inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Hydrates of tin tetrachloride

aSchool of Chemistry, University of Southampton, Southampton SO17 1BJ, England
*Correspondence e-mail: m.webster@soton.ac.uk

(Received 18 February 2004; accepted 10 March 2004; online 31 March 2004)

The crystal structures of the tri- and tetrahydrate of tin tetrachloride, viz. diaquatetrachlorotin(IV) monohydrate, [SnCl4(H2O)2]·H2O, and diaquatetrachlorotin(IV) dihydrate, [SnCl4(H2O)2]·2H2O, are reported and shown to contain the cis-[SnCl4(H2O)2] species and water mol­ecules in both cases. The trihydrate contains chains of the tin species linked by a single hydrogen-bonded water mol­ecule, whilst the tetrahydrate has a three-dimensional network. In addition, there are O—H⋯Cl interactions present.

Comment

The literature reports several hydrates of tin tetrachloride, including the tri-, tetra- and pentahydrate, but only the last is commercially available [see Klug & Brasted (1958[Klug, H. P. & Brasted, R. C. (1958). Comprehensive Inorganic Chemistry, edited by M. C. Sneed & R. C. Brasted, Vol. 7. New York: Van Nostrand.]) and Gmelins Handbuch der Anorganischen Chemie (1972[Gmelins Handbuch der Anorganischen Chemie (1972). Vol. 46, Teil C1, Section 6.10, pp. 313-317. Weinheim, Germany: Verlag Chemie.])] and it has been structurally characterized using a crystal selected from a commercial bulk sample (Barnes et al., 1980[Barnes, J. C., Sampson, H. A. & Weakley, T. J. R. (1980). J. Chem. Soc. Dalton Trans. pp. 949-953.]). As part of a systematic study of interactions between main group elements and acyclic and macrocyclic chalcogenoether ligands, we have isolated and structurally characterized several new families of donor–acceptor compounds involving SnIV halides with thio-, seleno- and telluroether ligands (Levason & Reid, 2001[Levason, W. & Reid, G. (2001). J. Chem. Soc. Dalton Trans. pp. 2953-2960.]; Levason et al., 2003[Levason, W., Matthews, M. L., Patel, R., Reid, G. & Webster, M. (2003). New J. Chem. 27, 1784-1788.]). In the course of this work, we have also obtained crystals which have been shown to be hydrates of SnCl4. These experiments were carried out under `an­hydrous' conditions and clearly the products arose from small amounts of water in the solvents/reagents or ingress of water from the air during manipulations.

By this route, we have prepared and determined the crystal structures of the tri- and tetrahydrate of tin tetrachloride and this has provided an opportunity to compare the two title structures with that of the pentahydrate and to establish if there are features common to all three hydrates, both in the tin species present and in the nature of the hydrogen bonding. The structure analysis of the pentahydrate (Barnes et al., 1980[Barnes, J. C., Sampson, H. A. & Weakley, T. J. R. (1980). J. Chem. Soc. Dalton Trans. pp. 949-953.]) did not locate the H atoms, but the O⋯O and O⋯Cl distances gave convincing indications of O—H⋯O and O—H⋯Cl interactions.

The trihydrate, SnCl4·3H2O or [SnCl4(H2O)2]·H2O, has been isolated on two occasions and contains a cis-octahedral [SnCl4(H2O)2] group linked into chains by solvate water mol­ecules through O—H⋯O hydrogen bonds (Fig. 1[link]). The only initial problem arose from the closeness of the cell β parameter to 90° and one of the crystals was shown to be a twin. The data reported are for the non-twin crystal, but the results for the two determinations are essentially identical and gave rise to similar R values. All the H atoms were identified: the tin-bonded water mol­ecules are hydrogen bonded to O3 and by a second hydrogen bond to a Cl atom (Table 1[link]). The hydrate water, in contrast, is hydrogen bonded to Cl, with each H atom involved in a bifurcated hydrogen bond with rather small O—H⋯Cl angles (121–146°). The Sn—Cl [2.338 (1)–2.401 (1) Å] and Sn—O [2.138 (3) and 2.169 (3) Å] distances are unexceptional.

The tetrahydrate, SnCl4·4H2O or [SnCl4(H2O)2]·2H2O, like the trihydrate, contains cis-octahedral [SnCl4(H2O)2] groups, but with a more complicated three-dimensional network of O—H⋯O bonds (Fig. 2[link]). Only the H atoms of the bonded water mol­ecules were clearly identified and included in the model, although there was evidence for some H atoms of the hydrate waters, but this was not convincing. All eight H atoms of the coordinated water mol­ecules are involved in hydrogen bonding, with H1 and H8 forming O—H⋯Cl linkages, the remainder forming O—H⋯O linkages (Table 2[link]). Judged solely by distance (no H atoms being available), O5⋯O6 [2.745 (8) Å] and O7⋯O8a [2.966 (9) Å; symmetry code: (a) x, 1 − y, ½ + z] form O—H⋯O hydrogen bonds. Short chains of hydrogen-bonded O atoms linking [SnCl4(H2O)2] groups are easily recognized [e.g. O1⋯O5⋯O6⋯O4b; symmetry code: (b) ½ + x, [3 \over 2] − y, ½ + z]. The Sn—Cl [2.359 (2)–2.397 (2) Å] and Sn—O [2.106 (5)–2.137 (6) Å] distances are again unexceptional.

The structure of the pentahydrate, SnCl4·5H2O (Barnes et al., 1980[Barnes, J. C., Sampson, H. A. & Weakley, T. J. R. (1980). J. Chem. Soc. Dalton Trans. pp. 949-953.]), again shows the cis-[SnCl4(H2O)2] moiety linked into chains parallel to c through three hydrate water mol­ecules. There is further O—H⋯O linking to a parallel chain (Fig. 3[link]) and, judged by O⋯Cl distances, there is additional weak hydrogen bonding between the double chains. Finally, the [SnCl4(H2O)2] unit has been found in a number (ca six) of complexes of crown ethers and similar mol­ecules [see Cusack et al. (1984[Cusack, P. A., Patel, B. N., Smith, P. J., Allen, D. W. & Nowell, I. W. (1984). J. Chem. Soc. Dalton Trans. pp. 1239-1243.]) and Junk & Raston (2004[Junk, P. C. & Raston, C. L. (2004). Inorg. Chim. Acta, 357, 595-599.])]. Four examples are hydrates and involve hydrogen bonding between the tin residue and the hydrate water and organic O atoms. Surprisingly, one example (Hough et al., 1986[Hough, E., Nicholson, D. G. & Vasudevan, A. K. (1986). J. Chem. Soc. Dalton Trans. pp. 2335-2337.]) contains the trans-[SnCl4(H2O)2] group, with the rest containing the by now familiar cis geometric isomer.

[Figure 1]
Figure 1
Packing diagram for trihydrate SnCl4·3H2O, viewed along the a direction. O—H⋯O hydrogen bonds are shown as dotted lines and displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
Packing diagram for tetrahydrate SnCl4·4H2O, viewed along the b direction. H atoms are only included in the model for atoms O1 to O4, but are excluded from the diagram for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (a) x, 1 − y, ½ + z.]
[Figure 3]
Figure 3
Schematic diagram of the O—H⋯O hydrogen bonding in pentahydrate SnCl3·5H2O, showing the double chains. The O atoms shown are O1, which is part of [SnCl4(H2O)2], and the hydrate atoms O2 and O3.

Experimental

Crystals were obtained serendipitously during attempts to crystallize SnCl4 complexes of di­thio­ether and tetra­thia-macrocycles from CH2Cl2. Removal of the bulk thio­ether complex by filtration and slow evaporation of the residual filtrate unexpectedly yielded crystals of the tri- and tetrahydrate of SnCl4.

Trihydrate SnCl4·3H2O

Crystal data
  • [SnCl4(H2O)2]·H2O

  • Mr = 314.54

  • Monoclinic, P21/c

  • a = 6.362 (3) Å

  • b = 11.071 (4) Å

  • c = 11.895 (4) Å

  • β = 90.22 (2)°

  • V = 837.8 (6) Å3

  • Z = 4

  • Dx = 2.494 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 25 reflections

  • θ = 23.0–24.9°

  • μ = 4.26 mm−1

  • T = 150 (2) K

  • Block, colourless

  • 0.48 × 0.28 × 0.20 mm

Data collection
  • Rigaku AFC-7S diffractometer

  • ω/2θ scans

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.268, Tmax = 0.427

  • 1549 measured reflections

  • 1475 independent reflections

  • 1356 reflections with I > 2σ(I)

  • Rint = 0.011

  • θmax = 25.0°

  • h = −7 → 7

  • k = 0 → 13

  • l = 0 → 14

  • 3 standard reflections every 200 reflections intensity decay: none

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.082

  • S = 1.07

  • 1475 reflections

  • 92 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0569P)2 + 1.1933P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.83 e Å−3

  • Δρmin = −2.44 e Å−3

Table 1
Hydrogen-bonding geometry (Å, °) for trihydrate SnCl4·3H2O

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O3i 0.82 (2) 1.91 (3) 2.678 (5) 156 (6)
O1—H2⋯Cl2ii 0.84 (5) 2.44 (3) 3.238 (3) 158 (6)
O2—H3⋯Cl3iii 0.85 (5) 2.35 (6) 3.188 (4) 172 (7)
O2—H4⋯O3 0.83 (6) 1.85 (3) 2.675 (5) 169 (8)
O3—H5⋯Cl3iv 0.84 (6) 2.56 (4) 3.286 (4) 144 (5)
O3—H5⋯Cl2iii 0.84 (6) 2.80 (6) 3.309 (4) 121 (5)
O3—H6⋯Cl1v 0.83 (6) 2.59 (5) 3.315 (4) 146 (7)
O3—H6⋯Cl1vi 0.83 (6) 2.91 (6) 3.425 (4) 122 (6)
Symmetry codes: (i) [x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]; (ii) [1-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]; (iii) [x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]; (iv) [1+x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]; (v) 1+x,y,z; (vi) 1-x,-y,1-z.

