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In the title compound, C
10H
6N
4O
4S
2, (I), the molecule has a centre of inversion. The structure is a positional isomer of 5,5′-dinitro-2,2′-dithiodipyridine [Brito, Mundaca, Cárdenas, López-Rodríguez & Vargas (2007).
Acta Cryst. E
63, o3351–o3352], (II). The 3-nitropyridine fragment of (I) shows excellent agreement with the bonding geometries of (II). The most obvious differences between them are in the S—S bond length [2.1167 (12) Å in (I) and 2.0719 (11) Å in (II)], and in the C—C
ipso—N
ring [119.8 (2)° in (I) and 123.9 (3)° in (II)] and S—C—C [122.62 (18)° in (I) and 116.0 (2)° in (II)] angles. The crystal structure of (I) has an intramolecular C—H
O interaction, with an H
O distance of 2.40 (3) Å, whereas this kind of interaction is not evident in (II). The molecules of (I) are linked into centrosymmetric
R44(30) motifs by a C—H
O interaction. There are no aromatic π–π stacking and no C—H
π(arene) interactions. Compound (I) can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability.
Supporting information
CCDC reference: 682809
All reactions were carried out under an atmosphere of purified nitrogen.
Solvents were dried and distilled prior to use.
5,5'-dinitro-2,2'-dithiodipyridine and silver trifluoromethanesulfonate were
purchased from Aldrich and were used without further purification. The title
compound was obtained in an attempt to prepare coordination polymers with
silver trifluoromethanesulfonate and the ligand. A mixture of
5,5'-dinitro-2,2'-dithiodipyridine (1 mmol, 310 mg) and silver
trifluoromethanesulfonate (1 mmol, 256.9 mg) in methanol (20 ml) was refluxed
for 8 h. After slow cooling of the reaction system to room temperature,
pale-yellow prismatic crystals of (II) and colourless needle-shaped crystals
of (I) were formed. Samples of the two isomers were isolated manually at
ambient temperature. The spectroscopic properties of (I) were not determined
due to the small amount of sample available.
All H atoms were located in a difference map and their positional and isotropic
displacement parameters were refined.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
3,3'-Dinitro-2,2'-dithiodipyridine
top
Crystal data top
C10H6N4O4S2 | F(000) = 316 |
Mr = 310.31 | Dx = 1.691 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1177 reflections |
a = 3.8320 (17) Å | θ = 3.0–27.5° |
b = 21.4002 (12) Å | µ = 0.46 mm−1 |
c = 7.8301 (14) Å | T = 298 K |
β = 108.339 (10)° | Needle, colourless |
V = 609.5 (3) Å3 | 0.20 × 0.05 × 0.02 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1335 independent reflections |
Radiation source: fine-focus sealed tube | 1177 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ϕ scans, and ω scans with κ offsets | θmax = 27.3°, θmin = 2.9° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −4→4 |
Tmin = 0.970, Tmax = 0.987 | k = −21→27 |
4650 measured reflections | l = −10→9 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.0203P)2 + 0.4035P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.100 | (Δ/σ)max = 0.001 |
S = 1.22 | Δρmax = 0.26 e Å−3 |
1335 reflections | Δρmin = −0.22 e Å−3 |
103 parameters | |
Crystal data top
C10H6N4O4S2 | V = 609.5 (3) Å3 |
Mr = 310.31 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 3.8320 (17) Å | µ = 0.46 mm−1 |
b = 21.4002 (12) Å | T = 298 K |
c = 7.8301 (14) Å | 0.20 × 0.05 × 0.02 mm |
β = 108.339 (10)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1335 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1177 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.987 | Rint = 0.054 |
