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The title compound, C14H14N2O3, was prepared by the base-catalyzed condensation reaction of 3-nitro­benzaldehyde with 1-aza­bicyclo­[2.2.2]octan-3-one. The 3-nitro­phenyl ring is twisted by 27.29 (19)° with respect to the plane of the C=C double bond connected to the aza­bicyclic ring. The mol­ecule adopts the Z configuration.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028576/ac6200sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028576/ac6200Isup2.hkl
Contains datablock I

CCDC reference: 287432

Key indicators

  • Single-crystal X-ray study
  • T = 90 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.037
  • wR factor = 0.098
  • Data-to-parameter ratio = 15.9

checkCIF/PLATON results

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Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT230_ALERT_2_C Hirshfeld Test Diff for O2 - N2 .. 5.12 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

In continuation of our work with 2-(substituted benzylidene/heteroaryl-3-ylmethylene)-1-azabicyclo[2.2.2]octan-3-ones (Sonar et al., 2004), as precursors of medicinal agents, we synthesized the title compound, (I). The compound was prepared by base-catalyzed condensation of 3-nitrobenzaldehyde with 1-azabicyclo[2.2.2]octan-3-one, to afford a single geometrical isomer. To study the structural conformation of the molecule, its X-ray structure determination has been carried out.

In the title compound, the C1—C7 bond is in a trans disposition with respect to the C8—C9 bond and the molecule adopts the Z configuration. The double bond is nearly planar in the molecule, as indicated by the value of 0.0091 (7) Å for the r.m.s. deviation of atoms N1, C8, C9, C7 and C1 from the best plane passing through them. The Csp2—N bond associated with the nitro group attached to the phenyl ring is clearly of single-bond character [1.4739 (16) Å]. Deviations from the ideal bond-angle geometry around the sp2 C atoms of the double bonds are observed. While the N2—C5—C6, C6—C1—C7, C2—C1—C7 and C7—C8—C9 angles show values of 118.24 (11), 117.87 (11), 123.18 (11) and 121.26 (11)°, respectively, which are close to ideal geometry (120°), the C1—C7—C8, C7—C8—N1, N1—C8—C9, C8—C9—O1 and C8—C9—C10 angles are distorted because of steric hindrance of the double bond linking the two ring systems. They assume values of 128.62 (11), 125.40 (11), 113.33 (10), 124.75 (11) and 110.76 (10)°, respectively. These deviations contribute significantly to the release of the intramolecular non-bonded interactions present in this portion of the molecule. The C2—C1—C7—C8 torsion angle [27.29 (19)°] indicates a deviation of the 3-nitrophenyl ring from the plane of the double bond connected to the azabicyclic ring. However, the C4—C7 bond length [1.4660 (16) Å] suggests conjugation of the C7—C8 π electrons with those of the 3-nitrophenyl ring (Wilson, 1992).

The crystal packing of (I) (Fig. 2) shows that the molecules exist as hydrogen-bonded dimers, connected through weak C—H.·O hydrogen bonds.

Experimental top

A mixture of 3-nitrobenzaldehyde (0.499 g, 3 mmol) and 1-azabicyclo[2.2.2]octane hydrochloride (0.483 g, 3 mmol) was dissolved in 10% methanolic KOH (10 ml) and the solution refluxed for 5 h. The cooled reaction mixture was poured into crushed ice (100 g) and the yellow crystalline solid that separated was collected by filtration, washed with water and air dried. Recrystallization from methanol afforded yellow needles of (I), which were suitable for X-ray analysis. Spectroscopic analysis: 1H NMR (CDCl3, δ, p.p.m.): 2.04–2.09 (td, 4H), 2.66–2.7 (p, 1H), 2.95–3.06 (m, 2H), 3.18–3.28 (m, 2H), 7.03 (s, 1H), 7.51–7.57 (t, 1H), 8.15–8.24 (m, 2H), 9.02–9.03 (t, 1H); 13C NMR (CDCl3, δ, p.p.m.): 25.9, 40.4, 47.6, 122.3, 123.9, 126.6, 129.4, 135.6, 137.7, 146.9, 148.5, 205.7.

Refinement top

H atoms were positioned geometrically and refined as riding, with C—H distances in the range 0.95–0.99 Å and with Uiso(H) = 1.2Ueq(C). [Please check added text and correct as necessary.]

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 and local procedures.

Figures top
[Figure 1] Fig. 1. Please provide caption.
[Figure 2] Fig. 2. Please provide caption.
(Z)-2-(3-Nitrobenzylidene)-1-azabicyclo[2.2.2]octan-3-one top
Crystal data top
C14H14N2O3F(000) = 544
Mr = 258.27Dx = 1.441 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4654 reflections
a = 5.8095 (1) Åθ = 1–27.5°
b = 24.2920 (4) ŵ = 0.10 mm1
c = 8.5473 (2) ÅT = 90 K
β = 99.2211 (8)°Needle, yellow
V = 1190.64 (4) Å30.30 × 0.25 × 0.20 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
2739 independent reflections
Radiation source: fine-focus sealed tube2275 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
Detector resolution: 18 pixels mm-1θmax = 27.5°, θmin = 1.7°
ω scans at fixed χ = 55°h = 77
Absorption correction: multi-scan
SCALEPACK (Otwinowski & Minor, 1997)
k = 2931
Tmin = 0.970, Tmax = 0.980l = 1111
9090 measured reflections
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0463P)2 + 0.444P]
where P = (Fo2 + 2Fc2)/3
2739 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C14H14N2O3V = 1190.64 (4) Å3
Mr = 258.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.8095 (1) ŵ = 0.10 mm1
b = 24.2920 (4) ÅT = 90 K
c = 8.5473 (2) Å0.30 × 0.25 × 0.20 mm
β = 99.2211 (8)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
2739 independent reflections
Absorption correction: multi-scan
SCALEPACK (Otwinowski & Minor, 1997)
2275 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.980Rint = 0.027
9090 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.04Δρmax = 0.32 e Å3
2739 reflectionsΔρmin = 0.23 e Å3
172 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
N10.13636 (17)0.37496 (4)0.69584 (11)0.0142 (2)
O10.26010 (15)0.51717 (4)0.61669 (11)0.0207 (2)
C10.3331 (2)0.36044 (5)0.38323 (13)0.0143 (2)
N20.71988 (19)0.30897 (5)0.10506 (12)0.0241 (3)
O20.82297 (17)0.35203 (4)0.08570 (11)0.0295 (2)
C20.1891 (2)0.31439 (5)0.38853 (14)0.0170 (3)
H20.06690.31570.45020.020*
O30.75894 (18)0.26495 (5)0.04314 (12)0.0372 (3)
C30.2232 (2)0.26694 (5)0.30474 (15)0.0203 (3)
H30.12330.23620.30900.024*
C40.4017 (2)0.26396 (5)0.21472 (15)0.0214 (3)
H40.42930.23120.16000.026*
C50.5382 (2)0.31023 (5)0.20723 (13)0.0186 (3)
C60.5076 (2)0.35851 (5)0.28781 (13)0.0159 (2)
H60.60320.38970.27850.019*
C70.3061 (2)0.41158 (5)0.46954 (14)0.0146 (2)
H70.35820.44410.42440.018*
C80.21777 (19)0.41853 (5)0.60342 (14)0.0141 (2)
C90.1975 (2)0.47444 (5)0.67265 (14)0.0151 (2)
C100.0897 (2)0.47105 (5)0.82161 (14)0.0161 (3)
H100.07300.50840.86750.019*
C110.1492 (2)0.44243 (5)0.77922 (15)0.0175 (3)
H11A0.25460.46530.70290.021*
H11B0.22120.43770.87580.021*
C120.1130 (2)0.38538 (5)0.70491 (14)0.0170 (3)
H12A0.17110.35620.76950.020*
H12B0.20500.38370.59700.020*
C130.2496 (2)0.43407 (5)0.93859 (14)0.0177 (3)
H13A0.18300.42941.03740.021*
H13B0.40560.45110.96580.021*
C140.2704 (2)0.37742 (5)0.85903 (14)0.0166 (3)
H14A0.43670.36980.85500.020*
H14B0.21280.34840.92440.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0145 (5)0.0147 (5)0.0139 (5)0.0013 (4)0.0035 (4)0.0013 (4)
O10.0226 (5)0.0149 (4)0.0266 (5)0.0030 (4)0.0097 (4)0.0008 (4)
C10.0159 (6)0.0150 (6)0.0114 (5)0.0019 (4)0.0001 (4)0.0014 (4)
N20.0217 (6)0.0365 (7)0.0133 (5)0.0108 (5)0.0001 (4)0.0041 (5)
O20.0279 (5)0.0408 (6)0.0220 (5)0.0072 (5)0.0107 (4)0.0060 (4)
C20.0185 (6)0.0172 (6)0.0144 (6)0.0001 (5)0.0006 (4)0.0021 (5)
O30.0290 (5)0.0495 (7)0.0321 (6)0.0121 (5)0.0022 (4)0.0235 (5)
C30.0254 (6)0.0148 (6)0.0180 (6)0.0015 (5)0.0043 (5)0.0007 (5)
C40.0278 (7)0.0177 (6)0.0160 (6)0.0058 (5)0.0047 (5)0.0038 (5)
C50.0197 (6)0.0243 (7)0.0110 (5)0.0067 (5)0.0002 (5)0.0013 (5)
C60.0169 (6)0.0174 (6)0.0130 (5)0.0015 (5)0.0007 (4)0.0015 (5)
C70.0137 (5)0.0137 (6)0.0165 (6)0.0003 (4)0.0026 (4)0.0013 (4)
C80.0124 (5)0.0130 (6)0.0168 (6)0.0004 (4)0.0023 (4)0.0006 (4)
C90.0111 (5)0.0161 (6)0.0182 (6)0.0006 (4)0.0029 (4)0.0009 (5)
C100.0167 (6)0.0138 (6)0.0188 (6)0.0011 (4)0.0057 (5)0.0021 (5)
C110.0144 (6)0.0197 (6)0.0195 (6)0.0018 (5)0.0058 (5)0.0018 (5)
C120.0139 (6)0.0201 (6)0.0174 (6)0.0029 (5)0.0036 (4)0.0005 (5)
C130.0174 (6)0.0191 (6)0.0166 (6)0.0007 (5)0.0024 (5)0.0029 (5)
C140.0168 (6)0.0172 (6)0.0156 (6)0.0020 (5)0.0018 (4)0.0009 (5)
Geometric parameters (Å, º) top
N1—C81.4448 (15)C7—C81.3376 (17)
N1—C121.4846 (15)C7—H70.9500
N1—C141.4858 (15)C8—C91.4937 (16)
O1—C91.2223 (14)C9—C101.5085 (16)
C1—C61.4003 (16)C10—C131.5401 (17)
C1—C21.4020 (17)C10—C111.5426 (16)
C1—C71.4660 (16)C10—H101.0000
N2—O21.2297 (16)C11—C121.5529 (17)
N2—O31.2303 (15)C11—H11A0.9900
N2—C51.4739 (16)C11—H11B0.9900
C2—C31.3878 (17)C12—H12A0.9900
C2—H20.9500C12—H12B0.9900
C3—C41.3891 (19)C13—C141.5483 (17)
C3—H30.9500C13—H13A0.9900
C4—C51.3831 (19)C13—H13B0.9900
C4—H40.9500C14—H14A0.9900
C5—C61.3857 (17)C14—H14B0.9900
C6—H60.9500
C8—N1—C12108.14 (9)C8—C9—C10110.76 (10)
C8—N1—C14108.39 (9)C9—C10—C13106.92 (9)
C12—N1—C14108.24 (9)C9—C10—C11107.81 (10)
C6—C1—C2118.92 (11)C13—C10—C11108.41 (10)
C6—C1—C7117.87 (11)C9—C10—H10111.2
C2—C1—C7123.18 (11)C13—C10—H10111.2
O2—N2—O3123.65 (11)C11—C10—H10111.2
O2—N2—C5118.19 (11)C10—C11—C12108.82 (9)
O3—N2—C5118.16 (12)C10—C11—H11A109.9
C3—C2—C1120.72 (12)C12—C11—H11A109.9
C3—C2—H2119.6C10—C11—H11B109.9
C1—C2—H2119.6C12—C11—H11B109.9
C2—C3—C4120.67 (12)H11A—C11—H11B108.3
C2—C3—H3119.7N1—C12—C11111.76 (9)
C4—C3—H3119.7N1—C12—H12A109.3
C5—C4—C3117.90 (11)C11—C12—H12A109.3
C5—C4—H4121.1N1—C12—H12B109.3
C3—C4—H4121.1C11—C12—H12B109.3
C4—C5—C6123.00 (11)H12A—C12—H12B107.9
C4—C5—N2118.73 (11)C10—C13—C14108.35 (10)
C6—C5—N2118.24 (11)C10—C13—H13A110.0
C5—C6—C1118.72 (11)C14—C13—H13A110.0
C5—C6—H6120.6C10—C13—H13B110.0
C1—C6—H6120.6C14—C13—H13B110.0
C8—C7—C1128.62 (11)H13A—C13—H13B108.4
C8—C7—H7115.7N1—C14—C13112.46 (9)
C1—C7—H7115.7N1—C14—H14A109.1
C7—C8—N1125.40 (11)C13—C14—H14A109.1
C7—C8—C9121.26 (11)N1—C14—H14B109.1
N1—C8—C9113.33 (10)C13—C14—H14B109.1
O1—C9—C8124.75 (11)H14A—C14—H14B107.8
O1—C9—C10124.49 (11)
C6—C1—C2—C32.03 (17)C12—N1—C8—C959.84 (12)
C7—C1—C2—C3179.79 (11)C14—N1—C8—C957.30 (12)
C1—C2—C3—C40.46 (18)C7—C8—C9—O10.98 (19)
C2—C3—C4—C52.17 (18)N1—C8—C9—O1178.38 (11)
C3—C4—C5—C61.45 (18)C7—C8—C9—C10179.17 (11)
C3—C4—C5—N2176.53 (10)N1—C8—C9—C101.46 (14)
O2—N2—C5—C4172.24 (11)O1—C9—C10—C13120.35 (13)
O3—N2—C5—C47.34 (16)C8—C9—C10—C1359.50 (12)
O2—N2—C5—C65.84 (16)O1—C9—C10—C11123.26 (12)
O3—N2—C5—C6174.58 (11)C8—C9—C10—C1156.89 (12)
C4—C5—C6—C11.00 (18)C9—C10—C11—C1256.53 (12)
N2—C5—C6—C1179.00 (10)C13—C10—C11—C1258.88 (12)
C2—C1—C6—C52.72 (16)C8—N1—C12—C1157.98 (12)
C7—C1—C6—C5179.01 (10)C14—N1—C12—C1159.25 (12)
C6—C1—C7—C8154.52 (12)C10—C11—C12—N10.11 (13)
C2—C1—C7—C827.29 (19)C9—C10—C13—C1457.64 (12)
C1—C7—C8—N12.5 (2)C11—C10—C13—C1458.36 (12)
C1—C7—C8—C9178.24 (11)C8—N1—C14—C1357.12 (12)
C12—N1—C8—C7120.83 (12)C12—N1—C14—C1359.95 (12)
C14—N1—C8—C7122.04 (12)C10—C13—C14—N10.71 (13)

Experimental details

Crystal data
Chemical formulaC14H14N2O3
Mr258.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)90
a, b, c (Å)5.8095 (1), 24.2920 (4), 8.5473 (2)
β (°) 99.2211 (8)
V3)1190.64 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
SCALEPACK (Otwinowski & Minor, 1997)
Tmin, Tmax0.970, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
9090, 2739, 2275
Rint0.027
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.099, 1.04
No. of reflections2739
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.23

Computer programs: COLLECT (Nonius, 1999), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1995), SHELXL97 and local procedures.

Selected geometric parameters (Å, º) top
N1—C81.4448 (15)N2—O31.2303 (15)
N1—C121.4846 (15)N2—C51.4739 (16)
O1—C91.2223 (14)C7—C81.3376 (17)
C1—C71.4660 (16)C8—C91.4937 (16)
C2—C1—C7123.18 (11)C8—C7—C1128.62 (11)
O2—N2—O3123.65 (11)C7—C8—N1125.40 (11)
O2—N2—C5118.19 (11)N1—C8—C9113.33 (10)
C6—C5—N2118.24 (11)C8—C9—C10110.76 (10)
C6—C1—C7—C8154.52 (12)C1—C7—C8—N12.5 (2)
C2—C1—C7—C827.29 (19)C7—C8—C9—O10.98 (19)
 

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