research papers
Lead apatites: structural variations among Pb5(BO4)3Cl with B = P (pyromorphite), As (mimetite) and V (vanadinite)
aDepartment of Geoscience, University of Calgary, Calgary, Alberta, Canada T2N 1N4
*Correspondence e-mail: antao@ucalgary.ca
The 5(BO4)3Cl, was refined with synchrotron high-resolution powder X-ray diffraction data, Rietveld refinements, P63/m and Z = 2. For this isotypic series, B = P5+ is pyromorphite, B = As5+ is mimetite and B = V5+ is vanadinite. The ionic radius for As5+ (0.355 Å) is similar to that of V5+ (0.335 Å), and this is twice as large as that for P5+ (0.170 Å). However, the c unit-cell parameter for mimetite is surprisingly different from that of vanadinite, although their unit-cell volumes, V, are almost equal to each other. No explanation was available for this peculiar c-axis value for mimetite. Structural parameters such as average 〈B—O〉 [4], 〈Pb1—O9〉 [9] and 〈Pb2—O6Cl2〉 [8] distances increase linearly with V (the coordination numbers for the cations are given in square brackets). Mimetite has a short Pb2—O1 distance, so the O1 oxygen atom interacts with the 6s2 lone-pair electrons of the Pb2+ cation that causes the Cl—Cl distance (= c/2) to increase to the largest value in the series because of repulsion, which causes the c-axis to increase anomalously. Although Pb apatite minerals occur naturally in ore deposits, they are also formed as scaly deposits in lead water pipes that give rise to lead in tap water, as was found recently in Flint, Michigan, USA. It is important to identify Pb-containing phases in water-pipe deposits.
of four Pb apatite samples, PbKeywords: lead apatites; pyromorphite; mimetite; vanadinite; structure; chemistry; synchrotron high-resolution powder X-ray diffraction (HRPXRD); Rietveld refinement.
1. Introduction
Apatite is a mineral of interest in various fields because of its importance in geology and technology. Hydroxylapatite, Ca5(PO4)3(OH), is well known in biological sciences because it is the main constituent of dental enamel and human bones. Apatite, Ca5(PO4)3(OH,F,Cl), is the most abundant rock-forming phosphate-group mineral and is the main phosphorous host in crustal rocks (McConnell, 1973).
Lead apatites, Pb5(BO4)3(Cl), where B = P5+ is pyromorphite, B = As5+ is mimetite and B = V5+ is vanadinite, occur in various worldwide localities and as scaly deposits in lead water pipes. Recently, the issue of lead in tap water was highlighted in Flint, Michigan, USA, where high levels of lead were recorded (Robeznieks, 2015). Phosphate is added to drinking water in the UK to minimize the release of lead from lead water pipes (Hopwood et al., 2016). The phosphate addition promotes the formation of insoluble lead apatites on the walls of the water pipes where they occur as scaly deposits. Hydroxylpyromorphite, Pb5(PO4)3(OH), is the lead apatite that is used often to model lead levels in tap water. However, apatites on lead water pipes were shown to be solid solutions between pyromorphite and chlorapatite, (Ca5–xPbx)(PO4)3[(OH)yCl1–y] (Hopwood et al., 2016). The structure of a related lead apatite mineral, phosphohedyphane, Ca2Pb3(PO4)3Cl, is also known (Kampf et al., 2006). Oscillatory zoning in an arsenate mineral, erythrite, Co3(AsO4)2·8H2O, was recently discussed (Antao & Dhaliwal, 2017).
High ion conductivity in rare-earth silicate oxyapatites is of interest (e.g. Nakayama et al., 1995, 1999; Ali et al., 2009). Their conductivity at relatively low temperatures is of potential benefit for electrolyte materials in solid oxide fuel cells (Fergus, 2006). There is no rigorous explanation as to why only oxide ions in rare-earth silicate oxyapatites can move freely inside the channel whereas other ions [F, Cl and (OH)] in apatites were found to be localized at the (0,0,0) or (0,0,z) position.
Studies on the crystal chemistry of apatite ) and Náray-Szabó (1930) and continue to recent times (e.g. Okudera, 2013, and references therein). The crystal chemistry of apatites has been described in a few reviews (Elliott et al., 2002; White & Zhili, 2003; Pasero et al., 2010).
minerals began with the determination of the structure of fluorapatite by Mehmel (1930Based on other apatite-group minerals, pyromorphite was assumed to have hexagonal P63/m (Hendricks et al., 1932). The structure was refined to an R-factor of 12% by using visual estimates of intensities from precession photographs (Trotter & Barnes, 1958). The pyromorphite structure was refined with mixed isotropic and anisotropic displacement parameters (Dai & Hughes, 1989). Thereafter, the pyromorphite structure was refined with anisotropic displacement parameters (ADPs) (e.g. Akao et al., 1989; Hashimoto & Matsumoto, 1998; Laufek et al., 2006; Mills et al., 2012). The mimetite structure was refined by Calos et al. (1990) and that of vanadinite by Laufek et al. (2006). The structure of all three Pb apatites, using duplicate samples, was recently refined with ADPs (Okudera, 2013).
The general formula for the lead apatite isotypic series is Pb5(BO4)3Cl, Z = 2, P63/m, with B = P5+ (pyromorphite), V5+ (vanadinite) and As5+ (mimetite). In these isomorphs, the O atoms occupy special positions, O1 and O2, and a general position, O3. The divalent Pb1 and Pb2 cation sites are at the 4f and 6h positions, respectively. The Cl anion occurs at the 2b position (0,0,0). The Pb1 site is coordinated by nine O atoms of six BO4 tetrahedral groups. The Pb2 site is eight-coordinated by six O and two Cl atoms. The Cl atom is octahedrally coordinated by six Pb2 atoms and each O atom is tetrahedrally coordinated by one B and three Pb atoms (Fig. 1). The Pb2 site is commonly found in an off-centred coordination environment in lead-containing apatites (Rouse et al., 1984; Kampf et al., 2006).
In the isotypic Pb apatites, the main difference is in the effective ionic radius (IR) of the B tetrahedral cation (P5+ = 0.170, V5+ = 0.335, As5+ = 0.355 Å and O2− = 1.380 Å; Shannon, 1976). Based on IR, one may expect the unit-cell parameters for the As and V apatites to be nearly equal, but their c parameters are quite different. The reason for this difference is not known. Based on radii sum, one may also expect distances close to the following: P—O = 1.550, V—O = 1.735 and As—O = 1.715 Å. However, experimentally, P—O = 1.542 (8), V—O = 1.710 (12) and As—O = 1.664 (16) Å (Okudera, 2013), so there appears to be significant differences for both the V—O and As—O distances. Based on IR, the unit-cell volume for vanadinite is expected to be slightly smaller than mimetite, but the opposite is found. Moreover, significant differences occur for the c unit-cell parameter between mimetite and vanadinite although the IR for As and V are nearly the same. The reasons for these discrepancies are not clear and will be examined in this study.
