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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.115
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  O1      ..       2.81 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.17
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          N1
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          5
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

The carbon-bound H-atoms were placed in a calculated position (C–H 0.93 and 0.96 Å) and were included in the refinement in the riding model approximation, U(H) set to 1.2U(C). The amino and hydroxy H-atoms were located in a difference Fourier map, and were refined with distance restraints of N–H 0.88±0.01 Å, O–H 0.84±0.01 Å; their temperature factors were refined.

Computing details

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

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

Crystal data

2C2H8N^+·C6H4O8S2^2^−	F(000) = 380
Mr = 360.40	Dx = 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) Å^3	0.25 × 0.20 × 0.15 mm
Z = 2

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0776P)^2 + 0.1341P] where P = (Fo^2 + 2Fc^2)/3
1849 reflections	(Δ/σ)max = 0.001
112 parameters	Δρmax = 0.78 e Å^−3
3 restraints	Δρmin = −0.25 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—C1^i	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—C3^i	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—C1^i	120.76 (13)
O2—S1—C1	107.34 (7)	C2—C3—H3	119.6
O1—S1—C1	105.76 (7)	C1^i—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
C3^i—C1—C2	120.41 (13)	H5A—C5—H5B	109.5
C3^i—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—C3^i	126.33 (13)	C3^i—C1—C2—O4	178.89 (14)
O1—S1—C1—C3^i	−113.16 (13)	S1—C1—C2—O4	−0.5 (2)
O3—S1—C1—C3^i	5.58 (14)	C3^i—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—C1^i	−178.87 (14)
O3—S1—C1—C2	−175.03 (12)	C1—C2—C3—C1^i	0.1 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3^ii	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···O1^iii	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.