The iodo-Tamoxifens: molecular structures and syntheses of estrogens for external imaging of carcinoma

1983 ◽  
Vol 61 (3) ◽  
pp. 421-426 ◽  
Author(s):  
Duncan H. Hunter ◽  
Nicholas C. Payne ◽  
Asadur Rahman ◽  
John F. Richardson ◽  
Yolanda Zea Ponce
Keyword(s):  
Three Dimensional ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cell Dimensions ◽  
A Cell ◽  
E And Z Isomers ◽  
Unambiguous Assignment

The E- and Z-isomers of an iodo-Tamoxifen 1 (1-(p-(β-dimethylaminoethoxy)phenyl)-2-(p-iodophenyl)-1-phenyl-1-butenes) have been prepared from the corresponding E- and Z-amino-Tamoxifens 2 (2-(p-aminophenyl)-1-(p-(β-dimethylaminoethoxy)phenyl)-1-phenyl-1-butenes) and the molecular structures have been determined from three dimensional X-ray data. Crystals of E-1 are triclinic, space group [Formula: see text], with Z = 2 in a cell of dimensions a = 10.714(2), b = 14.125(3), c = 8.240(2) Å, α = 95.78(1), β = 92.91(1), and γ = 71.41(1)°; those of Z-1 are monoclinic, space group P21/n, with Z = 4 and cell dimensions a = 12.675(2), b = 19.553(3), c = 9.483(1) Å, and β = 92.22(1)°. Intensity data collected on an automated four circle diffractometer were used for full-matrix least-squares refinement on F, which converged for E-1 at R = 0.054, 2736 observations, and for Z-1 at R = 0.042, 3644 observations. The solution of these structures determines the configuration of these isomers as well as the respective amino precursors and allows an unambiguous assignment of the proton nmr spectra of 1, 2 and the Tamoxifens.

Metal complexes of dicamba: the crystal and molecular structures of dicamba(3,6-Dichloro-2-methoxybenzoic acid) and catena-μ-Aqua-diaquabis(3,6-dichloro-2-methoxybenzoato)zinc(II) dihydrate

1983 ◽  
Vol 36 (11) ◽  
pp. 2175 ◽  
Author(s):  
G Smith ◽  
EJ O'Reilly ◽  
CHL Kennard
Keyword(s):  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bridging Ligand ◽  
Methoxy Groups ◽  
A Cell ◽  
Methoxybenzoic Acid

The crystal structures of the herbicide, dicamba (3,6-dichloro-2-methoxybenzoic acid) and the zinc(II) complex of this acid, {[Zn(dicamba)2(H2O)3].2H2O}}n (1), have been determined from X-ray diffraction data and refined by least squares to final residuals of 0.034 and 0.043 respectively. Dicamba is triclinic, space group P1, Z 2 with a cell a 7.232(1), b 7.971(1), c 9.050(3) �, α 102.76(3), β 91.33(3), γ 110.38(1)�, while (1) is monoclinic, space group P21/n, Z 4 with a cell a 10.467(1), b 8.135(3), c 28.079(2) �, β 96.497(7)�. Dicamba forms hydrogen-bonded cyclic dimers [O---O, 2.655(7) �] with the carboxyl and the methoxy groups synclinal to the benzene ring. The dicamba ligands retain their conformation in the ZnII complex and are cis-related and unidentate [Zn-0,2.083,2.095(4) �]. Three of the waters are coordinated [Zn-0, 2.036, 2.055, 2.099(4) �] with one of these also acting as a bridging ligand between the octahedral zinc centres [Zn-0, 2.326(4) �], giving a 'linear' polymer structure [Zn-0-Zn bridge angle, 133.6(3)�]. The MnII and CoII complexes of dicamba [(2) and (3)] have been confirmed as isomorphous and isostructural with the ZnII analogue.

Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd)

1992 ◽  
Vol 70 (3) ◽  
pp. 792-801 ◽  
Author(s):  
Jagadese J. Vittal ◽  
Philip A. W. Dean ◽  
Nicholas C. Payne
Keyword(s):  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Bridging Ligands ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Space Groups ◽  
X Ray Crystallography ◽  
Cell Dimensions ◽  
Minimum Number

The structures of three tetramethylammonium salts containing anions of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd) were determined by single crystal X-ray diffraction techniques. The Zn salt crystallizes in different space groups depending upon the solvent combination used in the synthesis. Thus crystals of (Me4N)2[Zn4(SePh)10], 1, grown from a mixture of methanol, acetonitrile, and acetone are triclinic, space group [Formula: see text] with cell dimensions a = 13.214(2), b = 23.859(2), c = 13.072(1) Å, α = 91.134(8), β = 113.350(8), γ = 79.865(9)°, and Z = 2. In the absence of acetone, a solvated crystal (Me4N)2[Zn4(SePh)10]•CH3CN, 2, is formed, which belongs to the monoclinic space group P21/n with a = 14.248(1), b = 39.722(2), c = 13.408(1) Å, β = 97.132(5)°, and Z = 4. The Cd salt (Me4N)2[Cd4(SePh)10], 3, crystallizes in the monoclinic space group P21/c, with a = 20.830(2), b = 14.282(1), c = 25.872(1) Å, β = 99.626(6)°, and Z = 4. These three salts are the first examples of homoleptic, tetranuclear selenolatometal(II) anions with (μ-Se)6M4 cages of adamantane-type stereochemistry. In each case the phenyl substituents of the bridging ligands adopt the configuration [aae, aae, aee, aee], which has the minimum number of two 1,3-axial–axial non-bonding substituent interactions. Keywords: selenolate complexes, synthesis, X-ray crystallography, isomerism, adamantane stereochemistry.

Copper complexes of Picloram: The crystal and molecular structures of Bis(4-amino-3,5,6-trichloropyridine-2-carboxylato)aquacopper(II) dihydrate and Bis(4-amino-3,5,6-trichloropyridine-2-carboxylato)bis(pyrimidin-2-amine)copper(II)

1983 ◽  
Vol 36 (1) ◽  
pp. 183 ◽  
Author(s):  
EJ O'Reilly ◽  
G Smith ◽  
CHL Kennard ◽  
AH White
Keyword(s):  
Copper Complexes ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Trigonal Bipyramidal ◽  
Distorted Octahedral ◽  
A Cell ◽  
Amine Ligands

The crystal structures of two copper(II) complexes of the herbicide Picloram (4-amino-3,5,6-trichloro- pyridine-2-carboxylic acid) have been determined by single-crystal X-ray diffractometry. Bis(4-amino- 3,5,6-trichloropyridine-2-carboxylato)aquacopper(II) dihydrate (1) is monoclinic, space group C2/c, with Z 4 in a cell of dimensions a 15.593(6), b 7.940(6), c 16.983(6) �, β 107.58(3)�. The structure was refined to a residual R 0.046 for 905 'observed' reflections. Complex (1) is trigonal bipyramidal with the trigonal plane consisting of oxygens from two picolinate ligands [Cu-O 1.995(5) �] and a water molecule [Cu-O 2.080(5) �]. The apical positions are occupied by pyridine ring nitrogens from the Picloram ligands [Cu-N 2.021(5) �]. Bis(4-amino-3,5,6-trichloropyridine- 2-carboxylato)bis(pyrimidin-2-amine)copper(II) (2) is monoclinic, space group P2,/c, with Z 4 in a cell of dimensions a 12.3 11(5), b 15.435(5), c 15.320(6) �, β 115.95(3)�, and gave a final R 0.059 for 2429 'observed' reflections. In complex (2), the copper(II) atom has a tetragonally distorted octahedral stereochemistry with the Picloram ring nitrogens once again occupying the two axial positions [Cu-N 2.586(7) and 2.611(7) �]. The square plane consists of two carboxylato oxygens [Cu-O 1.941(6) and 1.960(7) �] and two hetero-nitrogens from pyrimidin-2-amine ligands [Cu-N 2.048(6) and 2.054(6) �].

Crystal structures of two lactones of the bicyclo[2,2,2]octane series

1982 ◽  
Vol 35 (2) ◽  
pp. 457 ◽  
Author(s):  
RM Carman ◽  
SS Smith ◽  
CHL Kennard ◽  
G Smith ◽  
AH White ◽  
...  
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Three Dimensional ◽  
Direct Methods ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
A Cell

The crystal structures of two γ-lactones of the bicyclo[2,2,2]octane series, endo-3-carboxy-exo-5- iodobicyclo[2,2,2]octane-2,6-carbolactone (2; R = CO2H) and exo-3-methoxycarbonyl-endo-5-acetoxybicyclo[2,2,2] octane-2,6-carbolactone (7b), have been determined by direct methods from three-dimensional X-ray data and refined by least-squares to final residuals of 0.033 (2; R = CO2H) and 0.036 (7b) for 1918 and 630 'observed' reflections respectively. Crystals for (2; R = CO2H) are monoclinic, space group P21/c with Z 8 in a cell of dimensions a 7.192(2), b 23.785(8), c 13.199(5) �, β 105.35(2)�, while (7b) crystallizes in the orthorhombic space group P212121 with Z 4 in a cell of dimensions a 13.347(7), b 11.839(7), c 8.227(11) �.

