Crystal structure of 3-amino-5,5-dimethyl-2-[(E)-2-nitro­ethen­yl]cyclo­hex-2-en-1-one

Vigante, B.; Stepanovs, D.; Pelss, A.; Mishnev, A.

doi:10.1107/S1600536814023009

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 379-381

doi:10.1107/S1600536814023009

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Crystal structure of 3-amino-5,5-dimethyl-2-[(E)-2-nitroethenyl]cyclohex-2-en-1-one

Brigita Vigante,^a Dmitrijs Stepanovs,^a ^* Andrejs Pelss ^a and Anatoly Mishnev ^a

^aLatvian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga, LV-1006, Latvia
^*Correspondence e-mail: dmitrijs.stepanovs@me.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 4 October 2014; accepted 20 October 2014; online 24 October 2014)

The asymmetric unit of the title compound, C₁₀H₁₄N₂O₃, contains two independent molecules with similar conformations. In the both molecules, the cyclohexene rings adopt the same envelope conformation with the flap C atoms lying 0.658 (3) and 0.668 (3) Å from the mean planes formed by the remaining atoms. In the crystal, adjacent molecules are connected via N—H⋯O hydrogen bonds and weak C—H⋯O interactions, forming supramolecular layers parallel to (-101).

Keywords: nitrodienamines; nitroacetaldehyde; Knoevenagel-type condensation; crystal structure; hydrogen bonds.

CCDC reference: 1027341

1. Chemical context

sec-Nitrodienamines appear to be potentially useful synthons in organic synthesis due to the enaminic, dienic and `push–pull' character of these molecules (Koike et al., 2000 ). Several methods are available for the synthesis of nitrodienamines, which include the reaction of acetaldehydes with 1-dimethylamino-2-nitroethylen followed by treatment with amines (Severin et al., 1971 ), the reaction of aminoacrolein with dimethylamine and subsequent treatment of the vinylamidinium salt with nitromethane (Takeuchi et al., 1988 ) and nitroalkenylation reactions of 2-methylindolines with nitroenamines (Attanasi et al., 2006 ).

Previously, we found that alpha-nitro acetaldehyde undergoes an unusual condensation with aldehydes and ammonium acetate to afford 3,5-dinitro-1,2-dihydropyridines (Vigante et al., 1993 ). Afterwards, the synthesis of N-substituted 1,2-dihydropyridines by heterocyclic annulation reaction of sec-nitrodienamines with acetaldehyde was reported (Koike et al., 1999 ). As part of our studies of synthetic pathways to fused 1,2-dihydropyridines, the title compound was synthesized and we report herein on its molecular and crystal structure.

2. Structural commentary

The asymmetric unit of the title compound (Fig. 1) contains two independent molecules (A and B) having coincident geometry. The bond lengths in the molecules are close to standard values. The cyclohexene rings adopt an envelope conformation, with flap atoms C3A and C3B lying 0.658 (3) and 0.668 (3) Å from the mean planes formed by the remaining atoms in molecules A and B, respectively.

Figure 1
The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering

3. Supramolecular features

In the crystal, the molecules form sheets parallel to ( $[\overline{1}]$ 01) by means of N—H⋯O hydrogen bonds. The network consists of two hydrogen-bond motifs, R₂²(16) and R₆⁶(32) (Fig. 2). Weak C—H⋯O interactions are also observed in the supramolecular networks (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O1Bⁱ	0.84 (2)	2.06 (3)	2.873 (2)	162 (2)
N1A—H2NA⋯O3Bⁱⁱ	0.88 (2)	2.10 (3)	2.961 (2)	167 (2)
N1B—H1NB⋯O3Aⁱⁱ	0.92 (2)	2.03 (3)	2.942 (2)	168 (2)
N1B—H2NB⋯O1Aⁱⁱⁱ	0.85 (3)	2.04 (2)	2.858 (2)	162 (2)
C2A—H2A1⋯O1Bⁱ	0.97	2.42	3.262 (2)	145
C2B—H2B1⋯O1Aⁱⁱⁱ	0.97	2.46	3.298 (2)	144
C7A—H7A⋯O3Bⁱⁱ	0.93	2.54	3.469 (2)	173
C7B—H7B⋯O3Aⁱⁱ	0.93	2.55	3.469 (2)	171
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The crystal packing of the title compound showing sheets parallel to ( $[\overline{1}]$ 01).

