PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): i54.
Published online 2010 July 3. doi:  10.1107/S1600536810025304
PMCID: PMC3007360

Calcium disodium hexa­thio­diphosphate(IV) octa­hydrate

Abstract

Single crystals of the title compound, CaNa2(P2S6)·8H2O, were obtained by adding calcium hydroxide to an aqueous solution of Na4(P2S6)·6H2O. The structure is isotypic with that of its strontium analogue and consists of one Ca2+ cation, two Na+ cations, one-half of a centrosymmetric (P2S6)4− anion with staggered confirmation and four water mol­ecules in the asymmetric unit. The crystal structure can be described as being built up from layers of cations and anions extending parallel to (101). Within a layer, each CaO8 polyhedron is connected via edge-sharing to two NaO4S2 octa­hedra and to one NaO2S4 octa­edron. The NaO4S2 octa­hedra are, in turn, linked with two (P2S6)4− anions through common corners. Various O—H(...)S hydrogen-bonding inter­actions lead to cohesion of adjacent layers. The Ca2+ and one Na+ cation are situated on a twofold rotation axis and the second Na+ cation is situated on an inversion centre.

Related literature

For background to thio­diphosphates(IV), including their crystal structures, see: Jörgens et al. (2003 [triangle]); Klingen et al. (1973 [triangle]). For the synthesis of Na4(P2S6)·6H2O, see: Fincher et al. (1998 [triangle]). For the isotypic structure of SrNa2(P2S6)·8H2O, see: Gjikaj & Ehrhardt (2010 [triangle]).

Experimental

Crystal data

  • CaNa2(P2S6)·8H2O
  • M r = 484.49
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00i54-efi1.jpg
  • a = 14.702 (2) Å
  • b = 9.3081 (14) Å
  • c = 14.052 (2) Å
  • β = 115.383 (11)°
  • V = 1737.3 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.34 mm−1
  • T = 223 K
  • 0.29 × 0.24 × 0.23 mm

Data collection

  • Stoe IPDS 2 diffractometer
  • 15223 measured reflections
  • 2650 independent reflections
  • 2369 reflections with I > 2σ(I)
  • R int = 0.050

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.065
  • S = 1.13
  • 2650 reflections
  • 122 parameters
  • All H-atom parameters refined
  • Δρmax = 0.68 e Å−3
  • Δρmin = −0.53 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2004 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025304/wm2364sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025304/wm2364Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Alkaline earth hypothiodiphosphates were first reported by Klingen et al. (1973). The structure of the title compound is isotypic with that of the strontium analogue, SrNa2(P2S6).8H2O (Ehrhardt & Gjikaj, 2010). The asymmetric unit of CaNa2(P2S6).8H2O contains one Ca2+ cation, two Na+ cations, one half of a (P2S6)4- anion in staggered conformation and four water molecules (Fig. 1).

Na(1) is octahedrally coordinated by four H2O molecules and two sulfur atoms of two (P2S6)4- anions (Fig 2). Na(2) is also octahedrally coordinated by two H2O molecules and four sulfur atoms of two (P2S6)4- anions (Fig. 3). The calcium cation is eightfold coordinated by water O atoms. The [CaO8] coordination polyhedron can be described as a bicapped trigonal prism. The crystal structure is built up from layers extending parallel to (101). These layers consists of edge-sharing CaO8 and Na(1)O4S2 polyedra, CaO8 and Na(2)O2S4 polyhadra, as well as corner-sharing Na(1)O4S2 and (P2S6)4- polyhedra.

The staggered (P2S6)4- anion is located on a centre of inversion, with a P—P distance of 2.2381 (8) Å. The P—P central bond links two PS3 groups with P—S distances ranging from 2.0156 (6) to 2.0282 (6) Å. These values agree well with those reported previously for another hypothiodiphosphate structure (Jörgens et al., 2003).

Neighbouring layers are held together by various O—H···S hydrogen bonding interactions. The donor—acceptor distances between O atoms of water molecules and S atoms of (P2S6)4- units range from 3.188 to 3.327 Å (Table 2).

Experimental

Na4(P2S6).6H2O has been prepared according to Fincher et al. (1998). The new ternary calcium disodium hexathiodiphosphate octahydrate was obtained by adding calcium hydroxide (2 mmol, 0.148 g) to a solution of Na4(P2S6).6H2O (2 mmol, 0.910 g) in 40 ml distilled water at 333 K. Slow cooling to room temperature yielded colorless crystals of the title compound within some days.

Refinement

Hydrogen atoms were found from the difference Fourier map and were refined independently from their respective oxygen atoms with individual isotropic displacement parameters.

Figures

Fig. 1.
The crystal structure of CaNa2(P2S6).8H2O in a projection along [010].
Fig. 2.
Coordination of Na1 with the atom labelling scheme. The displacement ellipsoids are drawn at the 50% probability level. Symmetry codes as in Table 1. H atoms are represented as spheres of arbirtary radius.
Fig. 3.
View of the edge-shared CaO8 and Na(2)O2S4 polyhedra with the atom labelling scheme. The displacement ellipsoids are drawn at the 50% probability level. Symmetry codes as in Table 1. H atoms are represented as spheres of arbirtary radius.

