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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): i55.
Published online 2010 July 3. doi:  10.1107/S1600536810025316
PMCID: PMC3007201

Strontium disodium hexa­thio­diphosphate(IV) octa­hydrate

Abstract

The crystal structure of SrNa2(P2S6)·8H2O is isotypic with that of its calcium analogue. The asymmetric unit consists of one Sr2+ cation (2 symmetry), two Na+ cations (2 and An external file that holds a picture, illustration, etc.
Object name is e-66-00i55-efi1.jpg symmetry, respectively), one-half of a centrosymmetric (P2S6)4− anion with a staggered confirmation and four water mol­ecules. The crystal structure is built up from layers of cations and anions extending parallel to (101). Each SrO8 polyhedron is connected via edge-sharing to two NaO4S2 octa­hedra and to one NaO2S4 octa­hedron. The NaO4S2 octa­edra are, in turn, connected with two (P2S6)4− anions through common corners. Adjacent layers are held together by several O—H(...)S hydrogen-bonding inter­actions.

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 CaNa2(P2S6)·8H2O, see: Ehrhardt &Gjikaj (2010 [triangle]).

Experimental

Crystal data

  • SrNa2(P2S6)·8H2O
  • M r = 532.03
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00i55-efi2.jpg
  • a = 14.9010 (19) Å
  • b = 9.3282 (7) Å
  • c = 14.1338 (19) Å
  • β = 114.918 (10)°
  • V = 1781.7 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.98 mm−1
  • T = 223 K
  • 0.28 × 0.26 × 0.25 mm

Data collection

  • Stoe IPDS 2 diffractometer
  • 14472 measured reflections
  • 2544 independent reflections
  • 2302 reflections with I > 2σ(I)
  • R int = 0.064

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.087
  • S = 1.12
  • 2544 reflections
  • 121 parameters
  • All H-atom parameters refined
  • Δρmax = 1.14 e Å−3
  • Δρmin = −0.89 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/S1600536810025316/wm2365sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025316/wm2365Isup2.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, SrNa2(P2S6).8H2O, is isotypic with that of its calcium analogue, CaNa2(P2S6).8H2O (Ehrhardt & Gjikaj, 2010). The asymmetric unit of SrNa2(P2S6).8H2O contains one Sr2+ cation, two Na+ cations, one half of a (P2S6)4- anion 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 strontium cation is eightfold coordinated by water O atoms with Sr—O distances from 2.573 (2) to 2.6459 (19) Å. The SrO8 coordination polyhedron can be described as a bicapped trigonal prism.

The crystal structure is built up from layers of cations and anions extending parallel to (101). Within the layer each SrO8 polyhedron is connected by edge-sharing to two Na(1)O4S2 octahedra and to one Na(2)O2S4 octaedron. Furthermore, the Na(1)O4S2 octaedra are connected through common corners with two (P2S6)4- anions.

The discrete ethane-like (P2S6)4- anion has a staggered conformation and is located on a centre of inversion associated with the midpoint of the P—P bond. The corresponding P—P distance is 2.2405 (12) Å; the P—S distances range from 2.0162 (9) to 2.0248 (9) Å. These values agree well with those reported previously for other hypothiodiphosphate structures (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 3.169 to 3.334 Å (Table 2).

With the exception of the M-O bond lengths (M = Ca, Sr), all other bond lengths and angles as well as the O—H···S hydrogen bonding scheme are very similar in the two isotypic MNa2(P2S6).8H2O structures.

Experimental

Na4(P2S6).6H2O has been prepared according to Fincher et al. (1998). The title compound was obtained by adding a molar equivalent of strontium hydroxide to a solution of Na4(P2S6).6H2O in 70 ml distilled water at 348 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

SrNa2(P2S6)·8H2OF(000) = 1064
Mr = 532.03Dx = 1.983 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 14971 reflections
a = 14.9010 (19) Åθ = 1.0–29.8°
b = 9.3282 (7) ŵ = 3.98 mm1
c = 14.1338 (19) ÅT = 223 K
β = 114.918 (10)°Block, colorless
V = 1781.7 (4) Å30.28 × 0.26 × 0.25 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer2302 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.064
graphiteθmax = 29.8°, θmin = 2.7°
ω–scansh = −20→20
14472 measured reflectionsk = −13→11
2544 independent reflectionsl = −19→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087All H-atom parameters refined
S = 1.12w = 1/[σ2(Fo2) + (0.0378P)2 + 5.0597P] where P = (Fo2 + 2Fc2)/3
2544 reflections(Δ/σ)max < 0.001
121 parametersΔρmax = 1.14 e Å3
0 restraintsΔρmin = −0.88 e Å3

