Sulfonated 1,3-bis­(4-pyrid­yl)propane

Kuyinu, O.; Purdy, A.P.; Butcher, R.J.

doi:10.1107/S1600536811018563

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1534

doi:10.1107/S1600536811018563

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Sulfonated 1,3-bis(4-pyridyl)propane

Ore Kuyinu,^a Andrew P. Purdy ^a ^* and Ray J. Butcher ^b

^aChemistry Division, Code 6120 Naval Research Laboratory, 4555 Overlook Avenue SW, Washington, DC 20375, USA, and ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: andrew.purdy@nrl.navy.mil

(Received 27 January 2011; accepted 16 May 2011; online 28 May 2011)

In the title compound, 4-[3-(3-sulfonatopyridin-1-ium-4-yl)propyl]pyridin-1-ium-3-sulfonate, C₁₃H₁₄N₂O₆S₂, the molecule is zwitterionic, with the sulfonic acid proton transfered to the basic pyridine N atom. Also, the structure adopts a butterfly-like conformation with the sulfonate groups on opposite sides of the `wings'. The dihedral angle between the two pyridinium rings is 83.56 (7)°, and this results in the molecule having a chiral conformation and packing. There is strong intermolecular hydrogen bonding between the pyridinium H and sulfonate O atoms of adjoining molecules. In addition, there are weaker intermolecular C—H⋯O interactions.

Related literature

For zwiterionic polymers, see: Estrin & Entelis (1974 ); Sundaram et al. (2010 ). For 1,3-bis(4-pyridyl)propane ligands, see: Chen et al. (2010 ); Correa et al. (2010 ); Sun et al. (2010 ); Zheng et al. (2010 ). For sulfonation of pyridine rings, see: McElvain & Goese (1943 ).

Experimental

Crystal data

C₁₃H₁₄N₂O₆S₂
M_r = 358.38
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.7132 (2) Å
b = 11.2624 (2) Å
c = 13.5369 (2) Å
V = 1480.85 (5) Å³
Z = 4
Cu Kα radiation
μ = 3.59 mm⁻¹
T = 295 K
0.77 × 0.25 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ), based on expressions derived by Clark & Reid (1995 )] T_min = 0.290, T_max = 0.626
3960 measured reflections
2714 independent reflections
2593 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.106
S = 1.06
2714 reflections
208 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ), 899 Friedel pairs
Flack parameter: 0.07 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O3Aⁱ	0.86	1.88	2.706 (3)	159
N1A—H1AA⋯S1ⁱ	0.86	2.79	3.633 (3)	165
N1B—H1BA⋯O2Bⁱⁱ	0.86	1.85	2.710 (3)	176
N1B—H1BA⋯S2ⁱⁱ	0.86	2.85	3.655 (2)	158
C3B—H3BA⋯O1Aⁱⁱⁱ	0.93	2.44	3.008 (3)	119
C4B—H4BA⋯O2A^iv	0.93	2.50	3.035 (3)	117
C5B—H5BA⋯O1B^v	0.93	2.58	3.416 (4)	150
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018563/fl2337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018563/fl2337Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811018563/fl2337Isup3.cml

checkCIF report

Comment top

From the titled compound C₁₃H₁₄N₂O₆S₂ we can see that the sulfonatation of 1,3-bis(4-pyridyl)propane occurs in the meta position under mercury catalysis, the same as when pyridine is sulfonated under similar conditions (McElvain & Goese, 1943). From recent studies, 1,3-bis(4-pyridyl)propane ligands have been shown (Chen et al., 2010; Correa et al., 2010; Sun et al., 2010; Zheng et al., 2010) to be very flexible, and this has been taken advantage of in supramolecular chemistry. Our interest was to link the sulfonated pyridines into a zwitterionic polymer. (Estrin & Entelis, 1974; Sundaram et al., 2010). Polymer zwitterions are very advantageous in the sense that their distinct polar ends have high electric dipoles, and can readily reorient to an applied electric field if the chain is flexible.

