Eur. J. Mineral.
2018, 30, 811–820
Published online 27 February 2018

Lavinskyite-1M, K(LiCu)Cu6(Si4O11)2(OH)4, the monoclinic MDO
equivalent of lavinskyite-2O (formerly lavinskyite), from the Cerchiara
manganese mine, Liguria, Italy
UWE KOLITSCH1,2,*, STEFANO MERLINO3, DONATO BELMONTE4, CRISTINA CARBONE4, ROBERTO CABELLA4,GABRIELLA LUCCHETTI4 and MARCO E. CIRIOTTI5
1

Mineralogisch-Petrographische Abt., Naturhistorisches Museum, Burgring 7, 1010 Wien, Austria*Corresponding author, e-mail: uwe.kolitsch@nhm-wien.ac.at2
Institut für Mineralogie und Kristallographie, Geozentrum, Universität Wien, Althanstraße 14, 1090 Wien, Austria
3
Università degli Studi di Pisa, Dipartimento di Scienze della Terra, Via S. Maria 53, 56126 Pisa, Italy
4
DISTAV, Università degli Studi di Genova, Corso Europa 26, 16132 Genova, Italy
5
Associazione Micromineralogica Italiana, Via San Pietro, 55, 10073 Devesi-Cirié, Italy

Abstract: Lavinskyite-1M, a monoclinic MDO (Maximum Degree of Order) polytype related to the orthorhombic MDO polytype
lavinskyite-2O (formerly lavinskyite, now redeﬁned), was identiﬁed in samples from the Cerchiara manganese mine (Liguria, Italy). Bothpolytypes have the same ideal chemical formula, K(LiCu)Cu6(Si4O11)2(OH)4. Lavinskyite-1M was originally approved as “liguriaite”,
but was subsequently redeﬁned as lavinskyite-1M (IMA proposal 16-E).
Lavinskyite-1M occurs as blue, micaceous aggregates embedded in calcite-ﬁlled microfractures and veinlets, where it is associatedwith calcite, quartz, norrishite and “schefferite” (a Mn-bearing variety of diopside). Lavinskyite-1M is translucent to transparent,
bluish to pale blue in colour with a very pale blue to whitish streak and vitreous lustre; it is non-ﬂuorescent. Individual, always
indistinct platelets are up to ∼0.15 mm in length. The crystals are tabular (100) and elongate along [001]. Lavinskyite-1M isbrittle with perfect cleavage parallel to {100}, and uneven fracture. The estimated Mohs hardness is ∼5. The calculated density is
3.613 g/cm3 (for empirical formula). Optically, it is biaxial positive, with a = 1.674(2); b = 1.692(3) and g = 1.730(3); 2Vg is very large,∼75° (est.), 2Vg (calc.) = 70°. Pleochroism is moderate: X (pale) blue, Y pale blue and Z pale blue with faint greenish tint; absorption
X ≥ Z ≥ Y. Orientation: X ^ a ∼20° (probably in obtuse beta), Y = b, Z ∼ c; optical elongation is positive and the optical axis plane isparallel to (010). No dispersion was observed.
Chemical analysis (quantitative SEM-EDS and LA-ICP-MS) of two samples yielded the empirical formulae (based on 26 O atoms)(Li0.89Cu0.35Mg0.28Na0.22Mn2þ0.04)S1.78(K1.08)S1.08(Li0.89Mg0.36Cu0.33Na0.22Mn2þ0.04)S1.86Cu6.00Si8.08O22(OH)4 and (K1.08)S1.08

Cu6.00Si8.12O22(OH)4. Strongest lines in the X-ray powder diffraction pattern are [d in A (Icalc) hkl]): 10.216 (100) 100, 9.007 (20)110, 4.934 (19) 210, 3.983 (19) 230, 3.353 (33) 310, 2.8693 (22) 241, 2.6155 (35) 161, 2.3719 (23) 20-2. The crystal structure has beensolved, using single-crystal X-ray diffractometer data (Rint = 4.60%), by direct methods and reﬁned in space group P21/c (no. 14) toreﬂections with Fo > 4s(Fo), 199 parameters]. Reﬁned unit-cell parameters are:
R1 = 5.10% and wR2all = 13.92% [1786 ‘observed’
a = 10.224(2), b = 19.085(4), c = 5.252(1) A, b = 92.23(3)°, V = 1024.0(4) A3 (Z = 2). The chemical composition and crystal structure aresupported by micro-Raman spectra.
Lavinskyite-1M has a sheet structure consisting of corrugated brucite-like (CuO2)n layers with amphibole-type (SiO3)n chainsjoined to both their upper and lower surfaces. Adjacent complex sheets are linked by [5]-coordinated Li atoms and Cu atoms in square
coordination (nearly planar) and interlayer K atoms. Lavinskyite-1M is isostructural with a hypothetical monoclinic MDO polytype ofplancheite, not yet found in nature, while lavinskyite-2O is isostructural with plancheite. It appears that a complex and delicate
interplay between the Li:Cu and Cu:Mg ratios (lower in lavinskyite-1M), along with an additional inﬂuence of impurity cations suchas Na and different conditions of formation, results in a stabilisation of the 1M polytype. The origin of lavinskyite-1M can be related to
a complex, multi-stage hydrothermal evolution of the primary Fe-Mn ore at Cerchiara, which experienced a diffuse alkali
metasomatism under strongly oxidising conditions and produced mineral assemblages enriched in Na, K and Li, while providing also
appreciable amounts of Ba, Sr, Ca and Cu.
Key-words: MDO polytype; lavinskyite-1M; copper silicate; crystal structure; Raman spectroscopy; manganese mine; Liguria; Italy.

