Crystal structure of Pb3(IO4(OH)2)2

Weil, M.

doi:10.1107/S1600536814009520

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Volume 70| Part 7| July 2014| Pages 14-17

https://doi.org/10.1107/S1600536814009520

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Crystal structure of Pb₃(IO₄(OH)₂)₂

Matthias Weil ^a ^*

^aInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, Vienna University of Technology, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria
^*Correspondence e-mail: mweil@mail.zserv.tuwien.ac.at

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 16 April 2014; accepted 25 April 2014; online 23 June 2014)

The structure of the title compound, trilead(II) bis[dihydroxidotetraoxidoiodate(VII)], was determined from a crystal twinned by non-merohedry with two twin domains present [twin fraction 0.73 (1):0.27 (1)]. It contains three Pb²⁺ cations and two IO₄(OH)₂³⁻ anions in the asymmetric unit. Each of the Pb²⁺ cations is surrounded by eight O atoms (cut-off value = 3.1 Å) in the form of a distorted polyhedron. The octahedral IO₄(OH)₂³⁻ anions are arranged in rows extending parallel to [021], forming a distorted hexagonal rod packing. The cations and anions are linked into a framework structure. Although H-atom positions could not be located, O⋯O distances suggest medium-strength hydrogen-bonding interactions between the IO₄(OH)₂ octahedra, further consolidating the crystal packing.

Keywords: crystal structure; lead; periodate; non-merohedral twinning.

CCDC reference: 1004265

1. Chemical context

Lead and mercury can both exist in different oxidation states and each of the two elements exhibits a peculiar crystal chemistry. In the case of Pb²⁺-containing compounds, the crystal chemistry is mainly dominated by the stereoactive 6s² lone-pair of lead (Holloway & Melnik, 1997 ), whereas Hg²⁺-containing compounds show a strong preference for a linear coordination of mercury (Breitinger, 2004 ). In this respect, it appears surprising that for some Pb²⁺- and Hg²⁺-containing compounds an isotypic relationship exists, e.g. for PbAs₂O₆ (Losilla et al., 1995 ) and HgAs₂O₆ (Mormann & Jeitschko, 2000b ; Weil, 2000 ), or for the mineral descloizite PbZn(VO₄)OH (Hawthorne & Faggiani, 1979 ) and the synthetic phase HgZn(AsO₄)OH (Weil, 2004 ). With this in mind, it seemed interesting to study the relation between phases in the systems Hg^II–I^VII–O–H and Pb^II–I^VII–O–H. Whereas in the system Hg^II–I^VII–O–H two compounds have been structurally characterized, viz. Hg₃(IO₄(OH)₂)₂ (Mormann & Jeitschko, 2000a ) and Hg(IO₃(OH)₃) (Mormann & Jeitschko, 2001 ), a phase in the system Pb^II–I^VII–O–H has not yet been structurally determined, although several lead(II) periodate phases have been reported to exist. Willard & Thompson (1934 ) claimed to have obtained only one phase with composition Pb₃H₄(IO₆)₂ in the system Pb^II–I^VII–O–H. However, Drátovský & Matějčková (1965a ,b ) reported the existence of three phases with composition Pb₃(IO₅)₂·H₂O, Pb₂I₂O₉·3H₂O and Pb₄I₂O₁₁·5H₂O in this system. To shed some light on the conflicting composition of the Pb:I 3:2 phase [Pb₃H₄(IO₆)₂ versus Pb₃(IO₅)₂·H₂O with a lower water content], the synthetic procedure described by Willard & Thompson (1934) was repeated for crystal growth of this lead periodate. The current structure determination of the obtained crystals showed the composition Pb₃H₄(IO₆)₂ as reported by Willard & Thompson (1934) to be correct. In a more reasonable crystal–chemical sense, the formula of these crystals should be rewritten as Pb₃(IO₄(OH)₂)₂.

2. Structural commentary

Three Pb²⁺ cations and two IO₄(OH)₂³⁻ octahedra are present in the asymmetric unit. The anions form a slightly distorted hexagonal rod packing with the rods extending parallel to [021]. Cations and anions are linked through common oxygen atoms into a framework structure (Fig. 1).