There are some experimental difficulties associated with structure refinements of lead apatites, despite the availability of high-quality museum specimens. X-ray scattering is dominated by highly absorbing Pb atoms among lighter atoms and the interaction of V atoms with neutrons is negligible. As a result, published e.g. Flis et al., 2010; Okudera, 2013). Therefore, despite successful structure refinements for Pb apatites, the errors are still large. However, synchrotron high-resolution powder X-ray diffraction (HRPXRD) data were successfully used to refine the crystal structures of Pb-containing materials such as PbCO3 and PbSO4 (Antao & Hassan, 2009; Antao, 2012).
refinements for all Pb apatites contain errors for positional coordinates in the third decimal place for the light O atoms, so errors occur in the second decimal place for bond distances (The study examines the s2 lone-pair electrons on the Pb2+ cation. Structural variations among Pb apatites are discussed.
of Pb apatites (pyromorphite, mimetite and vanadinite) using Rietveld structure refinements and HRPXRD data. The reason for the unusual unit-cell parameter for mimetite is explained based on Cl—Cl repulsion arising from interactions of the O1 atom with the 62. Experimental methods
2.1. Sample locality and description
Experiments were performed on samples of pyromorphite from (1) the Daoping Mine, Gunagxi Province, China, and (2) Ontario, Canada; (3) mimetite from the Pingtouling Mine, Guangdong, China, and (4) vanadinite from Mibladén, Morocco. All samples contain e.g. Laufek et al., 2006; Okudera, 2013). The pyromorphite sample used by Dai & Hughes (1989) was from Globe, Arizona, USA, and their vanadinite was from New South Wales, Australia. A mimetite sample from Durango, Mexico, was studied by Dai et al. (1991). Moreover, previous results from single-crystal and Rietvield structure refinements are compared in this study.
crystals with well developed faces. The colours of the crystals are (1) pale green, (2) yellow, (3) orange and (4) red. Except for the Ontario sample, single-crystal structure refinements of samples from localities (1), (3) and (4) above were carried out (2.2. Electron-probe micro-analyzer
Quantitative chemical compositions and backscattered electron images were collected with a Jeol JXA-8200 WD-ED electron-probe micro-analyzer (EPMA). The Jeol operating program on a Solaris platform was used for ZAF correction and data reduction. The wavelength-dispersive operating conditions were 15 kV accelerating voltage, 20 nA beam current and 5 µm beam diameter. Kα radiation and the following standards were used: gallium arsenide (As), vanadium oxide (V), pyromorphite (Pb, P), scapolite (Cl), hornblende (Fe, Na, Ca), cobalt (Co), nickel oxide (Ni), zinc oxide (Zn), barite (Ba) and strontianite (Sr). The EPMA results are listed in Table 1. The chemical composition of the Pb apatite samples are close to their ideal chemical formulae, which were used in previous structure refinements (see, for example, Okudera, 2013).
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2.3. Synchrotron high-resolution powder X-ray diffraction
The samples were studied using HRPXRD that was performed at beamline 11-BM, Advanced Photon Source, Argonne National Laboratory, USA. A small fragment (about 2 mm in diameter) of the sample was crushed to a fine powder using an agate mortar and pestle. The crushed sample was loaded into a Kapton capillary (0.8 mm internal diameter) and rotated during the experiment at a rate of 90 rotations per second. The data were collected at 23°C to a maximum 2θ of about 50° with a step size of 0.001° and a step time of 0.1 s per step. The HRPXRD traces were collected with a unique multi-analyzer detection assembly consisting of 12 independent silicon (111) crystal analyzers and LaCl3 scintillation detectors that reduce the angular range to be scanned and allow rapid acquisition of data. A silicon (NIST 640c) and alumina (NIST 676a) standard (ratio of by weight) was used to calibrate the instrument and refine the monochromatic wavelength used in the experiment (see Table 2). Additional details of the experimental setup are given elsewhere (Antao et al., 2008; Lee et al., 2008; Wang et al., 2008). Similar experiments were successfully used to examine other minerals (e.g. Antao et al., 2002; Antao & Hassan, 2002; Ehm et al., 2007; Skinner et al., 2012).
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2.4. Rietveld structure refinements
The HRPXRD traces were modelled using the ), as implemented in the GSAS program (Larson & Von Dreele, 2000), and using the EXPGUI interface (Toby, 2001). Scattering curves for neutral atoms were used in all refinements. For the structure of Pb apatite, the starting atom coordinates, unit-cell parameters and P63/m were taken from Hughes et al. (1989).
(Rietveld, 1969In the GSAS program, the reflection-peak profiles were fitted using a type-3 profile (pseudo-Voigt; Caglioti et al., 1958; Thompson et al., 1987). The background was modelled with a Chebyschev polynomial (eight terms). A full-matrix least-squares varying a scale factor, unit-cell parameters, zero shift, atom coordinates and isotropic displacement parameters converged rapidly. The number of data points and the number of observed reflections in the HRPXRD trace for each sample are given in Table 2. Synchrotron powder X-ray diffraction patterns are shown in Fig. 2. Table 2 contains the statistical indicators and unit-cell parameters. The atom coordinates are given in Table 3. Some site occupancy factors were refined and those for the O atoms were fixed (Table 3). Selected bond distances and angles are given in Table 4.
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3. Results and discussion
3.1. Structure of Pb apatites
This study reports Rietveld structure refinements of Pb apatite samples from some classical localities. Other researchers have also used samples from these localities, so the results from several studies can be compared. Pyromorphite and mimetite samples from China and vanadinite from Mibladén, Morocco, were also examined by other researchers (Laufek et al., 2006; Okudera, 2013). These studies reported the ideal chemical formulae Pb5(BO4)3Cl based on EPMA results and the ideal formulae were used in their structure refinements. In this study, some site occupancy factors (sofs) were refined (Table 3). Our sofs agree well with our EPMA results.
The . The Pb1 site is surrounded by nine O atoms, and the Pb2 site is surrounded by six O atoms and two Cl atoms. The B site is surrounded by four O atoms. The bond distances and angles of the two pyromorphite samples are in good agreement (Table 4). The distortions in the BO4 tetrahedra are similar to each other.
of Pb apatite is shown in Fig. 1The structure of Pb apatite isotypes is similar to those previously reported. The minerals crystallize with the chlorapatite structure, P63/m, and the Cl atom occurs at the 2b position with no evidence of site splitting. The Pb2 site is commonly found in an off-centric coordination environment (Rouse et al., 1984; Kampf et al., 2006).
The bond-valence sums (BVS) for the Pb2+ and B5+ cations are close to their formal valences (Table 4). The BVS value for Cl− is close to 1.0 valence unit (v.u.) for mimetite and vanadinite, but it is 1.16 v.u. for pyromorphite (Table 4). BVS values higher than 1.25 v.u. for Cl− were calculated for phosphohedyphane, Ca2Pb3(PO4)3Cl (Kampf et al., 2006), Sr2Ba3(AsO4)3Cl (Đordević et al., 2008), synthetic alforsite, Ba5(PO4)3Cl (Hata et al., 1979), and lower than 1.1 v.u. in Sr5(VO4)3Cl (Beck et al., 2006).
3.2. Variations among unit-cell parameters in Pb apatites
The relationships between unit-cell parameters are shown in Fig. 3. Data from the literature are included for comparison (see Fig. 3 and its caption for references). The unit-cell parameters fall along two straight lines representing the P–As and As–V apatite series. The volumes for mimetite and vanadinite are almost equal. However, vanadinite has the largest a unit-cell parameter (Fig. 3a). The c parameter for mimetite is significantly larger than that for vanadinite, which is nearly the same as that for pyromorphite (Fig. 3b). The c/a ratio for mimetite is larger than that for vanadinite (Fig. 3c). Pyromorphite and vanadinite have similar values for the c parameter, but that for mimetite is the largest (Fig. 3d). All unit-cell data from the literature seem reasonable, including single-crystal data, so there appears to be no difficulties in obtaining good unit-cell parameters.
