Sn Cl Bond Lengths Research Articles

(2-Amidoethyl)trichlorotin(IV)complexes with amido ligands and chloride ion: supramolecular arrays from H-bonds involving the amido and chloride ions

AbstractComplexes, (H2NCOCH2CH2-C,O)(L)SnCl3(2:L= XCH2CH2CONH2; X = H or Cl), rather than (H2NCOCH2CH2-C,O)SnCl3, have been isolated from reaction mixtures containing hydrochloric acid, tin and acrylamide in Et2O solution. Ligand exchange reactions occur between (2: L= EtCONH2) and HCONMe2or HCONHBu. The anionic complex, [pyridinium][(H2NCOCH2CH2-C,O)SnCl4],3, was isolated from a reaction mixture composed of pyridine and2. In both complex types,2and3, tin is hexacoordinate, in which the octahedral geometries are somewhat distorted due to variations in the Sn—Cl bond lengths, exemplifying thetranseffect, and the small bite angles of the chelating (2-amidoethyl-C,O) ligand. The supramolecular structures are dominated by intermolecular hydrogen-bonds with the NH2groups as the donor species. A feature of each crystal structure is a double chain in which the NH2group of the (2-amidoethyl-C,O) ligand acts as donor for N—H···X (X = Cl or O) intermolecular hydrogen-bonds.

N-Butyldichlorido(2-{(1E)-1-[2-(pyridin-2-yl)hydrazin-1-ylidene]ethyl}phenolato)tin(IV)

Two independent mol­ecules comprise the asymmetric unit of the title compound, [Sn(C4H9)(C13H12N3O)Cl2]. The Sn atom in each is coordinated by the tridentate ligand via the phenoxide O, hydrazine N and pyridyl N atoms, forming five- and six-membered chelate rings. The approximately octa­hedral coordination geometry is completed by the α-C atom of the n-butyl group (which is trans to the hydrazine N atom) and two mutually trans Cl atoms. Differences between the mol­ecules are evident in the relative planarity of the chelate rings and in the conformations of the n-butyl groups [C—C—C—C = 177.2 (5) and −64.4 (11)°]. Significant differences in the Sn—Cl bond lengths are related to the formation of N—H⋯Cl hydrogen bonds, which link the mol­ecules comprising the asymmetric unit into dimeric aggregates. These are consolidated in the crystal packing by C—H⋯Cl contacts. The structure was refined as an inversion twin; the minor twin component is 37 (3)%.

Room‐Temperature Synthesis of the Highly Polar Cluster Compound Sn[SnCl][W3Cl13

AbstractA new synthetic strategy is employed to synthesize a tungsten trinuclear cluster compound with an ionic liquid (IL) as the reaction medium. Dark brown block‐shaped crystals of Sn[SnCl][W3Cl13] were obtained at room temperature by reacting tin and WCl6 in Lewis acidic ionic liquid [BMIM]Cl/AlCl3 ([BMIM]+ = 1‐butyl‐3‐methylimidazolium). Compound Sn[SnCl][W3Cl13] crystallizes in the polar hexagonal space group P63 with cell parameters a = 959.8(1) and c = 1190.3(2) pm. The crystallographic point group of the [W3(μ3‐Cl)(μ‐Cl)3Cl9]3– cluster anions is C3, but C3v pseudosymmetry is observed within twice the standard deviation of the bond lengths. The W–W bond length is 272.18(6) pm. The tin(II) cations, which are in trigonal pyramidal and in distorted trigonal‐antiprismatic coordination spheres that comprise chloride ions, connect the clusters into layers that are stacked according to the 63 screw axis. One of the chloride ions is bound only to a single tin cation resulting in a [SnIICl]+ group with a Sn–Cl bond length of 236.1(5) pm. The pronounced polarity of the crystal structure means that its diffraction pattern exhibits huge deviations from Friedel's law. Most remarkable is that the intensity (Fc2) of reflection 004 is 175 % of the intensity of the 00$\bar {4}$ reflection.