Addition der schweren Chalkogen-Atome und Halogenonium-Ionen an Carbodiphosphorane / Addition of the Heavy Chalkogen Atoms and Halogenonium Ions to Carbodiphosphoranes

1985 ◽  
Vol 40 (10) ◽  
pp. 1293-1300 ◽  
Author(s):  
H. Schmidbaur ◽  
Chr. Zybill ◽  
D. Neugebauer ◽  
G. Müller
Keyword(s):  
Room Temperature ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Molar Ratios ◽  
Structure Factors ◽  
Elemental Iodine

Hexaphenylcarbodiphosphorane Ph3P=C=PPh3 (1) forms deeply coloured, crystalline 1:1 ad- ducts with elemental sulfur, selenium and tellurium (2, 3 and 7, respectively). A superior method of synthesis for 7 is the reaction of Na2Te with (Ph3P)2CCl⊕Cl⊖. All three compounds are thermally unstable and decompose at or below room temperature. A selenium adduct 5 was also obtained with Me3P = C = PPh, (4). The compounds 2 and 3 can be alkylated at the chalkogen atoms using MeOSO2F or PhCH2Cl. Oxydation of 3 leads to Se - Se coupling.Addition of elemental iodine to 1 in molar ratios 1:1. 2:3 and 1:2 affords salt-like products composed of the (Ph2P)2Cl⊕ cation associated with I⊖ and/or I3⊖ anions (8a-c).The crystal and molecular structures of 3 and 8b have been determined by single crystal X-ray diffraction. 3′, containing one half equivalent of disordered tetrahydrofuran, crystallizes in the monoclinic space group P21/n (a = 10.848(6), b = 17.433(8). c = 16.848(9) Å, β = 91.51(5)°. V = 3185.07 Å3, ϱx = 1359 gcm-3, Z = 4). Based on 3488 structure factors, the final R value was 0.103. The selenium is attached to the ylidic carbon atom without major changes of the Ph3P=C=PPh3 skeleton (C - Se = 1.99 Å). 8b crystallizes in the triclinic space group P1̄ (a = 9.935(2). b = 11.507(2), c = 16.646(3) Å, α = 90.91(1), β = 112.00(1), γ = 96.60(1)°, V = 1749.15 A3, ϱx = 1.741 gcm-3, Z = 2). Refinement of 382 parameters on 5096 structure factors converged at R = 0.043. The molecular structure shows close similarities to the selenium adduct 3 (C-I = 2.12 Å).

scholarly journals Two New Supramolecular Assemblies Obtained by Reaction Between Saccharin and Long-chain Diamines

2009 ◽  
Vol 64 (9) ◽  
pp. 1041-1045
Author(s):  
Eduardo E Castellano ◽  
Oscar E. Piro ◽  
Beatriz S. Parajón-Costa ◽  
Enrique J. Baran
Keyword(s):  
Three Dimensional ◽  
Supramolecular Assembly ◽  
Monoclinic Space Group ◽  
Ionic Crystals ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Anions And Cations ◽  
Bonding Characteristics

The crystal structures of heptamethylenediammonium bis(saccharinate) monohydrate, [H3N - (CH2)7 -NH3](sac)2・H2O (1) and octamethylenediammonium bis(saccharinate) hemihydrate, [H3N- (CH2)8-NH3](sac)2・0.5H2O (2), were determined by single-crystal X-ray diffraction methods. Compound 1 crystallizes in the triclinic space group P1̄ with 2 molecules per unit cell, and 2 in the monoclinic space group P21/a with Z = 4. The saccharinate moiety is planar in both compounds presenting bonding characteristics comparable to those found in other saccharinate salts. The ionic crystals are further stabilized by an extensive H-bonding network, which links the anions and cations into an infinite three-dimensional supramolecular assembly. The FTIR spectra of the adducts are briefly discussed in comparison with those of the constituent molecules.