Crystal data

CaNa2(P2S6)·8H2OF(000) = 992
Mr = 484.49Dx = 1.852 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 15599 reflections
a = 14.702 (2) Åθ = 1.0–30.5°
b = 9.3081 (14) ŵ = 1.34 mm1
c = 14.052 (2) ÅT = 223 K
β = 115.383 (11)°Block, colorless
V = 1737.3 (4) Å30.29 × 0.24 × 0.23 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer2369 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
graphiteθmax = 30.5°, θmin = 2.7°
ω–scansh = −20→20
15223 measured reflectionsk = −13→13
2650 independent reflectionsl = −20→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029All H-atom parameters refined
wR(F2) = 0.065w = 1/[σ2(Fo2) + (0.0256P)2 + 2.2311P] where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
2650 reflectionsΔρmax = 0.68 e Å3
122 parametersΔρmin = −0.53 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0046 (3)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Ca0.50000.24842 (5)0.25000.01531 (10)
Na10.25000.25000.00000.0240 (2)
Na20.50000.67523 (13)0.25000.0318 (2)
P0.20227 (3)0.76310 (4)0.04363 (3)0.01394 (9)
S10.06893 (3)0.67248 (4)−0.04913 (3)0.02064 (10)
S20.18887 (3)0.97575 (4)0.06497 (3)0.01807 (9)
S30.27954 (3)0.66563 (4)0.18473 (3)0.02051 (10)
O10.59411 (11)0.04315 (16)0.23418 (13)0.0268 (3)
O20.50720 (10)0.45732 (14)0.14604 (10)0.0217 (2)
O30.41702 (10)0.16862 (14)0.06107 (10)0.0216 (2)
O40.31872 (9)0.32895 (14)0.17753 (10)0.0199 (2)
H1A0.629 (4)0.053 (5)0.205 (4)0.096 (15)*
H1B0.627 (3)0.002 (4)0.287 (3)0.068 (12)*
H2A0.554 (3)0.462 (3)0.133 (3)0.048 (9)*
H2B0.453 (2)0.477 (3)0.088 (3)0.045 (8)*
H3A0.4123 (19)0.085 (3)0.059 (2)0.029 (6)*
H3B0.454 (2)0.192 (3)0.030 (2)0.042 (8)*
H4A0.288 (2)0.294 (3)0.212 (3)0.049 (8)*
H4B0.306 (2)0.416 (3)0.172 (2)0.040 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ca0.0144 (2)0.01655 (19)0.01458 (19)0.0000.00584 (15)0.000
Na10.0192 (5)0.0302 (5)0.0196 (5)−0.0001 (4)0.0053 (4)−0.0011 (4)
Na20.0283 (6)0.0396 (6)0.0249 (5)0.0000.0089 (4)0.000
P0.01509 (18)0.01411 (17)0.01436 (17)0.00019 (13)0.00797 (14)0.00016 (12)
S10.01688 (19)0.02004 (18)0.0257 (2)−0.00401 (14)0.00981 (15)−0.00281 (14)
S20.01954 (19)0.01504 (17)0.01967 (18)0.00092 (13)0.00844 (14)−0.00104 (13)
S30.0250 (2)0.02236 (19)0.01657 (17)0.00676 (15)0.01122 (15)0.00515 (14)
O10.0201 (6)0.0272 (6)0.0298 (7)0.0039 (5)0.0075 (5)−0.0023 (5)
O20.0197 (6)0.0261 (6)0.0187 (5)−0.0009 (5)0.0076 (5)0.0038 (5)
O30.0241 (6)0.0203 (6)0.0227 (6)0.0002 (5)0.0124 (5)−0.0026 (5)
O40.0210 (6)0.0195 (5)0.0214 (6)0.0014 (4)0.0112 (5)−0.0002 (4)

Geometric parameters (Å, °)