Tetrahydrate SnCl4·4H2O

Crystal data
  • [SnCl4(H2O)2]·2H2O

  • Mr = 332.55

  • Monoclinic, Cc

  • a = 23.987 (4) Å

  • b = 6.714 (6) Å

  • c = 11.580 (3) Å

  • β = 93.77 (2)°

  • V = 1860.9 (18) Å3

  • Z = 8

  • Dx = 2.374 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 25 reflections

  • θ = 23.6–24.9°

  • μ = 3.85 mm−1

  • T = 150 (2) K

  • Block, colourless

  • 0.42 × 0.34 × 0.28 mm

Data collection
  • Rigaku AFC-7S diffractometer

  • ω/2θ scans

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.241, Tmax = 0.340

  • 1717 measured reflections

  • 1717 independent reflections

  • 1704 reflections with I > 2σ(I)

  • θmax = 25.0°

  • h = −28 → 28

  • k = −7 → 0

  • l = 0 → 13

  • 3 standard reflections every 200 reflections intensity decay: none

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.074

  • S = 1.13

  • 1717 reflections

  • 164 parameters

  • H-atom parameters not refined

  • w = 1/[σ2(Fo2) + (0.0598P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.94 e Å−3

  • Δρmin = −2.23 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.])

  • Flack parameter = 0.11 (3)

Table 2
Hydrogen-bonding geometry (Å, °) for tetrahydrate SnCl4·4H2O

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯Cl1i 0.84 2.42 3.223 (5) 162
O1—H2⋯O5ii 0.84 1.78 2.600 (8) 164
O2—H3⋯O8iii 0.85 1.89 2.703 (7) 158
O2—H4⋯O7iv 0.84 1.83 2.653 (8) 165
O3—H5⋯O8ii 0.84 1.86 2.680 (8) 162
O3—H6⋯O6v 0.84 1.89 2.672 (8) 154
O4—H7⋯O6vi 0.83 1.83 2.653 (8) 167
O4—H8⋯Cl8vii 0.83 2.49 3.256 (6) 153
Symmetry codes: (i) [x,-y,{\script{1\over 2}}+z]; (ii) x,y-1,z; (iii) [x,1-y,{\script{1\over 2}}+z]; (iv) [x,-y,z-{\script{1\over 2}}]; (v) [x-{\script{1\over 2}},{\script{1\over 2}}-y,z-{\script{1\over 2}}]; (vi) [x-{\script{1\over 2}},{\script{3\over 2}}-y,z-{\script{1\over 2}}]; (vii) [x,1-y,z-{\script{1\over 2}}].

For the trihydrate, all the H atoms were located from a difference electron-density map and refined using restraints on the O—H bond distances (0.84 Å). H atoms were given a common refined displacement parameter. For the tetrahydrate, a difference electron-density map showed a number of peaks for potential H atoms, of which the eight of the tin-bonded water mol­ecules were the most convincing, with reasonable O—H, H—O—H and H—O—Sn geometry. Inclusion of these with restraints (DFIX) gave a satisfactory model. The H atoms on the hydrate water mol­ecules were incomplete, with poor H—O—H angles (in two cases where both H atoms were located), and refinement calculations gave unsatisfactory intermolecular H⋯H distances. Accordingly, these H atoms were excluded from the model. The Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter for the tetrahydrate was determined from a small number of reflections, which makes the absolute structure determination of the chosen crystals less reliable. The H atoms were fixed in the final cycle as the shift/error values were small but failing to converge probably due to the large correlation coefficients between the H-atom coordinates.

For both compounds, data collection and cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988[Molecular Structure Corporation (1988). MSC/AFC Diffractometer Control Software. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.]); data reduction: TEXSAN (Molecular Structure Corporation, 1995[Molecular Structure Corporation (1995). TEXSAN. Version 1.7-1. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); molecular graphics: ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The literature reports several hydrates of tin tetrachloride, including the tri-, tetra- and pentahydrates, but only the latter is commercially available [see, for examples, Klug & Brasted (1958) and Gmelins Handbuch der Anorganischen Chemie (1972)]. Only the pentahydrate has been structurally characterized using a crystal selected from a commercial bulk sample (Barnes et al., 1980). As part of a systematic study of interactions between main group elements and acyclic and macrocyclic chalcogenoether ligands, we have isolated and structurally characterized several new families of donor–acceptor compounds involving SnIV halides with thio-, seleno- and telluroether ligands (Levason & Reid, 2001; Levason et al., 2003). In the course of this work, we have also obtained crystals which have been shown to be hydrates of SnCl4. These experiments were carried out under `anhydrous' conditions and clearly the products arose from small amounts of water in the solvents/reagents or ingress of water from the air during manipulations.

