Bis(dimethyl­ammonium) 2,5-dihy­droxy­benzene-1,4-disulfonate

Gao, S.; Ng, S.W.

doi:10.1107/S1600536812003406

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o555

doi:10.1107/S1600536812003406

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Bis(dimethylammonium) 2,5-dihydroxybenzene-1,4-disulfonate

Shan Gao ^a and Seik Weng Ng ^b,^c ^*

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 23 January 2012; accepted 26 January 2012; online 31 January 2012)

In the crystal of the title salt, 2C₂H₈N⁺·C₆H₄O₈S₂²⁻, the anion lies on a center of inversion. The dimethylammonium cation forms one N—H⋯O hydrogen bond and another bifurcated N—H⋯O hydrogen bond. The hydroxy group links with the sulfonyl group via an intermolecular O—H⋯O hydrogen bond. These N—H⋯O and O—H⋯O hydrogen bonds generate a three-dimensional network.

Related literature

For the diethylammonium salt, see: Solans et al. (1982 ).

Experimental

Crystal data

2C₂H₈N⁺·C₆H₄O₈S₂²⁻
M_r = 360.40
Monoclinic, P 2₁ /c
a = 8.0136 (12) Å
b = 12.2741 (19) Å
c = 9.2061 (16) Å
β = 115.268 (5)°
V = 818.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.770, T_max = 1.000
7785 measured reflections
1849 independent reflections
1675 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.115
S = 1.07
1849 reflections
112 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.78 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
O4—H4⋯O3ⁱ	0.83 (1)	1.85 (1)	2.670 (2)	175 (2)
N1—H1⋯O1	0.88 (1)	2.13 (2)	2.866 (2)	140 (2)
N1—H1⋯O1ⁱⁱ	0.88 (1)	2.21 (2)	2.921 (2)	138 (2)
N1—H2⋯O2ⁱⁱⁱ	0.89 (1)	2.07 (2)	2.837 (2)	143 (3)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x, -y+1, -z+1; (iii) -x+1, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003406/xu5456sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003406/xu5456Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003406/xu5456Isup3.cml

checkCIF report

Comment top

Bis(diethylammonium) 2,5-dihydroxy-1,4-benzenedisulfonate is a commercial pharmacological chemical whose crystal structure has been described (Solans et al., 1982). The title dimethyammonium salt (Scheme I) is an unexpected product of a hydrothermal synthesis involving 2,5-dihydroxy-1,4-benzenesulfonate in DMS solvent; the dimethylammonium cation probably resulted from the decomposition of DMF. The anion lies on a center-of-inversion (Fig. 1). The dimethylammonium cation forms one N–H···O hydrogen bond and another bifurcated hydrogen bond. These N–H···O and O–H···O hydrogen bonds generate a three-dimensional network (Table 1).

Related literature top

For the diethylammonium salt, see: Solans et al. (1982).

Experimental top

DMF (8 ml), magnesium hydroxide (1 mmol) and 1,4-dihydroxy-2,5-benzenedisulfonic acid (1 mmol) were heated in a 23-ml, Teflon-lined, stainless-stell Parr bomb at 413 K for 3 days. Colorless crystals were isolated from the cool vessel.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of 2(CH₃)₂NH₂^.C₆H₂(OH)₂(SO₃)₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Bis(dimethylammonium) 2,5-dihydroxybenzene-1,4-disulfonate top

Crystal data top

2C₂H₈N⁺·C₆H₄O₈S₂²⁻	F(000) = 380
M_r = 360.40	D_x = 1.462 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5427 reflections
a = 8.0136 (12) Å	θ = 3.3–27.4°
b = 12.2741 (19) Å	µ = 0.36 mm⁻¹
c = 9.2061 (16) Å	T = 293 K
β = 115.268 (5)°	Prism, colorless
V = 818.9 (2) Å³	0.25 × 0.20 × 0.15 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1849 independent reflections
Radiation source: fine-focus sealed tube	1675 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scan	θ_max = 27.4°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→10
T_min = 0.770, T_max = 1.000	k = −15→15
7785 measured reflections	l = −11→11

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0776P)² + 0.1341P] where P = (F_o² + 2F_c²)/3
1849 reflections	(Δ/σ)_max = 0.001
112 parameters	Δρ_max = 0.78 e Å⁻³
3 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

