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Pyrobelonite [lead manganese(II) vanadate(V) hydroxide], PbMn
IIVO
4(OH), has been refined in space group
Pnma. It is isostructural with descloizite, PbZnVO
4(OH). Mn
IIO
4(OH)
2 octahedra share edges to form infinite chains parallel to the
b axis. Distorted VO
4 tetrahedra share vertices with the octahedra to form a compact framework, in which voids are occupied by [3+4]-coordinated Pb
2+ cations. All atoms except O3 are on special positions with site symmetry
(Mn) or .
m. (remaining atoms).
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (V-O) = 0.004 Å
- R factor = 0.018
- wR factor = 0.047
- Data-to-parameter ratio = 14.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: COLLECT (Nonius, 2001); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997b).
lead manganese(II) vanadate(V) hydroxide
top
Crystal data top
PbMnVO4(OH) | Dx = 5.828 Mg m−3 |
Mr = 394.08 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 898 reflections |
a = 7.646 (2) Å | θ = 3.5–30.0° |
b = 6.179 (1) Å | µ = 42.11 mm−1 |
c = 9.507 (2) Å | T = 293 K |
V = 449.15 (17) Å3 | Fragment, dark red |
Z = 4 | 0.08 × 0.08 × 0.05 mm |
F(000) = 684 | |
Data collection top
Nonius KappaCCD diffractometer | 714 independent reflections |
Radiation source: fine-focus sealed tube | 699 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ψ and ω scans | θmax = 30.0°, θmin = 3.4° |
Absorption correction: numerical maXus (Mackay et al., 1998) | h = −10→10 |
Tmin = 0.059, Tmax = 0.125 | k = −8→8 |
1242 measured reflections | l = −13→13 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.018 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.024P)2 + 1.30P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max < 0.001 |
714 reflections | Δρmax = 1.26 e Å−3 |
49 parameters | Δρmin = −1.80 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0086 (4) |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pb | 0.13286 (2) | 0.2500 | 0.177529 (19) | 0.01086 (11) | |
Mn | 0.0000 | 0.0000 | 0.5000 | 0.00650 (17) | |
V | 0.36513 (9) | 0.7500 | 0.31118 (9) | 0.00422 (19) | |
O1 | 0.1882 (5) | 0.7500 | 0.4274 (4) | 0.0082 (7) | |
O2 | 0.5407 (5) | 0.7500 | 0.4133 (4) | 0.0178 (8) | |
O3 | 0.3728 (3) | 0.5128 (5) | 0.2099 (3) | 0.0103 (5) | |
OH4 | 0.1565 (5) | 0.2500 | 0.4244 (4) | 0.0072 (7) | |
H | 0.243 (11) | 0.2500 | 0.465 (8) | 0.020* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pb | 0.01011 (15) | 0.01714 (16) | 0.00532 (14) | 0.000 | 0.00006 (5) | 0.000 |
Mn | 0.0089 (3) | 0.0049 (4) | 0.0057 (3) | −0.0007 (3) | 0.0002 (2) | 0.0008 (2) |
V | 0.0049 (4) | 0.0048 (4) | 0.0029 (4) | 0.000 | 0.0012 (2) | 0.000 |
O1 | 0.0099 (17) | 0.0087 (16) | 0.0058 (15) | 0.000 | 0.0028 (13) | 0.000 |
O2 | 0.0083 (16) | 0.034 (2) | 0.0106 (17) | 0.000 | −0.0038 (13) | 0.000 |
O3 | 0.0137 (12) | 0.0084 (13) | 0.0089 (12) | 0.0012 (9) | 0.0027 (8) | −0.0011 (11) |
OH4 | 0.0050 (14) | 0.0068 (17) | 0.0098 (18) | 0.000 | −0.0031 (12) | 0.000 |
Geometric parameters (Å, º) top
Pb—OH4 | 2.354 (4) | V—Pbxiv | 3.4829 (11) |
Pb—O3 | 2.470 (3) | V—Pbxv | 3.7077 (7) |
Pb—O3i | 2.470 (3) | V—Pbxvi | 3.7077 (7) |
Pb—O1ii | 2.744 (4) | V—Pbxvii | 3.7833 (7) |
Pb—O3iii | 2.781 (3) | O1—Mnx | 2.221 (3) |
