The determination of the crystal structure of the
M phase, (Mn
xZn
1–x)
2V
2O
7 (0.75 <
x < 0.913), in the pseudobinary Mn
2V
2O
7–Zn
2V
2O
7 system for
x ≃ 0.8 shows that the previously published triclinic unit-cell parameters for this thortveitite-related phase do not describe a true lattice for this phase. Instead, single-crystal X-ray data and Rietveld refinement of synchrotron X-ray powder data show that the
M phase has a different triclinic structure in the space group
P with
Z = 2. As prior work has suggested, the crystal structure can be described as a distorted version of the thortveitite crystal structure of β-Mn
2V
2O
7. A twofold superstructure in diffraction patterns of crystals of the
M phase used for single-crystal X-ray diffraction work arises from twinning by reticular pseudomerohedry. This superstructure can be described as a commensurate modulation of a pseudo-monoclinic basis structure closely related to the crystal structure of β-Mn
2V
2O
7. In comparison with the distortions introduced when β-Mn
2V
2O
7 transforms at low temperature to α-Mn
2V
2O
7, the distortions which give rise to the
M phase from the β-Mn
2V
2O
7 prototype are noticeably less pronounced.
Supporting information
CCDC references: 1857048; 1857047
Data collection: APEX3 (Bruker, 2016) for sc. Cell refinement: SAINT-Plus (Bruker, 2016) for sc. Data reduction: SAINT-Plus (Bruker, 2016) for sc. Program(s) used to solve structure: SHELXT (Sheldrick, 2015) for sc. Program(s) used to refine structure: TOPAS4.2 (Coelho, 2009) for powder; JANA2006 (Petříček et al., 2014) for sc. For both structures, molecular graphics: CrystalMaker (Palmer, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).
Manganese zinc divanadate (powder)
top
Crystal data top
Mn1.60O7V2Zn0.40 | γ = 84.6100 (1)° |
Mr = 327.94 | V = 279.97 (1) Å3 |
Triclinic, P1 | Z = 2 |
Hall symbol: -P 1 | Dx = 3.89 Mg m−3 |
a = 6.88143 (1) Å | Synchrotron radiation, λ = 0.826406 Å |
b = 7.92420 (1) Å | T = 298 K |
c = 5.45516 (1) Å | dark_grey |
α = 84.5309 (1)° | cylinder, 40 × 0.5 mm |
β = 71.3730 (1)° | |
Data collection top
Beamline_I11,_Diamond_Light_Source diffractometer | Scan method: continuous |
Specimen mounting: Borosilicate glass capillary | 2θmin = 5.5°, 2θmax = 151.746°, 2θstep = 0.001° |
Refinement top
