A New Host Lattice Built of the Werner-Type Copper(I,II) Cyanide Complex Involving a Macrocyclic Ligand

1998 ◽  
Vol 63 (5) ◽  
pp. 622-627 ◽  
Author(s):  
Hidetaka Yuge ◽  
Takayoshi Soma ◽  
Takeshi Ken Miyamoto
Keyword(s):  
Macrocyclic Ligand ◽  
Host Lattice ◽  
Macrocyclic Complex ◽  
Monoclinic Space Group ◽  
Cyanide Complex ◽  
New Host ◽  
Space Group

Crystals of a new clathrate [CuII(hmtd)CuI(CN)3]·CH2Cl2 were afforded from a Me2CO-EtOH-CH2Cl2 solution of a macrocyclic complex CuII(hmtd)CuI(CN)3·2 H2O (hmtd = 5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradeca- 4,11-diene). It crystallizes in the monoclinic space group P21/n, a = 7.936(5), b = 18.717(4), c = 17.783(6) Å, β = 98.55(4)°, Z = 4, R = 0.0558 for 1 870 reflections. Unprecedentedly, only one of the three nitrogen-ends of a CuI(CN)3 moiety is coordinated to the square-pyramidal Cu(II) center. The guest CH2Cl2 molecules are captured in the channel between the potlid-shaped [CuII(hmtd)CuI(CN)3] molecules.

Intermediate Products of the Reaction of (4,4,9,9-Tetramethyl-5,8-diazadodecane-2,11-dione dihydrazone)nickel(II) With Butane-2,3-dione; the Structure of cis-Aqua(3,4,7,9,9,14,14,16-octamethyl-1,2,5,6,10,13-hexaazacyclohexadeca-1(16),4,6-tien-3-Ol)nickel(II) Perchlorate Trihydrate

1994 ◽  
Vol 47 (10) ◽  
pp. 1885 ◽  
Author(s):  
NF Curtis ◽  
AR Davis ◽  
FWB Einstein
Keyword(s):  
Water Molecule ◽  
Hydroxy Group ◽  
Secondary Amine ◽  
Macrocyclic Ligand ◽  
Equilibrium Mixture ◽  
Monoclinic Space Group ◽  
Amine Nitrogen ◽  
Space Group ◽  
X Ray ◽  
Intermediate Products

Intermediate products have been isolated from the reaction of (4,4,9,9-tetramethyl-5,8-diazadodecane-2,11-dione dihydrazone )nickel(II) perchlorate with butane-2,3-dione which finally yields the macrocyclic product (3,4,7,9,9,14,14,16-octamethyl-1,2,5,6,10,13-hexaazacyclohexa-deca-2,4,6,16-tetraene)nickel(II) perchlorate , [Ni( omht )] (ClO4)2. An initial violet product is assigned a structure with the macrocyclic ligand 3-acetyl-3,6,8,8,13,13,15-heptamethyl-1,2,4,5,9,12-hexaazacyclopentadeca-5,15-diene. In water this converts into an equilibrium mixture of the tautomeric cations blue cis-aqua(3,4,7,9,9,14,14,16-octamethyl-1,2,5,6,10,13-hexaazacyclohexadeca-1(16),4,6-trien-3-ol)nickel(II), cis-[Ni(L2)(H2O)]2+, and orange (3,6,8,- 8,13,13-hexamethyl-4,5,9,12-tetraazahexadeca-3,5-diene-2,15-dione 15-hydrazone)nickel(II), [Ni(L3)]2+. The rates at 25°C of the forward and reverse reactions of this tautomerism, and of the slower conversion of the equilibrium mixture to [Ni( omht )](ClO4)2, are reported. The structure of cis -[Ni(L2)(H2O)](ClO4)2.3H2O has been determined by X-ray diffractometry (monoclinic, space group P21/n, a 9.694(8), b 19.218(14), c 16.652(9) Ǻ, β 94.88(1)°, R 0.079 for 3254 reflections). This has NiII in octahedral coordination by secondary amine nitrogen atoms 10 and 13, hydrazone nitrogen atoms 1 and 6, and the carbinolamine oxygen substituent at position 3 of the pentadentate macrocyclic ligand L2, with a water molecule coordinated cis to the hydroxy group. Compounds of the tautomeric cations [Ni(L2)]2+ and [Ni(L3)]2+ with coordinated thiocyanate, azide, nitrite, oxalate and acetate are described.

