Alkyl Substituent Effects in Diamagnetic Dithiocarbamate Cobalt(III) and Nickel(II) Complexes

1990 ◽  
Vol 43 (6) ◽  
pp. 1083 ◽  
Author(s):  
PC Healy ◽  
JW Connor ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Field Strength ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Aliphatic Hydrocarbon ◽  
Ligand Field ◽  
Space Group ◽  
X Ray ◽  
Dithiocarbamate Ligand ◽  
Structure Determinations ◽  
Study Support

Single-crystal X-ray structure determinations have been recorded at 295 K for the tris(dithiocarbamato)cobalt(III) compounds: [Co(S2CN(CH2)4)3], [Co(S2CNEt2)3] (redeterminations), [Co(S2CN(CH2Ph)2)3], and [Co(S2CNPri2)3] at 120 and 295 K. [Co(S2CN(CH2)4)3] crystallizes in the space group C2/c with a 28.984(15), b 14.416(2), c 16.206(15)Ǻ, β 104.20(5)°, Z 12; [Co(S2CNEt2)3] also crystallizes in space group C2/c with a 14.097(3), b 10.305(2), c 17.070(7)Ǻ, β 110.19(3)°, Z 4; [Co(S2CN(CH2Ph)2)3] crystallizes in space group P21 with a 11.851(6), b 29.920(8), c 12.395(3)Ǻ, β 97.74(4)°; [Co(S2CNPri2)3] crystallizes in space group R3c with a 13.367(6)Ǻ, α 58.04(2)° (295 K); a 13.155(6)Ǻ, α 58.59(3)° (120 K), Z 2. The structure of [Ni(S2CNPri2)2] has been redetermined, the complex crystallizing in the space group P21/c with a 8.147(2), b 17.820(3), c 15.630(3)Ǻ, β 110.32(2)°, Z 4. The results obtained from this study support the hypothesis, put forward by Ymen and Stahl, that the influence of aliphatic hydrocarbon substituents on the ligand-field strength at the sulfur atoms of the dithiocarbamate ligand is not through the π bonding network of the conjugated S2CN moiety, but, rather, intraligand S…H-C interactions which increase with increasing bulk of the substituent atoms. Unlike the free anion systems, or the iron(III) complexes, however, the changes in the S-C-S angles with increasing field strength, while observable, are very small.

Notizen: Einkristall-Strukturdaten einiger Fluoride und Cyanide A2IBIMIIIX6 der Elpasolithfamilie / Single Crystal Structural Data of Some Fluorides and Cyanides A2IBIMIIIX6 of the Elpasolite Family

1975 ◽  
Vol 30 (5-6) ◽  
pp. 462-464 ◽  
Author(s):  
R. Haegele ◽  
W. Verscharen ◽  
D. Babel
Keyword(s):  
Single Crystal ◽  
Structural Data ◽  
Space Group ◽  
X Ray ◽  
Lattice Constants ◽  
Structure Determinations ◽  
Crystal Structural Data ◽  
Crystal Structural

The parameters of complete X-ray structure determinations are given for the fluoridesRb2NaFeF6 and Rb2KFeF6 (cubic), Cs2NaCrF6 and Cs2NaFeF6 (hexagonal-rhom-bohedral) and Cs2LiGaF6 (hexagonal). Space group and lattice constants of the monoclinic cyanides Cs2BFe(CN)6 (B = Na, K, Rb) are reported as well.

Ligand-Field Strength and Symmetry-Restricted Covalency in CuIIComplexes - a Near-Edge X-ray Absorption Fine Structure Spectroscopy and Time-Dependent DFT Study

2015 ◽  
Vol 2015 (16) ◽  
pp. 2707-2713 ◽  
Author(s):  
Giulia Mangione ◽  
Luciano Pandolfo ◽  
Mauro Sambi ◽  
Giovanni Ligorio ◽  
Marco Vittorio Nardi ◽  
...  
Keyword(s):  
Fine Structure ◽  
Field Strength ◽  
Time Dependent ◽  
Dft Study ◽  
Ligand Field ◽  
X Ray ◽  
Absorption Fine ◽  
X Ray Absorption

