Ethane-1,2-diaminium 4,4′-sulfonyl­dibenzoate

Smith, G.; Wermuth, U.D.

doi:10.1107/S1600536811041274

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2966

doi:10.1107/S1600536811041274

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Ethane-1,2-diaminium 4,4′-sulfonyldibenzoate

Graham Smith ^a ^* and Urs D. Wermuth ^a

^aFaculty of Science and Technology, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 29 September 2011; accepted 7 October 2011; online 12 October 2011)

In the title salt, C₂H₁₀N₂²⁺·C₁₄H₈O₆S²⁻, both the ethylenediaminium cations and the 4,4′-sulfonyldibenzoate dianions have crystallographic twofold rotational symmetry. They are interlinked by aminium N—H⋯O_carboxylate hydrogen-bonding associations, giving sheets parallel to (101) and are further linked along [010], forming a three-dimensional structure.

Related literature

For the structure of 4,4′-sulfonyldibenzoic acid, see: Lian et al. (2007 ). For the structures of some metal complexes of the acid, see: Bannerjee et al. (2009 ); Jiao (2010 ); Pan et al. (2007 ); Wu et al. (2007 ); Zhuang & Jin (2007 ).

Experimental

Crystal data

C₂H₁₀N₂²⁺·C₁₄H₈O₆S²⁻
M_r = 366.39
Monoclinic, P 2/c
a = 15.2860 (8) Å
b = 4.8436 (2) Å
c = 11.9803 (6) Å
β = 111.812 (6)°
V = 823.51 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 200 K
0.35 × 0.25 × 0.08 mm

Data collection

Oxford Diffraction Gemini-S CCD detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.98, T_max = 0.99
5062 measured reflections
1607 independent reflections
1290 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.098
S = 1.05
1607 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H11A⋯O42ⁱ	0.89	1.87	2.760 (2)	174
N1A—H12A⋯O41ⁱⁱ	0.89	1.88	2.740 (2)	163
N1A—H13A⋯O42	0.89	1.93	2.798 (2)	164
Symmetry codes: (i) x, y+1, z; (ii) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ) within WinGX (Farrugia, 1999 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811041274/lh5347sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041274/lh5347Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811041274/lh5347Isup3.cml

checkCIF report

Comment top

The structure of the diprotic acid 4,4'-sulfonyldibenzoic acid (SDBA) is known (Lian et al., 2007) and although some metal complexes with SDBA alone have been reported, e.g. with Li (Bannerjee et al., 2009), Zn (Pan et al., 2007; Zhuang & Jin, 2007) and Cd (Jiao, 2010), most structures have been with mixed ligands including this acid (Wu et al., 2007). No structures of compounds of SDBA with Lewis bases are known. Our 1:1 stoichiometric reaction of this acid with ethylenediamine gave the the title compound C₂H₁₀N₂²⁺ C₁₄H₈O₆S^2-, and the structure is reported here. In this structure (Fig. 1), both the ethylenediaminium cations and the 4,4'-sulfonyldibenzoate dianions have crystallographic twofold rotational symmetry. In contrast, the two substituted ring systems of the parent molecule are mirror related (Lian et al., 2007). With the present salt, the central C1—S1—C1ⁱ bond angle is 104.90 (8)Å [for symmetry code (i), see Fig. 1], while the carboxyl group (defined by atoms C4–C41–O41–O42) lies slightly out of the plane of the benzene ring [dihedral angle 19.31 (9)°]. The ethylenediamine cation is essentially planar [torsion angle N1A—C1A—C1Aⁱⁱ—N1Aⁱⁱ, 171.97 (14)°]. For symmetry code (ii), see also Fig. 1.

Intermolecular cation aminium N—H···O_carboxyl hydrogen bonds (Table 1) interlink the SDBA dianions into sheets lying in the (101) planes, as well as down the b axis, forming a three-dimensional structure (Fig. 2). The sulfonyl O atoms are involved in inter-species C—H···O associations [C2—H2···O1^v, 3.200 (2) Å: symmetry code (v) -x + 2, -y + 1, -z + 1]. as well as in S—O···Cg interactions [minimum S1—O1···Cg(ring C1^viii–C6^viii) = 3.5409 (13) Å; S—O···Cg angle, 90.61 (5)°: symmetry code (viii) -x + 2, y + 1, -z + 3/2].

