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Single-crystal synchrotron X-ray diffraction at 297 K revealed the spinel-related low-temperature orthorhombic form of black octahedrally shaped single crystals of lithium dimanganate, LiMn2O4, grown by the flux method. Three of five MnO6 octahedra show typical Jahn-Teller distortions associated with MnIII states. The bond valence sums indicate that these three sites are enriched with MnIII and the other two with MnIV, though the charge distribution among these sites is still partially disordered.
Supporting information
Key indicators
- Single-crystal synchrotron study
- T = 297 K
- Mean (Mn-O) = 0.003 Å
- R factor = 0.038
- wR factor = 0.038
- Data-to-parameter ratio = 10.6
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT112_ALERT_2_A ADDSYM Detects Additional (Pseudo) Symm. Elem... 4
| Author Response:
The checkCIf software suggested the possibility of pseudosymmetry
I41/amd. However the merge R factor was 10.7% after transforming
the unit cell from orthorhombic to tetragonal. In addition the
difference between the a and b cell dimensions was 0.028(2)\%A,
which is 14 times larger than the esu. Therefore the tetragonality
was discarded.
|
PLAT112_ALERT_2_A ADDSYM Detects Additional (Pseudo) Symm. Elem... m
| Author Response:
The checkCIf software suggested the possibility of pseudosymmetry
I41/amd. However the merge R factor was 10.7% after transforming
the unit cell from orthorhombic to tetragonal. In addition the
difference between the a and b cell dimensions was 0.028(2)\%A,
which is 14 times larger than the esu. Therefore the tetragonality
was discarded.
|
PLAT112_ALERT_2_A ADDSYM Detects Additional (Pseudo) Symm. Elem... m
| Author Response:
The checkCIf software suggested the possibility of pseudosymmetry
I41/amd. However the merge R factor was 10.7% after transforming
the unit cell from orthorhombic to tetragonal. In addition the
difference between the a and b cell dimensions was 0.028(2)\%A,
which is 14 times larger than the esu. Therefore the tetragonality
was discarded.
|
PLAT113_ALERT_2_A ADDSYM Suggests Possible Pseudo/New Spacegroup . I41/amd
| Author Response:
The checkCIf software suggested the possibility of pseudosymmetry
I41/amd. However the merge R factor was 10.7% after transforming
the unit cell from orthorhombic to tetragonal. In addition the
difference between the a and b cell dimensions was 0.028(2)\%A,
which is 14 times larger than the esu. Therefore the tetragonality
was discarded.
|
Alert level B
DIFMX01_ALERT_2_B The maximum difference density is > 0.1*ZMAX*1.00
_refine_diff_density_max given = 3.046
Test value = 2.500
PLAT094_ALERT_2_B Ratio of Maximum / Minimum Residual Density .... 4.66
PLAT097_ALERT_2_B Maximum (Positive) Residual Density ............ 3.05 e/A 3
| Author Response:
Maximum (positive) residual density exists at 0.71\%A from Mn3
as stated in the experimental section.
|
PLAT110_ALERT_2_B ADDSYM Detects Potential Lattice Centering or Halving . ?
Alert level C
DIFMX02_ALERT_1_C The minimum difference density is > 0.1*ZMAX*0.75
The relevant atom site should be identified.
| Author Response:
Maximum (negative) residual density exists at 1.65\%A from Li2
as stated in the experimental section.
|
GOODF01_ALERT_2_C The least squares goodness of fit parameter lies
outside the range 0.80 <> 2.00
Goodness of fit given = 3.203
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.11 Ratio
PLAT087_ALERT_2_C Unsatisfactory S value (Too High) .............. 3.20
4 ALERT level A = In general: serious problem
4 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
10 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: Diff14A Software (Vaalsta & Hester, 1997); cell refinement: Xtal3.7 (Hall et al., 2000); data reduction: Xtal3.7; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: Xtal3.7; molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: Xtal3.7.
