electronic reprint
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
Editors: W.T. A. Harrison, J. Simpson and M. Weil
Redetermination of despujolsite, Ca3Mn4+(SO4)2(OH)6·3H2O
Madison C. Barkley, Hexiong Yang, Stanley H. Evans, Robert T. Downs and
Marcus J. Origlieri
Acta Cryst. (2011). E67, i47–i48
This open-access article is distributed under the terms of the Creative Commons Attribution Licence
http://creativecommons.org/licenses/by/2.0/uk/legalcode, which permits unrestricted use, distribution, and
reproduction in any medium, provided the original authors and source are cited.
ISSN 1600-5368
Volume 61
Part 11
November 2005
Acta Crystallographica Section E
Structure Reports
Online
Editors: W. Clegg and D. G. Watson
Inorganic compounds
Metal-organic compounds
Organic compounds
journals.iucr.org
International Union of Crystallography
*
Acta Crystallographica Section E: Structure Reports Online is the IUCr’s highly popular open-access structural journal. It provides a simple and easily accessible publication
mechanism for the growing number of inorganic, metal-organic and organic crystal structure determinations. The electronic submission, validation, refereeing and publication
facilities of the journal ensure very rapid and high-quality publication, whilst key indicators and validation reports provide measures of structural reliability. The journal publishes
over 4000 structures per year. The average publication time is less than one month.
Chester
Crystallography Journals Online is available from journals.iucr.org
Acta Cryst. (2011). E67, i47–i48
Barkley et al. · Ca3 Mn(SO4 )2 (OH)6 ·3H2 O
inorganic compounds
= 2.49 mm1
T = 293 K
Acta Crystallographica Section E
Structure Reports
Online
0.07 0.06 0.04 mm
Data collection
ISSN 1600-5368
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
Tmin = 0.845, Tmax = 0.907
Redetermination of despujolsite,
Ca3Mn4+(SO4)2(OH)63H2O
6018 measured reflections
871 independent reflections
758 reflections with I > 2(I)
Rint = 0.051
Refinement
Madison C. Barkley,*‡ Hexiong Yang, Stanley H. Evans,
Robert T. Downs and Marcus J. Origlieri
Department of Geosciences, University of Arizona, 1040 E. 4th Street, Tucson,
Arizona 85721-0077, USA
Correspondence e-mail: mbarkley@azhs.gov
Received 22 July 2011; accepted 1 August 2011
R[F 2 > 2(F 2)] = 0.024
wR(F 2) = 0.048
S = 1.06
871 reflections
49 parameters
All H-atom paramters refined
max = 0.45 e Å3
min = 0.30 e Å3
Absolute structure: Flack (1983),
305 Friedel pairs
Flack parameter: 0.0 (9)
Table 1
Key indicators: single-crystal X-ray study; T = 293 K; mean (Mn–O) = 0.006 Å;
R factor = 0.024; wR factor = 0.048; data-to-parameter ratio = 17.8.
The crystal structure of despujolsite [tricalcium manganese
bis(sulfate) hexahydroxide trihydrate], the Ca/Mn member of
the fleischerite group, ideally Ca3Mn4+(SO4)2(OH)63H2O,
was previously determined based on X-ray diffraction
intensity data from photographs, without H-atom positions
located [Gaudefroy et al. (1968). Bull. Soc. Fr. Minéral.
Crystallogr. 91, 43–50]. The current study redetermines the
structure of despujolsite from a natural specimen, with all H
atoms located and with higher precision. The structure of
despujolsite is characterized by layers of CaO8 polyhedra (m..
symmetry) interconnected by Mn(OH)6 octahedra (32.
symmetry) and SO4 tetrahedra (3.. symmetry) along [001].
The average Ca—O, Mn—O and S—O bond lengths are 2.489,
1.915, and 1.472 Å, respectively. There are two distinct
hydrogen bonds that stabilize the structural set-up. This work
represents the first description of hydrogen bonds in the
fleischerite group of minerals.
Related literature
For the previous determination of the despujolsite crystal
structure, see: Gaudefroy et al. (1968). For background to
fleischerite, see: Otto (1975). For the crystal structures of
sulfate minerals with split O sites, see: Hill (1977); Jacobsen et
al. (1998). For TLS (translation, libration, and screw motions)
rigid-body analysis, see: Downs (2000). Parameters for bondvalence analysis were taken from Brese & O’Keeffe (1991).
Selected bond lengths (Å).
Mn—OH3i
Ca—O2ii
Ca—OH3i
Ca—OH3iii
1.9149 (11)
2.3465 (11)
2.456 (5)
2.518 (5)
Ca—OW4
Ca—OW4iv
S—O2
S—O1
2.578 (9)
2.690 (9)
1.4697 (11)
1.4806 (18)
Symmetry codes: (i) x þ y þ 1; x þ 1; z; (ii) x; y; z þ 12; (iii) x 1; y; z þ 12; (iv)
x þ y; x þ 1; z.
Table 2
Hydrogen-bond geometry (Å, ).
D—H A
OH3—H1 O2
OW4—H2 O1vi
v
D—H
H A
D A
D—H A
0.75 (2)
0.77 (2)
2.11 (2)
2.10 (2)
2.8193 (16)
2.7892 (18)
158 (3)
150 (3)
Symmetry codes: (v) x þ 1; x þ y; z; (vi) y; x; z.
Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT
(Bruker, 2005); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: XtalDraw (Downs & Hall-Wallace, 2003); software used to prepare
material for publication: SHELXTL (Sheldrick, 2008b).
The authors gratefully acknowledge support of this study by
the Carnegie-DOE Alliance Center under cooperative
agreement DE FC52–08 N A28554, BP p.l.c., Tucson Gem and
Mineral Society and the Arizona Science Foundation.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: WM2518).
References
Experimental
Crystal data
Ca3Mn(SO4)2(OH)63H2O
Mr = 523.40
Hexagonal, P62c
a = 8.5405 (5) Å
c = 10.8094 (9) Å
V = 682.81 (8) Å3
Z=2
Mo K radiation
‡ Arizona Historical Society, 1502 W Washington Street, Phoenix, Arizona
85007, USA.
Acta Cryst. (2011). E67, i47–i48
Brese, N. E. & O’Keeffe, M. (1991). Acta Cryst. B47, 192–197.
Bruker (2003). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2005). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Downs, R. T. (2000). RiMG, 41, 61–88.
Downs, R. T. & Hall-Wallace, M. (2003). Am. Mineral. 88, 247–250.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Gaudefroy, P. C., Granger, M. M., Permingeat, F. & Protas, J. (1968). Bull. Soc.
Fr. Minéral. Crystallogr. 91, 43–50.
Hill, R. J. (1977). Can. Mineral. 15, 522–526.
doi:10.1107/S1600536811030911
electronic reprint
Barkley et al.
i47
inorganic compounds
Jacobsen, S. D., Smyth, J. R., Swope, R. J. & Downs, R. T. (1998). Can. Mineral.
36, 1045–1055.
Otto, H. H. (1975). Neues Jahrb. Mineral. Abh. 123, 160–190.
i48
Barkley et al.
Ca3Mn(SO4)2(OH)63H2O
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122.
electronic reprint
Acta Cryst. (2011). E67, i47–i48
electronic reprint
!"#$%&'$()&'*(+*)'
#",- .!*/0!*12!345#6'0 !"#$%%&'
&% (()* + , +-,* .* + ("* /,-,
"- +-,* 0) 1$%%&'
&% (. 0) $)$%2%%&'
&% " -,*
1#$%%&'
&%
3,+*",*-*+"+-,*+*(",-(/,,
%",.*,4)"*("1+*5'6%57),+/,-,/*)"8*
++*-"""(*+*(,.*,/,&("-
2"+-*+
'/)"
+*,*-*(+1+*5'
9"*++*"*",*.")""."4*"("
"."*",*",",,*.")"".-,(",("*+,+-,*.*"*-*/
",,*-*"+*("+")(*4
3,*-*+-"+*+%,*
((*"*-""-)!"%&'-,*
((*"$%*,* ((*
3,4*.!":%)"".,
57;3)
-"
+ )"4"- ( ". , *(* +*( <* = %>?++ 55 ' 4
+* !" "-". , ,
."4"-+#+*!"-""/,,*-*
3,4*.$:%)"".,
;
(*
.,-*"/,%&"&%(-"%(
3,4*.:%)"".,
5;
3,*
*/"-,*.")"@%& :&AAA%"%B:&AAA%3)
3,*-*("*+-,*/*4(%57/,+*,%"
$(*
+,+("*)*<$%*+",%(,"-"/,((&
5
&/4*&",,**"."+-"(*4("",*+"("/,(4*,
((*-"*"(
C*,**-**+"("/,."+-")*)D-)"55
3E$*"")*""-*/("*.)"/"+,+.*
3,*"-
,,$%.*),4*.)/,."+-"*""")*"("("*".,,%
(*"",,*.F+,-("*(**"*,*(("
9"-"*,+-,***+"("+""-
23E$"+,
-("*(*"-,,$%.*"),4G/*.)/,*""
(+
;"*.)*"".+
57H
3,)*"".+*,$%.*"/,-,
-""/,,HH*".+""-"".")*"-,,$I%)"".,*J
5;
".*,",**"4
9+,)*"".*."+-,*,",(--"+*,++-4"
+".,%)*"-,,%"+-,*("-
electronic reprint
3, -(" " , +*( K>,/"". 999 (" ?,* !"." + K*,*" 0*4"-$,2+*-"",--"+,LLMCC*-"K
L6,@NN**++
"+
3,-(
"/*("/,2!2$8-*"(-**),@NN**++
"+"".-*+*(,(
*"(,-*+*,--"+8*++*-"""
-*"(-**)"7
"/,7?O--*".4."2)(-**""7P()(F"(*--,(-
+*( 7!"#
'$
5'%%&'
&%)"%(
<--**")"*
,-*")(/,-,,)")*4)1+*5',-*"(-**)/*"+*
,("+-"*
3,--("/*(")-()""+(-**)"8**-*
"
+,(-,(*"*-*+*(--"-")+"",LLMCC0*-/)
,@NN**++
"+NL
3,&(/*-+*(++*"-C**(",*"/**+"/,*--("*
(*
3,+"*+"("("-,(*,4*++-+,*-("+C"$",+"
*-***"..)
3,,.,*G",++*"-C**(/-
'';+*(%"
,,/-
;+*(!"
C.
3,-**-*+
Q/*,***"$%.*
<
-,*"*,***"!"%&'.*"%%&&%.**
-4
E.,),***"&"&
C.
2("/,-**"".55R*))
$%.*
***.)",/"/*,*
<*"*
**"!""%(*-4
&*."(*,/".,)
,*
C.
&)""."*-""
Q/*,***"$%.*
0*
,***"%%&&%.*
L"),***"%"
&(*-4
!"$%%&'A &%
ST
7'!.(U
!
electronic reprint
T7 !V*"WT
;
&S."'
&()@0'--
*(*+*(7*+-"
XT
I H
T
777;
PT
5((U
T5 ?
T
55;
T'
;
T
T7 ,*/
Y
'Y
((
<*G*20899*-*
++*-(*
L"*-@+"+-)
"""*+-"
.*,
7*+-"/,Z[
"T
7
\"]-"
X(ST 'HX("T
H
2)*"-**-"@(-"
6$,*-G
("T
7(ST
5
'(**+-"
!TU^
"TU^
TU'^7
#
L+"(""
E_*(*S@+
Z[T
&*."-"@++*"-C**(
2&(*(**+"
$TN[#
#
''
/,*T#-N
$T
`N[(Sa
T
'
`b(ST
7;U
*+-"
`b("TU
;U
5*(*
S"-"-**-"@%&'(')*$,*-G
C-cTGC-#
SC-W N"XN
S"-"-++-"@
2)*-*@C-G5 7C**
**"
-"*"
0*(*(-"@*-*"4*"*-
C-G*(*@
5
(,
$-"*(-"@++*"-C**(
+
7.
2
>S-,
",,*".)/"/
"*(".,+-4*"-(
*S
3,-
>*G""--""4",("+
>""-"."*"".6-**"
)/"
>"-*(**"/,",*+")-*((*
2"*S(*-*("+
-
>+*(".
>"44".
"
L+"("+."2EE*+-"
3,/.,+-*$"."++*)"-"4""
+-**)"/,F*+*".4
3,,*,S*"+Z["+*--".
"
electronic reprint
+-*.
""*4",-,-+*+-"+**+"("
+-*)"*-)/-*.
,)""+-*)"2EE/)4"*.*
+
,-.
+++
/012
!"
$
%
%
%&
%B
&
&
3
4
5cN5_
7 5
57
7'
''
75
7
'''
'''
7
5''
7 7'
75
7
77
U
7 7
'5
7
'
5 '
7
5 '
'
5 7
'c
'c
++
/012
5
557
'
'
7
5
!"
$
%
%
%&
%B
5
557
55
'
'
'7
5
5
'
7
7
''
5
5'
7
7
''
5
U
''
5
U
'
6
+
/0782
!":%&
!":%&
!":%&
!":%&
4
!":%&
4
!":%&
4
4
7'7
:%&
77
55
:%&
S
77
55
:%B
55
55
55
4
'7
:%
:%
:%&
:%&
55
S
'5
S
$:%
$:%
$:%
'5
'7
7'7
$:%
'
%& :!":%&
%& :!":%&
7
7
%&
%& :!":%&
5 %&
%& :!":%&
4
%& :!":%&
4
%&
4
:!":%&
%& :!":%&
4
'55
:%B
%& :!":%&
75
S
'5
4
7
7
:!":%&
4
5'
7 4
:!":%&
4
7
7
%& 4:!":%&
4
7
7
5'
7 %S:$:%S
7
7
5'
7 7
S
7
S
7
% :$:%
% :$:%
#
electronic reprint
%& :!":%&
4
7
7
%S:$:%
'77
%&
:!":%&
4
%S:$:%
'77
%&
4
:!":%&
4
5 %:$:%
'77
4
5 %& :!":%&
$((*-@U3##U3#463UUUU463U464U3UU4643UU464U3#U3##U4643
U4#N64U3##U3#U4#N6S3UU4#N6SU3#U3#46SU#3U#4
%
9:9
/0782
:&AAA
:&
&AAA
AAA
:&AAA
7
5 '
7 %B:&AAA%
$((*-@SU3#U3#U46S3U4
5
7 S
%& :&AAA%
S
$
electronic reprint
%
electronic reprint
!
&
electronic reprint
"
'
electronic reprint