Mineralogical Magazine, February 2012, Vol. 76(1), pp. 45–57

Davidlloydite, ideally Zn3(AsO4)2(H2O)4, a new arsenate
mineral from the Tsumeb mine, Otjikoto (Oshikoto) region,
Namibia: description and crystal structure
F. C. HAWTHORNE1,*, M. A. COOPER1, Y. A. ABDU1, N. A. BALL1, M. E. BACK2 AND K. T. TAIT2
1
2

Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
Department of Natural History, Royal Ontario Museum, 100 Queen’s Park, Toronto, Ontario M5S 2C6, Canada[Received 27 October 2011; Accepted 6 December 2011; Associate Editor: Allan Pring]

ABSTR ACTDavidlloydite, ideally Zn3(AsO4)2(H2O)4, is a new supergene mineral from the Tsumeb mine, Otjikoto(Oshikoto) region, Namibia. It occurs as elongated prisms (~10:1 length-to-width ratio) that are
flattened on {010}, and up to 100620610 mm in size. The crystals occur as aggregates (up to 500 mm
across) of subparallel to slightly diverging prisms lying partly on and partly embedded in fine-grained
calcioandyrobertsite. Crystals are prismatic along [001] and flattened on {010}, and show the forms{010} dominant and {100} subsidiary. Davidlloydite is colourless with a white streak and a vitreous
lustre; it does not fluoresce under ultraviolet light. The cleavage is distinct on {010}, and no parting or
twinning was observed. The Mohs hardness is 3 4. Davidlloydite is brittle with an irregular to hackly
fracture. The calculated density is 3.661 g cm 3. Optical properties were measured with a Bloss spindle
stage for the wavelength 590 nm using a gel filter. The indices of refraction are a = 1.671, b = 1.687,
g = 1.695, all 0.002; the calculated birefringence is 0.024; 2Vobs = 65.4(6)º, 2Vcalc = 70º; thedispersion is r < v, weak; pleochroism was not observed. Davidlloydite is triclinic, space group P1̄,with a = 5.9756(4), b = 7.6002(5), c = 5.4471(4) Å, a = 84.2892(9), b = 90.4920(9), g = 87.9958(9)º,V = 245.99(5) Å3, Z = 1 and a:b:c = 0.7861:1:0.7167. The seven strongest lines in the X-ray powder
diffraction pattern [listed as d (Å), I, (hkl)] are as follows: 4.620, 100, (011, 1̄10); 7.526, 71, (010);
2.974, 49, (200, 02̄1); 3.253, 40, (021, 120); 2.701, 39, (2̄10, 002, 1̄2̄1); 5.409, 37, (001); 2.810, 37,(210). Chemical analysis by electron microprobe gave As2O5 43.03, ZnO 37.95, CuO 5.65, H2O(calc)
13.27, sum 99.90 wt.%. The H2O content and the valence state of As were determined by crystal
structure analysis. On the basis of 12 anions with H2O = 4 a.p.f.u., the empirical formula is(Zn2.53Cu0.39)S2.92As2.03O8(H2O)4.
The crystal structure of davidlloydite was solved by direct methods and refined to an R1 index of
1.51% based on 1422 unique observed reflections collected on a three-circle rotating-anode (MoKa
radiation) diffractometer equipped with multilayer optics and an APEX-II detector. In the structure ofdavidlloydite, sheets of corner-sharing (As5+O4) and (ZnO4) tetrahedra are linked by ZnO2(H2O)4octahedra. The structure is related to that of parahopeite.

K EY WORDS : Davidlloydite, new mineral species, arsenate, Tsumeb mine, Otjikoto (Oshikoto) region, Namibia,
crystal structure, electron microprobe analysis, optical properties.

Introduction
THE Tsumeb mine in the Otjikoto (Oshikoto)region of Namibia was a major source of Cu-Pb-* E-mail: frank_hawthorne@umanitoba.ca
DOI: 10.1180/minmag.2012.076.1.45# 2012 The Mineralogical Society

Zn ores for much of the twentieth century(Weber and Wilson, 1977) and is well known
for the large number of mineral species it has
produced (Pinch and Wilson, 1977).
Examination of a sample from the Charles Key
Collection, purchased by the Royal Ontario
Museum in 2003, resulted in the identiﬁcation

F. C. HAWTHORNE ET AL.

davidlloydite has been deposited in the mineralcollection of the Department of Natural History,
Royal Ontario Museum, catalogue number
M56120.

of a new hydrated zinc arsenate mineral. This
mineral is named davidlloydite after David
Lloyd (born 24 March 1943 in Bristol,England), a prominent mineral collector who
was a prime mover in the re-opening of the
Tsumeb mine for mineral collecting, and who
has made signiﬁcant contributions to mineralogy
through extensive ﬁeld collecting at many
localities in the British Isles.
The new mineral and mineral name have been
approved by the Commission on New Minerals,
Nomenclature and Classiﬁcation of theInternational Mineralogical Association (IMA
2 0 11 - 05 3 ) . T h e h o l o t y p e sp e c i m e n o f

OccurrenceDavidlloydite was discovered on a sample fromthe Tsumeb mine, Otjikoto (Oshikoto) region,
Namibia. It is associated with stranskiite,
geminite, adamite olivenite and calcioandyrobertsite, and is thought to have originated on
the 4400-foot level of the mine in an area known
as the third oxidation zone.

FIG. 1. The Raman spectrum of davidlloydite.

46

DAVIDLLOYDITE, A NEW ARSENATE MINERAL FROM TSUMEB, NAMIBIATABLE 1. Optical orientation (º) of davidlloydite.

X
Y
Z

a

b

c

118.3
142.7
67.8

117.4
56.1
46.3

142.8
77.3
124.2

T ABLE 3. X-ray powder diffraction data for
davidlloydite.

Physical properties
Davidlloydite crystals are elongated prisms(~10:1 length-to-width ratio) that are ﬂattenedon {010} and up to 100620610 mm in size. The
crystals occur as aggregates (up to 500 mm across)of subparallel to slightly diverging prisms lying
partly on and partly embedded in ﬁne-grained
calcioandyrobertsite. Crystals are prismatic along[001] and ﬂattened on {010}, and show the forms{010} dominant, {100} subsidiary. Davidlloydite
is colourless with a white streak and a vitreous toopalescent lustre; it does not ﬂuoresce underultraviolet light. The cleavage is distinct on{010}, and no parting or twinning was observed.
The Mohs hardness is 3 4, and davidlloydite isbrittle with an irregular to hackly fracture. The
density was not measured due to the paucity ofmaterial. The calculated density is 3.661 g cm 3.
Optical properties were measured with a Bloss
spindle stage for the wavelength 590 nm. The
indices of refraction are a = 1.671, b = 1.687, g =1.695, all 0.002; 2Vobs = 65.4(6)º (measured
with a spindle stage, data processed using
Excalibr II, Bartelmehs et al., 1992), 2Vcalc =70º; the dispersion is r < v, weak. No pleochroism
was observed; the optic orientation is given in
Table 1.