The unit-cell parameters occur in three groups, which may indicate limited solid solutions in nature. However, this observation may arise from the small number of natural samples examined. The unit-cell parameters of the synthetic samples show complete solid solutions between the pyromorphite–mimetite series (Flis et al., 2010). Although complete solid solutions may be possible along the mimetite–vanadinite and pyromorphite–vanadinite joins, unit-cell data are needed for synthetic samples along these joins. In nature, solid solutions occur to a very limited extent, so samples from different localities have similar unit-cell parameters that cluster in three groups. Why is the c parameter between mimetite and vanadinite so different (0.108 Å), whereas the effective ionic radii difference between As (0.335 Å) and V (0.355 Å) is quite small (Δc = 0.020 Å)? In contrast, the c parameter between pyromorphite and mimetite differ by a similar amount (Δr = 0.113 Å), but the effective ionic radii difference between P (0.170 Å) and As (0.335 Å) is quite large (0.165 Å). The answer to this question is based on the significant differences between mimetite and vanadinite and is related to the Cl—Cl and Pb2—O1 distances, as explained below.
Our two pyromorphite samples have different unit-cell parameters. The sample from Ontario has unit-cell data that coincide with that of the synthetic end-member, but the other sample from China has the smallest V, which indicates subtle chemical differences between the two samples (Table 1).
3.3. Structural variations in Pb apatites
Linear variations of selected distances with the unit-cell volume, V, are shown in Fig. 4. The average 〈Pb1—O〉 [9] distances increase linearly with V (Fig. 4a). The Pb2—Cl distance also increases linearly with V (Fig. 4b). The Cl—Cl distance (= c/2) increases linearly with the c parameter, as expected (not shown). Both the average 〈Pb2—O〉 [6] and 〈Pb2—O6,Cl2〉 [8] distances increase linearly with V [Figs. 4(c) and 4(d)]. The average 〈B—O〉 distance also increases linearly with V (Fig. 4e). Both mimetite and vanadinite have similar structural parameters because the radii for As and V are nearly the same (Fig. 4f).
A regular tetrahedron has six equal angles of 109.47°. Across the series, the O—B—O angles do not vary in a systematic manner. However, their average 〈O—B—O〉 [6] angle is close to the regular tetrahedron value (Table 4).
Some discrepancies are clearly observed between the present data and those from the literature (Fig. 4). Okudera (2013) selected two crystals from each of his three samples and presented six data points (duplicate runs). Chemical analyses of crystals from the same sample are not variable, so the differences observed between his duplicate samples arise only from experimental errors. This is clearly observed for some parameters shown for mimetite and vanadinite [Figs. 4(c) and 4(d)]. Other data from the literature, indicated by triangles, are off the red trend lines for data from this study, especially for pyromorphite [Figs. 4(c) and 4(d)]. For the synthetic samples along the pyromorphite–mimetite join [Figs. 4(a), 4(c) and 4(d)], the structural data fall on black trend lines that are different from the red trend lines of this study.
In Table 4, differences between mimetite and vanadinite are shown. The largest difference is between their c unit-cell parameter, Pb2—O1, and Cl—Cl distances. The Pb2—O1 distance is short in mimetite, whereas the Cl—Cl (= c/2) distance is long. The opposite is observed for vanadinite where the Pb2—O1 distance is long and the Cl—Cl distance is short.
The coordination of the Pb2 site in vanadinite is shown together with the distances within the Pb2—O6Cl2 polyhedra (Fig. 5). A large open space exists between the two Cl and O1 oxygen atoms where the 6s2 lone-pair electrons on the Pb2+ cation occurs (Kampf et al., 2006). As Pb2—O1 becomes shorter, the 6s2 lone-pair electrons move towards the two Cl atoms and cause them to move apart because of Cl—Cl repulsion. The opposite is the case for vanadinite. This feature explains the different and unusual c unit-cell parameters for mimetite and vanadinite, as discussed above.
From a structural point of view, solid solutions are expected among pyromorphite, mimetite and vanadinite (Figs. 3 and 4). However, synthetic samples for the various joins are needed and the structure of such samples needs to be well characterized. An analysis of compositions of natural members of the pyromorphite–mimetite–turneaureite–chlorapatite system suggests the existence of a complete among pyromorphite, mimetite, hedyphane and phosphohedyphane [Ca2Pb3(PO4)3Cl]. No stable solid solutions appear to exist between the joins phosphohedyphane–hedyphane and chlorapatite–turneaureite in natural systems (Kampf et al., 2006).
Calcian pyromorphite has been identified as the major lead-bearing phase in mine waste soils from the South Pennine orefield, UK (Cotter-Howells et al., 1994), and the Charterhouse mine in the Mendip Hills, UK (Cotter-Howells & Caporn, 1996). In experiments on the use of apatite amendments to Pb-contaminated soil (including associated grass roots) from a residential area near Oakland, California, USA, Laperche et al. (1997) noted that, when the soils were treated with phosphate rock (containing fluorapatite as the major constituent), all pyromorphite formed contained significant Ca. The apparent stability in natural systems of members of the chlorapatite–pyromorphite series between pyromorphite and phosphohedyphane, but not between phosphohedyphane and chlorapatite, may have important implications for the use of apatite to reclaim Pb-contaminated waters and soils.
This study shows that HRPXRD is a powerful technique that can be used to obtain reliable structural parameters on gem-quality crystals that diffract poorly. Moreover, highly penetrating synchrotron X-rays can also be used to study samples that contain strongly absorbing atoms.