Figure 1
The crystal structure of Pb₃(IO₄(OH)₂)₂ in a projection along [021]. Displacement ellipsoids are drawn at the 90% probability level. O atoms bearing the OH function are given in green, the other O atoms are white. Pb—O bonds are omitted for clarity; hydrogen-bonding interactions are shown as green dashed lines.

Each of the Pb²⁺ cations exhibits a coordination number of eight if Pb—O interactions less than 3.1 Å are considered to be relevant. The resulting [PbO₈] polyhedra are considerably distorted [Pb—O distances range from 2.433 (7) to 3.099 (8) Å]. The stereochemical activity of the electron lone pairs in each of the polyhedra appears not to be very pronounced (Fig. 2).

Figure 2
Coordination polyhedra of the three Pb²⁺ cations in the structure of Pb₃(IO₄(OH)₂)₂. Bonds shorter than 2.7 Å are given by solid black lines, longer bonds between 2.7 and 3.1 Å as open black lines. Displacement ellipsoids are drawn at the 90% probability level. [Symmetry codes: (i) −x, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iii) x, y − 1, z; (iv) −x + 1, −y + 1, −z; (v) −x, −y + 1, −z; (vi) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (vii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (viii) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Compounds and structures containing the periodate anion have been reviewed some time ago by Levason (1997 ). The compiled I—O bond lengths are in good agreement with the two IO₆ octahedra of the title compound, having a mean I—O distance of 1.884 Å. Very similar mean values are found for comparable periodate compounds with large divalent cations, for example in BaI₂O₆(OH)₄·2H₂O (one IO₆ octahedron, 1.895 Å; Häuseler, 2008 ), in Ba(IO₃(OH)₃) (one IO₆ octahedron, 1.879 Å; Sasaki et al., 1995 ), in Hg₃(IO₄(OH)₂)₂ (two IO₆ octahedra, 1.888 Å; Mormann & Jeitschko, 2000a) or in Sr(IO₂(OH)₄)₂·3H₂O (two IO₆ octahedra, 1.888 Å; Alexandrova & Häuseler, 2004 ).

Results of bond-valence calculations (Brown, 2002 ), using the parameters of Brese & O'Keeffe (1991 ) for I—O bonds and of Krivovichev & Brown (2001 ) for Pb—O bonds, are reasonably close to the expected values (in valence units): Pb1 1.89, Pb2 1.73, Pb3 1.89, I1 6.78, I2 6.90, O1 1.95, O2 1.49, O3 1.90, O4 1.15, O5 1.15, O6 1.92, O7 1.98, O8 1.95, O 9 1.97, O10 1.09, O11 1.34, O12 1.12. The O atoms involved in hydrogen bonding are readily identifiable. The donor O atoms O4, O5, O10 and O12 exhibit the longest I—O bonds and the lowest bond-valence sums. Atom O11 has also a low bond-valence sum, explainable by its role as a twofold acceptor atom of medium-strength hydrogen-bonding interactions (Table 2) that additionally stabilize the packing of the structure (Fig. 1).

Table 2
Hydrogen-bond geometry (Å)

D—H⋯A	D⋯A	D—H⋯A	D⋯A
O4⋯O7	2.849 (11)	O10⋯O11^iv	2.675 (11)
O4⋯O2ⁱ	2.849 (11)	O12⋯O2^iv	2.852 (11)
O5⋯O11ⁱⁱⁱ	2.634 (11)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Comparison of the structures of Pb₃(IO₄(OH)₂)₂ and of Hg₃(IO₄(OH)₂)₂ [P2₁/c; Z = 4, a = 8.5429 (7), b = 12.2051 (8) Å, c = 9.3549 (8) Å, β = 90.884 (7)°] reveals some close similarities. A `true' isotypic relationship (Lima-de-Faria et al., 1990 ) is difficult to derive for the two structures. However, they are isopointal and show the same type of arrangement in terms of the crystal packing. In the mercury compound, the IO₄(OH)₂³⁻ octahedra are likewise hexagonally packed in rods (Fig. 3). The cations are situated in between this arrangement which is further consolidated by O—H⋯O hydrogen bonding.

