Chloroxiphite Pb3cuo2(OH)2Cl2: Structure Refinement and Description in Terms of Oxocentred Opb4 Tetrahedra

Mineralogical Magazine, June 2008, Vol. 72(3), pp. 793–798

Chloroxiphite Pb3CuO2(OH)2Cl2: structure refinement and description in terms of oxocentred OPb4 tetrahedra

1, 1 2 3 O. I. SIIDRA *, S. V. KRIVOVICHEV ,R.W.TURNER AND M. S. RUMSEY 1 Department ofCrystallography, Geological Faculty, Saint-Petersburg State University, University emb. 7/9, St. Petersburg, 199034, Russia 2 The Drey, Allington Track, Allington, Salisbury SP4 0DD, Wiltshire, UK 3 Department ofMineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK [Received 6 June 2008; Accepted 9 September 2008]

ABSTRACT

The crystal structure ofchloroxiphite, Pb 3CuO2(OH)2Cl2, from Merehead Quarry (monoclinic, P21/m, a = 6.6972(8), b = 5.7538(5), c = 10.4686(14) A˚ , b = 97.747(10)º, V = 399.72(8) A˚ 3) has been refined to R1 = 0.041. The structure contains three symmetrically unique Pb sites and one Cu site. The strong distortion ofthe Pb 2+ coordination polyhedra is due to the stereoactivity ofthe s2 lone electron pairs on 2+ À the Pb cations. The Cu-site is coordinated by four OH groups to form an almost planar Cu(OH)4 À square that is complemented by two apical Cl anions, forming an elongated [Cu(OH)4Cl2] octahedron. Because ofthe large size and variability ofcoordination polyhedra around Pb 2+ cations and the strength ofthe MeÀO bonds in comparison to the MeÀCl bonds (Me = metal), it is convenient to describe the structure ofchloroxiphite in terms ofoxocentred OPb 4 tetrahedra. The O1 atom is tetrahedrally 2+ coordinated by four Pb cations forming relatively short and strong OÀPb bonds. The OPb4 tetrahedra 2+ link together via common edges to form [O2Pb3] double chains. The difference between chloroxiphite and other natural oxyhalides is the presence ofCu 2+ cations which form an independent structural unit that links to units formed by OPb4 tetrahedra. In this sense, chloroxiphite can be considered as a modular structure consisting ofboth strong cation- and anion-centred units.

KEYWORDS: lead oxyhalides, chloroxiphite, crystal structure, oxocentred tetrahedra, Merehead, UK.

Introduction Filatov (1993) in the products offumarolic LEAD oxy- and hydroxyhalides are common activity ofthe great Tolbachik fissure eruption minerals in alteration zones ofPb-containing (1975À1976, Kamchatka Peninsula, Russia). The sulphide deposits, where they form as a result of crystal structure ofchloroxiphite was solved by hydrolysis ofPb 2+ ions by aqueous chloride Finney et al. (1977) and refined to 11.5% without during oxidation ofPb sulphide minerals. anisotropic refinement ofthe displacement para- Chloroxiphite, Pb3CuO2(OH)2Cl2,wasfirst meters ofatoms. The structure was described as described by Spencer and Mountain (1923) from Pb6 clusters offace-sharingPb tetrahedra and Cu- the Mendip Hills, Somerset, England. It occurs centred hydroxide chloride polyhedra. here as olive-green bladed crystals embedded Here, we report results ofthe structure entirely in mendipite (Turner, 2006). Later, refinement ofchloroxiphite and describe its chloroxiphite was identified by Vergasova and structure in terms ofoxocentred tetrahedra, thus considering this structure type within the framework ofthe structural chemistry ofanion-centred tetrahedra (Krivovichev et al., 1998a; * E-mail: [email protected] Krivovichev and Filatov, 2001; Siidra et al. DOI: 10.1180/minmag.2008.072.3.793 2008a,b).