Supporting information
https://doi.org/10.1107/S1600577517014217/co5089sup1.cif
contains datablocks global, pyromor_ch_publ. DOI:https://doi.org/10.1107/S1600577517014217/co5089sup2.cif
contains datablocks global, pyromorphite_publ. DOI: contains datablocks global, 2profs_mimetite-chin_publ. DOI: contains datablocks global, 2profs_vanadinite_publ. DOI:Cl0.32O4PPb1.59 | V = 629.68 (1) Å3 |
Mr = 2614.89 | Z = 1 |
Hexagonal, P63/m | F(000) = 1097 |
Hall symbol: -P 6c | Dx = 6.896 Mg m−3 |
a = 9.96350 (2) Å | Synchrotron radiation |
c = 7.32427 (1) Å | T = 296 K |
11BM diffractometer | Detector resolution: 18.4 pixels mm-1 |
Radiation source: synchrotron, synchrotron |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pb1 | 0.33333 | 0.66667 | 0.0039 (2) | 0.0104 (1)* | 0.948 (5) |
Pb2 | 0.25449 (7) | 0.00550 (10) | 0.25000 | 0.0104 (1)* | 0.960 (4) |
P | 0.4093 (4) | 0.3773 (4) | 0.25000 | 0.0077 (9)* | |
Cl | 0.00000 | 0.00000 | 0.00000 | 0.0115 (12)* | 0.947 (9) |
O1 | 0.3426 (9) | 0.4905 (8) | 0.25000 | 0.011 (2)* | |
O2 | 0.5897 (9) | 0.4778 (9) | 0.25000 | 0.011 (2)* | |
O3 | 0.3639 (6) | 0.2755 (6) | 0.0784 (6) | 0.0155 (17)* |
Pb1—O1 | 2.550 (6) | Pb2—O3 | 2.659 (5) |
Pb1—O2i | 2.687 (10) | Pb2—O2ix | 2.326 (11) |
Pb1—O1ii | 2.550 (7) | Pb2—O3x | 2.627 (5) |
Pb1—O2iii | 2.687 (7) | Pb2—O3xi | 2.627 (5) |
Pb1—O1iv | 2.550 (9) | Pb2—O3xii | 2.659 (5) |
Pb1—O2v | 2.687 (8) | P—O1 | 1.570 (10) |
Pb1—O3vi | 2.839 (7) | P—O2 | 1.560 (10) |
Pb1—O3vii | 2.839 (7) | P—O3 | 1.534 (5) |
Pb1—O3viii | 2.839 (6) | P—O3xii | 1.534 (5) |
O1—Pb1—O2i | 126.9 (2) | O2v—Pb1—O3viii | 123.3 (2) |
O1—Pb1—O1ii | 75.5 (2) | O3vi—Pb1—O3vii | 115.62 (17) |
O1—Pb1—O2iii | 90.13 (19) | O3vi—Pb1—O3viii | 115.62 (19) |
O1—Pb1—O1iv | 75.5 (3) | O3vii—Pb1—O3viii | 115.6 (2) |
O1—Pb1—O2v | 149.9 (3) | O2ix—Pb2—O3 | 75.1 (3) |
O1—Pb1—O3vi | 83.6 (2) | O3—Pb2—O3x | 136.69 (18) |
O1—Pb1—O3vii | 146.60 (18) | O3—Pb2—O3xi | 82.08 (18) |
O1—Pb1—O3viii | 74.1 (2) | O3—Pb2—O3xii | 56.41 (14) |
O1ii—Pb1—O2i | 149.9 (3) | O2ix—Pb2—O3x | 83.39 (19) |
O2i—Pb1—O2iii | 77.4 (3) | O2ix—Pb2—O3xi | 83.39 (19) |
O1iv—Pb1—O2i | 90.1 (3) | O2ix—Pb2—O3xii | 75.1 (3) |
O2i—Pb1—O2v | 77.4 (3) | O3x—Pb2—O3xi | 132.6 (2) |
O2i—Pb1—O3vi | 123.3 (2) | O3x—Pb2—O3xii | 82.08 (18) |
O2i—Pb1—O3vii | 66.9 (2) | O3xi—Pb2—O3xii | 136.69 (18) |
O2i—Pb1—O3viii | 53.3 (2) | O1—P—O2 | 107.7 (5) |
O1ii—Pb1—O2iii | 126.9 (3) | O1—P—O3 | 112.6 (3) |
O1ii—Pb1—O1iv | 75.5 (3) | O1—P—O3xii | 112.6 (3) |
O1ii—Pb1—O2v | 90.1 (2) | O2—P—O3 | 106.8 (3) |
O1ii—Pb1—O3vi | 74.1 (2) | O2—P—O3xii | 106.8 (3) |
O1ii—Pb1—O3vii | 83.6 (2) | O3—P—O3xii | 110.0 (3) |
O1ii—Pb1—O3viii | 146.6 (2) | Pb1—O1—P | 132.0 (2) |
O1iv—Pb1—O2iii | 149.9 (2) | Pb1—O1—Pb1xiii | 90.0 (3) |
O2iii—Pb1—O2v | 77.4 (2) | Pb1xiii—O1—P | 132.0 (2) |
O2iii—Pb1—O3vi | 53.3 (2) | Pb1xiv—O2—P | 101.7 (3) |
O2iii—Pb1—O3vii | 123.27 (17) | Pb2xv—O2—P | 130.5 (5) |
O2iii—Pb1—O3viii | 66.9 (2) | Pb1vi—O2—P | 101.7 (3) |
O1iv—Pb1—O2v | 126.9 (3) | Pb1xiv—O2—Pb1vi | 87.6 (3) |
O1iv—Pb1—O3vi | 146.6 (2) | Pb2—O3—P | 96.8 (2) |
O1iv—Pb1—O3vii | 74.1 (2) | Pb2—O3—Pb2i | 114.22 (19) |
O1iv—Pb1—O3viii | 83.6 (2) | Pb2i—O3—P | 140.8 (4) |
O2v—Pb1—O3vi | 66.9 (3) | Pb1vi—O3—P | 96.2 (3) |
O2v—Pb1—O3vii | 53.3 (3) | ||
O3x—Pb2—O3—P | −17.4 (5) | O3—P—O1—Pb1 | −45.5 (7) |
O3xi—Pb2—O3—P | −165.5 (4) | O1—P—O3—Pb2 | −128.8 (4) |
O3xii—Pb2—O3—P | 1.6 (3) | O2—P—O3—Pb2 | 113.1 (4) |
O3—Pb2—O3xii—P | −1.6 (3) | O3xii—P—O3—Pb2 | −2.4 (5) |
O2—P—O1—Pb1 | 72.0 (5) | O3—P—O3xii—Pb2 | 2.4 (5) |
Symmetry codes: (i) x−y, x, z−1/2; (ii) −y+1, x−y+1, z; (iii) −x+1, −y+1, z−1/2; (iv) −x+y, −x+1, z; (v) y, −x+y+1, z−1/2; (vi) −x+1, −y+1, −z; (vii) y, −x+y+1, −z; (viii) x−y, x, −z; (ix) −y+1, x−y, z; (x) y, −x+y, z+1/2; (xi) y, −x+y, −z; (xii) x, y, −z+1/2; (xiii) −x+y, −x+1, −z+1/2; (xiv) x−y+1, x, z+1/2; (xv) −x+y+1, −x+1, z. |
ClO12P3Pb5 | V = 635.02 (1) Å3 |
Mr = 1356.36 | Z = 2 |
Hexagonal, P63/m | F(000) = 1136 |
Hall symbol: -P 6c | Dx = 7.094 Mg m−3 |
a = 9.99497 (2) Å | Synchrotron radiation |
