In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 47, No. 11 ( 1992-11-1), p. 1580-1592
Abstract:
The reactions of 1:1:1 molar ratio mixtures of NaSPh/MnCl 2 /Et 4 NBr and NaSPh/CoCl 2 / Et 4 NCl in methanol afford the compounds [Et 4 N] 4 [Mn(SPh) 3 Br][Mn(SPh) 3 Cl] (1) and [Et 4 N] 2 [Co 4 (SPh) 6 Cl 4 ] · MeCN (2), respectively, with the following crystal data: a = 14.408(5), b = 13.788(4), c = 17.984(5) Å, β = 90.16(2)°, space group P2 1 /c and Ζ = 4 for 1, and a = 21.976(4), b = 13.081(2), c = 22.012(4) Å, β = 105.48(1)°, space group P 2 1 /c for 2. The structures were refined to R values of 0.049 and 0.037, respectively. Crystals of 1 contain both of the paramagnetic (S = 5/2) mononuclear anions [Mn(SPh) 3 Br] 2- (3 a) and [Mn(SPh) 3 Cl] 2- (3b). The anions 3 a and 3 b are superimposed in an averaged unit cell and thus occupy crystallographically equivalent sites, the positions of the chlorine and bromine atoms being unresolved. The monohalide species are distributed statistically over 93% of the total anion positions. The remaining 7% are occupied by the dihalide species [Mn(SPh) 2 Br 2 ] 2- (4a) and [Mn(SPh) 2 BrCl] 2- (4b) in equal amounts. In all these cases the metal atoms exhibit a distorted tetrahedral stereochemistry. In crystals of 2 [Co 4 (SPh) 6 Cl 4 ] 2- anions (5) are observed which feature a {Co 4 S 6 Cl 4 } core consisting of a distorted (D 2d ) Co 4 tetrahedron inscribed in a moderately irregular S 6 octahedron defined by bridging S atoms of an adamantane type cage. The four chlorine atoms each bind to different Co atoms and define an outer Cl 4 tetrahedron, such that the overall symmetry of the {Co 4 S 6 Cl 4 } core comes close to T d . The results presented show that [M 3 (SPh) 3 Hal 6 ] 3- type species reported for M = Fe are not as readily formed for M = Mn and Co in methanolic solution, where other species are found instead. Physical properties such as solid state susceptibilities and 1 H NMR spectra confirm the identity of 1 and 2. Reactions of 4:1:2 molar ratio mixtures of NaSePh/MnCl 2 /Et 4 NCl and NaTePh/MnCl 2 /Et 4 NCl in methanol lead to [Et 4 N] 2 [Mn(SePh) 4 ] (6) and [Et 4 N] 2 [Mn(TePh) 4 ] (7). Both compounds crystallize in the monoclinic space group P2 1 /n with a = 16.162(4), b = 15.323(4), c = 16.949(4) Å, β = 91.28(2)°, Z = 4 for 6, and a = 16.367(6), b = 15.641(7), c = 17.220(7) Å, β = 92.00(3)°, Z = 4 for 7. Their structures were refined to R = 0.077 and 0.026, respectively. Four benzeneselenolate and benzenetellurolate ligands provide a slightly distorted tetrahedral coordination about the Mn(II) center for 6 and 7, respectively. The Mn–Se and Mn–Te distances average 2.567 and 2.742 Å, the Se– Mn– Se and Te–Mn–Te angles range from 99.1(1) to 124.2(1) and from 94.7(1) to 127.0(1)°, respectively.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-1992-1112
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
1992
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
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