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Acta Cryst. (2011). E67, o1923    [ doi:10.1107/S1600536811025694 ]

Bis(4-pyridyl) disulfide-2,2'-[(p-phenylenebis(oxy)]diacetic acid (1/1)

G.-Y. Wang

Abstract top

The asymmetric unit of the title 1:1 co-crystal, C10H8N2S2·C10H10O6, comprises two half-molecules, the bis(4-pyridyl) disulfide having twofold rotational symmetry and the 2,2'-[(p-phenylenebis(oxy)]diacetic acid having crystallographic inversion symmetry. In the disulfide molecule, the dihedral angle between the two pyridine rings is 86.8 (1)°, while the carboxyl groups of the substituted quinone lie essentially in the plane of the benzene ring [dihedral angle = 5.3 (1)°]. In the crystal, the components are linked via intermolecular O-H...N hydrogen bonds into zigzag chains which extend along c and are interlinked through C-H...[pi] associations.

Comment top

Bis(4-pyridyl)disulfide (bpds) is often used as a linker in the construction of coordination polymers because of its flexibility (Kondo et al., 2000; Zhu et al., 2010). The attempt at synthesizing a CdII coordination polymer using bis(4-pyridyl)disulfide and hydroquinone-O,O'-diacetic acid (H2qda) as ligands gave instead the 1:1 title co-crystal C10H8N2S2 . C10H10O6, and the crystal structure is reported here.

In the title compound, the asymmetric unit comprises two half molecules, the bis(4-pyridyl)disulfide having twofold rotational symmetry and the hydroquinone-O,O'-diacetic acid having crystallographic inversion symmetry (Fig. 1). In the disulfide molecule, the dihedral angle between the two pyridine rings is 93.2 (1)° while the carboxylic acid groups of the substituted quinone molecule lie essentially in the plane of the benzene ring [dihedral angle, 5.3 (1)°]. In the crystal, the two components are linked via intermolecular O—H···N hydrogen bonds into one-dimensional zigzag chains which extend along c (Fig. 2) and are inter-linked through C—H···π associations (Table 1, Fig. 3).

Related literature top

For the use of bis(4-pyridyl)disulfide (bpds) as a linker in the construction of coordination polymers, see: Kondo et al. (2000); Zhu et al. (2010).

Experimental top

A mixture of hydroquinone-O,O'-diacetic acid (H2qda) (0.023 g, 0.1 mmol), bis(4-pyridyl)disulfide (bpds) (0.022 g, 0.1 mmol) and Cd(NO3)2 . 4H2O (0.038 g, 0.1 mmol) in H2O (7.0 ml) was placed in a 16 ml Teflon-lined stainless steel vessel and heated to 160 °C for 48 h, then cooled to room temperature at a rate of -5 °C/h. The solution was filtered and the colorless filtrate was allowed to stand at room temperature. Slow evaporation for about one week afforded colorless block crystals.

