(E)-N′-Hy­droxy-N,N-dimethyl-2-(3-nitro­phen­yl)­acetimidamide

Ruan, Y.; Zhao, H.

doi:10.1107/S2414314619006072

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 5| May 2019| x190607

https://doi.org/10.1107/S2414314619006072

Open

access

(E)-N′-Hydroxy-N,N-dimethyl-2-(3-nitrophenyl)acetimidamide

Yao Ruan ^a and Hui Zhao ^b ^*

^aNational Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022, People's Republic of China, and ^bAnhui Engineering Technology Research Center for Extraction and Isolation of Active Components, Anhui Academy of Science and Technology, Hefei 230031, People's Republic of China
^*Correspondence e-mail: zh1986@iccas.ac.cn

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 30 March 2019; accepted 1 May 2019; online 14 May 2019)

In the crystal of the title compound, C₁₀H₁₃N₂O₃, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂²(6) loops. The dimers are linked by weak C—H⋯O and C—H⋯π interactions, resulting in a three-dimensional network. A short NO₂⋯NO₂ contact [3.107 (2) Å] is also seen.

Keywords: crystal structure; amidoxime; hydrogen bonds; NO₂⋯NO₂ interaction.

CCDC reference: 1897722

Structure description

Amidoxime, also referred to as N-hydroxy amidine, is a well-known amphoteric functional group that has been frequently grafted onto various surfaces for the recovery and removal of U^VI from aqueous media (e.g. sea water) owing to its high sorption capacity and fast sorption rate for uranium and its own low environmental effects (Saeed et al., 2008 ; Yuan et al., 2016 ; Zhao et al., 2014 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound.

The title compound crystallizes in the triclinic P $[\overline{1}]$ space group with one molecule in the asymmetric unit (Fig. 1). The bond lengths and angles are comparable to its known analogues (e.g. Röhrig et al., 2017 ) and the C8—N2—O3—H3 grouping has an anti conformation (torsion angle = −169°).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

In the crystal, the molecules are linked into a three-dimensional network by a combination of N—H⋯O, C—H⋯O and C—H⋯π (Table 1, Fig. 2) interactions. Inversion dimers linked by pairwise N—H⋯O bonds generate a classic R₂²(6) loop and the weak interactions link the dimers into a three-dimensional network. A short NO₂⋯NO₂ contact [O2⋯O2(−x, 2 − y, −z) = 3.017 (2) Å] is also observed.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N2ⁱ	0.82	2.11	2.8292 (19)	146
C10—H10C⋯O2ⁱⁱ	0.96	2.51	3.288 (3)	139
C10—H10B⋯Cg1	0.96	2.85	3.718 (3)	151
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y-1, z+1.

Figure 2
Packing diagram of the title compound viewed along the c-axis direction. Hydrogen bonds are drawn as dashed lines.

Synthesis and crystallization

To a solution of 1-(2,2-difluorovinyl)-3-nitrobenzene (1 mmol) in N,N-dimethylformamide (DMF, 10 ml) were added hydroxylamine hydrochloride (350 mg, 5 mmol), triethylamine (505 mg, 5 mmol) and powdery 4 Å molecular sieve (Gao et al., 2018 ). After stirring at room temperature for six h, dimethylamine (1 mmol, 40wt% water solution) was added and the resulting reaction mixture was stirred overnight. The reaction mixture was then added to cold water (50 ml) and the crude product was precipitated out. The crude product was purified by flash column chromatography [silica gel (#100–200), PE:EA = 10:1 to 5:1] to afford the title compound (27 mg, 12%) and colourless blocks were obtained by the slow evaporation of a petroleum ether/ethylacetate (v:v = 10:1) solution.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₃
M_r	223.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.7740 (6), 8.4772 (5), 9.6599 (7)
α, β, γ (°)	66.595 (6), 77.917 (6), 76.113 (6)
V (Å³)	562.49 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.22 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.976, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	6503, 2097, 1722
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.157, 1.08
No. of reflections	2097
No. of parameters	148
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.37
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1897722

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619006072/hb4291sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619006072/hb4291Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619006072/hb4291Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); 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: SHELXTL (Sheldrick, 2008).

(E)-N'-Hydroxy-N,N-dimethyl-2-(3-nitrophenyl)acetimidamide top

Crystal data top

C₁₀H₁₃N₃O₃	Z = 2
M_r = 223.23	F(000) = 236
Triclinic, P1	D_x = 1.318 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7740 (6) Å	Cell parameters from 2839 reflections
b = 8.4772 (5) Å	θ = 4.1–28.1°
c = 9.6599 (7) Å	µ = 0.10 mm⁻¹
α = 66.595 (6)°	T = 293 K
β = 77.917 (6)°	Block, colourless
γ = 76.113 (6)°	0.25 × 0.22 × 0.12 mm
V = 562.49 (7) Å³

Data collection top

Bruker APEXII CCD diffractometer	2097 independent reflections
Radiation source: fine-focus sealed tube	1722 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 25.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −9→9
T_min = 0.976, T_max = 0.988	k = −10→10
6503 measured reflections	l = −11→11

