Dicobalt(II) lead(II) hydrogenphos-phate(V) phos-phate(V) hydroxide monohydrate.

The title compound, Co(2)Pb(HPO(4))(PO(4))OH·H(2)O, which was synthesized under hydro-thermal conditions, crystallizes in a new structure type. Except for two O atoms in general positions and two Co atoms on centres of symmetry, all other atoms in the asymmetric unit (1 Pb, 2 Co, 2 P, 8 O and 4 H) are located on mirror planes. The structure is built up from two infinite linear chains, viz.(1) (∞)[CoO(2/1)(H(2)O)(2/2)O(2/2)] and (1) (∞)[CoO(2/1)(OH)(2/2)O(2/2)], of edge-sharing CoO(6) octa-hedra running along [010]. Adjacent chains are linked to each other through PO(4) and PO(3)(OH) tetra-hedra, leading to the formation of layers parallel to (100). The three-dimensional framework is formed by stacking along [100] of adjacent layers that are held together by distorted PbO(8) polyhedra. Hydrogen bonds of the type O-H⋯O involving the water mol-ecule are very strong, while those O atoms involving the OH groups form weak bifurcated and trifurcated hydrogen bonds.

Related literature

For catalytic properties of phosphates, see: Cheetham et al. (1999 ▶); Clearfield (1988 ▶); Trad et al. (2010 ▶). For compounds with related structures, see: Yakubovich et al. (2001 ▶); Lee et al. (2008 ▶); Effenberger (1999 ▶); Britvin et al. (2002 ▶); Assani et al. (2010 ▶). For bond-valence analysis, see: Brown & Altermatt (1985 ▶). For background to the Inorganic Crystal Structure Database (ICSD), see: Belsky et al. (2002 ▶).

Experimental

Crystal data

Co2Pb(HPO4)(PO4)OH·H2O

M = 551.02

Monoclinic,

a = 7.4299 (1) Å

b = 6.2949 (1) Å

c = 8.9057 (1) Å

β = 113.936 (1)°

V = 380.70 (1) Å3

Z = 2

Mo Kα radiation

μ = 26.83 mm−1

T = 296 K

0.18 × 0.12 × 0.08 mm

Data collection

Bruker X8 APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ▶) T min = 0.029, T max = 0.117

8321 measured reflections

1601 independent reflections

1558 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.039

S = 1.11

1601 reflections

86 parameters

H-atom parameters constrained

Δρmax = 1.76 e Å−3

Δρmin = −1.49 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) global. DOI: 10.1107/S1600536812014870/wm2609sup1.cif

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

Co2Pb(HPO4)(PO4)OH·H2O	F(000) = 500
Mr = 551.02	Dx = 4.807 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1601 reflections
a = 7.4299 (1) Å	θ = 2.5–33.5°
b = 6.2949 (1) Å	µ = 26.83 mm−1
c = 8.9057 (1) Å	T = 296 K
β = 113.936 (1)°	Prism, pink
V = 380.70 (1) Å3	0.18 × 0.12 × 0.08 mm
Z = 2

Bruker X8 APEXII diffractometer	1601 independent reflections
Radiation source: fine-focus sealed tube	1558 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 33.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	h = −9→11
Tmin = 0.029, Tmax = 0.117	k = −9→9
8321 measured reflections	l = −13→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.016	H-atom parameters constrained
wR(F2) = 0.039	w = 1/[σ2(Fo2) + (0.0153P)2 + 0.885P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
1601 reflections	Δρmax = 1.76 e Å−3
86 parameters	Δρmin = −1.49 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: 0.0061 (3)

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 > 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	0.006473 (17)	0.2500	0.232477 (15)	0.01414 (5)
Co1	−0.5000	0.0000	0.0000	0.00717 (8)
Co2	0.5000	0.5000	0.5000	0.00859 (8)
P1	−0.22391 (12)	−0.2500	0.32517 (9)	0.00646 (13)
P2	−0.21025 (11)	0.2500	−0.16270 (9)	0.00642 (13)
O1	−0.3205 (3)	−0.2500	0.4478 (3)	0.0088 (4)
O2	0.0058 (4)	−0.2500	0.4403 (3)	0.0145 (5)
H2	0.0642	−0.2500	0.3744	0.017*
O3	−0.2656 (2)	−0.0469 (3)	0.2228 (2)	0.0102 (3)
O4	0.0041 (4)	0.2500	−0.0355 (3)	0.0160 (5)
O5	−0.3411 (3)	0.2500	−0.0638 (3)	0.0096 (4)
O6	−0.2489 (3)	0.0525 (3)	−0.2742 (2)	0.0135 (3)
O7	−0.4341 (4)	0.2500	0.3936 (3)	0.0100 (4)
H7	−0.3197	0.2500	0.3910	0.012*
O8	−0.6059 (3)	0.2500	0.0885 (3)	0.0086 (4)
H8A	−0.7322	0.2500	0.0522	0.010*
H8B	−0.5660	0.2500	0.1937	0.010*

