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

Abstract

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,

• a = 8.4211 (17) Å

• b = 13.347 (3) Å

• c = 14.141 (3) Å

• β = 98.43 (3)°

• V = 1572.2 (6) ų

• 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[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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

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 U_iso(H) = 1.2 U_eq(C). The H atom bonded to O2 atoms was located in a difference Fourier map and its position refined with U_iso(H) = 1.5 Ueq(O).

Figures

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.

Crystal data

C10H8N2S2·C4H6O4	F(000) = 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 = 3.1–27.5°
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

Rigaku R-AXIS RAPID diffractometer	1799 independent reflections
Radiation source: fine-focus sealed tube	1490 reflections with I > 2σ(I)
graphite	Rint = 0.039
Detector resolution: 0 pixels mm-1	θmax = 27.5°, θmin = 3.1°
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

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(Fo2) + (0.0282P)2 + 3.2667P] where P = (Fo2 + 2Fc2)/3
1799 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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, °)

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, °)

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.