1. Introduction
An unusual blue, micaceous mineral, collected in 2004 on
the dumps of the Cerchiara manganese mine (eastern
https://doi.org/10.1127/ejm/2018/0030-2731

Liguria, northern Apennines, Italy) by Mr Fabrizio
Castellaro of Mezzanego, Genoa, Italy, was soonrecognised as a new alkali copper silicate and brieﬂymentioned as an unidentiﬁed species “UK4” in Castellaro
0935-1221/18/0030-2731 $ 4.50

© 2018 E. Schweizerbart’sche Verlagsbuchhandlung, D-70176 Stuttgart
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U. Kolitsch et al.

(2008). Preliminary results (Carbone et al., 2014)
suggested the new mineral to be a monoclinic polymorphof (orthorhombic) lavinskyite (Yang et al., 2014). The later
proposed species name liguriaite was originally chosen inrecognition of the mineral-rich region in which the type
locality is located (it is in fact the Italian region with thehighest density of mineral species). However, after themineral and its name had been approved by the IMA
Commission on New Minerals, Nomenclature andClassiﬁcation (IMA 2014-035), the authors, on re-reading
published information on the plancheite OD family,
realised that “liguriaite” was probably a monoclinic MDO
polytype of (orthorhombic) lavinskyite, a conclusion thenconﬁrmed by detailed calculations and comparisons doneby one of us (S. M.) and a careful re-reﬁnement of thecrystal structure. A subsequent proposal to redeﬁne“liguriaite” as lavinskyite-1M and type lavinskyite as
lavinskyite-2O was approved in 2016 (IMA proposal
16-E). The naming of the polytypes is in line with joint
IMA-IUCr recommendations (Guinier et al., 1984).
The studied lavinskyite-1M material consists of two
micromount-sized cotype specimens; the ﬁrst one ispreserved in the collection of the Dipartimento di Scienzedella Terra, dell’Ambiente e della Vita (DISTAV),
Università degli Studi di Genova, Italy (catalogue no.
MO482). The second cotype is preserved in the collection of
the Natural History Museum in Vienna, Austria (catalogue
no. N 9733). The total amount of material comprises three
micromount-sized specimens. The present article provides a
description of lavinskyite-1M and its relation to lavinskyite2O within the newly deﬁned lavinskyite OD family.

2. Occurrence and paragenesis
At the Cerchiara manganese mine, lavinskyite-1M occurs inmicrofractures and veinlets cross-cutting Jurassic metacherts (Lucchetti et al., 1988; Palenzona et al., 1988).
Associated minerals include calcite, quartz, norrishite and“schefferite” (a Mn-bearing variety of diopside).
Polyphase mineral assemblages in manganese ores occur
within metacherts of the northern Apennine ophiolitic units(“Diaspri di Monte Alpe” Formation), which underwent
prehnite-pumpellyite facies metamorphism (P = 2.5 ± 0.5
kbar, T = 275 ± 25 °C) followed by hydrothermal mobilisation along fractures under decreasing thermobaric
conditions (Cabella et al., 1991, 1998). Circulation of
ﬂuids along extensional fractures induced further concentration of dispersed elements such as Ba, Sr, As, V and Te,
and allowed the genesis of a great variety of rare and newminerals, both at Cerchiara (e.g. Basso et al., 1993, 1997,
2000; Cabella et al., 1993) and the nearby manganesemines of Val Graveglia (e.g. Lucchetti et al., 1981; Basso
et al., 2005, 2008; Bindi et al., 2011, 2013; Carbone et al.,2013; Ma et al., 2014; Kampf et al., 2017). Althoughmanganese mineralisations at the Cerchiara mine share acommon petrogenetic environment with those of Val
Graveglia, there are some relevant differences. The
presence of hematite, besides braunite, as the main

constituent of the ore body at Cerchiara suggests highly
oxidising conditions of the minerogenetic environment.
This would be conﬁrmed by the secondary mineralparageneses at Cerchiara, which are dominated by Mn3þand Fe3þ-rich silicates such as aegirine, piemontite,
namansilite, orientite–macfallite and cerchiaraite (Lucchetti
et al., 1988; Basso et al., 1989a, 1989b, 2000; Kampf
et al., 2013), at variance with the relatively reducing
johannsenite-, rhodonite-bearing assemblages of Val Graveglia (Cabella et al., 1991). The recent ﬁndings at Cerchiara
mine of a V5þ-bearing mica, balestraite (Lepore et al., 2015)
and of manganiceladonite, a new Mn3þ end-member of theceladonite family (Lepore et al., 2017), further support theevidence of a strongly oxidising character of the hydrothermal ﬂuids responsible for the mobilisation and subsequent
recrystallisation of the Fe-Mn ore. Finally, the manganesemineralisations at Cerchiara experienced a large hydrothermal metasomatism induced by diffuse interaction withalkali-rich ﬂuids, which produced peculiar mineral assemblages enriched in Na, K and Li and provided also appreciable
amounts of Ba, Sr, Ca and Cu, in strong analogy with similarassemblages described at the Bruce mine and Wessels mine
(Transvaal Supergroup in the Kalahari Manganese Field,
South Africa) (Gnos et al., 2003; Tsikos & Moore, 2005a;
Moore et al., 2011) and Hoskins mine (New South Wales,
Australia) (Ashley, 1986; Eggleton & Ashley, 1989). These
metasomatic mineralisations, concentrated in veins andvoids cross-cutting both the metacherts and the braunite–hematite ore, are represented by alkali-rich and oxidisedparageneses including characteristic (Na, K, Li)-richminerals such as aegirine, albite, balestraite, namansilite,
pectolite–serandite, richterite, magnesio-arfvedsonite, sugilite, nambulite and norrishite (Lucchetti et al., 1988; Cabella
et al., 1990; Palenzona & Selmi, 1990; Balestra, 2005;
Balestra et al., 2009; Lepore et al., 2015). The origin of
lavinskyite-1M can be related to this complex, multi-stagehydrothermal evolution of the primary Fe-Mn ore at
Cerchiara.