c = 7.33997 (2) Å | T = 296 K |
11BM diffractometer | Detector resolution: 18.4 pixels mm-1 |
Radiation source: synchrotron, synchrotron |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
x | y | z | Uiso*/Ueq | ||
Pb1 | 0.33333 | 0.66667 | 0.0052 (2) | 0.0241 (2)* | |
Pb2 | 0.25474 (8) | 0.00590 (10) | 0.25000 | 0.0234 (1)* | |
Cl | 0.00000 | 0.00000 | 0.00000 | 0.0141 (12)* | |
P | 0.4098 (5) | 0.3802 (5) | 0.25000 | 0.0150 (12)* | |
O1 | 0.3450 (10) | 0.4920 (10) | 0.25000 | 0.023 (3)* | |
O2 | 0.5890 (10) | 0.4740 (10) | 0.25000 | 0.017 (3)* | |
O3 | 0.3596 (8) | 0.2696 (8) | 0.0814 (8) | 0.030 (2)* |
Pb1—O1 | 2.548 (7) | Pb2—O3 | 2.610 (7) |
Pb1—O2i | 2.680 (10) | Pb2—Clix | 3.1150 (8) |
Pb1—O1ii | 2.548 (9) | Pb2—O2x | 2.363 (12) |
Pb1—O2iii | 2.680 (7) | Pb2—O3xi | 2.646 (7) |
Pb1—O1iv | 2.548 (11) | Pb2—O3xii | 2.646 (7) |
Pb1—O2v | 2.680 (9) | Pb2—O3xiii | 2.610 (7) |
Pb1—O3vi | 2.877 (9) | P—O1 | 1.547 (11) |
Pb1—O3vii | 2.877 (9) | P—O2 | 1.552 (12) |
Pb1—O3viii | 2.877 (7) | P—O3 | 1.565 (7) |
Pb2—Cl | 3.1150 (8) | P—O3xiii | 1.565 (7) |
O1—Pb1—O2i | 127.2 (3) | Clix—Pb2—O2x | 138.34 (14) |
O1—Pb1—O1ii | 75.8 (3) | Clix—Pb2—O3xi | 69.2 (2) |
O1—Pb1—O2iii | 90.5 (2) | Clix—Pb2—O3xii | 136.7 (2) |
O1—Pb1—O1iv | 75.8 (3) | Clix—Pb2—O3xiii | 69.61 (18) |
O1—Pb1—O2v | 150.0 (4) | O2x—Pb2—O3xi | 84.7 (2) |
O1—Pb1—O3vi | 84.2 (3) | O2x—Pb2—O3xii | 84.7 (2) |
O1—Pb1—O3vii | 147.2 (2) | O2x—Pb2—O3xiii | 75.2 (3) |
O1—Pb1—O3viii | 74.3 (2) | O3xi—Pb2—O3xii | 133.7 (3) |
O1ii—Pb1—O2i | 150.0 (4) | O3xi—Pb2—O3xiii | 82.1 (2) |
O2i—Pb1—O2iii | 76.5 (3) | O3xii—Pb2—O3xiii | 137.3 (2) |
O1iv—Pb1—O2i | 90.5 (3) | Pb2—Cl—Pb2i | 91.18 (2) |
O2i—Pb1—O2v | 76.5 (3) | Pb2—Cl—Pb2xiv | 88.82 (2) |
O2i—Pb1—O3vi | 122.3 (3) | Pb2—Cl—Pb2xv | 180.00 |
O2i—Pb1—O3vii | 66.3 (3) | Pb2—Cl—Pb2xvi | 88.82 (2) |
O2i—Pb1—O3viii | 53.5 (2) | Pb2—Cl—Pb2xvii | 91.18 (2) |
O1ii—Pb1—O2iii | 127.2 (3) | Pb2i—Cl—Pb2xiv | 91.18 (2) |
O1ii—Pb1—O1iv | 75.8 (3) | Pb2i—Cl—Pb2xv | 88.82 (2) |
O1ii—Pb1—O2v | 90.5 (3) | Pb2i—Cl—Pb2xvi | 180.00 |
O1ii—Pb1—O3vi | 74.3 (3) | Pb2i—Cl—Pb2xvii | 88.82 (2) |
O1ii—Pb1—O3vii | 84.2 (3) | Pb2xiv—Cl—Pb2xv | 91.18 (2) |
O1ii—Pb1—O3viii | 147.2 (2) | Pb2xiv—Cl—Pb2xvi | 88.82 (2) |
O1iv—Pb1—O2iii | 150.0 (3) | Pb2xiv—Cl—Pb2xvii | 180.00 |
O2iii—Pb1—O2v | 76.5 (3) | Pb2xv—Cl—Pb2xvi | 91.18 (2) |
O2iii—Pb1—O3vi | 53.5 (3) | Pb2xv—Cl—Pb2xvii | 88.82 (2) |
O2iii—Pb1—O3vii | 122.3 (2) | Pb2xvi—Cl—Pb2xvii | 91.18 (2) |
O2iii—Pb1—O3viii | 66.3 (3) | O1—P—O2 | 109.7 (6) |
O1iv—Pb1—O2v | 127.2 (3) | O1—P—O3 | 114.1 (4) |
O1iv—Pb1—O3vi | 147.2 (3) | O1—P—O3xiii | 114.1 (4) |
O1iv—Pb1—O3vii | 74.3 (3) | O2—P—O3 | 107.0 (4) |
O1iv—Pb1—O3viii | 84.2 (3) | O2—P—O3xiii | 107.0 (4) |
O2v—Pb1—O3vi | 66.3 (3) | O3—P—O3xiii | 104.5 (4) |
O2v—Pb1—O3vii | 53.5 (3) | Pb1—O1—P | 132.4 (3) |
O2v—Pb1—O3viii | 122.3 (2) | Pb1—O1—Pb1xviii | 89.7 (3) |
O3vi—Pb1—O3vii | 115.3 (2) | Pb1xviii—O1—P | 132.4 (3) |
O3vi—Pb1—O3viii | 115.3 (3) | Pb1xix—O2—P | 103.5 (3) |
O3vii—Pb1—O3viii | 115.3 (3) | Pb2xx—O2—P | 128.0 (6) |
Cl—Pb2—O3 | 69.61 (18) | Pb1vi—O2—P | 103.5 (3) |
Cl—Pb2—Clix | 72.18 (2) | Pb1xix—O2—Pb2xx | 112.9 (3) |
Cl—Pb2—O2x | 138.34 (14) | Pb1xix—O2—Pb1vi | 88.7 (3) |
Cl—Pb2—O3xi | 136.7 (2) | Pb1vi—O2—Pb2xx | 112.9 (3) |
Cl—Pb2—O3xii | 69.2 (2) | Pb2—O3—P | 99.4 (3) |
Cl—Pb2—O3xiii | 102.13 (18) | Pb2—O3—Pb2i | 115.7 (3) |
Clix—Pb2—O3 | 102.13 (18) | Pb1vi—O3—Pb2 | 100.0 (3) |
O2x—Pb2—O3 | 75.2 (3) | Pb2i—O3—P | 138.1 (4) |
O3—Pb2—O3xi | 137.3 (2) | Pb1vi—O3—P | 95.1 (4) |
O3—Pb2—O3xii | 82.1 (2) | Pb1vi—O3—Pb2i | 100.3 (2) |
O3—Pb2—O3xiii | 56.60 (19) | ||
Cl—Pb2—O3—P | 123.2 (5) | O3—P—O1—Pb1 | −47.3 (9) |
O3xi—Pb2—O3—P | −14.8 (7) | O1—P—O3—Pb2 | −128.5 (4) |
O3xii—Pb2—O3—P | −166.1 (5) | O2—P—O3—Pb2 | 109.9 (4) |
O3xiii—Pb2—O3—P | 2.3 (4) | O3xiii—P—O3—Pb2 | −3.3 (6) |
O3—Pb2—O3xiii—P | −2.3 (4) | O3—P—O3xiii—Pb2 | 3.3 (6) |
O2—P—O1—Pb1 | 72.7 (6) |