2C₂H₈N⁺·C₆H₄O₈S₂²⁻	V = 818.9 (2) Å³
M_r = 360.40	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0136 (12) Å	µ = 0.36 mm⁻¹
b = 12.2741 (19) Å	T = 293 K
c = 9.2061 (16) Å	0.25 × 0.20 × 0.15 mm
β = 115.268 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1849 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1675 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.037
7785 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	3 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.78 e Å⁻³
1849 reflections	Δρ_min = −0.25 e Å⁻³
112 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.31946 (5)	0.62757 (3)	0.66986 (4)	0.02663 (17)
O1	0.14241 (15)	0.57550 (9)	0.57815 (14)	0.0388 (3)
O2	0.44282 (17)	0.61906 (10)	0.59274 (16)	0.0405 (3)
O3	0.29844 (16)	0.73891 (8)	0.71461 (14)	0.0358 (3)
O4	0.4472 (2)	0.39499 (10)	0.71737 (15)	0.0439 (3)
H4	0.523 (2)	0.3448 (13)	0.742 (3)	0.047 (6)*
N1	0.1913 (2)	0.41948 (15)	0.3680 (2)	0.0466 (4)
H1	0.132 (3)	0.445 (2)	0.422 (3)	0.076 (8)*
H2	0.3121 (16)	0.432 (2)	0.410 (3)	0.085 (9)*
C1	0.4220 (2)	0.55462 (11)	0.85428 (17)	0.0274 (3)
C2	0.4752 (2)	0.44621 (12)	0.85763 (18)	0.0305 (3)
C3	0.5534 (2)	0.39234 (12)	1.00446 (19)	0.0308 (3)
H3	0.5897	0.3200	1.0083	0.037*
C4	0.1193 (3)	0.4894 (2)	0.2257 (3)	0.0727 (7)
H4A	0.1489	0.5640	0.2578	0.109*
H4B	−0.0122	0.4812	0.1710	0.109*
H4C	0.1741	0.4689	0.1551	0.109*
C5	0.1563 (3)	0.3028 (2)	0.3375 (4)	0.0769 (8)
H5A	0.2122	0.2637	0.4372	0.115*
H5B	0.2081	0.2784	0.2665	0.115*
H5C	0.0257	0.2898	0.2890	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0296 (2)	0.0240 (2)	0.0307 (3)	−0.00098 (12)	0.01698 (18)	0.00029 (12)
O1	0.0337 (6)	0.0388 (6)	0.0430 (7)	−0.0054 (5)	0.0156 (5)	−0.0072 (5)
O2	0.0418 (7)	0.0465 (7)	0.0445 (7)	0.0048 (5)	0.0293 (6)	0.0084 (5)
O3	0.0463 (6)	0.0230 (5)	0.0402 (6)	0.0005 (4)	0.0205 (5)	0.0012 (4)
O4	0.0667 (9)	0.0330 (6)	0.0303 (6)	0.0166 (6)	0.0192 (6)	−0.0040 (5)
N1	0.0400 (8)	0.0577 (10)	0.0451 (9)	0.0031 (7)	0.0211 (7)	−0.0086 (7)
C1	0.0334 (7)	0.0236 (7)	0.0302 (7)	−0.0008 (5)	0.0183 (6)	0.0001 (5)
C2	0.0409 (8)	0.0251 (7)	0.0300 (8)	0.0011 (6)	0.0194 (6)	−0.0040 (5)
C3	0.0423 (8)	0.0205 (6)	0.0346 (8)	0.0029 (6)	0.0211 (7)	−0.0017 (5)
C4	0.0601 (13)	0.110 (2)	0.0519 (13)	−0.0003 (14)	0.0279 (11)	0.0132 (13)
C5	0.0589 (13)	0.0636 (15)	0.120 (2)	−0.0071 (11)	0.0497 (15)	−0.0276 (14)

