Group 15 Complexes with α-Hydroxy Carboxylic Acids: 7. The Preparation and Structure Determination of Sodium (+)-Tartrato Arsenate(III), [Na8As10(C4H2O6)8(C4H3O6)2(H2O)19]n; Silver(I) (+)-Tartrato Arsenate(III), [Ag9As10(C4H2O6)9(C4H3O6)(H4As2O5) (H2O)10]n and Rubidium Citrato Antimonate(III), [Rb2Sb4(C6H5O7)2(C6H6O7)2(C6H7O7)4(H2O)2]

2000 ◽  
Vol 53 (12) ◽  
pp. 917 ◽  
Author(s):  
Raymond C. Bott ◽  
Graham Smith ◽  
Dalius S. Sagatys ◽  
Daniel E. Lynch ◽  
Colin H. L. Kennard
Keyword(s):  
Structure Determination ◽  
Mixed Valence ◽  
Water Molecules ◽  
Charge Balance ◽  
X Ray ◽  
Citrate Complex ◽  
Trigonal Bipyramidal ◽  
Ray Methods ◽  
Ligand Species

The structures of sodium (+)-tartrato arsenate(III),[Na8As10(C4H2O6)8(C4H3O6)2(H2O)19]n(1), silver (+)-tartrato arsenate(III),[Ag9As10(C4H2O6)9(C4H3O6)(H4As2O5)(H2O)10](2) and rubidium citrato antimonate(III)[Rb2Sb4(C6H6O7)6(C6H7O7)2(H2O)2](3) have been determined by X-ray methods and refined to residuals of 0.085(1), 0.072 (2) and 0.065 (3) for 5018, 4487 and 8207 observed reflections,respectively. The (+)-tartrato complexes (1) and (2) are similar instructure to the two known isomorphous silver(I) (+)-tartratoarsenate(III) complexes in that independent anionic[As2(tartrate)2] dimericcages are linked to the sodium or silver counter-cations, respectively,through free carboxyl oxygen atoms. However, the structures are made morecomplex by the presence of labile water molecules in the lattice, resulting insome disorder. Furthermore, charge balance in both (1) and (2) requires thepresence of two and one tri-negative tartrato units, respectively, among theten independent tartrate units in each structure, an unusual feature for Asand Sb complexes with this ligand species. Bond distances within the fivearsenic(III)-(+)-tartrate dimers in each structure are: As–O(hydroxy), 1.75(2)–1.84(2) Å (1); 1.75(3)–1.83(2) Å(2) and As–O (carboxy), 1.94(2)–2.13(3) Å (1);1.95(2)–2.14(2) Å (2). In addition, the structure of (2) has twoshort Ag–As bonds [2.500, 2.524(3) Å] in the terminalsites of two of the f ive independent dimers, as well as an additionalAg–As bond [2.613(4) Å] to an unusual dimeric arseniousacid residue(H4As2O5),part of an As2AgO3 hetero-ringforming the polymeric network structure. The antimony(III) citrate complex (3)is isomorphous and isostructural with the previously reported potassiumanalogue which involves mixed-valence citrato ligands in conventionalbis-chelate four-coordination about the antimony centres, linked by bothseven- and eight-coordinate rubidium ions [Rb–O,2.743(10)–3.102(9) Å]. The arsenic and antimony atoms in allcompounds have typical distorted pseudo-trigonal bipyramidal stereochemistry.

Group 15 Complexes With Carboxylic Acids. V. The Preparation and Crystal Structures of {Ag5As4(C4H2O6)4(H2O)5(X)}n[(C4H2O6) = (+)-Tartrate(4-); X = NO3-, ClO4-]

1993 ◽  
Vol 46 (7) ◽  
pp. 1055 ◽  
Author(s):  
RC Bott ◽  
G Smith ◽  
DS Sagatys ◽  
TCW Mak ◽  
DE Lynch ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Silver Atom ◽  
Silver Ions ◽  
Water Molecules ◽  
Monoclinic Space Group ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
A Chain ◽  
Polymer Framework ◽  
Ray Methods