3. Physical properties
Lavinskyite-1M forms millimetric blue aggregates of
subparallel platy crystals in association with quartz, calcite(partly etched away with dilute acid) and “schefferite” (aMn-bearing variety of diopside) in grey-pinkish ﬁbrousaggregates (Fig. 1). The mineral is tabular on (100) andelongate along [001], conﬁrmed by a single-crystal XRD
study of the morphology using video-based modelling of
the crystal faces with the help of a dedicated diffractometer
software module. Individual, always indistinct platelets
are up to ∼0.15 mm in length. Although the platy crystals
sometimes show a roughly rectangular outline, only theform {100} was clearly identiﬁed; other forms were notrecognisable. No twinning was observed during any of ourstudies. Lavinskyite-1M is brittle with perfect cleavage
parallel to {100}, and uneven fracture. The estimatedMohs hardness is ∼5 (by comparison with its polytype
lavinskyite-2O). The calculated density is 3.613 g/cm3 (forthe empirical formula).

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Lavinskyite-1M from the Cerchiara manganese mine

813

compositions. The ideal chemical formula is K(LiCu)
Cu6(Si4O11)2(OH)4, identical to that of its orthorhombic
polytype lavinskyite-2O (Yang et al., 2014, this work).
The Gladstone-Dale compatibility (Mandarino, 1981) issuperior (0.011) for the empirical formula.

5. Raman spectroscopy

Fig. 1. Millimetric blue aggregates of lavinskyite-1M associatedwith quartz, calcite (partly etched away) and “schefferite” (a Mnbearing variety of diopside) in grey-pinkish ﬁbrous aggregates. Fieldof view 6 mm across. Photo Harald Schillhammer.

Optically, lavinskyite-1M is biaxial positive, witha = 1.674(2); b = 1.692(3) and g = 1.730(3); 2Vg is verylarge, ∼75° (estimated using polarised-light microscopy),
2Vg (calc.) = 70°. Pleochroism is moderate: X (pale) blue, Y
pale blue and Z pale blue with faint greenish tint;
absorption X ≥ Z ≥ Y. Orientation is: X ^ a ∼20° (probably
in obtuse beta), Y = b, Z ∼ c; optical elongation is positive
and the optical axis plane is parallel to (010). No
dispersion was observed. The mineral is insoluble in cold
dilute HCl.

4. Chemical composition
Chemical analyses of two lavinskyite-1M samples (sectioned, polished and carbon-coated crystal aggregates) werecarried out using a Tescan Vega 3 LMU scanning-electron
microscope equipped with an energy-dispersive X-ray
spectrometer (EDAX Apollo X SDD) and TEAM EDS(Texture and Elemental Analytical Microscopy) software(e-ZAF correction). Operating conditions were: voltage
20 kV, sample current 1.2 nA, beam diameter 320 nm, countrate 60 s. Standards used were: Metals MAC std for Vand Fe,
Wollastonite MAC std for Ca and Si, Orthoclase MAC std
for K, Ilmenite USNM 96189 for Mn, Omphacite USNM
110607 for Mg and Chalcopyrite C23T for Cu. The mineral
was stable under the electron beam. The analyses showedsmall variations within and between grains. Na and Li
contents were measured separately by LA-ICP-MS. We
point out that Ca, Sr or Ba were detected neither by SEMEDS nor by EMP-WDS. The water content could not be
determined directly due to the meagre quantity of material,and hence was added for charge balance (Scations =þ52.00) and to bring the analytical total close to 100%. The
chemical analyses of the two samples, listed in Table 1,yielded the empirical formulae (based on 26 O atoms)(K1.08)S1.08(Li0.89Mg0.36Cu0.33Na0.22Mn2þ0.04)S1.86Cu6.00
Si8.08O22(OH)4 and (K1.08)S1.08(Li0.89Cu 0.35Mg0.28Na0.22
Mn2þ0.04)S1.78Cu6.00Si8.12O22(OH)4, i.e. very similar

Micro-Raman spectra (Fig. 2) were recorded on randomly
oriented grains in the Raman shift range 100–4000 cm1using a Renishaw Ramascope equipped with a He-Ne laser(633 nm) and connected to a Leica optical microscope
equipped with an Olympus SLM plan 20  long focal
objective. The Raman spectra of lavinskyite-1M andlavinskyite-2O (Yang et al., 2014, this work) are very
similar in the low-wavenumber region and in the OH
region. However, in the ﬁrst region some peaks are lesspronounced in lavinskyite-1M (region from 800 to
1200 cm1), and in the OH region lavinskyite-2O shows
three bands at 3630, 3662 and 3694 cm1 (Yang et al.,2014) whereas lavinskyite-1M has only two (at 3662 and3694 cm1). These two bands are assigned to OH
stretching vibrations, in accordance with the crystalstructure determination (see below). No bands indicating
any presence of CO32 were observed.

