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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 1| January 2005| Pages m34-m39
doi:10.1107/S0108270104029051

The effect of hydrogen-bonding anions on the structure of metal–sulf­imide complexes

CROSSMARK_Color_square_no_text.svg
Sophie H. Dale,a Mark R. J. Elsegood,a Kathryn E. Holmesa and Paul F. Kellya*

aChemistry Department, Loughborough University, Leicestershire LE11 3TU, England
*Correspondence e-mail: p.f.kelly@lboro.ac.uk

(Received 19 October 2004; accepted 9 November 2004; online 11 December 2004)

Investigations into the effects of the choice of anion on the hydrogen-bonding interactions between anions and metal–sulf­imide cationic complexes have led to the study of three novel compounds. Hexakis(S,S-di­phenyl­sulf­imide)­cobalt(II) diiodide S,S-di­phenyl­sulf­imide aceto­nitrile disolvate, [Co(C12H11NS)6]I2·C12H11NS·2C2H3N, crystallizes in the centrosymmetric space group P[\overline 1] with Z = 2. Six di­phenyl­sulf­imide ligands coordinate to the cobalt centre through their N atoms. Two iodide counter-ions hydrogen bond to the cation through N—H⋯I interactions, with N⋯I distances in the range 3.7302 (19)–3.8461 (19) Å. One extra mol­ecule of sulf­imide is included in the asymmetric unit, regardless of the metal–ligand ratio used in the synthesis, and this sulf­imide molecule also hydrogen bonds to one of the iodide counter-ions through one N—H⋯I hydrogen bond. The reaction of FeCl3·6H2O with S,S-di­phenyl­sulf­imide monohydrate yields hexakis(S,S-di­phenyl­sulf­imide)­iron(III) trichloride, [Fe(C12H11NS)6]Cl3. The complex crystallizes in the centrosymmetric cubic space group [Pa\overline 3] and the asymmetric unit contains one-sixth of a formula unit. Two of the chloride anions each hydrogen bond to three sulf­imide NH groups on opposite sides of the [Fe(Ph2SNH)6]3+ cation. The third chloride anion does not take part in any strong hydrogen bonding; instead it is surrounded by aromatic groups and is involved in C—H⋯Cl hydrogen bonds. The reaction of [Pt(Ph2SNH)4]Cl2 with I2 facilitates oxidation of the PtII metal centre to PtIV, producing tetrakis(S,S-di­phenyl­sulf­imide)­di­iodo­platinum(IV) dichloride di­chloro­methane disolvate, [PtI2(C12H11NS)4]Cl2·2CH2Cl2. The crystal structure is centrosymmetric, with the elongated octahedral cationic complex situated on an inversion centre. The chloride anions are hydrogen bonded to the cation through N—H⋯Cl hydrogen bonds, with two cis NH groups hydrogen bonded to each anion. Strong hydrogen bonding within these three compounds is limited to N—H⋯halide hydrogen bonds between the cation and two anions, with a three-up/three-down arrangement of the NH groups in the first two compounds. The anions also `cap' the NH groups in the third compound. In all three cases, the anions are also involved in weaker hydrogen bonds utilizing the plethora of relatively acidic aryl CH groups in the structures.

Comment

S,S-Di­phenyl­sulf­imide, Ph2SNH, has proven to be an extremely useful ligand for later transition metal centres in so far as the complexes produced invariably exhibit strong hydrogen bonding between the sulf­imide NH groups and the counter-ions. As a result, the complexes often show unusual structural properties; by way of example, the ostensibly simple reaction of the ligand with Cu(BF4)2 results in a multitude of products, including three polymorphs of [Cu(Ph2SNH)4](BF4)2, the inter-allogon [Cu(Ph2SNH)4]2(BF4)4 and the mixed coordination system [Cu(Ph2SNH)4][Cu(Ph2SNH)5](BF4)4 (Holmes et al., 2002[Holmes, K. E., Kelly, P. F. & Elsegood, M. R. J. (2002). CrystEngComm, 4, 545-547.]).

[Scheme 1]

One of the first examples of a metal–sulf­imide complex reported was [Co(Ph2SNH)6]Cl2, in which the ligands are arranged around the metal centre in such a way as to maximize the hydrogen-bonding interactions between the sulf­imide NH groups and the chloride counter-ions (Kelly et al., 1998[Kelly, P. F., Slawin, A. M. Z. & Waring, K. W. (1998). Inorg. Chem. Commun. 1, 249-250.]). Hence, each chloride ion acts as a trifurcated acceptor, with three NH bonds pointing upwards and three down. The isostructural nickel(II) complex has since been reported by Sellmann et al. (2001[Sellmann, D., Geipel, F. & Heinemann, F. W. (2001). Z. Anorg. Allg. Chem. 627, 1034-1038.]).

We describe here investigations into the effect of the modification of the anion on the hydrogen-bonding interactions between Co–, Fe– and Pt–sulf­imide complexes and uncoordinated anions.

In the light of the successful study of [Co(Ph2SNH)6]Cl2, the modification of the anion from the chloride to the larger, less electronegative, iodide was attempted. The reaction of Ph2SNH with CoI2 in aceto­nitrile results in pink crystals of [Co(Ph2SNH)6]I2·Ph2SNH·2MeCN, (I[link]), which crystallizes in a triclinic space group, indicating that the crystallographically imposed symmetry of the chloride complex has been broken. The crystal structure of (I[link]) is centrosymmetric and the asymmetric unit contains a complete formula unit. The CoII centre is octahedrally coordinated by six sulf­imide ligands, with trans angles lying between 178.44 (8) and 179.23 (8)° (Fig. 1[link] and Table 1[link]). The ligands are arranged in the same way as in the chloride complex, with three sulf­imide NH groups on either side of the metal. Each halide ion therefore acts as a trifurcated acceptor to the [Co(Ph2SNH)6]2+ cation, with N⋯I distances in the range 3.7302 (19)–3.8461 (19) Å and N—H⋯I angles in the range 157 (2)–165 (2)° (Fig. 2[link] and Table 2[link]). A mean distance of 3.66 (1) Å has been quoted for N⋯I contact distances for sp2-hybridized NH groups (Desiraju & Steiner, 1999[Desiraju, G. R. & Steiner, T. (1999). The Weak Hydro­gen Bond in Structural Chemistry and Biology, pp. 246-253. New York: Oxford University Press.]).

However, a seventh sulf­imide ligand is included in the structure, this time acting as an outer- rather than an inner-sphere ligand. The ligand is not coordinated to the metal centre but interacts with the [Co(Ph2SNH)6]I2 unit via an N—H⋯I hydrogen-bonding interaction, having an N⋯I distance of 3.987 (2) Å and a more linear N—H⋯I angle of 172 (2)°. Therefore, one of the iodide anions accepts four hydrogen bonds. Two aceto­nitrile mol­ecules of crystallization are also included in the crystal structure.

The structure appears rather asymmetric, with the second iodide anion only accepting three hydrogen bonds. It was expected that the system might, therefore, take up further units of Ph2SNH. The addition of excess sulf­imide, however, does not result in the incorporation of more of the free ligand. Compound (I[link]) appears to be the only product, even in the presence of a large excess of sulf­imide. The system also incorporates a number of weaker C—H⋯I hydrogen bonds using aromatic groups that surround the iodide anions. C⋯I contact distances lie in the range 4.072 (3)–4.423 (2) Å. A mean distance of 4.00 (2) Å has been quoted for the C⋯I contact distance for sp2-hybridized CH groups (Desiraju & Steiner, 1999[Desiraju, G. R. & Steiner, T. (1999). The Weak Hydro­gen Bond in Structural Chemistry and Biology, pp. 246-253. New York: Oxford University Press.]).

The `capping' of the NH groups within the three-up/three-down arrangement through N—H⋯I hydrogen bonding in (I[link]) clearly limits the extent of strong hydrogen bonding between complexes. N—H⋯I and C—H⋯I hydrogen bonds combine to create one-dimensional stacks of alternating cations and anions, propagating along the [223] direction. C—H⋯I interactions also link adjacent stacks together.

Interestingly, we have no evidence for the formation of simple [Co(Ph2SNH)6]I2, even when exactly six molar equi­valents (or slightly less) of sulf­imide are used. It is not clear why the observed structure should be such a favourable arrangement, and this result serves to highlight the unpredictability and structural diversity of complexes of Ph2SNH.

In the light of the fact that previous results indicate that the sulf­imide ligands can readily adjust the relative orientations of the NH groups in order to facilitate the maximum degree of interaction with anions (e.g. multiple acceptors such as BF4−, etc.), the question of the effect of introducing a third halide into the basic [ML6]n+ unit becomes germane.

Attempts to prepare [Co(Ph2SNH)6]Cl3 have proved unsuccessful; however, direct reaction of FeCl3 with six equi­valents of the ligand does provide a route to [Fe(Ph2SNH)6]Cl3, (II[link]), the first iron–sulf­imide complex. Unlike [Co(Ph2SNH)6]Cl2, which, though it has a low solubility in MeCN, may be recrystallized from the hot solvent, this product does not even show appreciable solubility upon heating. To circumvent this recrystallization problem, the reaction was performed without stirring after the initial mixing of reagents. This approach promoted the growth of small but usable crystals of (II[link]). The product crystallizes in a cubic space group with one-sixth of an FeIII centre on a site of [\overline 3] symmetry, one sulf­imide ligand and a total of one-half of a chloride anion in the asymmetric unit (Fig. 3[link]). Atom Cl1 lies on a site of threefold symmetry and has an occupancy of [1\over3], while atom Cl2 lies on a site of [\overline 3] symmetry and has an occupancy of [1\over6]. The angle at the metal centre is distorted from 90 to 86.21 (9)° (Table 3[link]). The complete structure contains three chloride anions, one of which is inequivalent to the other two. The arrangement of the sulf­imide ligands is identical to that in the structure of [Co(Ph2SNH)6]Cl2, with two Cl atoms, Cl1 and a symmetry-equivalent, placed above and below the metal centre, each accepting three hydrogen bonds (Fig. 4[link] and Table 4[link]). The third Cl atom, Cl2, is isolated in the structure and is not involved in any strong hydrogen-bonding interactions. Atom Cl2 is instead surrounded by phenyl groups of the Ph2SNH ligands and is involved in six symmetry-equivalent C—H⋯Cl hydrogen bonds, having a C⋯Cl distance of 3.607 (3) Å (C—H = 0.95 Å, H⋯Cl = 2.86 Å and C—H⋯Cl = 136°). In the light of the previously observed tendency of the sulf­imide ligands to maximize the hydrogen bonding in the system, this is a surprising observation, especially as the chloride anion is a strong acceptor. This result clearly indicates that the hydrogen-bonding arrangement within the [M(Ph2SNH)6]Cl2 unit is extremely stable.

In the course of our investigations of metal–sulf­imide complexes, we have observed two quite different types of reaction with platinum centres. When reacted with (PPh4)2[PtCl4] in CH2Cl2, a simple substitution to give [Pt(Ph2SNH)4]Cl2 takes place (Kelly et al., 2000[Kelly, P. F., Macklin, A. C., Slawin, A. M. Z. & Waring, K. W. (2000). Polyhedron, 19, 2077-2081.]); in this product, the NH groups of the ligands are seen to orientate themselves in such a way as to maximize the hydrogen bonding to the anions. In reactions involving starting materials bearing nitrile ligands, the metal actually mediates addition reactions of the sulf­imide to the nitriles; this phenomenon has been observed for PtII (Kelly & Slawin, 1999[Kelly, P. F. & Slawin, A. M. Z. (1999). Chem. Commun. pp. 1081-1082.]) and, most effectively, for PtIV starting materials (Makarycheva-Mikhailova et al., 2003[Makarycheva-Mikhailova, A. V., Bokach, N. A., Kukushkin, V. Yu., Kelly, P. F., Gilby, L. M., Kuznetsov, M. L., Holmes, K. E., Haukka, M., Parr, J., Stonehouse, J. M., Elsegood, M. R. J. & Pombeiro, A. J. L. (2003). Inorg. Chem. 42, 301-311.]).

We present here the results of an investigation into the reaction of [Pt(Ph2SNH)4]Cl2 with iodine. This reaction was undertaken for two reasons: firstly, it would ascertain whether or not a stable PtIV–sulf­imide complex (as opposed to a sulf­imide/nitrile hybrid) could be isolated. Note that some previous examples of iodo–PtIV species containing S,N-donor ligands have proven to be unstable; for example, the PtII species Pt(S2N2H)I(PMe2Ph) is the only isolable product from the reaction of Pt(S2N2H)(PMe2Ph)2 with iodine (Jones et al., 1988[Jones, R., Kelly, P. F., Williams, D. J. & Woollins, J. D. (1988). J. Chem. Soc. Dalton Trans. pp. 1569-1576.]). In addition, the aim was to observe the effect that introduction of the iodo ligands would have on the hydrogen-bonding arrangements of the sulf­imide ligands.

Reaction of [Pt(Ph2SNH)4]Cl2 with iodine in CH2Cl2 takes place rapidly, and the product [Pt(Ph2SNH)4I2]Cl2, (III[link]), appears stable both in solution and in the solid state. A structure determination confirms that oxidation to PtIV has taken place, giving an elongated octahedral coordination with the PtIV ion situated on an inversion centre (Fig. 5[link] and Table 5[link]); the asymmetric unit contains one-half of a formula unit and the two I atoms adopt mutually trans positions. It is likely that this conformation is favoured because it allows the NH units of the sulf­imide to become involved in significant hydrogen-bonding interactions with the chloride counter-ions (Table 6[link]). As in the PtII analogue (and indeed other homoleptic complexes of Ph2SNH), the ligands arrange themselves in such a way that the two pairs of cis S atoms extend from opposite sides of the MN4 plane; as a result, each pair of NH groups can co-operate in hydrogen bonding to a different chloride ion. The average H⋯Cl distance is thus 2.46 Å (somewhat longer than in the PtII analogue, where the H⋯Cl distance is 2.25 Å; Kelly et al., 2000[Kelly, P. F., Macklin, A. C., Slawin, A. M. Z. & Waring, K. W. (2000). Polyhedron, 19, 2077-2081.]), with average N—H⋯Cl angles of 166°. Although strong hydrogen bonds are limited to within the [Pt(Ph2SNH)4I2]Cl2 unit, weaker C—H⋯Cl hydrogen bonds (Table 6[link]) are apparent between aryl CH groups and atom Cl3.