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

xyzUiso*/Ueq
Sr0.50000.24637 (4)0.25000.01746 (10)
Na10.25000.25000.00000.0260 (3)
Na20.50000.6875 (3)0.25000.0440 (5)
P0.20406 (5)0.76351 (7)0.04496 (5)0.01570 (13)
S10.07286 (5)0.67170 (8)−0.04401 (6)0.02445 (15)
S20.18992 (5)0.97603 (7)0.06433 (5)0.01959 (14)
S30.28146 (5)0.66742 (8)0.18434 (5)0.02452 (15)
O10.59794 (17)0.0300 (3)0.2305 (2)0.0318 (5)
O20.50855 (17)0.4687 (2)0.14363 (17)0.0259 (4)
O30.41245 (15)0.1665 (2)0.05340 (16)0.0238 (4)
O40.31300 (14)0.3293 (2)0.17560 (15)0.0220 (4)
H1A0.627 (5)0.042 (7)0.197 (5)0.08 (2)*
H1B0.638 (4)0.000 (6)0.292 (5)0.065 (17)*
H2A0.555 (5)0.473 (6)0.127 (5)0.070 (17)*
H2B0.461 (4)0.486 (5)0.093 (4)0.046 (13)*
H3A0.404 (4)0.086 (7)0.048 (5)0.067 (17)*
H3B0.450 (5)0.195 (8)0.023 (5)0.09 (2)*
H4A0.282 (3)0.283 (5)0.214 (4)0.037 (11)*
H4B0.302 (4)0.425 (7)0.170 (4)0.059 (15)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sr0.01698 (15)0.01714 (16)0.01694 (15)0.0000.00585 (11)0.000
Na10.0230 (7)0.0303 (9)0.0221 (7)0.0003 (6)0.0068 (6)−0.0014 (6)
Na20.0384 (10)0.0598 (15)0.0284 (9)0.0000.0086 (8)0.000
P0.0192 (3)0.0137 (3)0.0171 (3)−0.0002 (2)0.0104 (2)−0.0003 (2)
S10.0209 (3)0.0200 (3)0.0336 (3)−0.0042 (2)0.0127 (3)−0.0043 (3)
S20.0232 (3)0.0145 (3)0.0219 (3)0.0012 (2)0.0103 (2)−0.0008 (2)
S30.0343 (3)0.0226 (3)0.0197 (3)0.0094 (3)0.0144 (3)0.0058 (2)
O10.0232 (10)0.0306 (12)0.0366 (12)0.0049 (8)0.0076 (9)−0.0042 (10)
O20.0237 (9)0.0299 (11)0.0224 (9)0.0016 (8)0.0081 (8)0.0062 (8)
O30.0277 (10)0.0218 (10)0.0236 (9)−0.0005 (8)0.0126 (8)−0.0037 (8)
O40.0242 (9)0.0205 (9)0.0229 (9)0.0013 (7)0.0115 (7)0.0007 (8)

Geometric parameters (Å, °)