In view of the interest in a flexible zwitterionic polymer backbone, the starting material, 1,3-bis(4-pyridyl)propane was sulfonated. The structure of this derivative is reported here. The structure shows that both pyridine rings have been sulfonated in the 3-position. As is to be expected for a moiety containing both acidic and basic substituents, the molecule is zwitterionic, with the sulfonic acid proton transfered to the basic pyridine N. The structure has adopted a "butterfly-like" conformation with the sulfonate groups on opposite sides of the "wings". The dihedral angle of 83.56 (7)° between the two pyridinium rings is shown in Figure 2. This has resulted in the molecule being chiral in the solid state even though it is not chiral in solution. There is strong intermolecular hydrogen bonding between the pyridinium H and sulfonate O atoms of adjoining molecules. In addition there are weaker intermolecular C—H···O interactions.

Related literature top

For zwiterionic polymers, see: Estrin & Entelis (1974); Sundaram et al. (2010). For 1,3-bis(4-pyridyl)propane ligands, see: Chen et al. (2010); Correa et al. (2010); Sun et al. (2010); Zheng et al. (2010). For sulfonation of pyridine rings, see: McElvain & Goese (1943).

Experimental top

The compound was prepared by adding a mercury catalyst (0.05 g) to 0.33 g of 1,3-bis(4-pyridyl)propane dissolved in 3.24 g of fuming sulfuric acid (oleum). The reaction mixture was placed in a quartz tube that was sealed under vacuum with a fill factor of 10/15.4 cm. The quartz tube was then placed into a pressurized hydrothermal vessel that was set in a furnace at a temperature of 245°C. The pressure vessel attained an internal temperature of 204°C, and the reaction continued for 5 days. After cooling, the quartz tube was removed from the chamber behind a blast shield in a fume hood, and was frozen with liquid nitrogen before opening. The liquid was then poured into an Erlenmeyer flask containing about 10 ml of triply distilled water and was allowed to stand. Crystals of the titled compound slowly appeared over a month at which point they were washed with alcohol and allowed to air dry on top of the oven at about 50°C. Approximately 0.15 g was isolated (25%). MP: dec 320. NMR: (D₂O/DSS): ¹H, 2.28 (CH₂, 2H), 3.44 (CH₂, 4H), 8.13 (py, 2H), 8.79 (py, 2H), 9.13 (py, 2H); ¹³C 31.75 (CH₂, 1 C), 35.39 (CH₂, 2 C), 131.97, 142.50, 144.09, 145.02, 164.74 (py).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Diagram of C₁₃H₁₄N₂O₆S₂ illustrating the atom numbering scheme used. Thermal ellipsoids are at the 30% probability level.
	Fig. 2. The molecular packing for C₁₃H₁₄N₂O₆S₂ viewed down the c axis showing the hydrogen bonds as dashed lines.

4-[3-(3-sulfonatopyridin-1-ium-4-yl)propyl]pyridin-1-ium-3-sulfonate top

Crystal data top

C₁₃H₁₄N₂O₆S₂	D_x = 1.607 Mg m⁻³
M_r = 358.38	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3437 reflections
a = 9.7132 (2) Å	θ = 4.6–77.4°
b = 11.2624 (2) Å	µ = 3.59 mm⁻¹
c = 13.5369 (2) Å	T = 295 K
V = 1480.85 (5) Å³	Needle, pale yellow
Z = 4	0.77 × 0.25 × 0.19 mm
F(000) = 744

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	2714 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2593 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 10.5081 pixels mm^-1	θ_max = 77.6°, θ_min = 5.1°
ω scans	h = −8→12
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]	k = −11→14
T_min = 0.290, T_max = 0.626	l = −16→13
3960 measured reflections

Refinement top

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0719P)² + 0.3816P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2714 reflections	Δρ_max = 0.51 e Å⁻³
208 parameters	Δρ_min = −0.52 e Å⁻³
12 restraints	Absolute structure: Flack (1983), 899 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (2)