Figure 3
The crystal structure of Hg₃(IO₄(OH)₂)₂ (Mormann & Jeitschko, 2000a

) in a projection along [011]. Colour code as in Fig. 1

. Hg—O and O—H⋯O interactions are omitted for clarity.

3. Synthesis and crystallization

The preparation conditions described by Willard & Thompson (1934) were modified slightly. Instead of using NaIO₄ as the periodate source, periodic acid was employed.

1.25 g Pb(NO₃)₂ was dissolved in 25 ml water, acidified with a few drops of concentrated nitric acid and heated until boiling. Then the periodic acid solution (0.85 g in 25 ml water) was slowly added to the lead solution. The addition of the first portion of the periodic acid solution (ca. 3–4 ml) resulted in an off-white precipitate near the drop point that redissolved under stirring. After further addition, the precipitate remained and changed the colour in the still boiling solution from off-white to yellow–orange within half an hour. After filtration of the precipitate, a few colourless crystals of the title compound formed in the mother liquor on cooling. X-ray powder diffraction data of the polycrystalline precipitate are in very good agreement with simulated data based on the refinement of Pb₃(IO₄(OH)₂)₂.

4. Refinement

All investigated crystals were twinned by non-merohedry. Intensity data of the measured crystal could be indexed to belong to two domains, with a refined twin domain ratio of 0.73 (1):0.27 (1). Reflections originating from the minor component as well as overlapping reflections of the two domains (less than 10% of all measured reflections) were separated and excluded. The H atoms of the IO₄(OH)₂ octahedra could not be located from difference maps and were therefore not considered in the final model. The O atoms were refined with isotropic displacement parameters. The remaining maximum and minimum electron densities are found 0.73 and 0.68 Å, respectively, from atom Pb2. Structure data were finally standardized with STRUCTURE-TIDY (Gelato & Parthé, 1987 ). It should be noted that the intensity statistics point to a pronounced C-centred basis cell (space group C2/c with lattice parameters of a ≃ 14.16, b ≃ 9.21, c ≃ 8.97 Å, β ≃ 117.4°) with weak superstructure reflections violating the C-centering.

Supporting information

CCDC reference: 1004265

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536814009520/hb0004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814009520/hb0004Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS for Windows (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Trilead(II) bis[dihydroxidotetraoxidoiodate(VII)] top

Crystal data top

Pb₃[IO₄(OH)₂]₂	F(000) = 1808
M_r = 1071.40	D_x = 6.857 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3673 reflections
a = 8.9653 (9) Å	θ = 3.2–30.5°
b = 9.2113 (9) Å	µ = 54.55 mm⁻¹
c = 12.8052 (13) Å	T = 296 K
β = 101.042 (2)°	Block, colourless
V = 1037.90 (18) Å³	0.06 × 0.06 × 0.05 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	3196 independent reflections
Radiation source: fine-focus sealed tube	2587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
ω scans	θ_max = 30.6°, θ_min = 2.3°
Absorption correction: multi-scan (TWINABS; Bruker, 2008)	h = −12→12
T_min = 0.253, T_max = 0.746	k = 0→13
3196 measured reflections	l = 0→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	H-atom parameters not refined
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0319P)² + 17.8096P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3196 reflections	Δρ_max = 2.88 e Å⁻³
94 parameters	Δρ_min = −1.95 e Å⁻³
0 restraints

