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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680400025X/wm6007sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680400025X/wm6007Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal synchrotron study
  • T = 297 K
  • Mean [sigma](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

Computing details top

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.

(I) top
Crystal data top
LiMn2O4F(000) = 6120
Mr = 180.82Dx = 4.28 Mg m3
Orthorhombic, FdddSynchrotron radiation, λ = 0.75044 (5) Å
Hall symbol: -f 2uv 2vwCell parameters from 24 reflections
a = 24.7550 (9) Åθ = 85.5–86.1°
b = 24.8832 (9) ŵ = 10.00 mm1
c = 8.2003 (3) ÅT = 297 K
V = 5051.3 (3) Å3Octahedron, black
Z = 720.05 × 0.05 × 0.05 mm
Data collection top
Tsukuba-BL-14A
diffractometer
Rint = 0.025
ω/2θ scansθmax = 36.5°, θmin = 2.5°
Absorption correction: analytical
(Xtal3.7 ABSORB; Hall et al., 2000)
h = 3939
Tmin = 0.693, Tmax = 0.720k = 390
10732 measured reflectionsl = 1212
2642 independent reflections6 standard reflections every 194 reflections
1557 reflections with F > 3σ(F) intensity decay: none
Refinement top
Refinement on F0 restraints
Least-squares matrix: full0 constraints
R[F2 > 2σ(F2)] = 0.038Weighting scheme based on measured s.u.'s
wR(F2) = 0.038(Δ/σ)max = 0.0004
S = 3.20Δρmax = 3.05 e Å3
1549 reflectionsΔρmin = 0.65 e Å3
146 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.250000.250000.500000.0092 (4)
Mn20.08098 (3)0.08515 (3)0.50078 (8)0.0097 (3)
Mn30.08407 (4)0.33028 (4)0.24970 (7)0.0093 (2)
Mn40.25330 (3)0.16797 (3)0.24552 (8)0.0087 (3)
Mn50.16670 (3)0.24425 (3)0.24413 (7)0.0083 (3)
Li10.125000.125000.125000.012 (6)
Li20.375000.2125 (4)0.375000.011 (5)
Li30.2057 (4)0.375000.375000.011 (5)
Li40.2904 (3)0.2941 (4)0.1238 (7)0.011 (3)
O10.17421 (13)0.16794 (14)0.2618 (4)0.0106 (12)
O20.07879 (13)0.00779 (13)0.4798 (4)0.0112 (12)
O30.07873 (15)0.33193 (14)0.4818 (4)0.0119 (12)
O40.25251 (16)0.17247 (12)0.4771 (4)0.0134 (13)
O50.00630 (12)0.00677 (12)0.2387 (4)0.0109 (13)
O60.25616 (14)0.09018 (12)0.2385 (4)0.0104 (13)
O70.16281 (14)0.32326 (12)0.2352 (3)0.0109 (13)
O80.09041 (11)0.24386 (12)0.2346 (4)0.0109 (13)
O90.08407 (19)0.16142 (13)0.5160 (4)0.0176 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0079 (4)0.0104 (3)0.0094 (5)0.0008 (3)0.0010 (3)0.0007 (3)