Symmetry codes: (i) x−y, x, z−1/2; (ii) −y+1, x−y+1, z; (iii) −x+1, −y+1, z−1/2; (iv) −x+y, −x+1, z; (v) y, −x+y+1, z−1/2; (vi) −x+1, −y+1, −z; (vii) y, −x+y+1, −z; (viii) x−y, x, −z; (ix) x−y, x, z+1/2; (x) −y+1, x−y, z; (xi) y, −x+y, z+1/2; (xii) y, −x+y, −z; (xiii) x, y, −z+1/2; (xiv) −y, x−y, z; (xv) −x, −y, z−1/2; (xvi) −x+y, −x, z; (xvii) y, −x+y, z−1/2; (xviii) −x+y, −x+1, −z+1/2; (xix) x−y+1, x, z+1/2; (xx) −x+y+1, −x+1, z. |
As3ClO12Pb5 | V = 677.93 (1) Å3 |
Mr = 1488.21 | Z = 2 |
Hexagonal, P63/m | F(000) = 1244 |
Hall symbol: -P 6c | Dx = 7.291 Mg m−3 |
a = 10.24823 (2) Å | Synchrotron radiation |
c = 7.45339 (2) Å | T = 296 K |
11BM diffractometer | Detector resolution: 18.4 pixels mm-1 |
Radiation source: synchrotron, synchrotron |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
x | y | z | Uiso*/Ueq | ||
Pb1 | 0.33333 | 0.66667 | 0.5064 (2) | 0.0139 (1)* | |
Pb2 | 0.00500 (9) | 0.25099 (6) | 0.25000 | 0.0139 (1)* | |
As | 0.38380 (10) | 0.40810 (10) | 0.25000 | 0.0047 (3)* | |
Cl | 0.00000 | 0.00000 | 0.00000 | 0.0141 (10)* | |
O1 | 0.4932 (8) | 0.3226 (8) | 0.25000 | 0.013 (2)* | |
O2 | 0.4853 (8) | 0.5986 (9) | 0.25000 | 0.022 (2)* | |
O3 | 0.2735 (6) | 0.3588 (6) | 0.0666 (7) | 0.042 (2)* |
Pb1—As | 3.5088 (12) | Pb2—Cl | 3.1558 (5) |
Pb1—O2 | 2.766 (7) | Pb2—O3 | 2.761 (6) |
Pb1—O1i | 2.505 (6) | Pb2—Cli | 3.1558 (5) |
Pb1—Asii | 3.5088 (13) | Pb2—O3i | 2.587 (6) |
Pb1—O2ii | 2.766 (8) | Pb2—O1viii | 3.031 (10) |
Pb1—O1iii | 2.505 (6) | Pb2—O2iv | 2.353 (7) |
Pb1—Asiv | 3.5088 (15) | Pb2—O3vii | 2.761 (6) |
Pb1—O2iv | 2.766 (8) | Pb2—O3ix | 2.587 (6) |
Pb1—O1v | 2.505 (7) | As—O1 | 1.734 (9) |
Pb1—O3vi | 2.948 (9) | As—O2 | 1.692 (8) |
Pb1—O3vii | 2.948 (6) | As—O3 | 1.682 (6) |
Pb2—As | 3.3782 (14) | As—O3vii | 1.682 (6) |
As—Pb1—O2 | 28.24 (17) | O2iv—Pb2—O3 | 74.8 (3) |
As—Pb1—O1i | 98.98 (18) | O3—Pb2—O3vii | 59.36 (17) |
As—Pb1—Asii | 93.16 (3) | O3—Pb2—O3ix | 80.9 (2) |
As—Pb1—O2ii | 99.62 (17) | Cli—Pb2—O3i | 70.93 (15) |
As—Pb1—O1iii | 93.36 (16) | Cli—Pb2—O1viii | 102.36 (15) |
As—Pb1—Asiv | 93.16 (4) | Cli—Pb2—O2iv | 137.93 (15) |
As—Pb1—O2iv | 65.5 (2) | Cli—Pb2—O3vii | 68.93 (11) |
As—Pb1—O1v | 165.88 (18) | Cli—Pb2—O3ix | 138.64 (12) |
As—Pb1—O3vi | 121.64 (11) | O1viii—Pb2—O3i | 68.11 (18) |
As—Pb1—O3vii | 28.55 (11) | O2iv—Pb2—O3i | 83.22 (17) |
O1i—Pb1—O2 | 125.5 (3) | O3i—Pb2—O3vii | 80.9 (2) |
Asii—Pb1—O2 | 65.48 (16) | O3i—Pb2—O3ix | 131.6 (3) |
O2—Pb1—O2ii | 77.5 (2) | O1viii—Pb2—O2iv | 97.7 (4) |
O1iii—Pb1—O2 | 92.0 (2) | O1viii—Pb2—O3vii | 148.86 (13) |
Asiv—Pb1—O2 | 99.62 (15) | O1viii—Pb2—O3ix | 68.11 (18) |
O2—Pb1—O2iv | 77.5 (3) | O2iv—Pb2—O3vii | 74.8 (3) |
O1v—Pb1—O2 | 152.4 (3) | O2iv—Pb2—O3ix | 83.22 (17) |
O2—Pb1—O3vi | 125.29 (18) | O3vii—Pb2—O3ix | 138.2 (2) |
O2—Pb1—O3vii | 56.3 (2) | Pb1—As—Pb2 | 77.98 (2) |
Asii—Pb1—O1i | 165.88 (13) | Pb1—As—O1 | 139.31 (14) |
O1i—Pb1—O2ii | 152.4 (3) | Pb1—As—O2 | 50.7 (2) |
O1i—Pb1—O1iii | 73.3 (3) | Pb1—As—O3 | 109.8 (2) |
Asiv—Pb1—O1i | 93.4 (2) | Pb1—As—Pb1vi | 66.00 (3) |
O1i—Pb1—O2iv | 92.0 (2) | Pb1—As—O3vii | 56.88 (19) |
O1i—Pb1—O1v | 73.3 (2) | Pb2—As—O1 | 129.7 (3) |
O1i—Pb1—O3vi | 86.8 (3) | Pb2—As—O2 | 116.6 (3) |
O1i—Pb1—O3vii | 70.5 (2) | Pb2—As—O3 | 54.4 (2) |
Asii—Pb1—O2ii | 28.2 (2) | Pb1vi—As—Pb2 | 77.98 (2) |
Asii—Pb1—O1iii | 98.98 (16) | Pb2—As—O3vii | 54.4 (2) |
Asii—Pb1—Asiv | 93.16 (4) | O1—As—O2 | 113.8 (4) |
Asii—Pb1—O2iv | 99.62 (13) | O1—As—O3 | 110.8 (2) |
Asii—Pb1—O1v | 93.36 (19) | Pb1vi—As—O1 | 139.31 (14) |
Asii—Pb1—O3vi | 93.00 (11) | O1—As—O3vii | 110.8 (2) |
Asii—Pb1—O3vii | 121.64 (12) | O2—As—O3 | 106.2 (3) |
O1iii—Pb1—O2ii | 125.5 (3) | Pb1vi—As—O2 | 50.7 (2) |
Asiv—Pb1—O2ii | 65.5 (2) | O2—As—O3vii | 106.2 (3) |
O2ii—Pb1—O2iv | 77.5 (2) | Pb1vi—As—O3 | 56.88 (19) |
O1v—Pb1—O2ii | 92.0 (2) | O3—As—O3vii | 108.7 (3) |
O2ii—Pb1—O3vi | 66.1 (3) | Pb1vi—As—O3vii | 109.8 (2) |
O2ii—Pb1—O3vii | 125.29 (19) | Pb2—Cl—Pb2x | 91.32 (2) |
Asiv—Pb1—O1iii | 165.88 (16) | Pb2—Cl—Pb2viii | 88.69 (2) |
O1iii—Pb1—O2iv | 152.4 (2) | Pb2—Cl—Pb2xi | 180.00 |
O1iii—Pb1—O1v | 73.3 (3) | Pb2—Cl—Pb2xii | 88.69 (2) |
O1iii—Pb1—O3vi | 142.32 (19) | Pb2—Cl—Pb2xiii | 91.32 (2) |
