organic papers
o326
Kubo, Tsuruta and Mori C11H11NO5 DOI: 101107/S1600536801003749 Acta Cryst.(2001). E57, o326±o327 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
2-Butanoyloxy-5-nitrotropone
Kanji Kubo,a* Tetsuya Tsurutab and Akira Moria²
aInstitute of Advanced Material Study, 86,
Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan, andbGraduate
School of Engineering Sciences, 39, Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan
² Additional correspondence author.
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 296 K
Mean(C±C) = 0.006 AÊ Rfactor = 0.055 wRfactor = 0.168
Data-to-parameter ratio = 15.8
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved
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 paraf®n chain has trans and gauche conformations. Intermolecular±interactions between the tropolone planes are observed in the crystalline state.
Comment
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 & Take-shita, 1995; Hashimotoet al., 2000). The crystal structures of cores such as tropolone, 5-nitrotropolone and 5-cyano-tropolone rings have been elucidated by X-ray analyses (Shimanouchi & Sasada, 1973; Kuboet 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 the least-squares plane A, de®ned by atoms C1±C7/O1/O2, are 0.033 (4), 0.064 (4), 0.048 (4), ÿ0.031 (5), ÿ0.064 (4), 0.022 (4), 0.083 (5), ÿ0.040 (3) and ÿ0.015 (3) AÊ. The dihedral angle between the least-squares planes throughAandB[de®ned by atoms O2, O5 and C8] is 71.8 (1), which is similar to that in
tropolonyl p-chlorobenzoate, 71.5 (Shaefer & Reed, 1971).
The CÐC 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 (Kuboet al., 2001). The paraf®n chain hastransandgaucheconformations.
Intermolecular±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) AÊ for C1ÐC4i[symmetry code: (i) 1ÿx,ÿy, 1ÿz],
which is similar to the distance of 3.40 AÊ found in 5-nitro-tropolone (Kuboet al., 2001). However, the packing in (I) is distinct from that of 5-nitrotropolone (Kubo et al., 2001), which features intermolecular NO2 ±interactions. Thus,
the substitution at O2 results in a different crystal-packing arrangement.
Experimental
Compound (I) was prepared by esteri®cation of 5-nitrotropolone with butanoyl chloride. The single crystals of (I) were obtained by recrystallization from a chloroform solution of the compound.
Crystal data C11H11NO5 Mr= 237.21 Monoclinic,P21/a a= 12.8585 (14) AÊ b= 10.7092 (11) AÊ c= 8.3657 (14) AÊ
= 103.052 (11)
V= 1122.2 (3) AÊ3 Z= 4
Dx= 1.404 Mg mÿ3
MoKradiation Cell parameters from 21
re¯ections
= 9.1±18.1
= 0.11 mmÿ1 T= 296 (2) K Prism, yellow 0.330.230.23 mm Data collection
Enraf±Nonius CAD-4 diffract-ometer
!±2scans
scan (Northet al., 1968) Tmin= 0.981,Tmax= 1.000
2559 measured re¯ections 2450 independent re¯ections 953 re¯ections withI> 2(I)
Rint= 0.073
max= 27.0 h= 0!16 k=ÿ13!0 l=ÿ10!10 3 standard re¯ections
frequency: 120 min intensity decay: 0.1% Re®nement
Re®nement onF2 R[F2> 2(F2)] = 0.055 wR(F2) = 0.168 S= 0.95 2450 re¯ections 155 parameters
H-atom parameters constrained
w= 1/[2(Fo2) + (0.0673P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.19 e AÊÿ3 min=ÿ0.18 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.018 (3)
All H atoms were ®xed at ideal positions and restrained withUiso held ®xed to 1.2Ueqof the parent atoms.
Data collection: CAD-4 Software (Enraf±Nonius, 1989); cell re®nement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure:SIR97 (Altomareet al., 1999); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:Xtal_GX(Hall & du Boulay, 1995); software used to prepare material for publication:SHELXL97.
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999).J. Appl. Cryst.32, 115±119.
Barrow, M. J., Mills, O. S. & Filippini, G. (1973).J. Chem. Soc. Chem. Commun. pp. 66±67.
Enraf±Nonius (1989).CAD-4Software. Version 5.0. Enraf±Nonius, Delft, The Netherlands.
Fair, C. K. (1990).MolEN.Enraf±Nonius, Delft, The Netherlands.
Hall, S. R. & du Boulay, D. (1995).Xtal_GX. University of Western Australia, Australia.
Hashimoto, M., Ujiie, S. & Mori, A. (2000).Chem. Lett.pp. 758±759. Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
Kubo, K. & Yamamoto, E. & Mori, A. (2001).Acta Cryst.C57. Accepted. Mori, A. & Takeshita, H. (1995).J. Synth. Org. Chem. Jpn,53, 197±206. North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351±
359.
