High-pressure, low-temperature, single-crystal neutron diffraction study of deuterated and hydrogenous ammonium hexaaquacopper(II) sulfate (Tutton's salt): A pressure-switchable Jahn-Teller distortion

Journal Article · Tue Nov 30 23:00:00 EST 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00077a032· OSTI ID:5154507

Simmons, C J ^[1]; Hitchman, M A; Stratemeier, H ^[2]; Schultz, A J ^[3]

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1. Brigham Young Univ., Laie, HI (United States)
2. Univ. of Tasmania, Hobart, Tasmania (Australia)
3. Argonne National Lab., IL (United States)

The first example of a pressure-induced Jahn-Teller distortion switch has been observed in a single-crystal time-of-flight neutron diffraction study of the Tutton salt (ND[sub 4])[sub 2][Cu(D[sub 2]O)[sub 6]](SO[sub 4])[sub 2] at T = 15 K, P = 1 bar (D[sub L]) and T = 15 K, P = 1.5 kbar (D[sub H]). Also studied was the hydrogenous salt (NH[sub 4])[sub 2][Cu(H[sub 2]O)[sub 6]](SO[sub 4])[sub 2] at T = 14 K, P = 1.4 kbar (H[sub H]). The unit cell parameters are as follows: D[sub L], a = 9.451(2) [angstrom], b = 12.736(3) [angstrom], c = 6.096(1) [angstrom], [beta] = 107.13(2)[degrees], Z = 2, V = 701.2(3) [angstrom][sup 3], space group = P2[sub 1]/a; D[sub H], a = 9.136(1) [angstrom], b = 12.285(2) [angstrom], c = 6.371(1) [angstrom], [beta] = 106.28(2)[degrees], Z = 2, V = 686.4(2) [angstrom][sup 3], space group = P2[sub 1]/a; H[sub H], a = 9.068(2) [angstrom], b = 12.232(2) [angstrom], c = 6.340(1) [angstrom], [beta] = 106.44(2), Z = 2, V = 674.5(2) [angstrom][sup 3], space group = P2[sub 1]/a. Application of 1.5 kbar of pressure to the deuterated crystal produces a decrease in the lengths of the a and b axes by 0.315(2) and 0.451(4) [angstrom], respectively, whereas the c axis increases by 0.275(1) [angstrom]. Comparison of the D[sub L] and D[sub H] structures shows that the long axis of the Jahn-Teller distortion has switched by 90[degrees], i.e., Cu(1)-O(7) = 2.022(2) and Cu(1)-O(8) = 2.310(2) [angstrom] for D[sub L] vs Cu(1)-O(7) = 2.290(2) and Cu(1)-O(8) = 2.014(2) [angstrom] for D[sub H], so that the D[sub H] and H[sub H] structures are similar. 38 refs., 6 figs., 3 tabs.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 5154507
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:24; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400100 -- Analytical & Separations Chemistry
400201* -- Chemical & Physicochemical Properties
AMMONIUM COMPOUNDS
COHERENT SCATTERING
COMPILED DATA
COPPER COMPOUNDS
COPPER SULFATES
CRYSTALLOGRAPHY
DATA
DEUTERIUM COMPOUNDS
DIFFRACTION
HYDRATES
HYDROGEN COMPOUNDS
INFORMATION
JAHN-TELLER EFFECT
NEUTRON DIFFRACTION
NUMERICAL DATA
OXYGEN COMPOUNDS
PRESSURE DEPENDENCE
SCATTERING
SULFATES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION