See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/240613232

The crystal structure and chemistry of mereheadite

Article  in  Mineralogical Magazine · January 2009

DOI: 10.1180/minmag.2009.073.1.75

CITATIONS READS

11 72

5 authors, including:

Sergey V Krivovichev R.W. Turner

Saint Petersburg State University Imbuia Holdings
642 PUBLICATIONS   7,196 CITATIONS    30 PUBLICATIONS   146 CITATIONS   

SEE PROFILE SEE PROFILE

Michael Rumsey Oleg I Siidra

Natural History Museum, London Saint Petersburg State University
104 PUBLICATIONS   313 CITATIONS    170 PUBLICATIONS   1,044 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Special Issue "Mathematical Crystallography 2019" View project

PhD2000 View project

All content following this page was uploaded by Oleg I Siidra on 27 May 2014.

The user has requested enhancement of the downloaded file.

Mineralogical Magazine, February 2009, Vol. 73(1), pp. 75–89

The crystal structure and chemistry of mereheadite

S. V. KRIVOVICHEV1,2,*, R. TURNER3, M. RUMSEY4, O. I. SIIDRA1 AND C. A. KIRK5
1
Department of Crystallography, Geological faculty, Saint-Petersburg State University, University Emb. 7/9,
St. Petersburg, 199034, Russia
2
Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 6, St. Petersburg, 199034, Russia
3
The Drey, Allington Track, Allington, Salisbury SP4 0DD, UK
4
Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
5
Department of Chemistry, Loughborough University, Leicestershire, LE11 3TU, UK
[Received 11 December 2008; Accepted 25 March 2009]

ABSTR ACT

The crystal structure of mereheadite (monoclinic, Cm, a = 17.372(1), b = 27.9419(19), c = 10.6661(6) Å,
b = 93.152(5)o, V = 5169.6(5) Å3) has been solved by direct methods and refined to R1 = 0.058 for 6279
unique observed reflections. The structure consists of alternating Pb
O/OH blocks and Pb
Cl sheets
oriented parallel to the (201) plane and belongs to the 1:1 type of lead oxide halides with PbO blocks. It
contains 30 symmetrically independent Pb positions, 28 of which belong to the PbO blocks, whilst two
positions (Pb12 and Pb16) are located within the tetragonal sheets of the Cl
anions. Mereheadite is thus
the first naturally occurring lead oxychloride mineral with inter-layer Pb ions. The coordination
configurations of the Pb atoms of the PbO blocks are distorted versions of the square antiprism. In one
half of the coordination hemisphere, they are coordinated by hard O2
and OH
anions whose number
varies from three to four, where as the other coordination hemisphere invariably consists of four soft Cl

anions located at the vertices of a distorted square. The Pb12 and Pb16 atoms in between the PbO blocks
have an almost planar square coordination of four Cl
anions. These PbCl4 squares are complemented by
triangular TO3 groups (T = B, C) so that a sevenfold coordination is achieved. The Pb
O/OH block in
mereheadite can be obtained from the ideal PbO block by the following list of procedures: (a) removal of
some PbO4 groups that results in formation of square-shaped vacancies; (b) insertion of TO3 groups into
these vacancies; (c) removal of some Pb atoms (that correspond to the Pb1A and Pb2A sites), thus
transforming coordination of associated O sites from tetrahedral OPb4 to triangular OHPb3;
(d) replacement of two O2
anions by one OH
anion with twofold coordination; this results in
formation of the 162 elongated rectangular vacancy. The structural formula that can be derived on the
basis of the results of single-crystal structure determination is Pb47O24(OH)13Cl25(BO3)2(CO3). Welch et
al. (1998) proposed the formula Pb2O(OH)Cl for mereheadite, which assumes that neither borate or
carbonate are essential constituents of mereheadite and their presence in the mineral is due to disordered
replacements of Cl
anions. However, our study demonstrates that this is not the case, as BO3 and CO3
groups have well-defined structural positions confined in the vacancies of the Pb
O/OH blocks and are
therefore essential constituents. Our results also show that mereheadite is not a polymorph of blixite, but
is in fact related to symesite. Symesite thus becomes the baseline member of a group of structurally
related minerals.

K EY WORDS : mereheadite; crystal structure; lead oxychlorides; borate; carbonate; Merehead, Mendips,
symesite.

Introduction
MINERALS and inorganic compounds with PbO-
derivative blocks are important phases that occur
* E-mail: skrivovi@mail.ru under a variety of natural and technological
DOI: 10.1180/minmag.2009.073.1.75 conditions. They are found as secondary minerals

# 2009 The Mineralogical Society

 S. V. KRIVOVICHEV ET AL.

in the oxidation zones of mineral deposits, the
species including: kombatite Pb14(VO4)2O9Cl4
(Cooper and Hawthorne, 1994), sahlinite
Pb 14 (AsO 4 ) 2 O 9 Cl 4 (Bonaccorsi and Pasero,
2003), asisite Pb7SiO8Cl2 (Rouse et al. 1988;
Welch, 2004), pinalite Pb3WO5Cl2 (Grice and
Dunn, 2000), parkinsonite Pb7MoO9Cl2 (Symes et
al. 1994; Welch et al 1996), mendipite Pb3O2Cl2
(Spencer and Mountain, 1923), damaraite
Pb3O2Cl(OH) Criddle et al., (1990), sidpietersite
Pb4(SO3S)O2(OH)2 (Cooper and Hawthorne,
1999), symesite Pb10(SO4)O7Cl4(H2O) (Welch et
al., 2000), blixite Pb8O5(OH)4Cl2 (Gabrielson et
al. 1960), schwartzembergite Pb 5 IO 6 H 2 Cl 3
(Welch et al., 2001) and seeligerite Pb3IO4Cl3
(Bindi et al., 2008). Several of these minerals are
known to occur with mereheadite (kombatite,
parkinsonite, mendipite, and symesite).
The phases Pb4O2(OH)2(SO4) and Pb5O4(SO4)
form during production of lead-acid batteries
(Steele et al., 1997; Steele and Pluth, 1998).
Post and Buseck (1985) identified mendipite-
related compounds Pb3O2X2 (X = Br, Cl) in
automobile exhaust gases. The latter phases have
also been found on the pistons of failed aircraft
engines and are considered to be responsible for
engine failure (Noren et al., 2002).
Lead oxychlorides with layered PbO-derived
blocks were first described as synthetic
compounds by Aurivillius (1982, 1983).
Structural investigations revealed that these
phases consist of PbO-like blocks alternating
with sheets of halide ions, X
(Fig. 1). In the
PbO-related Aurivillius phases, the stacking
sequence of sheets is: _XPbOPbOXPbOPbO_,
i.e. the (PbO):X ratio is 2:1. The 2:1 structure has
also been observed in minerals such as asisite
(Rouse et al., 1988) and parkinsonite (Symes et
al., 1994). Another possible stacking sequence is
1:1 (_ XPbOXPbOX_) with simple alternation
of the PbO blocks and X sheets, which has been
found in kombatite, sahlinite, symesite, schwart-
zembergite, and blixite.
In an ideal 1:1 structure, Pb atoms are
coordinated by four O atoms in one coordination
hemisphere and four X atoms in another. The
PbO 4 X 4 polyhedron is a square antiprism
(Fig. 2a). The X atoms have a cubic coordination
(Fig. 2b), whereas O atoms have fourfold
coordination, thus being central in the oxocentred

FIG. 1. The schematic illustration of structural architecture of 2:1 lead oxyhalides containing PbO blocks and
tetragonal X sheets of halide ions (X = Cl, Br, I). See text for details.

76
 STRUCTURE AND CHEMISTRY OF MEREHEADITE
FIG. 2. Coordination of Pb (a), X (b) and (c) O atoms in the structure of an ideal 1:1 lead oxyhalide with PbO blocks.
OPb4 tetrahedra (Fig. 2c). These tetrahedra are
important structural units in a number of lead
oxysalts (Siidra et al., 2008a) and particularly in
n a t u r a l an d sy n t h e t i c le a d o x y h a l i d e s
(Krivovichev and Burns, 2001, 2002; Siidra and
Krivovichev, 2008; Siidra et al., 2008b).
Since PbO blocks are electroneutral and X
sheets are negatively charged, the structure
requires a charge-balance mechanism to compen-
sate for the negative charge of the X sheets. This
may be achieved in three different ways:
1) Substitution of PbOn groups in the PbO
blocks by strongly-bonded MOm polyhedra,
where M = S (symesite), Mo (parkinsonite), V
(kombatite), As (sahlinite), I (schwartzembergite)
or Si (asisite) (Fig. 3a). The substitution may be
either ordered (symesite, kombatite and sahlinite)
or averaged (parkinsonite, asisite and all synthetic
phases reported by Aurivillius (1982, 1983)). In
ordered structures, vacancies in the PbO blocks
(Fig. 3b) have the form of a square (symesite:
Fig. 3c), or a double square (kombatite and
sahlinite: Fig. 3d). In the case of average
structures determined by X-ray diffraction, super-
structures have been observed by electron
diffraction (Welch et al., 1996, 2001; Welch,
2004), indicating that the substituent cation is
highly ordered within the PbO sheet. Hence, all
PbO-based lead-oxychloride sheet minerals have
ordered superstructures (Welch et al., 1996, 2001;
Welch, 2004).
2) By O2
$ OH
substitution in the PbO
blocks. This mechanism is realised in the structure
of blixite, Pb8O5(OH)2Cl4 (Krivovichev and
Burns, 2006), where three O2
anions are
replaced by two OH
anions. The vacancies in
the PbO block have the form of an elongated
rectangle (Fig. 3e).
3) Insertion of Pb atoms into the X sheet.
Fig. 3f shows that the Pb atom can be inserted
into the centre of a square formed by four X
atoms. In this case, the Pb atom forms four Pb
X
77
bonds in the X sheet, thus adopting square-planar
coordination. This structural mechanism was first
reported by Krivovichev et al. (2006) for the
synthetic compound Pb31O22Br10Cl8. As we
demonstrate in this paper, this structural feature
also occurs in mereheadite, which is the first lead
oxychloride mineral containing inter-layer Pb
ions. Note that the insertion of the Pb atom into
the X sheet is associated with formation of the
square-shaped vacancy in the PbO blocks above
and below the inserted Pb atom.
The aim of this paper is to report the structure
of mereheadite, which is shown to be another Pb
oxychloride based upon PbO blocks, and the
chemical formula resulting from this structure.
Mereheadite was first described by Welch et al.
(1998) as a new mineral from Merehead Quarry,
near Cranmore, Somerset, England, that was
formed as a result of the interaction of brines
with primary sulphides (Symes and Embrey,
1977). Turner (2006) showed that the formation
mechanism was more complex, involving the co-
precipitation of manganates from seawater and a
subsequent hydrothermal event which heated the
deposits to over 500ºC, forming sealed, internally-
buffered chemical micro-environments and initi-
ating a complicated sequence of secondary
mineralization within them. Mereheadite and
other oxychlorides are formed during the final
stages of secondary mineralization.
The empirical formula of mereheadite was
given by Welch et al. (1998) as
Pb8O4.19(BO3)0.51(CO3)0.62(OH)0.76Cl4.09 and the
ideal formula as Pb2O(OH)Cl. The mineral was
described as monoclinic, C2/c, a = 5.680(2) Å,
b = 5.565(3) Å, c = 13.143(9) Å, b = 90.64(4)º
and V = 415.4(8) Å3. Welch et al. (1998) also
noted that the structure of the mineral had been
determined and that it contained PbO blocks
which alternate along the c axis with layers of
Cl
anions. Although in this structural model
there are no positions for (BO3) and (CO3) groups,
 S. V. KRIVOVICHEV ET AL.

FIG. 3. Formation of vacancies in the PbO block due to removal of Pb and O atoms (a); the PbO block shown as an
array of oxocentered OPb4 tetrahedra (b); defect PbO blocks in the structures of symesite (c); kombatite (d); blixite
(e); insertion of additional Pb atoms in the X layer of halide ions (f).

it was suggested that they replace chlorine in
between the PbO blocks, as in bismutite,
Bi 2 O 2 (CO 3 ) and beyerite, CaBi 2 O 2 (CO 3 ) 2
(Lagercrantz and Sillén, 1948; Grice, 2002). The
role of the OH
groups was also unclear. Thus,
the structure model of mereheadite at that time
represented an average substructure, implying
disordered arrangements of borate, carbonate
and hydroxyl groups.
It seems likely that the sample of mereheadite
used by Welch et al. (1998) for their single-
crystal structure study was impure, as mereheadite
usually occurs intimately intergrown with a
number of other species, including cerussite and
mendipite. However, in July 2005 the second
author recovered a number of specimens from a
manganese pod at Merehead Quarry which
contained distinct crystals of mereheadite of

78
 STRUCTURE AND CHEMISTRY OF MEREHEADITE
better quality, and these were used for the
determination of superstructure reported here.
Experimental procedures
Structural studies of layered Pb oxyhalides are
challenging due to a number of factors, including
X-ray absorption by Pb2+ cations with diffuse
electron shells, strong pseudosymmetries, poorly
defined weak superstructure reflections and
twinning problems (Welch et al., 1996, 2001;
Krivovichev and Burns, 2006). Thus, the choice
of crystal for an XRD study is critically
important. In this work, we have used three
crystals of mereheadite extracted from the
material collected in 2005. The results reported
below have been obtained from the best of the
three samples. It was mounted on a Stoe IPDS II
Image-Plate based X-ray diffractometer operated
at 50 kV and 40 mA. More than a hemisphere of
three-dimensional data was collected using
monochromatic Mo-Ka X-radiation, with frame
widths of 2º in o, and with a 300 s count for each
frame. The unit-cell parameters (Table 1) were
refined using least-squares techniques and are in
disagreement with the subcell parameters reported
by Welch et al. (1998) (see above). Subcell
vectors (a’, b’, c’), similar to those reported
previously, can be obtained from the supercell
vectors (a, b, c) through the following transforma-
tions: a’ = (a
2c), b’ = b/5, c’ = (a + 2c)/5. The
subcell parameters calculated from these formulas
are a’ = 5.675 Å, b’ = 5.598 Å, c’ = 13.425 Å, b’ =
101.63º, V’ = 417.7 Å3. It is clear that the a’ and b’
parameters and unit-cell volume agree well with
those reported by Welch et al. (1998), whereas the
c’ parameter and the b’ angle do not. We suggest
that the difference is due to the fact that Welch et
TABLE 1. Crystallographic data and refinement parameters for mereheadite.
a (Å) 17.372(1)
b (Å) 27.9419(19)
c (Å) 10.6661(6)
b (o) 93.152(5)
V (Å3) 5169.6(5)
Radiation Mo-Ka
Total reflections 16893
Unique reflections 8855
Unique [Fo] 5 4sF 6279
R1 = &||Fo|
|Fc||/&|Fo|; wR2 = {&[w(F2o
F2c )2]/&[w(F2o)2]}1/2;
w =1/[&2(F2o)+(aP)2 + bP], where P = (F2o + 2F2c )/3;
S = {&[w(F2o
F2c )]/(n
p)}1/2 where n is the number of reflections and p is the number of refined parameters.
79
al. (1998) studied a crystal of mereheadite
twinned along the (201) plane of the real cell,
which is the (001) plane of the subcell.
Overlapping of the diffraction patterns resulting
from two twin components may lead to the
incorrect determination of the c’ parameter and
the b’ angle. In fact, in one of the crystals studied,
we observed this well defined twinning along the
(201) plane with the ratio of twin components
equal to 1:1.
The measured intensity data were integrated
and corrected for Lorentz, polarization, and
background effects using the Stoe program
X-Area. Systematic absences of reflections
indicated space groups C2/m, C2, or Cm, with
the latter being confirmed by the structure
determination. Absorption correction was done
analytically, taking into account the shape of the
crystal studied. Significant problems occurred
during structure determination due to poorly-
defined superstructure reflections that appeared in
high-angle areas of diffraction space. In parti-
cular, the positions of light atoms, such as B and
C, could not be directly determined due to the
presence of Pb atoms which dominate the X-ray
scattering. The use of diffraction data up to 2y =
50º provided essential improvement of the
refinement and allowed location of the positions
of the B and C atoms. It was not possible to
distinguish between B and C sites using electron
densities because of the background from the 30
independent Pb sites. Consequently, site assign-
ment was carried out on the basis of the
differences in the T
O bond lengths (T = B, C)
and the requirements of electroneutrality of the
whole structure. The structure solution revealed
partial disorder in the positions of Pb atoms

namely slight under-occupation of the Pb12 and
Space group Cm
Z 2
m, mm
1 76.892
Dx, g/cm3 7.236
Crystal size (mm) 0.1060.0960.09
2y max (º) 50.0
R1 0.058
wR2 0.137
S 0.960
 TABLE 2. Atomic coordinates, site-occupation factors (SOFs) and displacement parameters (Å2) for mereheadite.

Atom x y z SOF Ueq U11 U22 U33 U23 U13 U12

Pb1 0.8572(1) 0.89881(7) 0.4134(2) 1 0.0234(6) 0.027(1) 0.021(1) 0.023(1) 0.0024(9) 0.004(1) 0.0027(8)
Pb2 0.1633(2) 0.40752(8)
0.2085(3) 1 0.0246(6) 0.030(1) 0.022(1) 0.023(1)
0.0009(9) 0.002(1)
0.003(1)
Pb3
0.2337(1) 0.20451(9)
0.4239(2) 1 0.0230(6) 0.022(1) 0.021(1) 0.027(1) 0.0002(9) 0.005(1) 0.000(1)
Pb4 0.9556(3) 0 0.1510(4) 1 0.0390(10) 0.057(3) 0.031(2) 0.031(2) 0 0.005(2) 0
Pb5 0.0550(2) 0.3006(9)
0.0108(2) 1 0.0239(6) 0.026(1) 0.022(1) 0.024(1)
0.0024(9) 0.001(1)
0.0013(9)
Pb6
0.0255(1) 0.20338(8)
0.4337(2) 1 0.0245(6) 0.027(1) 0.023(1) 0.023(1) 0.0014(8) 0.002(1) 0.0023(9)
Pb7 0.6842(2) 0.90091(9) 0.1552(3) 1 0.0238(6) 0.022(1) 0.023(1) 0.026(1) 0.0010(9) 0.0005(10)
0.0006(9)
Pb8 0.3728(2) 0.19248(8) 0.4016(2) 1 0.0227(6) 0.024(1) 0.023(1) 0.021(1)
0.0004(9)
0.0007(10)
0.0029(9)
Pb9 0.4755(2) 0.10024(8) 0.1902(3) 1 0.0223(6) 0.020(1) 0.020(1) 0.027(1)
0.0037(9) 0.002(1)
0.0009(9)
Pb10
0.1159(2) 0.09839(8)
0.248(2) 1 0.0235(7) 0.029(2) 0.021(1) 0.020(1) 0.0008(9) 0.0002(12)
0.0021(9)
Pb11 0.2742(2) 0.10202(8)
0.4109(2) 1 0.0221(6) 0.022(1) 0.023(1) 0.021(1)
0.0020(9) 0.002(1)
0.0027(9)
Pb12 0.2895(2) 0 0.2769(3) 0.922(8) 0.0231(9) 0.026(2) 0.025(1) 0.019(2) 0 0.005(1) 0
Pb13
0.1090(2) 0.30524(8)
0.2534(2) 1 0.0215(6) 0.024(1) 0.021(1) 0.019(1)
0.0027(9)
0.002(1) 0.0035(9)
Pb14 0.1815(2) 0 0.7627(4) 1 0.0255(8) 0.024(2) 0.018(1) 0.034(2) 0 0.002(1) 0
Pb15 0.0001(2) 0.39648(8)
0.4400(3) 1 0.0230(6) 0.023(1) 0.022(1) 0.024(1) 0.001(1) 0.0005(10)
0.004(1)
Pb16 0.3694(1) 0.30180(6) 0.0606(2) 0.925(7) 0.0193(6) 0.019(1) 0.020(1) 0.019(1)
0.0001(9) 0.0001(9) 0.0010(8)

80
Pb17 0.0738(2) 0.10482(9)
0.0231(3) 1 0.0280(7) 0.022(1) 0.026(1) 0.036(2)
0.007(1) 0.0005(11)
0.0017(10)
Pb18 0.2055(2) 0.19920(8) 0.1320(2) 1 0.0286(6) 0.025(1) 0.028(1) 0.033(1)
0.006(1)
0.001(1) 0.0007(10)
Pb19 0.7727(2) 0 0.6024(3) 1 0.0196(8) 0.022(2) 0.022(2) 0.015(2) 0 0.002(1) 0
Pb20 0.5871(2) 0.19535(8) 0.3495(3) 1 0.0232(6) 0.019(1) 0.025(1) 0.026(1)
0.000(1)
0.0007(9)
0.001(1)
Pb21
0.2215(2) 0
0.0517(4) 1 0.0233(8) 0.019(2) 0.027(2) 0.024(2) 0
0.0003(14) 0
S. V. KRIVOVICHEV ET AL.

Pb22 0.1636(2) 0.19533(8)
0.2287(3) 1 0.0237(6) 0.023(1) 0.022(1) 0.027(1) 0.0016(9) 0.005(1) 0.0020(9)
Pb23 0.5670(2) 0 0.0102(4) 1 0.0231(8) 0.021(2) 0.024(2) 0.024(2) 0
0.0006(14) 0
Pb24 0.2904(2) 0.10332(9)
0.0690(2) 1 0.0235(6) 0.024(1) 0.025(1) 0.022(1)
0.0030(9) 0.0007(10) 0.0013(9)
Pb25 0.6048(2) 0 0.3585(4) 1 0.0246(9) 0.025(2) 0.027(2) 0.022(2) 0 0.005(1) 0
Pb26 0.3900(2) 0 0.7648(3) 1 0.0210(8) 0.018(2) 0.021(1) 0.024(2) 0 0.005(1) 0
Pb27 0.1006(2) 0.10703(9)
0.6403(3) 1 0.0293(6) 0.035(1) 0.030(1) 0.024(1) 0.001(1) 0.004(1)
0.003(1)
Pb28 0.9868(3) 0 0.5685(4) 1 0.030(1) 0.031(2) 0.029(2) 0.031(2) 0 0.005(2) 0
Cl1 0.172(1) 0.1983(6)
0.549(2) 1 0.034(4) 0.04(1) 0.040(8) 0.019(7) 0.003(6)
0.005(7)
0.023(7)
Cl2
0.020(1) 0.3989(6)
0.122(2) 1 0.042(5) 0.038(10) 0.028(8) 0.061(13)
0.002(7) 0.010(10)
0.006(7)
Cl3 0.359(2) 0 0.041(2) 1 0.033(5) 0.053(16) 0.036(10) 0.009(10) 0
0.010(9) 0
Cl4 0.179(2) 0 0.457(3) 1 0.038(7) 0.040(15) 0.022(11) 0.052(18) 0 0.015(13) 0
Cl5 0.375(1) 0.4014(5) 0.078(2) 1 0.041(5) 0.048(11) 0.026(7) 0.051(10) 0.004(7) 0.020(8)
0.002(7)
Cl6 0.085(1) 0.1032(6)
0.321(2) 1 0.040(5) 0.052(11) 0.024(6) 0.048(10) 0.015(7) 0.021(9) 0.005(7)
Cl7 0.097(1) 0.5
0.303(3) 1 0.035(7) 0.020(12) 0.027(10) 0.061(16) 0 0.028(11) 0
Cl8 0.763(2) 0 0.257(3) 1 0.039(7) 0.045(16) 0.030(10) 0.044(16) 0 0.031(15) 0
Cl9 0.3938(9) 0.1983(4) 0.081(2) 1 0.025(4) 0.009(8) 0.019(6) 0.049(10) 0.003(6) 0.013(7) 0.004(9)
 Cl10 0.977(2) 0 0.858(2) 1 0.032(5) 0.047(14) 0.036(11) 0.012(9) 0
0.010(9) 0
Cl11 0.064(1) 0.3030(4)
0.351(1) 1 0.022(3) 0.037(9) 0.015(6) 0.015(7)
0.001(5)
0.003(6)
0.003(5)
Cl12 0.267(1) 0.1021(5) 0.247(2) 1 0.036(5) 0.050(11) 0.021(7) 0.040(10)
0.011(6) 0.017(9) 0.007(7)
Cl13 0.480(1) 0.3015(6)
0.125(2) 1 0.034(4) 0.042(10) 0.038(8) 0.019(8) 0.001(6)
0.009(7)
0.000(7)
Cl14 0.289(1) 0.2981(5) 0.293(2) 1 0.034(5) 0.041(10) 0.017(6) 0.045(11)
0.004(6) 0.022(9)
0.008(6)
Cl15 0.681(1) 0.8973(5) 0.468(1) 1 0.020(3) 0.014(7) 0.029(7) 0.019(7)
0.000(5) 0.002(6) 0.007(5)
Pb1A 0.187(3) 0 0.157(5) 0.078(8) 0.020*
Pb2A 0.474(2) 0.303(1) 0.194(3) 0.075(7) 0.018(8)
O1
0.111(2) 0.359(1)
0.410(3) 1 0.014(6)
O2 0.273(2) 0.157(1)
0.250(3) 1 0.019(7)
O3 0.289(2) 0.053(1) 0.757(4) 1 0.031(8)
O4 0.582(2) 0.946(1) 0.206(3) 1 0.016(6)
O5 0.572(2) 0.153(1) 0.154(3) 1 0.020(7)
O6 0.171(2) 0.446(1)
0.025(3) 1 0.011(6)
O7
0.133(2) 0.254(1)
0.417(3) 1 0.026(8)
O8
0.009(2) 0.357(1)
0.625(3) 1 0.022(7)
O9
0.139(2) 0.1521(8)
0.417(2) 1 0.010(5)
O10 0.176(2) 0.154(1)
0.042(3) 1 0.014(6)
O11 0.775(2) 0.948(1) 0.766(3) 1 0.014(6)
O12
0.112(2) 0.050(1)
0.418(3) 1 0.018(6)
OH1 0.176(2) 0.050(1)
0.049(3) 1 0.028(8)

81
OH2
0.022(2) 0.136(1)
0.611(4) 1 0.032(8)
OH3 0.478(2) 0.2433(9) 0.386(3) 1 0.008(5)
OH4 0.093(3) 0.157(1) 0.184(4) 1 0.040(9)
OH5 0.064(2) 0.051(1) 0.186(4) 1 0.036(9)
OH6 0.948(4) 0 0.354(7) 1 0.062(18)
OH7 0.585(2) 0.258(1) 0.145(3) 1 0.028(8)
C 0.424(9) 0 0.466(14) 1 0.069(6)**
O1A 0.470(5) 0 0.385(7) 1 0.069(6)**
O1B 0.405(3) 0.037(2) 0.525(5) 1 0.069(6)**
B
0.270(7) 0.198(2)
0.116(10) 1 0.069(6)**
STRUCTURE AND CHEMISTRY OF MEREHEADITE

O2A
0.238(4) 0.173(2)
0.192(6) 1 0.069(6)**

O2B
0.283(3) 0.240(2)
0.085(6) 1 0.069(6)**
O2C
0.311(4) 0.167(20)
0.057(6) 1 0.069(6)**

* fixed during refinement

** constrained to be equal during refinement.
 S. V. KRIVOVICHEV ET AL.

TABLE 3. Selected bond lengths (Å) in the structure of mereheadite.