Geometric parameters (Å, º) top

S1—O2	1.4462 (12)	C1—C2	1.394 (2)
S1—O1	1.4531 (11)	C2—C3	1.391 (2)
S1—O3	1.4577 (11)	C3—C1ⁱ	1.391 (2)
S1—C1	1.7799 (15)	C3—H3	0.9300
O4—C2	1.3657 (18)	C4—H4A	0.9600
O4—H4	0.827 (9)	C4—H4B	0.9600
N1—C5	1.463 (3)	C4—H4C	0.9600
N1—C4	1.462 (3)	C5—H5A	0.9600
N1—H1	0.879 (10)	C5—H5B	0.9600
N1—H2	0.890 (10)	C5—H5C	0.9600
C1—C3ⁱ	1.391 (2)

O2—S1—O1	112.67 (8)	O4—C2—C1	119.56 (14)
O2—S1—O3	113.09 (7)	C3—C2—C1	118.83 (13)
O1—S1—O3	112.00 (7)	C2—C3—C1ⁱ	120.76 (13)
O2—S1—C1	107.34 (7)	C2—C3—H3	119.6
O1—S1—C1	105.76 (7)	C1ⁱ—C3—H3	119.6
O3—S1—C1	105.31 (7)	N1—C4—H4A	109.5
C2—O4—H4	106.1 (15)	N1—C4—H4B	109.5
C5—N1—C4	115.6 (2)	H4A—C4—H4B	109.5
C5—N1—H1	110.4 (19)	N1—C4—H4C	109.5
C4—N1—H1	101.2 (19)	H4A—C4—H4C	109.5
C5—N1—H2	110 (2)	H4B—C4—H4C	109.5
C4—N1—H2	103.1 (19)	N1—C5—H5A	109.5
H1—N1—H2	116 (3)	N1—C5—H5B	109.5
C3ⁱ—C1—C2	120.41 (13)	H5A—C5—H5B	109.5
C3ⁱ—C1—S1	118.67 (11)	N1—C5—H5C	109.5
C2—C1—S1	120.91 (11)	H5A—C5—H5C	109.5
O4—C2—C3	121.61 (13)	H5B—C5—H5C	109.5

O2—S1—C1—C3ⁱ	126.33 (13)	C3ⁱ—C1—C2—O4	178.89 (14)
O1—S1—C1—C3ⁱ	−113.16 (13)	S1—C1—C2—O4	−0.5 (2)
O3—S1—C1—C3ⁱ	5.58 (14)	C3ⁱ—C1—C2—C3	−0.1 (3)
O2—S1—C1—C2	−54.28 (14)	S1—C1—C2—C3	−179.49 (11)
O1—S1—C1—C2	66.23 (14)	O4—C2—C3—C1ⁱ	−178.87 (14)
O3—S1—C1—C2	−175.03 (12)	C1—C2—C3—C1ⁱ	0.1 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱⁱ	0.83 (1)	1.85 (1)	2.670 (2)	175 (2)
N1—H1···O1	0.88 (1)	2.13 (2)	2.866 (2)	140 (2)
N1—H1···O1ⁱⁱⁱ	0.88 (1)	2.21 (2)	2.921 (2)	138 (2)
N1—H2···O2^iv	0.89 (1)	2.07 (2)	2.837 (2)	143 (3)

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

Experimental details

Crystal data
Chemical formula	2C₂H₈N⁺·C₆H₄O₈S₂²⁻
M_r	360.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.0136 (12), 12.2741 (19), 9.2061 (16)
β (°)	115.268 (5)
V (Å³)	818.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.770, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7785, 1849, 1675
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.115, 1.07
No. of reflections	1849
No. of parameters	112
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.25

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.83 (1)	1.85 (1)	2.670 (2)	175 (2)
N1—H1···O1	0.88 (1)	2.13 (2)	2.866 (2)	140 (2)
N1—H1···O1ⁱⁱ	0.88 (1)	2.21 (2)	2.921 (2)	138 (2)
N1—H2···O2ⁱⁱⁱ	0.89 (1)	2.07 (2)	2.837 (2)	143 (3)

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

Acknowledgements

This work was supported by the Key Project of the Natural Science Foundation of Heilongjiang Province (grant No. ZD200903), the Key Project of the Education Bureau of Heilongjiang Province (grant Nos. 12511z023, 2011CJHB006), the Innovation Team of the Education Bureau of Heilongjiang Province (grant No. 2010 t d03), Heilongjiang University (grant No. Hdtd2010–04) and the Ministry of Higher Education of Malaysia (grant No. UM·C/HIR/MOHE/SC/12).

References

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