The structure of (III[link]) contains two mol­ecules of di­chloro­methane solvent per cationic complex; thus, the asymmetric unit contains one mol­ecule of di­chloro­methane, which was found to be disordered. The solvent mol­ecule was modelled over two sets of positions with a refined major occupancy of 80.6 (11)%. The metal-bound iodide has a close contact with one of the Cl atoms of the solvent mol­ecule [I1⋯Cl2(x, y + 1, z) = 3.815 (4) Å].

Comparison of the metal–nitrogen bond lengths in the three title complexes (Tables 1[link], 3[link] and 5[link]) shows that the Co—N bond lengths [mean 2.143 (6) Å] are significantly longer than the Pt—N [2.042 (3) Å] and Fe—N [2.078 (2) Å] bond lengths.

From the investigations presented here, it is clear that the three-up/three-down conformation of the [M(Ph2SNH)6]n+ ion is extremely stable. Attempts to alter this conformation through the introduction of less electronegative anions, or even extra anions, still leads to the same conformation being observed in (I[link]) and (II[link]), while the introduction of iodide ligands to give an elongated octahedron in (III[link]) still allows two sulf­imide NH groups on each side of the complex to hydrogen bond to the chloride anions. In all three compounds, there are weaker hydrogen-bonding interactions between relatively acidic CH groups and the halide anions, resulting from the halide anions being positioned in the gaps between close-packed Ph2SNH ligands.

[Figure 1]
Figure 1
A view of the cationic component of (I[link]), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. Alternate Ph2SNH ligands are shown using open bonds.
[Figure 2]
Figure 2
A view of the hydrogen bonding present in (I[link]). H atoms (except for those bound to N atoms), C atoms (apart from the Cα atoms of the phenyl rings) and two solvent mol­ecules have been omitted for clarity. N—S and S—C bonds are shown as open bonds in the metal-coordinated ligands. Hydro­gen bonding is indicated by dashed lines.
[Figure 3]
Figure 3
A view of the cationic component of (II[link]), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. Alternate Ph2SNH ligands are shown using open bonds. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) z − [1\over2], [1\over2] − x, 1 − y; (iii) [1\over2] − y, 1 − z, [1\over2] + x; (iv) [1\over2] − z, [1\over2] + x, y; (v) y − [1\over2], z, [1\over2] − x.]
[Figure 4]
Figure 4
A view of the hydrogen bonding present in (II[link]). H atoms (except for those bound to N atoms) and C atoms (apart from the Cα atoms of the phenyl rings) have been omitted for clarity. N—S and S—C bonds are shown as open bonds. Hydro­gen bonding is indicated by dashed lines. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) z − [1\over2], [1\over2] − x, 1 − y; (iii) [1\over2] − y, 1 − z, [1\over2] + x; (iv) [1\over2] − z, [1\over2] + x, y; (v) y − [1\over2], z, [1\over2] − x.]
[Figure 5]
Figure 5
A view of (III[link]), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, H atoms are represented by circles of arbitrary radii and hydrogen bonding is indicated by dashed lines. Solvent mol­ecules and H atoms, except for those bound to N atoms, have been omitted for clarity. [Symmetry code: (i) −x, 1 − y, −z.]

Experimental

For the preparation of compound (I[link]), CoI2 (51 mg, 0.16 mmol) was dissolved in MeCN (5 ml), and a solution of Ph2SNH·H2O (250 mg, 1.14 mmol) in MeCN (5 ml) was added with stirring to give an intense blue-coloured solution containing a pink precipitate. This solid was redissolved by heating to give a clear solution from which pink crystals of (I[link]) were grown by slow cooling. For the preparation of compound (II[link]), FeCl3·6H2O (44 mg, 0.16 mmol) was dissolved in MeCN (10 ml) and a solution of Ph2SNH·H2O (250 mg, 1.14 mmol) in MeCN (10 ml) was added. The solution was stirred only to mix the two solutions and was then left to stand. The product has very limited solubility in MeCN, and precipitation of an orange solid was observed, but, on standing, small yellow crystals of (II[link]) formed overnight. For the preparation of compound (III[link]), [PtI2(Ph2SNH)4]Cl2 was first pre­pared by the equimolar reaction of [Pt(Ph2SNH)4]Cl2 with iodine in CH2Cl2, followed by removal of the solvent in vacuo. Crystals of (III[link]) were grown by slow diffusion of ether into a solution of the product in CH2Cl2.

Compound (I)[link]

Crystal data

  • [Co(C12H11NS)6]I2·C12H11NS·2C2H3N

  • Mr = 1803.86

  • Triclinic, [P\overline 1]

  • a = 13.0776 (6) Å

  • b = 15.1667 (7) Å

  • c = 22.4675 (11) Å

  • α = 73.557 (2)°

  • β = 87.490 (2)°

  • γ = 78.807 (2)°

  • V = 4192.5 (3) Å3

  • Z = 2

  • Dx = 1.429 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 49 288 reflections

  • θ = 2.3–28.5°

  • μ = 1.17 mm−1

  • T = 150 (2) K

  • Block, pink

  • 0.18 × 0.11 × 0.06 mm
Data collection

  • Bruker SMART 1000 CCD diffractometer

  • ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.818, Tmax = 0.933

  • 49 288 measured reflections

  • 19 601 independent reflections

  • 12 795 reflections with I > 2σ(I)

  • Rint = 0.027

  • θmax = 29.0°

  • h = −17 → 17

  • k = −20 → 19

  • l = −30 → 30
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.064

  • S = 0.89

  • 19 601 reflections

  • 987 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0244P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.003

  • Δρmax = 0.64 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Selected geometric parameters (Å, °) for (I)[link]

Co1—N1 2.1486 (19)
Co1—N2 2.1679 (19)
Co1—N3 2.1187 (19)
Co1—N4 2.1400 (19)
Co1—N5 2.1454 (19)
Co1—N6 2.1367 (19)
N1—Co1—N2 84.82 (7) 
N1—Co1—N3 85.63 (7)
N1—Co1—N4 95.19 (7)
N1—Co1—N5 94.28 (7)
N1—Co1—N6 179.23 (8)
N2—Co1—N3 85.11 (7)
N2—Co1—N4 93.75 (7)
N2—Co1—N5 178.44 (8)
N2—Co1—N6 95.46 (7)
N3—Co1—N4 178.54 (8)
N3—Co1—N5 96.10 (7)
N3—Co1—N6 93.68 (7)
N4—Co1—N5 85.06 (7)
N4—Co1—N6 85.50 (7)
N5—Co1—N6 85.45 (7)

Table 2
Hydrogen-bonding geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯I1 0.80 (2) 3.07 (2) 3.8337 (19) 159 (2)
N2—H2A⋯I1 0.78 (2) 3.09 (2) 3.8207 (19) 157 (2)
N3—H3A⋯I1 0.81 (2) 2.95 (2) 3.7302 (19) 163 (2)
N4—H4A⋯I2 0.80 (2) 2.97 (2) 3.7413 (19) 165 (2)
N5—H5A⋯I2 0.81 (2) 3.09 (2) 3.8461 (19) 156 (2)
N6—H6A⋯I2 0.79 (2) 3.09 (2) 3.831 (2) 157 (2)
N7—H7A⋯I1 0.84 (2) 3.16 (2) 3.987 (2) 172 (2)

Compound (II)[link]

Crystal data

  • [Fe(C12H11NS)6]Cl3

  • Mr = 1369.93

  • Cubic, [Pa\overline 3]

  • a = 18.8566 (4) Å

  • V = 6704.9 (2) Å3

  • Z = 4

  • Dx = 1.357 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 28 769 reflections

  • θ = 2.9–27.5°

  • μ = 0.58 mm−1

  • T = 120 (2) K

  • Block, yellow

  • 0.10 × 0.08 × 0.05 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.942, Tmax = 0.970

  • 64 482 measured reflections

  • 2572 independent reflections

  • 1840 reflections with I > 2σ(I)

  • Rint = 0.133

  • θmax = 27.5°

  • h = −24 → 24

  • k = −24 → 21

  • l = −24 → 23
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.113

  • S = 1.04

  • 2572 reflections

  • 138 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.052P)2 + 4.568P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.66 e Å−3

  • Δρmin = −0.89 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.0011 (2)

Table 3
Selected geometric parameters (Å, °) for (II)[link]

Fe1—N1 2.078 (2)
N1—Fe1—N1ii 86.21 (9)
Symmetry code: (ii) [z-{\script{1\over 2}},{\script{1\over 2}}-x,1-y].

Table 4
Hydrogen-bonding geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯Cl1 0.82 (3) 2.50 (3) 3.272 (2) 157 (3)

Compound (III)[link]

Crystal data

  • [PtI2(C12H11NS)4]Cl2·2CH2Cl2

  • Mr = 1494.75

  • Monoclinic, P21/n

  • a = 13.7287 (5) Å

  • b = 10.8620 (4) Å

  • c = 18.3936 (6) Å

  • β = 93.864 (2)°

  • V = 2736.64 (17) Å3

  • Z = 2

  • Dx = 1.814 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 15 561 reflections

  • θ = 2.2–28.8°

  • μ = 4.18 mm−1

  • T = 150 (2) K

  • Block, red

  • 0.28 × 0.17 × 0.16 mm
Data collection

  • Bruker SMART 1000 CCD diffractometer

  • ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.357, Tmax = 0.511

  • 23 077 measured reflections

  • 6442 independent reflections

  • 5859 reflections with I > 2σ(I)

  • Rint = 0.016

  • θmax = 28.8°

  • h = −18 → 18

  • k = −13 → 14

  • l = −24 → 24
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.143

  • S = 1.07

  • 6442 reflections

  • 338 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.078P)2 + 27.27P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 3.60 e Å−3

  • Δρmin = −3.70 e Å−3

Table 5
Selected geometric parameters (Å, °) for (III)[link]

Pt1—N1 2.046 (5)
Pt1—N2 2.038 (5)
Pt1—I1 2.6470 (5)
N1—Pt1—N2 87.8 (2)
N1—Pt1—I1 87.39 (15)
N2—Pt1—I1 87.89 (16)

Table 6
Hydrogen-bonding geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯Cl3 0.77 (3) 2.46 (4) 3.210 (5) 165 (8)
N2—H2A⋯Cl3 0.78 (3) 2.47 (7) 3.242 (5) 168 (8)
C3—H3⋯Cl3ii 0.95 2.93 3.567 (7) 126
C4—H4⋯Cl3ii 0.95 2.99 3.601 (9) 123
C10—H10⋯Cl3iii 0.95 2.76 3.626 (8) 153
C14—H14⋯Cl3 0.95 2.84 3.716 (8) 154
C21—H21⋯Cl3iv 0.95 2.82 3.546 (7) 134
Symmetry codes: (ii) [-{\script{1\over 2}}-x,{\script{1\over 2}}+y,{\script{1\over 2}}-z]; (iii) [-{\script{1\over 2}}-x,y-{\script{1\over 2}},{\script{1\over 2}}-z]; (iv) [{\script{1\over 2}}-x,y-{\script{1\over 2}},] [{\script{1\over 2}}-z].

In all three structures, C-bound H atoms were placed geometrically [C—H = 0.95 (aromatic), 0.99 (CH2) and 0.98 Å (methyl)] and refined using a riding model. H atoms of NH groups were located in a difference Fourier map and their coordinates were refined freely in (I[link]) and (II[link]), and using restraints on the N—H bond length [target value 0.80 (3) Å in (III[link])]. Uiso(H) values were set at 1.2Ueq(C) for aryl H atoms, 1.2Ueq(C) for CH2 H atoms, and 1.5Ueq(N,C) for NH and methyl H atoms. The CH2Cl2 mol­ecule of crystallization in (III[link]) was found to be disordered and was modelled over two sets of positions using restraints on the anisotropic displacement parameters of the C and Cl atoms. The major and minor disorder components had refined occupancies of 80.6 (11) and 19.4 (11)%, respectively.

For compounds (I) and (III), data collection: SMART (Bruker, 2001[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT. For compound (II), data collection: COLLECT (Hooft, 1998[Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT. For all three compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2000[Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks global, I, II, III. DOI: 10.1107/S0108270104029051/bm1594sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104029051/bm1594Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270104029051/bm1594IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270104029051/bm1594IIIsup4.hkl


Comment top

Diphenylsulfimide, Ph2SNH, has proven to be an extremely useful ligand for later transition metal centres in so far as the complexes produced invariably exhibit strong hydrogen bonding between the sulfimide NH groups and the counter-ions. As a result, the complexes often show unusual structural properties; by way of example, the ostensibly simple reaction of the ligand with Cu(BF4)2 results in a multitude of products, including three polymorphs of [Cu(Ph2SNH)4][BF4]2, the inter-allogon [Cu(Ph2SNH)4]2[BF4]4 and the mixed coordination system [Cu(Ph2SNH)4][Cu(Ph2SNH)5][BF4]4 (Holmes et al., 2002).

One of the first examples of metal–sulfimide complexes reported was [Co(Ph2SNH)6]Cl2, in which the ligands are arranged around the metal centre in such a way as to maximize the hydrogen-bonding interactions between the sulfimide NH groups and the chloride couter-ions (Kelly et al., 1998). Hence, each chloride acts as a trifurcated acceptor with three NH bonds pointing upwards and three down. The isostructural nickel(II) complex has since been reported by Sellmann et al. (2001).

We describe here investigations into the effect of the modification of the anion on the hydrogen-bonding interactions between Co, Fe and Pt sulfimide complexes and uncoordinated anions.

In the light of the successful study of [Co(Ph2SNH)6]Cl2, the modification of the anion from chloride to the larger, less electronegative, iodide was attempted. The reaction of Ph2SNH with CoI2 in acetonitrile results in pink crystals of [Co(Ph2SNH)6]I2·Ph2SNH·2MeCN, (I), which crystallize in a triclinic space group, indicating that the symmetry of the chloride complex has been broken. The crystal structure of (I) is centrosymmetric, and the asymmetric unit contains a complete formula unit. The CoII centre is octahedrally coordinated by six sulfimide ligands, with trans angles lying between 178.44 (8) and 179.23 (8)° (Table 1). The ligands are arranged in the same way as in the chloride complex, with three sulfimide NH groups on either side of the metal. Each halide ion therefore acts as a trifurcated acceptor to the [Co(Ph2SNH)6]2+ cation, with N···I distances in the range 3.7302 (19)–3.8461 (19) Å and N—H···I angles in the range 157 (2)–165 (2)° (Table 2?). A mean distance of 3.66 (1) Å has been quoted for N···I contact distances for sp2-hybridized NH groups (Desiraju & Steiner, 1999).

