Dilead(II) trimanganese(II) bis(hydrogenphosphate) bis(phosphate).

The title compound, Pb(2)Mn(3)(HPO(4))(2)(PO(4))(2), was synthesized by a hydro-thermal method. All atoms are in general positions except for one Mn atom which is located on an inversion center. The framework of the structure is built up from PO(4) tetra-hedra and two types of MnO(6) octa-hedra, one almost ideal and the other very distorted with one very long Mn-O bond [2.610 (4) Å compared an average of 2.161 Å for the other bonds]. The centrosymetric octa-hedron is linked to two distorted MnO(6) octa-hedra by an edge common, forming infinite zigzag Mn(3)O(14) chains running along the b axis. Adjacent chains are linked by PO(4) and PO(3)(OH) tetra-hedra through vertices or by edge sharing, forming sheets perpendicular to [100]. The Pb(2+) cations are sandwiched between the layers and ensure the cohesion of the crystal structure. O-H⋯O hydrogen bonding between the layers is also observed.

Related literature

For properties of phosphates and their potential applications, see: Gao & Gao (2005 ▶); Viter & Nagornyi (2009 ▶); Clearfield (1988 ▶); Trad et al. (2010 ▶). For compounds with related structures, see: Assani et al. (2010 ▶, 2011a ▶,b ▶,c ▶, 2012 ▶); Effenberger (1999 ▶). For bond-valence analysis, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

Pb2Mn3(HPO4)2(PO4)2

M = 961.10

Monoclinic,

a = 7.9449 (2) Å

b = 8.8911 (2) Å

c = 9.5718 (3) Å

β = 100.917 (2)°

V = 663.90 (3) Å3

Z = 2

Mo Kα radiation

μ = 28.63 mm−1

T = 296 K

0.18 × 0.12 × 0.08 mm

Data collection

Bruker X8 APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003) ▶ T min = 0.029, T max = 0.117

8738 measured reflections

1225 independent reflections

1202 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.051

S = 1.10

1225 reflections

116 parameters

H-atom parameters constrained

Δρmax = 1.37 e Å−3

Δρmin = −2.03 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812033259/hp2043sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033259/hp2043Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Pb2Mn3(HPO4)2(PO4)2	F(000) = 858
Mr = 961.10	Dx = 4.808 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1225 reflections
a = 7.9449 (2) Å	θ = 2.6–25.4°
b = 8.8911 (2) Å	µ = 28.63 mm−1
c = 9.5718 (3) Å	T = 296 K
β = 100.917 (2)°	Prism, pink
V = 663.90 (3) Å3	0.18 × 0.12 × 0.08 mm
Z = 2

Bruker X8 APEXII diffractometer	1225 independent reflections
Radiation source: fine-focus sealed tube	1202 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
φ and ω scans	θmax = 25.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
Tmin = 0.029, Tmax = 0.117	k = −10→10
8738 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.020	H-atom parameters constrained
wR(F2) = 0.051	w = 1/[σ2(Fo2) + (0.0232P)2 + 2.912P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.001
1225 reflections	Δρmax = 1.37 e Å−3
116 parameters	Δρmin = −2.03 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0091 (4)

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.

	x	y	z	Uiso*/Ueq
Pb1	0.41097 (3)	0.52400 (2)	0.75343 (2)	0.01734 (13)
Mn1	0.0000	0.5000	0.5000	0.0091 (2)
Mn2	0.10770 (9)	0.13892 (8)	0.59303 (7)	0.00981 (19)
P1	0.14019 (16)	0.70441 (14)	0.23105 (12)	0.0076 (3)
P2	0.65619 (16)	0.70724 (14)	0.56583 (12)	0.0087 (3)
O1	0.0496 (5)	0.6808 (4)	0.3570 (4)	0.0123 (7)
O2	0.0740 (5)	0.5969 (4)	0.1080 (3)	0.0122 (7)
O3	0.1156 (5)	0.8690 (4)	0.1828 (4)	0.0127 (7)
O4	0.3370 (5)	0.6828 (4)	0.2816 (4)	0.0133 (7)
O5	0.7064 (5)	0.6754 (5)	0.7236 (4)	0.0208 (9)
O6	0.7536 (5)	0.6118 (4)	0.4742 (4)	0.0152 (8)
O7	0.6777 (5)	0.8718 (4)	0.5276 (4)	0.0212 (9)
O8	0.4617 (5)	0.6642 (4)	0.5341 (4)	0.0146 (7)
H8	0.4002	0.6667	0.4499	0.022*