Crystal data top

C₁₃H₁₄N₂O₆S₂	V = 1480.85 (5) Å³
M_r = 358.38	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 9.7132 (2) Å	µ = 3.59 mm⁻¹
b = 11.2624 (2) Å	T = 295 K
c = 13.5369 (2) Å	0.77 × 0.25 × 0.19 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	2714 independent reflections
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]	2593 reflections with I > 2σ(I)
T_min = 0.290, T_max = 0.626	R_int = 0.021
3960 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.106	Δρ_max = 0.51 e Å⁻³
S = 1.06	Δρ_min = −0.52 e Å⁻³
2714 reflections	Absolute structure: Flack (1983), 899 Friedel pairs
208 parameters	Absolute structure parameter: 0.07 (2)
12 restraints

Special details top

Experimental. CrysAlis Pro (Oxford Diffraction, 2007) Analytical numeric absorption correction using a multifaceted crystal model, based on expressions derived by Clark & Reid (1995)

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
S1	0.28273 (7)	0.82506 (6)	0.18353 (4)	0.03490 (17)
S2	0.25484 (7)	0.69702 (6)	0.73312 (6)	0.0450 (2)
O1A	0.1398 (2)	0.8521 (2)	0.16464 (17)	0.0501 (6)
O2A	0.3744 (3)	0.8523 (3)	0.10328 (15)	0.0587 (7)
O3A	0.3027 (2)	0.70553 (17)	0.22295 (16)	0.0444 (5)
O1B	0.2815 (3)	0.6781 (2)	0.8361 (2)	0.0741 (8)
O2B	0.3281 (3)	0.80026 (19)	0.69595 (18)	0.0521 (5)
O3B	0.1119 (3)	0.6967 (3)	0.7050 (3)	0.0883 (11)
N1A	0.4665 (3)	1.0862 (2)	0.3287 (2)	0.0478 (6)
H1AA	0.5265	1.1394	0.3135	0.057*
N1B	0.4929 (2)	0.4168 (2)	0.68491 (18)	0.0356 (5)
H1BA	0.5502	0.3772	0.7204	0.043*
C1	0.1965 (3)	0.8097 (3)	0.41421 (19)	0.0386 (6)
H1A	0.1477	0.7738	0.3593	0.046*
H1B	0.1293	0.8374	0.4620	0.046*
C2	0.2932 (3)	0.7187 (3)	0.4620 (2)	0.0424 (6)
H2A	0.3445	0.7570	0.5147	0.051*
H2B	0.3588	0.6912	0.4131	0.051*
C3	0.2151 (3)	0.6114 (3)	0.5045 (2)	0.0479 (7)
H3A	0.1350	0.6384	0.5409	0.057*
H3B	0.1841	0.5605	0.4512	0.057*
C1A	0.2832 (3)	0.9119 (2)	0.37844 (17)	0.0326 (5)
C2A	0.3323 (3)	0.9228 (2)	0.28185 (18)	0.0301 (5)
C3A	0.4240 (3)	1.0107 (2)	0.2592 (2)	0.0391 (6)
H3AA	0.4569	1.0178	0.1950	0.047*
C4A	0.4185 (4)	1.0818 (3)	0.4211 (3)	0.0553 (9)
H4AA	0.4473	1.1374	0.4675	0.066*
C5A	0.3276 (4)	0.9959 (3)	0.4470 (2)	0.0486 (7)
