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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 6| June 2005| Pages o411-o413
doi:10.1107/S010827010501437X

1λ4,4λ4,8λ4,11λ4-Tetra­thia­cyclo­tetra­decane-1,4,7,10-tetra­yl­idene­tetra­aminium tetra­kis­(2,4,6-tri­methylbenzene­sulfonate)

CROSSMARK_Color_square_no_text.svg
Sophie H. Dale,a Mark R. J. Elsegood,b Liam M. Gilby,b Kathryn E. Holmesb and Paul F. Kellyb*

aSchool of Natural Sciences, University of Newcastle-upon-Tyne, Newcastle-upon-Tyne NE1 7RU, England, and bChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, England
*Correspondence e-mail: p.f.kelly@lboro.ac.uk

(Received 24 March 2005; accepted 5 May 2005; online 31 May 2005)

Investigations of the reactivity of the thio-crown [14]aneS4 (1,4,8,11-tetra­thia­cyclo­tetra­decane) towards the aminating agent o-mesitylsulfonyl­hydroxylamine have lead to the crystallization of 1λ4,4λ4,8λ4,11λ4-tetra­thia­cyclo­tetra­decane-1,4,7,10-tetra­ylidenetetra­aminium tetra­kis­(2,4,6-trimethyl­benzene­sulfonate), C10H28N4S44+·4C9H11O3S−. The compound crystallizes in a centrosymmetric space group, with half a formula unit in the asymmetric unit. All S atoms within the cationic component are aminated, with the four NH2 substituents arranged in pairs on neighbouring S atoms on opposite faces of the crown. The macrocyclic cation in the compound forms hydrogen bonds with the 2,4,6-trimethyl­benzene­sulfonate anions to create chains, which are further linked into thick two-dimensional sheets.

Comment

As part of an ongoing investigation into the chemistry of novel sulfimide systems, we have recently investigated the reactivity of the thio-crown [9]aneS3 (1,4,7-trithia­cyclo­nonane) towards species capable of forming S—N bonds via reaction at thio­ether units (Elsegood et al., 2002[Elsegood, M. R. J., Holmes, K. E., Gilby, L. M. & Kelly, P. F. (2002). Can. J. Chem. 18, 1410-1414.]; Aucott et al., 2004[Aucott, S. M., Bailey, M. R., Elsegood, M. R. J., Gilby, L. M., Holmes, K. E., Kelly, P. F., Papageorgiou, M. J. & Pedrón-Haba, S. (2004). New J. Chem. pp. 959-966.]). In the case of the aminating agent MSH (o-mesitylsulfonyl­hydroxylamine), reaction on an equimolar scale generated a salt of the protonated sulfimide cation {[9]aneS2S(NH2)}+ (with the [Me3C6H2SO3]− anion which results from all MSH reactions; Elsegood et al., 2002[Elsegood, M. R. J., Holmes, K. E., Gilby, L. M. & Kelly, P. F. (2002). Can. J. Chem. 18, 1410-1414.]). While further addition of one equivalent of MSH resulted in {[9-ane]SS(NH2)S(NH2)}2+, addition of a third equivalent generated the {[9-ane]S(NH2)S2(μ-N)}2+ cation (in which an N atom bridges two of the S atoms), rather than the expected trisulfimidium cation {[9-ane][S(NH2)]3}3+. The reason for the latter reaction is not clear, although one possibility is that a combination of high charge and small ring size within the latter putative species destabilizes it relative to the transannularly bridged compound.

In order to gain some insight into the above observations, we have now investigated analogous reactions of the larger crown species [14]aneS4 (1,4,8,11-tetrathiacyclotetradecane), observing the products formed when an excess of MSH is added. In this case, the fully aminated title product, [{[14]ane[S(NH2)]4}4+][C6Me3SO3−]4, (I)[link], results and its crystal structure is presented here.

[Scheme 1]

Compound (I)[link] crystallizes in a centrosymmetric space group with half a formula unit in the asymmetric unit (Fig. 1[link] and Table 1[link]). The macrocyle is substituted with one NH2 group on each of the S atoms in the ring and lies on an inversion centre. The NH2 substituents are arranged in pairs on neighbouring S atoms on opposite faces of the crown. The two unique 2,4,6-trimethyl­benzene­sulfonate anions are almost perpendicular with respect to each other [the dihedral angle between the two aromatic rings is 89.4 (2)°]. The macrocyle was found to be disordered and was refined with atoms C4, N2 and C5 (and their associated H atoms) modelled over two sets of positions [major refined occupancy 59.5 (7)%]. The SO3- groups of the two unique anions were also found to be disordered. The SO3- group containing atom S4 was modelled over two sets of positions with a coincident S atom. The major refined occupancy of this group was found to be equal to that of the cation (due to hydrogen bonding between the disordered portion of the cation and this anion) and, therefore, the two occupancies were refined collectively. The SO3- group containing atom S3 was modelled in a similar manner, with a major refined occupancy of 72 (3)%. In the following analysis of the geometry and hydrogen bonding of compound (I)[link], only the major component of the disorder model will be discussed.

The NH2 groups in (I)[link] are involved in N—H⋯O hydrogen bonds with the SO3- groups of the 2,4,6-trimethyl­benzene­sulfonate anions (Table 2[link]). Hydrogen bonds utilizing the NH2 group containing atom N1 and the SO3- group containing atom S4 create a 12-membered hydrogen-bonded ring motif containing four N—H donor groups and four O acceptors, giving an R44(12) graph-set motif (Fig. 2[link]; Etter, 1990[Etter, M. C. (1990). Acc. Chem. Res. 23, 120-126.]; Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]; Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). A recent study of supramol­ecular synthons in organic sulfonate structures in the Cambridge Structural Database (Haynes et al., 2004[Haynes, D. A., Chisholm, J. A., Jones, W. & Motherwell, W. D. S. (2004). CrystEngComm, 6, 584-588.]) has highlighted this hydrogen-bonded ring motif as the most common in sulfonate compounds containing NH donors, occurring in 17.85% of all sulfonate–NH donor crystal structures. The R44(12) motifs link alternating cations and anions (containing atoms S4, O4, O5 and O6) into chains. Hydrogen bonds utilizing the NH2 group containing atom N2 link these chains into a thick two-dimensional sheet arrangement, in which the crown cations are sandwiched between two layers of anions. The sheets propagate in the crystallographic ab plane (Fig. 3[link]). The O atoms of the sulfonate groups also have close contacts with the S atoms of the crown cation, with O⋯S distances in the range 3.18 (3)–3.674 (13) Å.

