Acta Cryst. (2009). E65, o1213 [ doi:10.1107/S1600536809016213 ]
In the title compound, C10H8N2S2·C4H6O2, both components of the cocrystal lie on crystallographic twofold rotation axes. In the di-2-pyridyl disulfide molecule, the dihedral angle between the two pyridine rings is 66.6 (1)°. In the crystal structure, intermolecular O-H
N and weak C-HO hydrogen bonds link both types of molecules into columns along the c axis.
All chemicals were reagent grade quality obtained from commercial sources and without further purification. Dpds (0.2206 g, 1 mmol) and succinic acid (0.1181 g, 1 mmol) were dissolved in a H2O/EtOH solution (v/v = 2:1, 15 ml), which was stirred for 0.5 h and then filtrated, the filtrate was allowed to concentrate by slow evaporation to give colorless block crystals.
H atoms bonded to C atoms were palced in geometrically calculated positions (C-H = 0.93-0.97Å) and were refined in a riding-model approximation, with Uiso(H) = 1.2 Ueq(C). The H atom bonded to O2 atoms was located in a difference Fourier map and its position refined with Uiso(H) = 1.5 Ueq(O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./lh2792fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with dispalcement ellipsoids drawn at the 45% probability level. The complete molecules of di-2-pyridyl disulfide and succinic acid are generated by the symmetry operators (-x, y, -z+1/2) and (-x, y, -z+3/2) respectively. |
![[Figure 2]](./lh2792fig2thm.gif)
| Fig. 2. Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines. |
| C10H8N2S2·C4H6O4 | F000 = 704 |
| Mr = 338.39 | Dx = 1.430 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 4565 reflections |
| a = 8.4211 (17) Å | θ = 3.1–27.5º |
| b = 13.347 (3) Å | µ = 0.36 mm−1 |
| c = 14.141 (3) Å | T = 293 K |
| β = 98.43 (3)º | Block, colorless |
| V = 1572.2 (6) Å3 | 0.60 × 0.47 × 0.23 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID diffractometer | 1799 independent reflections |
| Radiation source: fine-focus sealed tube | 1490 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.039 |
| Detector resolution: 0 pixels mm-1 | θmax = 27.5º |
| T = 293 K | θmin = 3.1º |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −17→17 |
| Tmin = 0.822, Tmax = 0.921 | l = −18→16 |
| 7089 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0282P)2 + 3.2667P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.28 | (Δ/σ)max < 0.001 |
| 1799 reflections | Δρmax = 0.40 e Å−3 |
| 128 parameters | Δρmin = −0.30 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C10H8N2S2·C4H6O4 | V = 1572.2 (6) Å3 |
| Mr = 338.39 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 8.4211 (17) Å | µ = 0.36 mm−1 |
| b = 13.347 (3) Å | T = 293 K |
| c = 14.141 (3) Å | 0.60 × 0.47 × 0.23 mm |
| β = 98.43 (3)º |
| Rigaku R-AXIS RAPID diffractometer | 1799 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1490 reflections with I > 2σ(I) |
| Tmin = 0.822, Tmax = 0.921 | Rint = 0.039 |
| 7089 measured reflections |
| R[F2 > 2σ(F2)] = 0.053 | 128 parameters |
| wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.28 | Δρmax = 0.40 e Å−3 |
| 1799 reflections | Δρmin = −0.30 e Å−3 |
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 | ||
| N1 | −0.1474 (3) | 0.58448 (17) | 0.44834 (16) | 0.0396 (6) | |
| C1 | −0.1175 (3) | 0.56306 (19) | 0.36047 (19) | 0.0349 (6) | |
| C2 | −0.1815 (4) | 0.4813 (2) | 0.3079 (2) | 0.0436 (7) | |
| H2A | −0.1580 | 0.4692 | 0.2466 | 0.052* | |
| C3 | −0.2816 (4) | 0.4183 (2) | 0.3497 (3) | 0.0518 (8) | |
| H3A | −0.3273 | 0.3627 | 0.3165 | 0.062* | |
| C4 | −0.3132 (4) | 0.4382 (2) | 0.4408 (3) | 0.0540 (8) | |
| H4A | −0.3792 | 0.3961 | 0.4702 | 0.065* | |
| C5 | −0.2449 (4) | 0.5218 (2) | 0.4873 (2) | 0.0474 (7) | |
| H5A | −0.2673 | 0.5356 | 0.5484 | 0.057* | |
| S1 | 0.02142 (10) | 0.65005 (6) | 0.32235 (6) | 0.0473 (3) | |
| C6 | −0.0647 (3) | 0.7501 (2) | 0.63801 (19) | 0.0362 (6) | |
| C7 | 0.0187 (4) | 0.8324 (2) | 0.69918 (19) | 0.0395 (6) | |
| H7A | −0.0128 | 0.8965 | 0.6699 | 0.047* | |
| H7B | 0.1337 | 0.8254 | 0.7008 | 0.047* | |
| O1 | −0.1622 (3) | 0.69379 (16) | 0.66296 (15) | 0.0513 (6) | |
| O2 | −0.0193 (3) | 0.74777 (17) | 0.55229 (15) | 0.0523 (6) | |
