The syntheses and room-temperature single-crystal X-ray structural
characterization of 1 : 3 adducts formed between silver(I) (pseudo-) halides,
AgX, and triphenylstibine, SbPh3, are described for X
= Cl, I, SCN, NCS, CN, NO3 (1)-(6). The chloride,
as its methanol solvate (1a), is isomorphous with the arsine analogue:
triclinic, P-1,
a 13·373(4), b
14·48(6), c 14·702(3) Å, α
83·49(3), β 87·76(2), γ 76·45(3)°;
Z = 2, conventional R on
F being 0·046 for No 5514
independent ‘observed’ reflections (I > 3σ(I )). A new
form (1b) of the chloride has also been authenticated: monoclinic,
P 21/c,
a 12·832(2), b
54·24(1), c 18·519(8) Å, β
129·68(3)°; Z = 8
(R 0·065 for No 5672). No
bromide has been obtained; the iodide (2) is described as monoclinic,
P 21/n,
a 19·611(4), b
14·473(6), c 17·74(1) Å, β
98·28(3)°; Z = 4
(R 0·036 for No 6769). The
thiocyanate crystallizes from acetonitrile or pyridine as an
S-bonded form (3) isomorphous with the arsine analogue:
monoclinic, P
21/n, a
19·143(7), b 14·288(5),
c 18·694(6) Å, β 98·81(2)°;
Z = 4 (R 0·037 for
No 4482). From 2-methylpyridine, remarkably, a solvate
is obtained in which the thiocyanate is N-bonded (4):
triclinic, P-1,
a 27·261(5), b
14·767(3), c 13·319(1) Å, α
91·53(1), β 101·58(1), γ 92·29(2)°;
Z = 4 (R 0·045 for
No 6900). The cyanide is also monoclinic,
P 21/n,
a 19·442(7), b
14·267(3), c 17·741(6) Å, β
97·63(3)°, z = 4;
R 0·057 for No 2487. The
unsolvated 1 : 3 nitrate complex (6a) is monoclinic, P
21/n, a
19·602(5), b 14·455(1),
c 17·727(2) Å, β 97·19(2)°,
Z = 4; R was 0·034
for No 6522. The complex is isomorphous with the arsenic
and phosphorus analogues, being mononuclear
[(Ph3Sb)3Ag(O2NO)].
The ethanol solvate (6b) is triclinic,
P-1, a
13·352(5), b 14·548(9),
c 14·701(4) Å, α 81·64(4),
β 84·45(3), γ 75·32(4)°, Z
= 2; R was 0·058 for
No 4702. Ag-Sb range between 2·6980(8) and
2·843(3) Å in the precise determinations; Ag-X are
2·481(4) and 2·52(1) Å (the two chlorides),
2·757(1) (I), 2·533(3) (SCN),
2·21(1) (NCS), 2· 09(3) (CN),
2·377(7) Å (unidentate ONO2)
The Isomorphous Structures of Ammonium trans-Diiodobis(ethanedial-dioximato-(1–)-N,N′)cobaltate(III) and Ammonium trans-Diiodobis(ethanedial-dioximato-(1–)-N,N′)rhodate(III): Extended Metaloximate Chains with a Novel ···I–M–I···I–M–I··· Zigzagged Structure