Mineralogical Magazine, August 2017, Vol. 81(4), pp. 753–779

Klaprothite, péligotite and ottohahnite, three new minerals
with bidentate UO7–SO4 linkages from the Blue Lizard mine,
San Juan County, Utah, USA
ANTHONY R. KAMPF1,*, JAKUB PLÁŠIL2, ANATOLY V. KASATKIN3, JOE MARTY4 AND JIŘÍ ČEJKA5
1

Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard,
Los Angeles, CA 90007, USA
2
Institute of Physics ASCR, v.v.i., Na Slovance 1999/2, 18221 Prague 8, Czech Republic
3
Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninsky Prospekt, 18-2, 119071,
Moscow, Russia
45199 East Silver Oak Road, Salt Lake City, UT 84108, USA
5
Department of Mineralogy and Petrology, National Museum, Cirkusová 1740, 193 00, Prague 9, Czech Republic[Received 20 April 2016; Accepted 16 May 2016; Associate Editor: G. Diego Gatta]
ABSTR ACTThe new minerals klaprothite (IMA2015-087), Na6(UO2)(SO4)4(H2O)4, péligotite (IMA2015-088),
Na6(UO2)(SO4)4(H2O)4 and ottohahnite (IMA2015-098), Na6(UO2)2(SO4)5(H2O)7·1.5H2O, were foundin the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary phases. All
three minerals occur as yellowish-green to greenish-yellow crystals, are brittle with irregular fracture, haveMohs hardness of ∼2½ and exhibit bright bluish-green fluorescence, and all are easily soluble in roomtemperature H2O. Only klaprothite exhibits cleavage; perfect on {100} and {001}. Quantitative energydispersive spectroscopy analyses yielded the empirical formulas Na6.01(U1.03O2)(S0.993O4)4(H2O)4,
Na5.82(U1.02O2)(S1.003O4)4(H2O)4 and Na5.88(U0.99O2)2(S1.008O4)5(H2O)8.5 for klaprothite, péligotite andottohahnite, respectively. Their Raman spectra exhibit similar features. Klaprothite is monoclinic, P21/c,
a = 9.8271(4), b = 9.7452(3), c = 20.8725(15) Å, β = 98.743(7)°, V = 1975.66(17) Å3 and Z = 4. Péligotite is
triclinic, P1, a = 9.81511(18), b = 9.9575(2), c = 10.6289(8) Å, α = 88.680(6)°, β = 73.990(5)°, γ = 89.205(6)°,V = 998.22(8) Å3 and Z = 2. Ottohahnite is triclinic, P1, a = 9.97562(19), b = 11.6741(2), c = 14.2903(10)Å, α = 113.518(8)°, β = 104.282(7)°, γ = 91.400(6)°, V = 1464.59(14) Å3 and Z = 2. The structures ofklaprothite (R1 = 2.22%) and péligotite (R1 = 2.28%) both contain [(UO2)(SO4)4]6– clusters in which one
SO4 group has a bidentate linkage with the UO7 polyhedron; Na–O polyhedra link clusters into thickheteropolyhedral layers and link layers into frameworks; the structures differ in the configuration of Na–O
polyhedra that link the layers. The structure of ottohahnite (R1 = 2.65%) contains [(UO2)4(SO4)10]12–
clusters in which each UO7 polyhedron has a bidentate linkage with one SO4 group; Na–O polyhedra link
clusters into a thin heteropolyhedral slice and also link the slices into a framework. The minerals are
named for Martin Heinrich Klaproth (1743–1817), Eugène-Melchior Péligot (1811–1890) and Otto Hahn
(1879–1968).
K E Y WO R D S : klaprothite, péligotite, ottohahnite, new mineral, uranyl sulfate, crystal structure, Blue Lizard mine,Utah, USA.
Introduction*E-mail: akampf@nhm.org
https://doi.org/10.1180/minmag.2016.080.120© 2017 The Mineralogical Society

IN the last few years, the Blue Lizard uranium minein southeast Utah has proven to be a prolific sourceof new minerals, especially sodium uranyl sulfates(Table 1). To date, our investigations have yieldedTABLE 1. New uranyl sulfate minerals from the Blue Lizard mine, arranged by their charge deficiency per anion (CDA), and including their molar proportions of
H2O, S and U.
Structural formula

Shumwayite*
Plášilite
Alwilkinsite-(Y)Bobcookite
Wetherillite
Oppenheimerite
Ottohahnite
Fermiite
Meisserite
Klaprothtite
Péligotite
Bluelizardite
Belakovskiite[(UO2)(SO4)(H2O)2]2·H2O
Na(H2O)2[(UO2)(SO4)(OH)]
Y(H2O)7[(UO2)3(SO4)2O(OH)3](H2O)7
Na(H2O)2Al(H2O)6[(UO2)2(SO4)4(H2O)2]·8H2O
Na2(H2O)6(Mg,Zn)(H2O)6[(UO2)2(SO4)4(H2O)2]·4H2O
Na2(H2O)2[(UO2)(SO4)2(H2O)]
Na6(H2O)7[(UO2)2(SO4)5](H2O)2
Na4(H2O)3[(UO2)(SO4)3]Na5(SO3OH)(H2O)[(UO2)(SO4)3]
Na6(H2O)4[(UO2)(SO4)4]
Na6(H2O)4[(UO2)(SO4)4]
Na7Cl(H2O)2[(UO2)(SO4)4]
Na7(SO3OH)(H2O)3[(UO2)(SO4)4(H2O)]

CDA (vu)

mol. H2O (%)

mol. S (%)

mol. U (%)

0.10
0.17
0.20
0.22
0.22
0.22
0.25
0.29
0.29
0.33
0.33
0.33
0.34

0.56
0.45
0.72
0.69
0.67
0.38
0.41
0.27
0.13
0.27
0.27
0.13
0.21

0.22
0.18
0.09
0.15
0.15
0.25
0.23
0.27
0.35
0.27
0.27
0.27
0.30

0.22
0.18
0.14
0.08
0.07
0.13
0.09
0.09
0.09
0.07
0.07
0.07
0.06

Reference
Kampf et al. (2017b)
Kampf et al. (2015a)
Kampf et al. (2017a)
Kampf et al. (2015b)
Kampf et al. (2015b)
Kampf et al. (2015c)
This study
Kampf et al. (2015c)
Plášil et al. (2013)This study
This study
Plášil et al. (2014)
Kampf et al. (2014)*The type localities for shumwayite are the Giveaway-Simplot mine and the Green Lizard mine, but it has also been found at the Blue Lizard mine.
vu – valence units.

ANTHONY R. KAMPF ET AL.

754

MineralKLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

FIG. 2. Crystal drawing of klaprothite; clinographic
projection in nonstandard orientation, b vertical.

each of which subsequently resulted in a discreditation. The most recent discreditation occurred in
1947, when klaprotholite was shown to be a
mixture of wittichenite and emplectite. We thinkthat sufficient time has passed to again propose thenaming a new mineral in honour of this pioneer inanalytical chemistry and mineralogy.
Péligotite (/′pe li gou tait/) is named in honour of
the French chemist Eugène-Melchior Péligot(1811–1890), who isolated the first sample ofuranium metal in 1841 and proved that the material

FIG. 1. Klaprothite in incandescent light (top) and in
405 nm light (bottom); field of view = 1 mm across.

eight new uranyl sulfate minerals, belakovskiite,
bluelizardite, fermiite, meisserite, oppenheimerite,
plášilite, bobcookite and wetherillite. The ninth,
tenth and eleventh new uranyl sulfates from thismine, klaprothite, péligotite and ottohahnite, aredescribed herein. These three minerals, which
occur in association with one another, are the first
three minerals with structures containing bidentate
linkages (shared edges) between UO7 pentagonal
pyramids and SO4 tetrahedra. The twelfth new
uranyl sulfate from the Blue Lizard mine, alwilkinsite-(Y) will be described in a subsequent paper
and another new one occurring here, shumwayite,
was recently described from the nearby Green
Lizard and Giveaway-Simplot mines.
Klaprothite (/′klæp rout ait/) is named in honourof German chemist Martin Heinrich Klaproth(1743–1817), the discoverer of uranium (1789),
zirconium (1789) and cerium (1803). It should be
noted that the material that Klaproth identified as a
new element and named uranium was actually anoxide of the element. There have been several
previous attempts to name a mineral for Klaproth,

FIG. 3. Péligotite with tamarugite (white); field ofview = 1.1 mm across.

755

ANTHONY R. KAMPF ET AL.

Angeles County, 900 Exposition Boulevard, Los
Angeles, CA 90007, USA, have the catalogue
numbers 65610 (cotype for klaprothite, péligotite
and ottohahnite), 65611 (cotype for klaprothite andottohahnite), 65612 (cotype for klaprothite), 65613(cotype for klaprothite), 65614 (cotype for
péligotite and ottohahnite), 65615 (cotype for
péligotite), 65616 (cotype for péligotite) and
65617 (cotype for ottohahnite). One cotype foreach mineral is housed in the collections of theFersman Mineralogical Museum of the Russian
Academy of Sciences, Moscow, Russia, registration
number 4778/1 (klaprothite), 4779/1 (péligotite)
and 4782/1 (ottohahnite).

FIG. 4. Crystal drawing of péligotite; clinographic
projection in standard orientation.

described by Klaproth as the element in 1789 was
actually an oxide of uranium.
Ottohahnite (/au tOu ′ha:n ait/) is named inhonour of German chemist Otto Hahn (1879–1968)
who discovered nuclear fission (of uranium) in
1938, for which he received the Nobel Prize in
Chemistry. The compound name is proposed to
avoid the possible confusion of ‘hahnite’ withseveral other mineral names, i.e. hainite, gahnite
and cahnite. In particular, in Russian, the pronunciation of hahnite would be essentially the same asthat of gahnite.
The new minerals and their names were approvedby the Commission on New Minerals, Nomenclature
and Classification of the International Mineralogical
Association: klaprothite (IMA2015-087), péligotite(IMA2015-088) and ottohahnite (IMA2015-098).
The description of each mineral is based on fivecotype specimens. Those deposited in the collections of the Natural History Museum of Los

Occurrence

FIG. 5. Ottohahnite with tamarugite (white); field ofview = 0.7 mm across.