TABLE 2. Chemical composition of davidlloydite.
Constituent

Mean (wt.%)

Range

As2O5
ZnO
CuO
H2O(calc.)
Total

43.03(1.08)
37.95(1.62)
5.65(0.68)
13.27
99.90

41.18 43.95
35.86 40.23
4.70 6.55

Iobs

dobs

dcalc

h k l

71
16
37
100

7.526
5.960
5.409
4.620

25
10

4.200
3.999

9
30
24
40

3.768
3.635
3.393
3.253

49

2.974

11
37
39b*

2.885
2.810
2.701

20

2.626

13
23
17

2.514
2.459
2.404

2
22
19

2.299
2.225
2.175

6
2
4b*
10
9
8

2.138
2.066
2.035
2.014
1.996
1.887

6
6
3
3

1.839
1.819
1.781
1.740

3
2
5

1.721
1.698
1.672

7.547
5.964
5.420
4.627
4.600
4.208
4.031
3.991
3.773
3.633
3.394
3.253
3.241
2.982
2.961
2.886
2.808
2.740
2.710
2.688
2.636
2.618
2.516
2.458
2.409
2.402
2.302
2.226
2.184
2.172
2.137
2.067
2.041
2.016
1.996
1.890
1.887
1.884
1.840
1.816
1.781
1.742
1.741
1.721
1.697
1.672
1.677

0 1 0
1 0 0
0 0 1
0 1 1
1̄ 1 00 1̄ 1
1̄ 0 11 0 1
0 2 0
1̄ 1 1
1 1̄ 1
0 2 1
1 2 0
2 0 0
0 2̄ 11 2 1
2 1 0
2̄ 1 00 0 2
1̄ 2̄ 10 1 2
1 2̄ 10 3 0
1 0 2
1̄ 1 2
2 1̄ 11̄ 1̄ 22 2 1
1̄ 3 12̄ 2 12̄ 2̄ 12 2̄ 1
1 3̄ 1
2̄ 0 22 0 2
2̄ 3 0
0 4 0
2 3 1
2 2 2
2̄ 2 2
1̄ 4 02̄ 2̄ 22 3̄ 11 1 3
0 2 3
1̄ 4̄ 1
1 3̄ 2* The abbreviation b signiﬁes a broad line.

Not detected: P, Mg, Mn, Fe, Al, Si, Na, Ca, V, Cr.

47

F. C. HAWTHORNE ET AL.

TABLE 4. Summary of crystallographic, data collection and structure reﬁnement information for davidlloydite.
a (Å)b (Å)c (Å)
a (º)
b (º)
g (º)
V (Å3)
Space groupZ
dcalc (g cm 3)
Cell content

5.9756(4)7.6002(5)5.4471(4)84.2892(9)90.4920(9)87.9958(9)245.99(5)
P1̄
1
3.661
Zn3(AsO4)2(H2O)4

Crystal size (mm)Radiation/monochromaterNo. of reflections
No. in Ewald sphere
No. unique reflections
No. with (Fo > 4sF)
Rmerge%R1%
wR2%

20620680
MoKa/Graphite
8846
2946
1477
1422
0.91
1.51
4.13

R1 = S(|Fo| |Fc|)/S|Fo|.
wR2 = [Sw(F2o F2c )2/Sw(F2o)2], w = 1/[s2(F2o) + (0.0139P)2 + 0.34P] where P = (Max(F2o,0) + 2F2c )/3.

Raman spectroscopy
The Raman spectrum of davidlloydite is shown in
Fig. 1. In the 100 1200 cm 1 region, there is aprominent peak at 865 cm 1 and a strong but
subsidiary band at 841 cm 1, both of which may
be assigned to As5+ O stretching modes. Lowerenergy peaks at 550 (w), 504 (m), 454 (s) and420 (vw) cm 1 may be assigned to Zn O
stretching modes, and the numerous lowerenergy bands may be assigned to collective
lattice modes: 394 (vw), 353 (w), 305 (w),294 (w), 258 (w), 211 (w), 200 (w), 182 (w),
170 (w), 163 (w) and 121 (doublet, vw). In the2500 4000 cm 1 region, there is a broadenvelope with signiﬁcant structure, centred on~3200 cm 1 that may be assigned to various
stretching modes of the H2O group.

The empirical formula was calculated on the basisof 12 anions with H2O = 4 a.p.f.u. (atoms per
formula unit) as indicated by crystal-structure
solution and reﬁnement, giving(Zn2.53Cu0.39)S2.92As2.03O8(H2O)4, and an ideal
formula Zn3(AsO4)2(H2O)4.
X-ray powder diffraction
X-ray powder-diffraction data were obtainedusing a Gandolﬁ attachment mounted on a
Bruker D8 rotating-anode Discover SuperSpeed
micro-powder diffractometer with a multi-wire
2D detector. Data (in Å for CuKa) are listed inTable 3. Unit-cell parameters reﬁned from thepowder data are as follows: a = 5.968(4), b =7.589(4), c = 5.448(3) Å, a = 84.29(5)º, b =90.38(4), g = 88.01(5), V = 245.3(2) Å3.

Chemical composition
Crystal-structure solution and reﬁnement

Davidlloydite was analysed using a Cameca SX100 electron microprobe operating in wavelengthdispersive mode with an accelerating voltage of
15 kV, a specimen current of 10 nA and a beam
diameter of 10 mm. Different crystals were used
for the single-crystal structure reﬁnement andchemical analysis. The standards used wereadamite (As, Zn) and olivenite (Cu). The data
were reduced and corrected by the PAP method of
Pouchou and Pichoir (1985) and are given in
Table 2 (mean of ﬁve determinations). The
presence and quantity of H2O groups were
established by crystal-structure solution andreﬁnement. In addition, Raman spectroscopy(Fig. 1) indicates a broad intense band in theregion ~3200 cm 1, which is indicative of H2O.

A crystal was attached to a tapered glass ﬁbre andmounted on a Bruker D8 three-circle diffractometer equipped with a rotating-anode generator(MoKa), multilayer optics and an APEX-II
detector. A total of 2946 intensities (thosewithin the Ewald sphere) was collected to 60º2y
using 10 s per 0.2º frame, with a crystal-todetector distance of 5 cm. Empirical absorption
corrections (SADABS; Sheldrick, 2008) wereapplied and equivalent reﬂections were correctedfor Lorentz, polarization and background effects,
averaged and reduced to structure factors. The
unit-cell dimensions were obtained by leastsquares reﬁnement of the positions of 6593
reﬂections with I > 10sI and are given in48

0.01224(12)0.01226(7)0.00916(6)0.0153(3)0.0146(3)0.0128(3)0.0145(3)0.0181(3)0.0208(3)0.039(10)0.056(13)0.058(13)0.059(13)0.01178(19)0.01032(11)0.00869(10)0.0204(8)0.0096(7)0.0157(7)0.0105(7)0.0155(8)0.0270(9)0.00034(12)0.00186(8)0.00125(7)0.0045(6)0.0027(5)0.0002(5)0.0010(5)0.0007(6)0.0008(6)0.00126(12)0.00006(8)0.00025(7)0.0037(6)0.0011(5)0.0012(5)0.0006(6)0.0037(6)0.0031(7)0.00005(13)0.00121(9)0.00002(7)0.0007(5)0.0007(6)0.0014(5)0.0015(6)0.0009(6)0.0009(6)Table 4, together with other information
pertaining to data collection and structure
reﬁnement.
All calculations were done with the SHELXTL
PC (Plus) system of programs; R indices are of
the form given in Table 4 and are expressed aspercentages. The structure was solved in the spacegroup P1̄ by direct methods and reﬁned toconvergence by full-matrix least-squares
methods with anisotropic-displacement parameters for all atoms. At the later stages of
reﬁnement, difference-Fourier maps showed
weak density maxima approximately 1 Å fromthe O(5) and O(6) anions that incident bondvalence sums indicate are H2O groups. Thesemaxima were entered into the structure model as
H atoms and their parameters were reﬁned withthe soft constraint that the O H distance beapproximately 0.98 Å. The structure converged toa ﬁnal R 1 index of 1.51%. Reﬁned atom
coordinates and anisotropic-displacement parameters are listed in Table 5, selected interatomic
distances are given in Table 6, and bond valences,calculated with the parameters of Brown andAltermatt (1985), are given in Table 7. A table ofstructure factors and a crystallographic information ﬁle are available at www.minersoc.org/pages/
e_journals/dep_mat.html.
Crystal structure
Coordination of cations
In the structure of davidlloydite, the As site is
tetrahedrally coordinated by four O anions at amean distance of 1.687 Å, which is characteristicof As5+ [e.g. adamite: 1.681 Å (Hawthorne,
1976a); scorodite: 1.680 Å (Hawthorne, 1976b)],and the site-scattering is in accord with fulloccupancy of the site by As. There are two Znsites with different coordination numbers, which
are occupied primarily by Zn with minor Cu2+
(Table 2). The Zn(1) site is octahedrally coordinated by two O2 anions and four (H2O) groups
with a <Zn O> distance of 2.112 Å. The Zn(2)site is tetrahedrally coordinated by O2 anionswith a <Zn O> distance of 1.970 Å. The [4+2]distortion observed for the Zn(1) octahedronsuggests that the Cu measured by electronmicroprobe analysis (Table 2) is ordered at theoctahedrally coordinated Zn(1) site. The crystal
analysed by electron-microprobe analysis can be
described by the site-sp eciﬁc fo rmula[6](Zn0.6Cu0.4)[4]Zn2(AsO4)2(H2O)4.

