Acta Cryst. (2007). E63, o3351-o3352 [ doi:10.1107/S1600536807031091 ]
In the title disulfide, (5-O2NC5H3N)2S2 or C10H6N4O4S2, the molecule has a center of inversion. All bond lengths and angles are within normal ranges, and the molecules are linked into centrosymmetric R22(22) dimers by a simple C-H
O interaction. In the crystal structure, there are no aromatic ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking and no C-H(arene) interactions.
A sample of 2,2'-dithio-bis(5-nitropyridine) was purchased from Aldrich. Crystals suitable for single-crystal x-ray diffraction analysis were grown by slow evaporation of a solution in ethyl acetate. FT—IR (KBr pellet, cm−1): ν (w, C– H) 3087, ν (s, N ═ O of NO2 asymmetric) 1563, ν (v.s. N ═ O of NO2 symmetric) 1343, ν (w, C - H disubstitution 1,4) 1958, ν (s, C - H disubstitution 1,4) 856, ν (w, C - N) 1101, ν (s, C ═ C) 1590, ν (w, C - H) 1006, (s, C ═ N) 1519, ν (w, C - S) 735, ν (w, S—S) 540.
In the final cycles of the refinement, all H atoms were constrained to ride on their parent atoms, with aryl C - H distances of 0.93 Å, and with Uiso(H) = 1.2Ueq(C). 112 unique reflections were not included in the data set as they were either partially obscured by the beam stop or were eliminated during data reduction.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./om2142fig1thm.gif)
| Fig. 1. A view of the molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Unlabeled atoms are related to labeled atoms by the symmetry code (−x + 1, −y + 2, −z). |
![[Figure 2]](./om2142fig2thm.gif)
| Fig. 2. The molecular packing. Dashed lines indicate hydrogen bond [Symmetry code: (i) x + 1, y + 1, z]. H atoms not involved in hydrogen bonds have been omitted for clarity. |
| C10H6N4O4S2 | F(000) = 316 |
| Mr = 310.31 | Dx = 1.725 Mg m−3 |
| Monoclinic, P21/n | Melting point = 428–430 K |
| Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
| a = 5.2610 (15) Å | Cell parameters from 2999 reflections |
| b = 6.0440 (13) Å | θ = 3.5–27.5° |
| c = 18.8070 (19) Å | µ = 0.47 mm−1 |
| β = 92.839 (12)° | T = 293 K |
| V = 597.3 (2) Å3 | Prism, colourless |
| Z = 2 | 0.43 × 0.30 × 0.22 mm |
| Nonius KappaCCD area-detector diffractometer | 1267 independent reflections |
| Radiation source: fine-focus sealed tube | 1122 reflections with I > 2σ(I) |
| graphite | Rint = 0.067 |
| φ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.5° |
| Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −6→6 |
| Tmin = 0.842, Tmax = 0.901 | k = −6→7 |
| 3529 measured reflections | l = −19→24 |
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.059 | w = 1/[σ2(Fo2) + 1.3711P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.139 | (Δ/σ)max = 0.014 |
| S = 1.08 | Δρmax = 0.48 e Å−3 |
| 1267 reflections | Δρmin = −0.31 e Å−3 |
| 91 parameters |
| C10H6N4O4S2 | V = 597.3 (2) Å3 |
| Mr = 310.31 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 5.2610 (15) Å | µ = 0.47 mm−1 |
| b = 6.0440 (13) Å | T = 293 K |
| c = 18.8070 (19) Å | 0.43 × 0.30 × 0.22 mm |
| β = 92.839 (12)° |
| Nonius KappaCCD area-detector diffractometer | 1267 independent reflections |
| Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1122 reflections with I > 2σ(I) |
| Tmin = 0.842, Tmax = 0.901 | Rint = 0.067 |
| 3529 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
| wR(F2) = 0.139 | Δρmax = 0.48 e Å−3 |
| S = 1.08 | Δρmin = −0.31 e Å−3 |
| 1267 reflections | Absolute structure: ? |
| 91 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.64977 (15) | 0.47850 (13) | 0.03722 (4) | 0.0348 (3) | |
