organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4-[(E)-(Hy­dr­oxy­imino)­meth­yl]-N,N-di­methyl­anilinium chloride

aDepartment of Physics, Government Arts College for Women, Pudukkottaii 622 001, India, bDepartment of Physics, Shivani Institute of Technology, Tiruchirappalli 620 009, India, cDepartment of Physics, Cauvery College for Women, Tiruchirappalli 620 018, India, dLaboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad 500 007, India, and eDepartment of Physics, Kalasalingam University, Krishnankoil 626 126, India
*Correspondence e-mail: s_selvanayagam@rediffmail.com

(Received 3 May 2012; accepted 5 May 2012; online 12 May 2012)

In the title compound, C9H13N2O+·Cl, the cation, apart from the methyl groups, is almost planar, with a maximum deviation of 0.040 (1) Å; the methyl C atoms deviate by 0.389 (2) and −1.247 (1) Å, from the mean plane. In the crystal, cations and anions associate through C—H⋯Cl hydrogen bonds, forming a helical arrangement. In addition, inter­molecular O—H⋯Cl, N—H⋯Cl and C—H⋯N inter­actions are observed.

Related literature

For general background to hydroxyl­amine derivatives, see: Kataoka et al. (2002[Kataoka, H., Horiyama, S., Yamaki, M., Oku, H., Ishiguro, K., Katagi, T., Takayama, M., Semma, M. & Ito, Y. (2002). Biol. Pharm. Bull. 25, 1436-1441.]); Haldimann et al. (2011[Haldimann, P., Muriset, M., Vigh, L. & Goloubinoff, P. (2011). J. Biol. Chem. 286, 18784-18794.]) and to benzalde­hyde derivatives, see: Haraguchi et al. (2011[Haraguchi, S. K., Silva, A. A., Vidotti, G. J., dos Santos, P. V., Garcia, F. P., Pedroso, R. B., Nakamura, C. V., de Oliveira, C. M. A. & da Silva, C. C. (2011). Molecules, 16, 1166-1180.]); Johnston et al. (2011[Johnston, D. A., Mukerjea, R. & Robyt, J. F. (2011). Carbohydr. Res. 346, 2777-2784.]); Zhang et al. (2011[Zhang, H. J., Qin, X., Liu, K., Zhu, D. D., Wang, X. M. & Zhu, H. L. (2011). Bioorg. Med. Chem. 19, 5708-5715.]). For a related structure, see: Bachechi & Zambonelli (1972[Bachechi, F. & Zambonelli, L. (1972). Acta Cryst. B28, 2489-2494.]).

[Scheme 1]

Experimental

Crystal data
  • C9H13N2O+·Cl

  • Mr = 200.66

  • Monoclinic, P 21 /c

  • a = 11.2696 (10) Å

  • b = 11.7093 (10) Å

  • c = 7.6961 (7) Å

  • β = 90.108 (2)°

  • V = 1015.57 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.34 mm−1

  • T = 292 K

  • 0.24 × 0.20 × 0.19 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • 11453 measured reflections

  • 2405 independent reflections

  • 2240 reflections with I > 2σigma(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.093

  • S = 1.07

  • 2405 reflections

  • 125 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯Cl1i 0.82 2.34 3.147 (1) 167
N1—H1N⋯Cl1ii 0.91 (1) 2.14 (1) 3.040 (1) 173 (1)
C6—H6⋯N2iii 0.93 2.59 3.516 (2) 173
C7—H7⋯Cl1iv 0.93 2.81 3.697 (1) 160
C9—H9B⋯Cl1v 0.96 2.81 3.713 (2) 158
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) x, y, z-1; (iii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) -x+1, -y, -z+1; (v) -x, -y, -z+1.

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information


Comment top

Hydroxylamine derivatives possess anti-inflammatory and anti-allergic activities (Kataoka et al., 2002). The novel hydroxylamine derivative NG-094 suppresses polyglutamine protein toxicity in Caenorhabditis elegans (Haldimann et al., 2011). The benzaldehyde-modified starches and starch components have significantly higher water solubility than their native counterparts (Johnston et al., 2011). Benzaldehyde derivatives possess antibacterial (Zhang et al., 2011) and antitrypanasomal (Haraguchi et al., 2011) activities. In continuation of our work, we have undertaken the crystal structure determination of the present complex, and the results are presented here.

The X-ray study confirmed the molecular structure of the title compound as illustrated in Fig. 1. Atom H1N was located from a difference Fourier map and refined freely. The protonation on the N1 site of the cation is also confirmed from the C1—N1 bond distance of 1.4777 (14) Å in comparison with the C—N bond distance of 1.380 (4) Å observed in the crystal structure of the neutral α-p-dimethylaminobenzaldoxime (Bachechi & Zambonelli, 1972). The bond distance N2—C7 of 1.267 (2) Å confirms the double bond character. The cation is almost planar with a maximum deviation of -0.040 (1) Å for atom C3 and the two methyl carbon atoms C8 and C9 deviate by 0.389 (2) and -1.247 (1) Å, respectively, from this plane.

Cations and anions associate through intermolecular C—H···Cl hydrogen bonds. These two hydrogen bonds are run in opposite direction of the ab plane forming a helical shape arrangement (Fig. 2 and Table 1). Intermolecular O—H···Cl, N—H···Cl and C—H···N interactions are also observed in the crystal structure (Fig. 3). In addition, the molecules are also connected by C—H···π interactions, the H3 atom (bound to C3) is at 2.87 Å from the centroid Cg1i of the phenyl ring (symmetry code i = x, 1/2 - y, 1/2 + z), with a C3—H3···Cg1i angle of 135° and a C3···Cg1 distance of 3.589 (2) Å.

Related literature top

For general background to hydroxylamine derivatives, see: Kataoka et al. (2002); Haldimann et al. (2011) and to benzaldehyde derivatives, see: Haraguchi et al. (2011); Johnston et al. (2011); Zhang et al. (2011). For a related structure, see: Bachechi & Zambonelli (1972).

Experimental top

Commercially availbale hydroxylamine hydrochloride with p-dimethyl amino benzaldehyde was taken in equimolar ratio, were dissolved in double ethanol and stirred to yield a homogeneous mixture. The solution was allowed to evaporate at room temperature which yielded a brown crystalline salt. Single crystals were grown by slow evaporation from DMF.