Pb1
O9 2.31(2) Pb10
O12 2.27(3) Pb20
O80 2.26(3)

Pb1
O12 2.33(3) Pb10
O11 2.32(3) Pb20
OH3 2.38(3)
Pb1
OH2 2.35(4) Pb10
O9 2.37(3) Pb20
O5 2.41(3)
Pb1
Cl15 3.15(2) Pb10
O2A 3.07(5) Pb20
OH7 2.80(4)
Pb1
Cl14 3.30(2) Pb10
Cl10 3.36(2) Pb20
Cl11 3.25(1)
Pb1
OH6 3.32(4) Pb10
Cl13 3.48(2) Pb20
Cl15 3.29(2)
Pb1
Cl5 3.64(2) Pb10
Cl5 3.49(2) Pb20
Cl1 3.47(2)
Pb1
Cl8 3.64(2) Pb10
Cl6 3.64(2) Pb20
Cl14 3.61(2)

Pb2
O6 2.24(3) Pb11
O3 2.27(4) Pb21
O11 2.43(3) 2x

Pb2
O11 2.29(3) Pb11
O1 2.29(3) Pb21
O6 2.44(3) 2x
Pb2
O2C 2.67(6) Pb11
O2 2.32(3) Pb21
Cl8 3.33(3)
Pb2
O2A 2.85(6) Pb11
O1B 3.02(5) Pb21
Cl5 3.49(2) 2x
Pb2
Cl7 2.98(2) Pb11
Cl6 3.48(2) Pb21
Cl10 3.64(2)
Pb2
Cl2 3.40(2) Pb11
Cl1 3.51(2)
Pb2
Cl15 3.51(2) Pb11
Cl4 3.55(2) Pb22
O2 2.21(3)
Pb2
Cl11 3.69(2) Pb11
Cl12 3.66(2) Pb22
O10 2.30(3)
Pb22
O2B 2.52(6)
Pb3
O9 2.20(3) Pb12
Cl4 2.80(2) Pb22
Cl6 3.06(2)
Pb3
O7 2.24(3) Pb12
Cl3 2.86(2) Pb22
Cl13 3.44(2)
Pb3
O2A 2.64(6) Pb12
Cl12 2.90(1) 2x Pb22
Cl1 3.44(2)
Pb3
Cl14 3.08(2) Pb12
O1A 3.29(9) Pb22
Cl11 3.68(2)
Pb3
Cl15 3.39(2) Pb12
O1B 3.41(7) 2x
Pb3
Cl1 3.41(2) Pb23
O6 2.37(3) 2x
Pb3
Cl11 3.66(2) Pb13
O1 2.24(3) Pb23
O4 2.58(3) 2x
Pb13
O7 2.28(4) Pb23
Cl7 3.41(3)
Pb4
OH6 2.19(7) Pb13
O2 2.31(3) Pb23
Cl2 3.50(2) 2x
Pb4
OH5 2.38(4) 2x Pb13
Cl11 3.26(2) Pb23
Cl3 3.72(2)
Pb4
Cl5 3.17(2) 2x Pb13
Cl2 3.32(2)
Pb4
Cl10 3.18(2) Pb13
Cl9 3.58(2) Pb24
O3 2.34(4)
Pb4
Cl8 3.61(2) Pb13
Cl13 3.60(2) Pb24
O2 2.46(3)
Pb24
O10 2.48(3)
Pb5
O5 2.20(3) Pb14
O3 2.39(4) 2x Pb24
OH1 2.52(4)
Pb5
OH7 2.37(4) Pb14
OH1 2.47(4) 2x Pb24
Cl3 3.32(1)
Pb5
O2C 2.57(6) Pb14
Cl4 3.27(3) Pb24
Cl2 3.38(2)
Pb5
Cl9 3.03(1) Pb14
Cl6 3.43(2) 2x Pb24
Cl12 3.43(2)
Pb5
O2B 3.19(6) Pb14
Cl10 3.77(2) Pb24
Cl9 3.55(2)
Pb5
Cl2 3.25(2)
Pb5
Cl13 3.34(2) Pb15
O1 2.25(3) Pb25
O4 2.25(3) 2x
Pb5
Cl11 3.66(2) Pb15
O8 2.27(3) Pb25
O1A 2.39(8)
Pb15
O1B 2.50(6) Pb25
Cl8 3.02(2)
Pb6
O7 2.37(3) Pb15
Cl11 2.98(1) Pb25
Cl15 3.35(2) 2x
Pb6
OH3 2.45(3) Pb15
Cl15 3.37(2) Pb25
Cl7 3.64(2)
Pb6
O9 2.47(2) Pb15
Cl2 3.45(2)
Pb6
OH2 2.68(4) Pb15
O1A 3.47(5) Pb26
O3 2.30(4) 2x
Pb6
Cl11 3.29(1) Pb15
Cl7 3.63(2) Pb26
O1B 2.80(5) 2x
Pb6
Cl13 3.30(2) Pb26
Cl3 3.03(2)
Pb6
Cl6 3.58(2) Pb16
Cl5 2.80(1) Pb26
Cl2 3.42(2) 2x
Pb6
Cl1 3.74(2) Pb16
Cl13 2.85(2) Pb26
Cl7 3.73(2)
Pb16
Cl14 2.93(2)
Pb7
O4 2.27(3) Pb16
Cl9 2.93(1) Pb27
OH2 2.33(4)
Pb7
O6 2.30(3) Pb16
O2B 3.23(6) Pb27
OH4 2.34(4)
Pb7
O5 2.46(3) Pb16
O2A 3.28(7) Pb27
OH5 2.50(4)
Pb7
O2C 2.97(6) Pb16
O2C 3.44(7) Pb27
Cl1 2.98(3)
Pb7
Cl8 3.25(2) Pb27
Cl12 3.21(2)

82
 STRUCTURE AND CHEMISTRY OF MEREHEADITE

Pb7
Cl15 3.35(2) Pb17
O10 2.28(3) Pb27
Cl4 3.43(2)