Refinement top

All H atoms bonded to C atoms were added according to theoretical models, assigned isotropic displacement parameters and allowed to ride on their respective parent atoms [C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C)]. The carboxylic acid H atom was located from the Fourier map and allowed to ride on the parent O atom in the final cycles of refinement, with the O—H distance being fixed at 0.82 Å with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Atom numbering scheme and anisotropic displacement ellipsoid plot of (I) at the 50% probability level. H atoms are represented by circles of arbitrary size. Symmetry codes: (i) -x + 2, y, -z + 1/2; (ii) -x, -y + 2, -z.
[Figure 2] Fig. 2. The one-dimensional zigzag chain structure of the title compound. Non-associative H atoms are omitted and hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The packing diagram of the title compound showing C—H···π interactions.
Bis(4-pyridyl) disulfide–2,2'-[(p-phenylenebis(oxy)]diacetic acid (1/1) top
Crystal data top
C10H8N2S2·C10H10O6F(000) = 928
Mr = 446.50Dx = 1.461 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1634 reflections
a = 14.331 (1) Åθ = 2.8–25.2°
b = 5.057 (1) ŵ = 0.30 mm−1
c = 28.003 (3) ÅT = 296 K
β = 90.200 (5)°Block, colorless
V = 2029.4 (5) Å30.31 × 0.21 × 0.09 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1761 independent reflections
Radiation source: fine-focus sealed tube1450 reflections with I > 2σ(I)
graphiteRint = 0.026
φ and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −10→16
Tmin = 0.912, Tmax = 0.974k = −5→5
4893 measured reflectionsl = −33→32
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0548P)2 + 1.8236P]
where P = (Fo2 + 2Fc2)/3
1761 reflections(Δ/σ)max < 0.001
137 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C10H8N2S2·C10H10O6V = 2029.4 (5) Å3
Mr = 446.50Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.331 (1) ŵ = 0.30 mm−1
b = 5.057 (1) ÅT = 296 K
c = 28.003 (3) Å0.31 × 0.21 × 0.09 mm
β = 90.200 (5)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1761 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1450 reflections with I > 2σ(I)
Tmin = 0.912, Tmax = 0.974Rint = 0.026
4893 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.114Δρmax = 0.62 e Å−3
S = 1.05Δρmin = −0.29 e Å−3
1761 reflectionsAbsolute structure: ?
137 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
S10.92972 (4)−0.22476 (13)0.24909 (2)0.0514 (2)
O10.07968 (11)0.6344 (3)0.06109 (5)0.0485 (4)
O20.15067 (12)0.2818 (4)0.12321 (6)0.0596 (5)
N10.83733 (14)0.3882 (5)0.14055 (7)0.0543 (6)
O30.26328 (12)0.1757 (4)0.07197 (7)0.0683 (6)
H30.28430.09230.09470.102*
C80.04234 (15)0.8125 (4)0.02905 (8)0.0389 (5)
C9−0.02803 (15)0.9711 (5)0.04649 (8)0.0440 (6)
H9−0.04710.95190.07800.053*
C70.15542 (15)0.4802 (5)0.04525 (8)0.0465 (6)
H7A0.20610.59450.03530.056*
H7B0.13640.37370.01810.056*
C30.89942 (16)0.0216 (4)0.20664 (8)0.0425 (5)
C60.18774 (15)0.3037 (5)0.08524 (9)0.0462 (6)
C10.92798 (17)0.3451 (5)0.14718 (8)0.0517 (6)
H10.97030.44080.12890.062*
C20.96216 (16)0.1654 (5)0.17981 (8)0.0476 (6)
H21.02610.14140.18370.057*
C10−0.07061 (15)1.1580 (5)0.01785 (8)0.0443 (6)
H10−0.11811.26360.03000.053*
C40.80519 (17)0.0660 (6)0.19985 (10)0.0584 (7)
H40.7612−0.02830.21730.070*
C50.77771 (19)0.2495 (6)0.16724 (11)0.0639 (8)
H50.71420.28000.16330.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0554 (4)0.0495 (4)0.0492 (4)−0.0077 (3)−0.0039 (3)0.0034 (3)