4650 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.100 | All H-atom parameters refined |
S = 1.22 | Δρmax = 0.26 e Å−3 |
1335 reflections | Δρmin = −0.22 e Å−3 |
103 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 | x | y | z | Uiso*/Ueq | |
S1 | 0.12815 (15) | 0.04092 (3) | 0.56682 (7) | 0.0276 (2) | |
O1 | 0.4423 (6) | 0.14861 (10) | 0.6805 (2) | 0.0495 (5) | |
O2 | 0.6756 (6) | 0.21671 (10) | 0.5420 (3) | 0.0586 (6) | |
N1 | −0.0227 (6) | 0.05151 (10) | 0.2104 (3) | 0.0338 (5) | |
N2 | 0.4861 (6) | 0.17034 (10) | 0.5429 (3) | 0.0357 (5) | |
C1 | 0.1373 (6) | 0.08007 (11) | 0.3691 (3) | 0.0259 (5) | |
C2 | 0.3044 (6) | 0.13896 (11) | 0.3727 (3) | 0.0282 (5) | |
C3 | 0.3017 (8) | 0.16864 (14) | 0.2147 (4) | 0.0379 (6) | |
C4 | 0.1319 (8) | 0.13897 (15) | 0.0545 (4) | 0.0445 (7) | |
C5 | −0.0226 (8) | 0.08091 (14) | 0.0589 (4) | 0.0413 (7) | |
H3 | 0.414 (8) | 0.2052 (14) | 0.222 (4) | 0.039 (8)* | |
H4 | 0.122 (8) | 0.1571 (15) | −0.049 (4) | 0.051 (9)* | |
H5 | −0.152 (7) | 0.0574 (15) | −0.049 (4) | 0.046 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0318 (3) | 0.0282 (3) | 0.0236 (3) | −0.0021 (2) | 0.0097 (2) | 0.0014 (2) |
O1 | 0.0642 (14) | 0.0512 (13) | 0.0335 (10) | −0.0113 (10) | 0.0158 (10) | −0.0057 (9) |
O2 | 0.0698 (15) | 0.0427 (13) | 0.0672 (15) | −0.0241 (11) | 0.0269 (12) | −0.0123 (11) |
N1 | 0.0420 (12) | 0.0316 (12) | 0.0269 (11) | 0.0025 (9) | 0.0096 (9) | 0.0023 (8) |
N2 | 0.0353 (12) | 0.0289 (12) | 0.0434 (13) | 0.0009 (9) | 0.0129 (10) | −0.0056 (10) |
C1 | 0.0270 (12) | 0.0260 (13) | 0.0262 (11) | 0.0053 (9) | 0.0104 (9) | 0.0030 (9) |
C2 | 0.0280 (12) | 0.0279 (13) | 0.0301 (12) | 0.0041 (10) | 0.0112 (10) | 0.0016 (10) |
C3 | 0.0396 (15) | 0.0317 (16) | 0.0457 (16) | 0.0018 (12) | 0.0180 (12) | 0.0095 (12) |
C4 | 0.0561 (19) | 0.0457 (18) | 0.0358 (15) | 0.0080 (14) | 0.0201 (14) | 0.0156 (13) |
C5 | 0.0539 (17) | 0.0427 (17) | 0.0253 (13) | 0.0069 (13) | 0.0098 (12) | 0.0011 (12) |
Geometric parameters (Å, º) top
S1—C1 | 1.771 (2) | C1—C2 | 1.410 (3) |
S1—S1i | 2.1167 (12) | C2—C3 | 1.388 (4) |
O1—N2 | 1.233 (3) | C3—C4 | 1.373 (4) |
O2—N2 | 1.231 (3) | C3—H3 | 0.89 (3) |
N1—C5 | 1.343 (3) | C4—C5 | 1.382 (4) |
N1—C1 | 1.347 (3) | C4—H4 | 0.89 (3) |
N2—C2 | 1.458 (3) | C5—H5 | 0.97 (3) |
| | | |
C1—S1—S1i | 95.34 (9) | C1—C2—N2 | 120.9 (2) |
C5—N1—C1 | 118.4 (2) | C4—C3—C2 | 118.1 (3) |
O2—N2—O1 | 123.5 (2) | C4—C3—H3 | 123.4 (19) |
O2—N2—C2 | 118.6 (2) | C2—C3—H3 | 118.4 (19) |
O1—N2—C2 | 117.9 (2) | C3—C4—C5 | 118.4 (3) |
N1—C1—C2 | 119.8 (2) | C3—C4—H4 | 120 (2) |
N1—C1—S1 | 117.62 (18) | C5—C4—H4 | 121 (2) |
C2—C1—S1 | 122.62 (18) | N1—C5—C4 | 124.3 (3) |
C3—C2—C1 | 121.0 (2) | N1—C5—H5 | 112.4 (18) |
C3—C2—N2 | 118.1 (2) | C4—C5—H5 | 123.3 (18) |
| | | |
C5—N1—C1—C2 | −1.0 (3) | O1—N2—C2—C3 | 169.6 (2) |
C5—N1—C1—S1 | 179.12 (19) | O2—N2—C2—C1 | 169.1 (2) |
S1i—S1—C1—N1 | 3.70 (19) | O1—N2—C2—C1 | −10.6 (3) |
S1i—S1—C1—C2 | −176.16 (18) | C1—C2—C3—C4 | −0.1 (4) |
N1—C1—C2—C3 | 1.1 (4) | N2—C2—C3—C4 | 179.7 (2) |
S1—C1—C2—C3 | −179.09 (19) | C2—C3—C4—C5 | −0.9 (4) |
N1—C1—C2—N2 | −178.7 (2) | C1—N1—C5—C4 | 0.0 (4) |
S1—C1—C2—N2 | 1.1 (3) | C3—C4—C5—N1 | 1.0 (5) |
O2—N2—C2—C3 | −10.8 (4) | | |
Symmetry code: (i) −x, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2 | 0.89 (3) | 2.40 (3) | 2.714 (4) | 101 (2) |
C3—H3···O2ii | 0.89 (3) | 2.58 (3) | 3.335 (4) | 143 (2) |
Symmetry code: (ii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C10H6N4O4S2 |
Mr | 310.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 3.8320 (17), 21.4002 (12), 7.8301 (14) |
β (°) | 108.339 (10) |