O1iii—Pb1—O3vii | 86.8 (2) | Pb2x—Cl—Pb2viii | 91.32 (2) |
Asiv—Pb1—O2iv | 28.2 (2) | Pb2x—Cl—Pb2xi | 88.69 (2) |
Asiv—Pb1—O1v | 99.0 (2) | Pb2x—Cl—Pb2xii | 180.00 |
Asiv—Pb1—O3vi | 28.55 (10) | Pb2x—Cl—Pb2xiii | 88.69 (2) |
Asiv—Pb1—O3vii | 93.00 (13) | Pb2viii—Cl—Pb2xi | 91.32 (2) |
O1v—Pb1—O2iv | 125.5 (3) | Pb2viii—Cl—Pb2xii | 88.69 (2) |
O2iv—Pb1—O3vi | 56.3 (3) | Pb2viii—Cl—Pb2xiii | 180.00 |
O2iv—Pb1—O3vii | 66.1 (2) | Pb2xi—Cl—Pb2xii | 91.32 (2) |
O1v—Pb1—O3vi | 70.5 (2) | Pb2xi—Cl—Pb2xiii | 88.69 (2) |
O1v—Pb1—O3vii | 142.3 (2) | Pb2xii—Cl—Pb2xiii | 91.32 (2) |
O3vi—Pb1—O3vii | 116.67 (17) | Pb1xiv—O1—As | 127.0 (2) |
As—Pb2—Cl | 86.27 (2) | Pb2xii—O1—As | 99.6 (3) |
As—Pb2—O3 | 29.69 (12) | Pb1xv—O1—As | 127.0 (2) |
As—Pb2—Cli | 86.27 (2) | Pb1xiv—O1—Pb2xii | 103.3 (2) |
As—Pb2—O3i | 109.55 (17) | Pb1xiv—O1—Pb1xv | 92.9 (3) |
As—Pb2—O1viii | 169.24 (19) | Pb1xv—O1—Pb2xii | 103.3 (2) |
As—Pb2—O2iv | 71.5 (3) | Pb1—O2—As | 101.1 (3) |
As—Pb2—O3vii | 29.69 (12) | Pb1—O2—Pb2ii | 115.5 (2) |
As—Pb2—O3ix | 109.55 (17) | Pb1—O2—Pb1vi | 87.4 (3) |
Cl—Pb2—O3 | 68.93 (11) | Pb2ii—O2—As | 128.1 (5) |
Cl—Pb2—Cli | 72.38 (1) | Pb1vi—O2—As | 101.1 (3) |
Cl—Pb2—O3i | 138.64 (12) | Pb1vi—O2—Pb2ii | 115.5 (2) |
Cl—Pb2—O1viii | 102.36 (15) | Pb2—O3—As | 95.9 (2) |
Cl—Pb2—O2iv | 137.93 (15) | Pb2—O3—Pb2xiii | 115.1 (2) |
Cl—Pb2—O3vii | 103.02 (13) | Pb1vi—O3—Pb2 | 98.7 (2) |
Cl—Pb2—O3ix | 70.93 (15) | Pb2xiii—O3—As | 140.5 (4) |
Cli—Pb2—O3 | 103.02 (13) | Pb1vi—O3—As | 94.6 (2) |
O3—Pb2—O3i | 138.2 (2) | Pb1vi—O3—Pb2xiii | 103.55 (18) |
O1viii—Pb2—O3 | 148.86 (13) | ||
O2—Pb1—As—Pb2 | −139.9 (3) | Cl—Pb2—O3—As | −122.3 (2) |
O2—Pb1—As—O1 | 81.2 (4) | O3i—Pb2—O3—As | 18.6 (4) |
O2—Pb1—As—O3 | −95.1 (4) | O3vii—Pb2—O3—As | −1.75 (19) |
O3vi—Pb1—As—O3 | 11.6 (2) | O3ix—Pb2—O3—As | 164.7 (3) |
O3vii—Pb1—As—O3 | 99.9 (3) | O3—Pb2—O3vii—Pb1 | 97.3 (2) |
Cl—Pb2—As—Pb1 | 177.56 (2) | O3—Pb2—O3vii—As | 1.75 (19) |
Cl—Pb2—As—O1 | −36.28 (1) | Pb2—As—O2—Pb1 | 44.75 (18) |
Cl—Pb2—As—O2 | 143.72 (1) | O1—As—O2—Pb1 | −135.25 (18) |
Cl—Pb2—As—O3 | 52.2 (2) | O3—As—O2—Pb1 | 102.6 (3) |
O3—Pb2—As—Pb1 | 125.4 (2) | Pb1—As—O3—Pb2 | −57.97 (18) |
O3—Pb2—As—O1 | −88.5 (2) | O1—As—O3—Pb2 | 124.6 (3) |
O3—Pb2—As—O2 | 91.5 (2) | O2—As—O3—Pb2 | −111.4 (3) |
O3—Pb2—As—O3vii | −177.0 (3) | O3vii—As—O3—Pb2 | 2.6 (3) |
O3i—Pb2—As—O3 | −167.0 (3) | O3—As—O3vii—Pb1 | −101.9 (2) |
O3vii—Pb2—As—O3 | 177.0 (3) | O3—As—O3vii—Pb2 | −2.6 (3) |
O3ix—Pb2—As—O3 | −16.1 (3) |
Symmetry codes: (i) x−y, x, z+1/2; (ii) −y+1, x−y+1, z; (iii) −x+1, −y+1, z+1/2; (iv) −x+y, −x+1, z; (v) y, −x+y+1, z+1/2; (vi) −x+y, −x+1, −z+1/2; (vii) x, y, −z+1/2; (viii) −y, x−y, z; (ix) x−y, x, −z; (x) x−y, x, z−1/2; (xi) −x, −y, z−1/2; (xii) −x+y, −x, z; (xiii) y, −x+y, z−1/2; (xiv) x−y+1, x, z−1/2; (xv) −x+1, −y+1, −z+1. |
ClO12Pb5V3 | V = 678.07 (1) Å3 |
Mr = 1416.27 | Z = 2 |
Hexagonal, P63/m | F(000) = 1184 |
Hall symbol: -P 6c | Dx = 6.937 Mg m−3 |
a = 10.32464 (2) Å | Synchrotron radiation |
c = 7.34508 (2) Å | T = 296 K |
11BM diffractometer | Detector resolution: 18.4 pixels mm-1 |
Radiation source: synchrotron, synchrotron |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
x | y | z | Uiso*/Ueq | ||
Pb1 | 0.33333 | 0.66667 | 0.00710 (10) | 0.0137 (1)* | |
Pb2 | 0.25517 (5) | 0.01245 (7) | 0.25000 | 0.0142 (1)* | |
V | 0.4096 (2) | 0.3838 (2) | 0.25000 | 0.0061 (6)* | |
Cl | 0.00000 | 0.00000 | 0.00000 | 0.0125 (8)* | |
O1 | 0.3321 (9) | 0.4985 (8) | 0.25000 | 0.020 (3)* | |
O2 | 0.5987 (8) | 0.4839 (8) | 0.25000 | 0.008 (2)* | |
O3 | 0.3567 (6) | 0.2690 (6) | 0.0633 (6) | 0.0136 (17)* |
Pb1—O1 | 2.485 (6) | Pb2—O3 | 2.687 (5) |
Pb1—O2i | 2.751 (9) | Pb2—Clix | 3.1608 (5) |
Pb1—O1ii | 2.485 (7) | Pb2—O2x | 2.351 (10) |
Pb1—O2iii | 2.751 (6) | Pb2—O3xi | 2.556 (5) |
Pb1—O1iv | 2.485 (9) | Pb2—O3xii | 2.556 (5) |
Pb1—O2v | 2.751 (7) | Pb2—O3xiii | 2.687 (5) |
Pb1—O3vi | 2.971 (7) | V—O1 | 1.729 (9) |
Pb1—O3vii | 2.971 (7) | V—O2 | 1.692 (9) |
Pb1—O3viii | 2.971 (6) | V—O3 | 1.714 (5) |