756

Klaprothite, péligotite and ottohahnite were foundunderground in the Blue Lizard mine, Red Canyon,
White Canyon District, San Juan County, Utah,
USA (37°33′26″N 110°17′44″W). The Blue Lizard
mine is located ∼72 km west of the town ofBlanding, Utah and ∼22 km southeast of Good
Hope Bay on Lake Powell. It is on the north side of
Red Canyon and close to the Markey mine.
Information on the history and geology of thedeposit is taken largely from Chenoweth (1993).
The deposit was first recognized in the summerof 1898 by John Wetherill, while leading anarchaeological expedition into Red Canyon. He
noted yellow stains around a petrified tree. At that
spot, he built a rock monument, in which he placeda piece of paper to claim the minerals. Although henever officially recorded his claim, 45 years later, in
1943, he described the spot to Preston V. Redd ofBlanding, Utah, who went to the site, foundWetherill’s monument and claimed the area as theBlue Lizzard claim (note alternate spelling).
Underground workings to mine uranium were notdeveloped until the 1950s.
Mineralized channels are in the Shinarump
member of the Chinle Formation. The Shinarump
member consists of medium- to coarse-grainedsandstone, conglomeratic sandstone beds and thicksiltstone lenses. Ore minerals were deposited as
replacements of wood and other organic material
and as disseminations in the enclosing sandstone.
Since the mine closed in 1978, hydration-oxidation
weathering of primary uranium minerals, mainly
uraninite, by acidic solutions derived from thedecomposition of associated sulfides such as pyrite,
marcasite and chalcopyrite in the humid underground environment has produced a variety ofKLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

FIG. 6. The Raman spectra of klaprothite, péligotite and ottohahnite measured with a 532 nm laser.

secondary minerals, mainly sulfates, as efflorescentcrusts on the surfaces of mine walls.
The new minerals are rare in the secondary uranyl
sulfate mineral assemblage. Other secondary minerals found in direct association with klaprothite,
péligotite and ottohahnite include blödite, bluelizardite, bobcookite, epsomite, gypsum, hexahydrite, konyaite, plášilite and tamarugite. The bulk of
the matrix is comprised of subhedral to euhedral,equant quartz crystals that are recrystallized counterparts of the original grains of the sandstone. Other
minerals remaining from the original sandstone
include feldspar and rare almandine and zircon.
Minerals related to the ore deposition include baryte,
bornite, chalcopyrite, covellite, pyrite and uraninite.
Other secondary minerals in the general assemblage
include aluminocoquimbite, alwilkinsite-(Y),atacamite, belakovskiite, boyleite, brochantite,
calcite, chalcanthite, cobaltoblödite, copiapite,
coquimbite, cyanotrichite, d’ansite-(Mn), dickite,dietrichite, fermiite, ferrinatrite, gerhardtite,gordaite, halite, johannite, kaolinite, kieserite,
kröhnkite, lishizhenite, manganoblödite, meisserite,
metavoltine,
natrozippeite,
oppenheimerite,
pickeringite,
pseudojohannite,rhomboclase,römerite, rozenite, sideronatrite, shumwayite,thérèsemagnanite, wetherillite and other potentially
new minerals currently under investigation.
757

A detailed discussion of the origin and conditions of formation of the uranyl sulfate assemblages
at the Blue Lizard mine was provided by Plášil et al.
(2014). The minerals formed at ambient temperature by evaporative processes at the surface of arock with high relative porosity. The environment isrelatively oxidizing (high Eh) and solutions are
generally acidic (low pH). The relative acidity
prevalent during the formation of any given phasecan be interpreted from its charge deficiency peranion (CDA) calculated using the bond-valence
approach (cf. Hawthorne and Schindler, 2008;
Hawthorne, 2012); higher CDA correlates withhigher pH. The molar proportions of S and U in theformulas are indicative of the relative concentrations of these elements in solution during formationand the molar proportion of H2O can be expected toincrease with the relative humidity (RH) duringformation. Table 1 provides the CDA and molar
proportions of H2O, S and U for each of the newuranyl sulfates found at the Blue Lizard mine.
Klaprothite and péligotite are likely to have formed
from less acidic solutions than did ottohahnite, andmost of the other uranyl sulfates at the Blue Lizard
mine. Klaprothite and péligotite are presumed tohave formed under relatively low RH, while
ottohahnite is likely to have formed at moderate
RH. The molar proportions of S and U for these

ANTHONY R. KAMPF ET AL.

TABLE 2. Chemical analyses (in wt.%) for klaprothite, péligotite and ottohahnite.
Klaprothite

Na2O
UO3
SO3
H2O
Total

Péligotite

Ottohahnite

Mean

Range

S.D.

Mean

Range

S.D.

Mean

Range

S.D.

21.06
33.14
35.93
8.15*
98.28

19.67–22.85
31.07–36.92
33.15–38.40

1.08
1.82
1.38

20.55
33.27
36.60
8.22*
98.64

18.98–22.56
29.61–38.14
33.88–39.20

1.46
3.53
1.88

13.73
42.68
30.44
11.55§
98.40

12.92–15.66
41.01–44.39
28.86–31.45

0.84
0.99
0.97

S.D. – standard deviation.
*Calculated by stoichiometry on the basis of 22 O apfu.
§
Calculated by stoichiometry on the basis of 32.5 O apfu.

phases, with mol. S >> mol. U, suggest that they
formed relatively far from the source of U (uraninite).

Péligotite
Péligotite crystals are generally equant relatively
simple rhombs (Figs 3 and 4), up to ∼0.5 mm in
maximum dimension, but usually much smaller.
Crystal faces often are concave with rounded edges,
suggestive of incomplete growth or later dissolution/
deliquescence. Crystals typically occur in subparallel aggregates and drusy intergrowths.
Crystals exhibit the forms {001}, {110} and{110}; more complex forms are probably present,
but are difficult to measure because crystals occur
in tight intergrowths. No twinning was observed.
Crystals are yellow green and transparent with avitreous lustre. The streak is pale yellow green. The
mineral fluoresces bright bluish green under both
longwave and shortwave ultraviolet light. The Mohs
hardness is ∼2½. Crystals are brittle (slightly sectile)
with no cleavage and have irregular fracture. The
mineral is slightly deliquescent and is easily soluble
in room-temperature H2O. The density measured byflotation in a mixture of methylene iodide andacetone is 2.88(2) g cm–3. The calculated densitiesare 2.878 g cm–3 based on the empirical formulaand 2.875 g cm–3 based on the ideal formula.
Optically, péligotite is biaxial (–) with 1.493(1),β = 1.511(1), γ = 1.515(1) (measured in whitelight). The 2V measured directly on a spindle
stage is 50(1)°; the calculated 2V is 50.0°.
Dispersion is r > v, distinct. Pleochroism is X =colourless, Y = light yellowish green, Z = lightyellowish green; X < Y ≈ Z. The optical orientation
is X ∧ c = 3°, Y ∧ b = 43°, Z ∧ a = 40°.

Physical and optical properties
Klaprothite
Klaprothite crystals are equant to prismatic (Figs 1
and 2), up to ∼1 mm in maximum dimension, but
usually much smaller. Crystal faces often are
skeletal with rounded edges, suggestive of incomplete growth or later dissolution/deliquescence.
Crystals typically occur in parallel intergrowths
with surfaces made up of many stepped faces.
Prisms are elongated on [010] and crystals exhibit
the forms {100}, {001}, {110}, {011} and {012}.
No twinning was observed.
Crystals are yellow green and transparent with avitreous lustre. The streak is pale yellow green. The
mineral fluoresces bright bluish green under both
longwave and shortwave ultraviolet light. The
Mohs hardness is ∼2½. Crystals are brittle (slightly
sectile) with perfect cleavages on {100} and {001}and have irregular fracture. The mineral is slightly
deliquescent and is easily soluble in roomtemperature H2O. The density measured by flotation in a mixture of methylene iodide and acetone
is 2.90(2) g cm–3. The calculated densities are
2.923 g cm–3 based on the empirical formula and2.905 g cm–3 based on the ideal formula.
Optically, klaprothite is biaxial (–) with α =1.497(1), β = 1.517(1), γ = 1.519(1) (measured inwhite light). The 2V measured directly on aspindle stage is 34(1)°; the calculated 2V is
34.7°. Dispersion is r > v, distinct. Pleochroism is
X = colourless, Y = light yellowish green, Z = lightyellowish green; X < Y ≈ Z. The optical orientation
is Y = b, X ∧ c = 10° in obtuse angle β.

Ottohahnite

758

Ottohahnite crystals are generally equant (Fig. 5),
up to ∼0.1 mm in maximum dimension, but

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALSTABLE 3. Powder X-ray data for klaprothite, péligotite and ottohahnite.

usually much smaller. Crystal faces and edges areoften rounded, suggestive of incomplete growthor later dissolution/deliquescence. Crystals are
typically intergrown with tamarugite. No crystals
forms could be measured. No twinning wasobserved.
Crystals are green yellow and transparent with avitreous lustre. The streak is pale green yellow. The
mineral fluoresces bright bluish green under both759

longwave and shortwave ultraviolet light. The
Mohs hardness is ∼2½. Crystals are brittle (slightly
sectile) with no cleavage and have irregular
fracture. The mineral is slightly deliquescent andis easily soluble in room-temperature H2O. The
small size and difficulty of separating crystals fromtheir intergrowths with tamarugite made themeasurement of the density impractical. The
calculated densities are 2.858 g cm–3 based on

ANTHONY R. KAMPF ET AL.

TABLE 3. (contd.)the empirical formula and 2.973 g cm–3 based on
the ideal formula.
Optically, ottohahnite is biaxial (–) with α =1.511(1), β = 1.514(1), γ = 1.537(1) (measured inwhite light). The 2V measured directly on aspindle stage is 42(2)°; the calculated 2V is 40.2°.
Dispersion is r > v, strong. Pleochroism is X = lightyellowish green, Y = colourless, Z = yellowish

green; Y < X < Z. The optical orientation is X ∧ a= 43°, Y ∧ b = 11°, Z ∧ c = 29°.
Raman spectroscopy

760

The Raman spectra of klaprothite, péligotite andottohahnite were recorded on a Thermo-Scientific
DXR Raman microscope interfaced to an Olympus

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALSTABLE 3. (contd.)

Only calculated lines with I > 2 are shown.
The data in these three tables are also deposited with the Principal Editor of Mineralogical Magazine and areavailable from http://www.minersoc.org/pages/e_journals/dep_mat_mm.html.

microscope (objective 50×). The spectrometer wascalibrated by a software-controlled calibration
procedure (within Omnic 8 software) using multiple neon emission lines (wavelength calibration),
multiple polystyrene Raman bands (laser frequency
calibration), and standardized white light sources(intensity calibration). Spectral manipulation suchas background correction and band-component

analysis was done with Omnic 8 software. Spectraof all three minerals are displayed in Fig. 6.

OH stretching and H 2O bending vibrations

761

The bands attributable to the O–H stretchingvibrations were observed for all three minerals, inTABLE 4. Data collection and structure refinement details for klaprothite, péligotite and ottohahnite.
Péligotite

Ottohahnite

Structural formulaSpace group
Unit-cell dimensions

Na6(UO2)(SO4)4(H2O)4
P21/c
a = 9.8271(4) Å
b = 9.7452(3) Åc = 20.8725(15) Å
β = 98.743(7)°VZ
Density (for above formula)
Absorption coefficientF(000)
Crystal size (μm)
θ range
Index ranges

1975.66(17) Å3
4
2.906 g·cm–3
8.877 mm–1
1624
80 × 60 × 30
3.02 to 27.49°–12 ≤ h ≤ 12
–12 ≤ k ≤ 12
–27 ≤ l ≤ 27
23,627/4507; Rint = 0.035
4034
99.5%
12/325
1.098
R1 = 0.0222, wR2 = 0.0455
R1 = 0.0271, wR2 = 0.0470+1.09/–0.86 e A–3

Na6(UO2)(SO4)4(H2O)4
P1
a = 9.81511(18) Åb = 9.9575(2) Åc = 10.6289(8) Å
α = 88.680(6)°β = 73.990(5)°γ = 89.205(6)°998.22(8) Å322.875 g·cm–3
8.784 mm–1
812
60 × 45 × 25
3.20 to 27.44°–12 ≤ h ≤ 11
–12 ≤ k ≤ 12
–13 ≤ l ≤ 13
17,794/4512; Rint = 0.039
4146
99.1%
12/3251.089
R1 = 0.0228, wR2 = 0.0490
R1 = 0.0273, wR2 = 0.0506+1.14/–0.67 e A–3

Na6(UO2)2(SO4)5(H2O)7·1.5H2O
P1
a = 9.97562(19) Åb = 11.6741(2) Åc = 14.2903(10) Å
α = 113.518(8)°β = 104.282(7)°γ = 91.400(6)°1464.59(14) Å3
2
2.978 g·cm–3
11.611 mm–1
1216
80 × 60 × 50
3.00 to 27.44°–11 ≤ h ≤ 12
–15 ≤ k ≤ 15
–18 ≤ l ≤ 18
26,283/6658; Rint = 0.041
5721
99.6%
0/425
1.040
R1 = 0.0265, wR2 = 0.0581
R1 = 0.0341, wR2 = 0.0610+1.35/–1.38 e A–3

Reflections collected; unique
Reflections with Fo > 4σ(F )Completeness to θmax
Restraints/parameters
Goof
Final R indices [Fo > 4σ(F )]R indices (all data)
Largest diff. peak/hole*Rint = Σ|Fo2–Fo2(mean)|/Σ[Fo2]. Goof = S = {Σ[w(Fo2–F2c )2]/(n–p)}1/2. R1 = Σ||Fo|–|Fc||/Σ|Fo|. wR2 = {Σ[w(Fo2–F2c )2]/Σ[w(Fo2)2]}1/2; w = 1/[σ2(Fo2) + (aP)2 + bP] where P is
[2F2c + Max(Fo2,0)]/3; for klaprothite a is 0.0153 and b is 5.0943; for péligotite a is 0.2090 and b is 1.0734; for ottohahnite a is 0.0288 and b is 2.1310.

ANTHONY R. KAMPF ET AL.

762

KlaprothiteTABLE 5. Atom coordinates and displacement parameters (Å2) for klaprothite, péligotite and ottohahnite.

763

Na1
Na2
Na3
Na4
Na5
Na6
Na7
U
S1
S2
S3
S4
O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
OW1
H1a
H1b
OW2

x/a

y/b

z/c

Ueq

U 11

U 22

U 33

U 23

U 13

U 12

0.90437(17)0.26877(17)0.30983(19)0.40612(17)0.3506(2)0.0
0.5
0.99601(2)0.66470(9)0.16743(10)0.26752(9)0.22619(9)0.3707(3)0.5873(3)0.6440(3)0.8155(3)0.1284(4)0.8981(3)0.3169(3)0.8771(3)0.2088(3)0.3031(3)0.3860(3)0.1596(3)0.2590(3)0.3122(3)0.0770(3)0.2383(3)0.0502(3)0.9439(3)0.8704(4)0.937(5)0.880(6)0.4328(3)0.30192(16)0.23763(17)0.22928(17)0.81668(16)0.62409(19)0.5
0.5
0.20230(2)0.53766(9)0.04653(9)0.45861(9)0.49007(9)0.0712(3)0.6234(3)0.3917(3)0.5630(3)0.0692(4)0.6436(3)0.0514(3)0.4064(3)0.5943(3)0.4250(3)0.4425(3)0.3577(3)0.4444(3)0.4266(3)0.4683(3)0.6437(3)0.2256(3)0.1845(3)0.2477(6)0.203(5)0.317(4)0.7935(3)0.89756(8)0.75503(8)0.99039(8)0.90064(8)0.74617(9)0.5
00.60250(2)0.87958(4)0.88370(4)0.60626(4)0.87535(4)0.68903(13)0.91893(13)0.89178(14)0.90098(15)0.81476(15)0.57752(14)0.90312(14)0.59786(17)0.59533(18)0.67504(13)0.57219(13)0.57522(13)0.81359(14)0.92971(14)0.87985(13)0.87958(13)0.68669(13)0.51757(13)0.78456(18)0.783(3)0.761(3)0.01370(14)0.0239(3)0.0271(4)0.0303(4)0.0254(4)0.0410(5)0.0325(6)0.0988(19)0.01284(4)0.01520(18)0.01691(18)0.01456(18)0.01472(18)0.0309(7)0.0247(6)0.0272(6)0.0300(7)0.0445(9)0.0253(6)0.0274(7)0.0354(8)0.0373(8)0.0282(7)0.0211(6)0.0236(6)0.0298(7)0.0263(6)0.0211(6)0.0198(6)0.0218(6)0.0255(6)0.0576(12)
0.069
0.069
0.0270(6)0.0252(8)0.0240(9)0.0376(10)0.0240(8)0.0575(13)0.0346(14)0.075(3)0.01114(7)0.0154(4)0.0154(4)0.0114(4)0.0137(4)0.045(2)0.0220(15)0.0321(17)0.0157(15)0.040(2)0.0229(15)0.0146(14)0.0303(18)0.0297(17)0.0286(16)0.0150(13)0.0216(15)0.0390(18)0.0196(15)0.0139(13)0.0149(13)0.0190(14)0.0268(15)0.037(2)0.0193(8)0.0303(9)0.0256(9)0.0267(9)0.0289(10)0.0409(14)0.163(4)0.01244(7)0.0136(4)0.0165(4)0.0134(4)0.0136(4)0.0300(17)0.0252(15)0.0141(13)0.0303(16)0.071(3)0.0180(14)0.0322(16)0.0149(14)0.0169(15)0.0387(18)0.0248(14)0.0271(15)0.0257(15)0.0293(16)0.0159(13)0.0117(12)0.0271(15)0.0305(16)0.106(4)0.0268(8)0.0256(8)0.0247(8)0.0242(8)0.0411(11)0.0241(12)0.0460(19)0.01492(7)0.0170(4)0.0190(4)0.0190(4)0.0170(4)0.0176(14)0.0283(15)0.0345(16)0.0445(18)0.0219(16)0.0353(16)0.0361(17)0.060(2)0.068(2)0.0172(14)0.0244(14)0.0214(14)0.0275(15)0.0276(15)0.0334(15)0.0339(15)0.0197(13)0.0182(13)0.032(2)0.0013(7)–0.0052(7)0.0045(7)–0.0004(7)–0.0083(8)0.0123(11)0.059(2)0.00186(5)0.0001(3)0.0007(4)–0.0005(3)–0.0004(3)–0.0040(12)–0.0042(12)0.0026(12)0.0038(14)0.0061(16)0.0055(12)–0.0025(13)–0.0011(14)0.0035(15)–0.0008(12)0.0000(12)–0.0001(12)–0.0070(13)0.0103(12)–0.0014(11)–0.0009(11)–0.0016(11)0.0017(12)–0.010(2)0.0025(6)–0.0008(7)–0.0048(7)–0.0003(6)0.0219(9)0.0115(10)–0.0328(18)0.00187(4)0.0036(3)0.0034(3)0.0028(3)0.0026(3)0.0032(13)0.0087(12)0.0024(13)0.0061(13)0.0023(14)0.0052(12)0.0068(12)0.0026(15)0.0151(16)0.0030(12)0.0061(11)0.0007(11)0.0139(13)–0.0043(12)0.0035(11)0.0072(11)0.0042(11)0.0007(11)0.0101(17)–0.0041(7)0.0031(7)–0.0117(7)–0.0067(7)–0.0097(9)0.0166(12)–0.092(3)–0.00010(5)–0.0022(3)–0.0018(4)–0.0004(3)0.0013(3)0.0023(14)0.0022(12)–0.0063(12)–0.0052(13)0.0007(18)–0.0015(12)–0.0046(12)0.0069(13)0.0094(13)–0.0108(14)0.0023(11)–0.0119(12)0.0030(14)–0.0002(12)–0.0026(11)–0.0002(10)0.0008(12)–0.0029(13)–0.001(2)0.0331(17)0.0228(15)0.0272(15)0.0002(13)0.0115(13)0.0009(14)(continued)

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

KlaprothiteTABLE 5. (contd.)
Klaprothite (contd.)
x/a
H2a
H2b
OW3
H3a
H3b
OW4
H4a
H4b

U 11

U 22

U 33

U 23

U 13

U 12

0.0274(16)0.0260(16)0.0212(14)–0.0022(12)0.0019(12)–0.0053(13)0.0398(19)0.0300(17)0.0296(17)0.0014(14)0.0036(15)–0.0016(15)

Ueq

U 11

U 22

U 33

U 23

U 13

U 12

0.0321(4)0.0312(4)0.0302(4)0.0290(4)0.0405(5)0.0255(5)0.0826(15)0.01259(5)0.01805(19)0.01702(19)0.01466(18)0.01533(18)0.0397(8)0.0256(6)0.0364(8)0.0401(9)0.0386(8)0.0281(7)0.0408(9)0.0266(7)0.0287(7)0.0302(7)0.0242(6)0.0223(6)0.0449(11)0.0367(10)0.0367(10)0.0303(10)0.0411(11)0.0246(13)0.084(3)0.01248(8)0.0154(5)0.0156(5)0.0136(5)0.0143(5)0.049(2)0.0203(15)0.047(2)0.0176(17)0.059(2)0.0319(17)0.0172(17)0.0309(17)0.0282(17)0.0358(18)0.0130(14)0.0247(16)0.0279(10)0.0336(10)0.0285(10)0.0307(10)0.0445(12)0.0317(13)0.137(4)0.01214(8)0.0173(5)0.0146(5)0.0137(5)0.0147(5)0.048(2)0.0266(16)0.0201(17)0.0341(19)0.038(2)0.0185(15)0.036(2)0.0192(15)0.0177(15)0.0379(19)0.0239(16)0.0211(15)0.0257(9)0.0223(9)0.0291(9)0.0298(9)0.0295(10)0.0201(11)0.0279(16)0.01266(7)0.0218(5)0.0201(5)0.0164(4)0.0167(4)0.0190(16)0.0273(15)0.045(2)0.072(3)0.0192(15)0.0330(17)0.071(2)0.0303(16)0.0409(18)0.0155(14)0.0367(17)0.0223(14)–0.0057(7)–0.0064(7)–0.0105(7)–0.0052(7)–0.0090(8)0.0046(9)–0.0204(18)–0.00023(5)0.0013(4)–0.0015(3)–0.0018(3)–0.0023(3)0.0021(14)0.0020(12)–0.0065(14)0.0093(17)–0.0025(13)0.0052(12)–0.0167(17)–0.0019(12)0.0014(13)–0.0028(12)–0.0038(12)–0.0027(11)–0.0139(8)–0.0056(7)–0.0152(8)–0.0146(7)0.0028(8)–0.0062(9)–0.0191(16)–0.00267(5)–0.0059(4)–0.0038(4)–0.0035(3)–0.0036(3)–0.0037(14)–0.0022(12)–0.0165(16)–0.0188(16)–0.0108(15)–0.0078(13)–0.0140(16)–0.0099(13)–0.0111(14)–0.0042(12)–0.0083(12)–0.0082(12)0.0180(8)–0.0115(8)0.0145(8)0.0090(8)–0.0229(9)0.0020(10)0.089(3)–0.00012(5)0.0024(4)0.0032(4)–0.0008(4)–0.0015(4)0.0052(17)–0.0029(12)0.0092(15)0.0027(14)0.0101(17)–0.0001(13)0.0066(14)0.0081(13)0.0068(12)–0.0103(14)0.0028(12)–0.0068(12)

y/b

z/c

Ueq

0.414(5)0.393(5)0.4801(3)0.526(4)0.454(5)0.4137(4)0.376(4)0.499(3)0.869(3)0.744(4)0.1886(3)0.252(4)0.143(4)0.8479(3)0.903(4)0.868(5)0.023(2)0.035(2)0.82167(13)0.840(2)0.8493(18)0.78808(15)0.763(2)0.791(2)

0.032
0.032
0.0251(6)
0.030
0.030
0.0333(7)
0.040
0.040

x/a

y/b

z/c

0.0173(2)0.13381(19)0.32017(19)0.48329(18)0.6224(2)00.5
0.09294(2)0.23359(10)0.27155(10)0.15332(10)0.33207(10)0.2244(4)0.3376(3)0.2676(4)0.0921(3)0.2572(4)0.1923(3)0.4194(3)0.2080(3)0.1136(3)0.1011(3)0.3065(3)0.0866(3)0.21679(18)0.60608(18)0.28083(18)0.30651(18)0.1241(2)0.5
00.80723(2)0.02517(10)0.47726(9)0.45960(9)0.01303(9)0.0221(4)0.1233(3)0.8920(3)0.0632(3)0.4774(3)0.3676(3)0.4725(3)0.6058(3)0.5881(3)0.4443(3)0.4391(3)0.3520(3)0.78354(16)0.49903(16)0.98490(17)0.21999(16)0.52127(18)000.80855(2)0.23419(9)0.76028(9)0.21644(9)0.76845(9)0.3731(3)0.1628(3)0.1791(3)0.2179(4)0.6279(3)0.8403(3)0.7621(4)0.8259(3)0.1683(3)0.3582(3)0.1685(3)0.1543(3)Péligotite(continued)

ANTHONY R. KAMPF ET AL.

764

Na1
Na2
Na3
Na4
Na5
Na6
Na7
U
S1
S2
S3
S4
O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12

TABLE 5. (contd.)

765

O13
O14
O15
O16
O17
O18
OW1
H1a
H1b
OW2
H2a
H2b
OW3
H3a
H3b
OW4
H4a
H4b

0.4120(3)0.3831(3)0.1781(3)0.3355(3)0.1527(3)0.9593(3)0.0212(6)0.030(7)0.106(4)0.5681(3)0.588(5)0.642(4)0.3404(3)0.321(5)0.403(4)0.4291(7)0.359(5)0.486(7)Ottohahnite
x/a
U1
U2
S1
S2
S3
S4
S5
Na1
Na2
Na3
Na4
Na5

0.76518(2)0.43880(2)0.64717(12)0.74046(12)0.42597(12)0.01287(13)0.86118(12)0.8619(2)0.5133(2)0.0619(2)0.8728(2)0.6421(3)

y/b

z/c

Ueq

U 11

U 22

U 33

U 23

U 13

U 12

0.0350(3)0.0928(3)0.0374(3)0.8660(3)0.7912(3)0.1796(3)0.2052(6)0.129(3)0.233(7)0.3171(3)0.392(3)0.277(4)0.6990(3)0.742(4)0.647(4)0.2766(5)0.303(7)0.342(7)0.6332(3)0.8573(3)0.7821(3)0.8039(3)0.6350(3)0.0190(3)0.5629(4)0.539(7)0.536(7)0.9800(3)0.944(5)0.961(5)0.3532(3)0.294(4)0.317(4)0.4487(4)0.510(6)0.454(8)0.0308(7)0.0254(6)0.0200(6)0.0235(6)0.0218(6)0.0241(6)0.0723(15)
0.087
0.087
0.0285(7)
0.034
0.034
0.0289(7)
0.035
0.035
0.0841(18)
0.101
0.101

0.0260(17)0.0262(16)0.0141(14)0.0175(15)0.0268(16)0.0292(16)0.109(4)0.0421(19)0.0253(16)0.0168(14)0.0137(14)0.0217(15)0.0253(16)0.078(3)0.0198(15)0.0291(16)0.0305(15)0.0404(17)0.0159(13)0.0164(13)0.034(2)–0.0039(13)–0.0104(12)0.0014(11)0.0007(12)–0.0011(11)–0.0030(11)–0.008(2)0.0018(12)–0.0144(13)–0.0085(11)–0.0099(12)–0.0040(11)–0.0038(11)–0.028(3)–0.0100(14)0.0019(13)0.0001(11)0.0003(11)–0.0041(12)–0.0017(13)0.044(3)0.0239(17)0.0277(18)0.0301(17)0.0024(13)–0.0013(13)0.0008(14)0.0315(18)0.0283(18)0.0245(16)–0.0021(13)–0.0037(13)0.0029(14)0.126(5)0.081(4)0.034(2)0.004(2)–0.005(3)0.052(3)y/b0.92310(2)0.47704(2)0.22386(10)0.58141(10)0.80033(10)0.99886(11)0.63587(11)0.28948(17)0.33816(19)0.6873(2)0.1325(2)0.8889(2)z/c0.59278(2)0.20323(2)0.18552(9)0.43301(8)0.39688(9)0.79367(9)0.93924(9)0.81894(15)0.41652(16)0.61423(17)0.02411(18)0.02774(19)Ueq0.01693(6)0.01589(5)0.0213(3)0.0173(2)0.0180(2)0.0228(3)0.0214(2)0.0293(5)0.0312(5)0.0344(5)0.0390(5)0.0401(6)U 11
0.01595(10)0.01530(10)0.0182(6)0.0161(6)0.0164(6)0.0211(6)0.0182(6)0.0302(12)0.0337(12)0.0444(14)0.0364(13)0.0458(14)U 220.01423(9)0.01535(9)0.0170(5)0.0153(5)0.0160(5)0.0225(6)0.0210(6)0.0235(10)0.0311(11)0.0287(11)0.0345(12)0.0238(11)U 33
0.01643(9)0.01348(8)0.0233(6)0.0150(5)0.0164(5)0.0176(5)0.0189(5)0.0255(10)0.0323(11)0.0371(12)0.0441(13)0.0443(13)U 23
0.00435(7)0.00398(7)0.0042(5)0.0029(4)0.0043(4)0.0052(5)0.0064(4)0.0055(8)0.0166(9)0.0165(9)0.0218(10)0.0058(10)

U 13

U 12

0.00092(7)0.00148(7)0.0036(5)0.0011(4)–0.0003(4)–0.0016(5)–0.0012(5)0.0013(9)0.0093(9)0.0174(10)–0.0008(10)0.0160(11)0.00139(7)0.00216(7)0.0043(5)0.0015(4)0.0041(4)0.0036(5)–0.0023(5)0.0041(9)0.0046(9)0.0182(10)–0.0028(10)0.0064(10)(continued)

