4,4′-Methyl­enedianilinium bis­(3-carb­oxy-4-hydroxy­benzene­sulfonate) monohydrate

Du, G.; Liu*, Z.; Chu, Q.; Li, Z.; Zhang, S.

doi:10.1107/S1600536808029115

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages o1947-o1948

doi:10.1107/S1600536808029115

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4,4′-Methylenedianilinium bis(3-carboxy-4-hydroxybenzenesulfonate) monohydrate

Guihuan Du,^a ^* Zuli Liu,^a Qian Chu,^b Zhen Li ^b and Suming Zhang ^b

^aDepartment of Physics, Huazhong University of Science and Technology, Wuhan 430074, People's Republic of China, and ^bTongji Hospital, Huazhong University of Science and Technology, Wuhan 430070, People's Republic of China
^*Correspondence e-mail: duguihuan@126.com

(Received 1 September 2008; accepted 10 September 2008; online 17 September 2008)

Co-crystallization of 4,4′-methylenediphenylamine (MDA) and 5-sulfosalicylic acid (5-H₂SSA) yields the title salt, C₁₃H₁₆N₂²⁺·2C₇H₅O₆S⁻·H₂O. The asymmetric unit is comprised of one dication, two anions and one water molecule. In the crystal structure, the components of the salt are linked by a combination of intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds into a three-dimensional framework. In addition, two weak π–π interactions [with centroid–centroid distances of 3.8734 (15) and 3.7465 (15) Å] and one C—H⋯π interaction further stabilize the crystal structure.

Related literature

For related structures, see: Smith (2005 ); Smith et al. (2005a ,b , 2006 ). For background information, see: Wang et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₆N₂²⁺·2C₇H₅O₆S⁻·H₂O
M_r = 652.63
Monoclinic, P 2₁
a = 5.8769 (1) Å
b = 18.8659 (3) Å
c = 12.9864 (2) Å
β = 94.668 (1)°
V = 1435.06 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 (2) K
0.40 × 0.30 × 0.04 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.894, T_max = 0.990
16262 measured reflections
6379 independent reflections
5671 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.106
S = 1.09
6379 reflections
433 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 3009 Friedel pairs
Flack parameter: 0.05 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.90 (4)	2.03 (4)	2.896 (4)	161 (3)
N1—H1B⋯O1ⁱⁱ	0.82 (4)	2.47 (3)	2.751 (3)	101 (3)
N1—H1B⋯O12	0.82 (4)	2.01 (4)	2.814 (4)	168 (3)
N1—H1C⋯O11ⁱⁱⁱ	0.99 (4)	1.92 (4)	2.870 (3)	161 (3)
N2—H2A⋯O4ⁱⁱⁱ	0.82 (4)	2.07 (4)	2.801 (4)	149 (3)
N2—H2C⋯O5	0.97 (4)	2.16 (4)	2.927 (4)	135 (3)
N2—H2B⋯O6	0.84 (4)	2.20 (4)	2.889 (4)	139 (3)
N2—H2C⋯O3ⁱ	0.97 (4)	2.19 (4)	2.940 (3)	134 (3)
O2—H2D⋯O11^iv	0.80 (4)	1.91 (4)	2.688 (3)	164 (4)
O3—H3A⋯O1	0.86 (4)	1.77 (4)	2.569 (3)	153 (4)
O8—H8A⋯O13^v	0.87 (5)	1.76 (5)	2.598 (4)	160 (4)
O9—H9A⋯O7	0.86 (5)	1.96 (4)	2.678 (3)	141 (4)
O9—H9A⋯O6^vi	0.86 (5)	2.38 (4)	2.872 (3)	117 (3)
O13—H13A⋯O10^vii	0.83 (8)	1.93 (8)	2.759 (4)	176 (7)
O13—H13B⋯O6	0.89 (7)	2.39 (7)	3.064 (4)	132 (6)
C2—H2⋯O5^viii	0.93	2.54	3.452 (4)	168
C6—H6⋯O12	0.93	2.48	3.210 (3)	136
C12—H12⋯O9^ix	0.93	2.55	3.428 (4)	158
C16—H16⋯Cg^x	0.93	2.85	3.727 (3)	157
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+2]$ ; (ii) x, y-1, z; (iii) x+1, y, z; (iv) x+1, y+1, z; (v) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (vi) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (vii) x, y+1, z; (viii) $[-x+2, y-{\script{1\over 2}}, -z+2]$ ; (ix) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (x) $[-x+1, y+{\script{1\over 2}}, -z+2]$ . Cg is the centroid of the C8–C13 ring.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808029115/lh2691sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029115/lh2691Isup2.hkl

checkCIF report

Comment top

In a continuation of our studies on the molecular and supra-molecular structures in organic salts formed by 5-sulfosaliyclic acid (5-H₂SSA) and N-containing lewis bases (Wang et al., 2008), we now report our findings on the title compound (Scheme I).

