Literature DB >> 24046541

A new mixed-valence lead(II) mangan-ese(II/III) phosphate(V): PbMn(II) 2Mn(III)(PO4)3.

Ghaleb Alhakmi1, Abderrazzak Assani, Mohamed Saadi, Lahcen El Ammari.   

Abstract

The title compound, lead trimanganese tris(orthophosphate), has been synthesized by hydro-thermal methods. In this structure, only two O atoms are in general positions and all others atoms are in the special positions of the Imma space group. Indeed, the atoms in the Wyckoff positions are namely: Pb1 and P1 on 4e (mm2); Mn1 on 4b (2/m); Mn2 and P2 on 8g (2); O1 on 8h (m); O2 on 8i (m). The crystal structure can be viewed as a three-dimensional network of corner- and edge-sharing PO4 tetra-hedra and MnO6 octa-hedra, building two types of chains running along the b axis. The first is an infinite linear chain, formed by alternating Mn(III)O6 octa-hedra and PO4 tetra-hedra which share one vertex. The second chain is built up from two adjacent edge-sharing octa-hedra (Mn(II) 2O10 dimers) whose ends are linked to two PO4 tetra-hedra by a common edge. These chains are linked together by common vertices of polyhedra in such a way as to form porous layers parallel to (001). These sheets are bonded by the first linear chains, leading to the appearance of two types of tunnels, one propagating along the a axis and the other along b. The Pb(II) ions are located within the inter-sections of the tunnels with eight neighbouring O atoms in form of a trigonal prism that is capped by two O atoms on one side. The three-dimensional framework of this structure is compared with similar phosphates such as Ag2Co3(HPO4)(PO4)2 and Ag2Ni3(HPO4)(PO4)2.

Entities:  

Year:  2013        PMID: 24046541      PMCID: PMC3772398          DOI: 10.1107/S1600536813016504

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN: 1600-5368


Related literature

For compounds with related structures see: Assani et al. (2011a ▶,b ▶,c ▶); Moore & Ito (1979 ▶). For applications of related compounds, see: Trad et al. (2010 ▶). For compounds with mixed-valence manganese(II/III) lead(II) triphosphates(V), see: Adam et al. (2009 ▶). For bond-valence analysis, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

PbMn3(PO4)3 M = 656.92 Orthorhombic, a = 10.2327 (8) Å b = 13.9389 (9) Å c = 6.6567 (4) Å V = 949.46 (11) Å3 Z = 4 Mo Kα radiation μ = 22.15 mm−1 T = 296 K 0.36 × 0.23 × 0.10 mm