However, a seventh sulfimide ligand is included in the structure, this time acting as an outer- rather than an inner-sphere ligand. The ligand is not coordinated to the metal centre but interacts with the [Co(Ph2SNH)6]I2 unit via an N—H···I hydrogen-bonding interaction, having an N···I distance of 3.987 (2) Å and a more linear N—H···I angle of 172 (2)°. Therefore, one of the iodide anions accepts four hydrogen bonds. Two acetonitrile molecules of crystallization are also included in the crystal structure.

The structure appears rather asymmetric, with the second iodide anion only accepting three hydrogen bonds. It was expected that the system might, therefore, take up further units of Ph2SNH. The addition of excess sulfimide, however, does not result in the incorporation of more of the free ligand. The title compound appears to be the only product, even in the presence of a large excess of sulfimide. The system also incorporates a number of weaker C—H···I hydrogen bonds using aromatic groups that surround the iodide anions. C···I contact distances lie in the range 4.072 (3)–4.423 (2) Å. A mean distance of 4.00 (2) Å has been quoted for the C···I contact distance for sp2-hybridized CH groups (Desiraju & Steiner, 1999).

The `capping' of the NH groups within the three-up three-down arrangement through N—H···I hydrogen bonding in (I) clearly limits the extent of strong hydrogen bonding between complexes. N—H···I and C—H···I hydrogen bonds combine to create one-dimensional stacks of alternating cations and anions, propagating along the [223] direction. C—H···I interactions also link adjacent stacks together.

Interestingly, we have no evidence for the formation of simple [Co(Ph2SNH)6]I2, even when exactly six molar equivalents (or slightly less) of sulfimide are used. It is not clear why the observed structure should be such a favourable arrangement, and this result serves to highlight the unpredictability and structural diversity of complexes of Ph2SNH.

In the light of the fact that previous results indicate that the sulfimide ligands can readily adjust the relative orientations of the NH groups in order to facilitate the maximum degree of interaction with anions (e.g. multiple acceptors such as [BF4]− etc) the question of the effect of introducing a third halide into the basic [ML6]2+ unit becomes germane.

Attempts to prepare [Co(Ph2SNH)6]Cl3 have proved unsuccessful; however, direct reaction of FeCl3 with six equivalents of the ligand does provide a route to [Fe(Ph2SNH)6]Cl3, the first iron sulfimide complex. Unlike [Co(Ph2SNH)6]Cl2, which, though it has a low solubility in MeCN, may be recrystallized from the hot solvent, this product does not even show appreciable solubility upon heating. To circumvent this recrystallization problem, the reaction was performed without stirring after the initial mixing of reagents. This approach promoted the growth of small but usable crystals of the product, (II). The product crystallizes in a cubic space group with one sixth of an FeIII centre on a position having 3 symmetry, one sulfimide ligand and a total of one-half of a chloride anion in the unit cell (Fig. 2). Atom Cl1 lies on a position having threefold symmetry and has an occupancy of 1/3, while atom Cl2 lies on a position having 3 symmetry and has an occupancy of 1/6. The angle at the metal centre is distorted from 90 to 86.21 (9)° (Table 3). The complete structure contains three chloride anions, one of which is inequivalent to the other two. The arrangement of the sulfimide ligands is identical to that seen in the structure of [Co(Ph2SNH)6]Cl2 with two chloride ions, Cl1− and a symmetry-equivalent, placed above and below the metal centre, each accepting three hydrogen bonds (Table 4). The third chloride ion, Cl2−, is isolated in the structure and is not involved in any strong hydrogen-bonding interactions. Atom Cl2 is instead surrounded by Ph groups of the Ph2SNH ligands and is involved in six symmetry-equivalent C—H···Cl hydrogen bonds, having a C···Cl distance of 3.607 (3) Å (C—H = 0.95 Å, H···Cl = 2.86 Å and C—H···Cl = 136°). In the light of the previously observed tendency of the sulfimide ligands to maximize the hydrogen bonding in the system this is a surprising observation, especially as the chloride anion is a strong acceptor. This result clearly indicates that the hydrogen-bonding arrangement within the [M(Ph2SNH)6]Cl2 unit is extremely stable.

In the course of our investigations of metal–sulfimide complexes, we have observed two quite different types of reaction with platinum centres. When reacted with [PPh4]2[PtCl4] in CH2Cl2 a simple substitution to give [Pt(Ph2SNH)4]Cl2 takes place (Kelly et al., 2000); in this product the NH groups of the ligands are seen to orientate themselves in such a way as to maximize the hydrogen-bonding to the anions. In reactions involving starting materials bearing nitrile ligands, the metal actually mediates addition reactions of the sulfimide to the nitriles – this phenomenon has been observed for PtII (Kelly & Slawin, 1999) and, most effectively, for PtIV starting materials (Makarycheva-Mikhailova et al., 2003).

We present here the results of an investigation into the reaction of [Pt(Ph2SNH)4]Cl2 with iodine. This reaction was undertaken for two reasons; firstly it would ascertain whether or not a stable PtIV sulfimide complex (as opposed to a sulfimide/nitrile hybrid) could be isolated. Note that some previous examples of iodo–PtIV species containing SN ligands have proven to be unstable; for example, the PtII species Pt(S2N2H)I(PMe2Ph) is the only isolable product from the reaction of Pt(S2N2H)(PMe2Ph)2 with iodine (Jones et al., 1988). In addition, the aim was to observe the effect that introduction of the iodo ligands would have on the hydrogen-bonding arrangements of the sulfimide ligands.

Reaction of [Pt(Ph2SNH)4]Cl2 with iodine in CH2Cl2 takes place rapidly, and the product [Pt(Ph2SNH)4I2]Cl2, (III), appears stable both in solution and in the solid state. A structure determination confirms that oxidation to PtIV has taken place, giving an elongated octahedral coordination with the PtIV ion situated on an inversion centre (Fig. 3 and Table 5); the asymmetric unit contains one-half of a formula unit and the two I atoms adopt mutually trans positions. It is likely that this conformation is favoured because it allows the NH units of the sulfimide to become involved in significant hydrogen-bonding interactions with the chloride counter-ions (Table 6). As in the PtII analogue (and indeed other homoleptic complexes of Ph2SNH), the ligands arrange themselves in such a way that the two pairs of cis S atoms extend from opposite sides of the MN4 plane; as a result, each pair of NH groups can cooperate in hydrogen-bonding to a different chloride ion. The average H···Cl distance is thus 2.46 Å [somewhat longer than in the PtII analogue, where the H···Cl distance was measured as 2.25 Å (Kelly et al., 2000)], with average N—H···Cl angles of 166°. Although strong hydrogen bonds are limited to within the [Pt(Ph2SNH)4I2]Cl2 unit, weaker C—H···Cl hydrogen bonds (Table 6) are apparent between aryl CH groups and atom Cl3.

The structure of (III) contains two molecules of dichloromethane solvent per cationic complex; thus the asymmetric unit contains one molecule of dichloromethane, which was found to be disordered. The solvent molecule was modelled over two sets of positions with a refined major occupancy of 80.6 (11)%. The metal-bound iodide has a close contact with one of the Cl atoms of the solvent molecule [I1···Cl2i = 3.815 (4) Å; symmetry code: (i) x, y + 1, z].

Comparison of the metal–N bond lengths (Tables 1, 3 and 5) shows that the Co—N bond lengths (average 2.143 Å) are significantly longer than the Pt—N (2.042 Å) and Fe—N (2.078 Å) bond lengths.

From the investigations presented here, it is clear that the three-up/three-down conformation of the [M(Ph2SNH)6]n+ ion is extremely stable. Attempts to alter this conformation through the introduction of less electronegative anions, or even extra anions, still leads to the same conformation being observed in (I) and (II), respectively, while the introduction of iodide ligands to give an elongated octahedron in (III) still allows two sulfimide NH groups on each side of the complex to hydrogen bond to the chloride anions. In all three compounds (I)–(III), there are weaker hydrogen-bonding interactions between relatively acidic CH groups and the halide anions, resulting from the halide anions being positioned in the gaps between close-packed Ph2SNH ligands.

Experimental top

Compound (I) was prepared as follows: CoI2 (51 mg, 0.16 mmol) was dissolved in MeCN (5 ml), and Ph2SNH·H2O (250 mg, 1.14 mmol) in MeCN (5 ml) was added with stirring to give an intense blue-coloured solution containing a pink precipitate. This solid was redissolved by heating to give a clear solution from which pink crystals of (I) were grown by slow cooling. Compound (II) was prepared as follows: FeCl3·6H2O (44 mg, 0.16 mmol) was dissolved in MeCN (10 ml), and Ph2SNH·H2O (250 mg, 0.114 mmol) in MeCN (10 ml) was added. The solution was stirred only to mix the two solutions and was then left to stand. The product has very limited solubility in MeCN, and precipitation of an orange solid was observed, but, on standing, microscopic crystals of (II) formed overnight. Compound (III) was prepared as follows: [Pt(Ph2SNH)4I2]Cl2 was prepared by the equimolar reaction of [Pt(Ph2SNH)4]Cl2 with iodine in CH2Cl2, followed by removal of the solvent in vacuo. Crystals of (III) were grown by slow diffusion of ether into a solution of the product in CH2Cl2.

Refinement top

In all three structures, C-bound H atoms were placed geometrically [C—H = 0.95 (aromatic), 0.99 (CH2) and 0.98 Å (methyl)] and refined using a riding model. NH atoms were located in the difference Fourier map and their coordinates were refined freely in (I) and (II), and [## AUTHOR: check s.u. for target value for N—H below:] using restraints on the N—H bond length [target value 0.80 (1) Å] in (III). Uiso(H) values were set at 1.2Ueq(C) for aryl H and 1.5Ueq(N,C) for NH and methyl H atoms, respectively. The CH2Cl2 molecule of crystallization in (III) was found to be disordered, and it was modelled over two sets of positions using restraints on the anisotropic displacement parameters of the C and Cl atoms. The major amd minor disorder components had refined occupancies of 80.6 (11) and 19.4 (11)%, respectively.