Two 5-HSSA^-anions, one 4,4'-methylenediphenylammonium dication (MDA²⁺) and one water molecules comprise the asymmetric unit of (I) (Fig. 1). As in similar analogous organic adducts which have been previuosly reported (Smith et al., 2005a,b; Smith, 2005; Smith et al., 2006), both the sulfonic H atoms are transferred to the amine N atom, yielding the title organic salt. However, the conformations of the sulfonate groups are different in the two anions. The perpendicular distances of the sulfonate O4, O5 and O6 atoms to their adjacent benzene plane are 0.585 (1), 1.263 (1) and 0.967 (1) Å, respectively. The corresponding distances are 1.456 (1), 0.844 (1) and 0.312 (1)Å for O10, O11 and O12 atoms, respectively.

In the crystal structure, the component ions are linked by a combination of O—H···O, N—H···O and C—H···O hydrogen bonds (Table 1), forming a three-dimensional network (Fig.2). An analysis using PLATON (Spek, 2003) showed that two π-π [Cg1···Cg3 = 3.8734 (15) and d_{perpendicular} = 3.522 (2) Å, symmetry code: 1 + x, y, z; Cg2···Cg3 = 3.7465 (15) and d_{perpendicular} = 3.526 (2), symmetry code: 1 - x,1/2 + y,1 - z, where Cg1, Cg2 and Cg3 are the centroids of the C1—C6, C8—C13 and C21—C26 benzene rings, respectively] and one C—H···π [d_H16—_Cg₂= 2.85 Å, d_C16—_Cg₂= 3.727 (3) Å, A_{C16—H16···}_Cg₂=157°, symmetry code: 1 - x,1/2 + y,2 - z] interactions exist, which further consolidate the crystal structure.

Related literature top

For related structures, see: Smith (2005); Smith et al. (2005a,b, 2006). For background information, see: Wang et al. (2008). Cg is the centroid of the C8–C13 ring.

Experimental top

All reagents and solvents were used as obtained without further purification. Equivalent molar amount of 4,4'-methylenediphenylamine and 5-sulfosalicylic acid dihydrate were dissolved in 95% methanol (20 ml). The mixture was stirred for 30 minutes at 300 K and then filtered. Colorless plate crystals of (I) suitable for single-crystal X-ray diffraction analysis grew at the bottom of the vessel in two weeks after slow evaporation of the solution.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H-bonds are shown as dashed lines.
	Fig. 2. Part of the crystal structure of (I), showing the formation of the three-dimensional framework structure. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted from the drawing.

4,4'-Methylenedianilinium bis(3-carboxy-4-hydroxybenzenesulfonate) monohydrate top

Crystal data top

C₁₃H₁₆N₂²⁺·2C₇H₅O₆S⁻·H₂O	F(000) = 680
M_r = 652.63	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7439 reflections
a = 5.8769 (1) Å	θ = 2.7–27.0°
b = 18.8659 (3) Å	µ = 0.26 mm⁻¹
c = 12.9864 (2) Å	T = 296 K
β = 94.668 (1)°	Plate, colorless
V = 1435.06 (4) Å³	0.40 × 0.30 × 0.04 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	6379 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	5671 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
0.3° wide ω exposures scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.894, T_max = 0.990	k = −24→24
16262 measured reflections	l = −16→16

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0586P)² + 0.1606P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
6379 reflections	Δρ_max = 0.33 e Å⁻³
433 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 3009 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (6)

Crystal data top

C₁₃H₁₆N₂²⁺·2C₇H₅O₆S⁻·H₂O	V = 1435.06 (4) Å³
M_r = 652.63	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.8769 (1) Å	µ = 0.26 mm⁻¹
b = 18.8659 (3) Å	T = 296 K
c = 12.9864 (2) Å	0.40 × 0.30 × 0.04 mm
β = 94.668 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	6379 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5671 reflections with I > 2σ(I)
T_min = 0.894, T_max = 0.990	R_int = 0.023
16262 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	Δρ_max = 0.33 e Å⁻³
S = 1.09	Δρ_min = −0.17 e Å⁻³
6379 reflections	Absolute structure: Flack (1983), 3009 Friedel pairs
433 parameters	Absolute structure parameter: 0.05 (6)
1 restraint

