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

Devi, T.U.; Kalpana, G.; Priya, S.; Ravikumar, K.; Selvanayagam, S.

doi:10.1107/S1600536812020211

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1705

doi:10.1107/S1600536812020211

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

T. Uma Devi,^a G. Kalpana,^b S. Priya,^c K. Ravikumar ^d and S. Selvanayagam ^e ^*

^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 ); 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

Crystal data

C₉H₁₃N₂O⁺·Cl⁻
M_r = 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)
R_int = 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
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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⋯Cl1^iv	0.93	2.81	3.697 (1)	160
C9—H9B⋯Cl1^v	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 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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 and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812020211/zq2166sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020211/zq2166Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020211/zq2166Isup3.cml

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level
	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.
	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⁺·Cl⁻	F(000) = 424
M_r = 200.66	D_x = 1.312 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7257 reflections
a = 11.2696 (10) Å	θ = 2.3–26.6°
b = 11.7093 (10) Å	µ = 0.34 mm⁻¹
c = 7.6961 (7) Å	T = 292 K
β = 90.108 (2)°	Needle, brown
V = 1015.57 (16) Å³	0.24 × 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 tube	R_int = 0.025
Graphite monochromator	θ_max = 28.0°, θ_min = 1.8°
ω scans	h = −14→14
11453 measured reflections	k = −15→15
2405 independent reflections	l = −9→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0536P)² + 0.1829P] where P = (F_o² + 2F_c²)/3
2405 reflections	(Δ/σ)_max < 0.001
125 parameters	Δρ_max = 0.23 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₁₃N₂O⁺·Cl⁻	V = 1015.57 (16) Å³
M_r = 200.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.2696 (10) Å	µ = 0.34 mm⁻¹
b = 11.7093 (10) Å	T = 292 K
c = 7.6961 (7) Å	0.24 × 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 reflections	R_int = 0.025
2405 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.23 e Å⁻³
2405 reflections	Δρ_min = −0.20 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cl1	0.16123 (3)	0.02780 (2)	0.86101 (4)	0.04216 (12)
O1	0.81494 (8)	0.28038 (8)	0.48301 (14)	0.0490 (2)
H1	0.8321	0.3407	0.5309	0.073*
N1	0.17646 (8)	0.07318 (8)	0.24932 (13)	0.0370 (2)
H1N	0.1744 (14)	0.0531 (13)	0.1354 (18)	0.050 (4)*
N2	0.69124 (9)	0.27159 (9)	0.46814 (14)	0.0405 (2)
C1	0.30082 (10)	0.10295 (10)	0.29034 (14)	0.0354 (2)
C2	0.32816 (11)	0.20083 (11)	0.38181 (18)	0.0472 (3)
H2	0.2683	0.2494	0.4197	0.057*
C3	0.44580 (11)	0.22569 (11)	0.41636 (18)	0.0471 (3)
H3	0.4647	0.2913	0.4787	0.057*
C4	0.53633 (10)	0.15418 (9)	0.35930 (14)	0.0351 (2)
C5	0.50650 (11)	0.05628 (10)	0.26681 (16)	0.0395 (3)
H5	0.5661	0.0076	0.2283	0.047*
C6	0.38908 (11)	0.03048 (9)	0.23151 (16)	0.0400 (3)
H6	0.3697	−0.0349	0.1689	0.048*
C7	0.66167 (10)	0.18062 (10)	0.38936 (15)	0.0370 (2)
H7	0.7199	0.1305	0.3506	0.044*
C8	0.08882 (12)	0.16749 (13)	0.2724 (2)	0.0568 (4)
H8A	0.0145	0.1459	0.2209	0.085*
H8B	0.1179	0.2354	0.2172	0.085*
H8C	0.0776	0.1818	0.3941	0.085*
C9	0.13654 (13)	−0.03099 (11)	0.34631 (19)	0.0494 (3)
H9A	0.1896	−0.0931	0.3223	0.074*
H9B	0.0577	−0.0512	0.3100	0.074*
H9C	0.1367	−0.0154	0.4688	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.04579 (19)	0.03872 (18)	0.04194 (19)	0.00255 (10)	−0.00722 (12)	−0.00218 (10)
O1	0.0383 (5)	0.0437 (5)	0.0649 (6)	−0.0055 (3)	−0.0106 (4)	−0.0029 (4)
N1	0.0367 (5)	0.0376 (5)	0.0367 (5)	−0.0020 (4)	−0.0068 (4)	−0.0022 (4)
N2	0.0368 (5)	0.0381 (5)	0.0467 (5)	−0.0010 (4)	−0.0075 (4)	0.0001 (4)
C1	0.0351 (5)	0.0366 (5)	0.0344 (5)	−0.0020 (4)	−0.0050 (4)	−0.0021 (4)
C2	0.0380 (6)	0.0472 (7)	0.0564 (7)	0.0046 (5)	−0.0034 (5)	−0.0200 (6)
C3	0.0412 (6)	0.0445 (6)	0.0555 (7)	0.0002 (5)	−0.0067 (5)	−0.0213 (6)
C4	0.0376 (5)	0.0343 (5)	0.0334 (5)	0.0002 (4)	−0.0050 (4)	−0.0008 (4)
C5	0.0393 (6)	0.0339 (5)	0.0453 (6)	0.0036 (4)	−0.0021 (5)	−0.0059 (5)
C6	0.0425 (6)	0.0324 (5)	0.0450 (6)	−0.0012 (4)	−0.0047 (5)	−0.0089 (4)
C7	0.0371 (6)	0.0359 (5)	0.0379 (5)	0.0022 (4)	−0.0046 (4)	−0.0004 (4)
C8	0.0409 (7)	0.0507 (7)	0.0786 (10)	0.0058 (6)	−0.0136 (6)	−0.0133 (7)
C9	0.0463 (7)	0.0514 (8)	0.0506 (7)	−0.0096 (5)	−0.0054 (6)	0.0100 (5)