Synthesen und Kristallstrukturen von [PPh3Me]NO2 und [PPh3 Me]HCO2H2O / Syntheses and Crystal Structures of [PPh3Me]NO2 and [PPh3Me]HCO2H2O

1988 ◽  
Vol 43 (10) ◽  
pp. 1279-1284 ◽  
Author(s):  
Mervat El Essawi ◽  
H Gosmann ◽  
D Fenske ◽  
F Schmock ◽  
K Dehnicke
Keyword(s):  
Crystal Structure ◽  
Aqueous Solutions ◽  
Ir Spectra ◽  
Bond Angle ◽  
Water Molecules ◽  
Moist Air ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Structure Determinations

Triphenylmethylphosphonium nitrite and formate have been prepared by the reaction of [PPh3Me]I with silver nitrite, and lead formate, respectively, in aqueous solutions. [PPh3Me]NO2 (1) forms pale yellow crystals, and [PPh3Me]HCO2·H2O (2) forms white crystals. Both compounds are soluble in water, ethanol, and dichloromethane. In moist air 2 is hydrated to yield [PPh3Me]HCO2·2H2O (3). The compounds were characterized by their IR spectra, 1 and 2 also by X-ray crystal structure determinations.[PPh3Me]NO2 (1): space group P21/n, Z = 4, 2088 independent observed reflexions, R = 0.062. Lattice dimensions (20 °C): a = 914.7(3), b = 1887.5(9), c = 1080.0(4) pm, β = 110.29(3)°. The compound consists of PPh3Me+ ions and NO2- anions with bond lengths of 114.2(6) pm and a bond angle of 124.1(7)°. [PPh3Me]HCO2·H2O (2): space group P21/n, Z = 4, 2973 independent observed reflexions, R = 0.069. Lattice dimensions (-20 °C): a = 931(2), b = 1558(3), c = 1281(2) pm, β = 105.9(1)°. The compound consists of PPh3Me+ ions and formate anions which form centrosymmetric dimeric units [HCO2·H2O]22- through hydrogen bridges of the water molecules. Bond lengths CO 122.4(4) and 120.9(4) pm. bond angle OCO 129.9(4)°.

One-dimensional ribbons of solvated Ag sulfonates

1999 ◽  
Vol 77 (3) ◽  
pp. 313-318 ◽  
Author(s):  
George KH Shimizu ◽  
Gary D Enright ◽  
Gabriela S Rego ◽  
John A Ripmeester
Keyword(s):  
Coordination Polymer ◽  
Single Crystal ◽  
The Other ◽  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
One Dimensional ◽  
X Ray ◽  
Structure Determinations

Single crystal X-ray structure determinations of two solvated silver sulfonates have been obtained and these compounds have been shown to adopt infinite one-dimensional motifs. {AgOTs(MeCN)}[Formula: see text] (OTs = p-toluenesulfonate) crystallizes in the monoclinic space group, P21, a = 8.4278(5) Å, b = 5.7413(3) Å, c = 12.1057(7) Å, β = 109.24(1)°. {Ag(NDSA)(MeCN)2(H3O)(H2O)2}[Formula: see text] (NDSA = 1,5-naphthalenedisulfonate) crystallizes in the triclinic space group, P[Formula: see text], a = 8.3407(4) Å, b = 10.4374(5) Å, c = 12.3399(6) Å, α = 101.941(8)°, β = 109.24(1)°, γ = 102.190(8)°. Despite one compound containing a monosulfonate and the other a disulfonate, both complexes form infinite one-dimensional arrays.Key words: silver, sulfonates, coordination polymer.

Donor-Akzeptor-Komplexe von Halogenidionen mit 1.4-Diiodtetrafluorbenzol/Donor-Acceptor Complexes of Halide Ions with 1,4-Diiodotetrafluorobenzene

1999 ◽  
Vol 54 (1) ◽  
pp. 77-86 ◽  
Author(s):  
Jutta Grebe ◽  
Gertraud Geiseler ◽  
Klaus Harms ◽  
Kurt Dehnicke
Keyword(s):  
Three Dimensional ◽  
Crystallographic Structure ◽  
Acceptor Molecule ◽  
Halide Ions ◽  
Space Group ◽  
X Ray ◽  
Bond Angles ◽  
Structure Determinations ◽  
Donor Acceptor