By this route, we have prepared and determined the crystal structures of the tri- and tetrahydrate and this has provided an opportunity to compare the three structures and to establish if there are features common to all, both in the tin species present and the nature of the hydrogen bonding. The structure analysis of the pentahydrate (Barnes et al., 1980) did not locate the H atoms but the O···O and O···Cl distances gave convincing indications of O—H···O and O—H···Cl interactions.

The trihydrate, SnCl4·3H2O or [SnCl4(H2O)2]·H2O, has been isolated on two occasions and contains a cis-octahedral SnCl4(H2O)2 group linked into chains by solvate water molecules through O—H···O hydrogen bonds (Fig. 1). The only initial problem arose from the closeness of the cell β parameter to 90° and one of the crystals was shown to be a twin. The data reported are from the non-twin crystal, but the results for the two determinations are essentially identical and give rise to similar R values. All the H atoms were identified: the tin-bonded water molecules are hydrogen bonded to O3 and by a second hydrogen bond to a Cl atom (Table 1). The hydrate water, in contrast, is hydrogen bonded to Cl, with each H atom involved in a bifurcated hydrogen bond with rather small O—H···Cl angles (121–146°). The Sn—Cl [2.338 (1)–2.401 (1) Å] and Sn—O [2.138 (3) and 2.169 (3) Å] distances are unexceptional.

The tetrahydrate, SnCl4·4H2O or [SnCl4(H2O)2]·2H2O, like the trihydrate, contains cis-octahedral SnCl4(H2O)2 groups, but with a more complicated three-dimensional network of O—H···O bonds (Fig. 2). Only the H atoms of the bonded water molecules were clearly identified and included in the model, although there was evidence for some H atoms of the hydrate waters but this was not convincing. All eight H atoms of the coordinated water molecules are involved in hydrogen bonding with H1 and H8, forming O—H···Cl linkages, the remainder being O—H···O (Table 2). Judged solely by distance (no H atoms being available), O5···O6 [2.745 (8) Å] and O7···O8a [2.966 (9) Å; symmetry code: (a) x, 1 − y, 1/2 + z] form O—H···O bonds. Short chains of hydrogen-bonded O atoms linking SnCl4(H2O)2 groups are easily recognized [e.g. O1—O5—O6—O4b; symmetry code: (b) 1/2 + x, 3/2 − y, 1/2 + z]. The Sn—Cl [2.359 (2)–2.397 (3) Å] and Sn—O [2.106 (5)–2.137 (6) Å] distances are unexceptional.

The structure of the pentahydrate, SnCl4·5H2O (Barnes et al., 1980), again shows the cis-[SnCl4(H2O)2] moiety linked into chains parallel to c through three hydrate water molecules. There is further O—H···O linking to a parallel chain (Fig. 3) and, judged by O···Cl distances, there is additional weak hydrogen bonding between the double chains. Finally, the SnCl4(H2O)2 unit has been found in a number (ca six) of complexes of crown ethers and similar molecules [see, for example, Cusack et al. (1984) and Junk & Raston (2004)]. Four examples are hydrates and involve hydrogen bonding between the tin residue and hydrate water and the organic O atoms. Surprisingly, one example (Hough et al., 1986) contains the trans-[SnCl4(H2O)2] group, with the rest containing the by now familiar cis geometric isomer.

Experimental top

Crystals were obtained serendipitously during attempts to crystallize SnCl4 complexes of dithioether and tetrathia-macrocycles from CH2Cl2. Removal of the bulk thioether complex by filtration and slow evaporation of the residual filtrate unexpectedly yielded crystals of the tri- and tetrahydrates of SnCl4.

Refinement top

For the trihydrate, all the H atoms were located from a difference electron-density map and refined using restraints on the O—H bond distances (0.84 Å). H atoms were given a common refined displacement parameter. For the tetrahydrate, a difference electron-density map showed a number of peaks for potential H atoms, of which the eight of the tin-bonded water molecules were the most convincing, with reasonable O—H, H—O—H and H—O—Sn geometry. Inclusion of these with restraints (DFIX) gave a satisfactory model. The H atoms on the hydrate water molecules were incomplete, with poor H—O—H angles (in two cases where both H atoms were located) and refinement calculations gave unsatisfactory intermolecular H···H distances. Accordingly, these H atoms were excluded from the model. The Flack (1983) parameter for the tetrahydrate was determined from a small number of reflections which makes the absolute structure determination of the chosen crystals less reliable. The H atoms were fixed in the final cycle as the shift/error values were small but failing to converge probably due to the large correlation coefficients between the H-atom coordinates.