Crystal data top
LiMn2O4 | F(000) = 6120 |
Mr = 180.82 | Dx = 4.28 Mg m−3 |
Orthorhombic, Fddd | Synchrotron radiation, λ = 0.75044 (5) Å |
Hall symbol: -f 2uv 2vw | Cell parameters from 24 reflections |
a = 24.7550 (9) Å | θ = 85.5–86.1° |
b = 24.8832 (9) Å | µ = 10.00 mm−1 |
c = 8.2003 (3) Å | T = 297 K |
V = 5051.3 (3) Å3 | Octahedron, black |
Z = 72 | 0.05 × 0.05 × 0.05 mm |
Data collection top
Tsukuba-BL-14A diffractometer | Rint = 0.025 |
ω/2θ scans | θmax = 36.5°, θmin = 2.5° |
Absorption correction: analytical (Xtal3.7 ABSORB; Hall et al., 2000) | h = −39→39 |
Tmin = 0.693, Tmax = 0.720 | k = −39→0 |
10732 measured reflections | l = −12→12 |
2642 independent reflections | 6 standard reflections every 194 reflections |
1557 reflections with F > 3σ(F) | intensity decay: none |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.038 | Weighting scheme based on measured s.u.'s |
wR(F2) = 0.038 | (Δ/σ)max = 0.0004 |
S = 3.20 | Δρmax = 3.05 e Å−3 |
1549 reflections | Δρmin = −0.65 e Å−3 |
146 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.25000 | 0.25000 | 0.50000 | 0.0092 (4) | |
Mn2 | 0.08098 (3) | 0.08515 (3) | 0.50078 (8) | 0.0097 (3) | |
Mn3 | 0.08407 (4) | 0.33028 (4) | 0.24970 (7) | 0.0093 (2) | |
Mn4 | 0.25330 (3) | 0.16797 (3) | 0.24552 (8) | 0.0087 (3) | |
Mn5 | 0.16670 (3) | 0.24425 (3) | 0.24413 (7) | 0.0083 (3) | |
Li1 | 0.12500 | 0.12500 | 0.12500 | 0.012 (6) | |
Li2 | 0.37500 | 0.2125 (4) | 0.37500 | 0.011 (5) | |
Li3 | 0.2057 (4) | 0.37500 | 0.37500 | 0.011 (5) | |
Li4 | 0.2904 (3) | 0.2941 (4) | 0.1238 (7) | 0.011 (3) | |
O1 | 0.17421 (13) | 0.16794 (14) | 0.2618 (4) | 0.0106 (12) | |
O2 | 0.07879 (13) | 0.00779 (13) | 0.4798 (4) | 0.0112 (12) | |
O3 | 0.07873 (15) | 0.33193 (14) | 0.4818 (4) | 0.0119 (12) | |
O4 | 0.25251 (16) | 0.17247 (12) | 0.4771 (4) | 0.0134 (13) | |
O5 | 0.00630 (12) | 0.00677 (12) | 0.2387 (4) | 0.0109 (13) | |
O6 | 0.25616 (14) | 0.09018 (12) | 0.2385 (4) | 0.0104 (13) | |
O7 | 0.16281 (14) | 0.32326 (12) | 0.2352 (3) | 0.0109 (13) | |