0
0.23922(4)0.25896(3)0.4813(3)0.2996(3)0.0271(3)0.1952(3)0.2229(3)0.2711(3)0.211(6)0.232(7)0.413(4)0.325(7)
Zn(1)
Zn(2)
As(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
H(1)
H(2)
H(3)
H(4)


0.10407(3)0.87032(3)0.7644(2)0.8972(2)0.7464(2)0.0630(2)0.4010(2)0.5420(2)0.2762(14)0.453(5)0.481(5)0.662(2)
0.81081(4)0.33696(4)0.2259(3)0.6354(3)0.3144(3)0.1674(3)0.2726(3)0.7834(4)0.245(7)0.101(3)0.748(8)0.791(8)0.01425(19)0.01204(12)0.00945(10)0.0119(7)0.0200(8)0.0103(6)0.0209(8)0.0253(9)0.0190(8)0.01053(18)0.01445(12)0.00940(10)0.0140(7)0.0144(7)0.0120(7)0.0116(7)0.0134(7)0.0162(8)

U23
U33
U22
U11
z/c
y/b
x/a
Atom

TABLE 5. Atom coordinates and displacement parameters (Å2) for davidlloydite.

U13

U12

Ueq

DAVIDLLOYDITE, A NEW ARSENATE MINERAL FROM TSUMEB, NAMIBIA

49

F. C. HAWTHORNE ET AL.

TABLE 6. Selected interatomic distances (Å) and angles (o) in davidlloydite.
Zn(1) O(3)Zn(1) O(5)Zn(1) O(6)<Zn(1) O>

62
62
62

2.050(2)2.005(2)2.281(2)2.112

Zn(2) O(1)Zn(2) O(2)Zn(2) O(3)Zn(2) O(4)<Zn(2) O>

1.978(2)1.944(2)1.998(2)1.958(2)1.970

As O(1)
As O(2)As O(3)
As O(4)<As O>

1.678(2)1.675(2)1.713(2)1.682(2)
1.687

O(5)
O(5)
O(5)
O(5)

H(1)
H(2)
H(1)_O(4)H(2)_O(6)0.980(1)0.980(1)
175(3)
176(4)

H(1)_O(4)H(2)_O(6)1.720(4)1.814(4)

O(6)
O(6)
O(6)
O(6)

H(3)
H(4)
H(3)_O(1)H(4)_O(2)0.980(1)0.980(1)
135(3)
143(4)

H(3)_O(1)H(4)_O(2)1.94(3)1.90(3)

Anion identities and hydrogen bonding

Table 6. The O(4) and O(6) anions are acceptor
anions for hydrogen bonds from the donor O(5)anion, and the O(1) and O(2) anions are acceptor
anions for hydrogen bonds from the donor O(6)anion. The resulting incident bond-valence sums
at all of the anions in the structure accord with thevalence-sum rule to within 0.05 vu or less
(Table 7) and the anion part of the formula isO8(H2O)4 for Z = 1.

There are six crystallographically distinct anions,O(1) O(6) (Table 5). Inspection of the bondvalence table (Table 7) shows that the bondvalence incident at O(1) to O(4), omitting any
contribution from H, is 51.75 vu, indicating thatthese anions are O2 . The corresponding bondvalence incident at O(5) and O(6) is 0.44 and0.21 vu, indicating that both O(5) and O(6) are
H2O groups. In accord with this conclusion, four
H sites were identiﬁed in difference-Fourier maps
close to the O(5) and O(6) sites and reﬁned in theﬁnal stages of structure reﬁnement. The resultinghydrogen-bond arrangements are given in

Bond topology
A very unusual aspect of the structure ofdavidlloydite is its relation to the structure of

TABLE 7. Bond-valence* table for davidlloydite.

O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
S

Zn(1)

Zn(2)

As

S

0.3962;

0.48
0.52
0.45
0.50

1.27
1.28
1.16
1.26

1.75
1.80
2.00
1.76
0.44
0.21

0.44 62;
0.21 62;
2.08

1.95

H(1)

H(2)

H(3)

H(4)

0.2
0.2
0.2
0.8

4.97

1.00

* See Brown and Altermatt (1985).

50

0.8
0.2
1.00

0.8
1.00

0.8
1.00

S
1.95
2.00
2.00
1.96
2.04
2.01

DAVIDLLOYDITE, A NEW ARSENATE MINERAL FROM TSUMEB, NAMIBIA

FIG. 2. Part of the crystal structures of (a) davidlloydite and (b) parahopeite projected onto (010), showing theconnectivity of the (Zn(2)O4) tetrahedra (yellow), the (AsO4) tetrahedra (blue in davidlloydite) and the (PO4)
tetrahedra (pink in parahopeite) to form sheets of corner-sharing tetrahedra of the form [ZnT5+O4]. Green circle:
Zn(1) site above the [ZnT5+O4] sheet; the origin in parahopeite is shifted by (0, , 0).

translational repeat in the b direction is different
in each structure (Fig. 3). This results in aseemingly different linkage between the[ZnTO4] sheets in each structure. As is apparent
in Fig. 3, the ZnO2(H2O)4 octahedra linking
adjacent sheets are inclined to the right indavidlloydite (Fig. 3a) and to the left in parahopeite (Fig. 3b), and these different linkages
impart quite different degrees of geometrical
distortion to the constituent layers (Fig. 2).

parahopeite, Zn3(PO4)2(H2O)4 (Chao, 1969). The
details of this relation seem to be affected by the
relative orientation of the structural units in thetwo structures (see below). Of course, this is notreally the case; the structures are as they are, andtheir relation cannot be affected by issues ofrelative orientation. However, this issue is quite
subtle in the present case, and is of interest, as
failure to recognize such a relation could easily
lead to the erroneous identiﬁcation of the samestructure as two distinct minerals.

Davidlloydite as an inverse parahopeite
structure
We may select a different unit cell for
davidlloydite that is geometrically congruent tothat of parahopeite. The matrix transformation
between the two orientations of davidlloydite is[ 1 0 0 / 0 1 0 / 0 0 1]. In this orientation, theunit cells and site coordinates of davidlloydite
and parahopeite are congruent (Table 8). The
only apparent difference between the two
structures is the distinction in cation identity at
the two tetrahedrally coordinated sites; thelocations of the pentavalent and divalentcations appear interchanged in the two structures(Fig. 4).