The results of a search of the Cambridge Structural Database (CSD, Version 5.26, February 2005 update; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]; Fletcher et al., 1996[Fletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746-749.]) for tetrasubstituted [14]aneS4 crown species, similar to the cationic component of compound (I)[link], are shown in Table 3[link]. There are very few suitable entries in the CSD which are not metal-coordinated species, and so all entries have been included in the analysis. The C—C and S—C bond lengths of the cationic species in (I)[link] show good simil­arities to those shown in Table 3[link], although it should be noted that restraints have been applied to the bond lengths of the cation due to the disorder present.

It is not immediately obvious why there should be the contrasting reactivity of an excess of MSH towards trithia and tetrathia crowns. On the basis of the trithia crown reactions, one might have expected the fully substituted ring in (I)[link] to rearrange (via loss of ammonium ions) to lower-charged N-bridged systems analagous to the {[9-ane]S(NH2)S2(μ-N)}2+ cation noted above. That it does not presumably indicates that there are many factors to consider within the energetics of such systems. Further investigations into such effects are underway.

[Figure 1]
Figure 1
A view of (I)[link], showing the atom-labelling scheme. H atoms (except for NH) and the minor component of the disorder model have been omitted for clarity. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) 1 − x, −y, 1 − z.]
[Figure 2]
Figure 2
The hydrogen-bonded chains of (I)[link], formed from cations and symmetry equivalents of the anion containing atom S4, viewed along the [[\overline{1}]10] direction. The minor component of the disorder model, the anion containing atom S3 and H atoms except for NH have been omitted for clarity. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) 1 − x, −y, 1 − z; (ii) 2 − x, 1 − y, 1 − z.]
[Figure 3]
Figure 3
A packing plot of (I)[link], viewed along the crystallographic a axis (b axis horizontal). The minor component of the disorder model and H atoms except for NH have been omitted for clarity. Hydrogen bonds are shown as dashed lines.

Experimental

The title compound was prepared by addition of an excess (i.e. more than four molar equivalents) of MSH to [14]aneS4, in a manner analogous to previously published reactions of [9]aneS3 (Elsegood et al., 2002[Elsegood, M. R. J., Holmes, K. E., Gilby, L. M. & Kelly, P. F. (2002). Can. J. Chem. 18, 1410-1414.]; Aucott et al., 2004[Aucott, S. M., Bailey, M. R., Elsegood, M. R. J., Gilby, L. M., Holmes, K. E., Kelly, P. F., Papageorgiou, M. J. & Pedrón-Haba, S. (2004). New J. Chem. pp. 959-966.]). Compound (I)[link] was crystallized by slow diffusion of diethyl ether into an acetonitrile solution of the compound.

Crystal data

  • C10H28N4S44+·4C9H11O3S−

  • Mr = 1129.56

  • Triclinic, [P \overline 1]

  • a = 8.750 (2) Å

  • b = 11.566 (3) Å

  • c = 14.383 (4) Å

  • α = 98.540 (4)°

  • β = 104.135 (4)°

  • γ = 99.119 (4)°

  • V = 1366.8 (6) Å3

  • Z = 1

  • Dx = 1.372 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1398 reflections

  • θ = 2.5–26.7°

  • μ = 0.39 mm−1

  • T = 150 (2) K

  • Needle, colourless

  • 0.09 × 0.02 × 0.01 mm
Data collection

  • Bruker SMART 1000 CCD diffractometer

  • ω rotation scans with narrow frames

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.945, Tmax = 0.996

  • 10 556 measured reflections

  • 5312 independent reflections

  • 2257 reflections with I > 2σ(I)

  • Rint = 0.075

  • θmax = 26.0°

  • h = −10 → 10

  • k = −13 → 14

  • l = −17 → 17
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.077

  • wR(F2) = 0.233

  • S = 1.01

  • 5312 reflections

  • 424 parameters

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

  • w = 1/[σ2(Fo2) + (0.0916P)2 + 1.6284P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.56 e Å−3

  • Extinction correction: SHELXTL (Sheldrick, 2000[Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.])

  • Extinction coefficient: 0.016 (3)

Table 1
Selected geometric parameters (Å)[link]

C1—C5i 1.550 (8)
C1—C2 1.551 (7)
C3—C4 1.554 (9)
S1—N1 1.676 (6)
S1—C2 1.782 (5)
S1—C3 1.786 (5)
S2—N2 1.705 (6)
S2—C4 1.770 (6)
S2—C5 1.772 (5)
Symmetry code: (i) 1-x, -y, 1-z.

Table 2
Hydrogen-bond geometry (Å, °)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯O4ii 0.89 (2) 2.40 (6) 3.090 (12) 135 (6)
N1—H1A⋯O4Xii 0.89 (2) 2.02 (6) 2.683 (12) 130 (6)
N1—H1B⋯O5 0.90 (2) 2.01 (2) 2.905 (11) 177 (7)
N1—H1B⋯O5X 0.90 (2) 1.85 (4) 2.681 (9) 154 (7)
N2—H2A⋯O2 0.90 (2) 2.25 (10) 2.969 (19) 136 (12)
N2—H2B⋯O4iii 0.89 (2) 2.19 (8) 2.897 (15) 136 (10)
N2X—H2C⋯O1Xi 0.90 (2) 2.39 (13) 3.10 (4) 136 (15)
Symmetry codes: (i) 1-x, -y, 1-z; (ii) 2-x, 1-y, 1-z; (iii) 1-x, 1-y, 1-z.

Table 3
S—C and C—C bond lengths (Å) for tetrasubstituted [14]aneS4 crown species, obtained from a search of the CSD (Version 5.26, February 2005 update; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.])