	U11	U22	U33	U12	U13	U23
Pb1	0.01157 (7)	0.02066 (8)	0.01059 (7)	0.000	0.00492 (4)	0.000
Co1	0.00890 (17)	0.00553 (19)	0.00703 (16)	0.00041 (14)	0.00319 (14)	0.00011 (13)
Co2	0.01066 (18)	0.0070 (2)	0.00765 (16)	−0.00114 (14)	0.00323 (14)	−0.00053 (13)
P1	0.0091 (3)	0.0062 (3)	0.0048 (3)	0.000	0.0035 (3)	0.000
P2	0.0068 (3)	0.0075 (3)	0.0052 (3)	0.000	0.0028 (2)	0.000
O1	0.0122 (10)	0.0082 (10)	0.0084 (9)	0.000	0.0067 (8)	0.000
O2	0.0080 (10)	0.0233 (14)	0.0106 (10)	0.000	0.0022 (8)	0.000
O3	0.0119 (7)	0.0090 (7)	0.0083 (6)	−0.0011 (6)	0.0027 (5)	0.0010 (6)
O4	0.0073 (10)	0.0287 (15)	0.0101 (10)	0.000	0.0016 (8)	0.000
O5	0.0110 (10)	0.0101 (10)	0.0105 (9)	0.000	0.0071 (8)	0.000
O6	0.0156 (8)	0.0124 (8)	0.0088 (6)	0.0056 (7)	0.0010 (6)	−0.0041 (6)
O7	0.0113 (10)	0.0130 (11)	0.0074 (9)	0.000	0.0055 (8)	0.000
O8	0.0097 (9)	0.0100 (10)	0.0072 (9)	0.000	0.0047 (8)	0.000