Davidlloydite and parahopeite as stacking
variants
In the crystal structure of davidlloydite, ZnO4
and AsO4 tetrahedra share corners to form a sheet(Fig. 2a) of the form [ZnAsO4] in which thecations occur at the vertices of a 44 net. This sheet
is topologically identical to the [ZnPO4] sheet inparahopeite (Fig. 2b). In both davidlloydite andparahopeite, the sheets stack in the b direction(Fig. 3) and are linked by sharing corners with
ZnO2(H2O)4 octahedra. The position of [6]Znabove the sheet differs in each structure (Fig. 2):
it is located at 0  0 in parahopeite and 0   indavidlloydite. As a result, the sense of the51

F. C. HAWTHORNE ET AL.

FIG. 3. The crystal structure of (a) davidlloydite and (b) parahopeite projected along [100], showing the stacking of
the [ZnT5+O4] sheets in the b direction. The (Zn(2)O4) tetrahedra are yellow, the (AsO4) tetrahedra are blue in
davidlloydite and the (PO4) tetrahedra are pink in parahopeite, Zn(1) octahedra are green.

FIG. 4 (facing page). All three principal axial projections (a, c, e) for davidlloydite transformed via [ 1 0 0 / 0 1 0 /0 0 1] and (b, d, f) parahopeite. The (Zn(2)O4) tetrahedra are yellow, the (AsO4) tetrahedra are blue in davidlloydite
and the (PO4) tetrahedra are pink in parahopeite, Zn(1) octahedra are green. The origin for the parahopeite structureis that used by Chao (1969).

52

DAVIDLLOYDITE, A NEW ARSENATE MINERAL FROM TSUMEB, NAMIBIA

53

F. C. HAWTHORNE ET AL.

TABLE 8. Davidlloydite and parahopeite analogous cell and structure comparison.
——— Davidlloydite —————— Parahopeite ———

5.976
7.600
5.447
95.71
90.49
92.00
246.0

5.768
7.550
5.276
93.42
91.18
91.37
229.2

a (Å)
b
c
a (º)
b
g
V (Å3)Zn(1)As / Zn(2)Zn(2) / P
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)

x/a

y/b

z/c

x/a

y/b

z/c

0
0.259
0.239
0.519
0.195
0.027
0.300
0.271
0.223

0
0.630
0.396
0.264
0.437
0.246
0.603
0.958
0.099

0
0.837
0.311
0.274
0.667
0.186
0.135
0.283
0.773

0
0.252
0.250
0.468
0.233
0.029
0.251
0.230
0.266

0
0.598
0.362
0.259
0.391
0.252
0.542
0.891
0.059

0
0.817
0.296
0.227
0.586
0.197
0.171
0.261
0.748

Hydrogen bonding in davidlloydite andparahopeite

group; in the classiﬁcation of Dana (Gaines etal., 1997), it is a class 40 normal hydrated
phosphate-arsenate-vanadate related to parahopeite (Kumbasar and Finney, 1968) (40.3.3.1)
and hopeite (Hill and Jones, 1976) (40.3.4.1).
Structurally, davidlloydite is similar to parahopeite (as discussed above) and it is a triclinic
polytype of arsenohopeite (orthorhombic
Zn 3 (AsO 4 ) 2 (H 2 O) 4 , Neuhold et al., 2011).
Arsenohopeite is the arsenate analogue ofhopeite. The structural relations between parahopeite (Kumbasar and Finney, 1968) and hopeite

The arrangement of the hydrogen bonds for
davidlloydite is shown in Fig. 5a. For the H2Ogroup at O(5), the hydrogen bond from H(1) isdirected toward the O(4) anion of the neighbouring sheet of tetrahedra, and the hydrogenbond from H(2) is directed across the interstitialregion to the neighbouring O(6) anion (the other
H2O group in the structure) of the adjacent Zn(1)octahedron. For the H2O group at O(6), thehydrogen bonds from H(3) and H(4) are directed
toward opposing O(1) and O(2) anions, respectively, belonging to the sheets on either side of theZn(1) octahedron. We have inferred the samestyle of hydrogen bonding for parahopeite(Fig. 5b). Note that the two structures differ
only in the relative sense of alternating Zn(1)occupancy and neighbouring hydrogen bonding in
the interlayer region. The stereochemistry of thedonor-acceptor anions is given for the two
structures in Table 9.

TABLE 9. Donor-acceptor anion distances (Å) andangles (º) for the hydrogen bonding in davidlloydite and parahopeite.

Related minerals
In the classiﬁcation of Strunz (Strunz and Nickel,2001), davidlloydite is a class 8 phosphatearsenate-vanadate of the 08.CA.30 hopeite
54

Davidlloydite

Parahopeite

O(5)_O(4)O(5)_O(6)O(4) O(5) O(6)

2.70
2.79
95.2

2.66
2.80
123.3

O(6)_O(1)O(6)_O(2)O(1) O(6) O(2)

2.72
2.75
139.4

2.89
2.71
148.1

DAVIDLLOYDITE, A NEW ARSENATE MINERAL FROM TSUMEB, NAMIBIA

FIG. 5. Hydrogen bonding in (a) davidlloydite and proposed hydrogen-bonding in (b) parahopeite projected down anaxis rotated slightly from [100]. The (Zn(2)O4) tetrahedra are yellow, the (AsO4) tetrahedra are blue in davidlloydite
and the (PO4) tetrahedra are pink in parahopeite, Zn(1) octahedra are green.

55

F. C. HAWTHORNE ET AL.

TABLE 10. Comparative table for selected minerals of the hopeite group.
Davidlloydite

Parahopeite

HopeiteArsenohopeite*

FormulaSymmetry
Space groupa (Å)b (Å)c (Å)
a (º)
b (º)
g (º)
Z
d (g cm 3)
ColourCleavage

Zn3(AsO4)2(H2O)4
Triclinic
P1̄
5.97567.60025.447184.2892
90.492087.9958
1
3.661
Colourless{010} distinct

Zn3(PO4)2(H2O)4
Triclinic
P1̄
5.768
7.550
5.296
93.42
91.18
91.37
1
3.32
Colourless{010} perfect

Zn3(AsO4)2(H2O)4
Orthorhombic
Pnma
10.80419.003
5.112
90
90
90
4
3.46

Hardness
Occurrence

3 4
Cu-Zn deposits

3 4
Cu-Zn deposits

Zn3(PO4)2(H2O)4
Orthorhombic
Pnma
10.59418.333
5.029
90
90
90
4
2.94
Colourless to greyish white{010} perfect, {100} good,{001} poor
3Cu-Zn deposits* From Neuhold et al. (2011).

Acknowledgements

were discussed by Hill and Jones (1976). Selected
properties of davidlloydite, parahopeite, hopeite
and arsenohopeite are listed in Table 10. Other
minerals of the form (M2+)3(T5+O4)2(H2O)4, suchas phosphophyllite, Zn2Fe(PO4)2(H2O)4; ludlami te , F e 3 ( P O 4 ) 2 (H 2 O ) 4 a n d r o l l a n d i t e ,Cu3(AsO4)2(H2O)4, have different M-coordination environments (i.e. not [6]M [4]M2) andrepresent structural variants (Hill, 1977;
Abrahams and Bernstein, 1966; Sarp and Černy,2000).

We thank Tony Kampf and an anonymous
reviewer for their comments on this paper. This
work was supported by a Canada Research Chair
in Crystallography and Mineralogy and by
Natural Sciences and Engineering ResearchCouncil of Canada Discovery, Equipment andMajor Installation grants of the Natural Sciencesand Engineering Research Council of Canada, andby Innovation grants from the Canada Foundation
for Innovation to FCH.

