in R′OH were shown to produce 10
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[(RO)bis(pyridin-2-yl)methanolato-N,O,N]SnX3)
and
[(RO)bis(pyridin-2-yl)methanolato-
N,O,N]RSnX2, respectively, including for [(CH2CH2CO2Me-C,O)SnCl3] [22]. The attempt to produce the analogous product with [Sn(CH2CH2CONH2C,O)SnCl3] failed, with 4 being the only reaction of the amidotin starting material has occurred. 3.8. Crystal structure of 4
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product identified. The formation of this product suggests that another ligand disproportionation
The molecular structure of 4 is a neutral molecular complex (Fig. 5) consisting of an N,N,O-
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tridentate ligand deprotonated at O1, i.e.: C11H9N2O2–, and three chloride ions bound to the tin atom to generate an octahedral SnN2OCl3 donor set (Table 5) with the chloride ions defining one triangular face of the octahedron.
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The dihedral angle between the pyridine rings is 69.4 (3)ο. The Sn atom deviates from the N1 ring by –0.270 (15) Å; conversely it is exactly co-planar with the N2 ring [deviation = 0.000 (16) Å. The bridging C5–C6–C7 bond angle is 109.0 (8)ο and the tin atom deviates from the O1/C6/O2 plane by 0.15 (2) Å. The cis octahedral bond angles vary from 74.6 (3) to 97.97 (9)°, with the smaller values corresponding to chelate bite angles [O1–Sn1–N2 = 75.5 (3)°, O1–Sn1–
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N2 = 74.6 (3)°, N1–Sn1–N2 = 81.7 (3)°]. Both chelate rings (Sn1/N1/C5/C6/O1 and Sn1/N2/C7/C6/O1) can be described as envelopes, with O1 being the flap in each case [deviations = –0.814 (10) and 0.784 (11) Å, respectively]. In the extended structure of 4, dimers related by a crystallographic twofold axis and linked by
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pairs of O–HLO hydrogen bonds (supplementary Fig. S3) occur, generating
(8) loops.
Several weak C–HLCl links are also present.
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4 Conclusions
Four new tin complexes have been prepared and spectroscopically and structurally characterised. Compound 1, (H2NCOCH2CH2-C)(Et2NCS2-S,S′)3Sn, features the uncommon situation of a nonchelating amidoethyl ligand as part of a pentagonal bipyramidal SnS6C coordination polyhedron. Compound 2, (H2NCOCH2CH2-C,O)2SnCl2, is a triclinic polymorph crystallised from mixed solvents (water and ethanol) of two previously described monoclinic forms: its formation is surprising given the tendency for diamidoethyltin dihalides to hydrolyse. Compound 3, (H2NCOCH2CH2-C,O)(2-H2NCOC6H4S-O,S)SnCl2, was isolated as an unexpected product from 11
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a reaction that featured both ligand disproportionation and trans-esterification of the starting materials. Compound 4, Sn(C11H9N2O2)Cl3, is a classical complex, which must also arise from a
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facile ligand disproportionation of the starting di(amidoethyl)tin compound.
Acknowledgements
We thank the EPSRC National Crystallography Service (University of Southampton) for the intensity data collection
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References
(a) R.E. Hutton, V. Oakes, Adv. Chem. Ser. 157 (1976) 123; (b) D. Lanigen, E.L. Weinberg, Adv. Chem. Ser. 157 (1976) 134; (c) J.W. Burley, O. Hope, R.E. Hutton, J. Groenenboom, J. Organomet. Chem. 170 (1979) 21; (d) J.W. Burley, R.D. Dworkin, J. Vinyl Tech. 8 (1986) 15.
[2]
(a) R.A. Howie, E.S. Paterson, J.L. Wardell, J.W. Burley, J. W. (1986). J. Organomet. Chem. 304 (1986) 301; (b) R. Balasubramanian, Z.H. Chohan, S.M.S.V. Doidge-Harrison, R.A. Howie, J.L. Wardell, Polyhedron 16 (1997) 4283; (c) L.J. Tian, Z. Zhou, Q. Yu, X. Liu, X. (2003). Synth. React. Inorg. Met.-Org. Chem. 33 (2003) 259; (d) L.J. Tian, Q. Yu, Z. Shang, Y. Sun, L. Zhang, L. (2005). Appl. Organomet. Chem. 19 (2005) 677; (e) L.J. Tian, Y.X. Sun, X.J. Liu, G.M. Yang, Z.C. Shang, Z. C. (2005). Polyhedron 24 (2005) 2027.