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.085P)² + 0.0695P] where P = (F_o² + 2F_c²)/3
2097 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

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
N1	0.2028 (2)	1.0701 (2)	−0.00206 (19)	0.0528 (5)
O2	0.1524 (2)	1.07407 (18)	−0.11426 (17)	0.0637 (5)
O1	0.1824 (3)	1.1983 (2)	0.0307 (2)	0.0957 (7)
C2	0.2750 (2)	0.7507 (2)	0.08584 (18)	0.0391 (4)
H2	0.2107	0.7551	0.0129	0.047*
C3	0.3558 (2)	0.5920 (2)	0.18285 (18)	0.0382 (4)
C1	0.2920 (2)	0.9027 (2)	0.09979 (19)	0.0407 (4)
C4	0.4542 (3)	0.5915 (3)	0.2875 (2)	0.0483 (5)
H4	0.5103	0.4856	0.3519	0.058*
C6	0.3873 (3)	0.9029 (3)	0.2038 (2)	0.0504 (5)
H6	0.3958	1.0069	0.2109	0.060*
C5	0.4703 (3)	0.7449 (3)	0.2977 (2)	0.0557 (5)
H5	0.5374	0.7417	0.3683	0.067*
C8	0.2728 (2)	0.2961 (2)	0.32899 (19)	0.0404 (4)
C7	0.3362 (3)	0.4217 (2)	0.17492 (19)	0.0473 (5)
H7A	0.2516	0.4460	0.1051	0.057*
H7B	0.4505	0.3681	0.1357	0.057*
N2	0.3767 (2)	0.16518 (18)	0.41274 (17)	0.0453 (4)
O3	0.55854 (18)	0.15786 (19)	0.34362 (18)	0.0665 (5)
H3	0.6176	0.0640	0.3900	0.100*
N3	0.0994 (2)	0.3282 (2)	0.38795 (19)	0.0583 (5)
C10	0.0425 (4)	0.2126 (4)	0.5410 (3)	0.0842 (8)
H10A	0.0344	0.1025	0.5387	0.126*
H10B	−0.0722	0.2645	0.5782	0.126*
H10C	0.1280	0.1947	0.6070	0.126*
C9	−0.0412 (3)	0.4295 (4)	0.2971 (3)	0.0848 (8)
H9A	0.0017	0.5260	0.2141	0.127*
H9B	−0.1400	0.4726	0.3584	0.127*
H9C	−0.0796	0.3576	0.2579	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0528 (10)	0.0383 (9)	0.0583 (10)	−0.0045 (7)	−0.0095 (8)	−0.0092 (8)
O2	0.0677 (10)	0.0513 (9)	0.0571 (9)	−0.0024 (7)	−0.0219 (7)	−0.0022 (7)
O1	0.1332 (18)	0.0386 (9)	0.1205 (15)	0.0089 (9)	−0.0488 (13)	−0.0320 (9)
C2	0.0387 (10)	0.0398 (10)	0.0346 (8)	−0.0017 (7)	−0.0061 (7)	−0.0116 (7)
C3	0.0347 (9)	0.0367 (9)	0.0356 (8)	−0.0014 (7)	−0.0007 (7)	−0.0102 (7)
C1	0.0390 (10)	0.0351 (9)	0.0401 (9)	−0.0046 (7)	−0.0014 (7)	−0.0084 (7)
C4	0.0432 (10)	0.0466 (11)	0.0431 (10)	−0.0056 (8)	−0.0117 (8)	−0.0022 (8)
C6	0.0540 (12)	0.0489 (11)	0.0503 (11)	−0.0186 (9)	−0.0032 (9)	−0.0166 (9)
C5	0.0571 (13)	0.0636 (13)	0.0488 (11)	−0.0222 (10)	−0.0172 (9)	−0.0111 (9)
C8	0.0478 (11)	0.0308 (9)	0.0410 (9)	0.0010 (7)	−0.0087 (8)	−0.0144 (7)
C7	0.0591 (12)	0.0357 (10)	0.0402 (9)	0.0032 (8)	−0.0065 (8)	−0.0131 (8)
N2	0.0419 (9)	0.0355 (8)	0.0483 (9)	0.0013 (6)	−0.0071 (7)	−0.0085 (6)
O3	0.0435 (8)	0.0507 (9)	0.0762 (10)	0.0071 (6)	−0.0023 (7)	−0.0045 (7)
N3	0.0421 (10)	0.0573 (10)	0.0576 (10)	0.0055 (8)	−0.0053 (7)	−0.0110 (8)
C10	0.0610 (15)	0.0939 (19)	0.0661 (14)	−0.0061 (13)	0.0136 (12)	−0.0117 (13)
C9	0.0521 (14)	0.0740 (16)	0.108 (2)	0.0076 (12)	−0.0260 (14)	−0.0152 (14)