Synthesis of a Cis-N2s2 Donor Macrocycle by Metal-Directed Condensation of Formaldehyde, Nitroethane and a Diaminodithiaalkane - Crystal-Structure of the (6-Methyl-6-Nitro-1,11-Dithia-4,8-Diazacyclotetradecane)-Copper(II) Perchlorate Product

1988 ◽  
Vol 41 (5) ◽  
pp. 773 ◽  
Author(s):  
P Comba ◽  
GA Lawrance ◽  
M Rossignoli ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Crystal Structure ◽  
Structural Properties ◽  
Copper Ion ◽  
Macrocyclic Complex ◽  
High Yield ◽  
Monoclinic Space Group ◽  
Space Group ◽  
Complex Ion ◽  
Perchlorate Salt

Reaction of (3,7-dithianonane-1,9-diamine)copper(II) ion with nitroethane and formaldehyde in basic methanol gives the macrocyclic complex ion (6-methyl-6-nitro-1,II-dithia-4,8- diazacyclotetradecane )copper(II) in high yield. The complex as the perchlorate salt crystallizes in the monoclinic space group P21/n, a 15.008(5), b 8.606(3), c 17.967(4)Ǻ, β 113.79(2)�. The copper ion lies in a square plane of two nitrogen (average Cu-N 2.02 Ǻ) and two thioether (average Cu-S 2.295 Ǻ) donors, with perchlorate oxygens (Cu-O 2.46 and 2.70 Ǻ) in axial sites. Physical and structural properties of the CuIII complexes of the 14-membered cis-N2S2 macrocycle and the known analogous 14-membered N4-donor macrocycle 6-methyl-6-nitro-1,4,8,11- tetraazacyclotetradecane are compared.

Mercury(II) and Lead(II) Complexes of 1-Oxa-7-thia-4,10-diazacyclododecane ([12]aneN2OS)

1999 ◽  
Vol 52 (1) ◽  
pp. 1 ◽  
Author(s):  
Trevor W. Hambley ◽  
Shahara Afshar ◽  
Sebastian T. Marcus ◽  
Lawrence R. Gahan
Keyword(s):  
Stability Constants ◽  
Macrocyclic Ligand ◽  
Protonation Constants ◽  
Secondary Amines ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
The Stability ◽  
Lead Complex

The mixed donor 12-membered macrocyclic ligand 1-oxa-7-thia-4,10-diazacyclododecane ([12]aneN2OS) has been synthesized and the mercury(II) and lead(II) complexes, [Hg([12]aneN2OS)(NO3)2] and [Pb([12]aneN2OS)(NO3)2], have been isolated and characterized by X-ray crystallography. Crystals of the mercury complex are monoclinic, space group P 21/c, a 9·576(2), b 10·757(2), c 14·789(4) Å, β 93·58(2)°, whilst crystals of the lead complex are monoclinic, space group P 21/n, a 19·490(7), b 8·010(2), c 19·576(6) Å, β 109·90(2)°. The protonation constants and stability constants have been determined potentiometrically in aqueous solution. The protonation constants for [12]aneN2OS (log KHL 9·13; log K H2L 6·85) appear typical for secondary amines in similar trans-substituted 12-membered macrocycles. The magnitudes of the stability constants (HgII, log KHgL 10·5; PbII, log KPbL 6·6) are consistent with trends observed previously for macrocyclic ligands as secondary amine donors are replaced with oxygen and thioether donors.

Koordination des dreizähnigen makrocyclischen Liganden 1-Thia-4,7-diazacyc!ononan an Palladium(II) und Platin(II) / Coordination of the Tridentate Macrocyclic Ligand 1-Thia-4,7-diazacyclononane to Palladium(II) and Platinum(II)

1988 ◽  
Vol 43 (3) ◽  
pp. 261-264 ◽  
Author(s):  
Peter Hoffmann ◽  
Rainer Mattes
Keyword(s):  
Bond Length ◽  
Central Atom ◽  
Macrocyclic Ligand ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Ligand Environment ◽  
Space Group ◽  
Square Planar

The reaction of PdAc2 and K2PtCl4 with the ligand 1-thia-4,7-diazacyclononan (C6H14N2S - L) yield crystals of [PdL2](PF6)2 (4) and [PtL2]Br2-H2O (5), respectively. The structures of 4 and 5 have been determined.Crystal data: 4, monoclinic, space group P21/c, a = 719.2(1), b = 1712.5(3), c = 936.8(2) pm. β = 99.15°, Z = 2; 1708 reflections, R = 0.029.5, monoclinic, space group P21/c, a = 1682(2). b = 786(1), c = 1573(1) pm. β = 108.1(1)°, Z - 4; 1706 reflections, R = 0.070. 4 contains octahedrally coordinated Pd(II); in addition to the square planar PdN4 group (mean Pd -N bond length 206 pm) the S-donor atoms are weakly coordinated in the axial positions (Pd-S: 303.4(1) pm). In 5, however, Pt(II) is in a square planar ligand environment. The S-donor atoms are bent away from the axial positions of the central atom.

