non-ambient crystallography
The high-pressure structural chemistry of α-zirconium phosphate, α-Zr(HPO4)2·H2O, was studied using in-situ high-pressure diffraction and synchrotron radiation. The layered phosphate was studied under both hydrostatic and non-hydrostatic conditions and Rietveld refinement carried out on the resulting diffraction patterns. It was found that under hydrostatic conditions no uptake of additional water molecules from the pressure-transmitting medium occurred, contrary to what had previously been observed with some zeolite materials and a layered titanium phosphate. Under hydrostatic conditions the sample remained crystalline up to 10 GPa, but under non-hydrostatic conditions the sample amorphized between 7.3 and 9.5 GPa. The calculated bulk modulus, K0 = 15.2 GPa, showed the material to be very compressible with the weak linkages in the structure of the type Zr—O—P.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614011317/zb5035sup1.cif | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614011317/zb5035sup2.rtv | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520614011317/zb5035sup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2052520614011317/zb5035sup4.pdf |
(ZRP_10_publ) top
Crystal data top
O9P2Zr | c = 13.8705 (15) Å |
Mr = 297.16 | β = 101.296 (9)° |
Monoclinic, P21/n | V = 558.54 (8) Å3 |
a = 8.3593 (4) Å | Z = 4 |
b = 4.9123 (2) Å | T = 298 K |
Refinement top
Least-squares matrix: full | Profile function: CW Profile function number 3 with 19 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. #1(GU) = 0.000 #2(GV) = 242.518 #3(GW) = 0.378 #4(GP) = 0.000 #5(LX) = 1.991 #6(LY) = 0.000 #7(S/L) = 0.0104 #8(H/L) = 0.0005 #9(trns) = 0.00 #10(shft)= 0.0000 #11(stec)= 0.00 #12(ptec)= 1.90 #13(sfec)= 0.00 #14(L11) = 0.000 #15(L22) = 0.000 #16(L33) = 0.000 #17(L12) = 0.000 #18(L13) = 0.000 #19(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0019 times the peak Aniso. broadening axis 0.0 0.0 1.0 |
Rp = 0.008 | 44 parameters |
Rwp = 0.012 | 8 restraints |
Rexp = 0.069 | (Δ/σ)max = 6.71 |
R(F2) = 0.14837 | Background function: GSAS Background function number 7 with 1 terms. Linear interpolation 1: -0.308080 |
3125 data points | Preferred orientation correction: March-Dollase AXIS 1 Ratio= 1.365 Frac 1.000 h= 0.000 k= 0.000 l= 1.000 AXIS 2 Ratio= 1.000 Frac 0.000 h= 0.000 k= 1.000 l= 1.000 AXIS 3 Ratio= 1.000 Frac 0.000 h= 0.000 k= 0.000 l= 1.000 Prefered orientation correction range: Min= 0.39602, Max= 1.58906 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
ZR1 | 0.2510 (12) | 0.244 (2) | 0.4970 (10) | 0.0153 (7)* | |
P2 | 0.382 (2) | 0.747 (6) | 0.3697 (14) | 0.01* | |
P3 | −0.1317 (18) | 0.250 (5) | 0.3826 (14) | 0.01* | |
O4 | 0.537 (3) | 0.896 (5) | 0.416 (3) | 0.01* | |
O5 | 0.371 (5) | 0.465 (6) | 0.413 (4) | 0.01* | |
O6 | 0.231 (3) | 0.859 (6) | 0.393 (4) | 0.01* | |
O7 | 0.345 (4) | 0.751 (10) | 0.2569 (17) | 0.01* | |
O8 | −0.255 (4) | 0.412 (5) | 0.429 (3) | 0.01* | |
O9 | −0.119 (5) | −0.044 (6) | 0.410 (4) | 0.01* | |
O10 | −0.169 (4) | 0.251 (12) | 0.2695 (17) | 0.01* | |
O11 | 0.037 (3) | 0.351 (5) | 0.383 (3) | 0.01* | |
O12 | −0.004 (7) | 0.747 (10) | 0.257 (4) | 0.01* |
Geometric parameters (Å, º) top
ZR1—P2i | 3.26 (2) | P3—O10 | 1.538 (14) |
ZR1—P3ii | 3.21 (3) | P3—O11 | 1.491 (15) |
ZR1—P3iii | 3.26 (2) | O4—ZR1i | 2.06 (4) |
ZR1—O4i | 2.06 (4) | O4—P2 | 1.515 (15) |
ZR1—O5 | 2.00 (4) | O5—ZR1 | 2.00 (4) |
ZR1—O6iv | 2.37 (3) | O5—P2 | 1.519 (15) |
ZR1—O8iii | 1.97 (3) | O6—ZR1v | 2.37 (3) |
ZR1—O9ii | 2.10 (4) | O6—P2 | 1.469 (15) |
ZR1—O11 | 2.21 (4) | O7—P2 | 1.534 (14) |
P2—ZR1i | 3.26 (2) | O8—ZR1iii | 1.97 (3) |
P2—O4 | 1.515 (15) | O8—P3 | 1.538 (15) |
P2—O5 | 1.519 (15) | O9—ZR1ii | 2.10 (4) |
P2—O6 | 1.469 (15) | O9—P3 | 1.492 (15) |
P2—O7 | 1.534 (14) | O10—P3 | 1.538 (14) |
P3—ZR1ii | 3.21 (3) | O10—O11 | 2.15 (5) |
P3—ZR1iii | 3.26 (2) | O11—ZR1 | 2.21 (4) |
P3—O8 | 1.538 (15) | O11—P3 | 1.491 (15) |
P3—O9 | 1.492 (15) | O11—O10 | 2.15 (5) |
O4i—ZR1—O5 | 92.7 (16) | O4—P2—O7 | 114 (3) |
O4i—ZR1—O6iv | 92.4 (13) | O5—P2—O6 | 98 (2) |
O4i—ZR1—O8iii | 93.3 (16) | O5—P2—O7 | 113 (4) |
O4i—ZR1—O9ii | 89.0 (16) | O6—P2—O7 | 102 (3) |
O4i—ZR1—O11 | 169.9 (15) | O8—P3—O9 | 115 (3) |
O5—ZR1—O6iv | 93.5 (16) | O8—P3—O10 | 114 (3) |
O5—ZR1—O8iii | 83.1 (18) | O8—P3—O11 | 122 (2) |
O5—ZR1—O9ii | 175 (2) | O9—P3—O10 | 105 (3) |
O5—ZR1—O11 | 83.4 (18) | O9—P3—O11 | 107 (2) |
O6iv—ZR1—O8iii | 174 (2) | O10—P3—O11 | 90 (2) |
O6iv—ZR1—O9ii | 91.1 (18) | ZR1i—O4—P2 | 131 (2) |
O6iv—ZR1—O11 | 78.6 (12) | ZR1—O5—P2 | 143 (3) |
O8iii—ZR1—O9ii | 92.1 (17) | ZR1v—O6—P2 | 117.9 (19) |
O8iii—ZR1—O11 | 95.5 (14) | ZR1iii—O8—P3 | 136 (2) |
O9ii—ZR1—O11 | 95.7 (14) | ZR1ii—O9—P3 | 126 (3) |
O4—P2—O5 | 113 (3) | ZR1—O11—P3 | 124 (3) |
O4—P2—O6 | 115 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) −x, −y+1, −z+1; (iv) x, y−1, z; (v) x, y+1, z. |