6. X-ray crystallography
The crystal structure was solved using single-crystal X-ray
intensity data collected at ambient temperature from asuitable tiny crystal fragment on a Nonius KappaCCD
single-crystal X-ray diffractometer equipped with a CCD
detector and a 300 mm diameter capillary-optics collimator to provide increased resolution. The measured intensity
data were processed with the Nonius program suite
DENZO-SMN and corrected for Lorentz, polarisation,
background and absorption effects, the latter by the multiscan method (Otwinowski et al., 2003). The crystalstructure solution employed direct methods (SHELXS-97,
Sheldrick, 2008) in space group P21/c (no. 14), as
indicated by the observed systematic extinctions andintensity statistics. The model was smoothly reﬁned byfull-matrix least-squares techniques on F2 (SHELXL-97,
Sheldrick, 2008) to R1 = 5.10% and wR2all = 13.92%[1786 ’observed’ reﬂections with Fo > 4s(Fo), 199
parameters]. The topology obtained was identical to thatof the orthorhombic polytype lavinskyite-2O (Yang et al.,2014, this work). Speciﬁcally, the M4 site was found to be
split in the same manner as in lavinskyite-2O, i.e. into an(ideally) half-occupied Cu site [M(4a)] and an (ideally)
half-occupied Li site [M(4b)]. The occupancy of the Cu
site, if freely reﬁned, is 0.594(4), with an Ueq of 0.0217(5) A2, only slightly higher than the Ueq values of the threeremaining metal sites M1-3 occupied by Cu (and minor
Mg). Free isotropic reﬁnement of the Li site resulted in aphysically unrealistic Uiso of 0.00001 A2 and an occupancy
of 0.23.
Therefore, Uiso was ﬁxed to a reasonable value of
0.05 A2, resulting in a Li-site occupancy of 0.36(3). The

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U. Kolitsch et al.

Table 1. Chemical-analytical data (wt%) for lavinskyite-1M.
Cerch1 (7 points)

Cerch2 (7 points)

Constituent

Wt%

Range

SD

Wt%

Range

SD

Probe standard

SiO2
CuO
MgO
MnO
Na2O*
K2O
Li2O*
H2O**
Total

42.51
44.12
1.27
0.27
0.61
4.46
1.17
3.16
97.58

40.94–45.37
40.69–45.97
0.26–3.76
0.21–0.38
0.55–0.70
4.37–4.58
1.10–1.26

1.31
1.77
1.21
0.07
0.05
0.07
0.05

42.98
44.53
0.99
0.23
0.61
4.48
1.17
3.18
98.29

42.20–43.41
43.71–45.78
0.00–1.90
0.00–0.32
0.55–0.70
4.39–4.59
1.10–1.26

0.44
0.66
0.65
0.10
0.05
0.07
0.05

wollastonite
chalcopyriteomphacite
metallic Mn–orthoclase––*
Measured separately by LA-ICP-MS (average values, 12 data points). Na was also measured by EPMA-WDS and gave 0.66 wt% Na2O on
average, close to the average value of 0.61 wt% Na2O obtained by LA-ICP-MS.
**
Water added for charge balance (Scations = þ52.00) and to bring analytical total close to 100%.
Ca, Sr or Ba were neither detected by SEM-EDS nor by EMPA-WDS.

Fig. 2. Single-crystal laser-Raman spectrum of lavinskyite-1M in the low-wavenumber region (<1300 cm1) and in the O-H stretchingregion (inset).

latter is reasonably close to the ideal value of 0.5,
considering the low electron density involved and theimperfect quality of the dataset. If the Li-atomcoordinates were reﬁned with a ﬁxed Uiso of 0.05 A2
and freely variable occupancy, the following values wereobtained: 0.098(4), 0.796(2), 0.157(8). In contrast, for aﬁxed half-occupancy, the coordinates reﬁned to 0.106(9),0.748(5), 0.26(2), i.e. values with approximately doubled
s.u.s, and the M(4a)–M(4b) distance was unrealisticallyshort (∼0.06 A); furthermore, the value for (D/s)max inthe reﬁnement was ∼1.00, again unrealistic and far fromthe commonly observed value of ∼0.00. Consequently,
the coordinates were ﬁxed to those obtained from thereﬁnement with freely variable occupancy, which
resulted in a much more reasonable (D/s)max of 0.000
and a M(4a)–M(4b)distance similar to that in lavinsky
ite-2O (∼1.0 A, for details see below). In the ﬁnal model,
the occupancies of both M(4a) and M(4b) were ﬁxed to
0.5, to obtain a charge-balanced formula. Note, however,
that, ﬁrstly, this increased the R(F) value from 4.8% to
5.1%. Secondly, the freely reﬁned occupancies of the M(4a) and M(4b) sites, 0.594(4) and 0.36(3), would result

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Lavinskyite-1M from the Cerchiara manganese mine

Table 2. Crystal data, data collection information and reﬁnement
details for lavinskyite-1M.
Crystal data
Formula (idealised)
Formula weightSpace group,Za, b, c (A)b (°)V (A3)
F(000), rcalc (g cm3)m (mm1)
Absorption correction
Crystal dimensions (mm)Data collection and reﬁnement
Diffractometerl (Mo-Ka) (A), T (K)Crystal-detector distance
Rotation axis, width (°)
Total no. of frames
Collect. time per frame (s)Collection mode, 2umax (°)
h, k, l ranges
Total reﬂections measured
Unique reﬂections
Reﬁnement on
R1(F), wR2all(F2)*’Observed’ reﬂs.
Extinct. coefﬁcient
No. of reﬁned parameters
GooF(D/s)maxDrmin, Drmax (e/A3)

K(LiCu)S2(Cu4.41Mg1.59)S6(Si4O11)2(OH)4
1087.17
P21/c (no. 14), 2
10.224(2), 19.085(4), 5.252(1)92.23(3)°1024.0(4)1044, 3.480
6.375
multi-scan(Otwinowski et al., 2003)
0.015  0.05  0.10 mm
Nonius KappaCCD system
0.71073, 293
34 mm
f, v, 1
914
370
sphere, 60
13→13, 25→25, 7→7
5072
2619 (Rint = 4.60%)
F2
5.10%, 13.92%
1786 [Fo > 4s (Fo)]
0.0
199
1.056
0.000
1.11, 1.42