Computing details top

For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Packing diagram for [SnCl4(H2O)2]·H2O, viewed along the a direction. O—H···O hydrogen bonds are shown as dotted lines and displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram for [SnCl4(H2O)2]·2H2O, viewed along the b direction. H atoms are only included in the model for atoms O1 to O4, but are excluded from the diagram for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (a) x, 1 − y, 1/2 + z.]
[Figure 3] Fig. 3. Schematic diagram of the O—H···O hydrogen bonding in [SnCl4(H2O)2]·3H2O, showing the double chains. The only O atoms shown are O1, part of [SnCl4(H2O)2], and the hydrate atoms O2 and O3.
(I) Tetrachlorodiaquatin(IV) monohydrate top
Crystal data top
[SnCl4(H2O)2]·H2OF(000) = 592
Mr = 314.54Dx = 2.494 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 6.362 (3) Åθ = 23.0–24.9°
b = 11.071 (4) ŵ = 4.26 mm1
c = 11.895 (4) ÅT = 150 K
β = 90.22 (2)°Block, colourless
V = 837.8 (6) Å30.48 × 0.28 × 0.20 mm
Z = 4
Data collection top
Rigaku AFC-7S
diffractometer
1356 reflections with I > 2σ(I)
Radiation source: fine-focus Mo sealed tubeRint = 0.011
Graphite monochromatorθmax = 25.0°, θmin = 2.5°
ω/2θ scansh = 77
Absorption correction: ψ scan
(North et al., 1968)
k = 013
Tmin = 0.268, Tmax = 0.427l = 014
1549 measured reflections3 standard reflections every 200 reflections
1475 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: difference Fourier map
wR(F2) = 0.082H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0569P)2 + 1.1933P]
where P = (Fo2 + 2Fc2)/3
1475 reflections(Δ/σ)max = 0.001
92 parametersΔρmax = 0.83 e Å3
7 restraintsΔρmin = 2.44 e Å3
Crystal data top
[SnCl4(H2O)2]·H2OV = 837.8 (6) Å3
Mr = 314.54Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.362 (3) ŵ = 4.26 mm1
b = 11.071 (4) ÅT = 150 K
c = 11.895 (4) Å0.48 × 0.28 × 0.20 mm
β = 90.22 (2)°
Data collection top
Rigaku AFC-7S
diffractometer
1356 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.011
Tmin = 0.268, Tmax = 0.4273 standard reflections every 200 reflections
1549 measured reflections intensity decay: none
1475 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0297 restraints
wR(F2) = 0.082H-atom parameters constrained
S = 1.07Δρmax = 0.83 e Å3
1475 reflectionsΔρmin = 2.44 e Å3
92 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