[3]
(a) B.F. Milne, R.P. Pereira, A.M. Rocco, J.M.S. Skakle, A.J. Travis, J.L. Wardell, J. L. & Wardell, S. M. S. V. Appl. Organomet. Chem, 19 (2005) 363; (b) R.A. Howie, J.L. Wardell, Acta Cryst. C57 (2001) 1041; (c) E.R.T. Tiekink, J.L. Wardell, W.B. Welte, Acta Cryst. E62 (2006) m1763 (a) P.G. Harrison, T.J. King, M.A. Healy, J. Organomet. Chem. 182 (1979) 17; (b) E.R.T. Tiekink, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2006). Acta Cryst. E62 (2006) m971; (c) S.M.S.V. Wardell, W.T.A. Harrison, E.R.T. Tiekink, G.M. de Lima, J.L. Wardell, J. L. (2010). Acta Cryst. E66 (2010) m312; (d) G.M. de Lima, E.R.T. Tiekink, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2011). Acta Cryst. E67 (2011) m1536. R.A. Howie, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, N.M. Comerlato, N. M. (2011). Z. Krist. 226 (2011) 535–552. R.A. Howie, W.T.A. Harrison, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2011). Z. Krist. 226 (2011) 739.
[5] [6]
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[4]
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[1]
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[20] [21] [22] [23] [24] [25]
[26] [27] [28]
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M AN U
[15] [16] [17] [18] [19]
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[9] [10] [11] [12] [13] [14]
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[8]
R.A. Howie, G.M. de Lima, E.R.T. Tiekink, J.L. Wardell, S.M.S.V. Wardell, S. M. S. V. (2011). Z. Krist. 226 (2011) 837. R.A. Howie, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, W. T. A. Harrison, J. Organomet. Chem. 716 (2012) 62. D. Potts, H.D. Sharma, A.J. Carty, A. Walker, Inorg. Chem. 13 (1974) 1205. G.M. Sheldrick, Acta Cryst. C71 (2015) 3. A.L. Spek, Acta Cryst. D65 (2009) 148. L.J. Farrugia, J. Appl. Cryst. 45 (2012) 849. H.D. Flack, Acta Cryst. A39 (1983) 876–881. (a) J.S. Morris, E.O. Schlemper, J. Cryst. Mol. Struct. 8 (1978) 295; (b) J.S. Morris, E.O. Schlemper, J. Cryst. Mol. Struct. 9 (1979) 1. P. Zoufala, I. Cisarova, A. Ruzicka, Main Group Met. Chem. 26 (2003) 53. O.S. Jung, J.-H. Jeong, Y.S. Sohn, Polyhedron 8 (1989) 1413. O.S. Jung, J.-H. Jeong, Y.S. Sohn, Acta Cryst. C46 1990) 31. O.S. Jung, J.-H. Jeong, Y.S. Sohn, Polyhedron, 8 (1989) 2557–2563. B.P.de Morais, C.L. Donnici, B.L. Rodrigues, G.M. de Lima, J.L. Wardell, R.S. Bitzer, J. Organomet. Chem. 832 (2017) 57. O.S. Jung, J.-H. Jeong, Y.S. Sohn, J. Organomet. Chem. 399 (1990) 235. L.J. Tian, S. Zhang, Y.Z. Yao, X.W. Shi, Main Group Met. Chem. 39(2016) 209. R.A. Howie, G.M. de Lima, J.L. Wardell, S.M.S.V. Wardell, Polyhedron 29 (2010) 739. E.R.T. Tiekink, Appl. Organomet. Chem. 22 (2008) 533. J. Bernstein, R.E. Davis, L. Shimoni, N. Chang, Angew. Chem. Int. Ed. 34 (1995) 1555. (a) S.J. Blunden, P. Harston, R. Hill, R. J.L. Wardell, J. L. (1990). Appl. Organomet. Chem. 4, 383; (b) C. Pettinari, F. Marchetti, R. Pettinari, A. Cingolani, A. Drozdov, S. Troyanov, J. Chem. Soc. Dalton Trans. (2002) 1884; (c) D.V. Airapetyan, V.S.., Petrosyan, S.V. Gruener, K.V., Zaitsev, D.E. Arkhipov, A.A. Korlyukov, J. Organomet. Chem. 747 (2013) 241. Y. Xu, W. An, W. Ding, H. Liu, L. Tian, Commun. Inorg. Synth. 1 (2013) 60. K. Robinson, G.V. Gibbs, P.H. Ribbe, Science (Washington, DC) 172 (1971), 567. T.C. Stamatatos, C.G. Efthymiou, C.C. Stoumpos, S.P. Perlepes, Eur. J. Inorg. Chem. (2009) 3361.