Synthesis and characterization of [M(DMSO)6][SnCl6] complexes (M = Fe2+, Co2+, and Ni2+) — An old mystery solved

The synthesis of an "unknown" Fe(II) complex originally reported in 1973 and formulated then as [Fe(DMSO)5Cl][SnCl4] was thoroughly reproduced and the compound reformulated as the novel [Fe(DMSO)6][SnCl6] double complex salt. Current elemental analysis and IR and Mössbauer spectroscopy matched the original 1973 data, and Raman spectroscopy and single crystal X-ray diffraction provided additional confirmation of our reformulation. [Fe(DMSO)6][SnCl6] (1) crystallizes in the trigonal space group R[Formula: see text] with octahedral [Fe(DMSO)6]2+ and [SnCl6]2– complex ions with an Fe—O bond length of 2.121(3) Å. The same synthesis was extended to Co(II) and Ni(II) to generate the novel [Co(DMSO)6][SnCl6] (2), which crystallizes in the triclinic space group P[Formula: see text] with a Co—O bond length of 2.093(4)–2.113(5) Å, and [Ni(DMSO)6][SnCl6] (3), which crystallized in the trigonal R[Formula: see text] space group and has a Ni—O bond length of 2.062(2) Å. The Sn—Cl bond length in all three complexes ranged from 2.421(2) to 2.448(2) Å.Key words: DMSO complexes of Fe(II), Co(II) and Ni(II), SnCl62– salts, IR, Raman and Mössbauer spectroscopy, X-ray crystal structures.

The structure of tri(cyclohexyl)tin chloride between 108 and 298 K: a compound in which molecular dimensions vary with temperature.

Care is necessary when relating physical data obtained at one temperature on compounds showing significant intermolecular interactions to X-ray data obtained at other temperatures. This is revealed by the determination of the structure of tri(cyclohexyl)tin chloride at nine different temperatures between 108 and 298 K. In the crystal, the molecules pack in chains parallel to the c axis with the Sn and Cl atoms close to the plane, with y = 0.25. At low temperature, successive molecules in the chain are related by the glide plane in space group P2(1)/c, and there is significant intermolecular interaction. As the temperature is raised, the Cy(3)SnCl.Sn interactions weaken and the intramolecular Sn-Cl bonds strengthen. At about 248 K, there is an order-disorder transition to space group P2(1)/m with the c axis halved, and at room temperature the structure is best described as comprising discrete molecules, as previously reported. Thus, some of the molecular dimensions, in particular the Sn-Cl bond lengths, are not constant but are functions of temperature.

Chlorodimethyl(N-methylpyrrolidinone)tin(IV)-μ-chloro-dichlorodimethyltin(IV)

The synthesis and the X-ray structural analysis of the title compound, μ-chloro-1:2κ2Cl-tri­chloro-1κCl,2κ2Cl-tetra­methyl-1κ2C,2κ2C-(N-methyl­pyrrolidin-2-one)-1κO-ditin(IV), [Sn2Cl4(CH3)4(C5H9NO)], are described. The title compound is found to exhibit a distorted trigonal–bipyramidal geometry at both SnIV atoms. The Sn—Cl—Sn angle involving the bridging chlorine ligand is 135.56 (5)°, with the Sn—Cl bond lengths being 2.5704 (13) and 3.1159 (13) Å.

8-Methylaminoquinolinium Salts of Tetrachlorodimethylstannate(IV) and Tetrachlorodiphenylstannate(IV)

The title compounds, (C10H11N2)2[SnCl4(CH3)2] and (C10H11N2)2[SnCl4(C6H5)2], have been prepared from the reaction of 8-methylaminoquinoline with diorganotin dichlorides. In the methyl compound, the Sn atom is coordinated to two methyl groups, which are trans with respect to each other [Sn—C 2.102 (5) and 2.103 (4) A], and to four Cl atoms [Sn—Cl 2.442 (1), 2.461 (1), 2.894 (1) and 3.098 (1) A]. The two long Sn—Cl bonds are trans to the short ones and their Cl atoms are hydrogen bonded to the N—H groups of the 8-methylaminoquinolinium cations. The Sn—CH3 bonds are bent away from the short Sn—Cl bonds so that the CH3—Sn—CH3 angle is 155.7 (2)°. A correlation between the C—Sn—C angle and the Sn—Cl bond lengths was observed. The anion of the phenyl compound is close to being octahedral and has exact twofold symmetry; the phenyl groups are trans with respect to each other [Sn—C 2.143 (2) A] and Sn—Cl distances are in the range 2.497 (1)–2.672 (1) A. Two Cl atoms are hydrogen bonded to N—H groups of the cations.