The ranges of the S—C and C—C bond lengths are shown, with the average values in parentheses. The labels Ethyl and Propyl are used to distinguish between the two- and three-carbon bridges in the crown molecule. The statistics are taken from a small population of six structures containing tetra-substituted crowns.
Bridge S—C C—C
Ethyl 1.808–1.825 [1.818 (6)] 1.500–1.545 [1.523 (16)]
Propyl 1.804–1.818 [1.813 (4)] 1.499–1.533 [1.518 (13)]

Aromatic H (C—H distance = 0.95 Å) and methyl H (C—H distance = 0.98 Å) atoms were placed in geometric positions using a riding model. NH H atoms were located in a difference Fourier map and refined using restraints on the N—H bond length [target value 0.90 (2) Å] and 1,3-distances (SHELXTL SADI restraint; Sheldrick, 2000[Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.]). Uiso(H) values were set at 1.2Ueq(C,N) for aryl and NH H atoms, and 1.5Ueq(C) for methyl H atoms. The data set was truncated at 2θ = 52°, as only statistically insignificant data were present above this limit. Low bond precision and a low observed/unique ratio have resulted from poor crystal quality and weak data at higher angles. The macrocycle and both unique SO3- groups were found to be disordered. Atoms C4, C5, N2, H2A and H2B of the macrocyle and atoms O4, O5 and O6 of one anion were modelled over two sets of positions with a refined major occupancy of 59.5 (7)%. Atoms O1, O2 and O3 of the second anion were modelled over two sets of positions with a refined major occupancy of 72 (3)%. This second refined occupancy was less precisely determined due to fewer atoms within the disorder model. Restraints were applied to the S—C, C—C and S—N bond lengths of the macrocycle, and S—O bond lengths were refined to be approximately 1.44 Å (a CSD search for S—O bond lengths in aryl­sulfonates gave a mean of 1.44 Å from 964 hits). Restraints were applied to the anisotropic displacement parameters of all S and O atoms.

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; 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. DOI: 10.1107/S010827010501437X/sq1209sup1.cif

Structure factors: contains datablock . DOI: 10.1107/S010827010501437X/sq1209Isup2.hkl


Comment top

As part of an ongoing investigation into the chemistry of novel sulfimide systems, we have recently investigated the reactivity of the thio-crown [9]aneS3 (1,4,7-trithiacyclononane) towards species capable of forming S—N bonds via reaction at thioether units (Elsegood et al., 2002; Aucott et al., 2004). In the case of the aminating agent MSH (o-mesitylsulfonylhydroxylamine), reaction on an equimolar scale generated a salt of the protonated sulfimide cation {[9]aneS2S(NH2)}+ (with the [Me3C6H2SO3]− anion which results from all MSH reactions; Elsegood et al., 2002). While further addition of one equivalent of MSH resulted in {[9-ane]SS(NH2)S(NH2)}2+, addition of a third equivalent generated the {[9-ane]S(NH2)S2(µ-N)}2+ cation (in which an N atom bridges two of the S atoms), rather than the expected trisulfimidium cation {[9-ane][S(NH2)]3}3+. The reason for the latter reaction is not clear, although one possibility is that a combination of high charge and small ring size within the latter putative species destabilizes it relative to the transannularly bridged compound.

In order to gain some insight into the above observations, we have now investigated analogous reactions of the larger crown species [14]aneS4, observing the products formed when an excess of MSH is added. In this case, the fully aminated title product, [{[14]ane[S(NH2)]4}4+][C6Me3SO3]4, (I), results and its crystal structure is presented here.

Compound (I) crystallizes in a centrosymmetric space group with half of a formula unit in the asymmetric unit (Fig. 1 and Table 1). The macrocyle is substituted with one NH2 group on each of the S atoms in the ring and lies on an inversion centre. The NH2 substituents are arranged in pairs on neighbouring S atoms on opposite faces of the crown. The two unique 2,4,6-trimethylbenzenesulfonate anions are almost perpendicular with respect to each other [the dihedral angle between the two aromatic rings is 89.4 (2)°]. The macrocyle was found to be disordered and was refined with atoms C4, N2 and C5 (and their associated H atoms) modelled over two sets of positions [major refined occupancy 59.5 (7)%]. The SO3− groups of the two unique anions were also found to be disordered. The SO3− group containing atom S4 was modelled over two sets of positions with a coincident S atom. The major refined occupancy of this group was found to be equal to that of the cation (due to hydrogen bonding between the disordered portion of the cation and this anion) and, therefore, the two occupancies were refined collectively. The SO3− group containing atom S3 was modelled in a similar manner, with a major refined occupancy of 72 (3)%. In the following analysis of the geometry and hydrogen bonding of compound (I), only the major component of the disorder model will be discussed.

The NH2 groups in (I) are involved in N—H···O hydrogen bonds with the SO3− groups of the 2,4,6-trimethylbenzenesulfonate anions (Table 2). Hydrogen bonds utilizing the NH2 group containing atom N1 and the SO3− group containing atom S4 create a 12-membered hydrogen-bonded ring motif, containing four N—H donor groups and four O acceptors, giving an R44(12) graph-set motif (Fig. 2; Etter, 1990; Etter et al., 1990; Bernstein et al., 1995). A recent study of supramolecular synthons in organic sulfonate structures in the Cambridge Structural Database (Haynes et al., 2004) has highlighted this hydrogen-bonded ring motif as the most common in sulfonate compounds containing NH donors, occurring in 17.85% of all sulfonate–NH donor crystal structures. The R44(12) motifs link alternating cations and anions (containing atoms S4, O4, O5 and O6) into chains. Hydrogen bonds utilizing the NH2 group containing atom N2 link these chains into a thick two-dimensional sheet arrangement, in which the crown cations are sandwiched between two layers of anions. The sheets propagate in the crystallographic ab plane (Fig. 3). The O atoms of the sulfonate groups also have close contacts with the S atoms of the crown cation, with O···S distances in the range 3.18 (3)–3.674 (13) Å.

The results of a search of the Cambridge Structural Database (CSD, Version 5.26, February 2005 update; Allen, 2002; Fletcher et al., 1996) for tetra-substituted [14]aneS4 crown species, similar to the cationic component of compound (I), are shown in Table 3. There are very few suitable entries in the CSD which are not metal-coordinated species, and so all entries have been included in the analysis. The C—C and S—C bond lengths of the cationic species in (I) show good similarities to those shown in Table 3, although it should be noted that restraints have been applied to the bond lengths of the cation due to the disorder present.

It is not immediately obvious why there should be the contrasting reactivity of an excess of MSH towards tri-thia and tetra-thia crowns. On the basis of the tri-thia crown reactions, one might have expected the fully substituted ring in (I) to rearrange (via loss of aminium ions) to lower-charged N-bridged systems analagous to the {[9-ane]S(NH2)S2(µ-N)}2+ cation noted above. That it does not presumably indicates that there are many factors to consider within the energetics of such systems. Further investigations into such effects are underway.

Experimental top

The title compound was prepared by addition of an excess (i.e. > 4 molar equivalents) of MSH to [14]aneS4, in a manner analogous to previously published reactions of [9]aneS3 (Elsegood et al., 2002; Aucott et al., 2004). Compound (I) was crystallized by slow diffusion of diethyl ether into an acetonitrile solution of the compound.