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	U_iso*/U_eq
Pb1	0.12192 (5)	0.13042 (4)	0.11904 (3)	0.01318 (10)
Pb2	0.25685 (5)	0.51903 (5)	0.01540 (4)	0.01842 (11)
Pb3	0.37507 (5)	0.36874 (5)	0.38134 (3)	0.01409 (10)
I1	0.00670 (7)	0.23313 (7)	0.36046 (5)	0.00838 (13)
I2	0.50186 (7)	0.24738 (6)	0.14267 (5)	0.00735 (13)
O1	0.0343 (9)	0.3332 (8)	0.0015 (6)	0.0110 (14)*
O2	0.0389 (9)	0.7922 (8)	0.2811 (6)	0.0125 (15)*
O3	0.1058 (9)	0.4046 (8)	0.4090 (6)	0.0122 (15)*
O4	0.1088 (10)	0.5549 (9)	0.1797 (6)	0.0178 (17)*
O5	0.1831 (9)	0.8100 (8)	0.1159 (6)	0.0129 (15)*
O6	0.1842 (9)	0.1429 (8)	0.3433 (6)	0.0117 (15)*
O7	0.3161 (9)	0.3260 (8)	0.1618 (6)	0.0121 (15)*
O8	0.4052 (9)	0.0832 (8)	0.0785 (6)	0.0121 (15)*
O9	0.4802 (9)	0.3391 (8)	0.0121 (6)	0.0144 (16)*
O10	0.5247 (9)	0.1474 (8)	0.2794 (6)	0.0145 (16)*
O11	0.6146 (10)	0.3912 (8)	0.2170 (6)	0.0158 (16)*
O12	0.6856 (10)	0.1562 (9)	0.1172 (6)	0.0182 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.0134 (2)	0.01402 (19)	0.01215 (19)	−0.00236 (15)	0.00243 (15)	0.00042 (14)
Pb2	0.0168 (2)	0.01424 (19)	0.0236 (2)	0.00084 (17)	0.00251 (16)	0.00040 (16)
Pb3	0.0153 (2)	0.0173 (2)	0.01036 (18)	−0.00366 (16)	0.00426 (15)	−0.00050 (14)
I1	0.0075 (3)	0.0104 (3)	0.0072 (3)	−0.0003 (2)	0.0014 (2)	0.0006 (2)
I2	0.0066 (3)	0.0078 (3)	0.0076 (3)	−0.0002 (2)	0.0011 (2)	−0.0005 (2)

Geometric parameters (Å, º) top

Pb1—O1	2.433 (7)	Pb3—O9^vi	2.599 (8)
Pb1—O7	2.493 (8)	Pb3—O6	2.678 (8)
Pb1—O2ⁱ	2.577 (8)	Pb3—O12^vii	2.704 (8)
Pb1—O3ⁱⁱ	2.685 (7)	Pb3—O8^vii	2.767 (8)
Pb1—O8	2.723 (8)	Pb3—O7	2.787 (7)
Pb1—O6	2.821 (7)	Pb3—O10	2.886 (8)
Pb1—O3ⁱ	2.888 (8)	I1—O6	1.845 (8)
Pb1—O5ⁱⁱⁱ	3.004 (7)	I1—O3	1.860 (7)
Pb2—O7	2.564 (7)	I1—O2ⁱ	1.861 (7)
Pb2—O9	2.606 (8)	I1—O1^vi	1.877 (7)
Pb2—O1	2.609 (7)	I1—O5ⁱ	1.920 (8)
Pb2—O6ⁱⁱ	2.638 (7)	I1—O4ⁱ	1.956 (8)
Pb2—O4	2.714 (8)	I2—O11	1.820 (8)
Pb2—O9^iv	2.777 (8)	I2—O9	1.850 (8)
Pb2—O1^v	2.915 (7)	I2—O8	1.855 (7)
Pb2—O5	3.099 (8)	I2—O7	1.874 (8)
Pb3—O8^vi	2.527 (7)	I2—O12	1.932 (9)
Pb3—O3	2.528 (8)	I2—O10	1.954 (8)