4. Database survey

A search of the Cambridge Structural Database (Version 5.35; Groom & Allen, 2014 ) for 5,5-dimethylcyclohex-2-enones gave 609 hits. Only one of these is a 3-amino-5,5-dimethylcyclohex-2-enone, namely, 3-amino-5,5-dimethyl-2-phenylcyclohex-2-enone (Fun et al., 2007 ). The conformation of the cyclohexene ring is identical to that found in the title compound.

5. Synthesis and crystallization

A mixture of 3-amino-5,5-dimethylcyclohex-2-enone (140 mg, 1 mmol) and potassium salt of alpha-nitro acetaldehyde (190 mg, 1.5 mmol) in methanol (2 mL) and acetic acid (2 mL) was stirred for 5 days at room temperature. The solvents were removed under reduced pressure and the residue was purified by flash chromatography on silica gel, eluent: chloroform, hexane, acetone, methanol (9:7:1:1). The appropriate fraction was collected and crystallized from methanol, yielding 116 mg (55%) of bright-yellow crystals (m.p. 503 K).

MS (+ESI) m/z (relative intensity): 211.2 ([M+H]⁺, 100).¹H NMR (400 MHz, DMSO-d₆): δ 0.96 (s, 6H), 2.20 (s, 2H), 2.53 (s, 2H), 8.12 (d, J = 12.4 Hz, 1H), 8.39 (d, J = 12.4 Hz, 1H), 8.48 (s, 1H), 8.74 (s, 1H).

¹³C NMR (100.56 MHz, DMSO-d₆): δ 27.94, 31.41, 44.12, 51.46, 100.02, 131.82, 132.15, 172.30, 193.93. Analysis calculated for C₁₀H₁₄N₂O₃: C, 57.13; H, 6.71; N, 13.32; found: C, 56.98; H, 6.78; N, 13.16.

6. Refinement

Hydrogens on the amino group were located in a difference Fourier map and freely refined. The C-bound hydrogen atoms were positioned geometrically with C—H distances ranging from 0.93 to 0.97 Å and refined as riding on their parent atoms with U_iso(H) = 1.5U_eq(C) for methyl groups and U_iso(H) = 1.2U_eq(C) for other H atoms. The reflection whose intensity was affected by the beamstop was removed from the final refinement. Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₂O₃
M_r	210.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.3545 (3), 18.1097 (5), 10.4689 (3)
β (°)	100.119 (2)
V (Å³)	2119.20 (10)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.25 × 0.01

Data collection
Diffractometer	Nonius KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections	10741, 6174, 3235
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.158, 1.01
No. of reflections	6174
No. of parameters	287
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.29
Computer programs: KappaCCD Server Software (Nonius, 1997 ), HKL DENZO SCALEPACK (Otwinowski & Minor, 1997 ), SIR2011 (Burla et al., 2012 ), ORTEP-3 for Windows (Farrugia, 2012 ), SHELXL97 (Sheldrick, 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1027341

Crystal structure: contains datablocks I, globe. DOI: 10.1107/S1600536814023009/xu5825sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814023009/xu5825Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814023009/xu5825Isup3.cml

checkCIF report

Chemical context top

sec-Nitrodienamines appear to be potentially useful synthons in organic synthesis due to the enaminic, dienic and `push–pull' character of these molecules (Koike et al., 2000). Several methods are available for the synthesis of nitrodienamines, which include the reaction of acetaldehydes with 1-dimethylamino-2-nitroethylen followed by treatment with amines (Severin et al., 1971) or the reaction of aminoacrolein with dimethylamine and subsequent treatment of the vinylamidinium salt with nitromethane (Takeuchi et al., 1988) or by nitroalkenylation reactions of 2-methylindolines with nitroenamines (Attanasi et al., 2006).

Previously, we found that alpha-nitro acetaldehyde undergoes an unusual condensation with aldehydes and ammonium acetate to afford 3,5-dinitro-1,2-dihydropyridines (Vigante et al., 1993). Afterwards the synthesis of N-substituted 1,2-dihydropyridines by heterocyclic annulation reaction of sec-nitrodienamines with acetaldehyde was reported (Koike et al., 1999). As part of our studies of synthetic pathways to fused 1,2-dihydropyridines, the title compound was synthesized and we report herein its molecular and crystal structures.

