organic compounds
2-Hydroxyethanaminium 2-methyl-5-nitrobenzenesulfonate
aCollege of Chemical Engineering and Material Sciences, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, bDepartment of Pharmacy, 117th Hospital of PLA, Hangzhou 310013, People's Republic of China, and cCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
*Correspondence e-mail: awwxzy@sina.com
In the 2H8NO+·C7H6NO5S−, the cations and anions are linked together by N—H⋯O and O—H⋯O hydrogen bonds, forming layers parallel to (100). The plane of nitro group is skew with respect to the plane of benzene ring, making a dihedral angle of 17.5 (2)°.
of the title salt, CRelated literature
For the structures of pyridinium derivative, nickel, magnesium and potassium salts of 2-methyl-5-nitrobenzenesulfonate, see, respectively: Gu et al. (2007); Xie et al. (2007); Xie, Lui & Yuan (2006); Xie, Yang et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2007); cell 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
10.1107/S160053681203382X/is5129sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681203382X/is5129Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681203382X/is5129Isup3.cml
2-Methyl-5-nitrobenzenesulfonic acid (12.1 g) and 2-ethanolamine (5.0 g) were mixed and dissolved in sufficient water (25 ml) by heating to 373 K, at which point a clear solution resulted. The solution was then cooled slowly to room temperature. Crystals of the title compound (9.2 g) were formed upon the evaporation of water, then collected and washed with ethanol.
All H atoms of hydroxyl and ammonium groups were located in a difference Fourier map. The H atoms of ammonium group were refined freely, but the H atom of hydroxyl group was refined with a distance restraint O—H = 0.82 (1) Å, and with Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2007); cell
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).Fig. 1. The asymmetric unit of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level. One N—H···O hydrogen bond is illustrated as a dashed line. Fig. 2. The hydrogen bonding layer of the title compound viewed down along the b axis. Hydrogen bonds are drawn as dashed lines. The H atoms not involved in the hydrogen bonds have been omitted for clarity. |
C2H8NO+·C7H6NO5S− | F(000) = 584 |
Mr = 278.29 | Dx = 1.545 Mg m−3 |
Monoclinic, P21/c | Melting point < 424 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.8130 (5) Å | Cell parameters from 1766 reflections |
b = 9.5617 (4) Å | θ = 1.6–17.6° |
c = 8.6697 (3) Å | µ = 0.29 mm−1 |
β = 103.071 (1)° | T = 293 K |
V = 1196.14 (8) Å3 | Prism, colorless |
Z = 4 | 0.32 × 0.30 × 0.28 mm |
Bruker SMART APEX CCD diffractometer | 2739 independent reflections |
Radiation source: sealed tube | 2620 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −19→19 |
Tmin = 0.873, Tmax = 0.910 | k = −12→12 |
11263 measured reflections | l = −11→11 |
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)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0532P)2 + 0.342P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
2739 reflections | Δρmax = 0.28 e Å−3 |
181 parameters | Δρmin = −0.39 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.095 (5) |
C2H8NO+·C7H6NO5S− | V = 1196.14 (8) Å3 |