Pb7
Cl5 3.49(2) Pb17
OH1 2.37(4) Pb27
Cl6 3.44(2)
Pb7
Cl14 3.67(2) Pb17
OH4 2.67(4)
Pb17
OH5 2.71(4) Pb28
O12 2.24(3) 2x
Pb8
OH3 2.33(3) Pb17
Cl6 3.21(2) Pb28
OH6 2.36(8)
Pb8
O7 2.46(3) Pb17
Cl13 3.25(2) Pb28
Cl10 3.12(2)
Pb8
O1 2.48(3) Pb17
Cl10 3.59(2) Pb28
Cl6 3.53(2) 2x
Pb8
O8 2.51(3) Pb17
Cl5 3.68 Pb28
Cl4 3.63(2)
Pb8
Cl14 3.47(2)
Pb8
Cl12 3.48(2) Pb18
O10 2.28(3) Pb1A
OH5 2.61(6) 2x
Pb8
Cl9 3.48(2) Pb18
OH4 2.38(4) Pb1A
OH1 2.61(6) 2x
Pb8
Cl1 3.57(2) Pb18
OH7 2.44(4) Pb1A
Cl4 3.23(5)
Pb18
O2B 2.90(5) Pb1A
Cl12 3.30(3) 2x
Pb9
O4 2.27(3) Pb18
Cl12 3.15(2) Pb1A
Cl3 3.31(6)
Pb9
O5 2.29(3) Pb18
Cl9 3.36(1)
Pb9
O8 2.32(3) Pb18
Cl1 3.49(2) Pb2A
OH4 2.36(5)
Pb9
Cl9 3.28(1) Pb18
Cl14 3.53(2) Pb2A
OH7 2.38(5)
Pb9
Cl2 3.34(2) Pb2A
OH3 2.63(4)
Pb9
O1A 3.50(4) Pb19
O11 2.27(3) 2x Pb2A
OH2 2.69(5)
Pb9
Cl12 3.73(2) Pb19
O12 2.48(3) 2x Pb2A
Cl13 3.43(4)
Pb9
Cl3 3.77(2) Pb19
Cl7 3.28(2) Pb2A
Cl9 3.43(4)
Pb19
Cl15 3.55(2) 2x Pb2A
Cl5 3.46(4)
Pb19
Cl8 3.69(2) Pb2A
Cl14 3.47(4)

C
O1A 1.22(13) B
O2B 1.23(4)

C
O1B 1.27(8) 2x B
O2A 1.23(5)
B
O2C 1.32(5)

Pb16 sites, which are complemented by the
appearance of low-occupied Pb1A and Pb2A
sites (see details below). The SHELXL program
package was used for all structural calculations
(Sheldrick, 2008). The final model included all
atomic positional parameters, anisotropic-displa-
cement parameters for Pb and a refinable
weighting scheme of the structure factors. The
final refinement converged to an agreement index
(R1) of 0.058, calculated for the 6279 unique
reflections with |Fo| = 4sF. The final atomic
coordinates and anisotropic-displacement para-
meters are given in Table 2 and selected
interatomic distances in Table 3. The list of
observed and calculated structure factors can be
provided by the authors upon request.
Results
Cation coordination
The structure of mereheadite contains 30 non-
equivalent Pb positions (Fig. 4). Twenty eight out
of 30 sites belong to PbO blocks. The remaining
two positions, Pb12 and Pb16, lie within the
sheets of Cl
anions as depicted in Fig. 3f. These
interlayer positions are slightly under-occupied,
having site-occupancy factors (SOFs) of 0.922
and 0.925, respectively. These occupancies are
complemented by those of Pb1A and Pb2A sites
of the PbO blocks with SOFs of 0.078 and 0.075,
respectively. The Pb
Pb distances between
disordered sites are 2.14 and 2.26 Å for the
pairs Pb12
Pb1A and Pb16
Pb2A, respectively.
Replacement of Pb12 (Pb16) by Pb1A (Pb2A) is
associated with appearance of BO3 and CO3
groups within the defected PbO layers (see
below).
The coordination configurations of the Pb
atoms of the PbO blocks are distorted versions
of the square antiprism shown in Fig. 2a. In one
half of the coordination sphere, they are
coordinated by hard O2
and OH
anions, of
which there are three or four. The other
coordination hemisphere consists of four soft
Cl
anions located at the vertices of a distorted
square. The Pb12 and Pb16 atoms between the
PbO blocks have almost square-planar coordina-
tion of four Cl
. The PbCl 4 squares are
complemented by triangular TO3 groups (T = B,
C) so that a sevenfold coordination is achieved.

83
 S. V. KRIVOVICHEV ET AL.

FIG. 4. Coordination of Pb atoms in the structure of mereheadite. Pb, O and Cl atoms are shown as small black,
medium-white, and large grey circles, respectively.

Bond-valence analysis cannot be calculated unambiguously due to the

Bond-valence sums incident upon the cation and
anion sites have been calculated using bond-
valence parameters given by Krivovichev and
Brown (2001) for the Pb2+
O bond and by Brown
and Altermatt (1985) for other bonds. During the
analysis, it became clear that the all bonds within
the radii of 3.5 and 3.8 Å should be counted for
the Pb2+
O and Pb2+
Cl bonds, respectively.
The bond-valence sums for Pb sites are in the
range of 1.75
2.06 v.u. (valence units), for O
sites in the range of 1.88
1.99 v.u., for Cl sites in
the range of 0.60
1.13 v.u. and for OH sites in
the range of 0.98
1.17 v.u.. Bond-valence sums
for the T sites and O atoms of the TO3 groups
large standard deviations of the T
O bond lengths
(up to 0.13 Å).
Structure description
A projection of the structure of mereheadite onto
the (010) plane is shown in Fig. 5. The structure
belongs to the 1:1 type and consists of alternating
Pb
O/OH blocks and Pb
Cl sheets oriented
parallel to the (201) plane.
The atomic structure of the PbO block is shown
in Fig. 6a. In this figure, the Pb1A and Pb2A sites
are removed from consideration, owing to their
low occupancy. Fig. 6b shows the same block
viewed from the standpoint of oxocentered OPb4

84
 STRUCTURE AND CHEMISTRY OF MEREHEADITE

FIG. 5. The structure of mereheadite in projection along the b axis. Legend as in Fig. 4.

FIG. 6. The Pb
O/OH block in mereheadite without the low-occupancy Pb1A and Pb2A sites, shown in ball-and-
stick presentation (a) and in terms of OPb4 oxocentered tetrahedra (b). Legend as in Fig. 4.