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[7]
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Figure captions
Figure 1: the molecular structure of 1 showing 50% displacement ellipsoids. The H atoms of the
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dithiocarbamate ligands are omitted for clarity. Figure 2: detail of 1 showing the distorted pentagonal bipyramidal coordination of the tin atom. Figure 3: the molecular structure of the Sn1 molecule in 2 showing 50% displacement ellipsoids.
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Figure 4: the molecular structure of the Sn1 molecule in 3 showing 50% displacement ellipsoids.
Supplementary Figure captions
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Figure 5: the molecular structure of 4 showing 50% displacement ellipsoids.
Figure S1: fragment of a hydrogen-bonded chain in the crystal of 1: symmetry codes as in Table
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2.
Figure S2: fragment of a hydrogen-bonded chain in the crystal of 2: symmetry codes as in Table 3.
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Figure S3: a dimer with twofold symmetry in the crystal structure of 4 linked by a pair of O–
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HO hydrogen bonds. Symmetry code as in Table 5.
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Table 1: Key crystallographic data for 1–4
C18H36N4OS6Sn
C6H12Cl2N2O2Sn
C10H12Cl2N2O2SSn
C11H9Cl3N2O2Sn
Mr
635.56
333.77
413.87
426.24
Crystal system
Monoclinic
Triclinic
Orthorhombic
Orthorhombic
Space group
P21/n (No. 14)
1 (No. 2)
Pca21 (No. 29)
Pcca (No. 54)
a (Å)
14.40360 (10)
8.0191 (6)
10.8998 (2)
14.9717 (10)
b (Å)
12.4098 (2)
10.7786 (8)
7.7467 (2)
11.8709 (8)
c (Å)
17.1388 (2)
13.2081 (9)
33.411 (2)
15.6014 (11)
α (°)
90
89.365 (7)
90
90
β (°)
113.7167 (7)
77.118 (6)
90
90
90
88.339 (7)
90
90
V (Å )
2804.76 (6)
1112.42 (14)
2821.14 (19)
2772.8 (3)
Z
4
4
8
8
1304
648
1616
1648
ρcalc (g cm )
1.505
1.993
1.949
2.048
µ (mm–1)
1.375
2.750
2.332
2.418
Data collected
29904
5007
28981
25446
Unique data
6414
5007*
6439
3213
RInt
0.033
–
0.022
0.079
0.046
0.017
0.083
0.112
0.036
0.152
1547170
1547171
1547172
F(000) –3
R(F) [I > 2?(I)]
0.020
2
wR(F ) (all data) 0.048 CCDC code
%
1547169
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3
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γ (°)
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Emp. formula
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1 2 3 4 _____________________________________________________________________________________________
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_________________________________
*Refined as a non-merohedral twin and data not merged %
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Full crystallographic data for these structures including atom positions and geometrical parameters can be accessed at: http://www.ccdc.cam.ac.uk/Community/Requestastructure/Pages/DataRequest.aspx by citing the code number shown.