Pb2—Cl | 3.1608 (5) | V—O3xiii | 1.714 (5) |
O1—Pb1—O2i | 126.7 (2) | Clix—Pb2—O2x | 139.71 (11) |
O1—Pb1—O1ii | 74.2 (3) | Clix—Pb2—O3xi | 71.01 (16) |
O1—Pb1—O2iii | 90.67 (19) | Clix—Pb2—O3xii | 136.11 (17) |
O1—Pb1—O1iv | 74.2 (3) | Clix—Pb2—O3xiii | 69.51 (14) |
O1—Pb1—O2v | 150.4 (3) | O2x—Pb2—O3xi | 84.18 (19) |
O1—Pb1—O3vi | 84.8 (2) | O2x—Pb2—O3xii | 84.18 (19) |
O1—Pb1—O3vii | 142.77 (19) | O2x—Pb2—O3xiii | 76.3 (3) |
O1—Pb1—O3viii | 70.7 (2) | O3xi—Pb2—O3xii | 128.4 (2) |
O1ii—Pb1—O2i | 150.4 (3) | O3xi—Pb2—O3xiii | 82.31 (18) |
O2i—Pb1—O2iii | 78.1 (2) | O3xii—Pb2—O3xiii | 141.74 (19) |
O1iv—Pb1—O2i | 90.7 (3) | O1—V—O2 | 111.7 (4) |
O2i—Pb1—O2v | 78.1 (2) | O1—V—O3 | 112.2 (3) |
O2i—Pb1—O3vi | 126.3 (2) | O1—V—O3xiii | 112.2 (3) |
O2i—Pb1—O3vii | 66.0 (2) | O2—V—O3 | 107.1 (3) |
O2i—Pb1—O3viii | 57.05 (19) | O2—V—O3xiii | 107.1 (3) |
O1ii—Pb1—O2iii | 126.7 (3) | O3—V—O3xiii | 106.3 (3) |
O1ii—Pb1—O1iv | 74.2 (3) | Pb2—Cl—Pb2i | 90.36 (2) |
O1ii—Pb1—O2v | 90.7 (2) | Pb2—Cl—Pb2xiv | 89.64 (2) |
O1ii—Pb1—O3vi | 70.7 (2) | Pb2—Cl—Pb2xv | 180.00 |
O1ii—Pb1—O3vii | 84.8 (3) | Pb2—Cl—Pb2xvi | 89.64 (2) |
O1ii—Pb1—O3viii | 142.8 (2) | Pb2—Cl—Pb2xvii | 90.36 (2) |
O1iv—Pb1—O2iii | 150.4 (2) | Pb2i—Cl—Pb2xiv | 90.36 (2) |
O2iii—Pb1—O2v | 78.1 (2) | Pb2i—Cl—Pb2xv | 89.64 (2) |
O2iii—Pb1—O3vi | 57.1 (2) | Pb2i—Cl—Pb2xvi | 180.00 |
O2iii—Pb1—O3vii | 126.31 (15) | Pb2i—Cl—Pb2xvii | 89.64 (2) |
O2iii—Pb1—O3viii | 66.0 (2) | Pb2xiv—Cl—Pb2xv | 90.36 (2) |
O1iv—Pb1—O2v | 126.7 (3) | Pb2xiv—Cl—Pb2xvi | 89.64 (2) |
O1iv—Pb1—O3vi | 142.8 (2) | Pb2xiv—Cl—Pb2xvii | 180.00 |
O1iv—Pb1—O3vii | 70.7 (2) | Pb2xv—Cl—Pb2xvi | 90.36 (2) |
O1iv—Pb1—O3viii | 84.8 (2) | Pb2xv—Cl—Pb2xvii | 89.64 (2) |
O2v—Pb1—O3vi | 66.0 (2) | Pb2xvi—Cl—Pb2xvii | 90.36 (2) |
O2v—Pb1—O3vii | 57.1 (2) | Pb1—O1—V | 129.5 (3) |
O2v—Pb1—O3viii | 126.31 (17) | Pb1—O1—Pb1xviii | 91.8 (3) |
O3vi—Pb1—O3vii | 117.04 (17) | Pb1xviii—O1—V | 129.5 (3) |
O3vi—Pb1—O3viii | 117.04 (19) | Pb1xix—O2—V | 101.4 (2) |
O3vii—Pb1—O3viii | 117.0 (2) | Pb2xx—O2—V | 129.0 (5) |
Cl—Pb2—O3 | 69.51 (14) | Pb1vi—O2—V | 101.4 (2) |
Cl—Pb2—Clix | 71.04 (1) | Pb1xix—O2—Pb2xx | 114.8 (2) |
Cl—Pb2—O2x | 139.71 (11) | Pb1xix—O2—Pb1vi | 86.7 (2) |
Cl—Pb2—O3xi | 136.11 (17) | Pb1vi—O2—Pb2xx | 114.8 (2) |
Cl—Pb2—O3xii | 71.01 (16) | Pb2—O3—V | 96.1 (2) |
Cl—Pb2—O3xiii | 104.06 (14) | Pb2—O3—Pb2i | 117.6 (2) |
Clix—Pb2—O3 | 104.06 (14) | Pb1vi—O3—Pb2 | 98.9 (2) |
O2x—Pb2—O3 | 76.3 (3) | Pb2i—O3—V | 137.5 (3) |
O3—Pb2—O3xi | 141.74 (19) | Pb1vi—O3—V | 92.8 (3) |
O3—Pb2—O3xii | 82.31 (18) | Pb1vi—O3—Pb2i | 105.68 (17) |
O3—Pb2—O3xiii | 61.38 (14) | ||
Cl—Pb2—O3—V | 122.5 (3) | O3—V—O1—Pb1 | −51.7 (6) |
O3xi—Pb2—O3—V | −17.7 (5) | O1—V—O3—Pb2 | −126.6 (3) |
O3xii—Pb2—O3—V | −164.9 (3) | O2—V—O3—Pb2 | 110.5 (3) |
O3xiii—Pb2—O3—V | 2.6 (2) | O3xiii—V—O3—Pb2 | −3.7 (4) |
O3—Pb2—O3xiii—V | −2.6 (2) | O3—V—O3xiii—Pb2 | 3.7 (4) |
O2—V—O1—Pb1 | 68.5 (4) |
Symmetry codes: (i) x−y, x, z−1/2; (ii) −y+1, x−y+1, z; (iii) −x+1, −y+1, z−1/2; (iv) −x+y, −x+1, z; (v) y, −x+y+1, z−1/2; (vi) −x+1, −y+1, −z; (vii) y, −x+y+1, −z; (viii) x−y, x, −z; (ix) x−y, x, z+1/2; (x) −y+1, x−y, z; (xi) y, −x+y, z+1/2; (xii) y, −x+y, −z; (xiii) x, y, −z+1/2; (xiv) −y, x−y, z; (xv) −x, −y, z−1/2; (xvi) −x+y, −x, z; (xvii) y, −x+y, z−1/2; (xviii) −x+y, −x+1, −z+1/2; (xix) x−y+1, x, z+1/2; (xx) −x+y+1, −x+1, z. |
Acknowledgements
We thank the two anonymous reviewers and the Co-editor, A. F. Craievich, for useful comments that helped to improve this manuscript. R. Marr is thanked for his help with the electron probe. The HRPXRD data were collected at the X-ray Operations and Research beamline 11-BM, Advanced Photon Source, Argonne National Laboratory, USA. Use of the Advanced Photon Source was supported by the US Department. of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
Funding information
Funding for this research was provided by: Natural Sciences and Engineering Research Council of Canada (grant to SMA).
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