H5AA	0.2945	0.9929	0.5114	0.058*
C1B	0.3094 (3)	0.5428 (2)	0.57229 (19)	0.0356 (5)
C2B	0.3329 (3)	0.5730 (2)	0.67150 (19)	0.0310 (5)
C3B	0.4251 (3)	0.5075 (2)	0.72588 (19)	0.0338 (5)
H3BA	0.4405	0.5264	0.7918	0.041*
C4B	0.4747 (3)	0.3857 (2)	0.5911 (2)	0.0401 (6)
H4BA	0.5246	0.3229	0.5645	0.048*
C5B	0.3826 (3)	0.4462 (3)	0.53385 (19)	0.0414 (6)
H5BA	0.3684	0.4230	0.4687	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0363 (3)	0.0368 (3)	0.0316 (3)	0.0032 (3)	−0.0007 (2)	−0.0034 (2)
S2	0.0395 (4)	0.0328 (3)	0.0627 (4)	−0.0030 (3)	0.0108 (3)	−0.0146 (3)
O1A	0.0454 (12)	0.0517 (13)	0.0531 (12)	0.0097 (10)	−0.0129 (9)	−0.0057 (10)
O2A	0.0598 (14)	0.0826 (18)	0.0336 (9)	−0.0084 (14)	0.0095 (10)	−0.0077 (11)
O3A	0.0485 (11)	0.0315 (9)	0.0532 (11)	0.0056 (9)	−0.0039 (9)	−0.0078 (8)
O1B	0.102 (2)	0.0568 (14)	0.0640 (14)	0.0053 (16)	0.0363 (15)	−0.0128 (12)
O2B	0.0640 (14)	0.0320 (10)	0.0604 (13)	−0.0069 (10)	−0.0061 (11)	−0.0096 (9)
O3B	0.0386 (12)	0.0712 (18)	0.155 (3)	0.0011 (13)	0.0049 (16)	−0.055 (2)
N1A	0.0484 (14)	0.0281 (11)	0.0669 (17)	−0.0097 (10)	−0.0099 (13)	0.0047 (11)
N1B	0.0359 (11)	0.0312 (10)	0.0396 (11)	0.0001 (9)	0.0002 (9)	0.0083 (9)
C1	0.0378 (13)	0.0425 (14)	0.0354 (11)	0.0022 (12)	0.0038 (10)	0.0110 (11)
C2	0.0405 (14)	0.0468 (14)	0.0401 (13)	−0.0009 (13)	0.0002 (12)	0.0174 (11)
C3	0.0466 (16)	0.0459 (15)	0.0511 (15)	−0.0080 (14)	−0.0070 (14)	0.0181 (13)
C1A	0.0353 (12)	0.0307 (11)	0.0319 (11)	0.0061 (11)	0.0011 (10)	0.0021 (9)
C2A	0.0327 (11)	0.0260 (10)	0.0314 (10)	0.0043 (10)	−0.0011 (9)	0.0024 (9)
C3A	0.0415 (14)	0.0333 (12)	0.0425 (14)	−0.0003 (11)	−0.0002 (11)	0.0086 (11)
C4A	0.071 (2)	0.0360 (15)	0.0585 (18)	−0.0021 (15)	−0.0121 (17)	−0.0129 (14)
C5A	0.0600 (19)	0.0457 (16)	0.0401 (14)	0.0031 (15)	0.0010 (13)	−0.0098 (12)
C1B	0.0388 (13)	0.0312 (12)	0.0368 (12)	−0.0063 (11)	0.0020 (11)	0.0079 (10)
C2B	0.0337 (12)	0.0230 (10)	0.0363 (12)	−0.0032 (9)	0.0067 (10)	−0.0013 (9)
C3B	0.0383 (12)	0.0332 (12)	0.0299 (11)	−0.0069 (10)	0.0025 (10)	−0.0008 (10)
C4B	0.0488 (15)	0.0286 (12)	0.0428 (14)	0.0014 (12)	0.0105 (12)	−0.0010 (11)
C5B	0.0557 (16)	0.0412 (14)	0.0272 (11)	−0.0061 (14)	0.0046 (11)	−0.0023 (11)