85
 S. V. KRIVOVICHEV ET AL.
tetrahedra. The block can be described as a
highly-defected version of an ideal PbO block
(Fig. 1). It is noteworthy that the block contains
square-shaped vacancies occupied by TO3 groups,
these correlating with the positions of the
Pb(12)Cl4 and Pb(16)Cl4 squares in the Pb
Cl
sheets. There are seven OH groups in the
Pb
O/OH block. The OH1, OH2, OH3, OH4,
OH5, and OH7 groups are coordinated by three
Pb atoms each, whilst the OH6 group is
coordinated by two Pb atoms only. The
Pb
O/OH block can be obtained from the ideal
PbO block by the following procedure:
(1) removal of some PbO4 groups that results in
formation of square-shaped vacancies; (2) inser-
tion of TO 3 groups into these vacancies;
(3) removal of some Pb atoms (that correspond
to the Pb1A and Pb2A sites), thus transforming
coordination of associated O sites from tetra-
hedral OPb4 to triangular OHPb3; (4) replacement
of two O2
anions by one OH
anion with
twofold coordination; this results in formation of
the 162 elongated rectangular vacancy. To
clarify, Fig. 7a shows the atomic structure of the
Pb
O/OH blocks with Pb1A and Pb2A atoms.
The same structure represented as OPb4 tetrahedra
is shown in Fig. 7b. In the presence of the Pb1A
and Pb2A atoms, all OH sites except OH6 are
tetrahedrally coordinated by Pb. From this view-
point, the PbO block contains two types of
vacancies: square-shaped occupied by TO 3
groups and rectangular-shaped with attached
OH6 groups.
Figure 8 shows the structure of the Pb
Cl
sheet. It represents a planar arrangement of
isolated PbCl4 squares and Cl
. Note that the
positions of the squares correlate with the square-
shaped vacancies in the Pb
O/OH sheets.
Chemical formula
The structural formula that can be derived on the
basis of the results of single-crystal structure
determination is Pb47O24(OH)13Cl25(BO3)2(CO3).
Welch et al. (1998) provided for mereheadite the
empirical formula Pb8O4.19(BO3)0.51(CO3)0.62
(OH) 0.76Cl4.09 , which can be re-written as
Pb 48 O 25.14 (OH) 4.56 Cl 24.54 (BO 3 ) 3.06 (CO 3 ) 3.72 .
Compared to the structural formula, the empirical
formula shows a much higher CO3 content, a
reasonably higher BO3 content, and a much lower
OH content. On the other hand, the Pb:Cl ratio
that can be reliably determined using electron
microprobe analysis is in generally good agree-
86
ment with the diffraction experiment. In the
original study of Welch et al. (1998), the CO2
and B amounts were determined by wet-chemical
analysis using a CHN analyser and by the
Curcumin methods, respectively. Since merehea-
dite is closely associated with cerussite, it is
conceivable that the higher CO2 content may arise
from contamination by cerussite. We note that the
11
B MAS NMR study performed by Welch et al.
(1998) indicated that B is present as BO3 groups

in excellent agreement with the results of the
present study.
Welch et al. (1998) proposed the simplified
formula Pb2O(OH)Cl, for mereheadite which
assumes that neither borate or carbonate are
essential constituents, and suggested that their
presence in the mineral is due to disordered
replacement of Cl
anions. However, it has been
demonstrated above that this is not the case, as
BO3 and CO3 groups have well-defined structural
positions confined in the vacancies of the
Pb
O/OH blocks. Thus, the correct simplified
formula for mereheadite can be given as
Pb47O24(OH)13Cl25(BO3)2(CO3).
Discussion
Mereheadite is another example of 1:1 lead
oxyhalides consisting of PbO blocks. As
mentioned in the Introduction, there are three
basic mechanisms associated with transition of
the structure from the idealized version (ideal
PbO blocks alternating with tetragonal sheets of X
atoms) to the observed structure: replacement of
PbO4 groups by coordination groups of highly-
charged cations, O2
$ OH
substitution, and
insertion of additional Pb2+ cations into the X
sheet. From the results of this study, it is clear that
all three mechanisms are at work in the structure
of mereheadite. First, there are square-shaped
vacancies within the PbO blocks occupied by
triangular TO3 groups. This type of substitution
has been observed previously in symesite (Welch
et al., 2000), which points to a close relationship
between this mineral and mereheadite. Second,
the O2
$ OH
substitution of the kind observed
in blixite (Krivovichev and Burns, 2006) is also
displayed in this structure.
The structure of mereheadite is related to that
of symesite, which has a similar layered 1:1
Pb
O
OH/Pb
Cl structure containing square
defect sites. However, in the case of symesite,
these sites are occupied by SO4 groups. Therefore,
it seems likely that the occupancy of these square
 STRUCTURE AND CHEMISTRY OF MEREHEADITE

FIG. 7. The Pb
O/OH block in mereheadite with the low-occupancy Pb1A and Pb2A sites included, shown in ball-
and-stick presentation (a) and in terms of OPb4 oxocentered tetrahedra (b). Legend as in Fig. 4.

FIG. 8. The Pb
Cl sheet in the structure of mereheadite. Pb and Cl atoms are shown as small black and large grey
circles, respectively.

87
 S. V. KRIVOVICHEV ET AL.
sites is variable and that a range of minerals
including mereheadite exists within what we have
termed the ’Symesite Group’ (as this was the first
species to have the square defect structure and
substitution mechanism described).
The spatial distribution of square sites changes
between mereheadite and symesite (see Figs. 7b
and 3c, respectively) and this may be related to
the differences in chemistry or to anion shape

SO4 groups are tetrahedral whilst BO3 and CO3
groups are triangular, i.e. planar. It is possible to
outline pathways between the two minerals,
although it is not currently clear where the
transition points lie, nor if intermediate members
would be stable.
It is also possible that phases with other anions
and anion combinations will be recognised. In the
course of research work on other Merehead
material, two of the authors (MR and RT) have
discovered a mineral which has an XRD pattern
identical to that of symesite but which contains no
sulphate; it is possible that this is a carbonate
analogue of symesite.
Mereheadite is the first mineral which has
additional inter-layer Pb sites located within the
sheets of Cl
anions. The only other example of
such architecture is the synthetic compound
Pb 31O22Br 10Cl8 (Krivovichev et al., 2006).
Finally, the data conclusively show that merehea-
dite is not a polymorph of blixite.
Acknowledgements
We thank F. Camara and anonymous referee for
useful remarks and corrections, and Principal
Editor Mark Welch for suggestions that led to
considerable improvement of the initial version of
the paper. This study was supported by the
Russian Federation Ministry of Science and
Education (grant #RNP 2.1.1.3077), DFG (grant
DE 412/34-1 that supported O.I.S.) and the
Federal Agency on Education (SPbSU innovation
education project ‘Innovational educational envir-
onment in the classic University’) that provided
instrumental support.
References
Aurivillius, B. (1982) On the crystal structure of a
number of non-stoichiometric mixed lead oxide
halides composed of PbO like blocks and single
halogen layers. Chemica Scripta, 19, 97
107.
Aurivillius, B. (1983) On the crystal structure of some
non-stoichiometric mixed lead oxide halides and
88
their relation to the minerals "lorettoite" and
sundiusite. Chemica Scripta, 22, 5
11.
Bindi, L., Welch, M.D., Bonazzi, P., Pratesi, G. and
Menchetti, S. (2008) The crystal structure of
seeligerite Pb3IO4Cl3, a rare Pb
I oxychloride from
the San Rafael mine, Sierra Gorda, Chile.
Mineralogical Magazine, 72, 771
783.
Bonaccorsi, E. and Pasero, M. (2003) Crystal structure
refinement of sahlinite, Pb 1 4 (AsO 4 ) 2 O 9 Cl 4 .
Mineralogical Magazine, 67, 15
21.
Brown, I.D. and Altermatt, D. (1985) Bond-valence
parameters obtained from a systematic analysis of
the Inorganic Crystal Structure Database. Acta
Crystallographica B, 41, 244
247.
Cooper, M.A. and Hawthorne, F.C. (1994) The crystal
structure of kombatite, Pb14(VO4)2O9Cl4, a complex
heteropolyhedral sheet mineral. American
Mineralogist, 79, 550
554.
Cooper, M.A. and Hawthorne, F.C. (1999) The structure
topology of sidpietersite, Pb2+ 6+ 2

