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
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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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