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

	x	y	z	U_iso*/U_eq
C1	0.9685 (4)	0.25024 (11)	0.7833 (2)	0.0379 (5)
C2	1.1742 (5)	0.28453 (14)	0.8000 (2)	0.0466 (6)
H2	1.2839	0.2684	0.8502	0.056*
C3	1.2157 (5)	0.34335 (14)	0.7412 (3)	0.0490 (7)
H3	1.3549	0.3667	0.7521	0.059*
C4	1.0543 (5)	0.36826 (13)	0.6662 (2)	0.0430 (6)
C5	0.8515 (5)	0.33235 (15)	0.6504 (2)	0.0491 (7)
H5	0.7427	0.3477	0.5993	0.059*
C6	0.8060 (5)	0.27345 (14)	0.7097 (2)	0.0477 (6)
H6	0.6667	0.2501	0.6993	0.057*
C7	1.0939 (6)	0.43468 (15)	0.6053 (2)	0.0537 (7)
H7A	1.0142	0.4309	0.5371	0.064*
H7B	1.2556	0.4397	0.5969	0.064*
C8	1.0094 (5)	0.49994 (13)	0.6599 (2)	0.0419 (6)
C9	1.1433 (5)	0.53092 (14)	0.7404 (2)	0.0464 (6)
H9	1.2875	0.5125	0.7594	0.056*
C10	1.0668 (5)	0.58854 (14)	0.7929 (2)	0.0451 (6)
H10	1.1597	0.6096	0.8456	0.054*
C11	0.8526 (4)	0.61432 (12)	0.7664 (2)	0.0398 (5)
C12	0.7149 (4)	0.58484 (15)	0.6869 (2)	0.0442 (6)
H12	0.5702	0.6031	0.6689	0.053*
C13	0.7954 (5)	0.52752 (15)	0.6342 (2)	0.0486 (6)
H13	0.7032	0.5073	0.5805	0.058*
N1	0.9214 (5)	0.18836 (12)	0.8458 (2)	0.0443 (5)
H1B	0.804 (6)	0.1679 (19)	0.824 (3)	0.053*
H1A	0.928 (5)	0.1973 (18)	0.914 (3)	0.053*
H1C	1.040 (6)	0.1513 (18)	0.845 (3)	0.053*
N2	0.7665 (5)	0.67217 (14)	0.8262 (2)	0.0515 (6)
H2A	0.861 (6)	0.703 (2)	0.841 (3)	0.062*
H2B	0.665 (6)	0.696 (2)	0.793 (3)	0.062*
H2C	0.692 (6)	0.6611 (19)	0.888 (3)	0.062*
C14	0.5812 (4)	0.96279 (12)	0.95964 (18)	0.0340 (5)
C15	0.4353 (4)	0.99410 (13)	1.02603 (19)	0.0365 (5)
C16	0.2674 (5)	0.95376 (14)	1.0667 (2)	0.0445 (6)
H16	0.1755	0.9739	1.1138	0.053*
C17	0.2356 (5)	0.88431 (13)	1.0379 (2)	0.0407 (6)
H17	0.1199	0.8579	1.0643	0.049*
C18	0.3759 (4)	0.85330 (11)	0.96958 (19)	0.0347 (5)
C19	0.5485 (4)	0.89143 (12)	0.93132 (19)	0.0351 (5)
H19	0.6439	0.8701	0.8867	0.042*
C20	0.7674 (4)	1.00540 (13)	0.91927 (19)	0.0379 (5)
O1	0.7991 (3)	1.06703 (9)	0.94503 (16)	0.0494 (5)
O2	0.8919 (4)	0.97200 (11)	0.85615 (17)	0.0505 (5)
H2D	0.967 (7)	1.001 (2)	0.831 (3)	0.076*
O3	0.4490 (4)	1.06391 (9)	1.05113 (16)	0.0493 (5)
H3A	0.565 (7)	1.079 (2)	1.021 (3)	0.074*
O4	0.0960 (4)	0.74792 (10)	0.94941 (17)	0.0548 (5)
O5	0.4898 (4)	0.72016 (10)	0.99028 (16)	0.0533 (5)
O6	0.3678 (3)	0.76210 (11)	0.82021 (14)	0.0492 (4)
S1	0.32980 (11)	0.76440 (3)	0.92902 (5)	0.03782 (15)
C21	0.0913 (5)	0.20452 (12)	0.48434 (19)	0.0384 (5)
C22	−0.1231 (5)	0.17470 (14)	0.4583 (2)	0.0420 (6)
C23	−0.1983 (4)	0.11873 (15)	0.5176 (2)	0.0440 (6)
H23	−0.3442	0.1004	0.5028	0.053*
C24	−0.0591 (4)	0.09056 (13)	0.5976 (2)	0.0400 (5)
H24	−0.1094	0.0527	0.6355	0.048*
C25	0.1583 (4)	0.11918 (13)	0.62162 (18)	0.0368 (5)
C26	0.2297 (4)	0.17632 (13)	0.56590 (19)	0.0373 (5)
H26	0.3726	0.1962	0.5833	0.045*
C27	0.1761 (5)	0.26283 (15)	0.4210 (2)	0.0466 (6)
O7	0.0906 (5)	0.27667 (13)	0.33542 (18)	0.0716 (7)
O8	0.3540 (4)	0.29627 (12)	0.46501 (18)	0.0578 (6)
H8A	0.407 (7)	0.328 (3)	0.424 (3)	0.087*
O9	−0.2667 (4)	0.19688 (13)	0.37804 (16)	0.0554 (5)
H9A	−0.206 (7)	0.231 (2)	0.348 (3)	0.083*
O10	0.4348 (4)	0.01754 (12)	0.6798 (2)	0.0732 (7)
O11	0.2003 (3)	0.06836 (11)	0.80492 (16)	0.0520 (5)
O12	0.5149 (4)	0.13324 (13)	0.74758 (17)	0.0589 (5)
S2	0.34239 (10)	0.08090 (3)	0.72033 (5)	0.03813 (15)
O13	0.4004 (7)	0.87302 (16)	0.6497 (3)	0.0986 (11)
H13A	0.404 (11)	0.917 (4)	0.657 (5)	0.148*