Rp = 0.086 | Excluded region(s): 14.9-15.2, 19.25-19.35, 28.55-28.86, 28.925-29.05 degrees |
Rwp = 0.111 | 60 parameters |
Rexp = 0.068 | (Δ/σ)max = 0.001 |
RBragg = 0.086 | Background function: Chebychev polynomial, Coefficient
0 64.55935 1
-48.25469 2 31.42671
3 -21.91713 4
15.57408 5 -10.13776
6 5.686649 7
-2.320198 8 -1.271288
9 1.725147 10
-3.066357 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn1 | 0.16013 (8) | 0.14568 (6) | 0.81455 (9) | 0.0096 (1) | 0.8 |
Zn1 | 0.16013 (8) | 0.14568 (6) | 0.81455 (9) | 0.0096 (1) | 0.2 |
Mn2 | 0.65244 (7) | 0.66416 (6) | 0.81888 (9) | 0.0096 (1) | 0.8 |
Zn2 | 0.65244 (7) | 0.66416 (6) | 0.81888 (9) | 0.0096 (1) | 0.2 |
V1 | 0.82609 (7) | 0.42791 (6) | 0.24385 (9) | 0.0038 (1) | |
V2 | 0.30553 (8) | 0.90932 (6) | 0.28968 (9) | 0.0038 (1) | |
O1 | 0.2064 (3) | 0.7606 (3) | 0.5441 (4) | 0.0136 (1) | |
O2 | 0.4557 (3) | 0.1588 (2) | 0.8797 (4) | 0.0136 (1) | |
O3 | 0.9188 (3) | 0.6415 (2) | 0.9496 (4) | 0.0136 (1) | |
O4 | 0.3671 (3) | 0.5691 (3) | 0.8824 (4) | 0.0136 (1) | |
O5 | 0.8597 (3) | 0.0718 (3) | 0.8855 (4) | 0.0136 (1) | |
O6 | 0.6965 (4) | 0.9072 (3) | 0.5769 (4) | 0.0136 (1) | |
O7 | 0.2056 (3) | 0.4281 (3) | 0.5483 (4) | 0.0136 (1) | |
Geometric parameters (Å, º) top
Mn1—O5i | 2.107 (2) | Mn2—O4iii | 2.328 (2) |
Mn1—O6ii | 2.111 (2) | Zn2—O4 | 2.082 (2) |
Mn1—O3iii | 2.143 (2) | Zn2—O7ii | 2.097 (2) |
Mn1—O2 | 2.187 (2) | Zn2—O3 | 2.156 (2) |
Mn1—O5iv | 2.242 (2) | Zn2—O2iii | 2.165 (2) |
Mn1—O7 | 2.538 (2) | Zn2—O6 | 2.216 (2) |
Zn1—O5i | 2.107 (2) | Zn2—O4iii | 2.328 (2) |
Zn1—O6ii | 2.111 (2) | V1—O7ii | 1.636 (2) |
Zn1—O3iii | 2.143 (2) | V1—O4ii | 1.679 (3) |
Zn1—O2 | 2.187 (2) | V1—O1ii | 1.785 (2) |
Zn1—O5iv | 2.242 (2) | V1—O3v | 1.801 (2) |
Zn1—O7 | 2.538 (2) | V1—O3vi | 2.209 (2) |
Mn2—O4 | 2.082 (2) | V2—O2ii | 1.674 (2) |
Mn2—O7ii | 2.097 (2) | V2—O6vii | 1.684 (2) |
Mn2—O3 | 2.156 (2) | V2—O5ii | 1.692 (3) |
Mn2—O2iii | 2.165 (2) | V2—O1 | 1.737 (2) |
Mn2—O6 | 2.216 (2) | | |
| | | |
O5i—Mn1—O6ii | 102.45 (9) | O7ii—Mn2—O6 | 80.00 (7) |
O5i—Mn1—O3iii | 97.53 (8) | O7ii—Mn2—O4iii | 106.30 (7) |
O5i—Mn1—O2 | 157.57 (8) | O3—Mn2—O2iii | 81.75 (8) |
O5i—Mn1—O5iv | 77.60 (10) | O3—Mn2—O6 | 101.54 (8) |
O5i—Mn1—O7 | 109.79 (8) | O3—Mn2—O4iii | 70.19 (8) |
O6ii—Mn1—O3iii | 139.34 (7) | O2iii—Mn2—O6 | 80.30 (7) |