O1—Pb1—O7	73.1 (2)	O7—I2—O10	90.5 (3)
O1—Pb1—O2ⁱ	73.6 (2)	O12—I2—O10	90.0 (3)
O7—Pb1—O2ⁱ	84.6 (2)	I1ⁱⁱ—O1—Pb1	108.2 (3)
O1—Pb1—O3ⁱⁱ	61.5 (2)	I1ⁱⁱ—O1—Pb2	103.7 (3)
O7—Pb1—O3ⁱⁱ	102.0 (2)	Pb1—O1—Pb2	108.0 (3)
O2ⁱ—Pb1—O3ⁱⁱ	129.7 (2)	I1ⁱⁱ—O1—Pb2^v	97.4 (3)
O1—Pb1—O8	102.0 (2)	Pb1—O1—Pb2^v	125.6 (3)
O7—Pb1—O8	61.3 (2)	Pb2—O1—Pb2^v	111.1 (2)
O2ⁱ—Pb1—O8	144.9 (2)	I1ⁱⁱ—O1—Pb3ⁱⁱ	57.6 (2)
O3ⁱⁱ—Pb1—O8	70.3 (2)	Pb1—O1—Pb3ⁱⁱ	73.14 (18)
O1—Pb1—O6	125.2 (2)	Pb2—O1—Pb3ⁱⁱ	73.13 (17)
O7—Pb1—O6	75.7 (2)	Pb2^v—O1—Pb3ⁱⁱ	154.3 (2)
O2ⁱ—Pb1—O6	59.4 (2)	I1^viii—O2—Pb1^viii	106.0 (3)
O3ⁱⁱ—Pb1—O6	170.7 (2)	I1^viii—O2—Pb2^ix	156.0 (4)
O8—Pb1—O6	101.0 (2)	Pb1^viii—O2—Pb2^ix	97.4 (2)
O1—Pb1—O3ⁱ	109.8 (2)	I1^viii—O2—Pb1^x	75.1 (2)
O7—Pb1—O3ⁱ	174.4 (2)	Pb1^viii—O2—Pb1^x	155.4 (3)
O2ⁱ—Pb1—O3ⁱ	91.7 (2)	Pb2^ix—O2—Pb1^x	86.03 (16)
O3ⁱⁱ—Pb1—O3ⁱ	83.5 (2)	I1^viii—O2—Pb3^viii	62.0 (2)
O8—Pb1—O3ⁱ	121.6 (2)	Pb1^viii—O2—Pb3^viii	78.83 (19)
O6—Pb1—O3ⁱ	98.8 (2)	Pb2^ix—O2—Pb3^viii	129.9 (2)
O1—Pb1—O5ⁱⁱⁱ	141.7 (2)	Pb1^x—O2—Pb3^viii	80.39 (14)
O7—Pb1—O5ⁱⁱⁱ	126.3 (2)	I1—O3—Pb3	104.5 (3)
O2ⁱ—Pb1—O5ⁱⁱⁱ	134.1 (2)	I1—O3—Pb1^vi	99.4 (3)
O3ⁱⁱ—Pb1—O5ⁱⁱⁱ	81.0 (2)	Pb3—O3—Pb1^vi	104.8 (3)
O8—Pb1—O5ⁱⁱⁱ	70.2 (2)	I1—O3—Pb1^viii	106.8 (3)
O6—Pb1—O5ⁱⁱⁱ	93.0 (2)	Pb3—O3—Pb1^viii	138.4 (3)
O3ⁱ—Pb1—O5ⁱⁱⁱ	54.4 (2)	Pb1^vi—O3—Pb1^viii	96.5 (2)
O7—Pb2—O9	61.2 (2)	I1^viii—O4—Pb2	102.2 (3)
O7—Pb2—O1	69.1 (2)	I1^viii—O4—Pb3	146.5 (3)
O9—Pb2—O1	99.3 (2)	Pb2—O4—Pb3	98.2 (2)
O7—Pb2—O6ⁱⁱ	101.7 (2)	I1^viii—O4—Pb1^viii	71.6 (2)
O9—Pb2—O6ⁱⁱ	72.2 (2)	Pb2—O4—Pb1^viii	173.4 (3)
O1—Pb2—O6ⁱⁱ	60.6 (2)	Pb3—O4—Pb1^viii	88.39 (17)
O7—Pb2—O4	65.3 (2)	I1^viii—O4—Pb2^v	68.3 (2)
O9—Pb2—O4	125.5 (2)	Pb2—O4—Pb2^v	87.5 (2)
O1—Pb2—O4	69.6 (2)	Pb3—O4—Pb2^v	139.5 (2)
O6ⁱⁱ—Pb2—O4	129.6 (2)	Pb1^viii—O4—Pb2^v	87.94 (18)
O7—Pb2—O9^iv	110.9 (2)	I1^viii—O4—Pb1	143.6 (3)
