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ISSN: 2056-9890

Crystal structure of 4,4′-(disulfanediyl)di­butanoic acid–4,4′-bi­pyridine (1/1)

aFacultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Casilla 233, Santiago, Chile, bDepartamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Santiago de Chile, Chile, and cDepartamento de Física, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica, Buenos Aires, Argentina
*Correspondence e-mail: aatria@ciq.uchile.cl

Edited by M. Weil, Vienna University of Technology, Austria (Received 24 July 2014; accepted 14 August 2014; online 30 August 2014)

4,4′-(Disulfanediyl)dibutanoic acid (dtba) and 4,4′-bipyridine (4,4′-bpy) crystallize in an 1:1 ratio, leading to the title co-crystal with composition C8H14O4S2·C10H8N2. A distinctive feature of the crystal structure is the geometry of the dtba moiety, which appears to be stretched [with a 9.98 (1) Å span between outermost carbons] and acts as an hydrogen-bonding connector, forming linear chains along [-211] with the 4,4′-bpy moiety by way of O—H⋯N hydrogen bonds and C—H⋯O interactions. The influence of the mol­ecular shape on the hydrogen-bonding pattern is analysed by comparing the title compound and two other 4,4′-bpy co-crystals with closely related mol­ecules of similar formulation but different geometry, showing the way in which this correlates with the packing arrangement.

1. Chemical context

The object of the present study, the 4,4′-(disulfanediyl)di­butan­oic acid mol­ecule C8H12O4S2 (dtba), consists of a ten-membered C(H2)4S2C(H2)4 chain setting apart the carb­oxy­lic acid groups at each end. This suggests that the mol­ecule may be a good candidate for a `spacer' in the design of compounds with metal-organic framework (MOF) structures, provided that the mol­ecule connects the metal centres in an `extended' fashion. However, the `solid-state shape' of mol­ecules such as dtba is not directly discernible from first principles, as the chain includes many sp3 carbon atoms, which may possibly lead to twisted linkages.

[Scheme 1]

In addition, dtba is a rather uncommon ligand. The Cambridge Structure Database (Version 5.4, including June 2014 upgrades; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) does not at present include any entry whatsoever with the mol­ecule, either in its coordinating or free forms, for which any direct evidence of its shape is available. We have been trying for a while to coordinate the acid to some transition metals; however, so far we have been unsuccessful. During one of these numerous attempts, a co-crystal of dtba with 4,4′-bipyridine (4,4′-bpy), C10H8N2, was obtained instead. This serendipitous synthesis ended up being unique, since all subsequent attempts to obtain crystals with dtba ligand(s) in a more orthodox way have proved ineffective. We thus present herein the structural analysis of the 4,4′-bpy:dtba 1:1 co-crystal, C8H14O4S2·C10H8N2 (I)[link], which to our knowledge is the first crystal structure to be reported surveying the dtba group.

2. Structural commentary

Fig. 1[link] (top) presents an ellipsoid plot of the asymmetric unit of (I)[link]. The `topological' (non-crystallographic) symmetry of the dtba mol­ecule with a twofold rotation axis located at the center of the S1—S2 bond is obvious from inspection, and it is somehow reflected in the bond-length sequence, presented in Table 1[link] (corresponding bonds are presented in the same line). In fact, the pseudo-symmetry goes a bit further: the group presents a non-crystallographic C2v symmetry involving the mol­ecular core (C2–C7), which is reflected in the central torsion angles, viz. those involving S atoms (Table 1[link]). Fig. 1[link] (bottom) shows the least-squares fit of this core and its C2v-related image, with deviations falling in the tight range 0.011–0.015 Å. The outermost parts of the mol­ecule (the carb­oxy­lic functions at the ends) deviate significantly from this trend, probably as a result of the strong O—H⋯N inter­actions with neighbouring 4,4′-bpy mol­ecules (see discussion below), a fact also reflected in the torsion angles involved (last two lines in Table 1[link]). The double bonds in the –COOH groups are non-delocalized, with the C—O(H) bonds being distinctly longer than the C=O bonds (Table 1[link]).

Table 1
Selected geometric parameters (Å, °)

C1A—C2A 1.513 (3) C8A—C7A 1.497 (3)
C2A—C3A 1.487 (4) C7A—C6A 1.507 (3)
C3A—C4A 1.522 (3) C6A—C5A 1.522 (3)
C4A—S1A 1.811 (3) S2A—C5A 1.805 (3)
C1A—O1A 1.309 (3) O3A—C8A 1.325 (3)
C1A—O2A 1.198 (3) O4A—C8A 1.197 (3)
S1A—S2A 2.0369 (14)    
       
C2A—C3A—C4A—S1A −66.2 (3) S2A—C5A—C6A—C7A −67.6 (2)
C3A—C4A—S1A—S2A −68.2 (2) S1A—S2A—C5A—C6A −67.67 (19)
O2A—C1A—C2A—C3A −28.2 (4) C6A—C7A—C8A—O4A 4.3 (4)
C1A—C2A—C3A—C4A −165.0 (2) C5A—C6A—C7A—C8A 178.3 (2)
[Figure 1]
Figure 1
Top: the asymmetric unit of (I)[link], showing the H—O⋯N linkages as dashed lines. Displacement ellipsoids are drawn at the 40% probability level. Bottom: the least-squares superposition of one dtba mol­ecule and its C2 image, showing the pseudo-symmetry in its central core.