Shaefer, J. P. & Reed, L. L. (1971).J. Am. Chem. Soc.93, 3902±3904. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Shimanouchi, H. & Sasada, Y. (1973).Acta Cryst.B29, 81±90.
Figure 2
Packing diagram of (I) viewed down the baxis. H atoms have been omitted for clarity.
Figure 1
supporting information
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Acta Cryst. (2001). E57, o326–o327supporting information
Acta Cryst. (2001). E57, o326–o327 [doi:10.1107/S1600536801003749]
2-Butanoyloxy-5-nitrotropone
Kanji Kubo, Tetsuya Tsuruta and Akira Mori
S1. Comment
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-nitro-tropolone, 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 π–π 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 NO2—π–π interactions. Thus, the
substitution at O2 results in a different crystal-packing arrangement.
S2. Experimental
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.
S3. Refinement
Figure 1
The molecular structure of (I) showing 50% probability displacement ellipsoids (Johnson, 1976).
Figure 2
Packing diagram of (I) viewed down the b axis. H atoms have been omitted for clarity.
(I)
Crystal data
C11H11NO5
Mr = 237.21
Monoclinic, P21/a
[image:4.610.113.483.286.595.2]supporting information
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Acta Cryst. (2001). E57, o326–o327β = 103.052 (11)° V = 1122.2 (3) Å3
Z = 4 F(000) = 496 Dx = 1.404 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 21 reflections θ = 9.1–18.1°
µ = 0.11 mm−1
T = 296 K Prism, yellow
0.33 × 0.23 × 0.23 mm
Data collection
Enraf-Nonius CAD-4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω–2θ scans
Absorption correction: ψ scan (North et al., 1968)
Tmin = 0.981, Tmax = 1
2559 measured reflections
2450 independent reflections 953 reflections with I > 2σ(I) Rint = 0.073
θmax = 27.0°, θmin = 3.1°
h = 0→16 k = −13→0 l = −10→10
3 standard reflections every 120 min intensity decay: 0.1%
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.055
wR(F2) = 0.168
S = 0.95 2450 reflections 155 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0673P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.19 e Å−3
Δρmin = −0.18 e Å−3
Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.018 (3)
Special details
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)
x y z Uiso*/Ueq
C3 0.4674 (2) −0.0177 (3) 0.7161 (4) 0.0544 (9)
H3 0.4760 −0.0947 0.7688 0.065*
C4 0.3627 (2) 0.0088 (3) 0.6261 (4) 0.0494 (8)
H4 0.3126 −0.0541 0.6242 0.059*
C5 0.3266 (2) 0.1128 (3) 0.5436 (4) 0.0452 (8) C6 0.3820 (3) 0.2241 (3) 0.5300 (4) 0.0615 (10)
H6 0.3409 0.2877 0.4719 0.074*
C7 0.4855 (3) 0.2521 (3) 0.5882 (5) 0.0663 (10)
H7 0.5037 0.3338 0.5685 0.080*
C8 0.7031 (3) 0.0443 (4) 0.9621 (5) 0.0616 (10) C9 0.8117 (3) −0.0124 (4) 1.0177 (6) 0.0858 (13)
H9A 0.8060 −0.0867 1.0816 0.103*
H9B 0.8371 −0.0381 0.9221 0.103*
C10 0.8914 (4) 0.0733 (7) 1.1180 (5) 0.116 (2)
H10A 0.8634 0.1045 1.2087 0.139*
H10B 0.9559 0.0267 1.1637 0.139*
C11 0.9185 (4) 0.1800 (5) 1.0241 (11) 0.168 (3)
H11A 0.9697 0.2321 1.0951 0.252*