# 2008 The Mineralogical Society O. I. SIIDRA ET AL.

Experiment TABLE 1. Crystallographic data and refinement parameters for chloroxiphite. The sample used in this study was from the Natural History Museum, London, and was ˚ collected in situ at the Merehead Quarry, a (A) 6.6972 (8) b (A˚ ) 5.7538 (5) Somerset, England, in the late 1970s by Dr Bob c (A˚ ) 10.4686 (14) Symes and the late Dr Alan Criddle. The specimen b (o) 97.747 (10) appears to originate from the #1 vein and is V (A˚ 3) 399.72 (8) typical, consisting ofsmall bladed crystals of Radiation Mo-Ka chloroxiphite embedded entirely in mendipite Total reflections 3803 which in turn fills a calcite-lined cavity in a Unique reflections 1174 manganese-oxide matrix. This paragenesis was Unique [Fo] 5 4sF 1021 described previously (Symes and Embrey, 1977; GooF 1.212 Turner, 2006). Space group P21/m F 682 The crystal ofchloroxiphite selected fordata ooo Z 2 collection was mounted on a Stoe IPDS II Image- Crystal size (mm) 0.0560.0760.10 Plate-based X-ray diffractometer operated at m,cmÀ1 66.230 50 kV and 40 mA. More than a hemisphere of Maximum 2y(º) 58.5 three-dimensional data was collected using R1 0.0412 monochromatic Mo-Ka X-radiation, with frame wR2 0.0502 widths of2º in o, and a counting time of180 s for S 1.212 each frame. The unit-cell parameters (Table 1) were refined using least-squares techniques. The Note: R1 = S||Fo| À |Fc||/S|Fo|; unit-cell parameters are in good agreement with 2 2 2 2 2 1/2 wR2 ={S[w(Fo À Fc) ]/S[w(Fo) ]} ; 2 2 2 2 2 those reported by Finney et al. (1977). The w = 1/[s (Fo) + (aP) + bP], where P = (Fo +2Fc)/3; 2 2 1/2 intensity data were integrated and corrected for S ={S[w(Fo À Fc)]/(n À p)} where n is the number of Lorentz polarization and background effects using reflections and p is the number ofrefined parameters. the Stoe program X-area. Systematic absences of reflections indicate space group P21/m, also in agreement with the results obtained by Finney et the structure factors. The final refinement al. The atomic coordinates provided by these converged to an agreement index (R1) of0.041, authors were successfully refined on the basis of calculated for the 1021 unique reflections with 2 F for all unique data in this space group. The |Fo|=4sF. The final atom coordinates and SHELXL program package was used for all anisotropic-displacement parameters are given in structural calculations (Sheldrick, 1997). The Table 2, selected interatomic distances are shown final model included all atomic positional in Table 3. The list ofobserved and calculated parameters, anisotropic-displacement parameters structure factors can be provided by the authors for Pb, Cl, O and a refinable weighting scheme of upon request.

TABLE 3. Selected bond lengths (A˚ ) in the structure ofchloroxiphite.

Pb(1)ÀO(1) 2.378(6)62 Pb(3)ÀO(1) 2.242(7)62 Pb(1)ÀO(1) 2.427(6)62 Pb(3)ÀOH(2) 2.598(10) Pb(1)ÀCl(1) 3.3346(19)62 Pb(3)ÀCl(1) 3.023(3) Pb(1)ÀCl(1) 3.426(3) Pb(3)ÀCl(2) 3.474(4) Pb(3)ÀCl(2) 3.475(3)62 Pb(2)ÀO(1) 2.237(7)62 Pb(2)ÀOH(3) 2.516(9) Cu(1)ÀOH(3) 1.983(6)62 Pb(2)ÀCl(1) 3.085(3) Cu(1)ÀOH(2) 1.994(6)62 Pb(2)ÀCl(1) 3.460(2)62 Cu(1)ÀCl(2) 2.948(4)62 Pb(2)ÀCl(2) 3.486(4)

794 CRYSTAL STRUCTURE OF CHLOROXIPHITE

Results

12 Cation coordination U 0.001(2) 0.0034(6) The structure ofchloroxiphite contains three À À symmetrically unique Pb sites and one Cu site. The Pb1 cation is coordinated by four O1 atoms and three Cl1 atoms (Fig. 1a). The Pb2 cation is 13

U coordinated by the two O1 atoms, one O2 atom, three Cl1 and one Cl2 atoms. The Pb3 cation is 0.003(3) 0 0.0017(12) 0 0.00052(17) 0 0.0051(6) À À À À coordinated by the one O2 atom, two O1 atoms, three Cl2 and one Cl1 atoms. In accord with previous results on Pb oxyhalides, the general

23 feature of the Pb2+ coordination in chloroxiphite U is the presence ofseveral short Pb ÀOand PbÀOH bonds (2.24À2.60 A˚ ) located in one coordination hemisphere ofthe Pb 2+ cations. In the opposite hemisphere, the Pb2+ cations form

