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trans-(NH 4 ) 2 [Ru(SO 3 ) 2 (NH 3 ) 4 ]·4H 2 O(1) (monoclinic, P2 1 /n; a = 629.8(3), b = 1000.6(2), c = 1345.7(5) pm, β = 112.25(4)°, Z = 2; R = 0.021; Rw = 0.017) is obtained as pale greenish-yellow crystals by reaction of trans-[Ru(SO 3 H) 2 (NH 3 ) 4 ] (2) with aqueous ammonia, and crystallization at +5 °C. The compound, when isolated, is stable at room temperature for only a few days even under inert gas, but persists under the mother liquor. In the centrosymmetric anion trans-[Ru(SO 3 ) 2 (NH 3 ) 4 ]2 -  the bonds Ru-S = 230.5(1) pm are significantly longer than in the neutral complex 2 (227.6(1) pm), whereas the Ru-N bonds are the same in both com­plexes within experimental error (averages 214.1 and 214.0 pm). Hence, the mutual trans-influence of the sulfite ligands is weakened on protonation; the bonding of the co-ligands in cis-position is not affected. The internal structure of the sulfite ligand in 1 with long S-O bonds (average 151.2(5) pm) and small angles O-S-O (average 106.1(6)°) and the weakened Ru-S bond are a good match. The structure of 1 is held together by a complex network of hydrogen bonds, in which all potential hydrogen-bond donors (OH 2 , NH 4  + , NH 3 ) and acceptors (H 2 O ,SO 3 ) are involved. The structural findings are reflected in the vibrational spectra.

zeitschrift für naturforschung b

The Crystal Structure of Diammonium trans-Tetraammindisulfitonithenate(II)Tetrahydrate,trans-(NH 4 ) 2 [Ru(SO 3 ) 2 (NH 3 ) 4 ]·4H 2 O,and the Tuning of the trans-Influence of the Sulfite Ligand