Refinement top

Aromatic H (C—H distance = 0.95 Å) and methyl H (C—H distance = 0.98 Å) atoms were placed in geometric positions using a riding model. NH H atoms were located in a difference Fourier map and refined using restraints on the N—H bond length [target value 0.90 (2) Å] and 1,3-distances (SHEXTL SADI restraint; Sheldrick, 2000). Uiso(H) values were set at 1.2Ueq(C,N) for aryl and NH H atoms, and 1.5Ueq(C) for methyl H atoms. The dataset was truncated at 2θ = 52°, as only statistically insignificant data were present above this limit. Low bond precision and a low observed/unique ratio have resulted from poor crystal quality and weak data at higher angle. The macrocycle and both unique SO3− groups were found to be disordered. Atoms C4, C5, N2, H2A and H2B of the macrocyle and atoms O4, O5 and O6 of one anion were modelled over two sets of positions with a refined major occupancy of 59.5 (7)%. Atoms O1, O2 and O3 of the second anion were modelled over two sets of positions with a refined major occupancy of 72 (3)%. This second refined occupancy was less precisely determined due to fewer atoms within the disorder model. Restraints were applied to the S—C, C—C and S—N bond lengths of the macrocycle, and S—O bond lengths were refined to be approximately 1.44 Å (a CSD search for S—O bond lengths in arylsulfonates gave a mean of 1.44 Å from 964 hits). Restraints were applied to the anisotropic displacement parameters of all S and O atoms.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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 (I), showing the atom-labelling scheme. H atoms (except for NH) and the minor component of the disorder model have been omitted for clarity. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) 1 − x, −y, 1 − z.]
[Figure 2] Fig. 2. The hydrogen-bonded chains of (I), formed from cations and symmetry equivalents of the anion containing S4, viewed along the [110] direction. The minor component of the disorder model, the anion containing S3, and H atoms except for NH have been omitted for clarity. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) 1 − x, −y, 1 − z; (ii) 2 − x, 1 − y, 1 − z.]
[Figure 3] Fig. 3. A packing plot of (I), viewed along the crystallographic a axis (b axis horizontal). The minor component of the disorder model and H atoms except for NH have been omitted for clarity. Hydrogen bonds are shown as dashed lines.
1λ4,4λ4,8λ4,11λ4-Tetrathiacyclotetradecane-1,4,7,10- tetraylidenetetraaminium tetrakis(2,4,6-trimethylbenzenesulfonate) top
Crystal data top
C10H28N4S44+·4C9H11O3S−Z = 1
Mr = 1129.56F(000) = 600
Triclinic, P1Dx = 1.372 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.750 (2) ÅCell parameters from 1398 reflections
b = 11.566 (3) Åθ = 2.5–26.7°
c = 14.383 (4) ŵ = 0.39 mm−1
α = 98.540 (4)°T = 150 K
β = 104.135 (4)°Needle, colourless
γ = 99.119 (4)°0.09 × 0.02 × 0.01 mm
V = 1366.8 (6) Å3
Data collection top
Bruker SMART 1000 CCD
diffractometer		5312 independent reflections
Radiation source: sealed tube2257 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.075
ω rotation with narrow frames scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −10→10
Tmin = 0.945, Tmax = 0.996k = −13→14
10556 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: Geom except NH coords refined with restraints
R[F2 > 2σ(F2)] = 0.077H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.233 w = 1/[σ2(Fo2) + (0.0916P)2 + 1.6284P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
5312 reflectionsΔρmax = 0.56 e Å−3
424 parametersΔρmin = −0.56 e Å−3
226 restraintsExtinction correction: SHELXTL (Sheldrick, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.016 (3)
Crystal data top
C10H28N4S44+·4C9H11O3S−γ = 99.119 (4)°
Mr = 1129.56V = 1366.8 (6) Å3
Triclinic, P1Z = 1
a = 8.750 (2) ÅMo Kα radiation
b = 11.566 (3) ŵ = 0.39 mm−1
c = 14.383 (4) ÅT = 150 K
α = 98.540 (4)°0.09 × 0.02 × 0.01 mm
β = 104.135 (4)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		5312 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2257 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.996Rint = 0.075
10556 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.077226 restraints
wR(F2) = 0.233H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.56 e Å−3
5312 reflectionsΔρmin = −0.56 e Å−3
424 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.7133 (10)0.0279 (6)0.3117 (6)0.057 (2)
H1C0.73370.03460.24780.069*0.595 (7)
H1D0.81790.03220.35940.069*0.595 (7)