Sr—O12.573 (2)Na1—S2iv2.9741 (7)
Sr—O1i2.573 (2)Na2—O22.570 (3)
Sr—O2i2.596 (2)Na2—O2i2.570 (3)
Sr—O22.596 (2)Na2—S1iv2.9525 (15)
Sr—O32.631 (2)Na2—S1v2.9525 (15)
Sr—O3i2.631 (2)Na2—S32.9924 (9)
Sr—O42.6459 (19)Na2—S3i2.9925 (9)
Sr—O4i2.6459 (19)P—S12.0162 (9)
Na1—O3ii2.344 (2)P—S22.0243 (9)
Na1—O32.345 (2)P—S32.0248 (9)
Na1—O42.372 (2)P—Piv2.2405 (12)
Na1—O4ii2.372 (2)S1—Na2iv2.9525 (15)
Na1—S2iii2.9741 (7)S2—Na1vi2.9741 (7)
O1—Sr—O1i76.65 (12)O3—Na1—S2iii91.09 (6)
O1—Sr—O2i149.01 (7)O4—Na1—S2iii89.18 (5)
O1i—Sr—O2i113.34 (9)O4ii—Na1—S2iii90.82 (5)
O1—Sr—O2113.34 (9)O3ii—Na1—S2iv91.09 (6)
O1i—Sr—O2149.01 (7)O3—Na1—S2iv88.91 (6)
O2i—Sr—O273.96 (10)O4—Na1—S2iv90.82 (5)
O1—Sr—O373.49 (8)O4ii—Na1—S2iv89.18 (5)
O1i—Sr—O380.77 (8)S2iii—Na1—S2iv180.0
O2i—Sr—O3135.60 (7)O2—Na2—O2i74.82 (12)
O2—Sr—O374.82 (7)O2—Na2—S1iv82.23 (5)
O1—Sr—O3i80.78 (8)O2i—Na2—S1iv147.35 (8)
O1i—Sr—O3i73.50 (8)O2—Na2—S1v147.35 (8)
O2i—Sr—O3i74.82 (7)O2i—Na2—S1v82.23 (5)
O2—Sr—O3i135.59 (7)S1iv—Na2—S1v127.17 (10)
O3—Sr—O3i147.09 (10)O2—Na2—S394.85 (7)
O1—Sr—O4137.47 (7)O2i—Na2—S379.40 (6)
O1i—Sr—O473.86 (7)S1iv—Na2—S379.75 (3)
O2i—Sr—O472.30 (7)S1v—Na2—S3103.51 (3)
O2—Sr—O480.60 (7)O2—Na2—S3i79.40 (6)
O3—Sr—O472.10 (6)O2i—Na2—S3i94.85 (7)
O3i—Sr—O4118.24 (6)S1iv—Na2—S3i103.51 (3)
O1—Sr—O4i73.86 (7)S1v—Na2—S3i79.75 (3)
O1i—Sr—O4i137.47 (7)S3—Na2—S3i172.83 (11)
O2i—Sr—O4i80.60 (7)S1—P—S2111.81 (4)
O2—Sr—O4i72.30 (7)S1—P—S3115.08 (4)
O3—Sr—O4i118.23 (6)S2—P—S3110.55 (4)
O3i—Sr—O4i72.10 (6)S1—P—Piv105.20 (5)
O4—Sr—O4i145.98 (9)S2—P—Piv108.07 (5)
O3ii—Na1—O3180.0S3—P—Piv105.57 (5)
O3ii—Na1—O497.64 (7)P—S1—Na2iv106.45 (5)
O3—Na1—O482.36 (7)P—S2—Na1vi137.58 (3)
O3ii—Na1—O4ii82.36 (7)P—S3—Na2111.92 (4)
O3—Na1—O4ii97.64 (7)Na2—O2—Sr105.61 (9)
O4—Na1—O4ii180.0Na1—O3—Sr103.36 (8)
O3ii—Na1—S2iii88.91 (6)Na1—O4—Sr102.17 (7)

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···S3vii0.76 (7)2.66 (6)3.324 (3)146 (6)
O1—H1B···S2viii0.86 (6)2.53 (6)3.306 (3)151 (5)
O2—H2A···S2vii0.82 (6)2.51 (6)3.334 (2)176 (6)
O2—H2B···S2iv0.79 (5)2.43 (5)3.214 (2)176 (5)
O3—H3A···S1ii0.76 (7)2.44 (7)3.169 (2)163 (5)
O3—H3B···S1vii0.88 (7)2.40 (7)3.222 (2)157 (6)
O4—H4A···S3ix0.95 (5)2.29 (5)3.245 (2)175 (4)
O4—H4B···S30.91 (6)2.30 (6)3.199 (2)171 (5)

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: WM2365).

References

  • Brandenburg, K. (2004). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Ehrhardt, C. & Gjikaj, M. (2010). Acta Cryst. E66, i54. [PMC free article] [PubMed]
  • Fincher, T., LeBret, G. & Cleary, D. A. (1998). J. Solid State Chem.141, 274–281.
  • 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