In spite of the unavoidable twisting due to the individual sp3 carbon atoms in the chain, the mol­ecule can be considered to be stretched, with a C1⋯C8 span of 9.98 (1) Å and the terminal OH groups being almost anti-parallel to each other, subtending an angle of 175.5 (1)°. Thus, at least in the present structure, the mol­ecule can be considered as a potentially adequate spacer for MOF construction.

The 4,4′-bpy mol­ecule, in turn, is basically featureless, with slightly non-planar pyridine rings [maximum deviations from the least-squares planes: C2B 0.005 (3), N2B: 0.005 (3) Å], rotated to each other by 4.54 (13)°.

3. Supra­molecular features

There are only two strong hydrogen-bond donors (the dtba carb­oxy­lic acid OH functions) and two hydrogen-bond acceptors (the pyridine N atoms of 4,4′-bpy) present, defining the supra­molecular organization (first two entries in Table 2[link]) in the form of linear chains running along [[\overline{2}]11] (Fig. 2[link]) with graph-set descriptor C22(22) (for graph-set nomenclature, see Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). Neighbouring chains, in turn, are connected into strips along [001] by a (notably weaker) C—H⋯O contact involving the pyridyl C9A—H9A group and one of the two non-protonated carboxyl­ato O atoms (third entry in Table 2[link], shown as nearly vertical broken lines in Fig. 2[link]), giving rise to R44(16) centrosymmetric loops. The chains run parallel to each other, with no obvious second-order inter­actions linking them, either of the C—H⋯O, C—H⋯π or ππ types. There is, however, a different type of contact present, namely a C—O⋯π contact involving the non-protonated O atom [C1A—O2ACgi where Cg1 is the centroid of atoms N1A, C1A–C5A, symmetry code (i): 1 − x, 1 − y, 1 − z, with O2ACg1i = 3.619 (3) Å; O2ACg1i, π: 165.25°], which helps in connecting the strips together into a three-dimensional supra­molecular structure (drawn in double dashed lines in Fig. 3[link]). Thus, all potentially expected actors for the supra­molecular building (OH, O and N functionalities) end up fulfilling a relevant role in the overall organization.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1A—H1A⋯N1B 0.85 (1) 1.83 (1) 2.661 (3) 163 (3)
O3A—H3A⋯N2Bi 0.86 (1) 1.80 (1) 2.637 (3) 162 (3)
C9B—H9B⋯O4Aii 0.93 2.49 3.404 (3) 167
Symmetry codes: (i) x+2, y-1, z-1; (ii) -x+2, -y, -z+1.
[Figure 2]
Figure 2
A packing view of (I)[link], showing the slabs formed by neighbouring chains connected by C—H⋯O contacts (shown as dashed lines).
[Figure 3]
Figure 3
Packing view of (I)[link] at right angles to the view in Fig. 2[link], showing the slabs in projection (one of them has been hightlighted). Single dashed lines denote the C—H⋯O bonds. The C—O⋯π contacts linking the slabs into a three-dimensional structure are shown as double dashed lines.

4. Database survey

A brief search of the CSD confirmed that 4,4′-bpy:di­carb­oxy­lic acid adducts are rather frequent; among the most populated families, the one derived from alkanes/alkenes ranks on top. Many of these present `extended' mol­ecular shapes, generating chain structures with similar O—H⋯N synthons as in (I)[link]. Among these, alkane-types are relevant to the present discussion as they are made up of sp3 C atoms. There are cases with n = 5 (glutaric acid) and n = 6 (adipic acid; Pedireddi et al., 1998[Pedireddi, V. R., Chatterjee, S., Ranganathan, A. & Rao, C. N. R. (1998). Tetrahedron, 54, 9457-9474.]), n = 7 (heptane-1,7-dioic acid; Braga et al., 2008[Braga, D., Palladino, G., Polito, M., Rubini, K., Grepioni, F., Chierotti, M. R. & Gobetto, R. (2008). Chem. Eur. J. 14, 10149-10159.]) and n = 10 (sebacic acid; Yu et al., 2006[Yu, B., Wang, X.-Q., Wang, R.-J., Shen, G.-Q. & Shen, D.-Z. (2006). Acta Cryst. E62, o2757-o2758.]).