Geometric parameters (Å, º) top

S1—O2A	1.438 (2)	C2—H2A	0.9700
S1—O1A	1.444 (2)	C2—H2B	0.9700
S1—O3A	1.461 (2)	C3—C1B	1.509 (4)
S1—C2A	1.793 (3)	C3—H3A	0.9700
S2—O1B	1.433 (3)	C3—H3B	0.9700
S2—O3B	1.439 (3)	C1A—C5A	1.394 (4)
S2—O2B	1.453 (2)	C1A—C2A	1.397 (3)
S2—C2B	1.795 (2)	C2A—C3A	1.366 (4)
N1A—C3A	1.334 (4)	C3A—H3AA	0.9300
N1A—C4A	1.337 (5)	C4A—C5A	1.356 (5)
N1A—H1AA	0.8600	C4A—H4AA	0.9300
N1B—C4B	1.329 (4)	C5A—H5AA	0.9300
N1B—C3B	1.336 (3)	C1B—C5B	1.400 (4)
N1B—H1BA	0.8600	C1B—C2B	1.404 (4)
C1—C1A	1.506 (4)	C2B—C3B	1.375 (4)
C1—C2	1.534 (4)	C3B—H3BA	0.9300
C1—H1A	0.9700	C4B—C5B	1.366 (4)
C1—H1B	0.9700	C4B—H4BA	0.9300
C2—C3	1.539 (4)	C5B—H5BA	0.9300

O2A—S1—O1A	114.62 (15)	C1B—C3—H3B	109.8
O2A—S1—O3A	112.98 (15)	C2—C3—H3B	109.8
O1A—S1—O3A	112.74 (14)	H3A—C3—H3B	108.3
O2A—S1—C2A	105.27 (13)	C5A—C1A—C2A	117.2 (3)
O1A—S1—C2A	105.09 (12)	C5A—C1A—C1	118.5 (2)
O3A—S1—C2A	105.00 (11)	C2A—C1A—C1	124.0 (2)
O1B—S2—O3B	115.5 (2)	C3A—C2A—C1A	119.8 (2)
O1B—S2—O2B	111.54 (16)	C3A—C2A—S1	116.9 (2)
O3B—S2—O2B	112.5 (2)	C1A—C2A—S1	123.30 (19)
O1B—S2—C2B	105.08 (15)	N1A—C3A—C2A	120.4 (3)
O3B—S2—C2B	106.43 (15)	N1A—C3A—H3AA	119.8
O2B—S2—C2B	104.76 (13)	C2A—C3A—H3AA	119.8
C3A—N1A—C4A	121.9 (3)	N1A—C4A—C5A	119.7 (3)
C3A—N1A—H1AA	119.1	N1A—C4A—H4AA	120.1
C4A—N1A—H1AA	119.1	C5A—C4A—H4AA	120.1
C4B—N1B—C3B	122.2 (2)	C4A—C5A—C1A	120.9 (3)
C4B—N1B—H1BA	118.9	C4A—C5A—H5AA	119.5
C3B—N1B—H1BA	118.9	C1A—C5A—H5AA	119.5
C1A—C1—C2	107.7 (2)	C5B—C1B—C2B	117.5 (2)
C1A—C1—H1A	110.2	C5B—C1B—C3	118.7 (3)
C2—C1—H1A	110.2	C2B—C1B—C3	123.8 (3)
C1A—C1—H1B	110.2	C3B—C2B—C1B	119.2 (2)
C2—C1—H1B	110.2	C3B—C2B—S2	116.38 (19)
H1A—C1—H1B	108.5	C1B—C2B—S2	124.4 (2)
C1—C2—C3	112.4 (2)	N1B—C3B—C2B	120.6 (2)
C1—C2—H2A	109.1	N1B—C3B—H3BA	119.7
C3—C2—H2A	109.1	C2B—C3B—H3BA	119.7
C1—C2—H2B	109.1	N1B—C4B—C5B	119.9 (3)
C3—C2—H2B	109.1	N1B—C4B—H4BA	120.1
H2A—C2—H2B	107.9	C5B—C4B—H4BA	120.1
C1B—C3—C2	109.3 (2)	C4B—C5B—C1B	120.6 (2)
C1B—C3—H3A	109.8	C4B—C5B—H5BA	119.7
C2—C3—H3A	109.8	C1B—C5B—H5BA	119.7