Synthesis and Crystal Structure of Orthorhombic NaSn 2Cl 5: A New Type of AB2X5 Compound

The phase diagram of the quasi-binary system NaCl-SnCl 2 has been derived from DSC and X-ray investigations. In this system a dystectic NaSn 2Cl 5 compound phase was found, which was obtained by grinding mixtures of NaCl and SnCl 2 in a closed ball mill and then subsequent tempering at temperatures about 170°C in evacuated sealed silica ampoules. The single-crystal structure of NaSn 2Cl 5 was determined. It crystallizes with a new orthorhombic-type arrangement [space group Pnnm; a = 818.09(5), b = 1203.1(1), c = 871.63(8) pm; Z = 4]. The structure was solved by Patterson methods with the MolEN program, and refined to a final R value of 0.019 for 717 unique reflections. The sodium ions are located in almost octahedral voids of Cl ions. Two kinds of tin ions manifest themselves structurally by a great distortion of their coordination environment, three Cl ions are situated at <272.77 pm from the tin ion, which is a reasonable Sn-Cl bond length, but the other five or six are repelled by the lone pair to distances of >306.75 pm. Different from the structure of U 3Se 5, it is another distorted Rh 5Ge 3 structure. In this paper the structural relationship between NH 4Pb 2Cl 5 and NaSn 2Cl 5 is elucidated systematically by means of the group theoretical representation of group-subgroup relations.

Cis-Dichlorobis(N,N-diethyldithiocarbamato-S,S')tin(IV)

The structural features of the title complex, [SnCl 2 (C 5 H 10 NS 2 ) 2 ], are significantly different to those of the complexes Me 2 Sn(S 2 CNR 2 ) 2 that have been structurally characterized so far. In the title complex the geometry around the Sn atom is cis-octahedral with a Cl-Sn-Cl angle of 91.85 3) o and an average Sn-Cl bond length of 2.404 (7) A. Bothdithiocarbamato groups behave as bidentate chelating ligands with an average Sn-S bond length of 2.539 (6) A and an average S-Sn-S bond angle of 71.01 (2) o

Information from the mössbauer spectra of tin(IV) halide complexes with 1,3-diethylthiourea. A redetermination of the crystal structure of tetrachlorobis(1,3-diethylthiourea)tin(IV)

The Mössbauer quadrupole splitting of octahedral tin(IV) chloride complexes can give information about the Sn–Cl bond lengths. As the value of d(Sn–Cl) reported previously for SnCl4(detu)2(detu = 1,3-diethylthiourea) was too long for a complex showing a single line in the Mössbauer spectrum, we have redetermined the X-ray crystal structure, and found Sn–Cl distances which are compatible with the Mössbauer data. The compound crystallises in the centrosymmetric space group Rc, and the structure is disordered about a crystallographic two-fold axis passing through Sn and two Cl atoms. The disorder does not allow the unambiguous distinction between a cis or trans structure by X-ray crystallography, but IR and Raman spectroscopies show that both SnCl4(detu)2, and the new compound SnF4(detu)2, have a cis geometry. The isomer shift values for SnX4(detu)2 are –0.04, 0.62, 0.96 and 1.21 mm s–1 for X = F, Cl, Br and I, respectively. The values for X = Cl and Br are much higher than previous values, and fully consistent with S-co-ordination by the detu ligand. The information on the donor atom in SnX4L2 complexes, which can sometimes by obtained from the Mössbauer isomer shift, is discussed.