Mn20.0095 (3)0.0117 (3)0.0080 (3)0.0009 (2)0.0010 (2)0.0004 (2)
Mn30.0068 (2)0.0133 (2)0.0080 (3)0.0008 (2)0.0004 (2)0.0007 (2)
Mn40.0069 (3)0.0112 (2)0.0081 (3)0.0001 (2)0.0004 (2)0.0002 (3)
Mn50.0061 (3)0.0104 (2)0.0083 (3)0.0005 (2)0.0002 (3)0.0008 (2)
Li10.012 (7)0.020 (7)0.005 (6)0.000000.000000.00000
Li20.008 (4)0.016 (5)0.008 (4)0.000000.002 (4)0.00000
Li30.011 (5)0.016 (5)0.006 (4)0.000000.000000.001 (3)
Li40.009 (3)0.014 (3)0.011 (3)0.000 (2)0.002 (3)0.002 (3)
O10.0080 (13)0.0123 (11)0.0114 (12)0.0010 (10)0.0015 (10)0.0016 (11)
O20.0109 (13)0.0134 (12)0.0093 (12)0.0013 (10)0.0005 (13)0.0007 (11)
O30.0076 (13)0.0165 (12)0.0114 (11)0.0004 (11)0.0018 (12)0.0007 (12)
O40.0150 (14)0.0139 (13)0.0114 (13)0.0031 (12)0.0010 (12)0.0008 (12)
O50.0077 (12)0.0138 (12)0.0112 (16)0.0005 (10)0.0001 (11)0.0024 (11)
O60.0075 (13)0.0121 (12)0.0115 (14)0.0005 (9)0.0012 (11)0.0000 (11)
O70.0075 (13)0.0139 (13)0.0113 (13)0.0005 (11)0.0007 (11)0.0017 (10)
O80.0061 (12)0.0155 (13)0.0110 (13)0.0018 (9)0.0004 (11)0.0009 (11)
O90.0284 (18)0.0113 (12)0.0131 (13)0.0019 (13)0.0028 (15)0.0014 (11)
Geometric parameters (Å, º) top
Mn1i—O2ii1.967 (3)Li1i—O1iv1.971 (3)
Mn1i—O4i1.939 (3)Li2—O2ii2.000 (6)
Mn1i—O5ii2.155 (3)Li2—O31.978 (6)
Mn1i—O21.967 (3)Li2—O3i1.978 (6)
Mn1i—O41.939 (3)Li2—O22.000 (6)
Mn1i—O52.155 (3)Li3—O4i1.984 (6)
Mn2ii—O1i1.966 (3)Li3—O72.024 (6)
Mn2ii—O2ii1.933 (3)Li3—O72.024 (6)
Mn2ii—O4i2.085 (4)Li3—O41.984 (6)
Mn2ii—O9i2.108 (5)Li4i—O5ii1.955 (9)
Mn2ii—O9ii1.904 (3)Li4i—O61.968 (8)
Mn2ii—O91.915 (3)Li4i—O81.931 (8)
Mn3—O32.194 (4)Li4i—O91.938 (8)
Mn3—O6i1.947 (4)O1i—O2ii2.572 (5)
Mn3—O71.936 (3)O1i—O4i2.625 (5)
Mn3—O31.908 (3)O1i—O5ii2.550 (5)
Mn3—O71.961 (4)O1i—O8iv2.789 (4)
Mn3—O82.160 (3)O2ii—O4i2.657 (5)
Mn4i—O1i1.962 (3)O2ii—O5ii2.670 (4)
Mn4i—O31.871 (4)O3—O4i2.761 (5)
Mn4i—O4i1.903 (3)O3—O6i2.643 (5)
Mn4i—O5ii1.888 (3)O3—O32.768 (5)
Mn4i—O6i1.938 (3)O3—O6iii2.556 (5)
Mn4i—O6iii1.931 (3)O4i—O5ii2.640 (5)
Mn5i—O1i1.913 (3)O5ii—O8iv2.772 (4)
Mn5i—O2ii1.936 (3)O6i—O6iii2.543 (4)
Mn5i—O5ii1.907 (3)O7i—O8i2.668 (4)
Mn5i—O7i1.970 (3)O7i—O7iv2.602 (5)
Mn5i—O8i1.890 (3)O7i—O8iv2.675 (4)
Mn5i—O8iv1.884 (3)O8i—O8iv2.482 (4)
Li1i—O1i1.971 (3)O9i—O9ii2.719 (6)
Li1i—O1ii1.971 (3)O9i—O92.545 (5)
Li1i—O1iii1.971 (3)O9i—O92.702 (6)
