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Magnesium dichloride decahydrate (MgCl2·10H2O) and its deuterated counterpart (MgCl2·10D2O) are identified for the first time by in-situ powder synchrotron X-ray and spallation neutron diffraction. These substances are crystallized from a previously unidentified nanocrystalline compound, which originates from an amorphous state at low temperature. A combination of a recently developed autoindexing procedure and the charge-flipping method reveals that the crystal structure of MgCl2·10H2O consists of an ABCABC... sequence of Mg(H2O)6 octahedra. The Cl anions and remaining water molecules unconnected to the Mg2+ cations bind the octahedra, similar to other water-rich magnesium dichloride hydrates. The D positions in MgCl2·10D2O, determined by the difference Fourier methods using the neutron powder diffraction patterns at 2.5 GPa, show the features such as bifurcated hydrogen bonds and tetrahedrally coordinated O atoms, which were not found in other forms of magnesium chloride hydrates.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205252061500027X/ps5038sup1.cif
Contains datablocks 11615_publ, I, 11615_phase_1, 11615_phase_2, 11615_p_01

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Portable Document Format (PDF) file https://doi.org/10.1107/S205252061500027X/ps5038sup2.pdf
Extra experimental details and figures

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
(11615_phase_1) Deuterium oxide top
Crystal data top
D2.00OZ = 2
Mr = 20.03Dx = 1.773 Mg m3
Cubic, Pn3m? radiation
a = 3.347183 (18) ÅT = 298 K
V = 37.50 (1) Å3irregular, ? × ? × ? mm
Data collection top
PLANET (BL11), Materials and Life Science Experimental Facility, J-PARC Tokai, Ibaraki, Japan
diffractometer
Data collection mode: transmission
Radiation source: neutronScan method: time of flight
Specimen mounting: Pressure-tempearture variable system ('the MITO system')2θfixed = 90.00
Refinement top
Least-squares matrix: full3715 data points
Rp = 0.025Profile function: TOF Profile function number-3 with 21 terms Profile coefficients for exponential pseudovoigt convolution Von Dreele, 1990 (unpublished) #1 (alp ) = 0.0000 #2 (bet-0) = 0.000000 #3 (bet-1) = 0.000000 #4 (sig-0) = 12.6 #5 (sig-1) = 496.8 #6 (sig-2) = 2.2 #7 (gam-0) = 0.00 #8 (gam-1) = 6.72 #9 (gam-2) = 2.90 #10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00 #13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000 #16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000 #19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, TOF Profile function number-3 with 21 terms Profile coefficients for exponential pseudovoigt convolution Von Dreele, 1990 (unpublished) #1 (alp ) = 0.0000 #2 (bet-0) = 0.000000 #3 (bet-1) = 0.000000 #4 (sig-0) = 12.6 #5 (sig-1) = 547.3 #6 (sig-2) = 2.2 #7 (gam-0) = 0.00 #8 (gam-1) = 0.00 #9 (gam-2) = 5.69 #10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00 #13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000 #16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000 #19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rwp = 0.02847 parameters
Rexp = 0.0140 restraints
R(F2) = 0.20166(Δ/σ)max = 0.05
χ2 = 3.842Background function: GSAS Background function number 1 with 18 terms. Shifted Chebyshev function of 1st kind 1: 0.127013 2: -2.953800E-02 3: -5.451210E-03 4: -4.201140E-03 5: -1.768310E-03 6: 4.145860E-03 7: -5.281160E-03 8: 3.322800E-03 9: -1.798060E-0310: -8.129380E-0411: 2.257130E-0312: -1.843770E-03 13: 1.555140E-0314: -4.858040E-0415: 1.835960E-0316: -4.809670E-04 17: -4.887130E-0418: 1.330830E-03
Crystal data top
D2.00OZ = 2
Mr = 20.03? radiation
Cubic, Pn3mT = 298 K
a = 3.347183 (18) Åirregular, ? × ? × ? mm
V = 37.50 (1) Å3
