electronic reprint Redetermination of the Tutton's salt ...

electronic reprint Acta Crystallographica Section E

Structure Reports Online ISSN 1600-5368

Editors: W. Clegg and D. G. Watson

Redetermination of the Tutton’s salt Cs2[Cu(H2 O)6](SO4 )2 Paolo Ballirano, Girolamo Belardi and Ferdinando Bosi

Copyright © International Union of Crystallography Author(s) of this paper may load this reprint on their own web site or institutional repository provided that this cover page is retained. Republication of this article or its storage in electronic databases other than as specified above is not permitted without prior permission in writing from the IUCr. For further information see http://journals.iucr.org/services/authorrights.html

Acta Cryst. (2007). E63, i164–i165

Ballirano et al.

¯

Cs2 [Cu(H2 O)6 ](SO4 )2

inorganic compounds Acta Crystallographica Section E

Data collection

Structure Reports Online

3208 independent reflections 2728 reflections with I > 2
(I) Rint = 0.031 3 standard reflections every 47 reflections intensity decay: 1%

Siemens P4 diffractometer Absorption correction: scan (North et al., 1968) Tmin = 0.226, Tmax = 0.584 (expected range = 0.100–0.259) 3436 measured reflections

ISSN 1600-5368

Redetermination of the Tutton’s salt Cs2[Cu(H2O)6](SO4)2

Refinement

Paolo Ballirano,a,b* Girolamo Belardib and Ferdinando Bosic

R[F 2 > 2
(F 2)] = 0.034 wR(F 2) = 0.081 S = 1.09 3208 reflections

109 parameters Only H-atom coordinates refined ˚ 3
max = 1.53 e A ˚ 3
min = 2.57 e A

a

Dipartamento di Scienze della Terra, Universita´ di Roma ‘La Sapienza’, Piazzale Aldo Moro 5, Roma I-00185, Italy, bCNR–IGAG Istituto di Geologia Ambientale e Geoingegneria, Sede di Roma, Via Bolognola 7, Roma I-00138, Italy, and c Department of Mineralogy, Swedish Museum of Natural History, Box 50007, S-10405 Stockholm, Sweden. Correspondence e-mail: [email protected] Received 13 June 2007; accepted 18 June 2007 ˚; Key indicators: single-crystal X-ray study; T = 293 K; mean
(S–O) = 0.003 A R factor = 0.034; wR factor = 0.080; data-to-parameter ratio = 29.4.

The crystal structure of dicaesium hexaaquacopper(II) bis[sulfate(VI)], Cs2[Cu(H2O)6](SO4)2, has been redetermined from single-crystal X-ray diffraction data. In comparison with the previous refinement based on single-crystal neutron data [Shields & Kennard (1972). Cryst. Struct. Commun. 1, 189– 191], the results show an improved precision and benefit from inclusion of anisotropic displacement parameters for the nonH atoms. The structure is characterized by a mean Cu—O ˚ . The [Cu(H2O)6] octahedron (1 bond length of 2.094 A symmetry) is strongly distorted because of the Jahn–Teller effect, with a calculated distortion parameter
of 0.0054. The Cs+ cation is ninefold coordinated by seven O atoms and two ˚. water molecules, with a mean Cs—O bond length of 3.238 A

Related literature For related structures of other MI2[Cu(H2O)6](SO4)2 salts, see: Cotton et al. (1993) (M = NH4); Simmons et al. (2006) (M = K); Ballirano & Belardi (2007) (M = Rb). The distortion of the [Cu(H2O)6] octahedron was calculated according to Brown & Shannon (1973). A reasonable hydrogen-bonding geometry was obtained after value normalization following the procedure described by Jeffrey & Lewis (1978) and Taylor & Kennard (1983).

Table 1 ˚ ). Selected geometric parameters (A Cu—OW3 Cu—OW1 Cu—OW2 Cs—O1 Cs—O4i Cs—O3ii

1.965 2.005 2.311 3.098 3.114 3.151

(2) (2) (2) (2) (2) (3)

Cs—O2ii Cs—O1iii Cs—OW2iv Cs—O2iii Cs—OW1 Cs—O2i

3.179 3.182 3.233 3.239 3.422 3.528

(3) (2) (3) (3) (3) (3)

Symmetry codes: (i) x  12; y þ 12; z  1; (ii) x þ 12; y þ 12; z þ 1; (iii) x  12; y þ 12; z; (iv) x þ 12; y þ 12; z.

Table 2

˚ ,
). Hydrogen-bond geometry (A D—H  A

D—H

H  A

D  A

D—H  A

OW1—H11  O3 OW1—H12  O4v OW2—H21  O2vi OW2—H22  O4i OW3—H31  O3vii OW3—H32  O1viii

0.77 0.75 0.87 0.74 0.74 0.71

1.97 1.99 1.91 2.04 2.02 1.99

2.714 2.738 2.777 2.779 2.725 2.693

166 173 174 171 155 171

(7) (7) (6) (6) (7) (7)

(7) (7) (7) (6) (7) (6)

(2) (4) (3) (4) (3) (3)

(7) (7) (7) (6) (7) (6)

Symmetry codes: (i) x  12; y þ 12; z  1; (v) x; y; z  1; (vi) x  1; y; z  1; (vii) x; y; z þ 1; (viii) x þ 12; y  12; z þ 1.

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 2003); software used to prepare material for publication: PARST (Nardelli, 1982) and publCIF (Westrip, 2007).

This work received financial support from Universita´ di Roma ‘La Sapienza’. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2127).

References Experimental Crystal data Cs2[Cu(H2O)6](SO4)2 Mr = 629.61 Monoclinic, P21 =a ˚ a = 9.4383 (6) A ˚ b = 12.7605 (12) A ˚ c = 6.3130 (6) A  = 106.199 (7)


i164

˚3 V = 730.14 (11) A Z=2 Mo K radiation  = 6.76 mm1 T = 293 (2) K 0.30  0.20  0.20 mm

# 2007 International Union of Crystallography

Ballirano, P. & Belardi, G. (2007). Acta Cryst. E63, i56–i58. Brown, I. D. & Shannon, R. D. (1973). Acta Cryst. A29, 266–282. Cotton, F. A., Daniels, L. M., Murillo, C. A. & Quesada, J. F. (1993). Inorg. Chem. 32, 4861–4867. Dowty, E. (2003). ATOMS. Version 6.1. Shape Software, Kingsport, Tennessee, USA. http://www.shapesoftware.com. Jeffrey, G. A. & Lewis, L. (1978). Carbohydr. Res. 60, 179–182. Nardelli, M. (1982). PARST. University of Parma, Italy. North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351– 359.

doi:10.1107/S1600536807029790

electronic reprint

Acta Cryst. (2007). E63, m164–m165

inorganic compounds Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany. Shields, K. G. & Kennard, C. H. L. (1972). Cryst. Struct. Commun. 1, 189–191. Siemens (1994). XSCANS. Version 2.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Acta Cryst. (2007). E63, m164–m165

Simmons, C. J., Stratemeier, H., Hitchman, M. A. & Riley, M. J. (2006). Inorg. Chem. 45, 1021–1031. Taylor, R. & Kennard, O. (1983). Acta Cryst. B39, 133–138. Westrip, S. P. (2007). publCIF. In preparation.

electronic reprint

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Cs2[Cu(H2O)6](SO4)2

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