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

Zhang, C.; Yuan, L.; Liu, J.-Y.; Xu, W.

doi:10.1107/S1600536809016213

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1213

doi:10.1107/S1600536809016213

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

Cheng Zhang,^a Ling Yuan,^a Ji-Yong Liu ^a and Wei Xu ^a ^*

^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 ); Thalladi et al. (2007 ). For a related structure, see: Raghavan et al. (1977 ).

Experimental

Crystal data

C₁₀H₈N₂S₂·C₄H₆O₄
M_r = 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 ) T_min = 0.822, T_max = 0.921
7089 measured reflections
1799 independent reflections
1490 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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 code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016213/lh2792sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016213/lh2792Isup2.hkl

checkCIF report

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.

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

	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.
	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·C₄H₆O₄	F(000) = 704
M_r = 338.39	D_x = 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 = 3.1–27.5°
b = 13.347 (3) Å	µ = 0.36 mm⁻¹
c = 14.141 (3) Å	T = 293 K
β = 98.43 (3)°	Block, colorless
V = 1572.2 (6) Å³	0.60 × 0.47 × 0.23 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1799 independent reflections
Radiation source: fine-focus sealed tube	1490 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −17→17
T_min = 0.822, T_max = 0.921	l = −18→16
7089 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	w = 1/[σ²(F_o²) + (0.0282P)² + 3.2667P] where P = (F_o² + 2F_c²)/3
1799 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₀H₈N₂S₂·C₄H₆O₄	V = 1572.2 (6) Å³
M_r = 338.39	Z = 4
Monoclinic, C2/c	Mo Kα radiation
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)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1799 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1490 reflections with I > 2σ(I)
T_min = 0.822, T_max = 0.921	R_int = 0.039
7089 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	Δρ_max = 0.40 e Å⁻³
1799 reflections	Δρ_min = −0.30 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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 code: (iii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂S₂·C₄H₆O₄
M_r	338.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	8.4211 (17), 13.347 (3), 14.141 (3)
β (°)	98.43 (3)
V (Å³)	1572.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.60 × 0.47 × 0.23

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.822, 0.921
No. of measured, independent and observed [I > 2σ(I)] reflections	7089, 1799, 1490
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.139, 1.28
No. of reflections	1799
No. of parameters	128
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···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 code: (i) x, −y+1, z−1/2.

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

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