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

Péligotite (contd.)x/aTABLE 5. (contd.)
Ottohahnite (contd.)
y/b

z/c

Ueq

U 11

U 22

U 33

U 23

U 13

U 12

0.6328(5)0.5596(4)0.8601(4)0.6499(4)0.6615(4)0.7937(4)0.3898(4)0.4102(4)0.3319(4)0.5713(4)0.1514(4)0.9971(5)0.9695(4)0.9052(3)0.9285(4)0.0473(4)0.7297(4)0.8068(3)0.8678(4)0.6598(4)0.4849(4)0.3923(3)0.7096(5)0.9016(4)0.7482(4)0.9939(5)0.1271(4)0.2298(4)0.5335(8)0.5358(19)0.7656(7)0.6236(12)0.2402(4)0.3102(3)0.5142(3)0.5452(3)0.5619(3)0.7186(3)0.7619(4)0.6908(3)0.8863(3)0.8642(3)0.0527(4)0.9828(4)0.8768(3)0.0764(3)0.6428(3)0.3070(4)0.6946(3)0.5023(3)0.9717(3)0.8690(3)0.5240(3)0.4298(3)0.9473(4)0.5982(4)0.2485(4)0.3217(4)0.7924(4)0.5100(4)0.802(2)0.906(5)0.7849(5)0.0097(9)0.2889(3)0.1485(3)0.4276(3)0.4854(3)0.3236(2)0.4916(3)0.4731(3)0.2950(3)0.3723(3)0.4383(3)0.8109(3)0.8860(3)0.6967(3)0.7644(3)0.0433(3)0.0998(3)0.9403(3)0.8604(3)0.5275(3)0.6539(3)0.1106(3)0.2963(3)0.9026(3)0.6761(3)0.9332(3)0.7067(3)0.5167(3)0.9070(3)0.1177(13)0.180(3)0.2689(4)0.3142(8)0.0503(12)0.0324(9)0.0337(9)0.0314(8)0.0258(8)0.0312(8)0.0409(10)0.0333(9)0.0364(9)0.0295(8)0.0450(11)0.0468(11)0.0306(9)0.0250(8)0.0287(8)0.0418(10)0.0326(9)0.0235(7)0.0296(8)0.0302(8)0.0286(8)0.0265(8)0.0545(12)0.0448(11)0.0381(9)0.0489(11)0.0446(10)0.0369(9)0.076(5)0.090(16)0.0800(17)0.063(3)0.071(3)0.033(2)0.029(2)0.032(2)0.0211(18)0.035(2)0.031(2)0.042(2)0.037(2)0.0222(19)0.021(2)0.062(3)0.031(2)0.0218(18)0.0247(19)0.039(2)0.026(2)0.0138(16)0.026(2)0.0245(19)0.028(2)0.0201(18)0.050(3)0.036(2)0.038(2)0.059(3)0.038(2)0.035(2)0.037(4)0.034(10)0.095(5)0.087(8)0.059(3)0.0294(19)0.033(2)0.036(2)0.0326(19)0.0154(16)0.061(3)0.0164(17)0.0284(19)0.0328(19)0.042(2)0.056(3)0.0190(17)0.0180(16)0.035(2)0.051(2)0.0208(17)0.0215(16)0.0302(19)0.037(2)0.037(2)0.0322(19)0.062(3)0.064(3)0.044(2)0.046(2)0.054(3)0.043(2)0.113(14)0.15(4)0.084(4)0.050(6)0.045(2)0.0307(19)0.040(2)0.0237(18)0.0181(16)0.0300(19)0.037(2)0.0274(18)0.038(2)0.0256(18)0.062(3)0.032(2)0.0269(18)0.0242(17)0.0229(17)0.032(2)0.0309(19)0.0266(17)0.0319(19)0.0274(18)0.0225(17)0.0268(18)0.041(2)0.035(2)0.035(2)0.040(2)0.055(3)0.036(2)0.091(9)0.11(3)0.078(4)0.070(7)0.033(2)0.0100(16)0.0154(17)0.0104(16)0.0086(14)–0.0014(14)0.031(2)0.0001(14)0.0119(17)0.0115(15)0.019(2)0.027(2)0.0028(14)0.0028(14)0.0145(15)0.0154(19)–0.0012(15)0.0049(14)0.0116(16)0.0136(16)0.0142(15)0.0150(15)0.015(2)0.022(2)0.0197(18)0.017(2)0.033(2)0.0196(18)0.068(10)0.09(3)0.045(3)0.028(5)0.033(2)0.0048(16)0.0095(17)0.0064(16)0.0003(14)0.0043(16)0.0046(17)0.0009(17)0.0023(17)–0.0047(15)–0.0029(19)0.015(2)–0.0058(15)–0.0022(14)–0.0020(15)0.0073(18)–0.0059(16)0.0001(14)0.0104(16)0.0039(15)0.0058(15)0.0020(14)0.010(2)0.0098(18)0.0096(18)0.014(2)0.018(2)0.0093(18)0.001(4)0.004(11)0.033(3)0.048(6)0.028(2)0.0193(16)0.0177(17)–0.0033(17)–0.0040(15)0.0025(15)0.000(2)0.0086(16)0.0173(17)–0.0036(15)–0.0038(18)0.023(2)0.0099(15)0.0049(14)–0.0024(16)–0.0171(19)0.0053(15)0.0025(13)0.0011(16)0.0010(16)0.0061(16)–0.0026(15)–0.015(2)0.003(2)0.0092(19)–0.003(2)0.007(2)0.0060(18)–0.013(5)–0.018(13)0.018(3)0.019(5)*Occupancies: OW7a: 0.69(4); OW7b: 0.31(4); OW9: 0.5

ANTHONY R. KAMPF ET AL.

766

O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
O19
O20
O21
O22
O23
O24
OW1
OW2
OW3
OW4
OW5
OW6
OW7a*
OW7b*
OW8
OW9*

x/a

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALSTABLE 6. Selected bond distances (Å) and angles (°) for klaprothite, péligotite and ottohahnite.
Klaprothite
Na1–O9
Na1–OW1
Na1–O15
Na1–O6
Na1–O18
Na1–O3
Na1–O4<Na1–O>

2.325(3)2.390(4)2.415(3)2.472(3)2.479(3)2.690(3)2.694(3)2.495

Na2–OW3
Na2–O13
Na2–O17
Na2–O1Na2–O10
Na2–O5<Na2–O>2.366(3)2.366(3)2.394(3)2.440(3)2.531(3)2.583(4)2.447

Na3–O14
Na3–O11
Na3–O6
Na3–O2Na3–O7
Na3–OW2
Na3–O12<Na3–O>

2.305(3)2.427(3)2.450(3)2.467(3)2.523(3)2.553(4)2.613(3)2.477

Hydrogen bonds
D–H···A
OW1–H1a···O5
OW1–H1b···O17
OW2–H2a···O11
OW2–H2b···O3
OW3–H3a···O3
OW3–H3b···O7
OW4–H4a···O1
OW4–H4b···O10

D–H
0.79(3)0.84(3)0.80(3)0.79(3)0.83(3)0.80(3)0.80(3)0.86(3)Na4–OW2
Na4–O16
Na4–O11
Na4–OW4
Na4–O7
Na4–O2<Na4–O>2.345(3)2.353(3)2.376(3)2.381(4)2.453(3)2.580(3)2.415

Na5–OW4
Na5–OW3
Na5–O10
Na5–OW1
Na5–O13
Na5–O1<Na5–O>2.396(4)2.425(4)2.445(3)2.481(5)2.498(4)2.910(4)2.526

Na6–O6(×2)
Na6–O12(×2)
Na6–O8(×2)
Na6–O9(×2)<Na6–O>2.464(3)2.470(3)2.686(4)2.788(4)2.602

Na7–O14(×2)
Na7–O2(×2)
Na7–OW2(×2)

2.290(3)2.342(3)2.959(3)H···A
2.30(3)2.61(3)2.13(3)2.10(3)2.00(3)2.08(3)2.25(3)2.04(3)D···A
3.060(6)2.905(6)2.914(4)2.859(4)2.817(4)2.842(4)2.987(4)2.873(5)

S1–O1
S1–O2
S1–O3
S1–O4
<S1–O>

1.458(3)1.464(3)1.464(3)1.502(3)
1.472

S2–O5
S2–O6
S2–O7
S2–O8
<S2–O>

1.449(3)1.457(3)1.464(3)1.502(3)
1.468

S3–O9
S3–O10S3–O11
S3–O12<S3–O>

1.447(3)1.462(3)1.462(3)1.518(3)1.472

S4–O13S4–O14S4–O15S4–O16<S4–O>

1.446(3)1.447(3)1.498(3)1.503(3)
1.474

U–O17
U–O18
U–O12
U–O8
U–O4
U–O15
U–O16
<U–OUr><U–Oeq>1.772(3)1.777(3)2.301(3)2.306(3)2.341(3)2.435(3)2.456(3)
1.775
2.368

<DHA
161(6)
102(6)
166(5)
161(5)
174(4)
159(5)
154(4)
163(5)

the approximate range 3650–3300 cm−1. The bands
are very broad and of low intensity. Approximate
O–H···O hydrogen bond lengths inferred fromthe corresponding stretching wavenumbers using
Libowitzky’s empirical relation (Libowitzky, 1999)
vary in the range >3.2–2.77 Å.
Very weak bands at ∼1650 cm−1, attributed tothe ν2 (δ) H–O–H bending mode of the H2O
molecules, were observed in the spectra of all threeminerals. The low intensities of bands is typical ofRaman spectra, in contrast to the higher intensity ofν2 (δ) mode bands in infrared spectra.

Vibrations of SO4 groups

767

The vibrations of the sulfate tetrahedra are wellresolved in the spectra of all three minerals. The
activated antisymmetric vibration ν3 (SO4) and thesplitting of the degenerate modes suggest departurefrom the ideal Td symmetry. The distortion of thetetrahedra due to the bidentate linkage between the
SO4 and UO7 bipyramids is considerable (Plášil
et al., 2015). Multiple bands for ν1 (SO4) in all three
spectra are indicative of symmetrically
non-equivalent SO4 groups.

ANTHONY R. KAMPF ET AL.

TABLE 6. (contd.)
Péligotite
Na1–O9
Na1–OW1
Na1–O15
Na1–O18
Na1–O6
Na1–O3
Na1–O4<Na1–O>2.302(3)2.340(5)2.365(3)2.429(3)2.501(4)2.932(4)3.004(4)2.553

Na2–O10
Na2–OW3
Na2–O5
Na2–O17
Na2–O10
Na2–OW1<Na2–O>2.309(3)2.371(4)2.403(4)2.408(3)2.437(4)2.588(5)2.419

Na3–O14
Na3–O6
Na3–OW2
Na3–O2Na3–O11
Na3–O12
Na3–O7<Na3–O>2.313(3)2.378(3)2.452(4)2.470(3)2.510(3)2.596(3)2.961(4)2.526

Hydrogen bonds
D–H···A
OW1–H1a···O1
OW1–H1b···none
OW2–H2a···O11
OW2–H2b···O3
OW3–H3a···O3
OW3–H3b···O7
OW4–H4a···O5
OW4–H4b···none

D–H
0.80(3)0.85(3)0.83(3)0.80(3)0.82(3)0.82(3)0.85(3)0.87(3)Na4–O11
Na4–OW4
Na4–O16
Na4–O7
Na4–OW2
Na4–O2<Na4–O>2.342(3)2.353(5)2.422(3)2.443(4)2.455(4)2.519(3)2.422

Na5–O13
Na5–OW3
Na5–O13
Na5–O17
Na5–O1
Na5–OW4<Na5–O>2.262(3)2.325(4)2.401(3)2.511(3)2.537(4)2.679(6)2.453

Na6–O12(×2)
Na6–O9(×2)
Na6–O6(×2)
Na6–O8(×2)<Na6–O>2.492(3)2.532(3)2.540(3)2.567(4)2.533

Na7–O14(×2)
Na7–O2(×2)
Na7–O3(×2)<Na7–O>

2.311(3)2.359(3)2.750(3)
2.473

S1–O1
S1–O3
S1–O2
S1–O4
<S1–O>

1.454(3)1.459(3)1.463(3)1.489(3)
1.466

S2–O5
S2–O7
S2–O6
S2–O8
<S2–O>

1.452(3)1.457(3)1.462(3)1.514(3)
1.471

S3–O9
S3–O10S3–O11
S3–O12<S3–O>

1.455(3)1.456(3)1.461(3)1.518(3)1.473

S4–O14S4–O13S4–O15S4–O16<S4–O>

1.442(3)1.448(3)1.494(3)1.505(3)
1.472

H···A
2.46(3)D···A
3.037(6)<DHA
130(6)