However, examples of adducts with thio­dicarboxilyc acids are notably more rare and only two reported co-crystals of the sort can be found in the literature. These involve thio­dicarboxilyc acids closely related to dtba (see scheme below): thio­diglycolic acid (tdga) and thio­dipropionic acid (tdpa), viz. 4,4′-bpy:tdga and 4,4′-bpy:tdpa (Pedireddi et al., 1998[Pedireddi, V. R., Chatterjee, S., Ranganathan, A. & Rao, C. N. R. (1998). Tetrahedron, 54, 9457-9474.]). Surprisingly, in these structures the linkers behave in a different way from dtba. Fig. 4[link] (left) shows the geometry of the three mol­ecules under discussion, while Fig. 4[link] (right) presents the packing arrangements they give rise to.

[Scheme 2]
[Figure 4]
Figure 4
The three different mol­ecular shapes for tdga, tdpa and dtba, and the packing arrangements they give rise to, as described in the text.

In the first case, (tdga co-crystal) the mol­ecule is shaped like a horseshoe, and the terminal OH functions end up being almost parallel, subtending an angle of 12.5 (1)° to each other. The 4,4′-bpy aggregation motifs with this particular geometry give rise to isolated closed dimers as shown in Fig. 4[link] (upper right).

The tdpa mol­ecule presents a shape somehow similar to, but noticeably more open than tdga, with H—O⋯O—H bonds almost at a right angle to each other [97.1 (1)°]. The resulting packing mimics this mol­ecular geometry, in a tight herring-bone pattern (Fig. 4[link], mid-right). Finally, and as already discussed, the present dtba co-crystal displays a fully stretched geometry [H—O⋯O—H: 175.5 (1)°] and the basic packing unit is a linear chain.

From this analysis it can be concluded (at least for this type of terminal dicarboxilic acids) that the relative angular disposition of the outermost OH groups are relevant in defining the expected general aspect of the packing. In this context, dtba could be considered a potentially useful spacer for MOF construction, and further work to obtain transition-metal complexes with this ligand is in progress.

5. Synthesis and crystallization

The reported 4,4′-bpy:dtba co-crystal was obtained seren­dip­it­ously from an unsuccessful synthesis of a holmium complex, prepared from an Ho2O3:dtba:4,4-bpy solution (in a 1:2:1 ratio), dissolved in a mixture of water (200 ml) and ethanol (20 ml). After a few days of slow evaporation at room temperature, colourless block-like crystals were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. All H atoms were originally found in a difference Fourier map, but treated differently in refinement: C—H H atoms were repositioned in their expected positions and thereafter allowed to ride with Uiso(H) = 1.2Ueq(host) (d = 0.93 Å for C—Haromatic and d = 0.97 Å for C—Hmethyl­ene), while OH H atoms were refined with a restrained distance of 0.85 (1) Å.

Table 3
Experimental details

Crystal data
Chemical formula C8H14O4S2·C10H8N2
Mr 394.49
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 297
a, b, c (Å) 5.154 (3), 11.124 (7), 17.256 (11)
α, β, γ (°) 79.096 (10), 87.126 (10), 85.030 (12)
V3) 967.3 (10)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.30
Crystal size (mm) 0.23 × 0.14 × 0.11
 
Data collection
Diffractometer Bruker SMART CCD area detector
Absorption correction Multi-scan (SADABS; Sheldrick, 2008a[Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.])
Tmin, Tmax 0.94, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections 8306, 4185, 2376
Rint 0.031
(sin θ/λ)max−1) 0.656
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.131, 0.91
No. of reflections 4185
No. of parameters 243
No. of restraints 2
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.26, −0.16
Computer programs: SMART (Bruker, 2001[Bruker (2001). SMART. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2002[Bruker (2002). SAINT. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Chemical context top

The object of the present study, the 4,4'-(disulfanediyl)di­butanoic acid molecule C8H12O4S2 (dtba), consists of a ten-membered C(H2)4S2C(H2)4 chain setting apart the carb­oxy­lic acid groups at each end. This suggests that the molecule may be a good candidate for a `spacer' in the design of compounds with metal-organic framework (MOF) structures, provided that the molecule connects the metal centres in an `extended' fashion. However, the `solid-state shape' of molecules such as dtba is not directly discernible from first principles, as the chain includes many sp3 carbon atoms, which may lead to twisted linkages.

In addition, dtba is a rather uncommon ligand. The Cambridge Structure Database (Version 5.4, including June 2014 upgrades; Allen, 2002) does not at present include any entry whatsoever with the molecule, either in coordinating or free form, for which any direct evidence of its shape is available. We have been trying for a while to coordinate the acid to some transition metals; however, so far we have been unsuccessful. During one of these numerous attempts, a co-crystal of dtba with 4,4'-bi­pyridine (4,4'-bpy), C10H8N2, was obtained instead. This serendipitous synthesis ended up being unique, since all subsequent attempts to obtain crystals with dtba ligand(s) in a more orthodox way have proved ineffective. We thus present herein the structural analysis of the 4,4'-bpy:dtba 1:1 co-crystal, C8H14O4S2·C10H8N2 (I), which to our knowledge is the first crystal structure to be reported surveying the dtba group.

