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In the title compound, 4-nitro-7-oxo­cyclo­hepta-1,3,5-trienyl butanoate, C11H11NO5, the tropolone ring is approximately perpendicular to the ester plane [dihedral angle 71.8 (1)°] and the paraffin chain has trans and gauche conformations. Intermolecular π–π interactions between the tropolone planes are observed in the crystalline state.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003749/tk6006sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003749/tk6006Isup2.hkl
Contains datablock I

CCDC reference: 162817

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.055
  • wR factor = 0.168
  • Data-to-parameter ratio = 15.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

Troponoids have been an important building block for constructing liquid crystals (Mori & Takeshita, 1995). Recently, we prepared liquid crystals with a troponoid core which has enhanced the formation of smectic phases when compared with the corresponding benzenoids (Mori & Takeshita, 1995; Hashimoto et al., 2000). The crystal structures of cores such as tropolone, 5-nitrotropolone and 5-cyanotropolone rings have been elucidated by X-ray analyses (Shimanouchi & Sasada, 1973; Kubo et al., 2001). In order to reveal the effect upon crystal packing of substitution at O2 of 5-nitrotropolone, we now report the structure of the title compound, (I), as shown in Fig. 1.

The seven-membered ring in (I) is nearly planar; the respective deviations of each atom from least-squares plane A, defined by atoms C1–C7/O1/O2, are 0.033 (4), 0.064 (4), 0.048 (4), -0.031 (5), -0.064 (4), 0.022 (4), 0.083 (5), -0.040 (3) and -0.015 (3) Å. The dihedral angle between the least-squares planes through A and B [defined atoms by O2, O5 and C8] is 71.8 (1)°, which is similar to that in tropolonyl p-chlorobenzoate of 71.5° (Schaefer & Reed, 1971). The C—C bond lengths of the seven-membered ring of (I) are similar to those of tropone (Barrow et al., 1973), but are distinct from 5-nitrotropolone (Kubo et al., 2001). The paraffin chain has trans and gauche conformations.

Intermolecular ππ interactions are observed between the tropolone dimer planes (head-to-tail) of (I) (Fig. 2). The distance between intermolecular tropolone planes is 3.461 (5) Å for C1—C4i [symmetry code: (i) 1 - x, -y, 1 - z], which is similar to the distance of 3.40 Å found in 5-nitrotropolone (Kubo et al., 2001). However, the packing in (I) is distinct form that of 5-nitrotropolone (Kubo et al., 2001), which features intermolecular NO2ππ interactions. Thus, the substitution at O2 results in a different crystal-packing arrangement.

Experimental top

Compound (I) was prepared by esterification of 5-nitrotropolone with butanoyl chloride. The single crystals of (I) were obtained by recrystallization from a chloroform solution of the compound.