Structural commentary top

The asymmetric unit of the title compound (Fig. 1) contains two independent molecules A and B having coincident geometry. The bond lengths in the molecules are close to standard values. The cyclohexene rings adopt an envelope conformation, with flap atoms C3A and C3B lying 0.658 (3) and 0.668 (3) Å from the mean planes formed by the remaining atoms in molecules A and B, respectively.

Supramolecular features top

In the crystal, the molecules form two-dimensional network layers parallel to (101) by means of N—H···O-type hydrogen bonds. The network consists of two hydrogen-bond motifs, R²₂(16) and R⁶₆(32) (Fig. 2). Weak C—H···O interactions are also observed in the supramolecular networks (Table 1).

Database survey top

A search of the Cambridge Structural Database (Version 5.35; Groom & Allen, 2014) for 5,5-dimethylcyclohex-2-enones gave 609 hits. Only one of these is a 3-amino-5,5-dimethylcyclohex-2-enone, namely, 3-amino-5,5-dimethyl-2-phenylcyclohex-2-enone (Fun et al., 2007). The conformation of the cyclohexene ring is identical to that found in the title compound.

Synthesis and crystallization top

The mixture of 3-amino-5,5-dimethylcyclohex-2-enone (140 mg, 1 mmol) and potassium salt of alpha-nitro acetaldehyde (190 mg, 1.5 mmol) in methanol (2 mL) and acetic acid (2 mL) was stirred for 5 days at r.t. The solvents were removed under reduced pressure and the residue was purified by flash chromatography on silica gel, eluent: chloroform, hexane, acetone, methanol (9:7:1:1). The appropriate fraction was collected and crystallized from methanol, yielding 116 mg (55%) of bright-yellow crystals (m.p. 503 K).

Refinement top

All non-hydrogen atoms were refined anisotropically. Hydrogens on the amino group were refined isotropically. All hydrogen atoms were positioned geometrically with C—H distances ranging from 0.93 to 0.97 Å and refined as riding on their parent atoms with U_iso(H) = 1.5U_eq(C) for methyl groups and U_iso(H) = 1.2U_eq(C) for others. The reflection whose intensity was affected by the beamstop was removed from the final refinement. Crystal data, data collection and structure refinement details are summarized in Table 2.

Related literature top

For related literature, see: Groom & Allen (2014); Attanasi et al. (2006); Fun et al. (2007); Koike et al. (1999, 2000); Severin et al. (1971); Takeuchi et al. (1988); Vigante et al. (1993).

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering

The crystal packing of the title compound showing two-dimensional network layers parallel to (101).

3-Amino-5,5-dimethyl-2-[(E)-2-nitroethenyl]cyclohex-2-en-1-one top

Crystal data top

C₁₀H₁₄N₂O₃	F(000) = 896
M_r = 210.23	D_x = 1.318 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 503 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.3545 (3) Å	Cell parameters from 11852 reflections
b = 18.1097 (5) Å	θ = 1.0–30.0°
c = 10.4689 (3) Å	µ = 0.10 mm⁻¹
β = 100.119 (2)°	T = 173 K
V = 2119.20 (10) Å³	Plate, yellow
Z = 8	0.35 × 0.25 × 0.01 mm

Data collection top

Nonius KappaCCD diffractometer	3235 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.068
Graphite monochromator	θ_max = 30.1°, θ_min = 2.7°
CCD scans	h = −15→15
10741 measured reflections	k = −25→23
6174 independent reflections	l = −14→14

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0554P)² + 0.6139P] where P = (F_o² + 2F_c²)/3
6174 reflections	(Δ/σ)_max < 0.001
287 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₀H₁₄N₂O₃	V = 2119.20 (10) Å³
M_r = 210.23	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.3545 (3) Å	µ = 0.10 mm⁻¹
b = 18.1097 (5) Å	T = 173 K
c = 10.4689 (3) Å	0.35 × 0.25 × 0.01 mm
β = 100.119 (2)°