| O1 | 0.4118 (5) | −0.4104 (4) | 0.22547 (13) | 0.0486 (7) | |
| O2 | 0.0696 (5) | −0.3958 (5) | 0.15797 (16) | 0.0615 (9) | |
| N1 | 0.2791 (5) | −0.3234 (5) | 0.17826 (13) | 0.0345 (6) | |
| N2 | 0.3161 (5) | 0.1460 (4) | 0.05263 (13) | 0.0314 (6) | |
| C1 | 0.5303 (6) | 0.2418 (5) | 0.07878 (15) | 0.0285 (6) | |
| C2 | 0.6740 (6) | 0.1634 (5) | 0.13849 (16) | 0.0328 (7) | |
| H2 | 0.8211 | 0.2363 | 0.155 | 0.039* | |
| C3 | 0.5917 (6) | −0.0239 (5) | 0.17193 (16) | 0.0322 (7) | |
| H3 | 0.6816 | −0.0821 | 0.2114 | 0.039* | |
| C4 | 0.3700 (6) | −0.1227 (5) | 0.14469 (15) | 0.0281 (6) | |
| C5 | 0.2369 (6) | −0.0362 (5) | 0.08584 (16) | 0.0309 (6) | |
| H5 | 0.0886 | −0.1061 | 0.0688 | 0.037* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0363 (5) | 0.0301 (4) | 0.0372 (4) | −0.0081 (3) | −0.0048 (3) | 0.0063 (3) |
| O1 | 0.0510 (15) | 0.0434 (15) | 0.0504 (14) | −0.0051 (12) | −0.0078 (11) | 0.0192 (11) |
| O2 | 0.0546 (17) | 0.0570 (18) | 0.0706 (18) | −0.0317 (15) | −0.0185 (13) | 0.0224 (15) |
| N1 | 0.0384 (15) | 0.0303 (14) | 0.0346 (13) | −0.0055 (11) | 0.0002 (11) | 0.0023 (11) |
| N2 | 0.0293 (13) | 0.0298 (14) | 0.0347 (13) | −0.0020 (11) | −0.0022 (10) | 0.0018 (10) |
| C1 | 0.0319 (15) | 0.0249 (14) | 0.0289 (14) | −0.0001 (12) | 0.0037 (11) | −0.0011 (11) |
| C2 | 0.0306 (15) | 0.0326 (17) | 0.0347 (15) | −0.0058 (13) | −0.0029 (12) | −0.0004 (12) |
| C3 | 0.0338 (16) | 0.0321 (16) | 0.0300 (14) | 0.0016 (13) | −0.0042 (11) | 0.0025 (12) |
| C4 | 0.0298 (15) | 0.0236 (14) | 0.0311 (14) | 0.0000 (12) | 0.0026 (11) | −0.0002 (11) |
| C5 | 0.0299 (15) | 0.0299 (16) | 0.0327 (15) | −0.0043 (12) | −0.0006 (11) | −0.0007 (12) |
| S1—C1 | 1.761 (3) | C1—C2 | 1.405 (4) |
| S1—S1i | 2.0719 (15) | C2—C3 | 1.375 (4) |
| O1—N1 | 1.221 (3) | C2—H2 | 0.93 |
| O2—N1 | 1.229 (4) | C3—C4 | 1.386 (4) |
| N1—C4 | 1.459 (4) | C3—H3 | 0.93 |
| N2—C1 | 1.339 (4) | C4—C5 | 1.383 (4) |
| N2—C5 | 1.343 (4) | C5—H5 | 0.93 |
| C1—S1—S1i | 97.22 (11) | C1—C2—H2 | 120.9 |
| O1—N1—O2 | 123.0 (3) | C2—C3—C4 | 117.7 (3) |
| O1—N1—C4 | 119.0 (3) | C2—C3—H3 | 121.2 |
| O2—N1—C4 | 118.0 (3) | C4—C3—H3 | 121.2 |
| C1—N2—C5 | 117.3 (3) | C5—C4—C3 | 121.1 (3) |
| N2—C1—C2 | 123.9 (3) | C5—C4—N1 | 119.8 (3) |
| N2—C1—S1 | 120.0 (2) | C3—C4—N1 | 119.1 (3) |
| C2—C1—S1 | 116.0 (2) | N2—C5—C4 | 121.7 (3) |
| C3—C2—C1 | 118.3 (3) | N2—C5—H5 | 119.1 |
| C3—C2—H2 | 120.9 | C4—C5—H5 | 119.1 |
| C5—N2—C1—C2 | −0.3 (5) | C2—C3—C4—N1 | 179.1 (3) |
| C5—N2—C1—S1 | 178.9 (2) | O1—N1—C4—C5 | 172.6 (3) |
| S1i—S1—C1—N2 | 5.2 (3) | O2—N1—C4—C5 | −8.2 (4) |
| S1i—S1—C1—C2 | −175.5 (2) | O1—N1—C4—C3 | −6.4 (4) |
| N2—C1—C2—C3 | 0.6 (5) | O2—N1—C4—C3 | 172.8 (3) |
| S1—C1—C2—C3 | −178.6 (2) | C1—N2—C5—C4 | 0.0 (4) |
| C1—C2—C3—C4 | −0.5 (5) | C3—C4—C5—N2 | 0.1 (5) |
| C2—C3—C4—C5 | 0.2 (5) | N1—C4—C5—N2 | −178.9 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···O2ii | 0.93 | 2.58 | 3.389 (4) | 146 |
| Symmetry codes: (ii) x+1, y+1, z. |
| C1—S1—S1i | 97.22 (11) | C2—C1—S1 | 116.0 (2) |
| N2—C1—C2 | 123.9 (3) | C3—C2—C1 | 118.3 (3) |
| N2—C1—S1 | 120.0 (2) | C5—C4—N1 | 119.8 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···O2ii | 0.93 | 2.58 | 3.389 (4) | 146 |
| Symmetry codes: (ii) x+1, y+1, z. |
This work was supported by a grant from the Universidad de Antofagasta (DI-1324–06). We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge licence for the Cambridge Structural Database (Allen, 2002) system. AM thanks the Universidad de Antofagasta for a PhD fellowship.