35Cl NQR and X‐Ray Studies of Pentachloroethylstannate(IV) Salts

AbstractThe 35CI NQR spectra of pentachloroethylstannate(IV) complex salts A2[(C2H5)SnCl5)] with four different cations A⊕ (A⊕ = Tetra‐ methylamnionium, [(CH3)4N]⊕ (I), Pyridinium, [CSHSNH]⊕ (II). Methylammonium, [CH3NH3]⊕ (III), and 4‐Picolinium, [4‐CH3 ‐ C5H4NH]⊕ (IV)) have been recorded and their crystal structures were determined. The compounds crystallize with a distorted K2PtCI6‐type structure ((I): space group C62h/c, a = 1408.9 pm, b = 1123.2 pm, c = 1332.7 pm, β = 90.94°, Z = 4; (II): space group C52h/c, a = 1618.8 pm, b = 744.6 pm, c = 1520.0 pm, β = 90.515°, Z = 4; (IV): space group Ct‐Pi, a = 1093.4 pm, b = 938.8 pm, c = 722.6 pm, α = 108.37°, β = 90.84', γ = 93.90, Z = 2 = (IV): space group D42‐P212121, a = 2181.1 pm, b = 1088.3 pm, c = 858.2 pm, Z = 4). The effects of the substitution of one Cl⊖ ligand within a SnCl2⊖6 octahedron by the stronger electron donor C2H⊖5 are: (a) The mean strength of all 5 Sn—Cl bonds is lowered. This is reflected by a decrease of the mean 35Cl NQR frequencies and an increase in Sn—Cl bond length compared with hexachlorostannates; (b) There exists a distinct cis and trans influence of the ethyl group. The Sn—Cl bonds in cis position to the ethyl group are highly weakened (cis‐weakening), while the trans effect is much smaller in magnitude and probably of opposite sign (trans‐strengthening). The influence of hydrogen bonds weakens Sn—Cl bonds in addition to cis‐weakening. A correlation of 35Cl NQR frequencies and Sn—Cl bond lengths shows a slope of —0.6 MHz/pm. The ethyl group is ordered in (II) and (III), disordered in (IV) and rotates in (I). In (I) a phase transition at 180 K could be detected by 35Cl NQR and DTA, the reason of which may be a freezing in of the ethyl group rotation.

Crystal and molecular structure of tris(hexaamminerhodium(III)) tetrakis(trichlorostannato(II))(tetrachlorostannato(II)rhodate(I) hexachlorostannate(II) tetrahydrate

The crystal and molecular structure of the title compound, [Rh(NH 3) 6] 3[Rh(SnCl 3) 4(SnCl 4)] [SnCl 6] · 4H 2O, has been determined by the single-crystal X-ray diffraction method. The compound crystallizes in the monoclinic system, space group P2 n with a = 16.581(2), b = 11.010(4), c = 16.024(2)Å, β = 90.76(1), and two molecules per unit cell. The structure was solved by Patterson's method and refined by the least-squares technique to give a final R factor of 0.031. The three cations, [Rh(NH 3) 6] 3+, are a regular octahedron with an average RhN bond length of 2.07 Å. The rhodium anion, [Rh(SnCl 3) 4(SnCl 4)] 5−, is a trigonal bipyramid with the two axial RhSn bonds, 2.493 Å in length, and the three equatorial bonds, 2.546, 2.540, and 2.540 Å. One of the three tin atoms in the equatorial trigonal plane forms a distorted trigonal bipyramid with two short SnCl bonds 2.384 Å in length and two long bonds, 2.733 Å. The other four tin atoms have a distorted tetrahedral arrangement with an average SnCl bond length of 2.42 Å. The tin anion, [SnCl 6] 4−, which is not coordinated to rhodium, forms extremely long SnCl bonds of 2.763, 2.800, and 2.893 Å in a distorted octahedral arrangement.

Chlorine-35 nuclear quadrupole resonance studies on some tin(IV) chloride adducts

The 35Cl n.q.r. spectra of a series of tin(IV) chloride adducts SnCl4·2L [L = MeCN, CH2CHCN, ButCN, PhCN′ CH2(CN)2, 1,2-C6H4(CN)2, SMe2O, or tht (tetrahydrothiophen)] have been recorded at various temperatures and used to deduce whether these complexes are cis or trans. A trans structure is indicated for SnCl4·2tht, cis structures for the remainder. When compared with other published n.q.r. and structural data, our results indicate that the 35Cl n.q.r. frequencies are related to the Sn–Cl bond lengths in such systems. The higher 35Cl n.q.r. frequencies tend to be associated with the shorter bonds, though the frequencies also vary markedly with temperature.