O9—Pb2—O9^iv	67.9 (3)	Pb2—O4—Pb1	72.12 (18)
O1—Pb2—O9^iv	163.1 (2)	Pb3—O4—Pb1	68.44 (14)
O6ⁱⁱ—Pb2—O9^iv	103.9 (2)	Pb1^viii—O4—Pb1	111.3 (2)
O4—Pb2—O9^iv	126.5 (2)	Pb2^v—O4—Pb1	75.48 (15)
O7—Pb2—O1^v	115.8 (2)	I1^viii—O5—Pb1^x	101.0 (3)
O9—Pb2—O1^v	167.4 (2)	I1^viii—O5—Pb2	90.7 (3)
O1—Pb2—O1^v	68.9 (2)	Pb1^x—O5—Pb2	155.4 (3)
O6ⁱⁱ—Pb2—O1^v	97.3 (2)	I1^viii—O5—Pb1^v	69.1 (2)
O4—Pb2—O1^v	55.7 (2)	Pb1^x—O5—Pb1^v	75.90 (16)
O9^iv—Pb2—O1^v	122.7 (2)	Pb2—O5—Pb1^v	88.49 (18)
O7—Pb2—O5	109.1 (2)	I1^viii—O5—Pb3^vii	163.1 (3)
O9—Pb2—O5	141.5 (2)	Pb1^x—O5—Pb3^vii	92.88 (19)
O1—Pb2—O5	112.0 (2)	Pb2—O5—Pb3^vii	80.25 (17)
O6ⁱⁱ—Pb2—O5	142.9 (2)	Pb1^v—O5—Pb3^vii	124.4 (2)
O4—Pb2—O5	53.0 (2)	I1—O6—Pb2^vi	103.6 (3)
O9^iv—Pb2—O5	84.2 (2)	I1—O6—Pb3	99.4 (3)
O1^v—Pb2—O5	50.8 (2)	Pb2^vi—O6—Pb3	103.9 (3)
O8^vi—Pb3—O3	76.1 (3)	I1—O6—Pb1	97.6 (3)
O8^vi—Pb3—O9^vi	61.9 (2)	Pb2^vi—O6—Pb1	142.8 (3)
O3—Pb3—O9^vi	104.1 (2)	Pb3—O6—Pb1	102.2 (2)
O8^vi—Pb3—O6	105.1 (2)	I2—O7—Pb1	107.0 (3)
O3—Pb3—O6	62.2 (2)	I2—O7—Pb2	103.7 (3)
O9^vi—Pb3—O6	71.7 (2)	Pb1—O7—Pb2	107.6 (3)
O8^vi—Pb3—O12^vii	78.7 (2)	I2—O7—Pb3	100.6 (3)
O3—Pb3—O12^vii	70.9 (3)	Pb1—O7—Pb3	108.2 (3)
O9^vi—Pb3—O12^vii	140.0 (2)	Pb2—O7—Pb3	127.7 (3)
O6—Pb3—O12^vii	129.8 (2)	I2—O7—Pb3ⁱⁱ	56.96 (19)
O8^vi—Pb3—O8^vii	75.7 (3)	Pb1—O7—Pb3ⁱⁱ	72.30 (17)
O3—Pb3—O8^vii	123.1 (2)	Pb2—O7—Pb3ⁱⁱ	73.10 (17)
O9^vi—Pb3—O8^vii	104.4 (2)	Pb3—O7—Pb3ⁱⁱ	154.9 (3)
O6—Pb3—O8^vii	174.5 (2)	I2—O8—Pb3ⁱⁱ	104.5 (3)
O12^vii—Pb3—O8^vii	55.7 (2)	I2—O8—Pb1	99.1 (3)
O8^vi—Pb3—O7	174.9 (2)	Pb3ⁱⁱ—O8—Pb1	103.7 (3)
O3—Pb3—O7	99.1 (2)	I2—O8—Pb3^xi	104.1 (3)
O9^vi—Pb3—O7	121.4 (2)	Pb3ⁱⁱ—O8—Pb3^xi	104.3 (3)
O6—Pb3—O7	73.5 (2)	Pb1—O8—Pb3^xi	137.3 (3)
O12^vii—Pb3—O7	98.4 (2)	I2—O9—Pb3ⁱⁱ	102.0 (3)
O8^vii—Pb3—O7	106.2 (2)	I2—O9—Pb2	102.9 (3)
O8^vi—Pb3—O10	127.3 (2)	Pb3ⁱⁱ—O9—Pb2	107.1 (3)