Related literature top

For the structure of 4,4'-sulfonyldibenzoic acid, see: Lian et al. (2007). For the structures of some metal complexes of the acid, see: Bannerjee et al. (2009); Jiao (2010); Pan et al. (2007); Wu et al. (2007); Zhuang & Jin (2007).

Experimental top

The title compound was synthesized by heating together for 10 min under reflux, 1 mmol quantities of 4,4'-sulfonyldibenzoic acid and ethylenediamine in 50 ml of 50% ethanol–water. After evaporation of the solvent the non-crystalline product was recrystallized from a 50% methanol–isopropyl alcohol solution giving thin colourless crystal plates from which a specimen was cleaved for the X-ray analysis..

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular conformation and atom-numbering scheme for the title compound, with the inter-species hydrogen bond shown as a dashed line and with non-H atoms shown as 50% probability displacement ellipsoids. Both the dication and the dianion have twofold rotational symmetry [symmetry codes (i) -x + 2, y, -z + 3/2; (ii) -x + 1, y, -z + 1/2].
	Fig. 2. A perspective view of the three-dimensional structure looking along the b axial direction, showing hydrogen-bonding associations as dashed lines. Carbon-bound H atoms are omitted. For symmetry codes, see Table 1 and Fig. 1.

Ethane-1,2-diaminium 4,4'-sulfonyldibenzoate top

Crystal data top

C₂H₁₀N₂²⁺·C₁₄H₈O₆S²⁻	F(000) = 384
M_r = 366.39	D_x = 1.478 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 2936 reflections
a = 15.2860 (8) Å	θ = 3.5–28.6°
b = 4.8436 (2) Å	µ = 0.23 mm⁻¹
c = 11.9803 (6) Å	T = 200 K
β = 111.812 (6)°	Plate, colourless
V = 823.51 (8) Å³	0.35 × 0.25 × 0.08 mm
Z = 2

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	1607 independent reflections
Radiation source: Enhance (Mo) X-ray source	1290 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.4°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −5→5
T_min = 0.98, T_max = 0.99	l = −14→14
5062 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0627P)²] where P = (F_o² + 2F_c²)/3
1607 reflections	(Δ/σ)_max < 0.001
114 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂H₁₀N₂²⁺·C₁₄H₈O₆S²⁻	V = 823.51 (8) Å³
M_r = 366.39	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 15.2860 (8) Å	µ = 0.23 mm⁻¹
b = 4.8436 (2) Å	T = 200 K
c = 11.9803 (6) Å	0.35 × 0.25 × 0.08 mm
β = 111.812 (6)°