2.15(3)2.27(4)2.06(3)2.08(3)2.22(3)2.955(4)2.892(5)2.856(4)2.893(4)2.963(6)165(4)
135(5)
165(5)
172(5)
146(7)The bands located at ∼1250 cm−1 are attributable to split triply degenerate ν3 (SO4) antisymmetric stretching vibrations. Raman bands locatedin the range ∼1080 to ∼960 cm−1 are attributableto ν1 (SO4) symmetric stretching vibrations. The
intensities of the bands related to the symmetricstretching mode are considerably higher than those
attributed to the activated antisymmetric stretchingvibrations.
The medium-weak bands located at ∼650 cm−1
are attributed to the ν4 (δ) triply degenerated
antisymmetric stretching vibrations of SO4 tetrahedra and the bands at ∼450 cm−1 are assigned to the

U–O18
U–O17
U–O4
U–O8
U–O12
U–O15
U–O16
<U–OUr><U–Oeq>1.769(3)1.785(3)2.290(3)2.316(3)2.332(3)2.435(3)2.447(3)
1.777
2.364

split ν2 (δ) doubly degenerate bending vibrations of
the SO4 groups. The number of split ν2 (δ)
vibrations is in accordance with the presence ofseveral non-equivalent SO4 tetrahedra in the
structures of all three minerals.
Vibrations of UO2+
2

768

The bands related to the activated ν3 antisymmetricstretching vibration of the uranyl ion, (UO2)2+, wereobserved in the spectra of all three minerals. The
reason for activation of this mode in the Raman
spectra is the lowering of the factor group

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALSTABLE 6. (contd.)
Ottohahnite*
Na1–O17
Na1–O16
Na1–OW3
Na1–O20
Na1–OW4
Na1–O11
Na1–O10<Na1–O>2.349(4)2.377(4)2.386(4)2.425(4)2.439(5)2.853(4)2.867(4)2.528

Na4–O18
Na4–OW3
Na4–OW1
Na4–O14
Na4–O2
Na4–O14<Na4–O>2.343(4)2.399(4)2.404(5)2.406(4)2.634(5)2.655(5)2.474

Na2–O3
Na2–O9
Na2–O6
Na2–O24
Na2–O6
Na2–O22<Na2–O>2.352(5)2.357(4)2.439(4)2.462(4)2.486(4)2.615(4)2.452

Na5–O1
Na5–OW7a
Na5–OW1
Na5–O19
Na5–O13
Na5–OW7b
Na5–O1
Na5–O4<Na5–O>2.339(4)2.349(9)2.380(5)2.417(4)2.522(5)2.59(3)2.711(5)2.897(4)2.527*

Na3–OW5
Na3–O5
Na3–O15
Na3–OW2
Na3–O2Na3–O5
Na3–O8
Na3–O3<Na3–O>2.375(5)2.385(4)2.386(4)2.403(5)2.576(5)2.846(4)2.934(4)2.961(6)2.608

Na6–OW6
Na6–OW2
Na6–OW4
Na6–O2
Na6–O5
Na6–O18
Na6–O7<Na6–O>2.306(4)2.357(5)2.384(5)2.402(5)2.638(5)2.885(5)2.961(5)2.562

U1–O21
U1–O22
U1–O8
U1–O11
U1–O12
U1–O15
U1–O16<U1–OUr><U1–Oeq>1.762(4)1.768(4)2.313(3)2.365(3)2.388(3)2.419(3)2.420(3)
1.765
2.381

U2–O23U2–O24
U2–O4
U2–O7
U2–O10U2–O19U2–O20<U2–OUr><U2–Oeq>1.770(3)1.779(3)2.285(3)2.350(3)2.374(3)2.430(3)2.447(3)
1.775
2.377

S1–O1
S1–O2
S1–O3
S1–O4
<S1–O>

1.449(4)1.452(4)1.455(4)1.516(4)
1.470

S2–O5
S2–O6
S2–O7
S2–O8
<S2–O>

1.446(4)1.457(4)1.489(3)1.489(3)
1.468

S3–O9
S3–O10S3–O11
S3–O12<S3–O>

1.448(4)1.473(3)1.476(4)1.477(4)1.469

S4–O13S4–O14S4–O15S4–O16<S4–O>

1.426(4)1.449(4)1.495(3)1.509(3)
1.470

S5–O17S5–O18S5–O19S5–O20<S5–O>

1.441(3)1.452(4)1.496(4)1.500(3)1.472

Hydrogen bonds
OW1–O142.968(7)OW1–O22
3.198(5)OW2–O6
3.053(5)OW2–O18
2.842(6)OW3–OW6 2.793(6)OW3–OW7a 2.710(9)OW3–OW7b 3.01(2)OW4–OW5 2.838(6)OW4–OW8 2.739(7)OW5–O92.839(6)OW5–O213.064(5)OW6–O172.757(5)OW6–O23
2.941(5)OW7a–OW8 2.824(10)OW7a–OW9 2.790(17)OW7b–O1
2.93(5)
OW7b–OW8 3.00(3)OW8–O132.773(7)OW8–OW9 2.931(11)OW9–O32.867(10)OW9–O93.180(10)*The contributions of Na–OW7a and Na–OW7b to <Na–O> are weighted according to the refined occupancies of the
OW7a and OW7b sites.

(symmetry) due to the relatively low symmetry(monoclinic or triclinic) of these minerals. The
bands are of low or very low intensity and areobserved in the range ∼960 to ∼920 cm−1. Thevery strong bands observed at ∼830 cm−1 are
attributed to the ν1 symmetric stretching vibrationof the uranyl ion.
The approximate U–O bond-lengths inferredfrom the observed energies of the (UO2)2+ vibrations using the empirical relation of Bartlett andCooney (1989) is 1.79 Å, consistent with the bond769

lengths obtained in our X-ray studies (klaprothite∼1.78 Å, péligotite ∼1.79 Å, ottohahnite ∼1.77 Å)
and identical to the most common bond-length
given by Burns et al. (1997) for the uranyl
pentagonal bipyramid, 1.79 Å.
The very weak bands at ∼550 and ∼500 cm−1
may be attributable to the ν (U–Oligand) vibrations.
Bands of medium intensity at low wavenumbers,∼250 cm−1, can be assigned to the ν2 (δ) doubly
degenerate bending vibrations of (UO2)2+ (e.g.
Bullock and Parret, 1970; Ohwada, 1976; Brittain

TABLE 7. Bond-valence analysis for klaprothite, péligotite and ottohahnite. Values are expressed in valence units.*
Klaprothite
Na1

Na3

Na4

0.15

0.11

0.16

Na5

Na6

Na7

U

S1

0.57

1.57
1.54
1.54
1.39

0.04
0.21×2↓

0.08
0.08
0.11
0.14

0.15
0.13

0.15

0.21
0.12

0.61

0.15×2↓

0.62
0.48
0.46
1.71
1.70

0.20
0.18
0.14
0.18
0.20

1.04

0.18
1.03

0.19
1.00

0.15
–0.12,–0.15–0.15,–0.16–0.18,–0.17–0.13,–0.16

0.95

0.04×2↓
0.16
0.18
0.81

0.88

0.98

6.15

1.90
2.01
1.96
1.96
1.83
2.01
1.99
2.08
1.88
1.99
2.05
2.20
1.94
2.08
2.06
2.05
2.04
1.84
0.05
0.05
0.00
0.07

0.16
0.15

0.14
0.12

0.13

1.62
1.61
1.41
1.39

0.24×2↓

0.17

Σ

0.17

0.13
0.23

H bonds

0.12

1.61
1.55
1.55
1.33

0.19

0.19

S4

0.16,0.18

0.16
0.16
0.10

S3

1.60
1.57
1.54
1.39

0.15×2↓0.08×2↓0.06×2↓

S2

6.04

6.10

6.04

6.03

ANTHONY R. KAMPF ET AL.

770

O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
OW1
OW2
OW3
OW4
Σ

Na2

Péligotite
Na1

771

O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
OW1
OW2
OW3
OW4
Σ

Na2

Na3

Na4

0.15

0.13

Na5

Na6

Na7

U

S1

0.60

1.58
1.56
1.55
1.44

0.12
0.20×2↓0.07×2↓

0.04
0.03
0.17
0.13

0.19
0.04

0.16

0.23

0.63

0.14×2↓

0.58

0.17

0.48
0.47
1.67
1.72

0.13
0.15

0.98

0.20
1.00

0.19
1.00

1.03

0.21
0.08
0.98

0.98

0.97

6.15

1.83
2.03
1.98
2.07
1.90
2.01
1.90
2.09
1.93
1.96
2.03
2.15
2.04
2.08
2.09
2.01
1.97
1.88
0.19
0.01
0.08
0.14

0.14

–0.12
–0.14,–0.15–0.17,–0.15
–0.14

0.11
0.15

0.12

1.61
1.64
1.42
1.38

0.22×2↓

0.16
0.21

Σ

0.15

0.25,0.17
0.17

H bonds

0.14

1.58
1.57
1.55
1.33

0.21

0.19

S4

0.15,0.17

0.22,0.16
0.13
0.10
0.22

S3

1.59
1.57
1.55
1.35

0.12×2↓
0.11×2↓
0.12×2↓

S2

6.13

6.06

6.04

6.04

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALSTABLE 7. (contd.)

TABLE 7. (contd.)
Ottohahnite
Na1

OW6

Na3

Na4
0.09

0.20

0.11
0.04

Na5

Na6

U1

U2

S1

0.64

1.60
1.59
1.58
1.34

0.21,0.08
0.17
0.05
0.18,0.05

0.09

0.16,0.14
0.04
0.04

0.56
0.60

0.20
0.05
0.05

0.54
0.55
0.52
0.13
0.18

0.49
0.49
0.20

0.05
0.17

0.48
0.47

0.16
1.75
1.73

0.10

1.72
1.69

0.15
0.17
0.17
0.18
0.16

0.19
0.23

0.18
0.18
0.19
0.23

S3

S4

S5

H bonds

Σ

+0.05

1.94
1.96
1.90
2.03
1.94
1.99
2.04
2.08
2.03
2.09
2.09
2.01
2.04
2.00
2.09
2.04
2.04
2.01
2.06
2.03
1.87
1.93
1.86
1.84
0.12
0.11
–0.02
–0.04
0.07

+0.08
1.62
1.57
1.44
1.44

+0.12
1.61
1.50
1.49
1.49

+0.17,+0.05

1.71
1.60
1.42
1.36

0.17,0.09
0.19
0.20

S2

+0.20
+0.14
1.64
1.59
1.41
1.40

+0.20
+0.17
+0.12
+0.10
+0.14
–0.14,–0.10–0.12,–0.17–0.19,–0.19–0.17,–0.21+0.17,–0.17,–0.12+0.19,–0.20,
–0.14

0.08

ANTHONY R. KAMPF ET AL.