O6ii—Mn1—O2 | 92.18 (8) | O2iii—Mn2—O4iii | 92.63 (7) |
O6ii—Mn1—O5iv | 117.25 (8) | O6—Mn2—O4iii | 169.97 (9) |
O6ii—Mn1—O7 | 72.62 (7) | O4—Zn2—O7ii | 96.73 (9) |
O3iii—Mn1—O2 | 81.54 (8) | O4—Zn2—O3 | 143.61 (8) |
O3iii—Mn1—O5iv | 101.38 (8) | O4—Zn2—O2iii | 95.31 (8) |
O3iii—Mn1—O7 | 67.36 (7) | O4—Zn2—O6 | 113.77 (9) |
O2—Mn1—O5iv | 80.61 (8) | O4—Zn2—O4iii | 73.75 (10) |
O2—Mn1—O7 | 90.66 (7) | O7ii—Zn2—O3 | 97.79 (8) |
O5iv—Mn1—O7 | 166.84 (8) | O7ii—Zn2—O2iii | 159.79 (7) |
O5i—Zn1—O6ii | 102.45 (9) | O7ii—Zn2—O6 | 80.00 (7) |
O5i—Zn1—O3iii | 97.53 (8) | O7ii—Zn2—O4iii | 106.30 (7) |
O5i—Zn1—O2 | 157.57 (8) | O3—Zn2—O2iii | 81.75 (8) |
O5i—Zn1—O5iv | 77.60 (10) | O3—Zn2—O6 | 101.54 (8) |
O5i—Zn1—O7 | 109.79 (8) | O3—Zn2—O4iii | 70.19 (8) |
O6ii—Zn1—O3iii | 139.34 (7) | O2iii—Zn2—O6 | 80.30 (7) |
O6ii—Zn1—O2 | 92.18 (8) | O2iii—Zn2—O4iii | 92.63 (7) |
O6ii—Zn1—O5iv | 117.25 (8) | O6—Zn2—O4iii | 169.97 (9) |
O6ii—Zn1—O7 | 72.62 (7) | O7ii—V1—O4ii | 113.90 (11) |
O3iii—Zn1—O2 | 81.54 (8) | O7ii—V1—O1ii | 100.52 (10) |
O3iii—Zn1—O5iv | 101.38 (8) | O7ii—V1—O3v | 119.95 (11) |
O3iii—Zn1—O7 | 67.36 (7) | O4ii—V1—O1ii | 103.33 (10) |
O2—Zn1—O5iv | 80.61 (8) | O4ii—V1—O3v | 118.72 (10) |
O2—Zn1—O7 | 90.66 (7) | O1ii—V1—O3v | 93.80 (8) |
O5iv—Zn1—O7 | 166.84 (8) | O2ii—V2—O6vii | 111.52 (11) |
O4—Mn2—O7ii | 96.73 (9) | O2ii—V2—O5ii | 113.18 (10) |
O4—Mn2—O3 | 143.61 (8) | O2ii—V2—O1 | 109.11 (9) |
O4—Mn2—O2iii | 95.31 (8) | O6vii—V2—O5ii | 110.53 (11) |
O4—Mn2—O6 | 113.77 (9) | O6vii—V2—O1 | 106.70 (10) |
O4—Mn2—O4iii | 73.75 (10) | O5ii—V2—O1 | 105.39 (10) |
O7ii—Mn2—O3 | 97.79 (8) | V2—O1—V1ii | 162.74 (11) |
O7ii—Mn2—O2iii | 159.79 (7) | | |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) −x+1, −y, −z+2; (v) −x+2, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, −y+2, −z+1. |
Manganese zinc divanadate (sc)
top
Crystal data top
Mn1.612O7V2Zn0.388 | Z = 2 |
Mr = 327.8 | F(000) = 308 |
Triclinic, P1 | Dx = 3.907 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 6.8575 (2) Å | Cell parameters from 1679 reflections |
b = 7.9147 (3) Å | θ = 3.1–43.1° |
c = 5.4505 (6) Å | µ = 8.45 mm−1 |
α = 84.6178 (17)° | T = 100 K |
β = 71.450 (2)° | Irregular, black |
γ = 84.719 (2)° | 0.06 × 0.05 × 0.04 mm |
V = 278.61 (3) Å3 | |
Data collection top