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This paper forms part of our continuing study of the synthesis and structural characterization of divalent sulfur compounds (Brito et al., 2006 and references therein). We are particularly interested in the utility of the title compound, (Fig. 1 and Table 1), as a flexible ligand, and its binding modes, for the fabrication of different coordination polymer topologies. A database survey of C—S—S—C fragments (Allen et al., 1987) found that S—S bond distances are bimodally distributed; for torsion angles in the ranges 75–105° and 0–20°, S—S bond-distance means were found to be 2.031 (15) and 2.070 (22) Å respectively. The corresponding value in the title compound is 2.0719 (11) Å, placing it in the upper quartile for Allen's first set. Further more, the torsion angles X—C—S—S, (where X=N or C), N2—C1—S1—S1i = 5.2 (3)° (symmetry code (i): −x + 1, −y + 1, −z) are close to 0 or 180° and within the range found in other substituted aromatic disulfides with an equatorial conformation according to the Shefter classification (Shefter, 1970). A search in the Cambridge Structural Database (version 5.28; Allen 2002) for the pyridyl disulfide fragment yielded fifteen structures of those which only two have an equatorial conformation, namely S,S'-bis(3-(Ethoxycarbonyl)pyridin-2-yl)disulfide (refcode TATPUA; Toma et al., 2004), and S,S'-bis(3-(n-Butoxycarbonyl)pyridin-2-yl)disulfide (refcode OCOYIO; Cindric et al., 2001). The C—S bond length of 1.761 (3) Å is between the value for a C—S single-bond distance of about 1.81 (2) Å and that for a double-bond distance of about 1.56 (4) Å (Etter et al., 1992) and is shorter than to those observed in organic disulfides with an equatorial conformation. Also noteworthy are the C—C—C, C—C—S and C—C—N angles at the ipso positions (Table 1), where the C—C—C angles, in particular, are consistent with the electron-donating and electron-withdrawing properties of thiolate and nitro substituents, respectively (Domenicano & Murray-Rust, 1979). The nitro group is nearly coplanar with the adjacent aryl ring (Fig. 1). The C4—N1 bond distance is 1.459 (4) Å; this value is typical of C(aryl)-NO2 distances, where the mean value is 1.468 Å (Allen et al., 1987) with upper and lower quartile values of 1.476 and 1.460 Å respectively.
Molecules of the title compound are linked into centrosymmetric R22(22) dimers by a simple C—H···O interaction,. [H···O = 2.58 Å, O···O = 3.389 (4) Å and C—H···O = 146°]. Nitro atom O2 in the molecule at (x + 1, y + 1, −z) acts as hydrogen-bond acceptor to a C2 atom H2 in the molecule at (x, y, z), so generating a centro-symmetric dimer characterized by R22(22) motif and centred at (1/2, 1/2, 0), Fig. 2, (Bernstein et al., 1995). Such interactions are generally the dominant feature of the crystal structures of compounds containing nitroarenethiolate (O2NC6H4SX) fragments (Kucsman et al., 1984; Aupers et al., 1999; Low et al., 2000; Glidewell et al., 2000), as well as those of simple nitrobenzenes (Boonstra, 1963; Trotter & Williston, 1966; Choi & Abel, 1972, Herbstein & Kapon, 1990; Boese et al., 1992; Sekine et al., 1994). The title compound retains equatorial conformation in its complex formed with AgNO3 (to within 22°) (López-Rodríguez et al., 2006). The coordination of silver(I) ion to either sulfur or nitrogen atoms of the title compound has not required an unusual X—C—S—S angle (X=C or N) angle, therefore the S—S bond is unaffected by complexation (2.031 (2) for the complex and 2.0719 (15) Å for the title compound). The larger observed deviation due to complexation is in the phenyl ring orientation (C—S—S—C = 70.8 (2)° for the complex and 180° for the title compound).