The structures of two isomorphous silver(I) complexes with arsenic(III) (+)- tartrate [Ag5As4(C4H2O6)4(H2O)5(X)]n [X = NO3- (1), ClO4- (2)] have been determined by X-ray methods and refined to residuals R of 0.045 (1) and 0.028 (2) for 3822 and 3849 observed reflections respectively. Crystals are monoclinic, space group P21 with Z 2 in cells of dimensions a 12.057(3), b 10.651(1), c 12.496(3)Ǻ, β 93.37(2)° for (1), and a 12.170(5), b 10.570(1), c 12.634(4)Ǻ, β 92.74(2)° for (2). The two complexes are isostructural , with polymer framework structures based upon two configurationally identical [As2(C4H2O6)2]2- dimer ions, analogous to these in the tartar emetic structure [As-O (hydroxyl): 1.790(7)-1.804(8)Ǻ(1); 1.768(4)-1.818(4)Ǻ(2). As-O (carboxyl): 1.966(9)-2.118(8)Ǻ(1); 1.940(5)-2.127(5)Ǻ(2)]. However, an arsenic of one of the dimers forms a short bond to a silver atom [As-Ag, 2.729(2)Ǻ(1), and 2.723(1)Ǻ(2)], completing a trigonal-bipyramidal coordination about arsenic. The arsenic dimers are in turn linked by a chain of five silver cation centres through both carboxyl and hydroxyl oxygens which also form intrachain links. All five water molecules are bonded to silver ions, with three of them bridging silver centres. The main difference between the two structures arises from the replacement of the nitrate group in (1) by a perchlorate in (2).

Vier- und fünfgliedrige Phosphorheterocyclen, XXXVIII [1] Azaphospholo-benzoxazaphosphole - Synthese, Prototropie und Struktur / Four- and Five - membered Phosphorus Heterocycles, XXXVIII [1] Azaphospholo-benzoaxazaphospholes - Preparation, Proton Shift and Structure

1979 ◽  
Vol 34 (7) ◽  
pp. 906-910 ◽  
Author(s):  
Alfred Schmidpeter ◽  
Josef Helmut Weinmaier
Keyword(s):  
Structure Determination ◽  
Cinnamic Aldehyde ◽  
X Ray ◽  
Proton Shift ◽  
Trigonal Bipyramidal ◽  
Bicyclic Structure ◽  
Bicyclic System ◽  
Methyl Phenyl ◽  
The Ideal

Abstract The o-hydroxyanile of cinnamic aldehyde reacts with methyl, phenyl, oxy-, and aminochlorophosphanes in a combined substitution and oxidative addition to give phosphoranes with the above mentioned bicyclic structure containing phosphorus as bridgehead. For the aminosubstituted species the reaction is followed by a 1.3 proton shift in the C3 moiety from the cinnamic aldehyde. Whether the bicyclic system occupies meridional of facial positions of the phosphorus trigonal bipyramid is shown to depend on the nature of the phosphorus substituents. An X - ray structure determination of a tricyclic derivative with axial annelation shows the deviation from the ideal trigonal bipyramidal geometry to lie on the Berry pseudorotion pathway

Über die Darstellung neuer spirocyclischer N,N′-Dimethylsulfamid-substituierter Phosphorverbindungen und Ν,N′-Dimethylsulfamid-verbrückter Diphosphorverbindungen / The Preparation of New Spirocyclic N,N′-Dimethylsulphamide-Substituted Phosphorus Compounds, and of Some N,N′-Dimethylsulphamide-Bridged Diphosphorus Compounds

1990 ◽  
Vol 45 (2) ◽  
pp. 175-183 ◽  
Author(s):  
Peter G. Jones ◽  
Anke Meyer ◽  
Reinhard Schmutzler
Keyword(s):  
Crystal Structure ◽  
Nitrogen Atom ◽  
Structure Determination ◽  
Sodium Azide ◽  
Mixed Valence ◽  
Spectroscopic Properties ◽  
Phosphorus Compounds ◽  
Molar Ratio ◽  
X Ray ◽  
Trigonal Bipyramidal