(Ph4P)X as well as (Me4N)X (X = Cl, Br, I) react with 1,4-diiodotetrafluorobenzene in CH2C12 and CH3CN solutions, respectively, to give the donoracceptor complexes (Ph4PM (C6F4I2)Cl2]·4 CH2Cl2 (1), (Ph4P)2[(C6F4I2)Br2]·2 CH2Cl2 (2), (Me4N)[(C6F4I2)Cl] (3), (Me4N)[(C6F4I2)Br]·CH3CN (4), (Ph4P)2[(C6F4I2)3Br2]·4CH2Cl2 (5), (Ph4P)2[(C6F4I2)3I2] (6) and (Me4N)2[(C6F4I2)3I2] (7). All complexes have been characterized by single X-ray crystallographic structure determinations. 1: Space group P1̄, Z = 1, lattice dimensions at 203 K: a = 1090.2(1), b = 1206.2(1), c = 1242.8(1) pm, α = 91,84(1)°, β = 106.60(1)°, γ = 99.84(1)°.2: Space group P1̄, Z = 1, lattice dimensions at 233 K: a = 1129.7(2), b = 1183.9(1), c = 1293.4(1) pm, α = 65.52(1)°, β = 65.74(1)°, γ = 89.02(1)°.3: Space group P21/n, Z = 4, lattice dimensions at 243 K: a = 714.8(1), b = 2405.7(3), c = 930.8(1) pm, β = 96.38(1)°.4: Space group P21/c, Z = 4, lattice dimensions at 203 K: a = 1400.8(1), b = 1669.9(2), c = 795.9(1) pm, β = 102.81(1)°.5: Space group Pbca, Z = 4, lattice dimensions at 223 K: a = 2106.0(4), b = 1566.8(3), c = 2445.8(4) pm.6 : Space group P1̄, Z = 1, lattice dimensions at 203 K: a = 1150.9(1), b = 1278.9(1), c = 1292.9(2) pm, α = 65.47(1)°, β = 82.07(1)°, γ = 83.62(1)°.7: Space group Pbca, Z = 4, lattice dimensions at 223 K: a = 1210.5(5), b = 1429.0(6), c = 2470.3(12) pm.In all complexes the acceptor molecule C6F4I2 coordinates with the halide donor ions in linear arrangements C-I· · ·X- . In 1 and 2 the halide ions act as terminal donors to form the dianionic species [X· · ·I-C6F4-I· · ·X]2- (X = Cl, Br). Complexes 3 and 4 form polymeric anionic zigzag chains with μ-X- bridges and bond angles I· · ·Cl· · ·I of 77.2° and I· · ·Br· · ·I of 74.3°. Complexes 5 - 7 are characterized by three-dimensional anionic networks via /x3-X- bridging halide ions and μ-bridging 1,4-diiodotetrafluorobenzene molecules.

Synthesis and structure of 4-methylpyridine complexes of cobalt(II) and nickel(II) hexafluorophosphate and hexafluoroarsenate

1978 ◽  
Vol 56 (7) ◽  
pp. 985-991 ◽  
Author(s):  
Raymond M. Morrison ◽  
Robert C. Thompson
Keyword(s):  
Magnetic Properties ◽  
Field Strength ◽  
Single Crystal ◽  
Infrared Spectra ◽  
Electronic Spectra ◽  
Preliminary Report ◽  
Ligand Field ◽  
X Ray Diffraction ◽  
X Ray ◽  
Square Planar

The complexes M(4mepy)4A2 and M(H2O)2(4mepy)8A2 (where M is Ni or Co and A is PF6 or AsF6) have been prepared and their electronic spectra and magnetic properties studied. A preliminary report is made of single crystal X-ray diffraction studies on Ni(H2O)2(4mepy)8(PF6)2, Co(H2O)2(4mepy)8(PF6)2, and Co(4mepy)4(PF6)2. All of the complexes have structures involving complex cations and non-coordinated anions, consistent with extremely weak ligating abilities for both PF6− and AsF6−. Cations identified and characterized are the squashed tetrahedral [Co(4mepy)4]2+ ion, the square planar [Ni(4mepy)4]2+ ion, and the tetragonal [Co(4mepy)4((4mepy)2H2O)2]2+and [Ni(4mepy)4((4mepy)2H2O)2]2+ ions. The ligand field strength of 4-methylpyridine is found to be indistinguishable from that of pyridine in these complexes. Infrared spectra are reported and infrared criteria for establishing the presence of non-coordinated anions in PF6− and AsF6− complexes are suggested.

Kristallstrukturen der iodierten closo-Hexaborate trans-(Ph4P)2[B6H4I2], mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2, trans-(Ph4P)2[B6H2I4] · 2 CH3CN und (CH2Py2)[B6HI5]/Crystal Structures of the Iodized closo-Hexaborates trans-(Ph4P)2[B6H4I2], mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2, trans-(Ph4P )2[B6H2I4] · 2 CH3CN and (CH2Py2)[B6HI5]

1998 ◽  
Vol 53 (2) ◽  
pp. 206-210 ◽  
Author(s):  
D. Sonnak ◽  
W. Preetz
Keyword(s):  
Single Crystals ◽  
Crystal Structures ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations

Abstract X-ray structure determinations have been performed on single crystals of trans-(Ph4P)2-[B6H4I2] (1) (triclinic, space group P1̄, a = 9.9680(12), b = 10.9690(11), c = 11.0470(14) Å,α = 88.167(9), β = 80.466(12), γ = 68.839(11)°, Z = 1), mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2 (2)(triclinic, space group P1̄, a = 11.8694(11), b = 15.1699(13), c = 17.051(2) Å, α = 75.118(9), β = 71.953(10), γ = 69.331(8)°, Z = 2), trans-(Ph4P )2[B6H2I4] · 2 CH3CN (3) (monoclinic, space group P21/n, a = 14.9665(10), b = 7.6783(10), c = 23.385(3) Å, β = 95.78(9)°, Z = 2), and (CH2Py2)[B6HI5] (4) (orthorhombic, space group Pnma, a = 13.660(2), b = 11.8711(13), c = 13.839(2) Å, Z = 4). The B6 octahedra are compressed in the direction of the B-I bonds, resulting in shortened diagonal B ··· B distances with average values of the groups I-B ··· B-I = 2.37 and I-B ··· B-H = 2.43 Å as compared with H-B ··· B-H = 2.49 Å.

Isomers of Diformyl[2.2]paracyclophane; X-Ray Structure Determinations of the Pseudo-ortho Isomer and Two Polymorphs of the Pseudo-meta Isomer

2011 ◽  
Vol 66 (7) ◽  
pp. 705-710
Author(s):  
Peter G. Jones ◽  
Ina Dix ◽  
Mihaela Negru ◽  
Dieter Schollmeyer
Keyword(s):  
General Position ◽  
The Other ◽  
Independent Molecule ◽  
Space Group ◽  
X Ray ◽  
Ortho Isomer ◽  
Layer Structures ◽  
Structure Determinations ◽  
Independent Molecules ◽  
Meta Isomer

Pseudo-ortho- or 4,16-diformyl[2.2]paracyclophane (1) and two polymorphs of pseudo-meta- or 4,13-diformyl[2.2]paracyclophane (2) all display the usual features of [2.2]paracyclophane strain (lengthened C-C bonds and widened C-C(sp3)-C angles in the bridges, narrower sp2 ring angles at the bridgehead atoms, and flattened boat conformations of the rings). All bulk samples were racemates. Polymorph 2a crystallizes in space group P21/n with one molecule in a general position, whereas 2b crystallizes in space group C2 with two independent molecules, each with crystallographic twofold symmetry. All three molecules of 2 are different rotamers with respect to the formyl groups; in 2a one is endo and one exo to the neighbouring bridge, whereas in 2b both formyls are exo in one molecule and endo in the other. In all compounds, the packing patterns are preponderantly associated with C-H・ ・ ・O contacts. In 1 the molecules are connected to form tubes parallel to the short a axis. 2a consists of two interconnected layer structures. One is parallel to (100) and involves chains of molecules parallel to [01̄1]; the other is parallel to (001) and involves chains of molecules parallel to the b axis. 2b consists of two hexagonal layers, one for each independent molecule, parallel to (001). One layer contains bifurcated (C-H・ ・ ・ )2O systems, whereas the single H・ ・ ・O interactions in the other are long and markedly bent.

Dimethylmetallderivate substituierter Pyrrole (Metall = Al, Ga und In) / Dimethylmetal Derivatives of Substituted Pyrroles (Metal = Al, Ga, and In)

1993 ◽  
Vol 48 (11) ◽  
pp. 1437-1447 ◽  
Author(s):  
Jochen Tödtmann ◽  
Wolfgang Schwarz ◽  
Johann Weidlein ◽  
Arne Haaland
Keyword(s):  
Vibrational Spectra ◽  
High Melting ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations ◽  
Substituted Pyrroles ◽  
Derivatives Of ◽  
Ir And Raman

The reactions of indium trimethyl with the substituted pyrroles HNC4H2Me2-2,5 and HNC4Me4-2,3,4,5 (Me = CH3) yield the solid, high melting dimethylindium azolides Me2In—NC4H2Me2-2,5 and Me2In—NC4Me4, respectively. Colorless and crystalline N-methyl-2-dimethylmetal pyrrolides have been prepared from Me2MCl (M = Al, Ga, In) and lithiated N-methyl pyrrole. All compounds were investigated by MS, NMR (1H and 13C), and vibrational spectra (IR and Raman). The X-ray structure determinations of Me2Ga—C4H3NMe and Me2InNC4Me4 show the triclinic space group P T in both cases, with two formula units per cell forming “π-dimers” via short intermolecular M · · · C contacts of 248.1 (Ga) and 257.5 (In) pm.

Substitutionsreaktionen an der N-Chlornitrenogruppe des [WCl4(NCl)]2. Die Kristallstrukturen von [CH3CN—WCl4(NSMe)] und [WNCl3 · NC—CH3]4 / Substitution Reactions at the N-Chloronitreno Group of [WCl4(NCl)]2. The Crystal Structures of [CH3CN—WCl4(NSMe)] and [WNCl3 · NC—CH3]4

1989 ◽  
Vol 44 (8) ◽  
pp. 903-910 ◽  
Author(s):  
Astrid Görge ◽  
Ute Patt-Siebel ◽  
Ulrich Müller ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Ir Spectra ◽  
Structure Determination ◽  
Monoclinic Space Group ◽  
Trans Position ◽  
Crystal Data ◽  
Substitution Reactions ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations

[WCl4(NCl)]2 reacts in acetonitrile with the trimethylsilyl compounds Me3SiSR (R = Me, Ph), and Me3SiESiMe3 (E = S, Se), with substitution of the chlorine atom of the N-chloronitreno group W=N–Cl and formation of CH3CN–WCl4(NSR) and CH3CN–WCl4(NEN)WCl4–NCCH3, respectively. Excess Me3SiBr reacts with CH3CN–WCl4(NSMe) to afford CH3CN–WBr4(NSMe). [CH3CN–WNCl3]4 was obtained from CH3CN–WCl4(NCl) and N(SiMe3)3. The products were characterized by their IR spectra. Two X-ray crystal structure determinations were also carried out. CH3CN—WCl4(NSMe) forms twinned crystals, and only non-overlapping reflexions of one of the twin individuals were used for the structure determination (846 unique values, R = 0.055). Crystal data: a = 592.4(2), b = 758.8(2), c = 1203.7(8) pm, β = 95.06(4)°, monoclinic, space group P21/m, Z = 2. The compound is a monomer in which the acetonitrile ligand is situated in the trans position to the W≡N–S̱̅–Me group. The bond lengths (W≡N 174(2), N–S 161(2) pm) and bond angles (WNS 176(1), NSC 102.1(9)°) are in agreement with the proposed formula. Crystal data for [CH3CN–WNCl3]4: a = 1009.5(2), b = 1274.5(2), c = 1287.9(2) pm, β = 108.17(1)°, monoclinic, space group P21/c, Z = 2 (2113 unique reflexions, R = 0.057). The compound forms tetrameric units, in which the W atoms form a square and are linked with one another via N atoms at alternating distances (W=N 171(2), W–N 207(2), W–NCMe 238(2) pm).

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