Preparation, characterization, and structural determination of cubic and triclinic tris (tetra-n-butylammonium) hexakisisothiocyanatoscandate (III) (original) (raw)
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Structural analysis of tris(tetra-n-butylammonium) hexakisisothiocyanatoyttrate(III)
1999
The structural analysis of [(n-C 4 H 9) 4 N] 3 [Y(NCS) 6 ] (I) using single-crystal diffraction data and full-matrix least squares refinement has been carried out. The hexaisothiocyanate complex crystallizes in the centrosymmetric triclinic space group P1 ළ (No. 2) with unit cell constants of a ϭ 12.431(1), b ϭ 12.866(1), c ϭ 22.750(2) Å , Ͱ ϭ 90.78(1), ͱ ϭ 92.05(1), Ͳ ϭ 96.67(1)Њ, and Z ϭ 2. The molecular unit consists of three separate cationic tetra-n-butylammonium groups and an independent hexakisisothiocyanatoyttrate anionic group in which the six thiocyanate ligands are octahedrally coordinated through the N atom to the Y central ion. Selected bond distances and angles are presented as well as the synthesis and peripheral studies of (I).
European Journal of Chemistry
The reactions of Schiff base 1-(1-hydroxypropan-2-ylidene)thiosemicarbazide (H2L), with salt of thiocyanate metal (II) (Co, Ni, or Zn), provided one dinuclear and two new mononuclear complexes, formulated respectively as {[Co(LH)2]2·[Co(NCS)4] ·2(MeOH)} (1), {[Ni(H2L)2]·[(NCS)2]} (2) and [Zn(H2L)(NCS)2] (3). These compounds have been studied and characterized by elemental analysis, infrared, and ultraviolet-visible (UV-vis) spectroscopies. The structures of the three complexes have been resolved by X-ray crystallography technique. The dinuclear complex 1 crystallizes in the orthorhombic space group Fdd2 with the following unit cell parameters a = 33.1524 (3) Å, b = 19.3780 (2) Å, c = 13.2533 (2) Å, V = 8514.28 (17) Å3, Z = 16, R1 = 0.025 and wR2 = 0.063, the mononuclear complex 2 crystallizes in the monoclinic space group P21/n with the following unit cell parameters a = 11.5752 (1) Å, b = 12.3253 (1) Å, c = 14.2257 (2) Å, β = 106.855 (1)°, V = 1942 (4) Å3, Z = 4, R1 = 0.038 and wR2...
CCDC 2085329: Experimental Crystal Structure Determination
2021
Doubledecker silsesquioxane (DDSQ), a type of incompletely condensed silsesquioxane, has been used as a molecular precursor for synthesizing new organotin discrete and oligomeric compounds. The equimolar reaction between DDSQ tetrasilanol (DDSQ-4OH) and Ph 2 SnCl 2 in the presence of triethylamine leads to obtaining discrete [Ph 4 Sn 2 O 4 (DDSQ)(THF) 2 ] (1). The change of sterically bulky aryl Ph 2 SnCl 2 precursor to linear alkyl n Bu 2 SnCl 2 led to the isolation of oligomeric [ n Bu 4 Sn 2 O 4 (DDSQ)] (2). The structures of compounds 1 and 2 have been demonstrated using single-crystal X-ray diffraction measurements. Indeed, the formation of oligomeric organotin DDSQ compound (2) was determined using GPC and MALDI-TOF mass spectroscopy. In compound 1, the geometry of the tin atom is fivecoordinated trigonal bipyramidal by two phenyl groups, two Si-O from DDSQ and one tetrahydrofuran. Compound 2 contains four coordinated two peripheral tin atoms and two five-coordinated central tin atoms, in which, the fifth coordinating oxo groups in the central tin atoms create the bridge between two different DDSQ units that leads to the formation of oligomeric structure. Density functional theory calculations on organotin DDSQs infer that the obtained lattice energy for compound 1 is far higher than for the case of compound 2, which indicates that the crystal of compound 1 is better stabilized in its crystal lattice with stronger close packing via intermolecular interactions between discrete molecules with coordinated THF compared to the crystal of compound 2. The greater stability arises mainly due to the sterically bulkier phenyl groups attached to the tin centers in compound 1, which provide accessibility for accommodating the THF molecule per tin via Sn-THF bonding, while contrarily the smaller n-butyl groups aid the polymerization of the four repeating units of [SnSi 4 O 7 ] or two Sn 2 O 4 (DDSQ) through m-oxo groups. Both compounds 1 and 2 were chosen to be promising precursors for the synthesis of ceramic tin silicates. The thermolysis of 2 at 1000 1C afforded the mixture of crystalline SnSiO 4 and SiO 2 but the same mixture was only formed by thermolysis of 1 at relatively higher temperature (1500 1C), which infers that compound 1 is more stable than compound 2 that is in good synergy with theoretical lattice energy.