H13B	0.314 (12)	0.857 (4)	0.698 (5)	0.148*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0465 (14)	0.0255 (11)	0.0430 (13)	0.0029 (9)	0.0114 (11)	0.0018 (9)
C2	0.0433 (15)	0.0386 (13)	0.0572 (17)	0.0012 (11)	−0.0001 (12)	−0.0006 (12)
C3	0.0386 (14)	0.0371 (13)	0.072 (2)	−0.0061 (11)	0.0098 (13)	0.0020 (13)
C4	0.0540 (16)	0.0288 (11)	0.0487 (15)	0.0009 (11)	0.0189 (13)	−0.0001 (10)
C5	0.0567 (17)	0.0378 (13)	0.0515 (17)	−0.0028 (12)	−0.0034 (13)	0.0017 (12)
C6	0.0461 (15)	0.0360 (13)	0.0604 (17)	−0.0075 (11)	0.0012 (12)	−0.0022 (12)
C7	0.074 (2)	0.0380 (14)	0.0532 (17)	−0.0042 (13)	0.0280 (16)	0.0007 (12)
C8	0.0533 (16)	0.0303 (11)	0.0443 (14)	−0.0045 (11)	0.0166 (12)	0.0069 (10)
C9	0.0385 (14)	0.0394 (14)	0.0615 (17)	0.0006 (11)	0.0053 (12)	0.0073 (12)
C10	0.0426 (13)	0.0405 (13)	0.0516 (15)	−0.0040 (11)	−0.0003 (11)	−0.0008 (12)
C11	0.0439 (14)	0.0317 (11)	0.0450 (14)	−0.0026 (10)	0.0110 (11)	0.0057 (10)
C12	0.0395 (13)	0.0438 (13)	0.0489 (15)	−0.0009 (12)	0.0006 (11)	0.0020 (13)
C13	0.0526 (16)	0.0453 (14)	0.0476 (16)	−0.0092 (12)	0.0011 (12)	−0.0004 (12)
N1	0.0522 (14)	0.0327 (11)	0.0493 (14)	−0.0007 (10)	0.0109 (11)	0.0053 (10)
N2	0.0526 (16)	0.0430 (13)	0.0598 (17)	−0.0009 (11)	0.0102 (13)	−0.0071 (11)
C14	0.0373 (12)	0.0294 (10)	0.0354 (12)	−0.0008 (9)	0.0033 (10)	0.0028 (9)
C15	0.0399 (13)	0.0297 (10)	0.0399 (13)	−0.0018 (9)	0.0024 (10)	−0.0014 (10)
C16	0.0502 (15)	0.0355 (12)	0.0506 (16)	0.0006 (11)	0.0204 (12)	−0.0063 (11)
C17	0.0437 (14)	0.0350 (12)	0.0452 (14)	−0.0063 (10)	0.0155 (11)	−0.0015 (11)
C18	0.0416 (14)	0.0255 (10)	0.0373 (13)	−0.0028 (9)	0.0050 (10)	−0.0019 (9)
C19	0.0395 (13)	0.0295 (10)	0.0369 (13)	−0.0001 (9)	0.0076 (10)	−0.0003 (9)
C20	0.0408 (13)	0.0352 (12)	0.0378 (13)	−0.0018 (10)	0.0042 (10)	0.0072 (10)
O1	0.0584 (11)	0.0307 (9)	0.0610 (12)	−0.0109 (8)	0.0165 (9)	0.0016 (8)
O2	0.0503 (12)	0.0434 (10)	0.0609 (12)	−0.0058 (8)	0.0237 (9)	0.0028 (9)
O3	0.0632 (12)	0.0300 (9)	0.0572 (12)	−0.0089 (8)	0.0202 (10)	−0.0088 (8)
O4	0.0591 (12)	0.0426 (11)	0.0648 (13)	−0.0178 (9)	0.0169 (10)	−0.0127 (9)
O5	0.0722 (14)	0.0328 (9)	0.0542 (12)	0.0043 (9)	0.0013 (10)	0.0003 (8)
O6	0.0616 (12)	0.0444 (9)	0.0418 (10)	−0.0044 (9)	0.0053 (8)	−0.0081 (9)
S1	0.0465 (3)	0.0268 (2)	0.0410 (3)	−0.0056 (2)	0.0090 (2)	−0.0048 (2)
C21	0.0487 (14)	0.0309 (11)	0.0366 (12)	0.0026 (10)	0.0093 (11)	−0.0031 (10)
C22	0.0445 (14)	0.0435 (13)	0.0382 (13)	0.0094 (11)	0.0041 (11)	−0.0046 (11)
C23	0.0355 (13)	0.0548 (15)	0.0425 (14)	−0.0062 (11)	0.0078 (11)	−0.0064 (12)
C24	0.0403 (13)	0.0396 (12)	0.0415 (13)	−0.0027 (11)	0.0108 (10)	0.0017 (11)
C25	0.0403 (13)	0.0353 (12)	0.0352 (13)	0.0007 (10)	0.0063 (10)	−0.0040 (10)
C26	0.0375 (12)	0.0355 (11)	0.0398 (13)	−0.0009 (10)	0.0077 (10)	−0.0025 (10)
C27	0.0587 (16)	0.0359 (12)	0.0461 (15)	0.0022 (13)	0.0098 (12)	0.0003 (13)
O7	0.0983 (19)	0.0600 (15)	0.0541 (14)	−0.0140 (12)	−0.0090 (13)	0.0217 (11)
O8	0.0705 (14)	0.0522 (12)	0.0510 (13)	−0.0155 (10)	0.0072 (11)	0.0091 (10)
O9	0.0532 (12)	0.0598 (13)	0.0519 (12)	0.0058 (10)	−0.0041 (9)	0.0067 (10)
O10	0.0848 (17)	0.0520 (12)	0.0842 (17)	0.0241 (12)	0.0150 (14)	0.0013 (12)
O11	0.0452 (10)	0.0580 (12)	0.0537 (11)	−0.0025 (9)	0.0091 (8)	0.0180 (9)
O12	0.0511 (12)	0.0624 (13)	0.0609 (13)	−0.0159 (10)	−0.0087 (10)	0.0176 (10)
S2	0.0342 (3)	0.0355 (3)	0.0456 (3)	0.0013 (2)	0.0084 (2)	0.0066 (3)
O13	0.136 (3)	0.0565 (15)	0.112 (3)	0.0003 (17)	0.058 (2)	−0.0240 (16)

Geometric parameters (Å, º) top

C1—C6	1.368 (4)	C16—C17	1.371 (3)
C1—C2	1.373 (4)	C16—H16	0.9300
C1—N1	1.461 (3)	C17—C18	1.389 (3)
C2—C3	1.381 (4)	C17—H17	0.9300
C2—H2	0.9300	C18—C19	1.370 (3)
C3—C4	1.384 (4)	C18—S1	1.772 (2)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.372 (4)	C20—O1	1.220 (3)
C4—C7	1.510 (4)	C20—O2	1.305 (3)
C5—C6	1.390 (4)	O2—H2D	0.80 (4)
C5—H5	0.9300	O3—H3A	0.86 (4)
C6—H6	0.9300	O4—S1	1.454 (2)
C7—C8	1.524 (4)	O5—S1	1.446 (2)
C7—H7A	0.9700	O6—S1	1.4490 (19)
C7—H7B	0.9700	O6—O13	3.064 (4)
C8—C13	1.377 (4)	C21—C26	1.388 (4)
C8—C9	1.386 (4)	C21—C22	1.396 (4)
C9—C10	1.378 (4)	C21—C27	1.484 (4)
C9—H9	0.9300	C22—O9	1.353 (3)
C10—C11	1.367 (4)	C22—C23	1.400 (4)
C10—H10	0.9300	C23—C24	1.375 (4)
C11—C12	1.376 (4)	C23—H23	0.9300
C11—N2	1.454 (3)	C24—C25	1.399 (4)
C12—C13	1.384 (4)	C24—H24	0.9300
C12—H12	0.9300	C25—C26	1.382 (3)
C13—H13	0.9300	C25—S2	1.763 (3)
N1—H1B	0.82 (4)	C26—H26	0.9300
N1—H1A	0.90 (4)	C27—O7	1.211 (4)
N1—H1C	0.99 (4)	C27—O8	1.311 (4)
N2—H2A	0.82 (4)	O8—H8A	0.87 (5)
N2—H2B	0.84 (4)	O9—H9A	0.86 (5)
N2—H2C	0.97 (4)	O10—S2	1.431 (2)
C14—C15	1.396 (3)	O11—S2	1.4526 (19)
C14—C19	1.405 (3)	O12—S2	1.439 (2)
C14—C20	1.487 (3)	O13—H13A	0.83 (8)
C15—O3	1.357 (3)	O13—H13B	0.89 (7)
C15—C16	1.384 (4)

C6—C1—C2	121.0 (2)	C16—C15—C14	119.7 (2)
C6—C1—N1	119.4 (2)	C17—C16—C15	120.5 (2)
C2—C1—N1	119.5 (2)	C17—C16—H16	119.8
C1—C2—C3	119.0 (3)	C15—C16—H16	119.8
C1—C2—H2	120.5	C16—C17—C18	120.1 (2)
C3—C2—H2	120.5	C16—C17—H17	119.9
C2—C3—C4	121.4 (3)	C18—C17—H17	119.9
C2—C3—H3	119.3	C19—C18—C17	120.4 (2)
C4—C3—H3	119.3	C19—C18—S1	119.29 (18)
C5—C4—C3	118.3 (2)	C17—C18—S1	120.28 (18)
C5—C4—C7	120.0 (3)	C18—C19—C14	119.9 (2)
C3—C4—C7	121.6 (3)	C18—C19—H19	120.1
C4—C5—C6	121.1 (3)	C14—C19—H19	120.1
C4—C5—H5	119.5	O1—C20—O2	123.5 (2)
C6—C5—H5	119.5	O1—C20—C14	121.3 (2)
C1—C6—C5	119.2 (3)	O2—C20—C14	115.3 (2)
C1—C6—H6	120.4	C20—O2—H2D	106 (3)
C5—C6—H6	120.4	C15—O3—H3A	104 (3)
C4—C7—C8	110.9 (2)	S1—O6—H2B	111.3 (10)
C4—C7—H7A	109.5	S1—O6—O13	135.06 (12)
C8—C7—H7A	109.5	H2B—O6—O13	99.8 (10)
C4—C7—H7B	109.5	O5—S1—O6	111.97 (12)
C8—C7—H7B	109.5	O5—S1—O4	110.99 (13)
H7A—C7—H7B	108.1	O6—S1—O4	113.21 (12)
C13—C8—C9	118.4 (2)	O5—S1—C18	107.80 (12)
C13—C8—C7	121.2 (3)	O6—S1—C18	106.63 (12)
C9—C8—C7	120.4 (3)	O4—S1—C18	105.80 (11)
C10—C9—C8	121.2 (3)	C26—C21—C22	119.5 (2)
C10—C9—H9	119.4	C26—C21—C27	120.3 (2)
C8—C9—H9	119.4	C22—C21—C27	120.1 (2)
C11—C10—C9	119.2 (3)	O9—C22—C21	123.8 (2)
C11—C10—H10	120.4	O9—C22—C23	116.9 (2)
C9—C10—H10	120.4	C21—C22—C23	119.3 (2)
C10—C11—C12	121.2 (2)	C24—C23—C22	120.8 (2)
C10—C11—N2	119.1 (3)	C24—C23—H23	119.6
C12—C11—N2	119.7 (2)	C22—C23—H23	119.6
C11—C12—C13	118.9 (2)	C23—C24—C25	119.7 (2)
C11—C12—H12	120.6	C23—C24—H24	120.1
C13—C12—H12	120.6	C25—C24—H24	120.1
C8—C13—C12	121.2 (3)	C26—C25—C24	119.7 (2)
C8—C13—H13	119.4	C26—C25—S2	120.4 (2)
C12—C13—H13	119.4	C24—C25—S2	119.95 (19)
C1—N1—H1B	112 (2)	C25—C26—C21	120.9 (2)
C1—N1—H1A	114 (2)	C25—C26—H26	119.5
H1B—N1—H1A	114 (3)	C21—C26—H26	119.5
C1—N1—H1C	113.3 (19)	O7—C27—O8	123.6 (3)
H1B—N1—H1C	103 (3)	O7—C27—C21	122.4 (3)
H1A—N1—H1C	100 (3)	O8—C27—C21	114.0 (2)
C11—N2—H2A	114 (3)	C27—O8—H8A	112 (3)
C11—N2—H2B	113 (2)	C22—O9—H9A	109 (3)
H2A—N2—H2B	100 (4)	O10—S2—O12	112.51 (15)
C11—N2—H2C	119 (2)	O10—S2—O11	113.65 (14)
H2A—N2—H2C	107 (3)	O12—S2—O11	111.27 (13)
H2B—N2—H2C	102 (3)	O10—S2—C25	107.66 (14)
C15—C14—C19	119.3 (2)	O12—S2—C25	106.02 (12)
C15—C14—C20	119.7 (2)	O11—S2—C25	105.07 (11)
C19—C14—C20	121.0 (2)	O6—O13—H13A	127 (5)
O3—C15—C16	118.2 (2)	H13A—O13—H13B	106 (6)
O3—C15—C14	122.1 (2)

