Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003749/tk6006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003749/tk6006Isup2.hkl |
CCDC reference: 162817
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.
All H atoms were fixed at ideal positions and restrained with Uiso held fixed to 1.2Ueq of the parent atoms.
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.
Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids (Johnson, 1976). | |
Fig. 2. Packing diagram of (I) viewed down the b axis. H atoms have been omitted for clarity. |
C11H11NO5 | F(000) = 496 |
Mr = 237.21 | Dx = 1.404 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
a = 12.8585 (14) Å | Cell parameters from 21 reflections |
b = 10.7092 (11) Å | θ = 9.1–18.1° |
c = 8.3657 (14) Å | µ = 0.11 mm−1 |
β = 103.052 (11)° | T = 296 K |
V = 1122.2 (3) Å3 | Prism, yellow |
Z = 4 | 0.33 × 0.23 × 0.23 mm |
Enraf-Nonius CAD-4 diffractometer | 953 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.073 |
Graphite monochromator | θmax = 27.0°, θmin = 3.1° |
ω–2θ scans | h = 0→16 |
Absorption correction: ψ scan (North et al., 1968) | k = −13→0 |
Tmin = 0.981, Tmax = 1 | l = −10→10 |
2559 measured reflections | 3 standard reflections every 120 min |
2450 independent reflections | intensity decay: 0.1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-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 reflections | Δρmax = 0.19 e Å−3 |
155 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.018 (3) |
C11H11NO5 | V = 1122.2 (3) Å3 |
Mr = 237.21 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 12.8585 (14) Å | µ = 0.11 mm−1 |
b = 10.7092 (11) Å | T = 296 K |
c = 8.3657 (14) Å | 0.33 × 0.23 × 0.23 mm |
β = 103.052 (11)° |
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 = 1 | 3 standard reflections every 120 min |
2559 measured reflections | intensity decay: 0.1% |
2450 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.19 e Å−3 |
2450 reflections | Δρmin = −0.18 e Å−3 |
155 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2129 (2) | 0.1110 (3) | 0.4515 (4) | 0.0569 (8) | |
O1 | 0.66475 (19) | 0.2185 (2) | 0.7017 (3) | 0.0744 (8) | |
O2 | 0.65022 (17) | −0.0067 (2) | 0.8162 (3) | 0.0640 (7) | |
O3 | 0.15680 (19) | 0.0242 (2) | 0.4730 (4) | 0.0788 (9) | |
O4 | 0.18189 (18) | 0.1968 (2) | 0.3565 (3) | 0.0739 (8) | |
O5 | 0.6630 (2) | 0.1186 (3) | 1.0328 (3) | 0.0863 (9) | |
C1 | 0.5734 (3) | 0.1770 (3) | 0.6764 (4) | 0.0522 (9) | |
C2 | 0.5561 (3) | 0.0518 (3) | 0.7365 (4) | 0.0487 (8) | |
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* |
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) |
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 |
O1—C1 | 1.230 (4) | C7—H7 | 0.9300 |
O2—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) |
C2—C3—C4—C5 | −2.4 (6) | C2—O2—C8—C9 | −169.4 (3) |
C3—C4—C5—C6 | −2.7 (6) | O5—C8—C9—C10 | −32.4 (6) |
C3—C4—C5—N1 | 176.5 (3) | O2—C8—C9—C10 | 150.8 (4) |
O3—N1—C5—C4 | 9.3 (4) | C8—C9—C10—C11 | −67.5 (6) |
O4—N1—C5—C4 | −169.7 (3) |
Experimental details
Crystal data | |
Chemical formula | C11H11NO5 |
Mr | 237.21 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 296 |
a, b, c (Å) | 12.8585 (14), 10.7092 (11), 8.3657 (14) |
β (°) | 103.052 (11) |
V (Å3) | 1122.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.33 × 0.23 × 0.23 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.981, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2559, 2450, 953 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.168, 0.95 |
No. of reflections | 2450 |
No. of parameters | 155 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
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 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.