Data collection top

Nonius KappaCCD diffractometer	3235 reflections with I > 2σ(I)
10741 measured reflections	R_int = 0.068
6174 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.28 e Å⁻³
6174 reflections	Δρ_min = −0.28 e Å⁻³
287 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
O1A	0.44423 (12)	0.26776 (8)	0.25500 (13)	0.0295 (4)
O2A	0.55773 (14)	0.50926 (9)	0.20293 (17)	0.0471 (5)
O3A	0.38755 (15)	0.52829 (9)	0.07970 (17)	0.0470 (5)
N1A	0.09527 (15)	0.33969 (10)	−0.03942 (16)	0.0254 (4)
H1NA	0.034 (2)	0.3223 (13)	−0.087 (2)	0.030*
H2NA	0.1126 (19)	0.3869 (14)	−0.043 (2)	0.030*
N2A	0.45967 (16)	0.48703 (10)	0.14688 (17)	0.0307 (4)
C1A	0.16406 (16)	0.29331 (11)	0.03826 (18)	0.0209 (4)
C2A	0.11184 (17)	0.21747 (11)	0.0458 (2)	0.0247 (5)
H2A1	0.0619	0.2062	−0.0369	0.030*
H2A2	0.0608	0.2179	0.1110	0.030*
C3A	0.20444 (16)	0.15635 (11)	0.07868 (19)	0.0229 (4)
C4A	0.28813 (18)	0.18035 (11)	0.20157 (19)	0.0271 (5)
H4A1	0.2440	0.1807	0.2729	0.032*
H4A2	0.3518	0.1442	0.2217	0.032*
C5A	0.34312 (16)	0.25560 (11)	0.19190 (17)	0.0215 (4)
C6A	0.27637 (16)	0.31205 (11)	0.11171 (17)	0.0207 (4)
C7A	0.32346 (17)	0.38535 (11)	0.10523 (18)	0.0232 (4)
H7A	0.2738	0.4188	0.0543	0.028*
C8A	0.42972 (18)	0.41153 (11)	0.16320 (19)	0.0259 (5)
H8A	0.4840	0.3805	0.2141	0.031*
C9A	0.27396 (19)	0.14516 (13)	−0.0321 (2)	0.0329 (5)
H9A1	0.3107	0.1909	−0.0500	0.049*
H9A2	0.2202	0.1292	−0.1083	0.049*
H9A3	0.3347	0.1084	−0.0078	0.049*
C10A	0.14236 (19)	0.08427 (12)	0.1036 (2)	0.0356 (6)
H10A	0.2015	0.0475	0.1344	0.053*
H10B	0.0938	0.0676	0.0244	0.053*
H10C	0.0927	0.0924	0.1677	0.053*
O1B	0.92300 (13)	0.24275 (8)	0.28241 (13)	0.0322 (4)
O2B	1.04280 (14)	0.48418 (9)	0.22269 (17)	0.0487 (5)
O3B	0.88174 (16)	0.49987 (9)	0.08349 (18)	0.0521 (5)
N1B	0.59376 (15)	0.31138 (10)	−0.04246 (17)	0.0263 (4)
H1NB	0.6104 (19)	0.3611 (14)	−0.046 (2)	0.032*
H2NB	0.537 (2)	0.2930 (12)	−0.097 (2)	0.032*
N2B	0.94809 (15)	0.46084 (10)	0.16108 (17)	0.0315 (4)
C1B	0.66003 (16)	0.26509 (11)	0.03703 (18)	0.0208 (4)
C2B	0.61249 (16)	0.18770 (11)	0.03415 (19)	0.0233 (4)
H2B1	0.5699	0.1773	−0.0526	0.028*
H2B2	0.5553	0.1847	0.0927	0.028*
C3B	0.70757 (16)	0.12831 (11)	0.07177 (19)	0.0227 (4)
C4B	0.77921 (18)	0.15161 (11)	0.20286 (19)	0.0258 (5)
H4B1	0.7281	0.1477	0.2677	0.031*
H4B2	0.8451	0.1174	0.2267	0.031*
C5B	0.82867 (17)	0.22863 (11)	0.20607 (18)	0.0224 (4)
C6B	0.76642 (16)	0.28498 (11)	0.12114 (18)	0.0213 (4)
C7B	0.81399 (17)	0.35818 (11)	0.11657 (18)	0.0236 (4)
H7B	0.7678	0.3906	0.0596	0.028*
C8B	0.91564 (18)	0.38621 (11)	0.18294 (19)	0.0258 (5)
H8B	0.9651	0.3572	0.2432	0.031*