33 from three or four long PbÀCl bonds. The strong U distortion ofthe Pb 2+ coordination polyhedra is due to the stereoactivity of s2 lone electron pairs on the Pb2+ cations, and is in good agreement with general observations for structures containing ) ofatoms in chloroxiphite. ˚

22 cations with lone electron pairs (Brown, 1974). U Bond valences were calculated using the parameters ofKrivovichev and Brown (2001) forthe Pb2+ÀO bonds and Brese and O’Keeffe (1991) for the other bonds. Bond-valence sums for the Pb atoms range from 1.90 to 1.94 valence units (v.u.), 11

U whereas the bond-valence sum at the Cu site is 1.84 v.u. The bond-valence sums at the O1, O2, O3, Cl1 and Cll2 sites are 1.95, 1.11, 1.18, 0.96 and 0.47 v.u., in agreement with the assignment of these sites to O2À,OHÀ and ClÀ anions. The eq bond-valence sum at the Cl2 site is notably smaller than the expected value of1 v.u. The Cu site is coordinated by four OHÀ groups to form an almost planar Cu(OH)4 square that is complemented by two apical ClÀ anions. As a

2. Coordinates and displacement parameters (A result, an elongated [Cu(OH)4Cl2] octahedron is formed (Fig. 1b). This type ofcoordination is 2+ ABLE typical ofmixed-ligand Cu coordination poly- T hedra (Burns and Hawthorne, 1995a) and has been observed, for example, in allochalcoselite (Krivovichev et al., 2006), georgbokiite (Krivovichev et al., 1999) and chloromenite (Krivovichev et al., 1998b). The [Cu(OH)4Cl2] octahedra are distorted owing to the Jahn-Teller effect (Jahn and Teller, 1937; Burns and

xyzU Hawthorne, 1995a,b).

Description of the structure Because ofthe large size and variability of 2+ OH2OH3 0.9213(15) 1.1680(15) Ü Ü 0.3710(8) 0.5897(8) 0.0134(19) 0.0112(18) 0.012(5) 0.013(5) 0.013(5) 0.004(4) 0.014(4) 0.015(4) 0 0 0.001(4) 0 Cl2O1 0.6834(7) 0.6125(10) Ü 0.0016(11) 1.1311(6) 0.0123(14) 0.6147(4) 0.012(3) 0.0274(8) 0.007(3) 0.0197(18) 0.038(2) 0.018(3) 0.0238(17) 0.002(2) 0 0.001(3) 0.0012(14) 0 Cl1 0.1308(5) Ü 1.1205(3) 0.0170(7) 0.0156(16) 0.0162(15) 0.0180(14) 0 Pb3Cu1 0.53955(8) 1 Ü 0 1.28320(4) 0.01272(16) 0.0132(3) Ý 0.0120(2) 0.0128(2) 0 0.0151(4) 0.0185(9) 0.0107(7) 0.00098(17) 0 0.0141(7) 0.0017(6) Atom Pb1Pb2 0.65691(7) 1.13269(8) Ü Ü 0.94966(4) 0.82594(4) 0.01154(15) 0.01198(16) 0.0089(3) 0.0102(3) 0.0097(2)coordination 0.0114(2) 0.0160(2) 0.0138(2) 0 0 polyhedra 0.00163(18)around 0 Pb cations and

795 O. I. SIIDRA ET AL.

2+ 2+ FIG. 1. Coordination of( a)Pb ; and (b)Cu cations in the structure ofchloroxiphite.

the strength ofthe MeÀO bonds in comparison to bonds. From the viewpoint ofbond-valence the MeÀCl bonds, it is convenient to describe the theory, these bonds are the strongest in the structure ofchloroxiphite (Fig. 2) in terms of structure and thus it makes absolute sense to 2À oxocentred OPb4 tetrahedra. The structure consider the O anions as centres ofoxocentred 2À contains three O anions. The O2 and O3 OPb4 tetrahedra. The mean OÀPb length in the ˚ anions are OH groups and their bond-valence O1Pb4 tetrahedron is 2.32 A which is typical for requirements are strongly-inﬂuenced by the such units (Krivovichev et al., 1998a), whereas formation of the hydrogen (O_H) bonds. The the individual values vary in the range O1 atom is tetrahedrally coordinated by four Pb2+ 2.23À2.42 A˚ . The mean Pb···Pb distance for ˚ cations, forming relatively short and strong OÀPb OPb4 tetrahedra in chloroxiphite is 3.78 A, close

FIG. 2. The crystal structure ofchloroxiphite projected along the b axis. Only the PbÀO, PbÀOH and CuÀOH bonds are shown.