The reactions of 4-chloro-1,3,5,7-tetramethyl-2,2,6,6-tetraoxa-2,6-dithia-1,3,5,7-tetraaza-4λ5-phosphaspiro[3.3]heptane (1) with trimethylsilyl compounds and sodium azide led to a series of spirocyclic N,N′-dimethylsulphamide-substituted phosphoranes (2—5). The nature of the pentaaza-spirophosphorane (4) was confirmed by an X-ray crystal structure determination (C2/c, a = 991.8(4), b = 1185.6(6), c = 1224.9(5) pm,β = 108.64(3)°, Z = 4, R = 0.041 for 1065 unique observed reflections); a crystallographic twofold axis passes through phosphorus and the nitrogen atom of the NMe2 group. The geometry at phosphorus is to a good approximation trigonal bipyramidal. The azido-spirophosphorane (5) undergoes Staudinger-type reactions with phosphorus(III) compounds (PPh3, dppm) to form the mixed-valence phosphorus compounds 6—8. The reaction of N,N′-dimethylsulphamide or N,N′-dimethyl-N,N′-bis(trimethylsilyl)-sulphamide with dichlorophosphines RPCl2 (R = Me, Ph) in a molar ratio 1:2 leads to the formation of the acyclic N,N′-dimethylsulphamide-bridged diphosphorus compounds 9 and 10, respectively. The spectroscopic properties (and, for 4, the X-ray crystal structure) of the products are compared with those of analogous urea-bridged phosphorus compounds.

Structural Systematics of Rare Earth Complexes. XII Solvated 1 : 1 Adducts of Some Lanthanoid(III) Carboxylates with 1,10-Phenanthroline and 2,2′:6′,2″-Terpyridine

1999 ◽  
Vol 52 (6) ◽  
pp. 481 ◽  
Author(s):  
Cameron J. Kepert ◽  
Lioubov I. Semenova ◽  
Lu Wei-Min ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Rare Earth ◽  
Single Crystal ◽  
Structural Characterization ◽  
Structure Determination ◽  
Room Temperature ◽  
Water Molecules ◽  
X Ray ◽  
Structural Characterizations

A room-temperature single-crystal X-ray structure determination of the 1 : 1 adduct of 1,10-phenanthroline (`phen") with lutetium(III) acetate (as its dihydrate) is recorded. Crystals are triclinic, P 1, a 12·430(8), b 10·681(4), c 8·134(8) Å, α 74·76(6), β 84·81(7), γ 74·29(4)°, Z = 2 f.u.; conventional R on |F| was 0·031 for No 3939 independent ‘observed’ (I > 3σ(I)) diffractometer reflections. The complex [(N,N′-phen)(O,O′-ac)Lu(O-ac-O′)4Lu(O,O′-ac)(N,N′-phen)].2H2O is binuclear, the lutetium being eight-coordinated by bidentate phen and ac (acetate) ligands and four oxygen atoms from the bridging acetate ligands. Also recorded is the structural characterization of 1 : 1 Lu(ac)2Cl/tpy (tpy = 2,2′:6′,2″-terpyridine) as its pentahydrate; this complex is triclinic, P 1, a 12·410(3), b 11·559(4), c 9·976(4) Å, α 85·19(3), β 70·30(3), γ 65·70(2)°, Z = 2, R 0·049 for No 4717. The complex is shown to be [(tpy)(H2O)2Lu(O2CCH3)2]Cl.3H2O, with the lutetium nine-coordinated by tridentate tpy, a pair of bidentate acetates and two unidentate water molecules, with the chloride uncoordinated. Structural characterizations of a number of 1 : 1 adducts of variously solvated lanthanoid(III) trichloroacetates, Ln(tca)3, with tpy are also recorded. Yb(tca)3/tpy/MeOH (1 : 1 : 1) is triclinic, P 1, a 14·016(4), b 12·951(5), c 9·604(3) Å, α 73·89(3), β 76·56(3), γ 69·20(3)°, Z = 2 f.u., R 0·057 for No 4465. The complex is mononuclear, the eight-coordinate N3YbO5 array containing tridentate tpy, unidentate methanol, and two unidentate and one bidentate chelating anions. 1 : 1 : 1 Ln(tca)3/tpy/OH2 adducts for Ln = La(-)Nd are triclinic, P 1, a ≈ 13·4, b ≈ 12·47, c ≈ 11·5 Å, α ≈ 114·5, β ≈ 89·9, γ ≈ 115·6°, Z = 1 binuclear array, R 0·061, 0·071 for No 3240, 2394. The two Ln atoms are O,O′-bridged by a pair of anions, the N3LnO6 nine-coordinate lanthanoid environment being completed by a tridentate tpy, one water, one unidentate and one bidentate anion. A 1 : 1 : 1 Lu(tca)3/tpy/OH2 array, by contrast, is triclinic, P 1, a 16·569(8), b 14·815(5), c 14·375(6) Å, α 62·05(3), β 81·35(4), γ 77·97(3)°, Z = 4 ‘mononuclear’ f.u., R 0·067 for No 6710. The array, remarkably, contains species of both of the above types in a 1 : 2 binuclear-to-mononuclear ratio, but with water replacing methanol in the mononuclear array.