Computing details top

Data collection: SMART (Bruker, 2001) for (I), (III); COLLECT, (Hooft, 1998) for (II). Cell refinement: SAINT (Bruker, 2001) for (I), (III); DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (II). Data reduction: SAINT for (I), (III); DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (II). For all compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. A view of the cationic component of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. Alternate Ph2SNH ligands are shown using open bonds.
[Figure 2] Fig. 2. A view of the hydrogen bonding present in (I). H atoms, except those bound to N atom, C atoms, except the Cα atoms of the Ph rings, and two solvent molecules have been omitted for clarity. N—S and S—C bonds are shown as open bonds in the metal-coordinated ligands. Hydrogen bonding is shown by dashed lines.
[Figure 3] Fig. 3. A view of the cationic component of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms have been omitted for clarity. Alternate Ph2SNH ligands are shown using open bonds. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) z − 0.5, 0.5 − x, 1 − y; (iii) 0.5 − y, 1 − z, 0.5 + x; (iv) 0.5 − z, 0.5 + x, y; (v) y − 0.5, z, 0.5 − x.]
[Figure 4] Fig. 4. A view of the hydrogen bonding present in (II). H atoms, except those bound to N atoms, and C atoms, except the Cα atoms of the Ph rings, have been omitted for clarity. N—S and S—C bonds are shown as open bonds. Hydrogen bonding is shown by dashed lines. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) z − 0.5, 0.5 − x, 1 − y; (iii) 0.5 − y, 1 − z, 0.5 + x; (iv) 0.5 − z, 0.5 + x, y; (v) y − 0.5, z, 0.5 − x.]
[Figure 5] Fig. 5. A view of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, H atoms are represented by circles of arbitrary radii and hydrogen bonding is shown by dashed lines. Solvent molecules and H atoms, except those bound to N atoms, have been omitted for clarity. [Symmetry code: (i) −x, 1 − y, −z.]
(I) Hexakis(S,S-diphenylsulfimide)cobalt(II) diiodide diphenylsulfimide acetonitrile disolvate top
Crystal data top
[Co(C12H11NS)6]I2·C12H11NS·2C2H3NZ = 2
Mr = 1803.86F(000) = 1838
Triclinic, P1Dx = 1.429 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 13.0776 (6) ÅCell parameters from 49288 reflections
b = 15.1667 (7) Åθ = 2.3–28.5°
c = 22.4675 (11) ŵ = 1.17 mm−1
α = 73.557 (2)°T = 150 K
β = 87.490 (2)°Block, pink
γ = 78.807 (2)°0.18 × 0.11 × 0.06 mm
V = 4192.5 (3) Å3
Data collection top
Bruker SMART 1000 CCD
diffractometer		19601 independent reflections
Radiation source: sealed tube12795 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω rotation with narrow frames scansθmax = 29.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −17→17
Tmin = 0.818, Tmax = 0.933k = −20→19
49288 measured reflectionsl = −30→30
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)] = 0.030Hydrogen site location: placed geometrically except NH which were refined with restraints
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 0.89 w = 1/[σ2(Fo2) + (0.0244P)2]
where P = (Fo2 + 2Fc2)/3
19601 reflections(Δ/σ)max = 0.003
987 parametersΔρmax = 0.64 e Å−3
0 restraintsΔρmin = −0.34 e Å−3
Crystal data top
[Co(C12H11NS)6]I2·C12H11NS·2C2H3Nγ = 78.807 (2)°
Mr = 1803.86V = 4192.5 (3) Å3
Triclinic, P1Z = 2
a = 13.0776 (6) ÅMo Kα radiation
b = 15.1667 (7) ŵ = 1.17 mm−1
c = 22.4675 (11) ÅT = 150 K
α = 73.557 (2)°0.18 × 0.11 × 0.06 mm
β = 87.490 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		19601 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		12795 reflections with I > 2σ(I)
Tmin = 0.818, Tmax = 0.933Rint = 0.027
49288 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 0.89Δρmax = 0.64 e Å−3
19601 reflectionsΔρmin = −0.34 e Å−3
987 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I11.079886 (12)0.551999 (11)0.269873 (8)0.02930 (5)
I20.423016 (13)0.961543 (11)0.233693 (8)0.03237 (5)
Co10.75069 (2)0.75509 (2)0.251517 (15)0.01667 (6)
N10.78181 (15)0.60466 (13)0.27969 (9)0.0226 (5)
H1A0.8421 (18)0.5796 (16)0.2843 (11)0.027*
S10.70815 (4)0.53517 (4)0.27689 (3)0.02112 (13)
C10.72663 (19)0.43831 (15)0.34606 (11)0.0237 (5)
C20.6392 (2)0.41314 (17)0.37786 (12)0.0318 (6)
H20.57150.44540.36260.038*
C30.6512 (3)0.34017 (19)0.43241 (13)0.0434 (8)
H30.59160.32130.45420.052*
C40.7494 (3)0.29537 (19)0.45481 (13)0.0493 (9)
H40.75730.24640.49250.059*
C50.8367 (2)0.32085 (19)0.42301 (14)0.0471 (8)
H50.90430.28900.43860.057*
C60.8256 (2)0.39324 (17)0.36818 (12)0.0360 (7)
H60.88530.41150.34620.043*
C70.75808 (18)0.46968 (15)0.22271 (11)0.0235 (5)
C80.7095 (2)0.39883 (17)0.21663 (12)0.0331 (6)
H80.65100.38400.24140.040*
C90.7471 (2)0.35030 (18)0.17429 (13)0.0426 (7)
H90.71390.30220.16960.051*
C100.8318 (2)0.3710 (2)0.13912 (13)0.0497 (8)
H100.85780.33680.11040.060*
C110.8797 (3)0.4420 (2)0.14531 (14)0.0581 (10)
H110.93890.45590.12110.070*
C120.8414 (2)0.49274 (19)0.18670 (12)0.0389 (7)
H120.87260.54280.19010.047*
N20.87840 (15)0.74117 (13)0.31391 (9)0.0229 (5)
H2A0.9263 (18)0.7007 (16)0.3153 (11)0.027*
S20.87493 (5)0.77682 (4)0.37357 (3)0.02192 (13)
C130.99514 (19)0.81387 (16)0.38200 (11)0.0261 (6)
C141.0884 (2)0.77220 (18)0.36223 (12)0.0330 (6)
H141.09160.72060.34570.040*
C151.1780 (2)0.8067 (2)0.36685 (12)0.0421 (7)
H151.24290.77880.35330.051*
C161.1723 (2)0.8815 (2)0.39105 (14)0.0483 (8)
H161.23330.90580.39310.058*
C171.0790 (2)0.9217 (2)0.41236 (15)0.0538 (9)
H171.07680.97130.43070.065*
C180.9883 (2)0.88928 (18)0.40696 (13)0.0428 (7)
H180.92330.91780.41990.051*
C190.88432 (17)0.67963 (16)0.44313 (10)0.0238 (5)
C200.89475 (19)0.69319 (19)0.50118 (12)0.0324 (6)
H200.90300.75240.50470.039*
C210.89293 (19)0.6187 (2)0.55392 (12)0.0373 (7)
H210.90070.62680.59380.045*
C220.87992 (19)0.53324 (19)0.54883 (12)0.0354 (7)
H220.87980.48260.58520.042*
C230.86698 (18)0.52049 (18)0.49131 (12)0.0320 (6)
H230.85650.46170.48820.038*
C240.86931 (17)0.59430 (16)0.43779 (11)0.0260 (6)
H240.86070.58610.39810.031*
N30.86842 (15)0.74313 (13)0.18487 (9)0.0215 (5)
H3A0.9203 (18)0.7038 (16)0.1955 (11)0.026*
S30.88835 (4)0.81500 (4)0.12140 (3)0.01893 (12)
C251.00688 (17)0.85737 (15)0.12659 (11)0.0200 (5)
C261.04848 (18)0.90879 (16)0.07313 (11)0.0270 (6)
H261.02060.91500.03350.032*
C271.13159 (19)0.95100 (17)0.07843 (12)0.0326 (6)
H271.16040.98710.04230.039*
C281.1724 (2)0.94060 (17)0.13626 (12)0.0334 (6)
H281.22890.97000.13970.040*
C291.13133 (19)0.88746 (17)0.18927 (12)0.0325 (6)
H291.16070.87930.22880.039*
C301.04717 (18)0.84607 (16)0.18456 (11)0.0246 (5)
H301.01790.81060.22070.030*
C310.92745 (17)0.75186 (15)0.06516 (10)0.0191 (5)
C321.00546 (19)0.67280 (16)0.07798 (11)0.0273 (6)
H321.04620.65550.11490.033*
C331.0236 (2)0.61903 (17)0.03649 (12)0.0347 (6)
H331.07710.56480.04480.042*
C340.9634 (2)0.64490 (19)−0.01712 (13)0.0397 (7)
H340.97480.6074−0.04510.048*
C350.8875 (2)0.7240 (2)−0.03013 (12)0.0388 (7)
H350.84800.7419−0.06750.047*
C360.86814 (18)0.77841 (17)0.01113 (11)0.0279 (6)
H360.81500.83300.00240.034*
N40.63392 (15)0.76931 (13)0.31970 (9)0.0214 (5)
H4A0.5841 (18)0.8095 (15)0.3082 (11)0.026*
S40.61435 (4)0.69340 (4)0.38111 (3)0.01968 (13)
C370.57007 (17)0.75098 (16)0.43989 (10)0.0212 (5)
C380.49092 (19)0.82937 (16)0.42818 (11)0.0281 (6)
H380.45450.85130.38950.034*
C390.4657 (2)0.87521 (18)0.47369 (12)0.0361 (7)
H390.41190.92920.46620.043*
C400.5186 (2)0.84257 (19)0.52987 (13)0.0365 (7)
H400.50070.87430.56080.044*
C410.5967 (2)0.76493 (19)0.54153 (12)0.0356 (6)
H410.63240.74300.58040.043*
C420.62361 (18)0.71811 (17)0.49608 (11)0.0270 (6)
H420.67790.66450.50360.032*
C430.49848 (17)0.64915 (15)0.37330 (11)0.0204 (5)
C440.45455 (18)0.59657 (16)0.42579 (11)0.0287 (6)
H440.48090.58880.46610.034*
C450.3719 (2)0.55583 (18)0.41821 (12)0.0349 (7)
H450.34120.51990.45360.042*
C460.3336 (2)0.56693 (18)0.35967 (13)0.0343 (7)
H460.27710.53830.35500.041*
C470.3771 (2)0.61942 (18)0.30795 (12)0.0338 (6)
H470.35000.62730.26780.041*
C480.46088 (18)0.66108 (16)0.31431 (11)0.0262 (6)
H480.49150.69690.27880.031*
N50.62227 (15)0.76653 (13)0.19181 (9)0.0222 (5)
H5A0.5744 (18)0.8104 (15)0.1887 (11)0.027*
S50.62370 (5)0.72650 (4)0.13421 (3)0.02145 (13)
C490.61202 (17)0.82117 (16)0.06350 (10)0.0221 (5)
C500.63294 (17)0.90619 (16)0.06546 (11)0.0242 (5)
H500.64650.91630.10400.029*
C510.63394 (17)0.97701 (17)0.01014 (12)0.0286 (6)
H510.64821.03580.01090.034*
C520.61411 (18)0.96171 (18)−0.04584 (12)0.0329 (6)
H520.61451.0101−0.08340.039*
C530.59383 (19)0.87621 (19)−0.04712 (11)0.0331 (6)
H530.58090.8660−0.08570.040*
C540.59214 (18)0.80549 (18)0.00727 (11)0.0292 (6)
H540.57760.74690.00630.035*
C550.50372 (18)0.68799 (16)0.12955 (10)0.0232 (5)
C560.4075 (2)0.74582 (17)0.12971 (12)0.0335 (6)
H560.40360.80900.12980.040*
C570.3171 (2)0.71067 (18)0.12972 (12)0.0381 (7)
H570.25090.74990.12950.046*
C580.3236 (2)0.61823 (19)0.13001 (12)0.0381 (7)
H580.26170.59420.13000.046*
C590.4190 (2)0.56132 (18)0.13036 (12)0.0384 (7)
H590.42290.49800.13070.046*
C600.5102 (2)0.59588 (16)0.13019 (11)0.0301 (6)
H600.57620.55640.13050.036*
N60.72047 (15)0.90467 (13)0.22228 (10)0.0240 (5)
H6A0.6625 (18)0.9324 (16)0.2192 (11)0.029*
S60.79926 (4)0.97018 (4)0.22449 (3)0.02124 (13)
C610.78343 (19)1.06908 (15)0.15628 (11)0.0237 (5)
C620.8732 (2)1.09388 (17)0.12667 (12)0.0314 (6)
H620.94001.06230.14380.038*
C630.8641 (3)1.16541 (19)0.07173 (13)0.0439 (8)
H630.92491.18340.05110.053*
C640.7672 (3)1.21033 (19)0.04711 (13)0.0459 (8)
H640.76161.25900.00920.055*
C650.6777 (2)1.18561 (18)0.07681 (14)0.0464 (8)
H650.61111.21730.05950.056*
C660.6858 (2)1.11420 (17)0.13200 (12)0.0348 (6)
H660.62501.09660.15280.042*
C670.75929 (18)1.02965 (15)0.28354 (11)0.0224 (5)
C680.79395 (18)1.11072 (16)0.28354 (12)0.0285 (6)
H680.83171.14130.24930.034*
C690.77275 (19)1.14633 (17)0.33402 (12)0.0326 (6)
H690.79511.20230.33410.039*
C700.71961 (19)1.10139 (17)0.38400 (12)0.0339 (6)
H700.70741.12530.41900.041*
C710.68375 (19)1.02120 (17)0.38349 (12)0.0324 (6)
H710.64600.99090.41780.039*
C720.70323 (18)0.98539 (16)0.33272 (11)0.0251 (5)
H720.67820.93100.33180.030*
N71.18218 (18)0.43774 (15)0.13372 (10)0.0360 (6)
H7A1.159 (2)0.4561 (18)0.1643 (12)0.043*
S71.24063 (5)0.33282 (4)0.15444 (3)0.03109 (15)
C731.34309 (18)0.31352 (16)0.21095 (11)0.0252 (5)
C741.42446 (19)0.23800 (17)0.21648 (12)0.0335 (6)
H741.42640.19760.19080.040*
C751.50302 (19)0.22194 (18)0.25982 (12)0.0350 (6)
H751.55890.17010.26420.042*
C761.49997 (19)0.28109 (17)0.29647 (12)0.0317 (6)
H761.55380.26990.32620.038*
C771.41919 (19)0.35669 (17)0.29030 (12)0.0314 (6)
H771.41780.39740.31570.038*
C781.34032 (19)0.37348 (16)0.24733 (11)0.0298 (6)
H781.28480.42570.24290.036*
C791.16202 (19)0.25806 (17)0.20528 (12)0.0303 (6)
C801.0892 (2)0.2927 (2)0.24359 (16)0.0558 (9)
H801.07860.35690.24260.067*
C811.0322 (2)0.2337 (2)0.28327 (18)0.0701 (11)
H810.98240.25700.30990.084*
C821.0477 (2)0.1399 (2)0.28424 (17)0.0585 (9)
H821.00880.09890.31160.070*
C831.1193 (2)0.10706 (19)0.24547 (15)0.0498 (8)
H831.12940.04310.24600.060*
C841.1766 (2)0.16518 (18)0.20589 (13)0.0419 (7)
H841.22590.14170.17910.050*
N80.4789 (3)0.3767 (2)0.04876 (15)0.0751 (9)
C850.4065 (3)0.4269 (2)0.02585 (16)0.0556 (9)
C860.3147 (3)0.4907 (3)−0.00287 (16)0.0785 (11)
H86A0.26360.50000.02910.118*
H86B0.28470.4649−0.03190.118*
H86C0.33310.5509−0.02540.118*
N90.7987 (3)0.9160 (2)0.54372 (14)0.0794 (10)
