Oxonium trans-bis(oxalato)rhodate and related sodium salts: a rare example of crystalline complex acid

Author(s):  
Ilia Garkul ◽  
Andrey Zadesenets ◽  
Evgeny Filatov ◽  
Iraida Baidina ◽  
Sergey Tkachev ◽  
...  

New coordination compounds trans-bis(oxalato)diaquarhodiate sodium dihydrate Na[Rh(H2O)2Ox2]·2H2O (crystallizes in two polymorphic forms NaRh-1 and NaRh-2), trans-bis(oxalato)hydroxoaquarhodiate sodium tetrahydrate Na2[Rh(H2O)(OH)Ox2]·4H2O (Na2Rh) and trans-bis(oxalato)diaquarhodic acid tetrahydrate (H3O)[Rh(H2O)2Ox2]·4H2O (HRh) are synthesized. The compounds are characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction. NaRh-1, NaRh-2 and Na2Rh crystallize in space group P 1. Trans-bis(oxalato)diaquarhodic acid exists not only in solution, but can also crystallize as a tetrahydrate (space group C2/c). The formation of various species in solution of rhodium hydroxide in oxalic acid and their redistribution were studied using 103Rh NMR spectroscopy.

2000 ◽  
Vol 55 (6) ◽  
pp. 495-498 ◽  
Author(s):  
Katerina E. Gubina ◽  
Vladimir A. Ovchynnikov ◽  
Vladimir M. Amirkhanov ◽  
Viktor V. Skopenkoa ◽  
Oleg V. Shishkinb

N,N′-Tetramethyl-N"-benzoylphosphoryltriamide (I) and dimorpholido-N-benzoylphosphorylamide (II), and their sodium salts Nal, Nall were synthesized and characterized by means of IR and 1H, 31P NMR spectroscopy. The structures of I, II were determined by X-ray diffraction: I monoclinic, space group P2i/c with a = 10.162(3), b= 11.469(4), c = 12.286(4) Å , β = 94.04°, V = 1428.4(8) A 3, Z = 4, p(calcd) = 1.187 g/cm3; II monoclinic, space group C2/c with a = 15.503(4), b = 10.991(3), c = 22.000(6) Å, β = 106.39°, V = 3596.3(17) Å3, Z = 8, p(calcd.) = 1.253 g/cm3. The refinement of the structures converged at R = 0.0425 for I, and R = 0.068 for II. In both structures the molecules are connected into centrosymmetric dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups.


2000 ◽  
Vol 55 (11) ◽  
pp. 1015-1019 ◽  
Author(s):  
Katerina E. Gubina ◽  
Vladimir M. Amirkhanov

N,N′-Tetramethyl-N″-p-chlorobenzoylphosphoryltriamide (I), N,N′-tetramethyl-N″-o-fluorobenzoylphosphoryltriamide (II) and their sodium salts were synthesized and characterized by means of IR and 1H , 31P NMR spectroscopy. The structures of both compounds were determined by X-ray diffraction (I triclinic, space group P1̄ with a = 12.073(2), b = 12.869(3), c = 12.854(4) Å, α = 56.93(2), β = 62.45(2), γ = 66.34(2)° V = 1453.7(6)Å3, ρ(caled.) = 1.324 mg/cm3, Z = 4 and R = 0.0545, wR2 = 0.1425; II monoclinic, space group P2(1)/n with a = 10.051(2), b = 13.093(2), c = 10.856(2) Å, β = 108.36(2)°, V = 1355.9(4) Å3, ρ(caled.) = 1.339 mg/cm3, Z = 4 and R = 0.0533, wR2 = 0.1263). In both structures the molecules are associated into dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups. In I the unit cell consists of two independent molecules connected into non-symmetric dimers, in II of centrosymmetric dimer molecules.


Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 149-163
Author(s):  
Duncan Micallef ◽  
Liana Vella-Zarb ◽  
Ulrich Baisch

N,N′,N″,N‴-Tetraisopropylpyrophosphoramide 1 is a pyrophosphoramide with documented butyrylcholinesterase inhibition, a property shared with the more widely studied octamethylphosphoramide (Schradan). Unlike Schradan, 1 is a solid at room temperature making it one of a few known pyrophosphoramide solids. The crystal structure of 1 was determined by single-crystal X-ray diffraction and compared with that of other previously described solid pyrophosphoramides. The pyrophosphoramide discussed in this study was synthesised by reacting iso-propyl amine with pyrophosphoryl tetrachloride under anhydrous conditions. A unique supramolecular motif was observed when compared with previously published pyrophosphoramide structures having two different intermolecular hydrogen bonding synthons. Furthermore, the potential of a wider variety of supramolecular structures in which similar pyrophosphoramides can crystallise was recognised. Proton (1H) and Phosphorus 31 (31P) Nuclear Magnetic Resonance (NMR) spectroscopy, infrared (IR) spectroscopy, mass spectrometry (MS) were carried out to complete the analysis of the compound.


1993 ◽  
Vol 48 (6) ◽  
pp. 771-777 ◽  
Author(s):  
Ulrich Abram ◽  
Bernd Lorenz

Novel rhenium complexes with terminal thiocarbonyl groups have been synthesized from ReCl3(Me2PhP)3 and sodium diethyldithiocarbamate. mer-(Diethyldithiocarbamato)tris-(dimethylphenylphosphine)(thiocarbonyl)rhenium(I), mer-[Re(CS)(Me2PhP)3(Et2dtc)], and tris(diethyldithiocarbamato)(thiocarbonyl)rhenium(III), [Re(CS)(Et2dtc)3] have been studied by infrared and NMR spectroscopy, mass spectrometry and X-ray diffraction.mer-[Re(CS)(Me2PhP)3(Et2dtc)] crystallizes orthorhombic in the space group Pna21 with a = 1516.1(2), b = 2189.8(2) and c = 1035.6(1) pm. Structure solution and refinement converged at R = 0.042. The coordination geometry is a distorted octahedron. The Re—C bond length is found to be 184(2) pm.[Re(CS)(Et2dtc)3] crystallizes monoclinic in the space group P21/c with a = 962.2(6), b = 1744.0(2), c = 1537.4(6) pm and β = 96.21(1)°. The final R value is 0.028. In the monomeric complex the rhenium atom is seven-coordinate with an approximate pentagonal-bipyramidal coordination sphere and a rhenium-carbon distance of 181(1) pm.


2006 ◽  
Vol 61 (5) ◽  
pp. 577-582 ◽  
Author(s):  
Manfred Fild ◽  
Peter G. Jones ◽  
Michael Lorms ◽  
Stefan Jäger

The reaction of lithiated Ph(H)PCH2P(H)Ph with (ClCH2)2PPh yields 1,3,5-Triphenyl-1,3,5- triphosphorinane (1) as a mixture of two isomers. The isomers have been separated by column chromatography and characterized by NMR spectroscopy and single crystal X-ray diffraction as the eq-eq-eq (1a) and eq-eq-ax-isomers (1b). (1a) crystallizes with a = 1326.9(3) pm and c = 933.4(3) pm in the rhombohedral space group R3 and displays 3-fold symmetry, showing an eq-eq-eq conformation. (1b) crystallizes in the monoclinic space group P21/c with a = 984.09(12) pm, b = 1757.5(2) pm, c = 1083.13(12) pm, β = 93.329(2)° and displays an ax-eq-eq conformation.


Synthesis ◽  
2017 ◽  
Vol 49 (11) ◽  
pp. 2389-2393 ◽  
Author(s):  
Stefanie Pelzer ◽  
Beate Neumann ◽  
Hans-Georg Stammler ◽  
Nikolai Ignat’ev ◽  
Reint Eujen ◽  
...  