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	1607 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1290 reflections with I > 2σ(I)
T_min = 0.98, T_max = 0.99	R_int = 0.024
5062 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	Δρ_max = 0.35 e Å⁻³
1607 reflections	Δρ_min = −0.25 e Å⁻³
114 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	1.00000	0.61975 (12)	0.75000	0.0180 (2)
O1	1.03086 (9)	0.7681 (3)	0.66702 (11)	0.0249 (4)
O41	0.63470 (9)	−0.2635 (3)	0.51471 (11)	0.0301 (4)
O42	0.66855 (9)	−0.1734 (3)	0.35316 (10)	0.0243 (4)
C1	0.90679 (11)	0.3967 (3)	0.66620 (15)	0.0175 (5)
C2	0.90534 (12)	0.2888 (4)	0.55790 (16)	0.0225 (5)
C3	0.83192 (12)	0.1147 (4)	0.49238 (15)	0.0221 (5)
C4	0.76174 (11)	0.0437 (4)	0.53517 (14)	0.0176 (5)
C5	0.76491 (13)	0.1538 (4)	0.64426 (16)	0.0216 (5)
C6	0.83708 (12)	0.3320 (4)	0.71004 (16)	0.0221 (5)
C41	0.68270 (12)	−0.1474 (3)	0.46402 (15)	0.0192 (5)
N1A	0.61734 (10)	0.3312 (3)	0.23264 (13)	0.0242 (5)
C1A	0.51341 (13)	0.3110 (4)	0.19485 (16)	0.0273 (6)
H2	0.95280	0.33250	0.52980	0.0270*
H3	0.82960	0.04480	0.41900	0.0260*
H5	0.71830	0.10750	0.67330	0.0260*
H6	0.83850	0.40660	0.78220	0.0260*
H11A	0.63740	0.48570	0.27460	0.0290*
H12A	0.63270	0.33380	0.16790	0.0290*
H13A	0.64420	0.18630	0.27810	0.0290*
H14A	0.48380	0.46620	0.14350	0.0330*
H15A	0.49130	0.14250	0.14940	0.0330*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0190 (3)	0.0165 (3)	0.0174 (3)	0.0000	0.0055 (2)	0.0000
O1	0.0270 (7)	0.0217 (7)	0.0255 (7)	−0.0024 (5)	0.0091 (6)	0.0053 (6)
O41	0.0338 (8)	0.0381 (8)	0.0204 (7)	−0.0146 (6)	0.0123 (6)	−0.0022 (6)
O42	0.0310 (7)	0.0265 (7)	0.0153 (6)	−0.0061 (5)	0.0086 (5)	−0.0033 (5)
C1	0.0170 (8)	0.0169 (9)	0.0167 (8)	0.0018 (6)	0.0041 (7)	0.0021 (7)
C2	0.0214 (9)	0.0292 (10)	0.0195 (9)	−0.0025 (7)	0.0107 (7)	−0.0014 (8)
C3	0.0257 (9)	0.0265 (10)	0.0158 (9)	−0.0013 (8)	0.0098 (7)	−0.0031 (7)
C4	0.0177 (8)	0.0187 (9)	0.0148 (8)	0.0021 (7)	0.0041 (7)	0.0028 (7)
C5	0.0237 (9)	0.0244 (10)	0.0214 (9)	−0.0038 (7)	0.0140 (8)	−0.0008 (7)
C6	0.0268 (9)	0.0244 (10)	0.0169 (9)	−0.0014 (8)	0.0103 (8)	−0.0037 (7)
C41	0.0215 (9)	0.0185 (9)	0.0179 (9)	0.0027 (7)	0.0077 (7)	0.0027 (7)
N1A	0.0292 (9)	0.0254 (8)	0.0189 (8)	−0.0004 (7)	0.0099 (7)	−0.0003 (7)
C1A	0.0245 (10)	0.0361 (11)	0.0209 (10)	0.0020 (8)	0.0080 (8)	−0.0024 (8)

Geometric parameters (Å, º) top

S1—O1	1.4407 (14)	C2—C3	1.390 (3)
S1—C1	1.7726 (17)	C3—C4	1.393 (3)
S1—O1ⁱ	1.4407 (14)	C4—C41	1.509 (2)
S1—C1ⁱ	1.7726 (17)	C4—C5	1.396 (2)
O41—C41	1.247 (2)	C5—C6	1.392 (3)
O42—C41	1.270 (2)	C2—H2	0.9300
N1A—C1A	1.485 (3)	C3—H3	0.9300
N1A—H13A	0.8900	C5—H5	0.9300
N1A—H11A	0.8900	C6—H6	0.9300
N1A—H12A	0.8900	C1A—C1Aⁱⁱ	1.522 (3)
C1—C2	1.391 (2)	C1A—H14A	0.9700
C1—C6	1.388 (3)	C1A—H15A	0.9700