Pb—O3iv | 2.781 (3) | O1—Mnxvii | 2.221 (3) |
Pb—O2ii | 2.841 (4) | O1—Pbxiv | 2.744 (4) |
Pb—O2v | 3.2843 (15) | O1—Pbxvii | 3.920 (2) |
Pb—O2iv | 3.2843 (15) | O1—Pbviii | 4.487 (4) |
Pb—Vii | 3.4829 (11) | O1—Pbxv | 4.701 (3) |
Mn—OH4vi | 2.082 (3) | O1—Pbxvi | 4.701 (3) |
Mn—OH4 | 2.082 (3) | O2—Pbxiv | 2.841 (4) |
Mn—O1vii | 2.221 (3) | O2—Pbxvi | 3.2843 (15) |
Mn—O1viii | 2.221 (3) | O2—Pbxv | 3.2843 (15) |
Mn—O3iii | 2.221 (3) | O2—Pbxviii | 4.622 (4) |
Mn—O3ix | 2.221 (3) | O3—Mnxix | 2.221 (3) |
Mn—Mnx | 3.0895 (5) | O3—Pbxvi | 2.781 (3) |
Mn—Mnxi | 3.0895 (5) | O3—Pbxiv | 4.681 (3) |
Mn—Pbvi | 3.5801 (6) | OH4—Mnx | 2.082 (3) |
Mn—Pbiv | 3.6214 (6) | OH4—Pbxvi | 3.769 (4) |
Mn—Pbxii | 3.6214 (6) | OH4—Pbiv | 4.120 (4) |
V—O2 | 1.656 (4) | OH4—Pbxiv | 4.234 (3) |
V—O1 | 1.747 (4) | OH4—Pbxii | 4.234 (3) |
V—O3 | 1.755 (3) | OH4—H | 0.77 (9) |
V—O3xiii | 1.755 (3) | | |
| | | |
OH4—Pb—O3 | 79.55 (10) | O3iii—Pb—O2iv | 119.80 (9) |
OH4—Pb—O3i | 79.55 (10) | O3iv—Pb—O2iv | 53.02 (9) |
O3—Pb—O3i | 82.23 (13) | O2ii—Pb—O2iv | 70.57 (7) |
OH4—Pb—O1ii | 145.68 (13) | O2v—Pb—O2iv | 140.33 (13) |
O3—Pb—O1ii | 74.78 (9) | OH4vi—Mn—OH4 | 180.0 |
O3i—Pb—O1ii | 74.78 (9) | OH4vi—Mn—O1vii | 87.92 (10) |
OH4—Pb—O3iii | 70.81 (9) | OH4—Mn—O1vii | 92.08 (10) |
O3—Pb—O3iii | 150.13 (3) | OH4vi—Mn—O1viii | 92.08 (10) |
O3i—Pb—O3iii | 95.69 (9) | OH4—Mn—O1viii | 87.92 (10) |
O1ii—Pb—O3iii | 133.63 (8) | O1vii—Mn—O1viii | 180.0 |
OH4—Pb—O3iv | 70.81 (9) | OH4vi—Mn—O3iii | 91.85 (13) |
O3—Pb—O3iv | 95.69 (9) | OH4—Mn—O3iii | 88.15 (13) |
O3i—Pb—O3iv | 150.13 (3) | O1vii—Mn—O3iii | 88.83 (12) |
O1ii—Pb—O3iv | 133.63 (8) | O1viii—Mn—O3iii | 91.17 (12) |
O3iii—Pb—O3iv | 71.45 (12) | OH4vi—Mn—O3ix | 88.15 (13) |
OH4—Pb—O2ii | 156.57 (12) | OH4—Mn—O3ix | 91.85 (13) |
O3—Pb—O2ii | 117.21 (9) | O1vii—Mn—O3ix | 91.17 (12) |
O3i—Pb—O2ii | 117.21 (9) | O1viii—Mn—O3ix | 88.83 (12) |
O1ii—Pb—O2ii | 57.75 (12) | O3iii—Mn—O3ix | 180.0 |
O3iii—Pb—O2ii | 90.37 (9) | O2—V—O1 | 104.9 (2) |
O3iv—Pb—O2ii | 90.37 (9) | O2—V—O3 | 107.12 (11) |
OH4—Pb—O2v | 106.17 (7) | O1—V—O3 | 111.90 (10) |
O3—Pb—O2v | 144.17 (9) | O2—V—O3xiii | 107.12 (11) |
O3i—Pb—O2v | 64.76 (9) | O1—V—O3xiii | 111.90 (10) |
O1ii—Pb—O2v | 83.06 (7) | O3—V—O3xiii | 113.3 (2) |
O3iii—Pb—O2v | 53.02 (9) | Mn—OH4—H | 109 (4) |
O3iv—Pb—O2v | 119.80 (9) | Mnx—OH4—H | 109 (4) |
O2ii—Pb—O2v | 70.57 (7) | Pb—OH4—H | 125 (6) |
OH4—Pb—O2iv | 106.17 (7) | Pbxvi—OH4—H | 46 (6) |
O3—Pb—O2iv | 64.76 (9) | Pbiv—OH4—H | 163 (6) |
O3i—Pb—O2iv | 144.17 (10) | Pbxiv—OH4—H | 52 (2) |
O1ii—Pb—O2iv | 83.06 (7) | Pbxii—OH4—H | 52 (2) |
Symmetry codes: (i) x, −y+1/2, z; (ii) −x+1/2, −y+1, z−1/2; (iii) x−1/2, −y+1/2, −z+1/2; (iv) x−1/2, y, −z+1/2; (v) x−1/2, y−1, −z+1/2; (vi) −x, −y, −z+1; (vii) x, y−1, z; (viii) −x, −y+1, −z+1; (ix) −x+1/2, y−1/2, z+1/2; (x) −x, y+1/2, −z+1; (xi) −x, y−1/2, −z+1; (xii) −x+1/2, −y, z+1/2; (xiii) x, −y+3/2, z; (xiv) −x+1/2, −y+1, z+1/2; (xv) x+1/2, y+1, −z+1/2; (xvi) x+1/2, y, −z+1/2; (xvii) x, y+1, z; (xviii) −x+1, −y+1, −z+1; (xix) x+1/2, −y+1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OH4—H···O2xviii | 0.77 (9) | 2.02 (9) | 2.783 (5) | 176 (8) |
Symmetry code: (xviii) −x+1, −y+1, −z+1. |
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