O3—Pb3—O10	134.0 (2)	I2—O9—Pb2^iv	112.6 (4)
O9^vi—Pb3—O10	68.2 (2)	Pb3ⁱⁱ—O9—Pb2^iv	118.5 (3)
O6—Pb3—O10	72.9 (2)	Pb2—O9—Pb2^iv	112.1 (3)
O12^vii—Pb3—O10	143.8 (2)	I2—O10—Pb3	95.4 (3)
O8^vii—Pb3—O10	102.3 (2)	I2—O10—Pb2^xi	148.8 (4)
O7—Pb3—O10	57.2 (2)	Pb3—O10—Pb2^xi	98.9 (2)
O6—I1—O3	93.1 (3)	I2—O10—Pb3^xi	79.3 (2)
O6—I1—O2ⁱ	92.8 (3)	Pb3—O10—Pb3^xi	167.0 (3)
O3—I1—O2ⁱ	94.6 (3)	Pb2^xi—O10—Pb3^xi	91.50 (19)
O6—I1—O1^vi	90.6 (3)	I2—O10—Pb1	67.0 (2)
O3—I1—O1^vi	89.3 (3)	Pb3—O10—Pb1	78.32 (18)
O2ⁱ—I1—O1^vi	174.7 (3)	Pb2^xi—O10—Pb1	143.2 (2)
O6—I1—O5ⁱ	174.5 (3)	Pb3^xi—O10—Pb1	88.65 (17)
O3—I1—O5ⁱ	90.9 (3)	I2—O11—Pb3	85.6 (3)
O2ⁱ—I1—O5ⁱ	90.5 (3)	I2—O11—Pb2^iv	88.1 (3)
O1^vi—I1—O5ⁱ	85.8 (3)	Pb3—O11—Pb2^iv	157.4 (3)
O6—I1—O4ⁱ	90.9 (3)	I2—O11—Pb1^vii	171.0 (4)
O3—I1—O4ⁱ	174.5 (3)	Pb3—O11—Pb1^vii	95.8 (2)
O2ⁱ—I1—O4ⁱ	89.0 (3)	Pb2^iv—O11—Pb1^vii	93.74 (19)
O1^vi—I1—O4ⁱ	86.9 (3)	I2—O11—Pb2	64.5 (2)
O5ⁱ—I1—O4ⁱ	84.8 (3)	Pb3—O11—Pb2	83.53 (18)
O11—I2—O9	95.3 (3)	Pb2^iv—O11—Pb2	74.20 (15)
O11—I2—O8	172.0 (3)	Pb1^vii—O11—Pb2	124.5 (2)
O9—I2—O8	90.7 (3)	I2—O12—Pb3^xi	104.2 (4)
O11—I2—O7	93.9 (4)	I2—O12—Pb2^iv	85.5 (3)
O9—I2—O7	90.0 (3)	Pb3^xi—O12—Pb2^iv	151.9 (3)
O8—I2—O7	91.2 (3)	I2—O12—Pb3ⁱⁱ	68.4 (2)
O11—I2—O12	89.9 (4)	Pb3^xi—O12—Pb3ⁱⁱ	79.9 (2)
O9—I2—O12	89.5 (4)	Pb2^iv—O12—Pb3ⁱⁱ	79.42 (16)
O8—I2—O12	84.9 (3)	I2—O12—Pb1^xii	155.4 (4)
O7—I2—O12	176.1 (3)	Pb3^xi—O12—Pb1^xii	98.2 (2)
O11—I2—O10	85.5 (3)	Pb2^iv—O12—Pb1^xii	79.41 (17)
O9—I2—O10	179.1 (3)	Pb3ⁱⁱ—O12—Pb1^xii	126.6 (2)
O8—I2—O10	88.4 (3)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, y−1, z; (iv) −x+1, −y+1, −z; (v) −x, −y+1, −z; (vi) x, −y+1/2, z+1/2; (vii) −x+1, y+1/2, −z+1/2; (viii) −x, y+1/2, −z+1/2; (ix) x, −y+3/2, z+1/2; (x) x, y+1, z; (xi) −x+1, y−1/2, −z+1/2; (xii) x+1, y, z.