	U11	U22	U33	U12	U13	U23
Pb1	0.01783 (17)	0.01676 (17)	0.01923 (17)	0.00271 (7)	0.00812 (10)	0.00201 (7)
Mn1	0.0108 (6)	0.0084 (5)	0.0080 (5)	0.0006 (4)	0.0018 (4)	0.0002 (4)
Mn2	0.0096 (4)	0.0107 (4)	0.0082 (4)	0.0003 (3)	−0.0008 (3)	−0.0006 (3)
P1	0.0080 (6)	0.0090 (6)	0.0055 (6)	−0.0004 (5)	0.0003 (5)	0.0003 (4)
P2	0.0080 (6)	0.0111 (6)	0.0067 (6)	−0.0007 (5)	0.0009 (5)	−0.0005 (4)
O1	0.0154 (19)	0.0110 (17)	0.0120 (17)	−0.0005 (14)	0.0068 (14)	0.0016 (13)
O2	0.0154 (19)	0.0111 (17)	0.0076 (16)	0.0002 (14)	−0.0045 (14)	−0.0020 (13)
O3	0.0154 (19)	0.0099 (17)	0.0120 (17)	0.0005 (14)	0.0008 (14)	0.0026 (14)
O4	0.0083 (18)	0.0234 (19)	0.0078 (16)	0.0002 (14)	0.0004 (13)	−0.0002 (14)
O5	0.015 (2)	0.038 (2)	0.0076 (18)	0.0013 (17)	−0.0021 (14)	0.0035 (16)
O6	0.0113 (18)	0.0200 (19)	0.0153 (17)	0.0061 (15)	0.0048 (14)	0.0015 (15)
O7	0.030 (2)	0.0118 (18)	0.026 (2)	−0.0036 (16)	0.0151 (18)	−0.0013 (16)
O8	0.0087 (17)	0.0261 (19)	0.0079 (16)	−0.0034 (15)	−0.0012 (14)	0.0016 (15)