C870.7534 (3)0.9005 (2)0.58872 (15)0.0490 (8)
C880.6967 (2)0.8809 (2)0.64624 (13)0.0542 (9)
H88A0.72660.81830.67240.081*
H88B0.62330.88360.63730.081*
H88C0.70180.92760.66800.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02660 (10)0.03226 (10)0.02702 (10)0.00294 (7)−0.00413 (7)−0.01013 (8)
I20.02974 (10)0.03192 (10)0.03248 (11)0.00410 (8)−0.00554 (8)−0.01005 (8)
Co10.01862 (14)0.01768 (15)0.01479 (14)−0.00603 (11)0.00221 (11)−0.00485 (12)
N10.0209 (11)0.0201 (11)0.0283 (12)−0.0066 (9)0.0023 (10)−0.0075 (9)
S10.0209 (3)0.0193 (3)0.0233 (3)−0.0052 (2)0.0029 (3)−0.0055 (3)
C10.0304 (14)0.0213 (12)0.0233 (14)−0.0109 (11)0.0026 (11)−0.0088 (11)
C20.0398 (16)0.0269 (14)0.0323 (16)−0.0123 (12)0.0099 (13)−0.0117 (12)
C30.066 (2)0.0389 (17)0.0328 (17)−0.0277 (16)0.0177 (16)−0.0117 (14)
C40.096 (3)0.0319 (16)0.0236 (16)−0.0290 (18)−0.0084 (17)−0.0002 (13)
C50.058 (2)0.0341 (16)0.046 (2)−0.0123 (15)−0.0239 (16)0.0012 (14)
C60.0372 (17)0.0273 (14)0.0400 (17)−0.0111 (12)−0.0072 (13)0.0005 (13)
C70.0282 (14)0.0219 (12)0.0205 (13)−0.0052 (10)−0.0022 (11)−0.0056 (10)
C80.0417 (17)0.0310 (14)0.0314 (16)−0.0177 (13)0.0059 (13)−0.0099 (12)
C90.070 (2)0.0285 (15)0.0372 (17)−0.0209 (15)−0.0012 (16)−0.0133 (13)
C100.074 (2)0.0463 (18)0.0426 (19)−0.0195 (17)0.0147 (17)−0.0305 (16)
C110.066 (2)0.074 (2)0.059 (2)−0.0370 (19)0.0349 (18)−0.0473 (19)
C120.0434 (17)0.0468 (17)0.0402 (17)−0.0237 (14)0.0146 (14)−0.0260 (14)
N20.0225 (12)0.0251 (11)0.0211 (11)−0.0022 (9)−0.0030 (9)−0.0075 (9)
S20.0225 (3)0.0226 (3)0.0217 (3)−0.0033 (2)−0.0025 (3)−0.0081 (3)
C130.0278 (14)0.0261 (13)0.0236 (14)−0.0089 (11)−0.0054 (11)−0.0025 (11)
C140.0309 (15)0.0390 (15)0.0312 (15)−0.0111 (12)−0.0021 (12)−0.0100 (13)
C150.0295 (16)0.0575 (19)0.0373 (17)−0.0148 (14)−0.0025 (13)−0.0053 (15)
C160.0448 (19)0.0415 (18)0.057 (2)−0.0233 (15)−0.0172 (16)0.0016 (16)
C170.057 (2)0.0336 (17)0.075 (2)−0.0133 (15)−0.0222 (18)−0.0156 (16)
C180.0399 (17)0.0322 (15)0.061 (2)−0.0087 (13)−0.0093 (15)−0.0175 (15)
C190.0181 (13)0.0323 (14)0.0182 (13)−0.0043 (11)−0.0011 (10)−0.0026 (11)
C200.0265 (14)0.0455 (16)0.0292 (15)−0.0117 (12)−0.0018 (12)−0.0132 (13)
C210.0268 (15)0.0629 (19)0.0211 (14)−0.0106 (14)−0.0023 (11)−0.0080 (14)
C220.0216 (15)0.0471 (17)0.0280 (16)−0.0043 (13)0.0015 (12)0.0028 (13)
C230.0242 (15)0.0322 (15)0.0351 (16)−0.0035 (12)0.0048 (12)−0.0044 (13)
C240.0202 (13)0.0300 (14)0.0250 (14)−0.0020 (11)0.0017 (11)−0.0053 (12)
N30.0192 (11)0.0239 (11)0.0194 (11)−0.0039 (8)0.0029 (9)−0.0033 (9)
S30.0178 (3)0.0213 (3)0.0173 (3)−0.0032 (2)0.0011 (2)−0.0052 (3)
C250.0188 (13)0.0194 (12)0.0237 (13)−0.0053 (10)0.0023 (10)−0.0085 (11)
C260.0281 (15)0.0288 (14)0.0236 (14)−0.0089 (11)0.0035 (11)−0.0048 (11)
C270.0315 (16)0.0314 (15)0.0348 (16)−0.0133 (12)0.0082 (13)−0.0053 (13)
C280.0278 (15)0.0331 (15)0.0452 (18)−0.0144 (12)0.0040 (13)−0.0153 (14)
C290.0332 (16)0.0368 (15)0.0320 (16)−0.0085 (12)−0.0026 (12)−0.0153 (13)
C300.0253 (14)0.0261 (13)0.0242 (14)−0.0071 (11)0.0035 (11)−0.0090 (11)
C310.0186 (12)0.0216 (12)0.0181 (12)−0.0066 (10)0.0044 (10)−0.0060 (10)
C320.0304 (15)0.0286 (14)0.0204 (14)−0.0019 (11)0.0005 (11)−0.0056 (11)
C330.0379 (16)0.0258 (14)0.0373 (17)0.0003 (12)0.0106 (13)−0.0099 (13)
C340.0475 (18)0.0452 (17)0.0368 (17)−0.0127 (14)0.0111 (14)−0.0268 (15)
C350.0374 (17)0.0572 (19)0.0275 (15)−0.0092 (14)−0.0044 (12)−0.0199 (14)
C360.0229 (14)0.0365 (15)0.0248 (14)−0.0054 (11)0.0008 (11)−0.0095 (12)
N40.0198 (11)0.0236 (11)0.0194 (11)−0.0037 (8)0.0019 (9)−0.0041 (9)
S40.0180 (3)0.0232 (3)0.0181 (3)−0.0046 (2)0.0019 (2)−0.0059 (3)
C370.0202 (13)0.0280 (13)0.0188 (13)−0.0100 (10)0.0050 (10)−0.0092 (11)
C380.0276 (14)0.0311 (14)0.0241 (14)−0.0020 (11)0.0006 (11)−0.0076 (12)
C390.0358 (16)0.0367 (16)0.0368 (17)−0.0024 (13)0.0083 (13)−0.0162 (13)
C400.0355 (16)0.0486 (17)0.0372 (17)−0.0134 (14)0.0108 (13)−0.0288 (14)
C410.0325 (16)0.0544 (18)0.0246 (15)−0.0108 (13)−0.0005 (12)−0.0170 (13)
C420.0221 (14)0.0356 (14)0.0231 (14)−0.0049 (11)0.0014 (11)−0.0084 (12)
C430.0170 (12)0.0216 (12)0.0237 (13)−0.0050 (10)0.0035 (10)−0.0076 (11)
C440.0303 (15)0.0338 (14)0.0245 (14)−0.0122 (12)0.0045 (12)−0.0083 (12)
C450.0333 (16)0.0371 (16)0.0359 (17)−0.0179 (13)0.0101 (13)−0.0067 (13)
C460.0280 (15)0.0373 (16)0.0450 (18)−0.0163 (12)0.0041 (13)−0.0172 (14)
C470.0336 (16)0.0431 (16)0.0291 (16)−0.0104 (13)−0.0020 (12)−0.0147 (13)
C480.0256 (14)0.0302 (14)0.0235 (14)−0.0085 (11)0.0024 (11)−0.0067 (11)
N50.0204 (11)0.0247 (11)0.0221 (11)−0.0018 (8)−0.0007 (9)−0.0089 (9)
S50.0226 (3)0.0219 (3)0.0204 (3)−0.0044 (2)−0.0010 (3)−0.0066 (3)
C490.0176 (13)0.0267 (13)0.0209 (13)−0.0035 (10)0.0002 (10)−0.0052 (11)
C500.0181 (13)0.0297 (14)0.0239 (14)−0.0029 (11)0.0028 (11)−0.0076 (11)
C510.0184 (13)0.0284 (14)0.0359 (16)−0.0036 (11)0.0054 (12)−0.0054 (12)
C520.0204 (14)0.0390 (16)0.0296 (16)−0.0032 (12)0.0041 (12)0.0036 (13)
C530.0252 (14)0.0531 (18)0.0180 (14)−0.0051 (13)−0.0005 (11)−0.0067 (13)
C540.0294 (15)0.0367 (15)0.0236 (14)−0.0096 (12)0.0016 (11)−0.0099 (12)
C550.0288 (14)0.0230 (13)0.0194 (13)−0.0092 (11)−0.0034 (10)−0.0051 (11)
C560.0324 (16)0.0256 (14)0.0440 (17)−0.0092 (12)−0.0033 (13)−0.0091 (13)
C570.0304 (16)0.0386 (16)0.0457 (18)−0.0095 (13)−0.0035 (13)−0.0096 (14)
C580.0387 (17)0.0449 (17)0.0364 (17)−0.0252 (14)−0.0007 (13)−0.0090 (14)
C590.0545 (19)0.0299 (15)0.0382 (17)−0.0229 (14)0.0042 (14)−0.0120 (13)
C600.0377 (16)0.0249 (13)0.0288 (15)−0.0083 (11)0.0010 (12)−0.0076 (11)
N60.0246 (12)0.0197 (11)0.0289 (12)−0.0051 (9)0.0025 (10)−0.0085 (9)
S60.0198 (3)0.0189 (3)0.0251 (3)−0.0041 (2)0.0027 (3)−0.0063 (3)
C610.0314 (15)0.0182 (12)0.0227 (14)−0.0067 (10)0.0022 (11)−0.0066 (11)
C620.0361 (16)0.0283 (14)0.0322 (16)−0.0106 (12)0.0114 (12)−0.0110 (12)
C630.065 (2)0.0356 (16)0.0361 (18)−0.0232 (16)0.0222 (16)−0.0121 (14)
C640.084 (3)0.0300 (16)0.0259 (17)−0.0235 (17)−0.0009 (17)−0.0027 (13)
C650.061 (2)0.0293 (16)0.0444 (19)−0.0052 (15)−0.0224 (16)−0.0027 (14)
C660.0371 (16)0.0284 (14)0.0379 (17)−0.0091 (12)−0.0032 (13)−0.0056 (13)
C670.0210 (13)0.0219 (12)0.0244 (14)−0.0017 (10)−0.0015 (10)−0.0079 (11)
C680.0270 (14)0.0285 (14)0.0335 (15)−0.0089 (11)0.0004 (12)−0.0117 (12)
C690.0307 (15)0.0288 (14)0.0442 (17)−0.0081 (12)−0.0025 (13)−0.0175 (13)
C700.0326 (15)0.0379 (15)0.0345 (16)−0.0022 (12)−0.0004 (12)−0.0185 (13)
C710.0329 (15)0.0347 (15)0.0294 (15)−0.0060 (12)0.0056 (12)−0.0100 (12)
C720.0247 (13)0.0241 (13)0.0275 (14)−0.0049 (10)0.0009 (11)−0.0085 (11)
N70.0386 (14)0.0336 (13)0.0306 (14)−0.0002 (11)−0.0089 (11)−0.0038 (11)
S70.0334 (4)0.0323 (4)0.0285 (4)−0.0039 (3)−0.0063 (3)−0.0107 (3)
C730.0254 (13)0.0244 (13)0.0249 (14)−0.0057 (10)−0.0014 (11)−0.0046 (11)
C740.0336 (15)0.0343 (15)0.0369 (16)−0.0021 (12)−0.0007 (13)−0.0197 (13)
C750.0251 (14)0.0346 (15)0.0438 (17)0.0003 (12)−0.0002 (12)−0.0124 (13)
C760.0294 (15)0.0354 (15)0.0295 (15)−0.0107 (12)−0.0051 (11)−0.0039 (12)
C770.0322 (15)0.0306 (14)0.0350 (16)−0.0033 (12)−0.0050 (12)−0.0157 (12)
C780.0298 (15)0.0246 (13)0.0346 (16)−0.0013 (11)−0.0043 (12)−0.0093 (12)
C790.0265 (14)0.0265 (13)0.0380 (16)−0.0030 (11)−0.0094 (12)−0.0093 (12)
C800.0408 (18)0.0304 (16)0.096 (3)−0.0066 (14)0.0196 (18)−0.0196 (17)
C810.042 (2)0.045 (2)0.118 (3)−0.0115 (16)0.036 (2)−0.019 (2)
C820.0326 (18)0.0409 (19)0.095 (3)−0.0139 (15)−0.0026 (18)−0.0018 (18)
C830.057 (2)0.0263 (16)0.067 (2)−0.0121 (15)−0.0175 (18)−0.0094 (16)
C840.0497 (19)0.0332 (16)0.0435 (18)−0.0023 (14)−0.0145 (15)−0.0135 (14)
N80.081 (2)0.0545 (19)0.092 (3)0.0028 (17)−0.001 (2)−0.0345 (18)
C850.062 (2)0.054 (2)0.056 (2)−0.0091 (18)0.0131 (19)−0.0273 (19)
C860.065 (3)0.096 (3)0.063 (3)0.002 (2)0.007 (2)−0.016 (2)
N90.101 (3)0.096 (2)0.067 (2)−0.062 (2)0.027 (2)−0.039 (2)
C870.056 (2)0.053 (2)0.047 (2)−0.0271 (17)−0.0029 (17)−0.0185 (17)
C880.065 (2)0.071 (2)0.0349 (18)−0.0336 (19)−0.0016 (16)−0.0129 (17)
Geometric parameters (Å, º) top
Co1—N12.1486 (19)C43—C481.385 (3)
Co1—N22.1679 (19)C43—C441.394 (3)
Co1—N32.1187 (19)C44—C451.383 (3)
Co1—N42.1400 (19)C44—H440.9500
Co1—N52.1454 (19)C45—C461.382 (3)
Co1—N62.1367 (19)C45—H450.9500
N1—S11.5746 (19)C46—C471.379 (3)
N1—H1A0.80 (2)C46—H460.9500
S1—C11.798 (2)C47—C481.398 (3)
S1—C71.805 (2)C47—H470.9500
C1—C21.381 (3)C48—H480.9500
C1—C61.382 (3)N5—S51.5754 (19)
C2—C31.390 (3)N5—H5A0.81 (2)
C2—H20.9500S5—C551.794 (2)
C3—C41.374 (4)S5—C491.804 (2)
C3—H30.9500C49—C501.382 (3)
C4—C51.381 (4)C49—C541.394 (3)
C4—H40.9500C50—C511.395 (3)
C5—C61.390 (3)C50—H500.9500
C5—H50.9500C51—C521.386 (3)
C6—H60.9500C51—H510.9500
C7—C121.369 (3)C52—C531.381 (3)
C7—C81.390 (3)C52—H520.9500
C8—C91.380 (3)C53—C541.382 (3)
C8—H80.9500C53—H530.9500
C9—C101.367 (4)C54—H540.9500
C9—H90.9500C55—C601.379 (3)
C10—C111.388 (4)C55—C561.387 (3)
C10—H100.9500C56—C571.388 (3)
C11—C121.386 (3)C56—H560.9500
C11—H110.9500C57—C581.386 (3)
C12—H120.9500C57—H570.9500
N2—S21.5768 (19)C58—C591.371 (4)
N2—H2A0.78 (2)C58—H580.9500
S2—C131.803 (2)C59—C601.392 (3)
S2—C191.809 (2)C59—H590.9500
C13—C141.377 (3)C60—H600.9500
C13—C181.396 (3)N6—S61.5750 (19)
C14—C151.391 (3)N6—H6A0.79 (2)
C14—H140.9500S6—C611.802 (2)
C15—C161.378 (4)S6—C671.811 (2)
C15—H150.9500C61—C661.380 (3)
C16—C171.384 (4)C61—C621.387 (3)
C16—H160.9500C62—C631.385 (3)
C17—C181.390 (4)C62—H620.9500
C17—H170.9500C63—C641.374 (4)
C18—H180.9500C63—H630.9500
C19—C241.384 (3)C64—C651.384 (4)
C19—C201.393 (3)C64—H640.9500
C20—C211.390 (3)C65—C661.389 (3)
C20—H200.9500C65—H650.9500
C21—C221.376 (3)C66—H660.9500
C21—H210.9500C67—C721.382 (3)
C22—C231.382 (3)C67—C681.391 (3)
C22—H220.9500C68—C691.384 (3)
C23—C241.396 (3)C68—H680.9500
C23—H230.9500C69—C701.375 (3)
C24—H240.9500C69—H690.9500
N3—S31.577 (2)C70—C711.389 (3)
N3—H3A0.81 (2)C70—H700.9500
S3—C311.793 (2)C71—C721.390 (3)
S3—C251.809 (2)C71—H710.9500
C25—C301.379 (3)C72—H720.9500
C25—C261.387 (3)N7—S71.573 (2)
C26—C271.389 (3)N7—H7A0.84 (2)
C26—H260.9500S7—C791.807 (3)
C27—C281.382 (3)S7—C731.811 (2)
C27—H270.9500C73—C781.379 (3)
C28—C291.388 (3)C73—C741.385 (3)
C28—H280.9500C74—C751.385 (3)
C29—C301.390 (3)C74—H740.9500
C29—H290.9500C75—C761.373 (3)
C30—H300.9500C75—H750.9500
C31—C321.384 (3)C76—C771.379 (3)
C31—C361.386 (3)C76—H760.9500
C32—C331.388 (3)C77—C781.381 (3)
C32—H320.9500C77—H770.9500
C33—C341.386 (4)C78—H780.9500
C33—H330.9500C79—C841.381 (3)
C34—C351.369 (4)C79—C801.383 (4)
C34—H340.9500C80—C811.379 (4)
C35—C361.391 (3)C80—H800.9500
C35—H350.9500C81—C821.391 (4)
C36—H360.9500C81—H810.9500
N4—S41.574 (2)C82—C831.370 (4)
N4—H4A0.80 (2)C82—H820.9500
S4—C371.798 (2)C83—C841.372 (4)
S4—C431.806 (2)C83—H830.9500
C37—C421.385 (3)C84—H840.9500
C37—C381.387 (3)N8—C851.133 (4)
C38—C391.386 (3)C85—C861.435 (4)
C38—H380.9500C86—H86A0.9800
C39—C401.381 (4)C86—H86B0.9800
C39—H390.9500C86—H86C0.9800
C40—C411.371 (3)N9—C871.138 (4)
C40—H400.9500C87—C881.447 (4)
C41—C421.397 (3)C88—H88A0.9800
C41—H410.9500C88—H88B0.9800
C42—H420.9500C88—H88C0.9800
N1—Co1—N284.82 (7)C42—C41—H41120.1
N1—Co1—N385.63 (7)C37—C42—C41119.1 (2)
N1—Co1—N495.19 (7)C37—C42—H42120.5
N1—Co1—N594.28 (7)C41—C42—H42120.5
N1—Co1—N6179.23 (8)C48—C43—C44121.2 (2)
N2—Co1—N385.11 (7)C48—C43—S4118.71 (18)
N2—Co1—N493.75 (7)C44—C43—S4119.77 (18)
N2—Co1—N5178.44 (8)C45—C44—C43118.8 (2)
N2—Co1—N695.46 (7)C45—C44—H44120.6
N3—Co1—N4178.54 (8)C43—C44—H44120.6
N3—Co1—N596.10 (7)C46—C45—C44120.6 (2)