C9B	0.78776 (19)	0.12275 (13)	−0.0302 (2)	0.0341 (5)
H9B1	0.8237	0.1699	−0.0400	0.051*
H9B2	0.7408	0.1080	−0.1116	0.051*
H9B3	0.8493	0.0868	−0.0033	0.051*
C10B	0.6467 (2)	0.05431 (12)	0.0841 (2)	0.0357 (6)
H10D	0.7056	0.0184	0.1199	0.054*
H10E	0.6074	0.0383	0.0000	0.054*
H10F	0.5888	0.0596	0.1402	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0257 (8)	0.0261 (9)	0.0313 (8)	0.0026 (6)	−0.0102 (6)	0.0006 (6)
O2A	0.0386 (9)	0.0392 (11)	0.0589 (11)	−0.0172 (8)	−0.0045 (8)	−0.0057 (8)
O3A	0.0501 (10)	0.0252 (9)	0.0583 (11)	−0.0029 (7)	−0.0110 (9)	0.0062 (8)
N1A	0.0226 (9)	0.0198 (10)	0.0294 (9)	−0.0021 (7)	−0.0073 (7)	0.0016 (7)
N2A	0.0321 (10)	0.0267 (11)	0.0314 (10)	−0.0052 (8)	0.0002 (8)	−0.0035 (8)
C1A	0.0194 (9)	0.0242 (12)	0.0187 (9)	0.0018 (8)	0.0021 (8)	−0.0004 (8)
C2A	0.0196 (10)	0.0243 (12)	0.0280 (10)	−0.0023 (8)	−0.0020 (8)	0.0045 (8)
C3A	0.0217 (10)	0.0193 (11)	0.0258 (10)	−0.0003 (8)	−0.0009 (8)	0.0010 (8)
C4A	0.0284 (11)	0.0238 (12)	0.0258 (10)	−0.0005 (9)	−0.0039 (9)	0.0059 (8)
C5A	0.0226 (10)	0.0244 (11)	0.0165 (9)	0.0035 (8)	0.0007 (8)	−0.0021 (8)
C6A	0.0206 (9)	0.0195 (11)	0.0201 (9)	0.0007 (8)	−0.0012 (8)	−0.0009 (7)
C7A	0.0248 (10)	0.0226 (12)	0.0207 (10)	0.0033 (8)	−0.0006 (8)	−0.0005 (8)
C8A	0.0275 (10)	0.0198 (12)	0.0286 (11)	−0.0003 (8)	0.0000 (9)	0.0000 (8)
C9A	0.0339 (11)	0.0270 (13)	0.0376 (12)	−0.0004 (9)	0.0061 (10)	−0.0051 (10)
C10A	0.0330 (12)	0.0248 (13)	0.0458 (14)	−0.0049 (9)	−0.0016 (11)	0.0055 (10)
O1B	0.0286 (8)	0.0280 (9)	0.0332 (8)	0.0016 (6)	−0.0131 (7)	−0.0021 (6)
O2B	0.0387 (9)	0.0368 (11)	0.0635 (12)	−0.0169 (8)	−0.0108 (9)	−0.0058 (8)
O3B	0.0520 (11)	0.0271 (10)	0.0665 (12)	−0.0061 (8)	−0.0193 (9)	0.0124 (8)
N1B	0.0229 (9)	0.0220 (10)	0.0292 (9)	−0.0008 (7)	−0.0090 (7)	0.0009 (7)
N2B	0.0302 (10)	0.0253 (11)	0.0361 (10)	−0.0038 (8)	−0.0018 (8)	−0.0039 (8)
C1B	0.0203 (10)	0.0211 (11)	0.0204 (9)	0.0023 (8)	0.0015 (8)	−0.0028 (8)
C2B	0.0189 (9)	0.0215 (11)	0.0276 (10)	−0.0024 (8)	−0.0013 (8)	0.0024 (8)
C3B	0.0216 (10)	0.0183 (11)	0.0269 (10)	−0.0013 (8)	0.0006 (8)	−0.0006 (8)
C4B	0.0274 (10)	0.0204 (11)	0.0271 (11)	0.0003 (8)	−0.0022 (9)	0.0051 (8)
C5B	0.0227 (10)	0.0226 (12)	0.0209 (10)	0.0027 (8)	0.0011 (8)	−0.0031 (8)
C6B	0.0203 (10)	0.0209 (11)	0.0207 (10)	−0.0003 (8)	−0.0017 (8)	−0.0010 (8)
C7B	0.0242 (10)	0.0206 (12)	0.0242 (10)	0.0024 (8)	−0.0007 (8)	−0.0019 (8)
C8B	0.0274 (10)	0.0230 (12)	0.0257 (10)	0.0013 (8)	0.0007 (9)	−0.0022 (8)
C9B	0.0329 (12)	0.0297 (14)	0.0405 (13)	−0.0033 (9)	0.0091 (10)	−0.0092 (10)
C10B	0.0378 (12)	0.0243 (13)	0.0419 (13)	−0.0072 (10)	−0.0017 (11)	0.0036 (10)