Pb1—O4	2.380 (3)	P1—O1	1.531 (2)
Pb1—O6i	2.5429 (18)	P1—O2	1.595 (3)
Pb1—O6ii	2.5429 (18)	P2—O4	1.535 (3)
Pb1—O3	2.7284 (17)	P2—O6	1.5432 (18)
Pb1—O3iii	2.7284 (17)	P2—O6iii	1.5432 (18)
Pb1—O5	2.846 (2)	P2—O5	1.554 (2)
Pb1—O1iv	2.857 (2)	O1—Co2xi	2.2302 (16)
Pb1—O2iv	2.952 (3)	O1—Co2xii	2.2302 (16)
Co1—O8	2.0544 (14)	O1—Pb1iv	2.857 (2)
Co1—O8v	2.0544 (14)	O2—Pb1iv	2.952 (3)
Co1—O3v	2.0624 (16)	O2—H2	0.8600
Co1—O3	2.0624 (16)	O5—Co1xiii	2.1766 (15)
Co1—O5	2.1766 (15)	O6—Co2xiv	2.1426 (17)
Co1—O5v	2.1766 (15)	O6—Pb1ii	2.5429 (18)
Co2—O7vi	1.9978 (14)	O7—Co2xv	1.9978 (14)
Co2—O7vii	1.9978 (14)	O7—Co2xii	1.9978 (14)
Co2—O6i	2.1426 (17)	O7—H7	0.8600
Co2—O6viii	2.1426 (17)	O7—H8B	1.6474
Co2—O1ix	2.2302 (16)	O8—Co1xiii	2.0544 (14)
Co2—O1iv	2.2302 (16)	O8—H8A	0.8600
P1—O3x	1.5274 (18)	O8—H8B	0.8600
P1—O3	1.5274 (18)
O4—Pb1—O6i	82.12 (5)	O3v—Co1—O5	88.92 (8)
O4—Pb1—O6ii	82.12 (5)	O3—Co1—O5	91.08 (8)
O6i—Pb1—O6ii	97.00 (9)	O8—Co1—O5v	96.95 (6)
O4—Pb1—O3	105.34 (5)	O8v—Co1—O5v	83.05 (6)
O6i—Pb1—O3	171.63 (5)	O3v—Co1—O5v	91.08 (8)
O6ii—Pb1—O3	87.90 (7)	O3—Co1—O5v	88.92 (8)
O4—Pb1—O3iii	105.34 (5)	O5—Co1—O5v	180.00 (12)
O6i—Pb1—O3iii	87.90 (7)	O7vi—Co2—O7vii	180.0
O6ii—Pb1—O3iii	171.63 (5)	O7vi—Co2—O6i	87.93 (9)
O3—Pb1—O3iii	86.46 (8)	O7vii—Co2—O6i	92.07 (9)
O4—Pb1—O5	55.64 (7)	O7vi—Co2—O6viii	92.07 (9)
O6i—Pb1—O5	117.25 (4)	O7vii—Co2—O6viii	87.93 (9)
O6ii—Pb1—O5	117.25 (4)	O6i—Co2—O6viii	180.0
O3—Pb1—O5	65.72 (4)	O7vi—Co2—O1ix	100.06 (7)
O3iii—Pb1—O5	65.72 (4)	O7vii—Co2—O1ix	79.94 (7)
O4—Pb1—O1iv	132.09 (7)	O6i—Co2—O1ix	93.55 (8)
O6i—Pb1—O1iv	67.09 (5)	O6viii—Co2—O1ix	86.45 (8)
O6ii—Pb1—O1iv	67.09 (5)	O7vi—Co2—O1iv	79.94 (7)
O3—Pb1—O1iv	109.06 (5)	O7vii—Co2—O1iv	100.06 (7)
O3iii—Pb1—O1iv	109.06 (5)	O6i—Co2—O1iv	86.45 (8)
O5—Pb1—O1iv	172.27 (6)	O6viii—Co2—O1iv	93.55 (8)
O4—Pb1—O2iv	178.00 (7)	O1ix—Co2—O1iv	180.0
O6i—Pb1—O2iv	99.18 (5)	O3x—P1—O3	113.68 (14)
O6ii—Pb1—O2iv	99.18 (5)	O3x—P1—O1	112.68 (8)
O3—Pb1—O2iv	73.26 (5)	O3—P1—O1	112.68 (8)
O3iii—Pb1—O2iv	73.26 (5)	O3x—P1—O2	106.78 (8)
O5—Pb1—O2iv	122.36 (7)	O3—P1—O2	106.78 (8)
O1iv—Pb1—O2iv	49.91 (6)	O1—P1—O2	103.32 (13)
O8—Co1—O8v	180.00 (11)	O4—P2—O6	109.94 (9)
O8—Co1—O3v	87.37 (8)	O4—P2—O6iii	109.94 (9)
O8v—Co1—O3v	92.63 (8)	O6—P2—O6iii	107.30 (15)
O8—Co1—O3	92.63 (8)	O4—P2—O5	106.40 (14)
O8v—Co1—O3	87.37 (8)	O6—P2—O5	111.63 (9)
O3v—Co1—O3	180.00 (13)	O6iii—P2—O5	111.63 (9)
O8—Co1—O5	83.05 (6)	H8A—O8—H8B	104.5
O8v—Co1—O5	96.95 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6ii	0.86	2.28	3.027 (3)	145
O2—H2···O6xiv	0.86	2.28	3.027 (3)	145
O7—H7···O2iv	0.86	2.20	2.915 (3)	140
O7—H7···O3	0.86	2.53	2.986 (2)	114
O7—H7···O3iii	0.86	2.53	2.986 (2)	114
O8—H8A···O4xv	0.86	1.79	2.649 (3)	177
O8—H8B···O7	0.86	1.65	2.489 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O6i	0.86	2.28	3.027 (3)	145
O2—H2⋯O6ii	0.86	2.28	3.027 (3)	145
O7—H7⋯O2iii	0.86	2.20	2.915 (3)	140
O7—H7⋯O3	0.86	2.53	2.986 (2)	114
O7—H7⋯O3iv	0.86	2.53	2.986 (2)	114
O8—H8A⋯O4v	0.86	1.79	2.649 (3)	177
O8—H8B⋯O7	0.86	1.65	2.489 (3)	165

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .