Structures and bonding in some chloro complexes of trivalent metals

1970 ◽  
Vol 23 (11) ◽  
pp. 2205 ◽  
Author(s):  
DE Scaife
Keyword(s):  
Magnetic Data ◽  
Site Symmetry ◽  
Vanadium Compounds ◽  
Tetrahedral Symmetry ◽  
Chloro Complexes ◽  
X Ray ◽  
Quadrupole Resonance ◽  
Nuclear Quadrupole ◽  
A Site ◽  
Infrared Data

Compounds of the type (cation+)MCl4- form isomorphous series when (cation+) = Ph4P+ and Ph4As+, and M = Al, Ga, In, Tl, V, and Fe in their trivalent states. X-ray data, infrared data, and for the vanadium compounds, magnetic and electronic spectral data, also suggest that the series is isomorphous, with the MCl4- ion having a slightly distorted tetrahedral symmetry. 35Cl nuclear quadrupole resonance results for the Al and Tl compounds indicate a site symmetry of S4 for the MCl4- ion. Magnetic data for the vanadium compounds, and also for (Bun)4NVCl4, show some antiferromagnetic interaction of the VCl4- ions in these lattices. Infrared data are also presented for (Ph4As)2InCl5, Ph4PSbCl4, Ph4AsSbCl4, Ph4PBiCl4, and PhdAsTiCl4, none of which appears to contain tetrahedral MCl4- ions.

Studies of vanadium(III) aqua chloro complexes and some related compounds

1972 ◽  
Vol 25 (12) ◽  
pp. 2521 ◽  
Author(s):  
LPSPW Podmore
Keyword(s):  
Magnetic Data ◽  
Structural Studies ◽  
Chloro Complexes ◽  
X Ray ◽  
Rubidium Salt ◽  
Quadrupole Resonance ◽  
Nuclear Quadrupole ◽  
First Time ◽  
Related Compounds ◽  
Complex Ion

Preparative and structural studies on several series of vanadium(111) aqua chloro complexes and related compounds are reported. Results indicate that all compounds contain vanadium(111) in pseudo-octahedral coordination. Evidence is presented from electronic, infrared, and nuclear quadrupole resonance spectra, X-ray powder diffraction, and magnetic data. The compounds of empirical formulae VX3,6H2O (X = Cl, Br), RbVCl4,6H2O, and Cs2VX5,nH2O (X = Cl, n = 4; X = Br,n = 5) are all shown to contain the green trans-[V(OH2)4X2]+ ion. For compounds of formula AI2VCl5,H2O (A = Cs, Rb, K, NH4) prior methods of preparation are reexamined and a new method of preparation is given. Physical studies confirm that these compounds contain the red complex ion [V(OH2)Cl5I2-. The salts comprise structures of two types, one for A = Cs, the other for A = K, NH4, Rb; the latter salts are isostructural with K2FeCl5,H2O. The anhydrous compounds A12VCl5 (A = Cs, Rb) are also examined and the preparation of the rubidium salt is reported for the first time. For these compounds the magnetic results are interpreted in terms of a weak antiferromagnetic interaction in a proposed polymeric structure and this is supported by other evidence. Some data are reported for VBr3 and VI3.

Vibrational spectra of crystalline malononitrile

1976 ◽  
Vol 54 (20) ◽  
pp. 3293-3302 ◽  
Author(s):  
R. Savoie ◽  
R. Brousseau ◽  
C. Nolin
Keyword(s):  
Phase I ◽  
Metastable Phase ◽  
Phase Iii ◽  
Site Symmetry ◽  
Monoclinic System ◽  
X Ray ◽  
Data Phase ◽  
Quadrupole Resonance ◽  
Resonance Data ◽  
Nuclear Quadrupole

The infrared and Raman spectra of the four solid phases of malononitrile have been recorded. The crystal structures of these solids are now relatively well established from the present results and from previous X-ray and nuclear quadrupole resonance data. Phase I belongs to the P21/n space group of the monoclinic system, with four molecules per unit cell. In phase II, the molecules occupy two sets of general positions in a crystal of P21 symmetry. The molecular site symmetry is Cs in phase III which is highly symmetric. The structure of the low-temperature metastable phase IV appears to be very similar to that of phase I.

Chlorine nuclear quadrupole resonance in some chloro complexes of divalent copper

1971 ◽  
Vol 24 (10) ◽  
pp. 1993 ◽  
Author(s):  
DE Scaife
Keyword(s):  
Nuclear Quadrupole Resonance ◽  
Covalent Bonding ◽  
Divalent Copper ◽  
Chloro Complexes ◽  
35Cl Nucleus ◽  
Square Planar ◽  
Bonding Interaction ◽  
Quadrupole Resonance ◽  
Square Planar Complexes ◽  
Nuclear Quadrupole

Nuclear quadrupole resonance for the 35Cl nucleus has been observed in some chloro complexes of divalent copper. Square-planar complexes each show two resonance lines, with the following frequencies (at 77�K): (CH3NH3)2CuCl4, 10.780, 12.157 MHz; (C2H5NH3)2CuCl4, 10.817, 12.074 MHz; (enH2)CuCl4, 10.271, 11.901 MHz; and (C3H7NH3)2CuCl4 at 223�K, 11.290 and 11.781 MHz. NH4CuCl3, containing dimeric Cu2Cl62- units, has resonances, at 77�K, at 11.907, 11.993, and 12.448 MHz. The trigonal pyramidal anion in Co(NH3)6CuCl5 has two resonances at 9.642 and 10.352 MHz at 77�K. ��� These results are compared with previous results for copper chloro complexes, and the implications of covalent bonding are discussed. In particular, it is suggested that the long-bond interaction between units in square-planar complexes amounts to 7-16% of the bonding interaction within the units.

Halogen nuclear quadrupole resonance and structural relationships in some complex halides of zinc and copper

1972 ◽  
Vol 25 (11) ◽  
pp. 2301 ◽  
Author(s):  
WJ Asker ◽  
DE Scaife ◽  
JA Watts
Keyword(s):  
Nuclear Quadrupole Resonance ◽  
Room Temperature ◽  
X Ray Diffraction ◽  
Mean Values ◽  
X Ray ◽  
Rubidium Salt ◽  
Structural Relationships ◽  
Quadrupole Resonance ◽  
The Mean ◽  
Nuclear Quadrupole

X-ray diffraction and halogen nuclear quadrupole resonance (n.q.r.) methods show that Rb3ZnBr5, (NH4)3ZnBr5, and CsZnI5 are isostructural with orthorhombic (NH4)3ZnCl5, and that Rb3ZnCl5 has the tetragonal Cs3CoCl5 structure. ZnI2,2NH3 is isomorphous with the corresponding chloride and bromide diammines. Rb2ZnBr4 and (NH4)2ZnBr4 have structures of Cs2ZnBr4 type, although the rubidium salt shows some stacking faults. In the complex chlorides 35Cl n.q.r. frequencies are grouped about 9 MHz, while the bromides have 81Br frequencies grouped around 60 MHz. The � → 3/2 transitions of 127I in the iodides are in the region of 76 MHz. The diammine compounds ZnBr2,2NH3 and ZnI2,2NH3 have frequencies close to the mean values for the ZnBr42- and ZnI42- ions respectively, but in the hydrates ZnCl2,l⅓H2O,ZnBr2,2H2O, β-KZnBr3,2H2O, and KZnI3,2H2O the halogen frequencies are increased. N.q.r. and X-ray data are also reported for the compound Cs3CuCl5, formed by quenching the melt. This compound slowly disproportionates at room temperature into Cs2CuCl4 and CsCl.

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