815

Table 3. Fractional atomic coordinates and displacement parameters (A2) for lavinskyite-1M. Ueq according to Fischer &Tillmanns (1988).
Atom*

x

y

z

Ueq/Uiso

K
M(1)
M(2)
M(3)
M(4a)
M(4b)
Si(1)
Si(2)
Si(3)
Si(4)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
Oh(12)
Oh(13)

0.0
0.48692(10)0.44601(7)0.39742(8)0.10774(13)0.09800.28234(16)0.25634(16)0.18579(16)0.13786(17)0.5623(4)0.2462(5)0.2138(4)0.7894(4)0.5907(4)0.1685(4)0.1064(4)0.3373(4)0.1178(4)0.2851(4)0.0251(5)0.3791(4)0.4980(4)0.0
0.04036(5)0.37560(4)0.20720(4)0.75060(7)0.79600.64186(9)0.56241(8)0.09385(8)0.17167(8)0.1279(2)0.7234(2)0.6121(2)0.4010(2)0.4535(2)0.0088(2)0.1208(2)0.1191(2)0.3824(2)0.2003(2)0.2707(2)0.4612(2)0.2853(2)0.50.24540(18)0.21827(14)0.19849(14)0.2659(3)0.15700.0527(3)0.5484(3)0.0041(3)0.4929(3)0.4261(8)0.0261(9)0.3086(8)0.1894(8)0.4388(7)0.0126(8)0.2456(8)0.0247(8)0.2340(8)0.4889(8)0.0028(9)0.0492(8)0.3842(7)0.0371(6)0.0141(4)0.0140(3)0.0145(3)0.0133(3)0.050
0.0168(4)0.0165(4)0.0169(4)0.0172(4)0.0185(9)0.0264(10)0.0232(10)0.0240(10)0.0186(9)0.0230(10)0.0225(10)0.0183(9)0.0237(10)0.0214(10)0.0299(11)0.0208(9)0.0176(9)Oxygen atoms of hydroxyl groups are designated as Oh.
*
Reﬁned occupancies of mixed sites: M(1) = Cu0.455(6)Mg0.546(6), M(2) = Cu0.825(6)Mg0.175(6) and M(3) = Cu0.869(6)Mg0.131(6); the occupancies of the Cu [M(4a)] and Li [M(4b)] site were ﬁxed to 0.5 andthe coordinates of the nearly half-occupied, isotropically reﬁned Li
site [M(4b)] were ﬁxed (see text).

Unit-cell parameters were reﬁned from 3003 recorded reﬂections.
Scattering factors for neutral atoms were employed in thereﬁnement.
*
w = 1/[s2(Fo2) þ (0.0787P)2 þ 0.0P]; P = ([max of (0 or Fo2)] þ 2Fc2)/3.

7. Derivation and description of thelavinskyite OD family

in a total positive charge of 1.55þ, very close to the ideal
value of 1.50þ for a 50:50 occupancy. For further details
on the topological environment of these two sites, see thediscussion below.
Prior to the ﬁnal reﬁnement step, the coordinates werestandardised using STRUCTURE TIDY (Gelato & Parthé,1987), and the metal-atom labelling was adopted from thestructure description of lavinskyite-2O (Yang et al., 2014).
Version 1.16 of PLATON (Spek, 2003, 2009) conﬁrmed
the space-group choice and the validity of the structure
model. Detailed information about the crystal data, datacollection and reﬁnement are presented in Table 2.
Table 3 contains atomic coordinates and equivalentisotropic displacement parameters, the anisotropic ones
are given in Table 4 (deposited, i.e. freely available as
Supplementary Material linked to this article on the GSW
website of the journal: https://pubs.geoscienceworld.org/
eurjmin). Selected geometric parameters are provided inTable 5. Due to the meagre amount of available material,
indexed X-ray powder diffraction data (Table 6, deposited)were calculated from the crystal-structure model.

In their original description of lavinskyite, Yang et al.
(2014) stressed the close relationship of lavinskyite with
isostructural plancheite (Evans & Mrose, 1977) andindicated that the only substantial differences are in the
coupled substitutions of Kþ for H2O and Liþ for one halfof the fourfold coordinated Cu2þ. We may add that, as it
happens in plancheite (Merlino, 1997; Ferraris et al.,2004), lavinskyite, too, displays OD (Dornberger-Schiff,
1964, 1966; Ferraris et al., 2004) character.
Lavinskyite is built up by two distinct structural layers,both with translation vectors b, c (b = 19.046, c = 5.2497 A)
regularly alternating in the a0 direction (a0 = 10.1885 A);
note that we have exchanged the a and b directions withrespect to the choice of Yang et al. (2014). The ﬁrst layer isconstituted by the complex TOT block, with brucite-likeCuO2 sheets sandwiched by amphibole-like chains on bothsides, and by Liþ cations (L2n layers, with symmetry P21/c);
the second layer  separated from the previous one by
undulating border-planes  is constituted by half-occupied
ladder-like ribbons of copper atoms in (nearly) square
coordination running along c and by Kþ cations (L2n þ 1layer with layer symmetry Pncm).