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Table 2: selected geometrical data (Å,°) for 1 2.1647 (15)
Sn1–S1
2.4916 (4)
Sn1–S6
2.6455 (4)
Sn1–S3
2.6463 (4)
Sn1–S5
2.6974 (4)
Sn1–S2
2.7720 (4)
Sn1–S4
2.7808 (4)
C1–Sn1–S1
165.99 (4)
C1–Sn1–S6
98.02 (4)
S1–Sn1–S6
95.453 (13)
C1–Sn1–S3
97.83 (4)
S1–Sn1–S3
88.828 (13)
S6–Sn1–S3
77.415 (12)
C1–Sn1–S5
91.67 (4)
S1–Sn1–S5
S6–Sn1–S5
66.773 (12)
S3–Sn1–S5
C1–Sn1–S2
98.75 (4)
S1–Sn1–S2
S6–Sn1–S2
138.605 (13)
S3–Sn1–S2
136.535 (12)
S5–Sn1–S2
75.162 (12)
C1–Sn1–S4
86.09 (4)
S1–Sn1–S4
85.450 (13)
S6–Sn1–S4
143.079 (13)
S3–Sn1–S4
65.689 (12)
S5–Sn1–S4
150.086 (13)
S2–Sn1–S4
75.719 (12)
C5–H5aLS2
iii iv
C12–H12bLO1 C13–H13aLO1 C16–H16aLS2
v
vi
90.112 (13)
143.899 (12)
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68.306 (12)
0.88
2.12
2.9969 (17)
173
0.88
2.75
3.5897 (14)
160
0.99
2.91
3.7852 (17)
148
0.99
2.52
3.462 (2)
159
0.98
2.53
3.492 (2)
167
0.98
2.90
3.5702 (18)
126
TE D
N1–H1dLS3
ii
EP
N1–H1cLO1i
RI PT
Sn1–C1
SC
_________________________________________
____________________________________________________________________________
AC C
Symmetry codes: (i) 1–x, 2–y, –z; (ii) 1–x, 1–y, –z; (iii) ½–x, y–½, ½–z; (iv) 3/2–x, y–½, ½–z; (v) ½+x, 3/2–y, ½+z; (vi) x–½, 3/2–y, z–½.
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Table 3: selected geometrical data (Å,°) for 2 _________________________________________ 2.129 (5)
Sn1–C1
2.129 (5)
Sn1–O1
2.275 (4)
Sn1–O2
2.310 (4)
Sn1–Cl1
2.4972 (13)
Sn1–Cl2
2.5019 (13)
Sn2–C10
2.116 (6)
Sn2–C7
Sn2–O4
2.299 (4)
Sn2–O3
Sn2–Cl3
2.4939 (13)
Sn2–Cl4
N1–H1cLCl2i
RI PT
Sn1–C4
2.120 (5)
2.310 (4)
2.5200 (13)
2.60
3.461 (5)
N1–H1dLCl2
0.88
2.63
3.421 (5)
149
iii
0.88
2.05
2.865 (6)
153
N2–H2dLCl1
0.88
2.60
3.344 (6)
143
N2–H2dLCl4
0.88
2.79
3.422 (7)
130
C5–H5bLCl3
0.99
2.90
3.631 (5)
132
2.53
3.396 (5)
166
2.92
3.594 (5)
135
2.80
3.484 (5)
136
2.45
3.297 (5)
161
2.96
3.874 (6)
154
iv
0.88
iii
0.88
ii
0.88
vi
N4–H4dLCl3
0.88
C11–H11aLCl2vii
0.99
N3–H3aLCl4
N3–H3bLCl1
N3–H3bLCl4
TE D
v
M AN U
N2–H2LO2
167
SC
0.88
ii
___________________________________________________________________________ Symmetry codes: (i) 1–x, 1–y, 1–z; (ii) x–1, y, z; (iii) 1–x, –y, 1–z; (iv) 2–x, –y, 1–z; (v) 1–x, –y,
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–z; (vi) 2–x, 1–y, –z; (vii) x, y, z–1.