Pb1—O3i	2.504 (4)	P1—O3	1.536 (3)
Pb1—O8	2.539 (4)	P1—O4	1.559 (4)
Pb1—O6ii	2.614 (4)	P2—O5	1.514 (4)
Pb1—O4i	2.697 (4)	P2—O7	1.526 (4)
Pb1—O7iii	2.698 (4)	P2—O6	1.532 (4)
Pb1—O5	2.767 (4)	P2—O8	1.565 (4)
Pb1—O4ii	2.785 (4)	O1—Mn2vi	2.141 (4)
Mn1—O3iv	2.157 (3)	O2—Mn2viii	2.122 (4)
Mn1—O3i	2.157 (3)	O2—Mn2ix	2.208 (3)
Mn1—O6ii	2.168 (3)	O3—Mn1ix	2.157 (3)
Mn1—O6v	2.168 (3)	O3—Pb1x	2.504 (4)
Mn1—O1	2.195 (3)	O4—Pb1x	2.697 (4)
Mn1—O1vi	2.195 (3)	O4—Pb1ii	2.785 (4)
Mn2—O5iii	2.094 (4)	O5—Mn2xi	2.094 (4)
Mn2—O2vii	2.122 (4)	O6—Mn1xii	2.168 (3)
Mn2—O1vi	2.141 (4)	O6—Mn2ii	2.610 (4)
Mn2—O2iv	2.208 (3)	O6—Pb1ii	2.614 (4)
Mn2—O7ii	2.235 (4)	O7—Mn2ii	2.235 (4)
Mn2—O6ii	2.610 (4)	O7—Pb1xi	2.698 (4)
P1—O2	1.530 (3)	O8—H8	0.8600
P1—O1	1.531 (3)
O3i—Pb1—O8	82.97 (11)	O3i—Mn1—O1vi	89.35 (13)
O3i—Pb1—O6ii	69.84 (11)	O6ii—Mn1—O1vi	81.84 (13)
O8—Pb1—O6ii	70.75 (11)	O6v—Mn1—O1vi	98.16 (13)
O3i—Pb1—O4i	56.56 (11)	O1—Mn1—O1vi	180.000 (1)
O8—Pb1—O4i	71.32 (11)	O5iii—Mn2—O2vii	100.04 (15)
O6ii—Pb1—O4i	116.47 (11)	O5iii—Mn2—O1vi	92.62 (15)
O3i—Pb1—O7iii	91.78 (12)	O2vii—Mn2—O1vi	129.62 (14)
O8—Pb1—O7iii	173.95 (12)	O5iii—Mn2—O2iv	176.09 (15)
O6ii—Pb1—O7iii	104.65 (12)	O2vii—Mn2—O2iv	79.73 (13)
O4i—Pb1—O7iii	108.25 (11)	O1vi—Mn2—O2iv	90.49 (14)
O3i—Pb1—O5	123.87 (12)	O5iii—Mn2—O7ii	87.34 (15)
O8—Pb1—O5	53.50 (11)	O2vii—Mn2—O7ii	96.38 (14)
O6ii—Pb1—O5	116.03 (11)	O1vi—Mn2—O7ii	133.01 (14)
O4i—Pb1—O5	75.23 (12)	O2iv—Mn2—O7ii	88.81 (14)
O7iii—Pb1—O5	132.49 (12)	O5iii—Mn2—O6ii	79.12 (14)
O3i—Pb1—O4ii	151.26 (10)	O2vii—Mn2—O6ii	157.01 (13)
O8—Pb1—O4ii	89.67 (11)	O1vi—Mn2—O6ii	73.21 (12)
O6ii—Pb1—O4ii	81.50 (10)	O2iv—Mn2—O6ii	99.54 (12)
O4i—Pb1—O4ii	145.63 (8)	O7ii—Mn2—O6ii	60.65 (12)
O7iii—Pb1—O4ii	93.55 (11)	O2—P1—O1	112.1 (2)
O5—Pb1—O4ii	70.46 (12)	O2—P1—O3	111.0 (2)
O3iv—Mn1—O3i	180.000 (1)	O1—P1—O3	108.4 (2)
O3iv—Mn1—O6ii	94.68 (14)	O2—P1—O4	109.9 (2)
O3i—Mn1—O6ii	85.32 (14)	O1—P1—O4	109.4 (2)
O3iv—Mn1—O6v	85.32 (14)	O3—P1—O4	105.9 (2)
O3i—Mn1—O6v	94.68 (14)	O5—P2—O7	113.5 (2)
O6ii—Mn1—O6v	180.00 (19)	O5—P2—O6	113.7 (2)
O3iv—Mn1—O1	89.35 (13)	O7—P2—O6	107.6 (2)
O3i—Mn1—O1	90.65 (13)	O5—P2—O8	102.2 (2)
O6ii—Mn1—O1	98.16 (13)	O7—P2—O8	109.8 (2)
O6v—Mn1—O1	81.84 (13)	O6—P2—O8	109.9 (2)
O3iv—Mn1—O1vi	90.65 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O4	0.86	1.60	2.437 (5)	164
O8—H8···O1	0.86	2.76	3.393 (5)	132

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O4	0.86	1.60	2.437 (5)	164
O8—H8⋯O1	0.86	2.76	3.393 (5)	132