Geometric parameters (Å, º) top

O1A—C5A	1.240 (2)	O1B—C5B	1.245 (2)
O2A—N2A	1.231 (2)	O2B—N2B	1.228 (2)
O3A—N2A	1.233 (2)	O3B—N2B	1.230 (2)
N1A—C1A	1.324 (2)	N1B—C1B	1.320 (2)
N1A—H1NA	0.84 (2)	N1B—H1NB	0.92 (2)
N1A—H2NA	0.88 (2)	N1B—H2NB	0.86 (2)
N2A—C8A	1.426 (3)	N2B—C8B	1.430 (3)
C1A—C6A	1.410 (2)	C1B—C6B	1.411 (2)
C1A—C2A	1.504 (3)	C1B—C2B	1.500 (3)
C2A—C3A	1.524 (3)	C2B—C3B	1.526 (3)
C2A—H2A1	0.9700	C2B—H2B1	0.9700
C2A—H2A2	0.9700	C2B—H2B2	0.9700
C3A—C4A	1.522 (3)	C3B—C9B	1.523 (3)
C3A—C9A	1.527 (3)	C3B—C10B	1.524 (3)
C3A—C10A	1.528 (3)	C3B—C4B	1.527 (3)
C4A—C5A	1.510 (3)	C4B—C5B	1.502 (3)
C4A—H4A1	0.9700	C4B—H4B1	0.9700
C4A—H4A2	0.9700	C4B—H4B2	0.9700
C5A—C6A	1.449 (3)	C5B—C6B	1.453 (3)
C6A—C7A	1.437 (3)	C6B—C7B	1.435 (3)
C7A—C8A	1.338 (3)	C7B—C8B	1.338 (3)
C7A—H7A	0.9300	C7B—H7B	0.9300
C8A—H8A	0.9300	C8B—H8B	0.9300
C9A—H9A1	0.9600	C9B—H9B1	0.9600
C9A—H9A2	0.9600	C9B—H9B2	0.9600
C9A—H9A3	0.9600	C9B—H9B3	0.9600
C10A—H10A	0.9600	C10B—H10D	0.9600
C10A—H10B	0.9600	C10B—H10E	0.9600
C10A—H10C	0.9600	C10B—H10F	0.9600