DFIX used on the d(O—H) distances with a target distance 0.84 (2) Angstrom. H atoms given a common refined adp.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.36858 (4)0.23528 (3)0.66346 (2)0.01350 (15)
Cl10.23914 (17)0.09273 (10)0.53026 (9)0.0210 (3)
Cl20.69212 (16)0.13053 (9)0.68652 (9)0.0179 (2)
Cl30.21634 (17)0.13467 (10)0.82238 (9)0.0199 (3)
Cl40.09960 (18)0.37715 (10)0.64014 (10)0.0238 (3)
O10.5134 (5)0.3672 (3)0.7697 (3)0.0198 (7)
O20.5277 (5)0.3335 (3)0.5309 (3)0.0209 (7)
O30.8115 (5)0.2091 (3)0.4126 (3)0.0238 (7)
H10.582 (9)0.353 (7)0.827 (3)0.057 (9)*
H20.446 (10)0.425 (4)0.797 (5)0.057 (9)*
H30.450 (10)0.350 (7)0.475 (4)0.057 (9)*
H40.603 (10)0.289 (6)0.492 (5)0.057 (9)*
H50.884 (9)0.242 (6)0.362 (4)0.057 (9)*
H60.876 (10)0.161 (5)0.454 (5)0.057 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0129 (2)0.0107 (2)0.0169 (2)0.00045 (10)0.00213 (13)0.00132 (10)
Cl10.0221 (6)0.0173 (5)0.0235 (6)0.0010 (4)0.0064 (4)0.0064 (4)
Cl20.0145 (5)0.0143 (5)0.0248 (5)0.0022 (4)0.0031 (4)0.0007 (4)
Cl30.0184 (5)0.0205 (6)0.0209 (5)0.0029 (4)0.0003 (4)0.0002 (4)
Cl40.0191 (6)0.0182 (5)0.0339 (6)0.0073 (4)0.0045 (4)0.0025 (5)
O10.0218 (17)0.0121 (15)0.0254 (17)0.0012 (12)0.0075 (13)0.0062 (13)
O20.0195 (17)0.0211 (17)0.0222 (17)0.0014 (13)0.0008 (13)0.0035 (13)
O30.0185 (17)0.0308 (18)0.0221 (17)0.0008 (15)0.0024 (13)0.0070 (15)
Geometric parameters (Å, º) top
Sn1—Cl12.3810 (12)O1—H10.82 (2)
Sn1—Cl22.3775 (13)O1—H20.84 (5)
Sn1—Cl32.4013 (13)O2—H30.85 (5)
Sn1—Cl42.3384 (12)O2—H40.83 (6)
Sn1—O12.138 (3)O3—H50.84 (6)
Sn1—O22.169 (3)O3—H60.83 (6)
O1—Sn1—O283.46 (13)Cl2—Sn1—Cl192.90 (4)
O1—Sn1—Cl485.69 (9)Cl4—Sn1—Cl396.19 (5)
O2—Sn1—Cl485.43 (10)Cl2—Sn1—Cl391.98 (4)
O1—Sn1—Cl391.47 (10)Cl1—Sn1—Cl394.41 (5)
O2—Sn1—Cl3174.56 (9)Sn1—O1—H1126 (6)
O1—Sn1—Cl283.92 (9)Sn1—O1—H2122 (5)
O2—Sn1—Cl285.55 (9)H1—O1—H296 (6)
O1—Sn1—Cl1173.42 (10)Sn1—O2—H3114 (5)
O2—Sn1—Cl190.56 (9)Sn1—O2—H4112 (5)
Cl4—Sn1—Cl2166.94 (4)H3—O2—H491 (7)
Cl4—Sn1—Cl196.61 (5)H5—O3—H6115 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.82 (2)1.91 (3)2.678 (5)156 (6)
O1—H2···Cl2ii0.84 (5)2.44 (3)3.238 (3)158 (6)
O2—H3···Cl3iii0.85 (5)2.35 (6)3.188 (4)172 (7)
O2—H4···O30.83 (6)1.85 (3)2.675 (5)169 (8)
O3—H5···Cl3iv0.84 (6)2.56 (4)3.286 (4)144 (5)
O3—H5···Cl2iii0.84 (6)2.80 (6)3.309 (4)121 (5)
O3—H6···Cl1v0.83 (6)2.59 (5)3.315 (4)146 (7)
O3—H6···Cl1vi0.83 (6)2.91 (6)3.425 (4)122 (6)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y+1/2, z+3/2; (iii) x, y+1/2, z1/2; (iv) x+1, y+1/2, z1/2; (v) x+1, y, z; (vi) x+1, y, z+1.
(II) Tetrachlorodiaquatin(IV) dihydrate top
Crystal data top
[SnCl4(H2O)2]·2H2OF(000) = 1264
Mr = 332.55Dx = 2.374 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 25 reflections
a = 23.987 (4) Åθ = 23.6–24.9°
b = 6.714 (6) ŵ = 3.85 mm1
c = 11.580 (3) ÅT = 150 K
β = 93.77 (2)°Block, colourless
V = 1860.9 (18) Å30.42 × 0.34 × 0.28 mm
Z = 8
Data collection top
Rigaku AFC7S
diffractometer
1704 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 25.0°, θmin = 3.2°
ω/2θ scansh = 2828
Absorption correction: ψ scan
(North et al., 1968)
k = 70
Tmin = 0.241, Tmax = 0.340l = 013
1717 measured reflections3 standard reflections every 200 reflections
1717 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029H-atom parameters not refined
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.0598P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
1717 reflectionsΔρmax = 0.94 e Å3
164 parametersΔρmin = 2.23 e Å3
13 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.11 (3)
Crystal data top
[SnCl4(H2O)2]·2H2OV = 1860.9 (18) Å3
Mr = 332.55Z = 8
Monoclinic, CcMo Kα radiation
a = 23.987 (4) ŵ = 3.85 mm1
b = 6.714 (6) ÅT = 150 K
c = 11.580 (3) Å0.42 × 0.34 × 0.28 mm
β = 93.77 (2)°
Data collection top
Rigaku AFC7S
diffractometer
1704 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.241, Tmax = 0.3403 standard reflections every 200 reflections
1717 measured reflections intensity decay: none
1717 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters not refined
wR(F2) = 0.074Δρmax = 0.94 e Å3
S = 1.13Δρmin = 2.23 e Å3
1717 reflectionsAbsolute structure: Flack (1983)
164 parametersAbsolute structure parameter: 0.11 (3)
13 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

The H atoms of the Sn bonded waters were included in the model. The other H atoms were less convincing as not all were found, did not refine well and these were excluded from the model. Restraints on O—H were used.

Fixed H atoms in final cycle as shift/error were small but failing to converge probably due to large correlation between H atom parameters.