Geometric parameters (Å, º) top

O1—N2	1.4023 (13)	C4—C5	1.3903 (16)
O1—H1	0.8200	C4—C7	1.4640 (15)
N1—C1	1.4777 (14)	C5—C6	1.3838 (17)
N1—C8	1.4924 (17)	C5—H5	0.9300
N1—C9	1.4995 (16)	C6—H6	0.9300
N1—H1N	0.908 (13)	C7—H7	0.9300
N2—C7	1.2698 (15)	C8—H8A	0.9600
C1—C2	1.3796 (16)	C8—H8B	0.9600
C1—C6	1.3842 (16)	C8—H8C	0.9600
C2—C3	1.3827 (18)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C3—C4	1.3916 (17)	C9—H9C	0.9600
C3—H3	0.9300

N2—O1—H1	109.5	C6—C5—H5	119.6
C1—N1—C8	115.32 (9)	C4—C5—H5	119.6
C1—N1—C9	111.77 (9)	C5—C6—C1	119.30 (10)
C8—N1—C9	110.08 (11)	C5—C6—H6	120.4
C1—N1—H1N	106.8 (10)	C1—C6—H6	120.4
C8—N1—H1N	106.9 (10)	N2—C7—C4	120.34 (11)
C9—N1—H1N	105.3 (10)	N2—C7—H7	119.8
C7—N2—O1	111.13 (10)	C4—C7—H7	119.8
C2—C1—C6	121.09 (11)	N1—C8—H8A	109.5
C2—C1—N1	121.05 (10)	N1—C8—H8B	109.5
C6—C1—N1	117.86 (10)	H8A—C8—H8B	109.5
C1—C2—C3	119.09 (11)	N1—C8—H8C	109.5
C1—C2—H2	120.5	H8A—C8—H8C	109.5
C3—C2—H2	120.5	H8B—C8—H8C	109.5
C2—C3—C4	121.06 (11)	N1—C9—H9A	109.5
C2—C3—H3	119.5	N1—C9—H9B	109.5
C4—C3—H3	119.5	H9A—C9—H9B	109.5
C5—C4—C3	118.75 (11)	N1—C9—H9C	109.5
C5—C4—C7	119.18 (10)	H9A—C9—H9C	109.5
C3—C4—C7	122.05 (10)	H9B—C9—H9C	109.5
C6—C5—C4	120.72 (11)

C8—N1—C1—C2	14.77 (17)	C3—C4—C5—C6	0.22 (18)
C9—N1—C1—C2	−111.95 (13)	C7—C4—C5—C6	−178.05 (11)
C8—N1—C1—C6	−164.17 (12)	C4—C5—C6—C1	−0.43 (19)
C9—N1—C1—C6	69.11 (14)	C2—C1—C6—C5	0.67 (19)
C6—C1—C2—C3	−0.7 (2)	N1—C1—C6—C5	179.61 (11)
N1—C1—C2—C3	−179.60 (12)	O1—N2—C7—C4	−179.96 (10)
C1—C2—C3—C4	0.5 (2)	C5—C4—C7—N2	177.52 (11)
C2—C3—C4—C5	−0.2 (2)	C3—C4—C7—N2	−0.69 (18)
C2—C3—C4—C7	177.96 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···Cl1^iv	0.93	2.81	3.697 (1)	160
C9—H9B···Cl1^v	0.96	2.81	3.713 (2)	158

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y, z−1; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, −y, −z+1; (v) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₁₃N₂O⁺·Cl⁻
M_r	200.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	11.2696 (10), 11.7093 (10), 7.6961 (7)
β (°)	90.108 (2)
V (Å³)	1015.57 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.24 × 0.20 × 0.19

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σigma(I)] reflections	11453, 2405, 2240
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.093, 1.07
No. of reflections	2405
No. of parameters	125
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)	0.23, −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···A	D—H	H···A	D···A	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···Cl1^iv	0.93	2.81	3.697 (1)	160
C9—H9B···Cl1^v	0.96	2.81	3.713 (2)	158

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y, z−1; (iii) −x+1, y−1/2, −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.

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