N3—Co1—N693.68 (7)C46—C45—H45119.7
N4—Co1—N585.06 (7)C44—C45—H45119.7
N4—Co1—N685.50 (7)C47—C46—C45120.3 (2)
N5—Co1—N685.45 (7)C47—C46—H46119.9
S1—N1—Co1129.24 (11)C45—C46—H46119.9
S1—N1—H1A112.6 (16)C46—C47—C48120.2 (2)
Co1—N1—H1A116.3 (17)C46—C47—H47119.9
N1—S1—C1109.37 (11)C48—C47—H47119.9
N1—S1—C7110.10 (11)C43—C48—C47118.8 (2)
C1—S1—C797.20 (10)C43—C48—H48120.6
C2—C1—C6121.1 (2)C47—C48—H48120.6
C2—C1—S1118.0 (2)S5—N5—Co1127.53 (11)
C6—C1—S1120.84 (19)S5—N5—H5A110.4 (17)
C1—C2—C3119.3 (3)Co1—N5—H5A117.7 (16)
C1—C2—H2120.4N5—S5—C55109.95 (11)
C3—C2—H2120.4N5—S5—C49109.73 (10)
C4—C3—C2119.9 (3)C55—S5—C4999.29 (10)
C4—C3—H3120.0C50—C49—C54121.0 (2)
C2—C3—H3120.0C50—C49—S5118.68 (17)
C3—C4—C5120.6 (3)C54—C49—S5120.07 (18)
C3—C4—H4119.7C49—C50—C51119.1 (2)
C5—C4—H4119.7C49—C50—H50120.4
C4—C5—C6119.9 (3)C51—C50—H50120.4
C4—C5—H5120.1C52—C51—C50120.1 (2)
C6—C5—H5120.1C52—C51—H51120.0
C1—C6—C5119.2 (3)C50—C51—H51120.0
C1—C6—H6120.4C53—C52—C51120.2 (2)
C5—C6—H6120.4C53—C52—H52119.9
C12—C7—C8121.0 (2)C51—C52—H52119.9
C12—C7—S1119.28 (18)C52—C53—C54120.5 (2)
C8—C7—S1119.70 (19)C52—C53—H53119.7
C9—C8—C7119.3 (2)C54—C53—H53119.7
C9—C8—H8120.4C53—C54—C49119.2 (2)
C7—C8—H8120.4C53—C54—H54120.4
C10—C9—C8120.4 (2)C49—C54—H54120.4
C10—C9—H9119.8C60—C55—C56120.6 (2)
C8—C9—H9119.8C60—C55—S5117.32 (19)
C9—C10—C11120.0 (3)C56—C55—S5121.91 (17)
C9—C10—H10120.0C55—C56—C57119.5 (2)
C11—C10—H10120.0C55—C56—H56120.3
C12—C11—C10120.3 (3)C57—C56—H56120.3
C12—C11—H11119.9C58—C57—C56119.9 (3)
C10—C11—H11119.9C58—C57—H57120.1
C7—C12—C11119.0 (2)C56—C57—H57120.1
C7—C12—H12120.5C59—C58—C57120.3 (2)
C11—C12—H12120.5C59—C58—H58119.9
S2—N2—Co1127.82 (11)C57—C58—H58119.9
S2—N2—H2A110.9 (18)C58—C59—C60120.3 (2)
Co1—N2—H2A117.8 (18)C58—C59—H59119.8
N2—S2—C13110.17 (11)C60—C59—H59119.8
N2—S2—C19110.56 (11)C55—C60—C59119.4 (2)
C13—S2—C1998.77 (11)C55—C60—H60120.3
C14—C13—C18121.7 (2)C59—C60—H60120.3
C14—C13—S2121.39 (18)S6—N6—Co1126.64 (11)
C18—C13—S2116.8 (2)S6—N6—H6A111.1 (17)
C13—C14—C15119.0 (2)Co1—N6—H6A119.7 (18)
C13—C14—H14120.5N6—S6—C61110.24 (11)
C15—C14—H14120.5N6—S6—C67109.40 (11)
C16—C15—C14119.9 (3)C61—S6—C6799.97 (10)
C16—C15—H15120.1C66—C61—C62121.3 (2)
C14—C15—H15120.1C66—C61—S6121.22 (19)
C15—C16—C17121.0 (3)C62—C61—S6117.37 (19)
C15—C16—H16119.5C63—C62—C61119.0 (3)
C17—C16—H16119.5C63—C62—H62120.5
C16—C17—C18119.9 (3)C61—C62—H62120.5
C16—C17—H17120.0C64—C63—C62120.1 (3)
C18—C17—H17120.0C64—C63—H63120.0
C17—C18—C13118.5 (3)C62—C63—H63120.0
C17—C18—H18120.8C63—C64—C65120.8 (3)
C13—C18—H18120.8C63—C64—H64119.6
C24—C19—C20120.8 (2)C65—C64—H64119.6
C24—C19—S2118.24 (18)C64—C65—C66119.6 (3)
C20—C19—S2120.55 (19)C64—C65—H65120.2
C21—C20—C19118.9 (2)C66—C65—H65120.2
C21—C20—H20120.5C61—C66—C65119.2 (3)
C19—C20—H20120.5C61—C66—H66120.4
C22—C21—C20120.5 (2)C65—C66—H66120.4
C22—C21—H21119.8C72—C67—C68120.9 (2)
C20—C21—H21119.8C72—C67—S6117.24 (17)
C21—C22—C23120.6 (3)C68—C67—S6121.46 (18)
C21—C22—H22119.7C69—C68—C67119.1 (2)
C23—C22—H22119.7C69—C68—H68120.4
C22—C23—C24119.8 (2)C67—C68—H68120.4
C22—C23—H23120.1C70—C69—C68120.5 (2)
C24—C23—H23120.1C70—C69—H69119.7
C19—C24—C23119.4 (2)C68—C69—H69119.7
C19—C24—H24120.3C69—C70—C71120.2 (2)
C23—C24—H24120.3C69—C70—H70119.9
S3—N3—Co1130.12 (11)C71—C70—H70119.9
S3—N3—H3A109.6 (17)C70—C71—C72119.9 (2)
Co1—N3—H3A118.1 (17)C70—C71—H71120.1
N3—S3—C31108.59 (10)C72—C71—H71120.1
N3—S3—C25110.07 (11)C67—C72—C71119.4 (2)
C31—S3—C2599.57 (10)C67—C72—H72120.3
C30—C25—C26121.5 (2)C71—C72—H72120.3
C30—C25—S3118.62 (18)S7—N7—H7A111.3 (19)
C26—C25—S3119.48 (17)N7—S7—C79111.75 (12)
C25—C26—C27119.0 (2)N7—S7—C73112.35 (11)
C25—C26—H26120.5C79—S7—C7395.68 (11)
C27—C26—H26120.5C78—C73—C74120.8 (2)
C28—C27—C26120.1 (2)C78—C73—S7120.48 (18)
C28—C27—H27120.0C74—C73—S7118.71 (18)
C26—C27—H27120.0C73—C74—C75119.4 (2)
C27—C28—C29120.3 (2)C73—C74—H74120.3
C27—C28—H28119.8C75—C74—H74120.3
C29—C28—H28119.8C76—C75—C74119.9 (2)
C28—C29—C30120.1 (2)C76—C75—H75120.0
C28—C29—H29120.0C74—C75—H75120.0
C30—C29—H29120.0C75—C76—C77120.4 (2)
C25—C30—C29119.0 (2)C75—C76—H76119.8
C25—C30—H30120.5C77—C76—H76119.8
C29—C30—H30120.5C76—C77—C78120.3 (2)
C32—C31—C36120.8 (2)C76—C77—H77119.8
C32—C31—S3121.54 (18)C78—C77—H77119.8
C36—C31—S3117.22 (17)C73—C78—C77119.2 (2)
C31—C32—C33119.5 (2)C73—C78—H78120.4
C31—C32—H32120.2C77—C78—H78120.4
C33—C32—H32120.2C84—C79—C80120.3 (3)
C34—C33—C32119.7 (2)C84—C79—S7118.9 (2)
C34—C33—H33120.2C80—C79—S7120.8 (2)
C32—C33—H33120.2C81—C80—C79119.7 (3)
C35—C34—C33120.6 (2)C81—C80—H80120.1
C35—C34—H34119.7C79—C80—H80120.1
C33—C34—H34119.7C80—C81—C82119.8 (3)
C34—C35—C36120.4 (2)C80—C81—H81120.1
C34—C35—H35119.8C82—C81—H81120.1
C36—C35—H35119.8C83—C82—C81119.6 (3)
C31—C36—C35119.0 (2)C83—C82—H82120.2
C31—C36—H36120.5C81—C82—H82120.2
C35—C36—H36120.5C82—C83—C84121.0 (3)
S4—N4—Co1127.74 (11)C82—C83—H83119.5
S4—N4—H4A113.0 (18)C84—C83—H83119.5
Co1—N4—H4A115.9 (18)C83—C84—C79119.5 (3)
N4—S4—C37108.79 (10)C83—C84—H84120.3
N4—S4—C43110.51 (11)C79—C84—H84120.3
C37—S4—C4398.84 (10)N8—C85—C86179.7 (4)
C42—C37—C38121.1 (2)C85—C86—H86A109.5
C42—C37—S4117.14 (18)C85—C86—H86B109.5
C38—C37—S4121.64 (18)H86A—C86—H86B109.5
C39—C38—C37119.0 (2)C85—C86—H86C109.5
C39—C38—H38120.5H86A—C86—H86C109.5
C37—C38—H38120.5H86B—C86—H86C109.5
C40—C39—C38120.2 (2)N9—C87—C88179.4 (3)
C40—C39—H39119.9C87—C88—H88A109.5
C38—C39—H39119.9C87—C88—H88B109.5
C41—C40—C39120.8 (2)H88A—C88—H88B109.5
C41—C40—H40119.6C87—C88—H88C109.5
C39—C40—H40119.6H88A—C88—H88C109.5
C40—C41—C42119.8 (2)H88B—C88—H88C109.5
C40—C41—H41120.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.80 (2)3.07 (2)3.8337 (19)159 (2)
N2—H2A···I10.78 (2)3.09 (2)3.8207 (19)157 (2)
N3—H3A···I10.81 (2)2.95 (2)3.7302 (19)163 (2)
N4—H4A···I20.80 (2)2.97 (2)3.7413 (19)165 (2)
N5—H5A···I20.81 (2)3.09 (2)3.8461 (19)156 (2)
N6—H6A···I20.79 (2)3.09 (2)3.831 (2)157 (2)
N7—H7A···I10.84 (2)3.16 (2)3.987 (2)172 (2)
(II) hexakis(S,S-diphenylsulfimide)iron(III) trichloride top
Crystal data top
[Fe(C12H11NS)6]Cl3Dx = 1.357 Mg m−3
Mr = 1369.93Mo Kα radiation, λ = 0.71073 Å
Cubic, Pa3Cell parameters from 28769 reflections
Hall symbol: -P 2ac 2ab 3θ = 2.9–27.5°
a = 18.8566 (4) ŵ = 0.58 mm−1
V = 6704.9 (2) Å3T = 120 K
Z = 4Prism ## AUTHOR: what shape of prism?, yellow
F(000) = 28520.10 × 0.08 × 0.05 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		2572 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode1840 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.133
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scans to fill Ewald sphereh = −24→24
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)		k = −24→21
Tmin = 0.942, Tmax = 0.970l = −24→23
64482 measured reflections
Refinement top
Refinement on F2Hydrogen site location: placed geometrically except NH which were refined with restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.046 w = 1/[σ2(Fo2) + (0.052P)2 + 4.568P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.113(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.66 e Å−3
2572 reflectionsΔρmin = −0.89 e Å−3
138 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0011 (2)
Primary atom site location: structure-invariant direct methods
Crystal data top
[Fe(C12H11NS)6]Cl3Z = 4
Mr = 1369.93Mo Kα radiation
Cubic, Pa3µ = 0.58 mm−1
a = 18.8566 (4) ÅT = 120 K
V = 6704.9 (2) Å30.10 × 0.08 × 0.05 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		2572 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)		1840 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.970Rint = 0.133
64482 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.66 e Å−3
2572 reflectionsΔρmin = −0.89 e Å−3
138 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.00000.50000.50000.0180 (2)
N10.03185 (11)0.57209 (11)0.42297 (11)0.0220 (5)
H1A−0.0004 (17)0.5942 (16)0.4034 (16)0.033*
S10.10695 (3)0.60826 (3)0.41344 (3)0.02230 (18)
C10.12315 (14)0.61979 (13)0.32077 (13)0.0256 (5)
C20.06855 (15)0.63534 (14)0.27394 (14)0.0313 (6)
H20.02150.64230.29060.038*
C30.08410 (18)0.64050 (16)0.20221 (15)0.0412 (7)
H30.04750.65080.16920.049*
C40.15299 (19)0.63060 (16)0.17889 (16)0.0445 (8)
H40.16310.63400.12960.053*
C50.20720 (18)0.61597 (16)0.22546 (17)0.0433 (8)
H50.25440.61030.20870.052*
C60.19204 (15)0.60964 (15)0.29753 (15)0.0341 (6)
H60.22860.59850.33030.041*
C70.10215 (13)0.69942 (13)0.44071 (13)0.0237 (5)
C80.16229 (14)0.74159 (14)0.43413 (14)0.0315 (6)
H80.20410.72320.41290.038*
C90.16052 (15)0.81049 (15)0.45880 (15)0.0346 (6)
H90.20140.83960.45470.042*
C100.09977 (16)0.83715 (14)0.48932 (14)0.0338 (6)
H100.09870.88470.50580.041*
C110.04041 (15)0.79486 (14)0.49594 (14)0.0310 (6)
H11−0.00130.81350.51730.037*
C120.04108 (13)0.72533 (13)0.47173 (13)0.0264 (6)
H120.00030.69610.47640.032*
Cl1−0.12579 (3)0.62579 (3)0.37421 (3)0.0303 (3)
Cl20.00000.50000.00000.0911 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0180 (2)0.0180 (2)0.0180 (2)−0.00028 (18)0.00028 (18)−0.00028 (18)
N10.0199 (10)0.0208 (11)0.0252 (11)0.0008 (8)0.0010 (9)0.0026 (9)
S10.0206 (3)0.0216 (3)0.0246 (3)−0.0003 (2)0.0014 (2)0.0042 (2)
C10.0313 (14)0.0198 (12)0.0257 (13)−0.0024 (10)0.0065 (11)0.0023 (10)
C20.0354 (15)0.0303 (14)0.0282 (14)−0.0007 (12)0.0017 (11)0.0048 (11)
C30.0576 (19)0.0379 (17)0.0280 (15)−0.0058 (15)−0.0020 (14)0.0042 (12)
C40.068 (2)0.0356 (16)0.0296 (15)−0.0093 (15)0.0160 (15)0.0006 (13)
C50.0473 (18)0.0380 (16)0.0446 (18)−0.0018 (14)0.0229 (15)0.0012 (14)
C60.0317 (14)0.0318 (14)0.0390 (16)−0.0018 (12)0.0077 (12)0.0025 (12)
C70.0265 (13)0.0221 (12)0.0224 (12)−0.0033 (10)−0.0038 (10)0.0035 (10)
C80.0274 (13)0.0325 (15)0.0345 (15)−0.0034 (11)−0.0004 (11)0.0039 (12)
C90.0349 (15)0.0299 (14)0.0391 (16)−0.0107 (12)−0.0046 (13)0.0045 (12)
C100.0478 (17)0.0244 (13)0.0291 (14)−0.0051 (12)−0.0049 (13)0.0010 (11)
C110.0390 (16)0.0269 (14)0.0271 (14)0.0002 (11)0.0037 (12)−0.0010 (11)
C120.0283 (14)0.0253 (13)0.0255 (13)−0.0026 (10)0.0009 (11)0.0030 (10)
Cl10.0303 (3)0.0303 (3)0.0303 (3)0.0054 (2)−0.0054 (2)0.0054 (2)
Cl20.0911 (10)0.0911 (10)0.0911 (10)−0.0293 (8)0.0293 (8)0.0293 (8)
Geometric parameters (Å, º) top
Fe1—N12.078 (2)C5—H50.9500
N1—S11.582 (2)C6—H60.9500
N1—H1A0.82 (3)C7—C121.381 (4)
S1—C11.787 (3)C7—C81.391 (4)
S1—C71.797 (2)C8—C91.380 (4)
C1—C61.384 (4)C8—H80.9500
C1—C21.388 (4)C9—C101.377 (4)
C2—C31.387 (4)C9—H90.9500
C2—H20.9500C10—C111.380 (4)
C3—C41.384 (5)C10—H100.9500
C3—H30.9500C11—C121.388 (4)
C4—C51.376 (5)C11—H110.9500
C4—H40.9500C12—H120.9500
C5—C61.394 (4)
N1—Fe1—N1i86.21 (9)C1—C6—C5119.3 (3)
S1—N1—Fe1128.32 (13)C1—C6—H6120.4
S1—N1—H1A113 (2)C5—C6—H6120.4
Fe1—N1—H1A115 (2)C12—C7—C8121.0 (2)
N1—S1—C1108.45 (12)C12—C7—S1120.12 (19)
N1—S1—C7109.57 (11)C8—C7—S1118.7 (2)
C1—S1—C799.90 (11)C9—C8—C7119.2 (3)
C6—C1—C2121.6 (2)C9—C8—H8120.4
C6—C1—S1116.9 (2)C7—C8—H8120.4
C2—C1—S1121.4 (2)C10—C9—C8120.3 (3)
C3—C2—C1118.6 (3)C10—C9—H9119.8
C3—C2—H2120.7C8—C9—H9119.8
C1—C2—H2120.7C9—C10—C11120.1 (3)
C4—C3—C2119.9 (3)C9—C10—H10119.9
C4—C3—H3120.0C11—C10—H10119.9
C2—C3—H3120.0C10—C11—C12120.6 (3)
C5—C4—C3121.4 (3)C10—C11—H11119.7
C5—C4—H4119.3C12—C11—H11119.7
C3—C4—H4119.3C7—C12—C11118.7 (2)
C4—C5—C6119.2 (3)C7—C12—H12120.6
C4—C5—H5120.4C11—C12—H12120.6
C6—C5—H5120.4
Symmetry code: (i) z−1/2, −x+1/2, −y+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl10.82 (3)2.50 (3)3.272 (2)157 (3)