772

O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
O19
O20
O21
O22
O23
O24
OW1
OW2
OW3
OW4
OW5

Na2

6.11
6.10
6.13
0.99
0.90

1.00

0.14,0.03

0.96
0.95
0.99
Σ

OW9

OW8

OW7

*S6+–O bond strength from Brown and Altermatt (1985); Na+–O bond strength from Wood and Palenik (1999); U6+–O bond strength from Burns et al. (1997);
hydrogen-bond strengths based on O–O bond lengths from Ferraris, G. and Ivaldi, G. (1988).

6.04
6.09
6.09
6.07

S3
S2
S1
U2
U1
Na6
Na5
Na4
Na3
Na2
Na1
Ottohahnite

TABLE 7. (contd.)

et al., 1985; Plášil et al., 2010, 2015). Weak Raman
bands at ∼150 cm−1 are attributed to –Oeq–U–
Oeq– bending vibrations (Ohwada, 1976).

0.02

0.02

+0.19,–0.25,–0.09+0.21,+0.16,–0.20,–0.15+0.13,+0.15,–0.16,–0.10

S5
S4

0.02

Σ
H bonds

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

Vibrations of Na–O bonds and lattice modes
Weak Raman bands with shoulders at ∼280 cm−1
could be related to Na–O stretching vibrations or tothe ν (U–Oligand) stretching vibration (Plášil et al.,2010, 2015). The bands located below 100 cm−1
are related to the lattice modes.
Composition
Chemical analyses of klaprothite, péligotite andottohahnite were performed using a CamScan 4D
electron microprobe in energy-dispersive spectroscopy (EDS) mode (20 kV, 500 pA and beamrasterized on an area 8 μm × 8 μm in order tominimize sample damage). The EDS mode withthe above experimental conditions, rather thanwavelength-dispersive spectroscopy (WDS) mode,
was chosen because of the instability of theseminerals under the electron beam caused by thehigh contents of both Na and H2O. Attempts to use
the WDS mode with higher beam current were
unsuccessful because of significant decompositionof the minerals after several seconds under theelectron beam. Standards used were chkalovite forNa, synthetic UO2 for U and synthetic ZnS forS. H2O was not determined directly because of the
scarcity of pure material. The H2O content wascalculated by stoichiometry on the basis of thenumber of O apfu from crystal-structure determinations. The Raman spectra confirm the presence of
H2O groups and the absence of B–O, C–O and N–
O bonds in the minerals. No other elements withatomic numbers higher than 8 were observed.
Analytical data are given in Table 2.
The empirical formula of klaprothite, calculated
as the mean of 11 representative spot analyses, isNa6.01(U1.03O2)(S0.993O4)4(H2O)4 and that of
péligotite, calculated as the mean of 8 analyses, isNa5.82(U1.02O2)(S1.003O4)4(H2O)4, both based on
22 O apfu). The ideal formula for both minerals is
Na6(UO2)(SO4)4(H2O)4 which requires Na2O
21.51, UO3 33.10, SO3 37.05 and H2O 8.34, total
100 wt.%. The empirical formula of ottohahnite,
calculated as the mean of 12 analyses, is Na5.88(U0.99O2)2(S1.008O4)5(H2O)8.5 based on 32.5 O apfu.
Its ideal formula is Na6(UO2)2(SO4)5(H2O)7·
1.5H2O, which requires Na2O 14.18, UO3 43.62,
SO3 30.52 and H2O 11.68, total 100 wt.%.
773

ANTHONY R. KAMPF ET AL.

FIG. 7. (Left) The [(UO2)(SO4)4]6– cluster in the structures of klaprothite and péligotite. (Right) The [(UO2)4(SO4)10]12–
cluster constructed of four linked [(UO2)(SO4)4]6– clusters.

The Gladstone-Dale compatibility index 1 –(KP/KC) for the empirical formulas of klaprothite,
péligotite and ottohahnite are –0.008 (superior), –0.015 (superior) and –0.021 (excellent), respectively (Mandarino, 2007). As noted by Kampf et al.
(2015c), Gladstone-Dale calculations for uranyl
sulfates should utilize k(UO3) = 0.118, as provided
by Mandarino (1976).
X-ray crystallography and structurerefinement
Powder X-ray studies were carried out using a
Rigaku R-Axis Rapid II curved imaging plate
microdiffractometer,withmonochromatized
MoKα radiation (λ = 0.71075 Å). A Gandolfi-likemotion on the j and ω axes was used to randomize
the orientation of the sample and observed d-values
and intensities were derived by profile fitting using
JADE 2010 software (Materials Data, Inc.). The
powder data presented in Table 3 show good
agreement with the patterns calculated from thestructure determinations. Unit-cell parameters refinedfrom the powder data using JADE 2010 with whole
pattern fitting are for klaprothite: a = 9.812(4), b =9.739(4), c = 20.855(4) Å, β = 98.743(8)° and V =1969.7(12) Å3; for péligotite: a = 9.811(9), b =9.928(10), c = 10.635(10) Å, α = 88.79(3)°, β =74.00(3)°, γ = 89.27(2)° and V = 995.5(17) Å3;
and for ottohahnite: a = 9.979(8), b = 11.660(8),c = 14.277(8) Å, α = 113.48(3)°, β = 104.29(2)°,γ = 91.35(2)° and V = 1462.6(18) Å3.
The single-crystal structure data for klaprothite,
péligotite and ottohahnite were collected at room
temperature on a Rigaku R-Axis Rapid II curved
imaging plate microdiffractometer, also using
monochromatized MoKα radiation. The data were774

processed using the Rigaku CrystalClear software
package and empirical (multi-scan) absorption
corrections were applied using the ABSCOR
program (Higashi, 2001) in the CrystalClearsoftware suite. The structures were solved bydirect methods using SIR2011 (Burla et al.,2012). SHELXL-2013 (Sheldrick, 2008) was used
for the refinement of the structures. DifferenceFourier syntheses located all H atom positionsin the structures of klaprothite and péligotite;
however, H atom positions could not be locatedin the ottohahnite structure. For klaprothiteand péligotite, H atom positions were refined with
soft restraints of 0.82(3) Å on the O–H distancesand 1.30(3) Å on the H–H distances and with the
Ueq of each H set to 1.2 times that of its donor
O atom.
For the structures of both klaprothite andpéligotite, all non-hydrogen atoms refined to fulloccupancy, although the Na7 sites, at centres ofsymmetry in both structures, exhibited significant
displacement along a. Refining these as split sites
improved the R-factors slightly, but it was ultimately decided to report them as unsplit sites. The
same high displacement along a is noted for thissite in the structure of the synthetic phaseequivalent to klaprothite (Plášil et al., 2015). For
the structure of ottohahnite, all sites were refinedwith full occupancy except for three O sites inrelatively close proximity: The occupancies of
OW7a and OW7b (1.18 Å apart and coordinatedto Na5) refined to 0.74 and 0.37. The occupancy
of OW9 (1.77 Å from OW7b and not coordinatedto a cation) refined to 0.48. In the final refinement,
the OW7a and OW7b sites were constrained to a
total occupancy of 1 and the OW9 site was assigned
an occupancy of 0.5.

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

FIG. 8. The structures of klaprothite and péligotite viewed along [010]. Na polyhedra are turquoise blue. Unit-cell
outlines are shown as dashed lines.

Data collection and refinement details are
given in Table 4, atom coordinates and displacement parameters in Table 5, selected bonddistances in Table 6 and bond-valence analyses
in Table 7.

Description and discussion of the structures
In the structures of klaprothite, péligotite andottohahnite, the U sites are surrounded by seven
O atom sites forming squat pentagonal bipyramids.
This is the most typical coordination for U6+,

FIG. 9. Heteropolyhedral layers in the structures of klaprothite and péligotite viewed perpendicular to {001} (upper
images) and along [100] (lower images); [010] is horizontal in all cases.

775

ANTHONY R. KAMPF ET AL.

FIG. 10. Edge-sharing chains of NaO6 octahedra in the
structures of klaprothite and péligotite. The chain in
klaprothite is along [010] and that in péligotite is along[110].

particularly in uranyl sulfates (Krivovichev, 2010,2013), where the two short apical bonds of the
bipyramid constitute the uranyl group. The bondlengths in U6+-coordination polyhedron in all threestructures (klaprothite: <U1–Oap> = 1.775, <U1–
Oeq> = 2.368 Å; péligotite: <U1–Oap> = 1.777,<U1–Oeq> = 2.364 Å; ottohahnite: <U1–Oap> =1.765, <U1–Oeq> = 2.381, <U2–Oap> = 1.775,<U2–Oeq> = 2.377 Å) are consistent with themost typical lengths observed for [7]-coordinatedU6+ (Burns et al., 1997). In all three structures, allfive of the equatorial O atoms also participate in
SO4 tetrahedra and, in each case, three of the SO4
tetrahedra share single equatorial O atoms and one
shares two equatorial O atoms, i.e. a shared
polyhedral edge. Such a bidentate linkage
between a UO7 pentagonal bipyramid and a SO4
tetrahedron has previously been reported insynthetic phases, but never in minerals. The[(UO2)(SO4)4]6– uranyl sulfate cluster (Fig. 7) is
the fundamental building block in the structures ofklaprothite and péligotite; while in the structureof ottohahnite, four of these uranyl-sulfate
clusters are combined through shared SO4 tetrahedra to form a larger [(UO2)4(SO4)10]12– cluster(Fig. 7). Among synthetic Na uranyl sulfates, thestructure of the synthetic equivalent of klaprothite
was reported by Plášil et al. (2015) and thesame [(UO2)(SO4)4]6– cluster with a bidentate
U–S linkage was reported in the structures ofNa10[(UO2)(SO4)4](SO4)2·3H2O (Burns andHayden,2002),
KNa5[(UO2)(SO4)4](H2O)(Hayden and Burns, 2002a) and Na6(UO2)(SO4)4(H2O)2 (Hayden and Burns, 2002b). The[(UO2)4(SO4)10]12– cluster in the structure ofottohahnite has not previously been reported in
the structure of any mineral or synthetic phase.

FIG. 11. One slice parallel to {112} in the structure of ottohahnite containing the [(UO2)4(SO4)10]12–cluster and Na1,
Na3 and Na5 atoms. Na–O bonds are shown as sticks.

776

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

FIG. 12. The structure ottohahnite viewed down [111] with {112} horizontal. O atoms of H2O groups are shown as whitespheres. The unit cell outline is shown in red.