Ca—O12.4244 (14)Na2—S1iv2.9242 (8)
Ca—O1i2.4244 (15)Na2—S32.9673 (7)
Ca—O22.4614 (13)Na2—S3i2.9674 (7)
Ca—O2i2.4615 (13)P—S12.0156 (6)
Ca—O3i2.5122 (13)P—S22.0241 (6)
Ca—O32.5123 (13)P—S32.0282 (6)
Ca—O42.5249 (13)P—Piv2.2381 (8)
Ca—O4i2.5249 (13)S1—Na2iv2.9242 (8)
Na1—O32.3523 (14)S2—Na1vi2.9768 (5)
Na1—O3ii2.3523 (14)O1—H1A0.78 (5)
Na1—O42.3713 (13)O1—H1B0.79 (4)
Na1—O4ii2.3713 (13)O2—H2A0.79 (3)
Na1—S2iii2.9767 (5)O2—H2B0.88 (3)
Na1—S2iv2.9768 (5)O3—H3A0.78 (3)
Na2—O22.5282 (17)O3—H3B0.86 (3)
Na2—O2i2.5283 (17)O4—H4A0.85 (3)
Na2—S1v2.9242 (8)O4—H4B0.83 (3)
O1—Ca—O1i75.99 (8)O4ii—Na1—S2iii90.48 (3)
O1—Ca—O2113.37 (5)O3—Na1—S2iv89.02 (4)
O1i—Ca—O2148.04 (5)O3ii—Na1—S2iv90.98 (4)
O1—Ca—O2i148.04 (5)O4—Na1—S2iv90.48 (3)
O1i—Ca—O2i113.37 (5)O4ii—Na1—S2iv89.52 (3)
O2—Ca—O2i75.64 (6)S2iii—Na1—S2iv180.0
O1—Ca—O3i79.99 (5)O2—Na2—O2i73.30 (7)
O1i—Ca—O3i73.01 (5)O2—Na2—S1v149.72 (4)
O2—Ca—O3i137.37 (4)O2i—Na2—S1v85.08 (3)
O2i—Ca—O3i74.41 (4)O2—Na2—S1iv85.08 (3)
O1—Ca—O373.01 (5)O2i—Na2—S1iv149.72 (4)
O1i—Ca—O379.99 (5)S1v—Na2—S1iv122.01 (5)
O2—Ca—O374.42 (4)O2—Na2—S396.20 (4)
O2i—Ca—O3137.37 (4)O2i—Na2—S381.01 (4)
O3i—Ca—O3145.61 (6)S1v—Na2—S3101.16 (2)
O1—Ca—O4137.92 (5)S1iv—Na2—S380.537 (18)
O1i—Ca—O474.08 (5)O2—Na2—S3i81.01 (4)
O2—Ca—O480.36 (5)O2i—Na2—S3i96.20 (4)
O2i—Ca—O472.44 (4)S1v—Na2—S3i80.537 (17)
O3i—Ca—O4117.68 (4)S1iv—Na2—S3i101.16 (2)
O3—Ca—O473.21 (4)S3—Na2—S3i176.55 (5)
O1—Ca—O4i74.08 (5)S1—P—S2112.06 (3)
O1i—Ca—O4i137.92 (5)S1—P—S3115.28 (3)
O2—Ca—O4i72.44 (4)S2—P—S3109.99 (3)
O2i—Ca—O4i80.36 (5)S1—P—Piv105.34 (3)
O3i—Ca—O4i73.21 (4)S2—P—Piv108.14 (3)
O3—Ca—O4i117.68 (4)S3—P—Piv105.48 (3)
O4—Ca—O4i145.46 (6)P—S1—Na2iv105.07 (3)
O3—Na1—O3ii180.0P—S2—Na1vi137.04 (2)
O3—Na1—O478.97 (4)P—S3—Na2111.63 (3)
O3ii—Na1—O4101.03 (4)H1A—O1—H1B105 (4)
O3—Na1—O4ii101.03 (4)Ca—O2—Na2105.53 (5)
O3ii—Na1—O4ii78.97 (4)H2A—O2—H2B108 (3)
O4—Na1—O4ii179.999 (2)Na1—O3—Ca104.38 (5)
O3—Na1—S2iii90.98 (4)Na1—O4—Ca103.44 (5)
O3ii—Na1—S2iii89.02 (4)H4A—O4—H4B106 (3)
O4—Na1—S2iii89.52 (3)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, −y+1/2, −z; (iii) x, y−1, z; (iv) −x+1/2, −y+3/2, −z; (v) x+1/2, −y+3/2, z+1/2; (vi) x, y+1, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···S3vii0.78 (5)2.58 (5)3.2922 (17)153 (4)
O1—H1B···S2viii0.79 (4)2.62 (4)3.2892 (16)144 (4)
O2—H2A···S2vii0.79 (3)2.54 (3)3.3270 (15)172 (3)
O2—H2B···S2iv0.88 (3)2.30 (3)3.1877 (15)179 (3)
O3—H3A···S1ii0.78 (3)2.43 (3)3.1908 (15)168 (2)
O3—H3B···S1vii0.86 (3)2.39 (3)3.2174 (14)161 (3)
O4—H4A···S3ix0.85 (3)2.41 (3)3.2468 (14)171 (3)
O4—H4B···S30.83 (3)2.37 (3)3.1957 (14)171 (3)

Symmetry codes: (vii) x+1/2, y−1/2, z; (viii) −x+1, y−1, −z+1/2; (iv) −x+1/2, −y+3/2, −z; (ii) −x+1/2, −y+1/2, −z; (ix) −x+1/2, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2364).

References

  • Brandenburg, K. (2004). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Fincher, T., LeBret, G. & Cleary, D. A. (1998). J. Solid State Chem.141, 274–281.
  • Ehrhardt, C. & Gjikaj, M. (2010). Acta Cryst. E66, i55. [PMC free article] [PubMed]
  • Jörgens, S., Mewis, A., Hoffmann, R.-D., Pöttgen, R. & Mosel, B. D. (2003). Z. Anorg. Allg. Chem.629, 429–433.
  • Klingen, W., Ott, R. & Hahn, H. (1973). Z. Anorg. Allg. Chem.396, 271–278.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2008). X-AREA Stoe & Cie, Darmstadt, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography