organic compounds
Ethyl 9-dicyanomethylene-2,5,7-trinitrofluorene-4-carboxylate
aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England, and bL. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, Donetsk 83114, Ukraine
*Correspondence e-mail: a.s.batsanov@durham.ac.uk
The title compound, C19H9N5O8, has a warped fluorene ring system due to steric repulsion between the 4-ethoxycarbonyl and 5-nitro groups.
Comment
The title compound, (I), has been obtained in the course of our studies of electron acceptors of the fluorene series and their charge-transfer complexes and salts with π-electron donors, e.g. tetrathiafulvalene family donors (Perepichka et al., 1998, 2000, 2002; Batsanov et al., 2001, 2002; Kuz'mina et al., 2002).
The molecular structure of (I) is strongly influenced by steric repulsion between the nitro and ethoxycarbonyl groups in positions 4 and 5, respectively. This overcrowding, indicated, for example, by the short (intramolecular) non-bonding distances N4⋯O5 [2.730 (5) Å] and C17⋯O4 [2.711 (6) Å], causes the above-mentioned substituents to tilt out of the fluorene plane in opposite directions. Furthermore, the fluorene aromatic system itself loses planarity and adopts a warped (twisted) conformation, the deviations (Å) of its C atoms from the mean plane being: C1 −0.186 (4), C2 −0.149 (4), C3 0.135 (4), C4 0.245 (4), C5 −0.226 (4), C6 −0.145 (4), C7 0.070 (4), C8 0.138 (4), C9 0.033 (4), C10 −0.039 (4), C11 0.060 (5), C12 −0.013 (5) and C13 0.078 (4). Similar distortions are typical for other fluorene derivatives with bulky substituents in positions 4 and 5, e.g. 9-dicyanomethylene-2,4,5,7-tetranitrofluorene (Silverman et al., 1974; Batsanov et al., 2001), 9-dicyanomethylene-4,5-dinitrofluorene-2,7-disulfonamide (Batsanov & Perepichka, 2004) or 9-dicyanomethylene-4-bromo-2,5,7-trinitrofluorene (Perepichka et al., 2002).
Experimental
To a suspension of 2,5,7-trinitro-9-oxofluorene-4-carboxylic acid (10.0 g, 27.8 mmol), (II), in thionyl chloride (50 ml) a catalytic amount of N,N-dimethylformamide (2 drops) was added. The mixture was refluxed for 2 h (full dissolution occurring in 15–20 min) and then evaporated under reduced pressure until dry. Ethanol (50 ml) was added to the residue, the mixture was refluxed for 3 h and left to cool for crystallization. The precipitate was filtered off, washed with cold ethanol (2 × 20 ml) and dried to yield crude compound (III) (9.1 g, 84%; m.p. 426–430 K). This was dissolved in boiling dioxane (25 ml), filtered hot and the filtrate was diluted with hot ethanol (100 ml). On cooling, the solid was filtered off, washed with ethanol and dried. This procedure was repeated to give pure compound (III) (7.2 g, 67%) as yellow crystals (m.p. 434–435 K). 1H NMR (200 MHz, acetone-d6): δ 8.99 (1H, d, J = 2.0 Hz, H-3), 8.83 (1H, d, J = 2.0 Hz, H-6), 8.78 (1H, d, J = 2.2 Hz, H-8), 8.69 (1H, d, J = 2.2 Hz, H-1), 4.42 (2H, q, J = 7.2 Hz, CH2), 1.43 (3H, t, J = 7.2 Hz, CH3). 13C NMR (50 MHz, acetone-d6): δ 186.21 (C=O), 165.44 (–CO2–), 150.71, 150.56, 147.36, 144.19, 140.30, 140.08, 139.18, 132.90, 131.05, 126.38, 122.95, 122.00, 63.84 (CH2), 14.32 (CH3). MS (EI): m/z 387 (M+, 100%). HRMS (EI): m/z 387.03447; calculated exact mass: 387.03388. Analysis found: C 49.52, H 2.40, N 10.89%; C16H9N3O9 requires: C 49.62, H 2.34, N 10.85%.