Syntheses, spectroscopic characterization and crystal structures
Polyhedron, 2006
Some new phosphoramidates with formula 4-F-C 6 H 4 C(O)N(H)P(O)X 2 , X = NC 4 H 8 (1), NC 5 H 10 (2), 4-CH 3-NC 5 H 9 (3), NC 4 H 8 O (4), NC 6 H 12 (5), N(CH 2 CH 3) 2 (6), N(CH 2 CH 2 CH 3) 2 (7) were synthesized. The reaction of compound 2 with dimethyltin(IV) dichloride leads to an octahedral organotin(IV) complex, SnCl 2 (CH 3) 2 [4-F-C 6 H 4 C(O)N(H)P(O)(NC 5 H 10) 2 ] 2 (8) with equal ligands in trans positions. These compounds were characterized by IR, 1 H, 13 C, 31 P, 119 Sn NMR, mass spectroscopy and elemental analysis. The structures have been determined for compounds 1, 2, 4, 5 and 8. Compound 2 exists as four symmetrically independent molecules in the crystalline lattice. Compounds 1, 4 and 5 form dimmers via intermolecular-P@OÁ Á ÁH-Nhydrogen bonds that in 1 is centrosymmetric. In compound 2, two dimmers were formed; each of them was produced between two adjacent independent molecules. In compounds 1, 2, 3, 4 and 8, containing five-and six-membered ring amine groups, 3 J(P,C aliphatic) > 2 J(P,C aliphatic). Compound 5 with seven-membered ring amine, similar to compounds 6 and 7 with acyclic aliphatic amines, shows that 2 J(P,C aliphatic) > 3 J(P,C aliphatic). Mass spectra of these compounds indicate the 4-F-C 6 H 4 CO + and 4-F-C 6 H 4 CN + fragments.
Synthesis and characterization of new
di-n-butyl [bis{dimethyl-2-(3-oxo-5-phenyl(4-subtituted)-penten-5-ato)malonates}]tin(IV): The crystal structure of di-n-butyl[bis{dimethyl-2-[5-(4-nitrophenyl)-3-oxo-penten-5-ato]malonate}]tin(IV) Abstract The synthesis of four new di-n-butyl[bis{dimethyl-2-(3-oxo-5-phenyl(4-subtituted)penten-5-ato)malonates}]tin(IV) 2a–2d is reported. These complexes have been characterized by 1 H, 13 C, 119 Sn NMR, HMQC, HMBC, infrared spectroscopy and mass spec-trometry (FAB). Their structures in CDCl 3 solution show a distorted octahedral geometry with a trans disposition of the n-butyl substituents. The 119 Sn NMR study at low variable-temperature indicates the presence of trans anti-and syn-isomers, and solid-state 13 C and 119 Sn NMR spectra of compound 2d give also evidence of the mixture of trans isomers. The X-ray diffraction study of com-pound 2d at 168 K shows only the trans syn-isomer, where the metal is six-coordinated in a skewed trapezoidal bipyramidal (STB) geometry.
