Morpholinium 4-amino-5-meth­oxy-2-methyl­benzensulfonate

Shou, L.-G.; Li, M.-C.

doi:10.1107/S1600536811003722

organic compounds

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Volume 67| Part 3| March 2011| Page o631

doi:10.1107/S1600536811003722

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Morpholinium 4-amino-5-methoxy-2-methylbenzensulfonate

Ling-Gao Shou ^a and Mei-Chao Li ^a ^*

^aCollege of Chemical Engineering and Material Sciences, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: mcl1mcl2@sina.com

(Received 10 January 2011; accepted 29 January 2011; online 12 February 2011)

In the crystal structure of the title compound, C₄H₁₀NO⁺·C₈H₁₀NO₄S⁻, the components are linked by N—H⋯O hydrogen bonds, forming a centrosymmetric 2:2 aggregate. The aggregates are further connected by N—H⋯O hydrogen bonds between the anions, forming a double-tape structure along the a axis.

Related literature

For related structures, see: Barbour et al. (1996 ); Brito et al. (2004 ); Yin et al. (2006 ).

Experimental

Crystal data

C₄H₁₀NO⁺·C₈H₁₀NO₄S⁻
M_r = 304.37
Monoclinic, P 2₁ /c
a = 9.2141 (5) Å
b = 14.8227 (9) Å
c = 10.4740 (7) Å
β = 91.120 (2)°
V = 1430.24 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.34 × 0.25 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.910, T_max = 0.931
13039 measured reflections
3105 independent reflections
2962 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.117
S = 1.12
3105 reflections
191 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.90	1.92	2.795 (3)	162
N1—H1B⋯O2	0.90	2.56	3.126 (2)	121
N1—H1B⋯O3	0.90	1.89	2.790 (3)	175
N2—H2A⋯O1ⁱⁱ	0.86 (2)	2.23 (2)	3.054 (3)	159.1 (2)
N2—H2B⋯O5ⁱⁱⁱ	0.85 (2)	2.25 (2)	3.077 (4)	161.5 (2)
Symmetry codes: (i) -x+2, -y, -z+1; (ii) x-1, y, z; (iii) x-1, y, z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003722/is2665sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003722/is2665Isup2.hkl

checkCIF report

Comment top

Several supramolecular structures of morpholinium sulfonate have been reported previously (Barbour et al., 1996; Yin et al., 2006; Brito et al., 2004). As an extension of research, we report here the structure of the title compound, (I).

As shown in Figs. 1 and 2, the 4-amino-5-methoxy-2-methylbenzensulfonate anion is linked to the morpholinium cation by N1—H1B···O3, N1—H1B···O2 and N1—H1A···O2ⁱ hydrogen bonds (Table 1). Bond lengths of morpholine ring are very similar to those observed previously (Barbour et al., 1996; Yin et al., 2006; Brito et al., 2004). N2—H2A···O1ⁱⁱ and N2—H2B···O5ⁱⁱⁱ hydrogen bonds (Table 1) also play important roles in stabilizing the crystal.

Related literature top

For related structures, see: Barbour et al. (1996); Brito et al. (2004); Yin et al. (2006).

Experimental top

4-Amino-5-methoxy-2-methylbenzensulfonic acid (2.2 g) and morpholine (0.9 g), in a molar ratio of 1:1, were mixed and dissolved in sufficient ethanol by heating to 373 K, at which point a clear solution resulted. The system was then cooled slowly to room temperature. Crystals (2.5 g) were formed, collected and washed with ethanol.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability displacement ellipsoids for non-H atoms. Hydrogen bond is illustrated as dashed lines.
	Fig. 2. The crystal packing of the title compound, viewed down the a axis. Hydrogen bonds are drawn as dashed lines.