Triclinic polytypism in davidlloydite andparahopeite

References
Abrahams, S.C. and Bernstein, J.L. (1966) Crystal
structure of paramagnetic ludlamite,
Fe3(PO4)2·4(H2O), at 298ºK. Journal of Chemical
Physics, 44, 2223 2229.
Bartelmehs, K.L., Bloss, F.D., Downs, R.T. and Birch,
J . B . ( 1 9 9 2 ) E x c a l i b r I I . Z e i t s c h r i f t f ü r
Kristallographie, 199, 186 196.
Brown, I.D. and Altermatt, D. (1985) Bond-valence
parameters obtained from a systematic analysis of
the inorganic crystal structure database. Acta
Crystallographica, B41, 244 247.
Chao, G.Y. (1969) Reﬁnement of the crystal structure ofparahopeite. Zeitschrift für Kristallographie, 130,261 266.
Gaines, R.V., Skinner, H.C.W., Foord, E.E., Mason, B.
and Rosenwieg, A. (1997) Dana’s New Mineralogy,

The tetrahedral [ZnAsO4] sheet in davidlloydite
displays minor rotation of the tetrahedra relative
to the [ZnPO4] sheet in parahopeite (Fig. 2), andthe general freedom inherent in the simple corner
linkage of tetrahedra seems to easily accommodate the difference in radius of [4]As5+ and [4]P.
The similar patterns of intersheet linkage byinterstitial ZnO4(H2O)2 octahedra and associatedhydrogen bonding (Fig. 3) have the generalappearance of being compatible in both structures.
This suggests that two different triclinic polytypes
may be possible for both davidlloydite andparahopeite; however, the diffraction characteristics for both minerals suggest simple orderedstructures, rather than disordered mixtures ofpolytypes.
56

DAVIDLLOYDITE, A NEW ARSENATE MINERAL FROM TSUMEB, NAMIBIA

Minerals: a descriptive list. Mineralogical Record,
8(3), 17 37.
Pouchou, J.L. and Pichoir, F. (1985) ‘PAP’ j(rZ)procedure for improved quantitative microanalysis.
Pp. 104 106 in: Microbeam Analysis (J.T.
Armstrong, editor). San Francisco Press, San
Francisco, California, USA.
Sarp, H. and Cerný, R. (2000) Rollandite,Cu3(AsO4)2·4H2O, a new mineral: its description
and crystal structure. European Journal of
Mineralogy, 12, 1045 1050.
Sheldrick, G.M. (2008) A short history of SHELX. Acta
Crystallographica, A64, 112 122.
Strunz, H. and Nickel, E.H. (2001) Strunz Mineralogical
Tables, Ninth Edition. Schweizerbart’sche
Verlagsbuchhandlung, Stuttgart, Germany.
Weber, D. and Wilson, W.E. (1977) Tsumeb IV.
Geology. Mineralogical Record, 8(3), 14 16.

Eighth Edition. Wiley and Sons, New York, USA.
Hawthorne, F.C. (1976a) Reﬁnement of the crystal
structure of adamite. The Canadian Mineralogist, 14,
143 148.
Hawthorne, F.C. (1976b) The hydrogen positions inscorodite. Acta Crystallographica, B32, 2891 2892.
Hill, R.J. (1977) The crystal structure of phosphophyllite. American Mineralogist, 62, 812 817.
Hill, R.J. and Jones, J.B. (1976) The crystal structure ofhopeite. American Mineralogist, 61, 987 995.
Kumbasar, I. and Finney, J.J. (1968) The crystal
structure of parahopeite. Mineralogical Magazine,
36, 621 624.
Neuhold, F., Kolitsch, U., Bernhardt, H.-J. andLengauer, C.L. (2011) Arsenhopeite, IMA 2010-69.
CNMNC Newsletter No. 8, April 2011, page 291;
Mineralogical Magazine, 75, 289 294.
Pinch, W.W. and Wilson, W.E. (1977) Tsumeb V.

57

data_davidlloydite_audit_creation_method_chemical_name_systematic;?
;_chemical_name_common_chemical_melting_point_chemical_formula_moiety_chemical_formula_sum'H1.14 As0.29 O1.71 Zn0.43'_chemical_formula_weight

SHELXL-97

?
?
?
78.00

loop_
_atom_type_symbol_atom_type_description_atom_type_scat_dispersion_real_atom_type_scat_dispersion_imag_atom_type_scat_source'O' 'O'
0.01060.0060'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''H' 'H'
0.00000.0000'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''Zn' 'Zn'
0.28391.4301'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''As' 'As'
0.04992.0058'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'_symmetry_cell_setting_symmetry_space_group_name_H-M

?
?

loop_
_symmetry_equiv_pos_as_xyz'x, y, z''-x, -y, -z'_cell_length_a_cell_length_b_cell_length_c_cell_angle_alpha_cell_angle_beta_cell_angle_gamma_cell_volume_cell_formula_units_Z_cell_measurement_temperature_cell_measurement_reflns_used_cell_measurement_theta_min_cell_measurement_theta_max

5.9756(4)7.6002(5)5.4471(4)84.2892(9)90.4920(9)87.9958(9)245.99(3)7293(2)?
?
?

_exptl_crystal_description_exptl_crystal_colour_exptl_crystal_size_max_exptl_crystal_size_mid_exptl_crystal_size_min_exptl_crystal_density_meas

?
?
?
?
?
?

_exptl_crystal_density_diffrn_exptl_crystal_density_method_exptl_crystal_F_000_exptl_absorpt_coefficient_mu_exptl_absorpt_correction_type_exptl_absorpt_correction_T_min_exptl_absorpt_correction_T_max_exptl_absorpt_process_details

3.686'not measured'260
13.991?
?
?
?

_exptl_special_details;?
;_diffrn_ambient_temperature_diffrn_radiation_wavelength_diffrn_radiation_type_diffrn_radiation_source_diffrn_radiation_monochromator_diffrn_measurement_device_type_diffrn_measurement_method_diffrn_detector_area_resol_mean_diffrn_standards_number_diffrn_standards_interval_count_diffrn_standards_interval_time_diffrn_standards_decay_%_diffrn_reflns_number_diffrn_reflns_av_R_equivalents_diffrn_reflns_av_sigmaI/netI_diffrn_reflns_limit_h_min_diffrn_reflns_limit_h_max_diffrn_reflns_limit_k_min_diffrn_reflns_limit_k_max_diffrn_reflns_limit_l_min_diffrn_reflns_limit_l_max_diffrn_reflns_theta_min_diffrn_reflns_theta_max_reflns_number_total_reflns_number_gt_reflns_threshold_expression

293(2)
0.71073
MoK\a'fine-focus sealed tube'
graphite
?
?
?
?
?
?
?
2946
0.00910.0134
-8
8
-10
10
-7
7
2.70
30.24
1477
1422
>2sigma(I)_computing_data_collection_computing_cell_refinement_computing_data_reduction_computing_structure_solution_computing_structure_refinement_computing_molecular_graphics_computing_publication_material?
?
?
'SHELXS-97 (Sheldrick, 1990)''SHELXL-97 (Sheldrick, 1997)'?
?

_refine_special_details;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR andgoodness of fit S are based on F^2^, conventional R-factors R are basedon F, with F set to zero for negative F^2^. The threshold expression ofF^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors basedon F^2^ are statistically about twice as large as those based on F, and R-