Research on Chemical Intermediates, 2014
N-Benzyl-4-(3-benzylcarbamoyl-propyldisulfanyl)-butyramide (BBCPB, C 22 H 28 N 2 O 2 S 2) has been synthesized and a single crystal of the title compound was obtained. Moreover, the Raman (100-3,500 cm-1) and infrared (200-4,000 cm-1) spectra of the solid sample were recorded and the structure of BBCPB was characterized by single-crystal X-ray diffraction. The C=O and N-H moieties of two symmetrically independent molecules in the unit cell interact via intermolecular hydrogen bonds (C=OÁÁÁN-H)], whereas the benzene rings are oriented diagonally in opposite directions. The unit cell parameters are: a = 5.4500 (3) Å , b = 8.6362 (4) Å , and c = 23.4738 (14) Å. The molecular geometry and the vibrational frequencies of an isolated molecule was optimized using Density Functional Theory with the methods of B3LYP and B3PW91 utilizing the 6-31G(d) basis set. The computed bond lengths were found to be in excellent agreement with X-ray values (R 2 = of 0.96-0.97), whereas the bond angles were less congruent with the B3LYP and B3PW91 methods (R 2 = 0.58-0.74). These Electronic supplementary material The online version of this article (
2021
Received: 20 January 2021 Received in revised form: 05 April 2021 Accepted: 17 April 2021 Published online: 30 June 2021 Printed: 30 June 2021 Complexes of Co(II), [Co(C26H24N8O2)]·(ClO4)2·(H2O)2 (1), and Cu(II), [Cu(C26H23N8O2)]·(ClO4) (2), have been synthesized. The prepared two compounds were characterized by elemental analysis, infrared and their structures were determined by single-crystal X-ray diffraction. The compound 1 crystallizes in the triclinic space group P-1 with the following unit cell parameters: a = 8.880 (5) Å, b = 10.529 (5) Å, c = 18.430 (5) Å, α = 99.407 (5)°, β = 102.174 (5)°, γ = 100.652 (5)°, V = 1618.2 (13) Å3, Z = 2, T = 293(2), μ(MoKα) = 0.77 mm-1, Dcalc = 1.582 g/cm3, 16135 reflections measured (5.050° ≤ 2θ ≤ 59.152°), 7648 unique, Rint = 0.034 which were used in all calculations. The final R1 was 0.066 (I ≥ 2σ(I)) and wR2 was 0.22 (all data). The compound 2 crystallizes in the monoclinic space group P21/c with the following unit cell parameters : a = 11...
Inorganic Chemistry, 2000
The compounds (Me 4 N)[A{M(SC{O}Ph) 3 } 2 ] (A ) K, M ) Cd (2); A ) Na, M ) Hg (3); and A ) K, M ) Hg (4)) were synthesized by reacting the appropriate metal chloride with A + PhC{O}Sand Me 4 NCl in the ratios 1:3:1 and 2:6:1. The structures of these compounds were determined by single-crystal X-ray diffraction methods. All the compounds are isomorphous, isostructural, and crystallized in the space group P1 h with Z ) 1. Singlecrystal data for 2: a ) 10.6670(2) Å, b ) 11.1522(2) Å, c ) 11.9294 Å, R ) 71.782(1)°, ) 85.208(1)°, γ ) 69.418(1)°, V ) 1261.40(4) Å 3 , D calc ) 1.528 g cm -3 . Single-crystal data for 3: a ) 10.840(2) Å, b ) 10.946(4) Å, c ) 12.006(3) Å, R ) 72.18(2)°, ) 86.75(2)°, γ ) 67.43(2)°, V ) 1249.3(6) Å 3 , D calc ) 1.756 g cm -3 . Single-crystal data for 4: a ) 10.4780(1) Å, b ) 11.2563(2) Å, c ) 11.9827(2) Å, R ) 71.574(1)°, ) 85.084(1)°, γ ) 70.705(1)°, V ) 1265.23(3) Å 3 , D calc ) 1.755 g cm -3 . In the [A{M(SC{O}Ph) 3 } 2 ]anions, each M(II) atom is bonded to three thiobenzoate ligands through sulfur atoms, giving a trigonal planar MS 3 geometry. The carbonyl oxygen atoms from the two [M(SC{O}Ph) 3 ]anions are bonded to the alkali metal atom, providing an octahedral environment. Solution metal NMR studies showed the concentration-dependent dissociation of the alkali metal ions in the trinuclear anions.