H11B 0.8552 0.2275 0.9801 0.252*
H11C 0.9483 0.1500 0.9360 0.252*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
N1 0.0477 (17) 0.0522 (18) 0.067 (2) 0.0098 (16) 0.0056 (15) −0.0056 (16) O1 0.0505 (14) 0.083 (2) 0.0864 (18) −0.0152 (14) 0.0078 (13) 0.0173 (15) O2 0.0486 (13) 0.0644 (16) 0.0716 (16) 0.0120 (12) −0.0016 (12) 0.0002 (13) O3 0.0464 (14) 0.0535 (16) 0.129 (2) −0.0075 (13) 0.0032 (15) 0.0043 (15) O4 0.0616 (16) 0.0751 (19) 0.0762 (18) 0.0141 (14) −0.0031 (13) 0.0114 (15) O5 0.0777 (19) 0.122 (3) 0.0578 (16) 0.0102 (18) 0.0132 (14) −0.0087 (17) C1 0.049 (2) 0.053 (2) 0.055 (2) −0.0014 (17) 0.0129 (17) 0.0007 (17) C2 0.046 (2) 0.0495 (19) 0.050 (2) 0.0070 (17) 0.0095 (16) −0.0001 (16) C3 0.048 (2) 0.047 (2) 0.067 (2) 0.0037 (16) 0.0113 (17) 0.0128 (17) C4 0.0438 (18) 0.0417 (19) 0.063 (2) −0.0012 (16) 0.0124 (16) 0.0013 (16) C5 0.0383 (17) 0.0450 (19) 0.0530 (19) 0.0048 (15) 0.0117 (15) −0.0034 (17) C6 0.053 (2) 0.042 (2) 0.086 (3) 0.0063 (17) 0.0066 (19) 0.0125 (18) C7 0.058 (2) 0.0401 (18) 0.098 (3) −0.0049 (18) 0.012 (2) 0.013 (2) C8 0.057 (2) 0.070 (3) 0.054 (2) 0.003 (2) 0.0060 (19) 0.009 (2) C9 0.063 (3) 0.079 (3) 0.102 (3) 0.006 (2) −0.011 (2) 0.019 (2) C10 0.063 (3) 0.202 (6) 0.074 (3) 0.012 (4) −0.004 (2) −0.034 (4) C11 0.086 (4) 0.085 (4) 0.318 (10) −0.021 (3) 0.016 (5) −0.023 (5)
Geometric parameters (Å, º)
N1—O3 1.215 (3) C5—C6 1.406 (4)
N1—O4 1.221 (3) C6—C7 1.343 (4)
N1—C5 1.491 (4) C6—H6 0.9300
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Acta Cryst. (2001). E57, o326–o327O2—C8 1.370 (4) C8—C9 1.497 (5)
O2—C2 1.392 (3) C9—C10 1.486 (6)
O5—C8 1.178 (4) C9—H9A 0.9700
C1—C7 1.447 (4) C9—H9B 0.9700
C1—C2 1.466 (5) C10—C11 1.473 (8)
C2—C3 1.339 (4) C10—H10A 0.9700
C3—C4 1.415 (4) C10—H10B 0.9700
C3—H3 0.9300 C11—H11A 0.9600
C4—C5 1.337 (4) C11—H11B 0.9600
C4—H4 0.9300 C11—H11C 0.9600
O3—N1—O4 123.7 (3) C6—C7—H7 114.5
O3—N1—C5 118.6 (3) C1—C7—H7 114.5
O4—N1—C5 117.7 (3) O5—C8—O2 122.1 (3)
C8—O2—C2 116.8 (3) O5—C8—C9 127.0 (4)
O1—C1—C7 119.5 (3) O2—C8—C9 110.8 (3)
O1—C1—C2 119.0 (3) C10—C9—C8 113.6 (4)
C7—C1—C2 121.5 (3) C10—C9—H9A 108.8
C3—C2—O2 115.7 (3) C8—C9—H9A 108.8
C3—C2—C1 130.9 (3) C10—C9—H9B 108.8
O2—C2—C1 113.1 (3) C8—C9—H9B 108.8
C2—C3—C4 129.5 (3) H9A—C9—H9B 107.7
C2—C3—H3 115.2 C11—C10—C9 113.2 (4)
C4—C3—H3 115.2 C11—C10—H10A 108.9
C5—C4—C3 128.3 (3) C9—C10—H10A 108.9
C5—C4—H4 115.9 C11—C10—H10B 108.9
C3—C4—H4 115.9 C9—C10—H10B 108.9
C4—C5—C6 128.6 (3) H10A—C10—H10B 107.7
C4—C5—N1 116.2 (3) C10—C11—H11A 109.5
C6—C5—N1 115.1 (3) C10—C11—H11B 109.5
C7—C6—C5 129.7 (3) H11A—C11—H11B 109.5
C7—C6—H6 115.2 C10—C11—H11C 109.5
C5—C6—H6 115.2 H11A—C11—H11C 109.5
C6—C7—C1 131.0 (3) H11B—C11—H11C 109.5
C8—O2—C2—C3 −117.9 (3) O3—N1—C5—C6 −171.4 (3)
C8—O2—C2—C1 67.1 (3) O4—N1—C5—C6 9.5 (4)
O1—C1—C2—C3 −174.8 (4) C4—C5—C6—C7 3.9 (6)
C7—C1—C2—C3 5.1 (5) N1—C5—C6—C7 −175.3 (4)
O1—C1—C2—O2 −0.8 (4) C5—C6—C7—C1 3.0 (7)
C7—C1—C2—O2 179.1 (3) O1—C1—C7—C6 171.7 (4) O2—C2—C3—C4 −172.5 (3) C2—C1—C7—C6 −8.2 (6)
C1—C2—C3—C4 1.4 (6) C2—O2—C8—O5 13.6 (5)