O2ii—Mn1i—O4i85.73 (15)O3—Mn4i—O4i94.03 (15)
O2ii—Mn1i—O5ii80.60 (12)O3—Mn4i—O5ii97.04 (14)
O2ii—Mn1i—O2180.0000O3—Mn4i—O6i87.88 (15)
O2ii—Mn1i—O494.27 (15)O3—Mn4i—O6iii84.47 (14)
O2ii—Mn1i—O599.40 (12)O4i—Mn4i—O5ii88.29 (14)
O4i—Mn1i—O5ii80.12 (13)O4i—Mn4i—O6i95.10 (13)
O4i—Mn1i—O294.27 (15)O4i—Mn4i—O6iii176.93 (14)
O4i—Mn1i—O4180.0000O5ii—Mn4i—O6i173.83 (14)
O4i—Mn1i—O599.88 (13)O5ii—Mn4i—O6iii94.55 (14)
O5ii—Mn1i—O299.40 (12)O6i—Mn4i—O6iii82.18 (13)
O5ii—Mn1i—O499.88 (13)O1i—Mn5i—O2ii83.85 (14)
O5ii—Mn1i—O5180.0000O1i—Mn5i—O5ii83.77 (14)
O2—Mn1i—O485.73 (15)O1i—Mn5i—O7i176.45 (14)
O2—Mn1i—O580.60 (12)O1i—Mn5i—O8i95.46 (14)
O4—Mn1i—O580.12 (13)O1i—Mn5i—O8iv94.55 (13)
O1i—Mn2ii—O2ii82.55 (14)O2ii—Mn5i—O5ii88.02 (14)
O1i—Mn2ii—O4i80.72 (14)O2ii—Mn5i—O7i93.79 (13)
O1i—Mn2ii—O9i97.24 (14)O2ii—Mn5i—O8i95.68 (14)
O1i—Mn2ii—O9ii96.16 (14)O2ii—Mn5i—O8iv177.27 (14)
O1i—Mn2ii—O9178.50 (17)O5ii—Mn5i—O7i93.51 (14)
O2ii—Mn2ii—O4i82.72 (13)O5ii—Mn5i—O8i176.13 (14)
O2ii—Mn2ii—O9i94.23 (14)O5ii—Mn5i—O8iv94.01 (13)
O2ii—Mn2ii—O9ii178.50 (15)O7i—Mn5i—O8i87.40 (14)
O2ii—Mn2ii—O997.73 (14)O7i—Mn5i—O8iv87.91 (13)
O4i—Mn2ii—O9i176.51 (13)O8i—Mn5i—O8iv82.26 (13)
O4i—Mn2ii—O9ii97.84 (16)O1i—Li1i—O1ii110.62 (13)
O4i—Mn2ii—O997.84 (17)O1i—Li1i—O1iii103.64 (14)
O9i—Mn2ii—O9ii85.17 (17)O1i—Li1i—O1iv114.33 (14)
O9i—Mn2ii—O984.21 (16)O1ii—Li1i—O1iii114.33 (14)
O9ii—Mn2ii—O983.58 (14)O1ii—Li1i—O1iv103.64 (14)
O3—Mn3—O6i79.09 (14)O1iii—Li1i—O1iv110.62 (13)
O3—Mn3—O799.28 (13)O2ii—Li2—O3109.72 (14)
O3—Mn3—O384.57 (14)O2ii—Li2—O3i107.02 (13)
O3—Mn3—O798.80 (14)O2ii—Li2—O2111.3 (5)
O3—Mn3—O8179.02 (13)O3—Li2—O3i112.1 (5)
O6i—Mn3—O795.77 (14)O3—Li2—O2107.02 (13)
O6i—Mn3—O383.04 (15)O3i—Li2—O2109.72 (14)
O6i—Mn3—O7177.76 (14)O4i—Li3—O7103.94 (13)
O6i—Mn3—O8101.58 (12)O4i—Li3—O7107.82 (13)
O7—Mn3—O3175.70 (16)O4i—Li3—O4117.1 (5)
O7—Mn3—O783.80 (14)O7—Li3—O7116.8 (5)
O7—Mn3—O881.37 (13)O7—Li3—O4107.82 (13)
O3—Mn3—O797.55 (15)O7—Li3—O4103.94 (13)
O3—Mn3—O894.80 (14)O5ii—Li4i—O6107.6 (4)
O7—Mn3—O880.54 (12)O5ii—Li4i—O8110.3 (5)
O1i—Mn4i—O3179.56 (13)O5ii—Li4i—O9114.2 (3)
O1i—Mn4i—O4i85.52 (15)O6—Li4i—O8109.1 (3)
O1i—Mn4i—O5ii82.93 (14)O6—Li4i—O9109.4 (5)
O1i—Mn4i—O6i92.18 (15)O8—Li4i—O9106.1 (4)
O1i—Mn4i—O6iii95.98 (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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