Bruker Kappa APEXII CCD diffractometer | 3222 reflections with I > 3σ(I) |
Radiation source: X-ray tube | Rint = 0 |
ω– and φ–scans | θmax = 43.3°, θmin = 3.1° |
Absorption correction: multi-scan (TWINABS; Bruker, 2016) | h = −9→13 |
Tmin = 0.60, Tmax = 0.71 | k = −15→15 |
4889 measured reflections | l = −10→8 |
4889 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
R[F > 3σ(F)] = 0.042 | 31 constraints |
wR(F) = 0.102 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
S = 1.18 | (Δ/σ)max = 0.033 |
4889 reflections | Δρmax = 1.51 e Å−3 |
110 parameters | Δρmin = −1.54 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn1 | 0.15957 (12) | 0.14823 (12) | 0.81536 (13) | 0.01408 (14) | 0.798 (6) |
Zn1 | 0.15957 (12) | 0.14823 (12) | 0.81536 (13) | 0.01408 (14) | 0.202 (6) |
Mn2 | 0.65228 (11) | 0.66509 (12) | 0.81776 (13) | 0.01226 (13) | 0.814 (6) |
Zn2 | 0.65228 (11) | 0.66509 (12) | 0.81776 (13) | 0.01226 (13) | 0.186 (6) |
V1 | 0.82775 (17) | 0.42761 (14) | 0.2411 (4) | 0.0085 (2) | 0.843 (8) |
V2 | 0.30349 (16) | 0.90968 (14) | 0.2939 (4) | 0.0087 (2) | 0.843 (8) |
O1 | 0.2108 (3) | 0.7627 (2) | 0.5378 (4) | 0.0460 (9) | |
O2 | 0.4504 (3) | 0.1638 (3) | 0.8831 (5) | 0.0211 (7) | |
O3 | 0.9200 (3) | 0.6445 (3) | 0.9442 (5) | 0.0194 (6) | |
O4 | 0.3676 (5) | 0.5738 (5) | 0.8803 (8) | 0.0201 (8) | |
O5 | 0.8601 (5) | 0.0706 (5) | 0.8909 (7) | 0.0159 (7) | |
O6 | 0.6985 (5) | 0.9047 (5) | 0.5740 (7) | 0.0146 (7) | |
O7 | 0.2033 (6) | 0.4225 (5) | 0.5525 (7) | 0.0231 (9) | |
V2' | 0.3230 (8) | 0.9268 (7) | 0.2381 (15) | 0.0087 (2) | 0.157 (8) |
V1' | 0.8062 (8) | 0.4121 (7) | 0.2971 (14) | 0.0085 (2) | 0.157 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.01089 (16) | 0.0189 (2) | 0.0134 (2) | −0.00258 (14) | −0.00335 (11) | −0.00575 (13) |
Zn1 | 0.01089 (16) | 0.0189 (2) | 0.0134 (2) | −0.00258 (14) | −0.00335 (11) | −0.00575 (13) |
Mn2 | 0.01074 (17) | 0.0135 (2) | 0.0134 (2) | −0.00149 (13) | −0.00385 (11) | −0.00406 (11) |
Zn2 | 0.01074 (17) | 0.0135 (2) | 0.0134 (2) | −0.00149 (13) | −0.00385 (11) | −0.00406 (11) |
V1 | 0.0062 (2) | 0.0103 (2) | 0.0080 (5) | −0.00016 (15) | −0.0004 (2) | −0.0025 (2) |
V2 | 0.0093 (2) | 0.0075 (2) | 0.0100 (5) | 0.00110 (15) | −0.0043 (2) | −0.0010 (2) |
O1 | 0.0686 (14) | 0.0310 (12) | 0.0429 (13) | −0.0105 (10) | −0.0285 (11) | 0.0218 (9) |