Mossbauer spectrum, molecular and crystal structure of tin(II) diethyldithiocarbamate

1976 ◽  
Vol 29 (1) ◽  
pp. 213 ◽  
Author(s):  
BF Hoskins ◽  
RL Martin ◽  
NM Rohde
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Quadrupole Splitting ◽  
Structure Determination ◽  
Lone Pair ◽  
Molecular And Crystal Structure ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal

The syntheses and Mossbauer spectra of four sulphur-chelated compounds of tin(11) are reported. A single-crystal X-ray structure determination of Sn(dedtc)2 has established that the molecule possesses a strongly distorted trigonal bipyramidal configuration with a sterically active lone pair of electrons occupying an equatorial coordination position. While the Mossbauer quadrupole splitting for tin(11) compounds, in general, is consistent with a sterically active pair of electrons, its magnitude appears to be more sensitive to the nature of the ligand rather than the tin stereochemistry.

Ternäre Silicide des Lithiums mit Yttrium oder Neodym mit modifizierter U3Si2-Struktur /Ternary Silieides of Lithium with Yttrium or Neodymium in a Modified U3Si2-Type Structure

1979 ◽  
Vol 34 (9) ◽  
pp. 1237-1239 ◽  
Author(s):  
Gunter Steinberg ◽  
Hans-Uwe Schuster
Keyword(s):  
Crystal Structure ◽  
Structure Determination ◽  
Type Structure ◽  
Crystal Structure Determination ◽  
X Ray ◽  
Lattice Constants ◽  
Ray Methods

The two isotypic compounds LiY2Si2 and LiNd2Si2 were prepared and chemically characterized. The crystal structure determination of LiY2Si2 by means of X-ray methods revealed a modified U3Si2-structure. The lattice constants of the tetragonal cells are:LiY2Si2: a = 710.5 pm, c = 414.4 pm.LiNd2Si2 : a = 737.0 pm, c = 424.2 pm.

X-Ray Crystal Structure Determination of Some Sodium Anthraquinone Sulfonate Derivatives

1993 ◽  
Vol 46 (10) ◽  
pp. 1595 ◽  
Author(s):  
e Gamag ◽  
e Gamag ◽  
BM Peake ◽  
BM Peake ◽  
J Simpson ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Structure Determination ◽  
X Ray Diffraction ◽  
Molecular Mechanics Calculations ◽  
X Ray ◽  
Photochemical Behaviour ◽  
Sufficient Magnitude ◽  
Ray Methods