Geometric parameters (Å, º) top

N1—O2	1.213 (2)	C8—N3	1.357 (2)
N1—O1	1.214 (2)	C8—C7	1.509 (2)
N1—C1	1.472 (2)	C7—H7A	0.9700
C2—C3	1.386 (2)	C7—H7B	0.9700
C2—C1	1.387 (2)	N2—O3	1.429 (2)
C2—H2	0.9300	O3—H3	0.8200
C3—C4	1.387 (3)	N3—C9	1.434 (3)
C3—C7	1.521 (2)	N3—C10	1.458 (3)
C1—C6	1.368 (3)	C10—H10A	0.9600
C4—C5	1.379 (3)	C10—H10B	0.9600
C4—H4	0.9300	C10—H10C	0.9600
C6—C5	1.378 (3)	C9—H9A	0.9600
C6—H6	0.9300	C9—H9B	0.9600
C5—H5	0.9300	C9—H9C	0.9600
C8—N2	1.292 (2)

O2—N1—O1	122.95 (17)	C8—C7—C3	111.66 (14)
O2—N1—C1	118.80 (15)	C8—C7—H7A	109.3
O1—N1—C1	118.24 (18)	C3—C7—H7A	109.3
C3—C2—C1	118.62 (16)	C8—C7—H7B	109.3
C3—C2—H2	120.7	C3—C7—H7B	109.3
C1—C2—H2	120.7	H7A—C7—H7B	107.9
C4—C3—C2	118.85 (16)	C8—N2—O3	111.70 (14)
C4—C3—C7	120.66 (15)	N2—O3—H3	109.5
C2—C3—C7	120.50 (16)	C8—N3—C9	123.55 (18)
C6—C1—C2	122.78 (17)	C8—N3—C10	117.97 (17)
C6—C1—N1	119.16 (16)	C9—N3—C10	115.5 (2)
C2—C1—N1	118.06 (16)	N3—C10—H10A	109.5
C5—C4—C3	121.24 (17)	N3—C10—H10B	109.5
C5—C4—H4	119.4	H10A—C10—H10B	109.5
C3—C4—H4	119.4	N3—C10—H10C	109.5
C1—C6—C5	118.26 (18)	H10A—C10—H10C	109.5
C1—C6—H6	120.9	H10B—C10—H10C	109.5
C5—C6—H6	120.9	N3—C9—H9A	109.5
C6—C5—C4	120.23 (18)	N3—C9—H9B	109.5
C6—C5—H5	119.9	H9A—C9—H9B	109.5
C4—C5—H5	119.9	N3—C9—H9C	109.5
N2—C8—N3	117.67 (16)	H9A—C9—H9C	109.5
N2—C8—C7	123.72 (16)	H9B—C9—H9C	109.5
N3—C8—C7	118.47 (15)

C1—C2—C3—C4	−1.6 (2)	C1—C6—C5—C4	−1.0 (3)
C1—C2—C3—C7	178.20 (15)	C3—C4—C5—C6	0.4 (3)
C3—C2—C1—C6	0.9 (3)	N2—C8—C7—C3	−101.67 (19)
C3—C2—C1—N1	−178.90 (14)	N3—C8—C7—C3	73.9 (2)
O2—N1—C1—C6	164.10 (17)	C4—C3—C7—C8	51.8 (2)
O1—N1—C1—C6	−16.2 (3)	C2—C3—C7—C8	−128.00 (17)
O2—N1—C1—C2	−16.1 (3)	N3—C8—N2—O3	−173.71 (15)
O1—N1—C1—C2	163.65 (19)	C7—C8—N2—O3	1.9 (2)
C2—C3—C4—C5	1.0 (3)	N2—C8—N3—C9	−159.9 (2)
C7—C3—C4—C5	−178.82 (17)	C7—C8—N3—C9	24.3 (3)
C2—C1—C6—C5	0.4 (3)	N2—C8—N3—C10	−0.2 (3)
N1—C1—C6—C5	−179.78 (16)	C7—C8—N3—C10	−176.0 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N2ⁱ	0.82	2.11	2.8292 (19)	146
C10—H10C···O2ⁱⁱ	0.96	2.51	3.288 (3)	139
C10—H10B···Cg1	0.96	2.85	3.718 (3)	151

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

Funding information

Funding for this research was provided by: Natural Science Foundation of China (No. 21502076), Natural Science Foundation of Jiangxi Province (No. 20161BAB213068), Hundred–Talent Program (Hefei) and Outstanding Young Talent Program of Jiangxi Province (No. 20171BCB23039). .

References

Bruker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gao, F.-T., Fang, Z., Su, R.-R., Rui, P.-X. & Hu, X.-G. (2018). Org. Biomol. Chem. 16, 9211–9217. Web of Science CSD CrossRef CAS PubMed Google Scholar
Röhrig, U., Zoete, V. & Michielin, O. (2017). Biochemistry, 56, 4323–4325. Web of Science PubMed Google Scholar
Saeed, K., Haider, S., Oh, T.-J. & Park, S.-Y. (2008). J. Membr. Sci. 322, 400–405. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yuan, D., Chen, L., Xiong, X., Yuan, L., Liao, S. & Wang, Y. (2016). Chem. Eng. J. 285, 358–367. Web of Science CrossRef CAS Google Scholar
Zhao, Y., Li, J., Zhao, L., Zhang, S., Huang, Y., Wu, X. & Wang, X. (2014). Chem. Eng. J. 235, 275–283. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.