796 CRYSTAL STRUCTURE OF CHLOROXIPHITE

perpendicular orientations and are linked through weak PbÀCl bonds only. In contrast, in damar- 2+ aite, the [O2Pb3] chains are linked through OH groups to form [Pb3O2](OH) sheets. As is common in structures containing PbÀO/OH clusters, OH groups in damaraite form two short (OH)ÀPb bonds that result in (OH)Pb2 dimers. In the structures ofPb 7O4(OH)4X2 (X = Cl, Br) (Krivovichev and Burns, 2002; Siidra et al., 2+ 2007), the [O2Pb3] chains are linked by the (OH)Pb2 dimers into a 3-dimensional framework, 2+ À FIG. 3. Structure of[O 2Pb3] chains in the crystal that hosts Cl anions. structure ofchloroxiphite. Chloroxiphite differs from other natural oxyhalides in the presence ofCu 2+ cations that form an independent structural unit. In this sense, chlor- to the typical value of3.74 A ˚ given by oxiphite can be considered as a modular structure Krivovichev and Filatov (1999). consisting ofboth strongly bonded cation- and The OPb4 tetrahedra link together via common anion-centred units. Another such structure is 2+ edges to form [O2Pb3] double chains (Fig. 3). In philolithite, [Pb2O]6[Mn(Mg,Mn)2(Mn,Mg)4 this unit, each tetrahedron shares three ofsix (OH)12(SO4)(CO3)4]Cl4 (Moore et al., 2000), 2+ edges with adjacent tetrahedra. The [O2Pb3] that consists ofa complex frameworkofMn- double chains extend along the b axis. The Pb-Pb and Mg-centred octahedra, SO4 and CO3 groups shared edges are shorter than the non-shared ones. that host chains oftrans-edge-sharing OPb 4 Parallel to the chains ofoxocentred tetrahedra are tetrahedra. According to Kampf et al. (1998), 2À [Cu(OH)2Cl2] single chains (Fig. 4) formed by philolithite occurs as crust-like overgrowths and face-sharing Cu(OH)2Cl2 octahedra. The simple tetragonal tablets in a matrix ofcalcite- 2À 2+ [Cu(OH)2Cl2] and [O2Pb3] chains are rich Mn oxide from the La˚ngban Fe-Mn mineral connected via PbÀOH bonds to form layers deposit. The La˚ngban mine has many geochem- parallel to (1¯01) which are connected through ical and mineralogical similarities to the Mendip PbÀCl bonds only. manganese deposits that explain structural and chemical relations between chloroxiphite, philolithite and other Pb oxyhalide species (e.g. Turner, Discussion 2006). The structure ofchloroxiphite is an example ofa The combination ofPb-oxyhalide and transi- 2+ Pb oxyhalide based on [O2Pb3] chains (Siidra tion-metal chemistries (Cu, Zn, Mn, Fe, etc.) may and Krivovichev, 2008) built from the OPb4 be a productive pathway to the synthesis ofnew oxocentred tetrahedra. These chains have been compounds that combine properties and char- observed previously in crystal structures of acteristics ofboth. It is also possible that natural and synthetic lead oxyhalide compounds chloroxiphite and philolithite are not the only (Siidra et al., 2008a). In mendipite (Krivovichev mineral species with such architecture and that and Burns, 2001; Siidra et al., 2008b), the chains other minerals ofthis kind will be discovered. extend along the b axis. They have two mutually Acknowledgements We are grateful to F.C. Hawthorne, M. Pasero and M.D. Welch for helpful comments on the manuscript. We acknowledge the ﬁnancial support ofthe DFG (DE 412/34-1), the Ministry ofScience and Education (grant #RNP 2.1.1.3077), RFBR-DFG (07-05-91557) and also the Federal Agency on Education (SPbSU innovation education project ‘Innovational 2À FIG. 4. Structure of[Cu(OH) 2Cl2] chains in the crystal Educational Environment in the Classic structure ofchloroxiphite. University’) for their instrumental support.

797 O. I. SIIDRA ET AL.

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