Structural commentary top

Fig 1 (top) presents an ellipsoid plot of the asymmetric unit of (I). The `topological' (non-crystallographic) symmetry of the dtba molecule with a twofold rotation axis located at the center of the S1—S2 bond is obvious from inspection, and it is somehow reflected in the bond-length sequence, presented in Table 1 (corresponding bonds are presented in the same line). In fact, the pseudo-symmetry goes a bit further: the group presents a non-crystallographic C2v symmetry involving the molecular core (C2–C7), which is reflected in the central torsion angles, viz. those involving S atoms (Table 1). Fig. 1 (bottom) shows the least-squares fit of this core and its C2v-related image, with deviations falling in the tight range 0.011–0.015 Å. The outermost parts of the molecule (the carb­oxy­lic functions at the ends) deviate significantly from this trend, probably as a result of the strong O—H···N inter­actions with neighbouring 4,4'-bpy molecules (see discussion below), a fact also reflected in the torsion angles involved (last two lines in Table 1). The double bonds in the –COOH groups are non-delocalized, with the C—O(H) bonds being distinctly longer than the CO bonds (Table 1).

In spite of the unavoidable twisting due to the individual sp3 carbon atoms in the chain, the molecule can be considered to be stretched, with a C1···C8 span of 9.98 (1) Å and the terminal OH groups being almost anti-parallel to each other, subtending an angle of 175.5 (1)°. Thus, at least in the present structure, the molecule can be considered as a potentially adequate spacer for MOF construction.

The 4,4'-bpy molecule, in turn, is basically featureless, with slightly non-planar pyridine rings [maximum deviations from the least-squares planes: C1B 0.157 (3), C9B: 0.106 (3) Å], rotated to each other by 4.54 (13)°.

Supra­molecular features top

There are only two strong hydrogen-bond donors (the dtba carb­oxy­lic acid OH functions) and two hydrogen-bond acceptors (the pyridine N atoms of 4,4'-bpy) present, defining the supra­molecular organization (first two entries in Table 2) in the form of linear chains running along [211] (Fig. 2) with graph-set descriptor C22(22) (for graph-set nomenclature, see Bernstein et al., 1995). Neighbouring chains, in turn, are connected into strips along [001] by a (notably weaker) C—H···O contact involving the pyridyl C9A—H9A group and one of the two non-protonated carboxyl­ato O atoms (third entry in Table 2, shown as nearly vertical broken lines in Fig. 2), giving rise to R44(16) centrosymmetric loops. The chains run parallel to each other, with no obvious second-order inter­actions linking them, either of the C—H···O, C—H···π or ππ types. There is, however, a different type of contact present, namely a C—O···π contact involving the non-protonated O atom [C1A—O2A···Cgi where Cg1 is the centroid of atoms N1A, C1A–C5A, symmetry code (i): 1 - x, 1 - y, 1 - z, with O2A···Cg1i = 3.619 (3) Å; O2A···Cg1i, π: 165.25°], which helps in connecting the strips together into a three-dimensional supra­molecular structure (drawn in double dashed lines in Fig. 3). Thus, all potentially expected actors for the supra­molecular building (OH, O and N functionalities) end up fulfilling a relevant role in the overall organization.

Database survey top

A brief search of the CSD confirmed that 4,4'-bpy:di­carb­oxy­lic acid adducts are rather frequent; among the most populated families, the one derived from alkanes/alkenes ranks on top. Many of these present `extended' molecular shapes, generating chain structures with similar O—H···N synthons as in (I). Among these, alkane-types are relevant to the present discussion as they are made up of sp3 C atoms. There are cases with n = 5 (glutaric acid) and n = 6 (adipic acid; Pedireddi et al., 1998), n = 7 (heptane-1,7-dioic acid; Braga et al., 2008) and n = 10 (sebacic acid; Yu et al., 2006).

However, examples of adducts with thio­dicarboxilyc acids are notably more rare and only two reported co-crystals of the sort can be found in the literature. These involve thio­dicarboxilyc acids closely related to dtba (see scheme below): thio­diglycolic acid (tdga) and thio­dipropionic acid (tdpa), viz.: 4,4'-bpy:tdga and 4,4'-bpy:tdpa (Pedireddi et al., 1998). Surprisingly, in these structures the linkers behave in a different way from dtba. Fig. 4 (left) shows the geometry of the three molecules under discussion, while Fig. 4 (right) presents the packing arrangements they give rise to.

In the first case, (tdga co-crystal) the molecule is shaped like a horseshoe, and the terminal OH functions end up being almost parallel, subtending an angle of 12.5 (1)° to each other. The 4,4'-bpy aggregation motifs with this particular geometry give rise to isolated closed dimers as shown in Fig. 4 (upper right).

The tdpa molecule presents a shape somehow similar to, but noticeably more open than tdga, with H—O···O—H bonds almost at a right angle to each other [97.1 (1)°]. The resulting packing mimics this molecular geometry, in a tight herring-bone pattern (Fig. 4, mid-right). Finally, and as already discussed, the present dtba co-crystal displays a fully stretched geometry [H—O···O—H: 175.5 (1)°] and the basic packing unit is a linear chain.