O2 | 0.0153 (8) | 0.0207 (9) | 0.0328 (13) | 0.0077 (6) | −0.0143 (6) | −0.0145 (7) |
O3 | 0.0158 (8) | 0.0173 (8) | 0.0278 (12) | 0.0080 (6) | −0.0114 (6) | −0.0087 (6) |
O4 | 0.0159 (11) | 0.0195 (12) | 0.0279 (13) | −0.0015 (9) | −0.0110 (10) | −0.0010 (11) |
O5 | 0.0135 (10) | 0.0153 (10) | 0.0210 (11) | −0.0010 (8) | −0.0085 (9) | −0.0002 (9) |
O6 | 0.0189 (11) | 0.0145 (10) | 0.0122 (9) | −0.0016 (8) | −0.0060 (8) | −0.0048 (8) |
O7 | 0.0254 (12) | 0.0275 (15) | 0.0198 (12) | 0.0051 (10) | −0.0097 (10) | −0.0159 (12) |
V2' | 0.0093 (2) | 0.0075 (2) | 0.0100 (5) | 0.00110 (15) | −0.0043 (2) | −0.0010 (2) |
V1' | 0.0062 (2) | 0.0103 (2) | 0.0080 (5) | −0.00016 (15) | −0.0004 (2) | −0.0025 (2) |
Geometric parameters (Å, º) top
Mn1—O2 | 2.157 (3) | V1—V1' | 0.313 (7) |
Mn1—O3i | 2.119 (3) | V2—O1 | 1.683 (2) |
Mn1—O5ii | 2.100 (4) | V2—O2iii | 1.734 (2) |
Mn1—O6iii | 2.099 (3) | V2—O5iii | 1.719 (5) |
Mn2—O2i | 2.121 (3) | V2—O6v | 1.693 (4) |
Mn2—O3 | 2.145 (3) | V2—V2' | 0.314 (7) |
Mn2—O4 | 2.059 (4) | O1—V2' | 1.983 (7) |
Mn2—O6 | 2.198 (4) | O1—V1'iii | 1.570 (6) |
Mn2—O7iii | 2.098 (4) | O2—V2'iii | 1.611 (5) |
Zn2—O4 | 2.059 (4) | O3—V1'iv | 1.960 (5) |
V1—O1iii | 1.822 (2) | O4—V1'iii | 1.749 (9) |
V1—O3iv | 1.776 (2) | O5—V2'iii | 1.621 (9) |
V1—O4iii | 1.674 (5) | O6—V2'v | 1.724 (8) |
V1—O7iii | 1.664 (5) | O7—V1'iii | 1.594 (8) |
| | | |
O2—Mn1—O3i | 80.79 (10) | Mn2i—O2—V2'iii | 128.8 (3) |
O2—Mn1—O5ii | 156.43 (13) | V2iii—O2—V2'iii | 9.9 (3) |
O2—Mn1—O6iii | 92.92 (13) | Mn1i—O3—Mn2 | 98.25 (9) |
O3i—Mn1—O5ii | 97.32 (12) | Mn1i—O3—V1iv | 126.60 (15) |
O3i—Mn1—O6iii | 140.58 (13) | Mn1i—O3—V1'iv | 125.7 (2) |
O5ii—Mn1—O6iii | 102.73 (16) | Mn2—O3—V1iv | 125.62 (17) |
O2i—Mn2—O3 | 81.01 (10) | Mn2—O3—V1'iv | 120.7 (3) |
O2i—Mn2—O4 | 95.27 (13) | V1iv—O3—V1'iv | 7.8 (2) |
O2i—Mn2—O6 | 81.62 (12) | Mn2—O4—Zn2 | 0.0 (5) |
O2i—Mn2—O7iii | 159.11 (14) | Mn2—O4—V1iii | 144.3 (2) |
O3—Mn2—O4 | 144.71 (14) | Mn2—O4—V1'iii | 134.3 (3) |
O3—Mn2—O6 | 100.88 (13) | Zn2—O4—V1iii | 144.3 (2) |
O3—Mn2—O7iii | 97.24 (14) | Zn2—O4—V1'iii | 134.3 (3) |
O4—Mn2—O6 | 113.35 (16) | V1iii—O4—V1'iii | 10.18 (19) |
O4—Mn2—O7iii | 97.81 (17) | Mn1vi—O5—V2iii | 131.7 (2) |
O6—Mn2—O7iii | 78.26 (15) | Mn1vi—O5—V2'iii | 141.9 (3) |