O8 | 0.09041 (11) | 0.24386 (12) | 0.2346 (4) | 0.0109 (13) | |
O9 | 0.08407 (19) | 0.16142 (13) | 0.5160 (4) | 0.0176 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0079 (4) | 0.0104 (3) | 0.0094 (5) | −0.0008 (3) | −0.0010 (3) | −0.0007 (3) |
Mn2 | 0.0095 (3) | 0.0117 (3) | 0.0080 (3) | −0.0009 (2) | −0.0010 (2) | −0.0004 (2) |
Mn3 | 0.0068 (2) | 0.0133 (2) | 0.0080 (3) | 0.0008 (2) | 0.0004 (2) | −0.0007 (2) |
Mn4 | 0.0069 (3) | 0.0112 (2) | 0.0081 (3) | 0.0001 (2) | 0.0004 (2) | 0.0002 (3) |
Mn5 | 0.0061 (3) | 0.0104 (2) | 0.0083 (3) | 0.0005 (2) | −0.0002 (3) | 0.0008 (2) |
Li1 | 0.012 (7) | 0.020 (7) | 0.005 (6) | −0.00000 | −0.00000 | −0.00000 |
Li2 | 0.008 (4) | 0.016 (5) | 0.008 (4) | −0.00000 | −0.002 (4) | −0.00000 |
Li3 | 0.011 (5) | 0.016 (5) | 0.006 (4) | −0.00000 | −0.00000 | −0.001 (3) |
Li4 | 0.009 (3) | 0.014 (3) | 0.011 (3) | 0.000 (2) | −0.002 (3) | 0.002 (3) |
O1 | 0.0080 (13) | 0.0123 (11) | 0.0114 (12) | −0.0010 (10) | 0.0015 (10) | −0.0016 (11) |
O2 | 0.0109 (13) | 0.0134 (12) | 0.0093 (12) | 0.0013 (10) | 0.0005 (13) | 0.0007 (11) |
O3 | 0.0076 (13) | 0.0165 (12) | 0.0114 (11) | −0.0004 (11) | 0.0018 (12) | 0.0007 (12) |
O4 | 0.0150 (14) | 0.0139 (13) | 0.0114 (13) | 0.0031 (12) | −0.0010 (12) | 0.0008 (12) |
O5 | 0.0077 (12) | 0.0138 (12) | 0.0112 (16) | −0.0005 (10) | −0.0001 (11) | −0.0024 (11) |
O6 | 0.0075 (13) | 0.0121 (12) | 0.0115 (14) | −0.0005 (9) | −0.0012 (11) | 0.0000 (11) |
O7 | 0.0075 (13) | 0.0139 (13) | 0.0113 (13) | 0.0005 (11) | 0.0007 (11) | −0.0017 (10) |
O8 | 0.0061 (12) | 0.0155 (13) | 0.0110 (13) | −0.0018 (9) | −0.0004 (11) | 0.0009 (11) |
O9 | 0.0284 (18) | 0.0113 (12) | 0.0131 (13) | 0.0019 (13) | −0.0028 (15) | −0.0014 (11) |
Geometric parameters (Å, º) top
Mn1i—O2ii | 1.967 (3) | Li1i—O1iv | 1.971 (3) |
Mn1i—O4i | 1.939 (3) | Li2—O2ii | 2.000 (6) |
Mn1i—O5ii | 2.155 (3) | Li2—O3 | 1.978 (6) |
Mn1i—O2 | 1.967 (3) | Li2—O3i | 1.978 (6) |
Mn1i—O4 | 1.939 (3) | Li2—O2 | 2.000 (6) |
Mn1i—O5 | 2.155 (3) | Li3—O4i | 1.984 (6) |
Mn2ii—O1i | 1.966 (3) | Li3—O7 | 2.024 (6) |
Mn2ii—O2ii | 1.933 (3) | Li3—O7 | 2.024 (6) |