From this analysis it can be concluded (at least for this type of terminal dicarboxilic acids) that the relative angular disposition of the outermost OH groups are relevant in defining the expected general aspect of the packing. In this context, dtba could be considered a potentially useful spacer for MOF construction, and further work to obtain transition-metal complexes with this ligand is in progress.

Synthesis and crystallization top

The reported 4,4'-bpy:dtba co-crystal was obtained serendipitously from an unsuccessful synthesis of a holmium complex, prepared from an Ho2O3:dtba:4,4-bpy solution (in a 1:2:1 ratio), dissolved in a mixture of water (200 ml) and ethanol (20 ml). After a few days of slow evaporation at room temperature, colourless block-like crystals were obtained.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were originally found in a difference Fourier map, but treated differently in refinement: C—H H atoms were repositioned in their expected positions and thereafter allowed to ride with Uiso(H) = 1.2Ueq(host) (C—Haromatic: d = 0.93 Å, C—Hmethyl­ene, d = 0.97 Å), while OH H atoms were refined with a restrained distance of 0.85 (1) Å.

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Braga et al. (2008); Pedireddi et al. (1998); Yu et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Top: the asymmetric unit of (I), showing the H—O···N linkages as dashed lines. Displacement ellipsoids are drawn at the 40% probability level. Bottom: the least-squares superposition of one dtba molecule and its C2 image, showing the pseudo-symmetry in its central core.
[Figure 2] Fig. 2. A packing view of (I), showing the slabs formed by neighbouring chains connected by C—H···O contacts (shown as dashed lines).
[Figure 3] Fig. 3. Packing view of (I) at right angles to the view in Fig. 2, showing the slabs in projection (one of them has been hightlighted). Single dashed lines denote the C—H···O bonds. The C—O···π contacts linking the slabs into a three-dimensional structure are shown as double dashed lines.
[Figure 4] Fig. 4. The three different molecular shapes for tdga, tdpa and dtba, and the packing arrangements they give rise to, as described in the text.
4,4'-(Disulfanediyl)dibutanoic acid–4,4'-bipyridine (1/1) top
Crystal data top
C8H14O4S2·C10H8N2Z = 2
Mr = 394.49F(000) = 416
Triclinic, P1Dx = 1.354 Mg m3
a = 5.154 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.124 (7) ÅCell parameters from 1445 reflections
c = 17.256 (11) Åθ = 2.4–21.1°
α = 79.096 (10)°µ = 0.30 mm1
β = 87.126 (10)°T = 297 K
γ = 85.030 (12)°Block, colourless
V = 967.3 (10) Å30.23 × 0.14 × 0.11 mm
Data collection top
Bruker SMART CCD area detector
diffractometer
4185 independent reflections
Radiation source: fine-focus sealed tube2376 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
CCD rotation images, thin slices scansθmax = 27.8°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
h = 66
Tmin = 0.94, Tmax = 0.98k = 1414
8306 measured reflectionsl = 2222
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.0623P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.91(Δ/σ)max < 0.001
