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ISSN: 2056-9890

Di-2-pyridyl di­sulfide–succinic acid (1/1)

aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Institute of Solid Materials Chemistry, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
*Correspondence e-mail: zhengyueqing@nbu.edu.cn

(Received 19 March 2009; accepted 30 April 2009; online 7 May 2009)

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—H⋯O hydrogen bonds link both types of mol­ecules into columns along the c axis.

Related literature

For general background to the design of cocrystals, see: Desiraju (2003[Desiraju, G. R. (2003). J. Mol. Struct. 656, 5-15.]); Thalladi et al. (2007[Thalladi, V. R., Dabros, M., Gehrke, A., Weiss, H. C. & Boese, R. (2007). Cryst. Growth Des. 7, 598-599.]). For a related structure, see: Raghavan et al. (1977[Raghavan, N. V. & Seff, K. (1977). Acta Cryst. B33, 386-391.]).

[Scheme 1]

Experimental

Crystal data
  • C10H8N2S2·C4H6O4

  • Mr = 338.39

  • Monoclinic, C 2/c

  • a = 8.4211 (17) Å

  • b = 13.347 (3) Å

  • c = 14.141 (3) Å

  • β = 98.43 (3)°

  • V = 1572.2 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.36 mm−1

  • T = 293 K

  • 0.60 × 0.47 × 0.23 mm

Data collection
  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.822, Tmax = 0.921

  • 7089 measured reflections

  • 1799 independent reflections

  • 1490 reflections with I > 2σ(I)

  • Rint = 0.039

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.139

  • S = 1.28

  • 1799 reflections

  • 128 parameters

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

  • Δρmax = 0.40 e Å−3

  • Δρmin = −0.30 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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 code: (i) [x, -y+1, z-{\script{1\over 2}}].

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004[Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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).

Related literature top

For general background to the design of cocrystals, see: Desiraju (2003); Thalladi et al. (2007). For a related structure, see: Raghavan et al. (1977).