Cyclometallation Reactions. XXI. Some Chemistry of Binuclear Manganese Complexes Derived From Azobenzene: X-Ray Crystal-Structures of {Mn (CO)4}2(μ- C6H4N=NC6H4) and {Mn (CO)4}{ Mn (CO)3[P(OPh)3]}(μ-C6H4N=NC6H4)

1988 ◽  
Vol 41 (9) ◽  
pp. 1407 ◽  
Author(s):  
MI Bruce ◽  
MJ Liddell ◽  
MR Snow ◽  
ERT Tiekink
Keyword(s):  
Crystal Structures ◽  
Binuclear Complex ◽  
Hydrogen Transfer ◽  
Monoclinic Space Group ◽  
Subsequent Reaction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cell Dimensions ◽  
Unit Cell Dimensions

The reaction between azobenzene and Mn (CH2Ph)(CO)5, carried out in refluxing n-octane, afforded the binuclear complex {Mn (CO)4}2(μ- C6H4N=NC6H4) (2) as the first isolable product; subsequent reaction with azobenzene gave Mn (C6H4N= NPh )(CO)4. With P( OPh )3, the binuclear complex undergoes CO substitution but not hydrogen transfer, to give {Mn (CO)4}{ Mn (CO)3[P(OPh)3]}(μ-C6H4N=NC6H4)(3). The X-ray crystal structures of the title complexes have been determined. Compound (2) crystallizes in the monoclinic space group P21/c with unit cell dimensions a 10.161(2), b 23.586(4), c 13.091(4)Ǻ, β 97.10(2)° with Z = 6; crystals of (3) are triclinic, space group Pī , a 12.886(3), b 13.920(3), c 10.428(7)Ǻ, α 97.11(4),β 102.60(4), γ 81.78(2)°. The structures were refined by a full-matrix least-squares procedure to final R 0.041 and Rw 0.048 for 3459 reflections with I ≥ 2.5σ(I) for (2), and R 0.095 and Rw 0.106 for 3406 reflections for (3).

A comparison of the molecular structures of Dicyclohexyl(N-phenylthiocarbamoyl)-phosphine and Diphenyl(N-phenylthiocarbamoy1)phosphine as determined by X-ray crystallography

1984 ◽  
Vol 37 (10) ◽  
pp. 1991 ◽  
Author(s):  
SW Cowan ◽  
BF Hoskins ◽  
ERT Tiekink
Keyword(s):  
Three Dimensional ◽  
Unit Cell ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hydrogen Atoms ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Conformational Effects

The crystal and molecular structures of the title compounds, (C6H11)2PC(S)N(H)C6H5(1) and (C6H5)2PC(S)N(H)C6H5(2) have been determined by single-crystal three-dimensional X-ray diffraction techniques. Crystals of (1) are monoclinic, space group P21/c, with eight molecules in the unit cell of dimensions a 20.541(4), b 17.784(2), c 10.2564(9) � and β 94.54(1)�; (2) crystallizes in the triclinic space group P1 with two molecules in the unit cell which has the dimensions a 9.242(2), b 9.994(3), c 10.373(3) �, α 68.56(2), β 71.21(2) and γ 86.00(2)�. Both structures were refined by a least-squares procedure, applying anisotropic thermal parameters to all non-hydrogen atoms, with the use of 3119 and 2971 statistically significant reflections for (1) and (2) respectively; final R 0.055 for (1) and R 0.061 (Rw 0.062) for (2). The N, C(l), S moieties of both (1) and (2) display features consistent with the delocalization of π-electrons. There are notable differences in some of the bond angles between (I) and (2) which have been attributed to conformational effects arising from variations in steric pressures; this may account for the observed differences in reactivity between the two compounds.

The crystal and molecular structures of N,N′-di(2-acetylcyclohexenyl)ethylenediamine and its copper(II) complex

1993 ◽  
Vol 71 (3) ◽  
pp. 358-363 ◽  
Author(s):  
Juan N. Fernández-G. ◽  
Raúl G. Enríquez ◽  
Amalia Tobón-Cervantes ◽  
Margarita I. Bernal-Uruchurtu ◽  
René Villena-I ◽  
...  
Keyword(s):  
Solvent Molecule ◽  
Molecular Structures ◽  
Isomeric Form ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Nmr Study ◽  
Square Planar