H1E0.81360.05990.29580.069*0.405 (7)
H1F0.6373−0.02100.25070.069*0.405 (7)
C20.6388 (8)0.1342 (6)0.3456 (4)0.048 (2)
H2E0.52000.10940.32520.058*
H2F0.66850.20090.31340.058*
S10.7055 (2)0.18456 (17)0.47483 (14)0.0435 (5)
N10.8901 (7)0.2658 (6)0.4919 (5)0.0516 (17)
H1A0.947 (8)0.275 (6)0.554 (2)0.062*
H1B0.881 (9)0.334 (4)0.471 (5)0.062*
C30.5712 (8)0.2795 (6)0.4981 (5)0.049 (2)
H3A0.62100.36360.50150.059*0.595 (7)
H3B0.47010.25780.44440.059*0.595 (7)
H3C0.62100.33250.56280.059*0.405 (7)
H3D0.55830.33060.44840.059*0.405 (7)
S20.4231 (3)0.11895 (18)0.58369 (15)0.0527 (6)
N20.2396 (10)0.1364 (11)0.5195 (7)0.054 (3)0.595 (7)
H2A0.180 (12)0.062 (4)0.506 (10)0.065*0.595 (7)
H2B0.184 (11)0.193 (6)0.532 (9)0.065*0.595 (7)
C40.5343 (14)0.2650 (6)0.5966 (7)0.048 (4)0.595 (7)
H4A0.47150.32450.61460.057*0.595 (7)
H4B0.63610.27860.64900.057*0.595 (7)
C50.3976 (14)0.0945 (9)0.6982 (5)0.042 (3)0.595 (7)
H5A0.50400.09760.74360.050*0.595 (7)
H5B0.35030.15890.72640.050*0.595 (7)
N2X0.5212 (16)0.2155 (12)0.6912 (8)0.049 (5)0.405 (7)
H2C0.620 (9)0.218 (13)0.730 (11)0.059*0.405 (7)
H2D0.493 (17)0.288 (7)0.699 (12)0.059*0.405 (7)
C4X0.4028 (13)0.2138 (12)0.4974 (10)0.041 (5)0.405 (7)
H4C0.34630.16610.43130.050*0.405 (7)
H4D0.33810.27270.51400.050*0.405 (7)
C5X0.2472 (11)0.0551 (14)0.6128 (11)0.049 (5)0.405 (7)
H5C0.19940.11950.64050.059*0.405 (7)
H5D0.16730.00810.55240.059*0.405 (7)
C6−0.0061 (8)−0.0571 (6)0.1903 (5)0.0319 (16)
C7−0.1353 (8)−0.1522 (6)0.1302 (5)0.0362 (17)
C8−0.2400 (8)−0.1258 (6)0.0485 (5)0.0391 (18)
H8−0.3232−0.18850.00720.047*
C9−0.2286 (8)−0.0152 (6)0.0252 (5)0.0370 (17)
C10−0.1067 (8)0.0772 (7)0.0859 (5)0.0417 (18)
H10−0.09790.15490.07120.050*
C110.0027 (8)0.0578 (6)0.1681 (5)0.0390 (17)
C12−0.1674 (9)−0.2770 (6)0.1504 (6)0.0466 (19)
H12A−0.2693−0.32240.10520.070*
H12B−0.1739−0.27280.21790.070*
H12C−0.0797−0.31670.14130.070*
C13−0.3466 (9)0.0080 (7)−0.0648 (5)0.051 (2)
H13A−0.28950.0249−0.11350.076*
H13B−0.39270.0766−0.04550.076*
H13C−0.4330−0.0627−0.09290.076*
C140.1262 (9)0.1682 (7)0.2307 (7)0.061 (2)
H14A0.11890.17800.29830.092*
H14B0.10390.23920.20450.092*
H14C0.23480.15800.22940.092*
S30.1282 (2)−0.08465 (16)0.29527 (12)0.0377 (5)
O10.1551 (16)−0.2038 (6)0.2688 (10)0.052 (2)0.72 (3)
O20.0467 (13)−0.0767 (16)0.3716 (6)0.046 (2)0.72 (3)
O30.2758 (9)0.0034 (9)0.3207 (10)0.047 (2)0.72 (3)
O1X0.120 (4)−0.2100 (7)0.292 (2)0.044 (4)0.28 (3)
O2X0.080 (4)−0.028 (3)0.3762 (14)0.047 (3)0.28 (3)
O3X0.2844 (18)−0.023 (3)0.295 (2)0.043 (3)0.28 (3)
C150.7477 (10)0.4595 (6)0.2276 (6)0.0464 (19)
C160.9016 (9)0.4532 (6)0.2148 (5)0.0435 (19)
C170.9139 (9)0.4111 (6)0.1211 (6)0.0468 (19)
H171.01720.40580.11270.056*
C180.7806 (10)0.3767 (6)0.0397 (6)0.0464 (19)
C190.6291 (9)0.3873 (6)0.0536 (5)0.0439 (19)
H190.53710.3661−0.00140.053*
C200.6099 (9)0.4274 (6)0.1449 (5)0.0420 (18)
C211.0584 (10)0.4939 (8)0.2960 (7)0.068 (3)
H21A1.14600.46750.27280.102*
H21B1.04780.45910.35280.102*
H21C1.08250.58120.31460.102*
C220.7969 (11)0.3339 (8)−0.0612 (6)0.060 (2)
H22A0.83070.4029−0.08900.091*
H22B0.69310.2875−0.10330.091*
H22C0.87770.2836−0.05680.091*
C230.4402 (10)0.4354 (8)0.1492 (6)0.062 (2)
H23A0.36690.41210.08310.093*
H23B0.43800.51750.17710.093*
H23C0.40620.38160.19030.093*
S40.7326 (3)0.52036 (18)0.34695 (14)0.0540 (6)
O40.7774 (13)0.6468 (4)0.3568 (10)0.043 (2)0.595 (7)
O50.8581 (11)0.4817 (9)0.4147 (7)0.070 (2)0.595 (7)
O60.5787 (8)0.4714 (11)0.3578 (8)0.076 (3)0.595 (7)
O4X0.8243 (16)0.6401 (6)0.3776 (15)0.035 (3)0.405 (7)
O5X0.768 (2)0.4351 (11)0.4073 (10)0.069 (3)0.405 (7)
O6X0.5648 (8)0.5275 (13)0.3348 (11)0.064 (3)0.405 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.062 (6)0.063 (6)0.062 (5)0.014 (5)0.043 (5)0.014 (5)
C20.039 (5)0.051 (5)0.052 (5)0.010 (4)0.013 (4)0.003 (4)
S10.0431 (11)0.0472 (12)0.0471 (12)0.0170 (9)0.0185 (9)0.0119 (9)
N10.038 (4)0.072 (5)0.044 (4)0.016 (4)0.008 (3)0.011 (4)
C30.050 (5)0.053 (5)0.052 (5)0.023 (4)0.020 (4)0.013 (4)
S20.0716 (15)0.0505 (13)0.0543 (13)0.0298 (11)0.0390 (11)0.0118 (10)
N20.038 (7)0.073 (8)0.039 (6)0.032 (6)−0.012 (5)−0.011 (6)
C40.053 (8)0.055 (9)0.039 (8)0.025 (7)0.013 (6)0.004 (6)
C50.050 (8)0.057 (8)0.026 (6)0.025 (7)0.018 (6)0.007 (6)
N2X0.045 (10)0.055 (11)0.048 (10)0.029 (8)0.009 (8)0.002 (8)
C4X0.042 (11)0.042 (11)0.043 (11)0.024 (9)0.009 (9)0.003 (9)
C5X0.039 (11)0.050 (12)0.044 (12)0.007 (9)0.001 (9)−0.013 (10)
C60.030 (4)0.041 (4)0.026 (4)0.009 (3)0.012 (3)0.003 (3)
C70.037 (4)0.038 (4)0.036 (4)0.015 (3)0.012 (3)0.005 (3)
C80.028 (4)0.047 (5)0.038 (4)0.003 (3)0.005 (3)0.009 (4)