4 (S O3S )O2(OH)2, a
novel thiosulfate structure. The Canadian
Mineralogist, 37, 1275
1282.
Criddle, A.J., Keller, P., Stanley, C.J. and Innes, J.
(1990) Damaraite, a new lead oxychloride from the
Kombat mine, Namibia (South West Africa).
Mineralogical Magazine, 54, 593
598.
Gabrielson, O., Parwel, A. and Wickman, F.E. (1960)
Blixite, a new lead-oxyhalide mineral from Langban.
Arkiv foer Mineralogi och Geologi, 2, 411
415.
Grice, J.D. (2002) A solution to the crystal structures of
bismutite and beyerite. The Canadian Mineralogist,
40, 693
698.
Grice, J.D. and Dunn, P.J. (2000) Crystal structure
determination of pinalite. American Mineralogist,
85, 806
809.
Krivovichev, S.V. and Brown, I.D. (2001) Are the
compressive effects of encapsulation an artifact of
the bond valence parameters? Zeitschrift für
Kristallographie, 216, 245
247.
Krivovichev, S.V. and Burns, P.C. (2001) Crystal
chemistry of lead oxide chlorides. I. Crystal
structures of synthetic mendipite, Pb3O2Cl2, and
synthetic damaraite, Pb 3 O 2 (OH)Cl. European
Journal of Mineralogy, 13, 801
809.
Krivovichev, S.V. and Burns, P.C. (2002) Crystal
chemistry of lead oxide chlorides. II. Crystal
structure of Pb7O4(OH)4Cl2. European Journal of
Mineralogy, 13, 135
139.
Krivovichev, S.V. and Burns, P.C. (2006) The crystal
structure of Pb8O5(OH)2Cl4, a synthetic analogue of
blixite? The Canadian Mineralogist, 44, 515
522.
Krivovichev, S.V., Siidra, O.I., Nazarchuk, E.V., Burns,
P.C. and Depmeier, W. (2006) Exceptional topolo-
gical complexity of lead oxide blocks in Pb31O22X18
(X = Br, Cl). Inorganic Chemistry, 45, 3846
3848.
Lagercrantz, A. and Sillén, L.G. (1948) On the crystal
 STRUCTURE AND CHEMISTRY OF MEREHEADITE
structure of Bi2O2CO3 (bismutite) and
CaBi 2 O 2 (CO 3 ) 2 (beyerite). Arkiv foer Kemi,
Mineralogi och Geologi, A25(2), 1
21.
Noren, L., Tan, E.S.Q., Withers, R.L., Sterns, M. and
Rundlof, H. (2002) A neutron, X-ray and electron
diffraction study of the structures of Pb3O2X2 (X=Cl,
Br). Materials Research Bulletin, 37, 1431
1442.
Post, J.E. and Buseck, P.R. (1985) Quantitative energy-
dispersive analysis of lead halide particles from the
Phoenix urban aerosol. Environmental Science and
Technology, 19, 682
685.
Rouse, R.C., Peacor, D.R., Dunn, P.J., Criddle, A.J.,
Stanley, C.J. and Innes, J. (1988) Asisite, a silicon-
bearing lead oxychloride from the Kombat mine,
South West Afri ca (Namibi a). Ame rican
Mineralogist, 73, 643
650.
Sheldrick, G.M. (2008) A short history of SHELX. Acta
Crystallographica A, 64, 112
122.
Siidra, O.I. and Krivovichev, S.V. (2008) Crystal
chemistry of oxocentered chain lead oxyhalides and
their importance as perspective materials.
Pp. 129
142 in: Minerals as Advanced Materials I
(S.V. Krivovichev, editor). Springer-Verlag, Berlin,
Heidelberg.
Siidra, O.I., Krivovichev, S.V. and Filatov, S.K. (2008a)
Minerals and synthetic Pb(II) compounds with
oxocentered tetrahedra: review and classification.
Zeitschrift für Kristallographie, 223, 114
126.
Siidra, O.I., Krivovichev, S.V., Turner, R. and Rumsey,
M. (2008b) Chloroxiphite Pb3CuO2(OH)2Cl2: struc-
ture refinement and description in terms of oxocen-
tered OPb4 tetrahedra. Mineralogical Magazine, 72,
793
798.
Spencer, L.J. and Mountain, E.D. (1923) New lead-
copper minerals from the Mendip Hills, Somerset,
England. Mineralogical Magazine, 20, 67
92.
Steele, I.M. and Pluth, J.J. (1998) Crystal structure of
tetrabasic lead sulfate (4PbO.PbSO4). An intermedi-
ate phase in the production of lead-acid batteries.
Journal of Electrochemical Society, 145, 528
533.
89
View publication stats
Steele, I.M., Pluth, J.J. and Richardson, J.W. Jr. (1997)
Crystal structure of tribasic lead sulfate
(3PbO·PbSO4.H2O) by X-rays and neutrons: an
intermediate phase in the production of lead acid
batteries. Journal of Solid State Chemistry, 132,
173
181.
Symes, R.F. and Embrey, P.G. (1977) Mendipite and
other rare oxychloride minerals from the Mendip
Hills, Somerset, England. Mineralogical Record, 8,
298
303.
Symes, R.F., Cressey, G., Criddle, A.J., Stanley, C.J.,
Francis, J.G. and Jones, G.C. (1994) Parkinsonite,
(Pb,Mo,&)8O8Cl2, a new mineral from Merehead
Quarry, Somerset. Mineralogical Magazine, 58,
59
68.
Turner, R. (2006) A mechanism for the formation of the
mineralized Mn deposits at Merehead Quarry,
Cranmore, Somerset, England. Mineralogical
Magazine, 70, 629
653.
Welch, M.D. (2004) Pb-Si ordering in sheet-oxychloride
minerals: the super-structure of asisite, nominally
Pb7SiO8Cl2. Mineralogical Magazine, 68, 247
254.
Welch, M.D., Schofield, P.F., Cressey, G. and Stanley,
C.J. (1996) Cation ordering in lead-molybdenum-
vanadium oxychlorides. American Mineralogist, 81,
1350
1359.
Welch, M.D., Criddle, A.J. and Symes, R.F. (1998)
Mereheadite, Pb2O(OH)Cl: a new litharge-related
oxychloride from Merehead Quarry, Cranmore,
Somerset. Mineralogical Magazine, 62, 387
393.
Welch, M.D., Cooper, M.A., Hawthorne, F.C. and
Criddle, A.J. (2000) Symesite,
Pb10(SO4)O7Cl4(H2O), a new PbO-related sheet
mineral: description and crystal structure. American
Mineralogist, 85, 1526
1533.
Welch, M.D., Hawthorne, F.C., Cooper, M. and Kyser,
T.K. (2001) Trivalent iodine in the crystal structure
of schwartzembergite, Pb 2+ 3+
5 I O 6 H 2 Cl 3 . The
Canadian Mineralogist, 39, 785
795.