Mn2ii—O4i | 2.085 (4) | Li3—O4 | 1.984 (6) |
Mn2ii—O9i | 2.108 (5) | Li4i—O5ii | 1.955 (9) |
Mn2ii—O9ii | 1.904 (3) | Li4i—O6 | 1.968 (8) |
Mn2ii—O9 | 1.915 (3) | Li4i—O8 | 1.931 (8) |
Mn3—O3 | 2.194 (4) | Li4i—O9 | 1.938 (8) |
Mn3—O6i | 1.947 (4) | O1i—O2ii | 2.572 (5) |
Mn3—O7 | 1.936 (3) | O1i—O4i | 2.625 (5) |
Mn3—O3 | 1.908 (3) | O1i—O5ii | 2.550 (5) |
Mn3—O7 | 1.961 (4) | O1i—O8iv | 2.789 (4) |
Mn3—O8 | 2.160 (3) | O2ii—O4i | 2.657 (5) |
Mn4i—O1i | 1.962 (3) | O2ii—O5ii | 2.670 (4) |
Mn4i—O3 | 1.871 (4) | O3—O4i | 2.761 (5) |
Mn4i—O4i | 1.903 (3) | O3—O6i | 2.643 (5) |
Mn4i—O5ii | 1.888 (3) | O3—O3 | 2.768 (5) |
Mn4i—O6i | 1.938 (3) | O3—O6iii | 2.556 (5) |
Mn4i—O6iii | 1.931 (3) | O4i—O5ii | 2.640 (5) |
Mn5i—O1i | 1.913 (3) | O5ii—O8iv | 2.772 (4) |
Mn5i—O2ii | 1.936 (3) | O6i—O6iii | 2.543 (4) |
Mn5i—O5ii | 1.907 (3) | O7i—O8i | 2.668 (4) |
Mn5i—O7i | 1.970 (3) | O7i—O7iv | 2.602 (5) |
Mn5i—O8i | 1.890 (3) | O7i—O8iv | 2.675 (4) |
Mn5i—O8iv | 1.884 (3) | O8i—O8iv | 2.482 (4) |
Li1i—O1i | 1.971 (3) | O9i—O9ii | 2.719 (6) |
Li1i—O1ii | 1.971 (3) | O9i—O9 | 2.545 (5) |
Li1i—O1iii | 1.971 (3) | O9i—O9 | 2.702 (6) |
| | | |
O2ii—Mn1i—O4i | 85.73 (15) | O3—Mn4i—O4i | 94.03 (15) |
O2ii—Mn1i—O5ii | 80.60 (12) | O3—Mn4i—O5ii | 97.04 (14) |
O2ii—Mn1i—O2 | 180.0000 | O3—Mn4i—O6i | 87.88 (15) |
O2ii—Mn1i—O4 | 94.27 (15) | O3—Mn4i—O6iii | 84.47 (14) |
O2ii—Mn1i—O5 | 99.40 (12) | O4i—Mn4i—O5ii | 88.29 (14) |
O4i—Mn1i—O5ii | 80.12 (13) | O4i—Mn4i—O6i | 95.10 (13) |
O4i—Mn1i—O2 | 94.27 (15) | O4i—Mn4i—O6iii | 176.93 (14) |
O4i—Mn1i—O4 | 180.0000 | O5ii—Mn4i—O6i | 173.83 (14) |
O4i—Mn1i—O5 | 99.88 (13) | O5ii—Mn4i—O6iii | 94.55 (14) |
O5ii—Mn1i—O2 | 99.40 (12) | O6i—Mn4i—O6iii | 82.18 (13) |
O5ii—Mn1i—O4 | 99.88 (13) | O1i—Mn5i—O2ii | 83.85 (14) |
O5ii—Mn1i—O5 | 180.0000 | O1i—Mn5i—O5ii | 83.77 (14) |
O2—Mn1i—O4 | 85.73 (15) | O1i—Mn5i—O7i | 176.45 (14) |
O2—Mn1i—O5 | 80.60 (12) | O1i—Mn5i—O8i | 95.46 (14) |
O4—Mn1i—O5 | 80.12 (13) | O1i—Mn5i—O8iv | 94.55 (13) |
O1i—Mn2ii—O2ii | 82.55 (14) | O2ii—Mn5i—O5ii | 88.02 (14) |