Mr = 278.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.8130 (5) Å | µ = 0.29 mm−1 |
b = 9.5617 (4) Å | T = 293 K |
c = 8.6697 (3) Å | 0.32 × 0.30 × 0.28 mm |
β = 103.071 (1)° |
Bruker SMART APEX CCD diffractometer | 2739 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2620 reflections with I > 2σ(I) |
Tmin = 0.873, Tmax = 0.910 | Rint = 0.032 |
11263 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 1 restraint |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.28 e Å−3 |
2739 reflections | Δρmin = −0.39 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.320970 (19) | 0.93470 (3) | 0.27057 (3) | 0.02240 (13) | |
O1 | 0.16252 (9) | 0.44692 (11) | 0.12844 (15) | 0.0467 (3) | |
O2 | 0.07025 (8) | 0.46497 (13) | −0.10098 (15) | 0.0484 (3) | |
O3 | 0.37472 (7) | 1.00898 (11) | 0.17553 (11) | 0.0346 (2) | |
O4 | 0.28710 (7) | 1.02587 (12) | 0.37875 (11) | 0.0359 (3) | |
O5 | 0.37141 (7) | 0.81368 (10) | 0.35012 (11) | 0.0328 (2) | |
N1 | 0.12202 (8) | 0.51582 (12) | 0.01568 (14) | 0.0321 (3) | |
C1 | 0.22210 (8) | 0.86643 (13) | 0.13486 (13) | 0.0217 (2) | |
C2 | 0.15933 (9) | 0.95606 (13) | 0.03584 (15) | 0.0265 (3) | |
C3 | 0.08519 (9) | 0.89425 (16) | −0.07087 (16) | 0.0339 (3) | |
H3 | 0.0427 | 0.9514 | −0.1376 | 0.041* | |
C4 | 0.07288 (9) | 0.75096 (16) | −0.08063 (16) | 0.0328 (3) | |
H4 | 0.0236 | 0.7118 | −0.1537 | 0.039* | |
C5 | 0.13542 (8) | 0.66756 (13) | 0.02065 (15) | 0.0262 (3) | |
C6 | 0.21014 (8) | 0.72276 (13) | 0.12945 (14) | 0.0243 (3) | |
H6 | 0.2513 | 0.6646 | 0.1973 | 0.029* | |
C7 | 0.16737 (11) | 1.11277 (15) | 0.04080 (19) | 0.0385 (3) | |
H7A | 0.1641 | 1.1457 | 0.1440 | 0.046* | |
H7B | 0.1176 | 1.1527 | −0.0372 | 0.046* | |
H7C | 0.2256 | 1.1400 | 0.0188 | 0.046* | |
O6 | 0.59657 (8) | 0.94383 (12) | 0.32575 (13) | 0.0407 (3) | |
N2 | 0.49673 (8) | 0.71679 (12) | 0.15377 (14) | 0.0282 (2) | |
C8 | 0.55294 (10) | 0.81663 (14) | 0.08550 (15) | 0.0304 (3) | |
H8A | 0.5137 | 0.8929 | 0.0360 | 0.037* | |
H8B | 0.5771 | 0.7698 | 0.0040 | 0.037* | |
C9 | 0.63225 (10) | 0.87505 (16) | 0.20792 (17) | 0.0351 (3) | |
H9A | 0.6734 | 0.8001 | 0.2552 | 0.042* | |
H9B | 0.6673 | 0.9405 | 0.1589 | 0.042* | |
H6' | 0.6382 (11) | 0.954 (2) | 0.4039 (17) | 0.048 (5)* | |
H2A | 0.4547 (16) | 0.683 (2) | 0.072 (3) | 0.058 (6)* | |
H2B | 0.4688 (14) | 0.753 (2) | 0.220 (2) | 0.046 (5)* | |
H2C | 0.5324 (13) | 0.646 (2) | 0.208 (2) | 0.044 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01922 (18) | 0.02454 (19) | 0.02070 (18) | −0.00232 (10) | −0.00124 (12) | −0.00248 (10) |
O1 | 0.0523 (7) | 0.0270 (5) | 0.0529 (7) | −0.0034 (5) | −0.0043 (6) | 0.0035 (5) |
O2 | 0.0415 (6) | 0.0386 (6) | 0.0560 (7) | −0.0100 (5) | −0.0078 (5) | −0.0182 (5) |
O3 | 0.0285 (5) | 0.0414 (6) | 0.0327 (5) | −0.0116 (4) | 0.0039 (4) | 0.0007 (4) |
O4 | 0.0347 (5) | 0.0421 (6) | 0.0287 (5) | 0.0010 (4) | 0.0021 (4) | −0.0130 (4) |
O5 | 0.0274 (5) | 0.0326 (5) | 0.0316 (5) | 0.0020 (4) | −0.0079 (4) | 0.0026 (4) |
N1 | 0.0255 (5) | 0.0279 (6) | 0.0408 (6) | −0.0046 (4) | 0.0030 (5) | −0.0070 (5) |
C1 | 0.0180 (5) | 0.0247 (6) | 0.0207 (5) | −0.0007 (4) | 0.0005 (4) | −0.0020 (4) |
C2 | 0.0238 (6) | 0.0258 (6) | 0.0273 (6) | 0.0019 (5) | 0.0003 (5) | 0.0003 (5) |