Compound (III) (5.0 g, 12.9 mmol) was dissolved in N,N-dimethylformamide (25 ml), malonitrile (2.2 g, 33.3 mmol) was added to this solution and the mixture was stirred at room temperature for 1 h (the product began to precipitate in 30 min). 2-Propanol (100 ml) was added to the mixture and it was allowed to stand at 273 K for 1–2 h. The solid was filtered off, washed with 2-propanol and dried to yield crude compound (I) (5.2 g, 93%; m.p. 539–543 K). It was dissolved in boiling dioxane (75 ml), hot 2-propanol was added to the solution and the product left to crystallize. The solid was filtered off, washed with 2-propanol and dried. The purification procedure was repeated once more, to afford pure compound (I) (4.8 g, 85%) as bright-yellow crystals (m.p. 543–545 K). 1H NMR (200 MHz, acetone-d6 + half a drop CF3CO2D): δ 9.69 (1H, d, J = 2.0 Hz, H-8), 9.60 (1H, d, J = 2.0 Hz, H-1), 9.04 (1H, d, J = 2.0 Hz, H-6), 8.88 (1H, d J = 2.0 Hz, H-3), 4.43 (2H, q, J = 7.2 Hz, CH2), 1.44 (3H, t, J = 7.2 Hz, CH3). 13C NMR (100 MHz, acetone-d6 + 0.5 drop CF3CO2D): δ 165.30 (–CO2–), 154.81, 141.14, 140.14, 139.25, 137.49, 133.05, 130.49, 125.76, 124.75, 123.70, 121.52, 117.74, 113.96, 113.37, 113.32, 110.17, 63.96 (CH2), 14.36 (CH3). MS (EI): m/z 435 (M+, 100%). Analysis found: C 52.52, H 2.03, N 16.15%; C19H9N5O8 requires: C 52.42, H 2.08, N 16.09%. Compound (I) was dissolved in hot acetonitrile and left to cool slowly to yield single crystals of X-ray quality.
Crystal data
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Data collection
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Refinement
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The diffraction was rather weak, with a mean I/σ(I) ratio of 5.2. The methyl group was refined as a rigid body (C—H = 0.98 Å) rotating around the C—C bond, with a common (refined) Uiso value for all three H atoms. Other H atoms were treated as riding in idealized positions, with Csp3—H = 0.99 Å and Csp2—H = 0.95 Å, and Uiso(H) = 1.3Ueq(C) and 1.2Ueq(C), respectively.
Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536806003175/bt6807sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806003175/bt6807Isup2.hkl
Data collection: SMART (Bruker, 1997); cell
SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.C19H9N5O8 | F(000) = 888 |
Mr = 435.31 | Dx = 1.615 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1107 reflections |