Phase-transformation-induced twinning of an iron(III) calix[4]pyrrolidine complex

2014 ◽  
Vol 70 (7) ◽  
pp. 644-649 ◽  
Author(s):  
Guillaume Journot ◽  
Reinhard Neier ◽  
Helen Stoeckli-Evans
Keyword(s):  
Phase Transformation ◽  
Title Compound ◽  
Macrocyclic Ligand ◽  
Reduced Form ◽  
Slow Phase ◽  
Monoclinic Space Group ◽  
Space Group ◽  
Monoclinic Form ◽  
Independent Molecules ◽  
The Individual

The title compound, tetrachlorido-1κCl;2κ3Cl-(2,2,7,7,12,12,17,17-octamethyl-21,22,23,24-tetraazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosane-1κ4N,N′,N′′,N′′′)-μ2-oxido-diiron(III), [Fe2Cl4O(C28H52N4)], undergoes a slow phase transformation atca173 K from monoclinic space groupP21/n, denoted form (I), to the maximal non-isomorphic subgroup, triclinic space groupP\overline{1}, denoted form (II), which is accompanied by nonmerohedral twinning [twin fractions of 0.693 (4) and 0.307 (4)]. The transformation was found to be reversible, as on raising the temperature the crystal reverted to monoclinic form (I). In the asymmetric unit of form (I),Z′ = 1, while in form (II),Z′ = 2, with a very small reduction (ca1.8%) in the unit-cell volume. The two independent molecules (AandB) in form (II) are related by a pseudo-twofold screw axis along thebaxis. The molecular overlay of moleculeAon moleculeBhas an r.m.s. deviation of 0.353 Å, with the largest distance between two equivalent atoms being 1.202 Å. The reaction of calix[4]pyrrolidine, the fully reduced form ofmeso-octamethylporphyrinogen, with FeCl3gave a red–brown solid that was recrystallized from ethanol in air, resulting in the formation of the title compound. In both forms, (I) and (II), the FeIIIatoms are coordinated to the macrocyclic ligand and have distorted octahedral FeN4OCl coordination spheres. These FeIIIatoms lie out of the mean plane of the four N atoms, displaced towards the O atom of the [OFeCl3] unit by 0.2265 (5) Å in form (I), and by 0.2210 (14) and 0.2089 (14) Å, respectively, in the two independent molecules (AandB) of form (II). The geometry of the [OFeCl3] units are similar, with each FeIIIatom having a tetrahedral coordination sphere. The NH H atoms are directed below the planes of the macrocycles and are hydrogen bonded to the coordinated Cl−ions. There are also intramolecular C—H...Cl hydrogen bonds present in both (I) and (II). In form (I), there are no significant intermolecular interactions present. In form (II), the individual molecules are arranged in alternate layers parallel to theacplane. TheBmolecules are linked by a C—H...Cl hydrogen bond, forming chains along [100].

scholarly journals Molekül- und Kristallstruktur von 1.1-Dimethylsilylentitanocendichlorid, (CH3)2Si(C5H4)2TiCl2 / Molecular and Crystal Structure of l,r-Dimethylsilylene Titanocene Dichloride, (CH3)2Si(C5H4)2TiCl2

1981 ◽  
Vol 36 (10) ◽  
pp. 1208-1210 ◽  
Author(s):  
Hartmut Köpf ◽  
Joachim Pickardt
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Structure Determination ◽  
Titanocene Dichloride ◽  
Molecular And Crystal Structure ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Space Group ◽  
X Ray ◽  
Structural Dimensions

Abstract The molecular structure of the bridged [1]-titanocenophane 1,1'-dimethylsilylene titanocene dichloride, (CH3)2Si(C5H4)2TiCl2, has been investigated by an X-ray structure determination. Crystal data: monoclinic, space group C2/c, Z = 4, a = 1332.9(3), 6 = 988.7(3), c = 1068.9(3) pm, β = 113.43(2)°. The results are compared with the structural dimensions of similar compounds: 1,1'-methylene titanocene dichloride, CH2(C5H4)TiCl2, with the unbridged titanocene dichloride, (C5H5)2TiCl2 and the ethylene-bridged compound (CH2)2(C5H4)2TiCl2