4185 reflectionsΔρmax = 0.26 e Å3
243 parametersΔρmin = 0.16 e Å3
Crystal data top
C8H14O4S2·C10H8N2γ = 85.030 (12)°
Mr = 394.49V = 967.3 (10) Å3
Triclinic, P1Z = 2
a = 5.154 (3) ÅMo Kα radiation
b = 11.124 (7) ŵ = 0.30 mm1
c = 17.256 (11) ÅT = 297 K
α = 79.096 (10)°0.23 × 0.14 × 0.11 mm
β = 87.126 (10)°
Data collection top
Bruker SMART CCD area detector
diffractometer
4185 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
2376 reflections with I > 2σ(I)
Tmin = 0.94, Tmax = 0.98Rint = 0.031
8306 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0482 restraints
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 0.91Δρmax = 0.26 e Å3
4185 reflectionsΔρmin = 0.16 e Å3
243 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
S1A1.04515 (14)0.04804 (7)0.29204 (4)0.0744 (3)
S2A0.87636 (14)0.02612 (6)0.18771 (4)0.0673 (2)
O1A0.7237 (4)0.23802 (19)0.51914 (11)0.0781 (6)
H1A0.627 (5)0.292 (2)0.5388 (16)0.105 (11)*
O2A0.4101 (4)0.26892 (19)0.43314 (12)0.0884 (7)
O3A1.4882 (4)0.16886 (17)0.02741 (11)0.0745 (6)
H3A1.596 (5)0.222 (2)0.0447 (18)0.127 (13)*
O4A1.4099 (4)0.32979 (16)0.06596 (10)0.0775 (6)
C1A0.6119 (6)0.2170 (2)0.45711 (15)0.0640 (7)
C2A0.7747 (6)0.1205 (3)0.42096 (16)0.0794 (9)
H2AA0.90440.16040.38460.095*
H2AB0.86630.06430.46250.095*
C3A0.6193 (6)0.0492 (3)0.37810 (16)0.0738 (8)
H3AA0.56580.10070.32870.089*
H3AB0.46300.02760.40950.089*
C4A0.7675 (6)0.0675 (2)0.36052 (15)0.0735 (8)
H4AA0.64640.11450.33980.088*
H4AB0.82740.11620.41000.088*
C5A0.7684 (5)0.1061 (2)0.15574 (15)0.0623 (7)
H5AA0.66080.14950.19780.075*
H5AB0.65940.07770.11060.075*
C6A0.9844 (5)0.1966 (2)0.13303 (14)0.0586 (6)
H6AA1.10290.22050.17620.070*
H6AB0.90880.26980.12470.070*
C7A1.1351 (5)0.1431 (2)0.05930 (13)0.0550 (6)
H7AA1.01540.12110.01630.066*
H7AB1.20360.06820.06750.066*
C8A1.3562 (5)0.2257 (2)0.03466 (13)0.0549 (6)
N1B0.4619 (4)0.38299 (19)0.60732 (12)0.0634 (6)
N2B0.2001 (4)0.69792 (17)0.89024 (12)0.0619 (6)
C1B0.2496 (6)0.4565 (3)0.58974 (15)0.0752 (8)
H1B0.18600.46520.53930.090*
C2B0.1163 (5)0.5213 (2)0.64262 (14)0.0657 (7)
H2B0.03070.57320.62700.079*
C3B0.2016 (4)0.50899 (19)0.71826 (12)0.0482 (6)
C4B0.4247 (5)0.4314 (2)0.73679 (13)0.0568 (6)
H4B0.49190.42010.78690.068*
C5B0.5455 (5)0.3712 (2)0.68026 (14)0.0631 (7)
H5B0.69420.31940.69390.076*
C6B0.2730 (5)0.7174 (2)0.81551 (15)0.0655 (7)
H6B0.41520.77330.80120.079*
C7B0.1501 (5)0.6598 (2)0.75835 (14)0.0578 (6)
H7B0.20930.67670.70710.069*
C8B0.0639 (4)0.57597 (19)0.77791 (13)0.0477 (6)
C9B0.1404 (5)0.5567 (2)0.85557 (13)0.0577 (6)
H9B0.28270.50190.87150.069*
C10B0.0063 (5)0.6186 (2)0.90922 (14)0.0633 (7)
H10B0.06220.60450.96080.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0605 (5)0.0877 (5)0.0845 (5)0.0148 (4)0.0181 (4)0.0456 (4)
S2A0.0779 (5)0.0572 (4)0.0685 (4)0.0008 (3)0.0026 (4)0.0206 (3)
O1A0.0807 (14)0.0935 (14)0.0625 (11)0.0290 (11)0.0102 (10)0.0350 (11)
O2A0.0810 (15)0.1039 (15)0.0861 (14)0.0257 (12)0.0253 (12)0.0411 (12)
O3A0.0912 (15)0.0658 (11)0.0640 (11)0.0144 (10)0.0107 (10)0.0185 (10)
O4A0.0936 (15)0.0618 (11)0.0692 (12)0.0252 (10)0.0073 (10)0.0048 (9)
C1A0.0731 (19)0.0640 (16)0.0546 (15)0.0076 (14)0.0012 (14)0.0173 (13)