a = 19.481 (2) Å | θ = 3.1–22.6° |
b = 8.620 (1) Å | µ = 0.13 mm−1 |
c = 10.814 (1) Å | T = 110 K |
β = 99.40 (1)° | Prism, yellow |
V = 1791.6 (3) Å3 | 0.18 × 0.07 × 0.07 mm |
Z = 4 |
Bruker SMART 1 K CCD area-detector diffractometer | 1518 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.126 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
Detector resolution: 8 pixels mm-1 | h = −13→22 |
ω scans | k = −9→10 |
7993 measured reflections | l = −12→12 |
3079 independent reflections |
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)] = 0.067 | H-atom parameters constrained |
wR(F2) = 0.172 | w = 1/[σ2(Fo2) + (0.0632P)2 + 0.5406P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3079 reflections | Δρmax = 0.41 e Å−3 |
292 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.018 (2) |
Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of 4 sets of ω scans; each set at different φ and/or 2θ angles and each scan (46.5 sec exposure) covering 0.3° in ω. Crystal to detector distance 6.03 cm. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.53613 (17) | 0.2322 (4) | 0.2237 (4) | 0.0309 (9) | |
O2 | 0.55693 (17) | 0.2996 (4) | 0.4205 (3) | 0.0321 (10) | |
O3 | 0.34804 (18) | 0.4135 (4) | 0.6081 (3) | 0.0330 (10) | |
O4 | 0.28475 (17) | 0.5939 (4) | 0.5031 (3) | 0.0293 (9) | |
O5 | 0.21531 (18) | 0.2915 (4) | 0.4372 (3) | 0.0323 (10) | |
O6 | 0.13270 (17) | 0.4589 (4) | 0.4749 (3) | 0.0302 (10) | |
O7 | −0.00294 (18) | 0.6632 (5) | 0.0855 (4) | 0.0407 (11) | |
O8 | 0.04476 (17) | 0.6932 (5) | −0.0813 (4) | 0.0385 (11) | |
N2 | 0.5196 (2) | 0.2939 (5) | 0.3175 (5) | 0.0264 (11) | |
N4 | 0.3258 (2) | 0.4838 (5) | 0.5107 (4) | 0.0271 (11) | |
N7 | 0.0466 (2) | 0.6547 (5) | 0.0287 (4) | 0.0309 (12) | |
N15 | 0.4359 (2) | 0.4704 (5) | −0.1171 (4) | 0.0264 (11) | |
N16 | 0.2283 (2) | 0.6451 (5) | −0.2394 (4) | 0.0317 (12) | |
C1 | 0.4162 (2) | 0.4011 (6) | 0.1842 (5) | 0.0216 (12) | |
H1 | 0.4389 | 0.3905 | 0.1133 | 0.026* | |
C2 | 0.4497 (2) | 0.3643 (5) | 0.3044 (5) | 0.0198 (12) | |
C3 | 0.4208 (3) | 0.3903 (6) | 0.4109 (5) | 0.0246 (12) | |
H3 | 0.4471 | 0.3747 | 0.4920 | 0.029* | |
C4 | 0.3523 (2) | 0.4397 (5) | 0.3960 (5) | 0.0202 (12) | |
C5 | 0.1783 (3) | 0.4889 (6) | 0.2876 (5) | 0.0245 (13) | |
C6 | 0.1152 (2) | 0.5433 (6) | 0.2194 (5) | 0.0272 (13) | |
H6 | 0.0741 | 0.5440 | 0.2561 | 0.033* | |
C7 | 0.1136 (2) | 0.5954 (6) | 0.0985 (5) | 0.0225 (12) | |