Data collection top
PLANET (BL11), Materials and Life Science Experimental Facility, J-PARC Tokai, Ibaraki, Japan
diffractometer
Scan method: time of flight
Specimen mounting: Pressure-tempearture variable system ('the MITO system')2θfixed = 90.00
Data collection mode: transmission
Refinement top
Rp = 0.025χ2 = 3.842
Rwp = 0.0283715 data points
Rexp = 0.01447 parameters
R(F2) = 0.201660 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
D10.4254 (7)0.4254 (7)0.3768 (13)0.0182 (4)*0.1667
O10.250.250.250.01592 (18)*
Geometric parameters (Å, º) top
Mg1—O12.098 (10)O2—D40.927 (8)
Mg1—O1i2.098 (10)O3—D11.759 (9)
Mg1—O22.081 (7)O3—D1vii1.759 (9)
Mg1—O2i2.081 (7)O3—D30.977 (7)
Mg1—O2ii2.081 (7)O3—D3vii0.977 (7)
Mg1—O2iii2.081 (7)O4—D2viii1.840 (9)
Mg1—D12.742 (7)O4—D2ix1.840 (9)
Mg1—D1i2.742 (7)O4—D50.877 (12)
Mg1—D1ii2.742 (7)O4—D60.971 (11)
Mg1—D1iii2.742 (7)D1—Mg12.742 (7)
Mg1—D22.628 (6)D1—O11.010 (8)
Mg1—D2i2.628 (6)D1—O31.759 (9)
Mg1—D2ii2.628 (6)D1—D1iii1.631 (13)
Mg1—D2iii2.628 (6)D2—Mg12.628 (6)
Mg1—D42.671 (7)D2—O20.952 (7)
Mg1—D4i2.671 (7)D2—O4x1.840 (9)
Mg1—D4ii2.671 (7)D2—D41.479 (9)
Mg1—D4iii2.671 (7)D3—Cl1xi2.038 (7)
Cl1—D3iv2.038 (7)D3—O30.977 (7)
Cl1—D3v2.038 (7)D3—D3vii1.656 (11)
Cl1—D42.619 (10)D4—Mg12.671 (7)
Cl1—D4iii2.619 (10)D4—Cl12.619 (10)
Cl1—D4iv2.460 (9)D4—Cl1xi2.460 (9)
Cl1—D4v2.460 (9)D4—O20.927 (8)
Cl1—D5vi2.286 (11)D4—D21.479 (9)
O1—Mg12.098 (10)D5—Cl1vi2.286 (11)
O1—D11.010 (8)D5—O40.877 (12)
O1—D1iii1.010 (8)D5—D61.555 (10)
O2—Mg12.081 (7)D6—O40.971 (11)
O2—D20.952 (7)D6—D51.555 (10)
O1—Mg1—O1i180.0D3iv—Cl1—D3v79.4 (3)
O1—Mg1—O294.4 (3)Mg1—O1—D1119.6 (7)
O1—Mg1—O2i85.6 (3)Mg1—O1—D1iii119.6 (7)
O1—Mg1—O2ii85.6 (3)D1—O1—D1iii107.8 (14)
O1—Mg1—O2iii94.4 (3)Mg1—O2—D2114.9 (7)
O1i—Mg1—O285.6 (3)Mg1—O2—D4120.3 (8)
O1i—Mg1—O2i94.4 (3)D2—O2—D4103.8 (10)
O1i—Mg1—O2ii94.4 (3)D3—O3—D3vii115.9 (13)
O1i—Mg1—O2iii85.6 (3)D5—O4—D6114.5 (15)
O2—Mg1—O2i92.1 (4)O2—D2—D437.5 (6)
O2—Mg1—O2ii180.0Cl1xi—D3—O3170.1 (7)
O2—Mg1—O2iii87.9 (4)O2—D4—D238.7 (5)
O2i—Mg1—O2ii87.9 (4)O4—D5—D634.6 (9)
O2i—Mg1—O2iii180.0O4—D6—D530.9 (8)
O2ii—Mg1—O2iii92.1 (4)
Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) x+1/2, y+1/2, z; (iv) y+1/2, z1, x+3/2; (v) z+1/2, x, y+3/2; (vi) z+1, x, y+1; (vii) z, x, y+1; (viii) y+1/2, z1, x+1/2; (ix) z+1/2, x, y+1/2; (x) y+1/2, z, x+1/2; (xi) y+1/2, z, x+3/2.
(11615_phase_2) Magnesium chloride decadeuterate top
Crystal data top
Cl2D20MgO10V = 534.1 (5) Å3
Mr = 295.48Z = 2
Monoclinic, C2/mDx = 1.837 Mg m3
a = 10.3368 (2) Å? radiation
b = 7.4681 (3) ÅT = 298 K
c = 7.7232 (3) Åirregular, ? × ? × ? mm
β = 116.3813 (17)°
Data collection top
PLANET (BL11), Materials and Life Science Experimental Facility, J-PARC Tokai, Ibaraki, Japan
diffractometer
Data collection mode: transmission
Radiation source: neutronScan method: time of flight
Specimen mounting: Pressure-tempearture variable system ('the MITO system')2θfixed = 90.00
Refinement top
Least-squares matrix: full3715 data points
Rp = 0.025Profile function: TOF Profile function number-3 with 21 terms Profile coefficients for exponential pseudovoigt convolution Von Dreele, 1990 (unpublished) #1 (alp ) = 0.0000 #2 (bet-0) = 0.000000 #3 (bet-1) = 0.000000 #4 (sig-0) = 12.6 #5 (sig-1) = 496.8 #6 (sig-2) = 2.2 #7 (gam-0) = 0.00 #8 (gam-1) = 6.72 #9 (gam-2) = 2.90 #10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00 #13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000 #16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000 #19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, TOF Profile function number-3 with 21 terms Profile coefficients for exponential pseudovoigt convolution Von Dreele, 1990 (unpublished) #1 (alp ) = 0.0000 #2 (bet-0) = 0.000000 #3 (bet-1) = 0.000000 #4 (sig-0) = 12.6 #5 (sig-1) = 547.3 #6 (sig-2) = 2.2 #7 (gam-0) = 0.00 #8 (gam-1) = 0.00 #9 (gam-2) = 5.69 #10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00 #13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000 #16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000 #19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rwp = 0.02847 parameters
Rexp = 0.0140 restraints
R(F2) = 0.20166(Δ/σ)max = 0.05
χ2 = 3.842Background function: GSAS Background function number 1 with 18 terms. Shifted Chebyshev function of 1st kind 1: 0.127013 2: -2.953800E-02 3: -5.451210E-03 4: -4.201140E-03 5: -1.768310E-03 6: 4.145860E-03 7: -5.281160E-03 8: 3.322800E-03 9: -1.798060E-0310: -8.129380E-0411: 2.257130E-0312: -1.843770E-03 13: 1.555140E-0314: -4.858040E-0415: 1.835960E-0316: -4.809670E-04 17: -4.887130E-0418: 1.330830E-03
Crystal data top
Cl2D20MgO10β = 116.3813 (17)°
Mr = 295.48V = 534.1 (5) Å3
Monoclinic, C2/mZ = 2
a = 10.3368 (2) Å? radiation
b = 7.4681 (3) ÅT = 298 K
c = 7.7232 (3) Åirregular, ? × ? × ? mm
Data collection top
PLANET (BL11), Materials and Life Science Experimental Facility, J-PARC Tokai, Ibaraki, Japan
diffractometer
Scan method: time of flight
Specimen mounting: Pressure-tempearture variable system ('the MITO system')2θfixed = 90.00
Data collection mode: transmission
Refinement top
Rp = 0.025χ2 = 3.842
Rwp = 0.0283715 data points
Rexp = 0.01447 parameters
R(F2) = 0.201660 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mg10.00.00.00.005 (3)*
Cl10.2873 (6)0.00.5491 (10)0.029 (2)*
O10.0686 (10)0.00.2181 (16)0.022 (3)*
O20.1584 (8)0.1934 (10)0.1331 (12)0.022 (2)*
O30.00.2562 (15)0.50.031 (3)*
O40.4028 (14)0.00.0953 (15)0.035 (3)*
D10.0517 (8)0.1092 (9)0.3024 (8)0.0340 (8)*
D20.1412 (7)0.3047 (9)0.0662 (9)0.0340 (8)*
D30.0779 (6)0.3256 (8)0.4936 (9)0.0340 (8)*
D40.1849 (6)0.2264 (10)0.2601 (11)0.0340 (8)*
D50.4861 (9)0.00.1988 (14)0.0340 (8)*
D60.3192 (9)0.00.1215 (13)0.0340 (8)*
Geometric parameters (Å, º) top
Mg1—O12.098 (10)O2—D40.927 (8)
Mg1—O1i2.098 (10)O3—D11.759 (9)
Mg1—O22.081 (7)O3—D1vii1.759 (9)
Mg1—O2i2.081 (7)O3—D30.977 (7)
Mg1—O2ii2.081 (7)O3—D3vii0.977 (7)
Mg1—O2iii2.081 (7)O4—D2viii1.840 (9)
Mg1—D12.742 (7)O4—D2ix1.840 (9)
Mg1—D1i2.742 (7)O4—D50.877 (12)
Mg1—D1ii2.742 (7)O4—D60.971 (11)
Mg1—D1iii2.742 (7)D1—Mg12.742 (7)
Mg1—D22.628 (6)D1—O11.010 (8)
Mg1—D2i2.628 (6)D1—O31.759 (9)
Mg1—D2ii2.628 (6)D1—D1iii1.631 (13)
Mg1—D2iii2.628 (6)D2—Mg12.628 (6)
Mg1—D42.671 (7)D2—O20.952 (7)
Mg1—D4i2.671 (7)D2—O4x1.840 (9)
Mg1—D4ii2.671 (7)D2—D41.479 (9)
Mg1—D4iii2.671 (7)D3—Cl1xi2.038 (7)
Cl1—D3iv2.038 (7)D3—O30.977 (7)
Cl1—D3v2.038 (7)D3—D3vii1.656 (11)
Cl1—D42.619 (10)D4—Mg12.671 (7)
Cl1—D4iii2.619 (10)D4—Cl12.619 (10)
Cl1—D4iv2.460 (9)D4—Cl1xi2.460 (9)
Cl1—D4v2.460 (9)D4—O20.927 (8)
Cl1—D5vi2.286 (11)D4—D21.479 (9)
O1—Mg12.098 (10)D5—Cl1vi2.286 (11)
O1—D11.010 (8)D5—O40.877 (12)
O1—D1iii1.010 (8)D5—D61.555 (10)
O2—Mg12.081 (7)D6—O40.971 (11)
O2—D20.952 (7)D6—D51.555 (10)
O1—Mg1—O1i180.0D3iv—Cl1—D3v79.4 (3)
O1—Mg1—O294.4 (3)Mg1—O1—D1119.6 (7)
O1—Mg1—O2i85.6 (3)Mg1—O1—D1iii119.6 (7)
O1—Mg1—O2ii85.6 (3)D1—O1—D1iii107.8 (14)
O1—Mg1—O2iii94.4 (3)Mg1—O2—D2114.9 (7)
O1i—Mg1—O285.6 (3)Mg1—O2—D4120.3 (8)
O1i—Mg1—O2i94.4 (3)D2—O2—D4103.8 (10)
O1i—Mg1—O2ii94.4 (3)D3—O3—D3vii115.9 (13)
O1i—Mg1—O2iii85.6 (3)D5—O4—D6114.5 (15)
O2—Mg1—O2i92.1 (4)O2—D2—D437.5 (6)
O2—Mg1—O2ii180.0Cl1xi—D3—O3170.1 (7)
O2—Mg1—O2iii87.9 (4)O2—D4—D238.7 (5)
O2i—Mg1—O2ii87.9 (4)O4—D5—D634.6 (9)
O2i—Mg1—O2iii180.0O4—D6—D530.9 (8)
O2ii—Mg1—O2iii92.1 (4)
Symmetry codes: (i) x, y, z; (ii) x, y, z; (iii) x, y, z; (iv) x+1/2, y1/2, z+1; (v) x+1/2, y+1/2, z+1; (vi) x+1, y, z+1; (vii) x, y, z+1; (viii) x+1/2, y1/2, z; (ix) x+1/2, y+1/2, z; (x) x+1/2, y+1/2, z; (xi) x+1/2, y+1/2, z+1.