Refinement top

Atom H1N was located from a difference Fourier map and refined with a distance restraint of 0.89 (2) Å. The remaining H atoms were positioned geometrically and were treated as riding on their parent C and O atoms, with C—H = 0.93 Å and Uiso = 1.2Ueq(C) for aromatic H atoms, with C—H = 0.96 Å and Uiso = 1.5Ueq(C) for methyl H atoms, and with O—H = 0.82 Å and Uiso = 1.2Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level
[Figure 2] Fig. 2. Molecular packing of the title compound, viewed along the b axis (H-bonds are shown as dashed lines). For the sake of clarity, H atoms which are not involved in hydrogen bonds have been omitted.
[Figure 3] Fig. 3. Molecular packing of the title compound, viewed along the c axis (H-bonds are shown as dashed lines). For the sake of clarity, H atoms which are not involved in hydrogen bonds have been omitted.
4-[(E)-(Hydroxyimino)methyl]-N,N-dimethylanilinium chloride top
Crystal data top
C9H13N2O+·ClF(000) = 424
Mr = 200.66Dx = 1.312 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7257 reflections
a = 11.2696 (10) Åθ = 2.3–26.6°
b = 11.7093 (10) ŵ = 0.34 mm1
c = 7.6961 (7) ÅT = 292 K
β = 90.108 (2)°Needle, brown
V = 1015.57 (16) Å30.24 × 0.20 × 0.19 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2240 reflections with I > 2σigma(I)
Radiation source: fine-focus sealed tubeRint = 0.025
Graphite monochromatorθmax = 28.0°, θmin = 1.8°
ω scansh = 1414
11453 measured reflectionsk = 1515
2405 independent reflectionsl = 910
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0536P)2 + 0.1829P]
where P = (Fo2 + 2Fc2)/3
2405 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 0.23 e Å3
1 restraintΔρmin = 0.20 e Å3
Crystal data top
C9H13N2O+·ClV = 1015.57 (16) Å3
Mr = 200.66Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.2696 (10) ŵ = 0.34 mm1
b = 11.7093 (10) ÅT = 292 K
c = 7.6961 (7) Å0.24 × 0.20 × 0.19 mm
β = 90.108 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2240 reflections with I > 2σigma(I)
11453 measured reflectionsRint = 0.025
2405 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0311 restraint
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.23 e Å3
2405 reflectionsΔρmin = 0.20 e Å3
125 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
Cl10.16123 (3)0.02780 (2)0.86101 (4)0.04216 (12)
O10.81494 (8)0.28038 (8)0.48301 (14)0.0490 (2)
H10.83210.34070.53090.073*
N10.17646 (8)0.07318 (8)0.24932 (13)0.0370 (2)
H1N0.1744 (14)0.0531 (13)0.1354 (18)0.050 (4)*
N20.69124 (9)0.27159 (9)0.46814 (14)0.0405 (2)
C10.30082 (10)0.10295 (10)0.29034 (14)0.0354 (2)
C20.32816 (11)0.20083 (11)0.38181 (18)0.0472 (3)
H20.26830.24940.41970.057*
C30.44580 (11)0.22569 (11)0.41636 (18)0.0471 (3)
H30.46470.29130.47870.057*
C40.53633 (10)0.15418 (9)0.35930 (14)0.0351 (2)
C50.50650 (11)0.05628 (10)0.26681 (16)0.0395 (3)
H50.56610.00760.22830.047*
C60.38908 (11)0.03048 (9)0.23151 (16)0.0400 (3)
H60.36970.03490.16890.048*
C70.66167 (10)0.18062 (10)0.38936 (15)0.0370 (2)
H70.71990.13050.35060.044*
C80.08882 (12)0.16749 (13)0.2724 (2)0.0568 (4)
H8A0.01450.14590.22090.085*
H8B0.11790.23540.21720.085*
H8C0.07760.18180.39410.085*
C90.13654 (13)0.03099 (11)0.34631 (19)0.0494 (3)
H9A0.18960.09310.32230.074*
H9B0.05770.05120.31000.074*
H9C0.13670.01540.46880.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.04579 (19)0.03872 (18)0.04194 (19)0.00255 (10)0.00722 (12)0.00218 (10)
O10.0383 (5)0.0437 (5)0.0649 (6)0.0055 (3)0.0106 (4)0.0029 (4)
N10.0367 (5)0.0376 (5)0.0367 (5)0.0020 (4)0.0068 (4)0.0022 (4)
N20.0368 (5)0.0381 (5)0.0467 (5)0.0010 (4)0.0075 (4)0.0001 (4)
C10.0351 (5)0.0366 (5)0.0344 (5)0.0020 (4)0.0050 (4)0.0021 (4)