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] 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] Fig. 2. Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines.
Di-2-pyridyl disulfide–succinic acid (1/1) top
Crystal data top
C10H8N2S2·C4H6O4F(000) = 704
Mr = 338.39Dx = 1.430 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4565 reflections
a = 8.4211 (17) Åθ = 3.1–27.5°
b = 13.347 (3) ŵ = 0.36 mm1
c = 14.141 (3) ÅT = 293 K
β = 98.43 (3)°Block, colorless
V = 1572.2 (6) Å30.60 × 0.47 × 0.23 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1799 independent reflections
Radiation source: fine-focus sealed tube1490 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 0 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = 1010
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1717
Tmin = 0.822, Tmax = 0.921l = 1816
7089 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.28 w = 1/[σ2(Fo2) + (0.0282P)2 + 3.2667P]
where P = (Fo2 + 2Fc2)/3
1799 reflections(Δ/σ)max < 0.001
128 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C10H8N2S2·C4H6O4V = 1572.2 (6) Å3
Mr = 338.39Z = 4
Monoclinic, C2/cMo Kα radiation
a = 8.4211 (17) ŵ = 0.36 mm1
b = 13.347 (3) ÅT = 293 K
c = 14.141 (3) Å0.60 × 0.47 × 0.23 mm
β = 98.43 (3)°
Data collection top
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 = 0.921Rint = 0.039
7089 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.28Δρmax = 0.40 e Å3
1799 reflectionsΔρmin = 0.30 e Å3
128 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*/Ueq
N10.1474 (3)0.58448 (17)0.44834 (16)0.0396 (6)
C10.1175 (3)0.56306 (19)0.36047 (19)0.0349 (6)
C20.1815 (4)0.4813 (2)0.3079 (2)0.0436 (7)
H2A0.15800.46920.24660.052*
C30.2816 (4)0.4183 (2)0.3497 (3)0.0518 (8)
H3A0.32730.36270.31650.062*
C40.3132 (4)0.4382 (2)0.4408 (3)0.0540 (8)
H4A0.37920.39610.47020.065*
C50.2449 (4)0.5218 (2)0.4873 (2)0.0474 (7)
H5A0.26730.53560.54840.057*
S10.02142 (10)0.65005 (6)0.32235 (6)0.0473 (3)
C60.0647 (3)0.7501 (2)0.63801 (19)0.0362 (6)
C70.0187 (4)0.8324 (2)0.69918 (19)0.0395 (6)
H7A0.01280.89650.66990.047*
H7B0.13370.82540.70080.047*
O10.1622 (3)0.69379 (16)0.66296 (15)0.0513 (6)
O20.0193 (3)0.74777 (17)0.55229 (15)0.0523 (6)
H2H0.065 (5)0.701 (3)0.521 (3)0.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0424 (14)0.0434 (13)0.0345 (12)0.0021 (11)0.0106 (10)0.0002 (9)
C10.0338 (15)0.0335 (13)0.0394 (14)0.0023 (11)0.0122 (11)0.0003 (10)
C20.0500 (19)0.0368 (15)0.0474 (17)0.0022 (13)0.0184 (13)0.0075 (12)
C30.055 (2)0.0339 (15)0.069 (2)0.0067 (14)0.0180 (16)0.0032 (14)
C40.053 (2)0.0447 (17)0.069 (2)0.0020 (15)0.0237 (16)0.0166 (15)
C50.0502 (19)0.0556 (18)0.0399 (16)0.0046 (15)0.0177 (13)0.0109 (13)
S10.0518 (5)0.0440 (4)0.0515 (5)0.0135 (4)0.0255 (4)0.0117 (3)
C60.0394 (16)0.0363 (14)0.0330 (13)0.0031 (12)0.0057 (11)0.0053 (10)
C70.0424 (16)0.0387 (14)0.0372 (15)0.0043 (12)0.0054 (12)0.0025 (11)
O10.0617 (15)0.0510 (13)0.0432 (12)0.0169 (11)0.0140 (10)0.0003 (9)
O20.0669 (16)0.0549 (14)0.0390 (12)0.0156 (12)0.0205 (10)0.0064 (9)
Geometric parameters (Å, º) top
N1—C11.334 (3)C5—H5A0.9300
N1—C51.345 (4)S1—S1i2.0251 (17)
C1—C21.385 (4)C6—O11.204 (3)
C1—S11.787 (3)C6—O21.324 (3)
C2—C31.384 (4)C6—C71.507 (4)
C2—H2A0.9300C7—C7ii1.516 (5)
C3—C41.380 (5)C7—H7A0.9700
C3—H3A0.9300C7—H7B0.9700
C4—C51.378 (5)O2—H2H0.83 (4)
C4—H4A0.9300
C1—N1—C5117.2 (3)N1—C5—H5A118.5
N1—C1—C2123.9 (3)C4—C5—H5A118.5
N1—C1—S1111.3 (2)C1—S1—S1i106.10 (10)
C2—C1—S1124.8 (2)O1—C6—O2123.7 (3)
C3—C2—C1117.6 (3)O1—C6—C7124.6 (3)
C3—C2—H2A121.2O2—C6—C7111.7 (2)
C1—C2—H2A121.2C6—C7—C7ii113.6 (2)
C4—C3—C2119.7 (3)C6—C7—H7A108.8
C4—C3—H3A120.2C7ii—C7—H7A108.8
C2—C3—H3A120.2C6—C7—H7B108.8
C5—C4—C3118.5 (3)C7ii—C7—H7B108.8
C5—C4—H4A120.7H7A—C7—H7B107.7
C3—C4—H4A120.7C6—O2—H2H109 (3)
N1—C5—C4123.1 (3)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2H···N10.83 (4)1.94 (4)2.759 (3)173 (4)
C2—H2A···O1iii0.932.473.128 (4)127
Symmetry code: (iii) x, y+1, z1/2.

Experimental details

Crystal data
Chemical formulaC10H8N2S2·C4H6O4
Mr338.39
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)8.4211 (17), 13.347 (3), 14.141 (3)
β (°) 98.43 (3)
V3)1572.2 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.36
Crystal size (mm)0.60 × 0.47 × 0.23
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.822, 0.921
No. of measured, independent and
observed [I > 2σ(I)] reflections
7089, 1799, 1490
Rint0.039
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.139, 1.28
No. of reflections1799
No. of parameters128
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.40, 0.30

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2H···N10.83 (4)1.94 (4)2.759 (3)173 (4)
C2—H2A···O1i0.932.473.128 (4)127
Symmetry code: (i) x, y+1, z1/2.
 

Acknowledgements

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. 2006A610061).

References

First citationDesiraju, G. R. (2003). J. Mol. Struct. 656, 5-15.  Web of Science CrossRef CAS Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationJohnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationRaghavan, N. V. & Seff, K. (1977). Acta Cryst. B33, 386–391.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationThalladi, V. R., Dabros, M., Gehrke, A., Weiss, H. C. & Boese, R. (2007). Cryst. Growth Des. 7, 598–599.  Web of Science CSD CrossRef CAS Google Scholar

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COMMUNICATIONS
ISSN: 2056-9890
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