Supramoleküle aus Kronenethern und geminalen Sulfonen: Synthese von vier binären Komplexen und Kristallstruktur von (CH2CH2O)4·2H 2C(SO2C2H5)2/Supramolecules of Crown Ethers with Geminal Sulfones: Synthesis of Four Binary Complexes and Crystal Structure of (CH2CH2O )4·2H2C(SO2C2H5)2

1995 ◽  
Vol 50 (7) ◽  
pp. 1018-1024 ◽  
Author(s):  
Axel Michalides ◽  
Dagmar Henschel ◽  
Armand Blaschette ◽  
Peter G. Jones
Keyword(s):  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Binary Complexes ◽  
Cyclic Polyethers ◽  
Adjacent Unit ◽  
Methylene Group

In a systematic search for supramolecular complexes involving all combinations of the cyclic polyethers 12-crown-4 (12C4), 15-crown-5 (15C 5), 18-crown-6 (18C 6) and dibenzo- 18-crown-6 (DB -18C6), and the geminal di- or trisulfones H2C(SO 2Me)2, H2C (SO2Et)2 and HC (SO2Me)3-n (SO2Et)n (n = 0 -3 ) , only the following four complexes could be isolated and unequivocally characterized by elemental analysis and 1H NMR spectroscopy: [(12C4){H2C (SO2Et)2}2] (3), [(18C6){H2C (S O2Me)2}] (4), [(DB -18C 6){H2C (SO2Et)2}] (5) and [(D B -18C 6)2{HC (SO2Me )(SO2Et)2}3] (6). The structure of 3 (triclinic, space group P1̄) consists of crystallographically centrosymmetric formula units, in which the disulfone molecules are bonded on each side of the ring by two C -H ··· O(crown) interactions originating from the central methylene group (H···O 213 pm) and from the methylene group of one EtSO2 moiety ( H ··· O 237 pm). Formula units related by translation are connected into parallel strands by a third type of reciprocal C -H ···O bond (H ···O 232 pm) between the second H atom of the central methylene group and a sulfonyl oxygen atom of the adjacent unit. The structure of 4 (monoclinic, space group C2/c) showed severe disorder of the crown ether and could not be refined satisfactorily. Compounds 5 and 6 crystallized as long and extremely thin fibres, indicative of linear-polymeric supramolecular structures; single crystals for X-ray crystallography were not available.

New mixed-valent alkali chain sulfido ferrates A1+x[FeS2] (A = K, Rb, Cs; x = 0.333–0.787)

2020 ◽  
Vol 235 (8-9) ◽  
pp. 275-290
Author(s):  
Michael Schwarz ◽  
Pirmin Stüble ◽  
Katharina Köhler ◽  
Caroline Röhr
Keyword(s):  
Alkali Metal ◽  
General Structure ◽  
Variable Number ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Modulated Structure ◽  
Space Group ◽  
X Ray ◽  
Local Coordination ◽  
Natural Pyrite

AbstractFour new mixed-valent chain alkali metal (A) sulfido ferrates of the general structure family ${A}_{1+x}\left[{\text{Fe}}_{x}^{\text{II}}{\text{Fe}}_{1-x}^{\text{III}}{\text{S}}_{2}\right]$ were synthesized in the form of tiny green-metallic needles from nearly stoichiometric melts reacting elemental potassium with natural pyrite (A = K) or previously prepared Rb2S/Cs2S2 with elemental iron and sulfur (A = Rb/Cs). The crystal structures of the compounds were determined by means of single crystal X-ray diffraction: In the (3+1)D modulated structure of K7.15[FeS2]4 (space group Ccce(00σ3)0s0, a = 1363.87(5), b = 2487.23(13), c = 583.47(3) pm, q = 0,0,0.444, R1 = 0.055/0.148, x = 0.787), a position modulation of the two crystallographically different undulated ${}_{\infty }{}^{1}\left[{\text{FeS}}_{4/2}\right]$ tetrahedra chains and the surrounding K cations is associated with an occupation modulation of one of the three potassium sites. In the case of the new monoclinic rubidium ferrate Rb4[FeS2]3 (x = $\frac{1}{3}$; space group P21/c, a = 1640.49(12), b = 1191.94(9), c = 743.33(6) pm, β = 94.759(4)°, Z = 4, R1 = 0.1184) the undulation of the tetrahedra chain is commensurate, the repetition unit consists of six tetrahedra. In the second new Rb ferrate, Rb7[FeS2]5 (x = 0.4; monoclinic, space group C2/c, K7[FeS2]5-type; a = 2833.9(2), b = 1197.36(9), c = 744.63(6) pm, β = 103.233(4)°, Z = 4, R1 = 0.1474) and its isotypic mixed Rb/Cs-analog Rb3.6Cs3.4[FeS2]5 (a = 2843.57(5), b = 1226.47(2), c = 759.890(10) pm, β = 103.7170(9)°, R1 = 0.0376) the chain buckling leads to a further increased repetition unit of 10 tetrahedra. For all mixed-valent ferrates, the Fe–S bond lengths continuously increase with the amount (x) of Fe(II). The buckling of the chains is controlled through the local coordination of the S atoms by the variable number of A cations of different sizes.