C6—C1—C2—C3	0.1 (4)	C19—C14—C20—O1	−178.7 (3)
N1—C1—C2—C3	−179.4 (3)	C15—C14—C20—O2	−178.7 (2)
C1—C2—C3—C4	0.1 (4)	C19—C14—C20—O2	0.8 (4)
C2—C3—C4—C5	−0.9 (4)	H2B—O6—S1—O5	−2.9 (10)
C2—C3—C4—C7	176.9 (3)	O13—O6—S1—O5	−133.47 (18)
C3—C4—C5—C6	1.5 (4)	H2B—O6—S1—O4	−129.3 (10)
C7—C4—C5—C6	−176.3 (3)	O13—O6—S1—O4	100.15 (19)
C2—C1—C6—C5	0.5 (4)	H2B—O6—S1—C18	114.8 (10)
N1—C1—C6—C5	180.0 (3)	O13—O6—S1—C18	−15.8 (2)
C4—C5—C6—C1	−1.4 (4)	C19—C18—S1—O5	82.1 (2)
C5—C4—C7—C8	88.5 (3)	C17—C18—S1—O5	−99.1 (2)
C3—C4—C7—C8	−89.3 (3)	C19—C18—S1—O6	−38.3 (2)
C4—C7—C8—C13	−95.7 (3)	C17—C18—S1—O6	140.5 (2)
C4—C7—C8—C9	81.2 (3)	C19—C18—S1—O4	−159.1 (2)
C13—C8—C9—C10	−0.9 (4)	C17—C18—S1—O4	19.7 (3)
C7—C8—C9—C10	−177.9 (2)	C26—C21—C22—O9	−177.7 (2)
C8—C9—C10—C11	1.6 (4)	C27—C21—C22—O9	−1.6 (4)
C9—C10—C11—C12	−1.6 (4)	C26—C21—C22—C23	2.6 (4)
C9—C10—C11—N2	176.1 (2)	C27—C21—C22—C23	178.7 (2)
C10—C11—C12—C13	0.8 (4)	O9—C22—C23—C24	176.9 (2)
N2—C11—C12—C13	−176.8 (3)	C21—C22—C23—C24	−3.4 (4)
C9—C8—C13—C12	0.1 (4)	C22—C23—C24—C25	1.5 (4)
C7—C8—C13—C12	177.1 (2)	C23—C24—C25—C26	1.1 (4)
C11—C12—C13—C8	−0.1 (4)	C23—C24—C25—S2	−177.24 (19)
C19—C14—C15—O3	−175.8 (2)	C24—C25—C26—C21	−1.9 (4)
C20—C14—C15—O3	3.7 (4)	S2—C25—C26—C21	176.48 (18)
C19—C14—C15—C16	2.9 (4)	C22—C21—C26—C25	0.0 (4)
C20—C14—C15—C16	−177.6 (2)	C27—C21—C26—C25	−176.1 (2)
O3—C15—C16—C17	175.3 (3)	C26—C21—C27—O7	160.4 (3)
C14—C15—C16—C17	−3.5 (4)	C22—C21—C27—O7	−15.6 (4)
C15—C16—C17—C18	1.6 (4)	C26—C21—C27—O8	−17.9 (3)
C16—C17—C18—C19	0.8 (4)	C22—C21—C27—O8	166.1 (2)
C16—C17—C18—S1	−178.0 (2)	C26—C25—S2—O10	−101.6 (2)
C17—C18—C19—C14	−1.3 (4)	C24—C25—S2—O10	76.8 (2)
S1—C18—C19—C14	177.48 (19)	C26—C25—S2—O12	19.1 (2)
C15—C14—C19—C18	−0.5 (4)	C24—C25—S2—O12	−162.6 (2)
C20—C14—C19—C18	180.0 (2)	C26—C25—S2—O11	137.0 (2)
C15—C14—C20—O1	1.8 (4)	C24—C25—S2—O11	−44.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.90 (4)	2.03 (4)	2.896 (4)	161 (3)
N1—H1B···O1ⁱⁱ	0.82 (4)	2.47 (3)	2.751 (3)	101 (3)
N1—H1B···O12	0.82 (4)	2.01 (4)	2.814 (4)	168 (3)
N1—H1C···O11ⁱⁱⁱ	0.99 (4)	1.92 (4)	2.870 (3)	161 (3)
N2—H2A···O4ⁱⁱⁱ	0.82 (4)	2.07 (4)	2.801 (4)	149 (3)
N2—H2C···O5	0.97 (4)	2.16 (4)	2.927 (4)	135 (3)
N2—H2B···O6	0.84 (4)	2.20 (4)	2.889 (4)	139 (3)
N2—H2C···O3ⁱ	0.97 (4)	2.19 (4)	2.940 (3)	134 (3)
O2—H2D···O11^iv	0.80 (4)	1.91 (4)	2.688 (3)	164 (4)
O3—H3A···O1	0.86 (4)	1.77 (4)	2.569 (3)	153 (4)
O8—H8A···O13^v	0.87 (5)	1.76 (5)	2.598 (4)	160 (4)
O9—H9A···O7	0.86 (5)	1.96 (4)	2.678 (3)	141 (4)
O9—H9A···O6^vi	0.86 (5)	2.38 (4)	2.872 (3)	117 (3)
O13—H13A···O10^vii	0.83 (8)	1.93 (8)	2.759 (4)	176 (7)
O13—H13B···O6	0.89 (7)	2.39 (7)	3.064 (4)	132 (6)
C2—H2···O5^viii	0.93	2.54	3.452 (4)	168
C6—H6···O12	0.93	2.48	3.210 (3)	136
C12—H12···O9^ix	0.93	2.55	3.428 (4)	158
C16—H16···Cg^x	0.93	2.85	3.727 (3)	157