O1iii—V1—O3iv | 93.79 (11) | V2iii—O5—V2'iii | 10.2 (2) |
O1iii—V1—O4iii | 101.47 (17) | Mn1iii—O6—Mn2 | 109.52 (17) |
O1iii—V1—O7iii | 100.95 (18) | Mn1iii—O6—V2v | 126.5 (2) |
O1iii—V1—V1' | 33.3 (10) | Mn1iii—O6—V2'v | 136.8 (3) |
O3iv—V1—O4iii | 119.67 (19) | Mn2—O6—V2v | 120.5 (2) |
O3iv—V1—O7iii | 119.76 (18) | Mn2—O6—V2'v | 110.3 (3) |
O3iv—V1—V1' | 122.0 (10) | V2v—O6—V2'v | 10.5 (2) |
O4iii—V1—O7iii | 113.9 (2) | Mn2iii—O7—V1iii | 148.9 (2) |
O4iii—V1—V1' | 98.8 (12) | Mn2iii—O7—V1'iii | 138.5 (3) |
O7iii—V1—V1' | 71.8 (12) | V1iii—O7—V1'iii | 10.7 (2) |
O1—V2—O2iii | 107.63 (12) | V2—V2'—O1 | 15.6 (10) |
O1—V2—O5iii | 106.84 (16) | V2—V2'—O2iii | 108.0 (11) |
O1—V2—O6v | 107.87 (17) | V2—V2'—O5iii | 103.0 (12) |
O1—V2—V2' | 161.6 (12) | V2—V2'—O6v | 79.0 (13) |
O2iii—V2—O5iii | 111.34 (18) | O1—V2'—O2iii | 99.7 (3) |
O2iii—V2—O6v | 112.52 (16) | O1—V2'—O5iii | 98.1 (3) |
O2iii—V2—V2' | 62.1 (10) | O1—V2'—O6v | 94.5 (4) |
O5iii—V2—O6v | 110.4 (2) | O2iii—V2'—O5iii | 123.8 (5) |
O5iii—V2—V2' | 66.7 (13) | O2iii—V2'—O6v | 117.3 (4) |
O6v—V2—V2' | 90.5 (12) | O5iii—V2'—O6v | 113.7 (3) |
V1iii—O1—V2 | 165.08 (13) | V1—V1'—O1iii | 140.5 (12) |
V1iii—O1—V2' | 163.00 (19) | V1—V1'—O3iv | 50.2 (8) |
V1iii—O1—V1'iii | 6.3 (2) | V1—V1'—O4iii | 71.1 (13) |
V2—O1—V2' | 2.9 (2) | V1—V1'—O7iii | 97.5 (12) |
V2—O1—V1'iii | 159.2 (2) | O1iii—V1'—O3iv | 95.6 (3) |
V2'—O1—V1'iii | 156.9 (3) | O1iii—V1'—O4iii | 109.2 (4) |
Mn1—O2—Mn2i | 97.82 (8) | O1iii—V1'—O7iii | 116.5 (5) |
Mn1—O2—V2iii | 130.06 (17) | O3iv—V1'—O4iii | 107.0 (4) |
Mn1—O2—V2'iii | 133.3 (3) | O3iv—V1'—O7iii | 113.3 (3) |
Mn2i—O2—V2iii | 131.17 (16) | O4iii—V1'—O7iii | 113.5 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+2, −z+1; (vi) x+1, y, z. |
Comparison of atomic positions in the M phase (derived from the powder
synchrotron refinement), represented in a pseudo-monoclinic unit cell,
M', defined by Zhuravlev et al. (1993), and their
corresponding
positions in β-Mn2V2O7 representing the more general
β-(Mn,Zn)2V2O7 high-temperature solid solution. topAtom (M') | Atom (β) | x(M') | y(M') | z(M') | x(β) | y(β) | z(β) | Δx | Δy | Δz | Shift (Å) |
(Mn/Zn)1 | Mn | 0.0044 | 0.8102 | -0.0145 | 0.0 | 0.8109 | 0.0 | -0.0044 | 0.0007 | 0.0145 | 0.084 |
(Mn/Zn)2 | Mn | 0.0011 | 0.8177 | 0.0117 | 0.0 | 0.8109 | 0.0 | -0.0011 | -0.0068 | -0.0117 | 0.082 |