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Table 5. Selected geometric parameters (A) for the coordination
polyhedra in lavinskyite-1M.
M(1)–O(5)M(1)–Oh(12)M(1)–O(1)M(1)–O(5)M(1)–Oh(12)M(1)–O(8)<M(1)–O>
M(2)–O(12)M(2)–O(1)M(2)–Oh(13)M(2)–O(8)M(2)–O(5)M(2)–O(10)<M(2)–O>
M(3)–O(10)M(3)–Oh(13)0
M(3)–O(8)M(3)–Oh(13)M(3)–O(10)0
M(3)–O(1)<M(3)–O>
M(4a)–O(11)M(4a)–O(11)M(4a)–O(2)0
M(4a)–O(2)[M(4a)–O(3)][M(4a)–O(4)]<[4]M(4a)–O>
M(4b)–O(11)0
M(4b)–O(2)M(4b)–O(11)M(4b)–O(4)M(4b)–O(2)0<[5]M(4b)–O>

1.966(4)1.974(4)2.056(4)2.063(4)2.282(4)2.409(4)2.125
1.969(4)1.979(4)1.994(4)1.994(4)2.368(4)2.470(4)2.129
1.949(4)1.984(4)
1.999(4)2.038(4)2.356(4)2.531(4)2.143
1.896(4)1.963(4)1.992(4)2.000(4)[2.863(4)][3.063(4)]1.963
1.956(5)2.184(5)2.277(5)2.433(4)2.442(5)2.258

M(4a)–M(4b)1.0410(14)Si(1)–O(2)Si(1)–O(1)Si(1)–O(3)Si(1)–O(4)<Si(1)–O>

1.605(5)1.610(4)1.641(4)1.658(5)1.629

Si(2)–O(5)Si(2)–O(3)Si(2)–O(4)Si(2)–O(6)<Si(2)–O>

1.592(4)1.622(5)1.629(4)1.635(4)1.620

Si(3)–O(7)Si(3)–O(9)Si(3)–O(8)Si(3)–O(6)<Si(3)–O>

1.616(4)1.620(4)1.622(4)1.635(4)1.623

Si(4)–O(11)Si(4)–O(10)Si(4)–O(7)Si(4)–O(9)<Si(4)–O>

1.596(5)1.602(5)1.644(4)1.652(4)1.624

K–O(9)  2
K–O(7)  2
K–O(4)  2
K–O(6)  2
K–O(6)  2[K–O(3)  2]<[10]K–O>

2.808(4)2.897(4)3.061(4)3.144(4)3.145(4)[3.421(4)]3.011

Possible hydrogen bonds
Oh(12) · · · O(9)3.25
Oh(13) · · · O(2)2.89

The fact that the symmetry of the L2n þ 1 layer is higher
than that of L2n layer points to the possibility of polytypic
relationships. In the orthorhombic structure of lavinskyite,
L2n and L2n þ 2 layers are related through the glide
operators [n] (and twofold operator [2]) whichconvert the layer L2n þ 1, lying between them, into itself:
thus the pair (L2n; L2n þ 1) is converted by those operators
into the pair (L2n þ 2; L2n þ 1). However, because of thesymmetry displayed by the L2n þ 1 layer, a different
arrangement is also possible. In this arrangement thelayers L2n and L2n þ 2 are related through the operators [21 ] (and the inversion centres) which convert the layer
L2n þ 1, lying between them, into itself. As in the preceding
case, the pair (L2n; L2n þ 1) is converted by these operations
into the pair (L2n þ 2; L2n þ 1).
Inﬁnite ordered polytypes and disordered structures are
possible, corresponding to the various possible sequencesof operators that may be active in the L2n þ 1 layers. In allof them pairs of adjacent layers are geometricallyequivalent (principle of OD structures). The symmetry
relations common to all the polytypes of the family are
indicated by the OD groupoid family symbol:
Pð2=nÞ 21 =c 2=m
Pð1Þ 21 =c 1
½0:0;  0:0375

:The ﬁrst line presents the layer-group symmetry of the twokinds of layer, whereas the second line presents theirpositional relations, which is done giving in brackets the rand s components of the projection into the layer of thevector connecting the origins of the two subsequent layers(the values of r and s are referred to the basis vectors b andc of the common translation group).
Only one kind of (L2n1; L2n; L2n þ 1) triples exists,
whereas there are two kinds of (L2n; L2n þ 1; L2n þ 2) triples.
Consequently the minimum number of different triples is 2
and only two MDO (Maximum Degree of Order)
polytypes are possible, just corresponding to thosepolytypes presenting the minimum number of different
triples of layers (principle of MDO structures).
In the ﬁrst of them the glide [n] and the twofold axes
[2] are constantly active in the L2n þ 1 layers; thegenerating operation is a glide normal to c withtranslational component a0; the constant application ofthis operation generates an orthorhombic structure withbasis vectors a = 2a0, b, c and space-group symmetryPnca, corresponding to the type lavinskyite studied by
Yang et al. (2014) after the exchange of a and b vectors:
the [a] glide corresponds to the generating operation,
the [ c ] glide is the common symmetry element of both
OD layers, the [n] mirror of the L2n þ 1 layers is valid
for the whole structure.
In the second MDO structure the operators [ 21 ] andinversion centres are constantly active in the L2n þ 1 layer.
The generating operation is the translation t = a0 þ 2sc(s = 0.0375). The continuation of this operation gives rise
to a monoclinic polytype with space-group symmetry P21/cand basis vectors
a = a0 þ 2sc, b, c (a = 10.196, b = 19.046,

c = 5.2497 A, b = 92.22°). These unit-cell parameters areclosely similar to those obtained by Kolitsch et al. (2014)
for the originally approved “liguriaite”(IMA 2014-035):
a = 10.224, b = 19.085, c = 5.252 A, b = 92.23°.