O10.0518 (10)0.0482 (10)0.0455 (9)0.0114 (8)0.0044 (7)0.0065 (8)
O20.0509 (10)0.0769 (13)0.0511 (10)0.0127 (9)0.0051 (8)0.0143 (9)
N10.0542 (13)0.0617 (14)0.0470 (11)0.0169 (11)−0.0012 (9)0.0002 (10)
O30.0555 (11)0.0901 (15)0.0593 (11)0.0314 (10)0.0075 (9)0.0199 (10)
C80.0398 (12)0.0344 (12)0.0426 (12)−0.0008 (9)−0.0022 (9)0.0013 (9)
C90.0490 (13)0.0446 (14)0.0384 (12)0.0034 (11)0.0044 (10)0.0003 (10)
C70.0410 (12)0.0475 (15)0.0508 (13)0.0035 (10)0.0000 (10)0.0048 (11)
C30.0492 (13)0.0423 (13)0.0361 (11)0.0021 (10)−0.0012 (9)−0.0069 (10)
C60.0397 (13)0.0484 (14)0.0504 (14)−0.0009 (11)−0.0047 (11)0.0023 (11)
C10.0531 (15)0.0570 (16)0.0451 (13)0.0090 (12)0.0057 (11)0.0037 (12)
C20.0424 (13)0.0553 (15)0.0452 (13)0.0083 (11)0.0005 (10)0.0001 (11)
C100.0426 (12)0.0420 (13)0.0481 (13)0.0054 (10)0.0044 (10)−0.0011 (10)
C40.0454 (14)0.0656 (18)0.0643 (16)−0.0013 (13)0.0037 (12)0.0045 (14)
C50.0468 (15)0.075 (2)0.0701 (18)0.0106 (14)−0.0039 (13)0.0013 (16)
Geometric parameters (Å, °) top
S1—C31.775 (2)C7—C61.504 (3)
S1—S1i2.0150 (14)C7—H7A0.9700
O1—C81.378 (3)C7—H7B0.9700
O1—C71.409 (3)C3—C21.381 (3)
O2—C61.195 (3)C3—C41.381 (3)
N1—C11.330 (3)C1—C21.378 (3)
N1—C51.336 (4)C1—H10.9300
O3—C61.316 (3)C2—H20.9300
O3—H30.8200C10—C8ii1.384 (3)
C8—C91.379 (3)C10—H100.9300
C8—C10ii1.384 (3)C4—C51.359 (4)
C9—C101.380 (3)C4—H40.9300
C9—H90.9300C5—H50.9300
C3—S1—S1i105.02 (8)O2—C6—O3125.0 (2)
C8—O1—C7117.02 (17)O2—C6—C7125.5 (2)
C1—N1—C5117.5 (2)O3—C6—C7109.5 (2)
C6—O3—H3109.5N1—C1—C2123.1 (2)
C9—C8—O1115.61 (19)N1—C1—H1118.5
C9—C8—C10ii119.4 (2)C2—C1—H1118.5
O1—C8—C10ii125.0 (2)C1—C2—C3118.5 (2)
C8—C9—C10121.0 (2)C1—C2—H2120.7
C8—C9—H9119.5C3—C2—H2120.7
C10—C9—H9119.5C9—C10—C8ii119.7 (2)
O1—C7—C6109.23 (19)C9—C10—H10120.2
O1—C7—H7A109.8C8ii—C10—H10120.2
C6—C7—H7A109.8C5—C4—C3119.0 (2)
O1—C7—H7B109.8C5—C4—H4120.5
C6—C7—H7B109.8C3—C4—H4120.5
H7A—C7—H7B108.3N1—C5—C4123.4 (2)
C2—C3—C4118.5 (2)N1—C5—H5118.3
C2—C3—S1125.16 (18)C4—C5—H5118.3
C4—C3—S1116.30 (18)
C7—O1—C8—C9−176.4 (2)C5—N1—C1—C20.3 (4)
C7—O1—C8—C10ii3.2 (3)N1—C1—C2—C30.5 (4)
O1—C8—C9—C10179.7 (2)C4—C3—C2—C1−0.5 (3)
C10ii—C8—C9—C100.1 (4)S1—C3—C2—C1178.12 (18)
C8—O1—C7—C6178.70 (18)C8—C9—C10—C8ii−0.1 (4)
S1i—S1—C3—C23.2 (2)C2—C3—C4—C5−0.2 (4)
S1i—S1—C3—C4−178.13 (17)S1—C3—C4—C5−179.0 (2)
O1—C7—C6—O25.5 (3)C1—N1—C5—C4−1.1 (4)
O1—C7—C6—O3−174.7 (2)C3—C4—C5—N11.1 (4)
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
Cg1 is the centroid of the C8–C10/C8'–C10' ring.
D—H···AD—HH···AD···AD—H···A
O3—H3···N1iii0.821.812.629 (3)174
C7—H7B···Cg1iv0.972.763.528 (2)136
Symmetry codes: (iii) x−1/2, y−1/2, z; (iv) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
Cg1 is the centroid of the C8–C10/C8'–C10' ring.
D—H···AD—HH···AD···AD—H···A
O3—H3···N1i0.821.812.629 (3)174
C7—H7B···Cg1ii0.972.763.528 (2)136
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x, y−1, z.
Acknowledgements top

This work was supported financially by the Project of Shandong Province Higher Educational Science and Technology Program (grant No. J11LB56).

references
References top

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Kondo, M., Shimamura, M., Noro, S., Kimura, Y., Uemura, K. & Kitagawa, S. (2000). J. Solid State Chem. 152, 113–119.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhu, H.-L., Zhang, J. & Lin, J.-L. (2010). Acta Cryst. E66, m185.