Crystal and Molecular Structure of the Copper(I)-thiolate-selenide Complex [Ph4P][Cu(SeS2CNC4H8)(S2CN2C4H8)] with an Unusual Se-S Bond

1999 ◽  
Vol 54 (10) ◽  
pp. 1313-1317 ◽  
Author(s):  
Qianfeng Zhang ◽  
Jinxi Chen ◽  
Maochun Hong ◽  
Xinquan Xin ◽  
Hoong-Kun Fun
Keyword(s):  
Molecular Structure ◽  
Bond Length ◽  
Crystal And Molecular Structure ◽  
Monoclinic Space Group ◽  
Space Group ◽  
A Cell

Reaction of a DMF solution of Cu(S2CNC4H8) with [Ph4P]2[WSe4] affords [Ph4P]2[WSe4- (CuS2CNC4H8)3] (1) and [Ph4P][Cu(SeS2CNC4H )(S2CN2C4H8)] (2) in which a Se atom from the decomposition of the WSe42- anion has reacted with the pyrrolidyldithiocarbamate (C4H8dtc) ligand anion to form the new ligand anion SeS2CNC4H8⊖. Complex 2 crystallizes with four formula units in the monoclinic space group P21/c in a cell of dimensions a = 10.5824(2), b = 18.7575(3), c = 18.3268(4) Å and ß = 109.0980(10)°. 6055 independent reflections above background were measured with a diffractometer and the structure was refined anisotropically to R =0.073. The anion contains a three-coordinated copper(I) atom. The C4H8dtc⊖ ligand is bonded to the Cu+ cation in a terminal fashion, while SeS2CNC4H8⊖ chelates the Cu+ cation. The Se-S bond length is 2.231 (4) Å.

Zur Kenntnis von EuBeGd2O5 mit einem Beitrag über Phasen der Zusammensetzung M1-xM′xBeLn2O5: Ca0,4Sr0,6BeSm2O5, Ba0,25Ca0,75BeNd2O5 und Ba0,36Sr0,64BeNd2O5 / On EuBeGd2O5 and on Phases of the Composition M1-xM′xBeLn2O5: Ca0,4Sr0,6BeSm2O5, Ba0,25Ca0,75BeNd2O5 and Ba0,36Sr0,64BeNd2O5

1994 ◽  
Vol 49 (7) ◽  
pp. 919-922 ◽  
Author(s):  
Hk. Müller-Buschbaum ◽  
S. Frenzen
Keyword(s):  
Single Crystals ◽  
Plasma Torch ◽  
Monoclinic Space Group ◽  
Orthorhombic Symmetry ◽  
Laser Technique ◽  
Space Group

Abstract Single crystals of (I): EuBeGd2O5, (II): Ca0,4Sr0,6BeSm2O5, (III): Ba0,25Ca0,75BeNd2O5 and (IV): Ba0.36Sr0.64BeNd2O5 were prepared by (I): plasma torch and (II)-(IV ): CO2-LASER technique. X-Rayo investigations lead to (I) monoclinic (space group C52h-P21/c, a = 7.126, b = 6.457, c = 9.394 Å , β = 90.40°) and (II)-(IV) orthorhombic symmetry (D162h-Pnma). (II: a = 9.454, b = 7.142, c = 6.490 Å; III: a = 9.508, b = 7.188, c = 6.531 Å; IV: a = 9.642, b = 7.295, c = 6.614 Å). In contrary to the phases M1-xM′xBeLn2O5, EuBeGd2O5 is characterized by an ordered distribution of Eu2+ and Gd3+ inside of the Kagomé network.

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