factors based on ALL data will be even larger.
;_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full_refine_ls_weighting_scheme
calc_refine_ls_weighting_details'calc w=1/[\s^2^(Fo^2^)+(0.0139P)^2^+0.3444P] where P=(Fo^2^+2Fc^2^)/3'_atom_sites_solution_primary
direct_atom_sites_solution_secondary
difmap_atom_sites_solution_hydrogens
geom_refine_ls_hydrogen_treatment
mixed_refine_ls_extinction_methodnone_refine_ls_extinction_coef?
_refine_ls_number_reflns
1477_refine_ls_number_parameters96_refine_ls_number_restraints
4_refine_ls_R_factor_all
0.0159_refine_ls_R_factor_gt
0.0151_refine_ls_wR_factor_ref
0.0413_refine_ls_wR_factor_gt
0.0411_refine_ls_goodness_of_fit_ref
1.263_refine_ls_restrained_S_all
1.261_refine_ls_shift/su_max
0.001_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label_atom_site_type_symbol_atom_site_fract_x_atom_site_fract_y_atom_site_fract_z_atom_site_U_iso_or_equiv_atom_site_adp_type_atom_site_occupancy_atom_site_symmetry_multiplicity_atom_site_calc_flag_atom_site_refinement_flags_atom_site_disorder_assembly_atom_site_disorder_group
Zn1 Zn 0.0000 0.5000 0.5000 0.01224(12) Uani 0.937(2) 2 d SP . .
Zn2 Zn 0.23922(4) 0.10407(3) 0.81081(4) 0.01226(7) Uani 1 1 d . . .
As1 As 0.25896(3) 0.87032(3) 0.33696(4) 0.00916(6) Uani 1 1 d . . .
O1 O 0.4813(3) 0.7644(2) 0.2259(3) 0.0153(3) Uani 1 1 d . . .
O2 O 0.2996(3) 0.8972(2) 0.6354(3) 0.0146(3) Uani 1 1 d . . .
O3 O 0.0271(3) 0.7464(2) 0.3144(3) 0.0128(3) Uani 1 1 d . . .
O4 O 0.1952(3) 0.0630(2) 0.1674(3) 0.0145(3) Uani 1 1 d . . .
O5 O 0.2229(3) 0.4010(2) 0.2726(3) 0.0181(3) Uani 1 1 d D . .
O6 O 0.2711(3) 0.5420(2) 0.7834(3) 0.0208(3) Uani 1 1 d D . .
H1 H 0.211(6) 0.2762(14) 0.245(7) 0.039(10) Uiso 1 1 d D . .
H2 H 0.232(7) 0.453(5) 0.101(3) 0.056(13) Uiso 1 1 d D . .
H3 H 0.413(4) 0.481(5) 0.748(8) 0.058(13) Uiso 1 1 d D . .
H4 H 0.325(7) 0.662(2) 0.791(8) 0.059(13) Uiso 1 1 d D . .
loop__atom_site_aniso_label_atom_site_aniso_U_11

_atom_site_aniso_U_22_atom_site_aniso_U_33_atom_site_aniso_U_23_atom_site_aniso_U_13_atom_site_aniso_U_12
Zn1 0.01425(19) 0.01053(18) 0.01178(19) -0.00034(12) 0.00126(12) 0.00005(13)Zn2 0.01204(12) 0.01445(12) 0.01032(11) -0.00186(8) -0.00006(8) 0.00121(9)As1 0.00945(10) 0.00940(10) 0.00869(10) -0.00125(7) 0.00025(7) 0.00002(7)O1 0.0119(7) 0.0140(7) 0.0204(8) -0.0045(6) 0.0037(6) 0.0007(5)O2 0.0200(8) 0.0144(7) 0.0096(7) -0.0027(5) -0.0011(5) 0.0006(6)O3 0.0103(6) 0.0120(7) 0.0157(7) 0.0002(5) -0.0012(5) -0.0014(5)O4 0.0209(8) 0.0116(7) 0.0105(7) 0.0010(5) -0.0006(6) 0.0014(6)O5 0.0253(9) 0.0134(7) 0.0155(7) -0.0007(6) 0.0037(6) 0.0009(6)O6 0.0190(8) 0.0162(8) 0.0270(9) -0.0008(6) 0.0031(7) -0.0009(6)_geom_special_details;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are onlyused when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop__geom_bond_atom_site_label_1_geom_bond_atom_site_label_2_geom_bond_distance_geom_bond_site_symmetry_2_geom_bond_publ_flag
Zn1 O5 2.0048(17) 2_566 ?
Zn1 O5 2.0048(17) . ?
Zn1 O3 2.0496(15) . ?
Zn1 O3 2.0496(15) 2_566 ?
Zn1 O6 2.2806(19) 2_566 ?
Zn1 O6 2.2806(19) . ?
Zn2 O2 1.9444(16) 1_545 ?
Zn2 O4 1.9578(15) 1_556 ?
Zn2 O1 1.9778(16) 2_666 ?
Zn2 O3 1.9976(15) 2_566 ?
Zn2 O6 3.3290(18) . ?
Zn2 O5 3.5155(17) . ?
Zn2 O5 3.5422(17) 1_556 ?
As1 O2 1.6751(15) . ?
As1 O1 1.6777(15) . ?
As1 O4 1.6817(15) 1_565 ?
As1 O3 1.7129(15) . ?
As1 O6 3.3050(18) . ?
As1 O5 3.6325(17) . ?
O1 Zn2 1.9778(16) 2_666 ?
O1 O6 2.720(2) 2_666 ?
O1 O5 3.200(2) . ?
O1 O6 3.339(2) 1_554 ?
O1 O5 3.353(2) 2_666 ?
O2 Zn2 1.9444(16) 1_565 ?
O2 O6 2.751(2) . ?

O3 Zn2 1.9976(15) 2_566 ?
O3 O5 2.867(2) 2_566 ?
O3 O5 2.867(2) . ?
O3 O6 2.958(2) 2_566 ?
O3 O6 3.171(2) . ?
O4 As1 1.6817(15) 1_545 ?
O4 Zn2 1.9578(15) 1_554 ?
O4 O5 2.697(2) . ?
O5 O6 2.792(2) 1_554 ?
O5 O3 2.867(2) 2_566 ?
O5 O6 2.977(3) 2_566 ?
O5 O6 3.083(3) 2_666 ?
O5 O6 3.094(2) . ?
O5 O1 3.353(2) 2_666 ?
O5 Zn2 3.5422(17) 1_554 ?
O5 H1 0.9798(10) . ?
O5 H2 0.9800(10) . ?
O6 O1 2.720(2) 2_666 ?
O6 O5 2.792(2) 1_556 ?
O6 O3 2.958(2) 2_566 ?
O6 O5 2.977(3) 2_566 ?
O6 O5 3.083(3) 2_666 ?
O6 O1 3.339(2) 1_556 ?
O6 H3 0.9799(10) . ?
O6 H4 0.9799(11) . ?
loop__geom_angle_atom_site_label_1_geom_angle_atom_site_label_2_geom_angle_atom_site_label_3_geom_angle_geom_angle_site_symmetry_1_geom_angle_site_symmetry_3_geom_angle_publ_flag
O5 Zn1 O5 180.0 2_566 . ?
O5 Zn1 O3 90.00(6) 2_566 . ?
O5 Zn1 O3 90.00(6) . . ?
O5 Zn1 O3 90.00(6) 2_566 2_566 ?
O5 Zn1 O3 90.00(6) . 2_566 ?
O3 Zn1 O3 180.00(4) . 2_566 ?
O5 Zn1 O6 92.23(7) 2_566 2_566 ?
O5 Zn1 O6 87.77(7) . 2_566 ?
O3 Zn1 O6 86.01(6) . 2_566 ?
O3 Zn1 O6 93.99(6) 2_566 2_566 ?
O5 Zn1 O6 87.77(7) 2_566 . ?
O5 Zn1 O6 92.23(7) . . ?
O3 Zn1 O6 93.99(6) . . ?
O3 Zn1 O6 86.01(6) 2_566 . ?
O6 Zn1 O6 180.0 2_566 . ?
O2 Zn2 O4 117.06(6) 1_545 1_556 ?
O2 Zn2 O1 103.63(7) 1_545 2_666 ?
O4 Zn2 O1 104.91(7) 1_556 2_666 ?
O2 Zn2 O3 114.66(7) 1_545 2_566 ?
O4 Zn2 O3 104.64(7) 1_556 2_566 ?
O1 Zn2 O3 111.65(7) 2_666 2_566 ?
O2 Zn2 O6 144.68(6) 1_545 . ?
O4 Zn2 O6 96.76(6) 1_556 . ?