C8 | 0.1697 (2) | 0.5900 (6) | 0.0349 (5) | 0.0252 (13) | |
H8 | 0.1657 | 0.6200 | −0.0506 | 0.030* | |
C9 | 0.3006 (2) | 0.5089 (6) | 0.0615 (5) | 0.0206 (12) | |
C10 | 0.3476 (2) | 0.4543 (5) | 0.1728 (4) | 0.0190 (12) | |
C11 | 0.3132 (2) | 0.4608 (5) | 0.2780 (4) | 0.0191 (12) | |
C12 | 0.2382 (3) | 0.4980 (6) | 0.2302 (5) | 0.0237 (12) | |
C13 | 0.2325 (2) | 0.5381 (6) | 0.1038 (5) | 0.0204 (12) | |
C14 | 0.3158 (2) | 0.5339 (6) | −0.0545 (5) | 0.0222 (12) | |
C15 | 0.3831 (3) | 0.4987 (6) | −0.0877 (5) | 0.0224 (12) | |
C16 | 0.2665 (3) | 0.5949 (6) | −0.1573 (5) | 0.0235 (12) | |
C17 | 0.1782 (2) | 0.4036 (6) | 0.4085 (5) | 0.0261 (13) | |
C18 | 0.1288 (3) | 0.3746 (6) | 0.5921 (4) | 0.0294 (14) | |
H181 | 0.1753 | 0.3702 | 0.6450 | 0.038* | |
H182 | 0.1123 | 0.2671 | 0.5734 | 0.038* | |
C19 | 0.0786 (3) | 0.4606 (7) | 0.6594 (5) | 0.0380 (15) | |
H191 | 0.0952 | 0.5670 | 0.6766 | 0.049 (10)* | |
H192 | 0.0753 | 0.4081 | 0.7385 | 0.049 (10)* | |
H193 | 0.0327 | 0.4629 | 0.6066 | 0.049 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.025 (2) | 0.034 (2) | 0.036 (2) | 0.0071 (17) | 0.0116 (17) | 0.0019 (19) |
O2 | 0.022 (2) | 0.039 (3) | 0.031 (2) | 0.0037 (18) | −0.0046 (18) | 0.0040 (18) |
O3 | 0.034 (2) | 0.044 (3) | 0.019 (2) | 0.0073 (19) | −0.0010 (16) | 0.0118 (19) |
O4 | 0.023 (2) | 0.038 (2) | 0.028 (2) | 0.0037 (19) | 0.0053 (16) | −0.0030 (18) |
O5 | 0.030 (2) | 0.028 (2) | 0.040 (2) | 0.0083 (19) | 0.0079 (17) | 0.0064 (18) |
O6 | 0.022 (2) | 0.038 (2) | 0.031 (2) | 0.0013 (17) | 0.0063 (17) | 0.0005 (18) |
O7 | 0.019 (2) | 0.058 (3) | 0.046 (3) | 0.0080 (19) | 0.0083 (19) | 0.014 (2) |
O8 | 0.023 (2) | 0.062 (3) | 0.028 (2) | 0.0122 (19) | −0.0031 (17) | 0.006 (2) |
N2 | 0.022 (2) | 0.021 (3) | 0.036 (3) | −0.001 (2) | 0.004 (2) | 0.006 (2) |
N4 | 0.022 (3) | 0.030 (3) | 0.029 (3) | 0.004 (2) | 0.001 (2) | 0.004 (2) |
N7 | 0.020 (3) | 0.039 (3) | 0.033 (3) | 0.005 (2) | 0.001 (2) | 0.005 (2) |
N15 | 0.021 (3) | 0.033 (3) | 0.025 (3) | −0.001 (2) | 0.005 (2) | −0.001 (2) |
N16 | 0.025 (3) | 0.040 (3) | 0.030 (3) | 0.003 (2) | 0.004 (2) | 0.003 (2) |
C1 | 0.019 (3) | 0.015 (3) | 0.030 (3) | 0.000 (2) | 0.001 (2) | 0.000 (2) |
C2 | 0.019 (3) | 0.013 (3) | 0.028 (3) | 0.003 (2) | 0.005 (2) | 0.003 (2) |
C3 | 0.025 (3) | 0.022 (3) | 0.024 (3) | −0.002 (2) | −0.002 (2) | 0.003 (2) |
C4 | 0.021 (3) | 0.015 (3) | 0.023 (3) | 0.002 (2) | 0.001 (2) | −0.001 (2) |