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Table 4: selected geometrical data (Å,°) for 3 _________________________________________ 2.132 (4)
Sn1–O2
2.179 (3)
Sn1–O1
2.308 (3)
Sn1–S1
2.4141 (10)
Sn1–Cl2
2.4436 (10)
Sn1–Cl1
2.5541 (10)
Sn2–C11
2.137 (4)
Sn2–O6
Sn2–O5
2.303 (3)
Sn2–S2
Sn2–Cl5
2.4385 (10)
Sn2–Cl4
RI PT
Sn1–C1
2.199 (3)
2.4152 (11)
2.5328 (10)
N1–H1cLCl4i
0.88
2.49
3.335 (4)
ii
0.88
2.40
3.262 (4)
168
iii
0.99
2.90
3.651 (6)
134
iv
0.95
2.73
3.675 (4)
173
SC
C6–H6LCl2
M AN U
C2–H2bLS1
v
0.95 (5)
2.55 (5)
3.397 (4)
147 (4)
vi
0.79 (5)
2.57 (5)
3.343 (4)
166 (4)
vii
0.88
2.40
3.261 (4)
164
viii
0.88
2.44
3.274 (4)
159
ix
0.91 (5)
2.67 (5)
3.466 (4)
147 (4)
x
0.92 (5)
2.42 (5)
3.308 (4)
163 (4)
0.95
2.68
3.619 (4)
171
N2–H1nLCl2
N2–H2nLCl1 N3–H3cLCl1
N3–H3dLCl1 N4–H7nLCl5
N4–H8nLCl4
C16–H16LCl5iii
TE D
N1–H1dLO5
162
___________________________________________________________________________ Symmetry codes: (i) ½–x, y, z–½ ; (ii) 1–x, –y, z–½; (iii) ½+x, –y, z; (iv) x–½, 1–y, z;
(v) x–½ ,
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–y, z; (vi) x, y–1, z; (vii) 1–x, 1–y, ½+z; (viii) ½–x, y, ½+z; (ix) ½+x, 1–y, z; (x) x, 1+y, z.
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Table 5: selected geometrical data (Å,°) for 4 _________________________________________ 2.045 (6)
Sn1–N2
2.224 (8)
Sn1–N1
2.250 (8)
Sn1–Cl1
2.361 (3)
Sn1–Cl2
2.370 (3)
Sn1–Cl3
2.372 (3)
0.82
1.94
2.690 (9)
C1–H1LCl3
ii
0.93
2.94
3.539 (11)
C4–H4LCl2
iii
0.93
2.98
3.552 (10)
C4–H4LCl3
i
0.93
2.92
3.759 (11)
C8–H8LCl1
iii
0.93
2.86
3.534 (10)
153
124
121
151
SC
O2–H2aLO1i
RI PT
Sn1–O1
130
____________________________________________________________________________
AC C
EP
TE D
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Symmetry codes: (i) –x, –y, ½–z; (ii) –x, –y, –z; (iii) ½–x, y, ½+z.
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C18 C10
C11 S6
C6
S1
SC
C9
C12
TE D S2
S5 C1 C2
AC C
C7
C16
C4
EP
N2
N1
C8
C3 O1
N4 C15
Sn1
S4
C5
C14
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C13
C17
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S3
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S6
SC
RI PT
C1
Sn1
AC C
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TE D
S5
S2
S1
S3 S4
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N2
C6
SC
O2
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N1 C3
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TE D
O1
AC C
C2
C5
C4
Sn1
C1 Cl1
Cl2
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N2 O2
N1
C1
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C10
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C2
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C9
O1
Cl2
C4
Sn1
TE D
C8
C3
C7
AC C
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C5
C6
S1
Cl1
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C8
O2 C4
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C3
C6
C2
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C5
C9
C7 C10
O1
EP
C11 Sn1
AC C
C1
TE D
N1
N2
Cl1
Cl3 Cl2
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O
N
NH 2
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S
S
S
Sn
S
N
S
S
1
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SC
N
Et2N=CS2 -
O
SnCl2 HCl, EtOEt
NH 2
Cl Cl
Sn
TE D
Cl
NH 2
O
HCl
pyCOpy, moist EtOH
Sn, EtOEt
Cl O
N HO
O
Cl Sn
N
O Sn Cl
AC C
2
EP
NH 2
Cl
2-HS-C6H4CO2H
4
H 2N
S Cl Sn
3
Cl
O Cl O H 2N
NH 2
ACCEPTED MANUSCRIPT Highlights New types of amidotehyl tin complexes are presented
•
Ligand disproportionation and trans-esterification reactions occur
•
New insights into polymorphism and hydrolytic stability are offered
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•