inorganic compounds
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
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680400025X/wm6007sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680400025X/wm6007Isup2.hkl |
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
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. |