C90.035 (4)0.043 (4)0.035 (4)0.012 (3)0.010 (3)0.013 (3)
C100.040 (4)0.043 (4)0.043 (4)0.015 (4)0.008 (4)0.013 (4)
C110.037 (4)0.036 (4)0.044 (4)0.015 (3)0.005 (3)0.012 (3)
C120.039 (4)0.048 (5)0.046 (5)0.008 (4)−0.001 (4)0.014 (4)
C130.041 (5)0.067 (6)0.044 (5)0.014 (4)0.003 (4)0.021 (4)
C140.051 (5)0.041 (5)0.076 (6)0.009 (4)−0.007 (4)0.005 (4)
S30.0355 (10)0.0448 (11)0.0309 (10)0.0156 (8)0.0035 (8)0.0030 (8)
O10.056 (5)0.050 (3)0.044 (5)0.028 (3)−0.004 (3)0.004 (3)
O20.041 (4)0.069 (6)0.026 (3)0.012 (4)0.005 (3)0.008 (4)
O30.033 (3)0.061 (4)0.041 (5)0.011 (3)0.005 (3)−0.001 (4)
O1X0.051 (7)0.048 (3)0.032 (7)0.016 (4)−0.001 (6)0.014 (5)
O2X0.040 (6)0.067 (7)0.031 (5)0.017 (6)0.005 (5)0.000 (6)
O3X0.035 (5)0.054 (6)0.036 (7)0.010 (5)0.004 (5)0.000 (6)
C150.059 (5)0.034 (4)0.046 (5)−0.001 (4)0.020 (4)0.007 (4)
C160.045 (5)0.033 (4)0.046 (5)0.000 (3)0.006 (4)0.003 (4)
C170.041 (5)0.040 (4)0.060 (5)0.009 (4)0.014 (4)0.012 (4)
C180.058 (5)0.036 (4)0.046 (5)0.008 (4)0.019 (4)0.005 (4)
C190.046 (5)0.041 (4)0.040 (4)−0.001 (4)0.013 (4)0.000 (4)
C200.046 (5)0.034 (4)0.047 (5)0.006 (3)0.017 (4)0.007 (3)
C210.049 (5)0.064 (6)0.074 (6)−0.008 (4)−0.007 (5)0.020 (5)
C220.084 (7)0.060 (5)0.044 (5)0.019 (5)0.029 (5)0.006 (4)
C230.052 (5)0.077 (6)0.063 (6)0.016 (5)0.026 (4)0.013 (5)
S40.0747 (15)0.0468 (11)0.0377 (11)0.0019 (10)0.0192 (10)0.0043 (9)
O40.053 (6)0.043 (2)0.041 (6)0.016 (3)0.023 (4)0.006 (3)
O50.110 (5)0.051 (5)0.050 (4)0.018 (4)0.019 (4)0.019 (4)
O60.094 (3)0.087 (6)0.041 (5)−0.024 (4)0.031 (4)0.016 (5)
O4X0.037 (5)0.032 (3)0.042 (7)0.023 (3)0.007 (5)0.012 (4)
O5X0.113 (7)0.039 (5)0.056 (5)−0.009 (5)0.038 (6)0.017 (4)
O6X0.067 (3)0.081 (7)0.039 (6)−0.020 (4)0.030 (5)0.005 (5)
Geometric parameters (Å, º) top
C1—C5i1.550 (8)C9—C131.534 (9)
C1—C21.551 (7)C10—C111.400 (9)
C1—C5Xi1.566 (9)C10—H100.9500
C1—H1C0.9900C11—C141.535 (10)
C1—H1D0.9900C12—H12A0.9800
C1—H1E0.9900C12—H12B0.9800
C1—H1F0.9900C12—H12C0.9800
C2—H2E0.9900C13—H13A0.9800
C2—H2F0.9900C13—H13B0.9800
C3—C4X1.544 (9)C13—H13C0.9800
C3—C41.554 (9)C14—H14A0.9800
C3—H3A0.9900C14—H14B0.9800
C3—H3B0.9900C14—H14C0.9800
C3—H3C0.9900S3—O1X1.434 (4)
C3—H3D0.9900S3—O3X1.437 (4)
C4—H4A0.9900S3—O2X1.439 (4)
C4—H4B0.9900S3—O31.442 (4)
C5—H5A0.9900S3—O11.445 (4)
C5—H5B0.9900S3—O21.448 (4)
S1—N11.676 (6)C15—C161.414 (10)
S1—C21.782 (5)C15—C201.425 (10)
S1—C31.786 (5)C15—S41.801 (8)
N1—H1A0.89 (2)C16—C171.399 (10)
N1—H1B0.90 (2)C16—C211.523 (10)
S2—N21.705 (6)C17—C181.392 (10)
S2—N2X1.706 (7)C17—H170.9500
S2—C5X1.770 (6)C18—C191.410 (10)
S2—C41.770 (6)C18—C221.511 (10)
S2—C4X1.771 (6)C19—C201.385 (10)
S2—C51.772 (5)C19—H190.9500
N2—H2A0.90 (2)C20—C231.518 (10)
N2—H2B0.89 (2)C21—H21A0.9800
N2X—H2C0.903 (15)C21—H21B0.9800
N2X—H2D0.91 (2)C21—H21C0.9800
C4X—H4C0.9900C22—H22A0.9800
C4X—H4D0.9900C22—H22B0.9800
C5X—H5C0.9900C22—H22C0.9800
C5X—H5D0.9900C23—H23A0.9800
C6—C111.406 (9)C23—H23B0.9800
C6—C71.443 (9)C23—H23C0.9800
C6—S31.777 (7)S4—O5X1.429 (4)
C7—C81.409 (9)S4—O41.429 (4)
C7—C121.510 (10)S4—O61.430 (4)
C8—C91.364 (9)S4—O4X1.431 (4)
C8—H80.9500S4—O6X1.453 (5)
C9—C101.396 (9)S4—O51.455 (4)
C5i—C1—C2112.3 (7)C8—C7—C12118.1 (6)
C2—C1—C5Xi115.3 (8)C6—C7—C12124.4 (6)
C5i—C1—H1C109.1C9—C8—C7123.7 (7)
C2—C1—H1C109.1C9—C8—H8118.1
C5Xi—C1—H1C135.2C7—C8—H8118.1
C5i—C1—H1D109.1C8—C9—C10118.2 (6)
C2—C1—H1D109.1C8—C9—C13121.3 (7)
C5Xi—C1—H1D52.7C10—C9—C13120.5 (6)
H1C—C1—H1D107.9C9—C10—C11121.5 (7)
C5i—C1—H1E138.7C9—C10—H10119.3
C2—C1—H1E108.5C11—C10—H10119.3
C5Xi—C1—H1E108.5C10—C11—C6120.2 (7)
H1C—C1—H1E49.6C10—C11—C14116.0 (6)
H1D—C1—H1E61.2C6—C11—C14123.8 (6)
C5i—C1—H1F53.8C7—C12—H12A109.5
C2—C1—H1F108.1C7—C12—H12B109.5
C5Xi—C1—H1F108.6H12A—C12—H12B109.5
H1C—C1—H1F60.0C7—C12—H12C109.5
H1D—C1—H1F142.7H12A—C12—H12C109.5
H1E—C1—H1F107.5H12B—C12—H12C109.5
C1—C2—S1112.0 (5)C9—C13—H13A109.5
C1—C2—H2E109.2C9—C13—H13B109.5
S1—C2—H2E109.2H13A—C13—H13B109.5
C1—C2—H2F109.2C9—C13—H13C109.5
S1—C2—H2F109.2H13A—C13—H13C109.5
H2E—C2—H2F107.9H13B—C13—H13C109.5
N1—S1—C2102.8 (4)C11—C14—H14A109.5
N1—S1—C3110.3 (4)C11—C14—H14B109.5
C2—S1—C3103.4 (3)H14A—C14—H14B109.5
S1—N1—H1A110 (5)C11—C14—H14C109.5
S1—N1—H1B109 (5)H14A—C14—H14C109.5
H1A—N1—H1B115 (6)H14B—C14—H14C109.5
C4X—C3—S1115.0 (7)O1X—S3—O3X112.3 (10)
C4—C3—S1109.0 (6)O1X—S3—O2X112.6 (9)
C4X—C3—H3A134.7O3X—S3—O2X110.4 (9)
C4—C3—H3A109.9O3—S3—O1111.5 (5)
S1—C3—H3A109.9O3—S3—O2112.0 (4)
C4X—C3—H3B50.6O1—S3—O2111.6 (5)
C4—C3—H3B109.9O1X—S3—C6111.7 (13)
S1—C3—H3B109.9O3X—S3—C6104.8 (13)
H3A—C3—H3B108.3O2X—S3—C6104.3 (11)
C4X—C3—H3C108.3O3—S3—C6108.8 (5)