Morpholinium 4-amino-5-methoxy-2-methylbenzensulfonate top

Crystal data top

C₄H₁₀NO⁺·C₈H₁₀NO₄S⁻	F(000) = 648.0
M_r = 304.37	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 467 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.2141 (5) Å	Cell parameters from 3615 reflections
b = 14.8227 (9) Å	θ = 2.3–25.3°
c = 10.4740 (7) Å	µ = 0.25 mm⁻¹
β = 91.120 (2)°	T = 293 K
V = 1430.24 (15) Å³	Block, colorless
Z = 4	0.34 × 0.25 × 0.24 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3105 independent reflections
Radiation source: fine-focus sealed tube	2962 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 27.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.910, T_max = 0.931	k = −18→18
13039 measured reflections	l = −13→13

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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0661P)² + 0.3546P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
3105 reflections	Δρ_max = 0.27 e Å⁻³
191 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.083 (5)

Crystal data top

C₄H₁₀NO⁺·C₈H₁₀NO₄S⁻	V = 1430.24 (15) Å³
M_r = 304.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.2141 (5) Å	µ = 0.25 mm⁻¹
b = 14.8227 (9) Å	T = 293 K
c = 10.4740 (7) Å	0.34 × 0.25 × 0.24 mm
β = 91.120 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	3105 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2962 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.931	R_int = 0.034
13039 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.27 e Å⁻³
3105 reflections	Δρ_min = −0.52 e Å⁻³
191 parameters

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
H2A	0.152 (2)	0.1046 (13)	0.8007 (19)	0.044 (5)*
H2B	0.219 (2)	0.1123 (13)	0.925 (2)	0.052 (6)*
C1	0.48589 (15)	0.11584 (9)	0.87597 (13)	0.0312 (3)
C2	0.62334 (14)	0.11986 (9)	0.82610 (13)	0.0316 (3)
H2	0.7039	0.1236	0.8808	0.038*
C3	0.64240 (14)	0.11834 (8)	0.69411 (13)	0.0290 (3)
C4	0.52301 (15)	0.11504 (9)	0.61017 (13)	0.0316 (3)
C5	0.38583 (15)	0.10920 (10)	0.66357 (14)	0.0343 (3)
H5	0.3052	0.1060	0.6090	0.041*
C6	0.36395 (14)	0.10799 (9)	0.79442 (14)	0.0307 (3)
C7	0.53473 (19)	0.11758 (12)	0.46690 (14)	0.0450 (4)
H7A	0.4465	0.0951	0.4284	0.067*
H7B	0.6147	0.0806	0.4414	0.067*
H7C	0.5505	0.1786	0.4397	0.067*
C8	0.57504 (19)	0.12216 (13)	1.09045 (15)	0.0467 (4)
H8C	0.5405	0.1230	1.1763	0.070*
H8D	0.6294	0.1761	1.0748	0.070*
H8E	0.6363	0.0705	1.0790	0.070*
C9	0.91130 (17)	0.12103 (11)	0.23520 (16)	0.0427 (4)
H9A	0.8646	0.1790	0.2222	0.051*
H9B	0.8363	0.0758	0.2453	0.051*
C10	1.12875 (18)	0.18648 (12)	0.33325 (16)	0.0462 (4)
H10A	1.1928	0.1849	0.4078	0.055*
H10B	1.0931	0.2477	0.3228	0.055*
C11	1.21090 (17)	0.15881 (13)	0.21691 (16)	0.0471 (4)
H11A	1.2914	0.1999	0.2047	0.056*
H11B	1.2502	0.0987	0.2293	0.056*
C12	1.0018 (2)	0.09834 (14)	0.12131 (16)	0.0526 (4)
H12A	1.0400	0.0377	0.1310	0.063*
H12B	0.9408	0.0996	0.0448	0.063*
O1	0.91647 (12)	0.12197 (9)	0.75110 (12)	0.0501 (3)
O2	0.83977 (12)	0.02929 (7)	0.57210 (11)	0.0449 (3)
O3	0.83980 (11)	0.19031 (7)	0.55105 (10)	0.0416 (3)
O5	1.11893 (13)	0.15976 (10)	0.10715 (11)	0.0533 (3)
O4	0.45499 (12)	0.11751 (9)	1.00344 (10)	0.0447 (3)
N1	1.00509 (15)	0.12414 (9)	0.35140 (12)	0.0383 (3)
H1A	1.0389	0.0685	0.3690	0.046*
H1B	0.9527	0.1427	0.4181	0.046*
N2	0.22873 (14)	0.09542 (10)	0.84692 (15)	0.0416 (3)
S1	0.82261 (3)	0.11518 (2)	0.63924 (3)	0.03170 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0266 (7)	0.0409 (7)	0.0263 (6)	0.0017 (5)	0.0007 (5)	−0.0003 (5)
C2	0.0234 (6)	0.0425 (7)	0.0287 (6)	0.0004 (5)	−0.0023 (5)	0.0000 (5)
C3	0.0247 (6)	0.0331 (6)	0.0292 (6)	0.0013 (4)	0.0016 (5)	−0.0007 (5)
C4	0.0310 (7)	0.0359 (7)	0.0278 (6)	0.0026 (5)	−0.0022 (5)	−0.0020 (5)
C5	0.0261 (6)	0.0428 (8)	0.0337 (7)	0.0015 (5)	−0.0068 (5)	−0.0025 (5)
C6	0.0240 (6)	0.0330 (6)	0.0351 (7)	0.0022 (5)	−0.0005 (5)	−0.0005 (5)
C7	0.0442 (9)	0.0628 (10)	0.0279 (7)	0.0011 (7)	−0.0031 (6)	−0.0029 (6)
C8	0.0391 (8)	0.0722 (11)	0.0285 (7)	0.0002 (7)	−0.0041 (6)	0.0019 (7)
C9	0.0326 (8)	0.0515 (9)	0.0441 (9)	0.0013 (6)	0.0020 (6)	0.0035 (6)
C10	0.0465 (9)	0.0476 (9)	0.0444 (8)	−0.0033 (7)	−0.0013 (7)	−0.0057 (7)
C11	0.0357 (7)	0.0563 (10)	0.0495 (9)	−0.0041 (7)	0.0074 (7)	0.0044 (7)
C12	0.0480 (10)	0.0733 (12)	0.0366 (8)	−0.0010 (8)	0.0003 (7)	−0.0092 (8)
O1	0.0255 (5)	0.0828 (9)	0.0420 (6)	−0.0007 (5)	−0.0006 (5)	0.0016 (5)
O2	0.0445 (6)	0.0391 (6)	0.0515 (6)	0.0111 (4)	0.0101 (5)	−0.0029 (5)
O3	0.0421 (6)	0.0389 (6)	0.0442 (6)	−0.0001 (4)	0.0136 (5)	0.0033 (4)
O5	0.0477 (7)	0.0754 (9)	0.0371 (6)	0.0013 (6)	0.0099 (5)	0.0109 (6)
O4	0.0280 (5)	0.0799 (9)	0.0263 (5)	0.0004 (5)	0.0018 (4)	0.0003 (5)
N1	0.0404 (7)	0.0415 (7)	0.0336 (6)	0.0080 (5)	0.0096 (5)	0.0055 (5)
N2	0.0233 (6)	0.0583 (8)	0.0431 (7)	0.0010 (5)	0.0007 (5)	−0.0006 (6)
S1	0.0252 (2)	0.0379 (2)	0.0322 (2)	0.00271 (11)	0.00416 (14)	0.00068 (12)

