Composition Space of the (CuO, (1)/(2)Nb(2)O(5))/(HF)(x)().pyridine/H(2)O System. Structure and Synthesis of [pyH(+)](2)[CuNb(2)(py)(4)O(2)F(10)](2-) and CuNb(py)(4)OF(5).
Single crystals of [pyH(+)](2)[CuNb(2)(py)(4)O(2)F(10)](2)(-) and CuNb(py)(4)OF(5) were synthesized in a (HF)(x)().pyridine/pyridine/water solution (150 degrees C, 24 h, autogeneous pressure) using CuO and Nb(2)O(5) as reagents. The compound [pyH(+)](2)[CuNb(2)(py)(4)O(2)F(10)](2)(-) contains clusters of [CuNb(2)(py)(4)O(2)F(10)](2)(-) anions linked through N-H(+).F hydrogen bonds to the [pyH(+)] cations. In contrast CuNb(py)(4)OF(5) is a unidimensional compound consisting only of chains, perpendicular to the c axis, of alternating [Cu(py)(4)(O/F)(2/2)](0.5+) and [NbF(4)(O/F)(2/)(2)](0.5)(-) octahedra. The chains change direction between the [110] and [1&onemacr;0] every c/2. Crystal data for [pyH(+)](2)[CuNb(2)(py)(4)O(2)F(10)](2)(-): tetragonal, space group I4(1)22 (No. 98),with a = 11.408(3) Å, c = 30.36(1) Å, and Z = 4. Crystal data for CuNb(py)(4)OF(5): monoclinic, space group C2/c (No. 15), with a = 10.561(3) Å, b = 13.546(6) Å, c = 16.103(4) Å, beta = 97.77(2) degrees, and Z = 4.
Halasyamani
Paramasivan
P
Materials Research Center and Departments of Chemistry and Physics and Astronomy, Northwestern University, Evanston, Illinois 60208.
Willis
Michael J.
MJ
Stern
Charlotte L.
CL
Lundquist
Paul M.
PM
Wong
George K.
GK
Poeppelmeier
Kenneth R.
KR