Crystal structures of M 2SnCl 6 salts. An analysis of the “crystal field effect” in their nuclear quadrupole resonance and vibrational spectra

The effects of univalent cations, M = K +, NH 4 +, Rb +, Cs +, and (CH 3) 4N +, on divalent anions M′Cl 6 2−, where M′= So, Pt, Re, Te, and Pb, in M 2M′Cl 6 salts having space group F m3 m have been analyzed by nuclear quadrupole resonance and vibrational spectroscopy. Single crystal X-ray diffraction collected by counter methods was carried out on the SnC16 salts, and they were found to have SnCl bond lengths and unit cell dimensions respectively of 2.411(2), 9.9818(3) Å (K +); 2.421(l),10.0442(4) Å (NH 4 +); 2.423(4), 10.0961(3) Å (Rb +); 2.423(5),10.3552(2) Å (Cs +); 2.402(3), 12.835(2) Å ((CH 3) 4N +). Full matrix least-squares refinement led to R values of 0.048, 0.054, 0.092, 0.116, and 0.066, respectively. The riding and independent motion models also lead to similar bond lengths. The 35Cl NQR frequencies in the M′Cl 6 2− ion steadily increase in this series as the cation increases in size. For SnCl 6 2− the range is 15.063 to 16.674 MHz. The a 1 g vibrational motion steadily decreases and for the SnCl 6 2− ion the range is 321 to 305 cm −1. The 35Cl NQR data correlate with the Born repulsive potential, e −r ϱ , between ions and does not correlate with other reasonable potentials. This repulsive potential, probably operating through variable amounts of Sternheimer antishielding, is proposed to be the dominant factor in the crystal field effect in the NQR spectra of these salts. The decreases in the a 1 g vibrational frequencies also accompany this effect. The variable sensitivity of other M′Cl 6 2− ions to the cations is accountable in terms of differences in polarization of the anions as a function of their size.

Crystal structure of chlorotris(tetracarbonylcobalt)tin, ClSn[Co(CO) 4] 3

The molecular structure of the title compound is unequivocally established by X-ray crystallography. The coordination of Co atoms is trigonal-bipyramidal, whereas that of Sn atom being distorted tetrahedral. The mean Sn-Co distance is 2.60 «. The Sn-Cl bond length (2.54 «) is definitely greater than the sum of covalent radii (2.39 «.)

Metal–metal bonding in co-ordination complexes. Part VI. Crystal structure of dicarbonylcyclopentadienyl(trichlorostannyl)iron

The crystal and molecular structure of dicarbonyl-π-cyclopentadienyl(trichlorostannyl)iron has been determined by X-ray methods using the intensities of 2561 spectra measured by counter diffractometry. The crystals are triclinic, space group P, a= 11·018(2), b= 8·357(1), c= 6·627(1)A, α= 106·24(1), β= 84·77(1), γ= 96·39(1)°, Z= 2. The structure was determined by the heavy atom method and refined by block-diagonal least-squares techniques with individual anisotropic thermal parameters to R= 0·039.The molecule contains a short Sn–Fe bond, 2·467(2)A, and evidence is presented that this is a σ-bond. The Fe–Sn–Cl and Cl–Sn–Cl angles lie in the ranges 116–121° and 96–100° respectively. The Sn–Cl bond lengths are 2·350(2), 2·358(2), and 2·373(2)A. Mean bond lengths in the (π-C5H5)Fe(CO)2 moiety are : Fe–C(ring), 2·092(3); Fe–C, 1·785(6); C–O, 1·130(8); and C–C, 1·408(5)A. Molecular interactions are of normal van der Waals type and there are no abnormally short intra- or inter-molecular contacts.

The crystal structure of a compound containing tin(IV) in both 5-fold and 6-fold co-ordination: [(CH3)2SnCl,terpyridyl]+[(CH3)2SnCl3

A three-dimensional X-ray crystal structure analysis of the compound of composition (CH3)4Sn2Cl4, terpyridyl has established that it is monochlorobismethyl-2,2′,2″-terpyridyltin(IV) trichlorobismethylstannate(IV). The crystals are triclinic, space group P with a= 15·71, b= 10·04, c= 10·30 A, α= 67·7°, β= 115·9°, γ= 119·6°. There are two formula units per unit cell, observed and calculated densities being 1·75 and 1·80 g.cm.–1. 1589 photographically measured intensities were included in a full-matrix least-squares refinement which led to a conventional R of 13%. In the cations, the tin atom is bonded to a highly distorted octahedral arrangement of two trans-methyl groups, three nitrogen atoms, and a chlorine atom. The Sn–Cl bond length of 2·65(1)A is the greatest yet encountered. The anions are trigonal bipyramidal with both methyl groups equatorial and subtending an angle of 140° at the tin atoms. Sn–Cl bond lengths in the anion are 2·32(1)A(equatorial) and a mean of 2·54(2)A(axial).