Geometric parameters (Å, º) top

C1—O4	1.3707 (17)	C9—C12	1.507 (2)
C1—C2	1.3806 (19)	C9—H9A	0.9700
C1—C6	1.4029 (19)	C9—H9B	0.9700
C2—C3	1.3972 (19)	C10—N1	1.482 (2)
C2—H2	0.9300	C10—C11	1.504 (2)
C3—C4	1.3955 (19)	C10—H10A	0.9700
C3—S1	1.7683 (13)	C10—H10B	0.9700
C4—C5	1.395 (2)	C11—O5	1.415 (2)
C4—C7	1.507 (2)	C11—H11A	0.9700
C5—C6	1.389 (2)	C11—H11B	0.9700
C5—H5	0.9300	C12—O5	1.422 (2)
C6—N2	1.3842 (18)	C12—H12A	0.9700
C7—H7A	0.9600	C12—H12B	0.9700
C7—H7B	0.9600	O1—S1	1.4461 (12)
C7—H7C	0.9600	O2—S1	1.4645 (11)
C8—O4	1.4211 (18)	O3—S1	1.4575 (11)
C8—H8C	0.9600	N1—H1A	0.9000
C8—H8D	0.9600	N1—H1B	0.9000
C8—H8E	0.9600	N2—H2A	0.86 (2)
C9—N1	1.480 (2)	N2—H2B	0.86 (2)