C5 | 0.019 (3) | 0.028 (3) | 0.028 (3) | 0.003 (2) | 0.008 (2) | 0.001 (2) |
C6 | 0.015 (3) | 0.036 (4) | 0.031 (3) | 0.000 (2) | 0.005 (2) | −0.003 (3) |
C7 | 0.015 (3) | 0.029 (3) | 0.023 (3) | 0.003 (2) | −0.001 (2) | 0.000 (2) |
C8 | 0.021 (3) | 0.033 (3) | 0.020 (3) | −0.004 (2) | −0.001 (2) | −0.001 (2) |
C9 | 0.013 (3) | 0.019 (3) | 0.030 (3) | −0.002 (2) | 0.003 (2) | −0.005 (2) |
C10 | 0.014 (3) | 0.019 (3) | 0.023 (3) | −0.003 (2) | 0.000 (2) | −0.002 (2) |
C11 | 0.018 (3) | 0.016 (3) | 0.024 (3) | 0.004 (2) | 0.006 (2) | −0.001 (2) |
C12 | 0.022 (3) | 0.023 (3) | 0.025 (3) | 0.005 (2) | 0.001 (2) | −0.002 (2) |
C13 | 0.020 (3) | 0.019 (3) | 0.022 (3) | −0.002 (2) | 0.001 (2) | −0.001 (2) |
C14 | 0.021 (3) | 0.022 (3) | 0.024 (3) | −0.003 (2) | 0.003 (2) | 0.000 (2) |
C15 | 0.023 (3) | 0.025 (3) | 0.018 (3) | −0.002 (2) | −0.002 (2) | 0.003 (2) |
C16 | 0.018 (3) | 0.029 (3) | 0.023 (3) | −0.001 (2) | 0.001 (2) | −0.005 (3) |
C17 | 0.012 (3) | 0.032 (4) | 0.034 (3) | −0.003 (3) | 0.004 (2) | −0.002 (3) |
C18 | 0.028 (3) | 0.040 (4) | 0.020 (3) | −0.004 (3) | 0.001 (2) | 0.007 (3) |
C19 | 0.036 (3) | 0.052 (4) | 0.027 (3) | −0.007 (3) | 0.010 (3) | 0.002 (3) |
O1—N2 | 1.234 (5) | C5—C12 | 1.412 (7) |
O2—N2 | 1.228 (5) | C5—C17 | 1.500 (7) |
O3—N4 | 1.231 (5) | C6—C7 | 1.378 (7) |
O4—N4 | 1.235 (5) | C6—H6 | 0.9500 |
O5—C17 | 1.217 (6) | C7—C8 | 1.384 (6) |
O6—C17 | 1.317 (6) | C8—C13 | 1.398 (7) |
O6—C18 | 1.474 (6) | C8—H8 | 0.9500 |
O7—N7 | 1.228 (5) | C9—C14 | 1.352 (7) |
O8—N7 | 1.230 (5) | C9—C10 | 1.465 (7) |
N2—C2 | 1.476 (6) | C9—C13 | 1.495 (6) |
N4—C4 | 1.469 (6) | C10—C11 | 1.412 (6) |
N7—C7 | 1.487 (6) | C11—C12 | 1.502 (7) |
N15—C15 | 1.152 (6) | C12—C13 | 1.397 (7) |
N16—C16 | 1.147 (6) | C14—C16 | 1.444 (7) |
C1—C2 | 1.393 (6) | C14—C15 | 1.446 (7) |
C1—C10 | 1.401 (6) | C18—C19 | 1.505 (7) |
C1—H1 | 0.9501 | C18—H181 | 0.9900 |
C2—C3 | 1.381 (6) | C18—H182 | 0.9900 |
C3—C4 | 1.385 (6) | C19—H191 | 0.9800 |
C3—H3 | 0.9500 | C19—H192 | 0.9800 |
C4—C11 | 1.388 (6) | C19—H193 | 0.9799 |
C5—C6 | 1.407 (7) | ||
C17—O6—C18 | 115.1 (4) | C14—C9—C13 | 126.6 (4) |
O2—N2—O1 | 124.6 (4) | C10—C9—C13 | 105.6 (4) |
O2—N2—C2 | 118.1 (4) | C1—C10—C11 | 120.9 (4) |
O1—N2—C2 | 117.3 (4) | C1—C10—C9 | 129.5 (4) |
O3—N4—O4 | 124.7 (4) | C11—C10—C9 | 109.6 (4) |
O3—N4—C4 | 118.1 (4) | C4—C11—C10 | 118.3 (4) |
O4—N4—C4 | 117.1 (4) | C4—C11—C12 | 134.5 (4) |
O7—N7—O8 | 124.5 (4) | C10—C11—C12 | 107.1 (4) |