Refinement top

All H atoms were fixed at ideal positions and restrained with Uiso held fixed to 1.2Ueq of the parent atoms.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids (Johnson, 1976).
[Figure 2] Fig. 2. Packing diagram of (I) viewed down the b axis. H atoms have been omitted for clarity.
(I) top
Crystal data top
C11H11NO5F(000) = 496
Mr = 237.21Dx = 1.404 Mg m3
Monoclinic, P21/aMo Kα radiation, λ = 0.71073 Å
a = 12.8585 (14) ÅCell parameters from 21 reflections
b = 10.7092 (11) Åθ = 9.1–18.1°
c = 8.3657 (14) ŵ = 0.11 mm1
β = 103.052 (11)°T = 296 K
V = 1122.2 (3) Å3Prism, yellow
Z = 40.33 × 0.23 × 0.23 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
953 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.073
Graphite monochromatorθmax = 27.0°, θmin = 3.1°
ω–2θ scansh = 016
Absorption correction: ψ scan
(North et al., 1968)
k = 130
Tmin = 0.981, Tmax = 1l = 1010
2559 measured reflections3 standard reflections every 120 min
2450 independent reflections intensity decay: 0.1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.168 w = 1/[σ2(Fo2) + (0.0673P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max < 0.001
2450 reflectionsΔρmax = 0.19 e Å3
155 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.018 (3)
Crystal data top
C11H11NO5V = 1122.2 (3) Å3
Mr = 237.21Z = 4
Monoclinic, P21/aMo Kα radiation
a = 12.8585 (14) ŵ = 0.11 mm1
b = 10.7092 (11) ÅT = 296 K
c = 8.3657 (14) Å0.33 × 0.23 × 0.23 mm
β = 103.052 (11)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
953 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.073
Tmin = 0.981, Tmax = 13 standard reflections every 120 min
2559 measured reflections intensity decay: 0.1%
2450 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.168H-atom parameters constrained
S = 0.95Δρmax = 0.19 e Å3
2450 reflectionsΔρmin = 0.18 e Å3
155 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
N10.2129 (2)0.1110 (3)0.4515 (4)0.0569 (8)
O10.66475 (19)0.2185 (2)0.7017 (3)0.0744 (8)
O20.65022 (17)0.0067 (2)0.8162 (3)0.0640 (7)
O30.15680 (19)0.0242 (2)0.4730 (4)0.0788 (9)
O40.18189 (18)0.1968 (2)0.3565 (3)0.0739 (8)
O50.6630 (2)0.1186 (3)1.0328 (3)0.0863 (9)
C10.5734 (3)0.1770 (3)0.6764 (4)0.0522 (9)
C20.5561 (3)0.0518 (3)0.7365 (4)0.0487 (8)
C30.4674 (2)0.0177 (3)0.7161 (4)0.0544 (9)
H30.47600.09470.76880.065*
C40.3627 (2)0.0088 (3)0.6261 (4)0.0494 (8)
H40.31260.05410.62420.059*
C50.3266 (2)0.1128 (3)0.5436 (4)0.0452 (8)
C60.3820 (3)0.2241 (3)0.5300 (4)0.0615 (10)
H60.34090.28770.47190.074*
C70.4855 (3)0.2521 (3)0.5882 (5)0.0663 (10)
H70.50370.33380.56850.080*
C80.7031 (3)0.0443 (4)0.9621 (5)0.0616 (10)
C90.8117 (3)0.0124 (4)1.0177 (6)0.0858 (13)
H9A0.80600.08671.08160.103*
H9B0.83710.03810.92210.103*
C100.8914 (4)0.0733 (7)1.1180 (5)0.116 (2)
H10A0.86340.10451.20870.139*
H10B0.95590.02671.16370.139*
C110.9185 (4)0.1800 (5)1.0241 (11)0.168 (3)
H11A0.96970.23211.09510.252*
H11B0.85520.22750.98010.252*
H11C0.94830.15000.93600.252*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0477 (17)0.0522 (18)0.067 (2)0.0098 (16)0.0056 (15)0.0056 (16)
O10.0505 (14)0.083 (2)0.0864 (18)0.0152 (14)0.0078 (13)0.0173 (15)
O20.0486 (13)0.0644 (16)0.0716 (16)0.0120 (12)0.0016 (12)0.0002 (13)
O30.0464 (14)0.0535 (16)0.129 (2)0.0075 (13)0.0032 (15)0.0043 (15)