The crystal structures of N,N′-di(2-acetylcyclohexenyl)ethylenediamine (L1) and its copper(II) complex, which crystallizes with one solvent molecule of chloroform (Cu(L1-2H)•CHCl3), were determined. Crystallographic details are as follows: L1 is monoclinic, space group P21/c, with a = 8.280(2), b = 11.692(2), and c = 9.355(2) Å, β = 114.10(2)°, V = 826.7(3) Å3, Z = 2; ρc = 1.22 g cm−3, μ(Cu Kα) = 5.93 cm−1, with the final residual indices of R = 0.046 and Rw = 0.070 for 991 unique reflections. Cu(L1-2H)•CHCl3 is triclinic, space group[Formula: see text] with a = 11.121(3), b = 11.713(3), and c = 8.974(2) Å, α = 99.35(2)°, β = 110.83(2)°, γ = 82.33(2)°, V = 1074(1) Å3, Z = 2; ρc = 1.50 g cm−3, μ(Cu Kα) = 50.74 cm−1, with the final residual indices of R = 0.048 and Rw = 0.077 for 2369 unique reflections. The X-ray diffraction study shows that in the crystal state the ligand L1 is in the methylketonecyclohexanonenamine isomeric form. For the copper complex Cu(L1 2H)•CHC13, the geometry around the metal atom is distorted square planar, and the angle between the chelate ring planes in the complex is 15.1°. An NMR study shows that L1 in solution has the same structure as that observed in the solid state by X-ray diffraction.

"A-frame" vs. "open-book" geometries in binuclear complexes bridged by diphosphines and mercaptothiazolinate ligands. Unusual examples involving a bridging bis(diphenylphosphino)ethane group

1993 ◽  
Vol 71 (5) ◽  
pp. 726-737 ◽  
Author(s):  
Jianliang Xiao ◽  
Martin Cowie
Keyword(s):  
Monoclinic Space Group ◽  
Stable Form ◽  
Binuclear Complexes ◽  
Open Book ◽  
Solid Reaction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
A Cell

Reaction of the tetracarbonyl species [M(CO)2(µ-mtz)]2 (M = Rh, Ir; mtz = 2-mercaptothiazolinate) with 1 equivalent of the diphosphines (Ph2P(CH2)nPPh2; n = 1 (dppm), 2 (dppe)) yields the compounds [M2(CO)2(µ-L)(µ-mtz)2] (M = Rh, L = dppm (1), dppe (3); M = Ir, L = dppm (2)), which readily undergo oxidative addition of iodine to give [M2I2(CO)2(µ-L)(µ-mtz)2] (M = Rh, L = dppm (4), dppe (6); M = Ir, L = dppm (5)). When 2 equivalents of dppm are used, the A-frame compounds [M2(CO)2(η1-mtz)(µ-mtz)(dppm)2] (M = Rh (7), Ir (8)) are afforded. In solution the dangling mtz group of 7 undergoes exchange with both the free mtz anion and the bridging mtz ligand. Compounds 7 and 8 are also produced by treatment of trans-[MCl(CO)(dppm)]2 (M = Rh, Ir) with 2 equivalents of the mtz anion. Reaction of these dppm-bridged dichloro species with 1 equivalent of the mtz anion yields [M2Cl(CO)2(µ-mtz)(dppm)2] (M = Rh (9a), Ir (10)). Compound 9a undergoes reversible Cl− dissociation to give [Rh2(CO)2(µ-mtz)(dppm)2][Cl] (9b), which is also the stable form in the solid. Reaction of 9 with CO gives the carbonyl-bridged species [Rh2(CO)2(µ-CO)(µ-mtz)(dppm)2][Cl]. The structures of 6 and 9b have been determined by X-ray crystallography. Compound 6 crystallizes in the triclinic space group [Formula: see text] with one-half equivalent of THF per asymmetric unit in a cell having a = 9.856(3) Å, b = 14.078(6) Å, c = 16.245(5) Å, α = 103.66(3)°, β = 93.21(3)°, γ = 92.91(3)°, V = 2182(1) Å3, and Z = 2, and has refined to R = 0.045 and Rw = 0.057 on the basis of 433 parameters varied. Compound 9b crystallizes with one equivalent of CH2Cl2 in the monoclinic space group P21/n with a = 11.400(1) Å, b = 21.944(2) Å, c = 22.134(1) Å, β = 92.494(7)°, V = 5532(1) Å3, and Z = 4, and has refined to R = 0.062 and Rw = 0.082 on the basis of 613 parameters varied.

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