C4—C3—H3C52.6O1—S3—C6106.4 (5)
S1—C3—H3C108.5O2—S3—C6106.2 (5)
H3A—C3—H3C60.7C16—C15—C20119.7 (7)
H3B—C3—H3C141.5C16—C15—S4118.9 (6)
C4X—C3—H3D108.6C20—C15—S4121.2 (6)
C4—C3—H3D141.6C17—C16—C15118.8 (7)
S1—C3—H3D108.6C17—C16—C21116.7 (7)
H3A—C3—H3D48.9C15—C16—C21124.4 (7)
H3B—C3—H3D62.9C18—C17—C16122.4 (7)
H3C—C3—H3D107.6C18—C17—H17118.8
N2X—S2—C5X100.2 (8)C16—C17—H17118.8
N2—S2—C499.1 (6)C17—C18—C19117.8 (7)
N2X—S2—C4X103.1 (8)C17—C18—C22121.6 (7)
C5X—S2—C4X117.8 (6)C19—C18—C22120.6 (7)
N2—S2—C5104.9 (6)C20—C19—C18122.1 (7)
C4—S2—C5110.0 (5)C20—C19—H19118.9
S2—N2—H2A102 (8)C18—C19—H19118.9
S2—N2—H2B129 (8)C19—C20—C15119.1 (7)
H2A—N2—H2B113 (7)C19—C20—C23116.6 (7)
C3—C4—S2109.0 (5)C15—C20—C23124.3 (7)
C3—C4—H4A109.9C16—C21—H21A109.5
S2—C4—H4A109.9C16—C21—H21B109.5
C3—C4—H4B109.9H21A—C21—H21B109.5
S2—C4—H4B109.9C16—C21—H21C109.5
H4A—C4—H4B108.3H21A—C21—H21C109.5
C1i—C5—S2111.6 (6)H21B—C21—H21C109.5
C1i—C5—H5A109.3C18—C22—H22A109.5
S2—C5—H5A109.3C18—C22—H22B109.5
C1i—C5—H5B109.3H22A—C22—H22B109.5
S2—C5—H5B109.3C18—C22—H22C109.5
H5A—C5—H5B108.0H22A—C22—H22C109.5
S2—N2X—H2C128 (10)H22B—C22—H22C109.5
S2—N2X—H2D116 (10)C20—C23—H23A109.5
H2C—N2X—H2D111 (7)C20—C23—H23B109.5
C3—C4X—S2109.4 (6)H23A—C23—H23B109.5
C3—C4X—H4C109.8C20—C23—H23C109.5
S2—C4X—H4C109.8H23A—C23—H23C109.5
C3—C4X—H4D109.8H23B—C23—H23C109.5
S2—C4X—H4D109.8O4—S4—O6118.6 (7)
H4C—C4X—H4D108.2O5X—S4—O4X119.0 (8)
C1i—C5X—S2110.9 (6)O5X—S4—O6X107.9 (7)
C1i—C5X—H5C109.5O4X—S4—O6X106.9 (7)
S2—C5X—H5C109.5O4—S4—O5108.1 (6)
C1i—C5X—H5D109.5O6—S4—O5109.6 (6)
S2—C5X—H5D109.5O5X—S4—C15107.1 (7)
H5C—C5X—H5D108.0O4—S4—C15104.9 (6)
C11—C6—C7118.8 (6)O6—S4—C15110.1 (5)
C11—C6—S3121.6 (5)O4X—S4—C15109.1 (10)
C7—C6—S3119.5 (5)O6X—S4—C15106.1 (7)
C8—C7—C6117.5 (6)O5—S4—C15104.7 (5)
C5i—C1—C2—S194.3 (7)C7—C6—S3—O3X139.2 (15)
C5Xi—C1—C2—S130.1 (9)C11—C6—S3—O2X70.5 (17)
C1—C2—S1—N178.3 (6)C7—C6—S3—O2X−104.7 (17)
C1—C2—S1—C3−166.9 (5)C11—C6—S3—O3−26.4 (9)
N1—S1—C3—C4X−172.7 (6)C7—C6—S3—O3158.4 (8)
C2—S1—C3—C4X78.0 (7)C11—C6—S3—O1−146.7 (9)
N1—S1—C3—C4−107.1 (6)C7—C6—S3—O138.1 (9)
C2—S1—C3—C4143.6 (5)C11—C6—S3—O294.4 (9)
S1—C3—C4—S2−66.8 (8)C7—C6—S3—O2−80.8 (9)
N2—S2—C4—C3−76.6 (8)C20—C15—C16—C17−2.4 (10)
C5—S2—C4—C3173.8 (7)S4—C15—C16—C17−177.1 (6)
N2—S2—C5—C1i68.8 (8)C20—C15—C16—C21175.2 (7)
C4—S2—C5—C1i174.5 (7)S4—C15—C16—C210.6 (10)
S1—C3—C4X—S256.7 (11)C15—C16—C17—C181.0 (11)
N2X—S2—C4X—C359.5 (11)C21—C16—C17—C18−176.8 (7)
C5X—S2—C4X—C3168.6 (9)C16—C17—C18—C191.0 (11)
N2X—S2—C5X—C1i−70.4 (11)C16—C17—C18—C22178.7 (7)
C4X—S2—C5X—C1i178.8 (9)C17—C18—C19—C20−1.6 (11)
C11—C6—C7—C83.9 (9)C22—C18—C19—C20−179.3 (7)
S3—C6—C7—C8179.2 (5)C18—C19—C20—C150.1 (11)
C11—C6—C7—C12−174.8 (6)C18—C19—C20—C23179.5 (7)
S3—C6—C7—C120.5 (9)C16—C15—C20—C191.9 (11)
C6—C7—C8—C9−2.1 (10)S4—C15—C20—C19176.4 (5)
C12—C7—C8—C9176.7 (6)C16—C15—C20—C23−177.4 (7)
C7—C8—C9—C10−0.2 (10)S4—C15—C20—C23−2.9 (10)
C7—C8—C9—C13−179.8 (7)C16—C15—S4—O5X−71.2 (9)
C8—C9—C10—C110.7 (10)C20—C15—S4—O5X114.2 (9)
C13—C9—C10—C11−179.7 (7)C16—C15—S4—O478.1 (7)
C9—C10—C11—C61.2 (11)C20—C15—S4—O4−96.4 (7)
C9—C10—C11—C14−177.6 (7)C16—C15—S4—O6−153.3 (7)
C7—C6—C11—C10−3.6 (10)C20—C15—S4—O632.2 (9)
S3—C6—C11—C10−178.8 (5)C16—C15—S4—O4X58.8 (8)
C7—C6—C11—C14175.2 (7)C20—C15—S4—O4X−115.7 (8)
S3—C6—C11—C140.0 (10)C16—C15—S4—O6X173.7 (8)
C11—C6—S3—O1X−167.6 (16)C20—C15—S4—O6X−0.8 (9)
C7—C6—S3—O1X17.3 (16)C16—C15—S4—O5−35.5 (8)
C11—C6—S3—O3X−45.6 (15)C20—C15—S4—O5149.9 (7)
Symmetry code: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4ii0.89 (2)2.40 (6)3.090 (12)135 (6)
N1—H1A···O4Xii0.89 (2)2.02 (6)2.683 (12)130 (6)
N1—H1B···O50.90 (2)2.01 (2)2.905 (11)177 (7)
N1—H1B···O5X0.90 (2)1.85 (4)2.681 (9)154 (7)
N2—H2A···O20.90 (2)2.25 (10)2.969 (19)136 (12)
N2—H2B···O4iii0.89 (2)2.19 (8)2.897 (15)136 (10)
N2X—H2C···O1Xi0.90 (2)2.39 (13)3.10 (4)136 (15)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formulaC10H28N4S44+·4C9H11O3S−
Mr1129.56
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)8.750 (2), 11.566 (3), 14.383 (4)
α, β, γ (°)98.540 (4), 104.135 (4), 99.119 (4)
V (Å3)1366.8 (6)
Z1
Radiation typeMo Kα
µ (mm−1)0.39
Crystal size (mm)0.09 × 0.02 × 0.01
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.945, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections		10556, 5312, 2257
Rint0.075
(sin θ/λ)max (Å−1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.077, 0.233, 1.01
No. of reflections5312
No. of parameters424
No. of restraints226
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.56, −0.56