C1A—N1A—H1NA	117.6 (15)	C1B—N1B—H1NB	123.2 (12)
C1A—N1A—H2NA	122.0 (13)	C1B—N1B—H2NB	117.2 (15)
H1NA—N1A—H2NA	120 (2)	H1NB—N1B—H2NB	119.4 (19)
O2A—N2A—O3A	121.86 (19)	O2B—N2B—O3B	121.85 (19)
O2A—N2A—C8A	118.09 (17)	O2B—N2B—C8B	117.90 (17)
O3A—N2A—C8A	120.05 (16)	O3B—N2B—C8B	120.26 (16)
N1A—C1A—C6A	124.16 (19)	N1B—C1B—C6B	124.21 (19)
N1A—C1A—C2A	114.59 (16)	N1B—C1B—C2B	114.67 (16)
C6A—C1A—C2A	121.23 (16)	C6B—C1B—C2B	121.11 (16)
C1A—C2A—C3A	114.37 (16)	C1B—C2B—C3B	114.68 (15)
C1A—C2A—H2A1	108.7	C1B—C2B—H2B1	108.6
C3A—C2A—H2A1	108.7	C3B—C2B—H2B1	108.6
C1A—C2A—H2A2	108.7	C1B—C2B—H2B2	108.6
C3A—C2A—H2A2	108.7	C3B—C2B—H2B2	108.6
H2A1—C2A—H2A2	107.6	H2B1—C2B—H2B2	107.6
C4A—C3A—C2A	106.68 (16)	C9B—C3B—C10B	109.70 (18)
C4A—C3A—C9A	110.52 (16)	C9B—C3B—C2B	110.40 (17)
C2A—C3A—C9A	110.67 (17)	C10B—C3B—C2B	109.33 (16)
C4A—C3A—C10A	109.75 (16)	C9B—C3B—C4B	111.01 (16)
C2A—C3A—C10A	109.79 (16)	C10B—C3B—C4B	110.17 (17)
C9A—C3A—C10A	109.39 (18)	C2B—C3B—C4B	106.16 (16)
C5A—C4A—C3A	113.90 (16)	C5B—C4B—C3B	114.51 (16)
C5A—C4A—H4A1	108.8	C5B—C4B—H4B1	108.6
C3A—C4A—H4A1	108.8	C3B—C4B—H4B1	108.6
C5A—C4A—H4A2	108.8	C5B—C4B—H4B2	108.6
C3A—C4A—H4A2	108.8	C3B—C4B—H4B2	108.6
H4A1—C4A—H4A2	107.7	H4B1—C4B—H4B2	107.6
O1A—C5A—C6A	121.64 (18)	O1B—C5B—C6B	121.31 (18)
O1A—C5A—C4A	118.67 (16)	O1B—C5B—C4B	118.76 (17)
C6A—C5A—C4A	119.68 (16)	C6B—C5B—C4B	119.93 (16)
C1A—C6A—C7A	120.33 (17)	C1B—C6B—C7B	120.06 (17)
C1A—C6A—C5A	118.48 (17)	C1B—C6B—C5B	118.28 (17)
C7A—C6A—C5A	121.18 (16)	C7B—C6B—C5B	121.58 (16)
C8A—C7A—C6A	128.25 (18)	C8B—C7B—C6B	128.93 (18)
C8A—C7A—H7A	115.9	C8B—C7B—H7B	115.5
C6A—C7A—H7A	115.9	C6B—C7B—H7B	115.5
C7A—C8A—N2A	120.01 (18)	C7B—C8B—N2B	119.90 (18)
C7A—C8A—H8A	120.0	C7B—C8B—H8B	120.0
N2A—C8A—H8A	120.0	N2B—C8B—H8B	120.0
C3A—C9A—H9A1	109.5	C3B—C9B—H9B1	109.5
C3A—C9A—H9A2	109.5	C3B—C9B—H9B2	109.5
H9A1—C9A—H9A2	109.5	H9B1—C9B—H9B2	109.5
C3A—C9A—H9A3	109.5	C3B—C9B—H9B3	109.5
H9A1—C9A—H9A3	109.5	H9B1—C9B—H9B3	109.5
H9A2—C9A—H9A3	109.5	H9B2—C9B—H9B3	109.5
C3A—C10A—H10A	109.5	C3B—C10B—H10D	109.5
C3A—C10A—H10B	109.5	C3B—C10B—H10E	109.5
H10A—C10A—H10B	109.5	H10D—C10B—H10E	109.5
C3A—C10A—H10C	109.5	C3B—C10B—H10F	109.5
H10A—C10A—H10C	109.5	H10D—C10B—H10F	109.5
H10B—C10A—H10C	109.5	H10E—C10B—H10F	109.5