(III) diiodotetrakis(S,S-diphenylsulfimide)platinum(IV) dichloride dichloromethane disolvate, [Pt(C12H11NS)6]Cl2·2CH2Cl2 top
Crystal data top
[Pt(C12H11NS)4I2]Cl2·2CH2Cl2F(000) = 1452
Mr = 1494.75Dx = 1.814 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 15561 reflections
a = 13.7287 (5) Åθ = 2.2–28.8°
b = 10.8620 (4) ŵ = 4.18 mm−1
c = 18.3936 (6) ÅT = 150 K
β = 93.864 (2)°Block, red
V = 2736.64 (17) Å30.28 × 0.17 × 0.16 mm
Z = 2
Data collection top
Bruker SMART 1000 CCD
diffractometer		6442 independent reflections
Radiation source: sealed tube5859 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω rotation with narrow frames scansθmax = 28.8°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −18→18
Tmin = 0.357, Tmax = 0.511k = −13→14
23077 measured reflectionsl = −24→24
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)] = 0.044Hydrogen site location: placed geometrically except NH which were refined with restraints
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.078P)2 + 27.27P]
where P = (Fo2 + 2Fc2)/3
6442 reflections(Δ/σ)max = 0.001
338 parametersΔρmax = 3.60 e Å−3
50 restraintsΔρmin = −3.70 e Å−3
Crystal data top
[Pt(C12H11NS)4I2]Cl2·2CH2Cl2V = 2736.64 (17) Å3
Mr = 1494.75Z = 2
Monoclinic, P21/nMo Kα radiation
a = 13.7287 (5) ŵ = 4.18 mm−1
b = 10.8620 (4) ÅT = 150 K
c = 18.3936 (6) Å0.28 × 0.17 × 0.16 mm
β = 93.864 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		6442 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		5859 reflections with I > 2σ(I)
Tmin = 0.357, Tmax = 0.511Rint = 0.016
23077 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04450 restraints
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.078P)2 + 27.27P]
where P = (Fo2 + 2Fc2)/3
6442 reflectionsΔρmax = 3.60 e Å−3
338 parametersΔρmin = −3.70 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pt10.00000.50000.00000.01577 (10)
N1−0.1134 (3)0.5597 (5)0.0575 (3)0.0215 (10)
H1A−0.109 (6)0.556 (8)0.0996 (16)0.032*
S1−0.22456 (10)0.55368 (14)0.02638 (8)0.0201 (3)
C1−0.2807 (4)0.6903 (6)0.0575 (4)0.0240 (12)
C2−0.2680 (5)0.7287 (7)0.1295 (4)0.0295 (13)
H2−0.22600.68480.16340.035*
C3−0.3179 (5)0.8327 (7)0.1511 (5)0.0375 (16)
H3−0.31020.86010.20020.045*
C4−0.3785 (6)0.8962 (7)0.1011 (5)0.0444 (19)
H4−0.41250.96680.11620.053*
C5−0.3904 (7)0.8585 (8)0.0297 (5)0.049 (2)
H5−0.43240.9031−0.00390.059*
C6−0.3405 (5)0.7540 (7)0.0065 (4)0.0355 (15)
H6−0.34750.7276−0.04290.043*
C7−0.2900 (4)0.4419 (6)0.0767 (3)0.0228 (12)
C8−0.3908 (5)0.4527 (7)0.0779 (4)0.0308 (14)
H8−0.42400.52070.05520.037*
C9−0.4421 (5)0.3633 (7)0.1127 (4)0.0380 (16)
H9−0.51100.36950.11360.046*
C10−0.3940 (6)0.2655 (7)0.1461 (4)0.0373 (16)
H10−0.42970.20500.17040.045*
C11−0.2947 (6)0.2548 (7)0.1444 (4)0.0389 (16)
H11−0.26210.18590.16670.047*
C12−0.2411 (5)0.3445 (7)0.1101 (4)0.0309 (14)
H12−0.17210.33830.10990.037*
N20.0492 (4)0.4043 (5)0.0905 (3)0.0227 (10)
H2A0.031 (6)0.429 (8)0.127 (3)0.034*
S20.09381 (11)0.26965 (14)0.08776 (8)0.0213 (3)
C130.0201 (4)0.1596 (6)0.1317 (3)0.0246 (12)
C14−0.0215 (6)0.1861 (7)0.1962 (4)0.0349 (15)
H14−0.01430.26510.21800.042*
C15−0.0743 (6)0.0941 (7)0.2284 (5)0.0399 (17)
H15−0.10210.11020.27340.048*
C16−0.0869 (6)−0.0178 (8)0.1971 (5)0.045 (2)
H16−0.1244−0.07850.21970.054*
C17−0.0456 (8)−0.0448 (9)0.1322 (5)0.054 (2)
H17−0.0553−0.12350.11030.065*
C180.0106 (7)0.0442 (8)0.0988 (4)0.0437 (18)
H180.04110.02640.05520.052*
C190.1984 (4)0.2720 (6)0.1520 (3)0.0224 (11)
C200.2422 (5)0.1610 (6)0.1718 (4)0.0322 (14)
H200.21370.08540.15550.039*
C210.3290 (5)0.1618 (7)0.2161 (4)0.0377 (17)
H210.36000.08650.23020.045*
C220.3695 (5)0.2731 (8)0.2394 (4)0.0333 (15)
H220.42840.27360.26960.040*
C230.3256 (5)0.3831 (7)0.2192 (4)0.0316 (14)
H230.35410.45850.23570.038*
C240.2386 (5)0.3841 (6)0.1742 (3)0.0272 (13)
H240.20830.45950.15940.033*
I10.10034 (4)0.69162 (5)0.05323 (3)0.03901 (15)
Cl3−0.05466 (12)0.52092 (15)0.22788 (8)0.0272 (3)
C250.3646 (10)−0.2021 (12)0.1436 (7)0.057 (3)0.806 (11)
H25A0.4179−0.16090.17330.068*0.806 (11)
H25B0.3085−0.21140.17430.068*0.806 (11)
Cl10.4040 (9)−0.3483 (9)0.1179 (5)0.0601 (19)0.806 (11)
Cl20.3299 (3)−0.1097 (3)0.0684 (3)0.0712 (15)0.806 (11)
C25A0.361 (5)−0.235 (5)0.063 (3)0.057 (9)0.194 (11)
H25C0.2961−0.24580.03770.069*0.194 (11)
H25D0.4080−0.21680.02590.069*0.194 (11)
Cl1A0.393 (3)−0.365 (4)0.103 (2)0.047 (5)0.194 (11)
Cl2A0.3577 (16)−0.1083 (14)0.1233 (11)0.079 (7)0.194 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01193 (15)0.02058 (16)0.01501 (16)0.00134 (10)0.00255 (10)0.00117 (10)
N10.013 (2)0.034 (3)0.018 (2)0.0031 (19)0.0034 (17)−0.002 (2)
S10.0144 (6)0.0263 (7)0.0200 (6)0.0024 (5)0.0038 (5)0.0009 (5)
C10.016 (3)0.026 (3)0.031 (3)0.002 (2)0.009 (2)0.004 (2)
C20.024 (3)0.032 (3)0.033 (3)0.005 (3)0.007 (2)−0.005 (3)
C30.030 (3)0.032 (4)0.052 (4)−0.001 (3)0.010 (3)−0.012 (3)
C40.042 (4)0.027 (4)0.066 (5)0.011 (3)0.020 (4)0.003 (3)
C50.047 (5)0.044 (5)0.059 (5)0.025 (4)0.015 (4)0.017 (4)
C60.032 (3)0.043 (4)0.032 (4)0.012 (3)0.007 (3)0.007 (3)
C70.019 (3)0.025 (3)0.025 (3)−0.004 (2)0.005 (2)−0.004 (2)
C80.020 (3)0.033 (3)0.040 (4)−0.002 (3)0.007 (3)0.000 (3)
C90.028 (3)0.041 (4)0.046 (4)−0.011 (3)0.015 (3)−0.007 (3)
C100.044 (4)0.032 (4)0.037 (4)−0.012 (3)0.015 (3)−0.004 (3)
C110.047 (4)0.031 (4)0.039 (4)−0.003 (3)0.008 (3)0.005 (3)
C120.026 (3)0.033 (3)0.034 (3)−0.002 (3)0.004 (3)0.004 (3)
N20.026 (2)0.029 (3)0.014 (2)0.009 (2)0.0049 (18)0.0024 (19)
S20.0223 (7)0.0244 (7)0.0174 (6)0.0041 (5)0.0023 (5)0.0013 (5)
C130.023 (3)0.027 (3)0.022 (3)−0.001 (2)−0.003 (2)0.004 (2)
C140.038 (4)0.030 (3)0.038 (4)0.001 (3)0.010 (3)0.004 (3)
C150.039 (4)0.039 (4)0.043 (4)0.000 (3)0.013 (3)0.014 (3)
C160.037 (4)0.043 (4)0.053 (5)−0.010 (3)−0.008 (4)0.018 (4)
C170.069 (6)0.036 (4)0.056 (5)−0.024 (4)−0.011 (5)−0.002 (4)
C180.058 (5)0.037 (4)0.035 (4)−0.014 (4)0.000 (4)−0.004 (3)
C190.018 (3)0.028 (3)0.022 (3)0.003 (2)0.004 (2)0.004 (2)
C200.026 (3)0.026 (3)0.045 (4)0.002 (3)0.001 (3)0.007 (3)
C210.025 (3)0.042 (4)0.046 (4)0.007 (3)0.001 (3)0.019 (3)
C220.018 (3)0.052 (4)0.029 (3)0.000 (3)−0.003 (2)0.010 (3)
C230.026 (3)0.037 (4)0.031 (3)−0.002 (3)0.000 (3)0.000 (3)
C240.027 (3)0.028 (3)0.027 (3)0.003 (2)0.002 (2)0.002 (2)
I10.0362 (3)0.0428 (3)0.0381 (3)−0.0022 (2)0.00367 (19)−0.0027 (2)
Cl30.0326 (8)0.0308 (7)0.0178 (6)−0.0132 (6)0.0001 (6)−0.0021 (5)
C250.066 (8)0.057 (7)0.050 (6)0.007 (6)0.014 (5)−0.003 (5)
Cl10.070 (4)0.052 (3)0.057 (5)0.013 (3)0.001 (3)0.000 (3)
Cl20.072 (2)0.0488 (18)0.092 (4)0.0009 (15)−0.0037 (19)0.0193 (18)
C25A0.08 (2)0.047 (14)0.041 (18)−0.002 (18)0.010 (18)−0.004 (9)
Cl1A0.047 (8)0.056 (10)0.037 (10)0.016 (8)−0.016 (7)−0.014 (7)
Cl2A0.124 (15)0.047 (7)0.070 (12)0.011 (8)0.040 (11)−0.013 (7)
Geometric parameters (Å, º) top
Pt1—N12.046 (5)S2—C191.797 (6)
Pt1—N22.038 (5)C13—C141.382 (10)
Pt1—I12.6470 (5)C13—C181.394 (10)
N1—S11.595 (5)C14—C151.389 (10)
N1—H1A0.77 (3)C14—H140.9500
S1—C11.784 (6)C15—C161.351 (12)
S1—C71.803 (6)C15—H150.9500
C1—C21.388 (9)C16—C171.387 (15)
C1—C61.389 (9)C16—H160.9500
C2—C31.393 (9)C17—C181.403 (13)
C2—H20.9500C17—H170.9500
C3—C41.383 (12)C18—H180.9500
C3—H30.9500C19—C201.386 (9)
C4—C51.373 (13)C19—C241.387 (9)
C4—H40.9500C20—C211.397 (10)
C5—C61.408 (11)C20—H200.9500
C5—H50.9500C21—C221.387 (11)
C6—H60.9500C21—H210.9500
C7—C121.375 (9)C22—C231.378 (10)
C7—C81.391 (8)C22—H220.9500
C8—C91.382 (10)C23—C241.405 (9)
C8—H80.9500C23—H230.9500
C9—C101.374 (12)C24—H240.9500
C9—H90.9500C25—Cl11.753 (16)
C10—C111.371 (11)C25—Cl21.750 (14)
C10—H100.9500C25—H25A0.9900
C11—C121.396 (10)C25—H25B0.9900
C11—H110.9500C25A—Cl1A1.63 (7)
C12—H120.9500C25A—Cl2A1.77 (5)
N2—S21.588 (5)C25A—H25C0.9900
N2—H2A0.78 (3)C25A—H25D0.9900
S2—C131.793 (6)
N1—Pt1—N287.8 (2)C13—S2—C1999.4 (3)
N1—Pt1—I187.39 (15)C14—C13—C18121.8 (7)
N2—Pt1—I187.89 (16)C14—C13—S2121.8 (5)
S1—N1—Pt1123.0 (3)C18—C13—S2116.3 (5)
S1—N1—H1A111 (6)C13—C14—C15118.3 (7)
Pt1—N1—H1A120 (6)C13—C14—H14120.9
N1—S1—C1105.9 (3)C15—C14—H14120.9
N1—S1—C7109.9 (3)C16—C15—C14121.4 (8)
C1—S1—C798.9 (3)C16—C15—H15119.3
C2—C1—C6121.7 (6)C14—C15—H15119.3
C2—C1—S1121.8 (5)C15—C16—C17120.6 (8)
C6—C1—S1116.5 (5)C15—C16—H16119.7
C1—C2—C3119.0 (7)C17—C16—H16119.7
C1—C2—H2120.5C16—C17—C18119.9 (8)
C3—C2—H2120.5C16—C17—H17120.0
C4—C3—C2120.0 (8)C18—C17—H17120.0
C4—C3—H3120.0C13—C18—C17117.9 (8)
C2—C3—H3120.0C13—C18—H18121.0
C5—C4—C3121.0 (7)C17—C18—H18121.0
C5—C4—H4119.5C20—C19—C24121.9 (6)
C3—C4—H4119.5C20—C19—S2118.3 (5)
C4—C5—C6120.1 (8)C24—C19—S2119.4 (5)
C4—C5—H5119.9C19—C20—C21119.1 (7)
C6—C5—H5119.9C19—C20—H20120.5
C1—C6—C5118.3 (7)C21—C20—H20120.5
C1—C6—H6120.9C22—C21—C20119.6 (7)
C5—C6—H6120.9C22—C21—H21120.2
C12—C7—C8120.9 (6)C20—C21—H21120.2
C12—C7—S1120.2 (5)C23—C22—C21120.9 (6)
C8—C7—S1118.8 (5)C23—C22—H22119.6
C9—C8—C7119.2 (7)C21—C22—H22119.6
C9—C8—H8120.4C22—C23—C24120.3 (7)
C7—C8—H8120.4C22—C23—H23119.8
C10—C9—C8120.4 (7)C24—C23—H23119.8
C10—C9—H9119.8C19—C24—C23118.2 (6)
C8—C9—H9119.8C19—C24—H24120.9
C11—C10—C9120.3 (7)C23—C24—H24120.9
C11—C10—H10119.9Cl1—C25—Cl2112.3 (8)
C9—C10—H10119.9Cl1—C25—H25A109.2
C10—C11—C12120.4 (7)Cl2—C25—H25A109.2
C10—C11—H11119.8Cl1—C25—H25B109.2
C12—C11—H11119.8Cl2—C25—H25B109.2
C7—C12—C11118.9 (6)H25A—C25—H25B107.9
C7—C12—H12120.6Cl1A—C25A—Cl2A114 (3)
C11—C12—H12120.6Cl1A—C25A—H25C108.6
S2—N2—Pt1123.5 (3)Cl2A—C25A—H25C108.6
S2—N2—H2A119 (6)Cl1A—C25A—H25D108.6
Pt1—N2—H2A115 (6)Cl2A—C25A—H25D108.6
N2—S2—C13111.7 (3)H25C—C25A—H25D107.6
N2—S2—C19105.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl30.77 (3)2.46 (4)3.210 (5)165 (8)
N2—H2A···Cl30.78 (3)2.47 (7)3.242 (5)168 (8)
C3—H3···Cl3i0.952.933.567 (7)126
C4—H4···Cl3i0.952.993.601 (9)123
C10—H10···Cl3ii0.952.763.626 (8)153
C14—H14···Cl30.952.843.716 (8)154
C21—H21···Cl3iii0.952.823.546 (7)134
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x−1/2, y−1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formula[Co(C12H11NS)6]I2·C12H11NS·2C2H3N[Fe(C12H11NS)6]Cl3[Pt(C12H11NS)4I2]Cl2·2CH2Cl2
Mr1803.861369.931494.75
Crystal system, space groupTriclinic, P1Cubic, Pa3Monoclinic, P21/n
Temperature (K)150120150
a, b, c (Å)13.0776 (6), 15.1667 (7), 22.4675 (11)18.8566 (4), 18.8566 (4), 18.8566 (4)13.7287 (5), 10.8620 (4), 18.3936 (6)
α, β, γ (°)73.557 (2), 87.490 (2), 78.807 (2)90, 90, 9090, 93.864 (2), 90
V (Å3)4192.5 (3)6704.9 (2)2736.64 (17)
Z242
Radiation typeMo KαMo KαMo Kα
µ (mm−1)1.170.584.18
Crystal size (mm)0.18 × 0.11 × 0.060.10 × 0.08 × 0.050.28 × 0.17 × 0.16
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer		Nonius KappaCCD area-detector
diffractometer		Bruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SORTAV; Blessing, 1995)		Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.818, 0.9330.942, 0.9700.357, 0.511
No. of measured, independent and
observed [I > 2σ(I)] reflections		49288, 19601, 12795 64482, 2572, 1840 23077, 6442, 5859
Rint0.0270.1330.016
(sin θ/λ)max (Å−1)0.6810.6490.678
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.064, 0.89 0.046, 0.113, 1.04 0.044, 0.143, 1.07
No. of reflections1960125726442
No. of parameters987138338
No. of restraints0050
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0244P)2]
where P = (Fo2 + 2Fc2)/3		 w = 1/[σ2(Fo2) + (0.052P)2 + 4.568P]
where P = (Fo2 + 2Fc2)/3		 w = 1/[σ2(Fo2) + (0.078P)2 + 27.27P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å−3)0.64, −0.340.66, −0.893.60, −3.70