In the structures of klaprothite and péligotite,seven Na sites, in 6-, 7- and 8-coordinations, link to
the O atoms in the clusters and to four H2O groups,
yielding relatively loosely bonded frameworks(Fig. 8). In both structures, the Na1O7, Na3O7,
Na4O6, Na6O8 and Na7O6 polyhedra combine withthe uranyl sulfate clusters forming more tightly
bonded heteropolyhedral layers parallel to {001} inwhich the Na polyhedra share some faces andedges with one another, and edges and corners with
the UO7 and SO4 polyhedra of the uranyl sulfate
clusters. The polyhedral layers in the two structures(Fig. 9) are topologically identical except for aminor difference in the Na7O6 coordination. The
principal difference between the structures is theconfiguration of the Na2O6 and Na5O6 octahedra
between the layers. These octahedra form a zig-zag
edge-sharing chain parallel to [010] in the structureof klaprothite, while in the structure of péligotite
they form a straight edge-sharing chain parallel to[110] (Fig. 10).
In the structure of ottohahnite, the[(UO2)4(SO4)10]12– clusters are linked to one
another via bonds to six different Na atoms. The
Na atoms, with coordinations ranging from 6 to 8,
bond to O atoms in the clusters and to H2O groups.
There are seven different H2O groups (one of whichis split) bonded to Na atoms and two H2O groups,

one of which is half occupied, bonded only
though hydrogen bonds. The plane of the[(UO2)4(SO4)10]12– cluster is parallel to {112}.
Na1, Na3 and Na5 are in approximately the sameplane with the cluster. Figure 11 shows the linkages
between the clusters and Na1O7, Na3O8 andNa5O7 coordinations within one slice through thestructure parallel to {112}. The Na2, Na4 and Na6
atoms are placed between these slices linking them
together via Na–O bonds and yielding Na2O6,
Na4O6 and Na6O7 coordinations. The isolated H2Ogroups (OW8 and OW9) are also sandwiched in
between the slices (Fig. 12).
Acknowledgements

777

Structures Editor Peter Leverett and an anonymous
reviewer are thanked for their comments on the
manuscript. Atali A. Agakhanov and Ladislav Lapčák
are thanked for their assistance with the chemistry and
Raman measurements, respectively. A portion of thisstudy was funded by the John Jago Trelawney
Endowment to the Mineral Sciences Department of
the Natural History Museum of Los Angeles County.
This research was also financially supported by GACR
post-doctoral Grant no. 13-31276P to J.P. and by the
Ministry of Culture of the Czech Republic (DKRVO
2016/02; National Museum 00023272) to J.Č.

ANTHONY R. KAMPF ET AL.

References
Bartlett, J.R. and Cooney, R.P. (1989) On the determination of uranium-oxygen bond lengths in dioxouranium(VI) compounds by Raman spectroscopy.
Journal of Molecular Structure, 193, 295–300.
Brown, I.D. and Altermatt, D. (1985) Bond-valence
parameters from a systematic analysis of the inorganic
crystal structure database. Acta Crystallographica,
B41, 244–247.
Brittain, H.G., Ansari, P., Toivonen, J., Niinisto, L., Tsao, L.
and Perry, D.L. (1985) Photophysical Studies of Uranyl
Complexes. VIII. Luminiscence Spectra of UO2SO4·
31/2H2O and Two Polymorphs of Bis(urea) Uranyl
Sulfate. Journal of Solid State Chemistry, 59, 259–264.
Bullock, H. and Parret, F.W. (1970) The low frequency
infrared and Raman spectroscopic studies of some uranyl
complexes: the deformation frequency of the uranyl ion.
Canadian Journal of Chemistry, 48, 3095–3097.
Burla, M.C., Caliandro, R., Camalli, M., Carrozzini, B.,
Cascarano, G.L., Giacovazzo, C., Mallamo, M.,
Mazzone, A., Polidori, G. and Spagna, R. (2012)
SIR2011: a new package for crystal structure determination and refinement. Journal of Applied
Crystallography, 45, 357–361.
Burns, P.C. and Hayden, L.A. (2002) A uranyl sulfate
cluster in Na10[(UO2)(SO4)4](SO4)2·3H2O. Acta
Crystallographica, C58, i121–i123.
Burns, P.C., Ewing, R.C. and Hawthorne, F.C. (1997) The
crystal chemistry of hexavalent uranium: polyhedrongeometries, bond-valence parameters, and polymerization of polyhedra. The Canadian Mineralogist, 35,
1551–1570.
Chenoweth, W.L. (1993) The Geology and Production
History of the Uranium Deposits in the White Canyon
Mining District, San Juan County, Utah. Utah
Geological Survey Miscellaneous Publication, 93–3.
Ferraris, G. and Ivaldi, G. (1988) Bond valence vs. bondlength in O···O hydrogen bonds. Acta
Crystallographica, B44, 341–344.
Hawthorne, F.C. (2012) A bond-topological approach totheoretical mineralogy: crystal structure, chemicalcomposition and chemical reactions. Physics andChemistry of Minerals, 39, 841–874.
Hawthorne, F.C. and Schindler, M. (2008) Understanding
the weakly bonded constituents in oxysalt minerals.
Zeitschrift für Kristallographie, 223, 41–68.
Hayden, L.A. and Burns, P.C. (2002a) The sharing of anedge between a uranyl pentagonal bipyramid and sulfate
tetrahedron in the structure of KNa5[(UO2)(SO4)4](H2O). The Canadian Mineralogist, 40, 211–216.
Hayden, L.A. and Burns, P.C. (2002b) A novel uranyl
sulfate cluster in the structure of Na6(UO2)(SO4)4(H2O)2.
Journal of Solid State Chemistry, 163, 313–318.
Higashi, T. (2001) ABSCOR. Rigaku Corporation, Tokyo.
Kampf, A.R., Plášil, J., Kasatkin, A.V. and Marty, J.
(2014) Belakovskiite, Na7(UO2)(SO4)4(SO3OH)(H2O)3, a new uranyl sulfate mineral from the Blue
Lizard mine, San Juan County, Utah, USA.
Mineralogical Magazine, 78, 639–649.
Kampf, A.R., Kasatkin, A.V., Čejka, J. and Marty, J. (2015a)
Plášilite, Na(UO2)(SO4)(OH)·2H2O, a new uranyl
sulfate mineral from the Blue Lizard mine, San JuanCounty, Utah, USA. Journal of Geosciences, 60, 1–10.
Kampf, A.R., Plášil, J., Kasatkin, A.V. and Marty, J.
(2015b) Bobcookite, NaAl(UO2)2(SO4)4(H2O)18, andwetherillite, Na2Mg(UO2)2(SO4)4·18H2O, two new
uranyl sulfate minerals from the Blue Lizard mine, San
Juan County, Utah, USA. Mineralogical Magazine,79, 695–714.
Kampf, A.R., Plášil, J., Kasatkin, A.V., Marty, J. andČejka, J. (2015c) Fermiite, Na4(UO2)(SO4)3·3H2O,
and oppenheimerite, Na2(UO2)(SO4)2·3H2O, two new
uranyl sulfate minerals from the Blue Lizard mine, San
Juan County, Utah, USA. Mineralogical Magazine,
79, 1123–1142.
Kampf, A.R., Plášil, J., Čejka, J., Marty, J., Škoda, R. andLapčák, L. (2017a) Alwilkinsite-(Y), a new rare-earth
uranyl sulfate mineral from the Blue Lizard mine, San
Juan County, Utah, USA. Mineralogical Magazine,
81, https:doi.org/10.1180/minmag.2016.080.139.
Kampf, A.R., Plášil, J., Kasatkin, A.V., Marty, J. Čejka, J.
and Ladislav Lapčák (2017b) Shumwayite, [(UO2)(SO4)(H2O)2]2·H2O, a new uranyl sulfate mineralfrom Red Canyon, San Juan County, Utah, USA.
Mineralogical Magazine, 81, 273–285.
Krivovichev, S.V. (2010) Actinyl compounds withhexavalent elements (S, Cr, Se, Mo) – structural
diversity, nanoscale chemistry, and cellular automata
modeling. European Journal of Inorganic Chemistry,
2010, 2594–2603.
Krivovichev, S.V. (2013) Crystal chemistry of uraniumoxides and minerals. Pp. 611–640 in: Comprehensive
Inorganic Chemistry II, Vol 2 (J. Reedijk and K.
Poeppelmeier, editors). Elsevier, Oxford, UK.
Libowitzky, E. (1999) Correlation of O–H stretchingfrequencies and O–H···O hydrogen bond lengths inminerals. Monatshefte für Chemie, 130, 1047–1059.
Mandarino, J.A. (1976) The Gladstone-Dale relationship– Part 1: derivation of new constants. The Canadian
Mineralogist, 14, 498–502.
Mandarino, J.A. (2007) The Gladstone–Dale compatibility of minerals and its use in selecting mineral species
for further study. The Canadian Mineralogist, 45,
1307–1324.
Ohwada, K. (1976) Infrared spectroscopic studies of someuranyl nitrate complexes. Journal of Coordination
Chemistry, 6, 75–80.
Plášil, J., Buixaderas, E., Čejka, J., Sejkora, J., Jehlička, J.
and Novák, M. (2010) Raman spectroscopic study ofthe uranyl sulphate mineral zippeite: low wavenumber
and U–O stretching regions. Analytical andBioanalytical Chemistry, 397, 2703–2715.

778

KLAPROTHITE, PÉLIGOTITE AND OTTOHAHNITE: NEW URANYL SULFATE MINERALS

Plášil, J., Kampf, A.R., Kasatkin, A.V., Marty, J., Škoda,R., Silva, S. and Čejka, J. (2013) Meisserite, Na5(UO2)(SO4)3(SO3OH)(H2O), a new uranyl sulfate mineralfrom the Blue Lizard mine, San Juan County, Utah,
USA. Mineralogical Magazine, 77, 2975–2988.
Plášil, J., Kampf, A.R., Kasatkin, A.V. and Marty, J. (2014)
Bluelizardite, Na7(UO2)(SO4)4Cl(H2O)2, a new uranyl
sulfate mineral from the Blue Lizard mine, San JuanCounty,Utah,USA.JournalofGeosciences,59,145–158.

Plášil, J., Meisser, N. and Čejka, J. (2015) The crystal
structure of Na6[(UO2)(SO4)4](H2O)4: X-ray and
Raman spectroscopy study. The Canadian
Mineralogist, 54, 5–20.
Sheldrick, G.M. (2008) A short history of SHELX. Acta
Crystallographica, A64, 112–122.
Wood, R.M. and Palenik, G.J. (1999) Bond valence sumsin coordination chemistry. Sodium-oxygen complexes. Inorganic Chemistry, 38, 3926–3930.

779