Hydrogen-bond geometry (Å) top

D—H···A	D···A
O4···O7	2.849 (11)
O4···O2ⁱ	2.849 (11)
O5···O11^vii	2.634 (11)
O10···O11^xi	2.675 (11)
O12···O2^xi	2.852 (11)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (vii) −x+1, y+1/2, −z+1/2; (xi) −x+1, y−1/2, −z+1/2.

Acknowledgements

The X-ray centre of the Vienna University of Technology is acknowledged for providing access to the single-crystal diffractometer.

References

Alexandrova, M. & Häuseler, H. (2004). J. Mol. Struct. 706, 7–13. Web of Science CrossRef CAS Google Scholar
Breitinger, D. K. (2004). Cadmium and Mercury, in Comprehensive Coordination Chemistry II, edited by J. A. McCleverty & T. J. Meyer, ch. 6, pp. 1253–1292. Oxford: Elsevier. Google Scholar
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brown, I. D. (2002). In The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. Oxford University Press. Google Scholar
Bruker (2008). SMART, SAINT-Plus and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dowty, E. (2006). ATOMS for Windows. Shape Software, Kingsport, Tennessee, USA. Google Scholar
Drátovský, M. & Matějčková, J. (1965a). Chem. Zvesti, 19, 604–610. Google Scholar
Drátovský, M. & Matějčková, J. (1965b). Chem. Zvesti, 19, 447–455. Google Scholar
Gelato, L. M. & Parthé, E. (1987). J. Appl. Cryst. 20, 139–143. CrossRef Web of Science IUCr Journals Google Scholar
Häuseler, H. (2008). J. Mol. Struct. 892, 1–7. Google Scholar
Hawthorne, F. C. & Faggiani, R. (1979). Acta Cryst. B35, 717–720. CrossRef CAS IUCr Journals Web of Science Google Scholar
Holloway, C. E. & Melnik, M. (1997). Main Group Met. Chem. 20, 583–625. CAS Google Scholar
Krivovichev, S. V. & Brown, I. D. (2001). Z. Kristallogr. 216, 245–247. Web of Science CrossRef CAS Google Scholar
Levason, W. (1997). Coord. Chem. Rev. 161, 33–79. CrossRef CAS Web of Science Google Scholar
Lima-de-Faria, J., Hellner, E., Liebau, F., Makovicky, E. & Parthé, E. (1990). Acta Cryst. A46, 1–11. CrossRef CAS IUCr Journals Google Scholar
Losilla, E. R., Aranda, M. A. G., Ramirez, F. J. & Bruque, S. (1995). J. Phys. Chem. 99, 12975–12979. CrossRef CAS Web of Science Google Scholar
Mormann, T. J. & Jeitschko, W. (2000a). Z. Kristallogr. New Cryst. Struct., 215, 315–316. CAS Google Scholar
Mormann, T. J. & Jeitschko, W. (2000b). Z. Kristallogr. New Cryst. Struct., 215, 471–472. CAS Google Scholar
Mormann, T. J. & Jeitschko, W. (2001). Z. Kristallogr. New Cryst. Struct., 216, 1–2. CrossRef CAS Google Scholar
Sasaki, M., Yarita, T. & Sato, S. (1995). Acta Cryst. C51, 1968–1970. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Weil, M. (2000). Z. Naturforsch. Teil B, 55, 699–706. CAS Google Scholar
Weil, M. (2004). Acta Cryst. E60, i25–i27. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Willard, H. H. & Thompson, J. J. (1934). J. Am. Chem. Soc. 56, 1828–1830. CrossRef CAS Google Scholar