O1i—Mn2ii—O4i | 80.72 (14) | O2ii—Mn5i—O7i | 93.79 (13) |
O1i—Mn2ii—O9i | 97.24 (14) | O2ii—Mn5i—O8i | 95.68 (14) |
O1i—Mn2ii—O9ii | 96.16 (14) | O2ii—Mn5i—O8iv | 177.27 (14) |
O1i—Mn2ii—O9 | 178.50 (17) | O5ii—Mn5i—O7i | 93.51 (14) |
O2ii—Mn2ii—O4i | 82.72 (13) | O5ii—Mn5i—O8i | 176.13 (14) |
O2ii—Mn2ii—O9i | 94.23 (14) | O5ii—Mn5i—O8iv | 94.01 (13) |
O2ii—Mn2ii—O9ii | 178.50 (15) | O7i—Mn5i—O8i | 87.40 (14) |
O2ii—Mn2ii—O9 | 97.73 (14) | O7i—Mn5i—O8iv | 87.91 (13) |
O4i—Mn2ii—O9i | 176.51 (13) | O8i—Mn5i—O8iv | 82.26 (13) |
O4i—Mn2ii—O9ii | 97.84 (16) | O1i—Li1i—O1ii | 110.62 (13) |
O4i—Mn2ii—O9 | 97.84 (17) | O1i—Li1i—O1iii | 103.64 (14) |
O9i—Mn2ii—O9ii | 85.17 (17) | O1i—Li1i—O1iv | 114.33 (14) |
O9i—Mn2ii—O9 | 84.21 (16) | O1ii—Li1i—O1iii | 114.33 (14) |
O9ii—Mn2ii—O9 | 83.58 (14) | O1ii—Li1i—O1iv | 103.64 (14) |
O3—Mn3—O6i | 79.09 (14) | O1iii—Li1i—O1iv | 110.62 (13) |
O3—Mn3—O7 | 99.28 (13) | O2ii—Li2—O3 | 109.72 (14) |
O3—Mn3—O3 | 84.57 (14) | O2ii—Li2—O3i | 107.02 (13) |
O3—Mn3—O7 | 98.80 (14) | O2ii—Li2—O2 | 111.3 (5) |
O3—Mn3—O8 | 179.02 (13) | O3—Li2—O3i | 112.1 (5) |
O6i—Mn3—O7 | 95.77 (14) | O3—Li2—O2 | 107.02 (13) |
O6i—Mn3—O3 | 83.04 (15) | O3i—Li2—O2 | 109.72 (14) |
O6i—Mn3—O7 | 177.76 (14) | O4i—Li3—O7 | 103.94 (13) |
O6i—Mn3—O8 | 101.58 (12) | O4i—Li3—O7 | 107.82 (13) |
O7—Mn3—O3 | 175.70 (16) | O4i—Li3—O4 | 117.1 (5) |
O7—Mn3—O7 | 83.80 (14) | O7—Li3—O7 | 116.8 (5) |
O7—Mn3—O8 | 81.37 (13) | O7—Li3—O4 | 107.82 (13) |
O3—Mn3—O7 | 97.55 (15) | O7—Li3—O4 | 103.94 (13) |
O3—Mn3—O8 | 94.80 (14) | O5ii—Li4i—O6 | 107.6 (4) |
O7—Mn3—O8 | 80.54 (12) | O5ii—Li4i—O8 | 110.3 (5) |
O1i—Mn4i—O3 | 179.56 (13) | O5ii—Li4i—O9 | 114.2 (3) |
O1i—Mn4i—O4i | 85.52 (15) | O6—Li4i—O8 | 109.1 (3) |
O1i—Mn4i—O5ii | 82.93 (14) | O6—Li4i—O9 | 109.4 (5) |
O1i—Mn4i—O6i | 92.18 (15) | O8—Li4i—O9 | 106.1 (4) |
O1i—Mn4i—O6iii | 95.98 (14) | | |
Symmetry codes: (i) −x+3/4, −y+3/4, z; (ii) x+1/2, y+1/2, z; (iii) −x+3/4, y+1/2, −z+1/4; (iv) x+1/2, −y+3/4, −z+1/4. |
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