Probably not enough Friedel related reflections (90) for a reliable absolute structure determination.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.242986 (18)0.12803 (7)0.17477 (3)0.01388 (15)
Sn20.009876 (17)0.33648 (7)0.08266 (3)0.01389 (15)
Cl10.27173 (8)0.1780 (3)0.09203 (15)0.0199 (4)
Cl20.20962 (8)0.3850 (3)0.29478 (16)0.0215 (4)
Cl30.32761 (7)0.2997 (3)0.13795 (16)0.0224 (4)
Cl40.19213 (7)0.2397 (3)0.00579 (15)0.0228 (4)
Cl50.09836 (7)0.2192 (3)0.03083 (15)0.0234 (4)
Cl60.07409 (7)0.4236 (3)0.17073 (17)0.0223 (4)
Cl70.03933 (8)0.1873 (3)0.07930 (16)0.0257 (4)
Cl80.01963 (9)0.6577 (3)0.00414 (17)0.0235 (4)
O10.2850 (2)0.0240 (8)0.3316 (4)0.0189 (11)
O20.1741 (2)0.0426 (8)0.2246 (4)0.0205 (11)
O30.0049 (2)0.0798 (7)0.1859 (4)0.0182 (11)
O40.0534 (2)0.4506 (8)0.2354 (5)0.0240 (12)
O50.3170 (2)0.6573 (8)0.3650 (5)0.0224 (12)
O60.4130 (3)0.6733 (8)0.2488 (5)0.0230 (12)
O70.1290 (2)0.3042 (9)0.5742 (5)0.0296 (13)
O80.0935 (2)0.8945 (9)0.1473 (5)0.0267 (13)
H10.27730.03880.40050.037*
H20.28920.10030.33920.037*
H30.14560.01740.24770.037*
H40.16090.10990.16780.037*
H50.02290.01120.16180.037*
H60.03200.00120.18440.037*
H70.06370.56860.22960.037*
H80.05610.40420.30230.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0125 (2)0.0175 (2)0.0120 (2)0.00048 (19)0.00384 (17)0.0000 (2)
Sn20.0124 (3)0.0178 (2)0.0119 (2)0.00094 (18)0.00420 (17)0.00003 (19)
Cl10.0233 (10)0.0211 (8)0.0160 (8)0.0045 (7)0.0059 (7)0.0018 (7)
Cl20.0200 (9)0.0208 (9)0.0246 (10)0.0015 (6)0.0068 (7)0.0053 (7)
Cl30.0161 (8)0.0294 (10)0.0223 (9)0.0055 (7)0.0059 (7)0.0014 (8)
Cl40.0209 (8)0.0307 (10)0.0166 (8)0.0034 (8)0.0004 (6)0.0047 (8)
Cl50.0154 (8)0.0352 (11)0.0202 (9)0.0042 (8)0.0060 (6)0.0011 (8)
Cl60.0167 (8)0.0283 (10)0.0228 (9)0.0047 (7)0.0082 (7)0.0002 (8)
Cl70.0237 (9)0.0355 (11)0.0175 (9)0.0029 (8)0.0014 (7)0.0075 (8)
Cl80.0330 (11)0.0183 (8)0.0199 (9)0.0003 (7)0.0063 (8)0.0027 (7)
O10.027 (3)0.021 (3)0.009 (3)0.003 (2)0.0024 (19)0.000 (2)
O20.023 (3)0.024 (3)0.016 (3)0.003 (2)0.008 (2)0.007 (2)
O30.015 (3)0.015 (3)0.024 (3)0.002 (2)0.002 (2)0.007 (2)
O40.025 (3)0.028 (3)0.018 (3)0.007 (2)0.002 (2)0.005 (2)
O50.017 (3)0.029 (3)0.021 (3)0.006 (2)0.000 (2)0.001 (2)
O60.029 (3)0.026 (3)0.014 (3)0.003 (2)0.001 (2)0.001 (2)
O70.027 (3)0.031 (3)0.030 (3)0.006 (2)0.003 (2)0.006 (3)
O80.018 (3)0.034 (3)0.029 (3)0.000 (2)0.011 (2)0.005 (3)
Geometric parameters (Å, º) top
Sn1—O22.121 (5)Sn2—Cl62.3895 (18)
Sn1—O12.136 (5)Sn2—Cl82.397 (3)
Sn1—Cl42.3591 (19)O1—H10.8368
Sn1—Cl22.386 (2)O1—H20.8448
Sn1—Cl12.388 (2)O2—H30.8530
Sn1—Cl32.3968 (19)O2—H40.8430
Sn2—O32.106 (5)O3—H50.8420
Sn2—O42.137 (6)O3—H60.8380
Sn2—Cl72.371 (2)O4—H70.8336
Sn2—Cl52.3775 (19)O4—H80.8338
O2—Sn1—O185.7 (2)O3—Sn2—Cl682.94 (15)
O2—Sn1—Cl491.59 (15)O4—Sn2—Cl686.49 (17)
O1—Sn1—Cl4177.05 (16)Cl7—Sn2—Cl692.94 (7)
O2—Sn1—Cl286.28 (15)Cl5—Sn2—Cl6168.64 (7)
O1—Sn1—Cl284.19 (15)O3—Sn2—Cl8170.15 (15)
Cl4—Sn1—Cl294.49 (8)O4—Sn2—Cl888.20 (16)
O2—Sn1—Cl183.97 (15)Cl7—Sn2—Cl896.06 (8)
O1—Sn1—Cl185.83 (15)Cl5—Sn2—Cl894.51 (8)
Cl4—Sn1—Cl195.04 (8)Cl6—Sn2—Cl893.84 (8)
Cl2—Sn1—Cl1166.53 (7)Sn1—O1—H1130.5
O2—Sn1—Cl3172.71 (15)Sn1—O1—H2117.2
O1—Sn1—Cl387.15 (15)H1—O1—H292.9
Cl4—Sn1—Cl395.59 (7)Sn1—O2—H3119.1
Cl2—Sn1—Cl394.37 (8)Sn1—O2—H4109.8
Cl1—Sn1—Cl394.14 (8)H3—O2—H4103.2
O3—Sn2—O482.3 (2)Sn2—O3—H5109.4
O3—Sn2—Cl793.41 (16)Sn2—O3—H6115.5
O4—Sn2—Cl7175.73 (16)H5—O3—H6104.3
O3—Sn2—Cl587.55 (14)Sn2—O4—H7113.9
O4—Sn2—Cl586.09 (17)Sn2—O4—H8129.7
Cl7—Sn2—Cl593.82 (7)H7—O4—H8115.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl1i0.842.423.223 (5)162
O1—H2···O5ii0.841.782.600 (8)164
O2—H3···O8iii0.851.892.703 (7)158
O2—H4···O7iv0.841.832.653 (8)165
O3—H5···O8ii0.841.862.680 (8)162
O3—H6···O6v0.841.892.672 (8)154
O4—H7···O6vi0.831.832.653 (8)167
O4—H8···Cl8vii0.832.493.256 (6)153
Symmetry codes: (i) x, y, z+1/2; (ii) x, y1, z; (iii) x, y+1, z+1/2; (iv) x, y, z1/2; (v) x1/2, y+1/2, z1/2; (vi) x1/2, y+3/2, z1/2; (vii) x, y+1, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[SnCl4(H2O)2]·H2O[SnCl4(H2O)2]·2H2O
Mr314.54332.55
Crystal system, space groupMonoclinic, P21/cMonoclinic, Cc
Temperature (K)150150
a, b, c (Å)6.362 (3), 11.071 (4), 11.895 (4)23.987 (4), 6.714 (6), 11.580 (3)
β (°) 90.22 (2) 93.77 (2)
V3)837.8 (6)1860.9 (18)
Z48
Radiation typeMo KαMo Kα
µ (mm1)4.263.85
Crystal size (mm)0.48 × 0.28 × 0.200.42 × 0.34 × 0.28
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Rigaku AFC7S
diffractometer
Absorption correctionψ scan
(North et al., 1968)
ψ scan
(North et al., 1968)
Tmin, Tmax0.268, 0.4270.241, 0.340
No. of measured, independent and
observed [I > 2σ(I)] reflections
1549, 1475, 1356 1717, 1717, 1704
Rint0.0110.000
(sin θ/λ)max1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.082, 1.07 0.029, 0.074, 1.13
No. of reflections14751717
No. of parameters92164
No. of restraints713
H-atom treatmentH-atom parameters constrainedH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.83, 2.440.94, 2.23
Absolute structure?Flack (1983)
Absolute structure parameter?0.11 (3)

