
TY  - JOUR
A1  - Harrowfield, Jack M. 
A1  - Sharma, Raj Pal 
A1  - Skelton, Brian W. 
A1  - White, Allan H. 
T1  - Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. IV [Acid Salts] of the 4-Nitrophenoxides of Group 1
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1998
VL  - 51
IS  - 8
SP  - 747
EP  - 760
KW  - 
UR  - https://doi.org/10.1071/C97101 
N2  - Room-temperature single-crystal X-ray studies are recorded for a number of &#8216;acid salts&#8217; formed between Group 1 salts of 4-nitrophenol, M(4-np), and the parent ligand 4-npH, variously hydrated. The 1 : 1 salts M(4-np)(4-npH).x H2O are found for all of M = Li, Na, K, Rb and Cs. The lithium adduct (tetrahydrate) is monoclinic, C2/c, a 19&#183;438(4), b  11&#183;207(2), c 7&#183;421(2) &#197;, &#946; 91&#183;38(2)&#176;, Z = 4, conventional R on &#124;F&#124; being 0&#183;043 for 1369 independent &#8216;observed&#8217; (I &#62; 3&#963;(I)) diffractometer reflections. The sodium adduct (dihydrate) is monoclinic, C2, a 2&#183;174(3), b 3&#183;674(2), c 10&#183;358(1) &#197;, &#946; 117&#183;21(1)&#176;, Z = 2, R 0&#183;035 for No 1092; the potassium adduct (monohydrate) is monoclinic, C 2/c, a 22&#183;10(1), b 3&#183;798(3), c 21&#183;270(6) &#197;, &#946; 120&#183;97(4)&#176;, Z = 4, R 0&#183;050 for No 1065. The isomorphous rubidium and caesium monohydrates are triclinic, P-1, a &#x2248; 11&#183;9, b &#x2248; 10&#183;2,c &#x2248; 6&#183;3 &#197;, &#945; &#x2248; 90, &#946; &#x2248; 92, &#947; &#x2248; 112&#176;, Z = 2, R 0&#183;042, 0&#183;028 for No 2340, 3053 respectively. For M = Rb, a 1 : 3 adduct Rb(4-np).3(4-npH) is also obtained (with an isomorphous thallium counterpart recorded elsewhere): a 12&#183;143(5), b 11&#183;50(1), c 11&#183;36(1) &#197;, &#945; 114&#183;38(9), &#946; 110&#183;54(6), &#947; 96&#183;73(6)&#176;, Z = 2, R 0&#183;034 for No 3945. The lithium salt may be represented as &#91;Li(OH2)4&#93;+ (4-npH.4-np)&frac12;-. The cation lies disposed about a crystallographic 2 axis; the anion, close to an axis, confronts its rotational image, with the associated hydrogen atom modelled as disordered between them, rather than located on the 2 axis. The sodium salt is a sheet structure, the six-coordinate sodium atoms being disposed on a crystallographic 2 axis and linked up that axis ... Na(&#181;-O)2Na(&#181;-O)2Na ... by bridging water molecule oxygen atoms, while symmetry-related trans O-nitrophenoxide moieties are bridged by confronting phenoxide oxygen atoms about an associated hydrogen atom provisionally disposed on a 2 axis also. The potassium salt structure is developed from this array, modelled with disordered potassium atoms, now lying off the 2 axis, 0&#183;922(2) &#197; apart. In the rubidium/caesium structure, columns of oxygen-bridged metal ions are disposed about c, crosslinked by O-nitro-bonded phenoxide moieties, with confronting phenoxide oxygen atoms about a shared associated hydrogen. 
ER  -