C20.0380 (6)0.0472 (7)0.0564 (7)0.0046 (5)0.0034 (5)0.0200 (6)
C30.0412 (6)0.0445 (6)0.0555 (7)0.0002 (5)0.0067 (5)0.0213 (6)
C40.0376 (5)0.0343 (5)0.0334 (5)0.0002 (4)0.0050 (4)0.0008 (4)
C50.0393 (6)0.0339 (5)0.0453 (6)0.0036 (4)0.0021 (5)0.0059 (5)
C60.0425 (6)0.0324 (5)0.0450 (6)0.0012 (4)0.0047 (5)0.0089 (4)
C70.0371 (6)0.0359 (5)0.0379 (5)0.0022 (4)0.0046 (4)0.0004 (4)
C80.0409 (7)0.0507 (7)0.0786 (10)0.0058 (6)0.0136 (6)0.0133 (7)
C90.0463 (7)0.0514 (8)0.0506 (7)0.0096 (5)0.0054 (6)0.0100 (5)
Geometric parameters (Å, º) top
O1—N21.4023 (13)C4—C51.3903 (16)
O1—H10.8200C4—C71.4640 (15)
N1—C11.4777 (14)C5—C61.3838 (17)
N1—C81.4924 (17)C5—H50.9300
N1—C91.4995 (16)C6—H60.9300
N1—H1N0.908 (13)C7—H70.9300
N2—C71.2698 (15)C8—H8A0.9600
C1—C21.3796 (16)C8—H8B0.9600
C1—C61.3842 (16)C8—H8C0.9600
C2—C31.3827 (18)C9—H9A0.9600
C2—H20.9300C9—H9B0.9600
C3—C41.3916 (17)C9—H9C0.9600
C3—H30.9300
N2—O1—H1109.5C6—C5—H5119.6
C1—N1—C8115.32 (9)C4—C5—H5119.6
C1—N1—C9111.77 (9)C5—C6—C1119.30 (10)
C8—N1—C9110.08 (11)C5—C6—H6120.4
C1—N1—H1N106.8 (10)C1—C6—H6120.4
C8—N1—H1N106.9 (10)N2—C7—C4120.34 (11)
C9—N1—H1N105.3 (10)N2—C7—H7119.8
C7—N2—O1111.13 (10)C4—C7—H7119.8
C2—C1—C6121.09 (11)N1—C8—H8A109.5
C2—C1—N1121.05 (10)N1—C8—H8B109.5
C6—C1—N1117.86 (10)H8A—C8—H8B109.5
C1—C2—C3119.09 (11)N1—C8—H8C109.5
C1—C2—H2120.5H8A—C8—H8C109.5
C3—C2—H2120.5H8B—C8—H8C109.5
C2—C3—C4121.06 (11)N1—C9—H9A109.5
C2—C3—H3119.5N1—C9—H9B109.5
C4—C3—H3119.5H9A—C9—H9B109.5
C5—C4—C3118.75 (11)N1—C9—H9C109.5
C5—C4—C7119.18 (10)H9A—C9—H9C109.5
C3—C4—C7122.05 (10)H9B—C9—H9C109.5
C6—C5—C4120.72 (11)
C8—N1—C1—C214.77 (17)C3—C4—C5—C60.22 (18)
C9—N1—C1—C2111.95 (13)C7—C4—C5—C6178.05 (11)
C8—N1—C1—C6164.17 (12)C4—C5—C6—C10.43 (19)
C9—N1—C1—C669.11 (14)C2—C1—C6—C50.67 (19)
C6—C1—C2—C30.7 (2)N1—C1—C6—C5179.61 (11)
N1—C1—C2—C3179.60 (12)O1—N2—C7—C4179.96 (10)
C1—C2—C3—C40.5 (2)C5—C4—C7—N2177.52 (11)
C2—C3—C4—C50.2 (2)C3—C4—C7—N20.69 (18)
C2—C3—C4—C7177.96 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl1i0.822.343.147 (1)167
N1—H1N···Cl1ii0.91 (1)2.14 (1)3.040 (1)173 (1)
C6—H6···N2iii0.932.593.516 (2)173
C7—H7···Cl1iv0.932.813.697 (1)160
C9—H9B···Cl1v0.962.813.713 (2)158
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y, z1; (iii) x+1, y1/2, z+1/2; (iv) x+1, y, z+1; (v) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC9H13N2O+·Cl
Mr200.66
Crystal system, space groupMonoclinic, P21/c
Temperature (K)292
a, b, c (Å)11.2696 (10), 11.7093 (10), 7.6961 (7)
β (°) 90.108 (2)
V3)1015.57 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.34
Crystal size (mm)0.24 × 0.20 × 0.19
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σigma(I)] reflections
11453, 2405, 2240
Rint0.025
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.093, 1.07
No. of reflections2405
No. of parameters125
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.20

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl1i0.822.343.147 (1)167
N1—H1N···Cl1ii0.91 (1)2.14 (1)3.040 (1)173 (1)
C6—H6···N2iii0.932.593.516 (2)173
C7—H7···Cl1iv0.932.813.697 (1)160
C9—H9B···Cl1v0.962.813.713 (2)158
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y, z1; (iii) x+1, y1/2, z+1/2; (iv) x+1, y, z+1; (v) x, y, z+1.
 

Acknowledgements

SS acknowledges the Department of Science and Technology (DST), India, for providing computing facilities under the DST-Fast Track Scheme.

References

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First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhang, H. J., Qin, X., Liu, K., Zhu, D. D., Wang, X. M. & Zhu, H. L. (2011). Bioorg. Med. Chem. 19, 5708–5715.  Web of Science CrossRef CAS PubMed Google Scholar

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