Computer programs: SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.82 (2)1.91 (3)2.678 (5)156 (6)
O1—H2···Cl2ii0.84 (5)2.44 (3)3.238 (3)158 (6)
O2—H3···Cl3iii0.85 (5)2.35 (6)3.188 (4)172 (7)
O2—H4···O30.83 (6)1.85 (3)2.675 (5)169 (8)
O3—H5···Cl3iv0.84 (6)2.56 (4)3.286 (4)144 (5)
O3—H5···Cl2iii0.84 (6)2.80 (6)3.309 (4)121 (5)
O3—H6···Cl1v0.83 (6)2.59 (5)3.315 (4)146 (7)
O3—H6···Cl1vi0.83 (6)2.91 (6)3.425 (4)122 (6)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y+1/2, z+3/2; (iii) x, y+1/2, z1/2; (iv) x+1, y+1/2, z1/2; (v) x+1, y, z; (vi) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl1i0.842.423.223 (5)162
O1—H2···O5ii0.841.782.600 (8)164
O2—H3···O8iii0.851.892.703 (7)158
O2—H4···O7iv0.841.832.653 (8)165
O3—H5···O8ii0.841.862.680 (8)162
O3—H6···O6v0.841.892.672 (8)154
O4—H7···O6vi0.831.832.653 (8)167
O4—H8···Cl8vii0.832.493.256 (6)153
Symmetry codes: (i) x, y, z+1/2; (ii) x, y1, z; (iii) x, y+1, z+1/2; (iv) x, y, z1/2; (v) x1/2, y+1/2, z1/2; (vi) x1/2, y+3/2, z1/2; (vii) x, y+1, z1/2.
 

Acknowledgements

The authors thank the EPSRC for access to the chemical database service at Daresbury.

References

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