C3 | 0.0266 (6) | 0.0339 (7) | 0.0340 (7) | 0.0046 (5) | −0.0082 (5) | 0.0023 (5) |
C4 | 0.0245 (6) | 0.0359 (7) | 0.0319 (6) | −0.0018 (5) | −0.0065 (5) | −0.0061 (5) |
C5 | 0.0224 (5) | 0.0250 (6) | 0.0292 (6) | −0.0026 (5) | 0.0019 (5) | −0.0045 (5) |
C6 | 0.0208 (5) | 0.0249 (6) | 0.0248 (5) | 0.0001 (4) | 0.0001 (4) | −0.0008 (4) |
C7 | 0.0369 (7) | 0.0250 (7) | 0.0477 (8) | 0.0030 (6) | −0.0031 (6) | 0.0036 (6) |
O6 | 0.0391 (6) | 0.0446 (6) | 0.0330 (6) | 0.0013 (5) | −0.0030 (5) | −0.0150 (4) |
N2 | 0.0305 (6) | 0.0258 (5) | 0.0254 (5) | 0.0002 (4) | 0.0003 (5) | −0.0021 (4) |
C8 | 0.0391 (7) | 0.0272 (6) | 0.0230 (6) | −0.0027 (5) | 0.0030 (5) | −0.0006 (5) |
C9 | 0.0321 (6) | 0.0364 (7) | 0.0354 (7) | −0.0045 (6) | 0.0045 (6) | −0.0058 (6) |
S1—O4 | 1.4506 (10) | C6—H6 | 0.9300 |
S1—O3 | 1.4540 (10) | C7—H7A | 0.9600 |
S1—O5 | 1.4628 (10) | C7—H7B | 0.9600 |
S1—C1 | 1.7821 (11) | C7—H7C | 0.9600 |
O1—N1 | 1.2183 (16) | O6—C9 | 1.4141 (17) |
O2—N1 | 1.2234 (15) | O6—H6' | 0.813 (9) |
N1—C5 | 1.4638 (16) | N2—C8 | 1.4757 (17) |
C1—C6 | 1.3846 (17) | N2—H2A | 0.89 (2) |
C1—C2 | 1.4054 (16) | N2—H2B | 0.85 (2) |
C2—C3 | 1.3971 (18) | N2—H2C | 0.92 (2) |
C2—C7 | 1.5030 (18) | C8—C9 | 1.5016 (18) |
C3—C4 | 1.382 (2) | C8—H8A | 0.9700 |
C3—H3 | 0.9300 | C8—H8B | 0.9700 |
C4—C5 | 1.3774 (19) | C9—H9A | 0.9700 |
C4—H4 | 0.9300 | C9—H9B | 0.9700 |
C5—C6 | 1.3860 (16) | ||
O4—S1—O3 | 112.75 (7) | C5—C6—H6 | 120.7 |
O4—S1—O5 | 112.65 (6) | C2—C7—H7A | 109.5 |
O3—S1—O5 | 111.52 (6) | C2—C7—H7B | 109.5 |
O4—S1—C1 | 107.11 (6) | H7A—C7—H7B | 109.5 |
O3—S1—C1 | 106.16 (5) | C2—C7—H7C | 109.5 |
O5—S1—C1 | 106.10 (6) | H7A—C7—H7C | 109.5 |
O1—N1—O2 | 123.46 (13) | H7B—C7—H7C | 109.5 |
O1—N1—C5 | 118.26 (11) | C9—O6—H6' | 108.8 (15) |
O2—N1—C5 | 118.28 (12) | C8—N2—H2A | 105.8 (14) |
C6—C1—C2 | 121.49 (11) | C8—N2—H2B | 114.3 (14) |
C6—C1—S1 | 117.75 (9) | H2A—N2—H2B | 108.7 (19) |
C2—C1—S1 | 120.75 (9) | C8—N2—H2C | 111.7 (12) |
C3—C2—C1 | 117.32 (12) | H2A—N2—H2C | 111.0 (19) |
C3—C2—C7 | 119.08 (12) | H2B—N2—H2C | 105.5 (18) |
C1—C2—C7 | 123.59 (11) | N2—C8—C9 | 112.29 (11) |
C4—C3—C2 | 122.21 (12) | N2—C8—H8A | 109.1 |
C4—C3—H3 | 118.9 | C9—C8—H8A | 109.1 |
C2—C3—H3 | 118.9 | N2—C8—H8B | 109.1 |
C5—C4—C3 | 118.32 (12) | C9—C8—H8B | 109.1 |
C5—C4—H4 | 120.8 | H8A—C8—H8B | 107.9 |
C3—C4—H4 | 120.8 | O6—C9—C8 | 108.85 (12) |
C4—C5—C6 | 122.13 (12) | O6—C9—H9A | 109.9 |
C4—C5—N1 | 119.20 (12) | C8—C9—H9A | 109.9 |
C6—C5—N1 | 118.66 (11) | O6—C9—H9B | 109.9 |
C1—C6—C5 | 118.51 (11) | C8—C9—H9B | 109.9 |
C1—C6—H6 | 120.7 | H9A—C9—H9B | 108.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5i | 0.89 (2) | 2.04 (2) | 2.872 (2) | 156 (2) |
N2—H2B···O5 | 0.85 (2) | 2.10 (2) | 2.938 (2) | 166 (2) |
N2—H2C···O3ii | 0.92 (2) | 2.00 (2) | 2.914 (1) | 172 (2) |
O6—H6′···O4iii | 0.81 (1) | 1.97 (1) | 2.760 (1) | 165 (1) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C2H8NO+·C7H6NO5S− |
Mr | 278.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.8130 (5), 9.5617 (4), 8.6697 (3) |
β (°) | 103.071 (1) |
V (Å3) | 1196.14 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.32 × 0.30 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.873, 0.910 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11263, 2739, 2620 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.095, 1.11 |