The crystal structures of sodium 9,10-dioxo-9,10-dihydroanthracene-2-sulfonate hydrate (1) and sodium 9,10-dioxo-9,10-dihydroanthracene-1,5-disulfonate trihydrate (2) have been determined by single-crystal X-ray diffraction at 253 K and refined to R 0.03 for (1) (1535 reflections) and R 0.04 for (2) (1409 reflections). Crystals of (1) are monoclinic, P21, a 17.395(5), b 6.625(2), c 5.537(1)Ǻ, β 91.87(2)°, Z 2, and those of (2) are orthorhombic, Pnma, a 11.332(4), b 20.048(5), c 7.634(3)Ǻ, Z 4. The results of molecular mechanics calculations on these two molecules were in general agreement with those determined by X-ray methods. The effect of sulfonate substitution in the 1-position compared with that in the 2-position include a small lengthening of the C-S bond and a displacement of the sulfur and quinone oxygen atoms to opposite sides of the plane of the substituted aromatic ring. However, these differences do not appear to be of sufficient magnitude to account for the much greater differences in the electrochemical and photochemical behaviour of these two classes of anthraquinone sulfonate derivatives.

Characterization of a Crystalline Residue From a Swimming Pool: Disodium Copper(II) Tetrakis(isocyanurate) Hexahydrate

1992 ◽  
Vol 45 (11) ◽  
pp. 1927 ◽  
Author(s):  
RD Hart ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Chemical Analysis ◽  
Structure Determination ◽  
Title Compound ◽  
Swimming Pool ◽  
Water Molecules ◽  
Formula Unit ◽  
Sodium Ions ◽  
X Ray

Coupled with chemical analysis, a single-crystal X-ray structure determination of lilac deposit from a swimming pool, shows the deposit to be the title compound Na2Cu(C3H2N3O3)4.6H2O. Crystals are triclinic, P1, a 10.459(1), b 10.434(3), c 6.762(4) � , α: 71.73(4), β 83.67(4), γ 62.82(2), Z 1 formula unit; 1265 'observed' diffractometer reflections were refined to R 0.052. The copper atoms are located on crystallographic inversion centres, four-coordinated by a pair of water molecules [Cu-O, 1.937(6) � ] and a pair of ligand nitrogen atoms [Cu-N, 1.941(9) � ]. Interactions from ligand oxygen atoms to sodium ions link the structure into a polymeric array.

The protonation of the ethylenediphosphinetetraacetate anion and the crystal structure of the bis (hydrogen bromide) of ethylenediphosphinetetraacetic acid

1981 ◽  
Vol 46 (12) ◽  
pp. 3063-3073 ◽  
Author(s):  
Jana Podlahová ◽  
Bohumil Kratochvíl ◽  
Vratislav Langer ◽  
Josef Šilha ◽  
Jaroslav Podlaha
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Structure Determination ◽  
Free Acid ◽  
Hydrogen Bromide ◽  
Carboxyl Groups ◽  
Spectroscopic Methods ◽  
X Ray ◽  
Partial Formation

The equilibria and mechanism of addition of protons to the ethylenediphosphinetetraacetate anion (L4-) were studied in solution by the UV, IR, 1H and 31P NMR spectroscopic methods. A total of six protons can be bonded to the anion. They are added stepwise, first with partial formation of zwitterions containing P-H bonds, which then dissociate with formation of the free acid, H4L, where all four protons are bonded in carboxyl groups. The formation of zwitterions is strongly dependent on the concentration. In the final stage, the acid bonds two additional protons to form the bis-phosphonium cation, H6L2+. A number of isostructural salts containing this cation, H4L.2 HX (X = Cl, Br, I), have been prepared. The X-ray crystal structure determination of the bromide confirmed the expected arrangement. The bromide crystals are monoclinic, a = 578.2, b = 1 425.0, c = 1 046.7 pm, β = 103.07° with a space group of P21/c, Z = 2. The final R factor was 0.059 based on 1 109 observed reflections. The structure consists of H6L2+ cations containing protons bonded to phosphorus atoms (P-H distance 134 pm) and of bromide anions, located in gaps which are also sufficiently large for I- anions in the isostructural iodide. The interbonding of phosphonium cations proceeds through hydrogen bonds, C-OH...O=C, in which the O...O distance is 275.3 pm.

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