O7—N7—C7 | 117.6 (4) | C13—C12—C5 | 120.3 (4) |
O8—N7—C7 | 117.9 (4) | C13—C12—C11 | 107.9 (4) |
C2—C1—C10 | 116.9 (4) | C5—C12—C11 | 131.6 (5) |
C2—C1—H1 | 121.5 | C12—C13—C8 | 121.6 (4) |
C10—C1—H1 | 121.7 | C12—C13—C9 | 108.9 (4) |
C3—C2—C1 | 123.3 (4) | C8—C13—C9 | 129.4 (5) |
C3—C2—N2 | 118.8 (4) | C9—C14—C16 | 123.6 (4) |
C1—C2—N2 | 117.9 (4) | C9—C14—C15 | 122.7 (4) |
C2—C3—C4 | 118.0 (5) | C16—C14—C15 | 113.7 (4) |
C2—C3—H3 | 121.0 | N15—C15—C14 | 178.3 (5) |
C4—C3—H3 | 121.0 | N16—C16—C14 | 178.7 (6) |
C3—C4—C11 | 121.4 (4) | O5—C17—O6 | 125.0 (5) |
C3—C4—N4 | 116.5 (4) | O5—C17—C5 | 121.7 (5) |
C11—C4—N4 | 121.8 (4) | O6—C17—C5 | 113.2 (5) |
C6—C5—C12 | 117.7 (5) | O6—C18—C19 | 107.6 (4) |
C6—C5—C17 | 119.7 (4) | O6—C18—H181 | 110.2 |
C12—C5—C17 | 122.0 (4) | C19—C18—H181 | 110.1 |
C7—C6—C5 | 119.2 (5) | O6—C18—H182 | 110.3 |
C7—C6—H6 | 120.3 | C19—C18—H182 | 110.2 |
C5—C6—H6 | 120.4 | H181—C18—H182 | 108.5 |
C6—C7—C8 | 124.3 (5) | C18—C19—H191 | 109.5 |
C6—C7—N7 | 118.4 (4) | C18—C19—H192 | 109.6 |
C8—C7—N7 | 117.2 (5) | H191—C19—H192 | 109.5 |
C7—C8—C13 | 116.0 (5) | C18—C19—H193 | 109.4 |
C7—C8—H8 | 122.0 | H191—C19—H193 | 109.5 |
C13—C8—H8 | 122.0 | H192—C19—H193 | 109.5 |
C14—C9—C10 | 127.7 (4) | ||
C10—C1—C2—C3 | −5.7 (7) | C1—C10—C11—C4 | 11.1 (7) |
C10—C1—C2—N2 | 174.2 (4) | C9—C10—C11—C4 | −169.1 (4) |
O2—N2—C2—C3 | −19.5 (6) | C1—C10—C11—C12 | −171.2 (4) |
O1—N2—C2—C3 | 160.0 (4) | C9—C10—C11—C12 | 8.6 (5) |
O2—N2—C2—C1 | 160.6 (4) | C6—C5—C12—C13 | −9.2 (7) |
O1—N2—C2—C1 | −19.9 (6) | C17—C5—C12—C13 | 161.8 (5) |
C1—C2—C3—C4 | 7.2 (7) | C6—C5—C12—C11 | 175.6 (5) |
N2—C2—C3—C4 | −172.7 (4) | C17—C5—C12—C11 | −13.4 (9) |
C2—C3—C4—C11 | 0.8 (7) | C4—C11—C12—C13 | 167.2 (5) |
C2—C3—C4—N4 | −173.0 (4) | C10—C11—C12—C13 | −9.9 (5) |
O3—N4—C4—C3 | −33.3 (6) | C4—C11—C12—C5 | −17.1 (10) |
O4—N4—C4—C3 | 143.6 (4) | C10—C11—C12—C5 | 165.8 (5) |
O3—N4—C4—C11 | 152.9 (5) | C5—C12—C13—C8 | 8.5 (8) |
O4—N4—C4—C11 | −30.2 (6) | C11—C12—C13—C8 | −175.2 (4) |
C12—C5—C6—C7 | 3.2 (8) | C5—C12—C13—C9 | −169.0 (4) |
C17—C5—C6—C7 | −168.0 (5) | C11—C12—C13—C9 | 7.2 (5) |
C5—C6—C7—C8 | 4.0 (8) | C7—C8—C13—C12 | −1.5 (7) |
C5—C6—C7—N7 | −179.1 (4) | C7—C8—C13—C9 | 175.5 (5) |
O7—N7—C7—C6 | 4.4 (7) | C14—C9—C13—C12 | −179.7 (5) |
O8—N7—C7—C6 | −176.2 (5) | C10—C9—C13—C12 | −2.0 (5) |
O7—N7—C7—C8 | −178.4 (5) | C14—C9—C13—C8 | 3.0 (8) |