8. Description of the crystal structure
A comparison of the crystal structures of lavinskyite-1M
and lavinskyite-2O along two major axes is given in Fig. 3.
The asymmetric unit of lavinskyite-1M contains three (Cu,Mg) [M(1), M(2), M(3)], one split Cu/Li [M(4)], one K,
four Si, 13 O and two H sites (the latter could not belocated). All atoms are in general positions except K which
is located at (0, 0, 0.5). The atomic arrangement oflavinskyite-1M (Fig. 3a, b) is best described as a sheet
structure consisting of corrugated brucite-like (CuO2)nlayers with amphibole-type (SiO3)n chains joined to boththeir upper and lower surfaces. Adjacent complex sheets

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Lavinskyite-1M from the Cerchiara manganese mine

817

Fig. 3. Comparison of the crystal structures of lavinskyite-1M (bottom part) and lavinskyite-2O (top part). (a) View parallel to the corrugatedbrucite-like (CuO2)n layers, along c; (b) view perpendicular to the layers, along b (lavinskyite-2O) and a (lavinskyite-1M). Distorted MO6(M = Cu, Mg) octahedra are green; the split M(4) site in both polytypes is represented by a green Cu sphere and a turquoise Li sphere, both shownwith bonds in part (a) of the ﬁgure; SiO4 tetrahedra are white and marked with crosses; K atoms are shown as dark blue spheres and H atoms as
small grey spheres. The unit cells are outlined. Drawings done using ATOMS version 6.3 (Shape Software, 2006).(Online version in color)

are linked by [5]-coordinated Li atoms and Cu atoms insquare coordination (nearly planar) and interlayer K
atoms. The K site is fully occupied by K.
The three (Cu,Mg) sites M(1), M(2) and M(3) show
reﬁned occupancies of Cu0.455(6)Mg0.546(6), Cu0.825(6)Mg0.175(6) and Cu0.869(6)Mg0.131(6), respectively. Although
the reﬁnement suggests that Mg is very slightly dominant at
the M(1) site, the true experimental error of the reﬁned Cu:
Mg ratio is certainly higher (both the omission of several
poorly ﬁtting low-angle reﬂections and the treatment of the
split M4 site had a large impact on this ratio, for example)
and, consequently, there is no unambiguous proof for thedominance. The split Cu/Li [M(4)] site shows ideal
occupancies of 0.5 for both Cu [M(4a)] and Li [M(4b)].
The same ideal occupancies characterise lavinskyite-2Oto(Yang et al., 2014), in which M(4a)–M(4b) ∼0.9 A, similarthe equivalent distance in lavinskyite-1M, 1.0410(14) A.
From a purely topological point of view, the position of
the Li atom in lavinskyite-1M was found to be very close
to that in lavinskyite-2O (Yang et al., 2014). To quantify
this closeness, detailed MDO-geometrical calculations
were performed to obtain the coordinates of atoms inlavinskyite-1M from those in lavinskyite-2O (for details
see Appendix in Supplementary Material). The calculated
Li-atom coordinates (0.102, 0.792, 0.154) are very near to
those foundindependently and then reﬁned with ﬁxed Uisoof 0.05 A2 and freely reﬁned occupancy: 0.098(4), 0.796(2), 0.157(8). As mentioned above, the freely reﬁned Liatom occupancy in lavinskyite-1M is 0.36(3), reasonably
close to the ideal value of 0.5, considering the low electron
density involved and the imperfect quality of the dataset.
The Li atom has ﬁve O ligands within a Li–O bond-length
range of 1.96–2.44
A (sixth and seventh neighbours wouldboth be at 2.83 A). The coordination is thus somewhat
different from that in lavinskyite-2O, in which the Li atomshows a markedly distorted octahedral coordination, with
Li–O bonds ranging from 1.91 to 2.70 A. The coordinationof the Li atom in both lavinskyite-1M and 2O is within
the range reported for Liþ (coordination numbers 3–8;
Wenger & Armbruster, 1991). The Cu [M(4a)] site inlavinskyite-1M displays a distorted (nearly) planar fourcoordinated environment very similar to that in lavinskyite-2O. The mentioned small differences in Li coordination number (six in lavinskyite-2O vs. ﬁve in lavinskyite1M), in Li:Cu ratios and (Cu,Mg) site occupancies arethought to be the main reasons for the slight monoclinic
lattice distortion of the 1M polytype (deviation fromorthogonality ∼2.2°).
Lavinskyite-1M thus has the same topology as
orthorhombic lavinskyite-2O [K(LiCu)Cu6(Si4O11)2(OH)4, Pcnb (Yang et al., 2014, this work)], which isisostructural with plancheite (Evans & Mrose, 1977). The
close relation between lavinskyite-1M and lavinskyite-2O
is also evident from their unit-cell parameters:

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U. Kolitsch et al.

Table 7. Comparison of physico-chemical data for lavinskyite-1M, lavinskyite-2O and plancheite.
MineralLavinskyite-1M

Ref.
This work
FormulaK(Li,Cu)Cu6(Si4O11)2(OH)4
Empirical formulae (K1.08)S1.08(Li0.89Mg0.36Cu0.33Na0.22(both based on
Mn2þ0.04)S1.84Cu6.00Si8.08O22(OH)4.02
26 O apfu)
and(K1.08)S1.08(Li0.89Cu0.33Mg0.28
Na0.22Mn2þ0.04)S1.76Cu6.00Si8.09O22(OH)4.14
Symmetry
Monoclinic
Space
group
P21/c

a (A )
10.224(2)b (A)
19.085(4)
5.252(1)c (A)b (°)
92.23(3)V (A3)
1024.0(4)Z2
10.216 (100), 9.007 (20),
8 strongest lines
4.934 (19), 3.983 (19),in the powder
3.353 (33), 2.869 (22),pattern2.616 (35), 2.372 (23)D(meas.); (calc.)n.d.; 3.613 (Dx 3.526)
Mohs hardness∼5a1.674(2)b1.692(3)g1.730(3)Birefringence
0.056
Opt. character2 (þ)
2V (meas.); (calc.) ∼75°; 70°
Dispersion
None
Orientation
X ^ a ∼ 20° (in obtuse beta?), Y = b, Z ∼ cElongation
Positive
X (colour)(Pale) blue
Y (colour)
Pale blue
Z (colour)
Pale blue with faintgreenish tint
Absorption
X≥Z≥Y
Megascopic colour Bluish, pale blue
LustreStreakHabit
Twinning
Cleavage
Fracture*