Computer programs: SMART (Bruker, 2001), COLLECT, (Hooft, 1998), SAINT (Bruker, 2001), DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL and local programs.

Selected geometric parameters (Å, º) for (I) top
Co1—N12.1486 (19)Co1—N42.1400 (19)
Co1—N22.1679 (19)Co1—N52.1454 (19)
Co1—N32.1187 (19)Co1—N62.1367 (19)
N1—Co1—N284.82 (7)N2—Co1—N695.46 (7)
N1—Co1—N385.63 (7)N3—Co1—N4178.54 (8)
N1—Co1—N495.19 (7)N3—Co1—N596.10 (7)
N1—Co1—N594.28 (7)N3—Co1—N693.68 (7)
N1—Co1—N6179.23 (8)N4—Co1—N585.06 (7)
N2—Co1—N385.11 (7)N4—Co1—N685.50 (7)
N2—Co1—N493.75 (7)N5—Co1—N685.45 (7)
N2—Co1—N5178.44 (8)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.80 (2)3.07 (2)3.8337 (19)159 (2)
N2—H2A···I10.78 (2)3.09 (2)3.8207 (19)157 (2)
N3—H3A···I10.81 (2)2.95 (2)3.7302 (19)163 (2)
N4—H4A···I20.80 (2)2.97 (2)3.7413 (19)165 (2)
N5—H5A···I20.81 (2)3.09 (2)3.8461 (19)156 (2)
N6—H6A···I20.79 (2)3.09 (2)3.831 (2)157 (2)
N7—H7A···I10.84 (2)3.16 (2)3.987 (2)172 (2)
Selected geometric parameters (Å, º) for (II) top
Fe1—N12.078 (2)
N1—Fe1—N1i86.21 (9)
Symmetry code: (i) z−1/2, −x+1/2, −y+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl10.82 (3)2.50 (3)3.272 (2)157 (3)
Selected geometric parameters (Å, º) for (III) top
Pt1—N12.046 (5)Pt1—I12.6470 (5)
Pt1—N22.038 (5)
N1—Pt1—N287.8 (2)N2—Pt1—I187.89 (16)
N1—Pt1—I187.39 (15)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl30.77 (3)2.46 (4)3.210 (5)165 (8)
N2—H2A···Cl30.78 (3)2.47 (7)3.242 (5)168 (8)
C3—H3···Cl3i0.952.933.567 (7)126
C4—H4···Cl3i0.952.993.601 (9)123
C10—H10···Cl3ii0.952.763.626 (8)153
C14—H14···Cl30.952.843.716 (8)154
C21—H21···Cl3iii0.952.823.546 (7)134
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x−1/2, y−1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2.
 

Acknowledgements

The authors acknowledge the EPSRC for the provision of a studentship (KEH), the EPSRC National Crystallographic Service at the University of Southampton, England, for the collection of data for (II[link]) and Johnson Matthey for loans of precious metals.

References

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 1| January 2005| Pages m34-m39
doi:10.1107/S0108270104029051
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