O40.0616 (16)0.0751 (19)0.0762 (18)0.0141 (14)0.0031 (13)0.0114 (15)
O50.0777 (19)0.122 (3)0.0578 (16)0.0102 (18)0.0132 (14)0.0087 (17)
C10.049 (2)0.053 (2)0.055 (2)0.0014 (17)0.0129 (17)0.0007 (17)
C20.046 (2)0.0495 (19)0.050 (2)0.0070 (17)0.0095 (16)0.0001 (16)
C30.048 (2)0.047 (2)0.067 (2)0.0037 (16)0.0113 (17)0.0128 (17)
C40.0438 (18)0.0417 (19)0.063 (2)0.0012 (16)0.0124 (16)0.0013 (16)
C50.0383 (17)0.0450 (19)0.0530 (19)0.0048 (15)0.0117 (15)0.0034 (17)
C60.053 (2)0.042 (2)0.086 (3)0.0063 (17)0.0066 (19)0.0125 (18)
C70.058 (2)0.0401 (18)0.098 (3)0.0049 (18)0.012 (2)0.013 (2)
C80.057 (2)0.070 (3)0.054 (2)0.003 (2)0.0060 (19)0.009 (2)
C90.063 (3)0.079 (3)0.102 (3)0.006 (2)0.011 (2)0.019 (2)
C100.063 (3)0.202 (6)0.074 (3)0.012 (4)0.004 (2)0.034 (4)
C110.086 (4)0.085 (4)0.318 (10)0.021 (3)0.016 (5)0.023 (5)
Geometric parameters (Å, º) top
N1—O31.215 (3)C5—C61.406 (4)
N1—O41.221 (3)C6—C71.343 (4)
N1—C51.491 (4)C6—H60.9300
O1—C11.230 (4)C7—H70.9300
O2—C81.370 (4)C8—C91.497 (5)
O2—C21.392 (3)C9—C101.486 (6)
O5—C81.178 (4)C9—H9A0.9700
C1—C71.447 (4)C9—H9B0.9700
C1—C21.466 (5)C10—C111.473 (8)
C2—C31.339 (4)C10—H10A0.9700
C3—C41.415 (4)C10—H10B0.9700
C3—H30.9300C11—H11A0.9600
C4—C51.337 (4)C11—H11B0.9600
C4—H40.9300C11—H11C0.9600
O3—N1—O4123.7 (3)C6—C7—H7114.5
O3—N1—C5118.6 (3)C1—C7—H7114.5
O4—N1—C5117.7 (3)O5—C8—O2122.1 (3)
C8—O2—C2116.8 (3)O5—C8—C9127.0 (4)
O1—C1—C7119.5 (3)O2—C8—C9110.8 (3)
O1—C1—C2119.0 (3)C10—C9—C8113.6 (4)
C7—C1—C2121.5 (3)C10—C9—H9A108.8
C3—C2—O2115.7 (3)C8—C9—H9A108.8
C3—C2—C1130.9 (3)C10—C9—H9B108.8
O2—C2—C1113.1 (3)C8—C9—H9B108.8
C2—C3—C4129.5 (3)H9A—C9—H9B107.7
C2—C3—H3115.2C11—C10—C9113.2 (4)
C4—C3—H3115.2C11—C10—H10A108.9
C5—C4—C3128.3 (3)C9—C10—H10A108.9
C5—C4—H4115.9C11—C10—H10B108.9
C3—C4—H4115.9C9—C10—H10B108.9
C4—C5—C6128.6 (3)H10A—C10—H10B107.7
C4—C5—N1116.2 (3)C10—C11—H11A109.5
C6—C5—N1115.1 (3)C10—C11—H11B109.5
C7—C6—C5129.7 (3)H11A—C11—H11B109.5
C7—C6—H6115.2C10—C11—H11C109.5
C5—C6—H6115.2H11A—C11—H11C109.5
C6—C7—C1131.0 (3)H11B—C11—H11C109.5
C8—O2—C2—C3117.9 (3)O3—N1—C5—C6171.4 (3)
C8—O2—C2—C167.1 (3)O4—N1—C5—C69.5 (4)
O1—C1—C2—C3174.8 (4)C4—C5—C6—C73.9 (6)
C7—C1—C2—C35.1 (5)N1—C5—C6—C7175.3 (4)
O1—C1—C2—O20.8 (4)C5—C6—C7—C13.0 (7)
C7—C1—C2—O2179.1 (3)O1—C1—C7—C6171.7 (4)
O2—C2—C3—C4172.5 (3)C2—C1—C7—C68.2 (6)
C1—C2—C3—C41.4 (6)C2—O2—C8—O513.6 (5)
C2—C3—C4—C52.4 (6)C2—O2—C8—C9169.4 (3)
C3—C4—C5—C62.7 (6)O5—C8—C9—C1032.4 (6)
C3—C4—C5—N1176.5 (3)O2—C8—C9—C10150.8 (4)
O3—N1—C5—C49.3 (4)C8—C9—C10—C1167.5 (6)
O4—N1—C5—C4169.7 (3)

Experimental details

Crystal data
Chemical formulaC11H11NO5
Mr237.21
Crystal system, space groupMonoclinic, P21/a
Temperature (K)296
a, b, c (Å)12.8585 (14), 10.7092 (11), 8.3657 (14)
β (°) 103.052 (11)
V3)1122.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.33 × 0.23 × 0.23
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.981, 1
No. of measured, independent and
observed [I > 2σ(I)] reflections
2559, 2450, 953
Rint0.073
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.168, 0.95
No. of reflections2450
No. of parameters155
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.18

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), Xtal_GX (Hall & du Boulay, 1995), SHELXL97.

 

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