Experimental details

(11615_phase_1)(11615_phase_2)
Crystal data
Chemical formulaD2.00OCl2D20MgO10
Mr20.03295.48
Crystal system, space groupCubic, Pn3mMonoclinic, C2/m
Temperature (K)298298
a, b, c (Å)3.347183 (18), 3.347183, 3.34718310.3368 (2), 7.4681 (3), 7.7232 (3)
α, β, γ (°)90, 90, 9090, 116.3813 (17), 90
V3)37.50 (1)534.1 (5)
Z22
Radiation type??
µ (mm1)??
Specimen shape, size (mm)Irregular, ? × ? × ?Irregular, ? × ? × ?
Data collection
Data collection methodPLANET (BL11), Materials and Life Science Experimental Facility, J-PARC Tokai, Ibaraki, JapanPLANET (BL11), Materials and Life Science Experimental Facility, J-PARC Tokai, Ibaraki, Japan
Specimen mountingPressure-tempearture variable system ('the MITO system')Pressure-tempearture variable system ('the MITO system')
Data collection modeTransmissionTransmission
Scan methodTime of flightTime of flight
Absorption correction?
GSAS Absorption/surface roughness correction: function number 0 No correction is applied.
Tmin, Tmax1.000, 1.000
2θ values (°)2θfixed = 90.002θfixed = 90.00
Refinement
R factors and goodness of fitRp = 0.025, Rwp = 0.028, Rexp = 0.014, R(F2) = 0.20166, χ2 = 3.842Rp = 0.025, Rwp = 0.028, Rexp = 0.014, R(F2) = 0.20166, χ2 = 3.842
No. of data points37153715
No. of parameters4747

Computer programs: GSAS.

 

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