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- W2013184654 abstract "Structural phase transitions have been identified in two nickel linear-chain compounds which have been studied extensively in connection with the Haldane gap. The low-temperature crystal structures of ${mathrm{N}mathrm{i}(mathrm{C}}_{2}{mathrm{H}}_{8}{mathrm{N}}_{2}{)}_{2}{mathrm{NO}}_{2}{mathrm{ClO}}_{4}$ (NENP) and ${mathrm{N}mathrm{i}(mathrm{C}}_{2}{mathrm{H}}_{8}{mathrm{N}}_{2}{)}_{2}{mathrm{NO}}_{2}{mathrm{PF}}_{6}$ (NENF) have been determined by x-ray diffraction below the transition temperatures at 275 K (NENP) and 235 K (NENF). The low-temperature phase of NENP is isostructural with the room-temperature phase; the structure consists of infinite chains of ${mathrm{Ni}}^{2+}$ ions bridged by ${mathrm{NO}}_{2}$ groups aligned along the $b$ axis of the orthorhombic unit cell (space group $Pnma,$ $a=15.196(4)AA{},$ $b=10.271(2)AA{},$ $c=8.183(3)AA{},$ $Z=4,$ ${R(F}_{0})=0.0345,$ ${R}_{w}{(F}_{0})=0.0524$). The distinguishing feature of the low-temperature phase of NENP is the ordered perchlorate anion. In contrast, the low-temperature phase of NENF is remarkable for the loss of symmetry resulting from ordering of the nitrite anion for space group ${P2}_{1}/n.$ The low-temperature structure of NENF consists of infinite chains of two distinct types of ${mathrm{Ni}}^{2+}$ ions bridged by ordered ${mathrm{NO}}_{2}$ groups aligned along the $c$ axis of the monoclinic unit cell [$a=8.926(6)AA{},$ $b=15.207(11)AA{},$ $c=10.273(7)AA{},$ $ensuremath{beta}=92.28(5)ifmmode^circelsetextdegreefi{},$ $Z=4,$ ${R(F}_{0})=0.0636,$ ${R}_{w}{(F}_{0})=0.0975$]. These results show that NENP remains a uniform chain of $S=1$ ions at low temperatures. However, the two different nickel sites in NENF means it is a site-alternating chain at low temperatures and is no longer a simple Haldane system." @default.
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- W2013184654 date "1997-07-01" @default.
- W2013184654 modified "2023-09-24" @default.
- W2013184654 title "Low-temperature crystal structures of two Haldane-gap nickel chains, NENP and NENF" @default.
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- W2013184654 doi "https://doi.org/10.1103/physrevb.56.147" @default.
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