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL and local programs.

Selected bond lengths (Å) top
C1—C5i1.550 (8)S1—C31.786 (5)
C1—C21.551 (7)S2—N21.705 (6)
C3—C41.554 (9)S2—C41.770 (6)
S1—N11.676 (6)S2—C51.772 (5)
S1—C21.782 (5)
Symmetry code: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4ii0.89 (2)2.40 (6)3.090 (12)135 (6)
N1—H1A···O4Xii0.89 (2)2.02 (6)2.683 (12)130 (6)
N1—H1B···O50.90 (2)2.01 (2)2.905 (11)177 (7)
N1—H1B···O5X0.90 (2)1.85 (4)2.681 (9)154 (7)
N2—H2A···O20.90 (2)2.25 (10)2.969 (19)136 (12)
N2—H2B···O4iii0.89 (2)2.19 (8)2.897 (15)136 (10)
N2X—H2C···O1Xi0.903 (15)2.39 (13)3.10 (4)136 (15)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1.
S—C and C—C bond lengths (Å) for tetrasubstituted [14]aneS4 crown species, obtained from a search of the CSD top
CompoundS—CC—C
Tetrasubstituted crown1.808–1.825 [1.818 (6)] (Ethyl)1.500–1.545 [1.523 (16)] (Ethyl)
1.804–1.818 [1.813 (4)] (Propyl)1.499–1.533 [1.518 (13)] (Propyl)
The ranges of the S—C and C—C bond lengths from tetra-S-substituted [14]aneS4 crowns from the CSD (Version 5.26, February 2005 update; Allen, 2002) are shown, with the average values shown in parentheses. The labels Ethyl and Propyl are used to distinguish between the two-carbon and three-carbon bridges in the crown molecule. The statistics are taken from a small population of six structures containing tetra-substituted crowns.
 

Acknowledgements

The authors acknowledge the EPSRC for a Postdoctoral Research Assistantship (LMG) and the use of the EPSRC's Chemical Database Service at Daresbury (Fletcher et al., 1996[Fletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746-749.]).

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationAucott, S. M., Bailey, M. R., Elsegood, M. R. J., Gilby, L. M., Holmes, K. E., Kelly, P. F., Papageorgiou, M. J. & Pedrón-Haba, S. (2004). New J. Chem. pp. 959–966.  Web of Science CSD CrossRef Google Scholar
 First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
 First citationBruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationElsegood, M. R. J., Holmes, K. E., Gilby, L. M. & Kelly, P. F. (2002). Can. J. Chem. 18, 1410–1414.  Web of Science CSD CrossRef Google Scholar
 First citationEtter, M. C. (1990). Acc. Chem. Res. 23, 120–126.  CrossRef CAS Web of Science Google Scholar
 First citationEtter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationFletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746–749.  CrossRef CAS Web of Science Google Scholar
 First citationHaynes, D. A., Chisholm, J. A., Jones, W. & Motherwell, W. D. S. (2004). CrystEngComm, 6, 584–588.  Web of Science CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 6| June 2005| Pages o411-o413
doi:10.1107/S010827010501437X
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