O1—S1—C1	108.27 (8)	C4—C5—C6	120.77 (18)
O1—S1—O1ⁱ	120.17 (9)	C1—C6—C5	118.97 (17)
O1—S1—C1ⁱ	107.12 (8)	O42—C41—C4	116.17 (16)
O1ⁱ—S1—C1	107.12 (8)	O41—C41—O42	124.21 (16)
C1—S1—C1ⁱ	104.90 (8)	O41—C41—C4	119.61 (15)
O1ⁱ—S1—C1ⁱ	108.27 (8)	C3—C2—H2	121.00
C1A—N1A—H11A	109.00	C1—C2—H2	120.00
C1A—N1A—H12A	110.00	C2—C3—H3	120.00
C1A—N1A—H13A	109.00	C4—C3—H3	120.00
H11A—N1A—H12A	109.00	C4—C5—H5	120.00
H11A—N1A—H13A	109.00	C6—C5—H5	120.00
H12A—N1A—H13A	109.00	C5—C6—H6	120.00
C2—C1—C6	121.32 (16)	C1—C6—H6	121.00
S1—C1—C2	119.21 (14)	N1A—C1A—C1Aⁱⁱ	109.76 (15)
S1—C1—C6	119.47 (13)	N1A—C1A—H14A	110.00
C1—C2—C3	118.96 (17)	N1A—C1A—H15A	110.00
C2—C3—C4	120.83 (16)	H14A—C1A—H15A	108.00
C3—C4—C41	120.53 (15)	C1Aⁱⁱ—C1A—H14A	110.00
C3—C4—C5	119.13 (17)	C1Aⁱⁱ—C1A—H15A	110.00
C5—C4—C41	120.35 (16)

O1—S1—C1—C2	30.61 (16)	C2—C3—C4—C5	1.2 (3)
O1—S1—C1—C6	−149.72 (14)	C2—C3—C4—C41	−179.47 (17)
O1ⁱ—S1—C1—C2	161.56 (14)	C3—C4—C5—C6	−0.1 (3)
O1ⁱ—S1—C1—C6	−18.77 (16)	C41—C4—C5—C6	−179.47 (17)
C1ⁱ—S1—C1—C2	−83.51 (15)	C3—C4—C41—O41	162.10 (17)
C1ⁱ—S1—C1—C6	96.15 (15)	C3—C4—C41—O42	−19.4 (2)
S1—C1—C2—C3	−179.80 (14)	C5—C4—C41—O41	−18.5 (3)
C6—C1—C2—C3	0.5 (3)	C5—C4—C41—O42	159.93 (17)
S1—C1—C6—C5	−179.17 (14)	C4—C5—C6—C1	−0.7 (3)
C2—C1—C6—C5	0.5 (3)	N1A—C1A—C1Aⁱⁱ—N1Aⁱⁱ	171.97 (14)
C1—C2—C3—C4	−1.4 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O42ⁱⁱⁱ	0.89	1.87	2.760 (2)	174
N1A—H12A···O41^iv	0.89	1.88	2.740 (2)	163
N1A—H13A···O42	0.89	1.93	2.798 (2)	164
C2—H2···O1^v	0.93	2.51	3.200 (2)	131
C5—H5···O42^vi	0.93	2.56	3.344 (2)	143
C6—H6···O1ⁱ	0.93	2.55	2.915 (2)	104
C1A—H14A···O41^vii	0.97	2.46	3.384 (2)	160

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

Experimental details

Crystal data
Chemical formula	C₂H₁₀N₂²⁺·C₁₄H₈O₆S²⁻
M_r	366.39
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	200
a, b, c (Å)	15.2860 (8), 4.8436 (2), 11.9803 (6)
β (°)	111.812 (6)
V (Å³)	823.51 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.35 × 0.25 × 0.08

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.98, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	5062, 1607, 1290
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.098, 1.05
No. of reflections	1607
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.25

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O42ⁱ	0.89	1.87	2.760 (2)	174
N1A—H12A···O41ⁱⁱ	0.89	1.88	2.740 (2)	163
N1A—H13A···O42	0.89	1.93	2.798 (2)	164

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

Acknowledgements

The authors acknowledge financial support from the Australian Reseach Council and the Faculty of Science and Technology and the University Library, Queensland University of Technology.

References

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