This paper describes the synthesis and comprehensive characterization of tetrakis(pentafluoroethyl)germane. In addition to a complete NMR spectroscopic characterization, including the rarely used 73Ge NMR spectroscopy, Ge(C2F5)4 was studied by IR spectroscopy, mass spectrometry as well as X-ray diffraction analysis. A 73Ge NMR investigation as well as an X-ray diffraction study of the related germane Ge(CF3)4 are also included.


1997 ◽  
Vol 62 (8) ◽  
pp. 1239-1253 ◽  
Author(s):  
Jonathan Bould ◽  
Paul Brint ◽  
John D. Kennedy ◽  
Mark Thornton-Pett ◽  
Lawrence Barton ◽  
...  

[6-(CO)-6-H-6,9-(PPh3)2-6P,5C-μ-(2-Ph2PC6H4)-arachno-6-IrB9H11] (1) results from the reaction of [6-H-6-(PPh3)-6P,5C-μ-(2-Ph2PC6H4)-nido-6-IrB9H12] (2) with carbon monoxide in refluxing benzene. It is characterised by NMR spectroscopy and by single-crystal X-ray diffraction analysis. Crystals were triclinic, space group P1, with a = 10.688(2), b = 13.114(3), c = 22.356(5) Å, α = 78.33(2), β = 89.482(10), γ = 70.884(12)°, and Z = 2. The compound is of the little-examined arachno ten-vertex metallaborane structural type. A second compound of this type, [6-(CO)-6-H-6,6-(PMe2Ph)2-9-(PPh3)-arachno-6-IrB9H11] (3), isolated from a reaction system involving [Ir(CO)Cl(PPh3)2], PMe2Ph and the [nido-B9H12]- anion, has also been characterised crystallographically. Crystals were triclinic, space group P1, with a = 10.389(1), b = 10.511(1), c = 19.699(3) Å, α = 75.03(1), β = 85.53(1), γ = 74.88(1)°, and Z = 2.


2010 ◽  
Vol 65 (12) ◽  
pp. 1462-1466 ◽  
Author(s):  
Michaela K. Meyer ◽  
Jürgen Graf ◽  
Guido J. Reiß

[Me(HO)2P-(CH2)10-P(O)OHMe]2[I3]2・MeHO(O)P-(CH2)10-P(O)OHMe (1) was synthesized and characterized by IR, Raman and NMR spectroscopy. Its structure was determined by singlecrystal X-ray diffraction (T = 100 K; space group P1̄). The structure consists of decane-1,10-diyl-bis- (methylphosphinic acid) molecules and the analogous mono-protonated cations in a ratio 1:2 connected with each other by strong O-H···O hydrogen bonds to form a two-dimensional network. Between these hydrogen-bonded layers, there are elongated cavities each containing two triiodide anions. The intermolecular I· · · I distance of the two enclosed triiodide anions is 3.6317(4) Å and should be considered as an interhalogen bonding interaction.


2018 ◽  
Vol 74 (11) ◽  
pp. 1390-1394 ◽  
Author(s):  
Rami Al-Oweini ◽  
Bassem S. Bassil ◽  
Marwa Itani ◽  
Dilara Börte Emiroğlu ◽  
Ulrich Kortz

Interaction of the mixed-valent 12-manganese coordination complex [MnIII 8MnIV 4O12(CH3COO)16(H2O)4] with the lacunary 9-tungstoarsenate(V) [A-α-AsW9O34]9− resulted in the 10-manganese(III/IV)-containing 36-tungsto-4-arsenate(V), [MnIII 6MnIV 4O4(OH)12(H2O)12(A-β-AsW9O34)4]22− (1). Polyanion 1 was isolated as a hydrated mixed potassium–sodium salt, K14Na8[MnIII 6MnIV 4O4(OH)12(H2O)12(A-β-AsW9O34)4]·104H2O, which crystallizes in the orthorhombic space group Pbcn and was characterized by FT–IR spectroscopy and single-crystal X-ray diffraction, as well as elemental and thermogravimetric analyses. The title polyanion contains a unique [MnIII 6MnIV 4O4(OH)12(H2O)12]14+ core stabilized within the 36-tungsto-4-arsenate(V) framework.


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