Data collection

Bruker X8 APEX diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.046, T max = 0.215 4704 measured reflections 787 independent reflections 771 reflections with I > 2σ(I) R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.016 wR(F 2) = 0.040 S = 1.11 787 reflections 53 parameters Δρmax = 2.54 e Å−3 Δρmin = −0.98 e Å−3 Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813016504/br2227sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813016504/br2227Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
PbMn3(PO4)3F(000) = 1192
Mr = 656.92Dx = 4.596 Mg m3
Orthorhombic, ImmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2b 2Cell parameters from 787 reflections
a = 10.2327 (8) Åθ = 2.9–30.5°
b = 13.9389 (9) ŵ = 22.15 mm1
c = 6.6567 (4) ÅT = 296 K
V = 949.46 (11) Å3Sheet, brown
Z = 40.36 × 0.23 × 0.10 mm
Bruker X8 APEX diffractometer787 independent reflections
Radiation source: fine-focus sealed tube771 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
φ and ω scansθmax = 30.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −14→14
Tmin = 0.046, Tmax = 0.215k = −19→19
4704 measured reflectionsl = −9→9
Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.016Secondary atom site location: difference Fourier map
wR(F2) = 0.040w = 1/[σ2(Fo2) + (0.0205P)2 + 2.635P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
787 reflectionsΔρmax = 2.54 e Å3
53 parametersΔρmin = −0.98 e Å3
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.
xyzUiso*/Ueq
Pb10.00000.2500−0.11391 (3)0.01308 (7)
Mn10.00000.00000.50000.00488 (14)
Mn20.25000.36754 (4)0.25000.00774 (12)
P10.00000.25000.40554 (17)0.0044 (2)
P20.25000.57316 (6)0.25000.00507 (17)
O10.00000.16010 (18)0.5362 (4)0.0086 (5)
O20.1182 (3)0.25000.2619 (4)0.0084 (5)
O30.2066 (2)0.63321 (13)0.0719 (3)0.0101 (4)
O40.36271 (18)0.50018 (12)0.1977 (3)0.0078 (3)
U11U22U33U12U13U23
Pb10.01879 (13)0.01275 (10)0.00770 (10)0.0000.0000.000
Mn10.0038 (3)0.0069 (3)0.0040 (3)0.0000.0000.0000 (2)
Mn20.0093 (3)0.0054 (2)0.0085 (2)0.000−0.00019 (19)0.000
P10.0044 (6)0.0045 (5)0.0044 (5)0.0000.0000.000
P20.0056 (4)0.0047 (3)0.0049 (4)0.0000.0007 (3)0.000
O10.0092 (13)0.0067 (10)0.0100 (11)0.0000.0000.0033 (9)
O20.0069 (12)0.0086 (10)0.0098 (11)0.0000.0036 (9)0.000
O30.0123 (10)0.0118 (8)0.0061 (7)0.0036 (7)0.0014 (7)0.0030 (6)
O40.0070 (9)0.0078 (7)0.0086 (8)−0.0002 (6)0.0023 (7)0.0005 (6)
Pb1—O1i2.645 (3)Mn2—O3iv2.1881 (18)
Pb1—O1ii2.645 (3)Mn2—O3xii2.1881 (18)
Pb1—O3iii2.683 (2)Mn2—O4xiii2.2067 (18)
Pb1—O3iv2.683 (2)Mn2—O42.2067 (18)
Pb1—O3v2.683 (2)Mn2—P22.8660 (10)
Pb1—O3vi2.683 (2)P1—O2xiv1.542 (3)
Mn1—O4vii1.9249 (18)P1—O21.542 (3)
Mn1—O4viii1.9249 (18)P1—O1xiv1.525 (3)
Mn1—O4ix1.9249 (18)P1—O11.525 (3)
Mn1—O4x1.9249 (18)P2—O3xiii1.5180 (19)
Mn1—O12.245 (3)P2—O31.5180 (19)
Mn1—O1xi2.245 (3)P2—O4xiii1.5767 (19)
Mn2—O22.1237 (18)P2—O41.5767 (19)
Mn2—O2x2.1237 (18)
O1i—Pb1—O1ii56.57 (11)O1—Mn1—O1xi180.0
O1i—Pb1—O3iii78.72 (5)O2—Mn2—O2x79.02 (12)
O1ii—Pb1—O3iii112.30 (5)O2—Mn2—O3iv84.48 (8)
O1i—Pb1—O3iv112.30 (5)O2x—Mn2—O3iv95.10 (9)
O1ii—Pb1—O3iv78.72 (5)O2—Mn2—O3xii95.10 (9)
O3iii—Pb1—O3iv168.02 (8)O2x—Mn2—O3xii84.48 (8)
O1i—Pb1—O3v112.30 (5)O3iv—Mn2—O3xii179.45 (10)
O1ii—Pb1—O3v78.72 (5)O2—Mn2—O4xiii107.97 (8)
O3iii—Pb1—O3v74.73 (9)O2x—Mn2—O4xiii169.80 (8)
O3iv—Pb1—O3v103.98 (9)O3iv—Mn2—O4xiii93.00 (7)
O1i—Pb1—O3vi78.72 (5)O3xii—Mn2—O4xiii87.46 (7)
O1ii—Pb1—O3vi112.30 (5)O2—Mn2—O4169.80 (8)
O3iii—Pb1—O3vi103.98 (9)O2x—Mn2—O4107.97 (8)
O3iv—Pb1—O3vi74.73 (9)O3iv—Mn2—O487.46 (7)
O3v—Pb1—O3vi168.02 (8)O3xii—Mn2—O493.00 (7)
O4vii—Mn1—O4viii180.0O4xiii—Mn2—O466.18 (10)
O4vii—Mn1—O4ix93.75 (11)O2xiv—P1—O2103.3 (2)
O4viii—Mn1—O4ix86.25 (11)O2xiv—P1—O1xiv110.72 (7)
O4vii—Mn1—O4x86.25 (11)O2—P1—O1xiv110.72 (7)
O4viii—Mn1—O4x93.75 (11)O2xiv—P1—O1110.72 (7)
O4ix—Mn1—O4x180.0O2—P1—O1110.72 (7)
O4vii—Mn1—O185.71 (7)O1xiv—P1—O1110.5 (2)
O4viii—Mn1—O194.29 (7)O3xiii—P2—O3113.08 (15)
O4ix—Mn1—O185.71 (7)O3xiii—P2—O4xiii113.41 (10)
O4x—Mn1—O194.29 (7)O3—P2—O4xiii108.31 (11)
O4vii—Mn1—O1xi94.29 (7)O3xiii—P2—O4108.31 (11)
O4viii—Mn1—O1xi85.71 (7)O3—P2—O4113.41 (10)
O4ix—Mn1—O1xi94.29 (7)O4xiii—P2—O499.65 (13)
O4x—Mn1—O1xi85.71 (7)
  4 in total

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3.  Disilver(I) trinickel(II) hydrogenphos-phate bis-(phosphate), Ag(2)Ni(3)(HPO(4))(PO(4))(2).

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Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2011-06-11

4.  Disilver(I) tricobalt(II) hydrogenphos-phate bis-(phosphate), Ag(2)Co(3)(HPO(4))(PO(4))(2).

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Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2011-06-18
  4 in total
  8 in total

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Journal:  Acta Crystallogr E Crystallogr Commun       Date:  2015-06-20

2.  Crystal structure of strontium dicobalt iron(III) tris-(orthophosphate): SrCo2Fe(PO4)3.

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Journal:  Acta Crystallogr E Crystallogr Commun       Date:  2016-07-19

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Journal:  Acta Crystallogr E Crystallogr Commun       Date:  2017-05-26

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Journal:  Acta Crystallogr E Crystallogr Commun       Date:  2017-04-28

5.  K1+2x Ni1-x Fe2(AsO4)3 (x = 0,125): un nouvel arséniate à structure de type α-CrPO4.

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6.  Crystal structure of strontium dinickel iron orthophosphate.

Authors:  Said Ouaatta; Abderrazzak Assani; Mohamed Saadi; Lahcen El Ammari
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8.  SrMn(II) 2Mn(III)(PO4)3.

Authors:  Ghaleb Alhakmi; Abderrazzak Assani; Mohamed Saadi; Claudine Follet; Lahcen El Ammari
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2013-08-14
  8 in total

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