V (Å3) | 609.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.20 × 0.05 × 0.02 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.970, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4650, 1335, 1177 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.646 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.100, 1.22 |
No. of reflections | 1335 |
No. of parameters | 103 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.22 |
Selected bond and torsion angles (º) topN1—C1—C2 | 119.8 (2) | C4—C3—C2 | 118.1 (3) |
N1—C1—S1 | 117.62 (18) | C3—C4—C5 | 118.4 (3) |
C2—C1—S1 | 122.62 (18) | N1—C5—C4 | 124.3 (3) |
C3—C2—C1 | 121.0 (2) | | |
| | | |
S1i—S1—C1—N1 | 3.70 (19) | S1i—S1—C1—C2 | −176.16 (18) |
Symmetry code: (i) −x, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2 | 0.89 (3) | 2.40 (3) | 2.714 (4) | 101 (2) |
C3—H3···O2ii | 0.89 (3) | 2.58 (3) | 3.335 (4) | 143 (2) |
Symmetry code: (ii) x, −y+1/2, z−1/2. |
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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., 2007, and references therein). We report here the structure of the title compound, (I), isolated during attempts to synthesize coordination polymers with 5,5'-dinitro-2,2'-dithiodipyridine, (II), and silver trifluoromethanesulfonate. Compound (II) was purchased from Aldrich (purity 96%, CAS No. 2127–10-8). Impurities are not identified in the technical information accompanying the compound, but we believe that (I) was probably an impurity in the commercial sample of (II). To our knowledge, compound (I) is not commercially available.
The molecular structure of (I) is shown in Fig. 1 and selected geometric parameters are given in Table 1. The asymmetric unit of (I) consists of one-half molecule on an inversion centre. A 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°, the mean S—S bond distances are 2.031 (15) and 2.070 (22) Å, respectively. The corresponding value in (I) is 2.1166 (10) Å, placing it in the upper quartile for Allen's first set. In both isomers, the torsion angles X—C—S—S (where X = N or C) 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 of the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002) for the pyridyl disulfide fragment yielded 15 structures, of which only two have an equatorial conformation and S—S and C—S bond lengths similar to those of (I), namely S,S'-bis[3-(ethoxycarbonyl)pyridin-2-yl]disulfide (CSD refcode TATPUA; Toma et al., 2004), and S,S'-bis[3-(n-butoxycarbonyl)pyridin-2-yl]disulfide (CSD refcode OCOYIO; Cindric et al., 2001). The C1—S1 bond length of 1.771 (2) Å in (I) is between the C—S single-bond distance of 1.81 (2) Å and the double-bond distance of 1.56 (4) Å (Etter et al., 1992) and is similar 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-withdrawing properties of nitro substituents (Domenicano & Murray-Rust, 1979). The nitro group is rotated 11.0 (3)° out of the plane of the pyridine ring (Fig. 1). The molecular conformations are dominated by the near-orthogonality of the lone pairs on the two adjacent S atoms (Glidewell et al., 2000).
The molecular packing of (I) (Fig. 2) is completely different from that of the previous isomer. Only in the 3,3'-isomer, (I), does the nitropyridine ring participate in significant intramolecular C—H···O interactions, with an H···O distance of 2.40 (3) Å. These interactions may stabilize the conformation adopted by the molecule in the solid state (Fig. 1). The molecules are linked into centrosymmetric rings with an R44(30) motif (Bernstein et al., 1995) centred at (0,1/2,1/2) (Fig. 2, Table 2).