C1A—C1—C2—C3	178.2 (2)	C1—C1A—C5A—C4A	172.4 (3)
C1—C2—C3—C1B	−165.5 (3)	C2—C3—C1B—C5B	−94.3 (3)
C2—C1—C1A—C5A	−78.8 (3)	C2—C3—C1B—C2B	82.9 (3)
C2—C1—C1A—C2A	95.4 (3)	C5B—C1B—C2B—C3B	−0.1 (4)
C5A—C1A—C2A—C3A	2.3 (4)	C3—C1B—C2B—C3B	−177.4 (3)
C1—C1A—C2A—C3A	−172.0 (2)	C5B—C1B—C2B—S2	177.4 (2)
C5A—C1A—C2A—S1	−178.4 (2)	C3—C1B—C2B—S2	0.2 (4)
C1—C1A—C2A—S1	7.3 (4)	O1B—S2—C2B—C3B	−15.5 (3)
O2A—S1—C2A—C3A	9.9 (2)	O3B—S2—C2B—C3B	−138.4 (3)
O1A—S1—C2A—C3A	−111.5 (2)	O2B—S2—C2B—C3B	102.2 (2)
O3A—S1—C2A—C3A	129.4 (2)	O1B—S2—C2B—C1B	166.9 (2)
O2A—S1—C2A—C1A	−169.4 (2)	O3B—S2—C2B—C1B	44.0 (3)
O1A—S1—C2A—C1A	69.2 (2)	O2B—S2—C2B—C1B	−75.4 (2)
O3A—S1—C2A—C1A	−50.0 (2)	C4B—N1B—C3B—C2B	−0.1 (4)
C4A—N1A—C3A—C2A	−2.3 (5)	C1B—C2B—C3B—N1B	0.7 (4)
C1A—C2A—C3A—N1A	−0.2 (4)	S2—C2B—C3B—N1B	−177.00 (19)
S1—C2A—C3A—N1A	−179.5 (2)	C3B—N1B—C4B—C5B	−1.0 (4)
C3A—N1A—C4A—C5A	2.4 (5)	N1B—C4B—C5B—C1B	1.6 (4)
N1A—C4A—C5A—C1A	−0.1 (5)	C2B—C1B—C5B—C4B	−1.0 (4)
C2A—C1A—C5A—C4A	−2.2 (5)	C3—C1B—C5B—C4B	176.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O3Aⁱ	0.86	1.88	2.706 (3)	159
N1A—H1AA···S1ⁱ	0.86	2.79	3.633 (3)	165
N1B—H1BA···O2Bⁱⁱ	0.86	1.85	2.710 (3)	176
N1B—H1BA···S2ⁱⁱ	0.86	2.85	3.655 (2)	158
C3B—H3BA···O1Aⁱⁱⁱ	0.93	2.44	3.008 (3)	119
C4B—H4BA···O2A^iv	0.93	2.50	3.035 (3)	117
C5B—H5BA···O1B^v	0.93	2.58	3.416 (4)	150

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1/2, −y+3/2, −z+1; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂O₆S₂
M_r	358.38
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	9.7132 (2), 11.2624 (2), 13.5369 (2)
V (Å³)	1480.85 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.59
Crystal size (mm)	0.77 × 0.25 × 0.19

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.290, 0.626
No. of measured, independent and observed [I > 2σ(I)] reflections	3960, 2714, 2593
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.06
No. of reflections	2714
No. of parameters	208
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.52
Absolute structure	Flack (1983), 899 Friedel pairs
Absolute structure parameter	0.07 (2)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O3Aⁱ	0.86	1.88	2.706 (3)	159
N1A—H1AA···S1ⁱ	0.86	2.79	3.633 (3)	165
N1B—H1BA···O2Bⁱⁱ	0.86	1.85	2.710 (3)	176
N1B—H1BA···S2ⁱⁱ	0.86	2.85	3.655 (2)	158
C3B—H3BA···O1Aⁱⁱⁱ	0.93	2.44	3.008 (3)	119
C4B—H4BA···O2A^iv	0.93	2.50	3.035 (3)	117
C5B—H5BA···O1B^v	0.93	2.58	3.416 (4)	150

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1/2, −y+3/2, −z+1; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1/2, −y+1, z−1/2.

Acknowledgements

RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer, and we thank the Office of Naval Research for financial support.

References

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