N1A—C1A—C2A—C3A	152.82 (18)	N1B—C1B—C2B—C3B	152.97 (18)
C6A—C1A—C2A—C3A	−28.5 (3)	C6B—C1B—C2B—C3B	−28.1 (3)
C1A—C2A—C3A—C4A	52.7 (2)	C1B—C2B—C3B—C9B	−67.4 (2)
C1A—C2A—C3A—C9A	−67.5 (2)	C1B—C2B—C3B—C10B	171.80 (17)
C1A—C2A—C3A—C10A	171.61 (17)	C1B—C2B—C3B—C4B	53.0 (2)
C2A—C3A—C4A—C5A	−54.4 (2)	C9B—C3B—C4B—C5B	66.5 (2)
C9A—C3A—C4A—C5A	66.0 (2)	C10B—C3B—C4B—C5B	−171.79 (18)
C10A—C3A—C4A—C5A	−173.26 (18)	C2B—C3B—C4B—C5B	−53.5 (2)
C3A—C4A—C5A—O1A	−149.19 (18)	C3B—C4B—C5B—O1B	−150.83 (19)
C3A—C4A—C5A—C6A	31.9 (3)	C3B—C4B—C5B—C6B	29.2 (3)
N1A—C1A—C6A—C7A	−0.1 (3)	N1B—C1B—C6B—C7B	−5.0 (3)
C2A—C1A—C6A—C7A	−178.63 (19)	C2B—C1B—C6B—C7B	176.23 (19)
N1A—C1A—C6A—C5A	−179.33 (19)	N1B—C1B—C6B—C5B	178.3 (2)
C2A—C1A—C6A—C5A	2.2 (3)	C2B—C1B—C6B—C5B	−0.5 (3)
O1A—C5A—C6A—C1A	177.29 (19)	O1B—C5B—C6B—C1B	179.96 (19)
C4A—C5A—C6A—C1A	−3.9 (3)	C4B—C5B—C6B—C1B	−0.1 (3)
O1A—C5A—C6A—C7A	−1.9 (3)	O1B—C5B—C6B—C7B	3.3 (3)
C4A—C5A—C6A—C7A	176.91 (19)	C4B—C5B—C6B—C7B	−176.77 (19)
C1A—C6A—C7A—C8A	−176.7 (2)	C1B—C6B—C7B—C8B	−176.3 (2)
C5A—C6A—C7A—C8A	2.5 (3)	C5B—C6B—C7B—C8B	0.3 (3)
C6A—C7A—C8A—N2A	−178.8 (2)	C6B—C7B—C8B—N2B	178.4 (2)
O2A—N2A—C8A—C7A	179.2 (2)	O2B—N2B—C8B—C7B	−179.1 (2)
O3A—N2A—C8A—C7A	0.2 (3)	O3B—N2B—C8B—C7B	1.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1Bⁱ	0.84 (2)	2.06 (3)	2.873 (2)	162 (2)
N1A—H2NA···O3Bⁱⁱ	0.88 (2)	2.10 (3)	2.961 (2)	167 (2)
N1B—H1NB···O3Aⁱⁱ	0.92 (2)	2.03 (3)	2.942 (2)	168 (2)
N1B—H2NB···O1Aⁱⁱⁱ	0.85 (3)	2.04 (2)	2.858 (2)	162 (2)
C2A—H2A1···O1Bⁱ	0.97	2.42	3.262 (2)	145
C2B—H2B1···O1Aⁱⁱⁱ	0.97	2.46	3.298 (2)	144
C7A—H7A···O3Bⁱⁱ	0.93	2.54	3.469 (2)	173
C7B—H7B···O3Aⁱⁱ	0.93	2.55	3.469 (2)	171

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1Bⁱ	0.84 (2)	2.06 (3)	2.873 (2)	162 (2)
N1A—H2NA···O3Bⁱⁱ	0.88 (2)	2.10 (3)	2.961 (2)	167 (2)
N1B—H1NB···O3Aⁱⁱ	0.92 (2)	2.03 (3)	2.942 (2)	168 (2)
N1B—H2NB···O1Aⁱⁱⁱ	0.85 (3)	2.04 (2)	2.858 (2)	162 (2)
C2A—H2A1···O1Bⁱ	0.97	2.42	3.262 (2)	145
C2B—H2B1···O1Aⁱⁱⁱ	0.97	2.46	3.298 (2)	144
C7A—H7A···O3Bⁱⁱ	0.93	2.54	3.469 (2)	173
C7B—H7B···O3Aⁱⁱ	0.93	2.55	3.469 (2)	171

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₂O₃
M_r	210.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.3545 (3), 18.1097 (5), 10.4689 (3)
β (°)	100.119 (2)
V (Å³)	2119.20 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.25 × 0.01

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10741, 6174, 3235
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.158, 1.01
No. of reflections	6174
No. of parameters	287
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.28

Computer programs: KappaCCD Server Software (Nonius, 1997), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2011 (Burla et al., 2012), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

This work was supported by the European Social Fund (No. 1DP/1.1.1.2.0/13/APIA/VIAA/011).

References

Attanasi, O. A., Favi, G., Filippone, P., Forzato, C., Giorgi, G., Morganti, S., Nitti, P., Pitacco, G., Rizzato, E., Spinelli, D. & Valentin, E. (2006). Tetrahedron, 62, 6420–6434. Web of Science CSD CrossRef CAS Google Scholar
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Volume 70| Part 11| November 2014| Pages 379-381

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of 3-amino-5,5-di­methyl-2-[(E)-2-nitro­ethen­yl]cyclo­hex-2-en-1-one

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of 3-amino-5,5-dimethyl-2-[(E)-2-nitroethenyl]cyclohex-2-en-1-one

3. Supramolecular features