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

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.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.093
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         38

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          1
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso = 1.2U_eq(C) for aromatic H atoms, with C—H = 0.96 Å and U_iso = 1.5U_eq(C) for methyl H atoms, and with O—H = 0.82 Å and U_iso = 1.2U_eq(O).

Computing details

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

	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

Crystal data

C9H13N2O^+·Cl^−	F(000) = 424
Mr = 200.66	Dx = 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) Å^3	0.24 × 0.20 × 0.19 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2240 reflections with I > 2σigma(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 28.0°, θmin = 1.8°
ω scans	h = −14→14
11453 measured reflections	k = −15→15
2405 independent reflections	l = −9→10

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1^i	0.82	2.34	3.147 (1)	167
N1—H1N···Cl1^ii	0.91 (1)	2.14 (1)	3.040 (1)	173 (1)
C6—H6···N2^iii	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.