| H2H | −0.065 (5) | 0.701 (3) | 0.521 (3) | 0.079* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0424 (14) | 0.0434 (13) | 0.0345 (12) | 0.0021 (11) | 0.0106 (10) | 0.0002 (9) |
| C1 | 0.0338 (15) | 0.0335 (13) | 0.0394 (14) | 0.0023 (11) | 0.0122 (11) | 0.0003 (10) |
| C2 | 0.0500 (19) | 0.0368 (15) | 0.0474 (17) | −0.0022 (13) | 0.0184 (13) | −0.0075 (12) |
| C3 | 0.055 (2) | 0.0339 (15) | 0.069 (2) | −0.0067 (14) | 0.0180 (16) | −0.0032 (14) |
| C4 | 0.053 (2) | 0.0447 (17) | 0.069 (2) | −0.0020 (15) | 0.0237 (16) | 0.0166 (15) |
| C5 | 0.0502 (19) | 0.0556 (18) | 0.0399 (16) | 0.0046 (15) | 0.0177 (13) | 0.0109 (13) |
| S1 | 0.0518 (5) | 0.0440 (4) | 0.0515 (5) | −0.0135 (4) | 0.0255 (4) | −0.0117 (3) |
| C6 | 0.0394 (16) | 0.0363 (14) | 0.0330 (13) | 0.0031 (12) | 0.0057 (11) | 0.0053 (10) |
| C7 | 0.0424 (16) | 0.0387 (14) | 0.0372 (15) | −0.0043 (12) | 0.0054 (12) | 0.0025 (11) |
| O1 | 0.0617 (15) | 0.0510 (13) | 0.0432 (12) | −0.0169 (11) | 0.0140 (10) | 0.0003 (9) |
| O2 | 0.0669 (16) | 0.0549 (14) | 0.0390 (12) | −0.0156 (12) | 0.0205 (10) | −0.0064 (9) |
| N1—C1 | 1.334 (3) | C5—H5A | 0.9300 |
| N1—C5 | 1.345 (4) | S1—S1i | 2.0251 (17) |
| C1—C2 | 1.385 (4) | C6—O1 | 1.204 (3) |
| C1—S1 | 1.787 (3) | C6—O2 | 1.324 (3) |
| C2—C3 | 1.384 (4) | C6—C7 | 1.507 (4) |
| C2—H2A | 0.9300 | C7—C7ii | 1.516 (5) |
| C3—C4 | 1.380 (5) | C7—H7A | 0.9700 |
| C3—H3A | 0.9300 | C7—H7B | 0.9700 |
| C4—C5 | 1.378 (5) | O2—H2H | 0.83 (4) |
| C4—H4A | 0.9300 | ||
| C1—N1—C5 | 117.2 (3) | N1—C5—H5A | 118.5 |
| N1—C1—C2 | 123.9 (3) | C4—C5—H5A | 118.5 |
| N1—C1—S1 | 111.3 (2) | C1—S1—S1i | 106.10 (10) |
| C2—C1—S1 | 124.8 (2) | O1—C6—O2 | 123.7 (3) |
| C3—C2—C1 | 117.6 (3) | O1—C6—C7 | 124.6 (3) |
| C3—C2—H2A | 121.2 | O2—C6—C7 | 111.7 (2) |
| C1—C2—H2A | 121.2 | C6—C7—C7ii | 113.6 (2) |
| C4—C3—C2 | 119.7 (3) | C6—C7—H7A | 108.8 |
| C4—C3—H3A | 120.2 | C7ii—C7—H7A | 108.8 |
| C2—C3—H3A | 120.2 | C6—C7—H7B | 108.8 |
| C5—C4—C3 | 118.5 (3) | C7ii—C7—H7B | 108.8 |
| C5—C4—H4A | 120.7 | H7A—C7—H7B | 107.7 |
| C3—C4—H4A | 120.7 | C6—O2—H2H | 109 (3) |
| N1—C5—C4 | 123.1 (3) |
| Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2H···N1 | 0.83 (4) | 1.94 (4) | 2.759 (3) | 173 (4) |
| C2—H2A···O1iii | 0.93 | 2.47 | 3.128 (4) | 127 |
| Symmetry codes: (iii) x, −y+1, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2H···N1 | 0.83 (4) | 1.94 (4) | 2.759 (3) | 173 (4) |
| C2—H2A···O1i | 0.93 | 2.47 | 3.128 (4) | 127 |
| Symmetry codes: (i) x, −y+1, z−1/2. |
This project was sponsored by the K. C. Wong Magna Fund of Ningbo University and supported by the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Zhejiang Provincial Natural Science Foundation (grant No. Z203067) and the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061).
Desiraju, G. R. (2003). J. Mol. Struct. 656, 5-15.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Raghavan, N. V. & Seff, K. (1977). Acta Cryst. B33, 386–391.
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Thalladi, V. R., Dabros, M., Gehrke, A., Weiss, H. C. & Boese, R. (2007). Cryst. Growth Des. 7, 598–599.
The design of cocrystals has been a field of intensive research in recent years. With reliable design strategies, cocrystals could offer a modular approach to developing materials with desirable properties. (Desiraju, 2003; Thalladi et al., 2007). Weak noncovalent interactions such as hydrogen bonds are utilized to create cocrystals. Herein we report the structure of the title cocrystal.
The formula unit of the title compound (Fig. 1) contains one molecule of di-2-pyridyl disulfide (dpds) and one molecule succinic acid. The dihedral angle between the two pyridine rings of the dpds molecule is 66.6 (1)°, and the S—S bond length, 2.025 (2) Å, is not significantly different than that found in the structure of the free ligand, 2.016 (2) Å (Raghavan et al., 1977). The torsion angle of the C6-C7-C7ii-C6ii [symmetry code: (ii) -x, y, -z+3/2] backbone of succinic acid is 74.5 (3)°. The proton of the carboxylate O atom (O2) of the succinic acid molecule forms a strong hydrogen bond with atom N1 of the dpds molecule (see Table 1 for hydrogen bond geometry). In addition, in the crystal structure, weak intermolecular C-H···O hydrogen bonds supplement intermolecular N-H···O hydrogen bonds to form columns running parallel to the c-axis (Fig 2).