O1 Zn2 O6 54.77(5) 2_666 . ?
O3 Zn2 O6 61.62(5) 2_566 . ?
O2 Zn2 O5 94.15(5) 1_545 . ?
O4 Zn2 O5 148.54(5) 1_556 . ?
O1 Zn2 O5 68.81(6) 2_666 . ?
O3 Zn2 O5 54.63(5) 2_566 . ?
O6 Zn2 O5 53.67(4) . . ?
O2 Zn2 O5 162.52(5) 1_545 1_556 ?
O4 Zn2 O5 48.97(5) 1_556 1_556 ?
O1 Zn2 O5 74.37(5) 2_666 1_556 ?
O3 Zn2 O5 81.55(5) 2_566 1_556 ?
O6 Zn2 O5 47.83(4) . 1_556 ?
O5 Zn2 O5 101.03(4) . 1_556 ?
O2 As1 O1 110.45(8) . . ?
O2 As1 O4 112.10(8) . 1_565 ?
O1 As1 O4 111.91(8) . 1_565 ?
O2 As1 O3 107.90(8) . . ?
O1 As1 O3 109.35(8) . . ?
O4 As1 O3 104.87(8) 1_565 . ?
O2 As1 O6 56.20(6) . . ?
O1 As1 O6 85.40(6) . . ?
O4 As1 O6 162.43(6) 1_565 . ?
O3 As1 O6 70.37(6) . . ?
O2 As1 O5 108.82(6) . . ?
O1 As1 O5 61.76(6) . . ?
O4 As1 O5 137.54(6) 1_565 . ?
O3 As1 O5 50.54(6) . . ?
O6 As1 O5 52.72(4) . . ?
As1 O1 Zn2 116.90(9) . 2_666 ?
As1 O1 O6 148.09(9) . 2_666 ?
Zn2 O1 O6 88.79(7) 2_666 2_666 ?
As1 O1 O5 90.74(7) . . ?
Zn2 O1 O5 150.92(8) 2_666 . ?
O6 O1 O5 62.13(6) 2_666 . ?
As1 O1 O6 104.71(8) . 1_554 ?
Zn2 O1 O6 123.25(7) 2_666 1_554 ?
O6 O1 O6 71.96(7) 2_666 1_554 ?
O5 O1 O6 50.50(5) . 1_554 ?
As1 O1 O5 104.77(7) . 2_666 ?
Zn2 O1 O5 77.83(6) 2_666 2_666 ?
O6 O1 O5 60.20(6) 2_666 2_666 ?
O5 O1 O5 86.88(6) . 2_666 ?
O6 O1 O5 127.53(6) 1_554 2_666 ?
As1 O2 Zn2 129.56(9) . 1_565 ?
As1 O2 O6 93.41(8) . . ?
Zn2 O2 O6 131.07(8) 1_565 . ?
As1 O3 Zn2 111.52(8) . 2_566 ?
As1 O3 Zn1 122.77(8) . . ?
Zn2 O3 Zn1 122.64(8) 2_566 . ?
As1 O3 O5 124.48(8) . 2_566 ?
Zn2 O3 O5 90.74(6) 2_566 2_566 ?
Zn1 O3 O5 44.37(4) . 2_566 ?
As1 O3 O5 101.99(7) . . ?
Zn2 O3 O5 139.30(8) 2_566 . ?
Zn1 O3 O5 44.36(4) . . ?
O5 O3 O5 88.73(6) 2_566 . ?
As1 O3 O6 162.50(9) . 2_566 ?

Zn2 O3 O6 81.93(6) 2_566 2_566 ?
Zn1 O3 O6 50.27(5) . 2_566 ?
O5 O3 O6 64.15(6) 2_566 2_566 ?
O5 O3 O6 61.45(6) . 2_566 ?
As1 O3 O6 79.04(6) . . ?
Zn2 O3 O6 145.93(8) 2_566 . ?
Zn1 O3 O6 45.85(4) . . ?
O5 O3 O6 58.84(6) 2_566 . ?
O5 O3 O6 61.42(6) . . ?
O6 O3 O6 96.12(6) 2_566 . ?
As1 O4 Zn2 124.07(9) 1_545 1_554 ?
As1 O4 O5 131.30(9) 1_545 . ?
Zn2 O4 O5 97.83(7) 1_554 . ?
Zn1 O5 O4 119.61(8) . . ?
Zn1 O5 O6 122.65(8) . 1_554 ?
O4 O5 O6 95.24(7) . 1_554 ?
Zn1 O5 O3 45.64(5) . 2_566 ?
O4 O5 O3 79.12(6) . 2_566 ?
O6 O5 O3 153.98(9) 1_554 2_566 ?
Zn1 O5 O3 45.63(5) . . ?
O4 O5 O3 151.60(9) . . ?
O6 O5 O3 81.72(7) 1_554 . ?
O3 O5 O3 91.27(6) 2_566 . ?
Zn1 O5 O6 49.94(5) . 2_566 ?
O4 O5 O6 91.06(7) . 2_566 ?
O6 O5 O6 89.26(7) 1_554 2_566 ?
O3 O5 O6 65.68(6) 2_566 2_566 ?
O3 O5 O6 60.78(6) . 2_566 ?
Zn1 O5 O6 130.64(8) . 2_666 ?
O4 O5 O6 101.42(7) . 2_666 ?
O6 O5 O6 75.27(7) 1_554 2_666 ?
O3 O5 O6 130.68(8) 2_566 2_666 ?
O3 O5 O6 105.01(7) . 2_666 ?
O6 O5 O6 160.83(9) 2_566 2_666 ?
Zn1 O5 O6 47.43(5) . . ?
O4 O5 O6 128.49(8) . . ?
O6 O5 O6 135.36(9) 1_554 . ?
O3 O5 O6 59.35(6) 2_566 . ?
O3 O5 O6 64.13(6) . . ?
O6 O5 O6 97.37(7) 2_566 . ?
O6 O5 O6 86.28(7) 2_666 . ?
Zn1 O5 O1 90.70(6) . . ?
O4 O5 O1 149.59(8) . . ?
O6 O5 O1 67.33(6) 1_554 . ?
O3 O5 O1 127.32(7) 2_566 . ?
O3 O5 O1 53.91(5) . . ?
O6 O5 O1 112.47(7) 2_566 . ?
O6 O5 O1 51.26(5) 2_666 . ?
O6 O5 O1 69.40(6) . . ?
Zn1 O5 O1 87.87(6) . 2_666 ?
O4 O5 O1 86.17(6) . 2_666 ?
O6 O5 O1 142.26(8) 1_554 2_666 ?
O3 O5 O1 63.28(5) 2_566 2_666 ?
O3 O5 O1 113.43(7) . 2_666 ?
O6 O5 O1 128.46(7) 2_566 2_666 ?
O6 O5 O1 67.54(6) 2_666 2_666 ?
O6 O5 O1 49.71(5) . 2_666 ?