No. of reflections | 2739 |
No. of parameters | 181 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.39 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5i | 0.89 (2) | 2.04 (2) | 2.872 (2) | 156 (2) |
N2—H2B···O5 | 0.85 (2) | 2.10 (2) | 2.938 (2) | 166 (2) |
N2—H2C···O3ii | 0.92 (2) | 2.00 (2) | 2.914 (1) | 172 (2) |
O6—H6'···O4iii | 0.813 (9) | 1.967 (14) | 2.760 (1) | 165 (1) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+2, −z+1. |
References
Bruker (2002). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gu, J., Chen, W. Q., Wada, T., Hashizume, D. & Duan, X. M. (2007). CrystEngComm, 9, 541–544. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, Y.-R., Ge, G.-W., Yuan, X.-Y., Wan, D.-B. & Yang, R.-Q. (2007). Acta Cryst. E63, m812–m814. CrossRef IUCr Journals Google Scholar
Xie, Y.-R., Lui, G.-R. & Yuan, X.-Y. (2006). Acta Cryst. E62, m1016–m1017. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xie, Y.-R., Yang, Y.-C., Yuan, X.-Y. & Yang, R.-Q. (2006). Acta Cryst. E62, m2683–m2684. Web of Science CSD CrossRef IUCr Journals Google Scholar
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A few crystal structures containing 2-methyl-5-nitrobenzenesulfonate have been reported previously (Gu et al., 2007; Xie et al., 2007; Xie, Lui & Yuan, 2006; Xie, Yang et al., 2006).
In the asymmetric unit of the title compound, the 2-ethanolamine molecule is protonated and the 2-methyl-5-nitrobenzenesulfonic acid molecule loses its acid H atom, then they are linked by an N2—H2B···O5 hydrogen bond (Fig. 1 & Table 1). The plane of nitro group is skew with the plane of benzene ring in a dihedral angle of 17.5 (2)°. The C1—C2 bond [1.4054 (16) Å] is the longest one among the other aromatic C—C bond, this is consistent with the situations observed in the previous cases (1.405 Å, Gu et al., 2007; 1.404 Å, Xie, Lui & Yuan, 2006; 1.407 Å, Xie et al., 2007; 1.408 Å, Xie, Yang et al., 2006).
A few crystal structures containing 2-methyl-5-nitrobenzenesulfonate have been reported previously, they are pyridinium derivative (Gu et al., 2007), nickel (Xie, Yang et al., 2006), magnesium (Xie et al., 2007), and potassium salts (Xie, Lui & Yuan, 2006). In the potassium salt, all of the oxygen atoms of sulfonate and one oxygen atom of the nitro group is coordinated with potassium atom directly. However, there exists no covalent bond between the counter ion pair in the title compound, which is similar with the other three previous cases. In all of these cases, one of C-C bond of benzene rings are slightly abormal.
In the crystal, the 2-hydroxyethanaminium cations and the MNB anions are linked by N—H···O and O—H···O hydrogen bonds (Table 1) to form thick layers (Fig. 2) parallel to the (100) plane. The nearest separation between the centroid of MNB benzene rings is of 4.483 (3) Å, suggesting no π–π interaction. This situation is similar to that observed in the case containing a large sized organic cation as counter ion for MNB anion (Gu et al., 2007), but is different from those observed in other cases containing metal cations as counter ion for MNB anion (Xie et al., 2007; Xie, Lui & Yuan, 2006; Xie, Yang et al., 2006).