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆N₂²⁺·2C₇H₅O₆S⁻·H₂O
M_r	652.63
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	5.8769 (1), 18.8659 (3), 12.9864 (2)
β (°)	94.668 (1)
V (Å³)	1435.06 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.40 × 0.30 × 0.04

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.894, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	16262, 6379, 5671
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.106, 1.09
No. of reflections	6379
No. of parameters	433
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.17
Absolute structure	Flack (1983), 3009 Friedel pairs
Absolute structure parameter	0.05 (6)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.90 (4)	2.03 (4)	2.896 (4)	161 (3)
N1—H1B···O1ⁱⁱ	0.82 (4)	2.47 (3)	2.751 (3)	101 (3)
N1—H1B···O12	0.82 (4)	2.01 (4)	2.814 (4)	168 (3)
N1—H1C···O11ⁱⁱⁱ	0.99 (4)	1.92 (4)	2.870 (3)	161 (3)
N2—H2A···O4ⁱⁱⁱ	0.82 (4)	2.07 (4)	2.801 (4)	149 (3)
N2—H2C···O5	0.97 (4)	2.16 (4)	2.927 (4)	135 (3)
N2—H2B···O6	0.84 (4)	2.20 (4)	2.889 (4)	139 (3)
N2—H2C···O3ⁱ	0.97 (4)	2.19 (4)	2.940 (3)	134 (3)
O2—H2D···O11^iv	0.80 (4)	1.91 (4)	2.688 (3)	164 (4)
O3—H3A···O1	0.86 (4)	1.77 (4)	2.569 (3)	153 (4)
O8—H8A···O13^v	0.87 (5)	1.76 (5)	2.598 (4)	160 (4)
O9—H9A···O7	0.86 (5)	1.96 (4)	2.678 (3)	141 (4)
O9—H9A···O6^vi	0.86 (5)	2.38 (4)	2.872 (3)	117 (3)
O13—H13A···O10^vii	0.83 (8)	1.93 (8)	2.759 (4)	176 (7)
O13—H13B···O6	0.89 (7)	2.39 (7)	3.064 (4)	132 (6)
C2—H2···O5^viii	0.93	2.54	3.452 (4)	167.7
C6—H6···O12	0.93	2.48	3.210 (3)	135.7
C12—H12···O9^ix	0.93	2.55	3.428 (4)	157.7
C16—H16···Cg^x	0.93	2.85	3.727 (3)	157

Acknowledgements

This work was supported by the National Natural Science Foundation of China under grant Nos. 10574047, 10574048 and 20490210. This work was also supported by the National 973 Project under grant No. 2006CB921605.

References

Bruker (2007). SAINT-Plus and SMART. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G. (2005). Acta Cryst. E61, o3398–o3400. Web of Science CSD CrossRef IUCr Journals Google Scholar
Smith, G., Wermuth, U. D. & White, J. M. (2005a). Acta Cryst. E61, o313–o316. Web of Science CSD CrossRef IUCr Journals Google Scholar
Smith, G., Wermuth, U. D. & White, J. M. (2005b). Acta Cryst. C61, o105–o109. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Smith, G., Wermuth, U. D. & Healy, P. C. (2006). Acta Cryst. E62, o2313–o2315. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Z., Yao, K., Liu, Z. & Xu, H. (2008). Acta Cryst. E64, o1192. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 64| Part 10| October 2008| Pages o1947-o1948

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4,4′-Methyl­enedianilinium bis­­(3-carb­­oxy-4-hy­droxy­benzene­sulfonate) monohydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4,4′-Methylenedianilinium bis(3-carboxy-4-hydroxybenzenesulfonate) monohydrate