Author:
Harrowfield Jack M.,Sharma Raj Pal,Skelton Brian W.,White Allan H.
Abstract
Room-temperature single-crystal X-ray studies are recorded for 2- and
4-nitrophenoxide salts of silver(I) and thallium(I), M(2-np) and Tl(4-np)
(anhydrous), and Ag(4-np).H2O. Ag(2-np) is monoclinic,
P21/c,
a 9·012(4), b
5·743(5), c 12·594(5) Å, β
104·34(4)°, Z = 4; conventional
R on |F| was
0·042 for No 1378
independent ‘observed’ (I >
3σ(I)) reflections. Tl(2-np) is monoclinic,
C2/c, a
27·250(3), b 3·712(1),
c 15·147(3) Å, β 114·41(1)°,
Z = 8, R 0·025 for
No 1346.
Ag(4-np).H2O is monoclinic,
P21/a,
a 5·613(6), b
13·191(7), c 9·844(5) Å, β
92·50(6)°, Z = 4,
R 0 ·033 for
No 622. Tl(4-np) is tetragonal,
I 41/a,
a 18·037(8), c
8·979(8) Å, Z = 16,
R 0·043 for
No 924. An acid salt of the
latter, Tl(4-np).(4-npH)3, triclinic,
P-1, a
11·861(8), b 11·45(1),
c 11· 423(1) Å, α 114·00(6),
β 109·78(5), γ 96·87(7)°, Z
= 2, R 0·042 for
No 3814, is isomorphous with its
rubidium analogue. These comprise a novel array of structures: although the
structures of the silver(I) complexes are two-dimensional sheets with familiar
head-tail connecting ligands, a strong silver-aromatic carbon interaction is
found in Ag(2-np) (Ag–C 2·496(5) Å). Tl(2-np) and Tl(4-np)
both present unusual forms related to the stair-polymer and cubane adducts
found in 1 : 1 coinage metal(I)/halide-unidentate nitrogen base adducts;
Tl(2-np) is a double-stranded stair-polymer array, with the phenoxide oxygen
atoms incorporated in the stair and the nitro oxygen atoms linking successive
thallium atoms. The structure of Tl(4-np) is based on a tetranuclear cubane
motif of -4 symmetry,
[Tl(O-phenoxide)]4,
these being linked into a three-dimensional network by further Tl ·
· · O-nitro interactions from adjacent
units. The structure of silver(I) picrate monohydrate, isomorphous with its
sodium counterpart, is also recorded: monoclinic, C
2/m, a 12·818(7),
b 20·208(8), c 3·
741(1) Å, β 88·25(3)°, Z =
4, R 0·047 for
No 1042, void of any significant
Ag · · · C contacts.