C2A0.079 (2)0.0869 (19)0.0806 (19)0.0143 (16)0.0110 (16)0.0441 (17)
C3A0.075 (2)0.0852 (19)0.0631 (16)0.0072 (15)0.0015 (14)0.0248 (15)
C4A0.094 (2)0.0654 (16)0.0629 (16)0.0057 (15)0.0097 (15)0.0197 (14)
C5A0.0628 (17)0.0658 (15)0.0616 (15)0.0032 (13)0.0026 (13)0.0207 (13)
C6A0.0675 (18)0.0527 (13)0.0574 (14)0.0010 (12)0.0042 (13)0.0154 (12)
C7A0.0591 (16)0.0546 (13)0.0504 (13)0.0096 (12)0.0096 (11)0.0114 (11)
C8A0.0617 (16)0.0589 (15)0.0463 (13)0.0086 (12)0.0143 (12)0.0183 (12)
N1B0.0697 (15)0.0664 (13)0.0553 (12)0.0062 (11)0.0018 (11)0.0208 (11)
N2B0.0729 (15)0.0546 (12)0.0586 (12)0.0003 (11)0.0096 (11)0.0164 (10)
C1B0.076 (2)0.101 (2)0.0514 (15)0.0174 (17)0.0120 (14)0.0279 (15)
C2B0.0632 (17)0.0813 (18)0.0520 (14)0.0174 (14)0.0094 (12)0.0191 (13)
C3B0.0533 (15)0.0453 (12)0.0456 (12)0.0007 (11)0.0001 (11)0.0089 (10)
C4B0.0652 (17)0.0558 (14)0.0483 (13)0.0105 (12)0.0059 (12)0.0125 (11)
C5B0.0687 (18)0.0602 (15)0.0582 (15)0.0149 (13)0.0047 (13)0.0136 (13)
C6B0.0674 (18)0.0630 (15)0.0646 (16)0.0115 (13)0.0004 (14)0.0158 (13)
C7B0.0579 (16)0.0642 (15)0.0508 (13)0.0078 (12)0.0047 (12)0.0140 (12)
C8B0.0522 (14)0.0415 (11)0.0491 (12)0.0021 (10)0.0021 (11)0.0092 (10)
C9B0.0715 (18)0.0498 (13)0.0504 (13)0.0080 (12)0.0070 (12)0.0103 (11)
C10B0.086 (2)0.0576 (14)0.0460 (13)0.0022 (14)0.0018 (13)0.0129 (12)
Geometric parameters (Å, º) top
C1A—C2A1.513 (3)C6A—H6AB0.9700
C2A—C3A1.487 (4)C7A—H7AA0.9700
C3A—C4A1.522 (3)C7A—H7AB0.9700
C4A—S1A1.811 (3)N1B—C1B1.320 (3)
C1A—O1A1.309 (3)N1B—C5B1.330 (3)
C1A—O2A1.198 (3)N2B—C6B1.334 (3)
S1A—S2A2.0369 (14)N2B—C10B1.334 (3)
C8A—C7A1.497 (3)C1B—C2B1.388 (3)
C7A—C6A1.507 (3)C1B—H1B0.9300
C6A—C5A1.522 (3)C2B—C3B1.377 (3)
S2A—C5A1.805 (3)C2B—H2B0.9300
O3A—C8A1.325 (3)C3B—C4B1.389 (3)
O4A—C8A1.197 (3)C3B—C8B1.498 (3)
O1A—H1A0.851 (10)C4B—C5B1.379 (3)
O3A—H3A0.863 (10)C4B—H4B0.9300
C2A—H2AA0.9700C5B—H5B0.9300
C2A—H2AB0.9700C6B—C7B1.375 (3)
C3A—H3AA0.9700C6B—H6B0.9300
C3A—H3AB0.9700C7B—C8B1.393 (3)
C4A—H4AA0.9700C7B—H7B0.9300
C4A—H4AB0.9700C8B—C9B1.388 (3)
C5A—H5AA0.9700C9B—C10B1.380 (3)
C5A—H5AB0.9700C9B—H9B0.9300
C6A—H6AA0.9700C10B—H10B0.9300
C4A—S1A—S2A102.70 (10)C6A—C7A—H7AA108.5
C5A—S2A—S1A102.95 (9)C8A—C7A—H7AB108.5
C1A—O1A—H1A109 (2)C6A—C7A—H7AB108.5
C8A—O3A—H3A108 (2)H7AA—C7A—H7AB107.5
O2A—C1A—O1A123.6 (2)O4A—C8A—O3A123.4 (2)
O2A—C1A—C2A126.0 (3)O4A—C8A—C7A125.4 (2)
O1A—C1A—C2A110.4 (2)O3A—C8A—C7A111.2 (2)
C3A—C2A—C1A113.4 (2)C1B—N1B—C5B116.8 (2)
C3A—C2A—H2AA108.9C6B—N2B—C10B117.1 (2)
C1A—C2A—H2AA108.9N1B—C1B—C2B123.4 (2)
C3A—C2A—H2AB108.9N1B—C1B—H1B118.3
C1A—C2A—H2AB108.9C2B—C1B—H1B118.3
H2AA—C2A—H2AB107.7C3B—C2B—C1B120.0 (2)
C2A—C3A—C4A113.2 (2)C3B—C2B—H2B120.0
C2A—C3A—H3AA108.9C1B—C2B—H2B120.0
C4A—C3A—H3AA108.9C2B—C3B—C4B116.6 (2)
C2A—C3A—H3AB108.9C2B—C3B—C8B122.2 (2)
C4A—C3A—H3AB108.9C4B—C3B—C8B121.2 (2)
H3AA—C3A—H3AB107.8C5B—C4B—C3B119.4 (2)
C3A—C4A—S1A116.6 (2)C5B—C4B—H4B120.3
C3A—C4A—H4AA108.1C3B—C4B—H4B120.3
S1A—C4A—H4AA108.1N1B—C5B—C4B123.8 (2)
C3A—C4A—H4AB108.1N1B—C5B—H5B118.1
S1A—C4A—H4AB108.1C4B—C5B—H5B118.1
H4AA—C4A—H4AB107.3N2B—C6B—C7B123.8 (2)
C6A—C5A—S2A115.37 (18)N2B—C6B—H6B118.1
C6A—C5A—H5AA108.4C7B—C6B—H6B118.1