Vitreous
Very pale blue to white
Tabular (100), elongated [001]None observed
Perfect {100}UnevenLavinskyite-2O

Plancheite

Yang et al. (2014), this work
Evans & Mrose (1977)
K(LiCu)Cu6(Si4O11)2(OH)4
Cu8(Si4O11)2(OH)4 · H2O(K0.99Ba0.01)S1.00(Li1.04Cu0.93Na0.10)S2.07 –(Cu5.57Mg0.43Mn0.01)S6.01(Si4.00O11)2(OH)4

Orthorhombic
Pcnb
19.046(2)20.377(2)5.2497(6)Orthorhombic
Pcnb
19.043(3)20.129(5)5.269(1)2037.4(4)4
10.189 (100), 8.984 (17),4.921 (25), 3.973(19), 3.343 (32), 2.693(29), 2.522 (27), 2.316 (22)
3.61(3); 3.62
∼51.675(1)1.686(1)1.715(1)
0.040
2 (þ)
64(4)°; 64.2°
n.g.
X = a, Y = b, Z = cn.g.
Dark blue
Light blue
Light blue

2019.74
10.11 (100), 9.56 (40), 6.94(70), 4.87 (50), 4.06 (85),
3.95 (40), 3.31 (40)X>Y=ZLight blue
Vitreous
Very pale blue
Tabular (010), elongated [001]None observed
Perfect {010}
Uneven3.65-3.80; (Dx 3.815)
6
1.697
1.718
1.741
0.044
2 (þ)
n.d.; 88.5°
n.g.
X = c, Y = b, Z = a
Positive
Very pale blue
Blue
Blue
Z>X>Y
Pale blue to deep blue,
pale greenish blue
SatinyLight blue
Fibrous [001]None observed
n.g.
n.g.

Plancheite: Data from Handbook of Mineralogy (http://rruff.info/doclib/hom/plancheite.pdf) and Lacroix (1908).

Lavinskyite-1M:
a = 10.224(2), b = 19.085(4), c = 5.252
(1) A, b = 92.23(3)0, V = 1024.0(4) A3.
Lavinskyite-2O:
a = 19.046(2),b = 20.377(2),c = 5.2497(6) A, V = 2037.4(4) A3.
The comparison shows that aL1MsinbL1M ∼ 0.5bL2O,
bL1M ∼ aL2O, cL1M ∼ cL2O and VL1M ∼ 0.5VL2O.
Lavinskyite-1M and lavinskyite-2O have nearly thesame empirical formula: (K1.08)S1.08(Li0.89Mg0.36Cu0.33
Na0.22Mn2þ0.04)S1.84Cu6.00Si8.08O22(OH)4.02 and (K0.99
Ba0.01)S1.00(Li1.04Cu0.93Na0.10)S2.07(Cu5.57Mg0.43Mn0.01)
S6.01(Si4.00O11)2(OH)4, respectively. The chemical formulaobtained from the structure reﬁnement of lavinskyite-1M(neglecting the minor Na and the trace amounts of Mn) is: K(LiCu)S2(Cu4.41Mg1.59)S6(Si4O11)2(OH)4. This formula isin fairly good agreement with the empirical ones,
considering that the studied crystal fragment was notanalysed chemically and the Na content, neglected in thereﬁnement, might be distributed among several of the four Msites. The chemically analysed lavinskyite-1M fragments
contain less Mg (0.36 apfu for Cerch1 and 0.28 apfu for
Cerch2) and are somewhat closer to the end-member
composition.

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Lavinskyite-1M from the Cerchiara manganese mine

The question arises why lavinskyite-1M occurs at the
Cerchiara mine and not lavinskyite-2O? The latter appears
to be denser, but a complex and delicate interplay between
the Li:Cu and Cu:Mg ratios, along with an additional
inﬂuence of impurity cations such as Na and different
conditions of formation (mainly P, T) may result in astabilisation of the 1M polytype.
A detailed comparison of the physico-chemical properties of lavinskyite-1M, lavinskyite-2O and plancheite isgiven in Table 7. The X-ray powder diffraction patterns ofboth polytypes (Table 6, deposited) are similar, especiallyin the low-angle region, but distinct differences exist at
higher diffraction angles and can be used for identiﬁcation.
We point out that, if the hypothetical P21/c MDO
equivalent of plancheite (Merlino, 1997) would be foundin nature, this would entail a necessary name change toplancheite-1M and plancheite-2O.
Finally, we note that shattuckite [Cu5(SiO3)4(OH)2,
Evans & Mrose, 1977; Kawahara, 1976] has a similar
sheet-based crystal structure as the two lavinskyite
polytypes and plancheite, but its brucite-like (CuO2)nlayers have clinopyroxene-type silicate chains joined tothem, not amphibole-type chains.
Acknowledgements: The authors thank Fabrizio Castellaro, who found the mineral, for providing samples forstudy. We also thank Corrado Balestra for some
information on the occurrence of the lavinskyite-1M
specimens. The article beneﬁted from valuable reviews by
two anonymous referees, and editoral assistance by Sergey
Krivovichev.

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Received 3 May 2017
Modiﬁed version received 18 June 2017
Accepted 20 June 2017

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