V1 | V | 0.7551 | 0.0011 | 0.3982 | 0.7341 | 0.0 | 0.4032 | -0.0210 | -0.0011 | 0.0050 | 0.149 |
V2 | V | 0.7126 | -0.0023 | 0.3962 | 0.7341 | 0.0 | 0.4032 | 0.0215 | 0.0023 | 0.0070 | 0.142 |
O1 | O1 | 0.5386 | 0.0055 | 0.5542 | 0.5 | 0.0 | 0.5 | -0.0386 | -0.0055 | -0.0542 | 0.330 |
O2 | O2 | 0.8826 | -0.0029 | 0.7031 | 0.9093 | 0.0 | 0.7191 | 0.0267 | 0.0029 | 0.0160 | 0.180 |
O3 | O2 | 0.9447 | 0.0049 | 0.7227 | 0.9093 | 0.0 | 0.7191 | -0.0354 | -0.0049 | -0.0036 | 0.238 |
O4 | O3 | 0.7231 | 0.1593 | 0.2019 | 0.7322 | 0.1614 | 0.2123 | 0.0091 | 0.0021 | 0.0104 | 0.072 |
O5 | O3 | 0.7271 | 0.1585 | 0.2121 | 0.7322 | 0.1614 | 0.2123 | 0.0051 | 0.0029 | 0.0002 | 0.043 |
O6 | O3 | 0.7366 | 0.1598 | 0.2107 | 0.7322 | 0.1614 | 0.2123 | -0.0044 | 0.0016 | 0.0016 | 0.036 |
O7 | O3 | 0.7073 | 0.1590 | 0.2226 | 0.7322 | 0.1614 | 0.2123 | 0.0249 | 0.0024 | -0.0103 | 0.187 |
Note: the components Δx, Δy and Δz of the shifts
and the magnitudes of the shifts are all defined with respect to the
β-Mn2V2O7 set of basis vectors quoted by Liao et al.
(1996). |
Selected bond lengths and angles (Å, °) top | Powder data | Single-crystal data |
(Mn/Zn)1—O5i | 2.107 (2) | 2.100 (4) |
(Mn/Zn)1—O6ii | 2.111 (2) | 2.099 (3) |
(Mn/Zn)1—O3iii | 2.143 (2) | 2.119 (3) |
(Mn/Zn)1—O2 | 2.187 (2) | 2.157 (3) |
(Mn/Zn)1—O5iv | 2.242 (2) | 2.229 (4) |
(Mn/Zn)1—O7 | 2.538 (2) | 2.474 (4) |
(Mn/Zn)2—O4 | 2.082 (2) | 2.059 (4) |
(Mn/Zn)2—O7ii | 2.097 (2) | 2.098 (4) |
(Mn/Zn)2—O3 | 2.156 (2) | 2.145 (3) |
(Mn/Zn)2—O2iii | 2.165 (2) | 2.121 (3) |
(Mn/Zn)2—O6 | 2.216 (2) | 2.198 (4) |
(Mn/Zn)2—O4iii | 2.328 (2) | 2.371 (4) |
V1—O7ii | 1.636 (2) | 1.664 (5) |
V1—O4ii | 1.679 (3) | 1.674 (5) |
V1—O1ii | 1.785 (2) | 1.822 (2) |
V1—O3v | 1.801 (2) | 1.776 (2) |
V1—O3vi | 2.209 (2) | 2.234 (3) |
V1'—O7ii | - | 1.594 (8) |
V1'—O4ii | - | 1.749 (9) |
V1'—O1ii | - | 1.570 (6) |
V1'—O3v | - | 1.960 (5) |
V2—O2ii | 1.674 (2) | 1.734 (2) |
V2—O6vii | 1.684 (2) | 1.693 (4) |
V2—O5ii | 1.692 (3) | 1.719 (5) |
V2—O1 | 1.737 (2) | 1.683 (2) |
V2'—O2ii | - | 1.611 (5) |
V2'—O6vii | - | 1.724 (8) |
V2'—O5ii | - | 1.621 (9) |
V2'—O1 | - | 1.983 (7) |
V2—O1—V1ii | 162.74 (11) | 165.08 (13) |
V2—O1—V1'ii | - | 159.2 (2) |
V2'—O1—V1'ii | - | 156.9 (3) |
V2'—O1—V1ii | - | 163.00 (19) |