O1 O5 O1 93.12(6) . 2_666 ?
Zn1 O5 Zn2 74.49(5) . . ?
O4 O5 Zn2 68.42(5) . . ?
O6 O5 Zn2 161.60(7) 1_554 . ?
O3 O5 Zn2 34.62(4) 2_566 . ?
O3 O5 Zn2 116.67(6) . . ?
O6 O5 Zn2 99.10(6) 2_566 . ?
O6 O5 Zn2 99.01(6) 2_666 . ?
O6 O5 Zn2 60.08(4) . . ?
O1 O5 Zn2 122.93(6) . . ?
O1 O5 Zn2 33.36(3) 2_666 . ?
Zn1 O5 Zn2 138.67(8) . 1_554 ?
O4 O5 Zn2 33.20(4) . 1_554 ?
O6 O5 Zn2 62.08(5) 1_554 1_554 ?
O3 O5 Zn2 109.69(6) 2_566 1_554 ?
O3 O5 Zn2 135.49(7) . 1_554 ?
O6 O5 Zn2 91.99(6) 2_566 1_554 ?
O6 O5 Zn2 90.67(5) 2_666 1_554 ?
O6 O5 Zn2 159.97(7) . 1_554 ?
O1 O5 Zn2 122.89(6) . 1_554 ?
O1 O5 Zn2 111.07(5) 2_666 1_554 ?
Zn2 O5 Zn2 101.03(4) . 1_554 ?
Zn1 O5 H1 117(2) . . ?
O4 O5 H1 3(2) . . ?
O6 O5 H1 99(2) 1_554 . ?
O3 O5 H1 76(2) 2_566 . ?
O3 O5 H1 152(2) . . ?
O6 O5 H1 91(2) 2_566 . ?
O6 O5 H1 102(2) 2_666 . ?
O6 O5 H1 125(2) . . ?
O1 O5 H1 152(2) . . ?
O1 O5 H1 84(2) 2_666 . ?
Zn2 O5 H1 65(2) . . ?
Zn2 O5 H1 37(2) 1_554 . ?
Zn1 O5 H2 120(3) . . ?
O4 O5 H2 96(3) . . ?
O6 O5 H2 3(3) 1_554 . ?
O3 O5 H2 152(3) 2_566 . ?
O3 O5 H2 80(3) . . ?
O6 O5 H2 87(3) 2_566 . ?
O6 O5 H2 78(3) 2_666 . ?
O6 O5 H2 135(3) . . ?
O1 O5 H2 68(3) . . ?
O1 O5 H2 145(3) 2_666 . ?
Zn2 O5 H2 164(3) . . ?
Zn2 O5 H2 63(3) 1_554 . ?
H1 O5 H2 100(3) . . ?
Zn1 O6 O1 100.04(7) . 2_666 ?
Zn1 O6 O2 94.07(7) . . ?
O1 O6 O2 139.42(8) 2_666 . ?
Zn1 O6 O5 119.42(8) . 1_556 ?
O1 O6 O5 80.48(7) 2_666 1_556 ?
O2 O6 O5 124.30(8) . 1_556 ?
Zn1 O6 O3 43.72(4) . 2_566 ?
O1 O6 O3 70.65(6) 2_666 2_566 ?
O2 O6 O3 136.98(8) . 2_566 ?
O5 O6 O3 82.73(7) 1_556 2_566 ?

Zn1 O6 O5 42.29(4) . 2_566 ?
O1 O6 O5 128.38(8) 2_666 2_566 ?
O2 O6 O5 86.50(7) . 2_566 ?
O5 O6 O5 90.74(7) 1_556 2_566 ?
O3 O6 O5 57.77(6) 2_566 2_566 ?
Zn1 O6 O5 131.35(8) . 2_666 ?
O1 O6 O5 66.60(6) 2_666 2_666 ?
O2 O6 O5 75.49(6) . 2_666 ?
O5 O6 O5 104.73(7) 1_556 2_666 ?
O3 O6 O5 134.40(8) 2_566 2_666 ?
O5 O6 O5 160.83(9) 2_566 2_666 ?
Zn1 O6 O5 40.35(5) . . ?
O1 O6 O5 70.10(6) 2_666 . ?
O2 O6 O5 99.41(7) . . ?
O5 O6 O5 135.36(9) 1_556 . ?
O3 O6 O5 56.49(6) 2_566 . ?
O5 O6 O5 82.63(7) 2_566 . ?
O5 O6 O5 93.72(7) 2_666 . ?
Zn1 O6 O3 40.16(4) . . ?
O1 O6 O3 124.05(8) 2_666 . ?
O2 O6 O3 54.55(5) . . ?
O5 O6 O3 145.56(8) 1_556 . ?
O3 O6 O3 83.88(6) 2_566 . ?
O5 O6 O3 55.48(5) 2_566 . ?
O5 O6 O3 107.31(7) 2_666 . ?
O5 O6 O3 54.46(5) . . ?
Zn1 O6 As1 69.87(5) . . ?
O1 O6 As1 124.39(7) 2_666 . ?
O2 O6 As1 30.39(4) . . ?
O5 O6 As1 153.22(7) 1_556 . ?
O3 O6 As1 113.08(7) 2_566 . ?
O5 O6 As1 81.01(5) 2_566 . ?
O5 O6 As1 80.11(5) 2_666 . ?
O5 O6 As1 69.08(5) . . ?
O3 O6 As1 30.59(3) . . ?
Zn1 O6 Zn2 75.99(5) . . ?
O1 O6 Zn2 36.44(4) 2_666 . ?
O2 O6 Zn2 165.59(8) . . ?
O5 O6 Zn2 70.08(5) 1_556 . ?
O3 O6 Zn2 36.45(4) 2_566 . ?
O5 O6 Zn2 92.74(6) 2_566 . ?
O5 O6 Zn2 103.04(6) 2_666 . ?
O5 O6 Zn2 66.25(5) . . ?
O3 O6 Zn2 113.72(6) . . ?
As1 O6 Zn2 135.32(6) . . ?
Zn1 O6 O1 151.47(8) . 1_556 ?
O1 O6 O1 108.04(7) 2_666 1_556 ?
O2 O6 O1 67.75(6) . 1_556 ?
O5 O6 O1 62.17(6) 1_556 1_556 ?
O3 O6 O1 144.09(7) 2_566 1_556 ?
O5 O6 O1 112.15(7) 2_566 1_556 ?
O5 O6 O1 67.22(6) 2_666 1_556 ?
O5 O6 O1 158.79(7) . 1_556 ?
O3 O6 O1 120.55(7) . 1_556 ?
As1 O6 O1 97.35(5) . 1_556 ?
Zn2 O6 O1 125.36(6) . 1_556 ?
Zn1 O6 H3 112(3) . . ?

O1 O6 H3 30(3) 2_666 . ?
O2 O6 H3 109(3) . . ?
O5 O6 H3 99(3) 1_556 . ?
O3 O6 H3 97(3) 2_566 . ?
O5 O6 H3 152(3) 2_566 . ?
O5 O6 H3 38(3) 2_666 . ?
O5 O6 H3 72(3) . . ?
O3 O6 H3 115(3) . . ?
As1 O6 H3 101(3) . . ?
Zn2 O6 H3 66(3) . . ?
O1 O6 H3 95(3) 1_556 . ?
Zn1 O6 H4 118(3) . . ?
O1 O6 H4 128(3) 2_666 . ?
O2 O6 H4 24(3) . . ?
O5 O6 H4 106(3) 1_556 . ?
O3 O6 H4 160(3) 2_566 . ?
O5 O6 H4 103(3) 2_566 . ?
O5 O6 H4 62(3) 2_666 . ?
O5 O6 H4 119(3) . . ?
O3 O6 H4 79(3) . . ?
As1 O6 H4 53(3) . . ?
Zn2 O6 H4 163(3) . . ?
O1 O6 H4 45(3) 1_556 . ?
H3 O6 H4 99(4) . . ?
loop__geom_hbond_atom_site_label_D_geom_hbond_atom_site_label_H_geom_hbond_atom_site_label_A_geom_hbond_distance_DH_geom_hbond_distance_HA_geom_hbond_distance_DA_geom_hbond_angle_DHA_geom_hbond_site_symmetry_A
O5 H1 O4 0.9798(10) 1.720(4) 2.697(2) 175(3) .
O5 H2 O6 0.9800(10) 1.814(4) 2.792(2) 176(4) 1_554
O6 H3 O1 0.9799(10) 1.94(3) 2.720(2) 135(3) 2_666
O6 H4 O2 0.9799(11) 1.90(3) 2.751(2) 143(4) .
_diffrn_measured_fraction_theta_max_diffrn_reflns_theta_full_diffrn_measured_fraction_theta_full_refine_diff_density_max
0.608_refine_diff_density_min-0.703_refine_diff_density_rms
0.108

0.999
30.24
0.999