O4—C1—C2	125.26 (12)	N1—C10—C11	109.53 (13)
O4—C1—C6	114.54 (12)	N1—C10—H10A	109.8
C2—C1—C6	120.19 (12)	C11—C10—H10A	109.8
C1—C2—C3	120.51 (12)	N1—C10—H10B	109.8
C1—C2—H2	119.7	C11—C10—H10B	109.8
C3—C2—H2	119.7	H10A—C10—H10B	108.2
C4—C3—C2	120.74 (12)	O5—C11—C10	110.65 (13)
C4—C3—S1	121.87 (11)	O5—C11—H11A	109.5
C2—C3—S1	117.32 (10)	C10—C11—H11A	109.5
C5—C4—C3	117.32 (12)	O5—C11—H11B	109.5
C5—C4—C7	118.94 (13)	C10—C11—H11B	109.5
C3—C4—C7	123.74 (13)	H11A—C11—H11B	108.1
C6—C5—C4	123.13 (12)	O5—C12—C9	111.88 (15)
C6—C5—H5	118.4	O5—C12—H12A	109.2
C4—C5—H5	118.4	C9—C12—H12A	109.2
N2—C6—C5	122.87 (13)	O5—C12—H12B	109.2
N2—C6—C1	119.06 (13)	C9—C12—H12B	109.2
C5—C6—C1	118.01 (13)	H12A—C12—H12B	107.9
C4—C7—H7A	109.5	C11—O5—C12	110.65 (12)
C4—C7—H7B	109.5	C1—O4—C8	116.84 (12)
H7A—C7—H7B	109.5	C9—N1—C10	110.61 (12)
C4—C7—H7C	109.5	C9—N1—H1A	109.5
H7A—C7—H7C	109.5	C10—N1—H1A	109.5
H7B—C7—H7C	109.5	C9—N1—H1B	109.5
O4—C8—H8C	109.5	C10—N1—H1B	109.5
O4—C8—H8D	109.5	H1A—N1—H1B	108.1
H8C—C8—H8D	109.5	C6—N2—H2A	119.5 (13)
O4—C8—H8E	109.5	C6—N2—H2B	116.8 (15)
H8C—C8—H8E	109.5	H2A—N2—H2B	112.7 (19)
H8D—C8—H8E	109.5	O1—S1—O3	112.93 (7)
N1—C9—C12	109.57 (13)	O1—S1—O2	112.40 (7)
N1—C9—H9A	109.8	O3—S1—O2	110.23 (7)
C12—C9—H9A	109.8	O1—S1—C3	106.58 (7)
N1—C9—H9B	109.8	O3—S1—C3	107.47 (6)
C12—C9—H9B	109.8	O2—S1—C3	106.86 (6)
H9A—C9—H9B	108.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.90	1.92	2.795 (3)	162
N1—H1B···O2	0.90	2.56	3.126 (2)	121
N1—H1B···O3	0.90	1.89	2.790 (3)	175
N2—H2A···O1ⁱⁱ	0.86 (2)	2.23 (2)	3.054 (3)	159.1 (2)
N2—H2B···O5ⁱⁱⁱ	0.85 (2)	2.25 (2)	3.077 (4)	161.5 (2)

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

Experimental details

Crystal data
Chemical formula	C₄H₁₀NO⁺·C₈H₁₀NO₄S⁻
M_r	304.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.2141 (5), 14.8227 (9), 10.4740 (7)
β (°)	91.120 (2)
V (Å³)	1430.24 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.34 × 0.25 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.910, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	13039, 3105, 2962
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.117, 1.12
No. of reflections	3105
No. of parameters	191
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.52

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 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
N1—H1A···O2ⁱ	0.90	1.92	2.795 (3)	162
N1—H1B···O2	0.90	2.56	3.126 (2)	121
N1—H1B···O3	0.90	1.89	2.790 (3)	175
N2—H2A···O1ⁱⁱ	0.86 (2)	2.23 (2)	3.054 (3)	159.1 (2)
N2—H2B···O5ⁱⁱⁱ	0.85 (2)	2.25 (2)	3.077 (4)	161.5 (2)

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

References

Barbour, L. J., Damon, A. K., Orr, G. W. & Atwood, J. L. (1996). Supramol. Chem. 7, 209–211. CSD CrossRef CAS Web of Science Google Scholar
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Bruker (2007). SMART and SAINT. 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
Yin, C.-X., Huo, F.-J. & Yang, P. (2006). Acta Cryst. E62, o2084–o2085. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o631

doi:10.1107/S1600536811003722

Open

access