S2A—C5A—H5AA108.4C6B—C7B—C8B119.4 (2)
C6A—C5A—H5AB108.4C6B—C7B—H7B120.3
S2A—C5A—H5AB108.4C8B—C7B—H7B120.3
H5AA—C5A—H5AB107.5C9B—C8B—C7B116.6 (2)
C7A—C6A—C5A112.23 (19)C9B—C8B—C3B121.9 (2)
C7A—C6A—H6AA109.2C7B—C8B—C3B121.5 (2)
C5A—C6A—H6AA109.2C10B—C9B—C8B120.3 (2)
C7A—C6A—H6AB109.2C10B—C9B—H9B119.9
C5A—C6A—H6AB109.2C8B—C9B—H9B119.9
H6AA—C6A—H6AB107.9N2B—C10B—C9B122.8 (2)
C8A—C7A—C6A115.2 (2)N2B—C10B—H10B118.6
C8A—C7A—H7AA108.5C9B—C10B—H10B118.6
C2A—C3A—C4A—S1A66.2 (3)C1B—N1B—C5B—C4B0.4 (4)
C3A—C4A—S1A—S2A68.2 (2)C3B—C4B—C5B—N1B0.3 (4)
O2A—C1A—C2A—C3A28.2 (4)C10B—N2B—C6B—C7B0.8 (4)
C1A—C2A—C3A—C4A165.0 (2)N2B—C6B—C7B—C8B0.2 (4)
S2A—C5A—C6A—C7A67.6 (2)C6B—C7B—C8B—C9B0.4 (4)
S1A—S2A—C5A—C6A67.67 (19)C6B—C7B—C8B—C3B178.8 (2)
C6A—C7A—C8A—O4A4.3 (4)C2B—C3B—C8B—C9B175.5 (3)
C5A—C6A—C7A—C8A178.3 (2)C4B—C3B—C8B—C9B4.9 (4)
C6A—C7A—C8A—O3A175.9 (2)C2B—C3B—C8B—C7B3.7 (4)
C5B—N1B—C1B—C2B0.9 (5)C4B—C3B—C8B—C7B175.9 (2)
N1B—C1B—C2B—C3B1.2 (5)C7B—C8B—C9B—C10B0.3 (4)
C1B—C2B—C3B—C4B1.0 (4)C3B—C8B—C9B—C10B179.0 (2)
C1B—C2B—C3B—C8B179.5 (2)C6B—N2B—C10B—C9B0.9 (4)
C2B—C3B—C4B—C5B0.5 (4)C8B—C9B—C10B—N2B0.4 (4)
C8B—C3B—C4B—C5B179.9 (2)O1A—C1A—C2A—C3A152.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.85 (1)1.83 (1)2.661 (3)163 (3)
O3A—H3A···N2Bi0.86 (1)1.80 (1)2.637 (3)162 (3)
C9B—H9B···O4Aii0.932.493.404 (3)167
Symmetry codes: (i) x+2, y1, z1; (ii) x+2, y, z+1.
Selected geometric parameters (Å, º) top
C1A—C2A1.513 (3)C8A—C7A1.497 (3)
C2A—C3A1.487 (4)C7A—C6A1.507 (3)
C3A—C4A1.522 (3)C6A—C5A1.522 (3)
C4A—S1A1.811 (3)S2A—C5A1.805 (3)
C1A—O1A1.309 (3)O3A—C8A1.325 (3)
C1A—O2A1.198 (3)O4A—C8A1.197 (3)
S1A—S2A2.0369 (14)
C2A—C3A—C4A—S1A66.2 (3)S2A—C5A—C6A—C7A67.6 (2)
C3A—C4A—S1A—S2A68.2 (2)S1A—S2A—C5A—C6A67.67 (19)
O2A—C1A—C2A—C3A28.2 (4)C6A—C7A—C8A—O4A4.3 (4)
C1A—C2A—C3A—C4A165.0 (2)C5A—C6A—C7A—C8A178.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.851 (10)1.834 (13)2.661 (3)163 (3)
O3A—H3A···N2Bi0.863 (10)1.803 (14)2.637 (3)162 (3)
C9B—H9B···O4Aii0.932.493.404 (3)167.2
Symmetry codes: (i) x+2, y1, z1; (ii) x+2, y, z+1.

Experimental details

Crystal data
Chemical formulaC8H14O4S2·C10H8N2
Mr394.49
Crystal system, space groupTriclinic, P1
Temperature (K)297
a, b, c (Å)5.154 (3), 11.124 (7), 17.256 (11)
α, β, γ (°)79.096 (10), 87.126 (10), 85.030 (12)
V3)967.3 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.23 × 0.14 × 0.11
Data collection
DiffractometerBruker SMART CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008a)
Tmin, Tmax0.94, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
8306, 4185, 2376
Rint0.031
(sin θ/λ)max1)0.656
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.131, 0.91
No. of reflections4185
No. of parameters243
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b) and PLATON (Spek, 2009).

 

Acknowledgements

The authors acknowledge FONDECYT project No. 1110154.

References

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First citationYu, B., Wang, X.-Q., Wang, R.-J., Shen, G.-Q. & Shen, D.-Z. (2006). Acta Cryst. E62, o2757–o2758.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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