O8—N7—C7—C8 | 1.0 (7) | C10—C9—C13—C8 | −179.4 (5) |
C6—C7—C8—C13 | −4.8 (8) | C10—C9—C14—C16 | −177.0 (5) |
N7—C7—C8—C13 | 178.2 (4) | C13—C9—C14—C16 | 0.1 (8) |
C2—C1—C10—C11 | −3.7 (7) | C10—C9—C14—C15 | 4.3 (8) |
C2—C1—C10—C9 | 176.5 (5) | C13—C9—C14—C15 | −178.5 (5) |
C14—C9—C10—C1 | −6.9 (9) | C18—O6—C17—O5 | 0.3 (7) |
C13—C9—C10—C1 | 175.5 (5) | C18—O6—C17—C5 | 177.6 (4) |
C14—C9—C10—C11 | 173.3 (5) | C6—C5—C17—O5 | 140.5 (5) |
C13—C9—C10—C11 | −4.3 (5) | C12—C5—C17—O5 | −30.4 (8) |
C3—C4—C11—C10 | −9.7 (7) | C6—C5—C17—O6 | −36.9 (7) |
N4—C4—C11—C10 | 163.8 (4) | C12—C5—C17—O6 | 152.2 (5) |
C3—C4—C11—C12 | 173.5 (5) | C17—O6—C18—C19 | 175.8 (4) |
N4—C4—C11—C12 | −13.0 (8) |
Acknowledgements
The authors thank Professor M. R. Bryce for fruitful advice.
References
Batsanov, A. S., Bryce, M. R., Lyubchik, S. B. & Perepichka, I. F. (2002). Acta Cryst. E58, o1106–o1110. Web of Science CSD CrossRef IUCr Journals Google Scholar
Batsanov, A. S. & Perepichka, I. F. (2004). Acta Cryst. E60, o1892–o1894. Web of Science CSD CrossRef IUCr Journals Google Scholar
Batsanov, A. S., Perepichka, I. F., Bryce, M. R. & Howard, J. A. K. (2001). Acta Cryst. C57, 1299–1302. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bruker (1997). SMART (Version 5.054) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Version 6.01. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kuz'mina, L. G., Perepichka, I. F., Perepichka, D. F., Howard, J. A. K. & Bryce, M. R. (2002). Crystallogr. Rep. 47, 251–261. Web of Science CrossRef CAS Google Scholar
Perepichka, D. F., Bryce, M. R., Perepichka, I. F., Lyubchik, S. B., Christensen, C. A., Godbert, N., Batsanov, A. S., Levillain, E., McInnes, E. J. L. & Zhao, J. P. (2002). J. Am. Chem. Soc. 124, 14227–14238. Web of Science CSD CrossRef PubMed CAS Google Scholar
Perepichka, I. F., Kuz'mina, L. G., Perepichka, D. F., Bryce, M. R., Goldenberg, L. M., Popov, A. F. & Howard, J. A. K. (1998). J. Org. Chem. 63, 6484–6493. Web of Science CSD CrossRef CAS Google Scholar
Perepichka, I. F., Popov, A. F., Orekhova, T. V., Bryce, M. R., Andrievskii, A. M., Batsanov, A. S., Howard, J. A. K. & Sokolov, N. I. (2000). J. Org. Chem. 65, 3053–3063. Web of Science CSD CrossRef PubMed CAS Google Scholar
Silverman, J., Yannoni, N. F. & Krukonis, A. P. (1974). Acta Cryst. B30, 1474–1480. CSD CrossRef IUCr Journals Web of Science Google Scholar
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